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Proceedings of the Chemical Society, Vol. 20, No. 274 |
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Proceedings of the Chemical Society, London,
Volume 20,
Issue 274,
1904,
Page 1-16
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摘要:
Issued 301 1/04 PROCEEDINGS OF THE CHEMICAL SOCIETY. VOl. 19. No. 274. Wednesday, January 20th, 1904. Professor W, A. TILDEN,D.Sc., F.R.S., President, in the Chair. Messrs. U. 0. S. Kairne and J. T. Hall were formally admitted Fellows of the Society. Certificates were read for the first time in favour of Messrs. J. P. Ackroyd, B.Sc., 116, Richmond Street, Accrington, Lancs. Charles Thomas Bennett, 67, Larkhall Rise, Clspham, S.W. George E. P. Broderick, B.Sc., Lampeter, 8.Wales. Julian Drugman, Ph.D., La Bocca, Games, .France. George Fry, Carlin Brae, Berwick-on-Tweed. Francis D’Og ley Mears, jun., 4, Nyanza Terrace, Swansea. ,Jatindran&thSen, MA., 71, Cathedral Nission Lane, Calcutta. Raymond Louis Siau, 15, Merridale Lane, Wolverhampton. Henry E.Stevenson, Avondale, Ditton Hill, Surrey. Charles H. Thompson, Hillcroft, ‘Amblecote, Stourbridge. 2 Hubert ‘rhompson, B.Sc., Holmes Chapel, Cheshire. LQon Edward Walling, 43, Union Road, Rotherhithe. Charles Edward Whiteley, 9, Abyssinia Grove, Leeds. William Henry Woodcock, 10, Chesson Road, W. Kensington, W. Certificates in favour of the following were authorised by the Council for presentation for Ballot under Bye-Law I (3) : Anu Chose, 42, Shambazar Street, Calcutta. J. P. Montgomery, Agricultural College, Starkville, Miss., U.S.A. The PRESIDENTannounced that since the last meeting of the Society the Rev. T. J. Prout, M.A., F.G.S., Senior Student of Christ Church, Oxford, had presented to the Society a photograph of a portrait by Hayes of his father, Dr.William Prout, F.R.S., which was considered to be a very good likeness of the author of the famous paper ‘‘ On the Relation between the Specific Gravities of Bodies in their Gaseous State and the Weights of their Atoms,” published anonymously in Thornson’s Annals of Philosophy in November, 1815. The Council has ordered the following report to be printed in the Journal and in the Proceedings of the Society : Beport of the International Commit tee on Atomic Weights. The International Committee on Atomic Weights * has the honour to offer the following report : In the table of atomic weights for 1904, only two changes from 1903 are recommended. The atomic weight of caesium has been slightly modified to accord with the recent determinations by Richards and Archibald, and that of cerium in conformity witoh the nieasure- ments by Brauner.The value for lanthanum is still in controversy, and any change here would therefore be premature. The same consideration may also be urged with regard to iodine. Ladenburg has shown that the accepted number for iodine is probably too low, but other investigations upon the subject are known to be in progress, and until they have been completed it would be unwise to propose any a1tera tion. Many of the atomic weights given in the table are well known to be * The original members of the Committee take great pleasure in announcing the addition to their number of Professor Henri Moissan. They are confident that this increase will meet with universal approval.3 more or less uncertain. This is especially true with respect to the rarer elements, such as gallium, indium, columbium, tantalum, &c. But soae of the commoner elements also stand in need of revision, and we venture to call attention to a few of these. Among the metals, the atomic weights of mercury, tin, bismuth, and antimony should be redetermined, for the reaBon that the existing data are not sufficiently concordant. Pallrtdium also, on account of discrepancies between different observers, and possibly vanadium, for which the data are too few, deserve some attention. Among the non-metals, phosphorus has been peculiarly neglected, and our knowledge of the atomic weight of silicon rests upon a single ratio.In the latter case, confirmatory data are much to be desired. Upon any of these elements, new investigations would be most serviceable. There is one other point to which we may properly call attention. Many of the ratios from which atomic weights have been calculated were measured in vessels of glass, by procasses involving the use of strong acids. In such cases, the solubility of the glass becomes an important consideration, even when no transfer of material from one vessel to another has occurred. A slight conversion of silicate into chloride would cause an increase of weight during the operation, and so introduce an error into the determination. Such errors are doubtless very small, but still they ought not to be neglected.Now that vessels of pure silica, the so-called quartz-glass, are available for use, they might well replace ordinary glass in all processes for the determination of atomic weights. An investigation into the relative availability of the two kinds of glass is most desirable. F. W. CLARKE ) T. E. THORPE K. SEUBERT Committee. HENRIMOISSAN 1904. Interruitional Atomic Weights. I' O= 16. H=l. 0=16. H=1. Aluminium ......... A1 27.1 26.9 Neodymium ...... Nd 143.6 1425 Antimony .........Sb 120.2 119.3 Neon ............... Ne 20 19.9 ~Argon ..............A 39-9 39'6 Nickel ...............Ni 58.7 58-3 Arsenic ............ As 75.0 74.4 Nitrogen ............N 14.04 13-93 Barium ............ Ba 137'4 136.4 Osmium ............0s 191 189.6 Bismuth ............Bi 2085 15-88 Boron ..............B 11 105.7 Bromine ............ Rr 79-96 30.77 Cadmium ......... Cd 112.4 193.3 Cesium ............ Cs 132.9 38-86 Calcium ............Ca 40.1 139.4. Carbon ............ C 12.00 223.3 Cerium ............Ce 140.25 102.2 Chlorine ............C1 35-45 84.8 Chromium ........ Cr 52'1 100.9 Cobalt ............... Co 59-0 58.56 ' Samarium ........Sm 150 148.9 Colunibinm ...... Cb 94 93.3 Scandium ........ Sc 44.1 43*8 Copper ............Cu 63-6 63.1 Selenium............ Se 79.2 78% Erbium ............ Er 166 164-8 Silicon............... Si 28'4 28.2 Fluorine ............ F 19 18.9 I Silver ............... Ag 107'93 107.12 Gadolinium ......Gd 156 22.88 Gallium ............Ga 70 86-94 Germanium ..... Ge 72.5 31.83 Glucinum .........G1 9-1 181'6 Gold ............... Au 197.2 195.7 Tellurium ......... Te 127'6 126.6 Helium ............He 4 4 , Terbiurri ............ Tb 160 158% Hydrogen ......... H 1'008 1.000 . Thallium .........T1 204'1 202.6 Indium ............In 114 113'1 1 Thorium ............Th 232.5 230.8 Iodine ..............I 126.85 125.90 i Thulium ............ Tm 171 169.7 Iridium ............ Ir 193'0 118.1 Iron ..................Fc 55.9 47*7 Krypton ............ Kr 81'8 81.2 . Tungsten .........IT 184 182.6 Lanthanum ......La 138'9 137'9 , Uranium ...........U 238'5 236.7 Lead ...............Pb 206'9 205.35 Vanadium .........V 51'2 50.8 Lithium ............Li 7'03 6'98 Xenon ...............Xe 128 127 Magnesium ......... Mg 24'36 24-18 Ytterbium ......... Yb 173.0 171.7 Manganese .........Mn 55'0 54.6 Yttrium ............Yt 89'0 88-3 Mercury ............ Hg 200.0 198.5 Zinc..................Zn 65'4 64.9 Molybdenum ......1x0 96.0 95.3 Zirconium .........Zr 90.6 89-9 5 Of the following papers, those marked * were read : *l. “The chemical reactions of nickel carbonyl. Part I. Be-actions with the halogens and other inorganic substances.” By James Dewar and Humphrey Owen Jones. The previous study of the physical properties of nickel carbonyl (I’roc. Roy. Soc., 1903, 71, 627) showed that it was a com-paratively stable substance when heated under pressure. The authors have undertaken the investigation of its chemical behaviour mainly from a thermochemical standpoint, with the view of studying its con-stitution and its possible use as a synthetical agent.Nickel carbonyl is completely decomposed by solutions of chlorine, bromine, iodine, cyanogen, and sulphur in organic solvents, carbon nionoxide and a nickel compound being produced ; in no case was any combination of the carbon monoxide with the halogen or other reagent observed, even when a considerable excess of the latter was present. From Mittasch’s value (52.2 Cal.) for the heat of formation of nickel carbonyl and Thomsen’s values for nickel compounds, it was to be expected that chlorine and bromine would decompose it readily, but that iodine, cyanogen, and sulphur would not.In the case of iodine, the heat necessary to carry out the reaction appears to be obtained by the formation of molecular complexes of nickel iodide and the solvent (for example, ether and chloroform), and in the case of sulphur by the formation of a higher sulphide, probably Ni,S,. Liquid chlorine and bromine decompose solid nickel carbonyl, but solid iodine appears to have no action on liquid nickel carbonyl. Iodine mono-and tri-chlorides and cyanogen iodide in carbon tetrachloride solution react with nickel carbonyl in two distinct stages, the free iodine liberated at first subsequently decomposing a further quantity of nickel carbonyl. Hydrogen iodide readily interacts with nickel carbonyl, whereas the corresponding bromide and chloride do not affect it.Hydrogen sulphide reacts very slowly with nickel carbonyl, pro- ducing nickel monosulphide, hydrogen, and carbon monoxide. Sulphuric acid also decomposes the compound slowly, giving rise to nickel sulphate, hydrogen, and carbon monoxide. 6 *2. ‘‘The chemical reactions of nickei carbongl. Part 11. Reaction with aromatic hydrocarbons in presence of aluminium chloride. Synthesis of aldehydes and anthracene derivatives.” By James Dewar and Humphrey Owen Jones. Nickel carbonyl does not react with either aluminium chloride or benzene separately, but with a mixture of the two substances, a violent reaction begins immediately and torrents of hydrochloric acid are evolved. The reaction with various benzene homologues has been in- vestigated both at the ordinary temperature and also at looo.From benzene at the ordinary temperature, benzaldehyde is produced together with traces of oils having high boiling points. At looo, the quantity of benzaldehyde is much smaller, and anthracene, which is now the chief product, is produced in considerable quantities. The mechanism of this production of anthracene from benzaldehyde has not been elucidated, but the reduction is probably due to the action of the nickel produced by the decomposition of the nickel carbonyl. Toluene gives p-tolualdehyde and 2 :6-dimethylanthracene (m. p. 215-216O). m-Xylene similarly yields 2 :4-dimethylbenz-aldehyde and a tetramethylanthracene melting at 280°, which is in all probability 1 :3 :5 : 7-tetramethylanthracene.Mesitylene yields an aldehyde only, condensation to an anthracene derivative being in this case impossible. Naphthalene behaves in an entirely different way; no aldehyde is formed either in the cold or at looo, and a hydrocarbon, C16H12,is produced together with oily or resinous substances having very high boiling points, which appear to be further condensation products, since the quantity produced is much greater at the higher temperature. This hydrocarbon, which melts at 18O-18lo, is probably identical with that obtained by Bischoff by the interaction of naphthalene and methyl chloride in the presence of aluminium chloride, and may also be identical with that produced from ruficoccine or coccinine by distilla- tion with zinc dust.”3. ‘(Optically active asymmetric nitrogen compounds. d-and LPhenylbenzylmethylethylammon~um salts.” By Humphrey Owen Jones. The resolution of the phenylbenzyImethylethylammonium salts was undert,aken with the view of showing that optical activity in nitrogen compounds was independent of the existence of isomerides of the compound in question. 7 The only optically active nitrogen compounds known at present are the d-and I-a-phenylbenzylmethylallylammoniumsalts, and these are also the orily quinquevalent nitrogen compounds (not containing an asymmetric carbon atom) which have been shown to exist in definiie stable isomeric forms. Phenylbenzylmethylethylammoniurn iodide has been prepared in the three possible ways, namely, by the following combinations : (1) methylethylaniline and benzyl iodide, (2) benzylethylaniline and methyl iodide, (3) benzylmethylaniline and ethyl iodide.The velocity of formation of the iodide is remarkably different in the three cases, that in the first combination being the greatest and that in the third being the least. The compound produced, which is the same in all three cases, crystallises from alcohol in lustrous, prismatic prisms, the melting point of which is about 140-142', but this is to a certain extent dependent on the rate of heating. The iodide was converted into the a?-and I-camphorsulphonates by boiling molecular proportions of the salt and silver d-and I-camphor- sulphonates with ethyl acetate and a small quantity of alcohol.The camphorsulphonate was crystallised repeatedly from a mixture of dry ethyl acetate and ethylal at a comparatively low temperature until its rotatory power was constant. d-Phenylbenzylmethyl-ethylammonium d-camphorsulphonate crystallises in lustrous prisms melting at 180-181°. It is very sparingly soluble in ethyl acetate and acetone and has [MI, =71.0° in aqueous solution. The corresponding ZZ-salt is identical with its dd-isomeride in appear- ance and properties and has [M JD = -71.2". d-Phenylbenzylmethyl-ethylammonium iodide, which was obtained by mixing the calculated quantities of potassium iodide and the cl-cnmpborsulphonate in aqueous solution, has the same appearance, crystalline form, and melting point as the inactive iodide ;it is very sparingly soluble in alcohol and other solvents. Its rotatory power is small, so that determinations of this constant are difficult, the observed [MI, being about 30'.The cor-responding I-iodide, which was prepared from the I-camphorsulphonate in a similar manner, had [MI, =30° (approximately). The iodides undergo racemisation in chloroform solution, but their molecular weight in this solvent appears to be nearly normal at the ordinary temperature. The inactive and laevorotatory bromides were also prepared and were found to melt at 155-156O. The latter compound has a higher specific rotatory power than the I-iodide. The feeble rotatory power of these salts compared with that of the active a-phenylbenzylmethylallylammonium salts is remarkable, since the only difference is the replacement of an ally1 by an ethyl radicle.8 *4. ‘‘A microscopic method of determining molecular weights.” By George Barger. The author has continued the experiments of which a preliminary account has already been given (Proc., 1903, 19, 131). The method is based on the comparison of the vapour pressures of two solutions, of which biconcave, lenticular drops are placed in a capillary tube. A difference in the vapour pressures causes a mutual variation in the size of the drops, mbich is observed by means of an eye-piece micrometer. About one hundred determinations with various substances in eleven different solvents have now been made, and the experimental error is found to vary from 5 to 10 per cent.Solvents of widely differing boiling points have been employed, including ether, xylene, and light petroleum (b. p. SO-SO0). Some determinations were per-. formed with minute quantities of the dissolved substance. The method is being applied to the study of association in mixtures of associative and non-associative solvents. The behaviour of benzoic acid in mixtures of benzene and ethyl alcohol, and of cinnamic acid inmixtures of chloroform and methyl alcohol has so far been studied, the results showing that a small proportion of the alcohol suffices to give these acids a normal molecular weight. Should this phenomenon prove to be general, it wou!d be of practical value in determining mole- cular weights in those cases where associative solvents only can be employed.DISCUSSION. Dr. PHILIPasked whether it would be possible to carry out the experiments at a higher temperature, nearer the boiling point of the solvent, in order to shorten the time necessary for the establishment of equilibrium between the drops. Dr. HEWITTsuggested the possibility of using two graduated tubes fitted with tightly-fitting india-rubber stoppers and connected by a T-tube, the third branch of which should have a stop-cock. Into one of the graduated tubes a standard solution could be introduced, and into the other a weighed quantity of the substance, together with some of the solvent. It would then only be necessary to exhaust the apparatus, place it in a bath until equilibrium was attained, allow to cool, and measure the respective volumes of solution in the two graduated tubes.Mr.BARGER,in reply to Dr. Philip, said that the tubes must either be measured at the higher temperature or cooled down to that of the microscope. In the latter case, the solvent condenses between the 9 drops on the walls of the tube, and thus produces an error. In the former case, it has not been found possible to prevent the condensation of water vapour on the frontal lens of the microscope objective. Macroscopic methods similar to that suggested by Dr. Hewitt have been tried, both volumetrically and gravimetrically, but without the least success. The essential conditions which make the present method possible are : (1) The accuracy with which extremely small changes in volume of the drops can be detected under the microscope.(2) The large evaporating surface presented by the drops, as com-pared with their volume. "5. Studies in the acridine series. Part I." By John Jacob Fox and John Theodore Hewitt. The authors find that 6-acetamino-2 :7-dimethylttcridine (m.p. 270' uncorr., Ullmann gives 258O, Bey., 1903,3f3, 1025) unites with methyl iodide to form a quaternary acridinium iodide, a substance yielding a precipitate with ammonia. The isolation of the corresponding carbinol seems impracticable on account of the ease with which the acetyl group is hydrolgsed. To ensure complete hydrolysis, the solution obtained on boiling the precipitate with dilute sulphuric acid is treated with ammonia, when the base is liberated.This compound, which, when crystallised from acetone, bas a pale red colour, melts at 210' (uncorr.) and corresponds with the formula C,,H,,ON, ;it is probably a carbinol having the following constitution : c6H3iMe<~~~~>c~H,~~e*~H~. When the carbinol base is heated for some hours at 184O, partial dehydration occurs, and on warming the nitrobenzene solu- tion of the substance, a very appreciable evolution of water is observed. On filtering the hot solution and subsequently treating the cooled filtrate with light petroleum, a dark red compound, C,,H,,N,, is deposited, which is readily soluble in acids and probably has the constitution C,H,Me<CH>C,H,Me:NH, NMe because the oxygen removed as water was attached in the carbinol base to the carbon atom of the median ring.Such a formula For the anhydro- base agrees with the constitution C,H,<:?>/C,H,:NH, for the base of aposafranine, and does not correspond with the apo-safranine formula suggested by Kehrmann (compare Ber., 1896, 29, 2316 ; Annnlen, 1896, 290, 256). 10 6. '' o-Nitrobenzoylacetic acid." By Edward Rushton Needham and William Henry Perkin, jun, Ethyl sodioacetoacetate (2 mols.) reacts readily with o-nitrobenzoyl chloride (1 mol.), yielding the sodium compound of ethyl o-nitro- benzoylacetoacetate, NO,*C,H,*CO*CAcNa *CO,Et (Geveko th, Annalen, 1883, 221, 323), and when this product is digested with ammoniaand ammonium chloride (compare Claisen, Annalen, 1896, 291, 67) the acetyl group is eliminated and ethyl o-nits*obenzoyZacetute, NO;C,H;CO*C! H;CO,Et, is produced.This ester is a pale brown oil which, in alcoholic solu-tion, gives an orange-red coloration with ferric chloride ; it readily dissolves in diluie aqueous caustic potash yielding a yellow, crystalline potassium derivative, NOy*C,H4*CO*CHK*CO,Et, and when its ethereal solution is shaken with ammoniacal copper sulphate, the green, crystalline copper derivative, NO~*C,H,*CO*CH.Cu~*CO,Et,is obtained, Ethyl o-nitrobenzoylncetate dissolves in concentrated sulphuric acid, and if the solution is heated at 90' for a few minutes and then poured into water, o-nits80benxoylaceticacid, N O,*C,H,*CO*CH,*CO,H, separates, and may be purified by crystallisation from water.It melts at about 118", and, when boiled with water, is decomposed into o-nitro- acetophenone and carbon dioxide. 7. '' The cis-and trans-modifications of my-trimethylglutaconio acid." By William Henry Perkin, jun., and Alice Emily Smith. The authors have already shown (Trans.,1903, 83,772) that when ethyl aay-trimethylacetonedicarboxylate, C0,Et *CMe;CO*CHMe*CO,Et, is reduced with sodium amalgam, it is converted into a mixture of the cis-and trans-modi6catioas of P-hydroxy-aay-trimethylglutaricacid, C02H~CMe20CH(OH)*CHMemC02H,and both of these, by treatment first with phosphorus pentachloride and then with diethylnniline, yield trans-aay-trimethylglutaconicacid, CO,H*CMe;CH:CMe*CO,H, which melts at 150".They now show that on distillation both of the fore- going hydroxy-acids are converted into the anhydride of the cis-modi- fication of aay-trimetl~ylglutccconic acid, which melts at 88", and on hydrolysis yields the corresponding acid melting at about 125". On treatment with bromine, cis-trimethylglutaconic acid yields cis-Py-clibromo-aay-trinzetlTLylglzctccric acid, CO,H CMe, *CHBr CMeBr.CO2H, which melts at 168". During the di~t~illation of the hydroxy-acids, a considerable amount 11 of carbon dioxide and :;team is eliminated, and an oily acid is produced which distils at 213". This substance, crotoszyldimetl~ylacetic acid, CO,H*CMe;CH :CHMe, when treated with bromine, yields the lactone of P-bromo-y-hydroxy-my-trimethylbutyricacid (rn.p. 83"), ?bXe,*CHBr*YHMe co--0' and, when boiled with dilute sulphuric acid, is converted into the lactone of y-hy droxy-aay- trimethy 1but yric acid (a-d ime th ylvalero- lactone), QMe,*CH;F HMe which melts at 52" arid has already co--0 been described by Anschutz and Gillet (Annalen, 1888, 24'7,107), who obtained it by the reduction of aa-dimethyllsvulic acid, CO,H *CMe;CH;COMe. 8. '{The influence of substitution in the nucleus on the rate of oxidation of the side-chain. I. Oxidation of the mono- and di-chlorotoluenes." By Julius Berend Cohen and James Miller. The method of oxidation adopted was to heat about a gram of each of the isomerides with dilute nitric acid in a sealed tube for a length of time insufficient for complete oxidation and to estimate the pro- portion of the acid product and the unchanged substance.The vessel employed as air-bath was SL jacketed, tin-plate cylinder containing boiling coal-tar naphlha and furnished with a condenser, the tubes being heated in the inner compartment, which was kept at a nearly constant temperature. The results of several series of experiments show that the mono- halogen derivatives are more rapidly attacked than the dihalogen compounds. Of the three monochlorotoluenes, the meta-compound is least rapidly and the para-isomeride most rapidly oxidised. Of the dihalogen compounds, the 3 :5-compound is least affected ; then follow the 2 :5-and 2 :6-isomerides, which are oxidised about equally ; then the 2 :3-compound, and finally the 2 :4-and 3 : 4-compounds, which may be bracketed together as being most readily attacked.So far as these experiments are concerned, in which the oxidising agent is nitric acid, the results are perfectly definite. The meta-compounds retard and the para-derivatives asdst oxidation, whilst the ortho-compounds occupy an intermediate position. Thus, m-chlorotoluene and 3 :5-dichlorotoluene are least attacked by the acid, whereas p-chlorotoluene and the 2: 4-and 3: 4-dichlorotoluenep, which each contain a chlorine atom in the para-posi- tion with respect to the methyl group, are most rapidly oxidised. 12 9.“The interdependence of the physical and chemical criteria in the analysis of butter fat.” By Thomas Edward Thorpe. In the course of an investigation on the chemical nature of butter produced within the British Isles, which was instituted by the Board of Agriculture for the information of a Departmental Committee appointed to report as to what regulations might with advantage be made for determining what deficiency in any of the normal constitu- ents of butter $hould raise a presumption under the Food and Drugs Acts that the butter was not genuine, it became necessary to obtain at first-hand the values of butter of known origin and produced from milk given under varying conditions. Observation has shown that the chemical nature of butter fat is dependent, to a certain extent, on the climatic influences to which the cows are exposed, on the nature and amount of the food supplied, and on the breed, period of lactation, and idiosyncrasy of the individual cow.In order to give such weight as was practicable to the effect of these factors, the samples of butter were obtained from carefully selected districts, and often from cows set apart for the purpose of the inquiry, whilst particulars of the breed, diet, stabling, and period of lactation were supplied with the samples in nearly all cases. For example, to illustrate the effects of more rigorous climatic conditions than obtain in the United Kingdom generally, farms and dairies in Caithness, Sutherland, the Orkneys, Shetlands, and the Hebrides were laid under contribution, whilst a series of samples from Hollesley Bay, Suffolk, served to exemplify the effect on the cattle of exposure to the minds of the North Sea.Of the 430 samples received, 357 mere examined as regards their Reichert-Wollny number, their relative density, saponification value, and refractometric value, and in a certain number of typical cases their Hub1 value was ascertained. The main results of these observations have been tabulated and compared and their interdependence exhibited by means of curves. 10. A simple thermostat for use in connection with the refracto- metric examination of oils and fats.” By Thomas Edward Thorpe. The thermoStat is primarily intended for use in connection with the Zeiss butyro-refractorneter, in which a current of water, usually at about 45‘ or a little warmer, is caused to circulate round the prism casing. This arrangement is somewhat more convenient than that usually employed, occupies less space, and is sooner brought into action.It has for some years past been employed in the Government Labora- tory in the examination of butter. 13 11. '' The condensation of furfuraldehyde with sodium succinate." By Arthur Walsh Titherley and James Frederick Spencer. Fittig has shown (Anncden, 1883, 216,97 ; 1889, 255,1-142) that aldehydes condense with sodium succinate in the presenee of acetic anhydride, giving substituted paraconic and isocrotonic acids : R*CH:O+ yH,*WO,H CO,H)*CH,*CO0--I-CH,*CO, H -+ R*yH*CH( R *CH CH*CH,*CO,H, where R is any alkyl or aryl radicle. The authors in attempting to employ this method for the synthesis of p-f urfurylidenepropionic (f urf urylisocrotonic) acid by condensing furfuraldehyde with sodium succinate in presence of acetic anhydride found that neither it nor furfurylparaconic acid is formed, but two unexpected derivatives were produced, which were isolated with con-siderable difficulty, the yields being very small.One of these substances, which crystallised in dark orange-coloured needles melting at l87", was found to be difu~furyZid~~esuc~~n~c ccnhydvicle, C,,H,O,, and the other, which separated in bright yellow plates (m.p. 2 13O), was identified as a~-d.f~Llful'~Zi~~~~~o~'onicacid, C,,H,,O,. These results indicated that two furfuraldehyde molecules condensed with one molecnle of sodium succinate, and all attempts to prepare the corresponding monof urfurylidene derivatives failed.These products may be regarded as being produced from the difur- furylidene derivative in the following manner : C,H,O*CH :ygC02H C,H,O-CH :C*CO,H C,H,O*CH :y*CO C,€I,O*CH :YH C,H,O-CH: C*CO>o C,H,O CH C*C0,H m. p. 187". m. p. 213". The orange-coloured anhydride is decomposed with difficulty by sodium hydroxide, forming sodium dificvf~~licEenesuccinate; the acid is a yellow, crystalline powder melting at 185-187' and regenerating the anhydride. The acid is also converted into the anhydride on gently warming with acetyl chloride.The anhydride readily combines with bromine, yielding the well- defined tetrabromide, aapp-tetvabromo-s-d;fwrficryZsucccin;canhydride, C,H,O* CHBr-QBr-CO n bright yellow powder melting at 196"C,H,O*CHBr*CBr*CO>0, and giving fluorescent solutions. 14 The yellow ay-difurfurylidenepropionicacid (m.p. 213") was obtained asthe sole crystallisable product and in larger yield, on using succinic anhydride as the dehydrating agent instead of acetic anhydride, but in all cases the condensation of furfuraldehyde with sodium succinate was accompanied by the formation of large quantities of resinous matter. 12. ''The action of heat on a-hydroxycarboxglic acids. A prelimin-ary note." By Henry Rondel Le Sueur. The aldehyde,C,6H,,*CH0,which is produced by heating a-hydroxy- stearic acid, crystallises from light petroleum in needles melting at 36", and from alcohol in needles containing 1 mol.of the solvent and melt- ing at 52"; it forms a crystalline compound with sodium hydrogen sulphite, and the oxime and semicarbaxone melt at 89.5" and 107-108" respectively. The acid, C,6H3,*C0,H,obtained by oxidising the aldehyde with potassium permanganate, crgstallises from light petroleum in long needles melting at 60-61' ;the silver salt, C17Hs30,Ag,is amorphous. The author is investigating the action of heat on other mono- and di-basic a-hydroxy-acids. 13. "The fusion of isopilocarpine with caustic potash. A correc-tion." By Hooper Albert Dickinson Jowett. h a communication on the constitution of pilocarpine (Tvans., 1900, '7'7, 860), the author showed that an acid, then regarded as kbutyric acid, was produced by the fusion of isopilocarpine with caustic potash.The existence of the rh-butyl group in isopilocarpine, as proved by the formation of a-ethyltricarballylic acid from homo- pilopic acid, and t,he production of n-butyric acid by fusion of pilopic acid with caustic potasb, however, rendered it probable that the acid previously described as isobutyric acid was really n-butyric acid. The experiment has therefore been repeated. Ten grams of iaopilocarpine were fused with 100 grams of caustic potasb, and the fatty acid separated in the manner previously described (Zoc. cit.). The portion distilling between 120' and 160" was collected and converted into the calcium salt by neutralisation with calcium carbonate.The acid was not soluble in a small amount of water, but dissolved almost completely in a larger quantity. The calcium salt, which separated from the hot aqueous solution on con-centration, was collected while hot ;it formed white, pearly plates, which were dried in the air and analysed : 0-1982 lost 0.0162 H,O at 150". H,O =8.2. 0.1780 ,, 0.0144H,O ,, looo. H,O=8.1. (C,H70,),Ca,H20 requires H,O = 7.8 per cent. Calcium isobutyrate crystallises with 4 molecules of water. On warming an aqueous solution of the salt, saturated at O", crystals separated, which redissolved on cooling, The silver salt mas prepared and recrystallised from water.0.1312 gave 0.0726 Ag. Ag=55*3. C,H,O,Ag requires Ag =55 4 per cent. The volatile acid formed by the fusion of isopilocarpine with caustic potash is theielore n-butyric acid. 14. Organic derivatives of silicon. Preparation of alkylsilicon chlorides." By Frederic Stanley Kipping. It has been previously shown that tetra-alkyl derivatives of silicon can be obtained by treating silicon tetrachloride with alkyl halides in presence of sodium (Kipping and Lloyd, Trans., 1901, 79, 449). The investigation of silicon compounds has recently been resumed in con-junction with Mr. A. Hunter, and attempts have been made to pie- pare compounds of the type SiR,R,R,Cl with the following results. Silicon tetrachloride interacts vigorously with an ethereal solution of magnesium ethyl iodide, the product consisting of a mixture of ethylsilicon trichloride, diethylsilicon dichloride, triethylsilicon chloride, and silicon totrsethyl, the proportions of which depend on the relative quantity of the magliesium compound employed.Silicon tetrachloride also interacts very vigorously with an ethereal solution of magnesium ethyl bromide ; when molecular proportions of the two compounds are used, the product contains a small quantity of the di- and tri-ethyl derivatives, but consists principally of ethyl silicon trichloride, which can be isolated by fractional distillation and has the properties assigned to it by Ladenburg. Ethylsilicon trichloride and an ethereal solution of magnesium phen yl bromide interact very readily, and phanylethylsilicon dichloride can be isolated by fractional distillation; this compound is a fuming liquid boiling at about 228-230' and readily decomposed by water, giving an oil which appears to be the silicoketone, SiEtPhO.Phenylethy lsilicon dichloride and an ethereal solution of magnesium propyl bromide do not give an immediate precipitation of magnesium salt,, but on warming, a reaction occurs with the formation of phenyl-ethylpopyls&con chloride, which is obtained after fractional distillation, mixed apparently with unchanged dichloride, as a colourless liquid boiling indefinitely at about 340'. These and other alkyl derivatives of silicon tetrachloride are now being examined, and, in conjunction with Dr.Caven, analogoas experi- 16 ments have been commenced with the object of preparing mixed alkyl derivatives of phosphorus, more especially compounds of the type POR,R,R, or PORIR,*OH. 15. ‘(Derivatives of highly substituted milines.” By Frederick Daniel Chattaway and John Mello Wadmore. The authors described the preparation and properties of a series of highly substituted acyl- and chloro-amines obtained in the course of an investigation into the phenomena of intramolecular rearrangement in aromatic amines. ERRATUM. (PRoc.,1903, 19,No. 273.) Page 282, line 9 from bottom, for ‘I trialkylhydroxylamines” read ‘‘trialkyloxamine3.” At the next Meeting, on Thursday, February 6th, at 8 p.m., the following Papers will be communicated : “The tautomeric character of the acidic thiocyanates. A pre-liminary note.” By R. E. Doran. ‘‘ The resolution of ap-dihydroxybutyric acid into its optically active constituents.” By R. S. Morrell and E. K. Hanson. K. CLAS AKD SOX’S, LTD., BREAD ST. IIILL, E.C., AND BUNOAT, SUYFOLE.
ISSN:0369-8718
DOI:10.1039/PL9042000001
出版商:RSC
年代:1904
数据来源: RSC
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