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Proceedings of the Chemical Society, Vol. 25, No. 350 |
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Proceedings of the Chemical Society, London,
Volume 25,
Issue 350,
1909,
Page 1-20
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摘要:
Issued 29JllOiJ PROCEEDINGS OF TIf B CHEMICAL SOCIETY. Vol. 25. No.350. Thursday, January 21st, 1909, at 8.30 p.m., SIRWILLIAMRAMSAY, K.C.E., F.R.S., President, in the Chair. The minutes of the previcus meeting havinq been read and confirmed, Dr. DIVERSmade the following inqiiiriep. Whether one of the objects of the resolution adopted by the Council “to remove some of the disabilities experienced by women chemists ’’ mere not, as it appeared to be, to let duly qualified women be ‘‘ accepted ” to enjoy privileges in the Society which men, similarly qualified, were not to be per- mitted to enjoy OK) the same terms, and, that being so, whether that object were a just and lawful one? Whether the Council, in taking upon itself to (( enact a regulation ” (Charter, p.6) indistinguishable in form and substance from a bye-law, had avoided exceeding its powers merely by not proceeding to call the regiilation a bye-law ? In what did the resolution concerning Subscribers of the Society differ from the existing bye-law for Associates, except in that sin Associate inust have passed a ballot of the Fellows? Was it not dear from the Charter that any action by the Council on the resolu- tion would be invalid until the vote of II General Meeting should have made the resolution into a bye-lam 1 Whether the Council inubt not be exceeding its powers in legislating for women in any way what- ever, if it were indeed the case that it would be going beyond its powers mere it to accept women as candidates for the Fellowship, they being, it was said, outside the considerdtion of the Charter 2 Would not even a General Meeting be exceeding iti rnnch greater powers 2 mere it to attempt to frame quasi-bye-lams for those to whom the Charter did not apply? Did the Council in its words I‘ disabilities experienced by wonien ” refer to its assumption that the Charter really imposed upon it disability to receive the candidature of women for the Fellowship? If so, did it need to be pointed out that disabilities, like any other ordinances, were not ‘(experienced ” by anyone, but were imposed, and that a Charter did not attempt to limit the powers of any man or woman who was not enjoying the privileges which it bestowed ‘1 In speaking of ‘‘removing disabilities ” did the Council maintain that it could itsel€ escape from or could relieve others of a disability laid upon it or upon them by the Charter Z Lastly, was it to be understood tbat the Council believed, what its words implied, that it would be removing disnbili ties by granting privileges, supposing that it really could do either of these things1 Messrs.N. C. Akers, J. Brown, R. F. Easton, C. Everitt, A. F. GirvaG, C. L. Norman, G. E. Pearson, ’CV. B. Shaw, W. G, Winterson, and F. P. Worley mere formally admitted Fellows of the Society. The PRESIDENTannounced a proposal by the Institution of Gas Engineers to perpetuate the memory of the late Sir George Livesey by establishing a Livesey Professorship in Gas Engineering and Fuel at the Leeds University; contributions to the Pund should be addressed to the Secretary of the Institution of Gas Engineers, 39, Victoria Street, Westminster. Certificates were read for the first tinie in favour of Nessrs.: Alfred Bertram Coies, M.A., 42, Broadwater Road, Tottenham, N. John Thomas Fox, Glen Burn, Stollard Street, Clay Cross, near Chesterfield. John Thomas Furnell, 32, Grosvenor Park Road, Walthamstow. dlfrsd George Cooper Gwyer, Ph.D., B.Sc., Keate House, Durdham Down, Bristol. Robert Main Harland, 296, Willesden.Lane, Willesden Green, S.W. Henry Humphreys Jones, 18, Colquitt Street, Liverpool. Horace Keeble, Wereham, Stoke Ferry, Norfolk. Joseph Leedham, 176, Bromford Lane, West Bromwich. William George Martin, B.Sc., Royal School, Armagh.Xobert Robinson, M.Sc., Field House, Chesterfield. Herbert Rogers, Stenning House, CobwelI Road, Retford, Notts. J. H. Charles Schulten, Ph.D., 4, Pollock Street, Calcutta. Guy Ransom Warwick, B.A., 5 and 6, Fomkes Buildings, Great Tower Street, E.C. Percy Charles Henry West, 40, The Green, Norton, Co. Durham. Thomas Jabez Wild, Scott’s Laboratories, Southall, Xiddlesex. The Council has ordered the following letter and report to be printed in the Journal and Proceedings of the Society : GOVERNMENTLABORATORY, CLEXENT’SINNPASSAGE, STBAND, W.C.LONDON, 29th October, 190s. GEXTLEMEN, I beg to forward you, for presentation to the Council of the Chemical Society, the Report of the International Committee on Atomic Weights, 1909, to which I have affixed, as desired by them, the signatures of Professors OF;twnld and Urbain.The general revision of the values of the atomic weights of the elements, based on the fundamental values for hydrogen, nitrogen, the halogens, silver, etc., as ascertained by the laborious and accurate deter- minations which have been made in various laboratories during recent years, and to which reference mas made in precediug Reports, has now been completed and the Table submitted with the present Report embodies the results of the re-calculations. A number of atomic weights are shown to be slightly influenced by the adoption of the new values, but the changes thus introduced are, it must be admitted, less profound than was generally anticipated. Certain of the values still remain affected by errors far larger than those introduced by the selec- tion of a particular fundamental value of the element with which comparison is made.I am, Gentlemen, Your obedient Servant, T. E. THORPE. The Eon. Secretaries, The Chemical Society, Budington House, London, JK Report of the International Committee on Atomic Weights, 1909. Since the publication of our last Report, smeral important memoirs upon atomic weights have appeared containing data of fundamental significance. They may be summarised as follows : Hydrogen,-W. A. Noyes (J. Amer. Chem. Soc., 1907, 29, 171s) has made complete syntheses of water in five series of determinations.The first series, however, mas defective, and is therefore not published by the author. In mean, the four succe6sful series give H= 1.00787, as compared with Morley’s figure, 1.00762. The general mean of these values, combined with all other trustworthy determinations, is 1.00779. The rounded-off value, 1.008, is therefore retained in the table. Chlorine.-Noyes and Weber (J.Anzer. Ckem. Xoc., 19OS, 30, 13) have effected the synthesis of hydrochloric acid, weighing the hydrogen in palladium, the chlorine in potassium chloroplatinate, and also the hydrochloric acid produced by the union of the two elements. From the ratio H :C1, Cl=35-458, when H = 1.00779. From the ratio H :HC1, C1= 35.457. The same ratios have also been measured by Edgar (Pmc.Roy.sbc., 1908, 81,A, 216), but by a different method. The hydrogen, as in former determinations, was weighed in palladium, but the chlorine was prepared by the electrolysis of fused silver chloride, and weighed in the liquid form. The hydrogen chloride was weighed directly in three experiments, and in two others after absorption in water. From the ratio H :C1, C1-35.468. From the ratio H :HCI, Cl=35.467. With Morley’s value for H, the results are nearer C1= 35.46. Taking all the data together, the value C1= 35.46 seems to be as near the truth as can be positively asserted now. This includes the former work of Dixon and Edgar, and the density determinations by Guye and Gazarinn. SuZphur.*-From eighteen determinations of the density of hydrogen sulphide, Baume and Perrot deduce the value S=32*070.In an earlier investigation by Baume,? who determined the density of sulphur dioxide, he found lower values for S. The figure 32.07, however, is in close agreement with the value obtained by Richards and Jones, when Ag = 107.88, and is doubtless very nearly true. Lead.-Atomic weight determined by Baxter and Wilson (PYOC. Amer. Acad., 43, 365) from analyses of the chloride. With Ag = 107.93, Pb =207.19. With Ag = 107.88, Pb =207.10. This value is still much higher than that previously accepted. Cadmium.-Blum (Thesis, University ‘of Pennsylvania, 1908) has attempted to determine the atomic weight of cadmium by conversion of the oxide into the sulphide. The values obtained range from 112.50 to 112.88, and are admittedly of slight significance. TeZlurium.-Sn an elaborate memoir upon the atomic weight of tellurium, Baker and Bennett (Trans., 1907, 91,1849) give determina- * Private communication from Prof.P. A. Guye. t. J. Chim Phys., 1908, 6, 1. Baume also determined the densities of methyl oxide and methyl chloride. 5 tions by two new methods. By heating tellurium dioxide with sulphur in such a way that only sulphur dioxide could escape, the ratio TeO, to SO, was determined. From the mean oE twenty-five determinations, Te=12’1.609. By direct conversion of tellurium into the tetrabromide, the mean of eighteen determinations was Te = 127.601, when Br =79-96. Referred to Br = 79.92, this becomes 127=54.Several analyses of tellurium tetrachloride, for which the details are not published, gave values for Te between 127.58 and 127.64. On the basis of the modern values for Ag, C1, and Br, and with due regard to the earlier work of Pellini, Gutbier, Koethner, Norris, Scott, Staudenmaier, and others, the rounded-off figure, Te = 127.5, seems to be fairly acceptable. Marckwald,* however, by careful dehydration of telluric acid, found values for Te ranging from 126.65 to 126.94. Six experiments were made, the mean of five, rejecting the lowest of all, being Te = 126-85. This falls below the atomic weight of iodine, and is therefore in harmony with the periodic classification. In view of the general agreement between other investigators in favour of a higher figure, Marckwald’s work cannot be accepted without confirmation. The controversy over tellurium is evidently not ended.Rhodium-Huttlinger (Diss., Erlangen, 1907), working in Gutbier’s laboratory, made three reductions in hydrogen of rhodium pentamine chloride. His results, which seem to be preliminary in character, are practically identical with those obtained by Seubert and Kobbe, whose value for rhodium has been accepted since 1890. No change in this atomic weight is needed. Palladium.-Woerale (Sitzmgsber. phys. rraed. 802. Erlanggen, 38, 296) made seven analyses of palladosamine chloride: two by reductions in hydrogen, three electrolytically. The mean value obtained was Pd = 106.708, presumably computed with the old figures for N and C1.Haas (Diss., Erlangen, 1908), from similar reductions of pallados-amine bromide, found Pd = 106.75, calculated with N = 14.037 and Br = 79.953. These determinations, like those of Krell, were made under the direction of Professor Gutbier. The results obtained by Krell, Woernle, and Haas agree well together, and also with Amberg’s determinations, and are probably quite accurate. Recomputed, with modern values for N and C1, Pd=106.7 very nearly, with an uncertainty of not over 0.05. Lower values were found by Kemmerer (Thesis, University of Pennsylvania, 1908), working under Professor Edgar F. Smith. By reduction in hydrogen, palladosamine chloride gave Pd = 106.399 and * Bw., 1907,qQ, 4730. For a criticism of Marckwald, see Baker, Chem.Xews, 1908, 97, 209. 6 106.442 as the means of two series of observations. From palladosamine cyanide the value Pd = 106.453 was obtained, The mean of fifteen determinations, taken as one series, gave Pd = 106.434. The more concordant values cited above seem to be more trustworthy, at least so far as present evidence permits us to judge, Kemmerer’s computations were made with N = 14-01 and C1= 35-473. Europium-From analyses of the octahydrated sulphate, Jantsch (Compt. rend., 1908,146, 473) finds Eu= 152.03, when S= 32.06 and H= 1.008. The round number 152 is retained in the table. This is probably the nearest significant figure. &biurn.--By repeated fractionation of erbium compounds, Hofmann and Burger (Ber., 1908, 41, 308) have isolated an oxide of slightly higher molecular weight than that of the old erbia.To the new metal thus indicated they assign the name “neo-erbium,” and by synthesis of the sulphate they find its probable atomic weight to be 167.43. The rounded-off figure 167.4 is given provisionally in the table, to stand until more complete data have been obtained. Ytterbium-That the old ytterbium is a mixture of two elements has been proved by Urbain (Compt. rend., 1907, 145, 759, November 4, 1907. See also Compt. .Inend., 1908, 146, 406, and C’hem. Zeit., 1908,32,730), in Paris, and Auer von Welsbach,* in Vienna, working almost simultaneously and independently. In his earlier paper, Urbain names the two elements “neoytterbium ” and ‘‘ lutecium,” with approximate atomic weights of 170 and 174 respectively.In his second memoir, Urbain gives atomic weights for a series of ytterbium fractionations, ranging from 170.6 to 174.02. Welsbach, whose work appeared Inter than Urbain’s, names the two elements ‘‘ aldebaranium,” atomic weight 172.90, and “ cassiopeium,” atomic weight 174-23. Since Urbain has clear priority, his nomenclature should be preferred, but the atomic weights need to be more sharply determined. Incidentally, Urbain notes that the atomic weight of thulium is lower than 168.5. Columbium-A concordant series of determinations made under the direction of Edgar F. Smith T give columbium an atomic weight of 93.5. This is lower than the value hitherto accepted.Radium-Thorp (PYOC.Roy. Xoc., 1908, 80, A, 298) has re-determined the atomic weight of radium by analyses of the chloride. In mean his determinations, calculated with Ag = 107-88 and Cl= 35.46, give Ra = 226.64. Thorpe, however, gives preference to the determinations by Mme. Curie, who worked with larger quantities of material, regarding his own work as confirmatory. The re-calculated value is 226.4. * Monatsh., 29, 181, Feb., 1908. Read before the Vienna Academy, Dee. 19, 1907. t Private communication. The details are shortly to be published. In their Report for 1905 this Committee recognised the fact that a general revision of the atomic weight table was desirable, and such a revision has now been made. Modern investigations have shown that the fundamental values required modification, and through them many other atomic weights are affected, although the changes thus brought about are less important than they mere generally supposed to be.Many atomic weights remain practically unaltered, and in few instances are the changes large, as cz comparison of the new table with its predecessors will show. A carefnl scrutiny of all the evidence was, however, none the less necessary, and the table now offered gives the results thus obtained. The fundamental atomic weights, the standards of reference employed in t,he calculations, are as follows; when O= 16. H, 1.008. Br, 79.916. c, 12.0 0. Ag, 107.880. N, 14*007. K, 39.095. C1, 351.460. S, 32.070. The value for silver is possibly a trifle too low, by from three to five units in the third decimal place.A combination of the best measurements gives Ag=107*883. In this case, and in others as well, the second place of decimals is given in the table, the third place being uncertain. Thus we have K, 39.10, N, 14.01, Br, '79.92, etc. Only with hydrogen is the third place retained. In adjusting the other atomic weights, the determinations by Richards + and his colleagues have generally been given preference. They are certainly entitled to the highest weight, but probably not to exclusive consideration. The work of Guye and his associates at Geneva, and the recent direct measurements of the chlor'ine-hydrogen ratio are also of very great importance.It is to work of this order that we must look for ultimate precision. Important investigations upon atomic weights are now being carried out in several laboratories, and our knowledge of these constants will doubtless become much more exact within the near future. (Signed) F. W. CLARK, W. OSTWALD, T. E. THORPE, G. URBAIN. '-An excellent snmmary of the Harvard work is given by Richards in J. Chim. PIqs., 1908, 6, 92. 1909. Intewmtionat Atomic Weights. 0 =16. 0 =16. Aluminium ................. A1 27 -1 Molybdenum ............... Mo 96.0 Antimony .....................Sb Argon ...................... A 120.2 39.9 Neodyiiiium.................Nd Neon ........................... Ne 141.3 20 Arsenic ..................... As 76.0 Nickel ........................Ni 58*68 Barium ........................ Ba Bismuth .....................Bi 137.37 208.0 Nitrogen Osmium ..................... ..................... I% 0s 14.01 190.9 Boron ........................B 11.0 Oxygen ........................0 16-00 Bromine ..................... Br 79-92 Palladium .....................Pd 106.7 Cadmium ..................... Cd 112'40 Phosphoriis .................. P 31*O Cagsiuin .......................Cs 132-81 Platinum .....................Pt 195.0 Calcium........................ Ca 40.09 Potassium ..................... 1; 39.10 Carbon ........................ C Cerium ........................ Ce 12.00 140.25 Praseodymium...............Pr Radium ........................Ra 140.6 226 '4 Chlorine .....................C1 35-48 Rhodium ..................... Eh 108.9 Chromium .................. Cr 52 '1 Rubidium .....................Rb 85.45 Cobalt ........................ Co 58.97 Ruthenium ..................Ru 101.7 Columbium .................. Cb 93'5 Samarium ..................Sa 150.4 Copper ........................ Cu 63.57 Scandium .....................Sc 44.1 Erbium ........................ ErDysprosium .................DY 162.5 167.4 Seleniuni ..................... Se Silicon ........................ Si 79-2 28.3 Europium.,................... Eu 152.0 Silver ........................& 107'88 Fluorine ..................... F 19.0 Sodium ........................ Xa 23.00 Gadolinium ..................Gd 157.3 Strontium ..................Sr 87-62 Gallium .................... Ga 69'9 Sulphur ..................... S 32.07 Germanium .................. Ge 72 3 Tantalum .................... Ta 181*O Glucinum ..................... G1 9.1 Tellurium ..................... Te 127-5 Gold .............-............ Au 197'2 Terbium .....................Tb 159.2 Helium ........................ He 4.0 Thallium .....................T1 204 -0 Hydrogen ..................... H 1'008 Thorium ..................... Th 232-42 Indium ....................... In 114.8 Thulium ..................... Tm 168.5 Iodine ........................ I 12692 Tin ........................... Sn 119.0 Iridium .......................Ir 193.1 Titani-uni ..................... Ti 48'1 Iron ........................... Fe Krypton ..................... Kr 55.85 81% Tungsten ..................... W Uranium ..................... U 184.0 238.5 Lanthanum .................. La 139*O Vanadium ..................... V 51-2 Lead .......................... Pb 207.10 Xenon ........................ Se 128 Lithium ..................... Li 7 '00 Ytterbium (Neoytterbinni) Yb 172 Lutecinm ..................... Lu 174 Yttrium ..................... Y 59.0 Magnesium Nanganese .................. ITg ..................Mn %4*32 54.93 Zinc ........................... Zn Zirconium.....................Zr 65-37 90.6 Mercury .....................Hg 200'0 9 Of the following papers, those marked * were read : “1. 6‘ Organic derivatives of silicon. Part IX. Experiments on the resolution of dl-benzylethylpropylisobutyls~licanesulphon~cacid.” By Frederic Stanley Kipping and Harold Davies. dl-BenzylethylpropyZisobwtylsiZicane,SiEtPr(C,H,)-CE,Ph, a liquid boiling at 2S2-283’, has been prepared by treating benzylethyl- propylsilicyl chloride (Kipping, T+ans.,1907, 91,717) with magnesium isobutyl bromide; when treated with chlorosulphonic acid, it gives a monosulphonic derivative, which is isolated in the form of its E-ment h ylamine salt. 1-Merzthylaminedl-be~azylethyZ~rop~ZisobutylsiLican~suZp~onc~te, SiEtPr(C4H9)*CH,*66H4*S0,H,C,,H,1N,2H20, separates from moist light petroleum in lustrous leaflets, and, when dehydrated, melts at 127-128°; it is very similar in its properties to the corresponding salts of benzylmethylethylpropylsilicanesulphonic acid (Zoc.cit.) and of benzylethyldipro pylsilicanesulphonic acid (Marsden and Kipping, Tram.,1908, 93, 205), although the latter is not a dl-compound. The strychnine, brucine, cinchonidine, quinine, and cinchonine salts of the dl-acid and the corresponding hydrogen alkaloidal salts of the last- named three bases have been prepared; these eight compounds were systematically crystallised under various conditions, but in all cases, except in that of the cinchonine hydrogen salt,, the melting or decomposing points and the specific rotations of the extreme fractions of a given salt were identical.The cinchonine hydrogen salt gave fractions having the same decomposing points, but differing widely in specific rotation; whether this difference is due to a resolution of the acid or not is still an open question. “2. (‘The crystallisation of externally compensated mixtures.” By Frederic Stanley Kipping and William Jackson Pope. The recent publication of Ostromisslensky’s paper (Ber., 1908, 41, 3035) on this subject affords an occasion for briefly recording the results of some work commenced in 1898, but which has not been brought to a definite issue. On crystallising dl-sodium ammonium tartrate (prepared from purified racemic acid) from aqueous solutions nf dextrose, and then recrystallising the deposit, the product consisted, in nearly all cases, of the d-tartrate, almost or entirely free from the Lsalt (Proc., 1898, 14, 113).It is now shown that similar results are obtained in absence of 10 dextrose even when the racemic acid, used in the preparation of the sodium ammonium salt, has been repeatedly crystallised from water. This preferential deposition of the d-tartrate may be due to the seeding of the solutions by laboratory dust, or to the presence of a minute excess of the d-acid in the racemic acid employed; the results obtained on fractionally crystallising commercial racemic acid itself seem to shorn that the complete removal of extremely small quantities- of dextrorotatory impurity is a very difficult matter.*3. ''Formation of cyclohexanone derivatives from olefinic com-pounds." By Siegfried Ruhemann. Although the esters of acetylenic acids form additive products with phecols, olefinic monocarboxylic esters or olefinic monoketones do not unite with sodium phenoxide. Condensation, however, takes place if the number of electronegative groups in an olefinic compound is increased. The additive compound of ethyl benzylideneacetoacetate with sodium phenoxide at once condenses, thus : 2CHPh(OPh)*CHAc*CO,Et=C,,H,,O, + 2C,H,*OH, yielding a cornpound, C26132806,which has twice the molecular formula of ethyl benzyliclenencsto~cetste. The substance is regarded as a CHPh*CH(CO,"t)>co, and cyclohexanone derivative, C0,Et CAC<~HPhpc: H, this constitution is supported by n number of facts which the closer study of the reaction has furnished. Similar cyclohexanone derivatives have been obtained by the action of sodium phenoxide on benzylideneacetylacetone, CHPh:CA4c, and e thy1 e thylideneace toace tate, CHMe: CAc*CO,Et.On the other hand, but in harmony with the above view of the formation of these cplohexanone compounds, neither ethyl benzyl- idenemalonate, CHPh:C(CO,Et),, nor ethyl benzflidenebenzoylacetate, CHPh:CBz*C02Et, condenses to cyclic compounds, although uniting with sodium phenoxide. *4. '' Synthesis of para-urazine from carbamide. " By Frederick Daniel Chattaway. By means of dichlorocnrbamide, NHCl*CO*NHCl, recently described by the author (Proc.Roy. Xoc., 19OS, 81, A, 381), carbamide can be very simply converted into p-urazine, which has hitherto only been obtained by the employment of hydrazine. All that is necessary is to acld an aqueous solution of dichlorocarbamide to a strong solution of ammonia, when p-urnzine, which is very sparingly soluble in water, separates as a white, crystallice precipitate. 11 In the reaction, one of the chlorine atoms of the dichlorocarbamide is probably replaced by hydrogen, two iiiolecilles of the resulting monochlorocarbamide then condensing under the influence of the ammonia, thus : NHH +ClHN + 3NH,C1.CO<NHcl HHN>CO + 2NH, =CO<~~:~~>CO p-Urazine is readily liydrolyeed when heated with coiicentrated sulphurio acid, carbon dioxide and hydrazine sulphate being produced, thus : C2H,0,K4+2H,O + 2H,SO, =2C0, + 2NH,*NH,,H,S04.This reaction furnishes a very simple method for the preparation of small quantities of hydrazine. DISCUSSION. Dr. HEWITTcalled attention to the analogy between Dr. Chatt-away’s process for obtaining hydrazine and the method devised by Raschig, namely, the direct action of hypochlorites on ammonia. “5. (‘Chlorine derivatives of substituted carbamides.” By Frederick Daniel Chattaway and Donald Frederick Sandys Wunsch. The action of chlorine on csrbamide should give rise to a monochloro-, a symmetrical and an unsymmetrical dichloro-, a trichloro-, and a tetrachloro-carbamide. Of these, only the s-dichloro-derivative has so far been isolated.The action of chlorine on a number of subsbituted carbamides has been studied, and it has been shown that in such compounds it is possible to replace by chlorine all the hydrogen attached to nitrogen, atom by atom. Compounds of the types NHR*CO*”HCI, NCLR*CO*NHCl, NClR*CO*NCI,, NClR*CO*NClR, and NK,-CO-NCl, have been obkhed, R being an acyl or an alkyl group. The monochloroacylcarbamides are beautifully crystalline solids, which are among the most stable of the nitrogen chlorides known. The acyl compounds containing more chlorine, and most of those containing an alkyl group, are liquids which decompose easily on heating, Nearly all of the possible chlorine derivatives of acetyl-, benzoyl-, methyl-, s-and as-dimethyl-, ethyl-, s-diethyl-, and benzyl-carbamide have been prepared.It is thus proved that in carbamides the replacement of one hydrogen atom by chlorine does not prevent in any way the replacement of the second hydrogen atom attached to the same nitrogen. There is every reason, therefore, t.0 believe that the action of chlorine on carbamide itself gives rise to the other theoretically possible chlorocarbamides, and that these will be obtained when the conditions under which they can exist are ascertained, and when the difficulties attending their isolation have been overcome. *6. '' Chemical examination of Eriodictyon, Part 11." By Frank Tutin and Hubert William Bentley Clewer. Eriodictyon leaves were shown by Power and Tutin (Proc. Amer. Pharm. Assoc., 1906, 54, 352) to contain, in addition to other coin- pounds, three new, crystalline substances of a phenolic nature, namely, eriodictyol, C,,H,20G (m.p. 267O), homoeriodictyol, CI6H1,Oc (m. p. 223O), and a third substance, possessing 'the formula C1BH1308,which occurred only in very small amount. The present authors have employed a larger amount of the extract of eviodictyon leaves, and, after a prolonged process of separation, have isolated a larger amount of the last-mentioned compound, together with two new substances. Chvysoeriol, C1,H,,O,, the substance previously( isolated in small amount, forms golden-yellow leaflets, and does not melt at 337". It contains three hydroxyl groups, and yields triacet?/Zchr?/soerioZ, C16H906(C0mCH3)3, which melts at 211-212'.Xunthoeridol, Cl,H,,07, cry stallises in yellow needles melting at 258O. I'1.iacetyZxant~~oeri~oZ,C18H,10i(CO*CH3)3, melts at 175-1 76'. EriodonoZ, C,,H,,07, separates from dilute alcohol in pale yellow needles, which contain one molecule of water of crystallisation and melt at 199'; the anhydrous substance melts at 309'. It yields a tetw-acetgl derivative melting at 131'. "7. ('The hydration of precipitates." By Spencer U.Pickering. Many substances which are precipitated from aqueous solution are capable of emulsifying oils, and, by adjusting the amount of oil in the emulsion, the latter may be obtained of the same density as the liquid. By determining the density of this liquid, the density of the oil, arid that of the precipitate in the anhydrous conditions, and by ascertain- ing the weight of oil required to float a given weight of precipitate in two liquids of different densities, the weight of water combined with the anhydrous precipitate may be determined.The precipitate selected mas the compound 10Cu0,S03,CaS0,,Na,S04, which is of uniform composition when thrown down by adding lime-water to copper sulphate in the presence of varying quantities of sodium 13 sulphate. The amount of water combked with it was found to be about 42H,O. It was also ascertained that the water possessed the same specific gravity of ice, as in the case of the water of crystallisation of most hydrated salts. DISCUSSION. The PRESIDENTcalled attention to the fact that Dr.Chichester Bell had, more than ten years ago, made experiments on the velocity of sound in melted ice at +0*5*, and in cooled water at the same temperature. The velocities appeared to differ. Experiments by Dr. Wilsmore, unpublished, on the density of melted ice, and of cooled water, were indecisive, owing to the lapse of time before an accurate density could be determined. He also reminded Mr. Pickering that Playfair and Joule had con-cluded from their experiments that ‘‘water of crystallisation ” has the same molecular volume as ice. *8. “Studies of dynamic isomerism. Part VIII. The relation-ship between absorption spectra and isomeric change. Absorp-tion spectra of halogen, nitro-, and methyl derivatives of camphor.” By Thomas Xartin Lowry and Cecil Henry Desch.The band noted by Baly and by Hartley in the ultra-violet absorp- tion spectrum of camphor at a concentration of LV/10 appears also in the spectrum of /3-bromocamphor ; in both cases the band is weakened by diluting to iV/lOO,but is restored by the addition of alkali. A similar band of rather greater intensity is seen in the spectrum of a-bromocamphor at a concentration of X/100 ;as this band is developed by neutral solutions in which the a-bromo-compound is stable, and is only slightly intensified when a cocdition of equilibrium between isomerides is set up by the addition of alkali, its appearance cannot well be associated with the occurrence of reversible isomeric change. No marked change is seen in the absorption spectrum of a-bromo- camphor when a halogen is introduced into the p-or n-position, but the band is no longer developed when the second a-hydrogen atom is displaced by a halogen or by a nitro-group; it may therefore be associated with the presence of a displaceable hydrogen atom in the group -CHX*CO-, although not dependent on any actual transference of the atom ;a’-bromo-a-methylcamphor appears, however, to produce a shallow band.The weak band of nitrocamphor is greatly intensified by alkalis, but does not appear in the spectrum of the anhydride derived from the pseudo-form; it is therefore depencleut on the presence of a 14 displaceable hydrogen atom rather than on the occurrence of a pseudo-nitro-structure.The p-and rr-bromo-derivatives behave like nitrocamphor, but the a-halogen derivatives, which do not undergo isomeric change in sc ution, produce no absorption band. Nitro-caniphane does not gi e rise to a band either alone or in presence of alkali. 9. (( The relationship between the constitution and the absorption spectra of pyridine and various derivatives.” By John Edward Purvis. The absorption bands of 3 :5-dichloropyridine, two isomeric trichloro-pyridines, two isomeric tetrachloroaminopyridines, u-picoline and several of its derivatives, 2 :4 :6-trimethylpyridine and several of its derivatives, and chlorolutidine have been investigated. The results showed that : (1) the general effect of introducing atoms or groups of atoms into the nucleus is to increase the persistence of the absorption band as well as to shift it towards the red end of the spectrum, whilst when they are introduced into the side-chains they generally decrease the persistence.(2) The weighting of the nucleus does not, however, always mean that the absorption band is shifted towards the red end. The type and the spatial position of the intro- duced atoms 01-groups are factors iu determining the absxption. (3) In isomeric substances, the spatial positions of the substituting atoms in the nucleus are of considerable importance in influencing the position and the persistence of the absorbed rays. (4) The substitu- tion of atoms in the side-chains does not exert the same marked influence as when they are substituted in the nucleus.(5) The addition of hydrochloric acid to 2 :4 :6-trimethylpyridine and a-picoline (as well as to pyridine and lutidine) exerts a marked intluence on the vibrations of the nucleus, and the effect is very similar to that produced when chlorine atoms are introduced into the nucleus. Considerations on the influence of the changing valency of the nitrogen atom and other conditions in explanation of these facts were discussed. 10. “The action of mustard oils on the ethyl esters of malonic and cyanoacetic acids. Part 11.” By Siegfried Ruhemann. Irhe author showed that each of the cyclic compounds : which he described recently (Tmiz.~.,1908, 93,631) as existing in two modifications, namely, yellow and a colourless one, only occur in one form.He was led to this result in the course of a comparative study of these substances, and the similarly constituted compound : CH2*(?o Like the latter, the yellow cyclic compound (I) (ands<CO-NPh’ also 11) condenses with aldehydes with the formation of compounds of the general formula S< C( :CHR)*yO It was found that C(:NPh)-C(CN)* C0,Et the same prodncts were formed from the colourless compound, and this fact led to the view that both specimens of (I)were identical. The author was able to verify this conclusion. 11. ‘‘The interaction of hydrogen and chlorine.” By David Leonard Chapman and Patrick Sarsfield MacMahon. The authors have shown that the statement of Bunsen and Roscoe, that the rate of photochemical action between chlorine and hydrogen in a mixture containing equivalent amounts of these gases is reduced by the addition of a small volume either of hydrogen or chlorine, cannot be substantiated. Hydrogen and chlorine prepared by the electrolysis of concentrated hydrochloric acid do not possess the alleged inhibitive influence if sufficient precautions are taken to exclude air.It is considered likely that the hydrogen used by Bunsen and Roscoe contained oxygen. This is the more probable, as the gas employed by them mas prepared by the electrolysis of dilute sulphuric acid. 12. ‘‘Nitrogen chloride.” By David Leonard Chapman and Leonard Vodden. The authors have shown by a direct analysis that the amount of hydrogen contained in the vapour of nitrogen chloride prepared by the action of chlorine on a neutral solution of ammonium chloride is inappreciable. In harmony with this result, the ratio of nitrogen to chlorine is found to agree very closely with the formula NC1,.Gattermann’s conclusion that the freshly-prepared chloride contains hydrogen which can only be replaced by the continued action of chlorine is therefore called in question. *4method by which the ammonium chloride resulting from the hydrolysis of nitrogen chloride with hydrochloric acid can be isolated without the aid of a reducing agent mas described. The method affords the first entirely satisfactory demonstration of the reversibility of the change expressed by the equation : NH,Cl + 3C1, =NCl, + 4HC1.16 13. cc The atmospheric oxidation of P-methylhydrindone.” By Arthur Henry Salway and Frederic Stanley Kipping. P-Methylhydrindone, C,H,<:E!>CHMe (Kipping and Clarke, Tyam., 1903, 83,913), is slowly oxidised on exposure to the air, giving a mixture of compounds from which acetic, phthalic, and benzylmethylketone-o-carboxylicacid, CH3*CO*CHa.C,H,*C0,H, may be isolated ;a small amount of a neutral compound, melting at 211”, is also present in the crude oxidation product. It is suggested that the ketonic form of methylhydrindone (compare Kipping, Proc., 1902, 18, 34) first undergoes change to the enolic modification, which then combines directly with a molecule of oxygen in much the same way as unsaturated compounds combine with a molecule of ozone ;this additive product is then decomposed by water, giving benzylmethylketone-o-carboxylicacid, and by similar processes the latter is oxidised to phthalic and acetic acids.14. ‘‘A glucoside from Tephrosia purpurea.” (Preliminary note,) By George Clarke, jun., and S. C. Banerjee. Tephyosia purpurea, Pers. (nat. ord. leguminosae), a small woody annual, grows luxuriantly during the monsoon in many waste tracts of the United Provinces of Agra and Oudh. The leaves yield a crystalline glucoside on extraction with either ethyl alcohol or acetone, and subsequently treating the evaporated extract with water and light petroleum to separate tar. The yield from one extraction is approximately 2 per cent.on the dried leaves. The glucoside melts and decomposes at 180-185O (uncorr.), and on hydrolysis with dilut’e sulphuric acid yields quercetin and dextrose. It appears, therefore, to be identical with osyritrin (A. G. Perkin, Trans., 1897, 71, 1134). 15. Note on the constitution of the carboxyl group.” By Ida Smedley. From a consideration of the physical and chemical properties of the 0carboxylic acids, the constitution *C<l I is suggested for the carboxyl OH group as better representing its physical and chemical behaviour. 1.T 16. The relation between the chemical constitution and optical properties of the aromatic IX-and 7-diketones." By Ida Smedley. Yellow s-dibenzoylethylene (m. p. 11 1") was prepared by con- densing benzoylformaldehyde with acetophenone in the presence of acetic anhydride.This compound is identical with that obtained by Paal and Schulze (Ber., 1900, 33, 3784) by the action of heat on dibenzoylmalic acid. From a consideration of the solubility, melting point, refractive power, and colour of the cis-and trccns-isomerides, the yellow form, which has the greater solubility, iower melting point, and greater refraction, is regarded as the cis-isomeride, and not the trans-form as suggested by Paal and Schulze. These two forms furnish the first instance described of a marked difference in the refraction of cis-and ti*ans-isornerides. The molecular refractions of the following compounds were measured : phenyl methyl diketone (Ma=41 *32),benzoylformaldehyde (Ma =36-99), cis-dibenzoglethylene (m.p. 11 lo;D4, =73-96), trans-dibenzoylethylene (m. p. 134"; Ma= 71-84), cis-dibenzoylphenylethylene(Ma=99-57),cis-dibenzoyldiphenyl-ethylene (Ma= 122.76),trans-dibenzoyldiphenylethylene(Ma= 123.71). The evidence from a consideration of their refractive power is applied to determine the constitution of the a-diketones and s-diacylethylenes. Marked similarities are shown in the behaviour of these two classes of compounds. 17. '' The transformation of aliphatic nitriles into alicyclic imino- compounds.'' (Preliminary note.) By Jocelyn Field Thorpe. For some time past, experiments have been in progress having for their object the study of the conditions under which aliphatic di- nitriles having the nitrile groups separated by two, three, four, etc., carbon atoms pass into the corresponding alicyclic imino-compounds.Preliminary experiments indicate that there is a greater tendency to form a three-carbon ring in this manner than a ring of four carbon atoms, but that the cychpentane ring is produced with most remark-able ease. Thus, during some experiments on the formation of the eyelopropane ring by the interaction of ethyl sodiocyanoacetate and ethylene di- bromide, Carpenter and Perkin (Trans.,1899, 75, 921) isolated, as a by-product, a substance which melted at 119.5*, and to which they assigned the formula CN*CH,*CH,*CH,*CH(CN)'CO,Et(ethyl a8-di-cyanovalerate), owing to the fact that it yielded adipic acid on hydrolysis with alkaline hydrolysing agents.1s It is now found that this substance is ethyl 2-iniino-3-cyanocpZo- pentane-1-carboxylate (l), and that it is immediately converted by the action of cold concentrated hydrochloric acid into ethyl 3-cyanocgclo- pentan-2-one-1-carboxylate(11) : Co<c”(CO,Et).C;iH, CH(CN)-CH, (1.) (11 1 Ethyl 2-imi~zo-3-cyanocyclopentane-l-ca~~bozylntebe produced in can almost theoretical yield by the interaction of ethyl sodiocyanoacetate and ethyl 1-cyanocycZopropane-1-carboxylate in alcoholic solution, the sole products of the reaction being the sodium compound of the imino- compound and ethyl carbonate ; the equation representing the initial and final products of the reaction is therefore as follows : CN*CHNa*CO,Et+ C0,Et-C(CN)<~H2+ EtOH -+CH, A similar condensation product is obtained when ethyl sodiomalonate is substituted for ethyl sodiocyanoacetate in the above equation.The investigation of the properties of these cyclic ketones is in progress. 18. “Action of alcohols on metallic calcium.” By Frederick Mollwo Perkin and Lionel Pratt. When calcium is added to alcohols reaction ensues and the alkyl- oxide, Ca(OAlb),, is produced (PToc.,1907, 23,304). The reaction, however, is generally slow, but is greatly facilitated by heat. Calcium hydride reacts more readily than metallic calcium, but the product is less pure than when the metal is employed, owing to im- purities in the calcium hydride. Calcium ethoxide is soluble in ethyl alcohol, and crystallises with two molecules of alcohol of crystallisa-tion.Other alkyloxides are not so readily prepared, owing to their insolubility in the alcohols. Calcium ethoxide has been employed satisfactorily for organic condensations in place of sodium ethoxide. 19. ‘(The condensation of oxymethylenecamphor with primary and secondary amino-compounds.” By William Jackson Pope and John Read. On condensing externally compensated a-phenylethylnrnine with d-oxymethylenecamphor, two stereoisomeric products are obtained, one from each of the optically active components of the primary base ; a method is thus indicated for ascertaining whether a particular primary amino-compound is or is not externally compensated. The 19 two products exhibit marked mutarotation, and this is attributed to their conversion in solution into isodynamic mixtures.d-Oxymethylenecamphor itself and its condensation products with aniline, ptoluidine, and /3-naphthylamine exhibit mutarotation in various solutions and this is again attributed to isodynamic change. 20. “Note on the variation in the catalytic activity of mineral acids with changes in their concentration.” By Arthur Lapworth. Several recent investigations (Senter., Y’rccns., 1908, 91, 467 : Stieglitz, Ainei-. Chem. J., 1908, 39,29 et sep. ; Acree and others, Ber., 1908, 41, 3214 et sey.) suggest that during certain changes, in which electrolytes are concerned, not only simple and complex ions are directly concerned, but that intramolecular changes in, and interactions between, non-ionised substances may occur? and sometimes even to the extent of being a necessary part of the process.The author recently referred to such a possibility in the case of esterification as accelerated by an acid (Tram., 19OS, 93, 2196, 2197), inferring that the disproportionate increase in the velocity with increase in the amount of mineral acid may possibly be due to ;t secondary reaction of this nature. It is necessary to state that the discussion applied only to those cases where no relatively powerful base is present in such small quantity that this decreases rapidly on addition of mineral acid, as might conceivably be the condition in alcohol containing only a very little water; the general case, however, comes under the discussion mentioned, and, as has long been recognised, is doubtless intimately connected with neutral salt action.Attention must also be drawn to the fact that the expression for If2ld’(H2)qjz (?tot : loc. cit., p. 2197), which indicates the direction ’udA2 of change in relative quantity of non-ionised compounds with altera- tion in the amount of catalyst, is always positive, this not being limited even by the condition suggested. 21. The condensation of dimethgldihydroresorcin with ethylamine.” By Paul Haas. By the action of nitrous acid on the condensation product of ethyl-amine with dimethyldihydroresorcin, a compound of the constitution is produced. This substance crystallises from water with two niolecules of the solvent, and has a very intense carmine colour ; when dried in a vacuum it becomes anhydrous, and is then dark blue. 20 ANNIVERSARY DINNER.It has been decided by the Council to arrange for a Dinner of’ tlio Fellows of the Society and their friends, to be held at the Whitehall Rooms onThursday, March 25th, 1909, this being the day fixed for the Snnual General Meetiug. E’iwther particulars mill be announced shortly. ERRATA. PROCEEDINGS,1908. Page. Line. 274 7 fo?. (( hypoiodate ’’ read ‘(hypoiodite.” 380 20 title should be ‘‘Silicon researches. Part XIII. Silicon halides and pyridine, acetonitrile, etc.” ALthe next Ordinary Meeting on Thursday, February 4th, 1909, at 8.30 p.m ,the following papers will be communicated : ‘‘The triazo-group.Pilrt VII. Intermtion of benzhydcoxim ic chloride and sodium azide.” By 31. 0. Forster. bi The triazo-group. Part VIII. Azoimides of the monobasic aliphatic acids.” By M. 0. Forster and l-t. Miiller. -‘Nitro-derivatives of ortho-xylene.” By A. W. Crossley and Miss Xora Renouf *‘The divergence of the atomic weights of the lighter elements from whole number^.^' By A. C. G. Egerton. ‘& Benzyl and ethyl derivatives of silicon tetrachloride.” By Ci. Xartin and F. S. Kipping. ‘*The constituents o€ the bark of I’w.mzcs Skrotiwt. Isolation OF 1-niandelonitrile glucoside.” Ey F. B. Power and C. W. Noore. The mechanism of the reductiori of nitroanilines and nitrophenols.” By 13. Plurscheim.*‘The relatioh between the strength of acids and bases, and the quantitative distribution of atIinity in the molecule.” By B. Fliirscheim. 7‘ A simple notation for indicating the configuration of the sugars ant3 allied substances.” By T. S. Patterson. “Xote on tlie determination of the rate of chemical chi;cnge by measurement of the gases evolved.” By F. E. E. Lamplough. “ The formation and reactions of imino-compounds. Part VIII. The formation of methyl derivatives of 1 :3-diamino-2-phenylnsphtha-leiie from tJie three tolylacetoiiitIilesc.“ By 8. R. Best and J. F. Thospe. LL The effect of conjugated unsaturated groups on optical activity. Part I.” By T.P. Hilditch. K. CLAY .\SDSONS, L‘TD., BREAD S’T. HILL, E.C., AND BUXU.ll-, Sl-FL‘ULK.
ISSN:0369-8718
DOI:10.1039/PL9092500001
出版商:RSC
年代:1909
数据来源: RSC
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