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Proceedings of the Chemical Society, Vol. 23, No. 319 |
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Proceedings of the Chemical Society, London,
Volume 23,
Issue 319,
1907,
Page 1-23
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摘要:
Issued 30/ 1/07 PROCEEDINGS OF THE CHEMICAL SOCIETY. Vol. 23. No.319. Thursday, January 17th, 1907, at 8.30 pm., Professor K. MELDOLA,F.R.S., President, in the Chair. Messrs. P, S. Arup, W. C. Ball, and J. Hamer were formally admitted Fellows of the Society. The PRESIDENTannounced the decision of the Council that during the remainder of the present Session the Library shall be kept open for the use of Fellows every Thursday from 10 am. until 9 p.n~., except on those evenings on which the Society meets when it will remain open until 10.30 p.m. Certificates were read for the first time in favour of Messrs. : Leslie Hamilton Berry, B.Sc., Penshurst, Croham Park Avenue, 8. C'roydon. Mohan Nath Kedarnath Dikshit, 2 1, Burlington Ro.td, Bayswater, W.John Eclmin Farmel', Blelsoe, New Koad, Mitcham Junction. Percival John Fryer, 27, Minster Road, Cricklewood, N.W. William Heber Green, D.Sc., The University, Melbourne. Richard Higham, 133, Mauldeth Road, Withington, Mauchuster. William James Hoyten, X.K.U.S., F.K.C.P., 37, Kavelslvke Road, Wirnblodon Park, S.W. 2 Francis Townshend Cunynghame Hughels., Major, Koyal Xint, Calcutta, India. Sidney James Jennings, B.Sc., 367, Queen’s Road, New Cross, S.E. George Lunan, 50, Garscube Terrace, Murrayfield, Edinburgh. William George Twiney, B.Sc., St. Joseph’s College, Colombo, Ceglo u. Charles Rowlatt Watkins, B.A., Aldenham School, Elstree, Herts. William Henry Williams, Government Education Dept., Hong Koiig. The Council has ordered the following letter and report to be printed in the Journal and Proceedings of the Society : GOVERNMENTLABORATORY, CLEMENT’S INN PASSAGE, STRAND, W.C.LONDON, 15th Novembev, 1906.GENTLEMEN, I have the honour to forward to you, for presentation to the Council of the Chemical Society, the Report of the International Committee on Atomic Weights, 1907, to which I have aftixecl, as desired by them, the names of Professors Moissaii and Ostwald. The Committee, for reasons stated in the Report, have suggested new values for the atomic weights of bismuth, nitrogen, tantalum, and terbium, and they are further of opinion that alterations are needed in the atomic weights of silver and chlorine, but before recommending any change as regards these elements they consider it expedient to wait for fuller information of the results of deter-minations known to be in progress.The new values for silver and chlorine will, of courso, have an influence upon a large number of atomic weights. I am, Gentlemen, Your obedient Servant, T. E. THORPE. The Hon Xecretccries, The C?.emicaZ Society, Burlingtoy& House, London, IT. Report of the International Committee on Atomic Weights, 1907. Since the preparation of our last report, for 1906, a number of im-portant memoirs upon atomic weights have appeared, The results obtained may be briefly summarised as follows : Bisrnut?b.-Work done at Erlangeri under the directlion of Gutbier. (Zeit. Elektrochem,, 1905, 11, 831) has been published ill the form of three doctoral disscrtntions (1,.Birckenbnch, 1905 ; H. Mehler, 1905 ; R. L. Jnnssen, 1906). Birckenbach, by synthesis of the oxide from tlhemetal, foiincl, in mean, Bi =208.05. A series of reductions of the oxide gave Ki = 208.08. Mehler determined the ratio BiBrs :AgBr, and found Ri=208b05. By synthesis of the sulphate from tho metal, Janssen obtained the value Bi =208.074. These determinations are concordant, and also agree with the earlier measurements by Sclmeider mid Lame and with a series by Marignac. The atomic weight of bismuth, therefore, is to be taken as 208.0 in round num- bers, and the value 2085, as hitherto given in our table, is too high. Uromirzd.--Baxter’s (J. Anzer. Chena. Soc., 1906, 28, 1322) deter-minations of t’his constant are based upon the antecedent values Ag 7 107.93 2nd (31= 35.473.Eighteen syntheses of silver bromide gave, in mean, Br =79.953. Thirteen experiments upon the conver-sion of AgBr into AgCl gave Br =79.952. Cacl!wiuw.-The memoir by Baxter, Hines, and Frevert (ibid., 1906, 28, 770) is a continuation of the research which was noted last year. Vonr ratios were measured with the following results, when Ag = 207.9:; : CdBr2:2Ag. Cd = 112.470. CdBr, :2AgBr. Cd = 112.464. CdCl, : 2Ag. Cd = 11 2.471. CdCI, : 2AgCl. Cd = 112.470. Copper.-A series of analyses and syntheses of copper oxide by Murmann (LWonatsh.,1906, 2’7, 351) gave the value Cu =6353. The data are not concordant, and the determinations are not entitled to much weight.Iodine.-Gallo (Gaxxetta, 1906, 36, 116) has determined the atomic weight of iodine electrolytically, comparing the iodine liberated by a current with the silver deposited. His values range from 126.82 to 126.98, or, in mean, 126.89 when Ag=107*93. This result is more nearly in accord with the determination by Stas than with the later measureinen ts. iVitroyen,-Gray’s (Trans., 1905, 87, 1601) work upon the atomic weight of this element, noticed in our report for 1906, has since been published in full. His mean results are as follows : from the density of nitric oxide, N= 14,006; from the analysis of nitric oxide, N= 14.010; from the density of nitrogen, N = 14.008. The mean of all the determinations is N = 14.0085, or very nearly 14.01. This agrees closely with the earlier measurements by Guye, Rayleigh, and Leduc, and leaves no reasonable doubt but that the new value should replace the 14.04 as given in our annual table.In a later paper (Tmrzs., 1906, 89, 1173) Gray has gathered corroborative evidence from various soiirces, and has discussod Stas’s rntios in ordey to dis-corer their possible errors, Other discussions of simihr pnrport are by Guye * and Scott (Chent. News, IOOG, 93,20), butl they are not final. Experimental cvidence alone can reveal the cause of discrepancy between the new figure and the old. Palladium.-Amberg (Annalen? 1905, 341, 235) has redetermined the atomic weight of palladium by analysis of palladosoammine chloride, PdN,H,Cl,.The value obtained is Pd = 106.688, or 106.7 nearly. Five other analyses of the same salt, by Krell (haug, Dissertatim, Erlangen, 1906), gave a mean of Pd =. 106.694. Recalculated with Richards’s value for C1, and rejecting one experiment as defective, Krell concludes that Pd = 106.18, but this again would be lowered by the adoption of the newer value for N. Any change in this constmt may well be deferred until the antecedent atomic weights are more definitely known. Silver.-In an attempt to determine the source of error in Stas’s figures for nitrogen, Guje and Ter GazarianT examined the fundamental potassium chlorate ratio. They found that potassium chlorate crystnl-lises with a small quantity of chloride as an impurity, the amount being nearly constant and about 2.7 parts in ten thousand.Applying this correction to Stas’s ratios, his value for silver is lowered from 107.93 to 107.89. A re-discussion of ten fundamental ratios gave figures for silver ranging from 107.871 to 107.908, or 107.89 in mean. If this conclusion is sustained, the Stas’s ratios for silver nitrate will give a value for nitrogen in harmony with the figures obtained by Guye and Gray. 2’antaZum.-Hinrichsen and Sahlbom (Be?., 1906, 39, 2600) have determined the atomic weight of tantalum by conversion of the metal into the pentoxide. Five such syntheses gave Ta =180.59 to 181.77, or 181.0 in mean. This value should replace the old determination by Marignac as given in our previous tables.The Rare Earths--On the metals of this group a notable amount of work has been published during 1906. From five determinations of water in terbium sulphate, Urbain (Compt. vend., 1906, 142, 957) deduces the value Tb = 159.22 ; and this should supplant the older, questionable data, In another paper (ibid., 1906, 142, 785) Urbain gives an atomic weight of 163.49 to dysprosium, but without details or weighings. By a volumetric method, Feit and Przibylla (Zeit.anorg. Chern., 1906, * Ber., 1906, 39,1470. For Guye and Bogdan’s completc: memoir upon nitrous oxide, see J. Chiwt.php., 1905, 3,537. .f Cornpt. rend., 1906, 143, 411. See also J. Chiv2. phys., 1906, 4, 174, for a paper by Guye on the need of a general recalculation of atomic weights.5 50, 249) have determined the amount of sulphuric acid required to neutralm several of the oxides in this group, and have in that way obtained new estimates of the corresponding atomic weights. The final results, reduced to a vacuum standard, are as follows : Praseodymium ......... 140.62 Gadolinium.. ............. 157.35 Neodymium ............ 144.52 Ytterbium ............... 173.52 Samarium ............... 150.47 Yttrium .................. 89.40 In Abegg's Haiadbuch der unorgunische Chemie, Brauner has given full summaries of all atomic weight determinations. With these summaries, in connexion with the rare earth metals (in Bd. 3, Abth. 1,pp. 263, 376, 254, 304, 315, 335), he has cited some hitherto un-published determinations of his own.His results are : Praseodymium ......... 140.97 Gadolinium ............... 155.78 Neodymium ............ 143.89 Erbium .................. 167.14 Samarium ............... 150.71 Ytterbium ............... 173.08 Among these figures that for Gd is admittedly too low, and that for Sa is vitiated by the presence of europium in the material studied. From the evidence presented in this report, and in preceding years, we now feel justified in recommending the following changes in the table : Nitrogen, from 14.04 to 14.01. Bismuth, ,, 208.5 ,, 208.0. Tantalum, ,, 183.0 ,, 151.0. Terbium, ,, 160.0 ,, 159.2. Other changes which seem to be needed because of alterations in the atomic weights of silver and chlorine cannot yet be made with safety.The atomic weight of silver, as deduced from Stas's data, is probably too high, but by an unknown amount, and that will affect the entire table. If we assume, with Guye, that Ag= 107.89, with the proportional changes in C1 and Br, the atomic weight of barium, as determined by Richards, will be reduced by 0.05. Such a change, which is probably extreme, does not affect the utility of the accepted atomic weights at all seriously, and no important interest will suffer if we delay the suggested alterations until our knowledge of the corrections to be applied is more exact. Guye's conclusions, although strongly supported, are not final, and they should be neither accepted nor rejected except upon the basis of much more complete evidence than we now possess.The atomic weight of chlorine, as given in our last report, is certainly too low, but it depends in part upon the un- determined change to be applied to silver. For that reason, as well as for the reason that a change in chlorine affects many other values, we prefer to leave the figures as they are and to wait for fuller informa- tion. That information will doubtless be supplied by researches now known to be in progress, and the corrections which they will furnish ought not to be delayed very long. One addition to t.he table seems to be legitimate. Europium, with an approximate atomic weight of 152, appears to he a definite element, as shown by the investigations of Deniarqay, Urbain. and Lacombe, Eberhard, and Feit and Przibylla.Its existence is recognised in Abegg's Handbuch, and its claims to a place in the table are certainly as great as those of erbium, thulium, or terbium. As for dysprosium, its admission to the table may well be delayed until a better det ermina- tion of its atomic weight 'shall have been made. In conclusion, we urge upon all chemists who are engaged in the determination of atomic weights to send copies of their publications to all the members of this committee in order that their work may be promptly recognised and not overlooked. Data published in standard journals are of course easily found, but publications of local societies and doctoral dissertations might readily escape our notice. Professor Seubert, an original member of this committee, has resigned.Professor Ostwald has been designated as his successor.* The table offered for 1907 is appended hereto. F. W. .CLARKE, H<NRI %fOISSA4N, IVILHELM OSTWALD, 'l'. E. 'L'HORPE. * See Bcr., 1906, 39, 2176, for tile forriial a~~nou~iceiiieiitof this change. 7 Aluminium ................. A1 27 *1 Neodymium .................. Nd 143'6 Antimony....................Sb 120-2 Neon ...........................Ne 20 Argon ......................A Arsenic .....................As 39'9 76 *o Nickel ........................ Ni Nitrogen ..................... N 58-7 14.01 Barium .......................Ba 137'4 Osmium ..................... 0s 191 Bismuth....................Bi 208.0 Oxygen ........................ 0 16-00 Boron ......................B 11.0 Palladium ..................... Pd 106.5 Bromine ....................Br 79-96 Phosphoriis .................. P 31'0 Cadmium ..................... Cd 112'4 Platinum .....................Pt 194'8 CEesiuni.......................Cs 132.9 Potassium ..................... I< 39-15 Calcium........................ Ca 40 *1 Praseodymium ...............Pr 140-5 Carbon ........................C 12-00 Radium ........................Rd 225 Cerium ........................ Ce 140'26 Rhodiuin ..................... Rh 103.0 Chlorine ..................... C1 35.45 Rubidium ....................Rb 85.5 Chromium .................. Cr 52'1 Ruthenium ..................Ru 101.7 Cobalt ........................Co 59.0 Samarium ................. Sa 150'3 Columbium ..................Cb 94 Scandium .................. Sc 44-1 Copper ........................ Cu 63'6 Selenium ..................... Se 79'2 Erbium ........................Er 166 Silicon ......................Si 28.4 Europium .................... Eu Fluorine ................... F 152 19'0 Sodium ....................... Na ........................Silver Ag 107'93 23.05 Gadoliniuni .................. Gd 156 Strontium .................. Sr 87'6 Gallium .................. Ga 70 Sulphur ..................S 32'06 Germanium ..................Ge 72.5 Tantalum .................... Ta 181 Glucirium .................G1 9-1 Tellurium .................... Te 127.6 Gold ...........................AU 197.2 Terbium ..................... Tb 159'2 Helium ........................He 4.0 Thallium ................... T1 204.1 Hydrogen ..................... H 1.008 Thorium ..................... Th 232-5 Indium ...................... In 1-15 Thulium ..................... Tm 171 Iodine ........................I 126.97 Tin ........................... Sn 119.0 Iridium ....................... Ir 193.0 Titanium .....................Ti 48.1 Iron ........................... Fe Krypton ..................... Kr 55.9 81.8 Tungsten ..................... W Uranium ..................... U 184 238'5 Lanthanum .................La 138'9 Vanadium ..................... V 51'2 Lead .........................Pb 206'9 Xenon ........................ Xe 128 Lithium .................... Li 7'03 Ytterbiuni .................Yb 173.0 ManganeseMagnesium .................. Mn .................. Mg 24 '36 55.0 Yttrium ..................... Zinc ........................... Yt Zn 89.0 65'4 Mercury ..................... Hg 200.0 Zirconium.....................Zr 90-6 Molybdenum ...............Mi 96.0 8 Of the following papers, those marked * were read : "1. '(The relation between absorption spectra and optical rotatory power. Part I. The effect of unsaturation and stereoisomerism." By Alfred Walter Stewart. The author has examined the absorption spectra of certain saturated and unsaturated acids, and compared the results with the rotatory power of their amyl esters.The results show that a close relation exists between the general absorption power of compounds and their molecular rotation. The substance having the greater general absorp- tion has also the greater molecular rotation. The case of the amyl esters of hydrocinnamic, cinnamic, and phenylpropiolic acids, which seems anomalous at first sight, agrees with this. An examination of the spectra of some stereoisomeric acids of the ethylene series showed that the rule holds in their case also. Experiments are in progress in' other branches of the subject, for example, active and inactive isomerides, birotation, the influence of the solvent on the rotatory power, $c.DISCUSSION. Dr. .MCKENZIEpointed out that the values for the molecular rota- tions of the amyl esters of hydrocinnamic, cinnamic, and phenylpropiolic acid respectively, determined by Walden and quoted by the author, were obviously incorrect, since the amyl alcohol used by Walden in 1896 was a mixture. Since it was now possible to separate the optically active constituent of fuse1 oil in a pure state by means of 3-nitrophthslic acid (Bey., 1901, 34,485), he asked whether the author had prepared the pure esters in question and determined their rotations. Mr. STEWARTexplained that owing to the complexity of the amyl spectrum it had been found best to examine the spectra of the acids and not those of the amyl esters.The causeof the change in rotation evidentIy is to be sought in the acidic part of the ester molecule. The results obtained by Sir W. H. Perkin in the case of the magnetic rotation of saturated and unsaturated acids agree with those observed in the case of optically active esters of the saturated and unsaturated series. ”2. ‘6 Organic derivatives of silicon. Part 11. The synthesis of dl-benzylethylpropylsilicol,its sulphonation, and the resolution of the sulphonic derivative into optically active components.” By Frederic Stanley Kipping. dl-Benxylethylpropylsilicol, EtPrBzSi-OH, has been synthesised by the following series of reactions (compare Proc., 1904, 20, 15): SiCl, +MgEtRr =SiEtC1, +MgClBr. SiEtC1, +MgPhBr =SiEtPhC1, +MgClBr.SiEtPhC1, +MgPrBr =SiEtPhPrCl +MgClBr. SiEtPhPrCl +MgBzCl =SiEtPhPrBz +MgCl,. SiEtPhPrBz +H,O( +H,SO,) =SiEtPrBz*OH+ C6H6(+ H,SO,). The silicol thus initially produced yields, with sulphuric acid, a mixture of sulphonic acids of which one has been isolated in the form of its ammonium salt. This acid is probably a derivative of the corresponding oxide, having the constitution SOsH*C6H,~CH,*SiEtPr*O~PrEtSi~CH,*C6H,~S0,H; it is the externally compensated compound, and although many of its salts with optically active bases crystallise unchanged, the d-methyl- hydrindamine salt, can be resolved by crystallisiFg fractionally from aqueous methyl alcohol. The dBdA-salt is the more sparingly soluble and melts at about 205O ; the impure dBZA-salt from the most soluble fractions melts at about 135’.The ZBZA-salt has been prepared by resolving the acid with 2-methylhydrindamine. The two optically active acids have very low specific rotations +_ 4” roughly), but there is ample evidence of their enantio-morphous relationship. DISCUSSION. Dr. LEWKOWITSCH,referring to the statement that different melting points were obtained with one and the same substance, asked whether this phenomenon mas accompanied by the appearance of different colours, such as Jaeger had observed in the case of the liquid aniso- tropic phases of the esters of cholesterol and phytosterol at their different melting points. Prof. KIPPINGstated that the appearance of such colours had not been observed by him.10 “3. (‘The association of phenols in the liquid condition.” By John Theodore Hewitt and Thomas Field Winmill. The authors have determined the surface energy of several liquids, and find that the association of phenols is diminished or entirely inhibited by the presence of ortho-substituents. Comparison with meta- and para-isomerides has clearly shown that the effect is due more to the position than to the nature of the substituent group. The effect of steric hindrance is also seen with the aromatic alcohols. Monophenylcarbinol (benzyl alcohol) is markedly associated at the ordinary temperature; the molecular weights of fused di- and tri- phenylcarbinol are, however, normal. DISCUSSION.Dr. HEWITT,replying to the remarks of the President, said he sup- posed that probably they (the authors) had not encountered the best conditions for converting o-aminophenol into o-bromophenol. Respect -ing Mr. Baly’s contention that any hindrance to associakion was structural rather than sterical, it was at least remarkable that the groups of larger molecular volume had a more marked effect than those, such as methyl and chlorine, whose molecular volume was smaller. “4. (4 A new mercuric oxychloride,” By John Theodore Hewitt. On allowing solutions of sodium hydroxide and mercuric chloride in sodium chloride to diffuse into one another, a layer of sodium chloride solution of intermediate density being interposed, very dark red crystals having the formula Hg,O,CI, are deposited.These were at first considered to be red mercuric oxide or mercuric hydroxide, since on solution in hot dilute nitric acid and addition of silver nitrate solution no precipitate was obtained. It has now been found that if a silver chloride precipitate is suspended in dilute nitric acid and mercuric oxide added, not only is the latter dissolved but also the silver chloride. In the estimation of chlorine in the oxychloride the latter was dis-solved in warm dilute sulphuric acid, the mercury precipitated with sodium hyposulphite, and after oxidation of the excess of this reagent with dilute nitric acid, the chlorine was estimated in the usual way as silver chloride. 30ISCUSSION. Dr. HEWITTwas afraid he had not made the fact quite clear, that when silver chloride is dissolved in dilute nitric acid by addition 11 of mercuric oxide the result is not to be attributed to the formation of a complex silver ion, but to the employment of the chlorine in forming complex ions with the mercury.The solubility of silver salts in albumenoid solutions mentioned by Dr. Divers was hardly of a similar nature, in the latter case solution depended rather on colloidal suspension. “5. ‘‘Preparation of chromyl dichloride.” By Herbert Drake Law and Frederick Mollwo Perkin. The authors find that the best method for preparing chromyl dichloride is to dissolve chromic acid in rather more than the equivalent quantity of concentrated aqueous hydrochloric acid and to add to this solution concentrated sulphuric acid in small quantities at a time, the mixture being cooled between each addition.After standing for about twenty minutes in a tap funnel the heavy under layer of chromyl dichloride is drawn off. It can be purified by aspirating dry air through it and subsequent distillation. The yield is almost theoretical. *6. ‘‘ Oxidation of hydrocarbons of the benzene series.” By Herbert Drake Law and Frederick Mollwo Perkin. The authors have examined the products of oxidation of aromatic hydrocarbons by lead peroxide and manganese peroxide in acid solu- tion, by chromyl dichloride and by persulphates in acid solution in presence of silver salts. The hydrocarbons investigated were toluene, the three xylenes, mesitylene, $-cumem, and cymene.Iu all cases varying yields of the monoaldehydes were obtained. Toluene gave with lead peroxide 24 per cent. of benzaldehyde, with manganese peroxide 5 per cent,, with chromyl dichloride 44 per cent., and with persulphates 78 per cent. In the remaining cases, as a rule, the yield with chromyl dichloride was better than with the other oxidising agents, that obtained with persulphates being second. In general, lead peroxide gave a larger quantity of aldehyde than did manganese peroxide. 7. ‘(The constitution pf silver nitrite ; a correction,” By Edward Divers. In the opening paragraph of a paper which has just appeared (Trans., 1906, 89, 1900), RAy and Neogi state that the present writer is inclined to accept as fairly conclusive the evidence which they have adduced in favour of the oxylic constitution of silver nitrite.12 In his note in the Proceedings (1905, 21, ZSl), to which they make reference, no opinion at all is expressed as to the constitution of silver nitrite. The authors must have made the statement under some mis- apprehension of the writer’s words, which he cannot account for. I‘8. Aromatic selenonium bases.” By Samuel Smiles and Thomas Percy Kilditch. When anisole or phenetole are heated on the water-bath with selenium dioxide and aluminium chloride, the chlorides of the corre- sponding selenonium bases are formed. To isolate these substances, the reaction mixture is decomposed with water and freed from excess of phenolic ether by distillation in steam; finally the mixture is extracted with chloroform which, on evaporation, leaves the chloride of the base as a red oil.Yrianisyl-and ti.ip~~enetyl-seZenoPiiumchloi*ides are viscous oils, the aqueous solutions of which yield strongly basic h3droxides on treatment with silver oxide. The iodides are sparingly soluble oils. The pZatinic?do&?eswere obtained as brown precipitates, insoluble in water and very soluble in acetone. The platinichlode of triphenetylselenoniurn melts at 82-83”. The dichromates of these bases are insoluble in water and are precipitated in yellowish-brown flakes when an acid solution of potassium chromate is added to solu- tions of the chlorides. They are very unstable and turn dark on exposure to the air.Trianisylselenonium diclwomate melts at 65-70°. 9. ‘(The relation of colour and fluorescence to constitution.” By Arthur George Green. In a paper bearing the above title (Trans., 1906, 87, 1SS7), 0. Silberrad has recently described a number of complex phtbaleins formed by t.he condensation of mellitic and pgromellitic acids with resorcinol. From the fact that the silver salts of these phthaleins correspond to tbe substitution of hydrogen by silver, not osly in all the carboxyl groups of the mellitic residue, but also in the two phenolic hydroxyl groups of each xanthene ring, it is concluded that ‘‘neither the colour nor the fluorescence of these compouncls is dependent on the presence of quinone linkings, for in many cases tt quinonoid structure is impossible.” This conclusion Silberrad is inclined to extend to the phthaleins in general.A study of the phthaleins of phenol and quinol, which the author has had in progress for some time past, has brought to light several facts pointing to an opposite conclusion and strongly confirming the view that the coloured salts of these phthaleins have a quinonoid structure. It therefore appears advisable to point out that Silberrad’s 13 deductions are in no sense necessary, but that on the contrary his com- pounds may be represented with equal or greater probability upon a quinonoid type. For instance, in place of the carbinol formula (I)for the silver salt of the octabromohcxahydroxy-p-dixnnthylbenzenetetra-carboxylic acid, the orthoquinone formula (11) may be substituted.The latter is analogous to (111),the formula proposed by the author for the potassium salt of quinolphthalein (Ber., 1906, 39,2365) : Br Br Br OH Br Br\/-C(OH)--'I AgO/\-O----/\O \/Br A g Br,)-y=,)Br A g~/\-A=/\oag c,(CO,*g), C',(CO, Ad4 Br/\-d (OH)--{\Er AgOl I--@--\/Br \,0"9 Br Br OH Br (111.) 10.('Tetraketopiperazine." By Alfred Theophilus de Mouilpied and Alexander Rule. The authors have studied the action of sodium alkyloxides on esters of the type of ethyl oxamate, NH,*CO*CO,Et, whereby the elimina- tion of 1 molecule of alcohol would be expected to give rise to ring compounds containing an imino-group.Ethy1 oxamate should by such co a reaction furnish oxalimide, I >NH, which is referred to by Ost co and Mente (Bey., 1886, 19,3228), but its existence appears to be very doubtful. The authors were not able to obtain it, but prepared from ethyl oxamate, tetruketopipei*axine, which has twice the molecular weight of oxalimide and which seems to be the substance described under the latter name. Tetraketopiperazine was also obtained by the condensation of ethyl oxalate with oxamide; a hydrazone, silver and sodium salts have been prepared, and the folIowing constitutional formula is suggested : Methyl succinamate yields succinimide by a similar reaction, and ethyl malonamate gives a substance of formula C6HS05NS,resulting 14 from the condenJation of 2 molecules of malonamic acid through loss of 1 molecule of water.A general method for the preferential saponification of a cnrboxy-alkgl group occurring in the same compound with an acid amidegroup was described. Saponified with alkali in the usual way, ethyl oxamate yields the semi-ethyl ester and oxalic acid, and ammonia is simultaneously evolved. By using the theoretical amount of pure sodium alkyl- oxide in dry benzene solut,ion a large yield of sodium oxamate is obtained. 11. '( Transformations of highly substituted nitroaminobenzenes. 11. s-Tribromo-1-nitroaminobenzene." By Alice Emily Smith and Kennedy Joseph Previt6 Orton. Treatment of 2 : 4 : 6-tribromo- 1-nitroaminobenzene, C,H2Br,*NH*N0,, with sulphuric acid or a mixture of sulphuric and acetic acids leads to the replacement of a bromine atom by the nitro-group, and to the formation of 2 :6-dibromo-4-nitroaniline (Frans., 1902, 81, 806).Within very narrow limits of temperature and concentration of the sulphuric acid, the nitroamine is partly converted into bromophenyl- iminobenzoquinones, analogous to the hexachlorophenyliminobenzo-quinone obtained from s-trichloronitroaminobenzene(Trans.,1905,87, 389). In the case of the bromo-compounds, however, a mixture of two phenyliminobenzoquinones is always formed, namely, a penta- and a hexa-bromo-derivative, C,H2Br3*N:C6H,Br2:0and C,H213r,*N:C6HBr,:0 ; bromine is accordingly set free in the reaction. s-Tribromophenyliminodibs.omobenxopuinonecrystallises in dark red prisms or needles with a metallic lustre, and melts at 171'.On reduction it yields s-tribromophenyEdibromo-4-hydroxyphenylamine,which crystallises in white, silky needles melting at 155-156', and is freely soluble in alcohol and other solvents. The latter can thus be separated from the s-tribromophenyltribro~no-4-l~~~roxyp~~en~Zamine, which crystal- lises in colourless needles or prisms melting at-206'. On oxidation it is converted into s-tribromop7~enylittiinotribromobenxoquinone,which crystal- lises in pale red needles or: prisms melting at 134-135', and is more soluble than the pentabromo-derivative in all the usual solvents. 15 ‘(12. Resolution of tetrahydro-p-toluquinaldineinto its optically active components.” By Thomas Constantine Beck and William Jackson Pope.The d-up-bromocamphorsulphonicacid of Armstrong and Lomry mas shown to be applicable for the resolution of externally compensated bases, in accordance with the method of Pope and Peachey, by using it for the separation of the optically actiye tetrahydro-p-toluquinaldinesfrom the corresponding externally compensated mixture. By treating two equivalents of dl-tetrahydro-p-t oluquinaldine hydrochloride with one equivalent of the ammonium salt of the Armstrong and Lowry acid, under appropriate conditions, a nearly quantitative separation of d-tetrahydro-~-toluquinaldine-d-ap-bromocamphorsulphonateis ob-tained ; the salt gives the valiie [MID+ 4.45’ in aqueous solution.On treating the base retained by the mother liquors with Kipping and Pope’s d-bromocamphorsulphonic acid, nearly the whole of the E-base can be s’eparated in a pure state as described by Pope and Rich. The molecular rotatory powers of a, number of salts of the optically active bases have been examined and found to be in agreement with previous conclusions concerning these values for salts of strong optically active bases with strong acids. 13. Note on the theory of valency.” By William Barlow and William Jackson Pope. The homogeneous, close-packed assemblages of spheres corresponding to a series of homologous compounds, such as, for instance, the normal paraflins, are characterised by similarity of marshalling. Further, the assemblage representing ethane is derived from that of methane (Trccizs., 1906, 89, 1743) by an application of the second geometrical property (Zoc.cit., 1729) ; the substitution of one carbon sphere of volume 4 for a hydrogen sphere of volume 1 in each unit, CH,, of the partitioning of the methane assemblage necessitates the simultaneous addition of three hydrogen spheres in accordance with the second geometrical property, so that each unit of the ethane partitioning assumes the composition C2H6. The empirical compositions, CH, and CH,, of the ethane and methane assemblages differ, however, by one hydrogen sphere and a case is thus provided in which, so far as the packing of the spheres is concerned, two hydrogen spheres of volume 1 in the methane assemblage perform the functions of one hydrogen sphere of volume 1 in the ethane assemblage.This is therefore a case of the kind which Mr. D. L. Chapman (Proc., 1906, 22, 320) considers to oEer difbculty 16 in connexion with our theory of valency and to necessitate some modification of the fundamental assumptionP. From the fact that the methane and ethane assemblages are related through the second geometrical property, it is, however, clear that the application of hlr. Chapman’s argument to an actual instance merely brings out the very close correspondence between the geometrical properties in question and our knowledge of chemical constitution. Just as the bearings of the doctrine of valency on constitution and substitution do not appear when empirical compositions are considered, so the second geometrical property only serves to elucidate the doctrine of valency when it is applied in connexion with the molecular composition or the composition of the unit of the geometrical partitioning of the assemblage.A number of examples of the mode in which the property is applied have been already given (Zoc. cit., 17 29-1 736). We may perhaps be allowed to take this opportunity of emphasising the statement (Zoc. cit., 1691 and 1698) that the geometrical properties and the assemblages, which latter are for diagrammatic purposes represented as if composed of undeformed spheres, are in every case supposed to be subject to the condition that so much general pressure is operative on the system as practically to eliminate the interstitial space.It is, of course, not conceivable that the space occupied by the spheres of influence of a group of atoms in contact should include space unavailable for occupation by the atoms. 14. The condensation products of triacetic lactone with aceto- acetic ester and p-aminocrotonic ester.” By Frederick Noel Ashcroft Fleischmann. Triacetic lactone condenses in presence of strong sulphuric acid and hydrochloric acid, he., with aceto-acetic ester, to form a pyrone-lactone, CloH804,melting at 214’. The substance is extrsmely stable toFards acids, but unstable in presence of alkalis, with which it forms deep yellow solutions. It yields a stable byorno-compound (m. p. 190’) crystallising from benzene with benzene of crystallisation, and a .n?itro-derivatire(m. p.200° approx.) which on treatment with strong aqueous ammonia yields aminodehydracetic acid. An unstable abnormal ba~izcnz salt mas also prepared, from which an insoluble, unstable silver and a mercuric salt were obtained. A similar condensation takes place between triacetic lactone and p-aminocrotonic ester in presence of sulphuric, hydrochloric, or glacial acetic acids. The same pyrone-lactone is produced and, in the last instance, a second compound corresponding to the formula C,,H19O,N, the constitution of which is proved by its yielding the ethyl ester of $-lutidostyrilcarboxylic acid on treat riient with alcoholic potash. 17 15, "Derivatives of multivalent iodine.Part 11. Action of heat on p-iodoacetophenone dichloride, p-iodoacetanilide dichloride, and on the dichlorides derived from 0-,rn-, and p-iodotoluene." By William Caldwell and Emil Alphonse Werner. One of us (Werner, Trans., 1906, 89, 1632) has shown that p-iodo- acetophenone dichloride and p-iodoacetanilide dichloride when heated decompose with probable formation of substitution derivatives, thus differing from the general decomposition which has been hitherto recognised in connexion with the chlorides derived from tervalent iodine. When p-iodoacetophenone dichloride, CH,*CO*C,H,*ICJ,, is heated (Werner, TTans., 1906, 89, 1632) it decomposes suddenly at 93-94', only traces of chlorine (0.43 per cent.) being evolved in the free state, and chloro-p-iodoacetophenoneis produced to the extent of 98 per cent.of the theoretical, thus : CH,*CO*C,H,.ICl, =CH,Cl*CO*C,H,I +HC1. It forms long, slender prisms (m. p. 126-127'), and on oxidation it furnishes p-iodobenzoic acid. With chlorine it yields CH,C1*CO'C,H,*IC12, which decomposes at 128-1 30' with production of dichloro-p-iodo-acetophenone, CHCl,*CO*C,H,T (m. p. 62-63'). This also gives p-iodo- benzoic acid on oxidation and unites with chlorine to form CHCl,*CO C,H,*ICI which is decomposed by heat with evolution of most of the chlorine in the free state. p-Iodoacetanilide dichloride, CH,*CO*NH*CGH-,*ICI,, decomposes at Z 03' and yields chloro-p-iodoacetccnilide, CH3CO*NH*C,H,ClI (m. p. 144*), from which a c~~Eoi.oiodoa?ziEiize,C,H,ClI*NH, (NH, :I :C1= 1 :4:2 or 3) (m.p. 73O), is obtained. The picrate melts at 132'. Chloro-p-iodoacetanilide unites with chlorine, forming CH,CO*NH*C,H,C1*IC12, which decomposes at 131' and yields a substitution producb which has not yet been investigated. The action of heat on the chlorides of 0-,na-, and p-iodotoluenes, prepared by Willgerodt, has been examined. o-Tolyliodochloride decomposes at 85-86' and yields o-iodobenzyl chloride, C6H41*CH2Cl, which gives o-iodobenzoic acid on oxidation. m-Tolyliodochloride decomposes at 88', giving an iodochloride which yields on oxidation an acid melting at 210' and containing both chlorine and iodine. p-Tolyliodochloride decomposes at 1 1 O', giving p-iodobenzyl chloride.In each case a small proportion of the original iodotoluene is regenerated. 18 4L16. Disalicylamide.” By James McConnan. 0-Salicylsalicylamide does not possess the properties previously attributed to it (Patentschrift No. 11 1, 656) ;the compound thus named by Cohn was probably disalicylamide. Under suitable conditions, 0-salicylsalicylamide rearranges, forming disalicglamide and vice versa; this is another case of the metoxrtzone tautomerism peculiar to acyl derivatives of salicylamide, and already studied in the cases of the benzoyl and the acetyl derivatives (McConnan and Titherley, Truns.,1906, 89, 1318). 17. (‘Benzoyl derivatives of N-methylsalicylamide.” By James McConnan and Morris Edgar Marples. ,V-iV-Dimethylsalicylamide is a stable substance ;N-methyl-N-benzoyl-salicylamide, however, is unstable, and under the conditions of its formation it is either instantly hydrolysed or rearranges, forming 3-met hyl-0- benzoyl sal icylamid e.It thus appears that, a1though derivatives of the general formula C,H,<g~N*K, are stable, sub- stances of the type C,H,<~EN*R*Ac are too unstable to permit of isolation. This result is of considerable interest, since McConnan and Titherley have already shown (Trcms,, 1906, 89, 1327) that N-N-di-acylsalicylamides, OH*C,H4*CO*N<E,are too unstable to exist. 18. ((The velocity of reaction of bromine with some unsaturated acids in aqueous solution.” By Ernest Barrett and Arthur Lapworth. Recent, communications from W.Herz and B. Mylius (Bey., 1906, 39, 3816) and from J. J. Sudborough and J. Thomas (Proc., 1906, 22, 318) deal with the addition of bromine ta cinnamic acid and its esters in organic solvents. We have been engaged in the examination of addition of bromine to some unsaturated acids in aqueous solutions in the hope of throwing some light on the mecha.nism of such reactions. The changes are somewhat di6cult to follow, as the velocities are very considerable, and even in dilute solutions the time must be measured in seconds instead of hours. The temperature employed was 14.9’ in the first three cases and 25-5O with the monobromocinnarnic acids, and the experiments were carried out in artificial light. Cinnamnic Acid-With equimolecular proportions of acid and halogen in N/lOOO solutions, nearly the whole of the bromine dis- 19 appeared in thirty seconds.With excess of bromine, 1.5 mols. were absorbed in about eighty minutes, this effect being due to the formation of bromocinnamic acids from the initial product. With crotonic acid and bromine, in equimolecular proportions in N,200 solutions, more than 9/10ths of the bromine was used in forty-five seconds. Benzylidenemalonic Acid.-With N/200 solutions, about 0.5 mol. of bromine was absorbed in one minute, and the change had during the greater part of its course the form of a termolecular reaction. With the sodium salt the velocity is much greater, 9/10ths of the bromine disappearing in about thirty seconds.In N/2 sulphuric acid the velocity was about, l/lOth of its usual value. Potassium bromide also lowers the reaction velocity, but not so decidedly ;thus in N/S potass-ium bromide the velocity was about 3/5ths of its ordinary value. The reaction, towards its end, is complicated, the product losing hydrogen bromide and carbon dioxide, the resulting bromocinnamic acid accounting for some of the bromine. Thus with excess of bromine, 14 mols. of halogen disappeared in twenty minutes. P-Monobromocinnamic Acid.-With equimolecular proportions of acid and bromine in N/100 solutions, about 0.25 mol. of bromine disappeared during the first half-minute, The change, in presence of excess of hydrogen chloride or potassium chloride, is of the bimolecular form; in absence of these agents the decomposition of the initial addition product occurs with measurable speed.The sodium salt is brominated at about the same rate as the free acid at first, but later the secondary reactions are more evident. Hydrogen chloride or potassium bromide diminish the reaction velocity, but apparently never to more than half the normal value. In this case, mineral acids have considerably less effect than have bromides, an observa-tion consistent with the fact that the sodium salt and the acid have nearly the same velocity of bromination. The sodium salt of the stereoisomeric a-monobromocinnamic acid, it is interesting to note, absorbs bromine many times more rapidly than does the free acid. The results appeax inconsistent with the view that bromine dis-sociates into ions before addition at a double linking.They seem to show, however, that the ions of the acids, as well as the acids them- selves, unite with bromine directly. 19. “Note on the molecular complexity of liquids.” By Albert Ernest Dunstan and Ferdinand Bernard Thole. In a recent paper (Trans., 1906, 89, 1774) Holmes deals with the question of molecular complexity from the point of view of the volume changes produced on mixing. By calculating the greatest difference between the volume of alcohol actually present and the volume 20 which would be present assuming no contraction, he assumes, for mixtures of alcohol and water, for example, thah this maximum (lC,H,*OH,l H,O) implies approximation of the ratio of the radii of ‘I influential spheres ” to unity.The following table shows that the ratio does not approximate to unity, taking as a basis of calculation the true molecular volumes given by the author : Max. difference of alcohol Above ratio 1101. vol. nercentares bv vol. at : of radii. oi Ethyl alcohol ........ 3.22 C2H,*OH,1iH20 1.47.JF= n-Propyl alcohol ,.. 4.07 C,H,*OH,l &H20 Propionic acid ...... 4.06 C,H,*CO,H,l€€,O JFn-Butyric acid ...... 5.08 C,H7*C0,H,1H20 = 1-72. Throughout the paper the author refers to the one constituent of a mixture as possessing the more active molecule usually of greater mole- cular volume and carrying a preponderating effect into the mixture. It mould be more correct to look upon solution from the point of view of the reciprocal effect of the one component on the other ;when this is done, for example, in the case of alcohol and water, the maximum effects are to be noticed at the proportions lC2H,*OH,3H,0(Dunstan, Trans., 1904, 85, 823).Holmes regardsathe lower alcohols and acids of the paraffin series, from similar considerations, as having the same complexity as water ; water he assumes to have the aggregate formula (H20),. Now there is a considerable amount of evidence available which shows that the earlier liquids of homologous series tend to associate somewhat particularly those the members of which are hydroxylated. ViscosityIt has been shown that the quantity mollx 106 is nearly con- Benzene ...............65 Water ............493 Acetic acid ...195 Chloroform .........67 Methyl alcohol 138 Glycerol ...... 106,000 Carbon disulphide.. . 60 , Ethyl alcohol ... 189 21 clivcrgences nt, t,he beginnings of trhc serics ns to jnstify the iclea of increased associntlion. (ilycerol and nicotine arc the only unimoleculnr liquids quotled in tlic table (p. 1785); now glycerol is not only notably viscoiis, but also has a remarkably high temperature coefficient of viscosity ; both these facts indicate its association. Carbon disulphide (Zoc. cit.) is mentioned as possessing four tinies the complexity of nlcohol and is therefore represented by the formula [0S,l8; it is inconceivable from such data as, for example, its low boil- ing point, its low viscosity coefficient, the variation of its molecular surface energy with temperature, and its position in the molecular weight-viscosity chart. Pyrirline is quoted as a liquid which has the same iiiolecular com-plexity as water and the alcohols.If this is so it is extraordinary that the viscosity concentration curves of mixtures of pyridine with nlcoliol on the one hand and with water on the other should be so entirely diff ercnt. Froiii an investigation now in progress 011 pyridine solutions it is found that in aqueous solutions niaximuin occurs at tho proportions 2C,H,N,5H2O, and secondary irregularities at 3C,H,N, 2H,O, 2C5H,N,7H,O, 1C5H,N,5H,O, and 1C,H,N,lOH,O. These discontinuities can only be explained by the assumption of loosely held complexes in dynamic equilibrium, which ionise to a considerahle extent, and which generally behave like nmmoniuiii hydroxide, but in alcoholic solution no maximum point is noted; the curve is composed of two branches which represent (1) the viscosity curve of associated alcohol with dissociated pyridine, and (2) dissociated alcohol with associated pyridine.A precisely similar curve is afforded by alcohol-benzene mixtures, A study of the viscosity curves (Dunstan, Tram., 1905, 87,11, and Zoc. cit.) enables the changes in association which take place to be followed qualitatively, whilst the curves connecting molecular weight with viscosity coefficient give a quantitative idea as to the degree of association existing in any given liquid. Gibbs, J.JViZZnrd. The scientific papers of J. Willard Gihhs. (Eclited by fle.rzrz/ Andrezos Bumstead and Ralph Gibbs van Name.) 2 vols. pp. xxviii +434, ix + 284. London 1906. (122cc:I. 3/1/7.) From the Pnblishers : Messrs. Longmans, Green ((7 Chi. Japp, Frrmcio Robwt and Maitland, JPillimz, Knox, Joseph, Wood, ,Jm)ies. Researches in organic chemistry carried out in tlie lJriiversi ty of Aberdeen. pp. iv + 86. Aberdeen 1905. (liecd. 15;1,’7.) From the University of Aberdeen. Meldrum, Andrew N. Avogadro and Dalton. The standing in chemistry of their hypotheses. With n preface by Fmncis X.Japp. pp. viii + 113. Abercleen 1904. (Recd. 15/1/7.) From the University of Aberdeen. Meyer, Ernst uon. A history of chemistry from earliest times to the present day, being also an iiitroduction to the study of the science.Translated by George McGCowan. Third English edition. pp. xxvii + 691. London 1906. (Becd. 10/1/’7.) From Dr. George McGoman. Thresh, John C. and Porter, Arthur E. Preservatives in food and food examination. pp. xv + 484. ill. London 1906. (Recd. 29/12/6.) From Dr. J. C. Thresh. Vicarey, R. W. The treatment of storage batteries. pp. xi + 51. ill. London 1507. (Iiecd. 12/1/7.) From the Author. 11. By Purchase. Dowson, J.Eirzeswm, and Larter, A. T. Producer gas. pp. xiv+ 296. ill. London 1906. (Recd. 9/1/7.) 111. I’ccnzphEets. Caldwell, Robert J. The hydrolysis of sugars. [A paper red before the York Meeting of t,he British Association, 1906.1 pp.26. Crompton, Hohnd. Some molecular and latent heats. pp. 12. Salcombe 1906. Finlow, R.8. The extension of jute cultivation in India. (From the Bull. Agricukural Besearch Inst., I’usa, 1906.) Hughes, Frank. The occurrence of sodium salts in Egypt. With special reference to nitrate of soda. (From the Yearbook, Khediuinr! Agric. Xoc., Cairo. 1905.) 23 ANNIVERSARY DINNER. It has been decided by the Council to arrange for a Dinner of the Fellows of the Society and their friends on Friday, March Bnd, 1907, this being the day fixed for the Annual General Meeting. Further particulars will be announced shortly. At the next Ordinary Meetsing on Thursday, February 7th, 1907, the following papers will be communicated : “ The rapid electro-analytical deposition and separation of metals.Part I. The metals of the silver and copper groups and zinc.” ByHenry Julius Salomon Sand. ‘‘The alkaloids of ergot.” By G. Barger and F. H. Carr. ‘‘ Influence of substitution on the formation of diazoamines arid aminoazo-compounds. Part Vl. The partially methylated 4 :6-di-amino-7th-xylenes.” By G. T. Morgan and F. M. G. MickletJhwait. “The reduction of hydroxylarninodihydroumbelluloneoxime.” EyF. Tutin. The constitation of urnbellulone. Part 11. The reduction of uinbellulonic acid.” By F. ‘l’utin. ‘‘ Studies on optically active csrbimides. Part V. The argl esters and the aimides of I-menthylcarbamic acid.” By R. H. Pickard and W. Oswttld. “ Sotile constituents of natural indigo. Part. I.” By A. G. Perkin and W. P. Bloxaui. “The occurrence of isatin in some samples of Java indigo.” By A. G. Perkin. ‘(On the absorption spectra of benzoic acid, the benzoates, and benznmide.” By W. N.Hartley and E. Y.Hedley. “ The absorption spectra of phthalic, isophthalic, and terephthalic acids. Phthalic: anhydride and phthalimide.” By W. N. Hartley and J3. Y.Hedley. 11. ULAY SOHS, LTI)., BILEAD ST. HILL, E.c., ANU UUNGAY,BUFBOLK.
ISSN:0369-8718
DOI:10.1039/PL9072300001
出版商:RSC
年代:1907
数据来源: RSC
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