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Proceedings of the Chemical Society, Vol. 26, No. 375 |
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Proceedings of the Chemical Society, London,
Volume 26,
Issue 375,
1910,
Page 189-240
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摘要:
Issued 29/10/10 P 1'1.0C E E D I N G S OF THE CHEMICAL SOCIETY. VOl. 26. No. 375. The Council has ordered the following letter a.nd report to he printed in the Journal and Procccdings of tlis Society : IMPERIAL COLLEGE OF SCIENCE AND TECHNOLOGY, SOUTHKENSINGTON, TIONDON, s.\v. August 22nrl, 1910. GENTLEMEN, I beg to forward tho Annual Report of the Intcrnational Com- mittee on Atomic Weights for 1911, to which I have appended, by their desire, the signatures of Professors Ostwald and Urbain. The Committee, it will be seen, have acceded to the wish of the Council of the Chemical Society, and have prepared the Report in such time that it can be published prior to the commencement of the ensuing academic year. Slight changes have been made in the atomic weights of argon, helium, krypton, lithium, neon, phosphorus, platinum, strontium, vanadium, and xenon, but.otherwise the new table remains very mizch as iii 1910. I have the honour to be, Gentlemen, Your obedient servant, T. E. THORPE. To tAe Hon. Secretaries, The Chemicul Society, Brr dington HO~CSR, London) TV, 190 Report of the International Committee on Atomic Weights, 1911. In the autumn of 1909 the Council of the Chemical Society of London voted unanimously in favour of issuing the annual report of the International Committee on Atomic Weights in September or October instead of in January as heretofore. In that proposition the Chemical Society of France has concurred, and American sentiment has also been favourable t,o the suggcstcd change.There-fore the cliange is now made. Tlie rcasons offered for the ncw policy are very simplc. First,, t.hc school year, at least in most educational institutions, begins in the autumn. It is desirabIe that teachers should then have the latcst table of atomic weights at their command, in order to amid changes after school work has begun. Secondly, publishers of text-books are accustomed to issue their new works in the autumn, and often request ezrly information as to changes which are likely to be made. The proposed change in the time of issuing the table is therefore an aid to teachers, students, and publishers, and no dis-advantage to anyone else. The immediate usefulness of the ta.ble is increased, and to attain that end should be the main purpose of the Committee.Since the preparation of the report for 1910, a nuiiiber of important memoirs upon atomic weights havo appeared. The results obtained are, in brief, as follows: ChZo~i72e.-The density, composition by volume, and compressi- bility of hydrochloric acid have been measured by Gray and Burt (Trans., 1909, 95, 1633) with great care. From the density and volumetric composition, when H =1*00762,C1= 35.459. From the density and compressibility, C1= 35.461. The mean, 35.460, is the value given in the annual table of atomic weights for the past, tv?o or three years. The density of hydrochloric acid has also been determined by Scheuer (Zeitsch. PllysiEaZ. Chem., 1909, 68, 575), who gives measurements made under varying conditions.His final con-clusion, based upon his own work after comparison with that of Gray and Burt, is that C1=35*466. I;ithium.-Richnrds and Willard (-7. A mep. Chern. Soc., 1910, 32, 4), in their important resosrch upon the atoinic weigllt of lithiuul1, measured three distinct ratios, namely, silver to lithinm cllloridc, silver chloride to lithium chloride, and lithiwn perchlorate to lithium chloride. From these ratios, without the intcrvelltion of 191 any others, the following independent values for three atomic weights are obtained : Li=6 039. Cl= 35.454. Ag=107.571. The value for silver varies from the accepted value, 107.88, by about one part in 12,000, which is probabIy less than the actual uncertainty.That for chlorine diverges more widelv, namely, by about one part in 6000. The new figures are undoubtedly entitled to great weight, Eat in view of the excellent work done by others it would be unwise to make any hasty change in the table. For lithium, however, the value 6.94 may be taken, replacing the old 7-00. Strontium.-Thorpe and Francis (Proc. Roy. SOC.,1910, 83,A, 277), in their determinations of the atomic weight of strontium, measured six ratios, and obtained the following results : Ratio 2dg to SrlZr, ........... Sr=S7%45 ,, 2dgl:r to SrBr, ......... ,, =87'653 ,, 2Ag to SrCI, ............ ,, =87'642 ,, 2AgC1 to SrC1, ....... ,, =S7%15 ,, sr13r, to srso,............ ,, =S7.629 ,, SrCI, to SrSO, ...........,, =S7'6til -~ rclean of all ........ Sr =87'646 The value adopted by the authors is 87.65. Richards's figure is 87.62. An intermediate'Galue, 87.63, is adopted in the new table. Phosphorus.-Atomic weight redetermined by Baxter and Jones (J. Amer. Chem. SOC.,1910, 32, 298). From the ratio between silver and silver triphosphate, the authors find P =31.043, when Ag=107*88. The rounded-off figure 31.04 is to be adopted. i~ranadii~m.-From the ratio between silver chloride and vanadyl trichloride, Prandtl and Bleyer (Zeitsch. anorg. Chem., 1910, 65, 152) find V=50*963 and 51.133 in two series of experiments. 111 a later paper, Prandtl and Bleyer (Zeitsch. anorg. CIienz., 1910, 67, 257), also from analyses o,f vanadyl trichloride, find V=51.061.From reductions of V,05 to V,O,, they found V=51*374. Tho latter method, however, they regard as uncertain. The value V =51-06 may be provisionally adopted. TeZZzc,.ium.--R~arckwald and Foizik (Ber., 1910, 43, 1710; see also Browning and Flint, ilnzer. J. Sci., 1909, [iv], 28, 347, who adduce evidence to show that tellurium is possibly complex), by a somewhat complex volumetric process, based on the oxidation of TeO, by ICMnO,, conclude that Te =127.G1. This agrees with 192 many of tlie other recent determinations of thc constant, but is not sufficiently exact to supplant the value given in the table. Rhodium.-Two inaugural dissertations upon the atomic weight of rhodium have been issued from Gutbier's laboratory at Erlangen.Renz reduced rhodium pentaminc bromide in hydrogen and found Rh =102.92. H. Dittmar (reproduced in Sitzztngsber. pltys. med. Soz. Erlangeu, 40, 184), by similar reductions of the correspond- ing chloride, found Rh =102.93. Platinum.-The very elaborate investigation of Archibald (YTOC. Roy. SOC.Edin., 1909,29, 721) upon the atomic weight of platinum was based upon analyses of the chloroplatinates and bromoplatinates of potassium and ammonium. In all, 28 ratios were measure& giving values for Pt ranging between 195.19 and 195.25. Their arithmetical mean gives Pt =195-22. Archibald, however, in his final discussion, uses only 12 ratios, giving, in mean, Pt=195*23. The figure 195.2 is given in the table. The Inert Gases.-The densities and molecular weights of helium and neon have been redetermined by Watson (Trans., 1910, 97, 810). For the atomic weights he finds He=3*994 and Ne=20*200.In another paper (ibid., 97, 833) he applies the critical constants, of krypton and xenon to their densities as determined by Moore,. and finds Kr=82.92 and Xe=130*22. There are also new deter-minations of the density of argon by Fischer and Hehnel (Bcr.,. 1910, 43, 1435). Their mean value, referred to 0=16, is 19-945,. a figure rather higher than that given by Ramsay and Travers. Itr corresponds to an atomic weight of A= 39-89. It is also to be noted that a third, revised edition of Clarke's " Recalculation of the Atomic Weights " has recently been published by the Smithsonian Institution.The annual table of atomic weights for 1911 follows, with but few changes from that of the preceding year. F. W. CLARKE. W. OSTWALD. T. E. THORPE. G. URBAIN. I93 1911. Lntemalz'onal Atomic Weiyhls. 0=16 . 0 =16. Aluminium ................. A1 27 -1 Molybdenum ............... 110 96.0 Antimony .....................Sb 120'2 Neodymimn .................Ntl 144'3 Argon ...................... A 39'88 Neon ...........................Nc 20.2 Arsenic ..................... As 74.96 Nickel ........................Ni 58.65 Barium ........................ Ba 137'37 Nitrogen ..................... N 14-01 Bismuth .....................Bi 208.0 Osmium ..................... 0s 190.9 Boron ........................B 11.0 Oxygen ........................0 16.00 Bromine ....................Br 79.92 Palladium., ...................Pd 106.7 Cadmium ..................... Cd 112-40 Phosphorus .................. 1' 31 '04 Cssiuni .......................Cs 132.81 Plat iuu 111 .....................Pt 1952 Calcium........................Ca 40.09 Potassium......................K 39'10 Carbon ........................C 12-00 Praseodymiuiii...............Pr 140% Cerium ........................Ce 140.25 Radium ........................Ra 226'4 Chlorine ....................C1 35 *46 Rhodium ....................Ith 102'9 Chromium ................Cr 52-0 Rubidium .................... Rb 55-45 Cobalt ....................... Co 58-97 Ruthenium .................Itu 101.7 Columbium .................Cb 93'5 Samariuin ................. Sa 150'4 Copper ........................ CLI 63-57 Scandium .................... Sc 44.1 Erbium ........................ErDysprosiuni ................. DY 162.5 167'4 Selenium ..................... Se Silicon ...................... Si 79.2 28.3 Europimii....................Eu Fluoriiie ..................... F 152.0 19'0 AgSilver ........................ Sodium ........................ Na 107'85 23'00 Gadolinium .................. Gd 167.3 Strontium .................. Sr 87-63 Gallium ....................Ga 69-9 Sulphur ..................... S 32-07 Germanium ..................GI e 72.5 Tantaluni .................... Ta 181'0 Glucinum ...................G1 9 '1 Tellurium .....................Te 127#5 Gold ...........................Au 197.2 Terbium .....................Tb 159-2 Helium ........................ He 3.99 Thallium .................... T1 204.0 Hydrogen ..................... H 1-008 Thorium ..................... Th 232.0 Indium .......................In ii4.a Thulium ..................... Tm 168.5 Iodine ........................ I 126'92 Tin ........................... Sn 119'0 Iridium ....................... Ir 193.1 Titanium .....................Ti 48.1 Iron ...........................Fe 55.85 Tungsten ..................... W 184-0 Krypton .....................Kr 82.9 Uranium .....................U 238 *5 Lanthanum .................La 139-0 Vanadium., ...................V 51-06 Lead ..........................Pb 207.10 Xenon ........................ Xe 130.2 Lithium ..................... Li 6'94 Ytterbium (Neoytterbiuui) Yb 172.0 Lutecium ....................Lu 174.0 Yttrium .....................Y 89.0 Manganese .................. Mn ..................Magnesium Mg 24.32 54.93 Zinc ...........................Zn Zirconium .....................Zr 65-37 90.8 Mercury .....................Hg 200.0 194 The following are abstracts of papers received during the vacation and published or passed for publication in the Traasactions : 200. ‘‘ A3-p-Menthenol(8)and A-3:“g)-p-mentbadiene.” By William Henry Perkin, jun., and Otto Wallach.(Trans., 1910,1427.) The authors hive prepared the above substances and several OF their derivatives from two sources, namely, from l-methyl-A3-~ycIo- hexene-4-carboxylic acid and from 4-acetyl-1 -methyI-A3-cycZohexene : and they give a careful comparison of the physical properties of these substances with those of terpineol, limonene, and their corresponding derivatives. 201. ‘‘ Freezing-point curve for mixtures of camphor and phenol.” By John Kerfoot Wood and Janet Drummond Scott, (Trans., 1910, 1573.) The authors have determined the freezing points of a large number of mixtures of camphor and phenol, ranging in composition from pure phenol on the one hand to pure camphor on the other. The form of the freezing-point curve indicates the formation of a compound, the freezing point of which is -18*6O, between equi-molecular proportions of camphor and phenol.The curve also shows that eutectic mixtures are produced when the molecular percentage of camphor in the mixture amounts to either 29.5 or 59.21; in the former case the eutectic mixture is composed of phenol and the compound, and in the latter case of camphor and the compound. The freezing points of the two eutectic mixtures are respectively -30’5O and -32*0°. No evidence was obtained by the authors as to the existence of the hemi-camphoride of phenol mentioned by L6ger (Compt. rend., 1890, 111, 109). 202. “The] absorption spectra of aniline and its homologues as vapours, as liquids, and in solution.” By John Edward Purvis.(Trans., 1910, 1546.) The results of this investigation show that: (1) the vapour of aniline has a considerable number of absorption bands, which show relationships amongst themselves both in structure and in differences of wave-lengths; (2) the vapours of the homologues of aniline show none of these absorption bands; (3) the solutions in alcohol show 195 absorption bands in all the substances, and the type and position of the bands are regulated by the replacemelit, by rtlkyl groups, of the hydrogen in tho aniino-group or in the nuclous; (4) none of the substances in the liquid condition exhibit absorption bands through the thinnest films of 0.001 mm. thick. The phenomena are discussed from a consideration of the vibrations of symmetrically and unsymmetrically oriented molecules in different physical conditions.203. Condensations of phenanthraquinone with ethyl malonate and ethyl acetoacetate.” By Marion Brock Richards. (Trans., 1910, 1456.) Japp and Wood (Truns., 1905, 87,712) described some con-densations of phenanthraquinone with ketonic compounds under the influence of acetic anhydride containing a little concentrated sulphuric acid. The condensation products of phenanthraquinone with ethyl malonate and with ethyl acetoacetate, of which mention was made in that paper, have now been further investigated. In the case of the ethyl malonate reaction, two compounds were obtained, namely, ethyl phenant hro xy lacetoxymalonat e, C2,H2,0, (m.p. 109*5O), and ethyl 2-keto-3-acetoq-4:5-diphenylene-2 : 3-di-?bydrofuran-3-carboxylate, C21H1606 (m. p. 163*5O),and it was found that the former could be transformed into the latter compound by further action of the reagent. Reduction of the second compound with hydriodic acid yielded 2-keto-4 : 5-diphenylene-2 ; 3-dihydro-furan, C,,H1,)02 (m. p. 177O), from which the corresponding acid, 9-hydroxy-1 O-phenan thryluc etic acid, C16H1203(m. p. 182-183’) ) was also prepared. The ethyl acetoacetate reaction also gave two compounds, namely, ethy6 9-phenan t hrozylace t oxyace toacetate, C2,H,,O, (m. p . 148’) , and a substance, C22H1805(m. p. above 315O), and, again, further action of the reagent caused the first substance to be transformed into the second.204. ‘‘The constitution and mutarotation of sugar anilides.” By James Colquhoun Irvine and David McNicoll. (Tiaiis., 1910, 1449.) The anilides of tetramethyl mannose, tetramethyl galactose, and trimethyl rhamnose have each been obtained crystalline in muta- rotatory forms. The compounds are recovered unchanged after treatment with silver oxide and methyl iodide, and are thus to be regarded as derivatives of the y-oxidic forms of the parent sugars. As the anilides of the corresponding unsubstituted sugars are very readily hydrolysed, the method of determining their con-stitution by the rcsults of nlkylation (Trans., 1908, 93,1429) cmnot; be applied, but tlicii. structural resemb1anc.c t,o t l1c Inet,hylat8ed y-oxidic aiiiliclcs is slkowii in tlic mutarotation exliibited by tlic compounds.Mannoseanilide, galactoseanilide, and rhainnoseanilidc have accordingly been re-examined, and found to display optical changes which are comparable in every way with those shown by the methylated anilides. Comparison of the optical effects due to glucoside and anilido formation, from sugars, and from niethylated sugars, shows that the forins of the anilides isolated in the pure state by crystallisation are directly cornpaz-able with /3-glucosides. 205. '' Cyclic di-and tri-ketones." By Siegfried Ruhemann. (Trans., 1910, 1438.) The diketopyrrolines condense with o-phenylcneciia.niine with thc production of phenazines. Diketodiphenylpyrroline and diketo-phcnyl-ptolylpyrroline, respectively, yield thus : Clii7~~~"1'~7~y~roZino--. CGH, C--C: N >O,H,,II I or its homologue.Thesephenazine, C,H,*C.NR*C:N compounds, like ..all other members of bhis group, are yellow, but the condensation product, C2013,G0N2, which is formed from o -phenylenediamine and diketoacetylphenylmethylcy clopentene, is purple. This fact indica,tes tjhat the sub-stance C,HliON2 has not the constitution of the phenazines, but CPh:C*NHCNe<CAc,i,,N>CGH4, and that its formation is preceded by the change of the diketocyclopentene derivative, C,,H,,03, into its tautomeric form, which exists, also, in the blue salts of this diketonc (see Trans., 1909, 95, 984). With tlie view of preparing 1: 2-diketohydrindeneY the author studied the action of p-nitrosodimethylaniline on a-hydrinclone, C,H,< co->CH,, and found that the nitroso-compound CH2 attacks both CH, groups of the hydrindone.The green con-densation product, C25H2602N4, which is formed, is decomposed by dilute sulphuric acid, and yields the colourless hpdrute of triketo-cohydkzdene,C,H,<CO>C(OH),. Its physical properties and some of its interesting reactions are described. 107 206. (( The reiation between solubility and the physical state of the solvent in the case of the absorption of carbon dioxide in 31 azoxyphenetole.” By Ida Frances Hornfray. (Trans., 1910, 1669). A homogeneous solution phase, in the normal liquid or gaseoiw states, may be present in equilibrium with practically all solids, liquids, or gases in other co-existing phases.In the case of niix-tiires in the so-called solid state, however, a distinction must be drawn between the crystalline and the amorphous forms. The term solid should, strictly speaking, be confined to the former, the latter having rather the properties of a highly supercooled fluid. All available evidence appears to show that the directive forces of crystallisation almost entirely prevent molecular interpenetration. p-Azoxyphenetolo is a crystalline substance, which melts at 138O to a crystalline liquid, changing at 165O to an isotropic normal liquid. The absorption of carbon dioxide in these phases has been determined in a specially conshucted apparatus, unabsorbed gaseous volumes being measured.It was found that no absorption takes place in the solid, crystalline phase. After the first melting point, some abso,rption occurs. On further raising the temperature, thermal expansion continues until the clearing point is reached. Then, however, a second maximum volume is passed through, a very considerable increase of absorption occurring. After equi-librium has again’ been established, thermal expansion and decrease 01 solubility proceed regularly. On reversing the process, the same maximum and minimum readings are repeated. The remarkable result is thus obtained that, in spite of the lower temperature of the crystalline liquid phase, its solvent power is much smaller than that of the isotropic phase, whilst solution or adsorption in the solid phase is entirely absent.207. The triazo-group. Part XIV. Azoimides of the acetoacetic series.” By Martin Onslow Forster and Sidney Herbert Newman. (Tlnns., 1910, 1360). For the purpose of comparison with azoimides of the malonic series) na e t?by1 and e t hyl a-t riazom e tI~ylac e touce ta t es, e thy1 a-t ti-c~z o e t?byInc c t oci c e tat e, and et7~y1 aa-histria2:ouce tocc c etat e were pre-pared by interaction of the corresponding chloro-derivatives and sodium azide. In each case the triazo-ester was obtained with much greater difficulty than was presented by the triazomalonic esters. Ethyl a-triazomethylacetoacetate is transformed by ammonia into a-triazopropionamide, whilst liyclrot:lilo~~icarid resolves it into ciiacety1.208. “ Optically active methoxysuccinic acid from nialic acid.” By Thomas Purdie and George Ballingall Neave. (Trans., 1910, 1517). The authors have prepared the methyl, ethyl, and propyl esters of I-methoxysuccinic acid by methylating malic esters with methyl iodide and silver oxide with the object of cont.rolling and extending the polarimetric observations formerly made (Trans., 1893, 63, 217, and succeeding papers) on the same compounds, obtained by resolution of inactive methoxysuccinic acid with the aid of alkaloids. The values of the rotatory powers of the esters and acid from the two different sources are in fair agreement. The optical relationships of the ethereal I-methoxysuccinates with the d-dimethoxysuccinates (Trans., 1901, 79, 963), in the pure liquid state and in solution, are pointed out, also the relationships of these esters with the parent rnalates and tartrates.The diamide and dianilide of I-methoxysuccinic acid were pre-pared, and their rotatory powers in solution compared with those of maldiamide and maldianilide in similar solvents. 209. ‘‘Optically active derivatives of I-methoxy-and d-dimethoxy-succinic acids.” By Thomas Purdie and Charles Robert Young. (Trans., 1910, 1524). The authors have prepared further derivatives of these acids, including the anhydrides and dichlorides. Polarimetric examination of the lath afforded no evidence that they were mixtures of two tautomeric forms of the type frequently assigned to succinyl chloride.The molecular rotations of I-methoxysuccinic acid and a number of its derivatives approximate to the halved values of the corresponding dimethoxy-compounds. It is pointed out that the movements of rotation attending the conversion of alkylosy-, acyloxy-, and halogen-succinic acids of d-and Z-configuration into chloride, ester, and anhydride are always in the dextro- and lzvo- direction respectively, irrespective of the sign of rotation of the initial acid. The action of sodium methoxide on methyl I-methoxysuccinate gave an optically inactive condensation compound, apparently identical with a substance obtained similarly (Trans., 1891, 59, 472) from methyl fumarate. The products of the action of mag- nesium methyl iodide and of magnesium phenyl bromide on methyl a?-dime thoxysuccinat e were y&dim,et hoxy-Be-dimet hylhexane-&-dioE (m.p. 71O) and 3 : 4-&intethoxy-2 : 2 : 5 : 5-letraphenyltetrahydro-furan (m. p. 185O) respectively; both compounds are laevorotatory. I99 210. (( Action of GCrignard reagents on methyl Z-methoxysuccinate methyl maleate, and maleic anhydride.” By Thomas Purdie and Paul Seidelin Amp. (Trans., 1910, 1537). The action of magnesium methyl iodide on methyl Z-methoxy- succinate is similar to that of the same reagent on the d-dimethoxy- ester previously described, the product being optically active y -methoxy -PE.-dimethylhexane -&-diol. Dehydration, however, occurred in the course of isolating the compound by distillation, and the final product obtained was the oxide of the glycol, or possibly an isomeric unsaturated alcohol.The substance is dextro- rotatory. Two crystalline compounds were isolated from the product of the action of magnesium phenyl bromide on methyl Z-methoxysuccinate, namely, 2 :2 :5 :5-tetraphernyE-2 : 5-dihydrofu;ran (m. p. 190-191O) and a triphenyEbutyroZactone (m. p. 160-161°), both optically inactive. The latter compound, on being heated with mineral acids, was converted into an isomeric lactone (m. p. 197O). With the view of elucidating the reactions concerned in the production of these compounds, the authors examined the action of magnesium phenyl bromide on methyl fumarate and maleate and on maleic anhydride.The product in the case of methyl fumarate waa an uncrystallisable oil from which no pure substance could be isolated. Methyl maleate gave the above-mentioned dihydrofuran derivative, and maleic anhydride gave A. With’s desylacetophenone (Trans., 1890, 57, 643). 211. 4L The intramolecular rearrangement of diphenylamine ortho- sulphoxides. Part 111. The tri-and tetra-chlorosulphoxides.~’ By Oscar Lisle Brady and &muel Smiles. (Trans., 1910, 1559). In a previous paper the mechanism of this rearrangement was discussed, and the hypothesis was advanced that it depends on the preliminary formation of a salt of the sulphoxide. The tri-and tetrachloresulphoxides of diphenylamine have now been prepared by the action of hydrogen dioxide and hydrochloric acid on thie diphenylamine, and these have been fully investigated with the object of isolating their salts.This has been accomplished in the case of the trichloro-derivative, the hydrochloride of which is readily converted into the azothionium compound by warming in certain media,. It is considered that the explanation previously given to this reaction is thus confirmed, 200 212. ('The rate of hydration of aoid anhydrides : succinic, methyl sncoinic, itaconic, maleic, oitraconic, and phthalic. " By Albert Cherbnry David Bivett and Nevi1 Vincent Sidgwick. (Trans., 1910,1677). The authors have investigated the rate of hydration of these anhydrides by means of the conductivity, by a method described for acetic anhydride in a previous paper (Trans., 1910, 97, 732). In all cases the reaction waa found to be unimolecular, and not to be catalysed by hydrogen ions.The slight variation of the rate with concentration, previously found with acetic anhydride, was not observed with any of them cyclic anhydrides, with the possible exception of methylsuccinic. The velocities are given below (the mean value for acetic anhydride being added for comparison), together with the dissociation constants of the corresponding acids : Dissociation Anhydride. Velocity constant. constant of acid. Aiziz5zz. Abwve, [Acetic ........................... 0-001148 0.991 Snccinic ........................... 0'001155 1'00 0'0066 1'00 Methylsuccinic .................. 0.001609 1 '39 0-0086 1 '30 Itaconic (Methglenesuccinic) 0'001294 1-12 0.012 1 '82 Maleic ..............................0.0115 9.96 1 *2 182 Citraconic (Methylmaleic) .. 0 00765 6'62 0'34 51.5 Phthdic ........................... 0.00461 3.99 0.121 18.3 It will be seen that succinic anhydride, with its saturated, five- membered ring, which on Baeyer's theory has practically no strain, is hydrated with almost the same velocity as the open-chain acetic anhydride. The velocity is greatly increased by a double link, less by a benzene link. With the exception of methylsuccinic anhydride, the order of the velocities is the same as that of the dissociation constants. The introduction of a methyl group raises the velocity of succinic anhydride and lowers that of maleic; it has the same ef€ect on the dissociation constants of the corresponding acids.213. (( Ethyl 6-methyl-2-pyrone-3 :5 dicarboxylate and its conver-sion into methyltrimesic acid." By John Lionel Simonsen. (Trans.,1910, 1910. ) Ethyl 6-methyl-2-pyrone-3: 5-dicarboxylate (Trans., 1908, 98, 1022), on hydrolysis, is converted into methyltrirnesic acid, which on oxidation gives prehnitic acid. The condensation of ethyl propiolate and ethyl acetoacetate was also investigated. 201 214. <‘The action of bases on ap-dibromobutyric acid and its esters.” By Thomas Campbell James. (Trans., 1910, 1565). The action of various alkalis, tertiary bases, and alkaloids in abstracting hydrogen bromide from ap-dibromobutyric acid has been examined.The reaction of the acid with aqueous potassium hydroxide has been followed kinetically ad shown to be strictly bimolecular. In the cwe of all the bases used, the product consists of a mixture of a-bromo and a-bromoallo-crotonic acids, the proportion of the former being greater the weaker the base used. When esters are used instead of the free acid, the proportion of a-bromo-acid is not increased to anything like the same degree as in the case of the analogous decomposition of up-dibromo-p-phenyl-propionic acid (cinnamic acid dibromide). 215. I‘ The absorption spectra of furan, furfuraldehyde, thiophen, and pyrrole under different conditions.” By John Edward PPnrViS. (Trans., 1910, 1648). The results of the investigation are: (1) The vapour of furan exhibits absorption bands, some of which are similar in appearance and have similar differences in wavelengths; the vapour of furfur- aldehyde also exhibits bands which can be grouped together, but which are different from those of furan; the vapours of thiophen and pyrrole show a few bands, two of which are comparable with two in the vapours of furan and of furfuraldehyde.(2) Alcoholic solutions of furan, thiophen, and pyrrole show no absorption bands, whilst a N/lOOO-solution of furfuraldehyde shows a strong band in the ultra-violet. (3) The liquids, furfuraldehyde, thiophen, and pyrrole, show no absorption bands. 216. The viscosity of certain amides.” By Albert Ernest Dnnstan and Albert George Xussell.(Trans., 1910, 1935). The authors have determined the viscosities of a considerable number of amides in the free state in aqueous solution and in pyridine solution. They find that in aqueous solution the simple fatty amides are still associated to a considerable extent, and that formamide is largely dissociated. The amides in the fused con-dition are associated, but whilst acetanilide has a high molecular viscosity, pointing to great association, methylacetanilide exisb in a much more simple molecular condition. In pyridine solution the amides show little signs of the acidic character which would be 202 expected did they possess the hydroxyiminic structure. With the exceptions of thiocarbamide, diphenylthiocarbamide, and cyanuric acid, the molecular viscosities are normal.217. “Changes in volume in the formation of dilute solutions. Part 11. Relationship between change in volume and constitu- tion.” By Harry Medforth Dawson. (Trans., 1910,1896). It is shown that the change in volume which accompanies the formation of dilute solutions of a given substance in a series of solvents is determined by the internal pressures and the com-pressibilities of the solvents provided that the formation of the solution is unaccompanied by changes in the degree of complexity of the solute and solvent, and that the two kinds of molecules do not enter into combination. Such solutions are termed “normal ” solutions. Experimental observations relating to iodine solutions indicate that combination between iodine and the solvent is of frequent occurrence.Since this combination is accompanied by an alteration in volume, the observed changes in volume in the formation of iodine solutions are not as a rule in agreement with the requirementx of the equation deduced for “normal solutions.” In some few cases, however, the relative volume changes are such as are anticipated by theory. The absence of parallelism in the volume changes when two substances are dissolved in t,he same series of solvents is also con-sistent with the view that solvates are usually formed in dilute solutions. 218. ‘I ap-Dibenzylaminopropionicacid and 1:7-dibenzyltetrahydro-uric acid.” By Edward Percy Frankland. (Trans., 1910, 1686).Following the method adopted by the author in the recent synthesis of tetrahydrouric acid, a dibenzyltetrahydrouric acid was prepared by the action of cyanic acid on aS-d~benzytarni~olrroln’onic acid (I),one of the carbamide groups being condensed with the carboxyl group by means of 25 per cent,. hydrochloric acid: CH,Ph*NEI*FH, CH,Ph*NH*QH, CH*NHCH,Ph bO,H (1.1 CH,Ph*NH*QH, CH,Ph*v-qH, qH0N(CH,Ph) 90 ?H-N(CH,Ph) NH>GOco-NH, CO--NH>co The first product of the action of cyanic acid on the dibenzyl- aminopropionic acid wits probably 6-bensylamino-a-b enaylcarbamido- propionic acid (11) (m. p. 200-201°), which was condensed with hydrochloric acid to P-benayl-y-benzylaminomethylhydantoin,(111) (m. p. 112-115O). One of the benzylamino-groups remained unacted on, and was capable of salt formation with a molecule of hydrochloric acid.The free base was converted into 1 : 7-dibenzyl-tetrahydrouric acid (IV) by prolonged heating with an excess of potassium cyanate in aqueous methyl alcohol; it forms prismatic crystals, melting with slight decomposition at 177-178O (uncorr.). The aP-dibenzylaminopropionic acid was obtained by boiling a solution of benzylamine in chloroform with aS-dibromopropionic acid. The free dibenzylamino-acid is sparingly soluble in water with an alkaline reaction to litmus; it forms rhomboidal plates, melting and decomposing at 181-184O (uncorr.). 219. “Contributions to the chemistry of the terpenes. Part VII. Bynthesis of a monocyclic terpene from thymol.” By .Cleorge Clerald Henderson and Maggie Millen Jeffs Sutherland.(Trans., 1910,1616). From thymol, C‘,II,MePrS*OH, the authors prepared thymo-quinone, which, on reduction with sulphuric acid, yielded thymo-quinol, C,H,MePrB(OH),. This dihydric phenol, when heated with hydrogen in presence of nickel according to the method of Sabatier and Senderens, was converted into the saturated disecondary alcohol, menthane-2 : 5-&oZ, C,,H18(OH),. This compound forms very small, colourless crystals. It melts at 112O and boils at about 155O/15 mm. It is very readily soluble in alcohol, ether, or light petroleum, readily so in benzene, and very sparingly so in water. When heated at 1 10--200° with anhydrous potassium hydrogen sulphate, it yields a terpene, Cl0HI6,which is a, colourless liquid, boiling at 179O/760 mm.It has a rather faint odour somewhat like that of limonene, and is practically insoluble in water, but readily soluble in the usual organic solvents. It at once reduces permamganate, and unites additively with bromine, but apparently does not react with nitrous acid to form a nitrosite. It is probably A1:4-menthadiene, QMe:CH*yH, CH2*CH:C*CHMe,’ 220. Contributions to the chemistry of the terpenes. Part VIII. Dihydrocamphene and dihydrobornylene.” By George Gerald Henderson and Ernest Ferguson Pollock. (Trans., 1910, 1620). When heated with hydrogen in presence of nickel according to the method of Sabat,ier and Senderens, bornylene, C10H16, is easily 204 converted into dilLydrobornyZene, CIOHI8,which appears to be identical with the saturated hydrocarbon camphane.When cam- phene, CIOHl6,is hydrogenated in a similar manner, the reaction is not so complete, and the nature of the product depends on the temperature. At 120-180° a solid product, melting at about 64O, was obtained, which by fractional crystallisation from methyl alcohol wm proved to be a mixture of dihydrocamphene, CIOHl8,already prepared by Vavon (Com,pt. rend., 1909, 149, 997), with a small proportion of unchanged camphene. At a higher temperature a liquid was produced, which was also found to be a mixture, contain- ing dihydrocamphene, a little unchanged camphene, and a small proportion of a third substance which was not further investigated.Dihydrocamphene, unlike dihydrobornylene, differs widely from camphane in melting point and other physical properties. These results confirm the view that the arrangement of the carbon atoms in the molecule of bornylene is the same as in that of camphane, and that the structure of the molecule of camphene is of a different type. 221. “The oxidation of monohydric phenols with hydrogen per-oxide.” By George Gerald Henderson and Robert Boyd. (Trans., 191C, 1659). A 30 per cent. aqueous solution of hydrogen peroxide has been found to be a good oxidising agent for monohydric phenols of the benzene series, the products being either a dihydric phenol, or a quinone, or even in some cases a tetrahydric phenol.From the results obtained with a number of phenols, it appears that those monohydric phenols in which the para-position relative to the hydroxyl group is unoccupied are most easily attacked by the oxidising agent, and yield as the main product either a p-dihydric phenol or a quinone according to the conditions of the experiment. On the other hand, those monohydric phenols in which the para- position relative to the hydroxyl group is occupied are not so easily oxidised, and usually yield dihydric phenols in which the hydroxyl groups are in the ortho-position to each other. Several new compounds were obtained. Some experiments on the action of hydrogen peroxide on cyclic hydrocarbons were also made. The hydrocarbons of the benzene series which were examined appeared to be somewhat indifferent to the action of the oxidising agent, but naphthalene, anthracene, and phenanthrene were readily attacked, yielding phthalic acid, anthra- quinone, and phenanthraquinone respectively. 205 222.‘‘ Solubilities of orgaaic snbatanoes in organic solvents, a contribution to the theory of solubility.” By Dan Tyrer. (Trans., 1910, 1778). The solubility of a substance in a particular solvent is governed by two factors, namely, (1) the temperature, and (2) the con- centration of the solvent, or the amount of solvent in unit volume of the saturated solution. Expressed mathematically, the solubility of a solute in a particulir solvent under all possible conditions is given by the equation S=K.f(C).+(T), where S is the solubility, C the concentration of the solvent, T the temperature, and E a constant.The object of the work was to determine the form of the function f(C). In order to avoid complications arising from the existence or formation of associated molecules in the solutions, the solubility of organic substances in organic solvents was studied. These were chosen also so as not to contain hydroxyl, amino- or cyanogen groups in order to minimise the possible formation of associated molecules. The method of attacking the problem was to find a solute soluble in a solvent A and insoluble in another solvent B, which is miscible with A in all proportions. The solubility of the solute in the mixed solvent is then determined, and the results are plotted against the concentration of the solvent in the saturated solution. Whilst some of the cases investigated give results which approxi- mately represent the solubility at constant temperature as a linear function of the solvent concentration, the general conclusion deduced from the results is that no simple and common law governs the relation between the solubility and the concentration of the solvent.Incidentally, determinations of the solubility of some organic substances in organic solvents were made at varying temperatures, and also of the concentrations of the solvents in the saturated solu- tions. It was noticed that in all the cases investigated the con- centration of the solvent could be very approximately represented as it linear function of the temperature.223. ‘(The chlorination of toluene.” By Julius Berend Cohen, Harry Medforth Dawson,John Reginald Blockey, and Arnold Woodmansey. (Trans., 1910, 1623). Experiments have been made to determine the influence of various factors on the relative proportions of benzyl chloride and of o-and pchlorotoluenm, which are obtained in the chlorination of toluene. The results indicate that side-chain substitution is favoured by 206 light and by rise of temperature, whereas nuclear substitution is favoured by the presence of small quantities of water and by adding to the toluene substances like nitrobenzene, which tend to promote the formation of polyhalogen compounds. Electrolytic chlorine behaves practically the same as ordinary chlorine.In respect of the above-mentioned factors, the chlorination process appears to be influenced in the same way as the bromination process, and the view is adopted that side-chain substitution is effected by halogen molecules, whereas nuclear substitution is brought about by halogen which is combined with the halogen acid in the form of polyhalogen compounds. This theory has already been put forward by Holleman (Proc. K. Akad. Wetensch. Amsterdam, 1905, 8, 512; Rec. trav. chim., 1908, 27, 435) to account for observations relating to the action of bromine on toluene. A method for the analysis of mixtures of toluene, benzyl chloride, o-chlorotoluene, and p-chlorotoluene is described.I‘224. The constitution of the benzenet etracarboxylic acids.” By Hannah Bamford and John Lionel Simonsen. (Trans., 1910, 1904.) A synthesis of Baeyer’s mellophanic acid from 1: 4-dimethyl-naphthalene is described, and proof is adduced that the usual views on the constitution of mcllophanic and prehnitic acids are incorrect. Prehnitic acid is 1: 2 : 3 : 5-benzenetetracarboxylic acid, whilst mellophanic acid is the corresponding 1 : 2 : 3 : 4-compound. 225. Action of light on the stereoisomeric piperon ylideneacetones and on other unsaturated ketones.” By Hans Stobbe and Forsyth James Wilson. (Trans., 191 0, 1722.) The authors have recently shown (Annulen, 1910, 374, 237) that stereoisomeric ketones of the benzylidenedeoxybenzoin type, Ar*CH:CYh*COPh, can be converted into one another by the action of heat, small quantities of hydrochloric acid, or by direct sunlight, a state of equilibrium resulting.The two stereoisomeric piperonylideneacetones, CH,:0,:C6H3* CH:CH*CO-CM, (Haber, Bey., 1891, 24, 618), have been investigated along similar lines, and similar results obtained. It was next attempted to obtain the hitherto unknown stereo isom erides of anisylideneacet one, piperonylideneacet op henone, an isylideneacet ophenone, and o-methoxybenzyliden eacetoph enone but the experiments were unsuccessful. Phenyl o-methoxystyryl ketone, MeO*C,H,*CH:CH*COPh, was obtained by condensing o-methoxybenzaldehyde and acetophenone by means of sodium hydroxide in alcoholic solution. 207 Doubly unsaturated ketones of the type of cinnamylideneaceto-phenone, CHPh:CH*CH:CH*COPh, are, by the action of sunlight, converted not only into stereoisomerides but also into polymerides.226. “ cycZoHexane, its separation from, and its estimation in, mixtures containing benzene.” By Thomas Stewart Patterson and Alexander Fleck, (Trans., 1910, 1773.) A mixture of cyclohexane and benzene may be separated by shaking with a small amount of ethyl tartrate, when the mixture separates into two layers. When a larger quantity of ethyl tartrate is added to the mixture a, homogeneous solution results, and from the rotatory power of this the composition of the mixture can be determined by comparing the found rotatory power with that of mixtures of known composition.227. The vapour pressures and molecular volumes of the mercuric halides and the relations between atomic volumes of elements before and after combination.’’ By Edmund Brydges Rudhall Prideaux. The vapour pressures of the liquid compounds from their melting points to their boiling points have been determined. The tempera- tures of equal vnpour pressures were compared with those of fluoro-benzene by Ramsay and Young’s method. If in the equation : TB and PB are the temperatures of fluorobenzene, c(HgC1,) = 0.0005, c(HgBr,) = Oa0O037,and c(Hgl,) = 0.00025. Trouton’s constant for the boiling point under 760 mm. pressure was found to be : HgCl,, 24.1 ; HgBr,, 23.9 ; HgIz, 23.7. Tbe specific volumes of the liquids were measured in silica dilsto- meters-the expansion being represented by the following, where Dt =density at to.HgCl, (280-335O) ; Dt = 4.400-0.002218 (t -280’). HgBr, (240-340’) ; Dt = 5.116 -0.00338 (t -240’). HgI, (255-355’) j Dt == 5.238 -0.00322 (t -255’). The ratios between the molecular volumes of the liquid compounds and the sums of the atomic volumes of the liquid elements, all measured at equal pressures of saturated vapour, are constant over the range of pressures investigated. These ratios are probably much the same as the ratios of the volumes of the atoms before and after combination. There is a slight expansion on combination which, 208 stated a8 the percentage increase on the volumes of the elements, is equal to : For HgCl,, 1.8; HgBr,, 7.4 ; HgI,, 95.The numerical values of Trouton’s constant and the expansions of the liquids show a slight association, diminishing in the order : chloride +bromide -+ iodide. 228. ‘‘A study of some unsaturated compounds containing the tert.-butyryl group. Part I.” By Alfred Archibald Boon and Forsyth James Wilson, (Trans., 1910, 1751.) The authors have investigated the action of bromine on ~‘peronyZidene2aco~ine,CH,:O2:C6H3*CH:CH*C0*CMes.This compound melts at 94-95O, and was obtained by the condensation of piperonal with pinacoline by means of sodium hydroxide. It gives an oxime (m. p. 144-145O), and, in chloroform solution, yields a monobromide (m. p. 1 1O-11lo), CH2:02:C6H,*CH:C’Br*Co*CMe~ (a-compound), or @H,:02:C6H3~CBr:CH~CO~CMe~(&compound), and also a dibromide, C‘H,: O,:C,H,*~Br*CHBr*COOCMe,, which melts at 138--139O, and is the chief product of the reaction.When absolute alcohol was allowed to act on the latter, a sub-stance was obtained identical with that produced when the di- bromide, in alcoholic solution, wits treated with potassium hydroxide (1 mol.). This product, which melts at 82-83O, may be repre-sented either as CH,:0,:C,H3*CHBr-CH(OEt~)*CO~CMe,, (a) or ICH,: 0,: (OEt) CEIBr*CO*CMq(S).c16H3*CH As a result of the action of potassium hydroxide (2 mols.) on the dibromide (m. p. 138-139O) in alcoholic solution, the authors obtained a compound identical with that already referred to, melting at 82--83O, and two et,hoxy-derivatives of piperonylidenepinacoline, CH,:0,:C6H3*(;OR:CT(OEt)*CO*CM~(a) and CH2:0,:C6H3~C(OEt):CH*C’O*CMe,(B), melting at 86-87O and 112-1 13O respectively. These compounds may, however, be stereoisomeric.229. ‘‘A new method for the preparation of argl ethers of glycerol a-monochlorohydrin.” By David Runciman Boyd and Ernest Robert Harle. (Trans., 1910, 1788.) The aryl ethers of glycerol a-monochlorohydrin are conveniently prepared by leaving a mixture of the phenol, epichlorohydrin, and a small quantity of sodium hydroxide for some days at the ordinary temperature. y-Chloro-B-hydrow-a-o-tolyloxypropane(b. p. 166O/ 18 mm.) and the corresponding p-tolyl compound (b. p. lGO/ 209 14 mm.) have been prepared.The phenylurethane of y-chloro-P-hydroxy-a-phenoxypropanemelts at TOo, and the phenylurethanes of the etolyloxy-and p-tolylory-compounds at 80-81O and 113-1 14O respectively. 230. The action of ammonia on the glycide aryl ethers. Part 11. Phenoxypropanolamines.” By David Runciman Boyd. (Trans., 1910, 1791.) The constitution previously assigned to the primary base derived from o-tolyl glycide ether, C,H,*O*CH,*CH(OH)*CH2*NH,,has been confirmed by the preparation of the same substance from y-chloro- P-hydroxy-a-o-tolyloxypropaneand ammonia. Phenyl glycide ether, when treated with a solution of ammonia in 50 per cent. alcohol, gives a primary base, C,H,*O*C~*@H(OH).CH,.NH2-NHz(m. p. 97-98”), and a secondary base, [ C,H,*O*CH,- CH (OH) CH,],NH (m.p. 101-1 02.). 231. The relation of position isomerism to optical activity. Part VIII. The rotation of the menthyl esters of the alkyloxy-and alkylamino-derivatives of benzoic acid.” By Julius Berend Cohen and Harold Ward Dudley. (Trans., 1910, 1732.) The present investigation is a continuation of former studies on the same subject, and deals with substituted menthyl benzoates containing positive in place of negative groups. Ten series of isomeric esters have been prepared, and their rotational values ascertained. The authors find that temperature is an important factor in such determinations. Whilst the temperaturecoefficient for the orthcxompounds is small and in nearly all cases positive, that of the para-compounds is large and negative, the intermediate meta-compounds being small and also negative.It follows that if a comparison of the three isomerides is made at looo instead of 20°, the rotational values of the meta-and para-isomerides approximate to that of the unsubstituted menthyl benzoate at the same temperature, whereas the value of the ortho-compound is widely divergent. The general rule which was previously estab- lished in the case of the halogen, nitro- and nitro-halogen derivatives applies with equal truth to the menthyl esters containing positive groups, namely, the ortho-substituent exerts a preponderating effect on the rotational value of the active group. 210 232. ‘‘The volatile constituents of coal.” By Maurice John Burgess and Richard Vernon Wheeler.(Trans., 1910,1917.) It is shown that with all coals, whether bituminous, semi-bituminous, or anthracitic, there is a well-defined decomposition- point at a temperature lying between 700° and 800°, which corresponds with a marked increase in the quantity of hydrogen evolved. With bituminous coals, the increase in the quantity of hydrogen evolved falls off at temperatures above 900°, but with anthracitic coals it is maintained up to 1100O. It is further shown that ethane, propane, and butane, and, probably, higher members of the paraffin series of hydrocarbons, form a large percentage of the gases evolved at low temperatures, but that at temperatures above 700° the evolution of such hydre carbons practically ceases.The suggestion is advanced that coal of whatever geological age contains a compound which undergoes decomposition at tem-peratures above 700° (under the atmospheric pressure), and yields hydrogen as its principal gaseous product. It seems probable, also, that the same compound is responsible for the hydrocarbons of the paraffin series that make their appearance at low temperatures. 238. (( Tetramethyl ferrocyanide and some derivatives.” By Ernald George Justinian Hartley. (Trans., 1910, 1725.) Experiments have been made in continuation of the work recently published (Trans., 1910, 97, 1066) on the reaction between potassium f errocyanide and methyl sulphate. By taking care to exclude moisture aa far as possible, the reaction followed a somewhat different course, and a neutral methy2 sulphute, (CH3),FeC6N,(CH3*S0,),, was isolated of the same base, the acid salts of which had been previously obtained.Unlike the acid methyl sulphate, this salt does not undergo any change on keeping in a vacuum over sulphuric acid. In addition to this, there were formed some of the acid sulphate previously described and another neutral salt of the same base, probably the ethyl sulphate. The neutral sulphate, (CH&FeC6N,sO,, can be pre-pared from the acid sulphate by neutralising with barium hydroxide in aqueous solution, removing barium sulphate, and evaporating the filtrate in a vacuum. It is an unstable substance, differing from the acid salt in being soluble in ethyl alcohol. The corresponding chloride is prepared by neutralising with barium hydroxide as above, and then adding excess of barium chloride and 211 evaporating to dryness.The salt is extracted from the excess of barium chloride with alcohol and precipitated with ether. It is far more stable than the sulphate. On heating the chloride under diminished pressure to 140°, methyl chloride is given off quantit.atively, and almost pure tetra- methyl ferrocyanide is left. This resembles the corresponding ethyl compound prepared from silver f errocyanide and ethyl iodide in being soluble in chloroform and water, and giving in aqueous solution a white precipitate with mercuric chloride and a reddish-purple coloration with ferric chloride. It is deposited from chloro- form in well-formed crystals containing chloroform of crystallisation. 234.The molecular complexity of amides in various solvents. Part 11." By Andrew Norman Xeldrnm and William Ernest Stephen Turner. (Trans., 1910, 1605.) In continuation of their previous work (Trans., 1908, 93, 876) the authors have determined the molecular complexity of seventcen additional amides in the same organic solvents as before. The principal object of the work was to test the NernstiThomson hypothesis, that association of the solute tends to be high when the dielectric constant of the solvent is low, and vice versa. They regard their results as in good agreement wit.h the hypothesis. The following table summarises the results (for organic solvents) of both investigations, and includes the dielectric constants of the solvents : Ch 1or0-Solvent.Alcohol. Acetone. form. Ether. Benzene. No. of amides investi-gated ..................... 28 27 22 14 21 No. of amides which 3nnd 1 3and2 3nnd 1 form simple molecities } 24 2o 1 doubtful clonbtful doubtful. No. of ainidrs which ) 4 arid 3for111 associated mole-9 17 cules ..................... ( tloltht f,,, tloll1)thd } L)ielectric constant ..... 25 4 at 13'5" 21'2 at 22" 5 at 28" 4'4at 18" S 3 at 18" 235. '(The tautomerism of glyoxalines and the constitution of pilocarpine." By Frank Lee Pyman. (Trans., 1910, 1614.) Otto Fischer (J. pr. Chem., 1906, [ii], 73,419; 1907, [ii], 75,88) has already shown that benziminazoles are tautomeric, and Jainecke (Ber., 1899, 32,1098) and Gabriel (Ber., 1908, 41, 1926) have made it seem probable that simple glyoxalines behave similarly.Conclusive evidence that simple glyoxalines react as tautomeric compounds is now brought forward, for it is found that 4(or 5)-methylglyoxdine yields on metshylation a mixture of 212 the two isomerides, 1 : 4-dim,etitylglyoxdine (I) (b. p. 198-199O) and 1: 5-dimethtyl$yoxa&ne (11) (b. p. 224-225O) : (1.1 (11.) Jowett and Potter (Trans., 1903, 83,464) by the methylation of 4(or 5)-methylglyoxaline obtained a dimethylglyoxaline which they regarded a,s a simple substance, but which was not identical with the dimethylglyoxaline obtained by Jowett (Trans., 1903, 83,438) from isopilocarpine.It is now shown that the latter compound is identical with 1: 5-dimethylglyoxaline, and that Jowett and Potter’s dimethylglyoxaline was a rnixture of the 1 : 4- and 1: 5-isomerides, consisting mainly of the former. The methylation of bromo4(or 5)-methylglyoxaline and dibromo-4(or 5)-methylglyoxale yields in each case a mixture of two isomeric N-methyl derivatives which have been separated and characterised. The bromination of 1: 4- and 1: 5-dimethylglyoxaline leads to the formation of one of the bromodimethylglyoxalines and one of the dibromodimethylglyoxalines in each case. 236. “Kinetics of the reaction between silver salts and aliphatic iodides.” By Frederick George Donnan and Harold Edward Potts. (Trans., 1910, 1882.) The experiments of Burke and Donnan (Trans., 1904, 85,555) have shown that the reaction between silver nitrate and an”alky1 iodide in alcoholic solution is disturbed by an accelerating effect due to one of the products.In the present paper it is shown that in the reaction between silver lactate and ethyl iodide in aqueous alcohol, the accelerating effect disappears. It is also shown that in the reaction between silver nitrate and ethyl iodide in a non-hydroxylic solvent (acetonitrile) when no free (nitric) acid is pro- duced, the kinetic behaviour does not essentially differ from that observed in alcoholic and aqueous solutions. The reaction between iodoform and silver nitrate in alcoholic solution follows the same pseudo-bimolecular equation as the reaction between a mono-iodide and silver nitrate.It was found that methylene iodide reacts very sluggishly with silver nitrate in alcoholic solution. Owing to the rapid decomposition of carbon tetraiodide in alcoholic solution, comparative experiments with this substance could not be carried out with sufficient accuracy. Although the matter could not be decisively settled, the general trend of the experimental evidence is in favour of the view that it is the undissociated silver salt which reacts with the alkyl iodide in the first instance, with the formation, possibly, of a transient intermediate product. The suggestion is made that the constancy of the velocity-coefficient in any particular reaction is due to a compensation of the decrease due to the increasing relative ionisation of the silver salt by the acceleration referred to above.Senter’s suggestion that the acceleration is due to the silver halide produced is discussed. 237. “The identity of osyritrin, myrticolorin, violaquercitrin, and rutin.’’ By Arthur George Perkin. (Trans., 1910, 1776.) It has been shown (Trans., 1902, 81, 477) that osyritrin, myrticolorin, and violaquercitrin axe identical. Schmidt (Arch. Pharm., 1908, 246, 214) and Wunderlich ($bid., 246, 224) have found that when hydrolysed violaquercitrin gives, in addition to quercetin and dextrose, also rhamnose, and that this glucoside is identical with rutin, which yields the same products. It therefore appeared certain that myritrin and myrticolorin in reality consist of rutin, and this has been found to be the case.238. A glucoside from Tephrosia purpurea.” By George Clark, jun., and Shrish Chandra Banerjee. (Trans., 1910, 1833.) Tephrosia purprea (Pers.), nat. ord. leguminosae, contains a yellow, crystalline glucoside (Clarke and Banerjee, Proc., 1909, 25, 16). This substance has been further investigated, and has the formula Cz7H30016,3Hz0.When hydrolysed, it is decomposed into quercetin, dextrose, and rhamnose according to the equation Cz,H3,0,6 + 3H,0 =C15H1007 + Cf3H1,0(j + C6H1,05,H,0. It is identical with rutin described by Schunk (Trans., 1888, 53, 264), which therefore has the above formula, and not that hitherto ascribed to it. I‘239. The molecular complexity of amides in various solvents.Part 111. Amides in aqueous solution.” By Andrew Norman Meldrum and William Ernest Stephen Tnrner. (Trans., 1910, 1805.) In continuation of their previous work (Trans., 1908, 93,876; 1910, 97, 1605) the authors have determined the molecular com-plexity of fourteen additional amides in aqueous solution. Water, by reason of its high dielectric constant, should prevent association of the solute, according to the Nernst-Thomson rule. The authors find that fifteen out of the total of twenty-three amides examined are associated in water. The authors hold that association in water is of frequent occur- 214 rence, znd has been ignored in the study of aqueous solutions to an injurious extent. They find that during the hydrolysis of ethyl acetate, or the inversion of sucrose, by hydrochloric acid, the presence of methylacetanilide, an associated substance, has an effect similar to that caused by the presence of sodium chloride, as observed by Caldwell (Proc.Roy. sbc., 1906, 78, A, 272) and H. E. Armstrong (Zoc. cit., 1907, 79, A, 576). The accelerations due to equal weights of the two foreign substances are approximately the same. 240. Optically active salts of 4-oximinocycZohexanecarboxylicacid and the configuration of the oximino-group.” By William Hobson Mills and Alice Mary Bain. (Trans., 1910, 1866.) If morphine (1 mol.) is added to the ethyl-alcoholic solution of 4-oximinocycZohexanecarboxylic acid, the morphine salt which separates contains a dextrorotatory form of the acid, for on decom- posing it with excess of ammonia and removing the morphine, the solution of ammonium salt obtained is strongly dextrorotatory, the molecular rotation varying from [MID50° to [MI, 60° in different preparations.Similarly, from the quinine salt (Proc., 1909, 25, 178), which has been crystallised from water, the corresponding laevorotatory ammonium salt, [MI, -70° to -80°, has been obtained. That the substances to which these optically active solutions of ammonium salt owe their rotatory power are the normal ammonium salts of dextro- and lzevo-rotatory forms of 4-oximino- cyclohexanecarboxylic acid was shown by treating the solutions with silver nitrate. The substances thus precipitated were pure silver salts of this acid, and when treated with an aqueous solution of sodium chloride they gave respectively dextro- and lxvo-rotatory solutions of the corresponding sodium salts, the molecular rotations observed being [M], 7405~and -79.9O.Autoracemisation takes place very rapidly in neutral solutions of these optically active salts, but it is greatly retarded by the presence of excess of alkali. By these experiments the existence of a new type of optically active substances is demonstrated, the molecular asymmetry of which is determined by the peculiar configuration of the doubly linked tervalent nitrogen atom. In addition, direct proof is afforded that in the oximino-group the three valencies of the nitrogen atom are directed along the three edges of a trihedral angle, as was postulated by Hantzsch and Werner (Ber., 1890, 23, 11).215 241. (‘The resolution of benzoyloscine.” By Frank Tutin. (Trans., 1910, 1793.) Benzoyloscine (benzoylscopoline) has been resolved by the f rac-tional crystallisation of its d-bronzocamphorsulphonate. Benzoyl-d-oscine d-bromocampphorsulphonateforms needles, which melt at 246O, but b enzoyl-l-oscime d-brornocamphorsulphonute could not be obtained in a state of purity. Benzoyl-d-oscine hydrochloride melts at 283-284O; the corresponding nitrate at 200O; the picrate at 211-212O; and the aurichloride at 189-190°. Benzoyl-d-oscine has [aIn +3.5O in 50 per cent. alcohol, whilst the ion of this base has [ulD +lO*Oo, calculated from the rotation of its d-bromocamphorsulphonate.d-Oscine was prepared in the form of its hydrochloride by hydro- lysing benzoyl-d-oscine with hydrochloric acid. It has a specific rotation of about + 77.7O. Benzoyloscine d-camphorsulphonate melts at 167-1 68O, and forms microscopic, diamond-shaped crystals, but it could not be resolved by fractional crystallisation. 242. ‘6 Carboxylic acids of cyclohexanone and some of its deriv- atives.” By Henry Dent Gardner, William Henry Perkin, jun., and Hubert Watson. (Trans., 1910, 1756.) A detailed account of an investigation of which a preliminary note has already appeared (this vol., p. 136). 243. (‘Note on the constitution of a-elaterin.” By Charles Watson Moore. (Trans., 1910,1797.) The following formulze have, at various times, been suggested for elaterin : C20H2,0, (Zwenger) ; CBH,O, (Thoms) ; C,,H,O, (Hemmelmayr) ; and CZ8H3,O7 (Berg).The present author has now obtained results which prove the correctness of the empirical formula suggested by Berg. The presence of an acetyl group in elaterin has been confirmed, but it has been shown that this sub- stance contains no ketonic or aldehydic group. Two crystalline substances have been obtained by the oxidation of “ elateric acid,” which have been shown to possess the formulze C24H3204and C24H3005 respectively. The latter of these is a diketone, and has been designated elaterone. On distillation with zinc dust, elaterin yields 1: 4dimethylnaphthalene. 216 The results so far obtained indicate that the formula of elaterin may be represented as follows: -OH 244. ‘‘The viscosity of salt solutions.” By Malcolm Percival Applebey.(Trans., 1910, 2000.) By the use of specially standardised viscometers of a modified Ostwald type, the viscosities of aqueous solutions of lithium nitrate have been determined at 25O, 1S0, and Oo over wide ranges of con-centration with an error of not more than 0.01 per cent. for solutions less concentrated than normal. The formula of Griineisen (Wiss. Abh. Phys.-Tech. Reichs., 1905, 4, 151) is found not to represent the phenomena of dilute solution. A method of calculating the viscosity of salt solutions from their hydration numbers, or vice versa, has been described. The application of this method to the viscosities of solutions of lithium nitrate at 1S0 and 25O gives results consistent with the estimates of ionic hydration made by other observers. The application of the method to some other salts is discussed.246. ‘( Somereactions of keten. Combination with hydrocyanic acid.” By Stella Deakin and Norman Thomas Mortimer Wilsmore. (Trans., 1910, 1968.) The compound which was mentioned (Proc., 1908, 24, 77) &s being formed by the action of keten on hydrocyanic acid has been further investigated. In a pure state it is a colourless liquid, which boils undecomposed at 110*2°(corr.)/ 100 mm., and with slight decomposition at 173O/772 mm. It may be frozen to a white solid, which melts at -196O to -195O. Analysis and determination of molecular weight show that it has the composition C,H,02N.The new substance is decomposed by water with formation of acetic and hydrocyanic acids, and by alcohol in the presence of mineral acids, ethyl acetate and hydrocyanic acid being obtained. It also reacts with aniline, giving acetanilide and hydrocyanic acid. It -is tentatively suggested that the new compound may be a-acetoxy-acrylonitrile, CH,:C(CN)-O*CO*CH,, a constitution which is shown to be consistent with the molecular volume, refractivity, and dis- persion of the substance. The actions of magnesium methyl iodide and of nitrosyl chloride 217 on keten have also been studied. With the former acetone is produced, and with the latter chloroacetyl chloride; but in both cases the greater part of the keten condenses with the formation of brown resins.246. The polymerisation of keten. cyctoButan -1 : 3 -dione (‘ acetylketen ’).” By Frances Chick and Norman Thomas Mortimer Wilsmore. (Trans., 1910, 1978.) The research on the polymerisation of keten (Trans., 1908, 93, 946) has been continued, and the first or bimolecular polymeride has been more fully studied. This substance combines with bromine to form a bromoacetoacetyl bromide, which with alcohol gives y-bromoacetoacetic ester and not the a-derivative, showing conclusively that the bimolecular polymeride is cyclobutan-1 : 3-dione and not acetylketen, as previously supposed. From the bromo-acetoa.cety1 bromide, an anilide was also obtained, identical with the bromoacetoacetanilide described by Knorr (Annulen, 1886, 236,79), which shows that the bromine in this substance is in the y-and not in the a-position, as believed by him. As a further consequence, the bromohydroxymethylquinoline, obtained by Knorr by the action of sulphuric acid on bromoacetoacetanilide, would seem to have the bromine attached to the methyl group and not, to the nudeus, or else the bromine atom must wander from the methyl to the CH, group during the con-densation.With ammonia, cyclobutan-1 : 3-dione forms, in the first place, the acetoacetamide described by Claisen and Meyer (Ber., 1902, 35, 583); but by t,he further action of ammonia an oil is obtained, which appears to consist chiefly of aminocrotonamide, since on heating it.gives a compound having the composition C8HI3O2N3,which is in all probability a lutidine derivative, namely, 4-amino-2 : 4-dimet hyl-A2-tetrahydro-6-pyridone-3-carbowl-amide. With semicarbazide, cyclobutan-1 : 3-dione forms the semi- carbazone-semicarbazide of acetoacetic acid. With magnesium mehhyl iodide, diacetone alcohol appears to be formed in small quantity. With hydrogen in presence of plafinum black, cyclo-butan-1: 3-dione is reduced to butyraldehyde. It does not react with sodium, with phenylcarbimide, or with hydrocyanic acid. On long keeping, or on warming, it polymerism with formation of deh ydr acet ic acid. Much work has been done with a view to elucidating the nature of the yellow, crystalline compound, which is formed from cyclo-butan-1: 3-dione in the presence of quinoline; but so far no clue to its constitution has been found.Its empirical formula is, however, C,,H,,O,. It is possibly a naphthalene derivative. 218 247. “Aromatic antimony compounds. Part I, The oxidation and nitration of triphenylstibine.” By Percy May. (Trans., 1910, 1956.) A description is given of the nitration of triphenylstibine, a preliminary account of which has already appeared (this vol., p. 142). The behaviour of triphenylstibine towards vaTious oxidising agents, such as concentrated sulphuric acid, and potassium permanganate, is described, and the relation between various derivatives of triphenylstibine oxide, and the influence of the nitro- group in the molecule are also discussed.248, “Contributions to our knowledge of the sulphide dyestuffs. Part I,” By George Herbert Frank. It has been found that many colouring matters belonging to the “ sulphide ” clam readily combine with chloroacetic acid, giving carboxylic derivatives which are readily soluble in alkalis. The colouring matter known as immedial-indone gives a di-carboxylic derivative, C,,H,,O4NzS, (Found, M.W. =377), which requires, for its reduction to the leuco-compound, two atoms of hydrogen per molecule. The suggested constitution for this di- carboxylic derivative is : N /\ \/\f ICO,H* CH,-NH\/\//\/tS*CH,*CO,. 8 I 249. “The constituents of leptandra.” By Frederick Belding Power and Harold RogerRon.(Trans., 1910, 1944.) The material employed for this investigation was commercial ‘(leptandra,” consisting of the dried rhizome and roots of Veronica virginica, Linn6 (Leptandra virginica, Nuttall). A concentrated alcoholic extract of this material, when distilled in a current of steam, yielded a small amount of an essential oil. The latter was a dark-coloured liquid, which distilled between 1200 and 160°/25 mm. The portion of the extract which was soluble in water contained 3 : 4-dimethoxycinnamic acid, C,H,(QMe)2.CI~:CH*C‘0,H(m. p. 180-181°); a quantity of mannitoI, amounting to 2.14 per cent. of the weight of the drug; and a sugar which yielded d-phenyl- glucosazone (m. p. 209-211°), together with tannic and colouring matter.It yielded, furthermore, a quantity of an amorphous 219 product, which possessed an intensely bitter, nauseous taste, and amounted to 1.6 per cent. of the weight of the drug. By the hydrolysis of this product there were obtained, besides resinous material, cinnamic and pmethoxycinnamic acids. The portion of the extract which wzls insoluble in water con-sisted chiefly of a dark brown resin, which amounted to 6.2 per cent. of the weight of the drug. From this resin the following substances were obtained : a phytosterol, C2,H460 (m. p. 135-136O ; [u]~-33-Oo), the acetate of which melts at 119-120°, and which it is proposed to designate verosterol; a mixture of fatty acids, consisting apparently of oleic, linolic, palmitic, and stearic acids ; p-methoxycinnamic acid, OMe*C$&*CH:CH*CO,H (m.p. 170°), which waa present in the form of an ester, and a, very small amount of 3 : 4-dimethoxycinnamic acid. It has not been possible to confirm the statement recorded in the literature that ‘(leptandra ” contains a crystalline, bitter glucoside, designated as “ leptandrin,” to which its activity may be attributed, nor does it contain a saponin, zls has been asserted. 250. “The formation of tolane derivatives from p-chlorotoluene and 3 :4-dichlorotoluene.” By James Kenner and Ernest Witham. (Trans., 1910, 1960.) The anomalous formation of a tolane derivative during the preparation of benzotrichloride from toluene, described by Lieber- mann and Homeyer (Ber., 1879, 12, 1971), wm also observed by Armstrong and Wynne during the conversion of p-chlorotoluene and of 3 : 4-dichlorotoluene into the corresponding chlorobenzylidene dichlorides. The present authors have investigated these toluene derivatives with the view of determining the conditions leading to their formation.To aid in the study of this condensation, 4: 4/-dichlorotolane tetrachloride has been obtained by the action of copper powder on pchlorobenzotrichloride. ‘Ihe method gives only moderate yields, and, as previously found by Fox (Ber., 1893, 26, 653), an3 now confirmed by the authors, breaks down when applied to the case of o-chlorobenzotrichloride. cis-and trans4 : 4/-Dichlorotolane dichlorides, melting at 166-167O md 86-87O respectively, result from the action of zinc dust on the tetrachloride in alcoholic solution at 50° for two days, although under these conditions some of the cis-isomeride is further reduced to 4: 4/-dichlorotolane (m.p. 175-176O), whilst at the boiling point the conversion is complete. Both the cis-2: 21-and 4: 4’-dichlorotolane dichloridea under similar conditions give the corresponding dichlorotolanes. 220 251, ‘‘The effect of temperatureon the equilibrium 2CO CO,+C.”By Thomas Fred Eric Rhead and Richard Vernon Wheeler. The equilibrium between carbon monoxide, carbon dioxide, and carbon has been determined for every 50° between 850° and llOOQ and for 1200O. The method adopted has been to circulate carbon dioxide con- tinuously over purified wood charcoal heated in an electric resistance furnace of special construction until the pressure in the apparatus attained a constant value.The values obtained for the equilibrium are as follow: Carbon dioxide. Carbon monoxide. Per cent. by volume. Temperature.850” 6‘23 < A 93.77 \ 900 2‘22 97’78 950 1 -32 98-68 1000 0*59 99.41 1050 0‘37 99-63 1100 0.15 99-85 1200 0.06 99’94 From the equation (derived from Le Chatelier’s general equation for equilibrium in gaseous systems), the following values for k are obtained: T. k. 1123 20.01 1173 20-39 1223 20-24 1273 20‘44 1323 20-32 1373 20.70 1473 20.65 252. “The molecular complexity in the liquid state of tervalent nitrogen compounds,” By William Ernest Stephen Turner and Ernest Wyndham Merry.The molecular complexities of nearly forty organic nitrogen compounds, comprising amines, nitrosoamines, nitriles, and amides have been determined by Ramsay and Shields’ method; one, and the main, object of the investigation being to ascertain if the molecular association in the amides can be ascribed to the action of the unsaturated valencies of the nitrogen or oxygen atom present in the amido-group. Primary amines were found to be slightly associated. Secondary and tertiary amines gave abnormally high values of the Ramsay and Shields’ constant, and the result% raised the question of the validity of the Ramsay and Shields’ formula. The ctliphatic nitrosoarnines and aliphatic nitriles axe associated; 221 the aromatic members of these two groups of compounds are either oiily slightly or non-associated.The amides and anilides examined are associated, the extent of association being of the same order as found in the aliphatic alcohols and acids. The aromatic amides, benzamide and salicylamide, are strongly associated. Below 80°, formamide is more highly associated than water, but the molecular complexity decreases rapidly with rise of temperature. It was concluded that the cause of molecular association in the amides cannot be directly ascribed to the unsaturated character of hhe nitrogen or oxygen atom, and that association only occurs when these elements are found in combination in electronegative groups.Thursday, October 20th, 1910, at 8.30 p.m., Professor HAROLDB. DIXON,M.A., Ph.D., F.R.S., President, in the Chair. Messrs. H. A. Tempany and J. Haycock were formally admitted Fellows of the Society. Certificates were read for the first time in favour of Messrs.: Malcolm Percival Applebey, Hill View, Foxcombe, near Oxford. Manindranath Banerjee, 3, Padmanath Lane, Shambazar, Calcutta. Fred Wilkinson Barwick, Rathlyn, Kilmorey Gardens, St. Margaret’s-on-Thames. Sarat Chandra Bhattacharya, M.A., Hazaribagh, Bengal, India. Andr6 Bracher, 30, Guilford Street, W.C. Frederick Hugh Rochfort Brady, 12, Park View Avenue, Harold’s Cross, Dublin. Stewart McGregor Bosworth, B.Sc., 65, Abingdon Villas, Ken- sington, W. John C. Briggs, East View, Workington.John Brown, B.Sc., Technical Institute, Timaru, New Zealand. Frederick Challenger, B.Sc., 324, Mansfield Road, Carrington, Nottingham. Reginald Thomas Colgate, 26, Birdhurst Rise, S. Croydon. Thomas Watts Coslett, Steel Road, Northfield, Worcs. John Hughes Davies, B.Sc., Ph.D., St. Peter’s College, Peterboro’. James Hugh Duncan, 18, ParFPlace, Cardiff. William Gidley Emmett, B.A., Caius College, Cambridge. Ainslie Jackson Ensor, B.Sc., 67, Cannon Street, Wellingborough. John George Finlayson, B.A., 13, Monarch Terrace, Blaydon-on- Tyne. George Alexander Godden, 18, Rylett Crescent, Shepherd’s Bush. Edmund Knecht, M.Sc., Ph.D., Municipal School of Technology, Manchester. 222 William Arthur Knight, M.A., 5, The Green, Marlborough.Bertram Lambert, M.A., 34, Leckford Road, Oxford. Kenneth Stewart Low, 3, Luxemburg Gardens, W. Clement Ward Lowe, Thorneyholme, Knutsford. Malcolm McNish, Shortsands, St. Neots. James Irvine Orme Masson, M.Sc., 2, Chester Street, Edinburgh. Riko Majima, 37, Linden Gardens, Notting Hill Gate, W. Thomas R. Merton, B.Sc., 18, Grosvenor Street, W. Dhirendranath Mitra, B.A., 89/ 2, Musjeed Bari Street, Calcutta. Harold Moore, B.Sc., 84, .Kalashnikeff Quay, St. Petersburg. Valliyil Govindan Nair, B.A., B.Sc., 223, Upper Brook Street, C-on-M., Manchester. John Hamilton Paterson, M. Sc., Carmyle, Wellington Street, Grimsby. Alfred John Pennington, Oakley, Fallowfield, Manchester. Benjamin Ashwell Posford, Wood Dene, Kippington, Sevenoaks.Hari Prasad, B.A., B.Sc., 97, Roseneath Road, Urmston, Man- ches ter . Frederick Valentine Ramsden, Alexandra Street, E. St. Kilda, Victoria, N.S.W. Thomas John Rees, B.A., B.Sc., Cwmllynfell, Swansea Valley. Gangaram Rajendrarao Rele, 18, Entwistle Street, Manchester. Joseph Ridgway, B.A., Rownall Ball, Wetley Rocks, Stoke-on- Trent. James Beglar Robinson, Dairy School, Kilmarnock. Frederick Herbert Sharpe, The Ferns, Cressington Park, Liver- pool. Percy Lancelot James Smith, M.A., Army College, Storrington, Sussex. Jwala Prasad Srivastava, B.Sc.Tech., 20, Curzon Avenue, Victoria Park, Manchester. Augustus George Terrey, 47, Cann Hall Road, Leytonstone, N.E. Joseph Turner, Azo House, Birkby, Huddersfield. Robert Lauder Mackenzie Wallis, B.A., Llwyndu, Cardiff Road, Llanishen, S.Wales. Syed Muhammad Jusuf, B.Sc.Tech., Municipal School of Tech-nology, Manchester. Of the following papers, those marked * were read: "253. "The constitution of eriodictyol, of homoeriodictyol, and of hesperitin." By Frank Tutin. The author has methylated eriodictyol, homoeriodictyol, and hesperitin, and obtained from each of these compounds 2-hydroxy- 223 4 : 6-dimethoxyphenyl 3 : 4-dimethoxystyryl ketone (m. p. 154O) and 2: 4: 6-trimethoxyphewgl 3: 4-dimethoxystyryl ketone (m.p. 85' when air-dried, 117.5O when anhydrous), thus proving the correct- ness of the conclusions of Power and Tutin (Trans., 1907,91, 887) regarding the constitution of the three naturally-occurring sub-stances mentioned.These compounds are therefore represented as follows : OH OH CH:CH.CO/-\OH\-/ HO<-)CH:CH:CH-CO<_)OH HcJ OH MeO-OH Eriodictyol. Homoeriodictyol. OH M~o/-\cH: CH*CO<_)OH.\-/HO OH Hesperitin. The view was expressed that naringenin is not the phloroglucinyl ester of p-hydroxycinnamic acid, as concluded by Will (Ber., 1887, 20, 297), but 2 : 4 : 6-trihydroxyphenyI 4-hydroxystyryl ketone. "254. "The synthesis of 2 :4 :6-trimethoxyphenyl3 :4-dimethoxy-styryl ketone, a methyl derivative of eriodictyol, homoeriodictyol, and hesperitin." By Frank Tutin and Frederic William Caton, Vanillin methyl ether, when condensed with 2 : 4: 6-trimethoxy-acetophenone, yields 2 : 4 : 6-trimethoxyphenyt 3 : 4-dimethoxy-styryl ketone (m.p. 85O when air-dried, 117-5O when anhydrous), which is identical with the fully methylated product obtained from eriodictyol, homoeriodictyol, and hesperitin (compare preceding abstract). The action of aluminium chloride and acetyl chloride on phloro-glucinol trimethyl ether was shown to result in the formation of a ~~ydroxydiacetytdimethox~~enzene (m. p. 127-128O) possessing the following constitution : CH,*CO OMeHO<-)CV-CH, OMe "255. "Aniline-black and allied compounds. Part I." By Arthur George Green and Arthur Edmund Woodhead. The authors, after reviewing and criticising the recent work of Willstatter and Dorogi on aniline-black, gave an account of the preparation of certain intermediate substances obtained in the con-version of aniline hydrochloride into aniline-black. The first product is emeraldine, and from it four other substances have been prepared, namely, two by oxidation, nigraniline and pernigraniline, and two by reduction, protoemeraldine and leucoemeraldine.All ' 224 these compounds form a series, any member of which can be con-verted into any other by the use of a suitable oxidising or reducing agent. With the view of finding their molecular weight and probable constitution, these compounds have been analysed by deter- mining the amount of hydrogen necessary to convert the more highly oxidised substances into less highly oxidised ones, and, conversely, the amount of oxygen required to oxidise the latter.From the resulb obtained, the following formulae are assigned: Leucoemeraldine : NH NH NH NH NH NH Protoemeraldine : NH NH NE N \A/\/ \ \/\/ \/\/\/ \/\/'"'"'I"''NH NH NH Emeraldine : NH NH N N /\/\A A/\/ \/*NH NH N Nigraniline : NH N N N("f\() /\/\/\I '\/\/\ /\A/\I I I f' I I ' I I I'NH\/ \/\/\/ \A/\/ \/\/\/ \/*NH N N Pernigraniline : N N N N The question a8 to whether the chain is open or closed is, for the present, to be regarded as unsettled. An attempt has been made to clear up the present extremely involved nomenclature relating to aniline-black and allied sub-stances, and, further, it has been shown that the so-called '(aniline-blacks " of Kayser, Nietzki, Willstiitter, etc., consist essentially of emeraldine and nigraniline mixed with higher condensation products of at present unknown constitution.225 "256. "The colour changes of methyl-orange and methyl-red in acid solution." By Henry Thomas Tizard. The author has measured quantitatively the changes in molecular colour of methyl-orange and rnethyl-red in solutions of varying concentrations of hydrogen ions. From the results the following constants have been deduced : K,. Ka. Methgl-orange (at 25") .................. 4.25 x loW4 <10-14 NMe,'C,H,*N:N*C,H,*SO,HMethyl-red (at 18") ................... 1.05 x 3 x 10-13 NMe2*C,H,*N:N*C,H,-COzH The value of methyl-red as an indicator was discussed, and it WM shown that its '' neutral point " lies between concentrations of hydrogen ions of 10-5.7 and 10-7, which are very close to one another and to the theoretical neutral point at lo-'."257, ''The hydrolysis of aniline salts measured colorimetrically." By Henry Thomas Tizard. The author has applied the results of the preceding paper to the colorimetric measureaent of the hydrolysis of aniline hydrochloride and acetate in aqueous solution. A determination of the depth of colour of methyl-orange in such solutions gives directly the concentration of hydrogen ion. The method compares well in accuracy with other methods for meaauring hydrolysis when the base used is weaker than ammonia, as in the salts examined; at the same time measurements can be made eaaily and quickly. The results of Veley and other investigators in this field were discussed.DIscussION. Mr. BARON asked whether the author had, in comparing the depth of colour, considered the effect of fluorescence in the indicator employed. Mr. TIZARD, in reply, said that he had not observed any fluorescence in carrying out the experiments. 258. " The structure of xanthonium and acridinium salts." (Pre-liminary note.) By John Theodore Hewitt and Ferdinand Bernard Thole. The compounds formed by xanthenol and its derivatives with mineral acids, water being eliminated, have generally been regarded as oxonium salts (Hewitt, Zeitsch. physikul. Chem., 1900, 34, 9; Decker, Ber., 1901, 34, 3300). Gomberg and Cone claim that they are carbonium compounds (Annden, 1909, 370, 142), recogniaing the analogy to the acridinium compounds; the lat.ter also receive a carbonium structure from these authors. Kehrmann (Annalen, 1910, 373,287) opposes this view, and the 226 present authors find that whilst phenylxanthenol and phenylmethyl- acridol give nearly the same absorption spectra, acids effect a change in these spectra, pointing to the salts formed in the two cases having similar constitutions. Since the view that methyl iodide forms an additive product with phenylacridine of the constitution seems untenable, the present authors agree with Kehrmann in pre- ferring to retain an oxonium structure for the salts obtained from xanthenol and its derivatives.Amino-derivatives of both series are under investigation.259. ‘I The application of viscometry to the measurement of the rate of reaction.” (Preliminary note,) By Albert Ernest Dunstan. With the object of introducing a method for the measurement of reaction velocities which will be applicable to cases where diffi- culties may be met, wit.h in the chemical determination of the concentrations of the reacting compounds, and will also be free from the necessity of using a substance foreign to the reaction as an indicator of the course of events, the author has studied the viscosity-time curves for many reactions, amongst which are : (1) moto-isomeric change ; (2) isodynamic change of ethyl acetoacetate, ethyl malonate, and acetylacehne after distillation ; (3) tautomeric change of dextrose and lactose in aqueous solution; (4) hydration of aldehydes ; (5) formation of thiocarbamide and carbamide from ammonium thiocyanate and ammonium cyanate respectively ; (6) the benzidine transformation.In those examples where the viscosity of the end product or equilibrium mixture is sufficiently different from that of the initial compound, it is possible to calculate a velocity-constant. 260. “Iodoacenaphthene.”By Holland Crompton and Muriel Kate Harrison, Iodine acts on acenaphthene in the presence of yellow mercuric oxide. The acenaphthene is dissolved in boiling methyl alcohol, the solution is slightly cooled, and then a mixture of iodine (1 mol.) with rather more than the calculated amount of mercuric oxide is gradually added. The solution is finally raised to the boiling point and filtered.The crude iodoacenaphthene which crystallises out is first freed from mercuric iodide by dissolving it in cold chloroform, and then purified by crystallisation from methyl or ethyl alcohol. A complete purification is best effected by cou-verting it into the picrste, crystallising this from alcohol, and then washing out the picric acid with ammonia. Zodoacenaphthene, CI2H,I, crystallises from alcohol in colourless needles or prisms. Fine, highly refractive, prismatic crystals are 227 obtained on slow evaporation of an ethyl acetate solution. It melts at 65’5O, and decomposes at a little above 180°, with copious liberation of iodine. The picrate crystallises in fine, orangered needles, melting at, 102’5O.It is gradually decomposed on crys-tallisamtion from alcohol. On oxidation by sodium dichromate in acetic acid solut.ion, an iodonaphthalic acid is obtained, the anhydride of which melts at 231O. The copper salt of this acid, on heating with soda-lime, gave naphthalene and an oil which was obtained in too small an amount for identification. On fusing the acid with potassium hydroxide at 260°, 4-hydroxynaphthalic acid wi19 obtained. From this it is probable that the acid is 4-iodo-naphthalic acid derived from 4-iodoacenaphthene. It has been found, however, that whilst 4-chloro- and 4-bromo-acenaphthene form isomorphous mixtures with one another, they are not iso-morphous with the iodoacenaphthene which is here described.Further experiments are therefore being undertaken to investigate the constitution of this compound. 261. An improved form of extraction apparatus.” By James McConnell Sanders. The form of extraction apparatus illustrated in the accompanying diagram possesses several advantages over the usual form of Soxhlet extractor, or similar appliances in which the substance to be extracted is contained in a vertical tube the upper orifice of which is closed by the cork carrying the reflux condenser, the cork having to be removed each time a fresh quantity of material has to be introduced. Fig. 1 shows the simpler form of apparatus, which when once mounted with its condenser is always ready for use; successive quantities of material may be introduced by simply removing the glass stopper D, the extraction being cmried on with the tap A closed, when the apparatus acts as an intermittent extractor. When extraction is complete, the tap A is opened, and the solvent distilled off directly through the sidetube.When using very volatile solvents, such as ether or carbon di- sulphide, the subsequent distillation of the solvent is facilitated by removing the cartridge containing the exhausted material, and substituting a glass boiling tube containing cold water or crushed ice. The more elaborate form shown in Fig. 2 has two taps B and C, and when both these are kept closed the tubes t, t act as a siphon, and the extractor works intermittently. With C closed and B open, the apparatus works as a continuous extractor, or cm be used also as a reflux condenser, eapecially if an inner tube containing cold water or ice is used.228 With B closed and C open, the apparatus can be used for distilling off the solvent, a,s described in the case of Fig. 1. In the author’s laboratory a large model constructed of tinned copper has been in use for several months, and has proved of great value in cases where the probable amount of extractive matter was unknown, since in the event of too small a quantity of material being taken in the first instance, it was an emy matter to place a succession of weighed cartridges in the extractor and extract with the same amount of solvent without dismounting the apparatus.This copper extractor has an internal capacity of 1000 c.c., and in order to adapt it for use with smaller quantities of material a number of ‘‘ dummy ” cartridges of thin sheet copper are used to fill up a certain amount of space before placing the material in position. 262. ‘‘The synthesis of nitrognoscopine and allied substances.” (Preliminary note,) By Edward Hope and Robert Robinson. The synthesis of gnmcopine (r-nrtrcotine) has recently been accomplished (Perkin and Robinson, this vol., p. 46) by the eon- 229 densation of cotarnine amd meconine with the aid of potassium carbonate in alcoholic solution. The present authors have observed that the condensation of cotarnine and nitrophthalides or their methoxy-derivatives occurs with very much greater facility.Thus, nitrognoscopine is obtained in practically quantitative yields by boiling equimolecular quantities of cotarnine and nitro- meconine in alcoholic solution for a few minutes. The remtion proceeds in accordance with the following scheme : OMe O/\PHO CH2<Oi I NHMe v\C H,*CEl,/OMe OM0 CH2 OMe CH, OMe CO,H /\/\ MeO()/\o M*O/\/110 I1 '\/\/ NO,No"\/ co NO, CO \/\CO,H (1.1 (11.) (111.) The nitromeconine may be replaced by 5-nitrophthalide (I) or by nitro-$-meconine (II), the constitution of which is demonstrated by its oxidation with permanganate to the known nitrohemipinic acid (111). It is clear therefore that the nitro-group may be in the ortho-, meta-, or para-position in relation to the reactive *CH2*group of the phthalide ring.Nitrognoscopine, CH2:Oz:C18Hl,02(0Me)~*NOz,is very sparingly soluble in boiling alcohol and the usual organic solvents, but crystallism from hot trichloroethylene in bright yellow prisms, which melt and decompose to a red liquid at 191O. It is readily decomposed by warm glacial acetic acid, yielding cotarnine md ni tromeconine. The sparingly soluble, pale yellow hydrochloride, the aztmcMoride, and picrate have been prepared and analysed. The methiodide, C~:O2:CI8H,,O2(0Me)8.No,,MeI, is a yellow, crystalline powder, which melts at 205-206O. On boiling with silver chloride in aqueous solution, the metho- 230 chloride and silver iodide are obtained, and the addition of sodium hydroxide to the cooled and filtered solution gives a yellow, amorphous precipitate of the ammonium hydroxide.This substance dissolves in boiling water, and the solution, on cooling, deposits orange crystals of nitTonarceine, C23H26010N2,melting at 160-1 70°, and soluble both in dilute acids and alkalis. This decomposition is entirely similar to that by which narceine is produced from narcotine or gnoscopine. isAminognoscopine, CH2:02:Cl,Hl,0,(OMe)3*NH2,formed by the reduction of nitrognoscopine with tin and hydrochloric acid in the cold. It crystallises from ethyl acetate in colourless, lustrous prisms, melting at 205O, which are not decomposed by boiling glacial acetic acid. A cetylaminognoscopine occurs in highly characteristic bunches of needles, melting at 198O.Nitro-$-gnosco+e, prepared from cotarnine and nitro-$-meconine, crystallises from a mixture of chloroform and alcohol in pale yellow needles, melting at 184O. In general properties it resembles the isomeric nitrognoscopine. Anhydrocotarninenitrophthalide (n~trodesd~methoxygnoscop~ne), CH,:O,: C18H110Z(OMe)*NO,, crystallises in prisms melting at 176-177O. It is not so readily decomposed into its constituents by means of hot glacial acetic acid as is nitrognoscopine. Anhydrocotarnineaminophthdide, CH2:O2:C1,Hl,O2(0Me)*NH,, is prepared by reducing the nitro-compound with stannous chloride in glacial acetic acid solution. It crystallises from a mixture of chloroform and alcohol in rectangular plates, melting at 216-218O.The producta of these remarkable condensations me being studied in detail especially with a view to the elimination of the nitro-group and the consequent synthesis of some new alkaloids allied to nascotine and hydratine. 263. '' The constitution of coumarinic acid." By Arthur Clayton. Two methyl ethyl ether-esters of 5-nitrocoumarinic acid have been prepared. Michael's formula (I) for coumarinic acid is therefore incorrect. The dimetkyl ether-esters of 5-nitrocoumarinic acid and OH 231 5 nitrocoumaric acid form tlic same hrominc additive compound. Formula 11: is lhus csclndcd, and coumnrinic acid is proved to be a cis-isomeridc of o-cournaric acid (formula 111). 264. ‘I The reduction of chloric acid.” By Ralph Roscoe Enfield.A dilute solution of chloric acid free from the presence of other acids is not reduced by sodium amalgam. A dilute solution of chloric acid may be kept in contact with methyl alcohol for several days without any reduction taking place. The velocity of reduction of chloric acid is increased by the addition of other acids. It is suggested that this stimulating effect may be due (1) To the mass action of the hydrogen ions in increasing the concentration of non-ionised chloric acid, on the assumption that the primary reaction is the breaking down of the non-ionised chloric acid molecule, or (2) To the purely catalytic action of the hydrogen ions, on the assumption that the reaction is an ionic one, the reduction being that of the ClO, ion.The velocity of reduction of chloric acid by methyl alcohol in presence of certain concentrations of other acids was measured. Experiments were made for nitric, sulphuric, benzenesulphonic, and oxalic acids. The stimulating effects of these acids were found to be in the order of their relative strengths. The reaction between chloric acid and ferrous sulphate was examined in the same way, and the acceleration of the reaction by various acids was determined. Acceleration constants for the various acids were calculated, and shown to be in moderate agreement with the affinity constants of the acids. These results appear to favour the view that the reduction is that of the ClO, ion, accelerated by the catalytic influence of hydrogen ions. 265, “The dynamics of the decomposition of persulphuric acid and its salts in aqueous solution.” By Leila Green and Orme Masson, The authors confirm Levi and Migliorini’s work (Gazzetta, 1906, 36,ii, 599) as to the simple unimolecular character of the decom- position in aqueous solution of sodium, potassium, and ammonium persulphates, and as to the large acceleration produced by added acids.The deconposition of persulphuric acid differs from that of the sodium or potassium salt in being only apparently unimolecular, since its velocity-coefficient varies with the initial concentration, and is the sum of a true unimolecular constant (k,) and a quantity proportional to this concentration (EA); also k2 is nearly twice as large as the k, of the salts of the alkali metals.The barium salt yiclcls a curve with marked ckrtuge of flexure, showing large auto-acceleration, until, when the action is ha1f completed, a11 the barium 1ias heen precipitated as sulphnte, and a solution of pure persulphuric acid is obtained. Tlie authors suggest a thcory which explains quantitatively tlicse cases and also those of most of the mixtures studied. Each salt has its own normal unimolecular constant, which is increased by a quantity proportional to the hydrogen ions, or acid accelerator, present. The acid sulphate, which is an essential product of the action, and yet shows no catalytic effect (even although added at the outset), does not reckon in this connexion as an acid, whilst added sulphuric acid counts only as a monobasic acid.Persulphuric acid has its full dibasic value. The addition of alkalis does not alter the simple unimolecular character of the decomposition of the sodium or potassium salt, and hardly changes the value of the constant. Barium persulphate, when mixed with barium hydroxide, shows a much larger initial rate of decomposition than the pure salt, and there is also further auto acceleration. Most of the work was carried out at 80°. At 90° the velocities are- practically ten times as great as at 70°. 286. (‘Complete methylation by methyl sulphate.” By Raphael Meldola. In the course of some experiments having for their object the preparation of compounds containing an asymmetric quinquevalent nitrogen atom combined with at least one strongly acid radicle, it became necessary to obtain, if possible, a mono-alkylated 2: 6-di-nitro-4-aminophenol (isopicramic acid).Some of the latter was accordingly treated with methyl sulphate and alkali in the usual way, the quantity of methyl sulphate being a little in excess of that required to introduce one methyl group. It was thought that the protective action of the nitro-groups might possibly prevent the inethylation of the hydroxyl and direct the methyl group into the 4-amino-group. It was found, however, that the product was non- phenolic, and further examination showed that three methyl groups had entered the molecule, the unmethylated portion being mainly, but not entirely, unchanged isopicramic acid.Tlie tendency in this case is for complete methylation to take place, the yield of trimethyl derivative being very high, in spite of the deficiency of methyl sulphate. The compound is accordingly 2 : 6-diniti.0-dimethyl-p-anisidine, O*C)H, 233 0.0472 gave 7 C.C. N, (moist) at 13O and 761.7 miii. N=17.56. C,H,,0,N3 requires N= 17.43 per cent. The substrtncc is basic, dissolving in mineral arcid to a clear solution, from wliieli orange needles separate on neutralisation with ammonia. The melting point of the pure compound is above 300O. 267, ‘‘Astudy of the dissociation of the salts of hydroxylamine in aqueous solution.” By Ernest Barrett. The work is an outcome of the previously recorded influence of acids and alkalis on the rate of formation of acetoxime (Barrett and Lapworth, Trans., 1908, 93,85).Aqueous solutions of hydroxylamine sulphate and hydrochloride, to which various frac- tions of a molecular equivalent of alkali had been added, were exa.mined as to their electrolytic conductivity and degree of acidity, the latter colorimetrically, using o-nitrophenol as indicator. Whilst the first method gave a normal result, the latter method indicated that the gradual addition of alkali to hydroxylamine hydrochloridc does not produce a steady rise in the alkalinity of the solution, liut that sbrongly marked maxima and minima occur. 268. “The colour and constitution of bromine solutions.” By Alfred Francis Joseph and James Nadoris Jinendradasa.On adding a soluble bromide to aqueous bromine, the colour becomes lighter. This seems probably due to the formation of a polybromide which is lighter in colour than free bromine. The colour of bromine water was compared with that of solutions of bromine in aqueous bromides (using potassium dichromate as an intermediate standard), and it was found that after the con-centration of the bromide reached normal, further addition produced little effect on the colour. This agrees with the view that in normal bromide solution the bromine is practically wholly combined. The colorimetric results applied to the dissociation equation k(KBr,) =(KBr) x (Br2) give values of Ic varying from 0.03 to 0.07, which are similar to those obtained by Worley in the study of the strength of solutions of equal vapour pressure.Potassium and sodium bromides and hydrobromic acid gave similar results. 269. “The reactivity of ketones towards iodine and the relative rates of tautomeric change.” By Harry Medforth Dawson and Robert Wheatley. The rate at which iodine reacts with various ketones in aqueous nlcoholic solution has been measured in the presence of sulphuric acid as a catalyst. Dimctliyl, methyl et.hyl, methyl propyl, methyl butyl, methyl hcsyl, phenyl metliyl, diethyl and phenyl ethyl ketones 234 wcrc cxsmined. Tho mcchanism of the change appears to be the simc iii all cascs, and from the olxmvcd velocities with which tlic ketones react with iodiiic under comparable conditions, llie relative raty at which the various ketones are converted from the ketonic to the enolic form have been obtained.270. "The colour and absorption spectra of some sulphur compounds," By John Edward Purvis, Humphrey Owen Jones, and Hubert Sanderson Tasker. Dithio-oxalic esters have been shown to be coloured (Jones and Tasker, l'runs., 1909, 95, 1904), whilst the corresponding oxalic esters are colonrless; it was therefore considered of interest to examine the effect of the substitution of sulphur for oxygen in similar substances in order to obtain evidence as to the origin of the colour. To this end t,wenty-two sulphur compounds of various types have been prepared and their absorption spectra examined. The general results obtained may be summarised as follows : (1) The displacement of oxygen by sulphur causes a marked increase in the absorptive power of the compound, and often causes the production of an absorption band and of colour.(2) Definite absorption bands are given by sulphur compounds having the following st'ructures, but are not exhibited by thc corresponding oxygen compounds : (111.) Of these, compounds of the types I, 11, IV, and VI are yellow, and V may be considered as faintly yellow in colour. (3) The group C:S must be considered a powerful chromophore. (4) In certain aromatic compounds, such as phenol and benzyl alcohol, the displacement of oxygen by sulphur results in the obliteration of absorption bands, which is probably due to the increase in general absorption.(5) Oxalyl chloride, which is itself colourless, gives yellow solu- tions with a number of unsaturated compounds and compounds containing oxygen or sulphur. 271, "The interaction of phenyl mercaptan and thionyl chloride." By Hubert Sanderson Tasker and Humphrey Owen Jones. As a result of an examination of the interaction of phenyl mercaptan and thionyl chloride (TTQ~.,1909, 95, 1911)) the authors coiicliided that the cliange could be partly represented by the 235 aquation 8C,H,*SH + 4SOC1, =8HCl+ 2S0, + 3(C611,*S), + (C6R3)2S4, and suggested that sulphur dioxide was produced by the decom- position of sulphur suboxide (SO), which might be formed momentarily. The evidence in support of this was as follows: (1) The titre of the products of the interaction for alkali and for iodine was approximately that required by the above equation.(2) The liquid product of the reaction had the properties and mmposition of diphenyl tetrasulphide. (8) When thionyl chloride reacts with lead phenylmercaptide, Pb(S*c,H,),, or with nickel carbonyl, sulphur dioxide is formed, and in the latter case sulphur is also produced. In both cases it would appear that sulphur dioxide has been produced by the decomposition of sulphur suboxide. In a recent paper (Trans., 1910, 97, 1196) Smythe and Forster criticise these conclusions, and state that there is no reason to believe that the reaction is not completely represented by Holmberg’s equation (Annulen, 1907, 359, 81) : 4RSH + SOCl,= R2S2 + RZS, + HZO +2HCl.These authors have, however, entirely overlooked the evidencc mentioned under (2) and (3) above, and also the fact that watcr was always present at the end of the rea.ction, and that therefore all the sulphur dioxide could not have been due to the secondary interactioa between water and thionyl chloride. 272. ‘‘Triketohydrindene hydrate.” By Siegfried Ruhemann. Triketohydrindene hydrate, C6H4<&>C(@H), (l’1-nits,,1910, 97,CO 1438), yields with guanidine or benzamidine the compounds : C,I€,<gE>C(OH)*NH( NH)-NH, and C,H,<::>C(OH )-NII~J~I~:NII, with hydrogen cyanide, the unstable cyanohydrin, and with phosphorus pentachloride, 2 :2-dichloro-1: 3-diketohydrindet;e, The action of potassium hydroxide on triketohydrindene hydrate proceeds in three distinct phases, which are indicated by colour changes.First, a yellow coloration is formed, which is due to the production of phenylglyoxal-o-carboxylic acid, CO,,H*C,H,*CO*CHO, then the solution becomes blue, and finally colourless. The colour- 236 lcss liquid contains the potassium salt of o-carboxymandelic acid, C02H-C6H4-CH(OH)*C02H,because, with dilute sulphuric acid, it ’ yields phthalidecarboxylic acid, ~o‘o>CH*CO,H. As regards co=,tho intermediate phase of the reaction, which is characterised by the blue colour of the alkaline solution, the author puts forward an explanation based on the analogy to the similar reaction in the case of the diketopyrrolines, when unstable blue salts are formed.Triketohydrindene hydrate gives an intense blue coloration with a-aminoaliphatic or aliphatic aromatic acids, whereas no coloration is obtained with substituted amino-acids, for example, phenylglycine and hippuric acid, or with aromatic acids which contain the amino-group in the nucleus. So far, only two &amino- acids have been tested, and they were found to differ, in some respects, from their isomerides, the a-amin*acids, in their behaviour towards triketohydrindene hydrate. 273, “The influence of solvents on the rotation of optically active compounds. Part XVI. The relationship between the chemical constitution and the influence of a solvent.” By Thomas Stewart Patterson and Elizabeth Findlay Stevenson.The relationship between the chemical constitution and tlic! inhence, on the rotation of ethyl tartrate, of various solvents were discussed. 274. “Solubility of calcium phosphate in saturated solutions of carbon dioxide containing ammonia.” By Bernard Foster and Henry Allen Dugdale Neville. The solubility of calcium phosphate,. and of the phosphates in commercial phosphatic manures,. was determined in saturated solutions of carbon dioxide containing ammonia. With increasing quantities of ammonia the quantity of phosphate passing into solution increases at first rapidly, and then more slowly, the solu-bility of phosphate then being almost directly proportional to the amount of ammonia present. 275. ‘(The constitution of sodium a1urninate solutions.” By Roland Edgar Slade.Hantzsch’s experiments (Zeitsch. anorg. Chem., 1902, 30,276) on the conductivity of sodium aluminate solutions have been repeated and confirmed. These experiments show that the aluminium hydroxide behaves as a monobasic acid, 237 The author has been unablc to confirm tlie work of Herz (Zeitsch amrg. Chem., 1900, 25, 155) on the existence of the compound Na,AlO, in solution. The work of Ituss (Zeitsch. nnoyg. Chem., 1904, 41, 206) and of Wood (Trans., 1908, 93,421) on tlie equi-librium between crystallino aluminium hydroxide and sodium aluminate solutions was discussed. The assuinptions on which Woocl calculated the acidic dissociation constant of aluminium hydroxide were shown to be far from correct.The work of Wood (T~~uns.,1910, 97,878) on the acidic dis- sociation of the hydroxides of glucinum, zinc, and lead was similarly criticised. ADDITIONS TO THE LIBRARY. I. Bonations. Abderhalden, Emit. [Editor.] Handbuch der biacliemischen Arlroits- methoden. Vol. V [Contiiauotion of VoZ. 13. pp. xvi + 609 to 1627. ill. -Berlin 1910. (Necd. 6/5/10.) From the Publishers : Messrs. Urban und Schwarzenberg. Bell, Sir JViZZiarn J. The Sale of Food and Drugs Acts, 1875 to 1907. With Notes and Cases ; Together with an appendix containing the other acts relating to adulteration, chemical notes, etc. 5th edition. By Cl~arles3’. Lloyd. The chemical notes revised and enlarged by R. A. Robinson. pp. xl+303+43.London 1910. (Recd. 20/9/10.) From the Publishers : Messrs. Buttermorth & Co. Dyer, Bernurd. Fertilisers and feeding stuffs. Their properties and uses. With the full text of the Fertilisers and Feeding Stuffs Act, 1906, the regulations and forms of the Board of Agriculture, and notes on the Act by A. J. David. 6th edition. pp. viii + 152. London 1910. (Recd. 28/6/10.) From the Author. Elsden, James Vincent. Principles of chemical geology. A review of the application of the equilibrium theory to geological problems. pp. viii + 222. ill, London 1910. (Recd. 6/7/10.) From the Publishers : Messrs. Whittaker & Co. Friend, J. Newton. An introduction to the chemistry of paints. pp. x+204. ill. London 1910. (Recd. 3/8/10.) From the Author.Gissing, Charles E. Spark spectra of the metals. pp. vii + 21. ill, London 1910. (Recd. 13/7/10.) From the Publishers : Messrs. Baillibre, Tindall and Cox. Haas, PccuZ. Laboratory notes on organic chemistry for medical students, pp. viii + 128. ill. London 1910. (Recd. 30/9/10.) From the Author 238 Holleman, A. 4'. A text-book of organic chcinistry. Edited by A. Jair~iesonWalker, assisted by Owen E. Mott. 3rd English edition. pp. xx+599. 111. New York 1'310. (Kecd. 12/9/10.) From the Publishers : Blessrs. John Wiley and Sons. Howard, Albert, aud Howard, G'tsb~ieZZeL.G. Wheat in India. Its production, varieties and imp ovement. pp. ix + 288. ill. Calcutta 1'30'3. (Recd. 23/8/10.> From the Author+. Institute of Chemistry.Proceedings, 1877-1 S95. 19 vols, Loucion. From Dr. Alexander Scott, M.A., F.R.S. Koerner, GugZieZmo. L'Opera Classics di Guglielmo Koerner. La, determinazione del Iuogo chiuiico nei composti cosi detti aromatici. (Pubblicazioni di G. Koerner raccoite ecl ordinate in occasione del 50° Anniversario della sua Laurea.) pp. 2'74. Milano 1910. (RecJ. 2/8/10 ) From the Committee. Lister Institute of Preventive Medicine. Collected papers, NO. 6. London 190%-10. (Reed. 29/8/10.) From the Institute. Lodge, Siy Oliver. The ether of space. pp: xvi + 156. ill. London 190'3. (Ziecd. 1/7/10.) From the l'ublichers : Mews. Harper 9t Bro:., Martindale, lbTillia?n,Ifurrison. Organic analysis chart. pp. SO, London 19 10. (12ecd. 6/8/ 10.) From the Publishers : Messre.H. I<. 1,ewis. Martindale, TilEiccnz. Uuwisow, aud Westcott, IV. 7Fyi2n. 'l'hc extra pharrnacopceia. 14~hedition. pp. xxvii + 1054. London 1910. (Z2ec.d. 6/8/ 1 0.) From the Publishers: Mesers. H. K. Ilewis. Moore, F.J. Outlines of organic chemistry. pp. ix+315. New Yoyk 1910. (Recd. 16/6/10.) From the FublislieiF : Slesst 8. John Wiley and Sons. Moureu, Ch. Notlous fondamentak dr: chimie organique. 3rd ditiou. pp. iv + 35-1. Psiis 1910. (iiacd. 4/7/10.) From the Publishel s : Mews. Ganthier-Villars. Perkin, Fyederick Mollwo. Qualitative chemical analysis. 3rd editiou. pp. xi1 + 337. ill. London 191 0. (h'ecd. 23/6/10.) From the Author. Philip, Jcti)?es Cltades. Physical chemistry. Its bearing on biology arid medicine.pp. vii+ 312. ill. London 1910. (Ilecd. l/lO/lO.) From the Author. Sidgwick, ,%'evil Vincent. The organic chemistry of nitrogen. pp. xi+ 415. Oxford 1910. (h'ecd. 14/10/10.) From the Publishers : The Cllarendon Press. Smiles, Scirrzuel. The relations be:ween chemical constitution and sowe physical properties. pp. xiv + 5SY. ill. llondon 1910. (Recd. 12/6/10.) From the Autlior. Thompson, C. J.8. The compendium of medicine and pharmacy. 3rd edition. pp. vi + 336. London [1910]. (Recd. 21/6/10.) I'ltonl the Yublisheis: Blessrs. John Bale, Sons S: Danicleson, Ltd. 239 Tilden, Sir JVtZliam 8. The elements. Speculations as to their nature and origin, pp. xi + 130. ill. London 1910. (Recd. 1/7/10.) From tlie Publishers : Rlessrs. Harper & Bros.Treadwell, F. 1’. Analytical chemistry. Volnmc 11. Qiian t.ita-tive analysis. Authorised tmnslation from the German by JFilliant Y’. Hall. 2nd edition. pp. x+787. ill. New York 1910. (12eccl. 1 2/9/ 10.) From the Publishers : Messrs. Johu Wiley and Sons. II. 3y Z’urchase. Allen, AIJ-ed Ilenq. Commercial organic analysis. Vol. 11I. 4th edition. Edited by IfrillimnAlJred Davis and Smmel S. Sadtler. pp. x3-635. ill. London 1910. (Ziecd. 3/9/10.) Beythien, A. I)ie Nahrungsmittelverfiilschung, ibre Erkcnnung und Bekiimpfmg. (S,immlung, Vol. XVI.) Stuttgart 1910. Hamburger, ZI. J. Osmotischer Druck und Iouenlehrc in den medicitiischen Wissenschaften. Zugleich Lehrbuch physikalisch-chemischcr Methoden. 3 vols. pp. xiii + 539, x + 5 16, xiii + 508.ilI. Wiesb:iden 1902-1 904. (Recd. 3/8/ 10.) Kayser, H. Haudbuch der Spectroscopie. Vol. V. pp. vi+853. ill, Leipzig 1910. (Recd. 20/7/10.) Nierenstein, Jf. Chemie der Gerbstoffe. (Sammlung, Vol. XV.) Stuttgsr t 1910. Oppenheimer, Cud. Die Fermente und ihre W irkungen. Allgemeiner Teil. Nebst einem Sonderknpitel : Physikalisclie Chemie der Fermente und Fermentwirkungen von R.0. Herzog. pp. xv + 282. Leipzig 1910. (Red ll/lO/lO.) Ostwald, W., and Luther, 12. Hand- und Hiilfsbuch zur A usfuhrung physiko-chcxuisalier RSessungen. 3rd edition. Edited by R.Luther and K. Drucker. pp. xvi+573. ill. Leipzig 1910. (Reccl. 23/6/10.) Ubbelohde, L., and Goldschinidt, F. Handbuch der Chemie und l’echnologie der Oele ~indFette. Vol.3, part 1. pp. xx + 380. ill. Leipzig 19 10. (Recd. 14/1 O/10.) Walden, P. Die Losurigstheorien in ihrer geschichtlichen Aufoin- anderfolge. (Sammlung, VoI. XV.) Stuttgart 1910. 111. Pumphlels. Blum, L. Ueber den Abbaii von Fettsiiuren im Organismus nnd uber die gegensei tigon Beziehungen der Azetonkarper. (From the M<incJLenei*mecl. IIroch., 1 9 10.) Breinl, Anton, mid Nierenstein, M. Bio-chemical and therapetitical studies on trypmosomiasis. (From the Ann. Trop. il.IecZ. Par., 1909, 3.) Burian, Richard, and Drucker, Karl. Gefrieipmkt srnessungen an kleiuen Pliissigkeitsmengeu. (From the Zeiztr, Yhysiol., 1910, 23.) 240 BANQUET TO PAST PRESIDENTS. The Banquet, which was postponed from May 26th, will be held at the Savoy Hotel (Embanlrment Entrance) on Friday, Novcnibcr llth, 1910, at 7 for 7.30 pm., in honour of the following Past Presidents who have attained their Jubilee as Fellows of the Society : Served as Elected Presicler;t Prof.William Odling, F.R.S. ... ... 1848 1873-1875. The Rt. Hon. Sir Henry E. Roscoe, F.R.S. 1855 1580-1882. Sir William Crmkes, F.R.S. ... ... 1857 1587-1889. Dr. Hugo8Miillcr, F.R.S. ... ... .. . 1559 1885-1887. Dr. A. G. Vcrnon IIarcourt, F.R.S. ... IS59 18951897. The price of tickets will be Onc Guinea (21 1s.) each (including wine), or Half-a-Guinea (10s. 6d.) each (not including wine). A 12 npplications for tic7ietsmust be received not lafey t7mt Fridciy, Novwnber 4th, next. Tickets %ll be forwarded to Fellows on receipt of a rcmittnnce for tlic nunher required, made payable to “ Mr.S. E. Carr,” and addresscd to the Assistant Secretary, Chemical Society, Rniliiigt on House, W. At the next Ordinary Scientific Meeting on Thursday, Novcnrher 3rd, 1910, at 8.30 pm.,there will be a ballot for the election of Fellows, and the following papers will be corumunicatetl : “ Researches 011 blenching powder.” Ry R. T,, Taylor. “Azomethine azo-dyes.” By A. G. Green ant1 R. N. Sen. (‘Syntheses in the epinephrine series. P‘irt IT. The formation and properties of some 2 :5-and 2 : 8-substituted pyrazincs and their conversion into amino-ketones and irnino-diketoncs.” By F. Ttitin. ‘‘The absorption spectra of some snbstituted pyrazines and their salts.” By F.Tutin and F. W. &ton. (‘Studies in the camphans series.Part XSVTIT. Stereoisonitlt#ir* hydrnzones and sernicnrbazones of cnmphortlninono.” Ry M. 0. Forster and A. Zimmerli. ‘‘Tho constituents of gelsemiurn.” 1;y (1. W. 34oorc. L( Some phenolic dei-ivntives of /3-phenylet hylnmine.” Ey G. Barger and A. J. Ewins. “Chloroamine reactions. ISlethylenecliloroaiiiino.“ By C. F. Cross and E. J. Bevnn. ‘‘Preparation of secondary aillines from cnrboxylic acids. Part 1. Preparation of heptadecylanilitIc, perit,fldccylnnilinc, and tritlecyl-aniliiw.” By H. R.Le Sueur. 1L. CLAY AND SONJ, I.‘l’I>., FIIlE4D ST. IIILL, E C., ANI) UUNGAY, SUE’E’OI.&.
ISSN:0369-8718
DOI:10.1039/PL9102600189
出版商:RSC
年代:1910
数据来源: RSC
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