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Proceedings of the Chemical Society, Vol. 16, No. 230 |
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Proceedings of the Chemical Society, London,
Volume 16,
Issue 230,
1900,
Page 219-232
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摘要:
PROCEEDINGS OY 1'HC CHEAIICAL SOCIETY. EDlTEI) BY THE SECIZEY'ARIES. December 13th, 1900. Extra Meeting. Professor THORPE,C.B.; F.R.S., President, in the Chair. Professor H. A. &IIERS,D.Sc., F.R.S., delivered the Kakrnelsberg Memorial Lecture. Karl Friedrich Rammelsberg was born on April lst, 1813, at Berlin, and succeeded Heinrich Rose as Professor of Inorganic Chem- istry in the University of Berlin in 1874. He was also Instructor in Chemistry (1850-1883) at the Gemerbe-akademie, which became the Technische Hochschule and mas transferred to Charlott'enburg in 1883; from 1883 to 1891, he was Director of the Second Chemical Institute of the University. He was twice married; in 1846, to the daughter of Oberbergrath Zincken; in 1859, to the daughter of C.G. Ehrenberg. In 1841, as Privrttdocent, he started a private labora- tory, in which was given the first practical chemical instruction in Berlin. He published an immense number of papers dealing with inorganic chemistry, crystallography, and mineralogy, but never him- self engaged in any research work relating to organic chemistry. He was the author of numerous chemical text-books, one of which, G'm,nd~issder Chenaie gemuss dejz neueren Ansichen (1 866), was the first to explain the new principles of organic chemistry. He WAS also the first of the old school of chemists to adopt the new system of formulz. Two of his books were encyciop= lic works of reference : the Hcmdbuch der I;rystcc?Zogrc~~3I~ischp~~ysi~uZisciLer~Chemie (1 855-1881) contained the crystallographic, optical, and physical constants of all crystallised compounds; the Handbuch,der iWinera2chemie (1841-1895) mas an exhaustive twatise on t,he composition of all minerals.He was equally eminent as Inorganic Chemist, Crystallographer, and Mineralogist. In chemistry, his work upon the halogen com-pounds, the phosphates, and the cyanides may be taken as samples of his researches. He prepared and studied an enormous number of bromides, of the ammonia compounds of the bromides and iodides ; of bromates, iodates, and periodates ; of phosphates, phos- phites, and hypophosphites ;our knowledge of the double cyanides is almost entirely due to him; equally laborious and important were his researches upon the sulphantimonates, hyposulphites, sulphites, nitrites, vanadates, phosphomolybdates. One of his important papers, on the Mexican amalgamation process, was com-municated to this Society (1881).In crystallography, he did more than any other man to carry on the work of Mitscherlich, and inves- tigated an immense number of isomorphous compounds ; he studied the isomorphism of sulphur and selenium ;he pointed out the isomor- phism of vanadinite and pyromorphite, and first suggested that vanadic acid is V,05; in his work upon the crystallisation of the sulphates RSO4,7H,O from mixed solutions, he was one of the pioneers of modern physical cheniistry. In mineralogy also he contributed more than any one to our know-ledge of the composition of minerals and was practically the father of modern mineral chemistry ;he published more than 300 papers on mineralogical subjects (including those on the analysis of rocks and meteorites) ;he first established the presence and the relationship of the ferrous and ferric iron in the group of the augites and hornblendes; he was the first to accept Tschermak’s theory of the felspar group ; and his laborious aiinlyses ranged over about two-thirds of the mineral kingdom ; he was strongly opposed to Penfield’s views on the mutual replacement of fluorine and hydroxyl.Rammelsberg’s active labours in mineral chemistry continued to the end of his long life, and at the age of 82 he published an elaborate supplement to his Handbuch dei* Xineralclwwie.He died on December 2Sth, 1899, at Gross Lichter-felde, near Berlin, after n life of almost unexampled industry. On the motion of Dr. HUGOMULLER, seconded by Professor M’LEoD, a vote of thanks was passed to Professor Miers for his Lecture. December 20th, 1900. Professor THORPE,C.B., F.R.S., President, in the Chair. The following certificates were rend for the 6rst time: Nessrs. Merrick William Burrows, Dunkirk, Devizes ; Robert Waley Cohen, 11, Hyde Park Terrace, London, W, ; Reginald Williams Ferguson, 221 8, Havelock Terrace, Paisley Road, Glasgom ; John Lloyd Thomas Jones, United Service Club, Calcutta ; James Menzies, 39, Winter-brook Road, Herne Hill, London, S.E. ; Arthur W. Nunn, 313, Sydenham Road, Sydenham, S.E.; Herbert Kilburn Scott, P.O. Box 634, Rio de Janeiro, Brazil ; Albert Edward Thomas, 34 South Road, Kingswood, Bristol. Of the following papers, those marked * were read :-“169. I‘ On the union of hydrogen and chlorine.” By J. W. Mellor, B.Sc. At the suggestion of Professor H. B. Dixon the author undertook to investigate the mode in which light brings about the combination of hydrogen with chlorine. The electrolysis of hydrochloric acid and of the solution of chlorine in this acid were first studied, as an exact knowledge of these is necessary to interpret the work of previous investigators. Bunsen and Roscoe state that under certain conditions the gas resulting from the electrolysis of hydrochloric acid consists of a prac- tically pure mixture of hydrogen and chlorine. The author finds, however, that under the most favourable conditions oxygen is present to the extent of 0.009 per cent.In order to find out if the distribution of the gases in Bunsen and Roscoe’s insolation vessel is affected by the absorption of hydrogen chloride, a more complete investigation was made. By plotting the respective amounts of chlorine and hydrogen chloride in the solution, it is found that two distinct and intersecting curves appear : (1) If the hydrochloric acid be less than one-fifth of normal strength, the amount of chlorine absorbed decreasesas the amount of hydrogen chloride increases. The explanation is based on Jakowkin’s work on the dis- tribution ratio of chlorine between water and carbon tetrachloride where the action of chlorine on water (in darkness) is shown to be a trimolecular one f-Cl,Aq-(H + C1+ HOC1)Aq.-I--The number of H and C1 ions is evidently increased by the addition of hydrogen chloride, and therefore, in agreement with Nernst’s dis- tribution law, the number of ions derived from the chlorine is diminished. This involves a decrease in the solubility of that gas. (2) If the strength of the solutions of hydrochloric acid be greater than one-fifth of the normal the amount of chlorine (A) absorbed in-crease~as the amount of hydrogen chloride (p)increases. The increase is a linear function of the amount of hydrogen chloride present. X = 0.0713 + 1.528. The phenomenon is probably due to the formation of a compound of hydrogen chloride with the chlorine, say HCI,.There is no sharply +-defined point of transition, because the phases H + C1+ HCI,, &c., co- exist in the solution, A slight contraction occurs when chlorine and hydrogen chloride gases are allowed to diffuse into each other, *170.'' The nitration of the three tolueneazophenols." By J. T. Hewitt and J. H.Lindfield. The three tolueneazophenols have been nitrated by warm dilute nitric acid, and in each case the nitro-group has been found to enter the phenol nucleus in the ortho-position relatively to the hydroxyl. This agrees with the resnlts previously obtained in the cases of oxy-azobenzene and benzeneazosalicylic acid. The following substances were described : o-ToZueneccxo-o-~zitro~~~~e~~oZ, M.p. 146'; the cthy? ether, m. p. 93'; the ncetccte, m. p. 120.5'; the benzoate, m. p. 132'. m-l'oZuenenxo-o-?zilro~ll~enol,m. p. 128.5' ; the ethyl etllm, m. p. 92'. p-Tolueneuxo o-niti*ophenol, m. p. 147"; the ethyl ethev, m. p. 116' ; the acetate, m. p. 94'; the bemoccte, m. p. 129'. The conditions under which m-tolueneazo-o-nitrophenol can be acetylated or benzoylated have not been discovered, as excess of benzoyl chloride fails to change the substance. The other acylations take place easily and normally. it is also noteworthy that difficulty is experienced in alkylating o-tolueneazo o-nitrophenol with sodium ethoxide and ethyl bromide ; the other alkylations are, however, normal. The etiigl ethey of benxeneaxo-o-uiti.ophenolwas prepared for purposes of comparison ; it melts at 93".DISUJSSION. YOUNGDr. GEORGE inqiiired what evidence there was to show that acetylisation of a hydroxyazo-compound always produced an acetoxy- and not an acethydrszone derivative. It seemed curious that a change of position of a methyl group in the benzene should influence the acetylisation of the phenol side of the molecule. Dr. HEWITT,stated that tkough Goldschmidt jclaimed to have com- pletely reduced the acetj 1 ~leiivative of benzeneazo-jj-cresol to acetanilide and p-cresol, MacPherson had obtained compounds by the action ot benzoylphenylhydrazine on quinones which were isomeric and riot identical with the benzoyl derivatives of the xzophenols.Hence it would appear that the acetyl and benzoyl derivatives of the azophenols are true oxygen ethers. +l7l. "The brominationof the ortho-oxyazo-compounds and its bearing on their constitution." By J. T. Hewitt and H. A. Phillips. The effect of substituting agents on numerous oxyazo-compounds of thepara-series has been studied by one of the authors of this corn-munication and his pupils. So far, bromination or nitration of ortlho-oxyazo-compounds has not been examined, but it was expected that such compounds woulcl behave as orthoquinone-hydrazones,and substi- tute in the nucleus which had been derived from the diazotieed aromatic base. Thus benzeneazo-p-cresol was expected to give para-or ortho-bromobenzeneazo-p-cresoi, whereas experiment has showti that when the substance is dissolved in glacial acetic acid with ait excess of sodium acetate and then brominated, benzeneazo-o-bromo- p-cresol results.Ortho-oxyazo-compounds appear thus to react toward5 bromine as true oxyazo-compounds. In the course of this investigation, tlie following compounds have been prepared and their properties examined : Benxenenzo-o-bi.onzo-p-cresoZ,m. p. 123" ; belLxeiaenxo-o-broi7o-p-cres~l acetate, m. p. 83"; benzenecLzo-o-bronio-p-c~e~~~bewoccte, m. p. 110" ; o-bromobenzenect.zo-p-crr.esol,m. p. 1 1 6" ; o-bi.omobe?txeneuao-p-cresylacetate, m. p. 85 ; o-bronzobdizZeiiecLxo-p-c.,.esyl benzoate, m. p. 106.5"; m-byorno-benzenenzo-p-cresol, m. p. 112" ; rn-brontobe?ixei.leaao-p-cresyl ncetate, m.p. 61-62' ;rn-broiizobeizze?zeccxo-p-c?.es?/Zbemmte, m. p. 94" ;p-bronzo-benxeizec~xo-p-c.l.eso2,rn. p. 14'7" ; p-bromobe?aae?ietczo-p-ci*es?/lmetate, m. p. 123' ; p-bi.oi,zobe?zxe?zeazo-p-cyes~Zbenzoate, xu. 11. 112". 172. (( On the use of pyridine for molecular weight determinations by the ehullioscopic method." By William Ross Innes. The author described the precautions necessary to obtain accurate results. The constant for pyridine is 59.5. Acids, alcohols, and phenols were shown to give normal molecular weights. Pyridine, therefore, does not favour the association of dis- solved substances. 173. “The influence of the methyl group on ring formation.” ByA. W. Gilbody and C. H. G. Sprankling. The authors have prepared and analysed y-ethoxyphenylsuccin- amic acid and the following alkyl snbstituted derivatives.(1) p-etJbo~:y~JLenyZszcccilzccr,licmid, ni. p. 166-167O ; (2) metJbyZ-p-ethoxy-pJ~englsuccinan~ic acid, m. p. 149-150” ; (3) as-dinzetJq2 p-etJLoxg- pl~en~lszsccincc??zicacid, m. p. 160--161°; (4) trans-s-dinzetl~?ll-~-~t~~o~~-23l~enyZsucci.laa91tic mid, iu. p. 154-185”; (5) cis-s-dinzetJ~2/l-p-etJ~o~~-phenylsuccinunzic ncicl, M. p. 155-1 56’ ; (6) t?.i,,tetl~?/Z-p-etlox~23hen~Z-succimnzic acid, in. p. 128-1 29” : (7) isol-”‘o~~~l-p-etJ~ox~~~J~enylsuc-cinantic acid. in. p. 151-153°. Two forms of the asyninietrically snhtituted :wid.; slioulcl exist according to theory, but only one has been observed during the re-search. Tho anilides of the correbponding phenylsuccinnrnic acids dso seem to behave in R similar manner, for previous investigator.have found only one acid, where two might be expected. The scanty evidence at our disposal (Blake, Coqit. end., 1898, 126,753) tends to show that of the two fonnulz for methyl-y-ethoxy-phenylsuccinainic acid, for example, CH,*YH*CO,H ?Hi*COzHandCH,*CO*NH*U,H,OC,H, CH,*CH CO *NH-CGH40C2H5, the former is the correct one. 7-utler tliP contli tions employed, the lower members of the series 1 entLi1y yieldetl i11111) cl~wuzsodium salts, but the salts of the trimethyl-aud isopropyl-“aminic ” acids liuve not SO far been obtained pure', owing to the easy foimution of the ring compounds (pymntins). The above acids were then converted into the corresponding y-ethoxy- phenylsuccinimide (pyrantin) derivative and the stability of the hub- stituted succiriiinide ring so produced estimated according to the well-known equation, --’ /“A -x=Ac; the figures given being the mean of two or more determinations (compare Miolitti and Longo, Att.Accccd. Lincei Rend., 1894, [v], 3,515. 597 ; 1895, [v], 4, 351 ; Miolati and Lotti, 1896, [v], 6,88; Piatti, Ber., 1896, 29, SS). It was necessary to carry out the experiments in alcoholic solution because of the insolubility of the substances in water. l’yrantiii m. p. 155” Ac =0.0949 cis-s-Dimethyl- Methylpyran- pyrantiii 111. 1’. 114-115’ Ac=0*1393 tiu ......111. 1). 105-106” ,4c=0’1831 Trimethyl- trs-Dimethyl- pyrantin. 111.1). 87-88” Ac=O 0446 pyrantin 111. p. 7O-jl” Ac =O*OSif! isoI’ropy1- pyrantin. 111. p. 98-99’ Ac =0 ,1432 223 The stability constant was determined for phenylsuccinimide in both aqueous and alcoholic solution, in order to compare the results obtained with those of JIiolati for the tolyl- and sylyl-succinimides in aqueous solution. Phenylsuccininiide was found to be 40.03 times more stable in alcoholic than in aqueous solution, and a correction had also to be made for the value of the ethoxyl group which decreased the stability in alcoholic solution 1*704times. The results can then be calcrilated and tabulated, for the methyl siibst ituted phenylsnccini mides. Ac calculated.Ac calculated. Phenylsuccin-Ac found.Phenylsuccin-iiiiide in aqueous Pyrantin in micie in alcoholic solution (G. ancl alcoholic .;oIution. solution S. ) multiplied bylivided by 1’704. 40.03 ;or fount1 (Miolnti). Pyiantin ................... 0*0949 0.0557 2.23 Methylpyrantin. .......... 0.1831 0.1075 4-30 hopopglpyrctnt in ........ 0.1432 0.0840 3-38 cis-DiniRthylpyrantin ... 0.1393 0.0818 3.27 ........Alean of both Miolat & authors’ eq’er! iienti 2-23Phei~?llszccciiLzn.i~e ccs-Dimethylpyraiitin.. .. 0.0872 0-0512 2-05 3 :5-Xylylsuccinimicle ... --1.145 p-Tolylsuccininiide.. .... --1.12 7). -........ --1-10Y9 Trimethylpyrantin...... 0 0446 0’0262 1-05 42 :5-Xylylsuccininiitle ... -0.88 o-Tolylsuccinimide........ --0’856 2 :3-X~lylsnccinirnide . --0.815 -0 ‘1(i2 :6-79 A glance at the above table easily shows in how great a degree the stability of the succinimide ring can be decreased by the introduction of methyl groups into the fatty ring, whereas Miolati’s experiments prove that the introduction of methyl groups into the aromatic nucleus increase the stability.Substances having the constitution forniuluted above but containing methyl groups in both rings do not appear to have been prepared, although the list given is long enough to anticipate the result which might be expected in such cases. The renPon the authors chose the pyrantins and calculated the results was that they might obtain some information about, the antipyretic actioti of the methyl group, but unfortunately the subbt;inces obtained proved so insoluble in water that no definit,e result has been obta:necl.174. ''Experiments on the production of optically active corn-pounds from inactive substances." By F. Stanley Kipping, Ph.D., D.Sc., F.R.S. The note by Cohen and Whiteley under the above t'itle (this ~ol., p. 212) deals with experiments which are very similar to some in which the author, assisted by Ah. Hunter, has been recently engaged, the results of which it thus becomes desirable to place on record. Guided by practically the same considerations, and working with the same object as Cohen and Whiteley, attempts have been made to prepare directly unequal quantities of two enantiomorphously related substances by synthesising an asymmetric carbon group in presence of, or in combination with, some optically active compound, in the hope that the latter would have some directive action on the atoms or groups entering into combination.Among those experiments in which an opt,ically active substance mas used merely as a medium in which the synthesis took place, men- tion may be made of the preparation of benzoin by the action of potassiriin cycanide on benzaldehyde in a concentrated alcoholic solution of camphor ; mandelic nitrile was also prep.wed from benzaldehyde and hydrogen cyanide in an alcoholic solution of camphor and then hydrolysed with hydrochloric acid ; pyruvic acid and methyl ethyl ketone were also bepiirately reduced in concentrated glucose solution. The results were negative in all these cases.Among the experiments in which the optically active siibst,ance was combined with the inactive nucleus the following may be noted. The reduction of quinine pyruvate and of quinine lzevulinate with sodium amalgam or aluminium amalgam ; the reduction of bornyl pyruvate (b. p. 149-150", 15 mm.); the reduction of the oxifme (m.p. about 90°) of bornyl pyruvate, and the reduction of bornyl laevulinate (b. p. 170-171", 20-25 mm.). After eliminating the original optically active base or alcohol, the product, namely, lactic acid, a-amidopro- pionic acid, or y-hydroxyvaleric acid (9s lactone), as the case might be, was found to be inactive. Owing to its low specific rotation and the difficulty of isolating it, the experiments in which lactic acid mas obtained are by no means satisfactory, and mandelic acid, which has a high specific rotation, was therefore prepared by the reduction of bow$ heizzoylfomiate ; this ethereal salt separates from light petroleum in crystals melting at about 78”, and is reduced to the corresponding hydroxy-salt by sodium amalgam in presence of a little acetic acid; after hydrolysis with potash, it gave inactive mandelic acid. The failure of these experiments may be caused by racemisation taking place during hydrolysis of the original product, and this possi- bility is being investigated ; even the apparently strong evidence ob- tained by combining these results with those of Cohen and Whiteley can hardly be considered to settle the question as to the possibility of directly synthesising uneqzcnl quantities of enantiomorphously related forms, in view of the actual results obtained in the case of the sugars and the theoretical conclusions by which they may be supported.175. A lecture table experiment for the preparation of nitric oxide.” By Alfred Senier. When nitric oxide is prepared by the interaction of copper and diluted nitric acid in a flask in the ordinary way, a difficulty arises owing to the accumulation of water, This gives rise to the formation of a large proportion of nitrous oxide. By employing con -centrated nitric acid and an excess of copper in the apparatus shown this may be obviated. The figure ex-plains itself. In the apparatuq employed the U-tube has a diameter of 3 cm., and together with the small tube beneath measures 36 cm.in height. The larger tube is loosely packed with copper turnings, watei is put into the beaker below, and nitric acid (68 per cent.) is dropped from the stoppered funnel. Each drop of acid acts on the copper, liberating nitric oxide, while a solu-tion of cupric nitrate and dilute nitric acid passes into the beaker. The gas after ascending the second arm of the U-tube is quite colour- less, and contains only traces of nit.rous oxide as shown by absorption with ferrous sulphate. 176. "The action of ethylene dibromide on xylidine and pseudo- cwmidine." By Alfred Senier and William Goodwin. The reaction between ethylene dibromide and aniline originally htudied by Hofmann, and extended to hoiuologues of both compounds by subsequent observers, has been applied to xylidine and pseudocumidine. Dixylylethylenediamine and dicumylethylenediamine were obtained, together with their related piperazineg.From the diamines, derivatives were prepared homologous with those obtained by Jfills (Tra~zs., 1900, 77, 1020). DixyZ~Zetl~~Ze?zed~a??2i~a~,C,H,(NHC,H,JIe,) ?, white, feathery crystals, m. p. 74-75'. L)ix~lyletJ~~?/le?zedicL?,bi?2enitmte, C,H,(N H C6H3Me2),(HN0J2, in. p. 166'. DixyZ~Zet7LyZenedicL?Izine platinicldoride, C,H,( NHC,H31\Ie,),( HCl),,PtCI,, bright yellow crystals. Rix?/Z~Zetl~?lZenedianiinei,kercu?.icl~loritZe,C,H,( XHC',H3Me,),HgCl,, pale yellow crystals, m.p. about 118'. ~~tr*a~ziti.odim~Z?/Zetl~?/leriedia,nine, C,H,[NHC6H(N0,),Me,],, pale yellow crystals, m. p. 220'. An isonze?*ide, m, p. 52-5 3'. it~onoiaiti.otli~~:~~~Zet7~yZenediasrzine, m. p. 152-154', and a trinitro-derivative, 1n.p. 191-192'. DixylyZl,i~~el.cczi,ze, Me,H3C6N(C,H,),NCGH3Me,, consists of' shining, white leaflets, in. p. 151'. Dil3seudocumyZetl~yZe?aedicinLi?ze,C,II,(NHC,H,Rle:,), , brilliant, colourless needles, m. p. 168'. L)i~~seuclocur~ayZeth~Zenediu~zi~aenitrate, C,H,(NHC6H,Me,)2(HN0,),, colourless needles, m. p. 154'. Dipseudo-cum?/ZetlTL?/lenedin?ninepZatinichZo?*ide, C,H,( NHC6H,Me,),( HC/I),PtCl,, buff-coloured powder. Dipseudocui?iyZetkylenecZi(L~~aine?uercui*ichZoride C,H,( N HC,H,Me,),HgCI,, crystals me1 ting at 150'.Rinitrodipssudo-cunz?/leth?/lenediamine,C,H4[NHC,H(N0,)i\'Ie3]2,yellow powder, m. p. 97-98' ; an isomeyide, in. p. 49-50'. Uil)se.udocunzy~~ipe~a~ine, ~fe,H,Cf,N(C,H,),NC,H,~Ie,, colonrless needles, m. p. 148-150". 177. ('The action of phenyl carbimide on diphenyl-, dialphyl-, and dinaphthyl-diamines," By Alfred Senier and William Goodwin. When the two ethylenediamines described in the preceding ab-stract were treated with phenyl carbimide an interesting reaction resulting in the formation of ethylenediamines of the type C,H,(NR'*CO*NHPh), was brought to light. lhese diamines are analogous to the ethylenediamine of Volhard (Ann., 1861, 119, 349), and to the trimethylene carbanilide of Hanssen (Be?.., 1887, 20, 783).The reaction is shown to be a general one by the for-mation of the following homologues:-DicarbaniZido-dipl~en~Z-etlqdene-diamine, C,H,( NYh C0 NHPh) 2, n~.p. 220'. Biccsrbccdido-ditolyI ethyZe?aediamines, C,H,(r\'C,~H,~Ie.CO.NHPh)~. The ortho-derivative melts at 195-196", the nzetn-at 181-5', and the Pam-at 186". Dicai.bnniliclo-dircyl~leth~Zenediamine,C,H4!NC,H3nle,*CO*NHPh~,, melts at 167'. DicarbcLniliclo-cli~seudocuinylethylenediamine, C2H4(NC,H,Me,*CO*NHPh),, m. p. 19lo. Monocarbanilidodi-a-ncL~~l~t7,~leth?lZeenediamine,C2H4(NHC,,H7) (NC,,H,*CO*NHPh), -m. p. 266". 178. ''Note on the action of nitrous acid on P-nitroso-a-naphthyl-amine." By Arthur Harden and J. Okell. When /I-nitroso-a-naphthylarnine is treated in alcoholic solution with potassium nitrite and hydrochloric acid, it yields a potassium salt, C,,H,O,N,K, which crystallises in reddish-coloured needles and decom- poses vigorously at 250".A different salt, described in a previous paper (Ann., 1889, 255, 148) mas obtained by this reaction, which had the formula C,,H604N,K€I, and crystallised with 1iH,O, but on repeating the experiments the exact conditions necesytry for the formation of this salt could not be ascertained, and the simpler salt, which differs from it by the elements of nitrous acid, was always obtained. Sodium nitrite yields the corresponding salt, C,,H,O,N,Na. These salts behave towards acids in a manner similar to that already described, yielding, with hydrochloric wid and stannotis chloride, a compound, C,,H,N,* OH, which probably has the constitution of an -I imidazole, C,,H,< N>N (compare Zincke and Schwarz, Ann.,WH)1900, 311, 329).This substance crystallises with 1H,O, decomposes violently at 222O, and acts as an acid, yielding crystalline salts of sodium, potassium and harium. The silver salt has the formula, C,oHG.N,OA,a, and not that previously ascribed to it. The acetate melts at log', and the silver salt yields colourless, crystalline deriva- tives when heated with methyl and ethyl iodides. The isomeric a-nitroso-P-naphthylaminebehaves towards nitrous acid in a similar manner, yielding a potassium salt, C,,H,N,O,K +H20, which, with hydrochloric acid and stannotis chloride, gives a compound, CloH,N,*OH, which decomposes at 245O, and is isomeric with that described above, which it closely resemhles in its properties.179. ('1 : 2 :4-Metaxylidine-6 sulphonic acid." By Henry E. Armstrong and %. P. Wilson. One of the authors has on previous occasionc, discussed the conditions under which either ortho- or parn-or ineta-derivatives are formed from benzenoid amines, arid has argued that meta-derivatives are pro- 230 duced by the direct attack of the benzene nucleus, whilst ortho- and para-compounds are formed by a process of isomeric change in which the radicle is transferred from the nitrogen into the nucleus. An opportunity OF further testing this generalisation is afforded by 1:2 :4-metaxylidine. When sulphonated by an excess of fuming acid, this is readily converted into the 5-sulphonic acid, the only meta- xylidinesulphonic acid hitherto described ;it was to be supposed that the 6-sulphonic acid would be readily obtained on heating the sulphate, and this proves to be the case.When metaxylidine is mixed with a single molecular proportion of 100 per cent, sulphuric acid, and the mixture heated at 185' to 195' during 6 hours, the product then dissolved in water,and the solution neu- tralised with potassium carbonate, 90 per cent. of the theoretical amount of potassium-1 :2 :4 :6-m-xylidinesu~phonate,C,H,(CH,),(NH,)* SO,K, is obtained. Potassium1 ;2 ;4:6-aceto-m-xyZidinesuZ~?~os~~te, C6H2NH(CH,),Ac*S0,K, is obtained by heating the potassium sulphonate with acetic anhydride.It is a colourless substance crys- tallising from alcohol in spindle-shaped needles. On adding bromine to its solution in water, the sulphonic group is not affected, although it is easily displaced from the unacetylated acid. Potassium-1 :3 :5-rri-xyZenesuZp?~onccte, C,H,( CH,);SO,K,$H,O, is obtained from the 1:2 :4:6-rrz-xylidinesulphonate by diazotising, and then boiling with alcohol, or by means of the hydrazine; it crystallises from water in t'hin, colourless, lustrous leaves, and is nearly insoluble in alcohol. On fusing this salt with potash, it is converted into 1:3 : 5-m-xyleno1, m. p. 65". Bcwium-1 :3 ;5-m-xgZenesuZphonate, (C6H,Me2~S0,),Ba,2H,0, crystallises from water in fine, colour1e.s leaves, 1 :3 :5-rn-;il?/lenesuZp?~onicacid crystallises from water in thin, transparent, flattened needles. 1 : 3 : 5-m-X~ZenesulphochZos.icle, C,H3(CH,)2*S0,C!l, crystallises from light petroleum and benzece in needles, and from chloroform in massive crystals; m.p. 94". 1 : 3 :5-m-XyZes~esulpl~obro~~aide,C,H,(CH,),*SO, Br, resembles the snlphochloride in crystalline behaviour ;m. p. 92-93'. 1 :3 :5-m-XpZene-sulphonanzide, C,H,(CH,),*SO,NH,, crystallises from water in very lust -rous, colourless flakes, and from benzene in very fine needles; rn. p. 134'. 1 :3 :5-m-Xylenesulphanilide, C6H3(CH,),*S02-NH *C,H,, crys- tallises from alcohol in large, monosymmetric crystals; m. p. 119'-a:b :c = 0.8718 : 1 : 0.7341. p = 110'58'. 1 :3 :5-m-X~ZeneszcZpho-p-toZuidide, C6H3(CH,),*S02NH*C,H,. CH,, crystallises from alcohol in monosymmetric crystals resembling the anilide; m.p.121-123'. n:b :C = 1.18195 : 1 :0.9380. p = 101'7'. I‘180. The preparation of acetylchloraminobenzene and related compounds.” By F. D. Chattaway and I(.J. P.Orton. The authors reply to Armstrong’s recent criticism of the authors’ work. The statements which he calls in question are proved to be correct, and details are given of the method of preparing acetyl- chloraminobenzene. It is also shown that acetylchloramino-2 :4-dichlorobenzene can be obtained by the direct action of chlorine on acetanilide. ADDITIONS TO THE LIBRARY. I. Donations. Briihl, J. W., E. Hjelt, und 0. Aschm. Die Pflanzenalkaloide. Ill. Braunschweig 1900.From the Publishers. Gowland, W. Remains of a Roman silver refinery at Silchester (from Archceologia, vol. 57) 1900. From the Author. Idris, T. H. W. Notes on essential oils. Second edition. London 1900. From the Author. Ramsay, William. Modern chemistry. Part I. Theoretical. Part 11. Systematic. Lmdon 1900. From the Publishers. Rudorf, George. The periodic classification and the problem of cliemical evolution, London 1900. From the Publishers. IT. Pudmse. Glaser, Fritz. Indikatoren der acidimetrie und alkalimetrie. Wiesbaden 1901. At the next meeting, on Thursday, January 17611,1901, the following papers will be communicated :-“The preparation of esters from other esters of the same acid.” By T. S. Patterson and Cyril Dickinson. ‘‘Tecomin. A colouring matter derived from Biyno?Liatecomcc.” By T. H. Lee. ‘‘A new method for the measurement of ionic velocities in aqueous solution.” By B. D. Steele, R.8c.
ISSN:0369-8718
DOI:10.1039/PL9001600219
出版商:RSC
年代:1900
数据来源: RSC
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