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Proceedings of the Chemical Society, Vol. 16, No. 225 |
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Proceedings of the Chemical Society, London,
Volume 16,
Issue 225,
1900,
Page 121-142
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摘要:
P R O C E E D I N G 8 OF THE C H E M I C A L S O C I E T Y . EDITED BY THE SECRETABIES. No. 223. Vol. 16. _. May 3rd 1900. Professor THORPE F.R.S. President in the Chair. A ballot for the Election of Fellows was held and the following mere subsequently declared duly elected :-Messrs. Alexander William Bain B.A. Heinrich Romland Beringer Frank Curzon Britten B.A. John Richard Brooke A.I.C. Arthur Brand Chater Nicholas Cullinan M.D. John Cussons B.Sc. Arthur Charles Davis Noel Fielding Deerr William Donald Robert Eadie Frederic Richard Ellis Thomas FitzGi bbon Morris Broad Fowler Reginald Gordon Halstead James Herbert Haynes B.Sc. Henry Jennings James Henry Kershaw Adolf Liebmann M.A. PhD. Thomas Lamb Lockhart Thomas Macara Frederick Thomas Munton Robert Pettigrew Geoff reg Surtees Phillpotts B.A.James Wallace Sandford Bertram D. Steele B.Sc. James Walter Tilley Augustus John Walker B.Sc. Cert,ificntes mere read for the first time in favour of Messrs. George Edward Battle Totlands Dane Park Ramsgate ; John Henry Gough 22 Francis Street Chapeltown Road Leeds ; Percy John Hinks 16 Moreton Road South Croydon ; Tajiro Ichioka 8 Nottingham Place London ; David Herbert Patrick Earlsdon Coventry ; Timothy A. Smiddy Kilbarry House Cork Ireland. The following compounds are described o-illellL~l~lienyl-ncet~l-lzitl.oge~~ chloride (ortho-acet-chlorainino-tol- 102 Of llie following paper$ those marked * mere read :- “61. (‘ The substituted nitrogen chlorides and nitrogen bromides derived from ortho- and para-acet-toluide.” By F.D. Chattaway and K. J. P. Orton. Eolh 0- and y-acet-toluide when treated with hypochlorous or hypobromous acid produce nitrogen chlorides and bromides which readily undergo transforniation into the isomeric substituted toluides ; these in iheir turn forin nitrogen chlorides and bromides which pass into the disubstituted toluides in which the amino-hydrogen is again replaceable by chlorine or bromine. As with the substituted anilides when the ortho- and para-positions relatively to the acetamino-group are occupied the compounds undergo no further isomeric change Iiydrolysis or decomposition resulting from attempts to induce it. The halogen exactly as in the case of acetanilide or a substituted acetanilide is found always to take up the para-position when this is possible and when this position is occupied the ortho-position rela- tively t o the carbon to which the nitrogen is attached.The authors have shown (Y’vccns. 1899 75 1046 ; 1900 77 134 ; Ber. 1899 32 3513) that substitution by chlorine or bromine in anilines and anilides is uot a direct process but R result of the transformation of a nitrogen chloride or bromide a hypochlorike or hypobromite being probably formed first by the nitrogen becoming quinquevalent. The behaviour of the nitrogen chlorides and bromides derived from the toluides is in entire agreement with this conclusion. The properties of the nitrogen cliloiides and bromides obtained from the toluides reseiiible exactly those of other members of the class.The nitrogen chlorides are colourless the nitvogen bromides sulphur-yellow solids all crystallising well in four-sided prisms terminated by domes. All show the general reactions of uitrogen chlorides and bromides. They react with alcohol re-forming the toluide and producing ethyl hypochlorite or hypobromite although this action is usually accom- panied by a considerable amount of isomeric change. They react with ammonia liberating nitrogen with hydrocyanic acid formiug cyanogen chloride or bromide with hydrogen chloride brom- ide or iodide setting free the halogen and with hydrogen peroxide oxygen in each case the toluide being re-formed. On warming with dilute acids a certain amount of hydrolysis accompanies the isomeric change and this in the case of the nitrogen bromides is the chief action.ueiie) CH; C6H;NCI. COCH, m. p. 4 3 O . m. p. 118'. 103 Methyl-chlor-phenyl-acetyknitrogen chloride (ortho-ncet-chloraniino-5- chlor-toluene) CI-T,.Cl.C,H,.NCl.COCI-I ( X e C1 2 4) in. p. 66". dfetlLyl-dichlor-~,~ienyZ-ncetyl-~aitioye,~~ chloi*ide (o~tllo-acet-clilorni~iino- 3-5 dichlortoluene) CIS,. C1; C,IX,.NCl- COc:IT (3f.e C1 Cl 2 4 ; f) m. p. 78". p - ~ f e t ~ ? / l p ~ e ? a y l - a c e t y l - ) a ~ ~ r o g e ) i chloride (parn-acct-chlorainiiio-tol- uene) CH; C,H;NCI*CO(1113 ni. p. 91-92". ~~~etJiyZ-c?ilor-~,Iie7eyl acetyl nitroyen chloride (1'"~a-acet-chlor:Lnino- 3-chlo~tolueiie) CH; C1*C613,*NCl*COCH (Me C1 4 2) m. p. 48'. ~et?i?/l-r2ichlor-3,~Le~a?/l-acet~l nitrogen chloride (para-acet-cliloramino- 3 5-dichlor-toluene) Cl,.CH,. C,H;NCl*COCH (Me C1 C1 4 2 G ) in. p. 72'. O - ~ e t ~ ~ l - ~ ~ A e n y l - c c ~ t y l nitro,yeiz bronaide (ortho-acet-brommnino- toluene) CH,. C,H;NBr-COCH, ni. IJ. 100.5O. ilieth?ll-b,.o,n-plie~~~l-[Lcetyl-?Lit.,i bromide (ortho~acet-broni:~mi110-5- brom-toluene) CH3.Br-C6H::-NBr* COUH (Me Br 2 4) 111. p. 31". d~et71?/1-dibl.on~-~~?ienyl-r~cet~l-~~it~.o~e~a bromide (ortho-acet-broninmi~io- 3 5 - d i b ~ o m o t o l n e 1 i e ) ~ H ~ B ~ ~ ~ C ~ H ~ ~ N B r ~ O ~ G I ~ ~ ( ~ e 1 3 r :Br :2 :4 G ) m. p. 120. p-illetlLyl-l,heIzyl-ncetyl-~itl.ogen bromide (para-acet-bromnmino-tol- uene) CH; CsH,.NBr. COCH, m. p. 94-95'. 2lleth?jl-b1'01ii-~JienyI/I-acetyl-n~~.ogelz bromide (pnra-acet-broniarnino-3- brom-toluene) Br.CH,- C6H3.NBr.COOH (Me Er 4 2) m. p. 87". ~ e t ~ ~ ? / ~ - ~ ~ i b r o ~ ~ ~ ~ e ~ ~ ? / ~ - ~ i c e t ~ j ~ - ~ i ~ t ~ o g e ~ ~ bromide (p,zm-acct-bromainino- 3 5-dibromo-toluene) Br;C)B,.C,H,.NBr.COCI-F,(~le :13r :Br :4 2 :6) "62. "The estimation of hypoiodites and iodates; and the reaction of iodine monochloride with alkalis." By K. J. P. Orton and W. L. Blackman. The method of estimating hypoiodites is based on the oxidntion of sodium arsenite by hypoiodites but not by iodates. Excess of tlio standard arsenite is used and the unoxidised portion titrated with iodine aft'er the saturation of the alkali by carbon dioxide. The iod:Lte can then be determined by acidifying and titrating the iodine liberated.The hypoiodite solutions were prepared chiefly from iodine monochloride (dissolved in hydrochloric acid) and also from iodine solution. The initial reaction of iodine monochloride and alkalis is repreventod by the equation IC1 + 2MOH = MI0 + NC1+ H,O. With potash soda lime water and baryta water the whole of the iodine is for a short time (varying from 30 seconds to 5 minutes) present as hypoiodite. The transformation into iodate and iodide is practically complete after 24 hours. With ammonia tlie complete transformation requires 2 or 3 weeks. The solution obtained from 104 methylamine and iodine monochloride behaves in an exceptional manner the liypoiodite gradually disappearing probably oxidising the methylamine. The bleaching of indigo is shown to be unsuitable for the purpose of estimating hypoiodites owing to the direct action of even dilute alkalis on the indigo.The solutions obtained by shaking up iodine with mercuric oxide and water contain chiefly iodate and only a small quantity of hypo- iodite. DISCUSSION. In reply to the President Dr. ORTON said that the work of which lie had given an account was completed fifteen months before the abstract of R. L. Taylor’s paper (Proc. 1900 16 70) appoared. “63. ‘I Products of the action of sulphur dioxide on ammonia.” By Edward Divers. When the paper on ‘( Ammonium amidosulphite ’’ (Divers and Ogawa PIOC. 1900 16 38; Traw. 1900 ‘77 327) was communicated to the Society the authors were unaware that a paper on the subject of this note had been published by Schuinann (Zeit.nnovg. Chenz. 1900 23 43). Beyond the fact _that Schnmann also points out the incorrectness of Rose’s statement that sulphur dioxide combiues with only its own volume of ammonia the two papers have nothing in common. The main fact established in the paper by Ogamn nnd the author was the existence of ammonium amidosulphi te of which they ,had already given notice in a paper on “Ethyl ammoniumsulphite ” (T.l.cc?zs. 1899 75 534). Schumann has obtained a product of the same composition as ammonium amidosulphite in red masses not very hygroscopic i t dis- solves in water to a yellow solution forming ammonium sulphate sulphite thiosnlphate trithionate and pentathionate whilst am- iiionium amidosulphite is a white crystalline powder extremely deliquescent and soluble in mater forming ammonium sulphite only.Schumann obtained two other products having respectively the forinuls SO,,NH and 3S0,,4NH3 the aqueous solutions of which were similar to that given by the red substance SO,,PNH,. The author can only regard Schumann’s tliree products as mixtures of substances formed by the spontaneous decomposition of ammoninm amidosulphite. Since the publication of the paper on ammonium amidosulphite further work by Ogawa has fully established the existence amongst the products of the decomposition of this salt of the compound formu- lated (Zoc. cit. p. 334) as (NHJ2S203 but of which the true formula is 105 N2H,S,0,. Although only faintly acid t o litmus it forms salts of which the ammoniunzsalt NH4N2H3S,0, thepotassium SCdt ICN2H2S20, the bni*iunz mZt Ba(N2H3S,0,),,2H,0 and the lead salt Pb(N,H,,S,O.,), have been prepared.The constitutional formula NH,.S*NH.SO,II seems t o express the relations of this substance as Or "H<S?NH, so O 0 far as they are a t present known. This preliminary notice is published because unfortunately the circumstances in which the author and Ogawa are placed afford little hope of the full account of the products of the decomposition of ammonium amidosulphite being ready for publication for some con- siderable time to come. DISCUSSION. Dr. TRAVERS asked if the author attributed thc formula SO,.? to the compound he had described merely from analogy NH<s-NH with amidoacetic acid.Dr. HEWITT asked whether any decomposition products of the com- pound N,H4S20 had been obtained in which the sulphur and nitrogen were still linked together. There seemed to be a possibility of isolat- ing the sulphur analogue of hydroxylamine or some compound nearly related to it. Dr. DIVERS replied that this substance hydrolysed as EL sulphonic acid and yet mas not acid to litmus like all other sulphonic acids. Thc red substance soluble in carbon disulphide and ether might well bo the sulphur amide S(NH,), supposed to exist by Forchhammcr. 64. "On Brazilin. IV." By A. W. Gilbody W. H. Perkin jun. and J. Yates. I n a previous communication (Pvoc. 1899,15 27) i t was shown that trimethylbrazilin OH~C,,H,,O(OCIT,), when oxidised with chromic acid is converted into ti.iniethyZbraziZone OII~C,,H,O,(OCH,), and that this substance when heated loses water with formation of clelqdi-o- tvinietJ~~Zbi.aziZone OH-C,,H,O( OCH& a compound which yields an acetyl derivative and which is evidently identical with the acetyl com- pound which Herzig pisepared by the oxidation of acetyltrimethylbraziliu (Monatshefte 1895 16 913).The authors nom find that trimethyl- brazilone on treatment with phenylhydrazine is reduced to a substance having the formula C1SH,S04 which melts a t 173O and dissolves in nitric acid and other concentrated mineral acids yielding intense purple or orange solutions When trimethylbrazilin is oxidised with potassium permanganate 106 under various conditions a variety of substances are formed the prin- cipal of which are the following (1.) A dibirsic acid C,,H,,O, melting at 175".This acid contains one methoxyl group and is derived from the resorcinol portion of the molecule of brazilin because when fused with potnsh it yields a sub- stance which gives an intense violet coloration with ferric chloride. When heated with water at 200° this acid C,,H,,O, is decomposed with elimination of caibonic anhydride and formation of a monobasic i d C,H,,O (m. p. 119") which has been shown by synthesis to have the constitution .O-CH,*CO,H CH,O/\ I 1 \/ In synthesising this acid for which the name ~ ~ i e t h ~ l ~ e s o i ~ c i ~ ~ o l ~ ~ c e t i acid i s proposed pure methylresorcinol CHBO.C,H,* OH mas treated with sodium etlioxide and ethyl bromacetate and in this may ethyl ~ ~ ~ e t J ~ y b ~ e s o i ~ c i i ~ o l c i c e t a l e CH,O*C,H; OGH,.CO,Et was obtained as a thick colourless oil boiling at 184" (25 mm.) ; this on hydrolysis yielded tlie corresponding acid which melted a t 119" and was found to be identical with the acid C,H,,O, obtained from brazilin as de- scribed above. Since brazilin under other conditions (see below and PTOC. 1899 15 27-39) yields p-methoxy-salicylic acid it follows t h a t the acid CloHloOo iuust be the ~~zet/r~lcnrbo~~/resorcyZacet~c ncid having the formula melting at 129.5" (2.) A monobasic acid C,,H,O,(OCH,)-CO,H which has already been described (f'voc. 1899,15 29). W e find that this acid mhcn treated with conceutrnted sulphuric acid at SO" loses water xiid is converted into an acid C,21-11005 which melts a t 196" and when oxidised witrli periuauganate yields p-methoxy-salicylic acid.It is there- fore probxble that the acid C',,H,O,(OCH,).CO,H has the constitution 0 CH,O~\(\~H.CH,-CO,H \/\/CH(OH) CO (3.) An acidveryspringly soluble in water and meltingat 205". This acid has tlie formula C l ~ 1 3 ~ 8 0 ~ ~ ; it yields a silvei. salt C,7Hl,0,(C0,Ag), arid a tEimetliZ/E salt C,,H160,(C0,Me) (m. p. l l O o ) and is therefore dibasic. When fused with potash it yields a substance soluble in 107 water which with ferric chloride give3 an intense cihxhol reaclion ; it does not form a n oxime but when reduced with sodium amalgam it is converted into an acid C,~H,,O,(C!O,H), which melts at 227".When the acid C17H,,0,(C0,H) is heated a t 140' with alcoholic potash it is decomposed with formation of a neutral substance tho analysis of which agrees better with the formula ~171~2005 than with CI7H,,O ; it appears probable therefore that besides elimination ol equation C,7H,,0,(C0,H)z + 2H = C,;H,,O,+ 3C0,. This substaucc carbonic anhydride reduction has taken place according t o the crystallises from alcohol in needles melts a t 140° and appears to be a lactone. (4.) An acid very sparingly soluble in water which melts a t 214-215' with vigorous decomposition and gives also an intense catechol reaction after fusion with potash and treatment mitli forrjc chloride. The results of one analysis point t o this acid having the formula C1,H,,Os but unforhnately it has so far been obtained in such small quantity that the analysis could not be repeated.(5.) Metahemipinic acid. Constitution of B?-aziZin.-!l!he results described in this :xnd previous communications and especially the isolation of methylcarboxyresorcyl- acetic acid and of metahemipinic acid 0 OCH C H O ( ~ \ F H CO,H/ ' CO,H! \/ 'I,C!H \/\ UO,H from among the products of the oxidation of brazilin allow of only a very few formuls as possible expressions of the constitution of i h i h substance and after carefully considering all the facts tbc :tiiLhors are of the opinion that brazilin probably has the constitution repre- sented by the formula 65. "On Haematoxylin. V." By W.H. Perkin jun. and J. Pates. When telr~snetilyl~cenza~o~yZ~?z OH*C,,H,0(OC1H,)4 is oxidised by potassium permanganate under various conditions i t yields the follow- ing substances f 08 (1.) Metaheinipinic acid which was characterised by analysis and by conversion into the characteristic ethylimide melting at 230'. The formation of this acid from tetramethyl-hsematoxylin by oxidation with chromic acid has already been mentioned (Pvoc. 1899 15 241). (2.) An acid melting at 180° which evidently corresponds with the acid C,7Hl,0,(C0,H) (m. p. 208) obtained from trimethylbrazilin as described in the preceding abstract. This acid has the formula C,,H,,O,(CO,H), and is dibasic since it yields a silver salt C,,H,,O,(CO,Ag),. It dissolves in concentrated sulphuric acid with a crimson colour and when reduced with sodium amalgam is converted into an acid C,,H,,O,(CO,H), which melts at 194".(3.) An acid melting at 214" which when fused with potash is converted into a substance which with ferric chloride gives the pyrogallol reaction. This acid has the formula C,,H,,O, and is dibasic since its silver salt has the composition C,,EIl,cig,O,. I t contains two methoxyl groups and when heated with concentrated hydrochloric acid a t 200' it yields pyrogallol. When treated with acetic anhydride it gives an anhydride C,,H1,O (m. p. 154') ; it therefore has the constitution CH,O and corresponds with the methplcarboxyresorcylic acid obtained from brnzilin. The formation of this acid and of metahemipinic acid from hzmatoxyliu leads us t o believe that the constitution of this substance i s represented by the formula 66.Note on the function of the characteristic meta-orientating groups." By Arthur Lapworth. The author desires to draw attention to the following points the significance of which does not appear to be generally recoguised. The groups .CO*R *NO, .CN *SO$ are known to produce the followiug effects when in direct attachment to- (1.) A benzenoid nucleus.-They render the hydrogen atom in tile meta-position directly replaceable by all the characteristic substituting agents thus differing from all other known groups. 109 (2.) A :CH gvoup-They render the hydrogen atom directly re- placeable and the compounds exist in the tautomeric forms :CH*X:Y and :C:X*YH.(3.) A *CH group-The compounds are usually capable of conden- sation with aldehydes or of entering into the Claisen reaction with esters of oxalic formic and nitrous acids in presence of sodium ethoxide that is to say under conditions favourable to if not actually productive of the “ is0 ”-forms of the compounds in question. The connection between the foregoing facts is clearly brought out by the use of the mode of analysis suggested by the author {TTc~ws. 1898,73 446). The Claisen reaction is not applicable t o nitrobenzene in which there is no .CH group but should in accordance with the author’s view of the function of the above groups when attached to a benzenoid nucleus (Zoc. cit.) he applicable to benzenoid compounds containing x GH group in the ortho- or para-position to one of the groups in question.Reissert (Be? 1897 30 1030) states t h a t whilst the methyl group of o- and y-nitrotoluene reacts with ethyl oxalate in presence of alcohol and sodium no condensation occurs if ethyl nitrite is used. The author finds however that reaction occurs if alcohol-free sodium ethoxide and amyl nitrite are employed and under these conditions o-nitrotoluene readily affords o-nitrobenzaldoxime which on hydrolysis and treatment with potash and acetone yields indigo. pNitro- toluene also reacts though less readily with amyl nitrite affording p-nitrobenzaldoxime. If amyl formate be used in these reactions condensation appears to take place but the products are more difficull to isolate.The fact that m-nitrotoluene does not react in this respect like the ortho- and pra-compounds is in strict accordance with the author’s views. It is hoped that i t will be possible to show that the other meta-orientating groups behave in the same manner as the nitro-group. This occasion may be taken to point out that the application of recent views regarding the nature of unsaturated compounds (Thiele Anitalen 1899 306 87) to the case of substitution in the benzenoid series appears to lead inevitably to the conclusion already arrived at by the author (Zoc. c i t e ) that substitution in the metcc-position rela- tively to one of the above groups is probably preceded by the foima- tion of a tautomeric compound analogous to the L L i ~ o ” - f o r m ~ of the nitro- cyano- and keto-paraffins.110 ADDlTIONS TO THE LIBRARY. York 1900. I. Donations. Cross C F. E. J. Bevan and C. Beadle. La Cellulose. Trans- lated from the English edition of 1895 by R.-G. LQvy and M. Thomas. Paris 1900. From the Authors. Miller E. 13. The calculations of analytical chemistry. New From the Author. Garpon Jules. Rdpertoire g6oBral ou dictionnaire mhthodique de bibliographie des industries tinctorides e t des industries annexes. Vol. I. premier fascicule. Paris 1900. From the Publishers. l'umphlets. Ilartley W. N. On the occurrence of cyauogen compounds in coal gas and of the spectrum of cyanogen in that of the oxy-coal-gas flame. (Pvoc. I?oyul Dublin Soc. 1900 9 111.) Louis 1). A.Notes on gold and platinum niining in the Uial Dfountains. (I'Yoc. Inst. of ilIining tcnd JIetalluvyy 1900 vol. viii.) RESEARCH FUND. A meeting of the Research Fund Committee will be held in June Applications for Grants to be made on forms which can be obtained on application to the Assistant Secretary must be received on or before May 31st. A t the next meeting on Thursday M a y 17th the following paper will be communicated by the authors '( Ciilorine derivatives of pyridine. VI. The orientation of some aminocl~loropyridines." By W. J. Sell M.A. and F. W. Dootson M.A. RICUARIJ CLAd AND SONS LINIlED LUNUON ABD HIINGAY. Isswtl 24/5/1900 P R O C E E D I N G S OF THE C H E M I C A L S O C I E T Y . EDITED BY THE XECRETARIES. May 17th 1900.Professor TIIORPE F.R.S. President in the Chair. Messrs. John E. Brooke JWallace Sandford and Bertram D. Steele were formally admitted Felloms of the Society. Certificates mere read for the firs1 time in favour of Messrs. Charles Berjew Brooke Colne House near Nauuingtree Essex ; .ICriiest Owen Courtman Denford Ilouse At,kin’s Road Clxphaiu I’ark 8.W. ; Henry Bertie Gritton The Cottage Balmain Syduey X.S.ljr. Australia ; John Beresford Leatbes 10 Park MiLnsions h t t e r h e a Park S.W. ; Siduey Scrivener Napper 144 Highbury X e w P u k N. ; Oswald Silberrad Sunuy Croft Buckhurst Hill Essex ; J o h n T r q w i r Glenfield Starch Works Paisley. The following Certificates were approved by Coaucil Liuiler Byc-l.tw I (3) :-Angel0 Cantin Vacoas Nauritius ; AI.U. K\’sujuncl;L Eon, Mylapore Madras j M. Goolab Roy Chintadrepettah Xnclr~~s. Of the following papers those marked * were read :- “67. U The chlorine derivatives of pyridine. VI. The constitution of some aminochloropyridines.” By W. J. Sell M.A. and I?. W. Dootson E A . The authors gkve an account of their work on the constitution of various nminotrichloro- and aminotetrachloro-pyridines which IIILVC 112 I recently been described by them. The two compounds which result from tlie action oE aininonia 011 pentachloropyridine (Fmizs. 1S98 73 777) and which melt at 174-175' and at 212-213" are shown to have the constitutions represented by the formulce I and I1 re- spectively. 13otb compouuds heated with ammonia to a higher temperature give the same diaminotrichloropyridine which must therefore be repre- senked by formula 111.To the aminotrichloropyridine obtained by the action of ammonia ou tetracliloroisonicotinic acid (Tmiis. 1897 71 1083) the constitu- tion represented by formula IV \vas provisionally assigned (TVCC~LS. 1S99,75 980). This has now been completely established. The aininotricliloropyridine obtained (Yb'ans. 1 S99 75 980) by tlie action of sodium carbonate on n compound containing two pyridine rings was shown t o have the constitution represented by formula V. "68. 6' Ortho-substituted nitrogen chlorides and bromides and the entrance of halogen into the ortho-position in the trans- formation of nitrogen chlorides." By F. D. Chattaway and K. J. P. Orton.When phenylacetyl nitrogen chloride undergoes transformation a mixture of 0- and p-chloroacetanilide is produced in the proportion of 95-96 per cent. of the latter together with 4-5 per cent. of the former. The following compounds were described O r t l i o c ~ L l o i . o ~ l L e ~ ~ l ~ c e t y l t ~ ~ t ~ o ~ e ~ ~ chloride (nce tyl chloramino-2-chloro- benzene) C,H4C1*NC1.COCII, colourless long flAttened prisms 111. p. S8'. 0 i ~ t ~ ~ o b ~ ~ o i ~ ~ o p ~ i e i z y l i ~ c e t ~ l 1 i i t ~ ~ o ~ e 1 ~ bromide (acetyl bromamino-2- bromobenzene) C611,Br*NBr.COCH, yellow four-sided prisms m. p. 150- 152'. Both of these compounds undergo transformation into the 2 4-di- substituted acetanilides. DISCUSSION. Dr. HEIVITT pointed out that Beilstein and Iiurbatow (Amzrde?~ 1875 176 36) had separated the ortho- from the para-chloraniline by distilliug the mixed sulpliates with steum this method being 113 employed by them on account of the dificulty of isolating pure o-chloronitroberzene from the mixture obtained on nitrating chloro- benzene.Dr. COLLIE pointed out that if a compound were obtained in which the halogen was attached t o a nitrogen atom which was not directly united to the benzene nucleus it was possible that isomeric change involving the production of a meta-substitution liroduct might result. *69. Ammonium imidosulphite.” By Edward Divers and Masataka Ogawa. The authors have discovered a compound 3NH3,2S0, ~vhicli has tlie constitution HN(SO,NII,) and bears the same relation t o tlie amidosulphite as that which exists between imidosrilphate and amido- sulphate.When ammonim aniidosulphitc is allowed to decoiiipose completely in a current of well dried hydrogen or nitrogen a t a temperature not exceeding 354 it leaves a coloured residue wIiir.11 is practically insoluble ir? absolute alcohol. This residue freely solnble in mater can (with the exception of a small quantity of sulphate) be dissolved by repeated treatments with alcohol of 90 per cent. Reject- ing tlie coloured fractions first obtained the remainder of the solution on evaporation over sulphuric acid deposits bright micaceous crystals of the new salt amnoniusn imidoszdphife. The mother liquor which contains much ammonium amidosulphate must be removed by careful washing with 95 per cent.alcohol. The imidosulphice is very deli- quescent and all samples so far prepared have had an acid reaction towards litmus due to the loss of a little ammonia. By dissolving the ammonium salt in 75 per cent alcohol and adding exactly the equivalent quantity of alcoholic potash the pure crystalline potassium imidosulphite slightly alkaline to litmus is obtained. The imido- sulphites react with silver nitrate similarly to the amidosulphites and give with barium chloride a precipitate which readily dissolves in acids forming a solution which acquires the odour of sulphur dioxide and deposits barium sulphate. The constitution of ethyl sodiocyanacetate and of ethyl methylsodiocyanacetate.” By Jocelyn Field Thorpe.*70. The author pointed out that the reactions of ethyl sodiocyanacctate and of ethyl methylsodiocyanacetate are best represented by the formulre CN*CH:C(ONa)OEt and CN*C(CH,):C<ggr respectively. When et@Z sodiocyanacetate is dissolved in water the solution is ~ I 114 not alkaline nnd on evaporation in a vacuum leaves sodium cynn- acetate. The changes involved may be represented thus CN*CH:C<Eg + H,O = CN*CH,*C-OH = CN*CH,.CO,Na i- HOEt /ONa \OEt The production of acid ethyl salts frequently observed in the con- densation of ethyl cyanacetate with unsaturated ethyl salts can bo thus explained as the sodium compound of the condensation product on treatment with water would yield in a similar may the corre- sponding sodium ethyl salt.The acid ethyl salts on distillation lose carbon dioxide and pass into the corresponding nitriles. A nuniber of such condensations mere described and the conditions given under which the maximum quantity of acid ethyl salt is pro- duced. Experiments mere described showing that prolonging the timc of heating increases the quantity of neutral ethyl salt a t the expense of the acid ethyl salt. This is explained by assuming that the first step is the addition of a molecule of alcohol to the unsaturated sodium compound. Ethyl s7.1etl~ylsodiocyonacetc~t~ behaves in the same may as ethyl sodiocyanacetate but its solubility and deliquescent nature render its purification difficult. It condenses with unsaturated ethyl salts to form acid ethyl salts the yields of which however mere never more than 17 per cent.of those theoretically possible. The equation CN-CHNa.CO,Et + CH2:CCHS*C0,Et = CN*CH(C02 Et).CH,-CNa(OI-I,)C02Et usually supposed to represent a reaction of this kind is shown to be wrong because on treating the product of the reaction with methyl iodide the ethyl salt obtained gives on hydrolysis the symmetrical aa'-dimethylglutaric acids and not the unsymmetrical aa-dimethylglutaric acid Small quantities of cis- and tmns-acids such RS are obtained from ethyl cyanacetate and ethyl methylcyanacetate may be separated by the following method. The cyanoethyl salt is converted by treatment with methyl alcoholic potash into the cyano-acid which is then boiled with concentrated hydrocliloric acid as long as carbon dioxide is evolved.The cis- and trans-amides the intermediate products formed are finally converted the former into the imide the latter into the trans-acid. The imide is insoluble in dilute sodium carbonate solution and can thus be separated from the trrcns-acid. "71. '' The aalPP tetramethylglntaric acids." By Jocelyn Field Thorpe and W. J. Young. EtJqZ sodiocynnncetate CN. CH:C(ONa)OEt separates from absolute fiJcobo1 in lustrous plates j with mater i t gives (see preceding abstract) 115 sodium cyanacetate ; with an ice cold solut,ion of iodine in Pthci- it reacts to form ethyl iodocpnacetnte CN- CHI* CO,Et n brown oil which decomposes on distillation under diminishod prcssure ; an in1,er- mediate addition compound is however formed which reacts with unchanged sodiocyanncetnte at higher temperatures to form etlql clicyanosz~ccinnte thus Ethyl dicyanosuccinate separates from dilute alcohol in glistcning plates which melt at 120'.With bromine disfiolved in carbon bisulphidc only etkyl broliaoc?jccn- acetate CN*CHGr-CO,Et was obtained as a liromnish oil which decomposes on distillation under diminished pressure. Etlq19,1.et7illlsodiocynnncetrLte CN.C(CH~):C<:~~ is not precipitntcil on the addition of alcoholic sodium ethoxide to ethyl metliylcyan- acetate but is obtained as n gelat.inous precipitate on adding an equal voliime of dry ether to the solution. I t combines with iodine to form ethyl ~izetl~yliodocyn~zncetnte CN*C(C€T,)I.CIO.,Et~ a brown oil .decomposing on distillation under diminished pressure. It condenses with ethyl dimethylacrylate to give the acid salt CO,H*CH(CN)*C(CH,),*CH(CH,)*CO,Et which on distillation loscs carbon dioxide and gives ethyl a-nietIi?/l-P/3-dinieth~Z-y-cyano- butyntc CN.C€I,. C(CH,),. CH(CH,).CO,Et a fairly mobile oil boiling a t 224") which on hydrolysis gives a/3/3-tiimetliylglutaric acid melting a t 57". The proparation of etl~yl a-cyano-aa,/3/3-tetr~L- methyl ylutamte b. p. 174-176' and its convcrsion into t e t m - nzetliyl glutciriniide (m. p. 1 OS') and into trans-~/3/3a'-tetr(ci)ieth.!/l glutnric a c k ? (in. p. 95") are doscribcd. Tlic imide is converted by heating for 2 hours with 50 per cent. sulphuric acid into the cis-acid which melts at 140' and this on treatment with acetyl chloride yields its anhyclricle a liquid boiling at 155-160" (YO rnm.).Tho cis-wid is partially conocrtcd into the ti-a?zs-acid by heating i t in a scaled tube with concentrated hydrochloric acid. *72 (( /3-Isopropylglutaric acid and the cis- and tvccns-methyl By F. H. Rowles J. F. Thorpe and isopropyl glutaric acids." W. Udall. The main facts regarding /3-isopropylglutaric acid have already bcon described (Pvoc. 1899 15 103). By the action oE methyl iodide on the sodium compound of the product resulting from the condensation of ethyl sodiocyanacetate 116 with ctliyl /!-isopropylacrylate ethyl a - c l l ~ ~ ~ a o - a - i ~ e t ~ ~ ~ l - / ! - i s o l ~ o ~ ~ y l g l u - t n m t e is obtained as a thick oil boiling a t lS0-183O (25 mni.).This on hydrolysis with methyl alcoholic potash yields the corresponding potassium salt from the acidified aqueous solution of which the solid cyano-acid may bo obtained ; this on boiling with concentrated hydrochloric acid pnsses into a mixture of the iinide and the tiuns- acid. a-d~etlLyl-/!-isoln.o)ql glutarinde separates fromwater in colourless needles melting at 1 14-1 15". Trans-a ?)ietnl/l./!-isol~rol,yl glutaric acid separates from water in microscopic crystals melting a t 102' and is converted into the anhydride of the cis-niodification on heating with acetic anhydride in a sealed tube. The cis-modification (obtained from the imide by heating with 50 per cent. sulphuric acid) crystallises from water in glistening plates meltiiig a t 137" and on treatment with acetic anhydride is converted into the anhydride mliicli crystallises from light petroleum in prisms melting a t 44".Ethyl sodiocyanncotate condenses with ethyl cr-methyl acrylate t o form the mid ethyl salt CO,I-I.BH(CN).CH,.CH(CH,).CO,Et which on distillation yields e t l q l ~-~~~et7~~l-y-cyn~~obzetyrate a mobile oil boiling a t 305O giving on hydrolysis a-methylglataric acid. Ey a similar method to that above described ethyl a-cycbpzo-aa'- cEii,zetl~l/Zgl.cctai.[i~e jb. p. 1 S1-183') the potassium salt of the cyano- acid the cyano-acid and the cis- and trans-aa'-dii,ietJLylglutciric acids mere prepared. Ethyl P-),ietI~yLy-cyaiLobutyr~~ and P-inethylglutaric acid have also been obtained in a similar manner."'73. The racemisation of optically active tin compounds. Dextro- methylethylpropyl tin dextrobromocamphorsulphonate." By William Jackson Pope and Stanley John Peachey. The authors have shown (P.r.oc. 1900 16 42) that the aqueous solu- tion obtained by treating externally compensated methylethyl-n- propyl tin iodide with aqueous silver dextrocamphorsulphonate yields only dextromethylethylpropyl tin destrocamphorsulphonate on evapora- tion to dryness. They attributed this behaviour to progressive racem- isation of the limorotatory radicle (CH,)(C,H,)(C,H7)Sn. attending crystallisation of the sparingly soluble salt of the dextrorotatory radicle. As this the first well-determined case of the kind recorded has an important bearing upon the space configuration of quadrivalent sulphur compounds (Proc.1900 16 12) and upon the preparation of compounds owing their optical activity to the asymmetric nitrogen atom (T?.a7zs. 1899 75 1127) it seemed to merit further investigation. On treating externally compensated methylethyl-n-propyl tin iodide 117 with silver dextro-a-bromocamphorsulplionate in warm aqueous :;elution and evaporating the filtered liquid de~ti.o?,iutJL~lelJ~~~~)ro2,2/1 t i i b deztro- ~~oniocccnz~J~ors~Z~~IiolLale (CI-I,)(C,H,)(C,H,)Sn(C,,I-I,,13rOSO,) separ- ates in colourless plates which after crystallisation from acetone melt a t 104-1Y7° with previous softening; the mother liquors yield on evaporation further deposits of the same salt and no trace OF salt of the ltevorotatory base could be obtained.The behaviour of the dextro- camphorsulphonate and the dextrobromocamphorsulphonate is thus the same the whole of the lrevorotatory base (CB,)(C2€I~)(C~~II,)Sn.01i becoming converted into its dextrorotatory isomeride. In dilute aqueous solution the bromocamphorsulphonnte has the molecular rotation + 318" which accepting Walden's value [MI = + 270° for the bromocamphorsulphonic acid radicle allows [MIu = + 48' for tlic basic radicle ; the value [Ai] = + 45' previously obtained from the dextrocamphorsulphonnte is thus confirmed. A crucial test of the truth of the explanation based on progressive racemisation is now possible for if tlie intramolecular mobility of the base (CH,)(C,H,)(C,H7)SnOH is such that racemisation can effect total conversion of the externally compensated base into the dextro- rotatory component the reverse should occur under favourable con- ditions.Aoiie per cent. aqneous solution of the crystalline dextrobromo- csmphorsulphonate was made in the cold and the molecular rotation of tlie dissolved salt was found to be + 318'. The solution was then sealed up in a tube and heated on the water-bath for 2 hours; after cooling the molecular rotation was found t o be now only + 273'. As the molecular rotation of the acid is +270" the base must exist wholly racemised in the solution. Some of the solution was then evaporated to dryness on the mater-bath and after cooling made up t o its original volume by dissolving the residue in cold water ; the molecular rotation of the salt in this solution had risen t o +315" This experiment was repeated with similar results.Farther the addition of potassium iodide solution to aqueous solutions of dextro- methylethylpropyl tin dextrobromocampliorsulphonate before and after heating on the water-bath caused the deposition of dextrorotatory and of optically inactive methylethylpropyl tin iodide respectively. These facts afford the complete proof that on evaporating externally compensated methylethylpropyl tin hydroxide with either of the cpti- cally active acids the lzevo-base is wholly converted into tlie dextro- component by progressive racemisation. b I s c u s s I o N. Prof. PERCY PRANKLAND called attention to the remarkable mobility of tlie groups attached to the atom of tin which was quite without 118 parallel in the case of groups attached to carbon.I n no asymmetric carbon conipound with which he was acquainted had anything com- parable to this facility of racemisation been observed. 74. “Racemic and optically active forms of isoamarine.” By H. Lloyd Snape D.So. Ph,D. The author has examined the behaviour of the isoamarine previously described by Brooke and himself (TYCC~U. 1899 75 208) towards nitrous acid alkyl iodides acetyl chloride and nitric acid. Each of these agents acts upon ordinary amarine and it was desired to contrast the products obtained from the two bases. But although isoamarine entered readily into reaction in every case the products mere so unstable that as yet the author has failed to prepare them in pure condition.As the result of further investigation the anticipation of Japp and Moir (Z’l.nns. 1900 77 613) that isoamarine is the racemic form of amarine was fully confirmed. Isoamarine itself optically inactive was resolved by meam of tartaric acid into the acid tartrates C,1H,BNa.U,H,0,,2H,0 of the d- and I-bases the salt of the d-base being much less soluble than that of the I-isomeride. From the respec- tive tartrates the corresponding bases mere obtained by precipitation with ammoni:L. The I-base was more difficult to obtain in a stst,e of purity ; but i t was evident that the optical antipodes liad beeu obtained the one giving for [ a ] ‘ + 62tE0 and the other -61.30’ to - 58.65’ these values being determined in ethyl acetate solution after the rotation liad become constant.The racemic base has a higher melting point arid density but R smaller solubility tlian the optical antipodes. W. W. J. Yope has kindly measured the crystals of (2- aud Z-iso- ninarine and states that they are orthorhombic prisms sphenoidally hemihedral the crystals of the d-base showing the form 0 -k{l ll} whilst those of the I-isomeride show the forin 0 + k { l l l ) . The crystals of tlic two substances are thus enantiomorphously related. The racemic base was synthesised from the tl- and I-isomerides by mixing them iii alcoliolic solution ; but neither of the latter was r:Lccuiised wheii 1ie;ited aloiie with iilcoliol t o 200 11. L'IJ r)lL,'L'Jl(Ldt?. For~iiiiiiek J. S ~ ~ l r L I ~ t l ~ t 1 i ~ 1 ~ t i ~ c l 1 c S;icliwcis liiiustliclicr Lippmauii E.0. vo~i. Die Clheiiiie der Zucl<er;trtci~. 2uil ccl. Lcckyer Sir Normnn K.C.C. F.E.S. 1iiorg;niic evolutioii :is al;uJiccl Pettenkofer (illax VOU) :XIS Chciui@ 3-iil)illiniiis-i~iisg.:iLe orgauisalicr Fitr1)btuU'c. Ill. h r l i i i 1'JI)U. Brmnsclimeig lS95. by spectrum analysis. 111. London 1900. 1850-1900. 91s Anhniig Znr Atom-Tlicoric iiiit oilier 'l.'~tl~cik Xystoiii der Eleluente Studic von Julius Qnnglio. 111. 1;crliri 1 9 N . ltupe Hans. Die Chemic clcr n:itiirliclien Pubstolle. Cr:Liiiisaliwcig 1900. Siiverii Corl. Die liiinslliclic Scide i l m 1Ici.stull ~c~ig J3igc11- schaften uiid Verwenduiig. 111. I h h 1%J0. Wiesiier Julius. Die i?ohstoif'c des Pllauzciirciclics. 211tl ccl. Parts 1 and 5. Ill. Leipzig 1900. Ccricht iiber den 111. lnternstionalen Congr Clieiiiie Wie11 ISCIS. Drei Biilicle verfnsst voii clciu Gciicrdsccrel~iir des Congresses Friedrich Strohmer. \Vien 1 s9'3. Chemical Eeview The. A mont.hly journd for m:uiiif~icLuri iig cllemists and druggists dyers printers bleaclicrs sizers ~):LIJW ii~:tIccr;i Loricloii 18iY--d.?. and stainers lcatlier dressers k c . Vols. 7-13 Uictericli Karl. Analyse der I-Inrzc-Cal.~au~c uud c1 uinilri1i:ii'zc nebst ihrer Uhemie uud P1iixm:tcoguosie. Cerliii 1 900. Schultz Gustav. Die Cllie~~~ic des Stcinkolilcu thccrs. I h i t t e vollstiindige umgenrbeitete AuNage. Erster Bmd Die Rohmaleria- lien. Uraunscliweig 1900. RESEARCH FUND. A meeting of the Research Fund Committee mill be held in June Applications for Grants to be made on forms wliich can be obtained on application to the Assistant Secretary must be received on or before May 31st.
ISSN:0369-8718
DOI:10.1039/PL9001600121
出版商:RSC
年代:1900
数据来源: RSC
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