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Proceedings of the Chemical Society, Vol. 12, No. 161 |
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Proceedings of the Chemical Society, London,
Volume 12,
Issue 161,
1896,
Page 41-52
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摘要:
Is.sired 4/3/1896 PROCEEDINGS OF TEE CHEMICAL SOCIETY. EDITZD B17 TBE SECRETARIES. No. 161. Session 1895-96. Febi*uaq20th, 1896. Mia. A. G. Vernon Hal-court, President, in the chair. Xessrs. Jervis F:.Foakes aiid C. E. Hwrisoii were formally admitted Fellows of the Society. Certificates were yead for ths first time iiz favour of Messrs. Henry Thoinas Durant, c/o Messi-s. Loewensteiii and Co., Johannes-burg, South Africa ; Herbert, Edwin Macadam, Adam's Chernicd Go., Victoria Ilocks, E. ; Charles H. Reissinan, B.A., B.Sc., Saxony Villa, Oppid;-iiis Rod, Primrose Hiil, N.W. ; James Edwnrd Sllurn Tuckett, MA., 14, Hyde Road, Xastbourne. It was announced that the following changes in the Officers and Council were proposed by the Connci1:- As Vice-Prcrideizts : Professor Janies Dewar, F.R.S., and Profcssoi-W.A. Tilden, F.R.X., rice Dr. E. Atkinson and Ah. C. O'Sullivan, F.R.S. As Urdii~uryXenzbeias of Cozmc'1'1: Dr. E'orster Norley, Dr. G. H. Moi*ri\, Mi-. J. 11'. Roctger, and Professor Aiathnr Smithells, cice Pro-Cessoil EI. Dixoii, F.R.S., &. K. J. Friswell, Dr. Kipping, ar,d Dr: W. P. Wpnne. licssrs. Bertram Illourit, H. Brereton Baker, and Dr. J. Shiclds were appointed to audit the Society's accounts. The followiiiq were duly elected Fellows of the Society. Jol~izAllan, IVilliam Henry Barker, B.Sc., William Henry Bentleg, B.Sc., Jhurice Blood, U.A., Joseph Edw-in Alger Blyde, Joseph John Bowley, Hei-bert Lister Bowman, {B.A., Daniel Bray, James Kerry !3uibril!gc, Hugh Charles Herbert Candy, B.Sc., James Craig, M.A., 42 n.Sc., Frank Tlixon, Arnold Eiloart, Ph.D., Thonias Ewau, B.Sc .Ph.D., Charles James Pemmellcr Fuller, IYaIter Tlioinas Grist, William Harrington, James William Helps, Albert Howard, Ernest Ilnpes Jeff era, James Johnstone, Cass 11. ICeiinicott, Lnurence W. Xathieson, Joseph Edward Morrison, Harold Rostron, B.Sc., Thomas Francis Rutter, B.Sc., Chnrles Edward Sage, Arth~~Philip Salt, Peter B. Scotland, Aitken JIigget Simpson, Amrita La1 Sircar, L.M.S., Henry George Smith, Benjamin Bernard Turner, B.Sc. Of the following papers those marked * were read :-+21, ‘I The origin of colour. No. XI. The yelIow colour of 2 : 3-bydroxy-naphthoic acid.” By Henry E. Armstrong. Mohlau, in a recent most interesting note (Cer., 1895, 3100), draws attention to the remarlinble fact that 2 :3-hydroxynaphthoic acid :md a number of its derivatives are coloured (yellow) substances.On account of this peculiarity, he proposes to substitute for the H /\/\ OH conventional formula (),/LOOH , the isodgnamic expression B H2 /\A 0IO,&= , and se eks to explain the fa ct that the ethylic salt of the acid dissolves in alkali, yielding a yellow solution, by the xasnmption that a yellow sodium derivative is produced by the dis-placement of one of the two hydrogen atoms in position 1. These new formulz do not seem to harnioiiise with any conceptiou which can at present be formed as to the interrelationship of colour and stracture, a subject to which the present writer has so often directcd at tention in communications to the Society (compare Proc., 1890-93).It is not difficult, however, to account for the appear- ance of colour in such a case by an assumption siniilai. to that already tliade use of by him in the ctlse of certain terephthalic arid other benzenoid c3rnpou11:1s, as well as of certain quinoline derivatires (Proc., 1892, 103; 1893, 13, 52, 55, 20G ; ‘I‘rans., 1892, 789). Whatever the exact structure of ~naplit!ialeiie may bc, it is pre-sumably centric in form, and not ethenoid, although its great activit,g in comparison with thtit of benzene may bc regarded as evidence of a strong tendency to cliange its io~m. If it be supposed that, owing to the strong tendency wliicb oxygen exhibits in so many benzenoid compounds to assume the keto-form, 2 : 3-hSdroxynayhthoic acid can 43 pass from the hydroxy-to the isodynamic keto-form, and in so doing affect the structure of the cycloid itself, in the manner shown by the following symbols, the yellow colour is accounted for withogt difficalty, as such a com-pound would be not only an orthoquinonoid derivative of naphtha-lene, bnt also an orthoquinonoid derivative of benzene.The “ etJhemrl salt” of such an acid would contain a free hyclroxyl gro~ip,arid might therefore well be acid. The bebaviour of the acid with phenylhydrazine, t:, which Schiip€ has just drawn atteritioii (Ber., 1896, as;), is without difficultjy expressed by the formidn here suggested.%22. ‘I Note on etherification.” By Henry E, Armstrong. Mohlau, in the paper referred to in the foregoing note, calls atten- tion to V. Meyer’s observation that the 2 : 3-acid in question is con- verted into an ethylic salt more readily than is the isomeric a-hydr-oxynaphthoic acid, and regnrds this as strong evidence in favour of his view of the constitution of the acid. An acid represented b-j a formula such as is suggested above would probably be particularly prone to combine with an alcohol, thus Attention is now drawn to this with the object of raising the qucs-tion whether some such explanation may not apply to the ~~einarlcnlsle generalisation at which V. JIeycr has arrived in the case of diortho-substituted acids, and wliich hc has sought to justify by introducing space considerations.The formation of a salt is presuninbly preceded by that of a coni- bination of acid and “ alkaloid,” from which water is then eliminated. Jnst as the acid-attracting power of the NEI, radicle in aniline is affected by tlie introduclion, say, of chlorine, so, in like manner, the “alkaloid ” attracting power of the carboxyl group niay be n-,suniect to vary as radicles are introduced in its iie:’ghbourIioocl in place of hydrogen-more particula~lyin the case of beneenoid compounds. Apparently such eflects ai e not snfficiently taken into account-the observations ~iithe dimethylnnilincsulplior~ic acids niaclc in tile iy\.ritey’s lakoratory by Niss Eynns (compare PYGC.,1193, 235)) may I)e referred to as of considerable interest from this point of vieit-, 44 showing as they do that tlic mere introductioii olf two nictIiyl groups into tlic NH,-group in plnce of the hydrogen altogctlicr modifies the character of tlie coinpound, rendering it iiismsitivc to tlie actio:i of bromine in a most remayknblc niaii~iei*.Tt is iiitciiclc.ci to make ex-periments to ascertain if the intmduction of tli !’Tercnt :~lkylsinto thc carboxyl group att‘fectthe bclinJ-ioiw of aci(1s iii any similar ij~aii~icr. *23. “The re!ation of pinelie to citreiie.” By Henry E.Armstrong. A. v. Bacyer in liif; receiit (L3th) note on orientetion in the terpc:.c series, shcsxs in a most interesting iiianncr that the genetic connec-tion existing between piiiene and citrene is far closer than bils liitberto been supposed.It mas, illerefore, be desiixhle to briefly put on 1-ecordan idea ~’iit’lii-efereiice to pincne wliich has long been iii tllc, writer’s mind, and w-hieli has led hiin to i-eprri tlie pm1:lem of its constitution from a, point of vie\\- sonieivhat similar to that bJ-Tvliiclr v. Bac-j-el.appears to have been guided. The fact that, under certain conditions, piiicnc belinvcs as a man-stlienoid conipoiiiicl, and yet under others readily gives dcrivatives. sccti as the citreiie dihjdrochlorides, led him, scvcral years ago, to consider the possibility of its being trinietlijilen~clerivatirc, the, simplest expreFsioii foy which would be It is uniiecessary to point oiit liow such a compound would pass into a citrene-diliydrochloride snch as may be dcrirccl from Tiemann‘;; citrcne formtila, the formntioii of n-liicli from n dipentamethylene derioative such as pincnc is represented to be by both Bredt and Tiemann is very difficnlt to uiiderstancl-not to say eminently im-probable.The explanation of tlie formation of a coinponnd having the pro-perties of the hydr.ochloride obtained from pinznc-artificial camphor -offers perhaps the greatest dificulty at present. This cornpound can scarcely be a dimct cierivatire of pinaiic, aiid seems to be closelj-related to camplior--in fact, the wii tei-112s obtained a smnIl quantity of caniphoric acid by its oxidation with nitric acid. It appears not im-probable that mrne iiiore or less proPoiu~(lchaugc attends its fonnx-tion, and, with the aid of the formula abovo given, it, mould not be rfifficult to represent the yimductioii from the trinietliylene radicle or a iicm penta-or methyl-tetmmetliylcnc ring attached to contiguous carbon atoms of the hexamethylene ring, and thus to arrive at a formula such as the writer long ago attributed to camphor.That many of the derivatives obtained from camphor are the end products of a series of analytic and synthetic changes, there can be no doubt; it is impossible to explain the formation of snbstances so different as cymene, metacymene, ethyldimethylbenzene, carvacrol and acetylorthoxylene in any okher way. At one time we thought but of its relation to cymene; latterly the relation of camphor to trimethylsuccinic acid has monopolised attention : but it may well be that the latter, like the former, is an elusive slipport, and owes its formation to atomic redistribution. It may be pointed out that “arti6cial camphor,” pinene nitroso- chloride and pinene dibromide differ in a remarkable and significant, manner in optical properties, the first alone being optically active.It is to be remembered that the carbon atoms which are connected by an ethenoid linkage in pinene cannot be the origin of its optical activity, and, whatever its formula, it must be one containing at least one %symmetric carbon atom. But, this being the case, it is difficult to understand how the addition, either of bromine or of nitrosy1 chloride, can give rise to optically inactive products capable of affording an inactive pinene ; the Occurrence of “ra~ematisat~ion”in such a case would seem to indicate that the region in which the asymmetric carbon is situated also becomes affected, although, apparzntly, but temporarily: i.e., whatever be the change, it is subsequently re- versed-even when pinene is converted into the nitrosochloride.If we cannot accept this conclusion, we must admit that the formulae hitherto attributed to pinene are all unsatisfactory expressions to a far greater extent than we have ever supposed. The dificulty, it may be added, is greater in the case of such a formula as Tiemann’s -as this contains two asymmetric carbons-than in the case of those proposed by v.Baeyer, or by the writer. similar argument is applicable in the case of camphor. If the atrgumei;t of t’he following note be admitted, the production of an inactive campholide on reduction of camphoric anhydride (Haller, C. R., 1896, 295) may, in fact, be regarded not only as a proof that the CO gronp undergoing reduction is connected with an hydrogen- ised asymmetric carbon atom, but also as evidence of the presence of but a siugle asymmetric carboc in camphor. 24. “The conditions involved in the occurrence of inversion in the case of asymmetric (optically active) compounds. By Henry E. Armstrong. Having formed the opinion that the changes which attend the production of what are supposed to be pineie derivatives merit much 46 closer attention, the writer has been led to carefully consider Walden’s recent very remarkable observations on the formation from each of the two active malic acids by means of phosphorus pentachloride or bromide of an oppositely active chloro- or bromo-succinic acid, from each of which in turn a inalic acid of its own order of activity may be obtained (Ber., 1896, 1.33).It does not appear difficult to explain these results without any modification of our current theory, and attention is now called to consideratims which, perhaps, may prove to be of importance in discussions of the behavlour, and of other questions relating to, asymmetric compounds. When opheal inversion is effected by hydrolytic agents, in the case of mi aldose, or of a ketose or acid, it is probable that, in the first instance, the keto-group becomes hydrated, and that either an “ aldehydrol,” CH(OH),, or a “ ketohydrol,” C( OH),, or an “ acid-hydrol,” C(OH),, is produced.When water is withdrawn from such compounds, if the water be formed from an OH-group of the hydrol complex and a hydrogen atom attached to the carbon contiguous to that of the hydrol complex, an ethenoid derivative wili be formed,, thus On hydrat’ion, according as hydration takes place at the one or the other junction of the ethenoid linkage, such a compound will afford one or the other of tlhe two possible asymmetric forms ; and if, as in the case of tartaric acid, the compound 130 symmetrical, it is to be expected that the two forms will be produced in equal proportions.But if an unsymmetrical compound be thus changed, such as a hesose or an acid like gluconic acid, it is to be expected that the severance will take place to a greater extent at one of the two junctions, and in some cases perhaps only at one. The striking results recently obtained by Lobry de Rruyn, and all E. Fischer’s Observations, are in accordance with tliis view, which, in fact, is the generally accepted one. When malic acid is acted on by, say, phosphoiw pentachloride, probably the first action to occur is one involving the formation of a chlorphosphoninm compound, thus, a6 rt6 (1) CH*OH + €’CIS = CH*OPCI4+ HCl. The next st’age in the change may be assumed to be one involving “ internal condensation,” n 47 Snpposing that this compound be then acted 011 by hydrogen chloride and resolved into chlorosuccinic acid and phosphorus oxy-chloride, if the attack became directed by the phosphorus, so that the chlorine took up the position of the phosphorus, complete inrersion mould be effected : b nb (3) C<gcl, + HCl = CClH + POCI,.a It will be obvious that such an explanation may be of general application, especially in connection with the exclusive production, under natural conditions, of a single asymmetric form. "25. '' The production of naphthalene and of isoquinoline derivatives from dehydracetic acid." By J. Norman Collie, Ph.D., and N. T. M. Wilsmorc:, M.Sc, It vas shown by one of the authors (Trans., 63,329), ihat, under certain con dition,r, diacetglacetone condenms forming a jellow crystalline compo 11 nd, apparently a benzene derivative, and that this further condenses easily, forming a second yellow compound, which was shown to be a derivative of naphthalene.On the average, dehydracetic acid yields about a quarter of its weight of the first compound. A dioxiine of the first yellow corn-pound has been prepared in a nearly pure state. By distilling the cliacetate of the second yellow compound with zinc dust, a naphtha-lene hydrocarbon, m. p. 75-78", has been prepared. Its composition agrees well with that of a dimethylnaphthalene. On oxidation with dilut'e nitric acid it yields an acid, giving the fluorescein reaction.Analysis of the silver salt of this acid agrees with the composition C,B,O,Ag, ; and the melting point, 115-120", coincides fairly well with that found for benzene 1methyl 3, 4 dicarboxylic acid (Ber., 1892, 6108). . By the actioc of strong sulphuric acid on the second yellow compound (dime thylacetodinaphthol), a coloiirless substance results. By the action of strong ammonia on the first yellow compound, a yellow basic substance (C,,H,,NO,) is produced, soluble in water and in alcohol, forming interisely yellow solutions. The chloride and platinichloride were prepared and analysed. On heating with strong sulphuric acid, acetic acid is given off, and the sulphate of mother base is left. This base has the composition CI?lI,,NO.On oxidation it yielded an acid, which appeared to be a lutidine dicarboxylic acid, CgHSNO,. The authors consider it probable that these bases are derivatives- 48 of isoquinoline formed by condensation of the yellow bengene coni-pound with ammonia. CH/\ CH,.CO.CH, CH,'\'\,c H, -I-NH, = 1 I + 2L€,O. ICO~CH,~CO.CH:~ \/\/I'A OH CHyCO*CH, CH,/v\,CH3 The second base would be 1 1 N , and the lutidine dicmboxy- %2A3 HOZC lic acid, N *26. 'I Note on a difficulty encountered in the determination of nitrogen by the absolute method." By Wyndham R. Dunstall, F.R.S.,and F. H.Cwr. The percentage of nitrogen in aconitine determined by the soda-lime process, using the base, or by the absolute method, using the hydrochloride, agrees well with that calculated foom the formula C33H4.iN012,which is 2.1 per cent.A few years ago Richards and Rogers (Chemist aid Druggisf, 38:242) stated that ~vhei~ the amount of " nitrogen " in aconitine is determined in the usual manner by the absolute method, it is found to correspond with nearly twice the per-centage calculated from tlie formula given above, and they, therefore, proposed to alter the iorinula of aconitine to C3,H4,N,O,,,in accord- ance with the results of their determinations. At that time the present writers were unable to look into the cause of these high results, but they were satisfied as to the accuracy of previous de- terminations (with the hydrochloride), showing that the molecule of the alkaloid contains but one atom of nitrogen.Recently they have had occasion to determine the nitrogen in the base by the absolate method, the air beiug expelled from the combustion tube by carbon dioxide and the gas collected in an nzotometer. They were surprised to find that over 4 per cent. of gas was obtained instead of 2.1 per cent., the calculated quantity. The determination has since been repeated by four independent observers, every pecan tion being taken to ensure complete coinbustioil by employing a, long layer (about 60 cm.) of red-hot copper oxide, and by conducting the burning slowly. The perceiitages obtained were 4.4,5.3, 5.1, 3.8,4.0, 4*1,4.3, The highest percentages were obtained when the burning wits con-ducted at about the usual rate, the lowest numbers by burning ex- tremely slowly and maintaining the temperature as high as possible 49 thronghout the process.Similar results were obtaiiied wht.11 the combustion was conducted in n vacu~~iii,and tho gns drawl1 off through a Sprengel prrip in the manner suygestcd by Fraiikland and -4rmstrong. The hydrocldoride of the a91ka10’ic7,hcweve~.,whc 11 bni*ced in either ~ay,gives a percentage nilly slightly higher tha:i the calculated amoniit. Stiychnine and some other typical nitrogenous organic compounds hare been bnmt in pre&elj- tlie same manner as nconitine, hut tlie percentages fonncl wcrc. as ii$nal, only slightly highel-than those cslcnlnted from the formula. A qnantity of this gas having lxen collc~ctccl in clifTcrent experi- ments which had given too higb wsnlts, a complete analysis of it was made.Nitric oxide and carbon monQxidc were absent. By exploding with excess of oxygen, measuring the contmction, mtl absorbing thi. carbon dioxide, methane v7as proved to be present. Estirna,tigg the iiietliare in the mixed gas, and deducting it from the total volume taken, the nitrogen amounted to almost exactly 2.1 per cent’., corre-sponding with that calculated from the formnla Cj3H45N0,1. Experiments made mith artificially prepaiwl mixtures hare shown that when 1ai-gely diluted with nitrogen, rnetliniie is burnt ITery slowly and with difiiculty by red-hot copper oxide. In condnctipg the process in the usual inauner the iiifluencc of the carbon dioxide nsecl to expel the air froni the tube, no doubt p-eatly aggravates the difficulty. Aconitine seems to be exceptional in giving rise to PO much methane during combustion.PossiblJ-the diEculty might bc overcome by mixing the alkaloid, not rnerelj Kith finely powdered copper oxide, but also with a more powerful oxidising agent, as, for esaiiiple, lead chromate. Neither aconitine hydrochloride, benz-aconine, 1101’ aconine hydrochloride present this anomaly, and it has been observed that if aconitine is introduced into tlie tube along with a little cuprous chloride, the percentage of gas obtained corre- sponds very nearly with the calculated quantity. 27. Mixed diazoamides containing an orthonitro-group.” By Raphael Meldola, F.R.S.,and Frederick William Streatfeild, F.I.C.which -Tiis ~~reparcdOrthodinitrodiazoaini~o~~nze~e, and described by the nutliors in their last conmiiwicxticii o:i tLis subject (Trans., 1894, 52), does not appear to be capable of ethyl3tion by tlie usual inethods (Zm. cit.). As this is tlis first esccptioii that has yet been fouiid to the general mctliod of allqlxting tlie dinzoamides iiitrduceci by the authors in 1886 (Tmiis., 1186, 624), it becsinc of sptcinl inte- rest to ascertain whether the usual triplet of isoiiiericies could be pc-pared when an orthonitro-group mas present on one side of the elisin of nitrogen atoms. The mixed diazoamide from ortlio- and p8r:t- nitraniline was prepared by both metliods of combination in the usml 50 mayS-,and the product found to be identical irrespective of tlic order of diazotising.So far the production o€tlie compound is quitc normal. After crystallisatioii from alcohol it consists of goldenyellow scales melting with decomposition at 192-193" when tht: temperature is raised rapidly. The formula is written (o)KO,.CGH,.N,HoC,H,.~O~~~). The compound is decomposed by excess of strong Iiydrocliloric acid at ordinary temperatures into the usnal mixture of four products, viz., ortho- and para-nitranilinc and the correqwnding diazo-clilo-rides. It has the acid characters common to all tlie dinitrodinzo-amides, dissolviug in alkaline soliitious with a reddisli colour, and being precipitated unchnnged by acids. By the action of ethyl iodide on the potassium salt in alcoholic solution the ethyl derivative is oh-taiiied in the usu:11 way.The lntter consists of ornn3e necdles melting at 177-1 79'. A special attempt was made in this casc to separate tlie mixed diazoamide into isomerides by fractional ethylatioi~, bnt tlie resulk was negative, the proclnct being siniply a mixture of unethylxted compound (m. p. 192-193") ancl the ethyl derivative (m.p. 177-178"). Under all cii~curn~t~nces,the ethylation of this cliazoamiile is incom-plete, a certain amount of unclianged substance being loft in the mother liquor, even when potassium hyclroxide and ethyl iodide are used in excess. The behaviour of tlie ethyl derivative towards hydrochloric acid is quite exceptional, and the products of' its decomposition are ethyl-p- nitraniline and orthonitrodiazohenzene chloride.This is the first in- stance which has come under our observation in which an alkyl-diazoamide from tlie direct alkylation of s mixed diazoamide has given only two instead of four products on decompositicn by acid. This ethyl derivative is also remarkable for its stability towards hyclro- chloric acid, as it had to be kept at a temperature of about 80-9V for some hours in presence of a large excess of acid before deconi-position mas complew. Not a trace of nitrogen was evolved during the decomposition. The products were iclentifiecl by filtering the cold acid solution into an allraline solution of p-naphthol (Trans., l&8T,438)and collecting the briglit red precipitate which at once forincd.Tlie latter, after washiug with water, was extracted with liydrocliloric acid which removed ethyl-p-nitraiiili~ie ;melting point of iiitrossinine 119-120" (Trans., 1SS6, 631). The red residue proved to be ortIionitrohenzene~~o-~-n~pl~~lio~,m. 11. 210" (BIelclola and Hughes, Trans., 1W1,37.4). These results indicate for the cthyl derivative the clcfinite formula NO., 51 This view was confirmed by combining diazotised orthonitraniline with ethyl-p-nityaniline wheii the same compound (m. p. 177-179O) was obtained and not au isonieride. TLe explanation of the exceptional behaviour of this ethyl deriva- tive is bound up with the general question of the “protecting influ- aice ” of a nitro-group in the ortho-position, as shown more especidiy by the recent researches in Victor Meyer’s laboratory,which bring out vcry clearly the influence of ortho-substituents in preventing nlkylation of the carboxyl group.NOThe System X<NH2.N,.y is incapaEle of being allcylated .zohe?z NO, aid NH wein the ortho-position. An attempt to prepare the isomer- ide by the action of diazotised paranitraniline on ethyl-o-nitraniline brought out still more forcibly tlie influence of the orthonitro-group. Combination coulcl not be effected under any of the conditions which so readily f uriiish the other alkyldiazoamides ; paranitrodiazo benzene chloride does not appear to have any action on ethyi-o-nitraniline. It may be of interest to state in conclusion that these results are of great importance as establishing the fixity of the alkyl group whep-alee introduced into a diazosmide. If this gronp were at, all ‘‘labile,” it might have been expected that by the action of diazotised paranitraniline on ethyl-o-nitraniline tlie same compound would have been obtained as by the action of diazotised orthonitraniline on ethyl-p-nitraniline.In the former case, as we have proved, the compounds remain for days iu contwt without combining. The dihulty which we have experienced in preparing ethyl-o-nitrsmiline is also duc to this same influence of the orthonitro-group. Since orthodinitrodiazo-ninidobenzene cannot be ethylated, we were unable to prepare it bg tile decomposition of this conipound. Attempts to ethylate ortho-nitraniline direct17 gave unsatisfixtory results, as also did the pub-lished methods (Beiistehz, 1-01.11, 339).Tbe simplest method, accorciing to our expet*ience,is to heat orthonitrophenol ether (ethyl) with alcoholic: ethylamine in a sealed tube for 12 hours at 150’. 23. “Allyl-p-dinitrodiazoamidobenzene:a study of the relations between melting point and constitution.” By Raphael Meldola, F.R.S., and Frederick William Streatfeiid, F.I.C. As the introduction of alkyls into diazosmides always lowers the melting point, the lowering being granter the greater tlie weight of the lioixologous rsdicles introduced, the above compound was piw pared with a view to ascertaining whether the same rule holds good for unsaturate3 radicles.It wCisfoiuld tlmt paradinitrodiazoamido- lmizene could be quite readily converted icto nn alkyl derivative by the action of potassium liydroxide and al!rl ioJide in the usual way. The pure compound forms small j(:Ilo\v ncedics, m. p. 164--165”. 52 0.0826 gnve 15.1C.C. moist nitrogen at 1$.,j0and 759.4 min. = 21-42N. (p)N0,*C6?3,*N,*N(C,’FI,).C,H,.NO,(~,) requires N = 21.40 per cent. The melting point of Lhr; original cornpoiincl is about 236’ (if tlic: temperatiire is ruiscd very r~pidlq’),of the inethyl derivative 219’, of the etliF1 deriv;ltive 19i--19P, and oi’ tlic henzyl derivative 190” (Trans., 1837, 112). Taking the nppcr limit of tctiiperaturc at which the origiiinl compound decomposes (2:SG”) the &pression produced bj-icethy1 is 17”, etlij-1 &4”,hrjzyl W,and d1\1 71’.It thus :~ppew~ tlitlt the iwatumted radicle iowei-s the nieltin~point to the snmc cst~nt(Wj as the difference between the methyl aiid ethyl dwivn- Iivcs, and so far ally1 IXIZJ-be sitid to esort a normal influence. 111 .()they morcls, tlie diffcrciice between the ally1 and ethyl deriratlve is the s:;tmeas bctwceii tlie ethyl and rnethuvl dcriixtive. Since benzyl p:oCiaces practically the same l~wwi~ig ethyl, it would fnrtlieras appcai*that the nature oi’ the groiip in direct coinbination with the nitrogeu atom is of pararnDuiit influence, and lliaCJ any other r,xdicleS associated with this group, such RS C6Hj in CH,.C,H,, zre OF SLI.~S~-diayy influeace, The actual nreiqht of ttie introduced imlicie is thud -ofs:iirzll iruportrzncc ac; co:!ip,ared with its constitution. At the next meeting 011 rl’liu~sda~,March 5th, the Pollo~ing papei*swill bc read :-‘’ The explosion of cpiiogen.” Ey Professor 13..13.Dixon, F.R.S., E, H. Strmge, and E. C:mli:~111. ‘* l’lie mode of burning of carbon.” By Pmfessor 13. @. Dixon. ‘a The detonation oE chlorine peroxide.“ 13y Professor H. 3. Uixon and J. A, Harker. *-Thc cornbinahion of cnrbon aiid hydrL)gt~n.’’By 1)~.B~neand 11. S. Jcrtlan. 4i \BItISON AND EONS, PRINTEUS IX OJiDIN-CRl-TO IiEE XAJEPTT, ST. MAXTIN’S LANE.
ISSN:0369-8718
DOI:10.1039/PL8961200041
出版商:RSC
年代:1896
数据来源: RSC
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