摘要:

J O U R N A LOFTHE CHEMICAL SOCIETY.TRANSACTIONS.aJYmmittee o f @nblLatiotr :HORACE T. BROWN, LL.D., F.R.S.A. W. CROSSLEY, D.Sc., Ph.D., F.R.S.H. B. DIXON, M.A., Ph.D., F.R.S.81. 0. FORSTER, D.Sc., Ph.D., F.R.S.C. E. GROVES, P.R.S.J. T, HEWITT, M.A., D.Sc., Ph.D.,A. MCKENZIE, M.A., D.Sc., Yh.D.P. R. s.R. MELDOLA, F.R.S.G. T. MORGAN, D.Sc.Sir WILLIAM RAMBAY, I<. C.B., LL. D.,A. SCOTT, M.A., D.Sc., F.R.S.Sir EDWARD THORPE, C.B., LL.D.,F. R. S.F.R.S.$itittar :J. C. CAIN, D.Sc., Ph.D.Sub- &bitor :A. J. GREENAWAY.1910. Vol. XCVII. Part I.LONDON:GURNEY & JACKSON, 10, PATERNOSTER ROW,1910RICHARD CLAY & SONS, LIMITED,BREAD STREET HILL, E.C , ANDBUNUAY, SUFFOLK

ISSN:0368-1645    

DOI:10.1039/CT91097FP001

出版商:RSC    

年代:1910

数据来源: RSC

摘要:

J O U R N A LOFTHE CHEMICAL SOCIETY,TRANSACTIONS.HORACE T. BROWN, LL.D., F.R.S.A. W. CROSSLEY, D.Sc., Ph.D., F.R.S.H. I3. DIXON, M.A., Ph.D., F.R.S.M. 0. FOIWER, D.Sc., Ph.D., F.R.S.C. E. GROVES, F.R.S.J. T. HEWLTT, M A . , D.Sc., Ph.D.,A. MCKENZIE, M.A., DSc., Ph.D.F. R. S.R. MELDOLA, F.R.S.G. T. MORGAN, D.Sc.Sir WILLIAM RAMSAY, K.C. B., LL. D.,A. SCOTT, M.A., D.Sc., F.R.S.Sir EDWARD THORPE, C.B., LL.L).,F. R. S.F. R. S.&;bh :J. C. CAIN, D.Sc., Ph.D.SlIb- @Mar :A. J. GREENAWAY.v- ______1910. Vol. XCVII. Part 11.LONDON:GURNEY & JACKSON, 10, PATERNOSTER ROW.1910RICHARD CLAY & SONS, LIMITED,BREAD STREET HII.L, E.C., ANDBUNQAY, SUBFOLK

ISSN:0368-1645    

DOI:10.1039/CT91097FP003

出版商:RSC    

年代:1910

数据来源: RSC

摘要:

CLARKE AND LAPWORTH : CYANOCARONE. 11I I. - Cy a? LO ccwonc.By REGINALD WILLIAM LANE CLARKE and ARTHUR LAPWORTH.ALTHOUGH carvone and its dihydro-derivative only differ inasmuchas the six-carbon ring in the former contains an et.hylenic linking,the products which their hydrobromides yield by loss of hydrogenbromide under the influence of alkalis are quite different instructure, as carone contains a three-carbon and a six-carbonring, whilst neither nucleus is present in eucarvone, which appearsto contain only one seven-membered ring (Wallach, Annulen, 1905,339, 94, e t sep.).The explanation of the formation of eucarvone which mostnaturally suggests itself is the one indicated by Wallach, namely,that in the first stage of the action of potassium hydroxide oncarvone hydrobromide, halogen hydride is removed in the samemanner as in the case of dihydrocarvone hydrobromide, but thatthe molecule of the resulting compound is less stable than that ofcarone, owing to the additional strain produced by the ethyleniclinking, and consequently the cyczopropane ring is a t once resolved,but between the two carbon atoms which previously formed partof the six-ring of the carvone hydrobromide ; hitherto, however, nodirect evidence confirming this idea has been forthcoming Had i12 CLARKE AND LAPWOKTH : CYANOCARONE.been possible to remove two hydrogen atoms from carone, or toseparate two groups from adjacent carbon atoms in a substitutionproduct of carone, in such a way as to produce an ethylenic linkinga t the position where this is found in the hypothetical intermediatecompound, it would have been possible to ascertain whether this atonce resulted in the formation of eucarvone, and thus to confirmthe view referred to, but no substituted derivatives of carone yetappear to have been obtained either by direct substitution or bypreparing them from substituted dihydrocarvones.The investigation of the action of alkalis on cyanodihydrocarvoneseemed likely to lead to the formation of such a substituted carvone,and since it has been shown by one of us that 8-cyano-derivativesof ketones are frequently convertible into a8-unsaturated ketonesby the action of alkalis in presence of ferrous hydroxide, a possiblemode of attacking this question was promised.After many unsuccessful attempts, pure cyanocarone was obtainedby a method similar to that used in preparing carone from dihydro-carvone, and under certain conditions it was found that cyano-dihydrocarvone hydrobromide might be converted nearly quantita-tively into the new substance, only traces of cyanodihydrocarvonebeing regenerated :A mixture of isodynamic forms is doubtless produced in thefirst instance, but in presence of the alkali, which acts asequilibrator, these, during the process of solidification, change withsuch e a e that only one isomeride remains, the equilibrium mixturebeing saturated with respect to one form.The product, when nearly pure, crystalliss in massive, transparentforms, and has the properties which it might be anticipated asubstance having the above constitution would po_ssess.By theaction of mineral acids, the cyclopropane complex is attacked inall cases before the cyano-group is affected, and with halogenhydrides the first product appears invariably to be the compoundof the acid with cyanodihydrocarvone, the reaction above repre-sented taking place in the reverse sense.The nitrile is saturated in character, and is attacked by coIdpermanganate solution only with great difficulty, but a t the water-bath temperature it is oxidised in alkaline solution, yielding caronicacid, the presence of the dimethylcyclopropane nucleus thus beingconfirmed. With acid permanganate, another acid, apparentlyisomeric with caronic acid, but not yet described, is producedCLARKE AND LAPWORTH : CYANOCARONE.13By the action of alkalis, however, the substance loses the elementsof hydrogen cyanide, and if hot dilute aqueous alkali is used inpresence of ferrous hydroxide to facilitate this reaction, the volatileproduct being allowed to pass away a t once in the steam, eucarvoneis obtained. The product which cyanocarone should normally yieldby the action of alkali is the ap-unsaturated ketone:CMeHCH*CH;CH _.____ -\CMe2or the hypothctical intermediate product in the preparation ofeucarvone from carvone hydrobromide. It follows, therefore, thata t looo, even in presence of quite dilute aqueous alkali, thissubstance is unstable, and is at once converted into eucarvone. ' Asthe cyanocarone certainly contains the cy clopropane ring, whichis not stable to alkali, it seems certain that the presence of theethylenic linking in the six-carbon ring to which the cyclopropanenucleus is attached does in fact render the molecule unstable,and leads mainly to the opening of the three-carbon ring a t thepoint indicated by the dotted line.The matter is of further general interest, too, in contrasting themode in which the cyclopropane nucleus breaks down undervarying conditions.It would not appear reasonable t o suggestthat the complex *CMe,*CH: is less stable than :CH-CH:, as underthe influence of halogen hydride it is the former which is resolved.Nor can it be maintained that either is in such a position withreference t o the keto- or cyano-group as would render it more liableto attack on this account.It would rather appear that when thecarbon ring is saturated there is the less strain when the ring iscomposed of six atoms, bqt when there is an ethylenic linking inthe nucleus, at least in certain positions, then the reverse obtains.and the smaller ring is the less stable one.'420- CH/.EXPERIMENTAL.Formation of Cyanocarone,The hydrobromide of cyanodihydrocarvone, prepared as describedby Lapworth (Trans., 1906, 89, 1826), was rapidly crystallisedfrom alcohol, and treated in the following manner. The hydro-bromide (160 grams) was suspended in methyl alcohol (300 c.c.),cooled to Oo, and to the pasty mixture an ice-cold solution ofpotassium hydroxide (36 grams) in methyl alcohol (150 c.c.) wasadded gradually with frequent agitation. The resulting liqui14 CLARKE AND LAPWORTH : CYANOCAHONE.was kept for some hours, whiIe it gradually assumed a violet colour,potassium bromide being deposited.The whole was then saturatedwith carbon dioxide, and the precipitated potassium bromide andbicarbonate separated by filtration ; the methyl alcohol wasremoved by distillation, and the volatile material expelled with theaid of a rapid current of steam. I n some experiments the oilremaining in the distillation flask solidified on cooling, but it wasfound to be advantageous, as a rule, to shake the semi-solidmaterial for some time with an ice-cold solution of potassiumpermanganate, added gradually until the colour of the latter wasno longer discharged, the excess of permanganate and the pre-cipitated manganese dioxide being subsequently removed by sulphurdioxide. The crude cyanocarone, which solidified on again coolingthe liquid, was collected, and crystallised several times fromalcohol :0.2158 gave 0.589 CO, and 0.166 H,O.C=74*4; H=8*55.0.2206 ,, 0.606 CO, ,, 0.172 H,O. C=74.9; H=8*66.0.1264 ,, 9.0 C.C. N, (moist) at 19O and 757 mm. N=8*15.C,,H,,ON requires C = 74.6 ; H = 8-47 ; N = 7.92 per cent.Cya?zocuTome is very soluble in ethyl and methyl alcohols, ether,acetone, benzene, or ethyl bromide, fairly so in light petroleum,and almost insoluble in water. It crystallises with great readinessfrom its alcoholic solution in large, colourless, six-sided, transparentcrystals, which melt sharply at 54-55O.When strongly heated,cyanocarone boils and distils with some decomposition above 300O.0.201, made up to 25-05 C.C. with absolute alcohol, a t 18O gave,in a 2-dcm. tube, aD+4.79O, whence [a],+298O.0.2306, made up to 25.1 C.C. with absolute alcohol, at ZOO gave,in a 2-dcm. tube, a,? 5.45O, whence [aID + 297O.Cyanocarone is only very slowly attacked by a cold aqueoussolution of potassium permanganate, or by a solution of the samesalt in acetone at the boiling point of the solvent. It does notdecolorise a solution of bromine in glacial acetic acid in presence ofsodium acetate.The seniicarbazide, C11H1SN:NLH*CO*NH2, crystallises fromalcohol in thin, flat, rectangular plates, which melt ratherindefinitely, and decompose slightly a t 218-221O :0.1526 gave 31.6 C.C.N, (moist) at 15O and 758 mm.C,,H,,O", requires N = 23.93 per cent.Cyanocarone also yields an oxime, but this could not be obtainedN=24.18.in crystalline formCLARKE AND LAPWOHTH : CYANOCAEONE. 15Action of Alkali and Ferrous Hydroxide on Cyanocarone.On boiling cyanocarone with a 10 per cent. sodium hydroxidesolution, an oil with a peppermint-like odour is produced, and theaqueous solution gives the reactions of a cyanide. The removalof hydrogen cyanide appears to take place more readily in presenceof ferrous hydroxide, and for the investigation of this decom-position the following conditions were employed. Twenty gramsof cyanocarone, 12 grams of potassium hydroxide, 4 grams offerrous chloride, and 150 C.C.of water were gently heated in aflask attached to a condenser, and the water which distilled over,carrying with i t the odorous oil, was replaced by gradually addingwater to the flask. The process was continued until the aqueousdistillate no longer contained an appreciable quantity of oil. Thedistillate was then saturated with common salt, and the oilextracted with ether. On fractionation, 4.4 grams of liquid boilingbetween 205O and 208O, and 1.1 grams boiling between 208O and215O were obtained, a small amount of residue, which underwentdecomposition on further heating, remaining in the distilling flask.The oil thus obtained readily decolorised a solution of bromine,and gave a reddish-violet colour on boiling with methyl-alcoholicpot'ash. It yielded an easily crystallisable semicarbazide, which,on recrystallisation from alcohol, melted at 183-184O :0.1978 gave 35.5 C.C.N, (moist) at 19O and 751 mm.CllH,,ON, requires N = 20.29 per cent.On mixing this semicarbazide with eucarvone semicarbazide,prepared as described by Wallach and Lohr (Annalen, 1899, 305,237), the mixture melted at 183-184O; the product, after repeatedcrystallisation from methyl and ethyl aicohols, was opticallyinactive. The conversion of cyanocarone into eucarvone by theabove process is not quantitative, and a considerable amount of awhite substance crystallises out of the aqueous residue. This wasisolated by diluting the residual liquid in the flask with water,heating to boiling, and filtering, when, on cooling, the substanceseparated, and was purified by recrystallisation from water, andfinally from alcohol :N=20.38.0.2278 gave 0.5630 CO, and 0.1786 H,O.C = 67.43 ; H = 8.72.0.203 ,, 13.3 C.C. N, (moist) a t 20° and 756 mm. N=7*45.C,,H,,O,N requires C = 67.69 ; H = 8.72 ; N = 7'18 per cent.The substance has the properties of a saturated lactam oranhydramide, it is unaffected by a cold potassium permanganatesolution, or by boiling aqueous or alcoholic potassium hydroxid16 CLARKE AND LAPWORTH : CYANOCARONE.solutions, and is only slowly changed by fusion with potassiumhydroxide and a few drops of water. It crystallises from wateror alcohol in square plates or cubes, melting a t 210-212O.Action of Hydrogen Halides on Cyanocarone.When heated with concentrated hydrochloric acid on the water-bath, cyanocarone yielded an acidic substance, which appeared tobe a mixture of the stereoisomeric dihydrocarvonecarboxylic acids(Trans., 1906, 89, 1823) ; from this after repeated crystallisationfrom carbon tetrachloride and finally ethyl acetate, an unsaturatedacid melting a t 141-142O was obtained, which was identified by theniixed melting-point method as P-dihydrocarvonecarboxylic acid.With a cold saturated solution of hydrogen chloride, cyanocarone isfirst converted into a hydrogen chloride additive product identicalwith that obtained from cyanodihydrocarvone, the cyclopropane ringundergoing fission.This substance on further treatment withhydrochloric acid loses the elements of hydrogen chloride, and the*CN group is converted into the CO-NH, group, the amide of theunsaturated dihydrocarvonecarboxylic acid being formed.Twentygrams of cyanocarone were suspended in 100 C.C. of concentratedhydrochloric acid, and the mixture was saturated with hydrogenchloride in the cold. The cyanocarone dissolved, and after a shorttime a white, crystalline substance separated, which was purifiedby crystallisation from alcohol :0.3035, after being heated with fuming nitric acid and 0.325 ofsilver nitrate, required 4.5 C.C. of 0-ll2N-thiocyanate.C1= 16.5.C,,H,,ONCl requires C1= 16.6 per cent.The substance crystallised from alcohol in flattened, prismaticneedles, melting at 69O, and when mixed with cyanodihydrocarvonehydrochloride its melting point was unaltered.0.402, made up to 25 C.C.with absolute alcohol, a t 1 8 O , gave, ina 2-dcm. tube, a, + 0 ' 8 2 O , whence [a]= + 25*6O. Cyanodihydrocarvonehydrochloride has [aID + 25'3O a t 1 8 O (Trans., 1906, 89, 1826).When cyanocarone is dissolved in a saturated solution ofhydrogen bromide in glacial acetic acid, and kept for some time,a crystalline substance separates, of which a further amount canbe obtained by diluting the acetic acid solution with water; thiswas collected and crystallised from alcohol :0.2964, after being heated with fuming nitric acid and 0.2478of silver nitrate, required 2'68 C.C. of O.112N-thiocyanate.Br = 30.7.C,,H,,ONBr requires Br = 31.0 per centCLARKE AND LAPWORTH : CPANOCARONE.17The substance crystallised from alcohol ia flattened needles,melting a t 85O, and on mixing it with cyanodihydrocarvone hydro-bromide, its melting point was unaltered :0.3546, made up to 25.1 C.C. with absolute alcohol, a t 14O, gave,in a 2-dcm. tube, a, + OS72O, whence [a],+ 25'5O.0.3208 of cyalrodihydrocarvone hydrobromide, made up to 24.9C.C. with absolute alcohol, at 14O, gave, in a 2-dcm. tube, a,+ 0*665O,whence [aJD + 25.8O.Unsaturuted Amide.-Tx'hen cyanocarone is allowed to remainwith saturated aqueous hydrogen chloride for some hours, thehydrochloride a t first formed slowly dissolves. When the liquidno longer gave the reactions of a nitrile, it was diluted with twiceits volume of water, and rendered alkaline with strong ammonia.After cooling, the separated solid was collected and crystallisedseveral times from water:0.2055 gave 0.5120 CO, and 0.1648 H,O.C=68*0; H=8.91,0.2022 ,, 12-8 C.C. N, (moist) a t 1 8 O and 751 mm. hT=7*22.C,,H,,O,N requires C = 67.7 ; H = 8-72 ; N = 7-18 per cent.0.2335, made up to 25 C.C. with absolute alcohol, a t 18*5O, gave,in a 2-dcm. tube, a,+ 1*33O, whence [alD + 71.2O.The amide is readily soluble in hot water or benzene, very solublein alcohol, acetone, chloroform, or ethyl acetate, and sparingly soin cold water o r light petroleum. It crystallises from alcohol orwater in small, flattened, white needles, melting a t 130O.It evolves ammonia when boiled with 10 per cent. aqueoussodium hydroxide, reduces permanganate solution immediately inthe cold, and decolorises a solution of bromine in acetic acid inpresence of sodium acetate.When heated on the water-bath with concentrated hydrochloricacid, the amide was converted into an acidic substance, which, ondilution, was precipitated as an oil; this was collected, and finallyobtained as a solid, which was recrystallised several times fromethyl acetate.It melted at 141-142O, and when mixed withP-dihydrocarvonecarboxylic acid its melting point was unaltered.The amide was therefore in all probability an isomeride of thedihydrocarvonecarboxylic amide previously described (Trans., 1906,89, 958).Oxidation of Cyunocarone.An aqueous solution of potassium permanganate oxidises cyano-carone fairly rapidly when heated with it on the water-bath.Asolution of 140 grams of potassium permanganate in 3500 C.C. ofwater was added gradually to a mixture of 20 grams of cyano-carone and 200 C.C. of water. The liquid was filtered from theVOL. XCVII. 18 CLARKE AND LAPWOnTH : CYAKOCAROKE.precipitated manganese dioxide, evaporated to small bulk, saturatedwith salt, and extracted with ether twice t o remove any unchangedcyanocarone or other neutral material. The liquid was thenacidified with hydrochloric acid, and extracted twelve times withether. The extracted material was freed from volatile material inthe usual manner, and was finally obtained as a dark semi-solidmass. This was purified by triturating it with chloroform, andcrystallising from a relatively small quantity of chloroform, usinga Soxhlet extractor, as it is sparingly soluble in this solvent.Afterit subsequent crystallisation from water, it was dried a t looo:C = 52.98 ; H = 6.28. 0.2065 gave 0.4012 CO, and 0-1168 H20.C7HI0O4 requires C = 53.16 ; H = 6.33 per cent.0.1075 required 13.6 c c. of N/l0-sodium hydroxide a t - 5 O forneutralisation, using phenolphthalein as indicator, twhence theequivalent = 79.6. A dibasic acid, C,H,,O,, requires equivalent = 79.The acid crystallised from water in small, white masses, meltingat 173-174O. The anhydride, prepared from the acid by meansof acetyl chloride, was crystallised from light petroleum, an_d wasfound to melt a t 55O.The properties of the acid prove it t o be identical with the cis-caronic acid prepared by Baeyer and Ipatieff from carone (Ber.,1896, 29, 2796), and synthesised by Perkin and Tliorpe (Trans.,1899, 75, 48).The first experiment on the oxidation of cyanocarone was carriedout with an aqueous solution of potassium perrnanganate containingrather more sulphuric acid than that required to combine with thepotassium hydroxide which is formed during the oxidation. I nthis instance, an acid similar in solubility to caronic acid wasisolated, which melted, however, a t 204O. On titration withsodium hydroxi-de solution, 0.104 required 6.15 C.C. of 0.1075N-alkali for neutralisation, using phenolphthaleiii as indicator,whence equivalent = 157.3. On adding a further 7 C.C. of the alkaliand heating for one hour on the water-bath, the excess of alkalirequired 0.9 C.C. f 0~1003n’-hydrochloric acid for neutralisation,whence the equivalent calculated from the total amount of alkalineutralised = 79.The data indicate that the substance is the lactone of a saturatedhydroxydicarboxylic acid, and probably isomeric with terebic acid.GOLDSMITHS’ COLLEGE, NEW CROSS. ‘r HE UNIVERSITY,M ANCHESTER

ISSN:0368-1645    

DOI:10.1039/CT9109700011

出版商:RSC    

年代:1910

数据来源: RSC

摘要:

AVAILABILITY OF HYDROGEN CHLORIDE. 19111.-The InJEuence of Water. on the Auailability ofHydrogen Chloride in Alcoholic Solution.By ARTEUR LAPWORTH and JAMES RIDDICK PARTINGTON.J N recent communications by one of the authors, in part withE. Fitzgerald (Trans., 1908, 93, 2167 et seq.), evidence was adducedthat during the esterification of a carboxylic acid or the hydrolysis of anester, as brought about by the catalytic influence of hydrogen chloride,the velocity of reaction was nearly proportional to the concentrationof the alcohol and the water respectively, although super6ciaIly thevelocity of hydrolysis in alcohol or acetone, with a definite concentra-tion of catalyst, appeared t o be nearly independent of the concentra-tion of the water over a wide range.The latter effect was attributedto a change in the availability of the catalyst, and was shown to beconnected with the observations of Goldschmidt on the retardinginfluence of water on the esterification of carboxylic acids in alcoholicsolution under the influence of mineral acids. Some preliminaryexperiments were also described which indicated that the phenomenawere, as suggested, due in the main to changes in the salt-formingpower or availability of the acid acting as cataJytic agent, and onmeasuring the availability of the acid by the use of a weakly basicindicator, i t was found that this was greatly altered by small changesin the water-content to an extent which corresponded, in order ofmagnitude at least, with the simultaneous changes in the velocity ofesterification.Pursuing this train of reasoning, it was demonstrated that thechanges in the availability of the acid due to the introduction of waterinto its solution in alcohol, for example, could not be explained by aidof the view of salt-hydrolysis proposed by Arrhenius, hence, as thepower which an acid has of forming complex ions with a weak base ofthe ammonia, type must be proportional to the concentration of freehydrogen ions, other things being equal, it may be inferred that thewater acts by diminishing the concentration of the free hydrogen ionsif such are present.Consequently water appears to act by unitingwith hydrogen ions, as does ammonia, to form complex hydrions. Also,since alcohol and water appear to play similar parts, combination ofhydrogen ions with alcohol is probable.With respect to the concep-tion that hydrogen ions unite with water or alcohol, no novelty wasclaimed, the possibility, even the probability, having been realised bymany chemists since t.he date when the ionic-dissociation hypothesiswas first proposed, and especially since the recent development of theoxonium theory.c 20 LAPWORTH AND PARTINGTON: INFLUENCE OF WATER ONGoldschmidt and Udby (Zeitsch. phy8ikal. Chem., 1907, 60, 728)had previously used the conception in discussing the kinetics ofaccelerated esterification, although theirs was an ad hoc application ofthe hypothesis, no attempt having been mado by these authors toassociate experimentally the anti-catalytic effect of water in esterifica-tion processes with alterations in the availability, or salt-formingpower, of the acid, and even in applying the conception to the case ofa very weak base present in small quantity in an alcoholic solution ofhydrogen chloride (Zoc.cit., p. 731) they picture the hydrated hpdrionsproduced on addition of water as being formed exclusively at theexpense of the small amount of salt derived from the weak basejcarboxylic acid), which is very far from being the case, as all thesalts of weak bases present and the free hydrogen ions, if there,would be diminished in the same proportion.It is very important to realise that two quite distinct propositionsare here involved. The first o€ these is, that the change in thecatalytic activity of a mineral acid in organic solvents, on addition ofwater, is due to a change in the availability of the mineral acid, andis capable of experimental proof in the manner previously indicated byone of the present authors.The second one concerns the explanationwhich is to be given of this change in the availability of the mineralacid, and is at present almost wholly hypothetical in character. Fitz-gerald and Lapworth, who approached the question from this point ofview, were the first to advance the former as a definite proposition,and to indicate the manner in which it might be experimentally estab-lished. Goldschmidt and Udby, on the other hand, had previouslyemployed the hypothesis of combination of hydrogen ions withalcohol and water respectively, in explanation of the anti-catalyticeffect of water on esterification in alcoholic solution; but as they didnot fully realise that the determining factor was the change in theavailability of the mineral acid (which naturally depends almostwholly on the alcohol and the water, and only to an almost inappreciableextent on the small quantity of feebly basic carboxylic acid), theyapplied the hypothesis in an incorrect manner to the calculation of .8, the concentration of complex hydrions formed by the csrboxylicacid (Zoc.cit., p. 731), entirely overlooking the necessity of takinginto consideration the influence of the alcohol used as solvent.A suggestion made by Goldschmidt and Udby, previously misunder-stood by Lapworth, is of great importance in its bearing on thehypothesis of hydrogen ion hydration, and attention may again bedrawn to it here.These authors attribute the abnormally largeincrease in the esterification velocity constant with increasing concen-tration of catalyst observed in alcohol containing water to thAVAILABlLITY OF HYDROUEN CHLORIDE. 21removal of part of the free water by combination with part of thecatalyst (Zoc. cit., p. 733-735 and 751 et seq.; compare also Proc.,1909, 25, 19 ; Trans., 1908, 93,8196 and 2197, where the mass of thefree water was assumed nearly constant). This explanation (although,in the generalised form given by these authors, it disregards thewell-known stimulating effect of anions on the catalytic action ofstrong acids) is probably correct so far as it applies to the abnormalcase where the concentration of the catalyst and the water are cornparable, and further investigation of this particular point wouldappear to be one of the most promising modesof adducing directevidence as to the correctness or otherwise of the hypothesis ofchemical combination between hydrogen ions and solvent.The present paper contains an account of work done in the expecta-tion of finding that the determining factor in the influence of wateron catalysis by mineral acids in alcoholic solution is the availability ofthe acid for salt formation.The “availability” of an acid may bedefined as a function proportional to its capacity for forming complexhydrions with any mon-acid base, and a t any moment the concentrationof these complex ions is given by t=k.BP, where k is a constant forthe base in the medium used, B the concentration of the free base, andP the “availability” of the acid, or P=kx.A t present it is onlyfeasible to determine the relative values of k for different bases, henceP here has also only a relative magnitude.”In order to avoid for the present all hypothesis as to the state of amineral acid in alcoholic solution, an expression for the change in theavailability of a mineral acid in absolute alcohol may be developed onthe facts adduced by Goldschmidt and by Goldschmidt and Udby.These authors found that the velocity OP esterification in absolutealcoholic solution mas proportional to the number of hydrogen ions,”or with a monobasic mineral acid as catalyst, to the product of itsconcentration and the degree of dissociation.This, however, is alsoproportional to the concentration of complex hydrions which the acidwould yield with a definite concentration of a free mon-acid base, or,in other words, their work affords the proof that in absolute alcoholthe velocity of esterification is ceteq-is pclribzcs proportional to theavailability of the acid as above defined.Now Goldechmidt and Udby also find that with a given concentra-tion of mineral acid and carboxylic acid, the velocity of esterification isThe availability here corresponds with the function fi/ysMq, developed in il,previous paper (Zoe. cit., p. 2195), where €2 is the degree of dissociation of the acid ;Y= the volume which contains one gram-equivalent of acid, A1 and cp correspondingwith B and k respectively.22 LAPWORTH AND PARTINGTON : INFLUENCE OF WATER ONwhere r is a constant which depends onIy1nearly proportional to ____ r+w’on the alcohol, and w is the concentration of the water.The con-tribution which Fitzgerald and Lapmorth claim to have made here, isin pointing out that the form of the esterification curve in alcoholdeparts from the unimolecular type only to the extent that the1condition of the catalyst alters, ~ being merely a measure of theT + Wavailability of the catalyst ; in other words, the velocity of esterifica-tion is proportional to the availability of the catalyst, not only inabsolute alcohol, but in moist alcohol too, and P = ----> where Po isthe availability when w=O.It may be noted that with any givenstate of the misture of alcohol and water the availability is alsoproportional to the concentration of the catalyst, hencePOTr + wwhere c I= the concentration of the catalyst, p = its availability whenc = 1 and w = 0, and X= the degree of dissociation as measured by theelectrical conduetivity method in a medium having that particularcomposition. For the highly dilute solutions discussed in the followingparagraphs, X is assumed constant.One of the present authors has already shown that this is the con-clusion which must be derived if the hypothesis of combination of thehydrogen ions with the alcohol, the wat,er, and the carboxylic acid beadopted (Trans., 1908, 93, 2195), as the availability must be pro-portional to the concentration of the free hydrogen ions if theso arepresent,I n order to prove experimentally that this conclusion is the correctone, it is necessary to show that the salt-forming capacity of a very1dilute mineral acid varies as -, where T is identical with that r+wcalculated from the results of esterification velocity determinations.For the purpose a very weakly basic indicator may be used, and theamount of salt formed with a given concentration of base estimatedby colorimetric methods.In practice this is difficult to do, and asomewhat different mode of treatment must be employed, namely, tokeep the amount of salt and base nearly constant by varying theconcentration of the mineral acid and the water simultaneously.I nthis case the application of the law of mass action to the definition ofavailability gives ,t=k.B. P, which in terms of the authors’ theoryis = kB.EC.r where f = the concentration of the complex hydrioas, r+wAVAILABILITY OF HYDROGEN CHLORIDE. 23When 6 and B are constant, then P is also constant, consequently ’It is shown in the practical part of the paper that (1) in thesecircumstances ___ is experimentally nearly constant for salt forma-tion; and (2) with different indicators the value o€ r is identicalwith that obtained by observations on the velocity of esterificutioo,within the limits of experimental error, which, it must be admitted,are at present considerable owing to the very small value of r, themeasure of the basic afinity of absolute alcohol, and also becauseof the considerable influence of the merest traces of impurity onthe availability of the highly dilute acid which it was necessary touse.The accurate measurement of the availability of acids in organicmedia is at present very difficult, owing to circumstances which havealready been discussed, and the means which is the most generallyapplicable, as yet, is that based on determinations of the velocityof esterification, since the basic affinity of alcohols and carboxylicacids is small and less likely to disturb the availability of the highlydilute acid than when indicators, amides, or other definitely basiccompounds are introduced; moreover, a carboxylic acid may be chosento suit a solution of any desired degree of acidity.At the time of thepublication of his first paper, and that with E. Fitzgerald, one ofus had in view the determination of the availability of acids invarious media, simple and mixed, by the electrical method applied inthe hydrogen electrode, which, apart from disturbing influences andboundary effects, should tbeoretically be capable of giving the ratio ofthe availabilities of an acid in solutions contained in two inter-communicating cells, entirely apart from the reality or otherwiseof ‘‘ free hydrogen ions.” Acree has recently drawn attention to thepossibility of using the principle of the hydrogen electrode in connexionwith experiments on catalysis for the measurement of the concentrationof free hydrogen ions (Arner.Chem. J., 1909, 41, 482). It would bemost interesting to obtain confirmation by this means of the ‘* avail-is a constant, say K.T+WC9’ + wk.c.r + wability formula,” P = -, for hydrogen chloride in strong alcohol.The method should also be applicable to the determination ofthe relative strengths of bases, weaker than water, in alcoholic and othersolutions. Such estimation might also be made by using esterificationor tintometric processes, as was previously suggested (Trans., 1908, 93,2199), but in connexion with the preliminary numbers previouslygiven, it is necessary to state that the method of determinatio24 LAPWORTH AND PARTINGTON : INFLUENCE OF WATER ONemployed necessarily leads to quite discrepant values for the affinitiesof very weak bases, owing to a number of sources of error which werenot realised at that time.It was assumed, for example, that most ofthe base added was in the free state, which is by no means the casewhen a base snch as carbamide competes with alcohol for the acid;moreover, the presence of traces of basic impurities in the materialwill affect the availability of even a relatively large quantity of anacid when this happens t o beone whichis feebly ionised, as is the casewith trichloroacetic acid in benzene, and our experiments show clearlyhow difficult it is to be certain that basic impurities in importantquantities are absent. With a fuller realisation of these and otherpoints of difficulty it is proposed to undertake the study of affinityconstants of some very weak bases in alcoholic solution, in the hope ofdevising trustworthy methods of measurement.The hydrogen electrode may also prove useful in investigating thechanges in the availability of acids in acetone and in ether.I n these,which, as is well known, are poor ionising solvents for hydrogenchloride, acids behave in a remarkable manner towards the first tracesof moisture. I n pure dry acetone, the first small additions of water donot cause any marked fall in the availability of dissolved hydrogenchloride, although with larger amounts the availability falls off muchas it does in alcohol, as is indicated by the numbers given byFitzgerald and Lapworth for ester hydrolysis and for esterification inmoist acetone.I n dry ether, again, a verysmall quantity of wateractually causes a decided increase in the availability. These pointswere first noted during experiments which Mr. Fitzgerald has beenconducting on the velocity of esterification in initially dry acetone andether ; here abnormalities were observed in the esterification curvewith the former as solvent, while with the latter the curves showed apoint of inflexion ; tintometric experiments confirmed the conclusionthat this was a phenomenon dependent on the availability of thecatalyst, and were of interest as adding some weight to the contentionthat the much discussed changes in the velocity of esterification aredue to static causes not connected with the mechanism of reactionexcept in so far as the availability of the catalyst is concerned.Experiments on the application of the hydrogen electrode to thesequestions are now in progress.EXPERIMENTAL.The alcohol employed in these determinations was prepared fromfive distinct specimens, A , B, C, D, and E.A was made from a sampleof 96 per cent. spirit by heating it with lime for three days, andsubsequently treating the resulting nearly dry alcohol with excess oAVAILABILITY OF HY DROOEN CHLORIDE. 25calcium. Samples B, C; D, and E were made from three differentspecimens of commercial absolute alcohol. I n all cases the last tracesof moisture were removed by heating the alcohol with a considerableexcess of calcium turnings until a sample of the liquid on addition ofwater set to a jelly-like mass, indicating that calcium ethoxidewas present, and the dried liquid was then directly distilled, thevapour being passed through a trap containing glass wool, the first andlast portions rejected, and the middle fraction collected in adried flask provided with a soda-lime tube to ensure the absence ofmoisture.The test applied for the presence of calcium ethoxideafforded full proof that the dehydration was as complete as the processwas capable of effecting, and further treatment with calcium wasobviously superfluous ; this conclusion mas confirmed by the approxi-mate constancy of the low water value of the four specimens of alcoholobtained in this manner.Tintom etrk Exper~rnewts.Aminoazobenzene is an extremely sensitive indicator to hydrogenchloride in absolute alcohol, and was only suitable for concentrationsof acid between N/lO,OOO and N/lOO,OOO, so that errors due to tracesof impurities were liable to be unreasonably large.Many otherindicators were tried, but the only one having a very decided advan-tage over aminoazobenzene was an azo-derivative of diphenylamine,the sensitiveness of which was considerably less than that of amino-azobenzene. Further investigation may lead t o the discovery of stillless basic indicators, more useful than these, for investigations insuch solvents as absolute alcohol with higher concentrations of mineralacid.The principle of the method used throughout has already beondiscussed; the procedure was to run a definite volume of a solutionof alcoholic hydrogen chloride into the absolute alcohol under investiga-tion, partly to discharge the colour by addition of a minute quantityof water, and then to restore the original tint by adding more ofthe alcoholic hydrogen chloride.The alcoholic hydrogen chloride and the water xere measured fromnarrow, graduated tubes discharging the liquid from a capillary exit ;these tubes had been carefully calibrated, and the errors in readingthe small volumes of liquid and those due t o alterations in bulk of theoriginal alcohol under investigation were usually within the limits ofthe experimental error due to other causes.The discrepancies at firstwere very marked, often leading to differences of 25 per cent.in the“ water value” for any specimen of absolute alcohol, and this wasfinally traced to the effect of the laboratory air with which th26 LAPWORTH AND PARTLNOTON : INFLUENCE OF WATER ONsolutions were unavoidably brought into contact during the operationof thoroughly mixing the added acid or water. When the solutionswere stirred in the ordinary way with a bent glass rod, it was noticed,especially with the extremely dilute solution of hydrogen chlorideemployed and with aminoazobenzene as indicator, that very decidedchanges in the colour occurred in the tintometer, indicating a diminutionin the acidity of the solutions. This was due mainly neither to carbondioxide nor aqueous vapour, as pure dry carbon dioxide had noappreciable influence, and the laboratory air, after being passedthrough a tube of lime or soda-lime, still produced the same effect.I f air dried over sulphuric acid wa,s used to stir the solution, however,the tint did not change, so that the effect was doubtless due to tracesof ammonia or some other powerfully basic impurity in the atmosphere.Further, the solutions, if undisturbed or stirred by twisting a spiralglass rod in the solution, did not alter in t i n t appreciably duringthe time occupied in an experiment, so that the latter method wasfinally adopted when using the tubes of a colorimeter to contain thespecimens of a.lcoho1.In all cases 50 C.C.of the specimen of absolute alcohol were used,but three distinct modes of measurement were employed, the tempera-ture of the alcohol in all cases being within two degrees of 2 5 O , exceptwhen it is stated otherwise.(1) The alcohol containing the indicator was contained in a 50 C.C.flask, and alcoholic hydrogen chloride having the same concentrationof indicator as the original alcohol mas added until the tint wasas nearly as possible identical with that in a standard specimen ina similar flask; water was then introduced, and more alcoholichydrogen chloride to restore as nearly as possible the original tint,this process being repeated several times, the added volume notedin each caso, and the water value of the alcohol determined by agraphic method or by the method of least squares.(2) The alcohol with a trace of indicator was contained in one of thetubes of a colorirneter and tinted by alcoholic hydrogen chloride t onearly the same colour as that of the liquid i n the standard tubeof the instrument, the exact depth of the standard liquid required t oproduce a balance being noted.After addition of a measured volumeof water, more hydrogen chloride solution was added, and the t i n tbalanced by varying the depth of the standard solution, Morehydrogen chloride was then added, the tint again balanced, and so onuntil a reasonably large number of readings had been made; in thiscase the depth of the standard solution was found experimentallyto be proportional to the hydrogen chloride present when the amountof water mas constant, so that the corrections were easily applied.(3) As in (2), but much more indicator was employed, and the tinAVAILABILITY OF HYDROGEN CHLORiDE.27was viewed through a deep blue screen. The depth of the standardliquid was not proportional to the amount of hydrogen chloride in thealcohol, so that separate experiments had to be made to determine thecorrection formula.I n cases (2) and (3) the water values were at first estimated bya modification of the method of least squares, but this was afterwardsabandoned, as they could be obtained graphically within the limits ofexperimental error.It will be unnecessary to go into detail in each case, but one ortwo typical instances of each kind may be given, with the objectof indicating the mode of calculation, as well as to show that theformula P- -?- applies here.r+wTYPE I.Indimtor : Aminoazobenzeae.W = water present in C.C.H =volume of alcoholic hydrogen chloride added in C.C.A =total volume of alcohol.Hydrochloric acid = N/lOO nearly.h =cAo, or quantity of acid per 50 C.C.of alcohol.AR = the water value, in grams, of 50 C.C. of the alcohol used.Ty'=F-z or the amount of water per 50 C.C. of alcohol.Aw. H. A. h. W'. C.0 .oo 1 -00 51-0 1 '00 0~000 10'30'09 2 .oo 52'0 1'96 0.086 10'70.18 2'83 52 8 2 73 0.171 10 '20 -36 4 -70 54.7 4.31 0-329 10.19 7 2 8 '40 58.4 7.34 0.616 10'3B = water value per 50 C.C. of the alcohol at 2 5 O = 0.097 gram,For the applicability of the formula P= - (see above), the valuewhence r = 10.8.kcr + wof c! should be constant.TYPE 111.Indicator : p-Tolueneazodiphenylamine, used with blue screen.Strength of alcoholic hydrogen chloride added was between N/5 andN/10.(In these cases no correction was needed for the relativelysmall volume of alcoholic hydrogen chloride added, which did notamount to more than 2 per cent, of the total volume of alcohol used.)F=c.c, of water present (in 50 C.C. of alcohol)28 LAPWORTH AND PARTINGTON : INFLUENCE OF WATER ONH = volume of alcoholic hydrogen chloride in C.C.I =height of adjustable column of standard liquid in cm.A series of measurements showed that under the conditions andwithin the limits used, the product H x 0 04 was constant withabsolute alcohol, or with alccihol containing any fixed concentration ofwater. 0 04 , where Ho isthe volume of alcoholic hydrogen chloride which would be necessaryto produce any standard tint corresponding with the fixed height, I,.G- ' )Hence this product was equal to ,Yo x Go- * )As (t -0.04) is constant, then for any two observations therelation between the amounts of acid Ho and H,' required to produceH x (i - 0.04)a standard t i n t was given by a0 -,= - (:, - .); or the productH x (i - 0-04) is proportional to the amount of hydrogen chloriderequired t o produce any definite standard tint with a fixed water-content.The first to indicate the applicability ofthe foregoing correction formula, and the second to demonstrate thatthe formuk Ho= (r + w ) x a constant is applicable when the waterkvaries in amount, and, therefore, P=- when the amount of r + whydrogen chloride is constant (compare p.23).Ho E x - - 004Two instances are given.EXAMPLE I.FtT.0.00.00.00'0740'0740'0740.2210.2210'221I?.7.858'408-958.358 -708.958'108 558 *85B.0'08760-07900.07170.07980'07490.07170.08350.07700.0730H.0.250.280 '300.50c -530 550.900,971 #04HXB.0.02190-02210'021510'03990.03970.03940.075150*07480.0759tC.2-382'402 -332 '402'392'372'402 *392'42The water value, 22, of 50 C.C. of the alcohol used was =0*092 gramThe column headed B contains the values of - 0 04 , and C, thoseH X B of -- R+ W'The applicability of the correction formula H x (i - 0.04) is shownc- )by the close agreement between the bracketed values of H x BAVAILABILITY OF HYDROGEN CHLORIDE.29CT f WThe applicability of the availability formula P = k- is shown bythe approximate constancy in the values of C throughout.EXAMPLE 11.w.0.00.00'00'05520.05520'19350.26550'35190 -43290-4861.8-408-799-628.739.037 -897.557.627 '878-47B.0.07900.07380'06410.07450.07070.08670.09250.09120.08710.0781€T*0,1650'180 '200.290'800'460.530'68O'S51-01HXB.0-013040'01330.012820.02160'02120-03990.04900.06200-07400.0789C.1 -371.401.351'441-411-381.361.391 -401-36R, or water value, = 0,095 gram for 50 C.C. of the absolute alcohol,whence r = 0.106 (or 1 litre of the absolute alcohol used was equivalentto 0.106 gram-molecnles of water a t 2 5 O ) .Esterijcation Ezperiments.For the determination of the water value of the alcohol by theesterification process, purified phenylacetic acid dried in a vacuumover sulphuric acid was employed in all cases.The flasks employedwere subjected to the action of a current of steam for a quarterof an hour, and then carefully dried before each experiment.The dry acid was only roughly measured, but the water in each casewas weighed. From each sample of alcohol a solution of hydrogenchloride of about N/10 strength was prepared by passing the driedgas into a portion of the specimen, care being taken to excludemoisture. The alcoholic solutions before admixture were all firstheated to the temperature of the thermostat, and the moment whenthe reaction commenced was noted.One or two titrationswere always made near the commencement of the reaction for thepurpose of obtaining the true initial titre by extrapolation, as thisvalue was required for a knowledge of the exact amount of waterpresent at any stage. The titre of the hydrogen chloride present a tthe beginning and end of each experiment was taken, using N/lOO-silver nitrate, thus definitely ensuring constancy in the amount ofcatalyst.Two flasks were always examined simultaneously, one containing theinitially dry alcohol, and the other, alcohol containing initially aweighed quantity of water.The intermediate values of the constants being the most trustworthy,the approximate water value of the alcohol is best gauged by comparingthe intermediate values of the constants obtained for the two flasks.That is to say, the value of r was not ascertained by the reference t30 LAPWORTH AND PARTINGTON : INFLUENCE OF WATER ONthe constancy of the value for any one experiment, but.by comparingthe numbers obtained in the two experiments.This method commends itself as the best, since the more trustworthyvalues for the velocity are of course those calculated from the timewhen the change has become steady t o a point not far from halfmay towards the end. All the titres, 9, are corrected for thehydrochloric acid present.The bracketed values of the titre y for 2' = 0 were obtained bygraphic extrapolation from the first few observatioos, for which noconstant was calculated. R was calculated throughout from the formulacorresponding with that used by Goldschmidt and Udby aswhen the concentration of the catalyst is constant,( R + w+ yo)(logey, - l o w ) - (!I,-@,1'- 5!; whence kc =where R=the water equivalent of 10 C.C.of the alcohol usedin N/10 C.C.W= the equivalent of the initially added water.y = the titre of 10 C.C. of the solution at the time T.?/,=initial titre [bracketed value] of 10 C.C. of the solutiony1 =the first titre actually made at the time TI.calculated by extrapolation.The time is given in minutes, and the titres are C.C. of N/lO-alkalirequired to neutralise the free phenylacetic acid present i n 10 C.C.ofthe solution investigated.(I' in all cases in this paper refers to the water equivalent in gram-molecules of one litre of alcohol.)Esterijcation Results for Specimen A .Each flask had a capacity of 100 C.C. Amount of solution used for eachTitre given in C.C. of iV/lO-sodium titre= 10 C.C.hydroxide.Time in minutes.Hydrochloric acid during reaction mas 0 01 95N, nearly.Flask 1.-No water.kc, assumingT.294268137212287Y e9.9319.508 -327 '636 '474-443-092-18r=0'15.-10-7410.68105110'49Mean ....., ,.., 10'61- -8 *23 7.618-36 7.778-31 7 '808 -38 7-898 -32 7 -77- -r=o.o9.-6-957-177 '247 -347-18AVAILABILITY OF' HYDROGEN CHLORIDE. 31Flask 11.-Water = 0.36 gram.ke, assumingT.[O153069138216446r - Y.r=0'15.20.23 -19 *50 -18.81 -17.10 8.9614'52 9'1612.30 9 *087'91 8'56Mean ......... 9-02--- -7-87 7-768-21 7 -968-11 7.918 '04 7 -828-06 7 *87- -r=0'09.-7 -507 -707-687 -597.62-The value of r evidently lies between 0.10 and 0.11.A series of tintometric experiments for this specimen of absolutealcohol gave r=(i) 0.105, 0.101, 0.105.(ii) 0.093, 0.101.(iii) 0.105, 0.101, 0-101, 0.095.Se~ies B.-Each flask had a capacity of 50 C.C. Amount of solutionTitre given inHydrochloric acid during reaction wasused for each titration = 10 C.C. Time in minutes.C.C. N/lO-sodium hydroxide.0.01 40N, nearly.Flask I.-With no water.Iic, assumingI A \ T.Y- r=O'15. r=O'11. r = O * l O . r=O-O9.[O1298 7-52 7-32 5.63 5-81 4.77220 5 '02 6-95 5-18 5-11 4 . i 3303 3-75 7-17 5.73 6.36 5 -00Mean ......... 7'15 5-61 52.3 4'83- - - - 11'43110.80 - - - -- - - -Flask 11.-With 0.18 gram of water.ke, assumingT. Y-10 10.50110-30 1095 8'88205 7 -30300 6 '36Mean .....- - - -6.28 5.57 5-40 5 '236 '49 5.77 5 '61 5.436.41 6-74 5 -56 5'39.,. 6'39 5-69 5'52 5.35- - - -The value of r evidently lies just above 0.11.(ii) 0.098, 0.106, 0-108. Tintometric measurements gave r = (iii) 0,108, o.098, o.loo,Series C.-Each flask had a capacity of 50 C.C. Amount of solutionTitre given in C.C. of used for titration= 10 C.C. Time in minutes32 LAPWORTH AND PARTINGTON : INFLUENCE OF WATER ONkcT.y. (r=O*lO).[0 13.331 -14 12.05 -42 9.71 -66 8-19 0.987126 5.65 1-006221 3-48 0.985N/l O-sodium hydroxide. Hydrochloric acid during reaction was0.01 82N.Flask I. --No water.T.18447 1131225[OT. 2/.9-59]8.83[O1127 7.9396 5 36186 3'48Mean ...... ..kc, assumingL \'r=0.15. r=O*ll. r=0*10. r=O'O9.- - - -- - - --10.81 8-22 7 -53 6-8310.34 7-98 7.42 6.8410'00 7 -90 7.36 6'8310.38 8-03 7'44 6 '83- - -Flask 11.-Water = 0.1430 gram.kc, assuming - \ T. ?I. r=0.15. r=O-ll. r=0'10. ~ = 0 ' 0 9 .12.701 - - -11.73 - - - - 2267 10-35 9-04 7 -93 7-64 7.38260 6 '43 8 -80 7'79 7'54 7 '28487 3.85 8-76 7 -77 7.50 7 '2731 ean . . . . . . . . , 8 *8 7 7-83 7 -56 7 -31[O- - - -From above, r is evidently between 0.10 and 0.11.Tintometric experiments gave = r{Series D.-Each flask had a capacity of 100 C.C.Amount ofsolution titrated= 10 C.C. Time in minutes, Titres in terms ofN/1 O-sodium hydroxide. Hydrochloric acid during reaction mas0.0278 N, nearly,(ii) 0.098, 0,095.(iii) 0*101, 0.105.Flask 1.-No water. Flask 11.-Water = 0.10 gram.Flask 111.-Water = 0.20 gram.kcy. ( r = O . l O ) .13-33] -12'30 -10'69 -9'16 0.9866'83 0.9924.50 1.001kcIT. y. (1.=0-10).[0 13.331 -21 12.47 -46 11.08 -73 9-91 0'987131 9-73 1.001227 5.43 1.007Tintometric experiments gave T = 0.09 and 0.1 1 by (i).Series E.-Each flask had a capacity of 100 C.C. Amount ofsolution titrated=10 C.C. Time in minutes. Titres in terms ofN/1 O-sodium hydroxide.Hydrochloric acid during reaction was0*0201N, nearlyAVAILABILITY OF HYDROGEN CBLORIDE. 33Flask 1.-No water, Flask 11.-Water = 0.197 gram.T.l-01125116120272372Y*12-5111.510.46.256'153.162'12kc (r= 0'10).-0.8050.8030.7920'793Mean ......... 0.798T. Y. kc ( r = O lo),20 [O 11.7550 10.4512.73 -I -129 8 '18 0.787280 5.15 0.815369 4-05 0.805Mean ... .... - 0.802whence. r is almost exactly 0.10.(ii) 0.090, 0.089.(iii) 0.095, 0.098, 0.090. Tintometric experiments gave = -(The apparent discrepancy between the values of r found, as above,and the value 0.15 used by Goldschmidt and Udby is apparentlydue mainly to the circumstance that they calculated the value forhigher concentrations of catalyst.A comparison of the numbersfor the velocity of reaction at low concentrations indicates that thealcohol used by these authors was probably as dry as that used inthe experiments detailed in the present paper.Summary.availability )) of a very dilute solution of hydrogen chloridein moist alcohol is nearly an inverse linear function of the amount ofwater present for quantities of water not exceeding a concentrationof N/2.(ii) The effect is a static one, and there is no reason to believe thatthe anti-catalytic effect of water is due to any other cause than achacge in the availability of the acid; it is not, for instance, to anyappreciable extent the result of any influences, such as increase inviscosity, tending to lower the measured velocity of reaction(on this point compare, however, S.F. Acree, Amer. Chem. J., 1909,41, 471), nor is it the result of ester hydrolysis.(iii) The availahility within the above range may be very nearlywhere c = concentration of the hydrogenkrepresenbed by c*-I' + W'chloride, k being a constant, w the concentration of water present,T being the water equivalent of the alcohol present.(iv) r is a constant which depends on the alcohol (as Gtoldschmidtand Udby have demonstrated in the case of esterification), buttwithin the limits of experimental error, is the same whether theavailability of the acid be measured by means of esterificationvelocities or by estimating the amount of the salt which the acid canform with a weak mon-acid base.(i) TheVOL. XCVII. 34 MORQAN, MICKLETHWAIT, A S D WHI rBY :(v) For absolute alcohol dried ovor exce3s of calcium, 3' is about0.10 for very lorn concentrations of hydrogen chloride at 2 5 O ; thus, atthis temperature, the availability of hydrozhloric acid in absolutealcohol is lowered 50 per cent. by the addition of 1.8 grams of waterper litre of alcohol.(vi) If any free hydrogen ions exist in solutions of acids in wateror alcohoI, an assumption for which there is at present no directevidence, then for small changes in the composition of the mixture ofwater and alcohol it may be concluded that the concentration of theseis a measure of the availability of the acid.(vii) The fundamental differenx between the view of Goldechmidtand Udby and that of Fitzgerrtld and Lapmorth revolves on the pointthat the fir&-named workers, although realising that the catalyst ismostly shared between the alcohol and the water, neglected to considerthe change in the availability of the catalyst when water is added toits alcoholic solution, and consequently they formed an incorrect con-ception of the manner in which water would affect the equilibriumbetwaen a dissolved weak base and its salt.The authors desire to state that most of the cost of this investiga-tion was defrayed by a grant from the Government Grant ResearchFund of the Ro:al Society, and for this they wish to express theirindebtedness.SCUUNCK LABORATORY,Ux IVEKSITY OF MAN CH ESTER

ISSN:0368-1645    

DOI:10.1039/CT9109700019

出版商:RSC    

年代:1910

数据来源: RSC

摘要:

34 MORQAN, MICKLETHWAIT, A S D WHI I'BY :IV.-Organic Derivatives of Antimony. Part I.Ti-icurnphoylst ib ine Chloride and Triphenylst ibirieHydroxynitmte and Hpdroxysulphate.By GILBERT T. MORGAN, FRANCES M. G. MICKLETHWAIT, andGEORGE STAFFORD WHITBY, B.Sc., A.R.C.S.A COMPARATIVE study of the interactions taking place betweensodium camphor and the trichlorides of phosphorus, arsenic, andantimony has shown that in the case of the arsenic compound theprincipal products are dicamphorylarsinic and tricamphoryl-arsinic acids (Trans., 1908, 23, 2144; 1909, 95, 1473). Theexperiments with phosphorus trichloride are still in progress ; thepresent communication deals with the case of antimony trichloride.The interaction of sodium camphor and antimony trichloride i35 ORGANIC DERiVATIVES OF ANTIMONY.PART I.dry toluene does not lead to the production of any SUbshncessoluble in aqueous alkali hydroxides or carbonates. The onlyproduct definitely isolated and identified is tricamphorylstibinechloride, (C,H150)3SbC12. This substance undergoes destructivehydrolysis so readily that the resulting tricamphorylstibine oxide,(C,,H,,O),SbO, is always more or less contaminated with hydratedantimonic oxide arising from the decomposition of the chloride intohydrochloric and antimonic acids and camphor.As one object of this research was to obtain an organic derivativeof antimony sufficiently stable and soluble for employment as atherapeutic agent, attention was now directed to triphenylstibinechloride, (C,H,),SbCl,, obtained by &tichaelis and Reese by theinteraction of chlorobenzene, antimony trichloride, and sodium(dnnalen, 1886, 233, 43).As these investigators have stated that this aromatic antimonyderivative is possessed of considerable stability, attempts were madeto convert this substance into compounds dissolving more readilyin aqueous solutions.When treated with alcoholic silver nitrate, triphenylstibinechloride loses its chlorine quantitatively in accordance with thefollowing equation :(C,H,),SbCI, + ZAgNO, = 2AgCI + (C,H,),Sb(NO,),.The triphenylstibine nitrate is not stable under these conditions,and undergoes partial hydrolysis into a definitely crystalline sub-stance, triphenylstibine hydroxynitrate, (C,H,),Sb('OH)*NO,, whichmay be recrystallised from hot water without further hydrolysis.I n connexion with the formation of this substance, it is of interestto note that Michaelis and Reese describe a triphenylstibine nitrate,prepared by dissolving triphenylstibine in hot fuming nitric acid(Zoc.cit., p. 52), which is stated to be insoluble in water, butcrystallisable from alcohol.The substitution of silver sulphate for silver nitrate in theforegoing reaction leads to the production of the corresponding tri-PhenYlstibine hydroxysulphat e, ( C,H,),Sb (OH)*SO,*Sb (OH) (C,H5)3,which is less soluble in water than the hydroxynitrate.E x P E R I fii E N T A L.Tricamphorylstibine Chloride,--Oa adding a toluene solution ofantimony trichloride to sodiuin camphor suspended in the samemedium, considerable heat was generated, and a bulky precipitatewas produced.The mixture was warmed on the water-bath andleft for a few days, after which it was treated with water, whena white precipitate of antimony oxides separated, The tolueneD 36 MORGAN, MICRLETHWAJT, AND WRITBY :solution which drained from this precipitate was distilled in steam,and the residue extracted with benzene. From the concentratedbenzene extract, a substance separated in colourless, ice-likecrystals, this separation being promoted by t.he addition of lightpetroleum. After repeated crystallisation from benzene, theproduct melted and decomposed a t 244O, although when rapidlyheated it sometimes remained unchanged a t 24'7-248O :0.1314 gave 0.2660 CO, and 0.0840 H,O.C = 55-21 : H = 7.10.0.1830 ,, 0.3706 CO, ,, 0.1116 H20. C=55*22; H=6*77.0'2235 ,, 0'0591 Sb,S,. Sb=18*85.0.2483 ,, 0'1106 AgCl. C1=11*02.C,H,,O,ClSb requires C = 55-90 ; H = 7.0 ; Sb = 18.63 ;C1=11.02 per cent.0.3120, in 25 C.C. chloroform, at ZOO, gave ~ , + 9 . 1 7 ~ , whence[a]D = 367.3'.Tricamphorylstibine chloride dissolves only sparingly in alcohol,and is insoluble in water. In acid solutions it is fairly stable, andmay be boiled with 2N-hydrochloric acid without decomposition.On warming with 2N-sodium hydroxide, the chloride was readilyhydrolysed into antimoniu and hydrochloric acids and camphor.Destructive hydrolysis occurred on warming the chloride withaqueous sodium hydrogen carbonate at 55O, and continued heatingwith dilute ammonia led to the liberation of camphor.A similardecomposition took place when the chloride was digested withalcoholic silver nitrate.Triphenylstibine Hydroxynitrute.-O.621 Gram of triphenyl-stibine chloride gave 0.419 gram of silver chloride (the calculatedamount being 0.421 gram) on warming with two molecular pro-portions of silver nitrate in alcoholic solution. The filtrate, onconcentration, furnished white crystals, which, on analysis, gavenumbers corresponding with the partial hydrolysis of the initiallyformed dinitrate. This hydrolysis was brought to a definite end-point by dissolving the white crystals in boiling water, for, oncooling, the hydroxynitrate separated in lustrous, colourless leaflets,softening at 220°, and melting to a yellow liquid a t 224-225O.When carrying out the process on a larger scale, any slightexcess of silver retained in the solution was precipitated by theaddition of sodium chloride.The presence of excess of this saltin the filtrate promoted the crystallisation of the hydroxynitrate,the precipitation, under these conditions, being almost complete :0.2691 gave 0.4932 CO, and 0.0942 H,O.0'3765 ,, 0'1461 Sb&. Sb=27*72.C = 50,OO ; H = 3.80ORGANIC DERIVATIVES OF ANTIMONY. PART I. 370.3300 gave 9.6 C.C. N, a t 2 4 O and 759 mm. N=3.19.C,8H160,NSb requires C = 50.23 ; H = 3-72 ; Sb = 27.9 ;N = 3.26 per cent.Triphenylstibine hydroxynitrate is almost insoluble in coldwater, but dissolves very readily in alcohol, giving rise to a solutionwhich can be diluted with water very considerably without anydepasition of the hydroxynitrate taking place.When reducedwith Devarda’s alloy (Al-Cu couple) in the presence of alkali, tri-phenylstibine is produced, and the whole of the nitrogen iseliminated as ammonia. An estimation of nitrogen by this methodgave 3-62, the calculated value being 3.19 per cent.Triphenylstibine hydroxysulphate was prepared by adding analcoholic solution of triphenylstibine chloride (1 mol.) to it boilingaqueous solution of silver sulphate (2 mols.). The filtrate from thesilver chloride was concentrated to remove the alcohol, when thehydroxysulphate separated in colourless nodular crystals, the solu-tion being then distinctly acid, owing to the liberation of sulphuricacid :0.2602 gave 0.0761 BaXO,. S=4.01.C3,H3,0,SSb, requires S = 3.84 per cent.The hydroxysulphate is almost insoluble in cold water ; itdissolves in cold concentrated sulphuric acid, and remains insolution after considerable dilution with water, this increase insolubility indicating its conversion into the normal sulphate.Triphenylstibine hydroxysulphate melts and decomposes at 252O.Triphenylstibine hydroxgchloride was produced by adding analcoholic solution of triphenylstibine chloride to a large volume ofboiling water and evaporating until crystallisation began. Thecrystalline deposit, when dried and dissolved in benzene, separatedfrom this solvent in transparent, lustrous, colourless spicules,melting at 218O :0.2982 gave 0.1240 Sb,S3. Sb = 29.70.Cl,H1,OCISb requires Sb = 29.73 per cent.The authors desire to express their thanks to the Governmentgrant, which has Grant Committee of the Royal Society forpartly defrayed the expenses of this investigation.ROYAL COLLEGE OF SCIENCE, LONDON,~ O U T H KENSINGTON, S. W

ISSN:0368-1645    

DOI:10.1039/CT9109700034

出版商:RSC    

年代:1910

数据来源: RSC

摘要:

35 LAPWORTH AND WECHSLER : EXPERIMESTS ONV.-Expeyiments on Substituted AllenecarboxylicAcids. Pwt I.By ARTHUR LAPWORTH and ELKAN WECRSLER.SINCE the appearance of Thiele's papers on the conjugation ofunsaturated linkings, an increasing amount of attention has beenpaid to the question of the mutual influence of points of un-saturation within the molecule, and to the manner in which thisinfluence varies with the relative disposition of these centres ofactivity.Thiele has pointed out that the stability of the conjugatedsystem of atoms, X:Y:Z:W, is, as a rule, much greater than thatof isomeric systems in which the ethylenic and single linkings arenot arranged alternately. Such a system therefore has anabnormally small residual affinity, and abnormalities in chemicaland physical behaviour are naturally associated with the presenceof this structure.It would appear, a, priori, not improbable thatthe system X:Y:Z represents that with the greatest residual affinity;it might therefore be anticipated that any abnormalities displayedby substances containing it would, for the most part, be opposite insense to those shown by compounds containing the conjugatedsystem ; the resulting reactivity of the complex is doubtless thereason why so few allene derivatives have as yet been isolated, andis the most obvious explanation of the circumstance. Instabilitymight be expected to demonstrate itself in isomeric change of the sub-stance a t the moment of its formation into an acetylene derivative,or into the isomeric compound with the bonds in the conjugatedposition, where this is possible, o r by the rapid absorption of wateror other available reagent.The great activity of the ketensR,C:C:O is" suggestive in connexion with this point. I n order thatan allene derivative should possess a comparatively high degree ofstability, it seemed desirable that isomeric change by the migrationof double linkings should, as far as possible, be obviated, and,further, that the residual affinity of the complex should be made aslow as possible by associating each of the ethylenic linkings withanother centre of unsaturation, so as to introduce the effect ofconjugation. Thus it was to be anticipated that the systemC:C*C:C:C would have a degree of permanence intermediate betweenthat of a conjugated and a simple allene system.Some of the effects of conjugation are noticed when an aromaticnucleus or it carbonyl group is directly attached to two doublSUBSTITUTED ALLENECARBOXYLIC ACIDS.PART I. 39linked atoms, and a quite definite degree of stability might beanticipated in the case of an allene derivative,X>c: Y c : c<r,in which X, Y, W, Z are all either aromatic nuclei or carbonylgroups.With the view of ascertaining how far these extensions of theconceptions of Thiele would apply to such a case, it was decidedto attempt the preparation of a substance of this type. Such asubstance possesses an interest which is enhanced by the fact. thatits molecule is built on one of the types shown by van’t Hoffto be theoretically capable of exhibiting the phenomenon ofenantiomorphous isomerism associated with optical activity, inspite of the circumstance that no asymmetric atom in the strictsense is present.The latter property, i t may be pointed out, is notrestricted to the case in which the four groups X, Y, W, and Zare all different, but requires only the condition that X is notidentical with Y, and W is not the same as Z.The first substance which the authors sought to prepare wasay-diphenyl-y-1-naphthylallene-a-carboxylic acid,C ,,,H7-CPh:C :CPh*CO,H,in which all of those conditions are realised. The method adoptedwas to proceed from the ester of 8-benzoyl-a-phenylpropionic acid,CH2Bz*CHPh*C02Et. This was allowed to react with magnesiuma-naphthyl bromide, and, under the conditions finally imposed, gavethe lactone:C,,H7*$!Ph*CH,*~HPh0- co *I n the next stage of the process, the lactone was heated withphosphorus pentachloride on the water-bath, and the productpoured into absolute alcohol in the anticipation that the chloro-ester would thus be produced, but it was noticed that during thistreatment much hydrogen chloride was evolved, indicating thateither an unsaturated compound was in process of formation, orthat replacement of hydrogen by chlorine was taking place, butthe product, however, behaved as a saturated compound.Thegummy ester yielded no crystalline material, even after boiling withtertiary bases with the object of removing the hydrogen chloride,but finalIy it was discovered that, by using rather more than twomolecular proportions of phosphorus pentachloride, the product,treated as indicated above, gave a moderately good yield of acrystalline ester, free from chlorine.The new substance was for a long time thought to be theunsaturated ester, C,,H,*CPh:CEC*CHPh*CO,Et, formed by th40 LAPWORTH AND WECHSLER : EXPERIMESTS ONremoval of the elements of hydrogen chloride from the chloro-esterabove depicted, but the analyses of the pure compound and allits derivatives gave numbers for the hydrogen content which weredecidedly too low, and the analytical evidence shows that themolecules contain two hydrogen atoms less than required by sub-stances directly derived from one having the above formula.The phosphorus pentachloride had therefore replaced hydrogenas well as oxygen by chlorine, and doubtless a t the a-position withrespect to the carbonyl group, so that the necessity for using a tleast two molecular proportions of this agent was accounted for.*I n view of the concordance of all the analytical results and inspite of certain abnormal properties of some of the derivatives,we have no hesitation in affirming our view that the crystallineester has a formula containing two hydrogen atoms less than theDumber shown in the above structure, and may be regarded asbeing formed by the removal of two molecules of hydrogen chloridefrom a dichloro-ester or an unsaturated monochloro-ester.For a long time the authors were convinced that they had todeal here with phenyldinaphthylallenecarboxylic acid, with thesynthesis of which they had concerned themselves, but in view of apaper by Vorlander and Siebert (Ber., 1906, 39, 1024), to whichtheir attention was afterwards directed, their confidence is notcomplete. The communication referred to contains an accountof tetraphenylallene, which is formed, instead of tetraphenylacetone.when barium diphenylacetate is heated; the ease with which theallene grouping is formed in this instance illustrates again, in aclear manner, the effect of the aromatic nucleus from the point ofview discussed in the previous pages.Tetraphenylallene, like someof the unsaturated compounds, but unlike the arcid described inthe present paper, is stable towards permanganate (in acetonesolution), but is slowly oxidised by chromic acid; on treatmentwith acids, it yields an isomeric hydrocarbon, in which the allenestructure is apparently not present.Further the original hydro-carbon on bromination yields a monobromo-derivative of theisomeric hydrocarbon.Having regard to the characters and mode of formation of allthe substances here described and the work of Vorlander andSiebert, the most probable view seems to be that the acid itselfhas the allene structure, but that its lactone and the bromo-* The direct replacement of hydrogen by chlorine when phosphorus pentachlorideis used a t a temperature a t 100" is certainly unusual. Autenrieth, hqwever, foundthat anisole was chlorinated by this agent a t 30-70" (Arch.Phnrm., 1895,233, 31),and Titherley and Hicks noticed that phosphorus pentachloride replaces hydrogenby chlorine when it is heated with phenylbenzometoxazine in chloroform solutionat 60" (Trans., 1909, 95, 912)SUBSTITUTED ALLENECARBOXY LIC ACIDS. PART I. 41derivative are perhaps genetically related to the isonieride of tetra-phenylallene.The acid in question is very readily altered by treatment inalkaline solution with sodium amalgam, and although the reductionproducts have not yet been obtained in crystalline form, thisproperty indicates that the acid is probably an ap-unsaturatedacid.It very readily yields a lactone on treatment with mineral acids,so that it is probably a By-unsaturated acid. Further, the lactonethus obtained is not identical with the saturated lactone fromwhich the acid had originally been prepared, nor does it containa detectable quantity of this very characteristic substance.On the other hand, the acid and its ester only absorb onemolecular proportion of bromine, yielding a monobromo-lactone ;this exhibits great stability, and resists for some time the actionof hot permanganate solution.The acid unites with ether to form a very stable, crystallinesubstance, from which the ether is only removed with difficultyeven a t looo.The salts which the acid forms with bases, however,show little or no tendency t o crystallise; the salts with alkalisbehave as soaps, and the compounds of the acid with all the organicbases and alkaloids experimented with, piperidine excepted, didnot yield any trace of crystalline salt.Other methods applicable for resolving acids into their enantio-morphous constituents were tried, but in all cases without definiteresult.The results are presented in their present form, as the authorsare no longer able to work in collaboration.EXP ERI M E N T A L.I n preparing the P-benzoyl-a-phenylpropionitrile required forthe investigation, the process described by Hann and Lapworth(Trans., 1904, 85, 1358) was found to be tedious and wasteful ofalcohol when large quantities of material were dealt with.Aftera considerable number of experiments, the following modifiedprocess was found to give excellent results.A solution of benzyIideneacetophenone (23.4 grams) in 120 C.C.of 96 per cent.alcohol and 8.0 C.C. of glacial acetic acid was warmedto 50°, and into this was then introduced, by means of a test-tubedrawn out a t the end to a coarse capillary which rested on thebottom of the flask, a solution of potassium cyanide (15 grams) in25 C.C. of water. The temperature was maintained at 50-55O fora further fifteen minutes, when crystals of the nitrile were added,and the vessel was then cooled by a stream of cold water. Th42 LAPWORTH AND WECEISLER : EXPERIMENTS ONdeposited solid, which was obtained in nearly theoretical quantity,was purified by crystallisation from alcohol.The following modified process was used in hydrolysing thenitrile. Ten grams of the finely powdered compound were shakenwith a mixture of 50 grams of sulphuric acid and 25 grams ofwater, a t the temperature of the wa.ter-bath, until dissolved, and thewhole was subsequently allowed to remain on the bath for severalhours.After cooling, the cake of impure acid formed wasseparated, washed, and purified as before (Zoc. cit., p. 1361). Thepreparation of the ethyl ester was effected by warming the dryacid with half its weight of sulphuric acid and ten times its weightof alcohol for several hours, the liquid being then poured into alarge bulk of water, which was afterwards shaken with an equalbulk of light petroleum. After filtration, the fluids separaterapidly, and the petroleum solution, after being washed with dilutesodium carbonate solution, dried, and evaporated, deposits theester in magnificent crystals.a y-Diphenyl- y-1-napht hylb ut yrolac tone,C,,H7*$! Ph*CH,*$?HPh0-- coMagnesium a-naphthyl bromide in ethereal solution was preparedin the usual manner, and added to a solution containing onemolecular proportion of ethyl P-benzoyl-a-phenylpropionate inabout twenty times its weight of benzene.The solution was notcooled during this process, as it was found that a much better yieldof the desired product was thus obtained, owing probably to thefact that the solution, if cooled, deposited a viscid oil, which tendedto carry down with it much of the unaltered ester. At the endof the operation the solution was freed from magnesium compoundsin the usual manner, and the ether and benzene were afterwardsremoved by the use of a current of steam.The residual viscidmass was separated from the water and dissolved in hot acetone,the crystals which separated on cooling being removed a t the endof twenty-four hours, and recryst.allised fresh from a mixture ofacetone and alcohol, and finally from glacial acetic acid:0.4812 gave 1.5022 CO, and 0.2443 H20.C26H2002 requires C = 85.71 ; H = 5-49 per cent.The substance is insoluble in water, only very sparingly solublein boiling methyl and ethyl alcohols, ether, or light petroleum;it is fairly soluble in carbon disulphide, and readily so inglacial acetic acid, acetone, chloroform, carbon tetrachloride, orbenzene. It separates from acetone in colourless, transparentprisms, containing acetone of crystallisation, melting at aboutC = 8 5 * 1 4 ; H = 5 .6 4 SUBSTITUTED ALLENECXRBOXYLIC ACIDS. PART I. 4390° (when rapidly heated) to a colourless liquid, from which theacetone rapidly evaporates, leaving a white, crystalline solid, which,on further heating, melts a t 166O. The substance, when obtainedby crystallisation from hot glacial acetic acid, is free from acetoneand melts a t 166O.This lact,one dissolves very slowly in boiling aqueous alkalis, butmore rapidly in the presence of alcohol. On evaporating thesolution or on adding sodium hydroxide, the sodium salt separatesas a voluminous, white, gelatinous mass. The cold aqueous solutionof the sodium salt, on addition of hydrochloric acid, deposits thehydroxy-acid as a white, amorphous precipitate; this may beextracted with ether, in which it dissolves readily.A crystallinesubstance rapidly separates when the ethereal extract is allowedto evaporate, but this, on examination, is found to be identicalwith the original lactone. Owing t o the ease with which lactoneformation takes place, it is probably not possible to isolate the freeacid in a state of purity; the substance precipitated from thesolution of the sodium salt consists, nevertheless, of the hydroxy-acid and not of the lactone, for the freshly precipitated substanceis readily soluble in dilute aqueous sodium carbonate and in ether,whereas the lactone is insoluble in the former, and but slightlysoluble in the latter.Action of Phosphorzcs Pentachloride on ay-Dipheiayl-y-1-naphthyl-but yrola c t one.On heating an equimolecular mixture of the lactone and phos-phorus pentachloride on the water-bath, the mass gradually meltsto a brownish-red liquid, and a considerable quantity of hydrogenchloride is evolved.Several experiments were made withdifferent preparations which had been recrystallised from varioussolvents and thoroughly dried, but in no case was the evolutionof hydrogen chloride affected; even on employing a cold solutionof phosphorus pentachloride in chloroform, a considerable evolutionof hydrogen chloride was observed. With the object of isolatingthe corresponding chloro-ester, a mixture of the lactone (10 grams)with phosphorus pentachloride (8 grams) was heated in the water-bath until the evolution of hydrogen chloride had entirely ceased;the resulting liquid was then poured into about 100 C.C.of absolutealcohol, and heated to boiling for about one hour. The next daythe alcoholic liquid was diluted with water, neutralised with sodiumcarbonate, and extracted with ether. A yellowish-brown, resinousoil was then obtained, which, on cooling, set to a hard, transparent,glassy mass. All attempts t o prepare a crystalline product fro44 LAPWORTH AND WECHSLER : EXPERIMENTS ONthis by treatment with solvents were unsuccessful; it wm thereforedried at looo for about ten hours, and then analysed:0.1969 gave 0.0336 AgC1. C1=4*2.c,8H2s02c~ requires c1= 8.3 per Cent.The product analysed evidently consists of a mixture of achlorinated substance and an unchlorinated substance in roughlyequal amounts.This material did not absorb bromine in thepresence of sodium acetate, nor did it decolorise an acetone solutionof potassium permanganate even on boiling.Ethyl a y-Diphenyl-y-1 -nap,hthyZaZZene-a-carboxylat e,C1,H,*CPh :C :CPh*CO,E t.The impure chloro-ester readily loses hydrochloric acid on boilingwith pyridine or quinoline; the reaction, however, takes place muchmore smoothly with the former, and it is not even necessary hoboil the mixture, heating on the water-bath for a few hours beingquite sufficient.In the first experiments, in which the chloro-ester prepared froman equimolecular mixture of lactone and phosphorus pentachloridewas employed, many fractional crystallisations were required beforepure unsaturated ester was obtained, and the yield was poor.Better results were obtained as the proportion of phosphoruspentachloride to lactone in the preparation of the chloro-ester wasincreased, and after a number of experiments had been made, inwhich these substances were employed in varying proportions, thefollowing method was finally adopted. The chloro-ester is preparedby heating the lactono (1 mol.) with phosphorus pentachloride(2 mols.), and the product of subsequent decomposition withalcohol is heated with twelve times its weight of pyridine for threehours on the water-bath, and then to boiling for a few minutes.After cooling, the liquid is mixed with about twice its volume ofether, and extracted with hydrochloric acid until the pyridine iscompletely removed.The ethereal liquid is then dried and dis-tilled, and the residue crystallised from boiling alcohol.The yield amounts to about one-half of the weight of lactoneemployed. The substance was purified by recrystallisation fromglacial acetic acid and alcohol:0.1964 gave 0.1000 H,O and 0.6191 CO,. C =85*97 ; H =5.65,C2sE2,0, requires C = 85-71 ; H = 6.1 1 per cent.C28H,,O, ,, C=86*15; H=5*64 ,,The substance is readily soluble in hot alcohol, from which itseparates almost completely on cooling in stellar aggregates ofcolourless needles, which turn yellow on heating, and melt aSUBSTITUTED ALLENECARBOXYLIC ACIDS. PART I. 45118.5O. It is readily soluble in acetone, glacial acetic acid,benzene, chloroform, or carbon tetrachloride, and sparingly so inmethyl alcohol or light petroleum. A solution of the substance inglacial acetic acid quickly discharges the coloar of bromine evenin the presence of sodium acetate.ay-Diphenyl-y-1-nuphthylallene-a-carboxylic Acid,CloH7~CPh:C:CPh*C02H.The ester (23 grams) was heated on the water-bath with amixture of 100 C.C.of N-sodium hydroxide and 100 C.C. of pyridineduring five hours. The liquid was then diluted considerably withwater, boiled until the pyridine was completely removed, cooled,and decomposed with dilute acetic acid. The new acid, whichseparates as a very voluminous, gelatinous, white precipitate, wascollected, washed, and dried on porous porcelain. The substancewas then treated with a small quantity of ether, in which it readilydissolves, but separates again almost instantly in the form of adense, crystalline mass; at the sa.me time a considerable quantityof water separates, and this always adheres to the amorphousacid, even after drying on porous porcelain for several days.Thesubstance can be purified by crystallisation from boiling ether,when it is obtained, on cooling, in the form of large, colourless,transparent, highly refractive, rhombic crystals, which containether of crystallisation. For the purification of quantities exceed-ing one gram, it is expedient to carry out the extraction in aSoxhlet apparatus, owing to the very slight solubility of thesubstance in ether.For the determination of the ether of crystallisation, a weighedquantity was heated in a vacuum in a tube immersed in boilingxylene until the weight remained constant :0.5643 lost 0.0952.0.4840 required 11.2 C.C. X/lO-sodium hydroxide for neutral-C4HIoO = 16.87.isation.Equivalent = 432.C,,Hl,0,,C4H,o0 requires C,H,dO = 16.97 per cent.Equivalent =436.In the preparation of the ether free acid for analysis, a portionof the ether-containing crystals was dissolved in ammonia, thesolution heated to expel the ether, cooled, and acidified withhydrochloric acid. The precipitated acid waa collected and driedat looo, and finally purified by crystallisation from benzene:0,2387 gave 0.7545 CO, and 0.1117 H,O. C= 86-2 ; H = 5.2.0.2474 0.7809 CO, ,, 0.1103 HZO. C=86*1; H=4.95.C&3180, requires C = 86-19 j H =4-97 per cent46 LAYWORI'H AIVD WECHSLER : EXPERIMENTS OKThe pure acid can also be readily obtained by crystallising theA portion prepared inEquivalent =ether-containing acid from boiling anisole.this manner was titrated:0.4830 required 13-4 C.C.N [ 10-sodium hydroxide.CzsHI80, requires Equivalent = 362.The acid is slightly soluble in boiling ether, but much less soin cold ether. The ether-containing crystals melt only partly whenheated rapidly, the ether evaporating, and the substance thensolidifying; on further heat.ing, the substance changes colour a tabout 180°, and melts indefinitely a t 185-193O. The acid is readilysoluble in acetone or glacial acetic acid, and fairly soluble inbenzene, chloroform, or alcohol.It is insoluble in water, butdissolves in dilute aqpeous alkalis. On adding sodium hydroxidet o a solution of the sodium salt, a white, gelatinons precipitateseparates even from very dilute solutions. The acid decolorises asolution of bromine in glacial acetic acid, and an aqueous solutionof the sodium salt reacts at once with cold potassium permanganate.360.Attempts t o Resolve the Acid.A number of attempts were made to prepare crystalline saltsof the acid with the following active bases: quinine, strychnine,brucine, narcotine, cinchonine, cocaine, coniine, aminocamphor,nicotine, and menthylamine. Mixtures of acid and base in suitableorganic solvents, such as ether, alcohol, acetone, and chloroform,under varying conditions, in no case gave any crystalline salts.In many instances crystals were deposited, but these were invariablyfound to consist either of the unchanged acid or base.An attemptwits also made to resolve the acid by treating an alcoholic solutionwith one-half an equivalent of sodium ethoxide and one-half anequivalent of coniine, and fractionally precipitating the coniinesalt by successive additions of water. The acids isolated from thevarious fractions were all found to be inactive.An attempt was also made to prepare the menthyl ester byheating the acid with menthol, and also the coniide by heatingthe ester with coniine, but, although interaction occurred, no traceof any crystalline material could be isolated from the neutralgummy products.Formation of the Ulzsaturated Bromotactone, C,,R,,O,Br,An acetic acid solution of the ester rapidly absorbs bromine,even in the presence of sodium acetatme.Titration of the ester witha standardised solution of bromine in glacial acetic acid, employinSUBSTITUTED ALLENECARBOXY LIC ACIDS, PART I. 47potassium iodide as external indicator, proved that one molecule ofester reacts with two atoms of bromine. For the preparation of thebromine compound, a solution of the ester (2 grams) in glacialacetic acid (40 c.c.) was mixed with sodium acetate (1 gram), andthen with a 10 per cent. solution of bromine in glacial acetic acid(8.16 c.c.). After some minutes, water was added, when thebromine compound separated as a white, crystalline precipitate.This was collected, washed, and dried, then twice crystallised fromboiling glacial acetic acid, washed with alcohol, and dried a t looo :0.2977 gave 0.7688 CO, and 0.1029 H,O.C = 70.43 ; H = 3.84.0.3105 ,, 0.8041 CO, ,, 0'1086 HiO. C=70*62; H=3.88.0'3340 ,, 0.8660 CO, ,, 0.1159 H20. C=70*70; H=3*80.0.2526 ,, 0.1064 AgBr. Br=17.92.C26Hli02Br (unsaturated bromolactone) requires C = 70.75 ;H = 3-85 ; Br = 18.14 per cent.*The substance is fairly soluble in boiling glacial acetic acid, fromwhich it separates on cooling in slender, colourless needles, whichmelt on heating a t 192O. It is only very sparingly soluble inalcohol, ether, or benzene, almost insoluble in light petroleum, butfairly readily soluble in boiling acetone or chloroform. It does notdecolorise a solution of bromine in glacial acetic acid or a solutionof potassium permanganate in acetone.Action of Mineral Acids on t h e CTnsaturated Carboxylic Acid.On heating a solution ,of diphenylnaphthylallenecarboxylic acidin glacial acetic acid, to which a few drops of concentrated hydro-chloric acid have been added, a white, crystalline powder separates.The mixture was heated on the water-bath until no furtherseparation took place (about one hour), the crystalline precipitatewas then collected, and crystallised from boiling glacial acetic acid :0.2375 gave 0.7474 CO, and 0.1094 H,O.C,,H,,O, requires C=86.16; H=4.97 per cent.The substance is readily soluble in acetone, glacial acetic acid,benzene, chloroform, or ethyl acetate, sparingly so in boilingalcohol, but almost insoluble in the cold.It does not decolorisean acetone solution of potassium permanganate even on boiling.It does not dissolve appreciably in boiling aqueous sodium car-bonate or sodium hydroxide, and is only very slowly attacked byboiling ethyl- or amyl-alcoholic sodium hydroxide. It is reducedon adding sodium or sodium amalgam t o the hot amyl-alcoholicsolution. I n both cases, however, all attempts to isolate aC=85.83; H=5*11.* C2,H,0,Br (byorno-ester) rcquires C z 7 1 . 3 4 ; H=4*88. Br=16*98.C%H,,O2Br (bromo-lactoue) ,, C=50'41 ; H=4'32. Br=18*0548 MORGAN AND PICKARD : PRODUCTION OF PARA-DIAZOIMIDEScrystalline substance from the reduction product were unsuccessful,and no indication could be obtained of the formation of thesaturated lactone or of the hydroxy-acid corresponding with it.Some of the expense of this work was defrayed by the aid of aGovernment grant from t-he Royal Society, for which the authorsdesire to express their thanks.GOLDSMITHS’ COLLEGE, NEW CROSS, S.E

ISSN:0368-1645    

DOI:10.1039/CT9109700038

出版商:RSC    

年代:1910

数据来源: RSC

摘要:

48 MORGAN AND PICKARD : PRODUCTION OF PARA-DIAZOIMIDESVI.-The Production of para-Diaxoimides from Alkyl-and Aryl-sulphonyl-~ara-dia~~~~es. A GeneralReaction.By GILBERT T. MORGAN and JOSEPH A. PICKARD, B.Sc., A.R.C.S.CERTAIN derivatives of pphenylenediamine give rise to diazoniumsalts, from which diazoimines or diazoimides may be produced byinternal condensation. The earliest known pdiazoimine is theexplosive phenyl-p-diazoiminobenzene, C,H,*N*C,H,*N,, discoveredby Ikuta (Annulem, 1888, 243, ZSZ), and afterwards studied byHantzsch (Ber., 1902, 35, 895). In 1904, one of us, in conjunctionwith I?. M. G. Micklethwait, obtained the first p-diazoimide fromcamphor-j?-sulphonyl-pphenylenedismine (Trans., 1905, 87, 74),and subsequently showed that benzenesulphonyl-pphenylenediamineand its homologues readily yield arylsulphonyl-p-phenylenediazo-imides (Trans., 1905, 87, 921, 1302).Although these diazoimides are moderately stable substances, yetcomparative experiments proved that they and Ikuta’s unstablediazoimine are members of the same class of diazo-compounds.This relationship was demonstrated by the preparation of a con-necting series of mono-, di-, and tri-nitrophenyl-p-phenylenediazo-imines, the stability of which increases as nitro-groups are intro-duced successively into the molecule of p-aminodiphenylamine(Trans., 1908, 93, 605).These p-diazoimines and p-diazoimides are distinguished from theo-diazoimines and o-diazoimides by their intense colour, generallyeither yellow or orange, and by their very reactive character.When treated with cold concentrated mineral acids, they re-generate the corresponding diazoniurn salts, and with phenols andaromatic amines they couple additively to form azo-derivatives.On account of these properties, some of the more readily prepareFROM ALKTL- AND ARPL-SULPHONY L-PARA-DIAMINES.49members of the group can be turned to account in the productionof azo-colouring matters ( J . Soc. Dyers, 1909, 25, 107).These results render plausible the view that the property offorming p-diazoimino-compounds is possessed by all derivatives ofp-phenylenediamine having the formula RNH*C6H,*NH2, and evenby the base itself, but more experimental evidence would berequired before it could be definitely stated that the reaction isa perfectly general one.By the experiments described in the present communication wehave endeavoured t o show that, in all probability, the reactionis general for all organic sulphonyl derivatives of pphenylene-diamine. This demonstration may be conveniently divided intothree stages.I.-Para-diazoimides Containing Arylpolysulphoql Groups.The conversion of benzene1 : 3-disulphonylbis-p-phenylenedi-amine into the corresponding bis-diazoipide has already beenaccomplished (Trans., 1905, 87, 1309), and, in the present instance,the case of benzene-1 : 3 : 5-trisulphonylter-p-phenglenediamine (I)has been examined as a typical example of an amide derived froma complex polysulphonic acid.Apart from certain practical difficulties encountered in thepreparation of the triamine, it was found that the conversion ofthis base into b enzene-1 : 3 : 5-trisulphonylter-p-phenylenediazoimide(11) is a comparatively simple matter:(1.) (11.1This result justifies the conclusion that the production of thediazoimide is independent of the number of sulphonyl groupspresent in the molecule of the aromatic aminosulphonamide.II.--Par&diazo imid es Containing Mixed A ryl-at k ylsulphorylGroups.Former experiments on the constitution of diazoimides led tothe interesting observation that o-benzenesulphonyl-o-benzylene-VOL.XCVII. fjO MORGAN AND PICKBRD : PRODUCTIOX OF PARA-DIAZOIMIDESdiamine (111) gives rise to a diazoimide (IV) of mixed type (Trans.,1906, 89, 1162):but as the substituent groups of this product differ in theirorientation from those of the p-diazoimides, we now endeavouredt o obtain a mixed aryl-alkyl derivative of the general type bystarting from toluene-w-sulphonyl-p-nitroaniiine (V).The pre-paration of this substance presented some difficulty, however, owingto the circumstance that toluene-w-sulphonyl chloride, unlike thearylsulphonyl chlorides, does not condense satisfactorily withp-nitroaniline in pyridine or boiling toluene. The addition oftriethylamine to the latter solvent was finally found to bring aboutthe desired result, the following condensation then taking placealmost quantitatively :C,H,*CH,*SO,~Cl + H*iNH*C,H,*N02 - ~ NH<S02*CH,*C6H5iN( C2H,) s/ C, H,* NO,(T. 1......................Toluene-w-sulphonyl-p-phenylenedianaine (VI), prepared by re-ducing the nitro-compound (V), when successively diazotised andtreated with aqueous sodium acetate, furnishes toluene-w-sulphonyl-p-phenylenediazoimie (VII) :(TI.1 (VII.)This substance, containing a. mixed aromatic-alkyl group, behaveslike a typical pdiazoimide; it separates in bright yellow, sparinglysoluble needles, regenerates the diazonium chloride with cold con-centrated hydrochloric acid, and couples with phenols and aromaticamines, yielding azo-derivatives.111.-Para-diazoimides Containing Alkylsulphonyi? Groups.The existence of camphor-j3-sulphonyl-p-phenylenediazoimide(Zoc. cit.) shows that the presence of an aromatic group attachedto the sulphur atom is not an essential condition for the formationof a diazoimide of this type, and accordingly we took steps toobtain diazoimino-derivatives containing the simplest alkyl-sulphonyl groupsFROM ALKYL- AND ARYL-SULPHONYL-PARA-DIAMISES.Yj 1Methionic chloride condenses readily with pnitroaniline, yield-ing met hanedisdphonyl b is-p-nit roaniline, CH2( SO2*NH*C6H,*N0,),,which, on reduction, gives rise to methanedisulphonylb is-p-phenylenediamine (VIII), an amphoteric subst.ance, yielding bothit sodium derivative and a dihydrochloride. The latter compound,when diazotised, furnishes a fairly stable bisdiazonkm chloride,the colourless soIution of which turns yellow on the addition ofaqueous sodium acetate, thus indicating the formation of a diazo-imide.Met hanediszclphoity I b is-p-phenylenediazoimide (IX) is, however,isolated only when either the dry diazonium.chloride is dustedinto concentrated aqueous sodium acetate, or when crystals of thissalt are added t o a strong solution of the diazonium compound:(VIII.)This diazoimide has the physical and chemical properties whichcharacterise the group, but is less stable than the more complexmembers. It is somewhat soluble in water, although the solubilityis considerably diminished in the dried specimens.The production of the simplest possible alkylsulphonyl-p-phenylenediazoimide has been accomplished by the followingseries of operations. Methanesulphonyl-p-nitroaniline, produced bycondensing methanesulphonyl chloride and p-nitroaniline in thepresence of triethylamine, yields, on reduction, met?mmesuZphonyZ-p-phenylenediamine (X).The diazonium chloride and sulphate ofthis base are colourless salts, which give yellow solutions of thediazoimide on treatment with sodium acetate :- -(X. 1 (XI.)Met hanesulphonyl-p-phenylenediazoimide (XI) is soluble inwater, and as it rapidly decomposes into a resinous product evenin cold aqueous solutions, its isolation in the solid state is a matterof considerable difficulty. When silver nitrite is introduced intoa solution of methanesulphonyl-p-phenylenediamine hydrochloride,silver chloride is precipitated, and the solution then contains onlythe diazoimide, which may be obtained by evaporating to drynessE 58 AIORQAN AND PICKbRI) : PRODIJCTION OF PA RA-DIAZOIMIDESin a vacuum over phosphoric oxide. Unless this evaporation iseffected very rapidly, the product darkens, and some loss of nitrogenis apparent.When sodium nitrite is used in this experiment, thefiltered solution contains molecular proportions of the diazoimideand sodium chloride. The presence of this inorganic salt seemsto increase the stability of the diazoimide, and the solution maybe evaporated to dryness in a vacuum without loss of nitrogen.With the production of the two foregoing diazoimides, containingrespectively methanesixlphonyl and methanedisulphonyl groups, thetask of demonstrating the general character of this chemical changeis completed, and the reaction may be expressed in general termsin accordance with the following symbolical scheme, where R isany alkyl, aromatic, hydroaromatic, or mixed aromatic-alkyl radicle,and x is its valency:The conversion of t.he diazonium chloride into the p-diazoimide isa reversible change, and it is of interest, in connexion with themodern theories of solution, to notice that the reaction probablyoccurs in three or more successive phases.The inverse change isbrought about, not only by mineral acids, but even by acetic acidwhen present in excess, and this result indicates that the firstphase in the direct change is the formation of a diazonium acetate:R*S0,*NH*C6H4*N,C1 + CH,*CO,Na -+R*SO,*NH*C,H,*N,- C0,-CH,,which, in the absence of any considerable excess of free acetic acid,undergoes hydrolysis, the extent to which this second phase occursbeing determined by the concentration of the acetic acid :R-SO2*NH*C,H4*N2*CO,*CH3R*SO;NH-C6H;N2*OH + CH,*CO,H.The hypothetical diazo-hydroxide thus produced is an amphotericsubstance, having an acidic substituent, R*SO,*NH, and a basicgroup, N,*OH, each of which probably exists in solution in associa-tion with a certain characteristic number of water molecules.Butas the sodium acetate solution invariably assumes the yellow colourof the p-diazoimide, one must suppose that a certain proportion ofthis substance is actually formed in solution by the internal con-densation of the hydrated diazo-hydroxide :R*SO,*NH*C,H,*N,*OHThis mode of representing the final phase of the condensation isR*S02*N*C,H,*N2 + (x + y + 1)H20.I--.---.I xH20 YH2FROM ALKYL- AND ARYL-EULPHONYL-PARA-DIAMISES. 53probably true only when R is a complex group of comparativelyhigh molecular weight. In these cases, the precipitation of thepdiazoimide is immediate and practically complete, but when R iga simple alkyl group of low molecular weight, the p-diazoimideexhibits a tendency to remain in solution, probably in the hydratedform :R*SO,*N*C H *N,,zH20.4 1Methanesulphonyl-p-phenylenediazoimide is obtained only onevaporating its solution to dryness under greatly reduced pressure,and methanedisulphonylbis-p-phenylenediazoimide in the moist con-dition dissolves fairly readily in cold water, and becomes much lesssoluble only after desiccation over phosphoric oxide.Further evidence for the existence of hydrated forms of thediazoimides was obtained by F.M. G. Micklethwait, J. M. Hird,and one of us in the study of the arylsulphonylbenzidines. Inthese bases, where the acid and basic substituents are separated bytwo aromatic nuclei, the diazoimide separates with two molecularproportions of water, and has the general formula:R*S02*N*C6H4*C6H4*Nz,2Hz01 I(Trans., 1907, 91, 1509; 1908, 93, 615).The closely allied aromatic diazo-oxides exhibit the samephenomenon; the more complex members of the series separate inanhydrous forms, as, for example, dinitrophenylenediazo-oxide,O*C6H2(N0,),*N2, whereas Hantzsch and Davidson (Bey., 1896,I I29, 1530) found that the simplest member, p-phenylenediazo-oxide,separates with four molecules of water, and can be representedby the formula O*C6H4~N,,4Hz0.In connexion with the existence of hydrated forms of diazo-imines, attention should be directed to an interesting observationmade by the chemists of the Badische Anilin- und Soda-Fabrik(D.R.-P.205037). Acetyl-p-phenylenediamine was diazotised inhydrochloric acid, and the acetyldiazonium chloride hydrolysed bygently heating the solution. The dissolved product was then foundto couple with alkaline B-naphthol much less rapidly than theunhydrolysed acetyl-p-aminobenzenediazonium chloride. Altlioughthe product of hydrolysis was not isolated, it seems probable thatit consists of it hydrated form of p-diazoiminobenzene,1- INH0C6H4*N2,zHzO.1 54 MORGAN AND PICKARD : PRODUCTION OF PARA-DIAZOIMIDESEXPERIMENTAL.I.-Benzene-1 : 3 : 5-trisuZphonp?ter-p-phen~lenediazoim'de.A mixture of benzene-1 : 3 : 5-trisulphonyl chloride (1 mol.) andp-nitroaniline (3 mols.) was boiled in dry pyridine for severalhours, the solvent then removed by evaporation, and the residue,after extraction with water, was boiled with aqueous sodiumcarbonate.The alkaline filtrate, when acidified with dilute hydro-chloric acid, yielded a yellowish-white precipitate, which, afterrepeated crystallisation from methyl alcohol, separated as a white,crystalline powder, and melted at 278O :0.2202 gave 23.6 C.C. N, at 17O and 758.2 mm.0*2100 ,, 0.2162 BaSO,. S=14-15.Benzene-l : 3 : 5-trisulphonylter-p-nitroa?ziline,N=12*58.C2,H,,0,,N6S3 requires N = 12-40 ; s = 14.19 per cent.C6H3(S02*NH0C,H,*N0,),,is a distinctly acidic substance, and on treatment with alcoholicpotash gives a potassium derivative, separating in small, yellowcrystals.When diluted with an equal volume of water, the methyl-alcoholic mother liquors of the preceding compound deposited abrown oil, which gracually solidified t o radiating clusters of stout,yellow prisms.This product, when washed with cold ethyl acetateand crystallised from alcohol, was obtained in odourless, yellowcrystals? insoluble in water or dilute hydrochloric acid, butdissolving in cold aqueous sodium hydroxide to a yellow solutionhaving a strong odour of pyridine :0.1288 gave 12.8 C.C. N, at 2 4 O and 763 mm.This result, which agrees with the formula :N=11*19.C,3Hi,0,1N'5S3 requires N = 11'01 per cent.C6H3( S02*NH * C,H, NO2),* S03H,C,H,N,shows that a certain amount of the chloride,C,H,( S0,*NI<*C6H,oN0,),* So2c1,arises from the interaction of p-nitroaniline and benzene-1 : 3 : 5-tri-sulphonyl chloride, the subsequent action of water in the presenceof pyridine leading to the production of the above pyridine salt.A comparative experiment made with the other nitroanilinesshowed that the ortho-base gave only a small yield of crystallineproduct with benzene1 : 3 : 5-trisulphonyl chloride, whereas themeta-base reacted readily and quantitatively in boiling pyridineto form the following compound.Benzene-l : 3 : 5-trisdphonylter-m-nitroaniZine,C6H3 ( S 0, NH - C,H,*N 0,) 3separated from pyridine by removing the latter with cold dilutehydrochloric acid, was crystallised from 50 per cent.acetic acid,and thus obtained in small, white needles, melting a t 199O:N=12*28. 0.2657 gave 27.4 C.C. N, a t 14O and 767.4 mm.This trisulphonamide is readily soluble in aqueous alkaliBenzene-1 : 3 : 5-t~isuZp?fionyZter-p-p?~en-yZenediamine,C,,H,,0,,N,S3 requires N = 12-40 per cent.hydroxides or glacial acetic acid.C,H3( SO,*NH*C,H,*NH,),,was produced by adding iron filings (10 grams) to benzene-1 : 3 : 5-trisulphonylter-p-nitroaniline suspended in 100 C.C. of warmwater containing 1 C.C. of glacial acetic acid, the mixture beingheated for three hours. Excess of sodium bicarbonate was added,the mixture filtered, and the filtrate acidified with acetic acid,when the triamine separated, the yield being about 50 per cent.When crystallised from water or acetone, the triamine separatedin colourless nodules, and melted a t 256O:0.1580 gave 19.5 C.C.N, at 2 3 O and 775 mm.C24H2404N4S3 requires N = 14.29 per cent.The diazo-solution from 1 gram of base, 30 C.C. of 2N-hydrochloricacid, and 20 per cent. sodium nitrite solution was treated withaqueous sodium acetate until a slight permanent precipitate wasformed. From the filtered solution, excess of sodium acetatedeposited the diazoimide as a light yellow, microcrystalline pre-cipitate, which was washed successively with cold water, alcohol,and ether. The product retained water very tenaciously, its weightbecoming constant only after prolonged drying over sulphuric acidQr phosphoric oxide :N=14*55.0.1923 gave 0.3244 CO, and 0.0502 H,O.0.19880.2011 ,, 0.2235 BaSO,.S=15.26.C = 45.99 ; H = 2-70,N=19*75. ,, 34.8 C.C. N, a t 18O and 757.3 mm.C24H1506N9S3 requires C = 46-37 ; H = 2.43 ; N = 20.32 ;S=15*46 per cent.The filtrate from the diazoimide gave a red coloration withalkaline @-naphthol, showing that the precipitation of the con-densation product was not complete even in the presence of con-siderable excess of sodium acetate.Benzene-1 1 3 : 5-trisuZplion-ylter-p-phenyZened~azoinzide,C,H,(SO,.N*C,H,*N,),,I Iwhich explodes somewhat violently a t 146O, is too insoluble to becrystallised from the ordinary organic solvents; it can be preservedfor an indefinite t'ime in the dark, although on exposure t o lightit rapidly darkens and assumes ilr purple-brown colour.Whe56 MORGAN AND PlCKARD : PRODUCTlON OF PARA-DIAZOIMIDESdissolved in cold hydrochloric acid, the diazoimide is convertedinto diazonium chloride, as may be shown by adding the dilutedsolution to alkaline &naphthol.obtained either in the preceding reaction or by triturating the diazo-imide with &naphthol in the presence of pyridine, separated fromalcohol as a dark red, crystalline powder, melting a t 265-266O :0.1060 gave 10.4 C.C. N, at 21'5O and 762 mm.C,H,,09N9S, requires N = 11.92 per cent.This azo-&naphthol dissolves in concentrated sulphuric acid toa deep red solution; its alkali salts are sparingly soluble in watercontaining alkali hydroxides, and are decomposed by dilute aceticacid.11.-Toluene- o-sulp7~onyl-p-p7~enylened~zoim~e.It was not found possible to condense p-nitroaniline and toluene-w-sulphonyl chloride in boiling toluene, and in warm pyridine thesesubstances interacted to form tarry products.The difficulty wasovercome by dissolving molecular proportions of pnitroaniline,toluene-o-sulphonyl chloride, and triethylamine in toluene, theliquids being first carefully dried over sodium. Afterboiling for two to three hours, the condensation was com-plete, and the solvent wits then removed by evaporation.The residue was extracted repeatedly with boiling aqueoussodium carbonate, and the solution filtered while hot.On cooling, the sparingly soluble orange sodium derivative,C6H,*CH,*SO,*NNa*C6H4*NO,, separated ; this was decomposed a tOo with dilute hydrochloric acid, when the toZuene-o-suZp7~onyZ-p-nitroandine, which first appeared as a pasty, yellow mass, slowlysolidified, and was crystallised from alcohol and water (1 : 4) :N=11.39.0.1452 gave 12.5 C.C.N, a t 15O and 737 mm.0.1075 ,, 0.0868 BaSO,. S=11*09.After repeated crystallisation from dilute alcohol, the sulphon-Toluene-o-szllphonyI-p-p~e?~~lenedianzie,N=9.82.C13Hl,04N,S requires N = 9.60 and S = 10.96 per cent.amide melts at 155O.C6H6* CH,* SO,*NH*C6H,*NH,,was produced in almost quantitative yield by reducing the pre-ceding nitro-compound (4 grams) with iron filings (5 grams) in100 C.C.of 4 per cent. acetic acid. After boiling for thirty minutes,the mixture, rendered alkaline with sodium carbonate, was filtered,when the filtrate deposited white crystals of the base, a furtherquantity being extracted from the residue with alcohol. AfteFROM ALKYL- AND ARY L-SULPHONYL-PARA-DIAMINES, 57crystallisation from this solvent, the base was obtained in acicularprisms, melting at 121-122O :0-1241 gave 11.8 C.C. N, a t 16O and 753.5 mm.C,,H,,O,N,S requires N = 10.69 per cent.This diamine was diazotised in 6 per cent. hydrochloric acid,and the filtered solution treated with excess of aqueous sodiumacetate. The liquid became yellow, and subsequently depositedlemon-yellow needles of the diazoimide. These were washed suc-cessively with cold water, alcohol, and ether.The aqueous filtrategave only a slight coloration with 8-naphthol, showing that theprecipitation of diazoimide was complete. The product, a typicaldiazoimide, darkened a t 136O, and decomposed violently a t 1410 :0.1463 gave 0.3061 CO, and 0.0567 H20. C = 57.05 ; H =4.31.0.11360.1279 ,, 0.1056 BaSO,. S=11*33.N = 11.20.,, 15.9 C.C. N, at 18O and 735 mm. N=15.63.C,,H,,O,N,S requires C =57.14 ; H = 4.03 ; N = 15.38 ;S = 11.73 per cent.C6H,*CH2*SO,=N*C,H,*N2,like the arylsulphonyldiazoimides, is practically insoluble in theordinary solvents, but dissolves in cold hydrochloric acid, re-generating the diazonium chloride. Although stable in the dark,i t rapidly darkens on exposure to light, becoming orange, and finallydark brown.Toluene-o-swlphonyl-p-phenylenediazoirnide,I-.--.-- ITolu ene-o-sulphonyl-p-amino b enz eneazo-p-naph t hol,C6€€,*CH2* S02*NH*C6H4*N,*C,,H,*OH,prepared eit.her by triturating the diazoimide with &naphthol andpyridine, or by adding the acid solution of the diazoimide toalkaline @-naphthol, separated from alcohol as a bright red,crystalline powder, melting at 211O :0.2110 gave 19 C.C.N, a t 12O and 763 mm. N = 10.68.C23H1903N3S requires N= 10.10 per cent.[With F. M. G. MICKLETHWAIT.]III.--Methanedisulphonylbis-p-phenylertediazoimide.When methionic chloride * (1 mol.) and p-nitroaniline (2 mols.)were mixed in dry toluene, a vigorous reaction took place, andthe condensation was completed by warming the mixture for a fewminutes. After removing the toluene by evaporation, the residue+ For the specimen of methionic chloride employed in the following experiments,we are indebted t o the liberality of the Farbenfabriken vormals Friedrich Bayer& co58 MORGAN AND PICKARD : PRODUCTION OF PARA-DIAZOIMIDESwas extracted successively with boiling water to removep-nitroaniline, and with aqueous sodium carbonate to dissolvethe met Banedisdphonyl b is-p-nitroaniline, CH,( SO,*NH*C,H,-NO,),.The latter substance was then crystallised from alcohol, when itseparated in transparent, light yellow prisms, melting and decom-posing at 248-249O:0.1607 gave 19.0 C.C.N, a t 25O and 774 mm.0.1871 ,, 0.2216 BaSO,. S=16.27.C,H120,N4S2 requires N = 13.48 ; S = 15.41 per cent.Met hanedisdphonylbis-p-nitroaniline decomposes both soluble andinsoluble carbonates ; its sodium derivative is somewhat sparinglysoluble in cold water.N=13*54.Net hanedisulphonyl b is-p-pheny Zenediamine,CH,(SO,*NH*C,H,*NH,),,was prepared by reducing the preceding compound with iron filingsand 4 per cent. acetic acid.The reduction was completed after twohours' heating, and the mixture, rendered alkaline with sodiumcarbonate, was rapidly filtered. The base, which had passed intothe filtrate in the form of its sodium derivative, was precipitatedwith dilute acetic acid, and crystallised from ethyl acetate, whenit separated in small, colourless needles, melting a t 227O:N=15*72. 0.1505 gave 21.0 C.C. N2 at 26O and 771 mm.0.2036 ,, 0-2691 BaSO,.S=18-15.C,H1,O4N4S, requires N = 15-73 ; S = 17.97 per cent.Methanedisulphonylbis-pphenylenediamine is an amphoteric sub-stance, exhibiting in a remarkable degree the dual properties ofbase and acid. As a base, it forms a dihydrochloride soluble inwater, and dissolving more sparingly in alcohol. As an acid, itdecomposes calcium carbonate and other insoluble carbonates, andforms soluble sodium and even ammonium derivatives.Methanedisulphoizylbis-p-aminob enzenediasonium chloride,CH,( @O2*NH*C,H,*N2C1),.-The foregoing base was suspended in alcohol, concentrated hydro-chloric acid added, and the resulting solution rapidly filtered.Amy1 nitrite was then added. when the diazonium. chloride rapidlyseparated as a light grey, crystalline precipitate, insoluble inalcohol :0.1114 gave 17.6 C.C.N, at 2 2 O and 769 mm.0'2090 ,, 0.1276 AgCl. C1=15.10.Cl3Hl2O4N,C1,S2 requires N = 18.60 ; C1= 15.74 per cent.When prepared in the dark, the diazonium chIoride is almostcolourless, but when exposed t o light in contact with its motherN=18*10FROM ALKYL- AND ARYL-SULPHONY L-PAKA-DIAMINES. 59liqyor, the salt frequently assumes a reddish-brown colour, andbecomes almost insoluble in water.The corresponding diazonium sulphate was produced by diazo-tising the foregoing diamine in dilute sulphuric acid, and, beingless soluble than the diazonium chloride, it was precipitated byalcohol from its aqueous solution, These salts, when dissolved inwater, have an acid reaction.Methanedisulphonylbis-p-anzinob enzenediazonium nit rate,CH,(S0,*NH*C6H,*N2*N03),,and the following substance were obtained in unsuccessful attemptsto prepare the bisdiazoimide.The nitrate was formed by addingsilver nitrate to an aqueous solution of the foregoing diazoniumchloride, and concentrating the filtrate from the silver chlorideover potassium hydroxide under 5 mm. pressure. It separated inpale yellow needles, which, when dry, were somewhat sparinglysoluble in cold water, and decomposed violently a t 156-160°:0.0898 gave 17-7 C.C. N, a t 22O and 766 mm.0.1368 ,, 0.1580 CO, and 0.0365 H,O. C=31.50; H=2*96.C13Hl,01,N8$2 requires C = 30.95 ; H = 2-38 ; N = 22-22 per cent.A carefully purified portion of methanedisulphonylbis-p-phenylenediamine was dissolved in glacial acetic acid, and diazo-tised with ethyl nitrite.The filtered solution, when graduallydiluted with alcohol and ether, deposited a pale yellow, unstablesubstance, which, when rapidly collected and dried, gave analyticaldata corresponding with the diazoamine :N=22*51.0.1134 gave 0.1722 CO, and 0.0452 H,O.0.1324 ,, 22.0 C.C. N, a t l'i0 and 772 mm. N=19*60.C13H130,N,S2 requires C =42.50 ; H= 3.54 ; N = 19.07 per cent.Another portion of the base was dissolved in glacial acetic acid,diazotised with ethyl nitrite, and the solution evaporated to drynessat the ordinary temperature in a vacuum desiccator. The residue,a dark red substance resembling shellac, contained no combinedacetic acid, and only 15-38 per cent.of nitrogen, shomwing t.hat aportion of the diazo-nitrogen had been eliminated duringevaporation. Its composition approximated to that of a diazo-oxide or azo-phenol produced by internal condensation.The colourless aqueous solutions of the bisdiazonium salts, whentreated with excess of sodium acetate, assumed an intense yellowcolour. indicating the formation of the bisdiazoimide, but the sub-stance was not precipitated. After many fruitless attempts t oisolate the bisdiazoimide, it was found possible to precipikab ifiC=41.41; H=4*4360 MORGAN AND PICKAKD : PRODUCTION OF PARA-DIAZOIMIDESeither by adding the solid bisdiazonium chloride to concentratedaqueous sodium acetate or by introducing crystals of the lattersalt into strong aqueous solutions of the bisdiazonium chloride.Thelatter procedure is preferable, because by the former the productpasses through a viscid phase which is obviated by the secondmethod of mixing. The bisdiazoimide separates as an orange-yellow, microcrystalline mass, which, when once segregated, isremarkably insoluble in cold water, and can accordingly bethoroughly washed without serious loss, first with water, and thensuccessively with ether and light petroleum :0.1042 gave 0.1576 CO, and 0.0368 H20. C= 41.26 ; H= 3-87.0.1272 ,, 0.1926 CO, ,, 0'0414 H,O. C=41*29; H=3.61.0.11250.1712 ,, 0.2138 BaSO,. S=17.15.,, 21.9 C.C. N, at 19.5O and 761 mm. N=22.43.Cl3HlOO4N6S2 requires C =41*26 ; H = 2.64 ; N= 22.22 ;S=16#93 per cent.Met hanedisulphon yl b is-p-p h enylenediazoimide,CH,(SO2*N*C,H,*N2)2,1- Idecomposes violently a t 120°, and darkens rapidly on exposure tolight.When triturated with 8-naphthol in the presence ofpyridine, it combined additively with the former, giving rise tomet hanedisulphonyl b is-p-amino b enz eneaso-P-napJb t ho I ,CH,(S02*NH*C,H,*N,~Cl,H,~OH),,which was also produced in the form of its sparingly soluble darkred alkali derivative on adding the bisdiazonium chloride to alkalineP-napht-hol. The free azo-&naphthol is a red powder, varying con-siderably in tint, and only sparingly soluble in the ordinary organicmedia; it melts at 272O:0.1304 gave 14.4 C.C. N, a t 1 5 O and 752 mm. N=12*80.C13H2,0,N,S2 requires N = 12-61 per cent.IV.-Metlianesulphonyl- p-phenylenediazoiniide.The methanesulphonyl chloride employed in the following experi-ments was either purchased or prepared from methyl sulphate,this ester being converted into methyl thiocyanate by means ofaqueous potassium thiocyanate.Methanesulphonic acid was thenproduced by oxidising methyl thiocyanate with nitric acid, andfreed from water as completely as possible by repeated evaporation.Treatment with phosphorus pentachloride led to the formation ofa mixture of phosphoryl chloride and methanesulphonyl chloride,which was fractionated under the ordinary and also under reducedpressure. All the specimens of methanesulphonyl chloride employedcontained appreciable amounts of phosphorus compounds, whichFROM ALKYL- AND ARYL-SIJLPHONPI;-PARA-DIAMINES 6 1fortunately, did not interfere seriously with the following con-densation.Methanesulphonyl-p-nitroanaine, CH,*S'OZ*NH*C,H,*NO2.Ten grams of methanesulphonyl chloride were added to a warmtoluene solution of p-nitroaniline (10.5 grams) and triethylamine(10 grams); a heavy, oily layer separated, and rings of triethyl-amine hydrochloride were projected from the flask. After boilingfor fifteen minutes, the solvent was evaporated off, and the residueextracted with excess of aqueous sodium carbonate until only aslight amount of tar remained undissolved.The solution wasthoroughly cooled, and the crystallised p-nitroaniline separated ;the filtrate acidified with hydrochloric acid gave an almost colour-less precipitate of methanesulphonyl-p-nitroaniline, the yield beingabout 9 to 10 grams.Very little condensation occurs in the absence of triethylamine,and in this respect methanesulphonyl chloride differs considerablyfrom methionic chloride, which reacts energetically with p-nitro-aniline, even in the absence of any condensing agent.Methanesulphonyl-p-nitroaniline crystallises readily from dilutealcohol in pale yellow needles or transparent, amber-coloured prisms ;it melts a t 186O:0.1212 gave 13.9 C.C.N, a t 20° and 756 mm.C,H8O4NZS requires N = 12.96 per cent.This nitro-compound dissolves readily in aqueous sodium car-bonate or ammonia, and is slightly soluble in water; it is notreprecipitated from its alkaline solutions by acetic acid, but onlyby mineral acids.N=13*06.Methanesulpl~onyZ-p-phenylenylene&am&ne, CH,*S0,*NH*C,H4*NHz.The foregoing nitro-compound could not be reduced satisfactorilyby iron and dilute acetic acid, zinc and ammonia, aluminiumamalgam, stannous chloride, or ammonium sulphide.The bestresult was obtained by dissolving 2 grams of nitro-compound in20 C.C. of 50 per cent. alcohol, containing 0.5 gram of ammoniumchloride. On adding excess of zinc dust to the warm solution,reduction occurred, and was completed by boiling for a short time.The alcoholic filtrate was rapidly evaporated to dryness, and theresidue extracted with benzene. When crystallised from thissolvent, the base separated in colourless needles, melting a t 122O :0.1327 gave 18.1 C.C. N, a t 20° and 772 mm.0.1588 ,, 0-2036 BaSO,. S= 17.60.N=15*86.C7H,,0zNzS requires N = 15.05 ; S = 17.20 per cent62 MORGAN AND PICKARD : PRODUCTION OF DIAzOIMIDES.The hydrochloride of methanesulphonyl-p-phenylenediamine,which is readily soluble in water or alcohol, separates in colourlessleaflets, melting a t 223O:0.1192 gave 12.7 C.C.N, a t 21'5O and 761 mm.C,H;,O,N,S,HCl requires N = 12.53 per cent.The sulphate is somewhat less soluble in water, and is precipitatedby alcohol from its aqueous solution. The diazonium chlorideseparated in colourless plates on adding successively ethyl nitriteand dry ether to an alcoholic solution of the hydrochloride; itrapidly becomes brown and viscid on exposure to the atmosphere.The diazonium sulphate was more stable than the diazoniumchloride, and separated in colourless crystals on adding ethylnitrite aad ether successively to a solution of the sulphate in glacialacetic acid.These diazonium salts, when added to strong aqueous solutionsof sodium acetate, gave either a resinous product or an intenselyyellow solution, the result depending on the concentration of thesodium acetate.Only in two isolated cases was a, yellow, crystallineproduct obtained in this way. This compound decomposed violentlyon gently warming, whereas the resinous product burnt quietly.The former of these substances was evidently the diazoimide, aswas proved by coupling it with B-naphthol.The diazoimide was obtained in the solid condition by mixingcold aqueous solutions of methanesulphonyl-p-phenylenediaminehydrochloride and sodium nitrite, taking these salts in accuratelyweighed molecular proportions.The solution was rapidly filteredfour or five times, and when of a clear yellow colour was evaporateda t the ordinary temperature in a vacuum desiccator over phosphoricoxide and potassium hydroxide. An orangeyellow residue wasobtained, consisting of the diazoimide (decomposition point 150O)and sodium chloride in approximately molecular proportions. Themixture was ground up thoroughly, and the sodium chlorideestimated as sodium sulphate after heating with pure concentratedsulphuric acid. After making allowance for the proportion ofsodium chloride present, the following results were obtained :N=12*11.0.1765 gave 0.2668 CO, and 0.0646 H,O. C = 41-23 ; H = 4.06.0.1353C7H70,N,S requires C = 42.64 ; H = 3.65 ; N = 21.31 per cent.The diazotisation was now repeated, using silver nitrite insteadof sodium nitrite, the dry salt being thoroughly triturated withthe aqueous solution of methanesulphonyl-pphenylenediaminehydrochloride. After filtering off the silver chloride, the clearyellow solution contained only the methanesulphonyl-p-phenylene-diazoimide ; the substance appeared, however, to be less stable than,, 25.5 C.C. N, a t 20° and 772 mm. N=21*90THE ACTION OF HYDROGEN DIOXIDE ON THIOCARBAMIDES. 63in the presence of sodium chloride, and showed signs of losing someof its diazo-nitrogen. The final residue was shown to containdiazoimide by coupling with P-naphthol in pyridine solution. Abright red azo-P-napht-hol was produced, which melted a t 244-245*,and was identical with rnethanesulphonyl-p-ar&ohenzeneazo-P-naphthol, prepared by coupling methanesulphonyl-p-aminobenzene-diazoniurn chloride with alkaline &naphthol. In the latter pre-paration the azo-j?-naphthol was produced in the form of its solublealkali derivative, and was precipitated by dilute acetic acid. Thefree azo-j?-naphthol was almost insoluble in alcohol, but crystallisedreadily from glacial acetic acid in red, glossy, filamentous needles;it melted a t 244-246*, and dissolved in concentrated sulphuricacid to a deep red solution:0.1147 gave 12.3 C.C. N, at 19O and 758 mm. N=12*30.C,7H,,03N3S requires N = 12.31 per cent.We desire t o express our thanks to the Government Grant Com-mittee of the Royal Society and the Research Fund Committee ofthe Chemical Society for grants which have partly defrayed theexpenses of this investigation.ROYAL COLLEGE OF SCIENCE, LONDON.SOUTH KENSINGTON, S. W

ISSN:0368-1645    

DOI:10.1039/CT9109700048

出版商:RSC    

年代:1910

数据来源: RSC

摘要:

THE ACTION OF HYDROGEN DIOXIDE ON THIOCARBAMIDES. 63VIT -The Action of Hydrogeia Dioxide oia Thio-carbamides.By EDWARD DE BARRY BARNETT.THE action of hydrogen dioxide on thiocarbamide in oxalic acidsolution was investigated by Storch (Monatsh., 1890, 11, 452),who obtained a salt of the disulphide, NH:C(NH,)*S*S*C(NH,):NH,but was unable to isolate the free base. Storch also obtainedsalts of this disulphide by oxidising thiocarbamide with nitric acidand other acid oxidising agents. Evidently in this case the thio-carbamide reacts in the pseudo-form. It occurred to the authorto investigate the action of hydrogen dioxide on thiocarbamide inneutral or alkaline solution, as it seemed possible that in thesecircumstances it might react as a symmetrical diamide.Oxidation of Thiocar bamide.Fifteen grams of finely-powdered thiocarbamide were slowlyadded during an hour to 230 C.C.of 6 per cent. aqueous hydroge64 RARNETT: THE ACTION OFdioxide, the whole being cooled by surrounding with ice. Thethiocarbamide dissolved, and after an hour the oxidation productcrystallised in colourless needles. These were extracted withboiling alcohol to remove any unchanged thiocarbamide, and weredried in a vacuum over concentrated sulphuric acid. The yieldwits 9 grams:0.3400 gave 0.1387 CO, and 0.1103 H20. C = 11.13 ; H = 3.62.0.5125 ,, 0'2077 CO, ,, 0'1850 H20. cT=11*05; H=3.82.0.1465 ,, 0-3225 BaSO,. S=30*17.0.2077 N=26*2.0.0736, in 20.10 water, gave A t = - 0'072*.,, 45.4 C.C. N2 (moist) a t 1 2 O and 762 mrn.M.W.= 96.CH,0,N2S requires C = 11.1 1 ; H = 3-70 ; S = 29-63 ;N=25.9 per cent. M.W.=108.From the analytical results, it is clear that Storch's disulphideis not formed under these conditions, and the molecular weightdetermination shows that condensation does not take place, butthat each molecule of thiocarbamide takes up two atoms ofoxygen. The compound has faintly acidic properties, and it doesnot reduce metallic salts, as would be probable if it had thestructure OH=NH*CS*NH*OH. Further, the ease with which itevolves sulphur dioxide on heating points to the oxygen beingin direct union with the sulphur. It was also found that carbamidedoes not yieldl a similar compound.It would appear, therefore, that its constitution is to be repre-sented as NH:C(NH,)*SO,H, and, in order to confirm this,attempts were made to obtain a similar compound from thio-benzamide and thioacetamide, but these were not successful, amixture of the amide and the unchanged thioamide being theinvariable result.A minoiminomet hanesulphinic acid melts and decomposes at 144O.It is fairly soluble in cold water, to which it imparts a faintlyacid reaction, but is insoluble in organic solvents.It decomposesslowly a t looo and rapidly a t llOo, sulphur dioxide being evolved.It is rapidly decomposed by boiling water, and from the solutionthus obtained chloroplatinic acid precipitates an orange-red salt.This is probably formamidine platinichloride, but it has not beenpossible to obtain it in sufficient quantity for analysis. Amino-iminome t hanesulp hinic acid inst an tly reduces acid permanganatein the cold, and quantitative experiments showed that in doingso it takes up one atom of oxygen.Attempts to isolate thisoxidation product failed. On treatment with excess of per-manganate, hydrogen cyanide is evolved. It was not found possibleto prepare an acetyl derivative by treatment with acetyl chlorideHYDROQEN DIOXIDE ON THIOCARBAMIDES. 65The investigation was extended to some of the derivatives ofthiocarbamide in the hope of obtaining similar compounds whichwould yield more definite decomposition products.Oxidation of Allylthiocarbamide.Ten grams of finely-powdered allylthiocarbamide were graduallyadded during an hour to 110 C.C. of a 6 per cent.aqueous solutionof hydrogen dioxide a t Oo. The clear solution was evaporatedalmost to dryness in a vacuum over concentrated sulphuric acid,and the oily residue extracted with warm alcohol. The filteredsolution was evaporated in a vacuum a t the ordinary temperature,and the resulting colourless crystals were dried over concentratedsulphuric acid :0.2449 gave 0.2626 CO, and 0.1206 H,O.0.2558 ,, 0.3556 BaSO,. S=19*09.This allyb derivativeC = 29.24 ; H = 5.47.0.2615 ,, 0.2782 CO, ,, 0.1253 H20. C=29*01; H=5.32.C4HiO2N2S,H20 requires C = 28.92 ; H = 6.02 ; S = 19-27 per cent.[ C3H,* N :C (NH,) S0,H or C3H,= NH C ( :NH)- S02H]tends to form a viscous oil, which only crystallises with the utmostdifficulty, and hence was not obtained in a state of purity.Itmelts and decomposes a t 165-170°.Attempts were also made to prepare the substance in the purecondition by oxidising allylthiocarbamide in acetone solution withthe calculated amount of aqueous 30 per cent. hydrogen dioxide.On evaporating the acetone in a vacuum, an oil was obtained,which did not crystallise after remaining under anhydrous etherfor six weeks.All attempts to obtain a pure product by oxidising phenylthio-carbamide, either in aqueous or in acetone solution, with hydrogendioxide yielded a viscous oil which did not crystallise.The ease with which the oxidation of thiocarbamides takes placeseems to depend on the number of substituents present. Thus,with thiocarbamide itself, the action of hydrogen dioxide is violent,and must be carried out at a low temperature; with allylthio-carbamide and phenylthiocarbamide, the reaction is much lessviolent ; and hydrogen dioxide has no action on thiocarbanilide.This is probably to be attributed to the influence of the sub-stituents in hindering the formation of the pseudo-form.TEE ORCIANIC CHEMISTRY LABORATORY,UNIVERSITY COLLEGE, LONDON.VOL. XCVII

ISSN:0368-1645    

DOI:10.1039/CT9109700063

出版商:RSC    

年代:1910

数据来源: RSC

摘要:

66 USHER : THE INFLUENCE OF NON-ELECTROLYTESVIII.-The InJtuence of Non-electroltjtes on theSolubility of Cadma Dioxide in Water.By FRANCIS LAWRY USHER.THE object of the investigation to be described in this paper wasto place upon record a larger number of accurate measurementsof the solubility of a gas in solutions of non-electrolytes than hashitherto been available. Although there is a considerable massof experimental data relating to the solubility of gases in saltsolutions, the non-electrolytes examined have been confined tosome sugars, chloral hydrate, carbamide, and a few slightly dis-sociated organic acids (Roth, Zeitsch. physikal Chem., 1897, 24,114; Braun, ibid., 1900, 33, 721; Knopp, ibid., 1904, 48, 97;Christoff, ibid., 1905, 53, 321; Hufner, ibid., 1906, 57, 611;Steiner, Wied.Annalen, 1894, 52, 275). The experiments recordedhere were all carried out at 20°, and, except in the case of sucrose,a t only one concentration, namely, semi-normal. The gas usedwas carbon dioxide, chosen because its comparatively largeabsorption-coefficient permitted greater accuracy in the cleter-minations, whilst at the same time its slight deviation from Henry’slaw is not sufficient to preclude its use as an indifferent gas. Thesubstances studied were sucrose, dextrose, mannitol, glycine, pyro-gallol, quinol, catechol, resorcinol, carbamide, thiocarbamide,urethane, acetamide, antipyrine, acetic acid, and n-propyl alcohol.EX PE R I M E NTALExcept in the case of the two liquid substances examined, namely,acetic acid and n-propyl alcohol, the solutions were of exactly semi-normal strength, and were prepared in the absorption vessel itsell.The apparatus was designed with this end in view, and a descriptionof it will now be given. The carbon dioxide was prepared in anordinary Kipp’s apparatus, from marble which had been boiledfor some time in distilled water in order to remove adhering andoccluded air, and concentrated hydrochloric acid.The gas wasfound to contain less than 0.03 per cent. of foreign gas. Theoutlet tube from the Kipp’s apparatus was connected through a tapwith a large U-tube filled with marble chips, which served toprevent any acid spray from being carried over with the carbondioxide. The gas was next led through a wash-bottle containingconcentrated sulphuric acid, and finally through a phosphoric oxidetube. Wherever practicable, connexions between glass portions ofthe apparatus were made by sealing the glass together with ON THE SOLUBILITY OF CARBON DIOXIDE IN WATER.67mouth-blowpipe; in fact, the number of taps and ruljber con-nexions was kept as small as possible, and the fatter, when it wasnecessary to use them, consisted of short pieces of pressure tubingof small bore, inside of which the glass ends were brought together.The tap of the Kipp’s apparatus was left permanently open, so thatthe internal gas pressure was always in excess of the atmospheric,and no air could leak into the apparatus. The measuring burette( B ) was of 100 C.C. capacity. Of this, 50 C.C.were containedin the narrow upper part, which was graduated in tenths of ac.c., and was calibrated by weighing out mercury, whilst theremaining 50 C.C. were contained in a bulb blown below thisgraduated portion. The burettt was connected by rubber tubingwith a mercury reservoir H , carrying a levelling tube L of thesame diameter as the graduated part of the burette, and wasprovided at the top with a three-way tap G, by means of which itcould be connected either with the carbon dioxide supply or withthe absorption vessel. The absorption vessel d was of about 220C.C. capacity, and was provided near the bottom with a tubulure T,about 14 mm. wide, carrying two small glass hooks, and whichcould be closed by a ground glass stopper carrying a second pairF 68 USHER : THE INFLUENCE OF NON-ELECTROLYTESof hooks, by means of which it could be held firmly in positionwith two elastic bands.The solid substance was introducedthrough this tubulure. On the opposite side, and nearer the top,was a short capillary tube carrying a three-way tap C , so arrangedthat either the absorption vessel could be connected with a vessel Sdelivering a known volume of gas-free water, or the latter couldbe connected, independently of the absorption. vessel, with thestore of gas-free water employed.A flexible copper capillary, 2 metres long and of 1.5 mm. bore,was used to connect the absorption vessel with the burette, andwas cemented into the glass tubing with marine glue, the junctionsbeing subsequently enclosed in plaster-of-Paris blocks, to preventthem from becoming loose when the absorption vessel was shaken.A thermostat was employed for all the experiments, which werecarried out at 20° & 0'02O.When the room-temperature rose above20°, a cooling coil was introduced into the thermostat. The methodof carrying out a determination is as follows:In the first place, a semi-normal solution of the substance to beexamined was prepared, and its specific gravity a t 20° was deter-mined, and from this was calculated the weight of substance whichwould give it semi-normal solution when dissolved in 117 C.C. ofwater, this being the amount of water used in every case. Theexact quantity of the substance was then weighed into the driedabsorption vessel through the tubulure, after which the stopperwas inserted and fastened in position.The absorption vessel wasnow connected through the three-way tap with a Topler pumpand completely exhausted. After closing the tap, it was fillgd withpure dry carbon dioxide by alternately filling the burette fromthe supply and allowing the gas in the burette to pass into theabsorption vessel, by suitably turning the three-way tap G. Theabsorption vessel was now placed in the thermostat and left thereuntil the temperature of the contained gas was constant at 20°,and it was arranged that when it was full of gas a t 20° under theatmospheric pressure, the level of the mercury should be near thetop of the burette. The burette reading was then observed, andthe room-temperature and barometric height noted.Pure gas-freewater had now to be introduced. Ordinary distilled water wasused, and was previously boiled out in a vacuum in a round-bottomed flask provided with a rubber stopper carrying two glasstubes, one short, the other passing to the bottom of the flask. Assoon as all air had been completely removed, the flask was closed,cooled to a little below 20°, and the longer tube was then connectedwith the branch P of the three-way tap C, and so with the vessel S,which was filled with mercury, and of which the volume betweeON THE SOLUBILITY OF CARBON DIOXIDE IN WATER. 69two marks on the capillary stem a t a and d was accurately known :this was 117.0 C.C. a t 20°. By suitable manipulation all air wasremoved from the capillary tubing, and the tap C was now turnedand the vessel X filled with gas-free water to the lower mark ur.C was next turned in the other direction, and by raising thereservoir K and lowering the reservoir H , the exact quantity ofwater contained between a and ur was driven into the absorptionvessel.C was now closed, and the absorption vessel disconnected a tP and Q and placed in the thermostat. It was then shakenvigorously until all the solid was dissolved, and the resultingsolution saturated with carbon dioxide at 20° under the atmosphericpressure. When the burette reading was constant, the barometerheight and room-temperature were again noted, and the deter-mination was now finished. Care was taken that no gas or liquidpassed back from the absorption vessel to the burette, consequentlythe gas in the burette was always dry, whilst that in the absorptionvessel was only dry a t the commencement of the experiment. Forthe purposes of calculation the volume, and hence the densities ofthe solid substances, had to be known.The values of some of thesewere taken from papers by Schrodter (Ber., 1879, 12, 1611; 1880,13, 1070), and some were redetermined.The absorption-coefficients for the liquids, acetic acid andm-propyl alcohol, were determined by Ostwald’s method in anabsorption vessel containing 246.3 C.C. Since the volume of gasabsorbed in the case of these liquids was much greater than thecapacity of the burette, the latter had to be refilled several times.Although the error of reading was repeated as often as the burettewas filled, the volume of gas dealt with was proportionately larger,and the probable error in the final result therefore remained thesame as for the other solutions, for which a single filling of theburette sufficed.Two determinations were carried out with every solutionexamined, and four in the case of water.The maximum differencebetween the results of two such experiments was 1 in 250, whilstmost agreed to within 1 or 2 in 1000.Calculation of Results.The absorption-coefficients (a) given represent the volume ofcarbon dioxide, reduced to Oo and 760 mm., which is dissolved by1 C.C. of liquid at 20° when the partial pressure of the carbondioxide is 760 mm.Calculation of absorption-coefficient for solutions of solids :Let = volume of absorption vessel up to beginning of copper(i)xcapillary70 USHER : THE INFLUENCE OF NON-ELECTROLYTESLet y = volume from beginning of copper capillary to markon burette.66 0 'I.,, b, and 6, = initial and final burette readings.7 9 A =97 a =y , 23 =Y Y P =9 9 tThe corrected- -volume of solution.volume of solid substance.barometric height, corrected to Oo.vapour pressure of solution at 20'.room-temperature.initial volume of gas in the apparatus will beand the corrected final volume will be:2 73hence the volume dissolved by A C.C. of the solution- P 273 (b,-b,) + -{-(-a) 273 P - p - ( z - A)}c.c.,760 273+t 2'33 76U 760andP-p' m tA a =I f the room-temperature is itself 20°, the expression simplifies to :(ii) When water is used instead of a solution of a solid, if Ti1 isthe volume of water taken :273293W a = =orif the room-temperature is 20°.(iii) I n the case of the solutions of liquids examined, theabsorption-coefficient, measured in the Ostwsld vessel, is equal to :2 73I' - p a 273 + tAwhere b and 6' are the burette readings before and after introON THE S0,LUBILITY OF CARBON DIOXIDE IN WBTEI'L.7 1ducing the gas into the absorption vessel, and T Y is the volumeof solution run out from the absorption vessel.Nature and Magnitude of Errors.I n all the experiments, an accuracy of 1 in 1000 was aimed at,and the values of a given may be taken as correct t o 1 in 500.Since the measured volume difference between the first and lastreadings was always about 100 c.c., an error of 0.1 C.C.involves anerror of 1 in 1000 in the value of a. By far the most importantsources of error were (1) inexact levelling when reading the volumeof gas in the burette, and (2) variations in the temperature of thethermosta,t.There was no difficulty in reading the burette with a maximumerror of 0.05 c.c., but the exact adjustment of the levelling tubewas not so easy. Ia the initial reading, when the volume of gasin the apparatus is about 226 c.c., an error of 1 mm.*in thelevelling involves an error of about 0.33 C.C. In the final reading,when the volume of gas is only half as great, a similar error inlevelling involves an error of 0.17 C.C.The actual uncertainty oflevelling was probably about a quarter of a millimetre, and ifthe errors in the two readings were additive, this involves an errorof 1.2 in 1000 in the value of a. Thus the probable error intro-duced by this inaccuracy is 0.6 in 1000.Thus,if the temperature of the thermostat is not exactly 20°, not onlyis the volume of gas soluble in the liquid changed by expansionor contraction, but the absorption-coefficient is also directlyinfluenced. Supposing that at the initial reading the true tem-perature in the thermostat is (20--8)O, and a t the final reading itis (20 + O)O, it can be calculated that the difference between the trueand the apparent volume of gas absorbed is:Variations in temperature affect the resulks in two ways.where /3 is the difference between the volume of gas soluble in theliquid at 20° and the volume soluble at (20 + 8)O.This expression,after neglecting 8 and 82 in the denominator, and evaluation of fifrom the temperature-coefficient of solubility of carbon dioxide inwater, is equal to about 48 C.C. Now the maximum variation (28)in the temperature of the thermostat was 0*04O, and the maximumerror from this cause is therefore 0-08 c.c., that is, about 0.8 in1000.Compared with the above, the other errors are unimportant.The barometer was read with an accuracy of 0.1 mm., and theheight of the mercury column was corrected for expansion fro72 USHER : TEE INFLUENCE OF NON-ELECTROLYTESOo to the room-temperature.The time interval between the initialand final readings was usually about haIf an hour, and no sensibleerror was introduced through employing the mean of the twobarometer readings, since these never differed by more than 0.2mm., and could not as a rule be detected. Similarly, the room-temperature was always sufficiently constant during an experimentto preclude the introduction of any appreciable error throughemploying the mean temperature for the calculations. There isno doubt that the gas in the absorption vessel was completelysaturated with water vapour a t the second reading, on account ofthe vigorous shaking which always took place, or that the gas inthe burette was dry, since the burette tap was always closed whilethe absorption vessel was being shaken, and gas was never alIowedto pass from the latter into the burette.As already stated, twodeterminations were made in every case, in which the averagedifference is 1.7 in 1000, and consequently the probable accuracy ofthe results is about 1 in 1000.R e s d t s.A bsorption-coefficient in Wat er.-Four determinations weremade, and the values found were (i) 0.8775; (ii) 0.8766; (iii)0.8755; (iv) 0.8766; mean, 0-877.This value is in good agreement with that given by Bohr (Wied.Annalen, 1899, 68, 503), namely,Table I gives the absorption-coefficients (a') in the solutions ofsucrose examined, and the specific gravities of the solutions at 20°.=0*878O.TABLE I.Concentration. a'. Mean a'. 8p. gr................ 0.846 1'01518 N/8 {%E...............0.~15 N/4 { 8::::;N/2 -K;:t3" ............... 0.756N ............... { 8'E 0'6491.031251'06372i.12a09I n table I1 are given the absorption-coefficients in semi-normalsolutions of the other substances examined, and, for purposes ofreference, the specific gravities of the solutions a t 20° and thespecific gravities of the solid substances a t the same temperatureON THE SOLUBILITY OF CARBOX DIOXIDE 1N WATER. 73Substance.Dextrose ...............Msnnitol.. .............Glycine ...............Pyrogallol ............Quinol.. ........ - ......Resorcinol ............Catechol ..............Urethane ............Carbamide ............Thiocarbamide ......Antipyrine .........Acetamide ............Acetic acid ............n-Propyl alcohol ...TABLE 11.Mean a'.0.7920.7820.8430.8530'8870*9010.8680.8690'8640-8590.8590.8790.8680.869SP. €7.:N/2-solution.1 *03281 -030311 '01 4 131 '01 71 81'009461'009581'01071'00371.007151-009171.013391 *00051 -00260'9939Sp.gr.solid.1-56 *1-46 *1-61 *1-451 '331 -271-340 *991.33 *1.42 *1.19 *1.56- -* Redetermined.Biscussiom of Results.Since any theoretical deductions from the results must dependon the way in which the latter are expressed, it is first of alldesirable to consider briefly the methods which are usuallyemployed for this purpose. In order t o compare together a numberof different substances with respect to their influence on thesolubility of a third substance, it is, of course, only permissibleto employ solutions of the same molecular concentration. Herethe usual difficulty arises with regard to the calculation ofmolecular concentration (compare Abegg, Zeitsch.physikal. Chem .,1894, 15, 248). The semi-normal solutions used in this investi-gation all contained half a gram-molecule in a litre of the solution,and this concentration is in many cases considerably different fromthat of a solution containing the same weight of substance in1000 grams of water. Except in the case of sucrose, no experimentswith several different concentrations were carried out, but thefigures for this substance certainly suggest that the volume-norma1is more convenient for our present purpose than the weighbnormalmethod of calculation, and also that solutions of semi-norma74 USHER : THE INFLUENCE OF NON-ELECTROLYTESstrength are still sufficiently dilute to permit inferences whichmay be applied without serious error to very dilute solutions.I n table I11 are given values for the inolecular depression ofsolubility calculated according to the volume-normal and weight-normal methods for solutions of sucrose. a and at denote theabsorption-coefficients of carbon dioxide in pure water and thesolution respectively, N is the number of gram-molecules of sucrosein 1 litre of sohtion, and N’ the number in 1000 grams of water.TABLE 111.N. a - a’/N.0’125 0-2480 *25 0.2480.5 0’2421 ‘0 0 *228a - u’fN).0-2410-2340.2160-180It will be seen from these figures that the molecular depression,calculated by the volume-normal method, is constant for solutionsup to N / 4 , and is very little different for those of N/2-concentra-tion; and since sucrose produces a much greater effect than anyof the other substances examined, the deviations in the case ofthese must be still smaller. The purely empirical formula,a - af/iVe, suggested by Jahn for expressing the relation betweendepression of solubility and concentration in the case of electro-lytes, is obviously unsuitable for sucrose, and Roth (Zeitsch.phgsikal. Chew&., 1897, 24, 114) has shown that the figures forglycerol are better represented by the linear formula.* It istherefore probably safe to assume that for moderately dilutesolutions of non-electrolytes the effect on the solubility of carbondioxide, or of any indifferent slightly soluble third substance, isdirectly proportional to the amount of non-electrolyte present. Itnow remains to consider certain attempts a t generalisation 3n thelight of the experimental data recorded in this paper.One of the most recent of such attempts is that of Philip (Trans.,1907, 91, 711), who suggests that substances which have notendency to combine with the solvent are without influence on thesolubility of an indifferent gas, whilst those which do influence thesolubility do so because they remove a portion of the solvent byforming compounds with the latter.By “solubility” is heremeant the amount of gas dissolved by unit mass of the pure solvent;.For example, the absorption-coefficient of hydrogen in an aqueoussolution of chloral hydrate is smaller than in pure water (Knopp,Zeitsch.physikal. Chem., 1904, 48, 97), but the amount dissolved* It should be mentioned that Geffcken (Zeitsch. physikal. Chwn., 1904, 49, 257)has pointed out sources of error in the experiments of Gordon, Roth, and Rraun,which may invalidate the apparent support they afford to Jahn’s empirical formulaON THE SOLUBILITY OF CARBON DIOXIDE IN WATER, 75by 1000 grams of water is the same in each case. This statementis not true, however, for solutions of sucrose; and in order tobring this substance into line, it is assumed that the statementwould be true if it were not that a certain fraction of the wateris withdrawn by the sucrose, and the average number of watermolecules attached to one molecule of sucrose is calculated in away consistent with the theory.This method of calcuTationinvolves three assumptions : it presupposes (1) that hydrates areformed, (2) that the gas is insoluble in the dissolved substance, and(3) that it is insoluble in the hydrate.That such assumptions its these have little foundation in factmay be inferred from the following table, which shows the volumeof carbon dioxide dissolved by 1000 grams of pure water for thedifferent semi-normal solutions examined, calculated on the assump-tion that the water alone is responsible for the absorption of gasobserved.TABLE IV.Carbon dioxidedissolved by1000 grams ofSolution.water, in C.C.Water ............... 878Sucrose.. ............. 797Dextrose ............ 841Mannitol ........... 833Glycino.. ............. 864Py rogal lo1 ......... 894Quinol ............... 928Resorcinol ......... 946Carbon dioxidedissolved by1000 grams ofSolution. water, in C.C.Ca techol ............ $08Urethane ............ 907Carbamide ......... 884Thiocarbarnide ... 885Antipyrine ......... 935Acetamide ......... 906Acetic acid ......... 893n-Propyl alcohol.. . 902It is noticeable, in the first place, that in eleven out of the fifteensolutions examined a larger quantity of carbon dioxide is dissolvedthan can be accounted for if the water only is responsible for theabsorption.This fact alone suffices to show that if we wish toexpress the solvent properties of these solutions in terms of theproperties of their components, any conclusions depending on theassumption that the dissolved substance has no solvent power areworthless.It is instructive also to compare, from the point of view of thehydrate theory, the behaviour of some of these substances withthat of the solutions used by Jones and Getman (Amer. Chem. J.,1904, 32, 308) in their cryoscopic investigations. I f the " averagemolecular hydration " is calculated in the way described by Philipfrom the figures given above for sucrose, dextrose, and mannitol;we arrive at the conclusion that sucrose is hydrated to the extentof 3.6 molecules of water, dextrose 4.6 molecules, and mannitol 5.2molecules-values which are completely a t variance with thosededuced by Jones and Getman from their data for the molecula76 USHER : THE lNFLUENCE OF NON-ELECTROLYTESdepression of the freezing point.These authors conclude thatsucrose in semi-normal solution a t Oo forms complexes containingabout 5 molecules of water, whereas dextrose is hydrated only toa small extent, and the tendency of mannitol to form hydrates isinsignificant. It is not intended here to dispute the existence ofhydrates in solution, but it may be permissible to raise the questionwhether much is to be gained by referring abnormal depression ofsolubility to this cause, when by so doing it becomes necessary tomake other and more improbable assumptions.Of a different character is the generalisation deduced, on thermo-dynamic principles, by Jahn (compare Roth, Zeitsch.physikal.Chem., 1897, 24, 115). According to this, the molecular con-centration of a gas remains the same when it is dissolved tosaturation in a dilute solution of an indiff erentf non-volatile sub-stance as when it saturates the pure solvent under the sameconditions of temperature and pressure. I n other words, if C,denotes the ratio of the number of gas-molecules to the sum of themolecules of gas and solvent, and C2 is the ratio of gas-molecules tothe sum of those of gas, solvent, and third substance, the theoryrequires that C,jC2 shall be equal to unity, provided that thefollowing conditions are fulfilled: (i) The gas must exert nochemical action on the solvent or the solution; (ii) it must havethe same molecular weight in the liquid as in the gas phase;(iii) the solution must be dilute.I n a limited number of cases, results have been obtained whichare described as being in good agreement with the theory.Thus,Roth (Zoc. cit.), using nitrous oxide, found C,/C2=1.009 forcarbamide a t about semi-normal concentration, 1.013 for glycerol,and 1-009 for oxalic acid. Braun (Zoc. cit.) found 1.037 forcarbamide and 1.023 for propionic acid in the case of nitrogen;and, in the case of hydrogen, 1.015 for propionic acid. Knopp(Zoc. cit .) found €or chloral hydrate, when hydrogen was used,0.993, and when nitrous oxide was used, the ratio was 1.010 forchloral hydrate and 1.037 for propionic acid.Here we have values of C,/C, deviating by anything between0-7 and 3.7 per cent.from the theoretical value; but in view ofthe fact that the actual change of solubility effected lies betweenthe limits 1.3 and 4.5 per cent., it becomes obvious that theapparently good agreement has no significance whatever. It shouldbe mentioned that Knopp's experiments were all carried out at20°, whilst those of Roth and Braun were carried out a t 5O, loo,15O, 20°, and 25O. The figures quoted above refer to the meanof the results obtained a t these five temperatures; the actual valueof C,/C, was found to diminish with rising temperatureON THE SOLUBILITY OF CARBON DIOXIDE IN WATER. 77In table V the values of C,jC2 for the substance3 employed inthe present investigation are tabulated, and it is interesting t ocompare the percentage deviations from the theory, given in thethird column, with the percentage change in solubility of the gasbrought about by the non-electrolytes used, given in the fourthcolumn.TABLE V.Solution.N-Sucrose ...............N/8-Sucrose ............N/4-Sucrose ............N/B-Sucrose ............N/2- Uextrose ............N/B-M~rtnnitol.. ..........N/%Glycine ............N/2- Py rogallol .........N/2-Thiocarbamide ., .N/e-Carbarnide ........N/Z-Urethane ............N12-Antipyrine .........N/ 2 . Catec hol ............M/B-Quinol. ..............N12- Acetamide .........A7/2-Acetic acid ....Nj2-n-Propyl alcohol.N/i-Resorcinol .........Cl/G1.1011'0121 -0241 -0481 -0561.0651.0260.99211 *0021 -0030.97890.94940.97620-95540.93960.97950-99360.9817Percentage deviation Percentage changefrom Cl/C, = 1.of solnbility.10-1 26 .O1.2 3.52.4 7-14.8 13.85-6 9.76 -5 10.82-6 3.90.8 2-70.2 2.00.3 1 -52.1 1.05-1 2.02.4 1 '04.5 1.06.1 2.72 *1 0 . 20.6 1.01 -8 1-0It will be seen from this table that in no less than seven instancesthe deviation from the theory actually exceeds the magnitude ofthe effect which is being studied; and, in general, the extent ofthe discrepancy increases with the amount of the effect produced.There can, however, be no doubt that the formula deduced byJahn is inapplicable to the experimental data hitherto available ;in other words, that the conditions for which the formula is validare not fulfilled in the experiments. Indeed, the influence of mostnon-electrolytes is s,o small that it may reasonably be doubtedwhether a rigid confirmation of the theory is possible with ourpresent methods of determining gas-solubility ; and in any casethere is the possibility that the dissolved substance, althoughchemically indifferent, may itself be capable of dissolving the gasemployed.An attempt has been made by Roth (Zeitsch.physikal. Chem.,'5903, 43, 539) to find some common factor which will bring thedeviations from Jahn's thermodynamic formula into line withdeviations from van't Hoff's freezing-point law, and it was shownthat a parallelism did exist in the cases of glycerol and sucrose,both of which give too large a depression of the freezing point,and too great a value for C,/C',. Thiocarbamide and glycine,however, give too small depressions, whereas the values of C,/C78 POPE AND HOWARD: THE CONDENSATION OFfor these substances are respectively 1.002 and 1.026 in semi-normalsolution a t 20°, and would, of course, be greater still at Oo.It seems, therefore, that the effect on the solubility of a gas *produced by non-electrolytes is not capable of explanation byreference either to the formation of hydrates in solution or todeviations from the theory of osmotic pressure-conclusions whichhave already been expressed by Levin (Zeitsch. physikal. Chem.,1906, 55, 513); but that since these effects are, as Geffcken (Zoc.cit.) has shown, practically independent of the solubility of thegas and almost entirely determined by t.he nature of the solventor solution, it is only possible a t present to refer them to mutualinteraction among the molecules. It only remains to be mentionedthat the lasbnamed author has already called attention to aparallelism which exists between depression or elevation of solu-bility and such properties as compressibility and surface tension,and it is possible that the whole problem might be more success-fully attacked from this point of view.This research was carried out a t the suggestion ofProf. Rothmund, t o whom I am greatly indebted for much kindlyadvice snd criticism, as well as for placing at my disposal thenecessary apparatus and material.INSTITUTE OF PHYSICAL CHEMISTRY,GERMAN UNIVERBITY,PRAGUE

ISSN:0368-1645    

DOI:10.1039/CT9109700066

出版商:RSC    

年代:1910

数据来源: RSC

摘要:

78 POPE AND HOWARD: THE CONDENSATION OFIX.-The Condensation of Benxaldehyde withResorcinol,By FRANK GEORGE POPE and HUBERT HOWARD.THE reaction between benzaldehyde and resorcinol has apparentlybeen very little studied. Michael (Amer. Chem. J., 1884, 5, 338),by the addition of small quantities of hydrochloric acid to analcoholic solution of the two reacting substances, obtained it resinto which he assigned the empirical formula C2,H,o0,. This sub-stance yielded a tetraracetate, and also, on treatment with moreacid, was converted into a crystalline isomeride. Liebermann andLindenbaum (Ber., 1904, 37, 1171), by heating an alcoholic solu-* And also of a slightly soluble salt (compare Rothmund, Zeitsch. phyCsika2.Chem., 1909, 69,625)BENZALDEHYDE WITH RESORCINOL.79tion of the two components with concentrated sulphuric acid,obtained a compound having the composition CI3Hl0O3, which onacetylation yielded a triacetate. Since the above method ofprocedure was, t o all intents and purposes, unproductive, itoccurred to us that by using Manasse's method of condensation(Ber., 1894, 27, 2409) the two reacting components might yield2 : 4-dihydroxybenzhydrol, which would then be of considerableuse in the preparation of substituted fluorones and acridines.We have succeeded in obtaining the hydrol, and have condensedit with various phenols and a.mines and prepared the correspondingxanthens and dihydroacridines, as typical examples of which maybe taken the reaction between the hydrol and resorcinol and thehydro1 and p-toluidine, thus :0PhNH3 ; 6-Dihydroxy-9-phenylxanthen./\ v\\?=HOAOH = 2H20 + I ICHPh*OH+ vPh8-Hydroxy -5-phenyl-3-meth yldihydroacridine.EXPERIMENTAL.2 : 4-Dihydroxy b e m hydrol, C,H,( OH),*CH( OH) *C,H,.-Twenty-two grams of resorcinol were dissolved in 500 C.C.of water, con-taining 50 grams of sodium hydroxide, and shaken from time totime with the calculated amount of benzaldehyde (21.2 grams).The solution gradually darkened in colour, and became ultimatelydeep blood-red, the odour of the benzaldehyde gradually disappear-ing. The next day the solution was diluted with about its ownvolume of water, and then acidified with either dilute hydrochloricor acetic acid, when a pale brownish-white, microcrystalline pre-cipitate of the hydrol was obtained.This was collected, wellwashed with water, redissolved in sodium hydroxide solution, andagain precipitated and washed. It is to some extent soluble inalcohol or glacial acetic acid, and more readily so in pyridine, butcannot be recovered in it crystalline form from these solvents. Forpurposes of analysis, the reprecipitated hydrol was repeatedl80 POPE AND HOWARD: THE CONDENSATION OFextracted with hot water, collected, and well washed and finallydried in a desiccator over sulphuric acid:0*1100 gave 0.2916 CO, and 0.0585 H,O. C272.30; H=5.91.0'2222 ,, 0'5888 CO, ,, 0.1025 H,O. C=72*27; H=5.13.C,,H,,O, requires C = 72.22 ; H = 5-56 per cent.2 : 4-Dihydroxyb enzhydrol is a faintly yellowish-coloured sub-stance, which darkens rather rapidly on exposure to air.It doesnot melt, but chars a t about 200O. It is readily soluble in solutionsof the alkali hydroxides, the solutions possessing a dark blood-redcolour. By dissolving the hydrol in water containing the calculatedamount of potassium hydroxide and evaporating the solution todryness on the water-bath, a red &potassium compound is obtained.On recrystallisation from water, this gave, on analysis :0-328 gave 0.196 K,SO,. K=26*79.C,,H,,0,K2 requires K = 26.69 per cent.The diacetyl derivative was prepared by heating 5 grams of thehydro1 with 25 grams of acetic anhydride and 1 gram of zinc dustfor three hours under reflux. The solution was filtered and pouredinto a mixture of 300 C.C.of water and 50 C.C. of alcohol, and thewhole then warmed on the water-bath for some time to removeexcess of acetic anhydride. The solid product was collected,washed, and recrystallised from dilute acetic acid, when it wasobtained as a colourless solid, which decomposes when heated toabout 200O:0.1092 gave 0.2736 CO, and 0.048 H,O. C = 68.33 ; H =4.88.0.1042 ,, 0.2604 CO, ,, 0.0466 H20. C=68*15; H=4.97.CI7H,,O, requires C = 68-00 ; H = 5.33 per cent.2 : 4-Diacetoxybenzhydrot is soluble in acetone, chloroform,benzene, or acetic acid, but insoluble in light petroleum.The benzoyl derivative was prepared by dissolving 4-32 gramsof the hydrol in the calculated amount of sodium hydroxide(2 mols.) dissolved in 40 C.C. of water, and adding 5.62 grams ofbenzoyl chloride. The mixture was well shaken, and the paleyellow precipitate collected, washed, and crystallised from diluteacetio acid:0.1014 gave 0.284 CO, and 0.0429 H20.C = 76.38 ; H = 4.70.0.2262 ,, 0.6372 CO, ,, 0.096 H20. C=76*82; H=4.75,C27H200, requires C = 76.41 ; H = 4-72 per cent.2 : 4-DibenzoyZoxybenzhydroZ is an almost coluurless solid, whichdarkens somewhat on exposure. It is soluble in benzene, chloro-form, or acetic acid, but insoluble in light petroleum. On heating,it darkens a t about 170°, and melts and decomposes at about 195O.The dimethyl ether was obtained as follows. 4.5 Grams rBENZALDEHYDE WITH RESORCINOL. 81potassium hydroxide were dissolved in 50 C.C. of methyl alcohol,4 grams of the hydrol were added, along with 6 grams of methyliodide, and the whole was heated under reflux for four hours.Thesolution was then diluted with water, and rendered just acid. Thedark precipitate thus obtained was collected, washed, andcrystallised from dilute acetic acid, from which it was obtainedas a rather brownish-coloured, microcrystalline solid :0.093 gave 0.2516 CO, and 0.054 H;O. C = 73.78 ; H = 6.45.0.109 ,, 0.294 CO, ,, 0.062 H20. C=73*56; H=6*32.C15H1603 requires C = 73-77 ; H = 6.56 per cent.Since the above analyses would not absolutely exclude the possi-bility that the compound might be a monomethyl ether, C14H1403,which would require C=73*05, H=6.09 per cent., the methoxylgroups were estimated by the Zeisel method, with the followingresult :0.8104 gave 0.162 AgI.OMe=26-38.2 : 4-Dimetlioxy/benzhydrol is soluble in acetone, benzene, or6-Hydroxy-9-phenyl-2-met hylxantl~en,C,,H,,O(OMe), requires OMe = 25-41 per cent.It decomposes when heated above 130O. acetic acid.-Four grams of 2 : 4-dihydroxybenzhydrol were mixed with 2 gramsof pcresol and 4 grams of anhydrous zinc chloride, and the mixturewas heated to 170° for four hours. When cold, the product wasextracted with hot water several times to remove zinc salts, andfinally crystallised from alcohol. It is a red,* crystalline solid,which melts a t 112O, and it is readily soluble in alcohol, butsparingly so in acetic acid:0.111 gave 0.338 CO, and 0.057 H20.3 : 6-Dihydroxy-9-phenylxanthen, HO*C,B,<~~~>C,H3*OH,is obtained in a similar manner when 4 grams of dihydroxybenz-hydrol are heated with 2 grams of resorcinol and 4 grams ofanhydrous zinc chloride for four hours to 160O.It crystallisesfrom alcohol in small red* needles, which melt at 136O, and aresoluble in alcohol, pyridine, benzene, or glacial acetic acid :C=83.05; H=5*70.C2,H,g0, requires C = 83.33 ; H = 5-56 per cent.0,1068 gave 0.3075 C'O, and 0.0475 H20.CISH,,O, requires C = 78-62 ; H = 4-83 per cent.* In this case the colour observed is, in all probability, due to slight oxidatioiiwith consequent formation of small quantities of the corresponding fluorone deriv-atives, the xanthens being difficult to keep in a state of absolute purity.C=78.52; H=4.94.VOL. XCVII. 82 POPE AND HOWARD: TEE CONDENSATION OF3 : 6-Dibensoyl-9-phenylxant?~en was prepared by the Schotten-Baumann method, and on recrystallisation from dilute alcohol wasobtained as a rather reddish-coloured solid, melting and decomposinga t 125O:0.1082 gave 0.3148 CO, and 0.0446 H20.C,H,,O, requires C = 79.52 ; H =4*42 per cent.A bromo-derivative was obtained when the dihydroxyxanthenwas dissolved in glacial acetic acid, and the calculated amount ofbromine added gradually to the solution.A precipitate was formeda t first, but dissolved on adding more of the bromine. After sometime the solution was poured into water. The precipitate wascollected, washed, dried, and crystallised from amyl acetate, fromwhich it separated in small, red needles. It is soluble in amylacetate, pyridine, chloroform, or acetic acid, but sparingly so inalcohol, the solution obtained resembling that of eosin in alcohol,and possessing a yellowish-green fluorescence :C=79*35; H=4*58.0.15 gave 0.1866 AgBr.Br=52'94.C,,H,O,Br, requires Br =52*98 per cent.C,,H,,,O,Br, ,, Br=52.80 ,,It is most probable that this bromo-compound is tetrabromo-3-hydroxy-9-pkenylfEuorone, CI9H8O3Br4, the first action of thebromine being that of an oxidising agent, since an alcoholicalkaline solution of the bromo-compound, on treatment with zincdust, gives a colourless solution, which rapidly oxidises with theformation of the deep red colour shown by the bromo-derivative inalcoholic alkaline solution.8-Hydrox y-l 1 -ph eny Z-&naph t h a x m t ? ~ en,,0H o p / \ / / > \9~ 1 5 1\/ \/ \/\Q" II :I\ 10 A 11 /Ph '&/4 - 3 2 Grams of the hydro1 were mixed with 2.88 grams of&naphthol and 5 grams of anhydrous zinc chloride, and the mixturewas heated to 150° for six hours.The zinc salts were extractedwith water, and the residue was dissolved in dilute sodium hydroxidesolution. Acetic acid was then added, and the precipitate obtainedwas collected and well washed with water. On recrystallisationfrom alcohol, the compound separated as a dark red,* crystallinepowder, melting at 84O:0.1124 gave 0-3506 CO, and 0.0506 H,O. C=85*07; H=5*05.C2,H,,0, requires C = 85.18 ; H =4*94 per cent.* See footnote, p. 81BENZALDEHYDE WITH RESORCINOL. 83The benzoyl derivative (8-benzoyloxy-ll-p7~enyl-~-naphthu-xanthen) was prepared by the Schotten-Baumann method, and onrecrystallisation from alcohol was obtained in small, almost colour-less needles, decomposing when heated to about 103O:0.103 gave 0.318 CO, and 0.046 HiO.8-Hydroxy-5 -ph enyl-3-met hyldihydroucridine,C=84*20; H=4*96.C,H,,O, requires C = 84.11 ; H = 4-67 per cent.HO.C,H~~;>C,H,.M~.-This substance was prepared by heating 8.64 grams of the hydro1with 4-28 grams of p-toluidine and 10 grams of anhydrous zincchloride for four hours a t 160O.The product was then boiled withwater and crystallised from dilute alcohol. Owing to the obstinateretention of small traces of zinc salts, it was then found advisableto boil the product again with very dilute hydrochloric acid, filter,well wash, and again recrystallise. The product thus obtainedwas a light brownish-coloured * powder :0.1002 gave 0.3082 CO, and 0.055 H,O.0.115 ,, 5.0 C.C. N, (dry) a t 2 2 O and 761 mm. N=5*04.The b enzoyl derivative (8- b en20 y Zoxy-5-phenyl-3-me t hyldihyd ro-acridine) was prepared by the Schotten-Baumann reaction. Oncrystallisation from dilute alcohol it separated in almost colourlessneedles, which decomposed at about 135O :0-108 gave 0.3274 CO, and 0.0516 H,O.0-52 ,, 17.4 C.C. N , (dry) a t 21O and 740 mm. N=3.77.C = 83.88 ; H = 6.09.C,,H,,ON requires C = 83-62 ; H = 5.92 ; N = 4.88 per cent.C =82.67 ; H = 5.31.C2,H2,02N requires C = 82-86 ; H = 5-26 ; N = 3-58 per cent.We are at present engaged on the oxidation of the xanthen anddihydroacridine derivatives, also in the condensation of the sub-stituted benzaldehydes with phenols and amines, and hope to beable to lay the results before the Society later.EAST LONDON COLLEGE(UNIVERSITY OF LONDON).* The colour here again is to be attributed to slight oxidation.G

ISSN:0368-1645    

DOI:10.1039/CT9109700078

出版商:RSC    

年代:1910

数据来源: RSC