摘要:

THE HALF-LIFE PERIOD OF RADIUM; A CORRECTION. 185XIX.-T!ke HaljX;fe P e r i o d of Radium ; a, Correction.By ROBERT WHYTLAW GRAY and SIR WILLIAM RAMSAY, K.C.B.IN making the calculation of the half-life period of radium in thepaper which has recently appeared (Trans., 1909, 95, 1083), anerror, which Mr. Soddy was so good as t o point out to us, wasmade inadvertently. Half the reciprocal of the disintegration-constantof radium, equal to half the average life-period, was given as theperiod of half-decay, namely, 1258 years. The true half-life periodshould have been calculated from the equation : R = R,,e-*t, where Ris the initial amount of radium, R, the quantity remaining after halfhas decayed, e the base of natural logarithms, A the disintegration-constant for radium (the reciprocal of which is the average life-period),and t the time in years.To find A from the equilibrium-quantity, ATo, of emanation per gramof radium, the volume of which was 0.601 cub.mm., the amount ofemanation given off per second was calculated by means of the0.601 equation : qo=AN,= - = 1-25 x cubic millimetres per48 1,000second; the fraction 1/481,000 is the value of A, the disintegrationcoustant for the emanation, calculated from the half-life period of 3.86days. This volume is equal to the diminution in volume of 1 gram ofradium per second, supposing it to be a monatomic gas.Hence the fraction of the total quantity of radium changed persecond is 1.25 x of the volume of 1 gram of gaseous radium.This is equal to 1'25 226, 226 being the accepted atomic22.400 x 100186 BARNETT AND SMILES : THE INTRAMOLECULARweight for radium ; the expression is equivalent to 1/2516 per year,and is A, or the disintegration-constant for radium. I n decimals, itis 3.98 x 10-4 gram per year ; hence the half-life period for radium is1744 years, or, in other words, 1 gram of radium will have beenreduced to 0.5 gram after 1744 years,UNIVERSITY COLLEGE,LONDON

ISSN:0368-1645    

DOI:10.1039/CT9109700185

出版商:RSC    

年代:1910

数据来源: RSC

摘要:

186 BARNETT AND SMILES : THE INTRAMOLECULARXX.-The Intramolecular Rearrangement of Diphcnyl-amine ortho-Sulphoxides. Part 11.By EDWARD DE BARRY BARNETT and SAMUEL SMILES.IN a previous communication to the Society on this subject it wasshown that the ortho-sulphoxides of diphenylamine (type I) maybe transformed by the action of acid reagents into the sulphoniumhydrates (type 11). A t the same time it was observed that if theNH N NbH i c(1.1 (11.) (111).sulphonium grouping be sufficiently basie, the corresponding salt(type 111) may be formed. The tetranitro- and the two isomericdinitro-sulphoxides yielded the sulphonium hydrates, but the parentcompound (I) furnished phenazothionium chloride. In the fourcases examined, it was observed that the sulphonium derivativescontain an additional molecule of water; but usually this may beremoved by crystallisation from high boiling solvents.The investigation of this reaction has been continued with theobject of determining the mechanism by which the change takesplace, and the results are now collected in the following pages.From the mere inspection of the formulae (I and 11) representingthe initial and final products of the reaction, it might be supposedthat the sulphonium hydrate is formed simply by the migrationof hydrogen from the imino-group to the oxygen of the thionylgroup.In order to test whether this is actually the case or not,we have examined the behaviour of sulphoxides in which thisiminic hydrogen is replaced by alkyl. It has been found that thesederivatives undergo the change as readily as the unsubstitutedcompounds. The two chief examples studied were the dinitro-N-methyldiphenylamine ortho-sulphoxide (IV), which has been preREARRANGEMENT OF DIPHENYLAMINE ORTHO-SULPHOXIDES.187viously obtained by Bernthsen from the nitration of N-methylthio-diphenylamine, and the X-methyldiphenylamine sulphoxide (V),which we have prepared by oxidation of the sulphide.\/\AI l l\/A/\/ so(IV. 1 (V* )Assuming that the course of tThe reaction is the same with theseN-alkyl derivatives as with the imino-compounds, it might thenbe concluded that with the latter the reaction does not involve thedirect movement of the imino-hydrogen atom, for on a priorigrounds it is improbable that the alkyl group should be transferredwith such ease under the conditions favourable to the reaction.This conclusion, however, cannot be accepted until some actualproof is obtained of the immobility of the alkyl group, for manyinstances are known where the transposition of alkyl from one atomto another can be detected, although the treatment then requiredis usually more energetic than that necessary to the presentreaction.The proof that alkyl is not removed from nitrogen duringthe reaction has been obtained in the case of N-methyldiphenyl-amine o-sulphoxide. This sulphoxide, when treated with hydrogenchloride, absorbs one molecular proportion of the halogen acid, beingthen converted into the chloride of a base which is deep red incolour and has properties similar to those of the phenazothioniumderivatives described in a previous paper.It may be remarkedthat the quinonoid structure of this chloride is demonstrated bythe further action of hydrochloric acid, which yields a chloro-derivative of N-methylthiodiphenylamine. If the methyl group istransferred from the nitrogen in this reaction, the only alternativesare that it may either enter the aromatic nucleus (as in VI), orbecome attached to the thionyl group (as in VII). In either casethe substance which is formed would be represented as follows(VI and VII) :f /\/\/\“21 IN021 \/A/\/ soHO CH,\/N N 188 BARNETT AND SMILES : THE INTRAMOLECULARand on reduction it should furnish either a methylthiodiphenyl-amine (from VI) or thiodiphenylamine itself (from VII).We find,however, that reduction of the quinonoid salt does not yield eitherof these compounds, but that instead N-methylthiodiphenylamineis formed. It follows that the constitution of this substance mustbe as represented in the third of the foregoing (VIII) formulae;but it is impossible conclusively to show whether salt formationtakes place at the ammonium or sulphonium groups. Moreover, thesalt is not very stable, since, as previously noticed, it readilychanges to chloro-N-methylthiodiphenylamine, thus affordingfurther proof of the immobility of the methyl group. The experi-ments dealing with these derivatives of N-methylthiodiphenylamineare described in the following paragraphs.EXPERI M E NTALConversion of N-Methyldiphenylamine ortho-Sulphoxide into theSulphoniurn Derivative.Attempts to prepare this sulphoxide were made by treatingN-methylthiodiphenylamine with hydrogen dioxide in acetone solu-tion, but only small quantities of the substance could be obtainedby this method, almost the whole of the sulphide being recoveredunchanged after remaining with the reagent for about three weeks.Attention is drawn to this result, since thiodiphenylamine is readilyoxidised to the sulphoxide under these conditions.Bernthsen(Annalen, 1885, 230, 92) has shown that N-methylthiodiphenyl-amine may be converted into the sulphone by hot aqueous per-manganate, but we find that this reagent under similar conditionsfurnishes satisfactory yields of the sulphoxide.A solution of six grams of X-methylthiodiphenylamine in acetonewas acidified with dilute sulphuric acid, more acetone being added,if necessary, to retain all in solution.Two grams of finely powderedpotassium permanganate were then gradually added, the temper*ture being kept at about 1 5 O by immersing the flask in cold water.Care was taken to ensure the presence of a slight excess of sulphuricacid during the reaction. The mixture was shaken for a few hours;then the crystalline precipitate was collected, and well washed withwater. The residue was agitated with a cold aqueous solution ofsulphurous acid, and finally recrystallised from alcohol. The leastsoluble portion contained small quantities of the sulphone, and itwas therefore rejected.Nine grams of the crude sulphoxide wereobtain from 18 of sulphide.N-~ethyldil?henyZamine ortho-sdphoxide forms colourless leaflets,which melt a t 1 9 3 O . It is sparingly soluble in cold acetone oREARRANGEMENT OF DIPHENYLAMINE ORTHO-SULPHOXIDES. 189alcohol, and insoluble in water. Concentrated sulphuric or hydro-chloric acid forms bright red solutions, which contain the phenazo-thionium derivative. A sample which had been dried in a vacuumwas analysed:0.1009 gave 0.2520 CO, and 0.0443 H,O.0-2315CIBH,lONS requires C = 68.1 ; H = 4.8 ; N = 6.3 per cent.A ction. of A cia's.-This sulphoxide is readily soluble in concen-trated aqueous hydrochloric acid, being then converted into thedeep crimson hydrochloride. The attempts made to isolate thelatter in the pure condition were unsuccessful, chiefly .on accountof the hygroscopic nature of the substance, and the ease with whichit is transformed into the chloro-derivative of N-methylthiodi-phenylamine. The platinichloride was therefore prepared byaddition of chloroplatinic acid to the aqueous solution of the salt.The precipitate was collected, and after recrystallisation it wasdried in a vacuum before analysis :C = 67.9 ; H = 4-88.,, 12-6 C.C.N, a t 17O and 763 mm. N=6.4.0-2161 gave 0.0474 Pt. Pt =21*93.0.1184 ,, 0-1568 CO, and 0.0238 H,O. C=36.1; H=2*2.(C,3H,10NS,HC1)2PtC14 requires Pt = 22.4 ; C = 35.9.H = 2.7 per lent.The PlatinichZoride of N-rn~et~ylphenasot~ioniunt (VIII) formsminute, reddish-brown needles, which melt with profound decom-position a t about 255O.Reduction.-The hydrochloride was reduced as rapidly as possiblein methyl-alcoholic solution with tin and hydrochloric acid.Whenreduction was complete, the colourless solution was poured intowater, and the precipita,te was collected. The product contained asmall quantity of the chloro-derivative, and, in order to removethis, it was fractionally crystallised from methyl alcohol. Themelting point and solubility of the chloro-compound lie close tothose of N-methyhhiodiphenylamine, and a complete separation isnot easily made. However, after repeated crystallisation, a sample,which melted a t 9B0, was obtained, and this, when mixed withN-methylthiodiphenylamine (m. p. looo), melted at the same tem-perature.It contained traces of chlorine. I n order to obtainfurther proof that thiodiphenylamine is not formed during thereduction of the chloride, both the crude and purified (m. p. 98O)products of reduction were treated with nitric acid (D 1.4) underthe conditions which yield the dinitro-derivatives of the group.The nitro-derivative was insoluble in hot aqueous alkali hydroxide,whereas the nitro-derivatives of thiodiphenylamine are readilyattacked by this reagent, yielding deep red solutions of the alkal190 BARNETT AND SMILES : THE INTRAMOLECULARsalts. Experiments made with artificial mixtures showed that verysmall quantities of thiodiphenylamine may be detected in thepresence of a large excess of the N-methyl derivative by this method.These experiments show that the methyl group of N-methylthiodi-phenylamine remains undisturbed during the conversion to thequinonoid salt.Con version of N-Me t h ytdinit ro p hen ytamine o-SuZphoxide.-Thedinitro-sulphoxide was prepared from N-methylthiodiphenylamineby the action of nitric acid, and it was purified in the mannerrecommended by Bernthsen (Annulen, 1885, 230, 92).To ensurethe purity of the substance employed, a sample was analysed:C = 48.4 ; H = 3.2. 0.1037 gave 0.1841 CO, and 0.0298 H,O.CI3Hg'OjN3S requires C = 48-9 ; H= 2.8 per cent.The conversion of the sulphoxide into the sulphonium derivativewas effected by means of sulphuric or hydrochloric acid.(a) Concentrated Sulphuric Acid.-A solution of dinitro-N-methyldiphenylamine o-sulphoxide in this acid was set aside forhalf an hour at the atmospheric temperature, and then poured onto powdered ice.The solid precipitate was collected and washedwith water until free from splphuric acid; it was then trituratedwith dilute aqueous sodium hydroxide to remove a small quantityof soluble material. The latter is probably formed by replacementof the nitro- by the hydroxyl group (see Barnett and Smiles, Trans.,1909, 95, 1262), but it was not further investigated. After re-newed filtration and washing, the reddish-brown product wascrystdlised from hot glacial acetic acid. Samples of the once (1)and four times recrystallised (2) product were analysed after beingdried in the steam-oven.(6) Hydrogen C1doride.-Methyl alcohol was saturated withgaseous hydrogen chloride a t Oo, and excess of the solution wasmixed with the dinitro-sulphoxide.The mixture was shaken forsix hours, and then set aside at the atmospheric temperature.After the lapse of forty-eight hours, the dark brown liquid con-tained in suspension an orange-red, crystalline substance, and, sincethis evidently was different from the more soluble portion, it wascollected and separately treated. The solution, which was shown bysubsequent experiment to contain the bulk of the desired sulphoniumcompound, was mixed with a large quantity of water, and the nowinsoluble product was collected and purified by recrystallisationfrom glacial acetic acid. Analysis (3) was then made with asample from the fourth recrystallisation. The crude product con-tained traces of non-ionisable halogen REARRANGEMENT Ol? DIP€IENYLAMINE ORTHO-SULPHOXIDES.'1 91(1) 0*1010 gave 0.1774 CO, and 0,0296 H20. C=4?.9; H=3.26.(2) 0.1005 ,, 0,1752 CO, ,, 0.0260 H20. C=47.5; H=2*87.(3) 0.1006 ,, 0.1752 CO, ,, 0.0287 H20. C=47*5,; H=3*16.CI3H9O5N3S,&H20 requires C = 47.5 6 ; H = 3.0 per cent.The analyses show that, as with the nitro-derivatives of thio-diphenylamine which have been previously studied (Trans., 1909,95, 1257), the conversion of the sulphoxide to the sulphoniumderivative is accompanied by absorption of water; but here themolecular proportion is half that previously observed, and it ismore firmly retained, since it cannot be removed by heating or byrecrystallisation from high boiling solvents.Din~tro-N-~ethylplielzazotitiolziuml hydrate forms reddish-brownleaflets, which do not melt below 250O.It is sparingly soluble incold benzene or glacial acetic acid. By reduction and subsequentoxidation, the substance is converted into the greenish-blue dyewhich is obtained by the same process from the dinitro-sulphoxide;but in contrast with the latter it does not exhibit the reactioncharacteristic of the thionyl group (Trans., 1906, 89, 696), sinceit does not yield the S-phenetyl derivative when treated withphenet.de and sulphuric acid. The only formula which can beassigned to the anhydrous compound is the following:c=3 k/\A\AINOZI 0 ",I I \/\I/\/S(IX. )but from reasons which will presently be stated, it is probable thatthe additional water in these substances is of constitution.The insoluble portion of the product which was obtained by theaction of hydrochloric acid on the dinitro-sulphoxide was separatelycollected and recrystallised from hot glacial acetic acid.It wasthus obtained in bright orange-red leaflets, which remained un-decomposed at 250O. Samples from two different preparations wereanalysed :C=48*3; H=3*51. (1) 0.1004 gave 0.1777 CO, and 0.0303 H,O.(2) 0'2028 ,, 0'3616 CO, ,, 0'0516 H20. C=48*6; H=2*8.CI3H9O,N3S requires C = 48.90 ; H = 2-82 per cent.When crystallised from hot nitrobenzene, the substance is0'2000 gave 0.3718 CO, and 0.0656 H,O.obtained with solvent of crystallisation :C=50-7; H=3.6.2C&W&3S,C&j02N requires C = 50.6 ; H = 3.0 per cent192 BARNETT AND SMILES : THE INTRAMOLECULARThe presence of nitrobenzene in this substance was proved bymixing the sulphuric acid solution with water and passing a currentof sterrm through the liquid. The substance melts and decomposesa t about 280O.Further experiment showed that this compounddoes not contain the sulphonium grouping,- and since it yields the8-phenetylsulphonium salt when treated with phenetole in sulphuricacid solution, it may for the present be regarded as an isomericform of the original sulphoxide. Probably the isomerism involvesthe nitro-grouping.Assuming that the conversion of sulphoxide (I) to sulphoniurnbase (11) takes place in the same manner with the imino-compoundsas with these N-methyl derivatives, it is clear that the hypothesisof migration of hydrogen from the imino- to the thionyl groupcannot be accepted as an adequate explanation of the change.Theortho-sulphoxides of diphenylamine contain the imino- and thionylgroups, and it is well known that each of these in simple derivativespossesses basic properties. So far as the thionyl group is concerned,it has been shown that the aliphatic (Saytzeff, Annulen, 1867, 144,148) and aroma;tic (Smiles and Le Rossignol, Trans., 1906, 89, 697)sulphoxides form nitrates and hydrochlorides. From these con-siderations and from the fact that the reaction can be effectedonly by acid reagents, it seems probable that the salts of thesulphoxides are formed in an initial stage of the reaction, andthat these are subsequently changed into the sulphonium derivatives.That a causal relation exists between the formation of these saltsand the production of the sulphonium compounds may be shownby the following experiments.(1) The Action of the same Acid Reagent o n Sulpkoxides ofVarying Basic Power.-Experiments were made with the tetra-nitro-, di-p-nitro-, isodinitro-, and the unsubstituted diphenylaminesulphoxides, the reagent being alcohol saturated with hydrogenchloride at the atmospheric temperature.In each case the con-ditions adopted were the same: the sulphoxide was shaken with alarge excess of the acid reagent a t about 15--17O, and theapproximate time required for the complete conversion to thesulphoxide was observed.The results are collected in the followingtable :Substance. Approximate time required.Diphenylamine o-sulphoxide.. , . . . . . . , . . . .. .. .N-Methyldiphenylamine o-sulphoxide ... . ..Di-p-nitrodiphenylamine o-sulphoxide.. , . . .isoDinitrodiphenylamine o-sulplioxicle.. . ...Tetranitrocliyhenylamine o-sulphoxida . , . about three weeks.apparently instantaneous.apparently instantaneous.about five hours.about five hours.The data cannot be regarded as anything more than very roughapproximations; but they serve to show that by decreasing thREARRANGEMENT OF DIPHENYLAMINE ORTHO-SULPHOXIDES. 193basic function of the sulphoxides, the tendency to form the sul-phonium base is correspondingly diminished.(2) The Action of Acids of Varying Strength o n t h e sameSuZphoxide.-In these experiments the diphenylamine o-sulphoxidewas employed as the standard.The colourless solutions of thissubstance become deeply coloured on the addition of acids, thesalt of phenazothionium being then formed. Equal volumes(50 c.c.) of 2N-aqueous solutions of acetic, monochloroacetic, tri-chloroacetic, and hydrochloric acids were separately mixed at thesame moment with 50 C.C. of an alcoholic solution (0.1 per cent.) ofthe sulphoxide. After a suitable lapse of time (thirty minutes),the solutions were examined in layers of equal depbh. A differencebetween the intensity of colour in these solutions could be readilydetected, but quantitative measurements of the intensity were notmade, since the solutions containing the stronger acids were ofslightly different colour, probably owing to the formation of di-acidsalts. When arranged in order of increasing intensity of colour,the solutions fall into the following order:F i f t y C.C.of 0.1 per ce,nt. Solution of Diphenylamine Sdphoxide inA Zcohol.Relative coefficientsWith 50 C.C. of of saponification2N-solution of velocity. Remarks.Acetic acid ........................ 0-003 colour appeared after 1 hour.Monochloroacetic acid ......... 0 -043 faint colour immediately produced.Trichloroacetic acid ............ 0.682 immediate coloration.Hydrochloric acid ............... 1 '000 immediate coloration.It may be remarked that after the further lapse of time theintensity of colour in these solutions increases, and the differencebetween each solution becomes even more pronounced.The centrecolumn of the table shows the relative affinities of the acids; thedata were obtained by Ostwald ( J . pr. Chem., 1883, [ii], 28, 449)from measurements of the velocity of hydrolysis of methyl acetate.Assuming that the intensity of colour of these solutions isroughly proportionate to the quantity of azothionium salt present,it follows that the amount of this salt formed at the end of a, givenperiod is controlled by the strength of the acid employed. It isclear that these two sets of experiments justify the hypothesis thatthe conversion of the sulphoxides to the sulphonium compoundsdepends on the preliminary formation of salts of the former sub-stances with the acid reagent.It is, however, difficult conclusively to determine the process bywhich these salts are converted to the quinonoid compounds, sincethey cannot be isolated in the pure condition for separate trea8bVOL.XCVII. 194 BARNETT AND SMILES : THE INTRAMOLECULARment. There are, however, only two alternatives: either (a) thatthey lose the elements of water, or ( b ) that migration of hydroxyltakes place. These will be separately dealt with in the ordergiven.To assume that elimination of water takes place in the mono-acid sulphoxide salt ( X a ) is evidently incorrect, for on this basisthe conversion of the N-methyl derivative would be impossible,and no account would be forthcoming of the additional moleculeof water in the products.In all the examples studied, a largeexcess of acid is necessary completely to effect the reaction, andthis fact lends colour to the assumption that the salts which undergothe change are of the di-acid type (X). It is apparent that theseNH/\/\/\I l l 1\/\/\/ s/\OH C1HCl*k*H/\/\/\I I I I\/\/\/Ssalts would be converted into the azothionium salts by the loss ofthe elements of water, the complete process being represented asfollows :HNH C1.N -H/\OH c1HO H HO H\' \/N N61(XII.)6 H(XIII.)Moreover, it is apparent that whether the resulting quinonoidsalt (XI) can be isolated or not must depend on the basic characterof the sulphonium and ammonium groups, and this is controlledby the nature and number of the groups present in the aromatiREARRANGEMENT OF DIPHENY LAMINE ORTHO-SULPHOXIDES.195nuclei (Kehrmann, Ber., 1906,39, 914; Smiles and Hilditch, Trans.,1908, 93, 1691). For example, the parent phenazothionium com-pound is obtained as the monohalide (XII) (Trans., 1909,95,1259),whilst the di- and tetra-nitro-derivatives, being completely hydro-lysed during the process of isolation, appear as sulphoniumhydrates (XIII).It is necessary to observe that this explanation of the processsatisfactorily accounts for the invariable occurrence in the azo-thionium compounds of an additional molecule of water, which isso difficult to remove as t o give rise t o the suspicion that it is notmerely water of crystallisation.Moreover, a satisfactory account is given of the conversion ofthe N-methyl sulphoxide to the sulphonium compound.The follow-ing formulae represent the process :C1 CH, C1 CH3\/ \/NH NHO CH,\/NIn this case it must remain doubtful whether hydrolysis takesplace at the ammonium or sulphonium group, but the formulagiven for the product is the more probable of the two alternatives,for with the parent compound there can be no doubt that theproduct is the sulphonium halide, since it has been isolated in theanhydrous condition (Kehrmann, Ber., 1901, 34, 4170).The alternative hypothesis of migration of hydroxyl fromquadrivalent sulphur to tervalent nitrogen in the sulphoxide saltaffords an equally satisfactory explanation of the change.Fromthis point of view the reaction must be regarded as a true intra-molecular rearrangement, being represented as follows :HO H (or R)\/ NH (or R) N/\/\/\ /\//\/\I l l 1 -+ t i l l\A/\/ \/A/\/S SBut, as previously remarked, we are a t present unable to offerany decisive evidence for the preference of either alternativehypothesis. On general grounds, the former of the alternativesgiven seems the more probable.0 196 BEKRY: THE ADSORPTIOX OFIn conclusion, it must be stated that the hypothesis described(1) The immobility of the alkyl group during the conversion of(2) The more basic the character of the sulphoxide, the more(3) The conversion of a given sulphoxide proceeds more easily(4) The absorption of the elements of water during the reaction.The results of the study of this reaction may be summed up asfollows :(1) The conversion of diphenylamine sulphoxides t o phenazo-thionium derivatives does not take place by direct migration ofhydrogen from the imino-group t o the oxygen of the thionyl group.(2) The salts of the imino-sulphoxides are first formed with theacid reagent, and these are then converted into the phenazothioniumsalt either (u) by loss of the elements of water, or ( b ) by migrationof hydroxyl from the quadrivalent sulphur to tervalent nitrogen.Preliminary experiments have shown that the conversion of thethionyl group to the quinonoid thionium arrangement may beeffected not only in other cyclic systems, but also in hydroxy- andamino-sulphoxides.is advanced to account for the following facts:N-methyldiphenylamine o-sulphoxide.readily does the change take place with a given acid reagent.the stronger the acid employed.These substances are now being investigated.In conclusion, we desire to thank the Research Fund Committeeof the Chemical Society for a grant which has defrayed the expenseof this research.THE O~~GANIC CHEMISTRY LABORATORY,UNIVERSITY COLLEGE, LONDON

ISSN:0368-1645    

DOI:10.1039/CT9109700186

出版商:RSC    

年代:1910

数据来源: RSC

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196 BEKRY: THE ADSORPTIOX OFXXL- The Adsorption o f Ui-uniurn-X by BariumBy ARTHUR JOHN BERGY, B.A.BECQUEREL has shown (Conzpt. rend., 1900, 131, 137; 1901, 133,977) that when barium is precipitated as sulphate in a uraniumsolution, the photographic activity of the latter is removed by thebarium sulphate. A similar result was obtained by Sir WilliamCrookes (Proc. Roy. SOC., 1900, 66, 409), who found that uraniumcompounds could be obtained photographically inactive by a singlechemical operation, the whole of the photographic activity beingconcentrated in a small residue termed uranium-X by Crookes.Soddy (Trans., 1902, 81, 860) showed that the whole of the &rayXulphateURANIUM-X BY BARIUM SULPHATE. 197activity of uraniam is due to the uranium-9, which is one of thedisintegration products of uranium (Rutherford and Soddy,Phd. Mag., 1903, [vi], 5, 441).I n the present communication, the adsorption of uranium-X hasbeen investigated quantitatively, and evidence has been obtainedof a, definite “ partition coefficient ” between the uranium-X in thebarium sulphate and in the solution.As the experiments wereapproaching completion, the author’s attention was directed to apaper by Ritzel (Zeitsch. physikal. Chern., 1909, 67, 724). Ritzelinvestigated the absorption of uranium-X by carbon, and hementions (Zoc. cit., p. 727): “Als Adsorbens wollte ich zunachstBariumsulphat verwenden Vorversuche zeigten aber bald dass dasBariumsulphat, von Versuch zu Versuch, mit sehr schwankenderKristallgrosse ausfallt, und man kann deshalb keine guten Resultateerhalten.” The present writer did not experience any difficulty ofthat kind.It was usually found perfectly easy to repeat a resultunder any given conditions. However, the use of barium sulphateis a disadvantage in studying the effect of time in the adsorptionof uranium-X, as it is probable that the crystals would increase insize with lapse of time.EXPERIMENTAL.A solution of pure uranyl nitrate (Merck), containing 400 gramsper litre, was employed. This solution was in radioactive equi-librium. Experiments were always carried out with 25 C.C. of thissolution. The B-ray activity due to the uranium-X in this quantityof material was determined by Crookes’s original method (Zoc. cit.).The liquid was diluted considerably, heated to boiling, a trace offerric chloride added, and ammonium carbonate added in quantitysufficient t o redissolve the precipitate of uranium carbonate.Theliquid was then filtered from the ferric hydroxide, and the activityof the uranium-X, removed by the latter, measured by a &rayelectroscope.The caseof the instrument was a stout brass cylinder, the internal diameterbeing 10.1 cm., and the internal height 12.6 cm. The base of theelectroscope was of aluminium foil 0.1 mm. thick. The pre-parations were placed on a, board at a fixed distance (7.7 cm.)below the base of the instrument. The rate of leak was determinedin the usual way with a reading microscope and a stop-watch. I ncvery case, the “ natural leak ” of the instrument was determinedand allowed for.This natural leak varied but slightly, the usualvalue being 3.7 scale divisions per minute. The measurements werealways compared with the leak due to a standard consisting of blackThis electroscope was of the ordinary single-leaf type198 BERRY: THE ADSORPTION OFuranium oxide. The mean of three concordant determinations ofthe &ray activity in 10 grams of uranyl nitrate carried out in thismanner was 106.6 scale divisions per minute.It was always possible to separate more than 90 per cent. ofthe uranium-X in the first operation by Crookes's method. Onacidifying the filtrate with nitric acid, and repeating the process,practically all the remaining uranium-X was removed. This waschecked by testing the residue after ignition.Unless otherwise stated, the experiments were conducted asfollows.The measured quantity of uranyl nitrate solution wastaken, acidified with a given quantity of a 10 per cent. solution ofsulphuric acid, and a quantity of water added, which, togetherwith the quantity of standard barium nitrate (2.5 grams per litre)employed for precipitation, would make the solution up to somedefinite volume. The precipitation was carried out in the cold, andthe liquid kept overnight. The solution was then boiled for oneminute, the barium sulphate collected, and its &ray activitymeasured. The, absorption of the &radiation in the barium sul-phate may be neglected, since the greatest mass of precipitate onthe filter paper wi19 only 0.11 gram.If there is a definite equilibrium between the uranium-X in thebarium sulphate and in the liquid, we should have:where C is the concentration of the uranium-X, and k and n areconstants.The concentration in the barium sulphate is x / m ,where x is the amount of uranium-X adsorbed, and m the mass ofbarium sulphate. The concentration in the liquid is a - 5/21, wherea is the initial quantity of uranium-X and v is the volume of thesolution. If there is equilibrium we should have:Series I.--a = 106.6 divisions per minute.sulphuric acid added to liquid. v=150 C.C.m(gram).0.00440.00880'01100.01540.0330 0440.0660-088X(divisions perminute).2 75-36 *38.114 -719 -321.824 *11 C.C.of 10 per cent.0 '740'720'7209'30.740 '740.770 -7URANIUM-X BY BARIUM SULPHBTE. 199Series ZZ.-a=106*6 divisions per minute. 10 C.C. of 10 percent. sulphurk acid added to liquid. .v=250 C.C.?n(gram).0'00440'01100'0220.0330'0440.0550.0880'110x(divisions perminute).4 *115.138'747-754.760.370-376.9I_sg(a-X) 1 -_log ?- -nm0.680-630.570 5 60.560 *550-540'52Series Z2I.-In this series the procedure was somewhat different.The uranium-X from one quantity (25 c.c.) of uranyl nitrate wasremoved by successive precipitations on separate days. The filtrateswere always made up to a constant volume (140 c.c.), and pre-cipitated each day by 10 C.C. of the solution of barium nitrate;15 C.C.of 10 per cent. sulphuric acid were added a t the beginningof the series only. In calculating l/n, a correction wasmade for the value of (a- x), owing to the solution recovering itsuranium-X content with time. The correction wm made by itrecovery curve for uranium-X. a (initially) =106.6 divisions per minute.(a - x)v = 150 c;c.m = 0.022 gram.X log (a - x) (corrected)-- - . (divisions per (corrected for log 2. 5% minute). recovery of Ur.-X). m43'7 64-6 0 -5530 '4 35 -8 0 -5017-3 21.0 0 *4610'0 13.7 0 -435.6 11 *o 0 *43Series Z V.--This series is precisely similar to series 111, exceptingthat 20 C.C. of 10 per cent. sulphuric acid were added to start with.v = 150 c.c., m = 0.022 gram, and a (initially) = 106.6 divisions perminute.2 log (a - 2 ) (corrected) -- (a - z)- m (divisions per (corrected for log x .nminute).recovery of Ur. - X ) . m45-0 63 ' 0 0 -5430 '4 34.7 0'4917.0 20 *1 0.458.7 13.9 0 *445 *6 11'2 0 -44From series I and 11, it is evident that dilution and excess ofsulphuric acid favour the adsorption of uranium-X, other thingsbeing equal. The influence of these two factors, separately, wasconfirmed by numerous other experiments, which it is unnecessaryto describe hereZOO TlTHERLEY 2-PHENYL-1 : 3-BEEZOXAZINE-4-ONE.Series I11 and IV are of interest, inasmuch as continuallydiminishing the concentration of the uranium-X in the solutionscarcely affects the constancy of 1 /!a.With regard to the effect of time, the following experimentalfacts may be of interest.It was found that as much uranium-X wasadsorbed by the barium sulphate two hours after precipitation aswhen the liquid was kept all night after precipitation. But if theliquid was kept for three days before collecting t.he barium sulphate,the quantity of uranium-X adsorbed was greater. This wouldappear to indicate that adsorption takes place very rapidly atfirst, but that diffusion of the uranium-X into the barium sulphateparticles takes place afterwards, and this latter process goes onfor a considerable time. However, no great importance is to beattached to these time experiments, owing to the probable increasein size of the adsorbing particles. For the same reas~n, it isdifficult to obtain evidence as to whether there is a definiteequilibrium between the uranium-X in the solid and liquid phaseswhich can be approached from both sides. Such a reversibleequilibrium has been shown t o exist in the case of the partitionof uranium-X between carbon and solution by Ritzel (Zoc. cit.,p. 735); who finds that for this equilibrium the equationCl = constant x C k , where CJ and Ck denote the concentration of theuranium-X in the solution and in the carbon respectively.The author desires to express his sincere thanks to Mr. Soddy forthe interest he has taken in these experiments and for his valuablesuggestions.PHYSICAL CHEMISTRY LABORATORY,GLASGOW UNIVERSITY

ISSN:0368-1645    

DOI:10.1039/CT9109700196

出版商:RSC    

年代:1910

数据来源: RSC

摘要:

ZOO TlTHERLEY : 8-PHENYL-1 : 3-BEKZOXAZINE-4-ONE.XXII. -2 -Phen yl- 1 : 3 -benzoxaxine-4-one,BY ARTHUR WALSH TITHERLEY.IN his criticism of the metoxazone theory of labile isomerism in theacylsalicylamide group, Auwers (Bey., 1907, 40, 3506) attributed thechange of N-benzoylsalicylamide (I) to 0-benzoylsalicylamide (111) (byboiling with acetic acid) to the intermediate formation of the unsatur-ated ring (11) by loss of water, which then immediately decomposedthis hypothetical ring, yielding the 0-benzoyl derivative, thus TlTHERLEY : 2-PHENYL-1 : 3-BENZOXAZINE-4-ONE. 201This view was shown to be untenable by Titherley and Hicks(Trans., 1909, 95, 908), but it appeared desirable to effect if possiblethe synthesis of this ring-compound in order that a study of itsproperties might be made in relation to the derivatives in the acyl-salicylamide group.Several attempts were made to prepare it fromphenylbenzometoxazone," C 6 H 4 < ~ ~ ~ ~ & , h , by eliminating two hydro-gen atoms, and from 0- and N-benzoylsalicylamides by the action ofdehydrating agents, like phosphoric oxide and zinc chloride, butwithout success.Eventually the compound was synthesised from phenyl salicylateand phenylbenzamidine by loss of phenol and aniline, thus :c6H4<O--C 'O*p Ph + PhOH + PhNH,,and i t was later found that the same ring-compound could be obtainedwhen special precautions were observed, by the action of hydrogenchloride on either N- or 0-benzoylsalicylamide at temperaturesbetween l l O o and 140O.These independent syntheses, which arediscussed later, and the properties of the compound place its consti-tution beyond doubt, and i t is, therefore, 2-phenyl-1 : 3-benzoxazine-4-one.The compound has the same melting point, 1 0 6 O , as that of itsisomeride, benzoylsalicylnitrile, CN*C6H4* OBz, from which, however, itdiffers greatly. It is markedly additive in properties, and its moststriking addition is with water. With pure water or dilute alkalis itis almost unaffected, but in presence of hydrogen ions it rapidly addsone molecule of water, a quantitative yield of N-benzoylsalicylamidebeing produced. This simple circumstance finally disposes of AUWBL'S~Shypothetical contention which involves direcb hydrolytic rupture atthe double linking, but is intelligible on the author's theory that theintermediate hydroxy-derivative (IV) is too unstable to exist, asalready frequently indicated, and at once rearranges to N-benzoyl-salicylamide, thus.:The still alternative explanation that hydrolytic rupture takes place* The correct name of this compound is 2-phenyldihydro-1 : 3-benzosazine-4-onebut in view of its use in previous papers, '' phenylbenzometoxazone " is retained inthe present one202 TI’I’HERLEY : 8-PHENYL-1 : 3-BENZOXAZiNE-4-OKE.between the phenolic oxygen atom and the carbon atom to which thephenyl group is attached, is discounted by the comparatively greatstability of the unsaturated ring-compound with alkali, which wouldfavour such a rupture, and the only possible mechanism appears to bethe above, which is identical with that occurring in the conversionof nitriles into amides through the agency of acids.The above mechanism throws some light upon the decomposition bywater in presence of hydrogen ions of certain allied compounds inwhich the double linked C:N pair appews in the molecule. Auwersobserved (Ber., 1904, 37, 2249) that the comparatively stable unsatur-ated ring (V) yields a hydrobromide which in aqueous solution addswater and passes into the salt of o-aminobenzyl acetate (VII), whilstJ.F. Thorpe has shown that all true imino-compounds (VIlI) are at oncedecomposed by dilute acids, giving ketonic derivatives (X). In thesecases a similar mechanism is evidently at work, in which (1) thehydroxyl group attaches itself to carbon arid the hydrogen atom tonitrogen, and (2) the resulting unstable compcund (VI or IX) changeseither by wandering of a hydrogen atom or by loss of ammonia intoa stable derivative :(VIII.) (IX.) (X.That such intermediate hydroxy-compounds are first formed in thecases observed by Auwers and Thorpe appears to follow from thecomplete analogy of these reactions to that of 2-phenyl-1 : 3-benz-oxazine-4-oneY where the production of the intermediate hgdroxy-compound must be admitted on the grounds already stated andin view of’ the author’s previous observations.Contrasting the intermediate hydroxy-derivatives in the author’scase (XI) with that of Auwers (XII) :CO*TH NH*QMe*OH(XI. 1 (XII.)%H4<()-CPh.()H C6H4<CH2.0 2it is clear that when the hydrogen atom of the hydroxyl groupwanders, (XI) yields an N-acyl derivative, whilst (XII) yields an0-acyl derivative. Theoretically, each could yield an 0- or N-acylderivative according to whether the hydrogen atom wandered tonitrogen or to the phenolic oxygen atom, and the final result probablydepends on the conditions which favour one or other of thesealternatives. Thus, in Auwers’s case it is natural that the hydroTITHERLEY : 2-PHEKYL-1 : 3-BENZOXAZINE-4-ONE. 203bromic acid would favour the production of the 0-acyl derivative,which is a base and yielded the salt, rather than the neutral N-acylderivative, which is an amide. I n the author's case neither the0- nor N-benzoylsalicylamide is a base, and the rearrangement yieldsBimply the stable form (N-benzoyl).At t,he same time it must benoted that, although neither of the isomerides is a base in the ordinarysense, 0-benzoylsalicylamide as a primary amide must be more basicthan its isorneride, which is secondary. Experiments which have beenmade on the two isomerides show that the former is more basic, andyields a definite hydrochloride when treated in presence of benzenewith hydrogen chloride. It might therefore be anticipated thathydrogen chloride should effect the rearrangement of N-benzoyl-salicylamide into its isomeride [through the hydroxy-form (Xl)].Such a change has already been partly effected by continued boilingwith pure acetic acid (McConnan and Titherley, Trans., 1906, 89,1331), a fact which supports the supposition that the intermediatehydroxy-form may open in either of the two alternative waysaccording to conditions (acetic acid favouring the production of themore basic 0-benzoyl derivative).Experiments on the action ofhydrogen chloride on N-benzoylsalicylamide in benzene showed thatno change took place in the cold, but that in presence of boilingxylene slow and incomplete rearrangement to 0-benzoylsalicylamideoccurred. As the experiments proceeded, however, it became apparentthat, besides rearrangement, chemical elimination of water was takingplace at about 130'. By using ethylene dibromide or anisole assolvents and distilling off the water as produced, the latter action wasaccelerated, and 3-phenyl-1 : 3-benzoxazine-4-one was formed in largequantities.The latter was even more easily obtained by the action ofhydrogen chloride on 0-benzoylsalicylamide in boiling toluene orxylene if the water formed was continually removed. The hydrogenchloride virtually behaves as a catalyst, since relatively smallquantities were found to be suf€icient to effect the change. It isprobable that the loss of water is not due to direct dehydration,but to the intermediate formation of the chloro-derivative (XIII),which immediately loses hydrogen chloride and apparently is incapableof existence 204 TITHERLEY : 2-PHENYL-1 : 3-BENZOXAZINE-4-ONE.When 2-phenyl-1 : 3-benzoxazine-4-one (11) in benzene solution istreated with dry hydrogen chloride, a white, crystalline compoundcontaining chlorine is precipitated, which on exposure to atmosphericmoisture rapidly passes into N- benzoylsalicylamide, but on treatmentwith aniline yields a yellow, crystalline solid, melting at 106", whichwas found to have the constitution OH*C6H4*CO*N:CPh*NKPh(ealicylphenylbenzamidine). From this behaviour it was supposedthat the ring-compound had added hydrogen chloride, giving thechloro-compound (XIII), or, by rearrangement, the compoundOH*C,H,*CO*N:CCIPh, either of which might be expected to behaveas above with water and aniline (see below).But from the fact thatthe hydrogen chloride additive product in presence of benzeneregenerates the original ring-compound (1.1) with alkali, and from itsother properties, it must be concluded that the product is merely thesalt, C,H,<Co*8'Hc1, which with water would a t once give N-benzoyl-0-GPhsalicylamide (as explained above) ; whilst its curious behaviour withaniline subsequently became clear when it was found that the freering-compound itself readily unites with aniline, producing the aboveamidine derivative according to the following scheme :(XIV.)CO-IjTHc6H4<OH CPh:NPhco-fiC6H4<OH CPh-NHPh'(XVI.)The reaction is reversible, and the anilino-derivative (salicylphenyl-benzamidine) is a tautomeric substance.Its tautornerism comprisesthe three forms (XIV), (XV), and (XVI), of which the last tworepresent ordinary amidine tautomerism, and it is evident that one ofthese two formuls must be given to the substance itself, melting at106O, because of its phenolic properties.It loses aniline, however,below looo, and passes quantitatively into 2-phenyl-1 : 3-benzoxazine-4-oneY provided that the aniline is removed, and the easy reversibilityof the above process would seem to imply that the compound isbordering on the verge of ring-formation (XIV). That the phenolichydroxyl group and the group *CPh:NPh are in intimate stericassociation is confirmed by the difficulty with which the substancTITHERLEY 2-PHENYL-1 : 3-RENZOXAZINE-4-ONE. 205dissolves in dilute aqueous sodium hydroxide, and at first it wassupposed that the ring formula (XIV) must be adopted for thesubstance. This view, however, is inconsistent with the brightyellow colour of the substance, for whilst phenylbenzometoxazone and2-phenyl- 1 : 3-benzoxazine-4-one are colourless, the alkali and ammoniaderivatives of N-acylsalicylsmides are bright yellow, and the phenolicnature of the anilino-derivative is confirmed by the strong ferricchloride reaction it gives.In the synthesis of 2-phenyl-1 : 3-benzoxazine-4-0110 by heatingphenyl salicylate with phenylbenzamidine, t h i s anilino-compound isthe first product of the reaction, and it is owing to its reversibledecomposition, as above, that the unsaturated ring compound (IT)is obtained, and for the same reason the yield of the latter iscomparatively small, thus :(11.1A considerable quantity of diphenylbenzamidine (XVII) is alsoproduced as a, result of a secondary reaction, which also appears to bereversible, between the aniline and salicylphenylbenzamidine, thus :CO-YH PhNHz CO*NH, NPhC6H4<OH CPh:NPh C6H4<OH CPheNHPh.(XVII.)EXPERIMENTAL.2-Phenyl-l : 3-benxoxnxine-4-one.(a) Pmparation, from PIkn,yZ SaZicylate :-(a) 21.4 Grams of phenylsalicylate and 19.6 grams of phenylbenzamidine were heated at 110' forsix and a-half hours, during which aniline and phenol were producedin quantity.On cooling, the resulting viscid, yellow syrup was stirredwith 150 C.C. of water and 100 C.C. of 10 per cent. sodium hydroxideto remove phenol and salicylphenylbenzamidine, and the yellowalkaline solution was decanted off. The remaining syrup was washedwith water, dissolved in 200 C.C. of pure benzene, and the benzenesolution washed with alkali and water.In order to remove anilineand diphenylbenzamidine, the benzene solution was shaken for a fewminutes with abont 300 C.C. of 5 per cent. sulphuric acid, the upperbenzene solution washed with water, and $hen as rapidly as possibl206 TITHERLEY : 2-PHENYL-1 : 3-BENZOXAZlXE-4-ONE.shaken with dilute alkali, to remove the N-benzoylsalicylamide formedduring washing with acid and to neutralise the remaining traces ofacid. (During the former operation some losl; was entailed, because ofthe great instability of the ring compound* in presence of diluteacid.)The alkali extract was found to contain besides phenol, aconsiderable quantity of ssllicylphenylbenzamidine, which was pre-cipitated on adding acid and then decomposed, giving N-.benzoylsalicyl-amide. The acid extract contained aniline and diphenylbenz.lmidine.The latter was isolated (4 grams), and found to be identical withWallach's compound (Armalen, 1877, 184, 83).The clear benzene solution WAS washed twice with water, dried, andevaporated a t about 40".Massive crystals remained, together with asyrupy portion, which crystallised after several hours. After mashing.with a little ether and draining on porous porcelain, the crude product(12.5 grams) was crystallised from 700 C.C. of light petroleum, thesolution being allowed to cool very slowly to avoid deposition of syrup.White or transparent, colourless leaflets or plates (m. p. 104";10.5 grams) separated, which on recrystallisation from light petroleumwere obtained in the pure state and then molted sharply a t106-107°:0.2193 gave 0.6024 CO, and 0.0759 H,O.0.1688 ,, 9.3 C.C.N, (moist) at 20° and 757 mm. N=6*28.C1,H,O,N requires C: = 75.34 ; H = 4.03 ; N = 6.27 per cent.2- Plienyl-1 : 3-6enxoxaxine.4-one is very soluble in chloroform oracetone, readily so in benzene, methyl alcohol, or ethyl acetate, andrather less so in ethyl alcohol, ether, or pyridine. It dissolves in about'70 parts of light petroleum (b. p. 90-120"). It may be recoveredunchanged after solution in these solvents, even pyridino. Itssolutions give no coloration with alcoholic ferric chloride. I n glacialacetic acid it readily dissolves, but owing to the presence of rnoistur2the solution soon deposits N-benzoylsalicylamide.Behuvwu?* with Water.-Ths cornpound is insoluble in wLtter, but onboiling an oil is produced which dissolves appreciably.The clear hotaqueous solution if rapidly cooled becomes turbid, and after a shorttime fine needles of the unaltered compound separate, but not withoutproduction of some N-benzoylsalicylamide.was studied by diluting an alcoholic solution largely, but insufficiently,to induce separation. The clear solution remained clear for aboutthree hours, after which it became faintly turbid, owing to separatior~+i If ether is used instead of benzene as a solvent, the whole of the ring-compoundis decomposed during the washing with acid.C = 74.92 ; R = 3.85.0.3480, by Kjeldahl's method, required 16.0 c,c. N/lO-HGl. N = 6.3'3.Its bchaviour witTITHERLEY : 2-I'HENTL-1 : 3-BENZOXAZINE-4-ONE. 207of the highly insoluble N-benzoylsalicylamide, which, however, wasnot completely precipitated in twenty-four hours.Whether purewater free from carbonic acid would behave like ordinary distilledwater has not been tried. Traces of acids jinorg$nic and organic)enormously accelerate the action of the water, and it was shownroughly that the velocity depends on the concentration of the acidadded. If 20c.c. of a 0.05. per cent. solution are treated with 0.05 C.C.of 10 per cent. hydrochloric acid, the decomposition is complete inabout seventy seconds. Accurate velocity measurements have notbeen made, but the quantitative nature of the conversion was easilyshown by decomposing a known weight in dilute alcohol.Onacidifying the clear solution with a few drops of hydrochloric acid,after a few seconds a voluminous, microcrystalline precipitate *separated, which was collected and dried at 100' :0.2 2 30 gave 0.23 9 8 N-benzoylsalicylsmide.The purity of the N-benzoylsalicylamide was shonn by the sharpmelting point (206') before recrystallising.Behaviour with Acids.-The cyclic compound has only a weaklybasic character, and with aqueous acids is decomposed withoutpreviously dissolving. It does not yield a picrate in benzene oralcoholic s o h tion. Dry hydrogen chloride in benzene solutionprecipitates its hydrochloride, which, however, could not be isolated ina pure condition for analysis, owing to the great ease with which itis decomposed by atmospheric moisture.Behuviour with Alkalis.-With cold aqueous sodium hydroxide andammonia, the compound is comparatively stable and only very slowlychanged to the salt of N- benzoylsalicylamide, but sodium hydroxideimmediately decomposes it in alcoholic solution.Dry ammoniaproduces a yellow colour with an alcoholic solution of the compound,and probably an additive compound like that obtained with aniline isformed ; this is under investigation.Behaviour with Phosphorus Pentachloride-The compound, on treat-ment with phosphorus pentachloride in presence of chloroform,instantly gives a bright lemon-yellow, crystalline solid,C,4H,0NCI,,POC13,identical with th :t obtained by Titherley and Hicks (Zoc. cit.) by theaction of phosphorus pentachloride on phenylbenzometoxazone a thigher temperatures.Beduction.-The reduction of 2-phenyl-l : 3-benzoxazine-d-one* The reaction affords a very delicate test for 2-phenyl-1 : 3-benzoxazine-4-one.On dissolving mintite amourit in a drop of alcohol and treating with about 1 C.C. ofwater and a trace of any dilute acid, a precipitate appears suddenly after a fewseconds.C,,H,02N requires 0.2410 N-benzoylsalicylamide208 TITHERLEY : 2-PHENYL-1 : 3-BENZOXAZINE-4-ONE.cannot be effected by sodium amalgam, in alkaline solution, or byacid reducing agents, owing to ring rupture, With aluminiumamalgam, however, the reduction proceeds rapidly.A dilute alcoholic solution of the substance was treated withan excess of aluminium amalgam, and water added gradually.Whenthe reduction was complete, the alcoholic solution mas filtered andallowed to evaporate. The resulting solid was washed with dilutealkali, dried, and extracted with boiling alcohol. A white, sparinglysoluble solid remained behind, which has not yet been identified, and thealcoholic solution deposited needles consisting of impure phenylbenzo-metoxazone. By carefully recrystallising from alcohol, the latter wasobtained pure in fine needles melting at 169", and was easilyidentified. The melting point after mixing with a specimen ofphenylbenzometoxazone synthesised from salicylamide and benz-aldehyde mas 168-169'. The yield was about 30 per cent., and asimilar reduction performed in an ethereal solution containing5 per cent.of alcohol gave a yield of 40 per cent.(b) Preparation from O-BenxoyEsaZic~Zamide.-A mixture of 3 gramsof 0-benzoylsalicylamide and 30 C.C. of xylene contained in a distillingflask was heated in a bath to 145O, and when the solution becameclear a stream of dry hydrogen chloride was passed in for a fewminutes. By gradually raising the temperature of the bath to 155O,the xylene was allowed to distil over drop by drop, carrying with itthe water formed in the reaction. The hydrogen chloride actedcatalytically, and only a relatively small quantity was necessary, butin order to make good that lost by distillation, a few bubbles of thegas were passed into the liquid at intervals of three minutes, Therate of distillation was regulated so that the majority of the xylenehad passed over in an hour.About 0.2 gram of water passed overwith it, and an oil remained in the flask which partly crystallised oncooling and consisted of a mixture of 2-phenyl-1 : 3-benzoxazine-4-0110and its hydrochloride and unchanged 0-benzoylsalicylamide, togetherwith a little xylene. When cold it was treated with 20 C.C. of benzeneand well shaken with an excess of 3 per cent. sodium hydroxide.A considerable quantity of lemon-yellow solid (the sodium derivativeof N-benzoylsalicylamide produced by rearrangement of O-benzoyl-salicylamide) separated, which was mostly removed by repeatedlywashing the benzene extract with water. The benzene extract wasthen dried, filtered, and evaporated at 50°, when large, colourlessplates were left, together with an oil which crystallised on cooling.The solid was practically pure 2-phenyl-1 : 3-benzoxazine-4-one, andweighed 1.8 grams, or 65 per cent.of the theoretical yield. Onrecrystallising from about 100 C.C. of light petroleum and cooling slowlyTITHEIiLEY : 2-PHENYL-1 : 3-BENZOXAZINE-4-0EE. 209it separated in small, colourless, glistening plates, which meltedsharply at 106*, and a mixture with a specimen obtained by theamidine method of synthesis also melted at 106':0.2128 gave 0.6003 CO, and 0,0755 H,O. C=76.8; H=3.9.0.2362 ,, 13.7 C.C. N, (moist) at 23" and 755 mm. N = 6-49.C,,H90,N requires C = 75.34 ; H = 4.03 ; N = 6.27 per cent.The properties of the substance agreed in every particular withthose of the compound obtained by the amidine method.I n a similar preparation to the above, using toluene instead ofxylene as solvent, the compound was also obtained, but the yield waslower (36 per cent.of the theoretical).(c) Prepccration from ~ - ~ e n ~ o y ~ s c c ~ ~ c ~ ~ ~ r n ~ ~ e . - A similar method tothe above was employed, using anisole as a solvent at 130'. Abouttwo and a-half hours mere required for the completion of the change,and a yield of 60 per cent. of 2-phenyl-1 : 3-benzoxazine-4-one (m. p.106-107°) mas obtained. Ethylene dibromide mas also used withsuccess as a solvent, but xylene mas unsatisfactory, owing to the smallsolubility of ni-benzoglsalicylamide. During the action of the hydrogenchloride, some of the N-benzoylsalicylamide is rearranged t o O-benzoyl-salicylamide, and this was isolated in smal1:quantity in one experiment,when xylene was used as solvent, as needles melting with rearrange-ment a t 144".0.1812 ,, 0.50'70 CO, ,, 0.0635 H,O.C=76*39 ; H=3'89.Saliey Zpheny Zbenxamidine,OH*C,H 4* COON : CPh*NH P= OH* C6H,* CO *NH CPh: NPh,was obtained by the sction of aniline on 2-phenyl-1 : 3-benzoxazine-4-one or its hydrochloride by the following methods.One gram of 8-phenyl-1 : 3-benzoxazine-4-one and 0.5 ,gram ofaniline were warmed t o 50°, and the resulting yellow oil, which didnot crystallise on cooling, was dissolved in 50 C.C. of boiling lightpetroleum and the clear yellow solution allowed to cool slowly. Ayellow syrup was deposited, which, after being kept for twelve hoursin contact 'with the mother liquor, changed to a mass of beautifultransparent, yellow needles (1.3 grams), and the mother liquor yieldeda further quantity (0.1 gram), the total yield being 93 per cent.ofthe theoretical.When instead of light petroleum as a solvent, ether (15 c.c.) wasused, the pure compound separated after several hours in clusters ofneedles (0.9 gram) without any syrup being firsti deposited, and afurther quantity (0.2 gram) was obtained from the mother liquor.The substance was also prepared in the pure state by treating abenzene suspension of 2-phenyl-1 : 3-benzoxazine-4-one hydrochloridewith aniline. The identity of the yellow needles obtained by theVOL. XCVlI. 210 TITHERLEY : 2-PHENYL-1 : 3-BENZOXAZINE-4-0NE.different methods was shown by a comparison of melting point(1 05-10ri0) and other properties :0.2750 gave 19.8 C.C.N, (moist) at 17" and 772 mm.C,oH,,0,N2 requires N = 8.86 per cent.Salicylphenylbe~~xamidine is somewhat sparingly soluble in ether,moderately so in alcohol, and readily soluble in chloroform or benzene.Its solutions give a reddish colour with alcoholic or ethereal ferricchloride. Its solutions on evaporation at the laboratory temperatureyield syrups which crystallise completely only after several days, andit is probable that two or more isomeric forms in equilibrium areproduced by labile change when the yellow needles are dissolved inany solvent. If heated in a light petroleum solution for any length oftime, as in crystallising large quantities, the substance more or lessdissociates into aniline and 2-phenyl-1 : 3-benzoxazine-4-one, whichseparates to some extent on cooling in colourless needles or tuftsalongside the yellow needles of the unchanged substance. Prolongedboiling leads to decomposition of a portion, owing to the action of theaniline (see below) forming diphenylbenzamidine.Salicylphenylbenzamidine possesses weakly basic and weaklyphenolic characters; it is soluble in, but at once decomposed by,hydrochloric acid, yielding N-benzoylsalicylamide. I n a condition offine powder it is only very slowly soluble in dilute sodium hydroxide ;a yellow solution of the sodium salt results, from which, however, itis apparently impossible to recover the original substance ; on acidifica-tion with hydrochloric acid, a yellow precipitate is formed, solublein excess of acid to a nearly clear solution, from which dV-benzoyl-salicylamide is almost instantly precipitated. When salicylphenyl-benzamidine is heated a t 9 5 O , it dissociates, and eventually melts to aclear yellow liquid with an odour of aniline ; if the latter is allowedto evaporate slowly in an open shallow vessel, the yellow colourbecomes less conspicuous, and at the end of some hours a colourlessliquid results, which finally sets to a mass of colourless plates, con-sisting of 2-phenyl-1 : 3-benzoxazine-4-one, 'the yield of which wasalmost theoretical. When heated with aniline at 100' for severalhours, salicylphenylbenzamidine is partly decomposed into salicyl-amide and diphenylbenzamidine, the latter obtained in a yield of35 per cent.N=S.50.ORGANIC LABORATORY,[JNIVERSITY OF LIVERPOOL

ISSN:0368-1645    

DOI:10.1039/CT9109700200

出版商:RSC    

年代:1910

数据来源: RSC

摘要:

BOYLE : IODOBENZENEMONOSULPHONIC ACIDS. PART 11. 211XXIII.-Ioclobenze.ilemonosul~7~onic Acids. Pa,rt I . .Estem und Salts o j Bi- and T~,i-ioclo~c?nxe7ae,~~~l~~~~Acids.By MARY BOYLE.IN the first communication on this subject (Trans., 1909, 95, 1683)a brief account was given of the preparation of 2 : 5- and 3: 4-di-iodo-benzenesulphonic ethyl esters. It was stated that they wereobtained when the sulphonyl chloride was treated either withalcohol in the presence of sodium hydroxide or, when dissolved inether, with a solution of sodium ethoxide in alcohol, but beyondthe further statement that they melted a t 113O and 8 1 O respectively,no account of their properties was submitted, and no analyticalresults were given. Further experiments on ester formation havemade clear that neither of the above methods is satisfactory asregards yield and purity of the product unless careful attention ispaid to the proportions of interacting substances and to theduration of the action, and the ester melting at 1 1 3 O , preparedwithout such attention to detail, proved, on analysis, to be slightlycontaminated with the sulphonyl chloride from which it was formed,the pure ester melting about 6 O higher.Under the right con-ditions, however, it has been found possible to esterify all the iodo-benzenesulphonic acids discussed in Part I., and to obtain verywell-characterised methyl and ethyl derivatives,Methyl and ethyl benzenesulphonates were prepared by Hiibner(Annalen, 1884, 223, 237) by the action of sodium alkyloxidesfree from alcohol on solutions of the sulphonyl chlorides in absoluteether, and by IZrafft and Roos (Eer., 1892, 25, 2257) by allowingthe chloride to remain for many days a t low temperatures incontact with pure methyl and ethyl alcohols respectively; p-chloro-and p-bromo-benzenesulphonic and certain naphthalenesulphonicmethyl and ethyl esters were described by the same cxperimenters,and the corresponding p-iodo-derivative was prepared in 1895 byKastle and Murrill by the use of sodium ethoxide (Amer.Chenz. J.,17, 290).I n Krafft’s experiment with chloride and alcohol alone, theemployment of low temperatures seemed imperative, since, as wasstated in a later communication (Ber., 1893, 26, 2823), completehydrolysis occurred when the two were heated together in sealedtubes, or, in a few cases, when heated for a short time on thewater-bath.On the other hand, there is the statement byH. E. Armstrong (Proc., ‘1891, 7, 184) that many dibromo-P 21 2 BOYLE : IODOBEKZENEMONOSULPHONIC ACIDS. PART 11.naphthalenesulphonyl chlorides are readily converted into esters byboiling with excess of alcohol, the 1 : 4-dibromo-compound beingespecially remarkable for the ease with which it is esterified, a verysmall proportion only undergoing hydrolysis ; some isomeric sul-phony1 chlorides, however, are, according to him, hydrolysed almostcompletely under exactly the same conditions.I n preparing di- and tri-iodo-benzenesulphonic esters, bothmethods have been made use of, and it is interesting to note thatisomeric acids often behave very differently under similar experi-mental conditions, the orientation of the molecule appearing toinfluence to some extent the stability both of the sulphonyl chlorideand of the alkylated sulphonic group.The insolubility of mostof the sulphonyl chlorides in cold alcohol rendered the success ofKrafft’s method improbable, and the one experiment which wasmade proved quite unsuccessful; all of them, however, dissolved inhot alcohol with more or less ease, with gradual esterification.The tri-iodo- dissolved with much more difficulty than the di-iodo-compounds, and the crystals which separated from the cooled clearsolution were much less contaminated with unchanged chloride thanwas the case when di-iodo-compounds were under investigation.Ofthe three tri-iodobenzenesulphonyl chlorides investigated, the3 : 4 : 5-derivative dissolved in boiling absolute alcohol with mostdifficulty and yielded the purest product, the 2: 3 : 5-derivativedissolved with least difficulty, but yielded a product which onlybecame homogeneous after repeated re-solution; the 2 : 4 : 5-derivative seemed to lie intermediate between these two.It seems probable, then, that it is the contiguity of the iodineatom to the sulphonyl chloride group that renders the latter difficultof attack by the alcohol; in every case, however, a hydrolysingaction accompanies esterification, the yield of ester under the mostfavourable conditions never realising more than 60 to 70 per cent.I n the case of the di-iodosulphonyl chlorides, no quantitativeexperiments have been carried out, but none seem necessary inview of their very decided differences in behaviour towards alcohol.There is no doubt that the symmetrical 3 : 5-derivative yieldsan ester which is practically pure after one recrystallisation, thatthe 2 : 5- and 3 : 4-derivatives are attacked with about equaldifficulty, and that the 2 : 4-derivative cannot be made to yield anester at all by this method, so that here again, with the doubtfulexception of the 2 : 5-derivative, inhibition seems to be a questionof the contiguity of the iodine atom and sulphonic group.The exceptional behaviour of 2 : 5-di-iodobenzenesulphonylchloride towards alcohol is in accord with Armstrong’s statementwith respect to the behaviour of 1 : 4-dibromonaphthalenesulph~nyHOYLE : IODOHENZENEMONOSULPHOKIC ACIDS.PART 11. 213chloride in tke same circumstances (Zoc. cit.), and is also at one withthe peculiar behaviour of the corresponding 2 : 5-ester towardsalcohol, this ester being more easily hydrolysed by hot alcohol thanany of the other ethyl di-derivatives, hydrolysis occurring to theextent of about 39 to 40 per cent. when the two substances areboiled together for five minutes.The extent to which hydrolysis occurs when iodobenzenesulphonicesters are treated with hot alcohol was investigated in the firstinstance in order to ascertain the effect of the introduction of asecond iodine atom on the stability of the ester.Kastle andMurrill have investigated the behaviour of benzenesulphonic esterand its p-chloro-, p-bromo-, and p-iodo-derivatives towards alcoholboth a t the ordinary temperature and at looo (Am'er. Chem. J.,1895, 17, 292), and their results show clearly (1) that hydrolysisoccurs very slowly at the ordinary temperature, not more than19 per cent. being attacked in thirty days under the most favour-able conditions (one part of ester to 50-100 parts of alcohol), (2)that hydrolysis takes place much more rapidly a t looo, about 9 percent. undergoing change in five minutes, other conditions beingthe same, and (3) that the introduction of a halogen atom intothe nucleus considerably weakens the stability of the ester, 20 to21 per cent. now being changed in the same time as before; thethree halogens seem to exert practically the same influence.The introduction of a second and of a third iodine atom intothe nucleus would be expected, therefore, still further t o diminishthe stability of the ester towards alcohol, and experimental resultsentirely confirm such a view, the average hydrolysis f o r di-iodo-and tri-iodo-benzenesulphonic esters being, after five minutes atlooo, about 30 to 33 per cent.The experiments, unlike Eastle's,were conducted under atmospheric pressure, equivalent weights ofthe different esters mixed with the same volume (about fifty timesthe theoretical amount) of absolute alcohol being heated underreflux in boiling water for five minutes; the cooled mixture wi19then either diluted with alcohol and titrated with AT/ 10-sodiumhydroxide, or the unchanged ester was precipitated with water,collected, and the filtrate and washings titrated as before.Thelatter method is perhaps the better, since the unchanged esterpresent during titration is slowly hydrolysed by the added sodiumhydroxide; on the other hand, this hydrolysing action takes placeso slowly that it is comparatively easy t o detect the end-point of theacid-neutralisation.In these experiments it is difficult to compare the tri-iodo- withthe di-iodo-esters, and also the tri-iodo-esters among themselves,since two of these, namely, 3: 4 : 5-tri-iodo- and 2: 4 : 5-tri-iodo214 ROYLE : IODOBENZENEMONOSULPHONIC ACIDS. PART 11.benzenesulphonyl ethyl esters, are so sparingly soluble in alcohol,even after careful powdering, that at the end of the five minutes’heating only a small proportion has passed into solution to besubjected to the hydrolysing action of the alcohol; the 2 : 3 : 5-esterYhowever, is as soluble as the di-iodo-compounds, so that results in thelatter cases are strictly comparable.Such results show clearly thatthe greater the number of iodine atoms in the nucleus, the less thestability of the ethylated sulphonic group, ethyl monoiodobenzene-sulphonate, according to Kastle, being hydrolysed to the extent ofabout 20 per cent, when heated to looo with alcohol for five minutes,ethyl di-iodobenzenesulphonates, according to the author, under-going from 25 to 35 per cent. hydrolysis, and ethyl 2 : 3 : 5-tri-iodobenzenesulphonate from 45 to 55 per cent.The results obtained on directly titrating the hydrolysed solutionof the ester are always slightly lower than the corresponding onesobtained after precipitation of the unchanged ester, a fact no doubtdue to the hydrolysing action of water, which, although very slightand practically negligible at the ordinary temperature for it shortperiod of time, may become of some account after the twelve hoursnecessary for complete precipitation.From the experiments on the relative ease of hydrolysis of thefour ethyl di-iodobenzenesulphonates, no absolutely definite con-clusions can be drawn.All experiments seem to show that the2 : 5-ester is the most easily hydrolysed by boiling absolute alcohol,and that the 3 : 5-ester comes next in order; most experimentsplace the 2 : 4-ester next in order of stability, and the 3 : $-ester asthe most stable of all and least easily affected; some experiments,however, interchange the order of the two latter substances.Thefollowing table shows the percentage hydrolysis which occurred insix different experiments :Percentage hydrolysis.Ester. (1). (2). (3). (4). (5). (6).2 : 5- 39 39 - 27 32 -3 : 5- 35 363 : 4- 24 24 24 24 22 272 : 4- 22 29 29 15 29 30- - - 26- - 2 : 3 : 5 - 57 - 54 50The tri-iodo-ester is added for purposes of comparison.I n order to confirm Kastle’s statement that the methyl esters axemore easily attacked than are the ethyl derivatives by thecorresponding alcohols, the action of methyl alcohol on methyl2 : 5-di-iodobenzenesulphonate was investigated. Equivalent weightsof the ethyl and methyl esters were boiled for five minutes with10 C.C.of ethyl and methyl alcohol respectively, the unchangeBOYLE : ZODOBEN~ENEMONOSULPHON~C ACIDS. PART II. 215esters precipitated, and the filtrates t.itrated with N / 10-sodiumhydroxide.The following results were obtained :Ester. Percentage hydrolysis.2 : 5-ethyl ester ..................2 : 5-methyl ester ............... 4839’5in complete accordance with Kastle’s statement.Since Krafft’s method of preparing sulphonic esters had provedunsuccessful, and the method of boiling the sulphonyl chloride withalcohol unsatisfactory, since, also, the method consisting in treatingthe chloride with warm alcohol in presence of excess of sodiumhydroxide resulted, in some cases, in almost complete hydrolysis,and, in all others, in very small yields of ester, the use of sodiumalkyloxides was adopted.In this case, again, poor yields were obtained, until it wasrecognised that a slight excess of the sodium alkyloxides wassufficient to cause precipitation of sodium iodobenzenesulphonates.By using a standard solution of sodium alkyloxide in absolutealcohol (about 2-5-N), by adding the slightest excess over theamount necessary to precipitate the chlorine from the sulphonylchloride, and by keeping the mixture for about half a minuteonly before additibn of water and separation of the ethereal layer,an almost quantitative yield of the ester was obtained.Underthese conditions it was found unnecessary to use absolute ether assolvent ; methylated ether (dehydrated) dried for some weeks withcalcium chloride, and finally with sodium, was found pure enoughfor practical purposes.The methyl esters were prepared in exactly the same way, andafforded no difficulty in purification.Both ethyl and methyl esters crystallise extremely well fromalcohol, from ether, and from a mixture of alcohol and ether. I nthe case of ethyl 2 : 3 : 5-tri-iodobenzenesulphonate, two very dis-tinct sets of crystals were obtained from a mixture of alcohol andether; they melt at the same temperature, and give identicalanalyses; moreover, one form is transformed into the other onrecrystallisation from alcohol ; they are evidently the same sub-stance.Salts of 3 : 4: 5-, 2: 4: 5-, 2 : 3 : 5-tri-iodo-, and of 3 : 5- and2 : 4-di-iodobenzenesulphonic acids, which were not described inPart I, have now been investigated; they are described in theexperimental part of this paper.The following table shows the melting points of the chloride216 BOYLE : IODOBENZENEMONOSULPHONIC ACIDS.PART 11.and ethyl andacids :Acid.2 : 5-acid3 : 5-3 : 4-2 :4-2:3:4-2 : 4 : 5 -3:4:5-methyl esters of di-Chloride.132"938277122-5135145and tri-iodobenzenesulphonicEthyl ester.120.5"1128257110156143Methyl ester.106"959378137166157EX PER IM EN T A T ~ .2 : 4-Di-iodob enzenesulphonic Acid.The ethyl ester was prepared by dissolving the sulphonyl chloridein dry ether and adding the requisite amount of a solution ofsodium ethoxide in absolute alcohol; after half a minute, water wasadded, and the ethereal layer separated and evaporated; the esterseparated from alcohol in long needles, melting a t 5 7 O :0.1489 gave 0.1199 CO, and 0.0246 H,O.The methyl ester was prepared from the sulphonyl chloride byIt crystallisesC= 21.99 ; H = 1.83.C8H8031,S requires C = 21-92 ; H = 1.82 per cent.the use of sodium methoxide in pure methyl alcohol.from alcohol in large, plate-like needles, melting a t 98O0.1895 gave 0.1378 CO, and 0.0246 H,O.The sodium salt separates from water in white, glistening scales,0-2019 gave 0.1138 CO, and 0.0263 H,O.0.9138 lost 0.0702 at 150O.H,O=7*68.C = 19.84 ; H = 1.44.C,H6031,S requires C = 19-81 ; H = 1-41 per cent.containing two molecules of water of crystallisation :C = 15.37 ; H = 1.44.C6H30312SNa,2H;0 requires C = 15-38 ; H = 1-49 ;H,O=7.68 per cent.SoZubiZity.-One hundred grams of water dissolve 1-90 grams ofThe potassium salt crystallises with one molecule of water in0-2033 gave 0.1151 CO, and 0.0199 H,O.0'2059 ,, 0.0383 K,SO,. K=8*35.0.9375 lost 0.0407 a t 145O. H,O =4.34.anhydrous salt a t 13O.sparkling, platelike needles :C = 15.52 ; H = 1.09.C6H30312S~,H20 requires C = 15.45 ; H = 1.07 ; K= 8-37 ;H,O = 3-86 per cent,SoZu6iZity.-One hundred grams of water dissolve 0.76 gram ofThe ammonium salt crystallises in glistening, platelike needles,the anhydrous salt a t 11'5O.which are anhydrousBOYLE : lODOBENZENERlONOSULPHONIC ACIDS, PAKl' 11. 217SoZubiJlity.-One hundred grams of water dissolve 2.23 gramsat 14O.3 : 5-Di-iOdobenzenesztlpkonic Acid.The ethLyZ ester crystallises from ether or from a mixture of0,0591 gave 0-0406 CO, and 0-0103 H,O.The methyl ester separates slowly from alcohol in interlacing,0.1159 gave 0.0840 CO, and 0.0155 H,O.The sodium salt crystallises in white needles, containing one0.1286 gave 0-0769 CO, and 0.0131 H,O.0.4892 lost 0.0195 at 1 4 0 O .H,O=3*99.alcohol and ether in small, white needles, melting a t 112O:C=21.96; H=1*92.C,H,031,S requires C = 21-92 ; H= 1.83 per cent.plate-like needles, melting at 95O :C = 19-84 ; H = 1-48.C,H,O,I,S requires C = 19.81 ; H = 1.41 per cent.molecule of water of crystallisation :C= 16.30 ; H= 1.12.C6H30,1,SNa,H,0 requires C = 16.00; H = 1.11 ;H;O = 4.00 per cent.SoZuZ,ility.-One hundred grams of water dissolve 3-56 grams ofThe potassium salt crystallises in large, white plates; the crystals0-1710 gave 0*1014 CO, and 0-0112 H,O.Solubility.-One hundred grams of water dissolve 0.75 gram ofThe ammonium salt crystallises in fine, colourless, anhydrousSolubility.-One hundred grams of water dissolve 1-62 grams ofThe barium salt crystallises in colourless needles, containing 340.6225 lost 0.0380 a t 145O.anhydrous salt at 20°.are anhydrous :C=16-16; H=0*66.C,H3031,8K requires c = 16.07 ; H = 0.67 per cent.salt a t 18'5O.needles.salt a t 20°.molecules of water :R2O=6.lO.C,2H60,1,S,Ba,3~H,0 requires H,O = 6.18 per cent.3 : 4 : 5-Tri-iodobenzenesulphonic Acid.Ethpl 3 : 4 : 5-tri-iodobenzenesulphonate is obtained in a 55 percent.yield by boiling the sulphonyl chloride with alcohol, in 90 percent. yield by the use of sodium ethoxide. It separates fromalcohol in long, transparent needles, melting at 143O:0.1865 gave 0.1167 CO, and 0*0200 H,O. C = 17-09; H = 1-20.C,H,O,I,S requires C = 17-02 ; H = 1-24 per cent2 18 BOYLE : IODOBENZEKEMONOSULPHONIC ACIDS. PART 11.Methyl 3 : 4 : 5-tri-iodobenzenesulphonate crystallises from alcohol0.1461 gave 0.0811 CO, and 0.0130 H,O.The sodium salt crystallises in small, white, sparkling needles,0.2642 gave 0-1213 CO, and 0.172 H20.1.3331 lost 0-0421 a t 150O.R,O=3'15.in needles, melting a t 157O:C = 15.15 ; H = 0'98.C,H,O,I,S requires C = 15-27 ; H= 0.90 per cent.containing one molecule of water :C=12*52; H=0.71.C,H,O,I,SNa,H,O requires C = 12.50 ; H = 0.69 ;H20=3-12 per cent.Solubility.-One hundred grams of water dissolve 0.86 gram ofThe potassium salt separates from water in white, anhydrous0.2027 gave 0.0944 CO, and 0.0073 H,O.0'2073 ,, 0'0305 K2S04. K = 6.59.Solubility.-One hundred grams of water dissolve 0-*128 gram ofThe ammonium salt crystallises in long, anhydrous needles.Solubility.-One hundred grams of water dissolve 0.25 gram ofthe anhydrous salt a t 15O.needles :C = 12.69 ; H =0*39.C,H,0,13SK requires C = 12-54 ; H = 0.34 ; E = 6.79 per cent.salt a t 16*5O.salt a t 15O.2 : 4 : 5-Tri-iodo b enzenesulphonic A cid.Ethyl 2 : 4 : 5-tri-iodobenzenesulphonate separates from alcoholin glistening crystals, which redissolve with difficulty in alcohol andether.They melt a t 155-156O:0.1197 gave 0.1117 CO, and 0.0188 H20.Methyl 2 : 4 : 5-tr&iodobenzenesdphonate separates in small,It meltsc'=16.99; H=1*17.C,H,O,I,S requires C = 17.02 ; H = 1-24 per cent.glistening crystals from a mixture of alcohol and ether.at 166O:0.1176 gave 0.0656 CO, and 0.0089 H,O.The sodium salt crystallises in long, fine needles, slightly cream-coloured ; they contain 14 molecules of water :0.1532 gave0.0699 CO, and 0.0114 H,O.0.4245 loat 0*0200 at 135O. H20=4.71.C,H,O,T,SNa,l~H,O requires C = 12-31 ; H = 0.85 ;H,O =4.61 per cent.C=15.22; H=0.84.C7H,0,13S requires C = 15-27 ; H = 0.90 per cent.C=12*44; H=0*82.SoZmbility.-One hundred grams of water dissolve 0.64 gram ofthe anhydrous salt a t 1 6 ' 5 O BOYLE : IODOBEKZENEXONOSULPHONIC ACIDS.PART 11. 219The potassium salt, crystallising in fine, white needles, contains0.1458 gave 0.0660 CO, and 0.0088 H,O.0.4877 lost 0.0163 at 140°.0.2111 gave 0.0309 K,SO,. K=6*55.one molecule of water :C = 12.34 ; H = 0.66.H20=3'34.C,H,O,I,SK,H,O requires C= 12.16 ; H = 0.67 ; H20 = 3.04 ;K = 6.58 per cent.Solubility.-One hundred grams of water dissolve 0.31 gram ofThe ammonium salt crystallises in small, yellow, anhydrousSolubility.-One hundred grams of water dissolve 0.82 gramthe anhydrous salt a t 14O.nodules.a t 1 1 O .2 : 3 : 5-Triiodobenzenesu1phonic Acid.Ethyl 2 : 3 : 5-triiodobenzenesulphonate separates from a mixtureof alcohol and ether in crystals of definite form, somewhat resem-bling those of copper sulphate ; under certain conditions, which havenot been definitely fixed, long needles are sometimes obtained;the needles on re-solution in alcohol are changed into crystals ofthe other form.Both farms melt at l l O o , and give identicalanalytical numbers :First set (needles): 0.1370 gave 0.0849 CO, and 0.0167 H20.Second set: 0.1867 gave 0.1168 CO, and 0.0211 HiO. C=17.06;C = 16.91 ; H = 1-35.H = 1-25.C8H70,1,S requires C = 17.02 ; H = 1.24 per cent.Methyl 2 : 3 : 5-tri-iodobenzenesulphonate crystallises from a mix-ture of methyl alcohol and ether in long, transparent needles,melting a t 137O:0-1650 gave 0.0930 CO, and 0.0150 H,O.C = 15.33; H= 1-00,The sodium salt probably crystallises with one molecule of water :0.1531 gave 0.0697 CO, and 0*0100 H20.Solubility.-One hundred grams of water dissolve 0.55 gram ofsalt at 18O.The potussium salt separates from water in small, glisteningcrystals containing one molecule of water :0.2234 gave 0.1021 CO, and 0.0155 H,O.0.4643 lost 0-0144 a t 1 5 0 O . H20=3'10.C7H,0313S requrres C = 15-27; H=Os91 per cent.C=12.41; H=0*71.C,H2031,SNa,H20 requires C = 12.50 ; H = 0.69 per cent.C= 12.46; H =0*76.C,H20313SK,H20 requires C = 12.16 ; H = 0.67 ;H,O = 3'04 per cent220 PERKIN : A NATURAL SUBSTANTIVE DYESTUFF.Solubility.-One hundred grams of water dissolve 0.139 gramThe ammonium salt is anhydrous. One hundred grams of waterEthyl 2 : 5-di-iodob enzenesdphonate crystallises from a mixture0.1740 gave 0.1411 CO, and 0.0296 H,O.Methyl 2 : 5-di-iodob enzenesulphonate crystallises from alcohol in0.0958 gave 0.0693 CO, and 0.0112 H,O.Ethyl 3 : 4di-iodo b enzenesdphonate separates from alcohol in0.1851 gave 0.1483 CO, and 0.03 H,O. C=21.85; H=1-79.Methyl 3 : 4-di-iodo b enzenesulphonate crystallises from methyl0.1937 gave 0.1414 CO, and 0.0262 H,O.of the anhydrous salt a t 1 8 O .contain 0.69 gram at 1 8 O .of ether and alcohol in long, stout needles, melting a t 120'5O:C=22*11; H=1*89.C8H8031,S requires C = 21-92 ; H = 1.83 per cent.fine, woolly needles, melting a t 106O:C =19*72 ; H = 1-29.C7H,0,1,S requires C = 19.81 ; H = 1.41 per cent.needles, melting at 82'5O:C8R8O,I2S requires C = 21-92 ; H = 1.83 per cent.alcohol in glistening cubes ( ?), melting at 93O:C=19*90; H=1*49.C7H,0,12S requires C = 19.81 ; H = 1.41 per cent.THE ROYAL HOLLOWAY COLLEGE,ENGLEFIELD GREEN

ISSN:0368-1645    

DOI:10.1039/CT9109700211

出版商:RSC    

年代:1910

数据来源: RSC

摘要:

220 YERKIN : A NATURAL SUBSTANTIVE DYESTUFF.XXIV. -A Natural Substantive Dyestuff.By ARTHUR GEORGE PERKIN.SOME time ago a small sample of an Egyptian natural dyestuffwas received from the authorities of the Imperial Institute, underthe name of the “ red dura” of the Soudan, the dyeing propertiesof which proved to be specially interesting in that good shadesupon wool could be obtained from it without the aid of a mordant.The material consisted of the leaf sheaths of a, grass, smoothexternally, possessing a deep reddish-brown tint, and approximatelynine inches in length, together with cylindrical fragments of thestem (or pith) of a brighter, although feebler, colour. The follow-ing account of this plant was furnished by Mr. C. P. Browne,Inspector of the Blue Nile Province: ‘ I I attach a specimen of‘ Sikhytan,’ the species of durra used for producing a, red dye,practically utilised for staining a grass called ‘ lanzura,’ used in thPERKIN : A NATURAL SUBSTANTlVE DYESTUFF. 221manufacture of coloured ‘ bursh ’ (mats), but occasionally for theleather of ‘ markubs ’ (Sudanese shoes).This durra is speciallygrown for the purpose and not for eating. It occurs in this district,but comes mainly from Rahad, Dinder, and the south.” Theresults of the examination of this product a t the Royal BotanicGardens, Eew, indicated that it was apparently part of the stem,including the leaf sheaths, of the A ndropogon sorghum, var. wdgaris,and this was int.eresting because this plant, also known as theSorghum wulgare, constitutes the “ Great Millet,” the grain ofwhich is so important a foodstuff.An elaborate account of theSorghum vulgare is given by Watt (“Dictionary of the EconomicProducts of India,” Vol. 6, Part 111, p. 289), and it is worthyof note that in certain cases the grain is described as possessing abrick-red colour, and that a t Harihar this is used for preparing ared morocco from goat skin. Again, it is stated in connexion withthe Sorghum saccharaturn that when the pressed canes are allowedto ferment, their colour changes to a red or reddish-brown, andthat the dye thus produced can bs extracted by means ofdilute alkali, and is precipitated from this solution by means ofacid in the form of red flakes. The Indian, Persian, Abyssinian,and Egyptian forms would seem to be derived from the Andropogonsorghum, var.‘ I durrha” (ibid., p. 278)) but the fact that thisplant is so extensively cultivated in Egypt as a foodstuff, whereas,according to Browne (Zoc. cit.), the ‘‘ Sikhytan ” is grown entirelyon account of its dyeing properties, leaves one t o infer that thislatter is again a special variety. Unfortunately, but a few ouncesof this material were available for examination, and this did notpermit of any extended investigation of the colouring matter whichis present, but should it be possible to obtain a large quantity ofthis dyestuff, a more exhaustive study of the subject will then becarried out.Ex P ER IMENTAL.The leaf sheaths and stems (pith) were examined separately,but as experiment showed that the same products were presentin both cases, this was evidently not necessary.The material wasextracted in a Soxhlet apparatus with boiling acetone until nothingfurther dissolved, and by evaporating the deep brownish-colouredextract there was obtained from the sheaths 16-27 per cent., andfrom the pith 14.7 per cent., of a dark brittle resin. On agitatingthis residue with cold acetone, a small quantity of substance didnot. pass into solution, and the operation was repeated until thefinal product was entirely soluble under this treatment. Theamorphous substance thus removed, and which, when dry, possesseda Slight beetle-green lustre, on incineration yielded Some quantit222 PERKIN : A NATURAL SUBSTANTIVE DYESTUFF.of ash, and appeared to consist of a calcium salt of the colouringmatter.The partly evaporated acetone extract, on treatment witha little boiling benzene, deposited a dull ochre-coloured precipitatealmost devoid of tinctorial property, which was removed and thefiltrate fractionally evaporated. By this means a gradual separa-tion of the colouring matter was effected, the earlier fractionspossessing a deep maroon colour, and those obtained later having abeautiful scarlet tint. The final mother liquid contained, togetherwith some quantity of plant wax, a trace of a yellow, resinouscompound.The crude colouring matter redissolved in a mixture of acetoneand benzene was again fractionally crystallised as before, the firstand final deposits being rejected, and this appeared to be the onlymethod available in dealing with so small a quantity of the sub-stance.The product consisted of a bright red, almost scarlet,powder, which under the microscope appeared as nodules possessingfine, saw-like edges, and thus possessed an ill-defined crystallinestructure. The quantity of colouring matter thus isolated wasapproximately 3 grams, and of this four distinct preparations, driedat 160°, were analysed :Found, C = 67-27 ; 67.53 ; 67.66 ; 67.40; H = 4-40 ; 4.61 ; 4-73 ; 4.33.CI6Hl2O6 requires C = 67.60 ; H = 4.23 per cent.It is very readily soluble in alcohol, very sparingly so in boilingwater, and dissolves in alkaline solutions with a violetrred colour,which rapidly becomes brown owing to oxidation.It is only partlyprecipitated by excess of alcoholic lead acetate, forming a dullreddish-violet lake soluble in water, but is completely deposited bymeans of the basic acetate with formation of an insoluble lead salt.With alcoholic ferric chloride it gives a brown coloration, and itssolution in both sulphuric and nitric acid is yellow, the latter acidreacting to form a nitro-compound precipitated by water. It doesnot contain me thoxy-gr oups.The colouring matter was fused with potassium hydroxide and alittle water to 200-220° for twenty minutes, the brownish-colouredmass dissolved in water, and the solution acidified and extractedwith ether. The crystalline residue obtained by evaporating theether, when examined in the usual way, gave phloroglucinol (m.p.210O) and an acid, melting at 210°, which had all the propertiesof p-hydroxybenzoic acid, and could be admixed with it withoutalteration of melting point. A second experiment gave also a traceof a compound of lower melting point resembling p-hydroxy-acetophenone, but this point requires further corroboration,Merely a trace of the substance was available for dyeing experi-ments, but this ww sufficient to indicate that the tinctoriaEDMINSON AND HILDITCH: OPTICAL ACTIVITY. PART IV. 223properties of the plant were entirely due to this colouring matter.As was to be expected from its behaviour with lead acetate solution,it does not dye mordanted calico, although, as previously indicated,it is a substantive dyestuff towards wool.By the use of a boilingaqueous extract of the plant itself, a dull red shade was obtainedwith woollen cloth, and this became rather weaker when it wastreated with warm dilute soap solution. A very permanent andslightly fuller colour was produced by previously mordanting thewool with chromium or copper: and a similar result could beobtained by an application of the mordant after the dyeingoperation. In comparison with the better-known substantivenatural dyestuffs, the ‘( red dura ” very closely resembles in thisbehaviour the ‘‘ insoluble red woods,” which contain as the chiefcolouring matter santalin, and of which sanderswood (Pterocarpussantalinus) is a typical example. The shades given by the latter,although of a faintly yellower character, closely resemble thoseproduced by the “red dura,” and although the sanderswoodpossessed somewhat the stronger dyeing power, there was but atrifling distinction to be observed in this respect. Again, it wasascertained that by submitting sanderswood to a similar process tothat described above, the colouring matter thus isolated was verysimilar in appearance and general properties to that obtained fromthe ‘(red dura.” It therefore seems appropriate to term thislatter dura-santalin.The formula of santalin, C,,H,,O,(O=CH,) (Cain and May,J. SOC. Chem. Znd., 1909, 28, 697), does not suggest the existenceof a simple chemical relationship between these colouring matters,but it seems likely that they may possess in common a specialgrouping which will account for their close resemblance.CLOTHWORKERS’ RESEARCH LABOEATOI1Y,THE UNIVERSITY,LEEDS

ISSN:0368-1645    

DOI:10.1039/CT9109700220

出版商:RSC    

年代:1910

数据来源: RSC

摘要:

EDMINSON AND HILDITCH: OPTICAL ACTIVITY. PART IV. 223XXV. -The B f e c t of Contiguous Uksatui-ated Groupson Opticcd Activity. Purt IV. CoiajugutedSystems containiug more thun Two Umcu%ratedG7-oups.By SYDNEY ROBERT EDMINSON and THOMAS PERCY HILDITCIZ.IN the course of work on the effect of two adjacent unsaturated radicleson molecular rotatory power, some of which has already been publishedin earlier parts of this series, it has been established that a pronounce224 EDMINSON AND HILDITCH : THE EFFECT OF CONTIGUOUSincrease of optical activity invariably accompanies the conjunction oftwo such groups. At the same time, it has frequently been noticedthat when a third group, possessing marked residual afinity, happenst o occur in close proximity to the studied systems, the increase inrotatory power is not always maintained, and, indeed, is sometimesmarkedly lessened.This may be instanced from the rnenthyl esters of piperic and sorbicacids, recently studied by one of us (Trans., 1909, 95, 1570), of whichwe reproduce here the molecular rotatory powers and correspondingdifferences from the " normal value " of a menthyl ester (a quantitythe approximate estimation of which has already been explained, Zoc. cit.,p.1571):[MI:. Difference.CGH5'CH:CH*CH:CH*CO,'C,nH,S ......... - 188'8 +28'3CH3*CH:CH*CH:CH'C0,*C,oH,g ........ - 221 -3 + 56.7The brucine salts of these acids, on the other hand, show a'' difference " of + 218-8O for the piperate, and + 119.5' for the sorbate,under identical polarimetric conditions.Again, the brucine salts of anthranilic and salicylic acids and theiracylated derivatives give evidence of similar irregularities (Trans.,1908, 93, 1388):[MID.Difference.Brucine benzoate .................... - 131'1 +118'4 .. ant hranilato .................. - 47.8 + 201 -7 .. acetylanthranilate ......... I- 29'8 +279-3 .. benzoylanthranilate.. ....... + 156 '2 + 405'7 .. benzoate ..................... - 131'1 + 118% .. salicylate ..................... + 75 '5 + 325.0 .. acetylsalicylate. .............. -I- 86.7 $. 336.2 .. benzoylsalicylate ............ +o-0 -I- 249-5Since mono-aryl esters of camphoric acid and camphor-P-sulphonicacid can be readily prepared and obtained pure, and since phenolicsubstances containing as many as five adjacent unsaturated groupsare also easily obtainable, we thought it might prove interesting toexamine as extended a series as possible of these derivatives.DiE-culties appeared, however, in the case of the more complicated phenolsused, chiefly owing to the decreasing facility of reaction shown onascending the series, and to the anticipated fact that the higher esters,although not so strongly coloured as their parent phenols, began to besufficiently dark yellow to interfere with polarimetric accuracy.We have endeavoured to arrive a t a "normal value" for themolecular rotatory power of acid esters of camphoric acid and ofcamphor-/I-sulphonic esters, in accordance with the usual rule(Tschngaeff, Ber., 1898, 31, 360; Walden, Ber., 1905, 38, 355), byexamining the methyl, ethyl, sz-propyl, and n-butyl esters of the twoacids.I n the case of camphor-P-sulphonic acid, we did not succeeUNSATURATED GROUPS ON OPTICAL ACTIVLTY. PART IV. 225in obtaining the propyl and butyl compounds in the pure state, andwe have therefore used the molecular rotatory power of the ethylester as a basis of comparison, since it is well known that the firstmember of the series is almost always irregular.Wc will return to a discmsion of the polarimetric results aftergiving some account of the compounds studied.EXPERIMENTAL.The alkyl hydrogen camphorates were prepared according toJ. Walker's directions (Trans., 1892, 61, 1088) ; a quantity of sodiumbeing dissolved in excess of the respective alcohol, the equivalentamount of camphoric anhydride was added, and the mixture boiledfor half an hour.The ester was then readilyisolated from the sodiumsalt formed.Eriihl (fie?.., 1891, 24, 3409) has observed that ethyl hydrogencamphorate tends to decompose, on being distilled in a vacuum, intothe diethyl ester and camphoric anhydride. We invariably foundtraces of anhydride in the distillate (under a pressure of 20 raw.)from either the ethyl, n-propyl, or n-butyl hydrogen esters, andultimately we purified them by extracting the ethereal solution of thecrude product with aqueous sodium hydrogen camphorate. Thisextract was cooled to Oo, acidified with a slight excess of mineral acid,and extracted again with ether. The dried ethereal extract wasfiltered, the ether removed by distillation, and the residue heated onthe water-bath in a vacuum for two hours.No appreciable decom-position thus took place, and the ethyl hydrogen ester so obtainedshowed a slightly higher rotatiori than that hitherto observed.We should mention that Walker (Zoc. cit.) has proved that in theaction of sodium alkyloxides on camphoric anhydride no allo-estersare formed.Met?uJ ?bytIvoge?c, carnplhoncte, CO, H C,H,,* CO,Rlle. - Colourlessneedles, m. p. 77':0.1046 gave 0,2373 CO, and 0.0813 H20.h'thyl lqdroyeu cant,phorcde, C0,H*C,H,4*C0,Et.--A colourless,0.1004 gave 0.2344 CO, and 0.0788 H20.n-Propyl hyd?.ogerc, ccmphorute, C O , H * C , H , * * C Q , * C ~ ~ ~ - ~ colour-Ob1O40 gave 0.2456 GO, and 0*0816 H,O.VOL.XCVII. QC = 6 1.87 ; H a8.64.C,,H,,04 requires C: = 61 *ci3 ; €1 = S.41 per cent.viscous oil :C! = 63.66 ; lI = 8-75!.C1,H2,,O, requires C = 63.1 7 ; H = 8.77 per centless, viscous oil :C: = 64.40 ; H = 9-04.C13H2204 requires c! = 64-46 ; H = 9.09 per cent226 EDMINSON AND HILDITCH : THE EFFECT OF CONl'lGUOUSn-Butyl hydrogen camphorate, CO,H*C,€€l,*CO,* C,H,. -A colourlessoil, much more limpid than the two preceding :0,1866 gave 0.4525 CO, and 0,1516 H,O.C,,H,,O, requires C: = 65.63 ; HThe alkylcamphor-P-sulphonates were obtained by heating equi-valent amounts of sodium alkyloxide and camphor-P-sulphonyl chloridein the respective alcohols for a short time. The product was mixedwith ice-water, and, when it had completely solidified, i t was collectedand recrystallised from aqueous methyl alcohol,Methyl camp?ior-p-suZphonafe, C,,H,,O*SO,Me.-Sof t, white needles,melting at 61O :0.1041 gave 0.8046 CO, and 0,0664 H,O.0,1630 ,, 0,1524 BaSO,.S= 12-83.Zthy! camphor-p-suZphonale, C,,H,,O*SO,Et.-Wax-like plates,0.1064 gave 0.2156 00, and 0.0750 H20.The n-propyl and n-butyl esters mere not obtained solid, either bycrystallisation from a number of solvents or on standing in avacuum desiccator for several weeks, and they were therefore notexamined.The unsaturated compounds studied may be divided into thosederived from phenol (0-hydroxybenzylidene-acetone and -acetophenone)and from the naphthols (2-aceto- and 2-benzo-a-naphthol) respectively.The latter substances were prepared by heating 10 grams ofa-naphthol with 15 grams of zinc chloride and 20 grams of aceticor benzoic acid at 150° for half an hour (Friedlander, Ber., 1895, 28,1946).FriedlPnder has characterised 2-aceto-a-naphthol, and showni h t o possess the assigned structure, but the similarly fornied 2-benxo-a--naphthol does not seem t o have been described.I t is obtained in the form of a yellow, amorphous, partly hydrolysedsodium salt on pouring the cold reaction product (see above) intodilute aqueous sodium carbonate ; from this salt the phenol itself canbe isolated as a yellow, crystalline solid, melting, after recrystal-lisation from dilute alcohol, at 77" :C = 66.18 ; H = 9.03.9.38 per cent.C = 53.60 ; H = 7.09.C,,H,,O,S requires C = 53.67 ; €I = 7.32 ; S = 13-01 per cent.melting a t 47O :C=55*25; H z 7 .8 3 .C,,H,,O,S requires C = 55.39 ; H = 7.69 per cent.0,1039 gave 0.3123 CO, and 0.0486 H,O.C17H,,0, requires C = 82.24 ; H = 4.84 per cent.The benxoy1 derivative, prepared by the Schotten-Bizumann method,crystallises from light petroleum i n pale yellow leaflets, melting at154' to a dark red liquid :C = 82.00 ; H = 5.20UNSATURATED GROUPS ON OPTICAL ACTIVITY. PART IV. 2270.1326 gave 0.3969 CO, and 0.0528 H,O.C,,H1,O, requires C = 81.83 ; H = 4.55 per cent.2-Benao-a-naphthol displays a great tendency to form insoluble saltswith bases; the pale yellow, amorphous sodium and ammonium salts,and the yellow, crystalline piperidine salt, melting at 138O, are allpartly hydrolysed by cold water, but the still less soluble, brownish-yellow barium salt is much more stable :C=81*68 ; H = 4'43.0.2571 gave 0.0957 BaSO,.C,,H,,O,Ba requires Ba = 21.71 per cent.The phenolic hydrogen camphorates were obtained according toSchryver's method (Trans., 1899, 75, 661); since, however, i tappeared that his directions for preparing the phenolic sodium saltsmight in some of the present cases give rise to secondary reactions,owing to the presence of metallic sodium, these were prepared byadding the equivalent amount of sodium ethoxide t o the phenol i nalcohol.After evaporating the alcohol and drying the sodium salt ina vacuum on the water-bath, xylene and the requisite amount ofcamphoric anbydride were added. With some of the more complexphenols, too prolonged heating appeared to give rise to by-products,a maximum, although frequently not very satisfactory, yield beingobtained after heating a t 100" for about half-an-hour.Phenyl hydrogen camphorate, C0,H*C8H14-C0,Pb .-Slender needlesfrom methyl alcohol, melting a t 98" (100' : Schryver) :0.1217 gave 0.3096 CO, and 0.0815 H20.0- /3- Beet y lvin y lph en y l hydrogen c a rnphorat e,Ba = 21.91.C = 69.38 ; H = 7-49,Cl6HzOO4 requires C = 69.56 ; H = 7.25 per cent.CO,H-C,H,,~CO,*C,H,.C'H :CHAc.-Soft, yellow plates from alcohol, decomposing at 11 lo :0.1948 gave 0.5006 CO, and 0.1237 H20.o-P-Benxoylvinylphenyl hydrogen camphorate,C = 70.08 ; H = 7.05.C,oH,,O, requires C = 69.76 ; H = 6.98 per cent,CO,H C,H,,*CO,*C,H,*CH: CHBz,was not obtained in very good yield; it forms yellow crystalsfrom benzene by precipitation with light petroleum.The compound,which was rather easily hydrolysed, melted a t 145" :0.1104 gave 0.2961 CO, and 0.0606 H,O.P-NaprlAthyZ hydrogen camphorate, CO2H*C,H,,*CO2*C,,H7.-Purewhite crystals from aqueous alcohol, melting at 125O (121-122O:Schryver) :C = 73.38 ; H = 6-10,C,,H,,O, requires C = 73.89 ; H = 6.40 per cent.0.1128 gave 0.3073 GO, and 0-0740 H,O. C = 74.10 ; H = 7-29.C20H2204 requires C = 73.62 ; H = 6.75 per cent.Q 228 EDMINSON AND HILDITCH : THE EFFECT OF CONTIGUOUSa-Naphthyl hydrogen camphorate, CO,H* C8H14* CO,*C,,H~.-White0.1172 gave 0,3163 CO, and 0.0734 H,O.2-Aceto-a-napl~th$ hydrogen camphorate, CO,H*C,Hl,*CO,*Cl,H,Ac.0.1444 gave 0.3815 CO, and 0.0858 H,O.C,,H,,O, requires C = 71 *74 ; H = 6.52 per cent,2-L'enxo-a-naphthyl Ir ydyogen campho?.ate, CO,H* C, H,,- CO,* Cl,H,FhI-A yellow, crystalline powder from benzene, melting and decomposingat 172O :prisms, which melted somewhat indefinitely at about 170° :C2,H,,04 requires C = 73-62 ; H = 6.75 per cent.U=73.58; H=6*96.-White needles, melting at 102' :Cl=72*05; H=6*60.0,1059 gave 0.2924 CO, and 0.0572 H,O.C27H2605 requires C = 75-34 ; H = 6.05 per cent.The corresponding camphor-/3-sulphonates were all prepared by theSuhotten-Baumann method, using very dilute aqueous sodium hydro-oxide and maintaining the reaction solution at such a temperature thatthe camphor-p-sulphonyl chloride always remained a little above itspoint of fusion.Phenyl car)npr7Lor-P-sulp?~onate, C,oHl,O*SO,Ph, only solidified afterstanding some time in a vacuum, but thereafter crystallised from lightpetroleum in long, radiating, colourless needles, melting at 4s' :C = 75-30 ; H = 6.05.0.1055 gave 0.2414 CO, and 0.0610 H,O.o-P-AcetylvinyZphenyl camphor-/3-suZphonrte,C = 62.38 ; H = 6*42.C16H,c04S requires C = 62.32 ; H = 6.49 per cent.ClOHl5O* SO,* C,H,*CH: CH Ac,was fourid t o be a yellow oil, which would not crystallise, and, asno other means of purification besides crystallisation existed, it couldnot be utilised.o -P-Benoo ylvinylphenyl camphor- /3-s u Zphonate,C1,Hl,O*SO,*C,H;CH:CHf3z,crystallising in yellow needles from benzene, melted a t 102" :0.1000 gave 0.2497 CO, and 0.0548 H,O.~-~..~ap?&yl canziuhoi.-P-sulpronate, C,oH,50*S0,* Cl,H7, crystellised in0.0978 gave 0.2396 CO, and 0,0549 H,O.a - NaphthyZ cantphor - p - sulphorucle, Cl,Hl,0*S0,*Cl,H7,--W hite0.1097 gave 0.2697 UO, and 0.0624 H,O.C20€K2204S requires C = 67-04 ; H = 6.15 per cent.2-Aceto-a-mphth yl cccrr~~f~or-p-suzph~~t~, CloH1,0*80,* CloH6Ac.-C = 68910 ; H = 6.09.C25H2606S requires C = 68.48 ; H = 5-94 per cent.faintly pink prisms from aqueous alcohol, and melted at 100' :C = 66.82 ; H = 6.24.C,,H,,O,S requires C: = 67.04 ; H = 6.15 per cent.needles from dilute alcohol, melting at 109O:C = 67.04 ; H = 6.32UNSATURATED GROUPS ON OPTICAL ACTIVITY. PART IV. 229Small, hard, crenm-coloured needles from nlcohol, which molted fit1 0 2 O :0.1039 gave 0.2510 CO, and 0.0546 H,O.C= 65.90 ; H=5*84.C,2H240,S requires C = 66.00 ; H = 6.00 per cent.2-Benzo-a-napht?hyZ camphor-P-suzphonate \vas not obtained in thesolid stab, and therefore had to be omitted from the series.The polnrimetric observations were carried out exactly RS in previousinvestigations of this series, the temperature being maintained a t 2 3 O .For the alkyl esters, t h e following values were obtained :Chloroform solutions : 5 per cent. - [alw [MID.Methyl hydrogcii caiiiphorate ... + 57'71 -k 123.5Ethyl ,, ... 38.72 88'372-Propyl , , > 9 ... 38.76 93.8'/?-Rlltyl ,, ... 35.60 91.1,,3 , -Ifcan [M]Ei" (ethyl n-hntyl) ............ 91.124 per cent.[.ID.EMID. + 58-50 + 125.239-50 90.738.56 93'333-24 92.892'3--Methyl camphor-8-sn1phonat.e ... + 43.61 + 197.3 + 43-40 + 106.8Ethyl ,, .., 43'91 114-2 43-28 112%In certain instances it was found impossible to obtain an accuratereading with the 5 per cent. solutions of the phenolic esters, andtherefore, especially as in none of the other cases mas there any markedchange of rotatory power on dilution, we give only the valuesmeasured in 2-5 per cent. chloroform solution ; the numbers obtainedby one of us (Zoc. cit.) for the o-tolyl and o-aldehydophenyl estersme incorporated in the table,Hydrogen camphorate.lalo. [MI,. Diff.L r \Phenyl .................. +45*38 +125*2 4-329o-Tolyl .................. 45.0 130'5 38'2o-Alclehydophenyl ......48.1 146.2 53.9o-Acetylvinylplionyl ... 30.04 103.3 12'2o-8-Benxoylvinylphenyl 49.44 200.7 108.4P-Naphthyl ......... 53'25 173'7 81'4a-Naphthyl ............ 34-24 111.6 19.32-Aceto-a-1iaphthyl ... 38.00 139.5 47 52-Benm-a-naphthyl ... 52.82 227'2 134.9'Camphor-B-siilphonate.$40'56 f 1 2 4 - 9 +12-346.0 148.1 35.539-6 133.1 20.527.2 119.1 6.530.16 108'0 - 4 . 638.24 i.37-0 f24'450.02 200.1 87'5i.l,.]L)iff:- - -- - -There are thus included in the above summary four groups of sub-stances, namely, hydrogen camphorates of the phenyl and of the riaphthy 1series, and camphor-P-sulphonates of the same. Of these, the twofirst-mentioned show a steady increase of rotatory power with theincreasing number of conjugated groups, but the camphor-P-sixlphonicseries is, to all appearances, perfectly irregular.These results arefurther confused by the isomeric a- and P-naphthyl compounds, wherethere is a very notable difference of rotation in both the cnmphorioand the camphor-/?-sulphonic series, but in conflicting directions230 EDMINBOM AND HILDITCH : OPTICAT) ACTIVITY. PART IV.Eenzylidenecaniphor * ......... + 1020Cinnamylidenecamphor t ... 788We will refer, in conclusion, to three other series of this tFpe ofcompounds, which would seem to exhaust all the available data ; thefirst comprises the camphorates of certain aromatic arnines, comparedwith di-n-butylamine camphorate ([MI? 38% in 2.5 per cent. chloro-form solution) :Win. Difference.Di-p-toluidine cainphornte ............+ 99 -4 + 60%Di-p-aminoacetophenone camphorate. 91'2 52 '6Di-p-aminobenzophenone camphorate 73.6 35.0Next, there are certain condensation products of camphor witharomatic aldehydes :PJcnsylcamphor * ............ + 348y-Phenylpropylcaniphor I. 178* Haller, Compt. rend., 1899, 128, 1370.I. Rupe and Frisell, Ber., 1905, 38, 104.And, finally, certain esters recently examined by Rupe (Annnlen,1909, 369, 311) :[ Differencc.Mcnthyl diphenylacntate ............ - 233'4 + 75'6 ,, a-phenylcinnnmats ......... 193'5 -t. 35 -7,, fi-pheny!cinnninntc ......... 137'3 -21.5Rupe draws the empirical conclusion that a phenyl group in thenearest possible position to the asymmetric system enhances rotatorypower, but in others, further removed, depresses it ; it appears not alittle remarkable that one and the same group should exert a stronginfluence in two opposing directions, according as it is united with theQ- or y-carbon atoms.We may summarise these data by pointing out that of the elevenseries to which we have referred, four shorn a steady increase, foursbow a decrease, and the remaining three manifest indefinite changesin optical activity on increasing.beyond two the number of contiguousunsaturated systems.Sufficient facts for a profitable discussion as t owhether the indefinite numbers result from conflicting influences otherthan that due to conjugation, or whether the regular series are simplycoincidences, appears still to be lacking.It will be observed that the difference between the esters of evensuch nearly related bodies as phenol and o-cresol are considerable, andone cause of irregularity may lie in the fact that most of the estersstudied above are tbe earlier members of homologous series, and maythus be abnormal, as has so frequently been noticed in the firstmembers of other series. There is, indeed, little doubt that interestingand more comparable results would follow from a study of activeesters of, for example, one of the higher normal aliphatic alcohols,replacing successive methylene groups by a system of multipleTHE CONSTITUENTS OF RED CLOVER FLOWERS. 231identical unsaturated groups, but such a series would be very difficultto prepare.We desire to offer our hearty thanks t o Professor Knorr, in whoselaboratory this work has been carried out.UNIVERSITP OF JENA

ISSN:0368-1645    

DOI:10.1039/CT9109700223

出版商:RSC    

年代:1910

数据来源: RSC

摘要:

THE CONSTITUENTS OF RED CLOVER FLOWERS. 231XXVI.-The Constituents of Red Clove?- Flowem.By FREDERICK BELDING POWER and ARTHUR HENRY SALWAY.THE flowers of the common red clover (TrifoEium pratense, LinnB)have been used to some extent medicinally in recent years onaccount of their assumed alterative properties, and have even beenrecommended in the treatment of cancer (Anter. J . Pharm., 1881,53, 85). So far as known to us, these flowers have never beensubjected to a chemical examination, and the only knowledge oftheir constituents appears to be embodied in a statement that theycontain tannin, two resins, fat, and chlorophyll. I n this connexionit may incidentally be noted that Perkin and Phipps, in a paperentitled “ Notes on some Natural Colouring Matters ” (Trans.,1904, 85, SS), have recorded that it cursory examination of theflowers of the white clover (Trifolium repens) indicated the presenceof quercetin in the form of a glucoside.The same authors further-more remark that (( this colouring matter was recognised by themelting point of its acetyl derivative, and its decomposition productswith caustic alkali, and in consequence of these observations afuller investigation appeared unnecessary.”In view of the above considerations, and the fact that red cloverflowers are available in practically unlimited quantities, it appeareddesirable that a complete study of their constituents should beundertaken. The present investigation has disclosed the presenceof slr considerable number of new and interesting substances, anda summary of the results obtained is given at the end of thispaper.EXPERIMENTAL.The material employed in this investigation was carefullycollected for us under the superintendence of Mr.P. E. F. PerrBdBs,B.Sc., F.L.S., during the month of June, from a, field of cultivatedred clover (Trifolium prutense, LinnB) in Kent. The flowers orblossoms were separately gathered, and were therefore, so far aspossible, free from the green, herbaceous parts of the plant232 POWER AND SAJ,WAY:A portion (10 grams) of the dried flowers was tested for analkaloid, but the reactions obtained were so slight as to indicatcthe presence of not more than traces of such a substance.A further portion (25 grams) of the dried flowers was successivelyextracted in a Soxhlet apparatus with various solvents, when thefollowing amounts of extract, dried in a water-oven, were obtained :Petroleum (b.p. 35-50") extracted 0.50 gram 1 2.0 per cmit.Ether ,, 0.50 ), = 2.0 ,,Cliloroform ,, 0.35 ,) = 1'4 ,,Ethyl Acetate ,* 1.50 ,, = 6'0 ,,Alcohol ,, 4'50 ,, = 18.0 ,, - -Total 7.35 grams = 29-4 per cent.For the purpose of a complete examination, 264 kilograms of theflowers were collected. This material, after careful drying,amounted to 58.5 kilograms, or 22.16 per cent. of the originalweight. The. entire amount of this material was coarsely powdered,and then extracted by continuous percolation with hot alcohol.After the removal of the greater portion of the alcohol, which wasconducted a t a temperature not exceeding 8 5 O , a dark green, viscidextract was obtained, which amounted to 15.78 kilograms.7)istiklntio.n of t h Rafmrt with Steam..Separation, of an, Essrn tintOil.A quantity (1.5 kilograms) of the above-mentioned extract wasbrought into a suitable apparatus with a little water, and steampassed through the mixture for several hours. The distillate, whichcontained some oily drops, was extracted with ether, the etherealliquid being washed, dried, and the solvent removed. A smallamount (1.5 grams) of an essential oil was thus obtained, whichpossessed a rather unpIeasant odour. On subsequently treating10 kilograms of the alcoholic extract in the manner above described,a further quantity (10.5 grams) of essential oil was obtained.Theyield of oil was thus equivalent to 0.028 per cent. of the dried, or0.006 per cent. of the fresh clover flowers. This essential oil, whendistilled under diminished pressure, passed over between 90° and160°/20 mm. as a light yellow liquid, which, however, on keeping,ultimately became reddish-brown, and was found to contain fnrfur-aldehyde. It possessed the following constants : (I! 2Oo/2O0 - 0.9476 ;an +4OOf in a l-dcm. tube.iVon~-i~oZntiZa Constitmmts of t h e Elrf rnct.After the removal of the volatile constituents of the extract, bydistillation with steam, as above described, therc remained in tliTHE CONSTITUENTS OF RED CLOVER FLOWERS. 233(listillation flask a reddish-brown, aqueous liquid ( A ) and a quantityof a viscid resin (R), which became solid on cooling.The resin wascollected, and thoroughly washed with water, the washings beingadded to the main portion of the aqueous liquid.Examination of the Aqueous Liquid (A).The aqueous liquid was concentrated under diminished pressure,and then repeatedly extracted with large volumes of ether. Theethereal extracts, which were of a light green colour, were united,washed with a little water, dried, and the ether removed, when10 grams of a dark-coloured, soft solid were obtained. This wasfound by a preliminary examination to consist of a complex mixtureof crystalline compounds, and, in order to obtain a quantitysufficient for their separation and characterisation, 10 kilograms ofclover extract were treated as above described, the resulting aqueousliquid being extracted with ether.The yield of ethereal extractfrom this quantity of material was 64 grams.Isolation of a Xew Phenolic Substance, Pratol,C,,H80,(OH)*O* CH,.The above-mentioned ethereal extract was digested with aquantity of ether insufficient to dissolve the whole, and the sparinglysoluble portion, which amounted to 3 grams, separated by filtration.This product was repeatedly crystallised from alcohol, when asubstance was obtained which separated in colourless needles,melting a t 253O:0.1265 gave 0.3307 C02 and 0.0513 H,O. C=71.3; R z 4 . 5 .0.1213 ,, 0.3161 CO, ,, 0*0500 H2O. C=71*1; H=4.6.C,,H1204 requires C = 71.6 ; H = 4.5 per cent.The above compound, when heated with acetic anhydride, yieldedan acetyl derivative, which separated from alcohol in featheryneedles, melting a t 1 6 6 O .This was analysed, and its molecularweight determined, with the following results :0-1039 gave 0.2646 CO, and 0.0420 H,O.0.1485, in 33.26 of acetic acid, gave A t - 0'057O.Cl6Hl1O4(CO*CH3) requires C = 69.7 ; H =4.5 per cent. M.W. = 310.The substance C16H1204 was found to contain one methoxylgroup, as determined by Perkin's modification of the Zeisel method :0.0995 gave 0.0785 AgI. MeO=10*4.C1,€I,O3(0Me) requires Me0 = 11.6 per cent.No compound of the formula Cl6HI2O4, pcssessing the sameC = 69.5 ; H=4.5.0.1069 ,, 0.2715 CO2 ,, 0.0436 H,O. C=69*3; H=4*5.M.W. = 305234 POWER AND SALWAY:properties as that above described, appears to have hitherto beenrecorded.It is therefore proposed to designate the substance fromred clover flowers as pratol, with reference to its phenolic characterand the specific botanical name of the plant.Pmtol, C,,H80,(OH)*O*CH,, crystallises in a very characteristicform, since it separates from alcohol in needles, which, under themicroscope, are seen to have a talon-like shape with curved edges.It is moderately soluble in hot alcohol, but only sparingly solublein water, ether, chloroform, or benzene. It dissolves readily inhot aqueous sodium carbonate and sodium hydroxide, yielding paleyellow solutions. When dissolved in acetic anhydride, and a dropof sulphuric acid added, a yellow coloration is produced. Withferric chloride no appreciable change of colour was observed.Pratol is isomeric with several flavone derivatives, such as the2-met hox y- and 3-me thoxy-flavonol,prepared by Kostanecki and his co-workers (Ber., 1904, 37, 775;1905, 38, 993).The general behaviour of pratol is also very similarto that of the above-mentioned substances, and it therefore seemsprobable that it represents one of the many hydroxymethoxy-flavones which are theoretically possible.Acetylpratol, Cl,Hl,0,(CO*CH3), prepared, as above noted, byheating pratol with acetic anhydride, is very soluble in hot alcohol,but only moderately so in chloroform or benzene.The ethereal liquid from which the sparingly soluble pratol hadbeen separated by filtration, as above described, was subsequentlyshaken with an aqueous solution of ammonium carbonate (a) untilnothing further was removed by this reagent, then with successivesmall portions of aqueous sodium carbonate ( b ) , and finally withaqueous sodium hydroxide (c). These extracts were then separatelyexamined.Isolation of Scclicylic Acid.The liquids obtained by extraction with ammonium carbonate ( a )were united, acidified with sulphuric acid, and extracted withether.This ethereal liquid, on the removal of the solvent, yieldeda quantity (20 grams) of a dark green oil. The latter was digestedwith considerable quantities of hot light petroleum, these liquidsbeing decanted, and the solvent evaporated. I n this manner2 grams of colourless needles were obtained, which, after a fewcrystallisations from water, melted a t 1 5 4 O and gave an intenseviolet coloration with ferric chloride THE CONSTITUENTS OF RED CTAOVER FLOWERS.2350.1230 gave 0.2765 COz and 0.0507 H,O.This substance was thus identified as salicylic acid.The portion of the ammonium carbonate extract which wasinsoluble in light petroleum was heated for some time with methylalcohol in the presence of concentrated sulphuric acid. A productwas thus obtained which could be further separated into phenolicand non-phenolic methyl esters by shaking its ethereal solutionwith dilute aqueous sodium hydroxide. The portion insoluble inthe alkaline liquid, consisting of the non-phenolic esters, amountedto 10 grams, and was a dark-coloured oil. It was hydrolysed withalcoholic potassium hydroxide, and the regenerated acids distilledunder diminished pressure, when fractions were collected a t100-130° and 130-230°/20 mm., whilst a quantity of undistillableresin remained in the flask.These fractions were further examinedby neutralising them with aqueous sodium carbonate, and frac-tionally precipitating the solutions with silver nitrate. A seriesof silver salts w?s thus obtained, which, with the exception of thelast fraction (111), were more or less brown in colour. After dryingin a vacuum over sulphuric acid, they were analysed:C = 61.3 ; H = 4.6.C,H60, requires C = 60-9 ; H =4*3 per cent.Fraction 100-13Ooj20 mm.Fraction 130-230°/20 mm.0.1760 of salt gave 0.0852 Ag. Ag=48-4.(I) 0.4969 of salt gave 0-1904 Ag.Ag=38.4.(11) 0.1531 ,, ,, 0.0700 Ag. Ag=45.7.(111) 0.7246 ,, ,, 0.4444 Ag. Ag=61.3.It was evident from these results that the non-phenolic acidsconsisted of a complex mixture.Identification of p-Coumaric A cia?.The portion of the above-mentioned methylated product whichwas soluble in aqueous sodium hydroxide was benzoylated by theSchotten-Baumann method, and then subjected to fractionalcrystallisation from alcohol. After a quantity of gummy, amor-phous matter had been separated, a crystalline substance wasdeposited, which was ultimately obtained in slender needles, meltingat 129O:0.0783 gave 0.2079 CO, and 0.0390 H20.BzO*C6H,-CH:CH*C0,Me requires C = 72.3 ; H= 5.0 per cent.This compound is thus seen to agree in composition with thebenzoyl derivative of methyl p-cournarate, which hitherto appearsnot to have been described. A little of it wits therefore preparedfor the purpose of comparison, when it was found to crystallise inC = 72.4 ; H = 5.5236 POWER AND SALWAT:slender needles, melting a t 129O, and to be identical in all respectswith the compound obtained from the acid present in red cloverflowers.The identity of the latter acid was further confirmed bythe hydrolysis of the benzoyl derivative of its methyl ester, whenit substance was obtained which crystallised from water in colourlessneedles, melting at 215O with evolution of carbon dioxide, andotherwise exhibited all the characters of p-coumaric acid.Isolation of a New P ellow Compound, Cl6H1,,O7.The sodium carbonate extracts ( b ) , obtained as above described,were separately acidified, and the resulting precipitates collectedand examined.The product obtained from the first sodiumcarbonate extract consisted chiefly of chlorophyll, and nothingcrystalline could be isolated from it. The second sodium Carbonateextract yielded a yellow powder, which was dissolved in hotalcohol, in which it was freely soluble. This solution, after beingkept for some time, deposited a small amount of a, colourless,crystalline substance, which, after purification, melted a t 253O, andyielded an acetyl derivative melting a t 166O. It was found to beidentical with the substance C16H1204, designated as pratol, whichhas already been described. As the mother liquors, which stillcontained all of the yellow compound, deposited nothing furtheron standing, the alcohol was completely removed, and the residueacetylated by means of acetic anhydride.On distilling off thegreater part of the latter liquid, a crystalline product separated,which proved to be a mixture of substances. It was fractionallycrystallised from alcohol, when a small quantity (1.0 gram) of anncetyl derivative was obtained, which appeared to be homogeneous,and separated in colourless, glistening, prismatic needles, meltinga t 145-147O with evolution of gas:0.1530 gave 0.3347 CO, and 0.0555 H,O.The acetyl content of this compound was determined by heatingi t for some time with dilute sulphuric acid in the presence ofalcohol, the alcohol being then completely removed, and the pre-cipitated yellow substance, which was insoluble in cold water,collected and weighed :0.1690 gave 0.1108 of yellow substance, or 65.6 per cent.C,,H,O,Ac, requires C = 59.8 ; H = 3.7 ; C,,H,,O, = 65.1 per cent,.C,,€I,O7Ac4 ,, C = 59.5 ; H = 4.1 ; C,,H,;07 = 65.3 ,,It would appear from these results that the yellow compoundpossesses the formula CI6H,,O7, and that it' contains four hydroxylgroups.The presence of a methoxyl group was also established.The compound, C16H,UOi, as obtained from its scetyl derivative,C=59.7; H=4*0THE CONSTITUENTS OF RED CLOVER FLOWERS. 237crystallises from boiling dilute alcohol in thin, yellow plates, whichmelt and decompose at about 280O. It is readily soluble in alcoholor acetic acid, but sparingly so in water, ether, chloroform, orbenzene.It dissolves in alkalis with a yellow colour, and its solutionin concentrated sulphuric acid exhibits a brilliant greenfluorescence. In alcoholic solution it gives with ferric chloride abluish-black coloration. The amount of this substance availablcwas not sufficient for its further examination.Isolution of a New 1’1aenoZic Substance, Pg*atensol, C17H902(0H)3*The final sodium carbonate extract of the above-mentionedethereal liquid yielded, on acidification, a light brown powder.This was dissolved in hot alcohol, and the solution kept for sometime, when a small amount of the previously described pratol,C,,-J31204 (m. p. 253O), was deposited. The mother liquors fromhlie latter contained a quantity of a very soluble substance, whichcould not be obtained directly in a crystalline form.The alcoholwas therefore removed, and the residue acetylated, when a productwas obtained which, after a few crystallisations from alcohol,yielded a pure, colourless ucetyl derivative, melting at 189O :0.1071 gave 0.2569 CO, and 0.0445 H,O. C=65.4; H=4*6.O*1002 ,, 0.2410 CO, ,, 0*0406 H20. C=65*6; H=4.5.Tlie molecular weight of the acetyl derivative was determined0.3518, in 25-62 of benzene, gave At 0’094O.The number of acetyl groups in this compound was ascertainedby hydrolysing with aqueous sodium hydroxide, then adding aslight excess of sulphuric acid, and distilling the mixture in acurrent of steam:0,2057 gave acetic acid equivalent to 14.45 C.C.lV/10-Ba(OH)2.by the ebullioscopic method :M.W. =390.C23H1808 requires C = 65.4 ; H = 4.3 per cent. M.W. =423.CO*CH3 = 30.2.C,7H,0S(CO*CH3)3 requires CO-CH, = 30.6 per cent.From these results it may be concluded that the substance con-tained in red clover flowers, from which the above-described tri-acetyl derivative was prepared, possesses the formula C,,Hl20,.In order to obtain the parent compound, the acetyl derivative washeated for some time in alcoholic solution with dilute sulphuricacid, and the alcohol subsequently removed by distillation withsteam, when a colourless, crystalline substance separated. This waspurified by crystallisation from benzene, when it separated infeathery needles, melting a t 2 1 0 O .Although the amount of thissubstance w w insufficient for analysis, it was proved to represen238 POWER AND SALWAYthe original compound by the fact that when again acetylated, ityielded an m t y l derivative melting at 189O.No compound of the formula C,,H,,O,, possessing the sameproperties as that above described, appears to have hitherto beenrecorded. It is therefore proposed to designate the substame con-tained in red clover flowers as pratensol, with reference to itsphenolic character and the specific botanical name of the plant.Pratensol, C17Hg02(OH),, is very readily soluble in alcohol andacetic acid, but only sparingly soluble in water, chloroform, andbenzene. It dissolves in alkali carbonates, yielding yellow solutions,whilst its alcoholic solution gives with ferric chloride a greenish-black coloration.Triacetylp-at ensol, C17Hg0,(CO~CH3)3, crystallises from alcohol,in which it is only moderately soluble, in colourless, slender needles.It is readily soluble in glacial acetic acid, and moderately solublein benzene.When warmed with djlute aqueous sodium hydroxide,not only are the three acetyl groups removed, but the moleculealso undergoes further change, with the formation of a, compoundwhich crystallises from dilute alcohol in long, colourless needles,melting a t 183-184O. I f , on the other hand, the acetyl compoundis heated with aqueous sodium carbonate, the product is a yellow,crystalline substance, which melts and decomposes at 160O. It wasnot possible to ascertain the exact nature of these changes onaccount of the small amount of substance available, since 37.1kilograms of dried clover flowers yielded not more than 1.5 grams,or about 0.004 per cent., of pure triacetylpratensol.Isolation of a New Phenolic Substance, C15H703(0H)3.The sodium hydroxide extracts ( c ) of the previously mentionedethereal liquid, when acidified, yielded a light green powder, whichpossessed an odour resembling that of eugenol. An attempt toidentify the latter by distilling the product with steam wm, how-ever, unsuccessful.The light green powder was subsequentlydecolorised by treating its hot alcoholic solution with animalcharcoal, when, on cooling, colourless clusters of feathery needlesseparated. After several crystallisations, the substance wasobtained pure, and then melted at 225O:0.0931 gave 0.2133 GO2 and 0.0310 H,O.This compound yielded an acetyl derivative, which separatedfrom alcohol in thin, silky needles, melting a t 209O.The acetylcontent of this compound was ascertained by hydrolysing withdilute aqueous sodium hydroxide, then acidifying with sulphuricacid, and distilling the mixture in a current of steam:C = 62.5 ; H =3*7.C,,H1006 requires C = 62.9 ; H = 3.5 per centTHE CONSTlTUENT8 OF XED CLOVER FLOWERS. 2390.1750 gave acetic acid equivalent to 12.5 C.C. N/lO-Ba(OH),.CO*CH3 = 30.7.The molecular weight of the acetyl derivative was also ascertainedby the ebullioscopic method :0.1768, in 26.46 of benzene, gave A t 0-043O.C1,H,O,(CO*CH,), requires CO-CH,= 31.3 per cent.M.W. =412.The substance, Cl5Hl0O6, is soluble in alkali hydroxides, forminga colourless solution. I n alcoholic solution it gives with ferricchloride a dark green coloration. With concentrated sulphuricacid, only a faint yellow colour is produced.The yield of the substance C15H1006 was very small, not morethan 0.5 gram having been obtained from 37.1 kilograms of driedclover flowers.1solct.tion of a New Ghcoside, Trifolin, C22H220,,,H,0.The original aqueous liquid (A), which had been extracted withether, as already described, was kept foy a, considerable time, whenit was observed that a quantity (about 60 grams) of a light brownsolid had been deposited. This was collected, and purified byrepeated crystallisation from aqueous pyridine, when it separatedin minute, slender, pale yellow needles, melting and decomposinga t about 260O.The substance contained water of crystallisation,which was lost at 115O, but was again absorbed on exposing theanhydrous substance t o the air:M.W.=415.0.3051, on heating a t 115O, lost 0'0130 H20.0*1101* gave 0.2302 CO, and 0.0464 H20. C=57*0; H =4.7.0'1194* ,, 0.2481 (30, ,, 0*0506 H20. C=56*7; H=4*7.0*1010 * ,, 0.2115 CO, ,, 0.0440 H20. C=57.1; H=4*8.C2,H2,O,,,H20 requires H20 = 3.7 per cent.C22H2,011 requires C = 57.1 ; H = 4.8 per cent.H20=4'3.These results indicated the formula of the above-described sub-stance to be C22H22011, and it proved to be a glucoside. As it is anew compound, it is proposed to designate it trifolin, with referenceto the generic name of the plant from which it was obtained.Trif olin, C2,H2,OlI,H2O, is insoluble in chloroform, benzene, orcold water. It is not readily dissolved by alcohol, but is verysoluble in pyridine, and is best crystallised from a mixture of thelatter solvent with water.With aqueous sodium carbonate andthe alkali hydroxides, it gives intensely yellow solutions. It dis-solves in concentrated sulphuric acid, forming a t first a yellowsolution, but which rapidly develops a brilliant green fluorescence.I n alcoholic solution it gives with ferric chloride a dark browncoloration. No crystalline acetyl derivative of trifolin could beprepared.i+ Anhydrous substance240 POWER AND SALWBY:Hydimolysis of TiifoZin : Formution of u Yellow Colouriny Natter,T?if oli tin, C 16HTrifolin was dissolved in alcohol, it little dilute sulphuric acidadded, and the mixture heated on the water-bath for an hour.The alcohol was then removed by distillation in a current of steam,when a yellow, crystalline substance separated.This was collected,and washed with cold water, the filtrate having been set aside forthe subsequent examination of the sugar. Some difficulty wasexperienced in satisfactorily crystallising the yellow hydrolyticproduct, for it is extremely soluble in alcohol, and invariablyseparates from dilute alcohol at the ordinary temperature in anapparently amorphous condition. On the other hand, i f the alcoholis removed from the solution a t the boiling temperature, the sub-stance then separates from the hot liquid in thin, yellow needles.It is, however, best purified by crystallisation from moist nitro-benzene, when it separates in clusters of slender, yellow needles,which melt and decompose at about 275O.After drying a t 130°,it was analysed:0.0786 gave 0.1846 CO, and 0.0264 H,O. C = 64.1 ; H = 3.7.By heating the yellow hydrolytic product with acetic anhydridean acetyl derivative was obtained The latter, when crystallisedfrom alcohol, separated in colourless, silky needles, which, whenrapidly heated, melted a t about 116O, then resolidified, and finallymelted a t 182O. This behaviour was due to the presence of waterof crystallisation, the melting point of the anhydrous substancebeing 1 8 2 O :C,6H&6 requires C = 64.4 ; H = 3.4 per cent.0.5676, on heating at 105O, lost 0-0231 H,O.The anhydrous substance was analysed, and its molecular weight0.1078 gave 0.2426 CO, and 0.0401 H,O.0.4012, in 28.14 of phenol, gave ht-0*216°.C,,H6O6(C0*CH3), requires C= 61.8; H= 3.9 per cent.M.W. =466.In order to ascertain the number of acetyl groups in the abovccompound, it was dissolved in alcohol, dilute sulphuric acid added,and the mixture heated for several hours on the water-bath. Thealcohol was then completely removed by distillation in a current ofsteam, and, after cooling, the precipitated yellow substance wascollected and weighed, it having been found that the amountdissolved by the water was negligible:H,o=4'1.C,6Hti06(CO*CH3)4,H,0 requires H,O = 3.7 per cent.determined, with the following results :C = 61.4 ; H =4.1.M.W.=495.0.1056 ,, 0.2375 CO, ,, 0.0391 H20.C=61.3; H=4.1THE CONSTITUEN'I'S OF KED CLOVER FLOWERS. 2410*1811 gave 0.1160 of colouring matter, or 64.1 per cent.0.2922 ,, 0.1876 2, 9 , 64.2 ,,C1,HgO6(CO*CH3), requires C,,H,,O, = 63.9 per cent.The yellow colouring matter, as obtained from the above-described acetyl derivative, was crystallised from dilute alcohol,dried a t 120°, and again analysed:0.0855 gave 0.2000 CO, and 0.0276 H,O.C,,H,,06 requires C = 64.4 ; H = 3.4 per cent.It is evident from the above results that the yellow colouringmatter obtained by the hydrolysis of the glucoside trifolin possessesthe formula C,,H1,O,, and that it contains four hydroxyl groups.As no compound of this formula, having the same properties, hashitherto been recorded, it is proposed to designate it trifolitin.Trifolitin, C16H1006, is readily soluble in alcohol and glacialacetic acid, but only very sparingly soluble in benzene, chloroform,or ether.It dissolves in alkalis with an intense yellow colour, anddyes mordanted cotton wool a bright yellow. When dissolved inconcentrated sulphuric acid, it gives a yellow solution, followed bya brilliant green fluorescence. It is precipitated from its alcoholicsolution Sy basic lead acetate as an orange-yellow lead salt. I nalcoholic solution it gives with ferric chloride a dark greencoloration. Trifolitin is not altered when heated for several hourswith 30 per cent.aqueous potassium hydroxide, and it contains nomethoxyl group. It is evident from its empirical formula, CI6Hl0O6,that .it cannot belong to the flavone group of natural colouringmatters, and it differs, moreover, from the flavone compounds bythe fact that it forms no salt with sulphuric acid (Trans., 1896,80, 206), whilst it is only with difficulty that a potassium salt isdeposited from its concentrated alcoholic solution on the additionof potassium acetate. On the other hand, the composition andgeneral properties of trifolitin would agree with those of a tetra-hydroxy-derivative of phenylnaphthaquinone, but the amount ofmaterial availablc was not sufficient to enable us definiteIy toascertain the group of naturally occurring dyes to which it belongs.The aqueous liquid obtained in the course of hydrolysis of theglucoside trifolin was treated with barium carbonate for the removalof the sulphuric acid, and evaporated to the consistency of a syrup.This liquid readily reduced Fehling's solution, and yielded acrystalline osazone which, in the crude condition, melted anddecomposed a t 1 80°.When crystallised from aqueous pyridine, itseparated in needles, which melted and decomposed a t 194O:C=63*8; H=3*6.0.1258 gave 0.2902 CO, and 0.0738 H,O.The above result indicated that the sugar formed by theVOL. XCVJI. EtC = 62.9 ; H = 6.5.CI8H,,O3N, requires C = 63.2 ; H = 6.4 per cent242 POWER AND SALWAY:hydrolysis of trifolin has the formula C6H1205, and it appeared tobe rhamnose, the osazone of which, however, is stated t o melt a t180O.For the purpose of comparison, an osazone was preparedfrom a commercial specimen of rhamnose. This, when crystallisedfrom aqueous pyridine, was found to melt and decompose at.188O, and appeared to be identical with that above described.Trifolin is therefore converted by hydrolysis into trifolitin andrhamnose. A known weight of the glucoside was subsequentlyhydrolysed by dilufe sulphuric acid in aqueous alcohol, the alcoholthen removed by passing sfeam through the mixture, and, aftercooling, the precipitated trifolitin was collected, washed with coldwater, dried a t 120°, and weighed:0.2056 gave 0.1318 of hydrolytic product, or 64.1 per cent.0-2885 ,, 0-1859 9 , 7 9 64.4 ,,C22H220,, requires C16H1,06 = 64.5 per cent.The hydrolysis of trifolin therefore takes place according to thefollowing equation :C22H22011 = C16H1006 -k c6H1205*Trifolin.Trifolitin. Rhamnose.This equation would appear to indicate that the formation oftrif olitin and rhamnose from trifolin is unaccompanied by theabsorption of water, and would thus be analogous to that repre-senting the hydrolysis of quercitrin * :C21H22012 = C15H1007 + C6H1206*Quercitrin. Quercetin. Rhamnose.The explanation of this apparent anomaly may be, either thatthese glucosides tenaciously retain a molecule of water, or that therespective phenolic hydrolytic products suffer dehydration imme-diately after their formation.The dark-coloured aqueous liquid from which the above-describedglucoside, trifolin, had separated was next shaken repeatedly withhot amyl alcohol.The amyl alcohol extracts were united, washedwith a little water, and then concentrated under diminished pres-sure, when, on cooling, a yellow, gelatinous subdance was deposited.This was removed by filtration, and the filtrate again conceGtrated,when a further quantity of a yellow substance was obtained. Tothe final amyl-alcoholic filtrate, light petroleum was added, which* The hydrolysis of quercitrin is usually represented as fo!lows :This equation, Iiowever, is evidently illcorrect, inasmncli as it is now I ~ n o w nthat rhamiiose possesses the formula CGHl2O5, but crystallises with one nrolecnle ofwater (comlmre A.G. I’erkiu, J. Xoc. Chem. Ind., 1903, 22, 602, and Brauns, Amh.Phnrm., 1904, 24.2, 561).C2IHydOIZ i H,O=C,,H,o07 + CGHIjOGTHE CONSTITUENTS OF RED CLOVER FLOWERS. 243precipitated the remainder of the yellow substance as an amorphouspowder. The three fractions thus obtained were separatelyexamined.Fraction I.-This product consisted of a yellow, highly hygro-scopic substance. It was dissolved in hot alcohol, and the solutionkept for some time, when a gelatinous, brown mass separated. Thelatter was twice subjected to the preceding treatment with alcohol,when a crystalline substance was obtained, which was finally purifiedby crystallisation from dilute alcohol. It then formed colourless,glistening leaflets, melting at 214O. The amount of pure substanceisolated was 0.5 gram :0.0989 gme 0.2199 CO, and 0.0440 H,O.C = 60.6 ; H = 4.9.0'1154 ,, 0.2559 CO, ,, 0.0496 HZO. C=60.5; H=4.8.C,4H1206 requires C = 60.9 ; H = 4.3 per cent.This substance would thus appear to possess the formula Cl4HI2O6,and, as it differs in its properties from any substance of thisformula which has hitherto been recorded, it may be regarded asa new compound.The compound, C14H1206, is insoluble in water, chloroform, orbenzene, but readily soluble in hot alcohol. It is insoluble inaqueous sodium carbonate, but readily dissolves in alkali hydroxideswithout change of colour. It gives no coloration with concentratedsulphuric acid, and is not changed by heating with dilute sulphuricacid. Its alcoholic solution yields with ferric chloride a light greencoloration.Isolation of a Second Glucoside of TrifoEitin, isoTrifolin, C,,H,,O,,.Fraction ZZ.-This product, consisting of a light yellow powder,was fractionally crystallised from alcohol.The more solubleportion contained a substance which separated from very dilutealcohol in pale yellow needles, melting and decomposing at about250° with the formation of a deep red liquid. It was dried a t 115O :0.1100 gave 0.2282 CO, and 0.0451 H,O.The glucosidic character of this substance was proved by heatingwith dilute sulphuric acid in aqueous alcohol. On removing thealcohol, a yellow colouring matter separated from the hot solutionin thin needles, which melt.ed and decomposed at 275O. Thishydrolytic product yielded an acetyl derivative, which was foundto be identical with that prepared from the previously describedtrifolitin, C,,H,,O6.The aqueous liquid obtained in the course ofthe above hydrolysis readily reduced Fehling's solution, but theamount of glucoside available (0.5 gram) did not, permit of pre-paring an osazone from the sugar.C=56*6; H=4*6.C22H22011 requires C = 57.1 ; H = 4.8 per cent.R 244 POWER AND SALWAY :Although the above-described glucoside yields the same yellowhydrolytic product, and possesses apparently the same empiricalformula as the glucoside trifolin, the two compounds are evidentlynot identical. Thus trifolin (m. p. 260°) separates from dilutealcohol in small, globular aggregates of fine needles, whilst theglucoside, melting a t 250°, is much more soluble, and crystallises inclusters of comparatively large needles.It is therefore proposedto designate the second glucoside of trifolitin as isotrif olin.The general behaviour of isotrifolin, as might be expected, isvery similar to that of trifolin. It dissolves in alkalis with theformation of a deep yellow solution. With concentrated sulphuricacid, a yellow coloration is produced, together with a greenfluorescence, and in alcoholic solution i t gives with ferric chloride adeep brown colour.Isolation of u Gducoside of Quercetin.The sparingly soluble portion of the above-described fraction I1was finally purified by crystallisation from water, when it separatedin pale yellow, prismatic needles, melting and decomposing at 235O :0.1484, on heating at l l O o , lost 0.0161 H,O.0.1117, dried at l l O o , gave 0.2184 CO, and 0.0475 H,O.The substance dissolved readily in hot water, giving a yellowsolution, the colour of which was greatly intensified by the additionof alkalis. With concentrated sulphuric acid, a green fluorescencewas produced. I t s aqueous solution gave with ferric chloride adark green coloration.On heating the substance for a short time in aqueous solutionwith dilute sulphuric acid, a crystalline, yellow compound separated,and the filtrate from the latter readily reduced Fehling's solution.It was thus evident that the substance was a glucoside.The yellowhydrolytic product melted and decomposed at 305O, and, by meansof its acetyl derivative (m.p. 195O), was identified as quercetin.The amount of this glucoside obtained from 37.1 kilograms of driedred clover flowers was only about 0.5 gram, and it was thereforenot possible more definitely to daracterise it.Fraction ZZZ.-This was a yellow, amorphous solid, which wasfreely soluble in alcohol, giving a dark-coloured solution. Theattempts to obtain something crystallinc from this solution wereunsuccessful, and as a preliminary test indicated the presence ofglucosidic substances, the whole of the fraction, together with tlicmother liquors from fractions I a r d 11, was hydrolysed by heatingfor some time with dilute sulphuric acid in aqueous alcohol. Afterremoving the alcohol, a quantity of a dark-coloured solid separated,H20=10.8.C=53*3; H=4*7THE CONSTITUENTS OF RED CLOVER FLOWERS.245which was collected and washed with water. This product wasfound to be a highly coinplex mixture, which, however, by digestionwith ether, could be separated into readily and sparingly solubleportions. The ethereal solution of the readily soluble portion wasextracted with alkalis, when it yielded traces of salicylic acid, asmall amount of pratol, CI6Hl2O1, and a yellow coinpound meltinga t 305O, which, by means of its acetyl derivative (m. p. 194O), wasidentified as quercetin.Isolation of isoRhamnetin, Cl,H,,07.The portion of the above-mentioned hydrolytic product whichwas sparingly soluble in ether was treated with aqueous sodiumcarbonate, when it was found to be only partly soluble in thealkaline liquid.From the insoluble portion a, small amount ofthe previously described compound, CI4Hl2O6 (m. p. 214O), wasobtained, whilst the portion soluble in the alkali carbonate con-sisted chiefly of a yellow colouring matter, which was observed todiffer from any of the substances already isolated from the cloverflowers. This substance was sparingly soluble in acetic acid andalcohol; and was purified by conversion into its acetyl derivative,the latter being then fractionally crystallised from alcohol untilconstant in melting point. It then separated in thin, hair-likeneedles, melting at 198-200°. After being dried a t 120O:0.0927 gave 0.2017 CO, and 0.0354 H,O.CI6H8Oi(~*CH3), requires C = 59.5 ; H = 4.1 per cent,The number of acetyl groups in this derivative mas determinedby hydrolysis with dilute sulphuric acid, the hydrolytic productbeing then collected and weighed :C=59.3; H=4.2.0-1120 gave 0.0722 of colouring matter, or 64.5 per cent.0.1126 ,, 0.0734 ? 9 Y2 65.2 ,,Cl,H80,(CO~CH3), requires CI6H1,O7 = 65.3 per cent.The hydrolytic product, which melted and decomposed at about295O, was a deep yellow substance, only sparingly soluble in alcoholor acetic acid, and insoluble in chloroform or benzene.It dissolvedin alkalis, with the production of a deep yellow colour, and itssolution in sulphuric acid possessed a green fluorescence. It wasfound to contain one methoxyl group, as determined by Perkin’smodification of the Zeisel method :0.0941 of acetyl compound gave 0.0379 AgI.C,,H,O,(OCH,)(CO*CH,), requires Me0 = 6.4 per cent.From these analytical data it may be concluded that the yellowsubstance has the empirical formula Cl,H,,Oi, and that it containsfour hydroxyl groups and one methoxyl group.The compositionMe0 =5*3246 POWER AND SATJWAY:and characters of this substa.nce are thus in agreement with thoseof isorhamnetin, a colouring matter which was first isolated byA. G. Perkin (Trans., 1896, 69, 1658) from the petals of the yellowwallflower (Cheirnnthus Cheiri). The last-mentioned author had,however, recorded the melting point of tetra-acetylisorhamnetin asI n order to further confirm the identity of the substance con-tained in red clover flowers with isorhamnetin, the product resultingfrom the niethoxyl determination was examined.This separatedfrom the acid solution, on cooling, in yellow, silky needles, whichdid not melt, but partially volatilised, a t a temperature below3 0 0 O . It gave an acetyl derivative melting a t 190--192O, andpossessed the general characters of quercetin, thus affording con-clusive evidence that the respective substance in red clover flowerswas a monomethyl derivative of quercetin and identical with iso-rhamnetin.195-1 96'.The aqueous liquid which had been extracted with hot amylalcohol, as above described, was dark brown in colour, and gavean abundant yellow precipitate on the addition of basic leadacetate. This precipitate was examined in the usual way, but,with the exception of a small amount of yellow colouring matter,nothing definite could be isolated from it.The filtrate from thebasic lead acetate precipitate, after removal of the excess of lead,was of a bright yellow colour, and readily reduced Fehling'asolution. It, contained a large quantity of sugar, which yieldedd-phenylglucosazone, melting a t 2 0 5 O . The liquid was concentratedunder diminished pressure to t,he consistency of a, syrup, and keptfor a considerable time, but nothing crystalline separated from it.The Resins (B).The resinous material obtained from 1.5 kilograms of the originalalcoholic extract of red clover flowers was a dark green, soft solid,and amounted to 314 grams. It was dissolved in alcohol, thesolution mixed with purified sawdust, and the thoroughly driedmixture then successively extracted in a Soxhlet apparatus withvarious solvents, when the following amounts of extract., dried at100°, were obtained :Petroleum (h.p. 30-45") cstractod 190.0 grams = 60.5 1)er cent.Ether ) ) 19'0 ,, = 6'1 ,,Chloroform ,, 6.7 ,, = 2.1 ,,Alcohol ,, 43.0 ), = 13.7 ) )Ethyl Acetate ,, 10.3 ,, = 3.3 ,,- -Total 269'0 grams = 85.7 per centTHE CONSTITUENTS OF RED CLOVER FLOWERS. 247Petroleum Extract of the Resin.It washydrolysed by heating for a short time with an alcoholic solutionof potassium hydroxide, after which the alcohol was removed, wateradded, and the alkaline mixture repeatedly extracted with ether.The ethereal extracts were united, washed, dried, and the solventremoved, when a quantity (46.5 grams) of a brownish-yellow solidwas obtained.This extract consisted of a dark green, semi-solid fat.Isolation of .iVyricyl A Zcohol, C,,H,,*OH.The above-mentioned, brownish-yellow, unsaponifiable materialwas agitated with cold alcohol, and thus separated into a solubloand an insoluble portion. The latter consisted of a colourless, wax-like solid, melting somewhat indefinitely at 70-74O.It appearedto consist of a mixture of several substances, and was thereforesubjected t o prolonged fractional crystallisation from it mixtureof ethyl acetate and alcohol. I n this manner the least solubleconstituent was ultimately obtained pure, and then melted a t 85O.It crystallised from ethyl acetate in small, colourless needles, whilstfrom alcohol it separated in glistening leaflets :0.1250 gave 0.3776 CO, and 0.1597 HiO.The analysis and properties of this substance establish its identityC = 82.4 ; H = 14.2.C,,H,, requires c = 82.3 ; H = 14.2 per cent.as myricyl alcohol.Isolation of Heptacosane, C27H56, Hentriacontane, CZ1HG4, andSit 0s t ero I, C,,H,,O.The more soluble substances obtained in the course of the abovefractionation could not be further separated by crystallisation.Apreliminary examination having indicated that they consistedchiefly of hydrocarbons, with presumably a little myricyl alcohol,the mixture was heated at 130° for an hour with an equal weight ofphthalic anhxdride, in order to convert the myricyl alcohol into itsacid phthalic ester, and thus effect its removal.The product wassubsequently digested with a mixture of ether and chlorofoym, thesolution filtered, and shaken with aqueous sodium carbonate. Aninsoluble compound thus separated, which was collected, and foundto consist of myricyl sodium phthalate. The ether-chloroformsolution was then evaporated, and the residue heated with aqueoussodium hydroxide in order to remove unchanged phthalic anhydride.The portion insoluble in the alkali was afterwards dissolved inchloroform, the solution being washed, dried, and the solven248 POWER AND SALWAY:remcved. A wax-like solid was thus obtained, which was sub-jected to fractional crystallisation from ethyl acetate. The mostsparingly soluble fraction, which Separated in pearly leaflets, meltedat 65O, and this melting point was not changed by furthercrystallisation :0*1001 gave 0.3121 CO, and 0.1324 H,O.C,,H,, requires C = 85.3 ; H = 14.7 per cent.This substance was evidently hentriacontane (rn.p. 68O), thesomewhat low melting point being probably due to the presenceof a small amount of the following hydrocarbon.From the more readily soluble fractions, a substance was isolated,which separated in pearly leaflets, melting a t 58-59O:0,0944 gave 0.2943 CO, and 0.1229 H,O.C,,H,, requires C = 85.3 ; H = 14.7 per cent.This substance was thus identified as heptacosane.The portion of the unsaponifiable material which was soluble incold alcohol amounted t o 30.2 grams. It was twice distillea underdiminished pressure, and the following five fractions collected :200-210°; 210--220°; 220-290O; 290-300O; and above 300°/20mm.Fraction 200-210°/20 mm.-This was a pale yellow liquid, andcontained a considerable quantity of an unsaturated substance :0.1083 gaire 0.3256 CO, and 0.1289 H20. C =82.0; H = 13.2.0.1234 absorbed 0.1008 iodine.Fraction 210-220°/20 mm.-This was a brownish-yellow liquid,0.1064 gave 0.3141 CO, and 0.1288 H20.0.0990 absorbed 0.0832 iodine.Both the above fractions were evidently mixtures, and nothingof a definite nature could be obtained from them.Fractions 220--290° ; 290-300° ; and above 300°/20 mm.-Thesefractions solidified on cooling, and were found to consist chieflyof a phytosterol, with a small quantity of the previously mentionedhydrocarbons.After repeated crystallisation, a substance wasisolated which separated from a mixture of ethyl acetate andalcohol in colourless, glistening leaflets, melting a t 135-136O :C =85*0; H= 14-7.C=85.0; ;R=14*5.Iodine value = 81.7.and, like the preceding fraction, was unsaturated :C =80*5 ; H= 13.5.Iodine value = 84.0.0.3194, on heating at l l O o , lost 0.0160 H,O.0.0963, dried at l l O o , gave 0.2959 CO, and 0.1033 H,O.H,O=5.0.C,,H,,O,H,O requires H,O = 4.5 per cent.C = 83.8 ; H = 11.9.C27H46O requires C = 83.9 ; H = 11.9 per cent.0.2244 of anhydrous substance, made up to 25 C.C. with chloro-form, gave a, -Oo37/ in a 2 dcm. tube, whence [aID -34.4OTHE CONSTITUENTS OF RED CIAOVER FLOWERS.249The above-described substance was evidently a phytosterol, andit gave the colour reactions of this class of compounds. It yieldedan acetyl derivative, melting a t 12G0, and therefore i s identical mitJisitosterol (Monatsh., 1597, 18, 551).7solation of a New Dihydric Alcohol, Trifolinnol, C2,Hx02(OH)2.The aqueous alkaline solution of potassium salts resulting fromthe hydrolysis of the petroleum extract of the resin, having beenshaken with ether to remove unsaponifiable material, as alreadydescribed, was acidified with dilute sulphuric acid, when a dark-coloured semi-solid precipitate of fatty acids was produced. Onextracting the mixture with ether, however, it was observed that aportion of the precipitate was very sparingly soluble in thatliquid. The sparingly soluble material was therefore collected,when it formed a pale green solid, amounting to 3 grams.It waspurified by crystallisation from pyridine containing a little alcohol,from which it was deposited in minute, colourress needles, meltingand decomposing a t 295O. After being dried at l l O o :0.1049 gave 0.2746 CO, and 0.0982 H,O.This compound yielded an acetyl derivative, which separatedfrom alcohol in flat, colourless needles, melting at 165-166O. Ananalysis and the determination of its optical rotatory power gavethe following results :C = 71.4 ; H = 10.4.C21H3604 requires C = 71.6 ; H = 10.2 per cent.0.0968 gave 0.2442 GO2 and 0.0799 H20.0-2435, made up to 25 C.C. with chloroform, gave a, -Oo30/ in aFrom the above results it was evident that the compound meltingat 295O is a, dihydric alcohol, having the empirical formulaC2,H3604.As i t is a new substance, it is proposed to designateit trifolianol, with reference t o the generic name of the plant fromwhich it was obtained.5"rifoZianoZ, C,,H,,O,( OH),, is practically insoluble in water, andvery sparingly soluble in alcohol, ether, and chloroform, but readilysoluble in dilute pyridine, from which it crystallises in minuteneedles. When dissolved in chloroform with a little aceticanhydride, and a drop of concentrated salphuric acid subsequentlyadded, it gives a transient pink coloration, changing to blue, andfinally to gregn. The properties of trifolianol are similar to thoseof two other dihydric alcohols which have recently been isolated inthese laboratories, namely, ipuranol, C23H,80,(OH)z ( A nzer.,7.PJmrnz., 1908, 80, 264, 576; Trans., 19OS, 93, 907; 1909, 95, 249),C = 68.8 ; H = 9.2.C,,H,,O,(CO*CH,), requires C = 68.8 ; H = 9.2 per cent.2-dcm. tube, whence [a], -25'7O250 POWER AND SALWAY:and citrullol, C,,H3,02(OH), (this vol., p. 102). These alcoholstherefore appear to be members of a homologous series, which isrepresented by the general formula, C,,H2, ,@.,.K,ramin,ation of the Fatty A cids.The ethereal solution, from which the above-described trifolianolhad been removed by filtration, was washed, dried, and the solventremoved. The mixture of fatty acids thus obtained contained aconsiderable quantity of resinous material, which was insoluble inlight petroleum, and was therefore removed by digesting themixture with the latter solvent, and filtering.This resin was Bdark green solid, amounting to 10 grams, but no definite crystallinecompound could be isolated from it. The petroleum solution, onevaporation, yielded a dark-coloured mixture of fatty acids, whichwas distilled under diminished pressure. The pale yellow distillate,amounting to 60 grams, became partly solid on cooling. It wasdissolved in alcohol, when a substance separated which, after severalcrystallisations from alcohol, melted at GO-GlO :0.1182 gave 0.3236 CO, and 0.1341 H20. C=74.7; H=12.6.0.1280 required for neutralisation 5-02 C.C. N / 10-KOH.Neutralisation value= 220.C,,H3,02 requires C = 75.0 ; H = 12.5 per cent.Neutralisation value = 219.1.This substance was thus identified as palmitic acid.I n order to ascertain the nature of the remaining constituents ofthe mixed fatty acids, the mother liquors from the abovecrystallisations were united, and, while hot, fractionally precipitatedwith a concentrated aqueous solution of barium acetate.The finalprecipita.te was oily, and, as it consisted for the most part of thebarium salts of unsaturated acids, it was separately examined asdescribed below. From the other fractions of barium salt the fattyacids were regenerated, and, after one crystallisation from aceticacid, were titrated with a decinormal solution of potassiumhydroxide. The neutralisation values of the several fractions were199.0; 210.0; 213.0; 213.5; 214.8; and 216.9, whilst their meltingpoints were 53-55O; 53-56O; 53-56O; 53-56O; 54-56O; and5G-59O respectively.These results indicated that the satdratedacids consisted chiefly of a mixture of palmitic and stearic acids,the respective neutralisation values of which are 219.1 and 197.7.The acids obtained from the above-mentioned oily barium saltwere converted into their lead salts, and the latter treated withether. From the portion of lead salt which was undissolved bythe ether, a further small amount of palmitic acid was obtained.The acids regenerated from the soluble lead salt formed a palTHE COKSTITUENTS OF RED CLOVER FLOWERS. 251yellow oil, which was distilled under diminished pressure. Ananalysis and the determination of its constants gave the followingresults :0.1428 gave 0.4031 CO, and 0.1437 H,O.d 2Oo/2O0 = 0.9148. Neutralisation value 200.9.Iodine value 184.7.CI8H3,O2 requires C = 76-6 ; H = 12.1 per cent. NeutralisationCIBH32O2 requires C = 77.1 ; H = 11.4 per cent. NeutralisationC,,H,,O, requires C = 77.7 ; H = 10.8 per cent.. NeutralisationI n order to ascertain more definitely the nature of the unsaturatedacids, 10 grams of the mixture were dissolved in alkali, andoxidised with a 1.5 per cent. solution of potassium permanganate.The chief product of the oxidation, when crystallised from water,separated in thin needles, melting at 156-157O:C = 77.0; H = 11.2.value = 198.9.value= 200.4. Iodine value = 181.4.value= 201.8.Iodine value = 90.1.Iodine value = 274.0.0.0630 ga8ve 0.1426 CO, and 0.0594 H,O.This substance was evidently tetrahydroxystearic acid (sativicacid).I n addition to the latter acid, very small quantities ofdihydroxystearic acid (m. p. 130°), linusic acid (m. p. 200-205°),and isolinusic acid (m. p. 173-174O) were obtained.The above results would therefore indicate that the unsaturatedacids consisted chiefly of linolic acid, with smaller amounts of oleic,linolenic, and isolinolenic acids.C = 61.7 ; H = 10.5.C,,H3,0, requires C = 62.1 ; H = 10.3 per cent.Ethereal Extract of the Resin.This extract was a black, brittle solid, and amounted to 19 grams.It was digested with 500 C.C. of ether, when the greater portionpassed into solution, while a small amount of a light green powderremained undissolved. The latter was collected, and boiled withalcohol, in which it was very sparingly soluble, in order to removethe green colouring matter.It was finally crystallised from amixture of pyridine and alcohol, when it separated in colourlessneedles, melting and decomposing at about 290O. It yielded anacetyl derivative, melting a t 166O, which was analysed :0.0854 gave 0-2142 CO, and 0.0690 H,O.C2,H3,O,(CO*CH3), requires C = 68.8 ; H = 9.2 per cent.The above-described substance, when dissolved in chloroform witha little acetic anhydride, and a drop of concentrated sulphuric acidsubsequently added, gave a pink coloration, rapidly changing toblue, and finally to green. It was evidently identical with theC = 68.4 ; H = 9.0252 POWER AND SALWAY:dihydric alcohol designated as trif olimol, which had previouslybeen isolated from the petroleum sxtract of the resin.The above-mentioned ethereal solution of the ethereal extract,was shaken successively with aqueous ammonium carbonate, sodiumcarbonate, and sodium hydroxide, and the various extracts thusobtained were separately examined.The ammonium carbonateremoved only traces of a green resin. The first sodium carbonateextract yielded, on acidification, a dark green resin, which consistedchiefly of chlorophyll, whilst the subsequent sodium carbonateextract, when acidified, gave a nearly colourless precipitate. Thiswas collected and dissolved in alcohol, when a small amount of asubstance separated in colourless, talon-like needles, melting a t253O.This substance was found to be identical with the compounddesignated as pratol, CI6Hl2O4, which had previously been isolatedfrom the portion of the alcoholic extract of clover flowers whichwas soluble in water. The mother liquors from the crystallisationof the pratol deposited a little of a crystalline substance, meltingsomewhat indefinitely between 1 7 8 O and 183O, but the amount wastoo small to permit of its further examination. The final extractionof the ethereal liquid with sodium hydroxide yielded nothing butamorphous products, and on subsequently evaporating the etheronly traces of a soft resin remained.Chloroforna and EthLyl Acetate Extracts of the Resin.These extracts were black, brittle solids.They were small inamount, and nothing crystalline could be isolated from them,Alcohol Extruct of t h e Resin.This was a dark brown, brittle solid, amounting to 43 grams.I n order to ascertain whether it contained anything glucosidic, it,mas heated for some time with a 5 per cent. solution of sulphuricacid in aqueous alcohol, and the mixture subsequently distilledwith steam, but no volatile oil or acid passed over. The distillationflask then contained, besides the aqueous liquid, a quantity of ablack resin, which was collected and examined, but nothing definitecould be isolated from it. The aqueous liquid, on the other hand,when extracted with ether, yielded a small quantity of a viscid,vellow oil, which gradually deposited a solid substance.The latterwas crystallised from alcohol, when it separated in colourlessneedles, melting at 250°, and gave an acetyl derivative meltingat 166O. It proved to be identical with the previously describedsubstance, C,,H,,04, designated as pratol. The aqueous liquidTHE CONSTITUENTS OF RED CLOVER FLOWERS. 253which had been extracted with ether as above described, was freedfrom sulphuric acid by means of baryta, and concentrated to asmall volume. It then readily reduced Fehling's solution, andyielded a small quantity of an osazone, melting a t 203'.These facts indicated the presence of a glucoside in the alcoholicextract of the resin, and it is probable that the small amount ofpratol, ClGHl2O4, obtained from the latter represents one of itshydrolytic products.Sum?nary.The detailed results of the present investigation of red cloverflowers (Trifolium pratense, Linn6) may be summarised as follows :A quantity of the alcoholic extract, representing 37.1 kilogramsof the dried flowers, when distilled with steam, yielded 10.5 grams,or 0.028 per cent., of essential oil. This essential oil, whichcontained furfuraldehyde, possessed the following constants :d 2O0/2O0=0-9476; uD +4OO/ in a 1-dcm. tube.The portion of the alcoholic extract which was soluble in watercontained a large amount of sugar, which yielded d-phenyl-glucosazone (m. p. 205O), but from the aqueous liquid the followingdefinite substances were isolated : salicylic and p-coumaric acids ;isorhamnetin, CIGH1207 (m. p. 2 9 5 O ) , which wits probably presentin the form of a glucoside; a number of new phenolic substances:pratol, Cl,H802('OH)(OCH3), m. p. 253O, which apparent,ly is ahydroxymethoxyflavone, and yields an acetyl derivative melting a t166O; pratelzsol, C17H,02(OH),, m. p. 210°, which yields a triucetylderivative melting a t 189'; a yellow compound, C16H,,0, (m. p.280°), which yields a tetra-acetyl derivative melting at 145-147O;a substance, C15H703(OH)3, m. p. 225O, which yields a triacetglderivative melting at 209O; a substance, C14H,,0, (m. p. 214O);also the following new glucosides : trifolin, C2nH220,,,H20 (m. p.260°), which yields on hydrolysis a yellow colouring matter,trifolitin, C,,H,,O6 (m. p. 275O), and rhamnose, C6H1,0,; iso-trifolin, C22H220,1 (m. p. 250°), and a glucoside of quercetin, melt-ing at 235O.The portion of the alcoholic extract which was insoluble inwater consisted chiefly of resinous material, the amount of whichwas equivalent to 5.6, per cent. of the weight of dried clover flowers.From the resin the following compounds were obtained : myricylalcohol, C,,Ho,*OH ; heptacosane, C2,HGG, and hentriacontane,CY1HG.I; sitosterol, C27H460 (m. p. 135-136O; [ U ] ~ -3414"); a newdihydric alcohol, trifolianol, C,,H3,0,(0H), (m. p. 295O), whichappears to be a homologue of ipuranol, C2,H,802(0H),, and yieldsa diacetgl derivative melting at 165-166O and having [aID - 25'7O ;a mixture of fatty acids, consisting chiefly of palmitic, stearic, an254 FORSTER AND JUDD: THE TRIAZO-GROUP. PART X l I ,linolic acids, with small amounts of oleic, linolenic, and isolinolenicacids. A small amount of pratol, C16H1204, was likewise obtained,the latter having evidently been present in the resin in the formof a glucoside.THE WELLCOME CHEMICAL RESEARCH LABOILATO~LIES,LONDON, E.C

ISSN:0368-1645    

DOI:10.1039/CT9109700231

出版商:RSC    

年代:1910

数据来源: RSC

摘要:

254 FORSTER AND JUDD: THE TRIAZO-GROUP. PART X l I ,XXVIL-The Triaxo-y-oup. Pwt X I I . Deyivatives oj'para- T~.iaxobeizxaldehyde.By MARTIN ONSLOW FORSTER and HILDA MARY JUDD.AN investigation of the hydroxyphenylazoimides (Trans., 1907, 9 1,855 and 1350) brought to light a characteristic distinction betweenthe potassium derivative of the para-compound and those of the ortho-and meta-triazophenols depending on the change of colour whichtakes place when the solution in water or absolute alcohol is heated ;as a consequence of this treatment, the colourless substance is trans-formed into a dark blue material, which appears to be isomeric with i t sgenerator. The explanation of this behaviour which suggested itselfat the time depends on the possibility of rearrangement having takenplace in accordance with the following formulae :N N NKN f i ' KO*CGHh*N<j -+ O:CG'EI,:NK<* or O:C,H,:N<and although i t was not possible to recognise any substantialdifference between the acyl derivatives prepared from the bluecompound and those obtained from the colourless potassium salt,they were certainly more highly coloured ; moreover, whilst thep-triazophenol liberated from i t by acids appeara to have the generalproperties of the original material, the solid potassium derivativeregenerated by the action of alkali is not colourless, but bluish-green.The absence of any similiar colour change in the cme of ortho- andmeta-hydroxyphenylazoimides has led us t o examine certain para-derivatives of triazobenzene in which the.occurrence of hydrogen inthe group occupying the para-position afforded an opportunity ofrearrangement on the lines indicated above. The condensationproducts from p-triazobenzaldehyde with hydroxylamine, phenyl-hydrazine, and p-amiuophenol might have been expected, underfavourable circumstances, to yield coloured modifications depending ontransposition of hydrogen FORSTEK. AND JUDD: THE TRIAZO-GROUP. PART XII. 255N NNC,H,* N H N : CH*C,H,*N<* -+ C6H5*N : N*CH: CGH4: N H<gI n no case, however, has any indication of a colour change by alkalibeen observed, and although it certainly happens that a chloroformsolution of p-triazobenzaldehydephenylhydrazone ritpidly becomesbrown and ultimately purple when exposed t o light, the observationsof Chattaway (Trans., 1906,89,462) in connexion with the alterationwhich benzaldehydephenylhydrazone undergoes, would suggest corre-spondence betwean the two phenomena.There does not appear to be any tendency on the part of the triazo-group in p-triazobenzaldehyde t o enter into association with thealdehyde radicle in the manner brought to light by Bamberger andDemuth (Ber., 1901, 34, 1309) during an investigation of certainortho-aminobenzaldoximes. These authors found that on diazotisingo-aminobenzaldoxime there is produced indiazoneoxime, isomeric witho-triazobenzaldehyde, into which it passes on treatment with alkali orwarm water ; furthermore, they showed that o-triazobenzaldehyde maybe converted readily into anthranilic acid through anthranil, fromwhich they regenerated it by the combined action of hydroxylamineand oxygen (Zoc.cit., 3874 and 4015) :As the production of anthranil from o-triazobenzaldehyde mustdepend on an opening of the azoimide ring analogous t o that incurredby diazomethane when this compound transforms aldehydes intoketones (Schlotterbeck, Ber., 1907, 40, 479; 1909, 42, 2559), itseemed reasonable to expect a similar transformation in the case ofo-triazobenzonitrile :The substance in question was therefore prepared by the action ofhydrazoic acid on o-cyanobenzenediazonium chloride ; it was foundthat alkali, however, which transforms o-triazobenzzldehyde intoanthranilic acid with loss of nitrogen, leaves the triazo-group ino-trittzobenzonitrile intact, the substance being merely hy drolysed t 266 FOHSTER AND JUDD: THE TRIAZO-GROUP. PART XII.o-triazobenzoic acid.During this process there does not occur anyelimination of the triazo-group in the form of alkali azide, and thesame power of resistance is displayed by the triazo-group in p-triazo-benzaldoxime. These observations are of some interest in connexionwith the effect produced by other groups on the tenacity withwhich the azoimide complex is held by the benzene ring. Noelting,Grandmougin, and Michel (Ber., 1892, 25, 3328) mere the first toshow that a nitro-group in the ortho- or para-position unloosed thetriazo-group, which remained indifferent to the presence of methyl andthe meta-nitro-complex ; a similar relationship was found applicable tothe naphthalene series (Forster and Fierz, Trans., 1907, 91, 1942),with the addition that a heteronuclear nitro-group in the 5 : 1, 8 : 1,5 : 2, and S : 2 positions left the azoimide radicle unaffected by alkali.Furthermore it was shown (Zoc.cit., 1356) that boiling potassiumhydroxide solution eliminates 20 per cent, of hydrazoic acid fromp-hydroxyphenylazoimide without yielding a trace o€ this productfrom the ortho-derivative.We have taken this opportunity to study the relationship of theoximes obtainable from p-triazobenzaldehyde, and find that theproduction and properties of these substances are governed by thesame generalisations which prevail among their better knownanalogues. The anti-aldoxime, melting at 9So, is the direct productof treating the aldehyde with hydroxylamine, and is converted by theaction of hydrogen chloride in dry ether into the 89%-aldoxime, whichmelts at 142O. Tho latter modification is labile, being transformediuto the more fusible isomerido at looo, and on treatment withbenzoyl chloride in pyridine yields the same benzoyl derivative asthat obtained from the anti-aldoxime ; the p-triazobenzaldoximes thusresemble the unsubstituted compounds, from which only one benzoylderivative is obtainable.On consulting the literature we found thatthe benzoyl derivative of benz-anti-aldoxime was produced by directaction of benzoyl chloride (Minunni and Corselli, Gazzettts, 1892, 22,ii, 167), and consequently in presence of hydrogen chloride.Neverthe-less we have failed to obtain an isomeric benzoyl derivative undermodified conditions, the only product arising by the action of benzoylchloride on tbe dry sodium derivative of both benzaldoximes in etherconsisting of the substance melting at 101" described by Minunni andCorselli; benzoylation in dry pyridine or in presence of aqueousalkali was equally unsuccessful. The beozogl derivative of p-triazo-benzaldoxirne is readily decomposed into p-triazobenzonitrile andbenzoic acid, and on attempting to prepare the p-toluenesulphonylderivative, this nitrile was the sole recognisable product. From thesodium derivative oE benz-anti-aldoxime, however, a very unstablep-toluenesulphonyl compouod has been prepared, melting at 88", anFORSTER AND JUDD: THE TRIAZO-GROUP.PART XII. 257undergoing decomposition into benzonitrile at the laboratory tem-peratme ; the 8yn-aldoxime did not yield a p-tolueoesulphonyl deriv-ative, however, even when exactly the same conditions were observed,benzonitrile alone being formed, and it is noteworthy in this con-ncxion that the nitrile was produced from both oximes by the actionof benzenesulphonyl chloride in pyridine (Werner and Piguet, Ber.,1904, 37, 4308). P-NaphthalenesulphonIl choride appears to beincapable of attacking the isomeric benzaldoximes and their p-triazo-derivatives in pyridine a t zero.EX PE B IM ENTAL.The p-Triuxobeneak~oximes, N,*C,H,*C?:H:NOH,The p-triazobenzsldehyde required for the preliminary experimentswas prepared by the action of sodium carbonate on a solution ofdiazotised p-aminobenzaldeh yde to which hydroxylamine hydrochloridehad been added (Rupe and von Majewski, Ber., 1900, 33, 3401), butwe subsequently obtained a more satisfactory product by the followingprocess.Fifty grams of finely powdered p-aminobenzaldehyde were mixedwith crushed ice, stirred with 150 C.C.of concentrated hydrochloricacid, and diazotised with 25 grams of sodium nitrite in the minimumof water; after half an hour some carbamide was added, and theliquid filtered rapidly from tar. The ice-cold diazonium salt, nowclear and orange-yellow, was treated with 30 grams of sodium azide,added gradually in aqueous solution ; brisk evolution of nitrogenoccurred, and the triazobenzaldehyde separated in the form of a palebrown oil, which, after an hour, was extracted with ether, shakentwice with 10 per cent.hydrochloric acid, and dried with calciumchloride, thereby losing much of the brown impurity. The triazo-benzaldehyde weighed 33 grams,p-Triaxobenx-anti-aldoxime was prepared by adding 6 grams ofhydroxylamine hydrochloride to 5 grams of the aldehyde suspendedin 50 C.C. of 15 per cent. potassium hydroxide, the characteristicodour of p-triazobenzaldehyde, which recalls anise, being no longerperceptible after half an hour. Carbon dioxide was then passedthrough the liquid, and the deep brown precipitate recrystdlisedfrom dilute alcohol, forming lustrous plates which melt at 98" :0 1119 gave 33 C.C. N, at 16" and 769 mm.C7H,0N, requires N = 34.56 per cent.The substance is freely soluble in methyl and ethyl alcohols, ethylacetate, chloroform, ether, glacial acetic acid, acetone, or carbontetrachloride ; benzene dissolves it less readily, and petroleumN = 34.80.VOL XCVII.258 FORSTER AND JUDD: THE TRIAZO-GROUP. PARr XII.sparingly, depositing it in flat, pale yellow needles. It is volatilei n steam, and when crystallised from boiling water is practicallycolourless. Ether extracts small quantities from solutions in alkalihydroxide. When exposed to light the substance rapidly becomesdark brown, but there is no change of colour when a solution in50 per cent. potassium hydroxide is boiled, unaltered materialbeing recovered on acidification ; moreover, one gram of the substancewas heated with 20 per cent.aqueous potassium hydroxide duringfour hours on the water-bath without yielding a trace of potassiumazide. Torrents of gas were liberated by concentrated sulphuricacid, which formed a dark brown liquid indifferent towards Fehling'ssolution. Stannous chloride in !hydrochloric acid also sets free gas,yielding a bright red solution, from which a dark reddish-brownprecipitate quickly separated ; this material, probably an azo-compound,is insoluble in benzene, but dissolves i n alcohol, the deep redsolution becoming yellow with alkali and having its red colourrestored by acids.The methyl ether was obtained by the silver oxide method as acolourless oil having a powerful odour of anise, and also arises by theaction of diazomethane on a solution of the oxime in dry ether(Forster and Dunn, Trans., 1909, 95, 425) ; it is readily volatile insteam, and is not dissolved by alkalis.p-Friaxobenx-syn-atldoxime arose in the form of hydrochloride onpassing dry hydrogen chloride into a solution of the ad-oxime(m. p.9 8 O ) in ether. The salt, after being washed with ether, wassuspended in this medium and decomposed with sodium carbonate, theethereal solution of the syn-oxime being then dried by sodiumsulphate and evaporated at the laboratory temperature, The colour-less, crystalline residue was recrystallised from warm benzene, whichdeposited a felted mass of very pale yellow, silky needles :0,0498 gave 14-2 C.C. N, a t 10.5O and 775 mm.C7H,0E4 requires N = 34.56 per cent.The melting point, 142O, is sharp, although the substance decomposes,The oxime is readily soluble in methyl and ethyl alcohols, from whichwater precipitates lustrous, slender needles ; it is freely soluble incold ethyl acetate, chloroform, ether, acetone, or glacial acetic acid,but is only sparingly so in benzene, and almost insoluble in lightpetroleum. It resembles the more fusible isomeride in being verysensitive to light, volatile in steam, and extractable by ether from itsalkaline solutions.Unlike the sp-modification of benealdoxime andits nitro-derivatives, the triazo-compound appears to resist anytendency to undergo transformation into the anti-form on recrystalli-aation, and must be heated for several minutes at 100° before theN=34*64FORSTER AND JUDD: THE TRIAZO-GROUP.PART XII. 259isomeride is regenerated ; the syn-oxime may even be recoveredunchanged from a solution in 10 per cent. potassium hydroxide whichhas been heated in steam during fifteen minutes.Action, of AcyZ Chlorides on, the 0ximes.-On mixing pyridinesolutions containing 1.4 grams of benzoyl chloride and 1.6 grams of theanti-aldoxime, the temperature rose, and the liquid was thereforesurrounded with melting ice during one hour, and afterwards pouredinto cold water ; the oil precipitated in this manner became semi-solidon treatment with dilute acetic acid, and after being rubbed with afew drops of cold alcohol and drained on earthenware, yielded acolourless solid, only moderately soluble in alcohol, from which itcrystallised in minute, lustrous needles melting at 146' withdecom pod t ion :0.1325 gave 23*5 C.C.N, at 1l0 and 758 mm.On proceeding in exactly the same way with the sp-aldoxime, theproduct is identical.It was noticed that if the oil which is precipitated on pouring thepyridine solution into water is allowed to remain in the liquid without.adding acetic acid, the benzoyl derivative disintegrates in the courseof a few days, yielding p-triaxobenzonitrile, a specimen of which, aftercrjstallisation from alcohol, melted at 71°, and mas therefore identicalwith the substance obtained by Rupe and von Majewski (Zoc. cit.,3406) from p-cyanobenzenediazonium porbromide and ammonia.The action of p-toluenesulphonyl chloride in pyridine was alsostudied, and with this agent both oximes were converted into thenitrile. /?-Naphthalenesulphonyl chloride, however, appears to bedevoid of action, urichanged material being recovered in each casewhen the isomeric oximes were treated with this compound inpyridine.N=21*12.CI4H,,O,N, requires N = 2 1.05 per cent.Action of Potacssium Cganide on p-li.iaxobenxakde~~d.I n preparing p-triazobenzaldehyde by the process of Rupe and vonMajewski, we were led to suspect the occurrence of a subsidiary actionindicated by the comparative indifference of the product towardshydroxylamine and phenylhydraaine, As it seemed possible that aportion of the aldehyde had become converted into bis-p-triazobenzoin,we attempted to compare this compound by the action of potassiumcyanide, but it was soon evident that this agent, instead of effectingbenzoin synthesis, had attacked the trinzo-group in the mannerdescribed by Wolff and Lindenhayn (Bey., 1904, 37, 2374), givingrise to the potassium derivative of the corresponding triazen,0 :CuI * C,H,* N :N*N K a CN.s 260 FORSTER AND JUDD: THE TRIAZO-GROUP.PART XII.Ten grams of the aldehyde in 20 C.C. of absolute alcohol wereheated with 2 grams of potassium cyanide in 10 C.C. of water duringhalf an hour under reflux; the liquid deposited a small quantity ofpotassium cyanide as it cooled, and when filtered from this was allowedto evaporate spontaneously. Bright yellow crystals were obtainedembedded in oil, and on recrystallisation from alcohol formed radialgroups of long, pale yellow prisms :0.0435 gave 0.0179 K,SO,.I(= 18.40.C,H,ON,K requires K = 1840 per cent.The salt has not a definite melting point, decomposing at a hightemperature with extensive intumescence ; it is readily soluble inwater, the yellow colour of the solution being destroyed by hydro-chloric acid and restored by alkali.p- Triazobenxclldehyd~p~en ylh ydrasone, N,*c6H4*CH.: N*NH*C6H,.On mixing 4 grams of p-triazobenzaldehyde with 3 grams ofphenylhydrazine, water separated immediately, the liquid became hot,and solidified on cooling ; the product was recrgstallised from methylalcohol, followed by petroleum, which deposited minute, straw-colouredneedles melting at 190' without evolving gas, although steadyeffervescence began at 120' :0-1103 gave 28.2 C.C.N, at 17' and 767 mm.C13HllN5 requires N = 29.53 per cent.The phenylhydrazone is freely soluble in cold acetone, benzene, ethylacetate, and chloroform, the solution in the last named becoming deepbrown and ultimately purple when exposed to light; this colourchange has not been observed in the case of any other medium, andrecalls the observations of Chattaway in connexion with benzaldehyde-phenglhydrazone (Zoc. cit.). Concentrated sulphuric acid develops atransient, intense blue coloration, followed immediately by liberationof gas ; this was also set free by stannous chloride in hydrochloricacid, which ultimately gives rise to a deep reddish-brown precipitate.There is not any change of colour when the substance is heated withconcentrated potash in either alcohol or water.N = 29-95.Five grams of paminophenol hydrochloride in water were mixedwith 5 grams of sadium acetate and shaken with 5 grams of p-triazo-benzaldehyde, when the emulsion was transformed into a, paste ofcrystals ; after recrystallisation from benzene, the substance waFORSTER AND JUDD: THE TRIAZO-GROUP.PART XJI. 261obtained in lustrous, golden-brown, six-sided pln tes, melting a t 175"with vigorous intumewence :0.1378 gave 27.5 C.C. N, a t 14O and 765-5 mm.C,,H,,ON, requires N = 23.53 per cont.The substance is moderately soluble in boiling methyl alcohol, butonly sparingly soluble in boiling benzene, and insoluble in boilingpetroleum ; acetone and et,hyl acetate dissolve it readily when warm,depositing the substance in clear-cut, hexagonal prisms, whilst boilingchloroform dissolves it sparingly.When suspended in water andheated with potassium hydroxide, the deep yellow solution of thepotassium derivative quickly deposits lustrous crystals, but thesparingly soluble product undergoes no colour change when heatedwith concentrated potash, aqueous cr alcoholic. The substance isdecomposed immediately by concentrated sulphuric acid, liberatinggas, which is also set free by stannous cbloride in hydrochloricacid, the deep red solution rapidly depositing a dark reddish-brownprecipitate.N = 23.64.Condensation o j p-Triaxobenxalclehyde with CamphoryZ-~.semicarbcazide.Fonr grams of camphoryl-$-semicarbazide nitrate dissolved in waterwere warmed with two grams of p-triazobenzaldehyde, when thethe liquid became turbid and co!ourless needles separated.Thehighly insoluble product was exhausted with a small quantity ofboiling absolute alcohol, and then dissolred in a large proportion ofboiIing acetone; dilution with water led to the separation of trans-parent, pale yellow, rectangular prisms, infusible below 250°, althoughsuddenly becoming brown a t about 200' :0.1287 gave 0,2948 CO, and 0-0587 H,O.0.1371 ,, 30.S C.C. N, at 1 5 O and 763 mm. N=26*46.C = 62.45 ; H = 5.06.C,,H,,O,N, requires C = 61 -00 ; H = 6.21 ; N = 23-73 por cent.C,,H,,O3N, '3 C=62*11; H x 5 . 1 7 ; N=26*09 ,, ,,The constitution of the product is somewhat obscure.Theanalytical results are not in agreement with the empirical formulaC,,H,,0,N6, that of p-triazobenzaldehyde camphoryl-$-semicarbazone,and are equally incompatible with the anhydride, which, in view ofthe readiness with which camphoryl-$-semicarbazide loses lH,O,might possibly have arisen. The formula indicated is that of big-p-triazobenzoin camphoryl-$-semicarbazone,CHON" :C(C6H,*N,)*CH(C6H,*N,)*OH]CSHl&(()H)-- NR>"O,less lH,O, an expression which gains probability from the infusi-bility of the substance, because the camphoryl-#-semicarbaaone262 FORSTER AND JUDD: THE TRTAZO-GROUP. PART XJT.already described (Trans., 1905, 87, 727) melt bebow 250°, whilst theanhydride of camphoryl-+-semicarbazide is not fused until 280' isreached.A solution containing 0.1745 gram in 25 C.C.of chloroform gaveaD 7'46' in a 2-dcm. tube, whence [a],, 556*3O, whilst a pyridinesolution with 0.2600 gram in 25 C.C. gnvo aD 0'30' for the samelength, corresponding with [a], 24.0'.CNo-T~iaxobe~xonitrile, /-\IS3. \-/The azoimide was produced by the following steps from o-nitro-aniline :NO, NO, NH2 N3\/ \ \/ \/{)NH -+ / j C N -~ ()CN -+ /)CN. IAdopting the modification of Sandmeyor's method described byPinnow nnd Muller (Rer., 1895, 28, 151), we found that the o-nitro-.benzonitrile was more conveniently separated from the uninvitingproduct of treatment with cuprous cyanide by allowing the blackmass to become dry, extracting it with chloroform, and addingpetroleum to the filtered liquid; in this way, 50 grams of o-nitro-aniline furnished 37 grams of o-nitrobenzonitrile in crystalline form.The difficulties which beset the reduction of o-nitrobenzonitrile too-aminobenzonitrile have been already described by Pinnow andMuller (Zoc.cit.; comprtre also Reissert and Grube, Ber., 1903, 42,3710), and we isolated the hydrochloride of the base in the mannerindicated by them, removing the associated hydrochloride of o-amino.benzamide by treatment with cold water.Fifteen grams of o-aminobenzonitrile hydrochloride were simpendedin 80 C.C. of hydrochloric acid and diazotised with 25 grams of sodiumnitrite; by using a larger proportion of hydrochloric acid than thatemployed by Pinnow and Samann (Rev., 1896, 29, 630), the forma-tion of o-dicyanodiazoaminobenzene, which represented 80 per cent.ofthe theoretical amount in their experiment, ma3 almost entirelyavoided, and the filtered diazonium salt gave o-triazobenzouitrile inthe form of a colourless precipitate on adding 20 grams of sodiumazide. The dried product was rezrystallised from petroleum(b. p. 60-SOo), which deposits pale yellow, lustrous leaflets,quickly becoming brown when exposed to light ; it; sinters at 51°,and is completely fused at 58O :09792 gave 27.0 c.c.' N, at 17" and '748 mm. N= 38.92.C,H4N4 requires N = 38.S8 per centFORSTER AND JUDD: THE TRIAZO-GROUP. PART XII. 263The substance is freely soluble in cold chloroform, ethyl acetate,benzene, or acetone, readily so in alcohol, and more sparingly so in hotpetroleum.Although the solid material is odourless, the vapour insteam has a penetrating odour, without suggestion of anise. There isviolent decomposition with concentrated sulphuric acid.Action of A Zcoholic Potash,-An alcoholic solution of o-triazobenzo-nitrile was heated two hours under reflux with potassium hydroxidedissolved in the minimum quantity oE water, Nitrogen was not setfree, and on evaporating the solution, potassium azide could not bedetected in the residue, which was then dissolved in water and treatedwith dilute sulphuric acid. The precipitated o-triazobenzoic acid wasrecrystallised from boiling water, from which it separated in minute,lustrous needles, melting and decomposing at 146O ; analysis gave25.97 per cent.of nitrogen, 25.76 and 34-57 per cent. being requiredby the formulz C7H,0,N, (triazobenzoic acid) and C,H,ON, (triazo-benznmide) respectively, and the acid is therefore identical with theone obtained by Griess from anthranilic acid (Zeitsch. fiir Chem.,1867, 165) and by Bnmberger and Demuth (Bey., 1901, 34, 1337)from o-t riazo ben zal de h y d e.Aotion of AcyZ Chlorides on the I S O ~ ~ W ~ C Benxaldoximes.So far as we have been able to ascertain, the only benzoyl derivativeof benzaldoxime is that described by Minunni and Corselli (Zoo. cit.),who prepared it from benz-anti-aldosime and benzoyl chloride in dryether. I n view of the existence of two acetyl derivatives correspond-ing with the anti- and syn-aldoximes, it appeared worth while toattempt the production of a benzoyl derivative from benz-syn-ald-oxime under conditions excluding the presence of free hydrogenchloride.As a preliminary experiment, the sodium derivative of benz-anti-aldoxime suspended in dry ether was treated with the calculatedamount of benzoyl chloride, the very vigorous action which ensuedbeing checked by surrounding ice and water; after half an hour,anhydrous sodium carbonate was added to destroy any slight excess ofbenzoyl chloride, when the filtered solution deposited the knownbenzoyl derivative melting at 101".On treating the sodium deriv-ative of benz-syn-aldoxime in precisely the same way, the samesubstance was produced, no depression of melting point occurring onadmixture.An attempt to prepare a p-toluenesulphonyl derivative of benz-anti-aldoxime by the same process was unsuccessful; the residue left bythe solvent remained liquid, and decomposed explosively on slightlyraising the temperature, when torrents of gas were liberated, whils264 PYnlAN : ISOQUINOLINE DERIVATIVES.PART I\*.the tarry residue had the odour of phenylcarbylamine. On shakingthe sodium derivative of benz anti-nldoxime with p-toluenesulphonylchloride in 5 per cent. sodium hydroxide during two and a-half hours,a strong odour of benzonitrilo was developed, and a small proportionof a solid substance remained undiseoIved ; after crystallisation fromlight petroleum, this melted a t 8S0, and was prepared more con-veniently by rubbing the sodium derivative with p-toluenesulphonylchloride and wexk sodium carbonate solution. After remainingtwenty-four hours in the ice-chest, tho pasty mass, with the odourof phenylcarbylamine, had become brittle, and, when washed withsodium carbonate and dried in the desiccator, was dissolved in coldbenzene, from which petroleum precipitated it in lustrous, colourlessprisms melting with profound decomposition a t S8O :0.5359 gave 24.6 C.C. N, a t 24' and 755 mm.Cl,HI,O,NS requires N = 5.09 per cent.The substance is highly unstable, even when purified, especially ifkept in a stoppered bottle, undergoing decomposition after forty-eight hours in daylight t o a tarry mass which has the odour of benzwnitrile ; a specimen on a match-glass in a large desiccator protectedfrom light, however, remained many months without alteration.On proceeding in the same way with benz-syn-aldoxime, the onlyproduct was benzonitrile, and on substituting /3 -naphthalenesulphonylchloride for the toluene derivative, there did not appear to be anyactim with either oxime.N = 5.15.ROYAL COLLEGE OF SCIENCE, LOSDON.SOUTH KENSINGTON, S.V7

ISSN:0368-1645    

DOI:10.1039/CT9109700254

出版商:RSC    

年代:1910

数据来源: RSC

摘要:

264 PYMAN : ISOQUINOLINE DERIVATIVES. PART I\*.XXV~II.-isoQuinoli-I~c Deriva.tives. Part I V. ortho-Dih yd roxy-bases. The Cowvemion o f I -Keto-6 : ~ - d i m e t J ~ o x y - ~ - a l k . y l t e t c l . a h y d ~ ~ o ~ ~ o ~ ~ ~ ~ iw!o3 : 4 - D ih yd roxyplzcn y letl~y Zalky Zanaines.By FRANK LEE PYMAN.IN the preceding papers of this series (Trans., 1909, 95, 1266, 1610,1738) a number of 6 : 7-dimethoxgisoquinoline derivatives have beendescribed. Some of these proved t o be physiologically antivesubstances, and it was thought likely that the corresponding G : 7-di-hydroxy-bafies might be compounds of still more marked physiologicalaction.I n particular, it seemed possible that compounds of this type, such,for instance, as 6 : 7-dihydroxy-2-methyl-3 : 4-dihydroisoquinoliniumchloride (I), might praduce a pressor effect similar to thnt caused bPYMAW : ISOQUIXOLINE DERIVATIVES.PART 1V. 265p-3 : 4-trihydroxyphenyleth ylmethylamine (IT), the laevo-modification ofwhich is the active principle of the suprarenal gland, since they mouldbe in some respects similarly constituted :(1.1 (11.)With this object in view, several dimethoxyisoquinoline derivativeshave been converted by treatment with hydrochloric acid into thecorresponding dihydroxy-bases, which were then submitted tophysiological examination, but in no case where the isoquinoline ringremained intact had the resulting dihydroxy-base any marked pressorproperties. It was found, however, that the 1-keto-6 : 7-dimethoxy-2-alkyltetrahydroisoquinolines, when treated with hydrochloric acid a ta sufficiently high temperature, gave rise to bases of considerable pressorproperties, in which the isoquinoline ring was no longer preserved.1 -ket 0-6 : 7 - d i methox y-2 - met h yl tetrah y droisoquinoline(111) is heated with hydrochloric acid under pressure for three hoursat 175O, it is quantitatively converted into the hydrochloride of3 : 4-dill~yd~~oxyp7~snyZet~~ylmethyZanaine (VII).By working at tempera-tures lower than 175", however, two immediate products, 7(or 6)-hydroxy-l-kato-6(or 7)-methoxy-2-methyZtetrcthydroisoquinoZi~~e (IV) and6 : 7 - dihydroxy - 1 -&to - 2 - methyltetrahydroisoquinoline (V), may beisolated, and it is therefore evident that the mechanism of the changeat 175" consists in the successive hydrolysis of the two methoxylgroups, followed by hydration of the lactam, forming the correspond-ing amino-acid (VI), and subsequent decomposition of the latter intocarbon dioxide and the amine.The course of the reaction maytherefore be represented by the following scheme :Thus, whenCH2 CH,MeO/\/\CH, -+ Me H 1 \Ol O'\/\CH2 ' "Me --+ 31eob\, coCO\/A/ I lNMe(111.) (IV.)CH,(VII.266 PYMAN : ISOQUINOLINE DERIVATIVES. PART IV.It may be pointed out that the ring fission illustrated above isprecisely similar to that occurring in the formation of 8-aminovalericacid from a-piperidone (Schotten, Her. 1888, 21, 2242), whilst theloss of carbon dioxide from the resulting acid is a not uncommonproperty of hydroxybenzoic acids when ixnder the influence of hydro-chloric acid a t a high temperature. Proof of the presence of animino-group in the final product is afforded by the fact that it yieldsa neutral triacetyl derivative,CGHs( CH,*CO,),*CH,*CH,*N Me*CO*OH,.It was found that on increasing the size of tho alkyl group on thenitrogen atom, the ring fission and subsequent elimination of carbondioxide took place with greater difficulty ; thus, under the conditions(three hours at 175') which sufficed to convert I-keto-6 : 7-dimethoxy-2-methyltetrahydroisoquinoline almost completely into 3 : 4-dihydroxy-phenylethylmethylamine, the ethyl and propyl homologues were onlypartly converted into the corresponding 3 : 4-dihydroxyphenylethyl-alkylamines, the former giving 30 per cent.and the latter 79 per cent.of the theoretical yield of the corresponding 6 : 7-dihydroxy-1-keto-2-nl ky ltetrahy droisoquinoline.The similarity of structure between the 3 : 4-dihydroxyphenylethyl-alkylamiiies and p-3 : 4- trihydroxyphenylethylmethylamine (VIII) isobvious ; 3 : 4-dihydroxyphenylethylmethylamine (IX), in fact, differsonly from this valuable drug in being devoid of the alcoholic hydroxylgroup.The physiological action of this compound (and of the othersmentioned in this paper) has been examined by Dr. H. H. Dale of theWellcome Physiological Research Laboratories, to whom the author isindebted for the following report :3 : 4-DihydroxyphenylethylmethyIamine has the characteristicsuprarenal action in a high degree, being the nearest in action to thetrue active principle of any of the large series of related substanceswhich Dr.Dale has now examined; qualitatively there is littledifference in the action of the two on organs innervated by sympatheticnerves. The characteristic rise of blood-pressure ; acceleration andaugmentation of the heart's action ; contraction of the pregnant andinhibition of the non-pregnant uterus of the cat ; dilatation of thepupil; secretion of saliva-all are produced. A 1 in 1000 solutionproduced marked and sustained pallor of the conjunctival mucousmembrane when instilled into the eye.Quantitatively, by finding doses which produce rises of bloodPYMAK : ISOQUJNOLINE DERIVATIVES. PART IV. 267CH/+COpressure t o equal submnximal heights,* Dr. Dale has found that 3 : 4-dihydroxyphenylethylmethylamine has an activity approximately one-seventh of that of racemic @-3 : 4-t~rihydroxyphenylethylmethylamine,or one-tenth of that of the naturally-occurring lsvo-modification.The corresponding ethyl- and propyl-amines behave in a similarmanner, but to a lees extent, the ethylamine having about one-thirdand the propylamine less than one-twentieth of the activity of themethylamine.?The valuable properties of 3 : 4-dihydroxyphenylethylmefhylaminesuggested -the preparation of a trih ydroxyphenylethylmethylamine,and it was proposed to prepare such a compound by nitrating l-keto-6 : 7-dimethoxy-2-methyltetrahydroisoquinoline, reducing the nitro-compound, substituting a hydroxyl for the amino.group in the usualway, and decomposing the product with hydrochloric acid.Thissynthesis seemed a priori promising, since Freund ( B e y , , 1587, 20,2406) has described a nitro-oxyhydrastinine obtained by the action ofwarm dilute nitric acid on oxyhydrastinine. Unfortunately, theaction of this reagent on l-keto-6 : 7-dimethoxy-2-methyltetrahydroiso-quinoline (X) consisted not only in nitration, but also in simultaneousoxidation, two atoms of hydrogen being removed with the formationof a bright yellow nitro-compound having the formula C,,HI20,N,.This proved t o be 5(or S)-nitro-l-keto-6 : 7-dimethoxy-2-methyl-2 : 2-dihydroisoquinolinze$ (XI or XII), for it was readily obtained bynitrating 6 : 7-dimethoxy-N-methylisoquinolone (XIII) (l-koto-6 : 7CHMeO/\/\CHMeOl I "Me \/\/NO, coi NO., CH I NO, CH\/\/CH2MeO/\/%HMe01 I INMe OrUO C268 PYMAY : ISOQUTNOLINE DERIVATIVES.PART IV.dimethoxy-%met hyl-1 : ~-dihydroisoqlxinolin~), a compound preparedby Decker rand Pschorr (Rev., 1904, 37, 3401) by the oxidation ofN-met hy lisopapaverine.No further investigation of this compound was made, since 1-keto-2-alkyl-1 : 2-dihydroisoquinolines do not appear to become converted intophenylethylenealkylnmines under the influence of acids a t high tem-peratures ; thus, 1-keto-2-methyl-1 : 2-dihydroisoquinoline can be quanti-tatively recovered unchanged after heating with hydrochloric acidunder pressure for two hours at 1709Reference has already been made to the preparation of dihydroxy-bases containing the isoquinoline ring ; them are readily obtained ingood yield by the action of hydrochloric acid at 175O on the corre-sponding dimethoxy-compounds ; 6 : 7-dihyd~oxy-2-methyZtetrah ydro-isoquinoline (XIV) and 6 : 7-dihydroxy-2-methyl-3 : 4-dihydroiso-puinolinium chlovide (XV) have no decided physiological action :On tEe addition of sodium carbonate to a solution of the lattercompound, the phenolbekzine of the corresponding isoquinoliniumhydroxide is obtained.This compound has one of the two formulze(XVI) or (XVII), but no attexpt has been made to determine(XVI.) (XVI J. )which of the two is correctt, although for the purpose OF furtherdiscussion the former has been arbitrarily adopted throughout thiscommunication.This base exhibits the characteristic properties of phenol betaines(compare Decker and Dunant, Annden, 1908, 358, 396), amoagstothers that of forming the iodide of the corresponding methoxy-compound, 7(or 6)-hydroxy-6(or 7)-methoxy-2-methyZ-3 : 4-dihydroiso-puinolinum iodide (XVIII), when heated with methyl iodide.Atthe same time, a compound (XTX) of the latter with one moleculeof the phenolbetaine is found in accordance with the followingscheme PYMAK : ISOQUIKOLINE DERIVATIVES. PART 1V. 269(XVI.) (XVIII.)HO/\/\CH, MeO/\/\CH,01 ! "Me1 * HOI I jNMe-CH(XIS).CH, CH2\/\/ \/\/CHThis compound may be crystallised unchanged, and can be convertedinto the chloride by means of silver chloride, and crystallised assuch without breaking down, but is readily decomposed by hydr-iodic acid, the compounds from which it was formed being repro-duced.Mixed external phenolbetaines of this type do not appear tohave been previously observed, but simple external phenolbetaines ofthe type HO*RiN-O-RiNI have been obtained by Griess (Ber., 1880,13, 246) and by Claus and Hotvitx (J. pr. Chem., 1890, [ii], 42, 223)and their collaborators by the action of ammonia on substituted ammo-nium iodides of the type HOoRiNI ; a simple external phenolbetaine(XX) of this typo can be similarly obtained from 7(or 6)-hydroxy-6(or 7)-methoxy-2-methyl-3 : 4-dihydroisoquinoliniurn chloride (XVIII).Me0 '\I/)CH, a1 eO/\/\CH,CH2 CH,\/\/ 0) 1 IN3leCl' €10' NMe----CH\/\/CH(SX.)E x P E R I MENTAL.1 - Keto-6 : 7 -dimthoxy- 2 -nteth y Zte trah ydroiso pinoline.By the method of preparation of this compound by simultaneousoxidation and reduction of 4 : 5-dimethoxy-2-/3-methylaminoethylbenz-aldehyde (Trans., 1909, 95, 1272), only one-half of the originalmaterial is transformed into the above substance.It can, however,be prepared in almost theoretical yield from the same material bythe method devised by Freund (Bet-., 1889, 22, 457) for the conver-sion of hydrastinine into oxyhydrastinine, namely, by oxidation bypermanganate in the presence of alkali.Two grams of 6 : .7-dimethoxy-2-methy1-3 : 4-dihydroisoquinoliniumchloride were dissolved in 180 C.C. of water, rendered alkaline by theaddition of 20 C.C.of 10 per cent. aqueous sodium hydroxide, an270 PYMAN : ISOQUINOLINE DERIVATIVES. PART IV.mixed with a solution of 0.8 gram (a slight excess) oE potassiumpermanganate in 20 C.C. of water, After one hour, the solutionwas filtered from manganese dioxide, neutralised with dilute sulphuricacid, evaporated to low bulk, and extracted with ether. Afterevaporation of the solvent, 1.4 grams of pure 1-keto-6 : 7-dimethoxy-2-methyltetrahydroisoquinoline mere obtained, that is, 96 per cent.of the theoretical,To the description of this compovnd previously given (Zoc. cit.), thefollowing way be added. It can be distilled under diminishedpressure without decomposition, and passes over as a nearly colourlessoil, which solidifies on cooling, a t 24Qo(corr.)/16 mm.It is easily soluble in water, but, on agitating a strong aqueoussolution, an unstable hydrate separates as a mass of silky needles,which are sparingly soluble in water.When this bydrate is collectedand dried for half an hour on porous porcelain, it melts indefinitely a t40-70°, but on exposure to air for twelve hours becomes anhydrous,has the melting point 126' (corr.) of the anhydrous base, and is, asbefore, easily soluble in water.&(or 8)-Nitro-l-keto-6 ; 7-dimethoxg-2-methyZ-1 : 2-dihydroisopuitzoline(XI or XII, p. 267).Ten grams of 1 - ke to- 6 : 'I-dirne t hox y -2 -me t h y 1 te t rnhydroisoq uinolinewere dissolved in a solution of 10 grams of concentrated nitric acid in30 C.C. of water and heated on the water-bath. The liquor quicklybecame brown, and then effervesced vigorously with evolution of brownfumes, whilst a quantity of yellow needles continuously separated out.After a few minutes, the liquor was cooled, filtered from the separatedcrystals, and again heated, this time over a free flame, when a furtherquantity of crystals were obtained j these operations were againrepeated after the addition of another 5 C.C.of concentrated nitricacid, until no further quantity of the crystalline compound could beobtained.5 (or 8)-Nitro-6 ; 7-dimethoxy-2-methyl-1:: 2-dihydroisoquinoline crystal-lises from glacial acetic acid in fine bright, canary-yellow needles,which begin to soften at about 240' and melt at 244-245O (corr). Itis easily soluble in chloroform, fairly easily so in boiling glacial aceticacid or xylene, but almost insoluble in water or the other usual'organicsolvents :The total yield amounted to 6.4 grams.0*1521 gave 0.3032 CO, and 0.0641 H,O.C1,H1,O,N, requires C = 54.5 ; H = 4.6 per ccut.Like Freund's '' nitro-oxyhydrastinine " (Zoc.cib.), it is insoluble indilute acids or weak alkalis, but dissolves in warm aqueous sodiumC=54.4 ; H=4*7PYMAN : ISOQUINOLINE DERIVATIVES. PART IV. 271hydroxide, and is reprecipitated in a gelatinous form on the additionOF dilute acids.The same nitro-compound is readily obtained by warming 1 gram of1-keto-6 : 7-dimethoxy-2-methyl-1 : 2-dihydroisoquinoline with a mix-ture of 1 C.C. of concentrated nitric acid and 3 C.C. of water; theidentity of the product of this reaction with that described abovefollows from the fact that the two products and a mixture of both meltat the Eame temperature.7( or 6)-Hydroxy-l -keto-6 (or 7) -methoxy2 methgltetraiiydroiso-puinoline (IV, p.265).Five grams of 1 -keto-6 : 7-dimethoxy-2-methyltetrahydro~soquinolineand 30 C.C. of concentrated hydrochloric acid were heated togetherunder pressure for two hours at 130-135O. The product consisted ofa pale brown liquor containing a mass of cream-coloured needles, whichformed the hydrochloride of the new base. The solid matter wascollected, dissolved in a little hot water, and, after some time, 3.2grams of the base separated in spear-like crystals, which melted at200-208°, but contained some quantity of the dihydroxy-base, sincethey gave a green coloration with aqueous ferric chloride.After recrystallisation from absolute alcohol, 7(or 6)-hydroxy-l-ke to-6(or 7)-methoxy-2-methyltetrahydroisoquinoline forms colourless,glistening, diamond-shaped plates, which soften from ZOO0, melt at 210'(corr.), and give no coloration with aqueous ferric chloride :0.1529 gave 0.3562 CO, and 0.0864 H,O.C = 63.5 ; H = 6.3.0.1555 ,, 0.3635 CO, ,, 0.0880 H20. C=63*8 ; H= 6.3.C,,H,,O,N requires C = 63% ; H = 6.3 per cent.This compound is very sparingly soluble in cold water, sparingly soin hot water or cold alcoho1,readily so in hot alcohol, and sparinglyor very sparingly so in the other usual organic solvents. It is in-soluble in dilute acids, but soluble in aqueous sodium carbonate orammonia, and dissolves readily in aqueous sodium hydroxide, forming asodium salt which may be obtained as a crystalline mass by evaporatingthe solution to a very small bulk in a vacuum over sulphuric acid;this salt is very easily soluble in water or alcohol.6 : 7-Dih~drox~-l-ke~o-2-methyltetrahydroisoquinoline (V, p.265).Ten grams of 1-keto-6 : 7-dimethoxy-2-methyltetrahydroisoquinolineand 60 C.C. of concentrated hydrochloric acid were heated togetherunder pressure for three hours at 145-150'. The product consistedof a pale brown liquor containing pale brown needles; the latter werecollected and digested successively with warm water and a littl272 PP MAN : ISOQUINOLINE DERlVATlVES. PART IV.boiling alcohol. The residue amounted to 3.4 grams of nearly puredihydroxy-compound, and the alcohol deposited further small quantitiesof this compound.6 : 7-Dihydroxy-1-keto-2-methyltetrahydroisoquin-oline crystallises from absolute alcohol in beautiful colourless grains,which show a large number of sharply cut faces. I t begins to sinterat about 250°, and melts at 279' (corr.) :0.1504 gave 0.3400 GO, and 0.0788 H20.001555 ,, 10.2 C.C. N, at 25' and 768 mm. N = 7.4.This compound is sparingly soluble in boiling water or alcohol, andalmost insoluble in these solvents when. cold. It is insoluble in diluteacids, but easily soluble in aqueous ammonia, sodium carbonate, orsodium hydroxide, Forming ' yellow solutions which gradually darkenon exposure to air, Aqueous suspensions of this substance give, withferric chloride solution, a faint green coloration, which graduallydevelops to deep green as the substance dissolves.C = 61.7 ; H = 5.9.CloH,103N requires C = 62.1 ; H = 5.8 ; N = 7.3 per cent.3 ; 4-Dih~yd.roxyphenylethylmeth~lamine (VII, p.265).Ten grams of 1-lreto-6 : 7-dimethoxy-2-methyltetrahydroisoquinolineand 60 C.C. of concentrated hydrochloric acid were heated togetherunder pressure for three hours a t 170-175'.* The acid was thenremoved by distillation under diminished pressure, and the resultingslate-grey crystals of 3 : 4-dihydroxyphenylethylmethylamine hydro-chloride were washed with acetone. The yield amounted to 8.5 grams,that is, 92 per cent. of the theoretical, and the crude product waspurified by cry stallisation from water containing sulphurous acid.3 : 4-Dihydroxyphenylethyllnet~ykan~ine is liberated in a crystallineform on the addition of ammonia to an aqueous solution of the hydro-chloride.It crystallises from absolute alcohol in colourless clusters oftransparent spikes, which melt at 188-189O (corr.). It is sparicglysoluble in cold water, more easily so in hot water, sparingly so inboiling alcohol, and very sparingly so in cold alcohol and the usualorganic solvents :0.1524 gave 0.3611 CO, and 0.1090 H20.0.1567 ,, 11.0 C.C. N2 at 17" and 778 mm. N = 8.3.C,H130,N requires C = 64.6 ; H = 7.9 ; N = 8*4 per cent.Aqueous solutions of the salts of this base give with ferric chloridesolution a deep emerald-green coloration, which becomes orange-brownon the addition of aqueous sodium carbonate; such solutions reducewarm aqueous silver nitrate and boiling Fehling's solution ; they giveno precipitate with aqueous picric acid.* On opening the tube, a large volume of gases containing a quantity of carbondioxide escaped.C = 64.6 ; H = 8.0PYMAN : ISOQUINOLINE DERIVATIVES.PART IV. 273The hydrochZo?*ide crystallises from water in long, colourless prisms,which melt at 179-180O (corr,), This salt is anhydrous, and is easilysoluble in water or hot alcohol, but somewhat sparingly so in coldalcohol :0.1505 gave 0.2944 CO, and 0.0939 H,O. C = 53.3 ; H = 7.0.0.1843 ,, 0.1281 AgCI. C1=17*2.C,H,,O,N,HCl requires C = 53.1 ; H = 6.9 ; C1= 17.4 per cent.The sulphate cry stallises from water in colourless, transparent prisms,which melt to a brown liquid at 289-290' (corr,), after commencingto soften and turn brown several degrees earlier.This salt isanhydrous, and is somewhat sparingly soluble in cold water :0.1524 gave 0.2779 CO, and 0.0905 H20.(C,Hl,02N),,H,S04 requires C = 50.0 ; H = 6.5 per cent.The oxalate separates from water i n colourless, hexagonal plates,which melt a t 194-195O (corr,). This salt is anhydrous, and issparingly soluble in cold water :C=49*7; H=6*6.0.1524 gave 0.3168 CO, and 0,0938 H,O. C = 56.7 ; H = 6.9.(C,H130,N),,C,H,04 requires C = 56.6 ; H = 6.7 per cent.3 : 4- Diacetoxy-N-acet~l~henylethylmeth~Z~~~n~,(CH3*C0,),C,H3*CH2*CH2*NMe*CO*CH,.Two grams of 3 : 4-dihydroxyphenylethylmethylamine hydrochloride,5 grams of fused sodium acetate, and 20 C.C.of acetic anhydride wereboiled for half an hour under a reflux condenser. The product wasstirred into 100 C.C. of water, the resulting clear solution renderedalkaline with sodium carbonate, and extracted with ether. On dis-tilling the ether to low bulk and setting aside, 2.1 grams of the purecompound crystallised out, and a further small quantity was obtainedfrom the mother liquor.3 : 4-Diaicetoxy-N-acetylphen~ZethyZmethyZamine crgstallises from abso-lute alcohol in shimmering, hexagonal, monoclinic plates, which softenat 11 1" and melt a t 113-1 14O (corr.). I t is very sparingly solublein water or dilute acids, but dissolves slowly in dilute aqueousammonia or sodium hydroxide, giving respectively greenish-yellow andstramberryred solutions.It is sparingly soluble in cold alcohol orether :0.1728 gave 0-3895 CO, and 0.1006 H,O.0.1522 ,, 6.1 C.C. N, at 21' and 775 mm. N = 4.7.C = 61.5 ; H = 6.5.C,,H,,O,N requires C = 61 *4 ; H = 6.5 ; N = 4.8 per cent,VOL. XCVII. 274 PYMAN : ISOQUINOLINE DFRIVATlVES. PART IV.Action of HydroclJoric Acid at 175" on I -Keto-6 : 7-dimethoxy-2-etl~yl-tetrahydroisoquinoline.Four and a-half. grams of 1-keto-6 : 7-dimethoxy-2-ethyltetrahydro-isoquinoline and 30 C.C. of concentrated hydrochloric acid were heatedtogether under pressure for three hours at, 1'75'. The resulting clearbrown liquor was evaporated to dryness under diminished pressureand dissolved in 15 C.C. of water, when 0-8 gram of 6 : 7-dihydroxy-1-keto-2-ethyltetrahydroisoquinoline separated in pale brown crystals ;after removing these, the process was repeated, when a furtherquantity of 0.4 gram of the same product was obtained.The motherliquor gave on evaporation 3 : 4-dihydroxyphenylethylethylaminehydrochloride, of which 1.5 grams were obtained in a pure. form bycrystallisation from water.6 : 7-DiT~~d~~ox~-l-ksto-2-e~?~yltetra?~ydroisoqzlinoline,CH2HO(\/\CH,HOv()NEtcoThis compound crystallises from absolute alcohol in beautifullycrptalline rods, which begin to sinter at about 200°, and melt a t214-218' (corr.). Its chemical properties and solubilities aresimilar t o those of the methyl homologue, with the exception of itssolubility in absolute alcohol, which is greater :0.1524 gave 0.3573 CO, and 0.0866 H20.C = 63.9 ; H = 6.4.CllH,,O,N requires C = 63.8 ; H = 6-3 per cent.3 : 4-Dihydroxyphenylthylethylamine,HO/)CH,*CH2=NHEtHOI \/The hydrochloride crystallises from water in prismatic needles,which melt a t 177-17S0 (corr.). Its chemical properties and solu-bilities are similar to those of the methyl homologue, except that itsaqueow solution does not yield a precipitate of the corresponding baseon the addition of ammonia :0.1519 gave 0.3057 CO, and 0.1024 H,O. C=55*0; H=7.6.0.1819 ,, 0.1239 AgC1. C1=16*8.C1,H,,02N,HCl requires C = 55.1 ; H = 7.4 ; Cl = 16.3 per centPPMAh' : ISOQUINOLINE DERIVATIVES. PART 1V. 275Action of Hydrochloric Acid at 175' on 1-Keto-6 : 7-dimethoxy-2-propyl-letrahydroisoquinoli?ze.Two grams of 1-keto-6 : 7-dimethoxy-2-propyltetrah ydroisoquinolineand 15 C.C.of concentrated hydrochloric acid, heated together underpressure for three hours a t 175', and worked up as in the precedingcase, gave 1 *4 grams of 6 : 7-dihydroxy-1 -keto-2-propyltetrahydrobo-quinoline and 0 +4 gram of 3 : 4-dihydroxyphenylethylpropylaminehydrochloride.6 : 7 -Bih ydroxy-l -keto- 2-propyltetrahydroisopuinolin e,CH2HOA/\CH,\/\/ HOI 1 INPr'GOThis compound separates from absolute alcohol in oblong, rect-Its chemical pro- angular plates, which melt at 184-185' (corr.).perties and solubilities are similar to those of the ethyl homologue :0,1548 gave 0.3677 CO, and 0,0959 H,O. C = 64.8 ; H = 6.9.U12H,503N requires C = 65.1 ; H = 6.9 per cent.3 : 4 -Dih y drox yplielz yleth y lprop y lamine,The hydrochloride crystallises from water in clusters of transparent,irregular prisms, which melt a t 184-185' (corr,), Its chemicalproperties and solubilities are similar t o those of the ethyl homologue :0-1540 gave 0*3200 CO, and 0.1091 H20, C = 56.7 ; H = 7.9.C,,HI7O,N,HC1 requires C r= 57.0 ; H = 7.9 per cent.G ; 7-Dihydroxy-2 -met?b y Ztetrah ydroisoquino Zine (XIV, p.2 6 8).Eight and a-half grams of 6 : 7-dimethoxy-2-methyltetrahydroiso-quinoline hydrochloride (containing 3 molecules of water of crystal-lisation) and 30 C.C. of concentrated hydrochloric acid were heated ina sealed tube for five hours at 170'. On cooling, 4.7 grams of6 : 7-dihydrouy-2-methyltetrahydroi~oquinoline hydrochloride separatedin grey needles, that is, 76 per cent.of the theoretical.6 : 7 - Dih ydroxy-2-meth yltetrahydroisoquinoline separates on theaddition of sodium carbonate to an aqueous solution of tbe bydro-chloride. It crystallises from water in nearly colourless (pale buff)T 276 PYMAN : ISOQUINOLINE DERIVATIVES. PART IV.needles, which melt at 221-222' (corr.), and contain one molecule ofwater of crystallisation. It is very sparingly soluble in water and theusual organic solvents.Aqueous solutions of its salts give with ferric chloride a deep greencoloration, which becomes mauve on the addition of sodium carbonate.They reduce hot silver nitrate and also boiling Fehling's solution :C = 67.1 ; H = 7.4.0.1833" lost 0.0172 at 100'.0.1500 ? gave 0.3693 CO, and 0.0987 H20.H20=9'4.C,,H,,O,N,H,O requires H20 = 9.1 per cent.C1,H1,02N requires C = 67.0 ; H = 7.3 per cent.The hydrochloride crystallises from water in coloi~rless needles, whichIt is fairly easily soluble in are anhydrous and melt at 27'7' (corr.).water, but sparingly so in alcohol :0.1522 gave 0.3093 CO, and 0.0937 H20.C = 55.4 ; H = 6.9.0.1731 ,, 0.1144 AgCl. C1= 16.4.CloHl,02N,HCl requires C = 55.7 ; H = 6.6 ; C1= 16.4 per cent.The picrate crystallises from alcohol in transparent, yellow, monoclinic(hexagonal) plates, which melt at 191-192' (corr.).Phenolbetaim of 6 : 7-Dihydroxy-2-methyl-3 ; 4-dihydroisoquinoliniumHplyoxide (XVI or XVII, p. 268).Ten grams OF 6 : 7-dimethoxy-2-methyl-3 : 4-dihydroisoquinoliniumchloride and 60 C.C.of concentrated hydrochloric acid were heatedtogether under pressure for four hours at 170". The product wasevaporated to dryness under diminished pressure, and the crystallineresidue well washed with acetone. 6.5 Grams of nearly pureanhydrous 6 : 7-dihydroxy-2-methyl-3 : 4-dihydroisoquinolinium chloridewere obtained, the yield thus amounting to 93 per cent. of thetheoretical.The phenolbetaine of 6 ; 7-dihyd~oxy-2-methyl-3 : 4-dihydroisoquino-Zinium hydroxide separates in long, deep yellow needles containing oneand a-quarter molecular .proportions of water oE crystallisation on theaddition of the calculated quantity of aqueous sodium hydroxide, or anexcess of sodium carbonate to a strong solution of its chloride :0,1816 * lost 0.0201 at 100'.C1,Hl102N, 1 $H,O requires H,O = 1 1-3 per cent.After recry stallisation from moist alcohol it forms deep yellow,monoclinic plates, which melt to a reddish-black liquid, decompose at322' (corr.), and contain 1 molecule of water of crystallisation :H,O= 11.1.0.1543 * gave 0,2667 CO, and 0.0746 H20.C = 61.5 ; H = 7.0.* Air-dried. t Dried at 100"PYMAN : ISOQUINOLINE DERIVATIVES. PART IV. 2770.1380 * gave 0.3096 CO, and 0.0839 H20.CloHl,O,N,H,O requires C = 61 *5 ; H = 6.8 per cent.0.1388 t gave 0.3448 CO, and 0.0795 H20.CloHllO,N requires C = 67.8 ; H = 6.3 per cent.The phenolbetaine crystallises from absolute alcohol in anhydrous,yellowish-brown, serrated spikes, which have the same melting point asthe hydrated base, is moderately easily soluble in cold water, no$ moreso in aqueous sodium carbonate or ammonia, but readily in diluteacids or aqueous sodium hydroxide.It is rather sparingly soluble incold alcohol or chloroform, and very sparingly so in the other usualorganic solvents. Aqueous solutions of its salts give with aqueousferric chloride a deep green coloration, and on the subsequent additionof sodium carbonate yield a pale reddish-brown suspension, the super-natant liquor appearing a dull yellow after the settlement of the ferrichydroxide. Aqueous solutions of the salts of this base reduce hotsilver nitrate, but do not reduce Fehling's solution even on boiling.The chloride crystxllises from moist acetone in primrose needles,which contain one and a-half molecular proportions of water ofcrystallisation.After drying at looo, this salt melts and decomposesat 276' (corr.). It is easily soluble in water, but sparingly so inalcohol :C = 61.2 ; H = 6.8.C = 67.7 ; H = 6.4.0.4060, air-dried salt, lost 0.0437 at 100".0-1468 T gave 0.3019 GO, and 0.0743 H,O.0.1593 t ,, 0*1081 AgC1. C1= 16.8.The picrate crystallises from alcohol in yellow, transparent, irregularplates, which melt and decompose at 236' (corr.).The sodium salt separates in clusters of beautiful crimson needles onthe addition of alcohol t o a solution of the phenolbetaine in thecalculated quantity of 2N-aqueous sodium hydroxide. It is easilysoluble in water or alcohol.This salt contains 6 molecules of waterof crystallisation, of which five are lost after prolonged heatingat 120':H20 = 10.8.C,oHl,0,NC1,1~H20 requires H,O = 11.2 per cent.C = 56.1 ; H = 5.7.Cl,Hl,O,NC1 requires C = 56-2 ; H = 5.7 ; C1= 16.6 per cent.0.2530 * gave 0.0562 Na,SO,. Na = 7.2.0.2541 * lost 0.0763 at 120". H,O = 30.0.C,oHl,0,NNa,6H,0 requires Na = 7.5 ; loss of 5H,O = 29.3 per cent.Action of MethTlyZ Iodide on the Phenot?betatim of 6 ; 7-Bihydroxy-2-nzethyZ-3 : 4-dil~ydroisoq~ino~~n~~m Hydroxide.Eight grams of the phenolbetaine, which had been dried for sometime a t loo", were heated together with 16 grams of methyl iodide for* Air-dried, t Dried at 100"278 PYMAN : ISOQUINOLINE DERIVATIVES. PART IV.three hours a t 100".The crystalline product obtained was separatedby fractional crystallisation from absolute alcohol into :(1) 7.2 grams of 'i(or 6)-hydroxp-G(or 7)-msthoxy-2-methyZ-3 : 4-dihydl.oisoquii2olinium iodide, melting at 21 3' (corr.).(2) 2.0 grams of 6(or 7)-methozy-7(or 6)-[6 : 7-dihydroxy-2-metAyZ-3 : 4-di~yd~oisoqzcinoliniumox?/l-2-met~~yZ-3~~ 4-hydroisoquinolinium iodide,melting a t 181-182' (corr,), and( 3 ) a small quantity of a brown, gummy residue.I n a second experiment, in which the phenolbetaine was notpreviously dried at loo", a larger proportion of the latter compoundwas obtained, 11 grams of hydrated phenolbetaine and 25 grams ofmethyl iodide yielding 4.4 grams of the first-mentioned iodide and5-1 grams of the latter, besides an oily residue which was neglecteld.7(or 6)-Hydroxy-G(or 7)-methoxy-2-methyl-3 : 4-dihydroisoquinoliniumSalts (XVIII, p.269).The iodide crystallises from alcohol in fine long, golden needles,It is anhydrous, and isC = 41.5 ; H = 4.5.which melt and decompose at 218' (corr.).sparingly soluble in water or alcohol :0.1536 gave 0.2336 CO, and 0.061 1 E20.0.1876 ,, 0.1370 AgI. I = 3 9 * 5 .0.3046 ,, by Zeisel's method 0.2098 AgI. OMe = 9 . 1 .C11H,,02NI requires C = 41.4 ; H = 4.4 ; I = 39.8 ; OMe = 9.7 per cent.The chloride was obtained from the iodide by double decompositionwith silver chloride. It crystallises from aqueous acetone in yellowneedles, which contain one molecule of water of crystallisation, andeffervesce at 155" (corr.), after sintering from about 140'; afterdrying at loo', it decomposes a t 198' (corr.).It is easily soluble inwater or hot alcohol, and its aqueous solution gives no coloration withferric chloride solution :0.2011 * lost 0.0146 at 100".0-1400 T gave 0.2970 CO, and 0*0815 H,O. C = 57.9 ; H = 6.5.C,,E,,O,NCl requires C = 58.0 ; H = 6.2 ; C1= 15.6 per cent.On dissolving this salt in warm concentrated aqueous ammonia, adeep red solution is obtained, which deposits, on cooling, orange crystalsof the chloride of the external phenolbetaine, namely, 6(or 'I)-~nethoxy-7 (or 6)-[7( or 6)-h ydroxy-6 (or 7)-methoxy-2-methyl-3 : 4-dih ydroisoquino-liiziumoxy]-2-methyZ-3 : 4-dihydroisopuinoliniuvn chloride (XX, p. 269).After recrystallisation from absolute alcohol, this salt forms brightH,O= 7.3.C,,H,,02NCl,H,0 requires H20 = 7 .3 per cent.0.1818 + ,, 0.1134 AgC1. C1= 15.4* Air-dried. .1. Dried at 100"PYMAN : ISOQUINOLINE DERIVATlVES. PART 1V. 279orange prisms, which contain 3&H,O and melt and decompose at 1 3 5 O(corr.). It is easily soluble in water, but sparingly so in cold absolutealcohol; it, contains chlorine. On heating this salt a t loo', it firstbecomes crimson, and then melts to a deep red gum which retainsabout 1 per cent. of water of crystallisation :0.1413 *gave 0.2831 CO, and 0,0933 H,O.0.1193 * lost 0.0146 a t 100'. H20=12*2.0.1047 T gave 02397 CO, and 0.0624 H20.C=54*6 ; H = 7.3.C2,H,70,N2C1,3~H20 requires C = 54.8 ; H = 7.1 ; H20 = 13.1 per cent.C2,H270,N,Cl requires C = 63.1 ; H = 6.5 per cent.C = 62.4; H = 6.6.6(or 7)-Methoxy-7(or 6)-[6 : 7-dih ydroxy-2-methyl-3 : 4-dihydroisoquino-linizcmoxy]-2-meth?/l-3 : 4-dihydroisoquinolinizcln Salt8 (XIX, p.269).The iodide crystallises from absolute alcohol in hard, orange grains,It is anhydrous andIts aqueouswhich melt and decompose at 181-182O (corr.).easily solpble in water, but sparingly so in cold alcohol.solution gives a deep green coloration with ferric chloride solution :0.1524 gave 0.2826 CO, and 04713 H,O. C = 50.6 ; H = 5.2.C2,H2,0,N21 requires C = 50-8 ; H = 5.1 ; I = 25.6 per cent.On adding a molecular proportion of hydriodic acid to the deeporange aqueous solution of 2 grams of this salt, a pale yellow solutionwas obtained. On evaporating this to low bulk and adding absolutealcohol, 0.9 gram of 7(or 6)-hydroxy-6(or 7)-methoxy-Z-methyl-3 : 4-dihydroisoquinolinium iodide separated ; after recrystallisation, thismelted a t 218O(corr.), both alone and whenmixed with the pure salt, andgave no coloration with aqueous ferric chloride.On then addingammonia to the mother liquor, a small quantity of the phenolbetaineof 6 : 7-dihydroxy-2-methyl-3 : 4-dihydroisoquinolinium hydroxideseparated ; after recrystallisation from alcohol, this compound meltedat 222O (corr.), and its melting point suffered no depression when thecompound was mixed with the pure phenolbetaine.The chlorih was prepared from the iodide by double decompositionwith silver chloride. It crystallises from absolute alcohol in deepyellow, glistening prisms, which melt a t 186-1 87' (corr.), and containone molecule of water of crystallisation :0.1867 ,, 0.0896 AgI. I = 25.9.0.3360 * lost 0.0169 at 100'.0,1416 t gave 0.3251 CO, and 0*0810 H,O.H,0=5-0.C21H250,N2C1,H20 requires H,O = 4.3 per cent.C,,H,,O,N,CI requires C = 62.3 ; H = 6.2 per cent.C= 62.6 ; H= 6.4.* Air-dried. t Dried at 100280 HOMER AND PURVIS: THE ABSORPTION SPECTRA OFPhenolbetaine of 6 ; 7-di~ydroxy-2-ethyZ-3 : 4-dihydroisoquinoliniumHyd *oxid@,I IThe preparation and properties of this compound and its salts aresimilar to those of the corresponding met hyl-homologue.The phenolbetaine of 6 ; 7-dihydroxy-2-ethyl-3 : 4-dihydroisoquino-Zinium hydroxide crystallises from absolute alcohol in deep yellow rods,which melt and decompose at 235' (corr.). It is anhydrous :0,1442 gave 0.3661 CO, and 0.0919 H20.Cl1H1,0,N requires C = 69-1 ; H = 6.9 per cent.The chloride crystallises from water in fine yellow needles, whichmelt at 104' (corr), and contain 2 molecules of water of crystallisation.After drying at loo', this salt melts and decomposes at 201-202'(corr.) :C=69*2; H=7*1.0.2170 * lost 0°0300 at 100'.0.1517 + gave 0.3221 C 0 2 and 0.0845 H20.0'1475 t ,, 0.0943 AgCI. C1= 15.8.The picrate crystallises from alcohol in clusters of golden, spear-likeH20 = 13.8.C,,Hl,02NC1,2H20 requires H,O = 13.7 per cent.C = 58.0 ; H = 6.2.C1lH1,O,NC1 requires C = 58.0 ; H = 6.2 ; C1= 15.6 per cent.needles, which melt and decompose a t 191' (corr.).THE WELLCOME CHEMICAL WORKSDARTFORD, KENT

ISSN:0368-1645    

DOI:10.1039/CT9109700264

出版商:RSC    

年代:1910

数据来源: RSC