200 YOUNG AND ANNABLE : FORMATION OF SUBSTITUTED XVI. Fomnatioi8 of Substituted Oxyti-iaxoles fyeom P~~e?aylse172icc-s1.~uxiclc. By GEORGE YOUNG, Ph.D., and HENHY ANNABLE, Firth College, Sheffield. C,H, *N *N C,H,*C :N THE formation of diphenyloxytriazole, I >C*OH, by the oxidation of an alcoholic mixture of phenylsemicarbazide and benzalde- hyde, according to the equation I. C,I-I,*N,H,* CO 'NH, c C,HjUHO + 0 = (C,HJp(:qNy* OH + BH,O has already been described by one of us (Trans., 1895, 67, 1063). It was there shown that the action could be carried out in two stages: the first being the oxidation of phenylsemicarbazide to phenylazocar- bamide. IIcc. C,H,*NH*NHb CO*NH&, + 0 = C,H,*N:N* COaNH, + H,O, the second the condensation of phenylazocarbamide with benzaldebyde, 116.C,13,.N2* (30 *NH, + C,Hj*COH = (C6H5)2C,Ns* OH + H,O. This last equation might itself represent two stages, if, before forma- tion of the molecule of water, direct addition of benxaldehyde toOXYTRIAZOLES FROM PHENYLSE;1IICBRBAZIDE. 201 phenylazocarbamide were to take place, an action which mould prob- ably result in the formation of benzoylphenylsemicarbazide. C,;H;N*NH* CO *NH, I - 111. C,H,*N:N* CO *NH, I + C,H ,*COH qp-; C 0 Benzoylphenylsemicnrbazide niight also be formed in action I. with, out intermediate formation of phenylazocarbarnide, if oxidation took place according to the scheme IV. C,H,*NH*NH* CO*KH, C,;H;N*NH* CO *NH, - - + H,O. + C,3H,*COH + 0 C6H,* C 0 The possibility of the formation of benzoylphenylsemicarb,rl7,ide by either action 111.or action IV. WRS not overlooked, but it was thought improbable, in view & the fact that Widman (L’w., 1893, 28, 948) had prepared this substance by the action of benzoic chloride on phenylsemicarbazide, and ha‘d observed that i t showed no inclination t o undergo ring condensation, even under very varied conditions. Our attention has again been drawn to this subject by Widman’s recent paper (Ber., 1896, 29, 1946), in which i t is shown that benzoyl- phenylsemicarbazide does condense to diphenyloxytriazole, and that with surprising ease, under the influence of warm, dilute alkalis. This seemed to make a reinvestigation of action I. and of action 116. advis- able, more especially cf the latter, as the product obtained by heating benzaldehyde with phenylazocarbamide had been purified by dissolving it in warm alkali and reprecipitating i t by dilute sulphuric acid, a process which, as Widman’s results show, would lead to the condensa- tion of any benzoylphenylsemicarbazide which might be present in the product of the action.We have, therefore, repeated the experiments with benzaldehyde and phenylazocarbamide, omitting the purification by means of alkali, and we have made several experiments to determine whether benzoylphenylsemicarbazide, if formed in the course of action I. or of action IIb., mould be condensed to diphenyloxytriazole under the conditions of the action. Action of BeiaxnZdelu& o n P~~eia?/lrL,Nocniabct nzide. An alcoholic solution of benzaldehyde and phenylazocarbamide in molecular proportion was boiled for 5 minutes, similar experiments being made with the addition of ferrous chloride, and also of ferrous chloride and hydrochloric acid.In neither case m ~ s any trace of benzoylphenylsemicarbazide or of diphenyloxytriazole formed. The action was next tried in sealed tubes a t 120’; the product, after being washed with cold alcohol and with ether and recrystallised from dilute alcohol, melted a t 288--289’. Benzoylphenylsemicarbazide has been202 YOUNG AND ANNABLE : FORMATION OF SUESTITUTED observed by &Pich,zelis and Schmidt (fie).., lSS7, 20, 1715) to melt at, 203-203°, and by Widmnn (Bey-., 1593, 26, 945) a t 210--811". Tho melting point of diphenyloxytriazole is given by Widman as 290" (Be,*., 1896, 29, 1946), and me found it to be 288' (loc.cit.). As the treatment of the product with alkali was entirely omitted, there could here be 110 possibility that benzoylphenylsemicarbazide, if formed by the action, had been condensed during the process of purification. The same result was obtainel whether the benzaldehyde and phenyl- azocarbamide were heated alone, with the addition of alcohol, or with alcohol and ferrous chloride. The yield varied considerably, the best being obtained when ferrous chloride mas present ; when the latter was omitted, phenylazocarhxmide coulcl be recovered from the alcoholic and ethereal washings. ~ ' e ? 2 ~ o ? / ~ ~ 1 ~ e 1 a ? ? s ~ ~ ~ ~ ~ c ~ ~ y ~ ~ ~ ~ ~ Tide. I n order to determine whether benzoylphenylsemicarbazide would undergo condensation if formed in the course of the actions under con- sideration, i t was first necessary to prepare this compound.Of two alternative methods, namely, addition of cyanic acid to asymmetrical benzoylphenylhydrazine, first used by Miclmelis and Schmidt (Zoc. cit.), and Widman's proces?, the action of benzoic chloride on phenylsemi- carbazide suspended in benzene, me decided t o adopt the latter, and were considerably surprised t o find that the product which we obtained melted a t 202-203O, the melting point given by Michaelis and Schmidt, and not a t 210-211" (Widman). Widman also gives 2l0-21lo as the melting point of the product obtained by Michaelis and Schmidt's method. As alternate fractional recrystallisations from dcohol and benzene failed to alter the melting point of any portion of the sub- stance, the experiment was repeated, using carefully purified phenyl- semicarbazide melting sharply at 171', and the purest obtainable benzoic chloride.After boiling in a reflux apparatus until evolution of hydrogen chloride had ceased, the mixture was allowed t o cool, and the crystalline product was recrystallised from 99 per cent. alcohol ; both before and after recrystallisation it melted at 202-203'. The decanted benzene also, on standing, deposited a further crop of crystals, which melted at 202--203°. 0.3078 gave 29.0 C.C. moist nitrogen a t 12.5" and 750.1 mm. N = 16.31. CGH,*N(CO.C,Hj)*NH*CO.NH, requires N = 16.4'7 per cent. I n addition to the difference in the melting points, our preparation seemed to be considerably more soluble in benzene and i n alcoliol tlian Widman's was, The only chemical action to be compared was the condensation by means of caustic potash to diphenyloxytriazole, and in regard to this point our experience agrees with Widman's observations.The benzoylphenylsemicarbazide mas dissolved in warm caustic potash,OSYTRIAZOLES FROXI PHENYLSEJIICARRjiZInE. 203 nncl, on adding hydrochloric acid, a white, crystalline precipitate was formed which, after recrystallisation from alcohol, melted at 2S8-289", and was undoubtedly diphenyloxytriazole. I n view of these facts, it seems highly probable that there are two 1 -benzoyl-1-phenylsemicarbazides, both of which, according to the usually accepted constitution foip the semicarbazides, would be represented by formula I. C),H,-?J* N H* C(0H):NH I C,$H5* N N H CO NH, I 11.* CGHj*CO C,H,m C 0 It is quite possible that semicarbazides may contain the grouping - C(OH):NH, as in formula 11. The isomerism under consideration could hardly be due t o ono isomeride having the constitution represented by I., and the other that represented by II., as, in such a pair, one isomeride would be readily converted into the other, which does not seem to be the case in this instance. A similar objection might be urged to the suggestion that both substances may have constitution II., and that the isomerides may be represented by (' syn " and " anti " formulq similar t o those by which the isomerism of the oximes is explained by the Hantzsch- Werner theory, thus : H*N II II * C',H,*N(COC,H,)*NH* C *OH N*H and C,,H;X(COC',H;)*XR.C *OH A more probable explanation of the supposed isomerism may be founded on the fact that two of the nitrogen atoms are each attached to three different groups, The possibility of isomerism being produced by a difference in the arrangement of three different groups about a nitrogen atom has been recognised for some years (Hantzsch and Werner, Eel*., lS90, 23, 20), but it is only recently that v. Miller and Plochl (Be?*., 1896, 29, 1462) have succeeded in obtaining the first pair of isomerides in which the isomerism has been shown to be due to this cause. These authors have shown that the condensation of acetaldehyde and anisidine yields two products, both of which must be represented by the formula C,H:,(CH:~),*NH* CH(CH,)-CH.; CHO. They point out that, as neither isomeride is optically active, the iso- merism cannot be due to the asymmetric carbon atom, and that for the same reason the three valencies of the nitrogen atom must be con- sidered to lie in the same plane.To account for the isomerism, the following two formulse are suggested. C H(CH,)* CH,* COH I I I I C H(CH,)* CH,* COH N*C,H,(CH,), and NH H C,H,(CH:J,204 YOUNG AND ANNABLE : FORMATION OF SUBSTITUTED It is important to note that v. Miller and Plochl find that these two isomerides cannot be readily, if a t all, converted one into the other. I f in the case of benzoylphenylsemicarbazide we have to deal with a similar case of isom&ism, it seems probable that it is due to a differ- ence in the arrangement of the groups round that nitrogen atom to which benzoyl is attached, and the two isomerides might be repre- sented by bhe tentative formulze NH.CO *NH, O*C,H, N* CO*C,H, I and N*NH* CO*NH,. I CGH5 It might be interesting to note that the benzoylphenylsemicarbazide is not the only case in which Widman and Michaelis and Schmidt have observed different melting points for the same derivative of asym - benzoylphenylhydrazine. Benzylidenebenzoylphenylhydrazone, C,H,-N(COC,H,)*N:CH* CGH,, was observed by Widman (Bey., 1893,26, 947) to melt a t 115-116', and by Michaelis and Schmidt (loc. cit.) a t 122'. Both specimens were prepared by the action of benzaldehy de on benzoylphenylhydrazine which melted at 69-70'. As such cases of isomerism are, not only interesting, but also of great theoretical value, we regret we are unable to pursue this investi- gation," and hope that someone interested in this subject may be able to decide whether two isomeric benzoylphenylsemicarbazides exist, or a t least as to the cause of the difference in the products obtained, on the one hand by Widman, and on the other by Michaelis and Schmidt and by us, Attempts to Condense Be~a,zxoy~~en?/Zsemiccc?.bcc.2.ide. Benzoylphenylsemicarbazide (1 mol.), dissolved in boiling alcohol, was boiled with ferrous chloride (2 mols.).The product consisted wholly of unaltered benzoylphenglsemicarbazide, melting at 202-203". No trace of diphenyloxytriazole could be observed. The above ex- periment was repeated with the addition of hydrochloric acid, but the result was the same. The effect of heating the mixture under pressure at 130' for half an hour was next tried, but the benzoylphenylsemicarbazide was recovered unchanged.There was no diphenyloxytriazole formed. On * We have been compelled to cease our investigations into derivatives of phenyl- hydrazine, owing to one of us having become so extremely sensitive to these sub- stances that the merest trace of vapour or of substance in solution prodiices an acute attack of eczema on the exposed portions of the skin.OXYTRIAZOLES FROAI PHENYLSEMICARBAZIDE. 205 repeating the experiment with the addition of hydrochloric acid, hom- ever, the cooled tube showed a high internal pressure, and neither benzoylphenylsemicarbazide nor diphenyioxytriazole could be found in the alcoholic solution. We are of opinion that these failures to condense benzoylphenyl- semicarbazide, along with the resultss of the investigation on the action of benzaldehyde on pheny lazocarbamide, show that benzoylphenyl- semicarbazide is not formed by the oxidation of a mixture of phenyl- semicarbazide and benzaldehyde, or by the action of the latter on phenylazocarbamide.The equations Ilrc. and IIb., given at the com- mencement of this paper, may be, therefore, taken as fairly represent- ing the course of the action by which diphenyloxytriazole is formed from benzaldehyde and phenylsemicarbazide. I n order to obtain some idea as to the scope of this action, we have investigated the behaviour of a variety of aldehydes, and have ob- tained a series of oxytriazoles, which are described in the following pages.The aldehydes which have yielded oxybriazoles are : metanitro- benzaldehgde, paranitrobenzaldehyde, metatoluic aldehyde, terephthalic aldehyde, and cinnamic aldehyde. The following did not yield oxytriazoles : formaldehyde, acetalcle- hyde, paraldehyde, isobutaldehyde. This oxytriazole was prepared by the oxidation of an alcoholic solu- tion of phenylsemicarbazide and paranitrobenzaldehyde. The addition of water to the product precipitated a reddish-yellow substance, which, on treatment with warm ammonia, passed almost completely into solu- tion, leavinga red, tarry residue. On adding hydrochloric acid to this solution, a yellow, amorphous precipitate was obtained, which separated from 90 per cent. alcohol in the crystalline state. Dried a t looo, it gave figures agreeing with the formula which requires C = 59.57 ; H = 3.54, and N = 19-85 per cent.NO,* C,,H,C',N,* OH, I. 0,1329 gave 0.2902 CO, and 0.0441 H,O. 11. 0.2050 ,, 34.0 c.c.moist nitrogen a t 14Oand 768-0 mm. N = 19-72. Paranitrodiphenyloxytriazole is insoluble in water, easily soluble in boiling alcohol, less so in cold alcohol, and only slightly in boiling ether and benzene. It is easily soluble in alkalis, and in warm alkali carbonate solutions, and these solutions do not reduce Fehling's solu- tion,or silver nitrate, evenon prolonged boiling. No sharp melting point C = 59.55 ; H= 3.68.206 YOUNG AKD ANNABLE : FORMATION OF STJRSTITUTED could be observed, as, when heated in a capilinry tube, the su1)stanco begins to darken a t ?,TO", and melts and decomposes abont 2563-260'. The ammoniacnl sulntion is deep red, but on boiling, the red colour gradually disappeared, and, a t the samc time, a crystftllioe film formecl on the surface. When nmnionia could no longer be cletected in the steam, the liqiiid mas filtered and the filtrate acidified, but there mas no precipitation.The crystalline film melted a t about 256-260", and a nitrogen determination gave figures agreeing with the formula of the oxytriazole, C,,H1,N,O,, or N = 19.85 per cent. Found, N = 20.13 per cent, The ammonium salt is, therefore, completaly dissociated a t the temperature of boiling water. The same result followed an attempt to prepare the ammonium salt by allowing n concentrated ammoniacal solution of the oxytriazole to evaporate spontxneously.The residue consisted of unchanged oxytriazole. Paranitrodiphenyloxytrjazole is oxidised by boiling nitric acid to paranitrohenzoic acid, which was identified by its melting point, 237--238", and by a nitrogen determination. C7HSN0, requires N = 8-38 per cent. The silver salt of paranitrodiphenylox~+iazole, N0,C12H,C,N,0Ag + iH,O, is precipitated as a yellowish, crystalline powder on adcling silver nitrate to the amrnoniacal solution. It is easily soluble in excess of ammonia. When dry, i t seems to be stable, but if exposed to light while moist, it rapidly turns red. The water of crystallisa- tion is given up a t 110". Pound, N = 8.29 per cent. 0.6602 lost,, a t 110", 0.0152 II,O = 2.30. 0,6452, dried a t l l O o , gave 0,2394 AgC1. Cl,H,N,O,Ag + iH,O requires H,O = 2-26, Ag = 27.93.C1,H,N,O,Ag reqiiires Ag = 27.76 per cent. Ethg Z ~ ~ ( ~ . r . n l z i t i . o c T z J ~ e ~ ~ ~ ~ o ~ ~ t i , ~ t ~ ~ o Ze, NO, C, ?H,. C',N,O* C,H,. The ethyl derivative, prepared by the action of ethylic iodide on the dried silver salt, crystallised from alcohol in long, thin, slightly yellow plates, which melted a t 140". It is insoluble in water, slightly soluble in cold alcohol and ether, and easily in boiling alcohol and ether. The solution in benzene is precipitated by the addition of light petroleum. I t is not attacked by boiling alkalis or by boiling concentrated acids. 0.1'732 gave 26.4 C.C. moist nitrogen a t 12' and 758.9 mm. N = 18-06. CliH9N4O3*C2Hi requires N = 18.06 per cent. Acetg?ll;llniw Iziti.ocli~J~ei~yZorc?/tl.ictxole, KO; c', .H,* C,N30 C,H,O.The acetyl derivat ve, prepared by boiling the oxytriazole withOXYTRIAZOLES FROM PHENYI,SEI\IIC'ARRh%InE. 207 acetic anhydride and fused sodium acetate, was recrystallisecl from alcohol. I t formecl small, hard, fl:it needles, having a slight yellow tinge and melting a t 152". I t is easily soloblc in glacial acetic. acid, in cold ether, and in boiling alcohol. When 1)oiled with potassiiini carbonate solution, or with dilute hydrochloric acid, it is rapidly h ydrol ysed. 0.2000 gare 30.2 C.C. moist nitrogen at 12" and 722.1 mm. N = 17.02. C,,H,N,O,* C,H :O requires N = 17-28 per cent. The silver salt was warmed with benzoic chloride dissolved in ether, and t h e product recrystallised from alcohol. It formed yellowisli- white, feathery plates, which melted at 153".This derivative is insoluble in water, fairly soluble in boiling alcohol and ether, less so in cold alcohol and ether. It is easily soluble in benzene, and is pre- cipitated from the solution by the addition oE light petroleum. It is slowly hydrolysed by boiling potassium carbonate solution, and more rapidly by boiling dilute hydrochloric acid. 0.2193 gave 27.1 C.C. moist nitrogen at 15.5"and 759.1 mm. N = 1 4 4 ? . C1,H9N,03* C7H,0 requires N = 14.50 per cent. Reduct ioiz of Pnm n itraocl iph c jig Z o q t r icc zo Ze. Paranitrodipbenyloxytriazole was added in small quantities at a time to a warm mixture of stannous chloride and concentrated hydrochloric acid. After dilution, the tin was removed as sulphide, the filtrate concentrated, and the new base precipitated by the addition of am- monium acetate.Further purification was effected by dissolving i t in dilute, warm ammonia, precipitating by acetic acid, dissolving again in warm glacial acetic acid, and precipitating by water. 0.1576 gave 0-38-15 CO, and 0.0681 H.,O. 0,2155 48.0 C.C. moist nitrogen a t 1 5 5" and 748-9 m u . N = 22-42. NH,. C,,H,C',N,*OH reqnires C = 66 66 ; H = 4.76 ; N = 28-22 per cent. C: = 66.53 ; H = 4.80. ,, C,H;X*N Pn YCI nzido t l iph e 1 t g Z o q t 1- i CI Cole, I >C*OH,forms delicate, NH,.C .H C :N 4 mhite needles, which remained unchanged when heated t o 290'. It is easily soluble in dilute mineral acids and in warm glacial acetic acid ; from its solution in the latter, it is precipitated unchanged on the addition of water.It is easily soluble in dilute alkalis and in warm potassium carbonate solution, from which i t is precipitated by dilute acetic acid, The alkaline solutions do not reduce Fehlings solution,208 YOUNG AND ANNARLE : FORMATION OF SUBSTITUTED It is only slightly soluble in boiling alcohol, almost insoluhle in ether and benzene. The arnmoniacal solution, when warmed, became rapidly covered with a film of slender neeclles,whichanitrogendeterminationshowed to be the free amiclodiphenyloxytriazole. Found N = 22.44 per cent., C,+HI,N,O requiring N = 22.22 per cent. When paramidodiphenyloxgtriazole is dissolved in a small quantity of warm, concentrated hydrochloric acid, the hydrochloride crystallises out in long needles as the solution cools.These crystals, if air-dried on a porous plate, contain 3H,O; when dried in a vacuum over sul- phuric acid, or if heated to 90°, the water of crystallisation is given up, and if the temperature be raised, hydrochloric acid is also lost,, dissociation being complete at 11 0". The residue, dissolved in nitric acid, gave no precipitate with silver nitrate. 0~612810st,at90°,0~0980,andat I1O0,O*164L H,O= 15.97; HCl= 10.80. 0.8596 of the dried salt gave 0.4194 AgC1. 1.0223 lost over sulphuric acid 0.1627. Hal= 12.41. H,O = 15.93. C,,H,,N,O,HCl+ 3H,O requires H,O = 15.76 ; HC1= 10.66 per cent. C,,H,,N,O,HCl requires HCl= 13.66 per cent. The silver salt, NH,* C,,H,* C,N,OAg + H,O, is precipitated as a white, amorphous powder on adding silver nitrate to an animoniacal solu- tion of amidodiphenyloxytriazole.It is easily soluble in excess of ammonia and in nitric acid. After being dried over sulphuric acid, i t appears to be quite stable, but if exposed to light while moist i t rapidly turns red. Analysis gave the following figures agreeing with the above formula. 1.5092 lost, at 1 lo", 0.0'732 and then gave 0.5748 AgCl. H,O = 4.55 ; CI4Hl1N,OAg + H,O requires H,O = 4 77 per cent. Ag = 30.34. C1,H,,N,OAg requires Ag= 30.08 per cent. The diacetyl derivative, formed when amidodiphenyloxy triazole is boiled with acetic anhydride and fused sodium acetate, is easily soluble in glacial acetic acid, ether, and boiling alcohol ; recrystallised from 80 per cent. alcohol, it forms a white, crystalline powder which melts a t 2 15'.0.2148 gave 31.4 C.C. moist nitrogen a t 12" and 739.8 mm. N= 16-88, C,,H,,N,O*(C,H,O), requires N = 16-66 per cent.OXYTRIAZOLES FROM PHENYLSEMICARBAZIDE. 209 The diacetylamidodiphenyloxytriazole is insoluble in cold, dilute acids and alkalis, but when boiled with potassium carbonate solution, it gradually passes into solution ; on adding hydrochloric acid, the monacetyl derivative is precipitated. The same partial hydrolysis is effected by boiling with dilute hydrochloric acid. Morzucety~~ii1.a~Iiiclod;~l~esz?/ Zoxyt~iccole, LC:,H,*N*N C,II,O *NH* C,H,* C :N I YC-OH, 4 1 is easily soluble in alkalis, alcohol, and ether. dilute acids. which melt a t 278". the amidodiphenyloxy triazole is warmed with acetyl chIoride. It is insoluble in It crystallises from alcohol in white, hair-like needles, The same monacetyl derivative is formed when 0.1987 gave 32.9 C.C.moist nitrogen a t 15' and 745.4 mm. N = 19.01. C,H,O* C14H1,N40 requires N = 19 04 per cent. When the monacetyl derivative is boiled with concentrated hydro- chloric acid, it gradually becomes dissolved, and addition of dilute ammonium acetate solution precipitates p-amidodiphenyloxytriazole, as shown by the high melting point (over 290') and by a nitrogen determination. 0.1846 gave 35.8 C.C. moist nitrogen at 16-5"and 750-1 mm. N = 22.25 C,,H,,N,O requires N = 22.22 per cent. This oxytriazole was prepared by the oxidation of an alcoholic solu- tioh of phenylsemicarbazide and metanitroben zaIdeby de. As in the case of the paranitro-derivative, treatment of the product with am- monia left a small amount of a red, tarry matier undissolved; 011 acidifying the nminoniacal solution, a y ellowisli, crystalline precipi- tate was formed.This was dissolved in boiling benzene, and as the solution cooled, metanitrodiphenyloxytriazole crystallised out in yellowish, microscopic plates, which melted a t about 275-278". The melting point could not be observed sharply, as considerable decompo- sition takes place before it is reached. 0.1655 gave 0.3608 CO, and 04554 H,O*(: : 5'3.45 ; H- 3.7'1. 0.1608 ,, 27.4 C.C. moist nitrogen at 15" and 753.3 mm. N = 19.75, C1,€IE-I,,N,O, requires C = 59-57' ; H = 3.5 1 ; N = 19.S.5 per cent.210 YOUNG AND ANNABLE : FORMATION O F SUBSTITUTED Yhenylmetanitrophenyloxytriazole is very slightly soluble in water, more so in boiling alcohol, ether, benzene, and glacial acetic acid.It is easily soluble in dilute alkalis and in warm, dilute alkali carbonate solutions. It dissolves in warm, concentrated hydrochloric acid and is precipitated unchanged on the addition of water; it is not attacked by prolonged boiling with concentrated hydrochloric acid or alkalis, and the alka,line solution does not reduce Fehling's solution or silver nitrate. As the aqueous filtrates from metanitrodiphenyloxytriazoll: were found to be always more or less coloured, the solubility in water mas determined by boiling an excess of the substance with distilled water and filtering througha hot filter, It was found that 100 C.C. of water measured a t 15' dissolved, when boiling, only 0.0343 gram of metanitrodipheny loxy triazole.This oxytriazole is very easily soluble in warm, dilute ammonia, forming a somewhat opaque, deep, reddish-yellow solution. The am- monium salt is very easily dissociated, nitrodiphenyloxytriazole separating out in crystalline scales when the solution is kept warm. These melted a t 270-276", and on analysis gave N = 19.88 per cent ,, C,,H,,N,O, requiring N = 19.55 per cent. Xetanitrodiphenyloxytriazole, when boiled with dilute nitric acid, is oxidised t o metanit'robenzoic acid, which was recognised by its melt- ing point, and by a nitrogen determimation. Found, N = 8.31 per cent., NO,. C,H,* COOH requiring N = 8-38 per cent. The silver derivative, NO; C,,H,- C2Nij* OAg + 4 H,O was thrown down as a white, amorphous precipitate on adding silver nitrate t o an ammoniacal solution of the oxytriazole.It is easily soluble in excess of ammonia ; when dry, it seems t o be stable, but in the moist condition i t rapidly becomes red on exposure to light. The air-dried substance, when heated to 100-llOo, lost weight equivalent to &H,O. 0.3288 a t 110" lost 0.0082 H,O = 2.49. 0.5720, dried a t l l O o , gave 0.2113 AgCl. Ag=27*80. NO,* C1,H,C,N,*OAg + &H,O requires iH,O = 2.26 per cent. NO; C,,H,C,N; OAg requires Ag = 27.76 per cent. This derivative was prepared by the action of a n etliereal solution OF cthylic iodide on the dried silver salt. On evaporating the ethereal solu- tion, a mass of yellowish, silky needles was deposited. These needles melted at 9V, and after repeatedly recrystallising from dilute alcohol, were obtained as small, yellow, prismatic crystals, melting at 98'.N == 1S.23. 0.2105 gave 32.8 C.C. moist nitrogen at 16" and 761.11 mm. l3thylmetanitrodipheiiylosytriazole is insoluble in water, easily NO,* C,,H,:C,N,O-C,I€, requires N = lS.06 per cent.0 XY TRI AZO 1, ES FROM PHEN Y LS EJIIC ARB AZIDE. 211 soluble in alcohol and ether. alkalis. It is not acted on by boiling acids o r Acety~~izetc~~~it.i~o~l~~)~en~Zo.~~t~.icc.;oZe, NO; C,,H, : C,?J,O. C,I€,O. Prepared in the same way RS acetylparanitrodiplienyloxy triazole , it is left in clusters of small needles on evaporating the ethereal solution. It melts a t 116", and is moderately soluble in cold ether, easily in boiling ether, glacial acetic acid, or ethylic acetate.0.2173 gave 33.2 C.C. moist nitrogen at 12"and 720.1 mm. N = 17.17. NO,C,,H,* C,N,0*C2H,0 requires N = 17:28 per cent. The acetyl derivative is rapidly hjdrolysed when boiled with potas- sium carbonate solution or with dilute hydrochloric acid, giving meta- nitrodiphenyloxytriazole, melting at 275- 277". l ' e n ~ o ? / l n z e t ( ~ c l z i t . 1 ~ o ~ ~ ~ ~ J ~ e ~ ~ ~ l o ~ ~ t ~ ~ ~ ~ ~ o l ~ , NO,* C1,,Hc, : C,N,0*C7H,0, was prepared by warming the dried silver salt, suspended in dry ether, with a slight excess of benzoic chloride. The ethereal solution, after wash- ing with potassium carbonate, was dried a i d evaporated ; the yellow crystals thus obtained melted a t 148". It is fairly soluble in warm ether and in boiling alcohol. 0.1616 gave 21.1 C.C.moist nitrogen at 19.5" and 758.2 mm. N = 14-92. NO,C1,H; C,N,0*C7H,0 requires N = 14.50 per cent. Redzcct io of n-letcc )&rot1 iphe?Zy Zoxpti. icco Ze. The reduction was effected with iron filings and concentrated hydro- chloric acid, and on the completion of the reaction, water was added and the excess of hydrochloric acid removed by a current of steam. When the solution had cooled down, ammonium acetate was added to precipi- tate the new base, which was purified by dissolving it in ammonia and reprecipitating by dilute acetic acid. 0.1571 gave 0.3835 CO, and 0.0688 H,O*C = 66.57.H = 4 S7. 0.2004 ,, 35.6 C.C. moist nitrogen a t 13.5" and 752.2 mm. N = 22.35 C,,H,,N,O requires C: = 66.66 ; €I = 4.76 ; N = 22.22 per cent. in needles melting a t 278".It is easily soluble in dilute hydrochloric acid and in glacial acetic acid, and is precipitated from the latter solu- tion on adding water. It is easily soluble in dilute alkalis and in warm potassium carbonate solution, and is reprecipitated by acetic acid. It is slightly soluble in boiIing alcohol, hit insoluble in ether and benzene. The ammoniacal solution has a deep red colour which212 YOUNG AND ANNABLE : FORMATION OF STTBSTITUTED disappears on boiling, the free oxytriazole separating as a crystalline film melting at 27s"; on analysis, it gave N = 22*3'7,C1,H1,N,0 requiring N = 22.22 per cent. When metamidodiphenyloxytriazole is dissolved in a small quantity of warm, concentrated hydrochloric acid, the hydrochloride, NH,* C,,H,:C,N,* OH,HCl + 3H,O, crystallises out in brownish needles as the solution cools.The air- dried crystals contain 3H,O, which are given up a t l l O o , or when the salt is dried in a vacuum over sulphuric acid. This hydrochloride differs from the corresponding salt of paramidodiphenyloxytriazole in that at 110" dissociation into the free base and hydrochloric acid does not take place. 0.9898 lost, a t l l O o , 0.1565 H,O= 15.S2. 0 S333, dried at l l O o , gave 0.4084 AgCl. 0-9144, dried over sulphuric acid, gave 0.4415 AgCl. NH,*C,,H,:C,N,* OH,HCl+ 3H,O requires 3H,O = 15.76 per cent. NH,* C,,H,:C,N,*.OH,HCl requires HC1= 12.66 per cent. HCl = 12.47. HCl= 12.31. The silver salt, NH,. C12H!,: C,N,OAg + H,O, is a white, amorphous powder, which rapidly turns red if exposed to the light while moist, but seems to be stable when dry.It is easily soluble in ammoniaand in nitric acid. It loses its water of crystallisation a t 100-110". 1.6583 lost, at 110", 0.0799 H,O = 4*S(2. 1,5794, dried at l l O o , gave 0.6311 Ag Cl. Ag = 30.07. NH,. C,,H,:C,N,OAg + H,O requires H,O = 4-77 per cent. NH,* C,,H9:C,N,0Ag requires Ag = 30.08 per cent. B iacet yZnietaaLidod~~l~e.rL y Zoxpt&m Ze, The diacetyl derivative was prepared by boiling the oxytriazole with acetic anhydride and fused sodium acetate. The oil left on evaporating the ethereal solution was dissolved in boiling alcohol, and water added, when a white, crjstalline powder was precipitated whicb, after recrystallisation from dilute alcohol, formed small, white needles melting a t 117". 0.3678 gave 53.3 C.C.moist nitrogen at 17", and 759.5 mm. N = 16.82. ClsH16N,0~j requires N = 16.66. It is insoluble in cold, dilute alkalis and acids, but when boiled with dilute potassium carbonate solution it is rapidly converted into the mon- acetyl derivative ; the same change also takes place when the diacetyl derivative is boiled with dilute hydrochloric acid. iCloiiclcet~Z~~~etn~~~.iclotl~~7~es~~Zox.yt~~iaxoZe, C,H,O *NH* C,,-H9: C,N; OH, C,H,O*NH* C1,H,:C,N,O*C,H,O. This diacetyl derivative is easily soluble in ether and alcohol.OXYTRIAZOEES FROM PEIENYLSEMIChRBAZIDE. 213 is deposited from dilute alcohol as a white, crystalline powder which melts at 294". The same monacetyl derivative may be formed by warming amidodiphenyloxytriazole with acetic chloride.0,1682 gave 28.0 C.C. moist nitrogen a t 1 8 O , and 761.9 mm. N = 19.27. C1,H14N402 requires N = 19.04 per cent. The monacetyl derivative is easily soluble in alkalis, in warm potassium carbonate solution, in alcohol, and in ether. It is insoluble in dilute acids, but when boiled with concentrated hydrochloric acid the remaining acetyl group is removed, and on then adding ammonium acetate the free amidodiphenyloxytriazole is precipitated. It was recog- nised by its melting point, 278*, and a nitrogen determination. Found, N = 22.29 per cent., Cl,H12N,0 requiring N = 22.22 per cent. Phenylmetatolyloxytriazole was prepared by the oxidation of an alcoholic sohtion of phenylsernicarbazide and metatoluic aldehyde. Ten grams of phenylsernicarbazide yielded over 9 grams of phenyltolyl- oxytrinzole.The crude product was purified by dissolving it in ammonia and reprecipitating by sulphuric acid. It crystallised from alcohol in white, microscopic plates which melted sharply a t 256". 0.1624 gave 0,4268 CO, and 0.0767 H,O. 0.2219 C = 71.69 ; H = 5-25. ,, 32.4 C.C. moist nitrogen a t 15' and 749.1 mm. N = 16.85. C1,H,:,N30 requires C = 71.71 ; H= 5.17 ; N = 16.73 per cent. Phenylrnetatolyloxytriazole is sparingly soluble in boiling alcohol, ether, and benzene, and almost insoluble in boiling water and in light petroleum. It is easily soluble in alkalis, and in a boiiing, dilute sdution of potassium carbonate, from which it is reprecipitated by acetic acid. The alkaline solutions do not reduce Pehling's solution or silver nitrate, even on prolonged boiling.The ammoniacal solution is reddish-brown, but when boiled, it gradually becomes colourless, the oxytriazole at the same time being precipitated, The addition of silver nitrate to the aqlmoniacal solution precipitates the silver salt of phenyltolyloxytriazole as a white, amorphous powder. It is easily soluble in excess of ammonia, and separates from a warm, dilute ammoniacal solution, on cooling, in smalI, shining crystals. It becomes red when exposed to light while still moist, but seems quite stable when dry. Dried in n vacuum over sulphuric acid, i t contains lH,O, which is given up at 100-110". VOL. LXXI, Q214 YOUNG AND ANNABLE : FORMATION OF SUBSTITUTED 0,7433 lost, at l l O o , 0.0360 H,O = 4.85. 0.70'73, dried at 110', gave 0.2843 A@.Ag = 30.25. C,,H,,:C,N,OAg + H,O requires H,O = 4-78 per cent. C,,,Hl2:C,N3OAg requires Ag = 30.16 per cent. Etlz?l~J~e.n?/lnzetatol?lloxyts.iccxoZe, Cl,H12: C,N,O* C,TI,. The ethyl derivative was prepared from the silver salt by the action of ethylic iodide. On evaporating the ethereal solution, an oil was left which was dissolved in warm, light petroleum; on evaporating this solution, the ethyl derivative crystallised in clusters of plates which melted a t 59". It is easily soluble in alcohol, ether, benzene, and light petroleum, and separates from most of these solutions as an oil which solidifies on standing. 0.2086 gave 28.2 C.C. moist nitrogen at 14' and 736.6 mm. N = 15.40. It is not attacked by boiling acids or alkalis. C,,H,,- C,N,O*C,H, requires lS = 15-05 per cent.Acet?l~J~e~a?llnzetcclol~lox~t~inxole, C,,H,,: C,N,O*C,H,O. The acetyl derivative is formed on boiling the oxytriazole with acetic anhydride and fused sodium acetate ; the product was then neutralised with potassium carbonate and extracted with benzene. The brown oil left on distilling off the benzene was treated with small quantities of warm, light petroleum ; on cooling, a small quantity of oil was first de- posited and then white, crystalline nodules which melted at 65-68'. On recrystallisation from dilute alcohol, the acetyl derivative separated as an oil, which gradually solidified to white crystals melting at 69.5-70". After repeated recrystallisation, the melting point remained constant at 70". 0.2328 gave 20.2 C.C. moist nitrogen at 14' and 742.7 mm.N = 14.41. C13H12: C,N,O*C,H,O requires N = 14.33 per cent. The acetyl derivative is insoluble in water, easily soluble in alcohol, ethor, and benzene, and in warm, light petroleum. It is easily hydro- lysed by boiling potassium carbonate solution, or by boiling dilute hydrochloric acid, yielding phenyltolyloxytriazole melting at 256". Benso?ll~J~en?llbrtet~tol?llox?lt?.iwxole, C,,H,,: C,N,0*C7H,0. The benzoyl derivative, prepared by the action of benzoic chloride on the silver salt suspended in dry ether, crystallised from alcohol in clusters of small, white needles which melted at 1179 It is easily soluble in warm alcohol and ether, moderately so in benzene, insoluble in light petroleum and in water. 0,2477 gave 26.1 C.C. moist nitrogen at 14" and 755% mm.N = 12.32. C13H,,C,N,C7H,0 requires N = 12.38 per cent.OXYTRIAZOLES FROM PHENYLXEMICARBAZIDE. 215 The benzoyl derivative is hydrolysed by boiling alkalis and acids, more slowly by boiling potassium carbonate solution, yielding phenyl- metatolyloxytriazole melting at 256". This oxytriazole was prepared b y the oxidation of an alcoholic solution of rphenylsemicarbazide and cinnamaldehyde. After removnl of the alcohol by a current of steam, a yellowish, crystalline film separated, which was dissolved in dilute ammonia, filtered, and repre- cipitated by hydrochloric acid. The product, after several recrystalli- sations from alcohol, formed yellowish, shining leaves, which nielted at 2 8 4 O . 0.1404 gave 0.3'750 CO, and 0.0659 H,O. 0.2053 ,, 28.5 C.C.moist nitrogen a t 15fi"and 750.7 mm. N = 16.02. C,,H,,N,O requires C = 73.00 ; H = 4194 ; N = 15.96 per cent. Phenylstyrenyloxytriazole is only sparingly soluble in hot alcohol, and almost insoluble in ether, benzene, and water. It is easily soluble in alkalis and in warm potassium carbonate solution, from which i t is reprecipitated by acetic acid. The ammoniacal solution is slightly fluo- rescent, but, on boiling, the fluorescence gradually disappears and at the same time the oxytriazole separates as a crystalline film. The alkaline solutions do not reduce either Fehling's solution or silver nitrate. After repeated recrystallisation from alcohol and from glacial acetic acid, the substance was odourless, remained slightly yellow, and melted constantly a t 284'. Fractional recrystallisation, as also conversion into the acetyl- and the benzoyl-derivatives with subsequent hydrolysis failed to raise the melting point above 286".This was particularly noted, as Widman, who has also recently (Be?.. , 1806, 29, 1946) prepared phenylstyren yloxytriazole by the action of caustic potash on cinnamylphenylsemicarbazide, observed that i t melted at 287". I n other respects, the properties of our product agree with those described by Widman. The silver salt, CI4I3,,:C,N,OAg + l ~ H , O , is precipitated as a yel- lowish, amorphous powder on adding silver nitrate to a cold, dilute amtnoniacal solution of phenylstyrenyloxytriazolc. If the precipitatioii be carried out in a warm solution, or in one containing too great an excess of ammonia, the silver salt separates as a dark, tarry mass, which gradually changes to a yellowish powder when shaken with large quantities of water.Analysis gave figures agreeing with the above formula, the water being given off at 110'. ' " Styrenyl " is the term suggested by Widman (Bw., 1896, 29, 1946) for the nnsaturated univalent radicle C,H,* CH: CH-. C = 72.84 ; H = 5-21. Q 2216 YOUNG AND ANNABLE : FORMATION OF SUBSTITUTED 0.6573 lost, at 110', 0.0430 H,O = 6-54, 0.5887, dried at 1 loo, gave 0.2300 AgC1. Ag = 29.40. C,,I€,,:C,N,OAg + l&H,O requires H,O = 6-80 per cent. ; C,,H,,: C,N,OAg requires Ag = 29.19 per cent. The ethyl derivative, prepared by the action of ethylic iodide on the dried silver salt, crystallises from SO per cent. alcohol in clusters of white needles melting a t 89-90'.It is fairly soluble in ether, alcohol, and benzene, slightly so in lighb petroleum. 0.2635 gave 31.4 C.C. moist nitrogen at 13' and 769.3 mm. N = 14.26. C,,H,,:C,N,O*C,H, requires N = 14-44 per cent. When boiled with alkalis, the ethyl derivative is coiiverted into an oil, which, on treatment with benzene, again becomes crystalline and melts zt S9-90"; the same effect is produced by long boiling with concentrated hydrochloric acid. The acetyl derivative was prepared by the action of acetic chloride on the dry silver salt and also by boiling the oxytriazole with acetic anhydride and sodium acetate; both methods yielded an oily sub- stance which could not be properly purified. It was easily soluble in the various organic solvents, but on cooling or on evaporation of the solution, the substance separated as an oil; i t was, therefore, not analysed.It dissolved when boiled with dilute potassium carbonate solution, and on acidification phenylstyrenyloxytriazole melting at 283-284" separated. The benzoyl derivative, prepared by boiling the dry silver salt with an ethereal solution of benzoic chloride, crys tallised from alcohol in round tufts of small, yellowish needles melting a t 1 2 5 O . From benzene, it crystallised in brilliant, yellow, silky needles. It is easily soluble in warm benzene, ether, and alcohol. 0.2349 gave 23.1 C.C. moist nitrogen at 14" and 749.5 mm. N = 11.41. C,,H,,:C,N,O* C,H,O requires N = 1 1 a44 per cent. Hydrolysis takes place slowly when the benzoyl derivative is boiled with potassium carbonate solution, more quickly by the action of boiling acids and alkalis. The regenerated phenylstyrenyloxytriazole melted a t 283"-284".OXYTRIAZOLES FROM PHENPLSERIICARBAZIDE.a17 N -N C,H,C,H, N -N N=C - C,H, ---GIN HO.C< I I >C*OH. 1 4 This oxytriazole mas prepared by the oxidation of an alcoholic soh- tion of phenylsemicarbazide (2 mols.) and terephthalic aldehyde (I mol.) (melting point 11 6"). The product was washed with warm alcohol, and dissolved in dilute ammonia; on standing, the solution gradually de- posit ed the phen ylenedip h en y loxy triazole in white, cry st alline nodules, which remained unchanged when heated to over 340". 0.1563 gave 0.3802 CO; and 0.0590 H,O. C = 66.34 ; H= 4.19. 0.1283 ,, 23.5 C.C. moist nitrogen at 12Oand 747.7 mm. N = 21 -38. C,,H16N,0, requires C = 66.66 ; H = 4.04 ; N = 21.21 per cent. The substance seems to be quite insoluble in water, alcohol, ether, and benzene. It is, however, easily soluble in alkalis ; when its solution in dilute ammonia was allowed to stand, i t was reprecipitated in yellowish, minute crystals. On adding silver nitrate to the ammo- niacal solution, the silver salt was precipitated; this, when heated at l l O o , lost weight equivalent to about gH,O. 0.7773 lost, a t 110", 0.0160 H,O=2*05. 0.7613 gave 0.3590 AgC1. Ag. = 35.49. C,,H,,N,O,Ag, + $H,O requires $H,O= 2-16 per cent. C,,H1,N,jO,Ag, requires Ag, = 35.40 per cent. The acetyl derivative, prepared by boiling the oxytriazole with acetic anhydride and fused sodium acetate, crystallised from alcohol in clusters of white, delicate needles, which melted at 208-210". It mas easily soluble in alcohol, ether, and benzene. No analysis wasmscle, as me had not sufficient of the substance a t our disposal. When boiled with potassium carbonate solution, the acetyl deriva- tive rapidly passed into solution, and the addition of hydrochloric acid precipitated the high melting phenylenediphenyloxytriazole. Having shown, as described in the foregoing pages, that the forma- tion of an oxytriazole by the oxidation of a mixture of phenylsemicar- bazide and an aldehyde is a general action for aromatic and fatty aromatic aldehydes, we next turned our attention to the purely fatty aldehydes. Those which we have tried are formaldehyde, acetalde- hyde, paraldehyde, and isobutaldehyde. Alcoholic mixtures of these aldehydes with phenylsemicarbazide have been subjected to the action of various oxidising agents, both in open and in closed vessels, at temperatures varying from that of the atmosphere to 150", and for varying lengths of time, but in no instance have we been able218 SUDBOROUGEI : RESEARCHES IN TRE STIT,BENE SERIES. to isolnte an oxytrinzole as a product of the action. We have met with no better success in ~ i i r endeavours to condense these aldehydes with phenylazocnrbnmide. I n RS far as our experience goes, therefore, the action does not seem to be capable of extension t o the purely fatty aldehydes.