HYDROLYSIS OF MIXED SECONDARY AMIDES BY ALKALIS. 299XXXIII.-The Hydraolysis of Mixed Sccondary Amidcsby A lkalis.By ARTHUR WALSH TITHERLEY and LEONARD STUBBS.THE hydrolysis of mixed secondary amides of the typeR*CO-NH*COR’, which takes place readily under the influence ofalkalis, in the first stage may conceivably follow two courses, givingeither the acid, R-CO,H, and amide, R/*CO*NH2, or the acid,R’CO,H, and amide, R*CO*NH,. I n previous communications byone of the authors it has been noted that the hydrolysis of certainmixed secondary amides proceeds exclusively in one of the altermtivedirections. Thus, s-dibenzo-oxamide (Titherley, T., 1904, 85, 168 1)yieIds oxalic acid and benzamide, and not (as might be expectedfrom the stability of oxamide) benzoic acid and oxamide.Similarly,acetobenBamide yields only acetic acid and benzamide, if care istaken to avoid secondary hydrolysis of the latter, and it wouldappear likely that aliphatic-aromatic secondary amides in generaldecompose under the influence of alk.ali into the correspondingaliphatic acid .and aromatic amide exclusively, or virtually so. Thistype of hydrolysis is of interest as bearing on the ring-rupture ofcyclic secondary amides of the purine group, and on the positiontaken up by the mobile hydrogen atom in such pseudo-acids wheni t is repiaced by sodium. It is probable that the sodium compoundsof secondary amides contaic the unsaturated grouping CO-N:C*ONa,and that their more o r less ready hydrolysis in aqueous solution isto be referred t o the doubly linked C:N pair.I f this is so, thepreferential decomposition yielding aliphatic acid and aromaticamide, in mixed secondary amides of the type R-CO-NH-COR’(when R-CO. is an aliphatic acyl and R’*CO* is an aromatic acylgroup) could be explained by assuming that the sodium compoundsare derived from the tautomeric form R*C(OH):N*COR/ exclu-sively. On this assumption hydrolysis is preceded by water-additiona t the double link, as it probably is with amidines and all com-pounds containing the C:N-linking, and formation of the unstabledihydroxy-derivative, R*C(OH),*NH=COR’, which immediatelydecomposes into the aliphatic acid, R*CO,H*, and aromatic amide,R’*CO*NH,. The extreme ease with which most secondary amidessuffer hydrolysis by alkali, as compared with simple amides,R*CO*NH,, and their general similarity to amidines and imino-ethers in hydrolytic sensitivity, renders the above mechanism veryprobable.On the other hand, it is not clear why the mobilehydrogen atom in the tautomeric form should migrate exclusivelyto one of the two oxygen atoms, and it would appear that stericx 300 TITHERLEY AND STUBRS: THE HYDROLYSIS OFinfluence must also be a t work in favouring preferential fission.I f this is the case, i t would seem that the velocity of water-additiona t the double link in the form R-C(OH):N*COR/ must be so muchgreater than in the form R*CO*N:C(OH)R/ (where R/ is the largeraromatic group) that practically no hydrolysis of the latter formoccurs.This supposition is confirmed by the observation of theauthors (see curve, p. 306) that the velocity of alkaline hydrolysisof diacetamide, acetobenzamide, and acetylcarbamide is very muchgreater than that of dibenzamide and other purely aromatic amides;and further confirmation is fomd in the fact that benzo-o-toluamidesuffers fission in one direction exclusively, as described below(p. 301), whilst the para-isomeride decomposes in both possibledirections.It would seem therefore that whilst there are good reasons forbelieving that the mechanism of hydrolysis is one involving additionof water a t the unsaturated C:N pair, the fact that in the abovecases the hydrolysis follows ope course exclusively cannot be inter-preted as indicating the exclusive intermediate production of onetautomeric form.It is possible and probable that both sodiumcompounds, (I) R*C(ONa):N*COR/ and (11) R*CO.N:C(ONa)R’,are formed, in equilibrium, when the secondary amide,R*CO*NH*COR/, is treated with aqueous sodium hydroxide, butthat, owing to the vastly greater rate of hydrolysis of (I), theequilibrium is constantly disturbed as i t is decomposed into theacid R*CO,H and amide R’*CO*NH,; and the amount of acidR’-CO,H and amide R*CO*NH, formed would be thus too smallfor detection.I n order to obtain further evidence as t o the nature of thehydrolysis with mixed secondary aromatic amides, the case of benzo-o-toluamide and benzo-ptoluamide has been closely studied ; andsince each of the mixed secondary amides showed some evidence ofappearing in two desmotropic forms, attempts were also made toisolate the latter, but without success.The first, a modificationof the method of Titherley (T., 1904, 85, 1673), was by condensationof phenyl benzoate with the sodium derivatives of 0- and ptoluamiderespectively :C,H,Me*CO*NHNa + Ph*CO,Ph +Two methods of synthesis were adopted.C,H,Me*CO-NH*COPh + Ph-ONa.This method, however, gave poor results, owing to the occurrenceof secondary reactions leading (by a process analogous to doubledecomposition) t o the formation of dibenzamide and ditoluamide ;and it was found to be practically impossible to eliminate theseimpuritiesMIXED SECONDARY AMIDES BY ALKALIS. 301The second method, which was entirely satisfactory, was basedon the cautious hydrolysis of the acylamidines obtained in thecondensation between benzamidine and phenyl 0- and p-toluatesrespectively by the method of Titherley and Hughes (T., 1911,99, 1505), thus:(1) NH:CPh*NH, + C6H4Me*C02Ph +(2) NH:CPh*NH*CO*C,H,Me + H,O +NH:CPh*NH-CO*C6H4Me + Ph*OH.COPh*NH*CO*C6H4Me + NH,.Excellent yields of pure benzo-o- and -ptoluamides were obtainedin each case.I n studying the products of hydrolysis of benzo-o-toluamide andbenzo-p-toluamide, advantage was t-aken of the fact that in thepresence of aqueous sodium hydroxide the hydrolysis to amide andacid is complete within from three to four days at laboratory tem-peratures or within #a few minutes a t 90°; and under these con-ditions the further hydrolysis of amide was almost completelyavoided.No fundamental difference between the effect of coldand hot alkaline hydrolysis was observed, in the proportions ofthe resulting products. This important difference in the behaviourof the two isomerides was established, however, that whilst benzo-ptoluamide suffers fission under the influence of hot aqueous alkaliin both possible ways to a roughly equal extent (and in the coldt o a larger extent yielding ptoluamide and benzoic acid), benzo-o-toluamide suffers fission exclusively in one direction (at 1 5 O orgoo), yielding o-toluamide and benzoic acid. I n no case couldbenzamide be isol-ated from the products of hydrolysis. As therates of hydrolysis of benzo-o-toluamide and benzo-ptoluamide underthe same conditions are practically equal, and also the same as thatof dibenzamide (see curve, p.306), it. would seem- that sterichindmnce must be responsible for this preferential fission of theortho-derivative into o-toluamide and benzoic acid, since in theequilibrium :Ph*C( 0Na):N CO C,H,Me ZZ Ph CO N : C( ONa) C,H,Me(1.1 (11.)the rate of hydrolysis of I1 wpld be relatively very low, whilst thatof I, which is much higher and governs the entire decomposition,would be virtually the same as that of clibenzamide or of benzo-ptoluamide in its two forms (corresponding with I and 11).From a general consider,ation of the facts established withreference to the rate and direction of hydrolysis of secondary amidesby alkali, it would appear that two factors are a t work, namely,(1) the additive affinity (for water) of the tautomeric grouping*N:C(ONa)R, which is dependent on the nature of the group R 302 TITHERLEY AND STUBHS: THE HYDROLYSIS O Fas well as of that united to the nitrogen atom; and (2) the stericinfluence, more particularly of the group R, a.nd t o a less degreeof the other (acyl) group united t o the nitrogen atom.E XPER 1 MEN TA4L.Benzo-o-toZuaml.de, C,H,*CO*NH.CO*C,H,n/Ie.(1) Preparation from Benzamidine.-Phenyl o-toluate (requisitein the synthesis, and apparently not previously described) wasobtained by heating 13.6 grams of 0-toluic acid, 15 grams ofphosphoryl chloride, and 9 grams of phenol for four hours a t 75O.The resulting red oil, after cooling, was shaken with 10 per cent.sodium hydroxide, and the oil extr9acted by ether.A nearlytheoretical yield (20 grams) of phenyl o-toluate was obtained (dis-coloured), which distilled unchanged a t 306O/754 mm. as a faintlyyellow liquid, which did not solidify on cooling or long keeping.The product obtained by the action of o-toluoyl chloride on phenoland alkali had similar properties, and did not crystallise.o- ToZz~oy Zb e n zamidine, C,H,* C( :NH) *NH* CO C,H,Me.This compound was obtained readily by the condensation ofphenyl o-toluate (10 grams) and benzamidine (6 grams, freshly pre-pared from the hydrochloride) in alcoholic solution, the mixturebeing heated at 50° for five hours. Most of the alcohol was thenremoved by evaporation and the residue treated in the cold withwater and dilute hydrochloric acid.I n this way the o-toluoyl-benzamidine was brought into solution and removed from the smallquantity of unchanged phenyl o-toluate. The aqueous acid solutionwas then rendered alkaline, in the cold, with excess of aqueoussodium hydroxide, when the amidine derivative was precipitated asa colourless oil, which solidified after some time. The yield was5 grams (theory required 11.9 grams), and after recrystallisationfrom light petroleum the compound was obtained in long, trans-parent plates, melting a t 122':0.4646, by Kjeldahl's method, required 38.6 C.C. AT/ 10-HCl.N = 11-63,C,,H,,ON, requires N = 11.76 per cent.o-ToZuoyZ b enzamidine is readily soluble in alcohol, chloroform, oracetone, and insoluble in cold water.It is basic, and dissolves incold dilute hydrochloric acid without decompcsition, but, on heating,slow hydrolysis takes place with formation of ammonia and benzo-o-toluamide, which was obtained in quantity as follows.Ten grams of o-toluoylbenzamidine were dissolved in 850 C.C. offl/lO-hydrochloric acid (2 mols.), and the solution was heated a MIXED SECONDARY AMIDES BY ALKALIS. 30370°. After thirty minutes the solution became milky as thesecondary amide began t o separate, and after three and a-half hours,when the hydrolysis was complete, it had collected as a mass offine, colourless needles (10 grams), the yield being theoretical. Itwas practically pure, and after recrystallisation from 50 per cent.aqueous alcohol was obtained in long, silky needles, melting a t158-159O :0.4666, by Kjeldahi's method, required 19.9 C.C.N/10-HCl.N = 5.97.CI5Hl3O2N requires N = 5-86 per cent.Beizzo-o-tolmmide is moderately readily soluble in alcohol,sparingly so. in benzene, and practically insoluble in ether or lightpetroleum. It dissolves a t once in aqueous sodium hydroxide, andis precipitated unchanged by acids, but the alkaline solution isreadily decomposed on keeping or heating (p. 308).(2) Prepration from o-7'oluarriide.-An intimate mixture of 6.8grams of o-toluamide and 2 grams of sodamide, both previouslyfinely powdered, was moistened with benzene and heated in a refluxapparatus, in a bath the temperature of which was gradually raisedto 120O. After three hours, when no more ammonia was evolved,the resulting white solid (sodium o-toluamide) was covered withbenzene and treated with a solution of 10 grams of phenyl benzoate,dissolved in the least quantity of benzene. After heating themixture to boiling for two hours, the benzene was distilled off, thesolid residue treated with ice-cold water, and the last tr.aces ofbenzene removed by current of air.The discoloured mixturecontaining benzo-o-toluamide and its sodium compound, partlydissolved and partly in the solid state, was filtered, and the filtrateacidified a t Oo with 30 per cent. acetic acid. The solid residue wasrepeatedly extracted with ice-cold aqueous sodium hydroxide, andthe filtrates immediately acidified.The combined precipitates,obtained by acidification, which were oily a t first, solidified quicklya t OD, and after remaining for thirty minutes were collected ,andwashed (11 grams). The solid (crude benzo-o-toluamide) was puri-fied, first by dissolving in sodium hydroxide, and, after filtering,acidifying with acetic acid, and subsequently by repeated re-crystallisation from 50 per cent. alcohol. It was thus obtainedin colourless, silky needles, melting indefinitely a t 147O :0*4122, by Kjeldahl's method, required 17.6 C.C. N / 10-HCI.N = 5.98.C,5K&,N requires N = 5.86 per cent.The persistently low melting point a t first led tlie authors tosuppose that the product was an isomeride of that obtained by th304 TITHERLEY AND STUBBS : THE HYDROLYSIS OFamidine method (p.303), but since no differences in propertiescould be detected, and since the melting point was not depressed byadmixture with the pure substance (m. p. 1 5 8 O ) , there can be nodoubt that the product melting at 147O is benzo-o-koluamide witha little isomorphous impurity (probably dibenzamide), which cannotbe removed by recrystallisation.This compound has been described previously by Wheeler,Johnson, and McFarland ( J . Amer. Chem. SOC., 1903,25, 787), andTitherley and Holden (T,, 1912, 101, 1877, 1887). It was obtainedeasily by the following new method of synthesis.Preparation from Benzamidi?ie.-The phenyl ptoluate, requisitefor the synthesis, described by Kraut (Jahresber., 1858, 406) as asolid, melting a t 71-72O, was prepared from p-toluoyl chloride andphenol by the Schotten-Baumann method (m.p. 72O), but a bettermethod was as follows.13.6 Grams of p-toluic acid, 15 grams of pure phosphoryl chloride,and 9 grams of phenol were heated a t 75O for four hours. Theresulting red liquid, after cooling and digesting with aqueoussodium hydroxide, solidified, and the red colour was removed byfurther digesting. The ester (22 grams) separates from hot alcoholas a white, crystalline powder, melting a t 76O. After repeatedrecrystallisation from .alcohol the pure ester melts at 83O.p-Toho y l b eizzamidiize, C,H,* C( :NH)*NR*CO*C,H,Me.Benzamidine (3 grams), freshly prepared from its hydrochloride,and phenyl p-toluate (5 grams) in alcohol (10 c.c.) were heated forfive hours at 50°; the alcohol was then mostly evaporated off, andthe residual oil, after cooling, shaken with dilute hydrochloric acid.I n most cases the oil (crude ptoluoylbenzamidine) completely dis-solved, but sometimes a little unchanged phenyl p-toluate remainedand was filtered off.The acid solution was immediately renderedalkaline in the cold by sodium hydroxide, in order t o liberate thefree base, which separated QS a milky oil, and crystallised afterseveral hours (8.5 grams). From light petroleum i t separated as amass of fine, silky, white needles, melting a t lllo:0.4604, by Kjeldahl's method, required 38.8 C.C. N / 10-HC1.N = 11'80C,,H,,0N2 requires N = 11.76 per cent.p-Toluoylb e?izamidi?ze is fairly readily soluble in alcohol, ether,chloroform, or acetone. It dissolves a t once in concentrated hydro-chloric acid, and the solution, if containing excess of acid, quicklMIXED SECONDARY AMIDES BY ALKALIS. 305deposits a voluminous, microcrystalline precipitate of the hydro-chloride (m.p. 21S0), which is readily soluble in water, moderatelyso in alcohol or chloroform, but very sparingly so in acetone.On heating the hydrochloride with aqueous hydrochloric acid,slow hydrolysis takes place with the formation of ammonia andbenzo-ptoluamide, which was prepared thus. Four grams ofptoluoylbenzamide were dissolved in 370 C.C. of AT/ 10-hydrochloricwid (2 mols.), and the solution was heated a t 70° for two hours.After about thirty minutes, the solution became milky as thesecondary amide began to separate, and this finally collected as amass of colourless needles, weighing 3.5 grams (theoretical yield,4 grams).After recrystallisation from dilute alcohol, the benzo-p-toluamidemelted a t 1 1 8 O , and repeated recrystallisation only raised the meltingpoint to 119O (Found, N=5-88.C,,H,,O,N requires N=5.86 percent.). The product was identical with that obtained by Titherleyand Holden (m. p. 114O, loc. cit.), and by Wheeler, Johnson, andMcFarland (m. p. 112--113O, loc. cit.) by the converse method frombenzoyl-ptolylamidine, C,H,Me*C( :NH)*NH*COPh, by .acid hydro-'lysis. When prepared direct from sodium ptoluamide by the actionof phenyl benzoate, by a method similar to that (p. 303) used in thecorresponding synthesis of benzo-o-toluamide, a much lower yield(30 per cent.) was obtained, and in spite of repeated recrystallisationa pure product could not be obtained.The appearance of thecompound was different (pearly flakes), and the melting point higher(varying with different samples between 125O and 130O) than thatobtained by the amidine synthesis, but correct figures were obtainedon analysis. It was a t first believed t o be a definite isomericcompound, but from an exhaustive examination of its propertiesand the products it yields on hydrolysis by alkali, the authorsconclude that the substance is a solid solution consisting of benzo-ptoluamide, di-ptoluamide, and dibenzamide, which cannot beseparated by fractional crystallisation.Hydrolysis of Secondary Amides by Alkalis.The ,study of the initial products of hydrolysis of secondaryamides by aqueous alkali was rendered easy by the fact that thefirst stage leading t o acid and primary amide is very sharplydefined, and is complete before any appreciable further hydrolysisof amide oan occur.I n the cold the latter is completely prevented,and the decomposition to acid and primary amide is therefore, so faras could be measured, practically quantitative. The curves belowshow the comparative rdes in the cold a t which hydrolysis occursof diacetamide, acetobenzamid e and acetylcarbamide, on the on306 TITHERLEY AND STUBBS : THE HYDROLYSIS OFha.nd, and of dibenzamide, benzo-o-toluamide, and benzo-p-tolu-amide, on the other, using in each cme two molecular equivalentsFit..1.10090807060504030201002 4 6 8 10 12 14 Id 18 20 22 24 26 28 30 32Tirne in rniimtes.o Diacetnmirlc . + Acetobenzamide. x Acelylcnrbamide.Hydrolysis of dincetaatide, ncctobenznmidt, and amtyZcarbc;midc by alknZi at 15",vising 2 eqibiualents of N/lO-NaOI-T.of sodium hydroxide at N l 10-concentration. These curves areconstructed from the figures obtained by titrating the alkalineHydrolysis of dibenzamide, benzo-o-toluamide, and bcnzo- p-tolztamide b y alkaliat 15") t6sixg 2 epuivabnts of N/10-NaOH.solution with LT / 10-hydrochloric acid a t intervals in order toascertain the a"mount of alkali used, and thus the percentagenumber of molecules of secondary amide hydrolysedMIXED SECONDARY AMIDES BY ALKALIS.307From these curves it is apparent that whilst diacetamide, aceto-benzamide, and acetylcarbamide are completely hydrolysed by dilutealkali in the cold within forty minutes, wholly aromatic second-aryamides require about fifteen hours; but there is no sensible differencein the rates of hydrolysis between dibenzamide, benzo-o-toluamide,and benzo-ptoluamide. Contrary to expectation, it was observedthat whilst the hydrolysis of the two benzotoluamides is completein less than one deay, using two equivalents of iV/lO-sodiumhydroxide, three to four days were required for complete hydrolysisunder similar conditions with 2N-sodium hydroxide. That is,hydrolysis is inhibited, not accelerated, by increase in the con-centration of alkali, and this may be due to decreased concentrationof the ions R*C‘(O’):N*CO*R’, which are probably more sensitive tohydrolysis than the non-ionised sodium salts R-C(ONa):N-CO*R’,the concentration of which would relatively increase with decreasein the relative mass of water.I n comparing the curves (Fig.1) for diacetamide, acetobenzamide,and acetylcarbamide, it will be noticed that the rate of hydrolysisof the first is considerably greater than that of the other’two. I nall three cases acetic acid is eliminated almost quantitatively, pre-sumably by water addition a t the double link in the commongrouping, *N:C(ONa)*CH3, acetamide, benzamide, and carbamide,being respectively formed. Whilst with acetobenzamide there isreason to believe that the alternative tautomeric form,NaO*&h:N*CO*CH,is present in the alkaline solution, and that this form suffers noappreciable hydrolysis owing to the steric influence of the phenylgroup, in the case of acetylcarbamide probably the tautomericform, NH,*CO*N:C(ONa)*CH3, only, exi&s in alkaline solution.The higher rate of hydrolysis of diacetamide cannot well be referredto reduced steric effects (compare acetylcarbamidej, and must arisefrom inferior stability, and in general it may be concluded that theadditive affinity for water of the grouping *N:C(ONa)*CH, andconsequent rate of hydrolysis varies somewhat with the nature ofthe group united to the nitrogen atom.The products of decomposition of the two bsnzotoluamides wereinvestigated after hydrolysis with two equivalents of 2N-sodiumhydroxide (1) a t 15’ by keeping for four days,.and (2) a t 90° byheating for three t o four minutes, and immediately cooling. I nthe cold no secondary hydrolysis of the resulting primary amideoccurred, and a t 90° the extent of hydrolysis was only slight; thiswas evident from control experiments (using N-sodium hydroxidea t 90° for three minutes) with benzamide, of which 16 per cent. washydrolysed, o-toluamide, of which less than 1 per cent. was hydro308 HYDROLYSIS OF MIXED SECONDARY AMIDES BY ALKALIS.lysed, and ptoluamide, of which 3 per cent. was hydrolysed. Theamide (or mixture of amides), which separated after alkalinehydrolysis of the secondary amide, was removed, and the smallquantity dissolved in the alkaaline solution was extracted by meansof ether.From the residual alkaline solution the acid (or mixtureof acids) produced by the hydrolysis was precipitated by acidifying,the small amount remaining in solution being recovered by extract-ing with ether.A. Be?Ezo-o-toluurrLide.--(l) A t 15O with 2h7-NaOH for four days :1.2 Grams gave a total of 0.641 gram of pure o-toluamide (m. p.137-139O before recrystallisation : Found, N = 10.35. Calc.,N = 10.37 per cent.). This amounts to 96 per cent. of the theoreticalif o-toluamide is the only primary amide produced by hydrolysis.Benzamide was looked for carefully and repeatedly in differentexperiments, but never found.1.2 Grams gave a total of 0.528 gram of pure benzoic acid (m.p.119-120° before recrystallisation), o r 87 per cent. of theoreticalpossible. NO o-toluic acid was found.The following results were obtained:(2) A t 90° for three minutes:1.2 Gra.ms gave a total of 0.6234 gram of pure o-toluamide (m.p.136-137O), or 93 per cent. of theory (Found, N=10*32. Calc.,N=10*37 per cent.). NO benzamide was found. 1.2 Grams gave0.5324 gram of pure benzoic acid (m. p. 117-120° before recrys-tallisation), or 88 per cent. of the theoretical.No o-toluic acid was found, and it'is clear that, although, owingt'o experimental difficulties, 100 per cent. yields were not realised,nothing other than o-toluamide and benzoic acid is formed by thealkaline hydrolysis of benzo-o-toluamide in the hot or cold.B.Beuzo-p-toZuamide.-(1) A t 15O with 28-NaOH for four days.1.2 Grams gave a total of 0.596 gram of a mixture meIting between125O and 136O, containing 22 per cent. of benzamide and 78 percent. of p-toluamide. By fractionalcrystallisation, an imperfect separation of the two amides waseffected.1.2 Grams gave a total of 0.529 gram of a mixture of acidsmelting between l l O o and 153O, containng 11 per cent. of p-toluicacid and 89 per cent. of benzoic acid (mixed silver salts gaveAg = 46.88 per cent.). By fractional crystallisation, an imperfectseparation, only, of the two acids was possible.(Found, N = 10.63 per cent.)(2) A t 90° for three minutes:1-2 Grams gave a total of 0-554 gram of a mixture meltingbetween 125O acd 142O, contaiiiiiig 49 per cent.of benzamide and51 per cent. of y-toluamide. (Found, N= 10.96 per cent.) 1.2 Gramsgave a total of 0.573 gram of a mixture of acids melting betweeHARTLEY AND STUART: THE MISCIBILITY, RTC. 3091 1 6 O and 155O, containing 60 per cent. of p-toluic acid and 40 percent. of benzoic acid (mixed silver salts gave Ag=45*54 per cent.).The quantitative values are only very approximate, since theyare based on the nitrogen value of the mixed (uncrystallised) amides,and the silver value of the mixed silver salts obtained from themixture of acids. Slight errors due to differences in solubilitybecome greatly magnified in view of the fact that differences in thefigures for nitrogen and silver respectively are, of course, relativelysmall, between benzamide and ptoluamide and between silverbenzoate and silver ptoluate.I n the hydrolysis a t 90°, moreover, there is a further error arisingfrom the slight hydrolysis of the two primary amides found, andsince the extent of hydrolysis of benzamide is considerably greaterthan that of ptoluamide, the proportion of benzaniide actuallyproduced would be somewhat higher than 49 per cent.Whilst in general, owing to lack of accurate means of quantitativemeasurement, the above data can only be taken as a rough approxi-mation, the following facts are established.A . Benzo-o-toluamide by hydrolysis with alkali, whether at 90°or in the cold, yields exclusively o-toluamide and benzoic acid; thatis, decomposes in one only of the two possible directions.B. Benzo-ptoluamide, in similar circumstances, decomposes inboth possible ways, in. the cold mainly along the channel yieldingptoluamide and benzoic acid, and at 90° to a tolerably equal extentin both directions.ORGANIC LABOILATORY,UNIVERSITY OF LIVERPOOL