Chemistry. — ''On the replacement, in aiiiide.s, of an alky lanil mo- 

 group hij an aniline group, hy heating with aniline hydro- 

 chloride.'' By G. DE Bruin. (Communicated by Prof. P. v. 

 Romburgh). 



(Communicated in the meeting of December 29. 1917). 



¥ov the preparation of certain other carbamide derivatives, vv^hich 

 I hope to describe later, I required a quantity of methylcarbanilide 

 (CH3)(CeH,)N .CO.NH .C«H,. Gebhardt^) first obtained the hitter 

 compound from methylaniline and plienylisocyanate. Since, however, 

 a quantity of methylphenylcarbamic chloride (CH3)(C6H5)N . CO . CI 

 was already available, 1 attempted to utilise it for the preparation 

 of the desired substance. Accordingly one grammolecule of the chloride 

 was dissolved in ether and two grammolecules of aniline were 

 added. On warming under a reflux condenser aniline hydrochloride 

 at once separated. Since the precipitate caused violent bumping it 

 was found desirable to add a little water, in which it dissolves. 

 In order to complete the reaction boiling for about 30 hours was 

 necessary. After separation of the two layers, the ether was evaporated 

 and the crystalline residue was ground up with dilute hydrochloric 

 acid in order to remove adhereiit aniline. After one recrystallisation 

 from alcohol a pure |)roduct, melting at 104° C, was obtained in 

 practically theoretical yield. 



Since the reaction proceeds so smoothly, an attempt was made to 

 obtain the same result more rapidly by heating aniline with the 

 chloride without dilution with ether and at a higher temperature. 

 Two molecules of aniline were melted on a sand bath with one 

 molecule of methylphenylcarbamic chloride and heated to about 

 190°. Copious fumes of hydrochloric acid were evolved and the 

 liquid smelt strongly of methylaniline. After heating for two hours 

 the mass was poured into cold water and the liquid was acidified 

 with hydrochloric acid. The crystals were sucked off and recrystal- 

 lised twice from alcohol. The product melted at 236° C. and was 

 therefore not methylcarbanilide. A complete analysis gave the following 

 result : 



1) B. B. 17. 2093 (1884). 



