984 



C = 73.217» H=:5.62 7o N = 13.11 7„. 



These figures agree fairly closely with those calculated forsymm 

 diphenylcarbamide, which melts at 235°. 



C = 73.58 7„ H = 5.66 7„ N = 13.21 7.. 



There was no depression of the melting point of a mixture of the 

 substance with symm. diphenylcarbamide, so that the formation of the 

 latter was established. Probably in this reaction methylcarbanilide 

 was formed as an intermediate product, from which and from the 

 aniline hydrochloride, also formed in the reaction, the diphenyl- 

 carbamide would be formed by elimination of methylaniline. Therefore 

 an experiment was made to see whether symm. diphenylcarbamide 

 is formed by heating methylcarbanilide with aniline hydrochloride. 

 This was indeed found to be the case; the reaction product was 

 identified as such. 



Now Gebhardt^), who observed analogous transformations with 

 arylthiocarbamides already showed that methylcarbanilide breaks up 

 on distillation into methylaniline and phenylisocyanate. We might 

 therefore assume that in the present case phenylisocyanate is first 

 formed and that this substance subsequently combines with aniline 

 to form diphenylcarbamide. Against this view, however, is the fact 

 that methylphenylthiocarbamide, which on boiling with aniline also 

 gives diphenylthiocarbamide'), furnishes phenylthiocarbamide and 

 methylaniline already by heating with alcoholic ammonia to 100°. 

 Moreover the above mentioned transformation reminds one of the 

 displacement, described by van Romburgh ') and Miss Wensink, of 

 the dimethylamino group by NH, or NHCHj in 2:4-dinitro- 1:3- 

 phenylenediamine derivatives, with the aid of ammonia or methyl- 

 amine; in that case fission of the original product is pretty well 

 excluded. 



A few further examples of this reaction were investigated. 



Dimethylcarbanilide CO [N^CHj) (C^HJ],, prepared according to 

 MiCHi.ER*), and heated with 2 molecules of aniline hydrochloride, 

 again yielded symm. diphenylcarbamide. 



Diethylcarbanilide CO[N(C2H5)(CaH5)J also prepared according to 

 MiCHLER^) gave the same product when similarly heated with aniline 

 hydrochloride. 



') B. B. 17. 3036. (1884). 



2) loc. cit. pag. 3034. 



') These Proceedings. XVII p. 1034. In the organic chemical laboratory of Utrecht 

 other analogous cases have been demonstrated with alipbalic amines; they will 

 be examined systematically. 



*) B.. B. 12. 1166 (1879). 



5) B. B. 9. 712 (1876). 



