60 



Dr. Hofinann on the Action of Trichloride 



[Mar. 22, 



Aniline, toluidine, and naphthylamine being primary monamines, it 

 seemed of interest also to extend the examination to a secondary one. For 

 this purpose I selected diphe?iylamine. When a mixture of diphenylamine 

 and phenjlacetamide, in the proportion of their molecular weights, was 

 submitted to the action of trichloride of phosphorus, the reaction took 

 place in the ordinary way, but the mass precipitated from the solution of 

 the chloride by ammonia could not be crystallized. It had therefore to be 

 analyzed as platinum-salt. Determination of the platinum as well as com- 

 bustion showed, however, that the expected ethenyltriphenyldiamine 

 been formed, 



C,H, N + C. H, N= O + (C, H,), N,. 

 H I H J ^> (C,li,) J 



An entirely unexpected result, on the other hand, was obtained by the 

 action of trichloride of phosphorus on a mixture of acetic acid and methyl- 

 aniline. Working, as I did, exclusively with a secondary monamine, I had 

 expected to see the reaction take place according to the following equation: — 



C.H,|n |4-^^g'°}o = 2LH}oJ + (C H3)3 |n3. 



But this was not the case ; the action was found to have been very irre- 

 gular ; and amongst the products a chloride was observed, the base of 

 which, when liberated by oxide of silver, dissolved in water with an alka- 

 line reaction. When analyzed in the form of a platinum-salt, this body 

 proved to be ethenyldiphenyldiamine, which had twice appropriated the 

 methyl-group, having the composition 



[(C,H3r(C. H,),(CH3)NJCH3 jQ_ 



In this case evidently chloride of methyl had been eliminated from one of 

 the molecules of methylamlincj which, acting on the ethenyldiphenylme- 

 thyldiamine, had given rise to the formation of the chloride corresponding 

 to the above-mentioned oxide, 



2[(Ce H5) (C H3) HN] + C, H3 O C1=H, O 



4- [(C, H3)'" (C, H,), (C H3) NJ (C H3) CI. 



A few experiments made with the derivatives of valeric and benzoic acids 

 are still to be mentioned. 



Quint enyldiphenyldiamine. — For the preparation of this substance, 3 mo- 

 lecules of valeric acid were mixed with 6 molecules of aniline, and to the 

 liquid, after cooling, 2 molecules of trichloride of phosphorus were added. 

 Tins mixture, on being submitted for a couple of hours to a temperature of 

 150°, yielded a viscous mass soluble in water. From the solution hydrate 

 of sodium precipitated a crystalline base almost insoluble in water, which 

 v. as recrystallized from alcohol. This substance fused at 1 1 1°. The com- 



