[ 287 ] 



No. 36. 



THE ACTION OF THE OXIDES AND THE OXYACIDS OF NITROGEN 

 ON PHBNYLBENZYLETHER. 



By HUGH RYAN, D.Sc, 



AND 



JOHN KEANE, Ph.D., 

 Universitj" College, Dublin. 



(Read Decejsiber IS, 10:23. Piiuted February 27, 1924.) 



Introduction. 



In a previous communication [Proc. R.D.S., xvii, N.S., No. 17] it has been 

 bhovvn by H. Ryan and J. L. 'Donovan that phenylbenzylurethane is difficult 

 to nitrate, but that it can nevertheless be nitrated both in its phenyl and in 

 its benzyl radicle without decomposition of the urethane. Thus at the ordinary 

 temperature nitrogen peroxide converted it into a trinitrophenylbenzylurethane. 

 It was also converted by nitric acid at more or less high concentrations into a 

 tetranitro, and probably also a pentanitro, derivative. Secondary reactions, 

 resulting in the formation of nitrobenzoic acid and nitrophenylurethanes, also 

 occurred. But, in regard to ease of nitration at low temperatures and con- 

 centrations, the substance was very inferior to diphenylnitrosamine, and it 

 seemed of interest therefore to find how the somewhat analogous oxy-compound, 

 phenylben^ylether, would behave under similar conditions. 



The action of nitric acid on 4-nitro-, 4'-nitro-, 2-4-dinitro-, and 2-4'-dinitro- 

 phenylbenzylether^ has been already investigated by G. Kumpf [Lieb. Ann. d. 

 Chem. eciv, 1884, p. 96], but under conditions which are not evident from 

 his communication. In his experiments he obtained 2-4-4'-trinitro-, 4-4'-dinitro-, 

 and probably 4-2'-dinitrophenylbenzylethei\ In general in our experiments, 

 which were for the most part carried out at the laboratory temperature and 

 at low concentrations of the interacting substances, the same products were 

 obtained. 



Nitrogen peroxide reacted rapidly with a four per cent, solution of the 

 ether in carbon tetrachloride forming 4-nitrophenylbenzylether, which was 

 then very slowly converted into its 4-4'-dinitro derivative. During the prolonged 

 action of the peroxide secondary reactions also occurred, and these gave rise 

 to the formation of tarry bodies and a substance soluble in alkali. The main 



' The nomenclature adopted in this communication is based on the following formula : — 



<4 1> 1) CH, <1' 4> 



\L_!/ X*^' '/ 



SOIENT. PROC. E.D.S., VOL. XVII, NO. 36. 3 j 



