[ 131 ] 



No. 17. 



THE ACTION OF THE OXIDES AND THE OXYAGIDS OF NITKOGEN 

 ON PHENYL-BENZYLURETHANE. 



By HUGH EYAN, D.Sc, 



AND 



JAMES L. O'DONOVAN, M.Sc, 

 University College, Dublin. 



[Bead Decembku 19, 1922. Printed Febiiuaky 22, 1923.] 



Inteoduction. 



In previous communications the action of the oxides and the oxyacids of nitrosjen, 

 more especially at low temperatures and concentrations, on derivatives of some 

 aromatic amines has been described. H. and P. Eyan showed [Proc. E.I.A., 

 xxxiv, B, pp. 194 and 212] that diphenylnitrosamine nitrated more easily and 

 more smoothly than dipheuylamine. When, however, the imino hydrogen atom 

 of dipheuylamine was replaced by a earbethoxy radical, the urethane thus formed 

 nitrated [H. Eyan and A. Donnellan, p. 113, above] with difhculty at the ordinary 

 temperature and at low concentrations of the nitrating acid. 



Similar decreases in the ease of nitration due to the substitution of an ethyl 

 radical for an imino hydrogen atom were found by H. Eyan and N. Cullinane 

 (p. 119) with ethyl-o-tolylurethane, and by H. Ryan and A. Connolly 

 with ethyl-phenylure thane. Nitro derivatives of ethyl-phenylurethane were 

 formed by nitration at the ordinary temperature, but only nitro derivatives of 

 o-tolylurethane were got in similar experiments with ethyl-o-tolylurethane. 



Of the three urethanes examined, only diphenylurethane contained two 

 nitratable radicals, and these were both purely aromatic. For purposes of com- 

 parison it appeared of interest to examine the nitratability of a urethane, such as 

 phenyl-benzylurethane, which would contain two nitratable residues, only one of 

 which would be a purely aromatic radical. 



Neither phenyl-benzylurethane itself, which is a colourless oil, and for which 

 we are indebted to Nobel's Explosives Company, nor any of its nitro derivatives 

 has hitherto been described in the literature. 



By the action of nitrogen peroxide and of nitric acid on phenyl-benzylurethane, 

 Dr. Nolan [private communication from Nobel's Explosives Company] obtained 

 benzoic acid, paranitro-pheuylui'ethane, benzaldehyde, p-p'-phenyl-dinitro- 

 diphenylurea, o-nitro-phenylurethane, and an oil which must mainly have consisted 



SCIENT. PROC. R.D.S., VOL. XVII, NO. 17- 2 



