[ 157 i 



No. 19. 



THE ACTION OF THE OXIDES AND THE OXYACIDS OF NITEOGEN 



ON PHENYL-METHYLUEEA. 



By HUGH EYAN, D.Sc, 



AND 



MICHAEL J. SWEENEY, M.Sc, 

 University College, Dublin. 



[Read Decembek 19, 1922. Printed Februaky 22, 1923.] 



Introduction. 



It has already been shown that nrethanes are more difficultly nitratable [H. Eyan 

 and A. Donnellan, p. 113; H. Eyan and N. Cullinane, p. 119; H. Eyan and 

 A. Connolly, p. 125 ; H. Eyan and J. O'Donovan, p. 131] than secondary 

 amines or nitrosamines. It has been shown also that the phenylureas [H. Eyan 

 and P. O'Toole, p. 139] resemble the urethanes in respect to difficulty of nitration 

 at low temperatures and concentrations of tlie interacting substances. 



In the present communication we describe the results of experiments we have 

 tried with phenyl-methylurea, which form the last of the series of comparative 

 experiments made in this laboratory on the nitration of nitrogenous aromatic 

 substances. 



Nitro derivatives of phenyl-methylurea have not hitherto been obtained, nor 

 do they appear to be formed under the conditions which we employed in the 

 following experiments. 



Nitrous acid readily converts the urea into methylaniline, and such derivatives 

 as we have isolated in our experiments can all be obtained from this base. 



Nitrogen peroxide in the vapour phase converts phenyl-methylurea into tetryl, 

 while in solution it forms on short action 4-nitro-phenyl-methyl-nitrosamiue, and 

 on more prolonged action 2-4-dinitro- and 2--4-6-trinitro-methylaniline are the 

 chief products. 



Nitrous anhydride acts on a solution of the urea in the same way as it does on 

 the amine [cf. E. Stoermer and P. Hoffmann, Ber. d. Dtsch. Chem. Ges., xxxi 

 (1898), pp. 2523-2541], forming on short action 4-nitro-phenyl-methyl-nitrosamine. 



Pure nitric acid (in the presence of urea nitrate) at low temperatures and 

 concentrations has little, if any, nitrating action on the urea, but in ihe presence 

 of nitrous acid or at more or less high temperatures, especially in carbon teti'a- 

 ehloride solution, it behaves towards the urea in the same way as it does towards 

 methylaniline, converting it into phenyl-methyl-nitrosamine, 4-nitro-phenyl- 

 methyl-nitrosamine, 2'4-diiiitro-methylaniline, 2'4-6-trinitro-methylaniline, and 

 finally into tetryl. 



SCIENT. PROC. R.D.S., VOL. XVII, NO. 19. 2f 



