158 Scientific Proceedings^ Royal Dublin Society. 



The only nitrosamines we isolated were phenyl-methyl-nitrosamine and 4-nitro- 

 phenyl-methyl-niti'osamine. The other nitrosamines known, which include 2 4- 

 dinitro-phenyl-methyl-nitrosamine melting at 86° C. [R. Stoermer and P. Hoffmann, 

 Ber. xxxi (1898), pp. 2523-i!541] and 2'4'6-trinitro-phenyl-methvl-nitrosamine 

 melting at 106-5° C. [E. Bamberger and J. Miiller, Ber. xxxiii (1900,1, pp. 100- 

 113], were not isolated. The same remark applies to the lower nitramine 

 derivatives, which include the 2-nitro-phenyl-methyl-nitramine melting at 67° C. 

 and the 4-nitro-phenyl-metliyl-nitramine melting at 140° C. of E. Bamberger [Ber. 

 d. Dtsch. Chem. Ges., xxx (1897). pp. 1248-1263]. 



Attempts to prepare nitro substitution derivatives of phenyl-methylurea from 

 nitro derivatives of methylaniline and cyanic acid have not hitherto proved 

 successful. 



In conclusion, the course of the reactions between phenyl-methylurea and the 

 oxyacids of nitrogen may be summarized as follows : — 



Phenyl-methylurea (M.P. 82° C.) 

 Y 



Phenyl- metliylamiue 



\ 



Phenyl-methj-l-nitrosamine 



2-Nitro-phenyl-methyl-iiitrosamine 

 (M.P. 36° C.) 



4-Nitro-phenyl-melhyl-nitrosamine (M.P. 100° C.) 

 I 



>■■ 



2-4-Dmitro-phenyl-methylamine (M.P. 175° C.) 

 I 



2-4-6-Trinitro-phenyl-methylaniine (M.P. 111° C.) 



I 



2-4-6-Trinitro-phenyl-methyl-iiitramine (tetryl). (M.P. 129° C.) 



Experimental. 



h.— action of nitrogen peroxide on phenyl-methylurea. 



I. — In the Vapour Phase. 



Two shallow glass dishes containing 2 g. of phenyl-methylurea and liquid 

 nitrogen peroxide were placed side by side on a glass plate under a bell-jar 

 and allowed to remain for a month at the room temperature. When the dark 

 reddish-brown liquid into which the phenyl-methylurea had been converted was 

 allowed to remain exposed to the air overnight, it became crystalline. The solid, 

 which melted at first about 118° C, on recrystallisation from alcohol and acetone 

 gave faint yellow crystals, which melted at 126°-127° C, and proved to be 

 identical with tetryl. A very small amount of a dark-coloured oil was obtained 

 by concentrating the alcohol-acetone filtrates. 



