Ryan & Sweeney — Action of Oxides, Sfc, on Phenyl-Methylurea. 161 



and the mixture was heated for an hour on the water-bath. Nitrous fumes were 

 evolved, and a dark, somewhat oily solid separated when the solution was poured 

 into water. When this solid was crystallised from alcohol it melted, but not 

 quite sharply, about 111° C, and consisted of 2'4-6-trinitro-methylaniline. 



3. Phenyl-methyj-uitrosamine (4-5 g.) was dissolved in warm acetic acid 

 (10 c.c), and to the solution 2'3 c.e. of fuming nitric acid (sp. g. 1-51) were added 

 slowly. The mixture was heated to boiling for a few minutes, then diluted with 

 water and cooled. The solid which separated was filtered, washed with water, 

 and recrystallised from alcohol. About 3 g. of pure 2'4-dinitro-methylaniliue 

 melting at 175°C. were thus got ; the pai-ent liquid contained a small amount of an 

 oily solid, probably consisting of the same substance. 



(j3) At low concentrations. — To four solutions of 5 g. of phenyl-methylurea in 

 100 g. of glacial acetic acid quantities of nitric acid corresponding to one, two, 

 tliree, and four molecular amounts were added, and the solutions allowed to remain 

 at the temperature of the room for about three months. 



In no case was there any indication of the occurrence of any appreciable 

 amount of reaction between the constituents. No solid separated from the 

 mixtures, and when they were poured into water the solutions remained in all 

 cases clear. 



(d) Carbon tetrachloride. — At loiv concentrations. — As phenyl-methylurea is 

 only sparingly soluble in cold carbon tetrachloride, it was found inconvenient in 

 this case to carry out the reactions at the temperature of the room. 



Tour solutions were prepared, containing in each case 5 g. of phenyl-methyl- 

 urea in 100 g. of carbon tetrachloride at 60° C. Quantities of fuming nitric acid 

 (sp. g. 1'51) corresponding to one, two, three, and four molecular amounts were 

 added to these respectively. In each case a vigorous reaction set in, with evolution 

 of nitrous fumes and separation of a dark brown oily layer. The mixtures were 

 allowed to remain at the tempei'ature of the room for three months. 



They were then shaken with water, the carbon tetrachloride was in each case 

 separated, and the aqueous washings returned to the solid or tany matter in the 

 flask. 



1. By distilling the deep yellow carbon tetrachloride solution from the flask to 

 which one molecular amount of nitric acid had been added aboiit 0'5 g. of tetryl 

 was obtained. 



The aqueous portion was made alkaline and extracted with ether. Methyl- 

 aniline was extracted from the ether solution by means of hydi'ochloric acid, and 

 after reconversion into the free base and extraction with ether boiled at 

 192°-194° C. 



2. From the carbon tetrachloride solution to which two molecular amounts of 

 nitric acid had been added we isolated, on the other hand, a small amount of 4- 

 nitro-phenyl-methyl-nitrosaniine ; while Irom the mixture of the aqueous and 

 undissolved portions in the flask we obtained a further quantity of 4-nitro-phenyl- 

 methyl-nitrosamine and 2-4-dinitro-methylaniline. 



3. In the case of the solution to which three molecular proportions of nitric 

 acid had been added distillation of the neutralized carbon tetrachloride solution 

 gave a small amount of a crystalline residue, which, when washed with ether, 

 melted at 175° C, and consisted of 2-4-dinitro-methylaniline. 



The mixture of solid and- water in the flask was shaken with ether. The lower 

 aqueous layer was filtered from a yellow solid (O'S g.), which consisted of 2-4-dinitro- 

 methylaniline (M. P. 175° C), and the ether solution, after washing with dilute 

 sodium carbonate, gave a further quantity (0-75 g.) of 2 4-6-trinitro-methylaniline. 



SOIENT. PROC. R.D.S., VOL. XVII, NO. 19. 2 » 



