160 Scientific Proceedings^ Royal Dublin Society. 



2. An aqueous solution, containing 8'4 g. of nitric acid, was added slowly to a 

 cold solution of 5 g. of phenyl-methylurea and 5 g. of sodium nitrite in 25 c.c. of 

 water. A colourless oil first separated; but when the mixture was warmed for 

 some hours on the water-bath the oily nitrosamine was gradually converted into a 

 solid, which, when recrystallised from alcohol, melted at 99°-100°C., and proved 

 to be 4-nitro-phenyl-methyl-nitrosamine. 



In a similar experiment, in which, however, sodium nitrite was not added to 

 the reaction mixture, the only change observed consisted of the formation of a 

 small amount of methylaniline. 



(j3) At low concentrations. — Four solutions, each containing 1 g. of phenyl- 

 methylurea in 50 c.c. of water, to which one, two, three, and four molecular 

 amounts of nitric acid had been added respectively', were allowed to remain in. 

 stoppered bottles at the temperature of the room for about six weeks. The 

 solutions, which had remained nearly colourless, were neutralized with sodium 

 carbonate, saturated with sodium sulphate, and extracted with benzene. Almost 

 all the phenyl-methylurea was recovered unchanged in each case. 



(b) Alcohol.' — As phenyl-methylurea was recovered unchanged from an 

 alcoliolic solution of it to which nitric acid containing urea nitrate had been 

 added, and which had been allowed to remain at the temperature of the room for 

 a couple of weeks, the experiment was varied by including nitrous acid in the 

 interacting substances. 



For this purpose aniline was converted into methylaniline by the method of 

 G. T. Morgan (E.P. 102,834), and the methylaniline, without isolaling it, was 

 converted directly into its nitrosamine, which was separated from the simultaneously 

 formed diazoniiim salt by means of ether; the pheiiyl-methyl-nitrosamine left on 

 evaporation of the ether was further purified by distillation in a current of steam, 

 and the product thus got was employed in the reactions described below : — 



A solution of 5 g. of phenyl-methyl-nitrosamine in 100 c.c. of alcohol to which 

 0'75 c.c. of nitric acid (sp. g. 151) had been added was heated on the water-bath 

 for five hours. The solid which separated on cooling melted at OQ^-IOC^ C, and 

 consisted of 4-nitro-phenyl-methyl-nitrosamine. 



(c) Acetic acid, (a) At ordinary concentrations. — 1. To a mixture of 10 g. of 

 plienyl-methylureaand 20 c.c. of glacial acetic acid 5'5 c.c. (two molecular amounts) 

 of nitric acid (sp. g. I'Sl) were added slowly. A solution of 5 g. of sodium nitrite 

 in about 1 c.c. of water was then allowed to drop into the mixture, the temperature 

 of which was kept below 30" U. during the addition of the nitrite. A crystalline 

 solid separated from the solution, the latter becomiug almost black in colour. 

 After remaining overnight the solution was filtered and the solid was dissolved 

 in hot alcohol, from which it separated in the form of almost colourless acicular 

 prisnrs melting at 100" C, and consisting of pure 4-nitro-phenyl-methyl-nitro- 

 samine. 



On addition of water to the acetic acid filtrate a small amount of 2'4-dinitro- 

 meihylaniline was obtained. 



The nitro-nitrosamine obtained in this experiment was heated with con- 

 centrated hydrochloric acid and alcohol under a reflux condenser until the evolution 

 of nitrous fumes had ceased. The reddish yellow solution was cooled, diluted 

 with water, and neutralized with sodium carbonate. The yellow solid which 

 separated was filtered, washed with water, and recrystallised from alcohol. The 

 yellow crystals thus got melted at 151° 0., and consisted of 4-nitro-methylaniline. 



2. In anotlier experiment 20 c.c. of fuming nitric acid (sp. g. 1-51) were 

 added to a solution of 5 g. of phenyl-methylurea in 50 c.c. of glacial acetic acid, 



