Nolan and Clapham — The Utilisation of Monomethylaniline. 223 



commercial article, through its uitrosamine, for the production of tetryl, and 

 ' recovering- dimethylaniline from the add liquors, aftei- separating off the 

 nitrosamine, by neutralisation and subsequent steam distillation. It would 

 prolDably, however, be more suitable after the formation of the nitrosamine to 

 neutralise the residual solution of dimethylaniline hydrochloride, and add the 

 recovered dimethylaniline to the nitrosamine for nitration of the mixture. 



Experiment 4. — Nitration of Metkylaniline dissolved in sulphuric acid con- 

 taining sufficient nitrous acid to form the nitrosamine. 



24 g. of monomethylaniline were dissolved in 120 g. of suli)huric acid 

 97 per cent., and to this solution, which had been cooled to 0° C, was added a 

 solution of 285 g. of nitrosyl sulphuric acid dissolved in 120 g. of .sulphuric acid. 

 The mixture was nitrated in the manner described in j^revious experiments, 

 using 84 g. of 92 per cent, nitric acid. The nitration proceeded quite normallj^ 

 The nitro body as filtered off from the waste acid was very red in colour as 

 comjjared with products from previous nitrations. In the first boiling the 

 nitro body darkened considerabl.y, and the colour of the resulting wash water 

 was deep orange. On evaporation, 4'1 g. oJ' crude oxy-tetryl was obtained. 

 After the usual hot water washings, the nitro bodj' was yellowish brown. The 

 yield was 450 g., being 70 per cent, of tlie theoretical, and the product melted 

 at 126-127° C. (corr.). Eecrystallisation from aqueous acetone did not affect the 

 melting point. 



Experiment 5. — Nitration of a sulijliuric acid solution of pure methyl phenyl 

 nitrosamine allowed to stand in a closed vessel for 2i hours before nitration. 



The methyl phenyl nitrosamine (30 g.) dissolved in 97 per cent, sulphuric 

 acid (300 g.) was allowed to stand in a stoppered bottle at room temperature for 

 24 hours. It was then nitrated in the manner already described for the other 

 expei'iments. It was noted during the nitration that the nitro body did not 

 separate from the acid solution very quickly, and even then it tended to be 

 somewhat sticky, vigorous agitation being necessarj' to bring it down in a 

 workable condition. The same characteristics were noted with the product as 

 had been obser^'ed in Experiment 4. The wash waters gave 47 g. of crude oxj-- 

 tetryl. The yield of tetryl obtained was 39 g., being 62 per cent, of the 

 theoretical. Melting point, 1260-1270 C. (corr.), unchanged by recrystallising 

 from aqueous acetone. 



Experiment 6. — Nitration of p-nitrosu mononiethylaniline. 



The pure base, m.p. 114-114T)° C. (20 g.), was dissolved in 97 per cent, 

 sulphuric acid (200 g.), and nitrated as described in previous experiments, with 

 56 g. of 92 per cent, nitric acid. 



The nitration proceeded quite smoothly, and was easily controlled. The 

 nitro body, on filtering oft' from the waste acid, was deep red in colour ; and after 

 the usual hot-water washing was obtained as a brownish coloured product, with 

 a m.p. of 125-5-126-5° 0. (corr.). The yield obtained was 36 g., being 853 per 

 cent, of the theoretical. 



No ox3'-tetryl ^vas obtained from any of the wa.sli waters. On recrystallising 

 from aqueous acetone, the melting point was 1290-129'5° C. (corr.). 



We desire to thank Messrs. Nobel Industries, Ltd., for permission to publish 

 these results. 



Nobel Research Laboratories, Ardeer. 



3CIENT, PKOC. E.D.S., VOL. XVII, NO. 25. 2 S 



