Ryan and Glover — Nitro Derivatives of Dipheny /amine. 99 



derivatives of diphenylamine which are not usually met amongst the products 

 of the action of those acids on the hase. 



3-Nitro-diphenyIamine was converted by nitrous acid into its nitroso 

 derivative, and from the latter by the action of nitric acid in the cold a 

 crystalline compound, which melted at 184° C, and was apparently a trinitro- 

 diphenyluitrosamine, was obtained. 



On the other hand, 2.4.9-trinitro-diphenylamine was converted by 

 isoamylnitrite in acetic acid solution into a crystalline substance melting 

 at 190° C, the analysis of which agreed more closely with that required for 

 a tetra-uitro-diphenylamine than with that for a trinitro-diphenylnitrosamine. 

 A similar treatment of picryl-aniline yielded two compounds, one of which 

 melted at 236° C, and was probably 2.4.6. 8.10. 12-hexanitro-diphenylamine, 

 and the other melted at 193-194° C, and seemed to be 2.4.6.8.10-pentanitro- 

 diphenylamine. 



Experimental. 

 A. Mono-Nitro-Diphcniilamines. 



1. k-Niiro-diphenylamine O s N . C 6 H 4 . NH . C 6 H 5 . 



We obtained this substance in a manner similar to that by which it had been 

 previously prepared by Goldberg (foe. cit.). From the parent substances — 

 acetanilide and ^-nitro-bromo-benzene — utilised by us in the reaction, 

 the nitro-diphenylamine was formed in good yield. It was purified by 

 crystallisation from alcohol and carbon tetrachloride. From the latter 

 solvent it separated in large, beautiful, iridescent, yellow plates, which 

 became opaque on standing, or more rapidly on being heated. When dry it 

 melted at 133-134° C, and was found to be identical with the product 

 formed by the action of alcoholic potash on 4-nitro-diphenylnitrosamine. 

 According to Goldberg it should give a blue colouration with concentrated 

 sulphuric acid. We found, however, that its solution in concentrated 

 sulphurio acid was colourless, and became intensely violet on addition of 

 sodium nitrite. When warmed with alcoholic potash it formed a blood-red 

 coloured solution. 



2. 3-Nitro-Diphenylaminc 0,NC 6 H4 . NH . C 6 H 5 . 



We obtained 3-nitro-diphenylamine melting at 112° C. by the method 

 described by Goldberg (foe. cit.), and converted it by means of nitrous acid 

 into 3-iiitro-diphenylnitrosamine. To a well-cooled solution of 4 g. of 3-nitro- 

 diphenylamine and 3 g. of hydrochloric acid (sp. g. 1*19) in a little alcohol a 

 solution of 3 - 3 g. of sodium nitrite in 6 cc. of water was added slowly with 



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