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XII. 



ON THE ACTION OF NITRIC ACID AND NITROUS ACID ON 

 DIPHENTLAMINE 11. 



By PROFESSOR EUGB RYAN, D.Sc.and MISS PHYLLIS RYAN, M.Sc, 

 University College, Dublin. 



bhbbh 30, r.'is. Published Fbbudarv 13, 1919. 



In ..in iii — i communication [Proc. Royal Irish Acad., XXXIV, b, p. 104] the 

 ixperiments on the action of nitric acid on diphenylamine and 

 diphenylnitrosamine in acetic acid solution were described. With a view to 

 maintaining as full;- asible the conditions which obtain when the 



decomposition pi ellulosi powder interact with diphenylamine 



during I go of a powder stabilised with this base, we allowed the 



for Long periods at low temperatures and low 



entrations of the interacting bodies. 



It was found that when a 2 per cent, solution of diphenylamine in glacial 

 acetic acid was mixed with an equivalent amount of nitric acid the solution 



lually be in colour without separation of any solid. The 



dipheny nn this solution even 



when the solution had 1 a allowed to remain for six weeks at the room 



temperature. When the quantity of niti dded corresponded to two> 



three, four, or six equivalent amounts of the acid a brownish-red, resinous 



oxidation pr liphenylainin id, and in the case of the 



which tin i itnounts of nitric acid had been added the acetic 



usually contained 2.4.8. 10-tetranitro-diphenylamine. In some cases 4.10- 



dinitro-diphenylamine, and in our case a small amount of a dinitro-diphenyl- 



nitrosam mainly of 2.10-dinitro-diphenylnitrosamine, were 



Other products were obtained in small quantity which we were 



una' late in a pure state. 



In the experiments with diphenylnitrosamine, which were conducted 

 under similar conditi btained in relatively large amount a mixture of 



2.10- and 4.10-dinitro-diphenylnitrosamini 3ting mainly of the former 



nicrosamine. W liphenylnitrosamine, 4.10-dinitro- 



diphenylamine, and 2.4.8.10-tetranitro-diphenylamine. There wen- indications 



