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No. 39. 



THE ACTION OF THE OXIDES AND THE OXYACIDS OF NITROGEN 



ON DIPHENYLETHER. 



By HUGH RYAN, D.Sc, 



AND 



PETER J. DRUMM, M.Sc, 



University College, Dublin. 



(Read Decejieer IS, 1923. Printed February 27, 1924.) 



Introduction. 



In previous communications from this laboratory the behaviour of some 

 secondary amines, urethanes, ureas, and ethers towards the oxides and the 

 oxyacids of nitrogen has been described. 



Of the different substances examined, that which nitrated most smoothly 

 was diphenylnitrosamine. Its parent amine, diphenylamine, underwent complex 

 side-reactions during the course of its nitration [Proc. R.I. A., xxxiv, B, pp. 

 194, 212]. It seemed likely, therefore, that the diffei'ence in the behaviour 

 of the two bodies was due to the replacement of the oxidisable hydrogen 

 atom of the imino radicle by the nitroso group. It was shown later, however, 

 that when this hydrogen atom was replaced by a carbethoxy radicle the 

 urethane thus formed nitrated much less easily [Proc. R.D.S., xvii, N.S., No. 14] 

 than diphenylnitrosamine. 



Diphenylether corresponds closely in constitution with diphenylamine, and 

 as it does not contain an easily oxidisable radicle, it might be expected to 

 behave on niti'ation like diphenylnitrosamine. 



The action of nitric acid on diphenylether has been previously studied by 

 Mailhe and Muret [Comptes Rendus, cliv (1912), p. 715; Bull. Soc. Chim., x 

 (1913), p. 1011]. According to these chemists fuming nitric acid converted the 

 ether into 4-10-dinitrodiplienyIether, a trinitro derivative, a tetranitro derivative, 

 melting at 95° C, and a pentanitro derivative, melting at 86-88° C. In their 

 later communication they stated that this pentanitro derivative did not exist. 

 By the action of nitric acid on a solution of the ether in glacial acetic acid 

 they obtained 4-nitrodiphenylether. 



A. N. Cook [Journ. Amer. Chem. Soc, xxii (1910), p. 1285] converted 

 2-4-dinitrodiphenylether into a trinitro derivative, which we found to be 

 2-4-10-trinitrodiphenylether, and which we nitrated further to 2-4-810-tetranitro- 

 diphenylether, melting at 195° C. 



In our experiments nitric acid, in the absence of solvents, converted diphenyl- 

 ether into 4-nitro-, 2-10-, and 4-10-dinitro-, and 2-4-810-tetranitrodiphenylether. 

 Similarly from 2-4-6-trinitro- and 2-4-6-8-tetranitrodiphenylether we prepared 

 a pentanitro compound, melting at 210° C, and which was probably 2-4-6 8-10- 

 pentanitrodiphenylether. 



SCIENT. PEOC. R.D.S., VOL. X.VII, NO. 39. 3 N 



