314 Scientific Proceedings, Royal Dublin Society. 



At low concentrations of the interacting substances and at the ordinary 

 temperature, nitric acid had scarcely any action on diphenylether in acetic 

 acid solution. When, however, the solution contained 24 molecular amounts 

 of nitric acid 4-nitrodiphenyl ether, 2-4-dinitrophenol, and, probably, 2-nitro- 

 diphenylether were fonned. In carbon tetrachloride solution, even at low 

 concentrations of the acid and the ether, the latter was converted into 4-nitro-, 

 2-10-, and 4-10-dinitrodiphenylether, and 2-4-dinitrophenol. 



Nitrogen peroxide acted rapidly on diphenylether producing 4-nitro-, 2- 10-, 

 and 4ld-dinitrodiphenylether, with 2-4-dinitrophenol. Nitrogen sesquioxide 

 behaved like the peroxide. 



Although diphenylether nitrates more easily than diphenylurethane, and mon. 

 smoothly than diphenylamine, it is not in either of these respects so readily 

 acted upon as diphenylnitrosamine.. Moreover, its tetranitro derivative 

 decomposes rather easily into dinitrophenol. 



The course of the nitration of diphenylether and its nitro derivatives may 

 be conveniently represented by the following diagram : — 



Diplienvlether 



(M.P. 28°C.) 



I 



I ^ ] 



sl/ A/ 



2-Nitiodiiihenvlettiei- 4-Nitro.liphenylethei- 



(Oil.)' (M.P. 61° C.) 



2'10-Diniti-<Hlipheiiylethei' 

 (M.P. 103-o"C.) 



I 



s!/ 



4'10-niniti-odiptieiivlethei' 

 (M.P. 143° C.') 



2-4-8'10-Telranitrodiphenyletliei- 

 (M.P. 190° C.) 



t 

 'i-4-lO-TiinitiotliphenyIether 

 (M.P. 114° C.) 



.t 

 2'4-Dinitrodiphenylethei' 

 (M.P. 71° G.) 



2'4-6-Triiiiti-odiphenylether 2-4-6-8-Teti-anitrodiphenyIether 



I 



2-4'6-S-lO-Pentaiiitrodiphenyletliei- 

 (M.P. 210° C.) 



Experimental. 

 1. Preparation of Diphenyletlier and its Nitro Derivatives. 



Before examining the behaviour of diphenylether towards the oxides and 

 the oxyacids of nitrogen it was necessary to select a convenient method for its 

 preparation, and also to determine the properties of such derivatives of it 

 as could be obtained from the nitrophenols at our disposal. 



(a) Diphenyletlier. — We found the methods of Gladstone and Tribe [Journ. 

 Chem. Soc, xli (1882), p. 8] ; Merz and Weith [Ber. Dtsch. Chem. Ges., xiv 

 (1881), p. 189] ; and Hoffmeister [Liebig's Annalen, clix (1871), p. 191], 

 inconvenient for the preparation of this substance, which can, on the other 

 hand, be readily made by the method of Ullmann and Sponagel [Ber. Dtseh, 

 Chem. Ges., xxxviii (1905), p. 22117]. 



