Ryan & Kunny— ^4 ction of Oxides of Nitrogen on Diphenylethyleneether. 307 



Experimental. 

 1. Action of Nitrogen Peroxide on Diphenylethyleneether. 



(a) In the Absence of Solvents. — Diphenylethyleneether (10 g.) and dry 

 liquid nitrogen peroxide were placed in shallow dishes, side by side, under a 

 bell-jar. The ether absorbed the nitrogen peroxide, and quicldy changed into 

 a dark-brown, tarry mass. The nitrogen peroxide was renewed at intervals 

 during the first 15 days, after which time the absorption of the fumes 

 became much slower. At the end of 5 weeks the tarry mass had become 

 again, to a large extent, crystalline. On treating the mixture with chloroform 

 a portion (3-1 g.) dissolved, forming a red solution from which, on evaporation, 

 red crystals separated. These crystals became yellowish-white on standing 

 m the air and melted at 143-144° C. The portion which was not so readily 

 soluble in chloroform dissolved in hot alcohol, giving a green solution, from 

 which 2-2 g. of green crystals separated on cooling. These crystals also melted 

 at 143-144° C, and their melting-point was not affected by the addition to 

 them either of the red crystals mentioned above or of 4-10-dinitrodiphenyl- 

 ethyleneether, which was prepared by the method of Weddige [Journ. f. pr. 

 Ch. (2), xxi (18S0), p. 127] from p-nitrophenol and ethylene dibromide. When 

 the alcoholic filtrate was concentrated about 7 g. of an oil remained, from which 

 light petroleum separated a very small amount of a crystalline body melting, 

 and exploding violently, at 203° C. 



(&) In Carbon Tetrachloride Solution. — A solution of 5 g. of diphenyl- 

 ethyleneether in 200 g. of carbon tetrachloride was saturated in the cold with 

 nitrogen peroxide vapour and was allowed to remain several weeks in a 

 stoppered flask. A substance which rapidly separated gradually became 

 crystalline, the colour of the solution at the same time changing from brownish- 

 red to light orange-red. The crystalline solid was filtered and washed with 

 ether and alcohol. It weighed 4 g. After recrystailisation from xylene, it 

 melted at 143-144° C, and proved to be 4-10-dinitrodiphenylethyleneether. 

 A- further quantity of this substance mixed with some 2-4-dinitrophenol was 

 obtained from alcoholic filtrate. 



The carbon tetrachloride solution was washed with aqueous potash and 

 then, on evaporation, gave a small amount of unchanged diphenylethylene- 

 ether. From the reddish aqueous potash solution, by acidification and extraction 

 with ether, about 04 g. of 2-4-dinitrophenol was obtained. 



2. Action of Nitric Acid on Diphenylethyleneether. 



(o) In the Absence of Solvents. — Diphenylethyleneether (10 g.) was added 

 slowly to 12 g. of cold concentrated nitric acid (Sp. g. 1-4). P''rom the mixture, 

 which was allowed to remain at the temperature of the room for two days, 

 most of the original ether was recovered, together with a very small amount 

 of oily matter, which did not crystallise. When, however, the mixture was 

 heated on the water-bath for several hours, some 410-dinitrodiphenylethylene- 

 ether was obtained. 



{b) When cold fuming acid (Sp. g. 1-52) was employed, in an experiment 

 similar to the last, about 5 g. of 4-10-dinitrodiphenylethyleneether and 1 g. 

 of a substance which was less soluble in acetic acid were obtained. The less 

 soluble substance separated from boiling acetic acid and xylene in the form 

 of yellowish-white flat prisms, melting at 214" C. It gave on analysis the 

 following results : — 



01830 g. substance gave 224 c.c. moist nitrogen at 16° C. and 764 m.m. 

 corresponding to N 14-28 

 Ci^H.oOioN^ requires N 14-21. 



