316 Scieniific Proceedings, Royal Dublin Society. 



ether, and recrystallisation from dilute alcohol, 2-4-dinitrophenol was obtained. 

 When the ether solution, which had been washed with dilute alkali, was 

 allowed to evaporate, a dark-red oily substance remained, and this, when 

 shaken with acetone, to a large extent dissolved, leaving a small amount of 

 a crystalline solid,- which melted at 142° C, and which gave on analysis the 

 following results : — 



01000 g. substance gave 9-4 c.c. moist nitrogen at 16° C. and 764 m.m. 



corresponding to Nll-1 

 CjoHsO^N^ requires N 10-8. 



The latter compound was, therefore, a dinitrodiphenylether, and must have 

 been identical with the 410-dinitrodiphenylether, melting at 143° C, which 

 Haussermann and Teichmanu [Ber. Dtsch. Chem. Ges., xxix (1896), p. 1448] 

 obtained from 4-nitroehlorobenzene and the potassium derivative of 4-nitro- 

 phenol. 



The light-red oil, left on evaporation of the acetone, did not crj'-stallise. 



In another experiment, under somewhat different conditions of temperature, 

 the main product was 4-10-dinitrodiphenylether, and with it were mixed 

 2-4-dinitrophenol and some unchanged diphenylether. 



{h) In C avion Tetrachloride Solution. — Nitrogen peroxide vapour was passed 

 for some time through a solution of 4 g. of diphenylether in 80 g. of carbon 

 tetrachloride. After remaining for 6 weeks at the temperature of the room, 

 the reddish-coloured solution was filtered from the red tarry solid, which had 

 separated, and distilled. The tarry-red solid and the residue left on the 

 distillation of the carbon tetrachloride were together dissolved in hot alcohol. 

 When the solution was allowed to stand for some time colourless crystals 

 of 2-10-dinitrodiphenylether were deposited. By evaporating the parent liquid 

 from these crystals a red oil was again obtained. 2-4-Dinitrophenol was 

 separated from the oil by dissolving the latter in ether and extracting it 

 with dilute aqueous potash. The light-reddish oil, which remained when the 

 ether had evaporated, was subjected to a steam-distillation. Some unchanged 

 diphenylether passed over with the steam, but the light-yellow oil left in 

 the distillation-flask did not crystallise. It dissolved easily in all solvents 

 except benzene, and probably contained mononitrodiphenylethers. 



3. Action of Nitrotis Fumes on Diphenylether. 



(a) In Carbo7i Tetrachloride Solution. — Nitrous fumes, prepared from nitric 

 acid and arsenious oxide, were passed for a considerable time through a 

 5 per cent, solution of diphenylether in carbon tetrachloride. 



After remaining 4 weeks in a stoppered flask, the solution had a light-red 

 colour, and contained some colourless prismatic crystals floating on it. From it, 

 by a method analogous to that just described, we obtained 2-10-dinitrodiphenyl- 

 ether, 2-4-dinitrophenol, and a yellow oil, which did not, however, crystallise. 



_ (b) In Acetic Acid Solution. — In another experiment, in which glacial acetic 

 acid was employed as the solvent, no solid separated from the deep-red solution. 

 The latter, after remaining 4 weeks at the temperature of the room, was 

 poured into a large volume of water, and the oil which separated was extracted 

 with ether. The ethereal solution was freed from 2-4-dinitrophenol by washing 

 it with dilute alkali, and then on evaporation left a reddish oil, which 

 separated from hot alcohol as a light-yellow solid. The latter, when recrystallised 

 from a small amount of petroleum ether, was obtained in the form of colour- 



