Ryan & Keane — Action of Oxides of Nitrogen on Phenylhemylether. 289 



1. Action of Nitrogen Peroxide on Phenylhemylether. 



(a) In Carhon Tetrachloride Solution. — A current of nitrogen peroxide, 

 generated by heating lead nitrate, was passed for half an hour into a solution 

 of 2 g. of phenylbenzylether in 50 g. of carbon tetrachloride, and the solution, 

 which had a dark-brownish-red colour, was allowed to remain in a stoppered 

 flask at the room temperature for two days. 



On distilling off the carbon tetrachloride a brownish-red oily residue was 

 obtained, which solidified on cooling. The solid was washed with dilute aqueous 

 potash, and recrystallised from alcohol, from which it separated in brownish- 

 white crystals, melting at 105-5-106° C 



A mixture of it with p-nitrophenylbenzylether, obtained by the action of 

 benzyl chloride on the sodium derivative of p-nitrophenol, melted at the same 

 temperature, the two substances being therefore identical. 



Under these conditions nitrogen peroxide acts on phenylbenzylether forming 

 'p-nitrophenylbenzyl ether. 



(6) Proceeding as above, but allowing the mixture to stand for six weeks 

 instead of two days, a mixture containing two layers was obtained — a dark- 

 red lower layer and a blackish-red upper layer, which contained much crystalline 

 matter. 



The results got on examination of the mixture were very similar to those 

 obtained from the product of the action of 4 molecular amounts of nitric 

 acid on phenylbenzylether (q. v.) — the main product being 4-nitrophenylbenzyl- 

 ether, together with a little matter which was soluble in alkali. 



(c) "When a mixture similar to (a) . was allowed to stand four months 

 and was re-saturated with nitrogen peroxide at intervals of three weeks, the 

 solution became yellow with the separation of a white solid. 



The carbon tetrachloride was distilled off under reduced pressure. On 

 passing a current of steam through the yellow residue left in the flask, white 

 plates, not unlike benzoic acid, distilled with the steam, whilst a red tarry 

 substance, with mtich white solid matter, was left in the non-volatile portion. 

 The latter solid was extracted with a little ether and the ether solution was 

 washed with dilute potash. The ether layer gave colourless needles, melting 

 at 186° C, which proved to be identical with 4-4'-dinitrophenylbenzylether 

 prepared synthetically by the action of 2'-iiitrobenzyl chloride on sodium 

 p-nitrophenolate. The potash layer gave, on acidification and extraction with 

 ether, a yellowish-white solid and tarry matter, neither of which, however, 

 was obtained in sufficient quantity. to establish its identity. 



(d) In the Absence of Solvents. — A shallow glass vessel containing 4 g. 

 of phenylbenzylether was placed beside a similar vessel containing liquid 

 nitrogen peroxide, the two vessels being enclosed under a bell-.iar. The 

 phenylbenzylether immediately darkened in colour, and, after a few hours, 

 appeared as a black, more or less oily solid. After three days the brownish- 

 black oilv nitration product was examined. It possessed a pleasant aromatic 

 odour. The oily mass was mixed with ether, and the purnle ethereal solution 

 (A) was decanted from the brown tarry residue (B). After repeated 

 crystallisation from alcohol the latter substance, which weighed about 2-4 g., 

 melted at 105-106° C. A mixture of it with 4-nitrophenylbenzylether melted 

 at the same temperature, the two substances being, therefore, identical. The 

 ethereal solution (A) was washed with dilute potash, and in this way the 

 solute was divided into two portions (a) and (ft), the latter being soluble 

 and the former insoluble in potash. ' a (about 1 g.) consisted of a brownish 

 oily solid, which, after recrystallisation from alcohol, proved to be 4-nitro- 



