290 Scientific Proceedings, B.oyal Dahlin Society. 



phenylbenzylether. S (about 06 g.) was also oily in consistency and red in 

 colour. On extracting the crystalline matter with warm petroleum ether, 

 yellow leaves, melting at 106-109° C, were obtained, which, after recrystallisation 

 from dilute alcohol (25 per cent.), melted at 109-111° C. When further 

 purified by distillation with steam and sublimation, the product melted at 

 119-120° C, and proved to be benzoic acid. The nitration of phenylbenzyl- 

 ether by this method gave therefore 75 per cent, of 4-nitrophenylbenzylether, 

 15 per cent, of benzoic acid, and 10 per cent, of oily or tarry matter. 



(e) The experiment described above was repeated, allowing the phenylbenzyl- 

 ether to remain in the atmosphere of nitrogen peroxide for two months. The 

 nitrated product had a somewhat lighter brown colour than that in the last 

 experiment, and, as before, was separated by means of ether into two fractions, 

 A and B. These fractions were then separately distilled in a current of 

 steam, and the two portions which volatilized were united (C). The latter 

 was a yellow-coloured solution which deposited 0-4 g. of colourless leaves on 

 cooling. This substance, after recrj^stallisation, melted at 119-120° C, and 

 proved to be benzoic acicl. The mixture also contained a thin film of a brown- 

 coloured oil, which had an aromatic odour, and was possibly benzaldehyde. The 

 yellow aqueous portion of C was extracted with ether and the ether solution 

 was washed with potash. The ethereal layer on evaporation left only a trace 

 of a brown oily solid, whereas the potash layer, after acidification with diluted 

 hydrochloric acid and extraction with ether, gave grey plates, melting between 

 79° and 91° C. This mixture may have contained a nitrophenol, as its alkaline 

 solution had a yellow colour which disappeared on acidification. Fractional 

 crystallisation from either water or alcohol failed to isolate the impurity in 

 the body, the main constituent (D-6 g.) of which was benzoic acid. 



The "portion of A which remained (OS g.) in the distilling flask consisted of 

 an orange-coloured solid, which, after recrystallisation from alcohol, melted 

 at 105-106° C, and was identical with 4-nitrophenylbenzylether. The 

 corresponding portion of B consisted of a dark-coloured tar. This was dissolved 

 in a large volume of warm alcohol, and after some days 05 to 07 g. of a 

 black tar and 11 to 13 g. of a light red oily solid were obtained. The latter 

 was freed from oil by pressing it between absorption pads and then dissolved 

 in alcohol, from whicli it separated in the form of light yellow prisms, melting 

 at 103-105° C. As a mixture of it with 4-nitrophenylbenzylether melted at 

 104^105° C, it must have been slightly impure 4-nitrophenylbenzj'lether. 



The prolonged action of nitrogen peroxide on phenylbenzylether forms 

 therefore 50-55 per cent, of 4-nitrophenylbenzylether, 25 per cent, of benzoic 

 acid, and 23-18 per cent, of oily or tarry products containing a small amount 

 of a sweet-smelling oil. 



2. Action of Nitrous Fumes on Phenylbenzylether. 



A current of nitrous fumes, generated by the action of nitric acid on 

 arsenious oxide, was passed for half an hour into a solution of 2 g. of phenyl- 

 benzylether in 50 g. of carbon tetrachloride. The solution, which was brown 

 in colour, was allowed to stand for six weeks in a stoppered flask. At the time 

 of its examination the mixture contained two layers, a clear green lower layer 

 and a dark-reddish upper layer, which contained much crystalline matter. 



The carbon tetracUoride was driven off, as before, under reduced pressure. 

 A little alcohol was added to the reddish residue in the distilling flask, a clcEir 

 yellow solution resulting, with a little insoluble oily matter. The yellow solution 

 on evaporation gave a reddish product, which was dissolved in a little ether 



