RvAN & Kf>ane — Action of Oxides of Nitrogen on Phenylhensylether, 291 



and washed with dilvite potash. The ethereal layer on evaporation gave a 

 brownish solid, which, after a. few reerystallisations from methylated spirits, 

 yielded colourless crystals, melting at 104° C, identical with 4-nitrophenyl- 

 benzylether. 



The potash layer gave on acidification yellowish crystals, which melted 

 at 114° C. ; on crystallisation from methylated spirits they lost their yellow 

 colour, and were not unlike benzoic acid. 



3. Action of Nitric Acid on PhenylbenzyUther. 



(a) In the Absence of Solvents. — 2 g. of phenylbenzylether was slowly added 

 to 3 g. of nitric acid (Sp. g. 1-5) in a small round flask immersed in a freezing 

 mixture. 



On allowing the mixture to stand overnight a reddish oily solid, possessing 

 an odour like that of benzaldehyde, was obtained. The solid was pressed free 

 from oil and shaken up with a little ether. The ether solution was then 

 separated from the undissolved tar and washed with dilute aqueous potash. 

 The ether layer on evapoi'ation gave about 1 g. of 4-nitrophenylbenz3dether, 

 while the potash layer yielded on acidification a dark-red solid, the quantity of 

 which was insufficient for further investigation. 



When the acid (2 c.c.) was added graduallj^ to the phenylbenzylether (2 g.), 

 a rather violent reaction ensued with the formation of much charred matter. 



(b) In Ether Solution. — 1-92 c.c. (4 molecular amounts) of nitric acid 

 (Sp. g. 1-42) was added to a solution of 2 g. of phenylbenzylether in 50 g. 

 of ordinary ether. The mixture was allowed to remain in a stoppered flask 

 for sis weeks; it developed no coloration; and the phenylbenzylether was 

 recovered unchanged. 



Experiments similar to the foregoing were carried out, using 1, 2, and 3 

 molecular amounts of nitric acid, and, as might be expected, no interaction 

 was found to have taken place. 



(c) In Carbon Tetrachloride Solution. — Mixtures containing 1, 2, 3, and 4 

 molecular amounts of nitric acid (Sp. g. 15) and 2 g. of phenylbenzylether, 

 dissolved in 50 g. of carbon tetrachloride, were allowed to remain in stoppered 

 flasks for a period of six weeks. 



The mixtures were at first dark-red in colour. After some time the colours 

 became much clearer with the separation of crystalline matter in the cases of 

 the solutions to which 2, 3, and 4 molecular amounts of nitric acid had been 

 added. 



On examining the contents of the flask to which 1 molecular amount of nitric 

 acid had been added, phenylbenzylether was recovered unchanged together with 

 a little yellow oily matter. 



In the flasks to which 2 and 3 molecular amounts of nitric acid had been 

 added, 4-nitrophenylbenzylether was identified, with an increasing amount of 

 oily matter and traces of a reddish crystalline substance. 



In the case of the solution to which 4 molecular amounts of nitric acid had 

 been added, the red oil left after the distillation of the carbon tetrachloride was 

 steam-distilled. The portion volatile with steam was soluble in ammonia, 

 giving a yellow solution which became colourless on acidification with hydro- 

 chloric acid. The acid solution was extracted with ether; a while crystalline 

 substance, melting at 101-105° C, resulted, which was not unlike benzoic acid 

 in appearance, whilst a mixture of it with the latter melted at 113-115° C; 

 several reprecipitations and reerystallisations of this white substance, however, 

 failed to improve its melting-point. 



