172 Proceedings of ilm Roi/al Irisli Academy. 



at 32''-36° C, and were found to consist of 2mchanycd phcnyl-hcnzyl ctlio; wliicli 

 was obtained pure by recrystalHsatioii of tbe product from methylated spirit. 



(b) Nitrous fumes. — 1. Dry nitrons fumes were passed for ten miiuites into 

 an ice-cold solution of 2 grams of plienyl-benzyl ether in 20 grams of carbon 

 tetrachloride. The colouifcss solution' became first red and then bluish. The 

 product was allowed to remain in an open vessel overniglit, and a dark red 

 solid separated. It was dissolved in hot carbon tetrachloride, and obtained on 

 cooling the solution as red oil}' crystals, which, when pressed out on filter paper 

 and dried, melted at80°-9S°C. On redissolving the substance in alcohol and 

 boiling with animal charcoal, colourless leafy crystals were obtained, melting 

 at 101°-106°C., which were found to consist of 4--ni(ro-j>hniyl-bc)n]/l etlicr. 



2. When dry nitrous fumes were passed into a similar stilulion to the above 

 for a longer period — about thirty minutes — a thick red solid separated from 

 the blnish-red solution. Tiie red crystalline product which was obtained after 

 evaporation of the solvent at the ordinary temperature was heated with carbon 

 tetrachloride, in which a portion of it was insohdjle. This fraction consisted 

 of reddish, scaly crystals which, wlier. dry, melted at 182''-186° C. After 

 rocrystallisation from boiling xylene, fine, shining prismatic needles were 

 obtained. When mi.xed with an equal amount of i-JO dinitro-jilicnyl-hcnzj/l- 

 ethcr (m.p. 18G°), the melting point was 18-i"-lS6° C, while a mi.xture with 

 2-4-2'-trinitro-phenyl ether (m. p. 187°) melted at 148"-170° C. It must 

 therefore be 4--10-dinitro-phaujl-lcnzyl ether. 



The carbon tetrachloride solution on cooling deposited white acicular 

 prisms melting at 136^-164° C. It was not possible by repeated fractional 

 crystallisations of this mixture from alcohol and carbon tetrachloride to 

 separate its constituents. 



C. — Action of Nitrous Acid on Diphenylccmine. 



1. Six molecular amounts of butyl nitrite were added to a solution of 

 2-5 grams of diphenylamine in 50 grams of glacial acetic acid, and the 

 mixture was allowed to remain for six weeks in a stoppered flask at the 

 temperature of the room. The yellow-coloured solution was poured into 

 water, and the upper oily layer was separated. It solidified completely in 

 a few minutes, and when the butyl nitrite was removed in a ^■acuum, the 

 yellow crystals obtained melted at 102°-115°C. After recrystallisation from 

 methylated spirit, the pale yellow prismatic crystals proved to be 4-nitro- 

 diphenyl-nitrosamine melting at 133°-134° C. 



A minute cj^uantity of a green, oily substance was got by extraction of the 

 aqueous layer with ether. 



2. A 5 per cent, solution of diphenylamine in carbon tetrachloride, to 



