ACTION OF PHOSPHIDE OF SODIUM ON HALOID ETHERS. 213 
phosphonium. After three days’ heating at a temperature of 180°-190° most of 
the phosphide was acted on. The tube was then opened and repeatedly extracted 
with dry chloroform. The extract was distilled to dryness, and the residue 
treated with ether, which dissolved most of it, but left a small quantity of the 
oxide of tribenzyl-phosphine. The ethereal extract was evaporated to dry- 
ness, and left a light-coloured soft resin, which partly crystallised. A phos- 
phorus determination showed that this contained the quantity of that element 
calculated for tribenzyl phosphine, 
0-651 required* 29-1 cc. uranium solution = 9:9 per cent. P 
(C,H,),P requires NO Bre 
The quantity, however, of the resin at our disposal was so small that we could 
not make a thorough investigation of it. But we are inclined to the belief that 
both it and the resin obtained as a bye product in the preparation of the chloride 
of tetrabenzyl-phosphonium consisted mainly of tribenzyl-phosphine (see p. 209). 
Action of Heat on the Salts of Tetrabenzyl-Phosphonium. 
During the experiments we have described, we obtained on heating several 
of the salts of tetrabenzyl-phosphonium, results which invited a closer investiga- 
tion. Partly on this account, and partly from the interesting results which Drs 
Crum Brown and Buatkret have obtained by the action of heat on the salts of 
trimethyl-sulphine, we determined to study the behaviour of one or two of the 
compounds of tetrabenzyl-phosphonium when heated. 
Action of Heat on Chloride of Tetrabenzyl-Phosphonium—We hoped that 
the salt would dissociate when submitted to the action of heat into chloride of 
benzyl and tribenzyl-phosphine. 
A considerable quantity of the chloride previously dried and fused was 
placed in a small distilling flask and heated in an air bath. Nothing particular 
occurred until the temperature had risen to about 300° C., when the fused salt 
began to grow brown, and a colourless liquid distilled. When a considerable 
quantity of this had passed over, hydrochloric acid was evolved, and later the 
distillate was yellow, and contained an abundance of free phosphorus. The 
heating was continued until nothing further distilled. There remained a con- 
siderable residue, consisting chiefly of charcoal. 
The whole of the distillate was fractionated. Hydrochloric acid was evolved 
in abundance; the thermometer then rose to 109°, and by far the larger quantity 
of the product passed over between that temperature and 115°. This fraction 
on redistillation boiled constantly at 110°-113°, and had the odour of toluol. 
_ It was not further examined, and was considered to be that substance. 
* After fusion with a mixture of nitrate of potash and caustic potash. 
+ Proceedings Roy. Soc., Edin. 
VOL. XXX. PART I. 
i) 
A 
