28 Dr. N. Collie on the Action of Heat on 



This difference from the corresponding nitrogen and sulphur 

 compounds was explained by the reducing action of the ter- 

 tiary phosphine. 



In the former paper, already alluded to, the action of heat 

 only on the Tetrethylphosphonium salts was investigated ; 

 and as in some cases the results were of a somewhat compli- 

 cated nature and not perfectly simple of explanation, mixed 

 phosphonium salts, containing both aromatic and fatty radicals, 

 were chosen for examination, as it was thought that they might 

 throw some additional light on the general way in which these 

 phosphorus compounds decompose. 



Chloride of Triethylbenzylphosphonium. 



This salt has been previously prepared by Hofmann* by 

 heating a mixture of benzylidene chloride with triethyl- 

 phosphine and alcohol to 120°-130° C. A simpler method 

 was, however, employed, viz. treating triethylphosphine with 

 excess of chloride of benzyl, when complete combination 

 occurs, and the chloride of triethylbenzylphosphonium is pro- 

 duced, 



P(C 2 H 5 ) 3 + C 7 H,C1= P(CH„),(C 7 H 7 )C1. 



It was found necessary, however, to use an excess of the 

 chloride of benzyl in the reaction, on account of the heat which 

 is evolved when the combination occurs, which causes the 

 volatilization of some of the triethylphosphine. After all 

 reaction ceases the mixture solidifies, on cooling, to a mass of 

 crystals. On treatment with water the excess of benzyl chlo- 

 ride easily separates from the aqueous solution of the triethyl- 

 benzylphosphonium chloride, which can then be evaporated to 

 a small bulk and allowed to crystallize. As Hofmann gives 

 no description of the salt, and only prepared the platinochlo- 

 ride in a state fit for analysis, some of the salt was carefully 

 purified and its properties determined. 



(a) 2*041 grms. of salt, dried in vacuo over sulphuric acid, 



lost 0*137 grm. =6*71 per cent. 



(b) 0*446 grm. dry salt took 19*0 cubic centim. decinormal 



nitrate-of-silver solution =15*12 per cent. CI. 



(c) 0*283 grm. dry salt took 11*8 cubic centim. decinormal 



nitrate-of-silver solution =14*80 per cent CI. 

 (al) 0*363 grm. dry salt gave 0*842 grm. C0 2 and 0-2915 

 grm. H 2 0, 



C = 63*26, H = 8*92. 



Calculated for Found. 



(C 7 H 7 )(O a H 5 ),P01,H a O. (a) 



H 2 G 6*85 6*71 



* Ann. Spl. I. p. 323. 



