Tetrethylphosplionium and their Decomposition by Heat, 197 



tained, still another experiment with considerable quantities 

 (40-50 grins.) of the benzoate was made. It was prepared 

 by treating a solution of the hydrate with benzoic acid. The 

 solution was evaporated as far as possible on a water-bath, 

 transferred to a distilling flask, and heated. Slight decom- 

 position occurred before 200° C, but it did not become brisk 

 until the thermometer rose above 300°. The products of the 

 reaction consisted of an aqueous solution of oxide of triethyl- 

 phosphine, above which floated a yellow oil. On distilling 

 the former, eight grammes of triethylphosphine oxide were 

 obtained ; the oily liquid weighed about 32 grammes. It 

 was shaken with hydrochloric acid to remove triethylphos- 

 phine (which, when separated by potash, weighed nearly 8 

 grammes). The oil, after this treatment, was distilled, and 

 yielded 4-5grammes of benzol boiling from 78°-90° C, and suf- 

 ficiently pure to solidify in a freezing-mixture. The higher 

 boiling portions consisted chiefly of a liquid smelling strongly 

 of benzoic ether, and boiling from 208°-220° 0. On treating 

 this with ammonia gas it almost solidified into a crystalline 

 mass of benzamide. This was removed by boiling water, and 

 the oily liquid which remained once more fractionated, when 

 it all passed over between 208°-214° C. A combustion gave 

 the following results : — 



0-3347 grm. gave 0-952 grm. C0 2 and 0*2235 grm. H 2 0. 



Carbon = 77*5 per cent. Hydrogen = 7*4 per cent. 



The hydrocarbon ethyl benzol was carefully looked for in 

 this experiment, but could not be detected. 



The production of triethylphosphine, its oxide, ethylene, 

 benzol, ethylphenyl ketone, and carbonic anhydride, indicate 

 that the benzoate decomposes when heated in a similar manner 

 to the acetate and suffers two distinct changes — the one yield- 

 ing the free phosphine, the other yielding the oxide. The 

 two reactions may be represented by the following equa- 

 tions * : — 



(1) (C 2 H 5 ) 3 P<-§ J OC6H5 = (0 2 H 5 ) 3 PO + C 6 H 5 COC 2 H 5 . 



(2) (C 2 H 5 ) 3 P<d§§£ H5 = ^ E ^ F + °° 2 + CA + ° A ; 

 and 



(C 2 H 5 ) 3 P< ^ CeH =(C 2 H 5 ) 3 P + C 2 H 5 OCOC 6 H 5 . 



The production of ethyl benzol could be explained by the equation : — 



(Cja 5 ) 3 P<j 1..' =( c 2 H 5 ) 3 P+C0 o +C 6 H 5 C : H 5 . 



;\OCO;C 6 H 5 



