291 



rise to the formation of mono-, di-, tri-, and tetra-phosphonium-com- 

 pounds, the composition of which was pointed out in advance by 

 theory. 



Some of the products which are generated by the action of the 

 chlorinated substitutes of marsh-gas are already known. Chloride 

 of methyl fixes one molecule of triethylphosphine, giving rise to the 

 chloride of methyl-triethylphosphonium, 



C H 3 C1+ (C 2 H 5 ) 3 P= [(C H 3 ) (C a H 5 ) 3 P] Cl, 



which in combination with dichloride of platinum was examined several 

 years ago by Cahours and myself. 



The product which is generated by the action of chloroform on 

 triethylphosphine is likewise known. I have shown that chloroform 

 is capable of fixing three molecules of phosphorus-base, producing 

 the trichloride of formyl-nonethyltriphosphonium, 



r (C 2 H 5 ) 3 Pn'" 



(C H)'" C1 3 + 3[(C 2 H 5 ) 3 P]= I (C H)'" (C 2 H 5 ) 3 P |C1 3 . 



( C a H 5 ) 3 P -i 



A short account of this substance has been already communicated to 

 the Royal Society*. 



It remained therefore only to examine the deportment of triethyl- 

 phosphine with the second, and likewise with the fourth of the 

 chlorinated substitution-products. Dichloride of methylene, the 

 product obtained by the action of chlorine on chloride of methyl, 

 acts with considerable energy on triethylphosphine. Digestion of 

 the mixture for a few hours at a temperature of 100 in sealed tubes, 

 suffices to accomplish the reaction. The products vary considerably, 

 according to the proportion in which the two agents are mixed. 

 One molecule of dichloride of methylene and one molecule of tri- 

 ethylphosphine give rise to the formation of the beautifully crystal- 

 lized chloride of chloromethyl-triethylphosphonium, 



C H 2 C1 2 + (C 2 H 5 ) 3 P= [(C H 2 Cl) (C 2 H 5 ) 3 P] Cl. 

 This chloride forms with dichloride of platinum a double salt, beauti- 

 fully crystallized in needles, rather difficultly soluble in water, which 



contains 



[(CH 2 Cl)(C 2 H 5 ) 3 P]Cl,PtCl 2 . 



The chloromethylated triethylphosphonium-salt is capable of fixing 

 a second equivalent of triethylphosphine. The crystalline mass 

 * Proceedings, vol. x. p. 189. 



