ACTION OF PHOSPHIDE OF SODIUM ON HALOID ETHERS. 183 
important properties, and showed that in many respects they resemble the 
tertiary amines, especially in the readiness with which they combine with 
iodides of hydrocarbon radicals to give quaternary compounds. They found, 
however, that, unlike amines, tertiary phosphines are capable of directly 
combining with oxygen. 
HorFMANN continued the study of the tertiary phosphines, and communi- 
cated the results of his experiments to the Royal Society* in 1860. He 
confined his experiments chiefly to triethyl-phosphine, and, in his lengthy 
memoir, describes accurately its properties and reactions. He prepared 
and analysed oxide of triethyl-phosphine and the characteristic red com- 
pound which bisulphide of carbon forms with the phosphine itself, and he 
investigated the action of the latter on a considerable number of organic 
compounds. 
BERLEt attempted to obtain triethyl-phosphine by the action of phosphide 
of sodium on iodide of ethyl. The phosphide of sodium he prepared by the 
heating sodium and phosphorus together in rock oil. Iodide of ethyl only 
acted upon this at a high temperature, and he obtained only very small quantities 
of the tertiary phosphine. Berit next attempted to prepare the tertiary 
phosphine by heating sodium, phosphorus, and iodide of ethyl together in a 
sealed tube; but although the bodies reacted, he does not seem to have 
obtained any very satisfactory results. 
Canours, in 1859, prepared iodide of tetrethyl-phosphonium by the action of 
iodide of ethyl, on crystallised phosphide of zinc (prepared by heating the 
metal in phosphorus vapour) at 180° C. The next experiments on the pre- 
paration of phosphines are very interesting and important. 
Previous to these only tertiary and quaternary compounds had been 
obtained, but Hormann§ showed in an elegant manner that the primary and 
secondary bases may be formed by the action of phosphuretted hydrogen on 
the iodides of hydrocarbon radicals—a process exactly analogous to that 
employed by him for preparing the corresponding amines. Phosphuretted 
hydrogen, however, does not behave in exactly the same manner as ammonia 
in this reaction, for HormMAnn found that the replacement of hydrogen does 
not proceed further than the second atom; whereas with ammonia all the 
hydrogen is replaced step by step, and even quaternary compounds are 
formed. 
Moreover, ammonia acts on the iodides of hydrocarbon radicals much more 
readily than phosphuretted hydrogen, and at lower temperatures. 
* Transactions Royal Society, London, vol. cl. p. 409. 
¢ Journ. fiir. prac. Chem., lxvi. p. 73. 
{ Comptes Rendus, xlix. 
§ Berichte der. deutsch. chem. Ges., iv. pp. 205, 372; v. p. 100. 
