226 Dr. A. W. Hofmann on the Phosphorus Bases. [Mar. 21, 



The solution of the chlorhydrate in concentrated hydrochloric acid fur- 

 nishes with platinum perchloride a beautifully crystallized orange-red pla- 

 tinum salt. 



lodhydrate. — Of all the salts of the base, this is the one most readily 

 obtained ; it separates in bulky crystals when a current of methylphosphine 

 is passed into the most concentrated iodhydric acid. If a solution of the 

 gas in somewhat less concentrated iodhydric acid be mixed with ether, the 

 whole liquid solidifies to a mass of iridescent plates. By washing with 

 ether, pressing, and sublimation in a current of dry hydrogen, the salt may 

 be readily obtained in a state of purity. Analysis led to the formula 



CH 6 PI = (CH 3 )H 2 P,HI. 



The sulphate I have not yet seen in the solid state ; it is, however, rea- 

 dily formed by bringing the phosphorus base in contact with concentrated 

 sulphuric acid. The gas is absorbed without the acid colouring. On 

 addition of water, methylphosphine is again liberated. The sulphite is a 

 white amorphous mass which is formed when methylphosphine and sul- 

 phurous acid gases are collected together over mercury. 



With carbonic acid and sulphuretted hydrogen methylphosphine gas 

 may be mixed without any condensation taking place. Sulphur, carbon 

 bisulphide, and chlorocarbonic ether, when placed in contact with methyl- 

 phosphine, give rise to the formation of new compounds, which will be the 

 subject of a special communication. 



Among the products M. P. Thenard* describes, in the short notice of 

 his researches on the action of methylic chloride upon calcium phos- 

 phide, is an oily compound boiling at 250° containing C 2 H 6 P (perhaps 

 phosphoric kakodyl), which, when treated with water, splits into an 

 acid and a gaseous body. The latter, to which M. P. Thenard assigns the 

 formula C H. P, is said to combine with either one or two volumes of chlor- 

 hydric gas. It can scarcely be doubted that the phosphoretted gas disco- 

 vered by M. Thenard is identical with the body the chemical history of 

 which I have endeavoured to sketch in this paper. There are certainly 

 still some discrepancies to be explained, such as the observation just alluded 

 to, that M. Thenard's phosphorus body combined with chlorhydric acid in 

 two proportions. 



The somewhat complex reaction which gives rise to the formation of 

 methylphosphine, when generated by means of methylic chloride and cal- 

 cium phosphide, and indeed the difficulties attending this process/ which 

 appear to have prevented M. Thenard from pursuing his researches, have 

 hitherto deterred chemists from entering more thoroughly into the 

 investigation of this remarkable compound. By the method described 

 in this paper, methylphosphine may be readily and abundantly obtained in 

 a state of perfect purity, so that its further examination will present no 

 difficulty. 



* Compt. Rend. vol. xxv. p. 892. 



