ARTICLE 
Tur Preparation oF ALKyL-SuLPHINE, SELENINE, AND PuHospHontum SALTs, BY 
Orme Masson, M.A., D.Sc., anp J. B. Kirxuanp, F.C.S. 
(Read Thursday, Dec. 13, 1888.) 
The usual method of preparing the salts of triethyl-sulphine (which may be 
taken as the type of the sulphine radicles) consists in mixing ethyl sulphide and ethyl 
iodide, purifying the resulting solid triethyl-sulphine iodide by crystallisation, 
converting this into the hydroxide by the action of silver oxide, and finally 
neutralising the solution of the hydroxide with the appropriate acid. ‘The method 
is simple and gives a good yield. It is open, however, to one somewhat important 
objection, viz., that it involves, as a preliminary process, the preparation of ethyl 
sulphide —a liquid of such a poisonous character and possessed of such a penetrating 
and disagreeable odour that chemists are not generally willing to work with it. 
Triethyl-selenine salts are prepared by a perfectly analogous series of operations. 
A similar objection holds to an even greater extent, as ethyl selenide is of more 
disagreeable character than ethyl sulphide, Moreover, the loss of selenium, which 
necessarily occurs in the preliminary process of converting it into ethyl selenide, is 
here a fault of considerable importance. 
The salts of tetraethyl-phosphonium have been obtained by several methods, 
but none of them can be called wholly satisfactory. They were discussed at length 
by Professor Letts in a paper published in the Transactions of the Royal Society of 
Kdinburgh (1881); and the difficulty of the problem may be judged from the fact 
that this investigator rejected all known methods as practically unworkable and 
sought for a new method to supplant them. By far the best and easiest of all 
hitherto known methods is that devised by Hofmann, and which consists in heating 
phosphonium iodide with absolute alcohol in sealed tubes to 180° for some hours. 
The following reactions occur :— 
PH, 1 + 4C,H, OH = P (C,H,), 1 + 4 HO, 
PH, I + 3 0,H, OH = P (C,H,); HI + 3 H,0; 
and these two iodides are separated by addition of potash, which precipitates the 
former unchanged and converts the latter into’ the volatile free base triethyl 
phosphine. There are two objections to this process, however. The first is that the 
preliminary preparation of the phosphonium iodide is a troublesome operation if any 
large quantity be required ; and the second is that a very great pressure is always 
developed in the tubes in which the alcohol and phosphonium iodide are heated, so 
