184 PROFESSOR LETTS AND N. COLLIE ON THE 
Hormann’s process for obtaining primary and secondary: phosphines— 
which he employed successfully in the methyl, ethyl, and benzyl series 
—consists in heating a mixture of phosphonium iodide, zine white, and the 
hydrocarbon iodide, in sealed tubes for some hours at a temperature of 
160°-180°. The tubes are then found to contain a white crystalline mass, 
consisting of compounds of the hydriodates of the primary and secondary bases 
with zinc iodide. 
The reactions which occur are represented by the equations, 
2C,H,I +2PH,I + ZnO =2[(C,H,)H,P,HI}, ZnI, +H,0. 
2C,H,I+PH,I +Zn0=(C,H,),HP, HI, ZnI,+H,0. 
The separation of the primary from the secondary compound is accom- 
plished with the greatest ease. It is only necessary to add water to the con 
tents of the sealed tubes when the compound of the primary base is decom- 
posed and the base itself set at liberty. When it has been distilled off, the 
addition of potash to the residue separates the secondary base. 
Hormann also studied the action of phosphuretted hydrogen on the alcohols 
at a high temperature, and with a singularly interesting result. 
Not only does phosphuretted hydrogen act on the alcohol, but the bodies 
produced consist entirely of tertiary and quaternary compounds, no primary | 
or secondary compounds being formed at all. Thus the action of phos- 
phuretted hydrogen on an iodide of a hydrocarbon radical is exactly comple- 
mentary to its action on an alcohol. 
In employing the action of phosphuretted hydrogen on ordinary alcohol 
for the preparation of the tertiary and quaternary phosphines, Hormann places 
iodide of phosphonium at the bottom of a sealed tube, and above it the 
alcohol in a smaller tube. The vapour of the phosphonium iodide thus comes 
in contact gradually with the alcohol. The reaction is complete after six to 
eight hours digestion at 180°. The tubes are then found to be full of a white 
crystalline mass, from which caustic potash liberates the tertiary phosphine, 
whilst the iodide of the phosphonium remains in solution. 
The reactions which occur are represented by the equations 
3(C,H,OH) + PH,I=P(C,H,),HI + 3H,0. 
4(C,H,OH) +PH,I=P(C,H,),1 +4H,0. 
MicHAELIS* has comparatively recently added to our knowledge of the 
phosphines, and to the methods of preparing them. 
By passing the mixed vapours of terchloride of phosphorus and _ benzol 
through a red hot tube he obtained phosphenyl-chloride, 
PCl, + CsH,=(C,H;)PCl, + HCl. 
* Liebig’s Annalen, 181, p. 280. 
