432 
DE. A. W. HOFMAXX OX THE PHOSPHOEUS-BASES. 
On examining somewhat minutely into the deportment of triethylphosphine with 
sulphur-compounds, the organic sulphocyanates could not be left unnoticed. My 
attention was in the first place fixed by the sulphocyanate of phenyl, which I had just 
discovered at the time I was engaged in the study of these reactions. I owe to the 
kindness of Dr. Leibius a very considerable quantity of this somewhat difficultly 
obtainable sulphocyanate, the full description of which will be found in a paper on 
phenyl-derivatives shortly to be published. The deportment of this compound with 
triethylphosphine, however, is here given in connexion with the phosphorus-bases. 
Action of Sulphocyanate of Phenyl upon Triethylphosphine. 
The reaction betAveen the tAvo substances in the anhydrous state is very Aiolent, and 
frequently causes the inflammation of the phosphorus-base. The mixtm-e assumes a 
deep-yelloAv colour, and on cooling deposits sometimes splendid m-anium-yellow needles ; 
often, however, it remains liquid for hours, and even for days, but suddenly solidifies, 
Avhen touched with a glass rod, into a hard yelloAv crystalline mass. The new compound 
is most conA^eniently prepared by alloAving the sulphocyanate to act upon the triethyl- 
phosphine in the presence of a considerable volume of ether. The product of the 
reaction, being difficultly soluble in cold ether, often separates in the cn stalline state, 
more frequently as an oil, Avhich solidifies after some time. In order to ensure perfect 
purity, it is only necessary to crystallize the compound once or tAAice from boiling ether. 
I. 0‘2160 grm. of the yelloAV crystals, dried in vacuo over sulphuric acid, gave 
0-4923 grm. of carbonic acid and 0-1585 grm. of Avater. 
II. 0-2242 grm. of crystals of a second preparation gaA'e 0-5110 grm. of carbonic acid 
and 0-1675 grm. of Avater. 
III. 0-3491 grm. of substance, burnt Avith carbonate of sodium and oxide of mercm-y, 
gave 0-3250 grm. of sulphate of barium*. 
These numbers characterize the neAV body as a combmation of one molecule of tri- 
ethylphosphine Avith one molecule of sulphocyanate of phenyl : 
C 2 H 5 I 
^ CN I 
P + . „ S = C ,3 
^hJ ' 
H 20 N P S. 
Theory. 
Experiment. 
A 
' 
> 
r N 
I. II. III. 
^13 
156 
61-66 
62-16 62-16 
H^o 
20 
7-90 
8-14 8-30 
N 
14 
5-54 
P 
31 
12-25 
S 
32 
12-65 
12-79 
253 
100-00 
* 1711611 attemptiug to determine the sulphur as sulphide of silver, I found that on ehullitiou of the 
