Russian Journal of General Chemistry, Vol. 72, No. 10, 2002, pp. 1650 1651. Translated from Zhurnal Obshchei Khimii, Vol. 72, No. 10, 2002, p. 1751.
Original Russian Text Copyright
2002 by Timokhin, Kazantseva, Blazhev, Reutskaya, Gusarova.
LETTERS
TO THE EDITOR
Facile Exchange of Phosphoryl Oxygen by Sulfur
and Selenium in Teriary Phosphine Oxides
B. V. Timokhin, M. V. Kazantseva, D. G. Blazhev, A. G. Reutskaya, and N. K. Gusarova
Irkutsk State University, Irkutsk, Russia
Received September 27, 2001
It is known that tertiary phoshine oxides can be
converted into their sulfides by heating either with
silver sulfide [1] or with phosphorus pentasulfide [2]
at 110 150 C. Tertiary phosphine selenides can be
prepared by treatment of phosphine oxides with
selenium in the presence of potassium dihydrophos-
phate at 270 370 C [3].
ride first with tetraalkylammonium iodide or hexa-
ethylphosphoric triamide and then with elemental
sulfur, thiophosphoryl chloride, or selenium. In both
cases, no heating of the reaction mixtures is required.
Evidently, the first stage involves halophilic reduction
of chlorophosphonium salt with the easily polarizable
nucleophiles: phosphorous triamide or iodide ion. The
same transformation can also occur under the action
of a mixture of red phosphorus and a catalytic amount
of white phosphorus. In the second stage, the resulting
tertiary phosphine with chalcogen donor by known
schemes.
We found that such transformations can easily be
accomplished by treatment of triorganylchlorophos-
phonium dichlorophosphates, formed by reactions of
tertiary phosphine oxides with phosphorus oxychlo-
2
R NI, S
4
+
+
R PS + R N I Cl + R N PO Cl ,
3
4
2
4
2
2
+
(Et N) P,
2 3
R3PO + POCl3
R PCl PO Cl
3 2 2
PSCl (Se)
3
+
R PS(Se) + (Et N) PCl PO Cl + PCl ,
3
2
3
2
2
3
R = Et, CH Ph, Ph.
2
To a solution of 1.5 g of Ph P in 20 ml of dry
A day after, 1.8 g of (Et N) P was added. The mix-
2 3
3
benzene, 1.2 g of POCl was added, and the mixture
ture was stirred for 1 h, and then 0.23 g of sulfur was
added. After 2-h stirring, a precipitate formed and was
separated and recrystallized from chloroform to obtain
1.3 g (54%) of tribenzylphosphine sulfide, mp 269
3
was stirred for 4 h. The oily substance that formed
was separated, the solution was diluted with 20 ml of
+
benzene, and 3.7 g of Bu EtN I and 0.9 g of PSCl
3
3
were added to it one after another. After 4-h stirring,
an oil formed and was separated and washed with
benzene (3 20 ml). The combined benzene solutions
were evaporated. Recrystallization from ethanol gave
271 C,
47.1 ppm. Found, %: P 9.23; S 9.44.
P
C21H21PS. Calculated, %: P 9.22; H 9.52.
To a suspension of 2.2 g of Ph PO in 20 ml of dry
3
toluene, 1.2 g of phosphorus oxychloride was added,
and the reaction mixture was stirred for 4 h. After that,
1.95 g of (Et N) P was added, and after 2 h the reac-
1
g (63%) of triphenylphosphine sulfide was obtained,
mp 160 162 C, 40.5 ppm. Triethylphosphine
sulfide was obtained analogously, yield 35%, mp 96
7 C, 53.5 ppm (chloroform). Found, %: C 47.83;
P
2
3
tion mixture was treated with 0.63 g of selenium
powder. When the selenium had dissolved completely,
the precipitate that formed was separated and re-
crystallized from ethanol to obtain 2.3 g (85%) of tri-
9
P
H 10.39; P 19.67. C H PS. Calculated, %: C 48.0;
6
15
H 10.0; P 20.66.
phenylphosphine selenide, mp 184 185 C,
Found, %: C 63.5; H 4.25; P 23.0; Se 23.0. C H
15
PSe. Calculated, %: C 63.34; H 4.39; P 9.09; Se
34.7.
P
To a suspension of 2.3 g of tribenzylphosphine
1
8
oxide in 20 ml of toluene, 1.1 g of POCl was added.
3
1
070-3632/02/7210-1650$27.00 2002 MAIK Nauka/Interperiodica
Timokhin
