Chlorination of secondary phosphine selenides with the system CCl 4/NEt3

Full text of DOI:10.1134/S1070363210050348

ISSN 1070-3632, Russian Journal of General Chemistry, 2010, Vol. 80, No. 5, pp. 1043–1044. © Pleiades Publishing, Ltd., 2010.
Original Russian Text © S.F. Malysheva, A.V. Artem’ev, N.K. Gusarova, L.V. Klyba, A.A. Tatarinova, B.A. Trofimov, 2010, published in Zhurnal Obshchei
Khimii, 2010, Vol. 80, No. 5, pp. 873–874.
LETTERS
TO THE EDITOR
Chlorination of Secondary Phosphine Selenides
with the System CCl /NEt
4
3
S. F. Malysheva, A. V. Artem’ev, N. K. Gusarova,
L. V. Klyba, A. A. Tatarinova, and B. A. Trofimov
Favorskii Irkutsk Institute of Chemistry, Siberian Branch, Russian Academy of Sciences,
ul. Favorskogo 1, Irkutsk, 664033 Russia
e-mail: mal@irioch.irk.ru
Received November 30, 2009
DOI: 10.1134/S1070363210050348
R
R
R
R
Selenophosphoryl chlorides R P(Se)Cl are highly
Se
H
Se
Cl
2
CCl /NEt3
4
reactive selenophosphorylating reagents widely used in
the synthesis of organoelement compounds [1–5].
They readily react with alkylmagnesium halides [1],
al-cohols [2], amines [3] and other compounds [4, 5] to
form tertiary phosphine selenides as well as esters,
amides, and salts of selenophosphinic acids: ligands
for the design of single-source precursors of nano-
materials [6, 7], efficient iniferters [8], prospective
extragents of the rare-earth elements [9] and coor-
dination media for synthesis of semiconducting nano-
materials [10].
P
P
2
5oC, 10 min
I, II
III, IV
R = Ph,
.
O
(
10 mol %) but in this case more time is required for
completing the reaction (1 h). The reaction does not
proceed without triethylamine.
The elaborated reaction can be represented by the
following scheme described in the literature on the
example of hydrophosphoryl compounds and their thio
analogs [15–17]: P,Se-ambident selenophosphinite
anion А formed by deprotonation of the secondary
Traditional method of preparation of seleno-
phosphoryl chlorides based on the reaction of hardly
accessible diorganylchlorophosphines with elemental
selenium (reflux in benzene for 3 h) [3, 11] is labor-
consuming and does not meet modern ecological
requirements.
phosphine selenide by NEt react with carbon tetra-
3
chloride to form selenophosphoryl chlorides and tri-
chloromethyl carbanion B. Protonation of the latter
with the triethylammonium cation leads to recovery of
triethylamine and formation of chloroform (identified
in the reaction mixture by chromato-mass spectro-
metry).
Here, we report on a novel and convenient method
of synthesis of selenophosphoryl chlorides by the
reaction of secondary phosphine selenides with carbon
tetrachloride in the presence of triethylamine.
Chlorination of bis(2-phenylethyl)phosphine selenide
(
I) and bis[2-(2-furyl)ethyl]phosphine selenide (II)
prepared from red phosphorus, styrene or 2-vinylfuran
Se
Se
+ CCl
Cl
Et N
CCl4
3
R2P
R2P
Se
R2P
3
_
+
Et HN
and elemental selenium [12-14] proceeds under mild
3
H
о
A
B
conditions (25 С, 10 min, CCl , molar ratio phosphine
4
selenide : Et N = 1 : 1) with the formation of
selenophosphoryl chlorides III, IV in quantitative
3
B + Et HN
Et N + CHCl3
3
3
yield.
Therefore, the reaction of chlorination of secondary
phosphine selenides with the system CCl /NEt provides
a new and convenient approach to the synthesis of
It should be mentioned that the reaction occurs also
in the presence of catalytic amounts of triethylamine
4
3
1
043

1
044
MALYSHEVA et al.
selenophosphoryl chlorides, reactive intermediates and
synthons for organic and organoelement synthesis.
250°С, pressure 300 kPa; temperature programming
from 70 to 250°С, 10 deg min . All experiments were
–
1
run in an inert atmosphere (argon). The reactions were
followed by the Р NMR spectroscopy.
Bis(2-phenylethyl)selenophosphoryl chloride (III).
To the solution of bis(2-phenylethyl)phosphine
selenide I (0.32 g, 1 mmol) in 7 ml of CCl4
triethylamine (0.10 g, 1 mmol) was added and stirred
for 10 min at room temperature. Formation of
chloroform in the reaction mixture was proved by
3
1
ACKNOWLEDGMENTS
This work was financially supported by the Russian
Foundation for Basic Research (grants nis. 07-03-
0
0562 and 08-03-00251) and the President of RF
chromato-mass spectrometry (peak of molecular ion
+
(Program of support of leading scientific schools, grant
no. NSh-263.2008.3).
[
M] with m/z 118). The solvent was removed, the
residue washed with 5 ml of cold hexane, dried in
vacuum. Obtained 0.35 g (98%) of compound III as
colorless needles deliquescing in the air. Н NMR
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80
35
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.94–3.96 m (4H, CH -furan), 6.05–7.30 m (6H, H
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7
С
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1
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2 CP
3
PC
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77
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31
77
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1
77
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–
1
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 80 No. 5 2010