Chemoselective reaction of red phosphorus with 4-vinylbenzyl chloride: A convenient route to tris(4-vinylbenzyl)phosphine oxide

Full text of DOI:10.1134/S1070363206020289

ISSN 1070-3632, Russian Journal of General Chemistry, 2006, Vol. 76, No. 2, pp. 325 326.
Original Russian Text N.K. Gusarova, V.A. Kuimov, S.F. Malysheva, B.G. Sukhov, B.A. Trofimov, 2006, published in Zhurnal Obshchei Khimii, 2006,
Vol. 76, No. 2, pp. 342 343.
Pleiades Publishing, Inc., 2006.
LETTERS
TO THE EDITOR
Chemoselective Reaction of Red Phosphorus
with 4-Vinylbenzyl Chloride:
A Convenient Route to Tris(4-vinylbenzyl)phosphine Oxide
N. K. Gusarova, V. A. Kuimov, S. F. Malysheva, B. G. Sukhov, and B. A. Trofimov
Favorskii Irkutsk Institute of Chemistry, Siberian Division, Russian Academy of Sciences,
ul. Favorskogo 1, Irkutsk, 664033 Russia
Fax: (3952) 419346; E-mail: gusarova@irioch.irk.ru
Received June 28, 2005
DOI: 10.1134/S1070363206020289
Direct phosphorylation of electrophiles with
elemental phosphorus in superbasic medium such as
alkali metal hydroxide polar nonhydroxylic solvent
phile containing simultaneously benzyl chloride and
styrene fragments. In such a situation, the direction of
phosphorylation becomes ambiguous: the reaction can
proceed at the chlorine atom, at the double bond, or
at both electrophilic centers simultaneously.
(
DMSO, HMPA) or alkali metal hydroxide aqueous-
organic emulsion phase-transfer catalyst opened a
convenient route to formation of a C P bond and
synthesis of previously unknown or difficultly
available organophosphorus compounds, primarily
organic phosphines and phosphine oxides [1 7]. For
example, tribenzyl- and tris(2-phenylethyl)phosphine
oxides were prepared from red phosphorus and benzyl
chloride [8] and styrene [9], respectively, in the
presence of strong bases in high yield (50 60%).
We found that heating (45 50 C) of red phos-
phorus with 4-vinylbenzyl chloride in the system of
KOH H O dioxane phase-transfer catalyst (benzyl-
2
triethylammonium chloride) leads to chemoselective
formation of tris(4-vinylbenzyl)phosphine oxide (I),
a promising polyfunctional reagent for fine organic
synthesis, a cross-linking agent for preparation, e.g.,
fire-resistant polymers, and a building block for
construction of polydentate ligands for catalysts of
new generation [10].
Here we report on the reaction of red phosphorus
with 4-vinylbenzyl chloride, a bifunctional electro-
3
4
7
1
2
5
6
Cl
P
KOH/H O
2
Pn +
O
I
The yield of phosphine oxide I based on 4-vinyl-
benzyl chloride is 55% (not optimized). Polymeric
compounds are also formed in the course of the reac-
tion; their yield decreased when the reaction was
carried out in the presence of hydroquinone. The
synthetic potential of this reaction and the structure of
by-products are under investigation.
Tris(4-vinylbenzyl)phosphine oxide I. A solution
of 1.76 g of 4-vinylbenzyl chloride in 5.5 ml of di-
325

326
GUSAROVA et al.
oxane was added dropwise with stirring over a period
of 1.5 h to a suspension of 2.06 g of red phosphorus,
REFERENCES
0
.21 g of benzyltriethylammonium chloride, 11.7 g of
KOH, 6 ml of water, 15 ml of dioxane, and 0.1 g of
hydroquinone. The reaction mixture was stirred at
1. Trofimov, B.A., Rakhmatulina, T.N., Gusarova, N.K.,
and Malysheva, S.F., Usp. Khim., 1991, vol. 60,
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4
5 50 C for 1.5 h, cooled, diluted with a twofold
2
. Gusarova, N.K., Malysheva, S.F., Arbuzova, S.N.,
and Trofimov, B.A., Izv. Ross. Akad. Nauk, Ser. Khim.,
volume of water, and extracted with benzene; the
benzene extract was washed with water. The solvent
was removed at reduced pressure, and the residue was
reprecipitated from benzene with hexane. The product
was dried in a vacuum. Phosphine oxide I, 0.84 g
1
998, no. 9, p. 1695.
3
4
. Trofimov, B.A., Arbuzova, S.N., and Gusarova, N.K.,
Usp. Khim., 1999, vol. 68, no. 3, p. 240.
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2003, no. 6, p. 1172.
(
55%), was obtained, mp 137 140 C (hexane). IR
1
spectrum, , cm : 1180 (P=O), 1610 (CH=), 3080
1
(CH =). H NMR spectrum (CDCl ), , ppm, (J, Hz):
2
3
2
7
3
5. Malysheva, S.F. and Arbuzova, S.N., Sovremennyi
organicheskii sintez (Modern Organic Synthesis),
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p. 160.
2
.98 d (6H, H1, J 13.7), 5.22 d (3H, H , J
PH
HH
3
6
1
7
0.7), 5.71 d (3H, H7, J 17.6), 6.67 d.d (3H, H ),
HH
1
3
.17 7.33 m (12H, C H ). C NMR spectrum
6
4
1
1
(CDCl3), , ppm (J, Hz): 35.27 d (C , J 60.6),
C PC
7
4
3
2
6. Trofimov, B.A., Curr. Org. Chem., 2002, vol. 6,
1
13.89 (C ), 126.58 (C ), 130.01 (C ), 131.17 d (C ,
no. 13, p. 1121.
2
6
5
31
JPC 7.2), 136.28 (C ), 136.38 (C ). P NMR spec-
41.27 ppm. Found, %: C 80.78; H
7
. Trofimov, B.A., Sovremennye problemy organiches-
koi khimii (Current Problems of Organic Chemistry),
Potekhin, A.A., Kostikov, R.R., and Berd, M.S., Eds.,
St. Petersburg: Nauchno-Issled. Inst. Khim. Sankt-
Peterb. Gos. Univ., 2004, p. 131.
trum (CDCl3):
P
6
.85; P 8.00. C H OP. Calculated, %: C 81.38;
27 27
H 6.83; P 7.77.
The IR spectrum was recorded on a Specord IR-75
1
13
31
instrument (KBr). The H, C, and P NMR spectra
were measured on a Bruker DPX-400 instrument (400,
8
9
. Trofimov, B.A., Gusarova, N.K., Malysheva, S.F.,
Shaikhudinova, S.I., Belogorlova, N.A., Kazantse-
va, T.I., Sukhov, B.G., and Plotnikova G.V., Zh.
Obshch. Khim., 2005, vol. 75, no. 5, p. 724.
1
00, and 161.98 MHz, respectively). All manipula-
tions were performed under argon.
. Trofimov, B.A., Malysheva, S.F., Rakhmatulina, T.N.,
Gusarov, A.V., and Gusarova, N.K., Zh. Obshch.
Khim., 1991, vol. 61, no. 9, p. 1955.
ACKNOWLEDGMENTS
This study was financially supported by the Rus-
sian Foundation for Basic Research (project no. 05-
10. Herberhold, M., Milius, W., and Preifer, A., Z. Natur-
forsch. (b), 2003, vol. 58, no. 1, p. 1.
03-32859).
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 76 No. 2 2006