Russian Journal of General Chemistry, Vol. 71, No. 5, 2001, p. 813. Translated from Zhurnal Obshchei Khimii, Vol. 71, No. 5, 2001,
p. 866.
Original Russian Text Copyright
2001 by Borovinskii, Krivchun, Ionin.
LETTERS
TO THE EDITOR
Photochemical Chlorophosphination of Phenylacetylene
K. I. Borovinskii, M. N. Krivchun, and B. I. Ionin
St. Petersburg State Institute of Technology, St. Petersburg, Russia
Received December 26, 2000
It is known that under UV irradiation phosphorus
tribromide adds across multiple bonds to form the
corresponding P(III) adducts [1 3]. However, PCl3
does not add under these conditions. Although study
by chemically induced dynamic nuclear polarization
did reveal formation of products upon irradiation of
a mixture of phenylacetylene with PCl3, the reaction
products were not isolated [2]. Addition products were
isolated only when the reaction was induced by -ir-
radiation [4] or sensitized with PBr3 [3]. Addition of
PCl3 to alkylthiochloroacetylene under UV irradiation
was reported in [5].
spectrum, 97% E isomer I and 3% Z isomer II. E Iso-
mer I was isolated with a yield of 37.7 g (39% based
on phenylacetylene); bp 103 C (1 mm Hg), mp 26 C.
E-1-Phenyl-2-chlorovinyldichlorophosphine (I).
1H NMR spectrum (CDCl3), , ppm: 7.5 m (5H),
3
7.32 d (1H, JPH 10.81 Hz). 13C NMR spectrum
1
(CDCl3), C, ppm: 145.65 d (C1, JCP 65.02 Hz),
2
2
131.61 d (C2, JCP 89.48 Hz), 131.15 d (C4, JCP
4.58 Hz). 31P NMR spectrum (CDCl3), P, ppm:
152.48 d (3JPH 10.81 Hz).
Z-1-Phenyl-2-chlorovinyldichlorophosphine (II).
1H NMR spectrum (CDCl3), , ppm: 7.5 m (5H),
We found that under irradiation with an immersion
mercury lamp PCl3 regiospecifically and with a high
regioselectivity adds to phenylacetylene to form
1-phenyl-2-chlorovinyldichlorophosphine (isomer ratio
E : Z 97 : 3).
3
6.86 d (1H, JPH 14.61 Hz). 31P NMR spectrum
(CDCl3), P, ppm: 148.23 d (3JPH 14.61 Hz).
1
The H, 13C, and 31P NMR spectra were taken with
a Bruker C-200 spectrometer, working frequencies
200.132, 50.327, and 81.026 MHz, respectively. The
chemical shifts are given relative to internal TMS
(1H, 13C) and external 85% H3PO4 (31P).
Cl
H
Ph
Ph
h
Ph
+ PCl3
+
H
Cl
Cl2P
Cl2P
REFERENCES
I
II
The reaction does not occur without UV irradia-
tion. Compound I was isolated and oxidized to the
corresponding phosphonyl dichloride; the physico-
chemical parameters of the latter agree with published
data [6].
1. Sendyurev, M.V., Belyaeva, T.N., Kholmogorov, V.E.,
Petrov, A.A., Ionin, B.I., and Dogadina, A.V., Zh.
Obshch. Khim., 1981, vol. 51, no. 12, pp. 2803 2804.
2. Sendyurev, M.V., Gol’dfarb, E.I., Ionin, B.I., and Bu-
chachenko, A.L., Zh. Obshch. Khim., 1999, vol. 69,
no. 7, pp. 1184 1185.
3. Belyaeva, T.N., Krivchun, M.N., Sendyurev, M.V.,
Dogadina, A.V., Sokolov, V.V., Ionin, B.I., and Pet-
rov, A.A., Zh. Obshch. Khim., 1986, vol. 56, no. 5,
pp. 1184 1185.
1
The structure of the products was proved by H,
13C, and 31P NMR spectroscopy.
1-Phenyl-2-chlorovinyldichlorophosphine (I, II).
Phenylacetylene (40 g) was added dropwise with stir-
ring over a period of 1 h at 20 40 C to 345.4 g of
PCl3 irradiated with an immersion mercury UV lamp.
After adding the whole amount of phenylacetylene,
the mixture was irradiated for an additional 1 h. Then
unchanged PCl3 and phenylacetylene were distilled
off, and the residue was distilled in a vacuum. A frac-
tion (40.7 g) boiling at 100 105 C (1 mm Hg) was
obtained; it contained, according to the 31P NMR
4. Zagorets, P.A., Shostenko, A.G., and Dodonov, A.M.,
Zh. Obshch. Khim., 1975, vol. 45, no. 11, pp. 2365 2367.
5. D’yachkova, S.G., Beskrylaya, E.A., Gusarova, N.K.,
Afonin, A.V., Nikitin, M.V., and Trofimov, B.A., Zh.
Obshch. Khim., 2000, vol. 70, no. 10, pp. 1628 1630.
6. Kruglov, A.S., Dogadina, A.V., Ionin, B.I., and Pet-
rov, A.A., Zh. Obshch. Khim., 1978, vol. 48, no. 3,
p. 705.
1070-3632/01/7105-0813$25.00 2001 MAIK Nauka/Interperiodica
Borovinskii
