Russian Journal of General Chemistry, Vol. 72, No. 3, 2002, pp. 490 491. Translated from Zhurnal Obshchei Khimii, Vol. 72, No. 3, 2002,
pp. 525 526.
Original Russian Text Copyright
2002 by Mironov, Shtyrlina, Varaksina, Konovalov.
LETTERS
TO THE EDITOR
Reaction of Phenylacetylene with the at Complex on the Basis
of Trichloro(phenylenedioxy)phosphorane and Pyridine
V. F. Mironov, A. A. Shtyrlina, N. E. Varaksina, and A. I. Konovalov
Arbuzov Institute of Organic and Physical Chemistry, Kazan Research Center,
Russian Academy of Sciences, Kazan, Tatarstan, Russia
Received May 10, 2001
It is known that trichloro(phenylenedioxy)phos-
phorane (I) reacts with arylacetylenes unlike PCl5 to
give 2,6-dichlorobenzo[e][1,2]oxaphosphinine 2-oxide
as a result of multistage transformations involving an
extremely easy formation of the P C bond and the
phosphoryl group, as well as ipso substitution of the
oxygen atom and regioselective chlorination of the
aromatic ring in the para position with respect to the
endocyclic oxygen atom of the phosphinine heteroring
[1].
we showed for the first time that the so-called at
complexes, six-coordinate phosphorus derivatives, can
also react with arylacetylenes. For example, a crystal-
line complex of phosphorane I with pyridine [2],
which has the structure of phosphorate II (
129.7
P
and 137.1 ppm, CH2Cl2) readily reacts with phenyl-
acetylene to give chlorophosphinine III in high yield
2
(
16.1 ppm, JPCH 24.2 Hz, CH2Cl2). The reaction
P
involves dissolution of at complex II and precipita-
tion of pyridine hydrochloride. The latter was separa-
ted and identified by spectral methods.
Proceeding with these studies, in the present work
O
O
8
5
Cl
O
O
O
7
Cl
H2O
HCl
P
3
P
PhC CH
OH
Cl
P
Cl
Py HCl
Cl
Cl
O
Py
Ph
Ph
II
III
IV
The formation of pyridine hydrochloride points to
chlorination of the aromatic fragment. The position of
the chlorine atom in the benzene ring was established
solution of 3.0 g of phosphorane I in 10 ml of CH2Cl2.
Phenylacetylene, 1.35 ml, was added at 20 C to the
resulting precipitate of at complex III, and the reac-
tion mixture was allowed to warm to 20 C for 1
1.5 h. Therewith, the complex completely dissolved
and course crystals of pyridine hydrochloride formed
within 5 8 days. The crystals were filtered off, the
solvent was removed in a vacuum, the residue was
extracted with benzene, and the benzene extract was
evaporated. The light yellow glassy residue was dis-
solved in dioxane and treated with water to isolate
1
by comparison of the H and 13C NMR spectra of
phosphonic acid IV obtained by hydrolysis with the
sample of compound IV we prepared previously [1].
Note that use of the at complex of trichloro(phe-
nylenedioxy)phosphorane with pyridine (complex II)
in the reaction with phenylacetylene is preferred over
use of a double excess of the latter, because in this
case there is no need in purification of the reaction
product from 1-chloro-1-phenylethylene formed by
HCl reaction with the acetylene.
1
2.86 g (80%) of phosphorine IV, mp 258 260 C. H
NMR spectrum (250 MHz, DMSO-d6), , ppm (J, Hz):
2
4
6.36 d (H3, JPCH 17.3), 7.02 d (H5, JHCCCH 2.6),
7.49 d.d.d (H7, JHCCH 8.8, JHCCCH 2.6, JHCCCCH
3
4
5
6-Chloro-2-hydroxybenzo[e][1,2]oxaphosphinine
2-oxide (IV). Pyridine, 0.99 ml, in 5 ml of CH2Cl2
was added with stirring at 20 C under argon to a
1.6), 7.33 d (H8, JHCCH 8.8), 7.52 m and 7.39 m
3
(C6H5). For the 13C NMR spectrum, see [1]. Found,
1070-3632/02/7203-0490$27.00 2002 MAIK Nauka/Interperiodica
Mironov
