Reaction of benzyltrimethylammonium phenylenedioxy tetrachlorophosphorate with phenylacetylene and propargyl chloride

Full text of DOI:10.1080/10426500213423

Phosphorus, Sulfur and Silicon, 2002, Vol. 177:2031–2032
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Copyright 2002 Taylor & Francis
1042-6507/02 $12.00 + .00
DOI: 10.1080/10426500290094558
REACTION OF BENZYLTRIMETHYLAMMONIUM
PHENYLENEDIOXY TETRACHLOROPHOSPHORATE
WITH PHENYLACETYLENE AND
PROPARGYL CHLORIDE
Alfiya A. Shtyrlina, Vladimir F. Mironov, Elena N. Varaksina,
and Aleksander I. Konovalov
A. E. Arbuzov Institute of Organic and Physical Chemistry,
Russian Academy of Sciences, Russia
(Received July 29, 2001; accepted December 25, 2001)
The interaction of phenylenedioxytrichlorophosphorane 1 with benzyl-
trimethylammonium chloride 2 gives the hexacoordinated derivative 3
(
97 ppm), which easily reacts (20 C, CH2Cl2) with phenylacetylene
P
or propargylchloride and leads to the preferable formation (70–80%)
of the substituted 2,7-dichloro-4-R-2-oxobenzo[e]-1,2-oxaphosphorines
4. The selective chlorination of the benzo-substituent meta to endo-
cyclic oxygen of the phosphorine heterocycle takes place. As it has been
shown earlier,1 the reaction of phosphorane 1 with PhC CH without
salt 2 yields 2,6-dichloro-2-oxo-4-phenylbenzo[e]-1,2-oxaphosphorine,
and the reaction with propargyl chloride yields 2,8-dichloro-
2-oxo-4-chloromethylbenzo-[e]-1,2-oxaphosphorine. The structure of
2-chloro- and 2-hydroxy-derivatives 4, 5 was confirmed by 1H, 13C,
The work is supported by the Russian Foundation for Basic Research (grant 00-03-
32835).
Address correspondence to Vladmir F. Mironov, A. E. Arbuzov Institute of Organic
and Physical Chemistry, Russian Academy of Sciences, Arbuzov Str, 8, Kazan, 420088
Russia. E-mail: mironov@iopc.kcn.ru
2031

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A. A. Shtyrlina et al.
31P NMR. The location of the chlorine atom in seventh position was
established on the basis of multiplicity of the C5, C8, C8a signals in 13
NMR spectra.
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REFERENCE
[1] V. F. Mironov, A. I. Konovalov, I. A. Litvinov, A. T. Gubaidullin, R. R. Petrov, A. A.
Shtyrlina, T. A. Zyablikova, N. M. Azancheev, R. Z. Musin, and A. V. Il’yasov, Zh.
Obshch. Khim. 68, 1482 (1998).