The new data for the reaction of arylenedioxy trihalogenophosphoranes with alkyl- and arylacetylenes

Article abstract of DOI:10.1080/10426500212243

The new data concerning the reaction between substituted arylenedioxy trihalogenophosphoranes and monoalkyl- or arylacetylenes are summarized. The reaction leads to formation of six-membered heterocycles-2-oxo-4-R-benzo[e]-1,2-oxaphosphorin-3- enes. The substituent effects in the phosphorane and acetylene molecules on the ipso-substitution and halogenation regiochemistry are discussed. The ipso-substitution of tert-butyl group on chlorine and the exchange of bromine on chlorine and iodine on hydrogen have been observed, along with formation of benzophosphorines. The interaction of tetrachloro-ortho-benzoquinone with phosphorus trichloride and arylacetylenes is proposed as a new modification of the reaction leading to the formation of benzo[e]-1,2-oxaphosphorines. The structures of some benzo[e]-1,2-oxaphosphorines are determined by the single crystal X-ray diffraction.

Full text of DOI:10.1080/10426500212243

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Phosphorus, Sulfur, and Silicon and the Related
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The New Data for the Reaction of Arylenedioxy
Trihalogenophosphoranes with Alkyl- and
Arylacetylenes
Vladimir F. Mironov a , Alfiya A. Shtyrlina a , Ravil R. Petrov a , Tamara A. Baronova a , Fedor
F. Alekseev a , Elena N. Varaksina a & Aleksander I. Konovalov a
a A. E. Arbuzov Institute of Organic and Physical Chemistry , Russian Academy of Sciences ,
Kazan, Russia
Published online: 27 Oct 2010.
To cite this article: Vladimir F. Mironov , Alfiya A. Shtyrlina , Ravil R. Petrov , Tamara A. Baronova , Fedor F. Alekseev ,
Elena N. Varaksina & Aleksander I. Konovalov (2002) The New Data for the Reaction of Arylenedioxy Trihalogenophosphoranes
with Alkyl- and Arylacetylenes, Phosphorus, Sulfur, and Silicon and the Related Elements, 177:6-7, 1381-1385, DOI:
10.1080/10426500212243
To link to this article: http://dx.doi.org/10.1080/10426500212243
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Phosphorus, Sulfur and Silicon, 2002, Vol. 177:1381–1385
C
Copyright 2002 Taylor & Francis
1042-6507/02 $12.00 + .00
DOI: 10.1080/10426500290093766
THE NEW DATA FOR THE REACTION OF
ARYLENEDIOXY TRIHALOGENOPHOSPHORANES
WITH ALKYL- AND ARYLACETYLENES
Vladimir F. Mironov, Alfiya A. Shtyrlina, Ravil R. Petrov,
Tamara A. Baronova, Fedor F. Alekseev, Elena N. Varaksina,
and Aleksander I. Konovalov
A. E. Arbuzov Institute of Organic and Physical Chemistry,
Russian Academy of Sciences, Kazan, Russia
(Received July 29, 2001; accepted December 25, 2001)
The new data concerning the reaction between substituted arylenedioxy
trihalogenophosphoranes and monoalkyl- or arylacetylenes are sum-
marized. The reaction leads to formation of six-membered heterocycles–
2-oxo-4-R-benzo[e]-1,2-oxaphosphorin-3-enes. The substituent effects in
the phosphorane and acetylene molecules on the ipso-substitution and
halogenation regiochemistry are discussed. The ipso-substitution of
tert-butyl group on chlorine and the exchange of bromine on chlorine
and iodine on hydrogen have been observed, along with formation of
benzophosphorines. The interaction of tetrachloro-ortho-benzoquinone
with phosphorus trichloride and arylacetylenes is proposed as a new
modification of the reaction leading to the formation of benzo[e]-1,2-
oxaphosphorines. The structures of some benzo[e]-1,2-oxaphosphorines
are determined by the single crystal X-ray diffraction.
Keywords: Acetylenes; halogenation; ipso-substitution; phosphoranes;
phosphorus trichloride; reactions; tetrachloro-ortho-benzoquinone
Earlier1 we have shown that the interaction of the trichlorophospho-
rane 1 with arylacetylenes gives an unusual synthetic result. The
six-membered phosphorus heterocycle–benzoxaphosphorine 2 was ob-
tained with a high yield. An easy formation of phosphoryl group and
P C bond, ipso-substitution of oxygen, and selective chlorination in the
para-position to endocyclic oxygen took place under the soft conditions
in this reaction.
Address correspondence to V. 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.ken.ru
1381

1382
V. F. Mironov et al.
The further investigation of the reaction between cathehol tri-
halogenophosphoranes and monosubstituted acetylenes has been
considered in this report. To study the influence of the phosphorane
structure on the synthetic result, we introduced both donor and accep-
tor substituents to the benzene ring.
The presence of the ortho-chlorine atoms at the benzene ring of phos-
phorane 3 leads to appearance of some peculiarities in the reaction with
arylacetylene. The reaction mixture contains two isomeric vinylphos-
phonates 5 and 6 of the quinoid type along with the heterocyclic product
4. The isomeric phosphonates were identified according to their three
bonds phosphorus-carbon and proton-carbon couplings. Obviously, two
ortho-chlorine atoms essentially hinders cyclization.
The most interesting situation arises when the phosphorane
molecule contains two different kinds of halogen, such as chlorine and
bromine. The compound 7 reacts with phenylacetylene to give three
types of phosphorines: 8, 9 and 10. The identification of the compounds
has been made by the proton and carbon NMR as well as the comparison
with the spectra of the pure substances 8 and 9 described earlier.2

New Data on Arylenedioxy Trihalogenophosphoranes
1383
The high regioselectivity of the oxygen ipso-substitution has been
observed in the reaction of the unsymmetrical tribromophosphorane 11
with phenylacetylene. Exclusively, the ipso-substitution of the oxygen
connected with the brominated ortho-carbon occures. The major product
of the reaction is phosphorine 12.
The reaction of the phosphorane 13 containing bromine in a benzene
ring with phenylacetylene unexpectedly leads to the preferable forma-
tion of the monosubstituted compound 14 containing the bromine atom
meta to oxygen with a high yield. This result is in accordance with the
lower ability of bromine in comparison with chlorine to migrate to the
benzene ring.
Phosphorane 15 containing a donor methyl group easily reacts with
arylacetylenes, giving the compound 16 with a high regioselectivity.
The location of a chlorine atom was determined by the NMR and single
crystal X-ray diffraction. The similar reaction of bromophosphorane 17
with phenylacetylene turned out to yield two phosphorines, 18 and 19.
The main product 18 contains a bromine para to the endocyclic oxygen.
The ipso-substitution of the tert-butyl group situated para to oxy-
gen by the chlorine proceeds in the reaction of the phosphorane 20

1384
V. F. Mironov et al.
with phenylacetylene. The structure of 21 was determined by the single
crystal X-ray diffraction.
Alkylacetylenes like propargyl chloride can also react with phos-
phorane 1 to give phosphorine 22 under soft conditions. An un-
usual peculiarity of the reaction is an incorporation of chlorine in the
ortho-position to the endocyclic oxygen. The interaction of phosphorane
1 with propargyl chloride has lost the regioselectivity of the chlorina-
tion under heating—that is, three isomers 22–24 are formed. However
the para-isomer 23 predominates.
Disubstituted iodophenylacetylene can also react with phosphorane
1 and unexpectedly gives four compounds 2, 25–27. Phosphorines 2,
27 contain hydrogen instead of iodine. Compounds 2, 26 are predom-
inant. The structure of phosphorines was established by carbon NMR
spectroscopy.

New Data on Arylenedioxy Trihalogenophosphoranes
1385
In some cases, it is enough to use the mixture of quinone and phos-
phorus trihalogenide instead of phosphorane. So, the interaction of the
tetrachlorobenzoquinone with arylacetylene and PCl3 gives the hetero-
cycles 4 with the moderate yield. The open-chain structures 5, 6 were
also obtained.
ACKNOWLEDGMENTS
The work is supported by the Russian Foundation for Basic Research
(grant 00-03-32835).
REFERENCES
[1] V. F. Mironov, A. I. Konovalov, I. A. Litvinov, A. T. Gubaidullin, R. R. Petrov, A. A.
Shtyrlina et al., Zh. Obshch. Khim., 68, 1482 (1998).
[2] V. F. Mironov, I. A. Litvinov, A. A. Shtyrlina, A. T. Gubaidullin, R. R. Petrov, A. I.
Konovalov et al., Zh. Obshch. Khim., 70, 1117 (2000).