Biographical radiation-induced defect formation as a method for the activation of red phosphorus in reactions with arylalkenes

Full text of DOI:10.1023/A:1023460311174

Russian Chemical Bulletin, International Edition, Vol. 52, No. 2, pp. 511—512, February, 2003
511
Letters to the Editor
Biographical radiationꢀinduced defect formation as a method for
the activation of red phosphorus in reactions with arylalkenes
N. K. Gusarova,aꢀ S. I. Shaikhudinova,a B. G. Sukhov,a T. I. Kazantseva,a S. F. Malysheva,a
Yu. V. Smetannikov,b N. P. Tarasova,b V. A. Kuimov,a and B. A. Trofimova
aA. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences,
1 ul. Favorskogo, 664033 Irkutsk, Russian Federation.
Fax: +7 (395 2) 39 6046. Eꢀmail: gusarova@irioch.irk.ru
bD. I. Mendeleev Russian University for Chemical Technology,
9 Miusskaya pl., 125047 Moscow, Russian Federation.
Fax: +7 (095) 200 4204
In recent years, it has been reported that the modificaꢀ
tion of the chemical properties of red phosphorus (both in
inorganic1—2 and organic3—6 processes) can be regulated
by controlled defect formation in its structure.
tris[2ꢀ(2ꢀnaphthyl)ethyl]phosphine oxide (3), 2ꢀ(2ꢀnaphꢀ
thyl)ethylphosphinic acid (4), and bis[2ꢀ(2ꢀnaphꢀ
thyl)ethyl]phosphine oxide (5) as the major reaction prodꢀ
ucts in a total yield of 73% (product ratio 1.6 : 1.2 : 1).
Under comparable conditions, phosphorylation of
2ꢀvinylnaphthalene with P4 or Pn is less efficient but more
selective (phosphine oxide 3 is formed in 58 and 44%
yield, respectively). In addition, the above reaction with
Pn affords acid 4 in 11% yield.
New data on the effect of biographical defects on the
reactivity of elementary phosphorus were obtained in diꢀ
rect phosphorylation of arylalkenes in a KOH—DMSO
system. Red phosphorus *Pn synthesized by radiationꢀ
induced polymerization of white phosphorus in benzene
(with 60Co as the radiation source) and containing P—
P—Rꢀtype defects (R is a benzene fragment)5 reacts with
styrene at room temperature to give diphenethylphosphine
oxide (1) and phenethylphosphinic acid (2) in a total
yield of 15%. With commercial red phosphorus Pn proꢀ
duced by thermal polymerization of white phosphorus,
the total yield of organophosphorus compounds 1 and 2
did not exceed 2%. Under similar conditions, white phosꢀ
phorus P4 is more reactive: the total yield of compounds 1
and 2 is 30%.
The formation of oxygenꢀcontaining compounds 1—5
seems to be in accord with the proposed mechanism.7
Compounds 1—5 were isolated and identified by comꢀ
1
paring their H and 31P NMR spectra (Bruker DPXꢀ400;
400 and 161.98 MHz, respectively; CDCl3) with spectroꢀ
scopic data for authentic samples.8,9
References
In phosphorylation of 2ꢀvinylnaphthalene (90—96 °C),
defective *Pn is superior to both Pn and P4 to give
1. G. V. Astakhova, S. N. Kamorskii, V. V. Korolev, V. V.
Makarenko, and L. B. Soroka, Khim. Promꢀst´, 1990, 30.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 488—489, February, 2003.
1066ꢀ5285/03/5202ꢀ511 $25.00 © 2003 Plenum Publishing Corporation

512
Russ.Chem.Bull., Int.Ed., Vol. 52, No. 2, February, 2003
Gusarova et al.
2. G. T. Shechkov, A. V. Domin, and N. M. Neskorodova,
Zh. Prikl. Khim., 1993, 66, 1948 [Russ. J. Appl. Chem., 1993,
66 (Engl. Transl.)].
3. N. K. Gusarova, Yu. V. Smetannikov, B. G. Sukhov, S. F.
Malysheva, N. P. Tarasova, and B. A. Trofimov, Zh. Obshch.
Khim., 2001, 71, 688 [Russ. J. Gen. Chem., 2001, 71 (Engl.
Transl.)].
4. N. K. Gusarova, B. G. Sukhov, S. F. Malysheva, T. I.
Kazantseva, Yu. V. Smetannikov, N. P. Tarasova, and B. A.
Trofimov, Zh. Obshch. Khim., 2001, 71, 768 [Russ. J. Gen.
Chem., 2001, 71 (Engl. Transl.)].
5. N. K. Gusarova, S. I. Shaikhudinova, T. I. Kazantseva,
B. G. Sukhov, V. I. Dmitriev, L. M. Sinegovskaya, Yu. V.
Smetannikov, N. P. Tarasova, and B. A. Trofimov, Khim.
Geterotsikl. Soedin., 2001, 628 [Chem. Heterocycl. Compd., 2001
(Engl. Transl.)].
Martynovich, Dokl. Akad. Nauk, 2002, 382, 214 [Dokl. Chem.,
2002 (Engl. Transl.)].
7. N. K. Gusarova, S. F. Malysheva, S. N. Arbuzova, and B. A.
Trofimov, Izv. Akad. Nauk, Ser. Khim., 1998, 1695 [Russ.
Chem. Bull., 1998, 47, 1645 (Engl. Transl.)].
8. S. N. Arbuzova, N. K. Gusarova, S. F. Malysheva,
L. Brandsma, A. I. Albanov, and B. A. Trofimov, Zh. Obshch.
Khim., 1996, 66, 57 [Russ. J. Gen. Chem., 1996, 66 (Engl.
Transl.)].
9. N. K. Gusarova, S. I. Shaikhudinova, T. I. Kazantseva, S. F.
Malysheva, B. G. Sukhov, N. A. Belogorlova, V. I. Dmitriev,
and B. A. Trofimov, Zh. Obshch. Khim., 2002, 72, 768 [Russ.
J. Gen. Chem., 2002, 72 (Engl. Transl.)].
6. B. A. Trofimov, B. G. Sukhov, N. K. Gusarova, S. F.
Malysheva, V. V. Tirskii, L. I. Ruzhnikov, and E. F.
Received October 8, 2002;
in revised form November 26, 2002