CATALYTIC HYDROPHOSPHORYLATION OF DIALKYL 2-ALLYLMALONATES
1175
phine oxide, according to [25], and tetrakis(triphenyl-
phosphine)palladium(0), according to [26].
REFERENCES
1
2
. Reznikov, A.N., Sokolova, M.V., and Skvortsov, N.K.,
Zh. Obshch. Khim., 2004, vol. 74, no. 9, p. 1573.
Hydrophosphorylation of unsaturated compounds
was carried out by heating in the presence of 2 mol%
of [Pd(Ph P) ] in a dry ampule purged with argon for
. Mass-spektrometricheskie kharakteristiki organiches-
kikh and elementoorganicheskikh soedinenii (Mass-
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Nauk SSSR, 1987.
3
4
2
0 h at 120 C. Analysis of the reaction mixtures was
3
1
performed using P NMR spectroscopy and GC MS.
Compounds IIIa and IIIb were isolated by vacuum
fractionation.
3
4
. Vul’fson, N.S., Zaikin, V.G., and Mikaya, A.I., Mass-
spektrometriya organicheskikh soedinenii (Mass Spec-
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1986.
Dimethyl 2-[2-(dimethoxyphosphinoyl)pro-
pyl]malonate (IIIa) was prepared from 1.05 g di-
methyl hydrogen phosphite and 1.03 g of dimethyl
. Vasilevskii, S.V., Kireev, A.F., Rybal’chenko, I.V.,
and Suvorkin, V.N., Zh. Anal. Khim., 2002, vol. 57,
no. 6, p. 597.
2-allylmalonate in the presence of 219 mg of
[
Pd(Ph P) ], yield 451 mg (26.7%), bp 131 C (3 mm
3
4
1
Hg). H NMR spectrum, , ppm: 0.98 d.d (CH CH,
3
5
6
7
8
. Tsunoda, N., J. Mass. Spectrom. Soc. Jpn., 2005,
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3
H, JHH 7.5, JHP 7.5 Hz), 1.59 1.75 m [CH CH
2
(
COOMe) , 2H], 2.59 m (CH, 1H), 3.66?3.70 m
2
. Brodskii, E.S. and Kireev, A.F., Zh. Anal. Khim.,
[
CH O, 12H, CH(COOMe) , 1H].
3
2
1
997, vol. 52, no. 8, p. 884.
Dibutyl 2-[2-(dibutoxyphosphinoyl)propyl]-
. NIST Chemistry WebBook, http://www. webbook.nist.
malonate (IIIb) was prepared from 2.30 g of dibutyl
hydrogen phosphite and 3.04 g of dibutyl 2-allyl-
malonate in the presence of 274 mg of [Pd(Ph P) ],
gov./chemistry.
. Krapcho, A.P., Synthesis, 1982, no. 10, p. 805.
3
4
1
9. Krapcho, A.P. and Lovey, A.J., Tetrahedron Lett.,
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yield 1.09 g (20.4%), bp 175 C (3 mm Hg). H NMR
spectrum, , ppm: 0.83 t (CH , 12H, J 7.1 Hz),
1
3
HH
1
0. Ykman, P. and Hall, H.K., Tetrahedron Lett., 1975,
0
.96 d.d (CH CH, 3H, J 7.5, JHP 7.5 Hz), 1.27 m
3 HH
vol. 16, no. 29, p. 2429.
(
CH , 8H, J 7.0 Hz), 1.53 m (CH , 8H, JHH 7.0 Hz),
2 HH 2
1
3
4
.66 m [CH CH(COOBu) , 2H], 2.51 m (CH, 1H),
11. Purrington, S.T., Everett, T.S., and Burgarder, C.L.,
2
2
.67 m [CH(COOBu) , 1H], 3.91 m (CH O, 4H),
Tetrahedron Lett., 1984, vol. 25, no. 13, p. 1329.
2
2
.03 m (CH O, 4H).
2
12. Ho, T.-L., Synth. Commun., 1979, vol. 9, no. 7,
p. 609.
Radical reaction of hydrophosphoryl com-
pounds with dimethyl 2-allylmalonate (general
procedure). A mixture of hydrophosphoryl compound,
1
3. Dehmlow, E.V. and Kunesch, E., Synthesis, 1985,
no. 3, p. 320.
1
5.3 mmol, and 15.3 mmol of dialkyl 2-allylmalonate
14. Metody elementoorganicheskoi khimii. Tipy metallo-
organicheskikh soedinenii perekhodnykh metallov
(Methods of Organoelement Chemistry. Types of
Transition Metal Compounds), Nesmeyanov, A.N.
and Kocheshkov, K.A., Moscow: Nauka, 1975, p. 757.
was heated under argon in the presence of 3.10 mmol
of a radical initiator (benzoyl peroxide or AIBN) at
1
a DT-220 high-pressure mercury lamp for 20 h. Ac-
cording to 31P NMR data, the conversion in the reac-
tion of dimethyl hydrogen phosphite with dimethyl
00 C for 10 h or illuminated with unfiltered light of
1
1
1
5. Tsuji, J., Palladium Reagents and Catalysts. Innova-
tions in Organic Synthesis, Chichester: Wiley, 1995,
p. 297.
2-allylmalonate was 60.4% and in the reaction of di-
phenylphosphine oxide with dimethyl 2-allylmalonate
6. Crabtree, R.H., The Organometallic Chemistry of the
Transition Metals, Hoboken: Wiley, 2005, pp. 263,
79.5% (UV initiation) or 100% (AIBN initiation).
4
47.
ACKNOWLEDGMENTS
7. Grigg, R., Malone, J.F., Mitchell, T.R.B., Rama-
subbu, A., and Scott, R.M., J. Chem. Soc., Perkin
Trans. 1, 1984, p. 1745.
This work was financially supported by the Rus-
sian Foundation for Basic Research (project no. 04-
3-32632a) and Administration of St. Petersburg
project no. PD06-1.3-61).
0
(
18. Grigg, R., Mitchell, T.R.B., and Ramasubbu, A.,
J. Chem. Soc., Chem. Commun., 1980, no. 1, p. 27.
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