REACTIONS OF DIALKYL PHOSPHONATES
1749
= 28 Hz). P NMR spectrum
1
31
polar phosphonate metal hydride complex better than
δ –5.8 ppm, s ( J
H,W
1
does less polar dialkyl phosphonate–benzene medium.
Nevertheless, any intermediate product formed by
reaction of dialkyl phosphonate with metal carbonyl
ensures hydrophosphorylation of an unsaturated sub-
strate with a high efficiency.
(C D ): δ 16.2 ppm, s ( J = 355 Hz).
6
6
P
P, W
This study was performed under financial support
by the Ministry of Education of the Russian Federa-
tion, program “Universities of Russia” (project no. UR
05.01.007), and by CRDF (grant no. REC-007).
EXPERIMENTAL
REFERENCES
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The IR spectra were recorded on a Specord M-80
spectrometer from samples dispersed in mineral oil.
The H NMR spectra were recorded on Varian Unity
1
2
3
4
5
6
7
3
00 (299.94 MHz), Bruker 100 (100 MHz), and
Bruker Gemini 200 (199.827 MHz) instruments at
5°C using C D as solvent; the proton chemical shifts
2
6
6
were measured relative to the residual solvent signal.
3
1
The P NMR spectra were measured on a Varian
Unity 300 instrument (121.4 MHz). relative to external
8
5% H PO . Quantum-chemical calculations were
3 4
performed using GAMESS 98 software [9]. All experi-
ments were carried out under argon.
Reaction of diethyl phosphonate with hexacar-
bonyltungsten(0) in benzene. An ampule was purged
with argon and charged with a mixture of 0.5 g of
hexacarbonyltungsten(0), 3.6 ml of C D , and 0.40 ml
8
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6
6
of diethyl phosphonate. The ampule was sealed, and
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–1
ν, cm (film): 2050, 1980, 1890 (CO); 2600 (P–O–H).
1
H NMR spectrum (C D ): δ 4.20 ppm, s (POH).
6
6
3
1
1
P NMR spectrum (C D ): δ 156 ppm, s ( J
=
P, W
6
6
P
3
23 Hz).
1
1. Allen, A., Manke, D.R., and Lin, W., Tetrahedron Lett.,
000, vol. 41, p. 151.
Reaction of diethyl phosphonate with hexacar-
2
bonyltungsten(0) without a solvent. An ampule was
purged with argon and charged with a mixture of 0.5 g
of hexacarbonyltungsten(0) and 0.40 ml of diethyl
phosphonate. The ampule was sealed, and the mixture
heated for 20 h at 85°C. The ampule was opened,
1
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1
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2
–3 drops of C D were added, and the mixture was
6 6
15. Gordon, M.S. and Cundary, T.R., Coord. Chem. Rev.,
analyzed by NMR spectroscopy. The mixture was then
concentrated under reduced pressure to 1/3 of the
initial volume, and the residue was analyzed by IR
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1
–
1
spectroscopy. IR spectrum, ν, cm (film): 2010, 1970,
17. Pudovik, A.N., Konovalova, I.V., and Dedova, L.V.,
1
1
900, 1860 (CO). H NMR spectrum (C D ):
Zh. Obshch. Khim., 1963, vol. 42, p. 2167.
6
6
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 40 No. 12 2004