H. Firouzabadi et al. / Tetrahedron Letters 43 (2002) 477–480
479
conditions are worthy of mention for the presented
method.
13. Firouzabadi, H.; Iranpoor, N.; Sobhani, S.; Sardarian, A.
R. Tetrahedron Lett. 2001, 42, 4369.
14. Typical procedure for the preparation of h-ketophospho-
nates from h-hydroxyphosphonates with KMnO4 under
heterogeneous conditions (method A):
Acknowledgements
A solution of the a-hydroxyphosphonate 1 (5 mmol) in
dry benzene (50 ml) was prepared. Powdered potassium
permanganate (0.316–0.948 g, 2–6 mmol) was added and
the resulting mixture was stirred at room temperature
(3.25–12 h). Then, the reaction mixture was filtered and
the solvent was evaporated to give the crude product.
The pure product was obtained (82–98% yields) by bulb
to bulb vacuum distillation.
We thank Shiraz University and the National Research
Council of I.R. of Iran for grant no. 464 for support of
this work.
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solvent-free conditions (method B):
NASPP was prepared according to the literature.16
A
mixture of the a-hydroxyphosphonate 1 (5 mmol) and
NASPP (0.66–1.99 g, 2–6 mmol KMnO4) was stirred
vigorously (4–15 h). The reaction mixture was then
washed with CH2Cl2 (4×10 ml) and dried over Na2SO4.
The solvent was evaporated to give the desired crude
product. The pure product was obtained in 80–98% yields
by bulb to bulb vacuum distillation.
18. Spectral data of some a-ketophosphonates: 2a [1H NMR
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(CDCl3, TMS): l 1.37–1.68 (t, 6H, 2JHH=7 Hz, 2-
OCH2CH3
Hz, 2-OCH
ppm; 13C NMR (CDCl3, TMS): 16.64 (d, JCP=5.7 Hz,
2-OCH2C H2CH3),
H3), 64.31 (d, 2JCP=7.5 Hz, 2-OC
129.15, 130.06, 135.03, 136.29 (-C6H5), 199.12 (d, JCP
6
), 4.08–4.28 (dq, 4H, 2JPH=7.1 Hz, 2JHH=7
6
2CH3), 7.28–7.6 (m, 3H), 8.03–8.25 (m, 2H)
3
6
6
1
=
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177.5 Hz, CꢁO) ppm; IR (neat): w 1660 (CꢁO), 1250
(PꢁO) cm−1; MS: M+ (242)]. 2b [1H NMR (CDCl3, TMS):
l 1.29–1.42 (t, 6H, 2JHH=7 Hz, 2-OCH2CH3
6
), 2.35 (s,
3H, -CH3), 4.11–4.16 (dq, 4H, 2JPH=7.1 Hz, 2JHH=7 Hz,
2-OCH2CH3), 7.12–7.21 (m, 2H), 8.04–8.07 (m, 2H) ppm;
13C NMR (CDCl3, TMS): 16.67 (d, 3JCP=5.7 Hz, 2-
OCH2C
H3), 22.18 (-CH3), 64.24 (d, 2JCP=7.5 Hz, 2-
OCH2CH3), 127.35, 129.89, 130.31, 146.41 (-C6H4),
6
6
6
1
198.46 (d, JCP=176.6 Hz, CꢁO) ppm; IR (neat): w 1650
(CꢁO), 1260 (PꢁO) cm−1; MS: M+ (256)]. 2c [1H NMR
(CDCl3, TMS): l 1.11–1.29 (t, 6H, 2JHH=7 Hz, 2-
OCH2CH3
2JPH=7.1 Hz, 2JHH=7 Hz, 2-OCH2
2H), 7.42–7.50 (m, 2H) ppm; 13C NMR (CDCl3, TMS):
16.75 (d, 3JCP=5.7 Hz, 2-OCH2C
H3), 55.59 (-CH3), 63.46
(d, 2JCP=7.5 Hz, 2-OC
H2CH3), 114.03, 128.82, 129.21,
6
), 3.80 (s, 3H, -CH3), 3.90–4.10 (dq, 4H,
6
CH3), 6.84–6.90 (m,
6
6
159.78 (-C6H4), 198.01 (d, 1JCP=176.2 Hz, CꢁO) ppm; IR
(neat): w 1650 (CꢁO), 1265 (PꢁO) cm−1; MS: M+ (272)]. 2d
[1H NMR (CDCl3, TMS): l 1.25–1.32 (t, 6H, 2JHH=7
Hz, 2-OCH2CH6 3), 2.23 (s, 6H, 2,6-diCH3), 2.27 (s, 3H,
6
4-CH3), 4.06–4.17 (dq, 4H, 2JPH=7.1 Hz, 2JHH=7 Hz,
2-OCH
6
2CH3), 6.83 (s, 2H) ppm; 13C NMR (CDCl3,
3
TMS): 16.81 (d, JCP=5.7 Hz, 2-OCH2C
6
H3), 21.17 (2,6-
diCH3), 21.38 (4-CH3), 63.12 (d, 2JCP=7.5 Hz, 2-
OCH2CH3), 129.74, 130.3, 137.69, 137.75 (-C6H2), 199.01
6
1
(d, JCP=177.0 Hz, CꢁO) ppm; IR (neat): w 1660 (CꢁO),