118
J.-C. Monbaliu et al. / Journal of Molecular Structure 879 (2008) 113–118
128.35 (d, J1,P 12.6, C(1)), 128.97 (s, /), 140.14 (s, /),
171.96 (s, J 7.3, C@O), 188.52 (s, C@S); dP (121 MHz;
CDCl3, H3PO4) 28.84; m/z (APCI) 450 (M+H+, 100); mp
182–183ꢁC, ½aꢁD ꢀ 134:4 (c 1.25 in CHCl3).
azu company (SHIMADZU BENELUX). Dr R. Touillaux
and Dr D. Chapon are acknowledged for contribution in
NMR analyses. J.M.-B. is a senior research associate of
F.N.R.S. J.-C. M is a F.R.I.A. fellow.
20
4.3.3. 3(R)-[40-(R)-oxazolidin-2-thione-1-yl]-4-cyano-5-
diethoxyphosphoryl-1-cyclohexene (3c)
References
Obtained from 2c (0.41 g) as a slightly yellow solid
(0.49 g, 54%); Rf [ethyl acetate/cyclohexane (95/5)]: 0.38;
(Found: C, 57.1; H, 6; N, 6.6; S, 7.8; P, 7.4 C20H25N2O4PS
requires C, 57.1; H, 6; N, 6.7; S, 7.6; P, 7.4); mmax (film)/
cmꢀ1 2239, 1427 and 1247; dH (500 MHz; CDCl3, Me4Si)
1.33 (3H, m, J 6.7, PO2Et(OCH2CH3)), 1.34 (3H, m, J
6.7, PO2Et(OCH2CH3)), 2.46 (1H, tq, J6a,P 13.4, C(6)–
H), 2.57 (1H, dd, J5,6b7.3, J5,6a 0 and J5,P 22.4, C(5)–H),
2.69 (1H, m, J6b,6a 19.2 and J6b,P 30, C(6)–H), 4.14 (2H,
m, PO2Et(OCH2CH3)), 4.2 (2H, m, PO2Et(OCH2CH3)),
4.3 (1H, td, J4,5 2.7 and J4,P 6.6, C(4)–H), 4.35 (1H, dd,
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J5 a;4 1.92, C(50)–H), 5.15 (1H, dt, J2,3 2.2, J2,6b 2.2 and
0
0
0
0
0
0
J2,6a 2.2, C(2)–H), 4.81 (1H, t, J5 a;5 b 8:45 and J5 b;4 8.53,
C(50)–H), 5.15 (1H, dt, J2,3 2.2, J2,6a 2.2 and J2,6b 2.2,
C(2)–H), 5.29 (1H, dd, C(40)–H), 5.63 (1H, sept, J3,4 6.6,
C(3)–H), 5.73 (1H, m, J1,2 10.4, J1,6b 4.8, J1,6a 2.4 and
J1,6b 2.4, C(1)–H), 7.2-7.38 (5H, m, Ph); dC (125 MHz;
CDCl3, Me4Si) 16.31 (d, J 7.3, PO2Et(OCH2CH3)), 16.46
(d, J 7.3, PO2Et(OCH2CH3)), 20.71 (s, J6,P 0, C(6)),
28.32 (s, C(4)), 32.06 (s, J5,P 143, C(5)), 52.34 (s, J3,P 0,
C(3)), 61.9 (s, C(40)), 62.43 (d, J 5.5, PO2Et(OCH2CH3)),
63.27 (d, J 5.5, PO2Et(OCH2CH3)), 75.59 (s, C(50)),
118.62 (s, J 26, CN), 121.41 (s, C(2)), 125.56 (s, /), 128.7
(s, J1,P 0, C(1)), 128.86 (s, /), 129.46 (s, /), 140.06 (s, /),
180.01 (s, C@S); dP (121 MHz; CDCl3, H3PO4) 26.13; m/
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˜
[14] G. Grossmann, R. Lang, G. Ohms, D. Scheller, Magn. Res. Chem. 28
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z
(APCI) 421.3 (M+H+, 100); mp 124–125ꢁC,
20
½aꢁD ꢀ 139:1 (c 1.33 in CHCl3).
Acknowledgments
[15] L.D. Quin, M.J. Gallagher, G.T. Cunkle, D.B. Chesnut, J. Am.
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[16] G.M. Sheldrick, SHELXS-97 and SHELXL-97. Program for the
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´
This work was supported by the U.C.L. (Universite
Catholique de Louvain, Belgium), the F.N.R.S. (Fonds
National de la Recherche Scientifique, Belgium), the
`
F.R.I.A. (Fonds pour la Formation a la Recherche dans
[18] C.K. McClure, C.W. Grote, Tetrahedron Lett. 32 (1991) 5313.
l’Industrie et dans l’Agriculture, Belgium) and the Shimad-