3230
W. Al-Maksoud et al. / Journal of Organometallic Chemistry 694 (2009) 3222–3231
2
3
13C NMR (62.9 MHz, CDCl3): dppm: 140.5 (d, JC–P = 7.0 Hz, P–
132.3, 131.0, 130.3, 129.0, 128.6, 124.6 (d, JC–P = 10.0 Hz) and
3
CH@CH); 140.5 (Cq–C8H5S); 136.9 (Cq–C8H5S); 132.2 (d, JC–P
24.8 Hz, P–CH@CH), 127.5 (d, JC–P = 2.2 Hz, CH–C8H5S); 125.0,
124.9, 123.0 and 121.9 (CH–C8H5S); 114.6 (d, JC–P = 191.2 Hz, P–
CH@C); 61.9 (d, JC–P = 5.6 Hz, CHCH2O); 16.4 (d, JC–P = 6.3 Hz,
CH3CH2O). 31P NMR (101.2 MHz, CDCl3): 19.53. C14H17O3PS:
296.06 g/mol; MS m/z (%) = 296 [M+] (50).
=
124.3 (Cq–C16H9); 128.3, 128.2, 127.0, 126.0, 125.6, 125.5, 124.7,
123.6 and 122.1 (CH–C16H9); 128.3 (d, JC–P = 3.7 Hz, P–CH@CH);
4
3
1
1
2
115.5 (d, JC–P = 190.7 Hz, P–CH@CH); 62.0 (d, JC–P = 5.0 Hz,
CH3CH2O); 16.5 (d, JC–P = 6.3 Hz, CH3CH2O). 31P NMR (101.2 MHz,
2
3
3
CDCl3): 19.61. C22H21O3P: 364.12 g/mol; MS m/z (%) = 364 [M+]
(30).
O
O
OEt
OEt
OEt
OEt
4
5
8
P
P
9
3
6
7
2
10
N
1
60% as a yellow oil. 1H NMR (250 MHz, CDCl3): dppm: 9.01 (d, 1H,
4J = 2.2 Hz, H2); 8.16 (d, 1H, 4J = 1.7 Hz, H4); 7.91 (dd, 1H,
74% as a red oil. 1H NMR (250 MHz, C7D8): dppm: 8.51 (dd, 1H,
3
3J = 17.5 Hz, JH–P = 23.4 Hz, P–CH@CH); 7.70 (td, 1H, 3J = 6.5 Hz,
3
3J = 17.7 Hz, JH–P = 22.7 Hz, –P–CH@CH–); 8.25–8.2 (m, 2H,
4J = 1.5 Hz, H6); 7.60 (d, 1H, 3J = 6.5 Hz, H8); 7.53 (d, 1H,
3J = 6.5 Hz, H5); 7.6 (td, 1H, 3J = 6.5 Hz, 4J = 1.0 Hz, H7); 6.45 (dd,
C
14H9); 8.08 (s, 1H, C14H9); 7.76–7.70 (m, 2H, C14H9); 7.23–7.19
2
(m, 4H C14H9); 6.18 (dd, 1H, 3J = 17.7 Hz, JH–P = 19.7 Hz, –P–
CH@CH–); 4.08 (pseudo-q, 4H, 3J = 7.2 Hz, CH3–CH2O); 1.17 (t, 6H,
3J = 7.2 Hz, CH3–CH2O). 13C NMR (62.9 MHz, CD2Cl2): dppm: 146.7
2
1H, 3J = 17.5 Hz, JH–P = 16.7 Hz, P–CH@CH); 4.11 (pseudo-q, 4H,
3J = 7.2 Hz, CH3CH2O); 1.32 (t, 6H, 3J = 7.5 Hz,CH3CH2O). 13C NMR
(62.9 MHz, CDCl3): dppm: 148.6 (C2–C9H7N); 148.0 (C10–C9H7N);
2
3
(d, JC–P = 5.7 Hz, –P–CH@CH–); 132.3 (Cq–C14H9); 131.6 (d, JC–P
=
2
145.0 (d, JC–P = 6.8 Hz, P–CH@CH); 135.6 (C4–C9H7N); 130.7(C6–
22.5 Hz, Cq(vinyl)–C14H9); 129.9 (Cq–C14H9); 129.8 (C14H9); 129.8
(C14H9); 127.4 (C14H9); 126.5 (C14H9); 126.2 (C14H9); 126.1(d,
C9H7N); 129.1 (C5–C9H7N); 128.3 (C8–C9H7N); 127.9(C9–C9H7N);
3
127.6 (C7–C9H7N); 127.5 (d, C3–C9H7N, JC–P = 2.5 Hz); 116.7 (d,
2
1JC–P = 185.6 Hz, –P–CH@CH–); 62.4 (d, JC–P = 5.6 Hz, CH3–CH2O);
2
1JC–P = 191.3 Hz, P–CH@CH); 62.1 (d, JC–P = 5.6 Hz, CH3CH2O); 16.4
3
16.7 (d, JC–P = 6.2 Hz, CH3–CH2O). 31P NMR (101.2 MHz, C7D8):
3
(d, JC–P = 6.4 Hz, CH3CH2O). 31P NMR (101.2 MHz, CDCl3): 18.18.
17.08. C20H21O3P: 340.00 g/mol; MS m/z (%) = 340 [M+] (15); 202
C15H18NO3P: 291.10 g/mol; MS m/z (%) = 291[M+] (30).
[M+–(PO(OEt)2)] (100).
OEt
O
Acknowledgments
OEt
P
WAL thanks the municipality of Kalamoun for a grant. We
kindly acknowledge the research program ‘‘CEDRE” for funding.
5
8
3
9
6
7
4
N
2
10
References
1
[1] T. Minami, J. Motoyoshiya, Synthesis (1992) 333.
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65% as a red liquid. 1H NMR (250 MHz, CDCl3): dppm: 9.20 (s, 1H,
H1); 8.66 (s, 1H, H3); 8.2 (d, 1H, 3J = 17.5 Hz, H5); 8.13 (dd, 1H,
3
3J = 17.4 Hz, JH–P = 21.9 Hz, P–CH@CH); 8.05 (d, 1H, 3J = 18.0 Hz,
H8); 7.76 (td, 1H, 3J = 7.0 Hz, 4J = 1.5 Hz, –H6); 7.63 (td, 1H,
2
3J = 7.0 Hz, 4J = 1.0 Hz, H7); 6.41 (dd, 1H, 3J = 17.4 Hz, JH–P
=
17.9 Hz, P–CH@CH); 4.14 (pseudo-q, 4H, 3J = 7.2 Hz, CH3CH2O);
1.33 (t, 6H, 3J = 7.2 Hz,CH3CH2O). 13C NMR (62.9 MHz, CDCl3): dppm
:
153.7 (C1–C9H7N); 142.8 (d, JC–P = 7.0 Hz, P–CH@CH); 140.8 (C3–
C9H7N); 133.4 (C9–C9H7N); 131.4 (C6–C9H7N); 128.4 (C4–C9H7N);
128.3 (C8–C9H7N); 128.0 (C10–C9H7N); 127.8 (C7–C9H7N); 122.5
2
(C5–C9H7N); 119.4 (d, 1C, JC–P = 188.8 Hz, P–CH@CH); 62.1 (d,
1
2JC–P = 5.6 Hz, CH3CH2O); 16.4 (d, JC–P = 6.3 Hz, CH3CH2O). 31P
3
[12] P.J. Lennon, (M. Company (Ed.)), 1995.
[13] H.-J. Cristau, X.Y. Mbianda, Y. Beziat, M.-B. Gasc, J. Organomet. Chem. 529
(1977) 301.
NMR (101.2 MHz, CDCl3): 18.98. C15H18NO3P: 291.10 g/mol; MS
m/z (%) = 291 [M+] (20).
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[15] W.B. Jang, D.Y. Oh, C.-W. Lee, Tetrahedron Lett. 41 (2000) 5103.
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(1998) 6239.
EtO
EtO
O
P
[23] Y. Shen, G.-F. Jiang, Synthesis (2000) 99.
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161.
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31 (1995) 64.
70% as a dark orange oil. 1H NMR (250 MHz, CDCl3): dppm: 8.57 (dd,
1H, 3J = 17.2 Hz, 3JH–P = 22.5 Hz, P–CH@CH); 8.4–7.9 (m, 9H, C16H9);
2
6.47 (dd, 1H, 3J = 17.2 Hz, JH–P = 18.3 Hz, P–CH@CH); 4.17 (pseudo-
q, 4H, 3J = 7.0 Hz, CH3CH2O); 1.36 (t, 6H, 3J = 7.0 Hz, CH3CH2O). 13C
2
[28] Y. Xu, X. Jin, G. Huang, Y. Huang, Synthesis (1983) 556.
NMR (62.9 MHz, CDCl3): dppm: 145.3 (d, JC–P = 7.3 Hz, P–CH@CH);