96
Y. Matano et al. / Journal of Organometallic Chemistry 611 (2000) 89–99
1298, 1273, 1240, 1161, 1113, 1048, 1017, 899, 851, 785,
752, 729, 669, 419 cm−1. FABMS: m/z 837 [M++1].
Anal. Calc. for C34H31BiN2O10: C, 48.81; H, 3.73; N,
3.35. Found: C, 48.55; H, 3.71; N, 3.63%.
3.1.11. Ylide 4k
1
M.p. 158–159°C. H-NMR: l 0.91 (t, 3H, J=7.1),
1.39 (t, 3H, J=7.2), 2.42 (s, 9H), 4.00 (q, 2H, J=7.1),
4.40 (q, 2H, J=7.2), 7.38 (d, 6H, J=8.0), 7.60 (d, 6H,
J=8.0). 13C{1H}-NMR: l 13.7, 13.8, 21.5, 61.4, 62.7,
110.3, 119.7 (JCF=323), 132.2, 135.4, 135.8, 142.1,
163.8, 165.2, 166.0. IR: wmax 1728 (CꢀO), 1694 (CꢀO),
1538, 1489, 1448, 1393, 1374, 1337, 1262, 1227, 1220–
1150, 1130, 1057, 1020, 1005, 928, 893, 849, 799, 762,
741, 644, 610, 585, 507, 475 cm−1. FABMS: m/z 800
[M++1]. Anal. Calc. for C30H31BiF3NO6S: C, 45.06;
H, 3.91; N, 1.75. Found: C, 44.96; H, 3.87; N, 1.82%.
3.1.7. Ylide 4g
M.p. 179–181°C (dec.). 1H-NMR: l 3.36 (s, 3H),
3.63 (s, 9H), 4.01 (s, 3H), 6.99–7.09 (m, 6H), 7.14–7.28
(m, 3H), 7.39–7.51 (m, 4H), 7.71 (m, 3H, J=7.3). IR:
wmax 1750 (CꢀO), 1736 (CꢀO), 1676 (CꢀO), 1609, 1568,
1559, 1512, 1493, 1472, 1433, 1358, 1300, 1275, 1240,
1210, 1177, 1163, 1102, 1048, 1017, 939, 897, 860, 787,
774, 750, 569, 550, 477, 428 cm−1. FABMS: m/z 817
[M++1]. Although spectroscopic data clearly sup-
ported a high state of purity of 4g, we were not
successful in obtaining satisfactory analytical data.
3.1.12. Ylide 4l
M.p. 88–90°C. 1H-NMR: l 0.86 (t, 3H, J=7.1), 1.44
(t, 3H, J=7.1), 2.38 (s, 9H), 3.95 (q, 2H, J=7.1), 4.47
(q, 2H, J=7.1), 7.08–7.18 (m, 2H), 7.20–7.35 (m, 7H),
7.47–7.54 (m, 2H), 7.55 (d, 6H, J=8.2). 13C{1H}-
NMR: l 13.8, 13.9, 21.5, 60.5, 62.5, 104.1, 126.4, 127.9,
130.4, 131.3, 135.5, 136.6, 141.4, 143.6, 163.3, 167.0,
167.9. IR: wmax 1740 (CꢀO), 1673 (CꢀO), 1474, 1445,
1406, 1358, 1302, 1258, 1202, 1186, 1146, 1086, 1059,
1007, 912, 885, 841, 793, 752, 731, 712, 689, 629, 600,
569, 540, 477 cm−1. FABMS: m/z 808 [M++1]. Anal.
Calc. for C35H36BiNO6S: C, 52.05; H, 4.49; N, 1.73.
Found: C, 51.61; H, 4.51; N, 1.84%.
3.1.8. Ylide 4h
M.p. 196–198°C (dec.). 1H-NMR: l 2.42 (s, 9H),
3.47 (s, 3H), 3.93 (s, 3H), 7.38 (d, 6H, J=7.9), 7.59 (d,
6H, J=7.9). 13C{1H}-NMR: l 21.5, 52.0, 53.3, 110.0,
119.7 (JCF=323), 132.2, 135.4, 135.6, 142.1, 163.9,
165.7, 166.3. IR: wmax 1742 (CꢀO), 1684 (CꢀO), 1509,
1490, 1433, 1374, 1335, 1264, 1227, 1220–1150, 1127,
1065, 1007, 982, 959, 885, 835, 799, 735, 700, 646, 617,
583, 558, 507, 475 cm−1. FABMS: m/z 772 [M++1].
Anal. Calc. for C28H27BiF3NO6S: C, 43.59; H, 3.53; N,
1.82. Found: C, 42.95; H, 3.53; N, 1.82%.
3.1.13. Ylide 4m
M.p. 196–198°C (dec.). 1H-NMR: l 0.82 (t, 3H,
J=7.1), 1.44 (t, 3H, J=7.1), 2.31 (s, 3H), 3.93 (q, 2H,
J=7.1), 4.47 (q, 2H, J=7.1), 6.92 (d, 2H, J=8.1),
7.37 (d, 2H, J=8.1), 7.43–7.52 (m, 9H), 7.64–7.75 (m,
6H). 13C{1H}-NMR: l 13.8, 13.9, 21.4, 60.5, 62.5,
106.0, 126.4, 128.7, 131.0, 131.3, 135.7, 140.2, 140.5,
140.9, 163.2, 166.7, 167.0. IR: wmax 1736 (CꢀO), 1667
(CꢀO), 1568, 1485, 1435, 1397, 1356, 1298, 1285, 1256,
1211, 1144, 1080, 1059, 1018, 994, 914, 882, 841, 818,
787, 741, 727, 685, 662, 617, 590, 552, 542, 448, 438
cm−1. FABMS: m/z 780 [M++1]. Anal. Calc. for
C33H32BiNO6S: C, 50.84; H, 4.14; N, 1.80. Found: C,
50.52; H, 4.17; N, 1.83%.
3.1.9. Ylide 4i
M.p. 155–156°C (dec.). 1H-NMR: l 2.39 (s, 9H),
3.42 (s, 3H), 4.00 (s, 3H), 7.08–7.20 (m, 2H), 7.26 (d,
6H, J=8.0), 7.30 (m, 1H), 7.50 (m, 2H), 7.53 (d, 6H,
J=8.0). 13C{1H}-NMR: l 21.5, 51.4, 53.2, 104.9,
126.5, 128.0, 130.5, 131.9, 135.4, 136.3, 141.5, 143.4,
163.3, 167.2, 167.5. IR: wmax 1742 (CꢀO), 1669 (CꢀO),
1474, 1435, 1405, 1392, 1300, 1260, 1208, 1185, 1144,
1086, 1067, 1007, 980, 955, 874, 822, 801, 752, 735, 714,
689, 633, 608, 560, 538, 477 cm−1. FABMS: m/z 780
[M++1]. Anal. Calc. for C33H32BiNO6S·CH2Cl2: C,
47.23; H, 3.96; N, 1.62. Found: C, 47.67; H, 3.81; N,
1.60%.
3.2. Reaction of 4e with AcOH
3.1.10. Ylide 4j
Acetic acid (6.4 ml, 0.11 mmol) was added to a
CH2Cl2 solution (5 ml) of 4e (46 mg, 0.050 mmol), and
the resulting mixture was stirred for 4 h at room
temperature (r.t.). The solution was evaporated to leave
an oily residue, which was chromatographed on silica
gel to afford tris(2-methoxyphenyl)bismuth diacetate
(32 mg, 100%) and two separate isomers of olefin 5a
(total 20 mg, 100%; E/Z=40/60 before column chro-
matography; 20/80 after column chromatography). The
stereochemistry of 5a was assigned on the basis of the
solvent effect on the chemical shift of the NH proton in
1H-NMR. According to the change in solvent polarity,
M.p. 188–190°C (dec.). 1H-NMR: l 2.32 (s, 3H),
3.40 (s, 3H), 4.01 (s, 3H), 6.94 (d, 2H, J=8.2), 7.37 (d,
2H, J=8.2), 7.44–7.54 (m, 9H), 7.63–7.73 (m, 6H).
13C{1H}-NMR: l 21.4, 51.3, 53.2, 105.1, 126.4, 128.7,
131.1, 131.3, 135.7, 139.9, 140.3, 141.0, 163.2, 167.0,
167.5. IR: wmax 1742 (CꢀO), 1674 (CꢀO), 1568, 1507,
1474, 1433, 1393, 1374, 1268, 1211, 1180, 1144, 1086,
1065, 994, 955, 880, 826, 810, 800, 740, 687, 668, 631,
586, 552, 538, 444 cm−1. FABMS: m/z 752 [M++1].
Anal. Calc. for C31H28BiNO6S: C, 49.54; H, 3.75; N,
1.86. Found: C, 49.29; H, 3.75; N, 1.86%.