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5.49; N, 3.01. EI-MS m/z: 472 (M+, 2%), 430 (10%), 371
(100%), 328 (46%). 1H NMR d ppm: 0.99 (6H, d,
J = 6.42 Hz), 2.11 (1H, m), 2.66 (2H, d, J = 6.42 Hz), 3.90
(2H, d, J = 16.00 Hz), 3.94 (2H, d, J = 16.00 Hz), 7.06 (2H,
d, J = 7.33 Hz), 7.22–7.35 (7H, m), 7.59 (2H, d,
J = 8.24 Hz), 8.32 (2H, d, J = 7.33 Hz). 13C NMR d ppm:
22.9 (q), 25.8 (d), 57.4 (t), 61.4 (t), 97.1 (s), 110.3 (s), 124.7
(s), 126.3 (d), 127.7 (d), 128.2 (d), 128.3 (d), 128.5 (d), 131.9
(d), 135.4 (s), 136.6 (d), 143.0 (s). IR (cmꢁ1): 2119 (C„C).
7.5 mmol), BuLi (7.5 mmol), and 8f (2.26 g, 5.0 mmol)
was purified on silica gel column chromatography (hex-
ane:AcOEt = 1:1) to give 9f (3.17 g, 89% yield). Colorless
prisms (m.p. 163–164 °C, from benzene–hexane). Elemen-
tal analysis: Calcd. for C26H26NSb: C, 65.85; H, 5.53; N,
2.95. Found: C, 65.89; H, 5.59; N, 3.03. EI-MS m/z: 473
1
(M+, 4%), 416 (5%), 371 (13%), 314 (100%). H NMR d
ppm: 1.26 (9H, s), 3.76 (2H, d, J = 15.12 Hz), 4.18 (2H,
d, J = 15.12 Hz), 7.04 (2H, d, J = 7.33 Hz), 7.17–7.25
(4H, m), 7.28–7.36 (3H, m), 7.60 (2H, d, J = 8.25 Hz),
8.33 (2H, d, J = 7.33 Hz). 13C NMR d ppm: 26.8 (q),
54.9 (t), 58.2 (s), 97.5 (s), 110.8 (s), 124.8 (s), 125.6 (d),
127.6 (d), 127.9 (d), 128.2 (d), 128.3 (d), 131.8 (d), 135.3
(s), 136.5 (d), 145.2 (s). IR cmꢁ1: 2127 (C„C).
4.4.4. 12-Phenylethynyl-N-isopropyl-5,6,7,12-
tetrahydrodibenz[c,f][1,5]azastibocine (9d)
The ethynyl-azastibocine (9d) was prepared according to
the procedure described for 9a in Section 4.4.1. The crude
product obtained from ethynylbenzene (1.02 g, 10 mmol),
BuLi (10 mmol), and 8d (4.38 g, 10 mmol) was purified
on silica gel column chromatography (hexane:AcOEt =
1:1) to give 9d (4.50 g, 98% yield). Colorless prisms (m.p.
139–140 °C, from benzene–hexane). Elemental analysis:
Calcd. for C25H24NSb: C, 65.24; H, 5.26; N, 3.04. Found:
C, 65.29; H, 5.30; N, 3.10. EI-MS m/z: 459 (M+, 4%), 418
(7%), 357 (100%), 314 (66%). 1H NMR d ppm: 1.18 (6H, d,
J = 6.88 Hz), 3.26 (1H, septet, J = 6.88 Hz), 3.78 (2H, d, J
= 15.13 Hz), 3.94 (2H, d, J = 15.13 Hz), 7.06 (2H, d, J =
7.33 Hz), 7.20–7.35 (7H, m), 7.59 (2H, d, J = 7.56 Hz),
8.32 (2H, d, J = 7.33 Hz). 13C NMR d ppm: 18.7 (q),
53.5 (d), 54.6 (t), 97.6 (s), 110.5 (s), 124.8 (s), 126.0 (d),
127.6 (d), 128.2 (d), 128.3 (d), 128.3 (d), 131.9 (d), 135.5
(s), 136.5 (d), 143.8 (s). IR cmꢁ1: 2123 (C„C).
4.4.7. 12-Phenylethynyl-N-phenyl-5,6,7,12-
tetrahydrodibenz[c,f][1,5]azastibocine (9g)
The ethynyl-azastibocine (9g) was prepared according to
the procedure described for 9a in Section 4.4.1. The crude
product obtained from ethynylbenzene (510 mg,
5.0 mmol), BuLi (5.0 mmol), and 8g (2.36 g, 5.0 mmol)
was purified on silica gel column chromatography (hex-
ane:AcOEt = 1:1) to give 9g (2.17 g, 88% yield). Colorless
prisms (m.p. 177–180 °C, from benzene–hexane). Elemen-
tal analysis: Calcd. for C28H22NSb: C, 68.04; H, 4.49; N,
2.83. Found: C, 68.14; H, 4.81; N, 2.95. EI-MS m/z: 493
(M+, 2%), 391 (100%), 301 (16%), 269 (49%), 213 (29%),
1
179 (41%). H NMR d ppm: 4.34 (2H, d, J = 15.13 Hz),
4.64 (2H, d, J = 15.13 Hz), 6.99 (1H, t, J = 7.33 Hz), 7.09
(2H, d, J = 7.82 Hz), 7.17 (2H, d, J = 6.87 Hz), 7.22–7.35
(9H, m), 7.58 (2H, d, J = 7.82 Hz), 8.29 (2H, d,
J = 6.87 Hz). 13C NMR d ppm: 58.0 (t), 94.0 (s), 111.6
(s), 118.1 (d), 122.5 (d), 124.3 (s), 126.2 (d), 128.0 (d),
128.2 (d), 128.6 (d), 128.7 (d), 129.1 (d), 131.9 (d), 134.9
(s), 136.9 (d), 143.0 (s), 148.6 (s). IR cmꢁ1: 2121 (C„C).
4.4.5. 12-Phenylethynyl-N-cyclohexyl-5,6,7,12-
tetrahydrodibenz[c,f][1,5]azastibocine (9e)
The ethynyl-azastibocine (9e) was prepared according to
the procedure described for 9a in Section 4.4.1. The crude
product obtained from ethynylbenzene (612 mg,
6.0 mmol), BuLi (6.0 mmol), and 8e (1.91 g, 4.0 mmol)
was purified on silica gel column chromatography (hex-
ane:AcOEt = 1:1) to give 9e (1.09 g, 55% yield). Colorless
prisms (m.p. 125–126 °C, from benzene–hexane). Elemen-
tal analysis: Calcd. for C28H28NSb: C, 67.22; H, 5.64; N,
2.80. Found: C, 67.36; H, 5.52; N, 2.95. EI-MS m/z: 499
4.4.8. 12-p-Tolylethynyl-N-methyl-5,6,7,12-
tetrahydrodibenz[c,f][1,5]azastibocine (10a)
The same procedure as for the preparation of 9a using 8a
and p-tolylacetylene gave 10a (91% yield). Colorless prisms
(m.p. 142–145 °C, from ether–EtOH). Elemental analysis:
Calcd. for C24H22NSb: C, 64.60; H, 4.97; N, 3.14. Found:
C, 64.23; H, 5.36; N, 2.90. EI-MS m/z: 445 (M+, 6%), 329
1
(M+, 3%), 416 (8%), 397 (100%), 314 (54%). H NMR d
ppm: 1.01–1.13 (1H, m), 1.18–1.36 (4H, m), 1.63 (1H, d,
J = 12.83 Hz), 1.78 (2H, d, J = 12.83 Hz), 2.02 (2H, d,
J = 12.83 Hz), 2.85 (1H, m), 3.81 (2H, d, J = 15.12 Hz),
3.97 (2H, d, J = 15.12 Hz), 7.03 (2H, d, J = 7.33 Hz),
7.59 (2H, d, J = 8.25 Hz), 8.32 (2H, d, J = 7.33 Hz). 13C
NMR d ppm: 25.9 (t), 26.0 (t), 29.0 (t), 55.2 (t), 63.1 (d),
97.8 (s), 110.5 (s), 124.8 (s), 125.9 (d), 127.6 (d), 128.1
(d), 128.2 (d), 128.3 (d), 131.9 (d), 135.5 (s), 136.4 (d),
144.0 (s). IR cmꢁ1: 2115 (C„C).
1
(100%), 208 (26%), 179 (26%). H NMR d ppm: 2.36 (3H,
s), 2.52 (3H, s), 3.69 (2H, d, J = 14.29 Hz), 3.89 (2H, d,
J = 14.29 Hz), 7.05 (2H, d, J = 7.33 Hz), 7.13 (2H, d,
J = 8.06 Hz), 7.22 (2H, dd, J1,2 = J2,3 = 7.33 Hz), 7.29
(2H, dd, J2,3 = J3,4 = 7.33 Hz), 7.49 (2H,d, J = 8.06 Hz),
8.33 (2H, d, J = 7.33 Hz). 13C NMR d ppm: 21.5 (q), 41.9
(q), 60.2 (t), 96.8 (s), 110.2 (s), 121.7 (s), 126.2 (d), 128.3
(d), 128.5 (d), 128.9 (d), 131.8 (d), 136.2 (s), 136.7 (d),
137.6 (s). IR cmꢁ1: 2107 (C„C).
4.4.6. 12-Phenylethynyl-N-t-butyl-5,6,7,12-
tetrahydrodibenz[c,f][1,5]azastibocine (9f)
The ethynyl-azastibocine (9f) was prepared according
to the procedure described for 9a in Section 4.4.1. The
crude product obtained from ethynylbenzene (765 mg,
4.4.9. 12-p-Fluorophenylethynyl-N-methyl-5,6,7,12-
tetrahydrodibenz[c,f][1,5]azastibocine (11a)
The same procedure as for the preparation of 9a using
8a and p-fluorophenylacetylene gave 11a (86% yield). Col-