3228
J. Fournier Dit Chabert et al. / Tetrahedron 60 (2004) 3221–3230
J¼1.3, 7.2 Hz), 7.97 (dd, 1H, J¼1.3, 7.2 Hz), 8.40 (ddd, 1H,
J¼0.9, 8.1, 8.1 Hz), 8.70 (ddd, 1H, J¼0.9, 1.5, 4.7 Hz); dC
(75 MHz, CDCl3) 102.3 (C), 115.6 (CN), 121.6 (CH), 122.9
(CH), 123.0 (CH), 125.1 (CH), 126.5 (CH), 127.1 (CH),
137.7 (C), 138.7 (C), 139.8 (C), 150.1 (CH), 150.4 (C),
155.4 (C) ppm; m/z 236 (100), 209 (10), 78 (10).
4.4.9. 2-(40-Benzotrifluoride)-benzo[b]thiophene-3-car-
boxaldehyde 18. Prepared according to procedure
A. Isolated yield: 70%; pale brown solid; mp 96–98 8C;
Rf 0.6 (silica, cyclohexane/AcOEt 95:5); found C 62.64, H
2.76, F 18.81%, C16H9F3OS requires C 62.74, H 2.96, F
18.61%; dH (300 MHz, CDCl3) 7.48 (ddd, 1H, J¼1.2, 7.4,
8.2 Hz), 7.55 (ddd, 1H, J¼1.0, 7.4, 8.2 Hz), 7.72 (d, 2H,
J¼8.3 Hz), 7.80 (d, 2H, J¼8.3 Hz), 7.87 (d, 1H, J¼7.4 Hz),
8.80 (dd, 1H, J¼1.2, 8.0 Hz), 10.05 (s, 1H); dC (75 MHz,
CDCl3) 120.8 (CH), 122.8 (q, CF3, J¼272.8 Hz), 124.4
(CH), 124.9 (q, 2CH, J¼3.7 Hz), 125.4 (CH), 125.7 (CH),
129.9 (C), 130.0 (2CH), 131.0 (q, C, J¼32.7 Hz), 134.3 (C),
136.0 (C), 137.2 (C), 157.0 (C), 185.0 (CHO) ppm; m/z 306
(80), 305 (100), 237 (60), 208 (50), 160 (20).
4.4.5. 2-(30-Pyridine)-benzo[b]thiophene-3-carbonitrile
10. Prepared according to procedure C. Isolated yield:
52%; yellow solid; mp 150–152 8C; Rf 0.15 (silica,
cyclohexane/AcOEt 95:5); found C 71.28, H 3.54, N
11.71, S 13.69%, C14H8N2S requires C 71.16, H 3.41, N
11.86, S 13.57%; dH (300 MHz, CDCl3) 7.43 (ddd, 1H,
J¼1.3, 7.3, 8.1 Hz), 7.45 (dd, 1H, J¼4.0, 8.1 Hz), 7.52 (ddd,
1H, J¼1.0, 7.3, 7.5 Hz), 7.84 (d, 1H, J¼7.5 Hz), 7.94 (dd,
1H, J¼1.0, 8.1 Hz), 8.21 (ddd, 1H, J¼1.6, 1.6, 8.1 Hz), 8.73
(d, 1H, J¼4.0 Hz), 9.06 (d, 1H, J¼1.6 Hz); dC (75 MHz,
CDCl3) 103.9 (C), 114.9 (CN), 122.9 (CH), 123.2 (CH),
124.3 (CH), 126.8 (CH), 127.1 (CH), 128.2 (C), 135.6 (CH),
138.0 (C), 139.2 (C), 149.2 (CH), 151.0 (C), 151.6 (CH)
ppm; m/z 236 (100).
4.4.10. 2-(20-Nitrophenyl)-benzo[b]thiophene-3-carbox-
aldehyde 19. Prepared according to procedure A. Isolated
yield: 56%; yellow solid; mp 155–156 8C; Rf 0.1 (silica,
cyclohexane/AcOEt 95:5); found C 63.72, H 3.20, N 5.01, O
17.12%, C15H9NO3S requires C 63.59, H 3.20, N 4.94, O
16.94%; dH (300 MHz, CDCl3) 7.48 (ddd, 1H, J¼1.4, 7.2,
8.0 Hz), 7.55 (ddd, 1H, J¼1.4, 7.2, 8.0 Hz), 7.61 (dd, 1H,
J¼1.5, 6.2 Hz), 7.70 (ddd, 1H, J¼1.5, 6.2, 7.5 Hz), 7.75
(ddd, 1H, J¼1.5, 6.7, 7.5 Hz), 7.86 (dd, 1H, J¼1.5, 6.7 Hz),
8.16 (dd, 1H, J¼1.4, 7.2 Hz), 8.71 (dd, 1H, J¼1.4, 7.2 Hz),
9.86 (s, 1H); dC (75 MHz, CDCl3) 121.9 (CH), 125.0 (CH),
125.1 (CH), 126.4 (CH), 126.5 (C), 126.6 (CH), 131.1 (CH),
131.9 (C), 132.9 (CH), 133.7 (CH), 136.2 (C), 138.8 (C),
146.6 (C), 153.9 (C), 185.0 (CHO) ppm; m/z 283 (40), 163
(100), 119 (80), 93 (50).
4.4.6. 2-(40-Anisyl)-benzo[b]thiophene-3-carboxaldehyde
15. Prepared according to procedure A. Isolated yield: 64%;
pale yellow solid; mp 75–76 8C; Rf 0.4 (silica, cyclohex-
ane/AcOEt 95:5); found C 71.34, H 4.39, O 11.88, S
11.74%, C16H12O2S requires C 71.62, H 4.51, O 11.93, S
11.95%; dH (300 MHz, CDCl3) 3.87 (s, 3H, OCH3), 6.99
(d, 2H, J¼8.8 Hz), 7.39 (ddd, 1H, J¼0.6, 7.4, 8.1 Hz),
7.47 (m, 1H), 7.51 (d, 2H, J¼8.8 Hz), 7.79 (d, 1H,
J¼7.9 Hz), 8.76 (dd, 1H, J¼0.7, 7.4 Hz), 10.05 (s, 1H,
CHO); dC (75 MHz, CDCl3) 55.9 (CH3), 114.8 (2CH),
122.0 (CH), 124.2 (C), 125.4 (CH), 126.0 (CH), 126.6
(CH), 130.0 (C), 132.3 (2CH), 137.7 (C), 138.0 (C),
161.4 (C), 161.6 (C), 187.2 (CHO) ppm; m/z 268 (100),
267 (70), 237 (30).
4.4.11. 2-(20-Benzonitrile)-benzo[b]thiophene-3-carbox-
aldehyde 20. Prepared according to procedure A. Isolated
yield: 54%; orange crystals; mp 172–174 8C; Rf 0.1 (silica,
cyclohexane/AcOEt 95:5); found C 72.97, H 3.54, N 5.50%,
C16H9NOS requires C 72.98, H 3.45, N 5.32%; dH
(500 MHz, CDCl3) 7.53 (ddd, 1H, J¼1.3, 7.6, 7.6 Hz),
7.59 (ddd, 1H, J¼1.0, 7.6, 7.9 Hz), 7.68 (ddd, 1H, J¼1.2,
7.6, 8.2 Hz), 7.69 (d, 1H, J¼7.9 Hz), 7.77 (ddd, 1H, J¼1.3,
7.6, 7.9 Hz), 7.89 (dd, 1H, J¼1.3, 7.9 Hz), 7.91 (d, 1H,
J¼8.2 Hz), 8.71 (dd, 1H, J¼1.0, 7.6 Hz), 9.91 (s, 1H,
CHO); dC (75 MHz, CDCl3) 114.4 (C), 117.4 (C), 122.2
(CH), 125.8 (CH), 126.9 (CH), 127.0 (CH), 130.7 (CH),
132.6 (CH), 133.2 (CH), 134.0 (CH), 135.4 (C), 136.7 (C),
139.1 (C), 154.3 (C), 185.4 (CHO) ppm; m/z 262 (80), 235
(100), 190 (90).
4.4.7. 2-(40-Anisyl)-3-methoxybenzo[b]thiophene 16. Pre-
pared according to procedure A. Isolated yield 61%; pink
solid; mp 62–64 8C; Rf 0.35 (silica, cyclohexane/AcOEt
95:5); dH (300 MHz, CDCl3) 3.75 (s, CH3), 3.76 (s, CH3),
6.99 (d, 2H, J¼8.9 Hz), 7.34 (ddd, 1H, J¼1.3, 7.3, 7.3 Hz),
7.40 (ddd, 1H, J¼1.2, 7.3, 7.3 Hz), 7.72–7.78 (m, 2H), 7.81
(d, 2H, J¼8.9 Hz); dC (75 MHz, CDCl3) 55.7 (CH3), 61.1
(CH3), 114.6 (2CH), 121.1 (CH), 123.1 (CH), 124.7 (CH),
125.1 (CH), 125.9 (C), 127.1 (C), 129.6 (2CH), 135.3 (C),
135.7 (C), 146.8 (C), 159.7 (C) ppm; m/z 270 (70), 255
(100), 227 (80), 212 (70), 184 (60).
4.4.12. 2-(40-Benzonitrile)-benzo[b]thiophene-3-carbox-
aldehyde 21. Prepared according to procedure A. Isolated
yield: 41%; pale green solid; mp 168–169 8C; Rf 0.1 (silica,
cyclohexane/AcOEt 95:5); found C 72.67, H 3.45, N 5.31, O
6.43%, C16H9NOS requires C 72.98, H 3.45, N 5.32, O
6.08%; dH (300 MHz, CDCl3) 7.48 (ddd, 1H, J¼1.0, 7.3,
8.1 Hz), 7.55 (ddd, 1H, J¼1.1, 7.4, 8.1 Hz), 7.70 (d, 2H,
J¼7.5 Hz), 7.81 (d, 2H, J¼7.5 Hz), 7.89 (dd, 1H, J¼1.1,
7.3 Hz), 8.77 (dd, 1H, J¼1.0, 7.4 Hz), 10.03 (s, 1H); dC
(75 MHz, CDCl3) 113.9 (C), 118.1 (C), 121.9 (CH), 125.5
(CH), 126.6 (C), 126.8 (C), 131.1 (C), 131.3 (2CH), 132.7
(2CH), 136.3 (C), 137.0 (C), 138.3 (C), 157.1 (C), 185.7
(CHO) ppm; m/z 263 (70), 262 (100), 235 (20), 190 (60).
4.4.8. 2-(40-Anisyl)-3-(2,2,2-trifluoroethoxy)benzo[b]-
thiophene 17. Prepared according to procedure A.
Isolated yield 66%; pink crystals; mp 78–80 8C; Rf 0.10
(silica, cyclohexane); found
C
60.17,
H
3.96%,
C17H13F3O2S requires C 60.35, H 3.87%; dH (300 MHz,
CDCl3) 3.88 (s, OCH3), 4.23 (q, CH2, J¼8.4 Hz), 7.01 (d,
2H, J¼8.9 Hz), 7.36 (ddd, 1H, J¼1.4, 7.5, 7.9 Hz), 7.42
(ddd, 1H, J¼1.3, 7.4, 7.5 Hz), 7.74 (d, 2H, J¼8.9 Hz), 7.76
(m, 2H); dC (75 MHz, CDCl3) 55.7 (CH3), 69.4 (q, CH2,
J¼35.0 Hz), 114.9 (2CH), 116.3 (C), 120.8 (CH), 123.1
(CH), 124.7 (C), 125.1 (CH), 125.5 (CH), 129.9 (2CH),
134.4 (C), 135.6 (C), 143.8 (C), 160.2 (C); dF (282 MHz,
CDCl3) 274.9 (t, 3F, J¼8.4 Hz) ppm; m/z 340 (30), 338
(60), 255 (100).
4.4.13. 2-(40-Chloro-phenyl)-benzo[b]thiophene-3-car-
boxaldehyde 22. Prepared according to procedure