H, 2.6; N, 5.8%); nmax/cmꢀ1: 1549, 1398, 1211, 1163, 1109,
859, 791, 745 and 692; dH (300 MHz, CDCl3): 8.69 (2 H, m,
8,10-H), 8.09 (1 H, d, J = 6 Hz, 1-H), 8.02 (1 H, d, J = 8 Hz,
5-H), 7.84 (1 H, d, J = 8 Hz, 4-H), 7.77 (1 H, d, J = 6 Hz,
2-H) and 7.48 (1 H, dd, J = 8 and 6 Hz, 9-H); dC (75 Mz,
CDCl3): 162.1, 147.6, 138.1, 135.4, 135.0, 130.9, 129.8, 128.8,
127.0, 122.2, 121.0, 119.7 and 119.3; m/z = 241 (M+, 100%),
209 (7), 196 (20), 170 (15), 152 (5), 120 (17) and 107 (25).
(75 Mz, CDCl3): 164.0, 146.8, 142.0, 133.4, 133.1, 130.1, 128.9,
128.0, 125.9, 125.3, 124.1, 122.3 and 119.9; m/z = 241
(M+, 100%), 209 (9), 196 (5), 183 (7) and 121 (6).
Pyrolysis of ylide 18
FVP of the title compound (1.0 g) at 850 1C and 8–9 ꢂ
10ꢀ2 Torr gave a deep brown oil at the furnace exit. Column
chromatography of this material using diethyl ether–hexane
(1 : 3) as eluent gave a brown oil that solidified with time. The
solid was recrystallised from ethanol to give the product,
benzofuro[20,30:4,5]thieno[2,3-b]pyridine (20) (0.13 g, 31%),
as pale brown leaves. Mp 151–153 1C (found: C, 69.8; H,
2.8; N, 6.2; C13H7NOS requires C, 69.3; H, 3.1; N, 6.2%)
(HRMS: found M+ (225.0254); C13H7NOS requires M =
225.0248); nmax/cmꢀ1: 1553, 1436, 1402, 1368, 1364, 1302,
1190, 1131, 1108, 1063, 803 and 747; dH (300 MHz, CDCl3):
8.51 (1 H, d, J = 6 Hz, 2-H), 8.12 (1 H, d, J = 7 Hz, 4-H), 7.67
(1 H, d, J = 7 Hz, 9-H), 7.58 (1 H, d, J = 7 Hz, 6-H) and
7.42–7.24 (3 H, m); dC (75 Mz, CDCl3): 163.2, 158.3, 149.4,
146.4, 127.0, 125.7, 123.8, 123.7, 120.1, 120.1, 119.9, 118.2 and
112.6; m/z = 225 (M+, 100%), 196 (9), 135 (8) and 113 (5).
Pyrolysis of ylide 10
FVP of the title compound (1.0 g) at 850 1C and 1–2 ꢂ
10ꢀ2 Torr gave a brown oily solid at the furnace exit. Column
chromatography of this material using diethyl ether–hexane
(1 : 9) as the eluent gave a pale brown waxy solid, which was
recrystallised (EtOH) to give the product, benzofuro-
[40,5,50:4]thieno[2,3-b]pyridine (14) (0.18 g, 42%), as a pale
brown solid. Mp 144.5–146 1C (found: C, 69.6; H, 3.2; N, 6.2;
C13H7NOS requires C, 69.3; H, 3.1; N, 6.2%); nmax/cmꢀ1
:
1551, 1425, 1249, 1215, 1174, 1151, 1054, 913, 802, 782 and
748; dH (300 MHz, CDCl3): 8.69 (1 H, d, J = 5 Hz, 8-H), 8.55
(1 H, d, J = 7 Hz, 10-H), 7.88 (1 H, d, J = 2 Hz, 2-H), 7.80
(1 H, d, J = 8 Hz, 5-H), 7.72 (1 H, d, J = 8 Hz, 4-H), 7.48
(1 H, dd, J = 7 and 5 Hz, 9-H) and 7.35 (1 H, d, J = 2 Hz,
1-H); dC (75 Mz, CDCl3): 162.8, 153.7, 147.8, 146.2, 133.1,
130.3, 129.8, 125.5, 122.7, 119.6, 118.8, 112.0 and 104.8;
m/z = 225 (M+, 100%), 196 (29), 170 (13), 153 (18), 126
(10), 113 (27), 99 (32) and 85 (26).
References
1 R. A. Aitken and G. Burns, J. Chem. Soc., Perkin Trans. 1, 1994,
2455–2460.
2 R. A. Aitken, C. K. Bradbury, G. Burns and J. J. Morrison,
Synlett, 1995, 53–54; R. A. Aitken, G. Burns and J. J. Morrison,
J. Chem. Soc., Perkin Trans. 1, 1998, 3937–3941.
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Pyrolysis of ylide 17
FVP of the title compound (1.2 g) at 850 1C and 8–9 ꢂ
10ꢀ2 Torr gave a light brown solid at the furnace exit. Column
chromatography of this material using diethyl ether–hexane
(1 : 1) as eluent gave a beige solid, which was recrystallised
(EtOH) to give the product, benzothieno[20,30:4,5]thieno[2,3-b]-
pyridine (19) (0.50 g, 95%), as beige crystals. Mp 184–187 1C
(found: C, 65.2; H, 2.6; N, 5.6; C13H7NS2 requires C, 64.7; H,
2.9; N, 5.8%) (HRMS: found M+ (241.0023); C13H7NS2
requires M = 241.0020); nmax/cmꢀ1: 1547, 1344, 1325, 1304,
1257, 1103, 1063, 1019, 948, 793, 741 and 723; dH (300 MHz,
CDCl3): 8.57 (1 H, d, J = 5 Hz, 2-H), 8.12 (1 H, d, J = 8 Hz,
4-H), 7.98–7.86 (2 H, m, 6,9-H) and 7.55–7.32 (3 H, m); dC
11 R. A. Aitken and J. I. Atherton, J. Chem. Soc., Perkin Trans. 1,
1994, 1281–1284.
ꢁc
This journal is The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2009
2404 | New J. Chem., 2009, 33, 2402–2404