HETEROCYCLES, Vol. 68, No. 6, 2006
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3’-{[2.2]Paracyclophan-4-ylethynyl}-6’-[phenylethynyl]thiophene (5a). Dry THF (3 mL), 4-
ethynyl[2.2]paracyclophane (1) (0.094 g, 0.57 mmol), triphenylphosphine (0.010 g, 0.04 mmol), CuI
(0.004 g, 0.02 mmol), aryliodide (4a) (0.084g, 0.27 mmol), PdCl2(PPh3)2 (0.014 g, 0.02 mmol) and dry
triethylamine (1.3 mL) were placed in a flask and degassed with Ar. The mixture was kept at 25°C for 3h.
The solvent was then removed under reduced pressure and the residue was chromatographed on silica gel
(elution: petroleum ether/chloroform 24:1) to obtain 5a as pale yellow crystals (48% yield). mp 145-
146°C (MeOH). 1H-NMR (CDCl3): δ 2.90 (ddd, 1H, J = 13.1, 10.2, 5.3 Hz, H-2), 2.96-3.16 (m, 5H, H-1,
Hs-9, Hs-10), 3.23 (m, 1H, H-1), 3.59 (ddd, 1H, J = 13.1, 10.2, 2.8 Hz, H-2), 6.47-6.53 (m, 5H, H-7, H-8,
H-12, H-13, H-16), 6.57 (d, 1H, J = 1.8 Hz, H-5), 6.97 (dd, 1H, J = 7.8, 1.9 Hz, H-15), 7.17 (d, 1H, J =
3.8 Hz, H-4’ or H-5’), 7.19 (d, 1H, J = 3.8 Hz, H-4’ or H-5’), 7.36 (m, 2H, H-11’, H-13’), 7.37 (m, 1H,
H-12’), 7.53 (m, 2H, H-10’, H-14’). 13C-NMR (CDCl3): δ 34.6 (C-1), 34.8 (C-2), 35.4, 35.7 (C-9, C-10),
82.6, 85.8 (C-2’, C-7’), 94.3, 94.9 (C-1’, C-8’), 122.9 (C-9’), 124.5, 124.7 (C-3’, C-6’), 125.5 (C-4),
128.6 (C-11’, C-13’), 128.8 (C-12’), 130.4 (C-15), 131.4, 132.1 (C-4’, C-5’), 131.7 (C-10’, C-14’), 132.7,
132.9, 133.5 (C-12, C-13, C-16), 133.4 (C-7), 134.2 (C-8), 137.0 (C-5), 139.5 (C-11), 139.6 (C-14), 140.1
(C-6), 142.8 (C-3). UV-Vis (CHCl3): [λmax nm (logε)] 242 (4.14), 356 (4.46). Anal. Calcd for C30H22S: C,
86.92; H, 5.35. Found: C, 86.98; H, 5.34%.
3’-{[2.2]Paracyclophan-4-ylethynyl}-thiophene (2). Reaction temperature: 75°C; reaction time: 21 h.
Purified by column chromatography on silica gel eluting with petroleum ether/chloroform 4:1; white
1
plates (99%). mp 122-123°C (MeOH). H-NMR (CDCl3): δ 2.88 (ddd, 1H, J = 13.1, 10.3, 5.5 Hz, H-2),
2.90-3.15 (m, 5H, H-1, Hs-9, Hs-10), 3.24 (ddd, 1H, J = 13.2, 10.2, 5.3 Hz, H-1), 3.61 (ddd, 1H, J = 13.1,
10.3, 2.6 Hz, H-2), 6.48 (d, 1H, J = 7.9 Hz, H-8), 6.50-6.54 (m, 4H, H-7, H-12, H-13, H-16), 6.56 (d, 1H,
J = 1.7 Hz, H-5), 7.00 (dd, 1H, J = 7.8, 1.8 Hz, H-15), 7.05 (dd, 1H, J = 4.9, 3.9 Hz, H-5’), 7.31 (dd, 1H,
J = 4.9, 1.1 Hz, H-6’), 7.32 (dd, 1H, J = 3.9, 1.1 Hz, H-4’). 13C-NMR (CDCl3): δ 34.6 (C-1), 34.8 (C-2),
35.4, 35.7 (C-9, C-10), 86.2 (C-2’), 93.7 (C-1’), 124.2 (C-3’), 124.8 (C-4), 127.2 (C-6’), 127.4 (C-5’),
130.4 (C-15), 131.6 (C-4’), 132.7 (C-12), 132.9 (C-16), 133.2 (C-7), 133.5 (C-13), 134.2 (C-8), 137.0 (C-
5), 139.6 (C-11), 139.7 (C-14), 140.0 (C-6), 142.7 (C-3). UV-Vis (CHCl3) [λmax nm (logε)] 244 (4.19),
319 (4.32). Anal. Calcd for C22H18S: C, 84.03; H, 5.77. Found: C, 84.10; H, 5.78%.
4’-{[2.2]Paracyclophan-4-ylethynyl}-thiophene (3). Reaction temperature: 75°C; reaction time: 21 h.
Purified by column chromatography on silica gel eluting with petroleum ether/chloroform 4:1; white
1
plates (97%). mp 143-144°C (MeOH). H-NMR (CDCl3): δ 2.88 (ddd, 1H, J = 13.1, 10.4, 5.3 Hz, H-2),
2.92-3.15 (m, 5H, H-1, Hs-9, Hs-10), 3.25 (ddd, 1H, J = 13.1, 10.2, 5.4 Hz, H-1), 3.63 (ddd, 1H, J = 13.1,
10.3, 2.7 Hz, H-2), 6.49-6.53 (m, 5H, H-7, H-8, H-12, H-13, H-16), 6.58 (d, 1H, J = 1.8 Hz, H-5), 7.02
(dd, 1H, J = 7.8, 1.8 Hz, H-15), 7.27 (dd, 1H, J = 5.0, 3.0 Hz, H-5’), 7.35 (dd, 1H, J = 5.0, 1.2 Hz, H-6’),
7.55 (dd, 1H, J = 3.0, 1.2 Hz, H-3’). 13C-NMR (CDCl3): δ 34.6 (C-1), 34.8 (C-2), 35.4, 35.7 (C-9, C-10),