Arkivoc 2018, part vii, 0-0
Çapan, I. et al.
3.68 (1H, t, J 3.8 Hz), 3.30 (1H, s), 3.06 (1H, s), 2.98 (1H, s), ’ 1.83 (1H, d, A part of AB system, J 7.8 Hz), 1.54 (1H, d,
B part of AB system, J 8.1 Hz). 13C NMR (100 MHz, CDCl3): δC = 171.6, 170.9 (C=O), 159.5 (C=N), 133.9, (CAr-ipso),
133.9, 133.7 (C=C), 130.2, 130.1, 129.2, 128.2, 126.2, 126.0 (Ar CH), 54.4, 54.0 (CH2-N), 49.0, 48.1 (CHbridgehead),
48.5, 45.8 (O=C-CH), 48.0, 47.9 (CH2-N), 47.3, (CH2 bridge); Anal. calc. for C27H24Cl2N4O2 (507.41): C, 63.91; H,
4.77; N, 11.04; found C, 64.13; H, 4.83; N, 11.27%.
General synthesis of N-acyl substituted imidazolines with dibenzobarrelene skeleton 19-24. To a solution of
the requisite imidazolines (3.72 mmol, compounds 6, 7, 9-12) in dry THF (50 mL), triethylamine (0.37 g, 3.66
mmol, 0.51 mL) was added, and then stirred at room temperature for 30 minutes. Compound 18 (0.57 g, 1.72
mmol) was added to this mixture at 0 °C and stirred at room temperature for 24 hours. The formed colorless
solid was filtered. The solvent was removed in vacuo. The oily product was dissolved in methanol (10 mL) and
precipitated in ice-water (200 mL). The resulting colorless solid was filtered and dried at vacuum. The crude
products were crystallized from THF, except for compound 23, crystallized from methanol.
trans-11,12-Bis[(4,5-dihydro-2-phenyl-1H-imidazol-1-yl)carbonyl]-9,10-dihydro-9,10-ethanoanthracene (19).
o
Colorless powder, yield: 0.85 g (1.54 mmol, 90%); mp: 250-251 C; IR (ATR) (νmax, cm−1): 3059, 3026, 2948,
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2866, 1685, 1625, 1364, 1273, 1139, 1023, 767, 691; H NMR (400 MHz, DMSO-d6): δH = 7.47 -7.40 (4H, m),
7.38 (2H, s), 7.36-7.31 (5H, m), 7.28-7.22 (4H, m), 7.19 -7.15 (3H, m), 4.85 (2H, s), 4.32 (2H, dd, J 19.3, 9.7 Hz),
4.11- 4.04 (2H, m), 4.03 -3.96 (2H, m), 3.93- 3.81 (2H, m), 3.49 (2H, s) ; 13C NMR (100 MHz, DMSO-d6): δC =
170.2 (C=O), 160.1 (C=N), 143.2, 140.6 (dibenzobarrelene-Cipso), 132.6 (CAr-ipso), 128.5, 127.8
(dibenzobarrelene-CH), 129.9, 128.8, 126.6, 126.2, 125.5, 123.8 (CHphenyl), 54.5, 48.1 (CH2-N), 48.5 (CH-bridgehead),
46.1 (CH); Anal. calc. for C36H30N4O2 (550.65): C, 78.52; H, 5.49; N, 10.17; found C, 78.73; H, 5.66; N, 10.39%.
trans-11,12-Bis[[2-(3-chlorophenyl)-4,5-dihydro-1H-imidazol-1-yl]carbonyl]-9,10-dihydro-9,10-
o
ethanoanthracene (20). Colorless powder; yield: 0.86 g (1.40 mmol, 75%); mp: 241-243 C; IR (ATR) (νmax
,
cm−1): 3073, 3026, 2964, 2867, 1730, 1680, 1629, 1459, 1355, 1261, 1143, 1000, 791, 762, 700, 560; H NMR
(400 MHz, DMSO-d6): δH = 7.49 (2H, d, J 5.9 Hz), 7.45- 7.39 (4H, m,), 7.31 (4H, d, J 9.5 Hz), 7.15 (6H, dd, J 12.5,
4.9 Hz), 4.89 (2H, s), 4.35 (2H, d, J 9.3 Hz,), 4.14- 3.97 (4H, m,), 3.97- 3.84 (2H, m), 3.55 (1H, s), 3.46 (1H, s); 13C
NMR (100 MHz, DMSO-d6): δC = 170.2 (C=O), 158.9 (C=N), 143.1, 140.5 (dibenzobarrelene-Cipso), 134.8, 132.6
(CAr-ipso), 130.0, 129.8, 128.2, 126.9, 126.7, 126.6, 125.4, 125.2, 124.0, 123.7 (Ar-CH), 54.7, 47.9 (CH2-N), 52.5,
48.3, 46.0, 45.9 (CH); Anal. calc. for C36H28Cl2N4O2 (619.54): C, 69.79; H, 4.56; N, 9.04; found C, 69.81; H, 4.63;
N, 9.17%.
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trans-11,12-Bis[[4,5-dihydro-2-(2-thienyl)-1H-imidazol-1-yl]carbonyl]-9,10-dihydro-9,10-ethanoanthracene
o
(21). Colorless powder; yield: 0.90 g (1.60 mmol, 86%); mp: 256-258 C ; IR (ATR) (νmax, cm−1): 3069, 3034,
1
2956, 2871, 1689, 1671, 1609, 1357, 1266, 1080, 681; H NMR (400 MHz, DMSO-d6): δH = 7.60 (2H, dd, J 4.5,
1.7 Hz), 7.47 (2H, d, J 6.7 Hz), 7.43 (1H, s), 7.33 (1H, s), 7.23- 7.12 (4H, m), 7.01-6.90 (4H, m), 4.85 (2H, s), 4.34
(2H, q, J 9.8 Hz), 4.15 (2H, td, J 9.5, 4.7 Hz), 3.98 (2H, ddd, J 14.7, 9.8, 4.7 Hz), 3.84 (2H, dt, J 15.5, 9.6 Hz), 3.64
(2H, s); 13C NMR (100 MHz, DMSO-d6): δC = 170.6 (C=O), 154.6 (C=N), 143.1, 140.6 (dibenzobarrelene-Cipso),
133.7 (Cthiophene-ipso), 128.8, 127.2 (dibenzobarrelene-CH), 131.1, 129.4, 126.7, 126.3, 125.4, 123.9
(CHthiophene), 54.0, 48.7 (CH2-N), 49.0 (CH-bridgehead), 46.3 (CH) ; Anal. calc. for: C32H26N4O2S2 (562.70): C, 68.30; H,
4.66; N, 9.96; S, 11.40; found C, 68.53; H, 4.82; N, 10.11; S, 11.42%.
trans-11,12-Bis[[4,5-dihydro-2-(3-thienyl)-1H-imidazol-1-yl]carbonyl]-9,10-dihydro-9,10-ethanoanthracene
o
(22). Colorless powder; yield: 0.96 g (1.71 mmol, 92%); mp: 243-245 C; IR (ATR) (νmax, cm−1): 3105, 3026,
1
2949, 2862, 1688, 1679, 1620, 1457, 1365, 1259, 1208, 996, 767, 691, 564; H NMR (400 MHz, DMSO-d6): δH =
7.57 (2H, s), 7.47- 7.41 (2H, m), 7.38 (4H, dd, J 5.1, 2.8 Hz), 7.19- 7.12 (4H, m), 7.02 (2H, d, J 4.9 Hz), 4.80 (2H,
s), 4.29 (2H, dd, J 19.2, 9.6 Hz), 4.06 (2H, ddd, J 15.1, 10.2, 5.3 Hz), 3.97 (2H, td, J 10.2, 5.0 Hz), 3.91-3.81 (2H,
m), 3.55 (2H, s); 13C NMR (100 MHz, DMSO-d6): δC = 170.2 (C=O), 155.5 (C=N), 143.1, 140.6 (dibenzobarrelene-
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