´
M. Alajarın et al. / Tetrahedron 59 (2003) 9913–9918
9917
diphenylketene (0.19 g, 1 mmol) in the same solvent (2 ml)
was added. The reaction mixture was stirred first 30 min at
room temperature and then at reflux temperature for 2 h.
After cooling, the toluene was removed under reduced
pressure and the resulting solid was chromatographed on a
silica gel column using ethyl acetate/methanol as eluent
(3:2, v/v).
145.8 (s), 168.2 (s); MS m/z (%): 421 (Mþ2, 48), 420
(Mþ1, 37), 419 (M, 50), 401 (100). Anal. calcd for
C23H19BrN2O: C, 65.88; H, 4.57; N, 6.68. Found: C, 65.95;
H, 4.49; N, 6.76.
4.4.5. cis-5-(4-Cyanophenyl)-10-hydroxy-10-phenyl-
2,3,5,10-tetrahydroimidazo[1,2-b]isoquinoline (cis-9c).
Yield 17%, colorless prisms (Et2O), mp 183–1858C; IR
(Nujol) n 2228, 1607, 1596, 1277, 1189, 1177, 1134, 769,
4.4.1. cis-5-(4-Chlorophenyl)-10-hydroxy-10-phenyl-
2,3,5,10-tetrahydroimidazo[1,2-b]isoquinoline (cis-9a).
Yield 17%, colorless prisms (Et2O), mp 216–2188C; IR
(Nujol) n 3083, 1608, 1598, 1489, 1463, 1408, 1277, 1187,
1
721, 700 cm21; H NMR (CDCl3) d 3.03–3.33 (m, 2H),
3.52–3.75 (m, 2H), 5.32 (s, 1H), 6.60 (d, 1H, J¼7.6 Hz),
7.10–7.37 (m, 7H), 7.45 (d, 2H, J¼8.1 Hz), 7.61–7.71 (m,
3H); 13C NMR (CDCl3) d 49.9, 51.9, 62.5, 72.3 (s), 112.5
(s), 118.4 (s), 125.8, 126.8, 127.6, 127.7, 128.4, 128.5,
129.6, 132.9, 134.2 (s), 138.2 (s), 145.6 (s), 146.2 (s), 168.4
(s); MS m/z (%): 365 (M, 20), 348 (100). Anal. calcd for
C24H19N3O: C, 78.88; H, 5.24; N, 11.50. Found: C, 79.01;
H, 5.19; N, 11.43.
1
1091, 928, 751, 711 cm21; H NMR (CDCl3) d 3.13–3.29
(m, 2H), 3.55–3.78 (m, 2H), 5.26 (s, 1H), 6.67 (d, 1H,
J¼7.8 Hz), 7.13 (td, 1H, J¼7.7, 1.5 Hz), 7.21–7.31 (m,
7H), 7.35–7.38 (m, 3H), 7.62 (dd, 1H, J¼8.1, 1.5 Hz); 13C
NMR (CDCl3) d 50.1, 52.1, 62.1, 72.3 (s), 125.8, 127.0,
127.2, 127.5, 127.6, 128.3, 128.4, 129.3, 130.3, 134.3 (s),
135.3 (s), 138.2 (s), 139.4 (s), 145.7 (s), 168.6 (s); MS m/z
(%): 376 (Mþ2, 33), 375 (Mþ1, 60), 374 (M, 62), 263
(100). Anal. calcd for C23H19ClN2O: C, 73.69; H, 5.11; N,
7.47. Found: C, 73.83; H, 5.19; N, 7.54.
4.4.6. trans-5-(4-Cyanophenyl)-10-hydroxy-10-phenyl-
2,3,5,10-tetrahydroimidazo[1,2-b]isoquinoline (trans-
9c). Yield 23%, colorless prisms (CH2Cl2/Et2O), mp 151–
1538C; IR (Nujol) n 3180, 2227, 1623, 1281, 1256, 1145,
1
4.4.2. trans-5-(4-Chlorophenyl)-10-hydroxy-10-phenyl-
2,3,5,10-tetrahydroimidazo[1,2-b]isoquinoline (trans-
9a). Yield 24%, colorless prisms (CHCl3/Et2O), mp
1648C; IR (Nujol) n 3232, 1620, 1275, 1253, 1183, 1167,
1090, 1028, 927, 759, 738 cm21; 1H NMR (CDCl3) d 3.16–
3.33 (m, 1H), 3.53–3.67 (m, 2H), 3.74–3.91 (m, 1H), 5.16
(s, 1H), 5.68 (br s, 1H), 6.95–7.00 (m, 3H), 7.15–7.37 (m,
9H), 7.74 (d, 1H, J¼7.7 Hz); 13C NMR (CDCl3) d 52.3,
52.6, 65.6, 72.1 (s), 126.5, 126.6, 127.5, 127.7, 127.8, 127.9,
128.0, 128.7, 129.2, 133.6 (s), 134.3 (s), 137.4 (s), 140.1 (s),
145.8 (s), 168.1 (s); MS m/z (%): 376 (Mþ2, 22), 375
(Mþ1, 38), 374 (M, 70), 357 (100). Anal. calcd for
C23H19ClN2O: C, 73.69; H, 5.11; N, 7.47. Found: C, 73.74;
H, 5.25; N, 7.40.
1028, 928, 770, 715 cm21; H NMR (CDCl3) d 3.22–3.32
(m, 1H), 3.53–3.68 (m, 2H), 3.80–3.94 (m, 1H), 5.24 (s,
1H), 7.02 (d, 1H, J¼7.7 Hz), 7.10 (d, 2H, J¼8.2 Hz), 7.19–
7.46 (m, 9H), 7.81 (d, 1H, J¼7.3 Hz); 13C NMR (CDCl3) d
52.5, 53.0, 65.7, 72.3 (s), 111.8 (s), 118.5 (s), 126.6, 126.8,
127.8, 127.9, 128.0, 128.2, 128.4, 132.4, 133.6 (s), 137.6 (s),
145.0 (s), 146.7 (s), 168.1 (s); MS m/z (%): 365 (M, 25), 348
(100). Anal. calcd for C24H19N3O: C, 78.88; H, 5.24; N,
11.50. Found: C, 78.95; H, 5.29; N, 11.69.
4.4.7. cis-5-(3,5-Dimethoxyphenyl)-10-hydroxy-10-
phenyl-2,3,5,10-tetrahydroimidazo[1,2-b]isoquinoline
(cis-9d). Yield 26%, colorless prisms (CH2Cl2/Et2O), mp
2238C; IR (Nujol) n 3170, 1614, 1601, 1296, 1274, 1207,
1163, 1067, 839, 772, 697 cm21; 1H NMR (CDCl3) d 3.23–
3.31 (m, 2H), 3.55–3.73 (m, 2H), 3.75 (s, 6H), 5.18 (s, 1H),
6.42 (t, 1H, J¼2.4 Hz), 6.47 (d, 2H, J¼2.4 Hz), 6.79 (d, 1H,
J¼7.8 Hz), 7.13 (td, 1H, J¼7.5, 1.2 Hz), 7.18–7.31 (m,
4H), 7.35–7.39 (m, 2H), 7.61 (d, 1H, J¼7.8 Hz); 13C NMR
(CDCl3) d 49.9, 51.8, 55.5, 62.8, 72.3 (s), 100.1, 106.8,
125.9, 126.9, 127.0, 127.3, 127.4, 128.0, 128.3, 135.3 (s),
138.3 (s), 143.1 (s), 145.9 (s), 161.3 (s), 168.8 (s); MS m/z
(%): 400 (M, 23), 382 (100). Anal. calcd for C25H24N2O3:
C, 74.98; H, 6.04; N, 7.00. Found: C, 75.13; H, 6.19; N,
6.97.
4.4.3. cis-5-(4-Bromophenyl)-10-hydroxy-10-phenyl-
2,3,5,10-tetrahydroimidazo[1,2-b]isoquinoline (cis-9b).
Yield 25%, colorless prisms (Et2O), mp 200–2038C; IR
(Nujol) n 3200, 1599, 1280, 1187, 1071, 1011, 808, 768,
1
748 cm21; H NMR (CDCl3) d 3.14–3.28 (m, 2H), 3.50–
3.73 (m, 2H), 5.23 (s, 1H), 6.65 (d, 1H, J¼7.5 Hz), 7.13 (td,
1H, J¼7.5, 1.2 Hz), 7.18–7.31 (m, 6H), 7.34–7.38 (m, 2H),
7.52 (d, 2H, J¼8.4 Hz), 7.65 (dd, 1H, J¼7.8, 1.5 Hz); 13C
NMR (CDCl3) d 50.0, 52.0, 62.1, 72.3 (s), 122.4 (s), 125.8,
126.9, 127.2, 127.5, 127.6, 128.3, 128.4, 130.6, 132.2, 135.1
(s), 138.2 (s), 139.9 (s), 145.7 (s), 168.6 (s); MS m/z (%):
421 (Mþ2, 20), 420 (Mþ1, 20), 419 (M, 30), 401 (100).
Anal. calcd for C23H19BrN2O: C, 65.88; H, 4.57; N, 6.68.
Found: C, 65.70; H, 4.61; N, 6.57.
4.4.8. trans-5-(3,5-Dimethoxyphenyl)-10-hydroxy-10-
phenyl-2,3,5,10-tetrahydroimidazo[1,2-b]isoquinoline
(trans-9d). Yield 36%, colorless prisms (Et2O), mp 177–
1808C; IR (Nujol) n 3200, 1612, 1599, 1352, 1292, 1262,
4.4.4. trans-5-(4-Bromophenyl)-10-hydroxy-10-phenyl-
2,3,5,10-tetrahydroimidazo[1,2-b]isoquinoline (trans-
9b). Yield 31%, colorless prisms (Et2O), mp 138–1408C;
IR (Nujol) n 3187, 1625, 1277, 1140, 1073, 1012, 929, 761,
1208, 1152, 1065, 770, 697 cm21 1H NMR (CDCl3) d
;
3.26–3.36 (m, 1H), 3.58–3.79 (m, 8H), 3.94–4.04 (m, 1H),
5.12 (s, 1H), 6.29 (d, 2H, J¼2.4 Hz), 6.33 (t, 1H, J¼2.4 Hz),
7.09 (d, 1H, J¼8.1 Hz), 7.21–7.29 (m, 4H), 7.34 (t, 1H,
J¼7.5 Hz), 7.42–7.45 (m, 2H), 7.65 (dd, 1H, J¼7.8,
1.2 Hz); 13C NMR (CDCl3) d 52.3, 52.6, 55.3, 66.6, 72.0
(s), 99.9, 105.9, 126.7, 126.8, 127.5, 127.8, 127.9, 128.1,
134.5 (s), 136.9 (s), 144.2 (s), 146.3 (s), 161.0 (s), 168.0 (s);
MS m/z (%): 400 (M, 100). Anal. calcd for C25H24N2O3: C,
74.98; H, 6.04; N, 7.00. Found: C, 74.90; H, 5.99; N, 7.11.
1
700 cm21; H NMR (CDCl3) d 3.15–3.25 (m, 1H), 3.46–
3.63 (m, 2H), 3.65–3.86 (m, 1H), 5.14 (s, 1H), 6.91 (d, 2H,
J¼8.4 Hz), 6.96 (d, 1H, J¼7.8 Hz), 7.14–7.38 (m, 9H),
7.74 (dd, 1H, J¼8.1, 1.2 Hz); 13C NMR (CDCl3) d 52.3,
52.6, 65.7, 72.2 (s), 121.8 (s), 126.7, 127.4, 127.6, 127.8,
127.9, 128.1, 129.6, 131.7, 134.2 (s), 137.5 (s), 140.7 (s),