Nie, Duan & Ding
FULL PAPER
diate 3 was generated. The solvent was removed off
under reduced pressure. To the solution of 3 prepared
above in anhydrous acetonitrile (10 mL) was added I2
(6.0 mmol, 1.5 g) and K2CO3 (9.0 mmol, 1.3 g). After
the reaction mixture was stirred for 3 h, saturated aque-
ous Na2S2O3 solution was added to remove the unre-
acted I2. The mixture was extracted by methylene di-
chloride and the organic layer was evaporated under
reduced pressure. The crude product was purified by
flash chromatography (petroleum ether/diethyl ether,
V∶V=4∶1) to yield indole derivatives 4a—4k.
197 (1), 191 (4). Anal. calcd for C26H24IN3O: C 59.89,
H 4.64, N 8.06; found C 59.56, H 4.79, N 8.30.
N-[(3-Iodo-2-phenyl-1H-indol-1-yl)(morpholino)-
methylene]-3-methylaniline (4e): White solid (yield
1
81%), m.p. 170—172 ℃; H NMR (CDCl3, 600 MHz)
δ: 7.52—7.48 (m, 2H), 7.36—7.24 (m, 5H), 7.06—7.04
(m, 2H), 6.70—6.59 (m, 2H), 5.75—5.73 (m, 2H), 3.88
—3.80 (m, 3H), 3.62—3.56 (m, 3H), 3.20—3.15 (m,
2H), 1.98 (s, 3H); 13C NMR (CDCl3, 150 MHz) δ: 146.2,
143.6, 139.2, 137.7, 136.5, 130.8, 130.5, 129.8, 128.5,
128.0, 127.7, 124.5, 123.5, 123.2, 122.3, 122.1, 122.0,
117.8, 111.4, 66.5, 63.9, 46.6, 46.5, 21.1; MS (EI, 70 eV)
m/z (%): 521 (M+, 3), 203 (100), 197 (1), 191 (4), 175
(1). Anal. calcd for C26H24IN3O: C 59.89, H 4.64, N
8.06; found C 60.12, H 4.66, N 8.19.
4-Chloro-N-[(3-iodo-2-phenyl-1H-indol-1-yl)(mor-
pholino)methylene]aniline (4a): White solid (yield
1
77%), m.p. 223—225 ℃; H NMR (CDCl3, 600 MHz)
δ: 7.51—7.47 (m, 2H), 7.38—7.29 (m, 5H), 7.10—7.09
(m, 2H), 6.81—6.80 (m, 2H), 5.89 (d, J=8.4 Hz, 2H),
3.87—3.80 (m, 3H), 3.62—3.54 (m, 3H), 3.18—3.14
(m, 2H); 13C NMR (CDCl3, 150 MHz) δ: 145.0, 143.9,
138.9, 136.1, 130.8, 130.3, 129.8, 128.7, 128.3, 127.9,
127.8,124.8, 123.0, 122.5, 122.3, 111.2, 66.5, 64.3, 46.5,
46.0; MS (EI, 70 eV) m/z (%): 541 (M+, 4), 223 (100),
190 (6), 179 (12), 165 (3), 151 (6), 138 (4), 111 (10).
Anal. calcd for C25H21ClIN3O: C 55.42, H 3.91, N 7.76;
found C 55.71, H 4.12, N 7.90.
N,N-Dibutyl-3-iodo-N',2-diphenyl-1H-indole-1-car-
boximidamide (4f): White solid (yield 84%), m.p. 95—
1
97 ℃; H NMR (CDCl3, 600 MHz) δ: 7.46—7.45 (m,
1H), 7.37—7.30 (m, 4H), 7.27—7.22 (m, 4H), 6.86—
6.83 (m, 2H), 6.75—6.74 (m, 1H), 6.13 (d, J=7.2 Hz,
2H), 3.63—3.62 (m, 1H), 3.48—3.46 (m, 1H), 2.87—
2.84 (m, 2H), 1.59—1.56 (m, 2H), 1.44—1.41 (m, 2H),
1.27—1.26 (m, 2H), 1.04—1.00 (m, 2H), 0.92 (t, J=7.2
Hz, 3H ), 0.68 (t, J=7.2 Hz, 3H); 13C NMR (CDCl3,
150 MHz) δ: 147.2, 143.2, 139.0, 136.4, 130.7, 130.5,
130.0, 128.5, 128.2, 127.8, 124.1, 122.1, 121,8, 121.7,
111.8, 63.3, 47.5, 47.1, 30.6, 28.6, 20.4, 20.0, 14.0, 13.6;
MS (EI, 70 eV) m/z (%): 549 (M+, 2), 319 (2), 293 (3),
231 (100). Anal. calcd for C29H32IN3: C 63.39, H 5.87,
N 7.65; found C 63.56, H 6.08, N 7.83.
4-Fluoro-N-[(3-iodo-2-phenyl-1H-indol-1-yl)(mor-
pholino)methylene]aniline (4b): White solid (yield
1
80%), m.p. 196—198 ℃; H NMR (CDCl3, 600 MHz)
δ: 7.51—7.47 (m, 2H), 7.38—7.29 (m, 5H), 7.10—7.09
(m, 2H), 6.56—6.53 (m, 2H), 5.91—5.89 (m, 2H),
3.85—3.79 (m, 3H), 3.62—3.54 (m, 3H), 3.18—3.13
(m, 2H); 13C NMR (CDCl3, 150 MHz) δ: 159.7, 158.1,
143.8, 142.5, 138.9, 136.2, 130.8, 130.4, 129.7, 128.7,
127.9, 124.7,122.8, 122.4, 122.2, 114.9, 114.8, 111.3,
66.3, 64.2, 46.5, 46.0; MS (EI, 70 eV) m/z (%): 525 (M+,
3), 311 (1), 207 (100). Anal. calcd for C25H21FIN3O: C
57.15, H 4.03, N 8.00; found C 57.12, H 4.21, N 8.26.
N-[(3-Iodo-2-phenyl-1H-indol-1-yl)(morpholino)-
methylene]aniline (4c): White solid (yield 85%), m.p.
3-Iodo-N,N-diisopropyl-N',2-diphenyl-1H-indole-1-
carboximidamide (4g): White solid (yield 79%), m.p.
1
128—130 ℃; H NMR (CDCl3, 600 MHz) δ: 7.47—
7.45 (m, 1H), 7.37—7.34 (m, 6H), 7.25—7.22 (m, 2H),
6.87—6.85 (m, 2H), 6.74—6.72 (m, 1H), 6.20 (d, J=
7.8 Hz, 2H), 3.59—3.58 (m, 1H), 3.32—3.30 (m, 1H),
1.67 (d, J=6.0 Hz, 3H), 1.49 (d, J=6.0 Hz, 3H), 1.00
(d, J=6.0 Hz, 3H), 0.88 (d, J=6.0 Hz, 3H); 13C NMR
(CDCl3, 150 MHz) δ: 147.1, 139.9, 138.7, 136.6, 130.5,
130.4, 130.2, 128.7, 128.2, 127.7, 123.9, 122.0, 121.8,
111.6, 62.3, 49.1, 49.0, 46.6, 21.6, 21.2, 20.4, 19.7; MS
(EI, 70 eV) m/z (%): 521 (M+, 2), 293 (2), 203 (100).
Anal. calcd for C27H28IN3: C 62.19, H 5.41, N 8.06;
found C 62.34, H 5.53, N 8.28.
1
191—193 ℃; H NMR (CDCl3, 600 MHz) δ: 7.49—
7.47 (m, 2H), 7.37—7.23 (m, 5H), 7.09—7.07 (m, 2H),
6.85—6.76 (m, 3H), 6.00 (d, J=7.8 Hz, 2H), 3.84—
3.74 (m, 3H), 3.58—3.48 (m, 3H), 3.14—3.09 (m, 2H);
13C NMR (CDCl3, 150 MHz) δ: 146.3, 143.5, 139.0,
136.2, 130.8, 130.4, 129.8, 128.6, 128.2, 127.8, 124.5,
122.8, 122.3, 122.0, 121.6, 111.4, 66.3, 64.1, 46.4, 46.0;
MS (EI, 70 eV) m/z (%): 507 (M+, 3), 293 (1), 191 (5),
189 (100). Anal. calcd for C25H22IN3O: C 59.18, H 4.37,
N 8.28; found C 59.36, H 4.51, N 8.22.
3-Iodo-N',2-diphenyl-N,N-dipropyl-1H-indole-1-car-
boximidamide (4h): White solid (yield 84%), m.p. 111
1
—113 ℃; H NMR (CDCl3, 600 MHz) δ: 7.47—7.46
(m, 1H), 7.37—7.31 (m, 4H), 7.28—7.20 (m, 4H), 6.85
—6.83 (m, 2H), 6.75—6.73 (m, 1H), 6.09 (d, J=7.8 Hz,
2H), 3.57—3.45 (m, 2H), 2.88 (t, J=7.8 Hz, 2H), 1.66
—1.63 (m, 2H), 1.52—1.49 (m, 2H), 0.88 (t, J=7.2 Hz,
3H), 0.68 (t, J=7.2 Hz, 3H); 13C NMR (CDCl3, 150
MHz) δ: 147.2, 143.2, 139.0, 136.5, 130.8, 130.5, 130.0,
128.6, 128.2, 127.7, 124.1, 122.1, 121.8, 121.7, 121.6,
111.7, 63.4, 49.6, 21.8, 19.7, 11.7, 11.4; MS (EI, 70 eV)
m/z (%): 521 (M+, 2), 293 (2), 203 (100). Anal. calcd
for C27H28IN3: C 62.19, H 5.41, N 8.06; found C 62.28,
H 5.57, N 8.24.
N-[(3-Iodo-2-phenyl-1H-indol-1-yl)(morpholino)-
methylene]-4-methylaniline (4d): White solid (yield
1
84%), m.p. 214—216 ℃; H NMR (CDCl3, 600 MHz)
δ: 7.50—7.44 (m, 2H), 7.36—7.24 (m, 5H), 7.14—7.12
(m, 2H), 6.69—6.66 (m, 2H), 5.97 (d, J=7.8 Hz, 2H),
3.79—3.42 (m, 6H), 3.08—3.02 (m, 2H), 2.14 (s, 3H);
13C NMR (CDCl3, 150 MHz) δ: 146.7, 143.2, 139.0,
136.1, 132.2, 130.7, 130.5, 129.8, 128.9, 128.6, 127.8,
124.5, 122.2, 122.0, 121.5, 111.5, 66.4, 63.9, 46.3, 46.1,
20.7; MS (EI, 70 eV) m/z (%): 521 (M+, 2), 203 (100),
1808
© 2012 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Chin. J. Chem. 2012, 30, 1807—1812