A. V. Butin et al. / Tetrahedron 63 (2007) 474–491
487
compound 8c (2.1 g, 4.9 mmol) in AcOH (40 mL) under
cooling in water bath. The resulted reaction mixture was
maintained at room temperature for 2 h (TLC monitoring),
poured into water, neutralized with NaHCO3, and extracted
with CH2Cl2 (3ꢂ50 mL). The extract was dried over anhy-
drous Na2SO4 and evaporated to dryness. The residue was
purified on silica gel (50–160 mm) column with acetone–
CH2Cl2–hexane (5:3:20) as an eluent. The solvent was re-
moved in rotatory evaporator and residue was recrystallized
from CH2Cl2–hexane. Yield 1.45 g, 69% as a white solid,
mp 90 ꢀC [Found: C, 64.62; H, 6.51; N, 3.07. C23H27NO5S
requires C, 64.31; H, 6.34; N, 3.26%]; nmax(KBr) 1713,
1489, 1469, 1358, 1277, 1215, 1194, 1177, 1157, 1016,
852, 676 cmꢁ1; dH (300 MHz, CDCl3) 7.79 (1H, s, HInd),
7.48 (2H, d, J 8.2 Hz, HTs), 7.14 (2H, d, J 8.2 Hz, HTs),
6.80 (1H, s, HInd), 3.97 (3H, s, OMe), 3.91 (3H, s, OMe),
3.17–3.12 (2H, m, CH2), 2.92–2.87 (2H, m, CH2), 2.57
(2H, q, J 7.5 Hz, CH2Me), 2.32 (3H, s, Me), 2.17 (3H, s,
Me), 1.10 (3H, t, J 7.5 Hz, CH2Me); dC (50 MHz, CDCl3)
208.0, 147.6, 147.2, 144.6, 135.5, 133.8, 131.1, 129.7(2C),
126.1(2C), 124.3, 123.6, 100.4, 99.7, 56.5, 56.2, 44.7,
30.0, 21.6, 20.9, 17.6, 14.8; MS: m/z (%) 429 (M+, 20),
275 (20), 274 (100), 232 (32), 231 (42), 218 (16), 217
(41), 216 (68), 202 (21), 91 (20).
68.14; H, 5.81; N, 2.80. C27H27NO5S requires C, 67.90;
H, 5.70; N, 2.93%]; nmax(KBr) 1715, 1488, 1469, 1439,
1362, 1309, 1232, 1183, 1156, 1088, 1021, 946, 850, 816,
769, 708, 690, 663, 603 cmꢁ1; dH (250 MHz, CDCl3) 7.86
(1H, s, HInd), 7.59 (2H, d, J 8.2 Hz, HTs), 7.50–7.38 (3H,
m, Ph), 7.29–7.25 (2H, m, Ph), 7.19 (2H, d, J 8.2 Hz, HTs),
6.72 (1H, s, HInd), 4.02 (3H, s, OMe), 3.81 (3H, s, OMe),
3.23–3.14 (2H, m, CH2), 2.98–2.89 (2H, m, CH2), 2.36
(3H, s, Me), 2.13 (3H, s, Me); dC (50 MHz, CDCl3) 207.4,
147.9, 147.4, 144.8, 135.3, 134.8, 132.9, 130.8, 129.8(2C),
129.6(2C), 128.8(2C), 127.6, 126.1(2C), 124.7, 123.5,
100.8, 99.3, 56.4, 56.0, 44.8, 29.7, 21.5, 21.4; MS: m/z (%)
477 (M+, 33), 323 (28), 322 (60), 280 (25), 279 (21), 276
(31), 266 (21), 265 (36), 264 (77), 234 (39), 232 (16), 219
(25), 218 (100), 217 (24), 204 (19), 91 (26).
4.1.7.7.
4-[5,6-Dimethoxy-3-(4-methylphenyl)-1-(4-
methylphenylsulfonyl)-1H-2-indolyl]-2-butanone (9g).
Yield 0.82 g, 84% as a white solid, mp 154–155 ꢀC [Found:
C, 68.67; H, 6.13; N, 2.96. C28H29NO5S requires C, 68.41;
H, 5.95; N, 2.85%]; nmax(KBr) 1714, 1490, 1465, 1444,
1365, 1295, 1230, 1216, 1181, 1156, 1088, 1034, 1017,
850, 774, 663, 632, 576, 544 cmꢁ1; dH (200 MHz, CDCl3)
7.83 (1H, s, HInd), 7.58 (2H, d, J 8.2 Hz, HTs), 7.25 (2H, d,
J 7.8 Hz, HAr), 7.18 (2H, d, J 8.2 Hz, HTs), 7.14 (2H, d,
J 7.8 Hz, HAr), 6.71 (s, 1H, HInd), 4.01 (3H, s, OMe), 3.80
(3H, s, OMe), 3.20–3.12 (2H, m, CH2), 2.94–2.86 (2H, m,
CH2), 2.41 (3H, s, Me), 2.32 (3H, s, Me), 2.12 (3H, s, Me);
dC (50 MHz, CDCl3) 207.4, 147.8, 147.4, 144.8, 137.4,
135.3, 134.7, 130.7, 129.8(2C), 129.7(2C), 129.5(2C),
129.4, 126.1(2C), 124.7, 123.7, 100.9, 99.3, 56.4, 56.0,
44.8, 29.7, 21.5, 21.4, 21.2; MS: m/z (%) 491 (M+, 27),
337 (21), 336 (73), 294 (31), 293 (22), 280 (25), 279 (52),
278 (100), 264 (22), 234 (23), 218 (41), 91 (43).
4.1.7.4. 4-[3-Benzyl-5,6-dimethoxy-1-(4-methylphenyl-
sulfonyl)-1H-2-indolyl]-2-butanone (9d). Compound 9d
was obtained similarly to compounds 9c. Yield 1.61 g,
67% as a white solid, mp 135–136 ꢀC [Found: C, 68.65; H,
6.12; N, 2.96. C28H29NO5S requires C, 68.41; H, 5.95; N,
2.85%]; nmax(KBr) 1717, 1489, 1459, 1351, 1286, 1212,
1175, 1147, 1087, 1021, 895, 853, 736, 689, 655 cmꢁ1; dH
(300 MHz, CDCl3) 7.81 (1H, s, HInd), 7.49 (2H, d,
J 8.3 Hz, HTs), 7.16–7.14 (5H, m, Ph+HTs), 6.95–6.92 (2H,
m, Ph), 6.63 (1H, s, HInd), 3.97 (3H, s, OMe), 3.95 (2H, s,
CH2Ph), 3.77 (3H, s, OMe), 3.18–3.13 (2H, m, CH2),
2.80–2.75 (2H, m, CH2), 2.36 (3H, s, Me), 2.09 (3H, s,
Me); dC (50 MHz, CDCl3) 207.7, 147.8, 147.4, 144.7, 139.5,
135.7, 135.3, 131.3, 129.8(2C), 128.4(2C), 128.0(2C),
126.2(2C), 126.1, 124.2, 121.3, 100.8, 99.8, 56.5, 56.1,
44.1, 30.0, 21.6, 21.1; MS: m/z (%) 491 (M+, 63), 336
(100), 279 (18), 278 (15), 190 (16), 91(39).
4.1.7.8.
4-[3-(4-Chlorophenyl)-5,6-dimethoxy-1-(4-
methylphenylsulfonyl)-1H-2-indolyl]-2-butanone (9h).
Yield 0.83 g, 81% as a white solid, mp 123–124 ꢀC [Found:
C, 63.53; H, 5.22; N, 2.99. C27H26ClNO5S requires C, 63.34;
H, 5.12; N, 2.74%]; nmax(KBr) 1711, 1489, 1441, 1363,
1288, 1267, 1219, 1185, 1157, 1089, 1039, 1015, 852,
837, 678, 657, 613, 572, 548 cmꢁ1; dH (200 MHz, CDCl3)
7.83 (1H, s, HInd), 7.58 (2H, d, J 8.2 Hz, HTs), 7.42 (2H, d,
J 8.0 Hz, HAr), 7.20 (2H, d, J 8.0 Hz, HAr), 7.18 (2H, d, J
8.2 Hz, HTs), 6.66 (1H, s, HInd), 4.01 (3H, s, OMe), 3.80
(3H, s, OMe), 3.19–3.10 (2H, m, CH2), 2.94–2.85 (2H, m,
CH2), 2.36 (3H, s, Me), 2.13 (3H, s, Me); dC (50 MHz,
CDCl3) 207.2, 148.1, 147.6, 145.0, 135.3, 135.1, 133.7,
131.5, 131.1(2C), 130.8, 129.9(2C), 129.1(2C), 126.2(2C),
123.6, 123.3, 100.6, 99.4, 56.5, 56.1, 44.7, 29.8, 21.6,
21.4; MS: m/z (%) 513/511 (M+, 25/58), 358 (24), 357
(100), 356 (71), 314 (27), 313 (27), 301 (21), 300 (75),
299 (42), 298 (59), 265 (25), 221 (16), 220 (24), 91 (77).
4.1.7.5. 4-[8-Methyl-6-(4-methylphenylsulfonyl)-2,3-
dihydro-6H-[1,4]dioxino[2,3-f]indol-7-yl]-2-butanone
(9e). Yield 0.70 g, 85% as colorless cubes, mp 122–123 ꢀC
[Found: C, 64.20; H, 5.77; N, 3.28. C22H23NO5S requires
C, 63.91; H, 5.61; N, 3.39%]; nmax(KBr) 1720, 1579,
1477, 1353, 1168, 1145, 1113, 1067, 916, 885, 810, 670,
647, 574 cmꢁ1; dH (250 MHz, CDCl3) 7.72 (1H, s, HInd),
7.54 (2H, d, J 8.2 Hz, HTs), 7.16 (2H, d, J 8.2 Hz, HTs),
6.78 (1H, s, HInd), 4.29–4.25 (4H, m, CH2CH2), 3.17–3.11
(2H, m, CH2), 2.91–2.85 (2H, m, CH2), 2.33 (3H, s, Me),
2.15 (3H, s, Me), 2.05 (3H, s, Me); dC (50 MHz, CDCl3)
208.0, 144.5, 141.8, 141.4, 135.5, 134.8, 131.3, 129.7(2C),
126.3(2C), 125.9, 117.5, 105.6, 104.2, 64.5, 64.3, 43.9,
30.0, 21.6, 20.9, 9.1; MS: m/z (%) 413 (M+, 15), 259 (34),
258 (100), 216 (76), 215 (69), 202 (50), 201 (20), 159
(30), 145 (20), 101 (18), 91 (29).
4.1.7.9. 4-[6-(4-Methylphenylsulfonyl)-8-phenyl-2,3-
dihydro-6H-[1,4]dioxino[2,3-f]indol-7-yl]-2-butanone
(9i). Yield 0.67 g, 71% as a white solid, mp 186–188 ꢀC
[Found: C, 68.32; H, 5.48; N, 3.27. C27H25NO5S requires
C, 68.19; H, 5.30; N, 2.95%]; nmax(KBr) 1712, 1471,
1358, 1332, 1156, 1084, 1064, 1035, 1016, 938, 844, 703,
681, 660, 588, 548 cmꢁ1; dH (300 MHz, CDCl3) 7.79 (1H,
s, HInd), 7.62 (2H, d, J 8.2 Hz, HTs), 7.44–7.34 (3H, m,
Ph), 7.25–7.23 (2H, m, Ph), 7.20 (2H, d, J 8.2 Hz, HTs),
4.1.7.6. 4-[5,6-Dimethoxy-1-(4-methylphenylsulfonyl)-
3-phenyl-1H-2-indolyl]-2-butanone (9f). Yield 0.76 g,
80% as colorless needles, mp 175–176 ꢀC [Found: C,