A.S. Pilipenko et al. / Tetrahedron 68 (2012) 619e627
625
(300 mL). The formed precipitate was filtered off, washed sub-
1121, 1053, 814 cmꢁ1
;
dH (300 MHz, CDCl3) 7.94e7.91 (1H, m, HAr),
sequently with NaHCO3 solution and water, air-dried, and purified
by column chromatography on silica gel using benzene/petroleum
ether (1:3) mixture as an eluent.
7.67 (2H, d, J 8.4 Hz, HTs), 7.46e7.43 (1H, m, HAr), 7.27e7.16 (4H, m,
2HArþ2HTs), 6.51 (1H, s, HInd), 4.13 (2H, s, CH2), 2.32 (3H, s, CH3),
2.30 (3H, s, CH3); dC (75 MHz, CDCl3) 204.3, 144.9, 136.5, 135.7,
134.0, 129.8 (2C), 129.1, 126.6 (2C), 124.3, 123.4, 120.6, 114.3, 112.3,
43.6, 29.6, 21.5; m/z (EI, 70 eV) 327 (Mþ,100), 284 (82), 220 (54),172
(26), 130 (57), 91 (47%).
4.5.1. 1-{6-Methyl-1-[(4-methylphenyl)sulfonyl]-1H-indol-2-yl}ace-
tone (8a). White solid; yield 75% (2.30 g); mp 119e120 ꢀC (ben-
zene/petroleum ether). Found: C, 67.02; H, 5.90; N, 4.02.
C19H19NO3S requires C, 66.84; H, 5.61; N, 4.10%. Rf¼0.52 (CH2Cl2/
acetone/petroleum ether¼1:1:2); nmax (KBr) 1720, 1424, 1364,1263,
4.5.6. 1-{1-[(4-Methylphenyl)sulfonyl]-1H-indol-2-yl}butan-2-one
(8f). White solid; yield 80% (2.46 g); mp 111e112 ꢀC (benzene/pe-
troleum ether). Found: C, 67.02; H, 5.67; N, 3.94. C19H19NO3S re-
quires C, 66.84; H, 5.61; N, 4.10%. Rf¼0.60 (CH2Cl2/acetone/
petroleum ether¼1:1:2); nmax (KBr) 1715, 1594, 1450, 1366, 1172,
1172, 1135, 1050, 826 cmꢁ1
; dH (300 MHz, CDCl3) 7.76 (1H, d, J
1.2 Hz, HAr), 7.64 (2H, d, J 8.4 Hz, HTs), 7.32 (1H, d, J 7.8 Hz, HAr), 7.19
(2H, d, J 8.4 Hz, HTs), 7.02 (1H, dd, J 7.8, 1.2 Hz, HAr), 6.45 (1H, s, HInd),
4.07 (2H, s, CH2), 2.43 (3H, s, CH3), 2.33 (3H, s, CH3), 2.28 (3H, s,
CH3); dC (75 MHz, CDCl3) 204.4, 144.8, 137.0, 135.9, 134.4, 133.3,
129.8 (2C), 126.9, 126.5 (2C), 125.0, 120.1, 114.5, 112.2, 43.6, 29.5,
22.0, 21.5; m/z (EI, 70 eV) 341 (Mþ, 70), 298 (77), 234 (73),144 (100),
143 (69), 91 (56), 65 (14), 43 (14%).
1111, 809 cmꢁ1
; dH (300 MHz, CDCl3) 7.95e7.92 (1H, m, HAr), 7.66
(2H, d, J 8.4 Hz, HTs), 7.46e7.43 (1H, m, HAr), 7.26e7.16 (4H, m,
2HArþ2HTs), 6.50 (1H, s, HInd), 4.10 (2H, s, CH2), 2.60 (2H, q, J 7.4 Hz,
CH2), 2.32 (3H, s, CH3), 1.10 (3H, t, J 7.4 Hz, CH3); dC (75 MHz, CDCl3)
206.7, 144.8, 136.5, 135.7, 134.1, 129.7 (2C), 129.2, 126.5 (2C), 124.2,
123.4, 120.5, 114.3, 112.2, 42.6, 35.4, 21.5, 7.6; m/z (EI, 70 eV) 341
(Mþ, 94), 285 (47), 284 (76), 220 (100), 186 (30), 130 (79), 129 (25),
91 (29), 57 (24), 43 (28%).
4.5.2. 1-{6-Methoxy-1-[(4-methylphenyl)sulfonyl]-1H-indol-2-yl}ac-
etone (8b). White solid; yield 64% (2.06 g); mp 176e177 ꢀC (ben-
zene/petroleum ether). Found: C, 64.19; H, 5.34; N, 3.91.
C19H19NO4S requires C, 63.85; H, 5.36; N, 3.92%. Rf¼0.48 (CH2Cl2/
acetone/petroleum ether¼1:1:2); nmax (KBr) 1720, 1616, 1490, 1364,
4.5.7. 1-{1-[(4-Methylphenyl)sulfonyl]-1H-indol-2-yl}-3-phenylace-
tone (8g). White solid; yield 56% (2.03 g); mp 115e116 ꢀC (ben-
zene/petroleum ether). Found: C, 71.22; H, 5.21; N, 3.44.
C24H21NO3S requires C, 71.44; H, 5.25; N, 3.47%. Rf¼0.61 (CH2Cl2/
acetone/petroleum ether¼1:1:2); nmax (KBr) 1730, 1452, 1358, 1172,
1280, 1173, 1055, 972, 819 cmꢁ1
; dH (300 MHz, CDCl3) 7.65 (2H, d, J
8.4 Hz, HTs), 7.47 (1H, d, J 2.4 Hz, HAr), 7.31 (1H, d, J 8.7 Hz, HAr), 7.20
(2H, d, J 8.4 Hz, HTs), 6.82 (1H, dd, J 8.7, 2.4 Hz, HAr), 6.42 (1H, s,
HInd), 4.06 (2H, s, CH2), 3.82 (3H, s, OCH3), 2.33 (3H, s, CH3), 2.28
(3H, s, CH3); dC (75 MHz, CDCl3) 204.6, 157.6, 144.9, 137.6, 135.7,
132.7, 129.8 (2C), 126.5 (2C), 122.9, 121.0, 112.5, 112.1, 98.9, 55.6,
43.7, 29.5, 21.5; m/z (EI, 70 eV) 357 (Mþ, 47), 315 (23), 314 (92), 250
(21), 160 (100), 144 (39), 117 (19), 91 (31), 43 (19%).
1088, 1051 cmꢁ1
; dH (300 MHz, CDCl3) 7.96e7.93 (1H, m, HAr), 7.64
(2H, d, J 8.4 Hz, HTs), 7.45e7.42 (1H, m, HAr), 7.39e7.16 (9H, m,
7HArþ2HTs), 6.46 (1H, s, HInd), 4.11 (2H, s, CH2), 3.90 (2H, s, CH2),
2.31 (3H, s, CH3); dC (75 MHz, CDCl3) 203.7,144.9,136.6,135.8,133.9,
133.8, 129.8 (2C), 129.7 (2C), 129.2, 128.7 (2C), 127.1, 126.6 (2C),
124.3, 123.4, 120.6, 114.3, 112.4, 49.6, 42.2, 21.5; m/z (EI, 70 eV) (%)
403 (Mþ, 21), 284 (49), 220 (71), 205 (21), 130 (89), 102 (22), 91
(100), 77 (17), 65 (66%).
4.5.3. 1-{6-Chloro-1-[(4-methylphenyl)sulfonyl]-1H-indol-2-yl}ace-
tone (8c). White solid; yield 85% (2.76 g); mp 117e118 ꢀC (benzene/
petroleum ether). Found: C, 60.04; H, 4.28; N, 3.88. C18H16ClNO3S
requires C, 59.75; H, 4.46; N, 3.87%. Rf¼0.49 (CH2Cl2/acetone/pe-
troleum ether¼1:1:2); nmax (KBr) 1721, 1592, 1457, 1424, 1372, 1328,
4.5.8. 1-(4-Methylphenyl)-3-{1-[(4-methylphenyl)sulfonyl]-1H-in-
dol-2-yl}acetone (8h). White solid; yield 60% (2.25 g); mp
109e110 ꢀC (benzene/petroleum ether). Found: C, 72.03; H, 5.63; N,
3.25. C25H23NO3S requires C, 71.92; H, 5.55; N, 3.35%. Rf¼0.63
(CH2Cl2/acetone/petroleum ether¼1:1:2); nmax (KBr) 1724, 1456,
1273, 1173, 1091, 1048, 948, 830 cmꢁ1
; dH (300 MHz, CDCl3) 7.96
(1H, d, J 1.8 Hz, HAr), 7.65 (2H, d, J 8.4 Hz, HTs), 7.34 (1H, d, J 8.1 Hz,
HAr), 7.23 (2H, d, J 8.4 Hz, HTs), 7.17 (1H, dd, J 8.1, 1.8 Hz, HAr), 6.47
(1H, s, HInd), 4.10 (2H, s, CH2), 2.35 (3H, s, CH3), 2.29 (3H, s, CH3); dC
(75 MHz, CDCl3) 203.9, 145.3, 136.9, 135.4, 134.7, 130.3, 130.0 (2C),
127.6, 126.6 (2C), 124.1, 121.3, 114.5, 111.8, 43.5, 29.6, 21.6; m/z (EI,
70 eV) 363/361 (Mþ, 20/60), 320/318 (33/100), 256/254 (18/56), 219
(17), 206 (22), 166 (28), 164 (58), 91 (54), 43 (16%).
1386, 1256, 1192, 1180, 1088, 1068, 1052, 808 cmꢁ1
; dH (300 MHz,
CDCl3) 7.98e7.95 (1H, m, HAr), 7.66 (2H, d, J 8.1 Hz, HTs), 7.46e7.43
(1H, m, HAr), 7.28e7.16 (8H, m, 6HArþ2HTs), 6.46 (1H, s, HInd), 4.13
(2H, s, CH2), 3.88 (2H, s, CH2), 2.36 (3H, s, CH3), 2.31 (3H, s, CH3); dC
(75 MHz, CDCl3) 203.9, 144.8, 136.6, 136.5, 135.8, 133.9, 130.8, 129.7
(2C), 129.5 (2C), 129.3 (2C), 129.1, 126.6 (2C), 124.2, 123.4, 120.5,
114.2, 112.4, 49.2, 42.1, 21.5, 21.0; m/z (EI, 70 eV) 417 (Mþ, 13), 284
(57), 220 (70), 130 (71), 105 (100), 91 (62), 77(26), 65 (21%).
4.5.4. 1-{6-Chloro-1-[(4-methylphenyl)sulfonyl]-1H-indol-2-yl}bu-
tan-2-one (8d). White solid; yield 73% (2.46 g); mp 131e132 ꢀC
(benzene/petroleum ether). Found: C, 60.52; H, 4.78; N, 3.72.
C19H18ClNO3S requires C, 60.71; H, 4.83; N, 3.73%. Rf¼0.55 (CH2Cl2/
acetone/petroleum ether¼1:1:2); nmax (KBr) 1721, 1454, 1365, 1168,
4.5.9. 5-{6-Chloro-1-[(4-methylphenyl)sulfonyl]-1H-indol-2-yl}-4-
oxopentanoic acid (13a). White solid; yield 45% (1.70 g); mp
147e148 ꢀC (benzene/petroleum ether). Found: C, 56.84; H, 4.15; N,
3.13. C20H18ClNO5S requires C, 57.21; H, 4.32; N, 3.34%. Rf¼0.02
(CH2Cl2/acetone/petroleum ether¼1:1:2); nmax (KBr) 3430, 1712,
1092,1050, 952, 816 cmꢁ1
; dH (300 MHz, CDCl3) 7.97 (1H, d, J 1.8 Hz,
HAr), 7.65 (2H, d, J 8.4 Hz, HTs), 7.33 (1H, d, J 8.4 Hz, HAr), 7.22 (2H, d, J
8.4 Hz, HTs), 7.17 (1H, dd, J 8.4, 1.8 Hz, HAr), 6.46 (1H, s, HInd), 4.07
(2H, s, CH2), 2.59 (2H, q, J 7.5 Hz, CH2), 2.35 (3H, s, CH3), 1.10 (3H, t, J
7.5 Hz, CH3); dC (75 MHz, CDCl3) 206.4, 145.3, 136.9, 135.5, 134.8,
130.2, 129.9 (2C), 127.7, 126.6 (2C), 124.1, 121.2, 114.5, 111.8, 42.5,
35.5, 21.5, 7.6; m/z (EI, 70 eV) 377/375 (Mþ, 11/33), 320/318 (12/36),
254 (64), 219 (27), 164 (57), 128 (22), 91 (50), 57 (100%).
1424, 1360, 1276, 1260, 1172, 1088, 948 cmꢁ1
; dH (300 MHz, CDCl3)
9.92 (1H, br s, OH), 7.97 (1H, s, HAr), 7.63 (2H, d, J 8.2 Hz, HTs),
7.34e7.14 (4H, m, 2HArþ2HTs), 6.49 (1H, s, HInd), 4.11 (2H, s, CH2),
2.89e2.87 (2H, m, CH2), 2.69e2.66 (2H, m, CH2), 2.33 (3H, s, CH3);
dC (75 MHz, CDCl3) 203.9, 178.5, 145.3, 136.9, 135.4, 134.2, 130.3,
130.0 (2C), 127.6, 126.5 (2C), 124.2, 121.3, 114.5, 112.2, 42.7, 36.4,
27.8, 21.5; m/z (EI, 70 eV) 421/419 (Mþ, 2/6), 319 (33), 164 (100),
155(18), 101 (27), 91 (84) 65 (44%).
4.5.5. 1-{1-[(4-Methylphenyl)sulfonyl]-1H-indol-2-yl}acetone
(8e). White solid; yield 83% (2.44 g); mp 97e98 ꢀC (benzene/pe-
troleum ether). Found: C, 66.38; H, 5.11; N, 4.18. C18H17NO3S re-
quires C, 66.03; H, 5.23; N, 4.28%. Rf¼0.56 (CH2Cl2/acetone/
petroleum ether¼1:1:2); nmax (KBr) 1722, 1452, 1361, 1250, 1170,
4.5.10. 5-{6-Methyl-1-[(4-methylphenyl)sulfonyl]-1H-indol-2-yl}-4-
oxopentanoic acid (13b). White solid; yield 43% (1.54 g); mp