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brs, NH), 8.90 (1H, d, J=2.2Hz, C4-H), 8.67 (1H, s, C2-H), 5-bromo-3-methylthioindole 7h was obtained as pale colorless
8.19 (1H, dd, J=9.0, 2.2Hz, C6-H), 7.81 (1H, d, J=9.0Hz, needles. mp 76–78°C (hexane–benzene); 1H-NMR (CDCl3)
C7-H), 3.36 (6H, s, SMe2); IR (KBr) 3445, 1525, 1348cm−1; δ: 8.21 (1H, brs, NH), 7.89 (1H, brd, J=1.6Hz, C4-H), 7.32
HR-MS (EI): Calcd for C10H10N2O2S (M−H)+: 222.0457, (1H, dd, J=8.6, 1.6Hz, C6-H), 7.30 (1H, d, J=2.6Hz, C2-H),
Found: 222.0459; Elemental analysis Calcd for C10H11ClN2O6S: 7.24 (1H, d, J=8.6Hz, C7-H), 2.35 (3H, s, SMe); 13C-NMR
C, 37.22; H, 3.44; N, 8.68. Found: C, 37.12; H, 3.43; N, 8.49.
(CDCl3) δ: 134.9, 130.6, 129.0, 125.7, 122.0, 113.9, 112.9, 108.2,
3-Methylthio-5-nitroindole 7f According to the gen- 20.3; IR (KBr): 3410cm−1; HR-MS (EI): Calcd for C9H8NS79Br
eral procedure, from 8.94g (27.7mmol) of (5-nitroindol-3- (M+): 240.9561. Found: 240.9566; Elemental analysis Calcd
yl)dimethylsulfonium perchlorate 4f, 5.45g (94.4%) of for C9H8BrNS: C, 44.64; H, 3.33; N, 5.78. Found: C, 44.59; H,
3-methylthio-5-nitroindole 7f was obtained as pale yellow 3.32; N, 5.53.
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prisms. mp 157–158°C (hexane–AcOEt); H-NMR (CDCl3) δ:
(4-Bromoindol-3-yl)dimethylsulfonium Perchlorate 4i
8.70 (1H, d, J=2.2Hz, C4-H), 8.55 (1H, s, NH), 8.14 (1H, dd, According to the general procedure, from 454.9mg (2.32mmol)
J=8.9, 2.2Hz, C6-H), 7.44 (1H, d, J=2.2Hz, C2-H), 7.42 (1H, of 4-bromoindole 1i, 772.7mg (93.4%) of (4-bromoindol-3-yl)-
d, J=8.9Hz, C7-H), 2.40 (3H, s, SMe); 13C-NMR (CDCl3) δ: dimethylsulfonium perchlorate 4i was obtained as colorless
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142.4, 139.3, 130.4, 128.4, 118.4, 116.6, 111.7, 111.6, 20.2; IR prisms. mp 130–135°C (dec.); H-NMR (DMSO-d6) δ: 12.88
(KBr) 3312, 1326cm−1; HR-MS (EI): Calcd for C9H8N2O2S: (1H, brs, NH), 8.50 (1H, d, J=0.9Hz, C2-H), 7.64 (1H, d,
208.0307, Found: 208.0306; Elemental analysis Calcd for J=8.0Hz, C5 or 7-H), 7.49 (1H, d, J=8.0Hz, C6-H), 7.25 (1H, t,
C9H8N2O2S: C, 51.91; H, 3.87; N, 13.45. Found: C, 51.86; H, J=8.0Hz, C5 or 7-H), 3.34 (6H, s, SMe2); IR (KBr): 3420cm−1;
3.88; N, 13.44; EIMS m/z: 208 (M+, BP).
Elemental analysis Calcd for C10H11BrClNO4S: C, 33.68; H,
(5-Fluoroindol-3-yl)dimethylsulfonium Perchlorate 4g 3.11; N, 3.93. Found: C, 33.46; H, 3.04; N, 3.57.
According to the general procedure, from 137.5mg (1.02mmol)
4-Bromo-3-methylthioindole 7i According to the gen-
of 5-fluoroindole 1g, 260.2mg (86.5%) of (5-fluoroindol-3-yl)- eral procedure, from 772.7mg (2.17mmol) of (4-bromoindol-3-
dimethylsulfonium perchlorate 4g was obtained as colorless yl)dimethylsulfonium perchlorate 4i, 488.4mg (93.1%) of
prisms. mp 184–190°C (dec.); EI-MS m/z: 181 (M+−CH3), 4-bromo-3-methylthioindole 7i was obtained as pale brown
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166 (BP, M+−2·CH3); 1H-NMR (DMSO-d6) δ: 12.58 (1H, prisms. mp 54.5–56°C (hexane–AcOEt); H-NMR (CDCl3) δ:
brs, NH), 8.42 (1H, brs, C2-H), 7.90 (1H, dd, J=9.6, 2.4Hz, 8.23 (1H, brs, NH), 7.33 (1H, dd, J=7.9, 0.7Hz, C5 or 7-H), 7.31
C4-H), 7.64 (1H, dd, J=9.0, 4.6Hz, C7-H), 7.21 (1H, ddd, (1H, dd, J=7.9, 0.7Hz, C5 or 7-H), 7.30 (1H, d, J=0.7Hz, C2-H),
J=9.0, 9.0, 2.4Hz, C6-H), 3.32 (6H, s, SMe2); 13C-NMR 7.03 (1H, t, J=7.9Hz, C6-H), 2.43 (3H, s, SMe); 13C-NMR
(acetone-d6) δ: 159.9 (d, JC–F=237Hz), 136.2, 134.7, 126.0 (d, (100MHz, CDCl3) δ 137.6, 128.9, 126.0, 125.0, 123.5, 114.3,
JC–F=10.7Hz), 116.1 (d, JC–F=9.9Hz), 113.5 (d, JC–F=25.0Hz), 110.9, 109.5, 22.0; IR (KBr): 3248cm−1; HR-MS (EI): Calcd
104.6 (d, JC–F=26.4Hz), 94.2 (d, JC–F=4.1Hz), 29.7; IR (KBr): for C9H8NS79Br (M+) 240.9561, Found 240.9568; Elemental
3412 cm−1; Elemental analysis Calcd for C10H11ClFNO4S: C, analysis Calcd for C9H8BrNS: C, 44.64; H, 3.33; N, 5.78.
40.62; H, 3.75; N, 4.74. Found: C, 40.23; H, 3.68; N, 4.40.
Found: C, 44.71; H, 3.30; N, 5.48.
(2-Carboethoxyindol-3-yl)dimethylsulfonium
5-Fluoro-3-methylthioindole16) 7g According to the
Perchlo-
general procedure, from 130.0mg (0.440mmol) of (5-fluoro- rate 4j According to the general procedure, from 573.2mg
indol-3-yl)dimethylsulfonium perchlorate 4g, 78.5mg (98.5%) (3.03mmol) of ethyl indole-2-carboxylate 1j, 964.8mg (91.1%)
of 5-fluoro-3-methylthioindole 7g was obtained as colorless of (2-carboethoxyindol-3-yl)dimethylsulfonium perchlorate
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oil. H-NMR (CDCl3) δ: 8.20 (1H, brs, NH), 7.40 (1H, dd, 4j was obtained as colorless prisms. mp 211–219°C (dec.);
J=9.2, 2.4Hz, C4-H), 7.35 (1H, d, J=2.4Hz, C2-H), 7.30 (1H, 1H-NMR (DMSO-d6) δ: 13.34 (1H, brs, NH), 8.19 (1H, d,
dd, J=9.0, 4.2Hz, C7-H), 6.98 (1H, ddd, J=9.0, 9.0, 2.4Hz, J=8.2Hz, C4 or 7-H), 7.69 (1H, d, J=8.2Hz, C4 or 7-H), 7.50
C6-H), 2.35 (3H, s, SMe); 13C-NMR (CDCl3) δ: 158.4 (d, (1H, t, J=8.2Hz, C5 or 6-H), 7.38 (1H, t, J=8.2Hz, C5 or 6-H),
JC–F=236Hz), 132.7, 129.7, 129.5 (d, JC–F=9.9Hz), 112.2 (d, 4.46 (2H, q, J=7.1Hz, CH2CH3), 3.43 (6H, s, SMe2), 1.41 (3H,
JC–F=9.1Hz), 111.2 (d, JC–F=26.5Hz), 108.3 (d, JC–F=5.0Hz), t, J=7.1Hz, CH2CH3); 13C-NMR (100MHz, DMSO-d6) δ:
104.3 (d, JC–F=24.0Hz), 20.2; IR (KBr): 3462cm−1; HR-MS 159.1, 136.4, 131.7, 126.4, 124.8, 123.3, 120.2, 114.6, 97.4, 62.4,
(EI): Calcd for C9H8FNS (M+) 181.0361, Found 181.0389.
27.8, 14.1; IR (KBr): 3421, 1715cm−1; HR-MS (EI): Calcd for
(5-Bromoindol-3-yl)dimethylsulfonium Perchlorate 4h C13H15NO2S (M−H)+: 249.0818, Found: 249.0823; Elemental
According to the general procedure, from 784.2mg analysis Calcd for C13H16ClNO6S: C, 44.64; H, 4.61; N, 4.00.
(4.00mmol) of 5-bromoindole 1h, 1.218g (85.4%) of Found: C, 44.80; H, 4.54; N, 3.95.
(5-bromoindol-3-yl)dimethylsulfonium perchlorate 4h was ob-
Ethyl 3-Methylthioindole-2-carboxylate33) 7j Accord-
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tained as colorless prisms. mp 178–181°C; H-NMR (acetone- ing to the general procedure, from 536.5mg (1.53mmol) of
d6) δ: 11.74 (1H, brs, NH), 8.49 (1H, d, J=3.4Hz, C2-H), 8.21 (2-carboethoxyindol-3-yl)dimethylsulfonium perchlorate 4j,
(1H, brd, J=1.6Hz,, C4-H), 7.71 (1H, d, J=8.8Hz, C7-H), 7.521 295.5mg (81.9%) of ethyl 3-methylthioindole-2-carboxylate
(1H, dd, J=8.8, 1.6Hz, C6-H), 3.61 (6H, s, SMe2); 13C-NMR 7j was obtained as colorless prisms. mp 116–118°C (hex-
(acetone-d6) δ: 136.8, 135.8, 127.9, 127.2, 121.7, 116.5, 116.2, ane–AcOEt) (lit.33): mp 114–116°C); H-NMR (CDCl3) δ: 8.96
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94.2, 30.0; IR (KBr): 3428cm−1; EI-MS m/z: 241 (M+−CH3), (1H, brs, NH), 7.87 (1H, dd, J=8.2, 1.2Hz, C4 or 7-H), 7.39
226 (BP, M+−2·CH3), 243 (M+−CH3), 228 (BP, M+−2·CH3); (1H, dd, J=8.2, 1.2Hz, C4 or 7-H), 7.34 (1H, ddd, J=8.2, 7.0,
Elemental analysis Calcd for C10H11BrClNO4S: C, 33.68; H, 1.2Hz, C5 or 6-H), 7.20 (1H, ddd, J=8.2, 7.0, 1.2Hz, C5 or 6-H),
3.11; N, 3.93. Found: C, 33.63; H, 3.16; N, 3.71.
4.46 (2H, q, J=7.1Hz, CH2CH3), 2.48 (3H, s, SMe), 1.44 (3H,
5-Bromo-3-methylthioindole16) 7h According to the gen- t, J=7.1Hz, CH2CH3); IR (KBr): 3306, 1665cm−1; EI-MS
eral procedure, from 200.0mg (0.561mmol) of (5-bromoindol- m/z: 235 (M+, 42%), 146 (BP); Elemental analysis Calcd for
3-yl)dimethylsulfonium perchlorate 4h, 134.4mg (84.5%) of C12H13NO2S: C, 61.25; H, 5.57; N, 5.95. Found: C, 61.48; H,