M. Jha et al. / Tetrahedron 67 (2011) 982e989
987
(100), 162 (35), 129 (7). ESI-HRMS (amu): calcd C14H12ClNNaO4
100), 190 (100), 117 (14). ESI-HRMS (amu): calcd C11H12NOS
[MþNa]þ: 316.0353; found [MþNa]þ: 316.0353.
[MþH]þ: 206.0640; found [MþH]þ: 206.0629.
4.3.3. 1,10-(2-Hydroxy-1H-indole-1,3-diyl)dipropan-1-one (5). The
product was isolated using FCC (silica gel, hexanes/ethyl acetate) in
76% yield. Mp: 73e74 ꢀC (hexanes/ethyl acetate). 1H NMR
4.3.9. S-1H-Indol-2-yl ethanethioate (18). The product was isolated
using FCC (silica gel, hexanes/ethyl acetate) in 94% yield. Mp:
101e103 ꢀC (hexanes/ethyl acetate). 1H NMR (300 MHz, CDCl3):
(300 MHz, CDCl3):
2H), 7.24 (m, 2H), 3.18 (q, 2H), 2.82 (q, 2H), 1.34 (m, 6H). 13C NMR
(75 MHz, CDCl3): 180.2, 174.7, 172.3, 135.4, 125.6, 124.7, 122.6,
d
13.69 (s, 1H), 8.36 (d, J¼7.5 Hz, 1H), 7.35 (m,
d
8.66 (br s, 1H, D2O exchangeable), 7.64 (d, J¼8 Hz, 1H), 7.39 (d,
J¼8 Hz, 1H), 7.26 (dd, J¼8 Hz, 1H), 7.16 (dd, J¼7.5 Hz, 1H), 6.73 (s,
1H), 2.46 (s, 3H). 13C NMR (75 MHz, CDCl3):
194.9, 137.8, 127.9,
d
d
119.2, 116.5, 100.6, 32.2, 27.6, 9.6, 8.4. FT-IR nmax (KBr): 2934, 1717,
1661, 1475, 738 cmꢁ1. GCeMS (EI): m/z (% relative abundance) 245
(Mþ, 28), 289 (100), 150 (75), 133 (15). ESI-HRMS (amu): calcd
C14H15NNaO3 [MþNa]þ: 268.0950; found [MþNa]þ: 268.0937.
123.4, 121.3, 120.8, 120.4, 111.1, 109.9, 30.1. FT-IR nmax (KBr): 3343,
1685, 1438, 1110, 743 cmꢁ1. GCeMS (EI): m/z (% relative abundance)
191 (Mþ, 100), 149 (37), 121 (10). ESI-HRMS (amu): calcd
C10H9NNaOS [MþNa]þ: 214.0303; found [MþNa]þ: 214.0290.
4.3.4. 1,10-(2-Hydroxy-1H-indole-1,3-diyl)dibutan-1-one (6). The
product was isolated using FCC (silica gel, hexanes/ethyl acetate) in
82% yield. Mp: 52e54 ꢀC (hexanes/ethyl acetate). 1H NMR (300 MHz,
4.3.10. S-1-Acetyl-1H-indol-2-yl ethanethioate (19). The product was
isolated using FCC (silica gel, hexanes/ethyl acetate) in 78% yield. Mp:
52e54 ꢀC (hexanes/ethyl acetate). 1H NMR (300 MHz, CDCl3):
d 8.21
CDCl3):
d
13.70 (s,1H), 8.35 (d, J¼8.5 Hz,1H), 7.36 (s,1H), 7.24 (m, 2H),
(d, J¼8.5 Hz, 1H), 7.60 (d, J¼7.5 Hz, 1H), 7.41 (dd, J¼7.5 Hz, 1H), 7.30
(dd, J¼7.5 Hz,1H), 7.03 (s,1H), 2.79 (s, 3H), 2.47 (s, 3H). D2O exchange
experiment did not result any change in 1H NMR spectrum. 13C NMR
3.16 (t, J¼7.5 Hz, 2H), 2.78(t, J¼7.5 Hz, 2H),1.85(m, 4H)1.12(m, 6H).13C
NMR (75 MHz, CDCl3): d 179.5, 173.9, 172.3, 135.5, 125.9, 124.7, 122.6,
119.2,116.6,101.1, 40.5,36.0,19.2,17.8,14.0,13.8. FT-IRnmax (KBr):2952,
1713, 1670, 1457, 743 cmꢁ1. GCeMS (EI): m/z (% relative abundance)
273 (Mþ, 15), 203 (100), 160 (48), 133 (22). ESI-HRMS (amu): calcd
C16H19NNaO3 [MþNa]þ: 296.1263; found [MþNa]þ: 296.1261.
(75 MHz, CDCl3): d 193.3, 170.0, 138.3, 128.6, 126.2, 123.6, 122.4, 122.1,
121.0, 116.0, 29.8, 27.1. FT-IR nmax (KBr): 3347, 3011, 1690, 1440,
749 cmꢁ1. GCeMS (EI): m/z (% relative abundance) 234 (Mþ,100),191
(20), 149 (47). ESI-HRMS (amu): calcd C12H11NNaO2S [MþNa]þ:
256.0408; found [MþNa]þ: 256.0410.
4.3.5. 1-(2-Hydroxy-1-methyl-1H-indol-3-yl)ethanone (14)22a. The
product was isolated using FCC (silica gel, hexanes/ethyl acetate) in
81% yield. Mp: 110e111 ꢀC (hexanes/ethyl acetate). 1H NMR
4.3.11. 1,3-Diacetyl-5-fluoro-1H-indol-2-yl acetate (28). Melting
point: 133e135 ꢀC (methanol). 1H NMR (CDCl3, 300 MHz):
d 8.29
(300 MHz, CDCl3):
J¼7.5 Hz,1H), 7.12 (dd, J¼8 Hz,1H), 6.95 (d, J¼8 Hz, 1H), 3.35 (s, 3H),
2.46 (s, 3H). 13C NMR (75 MHz, CDCl3):
172.9, 171.0, 138.9, 125.2,
122.2, 122.1, 119.7, 108.4, 101.7, 25.6, 20.3. FT-IR nmax (KBr): 3058,
2932, 1655, 1466, 748 cmꢁ1. GCeMS (EI): m/z (% relative abun-
dance) 189 (Mþ, 100), 174 (80), 147 (17), 91 (24). ESI-HRMS (amu):
calcd C11H11NNaO2 [MþNa]þ: 212.0687; found [MþNa]þ: 212.0683.
d
13.67 (br s, 1H), 7.37 (d, J¼7.5 Hz, 1H), 7.23 (d,
(dd, J¼9.0, 5.0 Hz, 1H), 7.30 (dd, J¼8.7, 2.7 Hz, 1H), 7.04 (ddd, J¼9.0,
9.0, 2.7 Hz, 1H), 2.73 (s, 6H), 2.45 (s, 3H). 13C NMR (CDCl3, 75 MHz):
d
d
172.1, 168.9, 168.2, 164.5, 161.2 (d, 1JCeF¼242 Hz), 135.0, 124.1 (d,
3JCeF¼9 Hz),118.7 (d, 3JCeF¼9 Hz),116.6 (d, 2JCeF¼24 Hz),116.0,111.2
(d, 2JCeF¼26 Hz), 27.4, 21.8, 19.6. FT-IR nmax (KBr): 3452, 3122, 1738,
1700, 1650, 1474, 1194, 815 cmꢁ1
. ESI-HRMS (amu): calcd
C14H12FNNaO4 [MþNa]þ: 300.0643; found [MþNa]þ: 300.0644.
4.3.6. 1-(5-Chloro-2-hydroxy-1-methyl-1H-indol-3-yl)ethanone
(15)22b. The product was isolated using FCC (silica gel, hexanes/
ethyl acetate) in 78% yield. Mp: 126e128 ꢀC (hexanes/ethyl ace-
4.3.12. 1,3-Diacetyl-5-chloro-1H-indol-2-yl acetate (29). Melting
point: 127e128 ꢀC (methanol). 1H NMR (CDCl3, 300 MHz):
d
8.25 (d,
J¼8.9 Hz,1H), 7.57 (s, 1H), 7.30 (d, J¼8.5 Hz,1H), 2.73 (s, 6H), 2.46 (s,
3H). 13C NMR (CDCl3, 75 MHz):
171.1, 167.6, 167.2, 163.7, 136.4,
130.5, 129.2, 123.4, 117.8, 114.9, 27.3, 21.7, 19.5. FT-IR nmax (KBr):
tate). 1H NMR (300 MHz, CDCl3)
d
: 13.56 (br s, 1H), 7.34 (s, 1H), 7.21
d
(d, J¼8.5 Hz, 1H), 6.88 (d, J¼8.5 Hz, 1H), 3.36 (s, 3H), 2.47 (s, 3H). 13C
NMR (75 MHz, CDCl3):
d
174.3, 170.9, 137.3, 127.6, 124.9, 123.7, 119.8,
3436, 1701, 1163, 1014, 882 cmꢁ1
. ESI-HRMS (amu): calcd
109.1, 101.2, 25.8, 20.4. FT-IR nmax (KBr): 3441, 1653, 1486, 708 cmꢁ1
.
C14H12ClNNaO4 [MþNa]þ: 316.0347; found [MþNa]þ: 316.0345.
GCeMS (EI): m/z (% relative abundance) 225 (33), 223 (Mþ, 100),
210 (30), 208 (85), 117 (33). ESI-HRMS (amu): calcd C11H10ClNNaO2
[MþNa]þ: 246.0298; found [MþNa]þ: 246.0294.
4.3.13. 1,3-Diacetyl-5-bromo-1H-indol-2-yl acetate (30). Melting
point: 121e123 ꢀC (methanol). 1H NMR (CDCl3, 300 MHz):
d
8.20 (d,
J¼8.4 Hz, 1H), 7.73 (s, 1H), 7.45 (d, J¼8.1 Hz, 1H), 2.73 (s, 6H), 2.46 (s,
3H).13C NMR (CDCl3, 75 MHz):
177.2,171.0,167.1,163.7,136.8,132.0,
4.3.7. 1-(1-Benzyl-5-chloro-2-hydroxy-1H-indol-3-yl)ethanone
(16). The product was isolated using FCC (silica gel, hexanes/ethyl
acetate) in 80% yield. Mp: 127e128 ꢀC (hexanes/ethyl acetate). 1H
d
129.0, 126.2, 123.8, 118.2, 115, 27.3, 21.7, 19.5. FT-IR nmax (KBr): 3442,
1699, 1670, 1618, 1456, 1370, 1164 cmꢁ1. ESI-HRMS (amu): calcd
C14H12BrNNaO4 [MþNa]þ: 359.9842; found [MþNa]þ: 359.9846.
NMR (300 MHz, CDCl3):
d 13.52 (br s, 1H), 7.32 (m, 6H), 7.09 (d,
J¼8.5 Hz, 1H), 6.77 (d, J¼8.5 Hz, 1H), 5.04 (s, 2H), 2.48 (s, 3H). 13C
NMR (75 MHz, CDCl3):
d
174.7, 170.9, 136.3, 135.7, 128.9, 127.8, 127.7,
4.3.14. 1,3-Diacetyl-5-iodo-1H-indol-2-yl acetate (31). Melting point:
93e95 ꢀC (methanol). 1H NMR (CDCl3, 300 MHz): 8.09 (d, J¼8.7, 1H),
7.94 (s, 1H), 7.63 (d, J¼8.5, 1H), 2.72 (s, 6H), 2.45 (s, 3H). 13C NMR
127.2, 124.9, 123.8, 119.8, 110.1, 101.1, 43.4, 20.5. FT-IR nmax (KBr):
3031,1660,1434, 750 cmꢁ1. GCeMS (EI): m/z (% relative abundance)
301 (17), 299 (Mþ, 54), 179 (7), 91 (100). ESI-HRMS (amu): calcd
C17H15ClNO2 [MþH]þ: 300.0791; found [MþH]þ: 300.0777.
(CDCl3, 75 MHz): d 178.0, 171.1, 167.2, 163.4, 138.0, 135.1, 132.2, 128.2,
124.1, 118.5, 88.9, 27.3, 21.6, 19.5. FT-IR nmax (KBr): 3444, 1736, 1645,
1457, 1368, 1162 cmꢁ1
. ESI-HRMS (amu): calcd C14H12INNaO4
4.3.8. 1-(2-Mercapto-1-methyl-1H-indol-3-yl)ethanone (17). The
product was isolated using FCC (silica gel, hexanes/ethyl acetate) in
71% yield. Mp: 164e166 ꢀC (hexanes/ethyl acetate). 1H NMR
[MþNa]þ: 407.9703; found [MþNa]þ: 407.9683.
4.3.15. 1,3-Diacetyl-5-methyl-1H-indol-2-yl acetate (32). Melting
(300 MHz, CDCl3):
J¼7.5 Hz, 1H), 7.30 (m, 2H), 7.18 (d, J¼7.5, 1H), 3.73 (s, 3H), 2.66 (s,
3H). 13C NMR (75 MHz, CDCl3):
180.3, 177.6, 141.2, 125.6, 125.1,
d
15.66 (br s, 1H, D2O exchangeable), 7.52 (d,
point: 120e123 ꢀC (methanol). 1H NMR (CDCl3, 300 MHz):
d
8.15 (d,
J¼8.1 Hz, 1H), 7.37 (s, 1H), 7.12 (d, J¼8.2 Hz, 1H), 2.70 (s, 3H), 2.68 (s,
3H), 2.43 (s, 3H), 2.36 (s, 3H). 13C NMR (CDCl3, 75 MHz):
171.1,
d
d
123.2, 120.3, 112.1, 109.3, 29.3, 22.7. FT-IR nmax (KBr): 2935, 1595,
1443, 747 cmꢁ1. GCeMS (EI): m/z (% relative abundance) 205 (Mþ,
168.4, 167.4, 161.7, 136.0, 134.6, 130.3, 123.8, 121.9, 116.4, 116.0, 27.3,
21.8, 21.7, 19.4. FT-IR nmax (KBr): 3452, 2913, 1750, 1742, 1654, 1479,