+
d, J=8.5 Hz), 7.48 (1H, dd, J=8.5, 2 Hz), 7.84 (1H, s), 8.44 (1H, d, J=2 Hz). MS m/z: 301 (M ).
Anal. Calcd for C H NO I: C, 39.88; H, 2.67; N, 4.65. Found: C, 39.89; H, 2.59; N, 4.70. 8: mp
10 8
238.0—238.5°C (colorless prisms, recrystallized from MeOH). IR (KBr): 3200, 1670, 1513, 1198,
-1 1
2
1050, 802 cm . H-NMR (CDCl –CD OD, 9:1) δ: 3.91 (3H, s), 7.48 (1H, dd, J=8, 2 Hz), 7.76 (1H,
3
3
+
dd, J=2, 0.5 Hz), 7.84 (1H, s), 7.88 (1H, dd, J=8, 0.5 Hz). MS m/z: 301 (M ). Anal. Calcd for
C H NO I: C, 39.88; H, 2.67; N, 4.65. Found: C, 39.92; H, 2.57; N, 4.63. 9: mp 154.5—155.0°C
10 8
2
-1
(colorless prisms, recrystallized from MeOH). IR (KBr): 3210, 1675, 1444, 1300, 1190, 780, 720 cm .
1
H-NMR (CDCl –CD OD, 9:1) δ: 3.90 (3H, s), 6.98 (1H, dd, J=8, 7.4 Hz), 7.60 (1H, dd, J=7.4, 1
3
3
+
Hz), 7.96 (total 1H, s and d, J=3 Hz), 8.11 (1H, dd, J=8, 1 Hz). MS m/z: 301 (M ). Anal. Calcd for
C H NO I: C, 39.88; H, 2.67; N, 4.65. Found: C, 39.69; H, 2.51; N, 4.70.
10 8
2
Methyl 2-Methylthioindole-3-carboxylate (10) from 1a — Excess 15% aqueous sodium thio-
methoxide (9.0 mL) was added to a solution of 1a (62 mg, 0.30 mmol) in DMF (3.0 mL) and the mixture
was stirred for 6 h at 60°C. After addition of H O, the whole was made acidic by adding aqueous 1N HCl
2
with ice-cooling and extracted with AcOEt. The extract was washed with brine, dried over Na SO , and
2
4
evaporated under reduced pressure to leave an oil, which was column-chromatographed on SiO with
2
CHCl –MeOH (99:1, v/v) to give 10 (47 mg, 70%) and 5 (17 mg, 29%) in the order of elution. 10: mp
3
105—107°C (colorless fine needles, recrystallized from CHCl –hexane). IR (KBr): 3300, 1660 (br),
3
-1 1
1450, 1200, 1068, 758 cm . H-NMR (CDCl ) δ: 2.63 (3H, s), 3.96 (3H, s), 7.18 (1H, t, J=7.8 Hz),
3
7.22 (1H, t, J=7.8 Hz), 7.32 (1H, d, J=7.8 Hz), 8.03 (1H, d, J=7.8 Hz), 8.45 (1H, br s). MS m/z: 221
+
(M ). Anal. Calcd for C H NO S・1/2H O : C, 57.39; H, 5.21; N, 6.08. Found: C, 57.65; H, 5.02;
11 11
2
2
N, 5.96.
Methyl 2-(Indol-1-yl)indole-3-carboxylate (14) from 1a — A solution of indole (19 mg, 0.16
mmol) in anhydrous DMF (2.0 mL) was added to 60% NaH (4.8 mg, 0.12 mmol) with ice-cooling and
the mixture was stirred for 15 min at rt. To the resultant solution, a solution of 1a (17 mg, 0.08 mmol) in
anhydrous DMF (1.0 mL) was added and the mixture was stirred for 16 h at rt. After addition of H O, the
2
whole was extracted with AcOEt. The extract was washed with brine, dried over Na SO , and evaporated
2
4
under reduced pressure to leave an oil, which was column-chromatographed on SiO with CHCl –hexane
2
3
(1:1, v/v) to give 14 (18 mg, 77%). 14: mp 159—160°C (colorless prisms, recrystallized from CHCl –
3
-1 1
hexane). IR (KBr): 3210, 1658, 1560, 1465, 1442, 1204, 1141, 1090 cm . H- NMR (CDCl ) δ: 3.76
3
(3H, s), 6.72 (1H, dd, J=3.4, 0.7 Hz), 7.20 (1H, dt, J=1.7, 7.1 Hz), 7.24 (1H, dt, J=1.7, 7.1 Hz),
7.33—7.36 (2H, m), 7.37—7.40 (2H, m), 7.43 (1H, d, J=3.4 Hz), 7.68 (1H, dd, J=7.1, 1.7 Hz), 8.24
+
—8.26 (1H, m), 8.71 (1H, br s, disappeared on addition of D O). MS m/z: 290 (M ). Anal. Calcd for
2
C H N O ・1/3H O: C, 72.97; H, 4.95; N,9.46. Found: C, 72.74; H, 4.84; N, 9.41.
18 14 2 2
2
Methyl 2-(Imidazol-1-yl)indole-3-carboxylate (16) from 1a — A solution of imidazole (80
mg, 1.17 mmol) in anhydrous DMF (2.0 mL) was added to 60% NaH (21 mg, 0.88 mmol) with ice-
cooling and the mixture was stirred for 15 min at rt. To the resultant solution, a solution of 1a (60 mg,
0.29 mmol) in anhydrous DMF (3.0 mL) was added and the mixture was stirred for 25 h at 60°C. After
addition of H O, the whole was extracted with AcOEt. The extract was washed with brine, dried over
2
Na SO , and evaporated under reduced pressure to leave a solid, which was recrystallized from MeOH to
2
4