7562 J . Org. Chem., Vol. 61, No. 21, 1996
Katritzky et al.
123.0, 120.1, 119.0, 117.7, 109.3, 32.7. Anal. Calcd for
C25H19N: C, 90.06; H, 5.74; N, 4.20. Found: C, 89.67; H, 5.54;
N, 4.09.
133.6, 133.5, 129.8, 128.0, 126.4, 125.3, 122.9, 121.4, 120.9,
120.0, 118.8, 109.5, 108.4, 29.0, 21.7. Anal. Calcd for
C20H17N: C, 88.52; H, 6.31; N, 5.16. Found: C, 88.18; H, 6.31;
N, 5.02.
1,9-Dim eth yl-3-p h en ylca r ba zole (6b). Hexane/ethyl ac-
etate (6:1) was used as the eluent to give 6b in 80% yield as
colorless needles, mp 170-171 °C: 1H NMR δ 8.04 (d, J ) 1.4
Hz, 1H), 8.00 (d, J ) 7.6 Hz, 1H), 7.61 (d, J ) 7.4 Hz, 2H),
7.38-7.30 (m, 4H), 7.25-7.20(m, 2H), 7.15-7.10 (m, 1H), 3.89
(s, 3H), 2.72 (s, 3H); 13C NMR δ 142.0, 141.9, 139.2, 132.4,
128.7, 128.2, 127.1, 126.3, 125.7, 124.1, 123.1, 120.5, 120.0,
119.0, 116.5, 108.6, 32.1, 20.3. Anal. Calcd for C20H17N: C,
88.52; H, 6.31; N, 5.16. Found: C, 88.89; H, 6.45; N, 5.07.
1-(2-P h en ylvin yl)-3-p h en yl-9-m et h ylca r b a zole (6c).
Hexane/methylene chloride (6:1) was used as the eluent to give
6c in 66% yield as a white solid, mp 174-175 °C: 1H NMR δ
8.19 (d, J ) 1.8 Hz, 1H), 8.07 (d, J ) 7.8 Hz, 1H), 7.80 (d, J )
15.9 Hz, 1H), 7.73-7.70 (m, 3H), 7.52-7.22 (m, 11H), 6.99 (d,
J ) 15.9 Hz, 1H), 3.95 (s, 3H); 13C NMR δ 142.3, 141.7, 138.1,
137.5, 132.6, 131.4, 128.8, 127.7, 127.2, 126.5, 126.4, 126.2,
126.0, 124.8, 124.6, 123.0, 120.1, 119.3, 118.1, 108.8, 33.0.
Anal. Calcd for C27H21N: C, 90.22; H, 5.89; N, 3.90. Found:
C, 90.27; H, 5.96; N, 3.58.
2-P h en yl-3-(2-m eth ylpr opyl)-9-m eth ylcar bazole (6j) an d
2-(2-Meth ylp r op yl)-3-p h en yl-9-m eth ylca r ba zole (8). Hex-
ane/ethyl acetate (6:1) was used as the eluent to give an
inseparable mixture of 6j and 8 in 67% total yield in a ratio of
2:3 as a colorless oil (signals for minor isomer are quoted in
brackets): 1H NMR δ 7.89 [7.97] (d, J ) 7.7 Hz, 1H), 7.80 [7.83]
(s, 1H), 7.34-7.17 (m, 7H), 7.12-6.98 (m, 2H), 3.65 [3.59] (s,
3H), 2.58 [2.54] (d, J ) 7.3 Hz, 2H), 1.66-1.23 (m, 1H), 0.66
[0.65] (d, J ) 6.6 Hz, 6H); 13C NMR δ 143.2 [143.3], 141.4
[141.5], 140.5 [139.4], 137.5, 134.0, 130.1 [129.7], 127.9, 126.3
[126.6], 125.4 [125.5], 122.9 [122.6], 121.6 [121.2], 120.7
[121.9], 120.0 [120.2], 118.8 [118.7], 109.2 [109.8], 108.3, 43.3
[42.5], 30.0 [30.1], 29.0 [28.9], 22.5 [22.4]. Anal. Calcd for
C23H23N: C, 88.14; H, 7.40; N, 4.47. Found: C, 88.36; H, 7.50;
N, 4.38.
Gen er a l P r oced u r e for th e P r ep a r a tion of Cyclop en t-
[b]in d oles 14a -c. To a solution of 1-methyl-3-(benzotriazol-
1-ylmethyl)indole (1) (0.78 g, 3 mmol) in CH2
Cl2 (60 mL) at 0
1,3-Dip h en yl-2-cya n o-9-m eth ylca r ba zole (6d ). Hexane/
ethyl acetate (7:1) was used as the eluent to give 6d in 45%
yield as a colorless solid, mp 160-161 °C: 1H NMR δ 8.17 (s,
1H), 8.13 (d, J ) 7.9 Hz, 1H), 7.70-7.67 (m, 2H), 7.57-7.42
(m, 9H), 7.36-7.27 (m, 2H), 3.26 (s, 3H); 13C NMR δ 143.5,
139.6, 136.9, 136.3, 130.4, 130.3, 129.4, 128.9, 128.5, 128.4,
127.9, 126.8, 121.7, 120.9, 120.6, 120.1, 118.4, 109.5, 109.3,
32.1. Anal. Calcd for C26H18N2: C, 87.12; H, 5.06; N, 7.82.
Found: C, 87.46; H, 5.22; N, 7.89.
1-Meth yl-2-(eth oxyca r bon yl)-3-p h en yl-9-m eth ylca r ba -
zole (6e). Hexane/ethyl acetate (7:1) was used as the eluent
to give a solid, which was recrystallized from ethyl acetate and
hexane to give 6e in 38% yield as a colorless solid, mp 168-
169 °C: 1H NMR δ 8.03 (d, J ) 7.9 Hz, 1H), 7.92 (s, 1H), 7.51-
7.44 (m, 3H), 7.43-7.30 (m, 4H), 7.25-7.19 (m, 1H), 4.11 (s,
3H), 4.08 (q, J ) 7.2 Hz, 2H), 2.85 (s, 3H), 0.97 (t, J ) 7.2 Hz,
3H); 13C NMR δ 170.5, 142.9, 141.9, 138.9, 132.7, 131.8, 128.9,
128.1, 126.8, 126.4, 124.2, 122.5, 120.3, 119.4, 119.3, 117.9,
108.9, 61.1, 33.0, 16.8, 13.7. Anal. Calcd for C23H21NO2: C,
80.44; H, 6.16; N, 4.08. Found: C, 80.11; H, 6.08; N, 4.00.
1,9-Dim eth yl-2-(eth oxycar bon yl)-3-pr opylcar bazole (6f).
Hexane/ethyl acetate (7:1) was used as the eluent to give 6f
in 36% yield as a colorless solid, mp 111-112 °C: 1H NMR δ
7.98 (d, J ) 7.8 Hz, 1H), 7.72 (s, 1H), 7.42-7.37 (m, 1H), 7.23-
7.13 (m, 2H), 4.45 (q, J ) 7.1 Hz, 2H), 3.88 (s, 3H), 2.70 (t, J
) 7.6 Hz, 2H), 2.67 (s, 3H), 1.76-1.68 (m, 2H), 1.41 (t, J ) 7.1
Hz, 3H), 1.00 (t, J ) 7.6 Hz, 3H); 13C NMR δ 170.9, 142.6,
137.9, 133.3, 129.9, 125.9, 124.1, 122.2, 120.0, 118.9, 118.3,
116.9, 108.6, 60.9, 35.9, 32.6, 24.9, 16.6, 14.2, 14.1. Anal. Calcd
for C20H23NO2: C, 77.64; H, 7.49; N, 4.53. Found: C, 77.69;
H, 7.75; N, 4.45.
2-P h en yl-3,9-d im eth ylca r ba zole (6g). Hexane/methyl-
ene chloride (6:1) was used as the eluent to give 6g in 62%
yield as a colorless solid, mp 135-136 °C: 1H NMR δ 8.00 (d,
J ) 7.7 Hz, 1H), 7.88 (s, 1H), 7.40-7.33 (m, 5H), 7.32-7.25
(m, 2H), 7.16 (s, 1H), 7.12 (d, J ) 8.1 Hz, 1H), 3.69 (s, 3H),
2.34 (s, 3H); 13C NMR δ 143.1, 141.5, 140.2, 139.6, 129.5, 128.0,
126.7, 126.0, 125.5, 122.5, 122.0, 121.3, 120.2, 118.7, 109.6,
108.3, 29.0, 20.7. Anal. Calcd for C20H17N: C, 88.52; H, 6.31;
N, 5.16. Found: C, 88.52; H, 6.54; N, 5.10.
2-P h en yl-3-eth yl-9-m eth ylca r ba zole (6h ). Hexane/me-
thylene chloride (6:1) was used as the eluent to give 6h in 60%
yield as a colorless solid, mp 76-77 °C: 1H NMR δ 8.08 (d, J
) 7.7 Hz, 1H), 7.99 (s, 1H), 7.45-7.29 (m, 7H), 7.23-7.18 (m,
2H), 3.71 (s, 3H), 2.75 (q, J ) 7.5 Hz, 2H), 1.17 (t, J ) 7.5 Hz,
3H); 13C NMR δ 143.1, 141.5, 140.0, 139.4, 132.6, 129.6, 128.0,
126.7, 125.5, 122.6, 122.2, 120.2, 119.7, 118.7, 109.8, 108.3,
29.0, 26.4, 16.3. Anal. Calcd for C21H19N: C, 88.38; H, 6.71;
N, 4.91. Found: C, 88.38; H, 6.61; N, 4.71.
°C under nitrogen was added zinc bromide (1.35 g, 6 mmol).
After 1 h, the appropriate styrene (3.15 mmol) in CH2Cl2 (3
mL) was added. The reaction mixture was stirred at 0 °C for
an additional 3 h. After the zinc bromide was filtered off,
aqueous sodium hydroxide (1 N, 20 mL) was added. The
aqueous layer was extracted with diethyl ether (3 × 30 mL).
The combined organic solution was dried (MgSO4) and solvent
evaporated. The residue was purified by column chromatog-
raphy (silica gel, hexane/methylene chloride ) 1:1) to give the
pure product.
3-(4-Meth ylp h en yl)-4-m eth yl-1,2,3,4-tetr a h yd r ocyclo-
p en t[b]in d ole (14a ): colorless solid; yield 61%; mp 108-109
1
°C; H NMR δ 7.49 (d, J ) 6.8 Hz, 1H), 7.18-7.01 (m, 5H),
7.00-6.94 (m, 2H), 4.31 (dd, J ) 7.4 and 5.1 Hz, 1H), 3.28 (s,
3H), 3.04-2.95 (m, 2H), 2.87-2.82 (m, 1H), 2.39-2.30 (m, 1H),
2.28 (s, 3H); 13C NMR δ 147.2, 141.7, 141.6, 135.9, 129.3, 127.2,
124.0, 120.3, 119.0, 118.8, 118.7, 109.4, 44.3, 40.8, 30.4, 23.9,
21.0. Anal. Calcd for C19H19N: C, 87.31; H, 7.33; N, 5.36.
Found: C, 87.32; H, 7.41; N, 5.30.
3,4-Dim eth yl-3-p h en yl-1,2,3,4-tetr a h yd r ocyclop en t[b]-
1
in d ole (14b): colorless plates; yield 64%; mp 66-67 °C; H
NMR δ 7.51 (d, J ) 6.9 Hz, 1H), 7.29-7.04 (m, 8H), 3.30 (s,
3H), 2.88 (t, J ) 6.9 Hz, 2H), 2.73-2.55 (m, 2H), 1.76 (s, 3H);
13C NMR δ 150.2, 148.0, 141.7, 128.4, 126.1, 124.0, 120.4,
119.0, 118.9, 117.7, 109.3, 50.2, 47.3, 30.1, 25.2, 22.9. Anal.
Calcd for C19H19N: C, 87.31; H, 7.33; N, 5.36. Found: C, 86.94;
H, 7.51; N, 5.41.
3,3-Dip h en yl-4-m eth yl-1,2,3,4-tetr a h yd r ocyclop en t[b]-
1
in d ole (14c): colorless solid; yield 72%; mp 157-158 °C; H
NMR δ 7.52 (d, J ) 7.0 Hz, 1H), 7.30-7.08 (m, 13H), 3.24 (t,
J ) 6.4 Hz, 2H), 3.21 (s, 3H), 2.93 (t, J ) 6.4 Hz, 2H); 13C
NMR δ 148.7, 146.2, 141.8, 128.4, 128.1, 126.3, 124.0, 120.6,
119.2, 119.1, 118.6, 109.5, 57.8, 52.4, 30.6, 23.5. Anal. Calcd
for C24H21N: C, 89.13; H, 6.54; N, 4.33. Found: C, 88.80; H,
6.57; N, 4.30.
Gen er a l P r oced u r e for th e P r ep a r a tion of 1-Su bsti-
tu ted Cyclop en t[b]in d oles 15a -d a n d 16a -d . To a solu-
tion of 1-methyl-3-(benzotriazol-1-ylmethyl)indole (1) (0.79 g,
3 mmol) in THF (75 mL) at -78 °C under argon was added
n-BuLi (1.3 mL, 2.5 M in hexane, 3.3 mmol). After 1 h, the
appropriate electrophile (methyl iodide for 15a , 16a , 15b, and
16b; cyclohexanone for 15c and 16d ; 3-pentanone for 15d and
16d ) in THF (10 mL) was added. The reaction mixture was
stirred at -78 °C for additional 3 h and then allowed to warm
to room temperature overnight. Water (50 mL) was added,
and the aqueous layer was extracted with diethyl ether (2 ×
30 mL). The combined organic solution was dried (MgSO4)
and solvent evaporated to give the corresponding crude
compound 9, which was dissolved in CH2Cl2 (60 mL). To this
solution at 0 °C under nitrogen was added zinc bromide (1.35
g, 6 mmol). After 1 h, the appropriate styrene (3.15 mmol) in
CH2Cl2 (3 mL) was added. The reaction mixture was stirred
at 0 °C for additional 3 h and at room temperature for 2 days.
After the zinc bromide was filtered off, aqueous sodium
2,9-Dim eth yl-3-p h en ylca r ba zole (6i). Hexane/methylene
chloride (6:1) was used as the eluent to give 6i in 31% yield
as a colorless solid, mp 115-115.5 °C: 1H NMR δ 8.02 (d, J )
7.7 Hz, 1H), 7.94 (s, 1H), 7.46-7.33 (m, 7H), 7.24-7.17 (m,
2H), 3.79 (s, 3H), 2.46 (s, 3H); 13C NMR δ 142.7, 141.3, 140.6,