900
Russ.Chem.Bull., Int.Ed., Vol. 53, No. 4, April, 2004
Taidakov et al.
1H NMR (CDCl3), δ: 7.68 (d, 1 H, J = 7.4 Hz); 7.41, 7.34, 7.16
(all m, 1 H each); 3.90 (s, 3 H); 3.05, 3.12, 2.97 (all m, 2 H each).
4,5,8ꢀTrimethylꢀ3ꢀphenylꢀ1,2,3,4ꢀtetrahydrocyclopenꢀ
ta[b]indolꢀ3ꢀol (1a). A suspension of ketone 4a (4.3 g, 20 mmol)
in 20 mL of ether was treated with 1.2 M phenyllithium
(25.2 mmol, 21 mL) in ether. The target alcohol was isolated as
a viscous oil in a conventional way. The yield of product 1a was
3.6 g (61%). An analytical sample was purified by chromatograꢀ
phy in benzene and recrystallized from ether—pentane, m.p.
117—118 °C. Found (%): C, 82.46; H, 7.22; N, 4.83. C10H21NO.
Calculated (%): C, 82.44; H, 7.26; N, 4.81. 1H NMR (C6D6), δ:
7.75 (m, 1 H); 7.20 (m, 5 H); 6.90 (dd, 1 H, J = 7.3 Hz); 3.30 (s,
3 H); 2.90 (m, 2 H); 2.75 (m, 1 H); 2.62 (s, 3 H); 2.52 (m, 1 H);
2.35 (s, 3 H); 1.80 (br.s, 1 H).
3,4ꢀDimethylꢀ1,2,3,4ꢀtetrahydrocyclopenta[b]indolꢀ3ꢀol
(1b). A solution of MeLi in ether was prepared as follows.
A solution of MeI (2.5 mL, 40 mmol) in 15 mL of ether was
added dropwise under argon to a stirred suspension of finely
divided lithium (0.56 g, 80 mmol) in 30 mL of ether. The addiꢀ
tion rate was such as to provide uniform boiling of the reaction
mixture. After the reaction was completed, the mixture was
refluxed for an additional 2 h. Then the solution was cooled with
ice, ketone 4b (5.6 g, 30 mmol) was carefully added, and the
resulting suspension was refluxed for 3 h. The mixture was cooled
to 0 °C and 10% NH4Cl (30 mL) was added dropwise. The
organic phase was separated, washed with water, dried with
MgSO4, and concentrated in vacuo to 1/4 of the initial volume.
The solid product was filtered off and dried in vacuo to give
a fine crystalline yellowish substance (4.8 g, 78%), m.p.
124—126 °C. Found (%): C, 77.60; H, 7.53; N, 6.93. C13H15NO.
Calculated (%): C, 77.58; H, 7.51; N, 6.96. 1H NMR (C6D6), δ:
7.65 (m, 1 H); 7.30 (m, 2 H); 7.15 (m, 1 H); 3.30 (s, 3 H); 2.80,
2.65, 2.45, 2.30 (all m, 1 H each); 1.95 (br.s, 1 H); 1.50 (s, 3 H).
4ꢀMethylꢀ3ꢀphenylꢀ1,2,3,4ꢀtetrahydrocyclopenta[b]indolꢀ3ꢀ
ol (1c) was obtained by analogy with compound 1b. Ketone 4b
(5.6 g, 30 mmol) was treated with a solution of phenyllithium
prepared from lithium (0.56 g, 80 mmol) and bromobenzene
(4.2 mL, 40 mmol) in 45 mL of ether. The yield of compound 1c
was 6.8 g (86%), m.p. 117—119 °C. Found (%): C, 82.12;
H, 6.55; N, 5.30. C18H17NO. Calculated (%): C, 82.10; H, 6.51;
N, 5.32. 1H NMR (C6D6), δ: 7.75 (m, 1 H); 7.45, 7.33, 7.20
(all m, 2 H each); 7.15, 7.10 (both m, 1 H each); 3.05 (s, 3 H);
2.85 (m, 3 H); 2.60 (m, 1 H); 1.80 (br.s, 1 H).
44.7 (>CH—); 50.3, 32.3 (—CH2); 38.5, 34.1, 34.05, 19.8, 19.4,
19.05 (—CH3).
2ꢀ(3,4ꢀDimethylꢀ1,2,3,4ꢀtetrahydrocyclopenta[b]indolꢀ1ꢀ
yl)ꢀ3,4ꢀdimethylꢀ1,4ꢀdihydrocyclopenta[b]indole (3b). A solution
of alcohol 1b (4 g, 20 mmol) in 100 mL of benzene containing
trace amounts of TsOH was refluxed in a flask fitted with a
Dean—Stark trap until the starting alcohol disappeared (TLC,
benzene—ethyl acetate (4 : 1)). After the reaction was comꢀ
pleted, the mixture was cooled, washed with a solution of
KHCO3, and dried with MgSO4. The solution in benzene was
filtered through a short column filled with silica gel, concenꢀ
trated to half the initial volume, and mixed with hexane (50 mL).
The precipitate that formed was filtered off and dried in vacuo to
give a light yellow crystalline substance (2.2 g, 65%), m.p.
215—216 °C. Found (%): C, 85.19; H, 7.14; N, 7.62. C26H26N2.
Calculated (%): C, 85.21; H, 7.15; N, 7.64. 1H NMR (C6D6), δ:
7.65 (m, 2 H); 7.35—7.15 (set of m, 6 H); 4.56 (m, 1 H); 3.34
(m, 2 H); 3.30 (s, 3 H); 3.25 (m, 1 H); 3.16 (s, 3 H); 2.65 (m,
1 H); 2.40 (m, 1 H); 2.17 (s, 3 H); 1.21 (d, 3 H). 13C NMR
(C6D6), δ: 149.8, 149.7, 149.4, 149.1, 149.0, 142.3,142.1, 141.4,
129.3, 128.5 (>C<); 120.7, 119.9, 119.8, 119.7, 119.5, 118.9,
118.2, 116.9 (=CH—); 109.6, 36.0 (>CH—); 45.7, 31.3 (—CH2);
32.7, 29.8, 20.3, 11.6 (—CH3).
4ꢀMethylꢀ2ꢀ(4ꢀmethylꢀ3ꢀphenylꢀ1,2,3,4ꢀtetrahydrocycloꢀ
penta[b]indolꢀ1ꢀyl)ꢀ3ꢀphenylꢀ1,4ꢀdihydrocyclopenta[b]indole
(3c). A solution of alcohol 1c (0.8 g, 3 mmol) in 15 mL of
benzene containing trace amounts of TsOH was refluxed in a
flask fitted with a Dean—Stark trap until the starting alcohol
disappeared (TLC, benzene—ethyl acetate (4 : 1)). After the
reaction was completed, the mixture was cooled, washed with a
solution of KHCO3, and dried with MgSO4. The residue was
chromatographed on silica gel in benzene and recrystallized
from ether. The yield of compound 3c was 0.25 g (34%), m.p.
207—209 °C. Found (%): C, 88.15; H, 6.18; N, 5.69. C36H30N2.
Calculated (%): C, 88.13; H, 6.16; N, 5.71. 1H NMR (CDCl3),
δ: 7.75 (m, 2 H); 7.40—7.10 (set of m, 14 H); 6.90 (m, 2 H);
4.80, 4.35 (both m, 1 H each); 3.41 (s, 2 H); 3.14 (s, 3 H); 3.05
(s, 1 H); 2.96 (s, 3 H); 2.70 (s, 1 H). 13C NMR (C6D6), δ: 152.0,
151.8, 148.7, 146.8, 144.7, 142.5, 141.6, 135.9, 133.0, 126.7,
124.9, 124.4 (>C<); 129.8, 129.7, 129.0, 128.7, 127.5, 127.4,
126.7,125.7, 125.2, 122.0, 121.2, 120.0, 119.7, 119.1, 118.7,
117.2, 110.0, 109.9 (=CH—); 120.0, 44.7 (>CH—); 50.5, 31.4
(—CH2); 30.4, 30.0(—CH3).
4,5,8ꢀTrimethylꢀ3ꢀphenylꢀ2ꢀ(4,5,8ꢀtrimethylꢀ3ꢀphenylꢀ
1,2,3,4ꢀtetrahydrocyclopenta[b]indolꢀ1ꢀyl)ꢀ1,4ꢀdihydrocycloꢀ
penta[b]indole (3a). Alcohol 1a (3.56 g, 12.2 mmol) was dehyꢀ
drated in 150 mL of benzene containing trace amounts of TsOH.
After routine workup, the product was purified by chromatoꢀ
graphy in benzene. The solution in benzene was concentrated
in vacuo to 50 mL and then hexane (30 mL) was added. The
precipitate that formed was filtered off and dried in vacuo to give
a fine crystalline light yellow powder (1.56 g, 47%), m.p.
218—219 °C (decomp.). Found (%): C, 87.84; H, 7.05; N, 5.11.
C40H38N2. Calculated (%): C, 87.87; H, 7.01; N, 5.12. 1H NMR
(CDCl3), δ: 7.45, 7.30 (both m, 5 H each); 7.15, 6.70, 4.70
(all m, 2 H each); 3.72, 3.66 (both s, 3 H each); 3.46, 3.32
(both d, 1 H each, J = 23 Hz); 3.10 (m, 1 H); 2.80 (m, 1 H); 2.72
(s, 6 H); 2.50 (s, 3 H); 2.31 (s, 3 H). 13C NMR (CDCl3), δ:
153.7, 148.5, 147.0, 144.6, 140.2, 138.9, 135.5, 131.7, 129.3,
127.8, 127.1, 124.9, 124.4, 121.1, 119.1, 118.8, 116.4 (>C<);
128.6, 127.7, 127.3, 126.4, 123.7, 122.9, 119.7 (=CH—); 119.6,
References
1. J. F. van Baar, A. D. Horton, K. P. de Kloe, I. V. Taidakov,
I. E. Nifant´ev, E. Kragtwijk, S. G. Mkoyan, and P. A.
Schut, Organometallics, 2003, 22, 2711.
2. J. Bergman and J. E. Backvall, Tetrahedron, 1975, 31, 2063.
3. J. Bergman, P.ꢀO. Norrby, U. Tilstam, and L. Venemalm,
Tetrahedron, 1989, 45, 5549.
4. A. G. M. Barret, D. Dauzonne, I. O´Neil, and A. Renaud,
J. Org. Chem., 1984, 49, 4409.
5. J. Jennings, J. Chem. Soc., 1957, 497.
6. H. Cho and S. Matsuki, Heterocycles, 1996, 43, 127.
7. S. Harts and J. P. Pots, J. Org. Chem., 1962, 27, 2940.
8. M. L. Baron, L. L. Martin, D. Rae, P. M. Simmonds, and
M. L. Woolcock, Aust. J. Chem., 1990, 43, 741.
9. N. Ishizumi, Chem. Pharm. Bull., 1967, 15, 863.
Received December 29, 2003