59
6.1.5.2.
2-(2-Hydroxy-5,6,7,8,9,10-hexahydrocyclo-
CH), 127.55 (arom. CH), 112.37 (arom. C), 110.91
(arom. CH), 108.87 (arom. CH), 102.00 (arom. CH),
70.97 (OCH2), 61.40 (COOCH2), 44.76 (NCH2), 30.17
(CH2), 28.66 (CH2), 25.83 (CH2), 25.78 (CH2), 23.05
(CH2), 22.87 (CH2), 14.06 (COOCH2CH3). Anal. calc.
for C25H29O3N: C, 76.69; H, 7.46; N, 3.57. Found: C,
76.76; H, 7.51; N, 3.61.
hept[b]indol-5-yl)ethyl acetate 10b
Liquid. IR (NaCl): 3403 cm–1 (OH), 2921–2850 cm–1
(CH), 1738 cm–1 (C=O). 1H-NMR (CDCl3): δ 7.00–6.50
(3 H, m, arom. H), 6.07 (1 H, s, OH), 4.68 (2 H, s,
NCH2), 4.20–4.00 (2 H, q, COOCH2), 2.75–2.60 (4 H, m,
2CH2), 1.90–1.65 (6 H, m, 3CH2), 1.30–1.10 (3 H, t,
COOCH2CH3). 13C-NMR (CDCl3): δ 169.47 (C=O),
149.42 (arom. COH), 139.51 (arom. C), 130.89 (arom.
C), 128.68 (arom. C), 113.75 (arom. C), 110.10 (arom.
CH), 108.67 (arom. CH), 102.73 (arom. CH), 61.50
(COOCH2), 44.64 (NCH2), 31.38 (CH2), 28.08 (CH2),
26.74 (CH2), 26.28 (CH2), 24.20 (CH2), 13.94
(COOCH2CH3). Anal. calc. for C17H21O3N: C, 71.05; H,
7.36; N, 4.87. Found: C, 71.00; H, 7.65; N, 4.78.
6.1.6.2.
2-{2-[Quinol-2-yl)methyloxy]-5,6,7,8,9,10-
hexahydrocyclohept[b]indol-5-yl)}ethyl acetate 11b
M.p.: 64–67 °C. IR (NaCl): 2921–2849 cm–1 (CH),
1
1753 cm–1 (C=O). H-NMR (CDCl3): δ 8.10–7.10 (6 H,
m, arom. H), 7.00–6.60 (3 H, m, arom. H), 5.25 (2 H, s,
NCH2), 4.50 (2 H, s, OCH2), 4.20–3.80 (2 H, q,
COOCH2), 2.90–2.40 (4 H, m, 2CH2), 2.00–1.50 (6 H, m,
3CH2), 1.40–1.00 (3 H, t, COOCH2CH3). 13C-NMR
(CDCl3): δ 168.59 (C=O), 158.50 (arom. C), 152.59
(arom. C–O), 147.14 (arom. C), 139.36 (arom. C), 136.40
(arom. CH), 131.06 (arom. C), 129.19 (arom. CH),
128.44 (arom. CH), 128.31 (arom. C), 127.33 (arom.
CH), 127.15 (arom. C), 125.86 (arom. CH), 118.88
(arom. CH), 113.85 (arom. C), 110.38 (arom. CH),
108.73 (arom. CH), 101.79 (arom. CH), 71.69 (OCH2),
61.01 (COOCH2), 44.35 (NCH2), 31.10 (CH2), 27.85
(CH2), 26.51 (CH2), 26.06 (CH2), 24.00 (CH2), 13.76
(COOCH2CH3). Anal. calc. for C27H28O3N2: C, 75.67;
H, 6.58; N, 6.53. Found: C, 75.49; H, 6.37; N, 6.42.
6.1.5.3.
2-(2-Hydroxy-6,7,8,9,10,11-hexahydro-5H-
cyclooct[b]indol-5-yl) ethyl acetate 10c
M.p.: 99–101 °C. IR (NaCl): 3406 cm–1 (OH),
2980–2927–2850 cm–1 (CH), 1753 cm–1 (C=O). 1H-
NMR (CDCl3): δ 7.00–6.60 (3 H, m, arom. H), 6.31 (1 H,
s, OH), 4.67 (2 H, s, NCH2), 4.20–4.00 (2 H, q,
COOCH2), 2.80–2.60 (4 H, m, 2CH2), 1.70–1.23 (8 H, m,
4CH2), 1.21–1.00 (3 H, t, COOCH2CH3). 13C-NMR
(CDCl3): δ 169.53 (C=O), 149.31 (arom. COH), 137.14
(arom. C), 131.55 (arom. C), 128.17 (arom. C), 111.75
(arom. C), 110.05 (arom. CH), 108.55 (arom. CH),
102.65 (arom. CH), 61.43 (COOCH2), 44.52 (NCH2),
29.95 (2CH2), 28.43 (CH2), 25.58 (CH2), 22.77 (CH2),
22.61 (CH2), 13.76 (COOCH2CH3). Anal. calc. for
C18H23O3N: C, 71.73; H, 7.69; N, 4.64. Found: C, 71.49;
H, 7.67; N, 4.77.
6.1.6.3. 2-{2-[Quinol-2-yl)methyloxy]-6,7,8,9,10,11-
hexahydro-5H-cyclooct[b]indol-5-yl)}ethyl acetate 11c
M.p.: 59–61 °C. IR (NaCl): 2925–2852 cm–1 (CH),
1
1753 cm–1 (C=O). H-NMR (CDCl3): δ 8.20–8.00 (2 H,
m, arom. H), 7.80–7.60 (3 H, m, arom. H), 7.55–7.40 (1
H, m, arom. H), 7.20–6.85 (3 H, m, arom. H), 5.42 (2 H,
s, NCH2), 4.68 (2 H, s, OCH2), 4.20–4.00 (2 H, q,
COOCH2), 2.90–2.70 (4 H, m, 2CH2), 1.75–1.60 (4 H, m,
2CH2), 1.45–1.30 (4 H, m, 2CH2), 1.30–1.10 (3 H, t,
COOCH2CH3). 13C-NMR (CDCl3): δ 168.82 (C=O),
158.65 (arom. C), 152.67 (arom. C–O), 147.31 (arom. C),
137.29 (arom. C), 136.58 (arom. CH), 131.89 (arom. C),
129.37 (arom. CH), 128.63 (arom. CH), 127.49 (arom.
CH), 126.03 (arom. CH), 127.99 (arom. C), 127.32
(arom. C), 119.05 (arom. CH), 112.21 (arom. C), 110.42
(arom. CH), 108.83 (arom. CH), 101.85 (arom. CH),
71.79 (OCH2), 61.22 (COOCH2), 44.55 (NCH2), 29.97
(2CH2), 28.48 (CH2), 25.63 (CH2), 22.88 (CH2), 22.69
(CH2), 13.91 (COOCH2CH3). Anal. calc. for
C28H30O3N2: C, 75.98; H, 6.83; N, 6.33. Found: C,
75.70; H, 6.79; N, 6.05.
6.1.6. Procedure for the synthesis of compounds 11
To a stirred solution of 1 eq. of indole 10 in DMF
(10 mL/1 mmol) was added 1.8 eq. (R = Ph) or 4 eq. (R
= 2-quinolyl) of K2CO3, 1.2 eq. of benzyl chloride or 1.5
eq. of 2-methylquinoline hydrochloride, and 0.2 eq. (R =
Ph) or 0.4 eq. (R = 2-quinolyl) of PhCH2N+Et3Cl– at RT.
The mixture was warmed to 35–40 °C for 5 h (R = Ph) or
20 h (R = 2-quinolyl). Compounds 11 were isolated by
flash chromatography using EtOAc/PE 15% as eluent.
6.1.6.1. 2-(2-Benzyloxy-6,7,8,9,10,11-hexahydro-5H-
cyclooct[b]indol-5-yl)ethyl acetate 11a
Liquid. IR (NaCl): 3032–2927–2850 cm–1 (CH),
1
1753 cm–1 (C=O). H-NMR (CDCl3): δ 7.60–6.60 (8 H,
m, arom. H), 4.95 (2 H, s, NCH2), 4.55 (2 H, s, OCH2),
4.40–3.85 (2 H, q, COOCH2), 3.10–2.60 (4 H, m, 2CH2),
2.10–1.00 (11 H, m + t, 4CH2 + COOCH2CH3). 13C-
NMR (CDCl3): δ 169.04 (C=O), 153.27 (arom. C–O),
137.82 (arom. C), 137.31 (arom. C), 131.99 (arom. C),
128.39 (2arom. CH), 128.09 (arom. C), 127.62 (2arom.
6.1.7. Procedure for the synthesis of indoles 12
A stirred solution of 1 eq. of indole 11 in KOH/EtOH
(10%) was refluxed until all the ester had disappeared