K. Kobayashi et al.
Bull. Chem. Soc. Jpn., 78, No. 12 (2005) 2173
(1H, d, J ¼ 8:2 Hz), 8.31 (1H, d, J ¼ 7:9 Hz), 8.72 (1H, d, J ¼ 7:9
Hz), and 9.04 (1H, dd, J ¼ 8:2 and 1.0 Hz); 13C NMR (125 MHz,
DMSO-d6) ꢀ 9.54, 28.66, 34.32, 69.50, 110.03, 112.01, 115.82,
120.13, 121.36, 122.74, 123.81, 124.39, 127.56, 127.80, 131.57,
135.76, 141.79, 142.90, and 157.05; MS (EI) m=z (%) 290 (Mþ,
19) and 261 (100). Found: C, 78.89; H, 6.14; N, 9.34%. Calcd
for C19H18N2O: C, 78.59; H, 6.25; N, 9.65%.
6-(1-Hydroxy-2-methylpropyl)-11-methyl-11H-indolo[3,2-c]-
quinoline (4b): A pale-yellow solid; mp 208–209 ꢁC (hexane–
AcOEt); IR 3367 cmꢂ1; 1H NMR ꢀ 0.61 (3H, d, J ¼ 6:6 Hz), 1.41
(3H, d, J ¼ 6:6 Hz), 2.4–2.55 (1H, m), 4.42 (3H, s), 5.54 (1H,
brs), 5.62 (1H, br), 7.44 (1H, ddd, J ¼ 8:2, 6.9, and 1.3 Hz), 7.5–
7.65 (3H, m), 7.73 (1H, ddd, J ¼ 8:2, 6.9, and 1.3 Hz), 8.03 (1H,
d, J ¼ 7:9 Hz), 8.27 (1H, dd, J ¼ 8:2 and 1.3 Hz), and 8.64 (1H,
dd, J ¼ 8:6 and 1.0 Hz); 13C NMR ꢀ 14.17, 20.99, 32.44, 33.60,
74.82, 109.49, 111.31, 117.68, 120.97, 121.32, 121.77, 122.14,
125.18, 125.21, 127.85, 129.95, 140.51, 140.68, 144.53, and
157.42; MS (EI) m=z (%) 304 (Mþ, 12) and 261 (100). Found:
C, 78.75; H, 6.70; N, 9.11%. Calcd for C20H20N2O: C, 78.92; H,
6.62; N, 9.20%.
8.40 (1H, d, J ¼ 8:2 Hz), and 8.68 (1H, dd, J ¼ 8:2 and 1.0 Hz);
13C NMR ꢀ 8.30, 26.08, 32.27, 34.00, 73.89, 109.58, 110.85,
117.45, 120.48, 121.04, 121.86, 124.31, 125.15, 125.43, 128.07,
129.74, 140.79, 141.97, 143.44, and 159.97; MS (EI) m=z (%)
304 (Mþ, 11) and 275 (100). Found: C, 78.93; H, 6.64; N,
9.18%. Calcd for C20H20N2O: C, 78.92; H, 6.62; N, 9.20%.
6-(1-Ethyl-1-hydroxypropyl)-11-methyl-11H-indolo[3,2-c]-
quinoline (4g): A pale-yellow solid; mp 242–243 ꢁC (hexane–
CH2Cl2); IR 3423 cmꢂ1; 1H NMR ꢀ 0.73 (6H, t, J ¼ 7:3 Hz), 2.2–
2.4 (2H, m), 2.55–2.7 (2H, m), 4.46 (3H, s), 7.25 (1H, br), 7.44
(1H, ddd, J ¼ 8:2, 6.9, and 1.3 Hz), 7.55–7.7 (3H, m), 7.75 (1H,
ddd, J ¼ 8:2, 6.9, and 1.3 Hz), 8.28 (1H, dd, J ¼ 8:2 and 1.0 Hz),
8.44 (1H, d, J ¼ 7:9 Hz), and 8.69 (1H, dd, J ¼ 8:2 and 1.0 Hz);
13C NMR ꢀ 8.15, 30.88, 34.10, 76.67, 109.60, 111.19, 117.41,
120.58, 121.00, 121.91, 124.38, 125.15, 125.41, 128.05, 129.80,
140.82, 141.93, 143.36, and 159.10; MS (EI) m=z (%) 318 (Mþ,
7.5) and 289 (100). Found: C, 79.33; H, 6.86; N, 8.75%. Calcd
for C21H22N2O: C, 79.21; H, 6.96; N, 8.80%.
6-(1-Ethoxyethyl)-11-methyl-11H-indolo[3,2-c]quinoline (5a):
Colorless needles; mp 143–144 ꢁC (hexane–EtOAc); IR 1612
1
6-(1-Cyclohexyl-1-hydroxymethyl)-11-methyl-11H-indolo-
[3,2-c]quinoline (4c): A pale-yellow solid; mp 263–265 ꢁC (hex-
cmꢂ1; H NMR ꢀ 1.19 (3H, t, J ¼ 6:9 Hz), 1.81 (3H, d, J ¼ 6:9
Hz), 3.4–3.65 (2H, m), 4.44 (3H, s), 5.30 (1H, q, J ¼ 6:9 Hz), 7.41
(1H, ddd, J ¼ 8:2, 6.9, and 1.3 Hz), 7.5–7.65 (3H, m), 7.73 (1H,
ddd, J ¼ 8:2, 6.9, and 1.3 Hz), 8.30 (1H, dd, J ¼ 8:2 and 1.3 Hz),
8.66 (1H, d, J ¼ 8:2 Hz), and 8.81 (1H, d, J ¼ 7:9 Hz); 13C NMR
(DMSO-d6) ꢀ 15.64, 19.97, 33.75, 64.52, 80.74, 108.95, 112.40,
117.81, 120.87, 121.09, 121.74, 125.15, 125.18, 125.21, 127.70,
130.33, 140.64, 141.23, 145.87, and 159.08; MS (EI) m=z (%)
304 (Mþ, 0.71) and 260 (100). Found: C, 78.91; H, 6.64; N,
9.20%. Calcd for C20H20N2O: C, 78.92; H, 6.62; N, 9.20%.
6-(1-Ethoxy-1-methylethyl)-11-methyl-11H-indolo[3,2-c]-
quinoline (5b): Colorless needles; mp 162 ꢁC (hexane–Et2O); IR
1613 cmꢂ1; 1H NMR ꢀ 1.01 (3H, t, J ¼ 6:9 Hz), 1.92 (6H, s), 3.27
(2H, q, J ¼ 6:9 Hz), 4.44 (3H, s), 7.39 (1H, ddd, J ¼ 8:2, 6.9, and
1.3 Hz), 7.5–7.65 (3H, m), 7.70 (1H, ddd, J ¼ 8:2, 6.9, and 1.3
Hz), 8.24 (1H, dd, J ¼ 8:2 and 1.3 Hz), 8.67 (1H, d, J ¼ 8:2 Hz),
and 9.19 (1H, d, J ¼ 8:2 Hz); 13C NMR ꢀ 15.99, 26.34, 33.88,
59.12, 80.68, 108.59, 112.85, 117.71, 120.40, 121.25, 121.72,
125.02, 125.21, 127.08, 127.42, 130.72, 140.60, 141.38, 145.34,
and 160.40; MS (EI) m=z (%) 318 (Mþ, 1.2) and 274 (100).
Found: C, 79.10; H, 6.96; N, 8.79%. Calcd for C21H22N2O: C,
79.21; H, 6.96; N, 8.80%.
1
ane–CH2Cl2); IR 3382 cmꢂ1; H NMR ꢀ 0.85–1.4 (5H, m), 1.5–
1.6 (2H, m), 1.8–1.9 (2H, m), 2.0–2.1 (2H, m), 4.40 (3H, s), 5.49
(1H, brs), 5.60 (1H, br), 7.44 (1H, ddd, J ¼ 8:2, 6.9, and 1.3 Hz),
7.5–7.65 (3H, m), 7.72 (1H, ddd, J ¼ 8:2, 6.9, and 1.3 Hz), 8.01
(1H, d, J ¼ 7:9 Hz), 8.24 (1H, dd, J ¼ 8:2 and 1.3 Hz), and 8.62
(1H, dd, J ¼ 7:9 and 1.3 Hz); 13C NMR ꢀ 24.66, 25.89, 26.31,
26.82, 31.28, 33.65, 42.66, 74.86, 109.50, 111.44, 117.69, 121.09,
121.38, 121.80, 122.14, 125.18, 125.19, 127.88, 129.95, 140.57,
140.73, 144.53, and 157.26; MS (EI) m=z (%) 344 (Mþ, 24) and
262 (100). Found: C, 80.15; H, 7.02; N, 8.05%. Calcd for C23H24-
N2O: C, 80.20; H, 7.02; N, 8.13%.
6-(1-Hydroxy-2,2-dimethylpropyl)-11-methyl-11H-indolo-
A pale-yellow solid; mp 225–228 ꢁC
[3,2-c]quinoline (4d):
(hexane–EtOAc); IR 3432 cmꢂ1
;
1H NMR ꢀ 1.06 (9H, s), 4.41
(3H, s), 4.90 (1H, br), 5.55 (1H, brs), 7.41 (1H, ddd, J ¼ 8:2, 6.9,
and 1.3 Hz), 7.5–7.65 (3H, m), 7.72 (1H, ddd, J ¼ 8:2, 6.9, and
1.3 Hz), 8.24 (1H, dd, J ¼ 8:2 and 1.0 Hz), 8.35 (1H, d, J ¼ 8:2
Hz), and 8.65 (1H, dd, J ¼ 8:2 and 1.0 Hz); 13C NMR ꢀ 26.37,
33.66, 38.41, 77.20, 109.40, 113.70, 117.50, 120.84, 121.59,
121.81, 123.03, 125.12, 125.17, 127.76, 130.07, 140.23, 140.70,
144.95, and 157.57; MS (EI) m=z (%) 318 (Mþ, 8.0) and 261
(100). Found: C, 79.23; H, 7.12; N, 8.58%. Calcd for C21H22N2O:
C, 79.21; H, 6.96; N, 8.80%.
6-Dimethylaminomethyl-11-methyl-11H-indolo[3,2-c]quin-
oline (7a). To a stirred solution of N,N-dimethylmethaniminium
iodide (6a) (0.17 g, 0.92 mmol) in 1,2-dichloroethane (10 mL) at
0 ꢁC was added a solution of the isocyanide 3 (0.21 g, 0.92 mmol)
in 1,2-dichloroethane (3 mL). After stirring for 10 min, the white
precipitate was collected by suction and treated with saturated
aqueous NaHCO3. The mixture was extracted with 1,2-dichloro-
ethane twice (10 mL each) and the extracts were dried over anhy-
drous Na2SO4. Evaporation of the solvent gave a residual solid,
which was recrystallized from hexane–CH2Cl2 to give 7a (0.25 g,
6-(1-Hydroxy-1-methylethyl)-11-methyl-11H-indolo[3,2-c]-
A pale-yellow solid; mp 228 ꢁC (hexane–
quinoline (4e):
CH2Cl2); IR 3224 cmꢂ1
;
1H NMR ꢀ 2.00 (6H, s), 4.47 (3H, s),
7.34 (1H, br), 7.46 (1H, ddd, J ¼ 8:2, 6.9, and 1.3 Hz), 7.55–7.7
(3H, m), 7.75 (1H, ddd, J ¼ 8:2, 6.9, and 1.3 Hz), 8.27 (1H, d,
J ¼ 8:2 Hz), 8.43 (1H, d, J ¼ 8:2 Hz), and 8.69 (1H, d, J ¼ 8:6
Hz); 13C NMR ꢀ 28.18, 33.98, 71.52, 109.57, 110.63, 117.52,
120.40, 121.09, 121.83, 124.35, 125.18, 125.47, 128.11, 129.75,
140.81, 142.01, 143.54, and 160.45; MS (EI) m=z (%) 290 (Mþ,
19) and 275 (100). Found: C, 78.71; H, 6.21; N, 9.47%. Calcd
for C19H18N2O: C, 78.59; H, 6.25; N, 9.65%.
93%) as pale-yellow needles; mp 153–154 ꢁC; IR 1613 cmꢂ1
;
1H NMR ꢀ 2.46 (6H, s), 4.23 (2H, s), 4.43 (3H, s), 7.43 (1H, ddd,
J ¼ 8:2, 6.9, and 1.3 Hz), 7.5–7.65 (3H, m), 7.72 (1H, ddd, J ¼
8:2, 6.9, and 1.3 Hz), 8.3–8.4 (2H, m), and 8.66 (1H, dd, J ¼
8:2 and 1.3 Hz); 13C NMR ꢀ 33.50, 45.90, 65.70, 109.00, 114.17,
117.75, 121.08, 121.64 (two overlapped C’s), 123.38, 125.09,
125.12, 127.50, 130.41, 140.54, 140.58, 146.00, and 154.88; MS
(CI) m=z (%) 290 [ðM þ 1Þþ, 100]. Found: C, 78.83; H, 6.78;
N, 14.51%. Calcd for C19H19N3: C, 78.86; H, 6.62; N, 14.52%.
6-(1-Dimethylaminopropyl)-11-methyl-11H-indolo[3,2-c]-
6-(1-Hydroxy1-1-methylpropyl)-11-methyl-11H-indolo[3,2-
c]quinoline (4f): A pale-yellow solid; mp 171–172 ꢁC (hexane–
Et2O); IR 3232 cmꢂ1
;
1H NMR ꢀ 0.83 (3H, t, J ¼ 7:3 Hz), 2.00
(3H, s), 2.3–2.55 (2H, m), 4.51 (3H, s), 7.28 (1H, br), 7.44 (1H,
ddd, J ¼ 8:2, 6.9, and 1.3 Hz), 7.5–7.7 (3H, m), 7.74 (1H, ddd,
J ¼ 8:2, 6.9, and 1.3 Hz), 8.27 (1H, dd, J ¼ 8:2 and 1.0 Hz),