PAPER
One-Pot Synthesis of 4-(1H-Indol-3-yl)quinolines
4089
Ethyl 4-[4-(2-Phenyl-1H-indol-3-yl)quinolin-2-yl]benzoate
(4ca)
Yield: 50%; mp 193–194 °C.
1H NMR (DMSO-d6): d = 2.60 (s, 3 H, CH3), 7.02 (t, J = 7.5 Hz,
1 H), 7.18 (d, J = 7.8 Hz, 1 H), 7.27 (t, J = 7.6 Hz, 1 H), 7.37 (t, J =
7.6 Hz, 1 H), 7.64–7.55 (m, 4 H), 7.76–7.67 (m, 3 H), 8.07 (d, J =
8.4 Hz, 2 H), 8.15 (s, 1 H), 8.19 (d, J = 8.4 Hz, 1 H), 8.37 (d, J =
8.2 Hz, 2 H), 12.15 (s, 1 H, NH).
IR (KBr): 3369, 3059, 2925, 2853, 1719, 1604, 1594, 1579, 1542,
1447, 1273, 1100 cm–1.
13C NMR (DMSO-d6): d = 26.6 (CH3), 109.7 (C), 111.0 (C), 111.8
(CH), 118.4 (CN), 119.0 (CH), 120.3 (CH), 120.8 (CH), 123.2
(CH), 125.6 (CH), 126.3 (C), 126.7 (CH), 127.3 (2CH), 127.7
(2CH), 128.5 (2CH), 128.7 (C), 129.8 (CH), 129.9 (CH), 132.3
(2CH), 133.6 (C), 136.2 (C), 136.6 (C), 137.2 (C), 142.5 (C), 143.0
(C), 148.3 (C), 154.7 (C), 197.3 (CO).
1H NMR (DMSO-d6): d = 1.42 (t, J = 7.0 Hz, 3 H, COOCH2CH3),
4.40 (q, J = 7.0 Hz, 2 H, COOCH2CH3), 7.11–7.03 (m, 1 H), 7.30–
7.24 (m, 5 H), 7.40 (d, J = 7.4 Hz, 1 H), 7.51–7.46 (m, 2 H), 7.66
(d, J = 8.3 Hz, 1 H), 7.79–7.75 (m, 2 H), 8.17–8.13 (m, 3 H), 8.18
(d, J = 8.8 Hz, 1 H), 8.33 (d, J = 8.1 Hz, 2 H), 12.05 (s, 1 H, NH).
13C NMR (DMSO-d6):
d
= 14.1 (COOCH2CH3), 60.7
MS (ESI): m/z (%) = 464 (50) [M + H]+.
(COOCH2CH3), 109.0 (C), 111.7 (CH), 118.7 (CH), 1120.0 (CH),
120.8 (CH), 122.3 (CH), 126.1 (CH), 126.4 (CH), 126.7 (C), 127.3
(2CH), 127.51 (2CH), 127.53 (CH), 128.5 (2CH), 128.9 (C), 129.5
(2CH), 129.8 (2CH), 130.5 (C), 131.9 (C), 136.0 (C), 136.3 (C),
143.0 (C), 143.9 (C), 148.5 (C), 154.7 (C), 165.4 (CO).
Ethyl 3-{3-[6,8-Difluoro-2-(2-methoxyphenyl) quinolin-4-yl]-
1H-indol-2-yl}benzoate (4ec)
Yield: 50%; mp 188–190 °C.
IR (KBr): 3320, 3038, 2905, 2830, 1715, 1587, 1572, 1260, 1085
cm–1.
MS (ESI): m/z (%) = 469 (100) [M + H]+.
Ethyl 4-{4-[2-(4-Acetylphenyl)-5,7-difluoro-1H-indol-3-
yl]quinolin-2-yl}benzoate (4ce)
Yield: 55%; mp 270 °C (dec.).
1H NMR (DMSO-d6): d = 1.21 (t, J = 7.0 Hz, 3 H, CH2CH3), 3.70
(s, 3 H, OCH3), 4.22 (q, J = 7.0 Hz, 2 H, CH2CH3), 7.21–7.09 (m,
5 H), 7.33 (t, J = 7.4 Hz, 2 H), 7.48 (t, J = 7.6 Hz, 2 H), 7.76–7.63
(m, 2 H), 7.87 (d, J = 7.5 Hz, 1 H), 7.94 (dd, J = 7.5, 1.7 Hz, 1 H),
8.06 (d, J = 9.1 Hz, 2 H), 12.28 (s, 1 H, NH).
IR (KBr): 3437, 3295, 3070, 2990, 2964, 2925, 1714, 1684, 1648,
1607, 1595 cm–1.
13C NMR (DMSO-d6): d = 13.8 (CH2CH3), 55.5 (OCH3), 60.7
(CH2CH3), 105.1 (m, 2CH), 109.1 (C), 112.0 (2CH), 118.6 (CH),
120.4 (CH), 120.8 (CH), 122.9 (CH), 127.1 (CH), 127.3 (C), 127.9
(C), 128.21 (CH), 128.26 (C), 128.32 (CH), 129.2 (CH), 130.2
(CH), 131.0 (2CH), 131.9 (C), 132.0 (C), 134.8 (C), 136.2 (t,
J = 7 Hz, C), 136.5 (C), 140.8 (t, J = 3 Hz, C), 155.7 (C), 157.1 (C),
157.1 (dd, J = 245.3, 10.3 Hz, CF), 158.9 (dd, J = 260.2, 11.7 Hz,
CF), 165.1 (CO).
1H NMR (DMSO-d6): d = 1.32 (t, J = 6.94 Hz, 3 H, OCH2CH3),
2.43 (s, 3 H, CH3), 4.32 (q, J = 6.94 Hz, 2 H, OCH2CH3), 6.78 (d, J
= 6.78 Hz, 1 H), 7.15 (t, J = 9.83 Hz, 1 H), 7.38 (t, J = 7.37 Hz,
1 H), 7.57–7.52 (m, 3 H), 7.79–7.70 (m, 3 H), 8.03 (d, J = 8.1 Hz,
2 H, A part of AB system), 8.17–8.14 (m, 2 H), 8.36 (d, J = 8.1 Hz,
2 H, B part of AB system), 12.64 (s, 1 H, NH).
13C NMR (DMSO-d6): d = 14.2 (OCH2CH3), 26.6 (CH3CO), 60.9
(OCH2CH3), 98.2 (t, J = 20 Hz, CH), 99.9 (d, J = 20 Hz, CH), 111.4
(C), 121.0 (CH), 121.5 (d, J = 14 Hz, C), 125.5 (CH), 126.3
(C),127.1 (CH), 127.5 (2 CH), 127.9 (2 CH), 128.4 (2 CH), 129.6
(2 CH), 129.9 (CH), 130.2 (CH), 130.5 (C), 131.2 (dd, J = 11, 7 Hz,
C), 135.3 (C), 135.9 (C), 137.6 (C), 142.3 (C), 142.6 (C), 148.3 (C),
148.4 (dd, J = 248, 14 Hz, CF), 154.8 (C), 156.5 (dd, J = 237, 10 Hz,
CF), 165.5 (COOEt), 197.2 (CH3CO).
MS (ESI): m/z (%) = 535 (100) [M + H]+.
4-(2-Cyclooct-1-en-1-yl-1H-indol-3-yl)-6,8-difluoro-2-(2-meth-
oxyphenyl)quinoline (4ef)
Yield: 56%; mp 217–218 °C.
IR (KBr): 3450, 2940, 2900, 2820, 1628, 1595, 1550, 1485, 1249
cm–1.
1H NMR (CDCl3): d = 1.38–1.33 (m, CH2, 8 H), 2.27–2.15 (m,
4 H), 3.82 (s, CH2, 3 H), 6.01 (t, J = 8.3 Hz, 1 H), 7.32–7.00 (m,
7 H), 7.45–7.37 (m, 2 H), 7.99 (dd, J = 7.5, 1.7 Hz, 1 H), 8.10 (s,
1 H), 8.46 (br s, NH, 1 H).
MS (ESI): m/z (%) = 547 (100) [M + H]+.
1-{4-[4-(2-Phenyl-1H-indol-3-yl)quinolin-2-yl]phenyl}etha-
none (4da)
Yield: 51%; mp 219–220 °C.
IR (KBr): 3219, 3062, 3040, 2919, 1686, 1595, 1579, 1540, 1504,
1450, 1356 cm–1.
13C NMR (CDCl3): d = 25.9 (CH2), 26.6 (CH2), 27.0 (CH2), 27.9
(CH2), 29.1 (CH2), 29.6 (CH2), 55.6 (CH3), 104.7 (dd, J = 29.6,
23.0 Hz, CH), 105.8 (dd, J = 22.5, 4.7 Hz, CH), 109.2 (C), 110.7
(CH), 111.4 (CH), 119.2 (CH), 120.5 (CH), 121.3 (CH), 122.7
(CH), 123.9 (C), 127.1 (C), 127.5 (CH),130.6 (CH), 130.8 (C),
131.2 (C), 131.7 (CH), 131.9 (CH), 133.1 (C), 135.1 (C), 138.0 (C),
141.7 (C), 156.2 (C), 157.5 (C), 158.0 (dd, J = 247.5, 11.3 Hz, CF),
158.7 (dd, J = 259.0, 13.0 Hz, CF).
1H NMR (CDCl3): d = 2.59 (s, 3 H, CH3), 7.34–7.07 (m, 9 H), 7.49
(d, J = 8.1 Hz, 1 H), 7.67 (t, J = 7.5 Hz, 1 H), 7.81 (d, J = 8.2 Hz,
1 H), 7.87 (s, 1 H), 8.01 (d, J = 8.2 Hz, 2 H, A part of AB system),
8.16 (d, J = 8.2 Hz, 2 H, B part of AB system), 8.25 (d, J = 8.4 Hz,
1 H), 8.77 (br s, 1 H, NH).
13C NMR (CDCl3): d = 26.6 (CH3CO), 111.0 (C), 111.2 (CH), 119.9
(CH), 120.9 (CH), 121.4 (CH), 123.2 (CH), 126.4 (CH), 126.6
(CH), 127.3 (C), 127.6 (2 CH), 127.7 (2 CH), 128.1 (CH), 128.7 (2
CH), 128.8 (2 CH), 129.6 (C), 129.7 (CH), 130.2 (CH), 132.0 (C),
136.1 (C), 136.2 (C), 137.5 (C), 143.6 (C), 144.1 (C), 149.2 (C),
155.7 (C), 197.7 (CO).
MS (ESI): m/z (%) = 495 (100) [M + H]+.
4-[4-(2-Phenyl-1H-indol-3-yl)quinolin-2-yl]benzonitrile (4fa)
Yield: 51%; mp 275 °C (dec.).
IR (KBr): 3318, 3940, 2900, 2822, 2200, 1720, 1590, 1572, 1438,
1223 cm–1.
1H NMR (DMSO-d6): d = 7.01 (d, J = 7.5 Hz, 1 H), 7.22–7.16 (m,
5 H), 7.41–7.35 (m, 3 H), 7.57 (d, J = 8.0 Hz, 1 H), 7.71 (d, J =
8.0 Hz, 2 H), 7.91 (d, J = 8.3 Hz, 2 H), 8.09 (s, 1 H), 8.16 (d, J =
8.6 Hz, 1 H), 8.39 (d, J = 8.3 Hz, 2 H), 11.94 (s, 1 H, NH).
MS (ESI): m/z (%) = 439 (100) [M + H]+.
4-{3-[2-(4-Acetylphenyl)quinolin-4-yl]-1H-indol-2-yl}benzoni-
trile (4dd)
Yield: 60%; mp 290 °C (dec.).
IR (KBr): 3366, 3058, 2926, 2866, 2226, 1679, 1605, 1267, 1239
cm–1.
13C NMR (DMSO-d6): d = 108.6 (C), 111.6 (CH), 111.9 (C), 118.6
(C), 118.7 (CH), 120.0 (CH), 120.7 (CH), 122.2 (CH), 126.1 (CH),
Synthesis 2011, No. 24, 4084–4090 © Thieme Stuttgart · New York