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Organic & Biomolecular Chemistry
obtain pure product 5n as a pale orange colour solid. Yield: 11.36 (bs, 1H), 9.08 (s, 1H), 8.36 (d, J = 7.5 Hz, 2H), 8.18 (d, J =
244 mg (95%); mp: 178–179 °C; IR (KBr): λmax/cm−1 = 3436, 7.5 Hz, 1H), 7.87 (d, J = 7.5 Hz, 2H), 7.67–7.52 (m, 4H), 7.32 (t,
3062, 1721, 1624, 1606, 1563, 1517, 1495, 1467, 1452, 1401, J = 7.5 Hz, 1H), 7.19 (dd, J = 8.3, 2.2 Hz, 1H); 13C NMR
1318, 1272, 1239, 1201, 1108, 1056, 923, 885, 845, 804, 721, (75 MHz, CDCl3 + DMSO[d6]) δ (ppm): 152.6, 140.9, 140.7,
746, 606, 569; 1H NMR (300 MHz, CDCl3 + DMSO[d6]) δ (ppm): 139.1, 136.7, 133.1, 129.8, 129.0, 128.5, 128.1, 127.6,
10.77 (bs, 1H), 9.10 (s, 1H), 8.21–8.05 (m, 3H), 7.95 (s, 1H), 124.2, 121.3, 120.4, 120.2, 119.2, 111.8, 111.5; MS (ESI, m/z):
7.66–7.48 (m, 4H), 7.32–7.22 (m, 3H); 13C NMR (75 MHz, 463 [M + 1]+; HRMS (ESI, m/z) calculated for C25H14N4F3Cl:
CDCl3 + DMSO[d6]) δ (ppm): 151.7, 143.4, 141.1, 137.2, 132.8, 463.13216, found: 463.13076 [M + 1]+.
130.1, 129.7, 127.7, 127.5, 124.3, 121.6, 120.9, 120.6, 119.3,
3-(6-Chloro-1H-benzo[d]imidazol-2-yl)-1-(4-fluorophenyl)-9H-
118.0, 117.4, 117.2, 116.4, 116.1, 111.6, 111.5, 110.7; MS (ESI, pyrido[3,4-b]indole (5r). This compound was prepared accord-
m/z): 397 [M + 1]+; HRMS (ESI, m/z) calculated for C24H15N4F2: ing to the general procedure, employing 4d (200 mg,
397.12593, found: 397.12534 [M + 1]+.
0.68 mmol) and 4-chlorobenzene-1,2-diamine (97 mg,
3-(6-Fluoro-1H-benzo[d]imidazol-2-yl)-1-(4-(trifluoromethyl)- 0.68 mmol) to obtain pure product 5r as a pale yellow solid.
phenyl)-9H-pyrido[3,4-b]indole (5o). This compound was pre- Yield: 244 mg (86%); mp: 157–159 °C; IR (KBr): λmax/cm−1
=
pared according to the general procedure, employing 4c 3429, 3061, 2924, 1717, 1622, 1603, 1506, 1450, 1397, 1318,
(200 mg, 0.58 mmol) and 4-fluorobenzene-1,2-diamine (74 mg, 1224, 1154, 1094, 1052, 973, 922, 840, 801, 744, 700, 590, 565,
0.58 mmol) to obtain pure product 5o as a pale yellow solid. 504, 434; 1H NMR (300 MHz, CDCl3 + DMSO[d6]) δ (ppm):
Yield: 217 mg (83%); mp: 302–304 °C; IR (KBr): λmax/cm−1
=
10.51 (bs, 1H), 9.07 (s, 1H), 8.62 (s, 1H), 8.20 (d, J = 7.9 Hz,
3456, 3067, 1623, 1598, 1566, 1549, 1999, 1455, 1396, 1321, 1H), 8.03–8.00 (m, 2H), 7.75 (d, J = 8.3 Hz, 1H), 7.62–7.59 (m,
1251, 1202, 1164, 1109, 1064, 844, 750, 607, 573; 1H NMR 1H), 7.55 (d, J = 8.0 Hz, 1H), 7.43 (d, J = 8.3 Hz, 1H), 7.39–7.32
(300 MHz, CDCl3 + DMSO[d6]) δ (ppm): 10.47 (bs, 1H), 9.13 (s, (m, 3H); 13C NMR (75 MHz, CDCl3 + DMSO[d6]) δ (ppm):
1H), 8.61 (s, 1H), 8.23 (d, J = 8.1 Hz, 1H), 8.16 (d, J = 8.1 Hz, 162.7, 161.5, 159.4, 152.1, 140.2, 139.2, 135.9, 132.5, 132.1,
2H), 7.94 (d, J = 8.1 Hz, 2H), 7.66–7.52 (m, 3H), 7.40 (t, J = 7.9 129.4, 129.3, 128.7, 126.8, 125.1, 120.5, 119.8, 119.6, 118.5,
Hz, 1H), 7.06 (dt, J = 9.4, 2.2 Hz, 1H); 13C NMR (175 MHz, 113.9, 113.6, 111.0, 110.6; MS (ESI, m/z): 413[M + 1]+; HRMS
CDCl3 + DMSO) δ (ppm): 158.5 (dd, J = 244.9 Hz, 54.6 Hz, (ESI, m/z) calculated for C24H15N4FCl: 413.09638, found:
ArC-CF), 153.6, 152.6, 144.2, 141.6, 141.3, 140.4, 139.6, 137.6, 413.09602 [M + 1]+.
133.5, 130.5, 129.3 (q, J = 32.4 Hz, CF3Ar-C), 129.2, 128.3,
3-(1H-Benzo[d]imidazol-2-yl)-1-(4-fluorophenyl)-9H-pyrido-
125.0, 123.8 (q, J = 272.1 Hz, ArC-CF3), 121.3, 120.8, 119.8, [3,4-b]indole (5s). This compound was prepared according to
119.0, 112.2 (m), 109.6 (m), 103.6, 97.8; MS (ESI, m/z): the general procedure, employing 4d (200 mg, 0.68 mmol) and
447 [M + 1]+; HRMS (ESI, m/z) calculated for C25H15N4F4: benzene-1,2-diamine (74 mg, 0.68 mmol) to obtain pure
447.12274, found: 447.12133 [M + 1]+.
product 5s as a pale yellow solid. Yield: 232 mg (89%); mp:
3-(1H-Benzo[d]imidazol-2-yl)-1-(4-(trifluoromethyl)phenyl)- 178–180 °C; IR (KBr): λmax/cm−1 = 3456, 3291, 3058, 2918,
9H-pyrido[3,4-b]indole (5p). This compound was prepared 1625, 1554, 1510, 1498, 1469, 1454, 1425, 1408, 1275, 1241,
1
according to the general procedure, employing 4c (200 mg, 1217, 1158, 1112, 1092, 837, 797, 730, 665, 577, 501; H NMR
0.58 mmol) and benzene-1,2-diamine (63 mg, 0.58 mmol) to (300 MHz, CDCl3) δ (ppm): 10.51 (bs, 1H), 9.10 (s, 1H), 8.65 (s,
obtain pure product 5p as a pale yellow solid. Yield: 214 mg 1H), 8.21 (d, J = 7.5 Hz, 1H), 8.06–7.99 (m, 2H), 7.87 (s, 1H),
(85%); mp: 299–301 °C; IR (KBr): λmax/cm−1 = 3458, 3067, 7.62–7.50 (m, 3H), 7.40–7.29 (m, 5H); 13C NMR (175 MHz,
2925, 2358, 1622, 1566, 1548, 1498, 1471, 1455, 1414, 1321, CDCl3 + DMSO) δ (ppm): 162.9 (d, J = 247.5 Hz, ArC-F), 152.8,
1
1168, 1149, 1106, 1064, 1017, 849, 750, 737, 622, 583, 561; H 142.1, 141.0, 138.2, 134.5, 133.9, 131.3, 131.2, 130.7, 128.7,
NMR (300 MHz, CDCl3 + DMSO[d6]) δ (ppm): 10.52 (bs, 1H), 122.6, 121.7, 121.5, 120.3, 115.7, 115.6, 112.9, 112.2; MS (ESI,
9.14 (s, 1H), 8.77 (s, 1H), 8.21 (s, 1H), 8.15 (d, J = 8.1 Hz, 2H), m/z): 379 [M + 1]+; HRMS (ESI, m/z) calculated for C24H16N4F:
7.90 (d, J = 7.9 Hz, 3H), 7.65–7.51 (m, 3H), 7.40–7.30 (m, 2H); 379.13535, found: 379.13529 [M + 1]+.
13C NMR (175 MHz, CDCl3 + DMSO) δ (ppm): 152.0, 141.6,
1-(4-Fluorophenyl)-3-(6-methyl-1H-benzo[d]imidazol-2-yl)-
141.4, 139.6, 137.9, 133.5, 130.4, 129.2, 129.1 (q, J = 31.7 Hz, 9H-pyrido[3,4-b]indole (5t). This compound was prepared
CF3Ar-C), 128.5, 128.3, 124.9, 123.8 (q, J = 272.1 Hz, ArC-CF3), according to the general procedure, employing 4d (200 mg,
112.3, 112.2; MS (ESI, m/z): 429 [M + 1]+; HRMS (ESI, m/z) cal- 0.68 mmol) and 4-methylbenzene-1,2-diamine (84 mg,
culated for C25H16N4F3: 429.13216, found: 429.13076 [M + 1]+.
0.68 mmol) to obtain pure product 5t as a pale yellow solid.
3-(6-Chloro-1H-benzo[d]imidazol-2-yl)-1-(4-(trifluoromethyl)- Yield: 237 mg (88%); mp: 236–238 °C; IR (KBr): λmax/cm−1
=
phenyl)-9H-pyrido[3,4-b]indole (5q). This compound was pre- 3454, 3252, 3053, 2920, 1626, 1604, 1509, 1455, 1470, 1425,
1
pared according to the general procedure, employing 4c 1404, 1320, 1278, 1218, 1157, 844, 806, 745, 608, 572, 504; H
(200 mg, 0.58 mmol) and 4-chlorobenzene-1,2-diamine NMR (300 MHz, CDCl3 + DMSO[d6]) δ (ppm): 10.37 (bs, 1H),
(83 mg, 0.58 mmol) to obtain pure product 5q as a pale yellow 9.08 (s, 1H), 8.63 (s, 1H), 8.19 (d, J = 7.5 Hz, 1H), 8.05–8.00 (m,
solid. Yield: 223 mg (82%); mp: 326–328 °C; IR (KBr): λmax
/
2H), 7.62–7.50 (m, 2H), 7.41–7.28 (m, 4H), 7.11 (d, J = 7.5 Hz,
cm−1 = 3453, 3065, 2923, 1722, 1625, 1565, 1547, 1466, 1454, 1H), 2.52 (s, 3H); 13C NMR (175 MHz, CDCl3 + DMSO) δ (ppm):
1396, 1321, 1248, 1165, 1108, 1064, 924, 882, 850, 747, 732, 162.3 (d, J = 247.9 Hz, ArC-F), 151.9, 141.4, 140.3, 137.7, 133.9,
596, 576; 1H NMR (300 MHz, CDCl3 + DMSO[d6]) δ (ppm): 133.2, 131.0, 130.6 (d, J = 8.2 Hz), 130.0, 128.0, 123.1, 120.9
2382 | Org. Biomol. Chem., 2014, 12, 2370–2387
This journal is © The Royal Society of Chemistry 2014