4
Tetrahedron
mol%, 25.4 mg) in DMF (5 mL) was added 30% aqueous
C1 H11FN2: C, 77.85; H, 4.23; N, 10.68%. Found: C, 77.81; H,
ACCEPTED MANUSCRIPT
7
solution of H2O2 (0.113 mL, 1 mmol). The reaction was stirred
at 100 C for 1 h. After completion of the reaction (TLC), the
4.28; N, 10.74%.
o
1-(2-(trifluoromethyl)phenyl)-9H-pyrido[3,4-b]indole (2f): White
reaction mixture was treated with a 5% hypo solution (5 mL).
The reaction mixture was then extracted with ethyl acetate (2 x
20 mL) and the combined ethyl acetate layer was washed with
water (2 x 5 mL). The organic layer was dried over anhydrous
Na2SO4 and concentrated under reduced pressure. The crude
product was purified over column chromatography to afford 1-
phenyl-β-carboline 2a (210 mg, 86% yield).19 mp 242-244 oC; IR
(neat) 3213, 3064, 2956, 2879, 1624, 1496, 1467, 1234, 736 cm-
o
solid: mp 114-116 C; IR (neat) 3623, 3066, 2923, 2853, 1627,
1500, 1311, 1170, 1114, 1062, 1033, 753 cm-1; H NMR (500
1
MHz, DMSO-d6) δ: 11.26 (s, 1H), 8.40 (d, J = 5.5 Hz, 1H), 8.28
(d, J = 8.0 Hz, 1H), 8.16 (d, J = 5.5 Hz, 1H), 7.98 (d, J = 7.5 Hz,
1H), 7.86 (t, J = 7.5 Hz, 1H), 7.79 (t, J = 8.0 Hz, 1H), 7.66 (d, J =
7.5 Hz, 1H), 7.54-7.53 (m, 2H),7.29-7.25 (m, 1H); 13C NMR
(125 MHz, DMSO-d6) δ: 141.7, 140.9, 137.4, 137.0, 134.0,
132.4, 131.6, 129.0, 128.2, 127.8, 126.6, 126.5, 121.7, 120.6,
119.4, 114.3, 112.1; GC-MS (EI): m/z 312; Anal. Calcd. for
molecular formula C18H11F3N2: C, 69.23; H, 3.55; N, 8.97%.
Found: C, 69.19; H, 3.56; N, 8.93%.
1; H NMR (500 MHz, DMSO-d6) δ: 11.52 (s, 1H), 8.48 (d, J =
1
5.0 Hz, 1H), 8.28 (d, J = 7.5 Hz, 1H), 8.13 (d, J = 5.5 Hz, 1H),
8.05 (d, J = 7.2 Hz, 2H), 7.68-7.61 (m, 3H), 7.58-7.52 (m, 2H),
7.28 (t, J = 7.9 Hz, 1H); 13C NMR (125 MHz, DMSO-d6) δ:
142.2, 141.1, 138.4, 138.3, 133.0, 129.1, 128.7, 128.5, 128.4,
128.1, 121.5, 120.8, 119.5, 113.8, 112.4; GC-MS (EI): m/z =
244; Anal. Calcd. for molecular formula C17H12N2: C, 83.58; H,
4.95; N, 11.47%. Found: C, 83.61; H, 4.89; N, 11.50%.
9H-pyrido[3,4-b]indole (2g)19: White solid: mp 196-197 C; IR
o
(neat) 3122, 3051, 2841, 1642, 1461, 1228, 1126, 1011, 818, 745
cm-1; 1H NMR (500 MHz, DMSO-d6) δ: 11.63 (s, 1H), 8.89 (d, J
= 0.5 Hz, 1H), 8.31 (d, J = 5.5 Hz, 1H), 8.2 (d, J = 7.0 Hz, 1H),
8.09 (dd, J1 = 0.5 Hz, J2 = 1.0 Hz, 1H), 7.60 (d, J = 10.0 Hz, 1H),
7.55-7.53 (m, 1H), 7.24-7.21 (m, 1H); 13C NMR (125 MHz,
DMSO-d6) δ: 140.5, 137.9, 135.9, 133.7, 128.5, 127.6, 121.7,
120.4, 119.4; 114.7, 112.1, GC-MS (EI): m/z 168; Anal. Calcd.
for molecular formula C11H8N2: C, 78.55; H, 4.79; N, 16.66%.
Found: C, 78.63; H, 4.73; N, 16.64%.
1-(4-methoxyphenyl)-9H-pyrido[3,4-b]indole (2b)20: White solid:
o
mp 158-159 C; IR (neat) 3123, 3055, 2928, 2851, 1625, 1513,
1251, 1236, 1173, 751 cm-1; H NMR (500 MHz, DMSO-d6) δ:
1
11.46 (s, 1H), 8.43 (d, J = 5.0 Hz, 1H), 8.26 (d, J = 7.5 Hz, 1H),
8.07 (d, J = 5.5 Hz, 1H), 8.01 (d, J = 9.0 Hz, 2H), 7.66 (d, J =
8.5 Hz, 1H), 7.55 (t, J = 8.0 Hz, 1H), 7.27 (t, J = 8.0 Hz, 1H),
7.18 (d, J = 8.5 Hz, 2H), 3.89 (s, 3H); 13C NMR (125 MHz,
DMSO-d6) δ: 159.6, 142.1, 141.0, 138.2, 132.7, 130.9, 129.6,
129.0, 128.0, 121.5, 120.9, 119.4, 114.1, 113.2, 112.4, 55.3; GC-
MS (EI): m/z 274; Anal. Calcd. for molecular formula
C18H14N2O: C, 78.81; H, 5.14; N, 10.21%. Found: C, 78.79; H,
5.21; N, 10.26%.
1-(p-tolyl)-9H-pyrido[3,4-b]indole (2c)19: White solid: mp 190-
193 oC; IR (neat) 3645, 3128, 3060, 2923, 1626, 1470, 1237, 739
cm-1; 1H NMR (500 MHz, DMSO-d6) δ: 11.46 (s, 1H), 8.45 (d, J
= 5.0 Hz, 1H), 8.26 (d, J = 7.5 Hz, 1H), 8.10 (d, J = 5.0 Hz, 1H),
7.95 (d, J = 8.0 Hz, 2H), 7.66 (d, J = 8.5 Hz, 1H), 7.56 (t, J = 8.0
Hz, 1H), 7.43 (d, J = 7.5 Hz, 2H),7.27 (t, J = 8.0 Hz, 1H), 2.45 (s,
3H); 13C NMR (125 MHz, DMSO-d6) δ: 142.3, 141.0, 138.3,
137.9, 135.6, 132.9, 129.3, 129.0, 128.2, 128.0, 121.5, 120.8,
119.4, 113.6, 112.4, 20.9; GC-MS (EI): m/z 258; Anal. Calcd. for
molecular formula C18H14N2: C, 83.69; H, 5.46; N, 10.84%.
Found: C, 83.63; H, 5.43; N, 10.94%.
1-Methyl-9H-pyrido[3,4-b]indole (2h)19: White solid: mp 235-
o
236 C; IR (neat) 3126, 3046, 2912, 2841, 1645, 1423, 1252,
1112, 1017, 827, 737 cm-1; H NMR (500 MHz, DMSO-d6) δ:
1
11.68 (s, 1H), 8.17-8.15 (m, 2H), 7.90 (d, J = 5.5 Hz, 1H), 7.60
(d, J = 8.5 Hz, 1H), 7.54-7.51 (m, 1H), 7.21 (t, J = 10.0 Hz, 1H),
2.75 (s, 3H); 13C NMR (125 MHz, DMSO-d6) δ: 141.9, 140.4,
137.0, 134.4, 128.0, 127.1, 120.8, 119.5, 112.8, 111.9; GC-MS
(EI): m/z 182; Anal. Calcd. for molecular formula C12H10N2: C,
79.10; H, 5.53; N, 15.37%. Found: C, 79.19; H, 5.56; N, 15.25%.
Methyl 1-phenyl-9H-pyrido[3,4-b]indole-3-carboxylate (4a)17:
White solid: mp 257-258 C; IR (neat) 3317, 3002, 2951, 1720,
o
1351, 1290, 1253, 756, 740 cm-1; 1H NMR (500 MHz, DMSO-d6)
δ: 11.96 (s, 1H), 8.94 (s, 1H), 8.44 (d, J = 7.5 Hz, 1H), 8.04 (d, J
= 7.0 Hz, 2H), 7.72 (d, J = 8.5 Hz, 1H), 7.66-7.58 (m, 4H), 7.34
(t, J = 7.5 Hz, 1H), 3.95 (s, 3H); 13C NMR (125 MHz, DMSO-d6)
δ: 166.1, 142.1, 141.5, 137.5, 136.7, 134.6, 129.2, 129.0, 128.8,
128.7, 128.6, 122.0, 121.1, 120.4, 116.6, 112.8, 52.00; GC-MS
(EI): m/z 302; Anal. Calcd. for molecular formula C19H14N2O2: C,
75.48; H, 4.67; N, 9.27%. Found: C, 75.50; H, 4.62; N, 9.31%.
1-(4-chlorophenyl)-9H-pyrido[3,4-b]indole (2d)19: Light yellow
o
solid: mp 197-198 C; IR (neat) 3136, 3064, 2922, 2851, 1623,
1423, 1234, 1090, 1013, 819, 746 cm-1; H NMR (500 MHz,
1
Methyl1-(4-methoxyphenyl)-9H-pyrido[3,4-b]indole-3-
carboxylate (4b)17: White solid: mp 228-230 C; IR (neat) 3267,
o
DMSO-d6) δ: 11.56 (s, 1H), 8.48 (d, J = 5.0 Hz, 1H), 8.28 (d, J =
8.0 Hz, 1H), 8.15 (d, J = 5.5 Hz, 1H), 8.07 (d, J = 9.0 Hz, 2H),
7.68-7.65 (m, 3H), 7.58 (t, J = 8.0 Hz, 1H), 7.29 (t, J = 8.0 Hz,
1H); 13C NMR (125 MHz, DMSO-d6) δ: 141.1, 140.8, 138.4,
137.2, 133.2, 133.0, 130.1, 129.4, 128.7, 128.3, 121.6, 120.8,
119.6, 114.2, 112.4; GC-MS (EI): m/z 278; Anal. Calcd. for
molecular formula C17H11ClN2: C, 73.25; H, 3.98; N, 10.05%.
Found: C, 73.31; H, 4.08; N, 9.94%.
3012, 2952, 2838, 1716, 1624, 1610, 1514, 1302, 1282, 1252,
1175, 839, 749 cm-1; 1H NMR (500 MHz, DMSO-d6) δ: 11.94 (s,
1H), 8.94 (s, 1H), 8.47 (d, J = 7.5 Hz, 1H), 8.05 (d, J = 9.0 Hz,
2H), 7.76 (d, J = 8.5 Hz, 1H), 7.66 (t, J = 8.0 Hz, 1H), 7.39 (t, J
= 7.0 Hz, 1H), 7.26 (d, J = 8.5 Hz, 2H), 3.99 (s, 3H), 3.95 (s,
3H); 13C NMR (125 MHz, DMSO-d6) δ: 166.1, 159.9, 142.0,
141.4, 136.6, 134.3, 130.0, 129.9, 129.0, 128.5, 121.9, 121.2,
120.3, 116.2, 114.2, 112.8, 55.4, 51.2; GC-MS (EI): m/z 332;
Anal. Calcd. for molecular formula C20H16N2O3: C, 72.28; H,
4.85; N, 8.43%. Found: C, 72.23; H, 4.79; N, 8.39%.
1-(3-fluorophenyl)-9H-pyrido[3,4-b]indole (2e)20: White solid:
mp 181-182 C; IR (neat) 3135, 3069, 1625, 1589, 1472, 1234.
o
1201, 796, 738 cm-1; 1H NMR (500 MHz, DMSO-d6) δ: 11.59 (s,
1H), 8.49 (d, J = 5.5 Hz, 1H), 8.29 (d, J = 8.0 Hz, 1H), 8.18 (d,
J = 6.0 Hz, 1H), 7.91 (d, J = 7.5 Hz, 1H), 7.82 (d, J = 10.0 Hz,
1H), 7.69-7.65 (m, 2H), 7.58 (t, J = 8.0 Hz, 1H), 7.37 (t, J = 9.0
Hz, 1H), 7.29 (t, J = 8.0 Hz, 1H); 13C NMR (125 MHz, DMSO-
d6) δ: 141.2, 138.4, 133.0, 130.7, 130.6, 129.5, 128.3, 124.5,
121.6, 120.8, 119.6, 115.4, 115.2, 115.1, 114.9, 114.4, 112.4;
GC-MS (EI): m/z 262; Anal. Calcd. for molecular formula
Methyl
1-(4-dimethylamino)-9H-pyrido[3,4-b]indole-3-
o
carboxylate (4c): White solid: mp 208-210 C; IR (neat) 3647,
3275, 2944, 1709, 1612, 1561, 1354, 1257, 1103, 746 cm-1; H
1
NMR (500 MHz, DMSO-d6) δ: 11.82 (s, 1H), 8.82 (s, 1H), 8.40
(d, J = 8.0 Hz, 1H), 7.94 (d, J = 9.0 Hz, 2H), 7.72 (d, J = 8.0
Hz, 1H), 7.60 (t, J = 8.0 Hz, 1H), 7.32 (t, J = 7.5 Hz, 1H), 6.97
(d, J = 9.0 Hz, 2H), 3.94 (s, 3H), 3.05 (s, 6H); 13C NMR (125
MHz, DMSO-d6) δ: 166.2, 150.8, 142.7, 141.3, 136.6, 134.1,