2,4-Dimethyl-9H-pyrido[2,3-b]indole (8b): White solid, 43%;
mp 222-224 °C; 1H NMR (400 MHz, CDCl3) δ 2.53 (3H, s, CH3),
2.74 (3H, s, CH3), 6.89 (1H, s, CH), 7.19 (1H, t, J ) 7.3 Hz, CH),
7.39 (1H, t, J ) 8.1 Hz, CH), 7.47 (1H, d, J ) 7.8 Hz, CH), 8.04
(1H, d, J ) 7.7 Hz, CH), 11.6 (1H, s, NH); 13C NMR δ 24.7, 29.3
(CH3), 116.3, 116.7 (CH), 121.5 (C), 124.5 (CH), 126.2 (C), 127.5,
130.5 (CH), 143.6, 146.9, 157.0, 159.8 (C); IR 3117, 2939, 1611,
1441 cm-1; HRMS (CI+) calcd for C13H13N2 197.1079, found
197.1081.
2-Phenyl-9H-pyrido[2,3-b]indole (8g):19 White solid, 52%; mp
245-246 °C; 1H NMR (400 MHz, CDCl3) δ 6.89 (1H, d, J ) 7.9
Hz, CH), 7.17 (1H, t, J ) 7.3 Hz, CH), 7.24-7.50 (4H, m, CH),
7.58 (1H, d, J ) 8.0 Hz, CH), 7.96 (1H, d, J ) 7.7 Hz, CH), 8.06
(2H, m, CH), 8.32 (1H, d, J ) 8.1 Hz, CH), 10.3 (1H, s, NH); 13
C
NMR δ 111.5, 113.2 (CH), 115.2 (C), 120.1, 120.8 (CH), 121.1
(C), 126.7 (CH), 127.6 (CH) × 2, 128.7 (CH), 129.0 (CH) × 2,
129.2 (CH), 138.9, 140.2, 152.4, 154.5 (C); IR 3128, 2927, 1602,
1442 cm-1; HRMS (CI+) calcd for C17H13N2 245.1079, found
245.1080.
2,6-Dimethyl-9H-pyrido[2,3-b]indole (8c): Solid; ca. 49%
6H-1,2,3,4-Tetrahydroindolo[2,3-b]quinoline (10):20 White
solid, 45%; mp 220-221 °C; 1H NMR (400 MHz, CDCl3) δ
1.79-1.98 (4H, m, CH2), 2.90 (2H, t, J ) 6.11 Hz, CH2), 3.10
(2H, t, J ) 6.5 Hz, CH2), 7.16 (1H, t, J ) 7.4 Hz, CH), 7.36 (1H,
t, J ) 7.5 Hz, CH), 7.43 (1H, d, J ) 8.1 Hz, CH), 7.91 (1H, d, J
) 7.7 Hz, CH), 7.96 (1H, s, CH), 10.20 (1H, s, NH); 13C NMR δ
22.2 (CH2 × 2), 28.0, 31.7 (CH2), 110.2 (CH), 113.9 (C), 118.8,
119.6 (CH), 120.1, 122.8 (C), 125.4, 128.5 (CH), 137.9. 149.4,
152.5 (C); IR 2931, 1609, 1458 cm-1; HRMS (CI+) calcd for
C15H15N2 223.1235, found 223.1231.
1
(could not be separated from byproduct by chromatography); H
NMR (400 MHz, CDCl3) δH 2.59 (3H, s, CH3), 2.76 (3H, s, CH3),
6.86 (1H, d, J ) 7.3 Hz, CH), 7.10 (2H, m, CH), 7.48 (1H, m,
CH), 8.01 (1H, m, CH), 11.4 (1H, s, NH).
6-Bromo-2-methyl-9H-pyrido[2,3-b]indole (8d): White solid,
1
40%; mp 233-235 °C; H NMR (400 MHz, CDCl3) δ 2.64 (3H,
s, CH3), 7.16 (1H, d, J ) 7.9 Hz, CH), 7.48 (1H, d, J ) 8.4 Hz,
CH), 7.57 (1H, dd, J ) 8.6, 1.9 Hz, CH), 8.40 (1H, d, J ) 1.8 Hz,
CH), 8.47 (1H, d, J ) 7.8 Hz, CH), 11.8 (1H, s, NH); 13C NMR δ
25.0 (CH3), 113.5, 115.5 (CH), 122.7 (C), 123.7 (CH), 127.3 (C),
128.6, 129.7 (CH), 137.2, 145.9, 152.0, 156.1 (C); IR 3128, 2931,
Biphenyl-2-carbonitrile (23):21 White solid, 97%; mp 35-37
1
°C; H NMR (400 MHz, CDCl3) δ 7.44-7.55 (7H, m, CH), 7.65
1607, 1455 cm-1
.
(1H, dt, J ) 1.3, 7.7 Hz, CH), 7.77 (1H, dd, J ) 1.1, 7.7 Hz, CH);
13C NMR δ 111.4, 118.5 (C), 127.7 (CH), 128.8 (CH × 2), 128.8
(CH), 129.9 (CH × 2), 130.2, 132.9, 133.8 (CH), 138.1, 145.3 (C).
6-Bromo-2,4-dimethyl-9H-pyrido[2,3-b]indole (8e): White solid,
1
39%; mp 244-246 °C; H NMR (400 MHz, CDCl3) δ 2.63 (3H,
s, CH3), 2.73 (3H, s, CH3), 6.91 (1H, s, CH), 7.42 (1H, d, J ) 8.5
Hz, CH), 7.52 (1H, dd, J ) 8.6, 3.0 Hz, CH), 8.14 (1H, d, J ) 1.8
Hz, CH), 11.8 (1H, s, NH); 13C NMR δ 19.4, 24.2 (CH3), 110.7
(CH), 111.2 (C), 112.9 (CH), 116.8 (C), 122.7 (CH), 124.2 (C),
127.8 (CH), 137.0, 142.4, 151.9, 155.7 (C); IR 3147, 2948, 1633,
1458 cm-1; HRMS (ES) calcd for C13H12N279Br 275.0184, found
275.0183.
Acknowledgment. We thank EaStChem for financial support.
Supporting Information Available: Experimental proce-
dures for carbonyl compounds, oximes, and oxime esters. Full
spectroscopic data for new compounds. This material is available
2-Methyl-9H-pyrido[2,3-b]indole-6-carbonitrile (8f): Solid; ca.
37% (could not be separated from byproduct by chromatography);
1H NMR (400 MHz, CDCl3) δH 2.71 (3H, s, CH3), 7.26 (1H, d, J
) 7.1 Hz, CH), 7.67 (1H, d, J ) 8.5 Hz, CH), 7.84 (1H, d, J )
8.5, 1.7 Hz, CH), 8.56 (1H, dd, J ) 7.8 Hz, CH), 8.75 (1H, m,
CH), 12.3 (1H, s, NH).
JO801751A
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H. J. Org. Chem. 2004, 69, 5760–5762.
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J. Org. Chem. Vol. 73, No. 20, 2008 8127