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accelerative voltage of 8 kV. Samples were introduced
by the standard direct insertion probe. High-resolution
data were obtained with the instrument using 10,000
resolution.
J = 6.0 Hz); 8.55; (s); 7.35–7.08 (m); 6.99 (s); 13C
NMR (CDCl3, d in ppm) 122.1, 120.1, 119.5, 147.8,
91.7, 149.2, 166.5, 135.0, 140.2, 116.7; EI (70 eV) m/z
(%): M+Å 285.01268 (100), 249.04243 (29).
General procedure: 4-(Phenylamino)thieno[2,3-b]pyri-
dine-5-carbonitrile (1–7 and 2a–7a)
4.1.7. (7) 4-(30-Bromophenylamino)thieno[2,3-b]pyridine-
5-carbonitrile. Yield: 81%; mp: 162 ꢁC; Rf = 0.43; IV
(KBr, cmꢀ1): (m NH 3271, m CN 2213); 1H NMR
(CDCl3, d in ppm) 7.30 (d, J = 6.0 Hz); 6.55 (d,
J = 6.0 Hz); 8.55; (s); 7.46–7.12 (m); 7.04 (s); 13C
NMR (CDCl3, d in ppm) 122.1, 119.8, 119.2, 147.5,
91.3, 148.8, 166.1, 122.4, 140.0, 116.0; EI (70 eV) m/z
(%): M+Å 330.96160 (100), 249.05335 (69).
Equimolar (5 mmol) amounts of 4-chlorothieno[2,3-
b]pyridine-5-carbonitrile and the appropriate aniline
were heated in a silicone oil bath at 140 ꢁC for 2 h.
The mixture was diluted with CH2Cl2 and purified by
preparative silica gel plates (Glass Backed TLC Silica
Gel, Hard Layer 250 lm, F-254), eluent CH2Cl2.
4.1.8. (2a) 4-(40-Methylphenylamino)thieno[2,3-b]pyri-
dine-5-carbonitrile. Yield: 92%, mp: 215 ꢁC; Rf = 0.47;
4.1.1. (1) 4-(Phenylamino)thieno[2,3-b]pyridine-5-carbo-
nitrile. Yield: 82%, mp: 176 ꢁC; Rf = 0.41; IR (KBr,
1
IR (KBr, cmꢀ1): (m NH 3303, m CN 2209); H NMR
1
cmꢀ1): (m NH 3283, m CN 2219); H NMR (CDCl3, d
(CDCl3, d in ppm) 7.84 (d, J = 6.0 Hz); 7.54 (d,
J = 6.0 Hz); 8.53 (s); 7.34 (d, J = 8.9 Hz); 7.28 (d,
J = 8.9 Hz); 9.70 (s); 2.45 (s); 13C NMR (CDCl3, d in
ppm) 130.1, 125.5, 118.7, 149.3, 90.2, 149.2, 166.5,
124.0, 120.5, 137.3, 136.0, 21.0, 116.7; EI (70 eV) m/z
(%): M+Å 265.06671 (100).
in ppm) 7.84 (d, J = 6.0 Hz), 7.39 (d, J = 6.0 Hz), 8.56
(s), 7.56–7.50 (m); 9.69 (s); 13C NMR (CDCl3, d in
ppm) 125.6, 125.9, 121.2, 148.4, 89.2, 151.4, 164.4,
129.1, 124.4, 139.2, 120.2, 116.7; EI (70 eV) m/z (%):
M+Å 251.05155 (100).
4.1.2. (2) 4-(30-Methylphenylamino)thieno[2,3-b]pyridine-
5-carbonitrile. Yield: 74%; mp: 185 ꢁC; Rf = 0.42; IR
(KBr, cmꢀ1): (m NH 3275, m CN 2221); 1H NMR
(CDCl3, d in ppm) 7.18 (d, J = 6.0 Hz); 6.42 (d,
J = 6.0 Hz); 8.48 (s); 7.30–7.05 (m); 2.35 (s); 13C NMR
(CDCl3, d in ppm) 122.1, 120.3, 119.0, 148.8, 90.5,
149.2, 166.4, 139.6, 138.6, 129.2, 127.7, 125.6, 124.1;
EI (70 eV) m/z (%): M+Å 265.06760 (100).
4.1.9. (3a) 4-(40-Methoxyphenylamino)thieno[2,3-b]pyri-
dine-5-carbonitrile. Yield: 73%, mp: 164 ꢁC; Rf = 0.34;
1
IR (KBr, cmꢀ1): (m NH 3296, m CN 2210); H NMR
(CDCl3, d in ppm) 7.15 (d, J = 6.0 Hz); 6.30 (d,
J = 6.0 Hz); 8.45 (s); 7.21 (d, J = 8.9 Hz); 6.96 (d,
J = 8.9 Hz); 3.87 (s); 13C NMR (CDCl3, d in ppm)
123.9, 120.3, 118.3, 149.1, 89.5, 149.9, 166.4, 127.9,
114.7, 131.2, 158.9, 55.4, 116.7; EI (70 eV) m/z (%):
M+Å 281.068282 (5), 265.05807 (100), 237.06463 (23).
4.1.3. (3) 4-(30-Methoxyphenylamino)thieno[2,3-b]pyri-
dine-5-carbonitrile. Yield: 77%; mp: 174 ꢁC; Rf = 0.34;
4.1.10. (4a) 4-(40-Nitrophenylamino)thieno[2,3-b]pyri-
dine-5-carbonitrile. Yield: 70%, mp: 104 ꢁC; Rf = 0.27;
1
IV (KBr, cmꢀ1): (m NH 3267, m CN 2212); H NMR
1
(CDCl3, d in ppm) 7.85 (d, J = 6.0 Hz); 7.57 (d,
J = 6.0 Hz); 8.58; (s); 7.45–6.92 (m); 9.76 (s); 3.15 (s);
13C NMR (CDCl3, d in ppm) 122.0, 120.9, 117.4,
151.9, 90.3, 160.5, 165.1, 55.9, 116.9; EI (70 eV) m/z
(%): M+Å 281.06251 (100).
IR (KBr, cmꢀ1): (m NH 3249, m CN 2218); H NMR
(CDCl3, d in ppm) 8.11 (d, J = 6.0 Hz); 7.82 (d,
J = 6.0 Hz); 8.86 (s); 8.28–7.93 (m); 13C NMR (CDCl3,
d in ppm) 129.9, 128.2, 122.2, 147.8, 90.8, 150.5, 164.1,
140.7, 146.9, 116.1; EI (70 eV) m/z (%): M+Å 296.03720
(100), 249.01103 (27).
4.1.4. (4) 4-(30-Nitrophenylamino)thieno[2,3-b]pyridine-5-
carbonitrile. Yield: 87%; mp: 227 ꢁC; Rf = 0.28; IV (KBr,
4.1.11. (5a) 4-(40-Fluorophenylamino)thieno[2,3-b]pyri-
dine-5-carbonitrile. Yield: 72%; mp: 209 ꢁC; Rf = 0.42;
1
cmꢀ1): (m NH 3360, m CN 2219); H NMR (CDCl3, d in
1
ppm) 7.40 (d, J = 6.0 Hz); 6.63 (d, J = 6.0 Hz); 8.62; (s);
8.14–7.39 (m); 7.10 (s); 13C NMR (CDCl3, d in ppm)
120.2, 120.3, 146.7, 93.0, 149.2, 140.5, 117.4; EI
(70 eV) m/z (%): M+Å 296.03661 (100), 249.04856 (58).
IV (KBr, cmꢀ1): (m NH 3332, m CN 2214); H NMR
(CDCl3, d in ppm) 7.22 (d, J = 6.0 Hz); 6.35 (d,
J = 6.0 Hz); 8.50; (s); 7.23 (dd, J = 9.0, 4.5 Hz); 7.16
(dd, J = 9.0, 8.1 Hz); 13C NMR (CDCl3, d in ppm)
124.4, 119.7, 118.4, 148.8, 90.1, 148.9, 166.3, 127.3
(d, 8.6), 116.3 (d, 22.9), 134.4 (d, 3.0), 161.1 (d,
246.0), 116.3; EI (70 eV) m/z (%): M+Å 268.06669
(100).
4.1.5. (5) 4-(30-Fluorophenylamino)thieno[2,3-b]pyridine-
5-carbonitrile. Yield: 92%; mp: 183 ꢁC; Rf = 0.40; IV
(KBr, cmꢀ1): (m NH 3277, m CN 2219); 1H NMR
(CDCl3, d in ppm) 7.30 (d, J = 6.0 Hz); 6.56 (d,
J = 6.0 Hz); 8.55; (s); 7.42–6.90 (m); 13C NMR (CDCl3,
d in ppm) 125.2, 120.2, 147.8, 91.7, 149.2, 166.5, 163.0
(d, 247.0), 130.7(d, 9.0), 140.6 (d, 9.7), 116.3; EI
(70 eV) m/z (%): M+Å 269.04214 (100).
4.1.12. (6a) 4-(40-Chlorophenylamino)thieno[2,3-b]pyri-
dine-5-carbonitrile. Yield: 96%, mp: 236 ꢁC; Rf = 0.48;
1
IR (KBr, cmꢀ1): (m NH 3295, m CN 2211); H NMR
(CDCl3, d in ppm) 7.27 (d, J = 6.0 Hz); 6.47 (d,
J = 6.0 Hz); 8.53 (s); 7.40 (d, J = 8.7 Hz); 7.16 (d,
J = 8.7 Hz); 6.99 (s); 13C NMR (CDCl3, d in ppm)
125.4, 120.6, 119.5, 148.7, 91.7, 149.6, 126.3, 130.1,
132.7, 137.9, 116.9; EI (70 eV) m/z (%): M+Å 285.01119
(100), 249.04793 (22).
4.1.6. (6) 4-(30-Chlorophenylamino)thieno[2,3-b]pyridine-
5-carbonitrile. Yield: 74%; mp: 169 ꢁC; Rf = 0.42; IV
(KBr, cmꢀ1): (m NH 3275, m CN 2220); 1H NMR
(CDCl3, d in ppm) 7.09 (d, J = 6.0 Hz); 6.54 (d,