Synthesis of Thiochromeno[2,3-b]pyridines
J ) 7.45, 7.60 Hz, 1H, 3-H), 7.40-8.28 (m, 17H, Ar-H), 8.43 (d,
J ) 7.45 Hz, 1H, N-H); 13C NMR (DMSO-d6, 125 MHz) δ 41.19,
53.58, 115.94, 124.32 127.34, 128.19, 128.73, 129.83, 129.89,
130.42, 130.65, 130.81, 132.08, 132.49, 132.56, 133.63, 134.00,
136.19, 144.86, 144.48, 152.72, 167.38, 167.66, 176.48; IR (KBr)
136.34, 150.86 166.76, 167.62, 177.13; IR (KBr) ν 3412, 3059,
3030, 1702, 1664, 1616, 1578, 1365, 751, 721, 694 cm-1; MS (ESI)
m/z 503.2 [M + H]+. Anal. Calcd for C31H22N2O3S: C, 74.08; H,
4.41; N, 5.57. Found: C, 73.99, H, 4.39; N, 5.25.
6s: yellow crystal; yield 58%; mp 198-200 °C; 1H NMR
(DMSO-d6, 500 MHz) δ 5.03 (d, J ) 7.40 Hz, 1H, 4-H), 5.71 (t,
J ) 7.30, 7.30 Hz, 1H, 3-H), 6.73-7.86 (m, 17H, Ar-H), 8.28 (d,
J ) 6.70 Hz, 1H, N-H); 13C NMR (DMSO-d6, 125 MHz) δ 39.96,
53.70, 116.97, 121.44, 123.58, 127.08, 127.63, 127.83, 128.14,
128.30, 130.05, 130.22, 131.55, 132.00, 133.75, 135.96, 146.62,
147.42, 150.67, 166.74, 167.65, 177.10; IR (KBr) ν 3425, 3066,
1705, 1661, 1616, 1590, 1235, 758, 723, 695 cm-1; MS (ESI) m/z
547.3 [M + H]+. Anal. Calcd for C32H22N2O5S: C, 70.32; H, 4.06;
N, 5.13. Found: C, 70.39; H, 4.08; N, 5.15.
ν 3411, 3062, 1712, 1697, 1638, 1620, 1223, 817, 732, 697 cm-1
;
MS (ESI) m/z 582.4 [M + H]+. Anal. Calcd for C31H20ClN3O5S:
C, 63.97; H, 3.46; N, 7.22. Found: C, 64.04; H, 3.42; N, 7.19.
6m: yellow crystal; yield 80%; mp 180-182 °C; 1H NMR
(DMSO-d6, 600 MHz) δ 5.40 (d, J ) 7.80 Hz, 1H, 4-H), 5.86 (t,
J ) 7.80, 7.80 Hz, 1H, 3-H), 7.44-8.58 (m, 17H, Ar-H), 8.59 (d,
J ) 7.32 Hz, 1H, N-H); 13C NMR (DMSO-d6, 150 MHz) δ 34.67,
53.11, 115.57, 123.57, 123.67, 125.02, 127.06, 127.80, 128.38,
129.45, 129.53, 129.56, 129.77, 129.82, 130.12, 130.41, 130.57,
130.61, 131.64, 132.18, 132.22, 133.30, 134.00, 136.03, 152.48,
162.20, 167.50, 176.24; IR (KBr) ν 3426, 3063, 1726, 1697, 1654,
1617, 1229, 848, 737, 698 cm-1; MS (ESI) m/z 555.2 [M + H]+.
Anal. Calcd for C31H20ClFN2O3S: C, 67.08; H, 3.63; N, 5.05.
Found: C, 67.01; H, 3.64; N, 5.02
6t: yellow crystal; yield 68%; mp 208-210 °C; 1H NMR
(DMSO-d6, 600 MHz) δ 5.17 (d, J ) 7.80 Hz, 1H, 4-H), 5.88 (t,
J ) 7.32, 7.80 Hz, 1H, 3-H), 7.46-8.26 (m, 18H, Ar-H), 8.46 (d,
J ) 7.38 Hz, 1H, N-H); 13C NMR (DMSO-d6, 150 MHz) δ 39.63,
53.24, 115.68, 124.00, 127.81, 127.93, 128.11, 128.44, 130.04,
133.38, 133.61, 135.94, 144.75, 147.13, 151.86, 167.31, 168.09,
177.28; IR (KBr) ν 3424, 3066, 1713, 1643, 1608, 1578, 1239,
746, 720, 691 cm-1; MS (ESI) m/z 570.6 [M + Na]+. Anal. Calcd
for C31H21N3O5S: C, 68.00; H, 3.87; N, 7.67. Found: C, 68.08;
H, 3.89; N, 7.65.
6n: yellow crystal; yield 75%; mp 195-198 °C; 1H NMR
(DMSO-d6, 500 MHz) δ 5.09 (d, J ) 7.35 Hz, 1H, 4-H), 5.71 (t,
J ) 7.05, 7.15 Hz, 1H, 3-H), 7.15-8.18 (m, 17H, Ar-H), 8.23 (d,
J ) 8.10 Hz, 1H, N-H); 13C NMR (DMSO-d6, 125 MHz) δ 40.48,
54.18, 117.61, 126.88, 127.35, 128.08, 128.77, 128.82, 128.91,
129.62, 129.78, 130.32, 130.68, 130.80, 130.93, 132.07, 133.50,
134.20, 135.49, 136.32, 136.69, 137.08, 137.46, 151.16, 167.23,
168.14, 176.22; IR (KBr) ν 3427, 3074, 1721, 1655, 1622, 1600,
1528, 1267, 832, 737, 692 cm-1; MS (ESI) m/z 571.2 [M + H]+.
Anal. Calcd for C31H20Cl2N2O3S: C, 65.15; H, 3.53; N, 4.90.
Found: C, 65.17; H, 3.54; N, 4.87.
6u: yellow crystal; yield 71%; mp 253-255 °C; 1H NMR
(DMSO-d6, 500 MHz) δ 5.42 (d, J ) 7.85 Hz, 1H, 4-H), 5.86 (t,
J ) 7.65, 7.70 Hz, 1H, 3-H), 7.13-8.26 (m, 18H, Ar-H), 8.53 (d,
J ) 7.50 Hz, 1H, N-H); 13C NMR (DMSO-d6, 125 MHz) δ 35.16,
53.86, 116.24, 124.40, 124.53, 125.57, 127.83, 128.42, 128.54,
128.80, 128.89, 130.09, 131.02, 132.10, 132.82, 134.04, 134.74,
136.79, 152.48, 167.76, 168.16, 177.83; IR (KBr) ν 3415, 3060,
1707, 1669, 1615, 1589, 1578, 1546, 1514, 1487, 1362, 1244, 760,
721, 694 cm-1; MS (ESI) m/z 521.2 [M + H]+. Anal. Calcd for
C31H21FN2O3S: C, 71.52; H, 4.07; N, 5.38. Found: C 71.59, H
4.11; N, 5.35.
6o: yellow crystal; yield 71%; mp 244-245 °C; 1H NMR
(DMSO-d6, 500 MHz) δ 2.26 (s, 3H, CH3), 5.10 (d, J ) 7.25 Hz,
1H, 4-H), 5.74 (t, J ) 7.05, 7.20 Hz, 1H, 3-H), 7.14-8.19 (m,
17H, Ar-H), 8.20 (d, J ) 7.10 Hz, 1H, N-H); 13C NMR (DMSO-
d6, 125 MHz) δ 21.09, 40.70, 54.12, 117.41, 127.36, 128.06, 128.74,
128.78, 129.59, 129.84, 129.96, 130.03, 130.79, 130.87, 130.98,
132.04, 132.39, 132.43, 133.50, 134.15, 136.32, 137.06, 151.72,
167.21, 168.11, 176.46; IR (KBr) ν 3435, 3062, 3030, 1721, 1662,
1604, 1568, 1356, 1225, 735, 692 cm-1; MS (ESI) m/z 551.5 [M
+ H]+. Anal. Calcd for C32H23ClN2O3S: C, 69.75; H, 4.21; N,
5.08. Found: C, 69.67, H 4.13; N, 5.16.
6v: yellow crystal; yield 65%; mp 276-280 °C; 1H NMR
(DMSO-d6, 500 MHz) δ 5.60 (d, J ) 7.25 Hz, 1H, 4-H), 5.98 (t,
J ) 7.20, 7.20 Hz, 1H, 3-H), 7.31-8.28 (m, 18H, Ar-H), 8.47 (d,
J ) 7.25 Hz, 1H, N-H); 13C NMR (DMSO-d6, 125 MHz) δ 37.94,
53.68, 117.39, 127.52, 128.28, 128.38, 128.56, 128.62, 129.19,
129.53, 130.27, 130.76, 131.72, 132.53, 133.78, 134.74, 136.55,
152.01 167.73, 167.97, 177.57; IR (KBr) ν 3421, 3060, 1715, 1670,
1614, 1589, 1241, 777, 722, 693 cm-1; MS (ESI) m/z 537.2 [M +
H]+. Anal. Calcd for C31H21ClN2O3S: C, 69.33; H, 3.94; N, 5.22.
Found: C, 69.39; H, 3.98; N, 5.25.
6p: yellow crystal; yield 74%; mp 200-202 °C; 1H NMR
(DMSO-d6, 500 MHz) δ 3.71 (s, 3H, OCH3), 5.06 (d, J ) 7.30
Hz, 1H, 4-H), 5.71 (t, J ) 7.10, 7.15 Hz, 1H, 3-H), 6.89-8.19 (m,
17H, Ar-H), 8.20 (d, J ) 7.55 Hz, 1H, N-H); 13C NMR (DMSO-
d6, 125 MHz) δ 39.48, 54.26, 55.48, 114.61, 117.61, 127.40, 128.11,
128.37, 128.11, 128.37, 128.81, 129.90, 129.96, 130.01, 130.83,
132.06, 132.44, 132.49, 133.53, 134.15, 136.37, 151.65, 159.13,
167.25, 168.18, 176.50; IR (KBr) ν 3400, 3068, 2964, 1723, 1670,
1613, 1512, 1355, 1233, 738, 694 cm-1; MS (ESI) m/z 567.4 [M
+ H]+. Anal. Calcd for C32H23ClN2O4S: C, 67.78; H, 4.09; N,
4.94. Found: C, 67.69, H 4.08; N, 4.93.
6w: yellow crystal; yield 54%; mp 248-250 °C; 1H NMR
(DMSO-d6, 500 MHz) δ 2.25 (s, 3H, CH3), 5.12 (d, J ) 7.80 Hz,
1H, 4-H), 5.72(t, J ) 7.20, 7.20 Hz, 1H, 3-H), 7.14-8.16 (m, 18H,
Ar-H), 8.27 (d, J ) 7.20 Hz, 1H, N-H); 13C NMR (DMSO-d6, 125
MHz) δ 21.73, 39.48, 54.85, 118.14, 128.18, 128.68, 128.95,
129.16, 129.27, 129.39, 129.44, 130.24, 130.36, 130.92, 131.26,
131.33, 131.55, 132.68, 133.10, 134.28, 134.33, 134.84, 137.09,
137.63, 151.78, 167.82, 168.78, 178.20; IR (KBr) ν 3419, 3039,
1719, 1652, 1618, 1576,1545, 1361, 1235, 751, 694 cm-1; MS (ESI)
m/z 517.2 [M + H]+. Anal. Calcd for C32H24N2O3S: C, 74.40; H,
4.68; N, 5.42. Found: C, 74.31; H, 4.64; N, 5.45.
6q: yellow crystal; yield 64%; mp 247-248 °C; 1H NMR
(DMSO-d6, 500 MHz) δ 5.08 (d, J ) 7.45 Hz, 1H, 4-H), 5.77 (t,
J ) 7.30, 7.30 Hz, 1H, 3-H), 7.26-8.28 (m, 18H, Ar-H), 8.40 (d,
J ) 7.15 Hz, 1H, N-H); 13C NMR (DMSO-d6, 125 MHz) δ 40.85,
54.04, 116.86, 127.65, 128.26, 128.38, 128.63, 128.68, 128.84,
129.22, 129.87, 130.38, 130.88, 132.15, 132.64, 133.81, 134.22,
135.97, 136.47, 151.73, 167.38, 168.01, 177.64; IR (KBr) ν 3426,
3065, 2957, 1717, 1657, 1615,1580, 1365, 1238, 796, 718, 693
cm-1; MS (ESI) m/z 537.1 [M + H]+. Anal. Calcd for C31H21-
ClN2O3S: C, 69.33; H, 3.94; N, 5.22. Found: C, 69.44; H, 3.90;
N, 5.25.
6x: yellow crystal; yield 55%; mp 240-242 °C; 1H NMR
(DMSO-d6, 500 MHz) δ 3.71(s,3H,OCH3), 5.08 (d, J ) 7.45 Hz,
1H, 4-H), 5.68 (t, J ) 7.20, 7.20 Hz, 1H, 3-H), 6.89-8.17 (m,
18H, Ar-H), 8.27 (d, J ) 9.00 Hz, 1H, N-H); 13C NMR (DMSO-
d6, 125 MHz) δ 39.49, 54.36, 55.49, 114.60, 127.59, 128.11, 128.34,
128.57, 128.64, 129.98, 130.73, 132.07, 132.50, 133.73, 134.27,
136.55, 151.07, 159.11, 167.23, 168.22, 177.59; IR (KBr) ν
3427, 3033, 1707, 1666, 1616, 1578, 1548, 1357, 1237, 755, 722,
693 cm-1; MS (ESI) m/z 533.2 [M + H]+. Anal. Calcd for
C32H24N2O4S: C, 72.16; H, 4.54; N, 5.26. Found: C 72.24, H 4.58;
N, 5.23.
6r: yellow crystal; yield 62%; mp 266-269 °C; 1H NMR
(DMSO-d6, 500 MHz) δ 5.10 (d, J ) 7.40 Hz, 1H, 4-H), 5.69 (t,
J ) 7.15, 7.10 Hz, 1H, 3-H), 7.21-8.16 (m, 19H, Ar-H), 8.23 (d,
J ) 8.00 Hz, 1H, N-H); 13C NMR (DMSO-d6, 125 MHz) δ 41.39,
53.67, 116.80, 127.09, 127.44, 127.58, 127.83, 128.12, 128.31,
128.41, 128.69, 130.24, 131.57, 132.03, 133.23, 133.72, 135.95
General Procedure for One-Pot Synthesis of Product 9 under
Microwave Irradiation (e.g., 9a). An equimolar mixture of â-(2,4-
J. Org. Chem, Vol. 73, No. 5, 2008 1861