9422
S.-L. Wang et al. / Tetrahedron 67 (2011) 9417e9425
1595, 1567, 1508, 1491, 1412, 1387, 1357, 1220, 1157, 1143, 1104, 1014,
839, 764, 694, 645. 1H NMR (400 MHz, DMSO-d6) (
, ppm): 8.23 (d,
ArH), 7.08 (d, J¼8.4 Hz, 2H, ArH), 3.84 (s, 3H, OCH3), 3.80 (s, 2H,
CH2), 3.55 (t, J¼6.0 Hz, 2H, CH2), 3.01 (t, J¼6.0 Hz, 2H, CH2), 2.74 (s,
d
J¼8.0 Hz, 2H, ArH), 7.67e7.63 (m, 2H, ArH), 7.51 (t, J¼8.0 Hz, 2H,
ArH), 7.36 (t, J¼8.8 Hz, 2H, ArH), 7.27 (t, J¼7.2 Hz, 1H, ArH), 3.76 (s,
2H, CH2), 3.59e3.56 (m, 2H, CH2), 3.01 (t, J¼6.0 Hz, 2H, CH2), 2.74 (s,
3H, CH3). 13C NMR (400 MHz, CDCl3) (
d, ppm): 159.9, 157.7, 149.4,
142.0, 141.8,139.8,132.6,130.8,128.9, 125.1,122.7,120.6, 114.6,113.7,
55.4, 28.1, 27.7, 25.7, 16.1. HRMS (ESI): m/z calcd for: C23H22N3OS,
388.1478, found: 388.1476.
3H, CH3). 13C NMR (400 MHz, CDCl3) (
d
, ppm): 162.9 (1JCF¼246.4),
156.9, 149.3, 142.2, 141.9, 139.6, 136.2 (4JCF¼3.2 Hz), 131.2
(3JCF¼8.2 Hz), 129.0, 125.3, 122.6, 120.6, 115.3 (2JCF¼21.4 Hz), 114.9,
113.2, 27.9, 27.7, 25.6, 16.1. HRMS (ESI): m/z calcd for: C22H19FN3S,
376.1278, found: 376.1278.
4.2.22. 5-(2,3-Dimethoxyphenyl)-1-methyl-3-phenyl-3,6,8,9-
tetrahydropyrazolo[3,4-b]thiopyrano[4,3-d]pyridine
solid, mp: 200e202 ꢀC. IR (KBr, , cmꢁ1): 3077, 2930, 2835, 1597,
1573, 1506, 1474, 1413, 1384, 1359, 1288, 1268, 1230, 1130, 1077,
1062, 1004, 757, 693. 1H NMR (400 MHz, DMSO-d6) (
, ppm): 8.22
4w. White
n
4.2.17. 5-(4-Bromophenyl)-1-methyl-3-phenyl-3,6,8,9-
d
tetrahydropyrazolo[3,4-b]thiopyrano[4,3-d]pyridine 4r. White solid,
(d, J¼8.0 Hz, 2H, ArH), 7.49 (t, J¼8.0 Hz, 2H, ArH), 7.24 (t, J¼7.2 Hz,
1H, ArH), 7.20e7.19 (m, 2H, ArH), 6.86e6.84 (m, 1H, ArH), 3.88 (s,
3H, OCH3), 3.57 (t, J¼6.0 Hz, 2H, CH2), 3.54 (s, 3H, OCH3), 3.50 (s, 2H,
CH2), 3.05e2.95 (m, 2H, CH2), 2.75 (s, 3H, CH3). 13C NMR (400 MHz,
mp: 206e207 ꢀC. IR (KBr, , cmꢁ1): 2996, 2888, 1588, 1576, 1506,
n
1489, 1417, 1382, 1103, 1009, 836, 756, 693. 1H NMR (400 MHz,
DMSO-d6) (
d
, ppm): 8.24 (d, J¼8.0 Hz, 2H, ArH), 7.74 (d, J¼7.6 Hz,
2H, ArH), 7.57 (d, J¼7.6 Hz, 2H, ArH), 7.51 (t, J¼7.6 Hz, 2H, ArH), 7.27
(t, J¼7.6 Hz, 1H, ArH), 3.78 (s, 2H, CH2), 3.58 (m, 2H, CH2), 3.03 (m,
CDCl3) (d, ppm): 155.9, 152.8, 149.2, 146.6, 141.9, 141.0, 139.8, 135.0,
128.9, 125.1, 124.3, 123.5, 122.3, 120.6, 115.2, 112.5, 61.4, 55.9, 27.9,
27.1, 25.4, 16.1. HRMS (ESI): m/z calcd for: C24H24N3O2S, 418.1584,
found: 418.1569.
2H, CH2), 2.76 (s, 3H, CH3). 13C NMR (400 MHz, CDCl3) (
d, ppm):
156.7, 149.3, 142.4, 141.9, 139.6, 139.1, 131.5, 131.1, 131.0, 129.0, 125.3,
122.9, 122.5, 120.6, 115.0, 27.9, 27.7, 25.6, 16.1. HRMS (ESI): m/z calcd
for: C22H19BrN3S, 436.0477, found: 436.0465.
4.2.23. 1-Methyl-3-phenyl-5-(3,4,5-trimethoxyphenyl)-3,6,8,9-
tetrahydropyrazolo[3,4-b]thiopyrano[4,3-d]pyridine 4x. White solid,
4. 2.18. 1-Methyl-5-(4-nitrophenyl)-3-phenyl-3, 6, 8, 9-
mp: 230e231 ꢀC. IR (KBr, , cmꢁ1): 2990, 2888, 1587, 1576, 1507,
n
tetrahydropyrazolo[3,4-b]thiopyrano[4,3-d]pyridine 4s. Yellow solid,
1413, 1371, 1288, 1230, 1126, 1017, 751, 696. 1H NMR (400 MHz,
DMSO-d6) (
mp: 206e207 ꢀC. IR (KBr,
n
, cmꢁ1): 3070, 2900, 1597, 1569, 1523,
d
, ppm): 8.27 (d, J¼8.0 Hz, 2H, ArH), 7.52 (d, J¼7.6 Hz,
1507, 1438, 1417, 1348, 757. 1H NMR (400 MHz, DMSO-d6) (
d
, ppm):
2H, ArH), 7.27 (t, J¼7.2 Hz, 1H, ArH), 6.85 (s, 2H, ArH), 3.83 (s, 6H,
OCH3), 3.82e3.80 (m, 2H, CH2), 3.74 (s, 3H, OCH3), 3.58 (t, J¼6.0 Hz,
2H, CH2), 3.02 (t, J¼6.0 Hz, 2H, CH2), 2.76 (s, 3H, CH3). 13C NMR
8.37 (d, J¼8.4 Hz, 2H, ArH), 8.23 (d, J¼8.0 Hz, 2H, ArH), 7.90 (d,
J¼8.4 Hz, 2H, ArH), 7.51 (t, J¼7.6 Hz, 2H, ArH), 7.27 (t, J¼7.2 Hz, 1H,
ArH), 3.79 (s, 2H, CH2), 3.61 (t, J¼6.0 Hz, 2H, CH2), 3.04 (t, J¼6.0 Hz,
(400 MHz, CDCl3) (d, ppm): 157.7, 153.1, 149.2, 142.3, 141.9, 139.7,
2H, CH2), 2.78 (s, 3H, CH3). 13C NMR (400 MHz, DMSO-d6) (
d, ppm):
138.5, 135.6, 129.0, 125.2, 122.6, 120.6, 114.8, 106.7, 61.0, 56.3, 27.9,
27.7, 25.6, 16.1. HRMS (ESI): m/z calcd for: C25H26N3O3S, 448.1689,
found: 448.1651.
155.2, 148.4,147.4, 146.1,143.6, 142.6, 139.0, 131.9,130.7,129.1, 125.3,
123.5, 122.8, 120.0, 115.2, 112.7, 27.2, 27.0, 24.5, 15.6. HRMS (ESI): m/
z calcd for: C22H19N4O2S, 403.1223, found: 403.1217.
4.2.24. 2-Methoxy-4-(1-methyl-3-phenyl-3,6,8,9-tetrahydropyrazolo
4.2.19. 4-(1-Methyl-3-phenyl-3,6,8,9-tetrahydropyrazolo[3,4-b]thio-
pyrano[4,3-d]pyridin-5-yl)-2-nitrophenol 4t. Yellow solid, mp:
[3,4-b]thiopyrano[4,3-d]pyridin-5-yl)phenol 4y. Gray white solid,
mp: 193e194 ꢀC. IR (KBr, , cmꢁ1): 3382, 3005, 2895, 2835, 1596,
n
199e200 ꢀC. IR (KBr,
n
, cmꢁ1): 3243, 3076, 2930, 2899, 1630, 1582,
1563, 1517, 1506, 1414, 1290, 1262, 1197, 1141, 1029, 819, 761, 693. 1H
NMR (400 MHz, DMSO-d6) ( , ppm): 9.38 (s, 1H, OH), 8.29 (d,
1539, 1509, 1417, 1356, 1320, 1289, 1178, 837, 756, 691, 649. 1H NMR
(400 MHz, DMSO-d6) (
d
d, ppm): 11.38 (s, 1H, OH), 8.24 (d, J¼8.0 Hz,
J¼8.0 Hz, 2H, ArH), 7.51 (t, J¼8.0 Hz, 2H, ArH), 7.26 (t, J¼7.2 Hz, 1H,
ArH), 7.16 (s, 1H, ArH), 7.04e7.01 (m, 1H, ArH), 6.90 (d, J¼8.0 Hz, 1H,
ArH), 3.84 (s, 2H, CH2), 3.83 (s, 2H, OCH3), 3.55 (t, J¼6.0 Hz, 2H,
CH2), 3.02 (t, J¼6.0 Hz, 2H, CH2), 2.74 (s, 3H, CH3). 13C NMR
2H, ArH), 8.10 (d, J¼2.0 Hz, 1H, ArH), 7.80 (dd, J1¼2.0 Hz, J2¼8.4 Hz,
1H, ArH), 7.51 (t, J¼7.6 Hz, 2H, ArH), 7.28e7.25 (m, 2H, ArH), 3.82 (s,
2H, CH2), 3.56 (t, J¼6.0 Hz, 2H, CH2), 3.01 (t, J¼6.0 Hz, 2H, CH2), 2.74
(s, 3H, CH3). 13C NMR (400 MHz, CDCl3) (
d, ppm): 155.1, 154.7, 149.2,
(400 MHz, DMSO-d6) (d, ppm): 157.6, 148.6147.2, 147.2, 142.7, 142.3,
142.7, 142.0, 139.5, 138.6, 133.2, 132.6, 129.1, 125.9, 125.5, 122.4,
120.5, 120.1, 115.2, 28.0, 27.7, 25.5, 16.1. HRMS (ESI): m/z calcd for:
C22H19N4O3S, 419.1172, found: 419.1171.
139.3, 130.8, 129.0, 125.0, 122.9, 122.1, 119.7, 115.1, 114.2, 113.5, 68.5,
55.7, 30.7, 27.4, 27.2, 24.7, 15.6. HRMS (ESI): m/z calcd for:
C23H22N3O2S, 404.1427, found: 404.1388.
4.2.20. 1-Methyl-3-phenyl-5-p-tolyl-3,6,8,9-tetrahydropyrazolo[3,4-
4. 2. 25. 1-Methyl-3-phenyl-5-(thiophen-2-yl)-3,6,8,9-
b]thiopyrano[4,3-d]pyridine 4u. Gray solid, mp: 198e199 ꢀC. IR
tetrahydropyrazolo[3,4-b]thiopyrano[4,3-d]pyridine 4z. Gray yellow
(KBr,
n
, cmꢁ1): 3067, 2920, 1595, 1567, 1506, 1415, 1383, 1353, 1275,
solid, mp: 164e165 ꢀC. IR (KBr, , cmꢁ1): 3067, 2893, 1600, 1568,
n
1141, 1018, 829, 759, 695, 684. 1H NMR (400 MHz, DMSO-d6) (
d
,
1506, 1442, 1416, 1384, 1358, 1291, 1237, 1137, 751, 708, 695. 1H NMR
(400 MHz, DMSO-d6) (
ppm): 8.26 (d, J¼8.0 Hz, 2H, ArH), 7.49 (d, J¼8.0 Hz, 4H, ArH), 7.35
(d, J¼7.6 Hz, 2H, ArH), 7.26 (d, J¼7.6 Hz, 1H, ArH), 3.78 (s, 2H, CH2),
3.57 (t, J¼6.4 Hz, 2H, CH2), 3.03 (t, J¼6.0 Hz, 2H, CH2), 2.76 (s, 3H,
d
, ppm): 8.33 (d, J¼8.0 Hz, 2H, ArH), 7.79 (d,
J¼4.8 Hz, 1H, ArH), 7.62 (d, J¼3.6 Hz, 1H, thienyleH), 7.54 (t,
J¼7.6 Hz, 2H, ArH), 7.28 (t, J¼3.6 Hz, 1H, thienyleH), 7.23 (t,
J¼4.0 Hz, 1H, thienyleH), 4.10 (s, 2H, CH2), 3.56 (t, J¼6.0 Hz, 2H,
CH2), 3.01 (t, J¼6.0 Hz, 2H, CH2), 2.70 (s, 3H, CH3). 13C NMR
CH3), 2.41 (s, 3H, CH3). 13C NMR (400 MHz, CDCl3) (
d, ppm): 158.1,
149.4,141.9,141.8,139.8,138.4,137.4,129.3,129.0,128.9,125.1,122.7,
120.6, 114.7, 28.0, 27.8, 25.6, 21.4, 16.1. HRMS (ESI): m/z calcd for:
C23H22N3S, 372.1529, found: 372.1526.
(400 MHz, CDCl3) (d, ppm): 150.6, 148.8, 144.2, 142.2, 142.0, 139.6,
129.0, 128.4, 128.3, 127.5, 125.2, 121.6, 120.3, 114.9, 28.4, 28.3, 25.2,
16.1. HRMS (ESI): m/z calcd for: C20H18N3S2, 364.0936, found:
364.0960.
4.2.21. 5-(4-Methoxyphenyl)-1-methyl-3-phenyl-3,6,8,9-
tetrahydropyrazolo[3,4-b]thiopyrano[4,3-d]pyridine 4v. White solid,
mp: 164e165 ꢀC. IR (KBr,
n
, cmꢁ1): 2975, 2914, 2836, 1589, 1505,
4.2.26. 5-(4-Bromophenyl)-2,6,8,9-tetrahydropyrazolo[3,4-b]thio-
1407, 1367, 1301, 1250, 1170, 1108, 1033, 836, 757, 680. 1H NMR
(400 MHz, DMSO-d6) (
, ppm): 8.27 (d, J¼7.6 Hz, 2H, ArH), 7.56 (d,
J¼8.4 Hz, 2H, ArH), 7.50 (t, J¼7.6 Hz, 2H, ArH), 7.25 (t, J¼7.2 Hz, 1H,
pyrano[4,3-d]pyridin-1-ol 4aa. Pink solid, mp: >300 ꢀC. IR (KBr,
n,
d
cmꢁ1): 3096, 2922, 1595, 1539, 1490, 1402, 1270, 1209, 1146, 1013,
829, 628. 1H NMR (400 MHz, DMSO-d6) (
, ppm): 11.99 (s, 1H, NH),
d