3.3. Characterization Data
3.3.1. Ethyl 4-(5-Bromothiophen-2-yl)-3-methyl-1-phenyl-1H-pyrazolo[3,4-b]pyridine-6-carboxylate (4)
(90%): mp = 203–205 °C: IR (v-cm−1); 2353 (C–H), 1705(C=O), 1258 (C–O), 749 (N–H): 1H-NMR (400 MHz, DMSO): 7.92 (s, 1H, Py–H), 7.00–8.00 (m, 5H, Ph), 8.30 (d, 2H, CH), 4.54 (q, 2H, OCH2), 2.70 (s, 3H, CH3), 1.51 (t, 3H, OCH3): 13C-NMR (126 MHz, DMSO): δ 14.46, 16.08, 62.67, 110.58, 113.85, 112.14, 120.89, 126.43, 128.34, 129.65, 130.38, 135.50, 139.11, 142.87, 144.89, 150.56, 150.99, 165.13: ESI-MS from LC-MS at t = 3.05 min. Calcd. for C20H16BrN3O2S = 441.01, found 442.94.
3.3.2. 4-(5-Bromothiophen-2-yl)-3-methyl-1-phenyl-1H-pyrazolo[3,4-b]pyridine-6-carbohydrazide (5)
(86%): mp = 265 °C: IR (v-cm−1): 2921 (C–H), 1653 (C=O), 3229 (NH2), 666 (NH), 1505 (amide): 1H-NMR (400 MHz, DMSO): 10.00 (s, 1H, NH), 7.20–8.00 (m, 5H, Ph), 8.27 (d, 1H, CH), 8.25 (d, 1H, CH) 4.75 (s, 2H, NH2), 2.57 (s, 3H, CH3):13C-NMR (126 MHz, DMSO) δ14.97, 110.47, 112.12, 112.64, 120.62, 126.24, 128.08, 129.69, 130.15, 139.32, 140.09, 143.10, 145.33, 150.48, 150.66, 164.66: ESI-MS from LC-MS at t = 3.36 min. Calcd. for C18H14BrN5OS = 427.01, found 429.9.
3.3.3. Ethyl 4-([2,2′-Bithiophen]-5-yl)-3-methyl-1-phenyl-1H-pyrazolo[3,4-b]pyridine-6-carboxylate (6a)
(70%): mp = 154–157 °C: 1H-NMR (400 MHz, CDCl3): 1.52 (t, 3H, OCH3), 2.78 (s, 3H, CH3), 4.56 (q, 2H, OCH2), 8.01 (s, 1H, Py–H), 7.00–7.80 (m, 5H, Ph), 7.9–8.9 (m, 5H, CH): 13C-NMR (101 MHz, CDCl3): δ 165.58, 151.64, 151.35, 145.10, 142.89, 139.41, 138.84, 136.87, 134.55, 129.14, 127.95, 125.92, 125.20, 124.37, 123.60, 123.20, 121.20, 113.88, 112.26, 62.40, 16.50, 14.47: ESI-MS from LC-MS at t = 3.79 min. Calcd. for C24H19N3O2S2 = 445.09, found 446.0.
3.3.4. Ethyl 3-Methyl-1-phenyl-4-(5-phenylthiophen-2-yl)-1H-pyrazolo[3,4-b]pyridine-6-carboxylate (6b)
(72%): mp = 171 °C: 1H-NMR (400 MHz, CDCl3): 1.52 (t, 3H, OCH3), 2.78 (s, 3H, CH3), 4.56 (q, 2H, OCH2), 8.04 (s, 1H, Py–H), 7.00–8.00 (m, 10H, Ph), 8.36 (d, 2H, CH): 13C-NMR (101 MHz, CDCl3): δ 165.47, 151.53, 144.90, 143.51, 142.76, 139.31, 135.49, 134.37, 129.00, 128.93, 127.53, 126.32, 125.75, 125.44, 123.93, 121.06, 113.78, 112.04, 62.23, 16.38, 14.34: ESI-MS from LC-MS at t = 3.79 min. Calcd. for C26H21N3O2S = 439.01, found 440.1.
3.3.5. Ethyl 4-(5-(Benzo[d][1,3]dioxol-4-yl)thiophen-2-yl)-3-methyl-1-phenyl-1H-pyrazolo[3,4-b]pyridine-6-carboxylate (6c)
(60%): mp = 127 °C: 1H-NMR (400 MHz, CDCl3): 1.52 (t, 3H, OCH3), 2.78 (s, 3H, CH3), 4.55 (q, 2H, OCH2), 6.01 (s, 2H, CH2), 8.04 (s, 1H, Py–H), 7.00–8.00 (m, 5H, Ph), 8.35 (d, 2H, CH): 13C-NMR (101 MHz, CDCl3): δ 165.58, 151.62, 148.31, 147.25, 144.89, 143.29, 142.88, 139.44, 134.47, 130.01, 129.12, 125.86, 125.51, 123.13, 121.17, 119.99, 113.88, 112.16, 108.77, 107.04, 101.37, 62.35, 16.50, 14.47: ESI-MS from LC-MS at t = 3.89 min. Calcd. for C27H21N3O4S = 483.13, found 484.0.
3.3.6. Ethyl 4-(5-(3,5-Dimethoxyphenyl)thiophene-2-yl)-3-methyl-1-phenyl-1H-pyrazolo[3,4-b]pyridine-6-carboxylate (6d)
(68%): mp = 147.5 °C: 1H-NMR (400 MHz, CDCl3): 1.52 (t, 3H, OCH3), 2.78 (s, 3H, CH3), 3.88 (s, 6H, CH6), 4.55 (q, 2H, OCH2), 8.03 (s, 1H, Py–H), 7.00–8.00 (m, 9H, Ph). 8.38 (d, 2H, CH): 13C-NMR (101 MHz, CDCl3): δ 165.62, 161.34, 151.68, 151.61, 144.95, 143.53, 142.89, 139.43, 137.56, 134.50, 129.13, 125.89, 125.66, 124.44, 121.18, 113.90, 112.17, 104.86, 99.52, 62.39, 55.63, 16.51, 14.47: ESI-MS from LC-MS at t = 3.52 min. Calcd. for C28H25N3O4S = 499.58, found 500.0.
3.3.7. Ethyl 4-(5-(3,5-Dimethylphenyl)thiophen-2-yl)-3-methyl-1-phenyl-1H-pyrazolo[3,4-b]pyridine-6-carboxylate (6e)
(55%): mp = 137 °C: 1H-NMR (400 MHz, CDCl3): 1.50 (t, 3H, OCH3), 2.38 (s, 3H, CH3, CH3), 2.78 (s, 3H, CH3), 3.88 (s, 6H, CH6), 4.55 (q, 2H, OCH2), 7.99 (s, 1H, Py–H), 7.00–8.30 (m, 8H, Ph), 8.36 (dd, 2H, CH): 13C-NMR (101 MHz, CDCl3): δ 165.46, 151.74, 151.62, 143.64, 143.46, 142.75, 139.35, 137.45, 135.49, 134.34, 133.33, 131.35, 129.52, 128.99, 128.40, 126.64, 126.20, 125.71, 121.02, 113.89, 111.95, 62.18, 20.71, 16.36, 14.30. ESI-MS from LC-MS at t = 3.61 min. Calcd. for C28H25N3O2S = 467.58, found 468.11.
3.3.8. Ethyl 4-(5-(3-(Tert-butyl)phenyl)thiophen-2-yl)-3-methyl-1-phenyl-1H-pyrazolo[3,4-b]pyridine-6-carboxylate (6f)
(69%): mp = 116.3 °C: 1H-NMR (400 MHz, CDCl3): 1.41 (s, 9H, CH9), 1.52 (t, 3H, OCH3), 2.79 (s, 3H, CH3), 4.56 (q, 2H, OCH2), 8.05 (s, 1H, Py–H), 7.00–8.00 (m, 9H, Ph), 8.37 (dd, 2H, CH): 13C-NMR (101 MHz, CDCl3): δ 165.71, 151.98, 151.75, 151.71, 144.87, 144.29, 142.86, 139.46, 135.41, 134.52, 129.13, 128.78, 125.88, 125.85, 124.80, 124.03, 123.79, 123.52, 121.19, 113.96, 112.11, 62.38, 34.98, 31.56, 16.50, 14.47: ESI-MS from LC-MS at t = 3.70 min. Calcd. for C30H29N3O2S = 495.64, found 496.8.
3.3.9. Ethyl 4-(5-(2,3-Difluorophenyl)thiophen-2-yl)-3-methyl-1-phenyl-1H-pyrazolo[3,4-b]pyridine-6-carboxylate (6g)
(60%): mp = 170.3 °C: 1H-NMR (400 MHz, CDCl3): 1.52 (t, 3H, OCH3), 2.78 (s, 3H, CH3), 4.56 (q, 2H, OCH2), 8.02 (s, 1H, Py–H), 7.00–8.00 (m, 8H, Ph), 8.34 (dd, 2H, CH): 13C-NMR (101 MHz, CDCl3): δ 177.18, 165.54, 151.64, 151.36, 144.78, 142.92, 139.41, 135.93, 134.61, 129.15, 127.81, 127.74, 126.51, 126.48, 125.93, 124.43, 124.02, 121.19, 116.24, 116.07, 113.86, 112.30, 62.40, 16.50, 14.46: ESI-MS from LC-MS at t = 3.70 min. Calcd. for C30H29N3O2S = 475.51, found 476.04.
3.3.10. Ethyl 3-Methyl-1-phenyl-4-(5-(3-(trifluoromethyl)phenyl)thiophene-2-yl)-1H-pyrazolo[3,4-b]pyridine-6-carboxylate (6h)
(63%): mp = 149.5 °C: 1H-NMR (400 MHz, CDCl3): 1.53 (t, 3H, OCH3), 2.79 (s, 3H, CH3), 4.57 (q, 2H, OCH2), 8.05 (s, 1H, Py–H), 7.00–8.20 (m, 9H, Ph), 8.35 (dd, 2H, CH): 13C-NMR (101 MHz, CDCl3): δ 165.57, 151.64, 151.33, 145.71, 142.93, 142.07, 139.39, 136.35, 134.69, 129.57, 129.16, 128.21, 125.97, 125.10, 124.99, 121.23, 113.83, 112.33, 62.44, 16.50, 14.48: ESI-MS from LC-MS at t = 2.85 min. Calcd. for C27H20F3N3O2S = 507.53, found 508.0.
3.3.11. Ethyl 4-(5′-Chloro-[2,2′-bithiophen]-5-yl)-3-methyl-1-phenyl-1H-pyrazolo[3,4-b]pyridine-6-carboxylate (6i)
(70%): mp = 165 °C: 1H-NMR (400 MHz, CDCl3): 1.52 (t, 3H, OCH3), 2.78 (s, 3H, CH3), 4.56 (q, 2H, OCH2), 7.99 (s, 1H, Py–H), 7.40–7.90 (m, 5H, Ph), 8.34 (dd, 2H, CH), 6.89 (d, 2H, CH), 7.03 (d, 2H, CH): 13C-NMR (101 MHz, CDCl3): δ 165.53, 151.61, 151.13, 145.44, 142.92, 139.37, 137.46, 136.06, 134.62, 129.15, 128.74, 127.01, 125.97, 124.55, 123.28, 122.74, 121.22, 113.83, 112.35, 62.43, 16.50, 14.47: ESI-MS from LC-MS at t = 9.91 min. Calcd. for C24H18ClN3O2S2 = 479, found 480.09.
3.3.12. 4-([2,2′-Bithiophen]-5-yl)-3-methyl-1-phenyl-1H-pyrazolo[3,4-b]pyridine-6-carbohydrazide (7a)
(80%): mp = 255 °C: 1H-NMR (400 MHz, DMSO): 2.58 (s, 3H, CH3), 4.75 (s, 2H, NH2), 8.04 (s, 1H, Py–H), 7.00–7.80 (m, 5H, Ph), 7.9–8.9 (m, 5H, CH), 10.04 (s, 1H, NH): 13C-NMR (101 MHz, DMSO): δ 164.42, 151.45, 150.37, 144.40, 142.63, 142.55, 139.45, 139.00, 134.69, 129.23, 128.95, 127.48, 126.55, 125.93, 125.67, 124.84, 120.09, 111.77, 111.71, 14.27: ESI-MS from LC-MS at t = 3.79 min. Calcd. for C22H17N5OS2 = 471.53, found 472.0.
3.3.13. 3-Methyl-1-phenyl-4-(5-phenylthiophen-2-yl)-1H-pyrazolo[3,4-b]pyridine-6-carbohydrazide (7b)
(81%): mp = 265 °C: 1H-NMR (400 MHz, DMSO): 2.58 (s, 3H, CH3), 4.76 (s, 2H, NH2), 8.07 (s, 1H, Py–H), 7.00–8.50 (m, 10H, Ph), 8.23 (dd, 2H, CH) 10.03 (s, 1H, NH): 13C-NMR (101 MHz, DMSO): δ 164.89, 151.92, 150.84, 144.87, 143.10, 143.02, 139.92, 139.47, 135.16, 129.70, 129.42, 127.95, 127.02, 126.40, 126.14, 125.31, 120.56, 112.24, 112.18, 14.74: ESI-MS from LC-MS at t = 2.85 min. Calcd. for C24H19N5OS = 425.51, found 425 + 41 = 466. M.W of ACN = 41.
3.3.14. 4-(5-(Benzo[d][1,3]dioxol-4-yl)thiophen-2-yl)-3-methyl-1-phenyl-1H-pyrazolo[3,4-b]pyridine-6-carbohydrazide (7c)
(70%): mp = 276 °C: 1H-NMR (400 MHz, DMSO): 2.57 (s, 3H, CH3), 4.75 (s, 2H, NH2), 6.07 (s, 2H, CH2), 8.05 (s, 1H, Py–H), 7.00–8.20 (m, 10H, Ph), 8.31 (dd, 2H, CH), 10.02 (s, 1H, NH): 13C-NMR (101 MHz, DMSO): δ 164.91, 151.95, 150.83, 148.42, 147.14, 144.61, 143.00, 142.82, 139.95, 139.47, 129.69, 129.53, 126.12, 120.53, 120.00, 112.20, 109.09, 106.96, 101.62, 79.65, 14.70: ESI-MS from LC-MS at t = 3.70 min. Calcd. for C25H19N5O3S = 469.52, found 469 + 41 = 510. M.W of acetonitrile = 41.
3.3.15. 4-(5-(3,5-Dimethoxyphenyl)thiophen-2-yl)-3-methyl-1-phenyl-1H-pyrazolo[3,4-b]pyridine-6-carbohydrazide (7d)
(83%): mp = 249 °C: 1H-NMR (400 MHz, DMSO): 2.32 (s, 3H, CH3), 2.37 (s, 3H, CH3), 2.58 (s, 3H, CH3), 4.73 (s, 2H, NH2), 7.98 (s, 1H, Py–H), 7.00–8.50 (m, 10H, Ph), 8.32 (m, 2H, CH), 10.01 (s, 1H, NH): 13C-NMR (101 MHz, DMSO): δ 164.84, 151.99, 150.90, 143.69, 143.36, 143.04, 139.85, 139.48, 137.19, 135.27, 133.21, 131.72, 129.77, 129.68, 127.51, 127.09, 126.12, 120.54, 112.16, 21.04, 14.80: ESI-MS from LC-MS at t = 3.92 min. Calcd. for C26H23N5O3S = 485.56, found 486.0 + 41 = 510. M.W of acetonitrile = 41.
3.3.16. 4-(5-(2,4-Dimethylphenyl)thiophen-2-yl)-3-methyl-1-phenyl-1H-pyrazolo[3,4-b]pyridine-6-carbohydrazide (7e)
(85%): mp = 290 °C: 1H-NMR (400 MHz, DMSO): 2.32 (s, 3H, CH3), 2.37 (s, 3H, CH3), 2.57 (s, 3H, CH3), 4.73 (s, 2H, NH2), 7.98 (s, 1H, Py–H), 7.00–8.20 (m, 8H, Ph), 8.32 (m, 2H, CH), 10.01 (s, 1H, NH): 13C-NMR (101 MHz, DMSO): δ 164.42, 151.57, 150.48, 143.27, 142.94, 142.62, 139.42, 139.06, 136.77, 134.85, 132.78, 131.30, 129.35, 129.26, 127.09, 126.67, 125.70, 120.12, 111.77, 20.72, 20.62, 14.38: ESI-MS from LC-MS at t = 3.93 min. Calcd. for C26H23N5OS = 453.56, found 454.09.
3.3.17. 4-(5-(3-(Tert-butyl)phenyl)thiophen-2-yl)-3-methyl-1-phenyl-1H-pyrazolo[3,4-b]pyridine-6-carbohydrazide (7f)
(76%): 1H-NMR (400 MHz, CDCl3): 1.41 (s, 9H, CH9), 2.79 (s, 3H, CH3), 4.56 (s, 2H, NH2), 8.05 (s, 1H, Py–H), 7.00–8.00 (m, 11H, Ph), 8.30–8.90 (m, 2H, CH), 10.01 (s, 1H, NH). 13C-NMR (101 MHz, DMSO): δ 164.42, 151.57, 150.48, 143.27, 142.94, 142.62, 139.42, 139.06, 136.77, 134.85, 132.78, 131.30, 129.35, 129.26, 127.09, 126.67, 125.70, 120.12, 111.77, 20.72, 20.62, 14.38: ESI-MS from LC-MS at t = 3.70 min. Calcd. for C28H27N5OS = 467.58, found 510.0.
3.3.18. 4-(5-(2,3-Fluorophenyl)thiophen-2-yl)-3-methyl-1-phenyl-1H-pyrazolo[3,4-b]pyridine-6-carbohydrazide (7g)
(71%): mp = 275 °C: 1H-NMR (400 MHz, DMSO): 2.57 (s, 3H, CH3), 4.74 (s, 2H, NH2), 8.01 (s, 1H, Py–H), 7.00–8.50 (m, 5H, Ph), 8.20–8.90 (m, 2H, CH), 10.01 (s, 1H, NH): 13C-NMR (101 MHz, DMSO): δ 164.36, 150.89, 150.40, 150.31, 147.21, 144.60, 143.41, 142.51, 139.42, 138.96, 138.20, 136.62, 135.84, 129.24, 126.49, 125.75, 123.91, 123.04, 120.12, 14.28: ESI-MS from LC-MS at t = 4.28 min. Calcd. for C24H17F2N5OS = 461.49, found 462.05.
3.3.19. 3-Methyl-1-phenyl-4-(5-(3-(trifluoromethyl)phenyl)thiophen-2-yl)-1H-pyrazolo[3,4-b]pyridine-6-carbohydrazide (7h)
(65%): mp = 278 °C: 1H-NMR (400 MHz, DMSO): 2.58 (s, 3H, CH3), 4.77 (s, 2H, NH2), 8.11 (s, 1H, Py–H), 7.00–8.50 (m, 9H, Ph), 8.29 (m, 2H, CH), 10.06 (s, 1H, NH): 13C-NMR (101 MHz, DMSO): δ 164.89, 151.76, 150.77, 145.28, 143.01, 141.35, 140.03, 139.43, 136.09, 130.50, 130.28, 130.20, 129.71, 126.98, 126.79, 126.18, 123.38, 120.57, 112.31, 112.19, 14.64: ESI-MS from LC-MS at t = 3.74 min. Calcd. for C25H18F3N5OS = 493.50, found 494.03.
3.3.20. 4-(5′-Chloro-[2,2′-bithiophen]-5-yl)-3-methyl-1-phenyl-1H-pyrazolo[3,4-b]pyridine-6-carbohydrazide (7i)
(79%): mp = 270 °C: 1H-NMR (400 MHz, DMSO): 2.57 (s, 3H, CH3), 4.76 (s, 2H, NH2), 8.01 (s, 1H, H), 7.00–8.50 (m, 5H, Ph), 7.95–8.32 (m, 4H, CH), Py- 10.00 (s, 1H, NH): 13C-NMR (101 MHz, DMSO): δ 164.80, 151.40, 150.75, 145.32, 143.04, 139.40, 137.68, 135.77, 129.70, 128.40, 127.09, 126.17, 124.25, 120.59, 112.41, 112.15, 14.71: ESI-MS from LC-MS at t = 3.63 min. Calcd. for C22H16ClN5OS2 = 465.98, found 466.1 + 41 = 510. M.W of acetonitrile = 41.