Dinesha et al. / European Journal of Medicinal Chemistry 104 (2015) 25e32
31
6.3.6. (5-(2,4-Dichlorophenyl)-3-(3-fluoro-4-methylphenyl)-5-
hydroxy-4,5-dihydropyrazol-1-yl) (3-fluoro-4-methoxyphenyl)
methanone (4f)
CH2, J ¼ 18.4 Hz), 3.91 (s, 3H, OCH3), 6.95 (s, 1H, OH), 7.15 (d, 2H,
J ¼ 8.4 Hz), 7.23e7.32 (m, 3H) 7.39 (d, 2H, J ¼ 8.4 Hz), 7.68e7.78 (m,
4H); 13C NMR (100 MHz, DMSO-d6, ppm):
d 22.1 (CH3), 53.5 (C-4),
2
IR (KBr) nmax (cmꢀ1): 3387 (OH), 3097 (Ar CeH), 2935 (CeH),
56.6 (OCH3), 94.7 (C-5), 112.8 (C-50), 114.9 (d, JCeF ¼ 21 Hz, C-20),
116.2 (d, 2JCeF ¼ 20 Hz), 116.7 (d, 2JCeF ¼ 20 Hz), 124.6, 126.8, 127.2
(C-60), 127.6 (d, 3JCeF ¼ 7 Hz, C-10), 129.5 (d, 4JCeF ¼ 1.6 Hz), 129.9 (d,
1620 (C]O), 1566 (C]C), 1178 (CeF); 1H NMR (400 MHz, CDCl3,
ppm):
d
2.76 (s, 3H, CH3), 3.97 (d, 1H, CH2, J ¼ 18 Hz), 4.08 (d, 1H,
3
CH2, J ¼ 18 Hz), 4.40 (s, 3H, OCH3), 5.86 (s, 1H, OH), 7.44 (d, 1H,
J ¼ 8.4 Hz), 7.65 (dd, 1H, J ¼ 2 Hz), 7.78 (d, 1H, J ¼ 2 Hz), 7.80e7.85
(m, 3H), 8.23e8.37 (m, 3H); 13C NMR (100 MHz, DMSO-d6, ppm):
3JCeF ¼ 11 Hz), 130.3 (d, JCeF ¼ 11 Hz), 136.5, 140.7, 150.1 (d,
2JCeF ¼ 12 Hz, C-40), 151.0 (d, 1JCeF ¼ 240 Hz, C-30), 153.2, 163.3 (d,
1JCeF ¼ 255 Hz), 164.9 (C]O); LC-MS (m/z, %): 421 ([MꢀH]ꢀ, 97).
d
14.7 (CH3), 48.8 (C-4), 56.6 (OCH3), 91.3 (C-5),113.0 (C-50),113.4 (d,
2JCeF ¼ 17 Hz), 117.8 (d, JCeF ¼ 20 Hz, C-20), 122.9, 124.1, 126.9 (d,
2
6.3.11. (3-(3-Chloro-2-fluorophenyl)-5-hydroxy-5-p-tolyl-4,5-
dihydropyrazol-1-yl) (3-fluoro-4-meth oxyphenyl)methanone (4k)
IR (KBr) nmax (cmꢀ1): 3397 (OH), 3085 (Ar CeH), 2930 (CeH),
1625 (C]O), 1536 (C]C), 1178 (CeF); 1H NMR (400 MHz, DMSO-d6,
2JCeF ¼ 16 Hz), 127.2, 127.4 (d, 3JCeF ¼ 8 Hz, C-10), 127.7 (C-60), 130.1,
3
3
130.6, 131.3 (d, JCeF ¼ 8 Hz), 132.6 (d, JCeF ¼ 7 Hz), 133.3, 139.0,
150.0 (d, JCeF ¼ 10 Hz, C-40), 151.9 (d, 1JCeF ¼ 242 Hz, C-30), 152.6,
2
1
162.4 (d, JCeF ¼ 242 Hz), 163.1 (C]O); LC-MS (m/z, %): 489
ppm):
d
2.30 (s, 3H, CH3), 3.50 (d, 1H, CH2, J ¼ 18.2 Hz), 3.65 (d, 1H,
([MꢀH]ꢀ, 98), 491 (([MꢀH]þ2)ꢀ, 58), 493 (([MꢀH]þ4)ꢀ, 10).
CH2, J ¼ 18.2 Hz), 3.98 (s, 3H, OCH3), 6.97 (s, 1H, OH), 7.32 (d, 2H,
J ¼ 8.4 Hz), 7.54 (d, 2H, J ¼ 8.4 Hz), 7.68e7.82 (m, 3H), 7.87e7.96 (m,
3H); 13C NMR (100 MHz, DMSO-d6, ppm):
d 22.5 (CH3), 54.7 (C-4),
6.3.7. (3-Fluoro-4-methoxyphenyl) (5-hydroxy-3-phenyl-5-p-tolyl-
4,5-dihydropyrazol-1-yl)methanone (4g)
2
56.4 (OCH3), 94.4 (C-5), 112.9 (C-50), 116.4 (d, JCeF ¼ 20 Hz, C-20),
121.2 (d, 2JCeF ¼ 18 Hz), 122.3 (d, 2JCeF ¼ 16 Hz), 124.1, 124.9, 126.7,
127.0 (d, 3JCeF ¼ 7 Hz, C-10),127.2 (C-60), 128.3 (d, 3JCeF ¼ 7 Hz),133.9
(d, 3JCeF ¼ 8 Hz), 135.6, 139.5, 149.8 (d, 2JCeF ¼ 11 Hz, C-40), 151.6 (d,
1JCeF ¼ 245 Hz, C-30), 153.0, 162.8 (d, 1JCeF ¼ 244 Hz), 164.7 (C]O);
LC-MS (m/z, %): 455 ([MꢀH]ꢀ, 90).
IR (KBr) nmax (cmꢀ1): 3393 (OH), 3062 (Ar CeH), 2924 (CeH),
1641 (C]O), 1583 (C]C), 1181 (CeF); 1H NMR (400 MHz, DMSO-d6,
ppm):
d
2.29 (s, 3H, CH3), 3.40 (d, 1H, CH2, J ¼ 18.2 Hz), 3.53 (d, 1H,
CH2, J ¼ 18.2 Hz), 3.95 (s, 3H, OCH3), 6.92 (s, 1H, OH), 7.18 (d, 2H,
J ¼ 8 Hz), 7.26 (d, 2H, J ¼ 7.3 Hz), 7.34 (d, 2H, J ¼ 7.3 Hz), 7.59 (d, 2H,
J ¼ 8 Hz), 7.73e7.81 (m, 3H), 7.96 (d, 1H, J ¼ 5.9 Hz); 13C NMR
(100 MHz, DMSO-d6, ppm):
d 21.8 (CH3), 51.1 (C-4), 56.4 (OCH3),
6.3.12. (3-Fluoro-4-methoxyphenyl) (3-(3-fluoro-4-methylphenyl)-
5-hydroxy-5-p-tolyl-4,5-dihydro pyrazol-1-yl)methanone (4l)
IR (KBr) nmax (cmꢀ1): 3418 (OH), 3093 (Ar CeH), 2915 (CeH),
1619 (C]O), 1563 (C]C), 1165 (CeF); 1H NMR (400 MHz, DMSO-d6,
2
93.8 (C-5), 112.9 (C-50), 117.6 (d, JCeF ¼ 21 Hz, C-20), 125.2, 126.5,
3
127.4 (d, JCeF ¼ 6 Hz, C-10), 127.7 (C-60), 129.0, 129.8, 134.8, 135.1,
136.9,140.5,149.8 (d, 2JCeF ¼ 10 Hz, C-40),151.5 (d, 1JCeF ¼ 244 Hz, C-
30), 153.6, 163.5 (C]O); LC-MS (m/z, %): 403 ([MꢀH]ꢀ, 95).
ppm):
d 2.28 (s, 3H, CH3), 2.36 (s, 3H, CH3), 3.48 (d, 1H, CH2,
J ¼ 18.4 Hz), 3.62 (d, 1H, CH2, J ¼ 18.4 Hz), 3.97 (s, 3H, OCH3), 6.96 (s,
6.3.8. (3-Fluoro-4-methoxyphenyl) (5-hydroxy-3,5-di-p-tolyl-4,5-
dihydropyrazol-1-yl)methanone (4h)
1H, OH), 7.34 (d, 2H, J ¼ 8 Hz), 7.58 (d, 2H, J ¼ 8 Hz), 7.83e7.92 (m,
3H), 8.13e8.27 (m, 3H); 13C NMR (100 MHz, DMSO-d6, ppm):
d 14.9
IR (KBr) nmax (cmꢀ1): 3402 (OH), 3020 (Ar CeH), 2927 (CeH),
(CH3), 21.3 (CH3), 49.6 (C-4), 56.3 (OCH3), 94.0 (C-5), 112.8 (C-50),
1633 (C]O), 1577 (C]C), 1176 (CeF); 1H NMR (400 MHz, DMSO-d6,
2
2
113.0 (d, JCeF ¼ 18 Hz), 116.1 (d, JCeF ¼ 20 Hz, C-20), 124.0, 125.6,
126.3 (d, 2JCeF ¼ 16 Hz), 127.2, 127.5 (d, 3JCeF ¼ 9 Hz, C-10), 128.0 (C-
60) 131.1 (d, 3JCeF ¼ 8 Hz), 132.8 (d, 3JCeF ¼ 8 Hz), 136.1, 140.4, 150.2
(d, 2JCeF ¼ 11 Hz, C-40), 151.7 (d, 1JCeF ¼ 238 Hz, C-30), 154.5, 163.4 (d,
1JCeF ¼ 246 Hz), 165.1 (C]O); LC-MS (m/z, %): 435 ([MꢀH]ꢀ, 98).
ppm):
d 2.27 (s, 3H, CH3), 2.33 (s, 3H, CH3), 3.44 (d, 1H, CH2,
J ¼ 18.4 Hz), 3.59 (d, 1H, CH2, J ¼ 18.4 Hz), 3.91 (s, 3H, OCH3), 6.90 (s,
1H, OH), 7.15 (d, 2H, J ¼ 8 Hz), 7.24e7.27 (m, 3H), 7.38 (d, 2H,
J ¼ 8 Hz), 7.61 (d, 2H, J ¼ 8 Hz), 7.69e7.76 (m, 2H); 13C NMR
(100 MHz, DMSO-d6, ppm): d 21.0 (CH3), 21.5 (CH3), 51.5 (C-4), 56.6
(OCH3), 94.1 (C-5), 113.1 (C-50), 117.8 (d, 2JCeF ¼ 19 Hz, C-20), 125.0,
Acknowledgments
3
126.9, 127.5 (C-60), 127.7 (d, JCeF ¼ 6 Hz, C-10), 128.9, 129.0, 129.8,
2
136.7, 140.6, 141.4, 149.9 (d, JCeF ¼ 11 Hz, C-40), 151.9 (d,
The authors are thankful to The Head, NMR Centre, IISc Banga-
lore and UGC-BSR for the financial assistance provided to one of the
authors, Dinesha. The authors also grateful to the Institution of
Excellence, Vijnana Bhavana, University of Mysore, for providing
the single-crystal X-ray diffractometer facility.
1JCeF ¼ 242 Hz, C-30), 153.0, 164.0 (C]O); LC-MS (m/z, %): 417
([MꢀH]ꢀ, 97).
6.3.9. (3-Fluoro-4-methoxyphenyl) (5-hydroxy-3-(4-
methoxyphenyl)-5-p-tolyl-4,5-dihydropyr azol-1-yl)methanone (4i)
IR (KBr) nmax (cmꢀ1): 3425 (OH), 3033 (Ar CeH), 2930 (CeH),
1621 (C]O), 1565 (C]C), 1184 (CeF); 1H NMR (400 MHz, DMSO-d6,
Appendix A. Supplementary data
ppm):
d
2.29 (s, 3H, CH3), 3.49 (d, 1H, CH2, J ¼ 18 Hz), 3.63 (d, 1H,
Supplementary data related to this article can be found at http://
CH2, J ¼ 18 Hz), 3.83 (s, 3H, OCH3), 3.96 (s, 3H, OCH3), 6.89 (d, 2H,
J ¼ 8.5 Hz), 6.97 (s, 1H, OH), 7.02 (d, 2H, J ¼ 8.1 Hz), 7.20 (d, 2H,
J ¼ 8.5 Hz), 7.41 (d, 2H, J ¼ 8.1 Hz), 7.81e7.93 (m, 3H); 13C NMR
References
(100 MHz, DMSO-d6, ppm):
d 21.0 (CH3), 51.9 (C-4), 55.7 (OCH3),
56.2 (OCH3), 94.3 (C-5), 113.6 (C-50), 114.7, 116.8 (d, 2JCeF ¼ 19 Hz, C-
20), 125.2,127.1, 127.5 (d, 3JCeF ¼ 7 Hz, C-10), 127.7, 128.2 (C-60), 129.5,
136.7,139.5,149.6 (d, 2JCeF ¼ 12 Hz, C-40),152.0 (d, 1JCeF ¼ 240 Hz, C-
30), 153.8, 161.3, 164.2 (C]O); LC-MS (m/z, %): 433 ([MꢀH]ꢀ, 99).
6.3.10. (3-Fluoro-4-methoxyphenyl) (3-(4-fluorophenyl)-5-
hydroxy-5-p-tolyl-4,5-dihydropyr azol-1-yl)methanone (4j)
IR (KBr) nmax (cmꢀ1): 3414 (OH), 3095 (Ar CeH), 2918 (CeH),
1620 (C]O), 1512 (C]C), 1165 (CeF); 1H NMR (400 MHz, DMSO-d6,
ppm):
d
2.28 (s, 3H, CH3), 3.47 (d, 1H, CH2, J ¼ 18.4 Hz), 3.61 (d, 1H,