Molecules 2012, 17
10663
6-((4-Bromo-3,5-dimethyl-1H-pyrazol-1-yl)methyl)-1-(3-mercaptopropyl)-4-oxo-1,4-dihydroquinoline-
1
3-carboxylic acid (14c). Yield: 42%; mp: 231–233 °C; H-NMR (DMSO-d6, δ ppm) 2.08–2.11 (m,
2H, -CH2CH2CH2SH), 2.12 (s, 3H, CH3-pyrazole), 2.21 (s, 3H, CH3-pyrazole), 2.55–2.58 (m, 2H,
-CH2CH2CH2SH), 4.62 (t, 2H, J = 7.2 Hz, -CH2CH2CH2SH), 5.51 (s, 2H, -CH2-pyrazole), 7.73 (dd,
1H, J = 2.0 and 8.8 Hz, H7), 8.06 (d, 1H, J = 8.8 Hz, H8), 8.14 (d, 1H, J = 2.0 Hz, H5), 9.03 (s, 1H,
H2), 15.09 (s, 1H, -COOH); 13C-NMR (DMSO-d6, δ ppm) 10.4, 12.5, 21.1, 28.4, 34.3, 52.5, 93.9,
108.3, 119.1, 124.5, 126.1, 133.6, 135.9, 137.8, 139.0, 145.6, 149.9, 166.4, 178.0; HRMS: m/z calcd
for C19H21BrN3O3S: 450.0481, 452.0466; found: 450.0489, 452.0467; HPLC purity 96.90%.
1-(4-Fluorobenzyl)-6-((3,5-dimethyl-1H-pyrazol-1-yl)methyl)-4-oxo-1,4-dihydro-quinoline-3-carboxylic
1
acid (15a). Yield: 63%; mp: 271–273 °C; H-NMR (DMSO-d6, δ ppm) 2.09 (s, 3H, CH3-pyrazole),
2.16 (s, 3H, CH3-pyrazole), 5.36 (s, 2H, -CH2-pyrazole), 5.82 (s, 2H, -CH2-Ar), 5.87 (s, 1H,
H-pyrazole), 7.19 (t, 2H, J = 8.8 Hz, Ar-H), 7.37 (q, 2H, J = 8.4 Hz, Ar-H), 7.60 (dd, 1H, J = 2.0 and
9.2 Hz, H7), 7.87 (d, 1H, J = 8.8 Hz, H8), 8.05 (d, 1H, J = 1.6 Hz, H5), 9.26 (s, 1H, H2), 15.06 (s, 1H,
-COOH); 13C-NMR (DMSO-d6, δ ppm) 11.1, 13.8, 51.1, 56.2, 105.7, 108.5, 116.1, 116.4, 119.5,
124.1, 126.2, 129.5, 129.5, 133.4, 136.9, 139.1, 139.4, 147.0, 150.5, 166.4, 178.2; HRMS: m/z calcd
for C23H21FN3O3: 406.1561; found: 406.1569; HPLC purity 99.70%.
1-(4-Fluorobenzyl)-6-((4-chloro-3,5-dimethyl-1H-pyrazol-1-yl)methyl)-4-oxo-1,4-dihydro-quinoline-3-
1
carboxylic acid (15b). Yield: 75%; mp: 239–241 °C; H-NMR (DMSO-d6, δ ppm) 2.17 (s, 3H,
CH3-pyrazole), 2.22 (s, 3H, CH3-pyrazole), 5.34 (s, 2H, -CH2-pyrazole), 5.49 (s, 2H, -CH2-Ar), 7.10 (t,
2H, J = 8.0 Hz, Ar-H), 7.14–7.18 (m, 2H, Ar-H), 7.42–7.49 (m, 2H, H7 H8), 8.35 (s, 1H, H5), 8.89 (s,
1H, H2), 14.68 (s, 1H, -COOH); 13C-NMR (DMSO-d6, 100 MHz, δ ppm) 9.5, 11.4, 52.7, 57.6, 108.7,
109.4, 116.6, 116.8, 118.1, 125.1, 126.7, 128.0, 128.1, 132.8, 135.4, 135.6, 139.0, 145.4, 149.1, 166.6,
178.3; HRMS: m/z calcd for C23H20ClFN3O3: 440.1171; found: 440.1169; HPLC purity 99.55%.
1-(4-Fluorobenzyl)-6-((4-bromo-3,5-dimethyl-1H-pyrazol-1-yl)methyl)-4-oxo-1,4-dihydro-quinoline-3-
1
carboxylic acid (15c). Yield: 73%; mp: 255–257 °C; H-NMR (DMSO-d6, δ ppm) 2.17 (s, 3H,
CH3-pyrazole), 2.21 (s, 3H, CH3-pyrazole), 5.35 (s, 2H, -CH2-pyrazole), 5.48 (s, 2H, -CH2-Ar), 7.08
(t, 2H, J = 7.6 Hz, Ar-H), 7.14 (s, 2H, Ar-H), 7.43 (s, 2H, H7 H8), 8.35 (s, 1H, H5), 8.88 (s, 1H, H2),
15.06 (s, 1H, -COOH); 13C-NMR (DMSO-d6, δ ppm) 10.4, 12.31, 52.8, 57.6, 109.4, 116.6, 116.8,
118.0, 125.2, 126.7, 128.0, 128.1, 132.8, 135.4, 137.4, 139.1, 139.0, 146.9, 149.1, 166.5, 178.3;
HRMS: m/z calcd for C23H20BrFN3O3: 484.0666, 486.0651; found: 484.0665, 486.0646; HPLC purity
99.57%.
1-(4-Nitrobenzyl)-6-((3,5-dimethyl-1H-pyrazol-1-yl)methyl)-4-oxo-1,4-dihydro-quinoline-3-carboxylic
1
acid (16a). Yield: 56%; mp: 274–276 °C; H-NMR (DMSO-d6, δ ppm) 2.08 (s, 3H, CH3-pyrazole),
2.16 (s, 3H, CH3-pyrazole), 5.36 (s, 2H, -CH2-pyrazole), 5.87 (s, 1H, H-pyrazole), 6.01 (s, 2H,
-CH2-Ar), 7.52 (d, 2H, J = 8.8 Hz, Ar-H), 7.58 (dd, 1H, J = 2.0 and 8.8 Hz, H7), 7.75 (d, 1H, J = 8.8 Hz,
H8), 8.07 (d, 1H, J = 2.0 Hz, H5), 8.18 (d, 2H, J = 8.8 Hz, Ar-H), 9.32 (s, 1H, H2), 15.01 (s, 1H,
-COOH); 13C-NMR (DMSO-d6, δ ppm) 11.1, 13.8, 51.1, 56.3, 105.7, 108.8, 119.3, 124.2, 124.4,
126.2, 128.3, 133.6, 137.1, 139.0, 139.4, 143.5, 147.0, 147.6, 150.9, 166.3, 178.4; HRMS: m/z calcd
for C23H21N4O5: 433.1506; found: 433.1508; HPLC purity 99.80%.