Molecules 2012, 17
5146
1-(3-Fluorophenethyl)-3-(5-chloro-1,3-dimethyl-1H-pyrazole-4-carbonyl)thiourea (6i). White solid,
yield 78.8%; m.p. 117–119 °C; 1H-NMR (CDCl3): δ 10.68 (1H, brs, CSNH), 9.08 (1H, brs, CONHCS),
7.30~6.91 (4H, m, Ph-H), 3.93~3.89 (2H, q, CH2), 3.82 (3H, s, CH3), 3.03 (2H, t, J = 8.00 Hz, CH2), 2.43
(3H, s, CH3); 13C-NMR: (CDCl3): δ 180.1, 161.1, 151.8, 140.8, 130.2, 127.4, 124.4, 115.7, 115.6,
19
113.7, 113.5, 109.0, 46.6, 36.6, 34.1, 14.6; F-NMR (CDCl3): δ -112.97; IR (KBr): ν 3377.3, 3228.8
(N–H), 1672.3 (C=O), 1168.9 (C=S); Anal. Calcd for C15H16ClFN4OS: C 50.77%, H 4.55%,
N 15.79%; Found: C 50.55%, H 4.21%, N 15.99%.
1-(5-Chloro-2-fluorophenyl)-3-(5-chloro-1,3-dimethyl-1H-pyrazole-4-carbonyl)thiourea (6j). White
1
solid, yield 72.1%; m.p. 158–160 °C; H-NMR (CDCl3): δ 12.56 (1H, brs, CSNH), 9.27 (1H, brs,
CONHCS), 8.38~7.15 (4H, m, Ph-H), 3.87 (3H, s, CH3), 2.51 (3H, s, CH3); 13C-NMR: (CDCl3): δ
179.0, 161.5, 152.3, 134.2, 127.7, 126.5, 124.2, 121.3, 121.1, 116.7, 116.6, 108.7, 36.7, 14.8;
19F-NMR (CDCl3): δ −116.72; IR (KBr): ν 3375.4, 2991.6 (N–H), 1670.4 (C=O), 1138.0 (C=S); Anal.
Calcd for C13H11Cl2FN4OS: C 43.23%, H 3.07%, N 15.51%; Found: C 43.61%, H 2.96%, N 15.61%.
1-(4-(Trifluoromethylthio)phenyl)-3-(5-chloro-1,3-dimethyl-1H-pyrazole-4-carbonyl)thiourea
(6k).
1
White solid, yield 74.4%; m.p. 145–147 °C; H-NMR (CDCl3): δ 12.75 (1H, brs, CSNH), 9.21 (1H,
13
brs, CONHCS), 7.92~7.52 (4H, m, Ph-H), 3.86 (3H, s, CH3), 2.49 (3H, s, CH3); C-NMR: (CDCl3):
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δ 178.2, 161.5, 152.3, 140.2, 137.0, 133.3, 127.7, 124.2, 121.6, 108.8, 36.7, 14.8; FNMR (CDCl3):
δ −42.66; IR (KBr): ν 3410.2, 3032.1 (N–H), 1666.5 (C=O), 1139.9 (C=S); Anal. Calcd for
C14H12ClF3N4OS2: C 41.13, H 2.96, N 13.70; Found: C 41.22, H 2.76, N 13.73.
1-(4-Bromo-2-(trifluoromethyl)phenyl)-3-(5-chloro-3-methyl-1-phenyl-1H-pyrazole-4-carbonyl) thiourea
1
(6l): White solid, yield 75.9%; m.p. 142–144 °C; H-NMR (CDCl3): δ 12.43 (1H, brs, CSNH), 9.48
(1H, brs, CONHCS), 7.89~7.52 (8H, m, Ph-H), 2.60 (3H, s, CH3); 13C-NMR (CDCl3): δ 180.7, 161.5,
153.5, 136.9, 135.4, 134.7, 131.4, 129.7, 129.5, 127.4, 127.2, 126.9, 125.6, 120.9, 110.2, 15.0;
19F-NMR (CDCl3): δ −61.39; IR (KBr): ν 3373.5, 3119.2 (N–H), 1670.4 (C=O), 1149.6 (C=S); Anal.
Calcd for C19H13BrClF3N4OS: C 44.08%, H 2.53%, N 10.82%; Found: C 44.13%, H 2.12%,
N 10.72%.
1-(2-Fluorobenzyl)-3-(5-chloro-3-methyl-1-phenyl-1H-pyrazole-4-carbonyl)thiourea (6m). White
1
solid, yield 82.9%; m.p. 106–108 °C; H-NMR (CDCl3): δ 10.93 (1H, brs, CSNH), 9.27 (1H, brs,
13
CONHCS), 7.54~7.07 (9H, m, Ph-H), 4.97 (2H, d, J = 5.75Hz, CH2), 2.53 (3H, s, CH3); C-NMR
(CDCl3): δ 180.1, 161.2, 152.9, 136.9, 130.5, 130.5, 129.9, 129.6, 129.4, 125.5, 124.4, 124.4, 115.7,
115.6, 110.6, 43.5, 14.8; 19F-NMR (CDCl3): δ −117.80; IR (KBr): ν 3394.7, 3248.1 (N–H), 1666.5
(C=O), 1165.0 (C=S); Anal. Calcd for C19H16ClFN4OS: C 56.64%, H 4.00%, N 13.91%; Found:
C 57.07%, H 4.46%, N 14.22%.
1-(2-Fluoro-5-(trifluoromethyl)phenyl)-3-(5-chloro-3-methyl-1-phenyl-1H-pyrazole-4-carbonyl) thiourea
1
(6n). White solid, yield 75.1%; m.p. 178–180 °C; H-NMR (CDCl3): δ 12.77 (1H, brs, CSNH), 9.35
(1H, brs, CONHCS), 7.92~7.52 (9H, m, Ph-H), 2.60 (3H, s, CH3); 13C-NMR (CDCl3): δ 178.7, 161.5,
153.4, 136.9, 129.7, 129.5, 127.4, 126.8, 126.7, 125.6, 124.5, 122.6, 116.2, 116.1, 110.2, 15.0;
19F-NMR (CDCl3): δ −61.98, −119.33; IR (KBr): ν 3215.3, 3076.5 (N–H), 1685.8 (C=O), 1157.3