Molecules 2017, 22, 1635
10 of 14
(N-H), 3253.05 (N-H), 3152.44 (ArC-H), 1595.04 (C=N), 1473.05 (C=C), 1235.36 (C-O), 1176.17 (C=S).
1H-NMR (ppm)
: 9.41 (s, 1H, OH), 8.11 (s, 1H, NH2), 8.00 (s, 1H, NH2), 7.90 (d, 2H, J = 8.0 Hz, Ar-H),
δ
7.54 (d, 2H, J = 12.0 Hz, Ar-H), 6.79 (s, 1H, Ar-H), 6.71 (s, 1H, Ar-H), 5.84 (dd, 1H, J = 4.0 and 12.0 Hz,
pyrazoline 5-H), 3.84 (dd, 1H, J = 12.0 and 20.0 Hz, pyrazoline 4-Hcis), 3.19 (dd, 1H, J = 4.0 and 20.0 Hz,
pyrazoline 4-Htrans), 3.78 (s, 3H, OCH3). 13C-NMR (DMSO-d6, ppm)
δ: 176.89, 154.46, 148.95, 143.20,
135.65, 135.33, 130.34 (2C), 129.36, 129.25, 120.97 (2C), 109.62, 109.48, 62.91, 56.65, 42.71. MS (ESI) (m/z):
440.3, 441.9 [M + H]+. HRMS: m/z [M + Na]+ calcd for C17H15ClN3O2S: 461.9634; found: 461.9631.
3-(4-Bromophenyl)-5-(3-bromo-4-hydroxy-5-methoxythiophenyl)-4,5-dihydro-1H-pyrazole-1-carbothioamide
◦
(
6b). White solid (yield 22.46%), m.p.: 228.2–228.6 C. IR (KBr,
(N-H), 3252.81 (N-H), 3152.79 (ArC-H), 1592.59 (C=N), 1496.38 (C=C), 1275.39 (C-O), 1173.55 (C=S).
1H-NMR (ppm)
: 9.39 (s, 1H, OH), 8.11 (s, 1H, NH2), 7.99 (s, 1H, NH2), 7.83 (d, 2H, J = 8.0 Hz, Ar-H),
ν
in cm−1): 3422.81 (O-H), 3408.02
δ
7.67 (d, 2H, J = 8.0 Hz, Ar-H), 6.79 (d, 1H, J = 4.0 Hz, Ar-H), 6.71 (d, 1H, J = 4.0 Hz, Ar-H), 5.83 (dd,
1H, J = 4.0 and 12.0 Hz, pyrazoline 5-H), 3.84 (dd, 1H, J = 12.0 and 20.0 Hz, pyrazoline 4-Hcis), 3.78 (s,
3H, OCH3), 3.19 (dd, 1H, J = 4.0 and 20.0 Hz, pyrazoline 4-Htrans). 13C-NMR (ppm)
δ: 176.79, 155.60,
148.79, 144.20, 138.22, 132.12(2C), 131.24(2C), 130.25, 125.46, 124.19, 113.16, 111.17, 62.62, 56.67, 42.81.
MS (ESI) (m/z): 484.1, 485.9 [M + H]+. HRMS: m/z [M + Na]+ calcd for C17H15Br2N3O2S: 507.9107;
found: 507.9097.
3-(2-Hydroxyphenyl)-5-(3-bromo-4-hydroxy-5-methoxythiophenyl)-4,5-dihydro-1H-pyrazole-1-carbothioamide
(
7b). White solid (yield 47.24%), m.p.: 263.9–264.5 ◦C. IR (KBr, in cm−1): 3414.47 (N-H), 3315.95
ν
(N-H), 3187.99 (ArC-H), 1609.38 (C=N), 1485.98 (C=C), 1249.05 (C-O), 1165.33 (C=S). 1H-NMR (ppm)
δ:
9.76 (s, 1H, OH), 9.41 (s, 1H, OH), 8.11 (s, 1H, NH2), 8.06 (s, 1H, NH2), 7.65 (d, 1H, J = 8.0 Hz, Ar-H),
7.34 (t, 1H, J = 8.0 Hz, Ar-H), 6.93 (m, 2H, Ar-H), 6.81 (s, 1H, Ar-H), 6.72 (s, 1H, Ar-H), 5.83 (dd, 1H,
J = 4.0 and 12.0 Hz, pyrazoline 5-H), 3.93 (dd, 1H, J = 12.0 and 20.0 Hz, pyrazoline 4-Hcis), 3.28 (dd, 1H,
J = 4.0 and 20.0 Hz, pyrazoline 4-Htrans), 3.79 (s, 3H, OCH3). 13C-NMR (ppm)
δ: 176.46, 157.03, 156.86,
148.96, 143.17, 135.36, 132.58, 130.06, 120.83, 120.00, 117.34, 116.63, 109.62, 109.42, 61.75, 56.64, 44.57.
MS (ESI) (m/z): 422.2, 424.1 [M + H]+. HRMS: m/z [M + Na]+ calcd for C17H16BrN3O3S: 443.9973;
found: 443.9968.
3-(2-Hydroxyphenyl)-5-(3-methoxy-4-hydroxy-5-methoxythiophenyl)-4,5-dihydro-1H-pyrazole-1-carbothioamide
(
8b). Yellow solid (yield 21.78%), m.p.: 230.2–230.6 ◦C. IR (KBr, in cm−1): 3430.11 (N-H), 3322.13
ν
(N-H), 3178.46 (ArC-H), 2991.86 (C-H), 1609.15 (C=N), 1589.30 (C=C), 1248.53 (C-O), 1118.29 (C=S).
1H-NMR (ppm)
δ: 9.77 (s, 1H, OH), 8.29 (s, 1H, OH), 8.06 (s, 1H, NH2), 8.03 (s, 1H, NH2), 7.64 (d, 1H, J
= 8.0 Hz, Ar-H), 7.33 (t, 1H, J = 8.0 Hz, Ar-H), 6.93 (m, 2 H, Ar-H), 6.39 (s, 2H, Ar-H), 5.82 (dd, 1H,
J = 4.0 and 12.0 Hz, pyrazoline 5-H), 3.91 (dd, 1H, J = 12.0 and 20.0 Hz, pyrazoline 4-Hcis), 3.27 (dd, 1H,
J = 4.0 and 20.0 Hz, pyrazoline 4-Htrans), 3.69 (s, 6H, OCH3). 13C-NMR (ppm)
δ: 176.61, 157.02, 156.97,
148.47, 135.23, 133.49, 132.49, 130.03 (2C), 119.98 (2C), 117.29, 116.73, 103.55, 62.41 (2C), 56.53, 44.69. MS
(ESI) (m/z): 374.1[M + H]+. HRMS: m/z [M + Na]+ calcd for C18H19N3O4S: 396.0984; found: 396.0972.
3-(2-Hydroxyphenyl)-5-(3-ethyoxyl-4-hydroxy-5-bromothiophenyl)-4,5-dihydro-1H-pyrazole-1-carbothioamide
(
9b). White solid (yield 12.49%), m.p.: 240.9–241.1 ◦C. IR (KBr, in cm−1): 3425.40 (N-H), 3320.10
ν
(N-H), 3176.22 (ArC-H), 1598.08 (C=N), 1476.57 (C=C), 1251.80 (C-O), 1131.23 (C=S). 1H-NMR (ppm)
δ:
9.75 (s, 1H, OH), 9.20 (s, 1H, OH), 8.11 (s, 1H, NH2), 8.05 (s, 1H, NH2), 7.65 (d, 1H, J = 4.0 Hz, Ar-H),
7.33 (m, 1H, Ar-H), 6.92 (m, 2H, Ar-H), 6.78 (s, 1H, Ar-H), 6.73 (s, 1H, Ar-H) , 5.81 (dd, 1H, J = 4.0 and
12.0 Hz, pyrazoline 5-H), 4.03 (q, 2H, J = 8.0Hz, CH2), 3.92 (dd, 1H, J = 12.0 and 20.0 Hz, pyrazoline
4-Hcis), 3.27 (dd, 1H, J = 4.0 and 16.0 Hz, pyrazoline 4-Htrans), 1.33 (t, 3H, J = 8.0 Hz, CH3). 13C-NMR
(ppm) δ: 176.44, 157.02, 156.87, 147.96, 143.44, 135.38, 132.57, 130.07, 120.91, 120.00, 117.34, 116.62,
110.67, 109.72, 65.05, 61.72, 44.54, 14.99. MS (ESI) (m/z): 436.1, 438.0 [M + H]+. HRMS: m/z [M + Na]+
calcd for C18H18BrN3O3S: 460.0129; found: 460.0108.
3-(2-Hydroxyphenyl)-5-(3,4,5-trimethoxythiophenyl)-4,5-dihydro-1H-pyrazole-1-carbothioamide (10b). Yellow
◦
solid (yield 23.86%), m.p.: 204.8 C. IR (KBr,
ν
in cm−1): 3436.42 (N-H), 3331.30 (N-H), 3181.19 (ArC-H),