Molecules 2021, 26, 2081
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H-400 an0d0 H-500), 7.72 (2H, m, H-9 and H-13), 7.98 (2H, dd, J = 2.0 Hz and 7.5 Hz, H-200
and H-6 ), 9.93 (1H, s, 7-NH CH3), 42.3 (4-
); 13C NMR (125 MHz, CD3COCD3): δC 20.2 (14-
C
H2), 63.3 (5-C
H), 124.3 (C-9 and C-13), 124.6 (C-11), 125.5 (C-20 and C-60), 127.2 (C-200
and C-600), 128.0 (C-10 and C-12), 128.7 (C-300 and C-500), 129.1 (C-30 and C-50), 130.7 (C-400),
131.3 (C-100), 136.5 (C-40), 139.8 (C-8), 140.1 (C-10), 155.3 (3-
394.1156 [M + Na]+ {calcd. 394.1354 for C23H21N3SNa}.
C=N), 174.2 (6-C=S); HRMS:
5-(4-methoxyphenyl)-N,3-diphenyl-4,5-dihydro-1H-pyrazole-1-carbothioamide (4b). Pale yellow
crystals; yield: 39%; m.p.: 173–175 ◦C; FTIR (ATR) cm−1: 3334 (N–H), 3058 (Csp2–H),
ν
max
2842 (Csp3–H), 1592 (C=N), 1510, 1445 (aromatic C=C), 1396 (C=S), 1244 (C–O); 1H-NMR
(500 MHz, CD3COCD3): δH 3.29 (1H, dd, J = 3.5 Hz and 18.0 Hz, 4 -C ), 3.78 (3H, s,
14-OCH3), 4.05 (1H, dd, J = 11.5 Hz and 18.0 Hz, 4 -C ), 6.13 (1H, dd, J = 3.5 Hz and
), 6.89 (2H, d, J = 9.0 Hz, H-3 and H-5 ), 7.15 (1H, t, J = 7.5 Hz, H-11), 7.22 (2H,
α
H
β
H
0
0
11.5 Hz, 5-C
d, J = 8.5 Hz, H-2 and H-6 ), 7.33 (2H, t, J = 7.5 Hz, H-10 and H-12), 7.50 (3H, m, H-3 , H-4
and H-500), 7.73 (2H, d, J = 7.5 Hz, H-9 and H-13), 7.99 (2H, m, H-200 and H-600), 9.92 (1H, s,
H
0
0
00
00
7-NH CH2), 54.6 (14-OCH3), 63.1 (5-CH),
); 13C NMR (125 MHz, CD3COCD3): δC 42.3 (4-
113.8 (C-30 and C-50), 124.3 (C-9 and C-13),010 24.6 (C-11), 126.9 (C-0200 and C-60), 01027.2 (C-200
00
00
and C-6 ), 128.0 (C-10 and C-12), 128.7 (C-3 and C-5 ), 130.7 (C-4 ), 131.4 (C-1 ), 135.1 (C-
0
0
C=N), 158.9 (C-4 ), 174.2 (6-C
=S); HRMS: 410.1098 [M + Na]+ {calcd.
1 ), 139.8 (C-8), 155.3 (3-
410.1303 for C23H21N3OSNa}.
5-(4-chlorophenyl)-N,3-diphenyl-4,5-dihydro-1H-pyrazole-1-carbothioamide (4c). Yellow solid;
◦
yield: 34%; m.p.: 150–153 C; FTIR (ATR)
1538, 1489 (aromatic C=C), 1380 (C=S); 1H-NMR (500 MHz, CD3COCD3): δH 3.33 (1H, dd,
J = 3.5 Hz and 18.0 Hz, 4 -C ), 4.11 (1H, dd, J = 11.5 Hz and 18.0 Hz, 4 -C ), 6.18 (1H,
dd, J = 3.5 Hz and 11.5 Hz, 5-C
), 7.16 (1H, t, J = 7.5 Hz, H-11), 7.35 (6H, m, H-20, H-30,
H-50, H-60, H-10 and H-12), 7.50 (3H, m, H-300, H-400 and H-500), 7.72 (2H, t, J = 7.5 Hz, H-9
ν
max cm−1: 3306 (N–H), 3034 (Csp2–H), 1594 (C=N),
α
H
β
H
H
00
00
and H-13), 7.99 (2H, d, J = 7.0 Hz, H-2 and H-6 ), 9.96 (1H, s, 7-N
H
); 13C-NMR (125 MHz,
CD3COCD3): δC 42.1 (4-CH2), 63.0 (5-C
H), 124.4 (C-9 and C-13), 124.7 (C-11), 127.2 (C-20
and C-60), 127.6 (C-200 and C-600), 128.1 (C-10 and C-12), 128.6 (C-30 and C-50), 128.7 (C-300
and C-500), 130.7 (C-400), 131.2 (C-100), 132.2 (C-40), 139.7 (C-8), 142.0 (C-10), 155.2 (3-C=N),
174.3 (6-C=S); HRMS: 392.0952 [M + H]+ {calcd. 392.0988 for (C22H19ClN3S}.
5-(4-dimethylaminohenyl)-N,3-diphenyl-4,5-dihydro-1H-pyrazole-1-carbothioamide (4d). Orange
oil; yield: 12%; FTIR (ATR)
1595 (C=N), 1517, 1446 (aromatic C=C), 1395 (C=S), 1320 (C–N); H-NMR (500 MHz,
ν
cm−1: 3338 (N–H), 3031 (Csp2–H), 2921 (Csp3–H),
max
1
CD3COCD3): δH 2.90(6H, s, 14-CH3 and 15-CH3), 3.09 (1H, dd, J = 3.5 Hz and 18.0 Hz,
4
α
-C
5-C
H-10 and H-12), 7.50 (3H, m, H-3 , H-4 and H-5 ), 7.74 (2H, m, H-9 and H-13), 7.98 (2H, m,
H
), 3.99 (1H, dd, J = 11.5 Hz and 18.0 Hz, 4
β
-C
H), 6.08 (1H, dd, J = 3.5 Hz and 11.0 Hz,
0
0
0
0
H
), 6.69 (2H, d, J = 9.0 Hz, H-3 and H-5 ), 7.13 (3H, m, H-2 , H-6 and H-11), 7.33 (2H, m,
00
00
00
00
00
H-2 and H-6 ), 9.88 (1H, s, 7-N
0 0
15- H3), 42.3 (4- H2), 63.2 (5-CH), 112.4 (C-3 and C-5 ), 124.2 (C-9 and C-13), 124.5 (C-11),
H CH3 and
); 13C-NMR (125 MHz, CD3COCD3): δC 39.8 (14-
C
C
126.6 (C-20 and C-60), 127.2 (C-200 a0n0 d C-600), 128.0 (C-10 and C-12), 128.7 (C-300 and C-500),
00
0
0
130.6 (C-4 ), 130.6 (C-1 ), 131.5 (C-1 ), 139.9 (C-8), 150.0 (C-4 ), 155.3 (3-C=N), 174.1 (6-
HRMS: 401.1848 [M + H]+ {calcd. 401.1800 for C24H25N4S}.
C=S);
5-(2,4-dichlorophenyl)-N,3-diphenyl-4,5-dihydro-1H-pyrazole-1-carbothioamide (4e). Yellowish
powder; yield: 15%; m.p.: 175–177 ◦C; FTIR (ATR) cm−1: 3345 (N–H), 3056 (Csp2–H),
ν
max
2925 (Csp3–H), 1589 (C=N), 1510, 1447 (aromatic C=C), 1398 (C=S); 1H-NMR (500 MHz,
CD3COCD3): δH 3.14 (1H, dd, J = 4.0 Hz and 18.0 Hz, 4
α
-CH
), 4.03 (1H, dd, J = 12.0 Hz and
18.0 Hz, 4
β
-C
H
), 6.25 (1H, dd, J = 4.5 Hz and 12.0 Hz, 5-C
H
), 7.04 (2H, m, H-10 and H-12),
7.21 (3H, m, H-50, H-60 and H-11), 7.36 (3H, m, H-300, H-400 and H-500), 7.40 (1H, s, H-30),
7.59 (2H, dd, J = 1.0 Hz and 8.5 Hz, H-9 and H-13), 7.84 (2H, dd, J = 1.5 Hz and 8.0 Hz,
H-200 and H-600), 9.88 (1H, s, 7-N
H
); 13C-NMR (125 MHz, CD3COCD3): δC 40.7 (4-
C
H2),
H), 124.4 (C-10 and C-12), 124.9 (C-11), 127.3 (C-200 and C-600), 127.6 (C-50 and
C-60), 128.1 (C-9 and C-13), 128.7 (C-300 and C-500), 129.2 (C-30), 130.8 (C-400), 131.1 (C-100),
61.1 (5-
C