Medicinal Chemistry Research
Synthesis of target compound 7a-h
[4-(Adamantan-1-yl)benzylidene]-N-(4-
methoxyphenyl)hydrazine-1-carbothioamide (7d)
4-(1-adamantyl)benzaldehyde (1.0 equiv) and thiosemi-
carbazone (6a–h) (1.2 equiv) were dissolved in ethanol
(6 mL). Then acetic acid was added and the solution was
continued to reflux for 3 h.
1
Light yellow solid, yield 57%, m.p. 177–179 °C; H NMR
(400 MHz,DMSO-d6) δ 11.68 (s, 1H), 9.95 (s, 1H), 8.11 (s,
1H), 7.80 (s, 2H), 7.41 (s, 4H), 6.94 (s, 2H), 3.77 (s, 3H);
13C NMR (100 MHz, DMSO-d6) δ 176.78, 157.42, 153.44,
143.23, 131.91, 127.90, 125.41, 113.78, 55.77, 42.92,
36.64, 28.78; FT-IR (KBr, cm−1) 3135.42, 2980.90,
2899.64, 1608.72, 1532.53, 1510.61, 1233.24, 1014.33,
804.52, 548.38; HRMS (ESI) calcd for C25H30N3OS
420.2110, found 420.2109.
2-[4-(Adamantan-1-yl)benzylidene]-N-
phenylhydrazine-1-carbothioamide (7a)
Light yellow solid, yield 49%, m.p. 170–171 °C; 1H
NMR (400 MHz, DMSO-d6) δ 11.90 (s, 1H), 10.18 (s,
1H), 8.16 (s, 1H), 7.82 (d, J = 8.0 Hz, 2H), 7.66–7.38
(m, 4H), 7.03 (t, J = 8.0 Hz, 1H), 2.06 (s, 3H), 1.87 (s,
6H), 1.74 (s, 6H); 13C NMR (100 MHz, DMSO-d6) δ
176.31, 153.50, 143.43, 139.57, 131.83, 128.48, 127.96,
126.07, 125.66, 125.44, 42.88, 36.62, 36.47, 28.76; FT-
IR (KBr, cm−1) 3138.58, 1198.23,803.73, 744.39,
493.02; HRMS (ESI) calcd for C24H28N3S 390.2004,
found 390.2001.
[4-(Adamantan-1-yl)benzylidene]-N-(2-fluorophenyl)
hydrazine-1-carbothioamide (7e)
Light yellow solid, yield 62%, m.p. 178–180 °C; 1H NMR
(400 MHz, DMSO-d6) δ 11.91 (s, 1H), 9.93 (s, 1H), 8.13
(s, 1H), 7.80 (d, J = 8.3 Hz, 2H), 7.55 (t, J = 7.5 Hz, 1H),
7.41 (d, J = 8.3 Hz, 2H), 7.26 (dd, J = 24.5, 9.3 Hz, 3H),
2.06 (s, 3H), 1.88 (s, 6H), 1.74 (s, 6H). 13C NMR
(100 MHz, DMSO-d6) δ 177.60, 158.82, 156.37, 153.62,
143.67, 131.81, 130.28, 127.92, 125.50, 124.39, 55.35,
42.91, 36.65, 28.79; FT-IR (KBr, cm−1) 3298.94, 3141.85,
2-[4-(Adamantan-1-yl)benzylidene]-N-(2-
methoxyphenyl)hydrazine-1-carbothioamide (7b)
Light yellow solid, yield 60%, m.p. 187–189 °C; 1H
NMR (400 MHz, DMSO-d6) δ 11.89 (s, 1H), 10.00 (s,
1H), 8.36 (d, J = 7.3 Hz, 1H), 8.17 (d, J = 16.8 Hz, 1H),
7.72 (d, J = 8.3 Hz, 2H), 7.46 (d, J = 8.3 Hz, 2H),
7.24–6.89 (m, 3H), 3.91 (s, 3H), 2.07 (s, 3H), 1.90 (d,
J = 12.0 Hz, 6H), 1.75 (s, 6H); 13C NMR (100 MHz,
DMSO-d6) δ 175.10, 153.73, 151.41, 143.06, 131.67,
127.53, 125.78, 123.50, 120.35, 111.70, 56.56,
42.86, 36.60, 28.74; FT-IR (KBr, cm−1) 3154.70,
2899.16, 1599.45, 1235.88, 1193.39, 1031.00, 743.44;
HRMS (ESI) calcd for C25H30N3OS 420.2110, found
420.2108.
2899.12,
2846.27,
1621.21,
1545.86,
1221.97,
805.11,745.76; HRMS (ESI) calcd for C24H27FN3S
408.1910, found 408.1908.
[4-(Adamantan-1-yl)benzylidene]-N-(3-fluorophenyl)
hydrazine-1-carbothioamide (7f)
1
Light yellow solid, yield 79%, m.p. 175–177 °C; H NMR
(400 MHz, DMSO-d6) δ 11.90 (s, 1H), 10.12 (s, 1H), 8.15
(s, 1H), 7.82 (d, J = 8.2 Hz, 2H), 7.63 (d, J = 11.3 Hz, 1H),
7.51–7.42 (m, 2H), 7.40 (d, J = 10.2 Hz, 1H), 7.03 (t, J =
8.8 Hz, 1H), 2.07 (s, 3H), 1.88 (s, 6H), 1.75 (s, 6H); 13C
NMR (100 MHz, DMSO-d6) δ 176.04, 163.19, 160.79,
153.66, 143.93, 141.37, 131.68, 129.86, 128.05, 125.46,
2-[4-(Adamantan-1-yl)benzylidene]-N-(3-
methoxyphenyl)hydrazine-1-carbothioamide (7c)
121.50, 112.57, 42.86, 36.60, 28.75; FT-IR (KBr, cm−1
)
3135.56, 2987.81, 2900.50, 2847.06, 1599.16, 1541.58,
1272.83, 1064.02, 548.94; HRMS (ESI) calcd for
C24H27FN3S 408.1910, found 408.1909.
Light yellow solid, yield 53%, m.p. 174–176 °C; 1H
NMR (400 MHz, DMSO-d6) δ 11.77 (s, 1H), 9.99 (s,
1H), 8.14 (s, 1H), 7.82 (d, J = 8.0 Hz, 2H), 7.41 (d,
J = 8.0 Hz, 2H), 7.34–7.15 (m, 3H), 6.78 (d, J = 7.9 Hz,
1H), 3.77 (s, 3H), 2.07 (s, 3H), 1.88 (s, 6H), 1.74 (s, 6H);
13C NMR (100 MHz, DMSO-d6) δ 176.03, 159.49,
153.55, 143.52, 140.65, 131.77, 129.18, 127.98, 125.46,
118.01, 111.53, 111.17, 55.64, 42.87, 36.60, 28.74; FT-
IR (KBr, cm−1) 3125.97, 2899.24, 2845.76, 1597.70,
1546.41, 1463.44, 1288.53, 767.71, 546.23, 448.62;
HRMS (ESI) calcd for C25H30N3OS 420.2110, found
420.2108.
[4-(Adamantan-1-yl)benzylidene]-N-(4-fluorophenyl)
hydrazine-1-carbothioamide (7g)
1
Light yellow solid, yield 50%, m.p. 188–190 °C; H NMR
(400 MHz, DMSO-d6) δ 11.81 (s, 1H), 10.07 (s, 1H), 8.14
(s, 1H), 7.83 (d, J = 8.0 Hz, 2H), 7.57 (s, 2H), 7.42 (d, J =
8.0 Hz, 2H), 7.21 (t, J = 8.0 Hz, 2H), 2.07 (s, 3H), 1.89 (s,
6H), 1.75 (s, 6H); 13C NMR (100 MHz, DMSO-d6) δ
176.72, 161.30, 158.89, 153.54, 143.56, 135.95, 128.49,