Molecules 2016, 21, 224
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1
1124 (O-CH3). H-NMR (400 MHz, DMSO-d6)
δ, ppm: 2.28 (s, 3H, CH3), O-CH3 [3.66 (s, 3H), 3.78
(s, 6H)], 5.11 (s, 2H, O-CH2), Ar.H [6.79 (s, 2H), 7.08–7.11 (m, 4H), 7.27 (d, J = 5.6 Hz, 2H), 7.91
(d, J = 8.8 Hz, 2H)], 9.59 (s, 1H, NH), 9.71 (bs, 1H, NH), 10.36 (s, 1H, NH). 13C-NMR (100 MHz,
DMSO-d6)
δ, ppm: 21.0 (CH3), O-
C
H3 (56.4, 60.5), 70.1 (O-
C
H2), Ar.C [105.8, 114.8, 125.4, 126.4, 128.9,
130.3, 132.6, 134.6, 137.2, 137.6, 153.4, 161.6], 166.0 (
[M + Na]+. Calcd. 504.1558.
C=O). HREIMS, C25H27N3O5S, m/z= 504.1570,
N-(m-Tolyl)-2-(4-(3,4,5-trimethoxybenzyloxy)benzoyl) Hydrazine Carbothioamide (3e). White solid (Ethanol,
˝
0.52 g, 90%), m.p. 89–101 C. IR: 3321 (NH), 3220 (NH), 3170 (NH), 1663 (C=O), 1597 (C=C), 1238 (C=S),
1
1127 (O-CH3). H-NMR (400 MHz, DMSO-d6)
δ, ppm: 2.29 (s, 3H, CH3), O-CH3 [3.66 (s, 3H), 3.78
(s, 6H)], 5.11 (s, 2H, O-CH2), Ar.H [6.80 (s, 2H), 6.98 (d, J = 7 Hz, 1H), 7.13 (d, J = 8 Hz, 2H), 7.20–7.22
(m, 2H), 7.37 (d, J = 6 Hz, 1H), 7.93 (d, J = 8 Hz, 2H), 9.61 (bs, 1H, NH), 9.72 (bs, 1H, NH), 10.37 (s, 1H,
NH). 13C-NMR (100 MHz, DMSO-d6)
δ, ppm: 21.4 (
C
H3), O-
C
H3 (56.4, 60.5), 70.1 (O-
C
H2), Ar.C [105.8,
114.8, 123.5, 125.4, 126.1, 126.9, 128.2, 130.3, 132.6, 137.6, 139.6, 153.4, 161.6], 166.0 (
HREIMS, C25H27N3O5S, m/z = 504.1571, [M + Na]+. Calcd. 504.1558.
C
=O), 181.6 ( =S).
C
N-(4-Nitrophenyl)-2-(4-(3,4,5-trimethoxybenzyloxy)benzoyl) Hydrazine Carbothioamide (3f). Light yellow
solid (Methanol, 0.57 g, 92%), m.p. 196–199 ˝C. IR: 3319 (NH), 3190 (NH), 3153 (NH), 1659 (C=O),
1593 (C=C), 1232 (C=S), 1123 (O-CH3), 1505, 1330 (NO2). 1H-NMR (400 MHz, DMSO-d6)
δ, ppm:
O-CH3 [3.66 (s, 3H), 3.78 (s, 6H)], 5.12 (s, 2H, O-CH2), Ar.H [6.80 (s, 2H), 7.14 (d, J = 8.5 Hz, 2H),
7.90–7.95 (m, 4H), 8.21 (d, J = 8.7 Hz, 2H)], 10.11 (bs, 2H, NH), 10.50 (bs, 1H, NH). 13C-NMR (100 MHz,
DMSO-d6)
δ
, ppm: O-
C
H3 (56.4, 60.5), 70.1 (O-
C
H2), Ar.C [105.8, 114.9, 124.0, 125.1, 125.3, 129.3, 130.3,
132.6, 137.6, 146.2, 153.4, 161.7], 166.1 (
C
=O), 181.3 ( =S). HREIMS, C24H24N4O7S, m/z = 535.1257,
C
[M + Na]+. Calcd. 535.1252.
3.2.2. General Procedure for the Synthesis of 4-(4-Aryl)-3-(4-(3,4,5-trimethoxy benzyloxy)
Phenyl)-1H-1,2,4-Triazole-5-(4H)-thiones 4a–f
A mixture of arylthiosemicarbazide 3a–f (0.80 mmol) and sodium hydroxide solution (4 M, 20 mL)
was refluxed for 5–6 h. After cooling, 100 mL ice water was added. The solution pH was adjusted to
5–6 using diluted hydrochloric acid. The precipitate was filtered, washed with cold water, dried and
recrystallized from a suitable solvent.
4-(4-Chlorophenyl)-3-(4-(3,4,5-trimethoxybenz˝yloxy)phenyl)-1H-1,2,4-triazole-5-(4H)-thione (4a). White
solid (ethanol, 0.31 g, 81%), m.p. 226–229 C. IR: 3105 (NH), 1611 (C=N), 1330 (C-N), 1225 (C=S),
1
1125 (O-CH3), 702 (C-Cl). H-NMR
δ, ppm: O-CH3 [3.65 (s, 3H), 3.76 (s, 6H)], 5.00 (s, 2H, O-CH2), 6.75
(s, 2H, ArH), 7.01 (d, J = 8.8 Hz, 2H, ArH), 7.26 (d, J = 8.8 Hz, 2H, ArH), 7.40 (d, J = 8.6 Hz, 2H, ArH),
7.58 (d, J = 8.6 Hz, 2H, ArH), 14.08 (s, 1H, NH). 13C-NMR
, ppm: O- H3 (56.3, 60.5), 70.1 (O- H2),
Ar.C [105.9, 115.3, 118.4, 129.9, 130.4, 131.2, 132.5, 134.0, 134.4, 137.6, 150.9 ( =N), 153.4, 160.3], 168.8
(C=S). HREIMS, C24H22ClN3O4S, m/z = 506.0915, 508.0901 [M + Na]+. Calcd. 506.0907, 508.0878.
δ
C
C
C
4-(4-Methoxyphenyl)-3-(4-(3,4,5-trimethoxybenzylo˝xy)phenyl)-1H-1,2,4-triazole-5-(4H)-thione (4b). White
solid (Ethanol: CHCl3, 0.30 g, 77%), m.p. 220–221 C. IR: 3109 (NH), 1608 (C=N), 1329 (C-N), 1228 (C=S),
1
1122 (O-CH3). H-NMR (400 MHz, DMSO-d6)
δ, ppm: O-CH3 [3.65 (s, 3H), 3.75 (s, 6H), 3.80 (s, 3H)],
4.99 (s, 2H, O-CH2), Ar.H [6.74 (s, 2H), 6.99 (d, J = 8 Hz, 2H), 7.03 (d, J = 8 Hz, 2H), 7.24–7.27 (m, 4H),
13.99 (s, 1H, NH). 13C-NMR (100 MHz, DMSO-d6)
, ppm: O- H3 (55.9, 56.3, 60.5), 70.1 (O- H2), Ar.C
=S).
δ
C
C
[105.9, 114.9, 115.3, 118.7, 127.7, 130.2, 130.4, 132.5, 137.6, 151.1 (C=N), 153.4, 160.0, 160.2], 169.1 (
C
HREIMS, C25H25N3O5S, m/z = 502.1408, [M + Na]+. Calcd. 502.1402.
4-(2-Methoxyphenyl)-3-(4-(3,4,5-trimethoxybenzyloxy)phenyl)-1H-1,2,4-triazole-5-(4H)-thione (4c). White
˝
solid (Ethyl acetate, 0.29 g, 75%), m.p. 239–242 C. IR: 3271 (NH), 1614 (C=N), 1329 (C-N), 1242 (C=S),
1
1122 (O-CH3). H-NMR (400 MHz, DMSO-d6)
δ
, ppm:O-CH3 [3.57 (s, 3H), 3.64 (s, 3H), 3.74 (s, 6H)],