246 J. Chin. Chem. Soc., Vol. 49, No. 2, 2002
Chiu et al.
1
cm-1; H NMR (DMSO-d6) d 8.31 (s, 1H), 7.91-6.99 (m,
3328, 1707, 1674 cm-1; 1H NMR (DMSO-d6) d 8.51 (s, 1H),
7.92 (d,J = 9.0 Hz, 2H), 7.66 (d, J = 9.0 Hz, 2H), 7.55 (d, J =
9.0 Hz, 2H), 7.48 (d,J = 9.0 Hz, 2H), 6.80 (d, J = 8.4 Hz, 1H),
6.73 (d,J = 8.4 Hz, 1H), 5.89 (s, 2H); EIMS (70 eV)m/z: 425
(M++4, 2), 423 (M++2, 8), 421 (M+, 11), 365 (4), 363 (25),
361 (37), 282 (3), 280 (8), 256 (5), 254 (36), 252 (72), 197
(4), 195 (9), 171 (6), 169 (17), 155 (16), 153 (48), 143 (30),
141 (100), 113 (20), 111 (60), 90 (20). Anal. Calcd for
C17H13Cl2N5O2S: C, 48.35; H, 3.10; Cl, 16.79; N, 16.58; S,
7.59. Found: C, 48.36; H, 3.20; Cl, 16.79; N, 16.58; S, 7.49.
11H), 5.18 (s, 2H), 3.69 (t, J = 6.3 Hz, 2H), 3.20-3.10 (m,
2H), 1.88-1.82 (m, 2H); EIMS (70 eV) m/z: 352 (M+, 5), 247
(12), 201 (21), 119 (13), 108 (100), 91 (21), 77 (23). Anal.
Calcd for C 18H20N6O2: C, 61.36; H, 5.68; N, 23.86. Found: C,
61.40; H, 5.64; N, 23.82.
4-[3-(2-p-Methylphenyl-2,4-dihydro-1,2,4-triazol-3-
on-4-yl)propyl]-2-p-methylphenylsemicarbazide (8b): col-
or less nee dles; mp > 240 °C; IR (KBr) 3412, 3364, 1683,
1662 cm-1; 1H NMR (DMSO-d6) d 8.27 (s, 1H), 7.62 (d, J =
8.4 Hz, 2H), 7.46-7.40 (m, 3H), 7.24 (d, J = 8.4 Hz, 2H), 7.05
(d, J = 8.4 Hz, 2H), 5.10 (s, 2H), 3.68 (t, J = 6.8 Hz, 2H),
3.18-3.10 (m, 2H), 1.90-1.83 (m, 2H); EIMS (70 eV) m/z: 380
(M+, 7), 258 (30), 203 (43), 175 (15), 122 (100), 105 (40), 91
(35). Anal. Calcd for C20H24N6O2: C, 63.14; H, 6.35; N,
22.09. Found: C, 63.12; H, 6.29; N, 22.14.
4-[3-(2-p-Chlorophenyl-2,4-dihydro-1,2,4-triazol-3-
on-4-yl)propyl]-2-p-chlorophenylsemicarbazide (8c): col or-
less nee dles; mp > 240 °C; IR (KBr) 3400, 3340, 1698, 1662
cm-1; 1H NMR (DMSO-d6) d 8.34 (s, 1H), 7.92 (d, J = 9.0 Hz,
2H), 7.62 (d, J = 9.0 Hz, 2H), 7.60 (br, 1H), 7.51 (d, J = 9.0
Hz, 2H), 7.30 (d,J = 9.0 Hz, 2H), 5.22 (s, 2H), 3.68 (t, J = 6.8
Hz, 2H), 3.19-3.10 (m, 2H), 1.88-1.82 (m, 2H); EIMS (70
eV) m/z: 422 (M++2, 2), 420 (M+, 4), 282 (5), 280 (35), 278
(80), 238 (14), 236 (43), 225 (43), 223 (100), 197 (8), 195
(25), 155 (9), 153 (27), 144 (32), 142 (100), 127 (39), 125 (78),
113 (11), 111 (32), 90 (31). Anal. Calcd for C18H18Cl2N6O2:
C, 51.32; H, 4.31; Cl, 16.83; N, 19.95. Found: C, 51.34; H,
4.36; Cl, 16.86; N, 19.91.
Synthesis of 10 from Reaction of 1 with
2-Amino-1,3-thiazole
0.6 g (2.90 mmol) 1a and 0.87 g (8.70 mmol) 2- amino-
1,3-thiazole were stirred in 6 mL isopropyl al co hol at room
temperaturefor2hoursandthenthemixturewaspouredinto
100 mL of ice wa ter. The pre cip i tate was recrystalized from
EtOAc + isopropyl al co hol to ob tain10a. Ac cord ing to this
procedure, reactionofvariousformsof 1 with 2-amino-1,3-
thiazole was achieved.
(1-p-Methylphenylhydrazino) carboxylic acid (2-(2-p-
methylphenyl-4-amino-2,4-dihydro-1,2,4-triazol-3-on-4-yl)-
vinyl)thiolate (10a): col or less nee dles; mp > 250 °C; IR
(KBr) 3466, 3364, 3304, 3208, 1710, 1671, 1644 cm-1; 1H
NMR (DMSO-d6) d 7.71 (d, J = 8.5 Hz, 2H), 7.46 (d, J = 8.5
Hz, 2H), 7.21-7.17 (m, 4H), 7.01 (d, J = 7.8 Hz, 1H), 6.38 (d,
J = 7.8 Hz, 1H), 6.24 (s, 2H), 5.71 (s, 2H), 2.28 (s, 6H); EIMS
(70 eV) m/z: 396 (M+, 41), 247 (26), 190 (38), 147 (18), 121
(34), 91 (100), 77 (34). Anal. Calcd for C19H20N6O2S: C,
57.56; H, 5.08; N, 21.20; S, 8.09. Found: C, 57.58; H, 5.04;
N, 21.21; S, 8.05.
Synthesis of 9 from Reaction of 1 with 1,3-Thiazole
0.74 g (8.70 mmol) 1,3-thiazole dis solved in 6 mL iso-
propyl al co hol was stirred with 0.6 g (2.90 mmol)1ain an ice
bath for 0.5 hour and then the mix ture was poured into 100
mL of ice wa ter. The pre cip i tate was recrystalized from THF
+isopropylalcoholtoobtain9a.Accordingtothisprocedure,
reactionofvariousformsof1 with 1,3-thiazole was achieved.
(1-Phenylhydrazino) carboxylic acid (2-(2-phenyl-
2,4-dihydro-1,2,4-triazol-3-on-4-yl)vinyl)thiolate(9a): col-
or less nee dles; mp > 250 °C; IR (KBr) 3340, 3274, 3214,
(1-p-Chlorophenylhydrazino) carboxylic acid (2-(2-p-
chlorophenyl-4-amino-2,4-dihydro-1,2,4-triazol-3-on-4-yl)-
vinyl)thiolate (10b): colorless needles; mp > 250 °C; IR
(KBr) 3466, 3346, 3208, 1713, 1647 cm-1; 1H NMR (DMSO-
d6) d 7.86 (d, J = 9.0 Hz, 2H), 7.64 (d,J = 9.0 Hz, 2H), 7.46 (d,
J = 9.0 Hz, 2H), 7.45 (d,J = 9.0 Hz, 2H), 7.01 (d, J = 5.8 Hz,
1H), 6.41 (d, J= 5.8 Hz, 1H), 6.38 (s, 2H), 5.81 (s, 2H); EIMS
(70 eV) m/z: 440 (M++4, 1), 438 (M++2, 5), 436 (M+, 9), 269
(9), 267 (20), 212 (4), 210 (14), 155 (7), 153 (23), 143 (14),
141 (55), 127 (13), 125 (38), 113 (32), 111 (100), 90 (33), 77
(84). Anal. Calcd for C17H14Cl2N6O2S: C, 46.70; H, 3.23; Cl,
16.21; N, 19.22; S, 7.33. Found: C, 46.69; H, 3.22; Cl, 16.21;
N, 19.22; S, 7.30.
1725, 1677 cm-1; H NMR (DMSO-d6) d 8.14 (s, 1H), 7.92-
1
7.13 (m, 10H), 6.81 (d, J = 8.5 Hz, 1H), 6.73 (d, J = 8.5 Hz,
1H), 5.86 (s, 2H); EIMS (70 eV) m/z: 353 (M+, 7), 293 (15),
248 (22), 161 (40), 135 (12), 105 (80), 77 (100). Anal. Calcd
for C 17H15N5O2S: C, 57.78; H, 4.28; N, 19.82; S, 9.07. Found:
C, 57.77; H, 4.30; N, 19.78; S, 9.16.
Synthesis of 11 from Reaction of 1 with
2-Amino-1,3,4-thiadiazole
0.6 g (2.71 mmol) 1b and 0.82 g (8.10 mmol) 2-amino-
1,3,4-thiadiazole were stirred in 6 mL isopropyl al co hol at 60
(1-p-Chlorophenylhydrazino) carboxylic acid (2-(2-
chlorophenyl-2,4-dihydro-1,2,4-triazol-3-on-4-yl)vinyl)-
thiolate (9b): col or less nee dles; mp 224-225 °C; IR (KBr)