2784
X.-H. Liu et al. / European Journal of Medicinal Chemistry 44 (2009) 2782–2786
Fig. 1. The pesticides containing 1,3,4-thiadizole ring.
7c: white crystal, yield 81.2%, m.p. 197–198 ꢂC; 1H NMR (CDCl3)
: 1.04–1.19 (m, 4H, cyclopropane–CH2), 1.38 (t, 3H, CH3), 2.21–2.26
Table 1
The antifungal activities of compounds 7a–7q in vivo at 500
m
g mLꢀ1
.
d
(m, 1H, cyclopropane–CH), 3.02 (q, 2H, CH2), 13.14 (s, 1H, NH);
FTICR-MS for C8H11N3OS: found 196.0556, calcd. 196.0550.
No.
Sclerotinia
sclerotiorum solanii
(Lib.) de
Rhizoctonia Fusarium
Corynespora Botrytis
oxysporum cassiicola
cinerea
7d: white crystal, yield 84.5%, m.p.175–176 ꢂC; 1H NMR (CDCl3)
d:
Bary
1.02 (t, 3H, CH3), 1.05–1.21 (m, 4H, cyclopropane–CH2), 1.81 (m, 2H,
CH2), 2.25–2.31 (m,1H, cyclopropane–CH), 2.98 (t, 2H, CH2),13.43 (s,
1H, NH); FTICR-MS for C9H13N3OS: found 210.0704, calcd. 210.0707.
7e: white crystal, yield 84.5%, m.p. 127–128 ꢂC; 1H NMR (CDCl3)
7a
7b
7c
7d
7e
7f
7g
7h
7i
7j
7k
7l
7m
7n
7o
7p
24.00
23.00
51.70
40.00
47.70
10.30
24.00
37.50
20.00
23.90
25.50
23.00
43.06
14.00
5.00
37.00
5.00
17.00
84.00
10.00
1.00
20.00
2.00
16.00
21.00
11.00
28.00
91.00
84.00
13.00
14.00
0
22.52
52.43
49.66
46.63
29.30
21.92
17.43
50.79
8.38
19.69
21.45
68.27
18.56
34.06
15.73
33.26
13.28
83.73
67.54
32.09
57.87
41.98
26.02
80.53
75.09
90.67
13.49
35.11
67.54
30.27
29.66
38.76
79.38
66.59
23.00
35.00
11.00
44.00
9.00
36.00
39.00
62.00
44.00
5.00
d: 0.92–0.96 (t, 3H, CH3), 1.04–1.19 (m, 4H, cyclopropane–CH2), 1.43
(m, 2H, CH2), 1.56 (m, 2H, CH2), 1.75 (m, 2H, CH2), 2.19–2.22 (m, 1H,
cyclopropane–CH), 13.00 (s, 1H, NH); FTICR-MS for C10H15N3OS:
found 210.0702, calcd. 210.0707.
7f: white crystal, yield 90.1%, m.p. 183–184 ꢂC; 1H NMR (CDCl3)
d: 1.03–1.29 (m, 4H, cyclopropane–CH2), 1.40 (d, 6H, CH3), 2.26–
2.28 (m, 1H, cyclopropane–CH), 3.33–3.40 (m, 1H, CH), 7.26–7.71
(m, 4H, Ar-H), 13.27 (s, 1H, NH); FTICR-MS for C9H13N3OS: found
224.0865, calcd. 224.0863.
16.00
8.00
0
7g: white crystal, yield 86.5%, m.p. 249–251 ꢂC; 1H NMR (CDCl3)
33.0
26.70
96.70
ꢀ9.00
12.00
37.00
7q
21.00
d: 1.11–1.26 (m, 4H, cyclopropane–CH2), 2.35 (m, 1H, cyclopropane–
dimehachlon
Jinggangmycin
Thiophanate
methyl
Chlorothalonil
Pyrimethanil
CH), 7.47–7.92 (m, 5H, Ar-H), 13.33 (bs, 1H, NH); FTICR-MS for
C12H11N3OS: found 244.0550, calcd. 244.0550.
92.10
97.00
7h: white crystal, yield 82.6%, m.p. 216–218 ꢂC; 1H NMR (CDCl3)
86.43
d: 1.04–1.25 (m, 4H, cyclopropane–CH2), 2.39–2.45 (m, 1H, cyclo-
99.17
propane–CH), 2.56 (s, 3H, CH3), 7.29–7.65 (m, 4H, Ar-H), 13.07
(bs, 1H, NH); FTICR-MS for C13H13N3OS: found 260.0841, calcd.
260.0852.
7i: white crystal, yield 80.6%, m.p. 262–265 ꢂC; 1H NMR (CDCl3)
4.2. Synthesis
d: 1.11–1.26 (m, 4H, cyclopropane–CH2), 2.31–2.36 (m, 1H, cyclo-
4.2.1. General procedure
propane–CH), 2.43 (d, 3H, CH3), 7.26–7.71 (m, 4H, Ar-H),13.19 (s,1H,
NH); FTICR-MS for C13H13N3OS: found 260.0841, calcd. 260.0852.
4.2.1.1. Preparation of 7a. The acid chloride was prepared according
the reference [12]. Dropwised the acid chloride to substituted 2-
amino-5-substituted-1,3,4-thiadiazoles (7.50 mmol), then vigor-
ously stirred at ambient temperature for 4 h. The corresponding
amide 7 precipitated immediately. The product was filtered,
washed with THF, dried, and recrystallized from EtOH–H2O to give
the title compounds 7.
7j: white crystal, yield 84.6%, m.p. > 300 ꢂC; 1H NMR (DMSO)
d:
0.93–1.02 (m, 4H, cyclopropane–CH2), 1.98–2.05 (m, 1H, cyclopro-
pane–CH), 7.60 (d, J ¼ 8.55 Hz, 2H, Ar-H), 7.95 (d, J ¼ 8.54 Hz, 2H, Ar-
H), 12.99 (bs, 1H, NH); FTICR-MS for C12H10ClN3OS: found 280.0296,
calcd. 280.0306.
7a: white crystal, yield 84.6%, m.p. 254–255 ꢂC; 1H NMR (CDCl3)
d: 1.08–1.25 (m, 4H, cyclopropane–CH2), 1.59 (s, 1H, Het-H), 2.29–
2.35 (m, 1H, cyclopropane–CH), 8.78 (s, 1H, NH); FTICR-MS for
C6H7N3OS: found 168.0229, calcd. 168.0237.
7b: white crystal, yield 85.1%, m.p. > 300 ꢂC; 1H NMR (CDCl3)
d:
1.05–1.19 (m, 4H, cyclopropane–CH2), 1.55 (t, 3H, CH3), 2.16–2.26
(m, 1H, cyclopropane–CH), 12.85 (s, 1H, NH); FTICR-MS for
C7H9N3OS: found 182.0395, calcd. 182.0394.
O
*
*
S
*
R
*
*
*
*
HN
*
N
*
N
*
Fig. 2. The asterisk skeleton of title compounds.
Fig. 3. Superposition modes of compounds.