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J. Agric. Food Chem., Vol. 57, No. 9, 2009
Sun et al.
(0.68 g, 5 mmol) in anhydrous diethyl ether cooled in an ice-salt
bath. The mixture was stirred for 1 h after the addition was complete
and filtered. Then, the filtrate was washed by saturated brine and
dried over anhydrous sodium sulfate. The filtrate was concentrated
in vacuo to give an oil, which was purified by flash-column
chromatography on a silica gel using a mixture of petroleum ether
(60-90 °C) and ethyl acetate (12:1, v/v) as the eluent to obtain
compound IVa as a pale yellow solid (1.30 g, 66.7%); mp 49-51 °C.
1H NMR (300 M, CDCl3) δ: 5.45 (s, 2H, NH), 6.98 (d, 4H, Ph), 7.40
(d, 4H, Ph). Intermediates IVb-IVe were prepared by following the
same procedure as for IVa, and disulfur dichloride was displaced by
sulfur dichloride when necessary.
9.75 (s, 1H, CONH). Anal. Calcd for C22H13F8N3O2S: C, 49.35; H,
2.45; N, 7.85. Found: C, 48.95; H, 2.55; N, 8.42.
N0-(2,6-Difluorobenzoyl)-N-(4-(trifluoromethoxyl)phe-
nylaminylthio)-N-(4-(trifluoromethoxyl)phenyl)urea (18).
Yield, 74.9%; white solid; mp 125 °C (dec). 1H NMR (300 M,
CDCl3) δ: 6.74 (d, 2H, 3JHH = 9.0 Hz, Ph), 6.94 (m, 4H, Ph), 7.02 (s,
1H, NH), 7.14 (m, 4H, Ph), 7.46 (m, 1H, Ph), 9.53 (s, 1H, CONH).
Anal. Calcd for C22H13F8N3O4S: C, 46.57; H, 2.31; N, 7.41. Found:
C, 46.30; H, 2.47; N, 7.58.
Synthesis of Bis(N0-(2,6-difluorobenzoyl)-N-(4-(trifluor-
omethoxy)phenyl)urea)disulfide (19). A solution of 2,6-di-
fluorobenzoyl isocyanates (0.09 g, 0.5 mmol) in dry
dichloromethane (3 mL) was added dropwise to a solution of
compound 13 (0.30 g, 0.5 mmol) in dry dichloromethane (5 mL)
at room temperature, and the mixture was stirred for 1 h after the
addition was complete. After removal of the solvent, the white solid
was purified by recrystallization from diethyl ether to give com-
pound 19 as a white crystal (0.28 g, 71.8%); mp 109 °C (dec).
1H NMR (300 M, CDCl3) δ: 6.95 (t, 4H, 3JHH = 8.4 Hz, Ph), 7.32
Bis(4-(trifluoromethoxy)phenylamine)disulfide
Yield, 70.4%; mp 37-38 °C.
Bis(4-(trifluoromethoxy)phenylamine)sulfide
(IVb).
(IVc).
Yield, 69.3%; mp 55-57 °C.
Bis(4-chloro-phenylamine)sulfide (IVd). Yield, 77.2%; mp
99-101 °C (from ref 20, 102-103 °C).
Bis(4-(trifluoromethyl)phenylamine)sulfide (IVe). Crude
3
yield, 67.3%; oil.
(d, 4H, JHH = 8.1 Hz, Ph), 7.37-7.46 (m, 2H, Ph), 7.57 (d, 4H,
3JHH = 9.0 Hz, Ph), 7.85 [s, 2H, 2(CONH)]. Anal. Calcd for
Synthesis of N0-(2,6-Difluorobenzoyl)-N-(4-(trifluoro-
methyl)phenyl)-N-((4-trifluoromethyl)benzenaminyldithio)
urea (12). A solution of 2,6-difluorobenzoyl isocyanates (0.18 g,
1.0 mmol) in dry dichloromethane (5 mL) was added dropwise to a
solution of compound IVa (0.38 g, 1.0 mmol) in dry dichloro-
methane (10 mL), which was cooled with an ice bath, and the
mixture was stirred for 1 h at room temperature. After removal of
the solvent, the white solid was purified by recrystallization from
diethyl ether to give compound 12 as a white solid (0.40 g, 71.4%);
mp 122 °C (dec). 1H NMR (300 M, CDCl3) δ: 6.17 (s, 1H, NH), 6.90
C
30H16F10N4O6S2: C, 46.04; H, 2.06; N, 7.16. Found: C, 45.91; H,
2.02; N, 7.29. The target compounds 20-24 were prepared by
following the same procedure as for compound 19.
1-(((30-(20-Chlorobenzoyl)-10-(40-(trifluoromethoxy)
phenyl)urea)-10-yl)dithio)-3-(2,6-difluorobenzoyl)-1-(4-
(trifluoromethoxy)phenyl)urea (20). Yield, 51.3%; white
1
solid; mp 142 °C (dec). H NMR (300 M, CDCl3) δ: 6.88 (t, 2H,
3JHH = 8.4 Hz, Ph), 7.32-7.43 (m, 8H, Ph), 7.65-7.71 (m, 5H, Ph),
7.88 (s, 1H, CONH), 8.24 (s, 1H, CONH). Anal. Calcd for
C30H17F8N4O6S2: C, 46.13; H, 2.19; N, 7.17. Found: C, 45.95; H,
2.24; N, 7.17.
3
3
(t, 2H, JHH = 8.4 Hz, Ph), 7.07 (d, 2H, JHH = 8.4 Hz, Ph),
7.35-7.48 (m, 5H, Ph), 7.63 (d, 2H, 3JHH = 8.4 Hz, Ph), 9.13 (s, 1H,
CONH). Anal. Calcd for C22H13F8N3O2S2: C, 46.56; H, 2.31;
N, 7.40. Found: C, 46.57; H, 2.32; N, 7.30. The target compounds
13-18 were prepared by following the same procedure as for
compound 12.
Bis(N0-(2-chlorobenzoyl)-N-(4-(trifluoromethoxy)phen-
yl)urea)disulfide (21). Yield, 64.1%; white solid; mp 131 °C
(dec). 1H NMR (300 M, CDCl3) δ: 7.28-7.38 (m, 10H, Ph), 7.71-
7.76 (m, 6H, Ph), 8.30 [s, 2H, 2(CONH)]. Anal. Calcd for
C30H18Cl2F6N4O6S2: C, 46.22; H, 2.33; N, 7.19. Found: C, 46.18;
H, 2.24; N, 7.04.
N0-(2,6-Difluorobenzoyl)-N-(4-(trifluoromethoxyl)phen-
yl)-N-((4-trifluoromethoxyl)benzenaminyldithio)urea (13).
Yield, 66.7%; white solid; mp 91 °C (dec). 1H NMR (300 M, CDCl3)
δ: 5.76 (s, 1H, NH), 6.92 (t, 2H, 3JHH = 8.4 Hz, Ph), 6.98 (d, 2H,
3JHH = 9.0 Hz, Ph), 7.08 (d, 2H, 3JHH = 9.0 Hz, Ph), 7.23 (d, 2H,
3JHH = 8.4 Hz, Ph), 7.34-7.45 (m, 3H, Ph), 8.93 (s, 1H, CONH).
Anal. Calcd for C22H13F8N3O4S2: C, 44.08; H, 2.19; N, 7.01.
Found: C, 44.05; H, 2.17; N, 7.06.
Bis(N0-(2,6-difluorobenzoyl)-N-(4-(trifluoromethoxy)
phenyl)urea)sulfide (22). Yield, 69.3%; white solid; mp 144 °C
(dec). 1H NMR (300 M, CDCl3) δ: 6.94 (t, 4H, 3JHH = 8.4 Hz, Ph),
7.26-7.43 (m, 10H, Ph), 9.10 [s, 2H, 2(CONH)]. Anal. Calcd for
C30H16F10N4O6S: C, 48.01; H, 2.15; N, 7.47. Found: C, 48.38; H,
2.42; N, 7.13.
N0-(2-Chlorobenzoyl)-N-(4-(trifluoromethoxyl)phenyl)-
Bis(N-(4-chlorophenyl)-N0-(2,6-difluorobenzoyl)urea)
sulfide (23). Yield, 58.6%; white solid; mp 135 °C (dec). 1H NMR
N-((4-trifluoromethoxyl)benzenaminyldithio)urea
(14).
Yield, 79.8%; white solid; mp 127 °C (dec). 1H NMR (300 M,
CDCl3) δ: 6.64 (s, 1H, NH), 6.94-7.11 (m, 5H, Ph), 7.18 (d, 2H,
3JHH = 9.0 Hz, Ph), 7.30-7.39 (m, 3H, Ph), 7.46 (d, 2H, 3JHH = 8.4
Hz, Ph), 9.39 (s, 1H, CONH). Anal. Calcd for C22H14ClF6N3O4S2:
C, 44.19; H, 2.36; N, 7.03. Found: C, 44.50; H, 2.76; N, 7.24.
3
(300 M, CDCl3) δ: 6.90 (t, 4H, JHH = 8.4 Hz, Ph), 7.02 (d, 4H,
3JHH = 8.0 Hz, Ph), 7.25 (d, 4H, 3JHH = 8.4 Hz, Ph), 7.35-7.42 (m,
2H, Ph), 9.58 [s, 2H, 2(CONH)]. Anal. Calcd for C28H16Cl2F4N4O4S:
C, 51.63; H, 2.48; N, 8.60. Found: C, 51.80; H, 2.42; N, 8.56.
1-(((30-(20-Chlorobenzoyl)-10-(40-(trifluoromethoxy)
phenyl)urea)-10-yl)thio)-3-(2,6-difluorobenzoyl)-1-(4-(tri-
fluoromethoxy)phenyl)urea (24). Yield, 62.3%; white solid; mp
139 °C (dec). 1H NMR (300 M, CDCl3) δ: 6.91 (t, 2H, 3JHH = 8.4
Hz, Ph), 7.01-7.59 (m, 13H, Ph), 8.82 (s, 1H, CONH), 10.48 (s, 1H,
CONH). Anal. Calcd for C30H17ClF8N4O6S: C, 48.11; H, 2.29; N,
7.48. Found: C, 48.00; H, 2.51; N, 7.32.
N0-(2-Chlorobenzoyl)-N-(4-(trifluoromethyl)phenyl)-N-
((4-trifluoromethyl)benzenaminyldithio)urea (15). Yield,
60.2%; white solid; mp 135 °C (dec). 1H NMR (300 M, CDCl3) δ:
6.94 (s, 1H, NH), 6.97-7.60 (m, 12H, Ph), 9.58 (s, 1H, CONH).
Anal. Calcd for C22H14ClF6N3O2S2: C, 46.69; H, 2.49; N, 7.42.
Found: C, 46.58; H, 2.44; N, 7.64.
N-(4-Chlorophenylaminylthio)-N0-(2,6-difluorobenzoyl)-
Biological Assay. All bioassays were performed on representa-
tive test organisms reared in the laboratory. The bioassay was
repeated at 25 ( 1 °C according to statistical requirements. Assess-
ments were made on a dead/alive basis, and mortality rates were
corrected using Abbott’s formula (21 ). Evaluations are based on a
percentage scale of 0-100, in which 0 = no activity and 100 = total
kill. The deviations of the tested biological values were (5%.
Larvicidal Activity against Oriental Armyworm (Mythimna
separata). The larvicidal activities of the target compounds 1-24
against oriental armyworm were evaluated by foliar application
using the reported procedure (16, 22, 23). For the foliar armyworm
tests, individual corn leaves were placed on moistened pieces of filter
N-(4-chlorophenyl)urea (16). Yield, 63.5%; white solid; mp
1
128-131 °C. H NMR (300 M, CDCl3) δ: 6.46 (s, 1H, NH), 6.75
(d, 2H, 3JHH = 8.4 Hz, Ph), 6.96 (t, 2H, 3JHH = 8.1 Hz, Ph), 7.07
(t, 4H, 3JHH = 7.5 Hz, Ph), 7.30 (d, 2H, 3JHH = 8.1 Hz, Ph), 7.42 (m,
1H, Ph), 9.52 (s, 1H, CONH). Anal. Calcd for C20H13Cl2F2N3O2S:
C, 51.29; H, 2.80; N, 8.97. Found: C, 50.86; H, 2.82; N, 9.35.
N0-(2,6-Difluorobenzoyl)-N-(4-(trifluoromethyl)phenyla-
minylthio)-N-(4-(trifluoromethyl)phenyl)urea (17). Yield,
1
52.3%; white solid; mp 126-127 °C. H NMR (300 M, CDCl3) δ:
=
6.72 (s, 1H, NH), 6.83 (d, 2H, 3JHH = 8.4 Hz, Ph), 6.98 (t, 2H, 3JHH
8.1 Hz, Ph), 7.30-7.49 (m, 5H, Ph), 7.59 (d, 2H, 3JHH = 8.4 Hz, Ph),