Synthesis and Insecticidal Activities of Derivatives of Neonicotinoid Compound
pounds 12a— 12j are listed in Table 1.
Propyl 2-{3-[(2-chlorothiazol-5-yl)methyl]-2-(ni-
troimino)imidazolidin-1-yl}-2-oxoacetate (13c)
1
Table 1 Boiling points, yields of the compounds 12a— 12j
White solid, yield 66.1%, m.p. 108—110 ℃; H NMR
(CDCl3, 400 MHz) δ: 7.54 (s, 1H, thiazole-H), 4.70 (s,
3
2H, thiazolyl-CH2), 4.24 (q, JHH=6.8 Hz, 2H, OCH2),
Compd.
R
b.p./℃
Yield/%
3
3
4.15 (t, JHH=8.0 Hz, 2H, CH2CH2), 3.73 (t, JHH=8.0
Hz, 2H, CH2CH2), 1.71—1.80 (m, 2H, CH2CH3), 0.98 (t,
3JHH=7.5 Hz, 3H, CH3); IR (KBr) ν: 3417, 2971, 1744,
12a
12b
12c
12d
12e
12f
12g
12h
12i
Methyl
Ethyl
118— 120
75.3
69.6
77.2
71.0
66.4
60.2
63.7
43.6
84.8
60.3
132— 135
-1
1725, 1571, 1502, 1262, 1+262, 1187, 1048, 701 cm ;
n-Propyl
i-Propyl
n-Butyl
150— 152
ESI-MS m/z: 376 (M + 1). Anal. calcd for
C12H14ClN5O5S: C 38.35, H 3.76, N 18.64; found C
38.41, H 4.00, N 18.89.
149— 151
77— 79 (400 Pa)
75— 76 (400 Pa)
76— 78 (400 Pa)
95— 97 (400 Pa)
63— 66 (400 Pa)
97— 99 (400 Pa)
i-Butyl
Isopropyl 2-{3-[(2-chlorothiazol-5-yl)methyl] 2-
(nitroimino)imidazolidin-1-yl}-2-oxoacetate
(13d)
s-Butyl
1
White solid, yield 61.6%, m.p. 140—141 ℃; H NMR
(CDCl3, 400 MHz) δ: 7.54 (s, 1H, thiazole-H), 5.12—
5.20 (m, 1H, OCH), 4.70 (s, 2H, thiazolyl-CH2), 4.14 (t,
3JHH=8.0 Hz, 2H, CH2CH2), 3.74 (t, 3JHH=8.0 Hz, 2H,
Cyclohexyl
Allyl
12j
2-Methoxyethyl
3
CH2CH2), 1.35 [d, JHH=6.3 Hz, 6H, CH(CH3)2]; IR
(KBr) ν: 3401, 2984, 17-48, 1736, 1569, 1529, 1450,
General synthetic procedure for the title compounds
13a— 13j
+
1
1287, 1225, 1046, 923 cm ; ESI-MS m/z: 376 (M +1).
Anal. calcd for C12H14ClN5O5S: C 38.35, H 3.76, N
18.64; found C 38.10, H 3.95, N 18.78.
The compound 11 (0.01 mol) was dissolved in dry
dimethylformamide (30 mL), and sodium hydride
(0.011 mol) was added at 10 ℃. The mixture was
stirred at room temperature until the generation of hy-
drogen ceased. Then, appropriate alkyloxyoxalyl chlo-
ride 12 (0.011 mol) was added, and the mixture was
stirred at 30 ℃ for 5 h, and poured into ice water (50
mL). The aqueous layer was extracted with dichloro-
methane (40 mL×3). The dichloromethane layer was
washed with water (40 mL×3) and dried over anhy-
drous sodium sulfate. Then the dichloromethane was
evaporated. The residue was purified by column chro-
matography on a silica gel using petroleum ether (60—
90 ℃) and ethyl acetate as the eluent to afford the title
compounds 13a—13j.
Butyl
2-{3-[(2-chlorothiazol-5-yl)methyl]-2-(ni-
(13e)
troimino)imidazolidin-1-yl}-2-oxoacetate
1
White solid, yield 63.7%, m.p. 105—107 ℃; H NMR
(CDCl3, 400 MHz) δ: 7.54 (s, 1H, thiazole-H), 4.71 (s,
3
2H, thiazolyl-CH2), 4.28 (t, JHH=6.7 Hz, 2H, OCH2),
3
3
4.15 (t, JHH=8.0 Hz, 2H, CH2CH2), 3.74 (t, JHH=8.0
Hz, 2H, CH2CH2), 1.66—1.74 (m, 2H, OCH2CH2), 1.36
3
—1.46 (m, 2H, CH2CH3), 0.95 (t, JHH=7.4 Hz, 3H,
CH3); IR (KBr) ν: 3400, 2961, 1749, 1740, 1682, 1533,
-1
1421, 1286, 1188, 1046, 927 cm ; ESI-MS m/z: 390
(M++1). Anal. calcd for C13H16ClN5O5S: C 40.05, H
4.14, N 17.97; found C 40.19, H 4.08, N 18.03.
Isobutyl
2-{3-[(2-chlorothiazol-5-yl)methyl]-2-(nitroimino)imi
dazolidin-1-yl}-2-oxoacetate (13f) White solid, yield
43.9%, m.p. 120—122 ℃; 1H NMR (CDCl3, 400 MHz)
δ: 7.54 (s, 1H, thiazole-H), 4.70 (s, 2H, thiazolyl-CH2),
4.15 (t, 3JHH=7.8 Hz, 2H, CH2CH2), 4.01 (d, 3JHH=6.6
Methyl 2-{3-[(2-chlorothiazol-5-yl)methyl]-2-(ni-
troimino)imidazolidin-1-yl}-2-oxoacetate
(13a)
1
White solid, yield 72.1%, m.p. 97—99 ℃; H NMR
(CDCl3, 400 MHz) δ: 7.54 (s, 1H, thiazole-H), 4.71 (s,
2H, thiazolyl-CH2), 4.16 (t, 3JHH=8.0 Hz, 2H, CH2CH2),
3.90 (s, 3H, CH3), 3.74 (t, 3JHH=8.0 Hz, 2H, CH2CH2);
IR (KBr) ν: 3404, 2-915, 1764, 1745, 1675, 1567, 1448,
3
Hz, 2H, OCH2), 3.74 (t, JHH=7.8 Hz, 2H, CH2CH2),
1.98—2.09 (m, 1H, CH2CH), 0.97 (d, 3JHH=6.6 Hz, 6H,
CH(CH3)2); IR (KBr) ν: 3428, 2964, 1744, 1723, 1595,
+
1
-1
1287, 1224, 925 cm ; ESI-MS m/z: 348 (M +1). Anal.
calcd for C10H10ClN5O5S: C 34.54, H 2.90, N 20.14;
found C 34.58, H 2.97, N 20.09.
1503, 1472, 1406, 1263, 1186, 1048, 943 cm ; ESI-MS
m/z: 390 (M++1). Anal. calcd for C13H16ClN5O5S: C
40.05, H 4.14, N 17.97; found C 40.00, H 4.05, N 17.86.
sec-Butyl 2-{3-[(2-chlorothiazol-5-yl)methyl]-2-
Ethyl
2-{3-[(2-chlorothiazol-5-yl)methyl]-2-(nitroimino)imi
dazolidin-1-yl}-2-oxoacetate (13b) White solid, yield
69.6%, m.p. 104—105 ℃; 1H NMR (CDCl3, 400 MHz)
δ: 7.54 (s, 1H, thiazole-H), 4.70 (s, 2H, thiazolyl-CH2),
(nitroimino)imidazolidin-1-yl}-2-oxoacetate
(13g)
1
White solid, yield 69.1%, m.p. 117—119 ℃; H NMR
(CDCl3, 400 MHz) δ: 7.54 (s, 1H, thiazole-H), 4.96—
5.01 (m, 1H, OCH), 4.70 (s, 2H, thiazolyl-CH2), 4.13 (t,
3JHH=8.2 Hz, 2H, CH2CH2), 3.72 (t, 3JHH=8.2 Hz, 2H,
CH2CH2), 1.58 — 1.75 (m, 2H, CH2CH3), 1.33 (d,
3
3
4.37 (q, JHH=7.1 Hz, 2H, OCH2), 4.14 (t, JHH=8.1
Hz, 2H, CH2CH2), 3.73 (t, 3JHH=8.1 Hz, 2H, CH2CH2),
1.38 (t, 3JHH=7.1 Hz, 3H, CH3); IR (KBr) ν: 3392, 2981,
3
3JHH=6.3 Hz, 3H, CHCH3), 0.95 (t, JHH=7.5 Hz, 3H,
-1
1746, 1722, 1592, 1572, 1472, 1262, 1185, 1047 cm ;
CH2CH3); IR (KBr) ν: 3392, 2938, 1747, 1735, 1680,
+
-1
ESI-MS m/z: 362 (M + 1). Anal. calcd for
1569, 1472, 1450, 1287, 1225, 1047, 925 cm ; ESI-MS
m/z: 390 (M++1). Anal. calcd for C13H16ClN5O5S: C
C11H12ClN5O5S: C 36.52, H 3.34, N 19.36; found C
36.57, H 3.40, N 19.49.
Chin. J. Chem. 2010, 28, 475— 479
© 2010 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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