July 2011
Synthesis and Insecticidal Activities of Novel Neonicotinoid Analogs
Bearing an Amide Moiety
905
3307.9, 3086.1, 3051.3, 2893.2, 2181.4, 1643.3, 1560.4,
1
2-(1-((2-Chlorothiazol-5-yl)methyl)imidazolidin-2-ylidene)-2-
cyano-N,N-dimethylacetamide (6m). Light yellow solid; yield:
76%; mp: 135.2–136.6ꢁC; IR (KBr): m 3290.5, 2906.7, 2164.3,
1500.6, 1462.0 cmꢀ1; H-NMR (CDCl3, 500 MHz) d: 9.43 (br,
1H, NAH), 8.35 (d, J ¼ 2.30 Hz, 1H, pyridine-H), 7.69–7.71
(m, 2H, NAH þ pyridine-H), 7.59 (d, J ¼ 8.55 Hz, 2H,
2PhAH), 7.55 (d, J ¼ 9.15 Hz, 2H, 2PhAH), 7.39 (d, J ¼
9.15 Hz, 2H, 2PhAH), 4.97 (s, 2H, CH2), 7.51 (br, 1H, NH),
7.39 (d, J ¼ 8.55 Hz, 1H, pyridine-H), 4.93 (s, 2H, CH2),
3.53–3.70 (m, 4H, CH2CH2); 13C-NMR (CDCl3, 125 MHz) d:
166.99, 163.70, 151.72, 148.93, 141.47, 138.36, 130.13,
126.23, 126.20, 125.51, 125.36, 125.25, 124.93, 123.20,
121.07, 119.57, 54.39, 49.28, 47.75, 41.49; Anal. Calc. for
C19H15ClF3N5O: C, 54.10; H, 3.58; N, 16.60. Found: C,
54.20; H, 3.27; N, 16.32.
1604.7, 1548.8, 1498.6, 1485.1, 1458.1 cmꢀ1
;
1H-NMR
(CDCl3, 500 MHz) d: 9.00 (br, 1H, NH), 7.53 (s, 1H, thiazole-
H), 5.00 (s, 2H, CH2), 3.57–3.59 (m, 4H, CH2CH2), 3.06 (s,
6H, 2CH3); 13C-NMR (CDCl3, 125 MHz) d: 170.45, 165.83,
153.18, 141.01, 134.45, 121.06, 53.18, 49.16, 43.77, 41.31,
38.33; Anal. Calc. for C12H14ClN5OS: C, 46.23; H, 4.53; N,
22.46. Found: C, 46.30; H, 4.33; N, 22.2.
2-(1-((2-Chlorothiazol-5-yl)methyl)imidazolidin-2-ylidene)-2-
cyano-N-(o-tolyl)acetamide (6n). Light yellow solid; yield:
72%; mp: 174.5–175.8ꢁC; IR (KBr): m 3321.4, 3282.8, 3024.8,
2936.0, 2879.7, 2171.8, 1616.2, 1568.1, 1473.6, 1458.1 cmꢀ1
;
2-(1-((6-Chloropyridin-3-yl)methyl)imidazolidin-2-ylidene)-
2-cyano-N,N-dimethylacetamide (6i). Light yellow solid;
yield: 75%; mp: 104.0–105.5ꢁC; IR (KBr): m 3296.3, 3086.4,
2924.0, 2171.8, 1636.5, 1575.84, 1558.48, 15.6.4, 1481.3
1H-NMR (CDCl3, 500 MHz) d: 9.47 (br, 1H, NH), 7.54 (s,
1H, thiazole-H), 7.04–7.76 (m, 4H, 4PhAH), 7.49 (br, 1H,
NH), 5.00 (s, 2H, CH2), 3.56–3.65 (m, 4H, CH2CH2), 2.30 (s,
3H, CH3); 13C-NMR (CDCl3, 125 MHz) d: 166.81, 163.31,
153.39, 141.00, 136.12, 134.45, 130.57, 129.68, 126.66,
124.84, 123.00, 121.46, 54.48, 48.90, 43.37, 41.43, 17.88;
Anal. Calc. for C17H16ClN5OS: C, 54.61; H, 4.31; N, 18.73.
Found: C, 54.72; H, 3.94; N, 18.51.
cmꢀ1 1H-NMR (CDCl3, 500 MHz) d: 9.03 (br, 1H, NAH),
;
8.34 (d, J ¼ 2.30 Hz, 1H, pyridine-H), 7.76 (dd, J ¼ 2.30 Hz,
8.60 Hz, 1H, pyridine-H), 7.35 (d, J ¼ 8.55 Hz, 1H, pyridine-
H), 4.87 (s, 2H, CH2), 3.49–3.63 (m, 4H, CH2CH2), 3.03 (s,
6H, 2CH3); 13C-NMR (CDCl3, 125 MHz) d: 170.76, 166.28,
151.46, 149.04, 138.68, 130.54, 124.75, 121.14, 52.60, 49.63,
48.44, 41.37, 38.36; Anal. Calc. for C22H19ClN4O4S2: C,
52.53; H, 3.81; N, 11.14. Found: C, 52.94; H, 3.29; N, 11.62.
N-(4-Chlorophenyl)-2-(1-((2-chlorothiazol-5-yl)methyl)imi-
dazolidin-2-ylidene)-2-cyanoacetamide (6j). Light yellow solid;
yield: 72%; mp: 201–203ꢁC; IR (KBr): m 3329.4, 3269.3,
3050.0, 2960.7, 2877.9, 2187.2, 1643.3, 1566.2, 1527.6,
2-(1-((2-Chlorothiazol-5-yl)methyl)imidazolidin-2-ylidene)-2-
cyanoacetamide (6o). Light yellow solid; yield: 70%; mp:
206.1–208.5ꢁC; IR (KBr): m 3360.0, 3184.4, 2972.3, 2889.3,
2187.2, 1636.4, 1608.6, 1558.4, 15.5.0 cmꢀ1
;
1H-NMR
(DMSO-d6, 500 MHz) d: 9.31 (br, 1H, NH), 7.69 (s, 1H, thia-
zole-H), 6.47 (br, 2H, NH2), 4.97 (s, 2H, CH2), 3.47–3.53 (m,
4H, CH2CH2); 13C-NMR (DMSO-d6, 125 MHz) d: 170.27,
163.59, 151.32, 141.47, 136.52, 121.94, 52.85, 48.99, 43.11,
41.80; Anal. Calc. for C10H10ClN5OS: C, 42.33; H, 3.55; N,
24.68. Found: C, 42.15; H, 3.49; N, 24.32.
1494.8 cmꢀ1 1H-NMR (CDCl3, 500 MHz) d: 9.42 (br, 1H,
;
NAH), 7.55 (br, 1H, NAH), 7.54 (s, 1H, thiazole-H), 7.40 (d,
J ¼ 9.15 Hz, 2H, 2PhAH), 7.28 (d, J ¼ 9.15 Hz, 2H,
2PhAH), 5.03 (s, 2H, CH2), 3.58–3.68 (m, 4H, CH2CH2); 13C-
NMR (CDCl3, 125 MHz) d: 166.69, 163.31, 153.45, 141.05,
136.75, 134.26, 128.99, 128.93, 121.62, 121.20, 54.57, 48.90,
43.35, 41.43; Anal. Calc. for C16H13Cl2N5OS: C, 48.74; H,
3.32; N, 17.76. Found: C, 48.9; H, 3.24; N, 17.74.
2-(1-((2-Chlorothiazol-5-yl)methyl)imidazolidin-2-ylidene)-
2-cyano-N-(4-(trifluoromethyl)phenyl)acetamide (6p). White
solid; yield: 68%; mp: 164.0–165.8ꢁC; IR (KBr): m 3282.8,
2980.0, 2899.0, 2181.4, 1647.2, 1564.2, 1508.3, 1483.2 cmꢀ1
;
1H-NMR (CDCl3, 500 MHz) d: 9.41 (br, 1H, NH), 7.70 (s,
1H, thiazole-H), 7.54–7.60 (m, 5H, 4PhAH þ NH), 5.04 (s,
2H, CH2), 3.60–3.70 (m, 4H, CH2CH2); 13C-NMR (CDCl3,
125 MHz) d: 166.77, 163.29, 153.49, 141.39, 141.09, 134.17,
126.26, 126.23, 125.35, 123.19, 121.07, 119.58, 54.76, 48.91,
43.55, 41.46; Anal. Calc. for C17H13ClF3N5OS: C, 47.72; H,
3.06; N, 16.37. Found: C, 47.75; H, 2.92; N, 16.41.
2-(1-((2-Chlorothiazol-5-yl)methyl)imidazolidin-2-ylidene)-
2-cyano-N-(1-phenylethyl)acetamide (6k). Light yellow solid;
yield: 73%; mp: 129.5–131.5ꢁC; IR (KBr): m 3327.2, 3032.1,
2976.1, 2887.4, 2177.8, 1610.5, 1564.2, 1509.0, 1417.8 cmꢀ1
;
1H-NMR (CDCl3, 500 MHz) d: 9.45 (br, 1H, NAH), 7.51 (s,
1H, thiazole-H), 7.24–7.35 (m, 5H, 5PhAH), 6.0 (d, J ¼ 7.45
Hz, 1H, NAH), 5.00–5.06 (m, 1H, N-CH), 4.96 (s, 2H, CH2),
3.44–3.60 (m, 4H, CH2CH2), 1.50 (d, J ¼ 6.90 Hz, 3H, CH3);
13C-NMR (CDCl3, 125 MHz) d: 167.67, 163.25, 153.30,
144.10, 140.87, 134.58, 128.54, 127.22, 125.90, 121.61, 53.80,
49.31, 48.83, 43.30, 41.31, 22.798; Anal. Calc. for
C18H18ClN5OS: C, 55.74; H, 4.68; N, 18.06; Found: C, 55.92;
H, 4.87; N, 18.26.
2-(1-((2-Chlorothiazol-5-yl)methyl)imidazolidin-2-ylidene)-2-
cyano-N-(p-tolyl)acetamide (6q). Yellow solid; yield: 78%;
mp: 197.1–198.5ꢁC; IR (KBr): m 3305.9, 3282.8, 3049.4,
2974.2, 2922.1, 2885.5, 2187.2, 1624.0, 1575.8, 1506.4,
1479.4 cmꢀ1 1H-NMR (CDCl3, 500 MHz) d: 9.48 (br, 1H,
;
NH), 7.53 (s, 1H, thiazole-H), 7.52 (br, 1H, NH), 7.31 (d, J ¼
8.60 Hz, 2H, 2PhAH), 7.12 (d, J ¼ 8.60 Hz, 2H, 2PhAH),
5.02 (s, 2H, CH2), 3.55–3.65 (m, 4H, CH2CH2); 13C-NMR
(CDCl3, 125 MHz) d: 166.75, 163.36, 153.38, 140.99, 135.46,
134.46, 133.69, 129.50, 121.44, 120.72, 54.46, 48.22, 43.36,
41.41, 20.94; Anal. Calc. for C17H16ClN5OS: C, 54.61; H,
4.31; N, 18.73. Found: C, 54.73; H, 4.29; N, 19.18.
N-Benzyl-2-(1-((2-chlorothiazol-5-yl)methyl)imidazolidin-2-
ylidene)-2-cyanoacetamide (6l). Light yellow solid; yield:
73%; mp: 181–183ꢁC; IR (KBr): m 3250.0, 3032.1, 2926.0,
2169.9, 1614.4, 1570.0, 1514.1, 1483.2, 1296.1 cmꢀ1 1H-
;
NMR (CDCl3, 500 MHz) d: 9.49 (br, 1H, NAH), 7.51 (s, 1H,
thiazole-H), 7.25–7.35 (m, 5H, 5PhAH), 6.20 (t, J ¼ 5.75 Hz,
1H, NAH), 4.99 (s, 2H, CH2), 4.48 (d, J ¼ 5.75, 2H, CH2),
3.55–3.62 (m, 4H, CH2CH2); 13C-NMR (CDCl3, 125 MHz) d:
168.36, 163.27, 153.32, 140.92, 138.74, 134.54, 128.74,
127.55, 127.42, 121.53, 53.80, 48.88, 43.67, 43.32, 41.37;
Anal. Calc. for C22H19ClN4O4S2: C, 52.53; H, 3.81; N, 11.14.
Found: C, 52.94; H, 3.29; N, 11.62.
2-(1-((2-Chlorothiazol-5-yl)methyl)imidazolidin-2-ylidene)-2-
cyano-N-phenylacetamide (6r). Yellow solid; yield: 73%; mp:
181.8–182.8ꢁC; IR (KBr): m 3300.2, 3055.2, 3047.5, 2968.4,
2906.7, 2166.0, 1639.4, 1558.4, 1508.3, 1448.5 cmꢀ1 1H-
;
NMR (CDCl3, 500 MHz) d: 9.48 (br, 1H, NH), 7.57 (s 1H,
NH), 7.53 (s, 1H, thiazole-H), 7.44 (d, J ¼ 8.05 Hz, 2H,
Journal of Heterocyclic Chemistry
DOI 10.1002/jhet