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CN106349236B - 1h-1,2,4-三唑脒类化合物及其制备方法和应用 - Google Patents

1h-1,2,4-三唑脒类化合物及其制备方法和应用 Download PDF

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CN106349236B
CN106349236B CN201610608404.8A CN201610608404A CN106349236B CN 106349236 B CN106349236 B CN 106349236B CN 201610608404 A CN201610608404 A CN 201610608404A CN 106349236 B CN106349236 B CN 106349236B
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CN106349236A (zh
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覃兆海
贾长青
马永强
杨冬燕
车传亮
刘雪莲
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Abstract

本发明属于农药开发技术领域，特别涉及1H‑1,2,4‑三唑脒类化合物及其制备方法和应用。所述化合物的结构通式为

Description

1H-1,2,4-三唑脒类化合物及其制备方法和应用
技术领域
本发明属于农药开发技术领域，特别涉及1H-1,2,4-三唑脒类化合物及其制备方法和应用。
背景技术
三唑是含三个氮原子的五元杂环，作为药效团，具有比咪唑类药物更低的毒性，广泛地应用于农药、医药中；三唑因其较强的络合金属离子和形成氢键的能力而在化学领域备受青睐。3-氨基-1,2,4-三唑及其多种衍生物都有杀虫、除草、抗菌、促进和调节农作物生长的功效，在农业和医药等领域得到了广泛的应用。脒是氮取代的羧酸类似物，某些脒类化合物是一些具有生理活性的物质的片段，同时，它们还是重要的合成中间体，广泛应用于抗生素、利尿剂、消炎药、驱虫剂和广谱杀螨剂。
脒类结构在药物分子结构中并不少见，但多取代-1H-1,2,4-三唑脒结构在农用化学品研究中鲜有报道。
发明内容
本发明公开了1H-1,2,4-三唑脒类化合物及其制备方法和应用，具体技术方案为：
1H-1,2,4-三唑脒类化合物，结构通式为其中，R1为氢、C1～C10饱和或不饱和脂肪烃基、取代或未取代的苯基、取代或未取代的吡啶基、取代或未取代的噻唑基、取代或未取代的呋喃基、取代或未取代的萘基；其中，所述取代苯基中的取代基为卤素、羟基、氨基、C1～C5烷基、C1～C5烷氧基、C1～C5氟代烷基或C1～C5氟代烷氧基、芳基、芳氧基；所述取代吡啶基中的取代基为卤素、C1～C5烷基、C1～C5烷氧基、C1～C5氟代烷基或C1～C5氟代烷氧基、芳氧基；所述取代呋喃基中的取代基为卤素、三氟甲基；所述取代萘基中的取代基为C1～C5烷基、羟基、硝基、卤素、氨基；
R2为氢、C1～C10饱和或不饱和脂肪烃基、C1～C10饱和或不饱和脂肪烃基、取代或未取代的苄基、取代或未取代的吡啶甲基、取代或未取代的噻唑甲基、取代或未取代的吡唑甲基、取代或未取代的恶唑甲基、取代或未取代的异恶唑甲基、或四氢呋喃甲基；其中，所述取代苄基、取代吡啶甲基、取代噻唑甲基、取代吡唑甲基、取代恶唑甲基和取代异恶唑甲基中的取代基可独立地选自下述基团中的任意一种或几种：卤素(具体可为F、Cl、Br、I)、氨基、羟基、C1～C5烷基、C1～C5烷氧基、C1～C5氟代烷基和C1～C5氟代烷氧基；
R3为氢、C1～C10饱和或不饱和脂肪烃基、取代或未取代的苯基、取代或未取代的吡啶基、取代或未取代的呋喃基、取代或未取代的萘基；其中，所述取代苯基中的取代基可为卤素、羟基、氨基、C1～C5烷基、C1～C5烷氧基、C1～C5氟代烷基或C1～C5氟代烷氧基、芳基、芳氧基。
优选地，R1为乙烯基、乙炔基、氯代吡啶基、氯代噻唑基、四氢呋喃-3-基；R2为C1～C10不饱和脂肪烃基、卤代吡啶甲基、卤代噻唑甲基、四氢呋喃甲基。
优选地，R1为氢、卤代苯基、C3～C7饱和或不饱和脂肪烃基；R2为氢、取代苯基、C1～C7饱和或不饱和脂肪烃基；R3为甲基、乙基、苄基、取代苯基、取代或未取代的吡啶基。
本发明中所述饱和或不饱和脂肪烃基可为直链或支链。
如上所述的1H-1,2,4-三唑脒类化合物的制备方法，具体步骤为：
将化合物I溶于溶剂，搅拌下使之完全溶解，加入化合物III，室温下搅拌3～6h，反应液浓缩后纯化，得到所述1H-1,2,4-三唑脒类化合物。
溶解化合物I的溶剂包括乙腈、N,N-二甲基乙酰胺、氯苯、四氢呋喃中的一种。
如上所述的1H-1,2,4-三唑脒类化合物用作杀虫剂，优选地，用于杀灭蚜虫。
本发明具有以下有益效果：
首次报道了含1,2,4-三唑脒结构的化合物在农用化学品领域中的应用，且该类多取代-1H-1,2,4-三唑脒类化合物(II)具有较好的杀虫活性。
具体实施方式
下面结合实施例对本发明做进一步的说明，但并不因此而限制本发明的保护范围。
表1实施例制备的1H-1,2,4-三唑脒类化合物及理化性质
实施例1：化合物II-2的制备
在100mL三口瓶中，加入1-正丁基-3-苯基-1H-1,2,4-三唑-5-胺(0.002mol,0.46g)，乙腈30mL,磁力搅拌下完全溶解，缓慢加入N,N-二甲基甲酰胺二甲缩醛(DMF-DMA，0.02mol，0.24g)加入完毕后，室温下搅拌3h，TLC检测反应完全后，停止搅拌，反应液减压浓缩后，用V乙酸乙酯:V石油醚＝1:4快速柱层析，得淡黄色油状物0.50g，产率91％。1H NMR(CDCl3,300MHz)δ8.49(s,1H,CH),8.07～8.03(m,2H,Ph),7.41～7.28(m,3H,Ph),4.17(d,J＝7.2Hz,2H,CH2),3.02(s,3H,CH3),3.01(s,3H,CH3),1.89～1.79(m,2H,CH2),1.42～1.25(m,2H,CH2),0.94(t,J＝7.50Hz,3H,CH3)；13C NMR(CDCl3,75MHz)δ158.8,158.3,156.6,132.1,128.1,128.1,125.7,45.6,40.2,34.1,31.4,19.5,13.4；HRMS calcd for C15H21N5(M+H)+272.1870,found 272.1870.
实施例2：化合物II-15的制备
在100mL三口瓶中，加入1-正丙基-3-(4-硝基苯基)-1H-1,2,4-三唑-5-胺(0.002mol,0.5g)，乙腈30mL,磁力搅拌下完全溶解，缓慢加入N,N-二甲基甲酰胺二甲缩醛(DMF-DMA，0.02mol，0.24g)加入完毕后，室温下搅拌3h，TLC检测反应完全后，停止搅拌，反应液减压浓缩后，用V乙酸乙酯:V石油醚＝1:4重结晶，得淡黄色粉末状固体0.55g，产率90％。1HNMR(CDCl3,300MHz)δ8.51(s,1H,CH),8.26～8.18(m,4H,Ph),4.09(t,J＝7.20Hz,2H,CH2),3.14(s,3H,CH3),3.10(s,3H,CH3),1.93～1.85(m,2H,CH2),0.95(t,J＝7.20Hz,3H,CH3)；13CNMR(CDCl3,75MHz)δ159.5,156.9,156.5,147.5,138.4,126.3,123.7,48.0,40.6,34.4,22.8,11.1；HRMS calcd for C14H18N6O2(M+H)+303.1564,found 303.1560.
其它化合物的合成方法与此相同。
化合物II-1.收率78％，1H NMR(300MHz，CDCl3)δ:8.42(s,1H,＝CH),7.49(s,1H,thiazole),5.29(s,2H,CH2),3.11(s,2H,CH3),3.09(s,1H,CH3),2.93～2.87(m,2H,CH2),1.29(s,3H,CH3),1.27(s,3H,CH3).13C NMR(75MHz,CDCl3)δ:166.8,158.0,156.8,152.2,139.7,136.2,42.0,40.5,34.5,28.6,21.5.HRMS(ESI)m/z calcd for C12H17ClN6S(M+H)+313.0997,found 313.1000。化合物II-3.收率85％，1H NMR(300MHz，CDCl3)δ:8.44(s,1H,CH),7.68～7.05(m,4H,Ph),4.08～4.01(m,2H,CH2),3.77(s,3H,OCH3),3.11(s,3H,CH3),3.01(s,3H,CH3),1.30(t,J＝7.20Hz,3H,CH3).13C NMR(75MHz,CDCl3)δ:157.5,157.1,156.9,156.2,130.3,129.5,121.8,120.0,112.1,55.6,40.1,34.1,14.7.HRMS(ESI)m/zcalcd for C14H19N5O(M+H)+274.1662,found 274.1664.
化合物II-4.收率90％，1H NMR(300MHz，CDCl3)δ:8.53(s,1H,CH),7.82～6.94(m,4H,Ph),6.10～5.97(m,1H,＝CH),5.26～5.17(m,1H,CH2＝),4.78～4.75(m,2H,CH2),3.89(s,3H,OCH3),3.08(s,3H,CH3),3.06(s,3H,CH3).13C NMR(75MHz,CDCl3)δ:158.2,157.4,157.3,156.9,133.1,130.7,129.6,121.8,120.3,117.3,112.4,55.9,48.7,40.3,34.3.HRMS(ESI)m/z calcd for C15H19N5O(M+H)+286.1662,found 286.1665.
化合物II-5.收率86％，1H NMR(300MHz，CDCl3)δ:8.51(s,1H,CH),7.78～7.26(m,4H,Ph),4.22～4.15(m,2H,CH2),3.09(s,3H,CH3),3.08(s,3H,CH3),1.44(t,J＝7.20Hz,3H,CH3).13C NMR(75MHz,CDCl3)δ:157.9,157.1,132.8,131.4,130.3,129.4,126.4,41.3,40.5,34.3,31.8,22.6,14.7,14.0.HRMS(ESI)m/z calcd for C13H16ClN5(M+H)+278.1167,found 278.1169.
化合物II-6.收率81％，1H NMR(300MHz，CDCl3)δ:8.49(s,1H,CH),7.79～7.23(m,4H,Ph),4.14(t,J＝7.2Hz,2H,CH2),3.07(s,2H,CH3),3.06(s,3H,CH3),1.90～1.80(m,2H,CH2),1.43～1.28(m,2H,CH2),0.95(t,J＝7.20Hz,CH3)；13C NMR(75MHz,CDCl3)δ:158.2,157.0,156.8,132.6,131.4,131.1,130.1,129.2,126.3,45.7,40.3,34.2,31.4,19.5,13.5.HRMS(ESI)m/z calcd for C15H20ClN5(M+H)+306.1480,found 306.1478.
化合物II-7.收率83％，1H NMR(300MHz，CDCl3)δ:8.46(s,2H,CH),7.82～7.37(m,4H,Ph),6.02～5.91(m,1H,＝CH),5.20～5.06(m,2H,CH2＝),4.70～4.68(m,2H,CH2),3.12(s,2H,CH3),3.01(s,3H,CH3).13C NMR(75MHz,CDCl3)δ:158.5,157.4,156.5,133.6,131.5,131.1,130.4,129.9,126.9,117.2,48.0,40.3,34.2.HRMS(ESI)m/z calcd for C14H16ClN5(M+H)+290.1167,found 290.1168.
化合物II-8.收率84％，1H NMR(300MHz，DMSO)δ:8.39(s,2H,CH),7.94～7.40(m,4H,Ph),4.09(t,J＝7.2Hz,2H,CH2),3.05(s,3H,CH3),3.03(s,3H,CH3),1.86～1.76(m,2H,CH2),1.40～1.26(m,2H,CH2),0.94(t,J＝7.20Hz,CH3)；13C NMR(300MHz,DMSO)δ:158.8,156.8,154.5,149.1,131.2,130.1,128.7,125.9,123.1,45.7,40.3,34.1,31.2,19.4,13.3.HRMS(ESI)m/z calcd for C15H20N6O2(M+H)+317.1721,found 317.1724.
化合物II-9.收率87％，1H NMR(300MHz，DMSO)δ:8.37(s,1H,CH),7.93～7.57(m,4H,Ph),6.00～5.88(m,1H,＝CH),5.18～5.02(m,2H,CH2＝),4.67～4.65(m,2H,CH2),3.11(s,3H,CH3),3.01(s,3H,CH3).13C NMR(75MHz,DMSO)δ:159.1,157.4,154.2,148.9,133.3,131.9,129.8,124.9,123.5,117.2,48.1,40.3,34.3.HRMS(ESI)m/z calcd for C14H16N6O2(M+H)+301.1408,found 301.1411.
化合物II-10.收率80％，1H NMR(300MHz，CDCl3)δ:8.49(s,1H,CH),4.15(q,J＝7.20Hz,2H,CH2),3.11(s,3H,CH3),3.08(s,3H,CH3),1.42(t,J＝7.20Hz,3H,CH3)；13C NMR(75MHz,CDCl3)δ:158.6,157.6,156.8,134.0,130.8,128.4,127.1,41.3,40.5,34.3,14.7.HRMS(ESI)m/z calcd for C13H16ClN5(M+H)+278.1167,found 278.1168.
化合物II-11.收率82％，1H NMR(300MHz，CDCl3)δ:8.48(s,1H,CH),7.95～7.45(m,4H,Ph),3.99(t,J＝6.9Hz,2H,CH2),3.12(s,3H,CH3),3.01(s,3H,CH3),1.80～1.73(m,2H,CH2),0.84(t,J＝7.20Hz,3H,CH3).13C NMR(75MHz,CDCl3)δ:159.2,157.2,156.5,133.0,131.1,128.6,127.1,47.2,34.1,22.5,11.1.HRMS(ESI)m/z calcd for C14H18ClN5(M+H)+292.1323,found 292.1326.
化合物II-12.收率82％，1H NMR(300MHz，CDCl3)δ:8.49(s,1H,CH),8.00～7.34(m,4H,Ph),4.10(t,J＝7.20Hz,2H,CH2),3.11(s,3H,CH3),3.07(s,3H,CH3),1.85～1.74(m,2H,CH2),1.39～1.32(m,2H,CH2),0.94(t,J＝7.20Hz,2H,CH3).13C NMR(75MHz,CDCl3)δ:159.0,157.6,156.8,134.1,130.8,128.4,127.2,45.8,40.5,34.3,31.5,19.7,13.5.HRMS(ESI)m/z calcd for C15H20ClN5(M+H)+306.1480,found 306.1479.
化合物II-13.收率86％，1H NMR(300MHz，CDCl3)δ:8.50(s,1H,CH),8.00～7.34(m,4H,Ph),6.06～5.96(m,1H,＝CH),5.24～5.17(m,2H,CH2＝),4.75～4.72(m,2H,CH2),3.11(s,3H,CH3),3.07(s,3H,CH3).13C NMR(75MHz,CDCl3)δ:159.0,158.0,156.9,134.2,132.8,130.6,128.4,127.2,117.4,48.6,40.5,34.4.HRMS(ESI)m/z calcd for C14H16ClN5(M+H)+290.1167,found 290.1169.
化合物II-14.收率84％，1H NMR(300MHz，CDCl3)δ:8.50(s,1H,CH),8.26～8.18(m,4H,Ph),4.18(q,J＝7.20Hz,2H,CH2),3.14(s,3H,CH3),3.10(s,3H,CH3),1.44(t,J＝7.20Hz,3H,CH3).13C NMR(75MHz,CDCl3)δ:159.0,156.9,156.5,147.5,138.4,126.3,123.7,41.5,40.6,34.4,14.6.HRMS(ESI)m/z calcd for C13H16N6O2(M+H)+289.1408,found289.1404.
化合物II-16.收率90％，1H NMR(300MHz，CDCl3)δ:8.52(s,1H,CH),8.26～8.19(m,4H,Ph),4.13(t,J＝7.20Hz,2H,CH2),3.14(s,3H,CH3),3.10(s,3H,CH3),1.89～1.80(m,2H,CH2),1.40～1.30(m,2H,CH2),0.96(t,J＝7.20Hz,3H,CH3).13C NMR(75MHz,CDCl3)δ:159.5,156.9,156.5,147.5,138.4,126.3,123.7,46.1,40.6,34.4,31.5,19.7,13.5.HRMS(ESI)m/z calcd for C15H20N6O2(M+H)+317.1721,found 317.1721.
化合物II-17.收率95％，1H NMR(300MHz，CDCl3)δ:8.52(s,1H,CH),8.27～8.19(m,4H,Ph),6.06～5.97(m,1H,＝CH),5.26～5.20(m,2H,CH2＝),4.78～4.75(m,2H,CH2),3.15(s,3H,CH3),3.10(s,3H,CH3)。13C NMR(75MHz,CDCl3)δ:159.5,157.1,156.9,147.6,138.2,132.6,126.4,123.6,117.4,48.8,40.6,34.4.HRMS(ESI)m/z calcd for C14H16N6O2(M+H)+301.1408,found 301.1411.
化合物II-18.收率93％，1H NMR(300MHz，CDCl3)δ:8.50(s,1H,CH),8.04～7.99(m,2H,Ph),7.10～7.04(m,2H,Ph),4.15(q,J＝7.2Hz,2H,CH2),3.11(s,3H,CH3),3.08(s,3H,CH3),1.42(t,J＝7.20Hz,3H,CH3).13C NMR(75MHz,CDCl3)δ:164.6,161.3,158.5,157.8,156.7,128.5,128.4,127.7,127.6,115.3,115.0,41.2,40.5,34.3,14.7.HRMS(ESI)m/zcalcd for C13H16FN5(M+H)+262.1463,found 262.1461.
化合物II-19.收率84％，1H NMR(300MHz，CDCl3)δ:8.50(s,1H,CH),8.04～7.99(m,2H,Ph),7.10～7.04(m,2H,Ph),4.06(t,J＝6.90Hz,2H,CH2),3.11(s,3H,CH3),3.08(s,3H,CH3),1.91～1.84(m,2H,CH2),0.94(t,J＝7.50Hz,CH3)；13C NMR(75MHz,CDCl3)δ:164.6,161.4,159.0,157.7,156.7,128.5,128.4,127.7,127.6,115.3,115.0,47.8,40.5,34.3,22.9,11.1.HRMS(ESI)m/z calcd for C14H18FN5(M+H)+276.1619,found 276.1618.
化合物II-20.收率87％，1H NMR(300MHz，CDCl3)δ:8.50(s,1H,CH),8.04～7.99(m,2H,Ph),7.10～7.04(m,2H,Ph),4.10(t,J＝6.90Hz,2H,CH2),3.11(s,3H,CH3),3.07(s,3H,CH3),1.88～1.78(m,2H,CH2),1.39～1.29(m,2H,CH2),0.94(t,J＝7.20Hz,3H,CH3)；13C NMR(75MHz,CDCl3)δ:164.6,161.4,158.9,157.8,156.7,128.5,128.5,127.7,127.6,115.3,115.0,45.8,40.5,34.3,31.5,19.7,13.5.HRMS(ESI)m/z calcd for C15H20FN5(M+H)+290.1776,found 290.1774.
化合物II-21.收率88％，1H NMR(300MHz，CDCl3)δ:8.51(s,1H,CH),8.05～8.00(m,2H,Ph),7.09～7.04(m,2H,Ph),6.06～5.97(m,1H,＝CH),5.24～5.17(m,2H,CH2＝),4.75～4.72(m,2H,CH2),3.11(s,3H,CH3),3.07(s,3H,CH3)；13C NMR(75MHz,CDCl3)δ:164.6,161.4,159.0,158.0,156.8,132.9,128.3,128.3,127.7,127.6,117.3,115.2,114.9,48.5,40.5,34.3.HRMS(ESI)m/zcalcd for C14H16FN5(M+H)+274.1463,found 274.1464.
化合物II-22.收率83％，1H NMR(300MHz，CDCl3)δ:8.51(s,1H,CH),7.98～7.96(m,2H,Ph),6.93～6.90(m,2H,Ph),4.15(q,J＝7.20Hz,2H,CH2),3.11(s,3H,CH3),3.08(s,3H,CH3),1.42(t,J＝7.20Hz,3H,CH3)；13C NMR(75MHz,CDCl3)δ:159.9,158.5,158.3,156.7,127.2,125.0,113.7,55.2,41.8,40.5,34.3,14.7.HRMS(ESI)m/z calcd for C14H19N5O(M+H)+274.1662,found 274.1664.
化合物II-23.收率84％，1H NMR(300MHz，CDCl3)δ:8.51(s,1H,CH),7.99～7.96(m,2H,Ph),6.93～6.90(m,2H,Ph),4.06(t,J＝7.20Hz,CH2),3.10(s,3H,CH3),3.07(s,3H,CH3),1.91～1.83(m,2H,CH2),0.93(t,J＝7.50Hz,CH3)；13C NMR(75MHz,CDCl3)δ:159.8,158.8,158.4,156.6,127.2,125.0,113.6,55.1,47.7,40.4,34.2,22.9,11.1.HRMS(ESI)m/z calcd for C15H21N5O(M+H)+288.1819,found 288.1820.
化合物II-24.收率81％，1H NMR(300MHz，CDCl3)δ:8.50(s,1H,CH),7.99～7.95(m,2H,Ph),6.94～6.89(m,2H,Ph),4.10(t,J＝7.20Hz,2H,CH2),3.10(s,3H,CH3),3.07(s,3H,CH3)，1.88～1.78(m,2H,CH2),1.39～1.32(m,2H,CH2),0.94(t,J＝7.20Hz,CH3)；13C NMR(75MHz,CDCl3)δ:159.8,158.7，158.4,156.6,127.2,125.0,113.6,55.1,45.7,40.4,34.2,31.5,19.6,13.5.HRMS(ESI)m/z calcd for C16H23N5O(M+H)+302.1975,found 302.1973.
化合物II-25.收率83％，1H NMR(300MHz，CDCl3)δ:8.51(s,1H,CH),8.00～7.95(m,2H,Ph),6.94～6.90(m,2H,Ph),6.06～5.97(m,1H,＝CH),5.23～5.17(m,CH2＝),4.75～4.72(m,2H,CH2),3.10(s,3H,CH3),3.07(s,3H,CH3)；13C NMR(75MHz,CDCl3)δ:159.9,158.8，158.7,156.8,133.0,127.3,124.9,117.2,113.6,55.1,48.5,40.5,34.3.HRMS(ESI)m/zcalcd for C15H19N5O(M+H)+286.1662,found 286.1661.
化合物II-26.收率87％，1H NMR(300MHz，CDCl3)δ:8.52(s,1H,CH),8.00～7.93(m,2H,Ph),6.92～6.90(m,2H,Ph),6.08～5.98(m,1H,＝CH),4.02(q,2H,CH2),3.82(q,2H,CH2),1.40(t,3H,CH3),1.24(s,3H,CH3)；13C NMR(75MHz,CDCl3)δ:162.8,160.3 155.7,153.6,129.1,128.4,116.0,48.8,42.5,38.8,15.0,12.8.HRMS(ESI)m/z calcd forC14H18FN5(M+H)+276.1619,found 276.1615.
化合物II-27.收率90％，1H NMR(300MHz，CDCl3)δ:8.50(s,1H,CH),8.01～7.90(m,2H,Ph),6.94～6.88(m,7H,Ph),6.05～5.90(m,1H,＝CH),4.03(t,2H,CH2),3.97(s,2H,CH2),2.74(m,2H,CH2),1.38(t,3H,CH3),1.22(s,3H,CH3)；13C NMR(75MHz,CDCl3)δ:162.9,160.1,153.4,153.2,136.4,129.1,128.5,128.1,127.9,127.0,116.0,49.0,57.3,38.4,23.3,11.2.HRMS(ESI)m/z calcd for C20H22FN5(M+H)+352.1932,found 352.1927.
化合物II-28.收率81％，1H NMR(300MHz，CDCl3)δ:8.52(s,1H,CH),8.12(d,2H,Ph),7.55(d,2H,Ph),7.37～6.96(m,4H,Ph),4.26(s,2H,CH2),3.97(t,2H,CH2),3.04(s,3H,CH3),1.38(t,3H,CH3)；13C NMR(75MHz,CDCl3)δ:160.1,153.4,153.2,134.5,134.3,132.6,130.6,130.3,129.3,128.9,128.6,42.8,38.4,15.0.HRMS(ESI)m/z calcd for C19H19Cl2N5(M+H)+388.1090,found 388.1089.
化合物II-29.收率76％，1H NMR(300MHz，CDCl3)δ:8.71(s,1H,Py),8.50(s,1H,CH),8.12～8.00(m,3H,Ar),7.55～7.23(m,3H,Ar),4.46(t,2H,CH2),4.26(s,2H,CH2),3.04(s,3H,CH3),1.70(m,2H,CH2),0.91(t,3H,CH3)；13C NMR(75MHz,CDCl3)δ:160.1,153.4,153.2,150.4,149.6,138.4,134.3,131.4,130.6,129.3,128.9,123.5,57.3,49.0,38.4,23.3,11.2.HRMS(ESI)m/z calcd for C19H20Cl2N6(M+H)+403.1199,found 403.1196.
实施例3：II系列化合物的杀虫活性测定
1)试验材料
供试药剂：II-1～II-29；
试验害虫:桃蚜(Myzus persicae)，采自田间的种群。
2)试验处理与方法
毒力测定方法如下：先将原药用N,N-二甲基甲酰胺配制成母液(质量分数2％)，再用TritonX-100的水溶液(质量分数0.05％)稀释至测定浓度。用药液浸渍法，将事先挑选好的带蚜叶片浸入药液，轻摇10s后取出，用吸水纸吸去多余药液，计数后放入培养皿内，皿内放有湿润吸水纸保湿，加保鲜膜加盖置25±1℃下恢复。用不含药水溶液作空白对照。48h后在台式放大镜下检查结果。以毛笔尖轻触虫体，无反应和不能正常爬行者为死亡。普筛时所测药剂浓度为500μg/mL。测定LC50时所测药剂浓度梯度设定为1，5，10，20，80，200，400μg/mL。每个梯度平行测定3次。试验结果用Probit软件进行统计分析，计算LC50值。目标化合物的杀虫活性数据见表2和表3。
3)测试结果
表2II系列化合物在500μg/mL浓度下对桃蚜的杀虫活性
在500μg/mL浓度下，II系列化合物对桃蚜表现出优秀的杀虫活性，大部分化合物的校正死亡率在85％以上。
表3 目标化合物III对桃蚜的LC50值及95％置信限
从表3可以看出，LC50测定中，化合物II-2、II-4、II-11、II-13、II-27、II-28、II-29的LC50在10μg/mL以下，对桃蚜表现出优秀的杀虫活性。

Claims (6)

1.1H-1,2,4-三唑脒类化合物，其特征在于，所述化合物的结构通式为其中，R1为氢、C1～C10饱和或不饱和脂肪烃基、取代或未取代的苯基、取代或未取代的吡啶基、取代或未取代的噻唑基、取代或未取代的呋喃基、取代或未取代的萘基；其中，所述取代苯基中的取代基为卤素、羟基、氨基、C1～C5烷基、C1～C5烷氧基、C1～C5氟代烷基或C1～C5氟代烷氧基、芳基、芳氧基；所述取代吡啶基中的取代基为卤素、C1～C5烷基、C1～C5烷氧基、C1～C5氟代烷基或C1～C5氟代烷氧基、芳氧基；所述取代呋喃基中的取代基为卤素、三氟甲基；所述取代萘基中的取代基为C1～C5烷基、羟基、硝基、卤素、氨基；
R2为氢、C1～C10饱和或不饱和脂肪烃基、C1～C10饱和或不饱和脂肪烃基、取代或未取代的苄基、取代或未取代的吡啶甲基、取代或未取代的噻唑甲基、取代或未取代的吡唑甲基、取代或未取代的恶唑甲基、取代或未取代的异恶唑甲基、或四氢呋喃甲基；其中，所述取代苄基、取代吡啶甲基、取代噻唑甲基、取代吡唑甲基、取代恶唑甲基和取代异恶唑甲基中的取代基可独立地选自下述基团中的任意一种或几种：卤素、氨基、羟基、C1～C5烷基、C1～C5烷氧基、C1～C5氟代烷基和C1～C5氟代烷氧基；
R3为氢、C1～C10饱和或不饱和脂肪烃基、取代或未取代的苯基、取代或未取代的吡啶基、取代或未取代的呋喃基、取代或未取代的萘基；其中，所述取代苯基中的取代基可为卤素、羟基、氨基、C1～C5烷基、C1～C5烷氧基、C1～C5氟代烷基或C1～C5氟代烷氧基、芳基、芳氧基；
所述的1H-1,2,4-三唑脒类化合物用作杀虫剂。
2.根据权利要求1所述的1H-1,2,4-三唑脒类化合物，其特征在于，R1为乙烯基、乙炔基、氯代吡啶基、氯代噻唑基、四氢呋喃-3-基；R2为C1～C10不饱和脂肪烃基、卤代吡啶甲基、卤代噻唑甲基、四氢呋喃甲基。
3.根据权利要求1所述的1H-1,2,4-三唑脒类化合物，其特征在于，R1为氢、卤代苯基、C3～C7饱和或不饱和脂肪烃基；R2为氢、取代苯基、C1～C7饱和或不饱和脂肪烃基；R3为甲基、乙基、苄基、取代苯基、取代或未取代的吡啶基。
4.权利要求1-3任一项所述的1H-1,2,4-三唑脒类化合物的制备方法，其特征在于，具体步骤为：
将化合物I溶于溶剂，搅拌下使之完全溶解，加入化合物III，室温下搅拌3～6h，反应液浓缩后纯化，得到所述1H-1,2,4-三唑脒类化合物。
5.根据权利要求4所述的制备方法，其特征在于，溶解化合物I的溶剂包括乙腈、N,N-二甲基乙酰胺、氯苯、四氢呋喃中的一种。
6.根据权利要求1所述的1H-1,2,4-三唑脒类化合物，其特征在于，所述1H-1,2,4-三唑脒类化合物用于杀灭蚜虫。
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