本發(fā)明屬于農(nóng)藥開發(fā)技術(shù)領(lǐng)域，特別涉及1H-1,2,4-三唑脒類化合物及其制備方法和應(yīng)用。
背景技術(shù)：
三唑是含三個(gè)氮原子的五元雜環(huán)，作為藥效團(tuán)，具有比咪唑類藥物更低的毒性，廣泛地應(yīng)用于農(nóng)藥、醫(yī)藥中；三唑因其較強(qiáng)的絡(luò)合金屬離子和形成氫鍵的能力而在化學(xué)領(lǐng)域備受青睞。3-氨基-1,2,4-三唑及其多種衍生物都有殺蟲、除草、抗菌、促進(jìn)和調(diào)節(jié)農(nóng)作物生長的功效，在農(nóng)業(yè)和醫(yī)藥等領(lǐng)域得到了廣泛的應(yīng)用。脒是氮取代的羧酸類似物，某些脒類化合物是一些具有生理活性的物質(zhì)的片段，同時(shí)，它們還是重要的合成中間體，廣泛應(yīng)用于抗生素、利尿劑、消炎藥、驅(qū)蟲劑和廣譜殺螨劑。
脒類結(jié)構(gòu)在藥物分子結(jié)構(gòu)中并不少見，但多取代-1H-1,2,4-三唑脒結(jié)構(gòu)在農(nóng)用化學(xué)品研究中鮮有報(bào)道。
技術(shù)實(shí)現(xiàn)要素：
本發(fā)明公開了1H-1,2,4-三唑脒類化合物及其制備方法和應(yīng)用，具體技術(shù)方案為：
1H-1,2,4-三唑脒類化合物，結(jié)構(gòu)通式為其中，R1為氫、C1～C10飽和或不飽和脂肪烴基、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為鹵素、羥基、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為鹵素、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為鹵素、三氟甲基；所述取代萘基中的取代基為C1～C5烷基、羥基、硝基、鹵素、氨基；
R2為氫、C1～C10飽和或不飽和脂肪烴基、C1～C10飽和或不飽和脂肪烴基、取代或未取代的芐基、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、取代或未取代的惡唑甲基、取代或未取代的異惡唑甲基、或四氫呋喃甲基；其中，所述取代芐基、取代吡啶甲基、取代噻唑甲基、取代吡唑甲基、取代惡唑甲基和取代異惡唑甲基中的取代基可獨(dú)立地選自下述基團(tuán)中的任意一種或幾種：鹵素(具體可為F、Cl、Br、I)、氨基、羥基、C1～C5烷基、C1～C5烷氧基、C1～C5氟代烷基和C1～C5氟代烷氧基；
R3為氫、C1～C10飽和或不飽和脂肪烴基、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為鹵素、羥基、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。
優(yōu)選地，R1為乙烯基、乙炔基、氯代吡啶基、氯代噻唑基、四氫呋喃-3-基；R2為C1～C10不飽和脂肪烴基、鹵代吡啶甲基、鹵代噻唑甲基、四氫呋喃甲基。
優(yōu)選地，R1為氫、鹵代苯基、C3～C7飽和或不飽和脂肪烴基；R2為氫、取代苯基、C1～C7飽和或不飽和脂肪烴基；R3為甲基、乙基、芐基、取代苯基、取代或未取代的吡啶基。
本發(fā)明中所述飽和或不飽和脂肪烴基可為直鏈或支鏈。
如上所述的1H-1,2,4-三唑脒類化合物的制備方法，具體步驟為：
將化合物I溶于溶劑，攪拌下使之完全溶解，加入化合物III，室溫下攪拌3～6h，反應(yīng)液濃縮后純化，得到所述1H-1,2,4-三唑脒類化合物。
溶解化合物I的溶劑包括乙腈、N,N-二甲基乙酰胺、氯苯、四氫呋喃中的一種。
如上所述的1H-1,2,4-三唑脒類化合物用作殺蟲劑，優(yōu)選地，用于殺滅蚜蟲。
本發(fā)明具有以下有益效果：
首次報(bào)道了含1,2,4-三唑脒結(jié)構(gòu)的化合物在農(nóng)用化學(xué)品領(lǐng)域中的應(yīng)用，且該類多取代-1H-1,2,4-三唑脒類化合物(II)具有較好的殺蟲活性。
具體實(shí)施方式
下面結(jié)合實(shí)施例對(duì)本發(fā)明做進(jìn)一步的說明，但并不因此而限制本發(fā)明的保護(hù)范圍。
表1實(shí)施例制備的1H-1,2,4-三唑脒類化合物及理化性質(zhì)
實(shí)施例1：化合物II-2的制備
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,磁力攪拌下完全溶解，緩慢加入N,N-二甲基甲酰胺二甲縮醛(DMF-DMA，0.02mol，0.24g)加入完畢后，室溫下攪拌3h，TLC檢測(cè)反應(yīng)完全后，停止攪拌，反應(yīng)液減壓濃縮后，用V乙酸乙酯:V石油醚＝1:4快速柱層析，得淡黃色油狀物0.50g，產(chǎn)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.
實(shí)施例2：化合物II-15的制備
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,磁力攪拌下完全溶解，緩慢加入N,N-二甲基甲酰胺二甲縮醛(DMF-DMA，0.02mol，0.24g)加入完畢后，室溫下攪拌3h，TLC檢測(cè)反應(yīng)完全后，停止攪拌，反應(yīng)液減壓濃縮后，用V乙酸乙酯:V石油醚＝1:4重結(jié)晶，得淡黃色粉末狀固體0.55g，產(chǎn)率90％。1H NMR(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)；13C NMR(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與此相同。
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/z calcd 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,found 289.1404.
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/z calcd 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/z calcd 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 for C14H18FN5(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.
實(shí)施例3：II系列化合物的殺蟲活性測(cè)定
1)試驗(yàn)材料
供試藥劑：II-1～I(xiàn)I-29；
試驗(yàn)害蟲:桃蚜(Myzus persicae)，采自田間的種群。
2)試驗(yàn)處理與方法
毒力測(cè)定方法如下：先將原藥用N,N-二甲基甲酰胺配制成母液(質(zhì)量分?jǐn)?shù)2％)，再用TritonX-100的水溶液(質(zhì)量分?jǐn)?shù)0.05％)稀釋至測(cè)定濃度。用藥液浸漬法，將事先挑選好的帶蚜葉片浸入藥液，輕搖10s后取出，用吸水紙吸去多余藥液，計(jì)數(shù)后放入培養(yǎng)皿內(nèi)，皿內(nèi)放有濕潤吸水紙保濕，加保鮮膜加蓋置25±1℃下恢復(fù)。用不含藥水溶液作空白對(duì)照。48h后在臺(tái)式放大鏡下檢查結(jié)果。以毛筆尖輕觸蟲體，無反應(yīng)和不能正常爬行者為死亡。普篩時(shí)所測(cè)藥劑濃度為500μg/mL。測(cè)定LC50時(shí)所測(cè)藥劑濃度梯度設(shè)定為1，5，10，20，80，200，400μg/mL。每個(gè)梯度平行測(cè)定3次。試驗(yàn)結(jié)果用Probit軟件進(jìn)行統(tǒng)計(jì)分析，計(jì)算LC50值。目標(biāo)化合物的殺蟲活性數(shù)據(jù)見表2和表3。
3)測(cè)試結(jié)果
表2II系列化合物在500μg/mL濃度下對(duì)桃蚜的殺蟲活性
在500μg/mL濃度下，II系列化合物對(duì)桃蚜表現(xiàn)出優(yōu)秀的殺蟲活性，大部分化合物的校正死亡率在85％以上。
表3 目標(biāo)化合物III對(duì)桃蚜的LC50值及95％置信限
從表3可以看出，LC50測(cè)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，對(duì)桃蚜表現(xiàn)出優(yōu)秀的殺蟲活性。