阅读说明：本技术 一类苯并咪唑类衍生物、其制备方法及应用 (Benzimidazole derivative, preparation method and application thereof ) 是由 许天明 邢家华 赵灵杰 魏优昌 黄红英 于 2019-11-21 设计创作，主要内容包括：本发明公共了一类具有通式A-1结构式的苯并咪唑类衍生物：各取代基的定义见说明书。本发明还公开了所述苯并咪唑类衍生物的制备方法及用途。本发明提供的苯并咪唑类衍生物适合用于农用杀虫。(The invention discloses a benzimidazole derivative with a structural formula of A-1:)

1. A benzimidazole derivative has the following general formula A-1:

wherein:

r is selected from hydrogen, halogen, cyano, amino substituted by C1-C20 alkyl, C1-C20 hydroxyalkylamino, C1-C20 alkylamide, C1-C20 alkoxy, imidazolyl, triazolyl, pyrazolyl, piperidinyl substituted by C1-C20 alkyl, morpholinyl substituted by C1-C20 alkyl, aryloxy substituted by at least one selected from halogen, C1-C20 alkyl, C1-C20 alkoxy and C1-C20 haloalkoxy, arylamino substituted by at least one selected from halogen, C1-C20 alkyl, C1-C20 alkoxy and C1-C20 haloalkoxy;

r1 is selected from C1-C20 alkyl, C1-C20 haloalkyl, C1-C20 cycloalkyl;

r2 is selected from hydrogen, C1-C20 alkyl, C1-C20 haloalkyl, C1-C20 cycloalkyl;

r3 is selected from hydrogen, C1-C20 alkyl, C1-C20 haloalkyl, C1-C20 alkylamino.

2. The benzimidazole derivatives according to claim 1, wherein in the general formula a-1:

r is selected from hydrogen, halogen, cyano, amino substituted by C1-C10 alkyl, C1-C10 hydroxyalkylamino, C1-C10 alkylamide, C1-C10 alkoxy, imidazolyl, triazolyl, pyrazolyl, piperidinyl substituted by C1-C10 alkyl, morpholinyl substituted by C1-C10 alkyl, aryloxy substituted by at least one selected from halogen, C1-C10 alkyl, C1-C10 alkoxy and C1-C10 haloalkoxy, arylamino substituted by at least one selected from halogen, C1-C10 alkyl, C1-C10 alkoxy and C1-C10 haloalkoxy;

r1 is selected from C1-C10 alkyl, C1-C10 haloalkyl, C1-C10 cycloalkyl;

r2 is selected from hydrogen, C1-C10 alkyl, C1-C10 haloalkyl, C1-C10 cycloalkyl;

r3 is selected from hydrogen, C1-C10 alkyl, C1-C10 haloalkyl, C1-C10 alkylamino.

3. The benzimidazole derivatives according to claim 2, wherein in the general formula a-1:

r is selected from hydrogen, halogen, cyano, amino substituted by C1-C6 alkyl, C1-C6 hydroxyalkylamino, C1-C6 alkylamide, C1-C6 alkoxy, imidazolyl, triazolyl, pyrazolyl, piperidinyl substituted by C1-C6 alkyl, morpholinyl substituted by C1-C6 alkyl, aryloxy substituted by at least one selected from halogen, C1-C6 alkyl, C1-C6 alkoxy and C1-C6 haloalkoxy, arylamino substituted by at least one selected from halogen, C1-C6 alkyl, C1-C10 alkoxy and C1-C10 haloalkoxy;

r1 is selected from C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 cycloalkyl;

r2 is selected from hydrogen, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 cycloalkyl;

r3 is selected from hydrogen, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkylamino.

4. The benzimidazole derivative according to claim 3, wherein in the general formula A-1:

r is selected from hydrogen, halogen, cyano, amino substituted by C1-C3 alkyl, C1-C3 hydroxyalkylamino, C1-C3 alkylamide, C1-C3 alkoxy, imidazolyl, triazolyl, pyrazolyl, piperidinyl substituted by C1-C3 alkyl, morpholinyl substituted by C1-C3 alkyl, aryloxy substituted by at least one selected from halogen, C1-C3 alkyl, C1-C3 alkoxy and C1-C3 haloalkoxy, arylamino substituted by at least one selected from halogen, C1-C3 alkyl, C1-C3 alkoxy and C1-C3 haloalkoxy;

r1 is selected from C1-C3 alkyl, C1-C3 haloalkyl, C1-C3 cycloalkyl;

r2 is selected from hydrogen, C1-C3 alkyl, C1-C3 haloalkyl, C1-C3 cycloalkyl;

r3 is selected from hydrogen, C1-C3 alkyl, C1-C3 haloalkyl, C1-C3 alkylamino.

5. The benzimidazole derivative according to claim 4, wherein in the general formula A-1:

r is independently selected from hydrogen, chlorine, fluorine, amino, cyano, C1-C3 alkyl substituted amino, C1-C3 hydroxyalkylamino, C1-C3 alkylamide, C1-C3 alkoxy, imidazolyl, triazolyl, pyrazolyl, piperidinyl substituted with C1-C3 alkyl, morphinyl substituted with C1-C3 alkyl, aryloxy substituted with at least one group selected from fluorine, chlorine, methyl, ethyl, methoxy, ethoxy and trifluoromethoxy, arylamino substituted with at least one group selected from fluorine, chlorine, methyl, ethyl, methoxy, ethoxy and trifluoromethoxy;

r1 is selected from methyl, ethyl, propyl, cyclopropyl, fluoromethyl, fluoroethyl;

r2 is selected from hydrogen, methyl, ethyl, propyl, cyclopropyl, fluoromethyl, fluoroethyl;

r3 is selected from hydrogen, methyl, ethyl.

6. The benzimidazole derivatives according to claim 5, wherein the benzimidazole derivative is selected from at least one of the following compounds:

7. a process for the preparation of benzimidazole derivatives according to claim 1, wherein the process for the preparation of said benzimidazole derivatives comprises:

the substituents R, R1, R2 and R3 are as defined in claim 1.

8. A process for the preparation of benzimidazole derivatives according to claim 7, wherein the process comprises:

when synthesizing the intermediate B-1, the esterifying reagent is at least one of dialkyl sulfate and halogenated alkane.

9. Use of a benzimidazole derivative according to claim 1, wherein the benzimidazole derivative is used for agricultural pesticides.

10. Use of benzimidazole derivatives according to claim 9, wherein the benzimidazole derivatives are used for controlling at least one pest selected from the group consisting of acarids, lepidopteran, homopteran, hemiptera and coleopteran.

11. An agricultural chemical insecticide, characterized in that the agricultural chemical insecticide contains 1-99% by mass of the benzimidazole derivative according to claim 1.

Technical Field

The invention belongs to the field of agricultural insecticides, and particularly relates to benzimidazole derivatives.

Background

Because the long-term use of the existing pesticide varieties causes the diseases to generate resistance to the existing pesticide varieties, new pesticide varieties with different action mechanisms are required to be continuously discovered. Meanwhile, with the excessive use of the existing pesticide, more pressure is brought to the environment, so that the development of new pesticide varieties with more efficient use amount is required.

In recent years, more and more benzimidazole organic heterocyclic compounds are successfully developed into pesticide chemicals, and recent published patents report that the benzimidazole organic heterocyclic compounds have insecticidal activity, and the compounds disclosed by WO2017134066, WO2017121674, WO2017133994, WO2017125340, WO2017093180, WO2017043385, WO2018033455 and WO2018130443 have excellent insecticidal activity and can be used as agricultural insecticides.

The benzimidazole derivatives protected by the present application are not disclosed in the prior art.

Disclosure of Invention

The present invention provides benzimidazole derivatives having the following general formula a-1:

wherein:

the substituent R of the benzimidazole derivative shown as the general formula A-1 is selected from hydrogen, halogen, cyano, amino, C1-C20 alkyl-substituted amino, C1-C20 hydroxyalkylamino, C1-C20 alkylamide, C1-C20 alkoxy, imidazolyl, triazolyl, pyrazolyl, piperidyl substituted by C1-C20 alkyl, morphinyl substituted by C1-C20 alkyl, aryloxy substituted by at least one group selected from halogen, C1-C20 alkyl, C1-C20 alkoxy and C1-C20 halogenated alkoxy, and arylamino substituted by at least one group selected from halogen, C1-C20 alkyl, C1-C20 alkoxy and C1-C20 halogenated alkoxy;

r1 is selected from C1-C20 alkyl, C1-C20 haloalkyl, C1-C20 cycloalkyl.

As a preferred embodiment, the substituent R is selected from the group consisting of hydrogen, halogen, cyano, amino, C1-C10 alkyl-substituted amino, C1-C10 hydroxyalkylamino, C1-C10 alkylamide, C1-C10 alkoxy, imidazolyl, triazolyl, pyrazolyl, piperidinyl substituted with C1-C10 alkyl, morphininyl substituted with C1-C10 alkyl, aryloxy substituted with at least one member selected from the group consisting of halogen, C1-C10 alkyl, C1-C10 alkoxy and C1-C10 haloalkoxy, arylamino substituted with at least one member selected from the group consisting of halogen, C1-C10 alkyl, C1-C10 alkoxy and C1-C10 haloalkoxy.

As another preferred embodiment, the substituent R is selected from the group consisting of hydrogen, halogen, cyano, amino, C1-C6 alkyl-substituted amino, C1-C6 hydroxyalkylamino, C1-C6 alkylamide, C1-C6 alkoxy, imidazolyl, triazolyl, pyrazolyl, piperidinyl substituted with C1-C6 alkyl, morphinyl substituted with C1-C6 alkyl, aryloxy substituted with at least one member selected from the group consisting of halogen, C1-C6 alkyl, C1-C6 alkoxy and C1-C6 haloalkoxy, arylamino substituted with at least one member selected from the group consisting of halogen, C1-C6 alkyl, C1-C10 alkoxy and C1-C10 haloalkoxy.

As a further preferred embodiment, the substituent R is selected from the group consisting of hydrogen, halogen, cyano, amino, C1-C3 alkyl-substituted amino, C1-C3 hydroxyalkylamino, C1-C3 alkylamide, C1-C3 alkoxy, imidazolyl, triazolyl, pyrazolyl, piperidinyl substituted with C1-C3 alkyl, morphininyl substituted with C1-C3 alkyl, aryloxy substituted with at least one member selected from the group consisting of halogen, C1-C3 alkyl, C1-C3 alkoxy and C1-C3 haloalkoxy, arylamino substituted with at least one member selected from the group consisting of halogen, C1-C3 alkyl, C1-C3 alkoxy and C1-C3 haloalkoxy.

As a more preferred embodiment, the substituents R are independently selected from hydrogen, chloro, fluoro, amino, cyano, C1-C3 alkyl substituted amino, C1-C3 hydroxyalkylamino, C1-C3 alkylamide, C1-C3 alkoxy, imidazolyl, triazolyl, pyrazolyl, piperidinyl substituted with C1-C3 alkyl, morpholinyl substituted with C1-C3 alkyl, aryloxy substituted with at least one group selected from fluoro, chloro, methyl, ethyl, methoxy, ethoxy and trifluoromethoxy, arylamino substituted with at least one group selected from fluoro, chloro, methyl, ethyl, methoxy, ethoxy and trifluoromethoxy.

The substituent R1 of the benzimidazole derivative shown in the general formula A-1 provided by the invention is selected from C1-C20 alkyl, C1-C20 haloalkyl and C1-C20 cycloalkyl.

As a preferred embodiment, the substituent R1 is selected from the group consisting of C1-C10 alkyl, C1-C10 haloalkyl, C1-C10 cycloalkyl.

As another preferred embodiment, the substituent R1 is selected from the group consisting of C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 cycloalkyl.

As a further preferred embodiment, the substituent R1 is selected from the group consisting of C1-C3 alkyl, C1-C3 haloalkyl, C1-C3 cycloalkyl.

As a more preferred embodiment, the substituent R1 is selected from the group consisting of methyl, ethyl, propyl, cyclopropyl, fluoromethyl, and fluoroethyl.

The substituent R2 of the benzimidazole derivative shown in the general formula A-1 provided by the invention is selected from hydrogen, C1-C20 alkyl, C1-C20 haloalkyl and C1-C20 cycloalkyl.

As a preferred embodiment, the substituent R2 is chosen from hydrogen, C1-C10 alkyl, C1-C10 haloalkyl, C1-C10 cycloalkyl.

As another preferred embodiment, the substituent R2 is selected from the group consisting of hydrogen, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 cycloalkyl.

As a further preferred embodiment, the substituent R2 is selected from the group consisting of hydrogen, C1-C3 alkyl, C1-C3 haloalkyl, C1-C3 cycloalkyl.

As a more preferred embodiment, the substituent R2 is selected from the group consisting of hydrogen, methyl, ethyl, propyl, cyclopropyl, fluoromethyl, and fluoroethyl.

The substituent R3 of the benzimidazole derivative shown in the general formula A-1 provided by the invention is selected from hydrogen, C1-C20 alkyl, C1-C20 haloalkyl and C1-C20 alkylamino.

As a preferred embodiment, the substituent R3 is selected from the group consisting of hydrogen, C1-C10 alkyl, C1-C10 haloalkyl, C1-C10 alkylamino.

As another preferred embodiment, the substituent R3 is selected from the group consisting of hydrogen, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkylamino.

As a further preferred embodiment, the substituent R3 is selected from the group consisting of hydrogen, C1-C3 alkyl, C1-C3 haloalkyl, C1-C3 alkylamino.

As a more preferred embodiment, the substituent R3 is selected from hydrogen, methyl, ethyl.

The benzimidazole derivative shown in the general formula A-1 provided by the invention is a most preferable mode, and is selected from at least one of the following compounds:

as an example, the benzimidazole derivatives represented by the above general formula A-1 may include the compounds described in the following Table 1.

TABLE 1

Typical compounds and physical properties of the benzimidazole derivatives represented by the general formula A-1 are as follows:

A1:¹H NMR(CDCl₃,600MHz)δ:9.10(s,1H,Triazole-H),8.63(d,2H,J＝8.4Hz,Pyridine-H),8.53(s,1H,Triazole-H),8.20(d,1H,J＝8.4Hz,Pyridine-H),8.20(d,2H,J＝7.2Hz,Ph-H),7.55(d,1H,J＝8.4Hz,Ph-H),3.76～3.80(m,5H,CH₂CH₃,Imidazole-CH₃),1.30(t,3H,J＝7.2Hz,CH₂CH₃).¹³C NMR(CDCl₃,150MHz)δ:169.6,165.7(J＝44.1Hz),154.0,151.0,149.7,149.0,143.4,142.5,142.4,138.2,136.1,123.5,120.7,119.8,116.1,113.9,111.2,51.8,31.4,29.3,7.3.ESI-MS([M+H]⁺)504.

A2:¹H NMR(CDCl₃,600 MHz)δ:8.55(s,1H,Pyridine-H),8.11(d,1H,J＝8.4Hz,Pyridine-H),8.07(d,1H,J＝9.0 Hz,Ph-H),7.54(d,1H,J＝8.4 Hz,Ph-H),6.51(d,1H,J＝9.0 Hz,Ph-H),3.79(s,3H,Imidazole-CH₃),3.64(q,2H,J＝7.2 Hz,CH₂CH₃),3.51～3.55(m,4H,Pyrrole-H),2.03～2.07(m,4H,Pyrrole-H),1.30(t,3H,J＝7.2 Hz,CH₂CH₃).¹³C NMR(CDCl₃,150 MHz)δ:169.8,165.5(q,J＝43.8 Hz),157.6,152.3,149.2,142.6,139.4,138.3,122.6(d,J＝6.0 Hz),120.4,116.1(q,J＝294.9 Hz),110.8,106.2,100.0,51.7,47.2,36.5,31.2,29.3,7.5.ESI-MS([M+H]⁺)506.

A3:¹H NMR(CDCl₃,600 MHz)δ:8.55(s,1H,Pyridine-H),8.11(d,1H,J＝8.4Hz,Pyridine-H),8.06(d,1H,J＝9.0 Hz,Ph-H),7.54(d,1H,J＝8.4 Hz,Ph-H),6.76(d,1H,J＝9.0 Hz,Ph-H),4.44(d,2H,J＝7.2 Hz,4-methylpiperidine-H),3.79(s,3H,Imidazole-CH₃),3.66(q,2H,J＝7.8 Hz,CH₂CH₃),2.97(t,2H,J＝12.0 Hz,4-methylpiperidine-H),1.74(d,2H,J＝13.8 Hz,4-methylpiperidine-H),1.31(t,3H,J＝7.8 Hz,CH₂CH₃),1.24～1.28(m,1H,4-methylpiperidine-H),1.17～1.21(m,2H,4-methylpiperidine-H),0.97(d,3H,J＝6.6 Hz,4-methylpiperidine-CH₃).¹³C NMR(CDCl₃,150 MHz)δ:169.8,165.6(q,J＝43.8 Hz),159.0,152.2,148.9,142.5,140.1,138.2,129.9,122.7(d,J＝19.4 Hz),,120.4,119.0,116.1(q,J＝272.1 Hz),110.8,105.8,51.7,45.3,33.7,31.1,29.3,27.2,7.5.ESI-MS([M+H]⁺)534.

A4:¹H NMR(CDCl₃,600 MHz)δ:8.56(s,1H,Pyridine-H),8.11～8.15(m,2H,Ph-H),7.55(d,1H,J＝8.4 Hz,Ph-H),6.77(d,1H,J＝9.6 Hz,Pyridine-H),4.19～4.29(m,2H,2,6-dimethylmorpholine-H),3.77(s,3H,Imidazole-CH₃),3.69～3.61(m,4H,CH₂CH₃,2,6-dimethylmorpholine-H),2.69(t,2H,J＝11.8 Hz,2,6-dimethylmorpholine-H),1.31(t,3H,J＝7.2 Hz,CH₂CH₃),1.26(d,6H,J＝6.0 Hz,2,6-dimethylmorpholine-CH₃).¹³C NMR(CDCl₃,150 MHz)δ:169.8,165.6(q,J＝44.1 Hz),159.0,152.0,148.9,142.5,140.3,138.2,124.1,122.8,120.4,119.2,116.1(q,J＝271.8 Hz),110.8,106.0,71.5,51.6,50.0,31.2,18.9,7.4.ESI-MS([M+H]⁺)550.

A5:¹H NMR(CDCl₃,600 MHz)δ:8.49(d,1H,J＝9.0 Hz,Pyridine-H),8.31～8.41(m,1H,Ph-H),8.05～8.09(m,2H,Ph-H),7.63～7.84(m,2H,NH₂),7.46～7.49(m,1H,Pyridine-H),3.77(d,2H,J＝9.6 Hz,CH₂CH₃),3.70(s,3H,Imidazole-CH₃),1.30(t,3H,J＝7.2 Hz,CH₂CH₃).ESI-MS([M+H]⁺)452.

A6:¹H NMR(CDCl₃,600 MHz)δ:8.56(d,1H,J＝8.4 Hz,Pyridine-H),8.52(s,1H,Pyridine-H),8.39(s,1H,Ph-H),8.12(d,1H,J＝7.2 Hz,Ph-H),7.64(s,1H,Ph-H),7.60(d,1H,J＝9.0 Hz,Imidazole-H),7.54(d,1H,J＝9.0 Hz,Imidazole-H),7.19(s,1H,Imidazole-H),3.84(q,2H,J＝7.2 Hz,CH₂CH₃),3.80(s,3H,Imidazole-CH₃),1.32(t,3H,J＝7.2 Hz,CH₂CH₃).¹³C NMR(CDCl₃,150 MHz)δ:169.6,165.7(q,J＝43.8 Hz),150.7,149.7(d,J＝26.4 Hz),143.2,142.4,138.3,135.5,135.0,132.0,123.4,120.7,119.8,117.0(q,J＝155.3 Hz),113.3,112.3,111.2,51.9,31.5,29.7,7.3.ESI-MS([M+H]⁺)503.

A7:¹H NMR(CDCl₃,600 MHz)δ:8.48(s,1H,Pyridine-H),8.04～8.09(m,2H,Ph-H),7.47(d,1H,J＝8.4 Hz,Ph-H),6.71(d,1H,J＝8.4 Hz,Pyridine-H),3.70～3.74(m,4H,Morpholine-H),3.71(s,3H,Imidazole-CH₃),3.53～3.63(m,4H,Morpholine-H),3.58(q,2H,J＝7.2 Hz,CH₂CH₃),1.24(s,3H,CH₂CH₃).¹³C NMR(CDCl₃,150 MHz)δ:169.8,165.5(q,J＝44.1 Hz),159.4,151.9,148.4,142.5,140.4,138.2,124.5,122.8,120.4,119.2,116.1(q,J＝271.8 Hz),110.8,105.9,66.4,51.7,44.9,31.2,7.4.ESI-MS([M+H]⁺)522.

A8:¹H NMR(CDCl₃,600 MHz)δ:8.48(dd,1H,J＝8.4 Hz,1.8 Hz,Pyridine-H),8.08(s,1H,Ph-H),7.61(d,1H,J＝8.4 Hz,Ph-H),7.46(d,1H,J＝9.0 Hz,Ph-H),7.35～7.37(m,2H,Ph-H),7.24(dd,1H,J＝8.4 Hz,1.8 Hz,Ph-H),7.08～7.10(m,2H,Ph-H),3.82(q,2H,J＝7.5 Hz,CH₂CH₃),3.60(s,3H,Imidazole-CH₃),1.36～1.39(m,3H,CH₂CH₃).¹³C NMR(CDCl₃,150 MHz)δ:164.9,151.2,150.8,150.3,143.3,138.2,14.0,132.0,131.3,129.9,126.9,125.3,123.0,119.6,112.5,111.3,106.0,51.8,31.3,29.7,7.3.ESI-MS([M+H]⁺)563.

A9:¹H NMR(CDCl₃,600 MHz)δ:8.32(dd,1H,J＝9.0 Hz,1.8 Hz,Pyridine-H),8.21(s,1H,Ph-H),7.91(dd,1H,J＝8.4 Hz,1.8 Hz,Pyridine-H),7.86(d,1H,J＝8.4 Hz,Ph-H),7.26(dd,1H,J＝9.0 Hz,1.8 Hz,Ph-H),4.43(q,2H,J＝6.6 Hz,OCH₂CH₃),3.79(s,3H,Imidazole-CH₃),3.74～3.78(m,2H,CH₂CH₃),1.35(t,3H,J＝7.4Hz,OCH₂CH₃),1.20(t,3H,J＝7.4 Hz,CH₂CH₃).¹³C NMR(CDCl₃,150 MHz)δ:165.5,160.4,158.3,151.4,147.6,142.4,142.0,138.1,129.8,121.4,118.6,117.8,113.1,112.6,100.0,63.8,51.4,31.6,14.7,7.5.ESI-MS([M+H]⁺)481.

A10:¹H NMR(CDCl₃,600 MHz)δ:8.55(s,1H,Pyridine-H),8.12(d,1H,J＝8.4Hz,Pyridine-H),8.08(d,1H,J＝8.4 Hz,Ph-H),7.54(d,1H,J＝8.4 Hz,Ph-H),6.55(d,1H,J＝9.0 Hz,Ph-H),5.24(s,1H,NH),3.78(s,3H,Imidazole-CH₃),3.61(q,2H,J＝7.2 Hz,CH₂CH₃),3.38～3.45(m,2H,NHCH₂CH₃),1.27～1.33(m,6H,NHCH₂CH₃,CH₂CH₃).¹³C NMR(CDCl₃,150 MHz)δ:169.8,165.5(q,J＝43.9 Hz),159.8,151.9,149.4,142.6,140.0,138.2,124.4,122.7,120.4,119.1,116.1(q,J＝36.9 Hz),110.8,51.6,36.9,31.2,29.3,27.2,7.4.ESI-MS([M+H]⁺)480.

A11:¹H NMR(CDCl₃,600 MHz)δ:8.55(s,1H,Pyridine-H),8.12(d,1H,J＝8.4Hz,Pyridine-H),8.08(d,1H,J＝8.4 Hz,Ph-H),7.54(d,1H,J＝8.4 Hz,Ph-H),6.56(d,1H,J＝9.0 Hz,Ph-H),5.30(s,1H,NH),3.78(s,3H,Imidazole-CH₃),3.61(q,2H,J＝7.2 Hz,CH₂CH₃),3.31～3.37(m,2H,NH(CH₂)₂CH₃),1.63～1.66(m,2H,NH(CH₂)₂CH₃),1.30(t,3H,J＝7.4 Hz,CH₂CH₃),0.99(t,3H,J＝7.2 Hz,NH(CH₂)₂CH₃).¹³C NMR(CDCl₃,150 MHz)δ:169.8,168.5,165.6(q,J＝43.9 Hz),159.9,151.9,149.4,142.6,140.1,138.2,124.3,122.7,120.4,119.1,116.1(q,J＝271.7 Hz),110.8,51.6,43.9,31.2,22.5,11.4,7.4.ESI-MS([M+H]⁺)494.

A12:¹H NMR(CDCl₃,600 MHz)δ:8.55(s,1H,Pyridine-H),8.13(d,2H,J＝8.4Hz,Pyridine-H),8.07～8.11(m,1H,Ph-H),7.54(d,1H,J＝8.4 Hz,Ph-H),6.57(d,1H,J＝9.0 Hz,Ph-H),5.35(s,1H,NH),3.78(s,3H,Imidazole-CH₃),3.62(q,3H,J＝7.2 Hz,CH₂CH₃),3.01(d,3H,J＝4.9 Hz,CH₃),1.30(t,3H,J＝7.2 Hz,CH₂CH₃).¹³C NMR(CDCl₃,150 MHz)δ:169.8,165.6(d,J＝43.9 Hz),160.5,151.9,149.4,142.6,140.1,138.2,124.5,120.4,119.1,116.1(q,J＝271.9 Hz),110.9,100.0,51.7,36.5,31.2,29.0,7.4.ESI-MS([M+H]⁺)466.

A13:¹H NMR(CDCl₃,600 MHz)δ:8.55(s,1H,Pyridine-H),8.12(d,1H,J＝8.4Hz,Ph-H),8.06(d,1H,J＝9.0 Hz,Ph-H),7.54(d,1H,J＝8.4 Hz,Ph-H),6.54(d,1H,J＝9.0 Hz,Pyridine-H),5.08(s,1H,NH),3.78(s,3H,Imidazole-CH₃),3.55～3.67(m,3H,NHCH,CH₂CH₃),1.42～1.48(m,1H,NHCHCH₂),1.31(t,3H,J＝7.2 Hz,CH₂CH₃),1.25～1.27(m,1H,NHCHCH₂),1.12(d,1H,J＝6.6 Hz,NHCH₃),0.92～0.96(m,5H,NHCH₃,NHCHCH₂CH₃).¹³C NMR(CDCl₃,150 MHz)δ:169.8,165.7,159.4,151.9,149.5,142.6,140.1,138.2,124.1,122.7,120.4,119.1,117.1,110.8,51.6,47.6,31.2,30.3,29.6,29.3,20.2,10.3,7.4.ESI-MS([M+H]⁺)508.

A15:¹H NMR(CDCl₃,600 MHz)δ:8.55(s,1H,Pyridine-H),8.12(d,1H,J＝8.4Hz,Ph-H),8.07(d,1H,J＝9.0 Hz,Ph-H),7.54(d,1H,J＝8.4 Hz,Ph-H),6.55(d,1H,J＝9.0 Hz,Pyridine-H),5.30(s,1H,NH),3.77(s,3H,Imidazole-CH₃),3.61(q,2H,J＝8.4 Hz,CH₂CH₃),3.36(q,2H,J＝6.6 Hz,NHCH₂),1.68～1.72(m,2H,NHCH₂CH₂),1.40～1.44(m,2H,NHCH₂CH₂CH₂),1.30(t,3H,J＝7.2 Hz,CH₂CH₃),0.95(t,3H,J＝7.2Hz,NH(CH₂)₃CH₃).¹³C NMR(CDCl₃,150 MHz)δ:169.8,165.7(q,J＝43.9 Hz),159.9,151.9,149.4,142.6,140.0,138.2,124.2,122.7,120.4,119.1,116.1(q,J＝271.8 Hz),110.8,51.6,41.8,31.2,29.3,27.2,20.1,13.8,7.4.ESI-MS([M+H]⁺)508.

A16:¹H NMR(CDCl₃,600 MHz)δ:8.55(s,1H,Pyridine-H),8.13(d,1H,J＝9.0Hz,Ph-H),8.07(d,1H,J＝9.0 Hz,Ph-H),7.55(d,1H,J＝8.4 Hz,Ph-H),6.63(d,1H,J＝9.0 Hz,Pyridine-H),5.64(s,1H,NH),3.81～3.84(m,2H,NHCH₂),3.77(s,3H,Imidazole-CH₃),3.60(q,4H,J＝8.4 Hz,CH₂CH₃,NHCH₂CH₂),1.29～1.33(m,3H,CH₂CH₃),0.86～0.89(m,1H,OH).¹³C NMR(CDCl₃,150 MHz)δ:169.8,165.7,159.9,151.8,149.2,142.5,138.2,124.9,122.8,120.4,119.2,116.2,112.5,110.9,61.6,51.6,44.1,31.2,29.7,7.4.ESI-MS([M+H]⁺)596.

A17:¹H NMR(CDCl₃,600 MHz)δ:8.55(s,1H,Pyridine-H),8.12(d,1H,J＝8.4Hz,Ph-H),8.06(d,1H,J＝8.4 Hz,Ph-H),7.54(d,1H,J＝8.4 Hz,Ph-H),6.54(d,1H,J＝9.0 Hz,Pyridine-H),5.20(s,1H,NH),3.78(s,3H,Imidazole-CH₃),3.59(d,2H,J＝7.2 Hz,CH₂CH₃),2.03(d,2H,J＝5.4 Hz,CH(CH₂)₅),1.93(d,1H,J＝12.0 Hz,CH(CH₂)₅),1.76(d,2H,J＝5.4 Hz,CH(CH₂)₅),1.36～1.40(m,4H,CH(CH₂)₅),1.30(t,3H,J＝7.2 Hz,CH₂CH₃),1.25～1.27(m,2H,CH(CH₂)₅).¹³C NMR(CDCl₃,150 MHz)δ:169.8,165.6(q,J＝44.1 Hz),159.1,151.9,149.5,142.6,138.2,124.0,122.7,120.4,119.1,116.1(q,J＝271.9 Hz),110.8,51.6,33.9,32.8,31.2,29.7,25.4,24.9,24.6,7.4.ESI-MS([M+H]⁺)534.

A18:¹H NMR(CDCl₃,600 MHz)δ:8.55(s,1H,Pyridine-H),8.13(d,1H,J＝9.0Hz,Ph-H),8.06(d,1H,J＝9.0 Hz,Ph-H),7.54(d,1H,J＝8.4 Hz,Ph-H),6.62(d,1H,J＝9.0 Hz,Pyridine-H),5.35(s,1H,NH),4.17(s,1H,NHCH),3.78(s,3H,Imidazole-CH₃),3.61～3.64(m,1H,OH),3.58～3.60(m,2H,CH₂CH₃),1.26～1.30(m,6H,CH₂CH₃,NHCHCH₃).¹³C NMR(CDCl₃,150 MHz)δ:215.4,207.7,169.8,142.5,138.2,122.8,120.4,119.2,110.9,100.5,97.9,77.1,66.4,51.64,31.2,29.3,27.2,17.3,7.4.ESI-MS([M+H]⁺)510.

A19:¹H NMR(CDCl₃,600MHz)δ:8.55(s,1H,Pyridine-H),8.13(d,1H,J＝8.4Hz,Ph-H),8.08(d,1H,J＝8.4Hz,Ph-H),7.54(d,1H,J＝8.4Hz,Ph-H),6.57(d,1H,J＝9.0Hz,Pyridine-H),5.33(s,1H,NH),4.07～4.14(m,1H,NHCH),3.78(s,3H,Imidazole-CH₃),3.59(t,2H,J＝7.2Hz,CH₂CH₃),2.06～2.10(m,2H,CH(CH₂)₄),1.75(s,3H,CH(CH₂)₄),1.51(s,3H,CH(CH₂)₄),1.30(t,3H,J＝7.2Hz,CH₂CH₃).¹³C NMR(CDCl₃,150MHz)δ:169.8,165.6(d,J＝43.8Hz),159.5,151.9,149.4,142.6,140.2,138.2,124.1,122.7,120.4,119.1,116.1(d,J＝271.9Hz),110.8,53.5,51.6,33.3,31.2,29.7,23.7,7.4.ESI-MS([M+H]⁺)520.

A20:¹H NMR(CDCl₃,600MHz)δ:8.55(s,1H,Pyridine-H),8.13(d,1H,J＝8.4Hz,Ph-H),8.05～8.09(m,1H,Ph-H),7.55(d,1H,J＝8.4Hz,Ph-H),6.56(d,1H,J＝9.0Hz,Pyridine-H),5.37(s,1H,NH),3.77(s,3H,Imidazole-CH₃),3.59(q,2H,J＝6.0Hz,CH₂CH₃),3.20(s,2H,NHCH₂),1.89～1.93(m,1H,CH(CH₃)₂),1.31(t,3H,J＝7.2Hz,CH₂CH₃),0.99(d,6H,J＝6.0Hz,CH(CH₃)₂).¹³C NMR(CDCl₃,150MHz)δ:169.8,165.6(q,J＝43.9Hz),160.1,151.9,149.4,142.5,140.1,138.2,124.3,122.7,120.4,119.1,116.1(q,J＝271.7Hz),110.8,77.1,51.6,49.6,31.1,29.7,28.3,20.2,7.4.ESI-MS([M+H]⁺)508.

the invention also provides a preparation method of the benzimidazole-containing derivative, which comprises the following steps:

in the above preparation methods, initiators, catalysts, bases, solvents, condensing agents, dehydrating agents, etc., which are commonly used in the art, can be used in the present invention.

R, R1, R2 is as described in claim 1, claim 2, claim 3, claim 4; when the intermediate B-1 is synthesized, the esterifying reagent is selected from dialkyl sulfate, halogenated alkane and the like;

the benzimidazole-containing derivative provided by the invention is suitable for agricultural insecticide. Is particularly suitable for controlling mites, lepidoptera, homoptera, hemiptera or coleopteran pests.

The invention also provides an agricultural chemical insecticide which contains 1-99% of benzimidazole-containing derivatives in percentage by mass.

When an agrochemical insecticide is formulated, the agrochemical insecticide may be formulated into various liquids, emulsifiable concentrates, suspending agents, aqueous suspensions, microemulsions, emulsions, aqueous emulsions, powders, wettable powders, soluble powders, granules, water-dispersible granules or capsules. The agricultural chemical pesticide comprises the quinoline compound and a carrier. The carrier includes at least two, at least one of which is a surfactant. The carrier may be a solid or a liquid. Suitable solid carriers include natural or synthetic clays and silicates, such as natural silica and diatomaceous earth; magnesium silicates such as talc; magnesium aluminum silicates such as kaolinite, montmorillonite and mica; white carbon black, calcium carbonate, light calcium carbonate; calcium sulfate; limestone; sodium sulfate; amine salts such as ammonium sulfate, hexamethylene diamine. Liquid carriers include water and organic solvents, which can also be used as adjuvants or antifreeze additives when water is used as a solvent or diluent. Suitable organic solvents include aromatic hydrocarbons such as benzene, xylene, toluene, and the like; chlorinated hydrocarbons such as chlorobenzene, vinyl chloride, chloroform, dichloromethane, and the like; aliphatic hydrocarbons such as petroleum fractions, cyclohexane, light mineral oil; alcohols such as isopropyl alcohol, butyl alcohol, ethylene glycol, glycerin, cyclohexanol, and the like; and ethers and esters thereof; and also ketones, such as acetone, cyclohexanone, and dimethylformamide and N-methyl-pyrrolidone.

The surfactant may be an emulsifier, dispersant or wetting agent; may be ionic or non-ionic. Nonionic emulsifiers such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, polyoxyethylene fatty ammonia, and commercially available emulsifiers: nongru 2201B, Nongru 0203B and Nongru 100^#Agricultural milk 500^#Agricultural milk 600^#Agricultural milk 600-2^#1601, 2201, NP-10, NP-15 and 507^#Agricultural milk OX-635, agricultural milk OX-622, agricultural milk OX-653, agricultural milk OX-667, Ningru 36^#. The dispersant comprises sodium lignosulfonate, nekal, calcium lignosulfonate, methyl naphthalene sulfonic acid formaldehyde condensate and the like. The wetting agent is: sodium lauryl sulfate, sodium dodecylbenzenesulfonate, sodium alkylnaphthalenesulfonate, and the like.

The agrochemical insecticides can be prepared by a general method. For example, the active substance is mixed with a liquid solvent and/or a solid carrier, with the addition of surfactants such as emulsifiers, dispersants, stabilizers, wetting agents, and also with the addition of other auxiliaries such as: binders, defoamers, oxidizing agents, and the like.

Detailed Description

The present invention is further illustrated by the following examples, which are not intended to limit the invention to these embodiments. It will be appreciated by those skilled in the art that the present invention encompasses all alternatives, modifications and equivalents as may be included within the scope of the claims.

Preparation of compounds

Example 1: synthesis of 3, 6-dichloropyridine-2-carboxylic acid methyl ester

3, 6-dichloropyridine-2-carboxylic acid (5.0g,26.0mmol) was dissolved in 50mL of acetone, potassium carbonate (4.3g,31.2mmol) was added, dimethyl sulfate (3.3g,26.0mmol) was slowly added dropwise, stirred at room temperature for 4h, and monitored by TLC. After the reaction was completed, the inorganic salt was removed by filtration, the organic phase was dried over anhydrous magnesium sulfate and then filtered, and the filtrate was desolventized to obtain 4.5g of a white solid with a yield of 89.2%.

The white solid obtained was 3, 6-dichloropyridine-2-carboxylic acid methyl ester and its nuclear magnetic data were:

m.p.59～60℃；¹H NMR(CDCl₃,600MHz)δ:7.77(d,1H,J＝8.4Hz,Pyridine-H),7.42(d,1H,J＝8.4Hz,Pyridine-H),4.00(s,3H,OCH₃).¹³C NMR(CDCl₃,150MHz)δ:163.5,148.9,147.1,141.3,53.2。

example 2: synthesis of 6-chloro-3-ethylthio pyridine-2-carboxylic acid methyl ester

Potassium tert-butoxide (6.6g,59.1mmol) was dissolved in 15mL of DMF and ethyl mercaptan (3.3g,53.7mmol) was added dropwise under ice bath conditions to give potassium ethyl mercaptide. Taking intermediate 3, 6-dichloropyridine-2-carboxylic acid methyl ester (10.0g,48.5mmol) to dissolve in DMF, slowly dropwise adding potassium ethyl mercaptide under the ice bath condition of-5 ℃, stirring for 30min at room temperature, and tracking and detecting by TLC. After the reaction was completed, the solvent was spin-dried, and column chromatography separation [ eluent: V (petroleum ether): V (ethyl acetate): 5:1] was performed to obtain 8.9g of a pale yellow solid, yield 79.1%.

The prepared light yellow solid is 6-chloro-3-ethylthio pyridine-2-carboxylic acid methyl ester, and the nuclear magnetic data thereof are as follows:

m.p.128～129℃；¹H NMR(CDCl₃,600MHz)δ:7.66(d,1H,J＝8.4Hz,Pyridine-H),7.41(d,1H,J＝8.4Hz,Pyridine-H),3.99(s,3H,OCH₃),2.94(q,2H,J＝7.2Hz,CH₂),1.39(t,3H,J＝7.2Hz,CH₂CH₃).¹³C NMR(CDCl₃,150MHz)δ:164.9,146.2,138.3,136.8,127.0,53.1,26.2,14.2,13.1。

example 3: synthesis of 6-chloro-3-ethylthio pyridine-2-carboxylic acid

Sodium hydroxide (1.7g, 43.2mmol) was dissolved in 15mL of water to prepare a 10% aqueous solution of sodium hydroxide. The intermediate 6-chloro-3-ethylthiopyridine-2-carboxylic acid methyl ester (5.0g, 21.6mmol) was dissolved in 20mL tetrahydrofuran, the prepared aqueous sodium hydroxide solution was added, and the reaction solution was transferred to an oil bath and refluxed for 2 h. And (5) TLC tracking detection. After the reaction was completed, the reaction mixture was cooled to room temperature, the solvent was evaporated under reduced pressure, the residue was poured into water (100mL), the pH was adjusted to weak acidity with dilute hydrochloric acid until all the solid was precipitated, and the filtrate was filtered to obtain a pale yellow powder (3.1 g) with a yield of 63.9%.

The prepared light yellow powder is 6-chloro-3-ethylthio pyridine-2-carboxylic acid, and the nuclear magnetic data thereof are as follows:

m.p.119～120℃；¹H NMR(CDCl₃,600MHz)δ:10.76(s,1H,COOH),7.71(d,1H,J＝8.4Hz,Pyridine-H),7.49(d,1H,J＝8.4Hz,Pyridine-H),2.97(q,2H,J＝7.2Hz,CH₂),1.44(t,3H,J＝7.2Hz,CH₂CH₃).¹³C NMR(CDCl₃,150MHz)δ:162.8,144.2,140.5,139.5,136.5,128.3,25.4,12.8。

example 4: synthesis of 6-chloro-3-ethylthio pyridine-2-formyl chloride

The intermediate 2-4(2.0g,9.2mmol) was dissolved in 10mL of thionyl chloride, a drop of N, N-dimethylformamide was added as a catalyst, and heated under reflux in an oil bath for 4 h. TLC tracking detection, after the reaction is finished, thionyl chloride is evaporated under reduced pressure to obtain 2.1g of earthy yellow solid, and the yield is 86.3%.

The prepared solid is 6-chloro-3-ethylthio pyridine-2-formyl chloride.

Example 5: synthesis of 4-methylamino-3-aminobenzonitrile

4-methylamino-3-nitrobenzonitrile (29.6g,190.0mmol) is dissolved in 200mL tetrahydrofuran, 5.0g of 5% palladium carbon is added as a catalyst, after air in a reaction bottle is replaced by nitrogen, hydrogen is continuously introduced into the system, the mixture is stirred for 4 hours at room temperature, and TLC tracking detection is carried out. After the completion of the reaction, the reaction mixture was filtered, the solvent was dried by spinning, and column chromatography was performed [ eluent: V (petroleum ether): V (ethyl acetate) ═ 5:1] to obtain 22.2g of a yellow powder, yield 93.2%.

The prepared yellow powder is 4-methylamino-3-aminobenzonitrile, and the nuclear magnetic data are as follows:

m.p.139～140℃；¹H NMR(CDCl₃,600MHz)δ:6.93(s,1H,Ph-H),7.19(d,1H,J＝8.4Hz,Ph-H),6.58(d,1H,J＝8.4Hz,Ph-H),6.27(s,2H,NH₂),3.82(s,1H,NH),2.91(s,3H,CH₃).¹³C NMR(CDCl₃,150MHz)δ:143.5,132.9,126.8,120.6,119.1,109.5,99.4,30.6。

example 6: synthesis of 6-chloro-N- (5-nitrile-2- (methylamino) phenyl-3- (ethylthio)) nicotinic acid amide

Taking intermediate 4-methylamino-3-aminobenzonitrile (6.9g,47.3mmol) to dissolve in 50mL tetrahydrofuran, adding triethylamine (4.8g,47.3mmol) as an acid-binding agent, and dropwise adding 50mL tetrahydrofuran solution containing intermediate 6-chloro-3-ethylthio pyridine-2-formyl chloride (11.2g,47.3mmol) under ice bath conditions. And (5) TLC tracking detection. After completion of the reaction, the solvent was dried by spinning, 500mL of ethyl acetate and 350mL of water were added to extract the organic layer, the organic layer was washed with saturated brine (50 mL. times.3), the organic layer was separated and dried over anhydrous magnesium sulfate, and filtration and desolventization were carried out to obtain 11.0g of a yellow solid with a yield of 67.1%.

The yellow solid prepared was 6-chloro-N- (5-cyano-2- (methylamino) phenyl-3- (ethylthio)) nicotinic acid amide with nuclear magnetic data:

m.p.178～179℃；¹H NMR(CDCl₃,600MHz)δ:9.29(s,1H,CONH),7.70(d,1H,J＝9.0Hz,Ph-H),7.66(s,1H,Ph-H),7.48(d,1H,J＝8.4Hz,Ph-H),7.44(d,1H,J＝9.0Hz,Ph-H),6.72(d,1H,J＝8.4Hz,Ph-H),4.60(s,1H,NHCH₃),2.92～2.96(m,5H,CH₂CH₃,NHCH₃),1.42(t,3H,J＝7.2Hz,CH₂CH₃).¹³C NMR(CDCl₃,150MHz)δ:147.5,136.4,132.3,129.7,127.1,122.1,119.7,118.7,118.2,111.0,100.0,76.9,30.2,25.6,12.7。

example 7: synthesis of 3- (6-chloro-3 (ethylthio) pyridin-2-yl) -1-methyl-1H-benzimidazole-5-nitrile group

The intermediate 6-chloro-N- (5-cyano-2- (methylamino) phenyl-3- (ethylthio)) nicotinic acid amide (11.0g,31.9mmol) was dissolved in 40mL of acetic acid, heated and refluxed for 2 hours in an oil bath, followed by TLC detection, after completion of the reaction, cooled to room temperature, excess acetic acid was spin-dried under reduced pressure, dichloromethane (200mL × 3) was added for extraction, the organic phase was washed with saturated brine (50mL × 3), the organic phase was separated and dried over anhydrous magnesium sulfate, filtered, desolventized, and subjected to column chromatography [ eluent: V (petroleum ether): V (ethyl acetate): 7:1] to obtain 9.1g of a yellow solid with a yield of 87.5%.

The yellow solid prepared was 3- (6-chloro-3 (ethylsulfanyl) pyridin-2-yl) -1-methyl-1H-benzimidazole-5-carbonitrile, which had nuclear magnetic data as follows:

m.p.169～170℃；¹H NMR(CDCl₃,600MHz)δ:8.22(s,1H,Ph-H),7.74(d,1H,J＝8.4Hz,Ph-H),7.63(d,1H,J＝8.4Hz,Pyridine-H),7.51(d,1H,J＝8.4Hz,Ph-H),7.40(d,1H,J＝8.4Hz,Pyridine-H),3.99(s,3H,Imidazole-CH₃),2.96(q,2H,J＝7.2Hz,CH₂CH₃),1.34(d,3H,J＝7.2Hz,CH₂CH₃).¹³C NMR(CDCl₃,150MHz)δ:150.9,146.3,145.4,141.7,138.6,137.2,136.9,126.9,125.7,125.1,119.8,111.0,105.9,32.2,27.0,13.3。

example 8: synthesis of 3- (6-chloro-3 (ethylthio) pyridin-2-yl) -1-methyl-1H-benzimidazole-5-carboxamide oxime

Dissolving the intermediate 3- (6-chloro-3 (ethylthio) pyridin-2-yl) -1-methyl-1H-benzimidazole-5-nitrile (9.1g,27.8mmol) in 150mL of absolute ethanol, adding hydroxylamine hydrochloride (8.1g,11.7mmol) and triethylamine (12.3g,121.9mmol), heating and refluxing in an oil bath for 4H, and performing TLC tracking detection. After completion of the reaction, the reaction mixture was cooled to room temperature, the solvent was spin-dried under reduced pressure, ethyl acetate (200 mL. times.3) was added for extraction, the organic phase was washed with saturated brine (50 mL. times.3), the organic phase was separated and dried over anhydrous magnesium sulfate, and filtration and desolventization were carried out to obtain 8.5g of a yellow solid in 85.1% yield. m.p.181-182 ℃.

The yellow solid prepared was 3- (6-chloro-3 (ethylsulfanyl) pyridin-2-yl) -1-methyl-1H-benzimidazole-5-carboxamide oxime.

Example 9: synthesis of 3- (2- (6-chloro-3 (ethylsulfanyl) pyridin-2-yl) -1-methyl-1H-benzimidazol-5-yl) -5 (trifluoromethyl) -1, 2, 4-dioxazole

Putting the intermediate 3- (6-chloro-3 (ethylthio) pyridin-2-yl) -1-methyl-1H-benzimidazole-5-formamide oxime (8.5g,23.6mmol) into a 100mL single-neck flask, slowly dropwise adding excessive trifluoroacetic anhydride under an ice bath condition, stirring at room temperature for 0.5H after dropwise adding is finished, transferring the reaction solution into an oil bath pot, heating and refluxing for 6H, and tracking and detecting by TLC. After completion of the reaction, the reaction mixture was poured into 500mL of ice water, the pH was adjusted to weak acidity with ammonia water, ethyl acetate (200mL × 3) was added for extraction, the organic phase was washed with saturated brine (50mL × 3), the organic phase was separated and dried over anhydrous magnesium sulfate, filtered, desolventized, and column chromatography was performed [ eluent: V (petroleum ether): V (ethyl acetate): 4:1] to obtain 5.1g of a white solid, and the yield was 51.1%.

The white solid prepared was 3- (2- (6-chloro-3 (ethylsulfanyl) pyridin-2-yl) -1-methyl-1H-benzimidazol-5-yl) -5 (trifluoromethyl) -1, 2, 4-dioxazole with nuclear magnetic data:

m.p.178～179℃；¹H NMR(CDCl₃,600MHz)δ:8.61(s,1H,Ph-H),8.07(d,1H,J＝8.4Hz,Ph-H),7.67(d,1H,J＝8.4Hz,Pyridine-H),7.49(d,1H,J＝8.4Hz,Ph-H),7.32(d,1H,J＝8.4Hz,Pyridine-H),3.94(s,3H,Imidazole-CH₃),2.99(q,2H,J＝7.2Hz,CH₂CH₃),1.29(t,3H,J＝7.2Hz,CH₂CH₃).¹³C NMR(CDCl₃,150MHz)δ:169.7,150.2,146.3,145.9,142.3,138.6,137.3,136.8,124.8,123.1,120.9,119.4,110.7,65.4,42.0,32.1,27.0,13.4。

example 10: synthesis of 3- (2- (6-chloro-3 (ethylsulfonyl) pyridin-2-yl) -1-methyl-1H-benzimidazol-5-yl) -5 (trifluoromethyl) -1, 2, 4-dioxazole

Intermediate 3- (2- (6-chloro-3 (ethylsulfanyl) pyridin-2-yl) -1-methyl-1H-benzimidazol-5-yl) -5 (trifluoromethyl) -1, 2, 4-dioxazole (5.1g,11.6mmol) was dissolved in 150mL dichloromethane, m-chloroperoxybenzoic acid (6.0g,34.8mmol) was added, stirred at room temperature for 2H and monitored by TLC tracking. After completion of the reaction, the pH was adjusted to neutral with an aqueous solution of sodium hydrogencarbonate, dichloromethane (200mL × 3) was added for extraction, the organic phase was washed with saturated brine (50mL × 3), the organic phase was separated and dried over anhydrous magnesium sulfate, filtered, desolventized, and separated by column chromatography [ eluent: V (petroleum ether): V (ethyl acetate): 4:1] to obtain 3.2g of a pale yellow solid, yield 55.6%.

The prepared light yellow solid is 3- (2- (6-chloro-3 (ethylsulfonyl) pyridine-2-yl) -1-methyl-1H-benzimidazole-5-yl) -5 (trifluoromethyl) -1, 2, 4-dioxazole, and the nuclear magnetic data of the light yellow solid are as follows:

m.p.168～169℃；¹H NMR(CDCl₃,600MHz)δ:8.57(s,1H,Ph-H),8.48(d,1H,J＝8.4Hz,Ph-H),8.16(d,1H,J＝8.4Hz,Pyridine-H),7.71(d,1H,J＝8.4Hz,Ph-H),7.59(d,1H,J＝8.4Hz,Pyridine-H),3.92(q,2H,J＝7.2Hz,CH₂CH₃),3.89(s,3H,Imidazole-CH₃),1.38(t,3H,J＝7.2Hz,CH₂CH₃).¹³C NMR(CDCl₃,150MHz)δ:169.6,165.5,155.2,149.7,149.5,142.4,142.1,138.3,136.3,125.5,123.4,120.7,119.7,115.2,111.1,51.9,31.5,7.2。

example 11: 3- (2- (6-Azotriazolyl-3 (ethylsulfonyl) pyridin-2-yl) -1-methyl-1H-benzimidazol-5-yl) -5 (trifluoromethyl) -1, 2, 4-dioxazole (A1)

To a 25mL single neck flask was added the intermediate 3- (2- (6-chloro-3 (ethylsulfonyl) pyridin-2-yl) -1-methyl-1H-benzimidazol-5-yl) -5 (trifluoromethyl) -1, 2, 4-dioxazole (0.2g,0.4mmol), dissolved in 10mL DMF, and the azole (0.4mmol), potassium carbonate (0.06g,0.4mmol) were added and stirred at room temperature for 2H. TLC (thin layer chromatography) tracking detection, after the reaction is finished, the solvent is evaporated under reduced pressure, ethyl acetate (50 mL. times.3) is added for extraction, an organic phase is washed with saturated salt water (35 mL. times.3), the organic phase is separated and dried with anhydrous magnesium sulfate, filtration and desolventization are carried out, and column chromatography separation is carried out [ eluent: V (petroleum ether): V (ethyl acetate): 5:1] to obtain the target compound.

The compound prepared is 3- (2- (6-azatriazolyl-3 (ethylsulfonyl) pyridin-2-yl) -1-methyl-1H-benzimidazol-5-yl) -5 (trifluoromethyl) -1, 2, 4-dioxazole (a1), and the nuclear magnetic data is as follows:

¹H NMR(CDCl₃,600MHz)δ:9.10(s,1H,Triazole-H),8.63(d,2H,J＝8.4Hz,Pyridine-H),8.53(s,1H,Triazole-H),8.20(d,1H,J＝8.4Hz,Pyridine-H),8.20(d,2H,J＝7.2Hz,Ph-H),7.55(d,1H,J＝8.4Hz,Ph-H),3.76～3.80(m,5H,CH₂CH₃,Imidazole-CH₃),1.30(t,3H,J＝7.2Hz,CH₂CH₃).¹³C NMR(CDCl₃,150MHz)δ:169.6,165.7(J＝44.1Hz),154.0,151.0,149.7,149.0,143.4,142.5,142.4,138.2,136.1,123.5,120.7,119.8,116.1,113.9,111.2,51.8,31.4,29.3,7.3.ESI-MS([M+H]⁺)504.

second, preparation of preparation

In the following examples 12 to 14, the components were prepared in mass percent.

Example 12, 30% suspending agent

Compound a1 and the other components are mixed thoroughly, the suspension thus obtained is diluted with water to give a dilution of any desired concentration.

Example 13, 30% emulsifiable concentrate

Dissolving the phosphorous acid in toluene, adding compound A1 and ethoxylated triglyceride to obtain transparent solution.

Example 14, 60% wettable powder

Compound a1, sodium dodecylnaphthalenesulfonate, sodium lignosulfonate, and diatomaceous earth were mixed together and ground in a grinder until the particles met the standard.

Third, biological activity test

Example 15 insecticidal Activity against armyworm

And (3) fully soaking a proper amount of corn leaves in the prepared liquid medicine, naturally drying in the shade, putting into a culture dish filled with filter paper, inoculating 10 heads/dish of armyworm larvae in the 3-instar middle stage, culturing in an observation room at 24-27 ℃, and investigating results after 48 hours. If the body of the insect is touched by a brush pen, no response is regarded as dead insect.

The results show that compounds A1-A20 showed 100% mortality at the tested concentration of 250 mg/L.

Example 16 insecticidal Activity against Plutella xylostella

The method comprises the steps of soaking a proper amount of cabbage leaves in prepared liquid medicine fully, naturally drying in the shade, placing the cabbage leaves in a culture dish filled with filter paper, inoculating 10 heads/dish of 2-instar middle-stage larvae of the diamondback moth, placing the cabbage leaves in an observation room at 24-27 ℃ for culture, and investigating results after 48 hours. If the body of the insect is touched by a brush pen, no response is regarded as dead insect.

The results show that compounds A1-A20 showed 100% mortality at the tested concentration of 500 mg/L.

Example 17 insecticidal Activity against Medicago Aphis

And (3) carrying out spray treatment on the broad bean leaf seedlings with the alfalfa aphids under a Potter spray tower, culturing the treated alfalfa aphids in an observation room at the temperature of 20-22 ℃, and investigating the result after 48 hours. If the body of the insect is touched by a brush pen, no response is regarded as dead insect.

The results show that the compounds A1-A20 showed over 90% mortality at the tested concentration of 500 mg/L.