pyridine-containing benzimidazole compounds or their salts, preparation methods, insecticides, acaricides, parasite control agents and their applications

Abstract

This invention relates to the field of insecticides, disclosing pyridine-containing benzimidazole compounds or their salts, their preparation methods, and their applications as insecticides, acaricides, parasite control agents, and related products. The pyridine-containing benzimidazole compounds have the structure shown in formula (I). The pyridine-containing benzimidazole compounds or their salts provided by this invention exhibit excellent insecticidal and acaricidal effects. In particular, the pyridine-containing benzimidazole compounds of this invention achieve acaricidal effects even at low concentrations.

Description

[0001] Cross-references to related applications

[0002] This application claims the benefit of Chinese Patent Application No. 202210976591.0, filed on August 15, 2022, entitled "Pyridyl-containing benzimidazole compounds or their salts and preparation methods, and insecticides, acaricides, parasite control agents and applications", the contents of which are incorporated herein by reference. Technical Field

[0003] This invention relates to the field of insecticides, specifically to a benzimidazole compound containing a pyridine group or its salt, a method for its preparation, and insecticides, acaricides, parasite control agents, and their applications. Background Technology

[0004] In crop production in agriculture and horticulture, the losses caused by pests are still significant, and pests that have developed resistance to existing pesticides are emerging. From the perspectives of environmental impact and labor saving, there is a desire to develop insecticides and acaricides for agriculture and horticulture that have new effects, have less impact on natural enemies and beneficial insects, and have penetration and transfer activity.

[0005] WO2019225663 discloses a type of benzimidazole compound with certain insecticidal and acaricidal activities (such as compounds KC-1, KC-2, KC-3, etc.).

[0006]

[0007] Advanced Materials Research Vols 236-238 (2011) pp.2570-2573 reported the following benzimidazole compounds. Some of these compounds, although possessing anti-inflammatory activity, did not disclose their insecticidal and acaricidal activities (such as compound KC-4).

[0008]

[0009] Currently, there is a need for compounds that can effectively kill insects and mites even at low concentrations. Summary of the Invention

[0010] The purpose of this invention is to overcome the shortcomings of existing benzimidazole compounds, which only exhibit insecticidal and acaricidal activity at high concentrations, making it difficult to meet the needs of controlling field mites. This invention provides a benzimidazole compound containing pyridyl groups and its salt, which is intended to be used as an active ingredient in insecticides and acaricides, and can achieve highly effective control at low concentrations (not higher than 100 ppm).

[0011] To achieve the above objectives, a first aspect of the present invention provides a pyridinyl-containing benzimidazole compound or a salt thereof, the pyridinyl-containing benzimidazole compound having the structure shown in formula (I):

[0012]

[0013] In equation (I),

[0014] R is selected from substituted or unsubstituted C1-C. 10 Alkyl, substituted or unsubstituted C3-C 10 Cycloalkyl, substituted or unsubstituted C2-C 10 alkenyl, substituted or unsubstituted C2-C 10 The alkynyl group, and the optional substituents are each independently selected from halogens, C1-C... 10 Alkyl, halogenated C1-C 10 Alkyl, C3-C 10 cycloalkyl, halogenated C3-C 10 cycloalkyl, C1-C 10 Alkoxy, halogenated C1-C 10 Alkoxy, C3-C 10 Cycloalkoxy, halogenated C3-C 10 At least one of the cycloalkoxy groups;

[0015] Y1, Y2, Y3, and Y4 are each independently selected from H, halogen, CN, NO2, formyl group, substituted or unsubstituted C1-C. 10 Alkyl, substituted or unsubstituted C3-C 10 cycloalkyl, substituted or unsubstituted C1-C 10 Alkoxy, substituted or unsubstituted C1-C 10 Alkylthio, substituted or unsubstituted C1-C 10 Alkyl sulfinyl, substituted or unsubstituted C1-C 10 Alkyl sulfonyl, substituted or unsubstituted C1-C 10 Alkylsulfonylamino, substituted or unsubstituted halogenated C1-C 10 Alkylsulfonylamino, substituted or unsubstituted C1-C 10 Alkyl carbonyl, substituted or unsubstituted C1-C 10 Alkoxycarbonyl, substituted or unsubstituted arylcarbonyl, substituted or unsubstituted aryloxycarbonyl, substituted or unsubstituted C2-C6 alkenyl, substituted or unsubstituted C2-C6 alkynyl, substituted or unsubstituted C2-C6 alkenyloxy, substituted or unsubstituted C2-C6 alkynyloxy, substituted or unsubstituted C1-C 10 Alkylcarbonyl group, substituted or unsubstituted C1-C 10 Cyanoalkyl, substituted or unsubstituted C1-C10 The substituted or unsubstituted silyl group, substituted or unsubstituted amino group, substituted or unsubstituted aryl group, substituted or unsubstituted aryl C1-C6 alkyl group, substituted or unsubstituted aryloxy group, substituted or unsubstituted aryl C1-C6 alkoxy group, substituted or unsubstituted arylsulfonyl group, substituted or unsubstituted arylsulfinyl group, substituted or unsubstituted arylthio group, substituted or unsubstituted aryl C1-C6 alkylsulfonyl group, substituted or unsubstituted aryl C1-C6 alkylsulfinyl group, substituted or unsubstituted aryl C1-C6 alkylthio group, substituted or unsubstituted heterocyclic group, substituted or unsubstituted heterocyclic C1-C6 alkyl group, substituted or unsubstituted heterocyclic oxy group, and optionally the substituents are each independently selected from halogens, C1-C6... 10 Alkyl, halogenated C1-C 10 Alkyl, C3-C 10 cycloalkyl, halogenated C3-C 10 cycloalkyl, C1-C 10 Alkoxy, halogenated C1-C 10 Alkoxy, C3-C 10 Cycloalkoxy, halogenated C3-C 10 At least one of the cycloalkoxy groups;

[0016] Z1, Z2, Z3, and Z4 are each independently selected from H, halogen, CN, NO2, formyl group, substituted or unsubstituted C1-C. 10 Alkyl, substituted or unsubstituted C3-C 10 cycloalkyl, substituted or unsubstituted C1-C 10 Alkoxy, substituted or unsubstituted C1-C 10 Alkylthio, substituted or unsubstituted C1-C 10 Alkyl sulfinyl, substituted or unsubstituted C1-C 10 Alkyl sulfonyl, substituted or unsubstituted C1-C 10 Alkyl carbonyl, substituted or unsubstituted C1-C 10 Alkoxycarbonyl, substituted or unsubstituted arylcarbonyl, substituted or unsubstituted aryloxycarbonyl, substituted or unsubstituted C2-C6 alkenyl, substituted or unsubstituted C2-C6 alkynyl, substituted or unsubstituted C2-C6 alkenyloxy, substituted or unsubstituted C2-C6 alkynyloxy, substituted or unsubstituted C1-C 10 Alkylcarbonyl group, substituted or unsubstituted C1-C 10 Cyanoalkyl, substituted or unsubstituted C1-C 10The substituted or unsubstituted silyl group, substituted or unsubstituted amino group, substituted or unsubstituted aryl group, substituted or unsubstituted aryl C1-C6 alkyl group, substituted or unsubstituted aryloxy group, substituted or unsubstituted aryl C1-C6 alkoxy group, substituted or unsubstituted arylsulfonyl group, substituted or unsubstituted arylsulfinyl group, substituted or unsubstituted arylthio group, substituted or unsubstituted aryl C1-C6 alkylsulfonyl group, substituted or unsubstituted aryl C1-C6 alkylsulfinyl group, substituted or unsubstituted aryl C1-C6 alkylthio group, substituted or unsubstituted heterocyclic group, substituted or unsubstituted heterocyclic C1-C6 alkyl group, substituted or unsubstituted heterocyclic oxy group, and optionally the substituents are each independently selected from halogens, C1-C6... 10 Alkyl, halogenated C1-C 10 Alkyl, C3-C 10 cycloalkyl, halogenated C3-C 10 cycloalkyl, C1-C 10 Alkoxy, halogenated C1-C 10 Alkoxy, C3-C 10 Cycloalkoxy, halogenated C3-C 10 At least one of the cycloalkoxy groups; optionally, any two adjacent groups of Z1, Z2, Z3, Z4 form a group, and at least one group forms at least one 3- to 8-membered ring with the bonded benzene ring via or without at least one heteroatom.

[0017] A second aspect of the present invention discloses a method for preparing benzimidazole compounds containing pyridinyl groups or salts thereof, the method comprising:

[0018] (1) In a first solvent, in the presence of a first basic substance and a condensing agent, compound V and compound IV undergo a first reaction to obtain compound III;

[0019] (2) In a second solvent, compound III and an acidic substance undergo a second reaction to obtain compound II;

[0020] (3) In a third solvent, in the presence of a second alkaline substance, the compound II and the sulfonyl compound are subjected to a third reaction to obtain the pyridine-containing benzimidazole compound;

[0021] Wherein, compound V has the structure shown in formula (V), compound IV has the structure shown in formula (IV), compound III has the structure shown in formula (III), compound II has the structure shown in formula (II), the pyridyl-containing benzimidazole compound has the structure shown in formula (I), and the sulfonyl-containing compound has the structure shown in formula (VI).

[0022]

[0023] In equations (I), (II), (III), (IV), (V), and (VI), the definitions of R, Y1, Y2, Y3, Y4, Z1, Z2, Z3, and Z4 correspond to the definitions described in the first aspect above, and X is selected from halogens.

[0024] A third aspect of the present invention provides benzimidazole compounds containing pyridinyl groups or salts thereof, prepared by the method described in the second aspect above.

[0025] The fourth aspect of the present invention provides the use of the pyridyl-containing benzimidazole compounds or their salts described in the first or third aspects above in the preparation of insecticides, acaricides and / or parasite control agents.

[0026] The fifth aspect of the present invention provides an insecticide and acaricide containing an active ingredient selected from at least one of the pyridyl-containing benzimidazole compounds or their salts described in the first or third aspects above.

[0027] The sixth aspect of the present invention provides the application of the aforementioned insecticides and acaricides in agriculture, forestry and horticulture for insecticidal and / or acaricidal purposes.

[0028] The seventh aspect of the present invention provides a parasite control agent containing an active ingredient selected from at least one of the pyridine-containing benzimidazole compounds or their salts described in the first or third aspects above.

[0029] The eighth aspect of the present invention provides the application of the aforementioned parasite control agent in the prevention and control of internal and external parasites in animals.

[0030] Compared with the prior art, the present invention has at least the following advantages:

[0031] The pyridine-containing benzimidazole compounds or their salts provided by this invention, when used as active ingredients as insecticides, acaricides and / or parasite control agents, can have excellent control effects even when used at low concentrations.

[0032] Other features and advantages of the present invention will be described in detail in the following detailed description section. Detailed Implementation

[0033] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0034] In this invention, the terms used are uniformly interpreted as follows:

[0035] Halogens refer to fluorine, chlorine, bromine, and iodine.

[0036] Alkyl refers to alkyl groups in the form of straight chains or branches, excluding cycloalkyl groups. The C1-C8 alkyl refers to alkyl groups having 1-8 carbon atoms, such as including but not limited to methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, etc.

[0037] Cycloalkyl refers to an alkyl group containing a cyclic chain. The C1-C8 cycloalkyl refers to a cycloalkyl group having 1-8 carbon atoms, such as including but not limited to cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc.

[0038] Alkenyl refers to straight-chain or branched alkenyl groups. The C2-C8 alkenyl refers to alkenyl groups having 2-8 carbon atoms, such as including but not limited to 1-propenyl, 2-propenyl and different butenyl, pentenyl and hexenyl isomers; alkenyl also includes polyenes, such as 1,2-propadienyl and 2,4-hexadienyl.

[0039] Alkyne refers to a straight-chain or branched alkyne group. The C2-C8 alkyne group refers to an alkyne group having 2-8 carbon atoms, such as including but not limited to 1-propynyl, 2-propynyl and different butynyl, pentynyl and hexynyl isomers; alkyne also includes groups containing multiple triple bonds, such as 2,5-hexadiynyl.

[0040] Alkoxy groups are alkyl groups, whether straight-chain or branched, with an oxygen atom attached to the alkyl end. 1-8 Alkoxy groups refer to alkoxy groups having 1 to 8 carbon atoms, such as but not limited to methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, etc.

[0041] Cycloalkoxy groups are cycloalkyl groups containing oxygen atoms, wherein the C 1-8 The cycloalkoxy group refers to a cycloalkoxy group having 1-8 carbon atoms, such as including but not limited to cyclopropoxy and cyclobutoxy.

[0042] Alkylthio groups are groups with a sulfur atom attached to the alkyl end, including but not limited to methylthio, ethylthio, n-propylthio, isopropylthio, tert-butylthio, etc.

[0043] Alkyl sulfinyl group refers to a group with a sulfinyl group attached to the alkyl end, such as including but not limited to methyl sulfinyl, ethyl sulfinyl, n-propyl sulfinyl, isopropyl sulfinyl, tert-butyl sulfinyl, etc.

[0044] Alkyl sulfonyl groups refer to groups with a sulfonyl group attached to the alkyl end, such as including but not limited to methyl sulfonyl, ethyl sulfonyl, n-propyl sulfonyl, isopropyl sulfonyl, tert-butyl sulfonyl, etc.

[0045] Halogenated alkyl, halogenated alkenyl, halogenated alkynyl, halogenated cycloalkyl, halogenated alkoxy, halogenated cycloalkoxy, halogenated alkylthio, halogenated alkylsulfinyl, and halogenated alkylsulfonyl are groups formed by replacing at least one hydrogen atom of alkyl, alkenyl, alkynyl, cycloalkyl, alkoxy, cycloalkoxy, alkylthio, alkylsulfinyl, and alkylsulfonyl groups with a halogen atom. When there are two or more halogen atoms, the halogen atoms can be the same or different.

[0046] In this invention, cycloalkyl-substituted alkyl, halocycloalkyl-substituted alkyl, cycloalkyl-substituted haloalkyl, alkoxy-substituted alkyl, haloalkoxy-substituted alkyl, alkoxy-substituted haloalkyl, cycloalkoxy-substituted alkyl, halocycloalkoxy-substituted alkyl, and cycloalkoxy-substituted haloalkyl respectively refer to at least one hydrogen atom in the alkyl group being substituted by cycloalkyl, halocycloalkyl, alkoxy, haloalkoxy, cycloalkoxy, or halocycloalkoxy.

[0047] In this invention, heteroatoms include, but are not limited to, O, S, and N atoms.

[0048] Other groups have similar definitions as described above, except that they have different substituents or different numbers of carbon atoms, and will not be described in detail here.

[0049] Other terms used in this invention may be interpreted in the manner commonly used in the art.

[0050] As previously described, a first aspect of the present invention provides a pyridinyl-containing benzimidazole compound or a salt thereof, the pyridinyl-containing benzimidazole compound having the structure shown in formula (I):

[0051]

[0052] In equation (I),

[0053] R is selected from substituted or unsubstituted C1-C. 10 Alkyl, substituted or unsubstituted C3-C 10 Cycloalkyl, substituted or unsubstituted C2-C 10 alkenyl, substituted or unsubstituted C2-C 10 The alkynyl group, and the optional substituents are each independently selected from halogens, C1-C... 10 Alkyl, halogenated C1-C 10 Alkyl, C3-C 10 cycloalkyl, halogenated C3-C 10 cycloalkyl, C1-C 10 Alkoxy, halogenated C1-C10 Alkoxy, C3-C 10 Cycloalkoxy, halogenated C3-C 10 At least one of the cycloalkoxy groups;

[0054] Y1, Y2, Y3, and Y4 are each independently selected from H, halogen, CN, NO2, formyl group, substituted or unsubstituted C1-C. 10 Alkyl, substituted or unsubstituted C3-C 10 cycloalkyl, substituted or unsubstituted C1-C 10 Alkoxy, substituted or unsubstituted C1-C 10 Alkylthio, substituted or unsubstituted C1-C 10 Alkyl sulfinyl, substituted or unsubstituted C1-C 10 Alkyl sulfonyl, substituted or unsubstituted C1-C 10 Alkylsulfonylamino, substituted or unsubstituted halogenated C1-C 10 Alkylsulfonylamino, substituted or unsubstituted C1-C 10 Alkyl carbonyl, substituted or unsubstituted C1-C 10 Alkoxycarbonyl, substituted or unsubstituted arylcarbonyl, substituted or unsubstituted aryloxycarbonyl, substituted or unsubstituted C2-C6 alkenyl, substituted or unsubstituted C2-C6 alkynyl, substituted or unsubstituted C2-C6 alkenyloxy, substituted or unsubstituted C2-C6 alkynyloxy, substituted or unsubstituted C1-C 10 Alkylcarbonyl group, substituted or unsubstituted C1-C 10 Cyanoalkyl, substituted or unsubstituted C1-C 10 The substituted or unsubstituted silyl group, substituted or unsubstituted amino group, substituted or unsubstituted aryl group, substituted or unsubstituted aryl C1-C6 alkyl group, substituted or unsubstituted aryloxy group, substituted or unsubstituted aryl C1-C6 alkoxy group, substituted or unsubstituted arylsulfonyl group, substituted or unsubstituted arylsulfinyl group, substituted or unsubstituted arylthio group, substituted or unsubstituted aryl C1-C6 alkylsulfonyl group, substituted or unsubstituted aryl C1-C6 alkylsulfinyl group, substituted or unsubstituted aryl C1-C6 alkylthio group, substituted or unsubstituted heterocyclic group, substituted or unsubstituted heterocyclic C1-C6 alkyl group, substituted or unsubstituted heterocyclic oxy group, and optionally the substituents are each independently selected from halogens, C1-C6... 10 Alkyl, halogenated C1-C 10 Alkyl, C3-C 10 cycloalkyl, halogenated C3-C 10 cycloalkyl, C1-C 10 Alkoxy, halogenated C1-C 10 Alkoxy, C3-C 10Cycloalkoxy, halogenated C3-C 10 At least one of the cycloalkoxy groups;

[0055] Z1, Z2, Z3, and Z4 are each independently selected from H, halogen, CN, NO2, formyl group, substituted or unsubstituted C1-C. 10 Alkyl, substituted or unsubstituted C3-C 10 cycloalkyl, substituted or unsubstituted C1-C 10 Alkoxy, substituted or unsubstituted C1-C 10 Alkylthio, substituted or unsubstituted C1-C 10 Alkyl sulfinyl, substituted or unsubstituted C1-C 10 Alkyl sulfonyl, substituted or unsubstituted C1-C 10 Alkyl carbonyl, substituted or unsubstituted C1-C 10 Alkoxycarbonyl, substituted or unsubstituted arylcarbonyl, substituted or unsubstituted aryloxycarbonyl, substituted or unsubstituted C2-C6 alkenyl, substituted or unsubstituted C2-C6 alkynyl, substituted or unsubstituted C2-C6 alkenyloxy, substituted or unsubstituted C2-C6 alkynyloxy, substituted or unsubstituted C1-C 10 Alkylcarbonyl group, substituted or unsubstituted C1-C 10 Cyanoalkyl, substituted or unsubstituted C1-C 10 The substituted or unsubstituted silyl group, substituted or unsubstituted amino group, substituted or unsubstituted aryl group, substituted or unsubstituted aryl C1-C6 alkyl group, substituted or unsubstituted aryloxy group, substituted or unsubstituted aryl C1-C6 alkoxy group, substituted or unsubstituted arylsulfonyl group, substituted or unsubstituted arylsulfinyl group, substituted or unsubstituted arylthio group, substituted or unsubstituted aryl C1-C6 alkylsulfonyl group, substituted or unsubstituted aryl C1-C6 alkylsulfinyl group, substituted or unsubstituted aryl C1-C6 alkylthio group, substituted or unsubstituted heterocyclic group, substituted or unsubstituted heterocyclic C1-C6 alkyl group, substituted or unsubstituted heterocyclic oxy group, and optionally the substituents are each independently selected from halogens, C1-C6... 10 Alkyl, halogenated C1-C 10 Alkyl, C3-C 10 cycloalkyl, halogenated C3-C 10 cycloalkyl, C1-C 10 Alkoxy, halogenated C1-C 10 Alkoxy, C3-C 10 Cycloalkoxy, halogenated C3-C 10At least one of the cycloalkoxy groups; optionally, any two adjacent groups of Z1, Z2, Z3, Z4 form a group, and at least one group forms at least one 3- to 8-membered ring with the bonded benzene ring via or without at least one heteroatom.

[0056] According to the present invention, the optional representation may or may not include a multi-ring structure.

[0057] According to the present invention, any two adjacent groups among Z1, Z2, Z3, and Z4 constitute a group, and at least one group forms at least one 3- to 8-membered ring with the bonded benzene ring via or without at least one heteroatom, indicating that at least one combination of Z1 and Z2, Z2 and Z3, and Z3 and Z4 forms at least one 3- to 8-membered ring with the bonded benzene ring via or without at least one heteroatom.

[0058] Preferably, in formula (I),

[0059] R is selected from C1-C 10 Alkyl, halogenated C1-C 10 Alkyl, C3-C 10 Cycloalkyl-substituted C1-C 10 Alkyl, halogenated C3-C 10 Cycloalkyl-substituted C1-C 10 Alkyl, C3-C 10 Cycloalkyl-substituted halogenated C1-C 10 Alkyl, C1-C 10 Alkoxy substitution C1-C 10 Alkyl, halogenated C1-C 10 Alkoxy substitution C1-C 10 Alkyl, C1-C 10 Alkoxy-substituted halogenated C1-C 10 Alkyl, C3-C 10 Cycloalkoxy-substituted C1-C 10 Alkyl, halogenated C3-C 10 Cycloalkoxy-substituted C1-C 10 Alkyl, C3-C 10 Cycloalkoxy-substituted halogenated C1-C 10 Alkyl, C3-C 10 cycloalkyl, halogenated C3-C 10 cycloalkyl, C1-C 10 Alkyl substitution C3-C 10 cycloalkyl, halogenated C1-C 10 Alkyl substitution C3-C 10 cycloalkyl, C1-C 10 Alkyl-substituted halogenated C3-C 10 cycloalkyl, C1-C 10 Alkoxy substitution C3-C 10cycloalkyl, halogenated C1-C 10 Alkoxy substitution C3-C 10 cycloalkyl, C1-C 10 Alkoxy-substituted halogenated C3-C 10 cycloalkyl, C3-C 10 Cycloalkoxy substitution of C3-C 10 cycloalkyl, halogenated C3-C 10 Cycloalkoxy substitution of C3-C 10 cycloalkyl, C3-C 10 Cycloalkoxy-substituted halogenated C3-C 10 cycloalkyl, C2-C 10 Alkenyl, halogenated C2-C 10 alkenyl, C2-C 10 Alkyne group, halogenated C2-C 10 alkynyl group;

[0060] Y1, Y2, Y3, and Y4 are each independently selected from H, halogens, CN, NO2, and Cl-C. 10 Alkyl, halogenated C1-C 10 Alkyl, C3-C 10 Cycloalkyl-substituted C1-C 10 Alkyl, halogenated C3-C 10 Cycloalkyl-substituted C1-C 10 Alkyl, C3-C 10 Cycloalkyl-substituted halogenated C1-C 10 Alkyl, C1-C 10 Alkoxy substitution C1-C 10 Alkyl, halogenated C1-C 10 Alkoxy substitution C1-C 10 Alkyl, C1-C 10 Alkoxy-substituted halogenated C1-C 10 Alkyl, C3-C 10 cycloalkyl, halogenated C3-C 10 cycloalkyl, C1-C 10 Alkyl substitution C3-C 10 cycloalkyl, halogenated C1-C 10 Alkyl substitution C3-C 10 cycloalkyl, C1-C 10 Alkyl-substituted halogenated C3-C 10 cycloalkyl, C1-C 10 Alkoxy, halogenated C1-C 10 Alkoxy, C1-C 10 Alkylthio, Halogenated C1-C 10 Alkylthio, C1-C 10 Alkyl sulfinyl, halogenated C1-C 10 alkyl sulfinyl, C1-C 10Alkyl sulfonyl, halogenated C1-C 10 Alkyl sulfonyl, C1-C 10 Alkylsulfonylamino, halogenated C1-C 10 Alkylsulfonylamino, formyl, C1-C 10 Alkyl carbonyl, halogenated C1-C 10 Alkyl carbonyl, C1-C 10 Alkoxy carbonyl, halogenated C1-C 10 Alkoxycarbonyl, arylcarbonyl, aryloxycarbonyl, C2-C6 alkenyl, C2-C6 alkynyl, halo-C2-C6 alkenyl, halo-C2-C6 alkynyl, C2-C6 alkenyloxy, C2-C6 alkynyloxy, halo-C2-C6 alkenyloxy, halo-C2-C6 alkynyloxy, C1-C 10 Alkylcarbonyl group, halogenated C1-C 10 Alkylcarbonyl group, C1-C 10 Cyanoalkyl, C1-C 10 cyanoalkoxy, C1-C 10 Alkyl-substituted silyl, substituted or unsubstituted amino, aryl, aryl C1-C6 alkyl, aryloxy, aryl C1-C6 alkoxy, arylsulfonyl, arylsulfinyl, arylthio, aryl C1-C6 alkylsulfonyl, aryl C1-C6 alkylsulfinyl, aryl C1-C6 alkylthio, heterocyclic, heterocyclic C1-C6 alkyl, heterocyclic oxy, and optionally the substituents are each independently selected from halogens, C1-C6... 10 Alkyl, halogenated C1-C 10 Alkyl, C3-C 10 cycloalkyl, halogenated C3-C 10 cycloalkyl, C1-C 10 Alkoxy, halogenated C1-C 10 Alkoxy, C3-C 10 Cycloalkoxy, halogenated C3-C 10 At least one of the cycloalkoxy groups;

[0061] Z1, Z2, Z3, and Z4 are each independently selected from H, halogens, CN, NO2, and Cl-C. 10 Alkyl, halogenated C1-C 10 Alkyl, C3-C 10 Cycloalkyl-substituted C1-C 10 Alkyl, halogenated C3-C 10 Cycloalkyl-substituted C1-C 10 Alkyl, C3-C 10 Cycloalkyl-substituted halogenated C1-C 10 Alkyl, C1-C 10 Alkoxy substitution C1-C 10 Alkyl, halogenated C1-C 10 Alkoxy substitution C1-C10 Alkyl, C1-C 10 Alkoxy-substituted halogenated C1-C 10 Alkyl, C3-C 10 cycloalkyl, halogenated C3-C 10 cycloalkyl, C1-C 10 Alkyl substitution C3-C 10 cycloalkyl, halogenated C1-C 10 Alkyl substitution C3-C 10 cycloalkyl, C1-C 10 Alkyl-substituted halogenated C3-C 10 cycloalkyl, C1-C 10 Alkoxy, halogenated C1-C 10 Alkoxy, C1-C 10 Alkylthio, Halogenated C1-C 10 Alkylthio, C1-C 10 Alkyl sulfinyl, halogenated C1-C 10 alkyl sulfinyl, C1-C 10 Alkyl sulfonyl, halogenated C1-C 10 Alkyl sulfonyl, formyl, C1-C 10 Alkyl carbonyl, halogenated C1-C10 alkyl carbonyl, C1-C 10 Alkoxycarbonyl, halogenated C1-C10 alkoxycarbonyl, arylcarbonyl, aryloxycarbonyl, C2-C6 alkenyl, C2-C6 alkynyl, halogenated C2-C6 alkenyl, halogenated C2-C6 alkynyl, C2-C6 alkenyloxy, C2-C6 alkynyloxy, halogenated C2-C6 alkenyloxy, halogenated C2-C6 alkynyloxy, C1-C 10 Alkylcarbonyl group, halogenated C1-C 10 Alkylcarbonyl group, C1-C 10 Cyanoalkyl, C1-C 10 cyanoalkoxy, C1-C 10 Alkyl-substituted silyl, substituted or unsubstituted amino, aryl, aryl C1-C6 alkyl, aryloxy, aryl C1-C6 alkoxy, arylsulfonyl, arylsulfinyl, arylthio, aryl C1-C6 alkylsulfonyl, aryl C1-C6 alkylsulfinyl, aryl C1-C6 alkylthio, heterocyclic, heterocyclic C1-C6 alkyl, heterocyclic oxy, and optionally the substituents are each independently selected from halogens, C1-C6... 10 Alkyl, halogenated C1-C 10 Alkyl, C3-C 10 cycloalkyl, halogenated C3-C 10 cycloalkyl, C1-C 10 Alkoxy, halogenated C1-C 10 Alkoxy, C3-C 10 Cycloalkoxy, halogenated C3-C10 At least one of the cycloalkoxy groups; optionally, any two adjacent groups of Z1, Z2, Z3, Z4 form a group, and at least one group forms at least one 3- to 8-membered ring with the bonded benzene ring via or without at least one heteroatom.

[0062] The following provides several particularly preferred embodiments of the pyridine-containing benzimidazole compounds of the present invention. Detailed Implementation Method 1

[0064] R is selected from C1-C8 alkyl, halogenated C1-C8 alkyl, C3-C8 cycloalkyl-substituted C1-C8 alkyl, halogenated C3-C8 cycloalkyl-substituted C1-C8 alkyl, C3-C8 cycloalkyl-substituted halogenated C1-C8 alkyl, C1-C8 alkoxy-substituted C1-C8 alkyl, halogenated C1-C8 alkoxy-substituted C1-C8 alkyl, C1-C8 alkoxy-substituted halogenated C1-C8 alkyl, C3-C8 cycloalkoxy-substituted C1-C8 alkyl, halogenated C3-C8 cycloalkoxy-substituted C1-C8 alkyl, C3-C8 cycloalkyl-substituted halogenated C1-C8 alkyl, C3-C8 cycloalkyl, halogenated C3-C8 cycloalkyl. C1-C8 alkyl-substituted C3-C8 cycloalkyl, halo-C1-C8 alkyl-substituted C3-C8 cycloalkyl, C1-C8 alkyl-substituted halo-C3-C8 cycloalkyl, C1-C8 alkoxy-substituted C3-C8 cycloalkyl, halo-C1-C8 alkoxy-substituted C3-C8 cycloalkyl, C1-C8 alkoxy-substituted halo-C3-C8 cycloalkyl, C3-C8 cycloalkoxy-substituted C3-C8 cycloalkyl, halo-C3-C8 cycloalkoxy-substituted C3-C8 cycloalkyl, C3-C8 cycloalkoxy-substituted halo-C3-C8 cycloalkyl, C2-C8 alkenyl, halo-C2-C8 alkenyl, C2-C8 ynyl, halo-C2-C8 ynyl;

[0065] Y1, Y2, Y3, and Y4 are each independently selected from H, halogen, CN, NO2, C1-C8 alkyl, halogenated C1-C8 alkyl, C3-C8 cycloalkyl-substituted C1-C8 alkyl, halogenated C3-C8 cycloalkyl-substituted C1-C8 alkyl, C3-C8 cycloalkyl-substituted halogenated C1-C8 alkyl, C1-C8 alkoxy-substituted C1-C8 alkyl, halogenated C1-C8 alkoxy-substituted C1-C8 alkyl, C1-C8 alkoxy-substituted halogenated C1-C8 alkyl, C3-C8 cycloalkyl, halogenated C3-C8 Cycloalkyl, C1-C8 alkyl-substituted C3-C8 cycloalkyl, halo-C1-C8 alkyl-substituted C3-C8 cycloalkyl, C1-C8 alkyl-substituted halo-C3-C8 cycloalkyl, C1-C8 alkoxy, halo-C1-C8 alkoxy, C1-C8 alkylthio, halo-C1-C8 alkylthio, C1-C8 alkylsulfinyl, halo-C1-C8 alkylsulfinyl, C1-C8 alkylsulfonyl, halo-C1-C8 alkylsulfonyl, C1-C8 alkylsulfonylamino, halo-C1-C8 alkylsulfonylamino;

[0066] Z1, Z2, Z3, and Z4 are each independently selected from H, halogen, CN, NO2, C1-C8 alkyl, halogenated C1-C8 alkyl, C3-C8 cycloalkyl, halogenated C3-C8 cycloalkyl, C1-C8 alkoxy, halogenated C1-C8 alkoxy, C1-C8 alkylthio, halogenated C1-C8 alkylthio, C1-C8 alkylsulfinyl, halogenated C1-C8 alkylsulfinyl, C1-C8 alkylsulfonyl, and halogenated C1-C8 alkylsulfonyl. Detailed Implementation Method 2

[0068] In equation (I),

[0069] R is selected from C1-C8 alkyl, halo-C1-C8 alkyl, C3-C8 cycloalkyl, halo-C3-C8 cycloalkyl, C2-C8 alkenyl, halo-C2-C8 alkenyl, C2-C8 ynyl and halo-C2-C8 ynyl;

[0070] Y1, Y2, Y3, and Y4 are each independently selected from H, halogen, CN, NO2, C1-C8 alkyl, halo-C1-C8 alkyl, C3-C8 cycloalkyl, halo-C3-C8 cycloalkyl, C1-C8 alkoxy, halo-C1-C8 alkoxy, C1-C8 alkylthio, halo-C1-C8 alkylthio, C1-C8 alkylsulfinyl, halo-C1-C8 alkylsulfinyl, C1-C8 alkylsulfonyl, halo-C1-C8 alkylsulfonyl, C1-C8 alkylsulfonylamino, and halo-C1-C8 alkylsulfonylamino.

[0071] Z1, Z2, Z3, and Z4 are each independently selected from H, halogen, CN, NO2, C1-C8 alkyl, halogenated C1-C8 alkyl, C1-C8 alkoxy, halogenated C1-C8 alkoxy, C1-C8 alkylthio, halogenated C1-C8 alkylthio, C1-C8 alkylsulfinyl, halogenated C1-C8 alkylsulfinyl, C1-C8 alkylsulfonyl, and halogenated C1-C8 alkylsulfonyl. Detailed Implementation Method 3

[0073] In equation (I),

[0074] R is selected from C1-C8 alkyl, halo-C1-C8 alkyl, C3-C8 cycloalkyl, halo-C3-C8 cycloalkyl, C2-C5 alkenyl, and C2-C5 alkynyl.

[0075] Y1 and Y4 are each independently selected from H, halogens, CN, NO2, C1-C8 alkyl, and halogenated C1-C8 alkyl;

[0076] Y2 and Y3 are each independently selected from H, halogen, CN, NO2, C1-C8 alkyl, halo-C1-C8 alkyl, C1-C8 alkoxy, halo-C1-C8 alkoxy, C1-C8 alkylsulfonylamino, and halo-C1-C8 alkylsulfonylamino.

[0077] Z1, Z2, Z3, and Z4 are each independently selected from H, halogen, CN, NO2, C1-C8 alkyl, halogenated C1-C8 alkyl, C1-C8 alkoxy, halogenated C1-C8 alkoxy, C1-C8 alkylthio, halogenated C1-C8 alkylthio, C1-C8 alkylsulfinyl, halogenated C1-C8 alkylsulfinyl, C1-C8 alkylsulfonyl, and halogenated C1-C8 alkylsulfonyl. Detailed Implementation Method 4

[0079] In equation (I),

[0080] R is selected from methyl, ethyl, n-propyl, isopropyl, allyl, and propargyl;

[0081] Y1 and Y4 are each independently selected from H, F, Cl, Br, I, CN, NO2, CH3, OCH3, CF3, OCF3, CF2Cl, CFCl2, and CCl3;

[0082] Y2 and Y3 are each independently selected from H, F, Cl, Br, I, CN, NO2, CH3, CF3, OCH3, OCH2CF3, OCH2CH2CF3, OCH2CF2CF3, OCF3, CF2Cl, CFCl2, CCl3, NHC(O)2CH3, NHC(O)2CF3, NHS(O)2CF3, NHS(O)2CH2CH3, SCF3, S(O)CF3, S(O)2CF3;

[0083] Z1, Z2, Z3, and Z4 are each independently selected from H, F, Cl, Br, I, CN, NO2, CH3, OCH3, CF3, OCF3, SCF3, S(O)CF3, and S(O)2CF3. Detailed Implementation Method 5

[0085] The pyridine-containing benzimidazole compounds are selected from at least one of the compounds shown in Table 1:

[0086] Table 1

[0087]

[0088]

[0089]

[0090]

[0091]

[0092]

[0093]

[0094]

[0095] The inventors of this invention have discovered that the pyridine-containing benzimidazole compounds or their salts in the above-mentioned preferred embodiments have better insecticidal and acaricidal effects. In particular, the compound in preferred embodiment 5 has better insecticidal and acaricidal effects, and can have excellent insecticidal and acaricidal effects when used at low concentrations (e.g., 6.25 mg / L).

[0096] Furthermore, the present invention provides performance data (NMR) of some compounds as shown in Table 2:

[0097] Table 2

[0098]

[0099] In this invention, the salts of the pyridyl-containing benzimidazole compounds or their salts include, but are not limited to, inorganic salts such as hydrochloride, sulfate, nitrate, and phosphate; and organic salts such as acetate, fumarate, maleate, oxalate, methanesulfonate, benzenesulfonate, and p-toluenesulfonate.

[0100] As previously described, a second aspect of the present invention provides a method for preparing a pyridinyl-containing benzimidazole compound or a salt thereof, the method comprising:

[0101] (1) In a first solvent, in the presence of a first basic substance and a condensing agent, compound V and compound IV undergo a first reaction to obtain compound III;

[0102] (2) In a second solvent, compound III and an acidic substance undergo a second reaction to obtain compound II;

[0103] (3) In a third solvent, in the presence of a second alkaline substance, the compound II and the sulfonyl compound are subjected to a third reaction to obtain the pyridyl-containing benzimidazole compound or its salt;

[0104] Wherein, compound V has the structure shown in formula (V), compound IV has the structure shown in formula (IV), compound III has the structure shown in formula (III), compound II has the structure shown in formula (II), the pyridyl-containing benzimidazole compound has the structure shown in formula (I), and the sulfonyl-containing compound has the structure shown in formula (VI).

[0105]

[0106] In equations (I), (II), (III), (IV), (V), and (VI), the definitions of R, Y1, Y2, Y3, Y4, Z1, Z2, Z3, and Z4 correspond to the definitions described in the first aspect above, and X is selected from halogens.

[0107] According to the present invention, in step (1), the first reaction is as follows:

[0108]

[0109] Preferably, in step (1), the conditions for the first reaction include: a temperature of -10°C to 150°C and a reaction time of 0.1-48h.

[0110] Preferably, in step (1), the molar ratio of compound V to compound IV is 0.5-2:1. Compound V and compound IV are commercially available.

[0111] Preferably, in step (1), the condensing agent is selected from at least one of 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide (EDC) or its hydrochloride (EDCI), carbonyl diimidazole (CDI), 1,3-dicyclohexylcarbodiimide (DCC), diethyl cyanophosphate (DEPC), chlorocarbonate compounds, and 2-chloro-1-methylpyridinium iodide.

[0112] Preferably, in step (1), the molar ratio of the condensing agent to compound IV is 1-2:1.

[0113] Preferably, in step (1), the first alkaline substance is selected from at least one of pyridine, dimethylaminopyridine (DMAP), triethylamine, diisopropylethylamine, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium acetate, potassium acetate, sodium methoxide, sodium ethoxide, sodium tert-butoxide, potassium tert-butoxide, and 1,8-diazabicyclo[5.4.0]undec-7-ene.

[0114] Preferably, in step (1), the molar ratio of the first alkaline substance to compound IV is 0.1-10:1.

[0115] Preferably, in step (1), the first solvent is selected from at least one of pyridine, dichloromethane, chloroform, benzene tetrachloride, toluene, xylene, chlorobenzene, dichlorobenzene, diethyl ether, methyl tert-butyl ether, dioxane, tetrahydrofuran, 2-methyltetrahydrofuran, N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMA), N-methylpyrrolidone (NMP), acetone, methyl ethyl ketone, dimethyl sulfoxide, and 1,3-dimethyl-2-imidazolium ketone.

[0116] Preferably, in step (1), the amount of the first solvent used is 1-20 mL relative to 1 mmol of compound IV.

[0117] According to the present invention, in step (1), the first solvent and the first alkaline substance can be the same, for example, both can be pyridine. Furthermore, it should be specifically noted that when the first solvent and the first alkaline substance are the same substance, they need to be measured separately.

[0118] According to the present invention, in step (2), the second reaction is as follows:

[0119]

[0120] Preferably, in step (2), the conditions for the second reaction include: a temperature of -10°C to 300°C and a reaction time of 0.1-48h.

[0121] Preferably, in step (2), the acidic substance is selected from at least one of p-toluenesulfonic acid or its hydrate, methanesulfonic acid, trifluoromethanesulfonic acid, hydrochloric acid, sulfuric acid, nitric acid, formic acid, acetic acid, propionic acid, trifluoroacetic acid, trichloroacetic acid, benzoic acid, and phosphoric acid. The p-toluenesulfonic acid hydrate is preferably p-toluenesulfonic acid monohydrate.

[0122] Preferably, in step (2), the molar ratio of the acidic substance to compound IV is 0.01-10:1.

[0123] Preferably, in step (2), the second solvent is selected from at least one of N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMA), N-methylpyrrolidone (NMP), diethyl ether, methyl tert-butyl ether, dioxane, tetrahydrofuran, 2-methyltetrahydrofuran, benzene, toluene, xylene, acetone, methyl ethyl ketone, dichloromethane, chloroform, carbon tetrachloride, chlorobenzene, dichlorobenzene, ethyl acetate, dimethyl sulfoxide, and 1,3-dimethyl-2-imidazolium ketone.

[0124] Preferably, in step (2), the amount of the second solvent is 1-20 mL relative to 1 mmol of compound III.

[0125] Preferably, step (2) further includes: adjusting the pH of the system to 7-10 using an alkaline solution after the second reaction, wherein the alkaline solution is, for example, an aqueous solution of sodium hydroxide.

[0126] According to the present invention, in step (3), the third reaction is as follows:

[0127]

[0128] Preferably, in step (3), the conditions for the third reaction include: a temperature of -10°C to 100°C and a reaction time of 0.1-48h.

[0129] Preferably, in step (3), the molar ratio of the sulfonyl compound to compound II is 0.8-10:1.

[0130] Preferably, in step (3), the sulfonyl compound is selected from at least one of methylsulfonyl chloride, ethylsulfonyl chloride, n-propylsulfonyl chloride and n-butylsulfonyl chloride, more preferably ethylsulfonyl chloride.

[0131] Preferably, in step (3), the second alkaline substance is selected from at least one of pyridine, dimethylaminopyridine (DMAP), triethylamine, diisopropylethylamine, sodium hydride, potassium hydride, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium acetate, potassium acetate, sodium methoxide, sodium ethoxide, sodium tert-butoxide, potassium tert-butoxide, and 1,8-diazabicyclo[5.4.0]undec-7-ene.

[0132] Preferably, in step (3), the molar ratio of the second alkaline substance to compound II is 1-10:1.

[0133] Preferably, in step (3), the third solvent is selected from at least one of diethyl ether, tetrahydrofuran (THF), 2-methyltetrahydrofuran, N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMA), N-methylpyrrolidone (NMP), dioxane, benzene, toluene, xylene, dichloromethane, chloroform, carbon tetrachloride, chlorobenzene, and dichlorobenzene.

[0134] Preferably, in step (3), the amount of the third solvent is 1-20 mL relative to 1 mmol of compound II.

[0135] According to a preferred embodiment of the present invention, step (3) includes: in a third solvent, in the presence of a second alkaline substance, the compound II is first subjected to a first-stage third reaction, and then the sulfonyl compound is added to carry out a second-stage third reaction to obtain the benzimidazole compound.

[0136] Preferably, the conditions for the third reaction in the first stage include: a temperature of -10°C to 100°C and a reaction time of 10-120 min.

[0137] Preferably, the conditions for the third reaction in the second stage include: a temperature of -10°C to 100°C and a reaction time of 0.5-48h.

[0138] According to the present invention, the method may also include various post-processing operations already used in the art, such as extraction, washing, drying, filtration, concentration, separation and purification. The present invention does not have any particular limitation on this, and various conventional operations in the art can be used, such as extraction with ethyl acetate; drying with anhydrous sodium sulfate; concentration with vacuum concentration; separation and purification with column chromatography, etc.

[0139] As previously stated, a third aspect of the invention provides a pyridinyl-containing benzimidazole compound or a salt thereof prepared by the method described in the second aspect.

[0140] As previously stated, the fourth aspect of the present invention provides the use of pyridyl-containing benzimidazole compounds or their salts as described in the first or third aspects above in the preparation of insecticides, acaricides and / or parasite control agents.

[0141] Preferably, the pyridine-containing benzimidazole compound or its salt is used as an active ingredient (i.e., effective ingredient) in the insecticide, acaricide and / or parasite control agent.

[0142] As previously described, a fifth aspect of the present invention provides an insecticide and acaricide containing an active ingredient selected from at least one of the pyridyl-containing benzimidazole compounds or their salts described in the first or third aspects above.

[0143] In a fifth aspect of the invention, preferably, the content of the active ingredient is 1-99% by weight, based on the total weight of the insecticide and acaricide. For example, the content of the active ingredient is 1% by weight, 5% by weight, 10% by weight, 15% by weight, 20% by weight, 25% by weight, 30% by weight, 35% by weight, 40% by weight, 45% by weight, 50% by weight, 55% by weight, 60% by weight, 65% by weight, 70% by weight, 75% by weight, 80% by weight, 85% by weight, 90% by weight, 95% by weight, 99% by weight, and any value within a range formed by any two of these values. More preferably, the content of the active ingredient is 5-60% by weight, based on the total weight of the insecticide and acaricide.

[0144] In a fifth aspect of the invention, preferably, the insecticide and acaricide further comprises a carrier. Preferably, the carrier in the insecticide and acaricide is a substance acceptable in agriculture, forestry, and horticulture and conducive to the application of the active ingredient. Particularly preferably, the carrier is a liquid carrier and / or a solid carrier, wherein the solid carrier is preferably selected from at least one solid substance selected from clay, natural or synthetic silicates, silica, resins, waxes, and solid fertilizers; the liquid carrier is preferably selected from water, alcohols, ketones, petroleum fractions, aromatics, chlorinated hydrocarbons, and liquid substances of liquefied petroleum gas.

[0145] In a fifth aspect of the present invention, the insecticide and acaricide may also contain other commonly used adjuvants in the art, such as surfactants, protective colloids, adhesives, thickeners, thixotropic agents, penetrants, chelating agents, colorants, and polymers. The present invention does not impose any particular restrictions on this, and those skilled in the art can select reasonable compositions and dosages according to actual needs.

[0146] In a fifth aspect of the invention, preferably, the formulations of the insecticides and acaricides are each independently selected from at least one of wettable powders, soluble powders, emulsifiable concentrates, aqueous suspensions, dispersible oil suspensions, water emulsions, suspension emulsions, microemulsions, aqueous solutions, granules, microcapsules, and water-dispersible granules. This makes the active ingredients easier to dissolve or disperse, thus improving their dispersibility when used as active substances in insecticides and acaricides and enhancing their application efficacy.

[0147] In the fifth aspect of the present invention, the present invention does not impose any particular limitation on the preparation method of the insecticide and acaricide. Those skilled in the art can refer to the methods in existing literature and standards in the art or use existing methods in the art to prepare the reagent to obtain the desired composition and dosage form.

[0148] As previously stated, the sixth aspect of the present invention provides the application of the aforementioned insecticides and acaricides in agriculture, forestry and horticulture for insecticidal and / or acaricidal purposes.

[0149] Preferably, the application includes: applying the insecticide and acaricide to pests and / or mites, or applying the insecticide and acaricide to the growth medium of pests and / or mites. According to the invention, the growth medium is, for example, plants or soil.

[0150] Preferably, the effective amount (i.e., the amount of active ingredient) applied is 10 to 1000 grams per hectare of soil, more preferably 20 to 500 grams per hectare of soil. According to the present invention, there are no particular limitations on the specific method of application; conventional methods in the art can be used, such as spraying the insecticide and / or acaricide onto pests and / or mites, or spraying it onto the growth medium of pests and / or mites.

[0151] According to the present invention, in the application of the insecticide and / or acaricide in agriculture, forestry, and horticulture, the insecticide and acaricide can also be compounded with existing fungicides, insecticides, herbicides, plant growth regulators, plant fertilizers, etc., to produce additive or synergistic effects, thereby obtaining better results. The present invention does not impose any particular limitations on this; provided that the benzimidazole compounds or their salts containing the present invention are used as active ingredients, those skilled in the art can rationally select appropriate amounts of substances for combination and compounding according to actual needs.

[0152] The seventh aspect of the present invention provides a parasite control agent containing an active ingredient selected from at least one of the pyridine-containing benzimidazole compounds or their salts described in the first or third aspects above.

[0153] In a seventh aspect of the invention, preferably, the content of the active ingredient is 1-99% by weight, based on the total weight of the parasite control agent. For example, the content of the active ingredient is 1% by weight, 5% by weight, 10% by weight, 15% by weight, 20% by weight, 25% by weight, 30% by weight, 35% by weight, 40% by weight, 45% by weight, 50% by weight, 55% by weight, 60% by weight, 65% by weight, 70% by weight, 75% by weight, 80% by weight, 85% by weight, 90% by weight, 95% by weight, 99% by weight, and any value within a range formed by any two of these values. More preferably, the content of the active ingredient is 5-60% by weight, based on the total weight of the parasite control agent.

[0154] In the seventh aspect of the present invention, the present invention does not impose any particular limitation on the preparation method of the parasite control agent. Those skilled in the art can refer to the methods in existing literature and standards in the art or use existing methods in the art to prepare the agent to obtain the desired composition and dosage form.

[0155] The eighth aspect of the present invention provides the application of the aforementioned parasite control agent in the prevention and control of internal and external parasites in animals.

[0156] The present invention will be described in detail below through examples.

[0157] In the following examples, unless otherwise specified, all raw materials used are commercially available products.

[0158] The sources of some raw materials are shown in Table 3:

[0159] Table 3

[0160] V-1 Beijing Ouhe Technology Co., Ltd. IV-1 Beijing Ouhe Technology Co., Ltd. IV-2 Beijing Ouhe Technology Co., Ltd. Condensing agent: HATU Beijing Ouhe Technology Co., Ltd. First alkaline substance: diisopropylethylamine Beijing Ouhe Technology Co., Ltd. Acidic substance: p-Toluenesulfonic acid monohydrate Beijing Ouhe Technology Co., Ltd. Sulfonyl compounds: Ethylsulfonyl chloride Beijing Ouhe Technology Co., Ltd.

[0161] In the following examples, unless otherwise specified, room temperature refers to 25±2℃.

[0162] Example 1

[0163] This example describes the preparation of compound I-29.

[0164]

[0165] The specific preparation process is as follows:

[0166] (1) The first solvent (pyridine, 15 mL) was added to the reaction flask, followed by the condensing agent (HATU, 15 mmol) and the first basic substance (diisopropylethylamine, 2 mmol). Compound V (V-1, 10 mmol) and compound IV (IV-1, 10 mmol) were then added. The reaction was carried out at room temperature for 3 h to induce the first reaction. Water was then added, and the mixture was extracted with ethyl acetate. The organic phase was washed with saturated brine and dried over anhydrous sodium sulfate. The mixture was filtered and the filtrate was concentrated under reduced pressure to obtain compound III.

[0167] (2) The obtained compound III was dissolved in a second solvent (NMP, 15 mL), and an acidic substance (p-toluenesulfonic acid monohydrate, 30 mmol) was added. The reaction was carried out at 160 °C for 4 h to carry out the second reaction. After cooling to room temperature, the pH of the system was adjusted to 9 by adding 10 wt% sodium hydroxide aqueous solution. The mixture was then extracted with ethyl acetate, the organic phase was washed with saturated brine, dried over anhydrous sodium sulfate, filtered, and the filtrate was concentrated under reduced pressure to obtain compound II (II-1, 8 mmol).

[0168] (3) Compound II was dissolved in a third solvent (THF, 30 mL), and a second basic substance (0.96 g of mineral oil-coated NaH, NaH content 60 wt%, NaH content 24 mmol) was added. After reacting at room temperature for 10 min, a sulfonyl compound (ethyl sulfonyl chloride, 24 mmol) was added, and the reaction was carried out at room temperature for 12 h. The reaction was quenched with saturated ammonium chloride, extracted with ethyl acetate, washed with saturated brine, dried over anhydrous sodium sulfate, filtered, and the filtrate was concentrated under reduced pressure. The product was purified by column chromatography to obtain compound I-29 (1.68 g), a white solid.

[0169] Example 2

[0170] This example describes the preparation of compound I-180.

[0171]

[0172] The specific preparation process is as follows:

[0173] (1) Add the first solvent (pyridine, 15 mL), the condensing agent (HATU, 15 mmol) and the first basic substance (diisopropylethylamine, 2 mmol) to the reaction flask, add compound V (V-1, 10 mmol) and compound IV (IV-2, 10 mmol) and react at room temperature for 3 h to carry out the first reaction, then add water, extract with ethyl acetate, wash the organic phase with saturated brine, dry with anhydrous sodium sulfate, filter, concentrate the filtrate under reduced pressure to obtain compound III;

[0174] (2) The obtained compound III was dissolved in a second solvent (NMP, 15 mL), and an acidic substance (p-toluenesulfonic acid monohydrate, 30 mmol) was added. The reaction was carried out at 160 °C for 4 h to carry out the second reaction. After cooling to room temperature, the pH of the system was adjusted to 10 by adding 10 wt% sodium hydroxide aqueous solution. Then, the mixture was extracted with ethyl acetate, the organic phase was washed with saturated brine, dried over anhydrous sodium sulfate, filtered, and the filtrate was concentrated under reduced pressure to obtain compound II (II-2, 8.2 mmol).

[0175] (3) Compound II was dissolved in a third solvent (THF, 30 mL), and a second basic substance (0.98 g of mineral oil-coated NaH, NaH content 60 wt%, NaH content 24.6 mmol) was added. After reacting at room temperature for 10 min, a sulfonyl compound (ethyl sulfonyl chloride, 24.6 mmol) was added, and the reaction was carried out at room temperature for 12 h. After the reaction, saturated ammonium chloride was added to quench the reaction, ethyl acetate was used for extraction, the organic phase was washed with saturated brine, dried over anhydrous sodium sulfate, filtered, and the filtrate was concentrated under reduced pressure. The obtained product was purified by column chromatography to obtain compound I-180 (2.10 g).

[0176] Bioactivity test

[0177] This test example examines the acaricidal activity of the compounds prepared above, specifically their acaricidal activity against the carmine spider mite. The specific test procedure is as follows:

[0178] (1) Dissolve the test compound in acetone and dilute it with 0.1 wt% Tween 80 aqueous solution to the required concentration (see Test Examples 1-A to 1-B below for details). The acetone content shall not exceed 5 wt% to prepare the reagent.

[0179] (2) Remove one true leaf from the bean seedlings that have grown to two true leaves, and inoculate them with spider mites (50-150 spider mites per bean seedling). 24 hours later, investigate the initial number of inoculated mites. Use a handheld sprayer to spray the three bean seedlings with the agent prepared in step (1) (0.5 mL per seedling). After treatment, place them in a constant temperature observation room (25℃) for observation. After 72 hours, investigate the number of live mites and calculate the mortality rate:

[0180] Mortality rate (%) = (Number of inoculated mites - Number of live mites after spraying) / Number of inoculated mites × 100%.

[0181] Test Example 1-A

[0182] Compounds I-180, I-261, and I-342 were diluted to a concentration of 6.25 mg / L, and then tested according to the procedure described above.

[0183] In this test, the mortality rate of adult Tetranychus cinnabarinus was over 90%.

[0184] Test Example 1-B

[0185] Compounds I-29, I-234, and I-288 were diluted to a concentration of 1.56 mg / L and then tested according to the procedure described above.

[0186] In this test, the mortality rate of adult Tetranychus cinnabarinus was over 90%.

[0187] Comparative test cases

[0188] This invention also tested the bioassay activity of the following compounds against *Tetranychus carmine*, following the same testing procedure as above. The test results showed that KC-1, KC-2, and KC-3 all exhibited a mortality rate of less than 50% against adult *Tetranychus carmine* at 100 ppm; compound KC-4 showed an 86% mortality rate against adult *Tetranychus carmine* at 25 ppm.

[0189]

[0190] The test results above show that the pyridine-containing benzimidazole compounds or their salts provided by the present invention have excellent insecticidal and acaricidal effects, and their insecticidal and acaricidal activity is far higher than that of known compounds. In particular, the pyridine-containing benzimidazole compounds of the present invention can have excellent insecticidal and acaricidal effects when used at low concentrations (e.g., 1.56 mg / L).

[0191] The preferred embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. A benzimidazole compound containing a pyridyl group or a salt thereof, characterized in that, The pyridinyl-containing benzimidazole compound has the structure shown in formula (I): Equation (I); In equation (I), R is ethyl, Y1 and Y4 are each independently H, Y2 is Cl, Y3 is CF3, and Z1, Z2, Z3, and Z4 are each independently H. Alternatively, R is ethyl, Y1 and Y4 are each independently H, Y2 and Y3 are each independently Cl, and Z1, Z2, Z3, and Z4 are each independently H; Alternatively, R is ethyl, Y1 and Y4 are each independently H, Y2 and Y3 are each independently Cl, Z1, Z2 and Z4 are each independently H, and Z3 is Cl; Alternatively, R is ethyl, Y1 and Y4 are each independently H, Y2 and Y3 are each independently Cl, Z1 and Z4 are each independently H, and Z2 and Z3 are each independently Cl; Alternatively, R is ethyl, Y1 and Y4 are each independently H, Y2 and Y3 are each independently Cl, Z1, Z3 and Z4 are each independently H, and Z2 is F; Alternatively, R is ethyl, Y1 and Y4 are each independently H, Y2 and Y3 are each independently Cl, Z1 and Z4 are each independently H, and Z2 and Z3 are each independently F.

2. A method for preparing benzimidazole compounds containing pyridinyl groups or their salts, characterized in that, The method includes: (1) In the first solvent, in the presence of the first basic substance and the condensing agent, compound V and compound IV are subjected to a first reaction to obtain compound III; (2) In a second solvent, compound III and an acidic substance undergo a second reaction to obtain compound II; (3) In a third solvent, in the presence of a second basic substance, the compound II and the sulfonyl compound are subjected to a third reaction to obtain the pyridyl-containing benzimidazole compound; Wherein, compound V has the structure shown in formula (V), compound IV has the structure shown in formula (IV), compound III has the structure shown in formula (III), compound II has the structure shown in formula (II), the pyridyl-containing benzimidazole compound has the structure shown in formula (I), and the sulfonyl-containing compound has the structure shown in formula (VI). Formula (I); Formula (II); Formula (III); Formula (IV); Formula (V); Formula (VI); In formulas (I), (II), (III), (IV), (V), and (VI), the definitions of R, Y1, Y2, Y3, Y4, Z1, Z2, Z3, and Z4 correspond to the definitions in claim 1, and X is selected from halogens.

3. The method according to claim 2, wherein, In step (1), the conditions for the first reaction include: a temperature of -10°C to 150°C and a reaction time of 0.1-48h.

4. The method according to claim 2, wherein, In step (1), the molar ratio of compound V to compound IV is 0.5-2:

1.

5. The method according to claim 2, wherein, In step (1), the condensing agent is selected from at least one of 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide or its hydrochloride, carbonyl diimidazole, 1,3-dicyclohexylcarbodiimide, diethyl cyanophosphate, chlorocarbonate compounds, and 2-chloro-1-methylpyridinium iodide.

6. The method according to claim 5, wherein, In step (1), the molar ratio of the condensing agent to compound IV is 1-2:

1.

7. The method according to claim 2, wherein, In step (1), the first alkaline substance is selected from at least one of pyridine, dimethylaminopyridine, triethylamine, diisopropylethylamine, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium acetate, potassium acetate, sodium methoxide, sodium ethoxide, sodium tert-butoxide, potassium tert-butoxide, and 1,8-diazabicyclo[5.4.0]undec-7-ene.

8. The method according to claim 7, wherein, In step (1), the molar ratio of the first alkaline substance to compound IV is 0.1-10:

1.

9. The method according to claim 2, wherein, In step (2), the conditions for the second reaction include: a temperature of -10°C to 300°C and a reaction time of 0.1-48h.

10. The method according to claim 2, wherein, In step (2), the acidic substance is selected from at least one of p-toluenesulfonic acid or its hydrate, methanesulfonic acid, trifluoromethanesulfonic acid, hydrochloric acid, sulfuric acid, nitric acid, formic acid, acetic acid, propionic acid, trifluoroacetic acid, trichloroacetic acid, benzoic acid, and phosphoric acid.

11. The method according to claim 10, wherein, In step (2), the molar ratio of the acidic substance to compound IV is 0.01-10:

1.

12. The method according to claim 2, wherein, In step (3), the conditions for the third reaction include: a temperature of -10°C to 100°C and a reaction time of 0.1-48h.

13. The method according to claim 2, wherein, The molar ratio of the sulfonyl compound to compound II is 0.8-10:

1.

14. The method according to claim 2, wherein, The second alkaline substance is selected from at least one of pyridine, dimethylaminopyridine, triethylamine, diisopropylethylamine, sodium hydride, potassium hydride, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium acetate, potassium acetate, sodium methoxide, sodium ethoxide, sodium tert-butoxide, potassium tert-butoxide, and 1,8-diazabicyclo[5.4.0]undec-7-ene.

15. The method according to claim 14, wherein, The molar ratio of the second alkaline substance to compound II is 1-10:

1.

16. A pyridinyl-containing benzimidazole compound or a salt thereof prepared by the method according to any one of claims 2-15.

17. The use of the pyridyl-containing benzimidazole compound or its salt as described in claim 1 or 16 in the preparation of insecticides, acaricides and / or parasite control agents.

18. An insecticide and acaricide, characterized in that, The insecticide and acaricide contains an active ingredient selected from at least one of the pyridyl-containing benzimidazole compounds or their salts as described in claim 1 or 16.

19. The insecticide and acaricide according to claim 18, wherein, Based on the total weight of the insecticide and acaricide, the content of the active ingredient is 1-99% by weight.

20. The insecticide and acaricide according to claim 19, wherein, Based on the total weight of the insecticide and acaricide, the content of the active ingredient is 5-60% by weight.

21. The use of the insecticide and acaricide according to any one of claims 18-20 in agriculture, forestry and horticulture for insecticidal and / or acaricidal purposes.

22. A parasite control agent, characterized in that, The parasite control agent contains an active ingredient selected from at least one of the pyridyl-containing benzimidazole compounds or their salts as described in claim 1 or 16.

23. The parasite control agent according to claim 22, wherein, Based on the total weight of the parasite control agent, the content of the active ingredient is 1-99% by weight.

24. The parasite control agent according to claim 23, wherein, Based on the total weight of the parasite control agent, the content of the active ingredient is 5-60% by weight.

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