CN117586248A - Thiazolyl-containing benzimidazole compound or salt thereof, preparation method, insecticidal acaricide, parasite control agent and application - Google Patents

Thiazolyl-containing benzimidazole compound or salt thereof, preparation method, insecticidal acaricide, parasite control agent and application Download PDF

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CN117586248A
CN117586248A CN202310964957.7A CN202310964957A CN117586248A CN 117586248 A CN117586248 A CN 117586248A CN 202310964957 A CN202310964957 A CN 202310964957A CN 117586248 A CN117586248 A CN 117586248A
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substituted
alkyl
halo
cycloalkyl
unsubstituted
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刘保红
陈瑜
唐盈盈
尹若飞
孟庆盖
刘瑞宾
盛国柱
李大为
祁建军
杜瑶瑶
王世玲
刘敏
范世恩
于海霞
王莹
项效忠
宫辰
柳英帅
李宁
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Qingdao Kangqiao Pharmaceutical Group Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
    • C07D417/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
    • A01N43/78—1,3-Thiazoles; Hydrogenated 1,3-thiazoles
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P33/00—Antiparasitic agents
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P33/00—Antiparasitic agents
    • A61P33/14—Ectoparasiticides, e.g. scabicides

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Abstract

The invention relates to the field of pesticides, and discloses a thiazolyl-containing benzimidazole compound or a salt thereof, a preparation method, an insecticidal acaricide, a parasite control agent and an application. The thiazolyl-containing benzimidazole compound or the salt thereof provided by the invention has excellent insecticidal and acaricidal effects, and particularly has the acaricidal effects when the thiazolyl-containing benzimidazole compound is used in low concentration

Description

Thiazolyl-containing benzimidazole compound or salt thereof, preparation method, insecticidal acaricide, parasite control agent and application
Cross Reference to Related Applications
The present application claims the benefit of chinese patent application 202210978291.6 entitled "thiazolyl-containing benzimidazole compound or its salt and preparation method, and insecticidal acaricide, parasite control agent and application", filed on month 08 and 15 of 2022, the contents of which are incorporated herein by reference.
Technical Field
The invention relates to the field of pesticides, in particular to a thiazolyl-containing benzimidazole compound or a salt thereof, a preparation method, an insecticidal acaricide, a parasite control agent and application.
Background
In crop production such as agriculture and horticulture, there is still a great loss caused by pests and the like, and there is a demand for development of an insecticidal/acaricidal agent for agriculture and horticulture which has a novel action, has little influence on natural enemy beneficial insects, and has osmotic transfer activity and the like from the viewpoints of influence on environmental organisms, labor saving and the like, as the presence of pests having resistance to existing drugs.
WO2021107113A1 discloses that benzimidazole compounds containing five-membered heterocyclic rings have certain insecticidal and acaricidal activity at a high concentration of 500 ppm. The general structural formula of the five-membered heterocyclic benzimidazole compound is shown as follows:
wherein the five-membered heterocyclic ring is selected from the above 15, for example, compounds KC-1, KC-2, KC-3, KC-4 are part of the representative compounds disclosed in WO2021107113A 1.
There is a need to provide compounds which have a high insecticidal and acaricidal effect when used at low concentrations.
Disclosure of Invention
The invention aims to overcome the defect that the existing benzimidazole compound containing heterocycle can only have insecticidal and acaricidal activity when used at high concentration and is difficult to meet the control requirement on field mites, and provides a thiazole-containing benzimidazole compound or salt thereof, a preparation method, an insecticidal and acaricidal agent, a parasite control agent and application, wherein the thiazole-containing benzimidazole compound is expected to be used as an active ingredient in the insecticidal and acaricidal agent, and can have high-efficiency control effect when used at low concentration (not higher than 100 ppm).
In order to achieve the above object, a first aspect of the present invention provides a thiazolyl-containing benzimidazole compound having a structure represented by formula (I):
wherein, in the formula (I),
r is selected from substituted or unsubstituted C 1 -C 10 Alkyl, substituted or unsubstituted C 3 -C 10 Cycloalkyl, substituted or unsubstituted C 2 -C 10 Alkenyl, substituted or unsubstituted C 2 -C 10 Alkynyl, and the optional substituents are each independently selected from halogen, C 1 -C 10 Alkyl, halogenated C 1 -C 10 Alkyl, C 3 -C 10 Cycloalkyl, halo C 3 -C 10 Cycloalkyl, C 1 -C 10 Alkoxy, halo C 1 -C 10 Alkoxy, C 3 -C 10 Cycloalkoxy, halo C 3 -C 10 CycloalkoxyAt least one of the groups;
Y 1 、Y 2 each independently selected from H, halogen, CN, NO 2 Formyl, substituted or unsubstituted C 1 -C 10 Alkyl, substituted or unsubstituted C 3 -C 10 Cycloalkyl, substituted or unsubstituted C 1 -C 10 Alkoxy, substituted or unsubstituted C 1 -C 10 Alkylthio, substituted or unsubstituted C 1 -C 10 Alkylsulfinyl, substituted or unsubstituted C 1 -C 10 Alkylsulfonyl, substituted or unsubstituted C 1 -C 10 Alkylsulfonylamino, substituted or unsubstituted halogenated C 1 -C 8 Alkylsulfonylamino, substituted or unsubstituted C 1 -C 10 Alkylcarbonyl, substituted or unsubstituted C 1 -C 10 Alkoxycarbonyl, substituted or unsubstituted arylcarbonyl, substituted or unsubstituted aryloxycarbonyl, substituted or unsubstituted C 2 -C 6 Alkenyl, substituted or unsubstituted C 2 -C 6 Alkynyl, substituted or unsubstituted C 2 -C 6 Alkenyloxy, substituted or unsubstituted C 2 -C 6 Alkynyloxy, substituted or unsubstituted C 1 -C 10 Alkylcarbonyloxy, substituted or unsubstituted C 1 -C 10 Cyanoalkyl, substituted or unsubstituted C 1 -C 10 Cyanoalkoxy, substituted or unsubstituted silyl, substituted or unsubstituted amino, substituted or unsubstituted aryl C 1 -C 6 Alkyl, substituted or unsubstituted aryloxy, substituted or unsubstituted aryl C 1 -C 6 Alkoxy, substituted or unsubstituted arylsulfonyl, substituted or unsubstituted arylsulfinyl, substituted or unsubstituted arylthio, substituted or unsubstituted arylC 1 -C 6 Alkylsulfonyl, substituted or unsubstituted aryl C 1 -C 6 Alkylsulfinyl, substituted or unsubstituted aryl C 1 -C 6 Alkylthio, substituted or unsubstituted heterocycle C 1 -C 6 Alkyl, takeSubstituted or unsubstituted heterocyclyloxy, and the optionally present substituents are each independently selected from halogen, C 1 -C 10 Alkyl, halogenated C 1 -C 10 Alkyl, C 3 -C 10 Cycloalkyl, halo C 3 -C 10 Cycloalkyl, C 1 -C 10 Alkoxy, halo C 1 -C 10 Alkoxy, C 3 -C 10 Cycloalkoxy, halo C 3 -C 10 At least one of the cycloalkoxy groups;
Z 1 、Z 2 、Z 3 、Z 4 Each independently selected from H, halogen, CN, NO 2 Formyl, substituted or unsubstituted C 1 -C 10 Alkyl, substituted or unsubstituted C 3 -C 10 Cycloalkyl, substituted or unsubstituted C 1 -C 10 Alkoxy, substituted or unsubstituted C 1 -C 10 Alkylthio, substituted or unsubstituted C 1 -C 10 Alkylsulfinyl, substituted or unsubstituted C 1 -C 10 Alkylsulfonyl, substituted or unsubstituted C 1 -C 10 Alkylcarbonyl, substituted or unsubstituted C 1 -C 10 Alkoxycarbonyl, substituted or unsubstituted arylcarbonyl, substituted or unsubstituted aryloxycarbonyl, substituted or unsubstituted C 2 -C 6 Alkenyl, substituted or unsubstituted C 2 -C 6 Alkynyl, substituted or unsubstituted C 2 -C 6 Alkenyloxy, substituted or unsubstituted C 2 -C 6 Alkynyloxy, substituted or unsubstituted C 1 -C 10 Alkylcarbonyloxy, substituted or unsubstituted C 1 -C 10 Cyanoalkyl, substituted or unsubstituted C 1 -C 10 Cyanoalkoxy, substituted or unsubstituted silyl, substituted or unsubstituted amino, substituted or unsubstituted aryl C 1 -C 6 Alkyl, substituted or unsubstituted aryloxy, substituted or unsubstituted aryl C 1 -C 6 Alkoxy, substituted or unsubstituted arylsulfonyl, substituted or unsubstituted arylsulfinyl, substituted Or unsubstituted arylthio, substituted or unsubstituted aryl C 1 -C 6 Alkylsulfonyl, substituted or unsubstituted aryl C 1 -C 6 Alkylsulfinyl, substituted or unsubstituted aryl C 1 -C 6 Alkylthio, substituted or unsubstituted heterocycle C 1 -C 6 Alkyl, substituted or unsubstituted heterocyclyloxy, and the optionally present substituents are each independently selected from halogen, C 1 -C 10 Alkyl, halogenated C 1 -C 10 Alkyl, C 3 -C 10 Cycloalkyl, halo C 3 -C 10 Cycloalkyl, C 1 -C 10 Alkoxy, halo C 1 -C 10 Alkoxy, C 3 -C 10 Cycloalkoxy, halo C 3 -C 10 At least one of the cycloalkoxy groups; optionally Z 1 、Z 2 、Z 3 、Z 4 Any adjacent two groups of (a) are a group, and at least one group of the groups and the bonded benzene ring are cyclized with or without at least one heteroatom to form at least one 3-to 8-membered ring.
In a second aspect, the present invention provides a method for preparing a thiazolyl-containing benzimidazole compound, the method comprising:
(1) In a first solvent, carrying out a first reaction on a compound V and a compound IV in the presence of a first alkaline substance and a condensing agent to obtain a compound III;
(2) In a second solvent, carrying out a second reaction on the compound III and an acidic substance to obtain a compound II;
(3) In a third solvent, in the presence of a second alkaline substance, carrying out a third reaction on the compound II and a sulfonyl-containing compound to obtain the thiazolyl-containing benzimidazole compound;
Wherein the compound V has a structure shown in a formula (V), the compound IV has a structure shown in a formula (IV), the compound III has a structure shown in a formula (III), the compound II has a structure shown in a formula (II), the thiazolyl-containing benzimidazole compound has a structure shown in a formula (I), and the sulfonyl-containing compound has a structure shown in a formula (VI);
r, Y in formula (I), formula (II), formula (III), formula (IV), formula (V) and formula (VI) 1 、Y 2 、Z 1 、Z 2 、Z 3 、Z 4 And X is selected from halogen as defined in the first aspect.
In a third aspect, the present invention provides a thiazolyl-containing benzimidazole compound or a salt thereof produced by the method of the second aspect.
In a fourth aspect, the present invention provides the use of a thiazolyl-containing benzimidazole compound according to the first or third aspect or a salt thereof for the preparation of an insecticidal acaricide and/or a parasiticide.
In a fifth aspect, the present invention provides an insecticidal/acaricidal agent comprising an active ingredient selected from at least one of the thiazolyl-containing benzimidazole compounds or salts thereof according to the first or third aspects.
In a sixth aspect, the present invention provides the use of the foregoing insecticidal and acaricidal agents in agriculture, forestry and horticulture.
In a seventh aspect, the present invention provides a parasite control agent comprising an active ingredient selected from at least one of the thiazolyl-containing benzimidazole compounds or salts thereof according to the foregoing first or third aspects.
In an eighth aspect, the present invention provides the use of the aforementioned parasite control agent for controlling parasites in and out of animals.
Compared with the prior art, the invention has at least the following advantages:
the thiazolyl-containing benzimidazole compound or the salt thereof provided by the invention is used as an active ingredient for an insecticidal and acaricidal agent, and has excellent control effect when being used in low concentration content.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
In the present invention, the terms involved are explained in a unified manner as follows:
halogen means fluorine, chlorine, bromine, iodine.
Alkyl refers to alkyl groups in straight or branched chain form, excluding cycloalkyl groups, said C 1 -C 8 Alkyl of (c) refers to an alkyl group having 1 to 8 carbon atoms and includes, for example, but is not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, and the like.
Cycloalkyl means an alkyl group containing a cyclic chain, said C 1 -C 8 Cycloalkyl of (c) refers to cycloalkyl groups having 1-8 carbon atoms, including for example, but not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and the like.
Alkenyl refers to straight or branched alkenyl, said C 2 -C 8 Alkenyl refers to alkenyl groups having 2-8 carbon atoms, including, for example, but not limited to, 1-propenyl, 2-propenyl, and the different butenyl, pentenyl, and hexenyl isomers; alkenyl groups also include polyenes such as 1, 2-allenyl and 2, 4-hexadienyl.
Alkynyl refers to straight or branched chain alkynyl, said C 2 -C 8 Alkynyl refers to alkynyl groups having 2-8 carbon atoms, including for example but not limited to 1-propynyl, 2-propynyl and the different butynyl, pentynyl and hexynyl isomers; alkynyl also includes groups containing multiple triple bonds, such as 2, 5-hexadiynyl.
Alkoxy refers to a straight or branched chain formA group having an oxygen atom at the terminal of the alkyl group, the C 1-8 Alkoxy of (c) refers to an alkoxy group having 1 to 8 carbon atoms, including, for example, but not limited to, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, and the like.
Cycloalkoxy is a group containing an oxygen atom in cycloalkyl, said C 1-8 Cycloalkoxy of (C) refers to a cycloalkyloxy group having 1-8 carbon atoms, including, for example, but not limited to, cyclopropyloxy, cyclobutoxy, and the like.
Alkylthio refers to a group having a sulfur atom attached to the end of the alkyl group, and includes, for example, but is not limited to, methylthio, ethylthio, n-propylthio, isopropylthio, terbutathio, and the like.
Alkylsulfinyl refers to a group having a sulfinyl group attached to the alkyl end, and includes, for example, but is not limited to, methylsulfinyl, ethylsulfinyl, n-propylsulfinyl, isopropylsulfinyl, t-butylsulfinyl, and the like.
Alkylsulfonyl refers to a group having a sulfonyl group attached to the alkyl end, and includes, for example, but is not limited to, methylsulfonyl, ethylsulfonyl, n-propylsulfonyl, isopropylsulfonyl, tert-butylsulfonyl, and the like.
The term "haloalkenyl", haloalkynyl, halocycloalkyl ", haloalkoxy, halocycloalkoxy, haloalkylthio, haloalkylsulfinyl and haloalkylsulfonyl" means a group in which at least one hydrogen atom of an alkyl group, alkenyl group, alkynyl group, cycloalkyl group, alkoxy group, cycloalkoxy group, alkylthio group, alkylsulfinyl group and alkylsulfonyl group is replaced with a halogen atom, and when two or more halogen atoms are present, the halogen atoms may be the same or different.
In the present invention, cycloalkyl-substituted alkyl, halocycloalkyl-substituted alkyl, cycloalkyl-substituted haloalkyl, alkoxy-substituted alkyl, haloalkoxy-substituted alkyl, alkoxy-substituted haloalkyl, cycloalkoxy-substituted alkyl, haloalkoxy-substituted haloalkyl means that at least one hydrogen atom in the alkyl group is substituted with cycloalkyl, halocycloalkyl, alkoxy, haloalkoxy, cycloalkoxy, or haloalkoxy, respectively.
In the present invention, heteroatoms include, but are not limited to, O, S, N atoms.
Other groups have similar definitions to those described above, except that the substituent groups or the number of carbon atoms are different and will not be described in detail.
Other terms in the present invention may be construed in a manner conventional in the art.
As described above, the first aspect of the present invention provides a thiazolyl-containing benzimidazole compound having a structure represented by formula (I):
wherein, in the formula (I),
r is selected from substituted or unsubstituted C 1 -C 10 Alkyl, substituted or unsubstituted C 3 -C 10 Cycloalkyl, substituted or unsubstituted C 2 -C 10 Alkenyl, substituted or unsubstituted C 2 -C 10 Alkynyl, and the optional substituents are each independently selected from halogen, C 1 -C 10 Alkyl, halogenated C 1 -C 10 Alkyl, C 3 -C 10 Cycloalkyl, halo C 3 -C 10 Cycloalkyl, C 1 -C 10 Alkoxy, halo C 1 -C 10 Alkoxy, C 3 -C 10 Cycloalkoxy, halo C 3 -C 10 At least one of the cycloalkoxy groups;
Y 1 、Y 2 each independently selected from H, halogen, CN, NO 2 Formyl, substituted or unsubstituted C 1 -C 10 Alkyl, substituted or unsubstituted C 3 -C 10 Cycloalkyl, substituted or unsubstituted C 1 -C 10 Alkoxy, substituted or unsubstituted C 1 -C 10 Alkylthio, substituted or unsubstituted C 1 -C 10 Alkylsulfinyl, substituted or unsubstituted C 1 -C 10 Alkylsulfonyl, substitutedOr unsubstituted C 1 -C 10 Alkylsulfonylamino, substituted or unsubstituted halogenated C 1 -C 8 Alkylsulfonylamino, substituted or unsubstituted C 1 -C 10 Alkylcarbonyl, substituted or unsubstituted C 1 -C 10 Alkoxycarbonyl, substituted or unsubstituted arylcarbonyl, substituted or unsubstituted aryloxycarbonyl, substituted or unsubstituted C 2 -C 6 Alkenyl, substituted or unsubstituted C 2 -C 6 Alkynyl, substituted or unsubstituted C 2 -C 6 Alkenyloxy, substituted or unsubstituted C 2 -C 6 Alkynyloxy, substituted or unsubstituted C 1 -C 10 Alkylcarbonyloxy, substituted or unsubstituted C 1 -C 10 Cyanoalkyl, substituted or unsubstituted C 1 -C 10 Cyanoalkoxy, substituted or unsubstituted silyl, substituted or unsubstituted amino, substituted or unsubstituted aryl C 1 -C 6 Alkyl, substituted or unsubstituted aryloxy, substituted or unsubstituted aryl C 1 -C 6 Alkoxy, substituted or unsubstituted arylsulfonyl, substituted or unsubstituted arylsulfinyl, substituted or unsubstituted arylthio, substituted or unsubstituted arylC 1 -C 6 Alkylsulfonyl, substituted or unsubstituted aryl C 1 -C 6 Alkylsulfinyl, substituted or unsubstituted aryl C 1 -C 6 Alkylthio, substituted or unsubstituted heterocycle C 1 -C 6 Alkyl, substituted or unsubstituted heterocyclyloxy, and the optionally present substituents are each independently selected from halogen, C 1 -C 10 Alkyl, halogenated C 1 -C 10 Alkyl, C 3 -C 10 Cycloalkyl, halo C 3 -C 10 Cycloalkyl, C 1 -C 10 Alkoxy, halo C 1 -C 10 Alkoxy, C 3 -C 10 Cycloalkoxy, halo C 3 -C 10 At least one of the cycloalkoxy groups;
Z 1 、Z 2 、Z 3 、Z 4 each independently selected from H, halogen, CN, NO 2 Formyl, substituted or unsubstituted C 1 -C 10 Alkyl, substituted or unsubstituted C 3 -C 10 Cycloalkyl, substituted or unsubstituted C 1 -C 10 Alkoxy, substituted or unsubstituted C 1 -C 10 Alkylthio, substituted or unsubstituted C 1 -C 10 Alkylsulfinyl, substituted or unsubstituted C 1 -C 10 Alkylsulfonyl, substituted or unsubstituted C 1 -C 10 Alkylcarbonyl, substituted or unsubstituted C 1 -C 10 Alkoxycarbonyl, substituted or unsubstituted arylcarbonyl, substituted or unsubstituted aryloxycarbonyl, substituted or unsubstituted C 2 -C 6 Alkenyl, substituted or unsubstituted C 2 -C 6 Alkynyl, substituted or unsubstituted C 2 -C 6 Alkenyloxy, substituted or unsubstituted C 2 -C 6 Alkynyloxy, substituted or unsubstituted C 1 -C 10 Alkylcarbonyloxy, substituted or unsubstituted C 1 -C 10 Cyanoalkyl, substituted or unsubstituted C 1 -C 10 Cyanoalkoxy, substituted or unsubstituted silyl, substituted or unsubstituted amino, substituted or unsubstituted aryl C 1 -C 6 Alkyl, substituted or unsubstituted aryloxy, substituted or unsubstituted aryl C 1 -C 6 Alkoxy, substituted or unsubstituted arylsulfonyl, substituted or unsubstituted arylsulfinyl, substituted or unsubstituted arylthio, substituted or unsubstituted arylC 1 -C 6 Alkylsulfonyl, substituted or unsubstituted aryl C 1 -C 6 Alkylsulfinyl, substituted or unsubstituted aryl C 1 -C 6 Alkylthio, substituted or unsubstituted heterocycle C 1 -C 6 Alkyl, substituted or unsubstituted heterocyclyloxy, and the optionally present substituents are each independently selected from halogen, C 1 -C 10 Alkyl, halogenated C 1 -C 10 Alkyl, C 3 -C 10 Cycloalkyl, halo C 3 -C 10 Cycloalkyl, C 1 -C 10 Alkoxy, halo C 1 -C 10 Alkoxy, C 3 -C 10 Cycloalkoxy, halo C 3 -C 10 At least one of the cycloalkoxy groups; optionally Z 1 、Z 2 、Z 3 、Z 4 Any adjacent two groups of (a) are a group, and at least one group of the groups and the bonded benzene ring are cyclized with or without at least one heteroatom to form at least one 3-to 8-membered ring.
According to the invention, said optional representation may or may not be present in a multi-membered ring structure.
According to the invention, said Z 1 、Z 2 、Z 3 、Z 4 Any adjacent two groups are a group, and at least one group of the groups and the bonded benzene ring are cyclized with or without at least one heteroatom to form at least one 3-to 8-membered ring, representing Z 1 And Z 2 、Z 2 And Z 3 、Z 3 And Z 4 At least one 3 to 8 membered ring is formed with the bonded benzene ring with or without at least one heteroatom.
Preferably, in the formula (I),
r is selected from C 1 -C 10 Alkyl, halogenated C 1 -C 10 Alkyl, C 3 -C 10 Cycloalkyl-substituted C 1 -C 10 Alkyl, halogenated C 3 -C 10 Cycloalkyl-substituted C 1 -C 10 Alkyl, C 3 -C 10 Cycloalkyl-substituted halo C 1 -C 10 Alkyl, C 1 -C 10 Alkoxy substituted C 1 -C 10 Alkyl, halogenated C 1 -C 10 Alkoxy substituted C 1 -C 10 Alkyl, C 1 -C 10 Alkoxy substituted halo C 1 -C 10 Alkyl, C 3 -C 10 Cycloalkoxy substituted C 1 -C 10 Alkyl, halogenated C 3 -C 10 Cycloalkoxy substituted C 1 -C 10 Alkyl, C 3 -C 10 Cycloalkoxy-substituted halos C 1 -C 10 Alkyl, C 3 -C 10 Cycloalkyl, halo C 3 -C 10 Cycloalkyl, C 1 -C 10 Alkyl substituted C 3 -C 10 Cycloalkyl, halo C 1 -C 10 Alkyl substituted C 3 -C 10 Cycloalkyl, C 1 -C 10 Alkyl-substituted halo C 3 -C 10 Cycloalkyl, C 1 -C 10 Alkoxy substituted C 3 -C 10 Cycloalkyl, halo C 1 -C 10 Alkoxy substituted C 3 -C 10 Cycloalkyl, C 1 -C 10 Alkoxy substituted halo C 3 -C 10 Cycloalkyl, C 3 -C 10 Cycloalkoxy substituted C 3 -C 10 Cycloalkyl, halo C 3 -C 10 Cycloalkoxy substituted C 3 -C 10 Cycloalkyl, C 3 -C 10 Cycloalkoxy-substituted halos C 3 -C 10 Cycloalkyl, C 2 -C 10 Alkenyl, halo C 2 -C 10 Alkenyl, C 2 -C 10 Alkynyl, halo C 2 -C 10 Alkynyl;
Y 1 、Y 2 each independently selected from H, halogen, CN, NO 2 、C 1 -C 10 Alkyl, halogenated C 1 -C 10 Alkyl, C 3 -C 10 Cycloalkyl-substituted C 1 -C 10 Alkyl, halogenated C 3 -C 10 Cycloalkyl-substituted C 1 -C 10 Alkyl, C 3 -C 10 Cycloalkyl-substituted halo C 1 -C 10 Alkyl, C 1 -C 10 Alkoxy substituted C 1 -C 10 Alkyl, halogenated C 1 -C 10 Alkoxy substituted C 1 -C 10 Alkyl, C 1 -C 10 Alkoxy substituted halo C 1 -C 10 Alkyl, C 3 -C 10 Cycloalkyl, halo C 3 -C 10 Cycloalkyl, C 1 -C 10 Alkyl substituted C 3 -C 10 Cycloalkyl, halo C 1 -C 10 Alkyl substituted C 3 -C 10 Cycloalkyl, C 1 -C 10 Alkyl-substituted halo C 3 -C 10 Cycloalkyl, C 1 -C 10 Alkoxy, halo C 1 -C 10 Alkoxy, C 1 -C 10 Alkylthio, halo C 1 -C 10 Alkylthio, C 1 -C 10 Alkylsulfinyl, halo C 1 -C 10 Alkylsulfinyl, C 1 -C 10 Alkylsulfonyl, haloC 1 -C 10 Alkylsulfonyl, C 1 -C 10 Alkylsulfonylamino, halo C 1 -C 8 Alkylsulfonylamino, formyl, C 1 -C 10 Alkylcarbonyl, halo C 1 -C 10 Alkylcarbonyl, C 1 -C 10 Alkoxycarbonyl, halo C 1 -C 10 Alkoxycarbonyl, arylcarbonyl, aryloxycarbonyl, C 2 -C 6 Alkenyl, C 2 -C 6 Alkynyl, halo C 2 -C 6 Alkenyl, halo C 2 -C 6 Alkynyl, C 2 -C 6 Alkenyloxy, C 2 -C 6 Alkynyloxy, halogenated C 2 -C 6 Alkenyloxy, halogenated C 2 -C 6 Alkynyloxy, C 1 -C 10 Alkylcarbonyloxy, halo C 1 -C 10 Alkylcarbonyloxy, C 1 -C 10 Cyanoalkyl, C 1 -C 10 Cyanoalkoxy, C 1 -C 10 Alkyl-substituted silane groups, substituted or unsubstituted amino groups, aryl groups C 1 -C 6 Alkyl, aryloxy, aryl C 1 -C 6 Alkoxy, arylsulfonyl, arylsulfinyl, arylthio and aryl C 1 -C 6 Alkylsulfonyl, aryl C 1 -C 6 Alkylsulfinyl, aryl C 1 -C 6 Alkylthio, heterocycle C 1 -C 6 Alkyl, heterocyclyloxy, and optionally substituents are each independently selected from halogen, C 1 -C 10 Alkyl, halogenated C 1 -C 10 Alkyl, C 3 -C 10 Cycloalkyl, halo C 3 -C 10 Cycloalkyl, C 1 -C 10 Alkoxy, halo C 1 -C 10 Alkoxy, C 3 -C 10 Cycloalkoxy, halo C 3 -C 10 At least one of the cycloalkoxy groups;
Z 1 、Z 2 、Z 3 、Z 4 each independently selected from H, halogen, CN, NO 2 、C 1 -C 10 Alkyl, halogenated C 1 -C 10 Alkyl, C 3 -C 10 Cycloalkyl-substituted C 1 -C 10 Alkyl, halogenated C 3 -C 10 Cycloalkyl-substituted C 1 -C 10 Alkyl, C 3 -C 10 Cycloalkyl-substituted halo C 1 -C 10 Alkyl, C 1 -C 10 Alkoxy substituted C 1 -C 10 Alkyl, halogenated C 1 -C 10 Alkoxy substituted C 1 -C 10 Alkyl, C 1 -C 10 Alkoxy substituted halo C 1 -C 10 Alkyl, C 3 -C 10 Cycloalkyl, halo C 3 -C 10 Cycloalkyl, C 1 -C 10 Alkyl substituted C 3 -C 10 Cycloalkyl, halo C 1 -C 10 Alkyl substituted C 3 -C 10 Cycloalkyl, C 1 -C 10 Alkyl-substituted halo C 3 -C 10 Cycloalkyl, C 1 -C 10 Alkoxy, halo C 1 -C 10 Alkoxy, C 1 -C 10 Alkylthio, halo C 1 -C 10 Alkylthio, C 1 -C 10 Alkylsulfinyl, halo C 1 -C 10 Alkylsulfinyl, C 1 -C 10 Alkylsulfonyl, haloC 1 -C 10 Alkylsulfonyl, formyl, C 1 -C 10 Alkylcarbonyl, haloC 1-C10 alkylcarbonyl, C 1 -C 10 Alkoxycarbonyl, halogenated C1-C10 alkoxycarbonyl, arylcarbonyl, aryloxycarbonyl, C 2 -C 6 Alkenyl, C 2 -C 6 Alkynyl, halo C 2 -C 6 Alkenyl, halo C 2 -C 6 Alkynyl, C 2 -C 6 Alkenyloxy, C 2 -C 6 Alkynyloxy, halogenated C 2 -C 6 Alkenyloxy, halogenated C 2 -C 6 Alkynyloxy, C 1 -C 10 Alkylcarbonyloxy, halo C 1 -C 10 Alkylcarbonyloxy, C 1 -C 10 Cyanoalkyl, C 1 -C 10 Cyanoalkoxy, C 1 -C 10 Alkyl-substituted silane groups, substituted or unsubstituted amino groups, aryl groups C 1 -C 6 Alkyl, aryloxy, aryl C 1 -C 6 Alkoxy, arylsulfonyl, arylsulfinyl, arylthio and aryl C 1 -C 6 Alkylsulfonyl, aryl C 1 -C 6 Alkylsulfinyl, aryl C 1 -C 6 Alkylthio, heterocycle C 1 -C 6 Alkyl, heterocyclyloxy, and optionally substituents are each independently selected from halogen, C 1 -C 10 Alkyl, halogenated C 1 -C 10 Alkyl, C 3 -C 10 Cycloalkyl, halo C 3 -C 10 Cycloalkyl, C 1 -C 10 Alkoxy, halo C 1 -C 10 Alkoxy, C 3 -C 10 Cycloalkoxy, halo C 3 -C 10 At least one of the cycloalkoxy groups; optionally Z 1 、Z 2 、Z 3 、Z 4 Any adjacent two groups of (a) are a group, and at least one group of the groups and the bonded benzene ring are cyclized with or without at least one heteroatom to form at least one 3-to 8-membered ring.
Several particularly preferred embodiments of the benzimidazole compounds of the present invention are provided below.
Description of the preferred embodiments 1
R is selected from C 1 -C 8 Alkyl, halogenated C 1 -C 8 Alkyl, C 3 -C 8 Cycloalkyl-substituted C 1 -C 8 Alkyl, halogenated C 3 -C 8 Cycloalkyl-substituted C 1 -C 8 Alkyl, C 3 -C 8 Cycloalkyl-substituted halo C 1 -C 8 Alkyl, C 1 -C 8 Alkoxy substituted C 1 -C 8 Alkyl, halogenated C 1 -C 8 Alkoxy substituted C 1 -C 8 Alkyl, C 1 -C 8 Alkoxy substituted halo C 1 -C 8 Alkyl, C 3 -C 8 Cycloalkoxy substituted C 1 -C 8 Alkyl, halogenated C 3 -C 8 Cycloalkoxy substituted C 1 -C 8 Alkyl, C 3 -C 8 Cycloalkoxy-substituted halos C 1 -C 8 Alkyl, C 3 -C 8 Cycloalkyl, halo C 3 -C 8 Cycloalkyl, C 1 -C 8 Alkyl substituted C 3 -C 8 Cycloalkyl, halo C 1 -C 8 Alkyl substituted C 3 -C 8 Cycloalkyl, C 1 -C 8 Alkyl-substituted halo C 3 -C 8 Cycloalkyl, C 1 -C 8 Alkoxy substituted C 3 -C 8 Cycloalkyl, halo C 1 -C 8 Alkoxy substituted C 3 -C 8 Cycloalkyl, C 1 -C 8 Alkoxy substituted halo C 3 -C 8 Cycloalkyl, C 3 -C 8 Cycloalkoxy substituted C 3 -C 8 Cycloalkyl, halo C 3 -C 8 Cycloalkoxy substituted C 3 -C 8 Cycloalkyl, C 3 -C 8 Cycloalkoxy-substituted halos C 3 -C 8 Cycloalkyl, C 2 -C 8 Alkenyl, halo C 2 -C 8 Alkenyl, C 2 -C 8 Alkynyl, halo C 2 -C 8 Alkynyl;
Y 1 、Y 2 each independently selected from H, halogen, CN, NO 2 、C 1 -C 8 Alkyl, halogenated C 1 -C 8 Alkyl, C 3 -C 8 Cycloalkyl-substituted C 1 -C 8 Alkyl, halogenated C 3 -C 8 Cycloalkyl-substituted C 1 -C 8 Alkyl, C 3 -C 8 Cycloalkyl-substituted halo C 1 -C 8 Alkyl, C 1 -C 8 Alkoxy substituted C 1 -C 8 Alkyl, halogenated C 1 -C 8 Alkoxy substituted C 1 -C 8 Alkyl, C 1 -C 8 Alkoxy substituted halo C 1 -C 8 Alkyl, C 3 -C 8 Cycloalkyl, halo C 3 -C 8 Cycloalkyl, C 1 -C 8 Alkyl substituted C 3 -C 8 Cycloalkyl, halo C 1 -C 8 Alkyl substituted C 3 -C 8 Cycloalkyl, C 1 -C 8 Alkyl-substituted halo C 3 -C 8 Cycloalkyl, C 1 -C 8 Alkoxy, halo C 1 -C 8 Alkoxy, C 1 -C 8 Alkylthio, halo C 1 -C 8 Alkylthio, C 1 -C 8 Alkylsulfinyl, halo C 1 -C 8 Alkylsulfinyl, C 1 -C 8 Alkylsulfonyl, haloC 1 -C 8 Alkylsulfonyl, C 1 -C 8 Alkylsulfonylamino, halo C 1 -C 8 Alkylsulfonylamino;
Z 1 、Z 2 、Z 3 、Z 4 each independently selected from H, halogen, CN, NO 2 、C 1 -C 8 Alkyl, halogenated C 1 -C 8 Alkyl, C 3 -C 8 Cycloalkyl, halo C 3 -C 8 Cycloalkyl, C 1 -C 8 Alkoxy, halo C 1 -C 8 Alkoxy, C 1 -C 8 Alkylthio, halo C 1 -C 8 Alkylthio, C 1 -C 8 Alkylsulfinyl, halo C 1 -C 8 Alkylsulfinyl, C 1 -C 8 Alkylsulfonyl, haloC 1 -C 8 An alkylsulfonyl group.
Description of the preferred embodiments 2
In the case of the formula (I),
r is selected from C 1 -C 8 Alkyl, halogenated C 1 -C 8 Alkyl, C 3 -C 8 Cycloalkyl, halo C 3 -C 8 Cycloalkyl, C 2 -C 8 Alkenyl, halo C 2 -C 8 Alkenyl, C 2 -C 8 Alkynyl and halo C 2 -C 8 Alkynyl;
Y 1 、Y 2 each independently selected from H, halogen, CN, NO 2 、C 1 -C 8 Alkyl, halogenated C 1 -C 8 Alkyl, C 3 -C 8 Cycloalkyl, halo C 3 -C 8 Cycloalkyl, C 1 -C 8 Alkoxy, halo C 1 -C 8 Alkoxy, C 1 -C 8 Alkylthio, halo C 1 -C 8 Alkylthio, C 1 -C 8 Alkylsulfinyl, halo C 1 -C 8 Alkylsulfinyl, C 1 -C 8 Alkylsulfonyl, haloC 1 -C 8 Alkylsulfonyl, C 1 -C 8 Alkylsulfonylamino, halo C 1 -C 8 Alkylsulfonylamino;
Z 1 、Z 2 、Z 3 、Z 4 each independently selected from H, halogen, CN, NO 2 、C 1 -C 8 Alkyl, halogenated C 1 -C 8 Alkyl, C 1 -C 8 Alkoxy, halo C 1 -C 8 Alkoxy, C 1 -C 8 Alkylthio, halo C 1 -C 8 Alkylthio, C 1 -C 8 Alkylsulfinyl, halo C 1 -C 8 Alkylsulfinyl, C 1 -C 8 Alkylsulfonyl, haloC 1 -C 8 An alkylsulfonyl group.
Description of the preferred embodiment 3
In the case of the formula (I),
r is selected from C 1 -C 8 Alkyl, halogenated C 1 -C 8 Alkyl, C 3 -C 8 Cycloalkyl, halo C 3 -C 8 Cycloalkyl, C 2 -C 5 Alkenyl, C 2 -C 5 Alkynyl;
Y 1 、Y 2 each independently selected from H, halogen, CN, NO 2 、C 1 -C 8 Alkyl, halogenated C 1 -C 8 Alkyl, C 1 -C 8 Alkoxy, halo C 1 -C 8 An alkoxy group;
Z 1 、Z 2 、Z 3 、Z 4 each independently selected from H, halogen, CN, NO 2 、C 1 -C 8 Alkyl, halogenated C 1 -C 8 Alkyl, C 1 -C 8 Alkoxy, halo C 1 -C 8 Alkoxy, C 1 -C 8 Alkylthio, halo C 1 -C 8 Alkylthio, C 1 -C 8 Alkylsulfinyl, halo C 1 -C 8 Alkylsulfinyl, C 1 -C 8 Alkylsulfonyl, haloC 1 -C 8 An alkylsulfonyl group.
Description of the preferred embodiments 4
In the case of the formula (I),
r is selected from methyl, ethyl, n-propyl, isopropyl, allyl, propargyl, CF 3 ；
Y 1 、Y 2 Each independently selected from H, F, cl, br, I, CN, NO 2 、CH 3 、CF 3 、OCH 3 、OCH 2 CF 3 、OCH 2 CH 2 CF 3 、OCH 2 CF 2 CF 3 、OCF 3 、CF 2 Cl、CFCl 2 、CCl 3 、SCF 3 、S(O)CF 3 、S(O) 2 CF 3 、NHC(O) 2 CH 3 、NHC(O) 2 CF 3 、NHS(O) 2 CF 3 、NHS(O) 2 CH 2 CH 3 ；
Z 1 、Z 2 、Z 3 、Z 4 Each independently selected from H, F, cl, br, I, CN, NO 2 、CH 3 、OCH 3 、CF 3 、OCF 3 、SCF 3 、S(O)CF 3 、S(O) 2 CF 3 。
Description of the preferred embodiment 5
The benzimidazole compound is selected from at least one of compounds shown in table 1:
TABLE 1
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The inventors of the present invention found that the thiazolyl group-containing benzimidazole compound or a salt thereof in the above-provided several preferred embodiments has a better insecticidal and acaricidal effect, and particularly the thiazolyl group-containing benzimidazole compound or a salt thereof in the preferred embodiments 3 to 5, particularly the compound of the preferred embodiment 5 has a better insecticidal and acaricidal effect, and can have an excellent insecticidal and acaricidal effect when used at a low concentration content (e.g., 6.25 mg/L).
Also, the present invention provides that the performance data (nuclear magnetism) of a part of the compounds are shown in table 2:
TABLE 2
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In the invention, the salts in the thiazolyl-containing benzimidazole compound or the salt thereof comprise, but are not limited to, inorganic salts such as hydrochloride, sulfate, nitrate, phosphate and the like; organic salts such as acetate, fumarate, maleate, oxalate, methanesulfonate, benzenesulfonate, and p-toluenesulfonate.
As described above, the second aspect of the present invention is a process for producing a thiazolyl group-containing benzimidazole compound or a salt thereof, which comprises:
(1) In a first solvent, carrying out a first reaction on a compound V and a compound IV in the presence of a first alkaline substance and a condensing agent to obtain a compound III;
(2) In a second solvent, carrying out a second reaction on the compound III and an acidic substance to obtain a compound II;
(3) In a third solvent, in the presence of a second alkaline substance, carrying out a third reaction on the compound II and the sulfonyl-containing compound to obtain the thiazolyl-containing benzimidazole compound or a salt thereof;
wherein the compound V has a structure shown in a formula (V), the compound IV has a structure shown in a formula (IV), the compound III has a structure shown in a formula (III), the compound II has a structure shown in a formula (II), the thiazolyl-containing benzimidazole compound has a structure shown in a formula (I), and the sulfonyl-containing compound has a structure shown in a formula (VI);
r, Y in formula (I), formula (II), formula (III), formula (IV), formula (V) and formula (VI) 1 、Y 2 、Z 1 、Z 2 、Z 3 、Z 4 And X is selected from halogen as defined in the first aspect.
According to the invention, in step (1), the first reaction is as follows:
preferably, in step (1), the conditions of the first reaction include: the temperature is between 10 ℃ below zero and 150 ℃ above zero, and the reaction time is between 0.1 and 48 hours.
Preferably, in step (1), the molar ratio of the amount of said compound V to the amount of said compound IV is between 0.5 and 2:1. the compound V and the compound IV are commercially available.
Preferably, in the step (1), the condensing agent is selected from at least one of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide (EDC) or its hydrochloride (EDCI), carbonyldiimidazole (CDI), 1, 3-Dicyclohexylcarbodiimide (DCC), diethyl cyanophosphate (DEPC), chlorocarbonate compounds, 2-chloro-1-methylpyridinium iodide.
Preferably, in step (1), the molar ratio of the condensing agent to the compound IV is used in the range of 1 to 2:1.
preferably, in step (1), the first basic 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, 1, 8-diazabicyclo [5.4.0] undec-7-ene.
Preferably, in step (1), the molar ratio of the first basic substance to the compound IV is used in an amount ranging from 0.1 to 10:1.
preferably, in step (1), the first solvent is selected from at least one of pyridine, dichloromethane, chloroform, carbon tetrachloride benzene, toluene, xylene, chlorobenzene, dichlorobenzene, diethyl ether, methyl tertiary butyl ether, dioxane, tetrahydrofuran, 2-methyltetrahydrofuran, N-Dimethylformamide (DMF), N-Dimethylacetamide (DMA), N-methylpyrrolidone (NMP), acetone, methyl ethyl ketone, dimethyl sulfoxide, 1, 3-dimethyl-2-imidazolidinone.
Preferably, in step (1), the first solvent is used in an amount of 1 to 20mL relative to 1mmol of the compound IV.
According to the present invention, in step (1), the first solvent and the first basic substance may be the same, for example, may be pyridine at the same time. In addition, when the first solvent and the first basic substance are the same, they need to be separately metered.
According to the invention, in step (2), the second reaction is as follows:
preferably, in step (2), the conditions of the second reaction include: the temperature is between minus 10 ℃ and minus 300 ℃ and the reaction time is between 0.5 and 48 hours.
Preferably, in step (2), the acidic substance is selected from at least one of p-toluene sulfonic acid or a hydrate thereof, 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.
Preferably, in step (2), the molar ratio of the acidic substance to the compound IV is in the range of 0.01 to 10:1.
preferably, in step (2), the second solvent is selected from at least one of N, N-Dimethylformamide (DMF), 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, 1, 3-dimethyl-2-imidazolidinone.
Preferably, in step (2), the second solvent is used in an amount of 1 to 20mL relative to 1mmol of the compound III.
Preferably, step (2) further comprises: the second reaction is followed by adjusting the pH of the system to 7-10 using an alkaline solution, for example aqueous sodium hydroxide.
According to the invention, in step (3), the third reaction is as follows:
preferably, in step (3), the conditions of the third reaction include: the temperature is between minus 10 ℃ and minus 100 ℃ and the reaction time is between 0.1 and 48 hours.
Preferably, in step (3), the sulfonyl-containing compound is used in a molar ratio to the compound II of from 0.8 to 10:1.
preferably, in step (3), the sulfonyl-containing compound is selected from at least one of methylsulfonyl chloride, ethylsulfonyl chloride, n-propylsulfonyl chloride and n-butylsulfonyl chloride, more preferably ethylsulfonyl chloride.
Preferably, in step (3), the second basic 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, 1, 8-diazabicyclo [5.4.0] undec-7-ene.
Preferably, in step (3), the molar ratio of the second basic substance to the compound II is used in an amount ranging from 1 to 10:1.
preferably, in the step (3), the third solvent is selected from at least one of diethyl ether, tetrahydrofuran (THF), 2-methyltetrahydrofuran, N-Dimethylformamide (DMF), N-Dimethylacetamide (DMA), N-methylpyrrolidone (NMP), dioxane, benzene, toluene, xylene, dichloromethane, chloroform, carbon tetrachloride, chlorobenzene, dichlorobenzene.
Preferably, in step (3), the third solvent is used in an amount of 1 to 20mL relative to 1mmol of the compound II.
According to a preferred embodiment of the present invention, step (3) comprises: and in a third solvent, in the presence of a second alkaline substance, performing a first-stage third reaction on the compound II, and then adding the sulfonyl-containing compound to perform a second-stage third reaction to obtain the thiazolyl-containing benzimidazole compound.
Preferably, the conditions of the first stage third reaction include: the temperature is between minus 10 ℃ and minus 100 ℃ and the reaction time is between 10 and 120 minutes.
Preferably, the conditions of the second stage third reaction include: the temperature is between minus 10 ℃ and minus 100 ℃ and the reaction time is between 0.5 and 48 hours.
According to the present invention, the method may further include various post-treatment operation means such as extraction, washing, drying, suction filtration, concentration, separation and purification, etc., which are currently used in the art, and the present invention is not particularly limited thereto, and may be performed by various conventional operations in the art, for example, extraction using ethyl acetate; drying with anhydrous sodium sulfate; concentrating under reduced pressure; the separation and purification adopts column chromatography separation purity and the like.
As previously described, a third aspect of the invention provides thiazolyl-containing benzimidazole compounds obtainable by the process according to the second aspect.
As described above, a fourth aspect of the present invention provides the use of the thiazolyl-containing benzimidazole compound according to the first aspect or the third aspect described above or a salt thereof for the preparation of an insecticidal acaricide and/or a parasiticide.
Preferably, the thiazolyl group-containing benzimidazole compound or a salt thereof is used as an active ingredient (i.e., an active ingredient) in the insecticidal and acaricidal agent.
As described above, the fifth aspect of the present invention provides an insecticidal/acaricidal agent comprising an active ingredient selected from at least one of the thiazolyl group containing benzimidazole compounds or salts thereof according to the first aspect or the third aspect.
In the fifth aspect of the present invention, the content of the active ingredient is preferably 1 to 99% by weight, for example, 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 in the range constituted by any two of these values, based on the total weight of the insecticidal and acaricidal agent. More preferably, the content of the active ingredient is 5 to 60% by weight based on the total weight of the insecticidal and acaricidal agent.
In the fifth aspect of the present invention, preferably, the insecticidal and acaricidal agent further comprises a carrier. Preferably, the carrier in the insecticidal acaricide is an agriculturally, forestry and horticulturally acceptable substance which aids in 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 at least one solid substance selected from the group consisting of china clay, natural or synthetic silicates, silica, resins, waxes, solid fertilizers; the liquid carrier is preferably a liquid substance selected from the group consisting of water, alcohols, ketones, petroleum fractions, aromatic hydrocarbons, chlorinated hydrocarbons, liquefied gases.
In the fifth aspect of the present invention, the insecticidal and acaricidal agent may further comprise other auxiliary components commonly used in the art, such as surfactants, protective colloids, binders, thickeners, thixotropic agents, penetrants, chelating agents, colorants, polymers, etc., and the present invention is not particularly limited thereto, and a person skilled in the art may select a reasonable composition and amount according to actual needs.
In the fifth aspect of the present invention, preferably, the dosage forms of the insecticidal and acaricidal agents are each independently selected from at least one of wettable powder, soluble powder, emulsifiable concentrate, aqueous suspension concentrate, dispersible oil suspension concentrate, aqueous emulsion, suspoemulsion, microemulsion, aqueous solution, granule, microcapsule and water dispersible granule, whereby the active ingredient is more easily dissolved or dispersed so as to be more easily dispersed when used as an active substance of an insecticidal and acaricidal agent, improving the application effect.
In the fifth aspect of the present invention, the present invention is not particularly limited in the method for preparing the insecticidal and acaricidal agent, and the person skilled in the art can refer to the methods in the prior art documents and standards or prepare the agent using the prior art methods to obtain the desired composition and dosage form.
As previously mentioned, a sixth aspect of the present invention provides the use of the foregoing insecticidal and acaricidal agents in agriculture, forestry and horticulture.
Preferably, the application method comprises the following steps: the insecticidal and acaricidal agent is applied to the insect pest and/or to the pest mites, or the insecticidal and acaricidal agent is applied to the growth medium of the insect pest and/or pest mites. According to the invention, the growth medium is, for example, plants, soil.
Preferably, the effective amount of the application (i.e. the amount of active ingredient) is from 10 to 1000 grams per hectare of soil, more preferably from 20 to 500 grams per hectare of soil. According to the present invention, the specific mode of application is not particularly limited, and may be carried out by methods conventional in the art, for example, spraying the insecticidal and acaricidal agent onto the insect pests and/or mites, or onto the growth medium of the insect pests and/or mites.
According to the invention, in the application of the insecticidal and acaricidal agent in agriculture, forestry and gardening for insecticidal and/or acaricidal, the insecticidal and acaricidal agent can be compounded with existing bactericides, insecticides, herbicides, plant growth regulators, plant fertilizers and the like in the field for application, so that additive or synergistic effects are generated by compounding, and better effects are obtained. The invention is not particularly limited, and on the premise of using the thiazolyl-containing benzimidazole compound or the salt thereof as an active component, a person skilled in the art can reasonably select a proper amount of substances for combination and compounding according to actual requirements.
In a seventh aspect, the present invention provides a parasite control agent comprising an active ingredient selected from at least one of the thiazolyl-containing benzimidazole compounds or salts thereof according to the foregoing first or third aspects.
In an eighth aspect, the present invention provides the use of the aforementioned parasite control agent for controlling parasites in and out of animals.
The invention will be described in detail below by way of examples.
In the following examples, all the raw materials used were commercially available ones unless otherwise specified.
The sources of some of the raw materials are shown in Table 3:
TABLE 3 Table 3
Raw materials Purchased from the manufacturer
V-1 Beijing coupling technologies Co Ltd
IV-1 Beijing coupling technologies Co Ltd
Condensing agent: HATU (Hash Transmission of Wireless local area network) Beijing coupling technologies Co Ltd
First alkaline substance: diisopropylethylamine Beijing coupling technologies Co Ltd
Acidic substance: para-toluenesulfonic acid monohydrate Beijing coupling technologies Co Ltd
Sulfonyl-containing compounds: ethylsulfonyl chloride Beijing coupling technologies Co Ltd
In the examples below, room temperature refers to 25.+ -. 2 ℃ unless otherwise specified.
Example 1
This example is the preparation of Compound I-2
The preparation process comprises the following steps:
(1) A first solvent (dichloromethane, 15 mL) was added to the reaction flask, a condensing agent (HATU, 15 mmol) and a first basic substance (diisopropylethylamine, 2 mmol) were added, and compound V (V-1, 10 mmol) and compound IV (IV-1, 10 mmol) were added to react at room temperature for 3 hours to perform a first reaction, followed by water addition, extraction with ethyl acetate, washing of the organic phase with saturated brine, and drying over anhydrous sodium sulfate. Suction filtering, concentrating the filtrate under reduced pressure to obtain a compound III;
(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 to react at 160℃for 4 hours to conduct a second reaction. Cooling to room temperature, adding 10wt% sodium hydroxide aqueous solution to adjust the pH value of the system to 9, extracting with ethyl acetate, washing the organic phase with saturated saline solution, drying with anhydrous sodium sulfate, suction filtering, and concentrating the filtrate under reduced pressure to obtain a compound II (II-1, 8 mmol);
(3) The compound II was dissolved in a third solvent (THF, 30 mL), a second basic substance (0.96 g of mineral oil-coated NaH, naH content 60wt%, naH 24 mmol) was added, and after 10min at room temperature, a sulfonyl-containing compound (ethylsulfonyl chloride, 24 mmol) was added and reacted at room temperature for 12h. Saturated ammonium chloride was added to quench, extraction was performed with ethyl acetate, the organic phase was washed with saturated brine, dried over anhydrous sodium sulfate, suction filtration and concentration of the filtrate under reduced pressure, and the resultant was separated and purified by column chromatography to give compound I-2 (1.56 g) as a white solid.
Biological Activity test
The test example tests the mite-killing activity of the compound prepared by the method, specifically the mite-killing activity of tetranychus cinnabarinus, and the specific test process is as follows:
(1) Dissolving a compound to be tested with acetone, diluting the compound to a required concentration by using 0.1wt% of Tween 80 aqueous solution, and preparing a medicament by using the compound to be tested, wherein the acetone content is not more than 5 wt%;
(2) Removing one true leaf of the bean seedlings growing to two true leaves, inoculating tetranychus cinnabarinus (the number of tetranychus cinnabarinus inoculated to each bean seedling is 50-150), investigating the number of inoculated mites in 24 hours, respectively carrying out whole-plant spraying treatment (the spraying amount of each plant is 0.5 mL) on three bean seedlings by using a handheld sprayer, placing the three bean seedlings in a constant-temperature observation room (25 ℃) for observation after treatment, investigating the number of live mites after 72 hours, and calculating the mortality:
mortality (%) = (number of inoculated mites-number of live mites after spraying)/number of inoculated mites×100%.
Test example 1-A
The biological activity test of the compounds was carried out according to the above procedure, and in the test, the compounds I-6, I-10, I-36 showed a mortality rate of more than 90% against tetranychus cinnabarinus at a concentration of 25 mg/L.
Test example 1-B
Compound bioactivity tests were performed according to the procedure described above, in which compound I-57 showed a mortality rate of more than 90% for tetranychus cinnabarinus at a concentration of 6.25 mg/L.
Test example 1-C
The biological activity test of the compounds was carried out according to the above procedure, in which the compounds I-2, I-81, I-135 showed a mortality rate of more than 90% for tetranychus cinnabarinus at a concentration of 1.56 mg/L.
Comparative test example
Compound bioactivity tests were performed according to the procedure described above, in which test experiments the comparative compounds KC-1, KC-2, KC-4 all showed a mortality of less than 50% for tetranychus cinnabarinus at 100 mg/L; the comparative compound KC-3 showed a mortality rate of less than 50% for tetranychus cinnabarinus at 25mg/L
As can be seen from the test results, the thienyl benzimidazole compound or the salt thereof provided by the invention has excellent insecticidal and acaricidal effects, and the insecticidal and acaricidal activity is far higher than that of the known compounds, and particularly, the thienyl benzimidazole compound provided by the invention has excellent insecticidal and acaricidal effects when being used in low concentration content (such as 6.25 mg/L).
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.

Claims (14)

1. A thiazolyl-containing benzimidazole compound or a salt thereof is characterized in that the thiazolyl-containing benzimidazole compound has a structure shown in a formula (I):
Wherein, in the formula (I),
r is selected from substituted or unsubstituted C 1 -C 10 Alkyl, substituted or unsubstituted C 3 -C 10 Cycloalkyl, substituted or unsubstituted C 2 -C 10 Alkenyl, substituted or unsubstituted C 2 -C 10 Alkynyl, and the optional substituents are each independently selected from halogen, C 1 -C 10 Alkyl, halogenated C 1 -C 10 Alkyl, C 3 -C 10 Cycloalkyl, halo C 3 -C 10 Cycloalkyl, C 1 -C 10 Alkoxy, halo C 1 -C 10 Alkoxy, C 3 -C 10 Cycloalkoxy, halo C 3 -C 10 At least one of the cycloalkoxy groups;
Y 1 、Y 2 each independently selected from H, halogen, CN, NO 2 Formyl, substituted or unsubstituted C 1 -C 10 Alkyl, substituted or unsubstituted C 3 -C 10 Cycloalkyl, substituted or unsubstituted C 1 -C 10 Alkoxy, substituted or unsubstituted C 1 -C 10 Alkylthio, substituted or unsubstituted C 1 -C 10 Alkylsulfinyl, substituted or unsubstituted C 1 -C 10 Alkylsulfonyl, substituted or unsubstituted C 1 -C 10 Alkylsulfonylamino, substituted or unsubstituted halogenated C 1 -C 8 Alkylsulfonylamino, substituted or unsubstituted C 1 -C 10 Alkylcarbonyl, substituted or unsubstituted C 1 -C 10 Alkoxycarbonyl, substituted or unsubstituted arylcarbonyl, substituted or unsubstituted aryloxycarbonyl, substituted or unsubstituted C 2 -C 6 Alkenyl, substituted or unsubstituted C 2 -C 6 Alkynyl, substituted or unsubstituted C 2 -C 6 Alkenyloxy, substituted or unsubstituted C 2 -C 6 Alkynyloxy, substituted or unsubstituted C 1 -C 10 Alkylcarbonyloxy, substituted or unsubstituted C 1 -C 10 Cyanoalkyl, substituted or unsubstituted C 1 -C 10 Cyanoalkoxy, substituted or unsubstituted silyl, substituted or unsubstituted amino, substituted or unsubstituted aryl C 1 -C 6 Alkyl, substituted or unsubstituted aryloxy, substituted or unsubstituted aryl C 1 -C 6 Alkoxy, substituted or unsubstituted arylsulfonyl, substituted or unsubstituted arylsulfinyl, substituted or unsubstituted arylthio, substituted or unsubstituted arylC 1 -C 6 Alkylsulfonyl, substituted or unsubstituted aryl C 1 -C 6 Alkylsulfinyl, substituted or unsubstituted aryl C 1 -C 6 Alkylthio, substituted or unsubstituted heterocycle C 1 -C 6 Alkyl, substituted or unsubstituted heteroEpoxy groups, and the optional substituents are each independently selected from halogen, C 1 -C 10 Alkyl, halogenated C 1 -C 10 Alkyl, C 3 -C 10 Cycloalkyl, halo C 3 -C 10 Cycloalkyl, C 1 -C 10 Alkoxy, halo C 1 -C 10 Alkoxy, C 3 -C 10 Cycloalkoxy, halo C 3 -C 10 At least one of the cycloalkoxy groups;
Z 1 、Z 2 、Z 3 、Z 4 each independently selected from H, halogen, CN, NO 2 Formyl, substituted or unsubstituted C 1 -C 10 Alkyl, substituted or unsubstituted C 3 -C 10 Cycloalkyl, substituted or unsubstituted C 1 -C 10 Alkoxy, substituted or unsubstituted C 1 -C 10 Alkylthio, substituted or unsubstituted C 1 -C 10 Alkylsulfinyl, substituted or unsubstituted C 1 -C 10 Alkylsulfonyl, substituted or unsubstituted C 1 -C 10 Alkylcarbonyl, substituted or unsubstituted C 1 -C 10 Alkoxycarbonyl, substituted or unsubstituted arylcarbonyl, substituted or unsubstituted aryloxycarbonyl, substituted or unsubstituted C 2 -C 6 Alkenyl, substituted or unsubstituted C 2 -C 6 Alkynyl, substituted or unsubstituted C 2 -C 6 Alkenyloxy, substituted or unsubstituted C 2 -C 6 Alkynyloxy, substituted or unsubstituted C 1 -C 10 Alkylcarbonyloxy, substituted or unsubstituted C 1 -C 10 Cyanoalkyl, substituted or unsubstituted C 1 -C 10 Cyanoalkoxy, substituted or unsubstituted silyl, substituted or unsubstituted amino, substituted or unsubstituted aryl C 1 -C 6 Alkyl, substituted or unsubstituted aryloxy, substituted or unsubstituted aryl C 1 -C 6 Alkoxy, substituted or unsubstituted arylsulfonyl, substituted or unsubstituted arylsulfinyl, substituted or unsubstituted arylthioAryl, substituted or unsubstituted aryl C 1 -C 6 Alkylsulfonyl, substituted or unsubstituted aryl C 1 -C 6 Alkylsulfinyl, substituted or unsubstituted aryl C 1 -C 6 Alkylthio, substituted or unsubstituted heterocycle C 1 -C 6 Alkyl, substituted or unsubstituted heterocyclyloxy, and the optionally present substituents are each independently selected from halogen, C 1 -C 10 Alkyl, halogenated C 1 -C 10 Alkyl, C 3 -C 10 Cycloalkyl, halo C 3 -C 10 Cycloalkyl, C 1 -C 10 Alkoxy, halo C 1 -C 10 Alkoxy, C 3 -C 10 Cycloalkoxy, halo C 3 -C 10 At least one of the cycloalkoxy groups; optionally Z 1 、Z 2 、Z 3 、Z 4 Any adjacent two groups of (a) are a group, and at least one group of the groups and the bonded benzene ring are cyclized with or without at least one heteroatom to form at least one 3-to 8-membered ring.
2. The compound or salt according to claim 1, wherein, in the formula (I),
r is selected from C 1 -C 10 Alkyl, halogenated C 1 -C 10 Alkyl, C 3 -C 10 Cycloalkyl-substituted C 1 -C 10 Alkyl, halogenated C 3 -C 10 Cycloalkyl-substituted C 1 -C 10 Alkyl, C 3 -C 10 Cycloalkyl-substituted halo C 1 -C 10 Alkyl, C 1 -C 10 Alkoxy substituted C 1 -C 10 Alkyl, halogenated C 1 -C 10 Alkoxy substituted C 1 -C 10 Alkyl, C 1 -C 10 Alkoxy substituted halo C 1 -C 10 Alkyl, C 3 -C 10 Cycloalkoxy substituted C 1 -C 10 Alkyl, halogenated C 3 -C 10 Cycloalkoxy substituted C 1 -C 10 Alkyl, C 3 -C 10 Cycloalkoxy-substituted halos C 1 -C 10 Alkyl, C 3 -C 10 Cycloalkyl, halo C 3 -C 10 Cycloalkyl, C 1 -C 10 Alkyl substituted C 3 -C 10 Cycloalkyl, halo C 1 -C 10 Alkyl substituted C 3 -C 10 Cycloalkyl, C 1 -C 10 Alkyl-substituted halo C 3 -C 10 Cycloalkyl, C 1 -C 10 Alkoxy substituted C 3 -C 10 Cycloalkyl, halo C 1 -C 10 Alkoxy substituted C 3 -C 10 Cycloalkyl, C 1 -C 10 Alkoxy substituted halo C 3 -C 10 Cycloalkyl, C 3 -C 10 Cycloalkoxy substituted C 3 -C 10 Cycloalkyl, halo C 3 -C 10 Cycloalkoxy substituted C 3 -C 10 Cycloalkyl, C 3 -C 10 Cycloalkoxy-substituted halos C 3 -C 10 Cycloalkyl, C 2 -C 10 Alkenyl, halo C 2 -C 10 Alkenyl, C 2 -C 10 Alkynyl, halo C 2 -C 10 Alkynyl;
Y 1 、Y 2 each independently selected from H, halogen, CN, NO 2 、C 1 -C 10 Alkyl, halogenated C 1 -C 10 Alkyl, C 3 -C 10 Cycloalkyl-substituted C 1 -C 10 Alkyl, halogenated C 3 -C 10 Cycloalkyl-substituted C 1 -C 10 Alkyl, C 3 -C 10 Cycloalkyl-substituted halo C 1 -C 10 Alkyl, C 1 -C 10 Alkoxy substituted C 1 -C 10 Alkyl, halogenated C 1 -C 10 Alkoxy substituted C 1 -C 10 Alkyl, C 1 -C 10 Alkoxy substituted halo C 1 -C 10 Alkyl, C 3 -C 10 Cycloalkyl, halo C 3 -C 10 Cycloalkyl, C 1 -C 10 Alkyl substituted C 3 -C 10 Cycloalkyl, halo C 1 -C 10 Alkyl substituted C 3 -C 10 Cycloalkyl, C 1 -C 10 Alkyl-substituted halo C 3 -C 10 Cycloalkyl, C 1 -C 10 Alkoxy, halo C 1 -C 10 Alkoxy, C 1 -C 10 Alkylthio, halo C 1 -C 10 Alkylthio, C 1 -C 10 Alkylsulfinyl, halo C 1 -C 10 Alkylsulfinyl, C 1 -C 10 Alkylsulfonyl, haloC 1 -C 10 Alkylsulfonyl, C 1 -C 10 Alkylsulfonylamino, halo C 1 -C 8 Alkylsulfonylamino, formyl, C 1 -C 10 Alkylcarbonyl, halo C 1 -C 10 Alkylcarbonyl, C 1 -C 10 Alkoxycarbonyl, halo C 1 -C 10 Alkoxycarbonyl, arylcarbonyl, aryloxycarbonyl, C 2 -C 6 Alkenyl, C 2 -C 6 Alkynyl, halo C 2 -C 6 Alkenyl, halo C 2 -C 6 Alkynyl, C 2 -C 6 Alkenyloxy, C 2 -C 6 Alkynyloxy, halogenated C 2 -C 6 Alkenyloxy, halogenated C 2 -C 6 Alkynyloxy, C 1 -C 10 Alkylcarbonyloxy, halo C 1 -C 10 Alkylcarbonyloxy, C 1 -C 10 Cyanoalkyl, C 1 -C 10 Cyanoalkoxy, C 1 -C 10 Alkyl-substituted silane groups, substituted or unsubstituted amino groups, aryl groups C 1 -C 6 Alkyl, aryloxy, aryl C 1 -C 6 Alkoxy, arylsulfonyl, arylsulfinyl, arylthio and aryl C 1 -C 6 Alkylsulfonyl, aryl C 1 -C 6 Alkylsulfinyl, aryl C 1 -C 6 Alkylthio, heterocycle C 1 -C 6 Alkyl, heterocyclyloxy, and optionally substituents are each independently selected from halogen, C 1 -C 10 Alkyl, halogenated C 1 -C 10 Alkyl, C 3 -C 10 Cycloalkyl, halo C 3 -C 10 Cycloalkyl, C 1 -C 10 Alkoxy, halo C 1 -C 10 Alkoxy, C 3 -C 10 Cycloalkoxy, halo C 3 -C 10 At least one of the cycloalkoxy groups;
Z 1 、Z 2 、Z 3 、Z 4 each independently selected from H, halogen, CN, NO 2 、C 1 -C 10 Alkyl, halogenated C 1 -C 10 Alkyl, C 3 -C 10 Cycloalkyl-substituted C 1 -C 10 Alkyl, halogenated C 3 -C 10 Cycloalkyl-substituted C 1 -C 10 Alkyl, C 3 -C 10 Cycloalkyl-substituted halo C 1 -C 10 Alkyl, C 1 -C 10 Alkoxy substituted C 1 -C 10 Alkyl, halogenated C 1 -C 10 Alkoxy substituted C 1 -C 10 Alkyl, C 1 -C 10 Alkoxy substituted halo C 1 -C 10 Alkyl, C 3 -C 10 Cycloalkyl, halo C 3 -C 10 Cycloalkyl, C 1 -C 10 Alkyl substituted C 3 -C 10 Cycloalkyl, halo C 1 -C 10 Alkyl substituted C 3 -C 10 Cycloalkyl, C 1 -C 10 Alkyl-substituted halo C 3 -C 10 Cycloalkyl, C 1 -C 10 Alkoxy, halo C 1 -C 10 Alkoxy, C 1 -C 10 Alkylthio, halo C 1 -C 10 Alkylthio, C 1 -C 10 Alkylsulfinyl, halo C 1 -C 10 Alkylsulfinyl, C 1 -C 10 Alkylsulfonyl, haloC 1 -C 10 Alkylsulfonyl, formyl, C 1 -C 10 Alkylcarbonyl, haloC 1-C10 alkylcarbonyl, C 1 -C 10 Alkoxycarbonyl, halo C 1 -C 10 Alkoxycarbonyl, arylcarbonyl, aryloxycarbonyl, C 2 -C 6 Alkenyl, C 2 -C 6 Alkynyl, halo C 2 -C 6 Alkenyl, halo C 2 -C 6 Alkynyl, C 2 -C 6 Alkenyloxy, C 2 -C 6 Alkynyloxy, halogenated C 2 -C 6 Alkenyloxy radical,Halogenated C 2 -C 6 Alkynyloxy, C 1 -C 10 Alkylcarbonyloxy, halo C 1 -C 10 Alkylcarbonyloxy, C 1 -C 10 Cyanoalkyl, C 1 -C 10 Cyanoalkoxy, C 1 -C 10 Alkyl-substituted silane groups, substituted or unsubstituted amino groups, aryl groups C 1 -C 6 Alkyl, aryloxy, aryl C 1 -C 6 Alkoxy, arylsulfonyl, arylsulfinyl, arylthio and aryl C 1 -C 6 Alkylsulfonyl, aryl C 1 -C 6 Alkylsulfinyl, aryl C 1 -C 6 Alkylthio, heterocycle C 1 -C 6 Alkyl, heterocyclyloxy, and optionally substituents are each independently selected from halogen, C 1 -C 10 Alkyl, halogenated C 1 -C 10 Alkyl, C 3 -C 10 Cycloalkyl, halo C 3 -C 10 Cycloalkyl, C 1 -C 10 Alkoxy, halo C 1 -C 10 Alkoxy, C 3 -C 10 Cycloalkoxy, halo C 3 -C 10 At least one of the cycloalkoxy groups; optionally Z 1 、Z 2 、Z 3 、Z 4 Any adjacent two groups in (a) are a group, and at least one group of the groups and the bonded benzene ring are cyclized with or without at least one heteroatom to form at least one 3-to 8-membered ring;
preferably, in the formula (I),
r is selected from C 1 -C 8 Alkyl, halogenated C 1 -C 8 Alkyl, C 3 -C 8 Cycloalkyl-substituted C 1 -C 8 Alkyl, halogenated C 3 -C 8 Cycloalkyl-substituted C 1 -C 8 Alkyl, C 3 -C 8 Cycloalkyl-substituted halo C 1 -C 8 Alkyl, C 1 -C 8 Alkoxy substituted C 1 -C 8 Alkyl, halogenated C 1 -C 8 Alkoxy substituted C 1 -C 8 Alkyl, C 1 -C 8 Alkoxy substituted halo C 1 -C 8 Alkyl, C 3 -C 8 Cycloalkoxy radicals are takenSubstitute C 1 -C 8 Alkyl, halogenated C 3 -C 8 Cycloalkoxy substituted C 1 -C 8 Alkyl, C 3 -C 8 Cycloalkoxy-substituted halos C 1 -C 8 Alkyl, C 3 -C 8 Cycloalkyl, halo C 3 -C 8 Cycloalkyl, C 1 -C 8 Alkyl substituted C 3 -C 8 Cycloalkyl, halo C 1 -C 8 Alkyl substituted C 3 -C 8 Cycloalkyl, C 1 -C 8 Alkyl-substituted halo C 3 -C 8 Cycloalkyl, C 1 -C 8 Alkoxy substituted C 3 -C 8 Cycloalkyl, halo C 1 -C 8 Alkoxy substituted C 3 -C 8 Cycloalkyl, C 1 -C 8 Alkoxy substituted halo C 3 -C 8 Cycloalkyl, C 3 -C 8 Cycloalkoxy substituted C 3 -C 8 Cycloalkyl, halo C 3 -C 8 Cycloalkoxy substituted C 3 -C 8 Cycloalkyl, C 3 -C 8 Cycloalkoxy-substituted halos C 3 -C 8 Cycloalkyl, C 2 -C 8 Alkenyl, halo C 2 -C 8 Alkenyl, C 2 -C 8 Alkynyl, halo C 2 -C 8 Alkynyl;
Y 1 、Y 2 each independently selected from H, halogen, CN, NO 2 、C 1 -C 8 Alkyl, halogenated C 1 -C 8 Alkyl, C 3 -C 8 Cycloalkyl-substituted C 1 -C 8 Alkyl, halogenated C 3 -C 8 Cycloalkyl-substituted C 1 -C 8 Alkyl, C 3 -C 8 Cycloalkyl-substituted halo C 1 -C 8 Alkyl, C 1 -C 8 Alkoxy substituted C 1 -C 8 Alkyl, halogenated C 1 -C 8 Alkoxy substituted C 1 -C 8 Alkyl, C 1 -C 8 Alkoxy substituted halo C 1 -C 8 Alkyl, C 3 -C 8 Cycloalkyl, halo C 3 -C 8 Cycloalkyl, C 1 -C 8 Alkyl substituted C 3 -C 8 Cycloalkyl, halo C 1 -C 8 Alkyl substituted C 3 -C 8 Cycloalkyl, C 1 -C 8 Alkyl-substituted halo C 3 -C 8 Cycloalkyl, C 1 -C 8 Alkoxy, halo C 1 -C 8 Alkoxy, C 1 -C 8 Alkylthio, halo C 1 -C 8 Alkylthio, C 1 -C 8 Alkylsulfinyl, halo C 1 -C 8 Alkylsulfinyl, C 1 -C 8 Alkylsulfonyl, haloC 1 -C 8 Alkylsulfonyl, C 1 -C 8 Alkylsulfonylamino, halo C 1 -C 8 Alkylsulfonylamino;
Z 1 、Z 2 、Z 3 、Z 4 each independently selected from H, halogen, CN, NO 2 、C 1 -C 8 Alkyl, halogenated C 1 -C 8 Alkyl, C 3 -C 8 Cycloalkyl, halo C 3 -C 8 Cycloalkyl, C 1 -C 8 Alkoxy, halo C 1 -C 8 Alkoxy, C 1 -C 8 Alkylthio, halo C 1 -C 8 Alkylthio, C 1 -C 8 Alkylsulfinyl, halo C 1 -C 8 Alkylsulfinyl, C 1 -C 8 Alkylsulfonyl, haloC 1 -C 8 An alkylsulfonyl group.
3. A chemical or salt thereof according to claim 1 or 2, wherein, in formula (I),
r is selected from C 1 -C 8 Alkyl, halogenated C 1 -C 8 Alkyl, C 3 -C 8 Cycloalkyl, halo C 3 -C 8 Cycloalkyl, C 2 -C 8 Alkenyl, halo C 2 -C 8 Alkenyl, C 2 -C 8 Alkynyl and halo C 2 -C 8 Alkynyl;
Y 1 、Y 2 each independently selected from H, halogen, CN, NO 2 、C 1 -C 8 Alkyl, halogenated C 1 -C 8 Alkyl, C 3 -C 8 Cycloalkyl, halo C 3 -C 8 Cycloalkyl, C 1 -C 8 Alkoxy, halo C 1 -C 8 Alkoxy, C 1 -C 8 Alkylthio, halo C 1 -C 8 Alkylthio, C 1 -C 8 Alkylsulfinyl, halo C 1 -C 8 Alkylsulfinyl, C 1 -C 8 Alkylsulfonyl, haloC 1 -C 8 Alkylsulfonyl, C 1 -C 8 Alkylsulfonylamino, halo C 1 -C 8 Alkylsulfonylamino;
Z 1 、Z 2 、Z 3 、Z 4 each independently selected from H, halogen, CN, NO 2 、C 1 -C 8 Alkyl, halogenated C 1 -C 8 Alkyl, C 1 -C 8 Alkoxy, halo C 1 -C 8 Alkoxy, C 1 -C 8 Alkylthio, halo C 1 -C 8 Alkylthio, C 1 -C 8 Alkylsulfinyl, halo C 1 -C 8 Alkylsulfinyl, C 1 -C 8 Alkylsulfonyl, haloC 1 -C 8 An alkylsulfonyl group.
4. A chemical compound or salt thereof according to claim 1 to 3, wherein, in formula (I),
r is selected from C 1 -C 8 Alkyl, halogenated C 1 -C 8 Alkyl, C 3 -C 8 Cycloalkyl, halo C 3 -C 8 Cycloalkyl, C 2 -C 5 Alkenyl, C 2 -C 5 Alkynyl;
Y 1 、Y 2 each independently selected from H, halogen, CN, NO 2 、C 1 -C 8 Alkyl, halogenated C 1 -C 8 Alkyl, C 1 -C 8 Alkoxy, halo C 1 -C 8 An alkoxy group;
Z 1 、Z 2 、Z 3 、Z 4 each independently selected from H, halogen, CN, NO 2 、C 1 -C 8 Alkyl, halogenated C 1 -C 8 Alkyl, C 1 -C 8 Alkoxy, halo C 1 -C 8 Alkoxy, C 1 -C 8 Alkylthio, halo C 1 -C 8 Alkylthio, C 1 -C 8 Alkylsulfinyl, halo C 1 -C 8 Alkylsulfinyl, C 1 -C 8 Alkylsulfonyl, haloC 1 -C 8 An alkylsulfonyl group;
preferably, in the formula (I),
r is selected from methyl, ethyl, n-propyl, isopropyl, allyl, propargyl, CF 3 ；
Y 1 、Y 2 Each independently selected from H, F, cl, br, I, CN, NO 2 、CH 3 、CF 3 、OCH 3 、OCH 2 CF 3 、OCH 2 CH 2 CF 3 、OCH 2 CF 2 CF 3 、OCF 3 、CF 2 Cl、CFCl 2 、CCl 3 、SCF 3 、S(O)CF 3 、S(O) 2 CF 3 、NHC(O) 2 CH 3 、NHC(O) 2 CF 3 、NHS(O) 2 CF 3 、NHS(O) 2 CH 2 CH 3 ；
Z 1 、Z 2 、Z 3 、Z 4 Each independently selected from H, F, cl, br, I, CN, NO 2 、CH 3 、OCH 3 、CF 3 、OCF 3 、SCF 3 、S(O)CF 3 、S(O) 2 CF 3 。
5. A process for preparing a thiazolyl-containing benzimidazole compound or a salt thereof, comprising:
(1) In a first solvent, carrying out a first reaction on a compound V and a compound IV in the presence of a first alkaline substance and a condensing agent to obtain a compound III;
(2) In a second solvent, carrying out a second reaction on the compound III and an acidic substance to obtain a compound II;
(3) In a third solvent, in the presence of a second alkaline substance, carrying out a third reaction on the compound II and the sulfonyl-containing compound to obtain the thiazolyl-containing benzimidazole compound or a salt thereof;
wherein the compound V has a structure shown in a formula (V), the compound IV has a structure shown in a formula (IV), the compound III has a structure shown in a formula (III), the compound II has a structure shown in a formula (II), the thiazolyl-containing benzimidazole compound has a structure shown in a formula (I), and the sulfonyl-containing compound has a structure shown in a formula (VI);
R, Y in formula (I), formula (II), formula (III), formula (IV), formula (V) and formula (VI) 1 、Y 2 、Z 1 、Z 2 、Z 3 、Z 4 Is defined as in any one of claims 1 to 4, and X is selected from halogen.
6. The method of claim 5, wherein in step (1), the conditions of the first reaction comprise: the temperature is between 10 ℃ below zero and 150 ℃ above zero, and the reaction time is between 0.1 and 48 hours;
preferably, the molar ratio of the compound V to the compound IV is used in the range of 0.5 to 2:1, a step of;
preferably, the condensing agent is selected from at least one of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide or hydrochloride thereof, carbonyl diimidazole, 1, 3-dicyclohexylcarbodiimide, diethyl cyanophosphate, chlorocarbonate compounds and 2-chloro-1-methylpyridinium iodide;
preferably, the molar ratio of the condensing agent to the compound IV is 1-2:1, a step of;
preferably, the first basic 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, 1, 8-diazabicyclo [5.4.0] undec-7-ene;
Preferably, the molar ratio of the first basic substance to the compound IV is between 0.1 and 10:1.
7. the method of claim 5 or 6, wherein in step (2), the conditions of the second reaction comprise: the temperature is between minus 10 ℃ and minus 300 ℃ and the reaction time is between 0.1 and 48 hours;
preferably, the acidic substance is selected from at least one of p-toluenesulfonic acid or hydrate thereof, methanesulfonic acid, trifluoromethanesulfonic acid, hydrochloric acid, sulfuric acid, nitric acid, formic acid, acetic acid, propionic acid, trifluoroacetic acid, trichloroacetic acid, benzoic acid, phosphoric acid;
preferably, the molar ratio of the acidic substance to the compound IV is in the range of 0.01 to 10:1.
8. the method according to any one of claims 5-7, wherein in step (3), the conditions of the third reaction comprise: the temperature is between minus 10 ℃ and minus 100 ℃ and the reaction time is between 0.1 and 48 hours;
preferably, the molar ratio of the sulfonyl-containing compound to the compound II is in the range of 0.8 to 10:1, a step of;
preferably, the second basic 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, 1, 8-diazabicyclo [5.4.0] undec-7-ene;
Preferably, the molar ratio of the second basic substance to the compound II is between 1 and 10:1.
9. thiazolyl-containing benzimidazole compounds or salts thereof produced by the process according to any one of claims 5 to 8.
10. Use of a thiazolyl-containing benzimidazole compound according to any one of claims 1 to 4 and 9 or a salt thereof for the preparation of an insecticidal acaricide and/or a parasiticide.
11. An insecticidal/acaricidal agent comprising an active ingredient selected from at least one of the thiazolyl-containing benzimidazole compounds or salts thereof according to any one of claims 1 to 4 and 9;
preferably, the active ingredient is present in an amount of 1 to 99% by weight, more preferably 5 to 60% by weight, based on the total weight of the insecticidal and acaricidal agent.
12. Use of the insecticidal and acaricidal agent according to claim 11 for insecticidal and/or acaricidal purposes in agriculture, forestry and horticulture.
13. A parasite control agent, characterized in that it contains an active ingredient selected from at least one of the thiazolyl-containing benzimidazole compounds or salts thereof according to any one of claims 1 to 4 and 9;
Preferably, the active ingredient is present in an amount of 1 to 99% by weight, more preferably 5 to 60% by weight, based on the total weight of the parasite control agent.
14. Use of the parasite control agent according to claim 13 for controlling parasites in and out of animals.
CN202310964957.7A 2022-08-15 2023-08-02 Thiazolyl-containing benzimidazole compound or salt thereof, preparation method, insecticidal acaricide, parasite control agent and application Pending CN117586248A (en)

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