CN112794845A - Isoxazoline pyrazole amide compounds, and preparation method and application thereof - Google Patents

Isoxazoline pyrazole amide compounds, and preparation method and application thereof Download PDF

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CN112794845A
CN112794845A CN201911106591.XA CN201911106591A CN112794845A CN 112794845 A CN112794845 A CN 112794845A CN 201911106591 A CN201911106591 A CN 201911106591A CN 112794845 A CN112794845 A CN 112794845A
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alkyl
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hydrogen
radical
isoxazoline
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CN112794845B (en
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彭伟立
许天明
赵灵杰
吴宁捷
郁季平
钟良坤
刘燕君
胡冬松
郑志文
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Zhejiang Chemical Industry Research Institute Co Ltd
Sinochem Lantian Co Ltd
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Sinochem Lantian Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
    • C07D413/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms 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
    • A01N43/80—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 1,2
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing three or more hetero rings
    • 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
    • C07D417/14—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 three or more hetero rings

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Abstract

The invention discloses an isoxazoline pyrazole amide compound, which has the following structural formula (I):

Description

Isoxazoline pyrazole amide compounds, and preparation method and application thereof
Technical Field
The invention belongs to the field of pesticides, and relates to an isoxazoline pyrazole amide compound.
Background
Effective management of the number of pests is an important agricultural topic. Excessive pest numbers can cause crop yield loss. In agriculture, different insecticides are often used to control pests.
In recent years, isoxazoline compounds show good effect on prevention and control of insects, and attract attention. For example: PCT patent application WO2015132592a1 discloses 4, 5-dihydro-isoxazole compounds useful for controlling endoparasitic and ectoparasitic infections caused by fleas and ticks in animals; PCT patent applications WO2010020522 and WO2018029102 disclose amides useful as harmful arthropod control agents. However, these patents have disclosed that the compounds therein are also capable of controlling only a part of pests and have no controlling effect on lepidopteran pests, mites, aphids and the like.
Therefore, there is a need for the development of new pesticidal compounds for controlling lepidopteran pests, mites, aphids and the like. The prior art does not disclose the compounds described herein, nor does it disclose that compounds having a structure similar to the compounds described herein have pesticidal activity.
Disclosure of Invention
The invention aims to provide a compound with a novel structure, namely: isoxazoline-linked pyrazole amide compounds represented by the general formula (I),
Figure BDA0002271498860000011
the invention provides an isoxazoline pyrazole amide compound represented by a general formula (I), and a substituent R of the isoxazoline pyrazole amide compound1、R2And R3Independently selected from hydrogen, halogen, C1-C20Alkyl radical, C2-C20Alkenyl radical, C2-C20Alkynyl, C1-C20Alkoxy radical, C1-C20Haloalkyl, C2-C20Haloalkenyl, C2-C20Halogenated alkynyl, C1-C20Haloalkoxy, phenoxy, cyano, nitro, hydroxy, formyl, carboxy, C1-C20An alkoxycarbonyl group.
As a preferred embodiment, the substituent R1、R2And R3Independently selected from hydrogen, halogen, C1-C10Alkyl radical, C2-C10Alkenyl radical, C2-C10Alkynyl, C1-C10Alkoxy radical, C1-C10Haloalkyl, C2-C10Haloalkenyl, C2-C10Halogenated alkynyl, C1-C10Haloalkoxy, phenoxy, cyano, nitro, hydroxy, formyl, carboxy, C1-C10An alkoxycarbonyl group.
As another preferred embodiment, the substituent R1、R2And R3Independently selected from hydrogen, halogen, C1-C6Alkyl radical, C2-C6Alkenyl radical, C2-C6Alkynyl, C1-C6Alkoxy radical, C1-C6Haloalkyl, C2-C6Haloalkenyl, C2-C6Halogenated alkynyl, C1-C6Haloalkoxy, phenoxy, cyano, nitro, hydroxy, formyl, carboxy, C1-C6An alkoxycarbonyl group.
As another preferred embodiment, the substituent R1、R2And R3Independently selected from hydrogen, halogen, C1-C3Alkyl radical, C2-C3Alkenyl radical, C2-C3Alkynyl, C1-C3Alkoxy radical, C1-C3Haloalkyl, C2-C3Haloalkenyl, C2-C3Halogenated alkynyl, C1-C3Haloalkoxy, phenoxy, cyano, nitro, hydroxy, formyl, carboxy, C1-C3An alkoxycarbonyl group.
The invention provides an isoxazoline pyrazole amide compound represented by a general formula (I), and a substituent R of the isoxazoline pyrazole amide compound4Selected from hydrogen, C1-C20Alkyl, halo C1-C20An alkyl group.
As a preferred embodiment, the substituent R4Selected from hydrogen, C1-C10Alkyl, halo C1-C10An alkyl group.
As another preferred embodiment, the substituent R4Selected from hydrogen, C1-C6Alkyl, halo C1-C6An alkyl group.
As another preferred embodiment, the substituent R4Selected from hydrogen, C1-C3Alkyl, halo C1-C3An alkyl group.
According to the isoxazoline linked pyrazole amide compound represented by the general formula (I), the carbon atom of the isoxazoline linked pyrazole ring is a chiral carbon atom, and the chiral carbon atom is in a levorotatory configuration and/or a dextrorotatory configuration. Namely, the chiral carbon atom can be in a levorotatory configuration, a dextrorotatory configuration or a mixture of the levorotatory configuration and the dextrorotatory configuration.
The invention provides an isoxazoline pyrazole amide compound represented by a general formula (I), a substituent R5Selected from hydrogen, C1-C20Alkyl radical, C1-C20Haloalkyl, cyano-substituted C1-C20Alkyl, alkynyl substituted C1-C20Alkyl radical, C1-C4Alkoxy-substituted C1-C20Alkyl radical, C1-C4Alkyl substituted C3-C20A cycloalkyl group.
As a preferred embodiment, the substituent R5Selected from hydrogen, C1-C10Alkyl radical, C1-C10Haloalkyl, cyano-substituted C1-C10Alkyl, alkynyl substituted C1-C10Alkyl radical, C1-C4Alkoxy-substituted C1-C10Alkyl radical, C1-C4Alkyl substituted C3-C10A cycloalkyl group.
As another preferred embodiment, the substituent R5Selected from hydrogen, C1-C6Alkyl radical, C1-C6Haloalkyl, cyano-substituted C1-C6Alkyl, alkynyl substituted C1-C6Alkyl radical, C1-C4Alkoxy-substituted C1-C6Alkyl radical, C1-C4Alkyl substituted C3-C6A cycloalkyl group.
As another preferred embodiment, the substituent R5Selected from hydrogen, C1-C3Alkyl radical, C1-C3Haloalkyl, cyano-substituted C1-C3Alkyl, alkynyl substituted C1-C3Alkyl radical, C1-C4Alkoxy-substituted C1-C3Alkyl radical, C1-C4Alkyl substituted C3-C6A cycloalkyl group.
The invention provides an isoxazoline pyrazole amide compound represented by a general formula (I), a substituent R6Selected from hydrogen, C1-C20Alkyl, -X-R7。
As a preferred embodiment, the substituent R6Selected from hydrogen, C1-C10Alkyl, -X-R7。
As another preferred embodiment, the substituent R6Selected from hydrogen, C1-C6Alkyl, -X-R7。
As another preferred embodiment, the substituent R6Selected from hydrogen, C1-C3Alkyl, -X-R7。
The above-mentioned substituent-X-R7And may be at least one selected from three structural formulae shown below:
Figure BDA0002271498860000031
in the three substituents shown in the structural formula, X is independently selected from a direct bond, -CH2-or-CHR8-, and: r8Is selected from C1-C20Alkyl radical, C1-C20Haloalkyl, with R8The connected carbon atoms are chiral carbon atoms, and the chiral carbon atoms are in a levorotatory configuration and/or a dextrorotatory configuration.
As a preferred embodiment, said X is independently selected from the group consisting of a direct bond, -CH2-or-CHR8-, and: r8Is selected from C1-C10Alkyl radical, C1-C10Haloalkyl, with R8The connected carbon atoms are chiral carbon atoms, and the chiral carbon atoms are in a levorotatory configuration and/or a dextrorotatory configuration.
As another preferred embodiment, said X is independently selected from the group consisting of a direct bond, -CH2-or-CHR8-, and: r8Is selected from C1-C6Alkyl radical, C1-C6Haloalkyl, with R8The connected carbon atoms are chiral carbon atoms, and the chiral carbon atoms are in a levorotatory configuration and/or a dextrorotatory configuration.
As another preferred embodiment, said X is independently selected from the group consisting of a direct bond, -CH2-or-CHR8-, and: r8Is selected from C1-C3Alkyl radical, C1-C3Haloalkyl, with R8The connected carbon atoms are chiral carbon atoms, and the chiral carbon atoms are in a levorotatory configuration and/or a dextrorotatory configuration.
In the three substituents shown in the structural formula, Y is independently selected from CH and N.
In the three substituents shown in the structural formula, Z is independently selected fromO、S、NR12And R is12Is selected from C1-C20An alkyl group.
As a preferred embodiment, Z is independently selected from O, S, NR12And R is12Is selected from C1-C10An alkyl group.
As another preferred embodiment, Z is independently selected from O, S, NR12And R is12Is selected from C1-C6An alkyl group.
As another preferred embodiment, Z is independently selected from O, S, NR12And R is12Is selected from C1-C4An alkyl group.
The invention provides an isoxazoline pyrazole amide compound represented by a general formula (I), a substituent R9、R10And R11Independently selected from hydrogen, halogen, C1-C20Alkyl radical, C2-C20Alkenyl radical, C2-C20Alkynyl, C1-C20Alkoxy radical, C1-C20Haloalkyl, C2-C20Haloalkenyl, C2-C20Halogenated alkynyl, C1-C20Haloalkoxy, phenoxy, cyano, nitro, hydroxy, formyl, carboxy, C1-C20Alkoxycarbonyl, halo C1-C20An alkoxycarbonyl group.
As a preferred embodiment, the substituent R9、R10And R11Independently selected from hydrogen, halogen, C1-C10Alkyl radical, C2-C10Alkenyl radical, C2-C10Alkynyl, C1-C10Alkoxy radical, C1-C10Haloalkyl, C2-C10Haloalkenyl, C2-C10Halogenated alkynyl, C1-C10Haloalkoxy, phenoxy, cyano, nitro, hydroxy, formyl, carboxy, C1-C10Alkoxycarbonyl, halo C1-C10An alkoxycarbonyl group.
As another preferred embodiment, the substitution isRadical R9、R10And R11Independently selected from hydrogen, halogen, C1-C6Alkyl radical, C2-C6Alkenyl radical, C2-C6Alkynyl, C1-C6Alkoxy radical, C1-C6Haloalkyl, C2-C6Haloalkenyl, C2-C6Halogenated alkynyl, C1-C6Haloalkoxy, phenoxy, cyano, nitro, hydroxy, formyl, carboxy, C1-C6Alkoxycarbonyl, halo C1-C6An alkoxycarbonyl group.
As another preferred embodiment, the substituent R9、R10And R11Independently selected from hydrogen, halogen, C1-C3Alkyl radical, C2-C3Alkenyl radical, C2-C3Alkynyl, C1-C3Alkoxy radical, C1-C3Haloalkyl, C2-C3Haloalkenyl, C2-C3Halogenated alkynyl, C1-C3Haloalkoxy, phenoxy, cyano, nitro, hydroxy, formyl, carboxy, C1-C3Alkoxycarbonyl, halo C1-C3An alkoxycarbonyl group.
The invention provides an isoxazoline pyrazole amide compound represented by a general formula (I), a substituent R5And R6In addition to the above definitions, it is also possible to: r5And R6Together with the attached N, form one of the following 5 ring structures:
Figure BDA0002271498860000041
among the above-mentioned 5 substituents represented by the cyclic structure, R12And R13Independently selected from hydrogen, halogen, C1-C20Alkyl radical, C1-C20Alkoxy radical, C1-C20Haloalkyl, C1-C20A haloalkoxy group.
As a preferred embodiment, theR12And R13Independently selected from hydrogen, halogen, C1-C10Alkyl radical, C1-C10Alkoxy radical, C1-C10Haloalkyl, C1-C10A haloalkoxy group.
As another preferred embodiment, the substituent R12And R13Independently selected from hydrogen, halogen, C1-C6Alkyl radical, C1-C6Alkoxy radical, C1-C6Haloalkyl, C1-C6A haloalkoxy group.
As another preferred embodiment, the substituent R12And R13Independently selected from hydrogen, halogen, C1-C3Alkyl radical, C1-C3Alkoxy radical, C1-C3Haloalkyl, C1-C3A haloalkoxy group.
In the substituents represented by the above 5 cyclic structures, A is selected from C, O, NR14And R is14Selected from hydrogen, C1-C20Alkyl, formyl, C1-C20Alkylcarbonyl, halo C1-C20An alkylcarbonyl group.
As a preferred embodiment, A is selected from C, O, NR14And R is14Selected from hydrogen, C1-C10Alkyl, formyl, C1-C10Alkylcarbonyl, halo C1-C10An alkylcarbonyl group.
As another preferred embodiment, the substituent A is selected from the group consisting of C, O, NR14And R is14Selected from hydrogen, C1-C6Alkyl, formyl, C1-C6Alkylcarbonyl, halo C1-C6An alkylcarbonyl group.
As another preferred embodiment, the substituent A is selected from the group consisting of C, O, NR14And R is14Selected from hydrogen, C1-C3Alkyl, formyl, C1-C3Alkylcarbonyl, halo C1-C3An alkylcarbonyl group.
In a more preferred embodiment, the isoxazoline-pyrazole amide compound represented by the general formula (I) provided by the present invention is at least one compound selected from the following compounds:
Figure BDA0002271498860000051
Figure BDA0002271498860000061
among the substituents described in the present invention: alkyl means straight or branched chain forms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, n-hexyl and the like; cycloalkyl is meant to include cyclic chain forms such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and the like; haloalkyl refers to a group in which the alkyl group is substituted with one or more halogen atoms; alkoxy means a group having an oxygen atom attached to the end of an alkyl group, such as methoxy, ethoxy, n-propoxy, isopropoxy, t-butoxy, etc.; haloalkoxy means a group in which an alkyl group is substituted with one or more halogen atoms and an oxygen atom is attached to the terminal; halogen refers to fluorine, chlorine, bromine, iodine; the direct bond being R7The group is directly attached to the N atom of the amide.
The typical compounds of the isoxazoline-pyrazole amide compound represented by the general formula (I) provided by the invention are listed in Table 1. The typical compounds shown in table 1 do not limit the scope of the isoxazoline-pyrazole amides represented by the general formula (I) of the present invention.
Figure BDA0002271498860000071
TABLE 1 partial typical Compounds and nuclear magnetic hydrogen Spectroscopy data
Figure BDA0002271498860000072
Figure BDA0002271498860000081
Figure BDA0002271498860000091
Figure BDA0002271498860000101
Figure BDA0002271498860000111
Figure BDA0002271498860000121
Figure BDA0002271498860000131
Figure BDA0002271498860000141
Figure BDA0002271498860000151
Figure BDA0002271498860000161
Figure BDA0002271498860000171
Figure BDA0002271498860000181
Figure BDA0002271498860000191
Figure BDA0002271498860000201
Figure BDA0002271498860000211
In table 1: s is singlet, b is broad singlet, d is doublet, dd is doublet, t is triplet, q is quartet, and m is multiplet. Chiral isomers exist when 2 chiral centers exist in the molecular structure, and the nuclear magnetic hydrogen spectrum part groups split at peak positions, such as I078, I084 and I111.
The invention also provides a preparation method of the isoxazoline pyrazole amide compound represented by the general formula (I), which comprises the following steps:
Figure BDA0002271498860000221
wherein: substituent R1、R2、R3、R4、R5、R6The definition of (a) and (b) is as described above.
As a preferred embodiment, the present invention provides a preparation method comprising:
(1) under the action of hydroxylamine hydrochloride, the raw material (I-1) generates an intermediate (I-2);
(2) in an organic solvent, the intermediate (I-2), N-chlorobutadiene diimide, R4Reacting the substituted intermediate (I-6) with triethylamine to generate an intermediate (I-3);
(3) the intermediate (I-3) is hydrolyzed and acidified to generate an intermediate (I-4);
(4) reacting the intermediate (I-4) with an acyl chlorination reagent in an organic solvent to generate an intermediate (I-5);
(5) the intermediate (I-5) is reacted with R in the presence of a base in an organic solvent6R5The substituted amine reacts to generate the isoxazoline pyrazole amide compound shown in the general formula (I).
As another preferred embodiment, the present invention provides a preparation method comprising:
(1) under the action of hydroxylamine hydrochloride, the raw material (I-1) generates an intermediate (I-2);
(2) reacting the intermediate (I-2) with N-chlorobutadiene diimide in an organic solvent at the temperature of 0-100 ℃, and then reacting with R4Reacting the substituted intermediate (I-6) with triethylamine to produce an intermediate (I-3), wherein the organic solvent is at least one selected from N, N-dimethylformamide, toluene, dichloromethane, trichloromethane, carbon tetrachloride, tetrahydrofuran and dimethylsulfoxide;
(3) in a sodium hydroxide-water soluble organic solvent system, the intermediate (I-3) is hydrolyzed and acidified to generate an intermediate (I-4);
(4) reacting the intermediate (I-4) with an acylchlorinating agent selected from at least one of thionyl chloride and oxalyl chloride in an organic solvent selected from at least one of N, N-dimethylformamide, toluene, dichloromethane, chloroform, carbon tetrachloride, tetrahydrofuran and dimethylsulfoxide to produce an intermediate (I-5);
(5) the intermediate (I-5) is reacted with R in the presence of a base in an organic solvent6R5The substituted amine reacts to generate the isoxazoline pyrazole amide compound represented by the general formula (I), wherein the base is at least one of organic base and inorganic base, and the organic solvent is at least one of N, N-dimethylformamide, toluene, dichloromethane, trichloromethane, carbon tetrachloride, tetrahydrofuran and dimethyl sulfoxide.
As another preferred embodiment, the present invention provides a preparation method comprising:
(1) under the action of hydroxylamine hydrochloride, the raw material (I-1) generates an intermediate (I-2);
(2) reacting the intermediate (I-2) with N-chlorobutadiene diimide in an organic solvent at the temperature of 0-100 ℃, and then reacting with R4In substitution ofReacting the intermediate (I-6) with triethylamine to generate an intermediate (I-3), wherein the organic solvent is at least one selected from N, N-dimethylformamide, toluene, dichloromethane, trichloromethane, carbon tetrachloride, tetrahydrofuran and dimethyl sulfoxide;
(3) in a sodium hydroxide-water soluble organic solvent system, the intermediate (I-3) is hydrolyzed and acidified to generate an intermediate (I-4);
(4) reacting the intermediate (I-4) with an acyl chlorination reagent selected from at least one of thionyl chloride and oxalyl chloride in an organic solvent selected from at least one of dichloromethane, trichloromethane and carbon tetrachloride to produce an intermediate (I-5);
(5) the intermediate (I-5) is reacted with R in the presence of a base in an organic solvent6R5Reacting substituted amine to generate isoxazoline pyrazole amide compounds represented by general formula (I), wherein the base is at least one of triethylamine and potassium carbonate which are organic bases; the organic solvent is at least one selected from the group consisting of toluene, dichloromethane, and tetrahydrofuran.
The invention also provides application of the isoxazoline pyrazole amide compound shown in the general formula (I), and the isoxazoline pyrazole amide compound is used for killing insects. As a preferred mode, the isoxazoline-linked pyrazole amide compound is particularly suitable for controlling at least one pest selected from lepidoptera pests, mites and aphids. As another preferable mode, the isoxazoline pyrazole amide compound represented by the formula (I) is suitably used for controlling at least one pest selected from the group consisting of diamond back moth, cabbage looper, prodenia litura, beet armyworm, spodoptera frugiperda, cotton bollworm, oriental armyworm, tobacco budworm, agrotis punctifera, portulaca punctata, codling moth, peach fruit moth, oriental fruit moth, black cutworm, potato beetle, yellow melon, aphid, whitefly, thrips, locust and leaf miner. As another more preferred mode, the isoxazoline-linked pyrazole amide-based compound is particularly suitable for controlling at least one pest selected from the group consisting of armyworm, cotton bollworm, aphid alfalfa, plutella xylostella, prodenia litura and spodoptera frugiperda.
The isoxazoline pyrazole amide compound shown in the general formula (I) is particularly suitable for controlling pests in rice, soybean, wheat, cotton, corn, vegetables and rape.
The invention also provides a pesticide preparation, which contains 0.001-99.99 wt% of isoxazoline pyrazole amide compounds shown in the general formula (I), and the balance of agriculturally acceptable carriers.
In formulating pesticide formulations, the carrier may be a solid or a liquid. Suitable solid carriers include natural or synthetic clays and silicates, such as natural silica and diatomaceous earth; magnesium silicates such as talc; magnesium aluminum silicates such as kaolinite, montmorillonite and mica; white carbon black, calcium carbonate, light calcium carbonate; calcium sulfate; limestone; sodium sulfate; amine salts such as ammonium sulfate, hexamethylene diamine. Liquid carriers include water and organic solvents, which can also be used as adjuvants or antifreeze additives when water is used as a solvent or diluent. Suitable organic solvents include aromatic hydrocarbons such as benzene, xylene, toluene, and the like; chlorinated hydrocarbons such as chlorobenzene, vinyl chloride, chloroform, dichloromethane, and the like; aliphatic hydrocarbons such as petroleum fractions, cyclohexane, light mineral oil; alcohols such as isopropyl alcohol, butyl alcohol, ethylene glycol, glycerin, cyclohexanol, and the like; and ethers and esters thereof; and also ketones, such as acetone, cyclohexanone, and dimethylformamide and N-methyl-pyrrolidone.
The carrier may also be a surfactant. Suitable surfactants may be emulsifying agents, dispersing agents or wetting agents; may be ionic or non-ionic. Nonionic emulsifiers such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, polyoxyethylene fatty ammonia, and commercially available emulsifiers: nongru 2201B, Nongru 0203B and Nongru 100#Agricultural milk 500#Agricultural milk 600#Agricultural milk 600-2#1601, 2201, NP-10, NP-15 and 507#Agricultural milk OX-635, agricultural milk OX-622, agricultural milk OX-653, agricultural milk OX-667, Ningru 36#. The dispersant comprises sodium lignosulfonate, nekal, calcium lignosulfonate, and methyl naphthalene sulfonic acidAcid formaldehyde condensates, and the like. The wetting agent is: sodium lauryl sulfate, sodium dodecylbenzenesulfonate, sodium alkylnaphthalenesulfonate, and the like.
The pesticide preparation provided by the invention can be prepared into missible oil, suspending agent, water suspending agent, microemulsion, (water) emulsion, powder, wettable powder, soluble powder, (water dispersible) granules or capsules and the like.
The pesticide preparation provided by the invention can be prepared by a general method. For example, the active substance is mixed with a liquid solvent and/or a solid carrier, with the addition of surfactants, such as, for example, emulsifiers, dispersants, stabilizers, wetting agents, and also with the addition of further auxiliaries, such as, for example: binders, defoamers, oxidizing agents, and the like.
The isoxazoline pyrazole amide compound shown in the general formula (I) can also be mixed with herbicides, bactericides, nematicides, plant growth regulators, fertilizers and other insecticides or other agricultural chemicals for use.
In the control of pests, the pesticidal preparation according to the present invention should be applied to pests to be controlled or a medium for their growth, wherein the effective amount of the active ingredient, i.e., the isoxazoline pyrazolecarboxamide-based compound represented by the general formula (I), is from 10 g to 1000 g per hectare.
Compared with the prior art, the isoxazoline pyrazole amide compound shown in the general formula (I) and the preparation thereof have the following advantages:
(1) the compound has novel structure;
(2) the insecticidal activity is high, and the insecticidal composition can be used for controlling insect pests;
(3) the safety is good, and the safety is good for partial crops such as wheat, soybean, cotton, corn, rice and the like.
Detailed Description
The present invention is further illustrated by the following examples, which are not intended to limit the invention to these embodiments. It will be appreciated by those skilled in the art that the present invention encompasses all alternatives, modifications and equivalents as may be included within the scope of the claims.
First, compound synthesis
Example 1 Synthesis of the target Compound I111
(1) Synthesis of intermediate (I-2): r1R2R3＝3-F
Preparation of aqueous hydroxylamine solution: an aqueous hydroxylamine solution was prepared by mixing 3.13g of hydroxylamine hydrochloride and 2.46g of sodium acetate, adding 15mL of water, and stirring at room temperature.
30mmol of 3-fluorobenzaldehyde were dissolved in 20mL of THF, the aqueous hydroxylamine solution prepared was added dropwise at room temperature, and stirring was continued for 2 hours after completion of the addition. After complete reaction, THF was removed by desolventizing, water was added, filtration was carried out, washing with water and air-drying to obtain 3.65g of a white solid.
R1R2R3As the starting material (I-1) for the other substituent, the corresponding intermediate (I-2) was synthesized using the same method as the reference.
(2) Synthesis of intermediate (I-3): r1R2R3＝3-F，R4＝Me
1.39g of intermediate (I-2) produced in the above (1) was charged into a 250mL round-bottomed flask, and 30mL of N, N-Dimethylformamide (DMF) was added as a solvent to dissolve it, 1.74g N-chlorosuccinimide (NCS) was added, and the mixture was heated to 60 ℃ and stirred for 2 hours, cooled to room temperature, and 1.71g of intermediate (I-6) (R)4Me), 1.40g of triethylamine was added dropwise thereto, the mixture was stirred at room temperature for 4 hours after the addition, the mixture was poured into 150mL of ice water, extracted with ethyl acetate (3 times 50mL each), dried and concentrated over magnesium sulfate, and then separated by column chromatography (developing solvent petroleum ether: ethyl acetate: 3:1) to obtain 1.40g of a viscous liquid.
R1R2R3R4The starting intermediate (I-3) which is another substituent can be synthesized by the same method as described above.
(3) Synthesis of intermediate (I-4): r1R2R3＝3-F，R4＝Me
Intermediate (I-3: R)1R2R3＝3-F，R4Me)1.40g was dissolved in a mixture of 10mL Tetrahydrofuran (THF) and 5mL water, 1.25 equivalents of sodium hydroxide was added, heated under reflux for 2h, cooled, and concentrated to remove THF, 20mL of water is added, the pH is adjusted to acidity with hydrochloric acid, and a white solid appears. The solution was filtered, washed with water and dried to obtain 1.14g of a white solid.
The nuclear magnetic data of the obtained white solid are as follows:
1H NMR(600MHz,DMSO)δ:7.31-7.58(m,4H,Ph-H),6.91(s,1H,Pyrazole-H),5.72-5.75(q,1H,Isoxazole-H),4.06(s,3H,Pyrazole-CH3),3.26-3.80(m,2H,Isoxazole-CH2).
R1R2R3R4the starting intermediate (I-4) which is another substituent can be synthesized by the same method as described above.
(4) Synthesis of intermediate (I-5) R1R2R3＝3-F，R4＝Me
Intermediate (I-4: R)1R2R3＝3-F,R4Me)0.3mmol was added to 10mL of dichloromethane, 1 drop of DMF was added, 0.4mmol of oxalyl chloride was dropped into the reaction solution, the reaction was heated under reflux for 1 hour, the solvent was distilled off at normal temperature, and the solvent was dried under reduced pressure with a diaphragm pump to obtain a residual liquid. The residue was used directly in the next step without work-up to synthesize the compound.
R1R2R3R4The starting intermediate (I-5) which is another substituent can be synthesized by the same method as described above.
(5) Synthesis of I111:
the intermediate (I-5: R) obtained in the above reaction (4)1R2R3＝3-F,R4Me)0.3mmol was dissolved in 5mL of anhydrous THF, 0.36mmol triethylamine was added, 0.3mmol 2-methylcyclohexylamine was added at room temperature, stirred at room temperature for 2 hours, and chromatographed (developing solvent petroleum ether: ethyl acetate 3:1) to give a white solid. The yield was 84%.
The white solid obtained was:
Figure BDA0002271498860000261
the nuclear magnetic data are:1H NMR(600MHZ,CDCl3/TMS):δ:7.09～7.44(m,6H,Ph-H),6.61(s,2H, Pyrazole-H),6.11(B,1H, isomer A-NH),6.10(B,1H, isomer B-NH),5.76-5.81(q,2H, Isoxazole-H),4.12(s,6H, Pyrazole-CH)3),3.61～3.69(m,4H,Isoxazole-CH2) 4.16-4.20(m,1H, isomer A-NCH),3.56-3.60(m,1H, isomer B-NCH), 1.09-1.98 (m,18H, cyclohexane grade CH + CH)2) 0.89 to 0.92(t,3H, isomer A-CH)3) 0.93-0.96(t,3H, isomer B-CH)3).
As 2 chiral carbon atoms exist in the molecule, one is the carbon atom connected with pyrazole on the isoxazole ring and the other is the carbon atom connected with methyl on the cyclohexyl, the raw materials are all mixed helices, the molecule has four configurations of chiral RR, RS, SR and SS, 2 of the chiral RR, RS, SR and SS can be distinguished in the nuclear magnetic hydrogen spectrum, and NH, NCH and CH can be seen without distinguishing and naming as isomer A and isomer B3The isoradical nuclear magnetic hydrogen spectrum is split into two types.
Other compounds of the invention may be synthesized by the same method as referenced above.
Second, preparation of preparation
The following examples show the preparation prepared by using the isoxazoline pyrazole amide compound shown in the general formula (I) provided by the invention as an active substance component. In the following examples, all "%" refer to weight percent.
Example 2 wettable powder
15% of compound (I) (i.e. the compound shown in Table 1, may be a single compound or a mixture of a plurality of compounds), 5% of lignosulfonate (M)q) Uniformly mixing 1% of lauryl alcohol polyoxyethylene ether (JFC), 40% of diatomite and 44% of light calcium carbonate, and crushing to obtain the wettable powder.
Example 3 emulsifiable concentrate
Heating and stirring 10% of compound (I) (i.e. the compound shown in Table 1 can be a single compound or a mixture of a plurality of compounds), 5% of Nongru No. 500 (calcium salt), 5% of Nongru No. 602, 5% of N-methyl-2-pyrrolidone and 75% of xylene uniformly to obtain the emulsifiable concentrate.
Example 4 granules
Uniformly mixing 5% of compound (I) (i.e., the compound shown in Table 1, which may be a single compound or a mixture of a plurality of compounds), 1% of polyvinyl alcohol (PVA), 4% of sodium naphthalene sulfonate formaldehyde condensate (NMO) and 90% of clay, pulverizing, adding 20 parts of water to 100 parts of the mixture, kneading, extruding into granules of 14-32 mesh, and drying to obtain granules.
Example 5 Water-dispersible granule
20% of the compound (I) (i.e., the compound shown in Table 1, which may be a single compound or a mixture of a plurality of compounds), 4% of a naphthalenesulfonate formaldehyde condensate, 1% of naphthalenesulfonate, 2% of white carbon black and 73% of kaolin were mixed and pulverized, and then kneaded with water, and then fed into a granulator equipped with a sieve of a predetermined size to granulate. Then drying and screening (according to the range of a screen) to obtain a granular product.
Example 6 aqueous suspension
20% of a compound (I) (namely the compound shown in the table 1 can be a single compound or a mixture of a plurality of compounds), 1% of fatty alcohol-polyoxyethylene ether, 3% of rosin block polyoxyethylene ether polyoxypropylene ether sulfonate, 1% of magnesium aluminum silicate, 0.4% of an organic silicon defoamer, 5% of propylene glycol and deionized water (69.5%) are mixed uniformly in advance, then the mixture is added into a sand mill for sand milling, suspension mother liquor is obtained after filtration, and the prepared xanthan gum (0.1%) aqueous solution is added for shearing and mixing uniformly.
Third, Activity test
Examples of biological activity assays using the compounds of the present invention are given below, it being noted that the present invention is not limited solely to the scope of the following examples.
Example 7 insecticidal Activity assay
The insecticidal activity evaluation test was carried out according to the following method:
weighing a certain mass of original drug by using an analytical balance (0.0001g), dissolving the original drug by using DMF (dimethyl formamide) containing 1% of Tween-80 emulsifier to prepare 1-2.5% of mother liquor, and then diluting the mother liquor by using distilled water for later use.
Leaf soaking method: the target for testing is armyworm, namely, a proper amount of corn leaves are fully soaked in prepared liquid medicine and then naturally dried in the shade, the corn leaves are placed into a culture dish filled with filter paper, 10 heads/dish of armyworm larvae in the 3-instar middle stage are connected, the corn leaves are placed into an observation room for culture at 24-27 ℃, and the result is investigated after 3 days. If the body of the insect is touched by a brush pen, no response is regarded as dead insect.
Spraying method: the test targets are tetranychus cinnabarinus and alfalfa aphid, namely broad bean leaves connected with tetranychus cinnabarinus and alfalfa aphid are respectively placed under a Potter spray tower for spray treatment, the tetranychus cinnabarinus after treatment is placed in an observation room at the temperature of 24-27 ℃ for culture, the alfalfa aphid is placed in the observation room at the temperature of 20-22 ℃ for culture, and the result is investigated after 48 hours. If the body of the insect is touched by a brush pen, no response is regarded as dead insect.
And (3) test statistics: and counting the number of dead insects and the number of live insects of each treatment, and calculating the mortality. The mortality calculation formula is as follows:
Figure BDA0002271498860000281
the CK control mortality rate is less than 20%, the test result is credible, the test result is corrected, and the CK control mortality rate can not be corrected when the CK control mortality rate is less than 5%.
The results of the biological tests show that:
at the concentration of 500mg/L, the death rates of armyworms treated by the compounds I034-I061, I063-I087, I089-I093, I095, I096, I098-I107, I110, I111, I113-I119, I121, I122 and I124-I126 are all higher than 80 percent, even reach 100 percent and are generally less in feeding.
At a concentration of 500mg/L, the mortality rate of tetranychus cinnabarinus treated by the compound I055I 085I 095I 096I 110I 111 is higher than 80%.
At a concentration of 500mg/L, the mortality of the alfalfa aphids treated with compounds I036, I014, I053, I054, I058, I061, I068, I069, I072, I077, I079, I088, I098, I099, I100, I101, I106, I108, I111, I113, I116, I118, I121, I124 was all higher than 80%.

Claims (15)

1. An isoxazoline-linked pyrazole amide compound represented by the general formula (I):
Figure RE-FDA0002349532280000011
wherein:
R1、R2and R3Independently selected from hydrogen, halogen, C1-C20Alkyl radical, C2-C20Alkenyl radical, C2-C20Alkynyl, C1-C20Alkoxy radical, C1-C20Haloalkyl, C2-C20Haloalkenyl, C2-C20Halogenated alkynyl, C1-C20Haloalkoxy, phenoxy, cyano, nitro, hydroxy, formyl, carboxy, C1-C20An alkoxycarbonyl group;
R4selected from hydrogen, C1-C20Alkyl, halo C1-C20An alkyl group;
the isoxazole ring carbon atom connected with the pyrazole ring is a chiral carbon atom, and the chiral carbon atom is in a levorotatory configuration and/or a dextrorotatory configuration;
R5selected from hydrogen, C1-C20Alkyl radical, C1-C20Haloalkyl, cyano-substituted C1-C20Alkyl, alkynyl substituted C1-C20Alkyl radical, C1-C4Alkoxy-substituted C1-C20Alkyl radical, C1-C4Alkyl substituted C3-C20A cycloalkyl group;
R6selected from hydrogen, C1-C20Alkyl, -X-R7And said-X-R7At least one selected from the three structural formulae shown below:
Figure RE-FDA0002349532280000012
and:
x is independently selected from a direct bond, -CH2-or-CHR8-, and: r8Is selected from C1-C20Alkyl radical, C1-C20Haloalkyl, with R8The connected carbon atoms are chiral carbon atoms, the chiral carbon atoms are in a levorotatory configuration and/or a dextrorotatory configuration,
y is independently selected from the group consisting of CH, N,
z is independently selected from O, S, NR12And R is12Is selected from C1-C20An alkyl group, a carboxyl group,
R9、R10and R11Independently selected from hydrogen, halogen, C1-C20Alkyl radical, C2-C20Alkenyl radical, C2-C20Alkynyl, C1-C20Alkoxy radical, C1-C20Haloalkyl, C2-C20Haloalkenyl, C2-C20Halogenated alkynyl, C1-C20Haloalkoxy, phenoxy, cyano, nitro, hydroxy, formyl, carboxy, C1-C20Alkoxycarbonyl, halo C1-C20An alkoxycarbonyl group;
the R is5And R6It is also possible to form, together with the N attached, one of the following 5 cyclic structures:
Figure RE-FDA0002349532280000021
and:
R12and R13Independently selected from hydrogen, halogen, C1-C20Alkyl radical, C1-C20Alkoxy radical, C1-C20Haloalkyl, C1-C20A halogenated alkoxy group,
a is selected from C, O, NR14And R is14Selected from hydrogen, C1-C20Alkyl, formyl, C1-C20Alkylcarbonyl, halo C1-C20An alkylcarbonyl group.
2. Isoxazoline-linked pyrazole amide compound represented by the general formula (I) according to claim 1, wherein in the general formula (I):
R1、R2and R3Independently selected from hydrogen, halogen, C1-C10Alkyl radical, C2-C10Alkenyl radical, C2-C10Alkynyl, C1-C10Alkoxy radical, C1-C10Haloalkyl, C2-C10Haloalkenyl, C2-C10Halogenated alkynyl, C1-C10Haloalkoxy, phenoxy, cyano, nitro, hydroxy, formyl, carboxy, C1-C10An alkoxycarbonyl group;
R4selected from hydrogen, C1-C10Alkyl, halo C1-C10An alkyl group;
R5selected from hydrogen, C1-C10Alkyl radical, C1-C10Haloalkyl, cyano-substituted C1-C10Alkyl, alkynyl substituted C1-C10Alkyl radical, C1-C4Alkoxy-substituted C1-C10Alkyl radical, C1-C4Alkyl substituted C3-C10A cycloalkyl group;
R6selected from hydrogen, C1-C10Alkyl, -X-R7And said-X-R7At least one selected from the three structural formulae shown below:
Figure RE-FDA0002349532280000022
and:
x is independently selected from a direct bond, -CH2-or-CHR8-, and: r8Is selected from C1-C10Alkyl radical, C1-C10Haloalkyl, with R8The connected carbon atoms are chiral carbon atoms, the chiral carbon atoms are in a levorotatory configuration and/or a dextrorotatory configuration,
y is independently selected from the group consisting of CH, N,
z is independently selected from O, S, NR12And R is12Is selected from C1-C10An alkyl group, a carboxyl group,
R9、R10and R11Independently selected from hydrogen, halogen, C1-C10Alkyl radical, C2-C10Alkenyl radical, C2-C10Alkynyl, C1-C10Alkoxy radical, C1-C10Haloalkyl, C2-C10Haloalkenyl, C2-C10Halogenated alkynyl, C1-C10Haloalkoxy, phenoxy, cyano, nitro, hydroxy, formyl, carboxy, C1-C10Alkoxycarbonyl, halo C1-C10An alkoxycarbonyl group;
the R is5And R6It is also possible to form, together with the N attached, one of the following 5 cyclic structures:
Figure RE-FDA0002349532280000031
and:
R12and R13Independently selected from hydrogen, halogen, C1-C10Alkyl radical, C1-C10Alkoxy radical, C1-C10Haloalkyl, C1-C10A halogenated alkoxy group,
a is selected from C, O, NR14And R is14Selected from hydrogen, C1-C10Alkyl, formyl, C1-C10Alkylcarbonyl, halo C1-C10An alkylcarbonyl group.
3. Isoxazoline-linked pyrazole amide-based compound represented by the general formula (I) according to claim 2, wherein in the general formula (I):
R1、R2and R3Independently selected from hydrogen, halogen, C1-C6Alkyl radical, C2-C6Alkenyl radical, C2-C6Alkynyl, C1-C6Alkoxy radical, C1-C6Haloalkyl, C2-C6Haloalkenyl, C2-C6Halogenated alkynyl, C1-C6Haloalkoxy, phenoxy, cyano, nitro, hydroxy, formyl, carboxy, C1-C6An alkoxycarbonyl group;
R4selected from hydrogen, C1-C6Alkyl, halo C1-C6An alkyl group;
R5selected from hydrogen, C1-C6Alkyl radical, C1-C6Haloalkyl, cyano-substituted C1-C6Alkyl, alkynyl substituted C1-C6Alkyl radical, C1-C4Alkoxy-substituted C1-C6Alkyl radical, C1-C4Alkyl substituted C3-C6A cycloalkyl group;
R6selected from hydrogen, C1-C6Alkyl, -X-R7And said-X-R7At least one selected from the three structural formulae shown below:
Figure RE-FDA0002349532280000032
and:
x is independently selected from a direct bond, -CH2-or-CHR8-, and: r8Is selected from C1-C6Alkyl radical, C1-C6Haloalkyl, with R8The connected carbon atoms are chiral carbon atoms, the chiral carbon atoms are in a levorotatory configuration and/or a dextrorotatory configuration,
y is independently selected from the group consisting of CH, N,
z is independently selected from O, S, NR12And R is12Is selected from C1-C6An alkyl group, a carboxyl group,
R9、R10and R11Independently selected from hydrogen, halogen, C1-C6Alkyl radical, C2-C6Alkenyl radical, C2-C6Alkynyl, C1-C6Alkoxy radical, C1-C6Haloalkyl, C2-C6Haloalkenyl, C2-C6Halogenated alkynyl, C1-C6Haloalkoxy, phenoxy, cyano, nitro, hydroxy, formyl, carboxy, C1-C6Alkoxycarbonyl, halo C1-C6An alkoxycarbonyl group;
the R is5And R6Can also be constructed together with the N connectedInto one of the following 5 cyclic structures:
Figure RE-FDA0002349532280000041
and:
R12and R13Independently selected from hydrogen, halogen, C1-C6Alkyl radical, C1-C6Alkoxy radical, C1-C6Haloalkyl, C1-C6A halogenated alkoxy group,
a is selected from C, O, NR14And R is14Selected from hydrogen, C1-C6Alkyl, formyl, C1-C6Alkylcarbonyl, halo C1-C6An alkylcarbonyl group.
4. Isoxazoline-linked pyrazole amide-based compound represented by the general formula (I) according to claim 3, wherein in the general formula (I):
R1、R2and R3Independently selected from hydrogen, halogen, C1-C3Alkyl radical, C2-C3Alkenyl radical, C2-C3Alkynyl, C1-C3Alkoxy radical, C1-C3Haloalkyl, C2-C3Haloalkenyl, C2-C3Halogenated alkynyl, C1-C3Haloalkoxy, phenoxy, cyano, nitro, hydroxy, formyl, carboxy, C1-C3An alkoxycarbonyl group;
R4selected from hydrogen, C1-C3Alkyl, halo C1-C3An alkyl group;
R5selected from hydrogen, C1-C3Alkyl radical, C1-C3Haloalkyl, cyano-substituted C1-C3Alkyl, alkynyl substituted C1-C3Alkyl radical, C1-C4Alkoxy-substituted C1-C3Alkyl radical, C1-C4Alkyl substituted C3-C6A cycloalkyl group;
R6selected from hydrogen, C1-C3Alkyl, -X-R7And said-X-R7At least one selected from the three structural formulae shown below:
Figure RE-FDA0002349532280000042
and:
x is independently selected from a direct bond, -CH2-or-CHR8-, and: r8Is selected from C1-C3Alkyl radical, C1-C3Haloalkyl, with R8The connected carbon atoms are chiral carbon atoms, the chiral carbon atoms are in a levorotatory configuration and/or a dextrorotatory configuration,
y is independently selected from the group consisting of CH, N,
z is independently selected from O, S, NR12And R is12Is selected from C1-C4An alkyl group, a carboxyl group,
R9、R10and R11Independently selected from hydrogen, halogen, C1-C3Alkyl radical, C2-C3Alkenyl radical, C2-C3Alkynyl, C1-C3Alkoxy radical, C1-C3Haloalkyl, C2-C3Haloalkenyl, C2-C3Halogenated alkynyl, C1-C3Haloalkoxy, phenoxy, cyano, nitro, hydroxy, formyl, carboxy, C1-C3Alkoxycarbonyl, halo C1-C3An alkoxycarbonyl group;
the R is5And R6It is also possible to form, together with the N attached, one of the following 5 cyclic structures:
Figure RE-FDA0002349532280000051
and:
R12and R13Independently selected from hydrogen, halogen, C1-C3Alkyl radical, C1-C3Alkoxy radical, C1-C3Haloalkyl, C1-C3A halogenated alkoxy group,
selection AFrom C, O, NR14And R is14Selected from hydrogen, C1-C3Alkyl, formyl, C1-C3Alkylcarbonyl, halo C1-C3An alkylcarbonyl group.
5. The isoxazoline-pyrazole amide compound represented by the general formula (I) according to claim 4, wherein the isoxazoline-pyrazole amide compound represented by the general formula (I) is at least one compound selected from the group consisting of:
Figure RE-FDA0002349532280000052
Figure RE-FDA0002349532280000061
Figure RE-FDA0002349532280000071
6. a process for producing an isoxazoline-pyrazolecarboxamide compound represented by the general formula (I) according to claim 1, which comprises:
Figure RE-FDA0002349532280000072
wherein: substituent R1、R2、R3、R4、R5、R6Is as defined in claim 1.
7. The method for producing an isoxazoline-pyrazolecarboxamide compound according to claim 6, characterized by comprising:
(1) under the action of hydroxylamine hydrochloride, the raw material (I-1) generates an intermediate (I-2);
(2) in an organic solvent, the intermediate (I-2), N-chlorobutadiene diimide, R4Reacting the substituted intermediate (I-6) with triethylamine to generate an intermediate (I-3);
(3) the intermediate (I-3) is hydrolyzed and acidified to generate an intermediate (I-4);
(4) reacting the intermediate (I-4) with an acyl chlorination reagent in an organic solvent to generate an intermediate (I-5);
(5) the intermediate (I-5) is reacted with R in the presence of a base in an organic solvent6R5The substituted amine reacts to generate the isoxazoline pyrazole amide compound shown in the general formula (I).
8. The process for producing an isoxazoline-pyrazolecarboxamide-based compound represented by the general formula (I) according to claim 7, which comprises:
(1) under the action of hydroxylamine hydrochloride, the raw material (I-1) generates an intermediate (I-2);
(2) reacting the intermediate (I-2) with N-chlorobutadiene diimide in an organic solvent at the temperature of 0-100 ℃, and then reacting with R4Reacting the substituted intermediate (I-6) with triethylamine to produce an intermediate (I-3), wherein the organic solvent is at least one selected from N, N-dimethylformamide, toluene, dichloromethane, trichloromethane, carbon tetrachloride, tetrahydrofuran and dimethylsulfoxide;
(3) in a sodium hydroxide-water soluble organic solvent system, the intermediate (I-3) is hydrolyzed and acidified to generate an intermediate (I-4);
(4) reacting the intermediate (I-4) with an acylchlorinating agent selected from at least one of thionyl chloride and oxalyl chloride in an organic solvent selected from at least one of N, N-dimethylformamide, toluene, dichloromethane, chloroform, carbon tetrachloride, tetrahydrofuran and dimethylsulfoxide to produce an intermediate (I-5);
(5) the intermediate (I-5) is reacted with R in the presence of a base in an organic solvent6R5Reacting substituted amine to generate isoxazoline pyrazole amide compound represented by general formula (I), wherein the base is at least one selected from organic base and inorganic baseThe organic solvent is at least one selected from N, N-dimethylformamide, toluene, dichloromethane, chloroform, carbon tetrachloride, tetrahydrofuran and dimethyl sulfoxide.
9. The process for producing an isoxazoline-pyrazolecarboxamide-based compound represented by the general formula (I) according to claim 8, which comprises:
(1) under the action of hydroxylamine hydrochloride, the raw material (I-1) generates an intermediate (I-2);
(2) reacting the intermediate (I-2) with N-chlorobutadiene diimide in an organic solvent at the temperature of 0-100 ℃, and then reacting with R4Reacting the substituted intermediate (I-6) with triethylamine to produce an intermediate (I-3), wherein the organic solvent is at least one selected from N, N-dimethylformamide, toluene, dichloromethane, trichloromethane, carbon tetrachloride, tetrahydrofuran and dimethylsulfoxide;
(3) in a sodium hydroxide-water soluble organic solvent system, the intermediate (I-3) is hydrolyzed and acidified to generate an intermediate (I-4);
(4) reacting the intermediate (I-4) with an acyl chlorination reagent selected from at least one of thionyl chloride and oxalyl chloride in an organic solvent selected from at least one of dichloromethane, trichloromethane and carbon tetrachloride to produce an intermediate (I-5);
(5) the intermediate (I-5) is reacted with R in the presence of a base in an organic solvent6R5Reacting substituted amine to generate isoxazoline pyrazole amide compounds represented by general formula (I), wherein the base is at least one of triethylamine and potassium carbonate which are organic bases; the organic solvent is at least one selected from the group consisting of toluene, dichloromethane, and tetrahydrofuran.
10. Use of isoxazoline-pyrazole amides of general formula (I) according to claim 1, characterized in that they are used for insecticidal purposes.
11. Use of isoxazoline-pyrazolecarboxamide-based compounds according to claim 10, characterized in that the isoxazoline-pyrazolecarboxamide-based compounds are used for controlling at least one pest selected from lepidopteran pests, mites and aphids.
12. Use of isoxazoline pyrazole amides according to claim 11, characterized in that they are used for controlling at least one pest selected from the group consisting of oriental armyworm, cotton bollworm, aphid alfalfa, diamond back moth, spodoptera litura and spodoptera frugiperda.
13. A pesticide preparation, characterized in that the pesticide preparation contains 0.001-99.99% by weight of isoxazoline pyrazole amide compound shown in the general formula (I) as in claim 1, and the balance is agriculturally acceptable carrier.
14. A method for controlling insect pests, characterized in that an isoxazoline-pyrazolopylamide compound represented by the general formula (I) according to claim 1 is applied to an insect pest to be controlled or a medium for its growth.
15. A method of controlling pests according to claim 14 wherein the isoxazoline pyrazolamide compound of formula (I) is applied in an effective amount of from 10 to 1000 grams per hectare.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102131804A (en) * 2008-08-22 2011-07-20 先正达参股股份有限公司 Insecticidal compounds
CN103068813A (en) * 2010-06-15 2013-04-24 拜耳知识产权有限责任公司 Anthranilic acid diamide derivatives
CN111362931A (en) * 2018-12-26 2020-07-03 浙江省化工研究院有限公司 Isoxazoline pyrazole amide compound, and preparation method and application thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102131804A (en) * 2008-08-22 2011-07-20 先正达参股股份有限公司 Insecticidal compounds
CN103068813A (en) * 2010-06-15 2013-04-24 拜耳知识产权有限责任公司 Anthranilic acid diamide derivatives
CN111362931A (en) * 2018-12-26 2020-07-03 浙江省化工研究院有限公司 Isoxazoline pyrazole amide compound, and preparation method and application thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
钟良坤等: "3-芳基异噁唑啉-吡唑-5-甲酰胺类化合物的合成及杀虫活性研究", 《有机化学》 *

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