N-substituted phenyl pyrazole derivative as well as preparation and application thereof

Abstract

The invention relates to an N-substituted phenyl pyrazole derivative as well as preparation and application thereof. Specifically, the invention relates to a compound as shown in a formula (I) as an N-substituted phenyl pyrazole derivative, or an isotope labeled compound thereof, or an optical isomer, a geometric isomer, a tautomer or an isomer mixture thereof, or a pharmaceutically acceptable salt thereof, and application of the compound in preparation of insecticides for pest control. The compound can achieve a better pest control effect at a lower dosage, especially for lepidoptera, coleoptera, homoptera, hemiptera, thysanoptera, isoptera, diptera, hymenoptera, esophagus, lice, orthoptera, cockroach, flea, acarus, nematode and other pests. # imgabs0 #

Description

Technical Field

[0001] The present invention relates to the field of agricultural chemicals, and in particular to an N-substituted phenylpyrazole derivative and a preparation method and application thereof. Background Art

[0002] Although there are many control measures for pests in agriculture at present, new, more effective and reasonable insecticidal compounds are still being explored and discovered. The present invention provides a new type of compound that can be further studied. Pyrazole compounds have excellent biological and physiological activities. In terms of medical care and plant protection, pyrazole compounds have shown a wide range of applications and development prospects. Especially in terms of plant protection, this type of compound has a different mechanism of action from most insecticides used in the field of pest control, and can solve the increasingly serious problem of pesticide resistance. Because of this, pyrazole compounds have opened up new horizons for the development of pesticide chemistry and provided a new way to find new pesticides with high efficiency and low toxicity. Summary of the invention

[0003] The present invention provides a phenylpyrazole derivative and a composition containing the derivative, wherein the pyrazole derivative and the composition are used for preventing and controlling pests in agriculture or gardening. In particular, the compound has a very good preventive effect on lepidopteran pests such as diamondback moth, fall armyworm, armyworm, armyworm or striped stem borer, and has low toxicity and more targeted insecticide, and is expected to solve the problem of low efficiency and high toxicity of current pesticides.

[0004] In a first aspect, the present invention provides a compound of formula (I) or an isotope-labeled compound thereof, or an optical isomer, geometric isomer, tautomer or isomer mixture thereof, or a pesticidally acceptable salt thereof as a phenylpyrazole derivative,

[0005]

[0006] in,

[0007] X1, X2, X3, and X4 are each independently selected from hydrogen, halogen, hydroxy, nitro, amino, cyano, carboxyl, C 1-6 Alkyl, C 2-6 Alkenyl, C 2-6 Alkynyl, C 1-6 Haloalkyl, C 1-6 Alkoxy or C 1-6 Haloalkoxy;

[0008] R1 is selected from hydrogen, halogen, hydroxy, cyano, nitro, amino, carboxyl, C 1-6 Alkyl, C 2-6 Alkenyl, C 2-6 Alkynyl, C 1-6 Haloalkyl, C 2-6Halogenated alkenyl, C 2-6 Haloalkynyl, C 6-10 Aryl, C 6-10 Halogenated aryl, C 6-10 Aryl-C 1-6 Alkyl or C 6-10 Halogenated Aryl-C 1-6 alkyl;

[0009] R2 is selected from hydrogen, C 1-6 Alkyl, C 1-6 Alkoxy, C 2-6 Alkenyl, C 2-6 Alkynyl, C 3-12 Cycloalkyl, C 3-6 Heterocyclic group, C 6-10 Aryl, C 5-12 Heteroaryl, C 1-6 Alkoxy C 1-6 Alkyl, C 3-12 Cycloalkyl C 1-6 Alkyl, and may be substituted or polysubstituted by one or more identical or different substituents selected from: halogen, cyano, C 1-6 Alkyl, C 1-6 Haloalkyl;

[0010] Q is selected from C 1-6 Alkyl, C 2-6 Alkenyl, C 2-6 Alkynyl, C 3-12 Cycloalkyl, C 3-6 Heterocyclic group, C 6-10 Aryl, C 5-12 Heteroaryl, C 1-6 Alkoxy C 1-6 Alkyl, C 1-6 Alkylthio C 1-6 Alkyl, C 3-12 Cycloalkyl C 1-6 Alkyl, C 3-6 Heterocyclyl C 1-6 Alkyl, C 6-10 Aryl C 1-6 Alkyl, C 5-12 Heteroaryl C 1-6 Alkyl, C 6-10 Aryloxy C 1-6 Alkyl, C 5-12 Heteroaryloxy C 1-6 Alkyl, and may be substituted or polysubstituted by one or more identical or different substituents selected from: halogen, cyano, nitro, C 1-6 Alkyl, C 1-6 Alkoxy, C 1-6 Haloalkyl, C 1-6 Alkoxycarbonyl, C 1-3Alkylamino, C 6-10 Aryl.

[0011] In one embodiment of the present invention,

[0012] X1, X2, X3, and X4 are each independently selected from hydrogen, halogen, hydroxy, nitro, amino, cyano, carboxyl, C 1-4 Alkyl, C 2-4 Alkenyl, C 2-4 Alkynyl, C 1-4 Haloalkyl, C 1-4 Alkoxy or C 1-4 Haloalkoxy;

[0013] R1 is selected from hydrogen, halogen, hydroxy, cyano, nitro, amino, carboxyl, C 1-4 Alkyl, C 2-4 Alkenyl, C 2-4 Alkynyl, C 1-4 Haloalkyl, C 2-4 Halogenated alkenyl, C 2-4 Haloalkynyl, C 6-10 Aryl, C 6-10 Halogenated aryl, C 6-10 Aryl-C 1-3 Alkyl or C 6-10 Halogenated Aryl-C 1-3 alkyl;

[0014] R2 is selected from hydrogen, C 1-3 Alkyl, C 1-3 Alkoxy, C 2-4 Alkenyl, C 2-4 Alkynyl, C 3-12 Cycloalkyl, C 3-6 Heterocyclic group, aryl group, C 5-12 Heteroaryl, C 1-3 Alkoxy C 1-3 Alkyl, C 3-12 Cycloalkyl C 1-3 Alkyl, and may be substituted or polysubstituted by one or more identical or different substituents, the substituents being selected from the group consisting of fluorine, chlorine, bromine, cyano, C 1-3 Alkyl, C 1-3 Haloalkyl;

[0015] Q is selected from C 1-6 Alkyl, C 2-4 Alkenyl, C 2-4 Alkynyl, C 3-12 Cycloalkyl, C 3-6 Heterocyclic group, C 6-10 Aryl, C 5-12 Heteroaryl, C 1-3 Alkoxy C 1-3 Alkyl, C 1-3Alkylthio C 1-3 Alkyl, C 3-12 Cycloalkyl C 1-3 Alkyl, C 3-6 Heterocyclyl C 1-3 Alkyl, C 6-10 Aryl C 1-3 Alkyl, C 5-12 Heteroaryl C 1-3 Alkyl, C 6-10 Aryloxy C 1-3 Alkyl, C 5-12 Heteroaryloxy C 1-3 Alkyl, and may be substituted or polysubstituted by one or more identical or different substituents, the substituents being selected from the group consisting of fluorine, chlorine, bromine, cyano, nitro, C 1-3 Alkyl, C 1-3 Alkoxy, C 1-3 Haloalkyl, C 1-3 Alkoxycarbonyl, C 1-3 Alkylamino, C 6-10 Aryl.

[0016] In another embodiment of the present invention, wherein

[0017] X1, X2, X3, and X4 are each independently selected from hydrogen, fluorine, chlorine, bromine, iodine, hydroxyl, cyano, nitro, amino, carboxyl, C 1-4 Alkyl, C 1-4 Haloalkyl, C 1-4 Alkoxy or C 1-4 Haloalkoxy;

[0018] R1 is selected from hydrogen, fluorine, chlorine, bromine, iodine, hydroxyl, cyano, nitro, amino, carboxyl, C 1-4 Alkyl or C 1-4 Haloalkyl;

[0019] R2 is selected from hydrogen, C 1-3 Alkyl, C 1-3 Alkoxy, C 3-6 Cycloalkyl, C 3-6 Heterocyclic group, C 1-3 Alkoxy C 1-3 Alkyl, C 3-6 Cycloalkyl C 1-3 Alkyl, and may be substituted or polysubstituted by one or more identical or different substituents, the substituents being selected from the group consisting of fluorine, chlorine, bromine, cyano, C 1-3 Alkyl, C 1-3 Haloalkyl;

[0020] Q is selected from C 1-6 Alkyl, C 2-4 Alkenyl, C 2-4 Alkynyl, C 3-6Cycloalkyl, C 3-6 Heterocyclic group, C 6-10 Aryl, C 5-12 Heteroaryl, C 1-3 Alkoxy C 1-3 Alkyl, C 1-3 Alkylthio C 1-3 Alkyl, C 3-6 Cycloalkyl C 1-3 Alkyl, C 3-6 Heterocyclyl C 1-3 Alkyl, C 6-10 Aryl C 1-3 Alkyl, C 5-12 Heteroaryl C 1-3 Alkyl, and may be substituted or polysubstituted by one or more identical or different substituents, the substituents being selected from the group consisting of fluorine, chlorine, bromine, cyano, nitro, C 1-3 Alkyl, C 1-3 Alkoxy, C 1-3 Haloalkyl, C 1-3 Alkoxycarbonyl, C 1-3 Alkylamino.

[0021] In another preferred embodiment of the present invention,

[0022] X1, X2, X3, X4 are each independently selected from hydrogen, fluorine, chlorine, bromine, iodine, -CH3, -CH2CH3, -CH2CH2CH3, -CH(CH3)2, -C(CH3)3, -CH2Cl, -CHF2, -CF3, -CH(CF3)2, -CF(CH3)2, -C(CF3)3, -CH2F, -CF2CH3, -CF(CF3)2, -C(OH)(CF3)2, -C(OCH3)(CF3)2;

[0023] R1 is selected from hydrogen, fluorine, chlorine, bromine, iodine, hydroxyl, cyano, nitro, amino, carboxyl, -CH3, -CH2CH3, -CH2CH2CH3, -CH(CH3)2, -C(CH3)3, -CH2Cl, -CHF2, -CF3;

[0024] R2 is selected from hydrogen, C 1-3 Alkyl, C 1-3 Alkoxy, C 3-6 Cycloalkyl, C 1-3 Alkoxy C 1-3 Alkyl, C 3-6 Cycloalkyl C 1-3 Alkyl, and may be substituted or polysubstituted by one or more identical or different substituents, the substituents being selected from the group consisting of fluorine, chlorine, bromine, cyano, C 1-3 Alkyl, C 1-3 Haloalkyl;

[0025] Q is selected from C 1-6 Alkyl, C 2-4 Alkenyl, C 2-4 Alkynyl, C 3-6 Cycloalkyl, C 1-3 Alkoxy C 1-3 Alkyl, C 1-3 Alkylthio C 1-3 Alkyl, C 3-6 Cycloalkyl C 1-3 Alkyl or the following groups,

[0026]

[0027] And it may be singly or polysubstituted by one or more identical or different substituents, and the substituents are selected from: fluorine, chlorine, bromine, cyano, nitro, -CH3, -CH2CH3, -CHF2, -CF3, -OCH3, -OCH2CH3, -OCF3, -NHCH3, -N(CH3)2.

[0028] In another preferred embodiment of the present invention, the compound of formula (I) has the following structure:

[0029]

[0030]

[0031] In another aspect, the present invention relates to a composition comprising at least one compound as described herein and at least one pesticidally acceptable adjuvant.

[0032] In yet another aspect, the present invention relates to use of the compound of the present invention or the composition of the present invention as a pest control agent in agriculture, forestry or horticulture.

[0033] Furthermore, in some embodiments, the present invention relates to the use of the compound described in the present invention or the composition described in the present invention in preventing and / or controlling pests, wherein the pests include at least one of the diamondback moth, the fall armyworm, the fall armyworm, the armyworm or the striped stem borer.

[0034] In yet another aspect, the present invention relates to a method for controlling pests, which comprises applying an effective amount of the compound or composition of the present invention to the pests or the locus of the pests.

[0035] Detailed description of the invention

[0036] Definitions and general terms

[0037] Certain embodiments of the present invention are now described in detail, and examples thereof are illustrated by the accompanying structural formula and chemical formula. The definitions and preferences described in one aspect of the present invention are equally applicable to other aspects. The embodiments of various aspects of the present invention can be combined in various ways without departing from the subject matter and ideas of the present invention, and these combinations are also included within the scope of the present invention.

[0038] It should be further appreciated that certain features of the invention, which for clarity are described in multiple separate embodiments, may also be provided in combination in a single embodiment. Conversely, various features of the invention, which for brevity are described in a single embodiment, may also be provided separately or in any suitable sub-combination.

[0039] Unless otherwise specified, all technical terms used in the present invention have the same meaning as commonly understood by those skilled in the art to which the present invention belongs. All patents and publications related to the present invention are incorporated herein by reference in their entirety.

[0040] Unless otherwise indicated, the following definitions used in the present invention shall apply. For purposes of the present invention, chemical elements are consistent with the Periodic Table of the Elements, CAS version, and Handbook of Chemistry and Physics, 75th edition, 1994. In addition, general principles of organic chemistry can be found in "Organic Chemistry", Thomas Sorrell, University Science Books, Sausalito: 1999, and "March's Advanced Organic Chemistry" by Michael B. Smith and Jerry March, John Wiley & Sons, New York: 2007, the entire contents of which are incorporated herein by reference.

[0041] Unless otherwise specified or there is a clear conflict in context, the articles "a", "an", and "the" as used herein are intended to include "at least one" or "one or more". Therefore, these articles as used herein refer to articles that refer to one or more than one (i.e., at least one) object. For example, "a component" refers to one or more components, i.e., there may be more than one component contemplated for use or use in the implementation of the described embodiment.

[0042] As described herein, the compounds of the present invention may be optionally substituted with one or more substituents, such as the general formula compounds above, or as specific examples in the embodiments, subclasses, and classes of compounds encompassed by the present invention. It should be understood that the term "optionally substituted" is used interchangeably with the term "substituted or unsubstituted". In general, the term "substituted" means that one or more hydrogen atoms in a given structure are replaced by a specific substituent. Unless otherwise indicated, an optional substituent group may be substituted at each substitutable position of the group. When more than one position in a given structural formula can be substituted by one or more substituents selected from a specific group, the substituents may be substituted at each position in the same or different manner. Specifically, examples of "one or more" refer to 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10. The substituents may be, but are not limited to, deuterium, fluorine, chlorine, bromine, iodine, cyano, hydroxy, nitro, amino, carboxyl, alkyl, alkoxy, alkoxyalkyl, alkoxyalkoxy, alkoxyalkylamino, aryloxy, heteroaryloxy, heterocyclyloxy, arylalkoxy, heteroarylalkoxy, heterocyclylalkoxy, cycloalkylalkoxy, cycloalkylalkylamino, alkylthio, haloalkyl, haloalkoxy, hydroxy-substituted alkyl, hydroxy-substituted alkylamino, cyano-substituted alkyl, cyano-substituted alkoxy, cyano-substituted alkylamino, amino-substituted alkyl, alkylacyl, heteroalkyl, cycloalkyl, cycloalkenyl, cycloalkylalkyl, heterocyclyl, heterocyclylalkyl, heterocyclylacyl, aryl, arylalkyl, arylamino, heteroaryl, heteroarylalkyl, heteroarylamino, amido, sulfonyl, aminosulfonyl and the like.

[0043] In addition, it should be noted that, unless explicitly stated otherwise, the description methods used in the present invention, "each... is independently" and "... are each independently" and "... are independently" can be interchanged and should be understood in a broad sense, which can mean that in different groups, the specific options expressed by the same symbols do not affect each other, or that in the same group, the specific options expressed by the same symbols do not affect each other.

[0044] In various parts of this specification, substituents of compounds disclosed in the present invention are disclosed according to group types or ranges. It is particularly noted that the present invention includes each independent subcombination of the individual members of these group types and ranges. For example, the term "C1-C6 alkyl" or "C 1-6 "Alkyl" specifically refers to methyl, ethyl, C3 alkyl, C4 alkyl, C5 alkyl and C6 alkyl as disclosed independently.

[0045] The term "alkyl" or "alkyl group" as used herein refers to a saturated straight or branched monovalent hydrocarbon group containing 1 to 6 carbon atoms; wherein the alkyl group is optionally substituted with one or more substituents described herein. Unless otherwise specified, the alkyl group contains 1-6 carbon atoms. In one embodiment, the alkyl group contains 1-5 carbon atoms; in one embodiment, the alkyl group contains 1-4 carbon atoms; in another embodiment, the alkyl group contains 1-3 carbon atoms.

[0046] Examples of alkyl groups include, but are not limited to, methyl (Me, -CH3), ethyl (Et, -CH2CH3), n-propyl (n-Pr, -CH2CH2CH3), isopropyl (i-Pr, -CH(CH3)2), n-butyl (n-Bu, -CH2CH2CH2CH3), isobutyl (i-Bu, -CH2CH(CH3)2), sec-butyl (s-Bu, -CH(CH3)CH2CH3), tert-butyl (t-Bu, -C(CH3)3), n-butyl (n-Bu, -CH2CH2CH2CH3), isobutyl (i-Bu, -CH2CH(CH3)2), sec-butyl (s-Bu, -CH(CH3)CH2CH3), tert-butyl (t-Bu, -C(CH3)3), n-butyl (n-Bu, -CH2CH2CH2CH3), Pentyl (-CH2CH2CH2CH2CH3), 2-pentyl (-CH(CH3)CH2CH2CH3), 3-pentyl (-CH(CH2CH3)2), 2-methyl-2-butyl (-C(CH3)2CH2CH3), 3-methyl-2-butyl (-CH(CH3)CH(CH3)2), 3-methyl-1-butyl (-CH2CH2CH(CH3)2), 2-methyl-1-butyl (-CH2CH(CH3)CH2CH3), and the like.

[0047] The term "alkoxy" means an alkyl group attached to the rest of the molecule via an oxygen atom, wherein the alkyl group has the meaning as described herein. Examples of alkoxy groups include, but are not limited to, methoxy (MeO, -OCH3), ethoxy (EtO, -OCH2CH3), 1-propoxy (n-PrO, n-propoxy, -OCH2CH2CH3), 2-propoxy (i-PrO, i-propoxy, -OCH(CH3)2), and the like.

[0048] The term "halogen" refers to fluorine (F), chlorine (Cl), bromine (Br) or iodine (I).

[0049] The term "haloalkyl" means an alkyl group substituted by one or more halogen atoms, such examples include, but are not limited to, -CF3, -CHF2, -CH2Cl, -CH2CF3, -CH2CHF2, -CH2CH2CF3 and the like.

[0050] The term "haloalkoxy" means an alkoxy group substituted by one or more halogen atoms, such examples include, but are not limited to, -OCF3, -OCHF2, -OCHCl2, -OCH2CHF2, -OCH2CHCl2, -OCH(CH3)CHF2 and the like.

[0051] The term "alkenyl" refers to a straight or branched chain monovalent hydrocarbon radical containing 2 to 6 carbon atoms, having at least one site of unsaturation, i.e., a carbon-carbon sp 2 Double bond, wherein the alkenyl group may be optionally substituted with one or more substituents described herein, including "cis" and "tans" orientations, or "E" and "Z" orientations. In one embodiment, the alkenyl group contains 2-5 carbon atoms; in another embodiment, the alkenyl group contains 2-4 carbon atoms; in yet another embodiment, the alkenyl group contains 2-3 carbon atoms. Examples of alkenyl groups include, but are not limited to, vinyl (-CH=CH2), allyl (-CH2CH=CH2), propenyl (CH3-CH=CH-), oxo-butenyl (CH3-C(=O)-CH=CH-), and the like.

[0052] The term "alkynyl" refers to a straight or branched monovalent hydrocarbon radical containing 2-6 carbon atoms, wherein at least one carbon-carbon sp triple bond exists, wherein the alkynyl group may be optionally substituted with one or more substituents described herein. In one embodiment, the alkynyl group contains 2-5 carbon atoms; in one embodiment, the alkynyl group contains 2-4 carbon atoms; in another embodiment, the alkynyl group contains 2-3 carbon atoms. Examples of alkynyl groups include, but are not limited to, -C≡CH, -C≡CCH3, -CH2-C≡CH, -CH2-C≡CCH3, -CH2CH2-C≡CH, -CH2-C≡CCH2CH3, -CH2CH2-C≡CCH3, and the like.

[0053] As used herein, the term "unsaturated" means that the group contains one or more degrees of unsaturation.

[0054] The term "heteroaryl" refers to monocyclic, bicyclic and tricyclic ring systems containing 5-12 ring atoms, or 5-10 ring atoms, or 5-6 ring atoms, wherein at least one ring system is aromatic and at least one ring system contains one or more heteroatoms, wherein each ring system contains 5-7 atoms to form a ring and has one or more points of attachment to the rest of the molecule. The term "heteroaryl" can be used interchangeably with the term "heteroaromatic ring" or "heteroaromatic compound". The heteroaryl group is optionally substituted with one or more substituents described herein.

[0055] The term "heteroatom" refers to O, S, N, P and Si, including N, S and P in any oxidation state; in the form of primary, secondary, tertiary amines and quaternary ammonium salts; or in the form of a nitrogen atom in a heterocyclic ring in which the hydrogen is substituted, for example, N (such as N in 3,4-dihydro-2H-pyrrolyl), NH (such as NH in pyrrolidinyl) or NR (such as NR in N-substituted pyrrolidinyl).

[0056] In one embodiment, the 5-10 atom heteroaryl group contains 1, 2, 3 or 4 heteroatoms independently selected from O, S and N.

[0057] In another embodiment, the ring atoms of the heteroaryl group contain 1-9 carbon atoms and 1-4 heteroatoms selected from N, O or S; in another embodiment, the ring atoms of the heteroaryl group contain 1-5 carbon atoms and 1-4 heteroatoms selected from N, O or S.

[0058] In another embodiment, heteroaryl represents a 5-membered or 6-membered heteroaryl containing 1-4 N heteroatoms; in another embodiment, heteroaryl represents a 5-membered heteroaryl containing 1-3 heteroatoms selected from N, O or S; in another embodiment, heteroaryl represents a 5-membered heteroaryl containing 1-3 heteroatoms selected from N or O; in another embodiment, heteroaryl represents a 5-membered heteroaryl containing 1-3 heteroatoms selected from N or S.

[0059] Examples of heteroaryl groups include, but are not limited to, 2-furanyl, 3-furanyl, N-imidazolyl, 2-imidazolyl, 4-imidazolyl, 5-imidazolyl, 3-isoxazolyl, 4-isoxazolyl, 5-isoxazolyl, 2-oxazolyl, 4-oxazolyl, 5-oxazolyl, N-pyrrolyl, 2-pyrrolyl, 3-pyrrolyl, 2-pyridyl, 3-pyridyl, 4-pyridyl, 2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl, pyridazinyl (e.g., 3-pyridazinyl), 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, tetrazolyl (e.g., 5-tetrazolyl), triazolyl (e.g., 2- triazolyl and 5-triazolyl), 2-thienyl, 3-thienyl, pyrazolyl, isothiazolyl, 1,2,3-oxadiazolyl, 1,2,5-oxadiazolyl, 1,2,4-oxadiazolyl, 1,2,3-triazolyl, 1,2,3-thiodiazolyl, 1,3,4-thiodiazolyl, 1,2,5-thiodiazolyl, pyrazinyl, 1,3,5-triazinyl, pyrimidinone, pyridone; also including the following bicyclic rings, but in no way limited to these bicyclic rings: benzimidazolyl, benzofuranyl, benzotetrahydrofuranyl, benzothienyl, indolyl (such as 2-indolyl), and the like.

[0060] The term "cycloalkyl" refers to a monovalent or polyvalent saturated monocyclic, bicyclic or tricyclic ring system containing 3-12 carbon atoms. In one embodiment, the cycloalkyl contains 3-12 carbon atoms; in one embodiment, the cycloalkyl contains 3-10 carbon atoms; in another embodiment, the cycloalkyl contains 3-8 carbon atoms; in yet another embodiment, the cycloalkyl contains 3-6 carbon atoms. The cycloalkyl group is optionally substituted with one or more substituents described herein. Such examples include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl, cyclododecyl, adamantyl, and the like.

[0061] The terms "heterocyclyl" and "heterocycle" are used interchangeably herein and refer to a saturated or partially unsaturated monocyclic, bicyclic or tricyclic ring containing 3-15 ring atoms, wherein the monocyclic, bicyclic or tricyclic ring does not contain an aromatic ring and at least one ring atom is selected from nitrogen, sulfur and oxygen atoms. Unless otherwise specified, the heterocyclyl group can be a carbon group or a nitrogen group, and the -CH2- group can be optionally replaced by -C(=O)-. The sulfur atom of the ring can be optionally oxidized to S-oxide. The nitrogen atom of the ring can be optionally oxidized to N-oxide. Examples of heterocyclic groups include, but are not limited to, oxirane, azetidinyl, oxetanyl, thietanyl, pyrrolidinyl (e.g., 2-pyrrolidinyl), 2-pyrrolinyl, 3-pyrrolinyl, pyrazolidinyl, imidazolinyl, imidazolidinyl, tetrahydrofuranyl, dihydrofuranyl, tetrahydrothiophenyl, dihydrothiophenyl, 1,3-dioxolane, dithiolanyl, tetrahydropyranyl, dihydropyranyl, 2H-pyranyl, 4H-pyranyl, pyranyl, tetrahydrothiopyranyl, piperidinyl (2-piperidinyl, 3-piperidinyl, 4-piperidinyl), morpholinyl, thiomorpholinyl, (1-oxo)-thiomorpholinyl, (1,1-dioxo)-thiomorpholinyl, piperazinyl, dioxanyl, dithianyl, thioxanyl, homopiperazinyl, homopiperidinyl, oxepanyl, thiepanyl, 2-oxa-5-azabicyclo[2.2.1]hept-5-yl, tetrahydropyridinyl. Examples of heterocyclic groups in which the -CH2- group is replaced by -C(=O)- include, but are not limited to, 2-oxopyrrolidinyl, oxo-1,3-thiazolidinyl, 2-piperidonyl, 3,5-dioxopiperidinyl. Examples of heterocyclic groups in which the sulfur atom is oxidized include, but are not limited to, sulfolane, 1,1-dioxothiomorpholinyl. The heterocyclyl group is optionally substituted with one or more substituents described herein.

[0062] The term "aryl" refers to monocyclic, bicyclic and tricyclic carbon ring systems containing 6-14 ring atoms, or 6-12 ring atoms, or 6-10 ring atoms, wherein at least one ring system is aromatic, wherein each ring system contains a ring consisting of 3-7 atoms and has one or more points of attachment to the rest of the molecule. The term "aryl" can be used interchangeably with the term "aromatic ring". Examples of aryl groups can include phenyl, indenyl, naphthyl and anthracenyl. The aryl group is optionally substituted with one or more substituents described herein.

[0063] Salts of the compounds of the present invention include those derived from alkali metals or alkaline earth metals and those derived from ammonia and amines. Preferred cations include sodium, potassium, magnesium and a cation having the formula N + (R AA R BB R CC R DD ) of an ammonium cation, wherein R AA , R BB , R CC and R DD Independently selected from hydrogen, C1-C6 alkyl and C1-C6 hydroxyalkyl. Salts of compounds of formula (I) can be prepared by treating compounds of formula (I) with metal hydroxides (e.g. sodium hydroxide) or amines (e.g. ammonia, trimethylamine, diethanolamine, 2-methylthiopropylamine, bisallylamine, 2-butoxyethylamine, morpholine, cyclododecylamine or benzylamine).

[0064] When the compounds of the present invention contain a basic moiety, acceptable salts may be formed from organic and inorganic acids such as acetic acid, propionic acid, lactic acid, citric acid, tartaric acid, succinic acid, fumaric acid, maleic acid, malonic acid, mandelic acid, malic acid, phthalic acid, hydrochloric acid, hydrobromic acid, phosphoric acid, nitric acid, sulfuric acid, methanesulfonic acid, naphthalenesulfonic acid, benzenesulfonic acid, toluenesulfonic acid, camphorsulfonic acid, and similarly known acceptable acids.

[0065] Compositions and preparations of the compounds of the present invention

[0066] The compound of the present invention can generally be used as an active ingredient of a pesticide in a composition and / or formulation, and usually also comprises adjuvants commonly used in pesticides. The adjuvants include surfactants and carriers.

[0067] The above-mentioned surfactant can be any surfactant known in the field of pesticide formulations. In the present invention, it is preferably one or more of an emulsifier, a dispersant and a wetting agent.

[0068] The other carriers except the above-mentioned surfactants can be various carriers known in the field of pesticide formulations, including various silicates, carbonates, sulfates, oxides, phosphates, plant carriers, and synthetic carriers. Specifically, for example: one or more of white carbon black, kaolin, diatomaceous earth, clay, talc, organic bentonite, pumice, titanium dioxide, dextrin, cellulose powder, light calcium carbonate, soluble starch, corn starch, sawdust powder, urea, amine fertilizer, a mixture of urea and amine fertilizer, glucose, maltose, sucrose, anhydrous potassium carbonate, anhydrous sodium carbonate, anhydrous potassium bicarbonate, anhydrous sodium bicarbonate, attapulgite, a mixture of anhydrous potassium carbonate and anhydrous potassium bicarbonate, and a mixture of anhydrous sodium carbonate and anhydrous sodium bicarbonate.

[0069] The emulsifier may be any emulsifier known in the field of pesticide formulations. Specifically, the emulsifier may be one or more of calcium dodecylbenzene sulfonate, triphenyl phenol polyoxyethylene ether phosphate, fatty alcohol polyoxyethylene ether, alkylphenol polyoxyethylene ether, alkylphenol polyoxyethylene polyoxypropylene ether, fatty amine, ethylene oxide adduct of fatty amide, fatty acid polyoxyethylene ester, rosin acid ethylene oxide adduct, polyol fatty acid ester and ethylene oxide adduct thereof, styrylphenyl polyoxyethylene ether, alkylphenol formaldehyde resin polyoxyethylene ether, terminal hydroxyl polyoxyethylene polyoxypropylene ether, styrylphenol formaldehyde resin polyoxyethylene polyoxypropylene ether and castor oil polyoxyethylene ether.

[0070] The above-mentioned dispersant can be various dispersants known in the field of pesticide formulations. Specifically, the dispersant is one or more of acrylic acid homopolymer sodium salt, maleic acid disodium salt, naphthalenesulfonic acid formaldehyde condensate sodium salt, rosin block polyoxyethylene ether polyoxypropylene ether sulfonate, terminal hydroxyl polyoxyethylene polyoxypropylene ether block copolymer, triphenyl phenol polyoxyethylene ether phosphate, fatty alcohol polyoxyethylene ether phosphate and p-hydroxyphenyl lignin sulfonate sodium salt.

[0071] The wetting agent can be any wetting agent known in the field of pesticide formulations. Specifically, the wetting agent can be one or more of sodium dodecyl sulfate, sodium secondary alkyl sulfate, sodium dodecylbenzene sulfonate, fatty alcohol polyoxyethylene ether, alkyl naphthalene sulfonate, and alkylphenol resin polyoxyethylene ether sulfate.

[0072] According to the insecticide composition of the present invention, the insecticide composition may also contain various formulation adjuvants commonly used in the field of pesticide formulations. Specifically, the formulation adjuvant may be one or more of a solvent, a co-solvent, a thickener, an antifreeze agent, an encapsulating material, a protective agent, a defoaming agent, a disintegrant, a stabilizer, a preservative and a binder.

[0073] The above-mentioned solvent may be any solvent known in the field of pesticide formulations. Specifically, the solvent may be one or more of an organic solvent, vegetable oil, mineral oil, solvent oil and water.

[0074] The organic solvent includes one or more of N-methylpyrrolidone, tetrahydrofuran, dimethyl sulfoxide, N,N-dimethyldecylamide, N,N-dimethylformamide, trimethylbenzene, tetramethylbenzene, xylene, toluene, octane, heptane, methanol, isopropanol, n-butanol, tetrahydrofurfuryl alcohol, tributyl phosphate, 1,4-dioxane and cyclohexanone.

[0075] The vegetable oil includes one or more of methylated vegetable oil, rosin-based vegetable oil, turpentine, epoxidized soybean oil, soybean oil, peanut oil, rapeseed oil, castor oil, corn oil and pine nut oil.

[0076] The mineral oil includes one or more of liquid wax, motor oil, kerosene and lubricating oil.

[0077] At the same time, the above solvents can also be used as co-solvents.

[0078] The antifreeze agent may be any antifreeze agent known in the field of pesticide formulations. In the present invention, the antifreeze agent is preferably one or more of ethylene glycol, propylene glycol, glycerol and urea.

[0079] The thickener may be any thickener known in the field of pesticide formulations. Specifically, the thickener may be one or more of xanthan gum, polyvinyl alcohol, polypropylene alcohol, polyethylene glycol, white carbon black, diatomaceous earth, kaolin, clay, sodium alginate, magnesium aluminum silicate, sodium aluminum silicate, carboxymethyl cellulose, sodium hydroxypropyl cellulose and organic bentonite.

[0080] The capsule material may be any capsule material known in the field of pesticide formulations, and in the present invention, preferably one or more of polyurethane, polyurea and urea-formaldehyde resin.

[0081] The protective agent can be any protective agent known in the field of pesticide formulations, and in the present invention, polyvinyl alcohol and / or polyethylene glycol are preferred.

[0082] The defoaming agent can be any defoaming agent known in the field of pesticide formulations. In the present invention, it is preferably one or more of organosiloxane, tributyl phosphate and silicone.

[0083] The stabilizer is selected from one or more of triphenyl phosphite, epichlorohydrin and acetic anhydride.

[0084] The preservative is selected from one or more of benzoic acid, sodium benzoate, 1,2-benzisothiazolin-3-one (BIT for short), kasone and potassium sorbate.

[0085] The present invention also provides a preparation prepared from the above insecticide composition, wherein the preparation is in the form of emulsifiable concentrate, aqueous emulsion, microemulsion, soluble liquid, aqueous suspension, suspoemulsion, ultra-low volume spray, oil suspension, microcapsule suspension, water film spreading oil, wettable powder, water dispersible granule, dry suspension, soluble powder, soluble granule, emulsifiable powder, emulsifiable granule, granule, solid microcapsule preparation, effervescent tablet, effervescent granule, water floating dispersible granule or seed coating. The above dosage forms can be prepared by conventional methods in the art.

[0086] The insecticide composition of the present invention can be provided in the form of a finished preparation, that is, the various substances in the composition have been mixed; it can also be provided in the form of a separate preparation, which can be mixed in a bucket or tank before use and selectively mixed with water for dilution according to the required concentration of the active substance.

[0087] For additional information related to the formulation field, see "The Formulator's Toolbox - Product Forms for Modern Agriculture" by TS Woods, in Pesticide Chemistry and Bioscience, The Food-Environment Challenge, edited by T. Brooks and TR Roberts, Proceedings of the 9th International Congress on Pesticide Chemistry, The Royal Society of Chemistry, Cambridge, 1999, pp. 120-133. See also U.S. Pat. No. 3,235,361, column 6, lines 16 to column 7, line 19, and Examples 10-41; U.S. Pat. No. 3,309,192, column 5, lines 43 to column 7, line 62, and Examples 8, 12, 15, 39, 41, 52, 53, 58, 132, 138-140, 162-164, 166, 167, and 169-182; U.S. Pat. No. 2,891,855, column 3, lines 66 to column 5, line 17, and Examples 1-4; Klingman, Weed Control as a Science, John Wiley and Sons, Inc., New York, 1961, pages 81-96; Hance et al., Weed Control Handbook, 8th edition, Blackwell Scientific Publications, Oxford, 1989; and Developments in formulation technology, PJB Publications, Richmond, UK, 2000.

[0088] Application of the compounds and compositions of the present invention

[0089] The compounds and / or compositions of the present invention are suitable for controlling pests such as arthropods, gastropods and nematodes in useful plants, including but not limited to:

[0090] From the order of the Homoptera, for example, Aleurodes brassicae, Bemisia tabaci, Trialeurodes vaporariorum, Aphis gossypii, Brevicoryne brassicae, Cryptomyzus ribis, Aphis fabae, Aphis pomi, Eriosoma lanigerum, Hyalopterus arundinis, Phylloxera vastatrix, Pemphigus spp., Macrosiphum avenae, Myzus spp., Phorodon humuli, Rhopalosiphum padi, Empoasca spp. spp.), Euscelis bilobatus, Nephotettix cincticeps, Lecanium corni, Saissetia oleae, Laodelphax striatellus, Nilaparvatalugens, Aonidiella aurantii, Aspidiotus hederae, Pseudococcus spp., Psylla spp.

[0091] Hemiptera: Planthoppers (Delphacidae) such as Nilaparvatalugens, Laodelphax striatellus; Leafhoppers (Deltocephalidae) such as Nephotettix cincticeps; Aphids (Aphididae) such as Aphis gossypii, Aphis craccivora Koch; Pentatomidae such as Nezaraantennata; Whiteflies (Aleyrodidae) such as Trialeurodes vaporariorum; Scales (Coccidae) such as Calformia red scale (Aonidiella aurantii); Tingidae; Homoptera, Psyllidea;

[0092] Lepidoptera: Pyralidae such as Chilo suppressalis; Noctuidae such as Spodoptera litura, Pseudaletia separata, Heliothis spp. and Helicoverpa spp.; Pieridae such as Pierisrapae; Tortricidae such as Adoxophyes; Gracilariidae such as Caloptilia theivora and Phyllonorycter ringoneella; Carposinidae such as Carposina niponensis; Lyonetiidae such as Lyonetia spp. spp.); Lymantriidae such as Lymantria spp. and Euproctis spp.; Yponomeutidae such as Plutella xylostella; Gelechiidae such as Pectinophora gossypiella and Phthorimaea operculella; Arctiidae such as Hyphantria cunea; and Tineidae such as Tinea translucens and Tineola bisselliella;

[0093] Thysanoptera: Frankliniella occidentalis, Thrips palmi, Scirtothrips dorsalis, Thrips tabaci, Frankliniella intonsa and Frankliniella fusca.

[0094] Diptera: Musca domestica, Culex popienspallens, Tabanus trigonus, Hylemya anitqua, Hylemyaplatura, Anopheles sinensis, Agromyza oryzae, Hydrellia griseola, Chlorops oryzae, Dacus cucurbitae, Ceratitis capitata and Liriomyza trifolii.

[0095] Coleoptera: Epilachna vigintioctopunctata, Phyllotreta striolata, Oulema oryzae, Echinocnemus squameus, Lissorhoptrus oryzophilus, Anthonomus grandis, Callosobruchus chinensis, Sphenophorus venatus, Popillia japonica, Anomala cuprea, Diabrotica spp., Leptinotarsa ​​decemlineata, Agriotes spp., Lasioderma serricorne, Anthrenus grandis verbasci), Tribolium castaneum, Lyctus brunneus, Anoplophora malasiaca, and Tomicus piniperda;

[0096] Orthoptera: East Asian migratory locust (Locusta migratoria), African mole cricket (Gryllotalpaafficana), Hokkaido rice locust (Oxya yezoensis) and Japanese rice locust (Oxya japanica);

[0097] Hymenoptera: Athalia rosae, Acromyrmex spp., and Solenopsis spp.

[0098] Nematodes: Aphelenchoides besseyi, Nothotylenchus acris, Heterodera glycines, Meloidogyne incognita, Pratylenchus penetrans, and Nacobbus aberrans.

[0099] From the order Blattariae: Blattella germanica, Periplaneta fuliginosa, Periplaneta Americana, Periplaneta brunnea and Blatta orientalis.

[0100] Order Acarina: Tetranychidae (e.g., Tetranychus cinnabarinus, Tetranychu surticae, Panonychus citri, and Oligonychus spp.); Eriophyidae (e.g., Aculops pelekassi); Tarsonemidae; Tenuipalpidae; Tuckerellidae; Tuckerellidae Acaridae; Pyroglyphidae (e.g., Dermatophagoides farinae and Dermatophagoides ptrenyssnus); Cheyletidae, Cheyletus malaccensis; malaccensis and Cheyletusmoorei; and Dermanyssidae.

[0101] In the context of the present invention, useful plants include the following plant species: cereals (wheat, barley, rye, oats, rice, corn, sorghum and related species); beets (sugar beet and fodder beet); pome, stone and soft fruits (apple, pear, plum, peach, almond, cherry, strawberry, raspberry and blackberry); legumes (lentil, bean, pea, soybean); oil crops (rapeseed, mustard, olive, sunflower, coconut, castor oil plant, cocoa bean, peanut or soybean); cucurbits (squash, cucumber, melon) ; fiber plants (cotton, flax, hemp, jute); citrus fruits (oranges, lemons, grapefruits, mandarins); vegetables (spinach, lettuce, asparagus, cabbage, carrots, onions, tomatoes, potatoes, red peppers); laurel plants (avocado, cinnamon, camphor) or plants such as tobacco, nuts, coffee, eggplant, sugar cane, tea, pepper, grapevines, hops, bananas and natural rubber plants, as well as turf, ornamental and forest plants, such as flowers, shrubs, broad-leaved trees or evergreen trees, such as conifers, and plant propagation material.

[0102] The term "plant propagation material" should be understood as meaning reproductive parts of the plant, such as seeds, which can be used for the multiplication of the plant, and vegetative material, such as cuttings or tubers (for example potatoes).

[0103] The compounds and / or compositions of the present invention can kill pests through an effective amount of active substances. Wherein, when the effective amount of the compound of formula (I) is within 5g-5kg per hectare, preferably 10g-1kg, the effect of controlling pests is better.

[0104] The present invention also relates to a method for controlling pests, which is carried out by applying the compound or composition of the present invention to seeds, plants or plant parts, fruits or soil where plants grow. The application can be carried out before and after the seeds, plants or plant parts, fruits or soil where plants grow are infested by pests.

[0105] The term "effective amount" used means an amount of the compounds of the present invention or compositions that is sufficient to control pests on cultivated plants or in material protection and does not cause significant damage to the treated plants. This amount can vary within a wide range and depends on various factors such as pest species, cultivated plants or materials to be treated, climatic conditions and the specific compound used.

[0106] The method of using the compound and / or composition of the present invention is simple, and the compound and / or composition of the present invention is applied to the pest or its growth medium. The application dosage of the compound and / or composition of the present invention varies according to weather conditions, dosage form, application timing, application method, application area, target disease, target crop, etc.

[0107] General synthesis process

[0108] The following schemes describe the preparation of the compounds of the present invention. Unless otherwise specified, the compounds of the present invention can be prepared in a variety of ways known to those skilled in the art of organic synthesis. Those skilled in the art can refer to the synthetic routes of the specific compounds of the specific embodiments of the present invention and make appropriate adjustments to the reaction raw materials and reaction conditions to obtain the synthetic methods of other compounds. The raw materials, reagents, etc. used to prepare the compounds of the present invention are all commercially available or can be prepared by conventional methods in the art. In this specification, if there is any difference between the chemical name and the chemical structure, the structure is dominant.

[0109] For the sake of simplicity, the "pyrazole derivatives", "compounds of formula (I)" or "compounds of the present invention" mentioned below may also include any isotope-labeled compounds of the compound of formula (I), or their optical isomers, geometric isomers, tautomers or isomer mixtures, or their pesticide-acceptable salts.

[0110] The compound of formula (I) of the present invention can be prepared by the following method:

[0111]

[0112] The remaining substituents are as described above.

[0113] The specific steps include: dissolving the raw material A in a suitable solvent, adding the corresponding acyl compound B, substituting under alkaline conditions, reacting at a temperature of 0-120° C. for 1-24 hours, and obtaining the target compound I.

[0114] In addition, the present invention also lists a number of exemplary compounds that have been synthesized, and their specific group selections are shown in Table 1 below. It should be understood that the scope of the present invention is not limited to the exemplary compounds listed in the following table, and the various group selections of the compounds in Table 1 below can be arbitrarily combined without particular limitation.

[0115] Table 1 Structures of some compounds

[0116]

[0117]

[0118]

[0119]

[0120]

[0121]

[0122]

[0123] Table 2 Physical properties and characterization data of some compounds

[0124]

[0125]

[0126]

[0127] DETAILED DESCRIPTION

[0128] The compounds of formula (I) of the present invention can be synthesized by various methods familiar to those skilled in the art of organic synthesis. The following specific examples provide some exemplary methods for synthesizing compounds of formula (I), which are well known in the field of synthetic chemistry. Obviously, referring to the exemplary schemes in this patent, those skilled in the art can easily design other synthetic routes of compounds of formula (I) by appropriately adjusting the reactants, reaction conditions and protecting groups.

[0129] The present invention is further described below with reference to the examples; however, these examples do not limit the scope of the present invention. Unless otherwise stated, all reactants used in the examples are obtained from commercial sources; the instruments and equipment used in the synthesis experiments and product analysis and detection are conventional instruments and equipment commonly used in organic synthesis.

[0130] Example 1: Synthesis of Compound 192

[0131]

[0132] 2-Chloro-N-cyclopropyl-5-(1-(2,6-dichloro-4-(perfluoropropane-2-yl)phenyl)-1H-pyrazol-4-yl)nicotinamide (0.57g, 1mmol) and 30ml THF were placed in a 100ml reaction bottle, 60% NaH (0.06g, 1.5mmol) was added in batches under stirring in an ice bath, and the mixture was reacted at 0°C for 30min, and then cyclopropanecarbonyl chloride (0.16g, 1.5mmol) was slowly added. After completion, the mixture was heated to 40-50°C and stirred for overnight reaction. The reaction was terminated after 12h, the mixture was cooled to room temperature, quenched with water, extracted with ethyl acetate 20ml*2 times, the organic phases were combined, washed with water and saturated brine in turn, dried with sodium sulfate, filtered, evaporated under reduced pressure, and purified by rapid column chromatography [petroleum ether / ethyl acetate (v / v) = 5 / 1]. A white solid (0.48g, yield: 76%) was obtained.

[0133] 1H NMR(400MHz,Chloroform-d)δ8.59(d,J=2.4Hz,1H),8.12(s,1H),7.90(s,1H),7.80(d,J=2.4Hz,1H),7.74(s,2H),3.01(dt,J=6.9,3.2Hz, 1H), 2.48 (ddd, J=7.7, 5.2, 3.0Hz, 1H), 1.23 (d, J=6.9Hz, 2H), 1.10 (dt, J=5.5, 3.0Hz, 2H), 1.06 (dt, J=7.8, 2.7Hz, 2H), 1.01–0.93 (m, 2H).

[0134] 19 F NMR(377MHz, CDCl3)δ-75.21,-181.58.

[0135] LC-MS: (M+1) m / z=643.1.

[0136] Other compounds in Table 1 can be prepared by methods similar to those exemplified above.

[0137] Example 2: Formulation Example

[0138] 1. Soluble liquid: Dissolve 10-50% of the compound of formula (I) and 5-20% of a wetting agent in 100% water and / or a water-soluble solvent to obtain the product.

[0139] 2. Emulsifiable concentrate: 10-70% of the compound of formula (I) and 5-10% of an emulsifier are dissolved in a water-insoluble organic solvent added to 100% to obtain the product.

[0140] 3. Water emulsion: Dissolve 5-30% of the compound of formula (I) and 1-10% of an emulsifier in 20-40% of a water-insoluble organic solvent. Use an emulsifier to introduce the mixture into 100% water and make a homogeneous emulsion to obtain the product.

[0141] 4. Suspension: 10-50% of the compound of formula (I) is ground in a stirred ball mill with 2-10% of a dispersant, 1-5% of a wetting agent, 0.1-5% of a thickener and water up to 100% to prepare an active substance suspension to obtain the product.

[0142] 5. Water dispersible granules: Grind 10-70% of the compound of formula (I) under the condition of adding up to 100% of dispersant and wetting agent and make it into water dispersible granules with the aid of industrial production equipment to obtain the product.

[0143] All the above are weight percentages.

[0144] Example 3: Bioassay Example

[0145] This example tests the insecticidal activities of some compounds against Plutella xylostella, Spodoptera frugiperda, Spodoptera litura, Armyworm, and Chilo suppressalis.

[0146] The specific implementation process is as follows:

[0147] 1) Compound preparation: Weigh a certain mass of the original drug using an analytical balance (0.0001 g), dissolve it in N,N-dimethylformamide containing 1‰ Tween-80 emulsifier to prepare a 1% mother solution, and then dilute it with distilled water for use.

[0148] 2) Test methods

[0149] 2.1 Determination of activity against Plutella xylostella

[0150] Leaf dipping method: soak appropriate amount of radish / corn leaves in the prepared solution for 30 seconds, place in a plastic petri dish with filter paper to dry naturally in the shade, and place 8 2-3 year old diamondback moths in each dish, and place in an observation room at 22℃ light (16 / 8h). Observe after 48 hours, touch the insect body with a brush, and consider it dead if there is no reaction. Repeat 3 times for each treatment, and set solvent control. The test concentration is 50mg / L.

[0151] Among some of the tested compounds, compounds 3, 9, 26, 31, 35, 39, 58, 76, 81, 86, 90, 93, 98, 102, 107, 111, 115, 119, 146, 172, 178, 189, 195, 199, 204, 209, 214, 219, 224, 228, 232, 237, 247, 258, 263, 268, 275, 289, 293, 306, 321, 331, 333, 345 and 351 showed significant protective effects against Plutella xylostella at a concentration of 50 mg / L, with a mortality rate of 100%.

[0152] 2.2 Determination of activity against fall armyworm

[0153] Leaf dipping method: soak appropriate amount of radish / corn leaves in the prepared solution for 30 seconds, place in a plastic petri dish with filter paper to dry naturally in the shade, and place 8 2-3 year old fall armyworms in each dish, and place in an observation room at 22℃ light (16 / 8h). Observe after 48 hours, touch the insect body with a brush, and consider it dead if there is no reaction. Repeat 3 times for each treatment, and set solvent control. The test concentration is 100mg / L.

[0154] Among some of the tested compounds, compounds 3, 9, 26, 31, 35, 39, 58, 76, 81, 86, 90, 93, 98, 102, 107, 111, 115, 119, 146, 172, 178, 189, 195, 199, 204, 209, 214, 219, 224, 228, 232, 237, 247, 258, 263, 268, 275, 289, 293, 306, 321, 331, 333, 345 and 351 showed significant protective effects against fall armyworm at a concentration of 100 mg / L, with a mortality rate of 100%.

[0155] 2.3 Determination of activity against Spodoptera litura

[0156] Artificial feed film method: first pour the prepared artificial feed into a 12-well plate while it is still hot, add 2.5 ml of artificial feed to each well, and wait for the feed to cool thoroughly before use. Make 3 12-well plates for each concentration gradient of each agent, each 12-well plate is a replicate, a total of 3 replicates, add 50 μL of the corresponding concentration gradient agent to each well and dry. Inoculate one Spodoptera litura larvae into each well. Control 3 12-well plates, a total of 3 replicates, add 50 μL of solvent control to each well. Put it in an insect breeding room with a temperature of 26±2℃, a light intensity of 16h:8h (L:D), and a humidity of 50=70%. Investigate the death of the test insects 48 hours after the test and count the mortality of the test insects. The test concentrations were 100 mg / L respectively.

[0157] Among some of the tested compounds, compounds 3, 9, 26, 31, 35, 39, 58, 76, 81, 86, 90, 93, 98, 102, 107, 111, 115, 119, 146, 172, 178, 189, 195, 199, 204, 209, 214, 219, 224, 228, 232, 237, 247, 258, 263, 268, 275, 289, 293, 306, 321, 331, 333, 345 and 351 showed significant protective effects against Spodoptera litura at a concentration of 100 mg / L, with a mortality rate of 100%.

[0158] 2.4 Determination of activity against armyworms

[0159] Potted method: The armyworms were raised with artificial feed, and the third-instar larvae were selected as the test insect targets. The wheat was first sprayed with a constant pressure sprayer. Each agent treatment was repeated twice, with one pot of wheat seedlings per repetition, and 2.5 ml of the solution was sprayed per pot. The control was treated with clean water. After the solution was completely dry, 10 third-instar armyworm larvae were inoculated in each pot of wheat seedlings. The wheat seedlings were placed in a plastic seedling cup, and the plastic seedling cup was turned upside down. The joints were glued with double-sided tape. The plastic seedling cup on the top was pierced with about 10 air holes with pointed tweezers. The wheat seedlings after the application of the pesticide were placed in an insect breeding room at 24±2℃, with a light cycle of D:L=16h:8h and a relative humidity of 50%-70%. After 48h, the number of deaths of the targets of each treatment was counted and the mortality rate was calculated. The test concentrations were 50mg / L respectively.

[0160] Among some of the tested compounds, compounds 3, 9, 26, 31, 35, 39, 58, 76, 81, 86, 90, 93, 98, 102, 107, 111, 115, 119, 146, 172, 178, 189, 195, 199, 204, 209, 214, 219, 224, 228, 232, 237, 247, 258, 263, 268, 275, 289, 293, 306, 321, 331, 333, 345 and 351 showed significant protective effects against armyworms at a concentration of 50 mg / L, with a mortality rate of 100%.

[0161] 2.5 Determination of activity against Chilo suppressalis

[0162] Leaf dipping method: Select rice seedlings about 25 cm tall that have grown in a 5 cm diameter pot for 3 weeks, about 30 per pot, remove old and dead leaves, pour a small amount of agar on the topsoil of the pot for fixation, and wait for the agar to solidify before use. Soak the rice seedlings in the liquid for 10 seconds, take them out, dry them until there is no clear water, cut the rice stems at the root, remove the upper leaves, and leave 5.5-6 cm of stems; put them in a pre-prepared culture dish with a diameter of 6.5 cm, put 4 layers of filter paper at the bottom of each dish, add 3 mL of sterile water to keep it moist, and put 15 stems in each dish; pick 10 2nd-instar larvae of the Chilo suppressalis with a brush, cover them with two layers of black cotton cloth, and then cover the culture dish to prevent the Chilo suppressalis larvae from escaping. Each experiment has 5-6 treatments, and each treatment is repeated 3 times. The treated larvae of Chilo suppressalis were placed in an incubator at 25°C, RH=70%, and a photoperiod of L:D=16:8. After 48 hours, the death of the larvae of Chilo suppressalis was checked. The death was considered when the insect body could not coordinate movement when the insect body was lightly touched with a brush. The test concentrations were 100 mg / L.

[0163] Among some of the tested compounds, compounds 3, 9, 26, 31, 35, 39, 58, 76, 81, 86, 90, 93, 98, 102, 107, 111, 115, 119, 146, 172, 178, 189, 195, 199, 204, 209, 214, 219, 224, 228, 232, 237, 247, 258, 275, 263, 268, 289, 293, 306, 321, 331, 333, 345 and 351 showed significant protective effects against Chilo suppressalis at a concentration of 100 mg / L, with a mortality rate of 100%.

[0164] 2.6 Comparative test: CN108137509A discloses an insecticide compound MC1 having a similar substitution structure. Some compounds of the general formula I of the present invention were selected to participate in the experiment and compared with MC1. The results are as follows:

[0165] Table 3 The lethality of the compounds of the present invention to Plutella xylostella at different dosages

[0166]

[0167] The test results show that the compounds of the present invention have a high mortality rate against diamondback moth, fall armyworm, fall armyworm, armyworm and striped stem borer at different dosages and using different test methods. Other compounds shown in the general formula I obtained by the preparation process described above also have the above corresponding characteristics and achieve unexpected effects. It can be predicted that even if the dosage of the compound is further reduced, the compounds of the present invention still have outstanding control effects and have good development prospects.

[0168] In addition to the pest control properties, the compounds according to the present invention unexpectedly show improved degradation properties compared to the compounds of the prior art. In addition, the compounds according to the present invention unexpectedly show lower toxicity to bees (or aquatic animals) compared to the compounds of the prior art.

[0169] The above embodiments are preferred implementation modes of the present invention, but the implementation modes of the present invention are not limited to the above embodiments. Any other changes, modifications, substitutions, combinations, and simplifications that do not deviate from the spirit and principles of the present invention should be equivalent replacement methods and are included in the protection scope of the present invention.

[0170] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the scope of protection of the present invention.

Claims

1. A compound of formula (I) or an isotope-labeled compound thereof, or an optical isomer, geometric isomer, tautomer or isomer mixture thereof, or a pesticidally acceptable salt thereof, which is an N-substituted phenylpyrazole derivative. in, X1, X2, X3, and X4 are each independently selected from hydrogen, halogen, hydroxy, nitro, amino, cyano, carboxyl, C 1-6 Alkyl, C 2-6 Alkenyl, C 2-6 Alkynyl, C 1-6 Haloalkyl, C 1-6 Alkoxy or C 1-6 Haloalkoxy; R1 is selected from hydrogen, halogen, hydroxy, cyano, nitro, amino, carboxyl, C 1-6 Alkyl, C 2-6 Alkenyl, C 2-6 Alkynyl, C 1-6 Haloalkyl, C 2-6 Halogenated alkenyl, C 2-6 Haloalkynyl, C 6-10 Aryl, C 6-10 Halogenated aryl, C 6-10 Aryl-C 1-6 Alkyl or C 6-10 Halogenated Aryl-C 1-6 alkyl; R2 is selected from hydrogen, C 1-6 Alkyl, C 1-6 Alkoxy, C 2-6 Alkenyl, C 2-6 Alkynyl, C 3-12 Cycloalkyl, C 3-6 Heterocyclic group, C 6-10 Aryl, C 5-12 Heteroaryl, C 1-6 Alkoxy C 1-6 Alkyl, C 3-12 Cycloalkyl C 1-6 Alkyl, and may be substituted or polysubstituted by one or more identical or different substituents selected from: halogen, cyano, C 1-6 Alkyl, C 1-6 Haloalkyl; Q is selected from C 1-6 Alkyl, C 2-6 Alkenyl, C 2-6 Alkynyl, C 3-12 Cycloalkyl, C 3-6 Heterocyclic group, C 6-10 Aryl, C 5-12 Heteroaryl, C 1-6 Alkoxy C 1-6 Alkyl, C 1-6 Alkylthio C 1-6 Alkyl, C 3-12 Cycloalkyl C 1-6 Alkyl, C 3-6 Heterocyclyl C 1-6 Alkyl, C 6-10 Aryl C 1-6 Alkyl, C 5-12 Heteroaryl C 1-6 Alkyl, C 6-10 Aryloxy C 1-6 Alkyl, C 5-12 Heteroaryloxy C 1-6 Alkyl, and may be substituted or polysubstituted by one or more identical or different substituents selected from: halogen, cyano, nitro, C 1-6 Alkyl, C 1-6 Alkoxy, C 1-6 Haloalkyl, C 1-6 Alkoxycarbonyl, C 1-3 Alkylamino, C 6-10 Aryl.

2. The compound of formula (I) according to claim 1 or its isotope-labeled compound, or its optical isomer, geometric isomer, tautomer or isomer mixture, or its pesticide-acceptable salt, wherein: X1, X2, X3, and X4 are each independently selected from hydrogen, halogen, hydroxy, nitro, amino, cyano, carboxyl, C 1-4 Alkyl, C 2-4 Alkenyl, C 2-4 Alkynyl, C 1-4 Haloalkyl, C 1-4 Alkoxy or C 1-4 Haloalkoxy; R1 is selected from hydrogen, halogen, hydroxy, cyano, nitro, amino, carboxyl, C 1-4 Alkyl, C 2-4 Alkenyl, C 2-4 Alkynyl, C 1-4 Haloalkyl, C 2-4 Halogenated alkenyl, C 2-4 Haloalkynyl, C 6-10 Aryl, C 6-10 Halogenated aryl, C 6-10 Aryl-C 1-3 Alkyl or C 6-10 Halogenated Aryl-C 1-3 alkyl; R2 is selected from hydrogen, C 1-3 Alkyl, C 1-3 Alkoxy, C 2-4 Alkenyl, C 2-4 Alkynyl, C 3-12 Cycloalkyl, C 3-6 Heterocyclic group, aryl group, C 5-12 Heteroaryl, C 1-3 Alkoxy C 1-3 Alkyl, C 3-12 Cycloalkyl C 1-3 Alkyl, and may be substituted or polysubstituted by one or more identical or different substituents, the substituents being selected from the group consisting of fluorine, chlorine, bromine, cyano, C 1-3 Alkyl, C 1-3 Haloalkyl; Q is selected from C 1-6 Alkyl, C 2-4 Alkenyl, C 2-4 Alkynyl, C 3-12 Cycloalkyl, C 3-6 Heterocyclic group, C 6-10 Aryl, C 5-12 Heteroaryl, C 1-3 Alkoxy C 1-3 Alkyl, C 1-3 Alkylthio C 1-3 Alkyl, C 3-12 Cycloalkyl C 1-3 Alkyl, C 3-6 Heterocyclyl C 1-3 Alkyl, C 6-10 Aryl C 1-3 Alkyl, C 5-12 Heteroaryl C 1-3 Alkyl, C 6-10 Aryloxy C 1-3 Alkyl, C 5-12 Heteroaryloxy C 1-3 Alkyl, and may be substituted or polysubstituted by one or more identical or different substituents, the substituents being selected from the group consisting of fluorine, chlorine, bromine, cyano, nitro, C 1-3 Alkyl, C 1-3 Alkoxy, C 1-3 Haloalkyl, C 1-3 Alkoxycarbonyl, C 1-3 Alkylamino, C 6-10 Aryl.

3. The compound of formula (I) according to claim 1 or its isotope-labeled compound, or its optical isomer, geometric isomer, tautomer or isomer mixture, or its pesticide-acceptable salt, wherein: X1, X2, X3, and X4 are each independently selected from hydrogen, fluorine, chlorine, bromine, iodine, hydroxyl, cyano, nitro, amino, carboxyl, C 1-4 Alkyl, C 1-4 Haloalkyl, C 1-4 Alkoxy or C 1-4 Haloalkoxy; R1 is selected from hydrogen, fluorine, chlorine, bromine, iodine, hydroxyl, cyano, nitro, amino, carboxyl, C 1-4 Alkyl or C 1-4 Haloalkyl; R2 is selected from hydrogen, C 1-3 Alkyl, C 1-3 Alkoxy, C 3-6 Cycloalkyl, C 3-6 Heterocyclic group, C 1-3 Alkoxy C 1-3 Alkyl, C 3-6 Cycloalkyl C 1-3 Alkyl, and may be substituted or polysubstituted by one or more identical or different substituents, the substituents being selected from the group consisting of fluorine, chlorine, bromine, cyano, C 1-3 Alkyl, C 1-3 Haloalkyl; Q is selected from C 1-6 Alkyl, C 2-4 Alkenyl, C 2-4 Alkynyl, C 3-6 Cycloalkyl, C 3-6 Heterocyclic group, C 6-10 Aryl, C 5-12 Heteroaryl, C 1-3 Alkoxy C 1-3 Alkyl, C 1-3 Alkylthio C 1-3 Alkyl, C 3-6 Cycloalkyl C 1-3 Alkyl, C 3-6 Heterocyclyl C 1-3 Alkyl, C 6-10 Aryl C 1-3 Alkyl, C 5-12 Heteroaryl C 1-3 Alkyl, and may be mono- or poly-substituted by one or more identical or different substituents selected from: Fluorine, chlorine, bromine, cyano, nitro, C 1-3 Alkyl, C 1-3 Alkoxy, C 1-3 Haloalkyl, C 1-3 Alkoxycarbonyl, C 1-3 Alkylamino.

4. The compound of formula (I) according to claim 1 or its isotope-labeled compound, or its optical isomer, geometric isomer, tautomer or isomer mixture, or its pesticide-acceptable salt, wherein: X1, X2, X3, X4 are each independently selected from hydrogen, fluorine, chlorine, bromine, iodine, -CH3, -CH2CH3, -CH2CH2CH3, -CH(CH3)2, -C(CH3)3, -CH2Cl, -CHF2, -CF3, -CH(CF3)2, -CF(CH3)2, -C(CF3)3, -CH2F, -CF2CH3, -CF(CF3)2, -C(OH)(CF3)2, -C(OCH3)(CF3)2; R1 is selected from hydrogen, fluorine, chlorine, bromine, iodine, hydroxyl, cyano, nitro, amino, carboxyl, -CH3, -CH2CH3, -CH2CH2CH3, -CH(CH3)2, -C(CH3)3, -CH2Cl, -CHF2, -CF3; R2 is selected from hydrogen, C 1-3 Alkyl, C 1-3 Alkoxy, C 3-6 Cycloalkyl, C 1-3 Alkoxy C 1-3 Alkyl, C 3-6 Cycloalkyl C 1-3 Alkyl, and may be substituted or polysubstituted by one or more identical or different substituents, the substituents being selected from the group consisting of fluorine, chlorine, bromine, cyano, C 1-3 Alkyl, C 1-3 Haloalkyl; Q is selected from C 1-6 Alkyl, C 2-4 Alkenyl, C 2-4 Alkynyl, C 3-6 Cycloalkyl, C 1-3 Alkoxy C 1-3 Alkyl, C 1-3 Alkylthio C 1-3 Alkyl, C 3-6 Cycloalkyl C 1-3 Alkyl or the following groups, And it may be singly or polysubstituted by one or more identical or different substituents, and the substituents are selected from: fluorine, chlorine, bromine, cyano, nitro, -CH3, -CH2CH3, -CHF2, -CF3, -OCH3, -OCH2CH3, -OCF3, -NHCH3, -N(CH3)2.

5. The compound of formula (I) according to claim 1 or its isotope-labeled compound, or its optical isomer, geometric isomer, tautomer or isomer mixture, or its pesticide-acceptable salt, which has the following structure:

6. An insecticide composition comprising a compound of formula (I) according to any one of claims 1 to 5 or an isotope-labeled compound thereof, or an optical isomer, geometric isomer, tautomer or isomer mixture thereof, or a pesticidally acceptable salt thereof, and a pesticidally acceptable carrier.

7. The insecticide composition according to claim 6, wherein the dosage form is selected from powders, granules, liquids, suspensions or sprays, preferably wettable powders, wettable liquids, soluble powders, dispersible liquids, aqueous solutions, microemulsions, emulsifiable concentrates, aqueous emulsions, sprayable solutions, dispersible oil suspensions, microcapsule suspensions, water-dispersible granules, water-soluble granules, large granules, granules for broadcasting and soil application, aerosols, ultra-low volume agents and wax products.

8. Use of a compound of formula (I) or an isotope-labeled compound thereof, or an optical isomer, geometric isomer, tautomer or isomer mixture thereof, or an acceptable salt thereof in pesticides, or a composition according to claim 6 as a pest control agent in agriculture, forestry or gardening.

9. The use according to claim 8, wherein the pests are selected from the group consisting of pests belonging to the phylum Arthropoda, the order Coleoptera, the order Diptera, the order Heteroptera, the order Homoptera, the order Hymenoptera, the order Isoptera, the order Lepidoptera, the order Orthoptera, the order Phylum Acropora, the order Thysanoptera, and the phylum Nematoda.

10. The use according to claim 9, wherein the pest is selected from the group consisting of Plutella xylostella, Spodoptera frugiperda, Armyworm, Spodoptera litura or Chilo suppressalis.

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