CN111943900B

CN111943900B - Isoxazoline derivatives and their use in agriculture

Info

Publication number: CN111943900B
Application number: CN201910412776.7A
Authority: CN
Inventors: 李义涛; 林健; 池伟林; 邱鹏飞
Original assignee: Ningxia Sulongda Chemical Co ltd
Current assignee: Ningxia Jianpai Agrochemical Technology Co.,Ltd.
Priority date: 2019-05-17
Filing date: 2019-05-17
Publication date: 2023-11-17
Anticipated expiration: 2039-05-17
Also published as: CN111943900A

Abstract

The invention provides isoxazoline derivatives and their use in agriculture; specifically, the invention provides a compound shown in a formula (I) or a stereoisomer, a nitrogen oxide or a salt of the compound shown in the formula (I), and a preparation method thereof; wherein R is ¹ 、R ² 、R ³ 、R ⁴ 、n、R ⁵ 、R ⁶ 、R ⁷ 、R ⁸ And Acy has the meaning as described in the present invention. Further, the invention provides compositions containing these compounds and their use in agriculture, in particular as herbicide active ingredients for controlling unwanted plants.

Description

Isoxazoline derivatives and their use in agriculture

Technical Field

The invention relates to the field of pesticides, and particularly provides a novel isoxazoline derivative and a preparation method thereof; compositions containing these compounds and their use in agriculture.

Background

Isoxazolines are a class of compounds with excellent biological activity, the herbicidal activity of which is reported, for example, in JP 2005213168A. However, the compounds of the present invention described in detail below are not described in these documents.

The active ingredients known from the above-cited documents have disadvantages in use, for example (a) have no or only inadequate herbicidal action on the weed plants, (b) have a too narrow spectrum of weed plants to be controlled or (c) have too low a selectivity in crops of useful plants.

Thus, there is a need to provide chemically active ingredients that can be advantageously used as herbicides or plant growth regulators.

Disclosure of Invention

The present invention provides a novel isoxazoline compound having excellent herbicidal action and excellent selectivity between crops and weeds.

In one aspect, the present invention provides a compound of formula (I) or a stereoisomer, oxynitride or salt thereof:

wherein:

R ¹ and R is ² Each independently is hydrogen, fluorine, chlorine, bromine, iodine, amino, nitro, cyano, hydroxy, carboxyl, C _1-6 Alkyl, C _3-8 Cycloalkyl or C _3-8 Cycloalkyl C _1-6 An alkyl group; or R is ¹ 、R ² And together with the carbon atoms to which they are attached form a ring consisting of 3 to 10 atoms;

R ³ and R is ⁴ Each independently is hydrogen, fluorine, chlorine, bromine, iodine, amino, nitro,Cyano, hydroxy, carboxyl, C _1-6 Alkyl, C _3-8 Cycloalkyl or C _3-8 Cycloalkyl C _1-6 An alkyl group; or R is ³ 、R ⁴ And together with the carbon atoms to which they are attached form a ring consisting of 3 to 10 atoms;

n is 0, 1 or 2;

R ⁵ and R is ⁶ Each independently is hydrogen, fluorine, chlorine, bromine, iodine, amino, nitro, cyano, hydroxy, carboxyl, C _1-6 Alkyl, C _2-6 Alkenyl or C _2-6 Alkynyl; or R is ⁵ 、R ⁶ And together with the carbon atoms to which they are attached form a ring consisting of 3 to 10 atoms;

R ⁷ And R is ⁸ Each independently is hydrogen, fluorine, chlorine, bromine, iodine, C _1-6 Alkyl, C _2-6 Alkenyl or C _2-6 Alkynyl;

acy is C _3-8 Cycloalkyl, C _2-10 Heterocyclyl, C _6-14 Aryl or C _1-9 Heteroaryl;

wherein R is ¹ 、R ² 、R ³ 、R ⁴ 、R ⁵ 、R ⁶ 、R ⁷ 、R ⁸ And Acy is optionally substituted with one or more groups selected from fluorine, chlorine, bromine, iodine, hydroxyl, cyano, nitro, amino, carboxyl, C _1-6 Alkyl, C _2-6 Alkenyl, C _2-6 Alkynyl, halo C _1-6 Alkyl, halogenated C _2-6 Alkenyl, halo C _2-6 Alkynyl, hydroxy-substituted C _1-6 Alkyl, amino substituted C _1-6 Alkyl-and cyano-substituted C _1-6 Alkyl, C _1-6 Alkoxy, halo C _1-6 Alkoxy, hydroxy-substituted C _1-6 Alkoxy, amino substituted C _1-6 Alkoxy, cyano-substituted C _1-6 Alkoxy, C _1-6 Alkylamino, C _3-8 Cycloalkyl, C _6-10 Aryl, C _6-10 Aryloxy or C _1-9 Substituents of heteroaryl groups are substituted;

the conditions are as follows:

when R is ¹ And R is ² Is methyl, R ³ And R is ⁴ Is hydrogen, n is 2, R ⁵ And R is ⁶ Is hydrogen, R ⁷ Is hydrogen or methyl, R ⁸ When hydrogen, acy is not unsubstituted phenyl.

In some embodiments, R ¹ And R is ² Each independently is hydrogen, fluorine, chlorine, bromine, iodine, amino, nitro, cyano, hydroxy, carboxyl, C _1-4 Alkyl, C _3-6 Cycloalkyl or C _3-6 Cycloalkyl C _1-4 An alkyl group; or R is ¹ 、R ² And together with the carbon atoms to which they are attached form a ring consisting of 3 to 8 atoms;

R ³ And R is ⁴ Each independently is hydrogen, fluorine, chlorine, bromine, iodine, amino, nitro, cyano, hydroxy, carboxyl, C _1-4 Alkyl, C _3-6 Cycloalkyl or C _3-6 Cycloalkyl C _1-4 An alkyl group; or R is ³ 、R ⁴ And together with the carbon atoms to which they are attached form a ring consisting of 3 to 8 atoms;

R ⁵ and R is ⁶ Each independently is hydrogen, fluorine, chlorine, bromine, iodine, amino, nitro, cyano, hydroxy, carboxyl, C _1-4 Alkyl, C _2-4 Alkenyl or C _2-4 Alkynyl; or R is ⁵ 、R ⁶ And together with the carbon atoms to which they are attached form a ring consisting of 3 to 8 atoms;

R ⁷ and R is ⁸ Each independently is hydrogen, fluorine, chlorine, bromine, iodine, C _1-4 Alkyl, C _2-4 Alkenyl or C _2-4 Alkynyl groups.

In other embodiments, R ¹ And R is ² Each independently is hydrogen, fluorine, chlorine, bromine, iodine, amino, nitro, cyano, hydroxy, carboxyl, methyl, ethyl, n-propyl, isopropyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl, cyclohexylmethyl, cyclopropylethyl or cyclohexylethyl; and

R ³ and R is ⁴ Each independently is hydrogen, fluorine, chlorine, bromine, iodine, amino, nitro, cyano, hydroxy, carboxyl, methyl, ethyl, n-propyl, isopropyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, cyclobutyl Methyl, cyclopentylmethyl, cyclohexylmethyl, cyclopropylethyl or cyclohexylethyl.

In some embodiments, acy is C _3-6 Cycloalkyl, C _2-6 Heterocyclyl, C _6-10 Aryl or C _1-6 Heteroaryl;

wherein Acy is optionally substituted with one or more groups selected from fluorine, chlorine, bromine, iodine, hydroxyl, cyano, nitro, amino, carboxyl, C _1-4 Alkyl, C _2-4 Alkenyl, C _2-4 Alkynyl, halo C _1-4 Alkyl, halogenated C _2-4 Alkenyl, halo C _2-4 Alkynyl, hydroxy-substituted C _1-4 Alkyl, amino substituted C _1-4 Alkyl-and cyano-substituted C _1-4 Alkyl, C _1-4 Alkoxy, halo C _1-4 Alkoxy, hydroxy-substituted C _1-4 Alkoxy, amino substituted C _1-4 Alkoxy, cyano-substituted C _1-4 Alkoxy, C _1-4 Alkylamino, C _3-6 Cycloalkyl, C _6-10 Aryl, C _6-10 Aryloxy or C _1-5 The substituents of heteroaryl groups are substituted.

In other embodiments, acy is phenyl or C _1-5 Heteroaryl;

wherein Acy is optionally substituted with one or more groups selected from fluorine, chlorine, bromine, iodine, hydroxyl, cyano, nitro, amino, carboxyl, C _1-3 Alkyl, C _2-3 Alkenyl, C _2-3 Alkynyl, halo C _1-3 Alkyl, halogenated C _2-3 Alkenyl, halo C _2-3 Alkynyl, hydroxy-substituted C _1-3 Alkyl, amino substituted C _1-3 Alkyl-and cyano-substituted C _1-3 Alkyl, C _1-3 Alkoxy, halo C _1-3 Alkoxy, hydroxy-substituted C _1-3 Alkoxy, amino substituted C _1-3 Alkoxy, cyano-substituted C _1-3 Alkoxy, C _1-3 Alkylamino, C _3-6 Cycloalkyl, C _6-10 Aryl, C _6-10 Aryloxy or C _1-5 The substituents of heteroaryl groups are substituted.

In some embodiments, the present invention provides a compound that is a compound of formula (II) or a stereoisomer, nitroxide, or salt thereof of a compound of formula (II):

wherein n, R ^a 、R ^b 、R ^c 、R ^d And R is ^e Has the meaning as described in the present invention.

In other embodiments, R ^a 、R ^b 、R ^c 、R ^d And R is ^e Each independently is hydrogen, fluorine, chlorine, bromine, iodine, hydroxyl, cyano, nitro, amino, carboxyl, C _1-3 Alkyl, C _2-3 Alkenyl, C _2-3 Alkynyl, halo C _1-3 Alkyl, halogenated C _2-3 Alkenyl, halo C _2-3 Alkynyl, hydroxy-substituted C _1-3 Alkyl, amino substituted C _1-3 Alkyl-and cyano-substituted C _1-3 Alkyl, C _1-3 Alkoxy, halo C _1-3 Alkoxy, hydroxy-substituted C _1-3 Alkoxy, amino substituted C _1-3 Alkoxy, cyano-substituted C _1-3 Alkoxy, C _1-3 Alkylamino, C _3-6 Cycloalkyl, C _6-10 Aryl, C _6-10 Aryloxy or C _1-5 Heteroaryl;

the conditions are as follows: r is R ^a 、R ^b 、R ^c 、R ^d And R is ^e At least one of which is other than hydrogen.

In some embodiments, the present invention provides a compound that is a compound of formula (III) or a stereoisomer, nitroxide, or salt thereof of a compound of formula (III):

Wherein n, R ^f 、R ^g And R is ^h Has the meaning as described in the present invention.

In other embodiments, R ^f 、R ^g And R is ^h Each independently is hydrogen, fluorineChlorine, bromine, iodine, hydroxyl, cyano, nitro, amino, carboxyl, C _1-3 Alkyl, C _2-3 Alkenyl, C _2-3 Alkynyl, halo C _1-3 Alkyl, halogenated C _2-3 Alkenyl, halo C _2-3 Alkynyl, hydroxy-substituted C _1-3 Alkyl, amino substituted C _1-3 Alkyl-and cyano-substituted C _1-3 Alkyl, C _1-3 Alkoxy, halo C _1-3 Alkoxy, hydroxy-substituted C _1-3 Alkoxy, amino substituted C _1-3 Alkoxy, cyano-substituted C _1-3 Alkoxy, C _1-3 Alkylamino, C _3-6 Cycloalkyl, C _6-10 Aryl, C _6-10 Aryloxy or C _1-5 Heteroaryl groups.

In other embodiments, R ^a 、R ^b 、R ^c 、R ^d 、R ^e 、R ^f 、R ^g And R is ^h Each independently is hydrogen, fluoro, chloro, bromo, iodo, hydroxy, cyano, nitro, amino, carboxy, methyl, ethyl, n-propyl, isopropyl, ethenyl, propenyl, allyl, ethynyl, difluoromethyl, trifluoromethyl, methoxy, difluoromethoxy, trifluoromethoxy, ethoxy, n-propoxy, isopropoxy, or phenoxy.

In other embodiments, R ^a Is fluorine, chlorine, bromine, iodine, methyl or trifluoromethyl.

In other embodiments, R ^c Is fluorine, chlorine, bromine, iodine, hydroxyl, methoxy or ethoxy.

In other embodiments, R ^d Hydrogen, fluorine, chlorine, bromine or iodine.

In other embodiments, R ^b And R is ^e Each independently is hydrogen.

In other embodiments, R ^f Is difluoromethyl or trifluoromethyl.

In other embodiments, R ^g Is methyl, ethyl, n-propyl or isopropyl.

In other embodiments, R ^h Hydrogen, fluorine or chlorine.

In another aspect, the present invention provides a composition comprising a compound of the present invention or a stereoisomer, oxynitride or salt thereof, further optionally comprising at least one pesticidally acceptable adjuvant.

Further, the present invention provides a herbicidal composition comprising as an active ingredient the compound of the present invention or a stereoisomer, nitrogen oxide or salt thereof, and further optionally at least one pesticidally acceptable adjuvant.

In another aspect, the invention provides the use of a compound of the invention or a composition comprising a compound of the invention in agriculture.

Further, the present invention provides the use of the compound of the present invention or a composition comprising the compound of the present invention in the control of plant diseases.

Still further, the present invention provides the use of a compound of the present invention or a composition comprising a compound of the present invention in agricultural weeding.

In some of these embodiments, the invention provides the use of a compound according to the invention or a composition comprising a compound according to the invention for controlling unwanted vegetation.

In another aspect, the present invention provides a method for controlling unwanted plants, characterized in that an effective amount of a compound of the present invention is applied to the plants, plant seeds, soil in or on which the plants are grown, or the cultivation area.

In a further aspect, the present invention provides a method of controlling weed growth in a useful plant comprising applying to the locus of the weed an effective amount of a compound of the invention.

The compounds of formula (I), formula (II) or formula (III) may exist in different stereoisomers or optical isomers or tautomeric forms. The present invention encompasses all such isomers and tautomers and mixtures thereof in various proportions, as well as isotopic forms such as heavy hydrogen-containing compounds.

The compound shown in the formula (I), the formula (II) or the formula (III) can be in a Z configuration, or in an E configuration, or a mixture of the Z configuration and the E configuration.

Isotopically enriched compounds have structures depicted by the formulae given herein except that one or more atoms are replaced by an atom having a selected atomic or mass number. Exemplary isotopes that can be incorporated into compounds of the application include isotopes of hydrogen, carbon, nitrogen, oxygen, phosphorus, sulfur, fluorine, and chlorine, such as ² H， ³ H， ¹¹ C， ¹³ C， ¹⁴ C， ¹⁵ N， ¹⁷ O， ¹⁸ O， ¹⁸ F， ³¹ P， ³² P， ³⁵ S， ³⁶ Cl and Cl ¹²⁵ I。

Any asymmetric atom (e.g., carbon, etc.) of the disclosed compounds may exist in racemic or enantiomerically enriched form, such as in the (R) -, (S) -or (R, S) -configuration.

The foregoing merely outlines certain aspects of the application and is not limited to these and other aspects, which are described more fully below.

Detailed description of the application

Definitions and general terms

Reference will now be made in detail to certain embodiments of the application, examples of which are illustrated in the accompanying structural and chemical formulas. The application is intended to cover all alternatives, modifications and equivalents, which may be included within the scope of the application as defined by the appended claims. Those skilled in the art will recognize that many methods and materials similar or equivalent to those described herein can be used in the practice of the present application. The present application is in no way limited to the methods and materials described herein. In the event of one or more of the incorporated references, patents and similar materials differing from or contradictory to the present application (including but not limited to defined terms, term application, described techniques, etc.), the present application controls.

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

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. All patents and publications referred to herein are incorporated by reference in their entirety.

The following definitions as used herein should be applied unless otherwise indicated. For the purposes of the present invention, chemical elements are in accordance with CAS version of the periodic Table of the elements, and handbook of chemistry and physics, 75 th edition, 1994. In addition, general principles of organic chemistry may be referenced to the descriptions in "Organic Chemistry", thomas Sorrell, university Science Books, sausalato: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.

The articles "a," "an," and "the" are intended to include "at least one" or "one or more" unless the context clearly dictates otherwise or otherwise. Thus, as used herein, these articles refer to one or to more than one (i.e., to at least one) object. For example, "a component" refers to one or more components, i.e., more than one component is contemplated as being employed or used in embodiments of the described embodiments.

The term "comprising" is an open-ended expression, i.e., including what is indicated by the invention, but not excluding other aspects.

"stereoisomers" refer to compounds having the same chemical structure but different arrangements of atoms or groups in space. Stereoisomers include enantiomers, diastereomers, conformational isomers (rotamers), geometric isomers (cis/trans), atropisomers, and the like.

"enantiomer" refers to two isomers of a compound that do not overlap but are in mirror image relationship to each other.

"diastereoisomers" refers to stereoisomers which have two or more chiralities and whose molecules are not mirror images of each other. Diastereomers have different physical properties, such as melting point, boiling point, spectral properties, and reactivity. The diastereomeric mixture may be separated by high resolution analytical procedures such as electrophoresis and chromatography, e.g., HPLC.

The stereochemical definitions and rules used in the present invention generally follow S.P. Parker, ed., mcGraw-Hill Dictionary of Chemical Terms (1984) McGraw-Hill Book Company, new York; and Eliel, e.and Wilen, s., "Stereochemistry of Organic Compounds", john Wiley & Sons, inc., new York, 1994.

Many organic compounds exist in optically active form, i.e., they have the ability to rotate the plane of plane polarized light. In describing optically active compounds, the prefixes D and L or R and S are used to represent the absolute configuration of the molecule with respect to one or more of its chiral centers. The prefixes d and l or (+) and (-) are symbols for specifying the rotation of plane polarized light by a compound, where (-) or l indicates that the compound is left-handed. The compound prefixed with (+) or d is dextrorotatory. One particular stereoisomer is an enantiomer, and a mixture of such isomers is referred to as an enantiomeric mixture. A50:50 mixture of enantiomers is referred to as a racemic mixture or racemate, which can occur when there is no stereoselectivity or stereospecificity in a chemical reaction or process.

The compounds of the invention may be optionally substituted with one or more substituents, as described in the present invention, such as the compounds of the general formula above, or as specific examples within the examples, subclasses, and classes of compounds encompassed by the invention. It is to be understood that the term "optionally substituted" may be 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 with a specific substituent. An optional substituent group may be substituted at each substitutable position of the group unless otherwise indicated. When more than one position in a given formula can be substituted with one or more substituents selected from a particular group, then the substituents may be the same or different at each position. Wherein the substituents may be, but are not limited to, deuterium, fluorine, chlorine, bromine, iodine, cyano, hydroxyl, nitro, amino, carboxyl, alkyl, alkoxy, alkoxyalkyl, alkoxyalkoxy, alkoxyalkylamino, aryloxy, heteroaryloxy, heterocyclyloxy, arylalkoxy, heteroarylalkoxy, heterocyclylalkoxy, cycloalkylalkoxy, alkylamino alkyl, alkylamino, cycloalkylamino, cycloalkylalkylamino, alkylthio, haloalkyl, haloalkoxy, hydroxyl-substituted alkyl, hydroxyl-substituted alkylamino, cyano-substituted alkyl, cyano-substituted alkoxy, cyano-substituted alkylamino, amino-substituted alkyl, alkanoyl, heteroalkyl, cycloalkyl, cycloalkenyl, cycloalkylalkyl, heterocyclyl, heterocyclylalkyl, heterocyclylacyl, aryl, arylalkyl, arylamino, heteroaryl, heteroarylalkyl, heteroarylamino, amido, sulfonyl, aminosulfonyl, and the like.

In addition, unless explicitly indicated otherwise, the descriptions used in this disclosure of the manner in which each … is independently "and" … is independently "and" … is independently "are to be construed broadly as meaning that particular items expressed between the same symbols in different groups do not affect each other, or that particular items expressed between the same symbols in the same groups do not affect each other.

In the various parts of the present specification, substituents of the presently disclosed compounds are disclosed in terms of the type or scope of groups. It is specifically noted that the present invention includes each individual subcombination of the individual members of these group classes and ranges. For example, the term "C ₁ -C ₆ Alkyl "or" C _1-6 Alkyl "means in particular methyl, ethyl, C independently disclosed ₃ Alkyl, C ₄ Alkyl, C ₅ Alkyl and C ₆ An alkyl group.

The term "alkyl" or "alkyl group" as used herein, means a saturated straight or branched monovalent hydrocarbon group containing 1 to 20 carbon atoms; wherein the alkyl group is optionally substituted with one or more substituents described herein. Unless otherwise specified, alkyl groups contain 1 to 20 carbon atoms. In one embodiment, the alkyl group contains 1 to 12 carbon atoms; in one embodiment, the alkyl group contains 1 to 10 carbon atoms; in one embodiment, the alkyl group contains 1 to 8 carbon atoms; in another embodiment, the alkyl group contains 1 to 6 carbon atoms; in yet another embodiment, the alkyl group contains 1 to 4 carbon atoms; in yet another embodiment, the alkyl group contains 1 to 3 carbon atoms.

Examples of alkyl groups include, but are not limited to, methyl (Me, -CH ₃ ) Ethyl (Et, -CH) ₂ CH ₃ ) N-propyl (n-Pr, -CH) ₂ CH ₂ CH ₃ ) Isopropyl (i-Pr, -CH (CH) ₃ ) ₂ ) N-butyl (n-Bu, -CH) ₂ CH ₂ CH ₂ CH ₃ ) Isobutyl (i-Bu, -CH) ₂ CH(CH ₃ ) ₂ ) Sec-butyl (s-Bu, -CH (CH) ₃ )CH ₂ CH ₃ ) Tert-butyl (t-Bu, -C (CH) ₃ ) ₃ ) N-pentyl (-CH) ₂ CH ₂ CH ₂ CH ₂ CH ₃ ) 2-pentyl (-CH (CH) ₃ )CH ₂ CH ₂ CH ₃ ) 3-pentyl (-CH (CH) ₂ CH ₃ ) ₂ ) 2-methyl-2-butyl (-C (CH) ₃ ) ₂ CH ₂ CH ₃ ) 3-methyl-2-butyl (-CH (CH) ₃ )CH(CH ₃ ) ₂ ) 3-methyl-1-butyl (-CH) ₂ CH ₂ CH(CH ₃ ) ₂ ) 2-methyl-1-butyl (-CH) ₂ CH(CH ₃ )CH ₂ CH ₃ ) N-hexyl (-CH) ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₃ ) 2-hexyl (-CH (CH) ₃ )CH ₂ CH ₂ CH ₂ CH ₃ ) 3-hexyl (-CH (CH) ₂ CH ₃ )(CH ₂ CH ₂ CH ₃ ) 2-methyl-2-pentyl (-C (CH) ₃ ) ₂ CH ₂ CH ₂ CH ₃ ) 3-methyl-2-pentyl (-CH (CH) ₃ )CH(CH ₃ )CH ₂ CH ₃ ) 4-methyl-2-pentyl (-CH (CH) ₃ )CH ₂ CH(CH ₃ ) ₂ ) 3-methyl-3-pentyl (-C (CH) ₃ )(CH ₂ CH ₃ ) ₂ ) 2-methyl-3-pentyl (-CH (CH) ₂ CH ₃ )CH(CH ₃ ) ₂ ) 2, 3-dimethyl-2-butyl (-C (CH) ₃ ) ₂ CH(CH ₃ ) ₂ ) 3, 3-dimethyl-2-butyl (-CH (CH) ₃ )C(CH ₃ ) ₃ ) N-heptyl, n-octyl, and the like.

The term "alkenyl" denotes a straight-chain or branched monovalent hydrocarbon radical containing 2 to 12 carbon atoms, in which there is at least one site of unsaturation, i.e. one carbon-carbon sp ² A double bond, wherein the alkenyl group may be optionally substituted with one or more substituents described herein, including the positioning of "cis" and "tans", or the positioning of "E" and "Z". In one embodiment, the alkenyl group contains 2 to 10 carbon atoms; in one embodiment, the alkenyl group contains 2 to 8 carbon atoms; in another embodiment, the alkenyl group comprises 2 to 6 carbon atoms; in yet another embodiment, the alkenyl group contains 2 to 4 carbon atoms. Examples of alkenyl groups include, but are not limited to, vinyl (-ch=ch) ₂ ) Allyl (-CH) ₂ CH＝CH ₂ ) Propenyl (CH) ₃ -CH＝CH-)，-CH ₂ CH ₂ CH＝CH ₂ 、-CH ₂ CH＝CHCH ₃ 、-CH ₂ CH ₂ CH ₂ CH＝CH ₂ 、-CH ₂ CH ₂ CH＝CHCH ₃ 、-CH ₂ CH ₂ CH ₂ CH＝CHCH ₃ Etc.

As described in connection with the present invention,the compound containing a double bond may be in the Z configuration, in the E configuration, or in a mixture of the Z and E configurations.

The term "alkynyl" denotes a straight or branched chain monovalent hydrocarbon radical containing 2 to 12 carbon atoms, wherein there is at least one carbon-carbon sp triple bond, wherein the alkynyl group may be optionally substituted with one or more substituents described herein. In one embodimentAlkynyl groups contain 2 to 10 carbon atoms; in one embodiment, the alkynyl group contains 2 to 8 carbon atoms; in another embodiment, the alkynyl group contains 2 to 6 carbon atoms; in yet another embodiment, the alkynyl group contains 2 to 4 carbon atoms. Examples of alkynyl groups include, but are not limited to, -C.ident.CH, -C.ident.CCH ₃ 、-CH ₂ -C≡CH、-CH ₂ -C≡CCH ₃ 、-CH ₂ CH ₂ -C≡CH、-CH ₂ -C≡CCH ₂ CH ₃ 、-CH ₂ CH ₂ -C≡CH ₂ CH ₃ Etc.

The term "alkoxy" means that the alkyl group is attached to the remainder of the molecule through an oxygen atom, wherein the alkyl group has the meaning as described herein. Unless otherwise specified, the alkoxy groups contain 1 to 12 carbon atoms. In one embodiment, the alkoxy group contains 1 to 10 carbon atoms; in one embodiment, the alkoxy group contains 1 to 8 carbon atoms; in one embodiment, the alkoxy group contains 1 to 6 carbon atoms; in another embodiment, the alkoxy group contains 1 to 4 carbon atoms; in yet another embodiment, the alkoxy group contains 1 to 3 carbon atoms. The alkoxy group may be optionally substituted with one or more substituents described herein.

Examples of alkoxy groups include, but are not limited to, methoxy (MeO, -OCH) ₃ ) Ethoxy (EtO, -OCH) ₂ CH ₃ ) 1-propoxy (n-PrO, n-propoxy, -OCH) ₂ CH ₂ CH ₃ ) 2-propoxy (i-PrO, i-propoxy, -OCH (CH) ₃ ) ₂ ) 1-butoxy (n-BuO, n-butoxy, -OCH) ₂ CH ₂ CH ₂ CH ₃ ) 2-methyl-l-propoxy (i-BuO, i-butoxy, -OCH) ₂ CH(CH ₃ ) ₂ ) 2-butoxy (s-BuO, s-butoxy, -OCH (CH) ₃ )CH ₂ CH ₃ ) 2-methyl-2-propoxy (t-BuO, t-butoxy, -OC (CH) ₃ ) ₃ ) 1-pentoxy (n-pentoxy, -OCH) ₂ CH ₂ CH ₂ CH ₂ CH ₃ ) 2-pentoxy (-OCH (CH) ₃ )CH ₂ CH ₂ CH ₃ ) 3-pentoxy (-OCH (CH) ₂ CH ₃ ) ₂ ) 2-methyl-2-butoxy (-OC (CH) ₃ ) ₂ CH ₂ CH ₃ ) 3-methyl-2-butoxy (-OCH (CH) ₃ )CH(CH ₃ ) ₂ ) 3-methyl-l-butoxy (-OCH) ₂ CH ₂ CH(CH ₃ ) ₂ ) 2-methyl-l-butoxy (-OCH) ₂ CH(CH ₃ )CH ₂ CH ₃ ) And so on.

The term "alkylamino" or "alkylamino" includes "N-alkylamino" and "N, N-dialkylamino" in which the amino groups are each independently substituted with one or two alkyl groups. Some of these are, for example, alkylamino groups of one or two C _1-6 Lower alkylamino groups wherein the alkyl group is attached to the nitrogen atom. Other embodiments are where the alkylamino group is C _1-3 Lower alkylamino groups of (a). Suitable alkylamino groups may be mono-or di-alkylamino, examples of which include, but are not limited to, N-methylamino, N-ethylamino, N, N-dimethylamino, N, N-diethylamino, and the like.

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

The term "haloalkyl" means an alkyl group substituted with one or more halogen atoms. Examples of haloalkyl groups include, but are not limited to, -CH ₂ F，-CHF ₂ ，-CH ₂ Cl，-CH ₂ Br，-CF ₃ ，-CH ₂ CF ₃ ，-CH ₂ CH ₂ F，-CH ₂ CH ₂ Cl，-CH ₂ CH ₂ Br，-CH ₂ CHF ₂ ，-CH ₂ CH ₂ CF ₃ ，-CH ₂ CH ₂ CH ₂ F，-CH ₂ CH ₂ CH ₂ Cl，-CH ₂ CH ₂ CH ₂ Br，-CHFCH ₂ CH ₃ ，-CHClCH ₂ CH ₃ And so on.

The term "haloalkoxy" means that the alkoxy group is substituted with one or more halogen atoms. Examples of haloalkoxy groups include, but are not limited to, -OCH ₂ F，-OCHF ₂ ，-OCH ₂ Cl，-OCH ₂ Br，-OCF ₃ ，-OCH ₂ CF ₃ ，-OCH ₂ CH ₂ F，-OCH ₂ CH ₂ Cl，-OCH ₂ CH ₂ Br，-OCH ₂ CHF ₂ ，-OCH ₂ CH ₂ CF ₃ ，-OCH ₂ CH ₂ CH ₂ F，-OCH ₂ CH ₂ CH ₂ Cl，-OCH ₂ CH ₂ CH ₂ Br，-OCHFCH ₂ CH ₃ ，-OCHClCH ₂ CH ₃ And so on.

The term "haloalkenyl" means that the alkenyl group is substituted with one or more halogen atoms.

The term "haloalkynyl" means that the alkynyl group is substituted with one or more halogen atoms.

The term "hydroxy-substituted alkyl" means that the alkyl group is substituted with one or more hydroxy groups.

The term "hydroxy-substituted alkoxy" means that the alkoxy group is substituted with one or more hydroxy groups.

The term "amino substituted alkyl" means that the alkyl group is substituted with one or more amino groups.

The term "amino-substituted alkoxy" means that the alkoxy group is substituted with one or more amino groups.

The term "cyano-substituted alkyl" means that the alkyl group is substituted with one or more cyano groups.

The term "cyano-substituted alkoxy" means that the alkoxy group is substituted with one or more cyano groups.

The term "ring of x atoms", where x is an integer, typically describes the number of ring-forming atoms in a molecule where the number of ring-forming atoms is x. For example, piperidinyl is a heterocyclic group consisting of 6 atoms.

The term "ring of 3 to 10 atoms" refers to a carbocyclic, heterocyclic or aromatic ring system of 3 to 10 atoms, i.e., a saturated, partially unsaturated or fully unsaturated ring system optionally containing one or more heteroatoms.

The term "3-8 atom ring" refers to a 3-8 atom carbocyclic, heterocyclic or aromatic ring system, i.e., a saturated, partially unsaturated or fully unsaturated ring system optionally containing one or more heteroatoms.

The term "3-6 atom ring" refers to a 3-6 atom carbocyclic, heterocyclic or aromatic ring system, i.e., a saturated, partially unsaturated or fully unsaturated ring system optionally containing one or more heteroatoms.

The term "carbocyclyl" or "carbocycle" means a monovalent or polyvalent, non-aromatic, saturated or partially unsaturated, mono-, bi-or tricyclic ring system containing 3 to 12 carbon atoms, 3 to 10 carbon atoms, 3 to 8 carbon atoms or 3 to 6 carbon atoms. Carbobicyclo groups include spirocarbobicyclo groups and fused carbobicyclo groups, and suitable carbocyclyl groups include, but are not limited to, cycloalkyl or cycloalkenyl groups. Examples of carbocyclyl groups further include cyclopropyl, cyclobutyl, cyclopentyl, 1-cyclopentyl-1-enyl, 1-cyclopentyl-2-enyl, 1-cyclopentyl-3-enyl, cyclohexyl, 1-cyclohexyl-1-enyl, 1-cyclohexyl-2-enyl, 1-cyclohexyl-3-enyl, cyclohexadienyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl, cyclododecyl, and the like.

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

The term "cycloalkylalkyl" means that the alkyl group is substituted with a cycloalkyl group, where the alkyl group and cycloalkyl group have the meanings as described herein.

The term "cycloalkenyl" means a monovalent or polyvalent mono-, bi-or tricyclic ring system containing from 3 to 12 carbon atoms, containing at least one carbon-carbon double bond, said ring system being non-aromatic. In one embodiment, cycloalkenyl groups contain 3 to 10 carbon atoms; in another embodiment, cycloalkenyl groups contain 3-8 carbon atoms; in yet another embodiment, cycloalkenyl groups contain 3-6 carbon atoms. The cycloalkenyl group is optionally substituted with one or more substituents described herein. Examples include, but are not limited to, cyclobutenyl, cyclopentenyl, cyclohexenyl, cyclohexadienyl, and the like.

The term "unsaturated" as used in the present invention means that the group contains one or more unsaturations.

The term "heteroatom" refers to O, S, N, P and Si, including N, S and any oxidation state forms of P; primary, secondary, tertiary and quaternary ammonium salt forms; or a form in which the hydrogen on the nitrogen atom in the heterocycle is substituted, for example, N (like N in 3, 4-dihydro-2H-pyrrolyl), NH (like NH in pyrrolidinyl) or NR (like NR in N-substituted pyrrolidinyl).

The terms "heterocyclyl" and "heterocycle" are used interchangeably herein to refer to a saturated or partially unsaturated monocyclic, bicyclic or tricyclic ring containing 3 to 15 ring atoms, wherein the monocyclic, bicyclic or tricyclic ring contains no aromatic rings and at least one ring atom is selected from the group consisting of nitrogen, sulfur and oxygen atoms. Unless otherwise indicated, a heterocyclic group may be a carbon or nitrogen group, and-CH ₂ The group may optionally be replaced by-C (=o) -. The sulfur atom of the ring may optionally be oxidized to an S-oxide. The nitrogen atom of the ring may optionally be oxidized to an N-oxide. Examples of heterocyclyl groups include, but are not limited to, oxiranyl, azetidinyl, oxetanyl, thietanyl, pyrrolidinyl (e.g., 2-pyrrolidinyl), 2-pyrrolinyl, 3-pyrrolinyl, pyrazolidinyl, imidazolinyl, imidazolidinyl, tetrahydrofuranyl, dihydrofuranyl, tetrahydrothienyl, dihydrothienyl, 1, 3-dioxacyclopentyl, dithiocyclopentyl, tetrahydropyranyl, dihydropyranyl, 2H-pyranyl, 4H-pyranyl, tetrahydrothiopyranyl, piperidinyl (2-piperidinyl, 3-piperidinyl, 4-piperidinyl), morpholinyl, thiomorpholinyl (1-oxo) -thiomorpholinyl, (1, 1-dioxo) -thiomorpholinyl, piperazinyl, dioxanyl, dithianyl, thiazanyl, homopiperazinyl, homopiperidinyl, oxaheptanyl, thiepanyl, 2-oxa-5-azabicyclo [2.2.1]Hept-5-yl, tetrahydropyridinyl. In heterocyclic groups-CH ₂ Examples of the substitution of the-group by-C (=o) -include, but are not limited to, 2-oxopyrrolidinyl, oxo-1, 3-thiazolidinyl, 2-piperidonyl, 3, 5-dioxopiperidyl. Examples of sulfur atoms in the heterocyclic group that are oxidized include, but are not limited to, sulfolane, 1-dioxothiomorpholino. The heterocyclyl group is optionally substituted with one or more substituents described herein.

The term "aryl" means a monocyclic, bicyclic and tricyclic carbocyclic ring system containing 6 to 14 ring atoms, or 6 to 12 ring atoms, or 6 to 10 ring atoms, wherein at least one ring system is aromatic, wherein each ring system contains a ring of 3 to 7 atoms, and wherein one or more attachment points are attached to the remainder of the molecule. The term "aryl" may be used interchangeably with the term "aromatic ring". Examples of aryl groups may include phenyl, indenyl, naphthyl and anthracenyl. The aryl group is optionally substituted with one or more substituents described herein.

The term "aryloxy" or "aryloxy" includes optionally substituted aryl groups, as defined herein, attached to and from an oxygen atom, with the aryl groups having the meaning as described herein, attached to the remainder of the molecule.

The term "heteroaryl" means monocyclic, bicyclic and tricyclic ring systems containing 5 to 12 ring atoms, or 5 to 10 ring atoms, or 5 to 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 a ring of 5 to 7 atoms and has one or more attachment points attached to the remainder of the molecule. The term "heteroaryl" may be used interchangeably with the term "heteroaromatic ring" or "heteroaromatic compound". The heteroaryl group is optionally substituted with one or more substituents described herein.

In one embodiment, the heteroaryl group of 5 to 10 atoms comprises 1,2,3 or 4 heteroatoms independently selected from O, S and N.

In another embodiment, the ring atoms of the heteroaryl group comprise 1 to 9 carbon atoms and 1 to 4 heteroatoms selected from N, O or S; in another embodiment, the ring atoms of the heteroaryl group comprise 1 to 5 carbon atoms and 1 to 4 heteroatoms selected from N, O or S.

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

Examples of heteroaryl groups include, but are not limited to, 2-furyl, 3-furyl, 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-triazolyl, 3-triazolyl, 1, 3-triazolyl, 3-thiotriazinyl, 1, 2-thiotriazinyl, 1-thiotriazinyl; the following bicyclic rings are also included, but are in no way limited to: benzimidazolyl, benzofuranyl, benzothienyl, indolyl (e.g., 2-indolyl), and the like.

When the compounds of the present invention contain one acid moiety, salts of the compounds of the present invention include those derived from alkali metals or alkaline earth metals, as well as those derived from ammonia and amines. Preferred cations include sodium, potassium, magnesium and have the formula N ⁺ (R ¹⁹ R ²⁰ R ²¹ R ²² ) Wherein R is an ammonium cation of ¹⁹ 、R ²⁰ 、R ²¹ And R is ²² Independently selected from hydrogen, C ₁ -C ₆ Alkyl and C ₁ -C ₆ A hydroxyalkyl group. Salts of compounds of formula (I) may be prepared by treating a compound of formula (I), formula (II) or formula (III) with a metal hydroxide (e.g., sodium hydroxide) or an amine (e.g., ammonia, trimethylamine, diethanolamine, 2-methylthiopropylamine, bisallylamine, 2-butoxyethylamine, morpholine, cyclododecamine or benzylamine).

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

Detailed description of the compounds of the invention

The invention aims to provide a novel isoxazoline compound, a herbicide composition and a preparation containing the compound and application thereof.

In one aspect, the present invention provides a compound which is a compound of formula (I) or a stereoisomer, oxynitride or salt thereof of a compound of formula (I):

wherein:

R ³ and R is ⁴ Each independently is hydrogen, fluorine, chlorine, bromine, iodine, amino, nitro, cyano, hydroxy, carboxyl, C _1-6 Alkyl, C _3-8 Cycloalkyl or C _3-8 Cycloalkyl C _1-6 An alkyl group; or R is ³ 、R ⁴ And together with the carbon atoms to which they are attached form a ring consisting of 3 to 10 atoms;

n is 0, 1 or 2;

the conditions are as follows:

In some embodiments, R ¹ And R is ² Each independently is hydrogen, fluorine, chlorine, bromine, iodine, amino, nitro, cyano, hydroxy, carboxyl, C _1-4 Alkyl, C _3-6 Cycloalkyl or C _3-6 Cycloalkyl C _1-4 An alkyl group; or R is ¹ 、R ² And together with the carbon atoms to which they are attached form a ring consisting of 3 to 8 atoms.

In some embodiments, R ³ And R is ⁴ Each independently is hydrogen, fluorine, chlorine, bromine, iodine, amino, nitro, cyano, hydroxy, carboxyl, C _1-4 Alkyl, C _3-6 Cycloalkyl or C _3-6 Cycloalkyl C _1-4 An alkyl group; or R is ³ 、R ⁴ And together with the carbon atoms to which they are attached form a ring consisting of 3 to 8 atoms.

In some embodiments, R ⁵ And R is ⁶ Each independently is hydrogen, fluorine, chlorine, bromine, iodine, amino, nitro, cyano, hydroxy, carboxyl, C _1-4 Alkyl, C _2-4 Alkenyl or C _2-4 Alkynyl; or R is ⁵ 、R ⁶ And together with the carbon atoms to which they are attached form a ring consisting of 3 to 8 atoms.

In some embodiments, R ⁷ And R is ⁸ Each independently is hydrogen, fluorine, chlorine, bromine, iodine, C _1-4 Alkyl, C _2-4 Alkenyl or C _2-4 Alkynyl groups.

In other embodiments, R ¹ And R is ² Each independently is hydrogen, fluorine, chlorine, bromine, iodine, amino, nitro, cyano, hydroxy, carboxyl, methyl, ethyl, n-propyl, isopropyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl, cyclohexylmethyl, cyclopropylethyl or cyclohexylethyl.

In other embodiments, R ³ And R is ⁴ Each independently is hydrogen, fluorine,Chlorine, bromine, iodine, amino, nitro, cyano, hydroxyl, carboxyl, methyl, ethyl, n-propyl, isopropyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl, cyclohexylmethyl, cyclopropylethyl or cyclohexylethyl.

In other embodiments, acy is phenyl or C _1-5 Heteroaryl;

In one embodiment, R ^a Is hydrogen, fluorine, chlorine, bromine, iodine, hydroxyl, cyano, nitro, amino, carboxyl, C _1-3 Alkyl, C _2-3 Alkenyl, C _2-3 Alkynyl, halo C _1-3 Alkyl, halogenated C _2-3 Alkenyl, halo C _2-3 Alkynyl, hydroxy-substituted C _1-3 Alkyl, amino substituted C _1-3 Alkyl-and cyano-substituted C _1-3 Alkyl, C _1-3 Alkoxy, halo C _1-3 Alkoxy, hydroxy-substituted C _1-3 Alkoxy, amino substituted C _1-3 Alkoxy, cyano-substituted C _1-3 Alkoxy, C _1-3 Alkylamino, C _3-6 Cycloalkyl, C _6-10 Aryl, C _6-10 Aryloxy or C _1-5 Heteroaryl groups.

In one embodiment, R ^b Is hydrogen, fluorine, chlorine, bromine, iodine, hydroxyl, cyano, nitro, amino, carboxyl, C _1-3 Alkyl, C _2-3 Alkenyl, C _2-3 Alkynyl, halo C _1-3 Alkyl, halogenated C _2-3 Alkenyl, halo C _2-3 Alkynyl, hydroxy-substituted C _1-3 Alkyl, amino substituted C _1-3 Alkyl-and cyano-substituted C _1-3 Alkyl, C _1-3 Alkoxy, halo C _1-3 Alkoxy, hydroxy-substituted C _1-3 Alkoxy, amino substituted C _1-3 Alkoxy, cyano-substituted C _1-3 Alkoxy, C _1-3 Alkylamino, C _3-6 Cycloalkyl, C _6-10 Aryl, C _6-10 Aryloxy or C _1-5 Heteroaryl groups.

In one embodiment, R ^c Is hydrogen, fluorine, chlorine, bromine, iodine, hydroxyl, cyano, nitro, amino, carboxyl, C _1-3 Alkyl, C _2-3 Alkenyl, C _2-3 Alkynyl, halo C _1-3 Alkyl, halogenated C _2-3 Alkenyl, halo C _2-3 Alkynyl, hydroxy-substituted C _1-3 Alkyl, amino substituted C _1-3 Alkyl-and cyano-substituted C _1-3 Alkyl, C _1-3 Alkoxy, halo C _1-3 Alkoxy, hydroxy-substituted C _1-3 Alkoxy, amino substituted C _1-3 Alkoxy, cyano-substituted C _1-3 Alkoxy, C _1-3 Alkylamino, C _3-6 Cycloalkyl, C _6-10 Aryl, C _6-10 Aryloxy or C _1-5 Heteroaryl groups.

In one embodiment, R ^d Is hydrogen, fluorine, chlorine, bromine, iodine, hydroxyl, cyano, nitro, amino, carboxyl, C _1-3 Alkyl, C _2-3 Alkenyl, C _2-3 Alkynyl, halo C _1-3 Alkyl, halogenated C _2-3 Alkenyl, halo C _2-3 Alkynyl, hydroxy-substituted C _1-3 Alkyl, amino substituted C _1-3 Alkyl-and cyano-substituted C _1-3 Alkyl, C _1-3 Alkoxy, halo C _1-3 Alkoxy, hydroxy-substituted C _1-3 Alkoxy, amino substituted C _1-3 Alkoxy, cyano-substituted C _1-3 Alkoxy, C _1-3 Alkylamino, C _3-6 Cycloalkyl, C _6-10 Aryl, C _6-10 Aryloxy or C _1-5 Heteroaryl groups.

In one embodiment, R ^e Is hydrogen, fluorine, chlorine, bromine, iodine, hydroxyl, cyano, nitro, amino, carboxyl, C _1-3 Alkyl, C _2-3 Alkenyl, C _2-3 Alkynyl, halo C _1-3 Alkyl, halogenated C _2-3 Alkenyl, halo C _2-3 Alkynyl, hydroxy-substituted C _1-3 Alkyl, amino substituted C _1-3 Alkyl-and cyano-substituted C _1-3 Alkyl, C _1-3 Alkoxy, halo C _1-3 Alkoxy, hydroxy-substituted C _1-3 Alkoxy, amino substituted C _1-3 Alkoxy, cyano-substituted C _1-3 Alkoxy, C _1-3 Alkylamino, C _3-6 Cycloalkyl, C _6-10 Aryl, C _6-10 Aryloxy or C _1-5 Heteroaryl groups.

wherein R is ^f 、R ^g And R is ^h Has the meaning as described in the present invention.

In one embodiment, R ^f Is hydrogen, fluorine, chlorine, bromine, iodine, hydroxyl, cyano, nitro, amino, carboxyl, C _1-3 Alkyl, C _2-3 Alkenyl, C _2-3 Alkynyl, halo C _1-3 Alkyl, halogenated C _2-3 Alkenyl, halo C _2-3 Alkynyl, hydroxy-substituted C _1-3 Alkyl, amino substituted C _1-3 Alkyl-and cyano-substituted C _1-3 Alkyl, C _1-3 Alkoxy, halo C _1-3 Alkoxy, hydroxy-substituted C _1-3 Alkoxy, amino substituted C _1-3 Alkoxy, cyano-substituted C _1-3 Alkoxy, C _1-3 Alkylamino, C _3-6 Cycloalkyl, C _6-10 Aryl, C _6-10 Aryloxy or C _1-5 Heteroaryl groups.

In one embodiment, R ^g Is hydrogen, fluorine, chlorine, bromine, iodine, hydroxyl, cyano, nitro, amino, carboxyl, C _1-3 Alkyl, C _2-3 Alkenyl, C _2-3 Alkynyl, halo C _1-3 Alkyl, halogenated C _2-3 Alkenyl, halo C _2-3 Alkynyl, hydroxy-substituted C _1-3 Alkyl, amino substituted C _1-3 Alkyl-and cyano-substituted C _1-3 Alkyl, C _1-3 Alkoxy, halo C _1-3 Alkoxy, hydroxy or takeSubstituted C _1-3 Alkoxy, amino substituted C _1-3 Alkoxy, cyano-substituted C _1-3 Alkoxy, C _1-3 Alkylamino, C _3-6 Cycloalkyl, C _6-10 Aryl, C _6-10 Aryloxy or C _1-5 Heteroaryl groups.

In one embodiment, R ^h Is hydrogen, fluorine, chlorine, bromine, iodine, hydroxyl, cyano, nitro, amino, carboxyl, C _1-3 Alkyl, C _2-3 Alkenyl, C _2-3 Alkynyl, halo C _1-3 Alkyl, halogenated C _2-3 Alkenyl, halo C _2-3 Alkynyl, hydroxy-substituted C _1-3 Alkyl, amino substituted C _1-3 Alkyl-and cyano-substituted C _1-3 Alkyl, C _1-3 Alkoxy, halo C _1-3 Alkoxy, hydroxy-substituted C _1-3 Alkoxy, amino substituted C _1-3 Alkoxy, cyano-substituted C _1-3 Alkoxy, C _1-3 Alkylamino, C _3-6 Cycloalkyl, C _6-10 Aryl, C _6-10 Aryloxy or C _1-5 Heteroaryl groups.

In other embodiments, R ^a Is hydrogen, fluoro, chloro, bromo, iodo, hydroxy, cyano, nitro, amino, carboxy, methyl, ethyl, n-propyl, isopropyl, ethenyl, propenyl, allyl, ethynyl, difluoromethyl, trifluoromethyl, methoxy, difluoromethoxy, trifluoromethoxy, ethoxy, n-propoxy, isopropoxy or phenoxy.

In other embodiments, R ^b Is hydrogen, fluoro, chloro, bromo, iodo, hydroxy, cyano, nitro, amino, carboxy, methyl, ethyl, n-propyl, isopropyl, ethenyl, propenyl, allyl, ethynyl, difluoromethyl, trifluoromethyl, methoxy, difluoromethoxy, trifluoromethoxy, ethoxy, n-propoxy, isopropoxy or phenoxy.

In other embodiments, R ^c Is hydrogen, fluorine, chlorine, bromine, iodine, hydroxyl, cyano, nitro, amino, carboxyl, methyl, ethyl, n-propyl, isopropyl, vinyl, propenyl, allyl, ethynyl, difluoromethyl, trifluoromethyl, methoxyA radical, difluoromethoxy, trifluoromethoxy, ethoxy, n-propoxy, isopropoxy or phenoxy.

In other embodiments, R ^d Is hydrogen, fluoro, chloro, bromo, iodo, hydroxy, cyano, nitro, amino, carboxy, methyl, ethyl, n-propyl, isopropyl, ethenyl, propenyl, allyl, ethynyl, difluoromethyl, trifluoromethyl, methoxy, difluoromethoxy, trifluoromethoxy, ethoxy, n-propoxy, isopropoxy or phenoxy.

In other embodiments, R ^e Is hydrogen, fluoro, chloro, bromo, iodo, hydroxy, cyano, nitro, amino, carboxy, methyl, ethyl, n-propyl, isopropyl, ethenyl, propenyl, allyl, ethynyl, difluoromethyl, trifluoromethyl, methoxy, difluoromethoxy, trifluoromethoxy, ethoxy, n-propoxy, isopropoxy or phenoxy.

In other embodiments, R ^f Is hydrogen, fluoro, chloro, bromo, iodo, hydroxy, cyano, nitro, amino, carboxy, methyl, ethyl, n-propyl, isopropyl, ethenyl, propenyl, allyl, ethynyl, difluoromethyl, trifluoromethyl, methoxy, difluoromethoxy, trifluoromethoxy, ethoxy, n-propoxy, isopropoxy or phenoxy.

In other embodiments, R ^g Is hydrogen, fluoro, chloro, bromo, iodo, hydroxy, cyano, nitro, amino, carboxy, methyl, ethyl, n-propyl, isopropyl, ethenyl, propenyl, allyl, ethynyl, difluoromethyl, trifluoromethyl, methoxy, difluoromethoxy, trifluoromethoxy, ethoxy, n-propoxy, isopropoxy or phenoxy.

In other embodiments, R ^h Is hydrogen, fluoro, chloro, bromo, iodo, hydroxy, cyano, nitro, amino, carboxy, methyl, ethyl, n-propyl, isopropyl, ethenyl, propenyl, allyl, ethynyl, difluoromethyl, trifluoromethyl, methoxy, difluoromethoxy, trifluoromethoxy, ethoxy, n-propoxy, isopropoxy or phenoxy.

One of the implementation modesIn the scheme, R ^a Is fluorine, chlorine, bromine, iodine, C _1-3 Alkyl or halo C _1-3 An alkyl group.

In one embodiment, R ^c Is fluorine, chlorine, bromine, iodine, hydroxy or C _1-3 An alkoxy group.

In other embodiments, R ^d Hydrogen, fluorine, chlorine, bromine or iodine.

In other embodiments, R ^b And R is ^e Each independently is hydrogen.

In one embodiment, R ^f Is halogenated C _1-3 An alkyl group.

In other embodiments, R ^f Is difluoromethyl or trifluoromethyl.

In one embodiment, R ^g Is C _1-3 An alkyl group.

In other embodiments, R ^g Is methyl, ethyl, n-propyl or isopropyl.

In other embodiments, R ^h Hydrogen, fluorine or chlorine.

In some embodiments, the invention provides a compound that is a stereoisomer, nitroxide, or salt thereof, of a compound having one of the following structures:

/>

in another aspect, the invention provides a composition comprising a compound of the invention or a stereoisomer, oxynitride or salt thereof.

In some of these embodiments, the compositions of the present invention optionally further comprise at least one pesticidally acceptable adjuvant.

In other embodiments, the compositions of the present invention are herbicidal compositions.

In some of these embodiments, the invention provides the use of a compound of the invention or a composition comprising a compound of the invention for controlling unwanted vegetation.

The compound provided by the invention is a novel compound which is more effective to weeds, lower in cost, lower in toxicity and safe to environment.

Compositions and formulations of the compounds of the invention

The compounds of the present invention are generally useful as herbicide active ingredients in compositions or formulations having at least one pesticidally acceptable adjuvant selected from the group consisting of surfactants, solid diluents, liquid diluents and the like, which meet the requirements of the pesticide application are within the scope of the present invention. The formulation or composition ingredients are selected to be compatible with the physical characteristics of the active ingredient, the mode of application, and environmental factors such as soil type, humidity and temperature.

Useful formulations include liquid compositions and solid compositions. Liquid compositions include solutions (including emulsifiable concentrates), suspensions, emulsions (including microemulsions and/or suspoemulsions), and the like, which may optionally be thickened to a gel. General types of aqueous liquid compositions are soluble concentrates, suspension concentrates, capsule suspensions, concentrated emulsions, microemulsions and suspoemulsions. The general types of non-aqueous liquid compositions are emulsifiable concentrates, microemulsifiable concentrates, dispersible concentrates and oil dispersions.

The general types of solid compositions are powders, granules, pellets, lozenges, tablets, filled films (including seed coatings), and the like, which may be water dispersible ("wettable") or water soluble. Films and coatings formed from film-forming solutions or flowable suspensions are particularly useful for seed treatment. The active ingredient may be (micro) encapsulated and further form a suspension or solid formulation; alternatively, the entire active ingredient formulation may be encapsulated (or "coated"). Encapsulation can control or delay the release of the active ingredient. Emulsifiable granules combine the advantages of both emulsifiable concentrate formulations and dry granule formulations. The high concentration compositions are mainly used as intermediates for other formulations.

Sprayable formulations are typically dispersed in a suitable medium prior to spraying. Such liquid and solid formulations are formulated as formulations that are readily diluted in a spray medium (typically water). The spray volume may be in the range of about one to several thousand litres per hectare, but more typically in the range of about ten to several hundred litres per hectare. The sprayable formulation may be mixed with water or another suitable medium in a sink for treatment of the foliage by air or ground application or into the growing medium of the plant. The liquid and dry formulations may be dosed directly into the drip irrigation system or into the furrow during planting.

The formulation will typically comprise an effective amount of the active ingredient, diluent and surfactant, the sum being 100% by weight.

Solid diluents include, for example, clays such as bentonite, montmorillonite, attapulgite and kaolin, gypsum, cellulose, titanium dioxide, zinc oxide, starch, dextrin, sugar (e.g., lactose, sucrose), silica, talc, mica, diatomaceous earth, urea, calcium carbonate, sodium carbonate and sodium bicarbonate, and sodium sulfate. Typical solid diluents are described in Watkins et al, handbook of Insecticide Dust Diluents and Carriers, 2 nd edition, dorland Books, caldwell, new Jersey.

Liquid diluents include, for example, water, N-dimethylalkanamide (e.g., N, N-dimethylformamide), limonene, dimethyl sulfoxide, N-alkylpyrrolidone (e.g., N-methylpyrrolidone), ethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, propylene carbonate, butylene carbonate, paraffins (e.g., white mineral oil, N-paraffins, isoparaffins), alkylbenzenes, alkylnaphthalenes, glycerol, glyceryl triacetate, sorbitol, aromatic hydrocarbons, dearomatized aliphatics, alkylbenzenes, alkylnaphthalenes, ketones (e.g., cyclohexanone, 2-heptanone, isophorone and 4-hydroxy-4-methyl-2-pentanone), acetates (e.g., isopentyl acetate, hexyl acetate, heptyl acetate, octyl acetate, nonyl acetate, tridecyl acetate and isobornyl acetate), other esters (e.g., alkylated lactate, dibasic esters and gamma-butyrolactone), and alcohols which may be linear, branched, saturated or unsaturated (e.g., methanol, ethanol, N-propanol, isopropanol, N-butanol, isobutanol, N-hexanol, 2-ethylhexanol, N-octanol, decanol, isodecanol, stearyl alcohol, lauryl alcohol, benzyl alcohol, and benzyl alcohol. Liquid diluents also include glycerides of saturated and unsaturated fatty acids (typically C6-C22), such as vegetable seed and fruit oils (e.g., olive oil, castor oil, linseed oil, sesame oil, corn oil, peanut oil, sunflower oil, grape seed oil, safflower oil, cottonseed oil, soybean oil, rapeseed oil, coconut oil, and palm kernel oil), animal-derived fats (e.g., tallow, lard, cod liver oil, fish oil), and mixtures thereof. Liquid diluents also include alkylated (e.g., methylated, ethylated, butylated) fatty acids, where the fatty acids can be obtained by hydrolysis of glycerides derived from plants and animals, and can be purified by distillation. Typical liquid diluents are described in solvent guides, 2 nd edition, interscience, new York,1950, of Marsden.

The solid and liquid compositions of the present invention generally comprise one or more surfactants. When added to a liquid, surfactants (also referred to as "surface-active agents") typically change, most typically lowering the surface tension of the liquid. Depending on the nature of the hydrophilic and lipophilic groups in the surfactant molecule, the surfactant may act as a wetting agent, dispersant, emulsifier or defoamer.

Surfactants can be classified as nonionic, anionic or cationic. Nonionic surfactants useful as the compositions of the present invention include, but are not limited to: alcohol alkoxylates, such as alcohol alkoxylates based on natural and synthetic alcohols (which are branched or linear) and prepared from alcohols and ethylene oxide, propylene oxide, butylene oxide or mixtures thereof; amine ethoxylated, alkanolamides and ethoxylated alkanolamides; alkoxylated triglycerides, such as ethoxylated soybeans, castor and rapeseed oils; alkylphenol ethoxylates, such as octylphenol ethoxylate, nonylphenol ethoxylate, dinonylphenol ethoxylate, and dodecylphenol ethoxylate (prepared from phenol and ethylene oxide, propylene oxide, butylene oxide, or mixtures thereof); a block polymer prepared from ethylene oxide or propylene oxide and a reverse block polymer, wherein the end block is prepared from propylene oxide; ethoxylated fatty acids; ethoxylated fatty esters and oils; ethoxylated methyl esters; ethoxylated tristyrylphenols (including those prepared from ethylene oxide, propylene oxide, butylene oxide, or mixtures thereof); fatty acid esters, glycerol esters, lanolin-based derivatives, polyethoxylated esters, such as polyethoxylated sorbitan fatty acid esters, polyethoxylated sorbitol fatty acid esters, and polyethoxylated glycerol fatty acid esters; other sorbitan derivatives such as sorbitan esters; polymeric surfactants such as random copolymers, block copolymers, alkyd PEG (polyethylene glycol) resins, grafted or comb polymers, and star polymers; polyethylene glycol (PEG); polyethylene glycol fatty acid esters; a silicone-based surfactant; and sugar derivatives such as sucrose esters, alkyl polyglucosides and alkyl polysaccharides.

Useful anionic surfactants include, but are not limited to: alkylaryl sulfonic acids and their salts; carboxylated alcohol or alkylphenol ethoxylates; diphenyl sulfonate derivatives; lignin and lignin derivatives, such as lignin sulfonates; maleic acid or succinic acid or their anhydrides; olefin sulfonate; phosphate esters such as phosphate esters of alcohol alkoxylates, phosphate esters of alkylphenol alkoxylates, and phosphate esters of styrylphenol ethoxylates; protein-based surfactants; sarcosine derivatives; styrylphenol ether sulfate; sulfates and sulfonates of oils and fatty acids; sulfates and sulfonates of ethoxylated alkylphenols; sulfate of alcohol; a sulfate salt of an ethoxylated alcohol; sulfonates of amines and amides, such as N, N-alkyl taurates; sulfonates of benzene, cumene, toluene, xylene, dodecylbenzene and tridecylbenzene; sulfonate of condensed naphthalene; sulfonates of naphthalene and alkyl naphthalenes; sulfonate of petroleum fraction; sulfosuccinamates; and sulfosuccinates and their derivatives, such as dialkyl sulfosuccinates.

Useful cationic surfactants include, but are not limited to: amides and ethoxylated amides; amines such as N-alkyl propylene diamine, tripropylene triamine and dipropylene tetramine, as well as ethoxylated amines, ethoxylated diamines and propoxylated amines (prepared from amines and ethylene oxide, propylene oxide, butylene oxide or mixtures thereof); amine salts such as amine acetate and diamine salts; quaternary ammonium salts such as quaternary salts, ethoxylated quaternary salts and di-quaternary salts; and amine oxides such as alkyl dimethyl amine oxide and di- (2-hydroxyethyl) -alkyl amine oxide.

Mixtures of nonionic and anionic surfactants, or mixtures of nonionic and cationic surfactants, may also be used in the compositions of the present invention. Nonionic, anionic and cationic surfactants and their proposed uses are disclosed in a number of published references, including McCutcheon's Division, the Manufacturing Confectioner Publishing co. Encyclopedia of Surface Active Agents by sisey and Wood, chemical publication.co., inc., new York,1964; and Synthetic Detergents by A.S. Davidson and B.Milwidsky, seventh edition, john Wiley and Sons, new York,1987.

The compositions of the present invention may also contain formulation aids and additives known to those skilled in the art as co-formulations (some of which may also be considered to act as solid diluents, liquid diluents or surfactants). Such formulation aids and additives can be controlled: pH (buffer), foaming during processing (defoamer such as polyorganosiloxane), sedimentation of active ingredient (suspending agent), viscosity (thixotropic thickener), microbial growth in the container (antimicrobial agent), product freezing (antifreeze), color (dye/pigment dispersion), elution (film former or binder), evaporation (anti-evaporation agent), and other formulation attributes. Film formers include, for example, polyvinyl acetate copolymers, polyvinylpyrrolidone-vinyl acetate copolymers, polyvinyl alcohol copolymers, and waxes. Examples of formulation aids and additives include McCutcheon's Volume 2 published by McCutcheon's Division, the Manufacturing Confectioner Publishing co: functional Materials, north America and International yearbook edition; and those listed in PCT publication WO 03/024322.

The compounds of the invention and any other active ingredients are typically incorporated into the compositions of the invention by dissolving the active ingredient in a solvent or by grinding the active ingredient in a liquid diluent or in a dry diluent. Solutions, including emulsifiable concentrates, can be prepared by simply mixing the ingredients. If the solvent used as the liquid composition of the emulsifiable concentrate is water-immiscible, an emulsifier is typically added to emulsify the solvent containing the active ingredient upon dilution with water. A media mill may be used to wet grind an active ingredient slurry having a particle size of up to 2,000 μm to obtain particles having an average diameter of less than 3 μm. The aqueous slurry may be prepared as a finished suspension concentrate (see, e.g., U.S.3,060,084) or further processed by spray drying to form water-dispersible granules. Dry formulations typically require a dry milling step that produces an average particle size in the range of 2 μm to 10 μm. Powders and powders may be prepared by mixing, and typically by grinding (e.g., with a hammer mill or fluid energy mill). Granules and pellets can be prepared by spraying the active material onto preformed particulate carriers or by agglomeration techniques. See Browning, "Agglomeration" (Chemical Engineering, 12/month 4/1967, pages 147-48; chemical Engineer's Handbook of Perry, 4 th edition, mcGraw-Hill, new York,1963, pages 8-57 and thereafter and WO91/13546. Pellets may be prepared as described in U.S.4,172,714. Water-dispersible and water-soluble granules may be prepared as set forth in U.S.4,144,050, U.S.3,920,442 and DE.3,246,493. Tablets may be prepared as set forth in U.S.5,180,587, U.S.5,232,701 and U.S.5,208,030. Films may be prepared as set forth in GB2,095,558 and U.S.3,299,566.

For additional information regarding The field of formulation, see "The Formulator's Toolbox-Product Forms for Modern Agriculture", pesticide Chemistry and Bioscience, the Food-Environment Challenge, edited by t.s. Brooks and t.r. roberts, proceedings of The 9th International Congress on Pesticide Chemistry,The Royal Society of Chemistry,Cambridge,1999, pages 120-133, of t.s. woods. See also U.S.3,235,361, column 6, line 16 to column 7, line 19 and examples 10-41; U.S.3,309,192, column 5, line 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.2,891,855, column 3, line 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, 8 th edition, blackwell Scientific Publications, oxford,1989; and Developments in formulation technology, PJB Publications, richmond, UK,2000.

Use of the compounds of the invention

The herbicides of the invention can be used by spraying plants, applying to the soil, applying to the water surface. The amount of the active ingredient is appropriately determined to meet the purpose of use. The content of the active ingredient is appropriately determined according to the purpose.

The amount of the compound of the present invention to be used depends on the kind of the compound used, the target weeds, the tendency of the weeds to appear, the environmental conditions, the kind of herbicide, etc. When the herbicide according to the invention is used by itself, for example in the form of a powder or granules, its amount is suitably chosen to be from 1g to 50kg, preferably from 10g to 10kg, of active ingredient per 1 hectare. When the herbicide of the present invention is used in liquid form, for example, in the form of emulsifiable concentrate, wettable powder or flowable formulation, its amount is suitably selected to be 0.1 to 50,000ppm, preferably 10 to 10,000ppm.

The present invention provides a method for controlling weeds in crops of useful plants, which method comprises applying to said weeds or to the locus of said weeds or to said useful plants or to the locus of said useful plants a compound or composition of the invention.

The present invention also provides a method of selectively controlling grasses and/or weeds in crops of useful plants, which comprises applying to the useful plants or to the locus thereof or to the cultivation area a herbicidally effective amount of a compound of formula (I), formula (II) or formula (III).

The term "herbicide" means a compound that controls or alters plant growth. The term "effective amount" means the amount of such a compound or a composition of such compounds that is capable of producing a controlled or altered plant growth effect. The effects of control or alteration include all naturally occurring deviations, e.g., killing, delay, leaf burn, albinism, dwarfing, etc. The term "plant" refers to all tangible parts of a plant, including seeds, seedlings, young plants, roots, tubers, stems, stalks, leaves, and fruits. The term "locus" is intended to include soil, seeds and seedlings, together with established plants (established vegetation) and includes not only areas where weeds may have grown, but also areas where weeds have not yet appeared, and also areas where crops of useful plants are grown. "area of planting" includes the land on which crop plants have grown, as well as the land intended for planting such crop plants. The term "weed" as used herein means any undesired plant and thus includes not only the important agronomic weeds as described below, but also volunteer crop plants.

Useful plant crops in which the compositions according to the invention may be used include, but are not limited to, perennial crops such as citrus fruits, vines, nuts, oil palm, olives, pomes, stone fruits and rubber, and annual cultivars such as cereals (e.g. barley and wheat), cotton, oilseed rape, maize, rice, soybean, sugar beet, sugarcane, sunflower, ornamental plants, switchgrass, turf and vegetables, especially cereals, maize and soybean.

The grass and weeds to be controlled may be monocotyledonous species such as, for example, agrimonia, myrtaria, avena, alternaria, bromus, tribulus, cyperus, crabgrass, barnyard, wild millet, lolium, july, panicum, poa, legionella, scirpus, setaria, sida and sorghum, or dicotyledonous species such as, for example, cannabis, amaranthus, chenopodium, chrysanthemum, euphorbia, lala, ipomoea, kochia, apocynum, polygonum, sida, sinapis, solanum, barbary, pogostemon, viola and Xanthium.

The compounds of the invention may show tolerance to important crops including, but not limited to, alfalfa, barley, cotton, wheat, canola, sugar beet, corn (maize), sorghum, soybean, rice, oat, peanut, vegetable, tomato, potato, perennial crops including coffee, cocoa, oil palm, rubber, sugarcane, citrus, grape, fruit tree, nut tree, banana, plantain, pineapple, hops, tea and forests such as in-tree and needle-leaved trees (e.g., loblolly pine), and turf species (e.g., bluegrass, st. Augustine grass), kentucky, and bermudagrass).

The compounds according to the invention of the formula (I), formula (II) or formula (III) can also be used, if desired, in combination with other active ingredients, for example other herbicides and/or insecticides and/or acaricides and/or nematicides and/or molluscicides and/or fungicides and/or plant growth regulators. These mixtures, and the use of these mixtures to control weeds and/or unwanted plant growth, form further aspects of the invention. For the avoidance of doubt, the inventive mixtures also include mixtures of two or more different compounds of formula (I), formula (II) or formula (III). In particular, the present invention also relates to a composition according to the invention comprising at least one further herbicide in addition to the compound according to formula (I), formula (II) or formula (III).

General synthetic procedure

In this specification, a structure is dominant if there is any difference between a chemical name and a chemical structure. In general, the compounds of the invention may be prepared by the methods described herein unless otherwise indicated. The starting materials, reagents, and the like used in preparing the compounds of the invention are all commercially available or may be prepared by methods conventional in the art.

The testing conditions of the nuclear magnetic resonance hydrogen spectrum of the invention are as follows: nuclear magnetic instrument of 400MHz or 600MHz of Bruker (Bruker) under room temperature condition, CDC1 ₃ ，d ⁶ -DMSO，CD ₃ OD or d ⁶ Acetone as solvent (reported in ppm) with TMS (0 ppm) or chloroform (7.26 ppm) as reference standard. When multiple peaks occur, the following abbreviations will be used: s (single, singlet), d (doublet ), t (triplet, quartet), q (quartet), m (multiplet ), br (broadened, broad), dd (doublet of doublets, doublet), dt (doublet of triplets, doublet). Coupling constants are expressed in hertz (Hz).

The mass spectrometry method used in the invention comprises the following steps: agilent 1260HPLC was used; agilent 6120ESI.

Phase A: water (0.1% formic acid); and B phase: acetonitrile (containing 0.1% formic acid).

Gradient elution: 0-3min,5-100% B;3-6min,100% B.

Flow rate: 0.6mL/min.

Detection wavelength: 254nm.

MS parameters: ESI is scanning, collision induced ionization: 70V.

And (3) drying nitrogen: 12L/min, atomization gas pressure: 40psi, gas temperature: 350 ℃.

Taking a proper amount of sample, dissolving in 0.5mL of methanol, sampling, and performing primary MS full scanning under a positive ESI mode to obtain an excimer ion peak [ M+H ] ] ⁺ And (5) reading.

The following abbreviations are used throughout the present invention:

petroleum ether: petroleum ether

DMF: n, N-dimethylformamide, dimethylformamide

EtOAc: acetic acid ethyl ester

NBS: n-bromosuccinimide

AIBN: azobisisobutyronitrile

The following synthetic schemes and examples are provided to further illustrate the teachings of the present invention.

Synthesis scheme one

The compounds of formula (E) can be prepared by synthesis scheme one, wherein n, R ^a 、R ^b 、R ^c 、R ^d And R is ^e Has the meaning as described in the present invention. Optionally substituted benzaldehyde (A) and ethyl triphenyl phosphonium bromide undergo a Witting reaction under alkaline conditions (such as potassium carbonate, sodium carbonate and the like) to obtain a compound (B); brominating the compound (B) under NBS and AIBN conditions to obtain a compound (C); the compound (C) and 5, 5-dimethyl-4, 5-dihydro-isoxazol-3-yl isothiourea hydrobromide undergo condensation reaction to obtain a compound of formula (D); further oxidation of the compound of formula (D) occurs to give the compound of formula (E).

Synthesis scheme II

The compound of formula (N) can be prepared by synthesis scheme II, wherein N and R ^f And R is ^g Having the meaning as described in the present invention; wherein X is halogen. Compounds of formula (F) and N ₂ H ₄ A ring closure reaction is carried out under an acidic condition to obtain a compound of a formula (G); compounds of formula (G) and POCl ₃ Performing a Vilsmeier-hacck reaction under DMF reflux condition to obtain a compound of formula (H); compounds of formula (H) and R ^g -X undergoes a substitution reaction under basic conditions to give a compound of formula (J); reacting the compound of formula (J) with ethyl triphenyl phosphonium bromide under alkaline conditions (such as potassium carbonate, sodium carbonate, etc.), to obtain compound (K); brominating the compound (K) under NBS and AIBN conditions to obtain a compound (L); the compound (L) and 5, 5-dimethyl-4, 5-dihydro-isoxazol-3-yl isothiourea hydrobromide undergo condensation reaction to obtain a compound of formula (M); further oxidation of the compound of formula (M) occurs to give the compound of formula (N).

Examples

Example 1: synthesis of Compound (E) -5, 5-dimethyl-3- ((3- (3- (trifluoromethyl) phenyl) allyl) sulfonyl) -4, 5-dihydroisoxazole

Step 1: synthesis of 5, 5-dimethyl-4, 5-dihydroisoxazol-3-yl isothiourea hydrobromide

Thiourea (6.00 g,79.00 mmol) was dissolved in acetonitrile (65 mL) at room temperature, hydrobromic acid (48%, 10 mL) was added dropwise, and the mixture was stirred at room temperature for 1h. To the above mixed solution was added dropwise 3-chloro-5, 5-dimethyl-4, 5-dihydroisoxazole (12.60 g,95.00 mmol), and the mixture was heated to 40℃and stirred overnight. The solvent was distilled off under reduced pressure, and the obtained solid was recrystallized from ethyl acetate to obtain 19.20g of white crystals, yield: 96.0%.

Step 2: synthesis of ethyl triphenyl phosphonium bromide

Triphenylphosphine (50.0 g,0.19 mol) was dissolved in anhydrous toluene (500 mL), then bromoethane (17.3 g,0.16 mol) was added dropwise to the reaction flask, the temperature was raised to 100 ℃ and refluxed overnight, after the reaction was completed, the temperature was lowered, and filtration was performed to obtain 41.6g of a white solid, yield: 70.5%.

Step 3: synthesis of Compound (E) -1- (prop-1-en-1-yl) -3- (trifluoromethyl) benzene

3- (trifluoromethyl) benzaldehyde (1.00 g,5.74 mmol) was dissolved in anhydrous dioxane (15.0 mL), then ethyl triphenylphosphonium bromide (2.35 g,6.32 mmol) and potassium carbonate (1.19 g,8.61 mmol) were added to the reaction flask, respectively, after the addition was completed, the temperature was raised to 110℃and stirred overnight, after the reaction was completed, the temperature was lowered, n-hexane (20 mL) was added, stirred at room temperature for 30 minutes, the filtration was performed, the solvent was removed from the filtrate under reduced pressure, and column chromatography (eluent: petroleum) was purified to give colorless liquid 500mg, yield: 43.5%.

MS-ESI:m/z 187.2[M+H] ⁺ .

Step 4: synthesis of Compound (E) -1- (3-bromoprop-1-en-1-yl) -3- (trifluoromethyl) benzene

(E) -1- (prop-1-en-1-yl) -3- (trifluoromethyl) benzene (500 mg,2.69 mmol) was dissolved in carbon tetrachloride (5.0 mL), NBS (526 mg,2.95 mmol) and AIBN (88 mg,0.54 mmol) were added to the reaction flask at room temperature, and then heated to 78℃and stirred overnight, after the reaction was completed, n-hexane (20 mL) was added, stirred at room temperature for 30 minutes, filtered, the solvent was removed from the filtrate under reduced pressure, and purified by column chromatography (eluent: petroleum) to give colorless liquid 400mg, yield: 56.2%.

MS-ESI:m/z 266.1[M+H] ⁺ .

Step 5: synthesis of Compound (E) -5, 5-dimethyl-3- ((3- (3- (trifluoromethyl) phenyl) allyl) thio) -4, 5-dihydroisoxazole

After dissolving (E) -1- (3-bromoprop-1-en-1-yl) -3- (trifluoromethyl) benzene (400 mg,1.51 mmol) and 5, 5-dimethyl-4, 5-dihydroisoxazol-3-yl isothiourea hydrobromide (460 mg,1.81 mmol) in acetonitrile (20 mL), stirring at room temperature for 10min, potassium carbonate (830 mg,6.04 mmol) was added to the above mixture, the reaction was stopped after 12h, acetonitrile was removed, water (30 mL) was washed, ethyl acetate (15 mL) was extracted three times, and the organic phase was combined and the solvent was removed under reduced pressure to give 400mg of a yellow liquid crude product, yield: 80.1%.

MS-ESI:m/z 316.4[M+H] ⁺ .

Step 6: synthesis of Compound (E) -5, 5-dimethyl-3- ((3- (3- (trifluoromethyl) phenyl) allyl) sulfonyl) -4, 5-dihydroisoxazole

(E) -5, 5-dimethyl-3- ((3- (3- (trifluoromethyl) phenyl) allyl) thio) -4, 5-dihydroisoxazole (400 mg,1.27 mmol) was dissolved in dichloromethane (10 mL), stirred at room temperature, then 75% m-chloroperoxybenzoic acid (284 mg,2.54 mmol) was added to the above mixture, the reaction was stopped after 12h, quenched with saturated aqueous sodium bisulphite (10 mL), extracted twice with dichloromethane (10 mL), washed with saturated aqueous sodium bicarbonate (10 mL), dried over anhydrous sodium sulphate, the solvent was removed under reduced pressure and column chromatography (eluent: petroleum ether/EtOAc (v/v) =5/1) was purified to give a white solid 0.30g, yield: 68.1%.

MS-ESI:m/z 348.4[M+H] ⁺ ；

¹ H NMR(400MHz,CDCl ₃ )δ7.65(s,1H),7.57(dd,J＝12.8,8.0Hz,2H),7.47(t,J＝7.7Hz,1H),6.80(d,J＝15.8Hz,1H),6.36–6.24(m,1H),4.27(d,J＝7.5Hz,2H),3.09(s,2H),1.48(s,6H).

Example 2: synthesis of Compound (E) -3- ((3- (2-chloro-4-fluorophenyl) allyl) sulfonyl) -5, 5-dimethyl-4, 5-dihydroisoxazole

Step 1: synthesis of Compound (E) -2-chloro-4-fluoro-1- (prop-1-en-1-yl) benzene

2-chloro-4-fluorobenzaldehyde (1.00 g,6.31 mmol) was dissolved in anhydrous dioxane (15.0 mL), and then ethyl triphenylphosphonium bromide (2.81 g,7.57 mmol) and potassium carbonate (1.31 g,9.46 mmol) were added to a reaction flask, respectively, after the addition was completed, the temperature was raised to 110℃and stirred overnight, after the completion of the reaction, the temperature was lowered, n-hexane (20 mL) was added, stirred at room temperature for 30 minutes, the filtrate was filtered, the solvent was removed under reduced pressure, and column chromatography (eluent: petroleum) was purified to give a colorless liquid 500mg, yield: 46.5%.

MS-ESI:m/z 171.6[M+H] ⁺ .

Step 2: synthesis of Compound (E) -1- (3-bromoprop-1-en-1-yl) -2-chloro-4-fluorobenzene

(E) -2-chloro-4-fluoro-1- (prop-1-en-1-yl) benzene (500 mg,2.93 mmol) was dissolved in carbon tetrachloride (5.0 mL), NBS (626 mg,3.52 mmol) and AIBN (96 mg,0.59 mmol) were added to the reaction flask at room temperature, then heated to 78℃and stirred overnight, after the reaction was completed, cooled, n-hexane (20 mL) was added, stirred at room temperature for 30 minutes, filtered, the solvent was removed from the filtrate under reduced pressure, and column chromatography (eluent: petroleum) was purified to give a colorless liquid 300mg, yield: 41.0%.

MS-ESI:m/z 250.5[M+H] ⁺ .

Step 3: synthesis of Compound (E) -3- ((3- (2-chloro-4-fluorophenyl) allyl) thio) -5, 5-dimethyl-4, 5-dihydroisoxazole

After dissolving (E) -1- (3-bromoprop-1-en-1-yl) -2-chloro-4-fluorobenzene (300 mg,1.20 mmol) and 5, 5-dimethyl-4, 5-dihydroisoxazol-3-yl isothiourea hydrobromide (367 mg,1.44 mmol) in acetonitrile (20 mL), stirring at room temperature for 10min, potassium carbonate (661mg, 4.81 mmol) was added to the above mixture, the reaction was stopped after 12h, acetonitrile was removed, washing with water (30 mL), ethyl acetate (15 mL) was extracted three times, the solvent was removed by combining the organic phases under reduced pressure, column chromatography (eluent: petroleum ether/EtOAc (v/v) =10/1) gave 200mg of yellow liquid, yield: 55.5%.

MS-ESI:m/z 300.8[M+H] ⁺ .

Step 4: synthesis of Compound (E) -3- ((3- (2-chloro-4-fluorophenyl) allyl) sulfonyl) -5, 5-dimethyl-4, 5-dihydroisoxazole

(E) -3- ((3- (2-chloro-4-fluorophenyl) allyl) thio) -5, 5-dimethyl-4, 5-dihydroisoxazole (200 mg,0.67 mmol) was dissolved in dichloromethane (10 mL), stirred at room temperature, then 75% m-chloroperoxybenzoic acid (307 mg,1.33 mmol) was added to the above mixture, the reaction was stopped after 12h, quenched with saturated aqueous sodium bisulphite (10 mL), extracted twice with dichloromethane (10 mL), washed with saturated aqueous sodium bicarbonate (10 mL), dried over anhydrous sodium sulphate, the solvent was removed by combining the organic phases under reduced pressure, and column chromatography (eluent: petroleum ether/EtOAc (v/v) =5/1) was purified to give 0.12g of white solid product, yield: 54.2%.

MS-ESI:m/z 332.8[M+H] ⁺ ；

¹ H NMR(400MHz,CDCl ₃ )δ7.63(d,J＝6.6Hz,1H),7.59(dd,J＝8.3,4.8Hz,1H),7.19(t,J＝9.2Hz,1H),6.75(d,J＝15.9Hz,1H),6.29–6.18(m,1H),4.26(d,J＝7.5Hz,2H),3.09(s,2H),1.48(s,6H).

Example 3: synthesis of Compound (E) -3- ((3- (4-fluoro-3- (trifluoromethyl) phenyl) allyl) sulfonyl) -5, 5-dimethyl-4, 5-dihydroisoxazole

Step 1: synthesis of Compound (E) -1-fluoro-4- (prop-1-en-1-yl) -2- (trifluoromethyl) benzene

4-fluoro-3- (trifluoromethyl) benzaldehyde (1.00 g,5.21 mmol) was dissolved in anhydrous dioxane (15.0 mL), then ethyl triphenylphosphonium bromide (2.32 g,6.25 mmol) and potassium carbonate (1.08 g,7.81 mmol) were added to the reaction flask, respectively, after the addition was completed, the temperature was raised to 110℃and stirred overnight, after the reaction was completed, n-hexane (20 mL) was added, stirred at room temperature for 30 minutes, the filtrate was filtered and the solvent was removed under reduced pressure, and column chromatography (eluent: petroleum) was purified to give colorless liquid 500mg, yield: 47.1%.

MS-ESI:m/z 205.2[M+H] ⁺ .

Step 2: synthesis of Compound (E) -4- (3-bromoprop-1-en-1-yl) -1-fluoro-2- (trifluoromethyl) benzene

(E) -1-fluoro-4- (prop-1-en-1-yl) -2- (trifluoromethyl) benzene (500 mg,2.45 mmol) was dissolved in carbon tetrachloride (5.0 mL), NBS (523 mg,2.94 mmol) and AIBN (80 mg,0.49 mmol) were added to the reaction flask at room temperature, and then heated to 78℃and stirred overnight, after the reaction was completed, n-hexane (20 mL) was added, stirred at room temperature for 30 minutes, the filtrate was filtered and the solvent was removed under reduced pressure, and column chromatography (eluent: petroleum) was purified to give 400mg of colorless liquid product, yield: 57.7%.

MS-ESI:m/z 284.1[M+H] ⁺ .

Step 3: synthesis of Compound (E) -3- ((3- (4-fluoro-3- (trifluoromethyl) phenyl) allyl) thio) -5, 5-dimethyl-4, 5-dihydroisoxazole

(E) -4- (3-bromoprop-1-en-1-yl) -1-fluoro-2- (trifluoromethyl) benzene (400 mg,1.41 mmol) and 5, 5-dimethyl-4, 5-dihydroisoxazol-3-yl isothiourea hydrobromide (431 mg,1.70 mmol) were dissolved in acetonitrile (20 mL), after stirring at room temperature for 10min, potassium carbonate (781 mg,5.65 mmol) was added to the above mixture, the reaction was stopped after 12h, acetonitrile was removed, washed with water (30 mL), ethyl acetate (15 mL) was extracted three times, the solvent was removed by combining the organic phases under reduced pressure, and column chromatography (eluent: petroleum ether/EtOAc (v/v) =10/1) was purified to give 400mg of yellow liquid, yield: 84.9%.

MS-ESI:m/z 334.3[M+H] ⁺ ；

¹ H NMR(400MHz,CDCl ₃ )δ7.50(dd,J＝8.7,6.1Hz,1H),7.09(dd,J＝8.5,2.6Hz,1H),6.98–6.86(m,2H),6.36–6.23(m,1H),3.86(d,J＝7.3Hz,2H),2.17(s,2H),1.42(s,6H).

Step 4: synthesis of Compound (E) -3- ((3- (4-fluoro-3- (trifluoromethyl) phenyl) allyl) sulfonyl) -5, 5-dimethyl-4, 5-dihydroisoxazole

(E) -3- ((3- (4-fluoro-3- (trifluoromethyl) phenyl) allyl) thio) -5, 5-dimethyl-4, 5-dihydroisoxazole (300 mg,0.90 mmol) was dissolved in dichloromethane (10 mL), stirred at room temperature, then 75% m-chloroperoxybenzoic acid (414 mg,1.80 mmol) was added to the above mixture, the reaction was stopped after 12h, quenched with saturated aqueous sodium bisulphite (10 mL), extracted twice with dichloromethane (10 mL), washed with saturated aqueous sodium bicarbonate (10 mL), dried over anhydrous sodium sulphate, the solvent was removed by combining the organic phases under reduced pressure, and column chromatography (eluent: petroleum ether/EtOAc (v/v) =5/1) was purified to give a white solid, 0.21g, yield: 63.9%.

MS-ESI:m/z 366.3[M+H] ⁺ ；

¹ H NMR(400MHz,CDCl ₃ )δ7.54(dd,J＝8.7,6.0Hz,1H),7.13(dd,J＝8.4,2.5Hz,1H),7.08(d,J＝15.8Hz,1H),6.99(td,J＝8.3,2.4Hz,1H),6.17(dt,J＝15.5,7.6Hz,1H),4.27(d,J＝7.4Hz,2H),3.09(s,2H),1.48(s,6H).

Example 4: synthesis of Compound (E) -3- ((3- (4-fluoro-2- (trifluoromethyl) phenyl) allyl) sulfonyl) -5, 5-dimethyl-4, 5-dihydroisoxazole

Step 1: synthesis of Compound (E) -4-fluoro-1- (prop-1-en-1-yl) -2- (trifluoromethyl) benzene

4-fluoro-2- (trifluoromethyl) benzaldehyde (1.00 g,5.21 mmol) was dissolved in anhydrous dioxane (15.0 mL), then ethyl triphenylphosphonium bromide (2.32 g,6.25 mmol) and potassium carbonate (1.08 g,7.81 mmol) were added to the reaction flask, respectively, after the addition was completed, the temperature was raised to 110℃and stirred overnight, after the reaction was completed, n-hexane (20 mL) was added, stirred at room temperature for 30 minutes, the filtrate was filtered and the solvent was removed under reduced pressure, and column chromatography (eluent: petroleum) was purified to give colorless liquid 500mg, yield: 47.1%.

MS-ESI:m/z 205.2[M+H] ⁺ .

Step 2: synthesis of Compound (E) -1- (3-bromoprop-1-en-1-yl) -4-fluoro-2- (trifluoromethyl) benzene

(E) -4-fluoro-1- (prop-1-en-1-yl) -2- (trifluoromethyl) benzene (500 mg,2.45 mmol) was dissolved in carbon tetrachloride (5.0 mL), NBS (523 mg,2.94 mmol) and AIBN (80 mg,0.49 mmol) were added to the reaction flask at room temperature, and then heated to 78℃and stirred overnight, after the reaction was completed, n-hexane (20 mL) was added, stirred at room temperature for 30 minutes, the filtrate was filtered and the solvent was removed under reduced pressure, and column chromatography (eluent: petroleum) was purified to give colorless liquid 300mg, yield: 43.3%.

MS-ESI:m/z 284.1[M+H] ⁺ .

Step 3: synthesis of Compound (E) -3- ((3- (4-fluoro-2- (trifluoromethyl) phenyl) allyl) thio) -5, 5-dimethyl-4, 5-dihydroisoxazole

(E) -1- (3-bromoprop-1-en-1-yl) -4-fluoro-2- (trifluoromethyl) benzene (300 mg,1.06 mmol) and 5, 5-dimethyl-4, 5-dihydroisoxazol-3-yl isothiourea hydrobromide (323 mg,1.27 mmol) were dissolved in acetonitrile (20 mL), after stirring at room temperature for 10min, potassium carbonate (586 mg,4.24 mmol) was added to the above mixture, the reaction was stopped after 12h, acetonitrile was removed, washed with water (30 mL), ethyl acetate (15 mL) was extracted three times, the solvent was removed by combining the organic phases under reduced pressure, and column chromatography (eluent: petroleum ether/EtOAc (v/v) =10/1) was purified to give 220mg of yellow liquid, yield: 62.3%.

MS-ESI:m/z 334.3[M+H] ⁺ .

Step 4: synthesis of Compound (E) -3- ((3- (4-fluoro-2- (trifluoromethyl) phenyl) allyl) sulfonyl) -5, 5-dimethyl-4, 5-dihydroisoxazole

(E) -3- ((3- (4-fluoro-2- (trifluoromethyl) phenyl) allyl) thio) -5, 5-dimethyl-4, 5-dihydroisoxazole (220 mg,0.66 mmol) was dissolved in dichloromethane (10 mL), stirred at room temperature, then 75% m-chloroperoxybenzoic acid (304 mg,1.32 mmol) was added to the above mixture, the reaction was stopped after 12h, quenched with saturated aqueous sodium bisulphite (10 mL), extracted twice with dichloromethane (10 mL), washed with saturated aqueous sodium bicarbonate (10 mL), dried over anhydrous sodium sulphate, the solvent was removed by combining the organic phases under reduced pressure, and column chromatography (eluent: petroleum ether/EtOAc (v/v) =5/1) was purified to give the product as a white solid, 0.15g, yield: 62.2%.

MS-ESI:m/z 366.3[M+H] ⁺ ；

¹ H NMR(600MHz,CDCl ₃ )δ7.63(dd,J＝8.6,5.3Hz,1H),7.37(dd,J＝8.8,2.6Hz,1H),7.26–7.22(m,1H),7.07(d,J＝15.5Hz,1H),6.17(dt,J＝15.4,7.5Hz,1H),4.27(d,J＝7.5Hz,2H),3.09(s,2H),1.48(s,6H).

Example 5: synthesis of Compound (E) -3- ((3- (4-fluoro-3-phenoxyphenyl) allyl) sulfonyl) -5, 5-dimethyl-4, 5-dihydroisoxazole

Step 1: synthesis of Compound (E) -1-fluoro-2-phenoxy-4- (prop-1-en-1-yl) benzene

4-fluoro-3-phenoxybenzaldehyde (1.00 g,4.63 mmol) was dissolved in anhydrous dioxane (15.0 mL), and then ethyl triphenylphosphonium bromide (2.06 g,5.55 mmol) and potassium carbonate (0.96 g,6.94 mmol) were added to the reaction flask, respectively, after the addition was completed, the temperature was raised to 110℃and stirred overnight, after the reaction was completed, cooled, n-hexane (20 mL) was added, stirred at room temperature for 30 minutes, filtered, the solvent was removed from the filtrate under reduced pressure, and column chromatography (eluent: petroleum) was purified to give 600mg of colorless liquid, yield: 56.8%.

MS-ESI:m/z 229.3[M+H] ⁺ .

Step 2: synthesis of Compound (E) -4- (3-bromoprop-1-en-1-yl) -1-fluoro-2-phenoxybenzene

(E) -1-fluoro-2-phenoxy-4- (prop-1-en-1-yl) benzene (600 mg,2.63 mmol) was dissolved in carbon tetrachloride (5.0 mL), NBS (561 mg,3.15 mmol) and AIBN (86 mg,0.53 mmol) were added to the reaction flask at room temperature, and then heated to 78℃and stirred overnight, after the reaction was completed, n-hexane (20 mL) was added, stirred at room temperature for 30 minutes, filtered, the solvent was removed from the filtrate under reduced pressure, and column chromatography (eluent: petroleum) was purified to give colorless liquid 500mg, yield: 61.9%.

MS-ESI:m/z 308.2[M+H] ⁺ .

Step 3: synthesis of Compound (E) -3- ((3- (4-fluoro-3-phenoxyphenyl) allyl) thio) -5, 5-dimethyl-4, 5-dihydroisoxazole

(E) -4- (3-Bromoprop-1-en-1-yl) -1-fluoro-2-phenoxybenzene (500 mg,1.63 mmol) and 5, 5-dimethyl-4, 5-dihydroisoxazol-3-yl isothiourea hydrobromide (496 mg,1.95 mmol) were dissolved in acetonitrile (20 mL), stirred at room temperature for 10min, then potassium carbonate (900 mg,6.51 mmol) was added to the above mixture, the reaction was stopped after 12h, acetonitrile was removed, washed with water (30 mL), ethyl acetate (15 mL) was extracted three times, the solvent was removed by combining the organic phases under reduced pressure, and column chromatography (eluent: petroleum ether/EtOAc (v/v) =10/1) was purified to give a yellow liquid 400mg, yield: 68.8%.

MS-ESI:m/z 358.4[M+H] ⁺ ；

¹ H NMR(600MHz,CDCl ₃ )δ7.33(d,J＝16.0Hz,2H),7.17–7.04(m,4H),6.98(d,J＝7.9Hz,2H),6.50(d,J＝15.7Hz,1H),6.23–6.16(m,1H),3.81(d,J＝6.6Hz,2H),2.78(s,2H),1.40(s,6H).

Step 4: synthesis of Compound (E) -3- ((3- (4-fluoro-3-phenoxyphenyl) allyl) sulfonyl) -5, 5-dimethyl-4, 5-dihydroisoxazole

(E) -3- ((3- (4-fluoro-3-phenoxyphenyl) allyl) thio) -5, 5-dimethyl-4, 5-dihydroisoxazole (220 mg,0.84 mmol) was dissolved in dichloromethane (10 mL), stirred at room temperature, then 75% m-chloroperoxybenzoic acid (3836 mg,1.68 mmol) was added to the above mixture, the reaction was stopped after 12h, quenched with saturated aqueous sodium bisulphite (10 mL), extracted twice with dichloromethane (10 mL), washed with saturated aqueous sodium bicarbonate (10 mL), dried over anhydrous sodium sulphate, the solvent was removed by combining the organic phases under reduced pressure, and column chromatography (eluent: petroleum ether/EtOAc (v/v) =5/1) was purified to give a white solid 0.26g, yield: 79.6%.

MS-ESI:m/z 390.4[M+H] ⁺ ；

¹ H NMR(400MHz,CDCl ₃ )δ7.34(t,J＝7.9Hz,2H),7.20–7.05(m,4H),6.98(d,J＝7.9Hz,2H),6.65(d,J＝15.8Hz,1H),6.08(dt,J＝15.5,7.6Hz,1H),4.20(d,J＝7.5Hz,2H),3.07(s,2H),1.46(s,6H).

Example 6: synthesis of Compound (E) -5, 5-dimethyl-3- ((3- (3, 4, 5-trifluorophenyl) allyl) sulfonyl) -4, 5-dihydroisoxazole

Step 1: synthesis of Compound (E) -1,2, 3-trifluoro-5- (prop-1-en-1-yl) benzene

3,4, 5-trifluorobenzaldehyde (1.00 g,6.25 mmol) was dissolved in anhydrous dioxane (15.0 mL), then ethyl triphenylphosphonium bromide (2.78 g,7.50 mmol) and potassium carbonate (1.29 g,9.37 mmol) were added to the reaction flask, after the addition was completed, the temperature was raised to 110℃and stirred overnight, after the reaction was completed, n-hexane (20 mL) was cooled, stirred at room temperature for 30 minutes, the filtrate was filtered and the solvent was removed under reduced pressure, and column chromatography (eluent: petroleum) was purified to give a colorless liquid, yield: 46.5%.

MS-ESI:m/z 173.2[M+H] ⁺ .

Step 2: synthesis of Compound (E) -5- (3-Bromoprop-1-en-1-yl) -1,2, 3-trifluorobenzene

(E) -1,2, 3-trifluoro-5- (prop-1-en-1-yl) benzene (600 mg,2.90 mmol) was dissolved in carbon tetrachloride (5.0 mL), NBS (620 mg,3.49 mmol) and AIBN (95 mg,0.58 mmol) were added to the reaction flask at room temperature, then the temperature was raised to 78℃and stirred overnight, after the reaction was completed, n-hexane (20 mL) was added, stirred at room temperature for 30 minutes, the filtrate was filtered and the solvent was removed under reduced pressure, and column chromatography (eluent: petroleum) was purified to give colorless liquid 500mg, yield: 68.6%.

MS-ESI:m/z 252.1[M+H] ⁺ .

Step 3: synthesis of Compound (E) -5, 5-dimethyl-3- ((3- (3, 4, 5-trifluorophenyl) allyl) thio) -4, 5-dihydroisoxazole

After dissolving (E) -5- (3-bromoprop-1-en-1-yl) -1,2, 3-trifluorobenzene (500 mg,1.99 mmol) and 5, 5-dimethyl-4, 5-dihydroisoxazol-3-yl isothiourea hydrobromide (607 mg,2.39 mmol) in acetonitrile (20 mL), stirring at room temperature for 10min, potassium carbonate (1.10 g,7.97 mmol) was added to the above mixture, the reaction was stopped after 12h, acetonitrile was removed, washed with water (30 mL), ethyl acetate (15 mL) was extracted three times, the solvent was removed by combining the organic phases under reduced pressure, and column chromatography (eluent: petroleum ether/EtOAc (v/v) =10/1) was purified to give a yellow liquid 380mg, yield: 63.3%.

MS-ESI:m/z 302.3[M+H] ⁺ ；

¹ H NMR(400MHz,CDCl ₃ )δ7.02–6.91(m,2H),6.47(d,J＝15.6Hz,1H),6.34–6.23(m,1H),3.82(d,J＝7.2Hz,2H),2.79(s,2H),1.42(s,6H).

Step 4: synthesis of Compound (E) -5, 5-dimethyl-3- ((3- (3, 4, 5-trifluorophenyl) allyl) sulfonyl) -4, 5-dihydroisoxazole

(E) -5, 5-dimethyl-3- ((3- (3, 4, 5-trifluorophenyl) allyl) thio) -4, 5-dihydroisoxazole (220 mg,0.73 mmol) was dissolved in dichloromethane (10 mL), stirred at room temperature, then 75% m-chloroperoxybenzoic acid (336 mg,1.46 mmol) was added to the above mixture, the reaction was stopped after 12h, quenched with saturated aqueous sodium bisulphite (10 mL), extracted twice with dichloromethane (10 mL), washed with saturated aqueous sodium bicarbonate (10 mL), dried over anhydrous sodium sulphate, the solvent was removed by combining the organic phases under reduced pressure, and column chromatography (eluent: petroleum ether/EtOAc (v/v) =5/1) was purified to give a white solid, 0.16g, yield: 65.8%.

MS-ESI:m/z 334.3[M+H] ⁺ ；

¹ H NMR(400MHz,CDCl ₃ )δ7.08–6.97(m,2H),6.63(d,J＝15.8Hz,1H),6.18(dt,J＝15.5,7.6Hz,1H),4.24(d,J＝7.6Hz,2H),3.09(s,2H),1.48(s,6H).

Example 7: synthesis of Compound (E) -3- ((3- (2, 5-dichloro-4-ethoxyphenyl) allyl) sulfonyl) -5, 5-dimethyl-4, 5-dihydroisoxazole

Step 1: synthesis of Compound (E) -methyl 3- (2, 5-dichloro-4-hydroxyphenyl) acrylate

4-bromo-2, 5-dichlorophenol (4.00 g,16.5 mmol) was dissolved in acetonitrile (50 mL), methyl acrylate (1.70 g,19.8 mmol), triethylamine (5.86 g,57.9 mmol) and triphenylphosphine (0.87 g,3.31 mmol) were added to the reaction flask at room temperature, nitrogen was replaced 3 times, palladium acetate (186 mg,0.83 mmol) was added to the reaction flask, nitrogen was replaced 3 times, then heated to 90 ℃ and stirred overnight, after the reaction was completed, water (100 mL) was added, extracted three times with ethyl acetate (50 mL), washed with saturated brine (100 mL), dried over sodium sulfate, filtered, the solvent was removed from the filtrate under reduced pressure, and column chromatography (eluent: petroleum ether/EtOAc (v/v) =4/1) was purified to give a yellow solid, 2.70g, yield: 66.1%.

MS-ESI:m/z 248.1[M+H] ⁺ .

Step 2: synthesis of Compound (E) -methyl 3- (2, 5-dichloro-4-ethoxyphenyl) acrylate

Methyl (E) -3- (2, 5-dichloro-4-hydroxyphenyl) acrylate (2.00 g,8.09 mmol) was dissolved in acetonitrile (20 mL), then potassium carbonate (2.24 g,16.2 mmol) and ethyl iodide (1.52 g,9.71 mmol) were added to the reaction flask at room temperature, stirred overnight at room temperature, after the reaction was completed, the solvent was removed under reduced pressure, water (50 mL) was added, extracted three times with methyl tert-butyl ether (20 mL), washed with saturated brine (50 mL), dried over sodium sulfate, filtered, the solvent was removed from the filtrate under reduced pressure, and column chromatography (eluent: petroleum ether/EtOAc (v/v) =10/1) was purified to give a yellow solid, 2.00g, yield: 89.8%.

MS-ESI:m/z 276.1[M+H] ⁺ .

Step 3: synthesis of Compound (E) -3- (2, 5-dichloro-4-ethoxyphenyl) prop-2-en-1-ol

Methyl (E) -3- (2, 5-dichloro-4-ethoxyphenyl) acrylate (1.00 g,3.63 mmol) was dissolved in anhydrous dichloromethane (20 mL), a toluene solution of diisobutylaluminum hydride (1.5M, 6.1 mL) was added dropwise to the reaction flask under ice bath, stirred under ice bath for 3 hours, after completion of the reaction, acetone (2.0 mL) was added to quench, stirred at room temperature for 30 minutes, water (30 mL) was added, extracted twice with dichloromethane (20 mL), washed with saturated brine (30 mL), dried over sodium sulfate, filtered, and the solvent was removed from the filtrate under reduced pressure to give 800mg of a yellow liquid crude product, yield: 89.1%.

MS-ESI:m/z 248.1[M+H] ⁺ .

Step 4: synthesis of Compound (E) -1- (3-bromoprop-1-en-1-yl) -2, 5-dichloro-4-ethoxybenzene

(E) -3- (2, 5-dichloro-4-ethoxyphenyl) prop-2-en-1-ol (800 mg,3.24 mmol) was dissolved in dichloromethane (15 mL), then phosphorus tribromide (1.31 g,4.86 mmol) was added to the reaction flask at room temperature, reacted for 1 hour at room temperature, after which time the temperature was lowered, water (30 mL) was added, extracted twice with dichloromethane (20 mL), washed with saturated brine (30 mL), dried over sodium sulfate, filtered, and the solvent was removed from the filtrate under reduced pressure to give 800mg of crude yellow liquid product, yield: 79.7%.

MS-ESI:m/z 311.0[M+H] ⁺ .

Step 5: synthesis of Compound (E) -3- ((3- (2, 5-dichloro-4-ethoxyphenyl) allyl) thio) -5, 5-dimethyl-4, 5-dihydroisoxazole

(E) -1- (3-Bromoprop-1-en-1-yl) -2, 5-dichloro-4-ethoxybenzene (800 mg,2.58 mmol) and 5, 5-dimethyl-4, 5-dihydro-isoxazol-3-yl isothiourea hydrobromide (787 mg,3.10 mmol) were dissolved in acetonitrile (20 mL), stirred at room temperature for 10min, then potassium carbonate (1.43 g,10.3 mmol) was added to the above mixture to react for 12h, the reaction was stopped, acetonitrile was removed, washed with water (30 mL), ethyl acetate (15 mL) was extracted three times, and the solvent was removed under reduced pressure to give 600mg of a yellow liquid crude product, yield: 64.5%.

MS-ESI:m/z 361.3[M+H] ⁺ .

Step 6: synthesis of Compound (E) -3- ((3- (2, 5-dichloro-4-ethoxyphenyl) allyl) sulfonyl) -5, 5-dimethyl-4, 5-dihydroisoxazole

(E) -3- ((3- (2, 5-dichloro-4-ethoxyphenyl) allyl) thio) -5, 5-dimethyl-4, 5-dihydroisoxazole (600 mg,1.67 mmol) was dissolved in dichloromethane (10 mL), stirred at room temperature, then 75% m-chloroperoxybenzoic acid (766 mg,3.33 mmol) was added to the above mixture to react for 12h, the reaction was stopped, quenched with saturated aqueous sodium bisulphite (10 mL), extracted twice with dichloromethane (10 mL), washed with saturated aqueous sodium bicarbonate (10 mL), dried over anhydrous sodium sulphate, the solvent was removed by combining the organic phases under reduced pressure, and column chromatography (eluent: petroleum ether/EtOAc (v/v) =5/1) was purified to give a white solid 0.30g, yield: 45.9%.

MS-ESI:m/z 393.3[M+H] ⁺ ；

¹ H NMR(600MHz,CDCl ₃ )δ7.56(s,1H),7.01(d,J＝15.9Hz,1H),6.90(s,1H),6.11(dt,J＝15.6,7.6Hz,1H),4.26(dd,J＝7.6,1.1Hz,2H),4.11(dd,J＝14.3,7.1Hz,2H),3.09(s,2H),1.50–1.46(m,9H).

Example 8: synthesis of Compound (E) -3- ((3- (5-chloro-3- (difluoromethyl) -1-ethyl-1H-pyrazol-4-yl) allyl) sulfonyl) -5, 5-dimethyl-4, 5-dihydroisoxazole

Step 1: synthesis of the Compound 5-chloro-3- (difluoromethyl) -1-ethyl-1H-pyrazole-4-carbaldehyde

Ethyl difluoroacetoacetate (83.06 g,0.50 mol) was dissolved in absolute ethanol (200 mL), stirred at 0 ℃, then hydrazine hydrate (37.50 g,0.75 mol) was slowly added dropwise to the above mixture, and after the addition was completed, the reaction was continued at room temperature for 4 hours, and continued at 80 ℃ for overnight reaction, and the reaction was stopped. The ethanol was removed, the mixture was washed with water (300 mL), extracted three times with ethyl acetate (150 mL), and the organic phases were combined and the solvent was removed under reduced pressure to give a pale yellow solid product.

DMF (38.01 g,0.52 mol) was stirred at 0deg.C, phosphorus oxychloride (239.20 g,1.56 mmol) was slowly added dropwise to DMF, the addition was completed, the mixture was stirred at room temperature, and the resulting pale yellow solid was added in portions to the above mixture, then the above mixture was warmed to 110deg.C and refluxed overnight, after completion of the reaction, washed with water (500 mL), extracted three times with ethyl acetate (150 mL), and the solvent was removed under reduced pressure to give a reddish brown solid product.

The above reddish brown solid product was dissolved with potassium carbonate (57.96 g,0.42 mol) in DMF (100 mL) and stirred at room temperature, and ethyl iodide (35.78 g,0.25 mmol) was added, and after completion of the addition, the mixture was stirred at 80 ℃ for 24 hours, washed with water (200 mL), extracted with ethyl acetate (100 mL) three times, the organic phases were combined and the solvent was removed under reduced pressure, and separated by column chromatography (eluent: petroleum ether/EtOAc (v/v) =10/1) to give a colorless transparent liquid 15.92g, yield: 15.3%.

MS-ESI:m/z 209.6[M+H] ⁺ .

Step 2: synthesis of Compound (E) -5-chloro-3- (difluoromethyl) -1-ethyl-4- (prop-1-en-1-yl) -1H-pyrazole

5-chloro-3- (difluoromethyl) -1-ethyl-1H-pyrazole-4-carbaldehyde (1.00 g,4.79 mmol) was dissolved in anhydrous dioxane (15.0 mL), and then ethyl triphenylphosphonium bromide (2.14 g,5.75 mmol) and potassium carbonate (0.94 g,7.19 mmol) were added to a reaction flask, respectively, and after the addition was completed, the mixture was stirred overnight at 100℃and after the completion of the reaction, the temperature was lowered, the solvent was removed under reduced pressure, ethyl acetate (20 mL) was added, stirred at room temperature for 30 minutes, filtered, the solvent was removed under reduced pressure from the filtrate, and column chromatography (eluent: petroleum) was purified to give colorless liquid 1.00g, yield: 94.5%.

MS-ESI:m/z 221.7[M+H] ⁺ .

Step 3: synthesis of Compound (E) -4- (3-bromoprop-1-en-1-yl) -5-chloro-3- (difluoromethyl) -1-ethyl-1H-pyrazole

(E) -5-chloro-3- (difluoromethyl) -1-ethyl-4- (prop-1-en-1-yl) -1H-pyrazole (1.00 g,4.53 mmol) was dissolved in carbon tetrachloride (15.0 mL), NBS (968 mg,5.44 mmol) and AIBN (149 mg,0.91 mmol) were added to the flask at room temperature, followed by stirring overnight at 78℃and then cooling after the completion of the reaction, n-hexane (20 mL) was added, stirring at room temperature for 30 minutes, filtration and removal of the solvent under reduced pressure to give 1.20g of a yellow liquid crude product, yield: 88.4%.

MS-ESI:m/z 300.5[M+H] ⁺ .

Step 4: synthesis of Compound (E) -3- ((3- (5-chloro-3- (difluoromethyl) -1-ethyl-1H-pyrazol-4-yl) allyl) thio) -5, 5-dimethyl-4, 5-dihydroisoxazole

(E) -4- (3-bromoprop-1-en-1-yl) -5-chloro-3- (difluoromethyl) -1-ethyl-1H-pyrazole (1.20 g,4.01 mmol) and 5, 5-dimethyl-4, 5-dihydro-isoxazol-3-yl isothiourea hydrobromide (1.22 g,4.81 mmol) were dissolved in acetonitrile (30 mL), stirred at room temperature for 10min, then potassium carbonate (2.21 g,16.0 mmol) was added to the mixture, the reaction was stopped after 12H, acetonitrile was removed, washed with water (50 mL), ethyl acetate (30 mL) was extracted three times, the solvent was removed under reduced pressure, and column chromatography (eluent: petroleum ether/EtOAc (v/v) =10/1) was purified to give a yellow liquid 700mg, yield: 53.0%.

MS-ESI:m/z 350.8[M+H] ⁺ ；

¹ H NMR(400MHz,CDCl ₃ )δ6.78–6.53(m,1H),6.50(s,1H),6.47–6.38(m,1H),4.29–4.15(m,2H),3.85(d,J＝6.8Hz,2H),2.82(s,2H),1.46(d,J＝7.3Hz,3H),1.43(s,6H).

Step 5: synthesis of Compound (E) -3- ((3- (5-chloro-3- (difluoromethyl) -1-ethyl-1H-pyrazol-4-yl) allyl) sulfonyl) -5, 5-dimethyl-4, 5-dihydroisoxazole

(E) -3- ((3- (5-chloro-3- (difluoromethyl) -1-ethyl-1H-pyrazol-4-yl) allyl) thio) -5, 5-dimethyl-4, 5-dihydroisoxazole (500 mg,1.52 mmol) was dissolved in dichloromethane (10 mL), stirred at room temperature, then 75% m-chloroperoxybenzoic acid (698 mg,3.04 mmol) was added to the above mixture, the reaction was stopped after 12H, quenched with saturated aqueous sodium hydrogen sulfite (10 mL), extracted twice with dichloromethane (10 mL), washed with saturated aqueous sodium hydrogen carbonate (10 mL), dried over anhydrous sodium sulfate, and the solvent was removed under reduced pressure, and column chromatography (eluent: petroleum ether/EtOAc (v/v) =5/1) was purified to give a white solid, 0.40g, yield: 72.9%.

MS-ESI:m/z 382.2[M+H] ⁺ ；

¹ H NMR(400MHz,CDCl ₃ )δ6.65(dd,J＝61.0,46.6Hz,2H),6.39–6.28(m,1H),4.21(dd,J＝14.6,7.3Hz,4H),3.10(s,2H),1.49(s,6H),1.46(t,J＝7.3Hz,3H).

Example 9: synthesis of Compound (E) -3- ((3- (5-chloro-3- (difluoromethyl) -1-isopropyl-1H-pyrazol-4-yl) allyl) sulfonyl) -5, 5-dimethyl-4, 5-dihydroisoxazole

Step 1: synthesis of the Compounds 5-chloro-3- (difluoromethyl) -1-isopropyl-1H-pyrazole-4-carbaldehyde and 3-chloro-5- (difluoromethyl) -1-ethyl-1H-pyrazole-4-carbaldehyde

Ethyl difluoroacetoacetate (5.00 g,30.1 mmol) was dissolved in absolute ethanol (100 mL) and stirred at 0 ℃, then hydrazine hydrate (1.45 g,45.2 mmol) was slowly added dropwise to the above mixture, and after the addition was completed, the reaction was continued at room temperature for 4h, and continued at 80 ℃ for overnight, the reaction was stopped. The ethanol was removed, the mixture was washed with water (50 mL), extracted three times with ethyl acetate (50 mL), and the organic phases were combined and the solvent was removed under reduced pressure to give a pale yellow solid product.

DMF (2.20 g,30.1 mmol) was stirred at 0deg.C, phosphorus oxychloride (13.8 g,90.3 mmol) was then slowly added dropwise to DMF, the mixture was warmed to room temperature and stirred, and the resulting pale yellow solid was added in portions to the mixture, then the mixture was warmed to 110deg.C and refluxed overnight, after the reaction was completed, washed with water (50 mL), extracted three times with ethyl acetate (50 mL), and the organic phases were combined and the solvent was removed under reduced pressure to give a reddish brown solid product.

The above reddish brown solid product was dissolved with potassium carbonate (4.16 g,30.1 mmol) in DMF (50 mL) and stirred at room temperature, 2-iodopropane (2.56 g,15.1 mmol) was added, stirred at 80 ℃ for 12H, after completion of the reaction, washed with water (50 mL), extracted three times with ethyl acetate (50 mL), the organic phases were combined and the solvent was removed under reduced pressure, and separated by column chromatography (eluent: petroleum ether/EtOAc (v/v) =10/1) to give colorless transparent liquid 5-chloro-3- (difluoromethyl) -1-isopropyl-1H-pyrazole-4-carbaldehyde 1.50g, yield: 22.4%.

MS-ESI:m/z 223.1[M+H] ⁺ .

Step 2: synthesis of Compound (E) -5-chloro-3- (difluoromethyl) -1-isopropyl-4- (prop-1-en-1-yl) -1H-pyrazole

5-chloro-3- (difluoromethyl) -1-isopropyl-1H-pyrazole-4-carbaldehyde (1.00 g,4.49 mmol) was dissolved in anhydrous dioxane (15.0 mL), and then ethyl triphenylphosphonium bromide (2.00 g,5.39 mmol) and potassium carbonate (0.93 g,6.74 mmol) were added to a reaction flask, respectively, and after the addition was completed, the mixture was stirred overnight at 100℃and after the completion of the reaction, the temperature was lowered, the solvent was removed under reduced pressure, ethyl acetate (20 mL) was added, stirred at room temperature for 30 minutes, filtered, the solvent was removed under reduced pressure from the filtrate, and column chromatography (eluent: petroleum) was purified to give colorless liquid 1.00g, yield: 94.9%.

MS-ESI:m/z 235.7[M+H] ⁺ .

Step 3: synthesis of Compound (E) -4- (3-bromoprop-1-en-1-yl) -5-chloro-3- (difluoromethyl) -1-isopropyl-1H-pyrazole

(E) -5-chloro-3- (difluoromethyl) -1-isopropyl-4- (prop-1-en-1-yl) -1H-pyrazole (1.00 g,4.26 mmol) was dissolved in carbon tetrachloride (15.0 mL), NBS (910 mg,5.11 mmol) and AIBN (140 mg,0.85 mmol) were added to the reaction flask at room temperature, followed by stirring overnight at 78℃and then cooling, n-hexane (20 mL) was added, stirring at room temperature for 30 minutes, filtration and removal of the solvent from the filtrate under reduced pressure to give 1.00g of a yellow liquid crude product, yield: 74.8%.

MS-ESI:m/z 314.6[M+H] ⁺ .

Step 4: synthesis of Compound (E) -3- ((3- (5-chloro-3- (difluoromethyl) -1-isopropyl-1H-pyrazol-4-yl) allyl) thio) -5, 5-dimethyl-4, 5-dihydroisoxazole

(E) -4- (3-bromoprop-1-en-1-yl) -5-chloro-3- (difluoromethyl) -1-isopropyl-1H-pyrazole (1.00 g,3.19 mmol) and 5, 5-dimethyl-4, 5-dihydro-isoxazol-3-yl isothiourea hydrobromide (973 mg,3.83 mmol) were dissolved in acetonitrile (30 mL), stirred at room temperature for 10min, potassium carbonate (1.76 g,12.8 mmol) was added to the above mixture, the reaction was stopped after 12H, acetonitrile was removed, washed with water (50 mL), ethyl acetate (30 mL) was extracted three times, the solvent was removed under reduced pressure, and column chromatography (eluent: petroleum ether/EtOAc (v/v) =10/1) was purified to give 600mg of yellow liquid, yield: 51.7%.

MS-ESI:m/z 364.9[M+H] ⁺ .

Step 5: synthesis of Compound (E) -3- ((3- (5-chloro-3- (difluoromethyl) -1-isopropyl-1H-pyrazol-4-yl) allyl) sulfonyl) -5, 5-dimethyl-4, 5-dihydroisoxazole

(E) -3- ((3- (5-chloro-3- (difluoromethyl) -1-isopropyl-1H-pyrazol-4-yl) allyl) thio) -5, 5-dimethyl-4, 5-dihydroisoxazole (600 mg,1.65 mmol) was dissolved in dichloromethane (10 mL), stirred at room temperature, then 75% m-chloroperoxybenzoic acid (759 mg,3.30 mmol) was added to the above mixture, the reaction was stopped after 12H, quenched with saturated aqueous sodium hydrogen sulfite (10 mL), extracted twice with dichloromethane (10 mL), washed with saturated aqueous sodium bicarbonate (10 mL), dried over anhydrous sodium sulfate, and the solvent was removed under reduced pressure, and column chromatography (eluent: petroleum ether/EtOAc (v/v) =5/1) was purified to give 0.32g of a white solid, yield: 49.0%.

MS-ESI:m/z 396.9[M+H] ⁺ ；

¹ H NMR(400MHz,CDCl ₃ )δ6.64(dd,J＝61.0,46.6Hz,2H),6.38–6.26(m,1H),4.69(dt,J＝13.2,6.6Hz,1H),4.21(d,J＝7.5Hz,2H),3.08(s,2H),1.47(d,J＝4.5Hz,12H).

Example 10: synthesis of Compound (E) -3- ((3- (5-chloro-1-methyl-3- (trifluoromethyl) -1H-pyrazol-4-yl) allyl) sulfonyl) -5, 5-dimethyl-4, 5-dihydroisoxazole

Step 1: synthesis of the Compounds 5-chloro-1-methyl-3- (trifluoromethyl) -1H-pyrazole-4-carbaldehyde and 3-chloro-1-methyl-5- (trifluoromethyl) -1H-pyrazole-4-carbaldehyde

Ethyl trifluoroacetoacetate (5.00 g,27.2 mmol) was dissolved in absolute ethanol (100 mL), stirred at 0deg.C, then hydrazine hydrate (1.31 g,40.7 mmol) was slowly added dropwise to the above mixture, after the dropwise addition was completed, the reaction was continued at room temperature for 4h, and continued at 80℃overnight, the reaction was stopped. The ethanol was removed, the mixture was washed with water (50 mL), extracted three times with ethyl acetate (50 mL), and the organic phases were combined and the solvent was removed under reduced pressure to give a pale yellow solid product.

DMF (1.99 g,27.2 mmol) was stirred at 0deg.C, phosphorus oxychloride (12.5 g,81.5 mmol) was then slowly added dropwise to DMF, the addition was completed, the mixture was stirred at room temperature, and the resulting pale yellow solid was added in portions to the above mixture, then the above mixture was warmed to 110deg.C and refluxed overnight, after completion of the reaction, washed with water (50 mL), extracted three times with ethyl acetate (50 mL), and the solvent was removed under reduced pressure to give a reddish brown solid product.

The above reddish brown solid product was dissolved with potassium carbonate (3.75 g,27.2 mmol) in DMF (50 mL) and stirred at room temperature, methyl iodide (1.93 g,13.6 mmol) was added, and after completion of the addition, the mixture was stirred at 80 ℃ for 12H, washed with water (50 mL), extracted three times with ethyl acetate (50 mL), the organic phases were combined and the solvent was removed under reduced pressure, and separated by column chromatography (eluent: petroleum ether/EtOAc (v/v) =10/1) to give colorless transparent liquid, 5-chloro-1-methyl-3- (trifluoromethyl) -1H-pyrazole-4-carbaldehyde, 1.50g, yield: 26.0%.

MS-ESI:m/z 223.6[M+H] ⁺ .

Step 2: synthesis of Compound (E) -5-chloro-1-methyl-4- (prop-1-en-1-yl) -3- (trifluoromethyl) -1H-pyrazole

5-chloro-1-methyl-3- (trifluoromethyl) -1H-pyrazole-4-carbaldehyde (1.00 g,4.70 mmol) was dissolved in anhydrous dioxane (15.0 mL), and then ethyl triphenylphosphonium bromide (2.10 g,5.65 mmol) and potassium carbonate (0.98 g,7.06 mmol) were added to a reaction flask, respectively, the addition was completed, the temperature was raised to 100deg.C and stirred overnight, after the completion of the reaction, the temperature was lowered, the solvent was removed under reduced pressure, ethyl acetate (20 mL) was added, stirred at room temperature for 30 minutes, filtered, the solvent was removed from the filtrate under reduced pressure, and column chromatography (eluent: petroleum) was purified to give colorless liquid, 0.70g, yield: 66.2%.

MS-ESI:m/z 225.6[M+H] ⁺ .

Step 3: synthesis of Compound (E) -4- (3-bromoprop-1-en-1-yl) -5-chloro-1-methyl-3- (trifluoromethyl) -1H-pyrazole

(E) -5-chloro-1-methyl-4- (prop-1-en-1-yl) -3- (trifluoromethyl) -1H-pyrazole (0.70 g,3.12 mmol) was dissolved in carbon tetrachloride (15.0 mL), NBS (610 mg,3.43 mmol) and AIBN (102 mg,0.62 mmol) were added to the reaction flask at room temperature, and then stirred overnight at 78℃to give a yellow crude product, after completion of the reaction, cooled, n-hexane (20 mL) was added, stirred at room temperature for 30 minutes, filtered, and the solvent was removed under reduced pressure to give 600mg of a yellow liquid crude product, yield: 63.4%.

MS-ESI:m/z 304.5[M+H] ⁺ .

Step 4: synthesis of Compound (E) -3- ((3- (5-chloro-1-methyl-3- (trifluoromethyl) -1H-pyrazol-4-yl) allyl) thio) -5, 5-dimethyl-4, 5-dihydroisoxazole

(E) -4- (3-bromoprop-1-en-1-yl) -5-chloro-1-methyl-3- (trifluoromethyl) -1H-pyrazole (600 mg,1.98 mmol) and 5, 5-dimethyl-4, 5-dihydroisoxazol-3-yl isothiourea hydrobromide (603 mg,2.37 mmol) were dissolved in acetonitrile (30 mL), stirred at room temperature for 10min, then potassium carbonate (1.09 g,7.91 mmol) was added to the above mixture, the reaction was stopped after 12H, acetonitrile was removed, washed with water (50 mL), ethyl acetate (30 mL) was extracted three times, the solvent was removed by combining the organic phases under reduced pressure, and column chromatography (eluent: petroleum ether/EtOAc (v/v) =10/1) was purified to give a yellow liquid 500mg, yield: 71.5%.

MS-ESI:m/z 354.8[M+H] ⁺ .

Step 5: synthesis of Compound (E) -3- ((3- (5-chloro-1-methyl-3- (trifluoromethyl) -1H-pyrazol-4-yl) allyl) sulfonyl) -5, 5-dimethyl-4, 5-dihydroisoxazole

(E) -3- ((3- (5-chloro-1-methyl-3- (trifluoromethyl) -1H-pyrazol-4-yl) allyl) thio) -5, 5-dimethyl-4, 5-dihydroisoxazole (500 mg,1.41 mmol) was dissolved in dichloromethane (10 mL), stirred at room temperature, then 75% m-chloroperoxybenzoic acid (650 mg,2.83 mmol) was added to the above mixture, the reaction was stopped after 12H, quenched with saturated aqueous sodium hydrogen sulfite (10 mL), extracted twice with dichloromethane (10 mL), washed with saturated aqueous sodium hydrogen carbonate (10 mL), dried over anhydrous sodium sulfate, and the solvent was removed under reduced pressure, and column chromatography (eluent: petroleum ether/EtOAc (v/v) =5/1) was purified to give a white solid, 0.30g, yield: 55.0%.

MS-ESI:m/z 386.8[M+H] ⁺ ；

¹ H NMR(400MHz,CDCl ₃ )δ6.58(d,J＝16.1Hz,1H),6.38–6.27(m,1H),4.23(d,J＝7.5Hz,2H),3.90(s,3H),3.08(s,2H),1.47(s,6H).

Biological embodiment

Compound preparation: the crude drug with a certain mass is weighed by an analytical balance (0.0001 g), dissolved by DMF containing 1wt% of Tween-80 emulsifier to prepare 1.0wt% of mother liquor, and then diluted by distilled water for standby.

The test method comprises the following steps: potted plant method, wherein the target is herba Portulacae, barnyard grass and semen Euphorbiae. Taking a flowerpot with the inner diameter of 7.5cm, loading composite soil (vegetable garden soil: seedling substrate, 1:2, v/v) to 3/4 positions, directly sowing the three weed targets (the bud rate is more than or equal to 85%), covering soil with 0.2cm, and adding water to keep the soil moist for 24 hours for later use. After each compound was applied in 300g a.i./ha dose in an automatic spray tower (model: 3 WPSH-700E), the soil surface liquid was allowed to air dry and transferred into a greenhouse for cultivation, and after 25 days, the activity (%) against weeds was investigated.

The test results are shown in Table A.

Table A

The results in Table A show that the herbicidal activity of the compound of the present invention against purslane, barnyard grass and euphorbia lathyris is better than that of Pyroxasulfone at 300g ai/ha.

The compound has good control effect on broadleaf weeds (such as abutilon, amaranthus retroflexus, snake intestine and purslane) and grassy weeds (such as crabgrass, barnyard grass, euphorbia lathyris and green bristlegrass), is safe to crops such as peanuts, wheat, rice and sunflowers, and has good application prospect.

Claims

1. A compound which is a compound represented by the formula (III):

wherein:

R ^f and R is ^h Each independently is fluorine, chlorine, bromine, iodine, halogenated C _1-3 Alkyl or halo C _1-3 An alkoxy group;

n is 2; r is R ^g Is C _1-3 An alkyl group.

2. A compound according to claim 1, wherein:

R ^f and R is ^h Each independently is fluorine, chlorine, bromine, iodine, difluoromethyl, trifluoromethyl, difluoromethoxy or trifluoromethoxy;

R ^g methyl, ethyl, n-propyl, isopropyl.

3. The compound according to any one of claims 1-2, which is a compound having one of the following structures or a salt thereof:

4. a composition comprising a compound of any one of claims 1-3 or a salt thereof.

5. Use of a compound according to any one of claims 1 to 3 or a composition according to claim 4 in agricultural weeding.

6. A method of controlling weed growth in a useful plant comprising applying to the locus of the weed an effective amount of a compound as claimed in any one of claims 1 to 3.