CN113527224A - Thiazole derivative and application thereof in agriculture - Google Patents

Abstract

The invention provides thiazole derivatives and application thereof in agriculture; specifically, the invention provides a compound shown as a formula (I) or a stereoisomer, a nitrogen oxide or a salt thereof of the compound shown as the formula (I), a preparation method, a composition containing the compounds and application thereof in agriculture, in particular to application of the compound as an active ingredient of a herbicide for controlling unwanted plants; wherein R is^a、R^b、R^c、R^d、R^e、R¹And X has the meaning as described in the present invention.

Description

Thiazole derivative and application thereof in agriculture

Technical Field

The invention provides a novel thiazole derivative and a preparation method thereof; compositions containing these compounds and their use in agriculture.

Background

The problem of weed resistance has become a key challenge facing the sustainable development of modern agriculture, and the creation of novel herbicides is a fundamental way to solve the challenge.

With the large use of pesticides, the known active ingredients have disadvantages in use, for example, (a) no or only an insufficient herbicidal action on the weed plants, (b) a too narrow spectrum of weed plants to be controlled or (c) too low selectivity in crops of useful plants.

Accordingly, 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 thiazole compound having excellent herbicidal action and excellent selectivity between crops and weeds.

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

wherein:

R^a、R^b、R^c、R^dand R^eEach independently is hydrogen, fluorine, chlorine, bromine, iodine, amino, nitro, cyano, hydroxyl, carboxyl, C_1-8Alkyl, halo C_1-8Alkyl radical, C_1-8alkyl-C (═ O) -, halo-C_1-8alkyl-C (═ O) -, C_2-8Alkenyl, halo C_2-8Alkenyl radical, C_2-8Alkynyl, halo C_2-8Alkynyl, C_1-8Alkoxy, halo C_1-8Alkoxy radical, C_1-8Alkylamino radical, C_1-8Alkylthio, halo C_1-8Alkylamino, halogeno C_1-8Alkylthio radical, C_3-12Cycloalkyl radical, C_6-14Aryl radical, C_6-14Aryloxy radical, C_1-9Heteroaryl or C_1-9A heteroaryloxy group;

R¹is hydrogen, fluorine, chlorine, bromine, iodine, C_1-8Alkyl, halo C_1-8Alkyl radical, C_2-8Alkenyl, halo C_2-8Alkenyl radical, C_2-8Alkynyl, halo C_2-8Alkynyl, C_1-8Alkoxy, halo C_1-8Alkoxy radical, C_1-8Alkylamino radical, C_1-8Alkylthio, halo C_1-8Alkylamino or halogeno C_1-8An alkylthio group;

is a single bond or a double bond;

x is N, CR²Or CR³R⁴；

When in use

When it is a single bond, X is CR³R⁴；

When in use

When it is a double bond, X is N or CR²；

R²、R³And R⁴Each independently is hydrogen, C_1-8Alkyl, halo C_1-8Alkyl radical, C_2-8Alkenyl, halo C_2-8Alkenyl radical, C_2-8Alkynyl or halo C_2-8Alkynyl.

In some of these embodiments, R^a、R^b、R^c、R^dAnd R^eEach independently is hydrogen, fluorine, chlorine, bromine, iodine, amino, nitro, cyano, hydroxyl, carboxyl, C_1-6Alkyl, halo C_1-6Alkyl radical, C_1-6alkyl-C (═ O) -, halo-C_1-6alkyl-C (═ O) -, C_2-6Alkenyl, halo C_2-6Alkenyl radical, C_2-6Alkynyl, halo C_2-6Alkynyl, C_1-6Alkoxy, haloC_1-6Alkoxy radical, C_1-6Alkylamino radical, C_1-6Alkylthio, halo C_1-6Alkylamino, halogeno C_1-6Alkylthio radical, C_3-8Cycloalkyl radical, C_6-10Aryl radical, C_6-10Aryloxy radical, C_1-5Heteroaryl or C_1-5A heteroaryloxy group.

In some of these embodiments, R¹Is hydrogen, fluorine, chlorine, bromine, iodine, C_1-6Alkyl, halo C_1-6Alkyl radical, C_2-6Alkenyl, halo C_2-6Alkenyl radical, C_2-6Alkynyl, halo C_2-6Alkynyl, C_1-6Alkoxy, halo C_1-6Alkoxy radical, C_1-6Alkylamino radical, C_1-6Alkylthio, halo C_1-6Alkylamino or halogeno C_1-6An alkylthio group.

In some of these embodiments, R²、R³And R⁴Each independently is hydrogen, C_1-6Alkyl, halo C_1-6Alkyl radical, C_2-6Alkenyl, halo C_2-6Alkenyl radical, C_2-6Alkynyl or halo C_2-6Alkynyl.

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

wherein: r^cAnd R¹Have the meaning as described in the present invention.

In other embodiments, R^cIs hydrogen, fluorine, chlorine, bromine, iodine, amino, nitro, cyano, hydroxyl, carboxyl, C_1-4Alkyl, halo C_1-4Alkyl radical, C_1-4alkyl-C (═ O) -, halo-C_1-4alkyl-C (═ O) -, C_1-4Alkoxy, halo C_1-4Alkoxy radical, C_3-6Cycloalkyl radical, C_6-10Aryl or C_6-10An aryloxy group.

In other embodiments, X is N orCR²(ii) a Wherein R is²Is hydrogen, C_1-4Alkyl, halo C_1-4Alkyl radical, C_2-4Alkenyl, halo C_2-4Alkenyl radical, C_2-4Alkynyl or halo C_2-4Alkynyl.

In other embodiments, R¹Is hydrogen, fluorine, chlorine, bromine, iodine, C_1-4Alkyl, halo C_1-4Alkyl radical, C_2-4Alkenyl, halo C_2-4Alkenyl radical, C_2-4Alkynyl, halo C_2-4Alkynyl, C_1-4Alkoxy, halo C_1-4Alkoxy radical, C_1-4Alkylamino radical, C_1-4Alkylthio, halo C_1-4Alkylamino or halogeno C_1-4An alkylthio group.

In other embodiments, R^cIs hydrogen, fluorine, chlorine, bromine, iodine, amino, nitro, cyano, hydroxyl, carboxyl, -CH₃、-CH₂CH₃、-CH₂CH₂CH₃、-CH(CH₃)₂、-CH₂CH₂CH₂CH₃、-CH₂CH(CH₃)₂、-CH(CH₃)CH₂CH₃、-C(CH₃)₃、-OCH₃、-OCH₂CH₃、-OCH₂CH₂CH₃、-OCH(CH₃)₂、-CH₂Br、-CF₃、-CHF₂、-OCF₃、-OCHF₂、-OCH₂CF₃or-OCH₂CHF₂。

In other embodiments, R¹Is hydrogen, fluorine, chlorine, bromine, iodine, -CH₃、-CH₂CH₃、-CH₂CH₂CH₃or-CH (CH)₃)₂。

In another aspect, the present invention provides a compound which is a compound having one of the following structures or a stereoisomer, a nitroxide or a salt thereof of the compound having one of the following structures:

in another aspect, the present invention provides a composition comprising a compound of the present invention, optionally further comprising 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 use of the compound of the present invention or a composition containing the compound of the present invention for controlling a plant disease.

Further, the present invention provides the use of a compound of the present invention or a composition comprising a compound of the present invention for agricultural weeding.

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

In particular, the invention provides the use of a compound of the invention or a composition comprising a compound of the invention for the control of purslane and barnyard grass.

In still other embodiments, the present invention provides a method of controlling weed development in useful plants comprising applying to the locus of the weeds an effective amount of a compound of the present invention or a composition comprising a compound of the present invention.

Further, the weeds include broadleaf weeds and grass weeds.

Still further, the broadleaf weeds include abutilon, purslane, Amaranthus retroflexus, and snakehead intestine; the grassy weeds include large crabgrass, barnyard grass and green bristlegrass.

Still further, the useful plants include rice, wheat, rape and sunflower.

In other embodiments, the present invention provides the use of a compound of the present invention or a composition comprising a compound of the present invention as a herbicide.

In other embodiments, the present invention provides the use of a compound of the present invention or a composition comprising a compound of the present invention as a pre-emergent herbicide.

In other embodiments, the present invention provides the use of a compound of the present invention or a composition comprising a compound of the present invention as a post-emergence herbicide.

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

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

Isotopically enriched compounds have the structure depicted by the formulae given herein, except that one or more atoms are replaced by an atom having a selected atomic mass or mass number. Exemplary isotopes that can be incorporated into compounds of the invention include isotopes of hydrogen, carbon, nitrogen, oxygen, phosphorus, sulfur, fluorine and chlorine, such as²H，³H，¹¹C，¹³C，¹⁴C，¹⁵N，¹⁷O，¹⁸O，¹⁸F，³¹P，³²P，³⁵S，³⁶Cl and¹²⁵I。

any asymmetric atom (e.g., carbon, etc.) of a compound disclosed herein can exist in racemic or enantiomerically enriched forms, such as the (R) -, (S) -or (R, S) -configuration.

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.

The foregoing has outlined only certain aspects of the present invention and is not intended to be limited in these or other respects to the details described herein.

Detailed description of the invention

Definitions and general terms

Reference will now be made in detail to certain embodiments of the invention, examples of which are illustrated by the accompanying structural and chemical formulas. The invention is intended to cover alternatives, modifications and equivalents, which may be included within the scope of the invention as defined by the appended claims. One 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 invention. The present invention is in no way limited to the methods and materials described herein. In the event that one or more of the incorporated documents, patents, and similar materials differ or contradict this application (including but not limited to defined terminology, application of terminology, described techniques, and the like), this application controls.

It will be further 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 subcombination.

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, the chemical elements are in accordance with the CAS version of the periodic Table of the elements, and the handbook of chemistry and Physics, 75 th edition, 1994. In addition, general principles of Organic Chemistry can be referred to as described in "Organic Chemistry", Thomas Sorrell, University Science Books, Sausaltito: 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" as used herein are intended to include "at least one" or "one or more" unless otherwise indicated or clearly contradicted by context. Thus, as used herein, the articles refer to articles of one or more than one (i.e., at least one) object. For example, "a component" refers to one or more components, i.e., there may be more than one component contemplated for use or use in embodiments of the described embodiments.

The term "comprising" is open-ended, i.e. includes the elements indicated in the present invention, but does not exclude other elements.

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

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

"diastereomer" refers to a stereoisomer that has two or more chiral neutrals and whose molecules are not mirror images of each other. Diastereomers have different physical properties, such as melting points, boiling points, spectral properties, and reactivities. Mixtures of diastereomers 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 the general definitions of S.P. Parker, Ed., McGraw-Hill Dictionary of Chemical Terms (1984) McGraw-Hill Book Company, New York; stereochemical definitions and rules as described in and Eliel, e.and Wilen, s, "Stereochemistry of Organic Compounds", John Wiley & Sons, inc, New York, 1994.

Many organic compounds exist in an 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 denote the absolute configuration of a molecule with respect to one or more of its chiral centers. The prefixes d and l or (+) and (-) are the symbols used to specify the rotation of plane polarized light by the compound, where (-) or l indicates that the compound is left-handed. Compounds prefixed with (+) or d are dextrorotatory. A 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 may occur when there is no stereoselectivity or stereospecificity in the chemical reaction or process.

By "room temperature" is meant a temperature of about 15 ℃ to 35 ℃ or about 20 ℃ to 30 ℃ or about 23 ℃ to 28 ℃ or about 25 ℃. In the context of the present invention, all numbers disclosed herein are approximate values, regardless of whether the word "about" or "approximately" is used. The numerical value of each number may vary by 1%, 2%, 3%, 4% or 5%.

The compounds of the invention may be optionally substituted with one or more substituents, as described herein, in compounds of the general formula above, or as specifically exemplified, sub-classes, and classes of compounds encompassed by the invention. It is 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 particular substituent. Unless otherwise indicated, an optional substituent group may be substituted at each substitutable position of the group. When more than one position in a given formula can be substituted with one or more substituents selected from a particular group, the substituents may be substituted at each position, identically or differently. Wherein said substituent may be, but is 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, alkylaminoalkyl, alkylaminoalkylamino, 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, aryl, arylalkyl, arylamino, heteroaryl, heteroarylalkyl, heteroarylamino, amido, sulfonyl, aminosulfonyl, and the like.

In addition, unless otherwise explicitly indicated, the descriptions of the terms "… independently" and "… independently" and "… independently" used in the present invention are interchangeable and should be understood in a broad sense to mean that the specific items expressed between the same symbols do not affect each other in different groups or that the specific items expressed between the same symbols in the same groups do not affect each other.

In the various parts of this specification, substituents of the disclosed compounds are disclosed in terms of group type or range. It is specifically intended that the invention includes each and every independent subcombination of the various members of these groups and ranges. For example, the term "C₁-C₆Alkyl "or" C_1-6Alkyl "means in particular independently disclosed methyl, ethyl, C₃Alkyl radical, C₄Alkyl radical, C₅Alkyl and C₆An alkyl group.

The term "alkyl" or "alkyl group" as used herein, denotes a saturated, straight or branched chain, monovalent hydrocarbon group containing from 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 1-20 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 group (Et, -CH)₂CH₃) N-propyl (n-Pr, -CH)₂CH₂CH₃) Isopropyl group (i-Pr, -CH (CH)₃)₂) N-butyl (n-Bu, -CH)₂CH₂CH₂CH₃) Isobutyl (i-Bu, -CH)₂CH(CH₃)₂) Sec-butyl (s-Bu, -CH (CH)₃)CH₂CH₃) Tert-butyl (t-Bu, -C (CH)₃)₃) N-pentyl (-CH)₂CH₂CH₂CH₂CH₃) 2-pentyl (-CH (CH)₃)CH₂CH₂CH₃) 3-pentyl (-CH (CH)₂CH₃)₂) 2-methyl-2-butyl (-C (CH)₃)₂CH₂CH₃) 3-methyl-2-butyl (-CH (CH)₃)CH(CH₃)₂) 3-methyl-1-butyl (-CH)₂CH₂CH(CH₃)₂) 2-methyl-1-butyl (-CH)₂CH(CH₃)CH₂CH₃) N-hexyl (-CH)₂CH₂CH₂CH₂CH₂CH₃) 2-hexyl (-CH (CH)₃)CH₂CH₂CH₂CH₃) 3-hexyl (-CH (CH)₂CH₃)(CH₂CH₂CH₃) 2-methyl-2-pentyl (-C (CH))₃)₂CH₂CH₂CH₃) 3-methyl-2-pentyl (-CH (CH)₃)CH(CH₃)CH₂CH₃) 4-methyl-2-pentyl (-CH (CH)₃)CH₂CH(CH₃)₂) 3-methyl-3-pentyl (-C (CH)₃)(CH₂CH₃)₂) 2-methyl-3-pentyl (-CH (CH)₂CH₃)CH(CH₃)₂) 2, 3-dimethyl-2-butyl (-C (CH)₃)₂CH(CH₃)₂) 3, 3-dimethyl-2-butyl (-CH (CH)₃)C(CH₃)₃) N-heptyl, n-octyl, and the like.

The term "alkenyl" denotes a straight or branched chain monovalent hydrocarbon radical containing 2 to 12 carbon atoms, wherein there is at least one site of unsaturation, i.e. one carbon-carbon sp²A double bond, wherein the alkenyl group mayOptionally substituted with one or more substituents as 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 contains 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)₂CH＝CH₂) Allyl (CH)₃-CH＝CH-)，-CH₂CH₂CH＝CH₂、-CH₂CH＝CHCH₃、-CH₂CH₂CH₂CH＝CH₂、-CH₂CH₂CH＝CHCH₃、-CH₂CH₂CH₂CH＝CHCH₃And so on.

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 radical may be optionally substituted with one or more substituents as described herein. In one embodiment, alkynyl groups contain 2-10 carbon atoms; in one embodiment, alkynyl groups contain 2-8 carbon atoms; in another embodiment, alkynyl groups contain 2-6 carbon atoms; in yet another embodiment, alkynyl groups contain 2-4 carbon atoms. Examples of alkynyl groups include, but are not limited to, -C.ident.CH, -C.ident.CCH₃、-CH₂-C≡CH、-CH₂-C≡CCH₃、-CH₂CH₂-C≡CH、-CH₂-C≡CCH₂CH₃、-CH₂CH₂-C≡CH₂CH₃And so on.

The term "alkoxy" means an alkyl group attached to the rest of the molecule through an oxygen atom, wherein the alkyl group has the meaning as described herein. Unless otherwise specified, the alkoxy group contains 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)₂CH₃) 1-propoxy (n-PrO, n-propoxy, -OCH)₂CH₂CH₃) 2-propoxy (i-PrO, i-propoxy, -OCH (CH)₃)₂) 1-butoxy (n-BuO, n-butoxy, -OCH)₂CH₂CH₂CH₃) 2-methyl-l-propoxy (i-BuO, i-butoxy, -OCH)₂CH(CH₃)₂) 2-butoxy (s-BuO, s-butoxy, -OCH (CH)₃)CH₂CH₃) 2-methyl-2-propoxy (t-BuO, t-butoxy, -OC (CH)₃)₃) 1-pentyloxy (n-pentyloxy, -OCH)₂CH₂CH₂CH₂CH₃) 2-pentyloxy (-OCH (CH)₃)CH₂CH₂CH₃) 3-pentyloxy (-OCH (CH))₂CH₃)₂) 2-methyl-2-butoxy (-OC (CH))₃)₂CH₂CH₃) 3-methyl-2-butoxy (-OCH (CH)₃)CH(CH₃)₂) 3-methyl-l-butoxy (-OCH)₂CH₂CH(CH₃)₂) 2-methyl-l-butoxy (-OCH)₂CH(CH₃)CH₂CH₃) 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. In some of these embodiments, the alkylamino group is one or two C_1-6Lower alkylamino groups in which the alkyl group is attached to the nitrogen atom. In other embodiments, the alkylamino group is C_1-3Lower alkylamino groups of (a). Suitable alkylamino groups may be monoalkylamino or dialkylamino, such entitiesExamples include, but are not limited to, N-methylamino, N-ethylamino, N, N-dimethylamino, N, N-diethylamino, and the like.

The term "alkylthio" refers to a straight or branched chain alkyl group attached to a divalent sulfur atom, wherein the alkyl group has the meaning as described herein. Examples of alkylthio groups include, but are not limited to, -SCH₃、-SCH₂CH₃、-SCH₂CH₂CH₃And so on.

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

The term "haloalkyl" denotes an alkyl group substituted with one or more halogen atoms. Examples of haloalkyl include, but are not limited to, -CH₂F，-CHF₂，-CH₂Cl，-CH₂Br，-CF₃，-CH₂CF₃，-CH₂CH₂F，-CH₂CH₂Cl，-CH₂CH₂Br，-CH₂CHF₂，-CH₂CH₂CF₃，-CH₂CH₂CH₂F，-CH₂CH₂CH₂Cl，-CH₂CH₂CH₂Br，-CHFCH₂CH₃，-CHClCH₂CH₃And so on.

The term "haloalkoxy" denotes an alkoxy group substituted with one or more halogen atoms. Examples of haloalkoxy include, but are not limited to, -OCH₂F，-OCHF₂，-OCH₂Cl，-OCH₂Br，-OCF₃，-OCH₂CF₃，-OCH₂CH₂F，-OCH₂CH₂Cl，-OCH₂CH₂Br，-OCH₂CHF₂，-OCH₂CH₂CF₃，-OCH₂CH₂CH₂F，-OCH₂CH₂CH₂Cl，-OCH₂CH₂CH₂Br，-OCHFCH₂CH₃，-OCHClCH₂CH₃And so on.

The term "haloalkylamino" denotes an alkylamino group substituted with one or more halogen atoms.

The term "haloalkylthio" denotes an alkylthio group substituted by one or more halogen atoms.

The term "haloalkenyl" denotes an alkenyl group substituted with one or more halogen atoms.

The term "haloalkynyl" denotes an alkynyl group substituted by one or more halogen atoms.

The term "cycloalkyl" denotes a monovalent or polyvalent saturated monocyclic, bicyclic or tricyclic ring system containing from 3 to 15 carbon atoms. In one embodiment, the cycloalkyl group contains 3 to 12 carbon atoms; in one embodiment, the cycloalkyl group contains 3 to 10 carbon atoms; in another embodiment, cycloalkyl contains 3 to 8 carbon atoms; in yet another embodiment, the cycloalkyl group contains 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 "unsaturated" as used herein 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 form of P; primary, secondary, tertiary amines and quaternary ammonium salt forms; or a form in which a hydrogen on a 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 term "aryl" denotes monocyclic, bicyclic and tricyclic carbon ring systems 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 comprises a ring of 3 to 7 atoms with one or more attachment points to the rest of the molecule. The term "aryl" may be used interchangeably with the term "aromatic ring". Examples of the aryl group may include phenyl, indenyl, naphthyl and anthryl. 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 linked from an oxygen atom to the rest of the molecule, wherein the aryl group has the meaning as described herein.

The term "heteroaryl" denotes 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 with one or more attachment points to the rest of the molecule. The term "heteroaryl" may be used interchangeably with the terms "heteroaromatic ring" or "heteroaromatic compound". The heteroaryl group is optionally substituted with one or more substituents described herein.

In one embodiment, a heteroaryl group of 5-10 atoms contains 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 group containing 1-3 heteroatoms selected from N, O or S; in yet another embodiment, heteroaryl represents a 5 membered heteroaryl group containing 1-3 heteroatoms selected from N or O; in yet another embodiment, heteroaryl represents a 5 membered heteroaryl group 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, 3-triazolyl, 1,2, 3-thiadiazolyl, 1,3, 4-thiadiazolyl, 1,2, 5-thiadiazolyl, pyrazinyl, 1,3, 5-triazinyl, pyrimidinonyl, pyridonyl; the following bicyclic rings are also included, but are in no way limited to these: benzimidazolyl, benzofuranyl, benzotetrahydrofuranyl, benzothienyl, indolyl (e.g., 2-indolyl), and the like.

The term "heteroaryloxy" or "heteroaryloxy" includes optionally substituted heteroaryl groups, as defined herein, attached to and linked by an oxygen atom to the rest of the molecule, wherein the heteroaryl group has the meaning as set forth herein.

When the compounds of the present invention contain an acid moiety, salts of the compounds of the present invention include those derived from alkali or alkaline earth metals as well as those derived from ammonia and amines. Preferred cations include sodium, potassium, magnesium and those of formula N⁺(R¹⁹R²⁰R²¹R²²) Ammonium cation of (2), wherein R is¹⁹、R²⁰、R²¹And R²²Independently selected from hydrogen, C₁-C₆Alkyl and C₁-C₆A hydroxyalkyl group. Salts of compounds having formula (I) or formula (II) may be prepared by treating a compound having formula (I) or formula (II) with a metal hydroxide (e.g., sodium hydroxide) or an amine (e.g., ammonia, trimethylamine, diethanolamine, 2-methylthiopropylamine, diallylamine, 2-butoxyethylamine, morpholine, cyclododecylamine, or benzylamine).

When a compound of the invention comprises a base moiety, acceptable salts can be formed from organic and inorganic acids, such as acetic, propionic, lactic, citric, tartaric, succinic, fumaric, maleic, malonic, mandelic, malic, phthalic, hydrochloric, hydrobromic, phosphoric, nitric, sulfuric, methanesulfonic, napthalenesulfonic, benzenesulfonic, toluenesulfonic, camphorsulfonic, and similarly known acceptable acids.

Compositions and formulations of the compounds of the invention

The compounds of the present invention are generally useful as herbicidal active ingredients in compositions or formulations having at least one pesticidally acceptable adjuvant selected from the group consisting of surfactants, solid diluents and liquid diluents, and the like, all of which 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, moisture 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 into gels. Common types of aqueous liquid compositions are soluble concentrates, suspension concentrates, capsule suspensions, concentrated emulsions, microemulsions and suspoemulsions. Common 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, prills, 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 formed into a suspension or solid formulation; alternatively, the entire active ingredient formulation may be encapsulated (or "coated"). Encapsulation may control or delay the release of the active ingredient. Emulsifiable granules combine the advantages of both emulsifiable concentrate formulations and dry granular 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 to be readily diluted in a spray medium, typically water. The spray volume may be in the range of about one to several thousand liters per hectare, but more typically in the range of about ten to several hundred liters per hectare. The sprayable formulation may be mixed with water or another suitable medium in a water tank for treatment of the foliage by air or ground application, or applied to the growing medium of the plant. The liquid and dry formulations can be dosed directly into the drip irrigation system or into the furrow during planting.

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

Solid diluents include, for example, clays, bentonite, montmorillonite, attapulgite and kaolin, gypsum, cellulose, titanium dioxide, zinc oxide, starches, dextrins, sugars (e.g., lactose, sucrose), silica, talc, mica, diatomaceous earth, urea, calcium carbonate, sodium carbonate and bicarbonate and sodium sulfate. Typical solid Diluents are described in Handbook of Instrument Dust Diluents and Cariers, 2 nd edition, Dorland Books, Caldwell, N.J. by Watkins et al.

Liquid diluents include, for example, water, N-dimethyl alkanamides (e.g., N-dimethylformamide), limonene, dimethyl sulfoxide, N-alkylpyrrolidones (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, triacetin, sorbitol, aromatic hydrocarbons, dealkylated aliphatic compounds, ketones (e.g., cyclohexanone, 2-heptanone, isophorone and 4-hydroxy-4-methyl-2-pentanone), acetates (e.g., isoamyl acetate, hexyl acetate, heptyl acetate, octyl acetate, nonyl acetate, tridecyl acetate, and isobornyl acetate), Other esters (such as alkylated lactates, dibasic esters and gamma-butyrolactones) and may be straight chain, branched chain, saturated or unsaturated alcohols (such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, n-hexanol, 2-ethylhexanol, n-octanol, decanol, isodecanol, isostearyl alcohol, cetyl alcohol, lauryl alcohol, tridecyl alcohol, oleyl alcohol, cyclohexanol, tetrahydrofurfuryl alcohol, diacetone alcohol and benzyl alcohol). Liquid diluents also include glycerol esters 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, grapeseed 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, which can be obtained by hydrolysis of vegetable and animal derived glycerides and can be purified by distillation. Typical liquid diluents are described in Marsden's Solvents Guide, 2 nd edition, Interscience, New York, 1950.

The solid and liquid compositions of the present invention typically comprise one or more surfactants. Surfactants (also known as "surface active agents") generally change when added to a liquid, most often lowering the surface tension of the liquid. Surfactants can be used as wetting agents, dispersing agents, emulsifying agents, or defoaming agents, depending on the nature of the hydrophilic and lipophilic groups in the surfactant molecule.

Surfactants can be classified as nonionic, anionic, or cationic surfactants. Nonionic surfactants useful as 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 ethoxylation, alkanolamides, and ethoxylated alkanolamides; alkoxylated triglycerides, such as ethoxylated soybean, castor and rapeseed oil; alkylphenol alkoxylates 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, glycerides, 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, graft 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: alkyl aryl sulfonic acids and their salts; carboxylated alcohols or alkylphenol ethoxylates; a diphenyl sulfonate derivative; lignin and lignin derivatives, such as lignosulfonates; maleic or succinic acid or anhydrides thereof; olefin sulfonates; phosphate esters such as phosphate esters of alcohol alkoxylates, phosphate esters of alkylphenol alkoxylates, and phosphate esters of styrylphenol ethoxylates; a protein-based surfactant; a sarcosine derivative; styrylphenol ether sulfate; sulfates and sulfonates of oils and fatty acids; sulfates and sulfonates of ethoxylated alkylphenols; sulfates of alcohols; sulfates of ethoxylated alcohols; amine and amide sulfonates, such as N, N-alkyl taurates; benzene, cumene, toluene, xylene, and sulfonates of dodecylbenzene and tridecylbenzene; a sulfonate of condensed polynaphthalene; sulfonates of naphthalene and alkylnaphthalenes; sulfonates of petroleum fractions; 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, and ethoxylated, ethoxylated and propoxylated amines (prepared from amines and ethylene oxide, propylene oxide, butylene oxide or mixtures thereof); amine salts, such as amine acetates and diamine salts; quaternary ammonium salts such as quaternary salts, ethoxylated quaternary salts and diquaternary salts; and amine oxides such as alkyldimethylamine oxide and bis- (2-hydroxyethyl) -alkylamine oxide.

Also useful in the compositions of the present invention are mixtures of nonionic and anionic surfactants or mixtures of nonionic and cationic surfactants. Nonionic, anionic and cationic surfactants and their proposed uses are disclosed in a number of published references, including McCutcheon's Emulsifiers and Detergents, north american and international yearbook versions, published by McCutcheon's Division, The Manufacturing conditioner Publishing co; the Encyclopdia of Surface Active Agents by Sisely and Wood, Chemical Publ.Co., Inc., New York, 1964; and Synthetic Detergents, seventh edition, John Wiley and Sons, New York, 1987, by a.s.davidson and b.milwidsky.

The compositions of the present invention may also contain formulation adjuvants 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 may control: pH (buffer), foaming during processing (antifoam such as polyorganosiloxane), sedimentation of the active ingredient (suspending agent), viscosity (thixotropic thickener), microbial growth in the container (biocide), 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 conditioner Publishing co: functional Materials, north american and international yearbook versions; and those listed in PCT publication WO 03/024222.

The compounds of the present invention and any other active ingredients are typically incorporated into the compositions of the present invention by dissolving the active ingredient in a solvent or by grinding the active ingredient in a liquid diluent or a dry diluent. Solutions, including emulsifiable concentrates, can be prepared by simply mixing the ingredients. If the solvent of the liquid composition used as an emulsifiable concentrate is water-immiscible, an emulsifier is usually 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 can 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, which results in an average particle size in the range of 2 to 10 μm. Powders and dusts can be prepared by mixing, and usually by grinding (e.g., with a hammer mill or fluid energy mill). Particles and granules can be prepared by spraying the active substance onto preformed particle carriers or by agglomeration techniques. See Browning "agglomerization" (Chemical Engineering, 12.4.1967, pages 147-48; Perry's Chemical Engineering' Handbook, 4 th edition, McGraw-Hill, New York, 1963, pages 8-57 and later and WO 91/13546. the pellets can be prepared as described in u.s.4,172,714. the water dispersible and water soluble particles can be prepared as set forth in u.s.4,144,050, u.s.3,920,442 and de.3,246,493. the tablets can be prepared as set forth in u.s.5,180,587, u.s.5,232,701 and u.s.5,208,030. the films can 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 formulations's Toolbox-Product Forms for model Agriculture" by T.S. woods, The Food-Environment Challenge, T.Brooks and T.R. Roberts eds, Proceedings of The 9th International conformation on Pesticide Chemistry, The Royal Society of Chemistry, Cambridge, 1999, p.120. 133. See also U.S.3,235,361, column 6, line 16 to column 7, line 19 and examples 10-41; U.S. Pat. No. 3,309,192, column 5, column 43 to column 7, column 62 and examples 8, 12, 15, 39, 41, 52, 53, 58, 132, 138, 162, 164, 166, 167 and 169, 182; U.S.2,891,855 at column 3, line 66 to column 5, line 17 and examples 1-4; wed Control as a Science by Klingman, John Wiley and Sons, Inc., New York, 1961, pages 81-96; weed Control Handbook, 8 th edition, Blackwell Scientific Publications, Oxford, 1989, by Hance et al; and Developments in simulation technology, PJB Publications, Richmond, UK, 2000.

Use of the Compounds of the invention

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

The amount of the compound of the present invention to be used is determined depending on the kind of the compound to be used, the target weed, the tendency of weed to appear, environmental conditions, the kind of herbicide, and the like. When the herbicides of the invention are used as such, for example in the form of powders or granules, the amount is suitably selected to be from 1g to 50kg per 1 hectare of active ingredient, preferably from 10g to 10kg per 1 hectare. When the herbicide of the present invention is used in a liquid form, for example, in the form of an emulsifiable concentrate, a wettable powder or a flowable formulation, the amount thereof is suitably selected from 0.1 to 50,000ppm, preferably from 10 to 10,000 ppm.

The present invention provides a method for controlling weeds in a crop of useful plants, comprising 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 the locus thereof or to the area of cultivation a herbicidally effective amount of a compound of formula (I) or (II).

The term "herbicide" means a compound that controls or modifies the growth of plants. The term "herbicidally effective amount" means the amount of such a compound or combination of such compounds that is capable of producing a control or modification of the growth of plants. The effects of control or modification include all deviations from natural development, e.g., kills, delays, leaf burns, albinism, dwarfing, etc. The term "plant" refers to all tangible parts of a plant, including seeds, seedlings, plantlets, roots, tubers, stems, stalks, leaves, and fruits. The term "locus" is intended to include soil, seeds and seedlings, as well as established plants (grassed habitat) and includes not only areas where weeds may have grown, but also areas where weeds have not yet emerged, and also areas for the planting of crops of useful plants. "planted area" includes the land on which crop plants have grown, as well as the land intended for planting such crop plants. The term "weeds" as used herein means any undesirable vegetation and thus includes not only important agronomic weeds as described below, but also volunteer crop plants.

Crops of useful plants in which the compositions according to the invention may be used include, but are not limited to, perennial crops such as citrus fruits, grapevines, nuts, oil palms, olives, pome fruits, stone fruits and rubber, and annual arable crops such as cereals (such as barley and wheat), cotton, oilseed rape, maize, rice, soya, sugar beet, sugar cane, sunflowers, ornamentals, switchgrass, turf and vegetables, especially cereals, maize and soya.

The grasses and weeds to be controlled can be both monocotyledonous species, such as agrostis, alopecurus, avena, brachiaria, bromus, tribulus, cyperus, digitaria, barnyard grass, kojima, lolium, monocrotonia, panicum, poa, cylindron, arrowhead, scirpus, setaria, sida and sorghum, and dicotyledonous species, such as kenaf, amaranthus, chenopodium, chrysanthemum, euphorbia, labra, ipomoea, kochia, eclipta, polygonum, rhodomyrtus, sinapis, solanum, chickweed, veronica, 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, oats, peanut, vegetables, tomato, potato, perennial plant crops including coffee, cocoa, oil palm, rubber, sugar cane, citrus, grapes, fruit trees, nut trees, bananas, plantains, pineapple, hops, tea and forests such as eucalyptus and conifer (e.g., loblolly pine), and turf varieties (e.g., prairie grass, san augustine grass (st. augustine grass), Kentucky grass and bermudagrass).

If desired, the compounds of the formula (I) or (II) according to the invention can also be used 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 for controlling the growth of weeds and/or undesired vegetation, form yet further aspects of the invention. For the avoidance of doubt, inventive mixtures also include mixtures of two or more different compounds of formula (I) or formula (II). In particular, the present invention also relates to a composition according to the invention comprising, in addition to the compound of formula (I) or formula (II), at least one further herbicide.

General synthetic procedure

In this specification, a structure is dominant if there is any difference between the chemical name and the 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 the preparation of the compounds of the present invention are commercially available or can be prepared by methods conventional in the art.

The test conditions of the nuclear magnetic resonance hydrogen spectrum of the invention are as follows: brookfield (Bruker) nuclear magnetic instrument at 400MHz or 600MHz in CDC1 at room temperature₃，d⁶-DMSO，CD₃OD or d⁶Acetone as solvent (reported in ppm) with TMS (0ppm) or chloroform (7.26ppm) as reference standard. When multiple peaks occur, the following abbreviations will be used: s (singlets, singlet)) D (duplet, doublet), t (triplet ), q (quatet, quartet), m (multiplet ), br (broadbanding, broad), dd (duplet of doublets), dt (duplet 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 6120 ESI.

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

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

Flow rate: 0.6 mL/min.

Detection wavelength: 254 nm.

MS parameters: ESI positive scan, collision induced ionization: 70V.

Drying nitrogen gas: 12L/min, atomizing gas pressure: 40psi, gas temperature: at 350 ℃.

Taking a proper amount of sample, dissolving in 0.5mL of methanol, injecting a sample, and performing primary MS full scanning in a positive ESI mode to obtain an excimer peak [ M + H ]]⁺And (6) reading.

The following abbreviations are used throughout the present invention:

DMF: n, N-dimethylformamide, dimethylformamide

EtOAc: ethyl acetate

Petroleum ether: petroleum ether

NBS: n-bromosuccinimide, N-bromosuccinimide

NCS: n-chlorosuccinimide, N-chlorosuccinimide

The following examples 1-17 serve to further illustrate the context of the invention.

Examples

Example 1: synthesis of Compound 2- (((Perfluorophenoxy) methyl) sulfonyl) thiazole

Step 1: synthesis of compound thiazole-2-thiol

2-bromothiazole (50.0g,305mmol) was added to a 1L three-necked flask, dissolved in ethanol (500mL), thiourea (116.0g,1.52mol) was added at room temperature, the temperature was raised to 80 ℃ and after 4 hours of reaction at 80 ℃, the reaction was monitored by TLC (thin layer chromatography) until the starting material reaction was complete. The temperature was reduced to room temperature, the solvent was removed and column chromatography was performed (eluent: Petroleum ether/EtOAc (v/v) ═ 5/1) to give 30.0g of a white solid in 84.0% yield.

MS-ESI:m/z 118.0[M+H]⁺.

Step 2: synthesis of the Compound 2- ((chloromethyl) thio) thiazole

Thiazole-2-thiol (30.0g,256mmol) was added to a 500mL three-necked flask, dissolved in DMF (300mL), potassium tert-butoxide (28.7g,256mmol) was added under ice bath, after 1h of reaction, bromochloromethane (36.4g,282mmol) was added to the reaction flask, after 2h of reaction under ice bath, and the reaction was monitored by TLC (thin layer chromatography) until the starting material was reacted completely. Water (500mL) was added to the reaction mixture and stirred. Extraction was performed twice with ethyl acetate (300mL), the organic phases were combined, dried over anhydrous sodium sulfate, the solvent was removed, and column chromatography was performed (eluent: Petroleum ether/EtOAc (v/v) ═ 10/1) to give 30.0g of a colorless liquid, with a yield of 70.4%.

MS-ESI:m/z 166.0[M+H]⁺.

And step 3: synthesis of compound 2- (((perfluorophenoxy) methyl) thio) thiazole

2,3,4,5, 6-pentafluorophenol (10.0g,54.3mmol) is added into a 500mL three-neck flask, DMF (100mL) is used for dissolution, potassium tert-butoxide (6.10g,54.3mmol) is added under ice bath, after 1h of reaction, 2- ((chloromethyl) thio) thiazole (9.00g,54.3mmol) and sodium iodide (407mg,2.72mmol) are respectively added into a reaction bottle, the temperature is increased to 80 ℃, after 16h of reaction at 80 ℃, TLC (thin layer chromatography) monitors the reaction until the raw materials are completely reacted, the temperature is reduced to room temperature, water (50mL) is added into the reaction mixture, and the mixture is stirred. Extraction was performed twice with ethyl acetate (30mL), the organic phases were combined, dried over anhydrous sodium sulfate, the solvent was removed, and column chromatography was performed (eluent: Petroleum ether/EtOAc (v/v) ═ 10/1) to give 12.0g of a colorless liquid, with a yield of 70.5%.

MS-ESI:m/z 314.0[M+H]⁺.

And 4, step 4: synthesis of Compound 2- (((Perfluorophenoxy) methyl) sulfonyl) thiazole

A100 mL flask was charged with 2- (((perfluorophenoxy) methyl) thio) thiazole (1.00g,3.19mmol) and dissolved in dichloromethane (20 mL). To the mixture was added 75% m-chloroperoxybenzoic acid (1.84g,7.98mmol), and the mixture was stirred at room temperature for 12 hours. And (5) finishing the reaction. The reaction mixture was washed with a saturated solution of sodium hydrogensulfite (30mL), a saturated solution of sodium hydrogencarbonate (30mL) and saturated solution of sodium chloride (30mL) in this order, extracted with dichloromethane (30mL) three times, the organic phases were combined, dried over anhydrous magnesium sulfate, the solvent was removed, and column chromatography was performed (eluent: Petroleum ether/EtOAc (v/v) ═ 10/1) to give 0.60g of a white solid in 54.4% yield.

MS-ESI:m/z 346.0[M+H]⁺.

¹H NMR(400MHz,CDCl₃)δ8.13(d,J＝2.9Hz,1H),7.87(d,J＝2.9Hz,1H),5.47(s,2H).

Example 2: synthesis of Compound 5-chloro-2- (((Perfluorophenoxy) methyl) sulfonyl) thiazole

Step 1: synthesis of compound 5-chloro-2- (((perfluorophenoxy) methyl) thio) thiazole

A50 mL flask was charged with 2- (((perfluorophenoxy) methyl) thio) thiazole (1.00g,3.19mmol) and dissolved in DMF (20 mL). NCS (469mg,3.51mmol) was added to the mixture in an ice bath, and the mixture was returned to room temperature and stirred at room temperature for 12 hours. And (5) finishing the reaction. Water (50mL) was added to the reaction mixture and stirred. Extraction was performed twice with ethyl acetate (30mL), the organic phases were combined, dried over anhydrous sodium sulfate, the solvent was removed, and column chromatography was performed (eluent: Petroleum ether/EtOAc (v/v) ═ 10/1) to give 0.40g of a colorless liquid, yield 36.0%.

MS-ESI:m/z 347.9[M+H]⁺.

Step 2: synthesis of Compound 5-chloro-2- (((Perfluorophenoxy) methyl) sulfonyl) thiazole

A50 mL flask was charged with 5-chloro-2- (((perfluorophenoxy) methyl) sulfonyl) thiazole (400mg,1.15mmol) and dissolved in dichloromethane (20 mL). To the mixture was added 75% m-chloroperoxybenzoic acid (662mg,2.88mmol), and the mixture was stirred at room temperature for 12 hours. And (5) finishing the reaction. The reaction mixture was washed with a saturated solution of sodium hydrogensulfite (30mL), a saturated solution of sodium hydrogencarbonate (30mL) and saturated solution of sodium chloride (30mL) in this order, extracted with dichloromethane (30mL) three times, the organic phases were combined, dried over anhydrous magnesium sulfate, the solvent was removed, and column chromatography was performed (eluent: Petroleum ether/EtOAc (v/v) ═ 10/1) to give 0.30g of a white solid in 68.7% yield.

MS-ESI:m/z 379.9[M+H]⁺.

¹H NMR(400MHz,CDCl₃)δ7.93(s,1H),5.42(s,2H).

Example 3: synthesis of Compound 5-bromo-2- (((Perfluorophenoxy) methyl) sulfonyl) thiazole

Step 1: synthesis of compound 5-bromo-2- (((perfluorophenoxy) methyl) thio) thiazole

A50 mL flask was charged with 2- (((perfluorophenoxy) methyl) thio) thiazole (1.00g,3.19mmol) and dissolved in DMF (20 mL). NBS (625mg,3.51mmol) was added to the mixture under ice-cooling, and the mixture was returned to room temperature and stirred at room temperature for 12 hours. And (5) finishing the reaction. Water (50mL) was added to the reaction mixture and stirred. Extraction was performed twice with ethyl acetate (30mL), the organic phases were combined, dried over anhydrous sodium sulfate, the solvent was removed, and column chromatography was performed (eluent: Petroleum ether/EtOAc (v/v) ═ 10/1) to give 0.50g of a colorless liquid, yield 39.9%.

MS-ESI:m/z 391.9[M+H]⁺.

Step 2: synthesis of Compound 5-bromo-2- (((Perfluorophenoxy) methyl) sulfonyl) thiazole

A50 mL flask was charged with 5-bromo-2- (((perfluorophenoxy) methyl) thio) thiazole (500mg,1.28mmol) and dissolved in dichloromethane (20 mL). To the mixture was added 75% m-chloroperoxybenzoic acid (733mg,3.19mmol), and the mixture was stirred at room temperature for 12 hours. And (5) finishing the reaction. The reaction mixture was washed with a saturated solution of sodium hydrogensulfite (30mL), a saturated solution of sodium hydrogencarbonate (30mL) and saturated solution of sodium chloride (30mL) in this order, extracted with dichloromethane (30mL) three times, the organic phases were combined, dried over anhydrous magnesium sulfate, the solvent was removed, and column chromatography was performed (eluent: Petroleum ether/EtOAc (v/v) ═ 10/1) to give 0.30g of a white solid in 55.5% yield.

MS-ESI:m/z 423.9[M+H]⁺.

¹H NMR(400MHz,CDCl₃)δ8.02(s,1H),5.42(s,2H).

Example 4: synthesis of Compound 2- (((4-ethoxy-2, 3,5, 6-tetrafluorophenoxy) methyl) sulfonyl) thiazole

Step 1: synthesis of Compound 2- (((4-ethoxy-2, 3,5, 6-tetrafluorophenoxy) methyl) thio) thiazole

A100 mL flask was charged with 2- (((perfluorophenoxy) methyl) thio) thiazole (2.00g,6.38mmol) and dissolved in ethanol (30 mL). Cesium carbonate (4.16g,12.8mmol) was added to the above solution at room temperature, the temperature was raised to 80 ℃, after reaction at 80 ℃ for 16 hours, TLC (thin layer chromatography) monitored the reaction until the reaction of the raw materials was completed, the temperature was lowered to room temperature, and water (50mL) was added to the reaction mixture and stirred. Extraction was performed twice with ethyl acetate (30mL), the organic phases were combined, dried over anhydrous sodium sulfate, the solvent was removed, and column chromatography was performed (eluent: Petroleum ether/EtOAc (v/v) ═ 10/1) to give 1.00g of a colorless liquid, yield 46.2%.

MS-ESI:m/z 340.0[M+H]⁺.

Step 2: synthesis of Compound 2- (((4-ethoxy-2, 3,5, 6-tetrafluorophenoxy) methyl) sulfonyl) thiazole

A50 mL flask was charged with 2- (((4-ethoxy-2, 3,5, 6-tetrafluorophenoxy) methyl) thio) thiazole (500mg,1.47mmol) and dissolved in dichloromethane (20 mL). To the mixture was added 75% m-chloroperoxybenzoic acid (848mg,3.68mmol), and the mixture was stirred at room temperature for 12 hours. And (5) finishing the reaction. The reaction mixture was washed with a saturated solution of sodium hydrogensulfite (30mL), a saturated solution of sodium hydrogencarbonate (30mL) and saturated solution of sodium chloride (30mL) in this order, extracted with dichloromethane (30mL) three times, the organic phases were combined, dried over anhydrous magnesium sulfate, the solvent was removed, and column chromatography was performed (eluent: Petroleum ether/EtOAc (v/v) ═ 10/1) to give 0.30g of a colorless liquid in 54.8% yield.

MS-ESI:m/z 372.0[M+H]⁺.

¹H NMR(400MHz,CDCl₃)δ8.12(d,J＝3.0Hz,1H),7.86(d,J＝3.0Hz,1H),5.45(s,2H),4.23(q,J＝7.0Hz,2H),1.40(t,J＝5.7Hz,3H).

Example 5: synthesis of Compound 5-chloro-2- (((4-ethoxy-2, 3,5, 6-tetrafluorophenoxy) methyl) sulfonyl) thiazole

Step 1: synthesis of compound 5-chloro-2- (((4-ethoxy-2, 3,5, 6-tetrafluorophenoxy) methyl) thio) thiazole

A50 mL flask was charged with 2- (((4-ethoxy-2, 3,5, 6-tetrafluorophenoxy) methyl) thio) thiazole (1.00g,2.95mmol) and dissolved in DMF (20 mL). To the mixture was added NCS (433mg,3.24mmol) under ice-cooling, and the mixture was returned to room temperature and stirred at room temperature for 12 hours. And (5) finishing the reaction. Water (50mL) was added to the reaction mixture and stirred. Extraction was performed twice with ethyl acetate (30mL), the organic phases were combined, dried over anhydrous sodium sulfate, the solvent was removed, and column chromatography was performed (eluent: Petroleum ether/EtOAc (v/v) ═ 10/1) to give 0.40g of a colorless liquid, yield 36.3%.

MS-ESI:m/z 374.0[M+H]⁺.

Step 2: synthesis of Compound 5-chloro-2- (((4-ethoxy-2, 3,5, 6-tetrafluorophenoxy) methyl) sulfonyl) thiazole

To a 50mL flask was added 5-chloro-2- (((4-ethoxy-2, 3,5, 6-tetrafluorophenoxy) methyl) thio) thiazole (400mg,1.07mmol) and dissolved in dichloromethane (20 mL). To the mixture was added 75% m-chloroperoxybenzoic acid (616mg,2.68mmol), and the mixture was stirred at room temperature for 12 hours. And (5) finishing the reaction. The reaction mixture was washed with a saturated solution of sodium hydrogensulfite (30mL), a saturated solution of sodium hydrogencarbonate (30mL) and a saturated solution of sodium chloride (30mL) in this order, extracted with dichloromethane (30mL) three times, the organic phases were combined, dried over anhydrous magnesium sulfate, the solvent was removed, and column chromatography was performed (eluent: Petroleum ether/EtOAc (v/v) ═ 10/1) to give 0.30g of a colorless liquid in 69.1% yield.

MS-ESI:m/z 406.0[M+H]⁺.

¹H NMR(400MHz,CDCl₃)δ7.91(s,1H),5.40(s,2H),4.25(q,J＝7.0Hz,2H),1.41(t,J＝7.0Hz,3H).

Example 6: synthesis of Compound 5-bromo-2- (((4-ethoxy-2, 3,5, 6-tetrafluorophenoxy) methyl) sulfonyl) thiazole

Step 1: synthesis of compound 5-bromo-2- (((4-ethoxy-2, 3,5, 6-tetrafluorophenoxy) methyl) thio) thiazole

A50 mL flask was charged with 2- (((perfluorophenoxy) methyl) thio) thiazole (1.00g,2.95mmol) and dissolved in DMF (20 mL). NBS (577mg,3.24mmol) was added to the mixture under ice-cooling, and the mixture was returned to room temperature and stirred at room temperature for 12 hours. And (5) finishing the reaction. Water (50mL) was added to the reaction mixture and stirred. Extraction was performed twice with ethyl acetate (30mL), the organic phases were combined, dried over anhydrous sodium sulfate, the solvent was removed, and column chromatography separation (eluent: Petroleum ether/EtOAc (v/v) ═ 10/1) gave 0.50g of yellow liquid in 40.6% yield.

MS-ESI:m/z 417.9[M+H]⁺.

Step 2: synthesis of Compound 5-bromo-2- (((4-ethoxy-2, 3,5, 6-tetrafluorophenoxy) methyl) sulfonyl) thiazole

To a 50mL flask was added 5-bromo-2- (((4-ethoxy-2, 3,5, 6-tetrafluorophenoxy) methyl) thio) thiazole (500mg,1.20mmol) and dissolved in dichloromethane (20 mL). To the mixture was added 75% m-chloroperoxybenzoic acid (688mg,2.99mmol), and the mixture was stirred at room temperature for 12 hours. And (5) finishing the reaction. The reaction mixture was washed with a saturated solution of sodium hydrogensulfite (30mL), a saturated solution of sodium hydrogencarbonate (30mL) and a saturated solution of sodium chloride (30mL) in this order, extracted with dichloromethane (30mL) three times, the organic phases were combined, dried over anhydrous magnesium sulfate, the solvent was removed, and column chromatography was performed (eluent: Petroleum ether/EtOAc (v/v) ═ 10/1) to give 0.30g of a colorless liquid in 55.7% yield.

MS-ESI:m/z 449.9[M+H]⁺.

¹H NMR(400MHz,CDCl₃)δ8.00(s,1H),5.40(s,2H),4.25(q,J＝7.1Hz,2H),1.41(t,J＝7.0Hz,3H).

By referring to the preparation methods of the foregoing examples, the objective compounds of table 1 can be prepared using the corresponding starting materials.

TABLE 1

Example 15: synthesis of Compound 2- (((4-chloro-2, 3,5, 6-tetrafluorophenoxy) methyl) sulfonyl) -4, 4-dimethyl-4, 5-dihydrothiazole

Step 1: synthesis of compound 4, 4-dimethyl-4, 5-dihydrothiazole-2-thiol

2-amino-2-methylpropan-1-ol (5.00g,56.1mmol) is added into a 250mL three-necked flask, dissolved by water (75mL), added with sodium hydroxide (9.00g,224mol) at room temperature, added with carbon disulfide (11.1g,146mol) again, heated to 100 ℃ for 16h, and monitored by TLC (thin layer chromatography) until the raw materials are completely reacted. The temperature was reduced to room temperature, the pH was adjusted to weak acidity with 1M dilute hydrochloric acid in ice bath, ethyl acetate (50mL) was extracted 2 times, the organic phases were combined, dried over anhydrous sodium sulfate, the solvent was removed, and column chromatography was performed (eluent: Petroleum ether/EtOAc (v/v) ═ 5/1) to give 2.90g of a white solid with a yield of 35.1%.

MS-ESI:m/z 148.0[M+H]⁺.

Step 2: synthesis of the compound 2- ((chloromethyl) thio) -4, 4-dimethyl-4, 5-dihydrothiazole

4, 4-dimethyl-4, 5-dihydrothiazole-2-thiol (1.00g,6.79mmol) was added to a 100mL three-necked flask, dissolved in DMF (15mL), and potassium tert-butoxide (762mg,6.79mmol) was added in ice bath to react for 1h, after which bromochloromethane (966mg,7.47mmol) was added to the flask and after 2h reaction in ice bath, the reaction was monitored by TLC (thin layer chromatography) until the starting material was reacted completely. Water (20mL) was added to the reaction mixture and stirred. Extraction was performed twice with ethyl acetate (30mL), the organic phases were combined, dried over anhydrous sodium sulfate, the solvent was removed, and column chromatography was performed (eluent: Petroleum ether/EtOAc (v/v) ═ 10/1) to give 0.80g of a colorless liquid, yield 60.2%.

MS-ESI:m/z 196.0[M+H]⁺.

And step 3: synthesis of compound 2- (((4-chloro-2, 3,5, 6-tetrafluorophenoxy) methyl) thio) -4, 4-dimethyl-4, 5-dihydrothiazole

4-chloro-2, 3,5, 6-tetrafluorophenol (0.80g,3.99mmol) was added to a 100mL three-necked flask, dissolved in DMF (10mL), potassium tert-butoxide (448mg,3.99mmol) was added under ice-bath, and after 1h of reaction, 2- ((chloromethyl) thio) -4, 4-dimethyl-4, 5-dihydrothiazole (781mg,3.99mmol) and sodium iodide (29.9mg,0.20mmol) were added to the reaction flask, respectively, and after heating to 80 ℃ and reaction at 80 ℃ for 16h, TLC (thin layer chromatography) was used to monitor the reaction until the starting materials were reacted completely, and after cooling to room temperature, water (30mL) was added to the reaction mixture and stirred. Extraction was performed twice with ethyl acetate (20mL), the organic phases were combined, dried over anhydrous sodium sulfate, the solvent was removed, and column chromatography was performed (eluent: Petroleum ether/EtOAc (v/v) ═ 10/1) to give 0.80g of a colorless liquid, yield 55.7%.

MS-ESI:m/z 360.0[M+H]⁺.

And 4, step 4: synthesis of Compound 5, 5-dimethyl-3- (((4-chloro-2, 3,5, 6-tetrafluorophenoxy) methyl) sulfonyl) -4, 5-dihydroisoxazole

To a 100mL flask was added 2- (((4-chloro-2, 3,5, 6-tetrafluorophenoxy) methyl) thio) -4, 4-dimethyl-4, 5-dihydrothiazole (0.80g,2.22mmol) and dissolved in dichloromethane (20 mL). To the mixture was added 75% m-chloroperoxybenzoic acid (1.28g,5.56mmol), and the mixture was stirred at room temperature for 12 hours. And (5) finishing the reaction. The reaction mixture was washed with a saturated solution of sodium hydrogensulfite (30mL), a saturated solution of sodium hydrogencarbonate (30mL) and saturated solution of sodium chloride (30mL) in this order, extracted with dichloromethane (30mL) three times, the organic phases were combined, dried over anhydrous magnesium sulfate, the solvent was removed, and column chromatography was performed (eluent: Petroleum ether/EtOAc (v/v) ═ 10/1) to give 0.60g of a white solid in 68.9% yield.

MS-ESI:m/z 392.0[M+H]⁺.

¹H NMR(400MHz,CDCl₃)δ5.91(s,2H),3.10(s,2H),1.39(s,6H).

Example 16: synthesis of compound 2- (((4-chloro-2, 3,5, 6-tetrafluorophenoxy) methyl) sulfonyl) -5-methyl-1, 3, 4-thiadiazole

Step 1: synthesis of compound 2- ((chloromethyl) thio) -5-methyl-1, 3, 4-thiadiazole

A250 mL three-necked flask was charged with 5-methyl-1, 3, 4-thiadiazole-2-thiol (5.00g,37.8mmol), dissolved in DMF (50mL), and potassium tert-butoxide (4.24g,37.8mmol) was added in ice bath, after 1h of reaction, bromochloromethane (5.38g,41.6mmol) was added to the flask, and after 2h of reaction in ice bath, TLC (thin layer chromatography) was used to monitor the reaction until the starting material was reacted completely. Water (20mL) was added to the reaction mixture and stirred. Extraction was performed twice with ethyl acetate (30mL), the organic phases were combined, dried over anhydrous sodium sulfate, the solvent was removed, and column chromatography was performed (eluent: Petroleum ether/EtOAc (v/v) ═ 10/1) to give 4.50g of a colorless liquid, yield 65.9%.

MS-ESI:m/z 181.0[M+H]⁺.

Step 2: synthesis of compound 2- (((4-chloro-2, 3,5, 6-tetrafluorophenoxy) methyl) thio) -5-methyl-1, 3, 4-thiadiazole

4-chloro-2, 3,5, 6-tetrafluorophenol (0.80g,3.99mmol) was added to a 100mL three-necked flask, dissolved in DMF (10mL), potassium tert-butoxide (448mg,3.99mmol) was added under ice-bath, after 1h of reaction, 2- ((chloromethyl) thio) -5-methyl-1, 3, 4-thiadiazole (721mg,3.99mmol) and sodium iodide (29.9mg,0.20mmol) were added to the reaction flask, respectively, heated to 80 ℃ and reacted at 80 ℃ for 16h, TLC (thin layer chromatography) was used to monitor the reaction until the starting material was reacted completely, cooled to room temperature, water (30mL) was added to the reaction mixture and stirred. Extraction was performed twice with ethyl acetate (20mL), the organic phases were combined, dried over anhydrous sodium sulfate, the solvent was removed, and column chromatography was performed (eluent: Petroleum ether/EtOAc (v/v) ═ 10/1) to give 0.80g of a yellow solid in 58.2% yield.

MS-ESI:m/z 345.0[M+H]⁺.

And step 3: synthesis of compound 2- (((4-chloro-2, 3,5, 6-tetrafluorophenoxy) methyl) sulfonyl) -5-methyl-1, 3, 4-thiadiazole

To a 100mL flask was added 2- (((4-chloro-2, 3,5, 6-tetrafluorophenoxy) methyl) thio) -5-methyl-1, 3, 4-thiadiazole (0.80g,2.32mmol) and dissolved in dichloromethane (20 mL). To the mixture was added 75% m-chloroperoxybenzoic acid (1.33g,5.80mmol), and the mixture was stirred at room temperature for 12 hours. And (5) finishing the reaction. The reaction mixture was washed with a saturated solution of sodium hydrogensulfite (30mL), a saturated solution of sodium hydrogencarbonate (30mL) and saturated solution of sodium chloride (30mL) in this order, extracted with dichloromethane (30mL) three times, the organic phases were combined, dried over anhydrous magnesium sulfate, the solvent was removed, and column chromatography was performed (eluent: Petroleum ether/EtOAc (v/v) ═ 5/1) to give 0.60g of a white solid in 68.6% yield.

MS-ESI:m/z 376.9[M+H]⁺.

¹H NMR(400MHz,CDCl₃)δ5.59(s,2H),2.96(s,3H).

Example 17: synthesis of compound 2-methyl-5- (((perfluorophenoxy) methyl) sulfonyl) -1,3, 4-thiadiazole

Step 1: synthesis of compound 2- (((perfluorophenoxy) methyl) thio) -5-methyl-1, 3, 4-thiadiazole

2,3,4,5, 6-pentafluorophenol (1.00g,5.43mmol) was added to a 100mL three-necked flask, dissolved in DMF (15mL), potassium tert-butoxide (610mg,5.43mmol) was added in ice bath, after 1h of reaction, 2- ((chloromethyl) thio) -5-methyl-1, 3, 4-thiadiazole (982mg,5.43mmol) and sodium iodide (40.7mg,0.27mmol) were added to the reaction flask, respectively, and after heating to 80 ℃ and reaction at 80 ℃ for 16h, TLC (thin layer chromatography) was used to monitor the reaction until the starting materials were reacted completely, and after cooling to room temperature, water (30mL) was added to the reaction mixture and stirred. Extraction was performed twice with ethyl acetate (20mL), the organic phases were combined, dried over anhydrous sodium sulfate, the solvent was removed, and column chromatography was performed (eluent: Petroleum ether/EtOAc (v/v) ═ 10/1) to give 1.00g of a yellow solid in 56.1% yield.

MS-ESI:m/z 329.0[M+H]⁺.

Step 2: synthesis of compound 2- (((perfluorophenoxy) methyl) sulfonyl) -5-methyl-1, 3, 4-thiadiazole

A100 mL flask was charged with 2- (((perfluorophenoxy) methyl) thio) -5-methyl-1, 3, 4-thiadiazole (1.00g,3.05mmol) and dissolved in dichloromethane (20 mL). To the mixture was added 75% m-chloroperoxybenzoic acid (1.75g,7.62mmol), and the mixture was stirred at room temperature for 12 hours. And (5) finishing the reaction. The reaction mixture was washed with a saturated solution of sodium hydrogensulfite (30mL), a saturated solution of sodium hydrogencarbonate (30mL) and saturated solution of sodium chloride (30mL) in this order, extracted with dichloromethane (30mL) three times, the organic phases were combined, dried over anhydrous magnesium sulfate, the solvent was removed, and column chromatography was performed (eluent: Petroleum ether/EtOAc (v/v) ═ 5/1) to give 0.60g of a white solid in 54.6% yield.

MS-ESI:m/z 361.0[M+H]⁺.

¹H NMR(400MHz,CDCl₃)δ5.55(s,2H),2.96(s,3H).

Biological examples

Compound preparation: weighing a certain mass of original drug by using an analytical balance (0.0001g), dissolving the original drug by using DMF containing 1 wt% of Tween-80 emulsifier to prepare 1.0 wt% of mother liquor, and then diluting the mother liquor by using distilled water for later use.

The test method comprises the following steps: the test targets of the potting method are barnyard grass and purslane. A flowerpot with the inner diameter of 7.5cm is taken, composite soil (vegetable garden soil: seedling raising matrix, 1:2, v/v) is filled to 3/4 positions, the two weed targets are directly sown (the germination rate is more than or equal to 85 percent), the soil is covered by 0.2cm, and water is added to keep the soil moist for 24 hours for later use. After each compound is applied to an automatic spray tower (model: 3WPSH-700E) according to 300g of a.i./ha dose, the soil surface liquid medicine is aired and then transferred to a greenhouse for culture, and the activity (%) of weeds is checked after 25 days.

Activity evaluation:

evaluation criteria of inhibition (%) of weed emergence by the compound were visually investigated and recorded:

the test results are shown in table a.

TABLE A Pre-emergent herbicidal Activity of the Compounds of the invention

Examples	Barnyard grass	Herba Portulacae
			Example 1	80	100
Example 2	80	100
			Example 5	85	100
Example 10	90	100
			Example 11	85	100
Example 13	85	100

The compound of the invention has good control effect on barnyard grass and purslane. Is safe to crops, has better control effect on weeds than commercial herbicides and thiazole compounds with similar structures, and has excellent application prospect.

Claims (9)

1. A compound which is a compound of formula (I) or a stereoisomer, a nitroxide or a salt thereof:

wherein:

R^a、R^b、R^c、R^dand R^eEach independently is hydrogen, fluorine, chlorine, bromine, iodine, amino, nitro, cyano, hydroxyl, carboxyl, C_1-8Alkyl, halo C_1-8Alkyl radical, C_1-8alkyl-C (═ O) -, halo-C_1-8alkyl-C (═ O) -, C_2-8Alkenyl, halo C_2-8Alkenyl radical, C_2-8Alkynyl, halo C_2-8Alkynyl, C_1-8Alkoxy, halo C_1-8Alkoxy radical, C_1-8Alkylamino radical, C_1-8Alkylthio, halo C_1-8Alkylamino, halogeno C_1-8Alkylthio radical, C_3-12Cycloalkyl radical, C_6-14Aryl radical, C_6-14Aryloxy radical, C_1-9Heteroaryl or C_1-9A heteroaryloxy group;

R¹is hydrogen, fluorine, chlorine, bromine, iodine, C_1-8Alkyl, halo C_1-8Alkyl radical, C_2-8Alkenyl, halo C_2-8Alkenyl radical, C_2-8Alkynyl, halo C_2-8Alkynyl, C_1-8Alkoxy, halo C_1-8Alkoxy radical, C_1-8Alkylamino radical, C_1-8Alkylthio, halo C_1-8Alkylamino or halogeno C_1-8An alkylthio group;

is a single bond or a double bond;

x is N, CR²Or CR³R⁴；

When in use

When it is a single bond, X is CR³R⁴；

When in use

When it is a double bond, X is N or CR²；

R²、R³And R⁴Each independently is hydrogen, C_1-8Alkyl, halo C_1-8Alkyl radical, C_2-8Alkenyl, halo C_2-8Alkenyl radical, C_2-8Alkynyl or halo C_2-8Alkynyl.

2. The compound of claim 1, wherein

R^a、R^b、R^c、R^dAnd R^eEach independently of the others being hydrogen, fluorine, chlorine, bromine, iodine, ammoniaRadical, nitro radical, cyano radical, hydroxyl radical, carboxyl radical, C_1-6Alkyl, halo C_1-6Alkyl radical, C_1-6alkyl-C (═ O) -, halo-C_1-6alkyl-C (═ O) -, C_2-6Alkenyl, halo C_2-6Alkenyl radical, C_2-6Alkynyl, halo C_2-6Alkynyl, C_1-6Alkoxy, halo C_1-6Alkoxy radical, C_1-6Alkylamino radical, C_1-6Alkylthio, halo C_1-6Alkylamino, halogeno C_1-6Alkylthio radical, C_3-8Cycloalkyl radical, C_6-10Aryl radical, C_6-10Aryloxy radical, C_1-5Heteroaryl or C_1-5A heteroaryloxy group;

R¹is hydrogen, fluorine, chlorine, bromine, iodine, C_1-6Alkyl, halo C_1-6Alkyl radical, C_2-6Alkenyl, halo C_2-6Alkenyl radical, C_2-6Alkynyl, halo C_2-6Alkynyl, C_1-6Alkoxy, halo C_1-6Alkoxy radical, C_1-6Alkylamino radical, C_1-6Alkylthio, halo C_1-6Alkylamino or halogeno C_1-6An alkylthio group;

R²、R³and R⁴Each independently is hydrogen, C_1-6Alkyl, halo C_1-6Alkyl radical, C_2-6Alkenyl, halo C_2-6Alkenyl radical, C_2-6Alkynyl or halo C_2-6Alkynyl.

3. The compound according to claim 1 or 2, which is a compound of formula (II) or a stereoisomer, a nitroxide or a salt thereof of a compound of formula (II):

4. the compound of claim 3, wherein

R^cIs hydrogen, fluorine, chlorine, bromine, iodine, amino, nitro, cyano, hydroxyl, carboxyl, C_1-4Alkyl, halo C_1-4Alkyl radical, C_1-4alkyl-C (═ O) -, halo-C_1-4alkyl-C (═ O) -, C_1-4Alkoxy, halo C_1-4Alkoxy radical, C_3-6Cycloalkyl radical, C_6-10Aryl or C_6-10An aryloxy group;

x is N or CR²；

R¹Is hydrogen, fluorine, chlorine, bromine, iodine, C_1-4Alkyl, halo C_1-4Alkyl radical, C_2-4Alkenyl, halo C_2-4Alkenyl radical, C_2-4Alkynyl, halo C_2-4Alkynyl, C_1-4Alkoxy, halo C_1-4Alkoxy radical, C_1-4Alkylamino radical, C_1-4Alkylthio, halo C_1-4Alkylamino or halogeno C_1-4An alkylthio group;

R²is hydrogen, C_1-4Alkyl, halo C_1-4Alkyl radical, C_2-4Alkenyl, halo C_2-4Alkenyl radical, C_2-4Alkynyl or halo C_2-4Alkynyl.

5. The compound of claim 4, wherein

R^cIs hydrogen, fluorine, chlorine, bromine, iodine, amino, nitro, cyano, hydroxyl, carboxyl, -CH₃、-CH₂CH₃、-CH₂CH₂CH₃、-CH(CH₃)₂、-CH₂CH₂CH₂CH₃、-CH₂CH(CH₃)₂、-CH(CH₃)CH₂CH₃、-C(CH₃)₃、-OCH₃、-OCH₂CH₃、-OCH₂CH₂CH₃、-OCH(CH₃)₂、-CH₂Br、-CF₃、-CHF₂、-OCF₃、-OCHF₂、-OCH₂CF₃or-OCH₂CHF₂；

R¹Is hydrogen, fluorine, chlorine, bromine, iodine, -CH₃、-CH₂CH₃、-CH₂CH₂CH₃or-CH (CH)₃)₂。

6. The compound according to any one of claims 1 to 5, which is a compound having one of the following structures or a stereoisomer, a nitroxide or a salt thereof of a compound having one of the following structures:

7. a composition comprising a compound of any one of claims 1-6; optionally comprising at least one pesticidally acceptable adjuvant.

8. Use of a compound according to any one of claims 1 to 6 or a composition according to claim 7 in agriculture.

9. A method of controlling weed development in useful plants comprising applying to the locus of the weeds an effective amount of a compound according to any one of claims 1 to 6 or a composition according to claim 7.