CN110577498B - Triazole compound and application thereof in agriculture - Google Patents

Abstract

The invention provides a triazole compound and application thereof in agriculture; specifically, the invention provides a compound shown as a formula (I) and a preparation method thereof; compositions and formulations containing these compounds and their use as fungicides; wherein R is¹、X、R²、R³、n、R⁴、R⁵、R⁶、R⁷、R⁸And R⁹Have the meaning as given in the present invention.

Description

Triazole compounds and their application in agriculture

technical field

The invention belongs to the field of pesticides, and provides a novel triazole compound and a preparation method thereof; a composition containing these compounds and its application in agriculture.

Background technique

Plant diseases that damage ornamental crops, vegetable crops, field crops, cereal crops and fruit tree crops can result in significantly lower yields and thus higher consumption costs. The control of plant diseases caused by phytopathogenic fungi is extremely important in order to obtain high crop yields. For this purpose, pesticide products can be used during plant cultivation, many are commercially available, but there is a continuing need for new compounds that are more effective, economical, less toxic, safer for the environment or have different sites of action.

The present invention provides a novel triazole compound with bactericidal activity.

SUMMARY OF THE INVENTION

The purpose of the present invention is to provide a novel fungicidal compound with a remarkable control effect on plant diseases, a fungicidal composition and formulation containing the fungicidal compound, and applications thereof.

In one aspect, the present invention provides a compound represented by formula (I) or a stereoisomer, N-oxide and salt thereof of the compound represented by formula (I):

in:

R ¹ is hydrogen, alkyl, alkenyl, alkynyl, alkoxy, alkenyloxy, alkynyloxy, aryl, arylalkyl, heteroaryl, heteroarylalkyl, cycloalkyl, cycloalkane R is optionally substituted with ¹ , 2, 3, 4 or 5 substituents selected from R ^a ;

X is a bond, -O-, -C(=O)-, -S-, -S(=O)-, -S(=O) ₂ -, -C(=O)-NR ^b -or- S(=O) ₂ -NR ^b -;

R2 and ^R3 are each independently ^hydrogen , fluorine, chlorine, bromine, iodine, hydroxy, cyano, nitro, amino, carboxyl, alkyl, alkenyl or alkynyl;

or -CR ² R ³ - is -C(=O)-;

n is 0, 1 or 2;

^R4 is hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, heterocyclyl, aryl, arylalkyl, cycloalkylalkyl or heterocyclylalkyl;

R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ are each independently hydrogen, fluorine, chlorine, bromine, iodine, hydroxy, cyano, nitro, amino, carboxyl, alkyl, alkenyl, alkynyl, haloalkane Alkyl, haloalkenyl, haloalkynyl, hydroxy substituted alkyl, amino substituted alkyl, cyano substituted alkyl, alkoxy, haloalkoxy, hydroxy substituted alkoxy, amino substituted alkoxy oxy, cyano-substituted alkoxy, alkylamino, alkylthio or aryloxy;

Each R ^is independently fluorine, chlorine, bromine, iodine, hydroxy, cyano, nitro, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, alkoxy, haloalkoxy radical, -C(=O)-OR ^c or aryloxy;

each R ^is independently hydrogen, alkyl, alkenyl, or alkynyl; and

Each ^Rc is independently hydrogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, cycloalkyl, heterocyclyl, aryl, or heteroaryl.

In some of these embodiments, R ¹ is hydrogen, C _1-6 alkyl, C _2-6 alkenyl, C _2-6 alkynyl, C _1-6 alkoxy, C _2-6 alkenyloxy, C _{2 -6} alkynyloxy, C _6-10 aryl, C _6-10 aryl, C _1-6 alkyl, C _1-9 heteroaryl, C _1-9 heteroaryl, C _1-6 alkyl, C _{3 -8} cycloalkyl, C _3-8 cycloalkyl C _1-6 alkyl, C _2-10 heterocyclyl or C _2-10 heterocyclyl C _1-6 alkyl; R ¹ is optionally 2, 3, 4 or 5 substituents selected from R ^a ;

X is a bond, -O-, -C(=O)-, -S-, -S(=O)-, -S(=O) ₂ -, -C(=O)-NR ^b -or- S(=O) ₂ -NR ^b -;

R ² and R ³ are each independently hydrogen, fluorine, chlorine, bromine, iodine, hydroxy, cyano, nitro, amino, carboxyl, C _1-6 alkyl, C _2-6 alkenyl, or C _2-6 alkyne base;

or -CR ² R ³ - is -C(=O)-;

n is 0, 1 or 2;

R ⁴ is hydrogen, C _1-6 alkyl, C _2-6 alkenyl, C _2-6 alkynyl, C _3-8 cycloalkyl, C _2-10 heterocyclyl, C _6-10 aryl, C _6-10 aryl C _1-6 alkyl, C _3-8 cycloalkyl C _1-6 alkyl or C _2-10 heterocyclyl C _1-6 alkyl;

R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ are each independently hydrogen, fluorine, chlorine, bromine, iodine, hydroxy, cyano, nitro, amino, carboxyl, C _1-6 alkyl, C _{2- 6} alkenyl, C _2-6 alkynyl, halogenated C _1-6 alkyl, halogenated C _2-6 alkenyl, halogenated C _2-6 alkynyl, hydroxy substituted C _1-6 alkyl, amino substituted C _1-6 alkyl, cyano substituted C _1-6 alkyl, C _1-6 alkoxy, halogenated 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 _1-6 alkylthio or C _6-10 aryloxy;

Each R is independently fluoro, chloro, bromo, iodo, hydroxy, cyano, nitro, C _1-6 alkyl, C _2-6 alkenyl, C _2-6 alkynyl, ^haloC _1-6 alkane group, halogenated C _2-6 alkenyl, halogenated C _2-6 alkynyl, C _1-6 alkoxy, halogenated C _1-6 alkoxy, -C(=O)-OR ^c or C _{6 -10} aryloxy;

each R ^b is independently hydrogen, C _1-6 alkyl, C _2-6 alkenyl, or C _2-6 alkynyl; and

Each R ^c is independently hydrogen, C _1-6 alkyl, C _2-6 alkenyl, C _2-6 alkynyl, haloC _1-6 alkyl, halo C _2-6 alkenyl, halo C _2-6 alkynyl, C _3-8 cycloalkyl, C _2-6 heterocyclyl, C _6-10 aryl or C _1-5 heteroaryl.

In other embodiments, R ² and R ³ are each independently hydrogen, fluorine, chlorine, bromine, iodine, hydroxy, cyano, nitro, amino, carboxyl, C _1-4 alkyl, C _2-4 alkenyl or C _2-4 alkynyl;

Or -CR ² R ³ - is -C(=O)-.

In other embodiments, R ⁴ is hydrogen, C _1-4 alkyl, C _2-4 alkenyl, C _2-4 alkynyl, C _3-6 cycloalkyl, C _2-6 heterocyclyl, C _{6 -10} aryl, C _6-10 aryl C _1-4 alkyl, C _3-6 cycloalkyl C _1-3 alkyl or C _2-6 heterocyclyl C _1-3 alkyl.

^In other embodiments, R4 is hydrogen, methyl, ethyl, n-propyl, isopropyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, phenyl, or benzyl.

In other embodiments, R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ are each independently hydrogen, fluoro, chloro, bromo, iodo, hydroxy, cyano, nitro, amino, carboxyl, C _1-4 Alkyl, C _2-4 alkenyl, C _2-4 alkynyl, halo C _1-4 alkyl, halo C _2-4 alkenyl, halo C _2-4 alkynyl, hydroxy substituted C _{1- 4} alkyl, amino substituted C _1-4 alkyl, cyano substituted C _1-4 alkyl, C _1-4 alkoxy, halogenated 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 _1-4 alkylthio or phenoxy.

In other embodiments, R ¹ is hydrogen, C _1-4 alkyl, C _2-4 alkenyl, C _2-4 alkynyl, C _1-4 alkoxy, C _2-4 alkenyloxy, C _{2 -4} alkynyloxy, C _6-10 aryl, C _6-10 aryl, C _1-3 alkyl, C _1-5 heteroaryl, C _1-5 heteroaryl, C _1-3 alkyl, C _{3 -6} cycloalkyl, C _3-6 cycloalkyl C _1-3 alkyl, C _2-6 heterocyclyl or C _2-6 heterocyclyl C _1-3 alkyl; R ¹ is optionally replaced by 1, 2, 3, 4 or 5 substituents selected from ^Ra ; and

Each R is independently fluoro, chloro, bromo, iodo, hydroxy, cyano, nitro, C _1-4 alkyl, C _2-4 alkenyl, C _2-4 alkynyl, ^haloC _1-4 alkane group, halogenated C _2-4 alkenyl, halogenated C _2-4 alkynyl, C _1-4 alkoxy, halogenated C _1-4 alkoxy, -C(=O)-OC _1-3 alkoxy or C _6-10 aryloxy.

^In other embodiments, R1 is hydrogen, methyl, ethyl, n-propyl, isopropyl, vinyl, allyl, propenyl, methoxy, ethoxy, n-propoxy, isopropyl oxy, phenyl, benzyl or pyridyl;

R1 is optionally substituted with ¹ , 2, 3, 4 or 5 substituents selected from ^Ra ; and

Each R is independently hydrogen, fluorine, chlorine, bromine, iodine, hydroxy, cyano, nitro, methyl, ethyl, ⁿ -propyl, isopropyl, phenoxy, methoxy, ethoxy, n-propoxy, isopropoxy or -C(=O) _-OCH3 .

In some of these embodiments, the present invention provides a compound, which is a compound of formula (II) or a stereoisomer, nitrogen oxide and salt of a compound of formula (II):

Wherein: R ¹ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ have the meanings as described in the present invention.

In other embodiments, the present invention provides a compound represented by formula (II), a stereoisomer of a compound represented by formula (II), nitrogen oxides and salts thereof, wherein R ¹ is C _1-4 alkyl or C _6-10 aryl C _1-3 alkyl; further preferably, R ¹ is methyl, ethyl, isopropyl or benzyl;

R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ are each independently hydrogen, fluorine, chlorine, bromine, iodine, hydroxy, cyano, nitro, amino, carboxy, methyl or methoxy.

In some of these embodiments, the present invention provides a compound, which is a compound represented by formula (III) or a stereoisomer, nitrogen oxide and salt of a compound represented by formula (III):

in:

X, R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ have the meanings as described in the present invention;

Y is N or CR ^a5 ;

R ^a1 , R ^a2 , R ^a3 , R ^a4 and R ^a5 have the meanings as described for R ^a in the present invention.

In other embodiments, the present invention provides compounds of formula (III), stereoisomers of compounds of formula (III), nitrogen oxides and salts thereof, wherein R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ are each independently hydrogen, fluorine, chlorine, bromine, iodine, hydroxy, cyano, nitro, amino, carboxy, methyl or methoxy;

X is a bond or -C(=O)-;

R ^a1 , R ^a2 , R ^a3 , R ^a4 and R ^a5 are each independently hydrogen, fluorine, chlorine, bromine, iodine, hydroxy, cyano, nitro, methyl, ethyl, n-propyl, isopropyl, Phenoxy, methoxy, ethoxy, n-propoxy, isopropoxy or -C(=O) _-OCH3 .

In some of these embodiments, the present invention provides a compound, which is a compound having one of the following structures or a stereoisomer, nitrogen oxide and salt of a compound having one of the following structures:

In another aspect, the present invention provides a composition comprising the compound of the present invention. Unless otherwise indicated, all tautomers, racemates, hydrates, solvates, metabolites, metabolic precursors and Prodrugs are also within the scope of the present invention.

In some embodiments, the composition further comprises a pesticide acceptable surfactant and/or carrier.

On the other hand, the present invention provides the use of the compound of the present invention or the composition of the present invention in the control of plant diseases, especially the use as a fungicide.

In some of these embodiments, the plant disease is caused by a phytopathogenic fungus.

The compounds represented by formula (I) may exist in different stereoisomers or optical isomers or tautomeric forms. The present invention includes all such isomers and tautomers and mixtures thereof in various ratios, as well as isotopic forms such as deuterium containing compounds.

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

Any asymmetric atom (eg, carbon, etc.) of the compounds disclosed herein may exist in racemic or enantiomerically enriched forms, such as (R)-, (S)- or (R,S)-configurations exist.

The foregoing merely outlines certain aspects of the present invention, but is not limited to these and other aspects, which will be described in greater detail below.

Detailed Description of the Invention

Definitions and General Terms

Certain embodiments of the invention will now be described in detail, examples of which are illustrated by the accompanying structural and chemical formulae. The present invention is intended to cover all alternatives, modifications and equivalents, which are included within the scope of the present invention as defined by the claims. One skilled in the art will recognize that many methods and materials similar or equivalent to those described herein could 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 literature, patents, and similar materials differs from or contradicts this application (including, but not limited to, terms defined, uses of terms, techniques described, etc.), this Application shall prevail.

It should further be appreciated that certain features of the invention, which are, for clarity, described in the context of multiple separate embodiments, can 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, can also be provided separately or in any suitable subcombination.

Unless otherwise defined, 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.

Unless otherwise stated, the following definitions used herein shall apply. For the purposes of the present invention, chemical elements are in accordance with the Periodic Table of the Elements, CAS Edition, and Handbook of Chemistry and Physics, 75th Edition, 1994. In addition, general principles of organic chemistry may be referred to as described in "Organic Chemistry", Thomas Sorrell, University Science Books, Sausalito: 1999, and "March's Advanced Organic Chemistry" by Michael B. Smith and Jerry March, John Wiley & Sons, New York: 2007, Its entire contents are incorporated herein by reference.

As used herein, the articles "a", "an" and "the" are intended to include "at least one" or "one or more" unless stated otherwise or otherwise clearly contradicted by context. Thus, as used herein, these articles refer to articles of one or more than one (ie, at least one) object. For example, "a component" refers to one or more components, ie, there may be more than one component contemplated for use or use in the implementation of the described embodiments.

The term "comprising" is an open-ended expression, that is, it includes the contents specified in the present invention, but does not exclude other aspects.

"Stereoisomers" refer to compounds that have the same chemical structure, but differ in the arrangement of atoms or groups in space. Stereoisomers include enantiomers, diastereomers, conformational isomers (rotamers), geometric isomers (cis/trans), atropisomers, etc. .

"Enantiomer" refers to two nonsuperimposable, but mirror-image isomers of a compound.

"Diastereomer" refers to a stereoisomer that has two or more chiral neutralities 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. Diastereomeric mixtures can be separated by high resolution analytical procedures such as electrophoresis and chromatography, eg HPLC.

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", described in John Wiley & Sons, Inc., New York, 1994.

Many organic compounds exist in optically active forms, that is, 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 the molecule about one or more of its chiral centers. The prefixes d and 11 or (+) and (-) are symbols used to designate the rotation of plane polarized light by the compound, where (-) or 1 indicates that the compound is levorotatory. Compounds prefixed with (+) or d are dextrorotatory. A specific stereoisomer is an enantiomer, and a mixture of such isomers is called an enantiomeric mixture. A 50:50 mixture of enantiomers is called a racemic mixture or racemate, which can occur when there is no stereoselectivity or stereospecificity in a chemical reaction or process.

Any asymmetric atom (eg, carbon, etc.) of the compounds disclosed herein may exist in racemic or enantiomerically enriched forms, such as (R)-, (S)- or (R,S)-configurations exist. In certain embodiments, each asymmetric atom has at least 50% enantiomeric excess, at least 60% enantiomeric excess, at least 70% enantiomeric excess, at least 70% enantiomeric excess in the (R)- or (S)-configuration 80% enantiomeric excess, at least 90% enantiomeric excess, at least 95% enantiomeric excess, or at least 99% enantiomeric excess.

Depending on the choice of starting materials and process, the compounds of the present invention may be present as one of the possible isomers or as mixtures thereof, such as racemates and mixtures of diastereomers (depending on the number of asymmetric carbon atoms) form exists. Optically active (R)- or (S)-isomers can be prepared using chiral synthons or chiral reagents, or resolved using conventional techniques. If the compound contains a double bond, the substituent may be in the E or Z configuration; if the compound contains a disubstituted cycloalkyl, the cycloalkyl substituent may have the cis or trans configuration.

The resulting mixtures of any stereoisomers may be separated into pure or substantially pure geometric isomers, enantiomers, diastereomers on the basis of differences in the physicochemical properties of the components, for example, by chromatography and/or fractional crystallization.

Any resulting racemate of the final product or intermediate can be resolved into the optical enantiomers by known methods by methods familiar to those skilled in the art, eg, by performing diastereomeric salts thereof obtained. separation. Racemic products can also be separated by chiral chromatography, eg, high performance liquid chromatography (HPLC) using chiral adsorbents. In particular, enantiomers can be prepared by asymmetric synthesis.

As described herein, the compounds of the present invention may be optionally substituted with one or more substituents, such as the compounds of the general formula above, or as in the Examples, subclasses, and subclasses encompassed by the present invention. a class of compounds. It is to be understood that the term "optionally substituted" is used interchangeably with the term "substituted or unsubstituted". In general, the term "substituted" means that one or more hydrogen atoms in a given structure have been replaced with a specified 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 can be substituted identically or differently at each position. Specifically, instances of "one or more" refer to 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10. The substituents mentioned therein can be, but are not limited to, deuterium, fluorine, chlorine, bromine, iodine, cyano, hydroxyl, nitro, amino, carboxyl, alkyl, alkoxy, alkoxyalkyl, alkane Oxyalkoxy, alkoxyalkylamino, aryloxy, heteroaryloxy, heterocyclyloxy, arylalkoxy, heteroarylalkoxy, heterocyclylalkoxy, cycloalkane Alkoxy, alkylamino, alkylaminoalkyl, alkylaminoalkylamino, cycloalkylamino, cycloalkylalkylamino, alkylthio, haloalkyl, haloalkoxy, hydroxy-substituted alkyl, hydroxy-substituted alkane Amino, cyano-substituted alkyl, cyano-substituted alkoxy, cyano-substituted alkylamino, amino-substituted alkyl, alkylacyl, heteroalkyl, cycloalkyl, cycloalkenyl, cycloalkylalkane radical, heterocyclyl, heterocyclylalkyl, heterocyclylacyl, aryl, arylalkyl, arylamino, heteroaryl, heteroarylalkyl, heteroarylamino, amido, sulfonyl, amino Sulfonyl, etc.

In addition, it should be noted that, unless clearly stated otherwise, the description modes "each independently" and "...independently" and "...independently" used in the present invention can be interchanged, and both are interchangeable. It should be understood in a broad sense. It can either mean that in different groups, the specific options expressed between the same symbols do not affect each other, or it can mean that in the same group, the specific options expressed between the same symbols do not affect each other.

In various parts of this specification, the substituents of the compounds disclosed in the present invention are disclosed in terms of group type or scope. Specifically, the present invention includes each and every independent subcombination of each member of these group species and ranges. For example, the term " _{C1 - C6} alkyl" or " _C1-6 alkyl" specifically refers to the independently disclosed methyl, ethyl, C3 alkyl, _C4 alkyl, _C5 alkyl and _C6 alkanes base.

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

Examples of alkyl groups include, but are not limited to, methyl (Me, _-CH3 ), ethyl (Et, -CH2CH3), n _{- propyl} (n _- Pr, _{-CH2CH2CH3 )} ), isopropyl (i-Pr, -CH(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 2CH2CH2CH2CH3), ₂ -pentyl (-CH( _{CH3 ) CH2CH2CH3 )} , _{3 -} pentyl (-CH( _{CH2CH3 ) 2 )} , ₂ -methyl -2-butyl(-C(CH3)2CH2CH3), ₃ -methyl- _{2-butyl(-CH(CH3)CH(CH3)2 ) , 3 - methyl} -1- Butyl ( _-CH2CH2CH ( _CH3 ) ₂ ), ₂ -methyl- ₁ -butyl (-CH2CH( _CH3 ) _{CH2CH3 )} , and the like.

The term "alkenyl" refers to a linear or branched monovalent hydrocarbon group containing 2 to 12 carbon atoms, wherein there is at least one site of unsaturation, i.e., a carbon-carbon sp ² double bond, wherein the alkenyl group A group can be optionally substituted with one or more substituents described herein, including the "cis" and "tans" positions, or the "E" and "Z" positions. In one embodiment, the alkenyl group contains 2-8 carbon atoms; in another embodiment, the alkenyl group contains 2-6 carbon atoms; in yet another embodiment, the alkenyl group contains 2 -4 carbon atoms. Examples of alkenyl groups include, but are not limited to, vinyl (-CH= _CH2 ), allyl (-CH2CH= _CH2 ), propenyl ( _{CH3 -} CH=CH-), oxo butenyl (CH ₃ -C(=O)-CH=CH-) and the like.

The term "alkynyl" denotes a straight or branched chain monovalent hydrocarbon group containing 2 to 12 carbon atoms having at least one carbon-carbon sp triple bond.

The term "alkoxy" means that an alkyl group is attached to the remainder of the molecule through an oxygen atom, wherein the alkyl group has the meaning as described herein. Examples of alkoxy groups include, but are not limited to, methoxy (MeO, -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 ) and the like.

The term "alkylthio" means that an alkyl group is attached to the remainder of the molecule through a sulfur atom, wherein the alkyl group has the meaning as described herein. Examples of alkylthio groups include, but are not limited to, _-SCH3 , _-SCH2CH3 , _-SCH2CH2CH3 , _{-SCH (CH3)2 , 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, the cycloalkyl group contains 3-10 carbon atoms; in another embodiment, the cycloalkyl group contains 3-8 carbon atoms; in yet another embodiment, the cycloalkyl group contains 3-6 carbon atoms carbon atom. The cycloalkyl group is optionally substituted with one or more substituents described herein. Such examples include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl, cyclododecyl Alkyl, etc.

The terms "heterocyclyl" and "heterocycle" are used interchangeably herein, and both refer to a saturated or partially unsaturated monocyclic, bicyclic or tricyclic ring containing 3 to 15 ring atoms, wherein a monocyclic, bicyclic or tricyclic ring The ring contains no aromatic rings and at least one ring atom is selected from nitrogen, sulfur and oxygen atoms. Unless otherwise specified, heterocyclyl can be carbon or nitrogen, and _-CH2- groups can be optionally replaced by -C(=O)-. Ring sulfur atoms can optionally be oxidized to S-oxides. The nitrogen atoms of the rings can be optionally oxidized to N-oxygen compounds. Examples of heterocyclyl groups include, but are not limited to, oxiranyl, azetidinyl, oxetanyl, thietanyl, pyrrolidinyl (eg 2-pyrrolidinyl), 2-pyrrole Linyl, 3-pyrrolinyl, pyrazolidinyl, imidazolinyl, imidazolidinyl, tetrahydrofuranyl, dihydrofuranyl, tetrahydrothienyl, dihydrothienyl, 1,3-dioxocyclopentyl, Dithiocyclopentyl, tetrahydropyranyl, dihydropyranyl, 2H-pyranyl, 4H-pyranyl, tetrahydrothiopyranyl, piperidinyl (2-piperidinyl, 3-piperidine base, 4-piperidinyl), morpholinyl, thiomorpholinyl, (1-oxo)-thiomorpholinyl, (1,1-dioxo)-thiomorpholinyl, piperazine base, dioxanyl, dithianyl, thioxanyl, homopiperazinyl, homopiperidinyl, oxepanyl, thiepanyl, 2-oxa-5-aza Bicyclo[2.2.1]hept-5-yl, tetrahydropyridyl. Examples of heterocyclyl groups where the _-CH2- group is substituted with -C(=O)- include, but are not limited to, 2-oxopyrrolidinyl, oxo-1,3-thiazolidinyl, 2-piperidine Keto, 3,5-dioxopiperidinyl. Examples of oxidized sulfur atoms in a heterocyclyl group include, but are not limited to, sulfolanyl, 1,1-dioxothiomorpholinyl. The heterocyclyl group is optionally substituted with one or more substituents described herein.

The term "unsaturated" as used herein means that the group contains one or more degrees of unsaturation.

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

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

The term "aryl" refers to monocyclic, bicyclic and tricyclic carbocyclic ring systems containing 6-14 ring atoms, or 6-12 ring atoms, or 6-10 ring atoms, wherein at least one ring system is aromatic A family of rings in which each ring system contains a ring of 3-7 atoms with one or more points of attachment to the rest of the molecule. The term "aryl" is 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 an optionally substituted aryl group, as defined herein, attached to an oxygen atom and through the oxygen atom to the remainder of the molecule, wherein the aryl group has meaning as described in the present invention.

The term "arylalkyl" or "aralkyl" means that an alkyl group is substituted with one or more aryl groups, wherein the alkyl and aryl groups have the meanings as described herein; such examples include, But not limited to, phenylmethyl (ie, benzyl), phenethyl and the like.

The term "heteroaryl" refers to monocyclic, bicyclic and tricyclic ring systems containing 5-12 ring atoms, or 5-10 ring atoms, or 5-6 ring atoms, wherein at least one ring system is aromatic, And at least one ring system contains one or more heteroatoms, wherein each ring system contains a ring of 5-7 atoms and has one or more points of attachment to the rest of the molecule. The term "heteroaryl" may be used interchangeably with the terms "heteroaromatic ring" or "heteroaromatic". 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.

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 (such as 3-pyridazinyl), 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, tetrazolyl (such as 5-tetrazolyl), triazolyl (such as 2-triazolyl and 5-triazolyl), 2-thienyl, 3-thienyl, pyrazolyl, iso Thiazolyl, 1,2,3-oxadiazolyl, 1,2,5-oxadiazolyl, 1,2,4-oxadiazolyl, 1,2,3-triazolyl, 1,2, 3-thioadiazolyl, 1,3,4-thiodiazolyl, 1,2,5-thiodiazolyl, pyrazinyl, 1,3,5-triazinyl, pyrimidinone, Pyridonyl; also including, but in no way limited to, the following bicyclic rings: benzimidazolyl, benzofuranyl, benzotetrahydrofuranyl, benzothienyl, indolyl (eg 2-indolyl), benzene and piperidinyl, etc.

Salts of the compounds described herein include those derived from alkali or alkaline earth metals and those derived from ammonia and amines. Preferred cations include sodium, potassium, magnesium, and ammonium cations of formula N ⁺ (R ¹⁹ R ²⁰ R ²¹ R ²² ), wherein R ¹⁹ , R ²⁰ , R ²¹ and R ²² are independently selected from hydrogen, C ₁ -C ₆ alkyl and C ₁ -C ₆ hydroxyalkyl. Salts of compounds of formula (I) can be prepared by using metal hydroxides such as sodium hydroxide or amines such as ammonia, trimethylamine, diethanolamine, 2-methylthiopropylamine, bisallylamine, 2-butane oxyethylamine, morpholine, cyclododecylamine or benzylamine) are prepared by treatment of compounds of formula (I).

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

Compositions and Formulations of Compounds of the Invention

The compounds of the present invention are generally useful as fungicidal active ingredients in compositions, ie formulations, which typically also include a pesticidally acceptable surfactant and/or carrier.

The above-mentioned surfactant can be various surfactants known in the field of pesticide formulations, and in the present invention, it is preferably one or more of an emulsifying agent, a dispersing agent and a wetting agent.

In addition to the above-mentioned surfactants, other carriers can be various carriers known in the field of pesticide formulations, including various silicates, carbonates, sulfates, oxides, phosphates, plant carriers, synthetic carrier class. Specifically, for example: silica, kaolin, diatomaceous earth, clay, talc, organobentonite, pumice, titanium dioxide, dextrin, cellulose powder, light calcium carbonate, soluble starch, corn starch, sawdust powder, urea, amine Fertilizers, mixtures of urea and amine fertilizers, glucose, maltose, sucrose, anhydrous potassium carbonate, anhydrous sodium carbonate, anhydrous potassium bicarbonate, anhydrous sodium bicarbonate, attapulgite, anhydrous potassium carbonate and anhydrous bicarbonate One or more of a mixture of potassium and a mixture of anhydrous sodium carbonate and anhydrous sodium bicarbonate.

The above-mentioned emulsifier can be various emulsifiers known in the field of pesticide formulations. Specifically, the emulsifier can be calcium dodecylbenzenesulfonate, tristyryl phenol polyoxyethylene ether phosphate, fatty alcohol polyoxyethylene Ethers, alkylphenol polyoxyethylene ethers, alkylphenol polyoxyethylene polyoxypropylene ethers, fatty amines, ethylene oxide adducts of fatty amides, fatty acid polyoxyethylene esters, rosin acid ethylene oxide adducts , polyol fatty acid ester and its ethylene oxide adduct, styryl phenyl polyoxyethylene ether, alkylphenol formaldehyde resin polyoxyethylene ether, hydroxyl terminated polyoxyethylene polyoxypropylene ether, styryl phenol One or more of formaldehyde resin polyoxyethylene polyoxypropylene ether and castor oil polyoxyethylene ether.

The above-mentioned dispersants can be various dispersants known in the field of pesticide formulations. Specifically, the dispersants are acrylic acid homopolymer sodium salt, maleic acid disodium salt, naphthalenesulfonic acid formaldehyde condensate sodium salt, rosin block polymer. Oxyethylene ether polyoxypropylene ether sulfonate, hydroxyl terminated polyoxyethylene polyoxypropylene ether block copolymer, tristyryl phenol polyoxyethylene ether phosphate, fatty alcohol polyoxyethylene ether phosphate and p-hydroxyphenyl One or more of lignosulfonic acid sodium salts.

Above-mentioned wetting agent can be various wetting agents known in the field of pesticide formulations, specifically, this wetting agent can be sodium lauryl sulfate, secondary alkyl sodium sulfate, sodium dodecylbenzenesulfonate, fat One or more of alcohol polyoxyethylene ether, alkylnaphthalene sulfonate, and alkylphenol resin polyoxyethylene ether sulfate.

According to the bactericide composition of the present invention, the bactericide composition may also contain various formulation auxiliaries commonly used in the field of pesticide formulations, specifically, the formulation auxiliaries may be solvents, cosolvents, thickeners, antifreeze One or more of agent, capsule material, protective agent, defoamer, disintegrant, stabilizer, preservative and binder.

The above-mentioned solvent can be various solvents known in the field of pesticide formulations, and specifically, the solvent can be one or more of organic solvents, vegetable oils, mineral oils, mineral oils and water.

Wherein, the organic solvent includes N-methylpyrrolidone, tetrahydrofuran, dimethyl sulfoxide, N,N-dimethyldecanamide, N,N-dimethylformamide, trimethylbenzene, tetramethylbenzene, xylene, One or more of toluene, octane, heptane, methanol, isopropanol, n-butanol, tetrahydrofurfuryl alcohol, tributyl phosphate, 1,4-dioxane and cyclohexanone.

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

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

At the same time, the above-mentioned solvents can also be used as co-solvents.

The above-mentioned antifreezing agent can be various antifreezing agents known in the field of pesticide formulations, and in the present invention, it is preferably one or more of ethylene glycol, propylene glycol, glycerin and urea.

The above-mentioned thickeners can be various thickeners known in the field of pesticide formulations, and specifically, the thickeners can be xanthan gum, polyvinyl alcohol, polypropylene alcohol, polyethylene glycol, silica, diatoms One or more of clay, kaolin, clay, sodium alginate, magnesium aluminum silicate, sodium aluminum silicate, carboxymethyl cellulose, sodium hydroxypropyl cellulose and organobentonite.

The above-mentioned capsule materials can be various capsule materials known in the field of pesticide formulations, and in the present invention, preferably one or more of polyurethane, polyurea and urea-formaldehyde resins.

The above-mentioned protective agent can be various protective agents known in the field of pesticide formulations, and in the present invention, polyvinyl alcohol and/or polyethylene glycol are preferred.

The above-mentioned antifoaming agent can be various antifoaming agents known in the field of pesticide formulations, and in the present invention, it is preferably one or more of organosiloxane, tributyl phosphate and silicone.

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

The above-mentioned preservatives are selected from one or more of benzoic acid, sodium benzoate, 1,2-benzisothiazolin-3-one (BIT for short), cassone and potassium sorbate.

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

The preparation method of the above-mentioned emulsifiable concentrate formulation may, for example, include mixing and stirring each active component, solvent, co-solvent and emulsifier to form a uniform and transparent oil phase, and then the emulsifiable concentrate formulation can be obtained.

The above water emulsion preparation method may include, for example, mixing active ingredients, emulsifiers, cosolvents and solvents to form a homogeneous oil phase; mixing water, thickener, antifreeze, etc. to form a homogeneous water phase. Under high shear, the water phase is added to the oil phase or the oil phase is added to the water phase to form an aqueous emulsion with good dispersibility.

The preparation method of the above-mentioned microemulsion can be, for example, mixing and stirring the active ingredient, the emulsifier and the solvent to form a uniform and transparent oil phase. Under stirring conditions, gradually add water to form a uniform and transparent microemulsion.

The preparation method of the above-mentioned water/oil suspending agent: for example, water or oil can be used as a medium, and auxiliary agents such as active components and surfactants are added into a sand grinding kettle, and after grinding to a certain particle size, it is filtered. Then add the metered thickener to the ground mother liquor, shear and disperse evenly. Made of oil or water suspension.

The preparation method of the above-mentioned water-dispersible granules and soluble granules: for example, each active component, dispersant, wetting agent, carrier, etc. can be mixed uniformly, then pulverized to a certain particle size by air flow, and then kneaded by adding water, Finally, it is added into a granulator for granulation, and water-dispersible granules or soluble granules can be obtained after drying.

The preparation method of the above-mentioned soluble powder and wettable powder: for example, each active component, various auxiliary agents and other fillers such as carriers can be fully mixed, and pulverized with a superfine pulverizer.

The bactericide composition of the present invention can be provided in the form of a finished preparation, that is, the various substances in the composition have been mixed; it can also be provided in the form of a separate preparation, which can be mixed in a barrel or tank before use, and selected according to the concentration of the desired active substance It can be diluted by mixing with water.

Use of the compounds and compositions of the present invention

The compounds of the present invention are useful as plant disease control agents. Accordingly, the present invention may also include a method for controlling plant diseases caused by phytopathogenic fungi, said method comprising applying to the plant to be protected or a part thereof or to the seed of the plant to be protected an effective amount of a compound of the invention or comprising said Fungicidal compositions of compounds. The compounds and/or compositions of the present invention can provide control of diseases caused by a broad spectrum of phytopathogenic fungi of the Basidiomycetes, Ascomycetes, Oomycetes and Deuteromycetes. They are effective in controlling a broad spectrum of plant diseases, especially foliar pathogens of ornamental crops, turf crops, vegetable crops, field crops, cereal crops and fruit tree crops. These pathogens include: Oomycetes, including Phytophthora diseases such as Phytophthora infestans, Phytophthora megasperma, Phytophthora parasitica, Phytophthora cinnamomi) and Phytophthora capsici, diseases of Pythium species such as Pythium aphanidermatum, and diseases of Peronosporaceae species such as downy mildew of grapes Plasmopara viticola, Peronospora spp. (including Peronospora tabacina and Peronospora parasitica), Pseudoperonospora spp. (including cucumber downy mildew) (Pseudoperonospora cubensis) and Bremia lactucae); Ascomycetes (including Alternaria pathogens such as Alternaria solani and Alternaria brassicae, Cocci (Guignardia) diseases such as Guignardiabidwell, Venturia diseases such as apple scab (Venturia inaequalis), Septoria diseases such as Septoria nodorum and leaf blight Bacteria (Septoria tritici), powdery mildew diseases such as Erysiphe spp. (including Erysiphegraminis and Erysiphe polygoni), grape powdery mildew (Uncinula necatur), cucumber powdery mildew Sphaerotheca fuligena and Podosphaera leucotricha, Pseudocercosporella herpotrichoides, Botrytis such as Botrytis cinerea, Monilinia fr ucticola), Sclerotinia diseases such as Sclerotinia sclerotiorum, Magnaporthe grisea, Phomopsis viticola, Helminthosporium diseases such as corn spot Bacteria (Helminthosporium tritici repentis), Pyrenophora teres, anthracnose fungi such as Glomerella or Colletotrichum spp. diseases (such as Colletotrichum graminicola and Colletotrichum orbiculare )), and Gaeumannomyces graminis; Basidiomycetes, including rust diseases caused by Puccinia spp. (eg Puccinia recondita, Puccinia striiformis, Puccinia hordei, Puccinia graminis, and Puccinia arachidis), Hemileia vastatrix, and Phakopsora pachyrhizi; other pathogens include Rhizoctonia species ( Rhizoctonia spp.) (eg Rhizoctonia solani); Fusarium species diseases such as Fusarium roseum, Fusariumgraminearum and Fusarium oxysporum ; Verticillium dahliae; Sclerotium rolfsii; Rynchosporium secalis; Cercosporidium personatum, Cercospora arachidicola and Cercospora beticola; and other classes and species closely related to these pathogens. In addition to their fungicidal activity, the compositions or combinations are effective against bacteria such as Erwinia amylovora, Xanthomonas campestris, Pseudomonas syringae and others Bacteria have resistance activity.

The application method of the fungicide composition of the present invention is simple. Before or after the germination of plant diseases, it is applied to crops and places where crops grow according to conventional methods, such as soil mixing, spraying, spraying, pouring, etc., and the application amount is based on climatic conditions. Or depending on the state of the crop, generally apply 10-5000g per mu, diluted to 10-400mg/L (preferably 100-300mg/L) for application. The diluent is preferably water.

The bactericidal effect of the bactericidal composition of the present invention is usually related to external factors such as weather, but the effect of weather can be mitigated by using an appropriate dosage form.

The compositions of the present invention can also be used in admixture with other compounds having fungicidal, insecticidal or herbicidal properties, as well as with nematicides, acaricides, repellants, herbicide safeners, growth regulators, phytonutrients or soil conditioners etc. mixed use.

General synthetic procedure

The following examples describe the preparation of compounds of the present invention. Unless otherwise stated, the compounds of the present invention can be prepared by the methods described herein. The raw materials, reagents, etc. used to prepare the compounds of the present invention are all commercially available, or can be prepared by conventional methods in the art. In this specification, if there is any difference between chemical name and chemical structure, the structure will prevail.

The following abbreviations are used throughout this disclosure:

g grams; mg milligrams; mol moles; mmol millimoles; h hours; min minutes; L liters; mL, ml milliliters; M mol/L;

PE petroleum ether; EtOAc; ethyl acetate; DMF N,N-dimethylformamide; THF tetrahydrofuran

Example

The synthesis of embodiment A intermediate N-benzyl cyclopropylamine

Cyclopropane (3.42g, 0.06mol), potassium carbonate (20.00g, 0.15mol) and DMF (80mL) were added to a 250mL reaction flask, and stirred at room temperature; then benzyl chloride (5.11g, 0.04mol) was added DMF (20 mL) solution was slowly added dropwise to the reaction (the drop was completed in 1 hour), and the reaction was carried out at 25°C for 48 hours after the dropwise addition; then water (80 mL) was added, extracted with ether (100 mL×3), and then saturated chlorinated The organic phase was washed with aqueous sodium solution (100 mL×2), dried over magnesium sulfate, concentrated, and purified by column chromatography (EtOAc/PE (v/v)=1/4) to obtain 3.06 g of yellow liquid with a yield of 52%.

¹ H-NMR (400MHz, DMSO-d ₆ ): δ(ppm) 7.3～7.2(m, 5H), 3.7(s, 2H), 2.0(m, 1H), 0.3～0.4(m, 4H);

¹³ C NMR (100 MHz, DMSO-d ₆ ): δ (ppm) 141.6, 128.4, 126.8, 53.4, 30.1, 6.6.

LC-MS: (M+1) m/z=148.2.

The intermediate compound in Table 1 can be obtained by the similar synthetic method of Example A, substituting the corresponding starting material for benzyl chloride.

Table 1

Synthesis of Example B Intermediate N-benzyl-N-cyclopropyl-1H-1,2,4-triazole-3-sulfonamide

Add N-cyclopropylbenzylamine (2.94g, 0.02mol), triethylamine (2.02g, 0.02mol) and tetrahydrofuran (30mL) to a 100mL single-neck flask; stir well at 0-5°C in an ice bath, and then A solution of 1H-1,2,4-triazole-3-sulfonyl chloride (3.32 g, 0.02 mol) in THF (15 mL) was slowly added dropwise (dropped within 1 hour), and after 12 hours of reaction, water (20 mL) was added. ) and adjusted the pH to 5 with hydrochloric acid; finally extracted with ether (100 mL×3), combined the organic phases, dried over magnesium sulfate, concentrated, washed with n-hexane to obtain 4.62 g of off-white solid, yield: 83.1%.

¹ H-NMR (400MHz, DMSO-d ₆ ): δ(ppm) 14.9(s, 1H), 8.9(s, 1H), 7.4～7.3(m, 5H), 4.5(s, 2H), 2.4(m ,1H),0.5～0.6(m,4H);

¹³ C NMR (100 MHz, DMSO-d ₆ ): δ (ppm) 161.4, 146.3, 137.1, 128.7, 128.4, 127.7, 54.2, 31.1, 7.2.

LC-MS: (M+1) m/z=279.1.

Through the similar synthetic method of Example B, the corresponding raw materials and conditions, the intermediate compounds in Table 2 can be obtained.

Table 2

Example 1 N,N,1-tribenzyl-1H-1,2,4-triazole-3-sulfonamide

N,N-Dibenzyl-1H-1,2,4-triazole-3-sulfonamide (0.33 g, 1.0 mmol), potassium carbonate (0.28 g, 2.0 mmol) and DMF (10 mL) were added to 100 mL In the three-necked flask, benzyl chloride (0.19g, 1.5mmol) was slowly added to the reaction system, and the reaction was carried out at room temperature at 25°C for 8 hours; water (20mL) was added to quench, extracted with ethyl acetate (15mL×3), and the organic phase was quenched with ethyl acetate (15mL×3). Washed with saturated brine (10 mL), dried over anhydrous magnesium sulfate, filtered, the filtrate was evaporated under reduced pressure to remove the solvent, and purified by column chromatography (EtOAc/PE (v/v)=1/3) to obtain 0.34 g of white solid , yield: 81.6%.

¹ H NMR (400 MHz, CDCl ₃ ): δ (ppm) 8.12 (s, 1H), 7.39-7.30 (m, 6H), 7.23-7.19 (m, 9H), 5.49 (s, 2H), 4.51 (s, 4H).

LC-MS: (M+1) m/z=419.0.

Example 2 N-benzyl-N-cyclopropyl-1-(4-fluorobenzyl)-1H-1,2,4-triazole-3-sulfonamide

Combine N-benzyl-N-cyclopropyl-1H-1,2,4-triazole-3-sulfonamide (0.28 g, 1.0 mmol), potassium carbonate (0.28 g, 2.0 mmol) and DMF (10 mL) It was added into a 100mL three-necked flask, and then 4-fluorobenzyl bromide (0.28g, 1.5mmol) was slowly added to the reaction system, and the reaction was carried out at room temperature at 25°C for 8 hours; water (20mL) was added to quench, and ethyl acetate was used for extraction (15mL× 3), the organic phase was washed with saturated brine (10 mL), dried over anhydrous magnesium sulfate, filtered, the filtrate was removed by rotary evaporator under reduced pressure, and purified by column chromatography (EtOAc/PE (v/v)=1/3) , to obtain 0.32 g of white solid, yield: 82.0%.

¹ H NMR (400MHz, CDCl ₃ ): δ(ppm) 8.08(s, 1H), 7.38-7.27(m, 7H), 7.14-7.10(m, 2H), 5.38(s, 2H), 4.55(s, 2H), 2.53-2.47(m, 1H), 0.82-0.78(m, 2H), 0.69-0.64(m, 2H).

LC-MS: (M+1) m/z=387.9.

Example 3 N-cyclopropyl-N,1-bis(2-nitrobenzyl)-1H-1,2,4-triazole-3-sulfonamide

N-cyclopropyl-N-(2-nitrobenzyl)-1H-1,2,4-triazole-3-sulfonamide (0.32g, 1.0mmol), potassium carbonate (0.28g, 2.0mmol) ) and DMF (10mL) were added in a 100mL there-necked flask, then 2-nitrobenzyl chloride (0.28g, 1.5mmol) was slowly added to the reaction system, and the reaction was carried out at room temperature at 25°C for 8 hours; Ethyl acetate extraction (15 mL×3), the organic phase was washed with saturated brine (10 mL), dried over anhydrous magnesium sulfate, filtered, the filtrate was removed by rotary evaporator under reduced pressure, and purified by column chromatography (EtOAc/PE (v/ v)=1/3), 0.35 g of white solid was obtained, yield: 76.6%.

¹ H NMR (400 MHz, DMSO-d ₆ ): δ(ppm) 8.18(s, 1H), 7.41-7.19(m, 8H), 5.41(s, 2H), 4.62(s, 2H), 2.55-2.49 (m,1H),0.83-0.79(m,2H),0.69-0.65(m,2H).

LC-MS: (M+1) m/z=459.1.

Example 4 Methyl 3-(N-benzyl-N-cyclopropylaminosulfonyl)-1H-1,2,4-triazole-1-carboxylate

Combine N-benzyl-N-cyclopropyl-1H-1,2,4-triazole-3-sulfonamide (0.28 g, 1.0 mmol), potassium carbonate (0.28 g, 2.0 mmol) and DMF (10 mL) It was added into a 100mL three-necked flask, and then methyl chloroformate (0.14g, 1.5mmol) was slowly added to the reaction system, and the reaction was performed at room temperature at 25°C for 8 hours; water (20mL) was added to quench, and ethyl acetate was used for extraction (15mL×3 ), the organic phase was washed with saturated brine, dried over anhydrous magnesium sulfate, filtered, and the filtrate was evaporated under reduced pressure to remove the solvent, and purified by column chromatography (EtOAc/PE (v/v)=1/3) to obtain a white solid 0.24g, yield: 71.0%.

¹ H NMR (400MHz, CDCl ₃ ): δ(ppm) 8.16(s, 1H), 7.36-7.35(m, 2H), 7.30-7.25(m, 3H), 4.52(s, 2H), 3.98(s, 3H), 2.52-2.46(m, 1H), 0.79-0.75(m, 2H), 0.67-0.62(m, 2H).

LC-MS: (M+1) m/z=337.3.

Example 5 Benzyl 3-(N-benzyl-N-cyclopropylaminosulfonyl)-1H-1,2,4-triazole-1-carboxylate

Combine N-benzyl-N-cyclopropyl-1H-1,2,4-triazole-3-sulfonamide (0.28 g, 1.0 mmol), potassium carbonate (0.28 g, 2.0 mmol) and DMF (10 mL) It was added into a 100mL three-necked flask, and then benzyl chloroformate (0.26g, 1.5mmol) was slowly added to the reaction system, and the reaction was carried out at room temperature at 25°C for 8 hours; quenched by adding water (20mL), and extracted with ethyl acetate (15mL×3 ), the organic phase was washed with saturated brine, dried over anhydrous magnesium sulfate, filtered, the filtrate was removed by rotary evaporator under reduced pressure, and the filtrate was purified by column chromatography (EtOAc/PE (v/v)=1/3) to obtain a white solid 0.29 g, yield: 70.1%.

¹ H NMR (400 MHz, CDCl ₃ ): δ (ppm) 8.06 (s, 1H), 7.44-7.42 (m, 3H), 7.38-7.32 (m, 4H), 7.29-7.27 (m, 3H), 5.41 ( s,2H),4.55(s,2H),2.53-2.48(m,1H),0.82-0.78(m,2H),0.69-0.64(m,2H).

LC-MS: (M+1) m/z=413.2.

Example 6 N-benzyl-N-cyclopropyl-1-(2-oxo-2-phenylethyl)-1H-1,2,4-triazole-3-sulfonamide

Combine N-benzyl-N-cyclopropyl-1H-1,2,4-triazole-3-sulfonamide (0.28 g, 1.0 mmol), potassium carbonate (0.28 g, 2.0 mmol) and DMF (10 mL) was added to a 100mL three-necked flask, then α-bromoacetophenone (0.30g, 1.5mmol) was slowly added to the reaction system, and the reaction was performed at room temperature at 25°C for 8 hours; water (20mL) was added to quench, and ethyl acetate was used for extraction ( 15mL×3), the organic phase was washed with saturated brine, dried over anhydrous magnesium sulfate, filtered, the filtrate was removed by rotary evaporator under reduced pressure, and purified by column chromatography (EtOAc/PE (v/v)=1/3), 0.31 g of white solid was obtained, yield: 78.0%.

¹ H NMR (400MHz, DMSO-d ₆ ): δ (ppm) 8.81 (s, 1H), 8.09-8.07 (m, 2H), 7.77-7.73 (m, 1H), 7.64-7.60 (m, 2H), 7.36-7.28(m, 5H), 6.18(s, 2H), 4.48(s, 2H), 2.48-2.44(m, 1H), 0.67-0.57(m, 4H).

LC-MS: (M+1) m/z=397.5.

Example 7 N-benzyl-N-cyclopropyl-1-(4-methylbenzyl)-1H-1,2,4-triazole-3-sulfonamide

Combine N-benzyl-N-cyclopropyl-1H-1,2,4-triazole-3-sulfonamide (0.28 g, 1.0 mmol), potassium carbonate (0.28 g, 2.0 mmol) and DMF (10 mL) It was added into a 100mL there-necked flask, and then 1-(bromomethyl)-4-methylbenzene (0.28g, 1.5mmol) was slowly added to the reaction system, and the reaction was carried out at room temperature at 25°C for 8 hours; water (20mL) was added to quench, Extracted with ethyl acetate (15 mL×3), the organic phase was washed with saturated brine, dried over anhydrous magnesium sulfate, filtered, the filtrate was removed by rotary evaporator under reduced pressure, and purified by column chromatography (EtOAc/PE (v/v) =1/3) to obtain 0.33 g of a white solid, yield: 84.0%.

¹ H NMR (400MHz, CDCl ₃ ): δ (ppm) 8.07 (s, 1H), 7.36-7.34 (m, 2H), 7.28-7.25 (m, 3H), 7.23-7.18 (m, 4H), 5.34 ( s,2H),4.53(s,2H),2.51-2.46(m,1H),2.36(s,3H),0.79-0.75(m,2H),0.66-0.62(m,2H).

LC-MS: (M+1) m/z=383.8.

Example 8 N-benzyl-N-cyclopropyl-1-methyl-1H-1,2,4-triazole-3-sulfonamide

Combine N-benzyl-N-cyclopropyl-1H-1,2,4-triazole-3-sulfonamide (0.28 g, 1.0 mmol), potassium carbonate (0.28 g, 2.0 mmol) and DMF (10 mL) It was added into a 100mL three-necked flask, and then methyl iodide (0.21g, 1.5mmol) was slowly added to the reaction system, and the reaction was carried out at room temperature at 25°C for 8 hours; water (20mL) was added to quench, and ethyl acetate was used for extraction (15mL×3), The organic phase was washed with saturated brine, dried over anhydrous magnesium sulfate, filtered, and the filtrate was evaporated under reduced pressure to remove the solvent, and purified by column chromatography (EtOAc/PE (v/v)=1/3) to obtain 0.22 g of a white solid , yield: 76.0%.

¹ H NMR (400 MHz, CDCl ₃ ): δ (ppm) 8.13 (s, 1H), 7.40-7.38 (m, 2H), 7.33-7.28 (m, 3H), 4.56 (s, 2H), 4.02 (s, 3H), 2.55-2.49(m, 1H), 1.26(d, J=6.9Hz, 6H), 0.83-0.79(m, 2H), 0.70-0.65(m, 2H).

LC-MS: (M+1) m/z=293.9.

Example 9 1-allyl-N-benzyl-N-cyclopropyl-1H-1,2,4-triazole-3-sulfonamide

Combine N-benzyl-N-cyclopropyl-1H-1,2,4-triazole-3-sulfonamide (0.28 g, 1.0 mmol), potassium carbonate (0.28 g, 2.0 _mmol ) and DMF (10 mL) ) was added into a 100mL there-necked flask, then 3-bromopropene (0.18g, 1.5mmol) was slowly added to the reaction system, and the reaction was performed at room temperature at 25°C for 8 hours; water (20mL) was added to quench, and ethyl acetate was used for extraction (15mL× 3), the organic phase was washed with saturated brine, dried over anhydrous magnesium sulfate, filtered, the filtrate was removed from the solvent under reduced pressure with a rotary evaporator, and purified by column chromatography (EtOAc/PE (v/v)=1/3) to obtain a white Solid 0.25g, yield: 79.0%.

¹ H NMR (400 MHz, CDCl ₃ ): δ (ppm) 8.18 (s, 1H), 7.37-7.36 (m, 2H), 7.31-7.25 (m, 3H), 6.07-5.97 (m, 1H), 5.41 ( d, J＝10.1Hz, 1H), 5.35(d, J＝17.0Hz, 1H), 4.85(d, J＝6.2Hz, 2H), 4.54(s, 2H), 2.52-2.47(m, 1H), 0.80-0.76(m,2H),0.68-0.63(m,2H).

LC-MS: (M+1) m/z=319.8.

Example 10 N-benzyl-N-cyclopropyl-1-(4-isopropylbenzyl)-1H-1,2,4-triazole-3-sulfonamide

Combine N-benzyl-N-cyclopropyl-1H-1,2,4-triazole-3-sulfonamide (0.28 g, 1.0 mmol), potassium carbonate (0.28 g, 2.0 mmol) and DMF (10 mL) was added to a 100mL three-necked flask, and then 1-(bromomethyl)-4-isopropylbenzene (0.32g, 1.5mmol) was slowly added to the reaction system, and the reaction was performed at room temperature at 25°C for 8 hours; water (20mL) was added to quench , extracted with ethyl acetate (15 mL×3), the organic phase was washed with saturated brine, dried over anhydrous magnesium sulfate, filtered, the filtrate was removed by rotary evaporator under reduced pressure, and purified by column chromatography (EtOAc/PE (v/v) )=1/3) to obtain 0.32 g of a white solid, yield: 78.0%.

¹ H NMR (400 MHz, CDCl ₃ ): δ (ppm) 8.09 (s, 1H), 7.37-7.34 (m, 2H), 7.28-7.25 (m, 7H), 5.36 (s, 2H), 4.54 (s, 2H), 3.00-2.88(m, 1H), 2.52-2.47(m, 1H), 1.26(d, J=6.9Hz, 6H), 0.81-0.77(m, 2H), 0.67-0.63(m, 2H) .

LC-MS: (M+1) m/z=411.8.

Example 11 N-benzyl-N-cyclopropyl-1-isobutyl-1H-1,2,4-triazole-3-sulfonamide

Combine N-benzyl-N-cyclopropyl-1H-1,2,4-triazole-3-sulfonamide (0.28 g, 1.0 mmol), potassium carbonate (0.28 g, 2.0 mmol) and DMF (10 mL) was added into a 100mL three-necked flask, and then bromoisobutane (0.21g, 1.5mmol) was slowly added to the reaction system, and the reaction was carried out at room temperature at 25°C for 8 hours; water (20mL) was added to quench, and ethyl acetate was used for extraction (15mL× 3), the organic phase was washed with saturated brine, dried over anhydrous magnesium sulfate, filtered, the filtrate was removed from the solvent under reduced pressure with a rotary evaporator, and purified by column chromatography (EtOAc/PE (v/v)=1/3) to obtain a white Solid 0.24 g, yield: 73.0%.

¹ H NMR (400 MHz, CDCl ₃ ): δ (ppm) 8.13 (s, 1H), 7.39-7.37 (m, 2H), 7.33-7.24 (m, 3H), 4.55 (s, 2H), 4.04 (d, J=7.2Hz, 2H), 2.50-2.45(m, 1H), 2.32-2.22(m, 1H), 0.95(d, J=6.7Hz, 6H), 0.80-0.76(m, 2H), 0.68-0.63 (m,2H).

LC-MS: (M+1) m/z=335.0.

Example 12 N-benzyl-N-cyclopropyl-1-isopropyl-1H-1,2,4-triazole-3-sulfonamide

Combine N-benzyl-N-cyclopropyl-1H-1,2,4-triazole-3-sulfonamide (0.28 g, 1.0 mmol), potassium carbonate (0.28 g, 2.0 mmol) and DMF (10 mL) was added to a 100mL three-necked flask, and then 2-iodopropane (0.26g, 1.5mmol) was slowly added to the reaction system, and the reaction was carried out at room temperature at 25°C for 8 hours; water (20mL) was added to quench, and ethyl acetate was used for extraction (15mL× 3), the organic phase was washed with saturated brine, dried over anhydrous magnesium sulfate, filtered, the filtrate was removed from the solvent under reduced pressure with a rotary evaporator, and purified by column chromatography (EtOAc/PE (v/v)=1/3) to obtain a white Solid 0.23 g, yield: 72.0%.

¹ H NMR (400 MHz, CDCl ₃ ): δ (ppm) 8.17 (s, 1H), 7.37-7.35 (m, 2H), 7.31-7.25 (m, 3H), 4.68-4.58 (m, 1H), 4.54 ( s, 2H), 2.53-2.48(m, 1H), 1.58(d, J=6.7Hz, 6H), 0.81-0.77(m, 2H), 0.68-0.63(m, 2H).

LC-MS: (M+1) m/z=321.1.

Example 13 Methyl 2-(3-(N-benzyl-N-cyclopropylaminosulfonyl)-1H-1,2,4-triazol-1-yl)acetate

Combine N-benzyl-N-cyclopropyl-1H-1,2,4-triazole-3-sulfonamide (0.28 g, 1.0 mmol), potassium carbonate (0.28 g, 2.0 mmol) and DMF (10 mL) It was added into a 100mL three-necked flask, and then methyl bromoacetate (0.23g, 1.5mmol) was slowly added to the reaction system, and the reaction was carried out at room temperature at 25°C for 8 hours; water (20mL) was added to quench, and ethyl acetate was used for extraction (15mL×3 ), the organic phase was washed with saturated brine, dried over anhydrous magnesium sulfate, filtered, the filtrate was removed by rotary evaporator under reduced pressure, and the filtrate was purified by column chromatography (EtOAc/PE (v/v)=1/3) to obtain a white solid 0.26g, yield: 74.0%.

¹ H NMR (400MHz, CDCl ₃ ): δ(ppm) 8.36(s, 1H), 7.37-7.27(m, 5H), 5.09(s, 2H), 4.53(s, 2H), 3.80(s, 3H) ,2.49-2.44(m,1H),0.78-0.74(m,2H),0.67-0.62(m,2H).

LC-MS: (M+1) m/z=351.9.

Example 14 N-benzyl-N-cyclopropyl-1-(2-phenoxybenzyl)-1H-1,2,4-triazole-3-sulfonamide

Combine N-benzyl-N-cyclopropyl-1H-1,2,4-triazole-3-sulfonamide (0.28 g, 1.0 mmol), potassium carbonate (0.28 g, 2.0 mmol) and DMF (10 mL) was added to a 100mL there-necked flask, and then 1-(chloromethyl)-2-phenoxybenzene (0.33g, 1.5mmol) was slowly added to the reaction system, and the reaction was carried out at room temperature at 25°C for 8 hours; water (20mL) was added to quench , extracted with ethyl acetate (15 mL×3), the organic phase was washed with saturated brine, dried over anhydrous magnesium sulfate, filtered, the filtrate was removed by rotary evaporator under reduced pressure, and purified by column chromatography (EtOAc/PE (v/v) )=1/3) to obtain 0.31 g of a white solid, yield: 67.0%.

¹ H NMR (400 MHz, CDCl ₃ ): δ (ppm) 8.08 (s, 1H), 7.39-7.36 (m, 5H), 7.31-7.27 (m, 3H), 7.18-7.14 (m, 1H), 7.03- 7.01(m,4H),6.97-6.95(m,1H),5.36(s,2H),4.54(s,2H),2.51-2.45(m,1H),0.81-0.77(m,2H),0.68- 0.63(m,2H).

LC-MS: (M+1) m/z=461.8.

Example 15 N-benzyl-N-cyclopropyl-1-(pyridin-4-ylmethyl)-1H-1,2,4-triazole-3-sulfonamide

Combine N-benzyl-N-cyclopropyl-1H-1,2,4-triazole-3-sulfonamide (0.28 g, 1.0 mmol), potassium carbonate (0.28 g, 2.0 mmol) and DMF (10 mL) It was added into a 100mL three-necked flask, and then 4-(chloromethyl)pyridine (0.19g, 1.5mmol) was slowly added to the reaction system, and the reaction was carried out at room temperature at 25°C for 8 hours; water (20mL) was added to quench, and ethyl acetate was used for extraction. (15mL×3), the organic phase was washed with saturated brine, dried over anhydrous magnesium sulfate, filtered, the filtrate was removed by rotary evaporator under reduced pressure, and purified by column chromatography (EtOAc/PE (v/v)=1/3) , 0.28 g of white solid was obtained, yield: 78.0%.

¹ H NMR (400 MHz, CDCl ₃ ): δ (ppm) 8.66-8.65 (m, 2H), 8.23 (s, 1H), 7.37-7.35 (m, 2H), 7.31-7.28 (m, 3H), 7.15- 7.14(m, 2H), 5.43(s, 2H), 4.55(s, 2H), 2.53-2.47(m, 1H), 0.82-0.78(m, 2H), 0.70-0.65(m, 2H).

LC-MS: (M+1) m/z=370.9.

Example 16 N-benzyl-N-cyclopropyl-1-(4-methoxybenzyl)-1H-1,2,4-triazole-3-sulfonamide

Combine N-benzyl-N-cyclopropyl-1H-1,2,4-triazole-3-sulfonamide (0.28 g, 1.0 mmol), potassium carbonate (0.28 g, 2.0 mmol) and DMF (10 mL) was added to a 100mL there-necked flask, and then 1-(chloromethyl)-4-methoxybenzene (0.23g, 1.5mmol) was slowly added to the reaction system, and the reaction was carried out at room temperature at 25°C for 8 hours; water (20mL) was added to quench , extracted with ethyl acetate (15 mL×3), the organic phase was washed with saturated brine, dried over anhydrous magnesium sulfate, filtered, the filtrate was removed by rotary evaporator under reduced pressure, and purified by column chromatography (EtOAc/PE (v/v) )=1/3) to obtain 0.31 g of a white solid, yield: 78.0%.

¹ H NMR (400MHz, CDCl ₃ ): δ (ppm) 8.03 (s, 1H), 7.38-7.35 (m, 2H), 7.30-7.27 (m, 5H), 6.95-6.93 (m, 2H), 5.33 ( s,2H),4.54(s,2H),3.83(s,3H),2.52-2.47(m,1H),0.81-0.77(m,2H),0.68-0.63(m,2H).

LC-MS: (M+1) m/z=399.8.

Example 17 N-benzyl-N-cyclopropyl-1-(4-nitrobenzyl)-1H-1,2,4-triazole-3-sulfonamide

Combine N-benzyl-N-cyclopropyl-1H-1,2,4-triazole-3-sulfonamide (0.28 g, 1.0 mmol), potassium carbonate (0.28 g, 2.0 mmol) and DMF (10 mL) was added to a 100mL there-necked flask, and then 1-(chloromethyl)-4-nitrobenzene (0.26g, 1.5mmol) was slowly added to the reaction system, and the reaction was carried out at room temperature at 25°C for 8 hours; water (20mL) was added to quench, Extracted with ethyl acetate (15 mL×3), the organic phase was washed with saturated brine, dried over anhydrous magnesium sulfate, filtered, the filtrate was removed by rotary evaporator under reduced pressure, and purified by column chromatography (EtOAc/PE (v/v) =1/3) to obtain 0.30 g of a white solid, yield: 73.0%.

¹ H NMR (400 MHz, CDCl ₃ ): δ (ppm) 8.26-8.24 (s, 3H), 7.46 (d, J=8.6 Hz, 2H) 7.36-7.35 (m, 2H), 7.30-7.28 (m, 3H) ), 5.53(s, 2H), 4.54(s, 2H), 2.52-2.47(m, 1H), 0.82-0.78(m, 2H), 0.70-0.65(m, 2H).

LC-MS: (M+1) m/z=414.8.

Example 18 Methyl 4-((3-(N-benzyl-N-cyclopropylaminosulfonyl)-1H-1,2,4-triazol-1-yl)methyl)benzoic acid ester

Combine N-benzyl-N-cyclopropyl-1H-1,2,4-triazole-3-sulfonamide (0.28 g, 1.0 mmol), potassium carbonate (0.28 g, 2.0 mmol) and DMF (10 mL) It was added into a 100mL there-necked flask, and then methyl 4-(chloromethyl)benzoate (0.28g, 1.5mmol) was slowly added to the reaction system, and the reaction was carried out at room temperature at 25°C for 8 hours; water (20mL) was added to quench, Extracted with ethyl acetate (15 mL×3), the organic phase was washed with saturated brine, dried over anhydrous magnesium sulfate, filtered, the filtrate was removed by rotary evaporator under reduced pressure, and purified by column chromatography (EtOAc/PE (v/v) =1/3) to obtain 0.33 g of a white solid, yield: 77.0%.

¹ H NMR (400 MHz, CDCl ₃ ): δ (ppm) 8.20 (s, 1H), 8.04 (d, J=8.2 Hz, 2H), 7.36-7.33 (m, 4H), 7.28-7.24 (m, 3H) ,5.46(s,2H),4.52(s,2H),3.92(s,3H),2.50-2.45(m,1H),0.79-0.75(m,2H),0.67-0.62(m,2H).

LC-MS: (M+1) m/z=427.5.

Example 19 Methyl 3-(N-(2-bromobenzyl)-N-cyclopropylaminosulfonyl)-1H-1,2,4-triazole-1-carboxylate

N-cyclopropyl-N-(2-bromobenzyl)-1H-1,2,4-triazole-3-sulfonamide (0.36g, 1.0mmol), potassium carbonate (0.28g, 2.0mmol) and DMF (10mL) were added into a 100mL there-necked flask, and then methyl chloroformate (0.14g, 1.5mmol) was slowly added to the reaction system, and the reaction was carried out at room temperature at 25°C for 8 hours; water (20mL) was added to quench, and ethyl acetate was used for quenching. Extraction (15 mL×3), the organic phase was washed with saturated brine, dried over anhydrous magnesium sulfate, filtered, the filtrate was removed by rotary evaporator under reduced pressure, and purified by column chromatography (EtOAc/PE (v/v)=1/3 ) to obtain 0.29 g of a white solid, yield: 70.1%.

¹ H NMR (400 MHz, CDCl ₃ ): δ (ppm) 7.97 (s, 1H), 7.58-7.53 (m, 2H), 7.36 (t, J=7.5Hz, 1H), 7.20-7.16 (m, 1H) ,4.79(s,2H),4.20(s,3H),2.81-2.76(m,1H),0.84-0.80(m,2H),0.72-0.67(m,2H).

LC-MS: (M+1) m/z=415.3.

Biological Examples of the Invention

In the following test examples, the control efficacy of the compounds of the present invention against harmful fungi was examined.

Test Example 1

Test targets: Rhizoctonia solani, Cucumber Botrytis cinerea, cucumber downy mildew, cucumber powdery mildew

Experimental treatment: Compounds were dissolved in DMF to 1% EC for use. The bactericidal activity of these compounds at different doses against the four tested targets was evaluated using the in vivo pot method.

1) Cucumber downy mildew test (Pseudoperonospora cubensis)

Select a potted cucumber seedling with the same growth at the true leaf stage (removing the growth point), dry it naturally after spraying treatment, inoculate 24 hours after treatment, take fresh cucumber downy mildew diseased leaves, and wash them with distilled water with a writing brush The sporangia on the back of the diseased leaves were made into a sporangia suspension (2-3×10 ⁵ /mL). Use an inoculation sprayer (pressure 0.1MPa) to evenly spray and inoculate the cucumber seedlings. After the inoculation, the test material is moved to an artificial climate room, and the relative humidity is kept at 100% and the temperature is about 21°C. After 24 hours, the temperature is kept at about 21°C and the relative humidity About 95% of the disease was induced by moisturizing, and after 5 days, the incidence of the blank control was investigated by grade, and the control effect was calculated according to the disease finger.

2) Cucumber powdery mildew test (Sphaerotheca fuliginea)

Choose a cucumber seedling at the true leaf stage with the same growth, and dry it in the shade for 24 hours after spraying. Wash the fresh powdery mildew spores on the cucumber leaves, filter with double-layer gauze, make a suspension with a spore concentration of about 100,000/mL, and spray and inoculate. After inoculation, the test materials were moved into an artificial climate chamber, the relative humidity was kept between 60 and 70%, and the temperature was kept at 21 to 23 °C. The disease situation of the blank control was investigated in grades for about 10 days, and the control effect was calculated according to the disease finger.

3) Botrytis cinerea

Using leaf inoculation method. Choose two potted cucumber seedlings with the same growth at the true leaf stage. After 24 hours of moisturizing in dark light at 24-26°C, restore natural light and moisturizing for about 3 days. After the control was fully developed, the diameter of each inoculation spot was measured with a caliper, and the control effect was calculated.

4) Rhizoctonia solani

Select potted corn seedlings with two leaves and one heart and the same growth, dry naturally after spraying, inoculate about 24 hours, and inoculate the bacteria cake on the leaves after the spray is dried. After 24 hours of moisturizing in dark light at 25-26°C, restore natural light and moisturizing for about 3 days. After the control was fully developed, the length of each inoculation spot was measured with a caliper, and the control effect was calculated.

Test results: The test results are shown in Tables 3 and 4.

Table 3 The control effect of the compound of the present invention at 200mg/L on cucumber downy mildew

Example Control effect (%) Example 2 80 Example 4 100 Example 5 98 Example 6 90 Example 12 80 Example 19 100

Table 4 Control effect of the compounds of the present invention at 100 mg/L on cucumber downy mildew

Example Control effect (%) Example 4 90 Example 5 80 Example 19 95

The results in Tables 3 and 4 show that the compounds of the present invention have significant control effects on cucumber downy mildew at different concentrations; especially Example 19 also shows good control effects on cucumber downy mildew at low concentrations, The control effect of Example 19 on cucumber downy mildew at 50 mg/L is 80%, and the control effect of Example 19 on cucumber downy mildew at 25 mg/L is 60%.

The preferred embodiments of the present invention are described in detail above, but the present invention is not limited to the specific details of the above-mentioned embodiments. Within the scope of the technical concept of the present invention, various simple modifications can be made to the technical solutions of the present invention. These simple modifications All belong to the protection scope of the present invention.

Claims (6)

1. A compound, which is a compound represented by formula (I) or a salt of a compound represented by formula (I):

in: R ¹ is hydrogen, C _1-4 alkyl, C _6-10 aryl or C _6-10 aryl C _1-3 alkyl; R ¹ is optionally substituted by 1 substituent selected from R ^a ; X is a key, -O- or -C(=O)-; R ² and R ³ are each independently hydrogen or C _1-4 alkyl; Or -CR ² R ³ - is -C(=O)-; n is 2; R ⁴ is C _3-6 cycloalkyl; R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ are each independently hydrogen, fluorine, chlorine, bromine, iodine, hydroxy, cyano, nitro, amino or carboxyl; R ^a is fluorine, chlorine, bromine, iodine, hydroxy, cyano, nitro, C _1-4 alkyl, C _1-4 haloalkyl, C _1-4 alkoxy, C _1-4 haloalkoxy or - C(=O)-OC _1-3 alkyl. 2. The compound of claim 1, wherein R ¹ is hydrogen, methyl, ethyl, n-propyl, isopropyl, phenyl or benzyl; R is optionally substituted with ¹ substituent selected from ^Ra ; R ^a is fluorine, chlorine, bromine, iodine, hydroxyl, cyano, nitro, methyl, ethyl, n-propyl, isopropyl, methoxy, ethoxy, n-propoxy, isopropoxy or -C(=O)-OCH ₃ . 3. The compound according to claim 1, which is a salt of a compound represented by formula (II) or a compound represented by formula (II):

4. A compound, which is a compound having one of the following structures or a salt of a compound having one of the following structures:

5. A composition comprising the compound of any one of claims 1-4; further comprising a pesticidally acceptable surfactant and/or a carrier. 6. Use of the compound of any one of claims 1-4 or the composition of claim 5 in plant disease control.