CN110577498A - 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 compound and application thereof in agriculture

Technical Field

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

Background

Plant diseases that damage ornamental, vegetable, field, cereal and fruit crops can cause significant reductions in yield, leading to increased costs of consumption. To achieve high crop yields, it is extremely important to control plant diseases caused by phytopathogenic fungi. To this end, pesticide products can be used in plant growing processes, many of which are commercially available, but there is a continuing need for new compounds that are more effective, more economical, less toxic, environmentally safer or have different sites of action.

The invention provides a novel triazole compound with bactericidal activity.

Disclosure of Invention

The invention aims to provide a novel bactericidal compound with remarkable control effect on plant diseases, a bactericidal composition containing the bactericidal compound, a preparation and application of the bactericidal composition.

In one aspect, the invention provides compounds of formula (I) or stereoisomers, N-oxides, and salts thereof of compounds of formula (I):

Wherein:

R¹Is hydrogen, alkyl, alkenyl, alkynyl, alkoxy, alkenyloxy, alkynyloxy, aryl, arylalkyl, heteroaryl, heteroarylalkyl, cycloalkyl, cycloalkylalkyl, heterocyclyl or heterocyclylalkyl; r¹Optionally substituted by 1,2,3, 4 or 5 substituents selected from R^aSubstituted with the substituent(s);

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

R²And R³Each independently is hydrogen, fluoro, chloro, bromo, iodo, hydroxy, cyano, nitro, amino, carboxy, alkyl, alkenyl, or alkynyl;

or-CR²R³-is-C (═ O) -;

n is 0, 1 or 2;

R⁴Is hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, heterocyclyl, aryl, arylalkyl, cycloalkylalkyl, or heterocyclylalkyl;

R⁵、R⁶、R⁷、R⁸And R⁹Each independently is hydrogen, fluoro, chloro, bromo, iodo, hydroxy, cyano, nitro, amino, carboxy, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, hydroxy-substituted alkyl, amino-substituted alkyl, cyano-substituted alkyl, alkoxy, haloalkoxy, hydroxy-substituted alkoxy, amino-substituted alkoxy, cyano-substituted alkoxy, alkylamino, alkylthio, or aryloxy;

Each R^aIndependently is fluorine, chlorine, bromine, iodine, hydroxyl, cyano, nitro, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, alkoxy, haloalkoxy, -C (═ O) -OR^cor an aryloxy group;

Each R^bIndependently hydrogen, alkyl, alkenyl or alkynyl; and

Each R^cIndependently hydrogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, cycloalkyl, heterocyclyl, aryl or heteroaryl.

In some of these embodiments, R¹Is hydrogen, C_1-6Alkyl radical, C_2-6Alkenyl radical, C_2-6Alkynyl, C_1-6Alkoxy radical, C_2-6Alkenyloxy radical, C_2-6Alkynyloxy, C_6-10aryl radical, C_6-10aryl radical C_1-6Alkyl radical, C_1-9Heteroaryl group, C_1-9Heteroaryl C_1-6Alkyl radical, C_3-8Cycloalkyl radical, C_3-8Cycloalkyl radical C_1-6Alkyl radical, C_2-10Heterocyclyl or C_2-10Heterocyclyl radical C_1-6an alkyl group; r¹Optionally substituted by 1,2,3, 4 or 5 substituents selected from R^aSubstituted with the substituent(s);

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

R²And R³Each independently of the otherIs hydrogen, fluorine, chlorine, bromine, iodine, hydroxyl, cyano, nitro, amino, carboxyl, C_1-6Alkyl radical, C_2-6Alkenyl or C_2-6An alkynyl group;

or-CR²R³-is-C (═ O) -;

n is 0, 1 or 2;

R⁴Is hydrogen, C_1-6Alkyl radical, C_2-6Alkenyl radical, C_2-6alkynyl, C_3-8Cycloalkyl radical, C_2-10Heterocyclic group, C_6-10Aryl radical, C_6-10Aryl radical C_1-6Alkyl radical, C_3-8Cycloalkyl radical C_1-6Alkyl or C_2-10Heterocyclyl radical C_1-6An alkyl group;

R⁵、R⁶、R⁷、R⁸And R⁹Each independently is hydrogen, fluorine, chlorine, bromine, iodine, hydroxyl, cyano, nitro, amino, carboxyl, C_1-6alkyl radical, C_2-6Alkenyl radical, C_2-6alkynyl, halo C_1-6Alkyl, halo C_2-6Alkenyl, halo C_2-6Alkynyl, hydroxy-substituted C_1-6Alkyl, amino substituted C_1-6alkyl, cyano-substituted C_1-6Alkyl radical, C_1-6Alkoxy, halo C_1-6alkoxy, hydroxy-substituted C_1-6alkoxy, amino substituted C_1-6alkoxy, cyano-substituted C_1-6Alkoxy radical, C_1-6alkylamino radical, C_1-6Alkylthio or C_6-10An aryloxy group;

Each R^aIndependently fluorine, chlorine, bromine, iodine, hydroxyl, cyano, nitro, C_1-6Alkyl radical, C_2-6Alkenyl radical, C_2-6Alkynyl, halo C_1-6Alkyl, halo C_2-6Alkenyl, halo C_2-6Alkynyl, C_1-6Alkoxy, halo C_1-6Alkoxy, -C (═ O) -OR^cOr C_6-10An aryloxy group;

each R^bIndependently of one another is hydrogen, C_1-6Alkyl radical, C_2-6Alkenyl or C_2-6An alkynyl group; and

Each R^cIndependently of one another is hydrogen, C_1-6Alkyl radical, C_2-6Alkenyl radical、C_2-6Alkynyl, halo C_1-6Alkyl, halo C_2-6Alkenyl, halo C_2-6Alkynyl, C_3-8Cycloalkyl radical, C_2-6heterocyclic group, C_6-10Aryl or C_1-5A heteroaryl group.

In other embodiments, R²And R³each independently is hydrogen, fluorine, chlorine, bromine, iodine, hydroxyl, cyano, nitro, amino, carboxyl, C_1-4Alkyl radical, C_2-4Alkenyl or C_2-4An alkynyl group;

or-CR²R³-is-C (═ O) -.

In other embodiments, R⁴Is hydrogen, C_1-4Alkyl radical, C_2-4Alkenyl radical, C_2-4Alkynyl, C_3-6Cycloalkyl radical, C_2-6Heterocyclic group, C_6-10Aryl radical, C_6-10aryl radical C_1-4Alkyl radical, C_3-6Cycloalkyl radical C_1-3Alkyl or C_2-6Heterocyclyl radical C_1-3An alkyl group.

In other embodiments, R⁴Hydrogen, methyl, ethyl, n-propyl, isopropyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, phenyl or benzyl.

In other embodiments, R⁵、R⁶、R⁷、R⁸And R⁹Each independently is hydrogen, fluorine, chlorine, bromine, iodine, hydroxyl, cyano, nitro, amino, carboxyl, C_1-4Alkyl radical, C_2-4Alkenyl radical, C_2-4Alkynyl, halo C_1-4alkyl, halo C_2-4Alkenyl, halo C_2-4Alkynyl, hydroxy-substituted C_1-4Alkyl, amino substituted C_1-4Alkyl, cyano-substituted C_1-4alkyl radical, C_1-4Alkoxy, halo C_1-4Alkoxy, hydroxy-substituted C_1-4Alkoxy, amino substituted C_1-4Alkoxy, cyano-substituted C_1-4Alkoxy radical, C_1-4Alkylamino radical, C_1-4alkylthio or phenoxy.

In other embodiments, R¹Is hydrogen, C_1-4Alkyl radical, C_2-4An alkenyl group,C_2-4Alkynyl, C_1-4Alkoxy radical, C_2-4Alkenyloxy radical, C_2-4Alkynyloxy, C_6-10Aryl radical, C_6-10aryl radical C_1-3Alkyl radical, C_1-5Heteroaryl group, C_1-5Heteroaryl C_1-3Alkyl radical, C_3-6Cycloalkyl radical, C_3-6Cycloalkyl radical C_1-3Alkyl radical, C_2-6Heterocyclyl or C_2-6Heterocyclyl radical C_1-3an alkyl group; r¹Optionally substituted by 1,2,3, 4 or 5 substituents selected from R^aSubstituted with the substituent(s); and

Each R^aIndependently fluorine, chlorine, bromine, iodine, hydroxyl, cyano, nitro, C_1-4Alkyl radical, C_2-4Alkenyl radical, C_2-4Alkynyl, halo C_1-4Alkyl, halo C_2-4Alkenyl, halo C_2-4Alkynyl, C_1-4Alkoxy, halo C_1-4Alkoxy, -C (═ O) -OC_1-3Alkyl or C_6-10an aryloxy group.

In other embodiments, R¹Is hydrogen, methyl, ethyl, n-propyl, isopropyl, vinyl, allyl, propenyl, methoxy, ethoxy, n-propoxy, isopropoxy, phenyl, benzyl or pyridyl;

R¹Optionally substituted by 1,2,3, 4 or 5 substituents selected from R^aSubstituted with the substituent(s); and

Each R^aIndependently hydrogen, fluorine, chlorine, bromine, iodine, hydroxyl, 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 that is a compound of formula (II) or a stereoisomer, nitroxide, or salt of a compound of formula (II):

Wherein: r¹、R⁵、R⁶、R⁷、R⁸And R⁹Has the following advantages thatThe meaning is stated.

In still other embodiments, the invention provides compounds of formula (II), stereoisomers, nitroxides and salts thereof, wherein R is¹Is C_1-4Alkyl or C_6-10Aryl radical C_1-3An alkyl group; further preferably, R¹Is methyl, ethyl, isopropyl or benzyl;

R⁵、R⁶、R⁷、R⁸And R⁹Each independently is hydrogen, fluoro, chloro, bromo, iodo, hydroxy, cyano, nitro, amino, carboxy, methyl or methoxy.

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

Wherein:

X、R⁵、R⁶、R⁷、R⁸And R⁹Have the meaning as described herein;

Y is N or CR^a5；

R^a1、R^a2、R^a3、R^a4And R^a5Having the formula R according to the invention^aThe meaning is stated.

In still other embodiments, the invention provides compounds of formula (III), stereoisomers, nitroxides, and salts thereof, wherein R is⁵、R⁶、R⁷、R⁸And R⁹Each independently is hydrogen, fluoro, chloro, bromo, iodo, hydroxy, cyano, nitro, amino, carboxy, methyl, or methoxy;

X is a bond or-C (═ O) -;

R^a1、R^a2、R^a3、R^a4And R^a5Each independently hydrogen, fluorine, chlorine, bromine, iodine, hydroxyl, cyano, nitro, methyl, ethyl, n-propylalkyl, isopropyl, phenoxy, methoxy, ethoxy, n-propoxy, isopropoxy or-C (═ O) -OCH₃。

In some of these embodiments, the present invention provides a compound that is a compound having one of the following structures or stereoisomers, nitroxides, and salts of compounds having one of the following structures:

In another aspect, the invention provides a composition comprising a compound of the invention. Unless otherwise indicated, all tautomers, racemates, hydrates, solvates, metabolites, metabolic precursors and prodrugs of the compounds of formula (I), formula (II) or formula (III) of the present invention are also within the scope of the present invention.

In some embodiments, the composition further comprises an agriculturally acceptable surfactant and/or carrier.

In another aspect, the invention provides the use of a compound of the invention or a composition of the invention for the control of plant diseases, particularly as a fungicide.

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

The compounds of formula (I) 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 hydrogen, carbon, nitrogen, oxygen, phosphorus, sulfur, fluorine, and chlorineIsotopes of (e.g. of²H，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 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 found in the descriptions of "Organic Chemistry", Thomas Sorrell, University Science Books, Sausaltito: 1999, and "March's Advanced Organic Chemistry" by Michael B.Smith and JerryMarch, 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 one or to more than one (i.e., to at least one) of the objects. 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; 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 1l 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.

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. In certain embodiments, each asymmetric atom has at least 50% enantiomeric excess, at least 60% enantiomeric excess, at least 70% enantiomeric excess, at least 80% enantiomeric excess, at least 90% enantiomeric excess, at least 95% enantiomeric excess, or at least 99% enantiomeric excess in the (R) -or (S) -configuration.

Depending on the choice of starting materials and methods, the compounds of the invention may exist as one of the possible isomers or as mixtures thereof, for example as racemates and mixtures of non-corresponding isomers (depending on the number of asymmetric carbon atoms). 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 substituents may be in the E or Z configuration; if the compound contains a disubstituted cycloalkyl group, the substituents of the cycloalkyl group may have cis or trans configuration.

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

the racemates of any of the resulting end products or intermediates can be resolved into the optical enantiomers by known methods using methods familiar to those skilled in the art, e.g., by separation of the diastereomeric salts obtained. The racemic product can also be separated by chiral chromatography, e.g., High Performance Liquid Chromatography (HPLC) using a chiral adsorbent. In particular, enantiomers can be prepared by asymmetric synthesis.

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. Specifically, examples of "one or more" refer to 1,2,3, 4, 5, 6, 7, 8, 9, or 10. 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 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) And so on.

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 may be optionally substituted with one or more substituents described herein, including the positioning of "cis" and "tans", or the positioning of "E" and "Z". In one embodiment, the alkenyl group contains 2 to 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-), oxo butenyl (CH)₃-C (═ O) -CH ═ CH-) and the like.

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.

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. Examples of alkoxy groups include, but are not limited toThen, 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) And so on.

The term "alkylthio" means an alkyl group attached to the rest 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)₂and so on.

The term "cycloalkyl" denotes a monovalent or polyvalent saturated monocyclic, bicyclic or tricyclic ring system containing from 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, and the like.

The terms "heterocyclyl" and "heterocycle" are used interchangeably herein and refer to a saturated or partially unsaturated monocyclic, bicyclic, or tricyclic ring containing 3 to 15 ring atoms, wherein no aromatic ring is included in the monocyclic, bicyclic, or tricyclic ring, and at least one ring atom is selected from the group consisting of nitrogen, sulfur, and oxygen atoms. Unless otherwise specified, heterocyclyl may be carbon-or nitrogen-based, and-CH₂-the group may optionally be replaced by-C (═ O) -. The sulfur atom of the ring may optionally be oxidized to the S-oxide. The nitrogen atom of the ring may optionally be oxidized to an N-oxygen compound. Examples of heterocyclyl groups include, but are not limited to, oxiranyl, azetidinyl, oxetanyl, thietanyl, pyrrolidinyl (e.g., 2-pyrrolidinyl), 2-pyrrolinyl, 3-pyrrolinyl, pyrazolidinyl, imidazolinyl, imidazolidinyl, tetrahydrofuranyl, dihydrofuranyl, tetrahydrothienyl, dihydrothienyl, 1, 3-di-n-butylOxocyclopentyl, dithiocyclopentyl, tetrahydropyranyl, dihydropyranyl, 2H-pyranyl, 4H-pyranyl, tetrahydrothiopyranyl, piperidinyl (2-piperidinyl, 3-piperidinyl, 4-piperidinyl), morpholinyl, thiomorpholinyl, (1-oxo) -thiomorpholinyl, (1, 1-dioxo) -thiomorpholinyl, piperazinyl, dioxanyl, dithianyl, thioxanyl, homopiperazinyl, homopiperidinyl, oxepanyl, thiepanyl, 2-oxa-5-azabicyclo [2.2.1]Hept-5-yl, tetrahydropyridinyl. In heterocyclic radicals of-CH₂Examples of-groups substituted by-C (═ O) -include, but are not limited to, 2-oxopyrrolidinyl, oxo-1, 3-thiazolidinyl, 2-piperidinonyl, 3, 5-dioxopiperidinyl. Examples of sulfur atoms in heterocyclic groups that are oxidized include, but are not limited to, sulfolane, 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 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 "halogen" refers to fluorine (F), chlorine (Cl), bromine (Br) or iodine (I).

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 "arylalkyl" or "aralkyl" means that the alkyl group is substituted with one or more aryl groups, wherein the alkyl and aryl groups have the meaning as described herein; examples include, but are not limited to, phenylmethyl (i.e., benzyl), phenylethyl, and the like.

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.

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), benzopiperidinyl, and the like.

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 of formula (I) may be prepared by treating a compound of formula (I) 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 invention are generally useful as fungicide active ingredients in compositions, i.e., formulations, typically also comprising an agriculturally acceptable surfactant and/or carrier.

The surfactant may be any of various surfactants known in the field of pesticide formulation, and one or more of an emulsifier, a dispersant and a wetting agent are preferred in the present invention.

The carrier other than the surfactant may be any of various carriers known in the field of pesticide formulation, including various silicates, carbonates, sulfates, oxides, phosphates, plant carriers, and synthetic carriers. Specifically, for example: white carbon black, kaolin, diatomite, clay, talc, organic bentonite, pumice, titanium dioxide, dextrin, cellulose powder, light calcium carbonate, soluble starch, corn starch, sawdust powder, urea, an amine fertilizer, a mixture of urea and an amine fertilizer, glucose, maltose, sucrose, anhydrous potassium carbonate, anhydrous sodium carbonate, anhydrous potassium bicarbonate, anhydrous sodium bicarbonate, attapulgite, a mixture of anhydrous potassium carbonate and anhydrous potassium bicarbonate, and a mixture of anhydrous sodium carbonate and anhydrous sodium bicarbonate.

The emulsifier may be any emulsifier known in the field of pesticide formulation, and specifically, the emulsifier may be one or more of calcium dodecylbenzenesulfonate, trisethylphenol polyoxyethylene ether phosphate, fatty alcohol polyoxyethylene ether, alkylphenol polyoxyethylene polyoxypropylene ether, fatty amine, ethylene oxide adduct of fatty amide, fatty acid polyoxyethylene ester, rosin acid ethylene oxide adduct, polyol fatty acid ester and ethylene oxide adduct thereof, styrylphenyl polyoxyethylene ether, alkylphenol formaldehyde resin polyoxyethylene ether, hydroxyl-terminated polyoxyethylene polyoxypropylene ether, styrylphenol formaldehyde resin polyoxyethylene polyoxypropylene ether, and castor oil polyoxyethylene ether.

The dispersing agent can be various dispersing agents known in the field of pesticide formulation, and specifically, the dispersing agent is one or more of acrylic acid homopolymer sodium salt, maleic acid disodium salt, naphthalene sulfonic acid formaldehyde condensation product sodium salt, rosin block polyoxyethylene ether polyoxypropylene ether sulfonate, hydroxyl-terminated polyoxyethylene polyoxypropylene ether block copolymer, triphenyl polyoxyethylene phenol phosphate, fatty alcohol polyoxyethylene ether phosphate and p-hydroxyphenyl lignosulfonate sodium salt.

The wetting agent can be various wetting agents known in the field of pesticide formulation, and specifically, the wetting agent can be one or more of sodium dodecyl sulfate, secondary alkyl sodium sulfate, sodium dodecyl benzene sulfonate, fatty alcohol-polyoxyethylene ether, alkyl naphthalene sulfonate and alkylphenol resin polyoxyethylene ether sulfate.

According to the bactericide composition, various preparation auxiliaries commonly used in the field of pesticide formulation can be further contained, and specifically, the preparation auxiliaries can be one or more of a solvent, a cosolvent, a thickening agent, an antifreezing agent, a capsule wall material, a protective agent, an antifoaming agent, a disintegrating agent, a stabilizing agent, a preservative and a binder.

The solvent may be any of various solvents known in the field of pesticide formulation, and specifically, the solvent may be one or more of an organic solvent, a vegetable oil, a mineral oil, a solvent oil and water.

Wherein the organic solvent comprises one or more of N-methylpyrrolidone, tetrahydrofuran, dimethyl sulfoxide, N-dimethyldecanamide, N-dimethylformamide, trimethylbenzene, tetramethylbenzene, dimethylbenzene, methylbenzene, octane, heptane, methanol, isopropanol, N-butanol, tetrahydrofurfuryl alcohol, tributyl phosphate, 1, 4-dioxane and cyclohexanone.

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

The mineral oil comprises one or more of liquid wax, engine oil, kerosene and lubricating oil.

Meanwhile, the solvent can also be used as a cosolvent.

The antifreeze can be various antifreeze agents known in the field of pesticide formulation, and the invention is preferably one or more of ethylene glycol, propylene glycol, glycerol and urea.

The thickener can be various thickeners known in the field of pesticide formulation, and specifically can be one or more of xanthan gum, polyvinyl alcohol, polypropylene alcohol, polyethylene glycol, white carbon black, diatomite, kaolin, clay, sodium alginate, magnesium aluminum silicate, sodium aluminum silicate, carboxymethyl cellulose, sodium hydroxypropyl cellulose and organic bentonite.

The capsule material can be various capsule materials known in the field of pesticide formulation, and the invention is preferably one or more of polyurethane, polyurea and urea-formaldehyde resin.

The protective agent may be any of various protective agents known in the field of pesticide formulation, and polyvinyl alcohol and/or polyethylene glycol is preferred in the present invention.

The defoaming agent may be any of those known in the field of agricultural agent formulation, and in the present invention, one or more of organosiloxane, tributyl phosphate and silicone are preferable.

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

The antiseptic is selected from one or more of benzoic acid, sodium benzoate, 1, 2-benzisothiazolin-3-one (BIT), Kathon and potassium sorbate.

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

The preparation method of the emulsifiable concentrate preparation can comprise, for example, mixing and stirring the active components, the solvent, the cosolvent and the emulsifier to form a uniform transparent oil phase, so as to obtain the emulsifiable concentrate preparation.

The preparation method of the aqueous emulsion can comprise, for example, mixing the active ingredient, the emulsifier, the cosolvent and the solvent to form a uniform oil phase; mixing water, thickener, antifreeze, etc. to obtain uniform water phase. Under high-speed shearing, adding the water phase into the oil phase or adding the oil phase into the water phase to form the aqueous emulsion with good dispersibility.

The microemulsion may be prepared, for example, by mixing and stirring the active ingredient, emulsifier, and solvent to form a uniform transparent oil phase. Under stirring, water is gradually added to form a uniform and transparent microemulsion.

The preparation method of the water/oil suspending agent comprises the following steps: for example, water or oil can be used as a medium, and an auxiliary agent such as an active component and a surfactant is added into a sanding kettle, and after grinding to a certain particle size, filtration is performed. And adding the weighed thickening agent into the ground mother liquor, and uniformly shearing and dispersing. Making into oil suspension or water suspension.

The preparation method of the water dispersible granule and the soluble granule comprises the following steps: for example, the active ingredients, the dispersing agent, the wetting agent, the carrier and the like are uniformly mixed, then are pulverized into a certain particle size through air flow, are added with water for kneading, are finally added into a granulator for granulation, and are dried to obtain the water dispersible granules or the soluble granules.

The preparation method of the soluble powder and the wettable powder comprises the following steps: for example, the active ingredients, various adjuvants and fillers such as other carriers can be thoroughly mixed and pulverized by a micronizer.

The germicide composition of the present invention may be provided in the form of a finished formulation, i.e., the components of the composition have been mixed; or in separate formulations which are self-mixing in a tub or tank prior to use and optionally diluted by mixing with water depending on the concentration of active desired.

Application of the inventive compounds and compositions

The compound of the present invention is useful as a plant disease control agent. The present invention therefore also comprises a method for controlling plant diseases caused by phytopathogenic fungi, which comprises applying to the plants to be protected or to parts thereof or to the seeds of the plants to be protected an effective amount of a compound according to the invention or of a fungicidal composition comprising said compound. The compounds and/or compositions of the present invention provide control of diseases caused by a broad spectrum of phytopathogenic fungi of the classes Basidiomycetes, Ascomycetes, Oomycetes and Deuteromycetes. They are effective in controlling a broad spectrum of plant diseases, particularly foliar pathogens of ornamental, turf, vegetable, field, cereal and fruit crops. These pathogens include: oomycetes, including Phytophthora (Phytophthora) diseases such as Phytophthora infestans, Phytophthora sojae (Phytophthora megasporum), Phytophthora citri (Phytophthora parasitica), Phytophthora citrullus (Phytophthora parasiti), Phytophthora cinnamomi (Phytophthora cinnamomi) and Phytophthora cucurbitae (Phytophthora capsici), Pythium graminum (Pythium) species diseases such as Pythium turtium (Pythium aphanidermatum) diseases, and Peronosporaceae (Peronospora) species diseases such as Plasmopara viticola (Plasmopara viticola), Peronospora (Peronospora spp.) (including P. nicotianae (Peronospora tabacina) and P. parasitica (Pseudoperonospora Pseudoperonospora), including P. nicotianae (Pseudoperonospora cinerea) and P. Pseudoperonospora (Pseudoperonospora Pseudoperonospora) diseases including P); ascomycetes (including Alternaria (Alternaria) such as Alternaria solani and Phytophthora brassicae (Alternaria solani), Mycoporia (Guignardia) diseases such as Staphylococcus viticola (Guignardiabidwell), Venturia (Venturia) diseases such as Venturia mali (Venturia inaequalis), Sphaerotheca (Sepia) diseases such as Microchaeta oryzae (Septoria nodorum) and Phytophthora parasitica (Septorii), Powderzia (Powderi) diseases such as Erysiphe graminis (Erysiphe spp.) and Sphaerotheca (Septoria), Powderiana (Potentilla graminis) diseases such as Microchaeta canis (Erysiphe sp.) and Pseudoperonospora cinerea (Pseudoperonospora cinerea), Microchaeta (Ucinula graminis), Pseudoperonospora cucumerina and Pseudoperonospora cinerea (Botrytis) diseases such as Microchaetobacter sphaera), Potentilla graminis (Potentilla), Potentilla (Potentilla graminis (Potentilla) diseases such as Microchaetotrichia cinerea), Sclerotiella (Sclerotiella) and Pseudoperonospora cinerea), Scleroticola (Potentilla fragi (Potentilla) diseases such as Microchaetotrichia cinerea), Scleroticola (Potentilla fragi (Potentilla) diseases, Pyricularia oryzae (Magnaporthe grisea), Rhizoctonia solani (Phomopsis viticola), Helminthosporium (Helminthosporium) diseases such as northern leaf blight (Helminthosporium tritici reptilis), Moss reticulata (Pyrenophora teres), anthrax bacteria such as Hedychium nigrum (Glomerella) or Anthrax (Colletochium spp.) diseases (such as Colletotrichum graminicum (Colestochium graminicum) and watermelon anthrax (Colletochium orbiculosum)), and wheat holothrix graminis (Gaeumannomyces graminis); basidiomycetes, including rust diseases caused by the genus Puccinia (Puccinia spp.), such as Puccinia recondita (Puccinia recondita), Puccinia striiformis (Puccinia striiformis), Puccinia purpurea (Puccinia hordei), Puccinia graminis (Puccinia graminis) and Puccinia arachidis (Puccinia arachidis), coffee rust (hemix) and soybean rust (Phakopsora pachyrhizi); other pathogens include Rhizoctonia species (Rhizoctonia spp.) (such as Rhizoctonia solani); fusarium species diseases such as Fusarium roseum (Fusarium roseum), Fusarium graminearum (Fusarium graminearum), and Fusarium oxysporum (Fusarium oxysporum); verticillium dahliae (Verticilliumdahliae); sclerotium rolfsii (sclerotiotium rolfsii); physalospora piricola (Rynchosporium secalis); black acerola (Cercosporium personatum), Episra nigrella (Cercospora arachidicola), and Episra fuscospora (Cercospora betacola); and other classes and species closely related to these pathogens. In addition to their fungicidal activity, the compositions or combinations also have a resistant activity against bacteria such as Erwinia amylovora (Erwinia amylovora), Xanthomonas campestris (Xanthomonas campestris), Pseudomonas syringae (Pseudomonas syringae) and other species.

The bactericide composition of the invention is simple in use method, and can be applied to crops and places where the crops grow by a conventional method such as soil mixing, spraying, pouring and the like before or after the germination of plant diseases, wherein the application amount is determined according to climatic conditions or crop states, generally 10-5000g is applied per mu, and the diluted application amount is 10-400mg/L (preferably 100-300 mg/L). The diluent is preferably water.

The bactericidal effect of the bactericide composition of the present invention is generally related to external factors such as climate, but the influence of climate can be alleviated by using appropriate dosage forms.

The compositions of the present invention may also be used in admixture with other compounds having fungicidal, insecticidal or herbicidal properties, as well as with nematicides, acaricides, protectants, herbicidal safeners, growth regulators, plant nutrients or soil conditioners, and the like.

General synthetic procedure

The following examples describe the preparation of the compounds of the present invention. Unless otherwise indicated, the compounds of the invention may be prepared by the methods described herein. 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. In this specification, a structure is dominant if there is any difference between the chemical name and the chemical structure.

The following acronyms are used throughout the invention:

g, g; mg; mol; mmol millimole; h hours; min; l liter; mL, mL; m mol/L;

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

Examples

EXAMPLE A Synthesis of intermediate N-benzylcyclopropylamine

Cyclopropane (3.42g,0.06mol), potassium carbonate (20.00g,0.15mol) and DMF (80mL) were added to a 250mL reaction flask and stirred well at room temperature; then, a solution of benzyl chloride (5.11g,0.04mol) in DMF (20mL) is slowly dripped into the reaction (dripping is finished within 1 hour), and the reaction is carried out for 48 hours at 25 ℃; then, water (80mL) was added, and extraction was performed with diethyl ether (100mL × 3), and the organic phase was washed with a saturated aqueous solution of sodium chloride (100mL × 2), dried over magnesium sulfate, concentrated, and purified by column chromatography (EtOAc/PE (v/v) ═ 1/4) to obtain 3.06g of a yellow liquid with a yield of 52%.

¹H-NMR(400MHz,DMSO-d₆):δ(ppm)7.3～7.2(m,5H),3.7(s,2H),2.0(m,1H),0.3～0.4(m,4H)；

¹³C NMR(100MHz,DMSO-d₆):δ(ppm)141.6,128.4,126.8,53.4,30.1,6.6.

LC-MS:(M+1)m/z＝148.2.

by a similar synthetic procedure to example a, substituting the corresponding starting material for benzyl chloride, the intermediate compounds of table 1 can be obtained.

TABLE 1

EXAMPLE B Synthesis of intermediate N-benzyl-N-cyclopropyl-1H-1, 2, 4-triazole-3-sulfonamide

N-cyclopropylbenzylamine (2.94g,0.02mol), triethylamine (2.02g,0.02mol) and tetrahydrofuran (30mL) were added to a 100mL single-neck bottle; stirring uniformly at 0-5 ℃ in an ice bath, slowly dropping a THF (15mL) solution of 1H-1,2, 4-triazole-3-sulfonyl chloride (3.32g,0.02mol) (dropping is completed within 1 hour), reacting for 12 hours, adding water (20mL), and adjusting the pH value to 5 with hydrochloric acid; finally, extraction with ether (100mL × 3) combined the organic phases, dried over magnesium sulfate, concentrated, washed with n-hexane to give an off-white solid 4.62g, yield: 83.1 percent.

¹H-NMR(400MHz,DMSO-d₆):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)；

¹³C NMR(100MHz,DMSO-d₆):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.

By a similar synthetic method to that of example B, the intermediate compounds of table 2 can be obtained from the corresponding starting materials and conditions.

TABLE 2

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

adding N, N-dibenzyl-1H-1, 2, 4-triazole-3-sulfonamide (0.33g,1.0mmol), potassium carbonate (0.28g,2.0mmol) and DMF (10mL) into a 100mL three-necked bottle, slowly adding benzyl chloride (0.19g,1.5mmol) into the reaction system, and reacting at room temperature of 25 ℃ for 8 hours; quenching with water (20mL), extraction with ethyl acetate (15mL × 3), washing of the organic phase with saturated brine (10mL), drying over anhydrous magnesium sulfate, filtration, removal of the solvent from the filtrate under reduced pressure with a rotary evaporator, and purification by column chromatography (EtOAc/PE (v/v) ═ 1/3) gave 0.34g of a white solid in yield: 81.6 percent.

¹H NMR(400MHz,CDCl₃):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 2N-benzyl-N-cyclopropyl-1- (4-fluorobenzyl) -1H-1,2, 4-triazole-3-sulfonamide

Adding N-benzyl-N-cyclopropyl-1H-1, 2, 4-triazole-3-sulfonamide (0.28g,1.0mmol), potassium carbonate (0.28g,2.0mmol) and DMF (10mL) into a 100mL three-necked bottle, slowly adding 4-fluorobenzyl bromide (0.28g,1.5mmol) into the reaction system, and reacting at room temperature of 25 ℃ for 8 hours; quenching with water (20mL), extraction with ethyl acetate (15mL × 3), washing of the organic phase with saturated brine (10mL), drying over anhydrous magnesium sulfate, filtration, removal of the solvent from the filtrate under reduced pressure with a rotary evaporator, and purification by column chromatography (EtOAc/PE (v/v) ═ 1/3) gave 0.32g of a white solid in yield: 82.0 percent.

¹H NMR(400MHz,CDCl₃):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 3N-cyclopropyl-N, 1-bis (2-nitrobenzyl) -1H-1,2, 4-triazole-3-sulphonamide

Adding 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) into a 100mL three-necked bottle, slowly adding 2-nitrobenzyl chloride (0.28g,1.5mmol) into the reaction system, and reacting at room temperature of 25 ℃ for 8 hours; quenching with water (20mL), extraction with ethyl acetate (15mL × 3), washing of the organic phase with saturated brine (10mL), drying over anhydrous magnesium sulfate, filtration, removal of the solvent from the filtrate under reduced pressure with a rotary evaporator, and purification by column chromatography (EtOAc/PE (v/v) ═ 1/3) gave 0.35g of a white solid in yield: 76.6 percent.

¹H NMR(400 MHz,DMSO-d₆):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

Adding N-benzyl-N-cyclopropyl-1H-1, 2, 4-triazole-3-sulfonamide (0.28g,1.0mmol), potassium carbonate (0.28g,2.0mmol) and DMF (10mL) into a 100mL three-necked bottle, slowly adding methyl chloroformate (0.14g,1.5mmol) into the reaction system, and reacting at room temperature of 25 ℃ for 8 hours; quenching with water (20mL), extraction with ethyl acetate (15mL × 3), washing of the organic phase with saturated brine, drying over anhydrous magnesium sulfate, filtration, removal of the solvent from the filtrate under reduced pressure with a rotary evaporator, and purification by column chromatography (EtOAc/PE (v/v) ═ 1/3) gave 0.24g of a white solid in yield: 71.0 percent.

¹H NMR(400MHz,CDCl₃):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

Adding N-benzyl-N-cyclopropyl-1H-1, 2, 4-triazole-3-sulfonamide (0.28g,1.0mmol), potassium carbonate (0.28g,2.0mmol) and DMF (10mL) into a 100mL three-necked bottle, slowly adding benzyl chloroformate (0.26g,1.5mmol) into the reaction system, and reacting at room temperature of 25 ℃ for 8 hours; quenching with water (20mL), extraction with ethyl acetate (15mL × 3), washing of the organic phase with saturated brine, drying over anhydrous magnesium sulfate, filtration, removal of the solvent from the filtrate under reduced pressure with a rotary evaporator, and purification by column chromatography (EtOAc/PE (v/v) ═ 1/3) gave 0.29g of a white solid in yield: 70.1 percent.

¹H NMR(400MHz,CDCl₃):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 6N-benzyl-N-cyclopropyl-1- (2-oxo-2-phenylethyl) -1H-1,2, 4-triazole-3-sulphonamide

Adding N-benzyl-N-cyclopropyl-1H-1, 2, 4-triazole-3-sulfonamide (0.28g,1.0mmol), potassium carbonate (0.28g,2.0mmol) and DMF (10mL) into a 100mL three-necked bottle, slowly adding alpha-bromoacetophenone (0.30g,1.5mmol) into a reaction system, and reacting at room temperature of 25 ℃ for 8 hours; quenching with water (20mL), extraction with ethyl acetate (15mL × 3), washing of the organic phase with saturated brine, drying over anhydrous magnesium sulfate, filtration, removal of the solvent from the filtrate under reduced pressure with a rotary evaporator, and purification by column chromatography (EtOAc/PE (v/v) ═ 1/3) gave 0.31g of a white solid in yield: 78.0 percent.

¹H NMR(400MHz,DMSO-d₆):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 7N-benzyl-N-cyclopropyl-1- (4-methylbenzyl) -1H-1,2, 4-triazole-3-sulfonamide

Adding N-benzyl-N-cyclopropyl-1H-1, 2, 4-triazole-3-sulfonamide (0.28g,1.0mmol), potassium carbonate (0.28g,2.0mmol) and DMF (10mL) into a 100mL three-necked bottle, slowly adding 1- (bromomethyl) -4-methylbenzene (0.28g,1.5mmol) into the reaction system, and reacting at room temperature of 25 ℃ for 8 hours; quenching with water (20mL), extraction with ethyl acetate (15mL × 3), washing of the organic phase with saturated brine, drying over anhydrous magnesium sulfate, filtration, removal of the solvent from the filtrate under reduced pressure with a rotary evaporator, and purification by column chromatography (EtOAc/PE (v/v) ═ 1/3) gave 0.33g of a white solid in yield: 84.0 percent.

¹H NMR(400MHz,CDCl₃):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 8N-benzyl-N-cyclopropyl-1-methyl-1H-1, 2, 4-triazole-3-sulfonamide

Adding N-benzyl-N-cyclopropyl-1H-1, 2, 4-triazole-3-sulfonamide (0.28g,1.0mmol), potassium carbonate (0.28g,2.0mmol) and DMF (10mL) into a 100mL three-necked bottle, slowly adding methyl iodide (0.21g,1.5mmol) into the reaction system, and reacting at room temperature of 25 ℃ for 8 hours; quenching with water (20mL), extraction with ethyl acetate (15mL × 3), washing of the organic phase with saturated brine, drying over anhydrous magnesium sulfate, filtration, removal of the solvent from the filtrate under reduced pressure with a rotary evaporator, and purification by column chromatography (EtOAc/PE (v/v) ═ 1/3) gave 0.22g of a white solid in yield: 76.0 percent.

¹H NMR(400MHz,CDCl₃):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 91-allyl-N-benzyl-N-cyclopropyl-1H-1, 2, 4-triazole-3-sulfonamide

N-benzyl-N-cyclopropyl-1H-1, 2, 4-triazole-3-sulfonamide (0.28g,1.0mmol), and potassium carbonate (0.28g,2.0mmol)_mmol) and DMF (10mL) are added into a 100mL three-necked bottle, and then 3-bromopropylene (0.18g,1.5mmol) is slowly added into the reaction system to react for 8 hours at room temperature of 25 ℃; quenching with water (20mL), extraction with ethyl acetate (15mL × 3), washing of the organic phase with saturated brine, drying over anhydrous magnesium sulfate, filtration, removal of the solvent from the filtrate under reduced pressure with a rotary evaporator, and purification by column chromatography (EtOAc/PE (v/v) ═ 1/3) gave 0.25g of a white solid in yield: 79.0 percent.

¹H NMR(400MHz,CDCl₃):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 10N-benzyl-N-cyclopropyl-1- (4-isopropylbenzyl) -1H-1,2, 4-triazole-3-sulfonamide

Adding N-benzyl-N-cyclopropyl-1H-1, 2, 4-triazole-3-sulfonamide (0.28g,1.0mmol), potassium carbonate (0.28g,2.0mmol) and DMF (10mL) into a 100mL three-necked bottle, slowly adding 1- (bromomethyl) -4-isopropyl benzene (0.32g,1.5mmol) into the reaction system, and reacting at room temperature of 25 ℃ for 8 hours; quenching with water (20mL), extraction with ethyl acetate (15mL × 3), washing of the organic phase with saturated brine, drying over anhydrous magnesium sulfate, filtration, removal of the solvent from the filtrate under reduced pressure with a rotary evaporator, and purification by column chromatography (EtOAc/PE (v/v) ═ 1/3) gave 0.32g of a white solid in yield: 78.0 percent.

¹H NMR(400MHz,CDCl₃):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 11N-benzyl-N-cyclopropyl-1-isobutyl-1H-1, 2, 4-triazole-3-sulphonamide

Adding N-benzyl-N-cyclopropyl-1H-1, 2, 4-triazole-3-sulfonamide (0.28g,1.0mmol), potassium carbonate (0.28g,2.0mmol) and DMF (10mL) into a 100mL three-necked bottle, slowly adding bromo-isobutane (0.21g,1.5mmol) into the reaction system, and reacting at room temperature of 25 ℃ for 8 hours; quenching with water (20mL), extraction with ethyl acetate (15mL × 3), washing of the organic phase with saturated brine, drying over anhydrous magnesium sulfate, filtration, removal of the solvent from the filtrate under reduced pressure with a rotary evaporator, and purification by column chromatography (EtOAc/PE (v/v) ═ 1/3) gave 0.24g of a white solid in yield: 73.0 percent.

¹H NMR(400MHz,CDCl₃):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 12N-benzyl-N-cyclopropyl-1-isopropyl-1H-1, 2, 4-triazole-3-sulfonamide

Adding N-benzyl-N-cyclopropyl-1H-1, 2, 4-triazole-3-sulfonamide (0.28g,1.0mmol), potassium carbonate (0.28g,2.0mmol) and DMF (10mL) into a 100mL three-necked bottle, slowly adding 2-iodopropane (0.26g,1.5mmol) into the reaction system, and reacting at room temperature of 25 ℃ for 8 hours; quenching with water (20mL), extraction with ethyl acetate (15mL × 3), washing of the organic phase with saturated brine, drying over anhydrous magnesium sulfate, filtration, removal of the solvent from the filtrate under reduced pressure with a rotary evaporator, and purification by column chromatography (EtOAc/PE (v/v) ═ 1/3) gave 0.23g of a white solid in yield: 72.0 percent.

¹H NMR(400MHz,CDCl₃):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

Adding N-benzyl-N-cyclopropyl-1H-1, 2, 4-triazole-3-sulfonamide (0.28g,1.0mmol), potassium carbonate (0.28g,2.0mmol) and DMF (10mL) into a 100mL three-necked bottle, slowly adding methyl bromoacetate (0.23g,1.5mmol) into the reaction system, and reacting at room temperature of 25 ℃ for 8 hours; quenching with water (20mL), extraction with ethyl acetate (15mL × 3), washing of the organic phase with saturated brine, drying over anhydrous magnesium sulfate, filtration, removal of the solvent from the filtrate under reduced pressure with a rotary evaporator, and purification by column chromatography (EtOAc/PE (v/v) ═ 1/3) gave 0.26g of a white solid in yield: 74.0 percent.

¹H NMR(400MHz,CDCl₃):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 14N-benzyl-N-cyclopropyl-1- (2-phenoxybenzyl) -1H-1,2, 4-triazole-3-sulfonamide

Adding N-benzyl-N-cyclopropyl-1H-1, 2, 4-triazole-3-sulfonamide (0.28g,1.0mmol), potassium carbonate (0.28g,2.0mmol) and DMF (10mL) into a 100mL three-necked bottle, slowly adding 1- (chloromethyl) -2-phenoxybenzene (0.33g,1.5mmol) into the reaction system, and reacting at room temperature of 25 ℃ for 8 hours; quenching with water (20mL), extraction with ethyl acetate (15mL × 3), washing of the organic phase with saturated brine, drying over anhydrous magnesium sulfate, filtration, removal of the solvent from the filtrate under reduced pressure with a rotary evaporator, and purification by column chromatography (EtOAc/PE (v/v) ═ 1/3) gave 0.31g of a white solid in yield: 67.0 percent.

¹H NMR(400MHz,CDCl₃):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 15N-benzyl-N-cyclopropyl-1- (pyridin-4-ylmethyl) -1H-1,2, 4-triazole-3-sulfonamide

Adding N-benzyl-N-cyclopropyl-1H-1, 2, 4-triazole-3-sulfonamide (0.28g,1.0mmol), potassium carbonate (0.28g,2.0mmol) and DMF (10mL) into a 100mL three-necked bottle, slowly adding 4- (chloromethyl) pyridine (0.19g,1.5mmol) into the reaction system, and reacting at room temperature of 25 ℃ for 8 hours; quenching with water (20mL), extraction with ethyl acetate (15mL × 3), washing of the organic phase with saturated brine, drying over anhydrous magnesium sulfate, filtration, removal of the solvent from the filtrate under reduced pressure with a rotary evaporator, and purification by column chromatography (EtOAc/PE (v/v) ═ 1/3) gave 0.28g of a white solid in yield: 78.0 percent.

¹H NMR(400MHz,CDCl₃):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 16N-benzyl-N-cyclopropyl-1- (4-methoxybenzyl) -1H-1,2, 4-triazole-3-sulphonamide

adding N-benzyl-N-cyclopropyl-1H-1, 2, 4-triazole-3-sulfonamide (0.28g,1.0mmol), potassium carbonate (0.28g,2.0mmol) and DMF (10mL) into a 100mL three-necked bottle, slowly adding 1- (chloromethyl) -4-methoxybenzene (0.23g,1.5mmol) into the reaction system, and reacting at room temperature of 25 ℃ for 8 hours; quenching with water (20mL), extraction with ethyl acetate (15mL × 3), washing of the organic phase with saturated brine, drying over anhydrous magnesium sulfate, filtration, removal of the solvent from the filtrate under reduced pressure with a rotary evaporator, and purification by column chromatography (EtOAc/PE (v/v) ═ 1/3) gave 0.31g of a white solid in yield: 78.0 percent.

¹H NMR(400MHz,CDCl₃):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 17N-benzyl-N-cyclopropyl-1- (4-nitrobenzyl) -1H-1,2, 4-triazole-3-sulphonamide

adding N-benzyl-N-cyclopropyl-1H-1, 2, 4-triazole-3-sulfonamide (0.28g,1.0mmol), potassium carbonate (0.28g,2.0mmol) and DMF (10mL) into a 100mL three-necked bottle, slowly adding 1- (chloromethyl) -4-nitrobenzene (0.26g,1.5mmol) into the reaction system, and reacting at room temperature of 25 ℃ for 8 hours; quenching with water (20mL), extraction with ethyl acetate (15mL × 3), washing of the organic phase with saturated brine, drying over anhydrous magnesium sulfate, filtration, removal of the solvent from the filtrate under reduced pressure with a rotary evaporator, and purification by column chromatography (EtOAc/PE (v/v) ═ 1/3) gave 0.30g of a white solid in yield: 73.0 percent.

¹H NMR(400MHz,CDCl₃):δ(ppm)8.26-8.24(s,3H),7.46(d,J＝8.6Hz,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) benzoate

Adding N-benzyl-N-cyclopropyl-1H-1, 2, 4-triazole-3-sulfonamide (0.28g,1.0mmol), potassium carbonate (0.28g,2.0mmol) and DMF (10mL) into a 100mL three-necked bottle, slowly adding methyl 4- (chloromethyl) benzoate (0.28g,1.5mmol) into the reaction system, and reacting at room temperature of 25 ℃ for 8 hours; quenching with water (20mL), extraction with ethyl acetate (15mL × 3), washing of the organic phase with saturated brine, drying over anhydrous magnesium sulfate, filtration, removal of the solvent from the filtrate under reduced pressure with a rotary evaporator, and purification by column chromatography (EtOAc/PE (v/v) ═ 1/3) gave 0.33g of a white solid in yield: 77.0 percent.

¹H NMR(400MHz,CDCl₃):δ(ppm)8.20(s,1H),8.04(d,J＝8.2Hz,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

Adding 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) into a 100mL three-necked bottle, slowly adding methyl chloroformate (0.14g,1.5mmol) into the reaction system, and reacting at room temperature of 25 ℃ for 8 hours; quenching with water (20mL), extraction with ethyl acetate (15mL × 3), washing of the organic phase with saturated brine, drying over anhydrous magnesium sulfate, filtration, removal of the solvent from the filtrate under reduced pressure with a rotary evaporator, and purification by column chromatography (EtOAc/PE (v/v) ═ 1/3) gave 0.29g of a white solid in yield: 70.1 percent.

¹H NMR(400MHz,CDCl₃):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 present 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, botrytis cinerea, peronospora cubensis and erysiphe necator

And (3) test treatment: the compound was dissolved in DMF to 1% EC for use. The bactericidal activity of these compounds at different doses against 4 test targets was evaluated using the in vivo potting method.

1) Pseudoperonospora cubensis test (Pseudoperonospora cubensis)

Selecting 1 potted cucumber seedling with consistent growth vigor in true leaf period (removing growing point), spraying, air drying, inoculating 24 hr later, taking fresh cucumber downy mildew diseased leaf, washing off sporocyst on back of diseased leaf with distilled water, and making into sporangium suspension (2-3X 10)⁵one/mL). Uniformly spraying and inoculating on cucumber seedlings by using an inoculation sprayer (the pressure is 0.1MPa), transferring inoculated test materials to an artificial climate chamber, keeping the relative humidity at 100% and the temperature at about 21 ℃, keeping the temperature at about 21 ℃ after 24 hours, keeping the relative humidity at about 95% for moisture induction, carrying out grading investigation according to blank control disease occurrence conditions after 5 days, and calculating the control effect according to disease indexes.

2) Cucumber powdery mildew test (Sphaerotheca fuliginea)

Selecting a cucumber seedling with a true leaf period and consistent growth vigor, and drying in the shade for 24 hours after spraying treatment. Washing fresh powdery mildew spores on cucumber leaves, filtering the fresh powdery mildew spores by using double-layer gauze to prepare suspension with the spore concentration of about 10 ten thousand/mL, and spraying for inoculation. And (3) transferring the inoculated test material into a climatic chamber, keeping the relative humidity between 60 and 70 percent, keeping the temperature between 21 and 23 ℃, carrying out grading investigation according to blank control disease occurrence conditions after about 10 days, and calculating the control effect according to disease indexes.

3) Cucumber gray mold (Botrytis cinerea)

The method adopts a leaf inoculation method. Two potted cucumber seedlings with the same growth vigor of the true leaf period are selected, and after the agent is sprayed and dried, a fungus cake is inoculated on the leaves. And (3) after 24-26 ℃ dark light moisture preservation is carried out for 24 hours, natural illumination moisture preservation culture is carried out for about 3 days. After the contrast is fully developed, the diameter of the lesion spot of each inoculation point is measured by a caliper, and the control effect is calculated.

4) Rhizoctonia solani (Rhizoctonia solani)

Selecting potted corn seedlings with two leaves and one heart and consistent growth vigor, naturally drying after spraying treatment, inoculating for about 24 hours, and inoculating a fungus cake on leaves after the medicament is sprayed and dried. And (3) after the dark light is moisturized for 24 hours at the temperature of 25-26 ℃, natural illumination is recovered for moisturizing and culturing for about 3 days. After the disease is sufficiently distributed in contrast, the length of the lesion spot of each inoculation point is measured by a caliper, and the control effect is calculated.

And (3) test results: the test results are shown in tables 3 and 4.

TABLE 3 control of cucumber downy mildew by the compounds of the invention at 200mg/L

Examples	control effect (%)
		Example 2	80
Example 4	100
		Example 5	98
example 6	90
		Example 12	80
Example 19	100

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

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

The results in tables 3 and 4 show that the compound has obvious control effect on cucumber downy mildew at different concentrations; in particular, example 19 showed good control of cucumber downy mildew even at low concentrations, wherein the control of cucumber downy mildew at 50mg/L of example 19 was 80% and the control of cucumber downy mildew at 25mg/L of example 19 was 60%.

The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.

Claims (10)

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

Wherein:

R¹Is hydrogen, alkyl, alkenyl, alkynyl, alkoxy, alkenyloxy, alkynyloxy, aryl, arylalkyl, heteroaryl, heteroarylalkyl, cycloalkyl, cycloalkylalkyl, heterocyclyl or heterocyclylalkyl; r¹Optionally substituted by 1,2,3, 4 or 5 substituents selected from R^aSubstituted with the substituent(s);

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

R²And R³Each independently is hydrogen, fluoro, chloro, bromo, iodo, hydroxy, cyano, nitro, amino, carboxy, alkyl, alkenyl, or alkynyl;

or-CR²R³-is-C (═ O) -;

n is 0, 1 or 2;

R⁴Is hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, heterocyclyl, aryl, arylalkyl, cycloalkylalkyl, or heterocyclylalkyl;

R⁵、R⁶、R⁷、R⁸And R⁹Each independently is hydrogen, fluoro, chloro, bromo, iodo, hydroxy, cyano, nitro, amino, carboxy, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, hydroxy-substituted alkyl, amino-substituted alkyl, cyano-substituted alkyl, alkoxy, haloalkoxy, hydroxy-substituted alkoxy, amino-substituted alkoxy, cyano-substituted alkoxy, alkylamino, alkylthio, or aryloxy;

Each R^aIndependently is fluorine, chlorine, bromine, iodine, hydroxyl, cyano, nitro, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, alkoxy, haloalkoxy, -C (═ O) -OR^cOr an aryloxy group;

Each R^bIndependently hydrogen, alkyl, alkenyl or alkynyl; and

each R^cIndependently hydrogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, cycloalkyl, heterocyclyl, aryl or heteroaryl。

2. The compound of claim 1, wherein

R¹is hydrogen, C_1-6Alkyl radical, C_2-6Alkenyl radical, C_2-6Alkynyl, C_1-6Alkoxy radical, C_2-6Alkenyloxy radical, C_2-6Alkynyloxy, C_6-10Aryl radical, C_6-10Aryl radical C_1-6Alkyl radical, C_1-9Heteroaryl group, C_1-9Heteroaryl C_1-6Alkyl radical, C_3-8Cycloalkyl radical, C_3-8Cycloalkyl radical C_1-6Alkyl radical, C_2-10Heterocyclyl or C_2-10Heterocyclyl radical C_1-6An alkyl group; r¹optionally substituted by 1,2,3, 4 or 5 substituents selected from R^aSubstituted with the substituent(s);

R²And R³Each independently is hydrogen, fluorine, chlorine, bromine, iodine, hydroxyl, cyano, nitro, amino, carboxyl, C_1-6Alkyl radical, C_2-6Alkenyl or C_2-6An alkynyl group;

or-CR²R³-is-C (═ O) -;

R⁴Is hydrogen, C_1-6Alkyl radical, C_2-6Alkenyl radical, C_2-6Alkynyl, C_3-8cycloalkyl radical, C_2-10Heterocyclic group, C_6-10Aryl radical, C_6-10Aryl radical C_1-6Alkyl radical, C_3-8Cycloalkyl radical C_1-6Alkyl or C_2-10Heterocyclyl radical C_1-6An alkyl group;

R⁵、R⁶、R⁷、R⁸And R⁹Each independently is hydrogen, fluorine, chlorine, bromine, iodine, hydroxyl, cyano, nitro, amino, carboxyl, C_1-6Alkyl radical, C_2-6Alkenyl radical, C_2-6Alkynyl, halo C_1-6Alkyl, halo C_2-6Alkenyl, halo C_2-6alkynyl, hydroxy-substituted C_1-6Alkyl, amino substituted C_1-6Alkyl, cyano-substituted C_1-6Alkyl radical, C_1-6Alkoxy, halo C_1-6Alkoxy, hydroxy-substituted C_1-6Alkoxy, amino substituted C_1-6Alkoxy, cyano-substituted C_1-6Alkoxy radical, C_1-6Alkylamino radical, C_1-6Alkylthio or C_6-10An aryloxy group;

Each R^aindependently fluorine, chlorine, bromine, iodine, hydroxyl, cyano, nitro, C_1-6alkyl radical, C_2-6Alkenyl radical, C_2-6Alkynyl, halo C_1-6Alkyl, halo C_2-6Alkenyl, halo C_2-6Alkynyl, C_1-6Alkoxy, halo C_1-6Alkoxy, -C (═ O) -OR^cOr C_6-10An aryloxy group;

Each R^bIndependently of one another is hydrogen, C_1-6Alkyl radical, C_2-6Alkenyl or C_2-6An alkynyl group; and

Each R^cIndependently of one another is hydrogen, C_1-6Alkyl radical, C_2-6Alkenyl radical, C_2-6Alkynyl, halo C_1-6Alkyl, halo C_2-6Alkenyl, halo C_2-6Alkynyl, C_3-8Cycloalkyl radical, C_2-6Heterocyclic group, C_6-10Aryl or C_1-5a heteroaryl group.

3. The compound of claim 2, wherein

R⁴Is hydrogen, C_1-4Alkyl radical, C_2-4Alkenyl radical, C_2-4Alkynyl, C_3-6Cycloalkyl radical, C_2-6Heterocyclic group, C_6-10Aryl radical, C_6-10Aryl radical C_1-4Alkyl radical, C_3-6Cycloalkyl radical C_1-3Alkyl or C_2-6Heterocyclyl radical C_1-3An alkyl group.

4. The compound of claim 3, wherein

R⁴Hydrogen, methyl, ethyl, n-propyl, isopropyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, phenyl or benzyl.

5. The compound of claim 2, wherein

R¹Is hydrogen, C_1-4Alkyl radical, C_2-4Alkenyl radical, C_2-4Alkynyl, C_1-4Alkoxy radical, C_2-4Alkenyloxy radical, C_2-4Alkynyloxy, C_6-10aryl radical, C_6-10Aryl radical C_1-3Alkyl radical, C_1-5Heteroaryl group, C_1-5Heteroaryl C_1-3Alkyl radical, C_3-6Cycloalkyl radical, C_3-6Cycloalkyl radical C_1-3Alkyl radical, C_2-6Heterocyclyl or C_2-6Heterocyclyl radical C_1-3An alkyl group; r¹Optionally substituted by 1,2,3, 4 or 5 substituents selected from R^asubstituted with the substituent(s); and

Each R^aIndependently fluorine, chlorine, bromine, iodine, hydroxyl, cyano, nitro, C_1-4Alkyl radical, C_2-4Alkenyl radical, C_2-4Alkynyl, halo C_1-4Alkyl, halo C_2-4Alkenyl, halo C_2-4Alkynyl, C_1-4alkoxy, halo C_1-4Alkoxy, -C (═ O) -OC_1-3Alkyl or C_6-10An aryloxy group.

6. The compound of claim 5, wherein

R¹Is hydrogen, methyl, ethyl, n-propyl, isopropyl, vinyl, allyl, propenyl, methoxy, ethoxy, n-propoxy, isopropoxy, phenyl, benzyl or pyridyl;

R¹Optionally substituted by 1,2,3, 4 or 5 substituents selected from R^aSubstituted with the substituent(s); and

Each R^aIndependently hydrogen, fluorine, chlorine, bromine, iodine, hydroxyl, cyano, nitro, methyl, ethyl, n-propyl, isopropyl, phenoxy, methoxy, ethoxy, n-propoxy, isopropoxy or-C (═ O) -OCH₃。

7. The compound of claim 1, which is a compound of formula (II) or a stereoisomer, nitroxide, and salt of a compound of formula (II):

8. The compound according to any one of claims 1 to 7, which is a compound having one of the following structures or a stereoisomer, a nitroxide or a salt of a compound having one of the following structures:

9. A composition comprising a compound of any one of claims 1-8; further comprises an agriculturally pharmaceutically acceptable surfactant and/or carrier.

10. Use of the compound according to any one of claims 1 to 8 or the composition according to claim 9 for controlling plant diseases.