CN113929665B - Aryl-substituted triazole sulfonamide derivative, and preparation method and application thereof - Google Patents

Abstract

The present invention relates to an aromatic substituted triazole sulfonamide derivative, a preparation method and application thereof; specifically, the present invention relates to an aromatic substituted triazole sulfonamide derivative represented by formula (I) or a stereoisomer, nitrogen oxide or salt thereof of the aromatic substituted triazole sulfonamide derivative represented by formula (I), and a preparation method of the aromatic substituted triazole sulfonamide derivative, and their use as fungicides in agriculture, and the form of a composition thereof, and a method for controlling plant diseases using these compounds or compositions; wherein ^R1 and ^R2 are each independently a _C1-4 alkyl group, Hy is a 5-10 membered heteroaryl group, and Hy is optionally substituted by a substituent described in the present invention.

Description

Aryl-substituted triazole sulfonamide derivative, and preparation method and application thereof

Technical Field

The invention belongs to the field of pesticides, and particularly relates to an aryl-substituted triazole sulfonamide derivative, a preparation method and application thereof as a bactericide in agriculture.

Background

In modern agricultural production, various pesticides are required to be used for ensuring healthy growth of crops, the bactericidal activity of the existing compounds is always insufficient under the condition of relatively low application rate, and the pesticide resistance of diseases on crops to the existing pesticides is caused by frequent use of the pesticides for a long time, so that the control effect of the pesticides is reduced, and in order to solve the problems of high efficiency or drug resistance, the novel compounds for controlling plant diseases are required to be continuously sent out.

Disclosure of Invention

The invention provides an aryl-substituted triazole sulfonamide derivative which has excellent control effect on plant diseases, especially on cucumber downy mildew at low dosage.

In particular, the method comprises the steps of,

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

Wherein:

R ¹ and R ² are each independently hydrogen, C _1-4 alkyl, C _2-4 alkenyl, C _2-4 alkynyl, C _3-6 cycloalkyl, C _3-6 cycloalkyl-C _1-3 alkylene-, phenyl optionally substituted with 1,2,3, 4 or 5 groups selected from fluoro, chloro, bromo, iodo, C _1-4 alkyl, C _1-4 alkoxy, halo C _1-4 alkyl or halo C _1-4 alkoxy, or benzyl optionally substituted with 1,2,3, 4 or 5 groups selected from fluoro, chloro, bromo, iodo, C _1-4 alkyl, C _1-4 alkoxy, halo C _1-4 alkyl or halo C _1-4 alkoxy;

Or R ¹、R² and the nitrogen atom to which it is attached form a 3-6 membered heterocyclic ring or a 5-10 heteroaryl group, said 3-6 membered heterocyclic ring or 5-10 heteroaryl group optionally being substituted with 1 or 2 groups selected from fluorine, chlorine, bromine, iodine or C _1-4 alkyl;

n is 0, 1 or 2;

Hy is a 5-to 10-membered heteroaryl group, wherein Hy is optionally substituted with 1,2 or 3 groups selected from fluorine, chlorine, bromine, iodine, cyano, hydroxy, nitro, carboxy, -C (=O) H, C _1-4 alkyl, C _1-4 alkoxy, C _1-4 alkylthio, Halogenated C _1-4 alkyl, halogenated C _1-4 alkoxy, halogenated C _1-4 alkylthio, C _3-6 cycloalkyl, C _3-6 cycloalkyl-C _1-3 alkylene-, C _1-4 alkoxy-C (=O) -, C _1-4 alkyl-C (=O) -, Phenyl optionally substituted with 1,2,3,4 or 5 groups selected from fluorine, chlorine, bromine, iodine, cyano, hydroxy, nitro, carboxyl, C _1-4 alkyl, C _1-4 alkoxy, halogenated C _1-4 alkyl or halogenated C _1-4 alkoxy or optionally substituted with 1,2,3 or 5 groups selected from fluorine, chlorine, bromine, iodine, cyano, hydroxy, nitro, carboxyl, C _1-4 alkyl, halogen C _1-4 alkoxy, halogen C _1-4 alkyl or halogen C _1-4 alkoxy, 2.3 or 4 5-6 membered heteroaryl substitutions selected from fluoro, chloro, bromo, iodo, cyano, hydroxy, nitro, carboxy, C _1-4 alkyl, C _1-4 alkoxy, halo C _1-4 alkyl or halo C _1-4 alkoxy.

In some embodiments, R ¹ and R ² are each independently hydrogen, C _1-4 alkyl, C _2-4 alkenyl, or C _2-4 alkynyl.

In other embodiments, R ¹ and R ² are each independently hydrogen 、-CH₃、-CH₂CH₃、-CH₂CH₂CH₃、-CH(CH₃)₂、-CH₂CH₂CH₂CH₃、-CH₂CH(CH₃)₂、-CH＝CH₂、-CH₂CH＝CH₂、-CCH or-CH ₂ CCH.

In some embodiments, R ¹、R² and the nitrogen atom to which it is attached form a 3-6 membered heterocyclic ring, said 3-6 membered heterocyclic ring optionally being substituted with 1 or 2 groups selected from fluorine, chlorine, bromine, iodine or-CH ₃.

In other embodiments, R ¹、R² and the nitrogen atom attached thereto form the following sub-structural formula:

Preferably, in some embodiments, R ¹ and R ² are each independently C _1-4 alkyl.

More preferably, in some embodiments, R ¹ and R ² are each independently-CH ₃.

Preferably, in some embodiments, n is 2.

In some embodiments, hy is

Wherein R ^a is phenyl optionally substituted with 1,2,3, 44, or 5 groups selected from fluoro, chloro, bromo, iodo, cyano, hydroxy, nitro, carboxy, C _1-4 alkyl, C _1-4 alkoxy, halo C _1-4 alkyl, or halo C _1-4 alkoxy or a 5-to 6-membered heteroaryl optionally substituted with 1,2,3, or 4 groups selected from fluoro, chloro, bromo, iodo, cyano, hydroxy, nitro, carboxy, C _1-4 alkyl, C _1-4 alkoxy, halo C _1-4 alkyl, or halo C _1-4 alkoxy;

r ^b is hydrogen, fluoro, chloro, bromo, iodo, cyano, hydroxy, nitro, carboxy, -C (=O) H, C _1-4 alkyl, C _1-4 alkoxy, C _1-4 alkylthio, halo C _1-4 alkyl, halo C _1-4 alkoxy, halo C _1-4 alkylthio, C _3-6 cycloalkyl, C _3-6 cycloalkyl-C _1-3 alkylene-, C _1-4 alkoxy-C (=O) -or C _1-4 alkyl-C (=O) -;

R ^c is hydrogen, fluoro, chloro, bromo, iodo, cyano, hydroxy, nitro, carboxy, -C (=O) H, C _1-4 alkyl, C _1-4 alkoxy, C _1-4 alkylthio, Halogenated C _1-4 alkyl, halogenated C _1-4 alkoxy, halogenated C _1-4 alkylthio, C _3-6 cycloalkyl, C _3-6 cycloalkyl-C _1-3 alkylene-, C _1-4 alkoxy-C (=O) -, C _1-4 alkyl-C (=O) -, Phenyl optionally substituted with 1,2,3, 4 or 5 groups selected from fluorine, chlorine, bromine, iodine, C _1-4 alkyl, C _1-4 alkoxy, halogenated C _1-4 alkyl or halogenated C _1-4 alkoxy or optionally substituted with 1, 2. 3 or 4 5-6 membered heteroaryl groups selected from fluorine, chlorine, bromine, iodine, C _1-4 alkyl, C _1-4 alkoxy, halogenated C _1-4 alkyl or halogenated C _1-4 alkoxy.

In other embodiments, hy is

Wherein R ^a is phenyl optionally substituted with 1,2, 3, 4, or 5 groups selected from fluorine, chlorine, bromine, iodine, cyano, hydroxy, nitro, carboxy, -CH ₃、-OCH₃、-CF₃, or-OCF ₃, pyridyl optionally substituted with 1,2, 3, or 4 groups selected from fluorine, chlorine, bromine, iodine, cyano, hydroxy, nitro, carboxy, -CH ₃、-OCH₃、-CF₃, or-OCF ₃, or thienyl optionally substituted with 1,2, or 3 groups selected from fluorine, chlorine, bromine, iodine, cyano, hydroxy, nitro, carboxy, -CH ₃、-OCH₃、-CF₃, or-OCF ₃;

R ^b is hydrogen, fluorine, chlorine, bromine, iodine, cyano, hydroxy, nitro, carboxyl, -C (=O) H, -CH ₃、-OCH₃、-SCH₃、-CF₃、-OCF₃, or-SCF ₃;

R ^c is hydrogen, fluorine, chlorine, bromine, iodine, cyano, hydroxyl, nitro, carboxyl, -C (=O) H, -CH ₃、-OCH₃、-SCH₃、-CF₃、-OCF₃、-SCF₃, phenyl optionally substituted with 1,2,3, 4 or 5 groups selected from fluorine, chlorine, bromine, iodine, -CH ₃、-OCH₃、-CF₃ or-OCF ₃, or pyridyl optionally substituted with 1,2,3 or 4 groups selected from fluorine, chlorine, bromine, iodine, -CH ₃、-OCH₃、-CF₃ or-OCF ₃, or thienyl optionally substituted with 1,2 or 3 groups selected from fluorine, chlorine, bromine, iodine, -CH ₃、-OCH₃、-CF₃ or-OCF ₃.

Preferably, in some embodiments, R ^a is phenyl optionally substituted with 1 or 2 substituents selected from fluorine, chlorine, bromine, iodine, cyano, hydroxy, nitro, carboxy, -CH ₃、-OCH₃、-CF₃, or-OCF ₃ or pyridin-2-yl optionally substituted with 1,2, 3, or 4 substituents selected from fluorine, chlorine, bromine, iodine, cyano, hydroxy, nitro, carboxy, -CH ₃、-OCH₃、-CF₃, or-OCF ₃.

More preferably, in some embodiments, R ^a is phenyl or pyridin-2-yl optionally substituted with 1 or 2 groups selected from fluorine, chlorine, bromine, iodine, -CH ₃、-OCH₃、-CF₃, or-OCF ₃.

The pyridine-2-yl isIndicating the attachment position to the other part of the molecule.

Preferably, in some embodiments, R ^b is hydrogen, fluoro, chloro, bromo, iodo, cyano, hydroxy, nitro, carboxyl, -C (=o) H, or-CH ₃.

More preferably, in some embodiments, R ^b is hydrogen or-CH ₃.

Preferably, in some embodiments, R ^c is hydrogen.

In some embodiments, hy is

In some embodiments, hy is

Wherein R ^d is phenyl optionally substituted with 1,2,3, 4, or 5 groups selected from fluoro, chloro, bromo, iodo, cyano, hydroxy, nitro, carboxy, C _1-4 alkyl, C _1-4 alkoxy, halo C _1-4 alkyl, or halo C _1-4 alkoxy or a 5-to 6-membered heteroaryl optionally substituted with 1,2,3, or 4 groups selected from fluoro, chloro, bromo, iodo, cyano, hydroxy, nitro, carboxy, C _1-4 alkyl, C _1-4 alkoxy, halo C _1-4 alkyl, or halo C _1-4 alkoxy;

r ^e is hydrogen, fluoro, chloro, bromo, iodo, cyano, hydroxy, nitro, carboxy, -C (=O) H, C _1-4 alkyl, C _1-4 alkoxy, C _1-4 alkylthio, halo C _1-4 alkyl, halo C _1-4 alkoxy, halo C _1-4 alkylthio, C _3-6 cycloalkyl, C _3-6 cycloalkyl-C _1-3 alkylene-, C _1-4 alkoxy-C (=O) -or C _1-4 alkyl-C (=O) -;

R ^f is hydrogen, fluoro, chloro, bromo, iodo, cyano, hydroxy, nitro, carboxy, -C (=O) H, C _1-4 alkyl, C _1-4 alkoxy, C _1-4 alkylthio, Halogenated C _1-4 alkyl, halogenated C _1-4 alkoxy, halogenated C _1-4 alkylthio, C _3-6 cycloalkyl, C _3-6 cycloalkyl-C _1-3 alkylene-, C _1-4 alkoxy-C (=O) -, C _1-4 alkyl-C (=O) -, Phenyl optionally substituted with 1,2,3, 4 or 5 groups selected from fluorine, chlorine, bromine, iodine, C _1-4 alkyl, C _1-4 alkoxy, halogenated C _1-4 alkyl or halogenated C _1-4 alkoxy or optionally substituted with 1, 2. 3 or 4 5-6 membered heteroaryl groups selected from fluorine, chlorine, bromine, iodine, C _1-4 alkyl, C _1-4 alkoxy, halogenated C _1-4 alkyl or halogenated C _1-4 alkoxy.

In other embodiments, hy is

Wherein R ^d is phenyl optionally substituted with 1,2, 3, 4, or 5 groups selected from fluorine, chlorine, bromine, iodine, cyano, hydroxy, nitro, carboxy, -CH ₃、-OCH₃、-CF₃, or-OCF ₃, pyridyl optionally substituted with 1,2, 3, or 4 groups selected from fluorine, chlorine, bromine, iodine, cyano, hydroxy, nitro, carboxy, -CH ₃、-OCH₃、-CF₃, or-OCF ₃, or thienyl optionally substituted with 1,2, or 3 groups selected from fluorine, chlorine, bromine, iodine, cyano, hydroxy, nitro, carboxy, -CH ₃、-OCH₃、-CF₃, or-OCF ₃;

R ^e is hydrogen, fluorine, chlorine, bromine, iodine, cyano, hydroxy, nitro, carboxyl, -C (=O) H, -CH ₃、-OCH₃、-SCH₃、-CF₃、-OCF₃, or-SCF ₃;

R ^f is hydrogen, fluorine, chlorine, bromine, iodine, cyano, hydroxyl, nitro, carboxyl, -C (=O) H, -CH ₃、-OCH₃、-SCH₃、-CF₃、-OCF₃、-SCF₃, phenyl optionally substituted with 1,2,3, 4 or 5 groups selected from fluorine, chlorine, bromine, iodine, -CH ₃、-OCH₃、-CF₃ or-OCF ₃, pyridyl optionally substituted with 1,2,3 or 4 groups selected from fluorine, chlorine, bromine, iodine, -CH ₃、-OCH₃、-CF₃ or-OCF ₃, or thienyl optionally substituted with 1,2 or 3 groups selected from fluorine, chlorine, bromine, iodine, -CH ₃、-OCH₃、-CF₃ or-OCF ₃.

Preferably, in some embodiments, R ^d is phenyl, pyridin-2-yl or thiophen-2-yl optionally substituted with 1 member selected from fluorine, chlorine, bromine or iodine.

The thiophene-2-radical is

Preferably, in some embodiments, R ^e is hydrogen or-C (=o) H.

Preferably, in some embodiments, R ^f is hydrogen.

In some embodiments, hy is

In some embodiments, hy is

Wherein R ^g is phenyl optionally substituted with 1,2,3, 4, or 5 groups selected from fluorine, chlorine, bromine, iodine, cyano, hydroxy, nitro, carboxyl, C _1-4 alkyl, C _1-4 alkoxy, halo C _1-4 alkyl, or halo C _1-4 alkoxy or a 5-6 membered heteroaryl optionally substituted with 1,2,3, or 4 groups selected from fluorine, chlorine, bromine, iodine, cyano, hydroxy, nitro, carboxyl, C _1-4 alkyl, C _1-4 alkoxy, halo C _1-4 alkyl, or halo C _1-4 alkoxy.

In other embodiments, hy is

Wherein R ^g is phenyl optionally substituted with 1,2,3,4, or 5 groups selected from fluorine, chlorine, bromine, iodine, cyano, hydroxy, nitro, carboxy, -CH ₃、-OCH₃、-CF₃, or-OCF ₃ or pyridyl optionally substituted with 1,2,3, or 4 groups selected from fluorine, chlorine, bromine, iodine, cyano, hydroxy, nitro, carboxy, -CH ₃、-OCH₃、-CF₃, or-OCF ₃.

Preferably, in some embodiments, R ^g is phenyl optionally substituted with 1 or 2 groups selected from fluorine, chlorine, bromine, iodine, C _1-4 alkyl or halogenated C _1-4 alkyl or pyridin-3-yl optionally substituted with 1 group selected from fluorine, chlorine, bromine or iodine.

More preferably, in some embodiments, R ^g is phenyl optionally substituted with 1 or 2 groups selected from fluorine, chlorine, bromine, iodine, or-CF ₃ or pyridin-3-yl optionally substituted with 1 group selected from fluorine, chlorine, bromine, or iodine.

The pyridine-3-yl is

In other embodiments, hy is

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

In another aspect, the present invention provides a composition comprising at least one compound of the invention and an adjuvant commonly used in agro-pharmaceuticals.

In yet another aspect, the present invention provides the use of a compound of the present invention or a composition of the present invention as a plant disease control agent in agriculture.

In yet another aspect, the present invention provides a method of controlling plant diseases comprising applying an effective amount of a compound of the present invention or a composition comprising an effective amount of a compound of the present invention to a plant, plant part or plant growing environment.

The disease is caused by phytopathogenic fungi.

The disease is preferably downy mildew.

The plant disease is preferably cucumber downy mildew.

Detailed description of the invention

Definitions and general terms

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

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

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

The following definitions as used herein should be applied unless otherwise indicated. For the purposes of the present invention, chemical elements are in accordance with CAS version of the periodic Table of the elements, and handbook of chemistry and physics, 75 th edition, 1994. In addition, the general principles of organic chemistry may be found in the descriptions of "Organic Chemistry", thomas Sorrell, university Science Books, sausalato 1999, and "March's Advanced Organic Chemistry"by Michael B.Smith and Jerry March,John Wiley&Sons,New York:2007, the entire contents of which are incorporated herein by reference.

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

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

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

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

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

The stereochemical definitions and rules used in the present invention generally follow the description in S.P.Parker,Ed.,McGraw-Hill Dictionary of Chemical Terms(1984)McGraw-Hill Book Company,New York;and Eliel,E.and Wilen,S.,"Stereochemistry of Organic Compounds",John Wiley&Sons,Inc.,New York,1994.

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

Any asymmetric atom (e.g., carbon, etc.) of the disclosed compounds may exist in racemic or enantiomerically enriched form, such as in the (R) -, (S) -or (R, S) -configuration. 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 be present in the form of one of the possible isomers or mixtures thereof, for example racemates and non-corresponding isomer mixtures, 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 substituent may be in E or Z configuration, and if the compound contains a disubstituted cycloalkyl, the substituent of the cycloalkyl may be in cis or trans configuration.

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

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

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

In addition, unless explicitly stated otherwise, the description as used in this disclosure is "each..and". Independently "and". Independently "can be interchanged, and is to be understood broadly as meaning that specific items expressed between the same symbols in different groups do not affect each other, or that specific items expressed between the same symbols in the same groups do not affect each other.

In the various parts of the present specification, substituents of the presently disclosed compounds are disclosed in terms of the type or scope of groups. It is specifically noted that the present invention includes each individual subcombination of the individual members of these group classes and ranges. For example, the term "C ₁-C₆ alkyl" or "C _1-6 alkyl" refers specifically to independently disclosed methyl, ethyl, C ₃ alkyl, C ₄ alkyl, C ₅ alkyl, and C ₆ alkyl.

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

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

The term "alkenyl" denotes a straight or branched chain monovalent hydrocarbon radical containing 2 to 12 carbon atoms, wherein there is at least one site of unsaturation, i.e. one carbon-carbon sp ² double bond, wherein the alkenyl group may be optionally substituted with one or more substituents as described herein, including the positioning of "cis" and "tans", or the positioning of "E" and "Z". In one embodiment, the alkenyl group comprises 2 to 8 carbon atoms, in another embodiment the alkenyl group comprises 2 to 6 carbon atoms, and in yet another embodiment the alkenyl group comprises 2 to 4 carbon atoms. Examples of alkenyl groups include, but are not limited to, vinyl (-ch=ch ₂), allyl (-CH ₂CH＝CH₂), propenyl (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, wherein the alkynyl group may be optionally substituted with one or more substituents described herein. In one embodiment, the alkynyl group contains 2 to 10 carbon atoms, in one embodiment the alkynyl group contains 2 to 8 carbon atoms, in another embodiment the alkynyl group contains 2 to 6 carbon atoms, and in yet another embodiment the alkynyl group contains 2 to 4 carbon atoms. Examples of alkynyl groups include, but are not limited to ,-C≡CH、-C≡CCH₃、-CH₂-C≡CH、-CH₂-C≡CCH₃、-CH₂CH₂-C≡CH、-CH₂-C≡CCH₂CH₃、-CH₂CH₂-C≡CCH₃, and the like.

The term "alkoxy" means that the alkyl group is attached to the remainder of the molecule through an oxygen atom, wherein the alkyl group has the meaning as described herein. Examples of alkoxy groups include, but are not limited to, methoxy (MeO, -OCH ₃), ethoxy (EtO, -OCH ₂CH₃), 1-propoxy (n-PrO, n-propoxy, -OCH ₂CH₂CH₃), 2-propoxy (i-PrO, i-propoxy, -OCH (CH ₃)₂), and the like.

The term "alkylthio" means that the 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, cycloalkyl groups comprise 3 to 10 carbon atoms, in another embodiment cycloalkyl groups comprise 3 to 8 carbon atoms, and in yet another embodiment cycloalkyl groups comprise 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 term "cycloalkyl-alkylene" means that the cycloalkyl group is attached to the rest of the molecule through an alkylene group, wherein alkylene and cycloalkyl groups have the meaning as described herein. Examples include, but are not limited to, cyclopropyl-CH ₂ -, cyclobutyl-CH ₂ -, cyclopentyl-CH ₂ -, cyclohexyl-CH ₂ -, and the like.

In the various parts of the present specification, linking substituents are described. When the structure clearly requires a linking group, the markush variables recited for that group are understood to be linking groups. For example, if the structure requires a linking group and the markush group definition for that variable enumerates an "alkyl" or "aryl" group, it will be understood that the "alkyl" or "aryl" represents a linked alkylene group or arylene group, respectively.

The term "alkylene" refers to a saturated divalent hydrocarbon group resulting from the removal of two hydrogen atoms from a saturated straight or branched hydrocarbon. Unless otherwise specified, alkylene groups contain 1 to 12 carbon atoms. In one embodiment, the alkylene groups contain 1 to 8 carbon atoms, in one embodiment the alkylene groups contain 1 to 6 carbon atoms, in another embodiment the alkylene groups contain 1 to 4 carbon atoms, in yet another embodiment the alkylene groups contain 1 to 3 carbon atoms, and in yet another embodiment the alkylene groups contain 1 to 2 carbon atoms. Examples include methylene (-CH ₂ -), ethylene (-CH ₂CH₂ -), propylene (-CH₂CH₂CH₂-),-CH(CH₃)CH₂-,-C(CH₃)₂-,-CH₂CH₂CH(CH₃)-,-CH₂CH₂C(CH₃)₂-,, and the like.

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

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

The terms "3-12 membered heterocyclyl", "3-10 membered heterocyclyl", "3-8 membered heterocyclyl" or "3-6 membered heterocyclyl", wherein "3-12 membered", "3-10 membered", "3-8 membered" or "3-6 membered" typically describes the number of ring forming atoms in the molecule. For example, tetrahydrofuranyl is a 5 membered heterocyclic group and piperidinyl is a 6 membered heterocyclic group.

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

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

The term "heteroaryl" means monocyclic, bicyclic and tricyclic ring systems containing 5 to 12 ring atoms, or 5 to 10 ring atoms, or 5 to 6 ring atoms, wherein at least one ring system is aromatic and at least one ring system contains one or more heteroatoms, wherein each ring system contains a ring of 5 to 7 atoms and has one or more attachment points attached to the remainder of the molecule. The term "heteroaryl" may be used interchangeably with the term "heteroaromatic ring" or "heteroaromatic compound". The heteroaryl group is optionally substituted with one or more substituents described herein. In one embodiment, the heteroaryl group of 5 to 10 atoms comprises 1,2,3 or 4 heteroatoms independently selected from O, S and N.

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, N-pyrazolyl, isothiazolyl, 1,2, 3-oxadiazolyl, 1,2, 5-oxadiazolyl, 1,2, 4-oxadiazolyl, 1,2, 3-triazolyl, 1,2, 3-thiodiazolyl, 1,3, 4-thiodiazolyl, 1,2, 5-thiodiazolyl, pyrazinyl, 1,3, 5-triazinyl, pyrimidinonyl, pyridonyl; also included are, but in no way limited to, bicyclic rings of benzimidazolyl, benzofuranyl, benzothienyl, indolyl (e.g., 2-indolyl), benzopiperidinyl, and the like.

The terms "5-12 membered heteroaryl", "5-10 membered heteroaryl" or "5-6 membered heteroaryl", wherein "5-12 membered", "5-10 membered" or "5-6 membered" typically describes the number of ring forming atoms in the molecule. For example, pyrrolyl, pyrazolyl, imidazolyl, thienyl, isothiazolyl, thiazolyl, furanyl, isoxazolyl and oxazolyl are 5 membered heteroaryl, and pyridyl, pyrimidinyl, pyrazinyl and pyridazinyl are 6 membered heteroaryl.

The term "haloalkyl" means an alkyl group substituted with one or more halogen atoms, examples of which include, but are not limited to ,-CF₃,-CHF₂,-CH₂Cl,-CH₂CF₃,-CH₂CHF₂,-CH₂CH₂F,-CH₂CH₂Cl,-CH₂CH₂CF₃, and the like.

The term "haloalkoxy" means that the alkoxy group is substituted with one or more halogen atoms, examples of which include, but are not limited to ,-OCF₃,-OCHF₂,-OCHCl₂,-OCH₂CHF₂,-OCH₂CHCl₂,-OCH(CH₃)CHF₂, and the like.

The term "haloalkylthio" means that the alkylthio group is substituted with one or more halogen atoms, examples of which include, but are not limited to, difluoromethylthio (-SCF ₂), trifluoromethylthio (-SCF ₃), and the like.

The term "cyano" refers to-CN.

The term "hydroxy" refers to-OH.

The term "nitro" refers to-NO ₂.

The term "carboxy" refers to-COOH.

Salts of the compounds of the present invention include those derived from alkali metals or alkaline earth metals, as well as those derived from ammonia and amines. Preferred cations include sodium, potassium, magnesium and ammonium cations of formula N ⁺(R^AR^BR^CR^D) wherein R ^A、R^B、R^C and R ^D are independently selected from the group consisting of hydrogen, C ₁-C₆ alkyl and C ₁-C₆ hydroxyalkyl. Salts of the compounds of formula (I) may be prepared by treating the compounds of formula (I) with a metal hydroxide (e.g., sodium hydroxide) or an amine (e.g., ammonia, trimethylamine, diethanolamine, 2-methylthiopropylamine, bisallylamine, 2-butoxyethylamine, morpholine, cyclododecamine, or benzylamine).

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

Compositions and formulations of the compounds of the invention

The compounds of the present invention are generally useful as bactericidal active ingredients in compositions or formulations, and typically also include adjuvants commonly used in agro-pharmaceuticals, including surfactants and/or carriers.

The surfactant may be any of various surfactants known in the art of agricultural chemical formulation, and the present invention is preferably one or more of an emulsifier, a dispersant and a wetting agent.

Other carriers besides the above surfactants may be various carriers well known in the art of agricultural chemical formulation, including various silicates, carbonates, sulfates, oxides, phosphates, plant carriers, synthetic carriers. Specifically, for example, one or more of white carbon black, kaolin, diatomaceous earth, clay, talc, organobentonite, 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 various emulsifiers known in the field of pesticide formulation, and specifically, the emulsifier may be one or more of calcium dodecyl benzene sulfonate, triphenyl ethyl phenol 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 pesticide formulation field, and specifically, the dispersing agent is one or more of acrylic acid homopolymer sodium salt, maleic acid disodium salt, naphthalene sulfonic acid formaldehyde condensate sodium salt, rosin block polyoxyethylene ether polyoxypropylene ether sulfonate, hydroxyl-terminated polyoxyethylene polyoxypropylene ether block copolymer, triphenyl ethyl phenol polyoxyethylene ether phosphate, fatty alcohol polyoxyethylene ether phosphate and p-hydroxyphenyl lignin sulfonic acid sodium salt.

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

The bactericidal composition according to the present invention may further contain various adjuvants for formulation commonly used in the field of agricultural chemical formulation, and specifically, the adjuvants for formulation may be one or more of solvents, co-solvents, thickeners, antifreezes, encapsulating materials, protectants, antifoaming agents, disintegrants, stabilizers, preservatives and binders.

The above solvent may be various solvents well known in the field of agricultural chemical formulation, and specifically, the solvent may be one or more of organic solvents, vegetable oils, mineral oils, solvent oils and water.

Wherein the organic solvent comprises one or more of N-methylpyrrolidone, tetrahydrofuran, dimethyl sulfoxide, N-dimethyl capramide, N-dimethylformamide, trimethylbenzene, tetramethylbenzene, xylene, toluene, 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, turpentine-based vegetable oil, turpentine, epoxidized soybean oil, peanut oil, rapeseed oil, castor oil, corn oil and pine seed oil.

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

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

The above antifreezing agent may be various antifreezing agents known in the field of agricultural chemical formulation, and the present invention is preferably one or more of ethylene glycol, propylene glycol, glycerin and urea.

The thickener may be various thickeners known in the field of pesticide dosage forms, and specifically, the thickener may be one or more of xanthan gum, polyvinyl alcohol, polyacrylate alcohol, polyethylene glycol, white carbon black, diatomaceous earth, kaolin, clay, sodium alginate, aluminum magnesium silicate, aluminum sodium silicate, carboxymethyl cellulose, hydroxypropyl cellulose sodium, and organic bentonite.

The capsule wall material can be various capsule wall materials known in the pesticide formulation field, 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 agricultural chemical formulations, and the present invention is preferably polyvinyl alcohol and/or polyethylene glycol.

The above defoamer may be various defoamers known in the field of pesticide formulation, and the present invention is preferably one or more of organosiloxane, tributyl phosphate and silicone.

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

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

The invention also provides a preparation prepared from the bactericidal composition, and the preparation formulation of the preparation is emulsifiable concentrate, aqueous emulsion, microemulsion, soluble liquid, aqueous suspension, suspension emulsion, ultra-low volume spray, oil suspension, microcapsule suspension, water spreading oil, wettable powder, water dispersible granules, dry suspension, soluble powder, soluble granules, emulsifiable powder, emulsifiable granules, solid microcapsule preparation, effervescent tablets, effervescent granules, water floating dispersible granules or seed coating. The above dosage forms 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, thus obtaining the emulsifiable concentrate preparation.

The aqueous emulsion may be prepared by mixing the active ingredient, the emulsifier, the cosolvent and the solvent to form a homogeneous oil phase, and mixing water, the thickener, the antifreezing agent and the like to form a homogeneous 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 by mixing and stirring the active ingredient, the emulsifier and the solvent into a uniform transparent oil phase. Under stirring, water was gradually added to form a uniform transparent microemulsion.

The preparation method of the water/oil suspending agent comprises the steps of taking water or oil as a medium, adding the active components, the surfactant and other auxiliary agents into a sanding kettle, grinding to a certain particle size, and filtering. And adding the metered thickener into the ground mother solution, and shearing and dispersing uniformly. Making into oil suspension or water suspension.

The water-dispersible granule and the soluble granule can be prepared by, for example, uniformly mixing the active components, the dispersing agent, the wetting agent, the carrier and the like, then crushing the mixture to a certain particle size by air flow, adding water for kneading, finally adding the mixture into a granulator for granulating, and drying the mixture to obtain the water-dispersible granule or the soluble granule.

The preparation method of the soluble powder and the wettable powder comprises the steps of fully mixing the active components, various auxiliary agents, other carriers and other fillers, and crushing the mixture by a superfine crusher.

The bactericidal composition of the invention can be provided in the form of finished preparations, i.e. the substances in the composition are mixed, or can be provided in the form of individual preparations, and can be mixed by itself in a barrel or a tank before use, and can be diluted by selectively mixing with water according to the concentration of the required active substances.

Use of the compounds and compositions of the invention

The compounds of the present invention are useful as plant disease controlling agents. Thus, 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 to a part thereof an effective amount of a compound of the invention or a fungicidal composition comprising said compound. The compounds and/or compositions of the present invention provide control of diseases caused by broad-spectrum plant pathogenic fungi of basidiomycetes, ascomycetes, oomycetes and deuteromycetes. They are effective in controlling a broad spectrum of plant diseases, especially foliar pathogens in ornamental, lawn, vegetable, field, cereal and fruit crops. These pathogens include oomycetes, including Phytophthora (Phytophthora) diseases such as Phytophthora infestans (Phytophthora infestans), phytophthora sojae (Phytophthora megasperma), foot-rot citrus bacteria (Phytophthora parasitica), Diseases of phytophthora cinnamomi (Phytophthora cinnamomi) and cucurbita moschata (Phytophthora capsici), diseases of the species Pythum species such as Pythum Pythium trichum (Pythium aphanidermatum), and diseases of the species of the family Peronospora such as Botrytis cinerea (Plasmopara viticola), diseases of the genus Peronospora (including Peronospora tabilis (Peronospora tabacina) and Peronospora parasitica (Peronospora parasitica)), diseases of the genus Pseudomonas (Pseudoperonospora spp) (including Peronospora cucumeria (Pseudoperonospora cubensis) and Bremia lactucae); ascomycetes (including Alternaria (Alternaria) pathogens such as Alternaria solani (ALTERNARIA SOLANI) and Alternaria brassicae (ALTERNARIA BRASSICAE), alternaria (Guignardia) pathogens such as Alternaria viticola (Guignardia bidwell), alternaria (Venturia) pathogens such as Alternaria mali (Venturia inaequalis), septoria (Septoria) pathogens such as Alternaria glumae (Septoria nodorum) and Alternaria leaf blight (Septoria tritici), erysiphe (powdery mildew) pathogens such as Alternaria graminis (Erysiphe spp.) (including Alternaria graminis (ERYSIPHE GRAMINIS) and Alternaria glonoides (Erysiphe polygoni)) Powdery mildew (Uncinula necatur), powdery mildew (Sphaerotheca fuligena) and powdery mildew (Podosphaera leucotricha) of cucumber, powdery mildew (Pseudocercosporella herpotrichoides) of wheat, botrytis (Botrytis) diseases such as Botrytis cinerea (Botrytis cinerea), brown rot of peach (Monilinia fructicola), sclerotinia (Sclerotinia) diseases such as Sclerotinia sclerotiorum (Sclerotinia sclerotiorum), pyricularia oryzae (Magnaporthe grisea), rhizoctonia solani (Phomopsis viticola), helminthosporium (Helminthosporium) diseases such as Rhizoctonia cerealis (Helminthosporium TRITICI REPENTIS), Anilox bacteria (Pyrenophora teres), anthrax bacteria such as black fruit bacteria (Glomerella) or Colletotrichum spp diseases such as Colletotrichum anthracis (Colletotrichum graminicola) and watermelon anthracis (Colletotrichum orbiculare), and wheat take-all bacteria (Gaeumannomyces graminis), basidiomycetes including rust diseases caused by rust (Puccinia spp.) such as Puccinia recondita (Puccinia recondita), puccinia recondita (Puccinia recondita), Rumex strigosus (Puccinia striiformis), rumex leaf (Puccinia hordei), rust (Puccinia graminis) and puccinia (Puccinia arachidis)), puccinia (Hemileia vastatrix) and soybean rust (Phakopsora pachyrhizi), other pathogens including Rhizoctonia species (Rhizoctonia spp.) (such as Rhizoctonia solani (Rhizoctonia solani)), fusarium (Fusarium) species diseases such as Fusarium roseum (Fusarium roseum), other pathogens such as Fusarium roseum, and other pathogens such as Fusarium venenatum, Fusarium graminearum (Fusarium graminearum) and Fusarium oxysporum (Fusarium oxysporum), verticillium dahliae (Verticillium dahliae), aphanotheca (Sclerotium rolfsii), rhizoctonia cerealis (Rynchosporium secalis), nicotiana nigrescens (Cercosporidium personatum), nicotiana nigrescens (Cercospora arachidicola) and brown spot (Cercospora beticola), and other classes and species closely related to these pathogens. In addition to their fungicidal activity, the compositions or combinations also have resistant activity against bacteria such as Pyricularia pyrifolia (Erwinia amylovora), xanthomonas campestris (Xanthomonas campestris), pseudomonas syringae (Pseudomonas syringae), and other species.

The fungicidal compound or composition of the present invention is simple to use, and is applied to plants, plant parts or sites where plants grow, by conventional methods, such as soil mixing, spraying, pouring, etc., before or after germination of plant diseases, in an amount of typically 10 to 5000g per mu, diluted to 10 to 400mg/L (preferably 100 to 300 mg/L) depending on the climatic conditions or the crop conditions. The diluent is preferably water.

The bactericidal compounds or compositions of the present invention have a bactericidal effect which is generally dependent on external factors such as the climate, but the effect of the climate can be slowed down by the use of suitable dosage forms.

The compound or the composition can be mixed with other compounds with sterilization, disinsection or weeding performance, and can also be mixed with nematicides, acaricides, protectants, herbicide safeners, growth regulators, plant nutrients or soil conditioners and the like.

General synthetic procedure

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

Synthetic scheme

Synthesis scheme one

The target compound shown in the formula (I-1) can be prepared by a preparation method of a synthesis scheme I. The intermediate compound A and the intermediate compound B undergo nucleophilic substitution reaction under alkaline conditions (such as triethylamine, sodium hydride, pyridine, potassium carbonate and the like) to obtain a target compound shown in a formula (I-1);

wherein R ¹、R² and Hy have the meaning described in the present invention.

Examples

Synthesis of intermediate 1:1- (N, N-dimethylaminosulfonyl) -1H-1,2, 4-triazole-3-sulfonyl chloride

First step, synthesis of 1, 2-bis (1H-1, 2, 4-triazol-3-yl) disulfane

3-Mercapto-1, 2, 4-triazole (101.0 g,1.00 mol) was dissolved in dichloromethane (500 mL), pyridine (79.0 g,1.00 mol) was added, and the mixture was stirred at 0℃and p-toluenesulfonyl chloride (95.3 g,0.50 mol) was slowly added dropwise over 2 hours. Stirring was carried out at 25℃for 18 hours after the addition was completed. The methylene chloride was distilled off under reduced pressure by a rotary evaporator, and water (500 mL) was added to the residue under mechanical stirring, followed by stirring for 1 hour. Filtration, washing the residue with water (800 mL) and ethyl acetate (300 mL), respectively, and air drying gave 95.2g of yellow powder in 95.2% yield.

LC-MS:(M+1)m/z=201.1。

Second step Synthesis of 3- ((1- (N, N-dimethylaminosulfonyl) -1H-1,2, 4-triazol-3-yl) disulfanyl) -N, N-dimethyl-1H-1, 2, 4-triazole-1-sulfonamide

1, 2-Bis (1H-1, 2, 4-triazol-3-yl) dithioalkane (60.0 g,0.30 mol) was dissolved in N, N-dimethylformamide (300 mL) under nitrogen, and potassium carbonate (69.0 g,0.50 mol) was added thereto and mixed under stirring at 0 ℃. N, N-dimethylaminosulfonyl chloride (93.3 g,0.65 mol) was slowly added dropwise thereto, and the reaction was continued for 6 hours after the completion of the addition for 2 hours. After the reaction was completed, the reaction solution was slowly poured into water and stirred for 1 hour. The solid was filtered and air-dried to give 107.2g of a white powder in 86.3% yield.

LC-MS:(M+1)m/z=415.0。

Third step, synthesis of 1- (N, N-dimethylamino sulfonyl) -1H-1,2, 4-triazole-3-sulfonyl chloride

3- ((1- (N, N-dimethylaminosulfonyl) -1H-1,2, 4-triazol-3-yl) disulphanyl) -N, N-dimethyl-1H-1, 2, 4-triazole-1-sulfonamide (41.40 g,0.10 mol) was dissolved in 1, 2-dichloroethane (150 mL), water (300 mL) was added, cooled to 0℃and acetic acid (100 mL) was added, the temperature was controlled at 10℃to 25℃and after 2 hours chlorine (35.50 g,0.50 mol) was introduced and the reaction was continued for half an hour. After the completion of the reaction, the solution was transferred to a separating funnel, left to stand for separation, and the organic phase was washed three times with water (30 mL), and the solvent was distilled off under reduced pressure using a rotary evaporator to give 48.11g of a white powder in a yield of 87.8%.

LC-MS:(M+1)m/z=274.8。

EXAMPLE 1 Synthesis of N, N-dimethyl-3- ((2-phenyl-1H-imidazol-1-yl) sulfonyl) -1H-1,2, 4-triazole-1-sulfonamide

2-Phenylimidazole (0.29 g,2.0 mmol), triethylamine (0.40 g,4.0 mol) and methylene chloride (15 mL) were added to a 100mL single-necked flask, stirred uniformly at 25℃and 1- (N, N-dimethylaminosulfonyl) -1H-1,2, 4-triazole-3-sulfonyl chloride (1.10 g,4.0 mmol) was slowly added to the reaction system and reacted at 25℃for 12 hours. The reaction was quenched with water (100 mL), extracted with ethyl acetate (50 mL x 3), the organic phase dried over anhydrous sodium sulfate, filtered, the solvent removed from the filtrate under reduced pressure using a rotary evaporator, and the residue was purified by column chromatography [ ethyl acetate/petroleum ether (v/v) =1/3 ], affording 0.33g of a pale yellow liquid in 43.2% yield.

Characterization data for example 1 are shown below:

¹H NMR(400MHz,DMSO-d₆)δ9.01(s,1H),8.02(d,J＝3.5Hz,2H),7.85(s,2H),7.67(d,J＝2.9Hz,3H),2.91(s,6H);

LC-MS:(M+1)m/z=383.0。

The corresponding materials and the intermediate 1 (namely, 1- (N, N-dimethylamino sulfonyl) -1H-1,2, 4-triazole-3-sulfonyl chloride are respectively used, and the corresponding structural formula is that The target compounds shown in Table 1 were obtained by preparing the reaction materials by the synthesis method of example 1.

TABLE 1

Synthesis of intermediate 2:2- (3-bromophenyl) -1H-benzo [ d ] imidazole

M-bromobenzaldehyde (0.93 g,5 mmol), o-phenylenediamine (0.54 g,5 mmol), sodium iodide (0.75 g,5 mmol) and N, N-dimethylformamide (15 mL) were added to a 100mL two-necked flask, and reacted at 80℃for 12 hours. The reaction was quenched with water (50 mL), extracted with ethyl acetate (50 mL. Times.3), the organic phase was dried over anhydrous sodium sulfate, filtered, and the filtrate was dried under reduced pressure to give 1.09g of a pale yellow oil in 80.4% yield.

LC-MS:(M+1)m/z=273.0。

The intermediate compounds in table 2 can be obtained by preparing o-phenylenediamine and corresponding benzaldehyde or benzaldehyde derivatives as reaction raw materials according to the synthesis method of the intermediate 2.

TABLE 2

EXAMPLE 18 Synthesis of 3- ((2- (3-bromophenyl) -1H-benzo [ d ] imidazol-1-yl) sulfonyl) -N, N-dimethyl-1H-1, 2, 4-triazole-1-sulfonamide

2- (3-Bromophenyl) -1H-benzo [ d ] imidazole (0.54 g,2 mmol), sodium hydride (0.16 g,4 mmol) and tetrahydrofuran (15 mL) were added to a 100mL two-necked flask at room temperature, stirred at 25℃for 1 hour, and then 1- (N, N-dimethylaminosulfonyl) -1H-1,2, 4-triazole-3-sulfonyl chloride (1.10 g,4 mmol) was slowly added thereto, and stirring was continued at room temperature for 3 hours. The reaction was quenched with water (150 mL), extracted with ethyl acetate (50 mL x 3), the organic phase dried over anhydrous sodium sulfate, filtered, the solvent removed under reduced pressure by rotary evaporation of the filtrate, and the residue was purified by column chromatography [ ethyl acetate/petroleum ether (v/v) =1/3 ], affording 0.67g of a white solid in 65.8% yield.

Characterization data for example 18 are shown below:

¹H NMR(400MHz,DMSO-d₆)δ9.00(s,1H),8.68(d,J＝5.1Hz,1H),8.61–8.55(m,1H),7.98–7.91(m,1H),7.87(dd,J＝6.1,3.1Hz,2H),7.56(dd,J＝6.1,3.1Hz,2H),7.36(d,J＝7.9Hz,1H),2.91(s,6H);

LC-MS:(M+1)m/z=511.0。

The target compounds in table 3 were obtained by carrying out the preparation by the synthesis method of example 18 using intermediate 1 and the corresponding intermediate compound in table 2 as reaction raw materials.

TABLE 3 Table 3

The preparation was carried out by referring to the synthetic methods of example 1 or example 18, using the corresponding materials and intermediate 1 as reaction raw materials, to obtain comparative compounds 1 to 4 in table 4.

TABLE 4 Table 4

Biological Activity test

In the following test examples, the inventors examined the control efficacy of the compounds of the present invention and the comparative compounds against harmful fungi, taking a part of the compounds of the present invention and the comparative compounds as examples.

Test target cucumber downy mildew (Pseudoperonospora cubensis)

Test treatment the compound was dissolved in DMF to 1% EC for later use. The bactericidal activity of these compounds against the test targets was evaluated at different doses (e.g. 200mg/L, 100mg/L, 50mg/L, 25 mg/L) using the in vivo potting method.

1 Pot cucumber seedling with the same growth vigor in the true leaf period (growing point is removed) is selected, the pot cucumber seedling is naturally dried after spray treatment, inoculation is carried out after 24 hours of treatment, fresh cucumber downy mildew disease leaves are taken, and the leaf back sporangium is dipped in distilled water by a writing brush to be washed out, so that sporangium suspension (2-3 x 10 ⁵/mL) is prepared. Uniformly spraying and inoculating on cucumber seedlings by using an inoculating sprayer (with the pressure of 0.1 MPa), transferring the inoculated test material to a climatic chamber, keeping the relative humidity at about 21 ℃, keeping the temperature at about 21 ℃ after 24 hours, keeping the relative humidity at about 95%, carrying out grading investigation according to blank control morbidity after 5 days, and calculating the control effect according to disease index.

The test results are shown below:

At 200mg/L dose, example 1, example 2, example 3, example 4, example 5, example 6, example 7, example 8, example 9, example 10, example 11, example 12, example 13, example 14, example 15, example 16, example 17, example 18, example 19, example 20, example 21, example 22, example 23, example 24, example 25, example 26, example 27, example 28, and the control effect on cucumber downy mildew was ≡80%;

At 100mg/L dose, the control effect of example 1, example 2, example 3, example 4, example 5, example 6, example 7, example 8, example 9, example 10, example 11, example 12, example 13, example 14, example 15, example 16, example 17, example 18, example 19, example 20, example 21, example 22, example 23, example 25, example 26, example 27, example 28, example 24 on cucumber downy mildew is equal to or greater than 80%;

The control effect of example 5, example 6, example 7, example 8, example 9, example 13, example 14, example 15, example 16, example 19, example 20, example 22, example 24, example 25 and example 26 on cucumber downy mildew at a dose of 50mg/L was not less than 80%, and the control effect of comparative compounds 1 to 4 on cucumber downy mildew at the same dose is shown in Table 5:

control of cucumber downy mildew at 50mg/L dose of the compound of Table 5

From the above test results, it is found that the compounds of the present invention have excellent control effects on plant diseases, particularly on cucumber downy mildew even at low doses (e.g., control effects of example 8, example 13, example 15, example 16, example 18, example 19, example 20, example 22, example 24, example 25 on cucumber downy mildew is not less than 80% at a dose of 25 mg/L), and can be used as fungicides in agriculture.

The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited to the specific details of the above embodiments, and various simple modifications can be made to the technical solution of the present invention within the scope of the technical concept of the present invention, and all the simple modifications belong to the protection scope of the present invention.

Claims (8)

1. A compound, which is a compound represented by formula (I) or a salt thereof: (I); in: R ¹ and R ² are each independently -CH ₃ ; n is 2; Hy , or ;in, ^Ra is phenyl or pyridyl optionally substituted by 1 or 2 groups selected from fluorine, chlorine, bromine, iodine, -halogenated _C1-4 alkyl; R ^b is hydrogen, -C _1-4 alkyl; R ^c is hydrogen; R ^d is phenyl, pyridyl or thienyl optionally substituted by 1 group selected from fluorine, chlorine, bromine or iodine; ^Re is hydrogen, -C(=O)H; ^Rf is hydrogen; ^Rg is phenyl optionally substituted by 1 or 2 groups selected from fluorine, chlorine, bromine, iodine or dihalogenated _C1-4 alkyl, or pyridyl optionally substituted by 1 group selected from fluorine, chlorine, bromine or iodine. 2. The compound according to claim 1, wherein: ^Ra is phenyl or pyridyl optionally substituted by 1 or 2 groups selected from fluorine, chlorine, bromine, iodine, _-CF3 ; R ^b is hydrogen or -CH ₃ ; R ^d is phenyl, pyridyl or thienyl optionally substituted by 1 group selected from fluorine, chlorine, bromine or iodine; ^Re is hydrogen or -C(=O)H. 3. The compound according to claim 2, wherein: Hy , , , , , , or ; Or Hy is , , , , or . 4. The compound according to claim 1, wherein: Hy ; Wherein, ^Rg is phenyl optionally substituted by 1 or 2 groups selected from fluorine, chlorine, bromine, iodine, _-CF3 , or pyridyl optionally substituted by 1 group selected from fluorine, chlorine, bromine, iodine. 5. The compound according to claim 4, wherein: Hy , , , , , , , , , or . 6. A compound having one of the following structures or a salt thereof: (1) (2) (3) (4) (5) (6) (7) (8) (9) (10) (11) (12) (13) (14) (15) (16) (17) (18) (19) (20) (twenty one), (twenty two), (twenty three), (twenty four), (25) (26) (27) or (28). 7. A composition comprising the compound according to any one of claims 1 to 6 and an adjuvant in pesticide science. 8. Use of the compound according to any one of claims 1 to 6 or the composition according to claim 7 as a plant disease control agent in agriculture, wherein the plant disease is cucumber downy mildew.