Aromatically substituted triazole sulfonamide derivatives and preparation methods and applications thereof

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), 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 R 1 and R 2 Each independently is C 1‑4 Alkyl, Hy is a 5-10 membered heteroaryl, wherein Hy is optionally substituted by a substituent described in the present invention.

Description

Technical Field

[0001] The present invention belongs to the field of pesticides, and in particular, relates to an aromatic substituted triazole sulfonamide derivative, a preparation method and application of the triazole sulfonamide derivative as a fungicide in agriculture. Background Art

[0002] In modern agricultural production, various types of pesticides are needed to ensure the healthy growth of crops. The fungicidal activity of existing compounds is always insufficient at relatively low application rates. In addition, due to the long-term and frequent use of pesticides, the diseases on crops develop resistance to existing pesticides, which reduces the control effect of pesticides. In order to solve the problem of high efficiency or resistance, it is necessary to continuously develop new compounds that can prevent and control plant diseases. Summary of the invention

[0003] The invention provides an aromatic-substituted triazole sulfonamide derivative, which has excellent protective effect on plant diseases, especially on cucumber downy mildew at a low dosage.

[0004] Specifically,

[0005] In one aspect, the present invention provides a compound, which is a compound represented by formula (I) or a stereoisomer, nitrogen oxide or salt thereof of the compound represented by formula (I):

[0006]

[0007] in:

[0008] R 1 and R 2 are 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-, optionally substituted by 1, 2, 3, 4 or 5 radicals 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-substituted phenyl or optionally substituted by 1, 2, 3, 4 or 5 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 substituted benzyl;

[0009] or R 1 , R 2and the nitrogen atom connected thereto form a 3-6 membered heterocyclic ring or a 5-10 membered heteroaryl group; the 3-6 membered heterocyclic ring or the 5-10 membered heteroaryl group is optionally substituted by 1 or 2 selected from fluorine, chlorine, bromine, iodine or C 1-4 Alkyl substitution;

[0010] n is 0, 1 or 2;

[0011] Hy is a 5-10 membered heteroaryl group; wherein Hy is optionally substituted by 1, 2 or 3 groups selected from fluorine, chlorine, bromine, iodine, cyano, hydroxyl, nitro, carboxyl, -C(=O)H, C 1-4 Alkyl, C 1-4 Alkoxy, C 1-4 Alkylthio, halo 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)-, optionally substituted by 1, 2, 3, 4 or 5 groups selected from fluorine, chlorine, bromine, iodine, cyano, hydroxyl, nitro, carboxyl, C 1-4 Alkyl, C 1-4 Alkoxy, halogenated C 1-4 Alkyl or halogenated C 1-4 Alkoxy substituted phenyl or optionally substituted by 1, 2, 3 or 4 selected from fluorine, chlorine, bromine, iodine, cyano, hydroxyl, nitro, carboxyl, C 1-4 Alkyl, C 1-4 Alkoxy, halogenated C 1-4 Alkyl or halogenated C 1-4 Alkoxy substituted 5-6 membered heteroaryl substituted.

[0012] In some embodiments, R 1 and R 2 are independently hydrogen, C 1-4 Alkyl, C 2-4 Alkenyl or C 2-4 Alkynyl.

[0013] In other embodiments, R 1 and R 2 Each is independently hydrogen, -CH3, -CH2CH3, -CH2CH2CH3, -CH(CH3)2, -CH2CH2CH2CH3, -CH2CH(CH3)2, -CH=CH2, -CH2CH=CH2, -CCH or -CH2CCH.

[0014] In some embodiments, R 1 , R 2Together with the nitrogen atom connected thereto, a 3-6 membered heterocyclic ring is formed; the 3-6 membered heterocyclic ring is optionally substituted by 1 or 2 groups selected from fluorine, chlorine, bromine, iodine or -CH3.

[0015] In other embodiments, R 1 , R 2 Together with the nitrogen atom connected to it, it forms the following substructure:

[0016]

[0017] Preferably, in some embodiments, R 1 and R 2 Each independently is C 1-4 alkyl.

[0018] More preferably, in some embodiments, R 1 and R 2 Each is independently -CH3.

[0019] Preferably, in some embodiments, n is 2.

[0020] In some embodiments, Hy is

[0021] Among them, R a is optionally substituted by 1, 2, 3, 4, 5 or 5 groups selected from fluorine, chlorine, bromine, iodine, cyano, hydroxyl, nitro, carboxyl, C 1-4 Alkyl, C 1-4 Alkoxy, halogenated C 1-4 Alkyl or halogenated C 1-4 Alkoxy substituted phenyl or optionally substituted by 1, 2, 3 or 4 selected from fluorine, chlorine, bromine, iodine, cyano, hydroxyl, nitro, carboxyl, C 1-4 Alkyl, C 1-4 Alkoxy, halogenated C 1-4 Alkyl or halogenated C 1-4 Alkoxy-substituted 5-6-membered heteroaryl;

[0022] R b is hydrogen, fluorine, chlorine, bromine, iodine, cyano, hydroxyl, nitro, carboxyl, -C(=O)H, C 1-4 Alkyl, C 1-4 Alkoxy, C 1-4 Alkylthio, halo 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)- or C 1-4 Alkyl-C(═O)-;

[0023] R c is hydrogen, fluorine, chlorine, bromine, iodine, cyano, hydroxyl, nitro, carboxyl, -C(=O)H, C 1-4 Alkyl, C 1-4 Alkoxy, C 1-4 Alkylthio, halo 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)-, optionally substituted by 1, 2, 3, 4 or 5 moieties 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-substituted phenyl or optionally substituted by 1, 2, 3 or 4 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-substituted 5-6 membered heteroaryl.

[0024] In other embodiments, Hy is

[0025] Among them, R a is phenyl optionally substituted by 1, 2, 3, 4 or 5 groups selected from fluorine, chlorine, bromine, iodine, cyano, hydroxyl, nitro, carboxyl, -CH3, -OCH3, -CF3 or -OCF3, pyridyl optionally substituted by 1, 2, 3 or 4 groups selected from fluorine, chlorine, bromine, iodine, cyano, hydroxyl, nitro, carboxyl, -CH3, -OCH3, -CF3 or -OCF3, or thienyl optionally substituted by 1, 2 or 3 groups selected from fluorine, chlorine, bromine, iodine, cyano, hydroxyl, nitro, carboxyl, -CH3, -OCH3, -CF3 or -OCF3;

[0026] R b is hydrogen, fluorine, chlorine, bromine, iodine, cyano, hydroxyl, nitro, carboxyl, -C(=O)H, -CH3, -OCH3, -SCH3, -CF3, -OCF3 or -SCF3;

[0027] R cIt is hydrogen, fluorine, chlorine, bromine, iodine, cyano, hydroxyl, nitro, carboxyl, -C(=O)H, -CH3, -OCH3, -SCH3, -CF3, -OCF3, -SCF3, phenyl optionally substituted by 1, 2, 3, 4 or 5 groups selected from fluorine, chlorine, bromine, iodine, -CH3, -OCH3, -CF3 or -OCF3, or pyridyl optionally substituted by 1, 2, 3 or 4 groups selected from fluorine, chlorine, bromine, iodine, -CH3, -OCH3, -CF3 or -OCF3, or thienyl optionally substituted by 1, 2 or 3 groups selected from fluorine, chlorine, bromine, iodine, -CH3, -OCH3, -CF3 or -OCF3.

[0028] Preferably, in some embodiments, R a It is phenyl which is optionally substituted by 1 or 2 groups selected from fluorine, chlorine, bromine, iodine, cyano, hydroxyl, nitro, carboxyl, -CH3, -OCH3, -CF3 or -OCF3, or pyridin-2-yl which is optionally substituted by 1, 2, 3 or 4 groups selected from fluorine, chlorine, bromine, iodine, cyano, hydroxyl, nitro, carboxyl, -CH3, -OCH3, -CF3 or -OCF3.

[0029] More preferably, in some embodiments, R a is phenyl or pyridin-2-yl optionally substituted by 1 or 2 groups selected from fluorine, chlorine, bromine, iodine, -CH3, -OCH3, -CF3 or -OCF3.

[0030] The pyridin-2-yl group is Indicates the location of connection to the rest of the molecule.

[0031] Preferably, in some embodiments, R b It is hydrogen, fluorine, chlorine, bromine, iodine, cyano, hydroxyl, nitro, carboxyl, -C(=O)H or -CH3.

[0032] More preferably, in some embodiments, R b It is hydrogen or -CH3.

[0033] Preferably, in some embodiments, R c For hydrogen.

[0034] In some embodiments, Hy is

[0035] In some embodiments, Hy is

[0036] Among them, R d is optionally substituted by 1, 2, 3, 4 or 5 groups selected from fluorine, chlorine, bromine, iodine, cyano, hydroxyl, nitro, carboxyl, C 1-4 Alkyl, C 1-4 Alkoxy, halogenated C1-4 Alkyl or halogenated C 1-4 Alkoxy substituted phenyl or optionally substituted by 1, 2, 3 or 4 selected from fluorine, chlorine, bromine, iodine, cyano, hydroxyl, nitro, carboxyl, C 1-4 Alkyl, C 1-4 Alkoxy, halogenated C 1-4 Alkyl or halogenated C 1-4 Alkoxy-substituted 5-6-membered heteroaryl;

[0037] R e is hydrogen, fluorine, chlorine, bromine, iodine, cyano, hydroxyl, nitro, carboxyl, -C(=O)H, C 1-4 Alkyl, C 1-4 Alkoxy, C 1-4 Alkylthio, halo 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)- or C 1-4 Alkyl-C(═O)-;

[0038] R f is hydrogen, fluorine, chlorine, bromine, iodine, cyano, hydroxyl, nitro, carboxyl, -C(=O)H, C 1-4 Alkyl, C 1-4 Alkoxy, C 1-4 Alkylthio, halo 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)-, optionally substituted by 1, 2, 3, 4 or 5 moieties 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-substituted phenyl or optionally substituted by 1, 2, 3 or 4 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-substituted 5-6 membered heteroaryl.

[0039] In other embodiments, Hy is

[0040] Among them, R d is phenyl optionally substituted by 1, 2, 3, 4 or 5 groups selected from fluorine, chlorine, bromine, iodine, cyano, hydroxyl, nitro, carboxyl, -CH3, -OCH3, -CF3 or -OCF3, pyridyl optionally substituted by 1, 2, 3 or 4 groups selected from fluorine, chlorine, bromine, iodine, cyano, hydroxyl, nitro, carboxyl, -CH3, -OCH3, -CF3 or -OCF3, or thienyl optionally substituted by 1, 2 or 3 groups selected from fluorine, chlorine, bromine, iodine, cyano, hydroxyl, nitro, carboxyl, -CH3, -OCH3, -CF3 or -OCF3;

[0041] R e is hydrogen, fluorine, chlorine, bromine, iodine, cyano, hydroxyl, nitro, carboxyl, -C(=O)H, -CH3, -OCH3, -SCH3, -CF3, -OCF3 or -SCF3;

[0042] R f It is hydrogen, fluorine, chlorine, bromine, iodine, cyano, hydroxyl, nitro, carboxyl, -C(=O)H, -CH3, -OCH3, -SCH3, -CF3, -OCF3, -SCF3, phenyl optionally substituted by 1, 2, 3, 4 or 5 groups selected from fluorine, chlorine, bromine, iodine, -CH3, -OCH3, -CF3 or -OCF3, pyridyl optionally substituted by 1, 2, 3 or 4 groups selected from fluorine, chlorine, bromine, iodine, -CH3, -OCH3, -CF3 or -OCF3, or thienyl optionally substituted by 1, 2 or 3 groups selected from fluorine, chlorine, bromine, iodine, -CH3, -OCH3, -CF3 or -OCF3.

[0043] Preferably, in some embodiments, R d is phenyl, pyridin-2-yl or thiophen-2-yl optionally substituted by 1 group selected from fluorine, chlorine, bromine or iodine.

[0044] The thiophene-2-yl group is

[0045] Preferably, in some embodiments, R e It is hydrogen or -C(=O)H.

[0046] Preferably, in some embodiments, R f For hydrogen.

[0047] In some embodiments, Hy is

[0048] In some embodiments, Hy is

[0049] Among them, R gis optionally substituted by 1, 2, 3, 4 or 5 groups selected from fluorine, chlorine, bromine, iodine, cyano, hydroxyl, nitro, carboxyl, C 1-4 Alkyl, C 1-4 Alkoxy, halogenated C 1-4 Alkyl or halogenated C 1-4 Alkoxy substituted phenyl or optionally substituted by 1, 2, 3 or 4 selected from fluorine, chlorine, bromine, iodine, cyano, hydroxyl, nitro, carboxyl, C 1-4 Alkyl, C 1-4 Alkoxy, halogenated C 1-4 Alkyl or halogenated C 1-4 Alkoxy-substituted 5-6 membered heteroaryl.

[0050] In other embodiments, Hy is

[0051] Among them, R g It is phenyl which is optionally substituted by 1, 2, 3, 4 or 5 groups selected from fluorine, chlorine, bromine, iodine, cyano, hydroxyl, nitro, carboxyl, -CH3, -OCH3, -CF3 or -OCF3, or pyridinyl which is optionally substituted by 1, 2, 3 or 4 groups selected from fluorine, chlorine, bromine, iodine, cyano, hydroxyl, nitro, carboxyl, -CH3, -OCH3, -CF3 or -OCF3.

[0052] Preferably, in some embodiments, R g is optionally substituted by 1 or 2 selected from fluorine, chlorine, bromine, iodine, C 1-4 Alkyl or halogenated C 1-4 Phenyl substituted with alkyl or pyridin-3-yl optionally substituted with 1 group selected from fluorine, chlorine, bromine or iodine.

[0053] More preferably, in some embodiments, R g is phenyl optionally substituted by 1 or 2 groups selected from fluorine, chlorine, bromine, iodine or -CF3 or pyridin-3-yl optionally substituted by 1 group selected from fluorine, chlorine, bromine or iodine.

[0054] The pyridin-3-yl group is

[0055] In other embodiments, Hy is

[0056] In some embodiments, the present invention provides a compound, which is a compound having one of the following structures or a stereoisomer, nitrogen oxide or salt thereof of a compound having one of the following structures:

[0057]

[0058]

[0059] In another aspect, the present invention provides a composition comprising at least one compound of the present invention and an adjuvant commonly used in pesticides.

[0060] In yet another aspect, the present invention provides use of the compound or composition of the present invention as a plant disease control agent in agriculture.

[0061] In yet another aspect, the present invention provides a method for controlling plant diseases, which comprises 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 plants, plant parts or plant growth environments.

[0062] The disease is caused by plant pathogenic fungi.

[0063] The disease is preferably downy mildew.

[0064] The plant disease is preferably cucumber downy mildew.

[0065] Detailed description of the invention

[0066] Definitions and general terms

[0067] Certain embodiments of the present invention are now described in detail, examples of which are illustrated by the accompanying structural formula and chemical formula. The present invention is intended to cover all substitutions, modifications and equivalent technical solutions, which are all included in the scope of the present invention as defined in the claims. It should be appreciated by those skilled in the art that many methods and materials similar or equivalent to those described in the present invention can be used to practice the present invention. The present invention is by no means limited to the methods and materials described in the present invention. In the event that one or more of the combined documents, patents and similar materials are different from or contradictory to the present application (including but not limited to defined terms, term applications, described technologies, etc.), the present application shall prevail.

[0068] It should be further appreciated that certain features of the invention, which for clarity are described in multiple separate embodiments, may also be provided in combination in a single embodiment. Conversely, various features of the invention, which for brevity are described in a single embodiment, may also be provided separately or in any suitable sub-combination.

[0069] Unless otherwise specified, all technical terms used in the present invention have the same meaning as commonly understood by those skilled in the art to which the present invention belongs. All patents and publications related to the present invention are incorporated herein by reference in their entirety.

[0070] Unless otherwise indicated, the following definitions used in the present invention shall apply. For purposes of the present invention, chemical elements are consistent with the Periodic Table of the Elements, CAS version, and Handbook of Chemistry and Physics, 75th edition, 1994. In addition, general principles of organic chemistry can be found in "Organic Chemistry", Thomas Sorrell, University Science Books, Sausalito: 1999, and "March's Advanced Organic Chemistry" by Michael B. Smith and Jerry March, John Wiley & Sons, New York: 2007, the entire contents of which are incorporated herein by reference.

[0071] Unless otherwise specified or there is a clear conflict in context, the articles "a", "an", and "the" as used herein are intended to include "at least one" or "one or more". Therefore, these articles as used herein refer to articles that refer to one or more than one (i.e., at least one) object. For example, "a component" refers to one or more components, i.e., there may be more than one component contemplated for use or use in the implementation of the described embodiment.

[0072] The term "comprising" is an open expression, that is, including the contents specified in the present invention but not excluding other contents.

[0073] "Stereoisomers" refer to compounds that have the same chemical constitution but differ in the way the atoms or groups are arranged in space. Stereoisomers include enantiomers, diastereomers, conformational isomers (rotamers), geometric isomers (cis / trans) isomers, atropisomers, and the like.

[0074] "Enantiomers" refer to two non-superimposable isomers of a compound that are mirror images of each other.

[0075] "Diastereoisomers" refer to stereoisomers that have two or more chiral neutrals and whose molecules are not mirror images of each other. Diastereoisomers have different physical properties, such as melting points, boiling points, spectral properties, and reactivity. Diastereomeric mixtures can be separated by high-resolution analytical procedures such as electrophoresis and chromatography, for example HPLC.

[0076] The stereochemical definitions and conventions used in the present invention generally follow those described in SP 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.

[0077] Many organic compounds exist in optically active forms, i.e. they have the ability to rotate the plane of plane polarized light. When describing an optically active compound, the prefixes D and L or R and S are used to indicate the absolute configuration of the molecule about its chiral center(s). The prefixes d and l or (+) and (-) are the symbols used to designate the rotation of plane polarized light caused by the compound, where (-) or l indicates that the compound is left-handed. Compounds prefixed with (+) or d are right-handed. A specific stereoisomer is an enantiomer, and a mixture of such isomers is called a mixture of enantiomers. A 50:50 mixture of enantiomers is called a racemic mixture or racemate, which can occur when there is no stereoselectivity or stereospecificity in a chemical reaction or process.

[0078] Any asymmetric atom (e.g., carbon, etc.) of the compounds disclosed herein can exist in a 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 terms of the (R)- or (S)-configuration.

[0079] Depending on the choice of starting materials and process, the compounds of the invention may exist in the form of one of the possible isomers or a mixture thereof, such as a racemate and a diastereomeric mixture (depending on the number of asymmetric carbon atoms). Optically active (R)- or (S)-isomers may 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 cycloalkyl substituents may be in the cis or trans configuration.

[0080] Any resulting mixture of stereoisomers can be separated into the pure or substantially pure geometric isomers, enantiomers, diastereomers on the basis of the differences in the constituent physicochemical properties, for example, by chromatography and / or fractional crystallization.

[0081] Any resulting racemate of the final product or intermediate can be separated into optical antipodes by known methods by methods familiar to those skilled in the art, such as by separation of the diastereoisomeric salts thereof obtained. The racemic product can also be separated by chiral chromatography, such as high performance liquid chromatography (HPLC) using a chiral adsorbent. In particular, enantiomers can be prepared by asymmetric synthesis.

[0082] As described herein, the compounds of the present invention may be optionally substituted with one or more substituents, such as the general formula compounds above, or as specific examples, subclasses, and classes of compounds included in the embodiments. It should be understood that the terms "optionally substituted" and "optionally substituted with..." substituents" are used interchangeably with "substituted or unsubstituted". In general, "optionally substituted" and "optionally substituted with..." substituents" mean that the given structure is unsubstituted or one or more hydrogen atoms in the given structure are replaced with the specified substituents. In general, the term "substituted" means that one or more hydrogen atoms in the given structure are replaced with the specified substituents. Unless otherwise indicated, an optional substituent group can be substituted at each substitutable position of the group. When more than one position in the given structure can be substituted with one or more substituents selected from the specified group, the substituents can be substituted at each position the same or different. Specifically, examples of "one or more" refer to 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10. The substituents may be, but are not limited to, deuterium, fluorine, chlorine, bromine, iodine, cyano, hydroxy, nitro, amino, carboxyl, alkyl, alkoxy, alkoxyalkyl, alkoxyalkoxy, alkoxyalkylamino, aryloxy, heteroaryloxy, heterocyclyloxy, arylalkoxy, heteroarylalkoxy, heterocyclylalkoxy, cycloalkylalkoxy, alkylamino, alkylaminoalkyl, alkylaminoalkylamino, cycloalkylamino, cycloalkylalkylamino, alkylthio, haloalkyl, haloalkoxy, hydroxy-substituted alkyl, hydroxy-substituted alkylamino, cyano-substituted alkyl, cyano-substituted alkoxy, cyano-substituted alkylamino, amino-substituted alkyl, alkylacyl, heteroalkyl, cycloalkyl, cycloalkenyl, cycloalkylalkyl, heterocyclyl, heterocyclylalkyl, heterocyclylacyl, aryl, arylalkyl, arylamino, heteroaryl, heteroarylalkyl, heteroarylamino, amide, sulfonyl, aminosulfonyl and the like.

[0083] In addition, it should be noted that, unless explicitly stated otherwise, the description methods used in the present invention, "each... is independently" and "... are each independently" and "... are independently" can be interchanged and should be understood in a broad sense, which can mean that in different groups, the specific options expressed by the same symbols do not affect each other, or that in the same group, the specific options expressed by the same symbols do not affect each other.

[0084] In various parts of this specification, substituents of compounds disclosed in the present invention are disclosed according to group types or ranges. It is particularly noted that the present invention includes each independent subcombination of the individual members of these group types and ranges. For example, the term "C1-C6 alkyl" or "C 1-6 "Alkyl" specifically refers to methyl, ethyl, C3 alkyl, C4 alkyl, C5 alkyl and C6 alkyl as disclosed independently.

[0085] The term "alkyl" or "alkyl group" used in the present invention refers to a saturated straight or branched monovalent hydrocarbon group containing 1 to 20 carbon atoms; wherein the alkyl group is optionally substituted with one or more substituents described in the present invention. Unless otherwise specified, the alkyl group contains 1-20 carbon atoms. In one embodiment, the alkyl group contains 1-12 carbon atoms; in one embodiment, the alkyl group contains 1-8 carbon atoms; in another embodiment, the alkyl group contains 1-6 carbon atoms; in another embodiment, the alkyl group contains 1-4 carbon atoms; in another embodiment, the alkyl group contains 1-3 carbon atoms.

[0086] Examples of alkyl groups include, but are not limited to, methyl (Me, -CH3), ethyl (Et, -CH2CH3), n-propyl (n-Pr, -CH2CH2CH3), isopropyl (i-Pr, -CH(CH3)2), n-butyl (n-Bu, -CH2CH2CH2CH3), isobutyl (i-Bu, -CH2CH(CH3)2), sec-butyl (s-Bu, -CH(CH3)CH2CH3), tert-butyl (t-Bu, -C(CH3)3), n-pentyl (-CH2CH2CH2 2-Methyl-2-butyl (-C(CH3)2CH2CH3), 3-methyl-2-butyl (-CH(CH3)CH(CH3)2), 3-methyl-1-butyl (-CH2CH2CH(CH3)2), 2-methyl-1-butyl (-CH2CH(CH3)CH2CH3), n-hexyl (-CH2CH2CH2CH2CH2CH3), and the like.

[0087] The term "alkenyl" refers to a straight or branched chain monovalent hydrocarbon radical containing 2 to 12 carbon atoms and having at least one site of unsaturation, i.e., a carbon-carbon sp 2 Double bond, wherein the alkenyl group may be optionally substituted with one or more substituents described herein, including "cis" and "tans" orientations, or "E" and "Z" orientations. In one embodiment, the alkenyl group contains 2-8 carbon atoms; in another embodiment, the alkenyl group contains 2-6 carbon atoms; in yet another embodiment, the alkenyl group contains 2-4 carbon atoms. Examples of alkenyl groups include, but are not limited to, vinyl (-CH=CH2), allyl (-CH2CH=CH2), propenyl (CH3-CH=CH-), oxo-butenyl (CH3-C(=O)-CH=CH-), and the like.

[0088] The term "alkynyl" refers to a straight or branched monovalent hydrocarbon radical containing 2 to 12 carbon atoms, wherein at least one carbon-carbon sp triple bond is present, 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; 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.

[0089] The term "alkoxy" means an alkyl group attached to the rest of the molecule via an oxygen atom, wherein the alkyl group has a meaning as described herein. Examples of alkoxy groups include, but are not limited to, methoxy (MeO, -OCH3), ethoxy (EtO, -OCH2CH3), 1-propoxy (n-PrO, n-propoxy, -OCH2CH2CH3), 2-propoxy (i-PrO, i-propoxy, -OCH(CH3)2), and the like.

[0090] The term "alkylthio" means an alkyl group attached to the rest of the molecule via a sulfur atom, wherein the alkyl group has a meaning as described herein. Examples of alkylthio groups include, but are not limited to, -SCH3, -SCH2CH3, -SCH2CH2CH3, -SCH(CH3)2, and the like.

[0091] The term "cycloalkyl" refers to a monovalent or polyvalent saturated monocyclic, bicyclic or tricyclic ring system containing 3-12 carbon atoms. In one embodiment, the cycloalkyl contains 3-10 carbon atoms; in another embodiment, the cycloalkyl contains 3-8 carbon atoms; in yet another embodiment, the cycloalkyl contains 3-6 carbon atoms. The cycloalkyl group is optionally substituted with one or more substituents described herein. Such examples include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl, cyclododecyl, and the like.

[0092] The term "cycloalkyl-alkylene" means that a cycloalkyl group is connected to the rest of the molecule via an alkylene group, wherein alkylene and cycloalkyl groups have the meanings as described herein. Such examples include, but are not limited to, cyclopropyl-CH2-, cyclobutyl-CH2-, cyclopentyl-CH2-, cyclohexyl-CH2-, and the like.

[0093] In various parts of this specification, linking substituents are described. When the structure clearly requires a linking group, the Markush variable listed for that group should be understood to be a linking group. For example, if the structure requires a linking group and the Markush group definition for that variable lists "alkyl" or "aryl", it should be understood that the "alkyl" or "aryl" represents an alkylene group or an arylene group, respectively, that is connected.

[0094] The term "alkylene" means a saturated divalent hydrocarbon radical derived from a saturated straight or branched hydrocarbon by removing two hydrogen atoms. Unless otherwise specified, an alkylene group contains 1-12 carbon atoms. In one embodiment, an alkylene group contains 1-8 carbon atoms; in one embodiment, an alkylene group contains 1-6 carbon atoms; in another embodiment, an alkylene group contains 1-4 carbon atoms; in yet another embodiment, an alkylene group contains 1-3 carbon atoms; in yet another embodiment, an alkylene group contains 1-2 carbon atoms. Such examples include methylene (-CH2-), ethylene (-CH2CH2-), propylene (-CH2CH2CH2-), -CH(CH3)CH2-, -C(CH3)2-, -CH2CH2CH(CH3)-, -CH2CH2C(CH3)2-, and the like.

[0095] The term "aryl" refers to monocyclic, bicyclic and tricyclic carbon ring systems containing 6-14 ring atoms, or 6-12 ring atoms, or 6-10 ring atoms, wherein at least one ring system is aromatic, wherein each ring system contains a ring consisting of 3-7 atoms and has one or more points of attachment to the rest of the molecule. The term "aryl" can be used interchangeably with the term "aromatic ring". Examples of aryl groups can include phenyl, indenyl, naphthyl and anthracenyl. The aryl group is optionally substituted with one or more substituents described herein.

[0096] The terms "heterocyclyl" and "heterocycle" are used interchangeably herein and refer to a saturated or partially unsaturated monocyclic, bicyclic or tricyclic ring containing 3-15 ring atoms, wherein the monocyclic, bicyclic or tricyclic ring does not contain an aromatic ring and at least one ring atom is selected from nitrogen, sulfur and oxygen atoms. Unless otherwise specified, the heterocyclyl group can be a carbon group or a nitrogen group, and the -CH2- group can be optionally replaced by -C(=O)-. The sulfur atom of the ring can be optionally oxidized to S-oxide. The nitrogen atom of the ring can be optionally oxidized to N-oxide. Examples of heterocyclic groups include, but are not limited to, oxirane, azetidinyl, oxetanyl, thietanyl, pyrrolidinyl (e.g., 2-pyrrolidinyl), 2-pyrrolinyl, 3-pyrrolinyl, pyrazolidinyl, imidazolinyl, imidazolidinyl, tetrahydrofuranyl, dihydrofuranyl, tetrahydrothiophenyl, dihydrothiophenyl, 1,3-dioxolane, dithiolanyl, tetrahydropyranyl, dihydropyranyl, 2H-pyranyl, 4H-pyranyl, 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. Examples of heterocyclic groups in which the -CH2- group is replaced by -C(=O)- include, but are not limited to, 2-oxopyrrolidinyl, oxo-1,3-thiazolidinyl, 2-piperidonyl, 3,5-dioxopiperidinyl. Examples of heterocyclic groups in which the sulfur atom is oxidized include, but are not limited to, sulfolane, 1,1-dioxothiomorpholinyl. The heterocyclyl group is optionally substituted with one or more substituents described herein.

[0097] 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 describe the number of ring atoms in the molecule. For example, tetrahydrofuranyl is a 5 membered heterocyclyl and piperidinyl is a 6 membered heterocyclyl.

[0098] The term "heteroatom" refers to O, S, N, P and Si, including N, S and P in any oxidation state; in the form of primary, secondary, tertiary amines and quaternary ammonium salts; or in the form of a nitrogen atom in a heterocyclic ring in which the hydrogen is substituted, for example, N (such as N in 3,4-dihydro-2H-pyrrolyl), NH (such as NH in pyrrolidinyl) or NR (such as NR in N-substituted pyrrolidinyl).

[0099] The term "halogen" refers to fluorine (F), chlorine (Cl), bromine (Br) or iodine (I).

[0100] The term "heteroaryl" refers to monocyclic, bicyclic and tricyclic ring systems containing 5-12 ring atoms, or 5-10 ring atoms, or 5-6 ring atoms, wherein at least one ring system is aromatic and at least one ring system contains one or more heteroatoms, wherein each ring system contains 5-7 ring atoms and has one or more points of attachment to the rest of the molecule. The term "heteroaryl" can 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, the 5-10 heteroaryl contains 1, 2, 3 or 4 heteroatoms independently selected from O, S and N.

[0101] Examples of heteroaryl groups include, but are not limited to, 2-furanyl, 3-furanyl, 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, pyrimidinyl, pyridinyl; also includes the following bicyclic rings, but is by no means limited to these bicyclic rings: benzimidazolyl, benzofuranyl, benzotetrahydrofuranyl, benzothienyl, indolyl (such as 2-indolyl), benzopiperidinyl, and the like.

[0102] 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 describe the number of ring atoms in the molecule. For example, pyrrolyl, pyrazolyl, imidazolyl, thienyl, isothiazolyl, thiazolyl, furanyl, isoxazolyl and oxazolyl are 5-membered heteroaryl groups, and pyridinyl, pyrimidinyl, pyrazinyl and pyridazinyl are 6-membered heteroaryl groups.

[0103] The term "haloalkyl" means an alkyl group substituted with one or more halogen atoms, such examples include, but are not limited to, -CF3, -CHF2, -CH2Cl, -CH2CF3, -CH2CHF2, -CH2CH2F, -CH2CH2Cl, -CH2CH2CF3, and the like.

[0104] The term "haloalkoxy" means an alkoxy group substituted with one or more halogen atoms, such examples include, but are not limited to, -OCF3, -OCHF2, -OCHCl2, -OCH2CHF2, -OCH2CHCl2, -OCH(CH3)CHF2, and the like.

[0105] The term "haloalkylthio" means an alkylthio group substituted with one or more halogen atoms, such examples include, but are not limited to, difluoromethylthio (-SCHF2), trifluoromethylthio (-SCF3), and the like.

[0106] The term "cyano" refers to -CN.

[0107] The term "hydroxy" refers to -OH.

[0108] The term "nitro" refers to -NO2.

[0109] The term "carboxyl" refers to -COOH.

[0110] Salts of the compounds of the present invention include those derived from alkali metals or alkaline earth metals and those derived from ammonia and amines. Preferred cations include sodium, potassium, magnesium and a cation having the formula N + (R A R B R C R D ) of an ammonium cation, wherein R A , R B , R C and R DIndependently selected from hydrogen, C1-C6 alkyl and C1-C6 hydroxyalkyl. Salts of compounds of formula (I) can be prepared by treating compounds of formula (I) with metal hydroxides (e.g. sodium hydroxide) or amines (e.g. ammonia, trimethylamine, diethanolamine, 2-methylthiopropylamine, bisallylamine, 2-butoxyethylamine, morpholine, cyclododecylamine or benzylamine).

[0111] When the compounds of the present invention contain a basic moiety, acceptable salts may be formed from organic and inorganic acids such as acetic acid, propionic acid, lactic acid, citric acid, tartaric acid, succinic acid, fumaric acid, maleic acid, malonic acid, mandelic acid, malic acid, phthalic acid, hydrochloric acid, hydrobromic acid, phosphoric acid, nitric acid, sulfuric acid, methanesulfonic acid, naphthalenesulfonic acid, benzenesulfonic acid, toluenesulfonic acid, camphorsulfonic acid, and similarly known acceptable acids.

[0112] Compositions and preparations of the compounds of the present invention

[0113] The compounds of the present invention can generally be used as fungicidal active ingredients in compositions or preparations, and usually also include adjuvants commonly used in pesticides; the adjuvants commonly used in pesticides include surfactants and / or carriers.

[0114] The above-mentioned surfactant can be any surfactant known in the field of pesticide formulations. In the present invention, it is preferably one or more of an emulsifier, a dispersant and a wetting agent.

[0115] The other carriers except the above-mentioned surfactants can be various carriers known in the field of pesticide formulations, including various silicates, carbonates, sulfates, oxides, phosphates, plant carriers, and synthetic carriers. Specifically, for example: one or more of white carbon black, kaolin, diatomaceous earth, clay, talc, organic bentonite, pumice, titanium dioxide, dextrin, cellulose powder, light calcium carbonate, soluble starch, corn starch, sawdust powder, urea, amine fertilizer, a mixture of urea and 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.

[0116] The emulsifier may be any emulsifier known in the field of pesticide formulations. Specifically, the emulsifier may be one or more of calcium dodecylbenzene sulfonate, triphenyl phenol polyoxyethylene ether phosphate, fatty alcohol polyoxyethylene ether, alkylphenol 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, terminal hydroxyl polyoxyethylene polyoxypropylene ether, styrylphenol formaldehyde resin polyoxyethylene polyoxypropylene ether and castor oil polyoxyethylene ether.

[0117] The above-mentioned dispersant can be various dispersants known in the field of pesticide formulations. Specifically, the dispersant is one or more of acrylic acid homopolymer sodium salt, maleic acid disodium salt, naphthalenesulfonic acid formaldehyde condensate sodium salt, rosin block polyoxyethylene ether polyoxypropylene ether sulfonate, terminal hydroxyl polyoxyethylene polyoxypropylene ether block copolymer, triphenyl phenol polyoxyethylene ether phosphate, fatty alcohol polyoxyethylene ether phosphate and p-hydroxyphenyl lignin sulfonate sodium salt.

[0118] The wetting agent can be any wetting agent known in the field of pesticide formulations. Specifically, the wetting agent can be one or more of sodium dodecyl sulfate, sodium secondary alkyl sulfate, sodium dodecylbenzene sulfonate, fatty alcohol polyoxyethylene ether, alkyl naphthalene sulfonate, and alkylphenol resin polyoxyethylene ether sulfate.

[0119] According to the fungicide composition of the present invention, the fungicide composition may also contain various formulation adjuvants commonly used in the field of pesticide formulations. Specifically, the formulation adjuvant may be one or more of a solvent, a co-solvent, a thickener, an antifreeze agent, an encapsulating material, a protective agent, a defoaming agent, a disintegrant, a stabilizer, a preservative and a binder.

[0120] The above-mentioned solvent may be any solvent known in the field of pesticide formulations. Specifically, the solvent may be one or more of an organic solvent, vegetable oil, mineral oil, solvent oil and water.

[0121] The organic solvent includes one or more of N-methylpyrrolidone, tetrahydrofuran, dimethyl sulfoxide, N,N-dimethyldecylamide, N,N-dimethylformamide, trimethylbenzene, tetramethylbenzene, xylene, toluene, octane, heptane, methanol, isopropanol, n-butanol, tetrahydrofurfuryl alcohol, tributyl phosphate, 1,4-dioxane and cyclohexanone.

[0122] The vegetable oil includes one or more of methylated vegetable oil, rosin-based vegetable oil, turpentine, epoxidized soybean oil, soybean oil, peanut oil, rapeseed oil, castor oil, corn oil and pine nut oil.

[0123] The mineral oil includes one or more of liquid wax, motor oil, kerosene and lubricating oil.

[0124] At the same time, the above solvents can also be used as co-solvents.

[0125] The antifreeze agent may be any antifreeze agent known in the field of pesticide formulations. In the present invention, the antifreeze agent is preferably one or more of ethylene glycol, propylene glycol, glycerol and urea.

[0126] The thickener may be any thickener known in the field of pesticide formulations. Specifically, the thickener may be one or more of xanthan gum, polyvinyl alcohol, polypropylene alcohol, polyethylene glycol, white carbon black, diatomaceous earth, kaolin, clay, sodium alginate, magnesium aluminum silicate, sodium aluminum silicate, carboxymethyl cellulose, sodium hydroxypropyl cellulose and organic bentonite.

[0127] The capsule material may be any capsule material known in the field of pesticide formulations, and in the present invention, preferably one or more of polyurethane, polyurea and urea-formaldehyde resin.

[0128] The protective agent can be any protective agent known in the field of pesticide formulations, and in the present invention, polyvinyl alcohol and / or polyethylene glycol are preferred.

[0129] The defoaming agent can be any defoaming agent known in the field of pesticide formulations. In the present invention, it is preferably one or more of organosiloxane, tributyl phosphate and silicone.

[0130] The stabilizer is selected from one or more of triphenyl phosphite, epichlorohydrin and acetic anhydride.

[0131] The preservative is selected from one or more of benzoic acid, sodium benzoate, 1,2-benzisothiazolin-3-one (BIT for short), kasone and potassium sorbate.

[0132] The present invention also provides a preparation prepared from the above-mentioned bactericidal composition, wherein the preparation is in the form of emulsifiable concentrate, aqueous emulsion, microemulsion, soluble liquid, aqueous suspension, suspoemulsion, ultra-low volume spray, oil suspension, microcapsule suspension, water-film spreading oil, wettable powder, water-dispersible granule, dry suspension, soluble powder, soluble granule, emulsifiable powder, emulsifiable granule, granule, solid microcapsule preparation, effervescent tablet, effervescent granule, water-floating dispersible granule or seed coating. The above-mentioned dosage forms can all be prepared by conventional methods in the art.

[0133] The preparation method of the emulsifiable concentrate preparation may include, for example, mixing and stirring the active components, solvent, co-solvent and emulsifier to form a uniform and transparent oil phase, thereby obtaining the emulsifiable concentrate preparation.

[0134] The preparation method of the aqueous emulsion may include, for example, mixing the active ingredient, emulsifier, cosolvent and solvent to form a uniform oil phase; mixing water, thickener, antifreeze agent, etc. to form a uniform water phase. Under high-speed shearing, the water phase is added to the oil phase or the oil phase is added to the water phase to form an aqueous emulsion with good dispersibility.

[0135] The preparation method of the microemulsion is, for example, to mix and stir the active ingredient, emulsifier and solvent into a uniform and transparent oil phase, and then gradually add water under stirring to form a uniform and transparent microemulsion.

[0136] The preparation method of the water / oil suspension is as follows: for example, water or oil can be used as the medium, active components, surfactants and other auxiliary agents are added to a sand mill, ground to a certain particle size, and then filtered. Then, a measured thickener is added to the ground mother liquid, sheared and dispersed evenly, to prepare an oil suspension or a water suspension.

[0137] The preparation method of the above-mentioned water-dispersible granules and soluble granules is, for example, to mix the active components, dispersant, wetting agent, carrier, etc. uniformly, then pulverize to a certain particle size by air flow, then add water for kneading, and finally add to a granulator for granulation. After drying, water-dispersible granules or soluble granules can be obtained.

[0138] The preparation method of the above-mentioned soluble powder and wettable powder is, for example, to fully mix the active components, various adjuvants and other fillers such as carriers, and grind them with an ultra-fine grinder.

[0139] The bactericidal composition of the present invention can be provided in the form of a finished preparation, that is, the various substances in the composition have been mixed; it can also be provided in the form of a separate preparation, which can be mixed in a bucket or tank before use and selectively mixed with water for dilution according to the required concentration of the active substance.

[0140] Application of the compounds and compositions of the present invention

[0141] The compounds of the present invention can be used as plant disease control agents. Therefore, the present invention can also include a method for controlling plant diseases caused by plant pathogenic fungi, the method comprising applying an effective amount of the compounds of the present invention or a fungicidal composition comprising the compounds to the plant to be protected or its part. The compounds and / or compositions of the present invention can provide control for diseases caused by a wide spectrum of plant pathogenic fungi of the classes Basidiomycetes, Ascomycetes, Oomycetes and Deuteromycetes. They can effectively control a wide spectrum of plant diseases, especially foliar pathogens of ornamental crops, turf crops, vegetable crops, field crops, cereal crops and fruit crops. These pathogens include: Oomycetes, including Phytophthora diseases such as Phytophthora infestans, Phytophthora megasperma, Phytophthora parasitica, Phytophthora cinnamomi, and Phytophthora capsici, Pythium species diseases such as Pythium aphanidermatum, and Peronosporaceae species diseases such as Plasmopara viticola, Peronospora spp. (including Peronospora tabacina and Peronospora parasitica), Pseudoperonospora spp.) diseases (including Pseudoperonospora cubensis and Bremia lactucae); Ascomycetes (including Alternaria such as Alternaria solani and Alternaria brassicae, Guignardia such as Guignardia bidwell, Venturia such as Venturia inaequalis, Septoria such as Septorianodorum and Septoria tritici, powdery mildew such as Erysiphe spp.) (including Erysiphe graminis and Erysiphe polygoni), Uncinula necatur, Sphaerotheca fuligena and Podosphaera leucotricha, Pseudocercosporella herpotrichoides, Botrytis diseases such as Botrytis cinerea, Monilinia fructicola, Sclerotinia diseases such as Sclerotinia sclerotiorum, Magnaporthe grisea, Phomopsis viticola, Helminthosporium diseases such as Helminthosporium tritici repentis), Pyrenophora teres, anthracnose pathogens such as Glomerella or Colletotrichum spp. diseases (e.g., Colletotrichum graminicola and Colletotrichum orbiculare), and Gaeumannomyces graminis; Basidiomycetes, including rust diseases caused by Puccinia spp. (e.g., Puccinia recondita, Puccinia striiformis, Puccinia hordei, Puccinia graminis, and Puccinia arachidis), Hemileia vastatrix, and Phakopsora pachyrhizi; other pathogens include Rhizoctonia spp.) (such as Rhizoctonia solani); Fusarium species diseases such as Fusarium roseum, Fusarium graminearum, and Fusarium oxysporum; Verticillium dahliae; Sclerotium rolfsii; Rynchosporium secalis; Cercosporidium personatum, Cercospora arachidicola, and Cercospora beticola; and other closely related species and fungi. In addition to their fungicidal activity, the compositions or combinations also have activity against bacteria such as Erwinia amylovora, Xanthomonas campestris, Pseudomonas syringae, and other species.

[0142] The method of using the fungicidal compound or composition of the present invention is simple. Before or after the emergence of plant diseases, the fungicidal compound or composition is applied to plants, plant parts or plant growth sites by conventional methods, such as mixing with soil, spraying, injection, pouring, etc. The application amount depends on the climatic conditions or the state of the crop. Generally, 10-5000 g per mu is applied, diluted to 10-400 mg / L (preferably 100-300 mg / L). The diluent is preferably water.

[0143] The fungicidal effect of the fungicidal compound or composition of the present invention is usually related to external factors such as climate, but the influence of climate can be mitigated by using appropriate formulations.

[0144] The compounds or compositions of the present invention may also be used in combination with other compounds having fungicidal, insecticidal or herbicidal properties, or with nematicides, miticides, protectants, herbicide safeners, growth regulators, plant nutrients or soil conditioners.

[0145] General synthesis process

[0146] The following schemes describe the preparation of the compounds of the present invention. Unless otherwise specified, the compounds of the present invention can be prepared by the methods described herein. The raw materials, reagents, etc. used to prepare the compounds of the present invention are all commercially available or can be prepared by methods conventional in the art. In this specification, if there is any difference between the chemical name and the chemical structure, the structure is dominant.

[0147] Synthesis scheme

[0148] Synthesis Scheme 1

[0149]

[0150] The target compound shown in formula (I-1) can be prepared by the preparation method of synthesis scheme 1. Intermediate compound A and intermediate compound B undergo nucleophilic substitution reaction under alkaline conditions (such as triethylamine, sodium hydride, pyridine, potassium carbonate, etc.) to obtain the target compound shown in formula (I-1); intermediate compound B can be purchased commercially or prepared by the preparation method in the prior art;

[0151] Among them, R 1 , R 2 and Hy have the meanings as defined in the present invention. Example

[0152] Intermediate 1: Synthesis of 1-(N,N-dimethylaminosulfonyl)-1H-1,2,4-triazole-3-sulfonyl chloride

[0153]

[0154] Step 1: Synthesis of 1,2-bis(1H-1,2,4-triazol-3-yl)disulfane

[0155]

[0156] Dissolve 3-mercapto-1,2,4-triazole (101.0 g, 1.00 mol) in dichloromethane (500 mL), add pyridine (79.0 g, 1.00 mol), stir at 0°C, slowly add p-toluenesulfonyl chloride (95.3 g, 0.50 mol), and add the solution over 2 hours. Stir at 25°C for 18 hours after the addition is complete. Use a rotary evaporator to evaporate the dichloromethane under reduced pressure, add water (500 mL) to the residue under mechanical stirring, and stir for 1 hour. Filter, wash the residue with water (800 mL) and ethyl acetate (300 mL), respectively, and air-dry to obtain 95.2 g of yellow powder with a yield of 95.2%.

[0157] LC-MS: (M+1) m / z=201.1.

[0158] Step 2: 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

[0159]

[0160] Under nitrogen protection, 1,2-bis(1H-1,2,4-triazole-3-yl)disulfane (60.0g, 0.30mol) was dissolved in N,N-dimethylformamide (300mL), potassium carbonate (69.0g, 0.50mol) was added, and the mixture was stirred at 0°C. N,N-dimethylaminosulfonyl chloride (93.3g, 0.65mol) was slowly added dropwise, and the addition was completed in 2 hours, and the reaction was continued for 6 hours. After the reaction was completed, the reaction solution was slowly poured into water and stirred for 1 hour. Filter and air-dry the solid to obtain 107.2g of white powder with a yield of 86.3%.

[0161] LC-MS: (M+1) m / z=415.0.

[0162] Step 3: Synthesis of 1-(N,N-dimethylaminosulfonyl)-1H-1,2,4-triazole-3-sulfonyl chloride

[0163]

[0164] 3-((1-(N,N-dimethylaminosulfonyl)-1H-1,2,4-triazol-3-yl)disulfanyl)-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°C, acetic acid (100 mL) was added, the temperature was controlled at 10°C to 25°C, chlorine gas (35.50 g, 0.50 mol) was introduced after 2 hours, and the reaction was continued for half an hour. After the reaction was completed, the solution was transferred to a separatory funnel, allowed to stand for separation, the organic phase was washed three times with water (30 mL), and the solvent was evaporated under reduced pressure using a rotary evaporator to obtain 48.11 g of white powder with a yield of 87.8%.

[0165] LC-MS: (M+1) m / z=274.8.

[0166] Example 1: Synthesis of N,N-dimethyl-3-((2-phenyl-1H-imidazol-1-yl)sulfonyl)-1H-1,2,4-triazole-1-sulfonamide

[0167]

[0168] 2-phenylimidazole (0.29g, 2.0mmol), triethylamine (0.40g, 4.0mol) and dichloromethane (15mL) were added to a 100mL single-mouth bottle and stirred at 25°C; 1-(N,N-dimethylaminosulfonyl)-1H-1,2,4-triazole-3-sulfonyl chloride (1.10g, 4.0mmol) was slowly added to the reaction system and reacted at 25°C for 12 hours. Water (100mL) was added to quench the reaction, and ethyl acetate (50mL x 3) was used for extraction. The organic phase was dried over anhydrous sodium sulfate, filtered, and the filtrate was decompressed to remove the solvent by rotary evaporator. The residue was purified by column chromatography [ethyl acetate / petroleum ether (v / v) = 1 / 3] to obtain 0.33g of light yellow liquid, with a yield of 43.2%.

[0169] The characterization data of Example 1 are as follows:

[0170] 1 H 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);

[0171] LC-MS: (M+1) m / z=383.0.

[0172] The corresponding materials and intermediate 1 (i.e., 1-(N,N-dimethylaminosulfonyl)-1H-1,2,4-triazole-3-sulfonyl chloride, the corresponding structural formula is The target compounds in Table 1 were obtained by using the synthetic method of Example 1 as the reaction raw materials.

[0173] Table 1

[0174]

[0175]

[0176]

[0177]

[0178] Intermediate 2: Synthesis of 2-(3-bromophenyl)-1H-benzo[d]imidazole

[0179]

[0180] m-Bromobenzaldehyde (0.93g, 5mmol), o-phenylenediamine (0.54g, 5mmol), sodium iodide (0.75g, 5mmol) were added to a 100mL two-necked flask, and then N,N-dimethylformamide (15mL) was added, and the mixture was reacted at 80°C for 12 hours. Water (50mL) was added to quench the reaction, and the mixture was extracted with ethyl acetate (50mL x 3). The organic phase was dried over anhydrous sodium sulfate, filtered, and the filtrate was dried under reduced pressure to obtain 1.09g of a light yellow oil with a yield of 80.4%.

[0181] LC-MS: (M+1) m / z=273.0.

[0182] Using o-phenylenediamine and corresponding benzaldehyde or benzaldehyde derivatives as reaction raw materials, refer to the synthesis method of intermediate 2 for preparation, and the intermediate compounds in Table 2 can be obtained.

[0183] Table 2

[0184]

[0185]

[0186] 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

[0187]

[0188] At room temperature, 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 100 mL two-necked flask, stirred at 25°C 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, and stirring continued at room temperature for 3 hours. Water (150 mL) was added to quench the reaction, and ethyl acetate (50 mL x 3) was used for extraction. The organic phase was dried over anhydrous sodium sulfate, filtered, and the filtrate was subjected to a rotary evaporator to remove the solvent under reduced pressure. The residue was purified by column chromatography [ethyl acetate / petroleum ether (v / v) = 1 / 3] to obtain 0.67 g of a white solid, with a yield of 65.8%.

[0189] The characterization data of Example 18 are as follows:

[0190] 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);

[0191] LC-MS: (M+1) m / z=511.0.

[0192] Using intermediate 1 and the corresponding intermediate compound in Table 2 as reaction raw materials, refer to the synthesis method of Example 18 to prepare the target compound in Table 3.

[0193] Table 3

[0194]

[0195]

[0196]

[0197] Using the corresponding materials and intermediate 1 as reaction raw materials and referring to the synthesis method of Example 1 or Example 18, the comparative compounds 1-4 in Table 4 can be obtained.

[0198] Table 4

[0199]

[0200]

[0201] Biological activity test

[0202] In the following test examples, the inventors took some compounds of the present invention and comparative compounds as examples to detect the control efficacy of the compounds of the present invention and comparative compounds on harmful fungi.

[0203] Test target: Cucumber downy mildew (Pseudoperonospora cubensis)

[0204] Test treatment: The compounds were dissolved in DMF to 1% EC for later use. The in vivo pot culture method was used to evaluate the fungicidal activity of these compounds at different doses (such as 200 mg / L, 100 mg / L, 50 mg / L, 25 mg / L) against the test target.

[0205] Select a potted cucumber seedling with the same growth in the true leaf stage (remove the growth point), spray it and dry it naturally. Inoculate it 24 hours after treatment. Take fresh cucumber downy mildew diseased leaves, use a brush dipped in distilled water to wash off the sporangium on the back of the diseased leaves, and prepare a sporangium suspension (2-3x 10 5 / mL). Use an inoculation sprayer (pressure 0.1MPa) to evenly spray inoculation on cucumber seedlings. Move the inoculated test materials to an artificial climate room and maintain a relative humidity of 100% and a temperature of about 21°C. After 24 hours, maintain a temperature of about 21°C and a relative humidity of about 95% to induce moisture. After 5 days, conduct a graded investigation based on the incidence of the blank control and calculate the prevention effect according to the disease index.

[0206] The test results are as follows:

[0207] At a dosage of 200 mg / L, the protective 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 24, Example 25, Example 26, Example 27, and Example 28 on cucumber downy mildew is ≥80%;

[0208] At a dosage of 100 mg / L, the protective 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, and Example 24 on cucumber downy mildew is ≥80%;

[0209] At a dosage of 50 mg / L, the protective effects of Examples 5, 6, 7, 8, 9, 13, 14, 15, 16, 19, 20, 22, 24, 25 and 26 on cucumber downy mildew were ≥ 80%; at the same dosage, the protective effects of comparative compounds 1-4 on cucumber downy mildew are shown in Table 5:

[0210] Table 5 The protective effect of the compounds on cucumber downy mildew at a dosage of 50 mg / L

[0211]

[0212] It can be seen from the above test results that the compounds of the present invention have excellent protective effects against plant diseases, especially cucumber downy mildew even at low doses (for example, at a dose of 25 mg / L, the protective effects of Examples 8, 13, 15, 16, 18, 19, 20, 22, 24, and 25 against cucumber downy mildew are ≥ 80%), and can be used as fungicides in agriculture.

[0213] The preferred embodiments of the present invention are described in detail above. However, the present invention is not limited to the specific details in the above embodiments. Within the technical concept of the present invention, a variety of simple modifications can be made to the technical solution of the present invention, and these simple modifications all belong to the protection scope of the present invention.

Claims

1. A compound, which is a compound represented by formula (I) or a salt thereof: (I)； in: R 1 and R 2 Each independently is -CH3; n is 2; Hy , or ;in, R a is optionally substituted by 1 or 2 selected from fluorine, chlorine, bromine, iodine, -halogenated C 1-4 Alkyl-substituted phenyl or pyridyl; R b 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; R e is hydrogen, -C(=O)H; R f is hydrogen; R g is optionally substituted by 1 or 2 selected from fluorine, chlorine, bromine, iodine, -halogenated C 1-4 Phenyl substituted with alkyl or pyridyl optionally substituted with 1 group selected from fluorine, chlorine, bromine and iodine.

2. The compound according to claim 1, wherein: R a is phenyl or pyridyl optionally substituted by 1 or 2 groups selected from fluorine, chlorine, bromine, iodine, -CF3; R b is hydrogen or -CH3; R d is phenyl, pyridyl or thienyl optionally substituted by 1 group selected from fluorine, chlorine, bromine or iodine; R e It 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 ; Among them, R g It is phenyl optionally substituted by 1 or 2 groups selected from fluorine, chlorine, bromine, iodine and -CF3, or pyridyl optionally substituted by 1 group selected from fluorine, chlorine, bromine and 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.

Images