Triazole sulfonamide derivatives and preparation method and application thereof

Abstract

The present invention relates to a triazole sulfonamide derivative and a preparation method and application thereof; specifically, the present invention relates to a triazole sulfonamide derivative represented by formula (I) or a stereoisomer, nitrogen oxide or salt thereof of the triazole sulfonamide derivative represented by formula (I), a preparation method of the triazole sulfonamide derivative, and their use as fungicides in agriculture, and the form of a composition thereof, as well as a method for controlling plant diseases using these compounds or compositions; wherein R 1 , R 2 , R 3 , R 4 and X have the meanings as defined in the present invention.

Description

Technical Field

[0001] The present invention belongs to the field of pesticides. Specifically, the present invention provides a novel triazole sulfonamide derivative and a preparation method thereof and an application of the derivative as a plant disease control agent in agriculture. Background Art

[0002] In order to obtain high crop yields, it is extremely important to control plant diseases caused by phytopathogenic fungi. Plant diseases caused by phytopathogenic fungi that damage ornamental crops, vegetable crops, field crops, cereal crops and fruit crops can cause a significant reduction in yield, thereby leading to rising consumer costs. In order to obtain high crop yields, it is extremely important to control plant diseases caused by phytopathogenic fungi. For this purpose, pesticide products can be used in plant planting and growth processes, and there are many products available commercially, but there is a continuous need for new compounds that are more effective, more economical, less toxic, safer for the environment, or have different sites of action. Summary of the invention

[0003] The object of the present invention is to provide a novel triazole sulfonamide derivative, which has excellent preventive effect on plant diseases caused by pathogenic fungi, especially cucumber downy mildew.

[0004] In order to achieve the purpose of the present invention, the following technical scheme is adopted:

[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 C 6-14 Aryl or 5-6 membered heteroaryl; wherein R 1 Optionally substituted by 1, 2, 3, 4 or 5 groups selected from halogen, hydroxy, cyano, nitro, amino, C 1-4 Alkyl, C 2-4 Alkenyl, C 2-4 Alkynyl, C 1-4 Alkoxy, C 1-4 Alkylthio, halo 1-4 Alkyl, halogenated C 1-4 Alkoxy, halogenated C 1-4 Alkylthio, C 1-4 Alkyl-C(=O)-, C 1-4 Alkyl-C(=O)O-, C 1-4 Alkoxy-C(=O)-, -NH-C 1-4 Alkyl, -N(C1-4 alkyl)2, optionally substituted by 1, 2, 3, 4 or 5 groups selected from halogen, hydroxy, cyano, nitro, 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 groups selected from halogen, hydroxy, cyano, nitro, C 1-4 Alkyl, C 1-4 Alkoxy, halogenated C 1-4 Alkyl or halogenated C 1-4 Alkoxy substituted phenoxy substituted;

[0009] R 2 For hydrogen, C 1-6 Alkyl, C 2-6 Alkenyl, C 2-6 Alkynyl, C 3-8 Cycloalkyl or C 3-8 Cycloalkyl-C 1-3 Alkylene-; wherein R 2 Optionally, 1, 2, 3, 4, 5 or 6 groups selected from halogen, cyano, hydroxy, nitro, amino, C 1-4 Alkyl, C 2-4 Alkenyl, C 2-4 Alkynyl, C 3-6 Cycloalkyl, C 3-6 Cycloalkyl-C 1-3 Alkylene-, halogenated C 1-4 Alkyl, C 1-4 Alkoxy or halogenated C 1-4 Alkoxy substitution;

[0010] R 3 and R 4 are independently hydrogen, C 1-6 Alkyl, C 2-6 Alkenyl, C 2-6 Alkynyl, C 3-8 Cycloalkyl, C 3-8 Cycloalkyl-C 1-3 alkylene-, phenyl optionally substituted by 1, 2, 3, 4 or 5 groups selected from halogen, or phenyl-C optionally substituted by 1, 2, 3, 4 or 5 groups selected from halogen 1-3 Alkylene-;

[0011] or R 3 , R 4 Together with the nitrogen atom to which it is attached, it forms a 3-8 membered heterocyclic group or a 5-10 membered heteroaryl group;

[0012] X is #-CR 5 R 6 -CR 7 R8 -CR 9 R 10 -*; where "#" indicates the connection end and -NR 2 - connected, the connection end indicated by "*" is connected to -R 1 Connected;

[0013] Among them, R 5 and R 6 are independently hydrogen or C 1-6 alkyl;

[0014] R 7 and R 8 are independently hydrogen or C 1-6 alkyl;

[0015] R 9 and R 10 are independently hydrogen or C 1-6 alkyl;

[0016] or R 5 , R 7 It forms a carbon-carbon double bond with the carbon atom it is connected to; R 5 , R 7 After forming a carbon-carbon double bond with the carbon atom it is connected to, X is #-CR 6 =CR 8 -CR 9 R 10 -*;

[0017] or R 7 , R 9 It forms a carbon-carbon double bond with the carbon atom it is connected to; R 7 , R 9 After forming a carbon-carbon double bond with the carbon atom it is connected to, X is #-CR 5 R 6 -CR 8 =CR 10 -*.

[0018] In some embodiments, R 1 C 6-14 Aryl or pyridyl; wherein R 1 Optionally substituted by 1, 2, 3, 4 or 5 groups selected from halogen, hydroxy, cyano, nitro, amino, C 1-4 Alkyl, C 2-4 Alkenyl, C 2-4 Alkynyl, C 1-4 Alkoxy, C 1-4 Alkylthio, halo 1-4 Alkyl, halogenated C 1-4 Alkoxy, halogenated C 1-4 Alkylthio, C1-4 Alkyl-C(=O)-, C 1-4 Alkyl-C(=O)O-, C 1-4 Alkoxy-C(=O)-, -NH-C 1-4 Alkyl, -N(C 1-4 alkyl)2, optionally substituted by 1, 2, 3, 4 or 5 groups selected from halogen, hydroxy, cyano, nitro, 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 groups selected from halogen, hydroxy, cyano, nitro, C 1-4 Alkyl, C 1-4 Alkoxy, halogenated C 1-4 Alkyl or halogenated C 1-4 Alkoxy substituted phenoxy substituted.

[0019] In other embodiments, R 1 is phenyl, naphthyl, anthracenyl or pyridin-3-yl; wherein R 1 Optionally substituted by 1, 2, 3, 4 or 5 groups selected from halogen, hydroxy, cyano, nitro, amino, C 1-4 Alkyl, C 2-4 Alkenyl, C 2-4 Alkynyl, C 1-4 Alkoxy, C 1-4 Alkylthio, halo 1-4 Alkyl, halogenated C 1-4 Alkoxy, halogenated C 1-4 Alkylthio, C 1-4 Alkyl-C(=O)-, C 1-4 Alkyl-C(=O)O-, C 1-4 Alkoxy-C(=O)-, -NH-C 1-4 Alkyl, -N(C 1-4 alkyl)2, optionally substituted by 1, 2, 3, 4 or 5 groups selected from halogen, hydroxy, cyano, nitro, 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 groups selected from halogen, hydroxy, cyano, nitro, C 1-4 Alkyl, C 1-4 Alkoxy, halogenated C 1-4 Alkyl or halogenated C 1-4 Alkoxy substituted phenoxy substituted.

[0020] R 1 is phenyl, naphthyl, anthracenyl or pyridin-3-yl, wherein the phenyl is The naphthyl group includes The anthracene group includes The pyridin-3-yl group is Indicates where a group is attached to the rest of the molecule.

[0021] In yet other embodiments, R 1 is phenyl, naphthyl, anthracenyl or pyridin-3-yl; wherein R 1 The invention is optionally substituted by 1, 2, 3, 4 or 5 groups selected from fluorine, chlorine, bromine, iodine, hydroxyl, cyano, nitro, amino, -CH3, -CH2CH3, -CH2CH2CH3, -CH(CH3)2, -CH2CH2CH2CH3, -CH2CH(CH3)2, -CH(CH3)CH2CH3, -C(CH3)3, -CH=CH2, -CH2CH=CH2, -C≡CH, -CH2C≡CH, -OCH3, -OCH2CH3, -OCH2CH2CH3, -OCH(CH3)2, -OCH2CH2CH2CH3, -OCH2CH(CH3)2, -OCH(CH3)CH2CH3, -OC(CH3)3, -SCH3, -SCH2CH3, -SC H2CH2CH3, -SCH(CH3)2, -CHF2, -CF3, -OCHF2, -OCF3, -SCF3, -C(=O)CH3, -C(=O)CH2CH3, -C(=O)CH2CH2CH3, -C(=O)CH(CH3)2, -OC(=O)CH3, -OC(=O)CH2CH3, -OC(=O)CH2CH2CH3, -OC(=O)CH(CH3)2, -C(=O)OCH3, -C(=O)OCH2CH3, -C(=O)OCH2CH2CH3, -C(=O)OCH(CH3)2, -NHCH3, -NHCH2CH3, -N(CH3)2, -N(CH2CH3)2, phenyl or phenoxy substituted.

[0022] In yet other embodiments, R 1 for

[0023] In some embodiments, X is #-CR 5 R 6 -CR 7 R 8 -CR 9 R 10 -*,#-CR 6 =CR 8 -CR 9 R 10 -* or #-CR 5 R6 -CR 8 =CR 10 -*; where "#" indicates the connection end and -NR 2 - connected, the connection end indicated by "*" is connected to -R 1 Connected;

[0024] Among them, R 5 and R 6 are independently hydrogen or C 1-6 alkyl;

[0025] R 7 and R 8 are independently hydrogen or C 1-6 alkyl;

[0026] R 9 and R 10 are independently hydrogen or C 1-6 alkyl.

[0027] In some embodiments, X is #-CH2-CH2-CH2-.

[0028] In other embodiments, X is #-CR 5 R 6 -CR 8 =CR 10 -*; where "#" indicates the connection end and -NR 2 - connected, the connection end indicated by "*" is connected to -R 1 Connected;

[0029] R 5 and R 6 each independently is hydrogen;

[0030] R 8 is hydrogen or C 1-6 alkyl;

[0031] R 10 is hydrogen or C 1-6 alkyl.

[0032] Preferably, in some embodiments, R 10 is hydrogen or C 1-4 More preferably, R 10 For hydrogen.

[0033] In yet other embodiments, X is #-CH2-CR 8 =CR 10 -*; where "#" indicates the connection end and -NR 2 - connected, the connection end indicated by "*" is connected to -R 1 Connected;

[0034] R 8 is hydrogen, -CH3, -CH2CH3, -CH2CH2CH3, -CH(CH3)2, -CH2CH2CH2CH3, -CH2CH2CH2CH2CH3 or -CH2CH2CH2CH2CH2CH3;

[0035] R 10 is hydrogen, -CH3, -CH2CH3, -CH2CH2CH3, -CH(CH3)2, -CH2CH2CH2CH3, -CH2CH2CH2CH2CH3 or -CH2CH2CH2CH2CH2CH3.

[0036] In some embodiments, R 2 For hydrogen, C 1-4 Alkyl, C 2-4 Alkenyl, C 2-4 Alkynyl, C 3-6 Cycloalkyl or C 3-6 Cycloalkyl-C 1-3 Alkylene-; wherein R 2 Optionally, 1, 2, 3, 4, 5 or 6 groups selected from halogen, cyano, hydroxy, nitro, amino, C 1-4 Alkyl, C 2-4 Alkenyl, C 2-4 Alkynyl, C 3-6 Cycloalkyl, C 3-6 Cycloalkyl-C 1-3 Alkylene-, halogenated C 1-4 Alkyl, C 1-4 Alkoxy or halogenated C 1-4 Alkoxy substitution.

[0037] In other embodiments, R 2 is hydrogen, -CH3, -CH2CH3, -CH2CH2CH3, -CH(CH3)2, -CH2CH2CH2CH3, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl or cyclopropyl-CH2-; wherein R 2 Optionally substituted by 1, 2, 3, 4, 5 or 6 groups selected from fluorine, chlorine, bromine, iodine, cyano, hydroxy, nitro, amino, -CH3, -CH2CH3, -CH2CH2CH3, -CH(CH3)2, -CH2CH2CH2CH3, -CH2CH(CH3)2, -CH(CH3)CH2CH3, -C(CH3)3, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl or cyclopropyl-CH2-.

[0038] Preferably, R 2 C 3-6 More preferably, R 2 It is cyclopropyl.

[0039] In some embodiments, R 3 and R 4 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-, phenyl or phenyl-C 1-3 Alkylene-.

[0040] In other embodiments, R 3 and R 4 Each is independently hydrogen, -CH3, -CH2CH3, -CH2CH2CH3, -CH(CH3)2, -CH2CH2CH2CH3, -CH2CH(CH3)2, -CH(CH3)CH2CH3, -CH=CH2, -CH2CH=CH2, cyclopropyl, cyclopropyl-CH2-, phenyl or benzyl.

[0041] Preferably, R 3 and R 4 are independently hydrogen or C 1-4 Alkyl; More preferably, R 3 and R 4 Each independently is C 1-4 Alkyl; further preferably, R 3 and R 4 Each is independently -CH3.

[0042] In some embodiments, R 3 , R 4 Together with the nitrogen atom to which it is attached, it forms a 3-6 membered heterocyclic group or a 5-10 membered heteroaryl group.

[0043] In other embodiments, R 3 , R 4 Together with the nitrogen atom connected to it, the substructure formula is:

[0044]

[0045] In some embodiments, the present invention provides a compound, which is a compound represented by formula (II) or a nitrogen oxide, salt, (E) isomer, (Z) isomer, and a mixture of (E) isomer and (Z) isomer of the compound represented by formula (II):

[0046]

[0047] Among them, R 1 , R 2, R 3 , R 4 , R 8 and R 10 Has the meaning as described in the present invention.

[0048] 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:

[0049]

[0050]

[0051] In another aspect, the present invention provides a composition comprising at least one compound described herein.

[0052] Furthermore, the composition of the present invention comprises adjuvants commonly used in pesticides.

[0053] In yet another aspect, the present invention provides use of the compound of the present invention and / or the composition of the present invention in controlling plant diseases.

[0054] Furthermore, the plant diseases described in the present invention are caused by plant pathogenic fungi.

[0055] The plant diseases include cucumber downy mildew, cucumber gray mold, cucumber powdery mildew and rice sheath blight.

[0056] Detailed description of the invention

[0057] Definitions and general terms

[0058] 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.

[0059] 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.

[0060] 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.

[0061] Unless otherwise indicated, the following definitions used in the present invention shall apply. For the 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.

[0062] 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.

[0063] The term "comprising" is an open expression, that is, including the contents specified in the present invention but not excluding other contents.

[0064] "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.

[0065] "Enantiomers" refer to two non-superimposable isomers of a compound that are mirror images of each other.

[0066] "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.

[0067] The stereochemical definitions and conventions used in this 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.

[0068] Many organic compounds exist in optically active forms, i.e. they have the ability to rotate the plane of plane polarized light. In 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 signs used to designate the rotation of plane polarized light caused by the compound, where (-) or l indicates that the compound is levorotatory. A compound prefixed with (+) or d is dextrorotatory. A specific stereoisomer is an enantiomer, and a mixture of such isomers is called an enantiomeric mixture. A 50:50 mixture of enantiomers is called a racemic mixture or racemate, which can occur when there is no stereoselectivity or stereospecificity in a chemical reaction or process.

[0069] 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.

[0070] 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.

[0071] 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.

[0072] The racemate of any resulting final product or intermediate can be split into optical antipodes by known methods by methods familiar to those skilled in the art, such as by separating the diastereomeric salts 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. The "stereoisomer" of the compound of the present invention mainly refers to the (E) type isomer and the (Z) type isomer of the compound. The compound of the present invention includes a mixture of (E) type isomers, (Z) type isomers, (E) type isomers and (Z) type isomers. Preferably, the configuration of the compound of the present invention is the (E) type isomer.

[0073] 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 the terms "substituted or unsubstituted". In general, "optionally substituted" and "optionally substituted with..." substituents" mean that the given structure is unsubstituted or that 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.

[0074] 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.

[0075] 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.

[0076] 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.

[0077] 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.

[0078] 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.

[0079] 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.

[0080] 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.

[0081] 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.

[0082] 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.

[0083] 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.

[0084] 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.

[0085] 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.

[0086] 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.

[0087] 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-dioxolanyl, dithiolanyl, tetrahydropyranyl, dihydropyranyl, 2H-pyranyl, 4H-pyranyl, 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.

[0088] 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.

[0089] 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).

[0090] The term "halogen" refers to fluorine (F), chlorine (Cl), bromine (Br) or iodine (I).

[0091] 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.

[0092] 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, 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 include the following bicyclic rings, but are by no means limited to these bicyclic rings: benzimidazolyl, benzofuranyl, benzotetrahydrofuranyl, benzothienyl, indolyl (such as 2-indolyl), benzopiperidinyl, and the like.

[0093] 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.

[0094] 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.

[0095] 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.

[0096] 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.

[0097] 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 D Independently selected from hydrogen, C1-C6 alkyl and C1-C6 hydroxyalkyl. Salts of compounds of formula (I) or (II) can be prepared by treating compounds of formula (I) or (II) with metal hydroxides (e.g. sodium hydroxide) or amines (e.g. ammonia, trimethylamine, diethanolamine, 2-methylthiopropylamine, bisallylamine, 2-butoxyethylamine, morpholine, cyclododecylamine or benzylamine).

[0098] 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.

[0099] Compositions and preparations of the compounds of the present invention

[0100] 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.

[0101] 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.

[0102] 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.

[0103] 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.

[0104] 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.

[0105] 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.

[0106] 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.

[0107] 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.

[0108] 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.

[0109] 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.

[0110] The mineral oil includes one or more of liquid wax, motor oil, kerosene and lubricating oil.

[0111] At the same time, the above solvents can also be used as co-solvents.

[0112] 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.

[0113] 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.

[0114] 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.

[0115] 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.

[0116] 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.

[0117] The stabilizer is selected from one or more of triphenyl phosphite, epichlorohydrin and acetic anhydride.

[0118] 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.

[0119] 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.

[0120] 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.

[0121] 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.

[0122] 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.

[0123] 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.

[0124] 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.

[0125] 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.

[0126] 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.

[0127] Application of the compounds and compositions of the present invention

[0128] 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. (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.

[0129] 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.

[0130] 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.

[0131] 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.

[0132] General synthesis process

[0133] 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.

[0134] Synthesis scheme

[0135] Synthesis Scheme 1

[0136]

[0137] The target compound represented by formula (I) can be prepared by the preparation method of synthesis scheme 1. The compound represented by formula (a) and the compound represented by formula (b) undergo nucleophilic substitution reaction under alkaline conditions (such as pyridine, sodium hydride, potassium carbonate, etc.) to obtain the target compound represented by formula (I);

[0138] Among them, X, R 1 , R 2 , R 3 and R 4 Has the meaning described in the present invention. Example

[0139] Intermediate 1: N 3 -Cyclopropyl-N 1 , N 1 Synthesis of dimethyl-1H-1,2,4-triazole-1,3-disulfonamide

[0140]

[0141] Step 1: Synthesis of 1,2-bis(1H-1,2,4-triazol-3-yl)disulfane

[0142]

[0143] 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 dropwise for 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 conditions, and stir for 1 hour. Filter, wash the filter 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%.

[0144] LC-MS: (M+1) m / z=201.2.

[0145] 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

[0146]

[0147] Under nitrogen protection, 1,2-bis(1H-1,2,4-triazole-3-yl)disulfane (60.0 g, 0.30 mol) was dissolved in N,N-dimethylformamide (300 mL), potassium carbonate (69.0 g, 0.50 mol) was added, and the mixture was stirred at 0°C. N,N-dimethylaminosulfonyl chloride (93.3 g, 0.65 mol) 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 107.2 g of white powder with a yield of 86.3%.

[0148] LC-MS: (M+1) m / z=415.0.

[0149] Step 3: Synthesis of 1-(N,N-dimethylaminosulfonyl)-1H-1,2,4-triazole-3-sulfonyl chloride

[0150]

[0151] 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 separating 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%.

[0152] LC-MS: (M+1) m / z=274.8.

[0153] Step 4: N 3 -Cyclopropyl-N 1 , N 1 Synthesis of dimethyl-1H-1,2,4-triazole-1,3-disulfonamide

[0154]

[0155] Under nitrogen protection, cyclopropylamine (1.14 g, 0.02 mol), triethylamine (2.22 g, 0.022 mol) and tetrahydrofuran (30 mL) were added to a 100 mL three-necked flask, stirred at 0°C, and a solution of 1-(N, N-dimethylaminosulfonyl)-1H-1,2,4-triazole-3-sulfonyl chloride (6.04 g, 0.02 mol) in tetrahydrofuran (20 mL) was added dropwise over 10 minutes. After the addition was completed, the mixture was reacted at 25°C for 2 hours. The solid was filtered off, and the filtrate was decompressed to remove the solvent using a rotary evaporator to obtain a light yellow solid, which was recrystallized [ethyl acetate / petroleum ether (v / v) = 5 / 1] to obtain 4.42 g of a white solid with a yield of 75.0%.

[0156] 1 H NMR (400MHz, DMSO-d6) δ (ppm) 9.30 (s, 1H), 7.49 (s, 1H), 2.96 (s, 6H), 2.48 (m, 1H), 0.63-0.56 (m, 2H), 0.50-0.43 (m, 2H).

[0157] LC-MS: (M+1) m / z=296.3.

[0158] Intermediate 2: Synthesis of (E)-(3-bromoprop-1-en-1-yl)benzene

[0159]

[0160] Synthesis method 1 of intermediate 2:

[0161] Step 1: Synthesis of (E)-prop-1-en-1-ylbenzene

[0162]

[0163] At room temperature, benzaldehyde (1.06 g, 10 mmol) and 1,4-dioxane (25 mL) were added to a 100 mL three-necked flask, stirred evenly, triphenylphosphine bromoethane (4.06 g, 11 mmol) and anhydrous potassium carbonate (2.07 g, 15 mmol) were added in sequence, and heated to 110°C and refluxed for 8 hours. Heating was stopped and the solvent was removed under reduced pressure, n-hexane was added to the residue and stirred for 10 minutes, the solid was removed by filtration, and the filtrate was decompressed and the solvent was removed by rotary evaporator to obtain 0.96 g of light yellow liquid, with a yield of 77.03%.

[0164] LC-MS: (M+1) m / z = 119.1.

[0165] Step 2: Synthesis of (E)-(3-bromoprop-1-en-1-yl)benzene

[0166]

[0167] At room temperature, (E)-prop-1-en-1-ylbenzene (0.83 g, 7 mmol) and carbon tetrachloride (25 mL) were added to a 100 mL single-mouth bottle and stirred evenly, and then N-bromosuccinimide (0.93 g, 7 mmol) and azobisisobutyronitrile (0.15 g, 1.5 mmol) were added in sequence, and heated to 80°C for 12 hours. After the reaction solution was cooled to room temperature, the sample was mixed with silica gel and purified by column chromatography [ethyl acetate / petroleum ether (v / v) = 1 / 3] to obtain 0.56 g of a light yellow liquid with a yield of 40.82%.

[0168] LC-MS: (M+1) m / z = 197.0.

[0169] Using corresponding materials as raw materials, referring to the synthesis method 1 of intermediate 2, or referring to the synthesis method in the prior art, after reaction, the intermediate compounds in Table 1 can be obtained.

[0170] Table 1

[0171]

[0172]

[0173]

[0174]

[0175] Intermediate 2: Synthesis of (E)-(3-bromoprop-1-en-1-yl)benzene

[0176]

[0177] Synthesis method 2 of intermediate 2:

[0178] Step 1: Synthesis of (E)-3-phenylprop-2-en-1-ol

[0179]

[0180] Cinnamaldehyde (1.32 g, 10 mmol) was dissolved in methanol (25 mL), stirred evenly in a 100 mL single-mouth bottle, and sodium borohydride (0.76 g, 20 mmol) was slowly added at 0°C to react for 3 hours. 10 mL of water was slowly added to the reaction solution to quench the reaction, and ethyl acetate (50 mL x 3) was used for extraction. The organic phase was dried over anhydrous magnesium sulfate, filtered, and the filtrate was decompressed and the solvent was removed by rotary evaporator to obtain 1.15 g of light yellow liquid with a yield of 85.78%.

[0181] LC-MS: (M+1) m / z=135.0

[0182] Step 2: Synthesis of (E)-(3-bromoprop-1-en-1-yl)benzene

[0183]

[0184] (E)-3-phenylprop-2-en-1-ol (0.94 g, 7 mmol) and dichloromethane (25 mL) were added to a 100 mL single-mouth bottle and stirred evenly. Phosphorus tribromide (3.79 g, 14 mmol) was slowly added dropwise at 0°C to react for 0.5 hours. 10 mL of water was slowly added to the reaction solution to quench the reaction, and ethyl acetate (50 mL x 3) was used for extraction. The organic phase was dried over anhydrous magnesium sulfate and filtered. The filtrate was decompressed and the solvent was removed by rotary evaporator to obtain 1.21 g of light yellow liquid with a yield of 88.19%.

[0185] LC-MS: (M+1) m / z = 197.0.

[0186] Using the corresponding materials as raw materials, referring to the synthesis method 2 of intermediate 2, or referring to the synthesis method in the prior art, after reaction, the intermediate compounds in Table 2 can be obtained.

[0187] Table 2

[0188]

[0189]

[0190] Example 1: N 3 -Cinnamyl-N 3 -Cyclopropyl-N 1 , N 1 Synthesis of dimethyl-1H-1,2,4-triazole-1,3-disulfonamide

[0191]

[0192] N 3 -Cyclopropyl-N 1 , N 1-Dimethyl-1H-1,2,4-triazole-1,3-disulfonamide (intermediate 1) (0.59 g, 2 mmol), anhydrous potassium carbonate (0.55 g, 4 mmol) and N, N-dimethylformamide (15 mL) were added to a single-mouth bottle, and a solution of (E)-(3-bromoprop-1-en-1-yl)benzene (intermediate 2) (0.78 g, 4 mmol) in N, N-dimethylformamide (5 mL) was added dropwise under stirring at 25°C, and the reaction was continued with stirring for 12 hours. 150 mL of water 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 decompressed to remove the solvent on a rotary evaporator. The residue was purified by column chromatography [ethyl acetate / petroleum ether (v / v) = 1 / 3] to obtain 0.63 g of a white solid, with a yield of 76.62%.

[0193] 1 H NMR (400MHz, CDCl3) δ (ppm) 8.61 (s, 1H), 7.35-7.31 (m, 4H), 7.28-7.26 (m, 1H), 6.56 (d, J = 15.8Hz, 1H), 6 .25 (m, 1H), 4.19 (d, J=6.8Hz, 2H), 3.03 (s, 6H), 2.68-2.63 (m, 1H), 1.03-0.96 (m, 2H), 0.89-0.81 (m, 2H).

[0194] LC-MS: (M+1) m / z=412.1.

[0195] Using intermediate 1 and the corresponding intermediate in Table 1 or Table 2 as reaction raw materials, refer to the synthesis method of Example 1, and after reaction, the target compounds in Table 3 can be obtained.

[0196] Table 3

[0197]

[0198]

[0199]

[0200]

[0201]

[0202]

[0203]

[0204]

[0205]

[0206]

[0207] Intermediate 1 and corresponding materials are used as reaction raw materials, respectively, and after reaction with reference to the synthesis method of Example 1, the target compounds in Table 4 can be obtained.

[0208] Table 4

[0209]

[0210]

[0211] Bio-test

[0212] Test targets: Rice sheath blight, cucumber gray mold, cucumber downy mildew, cucumber powdery mildew

[0213] Test treatment: The compounds were dissolved in DMF to 1% EC for later use. The in vivo pot 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, etc.) against the test target.

[0214] 1) Cucumber downy mildew test (Pseudoperonosporacubensis)

[0215] 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.

[0216] 2) Rice Sheath Blight Pathogen Test (Rhizoctonia solani)

[0217] Select potted rice seedlings with two leaves and one heart, with the same growth. After spraying, let them dry naturally. Inoculate them about 24 hours later. After the spray of the agent has dried, inoculate the fungus cake on the leaves. After 24 hours of dark light moisturizing at 25-26℃, restore natural light moisturizing and culture for about 3 days. After the control is fully diseased, use a caliper to measure the length of the lesion at each inoculation point and calculate the prevention effect.

[0218] 3) Cucumber gray mold test (Botrytis cmerea)

[0219] Use leaf inoculation method. Select two cucumber seedlings with the same growth in the true leaf stage, wait for the spray to dry, and then inoculate the fungus cake on the leaves. After 24 hours of dark light moisturizing at 24-26℃, restore natural light moisturizing and culture for about 3 days. After the control is fully diseased, use a caliper to measure the diameter of the lesion at each inoculation point and calculate the prevention effect.

[0220] 3) Cucumber powdery mildew test (Sphaerotheca fuliginea)

[0221] Select a cucumber seedling in the true leaf stage with uniform growth, spray it and dry it in the shade for 24 hours. Wash the fresh powdery mildew spores on the cucumber leaves, filter them with double-layer gauze, make a suspension with a spore concentration of about 100,000 / mL, and spray inoculate. Move the inoculated test material into an artificial climate, keep the relative humidity between 60 and 70%, and keep the temperature between 21 and 23°C. After about 10 days, conduct a graded investigation based on the incidence of the blank control, and calculate the prevention effect according to the disease index.

[0222] The test results are:

[0223] At a dosage of 100 mg / L, the control effect of Example 1, Example 2, Example 3, Example 4, Example 5, Example 6, Example 7, Example 8, Example 9, 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, Example 29, Example 30, Example 31, Example 32, Example 33, Example 34, Example 35, Example 36, Example 37, Example 38, Example 39, Example 40, Example 41, Example 42, Example 43, Example 44, Example 45, Example 46, Example 47, Example 48, Example 49, and Example 50 on cucumber downy mildew is more than 80%.

[0224] At a dosage of 50 mg / L, the control effects of Example 1, Example 2, Example 3, Example 4, Example 5, Example 6, Example 7, Example 8, Example 9, Example 11, Example 12, Example 13, Example 14, Example 15, Example 16, Example 17, Example 18, Example 19, Example 21, Example 22, Example 24, Example 27, Example 29, Example 30, Example 31, Example 32, Example 33, Example 34, Example 35, Example 36, Example 37, Example 38, Example 39, Example 40, Example 41, Example 42, Example 43, Example 44, Example 45, Example 46, Example 47, Example 48, Example 49, and Example 50 on cucumber downy mildew were above 70%; and the control effects of Example 51, Example 52, and Example 53 on cucumber downy mildew were 10%, 40%, and 50%, respectively, at a dosage of 50 mg / L.

[0225] The compounds of the present invention still have good protective effects on cucumber downy mildew at low dosages. For example, at a dosage of 25 mg / L, the protective effects of Example 4, Example 5, Example 6, Example 8, Example 9, Example 16, Example 18, Example 31, Example 32, Example 33, Example 37, Example 39, Example 47, Example 48, Example 49, and Example 50 on cucumber downy mildew are above 70%; while at a dosage of 25 mg / L, the protective effects of Example 51, Example 52, and Example 53 on cucumber downy mildew are 0%, 10%, and 30%, respectively.

[0226] In addition, the compounds of the present invention also have good preventive effects on other diseases, such as cucumber powdery mildew. For example, at 200 mg / L, the preventive effects of Example 2, Example 6, Example 8, Example 9, Example 14, Example 16, Example 18, Example 29, Example 31, Example 32, Example 33, Example 47, Example 48, Example 49, and Example 50 on cucumber powdery mildew are more than 70%.

[0227] 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: in, R 1 is phenyl, naphthyl, anthracenyl or pyridin-3-yl; wherein R 1 Optionally 1, 2 or 3 selected from halogen, nitro, C 1-4 Alkyl, C 1-4 Alkoxy, halogenated C 1-4 Alkyl, halogenated C 1-4 Alkoxy, C 1-4 Alkyl-C(=O)O-, -N(C 1-4 Alkyl)2, phenyl or phenoxy substituted; R 2 is cyclopropyl; R 3 and R 4 Each independently is -CH3; X is #-CR 5 R 6 -CR 8 =CR 10 -*; where "#" indicates the connection end and -NR 2 - is connected, and the connection end indicated by "*" is connected to -R 1 Connected; R 5 and R 6 each independently is hydrogen; R 8 is hydrogen or C 1-6 alkyl; R 10 For hydrogen.

2. The compound according to claim 1, wherein: R 1 is optionally substituted by 1, 2 or 3 selected from fluorine, chlorine, bromine, iodine, nitro, -CH3, -CH2CH3, -CH2CH2CH3, -CH(CH3)2, -CH2CH2CH2CH3, -CH2CH(CH3)2, -CH(CH3)CH2CH3, -C(CH3)3, -OCH3, -OCH2CH3, -OCH2CH2CH3, -OCH(CH3)2, -OCH2CH2CH 2CH3, -OCH2CH(CH3)2, -OCH(CH3)CH2CH3, -OC(CH3)3, -CHF2, -CF3, -OCHF2, -OCF3, -OC(=O)CH3, -OC(=O)CH2CH3, -OC(=O)CH2CH2CH3, -OC(=O)CH(CH3)2, -N(CH3)2, -N(CH2CH3)2, phenyl or phenoxy substituted.

3. The compound according to claim 1, wherein: R 8 For carbon, -CH3, -CH2CH3, -CH2CH2CH3, -CH(CH3)2, -CH2CH2CH2CH3, -CH2CH2CH2CH2CH3 or -CH2CH2CH2CH2CH2CH2CH3.

4. A compound having one of the following structures or a salt thereof:

5. A composition comprising the compound according to any one of claims 1 to 4 and an adjuvant commonly used in pesticides.

6. Use of the compound according to any one of claims 1 to 4 or the composition according to claim 5 in preventing and controlling plant diseases; in, The plant diseases are cucumber downy mildew and / or cucumber powdery mildew.

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