Triazole sulfonamide derivatives and their applications

Abstract

The present invention relates to a triazole sulfonamide derivative and its application; 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 represented by formula (I), and a composition thereof, as well as the use of these compounds or compositions as fungicides in agriculture, and a method for controlling plant diseases using these compounds or compositions; wherein R 1 , R 2 , R 3 , R 4 , R 5 and m have the meanings as defined in the present invention.

Description

Technical Field

[0001] The present invention relates to the field of pesticides, in particular to a triazole sulfonamide derivative and a preparation method thereof, and use of the triazole sulfonamide derivative as a plant disease control agent in agriculture, forestry or horticulture. Background Art

[0002] In modern agricultural production, various types of pesticides are needed to ensure the healthy growth of crops, but the fungicidal activity of existing fungicides is always insufficient; and due to the long-term and frequent use of pesticides, the diseases on crops develop resistance to existing fungicides, which reduces the prevention and control effect of pesticides. In order to solve the problem of high efficiency or resistance, new fungicides need to be continuously developed. Summary of the invention

[0003] The present invention provides a triazole sulfonamide derivative and a preparation method and application thereof. The triazole sulfonamide derivative and a composition containing the same provided by the present invention have excellent preventive effects on plant diseases, especially plant diseases caused by plant pathogenic fungi; specifically,

[0004] 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 represented by formula (I):

[0005]

[0006] in:

[0007] m is 0, 1 or 2;

[0008] R 1 For hydrogen, C 1-6 Alkyl, C 2-6 Alkenyl, C 2-6 Alkynyl, C 3-6 Cycloalkyl or -S(=O)2NR a R b ;

[0009] R a and R b are independently hydrogen, C 1-6 Alkyl, C 2-6 Alkenyl or C 2-6 Alkynyl;

[0010] R 2 is hydrogen, halogen, cyano, nitro, hydroxyl, carboxyl, C 1-6 Alkyl or halogenated C 1-6 alkyl;

[0011] R 3 is optionally substituted by 1, 2, 3, 4 or 5 groups selected from halogen, cyano, nitro, hydroxy, carboxyl, amino, formyl, C1-6 Alkyl, C 1-6 Alkoxy, C 1-6 Alkylthio, halo 1-6 Alkyl, halogenated C 1-6 Alkoxy or halogenated C 1-6 Alkylthio-substituted phenyl;

[0012] R 4 is hydrogen, halogen, cyano, nitro, hydroxyl, carboxyl, amino, formyl, C 1-6 Alkyl, halogenated C 1-6 Alkyl, -C(=O)NR c R d or -C(=O)OCH3;

[0013] R c and R d are independently hydrogen or C 1-6 alkyl;

[0014] or R c , R d and the nitrogen atom connected thereto form a 3-6 membered heterocyclic ring; the 3-6 membered heterocyclic ring is optionally substituted by 1, 2, 3, 4, 5 or 6 groups selected from halogen, cyano, nitro, C 1-6 Alkyl or halogenated C 1-6 Alkyl substitution;

[0015] R 5 is hydrogen, halogen, cyano, nitro, hydroxyl, carboxyl, C 1-6 Alkyl, halogenated C 1-6 Alkyl, -C(=O)OC 1-6 Alkyl or -C(=O)C 1-6 alkyl;

[0016] The conditions are:

[0017] When R 1 -S(=O)2N(CH3)2, m is 2, R 4 When -C(=O)OCH3, for

[0018] In some embodiments, R 1 For hydrogen, C 1-4 Alkyl, C 2-4 Alkenyl, C 2-4 Alkynyl, C 3-6 Cycloalkyl or -S(=O)2NR a R b ;

[0019] R a and R bare independently hydrogen, C 1-4 Alkyl, C 2-4 Alkenyl or C 2-4 Alkynyl.

[0020] In some other embodiments, R 1 is hydrogen, -CH3, -CH2CH3, -CH2CH2CH3, -CH2CH2CH2CH3, -CH=CH2, -CH2CH=CH2, -C≡CH, -CH2C≡CH or -S(=O)2NR a R b ;

[0021] R a and R b Each is independently hydrogen, -CH3, -CH2CH3, -CH2CH2CH3, -CH2CH2CH2CH3, -CH=CH2, -CH2CH=CH2, -C≡CH or -CH2C≡CH.

[0022] Preferably, in some embodiments, R 1 is hydrogen or -S(=O)2NR a R b ;

[0023] R a and R b Each independently is C 1-4 alkyl.

[0024] Preferably, in some other embodiments, R 1 is hydrogen or -S(=O)2NR a R b ;

[0025] R a and R b Each is independently -CH3, -CH2CH3, -CH2CH2CH3 or -CH2CH2CH2CH3.

[0026] In some embodiments, R 2 is hydrogen, halogen, cyano, nitro, hydroxyl, carboxyl, C 1-4 Alkyl or halogenated C 1-4 alkyl.

[0027] In some other embodiments, R 2 It is hydrogen, fluorine, chlorine, bromine, iodine, cyano, nitro, hydroxyl, carboxyl, -CH3 or -CF3.

[0028] Preferably, in some embodiments, R 2 For hydrogen.

[0029] In some embodiments, R 3is optionally substituted by 1, 2, 3, 4 or 5 groups selected from halogen, cyano, nitro, hydroxy, carboxyl, amino, formyl, C 1-4 Alkyl, C 1-4 Alkoxy, C 1-4 Alkylthio, halo 1-4 Alkyl, halogenated C 1-4 Alkoxy or halogenated C 1-4 Alkylthio-substituted phenyl.

[0030] In some other embodiments, R 3 is phenyl which is optionally substituted by 1, 2, 3, 4 or 5 groups selected from fluorine, chlorine, bromine, iodine, cyano, nitro, hydroxy, carboxyl, amino, formyl, -CH3, -OCH3, -SCH3, -CF3, -OCF3 or -SCF3.

[0031] Preferably, in some embodiments, R 3 The substructure is as follows:

[0032]

[0033] In some embodiments, R 4 is hydrogen, halogen, cyano, nitro, hydroxyl, carboxyl, amino, formyl, C 1-4 Alkyl, halogenated C 1-4 Alkyl or -C(=O)NR c R d ;

[0034] R c and R d are independently hydrogen or C 1-4 alkyl;

[0035] or R c , R d and the nitrogen atom connected thereto form a 3-6 membered heterocyclic ring; the 3-6 membered heterocyclic ring is optionally substituted by 1, 2, 3, 4, 5 or 6 groups selected from halogen, cyano, nitro, C 1-4 Alkyl or halogenated C 1-4 Alkyl substitution.

[0036] In some other embodiments, R 4 is hydrogen, fluorine, chlorine, bromine, iodine, cyano, nitro, hydroxyl, carboxyl, amino, formyl, -CH3, -CF3 or -C(=O)NR c R d ;

[0037] R c and R d are each independently hydrogen, -CH3 or -CH2CH3;

[0038] or Rc , R d and the nitrogen atom connected thereto form a 3-6 membered heterocyclic ring; the 3-6 membered heterocyclic ring is optionally substituted by 1, 2, 3, 4, 5 or 6 groups selected from fluorine, chlorine, bromine, iodine, cyano, nitro, -CH3 or -CF3.

[0039] Preferably, in some embodiments, R 4 is hydrogen or -C(=O)NR c R d ;

[0040] Among them, R c , R d and the nitrogen atom connected thereto form a 3-6 membered heterocyclic ring; the 3-6 membered heterocyclic ring is optionally substituted by 1, 2, 3, 4, 5 or 6 groups selected from halogen, cyano, nitro, C 1-4 Alkyl or halogenated C 1-4 Alkyl substitution.

[0041] Preferably, in some other embodiments, R 4 is hydrogen or -C(=O)NR c R d ;

[0042] Among them, R c , R d and the nitrogen atom connected thereto form a 3-6 membered heterocyclic ring; the 3-6 membered heterocyclic ring is optionally substituted by 1, 2, 3, 4, 5 or 6 groups selected from fluorine, chlorine, bromine, iodine, cyano, nitro, -CH3 or -CF3.

[0043] More preferably, in some embodiments, R 4 is hydrogen or -C(=O)NR c R d ;

[0044] Among them, R c , R d The nitrogen atom connected thereto forms a piperidine ring, a morpholine ring, a piperazine ring or a thiomorpholine ring; the piperidine ring, the morpholine ring, the piperazine ring or the thiomorpholine ring is optionally substituted by 1, 2, 3, 4, 5 or 6 groups selected from fluorine, chlorine, bromine, iodine, cyano, nitro, -CH3 or -CF3.

[0045] Further preferably, in some embodiments, R 4 is hydrogen, fluorine, chlorine, bromine, iodine, cyano, nitro,

[0046] More preferably, in some embodiments, R 4 For hydrogen,

[0047] In some embodiments, R 5 is hydrogen, halogen, cyano, nitro, hydroxyl, carboxyl, C 1-4 Alkyl, halogenated C 1-4 Alkyl, -C(=O)OC 1-4 Alkyl or -C(=O)C 1-4 alkyl.

[0048] In some other embodiments, R 5 It is hydrogen, fluorine, chlorine, bromine, iodine, cyano, nitro, hydroxy, carboxyl, -CH3, -CF3, -C(=O)OCH3, -C(=O)OCH2CH3 or -C(=O)CH3.

[0049] Preferably, in some embodiments, R 5 is hydrogen or -C(=O)OC 1-4 alkyl.

[0050] Preferably, in some other embodiments, R 5 It is hydrogen, -C(=O)OCH3 or -C(=O)OCH2CH3.

[0051] In some embodiments, the present invention provides a compound, which is a compound represented by formula (I-1) or a stereoisomer, nitrogen oxide or salt thereof represented by formula (I-1):

[0052]

[0053] in:

[0054] R a and R b Each independently is C 1-4 alkyl;

[0055] R 2 For hydrogen, halogen, cyano, nitro, C 1-4 Alkyl or halogenated C 1-4 alkyl;

[0056] R 3 is optionally substituted by 1, 2, 3, 4 or 5 groups selected from halogen, cyano, nitro, hydroxy, carboxyl, amino, formyl, C 1-4 Alkyl, C 1-4 Alkoxy, C 1-4 Alkylthio, halo 1-4 Alkyl, halogenated C 1-4 Alkoxy or halogenated C 1-4 Alkylthio-substituted phenyl;

[0057] R 4 For hydrogen, halogen, cyano, nitro, C 1-4 Alkyl or halogenated C 1-4 alkyl;

[0058] R 6 C 1-4 Alkoxy.

[0059] In other embodiments, the present invention provides a compound, which is a compound represented by formula (I-1) or a stereoisomer, nitrogen oxide or salt thereof represented by formula (I-1):

[0060] in:

[0061] R a and R b Each is independently -CH3, -CH2CH3, -CH2CH2CH3 or -CH2CH2CH2CH3;

[0062] R 2 is hydrogen, fluorine, chlorine, bromine, iodine, cyano, nitro, -CH3 or -CF3;

[0063] R 3 is phenyl optionally substituted by 1, 2, 3, 4 or 5 groups selected from fluorine, chlorine, bromine, iodine, cyano, nitro, hydroxyl, carboxyl, amino, formyl, -CH3, -OCH3, -SCH3, -CF3, -OCF3 or -SCF3;

[0064] R 4 is hydrogen, fluorine, chlorine, bromine, iodine, cyano, nitro, -CH3 or -CF3;

[0065] R 6 It is -OCH3 or -OCH2CH3.

[0066] Preferably, in some embodiments, the present invention provides a compound, which is a compound represented by formula (I-1) or a stereoisomer, nitrogen oxide or salt thereof represented by formula (I-1):

[0067] in:

[0068] R 3 The substructure is as follows:

[0069]

[0070] In some embodiments, the present invention provides a compound, which is a compound represented by formula (I-2) or a stereoisomer, nitrogen oxide or salt thereof represented by formula (I-2):

[0071]

[0072] in:

[0073] R c , R dand the nitrogen atom connected thereto form a 3-6 membered heterocyclic ring; the 3-6 membered heterocyclic ring is optionally substituted by 1, 2, 3, 4, 5 or 6 groups selected from halogen, cyano, nitro, C 1-4 Alkyl or halogenated C 1-4 Alkyl substitution;

[0074] R a and R b Each independently is C 1-4 alkyl;

[0075] R 2 For hydrogen, halogen, cyano, nitro, C 1-4 Alkyl or halogenated C 1-4 alkyl;

[0076] R 3 is optionally substituted by 1, 2, 3, 4 or 5 groups selected from halogen, cyano, nitro, hydroxy, carboxyl, amino, formyl, C 1-4 Alkyl, C 1-4 Alkoxy, C 1-4 Alkylthio, halo 1-4 Alkyl, halogenated C 1-4 Alkoxy or halogenated C 1-4 Alkylthio-substituted phenyl;

[0077] R 5 For hydrogen, halogen, cyano, nitro, C 1-4 Alkyl or halogenated C 1-4 alkyl.

[0078] In other embodiments, the present invention provides a compound, which is a compound represented by formula (I-2) or a stereoisomer, nitrogen oxide or salt thereof represented by formula (I-2):

[0079] in:

[0080] R c , R d and the nitrogen atom connected thereto form a 3-6 membered heterocyclic ring; the 3-6 membered heterocyclic ring is optionally substituted by 1, 2, 3, 4, 5 or 6 groups selected from fluorine, chlorine, bromine, iodine, cyano, nitro, -CH3 or -CF3;

[0081] R a and R b Each is independently -CH3, -CH2CH3, -CH2CH2CH3 or -CH2CH2CH2CH3;

[0082] R 2 is hydrogen, fluorine, chlorine, bromine, iodine, cyano, nitro, -CH3 or -CF3;

[0083] R 3is phenyl optionally substituted by 1, 2, 3, 4 or 5 groups selected from fluorine, chlorine, bromine, iodine, cyano, nitro, hydroxyl, carboxyl, amino, formyl, -CH3, -OCH3, -SCH3, -CF3, -OCF3 or -SCF3;

[0084] R 5 It is hydrogen, fluorine, chlorine, bromine, iodine, cyano, nitro, -CH3 or -CF3.

[0085] Preferably, in some embodiments, the present invention provides a compound, which is a compound represented by formula (I-2) or a stereoisomer, nitrogen oxide or salt thereof represented by formula (I-2):

[0086] in:

[0087] R c , R d Together with the nitrogen atom connected to it, it forms the following substructure:

[0088]

[0089] Preferably, in some embodiments, the present invention provides a compound, which is a compound represented by formula (I-2) or a stereoisomer, nitrogen oxide or salt thereof represented by formula (I-2):

[0090] in:

[0091] R 3 The substructure is as follows:

[0092]

[0093] 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 having one of the following structures:

[0094]

[0095]

[0096] In another aspect, the present invention provides a composition comprising at least one compound of the present invention and at least one adjuvant commonly used in pesticides.

[0097] 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.

[0098] In yet another aspect, the present invention provides a method for controlling plant diseases, which comprises applying an effective amount of the compound of the present invention or a composition comprising an effective amount of the compound of the present invention to plants and / or the plant growth environment.

[0099] Preferably, the plant disease is caused by a phytopathogenic fungus.

[0100] Detailed description of the invention

[0101] Definitions and general terms

[0102] 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.

[0103] 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.

[0104] 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.

[0105] 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.

[0106] 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.

[0107] The term "comprising" is an open expression, that is, including the contents specified in the present invention but not excluding other contents.

[0108] "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.

[0109] "Enantiomers" refer to two non-superimposable isomers of a compound that are mirror images of each other.

[0110] "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.

[0111] 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.

[0112] 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.

[0113] 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.

[0114] 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.

[0115] Any resulting mixture of stereoisomers can be separated into pure or substantially pure geometric isomers, enantiomers, diastereomers, depending on the differences in the physicochemical properties of the components, for example, by chromatography and / or fractional crystallization. Any resulting racemate of the final product or intermediate can be separated into optical antipodes by methods familiar to those skilled in the art, such as by separating the diastereoisomeric salts thereof obtained, using known methods. 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.

[0116] 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.

[0117] 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.

[0118] 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.

[0119] 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.

[0120] 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.

[0121] 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.

[0122] 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.

[0123] 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.

[0124] 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.

[0125] 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.

[0126] 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.

[0127] 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 and tetrahydropyrrolyl are 5 membered heterocyclyls, and piperidinyl, piperazinyl and morpholinyl are 6 membered heterocyclyls.

[0128] The term "halogen" refers to fluorine (F), chlorine (Cl), bromine (Br) or iodine (I).

[0129] 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.

[0130] 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.

[0131] 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.

[0132] The term "cyano" refers to -CN.

[0133] The term "hydroxy" refers to -OH.

[0134] The term "nitro" refers to -NO2.

[0135] The term "carboxyl" refers to -COOH.

[0136] The term "amino" refers to -NH2.

[0137] The term "formyl" refers to -C(=O)H.

[0138] 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 the compounds of the present invention can be prepared by treating the compounds of the present invention with a metal hydroxide (e.g., sodium hydroxide) or an amine (e.g., ammonia, trimethylamine, diethanolamine, 2-methylthiopropylamine, bisallylamine, 2-butoxyethylamine, morpholine, cyclododecylamine or benzylamine).

[0139] 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.

[0140] Compositions and preparations of the compounds of the present invention

[0141] 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.

[0142] 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.

[0143] 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.

[0144] 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.

[0145] 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.

[0146] 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.

[0147] 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.

[0148] 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.

[0149] 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.

[0150] 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.

[0151] The mineral oil includes one or more of liquid wax, motor oil, kerosene and lubricating oil.

[0152] At the same time, the above solvents can also be used as co-solvents.

[0153] 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.

[0154] 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.

[0155] 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.

[0156] 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.

[0157] 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.

[0158] The stabilizer is selected from one or more of triphenyl phosphite, epichlorohydrin and acetic anhydride.

[0159] 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.

[0160] 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.

[0161] 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.

[0162] 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.

[0163] 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.

[0164] 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.

[0165] 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.

[0166] 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.

[0167] 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.

[0168] Application of the compounds and compositions of the present invention

[0169] 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.

[0170] 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.

[0171] 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.

[0172] 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.

[0173] General synthesis process

[0174] The following scheme describes 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 in the present invention. The raw materials, reagents, etc. used to prepare the compounds of the present invention are all commercially available, or can be prepared by conventional methods in the art. In this specification, if there is any difference between the chemical name and the chemical structure, the structure is dominant. In the preparation process of the compounds of the present invention, unless otherwise specified, the preparation process of the compounds is carried out at room temperature. "Room temperature" refers to a temperature of about 15°C-35°C or about 20°C-30°C or about 23°C-28°C or about 25°C. In the context of the present invention, whether or not the words "about" or "approximately" are used, all numbers disclosed herein are approximate values.

[0175] Synthesis scheme

[0176] Synthesis Scheme 1

[0177]

[0178] The compound represented by formula (IA) can be prepared by synthetic scheme 1. The compound represented by formula (a) and the compound represented by formula (b) undergo nucleophilic substitution reaction at room temperature to obtain the compound represented by formula (IA);

[0179] Among them, R 1 , R 2 , R 3 , R 4 and R 5 Has the meaning as described in the present invention. Example

[0180] Intermediate 1: Preparation of 1-(N,N-dimethylsulfonyl)-1H-1,2,4-triazole-3-sulfonyl chloride

[0181]

[0182] Step 1: Preparation of 1,2-bis(1H-1,2,4-triazol-3-yl)disulfane

[0183]

[0184] 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), slowly drop p-toluenesulfonyl chloride (95.3 g, 0.50 mol) in dichloromethane (200 mL) at 0°C, and stir at room temperature for 18 hours after addition. Dichloromethane is evaporated under reduced pressure using a rotary evaporator, and water (500 mL) is added to the residue under mechanical stirring. After stirring 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%.

[0185] LC-MS: (M+1) m / z=201.1.

[0186] Step 2: Preparation of 3-((1-(N,N-dimethylsulfonyl)-1H-1,2,4-triazol-3-yl)disulfane)-N,N-dimethyl-1H-1,2,4-triazole-1-sulfonamide

[0187]

[0188] At 0°C, under nitrogen protection, potassium carbonate (69.0g, 0.50mol) was added to a solution of 1,2-bis(1H-1,2,4-triazole-3-yl)disulfane (60.0g, 0.30mol) in N,N-dimethylformamide (300mL), and then N,N-dimethylaminosulfonyl chloride (93.3g, 0.65mol) was slowly added dropwise. After the addition was complete, the reaction was continued to stir for 6 hours. The reaction solution was slowly poured into water (500mL), stirred for 1 hour, filtered, and the filter cake was air-dried to obtain 107.2g of white powder with a yield of 86.3%.

[0189] LC-MS: (M+1) m / z=415.0.

[0190] Step 3: Preparation of 1-(N,N-dimethylaminosulfonyl)-1H-1,2,4-triazole-3-sulfonyl chloride

[0191]

[0192] 3-((1-(N,N-dimethylaminosulfonyl)-1H-1,2,4-triazol-3-yl)disulfane)-N,N-dimethyl-1H-1,2,4-triazole-1-sulfonamide (41.40g, 0.10mol) was dissolved in 1,2-dichloroethane (150mL), and water (300mL) was added. The mixture was cooled to 0°C, acetic acid (100mL) was added, and the temperature was controlled at 10°C to 25°C. After stirring for 2 hours, chlorine gas (35.50g, 0.50mol) was introduced, and the reaction was continued for half an hour. After the reaction was completed, the solution was transferred to a separatory funnel, and the organic phase was washed three times with water (30mL). The solvent was evaporated under reduced pressure using a rotary evaporator to obtain 48.11g of white powder with a yield of 87.8%.

[0193] LC-MS: (M+1) m / z=274.8.

[0194] Intermediate 2: Preparation of 1H-1,2,4-triazole-3-sulfonyl chloride

[0195]

[0196] Dissolve 3-mercapto-1,2,4-triazole (10.1 g, 100 mmol) in 1,2-dichloroethane (100 mL), add water (200 mL), cool to 0°C, add acetic acid (50 mL), control the temperature between 10°C and 25°C, introduce chlorine (17.50 g, 250 mol) after 2 hours, and continue to react for half an hour. After the reaction is completed, transfer the solution to a separatory funnel, let stand for separation, wash the organic phase with water (30 mL) three times, and use a rotary evaporator to evaporate the solvent under reduced pressure to obtain 13.8 g of white powder with a yield of 82.3%.

[0197] LC-MS: (M+1) m / z=168.0.

[0198] Intermediate 3: Preparation of methyl 4-phenyl-1H-pyrrole-3-carboxylate

[0199]

[0200] Step 1: Preparation of methyl cinnamate

[0201]

[0202] After dissolving cinnamic acid (1.62 g, 10 mmol) in dioxane (30 mL), thionyl chloride (3.54 g, 30 mmol) was added in batches under stirring at 0°C, and after 30 minutes, a mixture of methanol (0.48 g, 15 mmol) and dioxane (10 mL) was added dropwise, and after the addition was completed, the mixture was stirred at 25°C for 12 hours. The solvent was evaporated under reduced pressure using a rotary evaporator to obtain 1.09 g of a colorless oil, with a yield of 67.2%.

[0203] LC-MS: (M+1) m / z=163.1.

[0204] Step 2: Preparation of methyl 4-phenyl-1H-pyrrole-3-carboxylate

[0205]

[0206] Dissolve methyl cinnamate (0.81 g, 5 mmol) in dimethyl sulfoxide (15 mL), add p-toluenesulfonylmethyl isocyanide (1.18 g, 6 mmol), add 60% sodium hydride (0.26 g, 6 mmol) in batches under stirring at 0°C, and stir at 25°C for 12 hours after the addition is complete. Use a rotary evaporator to evaporate the solvent under reduced pressure to obtain 0.46 g of a light yellow solid with a yield of 45.6%.

[0207] LC-MS: (M+1) m / z=202.1.

[0208] Intermediate 4: Preparation of (4-(4-fluorophenyl)-1H-pyrrol-3-yl)(morpholine)methanone

[0209]

[0210] Step 1: Preparation of (E)-3-(4-fluorophenyl)-1-morpholinoprop-2-en-1-one

[0211]

[0212] After dissolving 4-fluorocinnamic acid (1.80 g, 10 mmol) in dioxane (30 mL), thionyl chloride (3.54 g, 30 mmol) was added in batches at 0°C with stirring, and a mixture of morpholine (1.31 g, 15 mmol) and dioxane (10 mL) was added dropwise 30 minutes later. After the addition was complete, the mixture was stirred at 25°C for 12 hours. The solvent was evaporated under reduced pressure using a rotary evaporator to obtain 1.77 g of a colorless oil with a yield of 75.3%.

[0213] LC-MS: (M+1) m / z=236.1.

[0214] Step 2: Preparation of (4-(4-fluorophenyl)-1H-pyrrol-3-yl)(morpholine)methanone

[0215]

[0216] At room temperature, (E)-3-(4-fluorophenyl)-1-morpholinoprop-2-en-1-one (1.18 g, 5 mmol) was dissolved in dimethyl sulfoxide (15 mL), and p-toluenesulfonylmethyl isocyanide (1.18 g, 6 mmol) was added, cooled to 0°C, and 60% sodium hydride (0.26 g, 6 mmol) was added in batches under stirring. After the addition was completed, it was stirred at 25°C for 12 hours. The solvent was evaporated under reduced pressure using a rotary evaporator to obtain 0.56 g of a light yellow solid with a yield of 41.2%.

[0217] LC-MS: (M+1) m / z=275.1.

[0218] Intermediate 5: Preparation of methyl 4-(4-chlorophenyl)-1H-pyrrole-2-carboxylate

[0219]

[0220] At room temperature, 4-bromo-1H-pyrrole-2-carboxylic acid methyl ester (1.01 g, 5 mmol) was dissolved in ethanol (20 mL), and then p-chlorophenylboric acid (0.94 g, 6 mmol), palladium acetate (0.034 g, 0.15 mmol), and sodium carbonate (1.06 g, 10 mmol) were added. After the addition was completed, the mixture was stirred at room temperature for 12 hours. The solvent was evaporated under reduced pressure using a rotary evaporator to obtain 0.91 g of a colorless oil with a yield of 77.2%.

[0221] LC-MS: (M+1) m / z=236.0.

[0222] The intermediate compounds in Table 1 can be obtained by using the corresponding raw materials as starting materials and preparing them according to the preparation methods of the above intermediates or according to the preparation methods disclosed in the prior art.

[0223] Table 1

[0224]

[0225]

[0226]

[0227]

[0228] Example 1: Preparation of methyl 1-((1H-1,2,4-triazol-3-yl)sulfonyl)-4-phenyl-1H-pyrrole-3-carboxylate

[0229]

[0230] At room temperature, 4-phenyl-1H-pyrrole-3-carboxylic acid methyl ester (0.41 g, 2 mmol), sodium hydride (0.16 g, 4 mmol) and 15 mL of tetrahydrofuran were added to a 100 mL two-necked flask, stirred at room temperature for 1 hour, and then 1H-1,2,4-triazole-3-sulfonyl chloride (0.67 g, 4 mmol) was slowly added, and the reaction was stirred for 3 hours. 150 mL of water was added to quench the reaction, 100 mL of ethyl acetate was used for extraction, the organic phase was dried over anhydrous sodium sulfate, filtered, the filtrate was decompressed with a rotary evaporator to remove the solvent, and the residue was separated by column chromatography [ethyl acetate / petroleum ether (v / v) = 1 / 3] to obtain 0.41 g of a white solid, with a yield of 61.2%.

[0231] 1 H NMR (400MHz, DMSO-d6) δ14.25(t,J=3.4Hz,1H),8.78(m,1H),8.26(t,J=1.8Hz,1H),8.22–8.16( m,1H),7.96–7.92(m,1H),7.81(dd,J=6.1,3.1Hz,2H),7.53(dd,J=6.1,3.1Hz,2H),3.13(s,3H).

[0232] LC-MS: (M+1) m / z=333.1.

[0233] Example 2: Preparation of methyl 1-((1-(N,N-dimethylaminosulfonyl)-1H-1,2,4-triazol-3-yl)sulfonyl)-4-(4-fluorophenyl)-1H-pyrrole-3-carboxylate

[0234]

[0235] At room temperature, 4-(4-fluorophenyl)-1H-pyrrole-3-carboxylic acid methyl ester (0.44g, 2mmol), sodium hydride (0.16g, 4mmol) and 15mL tetrahydrofuran were added to a 100mL two-necked flask. After stirring at room temperature for 1 hour, 1-(N,N-dimethylaminosulfonyl)-1H-1,2,4-triazole-3-sulfonyl chloride (1.10g, 4mmol) was slowly added, and the reaction was continued to stir at room temperature for 3 hours. The reaction was quenched with 150mL of water, extracted with 100mL of ethyl acetate, and the organic phase was dried over anhydrous sodium sulfate and filtered. The filtrate was decompressed to remove the solvent by rotary evaporator, and the residue was separated by column chromatography [ethyl acetate / petroleum ether (v / v) = 1 / 3] to obtain 0.56g of white solid, with a yield of 61.4%.

[0236] 1H NMR(400MHz,DMSO-d6)δ8.84(s,1H),8.27(t,J=1.8Hz,1H),8.23–8.18(m,1H) ,7.32(dd,J=8.5,5.5Hz,2H),7.02(t,J=8.6Hz,2H),3.13(s,3H),2.94(s,6H).

[0237] LC-MS: (M+1) m / z = 458.1.

[0238] Using intermediate 1 or intermediate 2, and intermediate 3, intermediate 4, intermediate 5 and the intermediates in Table 1 as reaction materials, the target compounds in Table 2 can be obtained by preparing according to the synthesis method of Example 1 or Example 2.

[0239] Table 2

[0240]

[0241]

[0242]

[0243]

[0244]

[0245]

[0246] Biological activity test

[0247] Test target: Cucumber downy mildew

[0248] 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, 12.5 mg / L, 6.25 mg / L, etc.) against the test target.

[0249] Cucumber Downy Mildew Test (Pseudoperonosporacubensis)

[0250] 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 to dip in distilled water to wash off the sporangium on the back of the diseased leaves, and prepare a sporangium suspension (2-3x10 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.

[0251] The test results are as follows:

[0252] At a dosage of 200 mg / L, the protection efficacy 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, and Example 20 against cucumber downy mildew is ≥80%.

[0253] At a dosage of 50 mg / L, the prevention efficacy of Example 1, Example 3, Example 5, and Example 6 against cucumber downy mildew is ≤40%; at the same dosage, the prevention efficacy of Example 2, Example 4, Example 7, Example 8, Example 9, Example 10, Example 11, Example 12, Example 13, Example 14, Example 15, Example 16, Example 18, Example 19, and Example 20 against cucumber downy mildew is ≥80%.

[0254] At a dosage of 25 mg / L, the prevention efficacy of Example 2, Example 4, Example 7, Example 8, Example 15, Example 16, Example 17, Example 18, Example 19, Example 20, Example 21, and Example 22 against cucumber downy mildew is ≤50%; at the same dosage, the prevention efficacy of Example 9, Example 10, Example 11, Example 12, Example 13, and Example 14 against cucumber downy mildew is ≥80%.

[0255] At a dosage of 12.5 mg / L, the protective effect of the compound of the present invention on cucumber downy mildew is shown in Table 3:

[0256] Table 3

[0257]

[0258]

[0259] It can be seen from the test results that the compounds of the present invention have excellent preventive effects on cucumber downy mildew; after reducing the dosage (such as at a dosage of 6.25 mg / L), the compounds of the present invention still show good preventive effects, such as Example 9 at a dosage of 6.25 mg / L. The preventive effect of cucumber downy mildew is still ≥80%; the excellent preventive effect of the compounds of the present invention on plant diseases makes it have the prospect of further development as a commercial fungicide.

[0260] 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 having one of the following structures or a salt thereof:

2. A composition comprising the compound according to claim 1 and an adjuvant in pesticides.

3. The compound according to claim 1 or the composition according to claim 2 is used as a plant disease control agent in agriculture, wherein: The plant disease is cucumber downy mildew.

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