A phenyl-tetrazole oxime derivative, its preparation method and application

Abstract

The present application relates to a kind of phenyl-tetrazole oxime derivatives and its preparation method and application, wherein the phenyl-tetrazole oxime derivatives have the structure as shown in formula (I), wherein R 1 , R 2 , T, R a , R b , R c , R d , R e Have the meaning described in the present application;The phenyl-tetrazole oxime derivatives described in the present application have excellent prevention effect on cucumber downy mildew, rice sheath blight, cucumber gray mold, cucumber powdery mildew and the like, and can be further developed as a fungicide for application.

Description

Technical Field

[0001] This invention relates to the field of pesticides, specifically to a phenyl-tetrazole oxime derivative, its preparation method, and its application as a fungicide in agriculture. Background Technology

[0002] In modern agricultural production, various pesticides are frequently used to ensure the healthy growth of crops. However, the long-term and frequent use of pesticides has led to some crop diseases developing resistance to existing pesticides, reducing the control effect of existing pesticides. In order to achieve the purpose of disease control, it is necessary to increase the dosage of pesticides, which places a great burden on the economy and the environment. In order to meet the requirements of modern green and environmentally friendly pesticides, it is necessary to continuously develop new compounds with excellent control effects. Summary of the Invention

[0003] The present invention provides a compound, and a composition or formulation comprising such compound, for use as a fungicide in agriculture.

[0004] Specifically:

[0005] On one hand, the present invention provides a compound having the formula (I), or a nitrogen oxide, salt, (Z) isomer, (E) isomer, or mixture of (Z) and (E) isomers of the compound having the formula (I):

[0006]

[0007] in,

[0008] R 1 C 6-14 aryl or 6-10 heteroaryl; wherein, R 1 Optionally, 1, 2, 3, 4, or 5 groups are selected from halogen, cyano, nitro, hydroxy, carboxyl, amino, C 1-6 Alkyl, C 1-6 Alkoxy, halogenated C 1-6 Alkyl, Halogenated C 1-6 Alkyl groups, -NH(C 1-6 alkyl) or -N(C) 1-6 Alkyl)2-substituted;

[0009] R 2 For hydrogen, C 1-6 Alkyl, Halogenated C 1-6 Alkyl, C 2-6 alkenyl, C 2-6 alkynyl group, C 3-8 cycloalkyl or C 3-8 cycloalkyl-CH2-;

[0010] Ra R b R c R d and R e Each is independently hydrogen, halogen, cyano, nitro, C 1-6 Alkyl, C 1-6 Alkoxy, halogenated C 1-6 Alkyl or halogenated C 1-6 Alkoxy;

[0011] T is

[0012] R f and R g Each is independently hydrogen or C 1-6 alkyl.

[0013] In some implementation schemes, R 1 It is phenyl, pyridyl, or quinolinyl; wherein, R 1 Optionally, 1, 2, 3, 4, or 5 groups are selected from halogen, cyano, nitro, hydroxy, carboxyl, amino, C 1-4 Alkyl, C 1-4 Alkoxy, halogenated C 1-4 Alkyl, Halogenated C 1-4 Alkyl groups, -NH(C 1-4 alkyl) or -N(C) 1-4 Alkyl)2-substituted.

[0014] In other implementations, R 1 It is phenyl, pyridyl, or quinolinyl; wherein, R 1 Optionally substituted with 1, 2, 3, 4 or 5 groups selected from fluorine, chlorine, bromine, iodine, cyano, nitro, hydroxyl, carboxyl, amino, -CH3, -CH2CH3, -CH2CH2CH3, -CH(CH3)2, -CH2CH2CH2CH3, -C(CH3)3, -OCH3, -OCH2CH3, -OCH2CH2CH3, -OCH(CH3)2, -OCH2CH2CH2CH3, -OC(CH3)3, -CF3, -OCF3, -NH(CH3) or -N(CH3)2.

[0015] Preferably, in some embodiments, R 1 It is phenyl, pyridin-3-yl, or quinoline-3-yl; wherein, R 1 Optionally, 1, 2, 3, 4, or 5 groups are selected from halogen, cyano, nitro, hydroxy, carboxyl, amino, C 1-4 Alkyl, C 1-4 Alkoxy, halogenated C 1-4 Alkyl, Halogenated C 1-4 Alkyl groups, -NH(C 1-4alkyl) or -N(C) 1-4 Alkyl)2-substituted.

[0016] Preferably, in some embodiments, R 1 It is phenyl, pyridin-3-yl, or quinoline-3-yl; wherein, R 1 Optionally substituted with 1, 2, 3, 4 or 5 groups selected from fluorine, chlorine, bromine, iodine, cyano, nitro, hydroxyl, carboxyl, amino, -CH3, -CH2CH3, -CH2CH2CH3, -CH(CH3)2, -CH2CH2CH2CH3, -C(CH3)3, -OCH3, -OCH2CH3, -OCH2CH2CH3, -OCH(CH3)2, -OCH2CH2CH2CH3, -OC(CH3)3, -CF3, -OCF3, -NH(CH3) or -N(CH3)2.

[0017] The pyridine-3-yl group is The quinoline-3-yl is This indicates the connection point between the structural formula and the rest of the molecule.

[0018] In other implementation schemes, R 1 for

[0019] In some implementation schemes, R 2 For hydrogen, C 1-4 Alkyl, Halogenated C 1-4 Alkyl, C 2-4 alkenyl, C 2-4 alkynyl group, C 3-6 cycloalkyl or C 3-6 Cycloalkyl-CH2-.

[0020] In other implementations, R 2 It can be hydrogen, -CH3, -CH2CH3, -CH=CH2, -CH2-CH=CH2, -CH≡CH2, -CH2-C≡CH, cyclopropyl or cyclopropyl-CH2-.

[0021] Preferably, in some embodiments, R 2 It is hydrogen.

[0022] In some implementation schemes, R a R b R c R d and R e Each is independently hydrogen, halogen, cyano, nitro, C 1-4 Alkyl, C 1-4 Alkoxy, halogenated C 1-4 Alkyl or halogenated C1-4 Alkyl group.

[0023] In other implementations, R a R b R c R d and R e Each can be independently hydrogen, fluorine, chlorine, bromine, iodine, cyano, nitro, -CH3, -OCH3, -CF3 or -OCF3.

[0024] Preferably, in some embodiments, R a R b R c R d and R e Each is independently hydrogen.

[0025] In some implementation schemes, T is...

[0026] R f and R g Each is independently hydrogen or C 1-4 alkyl.

[0027] In other implementations, T is

[0028] R f and R g Each can be independently hydrogen, -CH3, or -CH2CH3.

[0029] Preferably, in some embodiments, T is Among them, R f It is -CH3.

[0030] In some embodiments, the present invention provides a compound having the formula (IA), or a nitride, stereoisomer, or salt thereof of the compound having the formula (IA):

[0031]

[0032] Among them, R 1 R 2 , T, R a R b R c R d and R e It has the meaning described in this invention; the compound represented by formula (IA) is the (Z) type isomer of the compound represented by formula (I).

[0033] In other embodiments, the present invention provides a compound having the formula (IB), or a nitride, stereoisomer, or salt thereof of a compound having the formula (IB):

[0034]

[0035] Among them, R 1 R 2 , T, R a R b R c R d and R e It has the meaning described in this invention; the compound represented by formula (IB) is an (E) type isomer of the compound represented by formula (I).

[0036] In some embodiments, the present invention provides a compound having the formula (IA), or a nitride, stereoisomer, or salt thereof of the compound having the formula (IA):

[0037]

[0038] in,

[0039] R a R b R c R d and R e Each is independently hydrogen;

[0040] T is Among them, R f C 1-4 alkyl;

[0041] R 1 It is phenyl, pyridyl, or quinolinyl; wherein, R 1 Optionally selected by one or two elements chosen from halogen, C 1-4 Alkyl, C 1-4 Alkoxy, halogenated C 1-4 Alkyl, Halogenated C 1-4 Alkyl groups, -NH(C 1-4 alkyl) or -N(C) 1-4 Alkyl)2-substituted;

[0042] R 2 It is hydrogen.

[0043] In other implementations, T is Among them, R f -CH3;

[0044] R 1 It is phenyl, pyridyl, or quinolinyl; wherein, R1 Optionally substituted with one or two of the following: fluorine, chlorine, bromine, iodine, -CH3, -CH2CH3, -CH2CH2CH3, -CH(CH3)2, -CH2CH2CH2CH3, -C(CH3)3, -OCH3, -OCH2CH3, -OCH2CH2CH3, -OCH(CH3)2, -OCH2CH2CH2CH3, -OC(CH3)3, -CF3, -OCF3, -NH(CH3) or -N(CH3)2.

[0045] In some embodiments, the present invention provides a compound having one of the following structures, or a nitrogen oxide, salt, (Z) isomer, (E) isomer, or mixture of (Z) and (E) isomers of a compound having one of the following structures:

[0046]

[0047]

[0048] On the other hand, the present invention provides a composition comprising at least one compound described herein and an adjuvant commonly used in pesticide science.

[0049] On the other hand, the present invention provides the application of the compounds or compositions described herein as fungicides in agriculture.

[0050] On the other hand, the present invention provides the use of the compounds or compositions described herein in the prevention and control of plant diseases.

[0051] Specifically, the plant disease is caused by plant pathogenic fungi.

[0052] Preferably, the plant disease is cucumber downy mildew, rice sheath blight, cucumber gray mold, or cucumber powdery mildew.

[0053] Detailed Description of the Invention

[0054] Definitions and general terms

[0055] Certain embodiments of the invention will now be described in detail, examples of which are illustrated by the accompanying structural and chemical formulas. The invention is intended to cover all alternatives, modifications, and equivalents, all of which are included within the scope of the invention as defined in the claims. Those skilled in the art will recognize that many similar or equivalent methods and materials can be used to practice the invention. The invention is by no means limited to the methods and materials described herein. In the event that one or more of the incorporated documents, patents, and similar materials differ from or contradict this application (including, but not limited to, defined terminology, application of terminology, described techniques, etc.), this application shall prevail.

[0056] It should be further appreciated that certain features of the invention, for clarity, have been described in multiple independent embodiments, but may also be provided in combination in a single embodiment. Conversely, various features of the invention, for brevity, have been described in a single embodiment, but may also be provided individually or in any suitable sub-combination.

[0057] Unless otherwise stated, all technical terms used in this invention have the same meaning as commonly understood by one of ordinary skill in the art. All patents and publications related to this invention are incorporated herein by reference in their entirety.

[0058] Unless otherwise stated, the following definitions as used in this invention shall apply. For the purposes of this invention, chemical elements are consistent with the periodic table (CAS edition) and the Handbook of Chemistry and Physics, 75th edition, 1994. Furthermore, 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.

[0059] Unless otherwise stated or there is an obvious conflict in the context, the articles “a,” “an,” and “described” as used in this invention are intended to include “at least one” or “one or more.” Therefore, these articles as used in this invention refer to articles for one or more (i.e., at least one) objects. For example, “a component” refers to one or more components, meaning that more than one component may be considered for use or employed in the embodiments described.

[0060] The term "comprising" is an open-ended expression, meaning it includes the contents specified in this invention, but does not exclude other aspects.

[0061] "Stereoisomers" are compounds that have the same chemical structure but whose atoms or groups are arranged differently in space. Stereoisomers include enantiomers, diastereomers, conformational isomers (rotational isomers), geometric isomers (cis / trans) isomers, and hindered isomers, etc.

[0062] "Enantiomers" refer to two non-overlapping but mirror-image isomers of a compound.

[0063] A diastereomer is a stereoisomer that has two or more chiral neutral molecules that are not mirror images of each other. Diastereomers possess different physical properties, such as melting point, boiling point, spectral properties, and reactivity. Mixtures of diastereomers can be separated using high-resolution analytical techniques such as electrophoresis and chromatography, for example, HPLC.

[0064] The stereochemical definitions and rules used in this invention generally follow the descriptions in S.P. Parker, Ed., McGraw-Hill Dictionary of Chemical Terms (1984), McGraw-Hill Book Company, New York; and Eliel, E. and Wilen, S., “Stereochemistry of Organic Compounds”, John Wiley & Sons, Inc., New York, 1994.

[0065] Many organic compounds exist in an optically active form, meaning they possess the ability to rotate the plane of plane-polarized light. In describing optically active compounds, the prefixes D and L or R and S are used to indicate the absolute configuration of the molecule with respect to one or more of its chiral centers. The prefixes d and l or (+) and (-) are symbols used to specify the plane-polarized light rotation caused by the compound, where (-) or l indicates that the compound is levorotatory. Compounds with the prefix (+) or d are 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 the chemical reaction or process.

[0066] Any asymmetric atom (e.g., carbon, etc.) in the compounds disclosed in this invention can exist in a racemic or enantiomerically enriched form, such as in (R)-, (S)-, or (R,S)- configurations. In some embodiments, each asymmetric atom has at least 50% enantiomeric excess, at least 60% enantiomeric excess, at least 70% enantiomeric excess, at least 80% enantiomeric excess, at least 90% enantiomeric excess, at least 95% enantiomeric excess, or at least 99% enantiomeric excess in the (R)- or (S)- configuration.

[0067] Depending on the choice of starting materials and methods, the compounds of this invention can exist as one or a mixture of possible isomers, such as racemic mixtures and mixtures of non-corresponding isomers (depending on the number of asymmetric carbon atoms). Optically active (R)- or (S)- isomers can be prepared using chiral synthons or chiral reagents, or resolved using conventional techniques. If the compound contains a double bond, the substituents may be E or Z configurations; if the compound contains a disubstituted cycloalkyl group, the cycloalkyl substituents may be cis or trans configurations.

[0068] Any mixture of stereoisomers obtained can be separated into pure or substantially pure geometric isomers, enantiomers, and diastereomers based on differences in the physicochemical properties of the components, for example, by chromatography and / or fractional crystallization.

[0069] Racemic derivatives of any resulting end product or intermediate can be separated into optical enantiomers using known methods familiar to those skilled in the art, such as by separating the obtained diastereomeric salts. Racemic products can also be separated by chiral chromatography, such as high-performance liquid chromatography (HPLC) using chiral adsorbents. In particular, enantiomers can be prepared via asymmetric synthesis.

[0070] As described in this invention, the compounds of this invention may optionally be substituted with one or more substituents, such as the general formula compounds above, or the specific examples, subclasses, and classes of compounds included in this invention, as described in the embodiments. It should be understood that the term "optionally substituted" is used interchangeably with the term "substituted or unsubstituted." Generally, the term "substituted" means that one or more hydrogen atoms in the given structure are substituted by a specific substituent. Unless otherwise indicated, an optional substituent group may be substituted at each substituted position of the group. When more than one position in the given structural formula can be substituted by one or more substituents selected from a specific group, the substituents may be substituted at the same or different positions. Specifically, examples of "one or more" refer to 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10. The substituents described therein can be, but are not limited to, deuterium, fluorine, chlorine, bromine, iodine, cyano, hydroxyl, nitro, amino, carboxyl, alkyl, alkoxy, alkoxyalkyl, alkoxyalkoxy, alkoxyalkylamino, aryloxy, heteroaryloxy, heterocyclic alkoxy, arylalkoxy, heteroarylalkoxy, heterocyclic alkoxy, cycloalkylalkoxy, alkylamino, alkylaminoalkyl, alkylaminoalkylamino, 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, heterocyclic, heterocyclic alkyl, heterocyclic acyl, aryl, arylalkyl, arylamino, heteroaryl, heteroarylalkyl, heteroarylamino, amide, sulfonyl, aminosulfonyl, etc.

[0071] Additionally, it should be noted that, unless otherwise explicitly stated, the descriptive terms “each…independently is”, “…each independently is”, and “…independently is” used in this invention are interchangeable and should be interpreted broadly. They can mean that the specific options expressed by the same symbols in different groups do not affect each other, or that the specific options expressed by the same symbols in the same group do not affect each other.

[0072] In various parts of this specification, the substituents of the compounds disclosed herein are disclosed according to the type or scope of the groups. In particular, this invention includes every independent secondary combination of the various members of these group types and scopes. For example, the terms "C1-C6 alkyl" or "C..." 1-6 "Alkyl" specifically refers to independently disclosed methyl, ethyl, C3 alkyl, C4 alkyl, C5 alkyl, and C6 alkyl.

[0073] As used in this invention, the term "alkyl" or "alkyl group" refers to a saturated straight-chain or branched monovalent hydrocarbon group containing 1 to 20 carbon atoms; wherein the alkyl group is optionally substituted by one or more substituents described in this invention. Unless otherwise specified, the alkyl group contains 1 to 20 carbon atoms. In one embodiment, the alkyl group contains 1 to 12 carbon atoms; in another embodiment, the alkyl group contains 1 to 8 carbon atoms; in yet another embodiment, the alkyl group contains 1 to 6 carbon atoms; in still another embodiment, the alkyl group contains 1 to 4 carbon atoms; and in yet another embodiment, the alkyl group contains 1 to 3 carbon atoms.

[0074] 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), and so on. Pentyl (-CH2CH2CH2CH2CH3), 2-pentyl (-CH(CH3)CH2CH2CH3), 3-pentyl (-CH(CH2CH3)2), 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), etc.

[0075] The term "alkoxy" indicates that an alkyl group is attached to the rest of the molecule by an oxygen atom, wherein the alkyl group has the meaning as described in this invention. 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), etc.

[0076] The term "halogen" refers to fluorine (F), chlorine (Cl), bromine (Br), or iodine (I).

[0077] The term “halogenated alkyl” means that an alkyl group is replaced by one or more halogen atoms. Examples of such substitutions include, but are not limited to, -CF3, -CHF2, -CH2Cl, -CH2CF3, -CH2CHF2, -CH2CH2CF3, etc.

[0078] The term “haloalkoxy” means that the alkoxy group is replaced by one or more halogen atoms. Examples of such substitutions include, but are not limited to, -OCF3, -OCHF2, -OCHCl2, -OCH2CHF2, -OCH2CHCl2, -OCH(CH3)CHF2, etc.

[0079] The term "aryl" refers to a monocyclic, bicyclic, or tricyclic carbocyclic system containing 6-14, 6-12, or 6-10 ring atoms, wherein at least one ring system is aromatic, and each ring system comprises a ring of 3-7 atoms with one or more attachment sites connected to the remainder of the molecule. The term "aryl" may be used interchangeably with the term "aromatic ring." Examples of aryl groups may include phenyl, indenyl, naphthyl, and anthraceneyl. The aryl group may optionally be substituted by one or more substituents described in this invention.

[0080] The term "heteroaryl" refers to a monocyclic, bicyclic, or tricyclic system containing 5-12, 5-10, 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 a ring consisting of 5-7 atoms and has one or more attachment sites connected to the remainder of the molecule. The term "heteroaryl" may be used interchangeably with the terms "heteroaryl ring" or "heteroaryl compound." The heteroaryl group may optionally be substituted by one or more substituents described in this invention. In one embodiment, the 5-10-atom heteroaryl group contains 1, 2, 3, or 4 heteroatoms independently selected from O, S, and N. Examples of heteroaryl groups include, but are not limited to, pyridin-3-yl, quinoline-3-yl, benzopiperidinyl, benzothiophene-3-yl, etc.

[0081] The term "cyano" refers to -CN.

[0082] The term "hydroxyl group" refers to -OH.

[0083] The term "nitro" refers to -NO2.

[0084] The term "carboxyl group" refers to -COOH.

[0085] The term "amino" refers to -NH2.

[0086] The term "alkenyl" refers to a straight-chain or branched monovalent hydrocarbon group containing 2-12 carbon atoms, with at least one unsaturated site, i.e., one carbon-carbon sp. 2The double bond, wherein the alkenyl group may optionally be substituted by one or more substituents described in this invention, including the orientation of "cis" and "tans", or the orientation of "E" and "Z". In one embodiment, the alkenyl group comprises 2-8 carbon atoms; in another embodiment, the alkenyl group comprises 2-6 carbon atoms; in yet another embodiment, the alkenyl group comprises 2-4 carbon atoms. Examples of alkenyl groups include, but are not limited to, vinyl (-CH=CH2), allyl (-CH2CH=CH2), propenyl (CH3-CH=CH-), oxobutenyl (CH3-C(=O)-CH=CH-), etc.

[0087] The term "alkynyl" refers to a straight-chain or branched monovalent hydrocarbon group containing 2 to 12 carbon atoms, with at least one carbon-carbon sp triple bond. Examples of alkynyl groups include, but are not limited to, ethynyl (-CH≡CH), propynyl (-CH₂C≡CH), etc.

[0088] The term "cycloalkyl" refers to a monovalent or polyvalent saturated monocyclic, bicyclic, or tricyclic system containing 3-12 carbon atoms. In one embodiment, the cycloalkyl group comprises 3-10 carbon atoms; in another embodiment, it comprises 3-8 carbon atoms; and in yet another embodiment, it comprises 3-6 carbon atoms. The cycloalkyl group may optionally be substituted by one or more substituents described in this invention. Examples of such substituents include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl, cyclododecyl, etc.

[0089] The salts of the compounds described in this invention include those derived from alkali metals or alkaline earth metals, as well as those derived from ammonia and amines. Preferred cations include sodium, potassium, magnesium, and those having the chemical formula N. + (R A R B R C R D The ammonium cation of ) where R A R B R C and R D The compounds are independently selected from hydrogen, C1-C6 alkyl, and C1-C6 hydroxyalkyl. Salts of the compounds described in this invention can be prepared by treating the compounds described in this invention with a metal hydroxide (e.g., sodium hydroxide) or an amine (e.g., ammonia, trimethylamine, diethanolamine, 2-methylthiopropylamine, diallylamine, 2-butoxyethylamine, morpholine, cyclododecylamine, or benzylamine).

[0090] When the compounds of the present invention contain a base moiety, the acceptable salts can 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.

[0091] Compositions and formulations of the compounds of the present invention

[0092] The compounds of the present invention can generally be used as fungicidal active ingredients in compositions or formulations, and usually also include adjuvants commonly used in pesticide science; said adjuvants include surfactants and / or carriers.

[0093] The surfactants mentioned above can be various surfactants known in the field of pesticide formulation, and the present invention is preferably one or more of emulsifiers, dispersants and wetting agents.

[0094] Other carriers besides the surfactants mentioned above can be any type of carrier known in the field of pesticide formulation, including various silicates, carbonates, sulfates, oxides, phosphates, plant carriers, and synthetic carriers. Specifically, examples include: silica, kaolin, diatomaceous earth, clay, talc, organobentonite, pumice, titanium dioxide, dextrin, cellulose powder, light calcium carbonate, soluble starch, corn starch, sawdust, urea, amine fertilizer, mixtures of urea and amine fertilizer, glucose, maltose, sucrose, anhydrous potassium carbonate, anhydrous sodium carbonate, anhydrous potassium bicarbonate, anhydrous sodium bicarbonate, attapulgite, mixtures of anhydrous potassium carbonate and anhydrous potassium bicarbonate, and mixtures of anhydrous sodium carbonate and anhydrous sodium bicarbonate, or one or more of these.

[0095] The emulsifier mentioned above can be any emulsifier known in the field of pesticide formulation. Specifically, the emulsifier can be one or more of the following: calcium dodecylbenzenesulfonate, triphenylethylphenol 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 its ethylene oxide adduct, styrene-based phenyl polyoxyethylene ether, alkylphenol formaldehyde resin polyoxyethylene ether, hydroxyl-terminated polyoxyethylene polyoxypropylene ether, styrene-based phenol formaldehyde resin polyoxyethylene polyoxypropylene ether, and castor oil polyoxyethylene ether.

[0096] The dispersant mentioned above can be any dispersant known in the field of pesticide formulation. Specifically, the dispersant is one or more of the following: sodium salt of acrylic acid homopolymer, disodium salt of maleate, sodium salt of naphthalene sulfonate formaldehyde condensate, rosin block polyoxyethylene ether polyoxypropylene ether sulfonate, hydroxyl-terminated polyoxyethylene polyoxypropylene ether block copolymer, triphenylethylphenol polyoxyethylene ether phosphate, fatty alcohol polyoxyethylene ether phosphate, and sodium salt of p-hydroxyphenyl lignin sulfonate.

[0097] The aforementioned wetting agent can be any wetting agent known in the field of pesticide formulation. 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.

[0098] 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 formulation. Specifically, the formulation adjuvant may be one or more of solvents, cosolvents, thickeners, antifreeze agents, encapsulating materials, protectants, defoamers, disintegrants, stabilizers, preservatives, and binders.

[0099] The solvents mentioned above can be various solvents known in the field of pesticide formulations. Specifically, the solvent can be one or more of organic solvents, vegetable oils, mineral oils, solvent oils, and water.

[0100] 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.

[0101] The vegetable oils include one or more of the following: methylated vegetable oils, rosin-based vegetable oils, turpentine oil, epoxidized soybean oil, soybean oil, peanut oil, rapeseed oil, castor oil, corn oil, and pine nut oil.

[0102] The mineral oil includes one or more of liquid wax, engine oil, kerosene, and lubricating oil.

[0103] In addition, the above solvents can also be used as cosolvents.

[0104] The antifreeze agent mentioned above can be any antifreeze agent known in the field of pesticide formulation, and the present invention preferably includes one or more of ethylene glycol, propylene glycol, glycerin and urea.

[0105] The aforementioned thickener can be any thickener known in the field of pesticide formulation. Specifically, the thickener can be one or more of xanthan gum, polyvinyl alcohol, polyacryl alcohol, polyethylene glycol, silica, diatomaceous earth, kaolin, clay, sodium alginate, magnesium aluminum silicate, sodium aluminum silicate, carboxymethyl cellulose, sodium hydroxypropyl cellulose, and organobentonite.

[0106] The aforementioned encapsulating material can be any of the encapsulating materials known in the field of pesticide formulations, and the present invention preferably uses one or more of polyurethane, polyurea, and urea-formaldehyde resin.

[0107] The aforementioned protective agent can be any of the protective agents known in the field of pesticide formulation, and the present invention preferably uses polyvinyl alcohol and / or polyethylene glycol.

[0108] The defoamer mentioned above can be any defoamer known in the field of pesticide formulations. The present invention preferably includes one or more of organosiloxanes, tributyl phosphate and silicones.

[0109] The stabilizer is selected from one or more of triphenyl phosphite, epichlorohydrin, and acetic anhydride.

[0110] The above-mentioned preservatives are selected from one or more of benzoic acid, sodium benzoate, 1,2-benzisothiazolin-3-one (BIT), Kathon and potassium sorbate.

[0111] This invention also provides a formulation prepared from the above-described bactericidal composition, wherein the formulation is in the form of an emulsifiable concentrate, an aqueous emulsion, a microemulsion, a soluble liquid, an aqueous suspension, a suspension emulsion, an ultra-low volume spray, an oil suspension, a microcapsule suspension, a water-spreading oil, a wettable powder, a water-dispersible granule, a dry suspension, a soluble powder, a soluble granule, an emulsifiable powder, an emulsifiable granule, granules, a solid microcapsule formulation, an effervescent tablet, an effervescent granule, a water-floating dispersible granule, or a seed coating agent. All of the above formulations can be prepared by conventional methods in the art.

[0112] The preparation method of the above-mentioned emulsifiable concentrate formulation may include, for example, mixing and stirring the active components, solvent, cosolvent and emulsifier to form a uniform and transparent oil phase, thereby obtaining the emulsifiable concentrate formulation.

[0113] The above-mentioned method for preparing water-in-water emulsions may include, for example, mixing active ingredients, emulsifiers, co-solvents, and solvents to form a homogeneous oil phase; or mixing water, thickeners, antifreeze, etc., to form a homogeneous aqueous phase. Under high-speed shearing, the aqueous phase is added to the oil phase or the oil phase is added to the aqueous phase to form a well-dispersible water-in-water emulsion.

[0114] The preparation method of the above-mentioned microemulsion may include, for example, mixing and stirring the active ingredient, emulsifier, and solvent to form a homogeneous and transparent oil phase. Under stirring conditions, water is gradually added to form a homogeneous and transparent microemulsion.

[0115] The preparation method of the above-mentioned water / oil suspension is as follows: For example, water or oil can be used as the medium. The active component, surfactant, and other additives are added to a sand mill and ground to a certain particle size, then filtered. A metered thickener is then added to the ground mother liquor and sheared to disperse it evenly. This produces an oil suspension or a water suspension.

[0116] The preparation methods of the above-mentioned water-dispersible granules and soluble granules are as follows: For example, the active components, dispersants, wetting agents, carriers, etc. are mixed evenly, then pulverized to a certain particle size by airflow, water is added and kneaded, and finally added to a granulator for granulation. After drying, water-dispersible granules or soluble granules can be obtained.

[0117] The preparation methods of the above-mentioned soluble powders and wettable powders include, for example, thoroughly mixing each active component, various additives and other carriers and fillers, and then pulverizing them using an ultrafine pulverizer.

[0118] The bactericide composition of the present invention can be provided in the form of a finished formulation, i.e., the substances in the composition have been mixed; or it can be provided in the form of a separate formulation, which can be mixed in a barrel or tank before use and selectively diluted with water according to the desired concentration of active substances.

[0119] Application of the compounds and compositions of the present invention

[0120] The compounds of this invention can be used as plant disease control agents. Therefore, this invention may also include a method for controlling plant diseases caused by plant pathogenic fungi, the method comprising applying an effective amount of the compounds of this invention or a fungicidal composition containing the compounds of this invention to the plant to be protected or to parts thereof or to the seeds of the plant to be protected. The compounds and / or compositions of this invention can provide control over diseases caused by broad-spectrum plant pathogenic fungi of the Basidiomycetes, Ascomycetes, Oomycetes, and Deuteromycetes classes. They can effectively control broad-spectrum plant diseases, especially leaf pathogens in ornamental crops, turf crops, vegetable crops, field crops, cereal crops, and fruit crops. These pathogens include: oomycetes, including diseases of the genus *Phytophthora* such as *Phytophthora infestans*, *Phytophthora megasperma*, *Phytophthora parasitica*, *Phytophthora cinnamomi*, and *Phytophthora capsici*; diseases of species in the genus *Pythium* such as *Pythium aphanidermatum*; and diseases of species in the family Peronosporaceae such as *Plasmopara viticola*, diseases of the genus *Peronospora* (including *Peronospora tabacina* and *Peronospora parasitica*), and diseases of the genus *Pseudoperonospora*. Diseases caused by fungi (including *Pseudoperonospora cubensis* and *Bremia lactucae*); ascomycetes (including *Alternaria* pathogens such as *Alternaria solani* and *Alternaria brassicae*, *Guignardia* pathogens such as *Guignardia bidwell*, *Venturia* pathogens such as *Venturia inaequalis*, *Septoria* pathogens such as *Septoria nodorum* and *Septoria tritici*, and powdery mildew pathogens such as *Erysiphe* spp.).(Including wheat powdery mildew (Erysiphegraminis) and radish powdery mildew (Erysiphe polygoni)), grape powdery mildew (Uncinula necatur), cucumber powdery mildew (Sphaerotheca fuligena) and apple powdery mildew (Podosphaera leucotricha), wheat basal rot (Pseudocercosporella herpotrichoides), Botrytis diseases such as strawberry gray mold (Botrytis cinerea) and peach brown rot (Monilinia fructicola), Sclerotinia diseases such as rapeseed sclerotinia sclerotiorum, rice blast (Magnaporthe grisea), grape twig blight (Phomopsis viticola), and Helminthosporium diseases such as corn leaf blight (Helminthosporium tritici) *Pyrenophora teres*, anthracnose fungi such as *Glomerella* or *Colletotrichum* spp. diseases (e.g., *Colletotrichum graminicola* and *Colletotrichum orbiculare*), and *Gaeumannomyces graminis*, the causal agent of wheat take-all; basidiomycetes, including rust diseases caused by *Puccinia* spp. (e.g., *Puccinia recondita*, *Puccinia striiformis*, *Puccinia hordei*, *Puccinia graminis*, and *Puccinia arachidis*), coffee rust (*Hemileia vastatrix*), and soybean rust (*Phakopsora pachyrhizi*); other pathogens include species of *Rhizoctonia* spp.(e.g., 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 categories and species closely related to these pathogens. In addition to their antifungal activity, the compositions or combinations also exhibit resistance to bacteria such as *Erwinia amylovora*, *Xanthomonas campestris*, *Pseudomonas syringae*, and other fungal species.

[0121] The fungicide composition of this invention is simple to use. It is applied to the crop and its growing area using conventional methods, such as mixing with soil, spraying, spraying, or watering, before or after the emergence of plant diseases. The application rate depends on climatic conditions or crop condition; generally, the effective amount per acre is 10-5000g, diluted to 10-400mg / L (preferably 100-300mg / L) before application. Water is the preferred diluent.

[0122] The bactericidal composition of the present invention has a bactericidal effect that is usually related to external factors such as climate, but the influence of climate can be mitigated by using appropriate formulations.

[0123] The compositions of the present invention can also be used in combination with other compounds that have bactericidal, insecticidal or herbicidal properties, or in combination with nematicides, acaricides, protective agents, herbicidal safeners, growth regulators, plant nutrients or soil conditioners.

[0124] General Synthesis Process

[0125] The following 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 herein. The raw materials, reagents, etc., used to prepare the compounds of the present invention are commercially available; or the raw materials, reagents, etc., can be prepared by conventional methods in the art. In this specification, if there are any differences between chemical names and chemical structures, the structure is preferred. Unless otherwise specified, room temperature in this invention is 5°C to 35°C.

[0126] The testing conditions for the proton NMR spectrum of this invention are: room temperature, a Bruker 400MHz or 600MHz NMR spectrometer, using CDCl3 or d... 6 - DMSO is used as the solvent (reported in ppm), with TMS (0ppm) as the reference standard. When multiplets are observed, the following abbreviations will be used: s (singlet), d (doublet), t (triplet), q (quartet), m (multiplet), br (broadened), dd (doublet of doublets), dt (doublet of triplets).

[0127] The conditions for determining the low-resolution mass spectrometry (MS) data of this invention are as follows: Agilent 6120 Quadrupole HPLC-MS (column model: Zorbax SB-C18, 2.1x30mm, 3.5μm, 6min, flow rate: 0.6mL / min, mobile phase: 5%-95% (CH3CN containing 0.1% formic acid) in (H2O containing 0.1% formic acid), detection at 210 / 254nm using UV, and electrospray ionization mode (ESI).

[0128] Synthesis scheme

[0129]

[0130] The target compound shown in formula (I) can be prepared by the above synthetic method. Specifically, the compound shown in formula (a) and the compound shown in formula (b) undergo a substitution reaction under alkaline conditions (such as potassium carbonate) to obtain the target compound shown in formula (I);

[0131] Among them, R 1 R 2 , T, R a R b R c R d and R eWith the meaning described in this invention, hal is fluorine, chlorine, bromine or iodine. Example

[0132] Intermediate 1: Synthesis of (Z)-(1-methyl-1H-tetrazol-5-yl)(phenyl)methyl ketone oxime

[0133]

[0134] Step 1: Synthesis of N-methyl-2-oxo-2-phenylacetamide

[0135]

[0136] At 0°C, methyl benzoylformate (164 g, 1 mol) was dissolved in methanol (500 mL), and methylamine aqueous solution (40%, 101 g, 1.3 mol) was added dropwise. After the addition was complete, the mixture was stirred at room temperature for 2 hours. The reaction was monitored by TLC until complete. The solvent was removed by concentration under reduced pressure, and the solution was diluted with ethyl acetate (300 mL). The solution was washed successively with water (200 mL), 1N sodium hydroxide (200 mL), 1N hydrochloric acid (200 mL), and saturated brine (200 mL). The solution was dried over anhydrous sodium sulfate, filtered, and the filtrate was concentrated under reduced pressure to give 130 g of pale yellow solid, yield: 80.4%.

[0137] LC-MS: (M+1)m / z = 164.1.

[0138] Step 2: Synthesis of (Z)-N-methyl-2-oxo-2-phenylacetylimine chloride

[0139]

[0140] At 0 °C, N-methyl-2-oxo-2-phenylacetamide (65 g, 0.4 mol) was dissolved in a mixed solution of N,N-dimethylformamide (2.9 g, 0.04 mol) and chloroform (500 mL), and thionyl chloride (71.4 g, 0.6 mol) was added dropwise. After the addition was complete, the mixture was stirred at room temperature for 2 hours, and then heated to 60 °C for 8 hours. The reaction was monitored by TLC until complete. The solvent was removed by concentration under reduced pressure, and the mixture was diluted with toluene (100 mL). The mixture was stirred at room temperature for 8 hours and then concentrated under reduced pressure to give 70 g of a brown oily liquid, yield: 96.2%.

[0141] LC-MS: (M+1)m / z = 182.0.

[0142] Step 3: Synthesis of (1-methyl-1H-tetrazol-5-yl)(phenyl) ketone

[0143]

[0144] Sodium azide (6.5 g, 100 mmol) and tetrabutylammonium bromide (1.62 g, 5 mmol) were dissolved in a mixture of toluene (20 mL) and water (20 mL) at room temperature. A toluene solution (60 mL) of (Z)-N-methyl-2-oxo-2-phenylacetylimino chloride (18.2 g, 100 mmol) was added dropwise. After the addition was complete, the mixture was stirred at room temperature for 2 hours. The reaction was monitored by TLC until complete. The solution was diluted with toluene (20 mL), washed with water (100 mL x 3) and saturated brine (100 mL), dried over anhydrous sodium sulfate, filtered, and the filtrate was concentrated to give 15.4 g of a brown oily liquid, yield: 85.4%.

[0145] LC-MS: (M+1)m / z = 189.1.

[0146] Step 4: Synthesis of (Z)-(1-methyl-1H-tetrazole-5-yl)(phenyl)methyl ketone oxime

[0147]

[0148] At room temperature, (1-methyl-1H-tetrazol-5-yl)(phenyl) ketone (15 g, 80 mmol) and hydroxylamine hydrochloride (11.1 g, 160 mmol) were dissolved in ethanol (100 mL), heated to 48 °C, and stirred for 12 hours. The reaction was monitored by TLC until complete. The ethanol was removed by vacuum concentration, diluted with water (100 mL), and extracted with ethyl acetate (50 mL x 3). The organic phases were combined, washed with saturated brine (100 mL), concentrated under reduced pressure, and the residue was separated by silica gel column chromatography [petroleum ether / ethyl acetate (v / v) = 4 / 1] to give 5.6 g of pale yellow solid, yield: 34.1%.

[0149] LC-MS: (M+1)m / z = 204.1.

[0150] Intermediate 2: Synthesis of 2-chloro-N-phenylacetamide

[0151]

[0152] Aniline (0.47 g, 5.0 mmol), triethylamine (0.51 g, 5.0 mol), and dichloromethane (30 mL) were added to a 100 mL single-necked flask. Chloroacetyl chloride (0.68 g, 6.0 mmol) was added dropwise with stirring at 0 °C. After the addition was complete, the mixture was brought to room temperature and stirred for 2 hours. The reaction was monitored by TLC until complete. The reaction was quenched with water (50 mL), and extracted with dichloromethane (20 mL x 3). The organic phases were combined, dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure to give 0.58 g of a yellow oily liquid, with a yield of 68%.

[0153] LC-MS: (M+1)m / z = 170.0.

[0154] Using the corresponding raw materials and chloroacetyl chloride as starting materials, the intermediate compounds in Table 1 were prepared by referring to the preparation method of intermediate 2 or the preparation method of the prior art.

[0155] Table 1

[0156]

[0157]

[0158]

[0159]

[0160] Example 1: Synthesis of (Z)-2-((((1-methyl-1H-tetrazol-5-yl)(phenyl)methylene)amino)oxy)-N-phenylacetamide

[0161]

[0162] Intermediate 1 (i.e., (Z)-(1-methyl-1H-tetrazol-5-yl)(phenyl)methyl ketone oxime) (0.41 g, 2 mmol), anhydrous potassium carbonate (0.55 g, 4 mmol), and N,N-dimethylformamide (15 mL) were added to a 50 mL single-necked flask. A solution of intermediate 2 (i.e., 2-chloro-N-phenylacetamide) (0.68 g, 4 mmol) in N,N-dimethylformamide (5 mL) was added dropwise. The mixture was stirred at room temperature for 12 h, and the reaction was monitored by TLC until the starting material was fully reacted. The reaction was quenched with water (150 mL), and the mixture was extracted with ethyl acetate (50 mL × 3). The organic phases were combined and dried over anhydrous sodium sulfate. The mixture was filtered, and the filtrate was concentrated under reduced pressure. The residue was purified by silica gel mixing and column chromatography [petroleum ether / ethyl acetate (v / v) = 4 / 1] to give 0.42 g of a white solid, yield: 62.6%.

[0163] 1 H NMR (400MHz, CDCl3) δ (ppm): 8.56 (s, 1H), 7.47 (d, J=8.3Hz, 3H), 7.39 (d, J= 8.1Hz,2H),7.32-7.28(m,3H),7.25–7.23(m,2H),4.25(s,2H),3.93(s,3H).

[0164] LC-MS: (M+1)m / z = 337.1.

[0165] Example 2: Synthesis of (Z)-N-(3-chloro-2-methylphenyl)-2-((((1-methyl-1H-tetrazol-5-yl)(phenyl)methylene)amino)oxy)acetamide

[0166]

[0167] Intermediate 1 (0.38 g, 2 mmol) and intermediate 3 (i.e., 2-chloro-N-(3-chloro-2-methylphenyl)acetamide) (0.87 g, 4 mmol) were prepared according to the preparation method in Example 1, and 0.51 g of white solid was obtained, with a yield of 65.3%.

[0168] 1 H NMR (400MHz, CDCl3) δ (ppm): 8.51 (s, 1H), 7.42 (d, J = 8.3Hz, 3H), 7.33 (d, J = 8.3Hz, 2H),7.30-7.27(m,1H),7.22–7.20(m,2H),4.22(s,2H),3.90(s,3H),2.51(s,3H).

[0169] LC-MS: (M+1)m / z = 385.1.

[0170] Example 3: Synthesis of (Z)-N-(2-fluoro-3-methylphenyl)-2-((((1-methyl-1H-tetrazol-5-yl)(phenyl)methylene)amino)oxy)acetamide

[0171]

[0172] Intermediate 1 (0.38 g, 2 mmol) and intermediate 4 (i.e., 2-chloro-N-(2-fluoro-3-methylphenyl)acetamide) (0.81 g, 4 mmol) were prepared according to the preparation method in Example 1, and 0.45 g of white solid was obtained, with a yield of 61.1%.

[0173] 1 H NMR (400MHz, CDCl3) δ (ppm): 8.53 (s, 1H), 7.45 (d, J = 8.1Hz, 3H), 7.36 (d, J = 8.2Hz, 2H),7.31-7.27(m,1H),7.23–7.20(m,2H),4.27(s,2H),3.92(s,3H),2.55(s,3H).

[0174] LC-MS: (M+1)m / z = 369.1.

[0175] Example 4: Synthesis of (Z)-N-(2-bromo-4-fluorophenyl)-2-((((1-methyl-1H-tetrazol-5-yl)(phenyl)methylene)amino)oxy)acetamide

[0176]

[0177] Intermediate 1 (0.38 g, 2 mmol) and intermediate 5 (i.e., N-(2-bromo-4-fluorophenyl)-2-chloroacetamide) (1.06 g, 4 mmol) were prepared according to the preparation method in Example 1, and 0.53 g of white solid was obtained, with a yield of 61.3%.

[0178] 1 H NMR (400MHz, CDCl3) δ (ppm): 8.51 (s, 1H), 7.42 (d, J=8.2Hz, 3H), 7.35 (d, J= 8.3Hz,2H),7.31-7.27(m,1H),7.22–7.20(m,2H),4.22(s,2H),3.90(s,3H).

[0179] LC-MS: (M+1)m / z = 433.0.

[0180] Example 5: Synthesis of (Z)-N-(3-fluorophenyl)-2-((((1-methyl-1H-tetrazol-5-yl)(phenyl)methylene)amino)oxy)acetamide

[0181]

[0182] Intermediate 1 (0.38 g, 2 mmol) and intermediate 6 (2-chloro-N-(3-fluorophenyl)acetamide) (0.75 g, 4 mmol) were prepared according to the preparation method in Example 1, and 0.44 g of white solid was obtained, with a yield of 63.2%.

[0183] 1 H NMR (400MHz, CDCl3) δ (ppm): 8.53 (s, 1H), 7.45 (d, J=8.1Hz, 3H), 7.36 (d, J= 8.2Hz,2H),7.31-7.27(m,2H),7.23–7.20(m,2H),4.24(s,2H),3.91(s,3H).

[0184] LC-MS: (M+1)m / z = 355.1.

[0185] Example 6: Synthesis of (Z)-N-(2-bromo-6-fluorophenyl)-2-((((1-methyl-1H-tetrazol-5-yl)(phenyl)methylene)amino)oxy)acetamide

[0186]

[0187] Intermediate 1 (0.38 g, 2 mmol) and intermediate 7 (i.e., N-(2-bromo-6-fluorophenyl)-2-chloroacetamide) (1.06 g, 4 mmol) were prepared according to the preparation method in Example 1, and 0.57 g of white solid was obtained, with a yield of 66.3%.

[0188] 1 H NMR (400MHz, CDCl3) δ (ppm): 8.50 (s, 1H), 7.43 (d, J=8.4Hz, 3H), 7.35 (d, J= 8.3Hz,2H),7.31-7.27(m,1H),7.21–7.18(m,2H),4.22(s,2H),3.91(s,3H).

[0189] LC-MS: (M+1)m / z = 433.0.

[0190] Example 7: Synthesis of (Z)-N-(3,4-difluorophenyl)-2-((((1-methyl-1H-tetrazol-5-yl)(phenyl)methylene)amino)oxy)acetamide

[0191]

[0192] Intermediate 1 (0.38 g, 2 mmol) and intermediate 8 (i.e., 2-chloro-N-(3,4-difluorophenyl)acetamide) (0.82 g, 4 mmol) were prepared according to the preparation method in Example 1, and 0.45 g of white solid was obtained, with a yield of 60.2%.

[0193] 1 H NMR (400MHz, CDCl3) δ (ppm): 8.53 (s, 1H), 7.45 (d, J=8.1Hz, 3H), 7.36 (d, J= 8.2Hz,2H),7.31-7.27(m,2H),7.23–7.20(m,1H),4.24(s,2H),3.91(s,3H).

[0194] LC-MS: (M+1)m / z = 373.1.

[0195] Example 8: Synthesis of (Z)-N-(2,6-dibromophenyl)-2-((((1-methyl-1H-tetrazol-5-yl)(phenyl)methylene)amino)oxy)acetamide

[0196]

[0197] Intermediate 1 (0.38 g, 2 mmol) and intermediate 9 (i.e., 2-chloro-N-(2,6-dibromophenyl)acetamide) (1.31 g, 4 mmol) were prepared according to the preparation method in Example 1, and 0.59 g of white solid was obtained, with a yield of 60.3%.

[0198] 1 H NMR (400MHz, CDCl3) δ (ppm): 8.50 (s, 1H), 7.43 (d, J=8.4Hz, 3H), 7.35 (d, J= 8.3Hz,2H),7.31-7.27(m,2H),7.21–7.18(m,1H),4.22(s,2H),3.91(s,3H).

[0199] LC-MS: (M+1)m / z = 493.0.

[0200] Example 9: Synthesis of (Z)-N-(2,4-dichlorophenyl)-2-((((1-methyl-1H-tetrazol-5-yl)(phenyl)methylene)amino)oxy)acetamide

[0201]

[0202] Intermediate 1 (0.38 g, 2 mmol) and intermediate 10 (i.e., 2-chloro-N-(2,4-dichlorophenyl)acetamide) (0.95 g, 4 mmol) were prepared according to the preparation method in Example 1, and 0.54 g of white solid was obtained, with a yield of 67.2%.

[0203] 1 H NMR (400MHz, CDCl3) δ (ppm): 8.51 (s, 1H), 7.45 (d, J=8.1Hz, 3H), 7.36 (d, J= 8.2Hz,2H),7.31-7.28(m,2H),7.23–7.20(m,1H),4.24(s,2H),3.93(s,3H).

[0204] LC-MS: (M+1)m / z = 405.1.

[0205] Example 10: Synthesis of (Z)-2-((((1-methyl-1H-tetrazol-5-yl)(phenyl)methylene)amino)oxy)-N-(2-(trifluoromethoxy)phenyl)acetamide

[0206]

[0207] Intermediate 1 (0.38 g, 2 mmol) and intermediate 11 (i.e., 2-chloro-N-(2-(trifluoromethoxy)phenyl)acetamide) (1.02 g, 4 mmol) were prepared according to the preparation method in Example 1, and 0.45 g of white solid was obtained, with a yield of 54.3%.

[0208] 1 H NMR (400MHz, CDCl3) δ (ppm): 8.52 (s, 1H), 7.44 (d, J=8.4Hz, 3H), 7.36 (d, J= 8.3Hz,2H),7.31-7.27(m,2H),7.21–7.18(m,2H),4.25(s,2H),3.94(s,3H).

[0209] LC-MS: (M+1)m / z = 421.1.

[0210] Example 11: Synthesis of (Z)-N-(3-isopropoxyphenyl)-2-((((1-methyl-1H-tetrazol-5-yl)(phenyl)methylene)amino)oxy)acetamide

[0211]

[0212] Intermediate 1 (0.38 g, 2 mmol) and intermediate 12 (2-chloro-N-(3-isopropoxyphenyl)acetamide) (0.91 g, 4 mmol) were prepared according to the preparation method in Example 1, and 0.49 g of white solid was obtained, with a yield of 63.2%.

[0213] 1 H NMR (400MHz, CDCl3) δ (ppm): 8.51 (s, 1H), 7.45 (d, J = 8.1Hz, 3H), 7.36 (d, J = 8.2Hz, 2H), 7.31-7.28 (m, 2H), 7. 23–7.20(m,1H),7.11(s,1H),4.56(dq,J=12.0,6.0Hz,1H),4.24(s,2H),3.93(s,3H),1.35(d,J=6.0Hz,6H).

[0214] LC-MS: (M+1)m / z = 395.2.

[0215] Example 12: Synthesis of (Z)-N-(3-bromophenyl)-2-((((1-methyl-1H-tetrazol-5-yl)(phenyl)methylene)amino)oxy)acetamide

[0216]

[0217] Intermediate 1 (0.38 g, 2 mmol) and intermediate 13 (i.e., N-(3-bromophenyl)-2-chloroacetamide) (0.99 g, 4 mmol) were prepared according to the preparation method in Example 1, and 0.42 g of white solid was obtained, with a yield of 51.3%.

[0218] 1 H NMR (400MHz, CDCl3) δ (ppm): 8.52 (s, 1H), 7.44 (d, J = 8.4Hz, 3H), 7.36 (d, J = 8.3Hz, 2H), 7.31-7.27 (m, 3H), 7.18 (s, 1H), 4.25 (s, 2H), 3.94 (s, 3H).

[0219] LC-MS: (M+1)m / z = 415.0.

[0220] Example 13: Synthesis of (Z)-N-(2-fluoro-5-methylphenyl)-2-((((1-methyl-1H-tetrazol-5-yl)(phenyl)methylene)amino)oxy)acetamide

[0221]

[0222] Intermediate 1 (0.38 g, 2 mmol) and intermediate 14 (i.e., 2-chloro-N-(2-fluoro-5-methylphenyl)acetamide) (0.81 g, 4 mmol) were prepared according to the preparation method in Example 1, and 0.40 g of white solid was obtained, with a yield of 54.1%.

[0223] 1 H NMR (400MHz, CDCl3) δ (ppm): 8.53 (s, 1H), 7.45 (d, J = 8.1Hz, 3H), 7.36 (d, J = 8.2Hz, 2H),7.31-7.27(m,1H),7.23–7.20(m,2H),4.27(s,2H),3.92(s,3H),2.55(s,3H).

[0224] LC-MS: (M+1)m / z = 369.1.

[0225] Example 14: Synthesis of (Z)-N-(4-(tert-butyl)phenyl)-2-((((1-methyl-1H-tetrazol-5-yl)(phenyl)methylene)amino)oxy)acetamide

[0226]

[0227] Intermediate 1 (0.38 g, 2 mmol) and intermediate 15 (i.e., N-(4-(tert-butyl)phenyl)-2-chloroacetamide) (0.90 g, 4 mmol) were prepared according to the preparation method in Example 1, and 0.48 g of white solid was obtained, with a yield of 61.7%.

[0228] 1 H NMR (400MHz, CDCl3) δ (ppm): 8.52 (s, 1H), 7.44 (d, J = 8.4Hz, 3H), 7.36 (d, J = 8.3Hz, 2H), 7.26(dd,J=9.4Hz,2H),7.19(dd,J=10.8Hz,2H),4.25(s,2H),3.94(s,3H),1.33(s,9H).

[0229] LC-MS: (M+1)m / z = 393.2.

[0230] Example 15: Synthesis of (Z)-N-(4-chloropyridin-3-yl)-2-((((1-methyl-1H-tetrazol-5-yl)(phenyl)methylene)amino)oxy)acetamide

[0231]

[0232] Intermediate 1 (0.38 g, 2 mmol) and intermediate 16 (2-chloro-N-(4-chloropyridin-3-yl)acetamide) (0.82 g, 4 mmol) were prepared according to the preparation method in Example 1, and 0.37 g of white solid was obtained, with a yield of 50.1%.

[0233] 1 H NMR (400MHz, CDCl3) δ (ppm): 8.53 (s, 1H), 7.45 (d, J=8.1Hz, 3H), 7.36 (d, J= 8.2Hz,2H),7.31-7.27(m,1H),7.23–7.20(m,2H),4.27(s,2H),3.92(s,3H).

[0234] LC-MS: (M+1)m / z = 372.1.

[0235] Example 16: Synthesis of (Z)-N-(2-bromopyridin-3-yl)-2-((((1-methyl-1H-tetrazol-5-yl)(phenyl)methylene)amino)oxy)acetamide

[0236]

[0237] Intermediate 1 (0.38 g, 2 mmol) and intermediate 17 (i.e., N-(2-bromopyridin-3-yl)-2-chloroacetamide) (0.99 g, 4 mmol) were prepared according to the preparation method in Example 1, and 0.45 g of white solid was obtained, with a yield of 54.1%.

[0238] 1 H NMR (400MHz, CDCl3) δ (ppm): 8.49 (s, 1H), 7.43 (d, J=8.5Hz, 3H), 7.34 (d, J= 8.1Hz,2H),7.30-7.27(m,1H),7.24–7.20(m,2H),4.25(s,2H),3.90(s,3H).

[0239] LC-MS: (M+1)m / z = 416.0.

[0240] Example 17: Synthesis of (Z)-N-(6-fluoropyridin-3-yl)-2-((((1-methyl-1H-tetrazol-5-yl)(phenyl)methylene)amino)oxy)acetamide

[0241]

[0242] Intermediate 1 (0.38 g, 2 mmol) and intermediate 18 (i.e., 2-chloro-N-(6-fluoropyridin-3-yl)acetamide) (0.76 g, 4 mmol) were prepared according to the preparation method in Example 1, and 0.39 g of white solid was obtained, with a yield of 55.5%.

[0243] 1 H NMR (400MHz, CDCl3) δ (ppm): 8.55 (s, 1H), 7.42 (d, J=8.1Hz, 3H), 7.34 (d, J= 8.2Hz,2H),7.30-7.26(m,1H),7.22–7.19(m,2H),4.24(s,2H),3.91(s,3H).

[0244] LC-MS: (M+1)m / z = 356.1.

[0245] Example 18: Synthesis of (Z)-N-(6-(dimethylamino)pyridin-3-yl)-2-((((1-methyl-1H-tetrazol-5-yl)(phenyl)methylene)amino)oxy)acetamide

[0246]

[0247] Intermediate 1 (0.38 g, 2 mmol) and intermediate 19 (i.e., 2-chloro-N-(6-(dimethylamino)pyridin-3-yl)acetamide) (0.86 g, 4 mmol) were prepared according to the preparation method in Example 1, and 0.47 g of white solid was obtained, with a yield of 62.2%.

[0248] 1 H NMR (400MHz, CDCl3) δ (ppm): 8.49 (s, 1H), 7.43 (d, J = 8.5Hz, 3H), 7.34 (d, J = 8.1 Hz,2H),7.27(s,1H),7.24–7.20(m,2H),4.24(s,2H),3.90(s,3H),3.13(s,6H).

[0249] LC-MS: (M+1)m / z = 381.2.

[0250] Example 19: Synthesis of (Z)-N-(5-chloropyridin-3-yl)-2-((((1-methyl-1H-tetrazol-5-yl)(phenyl)methylene)amino)oxy)acetamide

[0251]

[0252] Intermediate 1 (0.38 g, 2 mmol) and intermediate 20 (i.e., 2-chloro-N-(5-chloropyridin-3-yl)acetamide) (0.82 g, 4 mmol) were prepared according to the preparation method in Example 1, and 0.38 g of white solid was obtained, with a yield of 51.2%.

[0253] 1 H NMR (400MHz, CDCl3) δ (ppm): 8.55 (s, 1H), 7.42 (d, J = 8.1Hz, 3H), 7.34 (d, J = 8.2 Hz,2H),7.30(s,1H),7.22–7.19(m,1H),7.13(s,1H),4.24(s,2H),3.91(s,3H).

[0254] LC-MS: (M+1)m / z = 372.1.

[0255] Example 20: Synthesis of (Z)-2-((((1-methyl-1H-tetrazol-5-yl)(phenyl)methylene)amino)oxy)-N-(quinolin-3-yl)acetamide

[0256]

[0257] Intermediate 1 (0.38 g, 2 mmol) and intermediate 21 (i.e., 2-chloro-N-(quinoline-3-yl)acetamide) (0.89 g, 4 mmol) were prepared according to the preparation method in Example 1, and 0.51 g of white solid was obtained, with a yield of 66.2%.

[0258] 1 H NMR (400MHz, CDCl3) δ (ppm): 8.53 (s, 1H), 7.64–7.60 (m, 3H), 7.43 (d, J = 8.5Hz, 3H) ,7.34(d,J=8.1Hz,2H),7.27(s,1H),7.24–7.20(m,2H),4.24(s,2H),3.93(s,3H).

[0259] LC-MS: (M+1)m / z = 388.1.

[0260] Life test:

[0261] Test treatment: The compounds were dissolved in N,N-dimethylformamide to prepare a 1% EC (emulsifiable concentrate) for later use. The bactericidal activity of these compounds against the test targets at different dosages was evaluated using a live pot experiment.

[0262] 1) Cucumber downy mildew test (Pseudoperonosporacubensis)

[0263] Select one potted cucumber seedling with uniform growth at the true leaf stage (with the growing point removed). Spray the seedling with water and allow it to air dry naturally. Inoculate the seedling 24 hours after treatment. Take fresh cucumber leaves infected with downy mildew and use a brush dipped in distilled water to wash off the sporangia on the underside of the leaves. Prepare a sporangia suspension (2-3 x 10⁻⁶). 5 (number / mL). Inoculate cucumber seedlings evenly with an inoculation sprayer (pressure 0.1 MPa). After inoculation, transfer the test material to an artificial climate chamber 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 disease. Five days later, conduct a graded survey based on the disease incidence of the blank control and calculate the control efficacy according to the disease index.

[0264] 2) Gray mold of cucumber (Botrytis cinerea)

[0265] Leaf inoculation was used. Two potted cucumber seedlings with uniform growth at the true leaf stage were selected. After the pesticide spray had dried, the mycelial cake was inoculated onto the leaves. After 24 hours of indirect light and humidity at 24–26℃, the seedlings were incubated under natural light and humidity for approximately 3 days. Once the control group had fully developed disease, the diameter of the lesions at each inoculation point was measured with calipers to calculate the control efficacy.

[0266] The experimental results are shown below:

[0267] Table 2. The efficacy of compounds at different concentrations against cucumber downy mildew.

[0268]

[0269]

[0270] Note: / indicates that the compound has not undergone efficacy testing at that concentration.

[0271] Table 2 shows that the compounds of the present invention in Examples 1 to 19 exhibit excellent control efficacy against cucumber downy mildew at different concentrations. Compound 20 of the present invention shows control efficacy against cucumber downy mildew of 100%, 60%, and 30% at concentrations of 100 mg / L, 50 mg / L, and 25 mg / L, respectively. Furthermore, the compounds of the present invention still exhibit excellent control efficacy against cucumber downy mildew at low concentrations. For example, at a concentration of 12.5 mg / L, the control efficacy against cucumber downy mildew in Examples 2, 4, 5, 6, 7, 8, 9, 10, 11, and 13 is between 70% and 100%; and at a concentration of 6.25 mg / L, the control efficacy against cucumber downy mildew in Examples 5, 6, 7, and 8 is between 70% and 100%.

[0272] In addition, at a concentration of 200 mg / L, the compounds of the present invention in Examples 5, 6, 7, 8, 13, and 14 showed a control efficacy of 70%-100% against gray mold in cucumbers.

[0273] The preferred embodiments of the present invention have been described in detail above. However, the present invention is not limited to the specific details in the above embodiments. Within the scope of the technical concept of the present invention, various simple modifications can be made to the technical solution of the present invention, and these simple modifications all fall within the protection scope of the present invention.

Claims

1. A compound having the formula (IA), or a salt of the compound having the formula (IA): (I-A); in, R 1 for , , , , , , , , , , , , , , , , , , or ; R 2 It is hydrogen; R a R b R c R d and R e Each is independently hydrogen; T is ; R f It is -CH3.

2. A compound having one of the following structures, or a salt of a compound having one of the following structures: (1) (2) (3) (4) (5) (6) (7) (8) (9) (10) (11) (12) (13) (14) (15) (16) (17) (18) (19) or (20).

3. A composition comprising the compound of any one of claims 1-2 and an adjuvant commonly used in pesticide science.

4. The application of the compound according to any one of claims 1-2 or the composition according to claim 3 as a fungicide in agriculture, wherein, The fungicide is used to prevent and control cucumber downy mildew and / or cucumber gray mold.

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