CN114195763A - Benzoyl oxy substituted oxime derivative and application thereof - Google Patents

Abstract

The invention relates to a benzoyloxy-substituted oxime derivative and application thereof, wherein the benzoyloxy-substituted oxime derivative is shown as a formula (I),

wherein A is phenyl, T is tetrazolyl, R¹Is phenyl or optionally substituted by 1,2, 3, 4 or 5 substituents selected from halogen, cyano, nitro, hydroxy, C_1‑6Alkyl radical, C_1‑6Alkoxy, halo C_1‑6Alkyl and the like substituted phenyl; the oxime derivative has the advantages of low consumption and high control effect on cucumber downy mildew, and can be further developed and applied as a bactericide.

Description

Benzoyl oxy substituted oxime derivative and application thereof

Technical Field

The invention relates to the field of pesticide fungicides, in particular to a novel benzoyloxy-substituted oxime derivative, a preparation method thereof, a composition containing the oxime derivative, and application of the oxime derivative and the composition containing the oxime derivative as plant diseases, especially as plant disease control agents caused by plant pathogenic fungi in agriculture, forestry or horticulture.

Background

China is a big agricultural country, cultivated land is few, population is large, and the grain problem is one of the important problems to be solved urgently. Plant fungal diseases are always one of the limiting factors in the production and storage processes of food crops, and cause serious losses in the aspects of the development stage, the nutritional value, the limited shelf life and the like of products. At present, the control of plant diseases mainly depends on the use of chemical pesticides. The chemical pesticide is popular among people because of small dosage and quick response. However, due to the fine development of the chemical industry and the inaccurate medication technology of farmers, the problem of drug resistance, rampant and pesticide residue is getting worse and worse when the dosage is increased blindly for pursuing effect, so that the research and development of novel pesticides with high efficiency, low toxicity and low residue, which can effectively control harmful organisms, becomes the primary target of pesticide creation at present.

JP2011012088A, CN108947964A and CN109305964A report the control effect of various types of oximes against fungal plant diseases, while the benzoyloxy-substituted oximes derivatives related to the present invention are not specifically disclosed.

Disclosure of Invention

The invention relates to a novel benzoyloxy-substituted oxime derivative and a preparation method thereof, a composition containing the oxime derivative, and application of the oxime derivative and the composition containing the oxime derivative as fungicides in agriculture, forestry or gardening. The benzoyloxy-substituted oxime derivative of the present invention has an excellent preventive effect against diseases caused by phytopathogenic fungi, particularly cucumber downy mildew, at low concentrations, and can be developed as a novel fungicide.

Specifically, the method comprises the following steps:

in one aspect, the invention relates to a compound that is a compound having formula (I) or a nitroxide, a salt, (Z) isomer, (E) isomer, or a mixture of (Z) isomer and (E) isomer of a compound having formula (I):

wherein:

R¹is optionally substituted by 1,2, 3, 4 or 5 substituents selected from halogen, cyano, nitro, hydroxy, carboxy, amino, C_1-6Alkyl, halo C_1-6Alkyl radical, C_1-6Alkoxy, halo C_1-6Alkoxy radical, C_1-6Alkylthio, halo C_1-6Alkylthio, -NHC_1-6Alkyl, -N (C)_1-6Alkyl radical)₂、-C(＝O)C_1-6Alkyl, -OC (═ O) C_1-6Alkyl or-C (═ O) C_1-6Alkoxy-substituted phenyl;

a is

R^a、R^b、R^c、R^dAnd R^eEach independently is hydrogen, fluorine, chlorine, bromine, iodine, cyano, nitro, hydroxy, C_1-6Alkyl, halo C_1-6Alkyl radical, C_1-6Alkoxy or halo C_1-6An alkoxy group;

t is

R^fAnd R^gEach independently is hydrogen or C_1-6An alkyl group.

In some embodiments, R¹Is optionally substituted by 1,2, 3, 4 or 5 substituents selected from halogen, cyano, nitro, hydroxy, carboxy, amino, C_1-4Alkyl, halo C_1-4Alkyl radical, C_1-4Alkoxy, halo C_1-4Alkoxy radical, C_1-4Alkylthio, halo C_1-4Alkylthio, -NHC_1-4Alkyl, -N (C)_1-4Alkyl radical)₂、-C(＝O)C_1-4Alkyl, -OC (═ O) C_1-4Alkyl or-C (═ O) C_1-4Alkoxy-substituted phenyl.

In other embodiments, R¹Is optionally substituted by 1,2, 3, 4 or 5 substituents selected from fluoro, chloro, bromo, iodo, cyano, nitro, hydroxy, carboxy, amino, -CH₃、-CH₂CH₃、-CH₂CH₂CH₃、-CH(CH₃)₂、-CH₂CH₂CH₂CH₃、-C(CH₃)₃、-CH₂Cl、-CH₂F、-CHF₂、-CF₃、-CH₂CF₃、-OCH₃、-OCH₂CH₃、-OCH₂CH₂CH₃、-OCH(CH₃)₂、-OCH₂CH₂CH₂CH₃、-OC(CH₃)₃、-OCH₂Cl、-OCH₂F、-OCHF₂、-OCF₃、-OCH₂CF₃、-SCH₃、-SCH₂CH₃、-SCH₂CH₂CH₃、-SCH(CH₃)₂、-SCH₂CH₂CH₂CH₃、-SC(CH₃)₃、-SCF₃、-SCH₂CF₃、-NHCH₃、-NHCH₂CH₃、-N(CH₃)₂、-N(CH₂CH₃)₂、-C(＝O)CH₃、-C(＝O)CH₂CH₃、-OC(＝O)CH₃、-OC(＝O)CH₂CH₃、-C(＝O)OCH₃or-C (═ O) OCH₂CH₃A substituted phenyl group.

In still other embodiments, R¹Is composed of

In some technical schemes, A is

Wherein R is^a、R^b、R^c、R^dAnd R^eEach independently is hydrogen, fluorine, chlorine, bromine, iodine, cyano, nitro, hydroxy, C_1-4Alkyl, halo C_1-4Alkyl radical, C_1-4Alkoxy or halo C_1-4An alkoxy group.

In other technical schemes, A is

Wherein R is^a、R^b、R^c、R^dAnd R^eEach independently is hydrogen, fluorine, chlorine, bromine, iodine, cyano, nitro, hydroxy, -CH₃、-CF₃、-OCH₃or-OCF₃。

In some embodiments, T is

Wherein R is^fAnd R^gEach independently is hydrogen or C_1-4An alkyl group.

In other embodiments, T is

Wherein R is^fAnd R^gEach independently is hydrogen, -CH₃or-CH₂CH₃。

In some embodiments, the present invention provides a compound that is a compound having formula (II) or a nitroxide, a salt, (Z) isomer, (E) isomer, or a mixture of (Z) isomer and (E) isomer of a compound having formula (II):

wherein R is¹Have the meaning as described in the present invention.

In still other embodiments, the present invention provides a compound that is a nitroxide, a salt, (Z) isomer, (E) isomer, or a mixture of (Z) isomer and (E) isomer of a compound having formula (II):

wherein R is¹Is optionally substituted by 1 or 2 substituents selected from halogen, cyano, nitro, hydroxy, carboxy, amino, C_1-6Alkyl or halo C_1-6Alkyl-substituted phenyl.

In other embodiments, the present invention provides a compound that is a compound having formula (II) or a nitroxide, a salt, (Z) isomer, (E) isomer, or a mixture of (Z) isomer and (E) isomer of a compound having formula (II):

wherein R is¹Is optionally substituted by 1 or 2 substituents selected from halogen, cyano, nitro, hydroxy, carboxy, amino, C_1-4Alkyl or halo C_1-4Alkyl-substituted phenyl.

In still other embodiments, the present invention provides a compound represented by formula (II) or a nitroxide, a salt, (Z) -isomer, (E) -isomer, or a mixture of (Z) -isomer and (E) -isomer of a compound represented by formula (II):

wherein R is¹Is optionally substituted by 1 or 2 groups selected from fluoro, chloro, bromo, iodo, cyano, nitro, hydroxy, carboxy, amino, -CH₃、-CH₂CH₃、-CH₂CH₂CH₃、-CH(CH₃)₂、-CH₂CH₂CH₂CH₃、-C(CH₃)₃、-CH₂Cl、-CH₂F、-CHF₂、-CF₃or-CH₂CF₃A substituted phenyl group.

To representA (Z) -type isomer, (E) -type isomer or a mixture of the (Z) -type isomer and the (E) -type isomer of the compound shown in the formula (I); wherein the (Z) isomer of the compound shown in the formula (I) is shown in the formula (I-1):

the (E) isomer of the compound represented by the formula (I) is represented by the formula (I-2):

represents (Z) type isomer, (E) type isomer or a mixture of (Z) type isomer and (E) type isomer of the compound represented by the formula (II); wherein the (Z) isomer of the compound represented by the formula (II) is represented by the formula (II-1):

the (E) isomer of the compound represented by the formula (II) is represented by the formula (II-2):

wherein, the (Z) type isomer, (E) type isomer, (Z) type isomer and (E) type isomer mixture shown in formula (I) and formula (II) are all included in the invention, and the (Z) type isomer, (E) type isomer or (Z) type isomer and (E) type isomer mixture shown in formula (I) or formula (II) can be separated and identified by conventional separation methods, such as column chromatography, high performance liquid chromatography, single crystal diffraction method and nuclear magnetic resonance hydrogen spectroscopy.

In some embodiments, the present invention provides a compound which is a nitroxide, a stereoisomer, or a salt thereof of a compound having formula (II-1) or a compound having formula (II-1):

wherein R is¹Have the meaning as described in the present invention.

In still other embodiments, the present invention provides a compound which is a nitroxide, a stereoisomer or a salt thereof of a compound having formula (II-1) or a compound having formula (II-1):

wherein R is¹Is optionally substituted by 1 or 2 substituents selected from halogen, cyano, nitro, hydroxy, carboxy, amino, C_1-6Alkyl or halo C₁-₆Alkyl-substituted phenyl.

In other embodiments, the present invention provides a compound which is a nitroxide, a stereoisomer, or a salt thereof of a compound having formula (II-1) or a compound having formula (II-1):

wherein R is¹Is optionally substituted by 1 or 2 substituents selected from halogen, cyano, nitro, hydroxy, carboxy, amino, C_1-4Alkyl or halo C_1-4Alkyl-substituted phenyl.

In still other embodiments, the present invention provides a compound which is a nitroxide, a stereoisomer or a salt thereof of a compound represented by formula (II-1) or a compound represented by formula (II-1):

wherein R is¹Is optionally substituted by 1 or 2 groups selected from fluoro, chloro, bromo, iodo, cyano, nitro, hydroxy, carboxy, amino, -CH₃、-CH₂CH₃、-CH₂CH₂CH₃、-CH(CH₃)₂、-CH₂CH₂CH₂CH₃、-C(CH₃)₃、-CH₂Cl、-CH₂F、-CHF₂、-CF₃or-CH₂CF₃A substituted phenyl group.

In some embodiments, the present invention provides a compound that is a compound having one of the following structures or a nitroxide, a salt, (Z) isomer, (E) isomer, or a mixture of (Z) isomer and (E) isomer of a compound having one of the following structures:

in another aspect, the present invention provides a composition comprising at least one compound according to the invention and adjuvants conventionally used on pesticides.

In still another aspect, the present invention provides use of the compound of the present invention or the composition of the present invention as a plant disease controlling agent in agriculture, forestry, or horticulture.

In still another aspect, the present invention provides a method for controlling plant diseases, comprising: an effective amount of a compound of the present invention or a composition comprising an effective amount of a compound of the present invention is applied to a plant or plant growing environment by spraying, pouring, or the like, before or after germination of a plant disease.

Further, the plant diseases according to the present invention are caused by pathogenic fungi.

Detailed description of the invention

Definitions and general terms

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

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

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

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

The articles "a," "an," and "the" as used herein are intended to include "at least one" or "one or more" unless otherwise indicated or clearly contradicted by context. Thus, as used herein, the articles refer to one or to more than one (i.e., to at least one) of the objects. 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 embodiments of the described embodiments.

The term "comprising" or "comprises" is open-ended, i.e. comprising what is specified in the present invention, but not excluding other aspects.

"stereoisomers" refers to compounds having the same chemical structure but differing in the arrangement of atoms or groups in space. Stereoisomers include enantiomers, diastereomers, conformers (rotamers), geometric isomers (cis/trans), atropisomers, and the like.

"enantiomer" refers to two isomers of a compound that are not overlapping but are in mirror image relationship to each other.

"diastereomer" refers to a stereoisomer that has two or more chiral neutrals and whose molecules are not mirror images of each other. Diastereomers have different physical properties, such as melting points, boiling points, spectral properties, and reactivities. Mixtures of diastereomers may be separated by high resolution analytical procedures such as electrophoresis and chromatography, e.g., HPLC.

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

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

Any asymmetric atom (e.g., carbon, etc.) of a compound disclosed herein can exist in racemic or enantiomerically enriched forms, such as the (R) -, (S) -or (R, S) -configuration. In certain embodiments, each asymmetric atom has at least 50% enantiomeric excess, at least 60% enantiomeric excess, at least 70% enantiomeric excess, at least 80% enantiomeric excess, at least 90% enantiomeric excess, at least 95% enantiomeric excess, or at least 99% enantiomeric excess in the (R) -or (S) -configuration.

Depending on the choice of starting materials and methods, the compounds of the invention may exist as one of the possible isomers or as mixtures thereof, for example as racemates 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 in the E or Z configuration; if the compound contains a disubstituted cycloalkyl group, the substituents of the cycloalkyl group may have cis or trans configuration.

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

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

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

In addition, unless otherwise explicitly indicated, the descriptions of the terms "… independently" and "… independently" and "… independently" used in the present invention are interchangeable and should be understood in a broad sense to mean that the specific items expressed between the same symbols do not affect each other in different groups or that the specific items expressed between the same symbols in the same groups do not affect each other.

In the various parts of this specification, substituents of the disclosed compounds are disclosed in terms of group type or range. It is specifically intended that the invention includes each and every independent subcombination of the various members of these groups and ranges. For example, the term "C₁-C₆Alkyl "or" C_1-6Alkyl "means in particular independently disclosed methyl, ethyl, C₃Alkyl radical, C₄Alkyl radical, C₅Alkyl and C₆An alkyl group.

The term "alkyl" or "alkyl group" as used herein, denotes a saturated, straight or branched chain, monovalent hydrocarbon group containing from 1 to 20 carbon atoms; wherein the alkyl group is optionally substituted with one or more substituents described herein. Unless otherwise specified, alkyl groups contain 1-20 carbon atoms. In one embodiment, the alkyl group contains 1 to 12 carbon atoms; in one embodiment, the alkyl group contains 1 to 8 carbon atoms; in another embodiment, the alkyl group contains 1 to 6 carbon atoms; in yet another embodiment, the alkyl group contains 1 to 4 carbon atoms; in yet another embodiment, the alkyl group contains 1 to 3 carbon atoms.

Examples of alkyl groups include, but are not limited to, methyl (Me, -CH)₃) Ethyl group (Et, -CH)₂CH₃) N-propyl (n-Pr, -CH)₂CH₂CH₃) Isopropyl group (i-Pr, -CH (CH)₃)₂) N-butyl (n-Bu, -CH)₂CH₂CH₂CH₃) Isobutyl (i-Bu, -CH)₂CH(CH₃)₂) Sec-butyl (s-Bu, -CH (CH)₃)CH₂CH₃) Tert-butyl (t-Bu, -C (CH)₃)₃) N-pentyl (-CH)₂CH₂CH₂CH₂CH₃) 2-pentyl (-CH (CH)₃)CH₂CH₂CH₃) 3-pentyl (-CH (CH)₂CH₃)₂) 2-methyl-2-butyl (-C (CH)₃)₂CH₂CH₃) 3-methyl-2-butyl (-CH (CH)₃)CH(CH₃)₂) 3-methyl-1-butyl (-CH)₂CH₂CH(CH₃)₂) 2-methyl-1-butyl (-CH)₂CH(CH₃)CH₂CH₃) And so on.

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

The term "alkylthio" means an alkyl group attached to the rest of the molecule through a sulfur atom, wherein the alkyl group has the meaning as described herein. Examples of alkylthio groups include, but are not limited to, methylthio (MeS, -SCH)₃) Ethylthio (EtS, -SCH)₂CH₃) And so on.

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

The term "haloalkyl" denotes an alkyl group substituted with one or more halogen atoms, examples of which include, but are not limited to, -CF₃，-CHF₂，-CH₂Cl，-CH₂CF₃，-CH₂CHF₂，-CH₂CH₂CF₃And so on.

The term "haloalkoxy" denotes an alkoxy group substituted with one or more halogen atoms, examples of which include, but are not limited to, -OCF₃，-OCHF₂，-OCHCl₂，-OCH₂CHF₂，-OCH₂CHCl₂，-OCH(CH₃)CHF₂And so on.

The term "haloalkylthio" denotes an alkylthio group substituted with one or more halogen atoms, examples of which include, but are not limited to, -SCF₃，-SCH₂CHF₂And so on.

The term "cyano" refers to — CN.

The term "hydroxy" refers to-OH.

The term "nitro" means-NO₂。

The term "carboxy" refers to-COOH.

The term "amino" refers to the group-NH₂。

Salts of the compounds of the present invention include those derived from alkali or alkaline earth metals as well as those derived from ammonia and amines. Preference is given toThe cation of (A) includes sodium, potassium, magnesium and a cation of the formula N + (R)^AR^BR^CR^D) Ammonium cation of (2), wherein R is^A、R^B、R^CAnd R^DIndependently selected from hydrogen, C₁-C₆Alkyl and C₁-C₆A hydroxyalkyl group. Salts of the compounds of the invention may be prepared by treating the compounds of the invention with a metal hydroxide, such as sodium hydroxide, or an amine, such as ammonia, trimethylamine, diethanolamine, 2-methylthiopropylamine, diallylamine, 2-butoxyethylamine, morpholine, cyclododecylamine or benzylamine.

Where the compounds of the invention contain a base moiety, acceptable salts may be formed from organic and inorganic acids, for example acetic, propionic, lactic, citric, tartaric, succinic, fumaric, maleic, malonic, mandelic, malic, phthalic, hydrochloric, hydrobromic, phosphoric, nitric, sulfuric, methanesulfonic, napthalenesulfonic, benzenesulfonic, toluenesulfonic, camphorsulfonic, and similarly known acceptable acids.

Compositions and formulations of the compounds of the invention

The compounds of the invention are generally useful as bactericidal active ingredients in compositions or formulations, usually also including adjuvants commonly used in agro-pharmaceutical practice; the adjuvant commonly used in the agricultural pharmacy comprises a surfactant and/or a carrier.

The surfactant may be any of various surfactants known in the field of pesticide formulation, and one or more of an emulsifier, a dispersant and a wetting agent are preferred in the present invention.

The carrier other than the surfactant may be any of various carriers known in the field of pesticide formulation, including various silicates, carbonates, sulfates, oxides, phosphates, plant carriers, and synthetic carriers. Specifically, for example: white carbon black, kaolin, diatomite, clay, talc, organic bentonite, pumice, titanium dioxide, dextrin, cellulose powder, light calcium carbonate, soluble starch, corn starch, sawdust powder, urea, an amine fertilizer, a mixture of urea and an amine fertilizer, glucose, maltose, sucrose, anhydrous potassium carbonate, anhydrous sodium carbonate, anhydrous potassium bicarbonate, anhydrous sodium bicarbonate, attapulgite, a mixture of anhydrous potassium carbonate and anhydrous potassium bicarbonate, and a mixture of anhydrous sodium carbonate and anhydrous sodium bicarbonate.

The emulsifier may be any emulsifier known in the field of pesticide formulation, and specifically, the emulsifier may be one or more of calcium dodecylbenzenesulfonate, trisethylphenol polyoxyethylene ether phosphate, fatty alcohol polyoxyethylene ether, alkylphenol polyoxyethylene polyoxypropylene ether, fatty amine, ethylene oxide adduct of fatty amide, fatty acid polyoxyethylene ester, rosin acid ethylene oxide adduct, polyol fatty acid ester and ethylene oxide adduct thereof, styrylphenyl polyoxyethylene ether, alkylphenol formaldehyde resin polyoxyethylene ether, hydroxyl-terminated polyoxyethylene polyoxypropylene ether, styrylphenol formaldehyde resin polyoxyethylene polyoxypropylene ether, and castor oil polyoxyethylene ether.

The dispersing agent can be various dispersing agents known in the field of pesticide formulation, and specifically, the dispersing agent is one or more of acrylic acid homopolymer sodium salt, maleic acid disodium salt, naphthalene sulfonic acid formaldehyde condensation product sodium salt, rosin block polyoxyethylene ether polyoxypropylene ether sulfonate, hydroxyl-terminated polyoxyethylene polyoxypropylene ether block copolymer, triphenyl polyoxyethylene phenol phosphate, fatty alcohol polyoxyethylene ether phosphate and p-hydroxyphenyl lignosulfonate sodium salt.

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

According to the bactericidal composition, various preparation auxiliaries commonly used in the field of pesticide formulations can be further contained, and specifically, the preparation auxiliaries can be one or more of a solvent, a cosolvent, a thickening agent, an antifreezing agent, a capsule wall material, a protective agent, a defoaming agent, a disintegrating agent, a stabilizing agent, a preservative and a binder.

The solvent may be any of various solvents known in the field of pesticide formulation, and specifically, the solvent may be one or more of an organic solvent, a vegetable oil, a mineral oil, a solvent oil and water.

Wherein the organic solvent comprises one or more of N-methylpyrrolidone, tetrahydrofuran, dimethyl sulfoxide, N-dimethyldecanamide, N-dimethylformamide, trimethylbenzene, tetramethylbenzene, dimethylbenzene, methylbenzene, octane, heptane, methanol, isopropanol, N-butanol, tetrahydrofurfuryl alcohol, tributyl phosphate, 1, 4-dioxane and cyclohexanone.

The vegetable oil comprises one or more of methylated vegetable oil, rosin-based vegetable oil, turpentine oil, epoxidized soybean oil, peanut oil, rapeseed oil, castor oil, corn oil and pine seed oil.

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

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

The antifreeze can be various antifreeze agents known in the field of pesticide formulation, and the invention is preferably one or more of ethylene glycol, propylene glycol, glycerol and urea.

The thickener can be various thickeners known in the field of pesticide formulation, and specifically can be one or more of xanthan gum, polyvinyl alcohol, polypropylene alcohol, polyethylene glycol, white carbon black, diatomite, kaolin, clay, sodium alginate, magnesium aluminum silicate, sodium aluminum silicate, carboxymethyl cellulose, sodium hydroxypropyl cellulose and organic bentonite.

The capsule material can be various capsule materials known in the field of pesticide formulation, and the invention is preferably one or more of polyurethane, polyurea and urea-formaldehyde resin.

The protective agent may be any of various protective agents known in the field of pesticide formulation, and polyvinyl alcohol and/or polyethylene glycol is preferred in the present invention.

The defoaming agent may be any of those known in the field of agricultural agent formulation, and in the present invention, one or more of organosiloxane, tributyl phosphate and silicone are preferable.

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

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

The invention also provides a preparation prepared from the bactericidal composition, and the preparation is in the dosage form of missible oil, aqueous emulsion, microemulsion, soluble liquid, aqueous suspension, suspoemulsion, ultra-low volume spray, oil suspension, microcapsule suspension, water surface spreading oil, wettable powder, water dispersible granule, dry suspension, soluble powder, soluble granule, emulsifiable powder, emulsifiable granule, solid microcapsule preparation, effervescent tablet, effervescent granule, water floating dispersion granule or seed coating. The above formulations can be prepared by methods conventional in the art.

The preparation method of the emulsifiable concentrate preparation can comprise, for example, mixing and stirring the active components, the solvent, the cosolvent and the emulsifier to form a uniform transparent oil phase, so as to obtain the emulsifiable concentrate preparation.

The preparation method of the aqueous emulsion can comprise, for example, mixing the active ingredient, the emulsifier, the cosolvent and the solvent to form a uniform oil phase; mixing water, thickener, antifreeze, etc. to obtain uniform water phase. Under high-speed shearing, adding the water phase into the oil phase or adding the oil phase into the water phase to form the aqueous emulsion with good dispersibility.

The microemulsion may be prepared, for example, by mixing and stirring the active ingredient, emulsifier, and solvent to form a uniform transparent oil phase. Under stirring, water is gradually added to form a uniform and transparent microemulsion.

The preparation method of the water/oil suspending agent comprises the following steps: for example, water or oil can be used as a medium, and an auxiliary agent such as an active component and a surfactant is added into a sanding kettle, and after grinding to a certain particle size, filtration is performed. And adding the weighed thickening agent into the ground mother liquor, and uniformly shearing and dispersing. Making into oil suspension or water suspension.

The preparation method of the water dispersible granule and the soluble granule comprises the following steps: for example, the active ingredients, the dispersing agent, the wetting agent, the carrier and the like are uniformly mixed, then are pulverized into a certain particle size through air flow, are added with water for kneading, are finally added into a granulator for granulation, and are dried to obtain the water dispersible granules or the soluble granules.

The preparation method of the soluble powder and the wettable powder comprises the following steps: for example, the active ingredients, various adjuvants and fillers such as other carriers can be thoroughly mixed and pulverized by a micronizer.

The germicidal composition of the present invention may be provided in the form of a finished formulation, i.e., the materials in the composition have been mixed; or in separate formulations which are self-mixing in a tub or tank prior to use and optionally diluted by mixing with water depending on the concentration of active desired.

Application of the inventive compounds and compositions

The compound of the present invention is useful as a plant disease control agent. The invention therefore also comprises a method for controlling plant diseases caused by phytopathogenic fungi, which comprises applying to the plants or parts thereof to be protected an effective amount of a compound according to the invention or of a fungicidal composition comprising said compound. The compounds and/or compositions of the present invention provide control of diseases caused by a broad spectrum of phytopathogenic fungi of the classes Basidiomycetes, Ascomycetes, Oomycetes and Deuteromycetes. They are effective in controlling a broad spectrum of plant diseases, particularly foliar pathogens of ornamental, turf, vegetable, field, cereal and fruit crops. These pathogens include: oomycetes, including Phytophthora (Phytophthora) diseases such as Phytophthora infestans, Phytophthora sojae (Phytophthora megasporum), Phytophthora citri (Phytophthora parasitica), Phytophthora citrullus (Phytophthora parasiti), Phytophthora cinnamomi (Phytophthora cinnamomi) and Phytophthora cucurbitae (Phytophthora capsici), Pythium graminum (Pythium) species diseases such as Pythium turtium (Pythium aphanidermatum) diseases, and Peronosporaceae (Peronospora) species diseases such as Plasmopara viticola (Plasmopara viticola), Peronospora (Peronospora spp.) (including P. nicotianae (Peronospora tabacina) and P. parasitica (Pseudoperonospora Pseudoperonospora), including P. nicotianae (Pseudoperonospora cinerea) and P. Pseudoperonospora (Pseudoperonospora Pseudoperonospora) diseases including P); ascomycetes (including Alternaria (Alternaria) such as Alternaria solani and Phytophthora brassicae (Alternaria solani), Mycoporia globosa (Guignardia) diseases such as Staphylococcus viticola (Guignardia bidwell), Venturia (Venturia) diseases such as Venturia mali (Venturia inaequalis), Sphaerotheca (Sepia) diseases such as Microphyllum nodosum (Septorium nodorum) and Phytophthora parasitica (Septorii), Powderzia (Powdery) diseases such as Erysiphe graminis (Erysiphe spp.) and Sphaerotheca (Septoria oryzae), Powder Erysiphe (Erysiphe) diseases such as Microphyllum graminis (Erysiphe sp.) and Pseudoperonospora cinerea (Ostericola), Staphylococcus viticola (Uncinula necator), Pseudoperonospora cucumerina (Sphaerothecoides) and Pseudoperonospora cinerea (Botrytis), Scleroti cinerea) diseases such as Microphyllum cinerea (Botrytium cinerea), Scleroti cinerea) diseases such as Microphyllum cinerea (Botrytum cinerea), Scleroti cinerea (Potentilla) diseases such as Microphyllum cinerea (Botrytum cinerea), Scleroti cinerea) diseases such as Microphyllum cinerea (Potentilla cinerea), Scleroti cinerea (Potentilla cinerea), Scleroti cinerea) diseases such as Pseudoperonospora cinerea (Potentilla cinerea), Scleroti cinerea (Potentilla cinerea) diseases (Potentilla cinerea), Scleroti cinerea) diseases (Potentilla cinerea), Scedodes (Scleroti cinerea) diseases (Botrytum cinerea), Scedodes (Potentilla cinerea) diseases (Potentilla cinerea), Scytum cinerea), Scedodes (Potentilla cinerea), Scedodes (Botrytum cinerea) diseases (Potentilla cinerea) diseases (Pothium cinerea), and Gracilaria (Botrytum cinerea) diseases (Botrytum cinerea), and Gracilaria (Botrytum cinerea) diseases (Botrytum cinerea), and Gracilaria cinerea) diseases (Pothium cinerea), and Gracilaria (Pothium cinerea) diseases (Botrytum cinerea), and Gracilaria cinerea (Botrytum cinerea) diseases (Botrytum cinerea), and Gracilaria cinerea) diseases (Botrytum cinerea), and Gracilaria cinerea) diseases (Botrytum cinerea), and Gracilaria cinerea (Botrytum cinerea) diseases (Botrytum cinerea), and Gracilaria cinerea) diseases (Botrytum cinerea), and Botrytum cine, Pyricularia oryzae (Magnaporthe grisea), Rhizoctonia solani (Phomopsis viticola), Helminthosporium (Helminthosporium) diseases such as northern leaf blight (Helminthosporium tritici reptilis), Moss reticulata (Pyrenophora teres), anthrax bacteria such as Hedychium nigrum (Glomerella) or Anthrax (Colletochium spp.) diseases (such as Colletotrichum graminicum (Colestochium graminicum) and watermelon anthrax (Colletochium orbiculosum)), and wheat holothrix graminis (Gaeumannomyces graminis); basidiomycetes, including rust diseases caused by the genus Puccinia (Puccinia spp.), such as Puccinia recondita (Puccinia recondita), Puccinia striiformis (Puccinia striiformis), Puccinia purpurea (Puccinia hordei), Puccinia graminis (Puccinia graminis) and Puccinia arachidis (Puccinia arachidis), coffee rust (hemix) and soybean rust (Phakopsora pachyrhizi); other pathogens include Rhizoctonia species (Rhizoctonia spp.) (such as Rhizoctonia solani); fusarium species diseases such as Fusarium roseum (Fusarium roseum), Fusarium graminearum (Fusarium graminearum), and Fusarium oxysporum (Fusarium oxysporum); verticillium dahliae (Verticillium dahliae); sclerotium rolfsii (sclerotiotium rolfsii); physalospora piricola (Rynchosporium secalis); black acerola (Cercosporium personatum), Episra nigrella (Cercospora arachidicola), and Episra fuscospora (Cercospora betacola); and other classes and species closely related to these pathogens. In addition to their fungicidal activity, the compositions or combinations also have a resistant activity against bacteria such as Erwinia amylovora (Erwinia amylovora), Xanthomonas campestris (Xanthomonas campestris), Pseudomonas syringae (Pseudomonas syringae) and other species.

The bactericidal compound or composition of the present invention is used in a simple manner, and is applied to plants, plant parts or plant growing sites by conventional methods such as soil mixing, spraying, pouring and the like before or after germination of plant diseases, wherein the application amount is determined according to climatic conditions or crop conditions, generally 10-5000g per mu, and diluted to 10-400mg/L (preferably 100 mg/L) for application. The diluent is preferably water.

The bactericidal effect of the bactericidal compound or composition of the present invention is generally related to external factors such as climate, but the effect of climate can be alleviated by using appropriate dosage forms.

The compounds or compositions of the present invention may also be used in admixture with other compounds having fungicidal, insecticidal or herbicidal properties, as well as with nematicides, acaricides, protectants, herbicidal safeners, growth regulators, plant nutrients or soil conditioners, and the like.

General synthetic procedure

The following scheme describes the preparation of the compounds of the present invention. Unless otherwise indicated, the compounds of the invention may be prepared by the methods described herein. The starting materials, reagents and the like used in the preparation of the compounds of the present invention are commercially available or can be prepared by methods conventional in the art. In this specification, a structure is dominant if there is any difference between the chemical name and the chemical structure. In the preparation of the compounds of the present invention, the preparation of the compounds is carried out at room temperature unless otherwise specified. By "room temperature" is meant a temperature of about 15 ℃ to 35 ℃ or about 20 ℃ to 30 ℃ or about 23 ℃ to 28 ℃ or about 25 ℃. In the context of the present invention, all numbers disclosed herein are approximate values, regardless of whether the word "about" or "approximately" is used.

Synthetic schemes

Synthesis scheme I

The target compound shown in the formula (II-1) can be prepared by the first synthesis scheme. Carrying out condensation reaction on the compound (Z) - (1-methyl-1H-tetrazol-5-yl) (phenyl) methyl ketoxime and the compound shown in the formula (a) under alkaline conditions (such as potassium carbonate, cesium carbonate and the like) to obtain a target compound shown in the formula (II-1);

wherein X is fluorine, chlorine, bromine or iodine, R¹Have the meaning as described in the present invention.

Examples

Intermediate 1: preparation of (Z) - (1-methyl-1H-tetrazol-5-yl) (phenyl) methanone oxime

The first step is as follows: preparation of N-methyl-2-oxo-2-phenylacetamide

Methyl benzoylformate (164g, 1mol) was dissolved in methanol (500mL) at 0 deg.C, and aqueous methylamine solution (101g, 1.3mol) was added dropwise, after the addition was complete, the reaction mixture was allowed to warm to room temperature and stirred for 2 hours. The solvent was removed under reduced pressure, diluted with ethyl acetate (300mL), washed with water (200mL), 1N sodium hydroxide (200mL), 1N hydrochloric acid (200mL) and saturated brine (200mL) in that order, and dried over anhydrous Na₂SO₄Dried and concentrated under reduced pressure to give 130g of a pale yellow solid, yield: 80 percent.

The second step is that: preparation of (Z) -N-methyl-2-oxo-2-phenylaminoacetyl chloride

N-methyl-2-oxo-2-phenylacetamide (65g, 0.4mol) was dissolved in a mixed solution of N, N-dimethylformamide (2.9g, 0.04mol) and chloroform (500mL) at 0 ℃ and thionyl chloride (71.4g, 0.6mol) was added dropwise thereto, the mixture was allowed to stand at room temperature and stirred for reaction for 2 hours, followed by heating under reflux overnight. The solvent was removed under reduced pressure, diluted with toluene (100mL) and stirred at room temperature overnight, concentrated under reduced pressure to give 70g of a brown oily liquid, yield: 96 percent.

The third step: preparation of (1-methyl-1H-tetrazol-5-yl) (phenyl) methanone

Sodium azide (6.5g, 100mmol) and tetrabutylammonium bromide (1.62g, 5mmol) were dissolved in a mixed solution of toluene (20mL) and water (20mL) at room temperature, a toluene solution (60mL) of (Z) -N-methyl-2-oxo-2-phenylimidoacetyl chloride (18.2g,100mmol) was added dropwise, the reaction was stirred at room temperature for 2 hours after completion of the addition, toluene (20mL) was added for dilution, the mixture was washed with water (100mL × 3) and saturated brine (100mL), dried over anhydrous sodium sulfate, and concentrated under reduced pressure to give 15.4g of a brown oily liquid, yield: 85 percent.

The fourth step: preparation of (Z) - (1-methyl-1H-tetrazol-5-yl) (phenyl) methanone oxime

At room temperature, (1-methyl-1H-tetrazol-5-yl) (phenyl) methanone (15g, 80mmol) and hydroxylamine hydrochloride (11.1g, 160mmol) were dissolved in ethanol (100mL), warmed to 48 ℃, stirred for 12 hours, the solvent was removed under reduced pressure, water (100mL) was added for dilution, ethyl acetate (50mL x 3) was extracted, the organic phase was washed with saturated saline (100mL), the organic phases were combined, concentrated under reduced pressure, and the residue was subjected to column chromatography [ petroleum ether/ethyl acetate (v/v) ═ 4/1] to give 5.6g of a pale yellow solid, yield: 34 percent.

¹H NMR(400MHz,CDCl₃)δ10.48(s,1H),7.41(dd,J＝12.9,7.2Hz,3H),7.32(t,J＝7.4Hz,2H),3.97(s,3H).

LC-MS:m/z 204.1[M+H]⁺.

Intermediate 2: preparation of 6- (bromomethyl) pyridine-2-benzoic acid ester

The first step is as follows: preparation of 6-methylpyridine-2-benzoic acid ester

2-hydroxy-6-methylpyridine (10.9g,100mmol) was dissolved in dichloromethane (100mL) at room temperature, pyridine (7.91g,100mmol) was added, stirring was carried out at 0 deg.C, benzoyl chloride (14.1g,100mmol) was slowly added dropwise, and after the addition was completed for 2 hours, the reaction was stirred at room temperature for 18 hours. The solvent was removed under reduced pressure, diluted with water (100mL), extracted with ethyl acetate (50mL × 3), the organic phases combined, washed with saturated brine (100mL), concentrated under reduced pressure, and the residue subjected to column chromatography [ petroleum ether/ethyl acetate (v/v) ═ 4/1] to give 19.5g yellow powder, yield: 91.5 percent.

LC-MS:m/z＝214.10[M+H]⁺.

The second step is that: preparation of 6- (bromomethyl) pyridine-2-benzoic acid ester

6-methylpyridine-2-benzoic acid ester (2.13g,10mmol) was dissolved in carbon tetrachloride (150mL) at room temperature, and N-bromosuccinimide (1.78g,10mmol) and azobisisobutyronitrile (0.164g,1mmol) were added and reacted at 80 ℃ for 12 hours under nitrogen protection. Suction filtration, washing the filter residue three times with carbon tetrachloride (30mL), combining the organic phases, removing the solvent under reduced pressure to give 2.55g of a white powder with a yield of: 87.3 percent.

LC-MS:m/z＝291.80[M+H]⁺.

2-hydroxy-6-methylpyridine and the corresponding benzoyl chloride derivative are used as reaction raw materials, and the intermediate compounds in the table 1 can be obtained by preparation according to the preparation method of the intermediate 2 or the preparation method in the prior art.

TABLE 1

Example 1: preparation of (Z) -6- ((((((1-methyl-1H-tetrazol-5-yl) (phenyl) methylene) amino) oxy) methyl) pyridine-2-benzoic acid ester

(Z) - (1-methyl-1H-tetrazol-5-yl) (phenyl) methanone oxime (203mg,1mmol), potassium carbonate (276mg,2mmol), N, N-dimethylformamide (30mL) was added to a reaction flask, 6- (bromomethyl) pyridine-2-benzoic acid ester (292mg,1mmol) was added, and the reaction was carried out at room temperature for 6 hours. Ethyl acetate (50mL) was added, washed with saturated brine (50mL x 3), the organic phase was dried, filtered and the filtrate was concentrated to give the crude product which was isolated by silica gel column chromatography [ petroleum ether/ethyl acetate (v/v) ═ 5/1] to give 250mg of a white solid, yield: 60.3 percent.

¹H NMR(400MHz,CDCl₃)δ(ppm):8.01(m,2H),7.83-7.80(m,3H),7.56-7.45(m,4H),7.24(d,J＝10.5Hz,1H),6.51(d,J＝7.2Hz,1H),6.32(d,J＝10.6Hz,1H),6.22(d,J＝8.5Hz,1H),5.51(s,2H),4.13(s,3H).

LC-MS:m/z＝415.10[M+H]⁺.

Respectively takes intermediate 1((Z) - (1-methyl-1H-tetrazole-5-yl) (phenyl) methyl ketoxime with the corresponding structure

) Starting from the corresponding intermediates in Table 1, see example 1Or by referring to the preparation method in the prior art, the target compounds in the table 2 can be obtained.

TABLE 2

Biological activity assay

Test targets: cucumber downy mildew

And (3) test treatment: the compound was dissolved in N, N-dimethylformamide to 1% EC for use. The bactericidal activity of these compounds at different doses against the test target was evaluated using the in vivo potting method.

Pseudoperonospora cubensis test (Pseudoperonospora cubensis)

Selecting 1 potted cucumber seedling with consistent growth vigor in true leaf stage (removing growing point), spraying, air drying, inoculating 24 hr later, taking fresh cucumber downy mildew diseased leaf, washing off sporocyst on back of diseased leaf with distilled water by writing brush, and making into sporangium suspension (2-3x 10)⁵one/mL). By means of inoculation sprayers (pressure)0.1MPa) is evenly sprayed and inoculated on cucumber seedlings, the inoculated test material is moved to an artificial climate chamber, the relative humidity is kept at 100 percent, the temperature is about 21 ℃, the temperature is kept at about 21 ℃ after 24 hours, the relative humidity is kept at about 95 percent for inducing moisture, after 5 days, classification investigation is carried out according to blank control disease occurrence conditions, and the control effect is calculated according to disease indexes.

The test results are shown below:

at a dose of 50mg/L, the control effects 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 on cucumber downy mildew are not less than 90%, and the control effects of compound K1 and compound K2 on cucumber downy mildew at a dose of 50mg/L are shown in Table 3:

TABLE 3 control of cucumber downy mildew of the compounds at a dose of 50mg/L

The control effect of 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 on cucumber downy mildew is more than or equal to 80 percent at the dosage of 25 mg/L.

The control effect of example 14, example 15, example 16 and example 17 on cucumber downy mildew is more than or equal to 80 percent under the dosage of 12.5 mg/L.

From the test results, the compound has obvious control effect on plant diseases, particularly cucumber downy mildew, at low concentration, and can be further developed to be used as a pesticide bactericide.

The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.

Claims (10)

1. A compound which is a compound having the formula (I) or a nitroxide, a salt, (Z) isomer, (E) isomer or a mixture of (Z) isomer and (E) isomer of a compound having the formula (I):

wherein:

R¹is optionally substituted by 1,2, 3, 4 or 5 substituents selected from halogen, cyano, nitro, hydroxy, carboxy, amino, C_1-6Alkyl, halo C_1-6Alkyl radical, C_1-6Alkoxy, halo C_1-6Alkoxy radical, C_1-6Alkylthio, halo C_1-6Alkylthio, -NHC_1-6Alkyl, -N (C)_1-6Alkyl radical)₂、-C(＝O)C_1-6Alkyl, -OC (═ O) C_1-6Alkyl or-C (═ O) C_1-6Alkoxy-substituted phenyl;

a is

R^a、R^b、R^c、R^dAnd R^eEach independently is hydrogen, fluorine, chlorine, bromine, iodine, cyano, nitro, hydroxy, C_1-6Alkyl, halo C_1-6Alkyl radical, C_1-6Alkoxy or halo C_1-6An alkoxy group;

t is

R^fAnd R^gEach independently is hydrogen or C_1-6An alkyl group.

2. The compound of claim 1, wherein:

R¹is optionally substituted by 1,2, 3, 4 or 5 substituents selected from halogen, cyano, nitro, hydroxy, carboxy, amino, C_1-4Alkyl, halo C_1-4Alkyl radical, C_1-4Alkoxy, halo C_1-4Alkoxy radical, C_1-4Alkylthio, halo C_1-4Alkylthio, -NHC_1-4Alkyl, -N (C)_1-4Alkyl radical)₂、-C(＝O)C_1-4Alkyl, -OC (═ O) C_1-4Alkyl or-C (═ O) C_1-4Alkoxy-substituted phenyl.

3. The compound of claim 2, wherein:

R¹is optionally substituted by 1,2, 3, 4 or 5 substituents selected from fluoro, chloro, bromo, iodo, cyano, nitro, hydroxy, carboxy, amino, -CH₃、-CH₂CH₃、-CH₂CH₂CH₃、-CH(CH₃)₂、-CH₂CH₂CH₂CH₃、-C(CH₃)₃、-CH₂Cl、-CH₂F、-CHF₂、-CF₃、-CH₂CF₃、-OCH₃、-OCH₂CH₃、-OCH₂CH₂CH₃、-OCH(CH₃)₂、-OCH₂CH₂CH₂CH₃、-OC(CH₃)₃、-OCH₂Cl、-OCH₂F、-OCHF₂、-OCF₃、-OCH₂CF₃、-SCH₃、-SCH₂CH₃、-SCH₂CH₂CH₃、-SCH(CH₃)₂、-SCH₂CH₂CH₂CH₃、-SC(CH₃)₃、-SCF₃、-SCH₂CF₃、-NHCH₃、-NHCH₂CH₃、-N(CH₃)₂、-N(CH₂CH₃)₂、-C(＝O)CH₃、-C(＝O)CH₂CH₃、-OC(＝O)CH₃、-OC(＝O)CH₂CH₃、-C(＝O)OCH₃or-C (═ O) OCH₂CH₃A substituted phenyl group.

4. A compound according to claim 3, wherein:

R¹is composed of

5. The compound of claim 1, wherein:

a is

R^a、R^b、R^c、R^dAnd R^eEach independently is hydrogen, fluorine, chlorine, bromine, iodine, cyano, nitro, hydroxy, C_1-4Alkyl, halo C_1-4Alkyl radical, C_1-4Alkoxy or halo C_1-4An alkoxy group;

t is

R^fAnd R^gEach independently is hydrogen or C_1-4An alkyl group.

6. The compound of claim 5, wherein:

a is

R^a、R^b、R^c、R^dAnd R^eEach independently of the others is hydrogen, fluorine, chlorine, bromine,Iodine, cyano, nitro, hydroxy, -CH₃、-CF₃、-OCH₃or-OCF₃；

T is

R^fAnd R^gEach independently is hydrogen, -CH₃or-CH₂CH₃。

7. The compound of claim 1, which is a compound having formula (II) or a nitroxide, salt, (Z) -isomer, (E) -isomer, or a mixture of (Z) -isomer and (E) -isomer of a compound having formula (II):

8. a compound which is a compound having one of the following structures or a nitroxide, a salt, (Z) isomer, (E) isomer or a mixture of (Z) isomer and (E) isomer of a compound having one of the following structures:

9. a composition comprising a compound according to any one of claims 1 to 8 and adjuvants conventionally used in pesticides.

10. The compound of any one of claims 1 to 8 or the composition of claim 9 is used as a plant disease control agent in agriculture, forestry or horticulture.