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WO2019238095A1 - Oxadiazole oxime derivative and use thereof in agriculture - Google Patents

Oxadiazole oxime derivative and use thereof in agriculture Download PDF

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Publication number
WO2019238095A1
WO2019238095A1 PCT/CN2019/091137 CN2019091137W WO2019238095A1 WO 2019238095 A1 WO2019238095 A1 WO 2019238095A1 CN 2019091137 W CN2019091137 W CN 2019091137W WO 2019238095 A1 WO2019238095 A1 WO 2019238095A1
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Prior art keywords
alkyl
alkoxy
halo
och
formula
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PCT/CN2019/091137
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French (fr)
Chinese (zh)
Inventor
李义涛
林健
熊力
卢辉
田宇
李艳芳
张兵兵
Original Assignee
东莞市东阳光农药研发有限公司
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Priority to CN201980003310.XA priority Critical patent/CN110914261B/en
Publication of WO2019238095A1 publication Critical patent/WO2019238095A1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
    • C07D413/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing three or more hetero rings

Definitions

  • the present invention relates to the field of pesticides, in particular to oxadiazole oxime derivatives and pesticides containing such derivatives as active ingredients, especially phytopathogenic fungal control agents.
  • the present invention provides an oxadiazole oxime derivative and a composition containing the derivative.
  • the oxadiazole oxime derivative and a composition thereof are used for controlling plant pathogenic fungi.
  • the present invention provides a compound having a compound represented by Formula (IA) or a salt, nitrogen oxide, or (E) and (Z) isomers of a compound represented by Formula (IA), and mixture:
  • T is a 5-membered heteroaryl group containing 1, 2, 3, or 4 nitrogen atoms; wherein the 5-membered heteroaryl group is optionally substituted with one or more alkyl groups;
  • A is aryl or heteroaryl; wherein A is optionally substituted with 1, 2, 3, 4, 5 or 6 R b ;
  • each R b is independently halogen, hydroxy, cyano, nitro, amino, carboxyl, alkyl, alkoxy, haloalkyl, haloalkoxy, aryl or aryloxy;
  • B 1 is CR 1 or N
  • B is CR 2 or N
  • B 2 is CR 3 or N
  • B 1 , B and B 2 are N;
  • R 1 , R 2 , R 3 , R 4 and R 5 are each independently hydrogen, halogen, hydroxyl, cyano, nitro, amino, carboxyl, alkyl, haloalkyl, alkoxy or haloalkoxy;
  • R 1 , R 2 , R 3 , R 4 and R 5 are each independently the following substructure formula:
  • R 11 , R 22 , R 33 , R 44 and R 55 are each independently hydrogen, halogen, hydroxyl, cyano, nitro, amino, carboxyl, alkyl, haloalkyl, alkoxy, haloalkoxy, Alkylamino or alkylthio;
  • the present invention provides a compound represented by formula (I) or a salt, nitrogen oxide, or (E) and (Z) isomers of a compound represented by formula (I), and mixtures thereof :
  • T is a 5-membered heteroaryl group containing 1, 2, 3, or 4 nitrogen atoms; wherein the 5-membered heteroaryl group is optionally substituted with one or more alkyl groups;
  • A is aryl or heteroaryl; wherein A is optionally substituted with 1, 2, 3, 4, 5 or 6 R b ;
  • each R b is independently halogen, hydroxy, cyano, nitro, amino, carboxyl, alkyl, alkoxy, haloalkyl, haloalkoxy, aryl or aryloxy;
  • R 1 , R 2 , R 3 , R 4 and R 5 are each independently hydrogen, halogen, hydroxyl, cyano, nitro, amino, carboxyl, alkyl, haloalkyl, alkoxy or haloalkoxy;
  • R 1 , R 2 , R 3 , R 4 and R 5 are each independently the following substructure formula:
  • R 11 , R 22 , R 33 , R 44 and R 55 are each independently hydrogen, halogen, hydroxyl, cyano, nitro, amino, carboxyl, alkyl, haloalkyl, alkoxy, haloalkoxy, Alkylamino or alkylthio;
  • T is a 5-membered heteroaryl group containing 1, 2, 3, or 4 nitrogen atoms; wherein said 5-membered heteroaryl group is optionally substituted by one or more C 1-6 alkyl groups.
  • A is C 6-10 aryl or 5-10 membered heteroaryl; wherein A is optionally substituted with 1, 2, 3, 4, 5 or 6 R b ;
  • each R b is independently halogen, hydroxy, cyano, nitro, amino, carboxyl, C 1-6 alkyl, C 1-6 alkoxy, halo C 1-6 alkyl, halo C 1 -6 alkoxy, C 6-10 aryl or C 6-10 aryloxy;
  • R 1 , R 2 , R 3 , R 4 and R 5 are each independently hydrogen, halogen, hydroxyl, cyano, nitro, amino, carboxyl, C 1-6 alkyl, halo C 1-6 alkyl, C 1-6 alkoxy or halo C 1-6 alkoxy;
  • R 1 , R 2 , R 3 , R 4 and R 5 are each independently the following substructure formula:
  • R 11 , R 22 , R 33 , R 44 and R 55 are each independently hydrogen, halogen, hydroxyl, cyano, nitro, amino, carboxyl, C 1-6 alkyl, halo C 1-6 alkane Alkyl, C 1-6 alkoxy, halo C 1-6 alkoxy, C 1-6 alkylamino or C 1-6 alkylthio.
  • T is the following substructure formula:
  • each R a is independently hydrogen or C 1-4 alkyl
  • A is the following substructure formula:
  • each R b is independently halogen, hydroxy, cyano, nitro, amino, carboxyl, C 1-4 alkyl, C 1-4 alkoxy, halo C 1-4 alkyl, halo C 1 -4 alkoxy, C 6-10 aryl or C 6-10 aryloxy.
  • T is the following substructure formula:
  • each R a is independently hydrogen, -CH 3 or -CH 2 CH 3 ;
  • A is the following substructure formula:
  • each R b is independently fluorine, chlorine, bromine, iodine, hydroxyl, cyano, nitro, amino, carboxyl, -CH 3 , -CH 2 CH 3 , -CH 2 CH 2 CH 3 , -CH (CH 3 ) 2 , -CH 2 CH 2 CH 2 CH 3 , -C (CH 3 ) 3 , -OCH 3 , -OCH 2 CH 3 , -OCH 2 CH 2 CH 3 , -OCH (CH 3 ) 2 , -OC (CH 3 ) 3 , -CHF 2 , -CF 3 or -OCF 3 .
  • R 1 , R 2 , R 3 , R 4 and R 5 are each independently hydrogen, halogen, hydroxyl, cyano, nitro, amino, carboxyl, C 1-4 alkyl, haloC 1-4 alkyl, C 1-4 alkoxy or halo C 1-4 alkoxy;
  • R 1 , R 2 , R 3 , R 4 and R 5 are each independently the following substructure formula:
  • R 11 , R 22 , R 33 , R 44 and R 55 are each independently hydrogen, halogen, hydroxyl, cyano, nitro, amino, carboxyl, C 1-4 alkyl, halo C 1-4 alkane Alkyl, C 1-4 alkoxy, halo C 1-4 alkoxy, C 1-4 alkylamino or C 1-4 alkylthio.
  • R 1 , R 2 , R 3 , R 4 and R 5 are each independently hydrogen, fluorine, chlorine, bromine, iodine, hydroxyl, cyano, nitro, amino, carboxyl, -CH 3 , -CH 2 CH 3 , -CH 2 CH 2 CH 3 , -CH (CH 3 ) 2 , -CH 2 CH 2 CH 2 CH 3 , -C (CH 3 ) 3 , -CH 2 Cl, -CHF 2 , -CF 3 , -OCH 3 , -OCH 2 CH 3 , -OCH 2 CH 2 CH 3 , -OCH (CH 3 ) 2 , -OC (CH 3 ) 3 or -OCF 3 ;
  • R 1 , R 2 , R 3 , R 4 and R 5 are each independently the following substructure formula:
  • R 11 , R 22 , R 33 , R 44 and R 55 are each independently hydrogen, fluorine, chlorine, bromine, iodine, hydroxyl, cyano, nitro, amino, carboxyl, -CH 3 , -CH 2 CH 3 , -CH 2 CH 2 CH 3 , -CH (CH 3 ) 2 , -CH 2 CH 2 CH 2 CH 3 , -C (CH 3 ) 3 , -CF 3 , -OCH 3 , -OCH 2 CH 3 , -OCH 2 CH 2 CH 3 , -OCH (CH 3 ) 2 , -OC (CH 3 ) 3 , -OCF 3 , -N (CH 3 ) 2 or -SCH 3 .
  • the present invention provides a compound represented by formula (II) or a salt of a compound represented by formula (II) or a nitrogen oxide thereof:
  • R 1 , R 2 , R 3 , R 4, and R 5 are each independently hydrogen, halogen, C 1-4 alkyl, halo C 1-4 alkyl, C 1-4 alkoxy Or halo C 1-4 alkoxy;
  • R 1 , R 2 , R 3 , R 4 and R 5 are each independently the following substructure formula:
  • R 11 , R 22 , R 33 , R 44 and R 55 are each independently hydrogen, halogen, C 1-4 alkyl, C 1-4 alkoxy, halo C 1-4 alkyl or halo C 1-4 alkoxy;
  • R 1 , R 2 , R 3 , R 4 and R 5 are each independently hydrogen, fluorine, chlorine, bromine, iodine, -CH 3 , -CH 2 CH 3 , -CH 2 CH 2 CH 3 , -CH (CH 3 ) 2 , -CH 2 CH 2 CH 2 CH 3 , -C (CH 3 ) 3 , -CF 3 , -OCH 3 or -OCF 3 ;
  • R 1 , R 2 , R 3 , R 4 and R 5 are each independently the following substructure formula:
  • R 11 , R 22 , R 33 , R 44 and R 55 are each independently hydrogen, fluorine, chlorine, bromine, iodine, -CH 3 , -CH 2 CH 3 , -CH 2 CH 2 CH 3 , -CH (CH 3 ) 2 , -CH 2 CH 2 CH 2 CH 3 , -C (CH 3 ) 3 , -CF 3 , -OCH 3 or -OCF 3 .
  • the present invention provides a compound represented by formula (III) or a salt of a compound represented by formula (III) or a nitrogen oxide thereof:
  • R 2 , R 3 , R 4, and R 5 are each independently hydrogen, halogen, C 1-4 alkyl, or halo C 1-4 alkyl;
  • R 2 , R 3 , R 4 and R 5 are each independently the following substructure formula:
  • R 11 , R 22 , R 33 , R 44 and R 55 are each independently hydrogen, halogen, C 1-4 alkyl, C 1-4 alkoxy, halo C 1-4 alkyl, halo C 1-4 alkoxy, C 1-4 alkylamino or C 1-4 alkylthio;
  • R 2 , R 3 , R 4 and R 5 are each independently hydrogen, fluorine, chlorine, bromine, iodine, —CH 3 or —CF 3 ;
  • R 2 , R 3 , R 4 and R 5 are each independently the following substructure formula:
  • R 11 , R 22 , R 33 , R 44 and R 55 are each independently hydrogen, fluorine, chlorine, bromine, iodine, -CH 3 , -CH 2 CH 3 , -CH 2 CH 2 CH 3 , -CH (CH 3 ) 2 , -CH 2 CH 2 CH 2 CH 3 , -C (CH 3 ) 3 , -CF 3 , -OCH 3 , -OCF 3 , -N (CH 3 ) 2 or -SCH 3 .
  • the invention provides a composition comprising a compound of the invention, wherein the composition further comprises an agrochemically acceptable surfactant and / or carrier.
  • the present invention provides the use of a compound of the present invention or a composition of the present invention for controlling plant pathogenic fungi.
  • the articles "a,” “an,” and “said” as used herein are intended to include “at least one” or “one or more”.
  • the articles used in the present invention refer to the articles of one or more (ie, at least one) objects.
  • a component means one or more components, that is, more than one component may be considered for adoption or use in an embodiment of the described embodiment.
  • Stereoisomers refer to compounds that have the same chemical structure, but differ in the arrangement of atoms or groups in space. Stereoisomers include enantiomers, diastereomers, conformers (rotomers), geometric isomers (cis / trans) isomers, atropisomers, etc. .
  • Enantiomers refer to two isomers of a compound that cannot overlap but mirror image each other.
  • Diastereomer refers to a stereoisomer that has two or more chiral neutrality and whose molecules are not mirror images of each other. Diastereomers have different physical properties, such as melting points, boiling points, spectral properties, and reactivity. Diastereomeric mixtures can be separated by high resolution analytical operations such as electrophoresis and chromatography, such as HPLC.
  • optically active compounds Many organic compounds exist in optically active forms, that is, they have the ability to rotate the plane of plane-polarized light.
  • the prefixes D and L or R and S are used to indicate the absolute configuration of a molecule with respect to its one or more chiral centers.
  • the prefixes d and l or (+) and (-) are symbols used to specify the rotation of plane-polarized light caused by a compound, where (-) or l indicates that the compound is left-handed.
  • Compounds prefixed with (+) or d are right-handed.
  • a specific stereoisomer is an enantiomer, and a mixture of such isomers is called an enantiomeric mixture.
  • a 50:50 mixture of enantiomers is called a racemic mixture or a racemate, and this can occur when there is no stereoselection or stereospecificity in a chemical reaction or process.
  • any asymmetric atom (e.g., carbon, etc.) of a compound disclosed herein can exist in racemic or enantiomerically enriched form, such as (R)-, (S)-, or (R, S) -configuration presence.
  • each asymmetric atom has at least a 50% enantiomeric excess in the (R)-or (S) -configuration, 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.
  • the compounds of the invention may be in one of the possible isomers or mixtures thereof, such as racemates and non-corresponding isomer mixtures (depending on the number of asymmetric carbon atoms) Exists in the form.
  • 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 substituent may be in the E or Z configuration; if the compound contains a disubstituted cycloalkyl group, the substituent of the cycloalkyl group may have a cis or trans configuration.
  • the resulting mixture of any stereoisomers can be separated into pure or substantially pure geometric isomers, enantiomers, diastereomers, for example, by chromatography, based on differences in the physicochemical properties of the components. And / or fractional crystallization.
  • racemates of any of the resulting end products or intermediates can be resolved into optical enantiomers by methods known to those skilled in the art using known methods, for example, by subjecting the diastereomeric salts obtained Separation. Racemic products can also be separated by chiral chromatography, such as high performance liquid chromatography (HPLC) using a chiral adsorbent. In particular, enantiomers can be prepared by asymmetric synthesis.
  • HPLC high performance liquid chromatography
  • the compounds of the present invention may be optionally substituted with one or more substituents, such as the compounds of the general formula above, or like the specific examples, subclasses in the examples, and the compounds included in the present invention.
  • substituents such as the compounds of the general formula above, or like the specific examples, subclasses in the examples, and the compounds included in the present invention.
  • a class of compounds It is understood that the term “optionally substituted” is 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 specific substituent. Unless otherwise indicated, an optional substituent group may be substituted at each substitutable position of the group.
  • substituents 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.
  • substituents may be substituted at the same or different positions.
  • examples of "one or more" refer to 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10.
  • the substituents may be, but are not limited to, deuterium, fluorine, chlorine, bromine, iodine, cyano, hydroxyl, nitro, amino, carboxyl, alkyl, alkoxy, alkoxyalkyl, alkane Oxyalkoxy, alkoxyalkylamino, aryloxy, heteroaryloxy, heterocyclyloxy, arylalkoxy, heteroarylalkoxy, heterocyclylalkoxy, cycloalkane Alkylalkoxy, alkylamino, alkylaminoalkyl, alkylaminoalkylamino, cycloalkylamino, cycloalkylalkylamino, alkylthio, haloalkyl, haloalkoxy, hydroxy-substituted alkyl, hydroxy-substituted alkyl Amino, cyano-substituted alkyl, cyano-substituted alkoxy,
  • C 1 -C 6 alkyl or “C 1-6 alkyl” specifically refer to independently disclosed methyl, ethyl, C 3 alkyl, C 4 alkyl, C 5 alkyl, and C 6 alkyl base.
  • alkyl or "alkyl group” as used herein means a saturated straight or branched chain monovalent hydrocarbon group containing from 1 to 20 carbon atoms; wherein said alkyl group is optionally It is substituted with one or more substituents described in the present invention.
  • alkyl groups contain 1-20 carbon atoms. In one embodiment, the alkyl group contains 1-12 carbon atoms; in one embodiment, the alkyl group contains 1-8 carbon atoms; in another embodiment, the alkyl group contains 1- 6 carbon atoms; in yet another embodiment, the alkyl group contains 1-4 carbon atoms; and in still another embodiment, the alkyl group contains 1-3 carbon atoms.
  • alkyl groups include, but are not limited to, methyl (Me, -CH 3 ), ethyl (Et, -CH 2 CH 3 ), n-propyl (n-Pr, -CH 2 CH 2 CH 3 ), Isopropyl (i-Pr, -CH (CH 3 ) 2 ), n-butyl (n-Bu, -CH 2 CH 2 CH 2 CH 3 ), isobutyl (i-Bu, -CH 2 CH (CH 3 ) 2 ), sec-butyl (s-Bu, -CH (CH 3 ) CH 2 CH 3 ), tert-butyl (t-Bu, -C (CH 3 ) 3 ), n-pentyl (-CH 2 CH 2 CH 2 CH 3 ), 2-pentyl (-CH (CH 3 ) CH 2 CH 2 CH 3 ), 3-pentyl (-CH (CH 2 CH 3 ) 2 ), 2-methyl 2-butyl (-C (CH 3 ) 2 ),
  • alkoxy means that an alkyl group is connected to the rest of the molecule through an oxygen atom, wherein the alkyl group has the meaning as described in the present invention.
  • alkoxy groups include, but are not limited to, methoxy (MeO, -OCH 3 ), ethoxy (EtO, -OCH 2 CH 3 ), 1-propoxy (n-PrO, n- Propoxy, -OCH 2 CH 2 CH 3 ), 2-propoxy (i-PrO, i-propoxy, -OCH (CH 3 ) 2 ) and the like.
  • halogen refers to fluorine (F), chlorine (Cl), bromine (Br), or iodine (I).
  • aryl means a monocyclic, bicyclic, and tricyclic carbocyclic ring system containing 6-14 ring atoms, or 6-12 ring atoms, or 6-10 ring atoms, wherein at least one ring system is aromatic Family, where each ring system contains a ring of 3-7 atoms and has one or more attachment points connected to the rest of the molecule.
  • aryl may be used interchangeably with the term “aromatic ring”. Examples of the aryl group may include phenyl, indenyl, naphthyl, and anthracenyl. The aryl group is optionally substituted with one or more substituents described herein.
  • aryloxy means that an aryl group is connected to the rest of the molecule through an oxygen atom, wherein the aryl group has the meaning as described in the present invention.
  • heteroaryl means monocyclic, bicyclic, and tricyclic systems containing 5-12 ring atoms, or 5-10 ring atoms, or 5-6 ring atoms, at least one of which is aromatic, And at least one ring system contains one or more heteroatoms, wherein each ring system contains a ring of 5-7 atoms, and there are one or more attachment points connected to the rest of the molecule.
  • heteroaryl may be used interchangeably with the term “heteroaromatic ring” or “heteroaromatic compound”.
  • the heteroaryl group is optionally substituted with one or more substituents described herein.
  • a heteroaryl group of 5-10 atoms comprises 1, 2, 3 or 4 heteroatoms independently selected from O, S and N.
  • haloalkyl denotes an alkyl group is substituted with one or more halogen atoms, such examples include, but are not limited to, -CF 3, -CHF 2, -CH 2 Cl, -CH 2 CF 3, - CH 2 CHF 2 , -CH 2 CH 2 CF 3 and the like.
  • haloalkoxy means that an alkoxy group is substituted with one or more halogen atoms.
  • halogen atoms include, but are not limited to, -OCF 3 , -OCHF 2 , -OCHCl 2 , -OCH 2 CHF 2 , -OCH 2 CHCl 2 , -OCH (CH 3 ) CHF 2 and the like.
  • alkylamino or “alkylamino” includes "N-alkylamino" and "N, N-dialkylamino", wherein the amino groups are each independently replaced by one or two alkyl groups Group replaced. Some of these embodiments are that the alkylamino group is a lower alkylamino group having one or two C1-6 alkyl groups attached to a nitrogen atom. In other embodiments, the alkylamino group is a lower alkylamino group having a C 1-4 alkyl group attached to a nitrogen atom.
  • Suitable alkylamino groups may be monoalkylamino or dialkylamino, such examples include, but are not limited to, N-methylamino, N-ethylamino, N, N- Dimethylamino, N, N-diethylamino and the like.
  • alkylthio means that an alkyl group is connected to the rest of the molecule through a sulfur atom, wherein the alkyl group has the meaning as described in the present invention.
  • alkylthio groups include, but are not limited to, methylthio (MeS, -SCH 3 ), ethylthio (EtS, -SCH 2 CH 3 ), 1-propylthio (n-PrS, n- Propionyl, -SCH 2 CH 2 CH 3 ), 2-propylthio (i-PrS, i-propylthio, -SCH (CH 3 ) 2 ) and the like.
  • stereostructures of the (Z) form and the (E) form there are stereostructures of the (Z) form and the (E) form, and both of the stereoisomers and mixtures thereof are included in the present invention. These two stereoisomers can be separated according to methods well known to those skilled in the art.
  • Salts of the compounds of the invention include those derived from alkali or alkaline earth metals and those derived from ammonia and amines.
  • Preferred cations include sodium, potassium, magnesium, and ammonium cations having the chemical formula N + (R A R B R C R D ), wherein R A , R B , R C and R D are independently selected from hydrogen, C 1 -C 6 alkyl and C 1 -C 6 hydroxyalkyl.
  • Salts of compounds having formula (IA), formula (I), formula (II) or formula (III) can be obtained by using a metal hydroxide (e.g., sodium hydroxide) or an amine (e.g., ammonia, trimethylamine, diethanolamine, 2 -Methylthiopropylamine, diallylamine, 2-butoxyethylamine, morpholine, cyclododecylamine, or benzylamine) pairs having formula (IA), formula (I), formula (II), or formula ( The compounds of III) are prepared by treatment.
  • a metal hydroxide e.g., sodium hydroxide
  • an amine e.g., ammonia, trimethylamine, diethanolamine, 2 -Methylthiopropylamine, diallylamine, 2-butoxyethylamine, morpholine, cyclododecylamine, or benzylamine
  • 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 Acids, 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 Accepted acid.
  • organic and inorganic acids such as acetic acid, propionic acid, lactic acid, citric acid, tartaric acid, succinic acid, fumaric acid, maleic acid, malonic acid Acids, mandelic acid, malic acid, phthalic acid, hydrochloric acid, hydrobromic acid, phosphoric acid, nitric acid, sulfuric acid, methanes
  • the object of the present invention is to provide a compound having a significant effect on controlling phytopathogenic fungi, a composition and a preparation containing the compound, and an application thereof as a fungicide.
  • the present invention provides a compound having a compound represented by Formula (IA) or a salt, nitrogen oxide, or (E) and (Z) isomers of a compound represented by Formula (IA), and mixture:
  • T is a 5-membered heteroaryl group containing 1, 2, 3, or 4 nitrogen atoms; wherein the 5-membered heteroaryl group is optionally substituted with one or more alkyl groups;
  • A is aryl or heteroaryl; wherein A is optionally substituted with 1, 2, 3, 4, 5 or 6 R b ;
  • each R b is independently halogen, hydroxy, cyano, nitro, amino, carboxyl, alkyl, alkoxy, haloalkyl, haloalkoxy, aryl or aryloxy;
  • B 1 is CR 1 or N
  • B is CR 2 or N
  • B 2 is CR 3 or N
  • B 1 , B and B 2 are N;
  • R 1 , R 2 , R 3 , R 4 and R 5 are each independently hydrogen, halogen, hydroxyl, cyano, nitro, amino, carboxyl, alkyl, haloalkyl, alkoxy or haloalkoxy;
  • R 1 , R 2 , R 3 , R 4 and R 5 are each independently the following substructure formula:
  • R 11 , R 22 , R 33 , R 44 and R 55 are each independently hydrogen, halogen, hydroxyl, cyano, nitro, amino, carboxyl, alkyl, haloalkyl, alkoxy, haloalkoxy, Alkylamino or alkylthio;
  • the present invention provides a compound represented by formula (I) or a salt, nitrogen oxide, or (E) and (Z) isomers of a compound represented by formula (I), and mixtures thereof :
  • T is a 5-membered heteroaryl group containing 1, 2, 3 or 4 nitrogen atoms; wherein, the 5-membered heteroaryl group is optionally substituted with one or more alkyl groups;
  • A is aryl or heteroaryl; wherein A is optionally substituted with 1, 2, 3, 4, 5 or 6 R b ;
  • each R b is independently halogen, hydroxy, cyano, nitro, amino, carboxyl, alkyl, alkoxy, haloalkyl, haloalkoxy, aryl or aryloxy;
  • R 1 , R 2 , R 3 , R 4 and R 5 are each independently hydrogen, halogen, hydroxyl, cyano, nitro, amino, carboxyl, alkyl, haloalkyl, alkoxy or haloalkoxy;
  • R 1 , R 2 , R 3 , R 4 and R 5 are each independently the following substructure formula:
  • R 11 , R 22 , R 33 , R 44 and R 55 are each independently hydrogen, halogen, hydroxyl, cyano, nitro, amino, carboxyl, alkyl, haloalkyl, alkoxy, haloalkoxy, Alkylamino or alkylthio;
  • T is a 5-membered heteroaryl group containing 1, 2, 3, or 4 nitrogen atoms; wherein said 5-membered heteroaryl group is optionally substituted by one or more C 1-6 alkyl groups. To replace.
  • T is the following substructure formula:
  • W, X, Y, Z and V are each independently C (R a ) m or N (R a ) q ;
  • W, X, Y, Z and V is N (R a ) q ;
  • n and q are each independently 0 or 1;
  • each R a is independently hydrogen or C 1-6 alkyl.
  • T is the following substructure formula:
  • W, X, Y, Z and V are each independently C (R a ) m or N (R a ) q ;
  • W, X, Y, Z and V is N (R a ) q ;
  • n and q are each independently 0 or 1;
  • each R a is independently hydrogen or C 1-4 alkyl.
  • T is the following substructure formula:
  • each R a is independently hydrogen or C 1-4 alkyl.
  • T is the following substructure formula:
  • each R a is independently hydrogen, -CH 3 or -CH 2 CH 3 .
  • A is C 6-10 aryl or 5-10 membered heteroaryl; wherein A is optionally substituted with 1, 2, 3, 4, 5 or 6 R b ;
  • each R b is independently halogen, hydroxy, cyano, nitro, amino, carboxyl, C 1-6 alkyl, C 1-6 alkoxy, halo C 1-6 alkyl, halo C 1 -6 alkoxy, C 6-10 aryl or C 6-10 aryloxy.
  • A is the following substructure formula:
  • each R b is independently halogen, hydroxy, cyano, nitro, amino, carboxyl, C 1-4 alkyl, C 1-4 alkoxy, halo C 1-4 alkyl, halo C 1 -4 alkoxy, C 6-10 aryl or C 6-10 aryloxy.
  • A is the following substructure formula:
  • each R b is independently fluorine, chlorine, bromine, iodine, hydroxyl, cyano, nitro, amino, carboxyl, -CH 3 , -CH 2 CH 3 , -CH 2 CH 2 CH 3 , -CH (CH 3 ) 2 , -CH 2 CH 2 CH 2 CH 3 , -C (CH 3 ) 3 , -OCH 3 , -OCH 2 CH 3 , -OCH 2 CH 2 CH 3 , -OCH (CH 3 ) 2 , -OC (CH 3 ) 3 , -CHF 2 , -CF 3 or -OCF 3 .
  • R 1 is hydrogen, halogen, hydroxy, cyano, nitro, amino, carboxy, C 1-6 alkyl, halo C 1-6 alkyl, C 1-6 alkoxy, or halogen C 1-6 alkoxy.
  • R 1 is hydrogen, halogen, hydroxy, cyano, nitro, amino, carboxyl, C 1-4 alkyl, halo C 1-4 alkyl, C 1-4 alkoxy, or Halo C 1-4 alkoxy.
  • R 1 is hydrogen, fluorine, chlorine, bromine, iodine, hydroxyl, cyano, nitro, amino, carboxyl, -CH 3 , -CH 2 CH 3 , -CH 2 CH 2 CH 3 , -CH (CH 3 ) 2 , -CH 2 CH 2 CH 2 CH 3 , -C (CH 3 ) 3 , -CH 2 Cl, -CHF 2 , -CF 3 , -OCH 3 , -OCH 2 CH 3 , -OCH 2 CH 2 CH 3 , -OCH (CH 3 ) 2 , -OC (CH 3 ) 3 or -OCF 3 .
  • R 2 is hydrogen, halogen, hydroxy, cyano, nitro, amino, carboxyl, C 1-6 alkyl, halo C 1-6 alkyl, C 1-6 alkoxy, or halo C 1-6 alkoxy.
  • R 2 is hydrogen, halogen, hydroxy, cyano, nitro, amino, carboxy, C 1-4 alkyl, halo C 1-4 alkyl, C 1-4 alkoxy, or Halo C 1-4 alkoxy.
  • R 2 is hydrogen, fluorine, chlorine, bromine, iodine, hydroxyl, cyano, nitro, amino, carboxyl, -CH 3 , -CH 2 CH 3 , -CH 2 CH 2 CH 3 , -CH (CH 3 ) 2 , -CH 2 CH 2 CH 2 CH 3 , -C (CH 3 ) 3 , -CH 2 Cl, -CHF 2 , -CF 3 , -OCH 3 , -OCH 2 CH 3 , -OCH 2 CH 2 CH 3 , -OCH (CH 3 ) 2 , -OC (CH 3 ) 3 or -OCF 3 .
  • R 3 is hydrogen, halogen, hydroxy, cyano, nitro, amino, carboxyl, C 1-6 alkyl, halo C 1-6 alkyl, C 1-6 alkoxy, or halo C 1-6 alkoxy.
  • R 3 is hydrogen, halogen, hydroxy, cyano, nitro, amino, carboxyl, C 1-4 alkyl, halo C 1-4 alkyl, C 1-4 alkoxy, or Halo C 1-4 alkoxy.
  • R 3 is hydrogen, fluorine, chlorine, bromine, iodine, hydroxyl, cyano, nitro, amino, carboxyl, -CH 3 , -CH 2 CH 3 , -CH 2 CH 2 CH 3 , -CH (CH 3 ) 2 , -CH 2 CH 2 CH 2 CH 3 , -C (CH 3 ) 3 , -CH 2 Cl, -CHF 2 , -CF 3 , -OCH 3 , -OCH 2 CH 3 , -OCH 2 CH 2 CH 3 , -OCH (CH 3 ) 2 , -OC (CH 3 ) 3 or -OCF 3 .
  • R 4 is hydrogen, halogen, hydroxy, cyano, nitro, amino, carboxy, C 1-6 alkyl, halo C 1-6 alkyl, C 1-6 alkoxy, or halo C 1-6 alkoxy.
  • R 4 is hydrogen, halogen, hydroxy, cyano, nitro, amino, carboxy, C 1-4 alkyl, halo C 1-4 alkyl, C 1-4 alkoxy, or Halo C 1-4 alkoxy.
  • R 4 is hydrogen, fluorine, chlorine, bromine, iodine, hydroxyl, cyano, nitro, amino, carboxyl, -CH 3 , -CH 2 CH 3 , -CH 2 CH 2 CH 3 , -CH (CH 3 ) 2 , -CH 2 CH 2 CH 2 CH 3 , -C (CH 3 ) 3 , -CH 2 Cl, -CHF 2 , -CF 3 , -OCH 3 , -OCH 2 CH 3 , -OCH 2 CH 2 CH 3 , -OCH (CH 3 ) 2 , -OC (CH 3 ) 3 or -OCF 3 .
  • R 5 is hydrogen, halogen, hydroxy, cyano, nitro, amino, carboxy, C 1-6 alkyl, halo C 1-6 alkyl, C 1-6 alkoxy, or halogen C 1-6 alkoxy.
  • R 5 is hydrogen, halogen, hydroxy, cyano, nitro, amino, carboxy, C 1-4 alkyl, halo C 1-4 alkyl, C 1-4 alkoxy, or Halo C 1-4 alkoxy.
  • R 5 is hydrogen, fluorine, chlorine, bromine, iodine, hydroxyl, cyano, nitro, amino, carboxyl, -CH 3 , -CH 2 CH 3 , -CH 2 CH 2 CH 3 , -CH (CH 3 ) 2 , -CH 2 CH 2 CH 2 CH 3 , -C (CH 3 ) 3 , -CH 2 Cl, -CHF 2 , -CF 3 , -OCH 3 , -OCH 2 CH 3 , -OCH 2 CH 2 CH 3 , -OCH (CH 3 ) 2 , -OC (CH 3 ) 3 or -OCF 3 .
  • R 1 is the following sub-structure formula:
  • R 11 , R 22 , R 33 , R 44 and R 55 are each independently hydrogen, halogen, hydroxyl, cyano, nitro, amino, carboxyl, C 1-6 alkyl, halo C 1-6 alkane Alkyl, C 1-6 alkoxy, halo C 1-6 alkoxy, C 1-6 alkylamino or C 1-6 alkylthio.
  • R 1 is the following sub-structural formula:
  • R 11 , R 22 , R 33 , R 44 and R 55 are each independently hydrogen, halogen, hydroxyl, cyano, nitro, amino, carboxyl, C 1-4 alkyl, halo C 1-4 alkane Alkyl, C 1-4 alkoxy, halo C 1-4 alkoxy, C 1-4 alkylamino or C 1-4 alkylthio.
  • R 1 is the following substructure formula:
  • R 11 , R 22 , R 33 , R 44 and R 55 are each independently hydrogen, fluorine, chlorine, bromine, iodine, hydroxyl, cyano, nitro, amino, carboxyl, -CH 3 , -CH 2 CH 3 , -CH 2 CH 2 CH 3 , -CH (CH 3 ) 2 , -CH 2 CH 2 CH 2 CH 3 , -C (CH 3 ) 3 , -CF 3 , -OCH 3 , -OCH 2 CH 3 , -OCH 2 CH 2 CH 3 , -OCH (CH 3 ) 2 , -OC (CH 3 ) 3 , -OCF 3 , -N (CH 3 ) 2 or -SCH 3 .
  • R 2 is the following substructure:
  • R 11 , R 22 , R 33 , R 44 and R 55 are each independently hydrogen, halogen, hydroxyl, cyano, nitro, amino, carboxyl, C 1-6 alkyl, halo C 1-6 alkane Alkyl, C 1-6 alkoxy, halo C 1-6 alkoxy, C 1-6 alkylamino or C 1-6 alkylthio.
  • R 2 is the following sub-structural formula:
  • R 11 , R 22 , R 33 , R 44 and R 55 are each independently hydrogen, halogen, hydroxyl, cyano, nitro, amino, carboxyl, C 1-4 alkyl, halo C 1-4 alkane Alkyl, C 1-4 alkoxy, halo C 1-4 alkoxy, C 1-4 alkylamino or C 1-4 alkylthio.
  • R 2 is the following substructure formula:
  • R 11 , R 22 , R 33 , R 44 and R 55 are each independently hydrogen, fluorine, chlorine, bromine, iodine, hydroxyl, cyano, nitro, amino, carboxyl, -CH 3 , -CH 2 CH 3 , -CH 2 CH 2 CH 3 , -CH (CH 3 ) 2 , -CH 2 CH 2 CH 2 CH 3 , -C (CH 3 ) 3 , -CF 3 , -OCH 3 , -OCH 2 CH 3 , -OCH 2 CH 2 CH 3 , -OCH (CH 3 ) 2 , -OC (CH 3 ) 3 , -OCF 3 , -N (CH 3 ) 2 or -SCH 3 .
  • R 3 is the following substructure:
  • R 11 , R 22 , R 33 , R 44 and R 55 are each independently hydrogen, halogen, hydroxyl, cyano, nitro, amino, carboxyl, C 1-6 alkyl, halo C 1-6 alkane Alkyl, C 1-6 alkoxy, halo C 1-6 alkoxy, C 1-6 alkylamino or C 1-6 alkylthio.
  • R 3 is the following substructure formula:
  • R 11 , R 22 , R 33 , R 44 and R 55 are each independently hydrogen, halogen, hydroxyl, cyano, nitro, amino, carboxyl, C 1-4 alkyl, halo C 1-4 alkane Alkyl, C 1-4 alkoxy, halo C 1-4 alkoxy, C 1-4 alkylamino or C 1-4 alkylthio.
  • R 3 is the following substructure formula:
  • R 11 , R 22 , R 33 , R 44 and R 55 are each independently hydrogen, fluorine, chlorine, bromine, iodine, hydroxyl, cyano, nitro, amino, carboxyl, -CH 3 , -CH 2 CH 3 , -CH 2 CH 2 CH 3 , -CH (CH 3 ) 2 , -CH 2 CH 2 CH 2 CH 3 , -C (CH 3 ) 3 , -CF 3 , -OCH 3 , -OCH 2 CH 3 , -OCH 2 CH 2 CH 3 , -OCH (CH 3 ) 2 , -OC (CH 3 ) 3 , -OCF 3 , -N (CH 3 ) 2 or -SCH 3 .
  • R 4 is the following substructure:
  • R 11 , R 22 , R 33 , R 44 and R 55 are each independently hydrogen, halogen, hydroxyl, cyano, nitro, amino, carboxyl, C 1-6 alkyl, halo C 1-6 alkane Alkyl, C 1-6 alkoxy, halo C 1-6 alkoxy, C 1-6 alkylamino or C 1-6 alkylthio.
  • R 4 is the following substructure formula:
  • R 11 , R 22 , R 33 , R 44 and R 55 are each independently hydrogen, halogen, hydroxyl, cyano, nitro, amino, carboxyl, C 1-4 alkyl, halo C 1-4 alkane Alkyl, C 1-4 alkoxy, halo C 1-4 alkoxy, C 1-4 alkylamino or C 1-4 alkylthio.
  • R 4 is the following substructure formula:
  • R 11 , R 22 , R 33 , R 44 and R 55 are each independently hydrogen, fluorine, chlorine, bromine, iodine, hydroxyl, cyano, nitro, amino, carboxyl, -CH 3 , -CH 2 CH 3 , -CH 2 CH 2 CH 3 , -CH (CH 3 ) 2 , -CH 2 CH 2 CH 2 CH 3 , -C (CH 3 ) 3 , -CF 3 , -OCH 3 , -OCH 2 CH 3 , -OCH 2 CH 2 CH 3 , -OCH (CH 3 ) 2 , -OC (CH 3 ) 3 , -OCF 3 , -N (CH 3 ) 2 or -SCH 3 .
  • R 5 is the following sub-structure formula:
  • R 11 , R 22 , R 33 , R 44 and R 55 are each independently hydrogen, halogen, hydroxyl, cyano, nitro, amino, carboxyl, C 1-6 alkyl, halo C 1-6 alkane Alkyl, C 1-6 alkoxy, halo C 1-6 alkoxy, C 1-6 alkylamino or C 1-6 alkylthio.
  • R 5 is the following sub-structural formula:
  • R 11 , R 22 , R 33 , R 44 and R 55 are each independently hydrogen, halogen, hydroxyl, cyano, nitro, amino, carboxyl, C 1-4 alkyl, halo C 1-4 alkane Alkyl, C 1-4 alkoxy, halo C 1-4 alkoxy, C 1-4 alkylamino or C 1-4 alkylthio.
  • R 5 is the following sub-structural formula:
  • R 11 , R 22 , R 33 , R 44 and R 55 are each independently hydrogen, fluorine, chlorine, bromine, iodine, hydroxyl, cyano, nitro, amino, carboxyl, -CH 3 , -CH 2 CH 3 , -CH 2 CH 2 CH 3 , -CH (CH 3 ) 2 , -CH 2 CH 2 CH 2 CH 3 , -C (CH 3 ) 3 , -CF 3 , -OCH 3 , -OCH 2 CH 3 , -OCH 2 CH 2 CH 3 , -OCH (CH 3 ) 2 , -OC (CH 3 ) 3 , -OCF 3 , -N (CH 3 ) 2 or -SCH 3 .
  • the condition is that there is one and only one of R 1 , R 2 and R 3 is Among them, R 11 , R 22 , R 33 , R 44 and R 55 have the meanings described in the present invention.
  • condition is that there is one and only one of R 1 and R 3 is Among them, R 11 , R 22 , R 33 , R 44 and R 55 have the meanings described in the present invention.
  • the present invention provides a compound represented by Formula (II) or a salt of a compound represented by Formula (II) or a nitrogen oxide thereof:
  • R 1 , R 2 , R 3 , R 4 and R 5 have the meanings described in the present invention.
  • R 1 , R 2 , R 3 , R 4, and R 5 are each independently hydrogen, halogen, C 1-4 alkyl, halo C 1-4 alkyl, C 1-4 alkoxy Or halo C 1-4 alkoxy;
  • R 1 , R 2 , R 3 , R 4 and R 5 are each independently the following substructure formula:
  • R 11 , R 22 , R 33 , R 44 and R 55 are each independently hydrogen, halogen, C 1-4 alkyl, C 1-4 alkoxy, halo C 1-4 alkyl, halo C 1-4 alkoxy;
  • R 1 , R 2 , R 3 , R 4 and R 5 are each independently hydrogen, halogen, C 1-4 alkyl, halo C 1-4 alkyl, C 1- 4 alkoxy or halo C 1-4 alkoxy;
  • R 1 , R 2 , R 3 , R 4 and R 5 are each independently the following substructure formula:
  • R 11 , R 22 , R 33 , R 44 and R 55 are each independently hydrogen, halogen, C 1-4 alkyl, C 1-4 alkoxy, halo C 1-4 alkyl, halo C 1-4 alkoxy;
  • R 1 , R 2 , R 3 , R 4 and R 5 are each independently hydrogen, fluorine, chlorine, bromine, iodine, -CH 3 , -CH 2 CH 3 , -CH 2 CH 2 CH 3 , -CH (CH 3 ) 2 , -CH 2 CH 2 CH 2 CH 3 , -C (CH 3 ) 3 , -CF 3 , -OCH 3 or -OCF 3 ;
  • R 1 , R 2 , R 3 , R 4 and R 5 are each independently the following substructure formula:
  • R 11 , R 22 , R 33 , R 44 and R 55 are each independently hydrogen, fluorine, chlorine, bromine, iodine, -CH 3 , -CH 2 CH 3 , -CH 2 CH 2 CH 3 , -CH (CH 3 ) 2 , -CH 2 CH 2 CH 2 CH 3 , -C (CH 3 ) 3 , -CF 3 , -OCH 3 or -OCF 3 ;
  • R 1 , R 2 , R 3 , R 4 and R 5 are each independently hydrogen, fluorine, chlorine, bromine, iodine, -CH 3 , -CH 2 CH 3 , -CH 2 CH 2 CH 3 , -CH (CH 3 ) 2 , -CH 2 CH 2 CH 2 CH 3 , -C (CH 3 ) 3 , -CF 3 , -OCH 3 or -OCF 3 ;
  • R 1 , R 2 , R 3 , R 4 and R 5 are each independently the following substructure formula:
  • R 11 , R 22 , R 33 , R 44 and R 55 are each independently hydrogen, fluorine, chlorine, bromine, iodine, -CH 3 , -CH 2 CH 3 , -CH 2 CH 2 CH 3 , -CH (CH 3 ) 2 , -CH 2 CH 2 CH 2 CH 3 , -C (CH 3 ) 3 , -CF 3 , -OCH 3 or -OCF 3 ;
  • the present invention provides a compound represented by Formula (III) or a salt of a compound represented by Formula (III) or a nitrogen oxide thereof:
  • R 2 , R 3 , R 4 and R 5 have the meanings described in the present invention.
  • R 2 , R 3 , R 4, and R 5 are each independently hydrogen, halogen, C 1-4 alkyl, or halo C 1-4 alkyl;
  • R 2 , R 3 , R 4 and R 5 are each independently the following substructure formula:
  • R 11 , R 22 , R 33 , R 44 and R 55 are each independently hydrogen, halogen, C 1-4 alkyl, C 1-4 alkoxy, halo C 1-4 alkyl, halo C 1-4 alkoxy, C 1-4 alkylamino or C 1-4 alkylthio;
  • R 2 , R 4 and R 5 are each independently hydrogen, halogen, C 1-4 alkyl or halo C 1-4 alkyl;
  • R 11 , R 22 , R 33 , R 44 and R 55 are each independently hydrogen, halogen, C 1-4 alkyl, C 1-4 alkoxy, halo C 1-4 alkyl, halo C 1-4 alkoxy, C 1-4 alkylamino or C 1-4 alkylthio.
  • R 2 , R 3 , R 4 and R 5 are each independently hydrogen, fluorine, chlorine, bromine, iodine, —CH 3 or —CF 3 ;
  • R 2 , R 3 , R 4 and R 5 are each independently the following substructure formula:
  • R 11 , R 22 , R 33 , R 44 and R 55 are each independently hydrogen, fluorine, chlorine, bromine, iodine, -CH 3 , -CH 2 CH 3 , -CH 2 CH 2 CH 3 , -CH (CH 3 ) 2 , -CH 2 CH 2 CH 2 CH 3 , -C (CH 3 ) 3 , -CF 3 , -OCH 3 , -OCF 3 , -N (CH 3 ) 2 or -SCH 3 ;
  • R 2 , R 4 and R 5 are each independently hydrogen;
  • R 11 , R 22 , R 33 , R 44 and R 55 are each independently hydrogen, fluorine, chlorine, bromine, iodine, -CH 3 , -CH 2 CH 3 , -CH 2 CH 2 CH 3 , -CH (CH 3 ) 2 , -CH 2 CH 2 CH 2 CH 3 , -C (CH 3 ) 3 , -CF 3 , -OCH 3 , -OCF 3 , -N (CH 3 ) 2 or -SCH 3 .
  • the present invention provides a compound represented by Formula (II-1) or a salt of a compound represented by Formula (II-1) or a nitrogen oxide thereof:
  • R 2 , R 3 , R 4 , R 5 , R 11 , R 22 , R 33 , R 44 and R 55 have the meanings described in the present invention.
  • the present invention provides a compound having a compound represented by Formula (II-2) or a salt of a compound represented by Formula (II-2) or a nitrogen oxide thereof:
  • R 1 , R 2 , R 4 , R 5 , R 11 , R 22 , R 33 , R 44 and R 55 have the meanings described in the present invention.
  • the present invention provides a compound represented by Formula (III-1) or a salt of a compound represented by Formula (III-1) or a nitrogen oxide thereof:
  • R 2 , R 4 , R 5 , R 11 , R 22 , R 33 , R 44 and R 55 have the meanings described in the present invention.
  • the present invention provides a compound that is a compound having one of the following structures or a salt, nitrogen oxide, or (E) and (Z) isomers of a compound having one of the following structures, and their mixture:
  • Oxime in oxadiazole oxime derivatives Represents the (Z) isomer (E) Isomer And (Z) isomer and (E) isomer mixture, (Z) isomer, (E) isomer and (Z) isomer and (E) isomer
  • the mixtures are all included in the present invention, wherein (Z) isomers, (E) isomers, or mixtures of (Z) isomers and (E) isomers may be analyzed by nuclear magnetic resonance hydrogen spectroscopy, The structure is confirmed by a conventional method such as high-performance liquid chromatography and / or single crystal culture.
  • the present invention provides a composition comprising the compound of the present invention as an active ingredient.
  • composition of the invention further comprises an agrochemically acceptable surfactant and / or carrier.
  • the present invention provides the use of a compound of the present invention or a composition of the present invention for controlling plant pathogenic fungi.
  • the present invention provides an application of the compound of the present invention or the composition of the present invention in controlling cucumber downy mildew.
  • the present invention provides a method for using the compound according to the present invention or the composition according to the present invention for controlling plant pathogenic fungi.
  • compositions and formulations of the compounds of the invention are provided.
  • the compounds of the invention are generally useful as fungicide active ingredients in compositions, i.e. formulations, and generally also include agrochemically acceptable surfactants and / or carriers.
  • the aforementioned surfactants can be various surfactants known in the field of pesticide formulations, such as anionic surfactants, cationic surfactants, nonionic surfactants and amphoteric surfactants, block polymers, polyelectrolytes, and the like. mixture. Such surfactants can be used as emulsifiers, dispersants, wetting agents, penetration enhancers or adjuvants.
  • Suitable anionic surfactants are alkali metal, alkaline earth metal or ammonium salts of sulfonic acids, sulfuric acids, phosphoric acids, carboxylic acids and mixtures thereof.
  • sulfonates are alkylaryl sulfonates, diphenyl sulfonates, alpha-olefin sulfonates, lignosulfonates, sulfonates of fatty acids and oils, ethoxylated alkylphenols Sulfonate, alkoxylated arylphenol sulfonate, condensed naphthalene sulfonate, dodecyl- and tridecylbenzene sulfonate, naphthalene and alkylnaphthalene sulfonate, sulfonate Succinate or sulfosuccinate.
  • sulfates are sulfates of fatty acids and oils, sulfates of ethoxylated alkylphenols, sulfates of alcohols, sulfates of ethoxylated alcohols or sulfates of fatty acid esters.
  • An example of a phosphate is a phosphate ester.
  • carboxylates are alkyl carboxylates and carboxylated alcohols or alkylphenol ethoxylates.
  • Suitable nonionic surfactants are alkoxylates, N-substituted fatty acid amides, amine oxides, esters, sugar-based surfactants, polymer surfactants and mixtures thereof.
  • alkoxylates are compounds such as alcohols, alkylphenols, amines, amides, arylphenols, fatty acids or fatty acid esters that have been alkoxylated with 1-50 equivalents.
  • Ethylene oxide and / or propylene oxide can be used for alkoxylation, preferably ethylene oxide.
  • N-substituted fatty acid amides are fatty acid glucamides or fatty acid alkanolamides.
  • esters are fatty acid esters, glycerides or monoglycerides.
  • glycosyl surfactants are sorbitan, ethoxylated sorbitan, sucrose and glucose esters or alkyl polyglucosides.
  • polymer surfactants are homopolymers or copolymers of vinylpyrrolidone, vinyl alcohol or vinyl acetate.
  • Suitable cationic surfactants are quaternary surfactants, such as quaternary ammonium compounds having 1 or 2 hydrophobic groups, or salts of long-chain primary amines.
  • Suitable amphoteric surfactants are alkyl betaines and imidazolines.
  • Suitable block polymers are A-B or A-B-A type block polymers containing blocks of polyoxyethylene and polyoxypropylene, or A-B-C type block polymers containing alkanol, polyoxyethylene and polyoxypropylene.
  • Suitable polyelectrolytes are polyacids or polybases. Examples of polyacids are alkali metal salts of polyacrylic acid or polyacid comb polymers. Examples of the polybase are polyvinylamine or polyvinylamine.
  • the aforementioned carrier may be various carriers known in the field of pesticide preparations, including various silicates, carbonates, sulfates, oxides, phosphates, plant carriers, and synthetic carriers. Specifically, for example: white carbon black, kaolin, diatomaceous earth, clay, talc, organic bentonite, pumice, titanium dioxide, dextrin, cellulose powder, light calcium carbonate, soluble starch, corn starch, sawdust powder, urea, amine Fertilizer, a mixture of urea and amine fertilizer, glucose, maltose, sucrose, anhydrous potassium carbonate, anhydrous sodium carbonate, anhydrous potassium bicarbonate, anhydrous sodium bicarbonate, attapulgite, anhydrous potassium carbonate and anhydrous hydrogen carbonate One or more of a mixture of potassium and a mixture of anhydrous sodium carbonate and anhydrous sodium bicarbonate.
  • the fungicide composition may further contain various formulation adjuvants commonly used in the field of pesticide preparations.
  • the formulation adjuvant may be a solvent, a cosolvent, and a thickener.
  • Antifreeze capsule material, protective agent, antifoaming agent, disintegrating agent, stabilizer, preservative, adhesive, chelating agent.
  • Suitable solvents are water and organic solvents, such as medium to high boiling point mineral oil fractions, such as kerosene, diesel oil; oils of vegetable or animal origin; aliphatic, cyclic and aromatic hydrocarbons such as toluene, paraffin, tetrahydronaphthalene Alkyl naphthalenes; alcohols, such as ethanol, propanol, butanol, benzyl alcohol, cyclohexanol; glycols; DMSO; ketones, such as cyclohexanone; esters, such as lactate, carbonate, Fatty acid esters, ⁇ -butyrolactone; fatty acids; phosphonates; amines; amides, such as N-methylpyrrolidone, fatty acid dimethylamide; and mixtures thereof.
  • mineral oil fractions such as kerosene, diesel oil
  • oils of vegetable or animal origin oils of vegetable or animal origin
  • aliphatic, cyclic and aromatic hydrocarbons such as to
  • solvents can also be used as co-solvents.
  • Suitable thickeners are selected from polysaccharides (e.g. xanthan gum, carboxymethyl cellulose), inorganic clays (organically modified or unmodified), polycarboxylates and silicates.
  • Suitable antifreeze agents are selected from ethylene glycol, propylene glycol, glycerol, urea, glycerol and mixtures thereof.
  • Suitable capsules are selected from polyurethane, polyurea, urea resins and mixtures thereof.
  • Suitable protective agents are selected from polyvinyl alcohol and / or polyethylene glycol.
  • Suitable defoamers are selected from the group consisting of polysiloxanes, silicone milks, long-chain alcohols, fatty acids and their salts, and fluorine-containing organics and mixtures thereof.
  • Suitable disintegrants are selected from bentonite, urea, ammonium sulfate, aluminum chloride, citric acid, succinic acid, sodium bicarbonate and mixtures thereof
  • Suitable stabilizers are selected from triphenyl phosphite, epichlorohydrin, acetic anhydride, and mixtures thereof.
  • Suitable preservatives are selected from the group consisting of benzoic acid, sodium benzoate, 1,2-benzoisothiazolin-3-one (BIT for short), carson, potassium sorbate, and mixtures thereof.
  • Suitable binders are selected from polyvinylpyrrolidone, polyvinyl acetate, polyvinyl alcohol, polyacrylate, biowax or synthetic wax, and cellulose ether.
  • the fungicides according to the invention can be applied in the form of their formulations or in the use forms prepared therefrom, such as aerosols, capsule suspensions, cold-fogging concentrates, hot-fog concentrates, capsules Granules, fine granules, flowable concentrates for seed treatment, ready-to-use solutions, dustable powders, emulsifiable concentrates, oil-in-water emulsions, water-in-oil emulsions, Large granules, micro granules, oil-dispersible powders, oil-miscible flow concentrates, oil-miscible liquids, aerosols (under pressure), gas producing products, foaming agents, pastes, suspension concentrates, suspension emulsions Concentrates, soluble concentrates, suspensions, wettable powders, soluble powders, powders and granules, water-soluble and water-dispersible granules or tablets, water-soluble or water-dispersible powders for seed treatment,
  • the compounds of the present invention are useful as plant disease control agents. Accordingly, the present invention may further include a method for controlling a plant disease caused by a phytopathogenic fungus, the method comprising applying an effective amount of a compound of the present invention to a plant or a part thereof to be protected or a seed of a plant to be protected or comprising the Fungicidal compositions of the compounds.
  • the compounds and / or compositions of the present invention can provide control of diseases caused by broad-spectrum phytopathogenic fungi of the Basidiomycetes, Ascomycetes, Oomycetes, and Deuteromycetes. They can effectively control broad-spectrum plant diseases, especially leaf pathogens of ornamental crops, lawn crops, vegetable crops, field crops, cereal crops, and fruit tree crops.
  • pathogens include: Oomycetes, including Phytophthora diseases such as Phytophthora infestans, Phytophthora megasperma, Phytophthora parasitica, Phytophthora diseases of cinnamomi and Phytophthora capsici, diseases of Pythium species such as Pythium aphanidermatum, and diseases of species Peronosporaceae Pathogen (Plasmopara viticola), Downy mildew disease (Peronospora spp.) (Including tobacco downy mildew (Peronospora tabacina and Peronospora parasitica)), Pseudoperonospora disease (including cucumber downy mildew) (Pseudoperonospora cubensis) and Bremia lactucae); ascomycetes (including Alternaria bacterium such as Alternaria solani and cabbage black spot bacterium (Alternaria braccae)) (Guignardia
  • the composition or combination is effective against bacteria such as Erwinia amylovora, Xanthomonas campestris, Pseudomonas syringae, and others The strains are resistant.
  • the method of using the fungicide composition of the present invention is simple. Before plant disease germination or after germination, it is applied to crops and crop growth sites according to conventional methods, such as soil mixing, spraying, spraying, pouring, etc., and the application amount is according to the climate Depending on the conditions or the state of the crop, in general, 10-5000 g is applied per acre and diluted to 10-400 mg / L (preferably 100-300 mg / L).
  • the diluent is preferably water.
  • the fungicidal effect of the fungicide composition of the present invention is generally related to external factors such as climate, but the influence of climate can be slowed down by using a proper dosage form.
  • composition of the present invention can also be used in combination with other compounds having fungicidal, insecticidal or herbicidal properties. It can also be used with nematicides, acaricides, protective agents, herbicide safeners, growth regulators, phytonutrients or soil regulators. And so on.
  • the compounds of the present invention can be prepared by the methods described in the present invention, unless further specified, wherein the definition of each substituent is as described in the present invention.
  • the chemical reactions described in the present invention can be used to suitably prepare many other compounds of the present invention, and other methods for preparing the compounds of the present invention are considered to be within the scope of the present invention.
  • the synthesis of those non-exemplified compounds according to the present invention can be successfully accomplished by those skilled in the art through modification methods, such as appropriate protection of interference groups, through the use of other known reagents (except as described in the present invention), Or make some conventional modifications to the reaction conditions.
  • the reactions disclosed in the present invention or known reaction conditions are also recognized to be suitable for the preparation of other compounds of the present invention.
  • the reaction of the present invention is performed at room temperature, where the room temperature is 0 to 35 ° C.
  • test conditions of the nuclear magnetic resonance hydrogen spectrum of the present invention are as follows: at room temperature, a Bruker 400MHz or 600MHz nuclear magnetometer, using CDC1 3 , d 6 -DMSO, CD 3 OD or d 6 -acetone as a solvent (reported in ppm as Unit), using TMS (0ppm) or chloroform (7.26ppm) as the reference standard.
  • the mass spectrometry test conditions used in the present invention are:
  • the conditions for low-resolution mass spectrometry (MS) data measurement are: Agilent 6120 Quadrupole HPLC-MS (column model: Zorbax SB-C18, 2.1 x 30mm, 3.5 ⁇ m, 6min, flow rate 0.6mL / min, mobile phase: 5% -95% (proportion of CH 3 CN containing 0.1% formic acid) in (H 2 O containing 0.1% formic acid)), UV detection at 210 / 254nm, electrospray ionization mode (ESI).
  • MS mass spectrometry
  • the target compound (II) can be prepared by the first synthetic scheme.
  • Compound a undergoes esterification to give compound b; compound b reacts with hydrazine hydrate to give compound c; compound c is reacted with oxalyl chloride monoethyl ester under basic (such as triethylamine) conditions to give the bishydrazide intermediate, bisacyl
  • the hydrazine intermediate is cyclized under basic (such as triethylamine) conditions to obtain compound d; compound d is reduced by a reducing agent (such as sodium borohydride) to obtain compound e; compound e undergoes a substitution reaction to obtain compound f; compound f and Compound g is reacted under basic conditions (such as potassium carbonate) to obtain the target compound (II);
  • R 1 , R 2 , R 3 , R 4 and R 5 have the meanings described in the present invention.
  • the target compound (III) can be prepared by the second synthetic scheme.
  • Compound a1 undergoes esterification to obtain compound b1; compound b1 reacts with hydrazine hydrate to obtain compound c1; compound c1 reacts with oxalyl chloride monoethyl ester under basic (such as triethylamine) conditions to obtain the diacylhydrazine intermediate, diacyl
  • the hydrazine intermediate is cyclized under basic (such as triethylamine) conditions to obtain compound d1; compound d1 is reduced by a reducing agent (such as sodium borohydride) to obtain compound e1; substitution reaction of compound e1 to obtain compound f1; compound f1 and Compound g is reacted under basic conditions (such as potassium carbonate) to obtain the target compound (III);
  • R 2 , R 3 , R 4 and R 5 have the meanings described in the present invention.
  • methyl benzoylformate (164g, 1mol) was dissolved in methanol (500mL), and a 40% methylamine aqueous solution (101g, 1.3mol) was added dropwise. After the dropwise addition was completed, the reaction was stirred at room temperature. 2 hours. The methanol was concentrated under reduced pressure, diluted with ethyl acetate (300 mL), washed with water (200 mL), washed with sodium hydroxide (1N, 200 mL), washed with hydrochloric acid (1N, 200 mL), and washed with saturated brine (200 mL). Drying with sodium sulfate and concentration under reduced pressure gave 130 g of a pale yellow solid, yield: 80%.
  • N-methyl-2-oxo-2-phenylacetamide (65 g, 0.4 mol) was dissolved in a mixed solution of N, N-dimethylformamide (2.9 g) and chloroform (500 mL) at 0 ° C. Then, dichlorosulfoxide (71.4 g, 0.6 mol) was added dropwise. After the dropwise addition was completed, the reaction was stirred at room temperature for 2 hours, and the reaction was heated at reflux for 8 hours. The solvent was removed by concentration under reduced pressure, toluene (100 mL) was added, and the mixture was stirred at room temperature for 8 hours, and then concentrated under reduced pressure to obtain 70 g of a brown oily liquid, yield: 70%.
  • Step D Synthesis of (1-methyl-1H-tetrazol-5-yl) (phenyl) methanone oxime
  • Step A Synthesis of methyl 2- (2,4-difluorophenoxy) benzoate
  • Step B Synthesis of 2- (2,4-difluorophenoxy) benzoyl hydrazide
  • Step C 5- (2- (2,4-difluorophenoxy) phenyl) -1,3,4-oxadiazole-2-carboxylic acid ethyl ester
  • Step D Synthesis of (5- (2- (2,4-difluorophenoxy) phenyl) -1,3,4-oxadiazol-2-yl) methanol
  • Step E Synthesis of 2- (bromomethyl) -5- (2- (2,4-difluorophenoxy) phenyl) -1,3,4-oxadiazole
  • Step F (Z)-(1-methyl-1H-tetrazol-5-yl) (phenyl) methanone O-((5- (2- (2,4-difluorophenoxy) phenyl ) -1,3,4-oxadiazol-2-yl) methyl) oxime
  • Example 1 By using a similar preparation method of Example 1 and using the corresponding intermediate compounds, reaction reagents, reaction conditions, and post-treatment methods, the target compounds in Table 1 can be prepared.
  • Example 138 (Z)-(1-methyl-1H-tetrazol-5-yl) (phenyl) methanone O-((5- (4- (trifluoromethyl) phenyl) -1, Synthesis of 3,4-oxadiazol-2-yl) methyl) oxime
  • This test example is used to determine the fungicidal activity of the compounds prepared in the examples.
  • the test target in this test example is cucumber downy mildew.
  • In vivo pot method was used to evaluate the fungicidal activity of these compounds against test targets at a dose of 200 mg / L.
  • the test method uses a SOP (Fungicide Roll) to evaluate the biological activity of the created pesticide.
  • Example 1 Compound Prevention effect (%) Example 1 100 Example 2 100 Example 3 100 Example 4 100 Example 5 100 Example 6 100 Example 8 100 Example 10 100 Example 11 100 Example 12 100 Example 13 100 Example 14 100 Example 16 100
  • This test example is used to determine the fungicidal activity of the compound.
  • the test target in this test example is cucumber downy mildew. Dissolve into 1% EC with DMSO for future use.
  • In vivo pot method was used to evaluate the fungicidal activity of these compounds on test targets at 25 mg / L, 12.5 mg / L, 6.25 mg / L, 3.125 mg / L, and 1.5625 mg / L doses.
  • the test method uses a SOP (Fungicide Roll) to evaluate the biological activity of the created pesticide.
  • Example 1 Compound Prevention effect (%) Example 1 100 Example 2 100 Example 3 80 Example 4 100 Example 5 100 Example 6 100 Example 10 100 Example 11 95 Example 12 90 Example 13 95 Example 14 100 Example 16 85 Example 17 90 Example 18 100 Example 19 80 Example 20 100 Example 21 100 Example 22 100 Example 24 90 Example 25 100 Example 26 100 Example 28 100 Example 29 95 Example 30 90 Example 31 90
  • Example 33 100 Example 34 100 Example 35 98 Example 36 80 Example 37 100 Example 38 100 Example 39 100 Example 40 100 Example 42 98 Example 43 100 Example 44 98 Example 45 98 Example 47 98 Example 48 98 Example 49 93 Example 50 100 Example 52 98 Example 53 95 Example 54 100 Example 56 100 Example 57 100 Example 58 90 Example 59 100 Example 60 100 Example 62 96 Example 66 98 Example 67 98 Example 68 98 Example 69 100 Example 71 98 Example 74 90 Example 76 98 Example 78 93 Example 79 98 Example 80 100 Example 81 100 Example 82 90 Example 86 98 Example 87 95 Example 89 85 Example 90 87 Example 92 98
  • Example 93 98 Example 95 80
  • Example 97 96
  • Example 99 85
  • Example 100 96
  • Example 101 80
  • Example 102 100
  • Example 103 100
  • Example 108 90
  • Example 109 100
  • Example 110 100
  • Example 113 98
  • Example 115 100
  • Example 116 100
  • Example 119 98
  • Example 121 85
  • Example 122 85 Example 123 90
  • Example 128 100
  • Example 130 98
  • Example 131 85
  • Example 133 80
  • Example 134 100
  • Example 136 85
  • Example 1 Compound Prevention effect (%) Example 1 100 Example 5 100 Example 10 98 Example 14 80 Example 18 98 Example 20 95 Example 21 90 Example 22 90 Example 25 100 Example 33 100
  • Example 34 90 Example 35 95 Example 37 100 Example 38 100 Example 39 98 Example 40 100 Example 43 100 Example 44 93 Example 45 80 Example 49 80 Example 50 98 Example 52 90 Example 53 90 Example 54 100 Example 56 90 Example 59 85 Example 66 93 Example 67 95 Example 69 100 Example 74 80 Example 76 87 Example 79 90 Example 82 80 Example 97 80 Example 103 80 Example 113 95 Example 123 80 Example 128 90 Example 129 85 Example 130 85 Example 134 98
  • Example 10 Compound Prevention effect (%) Example 10 85 Example 18 85 Example 25 80 Example 33 98 Example 35 90 Example 37 100 Example 38 98
  • Example 39 85
  • Example 40 97
  • Example 43 100
  • Example 44 85
  • Example 50 80
  • Example 54 100
  • Example 66 85
  • Example 134 95
  • the compound of the present invention has a good control effect on phytopathogenic fungi, especially against cucumber downy mildew, and some of the compounds (such as Example 43 or Example 54) are at lower doses (such as 3.125). mg / L dose) against cucumber downy mildew is still more than 80%, so it has a good application prospect.

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Abstract

Disclosed are an oxadiazole oxime derivative and the use thereof in agriculture. Specifically, disclosed are: an oxadiazole oxime derivative as shown in formula (I-A), or a stereoisomer, a salt and an oxynitride of the oxadiazole oxime derivative as shown in formula (I-A), or (E)- and (Z)-isomers and a mixture thereof; a method for preparing the oxadiazole oxime derivative, the use of same as a fungicide, and the form thereof of a fungicide composition; and a the method for preventing and controlling phytopathogenic fungi using such compounds or compositions. A, T, B, B1, B2, R4 and R5 have the meaning as described in the claims and the description.

Description

噁二唑类肟衍生物及其在农业中的应用Oxadiazole derivatives and their application in agriculture 技术领域Technical field
本发明涉及农药领域，具体地涉及噁二唑类肟衍生物及含有该类衍生物作为有效成分的农药，特别是植物病原性真菌防除剂。The present invention relates to the field of pesticides, in particular to oxadiazole oxime derivatives and pesticides containing such derivatives as active ingredients, especially phytopathogenic fungal control agents.
背景技术Background technique
现代农业生产中，需要使用各类农药用于确保作物的健康生长，现有化合物在相对低的施用率下，杀菌活性总是不够的；并且由于长时间频繁地使用农药，导致作物上的病害对现有的农药产生抗药性，使农药的防治效果降低，为了解决高效或抗药性的问题，需要不断开发出具有防治作物病害的新型化合物。In modern agricultural production, various pesticides are used to ensure the healthy growth of crops. The existing compounds have insufficient bactericidal activity at relatively low application rates; and due to frequent and frequent use of pesticides, they cause diseases on crops. To produce resistance to existing pesticides and reduce the control effect of pesticides. In order to solve the problem of high efficiency or resistance, new compounds with crop disease prevention and control needs to be continuously developed.
发明内容Summary of the Invention
本发明提供一种噁二唑类肟衍生物，以及包含这种衍生物的组合物，该噁二唑类肟衍生物及其组合物用于防治植物病原性真菌。The present invention provides an oxadiazole oxime derivative and a composition containing the derivative. The oxadiazole oxime derivative and a composition thereof are used for controlling plant pathogenic fungi.
具体地：specifically:
一方面，本发明提供一种化合物，其为具有式(I-A)所示的化合物或式(I-A)所示的化合物的盐、氮氧化物、或(E)和(Z)异构体以及它们的混合物：In one aspect, the present invention provides a compound having a compound represented by Formula (IA) or a salt, nitrogen oxide, or (E) and (Z) isomers of a compound represented by Formula (IA), and mixture:
Figure PCTCN2019091137-appb-000001
Figure PCTCN2019091137-appb-000001
其中，among them,
T为含有1、2、3或4个氮原子的5元杂芳基；其中，所述的5元杂芳基任选地被一个或多个烷基取代；T is a 5-membered heteroaryl group containing 1, 2, 3, or 4 nitrogen atoms; wherein the 5-membered heteroaryl group is optionally substituted with one or more alkyl groups;
A为芳基或杂芳基；其中A任选地被1、2、3、4、5或6个R b取代； A is aryl or heteroaryl; wherein A is optionally substituted with 1, 2, 3, 4, 5 or 6 R b ;
其中，各R b独立地为卤素、羟基、氰基、硝基、氨基、羧基、烷基、烷氧基、卤代烷基、卤代烷氧基、芳基或芳氧基； Wherein each R b is independently halogen, hydroxy, cyano, nitro, amino, carboxyl, alkyl, alkoxy, haloalkyl, haloalkoxy, aryl or aryloxy;
B 1为CR 1或N； B 1 is CR 1 or N;
B为CR 2或N； B is CR 2 or N;
B 2为CR 3或N； B 2 is CR 3 or N;
条件为：B 1、B和B 2中至多有一个为N； Provided that at least one of B 1 , B and B 2 is N;
R 1、R 2、R 3、R 4和R 5各自独立地为氢、卤素、羟基、氰基、硝基、氨基、羧基、烷基、卤代烷基、烷氧基或卤代烷氧基； R 1 , R 2 , R 3 , R 4 and R 5 are each independently hydrogen, halogen, hydroxyl, cyano, nitro, amino, carboxyl, alkyl, haloalkyl, alkoxy or haloalkoxy;
或R 1、R 2、R 3、R 4和R 5各自独立地为以下子结构式： Or R 1 , R 2 , R 3 , R 4 and R 5 are each independently the following substructure formula:
Figure PCTCN2019091137-appb-000002
Figure PCTCN2019091137-appb-000002
其中，R 11、R 22、R 33、R 44和R 55各自独立地为氢、卤素、羟基、氰基、硝基、氨基、羧基、烷基、卤代烷基、烷氧基、卤代烷氧基、烷基胺基或烷硫基； Among them, R 11 , R 22 , R 33 , R 44 and R 55 are each independently hydrogen, halogen, hydroxyl, cyano, nitro, amino, carboxyl, alkyl, haloalkyl, alkoxy, haloalkoxy, Alkylamino or alkylthio;
条件为：R 1、R 2、R 3、R 4和R 5中有且只有一个为
Figure PCTCN2019091137-appb-000003
The conditions are: there is only one of R 1 , R 2 , R 3 , R 4 and R 5 is
Figure PCTCN2019091137-appb-000003
在一些实施方案中，本发明提供一种式(I)所示的化合物或式(I)所示的化合物的盐、氮氧化物、或(E)和(Z)异构体以及它们的混合物：In some embodiments, the present invention provides a compound represented by formula (I) or a salt, nitrogen oxide, or (E) and (Z) isomers of a compound represented by formula (I), and mixtures thereof :
Figure PCTCN2019091137-appb-000004
Figure PCTCN2019091137-appb-000004
其中，among them,
T为含有1、2、3或4个氮原子的5元杂芳基；其中，所述的5元杂芳基任选地被一个或多个烷基取代；T is a 5-membered heteroaryl group containing 1, 2, 3, or 4 nitrogen atoms; wherein the 5-membered heteroaryl group is optionally substituted with one or more alkyl groups;
A为芳基或杂芳基；其中A任选地被1、2、3、4、5或6个R b取代； A is aryl or heteroaryl; wherein A is optionally substituted with 1, 2, 3, 4, 5 or 6 R b ;
其中，各R b独立地为卤素、羟基、氰基、硝基、氨基、羧基、烷基、烷氧基、卤代烷基、卤代烷氧基、芳基或芳氧基； Wherein each R b is independently halogen, hydroxy, cyano, nitro, amino, carboxyl, alkyl, alkoxy, haloalkyl, haloalkoxy, aryl or aryloxy;
R 1、R 2、R 3、R 4和R 5各自独立地为氢、卤素、羟基、氰基、硝基、氨基、羧基、烷基、卤代烷基、烷氧基或卤代烷氧基； R 1 , R 2 , R 3 , R 4 and R 5 are each independently hydrogen, halogen, hydroxyl, cyano, nitro, amino, carboxyl, alkyl, haloalkyl, alkoxy or haloalkoxy;
或R 1、R 2、R 3、R 4和R 5各自独立地为以下子结构式： Or R 1 , R 2 , R 3 , R 4 and R 5 are each independently the following substructure formula:
Figure PCTCN2019091137-appb-000005
Figure PCTCN2019091137-appb-000005
其中，R 11、R 22、R 33、R 44和R 55各自独立地为氢、卤素、羟基、氰基、硝基、氨基、羧基、烷基、卤代烷基、烷氧基、卤代烷氧基、烷基胺基或烷硫基； Among them, R 11 , R 22 , R 33 , R 44 and R 55 are each independently hydrogen, halogen, hydroxyl, cyano, nitro, amino, carboxyl, alkyl, haloalkyl, alkoxy, haloalkoxy, Alkylamino or alkylthio;
条件为：R 1、R 2、R 3、R 4和R 5中有且只有一个为
Figure PCTCN2019091137-appb-000006
The conditions are: there is only one of R 1 , R 2 , R 3 , R 4 and R 5 is
Figure PCTCN2019091137-appb-000006
在一些实施方案中，T为含有1、2、3或4个氮原子的5元杂芳基；其中，所述的5元杂芳基任选地被一个或多个C 1-6烷基取代； In some embodiments, T is a 5-membered heteroaryl group containing 1, 2, 3, or 4 nitrogen atoms; wherein said 5-membered heteroaryl group is optionally substituted by one or more C 1-6 alkyl groups. Replace
A为C 6-10芳基或5-10元杂芳基；其中A任选地被1、2、3、4、5或6个R b取代； A is C 6-10 aryl or 5-10 membered heteroaryl; wherein A is optionally substituted with 1, 2, 3, 4, 5 or 6 R b ;
其中，各R b独立地为卤素、羟基、氰基、硝基、氨基、羧基、C 1-6烷基、C 1-6烷氧基、卤代C 1-6烷基、卤代C 1-6烷氧基、C 6-10芳基或C 6-10芳氧基； Wherein each R b is independently halogen, hydroxy, cyano, nitro, amino, carboxyl, C 1-6 alkyl, C 1-6 alkoxy, halo C 1-6 alkyl, halo C 1 -6 alkoxy, C 6-10 aryl or C 6-10 aryloxy;
R 1、R 2、R 3、R 4和R 5各自独立地为氢、卤素、羟基、氰基、硝基、氨基、羧基、C 1-6烷基、卤代C 1-6烷基、C 1-6烷氧基或卤代C 1-6烷氧基； R 1 , R 2 , R 3 , R 4 and R 5 are each independently hydrogen, halogen, hydroxyl, cyano, nitro, amino, carboxyl, C 1-6 alkyl, halo C 1-6 alkyl, C 1-6 alkoxy or halo C 1-6 alkoxy;
或R 1、R 2、R 3、R 4和R 5各自独立地为以下子结构式： Or R 1 , R 2 , R 3 , R 4 and R 5 are each independently the following substructure formula:
Figure PCTCN2019091137-appb-000007
Figure PCTCN2019091137-appb-000007
其中，R 11、R 22、R 33、R 44和R 55各自独立地为氢、卤素、羟基、氰基、硝基、氨基、羧基、C 1-6烷基、卤代C 1-6烷基、C 1-6烷氧基、卤代C 1-6烷氧基、C 1-6烷基胺基或C 1-6烷硫基。 Among them, R 11 , R 22 , R 33 , R 44 and R 55 are each independently hydrogen, halogen, hydroxyl, cyano, nitro, amino, carboxyl, C 1-6 alkyl, halo C 1-6 alkane Alkyl, C 1-6 alkoxy, halo C 1-6 alkoxy, C 1-6 alkylamino or C 1-6 alkylthio.
还在另一些实施方案中，T为以下子结构式：In still other embodiments, T is the following substructure formula:
Figure PCTCN2019091137-appb-000008
Figure PCTCN2019091137-appb-000008
其中，各R a独立地为氢或C 1-4烷基； Wherein each R a is independently hydrogen or C 1-4 alkyl;
A为以下子结构式：A is the following substructure formula:
Figure PCTCN2019091137-appb-000009
Figure PCTCN2019091137-appb-000009
其中，z为0、1、2、3、4或5；Where z is 0, 1, 2, 3, 4 or 5;
其中，各R b独立地为卤素、羟基、氰基、硝基、氨基、羧基、C 1-4烷基、C 1-4烷氧基、卤代C 1-4烷基、卤代C 1-4烷氧基、C 6-10芳基或C 6-10芳氧基。 Wherein each R b is independently halogen, hydroxy, cyano, nitro, amino, carboxyl, C 1-4 alkyl, C 1-4 alkoxy, halo C 1-4 alkyl, halo C 1 -4 alkoxy, C 6-10 aryl or C 6-10 aryloxy.
还在另一些实施方案中，T为以下子结构式：In still other embodiments, T is the following substructure formula:
Figure PCTCN2019091137-appb-000010
Figure PCTCN2019091137-appb-000010
其中，各R a独立地为氢、-CH 3或-CH 2CH 3； Wherein each R a is independently hydrogen, -CH 3 or -CH 2 CH 3 ;
A为以下子结构式：A is the following substructure formula:
Figure PCTCN2019091137-appb-000011
Figure PCTCN2019091137-appb-000011
其中，z为0、1、2、3、4或5；Where z is 0, 1, 2, 3, 4 or 5;
其中，各R b独立地为氟、氯、溴、碘、羟基、氰基、硝基、氨基、羧基、-CH 3、-CH 2CH 3、-CH 2CH 2CH 3、-CH(CH 3) 2、-CH 2CH 2CH 2CH 3、-C(CH 3) 3、-OCH 3、-OCH 2CH 3、-OCH 2CH 2CH 3、-OCH(CH 3) 2、-OC(CH 3) 3、-CHF 2、-CF 3或-OCF 3。 Among them, each R b is independently fluorine, chlorine, bromine, iodine, hydroxyl, cyano, nitro, amino, carboxyl, -CH 3 , -CH 2 CH 3 , -CH 2 CH 2 CH 3 , -CH (CH 3 ) 2 , -CH 2 CH 2 CH 2 CH 3 , -C (CH 3 ) 3 , -OCH 3 , -OCH 2 CH 3 , -OCH 2 CH 2 CH 3 , -OCH (CH 3 ) 2 , -OC (CH 3 ) 3 , -CHF 2 , -CF 3 or -OCF 3 .
在一些实施方案中，R 1、R 2、R 3、R 4和R 5各自独立地为氢、卤素、羟基、氰基、硝基、氨基、羧基、C 1-4烷基、卤代C 1-4烷基、C 1-4烷氧基或卤代C 1-4烷氧基； In some embodiments, R 1 , R 2 , R 3 , R 4 and R 5 are each independently hydrogen, halogen, hydroxyl, cyano, nitro, amino, carboxyl, C 1-4 alkyl, haloC 1-4 alkyl, C 1-4 alkoxy or halo C 1-4 alkoxy;
或R 1、R 2、R 3、R 4和R 5各自独立地为以下子结构式： Or R 1 , R 2 , R 3 , R 4 and R 5 are each independently the following substructure formula:
Figure PCTCN2019091137-appb-000012
Figure PCTCN2019091137-appb-000012
其中，R 11、R 22、R 33、R 44和R 55各自独立地为氢、卤素、羟基、氰基、硝基、氨基、羧基、C 1-4烷基、 卤代C 1-4烷基、C 1-4烷氧基、卤代C 1-4烷氧基、C 1-4烷基胺基或C 1-4烷硫基。 Among them, R 11 , R 22 , R 33 , R 44 and R 55 are each independently hydrogen, halogen, hydroxyl, cyano, nitro, amino, carboxyl, C 1-4 alkyl, halo C 1-4 alkane Alkyl, C 1-4 alkoxy, halo C 1-4 alkoxy, C 1-4 alkylamino or C 1-4 alkylthio.
在另一些实施方案中，R 1、R 2、R 3、R 4和R 5各自独立地为氢、氟、氯、溴、碘、羟基、氰基、硝基、氨基、羧基、-CH 3、-CH 2CH 3、-CH 2CH 2CH 3、-CH(CH 3) 2、-CH 2CH 2CH 2CH 3、-C(CH 3) 3、-CH 2Cl、-CHF 2、-CF 3、-OCH 3、-OCH 2CH 3、-OCH 2CH 2CH 3、-OCH(CH 3) 2、-OC(CH 3) 3或-OCF 3； In other embodiments, R 1 , R 2 , R 3 , R 4 and R 5 are each independently hydrogen, fluorine, chlorine, bromine, iodine, hydroxyl, cyano, nitro, amino, carboxyl, -CH 3 , -CH 2 CH 3 , -CH 2 CH 2 CH 3 , -CH (CH 3 ) 2 , -CH 2 CH 2 CH 2 CH 3 , -C (CH 3 ) 3 , -CH 2 Cl, -CHF 2 , -CF 3 , -OCH 3 , -OCH 2 CH 3 , -OCH 2 CH 2 CH 3 , -OCH (CH 3 ) 2 , -OC (CH 3 ) 3 or -OCF 3 ;
或R 1、R 2、R 3、R 4和R 5各自独立地为以下子结构式： Or R 1 , R 2 , R 3 , R 4 and R 5 are each independently the following substructure formula:
Figure PCTCN2019091137-appb-000013
Figure PCTCN2019091137-appb-000013
其中，R 11、R 22、R 33、R 44和R 55各自独立地为氢、氟、氯、溴、碘、羟基、氰基、硝基、氨基、羧基、-CH 3、-CH 2CH 3、-CH 2CH 2CH 3、-CH(CH 3) 2、-CH 2CH 2CH 2CH 3、-C(CH 3) 3、-CF 3、-OCH 3、-OCH 2CH 3、-OCH 2CH 2CH 3、-OCH(CH 3) 2、-OC(CH 3) 3、-OCF 3、-N(CH 3) 2或-SCH 3。 Among them, R 11 , R 22 , R 33 , R 44 and R 55 are each independently hydrogen, fluorine, chlorine, bromine, iodine, hydroxyl, cyano, nitro, amino, carboxyl, -CH 3 , -CH 2 CH 3 , -CH 2 CH 2 CH 3 , -CH (CH 3 ) 2 , -CH 2 CH 2 CH 2 CH 3 , -C (CH 3 ) 3 , -CF 3 , -OCH 3 , -OCH 2 CH 3 , -OCH 2 CH 2 CH 3 , -OCH (CH 3 ) 2 , -OC (CH 3 ) 3 , -OCF 3 , -N (CH 3 ) 2 or -SCH 3 .
又在另一些实施方案中，本发明提供一种式(II)所示的化合物或式(II)所示的化合物的盐或其氮氧化物：In still other embodiments, the present invention provides a compound represented by formula (II) or a salt of a compound represented by formula (II) or a nitrogen oxide thereof:
Figure PCTCN2019091137-appb-000014
Figure PCTCN2019091137-appb-000014
在一些实施方案中，R 1、R 2、R 3、R 4和R 5各自独立地为氢、卤素、C 1-4烷基、卤代C 1-4烷基、C 1-4烷氧基或卤代C 1-4烷氧基； In some embodiments, R 1 , R 2 , R 3 , R 4, and R 5 are each independently hydrogen, halogen, C 1-4 alkyl, halo C 1-4 alkyl, C 1-4 alkoxy Or halo C 1-4 alkoxy;
或R 1、R 2、R 3、R 4和R 5各自独立地为以下子结构式： Or R 1 , R 2 , R 3 , R 4 and R 5 are each independently the following substructure formula:
Figure PCTCN2019091137-appb-000015
Figure PCTCN2019091137-appb-000015
其中，R 11、R 22、R 33、R 44和R 55各自独立地为氢、卤素、C 1-4烷基、C 1-4烷氧基、卤代C 1-4烷基或卤代C 1-4烷氧基； Wherein R 11 , R 22 , R 33 , R 44 and R 55 are each independently hydrogen, halogen, C 1-4 alkyl, C 1-4 alkoxy, halo C 1-4 alkyl or halo C 1-4 alkoxy;
条件为：R 1、R 2和R 3中有且只有一个为
Figure PCTCN2019091137-appb-000016
The condition is: there is only one of R 1 , R 2 and R 3 is
Figure PCTCN2019091137-appb-000016
在另一些实施方案中，R 1、R 2、R 3、R 4和R 5各自独立地为氢、氟、氯、溴、碘、-CH 3、-CH 2CH 3、-CH 2CH 2CH 3、-CH(CH 3) 2、-CH 2CH 2CH 2CH 3、-C(CH 3) 3、-CF 3、-OCH 3或-OCF 3； In other embodiments, R 1 , R 2 , R 3 , R 4 and R 5 are each independently hydrogen, fluorine, chlorine, bromine, iodine, -CH 3 , -CH 2 CH 3 , -CH 2 CH 2 CH 3 , -CH (CH 3 ) 2 , -CH 2 CH 2 CH 2 CH 3 , -C (CH 3 ) 3 , -CF 3 , -OCH 3 or -OCF 3 ;
或R 1、R 2、R 3、R 4和R 5各自独立地为以下子结构式： Or R 1 , R 2 , R 3 , R 4 and R 5 are each independently the following substructure formula:
Figure PCTCN2019091137-appb-000017
Figure PCTCN2019091137-appb-000017
其中，R 11、R 22、R 33、R 44和R 55各自独立地为氢、氟、氯、溴、碘、-CH 3、-CH 2CH 3、-CH 2CH 2CH 3、-CH(CH 3) 2、-CH 2CH 2CH 2CH 3、-C(CH 3) 3、-CF 3、-OCH 3或-OCF 3。 Among them, R 11 , R 22 , R 33 , R 44 and R 55 are each independently hydrogen, fluorine, chlorine, bromine, iodine, -CH 3 , -CH 2 CH 3 , -CH 2 CH 2 CH 3 , -CH (CH 3 ) 2 , -CH 2 CH 2 CH 2 CH 3 , -C (CH 3 ) 3 , -CF 3 , -OCH 3 or -OCF 3 .
又还在另一些实施方案中，本发明提供一种式(III)所示的化合物或式(III)所示的化合物的盐或其氮氧化物：In still other embodiments, the present invention provides a compound represented by formula (III) or a salt of a compound represented by formula (III) or a nitrogen oxide thereof:
Figure PCTCN2019091137-appb-000018
Figure PCTCN2019091137-appb-000018
在一些实施方案中，R 2、R 3、R 4和R 5各自独立地为氢、卤素、C 1-4烷基或卤代C 1-4烷基； In some embodiments, R 2 , R 3 , R 4, and R 5 are each independently hydrogen, halogen, C 1-4 alkyl, or halo C 1-4 alkyl;
或R 2、R 3、R 4和R 5各自独立地为以下子结构式： Or R 2 , R 3 , R 4 and R 5 are each independently the following substructure formula:
Figure PCTCN2019091137-appb-000019
Figure PCTCN2019091137-appb-000019
其中，R 11、R 22、R 33、R 44和R 55各自独立地为氢、卤素、C 1-4烷基、C 1-4烷氧基、卤代C 1-4烷基、卤代C 1-4烷氧基、C 1-4烷基胺基或C 1-4烷硫基； Among them, R 11 , R 22 , R 33 , R 44 and R 55 are each independently hydrogen, halogen, C 1-4 alkyl, C 1-4 alkoxy, halo C 1-4 alkyl, halo C 1-4 alkoxy, C 1-4 alkylamino or C 1-4 alkylthio;
条件为：R 2、R 3、R 4和R 5中有且只有一个为
Figure PCTCN2019091137-appb-000020
The conditions are: there is only one of R 2 , R 3 , R 4 and R 5 is
Figure PCTCN2019091137-appb-000020
在另一些实施方案中，R 2、R 3、R 4和R 5各自独立地为氢、氟、氯、溴、碘、-CH 3或-CF 3； In other embodiments, R 2 , R 3 , R 4 and R 5 are each independently hydrogen, fluorine, chlorine, bromine, iodine, —CH 3 or —CF 3 ;
或R 2、R 3、R 4和R 5各自独立地为以下子结构式： Or R 2 , R 3 , R 4 and R 5 are each independently the following substructure formula:
Figure PCTCN2019091137-appb-000021
Figure PCTCN2019091137-appb-000021
其中，R 11、R 22、R 33、R 44和R 55各自独立地为氢、氟、氯、溴、碘、-CH 3、-CH 2CH 3、-CH 2CH 2CH 3、-CH(CH 3) 2、-CH 2CH 2CH 2CH 3、-C(CH 3) 3、-CF 3、-OCH 3、-OCF 3、-N(CH 3) 2或-SCH 3。 Among them, R 11 , R 22 , R 33 , R 44 and R 55 are each independently hydrogen, fluorine, chlorine, bromine, iodine, -CH 3 , -CH 2 CH 3 , -CH 2 CH 2 CH 3 , -CH (CH 3 ) 2 , -CH 2 CH 2 CH 2 CH 3 , -C (CH 3 ) 3 , -CF 3 , -OCH 3 , -OCF 3 , -N (CH 3 ) 2 or -SCH 3 .
另一方面，本发明提供一种包含本发明化合物的组合物，其中所述的组合物进一步包含农药学上可接受的表面活性剂和/或载体。In another aspect, the invention provides a composition comprising a compound of the invention, wherein the composition further comprises an agrochemically acceptable surfactant and / or carrier.
另一方面，本发明提供本发明所述的化合物或本发明所述组合物在防治植物病原性真菌中的应用。In another aspect, the present invention provides the use of a compound of the present invention or a composition of the present invention for controlling plant pathogenic fungi.
本发明的详细说明Detailed description of the invention
定义和一般术语Definitions and general terms
现在详细描述本发明的某些实施方案，其实例由随附的结构式和化学式说明。本发明意图涵盖所有的替代、修改和等同技术方案，它们均包括在如权利要求定义的本发明范围内。本领域技术人员应认识到，许多与本发明所述类似或等同的方法和材料能够用于实践本发明。本发明绝不限于本发明所述的方法和材料。在所结合的文献、专利和类似材料的一篇或多篇与本申请不同或相矛盾的情况下(包括但不限于所定义的术语、术语应用、所描述的技术，等等)，以本申请为准。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 equivalent technical solutions, which are all included within the scope of the invention as defined by the claims. Those 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 invention is in no way limited to the methods and materials described herein. In the case where one or more of the incorporated documents, patents and similar materials are different or inconsistent with this application (including but not limited to the defined terms, term applications, described technologies, etc.), Application shall prevail.
应进一步认识到，本发明的某些特征，为清楚可见，在多个独立的实施方案中进行了描述，但也可以在单个实施例中以组合形式提供。反之，本发明的各种特征，为简洁起见，在单个实施方案中进行了描述，但也可以单独或以任意适合的子组合提供。It should be further recognized that certain features of the invention have been described in multiple independent embodiments for clarity, but may also be provided in combination in a single embodiment. Conversely, various features of the invention have been described in a single embodiment for the sake of brevity, but may also be provided separately or in any suitable subcombination.
除非另外说明，本发明所使用的所有科技术语具有与本发明所属领域技术人员的通常理解相同的含 义。本发明涉及的所有专利和公开出版物通过引用方式整体并入本发明。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 related to the present invention are incorporated herein by reference in their entirety.
除非另外说明，应当应用本发明所使用的下列定义。出于本发明的目的，化学元素与元素周期表CAS版，和《化学和物理手册》，第75版，1994一致。此外，有机化学一般原理可参考"Organic Chemistry",Thomas Sorrell,University Science Books,Sausalito:1999,和"March's Advanced Organic Chemistry"by Michael B.Smith and Jerry March,John Wiley&Sons,New York:2007中的描述，其全部内容通过引用并入本发明。Unless otherwise stated, the following definitions used in the present invention shall apply. For the purposes of the present invention, the chemical elements are in accordance with the CAS version of the Periodic Table of Elements, in accordance with the Handbook of Chemistry and Physics, 75th edition, 1994. In addition, the 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.
除非另有说明或者上下文中有明显的冲突，本发明所使用的冠词“一”、“一个(种)”和“所述”旨在包括“至少一个”或“一个或多个”。因此，本发明所使用的这些冠词是指一个或多于一个(即至少一个)宾语的冠词。例如，“一组分”指一个或多个组分，即可能有多于一个的组分被考虑在所述实施方案的实施方式中采用或使用。Unless stated otherwise or there is a clear conflict in context, the articles "a," "an," and "said" as used herein are intended to include "at least one" or "one or more". Thus, the articles used in the present invention refer to the articles of one or more (ie, at least one) objects. For example, "a component" means one or more components, that is, more than one component may be considered for adoption or use in an embodiment of the described embodiment.
术语“包含”为开放式表达，即包括本发明所指明的内容，但并不排除其他方面的内容。The term "comprising" is an open-ended expression, which includes the content specified in the present invention, but does not exclude other aspects.
“立体异构体”是指具有相同化学构造，但原子或基团在空间上排列方式不同的化合物。立体异构体包括对映异构体、非对映异构体、构象异构体(旋转异构体)、几何异构体(顺/反)异构体、阻转异构体，等等。"Stereoisomers" refer to compounds that have the same chemical structure, but differ in the arrangement of atoms or groups in space. Stereoisomers include enantiomers, diastereomers, conformers (rotomers), geometric isomers (cis / trans) isomers, atropisomers, etc. .
“对映异构体”是指一个化合物的两个不能重叠但互成镜像关系的异构体。"Enantiomers" refer to two isomers of a compound that cannot overlap but mirror image each other.
“非对映异构体”是指有两个或多个手性中性并且其分子不互为镜像的立体异构体。非对映异构体具有不同的物理性质，如熔点、沸点、光谱性质和反应性。非对映异构体混合物可通过高分辨分析操作如电泳和色谱，例如HPLC来分离。"Diastereomer" refers to a stereoisomer that has two or more chiral neutrality and whose molecules are not mirror images of each other. Diastereomers have different physical properties, such as melting points, boiling points, spectral properties, and reactivity. Diastereomeric mixtures can be separated by high resolution analytical operations such as electrophoresis and chromatography, such as HPLC.
本发明所使用的立体化学定义和规则一般遵循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中的描述。The definition and rules of stereochemistry used in the present invention generally follow SPParker, 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.
许多有机化合物以光学活性形式存在，即它们具有使平面偏振光的平面发生旋转的能力。在描述光学活性化合物时，使用前缀D和L或R和S来表示分子关于其一个或多个手性中心的绝对构型。前缀d和l或(+)和(-)是用于指定化合物所致平面偏振光旋转的符号，其中(-)或l表示化合物是左旋的。前缀为(+)或d的化合物是右旋的。一种具体的立体异构体是对映异构体，这种异构体的混合物称作对映异构体混合物。对映异构体的50:50混合物称为外消旋混合物或外消旋体，当在化学反应或过程中没有立体选择性或立体特异性时，可出现这种情况。Many organic compounds exist in optically active forms, that is, 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 indicate the absolute configuration of a molecule with respect to its one or more chiral centers. The prefixes d and l or (+) and (-) are symbols used to specify the rotation of plane-polarized light caused by a compound, where (-) or l indicates that the compound is left-handed. Compounds prefixed with (+) or d are right-handed. A specific stereoisomer is an enantiomer, and a mixture of such isomers is called an enantiomeric mixture. A 50:50 mixture of enantiomers is called a racemic mixture or a racemate, and this can occur when there is no stereoselection or stereospecificity in a chemical reaction or process.
本发明公开化合物的任何不对称原子(例如，碳等)都可以以外消旋或对映体富集的形式存在，例如(R)-、(S)-或(R,S)-构型形式存在。在某些实施方案中，各不对称原子在(R)-或(S)-构型方面具有至少50％对映体过量，至少60％对映体过量，至少70％对映体过量，至少80％对映体过量，至少90％对映体过量，至少95％对映体过量，或至少99％对映体过量。Any asymmetric atom (e.g., carbon, etc.) of a compound disclosed herein can exist in racemic or enantiomerically enriched form, such as (R)-, (S)-, or (R, S) -configuration presence. In certain embodiments, each asymmetric atom has at least a 50% enantiomeric excess in the (R)-or (S) -configuration, 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.
依据起始物料和方法的选择，本发明化合物可以以可能的异构体中的一个或它们的混合物，例如外消旋体和非对应异构体混合物(这取决于不对称碳原子的数量)的形式存在。光学活性的(R)-或(S)-异构体可使用手性合成子或手性试剂制备，或使用常规技术拆分。如果化合物含有一个双键，取代基可能为E或Z构型；如果化合物中含有二取代的环烷基，环烷基的取代基可能有顺式或反式构型。Depending on the choice of starting materials and methods, the compounds of the invention may be in one of the possible isomers or mixtures thereof, such as racemates and non-corresponding isomer mixtures (depending on the number of asymmetric carbon atoms) Exists in the form. 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 substituent may be in the E or Z configuration; if the compound contains a disubstituted cycloalkyl group, the substituent of the cycloalkyl group may have a cis or trans configuration.
所得的任何立体异构体的混合物可以依据组分物理化学性质上的差异被分离成纯的或基本纯的几何异构体，对映异构体，非对映异构体，例如，通过色谱法和/或分步结晶法。The resulting mixture of any stereoisomers can be separated into pure or substantially pure geometric isomers, enantiomers, diastereomers, for example, by chromatography, based on differences in the physicochemical properties of the components. And / or fractional crystallization.
可以用已知的方法将任何所得终产物或中间体的外消旋体通过本领域技术人员熟悉的方法拆分成光学对映体，如，通过对获得的其非对映异构的盐进行分离。外消旋的产物也可以通过手性色谱来分离，如，使用手性吸附剂的高效液相色谱(HPLC)。特别地，对映异构体可以通过不对称合成制备。The racemates of any of the resulting end products or intermediates can be resolved into optical enantiomers by methods known to those skilled in the art using known methods, for example, by subjecting the diastereomeric salts obtained Separation. Racemic products can also be separated by chiral chromatography, such as high performance liquid chromatography (HPLC) using a chiral adsorbent. In particular, enantiomers can be prepared by asymmetric synthesis.
像本发明所描述的，本发明的化合物可以任选地被一个或多个取代基所取代，如上面的通式化合物，或者像实施例里面特殊的例子，子类，和本发明所包含的一类化合物。应了解“任选取代的”这个术语与 “取代或非取代的”这个术语可以交换使用。一般而言，术语“取代的”表示所给结构中的一个或多个氢原子被具体取代基所取代。除非其他方面表明，一个任选的取代基团可以在基团各个可取代的位置进行取代。当所给出的结构式中不只一个位置能被选自具体基团的一个或多个取代基所取代，那么取代基可以相同或不同地在各个位置取代。具体地，“一个或多个”的实例是指1、2、3、4、5、6、7、8、9或10个。其中所述的取代基可以是，但并不限于，氘，氟，氯，溴，碘，氰基，羟基，硝基，氨基，羧基，烷基，烷氧基，烷氧基烷基，烷氧基烷氧基，烷氧基烷氨基，芳氧基，杂芳基氧基，杂环基氧基，芳基烷氧基，杂芳基烷氧基，杂环基烷氧基，环烷基烷氧基，烷氨基，烷氨基烷基，烷氨基烷氨基，环烷基氨基，环烷基烷氨基，烷硫基，卤代烷基，卤代烷氧基，羟基取代的烷基，羟基取代的烷氨基，氰基取代的烷基，氰基取代的烷氧基，氰基取代的烷氨基，氨基取代的烷基，烷基酰基，杂烷基，环烷基，环烯基，环烷基烷基，杂环基，杂环基烷基，杂环基酰基，芳基，芳基烷基，芳氨基，杂芳基，杂芳基烷基，杂芳基氨基，酰胺基，磺酰基，氨基磺酰基等等。As described in the present invention, the compounds of the present invention may be optionally substituted with one or more substituents, such as the compounds of the general formula above, or like the specific examples, subclasses in the examples, and the compounds included in the present invention. A class of compounds. It is understood that the term "optionally substituted" is 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 specific substituent. Unless otherwise indicated, an optional substituent group may be substituted at each substitutable 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, the examples of "one or more" refer to 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10. The substituents may be, but are not limited to, deuterium, fluorine, chlorine, bromine, iodine, cyano, hydroxyl, nitro, amino, carboxyl, alkyl, alkoxy, alkoxyalkyl, alkane Oxyalkoxy, alkoxyalkylamino, aryloxy, heteroaryloxy, heterocyclyloxy, arylalkoxy, heteroarylalkoxy, heterocyclylalkoxy, cycloalkane Alkylalkoxy, alkylamino, alkylaminoalkyl, alkylaminoalkylamino, cycloalkylamino, cycloalkylalkylamino, alkylthio, haloalkyl, haloalkoxy, hydroxy-substituted alkyl, hydroxy-substituted alkyl Amino, cyano-substituted alkyl, cyano-substituted alkoxy, cyano-substituted alkylamino, amino-substituted alkyl, alkylacyl, heteroalkyl, cycloalkyl, cycloalkenyl, cycloalkylalkane , Heterocyclyl, heterocyclylalkyl, heterocyclylacyl, aryl, arylalkyl, arylamino, heteroaryl, heteroarylalkyl, heteroarylamino, amido, sulfonyl, amino Sulfonyl and more.
另外，需要说明的是，除非以其他方式明确指出，在本发明中所采用的描述方式“各…独立地为”与“…各自独立地为”和“…独立地为”可以互换，均应做广义理解，其既可以是指在不同基团中，相同符号之间所表达的具体选项之间互相不影响，也可以表示在相同的基团中，相同符号之间所表达的具体选项之间互相不影响。In addition, it should be noted that unless explicitly stated otherwise, the description methods used in the present invention "each independently are" and "... each independently are" and "... independently are" are interchangeable, both It should be understood in a broad sense, which can mean that the specific options expressed between the same symbols in different groups do not affect each other, or that the specific options expressed between the same symbols in the same group Do not affect each other.
在本说明书的各部分，本发明公开化合物的取代基按照基团种类或范围公开。特别指出，本发明包括这些基团种类和范围的各个成员的每一个独立的次级组合。例如，术语“C 1-C 6烷基”或“C 1-6烷基”特别指独立公开的甲基、乙基、C 3烷基、C 4烷基、C 5烷基和C 6烷基。 In each part of the present specification, the substituents of the compounds disclosed in the present invention are disclosed according to the kind or scope of the group. In particular, the present invention includes each independent subcombination of each member of these group types and ranges. For example, the terms “C 1 -C 6 alkyl” or “C 1-6 alkyl” specifically refer to independently disclosed methyl, ethyl, C 3 alkyl, C 4 alkyl, C 5 alkyl, and C 6 alkyl base.
本发明使用的术语“烷基”或“烷基基团”，表示含有1至20个碳原子，饱和的直链或支链一价烃基基团；其中所述烷基基团任选地被一个或多个本发明描述的取代基所取代。除非另外详细说明，烷基基团含有1-20个碳原子。在一实施方案中，烷基基团含有1-12个碳原子；在一实施方案中，烷基基团含有1-8个碳原子；在另一实施方案中，烷基基团含有1-6个碳原子；在又一实施方案中，烷基基团含有1-4个碳原子；还在一实施方案中，烷基基团含有1-3个碳原子。The term "alkyl" or "alkyl group" as used herein means a saturated straight or branched chain monovalent hydrocarbon group containing from 1 to 20 carbon atoms; wherein said alkyl group is optionally It is substituted with one or more substituents described in the present invention. Unless otherwise specified, alkyl groups contain 1-20 carbon atoms. In one embodiment, the alkyl group contains 1-12 carbon atoms; in one embodiment, the alkyl group contains 1-8 carbon atoms; in another embodiment, the alkyl group contains 1- 6 carbon atoms; in yet another embodiment, the alkyl group contains 1-4 carbon atoms; and in still another embodiment, the alkyl group contains 1-3 carbon atoms.
烷基基团的实例包含，但并不限于，甲基(Me、-CH 3)，乙基(Et、-CH 2CH 3)，正丙基(n-Pr、-CH 2CH 2CH 3)，异丙基(i-Pr、-CH(CH 3) 2)，正丁基(n-Bu、-CH 2CH 2CH 2CH 3)，异丁基(i-Bu、-CH 2CH(CH 3) 2)，仲丁基(s-Bu、-CH(CH 3)CH 2CH 3)，叔丁基(t-Bu、-C(CH 3) 3)，正戊基(-CH 2CH 2CH 2CH 2CH 3)，2-戊基(-CH(CH 3)CH 2CH 2CH 3)，3-戊基(-CH(CH 2CH 3) 2)，2-甲基-2-丁基(-C(CH 3) 2CH 2CH 3)，3-甲基-2-丁基(-CH(CH 3)CH(CH 3) 2)，3-甲基-1-丁基(-CH 2CH 2CH(CH 3) 2)，2-甲基-1-丁基(-CH 2CH(CH 3)CH 2CH 3)，等等。 Examples of alkyl groups include, but are not limited to, methyl (Me, -CH 3 ), ethyl (Et, -CH 2 CH 3 ), n-propyl (n-Pr, -CH 2 CH 2 CH 3 ), Isopropyl (i-Pr, -CH (CH 3 ) 2 ), n-butyl (n-Bu, -CH 2 CH 2 CH 2 CH 3 ), isobutyl (i-Bu, -CH 2 CH (CH 3 ) 2 ), sec-butyl (s-Bu, -CH (CH 3 ) CH 2 CH 3 ), tert-butyl (t-Bu, -C (CH 3 ) 3 ), n-pentyl (-CH 2 CH 2 CH 2 CH 2 CH 3 ), 2-pentyl (-CH (CH 3 ) CH 2 CH 2 CH 3 ), 3-pentyl (-CH (CH 2 CH 3 ) 2 ), 2-methyl 2-butyl (-C (CH 3 ) 2 CH 2 CH 3 ), 3-methyl-2-butyl (-CH (CH 3 ) CH (CH 3 ) 2 ), 3-methyl-1- Butyl (-CH 2 CH 2 CH (CH 3 ) 2 ), 2-methyl-1-butyl (-CH 2 CH (CH 3 ) CH 2 CH 3 ), and so on.
术语“烷氧基”表示烷基基团通过氧原子与分子其余部分相连，其中烷基基团具有如本发明所述的含义。烷氧基基团的实例包括，但并不限于，甲氧基(MeO、-OCH 3)，乙氧基(EtO、-OCH 2CH 3)，1-丙氧基(n-PrO、n-丙氧基、-OCH 2CH 2CH 3)，2-丙氧基(i-PrO、i-丙氧基、-OCH(CH 3) 2)等等。 The term "alkoxy" means that an alkyl group is connected to the rest of the molecule through an oxygen atom, wherein the alkyl group has the meaning as described in the present invention. Examples of alkoxy groups include, but are not limited to, methoxy (MeO, -OCH 3 ), ethoxy (EtO, -OCH 2 CH 3 ), 1-propoxy (n-PrO, n- Propoxy, -OCH 2 CH 2 CH 3 ), 2-propoxy (i-PrO, i-propoxy, -OCH (CH 3 ) 2 ) and the like.
术语“卤素”是指氟(F)、氯(Cl)、溴(Br)或碘(I)。The term "halogen" refers to fluorine (F), chlorine (Cl), bromine (Br), or iodine (I).
术语“芳基”表示含有6-14个环原子，或6-12个环原子，或6-10个环原子的单环、双环和三环的碳环体系，其中，至少一个环体系是芳香族的，其中每一个环体系包含3-7个原子组成的环，且有一个或多个附着点与分子的其余部分相连。术语“芳基”可以和术语“芳香环”交换使用。芳基基团的实例可以包括苯基，茚基，萘基和蒽基。所述芳基基团任选地被一个或多个本发明所描述的取代基所取代。The term "aryl" means a monocyclic, bicyclic, and tricyclic carbocyclic ring system containing 6-14 ring atoms, or 6-12 ring atoms, or 6-10 ring atoms, wherein at least one ring system is aromatic Family, where each ring system contains a ring of 3-7 atoms and has one or more attachment points connected to the rest of the molecule. The term "aryl" may be used interchangeably with the term "aromatic ring". Examples of the aryl group may include phenyl, indenyl, naphthyl, and anthracenyl. The aryl group is optionally substituted with one or more substituents described herein.
术语“芳氧基”表示芳基基团通过氧原子与分子其余部分相连，其中芳基基团具有如本发明所述的含义。The term "aryloxy" means that an aryl group is connected to the rest of the molecule through an oxygen atom, wherein the aryl group has the meaning as described in the present invention.
术语“杂芳基”表示含有5-12个环原子，或5-10个环原子，或5-6个环原子的单环、双环和三环体系，其中至少一个环体系是芳香族的，且至少一个环体系包含一个或多个杂原子，其中每一个环体系包含 5-7个原子组成的环，且有一个或多个附着点与分子其余部分相连。术语“杂芳基”可以与术语“杂芳环”或“杂芳族化合物”交换使用。所述杂芳基基团任选地被一个或多个本发明所描述的取代基所取代。在一实施方案中，5-10个原子组成的杂芳基包含1，2，3或4个独立选自O，S和N的杂原子。The term "heteroaryl" means monocyclic, bicyclic, and tricyclic systems containing 5-12 ring atoms, or 5-10 ring atoms, or 5-6 ring atoms, at least one of which is aromatic, And at least one ring system contains one or more heteroatoms, wherein each ring system contains a ring of 5-7 atoms, and there are one or more attachment points connected to the rest of the molecule. The term "heteroaryl" may be used interchangeably with the term "heteroaromatic ring" or "heteroaromatic compound". The heteroaryl group is optionally substituted with one or more substituents described herein. In one embodiment, a heteroaryl group of 5-10 atoms comprises 1, 2, 3 or 4 heteroatoms independently selected from O, S and N.
术语“卤代烷基”表示烷基基团被一个或多个卤素原子所取代，这样的实例包含，但并不限于，-CF 3，-CHF 2，-CH 2Cl，-CH 2CF 3，-CH 2CHF 2，-CH 2CH 2CF 3等。 The term "haloalkyl" denotes an alkyl group is substituted with one or more halogen atoms, such examples include, but are not limited to, -CF 3, -CHF 2, -CH 2 Cl, -CH 2 CF 3, - CH 2 CHF 2 , -CH 2 CH 2 CF 3 and the like.
术语“卤代烷氧基”表示烷氧基基团被一个或多个卤素原子所取代，这样的实例包含，但并不限于，-OCF 3，-OCHF 2，-OCHCl 2，-OCH 2CHF 2，-OCH 2CHCl 2，-OCH(CH 3)CHF 2等。 The term "haloalkoxy" means that an alkoxy group is substituted with one or more halogen atoms. Such examples include, but are not limited to, -OCF 3 , -OCHF 2 , -OCHCl 2 , -OCH 2 CHF 2 , -OCH 2 CHCl 2 , -OCH (CH 3 ) CHF 2 and the like.
术语“烷基胺基”或“烷胺基”包括“N-烷基胺基”和“N,N-二烷基胺基”，其中氨基基团分别独立地被一个或两个烷基基团所取代。其中一些实施例是，烷基胺基是一个或两个C 1-6烷基连接到氮原子上的较低级的烷基胺基基团。另外一些实施例是，烷基胺基是C 1-4烷基连接到氮原子上的较低级的烷基胺基基团。合适的烷基胺基基团可以是单烷基胺基或二烷基胺基，这样的实例包括，但并不限于，N-甲基胺基，N-乙基胺基，N,N-二甲基胺基，N,N-二乙基胺基等等。 The term "alkylamino" or "alkylamino" includes "N-alkylamino" and "N, N-dialkylamino", wherein the amino groups are each independently replaced by one or two alkyl groups Group replaced. Some of these embodiments are that the alkylamino group is a lower alkylamino group having one or two C1-6 alkyl groups attached to a nitrogen atom. In other embodiments, the alkylamino group is a lower alkylamino group having a C 1-4 alkyl group attached to a nitrogen atom. Suitable alkylamino groups may be monoalkylamino or dialkylamino, such examples include, but are not limited to, N-methylamino, N-ethylamino, N, N- Dimethylamino, N, N-diethylamino and the like.
术语“烷硫基”表示烷基基团通过硫原子与分子其余部分相连，其中烷基基团具有如本发明所述的含义。烷硫基基团的实例包括，但并不限于，甲硫基(MeS、-SCH 3)，乙硫基(EtS、-SCH 2CH 3)，1-丙硫基(n-PrS、n-丙硫基、-SCH 2CH 2CH 3)，2-丙硫基(i-PrS、i-丙硫基、-SCH(CH 3) 2)等等。 The term "alkylthio" means that an alkyl group is connected to the rest of the molecule through a sulfur atom, wherein the alkyl group has the meaning as described in the present invention. Examples of alkylthio groups include, but are not limited to, methylthio (MeS, -SCH 3 ), ethylthio (EtS, -SCH 2 CH 3 ), 1-propylthio (n-PrS, n- Propionyl, -SCH 2 CH 2 CH 3 ), 2-propylthio (i-PrS, i-propylthio, -SCH (CH 3 ) 2 ) and the like.
在本发明所述的噁二唑类肟衍生物中的肟部位中，存在(Z)体和(E)体的立体结构，这两个立体异构体及其混合物都包含在本发明中。这两个立体异构体可以根据本领域技术人员所熟知的方法进行分离。In the oxime site in the oxadiazole oxime derivative according to the present invention, there are stereostructures of the (Z) form and the (E) form, and both of the stereoisomers and mixtures thereof are included in the present invention. These two stereoisomers can be separated according to methods well known to those skilled in the art.
本发明所述化合物的盐，包括衍生自碱金属或碱土金属的那些以及衍生自氨和胺的那些。优选的阳离子包括钠、钾、镁以及具有化学式N +(R AR BR CR D)的铵阳离子，其中R A、R B、R C和R D独立地选自氢、C 1-C 6烷基和C 1-C 6羟基烷基。具有式(I-A)、式(I)、式(II)或式(III)的化合物的盐可以通过用金属氢氧化物(例如氢氧化钠)或胺(例如氨、三甲胺、二乙醇胺、2-甲硫基丙胺、双烯丙基胺、2-丁氧基乙胺、吗啉、环十二胺或苄胺)对具有式(I-A)、式(I)、式(II)或式(III)的化合物进行处理来制备。 Salts of the compounds of the invention include those derived from alkali or alkaline earth metals and those derived from ammonia and amines. Preferred cations include sodium, potassium, magnesium, and ammonium cations having the chemical formula N + (R A R B R C R D ), wherein R A , R B , R C and R D are independently selected from hydrogen, C 1 -C 6 alkyl and C 1 -C 6 hydroxyalkyl. Salts of compounds having formula (IA), formula (I), formula (II) or formula (III) can be obtained by using a metal hydroxide (e.g., sodium hydroxide) or an amine (e.g., ammonia, trimethylamine, diethanolamine, 2 -Methylthiopropylamine, diallylamine, 2-butoxyethylamine, morpholine, cyclododecylamine, or benzylamine) pairs having formula (IA), formula (I), formula (II), or formula ( The compounds of III) are prepared by treatment.
当本发明的化合物包含一个碱部分时，可接受的盐可以由有机酸和无机酸形成，例如乙酸、丙酸、乳酸、柠檬酸、酒石酸、琥珀酸、富马酸、马来酸、丙二酸、扁桃酸、苹果酸、邻苯二甲酸、盐酸、氢溴酸、磷酸、硝酸、硫酸、甲磺酸、萘磺酸、苯磺酸、甲苯磺酸、樟脑磺酸以及类似地已知可接受的酸。When the compound of the present invention contains a basic moiety, 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 Acids, 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 Accepted acid.
本发明化合物的详细描述Detailed description of the compounds of the invention
本发明的目的在于提供一种对防治植物病原性真菌有显著效果的化合物、含有该化合物的组合物和制剂及其作为杀真菌剂的应用。The object of the present invention is to provide a compound having a significant effect on controlling phytopathogenic fungi, a composition and a preparation containing the compound, and an application thereof as a fungicide.
一方面，本发明提供一种化合物，其为具有式(I-A)所示的化合物或式(I-A)所示的化合物的盐、氮氧化物、或(E)和(Z)异构体以及它们的混合物：In one aspect, the present invention provides a compound having a compound represented by Formula (IA) or a salt, nitrogen oxide, or (E) and (Z) isomers of a compound represented by Formula (IA), and mixture:
Figure PCTCN2019091137-appb-000022
Figure PCTCN2019091137-appb-000022
其中，among them,
T为含有1、2、3或4个氮原子的5元杂芳基；其中，所述的5元杂芳基任选地被一个或多个烷基取代；T is a 5-membered heteroaryl group containing 1, 2, 3, or 4 nitrogen atoms; wherein the 5-membered heteroaryl group is optionally substituted with one or more alkyl groups;
A为芳基或杂芳基；其中A任选地被1、2、3、4、5或6个R b取代； A is aryl or heteroaryl; wherein A is optionally substituted with 1, 2, 3, 4, 5 or 6 R b ;
其中，各R b独立地为卤素、羟基、氰基、硝基、氨基、羧基、烷基、烷氧基、卤代烷基、卤代烷氧 基、芳基或芳氧基； Wherein each R b is independently halogen, hydroxy, cyano, nitro, amino, carboxyl, alkyl, alkoxy, haloalkyl, haloalkoxy, aryl or aryloxy;
B 1为CR 1或N； B 1 is CR 1 or N;
B为CR 2或N； B is CR 2 or N;
B 2为CR 3或N； B 2 is CR 3 or N;
条件为：B 1、B和B 2中至多有一个为N； Provided that at least one of B 1 , B and B 2 is N;
R 1、R 2、R 3、R 4和R 5各自独立地为氢、卤素、羟基、氰基、硝基、氨基、羧基、烷基、卤代烷基、烷氧基或卤代烷氧基； R 1 , R 2 , R 3 , R 4 and R 5 are each independently hydrogen, halogen, hydroxyl, cyano, nitro, amino, carboxyl, alkyl, haloalkyl, alkoxy or haloalkoxy;
或R 1、R 2、R 3、R 4和R 5各自独立地为以下子结构式： Or R 1 , R 2 , R 3 , R 4 and R 5 are each independently the following substructure formula:
Figure PCTCN2019091137-appb-000023
Figure PCTCN2019091137-appb-000023
其中，R 11、R 22、R 33、R 44和R 55各自独立地为氢、卤素、羟基、氰基、硝基、氨基、羧基、烷基、卤代烷基、烷氧基、卤代烷氧基、烷基胺基或烷硫基； Among them, R 11 , R 22 , R 33 , R 44 and R 55 are each independently hydrogen, halogen, hydroxyl, cyano, nitro, amino, carboxyl, alkyl, haloalkyl, alkoxy, haloalkoxy, Alkylamino or alkylthio;
条件为：R 1、R 2、R 3、R 4和R 5中有且只有一个为
Figure PCTCN2019091137-appb-000024
The conditions are: there is only one of R 1 , R 2 , R 3 , R 4 and R 5 is
Figure PCTCN2019091137-appb-000024
在一些实施方案中，本发明提供一种式(I)所示的化合物或式(I)所示的化合物的盐、氮氧化物、或(E)和(Z)异构体以及它们的混合物：In some embodiments, the present invention provides a compound represented by formula (I) or a salt, nitrogen oxide, or (E) and (Z) isomers of a compound represented by formula (I), and mixtures thereof :
Figure PCTCN2019091137-appb-000025
Figure PCTCN2019091137-appb-000025
其中，among them,
T为含有1、2、3或4个氮原子的5元杂芳基；其中，所述的5元杂芳基任选地一个或多个被烷基取代；T is a 5-membered heteroaryl group containing 1, 2, 3 or 4 nitrogen atoms; wherein, the 5-membered heteroaryl group is optionally substituted with one or more alkyl groups;
A为芳基或杂芳基；其中A任选地被1、2、3、4、5或6个R b取代； A is aryl or heteroaryl; wherein A is optionally substituted with 1, 2, 3, 4, 5 or 6 R b ;
其中，各R b独立地为卤素、羟基、氰基、硝基、氨基、羧基、烷基、烷氧基、卤代烷基、卤代烷氧基、芳基或芳氧基； Wherein each R b is independently halogen, hydroxy, cyano, nitro, amino, carboxyl, alkyl, alkoxy, haloalkyl, haloalkoxy, aryl or aryloxy;
R 1、R 2、R 3、R 4和R 5各自独立地为氢、卤素、羟基、氰基、硝基、氨基、羧基、烷基、卤代烷基、烷氧基或卤代烷氧基； R 1 , R 2 , R 3 , R 4 and R 5 are each independently hydrogen, halogen, hydroxyl, cyano, nitro, amino, carboxyl, alkyl, haloalkyl, alkoxy or haloalkoxy;
或R 1、R 2、R 3、R 4和R 5各自独立地为以下子结构式： Or R 1 , R 2 , R 3 , R 4 and R 5 are each independently the following substructure formula:
Figure PCTCN2019091137-appb-000026
Figure PCTCN2019091137-appb-000026
其中，R 11、R 22、R 33、R 44和R 55各自独立地为氢、卤素、羟基、氰基、硝基、氨基、羧基、烷基、卤代烷基、烷氧基、卤代烷氧基、烷基胺基或烷硫基； Among them, R 11 , R 22 , R 33 , R 44 and R 55 are each independently hydrogen, halogen, hydroxyl, cyano, nitro, amino, carboxyl, alkyl, haloalkyl, alkoxy, haloalkoxy, Alkylamino or alkylthio;
条件为：R 1、R 2、R 3、R 4和R 5中有且只有一个为
Figure PCTCN2019091137-appb-000027
The conditions are: there is only one of R 1 , R 2 , R 3 , R 4 and R 5 is
Figure PCTCN2019091137-appb-000027
在一些实施方案中，T为含有1、2、3或4个氮原子的5元杂芳基；其中，所述的5元杂芳基任选地被一个或多个C 1-6烷基取代。 In some embodiments, T is a 5-membered heteroaryl group containing 1, 2, 3, or 4 nitrogen atoms; wherein said 5-membered heteroaryl group is optionally substituted by one or more C 1-6 alkyl groups. To replace.
还在另一些实施方案中，T为以下子结构式：In still other embodiments, T is the following substructure formula:
Figure PCTCN2019091137-appb-000028
Figure PCTCN2019091137-appb-000028
其中，W、X、Y、Z和V各自独立地为C(R a) m或N(R a) q； Wherein W, X, Y, Z and V are each independently C (R a ) m or N (R a ) q ;
条件为：W、X、Y、Z和V至少一个为N(R a) q； Provided that at least one of W, X, Y, Z and V is N (R a ) q ;
其中，m和q各自独立地为0或1；Where m and q are each independently 0 or 1;
其中，各R a独立地为氢或C 1-6烷基。 Wherein each R a is independently hydrogen or C 1-6 alkyl.
还在另一些实施方案中，T为以下子结构式：In still other embodiments, T is the following substructure formula:
Figure PCTCN2019091137-appb-000029
Figure PCTCN2019091137-appb-000029
其中，W、X、Y、Z和V各自独立地为C(R a) m或N(R a) q； Wherein W, X, Y, Z and V are each independently C (R a ) m or N (R a ) q ;
条件为：W、X、Y、Z和V至少一个为N(R a) q； Provided that at least one of W, X, Y, Z and V is N (R a ) q ;
其中，m和q各自独立地为0或1；Where m and q are each independently 0 or 1;
其中，各R a独立地为氢或C 1-4烷基。 Wherein each R a is independently hydrogen or C 1-4 alkyl.
还在另一些实施方案中，T为以下子结构式：In still other embodiments, T is the following substructure formula:
Figure PCTCN2019091137-appb-000030
Figure PCTCN2019091137-appb-000030
其中，各R a独立地为氢或C 1-4烷基。 Wherein each R a is independently hydrogen or C 1-4 alkyl.
还在另一些实施方案中，T为以下子结构式：In still other embodiments, T is the following substructure formula:
Figure PCTCN2019091137-appb-000031
Figure PCTCN2019091137-appb-000031
其中，各R a独立地为氢、-CH 3或-CH 2CH 3。 However, each R a is independently hydrogen, -CH 3 or -CH 2 CH 3 .
在一些实施方案中，A为C 6-10芳基或5-10元杂芳基；其中A任选地被1、2、3、4、5或6个R b取代； In some embodiments, A is C 6-10 aryl or 5-10 membered heteroaryl; wherein A is optionally substituted with 1, 2, 3, 4, 5 or 6 R b ;
其中，各R b独立地为卤素、羟基、氰基、硝基、氨基、羧基、C 1-6烷基、C 1-6烷氧基、卤代C 1-6烷基、卤代C 1-6烷氧基、C 6-10芳基或C 6-10芳氧基。 Wherein each R b is independently halogen, hydroxy, cyano, nitro, amino, carboxyl, C 1-6 alkyl, C 1-6 alkoxy, halo C 1-6 alkyl, halo C 1 -6 alkoxy, C 6-10 aryl or C 6-10 aryloxy.
在另一些实施方案中，A为以下子结构式：In other embodiments, A is the following substructure formula:
Figure PCTCN2019091137-appb-000032
Figure PCTCN2019091137-appb-000032
其中，z为0、1、2、3、4或5；Where z is 0, 1, 2, 3, 4 or 5;
其中，各R b独立地为卤素、羟基、氰基、硝基、氨基、羧基、C 1-4烷基、C 1-4烷氧基、卤代C 1-4烷基、卤代C 1-4烷氧基、C 6-10芳基或C 6-10芳氧基。 Wherein each R b is independently halogen, hydroxy, cyano, nitro, amino, carboxyl, C 1-4 alkyl, C 1-4 alkoxy, halo C 1-4 alkyl, halo C 1 -4 alkoxy, C 6-10 aryl or C 6-10 aryloxy.
还在另一些实施方案中，A为以下子结构式：In still other embodiments, A is the following substructure formula:
Figure PCTCN2019091137-appb-000033
Figure PCTCN2019091137-appb-000033
其中，z为0、1、2、3、4或5；Where z is 0, 1, 2, 3, 4 or 5;
其中，各R b独立地为氟、氯、溴、碘、羟基、氰基、硝基、氨基、羧基、-CH 3、-CH 2CH 3、-CH 2CH 2CH 3、-CH(CH 3) 2、-CH 2CH 2CH 2CH 3、-C(CH 3) 3、-OCH 3、-OCH 2CH 3、-OCH 2CH 2CH 3、-OCH(CH 3) 2、-OC(CH 3) 3、-CHF 2、-CF 3或-OCF 3。 Among them, each R b is independently fluorine, chlorine, bromine, iodine, hydroxyl, cyano, nitro, amino, carboxyl, -CH 3 , -CH 2 CH 3 , -CH 2 CH 2 CH 3 , -CH (CH 3 ) 2 , -CH 2 CH 2 CH 2 CH 3 , -C (CH 3 ) 3 , -OCH 3 , -OCH 2 CH 3 , -OCH 2 CH 2 CH 3 , -OCH (CH 3 ) 2 , -OC (CH 3 ) 3 , -CHF 2 , -CF 3 or -OCF 3 .
在一些实施方案中，R 1为氢、卤素、羟基、氰基、硝基、氨基、羧基、C 1-6烷基、卤代C 1-6烷基、C 1-6烷氧基或卤代C 1-6烷氧基。 In some embodiments, R 1 is hydrogen, halogen, hydroxy, cyano, nitro, amino, carboxy, C 1-6 alkyl, halo C 1-6 alkyl, C 1-6 alkoxy, or halogen C 1-6 alkoxy.
在另一些实施方案中，R 1为氢、卤素、羟基、氰基、硝基、氨基、羧基、C 1-4烷基、卤代C 1-4烷基、C 1-4烷氧基或卤代C 1-4烷氧基。 In other embodiments, R 1 is hydrogen, halogen, hydroxy, cyano, nitro, amino, carboxyl, C 1-4 alkyl, halo C 1-4 alkyl, C 1-4 alkoxy, or Halo C 1-4 alkoxy.
还在另一些实施方案中，R 1为氢、氟、氯、溴、碘、羟基、氰基、硝基、氨基、羧基、-CH 3、-CH 2CH 3、-CH 2CH 2CH 3、-CH(CH 3) 2、-CH 2CH 2CH 2CH 3、-C(CH 3) 3、-CH 2Cl、-CHF 2、-CF 3、-OCH 3、-OCH 2CH 3、-OCH 2CH 2CH 3、-OCH(CH 3) 2、-OC(CH 3) 3或-OCF 3。 In still other embodiments, R 1 is hydrogen, fluorine, chlorine, bromine, iodine, hydroxyl, cyano, nitro, amino, carboxyl, -CH 3 , -CH 2 CH 3 , -CH 2 CH 2 CH 3 , -CH (CH 3 ) 2 , -CH 2 CH 2 CH 2 CH 3 , -C (CH 3 ) 3 , -CH 2 Cl, -CHF 2 , -CF 3 , -OCH 3 , -OCH 2 CH 3 , -OCH 2 CH 2 CH 3 , -OCH (CH 3 ) 2 , -OC (CH 3 ) 3 or -OCF 3 .
在一些实施方案中，R 2为氢、卤素、羟基、氰基、硝基、氨基、羧基、C 1-6烷基、卤代C 1-6烷基、C 1-6烷氧基或卤代C 1-6烷氧基。 In some embodiments, R 2 is hydrogen, halogen, hydroxy, cyano, nitro, amino, carboxyl, C 1-6 alkyl, halo C 1-6 alkyl, C 1-6 alkoxy, or halo C 1-6 alkoxy.
在另一些实施方案中，R 2为氢、卤素、羟基、氰基、硝基、氨基、羧基、C 1-4烷基、卤代C 1-4烷基、C 1-4烷氧基或卤代C 1-4烷氧基。 In other embodiments, R 2 is hydrogen, halogen, hydroxy, cyano, nitro, amino, carboxy, C 1-4 alkyl, halo C 1-4 alkyl, C 1-4 alkoxy, or Halo C 1-4 alkoxy.
还在另一些实施方案中，R 2为氢、氟、氯、溴、碘、羟基、氰基、硝基、氨基、羧基、-CH 3、-CH 2CH 3、-CH 2CH 2CH 3、-CH(CH 3) 2、-CH 2CH 2CH 2CH 3、-C(CH 3) 3、-CH 2Cl、-CHF 2、-CF 3、-OCH 3、-OCH 2CH 3、-OCH 2CH 2CH 3、-OCH(CH 3) 2、-OC(CH 3) 3或-OCF 3。 In still other embodiments, R 2 is hydrogen, fluorine, chlorine, bromine, iodine, hydroxyl, cyano, nitro, amino, carboxyl, -CH 3 , -CH 2 CH 3 , -CH 2 CH 2 CH 3 , -CH (CH 3 ) 2 , -CH 2 CH 2 CH 2 CH 3 , -C (CH 3 ) 3 , -CH 2 Cl, -CHF 2 , -CF 3 , -OCH 3 , -OCH 2 CH 3 , -OCH 2 CH 2 CH 3 , -OCH (CH 3 ) 2 , -OC (CH 3 ) 3 or -OCF 3 .
在一些实施方案中，R 3为氢、卤素、羟基、氰基、硝基、氨基、羧基、C 1-6烷基、卤代C 1-6烷基、C 1-6烷氧基或卤代C 1-6烷氧基。 In some embodiments, R 3 is hydrogen, halogen, hydroxy, cyano, nitro, amino, carboxyl, C 1-6 alkyl, halo C 1-6 alkyl, C 1-6 alkoxy, or halo C 1-6 alkoxy.
在另一些实施方案中，R 3为氢、卤素、羟基、氰基、硝基、氨基、羧基、C 1-4烷基、卤代C 1-4烷基、C 1-4烷氧基或卤代C 1-4烷氧基。 In other embodiments, R 3 is hydrogen, halogen, hydroxy, cyano, nitro, amino, carboxyl, C 1-4 alkyl, halo C 1-4 alkyl, C 1-4 alkoxy, or Halo C 1-4 alkoxy.
还在另一些实施方案中，R 3为氢、氟、氯、溴、碘、羟基、氰基、硝基、氨基、羧基、-CH 3、-CH 2CH 3、-CH 2CH 2CH 3、-CH(CH 3) 2、-CH 2CH 2CH 2CH 3、-C(CH 3) 3、-CH 2Cl、-CHF 2、-CF 3、-OCH 3、-OCH 2CH 3、-OCH 2CH 2CH 3、-OCH(CH 3) 2、-OC(CH 3) 3或-OCF 3。 In still other embodiments, R 3 is hydrogen, fluorine, chlorine, bromine, iodine, hydroxyl, cyano, nitro, amino, carboxyl, -CH 3 , -CH 2 CH 3 , -CH 2 CH 2 CH 3 , -CH (CH 3 ) 2 , -CH 2 CH 2 CH 2 CH 3 , -C (CH 3 ) 3 , -CH 2 Cl, -CHF 2 , -CF 3 , -OCH 3 , -OCH 2 CH 3 , -OCH 2 CH 2 CH 3 , -OCH (CH 3 ) 2 , -OC (CH 3 ) 3 or -OCF 3 .
在一些实施方案中，R 4为氢、卤素、羟基、氰基、硝基、氨基、羧基、C 1-6烷基、卤代C 1-6烷基、C 1-6烷氧基或卤代C 1-6烷氧基。 In some embodiments, R 4 is hydrogen, halogen, hydroxy, cyano, nitro, amino, carboxy, C 1-6 alkyl, halo C 1-6 alkyl, C 1-6 alkoxy, or halo C 1-6 alkoxy.
在另一些实施方案中，R 4为氢、卤素、羟基、氰基、硝基、氨基、羧基、C 1-4烷基、卤代C 1-4烷基、C 1-4烷氧基或卤代C 1-4烷氧基。 In other embodiments, R 4 is hydrogen, halogen, hydroxy, cyano, nitro, amino, carboxy, C 1-4 alkyl, halo C 1-4 alkyl, C 1-4 alkoxy, or Halo C 1-4 alkoxy.
还在另一些实施方案中，R 4为氢、氟、氯、溴、碘、羟基、氰基、硝基、氨基、羧基、-CH 3、-CH 2CH 3、-CH 2CH 2CH 3、-CH(CH 3) 2、-CH 2CH 2CH 2CH 3、-C(CH 3) 3、-CH 2Cl、-CHF 2、-CF 3、-OCH 3、-OCH 2CH 3、 -OCH 2CH 2CH 3、-OCH(CH 3) 2、-OC(CH 3) 3或-OCF 3。 In still other embodiments, R 4 is hydrogen, fluorine, chlorine, bromine, iodine, hydroxyl, cyano, nitro, amino, carboxyl, -CH 3 , -CH 2 CH 3 , -CH 2 CH 2 CH 3 , -CH (CH 3 ) 2 , -CH 2 CH 2 CH 2 CH 3 , -C (CH 3 ) 3 , -CH 2 Cl, -CHF 2 , -CF 3 , -OCH 3 , -OCH 2 CH 3 , -OCH 2 CH 2 CH 3 , -OCH (CH 3 ) 2 , -OC (CH 3 ) 3 or -OCF 3 .
在一些实施方案中，R 5为氢、卤素、羟基、氰基、硝基、氨基、羧基、C 1-6烷基、卤代C 1-6烷基、C 1-6烷氧基或卤代C 1-6烷氧基。 In some embodiments, R 5 is hydrogen, halogen, hydroxy, cyano, nitro, amino, carboxy, C 1-6 alkyl, halo C 1-6 alkyl, C 1-6 alkoxy, or halogen C 1-6 alkoxy.
在另一些实施方案中，R 5为氢、卤素、羟基、氰基、硝基、氨基、羧基、C 1-4烷基、卤代C 1-4烷基、C 1-4烷氧基或卤代C 1-4烷氧基。 In other embodiments, R 5 is hydrogen, halogen, hydroxy, cyano, nitro, amino, carboxy, C 1-4 alkyl, halo C 1-4 alkyl, C 1-4 alkoxy, or Halo C 1-4 alkoxy.
还在另一些实施方案中，R 5为氢、氟、氯、溴、碘、羟基、氰基、硝基、氨基、羧基、-CH 3、-CH 2CH 3、-CH 2CH 2CH 3、-CH(CH 3) 2、-CH 2CH 2CH 2CH 3、-C(CH 3) 3、-CH 2Cl、-CHF 2、-CF 3、-OCH 3、-OCH 2CH 3、-OCH 2CH 2CH 3、-OCH(CH 3) 2、-OC(CH 3) 3或-OCF 3。 In still other embodiments, R 5 is hydrogen, fluorine, chlorine, bromine, iodine, hydroxyl, cyano, nitro, amino, carboxyl, -CH 3 , -CH 2 CH 3 , -CH 2 CH 2 CH 3 , -CH (CH 3 ) 2 , -CH 2 CH 2 CH 2 CH 3 , -C (CH 3 ) 3 , -CH 2 Cl, -CHF 2 , -CF 3 , -OCH 3 , -OCH 2 CH 3 , -OCH 2 CH 2 CH 3 , -OCH (CH 3 ) 2 , -OC (CH 3 ) 3 or -OCF 3 .
还在一些实施方案中，R 1为以下子结构式： In some embodiments, R 1 is the following sub-structure formula:
Figure PCTCN2019091137-appb-000034
Figure PCTCN2019091137-appb-000034
其中，R 11、R 22、R 33、R 44和R 55各自独立地为氢、卤素、羟基、氰基、硝基、氨基、羧基、C 1-6烷基、卤代C 1-6烷基、C 1-6烷氧基、卤代C 1-6烷氧基、C 1-6烷基胺基或C 1-6烷硫基。 Among them, R 11 , R 22 , R 33 , R 44 and R 55 are each independently hydrogen, halogen, hydroxyl, cyano, nitro, amino, carboxyl, C 1-6 alkyl, halo C 1-6 alkane Alkyl, C 1-6 alkoxy, halo C 1-6 alkoxy, C 1-6 alkylamino or C 1-6 alkylthio.
还在另一些实施方案中，R 1为以下子结构式： In still other embodiments, R 1 is the following sub-structural formula:
Figure PCTCN2019091137-appb-000035
Figure PCTCN2019091137-appb-000035
其中，R 11、R 22、R 33、R 44和R 55各自独立地为氢、卤素、羟基、氰基、硝基、氨基、羧基、C 1-4烷基、卤代C 1-4烷基、C 1-4烷氧基、卤代C 1-4烷氧基、C 1-4烷基胺基或C 1-4烷硫基。 Among them, R 11 , R 22 , R 33 , R 44 and R 55 are each independently hydrogen, halogen, hydroxyl, cyano, nitro, amino, carboxyl, C 1-4 alkyl, halo C 1-4 alkane Alkyl, C 1-4 alkoxy, halo C 1-4 alkoxy, C 1-4 alkylamino or C 1-4 alkylthio.
还在另一些实施方案中，R 1为以下子结构式： In still other embodiments, R 1 is the following substructure formula:
Figure PCTCN2019091137-appb-000036
Figure PCTCN2019091137-appb-000036
其中，R 11、R 22、R 33、R 44和R 55各自独立地为氢、氟、氯、溴、碘、羟基、氰基、硝基、氨基、羧基、-CH 3、-CH 2CH 3、-CH 2CH 2CH 3、-CH(CH 3) 2、-CH 2CH 2CH 2CH 3、-C(CH 3) 3、-CF 3、-OCH 3、-OCH 2CH 3、-OCH 2CH 2CH 3、-OCH(CH 3) 2、-OC(CH 3) 3、-OCF 3、-N(CH 3) 2或-SCH 3。 Among them, R 11 , R 22 , R 33 , R 44 and R 55 are each independently hydrogen, fluorine, chlorine, bromine, iodine, hydroxyl, cyano, nitro, amino, carboxyl, -CH 3 , -CH 2 CH 3 , -CH 2 CH 2 CH 3 , -CH (CH 3 ) 2 , -CH 2 CH 2 CH 2 CH 3 , -C (CH 3 ) 3 , -CF 3 , -OCH 3 , -OCH 2 CH 3 , -OCH 2 CH 2 CH 3 , -OCH (CH 3 ) 2 , -OC (CH 3 ) 3 , -OCF 3 , -N (CH 3 ) 2 or -SCH 3 .
还在一些实施方案中，R 2为以下子结构式： In some embodiments, R 2 is the following substructure:
Figure PCTCN2019091137-appb-000037
Figure PCTCN2019091137-appb-000037
其中，R 11、R 22、R 33、R 44和R 55各自独立地为氢、卤素、羟基、氰基、硝基、氨基、羧基、C 1-6烷基、卤代C 1-6烷基、C 1-6烷氧基、卤代C 1-6烷氧基、C 1-6烷基胺基或C 1-6烷硫基。 Among them, R 11 , R 22 , R 33 , R 44 and R 55 are each independently hydrogen, halogen, hydroxyl, cyano, nitro, amino, carboxyl, C 1-6 alkyl, halo C 1-6 alkane Alkyl, C 1-6 alkoxy, halo C 1-6 alkoxy, C 1-6 alkylamino or C 1-6 alkylthio.
还在另一些实施方案中，R 2为以下子结构式： In still other embodiments, R 2 is the following sub-structural formula:
Figure PCTCN2019091137-appb-000038
Figure PCTCN2019091137-appb-000038
其中，R 11、R 22、R 33、R 44和R 55各自独立地为氢、卤素、羟基、氰基、硝基、氨基、羧基、C 1-4烷基、卤代C 1-4烷基、C 1-4烷氧基、卤代C 1-4烷氧基、C 1-4烷基胺基或C 1-4烷硫基。 Among them, R 11 , R 22 , R 33 , R 44 and R 55 are each independently hydrogen, halogen, hydroxyl, cyano, nitro, amino, carboxyl, C 1-4 alkyl, halo C 1-4 alkane Alkyl, C 1-4 alkoxy, halo C 1-4 alkoxy, C 1-4 alkylamino or C 1-4 alkylthio.
还在另一些实施方案中，R 2为以下子结构式： In still other embodiments, R 2 is the following substructure formula:
Figure PCTCN2019091137-appb-000039
Figure PCTCN2019091137-appb-000039
其中，R 11、R 22、R 33、R 44和R 55各自独立地为氢、氟、氯、溴、碘、羟基、氰基、硝基、氨基、羧基、-CH 3、-CH 2CH 3、-CH 2CH 2CH 3、-CH(CH 3) 2、-CH 2CH 2CH 2CH 3、-C(CH 3) 3、-CF 3、-OCH 3、-OCH 2CH 3、-OCH 2CH 2CH 3、-OCH(CH 3) 2、-OC(CH 3) 3、-OCF 3、-N(CH 3) 2或-SCH 3。 Among them, R 11 , R 22 , R 33 , R 44 and R 55 are each independently hydrogen, fluorine, chlorine, bromine, iodine, hydroxyl, cyano, nitro, amino, carboxyl, -CH 3 , -CH 2 CH 3 , -CH 2 CH 2 CH 3 , -CH (CH 3 ) 2 , -CH 2 CH 2 CH 2 CH 3 , -C (CH 3 ) 3 , -CF 3 , -OCH 3 , -OCH 2 CH 3 , -OCH 2 CH 2 CH 3 , -OCH (CH 3 ) 2 , -OC (CH 3 ) 3 , -OCF 3 , -N (CH 3 ) 2 or -SCH 3 .
还在一些实施方案中，R 3为以下子结构式： In some embodiments, R 3 is the following substructure:
Figure PCTCN2019091137-appb-000040
Figure PCTCN2019091137-appb-000040
其中，R 11、R 22、R 33、R 44和R 55各自独立地为氢、卤素、羟基、氰基、硝基、氨基、羧基、C 1-6烷基、卤代C 1-6烷基、C 1-6烷氧基、卤代C 1-6烷氧基、C 1-6烷基胺基或C 1-6烷硫基。 Among them, R 11 , R 22 , R 33 , R 44 and R 55 are each independently hydrogen, halogen, hydroxyl, cyano, nitro, amino, carboxyl, C 1-6 alkyl, halo C 1-6 alkane Alkyl, C 1-6 alkoxy, halo C 1-6 alkoxy, C 1-6 alkylamino or C 1-6 alkylthio.
还在另一些实施方案中，R 3为以下子结构式： In still other embodiments, R 3 is the following substructure formula:
Figure PCTCN2019091137-appb-000041
Figure PCTCN2019091137-appb-000041
其中，R 11、R 22、R 33、R 44和R 55各自独立地为氢、卤素、羟基、氰基、硝基、氨基、羧基、C 1-4烷基、卤代C 1-4烷基、C 1-4烷氧基、卤代C 1-4烷氧基、C 1-4烷基胺基或C 1-4烷硫基。 Among them, R 11 , R 22 , R 33 , R 44 and R 55 are each independently hydrogen, halogen, hydroxyl, cyano, nitro, amino, carboxyl, C 1-4 alkyl, halo C 1-4 alkane Alkyl, C 1-4 alkoxy, halo C 1-4 alkoxy, C 1-4 alkylamino or C 1-4 alkylthio.
还在另一些实施方案中，R 3为以下子结构式： In still other embodiments, R 3 is the following substructure formula:
Figure PCTCN2019091137-appb-000042
Figure PCTCN2019091137-appb-000042
其中，R 11、R 22、R 33、R 44和R 55各自独立地为氢、氟、氯、溴、碘、羟基、氰基、硝基、氨基、羧基、-CH 3、-CH 2CH 3、-CH 2CH 2CH 3、-CH(CH 3) 2、-CH 2CH 2CH 2CH 3、-C(CH 3) 3、-CF 3、-OCH 3、-OCH 2CH 3、-OCH 2CH 2CH 3、-OCH(CH 3) 2、-OC(CH 3) 3、-OCF 3、-N(CH 3) 2或-SCH 3。 Among them, R 11 , R 22 , R 33 , R 44 and R 55 are each independently hydrogen, fluorine, chlorine, bromine, iodine, hydroxyl, cyano, nitro, amino, carboxyl, -CH 3 , -CH 2 CH 3 , -CH 2 CH 2 CH 3 , -CH (CH 3 ) 2 , -CH 2 CH 2 CH 2 CH 3 , -C (CH 3 ) 3 , -CF 3 , -OCH 3 , -OCH 2 CH 3 , -OCH 2 CH 2 CH 3 , -OCH (CH 3 ) 2 , -OC (CH 3 ) 3 , -OCF 3 , -N (CH 3 ) 2 or -SCH 3 .
还在一些实施方案中，R 4为以下子结构式： In some embodiments, R 4 is the following substructure:
Figure PCTCN2019091137-appb-000043
Figure PCTCN2019091137-appb-000043
其中，R 11、R 22、R 33、R 44和R 55各自独立地为氢、卤素、羟基、氰基、硝基、氨基、羧基、C 1-6烷基、卤代C 1-6烷基、C 1-6烷氧基、卤代C 1-6烷氧基、C 1-6烷基胺基或C 1-6烷硫基。 Among them, R 11 , R 22 , R 33 , R 44 and R 55 are each independently hydrogen, halogen, hydroxyl, cyano, nitro, amino, carboxyl, C 1-6 alkyl, halo C 1-6 alkane Alkyl, C 1-6 alkoxy, halo C 1-6 alkoxy, C 1-6 alkylamino or C 1-6 alkylthio.
还在另一些实施方案中，R 4为以下子结构式： In still other embodiments, R 4 is the following substructure formula:
Figure PCTCN2019091137-appb-000044
Figure PCTCN2019091137-appb-000044
其中，R 11、R 22、R 33、R 44和R 55各自独立地为氢、卤素、羟基、氰基、硝基、氨基、羧基、C 1-4烷基、卤代C 1-4烷基、C 1-4烷氧基、卤代C 1-4烷氧基、C 1-4烷基胺基或C 1-4烷硫基。 Among them, R 11 , R 22 , R 33 , R 44 and R 55 are each independently hydrogen, halogen, hydroxyl, cyano, nitro, amino, carboxyl, C 1-4 alkyl, halo C 1-4 alkane Alkyl, C 1-4 alkoxy, halo C 1-4 alkoxy, C 1-4 alkylamino or C 1-4 alkylthio.
还在另一些实施方案中，R 4为以下子结构式： In still other embodiments, R 4 is the following substructure formula:
Figure PCTCN2019091137-appb-000045
Figure PCTCN2019091137-appb-000045
其中，R 11、R 22、R 33、R 44和R 55各自独立地为氢、氟、氯、溴、碘、羟基、氰基、硝基、氨基、羧基、-CH 3、-CH 2CH 3、-CH 2CH 2CH 3、-CH(CH 3) 2、-CH 2CH 2CH 2CH 3、-C(CH 3) 3、-CF 3、-OCH 3、-OCH 2CH 3、-OCH 2CH 2CH 3、-OCH(CH 3) 2、-OC(CH 3) 3、-OCF 3、-N(CH 3) 2或-SCH 3。 Among them, R 11 , R 22 , R 33 , R 44 and R 55 are each independently hydrogen, fluorine, chlorine, bromine, iodine, hydroxyl, cyano, nitro, amino, carboxyl, -CH 3 , -CH 2 CH 3 , -CH 2 CH 2 CH 3 , -CH (CH 3 ) 2 , -CH 2 CH 2 CH 2 CH 3 , -C (CH 3 ) 3 , -CF 3 , -OCH 3 , -OCH 2 CH 3 , -OCH 2 CH 2 CH 3 , -OCH (CH 3 ) 2 , -OC (CH 3 ) 3 , -OCF 3 , -N (CH 3 ) 2 or -SCH 3 .
还在一些实施方案中，R 5为以下子结构式： In some embodiments, R 5 is the following sub-structure formula:
Figure PCTCN2019091137-appb-000046
Figure PCTCN2019091137-appb-000046
其中，R 11、R 22、R 33、R 44和R 55各自独立地为氢、卤素、羟基、氰基、硝基、氨基、羧基、C 1-6烷基、卤代C 1-6烷基、C 1-6烷氧基、卤代C 1-6烷氧基、C 1-6烷基胺基或C 1-6烷硫基。 Among them, R 11 , R 22 , R 33 , R 44 and R 55 are each independently hydrogen, halogen, hydroxyl, cyano, nitro, amino, carboxyl, C 1-6 alkyl, halo C 1-6 alkane Alkyl, C 1-6 alkoxy, halo C 1-6 alkoxy, C 1-6 alkylamino or C 1-6 alkylthio.
还在另一些实施方案中，R 5为以下子结构式： In still other embodiments, R 5 is the following sub-structural formula:
Figure PCTCN2019091137-appb-000047
Figure PCTCN2019091137-appb-000047
其中，R 11、R 22、R 33、R 44和R 55各自独立地为氢、卤素、羟基、氰基、硝基、氨基、羧基、C 1-4烷基、卤代C 1-4烷基、C 1-4烷氧基、卤代C 1-4烷氧基、C 1-4烷基胺基或C 1-4烷硫基。 Among them, R 11 , R 22 , R 33 , R 44 and R 55 are each independently hydrogen, halogen, hydroxyl, cyano, nitro, amino, carboxyl, C 1-4 alkyl, halo C 1-4 alkane Alkyl, C 1-4 alkoxy, halo C 1-4 alkoxy, C 1-4 alkylamino or C 1-4 alkylthio.
还在另一些实施方案中，R 5为以下子结构式： In still other embodiments, R 5 is the following sub-structural formula:
Figure PCTCN2019091137-appb-000048
Figure PCTCN2019091137-appb-000048
其中，R 11、R 22、R 33、R 44和R 55各自独立地为氢、氟、氯、溴、碘、羟基、氰基、硝基、氨基、羧基、-CH 3、-CH 2CH 3、-CH 2CH 2CH 3、-CH(CH 3) 2、-CH 2CH 2CH 2CH 3、-C(CH 3) 3、-CF 3、-OCH 3、-OCH 2CH 3、-OCH 2CH 2CH 3、-OCH(CH 3) 2、-OC(CH 3) 3、-OCF 3、-N(CH 3) 2或-SCH 3。 Among them, R 11 , R 22 , R 33 , R 44 and R 55 are each independently hydrogen, fluorine, chlorine, bromine, iodine, hydroxyl, cyano, nitro, amino, carboxyl, -CH 3 , -CH 2 CH 3 , -CH 2 CH 2 CH 3 , -CH (CH 3 ) 2 , -CH 2 CH 2 CH 2 CH 3 , -C (CH 3 ) 3 , -CF 3 , -OCH 3 , -OCH 2 CH 3 , -OCH 2 CH 2 CH 3 , -OCH (CH 3 ) 2 , -OC (CH 3 ) 3 , -OCF 3 , -N (CH 3 ) 2 or -SCH 3 .
优选地，条件为：R 1、R 2和R 3中有且只有一个为
Figure PCTCN2019091137-appb-000049
其中，R 11、R 22、R 33、R 44和R 55具有本发明所述的含义。 Preferably, the condition is that there is one and only one of R 1 , R 2 and R 3 is
Figure PCTCN2019091137-appb-000049
Among them, R 11 , R 22 , R 33 , R 44 and R 55 have the meanings described in the present invention.
进一步优选地，条件为：R 1和R 3中有且只有一个为
Figure PCTCN2019091137-appb-000050
其中，R 11、R 22、R 33、R 44和R 55具有本发明所述的含义。 Further preferably, the condition is that there is one and only one of R 1 and R 3 is
Figure PCTCN2019091137-appb-000050
Among them, R 11 , R 22 , R 33 , R 44 and R 55 have the meanings described in the present invention.
在一些实施方案中，本发明提供一种具有式(II)所示的化合物或式(II)所示的化合物的盐或其氮氧化物：In some embodiments, the present invention provides a compound represented by Formula (II) or a salt of a compound represented by Formula (II) or a nitrogen oxide thereof:
Figure PCTCN2019091137-appb-000051
Figure PCTCN2019091137-appb-000051
其中，R 1、R 2、R 3、R 4和R 5具有本发明所述的含义。 Among them, R 1 , R 2 , R 3 , R 4 and R 5 have the meanings described in the present invention.
在一些实施方案中，R 1、R 2、R 3、R 4和R 5各自独立地为氢、卤素、C 1-4烷基、卤代C 1-4烷基、C 1-4烷氧基或卤代C 1-4烷氧基； In some embodiments, R 1 , R 2 , R 3 , R 4, and R 5 are each independently hydrogen, halogen, C 1-4 alkyl, halo C 1-4 alkyl, C 1-4 alkoxy Or halo C 1-4 alkoxy;
或R 1、R 2、R 3、R 4和R 5各自独立地为以下子结构式： Or R 1 , R 2 , R 3 , R 4 and R 5 are each independently the following substructure formula:
Figure PCTCN2019091137-appb-000052
Figure PCTCN2019091137-appb-000052
其中，R 11、R 22、R 33、R 44和R 55各自独立地为氢、卤素、C 1-4烷基、C 1-4烷氧基、卤代C 1-4烷基、卤代C 1-4烷氧基； Among them, R 11 , R 22 , R 33 , R 44 and R 55 are each independently hydrogen, halogen, C 1-4 alkyl, C 1-4 alkoxy, halo C 1-4 alkyl, halo C 1-4 alkoxy;
条件为：R 1、R 2和R 3中有且只有一个为
Figure PCTCN2019091137-appb-000053
The condition is: there is only one of R 1 , R 2 and R 3 is
Figure PCTCN2019091137-appb-000053
优选地，在一些实施方案中，R 1、R 2、R 3、R 4和R 5各自独立地为氢、卤素、C 1-4烷基、卤代C 1-4烷基、 C 1-4烷氧基或卤代C 1-4烷氧基； Preferably, in some embodiments, R 1 , R 2 , R 3 , R 4 and R 5 are each independently hydrogen, halogen, C 1-4 alkyl, halo C 1-4 alkyl, C 1- 4 alkoxy or halo C 1-4 alkoxy;
或R 1、R 2、R 3、R 4和R 5各自独立地为以下子结构式： Or R 1 , R 2 , R 3 , R 4 and R 5 are each independently the following substructure formula:
Figure PCTCN2019091137-appb-000054
Figure PCTCN2019091137-appb-000054
其中，R 11、R 22、R 33、R 44和R 55各自独立地为氢、卤素、C 1-4烷基、C 1-4烷氧基、卤代C 1-4烷基、卤代C 1-4烷氧基； Among them, R 11 , R 22 , R 33 , R 44 and R 55 are each independently hydrogen, halogen, C 1-4 alkyl, C 1-4 alkoxy, halo C 1-4 alkyl, halo C 1-4 alkoxy;
条件为：R 1和R 3中有且只有一个为
Figure PCTCN2019091137-appb-000055
The condition is: there is only one of R 1 and R 3 is
Figure PCTCN2019091137-appb-000055
在另一些实施方案中，R 1、R 2、R 3、R 4和R 5各自独立地为氢、氟、氯、溴、碘、-CH 3、-CH 2CH 3、-CH 2CH 2CH 3、-CH(CH 3) 2、-CH 2CH 2CH 2CH 3、-C(CH 3) 3、-CF 3、-OCH 3或-OCF 3； In other embodiments, R 1 , R 2 , R 3 , R 4 and R 5 are each independently hydrogen, fluorine, chlorine, bromine, iodine, -CH 3 , -CH 2 CH 3 , -CH 2 CH 2 CH 3 , -CH (CH 3 ) 2 , -CH 2 CH 2 CH 2 CH 3 , -C (CH 3 ) 3 , -CF 3 , -OCH 3 or -OCF 3 ;
或R 1、R 2、R 3、R 4和R 5各自独立地为以下子结构式： Or R 1 , R 2 , R 3 , R 4 and R 5 are each independently the following substructure formula:
Figure PCTCN2019091137-appb-000056
Figure PCTCN2019091137-appb-000056
其中，R 11、R 22、R 33、R 44和R 55各自独立地为氢、氟、氯、溴、碘、-CH 3、-CH 2CH 3、-CH 2CH 2CH 3、-CH(CH 3) 2、-CH 2CH 2CH 2CH 3、-C(CH 3) 3、-CF 3、-OCH 3或-OCF 3； Among them, R 11 , R 22 , R 33 , R 44 and R 55 are each independently hydrogen, fluorine, chlorine, bromine, iodine, -CH 3 , -CH 2 CH 3 , -CH 2 CH 2 CH 3 , -CH (CH 3 ) 2 , -CH 2 CH 2 CH 2 CH 3 , -C (CH 3 ) 3 , -CF 3 , -OCH 3 or -OCF 3 ;
条件为：R 1、R 2和R 3中有且只有一个为
Figure PCTCN2019091137-appb-000057
The condition is: there is only one of R 1 , R 2 and R 3 is
Figure PCTCN2019091137-appb-000057
优选地，在另一些实施方案中，R 1、R 2、R 3、R 4和R 5各自独立地为氢、氟、氯、溴、碘、-CH 3、-CH 2CH 3、-CH 2CH 2CH 3、-CH(CH 3) 2、-CH 2CH 2CH 2CH 3、-C(CH 3) 3、-CF 3、-OCH 3或-OCF 3； Preferably, in other embodiments, R 1 , R 2 , R 3 , R 4 and R 5 are each independently hydrogen, fluorine, chlorine, bromine, iodine, -CH 3 , -CH 2 CH 3 , -CH 2 CH 2 CH 3 , -CH (CH 3 ) 2 , -CH 2 CH 2 CH 2 CH 3 , -C (CH 3 ) 3 , -CF 3 , -OCH 3 or -OCF 3 ;
或R 1、R 2、R 3、R 4和R 5各自独立地为以下子结构式： Or R 1 , R 2 , R 3 , R 4 and R 5 are each independently the following substructure formula:
Figure PCTCN2019091137-appb-000058
Figure PCTCN2019091137-appb-000058
其中，R 11、R 22、R 33、R 44和R 55各自独立地为氢、氟、氯、溴、碘、-CH 3、-CH 2CH 3、-CH 2CH 2CH 3、-CH(CH 3) 2、-CH 2CH 2CH 2CH 3、-C(CH 3) 3、-CF 3、-OCH 3或-OCF 3； Among them, R 11 , R 22 , R 33 , R 44 and R 55 are each independently hydrogen, fluorine, chlorine, bromine, iodine, -CH 3 , -CH 2 CH 3 , -CH 2 CH 2 CH 3 , -CH (CH 3 ) 2 , -CH 2 CH 2 CH 2 CH 3 , -C (CH 3 ) 3 , -CF 3 , -OCH 3 or -OCF 3 ;
条件为：R 1和R 3中有且只有一个为
Figure PCTCN2019091137-appb-000059
The condition is: there is only one of R 1 and R 3 is
Figure PCTCN2019091137-appb-000059
还在一些实施方案中，本发明提供一种具有式(III)所示的化合物或式(III)所示的化合物的盐或其氮氧化物：In some embodiments, the present invention provides a compound represented by Formula (III) or a salt of a compound represented by Formula (III) or a nitrogen oxide thereof:
Figure PCTCN2019091137-appb-000060
Figure PCTCN2019091137-appb-000060
其中，R 2、R 3、R 4和R 5具有本发明所述的含义。 Among them, R 2 , R 3 , R 4 and R 5 have the meanings described in the present invention.
在一些实施方案中，R 2、R 3、R 4和R 5各自独立地为氢、卤素、C 1-4烷基或卤代C 1-4烷基； In some embodiments, R 2 , R 3 , R 4, and R 5 are each independently hydrogen, halogen, C 1-4 alkyl, or halo C 1-4 alkyl;
或R 2、R 3、R 4和R 5各自独立地为以下子结构式： Or R 2 , R 3 , R 4 and R 5 are each independently the following substructure formula:
Figure PCTCN2019091137-appb-000061
Figure PCTCN2019091137-appb-000061
其中，R 11、R 22、R 33、R 44和R 55各自独立地为氢、卤素、C 1-4烷基、C 1-4烷氧基、卤代C 1-4烷基、卤代C 1-4烷氧基、C 1-4烷基胺基或C 1-4烷硫基； Among them, R 11 , R 22 , R 33 , R 44 and R 55 are each independently hydrogen, halogen, C 1-4 alkyl, C 1-4 alkoxy, halo C 1-4 alkyl, halo C 1-4 alkoxy, C 1-4 alkylamino or C 1-4 alkylthio;
条件为：R 2、R 3、R 4和R 5中有且只有一个为
Figure PCTCN2019091137-appb-000062
The conditions are: there is only one of R 2 , R 3 , R 4 and R 5 is
Figure PCTCN2019091137-appb-000062
优选地，在另一些实施方案中，R 2、R 4和R 5各自独立地为氢、卤素、C 1-4烷基或卤代C 1-4烷基； Preferably, in other embodiments, R 2 , R 4 and R 5 are each independently hydrogen, halogen, C 1-4 alkyl or halo C 1-4 alkyl;
R 3为
Figure PCTCN2019091137-appb-000063
R 3 is
Figure PCTCN2019091137-appb-000063
其中，R 11、R 22、R 33、R 44和R 55各自独立地为氢、卤素、C 1-4烷基、C 1-4烷氧基、卤代C 1-4烷基、卤代C 1-4烷氧基、C 1-4烷基胺基或C 1-4烷硫基。 Among them, R 11 , R 22 , R 33 , R 44 and R 55 are each independently hydrogen, halogen, C 1-4 alkyl, C 1-4 alkoxy, halo C 1-4 alkyl, halo C 1-4 alkoxy, C 1-4 alkylamino or C 1-4 alkylthio.
在一些实施方案中，R 2、R 3、R 4和R 5各自独立地为氢、氟、氯、溴、碘、-CH 3或-CF 3； In some embodiments, R 2 , R 3 , R 4 and R 5 are each independently hydrogen, fluorine, chlorine, bromine, iodine, —CH 3 or —CF 3 ;
或R 2、R 3、R 4和R 5各自独立地为以下子结构式： Or R 2 , R 3 , R 4 and R 5 are each independently the following substructure formula:
Figure PCTCN2019091137-appb-000064
Figure PCTCN2019091137-appb-000064
其中，R 11、R 22、R 33、R 44和R 55各自独立地为氢、氟、氯、溴、碘、-CH 3、-CH 2CH 3、-CH 2CH 2CH 3、-CH(CH 3) 2、-CH 2CH 2CH 2CH 3、-C(CH 3) 3、-CF 3、-OCH 3、-OCF 3、-N(CH 3) 2或-SCH 3； Among them, R 11 , R 22 , R 33 , R 44 and R 55 are each independently hydrogen, fluorine, chlorine, bromine, iodine, -CH 3 , -CH 2 CH 3 , -CH 2 CH 2 CH 3 , -CH (CH 3 ) 2 , -CH 2 CH 2 CH 2 CH 3 , -C (CH 3 ) 3 , -CF 3 , -OCH 3 , -OCF 3 , -N (CH 3 ) 2 or -SCH 3 ;
条件为：R 2、R 3、R 4和R 5中有且只有一个为
Figure PCTCN2019091137-appb-000065
The conditions are: there is only one of R 2 , R 3 , R 4 and R 5 is
Figure PCTCN2019091137-appb-000065
优选地，在另一些实施方案中，R 2、R 4和R 5各自独立地为氢； Preferably, in other embodiments, R 2 , R 4 and R 5 are each independently hydrogen;
R 3为
Figure PCTCN2019091137-appb-000066
R 3 is
Figure PCTCN2019091137-appb-000066
其中，R 11、R 22、R 33、R 44和R 55各自独立地为氢、氟、氯、溴、碘、-CH 3、-CH 2CH 3、-CH 2CH 2CH 3、-CH(CH 3) 2、-CH 2CH 2CH 2CH 3、-C(CH 3) 3、-CF 3、-OCH 3、-OCF 3、-N(CH 3) 2或-SCH 3。 Among them, R 11 , R 22 , R 33 , R 44 and R 55 are each independently hydrogen, fluorine, chlorine, bromine, iodine, -CH 3 , -CH 2 CH 3 , -CH 2 CH 2 CH 3 , -CH (CH 3 ) 2 , -CH 2 CH 2 CH 2 CH 3 , -C (CH 3 ) 3 , -CF 3 , -OCH 3 , -OCF 3 , -N (CH 3 ) 2 or -SCH 3 .
还在一些实施方案中，本发明提供一种具有式(II-1)所示的化合物或式(II-1)所示的化合物的盐或其氮氧化物：In still other embodiments, the present invention provides a compound represented by Formula (II-1) or a salt of a compound represented by Formula (II-1) or a nitrogen oxide thereof:
Figure PCTCN2019091137-appb-000067
Figure PCTCN2019091137-appb-000067
其中，R 2、R 3、R 4、R 5、R 11、R 22、R 33、R 44和R 55具有本发明所述的含义。 Among them, R 2 , R 3 , R 4 , R 5 , R 11 , R 22 , R 33 , R 44 and R 55 have the meanings described in the present invention.
还在一些实施方案中，本发明提供一种具有式(II-2)所示的化合物或式(II-2)所示的化合物的盐或其氮氧化物：In still other embodiments, the present invention provides a compound having a compound represented by Formula (II-2) or a salt of a compound represented by Formula (II-2) or a nitrogen oxide thereof:
Figure PCTCN2019091137-appb-000068
Figure PCTCN2019091137-appb-000068
其中，R 1、R 2、R 4、R 5、R 11、R 22、R 33、R 44和R 55具有本发明所述的含义。 Among them, R 1 , R 2 , R 4 , R 5 , R 11 , R 22 , R 33 , R 44 and R 55 have the meanings described in the present invention.
又还在一些实施方案中，本发明提供一种具有式(III-1)所示的化合物或式(III-1)所示的化合物的盐或其氮氧化物：In still other embodiments, the present invention provides a compound represented by Formula (III-1) or a salt of a compound represented by Formula (III-1) or a nitrogen oxide thereof:
Figure PCTCN2019091137-appb-000069
Figure PCTCN2019091137-appb-000069
其中，R 2、R 4、R 5、R 11、R 22、R 33、R 44和R 55具有本发明所述的含义。 Among them, R 2 , R 4 , R 5 , R 11 , R 22 , R 33 , R 44 and R 55 have the meanings described in the present invention.
在一些实施方案中，本发明提供一种化合物，其为具有下列之一结构的化合物或具有下列之一结构化合物的盐、氮氧化物、或(E)和(Z)异构体以及它们的混合物：In some embodiments, the present invention provides a compound that is a compound having one of the following structures or a salt, nitrogen oxide, or (E) and (Z) isomers of a compound having one of the following structures, and their mixture:
Figure PCTCN2019091137-appb-000070
Figure PCTCN2019091137-appb-000070
Figure PCTCN2019091137-appb-000071
Figure PCTCN2019091137-appb-000071
Figure PCTCN2019091137-appb-000072
Figure PCTCN2019091137-appb-000072
Figure PCTCN2019091137-appb-000073
Figure PCTCN2019091137-appb-000073
Figure PCTCN2019091137-appb-000074
Figure PCTCN2019091137-appb-000074
Figure PCTCN2019091137-appb-000075
Figure PCTCN2019091137-appb-000075
Figure PCTCN2019091137-appb-000076
Figure PCTCN2019091137-appb-000076
Figure PCTCN2019091137-appb-000077
Figure PCTCN2019091137-appb-000077
Figure PCTCN2019091137-appb-000078
Figure PCTCN2019091137-appb-000078
Figure PCTCN2019091137-appb-000079
Figure PCTCN2019091137-appb-000079
Figure PCTCN2019091137-appb-000080
Figure PCTCN2019091137-appb-000080
Figure PCTCN2019091137-appb-000081
Figure PCTCN2019091137-appb-000081
除非其他方面表明，本发明式(I-A)、式(I)、式(II)、式(II-1)、式(II-2)、式(III)或式(III-1)所示的化合物所有的立体异构体、互变异构体，消旋体，水合物，溶剂化物，代谢产物，代谢前体和前药也都属于本发明的范围。Unless otherwise indicated, the formula (IA), (I), (II), (II-1), (II-2), (III) or (III-1) All stereoisomers, tautomers, racemates, hydrates, solvates, metabolites, metabolic precursors and prodrugs of the compounds also fall within the scope of the invention.
本发明所述的噁二唑类肟衍生物中的肟
Figure PCTCN2019091137-appb-000082
表示(Z)体异构体
Figure PCTCN2019091137-appb-000083
(E)体异构体
Figure PCTCN2019091137-appb-000084
及(Z)体异构体和(E)体异构体的混合物，(Z)体异构体、(E)体异构体及(Z)体异构体和(E)体异构体的混合物均包含在本发明中，其中(Z)体异构体、(E)体异构体或(Z)体异构体和(E)体异构体的混合物可以通过核磁共振氢谱、高效液相色谱法和/或单晶培养等常规方法进行结构确认。 Oxime in oxadiazole oxime derivatives according to the present invention
Figure PCTCN2019091137-appb-000082
Represents the (Z) isomer
Figure PCTCN2019091137-appb-000083
(E) Isomer
Figure PCTCN2019091137-appb-000084
And (Z) isomer and (E) isomer mixture, (Z) isomer, (E) isomer and (Z) isomer and (E) isomer The mixtures are all included in the present invention, wherein (Z) isomers, (E) isomers, or mixtures of (Z) isomers and (E) isomers may be analyzed by nuclear magnetic resonance hydrogen spectroscopy, The structure is confirmed by a conventional method such as high-performance liquid chromatography and / or single crystal culture.
另一方面，本发明提供一种包含本发明化合物作为有效成分的组合物。In another aspect, the present invention provides a composition comprising the compound of the present invention as an active ingredient.
在一些实施方案中，本发明所述的组合物进一步包含农药学上可接受的表面活性剂和/或载体。In some embodiments, the composition of the invention further comprises an agrochemically acceptable surfactant and / or carrier.
另一方面，本发明提供本发明所述的化合物或本发明所述组合物在防治植物病原性真菌中的应用。In another aspect, the present invention provides the use of a compound of the present invention or a composition of the present invention for controlling plant pathogenic fungi.
进一步地，本发明提供本发明所述的化合物或本发明所述组合物在防治黄瓜霜霉病中的应用。Further, the present invention provides an application of the compound of the present invention or the composition of the present invention in controlling cucumber downy mildew.
另一方面，本发明提供本发明所述的化合物或本发明所述组合物在防治植物病原性真菌中的使用方法。In another aspect, the present invention provides a method for using the compound according to the present invention or the composition according to the present invention for controlling plant pathogenic fungi.
本发明化合物的组合物和制剂Compositions and formulations of the compounds of the invention
本发明的化合物一般可用作组合物即制剂中的杀真菌剂活性成分，通常还包括农药学上可接受的表面活性剂和/或载体。The compounds of the invention are generally useful as fungicide active ingredients in compositions, i.e. formulations, and generally also include agrochemically acceptable surfactants and / or carriers.
上述表面活性剂可以为农药制剂领域所公知的各种表面活性剂，如阴离子表面活性剂、阳离子表面活性剂、非离子表面活性剂和两性表面活性剂，嵌段聚合物，聚电解质，以及它们的混合物。该类表面活性剂可以用作乳化剂、分散剂、润湿剂、渗透促进剂或辅助剂。The aforementioned surfactants can be various surfactants known in the field of pesticide formulations, such as anionic surfactants, cationic surfactants, nonionic surfactants and amphoteric surfactants, block polymers, polyelectrolytes, and the like. mixture. Such surfactants can be used as emulsifiers, dispersants, wetting agents, penetration enhancers or adjuvants.
合适的阴离子表面活性剂是磺酸、硫酸、磷酸、羧酸的碱金属、碱土金属或铵盐以及它们的混合物。磺酸盐的实例是烷基芳基磺酸盐、二苯基磺酸盐、α-烯烃磺酸盐、木素磺酸盐、脂肪酸和油的磺酸盐、乙氧基化烷基酚的磺酸盐、烷氧基化芳基酚的磺酸盐、缩合萘的磺酸盐、十二烷基-和十三烷基苯的磺酸盐、萘和烷基萘的磺酸盐、磺基琥珀酸盐或磺基琥珀酰胺酸盐。硫酸盐的实例是脂肪酸和油的硫酸盐、乙氧基化烷基酚的硫酸盐、醇的硫酸盐、乙氧基化醇的硫酸盐或脂肪酸酯的硫酸盐。磷酸盐的实例是磷酸盐酯。羧酸盐的实例是烷基羧酸盐以及羧化醇或烷基酚乙氧基化物。Suitable anionic surfactants are alkali metal, alkaline earth metal or ammonium salts of sulfonic acids, sulfuric acids, phosphoric acids, carboxylic acids and mixtures thereof. Examples of sulfonates are alkylaryl sulfonates, diphenyl sulfonates, alpha-olefin sulfonates, lignosulfonates, sulfonates of fatty acids and oils, ethoxylated alkylphenols Sulfonate, alkoxylated arylphenol sulfonate, condensed naphthalene sulfonate, dodecyl- and tridecylbenzene sulfonate, naphthalene and alkylnaphthalene sulfonate, sulfonate Succinate or sulfosuccinate. Examples of sulfates are sulfates of fatty acids and oils, sulfates of ethoxylated alkylphenols, sulfates of alcohols, sulfates of ethoxylated alcohols or sulfates of fatty acid esters. An example of a phosphate is a phosphate ester. Examples of carboxylates are alkyl carboxylates and carboxylated alcohols or alkylphenol ethoxylates.
合适的非离子表面活性剂是烷氧基化物，N-取代的脂肪酸酰胺，胺氧化物，酯类，糖基表面活性剂，聚合物表面活性剂及其混合物。烷氧基化物的实例是诸如已经被1-50当量烷氧基化的醇、烷基酚、胺、酰胺、芳基酚、脂肪酸或脂肪酸酯的化合物。可以将氧化乙烯和/或氧化丙烯用于烷氧基化，优选氧化乙烯。N-取代的脂肪酸酰胺的实例是脂肪酸葡糖酰胺或脂肪酸链烷醇酰胺。酯类的实例是脂肪酸酯，甘油酯或甘油单酯。糖基表面活性剂的实例是脱水山梨醇、乙氧基化脱水山梨醇、蔗糖和葡萄糖酯或烷基聚葡糖苷。聚合物表面活性剂的实例是乙烯基吡咯烷酮、乙烯醇或乙酸乙烯酯的均聚物或共聚物。Suitable nonionic surfactants are alkoxylates, N-substituted fatty acid amides, amine oxides, esters, sugar-based surfactants, polymer surfactants and mixtures thereof. Examples of alkoxylates are compounds such as alcohols, alkylphenols, amines, amides, arylphenols, fatty acids or fatty acid esters that have been alkoxylated with 1-50 equivalents. Ethylene oxide and / or propylene oxide can be used for alkoxylation, preferably ethylene oxide. Examples of N-substituted fatty acid amides are fatty acid glucamides or fatty acid alkanolamides. Examples of esters are fatty acid esters, glycerides or monoglycerides. Examples of glycosyl surfactants are sorbitan, ethoxylated sorbitan, sucrose and glucose esters or alkyl polyglucosides. Examples of polymer surfactants are homopolymers or copolymers of vinylpyrrolidone, vinyl alcohol or vinyl acetate.
合适的阳离子表面活性剂是季型表面活性剂，例如具有1或2个疏水性基团的季铵化合物，或长链伯胺的盐。合适的两性表面活性剂是烷基甜菜碱和咪唑啉类。合适的嵌段聚合物是包含聚氧乙烯和聚氧丙烯的嵌段的A-B或A-B-A类型嵌段聚合物，或包含链烷醇、聚氧乙烯和聚氧丙烯的A-B-C类型嵌段聚合物。合适的聚电解质是聚酸或聚碱。聚酸的实例是聚丙烯酸的碱金属盐或聚酸梳状聚合物。聚碱的实例是聚乙烯基胺或聚乙烯胺。Suitable cationic surfactants are quaternary surfactants, such as quaternary ammonium compounds having 1 or 2 hydrophobic groups, or salts of long-chain primary amines. Suitable amphoteric surfactants are alkyl betaines and imidazolines. Suitable block polymers are A-B or A-B-A type block polymers containing blocks of polyoxyethylene and polyoxypropylene, or A-B-C type block polymers containing alkanol, polyoxyethylene and polyoxypropylene. Suitable polyelectrolytes are polyacids or polybases. Examples of polyacids are alkali metal salts of polyacrylic acid or polyacid comb polymers. Examples of the polybase are polyvinylamine or polyvinylamine.
上述载体可以为农药制剂领域所公知的各种载体，包括各种硅酸盐类、碳酸盐类、硫酸盐类、氧化物类、磷酸盐类、植物载体类、合成载体类。具体地，例如：白炭黑、高岭土、硅藻土、粘土、滑石、有机膨润土、浮石、二氧化钛、糊精、纤维素粉、轻质碳酸钙、可溶性淀粉、玉米淀粉、锯末粉、尿素、胺肥、 尿素和胺肥的混合物、葡萄糖、麦芽糖、蔗糖、无水碳酸钾、无水碳酸钠、无水碳酸氢钾、无水碳酸氢钠、凹凸棒土、无水碳酸钾与无水碳酸氢钾的混合物和无水碳酸钠与无水碳酸氢钠的混合物中的一种或多种。The aforementioned carrier may be various carriers known in the field of pesticide preparations, including various silicates, carbonates, sulfates, oxides, phosphates, plant carriers, and synthetic carriers. Specifically, for example: white carbon black, kaolin, diatomaceous earth, clay, talc, organic bentonite, pumice, titanium dioxide, dextrin, cellulose powder, light calcium carbonate, soluble starch, corn starch, sawdust powder, urea, amine Fertilizer, a mixture of urea and amine fertilizer, glucose, maltose, sucrose, anhydrous potassium carbonate, anhydrous sodium carbonate, anhydrous potassium bicarbonate, anhydrous sodium bicarbonate, attapulgite, anhydrous potassium carbonate and anhydrous hydrogen carbonate One or more of a mixture of potassium and a mixture of anhydrous sodium carbonate and anhydrous sodium bicarbonate.
根据本发明的杀真菌剂组合物，该杀真菌剂组合物还可以含有农药制剂领域所常用的各种制剂用助剂，具体地，该制剂用助剂可以为溶剂、助溶剂、增稠剂、防冻剂、囊材、保护剂、消泡剂、崩解剂、稳定剂、防腐剂、粘合剂、螯合剂中的一种或多种。According to the fungicide composition of the present invention, the fungicide composition may further contain various formulation adjuvants commonly used in the field of pesticide preparations. Specifically, the formulation adjuvant may be a solvent, a cosolvent, and a thickener. , Antifreeze, capsule material, protective agent, antifoaming agent, disintegrating agent, stabilizer, preservative, adhesive, chelating agent.
合适的溶剂是水和有机溶剂，如中到高沸点的矿物油馏分，例如煤油、柴油；植物或动物来源的油；脂族、环状和芳族烃类，例如甲苯、石蜡、四氢萘、烷基化萘；醇类，如乙醇、丙醇、丁醇、苄醇、环己醇；二醇类；DMSO；酮类，例如环己酮；酯类，例如乳酸酯、碳酸酯、脂肪酸酯、γ-丁内酯；脂肪酸；膦酸酯；胺类；酰胺类，例如N-甲基吡咯烷酮，脂肪酸二甲基酰胺；以及它们的混合物。Suitable solvents are water and organic solvents, such as medium to high boiling point mineral oil fractions, such as kerosene, diesel oil; oils of vegetable or animal origin; aliphatic, cyclic and aromatic hydrocarbons such as toluene, paraffin, tetrahydronaphthalene Alkyl naphthalenes; alcohols, such as ethanol, propanol, butanol, benzyl alcohol, cyclohexanol; glycols; DMSO; ketones, such as cyclohexanone; esters, such as lactate, carbonate, Fatty acid esters, γ-butyrolactone; fatty acids; phosphonates; amines; amides, such as N-methylpyrrolidone, fatty acid dimethylamide; and mixtures thereof.
上述溶剂也可以作为助溶剂使用。These solvents can also be used as co-solvents.
合适的增稠剂选自多糖(例如黄原胶、羧甲基纤维素)、无机粘土(有机改性或未改性的)、聚羧酸盐和硅酸盐。Suitable thickeners are selected from polysaccharides (e.g. xanthan gum, carboxymethyl cellulose), inorganic clays (organically modified or unmodified), polycarboxylates and silicates.
合适的防冻剂选自乙二醇、丙二醇、丙三醇、尿素、甘油及其它们的混合物。Suitable antifreeze agents are selected from ethylene glycol, propylene glycol, glycerol, urea, glycerol and mixtures thereof.
合适的囊材选自聚氨酯、聚脲、脲醛树脂及其它们的混合物。Suitable capsules are selected from polyurethane, polyurea, urea resins and mixtures thereof.
合适的保护剂选自聚乙烯醇和/或聚乙二醇。Suitable protective agents are selected from polyvinyl alcohol and / or polyethylene glycol.
合适的消泡剂选自聚硅氧烷、硅酮乳、长链醇、脂肪酸及其盐、以及含氟有机物及其它们的混合物。Suitable defoamers are selected from the group consisting of polysiloxanes, silicone milks, long-chain alcohols, fatty acids and their salts, and fluorine-containing organics and mixtures thereof.
合适的崩解剂选自膨润土、尿素、硫酸铵、氯化铝、柠檬酸、丁二酸、碳酸氢钠及其它们的混合物Suitable disintegrants are selected from bentonite, urea, ammonium sulfate, aluminum chloride, citric acid, succinic acid, sodium bicarbonate and mixtures thereof
合适的稳定剂选自亚磷酸三苯酯、环氧氯丙烷、醋酐及其它们的混合物。Suitable stabilizers are selected from triphenyl phosphite, epichlorohydrin, acetic anhydride, and mixtures thereof.
合适的防腐剂选自苯甲酸、苯甲酸钠、1,2-苯并异噻唑啉-3-酮(简称BIT)、卡松、山梨酸钾及其它们的混合物。Suitable preservatives are selected from the group consisting of benzoic acid, sodium benzoate, 1,2-benzoisothiazolin-3-one (BIT for short), carson, potassium sorbate, and mixtures thereof.
合适的粘合剂选自聚乙烯吡咯烷酮、聚乙酸乙烯酯、聚乙烯醇、聚丙烯酸酯、生物蜡或合成蜡以及纤维素醚。Suitable binders are selected from polyvinylpyrrolidone, polyvinyl acetate, polyvinyl alcohol, polyacrylate, biowax or synthetic wax, and cellulose ether.
本发明所述杀真菌剂可以以其制剂形式或由其制备的使用形式施用，所述使用形式例如气溶胶、胶囊悬浮剂、冷雾浓缩剂(cold-fogging concentrate)、热雾浓缩剂、胶囊化的颗粒剂、细颗粒剂、用于种子处理的流动性浓缩剂(flowable concentrate)、即用型溶液、可撒粉的粉剂、可乳化的浓缩剂、水包油乳剂、油包水乳剂、大颗粒剂、微颗粒剂、油分散性粉末剂、油混溶性流动浓缩剂、油混溶性液体、气剂(在压力下)、产气产品、泡沫剂、糊剂、悬浮浓缩剂、悬乳浓缩剂、可溶性浓缩剂、混悬剂、可湿性粉剂、可溶性粉剂、粉剂和颗粒剂、水溶性和水分散性的颗粒剂或片剂、用于种子处理的水溶性或水分散性粉剂，可湿性粉剂、经活性物质浸渍的天然产物及合成物质，以及聚合物和种子包衣材料中的微胶囊，以及ULV(ultra low volume)冷雾和热雾制剂。上述使用形式均可由本领域的常规手段制备得到。The fungicides according to the invention can be applied in the form of their formulations or in the use forms prepared therefrom, such as aerosols, capsule suspensions, cold-fogging concentrates, hot-fog concentrates, capsules Granules, fine granules, flowable concentrates for seed treatment, ready-to-use solutions, dustable powders, emulsifiable concentrates, oil-in-water emulsions, water-in-oil emulsions, Large granules, micro granules, oil-dispersible powders, oil-miscible flow concentrates, oil-miscible liquids, aerosols (under pressure), gas producing products, foaming agents, pastes, suspension concentrates, suspension emulsions Concentrates, soluble concentrates, suspensions, wettable powders, soluble powders, powders and granules, water-soluble and water-dispersible granules or tablets, water-soluble or water-dispersible powders for seed treatment, can be Wet powders, natural products and synthetic materials impregnated with active substances, and microcapsules in polymer and seed coating materials, as well as ULV (ultra low volume) cold and hot mist formulations. The above use forms can be prepared by conventional means in the art.
本发明化合物及组合物的应用Application of the compounds and compositions of the present invention
本发明的化合物可用作植物病害控制剂。因此，本发明还可包括用于控制由植物病原真菌引起的植物病害的方法，所述方法包括向待保护植物或其部分或向待保护植物种子施用有效量的本发明的化合物或包含所述化合物的杀真菌组合物。本发明的化合物和/或组合物可对由担子菌纲、子囊菌纲、卵菌纲和半知菌纲广谱植物病原真菌引起的病害提供控制。它们可有效地控制广谱植物病害，尤其是观赏作物、草坪作物、蔬菜作物、大田作物、谷类作物和果树作物的叶片病原体。这些病原体包括：卵菌纲，包括疫霉属(Phytophthora)病害诸如致病疫霉菌(Phytophthora infestans)、大豆疫霉病菌(Phytophthora megasperma)、柑桔脚腐病菌(Phytophthora parasitica)、樟疫霉菌(Phytophthora cinnamomi)和南瓜疫病菌(Phytophthora capsici)的病害，草腐霉枯萎属(Pythium)物种病害诸如坪草腐霉枯萎病菌(Pythium aphanidermatum)的病害，以及霜霉科(Peronosporaceae)物种病害诸如葡萄霜霉病菌(Plasmopara viticola)，霜霉属病害 (Peronospora spp.)(包括烟草霜霉菌(Peronospora tabacina)和寄生霜霉菌(Peronospora parasitica))，假霜霉属(Pseudoperonospora spp.)病害(包括黄瓜霜霉病菌(Pseudoperonospora cubensis)和盘梗霉菌病菌(Bremia lactucae))；子囊菌(包括链格孢属(Alternaria)病菌如番茄早疫病菌(Alternaria solani)和甘蓝黑斑病菌(Alternaria brassicae)，球座菌属(Guignardia)病害如葡萄黑腐病菌(Guignardia bidwell)，黑星菌属(Venturia)病害如苹果黑星病菌(Venturia inaequalis)，壳针孢属(Septoria)病害如颖枯病菌(Septoria nodorum)和叶枯病菌(Septoria tritici)，白粉(powdery mildew)病害如白粉菌属病菌(Erysiphe spp.)(包括小麦白粉病菌(Erysiphe graminis)和萝白粉病菌(Erysiphe polygoni))、葡萄白粉病菌(Uncinula necatur)、黄瓜白粉病菌(Sphaerotheca fuligena)和苹果白粉病菌(Podosphaera leucotricha)、小麦基腐病菌(Pseudocercosporella herpotrichoides)，灰霉菌属(Botrytis)病害如草莓灰霉病菌(Botrytis cinerea)、桃褐腐病菌(Monilinia fructicola)，菌核菌属(Sclerotinia)病害如油菜菌核病菌(Sclerotinia sclerotiorum)、稻瘟病菌(Magnaporthe grisea)、葡萄枝枯病菌(Phomopsis viticola)，蠕形菌属(Helminthosporium)病害如玉米大斑病菌(Helminthosporium tritici repentis)、网纹病菌(Pyrenophora teres)，炭疽病菌如黑果病菌(Glomerella)或炭疽菌属(Colletotrichum spp.)病害(如粱炭疽病菌(Colletotrichum graminicola)和西瓜炭疽病菌(Colletotrichum orbiculare))，和小麦全蚀病菌(Gaeumannomyces graminis)；担子菌，包括由锈菌属(Puccinia spp.)造成的锈菌病害(如隐匿柄锈菌(Puccinia recondita)、条锈菌(Puccinia striiformis)、叶锈菌(Puccinia hordei)、杆锈菌(Puccinia graminis)和柄锈菌(Puccinia arachidis))，咖啡锈菌(Hemileia vastatrix)和大豆锈菌(Phakopsora pachyrhizi)；其它病原体包括丝核菌属物种(Rhizoctonia spp.)(如立枯丝核菌(Rhizoctonia solani))；镰刀菌属(Fusarium)物种病害诸如粉红镰刀菌(Fusarium roseum)、禾谷镰刀菌(Fusarium graminearum)和尖孢镰刀菌(Fusarium oxysporum)；大丽轮枝菌(Verticillium dahliae)；白绢菌(Sclerotium rolfsii)；云纹菌(Rynchosporium secalis)；黑涩病菌(Cercosporidium personatum)、黑斑病菌(Cercospora arachidicola)和褐斑病菌(Cercospora beticola)；以及其它与这些病原体密切相关的类别和菌种。除了它们的杀真菌活性之外，所述组合物或组合还对细菌诸如梨火疫病菌(Erwinia amylovora)、野油菜黄单胞菌(Xanthomonas campestris)、丁香假单胞菌(Pseudomonas syringae)以及其它菌种具有抵抗活性。The compounds of the present invention are useful as plant disease control agents. Accordingly, the present invention may further include a method for controlling a plant disease caused by a phytopathogenic fungus, the method comprising applying an effective amount of a compound of the present invention to a plant or a part thereof to be protected or a seed of a plant to be protected or comprising the Fungicidal compositions of the compounds. The compounds and / or compositions of the present invention can provide control of diseases caused by broad-spectrum phytopathogenic fungi of the Basidiomycetes, Ascomycetes, Oomycetes, and Deuteromycetes. They can effectively control broad-spectrum plant diseases, especially leaf pathogens of ornamental crops, lawn crops, vegetable crops, field crops, cereal crops, and fruit tree crops. These pathogens include: Oomycetes, including Phytophthora diseases such as Phytophthora infestans, Phytophthora megasperma, Phytophthora parasitica, Phytophthora diseases of cinnamomi and Phytophthora capsici, diseases of Pythium species such as Pythium aphanidermatum, and diseases of species Peronosporaceae Pathogen (Plasmopara viticola), Downy mildew disease (Peronospora spp.) (Including tobacco downy mildew (Peronospora tabacina and Peronospora parasitica)), Pseudoperonospora disease (including cucumber downy mildew) (Pseudoperonospora cubensis) and Bremia lactucae); ascomycetes (including Alternaria bacterium such as Alternaria solani and cabbage black spot bacterium (Alternaria braccae)) (Guignardia) diseases such as Guignardia bidwell, Venturia ) Diseases such as Venturia inaequalis, Septoria diseases such as Septoria nodorum and Septoria tritici, powdery mildew diseases such as Erysiphe spp.) (including wheat powdery mildew (Erysiphe gramminis and Erysiphe polygoni)), grape powdery mildew (Uncinula necatur), cucumber powdery mildew (Sphaerotheca fuligena), and apple powdery mildew (Podosphaera leucotcotricha) (Pseudocercosporella herpotrichoides), Botrytis diseases such as Botrytis cinerea, Monilinia fructicola, Sclerotinia diseases such as Sclerotinia sclerotiorum, rice Magnaporthe grisea, Phomopsis viticola, Helminthosporium diseases such as Helminthosporium tritici repentis, Pyrenophora quateres, and anthracnose bacterium such as black fruit disease Glomerella) or Colletotrichum sp. (Colletotrichum graminicola) and watermelon anthracnose (Colletotrichum orbiculare), and Gaeumannomyces graminis; Basidiomycetes, including rust diseases caused by Puccinia spp. (Such as Puccinia recondita, Puccinia striiformis, Puccinia hordei, Puccinia graminis and Puccinia arachidis), coffee rust (Hemileia vastatrix) and soybean rust (Phakopsora pachyrhizi) ); Other pathogens include Rhizoctonia spp. (Such as Rhizoctonia solani); Fusarium species diseases such as Fusarium fusarium, Fusarium graminearum ( Fusarium graminearum and Fusarium oxysporum; Verticillium dahliae; Sclerotium rolfsii; Rynchosporium secalis; Cercosporidium personalatum, Black spot fungus (Cercosporaarachidicola) and Cercospora beticola; and other species and strains closely related to these pathogensIn addition to their fungicidal activity, the composition or combination is effective against bacteria such as Erwinia amylovora, Xanthomonas campestris, Pseudomonas syringae, and others The strains are resistant.
本发明的杀真菌剂组合物的使用方法简单，在植物病害萌发之前或萌发之后，向作物及作物生长的场所按常规方法施用，如拌土、喷雾、喷射、浇注等，其施用量根据气候条件或作物状态而定，一般情况下每亩施用10-5000g，稀释成10-400mg/L(优选为100-300mg/L)施用。稀释剂优选为水。The method of using the fungicide composition of the present invention is simple. Before plant disease germination or after germination, it is applied to crops and crop growth sites according to conventional methods, such as soil mixing, spraying, spraying, pouring, etc., and the application amount is according to the climate Depending on the conditions or the state of the crop, in general, 10-5000 g is applied per acre and diluted to 10-400 mg / L (preferably 100-300 mg / L). The diluent is preferably water.
本发明的杀真菌剂组合物，其杀真菌效果通常与外界因素如气候有关，但通过使用适当的剂型可以减缓气候的影响。The fungicidal effect of the fungicide composition of the present invention is generally related to external factors such as climate, but the influence of climate can be slowed down by using a proper dosage form.
本发明的组合物还可与其它具有杀菌、杀虫或除草性能的化合物混合使用，也可与杀线虫剂、杀螨剂、防护剂、除草安全剂、生长调节剂、植物营养素或土壤调节剂等混合使用。The composition of the present invention can also be used in combination with other compounds having fungicidal, insecticidal or herbicidal properties. It can also be used with nematicides, acaricides, protective agents, herbicide safeners, growth regulators, phytonutrients or soil regulators. And so on.
一般合成过程General Synthesis Process
在本说明书中，如果在化学名称和化学结构间存在任何差异，结构是占优的。一般地，本发明的化合物可以通过本发明所描述的方法制备得到，除非有进一步的说明，其中各取代基的定义如本发明所述。In this specification, if there is any difference between the chemical name and the chemical structure, the structure is dominant. Generally, the compounds of the present invention can be prepared by the methods described in the present invention, unless further specified, wherein the definition of each substituent is as described in the present invention.
所属领域的技术人员将认识到：本发明所描述的化学反应可以用来合适地制备许多本发明的其他化合物，且用于制备本发明的化合物的其它方法都被认为是在本发明的范围之内。例如，根据本发明那些非例证的化合物的合成可以成功地被所属领域的技术人员通过修饰方法完成，如适当的保护干扰基团，通过利用其他已知的试剂(除了本发明所描述的)，或将反应条件做一些常规的修改。另外，本发明所公开的反应或已知的反应条件也公认地适用于本发明其他化合物的制备。另外，在一些实施方案中，如无特殊说明，本发明所述的反应是在室温下进行，其中室温为0～35℃。Those skilled in the art will recognize that the chemical reactions described in the present invention can be used to suitably prepare many other compounds of the present invention, and other methods for preparing the compounds of the present invention are considered to be within the scope of the present invention. Inside. For example, the synthesis of those non-exemplified compounds according to the present invention can be successfully accomplished by those skilled in the art through modification methods, such as appropriate protection of interference groups, through the use of other known reagents (except as described in the present invention), Or make some conventional modifications to the reaction conditions. In addition, the reactions disclosed in the present invention or known reaction conditions are also recognized to be suitable for the preparation of other compounds of the present invention. In addition, in some embodiments, unless otherwise specified, the reaction of the present invention is performed at room temperature, where the room temperature is 0 to 35 ° C.
本发明核磁共振氢谱的测试条件是：室温条件下，布鲁克(Bruker)400MHz或600MHz的核磁仪，以 CDC1 3，d 6-DMSO，CD 3OD或d 6-丙酮为溶剂(报导以ppm为单位)，用TMS(0ppm)或氯仿(7.26ppm)作为参照标准。当出现多重峰的时候，将使用下面的缩写：s(singlet，单峰)，d(doublet，双峰)，t(triplet，三重峰)，q(quartet，四重峰)，m(multiplet，多重峰)，br(broadened，宽峰)，dd(doublet of doublets，双二重峰)，dt(doublet of triplets，双三重峰)。偶合常数，用赫兹(Hz)表示。 The test conditions of the nuclear magnetic resonance hydrogen spectrum of the present invention are as follows: at room temperature, a Bruker 400MHz or 600MHz nuclear magnetometer, using CDC1 3 , d 6 -DMSO, CD 3 OD or d 6 -acetone as a solvent (reported in ppm as Unit), using TMS (0ppm) or chloroform (7.26ppm) as the reference standard. When multiple peaks appear, the following abbreviations will be used: s (singlet, singlet), d (doublet, doublet), t (triplet, triplet), q (quartet, quadruple), m (multiplet, Multiples), br (broadened), dd (doublet of doublets), dt (doublet of triplets). Coupling constant, expressed in Hertz (Hz).
本发明所用质谱测试条件为：低分辨率质谱(MS)数据测定的条件是：Agilent 6120 Quadrupole HPLC-MS(柱子型号：Zorbax SB-C18,2.1 x 30mm,3.5μm,6min,流速为0.6mL/min，流动相：5％-95％(含0.1％甲酸的CH 3CN)在(含0.1％甲酸的H 2O)中的比例))，在210/254nm用UV检测，用电喷雾电离模式(ESI)。 The mass spectrometry test conditions used in the present invention are: The conditions for low-resolution mass spectrometry (MS) data measurement are: Agilent 6120 Quadrupole HPLC-MS (column model: Zorbax SB-C18, 2.1 x 30mm, 3.5 μm, 6min, flow rate 0.6mL / min, mobile phase: 5% -95% (proportion of CH 3 CN containing 0.1% formic acid) in (H 2 O containing 0.1% formic acid)), UV detection at 210 / 254nm, electrospray ionization mode (ESI).
下列合成方案描述了制备本发明公开化合物的步骤。The following synthetic schemes describe the steps for preparing the compounds disclosed herein.
合成方案Synthesis scheme
合成方案一Synthesis scheme one
Figure PCTCN2019091137-appb-000085
Figure PCTCN2019091137-appb-000085
目标化合物(II)可以通过合成方案一制备得到。化合物a发生酯化反应得到化合物b；化合物b与水合肼反应得到化合物c；化合物c在碱性(如三乙胺)条件下与草酰氯单乙酯反应后得到双酰肼中间体，双酰肼中间体在碱性(如三乙胺)条件下发生环合，得到化合物d；化合物d被还原剂(如硼氢化钠)还原得到化合物e；化合物e发生取代反应得到化合物f；化合物f与化合物g在碱性在条件(如碳酸钾)下反应，得到目标化合物(II)；The target compound (II) can be prepared by the first synthetic scheme. Compound a undergoes esterification to give compound b; compound b reacts with hydrazine hydrate to give compound c; compound c is reacted with oxalyl chloride monoethyl ester under basic (such as triethylamine) conditions to give the bishydrazide intermediate, bisacyl The hydrazine intermediate is cyclized under basic (such as triethylamine) conditions to obtain compound d; compound d is reduced by a reducing agent (such as sodium borohydride) to obtain compound e; compound e undergoes a substitution reaction to obtain compound f; compound f and Compound g is reacted under basic conditions (such as potassium carbonate) to obtain the target compound (II);
其中，R 1、R 2、R 3、R 4和R 5具有本发明所述的含义。 Among them, R 1 , R 2 , R 3 , R 4 and R 5 have the meanings described in the present invention.
合成方案二Synthesis scheme two
Figure PCTCN2019091137-appb-000086
Figure PCTCN2019091137-appb-000086
目标化合物(III)可以通过合成方案二制备得到。化合物a1发生酯化反应得到化合物b1；化合物b1与水合肼反应得到化合物c1；化合物c1在碱性(如三乙胺)条件下与草酰氯单乙酯反应后得到双酰肼中间体，双酰肼中间体在碱性(如三乙胺)条件下发生环合，得到化合物d1；化合物d1被还原剂(如硼氢化钠)还原得到化合物e1；化合物e1发生取代反应得到化合物f1；化合物f1与化合物g在碱性在条件(如碳酸钾)下反应，得到目标化合物(III)；The target compound (III) can be prepared by the second synthetic scheme. Compound a1 undergoes esterification to obtain compound b1; compound b1 reacts with hydrazine hydrate to obtain compound c1; compound c1 reacts with oxalyl chloride monoethyl ester under basic (such as triethylamine) conditions to obtain the diacylhydrazine intermediate, diacyl The hydrazine intermediate is cyclized under basic (such as triethylamine) conditions to obtain compound d1; compound d1 is reduced by a reducing agent (such as sodium borohydride) to obtain compound e1; substitution reaction of compound e1 to obtain compound f1; compound f1 and Compound g is reacted under basic conditions (such as potassium carbonate) to obtain the target compound (III);
其中，R 2、R 3、R 4和R 5具有本发明所述的含义。 Among them, R 2 , R 3 , R 4 and R 5 have the meanings described in the present invention.
实施例Examples
中间体1：2-(2,4-二氟苯氧基)苯甲酸的合成Intermediate 1: Synthesis of 2- (2,4-difluorophenoxy) benzoic acid
Figure PCTCN2019091137-appb-000087
Figure PCTCN2019091137-appb-000087
步骤A：2-(2,4-二氟苯氧基)苯甲腈的合成Step A: Synthesis of 2- (2,4-difluorophenoxy) benzonitrile
将2,4-二氟苯酚(2.3mL,24mmol)，邻氟苯腈(2.2mL,20mmol)和碳酸钾(4.1g,30mmol)加入到反应瓶中，加入N,N-二甲基甲酰胺(30mL)后，升温至110℃并搅拌反应12小时。冷却至室温，加水(100mL)淬灭反应，再用乙酸乙酯(50mL x 3)萃取，饱和食盐水(100mL)洗，合并有机相后，用无水硫酸钠干燥，减压浓缩得到5.1g棕色固体，产率：97％。Add 2,4-difluorophenol (2.3 mL, 24 mmol), o-fluorobenzonitrile (2.2 mL, 20 mmol) and potassium carbonate (4.1 g, 30 mmol) to the reaction flask, and add N, N-dimethylformamide (30 mL), the temperature was raised to 110 ° C, and the reaction was stirred for 12 hours. Cool to room temperature, add water (100 mL) to quench the reaction, extract with ethyl acetate (50 mL), wash with saturated brine (100 mL), combine the organic phases, dry over anhydrous sodium sulfate, and concentrate under reduced pressure to obtain 5.1 g Brown solid, yield: 97%.
步骤B：2-(2,4-二氟苯氧基)苯甲酸的合成Step B: Synthesis of 2- (2,4-difluorophenoxy) benzoic acid
在冰浴条件下，将2-(2,4-二氟苯氧基)苯甲腈(4.6g,20mmol)和氢氧化钾(20.2g,360mmol)悬浮于甲醇(12mL,0.6mL/mmol)和乙醇(52mL,2.6mL/mmol)的混合溶液中。滴加30％的过氧化氢溶液(20mL,1.0mL/mmol)，升温至60℃回流4小时后，在冰浴条件下滴加浓盐酸酸化，再用二氯甲烷(50mL x 3)萃取，饱和食盐水(100mL)洗，合并有机相后，用无水硫酸钠干燥，减压浓缩得到4.8g棕色固体，产率：96％。Under ice-bath conditions, 2- (2,4-difluorophenoxy) benzonitrile (4.6 g, 20 mmol) and potassium hydroxide (20.2 g, 360 mmol) were suspended in methanol (12 mL, 0.6 mL / mmol) And ethanol (52mL, 2.6mL / mmol). 30% hydrogen peroxide solution (20mL, 1.0mL / mmol) was added dropwise, the temperature was raised to 60 ° C and refluxed for 4 hours, and then concentrated hydrochloric acid was added dropwise under an ice bath to acidify, and then extracted with dichloromethane (50mL × 3), It was washed with saturated brine (100 mL), and the organic phases were combined, dried over anhydrous sodium sulfate, and concentrated under reduced pressure to obtain 4.8 g of a brown solid. Yield: 96%.
LC-MS:m/z 251.3[M+H] +。 LC-MS: m / z 251.3 [M + H] + .
中间体2：(1-甲基-1H-四唑-5-基)(苯基)甲酮肟的合成Intermediate 2: Synthesis of (1-methyl-1H-tetrazol-5-yl) (phenyl) methanone oxime
Figure PCTCN2019091137-appb-000088
Figure PCTCN2019091137-appb-000088
步骤A：N-甲基-2-氧代-2-苯乙酰胺的合成Step A: Synthesis of N-methyl-2-oxo-2-phenylacetamide
0℃条件下，将苯甲酰甲酸甲酯(164g,1mol)溶于甲醇(500mL)中，并逐滴加入40％甲胺水溶液(101g,1.3mol)，滴加完成，转至室温搅拌反应2小时。减压浓缩除去甲醇，加乙酸乙酯(300mL)稀释，经水(200mL)洗、氢氧化钠(1N,200mL)洗、盐酸(1N,200mL)洗和饱和食盐水(200mL)洗，并用无水硫酸钠干燥，减压浓缩得到130g淡黄色固体，产率：80％。At 0 ° C, methyl benzoylformate (164g, 1mol) was dissolved in methanol (500mL), and a 40% methylamine aqueous solution (101g, 1.3mol) was added dropwise. After the dropwise addition was completed, the reaction was stirred at room temperature. 2 hours. The methanol was concentrated under reduced pressure, diluted with ethyl acetate (300 mL), washed with water (200 mL), washed with sodium hydroxide (1N, 200 mL), washed with hydrochloric acid (1N, 200 mL), and washed with saturated brine (200 mL). Drying with sodium sulfate and concentration under reduced pressure gave 130 g of a pale yellow solid, yield: 80%.
步骤B：N-甲基-2-氧代-2-苯基亚氨代乙酰氯的合成Step B: Synthesis of N-methyl-2-oxo-2-phenyliminoacetyl chloride
0℃条件下，将N-甲基-2-氧代-2-苯乙酰胺(65g,0.4mol)溶于N,N-二甲基甲酰胺(2.9g)和氯仿(500mL)混合溶液中，并逐滴加入二氯亚砜(71.4g,0.6mol)，滴加完成，转至室温搅拌反应2小时后，升温回流反应8小时。减压浓缩除去溶剂，加入甲苯(100mL)，并在室温下搅拌8小时后，减压浓缩得到70g棕色油状液体，产率：70％。N-methyl-2-oxo-2-phenylacetamide (65 g, 0.4 mol) was dissolved in a mixed solution of N, N-dimethylformamide (2.9 g) and chloroform (500 mL) at 0 ° C. Then, dichlorosulfoxide (71.4 g, 0.6 mol) was added dropwise. After the dropwise addition was completed, the reaction was stirred at room temperature for 2 hours, and the reaction was heated at reflux for 8 hours. The solvent was removed by concentration under reduced pressure, toluene (100 mL) was added, and the mixture was stirred at room temperature for 8 hours, and then concentrated under reduced pressure to obtain 70 g of a brown oily liquid, yield: 70%.
步骤C：(1-甲基-1H-四唑-5-基)(苯基)甲酮的合成Step C: Synthesis of (1-methyl-1H-tetrazol-5-yl) (phenyl) methanone
室温下，将叠氮化钠(6.5g,100mmol)和四叔丁基溴化铵(1.62g,5mmol)溶于甲苯(20mL)和水(20mL)的混合溶液中，滴加N-甲基-2-氧代-2-苯基亚氨代乙酰氯(18.2g,100mmol)的甲苯(60mL)溶液，滴加完成，搅拌反应2小时。加入甲苯(20mL)，经水(100mL x 3)和饱和食盐水(100mL)洗涤，并用无水硫酸钠干燥后，浓缩得到15.4g棕色油状液体，产率：85％。At room temperature, dissolve sodium azide (6.5g, 100mmol) and tetra-tert-butylammonium bromide (1.62g, 5mmol) in a mixed solution of toluene (20mL) and water (20mL), and dropwise add N-methyl A solution of 2-oxo-2-phenyliminoacetyl chloride (18.2 g, 100 mmol) in toluene (60 mL) was added dropwise, and the reaction was stirred for 2 hours. Toluene (20 mL) was added, washed with water (100 mL) and saturated brine (100 mL), dried over anhydrous sodium sulfate, and concentrated to obtain 15.4 g of a brown oily liquid. Yield: 85%.
步骤D：(1-甲基-1H-四唑-5-基)(苯基)甲酮肟的合成Step D: Synthesis of (1-methyl-1H-tetrazol-5-yl) (phenyl) methanone oxime
室温下，将(1-甲基-1H-四唑-5-基)(苯基)甲酮(15g,80mmol)和盐酸羟胺(11.1g,160mmol)溶于乙醇(100mL)中，升温至48℃，搅拌反应12小时。减压浓缩除去乙醇，加水(100mL)，再用乙酸乙酯(50mL x 3)萃取，有机相用饱和食盐水(100mL)洗，浓缩，残留物经柱层析分离[石油醚/乙酸乙酯(v/v)＝4/1]，得到5.6g浅黄色固体，产率：34％。(1-methyl-1H-tetrazol-5-yl) (phenyl) methanone (15 g, 80 mmol) and hydroxylamine hydrochloride (11.1 g, 160 mmol) were dissolved in ethanol (100 mL) at room temperature, and the temperature was raised to 48 The reaction was stirred at 12 ° C for 12 hours. The ethanol was concentrated under reduced pressure, water (100 mL) was added, and the mixture was extracted with ethyl acetate (50 mL). The organic phase was washed with saturated brine (100 mL), concentrated, and the residue was separated by column chromatography. [Petroleum ether / ethyl acetate (v / v) = 4/1], obtaining 5.6 g of a pale yellow solid, yield: 34%.
1H NMR(400MHz,CDCl 3)δ(ppm):10.48(s,1H),7.41(dd,J＝12.9,7.2Hz,3H),7.32(t,J＝7.4Hz,2H),3.97(s,3H)； 1H NMR (400MHz, CDCl 3 ) δ (ppm): 10.48 (s, 1H), 7.41 (dd, J = 12.9, 7.2 Hz, 3H), 7.32 (t, J = 7.4 Hz, 2H), 3.97 (s, 3H);
LC-MS:m/z 204.1[M+H] +。 LC-MS: m / z 204.1 [M + H] + .
实施例1：(Z)-(1-甲基-1H-四唑-5-基)(苯基)甲酮O-((5-(2-(2,4-二氟苯氧基)苯基)-1,3,4-噁二唑-2-基)甲基)肟的合成Example 1: (Z)-(1-methyl-1H-tetrazol-5-yl) (phenyl) methanone O-((5- (2- (2,4-difluorophenoxy) benzene Of phenyl) -1,3,4-oxadiazol-2-yl) methyl) oxime
Figure PCTCN2019091137-appb-000089
Figure PCTCN2019091137-appb-000089
步骤A：2-(2,4-二氟苯氧基)苯甲酸甲酯的合成Step A: Synthesis of methyl 2- (2,4-difluorophenoxy) benzoate
室温下，将2-(2,4-二氟苯氧基)苯甲酸(5.0g,20mmol)溶于甲醇(100mL)中，加入浓硫酸(2.0mL)，升温至75℃回流8小时后，减压浓缩除去甲醇，加水(100mL)稀释，再用乙酸乙酯(50mL x 3)萃取，饱和食盐水(100mL)洗，合并有机相后，用无水硫酸钠干燥，减压浓缩得到5.1g棕色油状液体，产率：97％。At room temperature, 2- (2,4-difluorophenoxy) benzoic acid (5.0 g, 20 mmol) was dissolved in methanol (100 mL), concentrated sulfuric acid (2.0 mL) was added, and the temperature was raised to 75 ° C under reflux for 8 hours. The methanol was concentrated under reduced pressure, diluted with water (100 mL), and extracted with ethyl acetate (50 mL), washed with saturated brine (100 mL), and the organic phases were combined, dried over anhydrous sodium sulfate, and concentrated under reduced pressure to obtain 5.1 g. Brown oily liquid, yield: 97%.
步骤B：2-(2,4-二氟苯氧基)苯甲酰肼的合成Step B: Synthesis of 2- (2,4-difluorophenoxy) benzoyl hydrazide
室温下，将2-(2,4-二氟苯氧基)苯甲酸甲酯(5.3g,20mmol)和水合肼(4.9mL,100mmol)充分溶于甲醇(100mL)中，升温至75℃回流8小时后，将反应液冷却至室温，减压浓缩除去甲醇，加水(200mL)，减压抽滤，滤饼烘干后，得到4.8g白色固体，产率：91％。At room temperature, methyl 2- (2,4-difluorophenoxy) benzoate (5.3 g, 20 mmol) and hydrazine hydrate (4.9 mL, 100 mmol) were sufficiently dissolved in methanol (100 mL), and the temperature was raised to 75 ° C and refluxed. After 8 hours, the reaction solution was cooled to room temperature, concentrated under reduced pressure to remove methanol, water (200 mL) was added, and filtered under reduced pressure, and the filter cake was dried to obtain 4.8 g of a white solid. Yield: 91%.
步骤C：5-(2-(2,4-二氟苯氧基)苯基)-1,3,4-噁二唑-2-羧酸乙酯Step C: 5- (2- (2,4-difluorophenoxy) phenyl) -1,3,4-oxadiazole-2-carboxylic acid ethyl ester
0℃条件下，将2-(2,4-二氟苯氧基)苯甲酰肼(5.3g,20mmol)和三乙胺(5.6mL,40mmol)充分溶于二氯甲烷(100mL)中，并逐滴加入草酰氯单乙酯(2.5mL,22mmol)，滴加完成，转至室温搅拌反应8小时后，加入三乙胺(2.8mL,20mmol)和对甲苯磺酰氯(3.8g,20mmol)，继续搅拌反应12小时。加入二氯甲烷(100mL)，经水(150mL)洗、饱和碳酸氢钠溶液(150mL)洗和饱和食盐水(150mL)洗后，合并有机相，减压浓缩，残留物经柱层析分离[石油醚)/乙酸乙酯(v/v)＝8/1]，得到4.2g白色固体，产率：61％。At 0 ° C, 2- (2,4-difluorophenoxy) benzoyl hydrazide (5.3 g, 20 mmol) and triethylamine (5.6 mL, 40 mmol) were sufficiently dissolved in dichloromethane (100 mL). Monoethyl oxalyl chloride (2.5 mL, 22 mmol) was added dropwise. After the dropwise addition was completed, the reaction was stirred at room temperature for 8 hours. Triethylamine (2.8 mL, 20 mmol) and p-toluenesulfonyl chloride (3.8 g, 20 mmol) were added. The reaction was continued with stirring for 12 hours. Dichloromethane (100 mL) was added, washed with water (150 mL), saturated sodium bicarbonate solution (150 mL), and saturated brine (150 mL). The organic phases were combined, concentrated under reduced pressure, and the residue was separated by column chromatography. Petroleum ether) / ethyl acetate (v / v) = 8/1] to obtain 4.2 g of a white solid, yield: 61%.
步骤D：(5-(2-(2,4-二氟苯氧基)苯基)-1,3,4-噁二唑-2-基)甲醇的合成Step D: Synthesis of (5- (2- (2,4-difluorophenoxy) phenyl) -1,3,4-oxadiazol-2-yl) methanol
0℃条件下，将5-(2-(2,4-二氟苯氧基)苯基)-1,3,4-噁二唑-2-羧酸乙酯(4.2g,12mmol)和氯化钙(2.7g,24mmol)悬浮于乙醇(100mL)中，并分三次加入硼氢化钠(1.36g,36mmol)。转至室温搅拌反应8小时，加水(100mL)淬灭反应，再用二氯甲烷(50mL x 3)萃取，饱和食盐水(100mL)洗，合并有机相后，用无水硫酸钠干燥，减压浓缩得到3.5g白色固体，产率：95％。At 0 ° C, 5- (2- (2,4-difluorophenoxy) phenyl) -1,3,4-oxadiazole-2-carboxylic acid ethyl ester (4.2 g, 12 mmol) and chlorine Calcium chloride (2.7 g, 24 mmol) was suspended in ethanol (100 mL), and sodium borohydride (1.36 g, 36 mmol) was added in three portions. The reaction was stirred at room temperature for 8 hours. The reaction was quenched by adding water (100 mL), and then extracted with dichloromethane (50 mL), washed with saturated brine (100 mL), combined organic phases, dried over anhydrous sodium sulfate, and decompressed. Concentration gave 3.5 g of a white solid, yield: 95%.
步骤E：2-(溴甲基)-5-(2-(2,4-二氟苯氧基)苯基)-1,3,4-噁二唑的合成Step E: Synthesis of 2- (bromomethyl) -5- (2- (2,4-difluorophenoxy) phenyl) -1,3,4-oxadiazole
0℃条件下，将(5-(2-(2,4-二氟苯氧基)苯基)-1,3,4-噁二唑-2-基)甲醇(609mg,2mmol)溶于无水二氯甲烷(8mL)中，滴加三溴化磷(0.19mL,2mmol)的二氯甲烷溶液(4mL)。转至室温搅拌反应8小时，减压浓缩，残留物经柱层析分离[石油醚/乙酸乙酯(v/v)＝10/1]，得到235mg白色固体，产率：32％。(5- (2- (2,4-difluorophenoxy) phenyl) -1,3,4-oxadiazol-2-yl) methanol (609 mg, 2 mmol) was dissolved in In water dichloromethane (8 mL), a dichloromethane solution (4 mL) of phosphorus tribromide (0.19 mL, 2 mmol) was added dropwise. The reaction was stirred at room temperature for 8 hours, concentrated under reduced pressure, and the residue was separated by column chromatography [petroleum ether / ethyl acetate (v / v) = 10/1] to obtain 235 mg of a white solid, yield: 32%.
步骤F：(Z)-(1-甲基-1H-四唑-5-基)(苯基)甲酮O-((5-(2-(2,4-二氟苯氧基)苯基)-1,3,4-噁二唑-2-基)甲基)肟的合成Step F: (Z)-(1-methyl-1H-tetrazol-5-yl) (phenyl) methanone O-((5- (2- (2,4-difluorophenoxy) phenyl ) -1,3,4-oxadiazol-2-yl) methyl) oxime
室温条件下，将2-(溴甲基)-5-(2-(2,4-二氟苯氧基)苯基)-1,3,4-噁二唑(235mg,0.64mmol)，(1-甲基-1H-四唑-5-基)(苯基)甲酮肟(130mg,0.64mmol)和碳酸钾(133mg,0.96mmol)加入到反应瓶中，加入N,N-二甲基甲酰胺(10mL)后，搅拌反应12小时。加水(50mL)淬灭反应，乙酸乙酯(30mL x 3)萃取，饱和食盐水(50mL)洗，合并有机相后，减压浓缩得到粗品，粗品经柱层析分离[石油醚/乙酸乙酯(v/v)＝5/1]，得到144mg白色固体，产率：46％。At room temperature, 2- (bromomethyl) -5- (2- (2,4-difluorophenoxy) phenyl) -1,3,4-oxadiazole (235 mg, 0.64 mmol), ( 1-Methyl-1H-tetrazol-5-yl) (phenyl) methanone oxime (130 mg, 0.64 mmol) and potassium carbonate (133 mg, 0.96 mmol) were added to the reaction flask, and N, N-dimethyl was added After formamide (10 mL), the reaction was stirred for 12 hours. Water (50 mL) was added to quench the reaction, and the mixture was extracted with ethyl acetate (30 mL), washed with saturated brine (50 mL), the organic phases were combined, and concentrated under reduced pressure to obtain a crude product, which was separated by column chromatography [petroleum ether / ethyl acetate (v / v) = 5/1], 144 mg of a white solid was obtained, yield: 46%.
1H NMR(400MHz,DMSO-d 6)δ(ppm):8.03(d,J＝6.1Hz,1H),7.62-7.25(m,9H),7.10(s,1H),6.95(d,J＝7.1Hz,1H),5.68(s,2H),4.05(s,3H)； 1 H NMR (400MHz, DMSO-d 6 ) δ (ppm): 8.03 (d, J = 6.1 Hz, 1H), 7.62-7.25 (m, 9H), 7.10 (s, 1H), 6.95 (d, J = 7.1Hz, 1H), 5.68 (s, 2H), 4.05 (s, 3H);
LC-MS:m/z 490.8[M+H] +。 LC-MS: m / z 490.8 [M + H] + .
通过实施例1的类似制备方法，采用相应的中间体化合物、反应试剂、反应条件及后处理方式，即可制备得到表1中的目标化合物。By using a similar preparation method of Example 1 and using the corresponding intermediate compounds, reaction reagents, reaction conditions, and post-treatment methods, the target compounds in Table 1 can be prepared.
表1Table 1
Figure PCTCN2019091137-appb-000090
Figure PCTCN2019091137-appb-000090
Figure PCTCN2019091137-appb-000091
Figure PCTCN2019091137-appb-000091
Figure PCTCN2019091137-appb-000092
Figure PCTCN2019091137-appb-000092
Figure PCTCN2019091137-appb-000093
Figure PCTCN2019091137-appb-000093
Figure PCTCN2019091137-appb-000094
Figure PCTCN2019091137-appb-000094
Figure PCTCN2019091137-appb-000095
Figure PCTCN2019091137-appb-000095
Figure PCTCN2019091137-appb-000096
Figure PCTCN2019091137-appb-000096
Figure PCTCN2019091137-appb-000097
Figure PCTCN2019091137-appb-000097
Figure PCTCN2019091137-appb-000098
Figure PCTCN2019091137-appb-000098
Figure PCTCN2019091137-appb-000099
Figure PCTCN2019091137-appb-000099
Figure PCTCN2019091137-appb-000100
Figure PCTCN2019091137-appb-000100
Figure PCTCN2019091137-appb-000101
Figure PCTCN2019091137-appb-000101
Figure PCTCN2019091137-appb-000102
Figure PCTCN2019091137-appb-000102
Figure PCTCN2019091137-appb-000103
Figure PCTCN2019091137-appb-000103
Figure PCTCN2019091137-appb-000104
Figure PCTCN2019091137-appb-000104
Figure PCTCN2019091137-appb-000105
Figure PCTCN2019091137-appb-000105
Figure PCTCN2019091137-appb-000106
Figure PCTCN2019091137-appb-000106
Figure PCTCN2019091137-appb-000107
Figure PCTCN2019091137-appb-000107
Figure PCTCN2019091137-appb-000108
Figure PCTCN2019091137-appb-000108
Figure PCTCN2019091137-appb-000109
Figure PCTCN2019091137-appb-000109
Figure PCTCN2019091137-appb-000110
Figure PCTCN2019091137-appb-000110
Figure PCTCN2019091137-appb-000111
Figure PCTCN2019091137-appb-000111
Figure PCTCN2019091137-appb-000112
Figure PCTCN2019091137-appb-000112
Figure PCTCN2019091137-appb-000113
Figure PCTCN2019091137-appb-000113
Figure PCTCN2019091137-appb-000114
Figure PCTCN2019091137-appb-000114
Figure PCTCN2019091137-appb-000115
Figure PCTCN2019091137-appb-000115
Figure PCTCN2019091137-appb-000116
Figure PCTCN2019091137-appb-000116
Figure PCTCN2019091137-appb-000117
Figure PCTCN2019091137-appb-000117
Figure PCTCN2019091137-appb-000118
Figure PCTCN2019091137-appb-000118
Figure PCTCN2019091137-appb-000119
Figure PCTCN2019091137-appb-000119
Figure PCTCN2019091137-appb-000120
Figure PCTCN2019091137-appb-000120
Figure PCTCN2019091137-appb-000121
Figure PCTCN2019091137-appb-000121
Figure PCTCN2019091137-appb-000122
Figure PCTCN2019091137-appb-000122
实施例137：(Z)-(1-甲基-1H-四唑-5-基)(苯基)甲酮O-((5-(4-溴苯基)-1,3,4-噁二唑-2-基)甲基)肟的合成Example 137: (Z)-(1-methyl-1H-tetrazol-5-yl) (phenyl) methanone O-((5- (4-bromophenyl) -1,3,4-oxazine Synthesis of Diazol-2-yl) methyl) oxime
Figure PCTCN2019091137-appb-000123
Figure PCTCN2019091137-appb-000123
室温条件下，将2-(溴甲基)-5-(4-溴苯基)-1,3,4-噁二唑(381mg,1.2mmol,采用相应的原料通过实施例1步骤A至步骤E的类似合成方法制备得到)，(1-甲基-1H-四唑-5-基)(苯基)甲酮肟(243mg,1.2mmol)和碳酸钾(162mg,1.2mmol)加入到反应瓶中，加入N,N-二甲基甲酰胺(10mL)后，搅拌反应12小时。加水(50mL)淬灭反应，再用乙酸乙酯(30mL x 3)萃取，饱和食盐水(50mL)洗，合并有机相后，浓缩得到粗品，粗品经柱层析[石油醚/乙酸乙酯(v/v)＝5/1]，得到250mg白色固体，产率：74％。At room temperature, 2- (bromomethyl) -5- (4-bromophenyl) -1,3,4-oxadiazole (381 mg, 1.2 mmol) was passed through Step A to Step 1 of Example 1 using the corresponding raw materials. Prepared by a similar synthetic method of E), (1-methyl-1H-tetrazol-5-yl) (phenyl) methanone oxime (243 mg, 1.2 mmol) and potassium carbonate (162 mg, 1.2 mmol) were added to the reaction flask After adding N, N-dimethylformamide (10 mL), the reaction was stirred for 12 hours. Water (50 mL) was added to quench the reaction, and the mixture was extracted with ethyl acetate (30 mL) and washed with saturated brine (50 mL). The organic phases were combined and concentrated to obtain a crude product. v / v) = 5/1] to obtain 250 mg of a white solid, yield: 74%.
1H NMR(400MHz,DMSO-d 6)δ(ppm):7.94(d,J＝8.5Hz,2H),7.8.3(d,J＝8.5Hz,2H),7.59-7.43(m,5H),5.66(s,2H),4.11(s,3H)； 1 H NMR (400MHz, DMSO-d 6 ) δ (ppm): 7.94 (d, J = 8.5 Hz, 2H), 7.8.3 (d, J = 8.5 Hz, 2H), 7.59-7.43 (m, 5H) , 5.66 (s, 2H), 4.11 (s, 3H);
LC-MS:m/z 440.6[M+H] +。 LC-MS: m / z 440.6 [M + H] + .
实施例138：(Z)-(1-甲基-1H-四唑-5-基)(苯基)甲酮O-((5-(4-(三氟甲基)苯基)-1,3,4-噁二唑-2-基)甲基)肟的合成Example 138: (Z)-(1-methyl-1H-tetrazol-5-yl) (phenyl) methanone O-((5- (4- (trifluoromethyl) phenyl) -1, Synthesis of 3,4-oxadiazol-2-yl) methyl) oxime
Figure PCTCN2019091137-appb-000124
Figure PCTCN2019091137-appb-000124
室温条件下，将2-(溴甲基)-5-(4-(三氟甲基)苯基)-1,3,4-噁二唑(240mg,0.8mmol，采用相应的原料通过实施例1步骤A至步骤E的类似合成方法制备得到)，(1-甲基-1H-四唑-5-基)(苯基)甲酮肟(158mg,0.8mmol)和碳酸钾(162mg,1.2mmol)加入到反应瓶中，加入N,N-二甲基甲酰胺(10mL)后，搅拌反应12小时。加水(50mL)淬灭反应，再用乙酸乙酯(30mL x 3)萃取，饱和食盐水(50mL)洗，合并有机相后，浓缩得到粗品，粗品经柱层析[石油醚/乙酸乙酯(v/v)＝5/1]，得到250mg白色固体，产率：74％。At room temperature, 2- (bromomethyl) -5- (4- (trifluoromethyl) phenyl) -1,3,4-oxadiazole (240 mg, 0.8 mmol) was passed through the examples using the corresponding raw materials. 1 Prepared by a similar synthetic method from step A to step E), (1-methyl-1H-tetrazol-5-yl) (phenyl) methanone oxime (158 mg, 0.8 mmol) and potassium carbonate (162 mg, 1.2 mmol ) Was added to the reaction flask, and after adding N, N-dimethylformamide (10 mL), the reaction was stirred for 12 hours. Water (50 mL) was added to quench the reaction, and the mixture was extracted with ethyl acetate (30 mL) and washed with saturated brine (50 mL). The organic phases were combined and concentrated to obtain a crude product. The crude product was subjected to column chromatography [petroleum ether / ethyl acetate ( v / v) = 5/1] to obtain 250 mg of a white solid, yield: 74%.
1H NMR(400MHz,DMSO-d 6)δ(ppm):8.22(d,J＝8.0Hz,2H),7.99(d,J＝8.2Hz,2H),7.58-7.44(m,5H),5.70(s,2H),4.14(s,3H)； 1 H NMR (400MHz, DMSO-d 6 ) δ (ppm): 8.22 (d, J = 8.0 Hz, 2H), 7.99 (d, J = 8.2 Hz, 2H), 7.58-7.44 (m, 5H), 5.70 (s, 2H), 4.14 (s, 3H);
LC-MS:m/z 430.7[M+H] +。 LC-MS: m / z 430.7 [M + H] + .
活性测试Activity test
1.测试例Test case
本测试例用于测定实施例中制得的化合物的杀真菌活性。本测试例中的试验靶标为黄瓜霜霉病菌。用N,N-二甲基甲酰胺溶解成1％EC备用。采用活体盆栽法，评价这些化合物在200mg/L剂量下对试验靶标的杀真菌活性。试验方法采用创制农药生物活性评价SOP(杀菌剂卷)。This test example is used to determine the fungicidal activity of the compounds prepared in the examples. The test target in this test example is cucumber downy mildew. Use N, N-dimethylformamide to dissolve into 1% EC for future use. In vivo pot method was used to evaluate the fungicidal activity of these compounds against test targets at a dose of 200 mg / L. The test method uses a SOP (Fungicide Roll) to evaluate the biological activity of the created pesticide.
黄瓜霜霉病菌(Pseudoperonospora cubensis)：Cucumber downy mildew (Pseudoperonospora cubensis):
选择1张真叶期(摘去生长点)长势一致的盆栽黄瓜苗，喷雾处理后自然晾干，处理后24h后进行接种，取新鲜黄瓜霜霉病病叶，用毛笔蘸取蒸馏水洗下病叶背面孢子囊，配成孢子囊悬浮液(2-3×10 5个/mL)。用接种喷雾器(压力0.1MPa)在黄瓜苗上均匀喷雾接种，接种后的试材移至人工气候室，保持相对湿度100％，温度为21℃左右，24h后保持温度21℃左右，相对湿度95％左右保湿诱发，5d后视空白对照发病情况进行分级调查，按病指计算防效。 Select a potted cucumber seedling with the same growth period at the true leaf stage (removal of growth points), spray dry after treatment, and inoculate 24 hours after treatment. Take fresh cucumber downy mildew diseased leaves, dip in distilled water with a brush to wash the disease sporangia surface of leaf, dubbed sporangia suspension (2-3 × 10 5 th / mL). Use an inoculation sprayer (pressure 0.1 MPa) to uniformly inoculate the cucumber seedlings. The inoculated specimens are moved to an artificial climate chamber and maintained at a relative humidity of 100% at a temperature of about 21 ° C. After 24 hours, the temperature is maintained at about 21 ° C and a relative humidity of 95. Induced by moisturizing at about%, 5 days later, the incidence of the blank control group was graded, and the prevention effect was calculated according to the diseased fingers.
测试结果如表2所示。The test results are shown in Table 2.
表2Table 2
化合物Compound 防效(％)Prevention effect (%)
实施例1Example 1 100100
实施例2Example 2 100100
实施例3Example 3 100100
实施例4Example 4 100100
实施例5Example 5 100100
实施例6Example 6 100100
实施例8Example 8 100100
实施例10Example 10 100100
实施例11Example 11 100100
实施例12Example 12 100100
实施例13Example 13 100100
实施例14Example 14 100100
实施例16Example 16 100100
化合物Compound 防效(％)Prevention effect (%)
实施例17Example 17 100100
实施例18Example 18 100100
2.测试例2. Test case
本测试例用于测定化合物的杀真菌活性。本测试例中的试验靶标为黄瓜霜霉病菌。用DMSO溶解成1％EC备用。采用活体盆栽法，评价这些化合物在25mg/L、12.5mg/L、6.25mg/L、3.125mg/L、1.5625mg/L剂量下对试验靶标的杀真菌活性。试验方法采用创制农药生物活性评价SOP(杀菌剂卷)。This test example is used to determine the fungicidal activity of the compound. The test target in this test example is cucumber downy mildew. Dissolve into 1% EC with DMSO for future use. In vivo pot method was used to evaluate the fungicidal activity of these compounds on test targets at 25 mg / L, 12.5 mg / L, 6.25 mg / L, 3.125 mg / L, and 1.5625 mg / L doses. The test method uses a SOP (Fungicide Roll) to evaluate the biological activity of the created pesticide.
黄瓜霜霉病菌(Pseudoperonospora cubensis)：Cucumber downy mildew (Pseudoperonospora cubensis):
选择1张真叶期(摘去生长点)长势一致的盆栽黄瓜苗，喷雾处理后自然晾干，处理后24h后进行接种，取新鲜黄瓜霜霉病病叶，用毛笔蘸取蒸馏水洗下病叶背面孢子囊，配成孢子囊悬浮液(2-3×10 5个/mL)。用接种喷雾器(压力0.1MPa)在黄瓜苗上均匀喷雾接种，接种后的试材移至人工气候室，保持相对湿度100％，温度为21℃左右，24h后保持温度21℃左右，相对湿度95％左右保湿诱发，5d后视空白对照发病情况进行分级调查，按病指计算防效。 Select a potted cucumber seedling with the same growth period at the true leaf stage (removal of growth points), spray dry after treatment, and inoculate 24 hours after treatment. Take fresh cucumber downy mildew diseased leaves, dip in distilled water with a brush to wash the disease sporangia surface of leaf, dubbed sporangia suspension (2-3 × 10 5 th / mL). Use an inoculation sprayer (pressure 0.1 MPa) to uniformly inoculate the cucumber seedlings. The inoculated specimens are moved to an artificial climate chamber and maintained at a relative humidity of 100% at a temperature of about 21 ° C. After 24 hours, the temperature is maintained at about 21 ° C and a relative humidity of 95. Induced by moisturizing at about%, 5 days later, the incidence of the blank control group was graded, and the prevention effect was calculated according to the disease index.
测试结果如表3-5所示。The test results are shown in Table 3-5.
表3本发明化合物在25mg/L剂量下对黄瓜霜霉病菌的防效Table 3 Control effect of the compound of the present invention on downy mildew of cucumber at a dose of 25 mg / L
化合物Compound 防效(％)Prevention effect (%)
实施例1Example 1 100100
实施例2Example 2 100100
实施例3Example 3 8080
实施例4Example 4 100100
实施例5Example 5 100100
实施例6Example 6 100100
实施例10Example 10 100100
实施例11Example 11 9595
实施例12Example 12 9090
实施例13Example 13 9595
实施例14Example 14 100100
实施例16Example 16 8585
实施例17Example 17 9090
实施例18Example 18 100100
实施例19Example 19 8080
实施例20Example 20 100100
实施例21Example 21 100100
实施例22Example 22 100100
实施例24Example 24 9090
实施例25Example 25 100100
实施例26Example 26 100100
实施例28Example 28 100100
实施例29Example 29 9595
实施例30Example 30 9090
实施例31Example 31 9090
化合物Compound 防效(％)Prevention effect (%)
实施例33Example 33 100100
实施例34Example 34 100100
实施例35Example 35 9898
实施例36Example 36 8080
实施例37Example 37 100100
实施例38Example 38 100100
实施例39Example 39 100100
实施例40Example 40 100100
实施例42Example 42 9898
实施例43Example 43 100100
实施例44Example 44 9898
实施例45Example 45 9898
实施例47Example 47 9898
实施例48Example 48 9898
实施例49Example 49 9393
实施例50Example 50 100100
实施例52Example 52 9898
实施例53Example 53 9595
实施例54Example 54 100100
实施例56Example 56 100100
实施例57Example 57 100100
实施例58Example 58 9090
实施例59Example 59 100100
实施例60Example 60 100100
实施例62Example 62 9696
实施例66Example 66 9898
实施例67Example 67 9898
实施例68Example 68 9898
实施例69Example 69 100100
实施例71Example 71 9898
实施例74Example 74 9090
实施例76Example 76 9898
实施例78Example 78 9393
实施例79Example 79 9898
实施例80Example 80 100100
实施例81Example 81 100100
实施例82Example 82 9090
实施例86Example 86 9898
实施例87Example 87 9595
实施例89Example 89 8585
实施例90Example 90 8787
实施例92Example 92 9898
化合物Compound 防效(％)Prevention effect (%)
实施例93Example 93 9898
实施例95Example 95 8080
实施例97Example 97 9696
实施例99Example 99 8585
实施例100Example 100 9696
实施例101Example 101 8080
实施例102Example 102 100100
实施例103Example 103 100100
实施例108Example 108 9090
实施例109Example 109 100100
实施例110Example 110 100100
实施例113Example 113 9898
实施例115Example 115 100100
实施例116Example 116 100100
实施例117Example 117 9898
实施例119Example 119 9898
实施例121Example 121 8585
实施例122Example 122 8585
实施例123Example 123 9090
实施例127Example 127 8080
实施例128Example 128 100100
实施例129Example 129 9090
实施例130Example 130 9898
实施例131Example 131 8585
实施例133Example 133 8080
实施例134Example 134 100100
实施例136Example 136 8585
表4本发明化合物在12.5mg/L剂量下对黄瓜霜霉病菌的防效Table 4 Control effects of the compounds of the present invention on cucumber downy mildew at a dose of 12.5 mg / L
化合物Compound 防效(％)Prevention effect (%)
实施例1Example 1 100100
实施例5Example 5 100100
实施例10Example 10 9898
实施例14Example 14 8080
实施例18Example 18 9898
实施例20Example 20 9595
实施例21Example 21 9090
实施例22Example 22 9090
实施例25Example 25 100100
实施例33Example 33 100100
化合物Compound 防效(％)Prevention effect (%)
实施例34Example 34 9090
实施例35Example 35 9595
实施例37Example 37 100100
实施例38Example 38 100100
实施例39Example 39 9898
实施例40Example 40 100100
实施例43Example 43 100100
实施例44Example 44 9393
实施例45Example 45 8080
实施例49Example 49 8080
实施例50Example 50 9898
实施例52Example 52 9090
实施例53Example 53 9090
实施例54Example 54 100100
实施例56Example 56 9090
实施例59Example 59 8585
实施例66Example 66 9393
实施例67Example 67 9595
实施例69Example 69 100100
实施例74Example 74 8080
实施例76Example 76 8787
实施例79Example 79 9090
实施例82Example 82 8080
实施例97Example 97 8080
实施例103Example 103 8080
实施例113Example 113 9595
实施例123Example 123 8080
实施例128Example 128 9090
实施例129Example 129 8585
实施例130Example 130 8585
实施例134Example 134 9898
表5本发明化合物在6.25mg/L剂量下对黄瓜霜霉病菌的防效Table 5 Control effect of the compound of the present invention on cucumber downy mildew at a dose of 6.25 mg / L
化合物Compound 防效(％)Prevention effect (%)
实施例10Example 10 8585
实施例18Example 18 8585
实施例25Example 25 8080
实施例33Example 33 9898
实施例35Example 35 9090
实施例37Example 37 100100
实施例38Example 38 9898
化合物Compound 防效(％)Prevention effect (%)
实施例39Example 39 8585
实施例40Example 40 9797
实施例43Example 43 100100
实施例44Example 44 8585
实施例50Example 50 8080
实施例54Example 54 100100
实施例66Example 66 8585
实施例134Example 134 9595
由上述试验结果可知本发明化合物对植物病原性真菌，尤其是对黄瓜霜霉病菌具有很好的防治效果，其中部分化合物(如实施例43或实施例54)在更低的剂量下(如3.125mg/L剂量下)对黄瓜霜霉病菌的防效仍在80％以上，具备很好的应用前景。It can be known from the above test results that the compound of the present invention has a good control effect on phytopathogenic fungi, especially against cucumber downy mildew, and some of the compounds (such as Example 43 or Example 54) are at lower doses (such as 3.125). mg / L dose) against cucumber downy mildew is still more than 80%, so it has a good application prospect.
以上详细描述了本发明的优选实施方式，但是，本发明并不限于上述实施方式中的具体细节，在本发明的技术构思范围内，可以对本发明的技术方案进行多种简单变型，这些简单变型均属于本发明的保护范围。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 idea of the present invention, various simple modifications can be made to the technical solution of the present invention. These simple modifications All belong to the protection scope of the present invention.

Claims (16)

  1. 一种化合物，其为具有式(I-A)所示的化合物或式(I-A)所示的化合物的盐、氮氧化物、或(E)和(Z)异构体以及它们的混合物：A compound which is a salt, nitrogen oxide, or (E) and (Z) isomer and a mixture thereof having a compound represented by formula (I-A) or a compound represented by formula (I-A):
    Figure PCTCN2019091137-appb-100001
    Figure PCTCN2019091137-appb-100001
    其中，among them,
    T为含有1、2、3或4个氮原子的5元杂芳基；其中，所述的5元杂芳基任选地被一个或多个烷基取代；T is a 5-membered heteroaryl group containing 1, 2, 3, or 4 nitrogen atoms; wherein the 5-membered heteroaryl group is optionally substituted with one or more alkyl groups;
    A为芳基或杂芳基；其中A任选地被1、2、3、4、5或6个R b取代； A is aryl or heteroaryl; wherein A is optionally substituted with 1, 2, 3, 4, 5 or 6 R b ;
    其中，各R b独立地为卤素、羟基、氰基、硝基、氨基、羧基、烷基、烷氧基、卤代烷基、卤代烷氧基、芳基或芳氧基； Wherein each R b is independently halogen, hydroxy, cyano, nitro, amino, carboxyl, alkyl, alkoxy, haloalkyl, haloalkoxy, aryl or aryloxy;
    B 1为CR 1或N； B 1 is CR 1 or N;
    B为CR 2或N； B is CR 2 or N;
    B 2为CR 3或N； B 2 is CR 3 or N;
    条件是：B 1、B和B 2中至多有一个为N； Provided that at most one of B 1 , B and B 2 is N;
    R 1、R 2、R 3、R 4和R 5各自独立地为氢、卤素、羟基、氰基、硝基、氨基、羧基、烷基、卤代烷基、烷氧基或卤代烷氧基； R 1 , R 2 , R 3 , R 4 and R 5 are each independently hydrogen, halogen, hydroxyl, cyano, nitro, amino, carboxyl, alkyl, haloalkyl, alkoxy or haloalkoxy;
    或R 1、R 2、R 3、R 4和R 5各自独立地为以下子结构式： Or R 1 , R 2 , R 3 , R 4 and R 5 are each independently the following substructure formula:
    Figure PCTCN2019091137-appb-100002
    Figure PCTCN2019091137-appb-100002
    其中，R 11、R 22、R 33、R 44和R 55各自独立地为氢、卤素、羟基、氰基、硝基、氨基、羧基、烷基、卤代烷基、烷氧基、卤代烷氧基、烷基胺基或烷硫基； Among them, R 11 , R 22 , R 33 , R 44 and R 55 are each independently hydrogen, halogen, hydroxyl, cyano, nitro, amino, carboxyl, alkyl, haloalkyl, alkoxy, haloalkoxy, Alkylamino or alkylthio;
    条件为：R 1、R 2、R 3、R 4和R 5中有且只有一个为
    Figure PCTCN2019091137-appb-100003
    The conditions are: there is only one of R 1 , R 2 , R 3 , R 4 and R 5 is
    Figure PCTCN2019091137-appb-100003
  2. 根据权利要求1所述的化合物，其为具有式(I)所示的化合物或式(I)所示的化合物的盐、氮氧化物、或(E)和(Z)异构体以及它们的混合物：The compound according to claim 1, which has a compound represented by formula (I) or a salt, nitrogen oxide, or (E) and (Z) isomers of a compound represented by formula (I) and their mixture:
    Figure PCTCN2019091137-appb-100004
    Figure PCTCN2019091137-appb-100004
    其中，among them,
    T为含有1、2、3或4个氮原子的5元杂芳基；其中，所述的5元杂芳基任选地被一个或多个烷基取代；T is a 5-membered heteroaryl group containing 1, 2, 3, or 4 nitrogen atoms; wherein the 5-membered heteroaryl group is optionally substituted with one or more alkyl groups;
    A为芳基或杂芳基；其中A任选地被1、2、3、4、5或6个R b取代； A is aryl or heteroaryl; wherein A is optionally substituted with 1, 2, 3, 4, 5 or 6 R b ;
    其中，各R b独立地为卤素、羟基、氰基、硝基、氨基、羧基、烷基、烷氧基、卤代烷基、卤代烷氧基、芳基或芳氧基； Wherein each R b is independently halogen, hydroxy, cyano, nitro, amino, carboxyl, alkyl, alkoxy, haloalkyl, haloalkoxy, aryl or aryloxy;
    R 1、R 2、R 3、R 4和R 5各自独立地为氢、卤素、羟基、氰基、硝基、氨基、羧基、烷基、卤代烷基、烷氧基或卤代烷氧基； R 1 , R 2 , R 3 , R 4 and R 5 are each independently hydrogen, halogen, hydroxyl, cyano, nitro, amino, carboxyl, alkyl, haloalkyl, alkoxy or haloalkoxy;
    或R 1、R 2、R 3、R 4和R 5各自独立地为以下子结构式： Or R 1 , R 2 , R 3 , R 4 and R 5 are each independently the following substructure formula:
    Figure PCTCN2019091137-appb-100005
    Figure PCTCN2019091137-appb-100005
    其中，R 11、R 22、R 33、R 44和R 55各自独立地为氢、卤素、羟基、氰基、硝基、氨基、羧基、烷基、卤代烷基、烷氧基、卤代烷氧基、烷基胺基或烷硫基； Among them, R 11 , R 22 , R 33 , R 44 and R 55 are each independently hydrogen, halogen, hydroxyl, cyano, nitro, amino, carboxyl, alkyl, haloalkyl, alkoxy, haloalkoxy, Alkylamino or alkylthio;
    条件为：R 1、R 2、R 3、R 4和R 5中有且只有一个为
    Figure PCTCN2019091137-appb-100006
    The conditions are: there is only one of R 1 , R 2 , R 3 , R 4 and R 5 is
    Figure PCTCN2019091137-appb-100006
  3. 根据权利要求1或2所述的化合物，其中，The compound according to claim 1 or 2, wherein:
    T为含有1、2、3或4个氮原子的5元杂芳基；其中，所述的5元杂芳基任选地被一个或多个C 1-6烷基取代； T is a 5-membered heteroaryl group containing 1, 2, 3 or 4 nitrogen atoms; wherein the 5-membered heteroaryl group is optionally substituted with one or more C 1-6 alkyl groups;
    A为C 6-10芳基或5-10元杂芳基；其中A任选地被1、2、3、4、5或6个R b取代； A is C 6-10 aryl or 5-10 membered heteroaryl; wherein A is optionally substituted with 1, 2, 3, 4, 5 or 6 R b ;
    其中，各R b独立地为卤素、羟基、氰基、硝基、氨基、羧基、C 1-6烷基、C 1-6烷氧基、卤代C 1-6烷基、卤代C 1-6烷氧基、C 6-10芳基或C 6-10芳氧基； Wherein each R b is independently halogen, hydroxy, cyano, nitro, amino, carboxyl, C 1-6 alkyl, C 1-6 alkoxy, halo C 1-6 alkyl, halo C 1 -6 alkoxy, C 6-10 aryl or C 6-10 aryloxy;
    R 1、R 2、R 3、R 4和R 5各自独立地为氢、卤素、羟基、氰基、硝基、氨基、羧基、C 1-6烷基、卤代C 1-6烷基、C 1-6烷氧基或卤代C 1-6烷氧基； R 1 , R 2 , R 3 , R 4 and R 5 are each independently hydrogen, halogen, hydroxyl, cyano, nitro, amino, carboxyl, C 1-6 alkyl, halo C 1-6 alkyl, C 1-6 alkoxy or halo C 1-6 alkoxy;
    或R 1、R 2、R 3、R 4和R 5各自独立地为以下子结构式： Or R 1 , R 2 , R 3 , R 4 and R 5 are each independently the following substructure formula:
    Figure PCTCN2019091137-appb-100007
    Figure PCTCN2019091137-appb-100007
    其中，R 11、R 22、R 33、R 44和R 55各自独立地为氢、卤素、羟基、氰基、硝基、氨基、羧基、C 1-6烷基、卤代C 1-6烷基、C 1-6烷氧基、卤代C 1-6烷氧基、C 1-6烷基胺基或C 1-6烷硫基。 Among them, R 11 , R 22 , R 33 , R 44 and R 55 are each independently hydrogen, halogen, hydroxyl, cyano, nitro, amino, carboxyl, C 1-6 alkyl, halo C 1-6 alkane Alkyl, C 1-6 alkoxy, halo C 1-6 alkoxy, C 1-6 alkylamino or C 1-6 alkylthio.
  4. 根据权利要求1-3任意一项所述的化合物，其中，The compound according to any one of claims 1-3, wherein:
    T为以下子结构式：T is the following substructure formula:
    Figure PCTCN2019091137-appb-100008
    Figure PCTCN2019091137-appb-100008
    其中，各R a独立地为氢或C 1-4烷基； Wherein each R a is independently hydrogen or C 1-4 alkyl;
    A为以下子结构式：A is the following substructure formula:
    Figure PCTCN2019091137-appb-100009
    Figure PCTCN2019091137-appb-100009
    其中，z为0、1、2、3、4或5；Where z is 0, 1, 2, 3, 4 or 5;
    其中，各R b独立地为卤素、羟基、氰基、硝基、氨基、羧基、C 1-4烷基、C 1-4烷氧基、卤代C 1-4烷基、卤代C 1-4烷氧基、C 6-10芳基或C 6-10芳氧基。 Wherein each R b is independently halogen, hydroxy, cyano, nitro, amino, carboxyl, C 1-4 alkyl, C 1-4 alkoxy, halo C 1-4 alkyl, halo C 1 -4 alkoxy, C 6-10 aryl or C 6-10 aryloxy.
  5. 根据权利要求1-4任意一项所述的化合物，其中，The compound according to any one of claims 1 to 4, wherein:
    T为以下子结构式：T is the following substructure formula:
    Figure PCTCN2019091137-appb-100010
    Figure PCTCN2019091137-appb-100010
    其中，各R a独立地为氢、-CH 3或-CH 2CH 3； Wherein each R a is independently hydrogen, -CH 3 or -CH 2 CH 3 ;
    A为以下子结构式：A is the following substructure formula:
    Figure PCTCN2019091137-appb-100011
    Figure PCTCN2019091137-appb-100011
    其中，z为0、1、2、3、4或5；Where z is 0, 1, 2, 3, 4 or 5;
    其中，各R b独立地为氟、氯、溴、碘、羟基、氰基、硝基、氨基、羧基、-CH 3、-CH 2CH 3、-CH 2CH 2CH 3、-CH(CH 3) 2、-CH 2CH 2CH 2CH 3、-C(CH 3) 3、-OCH 3、-OCH 2CH 3、-OCH 2CH 2CH 3、-OCH(CH 3) 2、-OC(CH 3) 3、-CHF 2、-CF 3或-OCF 3。 Among them, each R b is independently fluorine, chlorine, bromine, iodine, hydroxyl, cyano, nitro, amino, carboxyl, -CH 3 , -CH 2 CH 3 , -CH 2 CH 2 CH 3 , -CH (CH 3 ) 2 , -CH 2 CH 2 CH 2 CH 3 , -C (CH 3 ) 3 , -OCH 3 , -OCH 2 CH 3 , -OCH 2 CH 2 CH 3 , -OCH (CH 3 ) 2 , -OC (CH 3 ) 3 , -CHF 2 , -CF 3 or -OCF 3 .
  6. 根据权利要求1-5任意一项所述的化合物，其中，The compound according to any one of claims 1 to 5, wherein:
    R 1、R 2、R 3、R 4和R 5各自独立地为氢、卤素、羟基、氰基、硝基、氨基、羧基、C 1-4烷基、卤代C 1-4烷基、C 1-4烷氧基或卤代C 1-4烷氧基； R 1 , R 2 , R 3 , R 4 and R 5 are each independently hydrogen, halogen, hydroxyl, cyano, nitro, amino, carboxyl, C 1-4 alkyl, halo C 1-4 alkyl, C 1-4 alkoxy or halo C 1-4 alkoxy;
    或R 1、R 2、R 3、R 4和R 5各自独立地为以下子结构式： Or R 1 , R 2 , R 3 , R 4 and R 5 are each independently the following substructure formula:
    Figure PCTCN2019091137-appb-100012
    Figure PCTCN2019091137-appb-100012
    其中，R 11、R 22、R 33、R 44和R 55各自独立地为氢、卤素、羟基、氰基、硝基、氨基、羧基、C 1-4烷基、卤代C 1-4烷基、C 1-4烷氧基、卤代C 1-4烷氧基、C 1-4烷基胺基或C 1-4烷硫基。 Among them, R 11 , R 22 , R 33 , R 44 and R 55 are each independently hydrogen, halogen, hydroxyl, cyano, nitro, amino, carboxyl, C 1-4 alkyl, halo C 1-4 alkane Alkyl, C 1-4 alkoxy, halo C 1-4 alkoxy, C 1-4 alkylamino or C 1-4 alkylthio.
  7. 根据权利要求1-6任意一项所述的化合物，其中，The compound according to any one of claims 1 to 6, wherein:
    R 1、R 2、R 3、R 4和R 5各自独立地为氢、氟、氯、溴、碘、羟基、氰基、硝基、氨基、羧基、-CH 3、-CH 2CH 3、-CH 2CH 2CH 3、-CH(CH 3) 2、-CH 2CH 2CH 2CH 3、-C(CH 3) 3、-CH 2Cl、-CHF 2、-CF 3、-OCH 3、-OCH 2CH 3、-OCH 2CH 2CH 3、-OCH(CH 3) 2、-OC(CH 3) 3或-OCF 3； R 1 , R 2 , R 3 , R 4 and R 5 are each independently hydrogen, fluorine, chlorine, bromine, iodine, hydroxyl, cyano, nitro, amino, carboxyl, -CH 3 , -CH 2 CH 3 , -CH 2 CH 2 CH 3 , -CH (CH 3 ) 2 , -CH 2 CH 2 CH 2 CH 3 , -C (CH 3 ) 3 , -CH 2 Cl, -CHF 2 , -CF 3 , -OCH 3 , -OCH 2 CH 3 , -OCH 2 CH 2 CH 3 , -OCH (CH 3 ) 2 , -OC (CH 3 ) 3 or -OCF 3 ;
    或R 1、R 2、R 3、R 4和R 5各自独立地为以下子结构式： Or R 1 , R 2 , R 3 , R 4 and R 5 are each independently the following substructure formula:
    Figure PCTCN2019091137-appb-100013
    Figure PCTCN2019091137-appb-100013
    其中，R 11、R 22、R 33、R 44和R 55各自独立地为氢、氟、氯、溴、碘、羟基、氰基、硝基、氨基、羧基、-CH 3、-CH 2CH 3、-CH 2CH 2CH 3、-CH(CH 3) 2、-CH 2CH 2CH 2CH 3、-C(CH 3) 3、-CF 3、-OCH 3、-OCH 2CH 3、-OCH 2CH 2CH 3、-OCH(CH 3) 2、-OC(CH 3) 3、-OCF 3、-N(CH 3) 2或-SCH 3。 Among them, R 11 , R 22 , R 33 , R 44 and R 55 are each independently hydrogen, fluorine, chlorine, bromine, iodine, hydroxyl, cyano, nitro, amino, carboxyl, -CH 3 , -CH 2 CH 3 , -CH 2 CH 2 CH 3 , -CH (CH 3 ) 2 , -CH 2 CH 2 CH 2 CH 3 , -C (CH 3 ) 3 , -CF 3 , -OCH 3 , -OCH 2 CH 3 , -OCH 2 CH 2 CH 3 , -OCH (CH 3 ) 2 , -OC (CH 3 ) 3 , -OCF 3 , -N (CH 3 ) 2 or -SCH 3 .
  8. 根据权利要求1-7任意一项所述的化合物，其为具有式(II)所示的化合物或式(II)所示的化合物的盐及其氮氧化物：The compound according to any one of claims 1 to 7, which is a compound having a compound represented by Formula (II) or a salt of a compound represented by Formula (II) and its nitrogen oxide:
    Figure PCTCN2019091137-appb-100014
    Figure PCTCN2019091137-appb-100014
  9. 根据权利要求8所述的化合物，其中，The compound according to claim 8, wherein:
    R 1、R 2、R 3、R 4和R 5各自独立地为氢、卤素、C 1-4烷基、卤代C 1-4烷基、C 1-4烷氧基或卤代C 1-4烷氧基； R 1 , R 2 , R 3 , R 4 and R 5 are each independently hydrogen, halogen, C 1-4 alkyl, halo C 1-4 alkyl, C 1-4 alkoxy, or halo C 1 -4 alkoxy;
    或R 1、R 2、R 3、R 4和R 5各自独立地为以下子结构式： Or R 1 , R 2 , R 3 , R 4 and R 5 are each independently the following substructure formula:
    Figure PCTCN2019091137-appb-100015
    Figure PCTCN2019091137-appb-100015
    其中，R 11、R 22、R 33、R 44和R 55各自独立地为氢、卤素、C 1-4烷基、C 1-4烷氧基、卤代C 1-4烷基或卤代C 1-4烷氧基； Wherein R 11 , R 22 , R 33 , R 44 and R 55 are each independently hydrogen, halogen, C 1-4 alkyl, C 1-4 alkoxy, halo C 1-4 alkyl or halo C 1-4 alkoxy;
    条件为：R 1、R 2和R 3中有且只有一个为
    Figure PCTCN2019091137-appb-100016
    The condition is: there is only one of R 1 , R 2 and R 3 is
    Figure PCTCN2019091137-appb-100016
  10. 根据权利要求9所述的化合物，其中，The compound according to claim 9, wherein:
    R 1、R 2、R 3、R 4和R 5各自独立地为氢、氟、氯、溴、碘、-CH 3、-CH 2CH 3、-CH 2CH 2CH 3、-CH(CH 3) 2、-CH 2CH 2CH 2CH 3、-C(CH 3) 3、-CF 3、-OCH 3或-OCF 3； R 1 , R 2 , R 3 , R 4 and R 5 are each independently hydrogen, fluorine, chlorine, bromine, iodine, -CH 3 , -CH 2 CH 3 , -CH 2 CH 2 CH 3 , -CH (CH 3 ) 2 , -CH 2 CH 2 CH 2 CH 3 , -C (CH 3 ) 3 , -CF 3 , -OCH 3 or -OCF 3 ;
    或R 1、R 2、R 3、R 4和R 5各自独立地为以下子结构式： Or R 1 , R 2 , R 3 , R 4 and R 5 are each independently the following substructure formula:
    Figure PCTCN2019091137-appb-100017
    Figure PCTCN2019091137-appb-100017
    其中，R 11、R 22、R 33、R 44和R 55各自独立地为氢、氟、氯、溴、碘、-CH 3、-CH 2CH 3、-CH 2CH 2CH 3、-CH(CH 3) 2、-CH 2CH 2CH 2CH 3、-C(CH 3) 3、-CF 3、-OCH 3或-OCF 3。 Among them, R 11 , R 22 , R 33 , R 44 and R 55 are each independently hydrogen, fluorine, chlorine, bromine, iodine, -CH 3 , -CH 2 CH 3 , -CH 2 CH 2 CH 3 , -CH (CH 3 ) 2 , -CH 2 CH 2 CH 2 CH 3 , -C (CH 3 ) 3 , -CF 3 , -OCH 3 or -OCF 3 .
  11. 根据权利要求1-7任意一项所述的化合物，其为具有式(III)所示的化合物或式(III)所示的化合物的盐及其氮氧化物：The compound according to any one of claims 1 to 7, which is a salt having a compound represented by formula (III) or a compound represented by formula (III) and its nitrogen oxide:
    Figure PCTCN2019091137-appb-100018
    Figure PCTCN2019091137-appb-100018
  12. 根据权利要求11所述的化合物，其中，The compound according to claim 11, wherein:
    R 2、R 3、R 4和R 5各自独立地为氢、卤素、C 1-4烷基或卤代C 1-4烷基； R 2 , R 3 , R 4 and R 5 are each independently hydrogen, halogen, C 1-4 alkyl or halo C 1-4 alkyl;
    或R 2、R 3、R 4和R 5各自独立地为以下子结构式： Or R 2 , R 3 , R 4 and R 5 are each independently the following substructure formula:
    Figure PCTCN2019091137-appb-100019
    Figure PCTCN2019091137-appb-100019
    其中，R 11、R 22、R 33、R 44和R 55各自独立地为氢、卤素、C 1-4烷基、C 1-4烷氧基、卤代C 1-4烷基、卤代C 1-4烷氧基、C 1-4烷基胺基或C 1-4烷硫基； Among them, R 11 , R 22 , R 33 , R 44 and R 55 are each independently hydrogen, halogen, C 1-4 alkyl, C 1-4 alkoxy, halo C 1-4 alkyl, halo C 1-4 alkoxy, C 1-4 alkylamino or C 1-4 alkylthio;
    条件为：R 2、R 3、R 4和R 5中有且只有一个为
    Figure PCTCN2019091137-appb-100020
    The conditions are: there is only one of R 2 , R 3 , R 4 and R 5 is
    Figure PCTCN2019091137-appb-100020
  13. 根据权利要求12所述的化合物，其中，The compound according to claim 12, wherein:
    R 2、R 3、R 4和R 5各自独立地为氢、氟、氯、溴、碘、-CH 3或-CF 3； R 2 , R 3 , R 4 and R 5 are each independently hydrogen, fluorine, chlorine, bromine, iodine, -CH 3 or -CF 3 ;
    或R 2、R 3、R 4和R 5各自独立地为以下子结构式： Or R 2 , R 3 , R 4 and R 5 are each independently the following substructure formula:
    Figure PCTCN2019091137-appb-100021
    Figure PCTCN2019091137-appb-100021
    其中，R 11、R 22、R 33、R 44和R 55各自独立地为氢、氟、氯、溴、碘、-CH 3、-CH 2CH 3、-CH 2CH 2CH 3、-CH(CH 3) 2、-CH 2CH 2CH 2CH 3、-C(CH 3) 3、-CF 3、-OCH 3、-OCF 3、-N(CH 3) 2或-SCH 3。 Among them, R 11 , R 22 , R 33 , R 44 and R 55 are each independently hydrogen, fluorine, chlorine, bromine, iodine, -CH 3 , -CH 2 CH 3 , -CH 2 CH 2 CH 3 , -CH (CH 3 ) 2 , -CH 2 CH 2 CH 2 CH 3 , -C (CH 3 ) 3 , -CF 3 , -OCH 3 , -OCF 3 , -N (CH 3 ) 2 or -SCH 3 .
  14. 根据权利要求1-13任意一项所述的化合物，其为具有下列之一结构的化合物或具有下列之一结构化合物的盐、氮氧化物、或(E)和(Z)异构体以及它们的混合物：The compound according to any one of claims 1 to 13, which is a compound having one of the following structures or a salt, nitrogen oxide, or (E) and (Z) isomers of the compound having one of the following structures, and mixture:
    Figure PCTCN2019091137-appb-100022
    Figure PCTCN2019091137-appb-100022
    Figure PCTCN2019091137-appb-100023
    Figure PCTCN2019091137-appb-100023
    Figure PCTCN2019091137-appb-100024
    Figure PCTCN2019091137-appb-100024
    Figure PCTCN2019091137-appb-100025
    Figure PCTCN2019091137-appb-100025
    Figure PCTCN2019091137-appb-100026
    Figure PCTCN2019091137-appb-100026
    Figure PCTCN2019091137-appb-100027
    Figure PCTCN2019091137-appb-100027
    Figure PCTCN2019091137-appb-100028
    Figure PCTCN2019091137-appb-100028
    Figure PCTCN2019091137-appb-100029
    Figure PCTCN2019091137-appb-100029
    Figure PCTCN2019091137-appb-100030
    Figure PCTCN2019091137-appb-100030
    Figure PCTCN2019091137-appb-100031
    Figure PCTCN2019091137-appb-100031
    Figure PCTCN2019091137-appb-100032
    Figure PCTCN2019091137-appb-100032
    Figure PCTCN2019091137-appb-100033
    Figure PCTCN2019091137-appb-100033
    Figure PCTCN2019091137-appb-100034
    Figure PCTCN2019091137-appb-100034
  15. 一种组合物，包含权利要求1-14任意一项所述的化合物及农药学上可接受的表面活性剂和/或载体。A composition comprising a compound according to any one of claims 1 to 14 and an agrochemically acceptable surfactant and / or carrier.
  16. 权利要求1-14任意一项所述的化合物或权利要求15所述的组合物在防治植物病原性真菌中的应用。Use of a compound according to any one of claims 1 to 14 or a composition according to claim 15 for controlling plant pathogenic fungi.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009130193A1 (en) * 2008-04-22 2009-10-29 Bayer Cropscience Sa Fungicide hydroximoyl-heterocycles derivatives
JP2011012088A (en) * 2010-08-10 2011-01-20 Nippon Soda Co Ltd Oxime compound or salt thereof, and fungicide
CN104892591A (en) * 2015-04-09 2015-09-09 南通大学 Preparation method of pyrazole oxime compound containing 3-aryl-1,2,4-oxdiazole heterocycle structure and application thereof

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Publication number Priority date Publication date Assignee Title
US6340697B1 (en) * 1997-12-10 2002-01-22 Dainippon Ink And Chemicals, Inc. Oxime derivatives and agricultural chemicals containing the same

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009130193A1 (en) * 2008-04-22 2009-10-29 Bayer Cropscience Sa Fungicide hydroximoyl-heterocycles derivatives
JP2011012088A (en) * 2010-08-10 2011-01-20 Nippon Soda Co Ltd Oxime compound or salt thereof, and fungicide
CN104892591A (en) * 2015-04-09 2015-09-09 南通大学 Preparation method of pyrazole oxime compound containing 3-aryl-1,2,4-oxdiazole heterocycle structure and application thereof

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