WO2021243480A1 - 三唑磺酰胺类衍生物及其制备方法和应用 - Google Patents

三唑磺酰胺类衍生物及其制备方法和应用 Download PDF

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WO2021243480A1
WO2021243480A1 PCT/CN2020/093562 CN2020093562W WO2021243480A1 WO 2021243480 A1 WO2021243480 A1 WO 2021243480A1 CN 2020093562 W CN2020093562 W CN 2020093562W WO 2021243480 A1 WO2021243480 A1 WO 2021243480A1
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alkyl
alkoxy
halogenated
compound
cycloalkyl
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PCT/CN2020/093562
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English (en)
French (fr)
Inventor
李义涛
林健
姚文强
张少凯
高国良
李法霖
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东莞市东阳光农药研发有限公司
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Priority to CN202080101567.1A priority Critical patent/CN115667229A/zh
Priority to PCT/CN2020/093562 priority patent/WO2021243480A1/zh
Publication of WO2021243480A1 publication Critical patent/WO2021243480A1/zh

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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
    • A01N43/647—Triazoles; Hydrogenated triazoles
    • A01N43/653—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
    • A01P3/00—Fungicides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
    • C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
    • C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
    • C07D249/10—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D249/12—Oxygen or sulfur atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a chain containing hetero atoms as chain links

Definitions

  • the present invention belongs to the field of pesticides. Specifically, the present invention provides a novel triazole sulfonamide derivative, a preparation method thereof, and application as a plant disease control agent in agriculture.
  • the purpose of the present invention is to provide a novel triazole sulfonamide derivative, which has excellent control effect on plant diseases caused by pathogenic fungi, especially cucumber downy mildew.
  • the present invention provides a compound, which is a compound represented by formula (I) or a stereoisomer of a compound represented by formula (I), nitrogen oxide or a salt thereof:
  • R 2 is hydrogen, C 1-6 alkyl, C 2-6 alkenyl, C 2-6 alkynyl, C 3-8 cycloalkyl or C 3-8 cycloalkyl-C 1-3 alkylene- ; Wherein, R 2 is optionally selected from the group consisting of 1, 2, 3, 4, 5 or 6 halogen, cyano, hydroxy, nitro, amino, C 1-4 alkyl, C 2-4 alkenyl, C 2-4 alkynyl, C 3-6 cycloalkyl, C 3-6 cycloalkyl-C 1-3 alkylene-, halogenated C 1-4 alkyl, C 1-4 alkoxy or halogenated C 1-4 alkoxy substitution;
  • R 3 and R 4 are each independently hydrogen, C 1-6 alkyl, C 2-6 alkenyl, C 2-6 alkynyl, C 3-8 cycloalkyl, C 3-8 cycloalkyl-C 1 -3 Alkylene-, phenyl optionally substituted with 1, 2, 3, 4 or 5 selected from halogen or phenyl optionally substituted with 1, 2, 3, 4 or 5 selected from halogen -C 1-3 alkylene-;
  • R 3 , R 4 and the nitrogen atom to which they are connected together form a 3-8 membered heterocyclic group or a 5-10 membered heteroaryl group;
  • X is #-CR 5 R 6 -CR 7 R 8 -CR 9 R 10 -*; among them, the connection terminal indicated by “#” is connected to -NR 2 -, and the connection terminal indicated by "*" is connected to -R 1 connect;
  • R 5 and R 6 are each independently hydrogen or C 1-6 alkyl
  • R 7 and R 8 are each independently hydrogen or C 1-6 alkyl
  • R 9 and R 10 are each independently hydrogen or C 1-6 alkyl
  • R 1 is phenyl, naphthyl, anthryl, or pyridin-3-yl; wherein R 1 is optionally substituted by 1, 2, 3, 4, or 5 selected from the group consisting of halogen, hydroxy, and cyano.
  • R 1 is a phenyl group, a naphthyl group, an anthryl group or a pyridin-3-yl group, and the phenyl group is The naphthyl includes The anthracene group includes The pyridin-3-yl is Indicates the connection position of the group to other parts of the molecule.
  • R 1 is
  • the connection terminal indicated by “#” is connected to -NR 2 -, and the connection terminal indicated by "*" is connected to -R 1 ;
  • R 5 and R 6 are each independently hydrogen or C 1-6 alkyl
  • R 7 and R 8 are each independently hydrogen or C 1-6 alkyl
  • R 9 and R 10 are each independently hydrogen or C 1-6 alkyl.
  • X is #-CH 2 -CH 2 -CH 2 -*.
  • R 5 and R 6 are each independently hydrogen
  • R 8 is hydrogen or C 1-6 alkyl
  • R 10 is hydrogen or C 1-6 alkyl.
  • R 10 is hydrogen or C 1-4 alkyl; more preferably, R 10 is hydrogen.
  • R 8 is hydrogen, -CH 3 , -CH 2 CH 3 , -CH 2 CH 2 CH 3 , -CH(CH 3 ) 2 , -CH 2 CH 2 CH 2 CH 3 , -CH 2 CH 2 CH 2 CH 3 or -CH 2 CH 2 CH 2 CH 2 CH 3 ;
  • R 10 is hydrogen, -CH 3 , -CH 2 CH 3 , -CH 2 CH 2 CH 3 , -CH(CH 3 ) 2 , -CH 2 CH 2 CH 2 CH 3 , -CH 2 CH 2 CH 2 CH 3 or -CH 2 CH 2 CH 2 CH 2 CH 3 .
  • R 2 is hydrogen, C 1-4 alkyl, C 2-4 alkenyl, C 2-4 alkynyl, C 3-6 cycloalkyl, or C 3-6 cycloalkyl-C 1- 3 alkylene-; wherein R 2 is optionally substituted by 1, 2, 3, 4, 5 or 6 selected from halogen, cyano, hydroxy, nitro, amino, C 1-4 alkyl, C 2- 4 Alkenyl, C 2-4 alkynyl, C 3-6 cycloalkyl, C 3-6 cycloalkyl-C 1-3 alkylene-, halogenated C 1-4 alkyl, C 1-4 alkane Substituted by oxy or halo C 1-4 alkoxy.
  • R 2 is hydrogen, -CH 3 , -CH 2 CH 3 , -CH 2 CH 2 CH 3 , -CH(CH 3 ) 2 , -CH 2 CH 2 CH 2 CH 3 , cyclopropyl , Cyclobutyl, cyclopentyl, cyclohexyl or cyclopropyl -CH 2 -; wherein R 2 is optionally 1, 2, 3, 4, 5 or 6 selected from fluorine, chlorine, bromine, iodine, Cyano, hydroxyl, nitro, amino, -CH 3 , -CH 2 CH 3 , -CH 2 CH 2 CH 3 , -CH(CH 3 ) 2 , -CH 2 CH 2 CH 2 CH 3 , -CH 2 CH (CH 3 ) 2 , -CH(CH 3 )CH 2 CH 3 , -C(CH 3 ) 3 , cyclopropyl, cyclobutyl, cyclopentyl, cyclohexy
  • R 2 is C 3-6 cycloalkyl; more preferably, R 2 is cyclopropyl.
  • R 3 and R 4 are each independently hydrogen, C 1-4 alkyl, C 2-4 alkenyl, C 2-4 alkynyl, C 3-6 cycloalkyl, C 3-6 ring Alkyl-C 1-3 alkylene-, phenyl or phenyl-C 1-3 alkylene-.
  • R 3 and R 4 are each independently hydrogen or C 1-4 alkyl; more preferably, R 3 and R 4 are each independently C 1-4 alkyl; further preferably, R 3 and R 4 Each independently is -CH 3 .
  • R 3 , R 4 and the nitrogen atom to which they are attached together form a 3-6 membered heterocyclic group or a 5-10 membered heteroaryl group.
  • the sub-structure formed by R 3 , R 4 and the nitrogen atom to which they are connected is:
  • the present invention provides a compound, which is a compound represented by formula (II) or a nitrogen oxide, salt, (E) type isomer, (Z) type of a compound represented by formula (II) Isomers and mixtures of (E) isomers and (Z) isomers:
  • R 1 , R 2 , R 3 , R 4 , R 8 and R 10 have the meanings described in the present invention.
  • the present invention provides a compound, which is a compound having one of the following structures or a stereoisomer, nitrogen oxide, or a salt of a compound having one of the following structures:
  • the present invention provides a composition comprising at least one compound according to the present invention.
  • composition of the present invention contains auxiliary agents commonly used in pesticides.
  • the present invention provides the use of the compound of the present invention and/or the composition of the present invention in controlling plant diseases.
  • plant diseases described in the present invention are caused by phytopathogenic fungi.
  • the plant diseases include cucumber downy mildew, cucumber gray mold, cucumber powdery mildew and rice sheath blight.
  • the articles “a”, “an” and “said” used in the present invention are intended to include “at least one” or “one or more”. Therefore, the articles used in the present invention refer to articles of one or more than one (ie, at least one) object.
  • a component refers to one or more components, that is, more than one component may be considered to be adopted or used in an embodiment of the described embodiment.
  • Stereoisomers refer to compounds that have the same chemical structure but differ in the arrangement of the atoms or groups in space. Stereoisomers include enantiomers, diastereomers, conformational isomers (rotamers), geometric isomers (cis/trans) isomers, atropisomers, etc. .
  • Enantiomers refer to two isomers of a compound that cannot be superimposed but are mirror images of each other.
  • Diastereoisomers refer to stereoisomers that have two or more chiral neutralities and whose molecules are not mirror images of each other. Diastereomers have different physical properties, such as melting point, boiling point, spectral properties and reactivity. Diastereomeric mixtures can be separated by high-resolution analytical procedures such as electrophoresis and chromatography, such as HPLC.
  • optically active compounds 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 the molecule with respect to one or more of its chiral centers.
  • the prefixes d and l or (+) and (-) are symbols used to specify the rotation of plane-polarized light caused by the compound, where (-) or l indicates that the compound is levorotatory.
  • Compounds prefixed with (+) or d are dextrorotatory.
  • a specific stereoisomer is an enantiomer, and a mixture of such isomers is called an enantiomeric mixture.
  • a 50:50 mixture of enantiomers is called a racemic mixture or a racemate, which can occur when there is no stereoselectivity or stereospecificity in a chemical reaction or process.
  • any asymmetric atom (for example, carbon, etc.) of the compound disclosed in the present invention may exist in a racemic or enantiomerically enriched form, such as (R)-, (S)- or (R,S)-configuration form exist.
  • each asymmetric atom has at least 50% enantiomeric excess in (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 compound of the present invention can be one of the possible isomers or a mixture of them, such as racemates and diastereomer mixtures (depending on the number of asymmetric carbon atoms) The form exists.
  • 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 have an E or Z configuration; if the compound contains a disubstituted cycloalkyl, the substituent of the cycloalkyl may have a cis or trans configuration.
  • Any resulting mixture of stereoisomers can be separated into pure or substantially pure geometric isomers, enantiomers, and diastereomers based on differences in the physical and chemical properties of the components, for example, by chromatography Method and/or fractional crystallization method.
  • racemates of any final product or intermediate obtained can be resolved into optical enantiomers by methods familiar to those skilled in the art by known methods, for example, by performing diastereomeric salts thereof. Separate.
  • the racemic product can also be separated by chiral chromatography, such as high performance liquid chromatography (HPLC) using a chiral adsorbent.
  • enantiomers can be prepared by asymmetric synthesis.
  • the "stereoisomers" of the compounds described in the present invention mainly refer to the (E) isomers and (Z) isomers of the compounds.
  • the compounds of the present invention include (E) type isomers, (Z) type isomers, (E) type isomers and (Z) type isomer mixtures.
  • the configuration of the compound of the present invention is the (E) isomer.
  • the compounds of the present invention can be optionally substituted by one or more substituents, such as the above formula compounds, or as the specific examples, subclasses, and subclasses contained in the examples.
  • substituents such as the above formula compounds, or as the specific examples, subclasses, and subclasses contained in the examples.
  • a class of compounds can be used interchangeably.
  • “optionally substituted” and “optionally substituted with...substituents” mean that the given structure is unsubstituted or one or more hydrogen atoms in the given structure are replaced by specific substituents.
  • substituted means that one or more hydrogen atoms in a given structure are replaced by a specific substituent. Unless otherwise indicated, an optional substituent group can be substituted at each substitutable position of the group. When more than one position in the given structural formula can be substituted by one or more substituents selected from specific groups, then the substituents can be substituted at each position with the same or different substitutions. Specifically, examples of "one or more” refer to 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10.
  • the substituents mentioned herein can be, but are not limited to, deuterium, fluorine, chlorine, bromine, iodine, cyano, hydroxyl, nitro, amino, carboxy, alkyl, alkoxy, alkoxyalkyl, alkane Oxyalkoxy, alkoxyalkylamino, aryloxy, heteroaryloxy, heterocyclyloxy, arylalkoxy, heteroarylalkoxy, heterocyclylalkoxy, cycloalkane Alkoxy, alkylamino, alkylaminoalkyl, alkylaminoalkylamino, cycloalkylamino, cycloalkylalkylamino, alkylthio, haloalkyl, haloalkoxy, hydroxy-substituted alkyl, hydroxy-substituted alkyl Amino, cyano-substituted alkyl, cyano-substituted alkoxy, cyan
  • C 1 -C 6 alkyl or “C 1-6 alkyl” specifically refers 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 in the present invention means a saturated linear or branched monovalent hydrocarbon group containing 1 to 20 carbon atoms; wherein the alkyl group is optionally One or more substituents described in this invention are substituted. 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; in yet 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
  • alkenyl means a linear or branched monovalent hydrocarbon group containing 2-12 carbon atoms, in which there is at least one site of unsaturation, that is, a carbon-carbon sp 2 double bond, wherein the alkenyl group
  • the group can be optionally substituted with one or more substituents described in the present invention, which includes the positioning of "cis” and “tans", or the positioning of "E” and "Z”.
  • the alkenyl group contains 2-8 carbon atoms; in another embodiment, the alkenyl group contains 2-6 carbon atoms; in yet another embodiment, the alkenyl group contains 2 -4 carbon atoms.
  • alkynyl means a linear or branched monovalent hydrocarbon group containing 2-12 carbon atoms, in which there is at least one carbon-carbon sp triple bond, wherein the alkynyl group may optionally be substituted by one or more One of the substituents described in this invention is substituted.
  • the alkynyl group contains 2-10 carbon atoms; in one embodiment, the alkynyl group contains 2-8 carbon atoms; in another embodiment, the alkynyl group contains 2- 6 carbon atoms; in yet another embodiment, the alkynyl group contains 2-4 carbon atoms.
  • alkynyl groups include, but are not limited to, -C ⁇ CH, -C ⁇ CCH 3 , -CH 2 -C ⁇ CH, -CH 2 -C ⁇ CCH 3 , -CH 2 CH 2 -C ⁇ CH , -CH 2 -C ⁇ CCH 2 CH 3 , -CH 2 CH 2 -C ⁇ CCH 3 , and so on.
  • alkoxy means that the 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 ), etc.
  • alkylthio means that the alkyl group is connected to the rest of the molecule through a sulfur atom, where the alkyl group has the meaning as described in the present invention.
  • alkylthio groups include, but are not limited to, -SCH 3 , -SCH 2 CH 3 , -SCH 2 CH 2 CH 3 , -SCH(CH 3 ) 2 , and the like.
  • cycloalkyl refers to a monovalent or multivalent saturated monocyclic, bicyclic or tricyclic ring system containing 3-12 carbon atoms.
  • the cycloalkyl group contains 3-10 carbon atoms; in another embodiment, the cycloalkyl group contains 3-8 carbon atoms; in another embodiment, the cycloalkyl group contains 3-6 carbon atoms. carbon atom.
  • the cycloalkyl group is optionally substituted with one or more substituents described in the present invention.
  • Examples of this include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl, cyclododecyl Alkyl, etc.
  • cycloalkyl-alkylene means that the cycloalkyl group is connected to other parts of the molecule through the alkylene group, wherein the alkylene group and the cycloalkyl group have the meanings as described in the present invention.
  • alkylene group and the cycloalkyl group have the meanings as described in the present invention.
  • examples include, but are not limited to, cyclopropyl -CH 2 -, cyclobutyl -CH 2 -, cyclopentyl -CH 2 -, cyclohexyl -CH 2 -, and the like.
  • linking substituents are described.
  • the Markush variables listed for the group should be understood as the linking group.
  • the Markush group definition of the variable lists “alkyl” or “aryl” it should be understood that the “alkyl” or “aryl” respectively represents the attached Alkylene group or arylene group.
  • alkylene refers to a saturated divalent hydrocarbon group obtained by removing two hydrogen atoms from a saturated linear or branched hydrocarbon. Unless otherwise specified, alkylene groups contain 1-12 carbon atoms. In one embodiment, the alkylene group contains 1-8 carbon atoms; in one embodiment, the alkylene group contains 1-6 carbon atoms; in another embodiment, the alkylene group Contains 1-4 carbon atoms; in yet another embodiment, the alkylene group contains 1-3 carbon atoms; in yet another embodiment, the alkylene group contains 1-2 carbon atoms.
  • Such examples include methylene (-CH 2 -), ethylene (-CH 2 CH 2 -), propylene (-CH 2 CH 2 CH 2 -), -CH(CH 3 )CH 2 -, -C(CH 3 ) 2 -, -CH 2 CH 2 CH(CH 3 )-, -CH 2 CH 2 C(CH 3 ) 2 -, and so on.
  • 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 composed of 3-7 atoms, and has one or more attachment points connected to the rest of the molecule.
  • aryl can be used interchangeably with the term “aromatic ring”. Examples of aryl groups may include phenyl, indenyl, naphthyl, and anthracenyl. The aryl group is optionally substituted with one or more substituents described in the present invention.
  • heterocyclic group and “heterocyclic ring” are used interchangeably herein, and both refer to a saturated or partially unsaturated monocyclic, bicyclic or tricyclic ring containing 3-15 ring atoms, wherein monocyclic, bicyclic or tricyclic ring
  • the ring does not contain an aromatic ring, and at least one ring atom is selected from nitrogen, sulfur and oxygen atoms.
  • the sulfur atom of the ring can optionally be oxidized to S-oxide.
  • the nitrogen atom of the ring can optionally be oxidized to an N-oxygen compound.
  • heterocyclic groups include, but are not limited to, oxirane, azetidinyl, oxetanyl, thietanyl, pyrrolidinyl (such as 2-pyrrolidinyl), 2-pyrrole Linyl, 3-pyrrolinyl, pyrazolidinyl, imidazolinyl, imidazolidinyl, tetrahydrofuranyl, dihydrofuranyl, tetrahydrothienyl, dihydrothienyl, 1,3-dioxocyclopentyl, Dithiocyclopentyl, tetrahydropyranyl, dihydropyranyl, 2H-pyranyl, 4H-pyranyl, tetrahydrothiopyranyl, piperidinyl (2-piperidinyl, 3-piperidine , 4-piperidinyl), morpholin
  • Examples in which the sulfur atom in the heterocyclic group is oxidized include, but are not limited to, sulfolane and 1,1-dioxothiomorpholinyl.
  • the heterocyclyl group is optionally substituted with one or more substituents described in the present invention.
  • 3-12 membered heterocyclic group typically describes the number of ring atoms in the molecule.
  • tetrahydrofuranyl is a 5-membered heterocyclic group
  • piperidinyl is a 6-membered heterocyclic group.
  • heteroatom refers to O, S, N, P, and Si, including any oxidation state of N, S, and P; primary, secondary, and tertiary amines and quaternary ammonium salt forms; or on the nitrogen atom in the heterocycle
  • the form in which hydrogen is substituted for example, N (like the N in 3,4-dihydro-2H-pyrrolyl), NH (like the NH in pyrrolidinyl), or NR (like the N-substituted pyrrolidinyl in NR).
  • halogen refers to fluorine (F), chlorine (Cl), bromine (Br) or iodine (I).
  • heteroaryl refers to monocyclic, bicyclic and tricyclic ring systems containing 5-12 ring atoms, or 5-10 ring atoms, or 5-6 ring atoms, in which at least one ring system is aromatic, And at least one ring system contains one or more heteroatoms, wherein each ring system contains a ring composed of 5-7 atoms, and has one or more attachment points connected to the rest of the molecule.
  • heteroaryl can be used interchangeably with the terms “heteroaromatic ring” or “heteroaromatic compound”.
  • the heteroaryl group is optionally substituted with one or more substituents described in the present invention.
  • the 5-10 atom heteroaryl group contains 1, 2, 3, or 4 heteroatoms independently selected from O, S, and N.
  • heteroaryl groups include, but are not limited to, 2-furyl, 3-furyl, N-imidazolyl, 2-imidazolyl, 4-imidazolyl, 5-imidazolyl, 3-isoxazolyl , 4-isoxazolyl, 5-isoxazolyl, 2-oxazolyl, 4-oxazolyl, 5-oxazolyl, N-pyrrolyl, 2-pyrrolyl, 3-pyrrolyl, 2- Pyridyl, 3-pyridyl, 4-pyridyl, 2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl, pyridazinyl (such as 3-pyridazinyl), 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, tetrazolyl (such as 5-tetrazolyl), triazolyl (such as 2-triazolyl and 5-triazolyl), 2-thienyl, 3-thienyl, pyrazolyl, iso Thi
  • 5-12 membered heteroaryl typically describes the number of ring atoms in the molecule.
  • pyrrolyl, pyrazolyl, imidazolyl, thienyl, isothiazolyl, thiazolyl, furyl, isoxazolyl and oxazolyl are 5-membered heteroaryl groups
  • pyridyl, pyrimidinyl, pyrazinyl and Pyridazinyl is a 6-membered heteroaryl group.
  • haloalkyl means that the alkyl group is substituted by one or more halogen atoms. Examples of this 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 F, -CH 2 CH 2 Cl, -CH 2 CH 2 CF 3 , and so on.
  • haloalkoxy means that the alkoxy group is substituted by one or more halogen atoms. Examples of this 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 , etc.
  • haloalkylthio means that the alkylthio group is substituted by one or more halogen atoms. Examples of this include, but are not limited to, difluoromethylthio (-SCHF 2 ), trifluoromethylthio (- SCF 3 ), etc.
  • the salts of the compounds of the present invention include those derived from alkali metals or alkaline earth metals and those derived from ammonia and amines.
  • Preferred cations include sodium, potassium, magnesium, and having the formula N + (R A R B R C R D) ammonium cation, where R A, R B, R C and R D are independently selected from hydrogen, C 1 -C 6 alkyl groups and C 1 -C 6 hydroxyalkyl groups.
  • the salt of the compound of formula (I) or (II) can be obtained by using metal hydroxides (e.g. sodium hydroxide) or amines (e.g. ammonia, trimethylamine, diethanolamine, 2-methylthiopropylamine, diallylamine). , 2-butoxyethylamine, morpholine, cyclododecylamine or benzylamine) are prepared by treating the compound of formula (I) or (II).
  • metal hydroxides e.g. sodium hydroxide
  • 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, and malonic acid. Acid, mandelic acid, malic acid, phthalic acid, hydrochloric acid, hydrobromic acid, phosphoric acid, nitric acid, sulfuric acid, methanesulfonic acid, naphthalenesulfonic acid, benzenesulfonic acid, toluenesulfonic acid, camphorsulfonic acid and similarly known Accepted acid.
  • organic and inorganic acids such as acetic acid, propionic acid, lactic acid, citric acid, tartaric acid, succinic acid, fumaric acid, maleic acid, and malonic acid. Acid, mandelic acid, malic acid, phthalic acid, hydrochloric acid, hydrobromic acid, phosphoric acid, nitric acid, sulfuric acid, methane
  • compositions and formulations of the compounds of the present invention are provided.
  • the compound of the present invention can generally be used as a bactericidal active ingredient in a composition or preparation, and usually also includes a commonly used adjuvant in pesticide science; the commonly used adjuvant in pesticide science includes a surfactant and/or a carrier.
  • the above-mentioned surfactants may be various surfactants known in the field of pesticide formulations. In the present invention, it is preferably one or more of emulsifiers, dispersants and wetting agents.
  • other carriers can be various carriers known in the field of pesticide formulations, including various silicates, carbonates, sulfates, oxides, phosphates, plant carriers, and synthetics. Carrier class.
  • One or more of potassium mixture and anhydrous sodium carbonate and anhydrous sodium bicarbonate mixture One or more of potassium mixture and anhydrous sodium carbonate and anhydrous sodium bicarbonate mixture.
  • the above-mentioned emulsifier may be various emulsifiers known in the field of pesticide formulations.
  • the emulsifier may be calcium dodecylbenzene sulfonate, triphenylethylphenol polyoxyethylene ether phosphate, fatty alcohol polyoxyethylene Ether, alkylphenol polyoxyethylene ether, alkylphenol polyoxyethylene polyoxypropylene ether, fatty amine, fatty amide ethylene oxide adduct, fatty acid polyoxyethylene ester, rosin acid ethylene oxide adduct , Polyol fatty acid esters and their ethylene oxide adducts, styryl phenyl polyoxyethylene ether, alkylphenol formaldehyde resin polyoxyethylene ether, hydroxyl-terminated polyoxyethylene polyoxypropylene ether, styryl phenol One or more of formaldehyde resin polyoxyethylene polyoxypropylene ether and castor oil polyoxyethylene ether.
  • the above-mentioned dispersant may be various dispersants well-known in the field of pesticide formulations.
  • the dispersant is acrylic acid homopolymer sodium salt, maleic acid disodium salt, naphthalenesulfonic acid formaldehyde condensate sodium salt, rosin block poly Oxyethylene ether polyoxypropylene ether sulfonate, hydroxyl-terminated polyoxyethylene polyoxypropylene ether block copolymer, triphenylethyl phenol polyoxyethylene ether phosphate, fatty alcohol polyoxyethylene ether phosphate and p-hydroxyphenyl One or more of lignosulfonate sodium salt.
  • the above-mentioned wetting agent can be various wetting agents known in the field of pesticide formulations.
  • the wetting agent can be sodium lauryl sulfate, sodium secondary alkyl sulfate, sodium dodecylbenzene sulfonate, and fat.
  • the bactericidal composition may also contain various formulation auxiliary agents commonly used in the field of pesticide formulations.
  • the formulation auxiliary may be a solvent, a cosolvent, a thickener, an antifreeze, One or more of capsule materials, protective agents, defoamers, disintegrants, stabilizers, preservatives and binders.
  • the above-mentioned solvent may be various solvents known in the field of pesticide formulations.
  • the solvent may be one or more of organic solvents, vegetable oils, mineral oils, mineral spirits, and water.
  • the organic solvent includes N-methylpyrrolidone, tetrahydrofuran, dimethyl sulfoxide, N,N-dimethyldecamide, N,N-dimethylformamide, trimethylbenzene, tetramethylbenzene, xylene, One or more of toluene, octane, heptane, methanol, isopropanol, n-butanol, tetrahydrofurfuryl alcohol, tributyl phosphate, 1,4-dioxane and cyclohexanone.
  • the vegetable oil includes one or more of methylated vegetable oil, turpentine-based vegetable oil, turpentine oil, epoxidized soybean oil, soybean oil, peanut oil, rapeseed oil, castor oil, corn oil, and pine seed oil.
  • the mineral oil includes one or more of liquid wax, motor oil, kerosene and lubricating oil.
  • the above-mentioned solvents can also be used as auxiliary solvents.
  • the aforementioned antifreeze agent may be various antifreeze agents known in the field of pesticide formulations.
  • it is preferably one or more of ethylene glycol, propylene glycol, glycerin and urea.
  • the above-mentioned thickener can be various thickeners known in the field of pesticide formulations.
  • the thickener can be xanthan gum, polyvinyl alcohol, polyacryl alcohol, polyethylene glycol, white carbon black, and diatoms.
  • the above-mentioned capsule material may be various capsule materials known in the field of pesticide formulations.
  • it is preferably one or more of polyurethane, polyurea and urea-formaldehyde resin.
  • the above-mentioned protective agent may be various protective agents known in the field of pesticide formulations, and the present invention is preferably polyvinyl alcohol and/or polyethylene glycol.
  • the above-mentioned defoaming agent may be various defoaming agents known in the field of pesticide formulations.
  • it is preferably one or more of organosiloxane, tributyl phosphate and silicone.
  • the aforementioned stabilizer is selected from one or more of triphenyl phosphite, epichlorohydrin and acetic anhydride.
  • preservatives are selected from one or more of benzoic acid, sodium benzoate, 1,2-benzisothiazolin-3-one (abbreviated as BIT), cassone and potassium sorbate.
  • the present invention also provides a preparation prepared from the above-mentioned bactericidal composition.
  • the dosage forms of the preparation are emulsifiable concentrates, water emulsions, microemulsions, soluble liquids, water suspensions, suspoemulsions, ultra-low volume sprays, and oil suspensions.
  • Microcapsule suspension agent water surface spreading oil agent, wettable powder, water dispersible granule, dry suspension agent, soluble powder, soluble granule, emulsifiable powder, emulsifiable granule, granule, solid microcapsule preparation, Effervescent tablets, effervescent granules, water floating dispersible granules or seed coatings.
  • the above dosage forms can all be prepared by conventional methods in the art.
  • the preparation method of the above-mentioned emulsifiable concentrate preparation may include, for example, mixing and stirring each active component, solvent, cosolvent, and emulsifier to form a uniform and transparent oil phase to obtain emulsifiable concentrate preparation.
  • the preparation method of the above-mentioned aqueous emulsion may include, for example, mixing the active ingredient, emulsifier, cosolvent and solvent to make it into a homogeneous oil phase; mixing water, thickener, antifreeze, etc. to make it into a homogeneous water phase. Under high-speed shear, the water phase is added to the oil phase or the oil phase is added to the water phase to form a water emulsion with good dispersibility.
  • the preparation method of the above-mentioned microemulsion may be, for example, mixing and stirring the active ingredient, emulsifier, and solvent to form a uniform and transparent oil phase. Under stirring conditions, gradually add water to form a uniform and transparent microemulsion.
  • water or oil can be used as a medium, and additives such as active components and surfactants are added to a sand milling kettle, and after grinding to a certain particle size, it is filtered. Then add the metered thickener to the ground mother liquor, and shear and disperse uniformly. Made into oil suspension or water suspension.
  • the preparation method of the above-mentioned water-dispersible granules and soluble granules for example, the active components, dispersants, wetting agents, carriers, etc. can be mixed uniformly, then pulverized by airflow to a certain particle size, and then water is added for kneading. Finally, it is added to a granulator for granulation, and after drying, water-dispersible granules or soluble granules can be obtained.
  • the preparation method of the above-mentioned soluble powder and wettable powder for example, the active components, various auxiliary agents and other carriers and other fillers can be fully mixed, and then pulverized with an ultrafine pulverizer.
  • the bactericidal composition of the present invention can be provided in the form of a finished preparation, that is, the substances in the composition have been mixed; it can also be provided in the form of a separate preparation, which is self-mixed in a barrel or tank before use, and is selectively based on the concentration of the required active substance Mix the ground with water for dilution.
  • the compound of the present invention can be used as a plant disease control agent. Therefore, the present invention may also include a method for controlling plant diseases caused by phytopathogenic fungi, the method comprising applying an effective amount of the compound of the present invention or a fungicidal composition containing the compound to the plant or part thereof to be protected .
  • 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 a broad spectrum of plant diseases, especially leaf pathogens in 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 cinnamomi and Phytophthora capsici, Pythium species diseases such as Pythium aphanidermatum, and Peronosporaceae species diseases such as Peronospora grape Plasmopara viticola, Peronospora spp. (including Peronospora tabacina and Peronospora parasitica), Pseudoperonospora spp.
  • Phytophthora diseases such as Phytophthora infestans, Phytophthora megasperma, Phytophthora parasitica, Phytophthora cinnamomi and Phytophthora capsici
  • Pythium species diseases such as Pythium aphanidermatum
  • pathogens include Rhizoctonia species ( Rhizoctonia spp.) (such as Rhizoctonia solani); Fusarium species diseases such as Fusarium roseum, Fusarium graminearum and Fusarium oxysporum ); Verticillium dahliae; Sclerotium rolfsii; Rynchosporium secalis; Cercosporidium personatum, Cercospora arachidicola and Cercospora betic ); and other types and strains closely related to these pathogens.
  • composition or combination is also effective against bacteria such as Erwinia amylovora, Xanthomonas campestris, Pseudomonas syringae and others.
  • the strain has resistance activity.
  • the method of using the bactericidal compound or composition of the present invention is simple. Before or after the germination of the plant disease, it is applied to plants, plant parts or places where plants grow according to conventional methods, such as soil mixing, spraying, spraying, pouring, etc.
  • the dosage is determined according to climatic conditions or crop conditions, generally 10-5000g per mu, diluted to 10-400mg/L (preferably 100-300mg/L) for application.
  • the diluent is preferably water.
  • the bactericidal effect of the bactericidal compound or composition of the present invention is usually related to external factors such as climate, but the influence of climate can be alleviated by using an appropriate dosage form.
  • the compound or composition of the present invention can also be mixed with other compounds with bactericidal, insecticidal or herbicidal properties, and can also be used with nematicides, acaricides, protective agents, herbicide safeners, growth regulators, phytonutrients or soil regulators. Mixing agent and so on.
  • the compounds of the present invention can be prepared by the methods described in the present invention.
  • the raw materials, reagents, etc. used to prepare the compound of the present invention are all commercially available, or can be prepared by conventional methods in the art. In this specification, if there is any difference between the chemical name and the chemical structure, the structure is dominant.
  • the target compound represented by formula (I) can be prepared by the preparation method of Synthetic Scheme 1.
  • the compound represented by formula (a) and the compound represented by formula (b) undergo a nucleophilic substitution reaction under alkaline conditions (such as pyridine, sodium hydride, potassium carbonate, etc.) to obtain the target compound represented by formula (I);
  • X, R 1 , R 2 , R 3 and R 4 have the meanings described in the present invention.
  • the second step 3-((1-(N,N-dimethylaminosulfonyl)-1H-1,2,4-triazol-3-yl)disulfanyl)-N,N-di Synthesis of methyl-1H-1,2,4-triazole-1-sulfonamide
  • the third step Synthesis of 1-(N,N-dimethylaminosulfonyl)-1H-1,2,4-triazole-3-sulfonyl chloride
  • Cinnamaldehyde (1.32g, 10mmol) was dissolved in methanol (25mL), stirred in a 100mL single-necked flask, and sodium borohydride (0.76g, 20mmol) was slowly added to react for 3 hours at 0°C.
  • the reaction was quenched by slowly adding 10 mL of water to the reaction solution, extracted with ethyl acetate (50 mL x 3), the organic phase was dried over anhydrous magnesium sulfate, filtered, and the filtrate was decompressed with a rotary evaporator to remove the solvent to obtain 1.15 g of light yellow liquid.
  • the yield was 85.78%.
  • Test target Rhizoctonia solani, cucumber gray mold, cucumber downy mildew, cucumber powdery mildew
  • Test treatment The compound was dissolved into 1% EC with DMF for later use. Using the in vivo pot culture method, evaluate the bactericidal activity of these compounds against the test target at different doses (such as 200 mg/L, 100 mg/L, 50 mg/L, 25 mg/L, etc.).
  • leaf inoculation method Choose two potted cucumber seedlings at the true leaf stage with consistent growth. After the agent is sprayed and dried, the mushroom cake is inoculated on the leaves. After 24 hours of dark light moisturizing at 24 ⁇ 26°C, natural light is restored and moisturizing culture is about 3 days. After the control is fully onset, the diameter of the lesions at each inoculation point is measured with a caliper, and the control effect is calculated.
  • test results are:
  • Example 1 At a dose of 100 mg/L, Example 1, Example 2, Example 3, Example 4, Example 5, Example 6, Example 7, Example 8, Example 9, Example 11, Example 12 , Example 13, Example 14, Example 15, Example 16, Example 17, Example 18, Example 19, Example 20, Example 21, Example 22, Example 23, Example 24, Implementation Example 25, Example 26, Example 27, Example 28, Example 29, Example 30, Example 31, Example 32, Example 33, Example 34, Example 35, Example 36, Example 37 , Example 38, Example 39, Example 40, Example 41, Example 42, Example 43, Example 44, Example 45, Example 46, Example 47, Example 48, Example 49, Implementation
  • the control effect of Example 50 on cucumber downy mildew is more than 80%.
  • Example 1 At a dose of 50mg/L, Example 1, Example 2, Example 3, Example 4, Example 5, Example 6, Example 7, Example 8, Example 9, Example 11, Example 12 , Example 13, Example 14, Example 15, Example 16, Example 17, Example 18, Example 19, Example 21, Example 22, Example 24, Example 27, Example 29, Implementation Example 30, Example 31, Example 32, Example 33, Example 34, Example 35, Example 36, Example 37, Example 38, Example 39, Example 40, Example 41, Example 42
  • the control effect of Example 43, Example 44, Example 45, Example 46, Example 47, Example 48, Example 49, and Example 50 on cucumber downy mildew is more than 70%; and Example 51,
  • the control effects of Example 52 and Example 53 against cucumber downy mildew were 10%, 40%, and 50% at a dose of 50 mg/L.
  • the compound of the present invention still has a good control effect against cucumber downy mildew at a low dose, for example, at a dose of 25 mg/L, Example 4, Example 5, Example 6, Example 8, Example 9, and Example 16 , Example 18, Example 31, Example 32, Example 33, Example 37, Example 39, Example 47, Example 48, Example 49, Example 50 for the control effect of cucumber downy mildew in 70 % Or more; and Example 51, Example 52, and Example 53 have 0%, 10%, and 30% control effects against cucumber downy mildew at a dose of 25 mg/L.
  • the compound of the present invention has a good control effect on other diseases, such as cucumber powdery mildew.
  • other diseases such as cucumber powdery mildew.
  • cucumber powdery mildew For example, at 200 mg/L, Example 2, Example 6, Example 8, Example 9, Example 14, and Example 16.
  • the control effect of Example 18, Example 29, Example 31, Example 32, Example 33, Example 47, Example 48, Example 49, and Example 50 on cucumber powdery mildew is more than 70%.

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Abstract

一种三唑磺酰胺类衍生物及其制备方法和应用；具体地，涉及式(I)所示的三唑磺酰胺类衍生物或式(I)所示三唑磺酰胺类衍生物的立体异构体、氮氧化物或其盐，及三唑磺酰胺类衍生物的制备方法，及它们在农业中作为杀菌剂的用途，及其组合物的形式，以及用这些化合物或组合物来防治植物病害的方法；其中，R 1、R 2、R 3、R 4和X具有说明书所述的含义。

Description

三唑磺酰胺类衍生物及其制备方法和应用 技术领域
本发明属于农药领域，具体地，本发明提供一种新型三唑磺酰胺类衍生物及其制备方法和在农业中作为植物病害防治剂的应用。
背景技术
为获得高农作物收率，控制植物病原真菌引起的植物病害是极其重要的。对观赏作物、蔬菜作物、大田作物、谷类作物和果树作物有损害的植物病原真菌引起的植物病害会造成产量显著降低，从而导致消费成本上升。为获得高农作物收率，控制植物病原真菌引起的植物病害是极其重要的。为此目的，可以在植物种植及生长过程中使用农药产品，有许多产品可商购获得，但是持续需要更有效、更经济、更低毒、对环境更安全或具有不同作用位点的新型化合物。
发明内容
本发明的目的在于提供一种新型三唑磺酰胺类衍生物，该类衍生物对由病原性真菌引起的植物病害，特别是黄瓜霜霉病具有优异的防效。
为了达到本发明的目的，采取如下的技术方案：
一方面，本发明提供一种化合物，其为具有式(I)所示的化合物或式(I)所示化合物的立体异构体、氮氧化物或其盐：
Figure PCTCN2020093562-appb-000001
其中，
R 1为C 6-14芳基或5-6元杂芳基；其中，R 1任选地被1、2、3、4或5个选自卤素、羟基、氰基、硝基、氨基、C 1-4烷基、C 2-4烯基、C 2-4炔基、C 1-4烷氧基、C 1-4烷硫基、卤代C 1-4烷基、卤代C 1-4烷氧基、卤代C 1-4烷硫基、C 1-4烷基-C(＝O)-、C 1-4烷基-C(＝O)O-、C 1-4烷氧基-C(＝O)-、-NH-C 1-4烷基、-N(C 1-4烷基) 2、任选地被1、2、3、4或5个选自卤素、羟基、氰基、硝基、C 1-4烷基、C 1-4烷氧基、卤代C 1-4烷基或卤代C 1-4烷氧基取代的苯基或任选地被1、2、3、4或5个选自卤素、羟基、氰基、硝基、C 1-4烷基、C 1-4烷氧基、卤代C 1-4烷基或卤代C 1-4烷氧基取代的苯氧基取代；
R 2为氢、C 1-6烷基、C 2-6烯基、C 2-6炔基、C 3-8环烷基或C 3-8环烷基-C 1-3亚烷基-；其中，R 2任选地被1、2、3、4、5或6个选自卤素、氰基、羟基、硝基、氨基、C 1-4烷基、C 2-4烯基、C 2-4炔基、C 3-6环烷基、C 3-6环烷基-C 1-3亚烷基-、卤代C 1-4烷基、C 1-4烷氧基或卤代C 1-4烷氧基取代；
R 3和R 4各自独立地为氢、C 1-6烷基、C 2-6烯基、C 2-6炔基、C 3-8环烷基、C 3-8环烷基-C 1-3亚烷基-、任选地被1、2、3、4或5个选自卤素取代的苯基或任选地被1、2、3、4或5个选自卤素取代的苯基-C 1-3亚烷基-；
或R 3、R 4和与之相连的氮原子一起形成3-8元杂环基或5-10元杂芳基；
X为#-CR 5R 6-CR 7R 8-CR 9R 10-*；其中，“#”表示的连接端与-NR 2-相连接，“*”表示的连接端与-R 1相连接；
其中，R 5和R 6各自独立地为氢或C 1-6烷基；
R 7和R 8各自独立地为氢或C 1-6烷基；
R 9和R 10各自独立地为氢或C 1-6烷基；
或R 5、R 7和与之相连接的碳原子形成碳碳双键；R 5、R 7和与之相连接的碳原子形成碳碳双键后，X为#-CR 6＝CR 8-CR 9R 10-*；
或R 7、R 9和与之相连接的碳原子形成碳碳双键；R 7、R 9和与之相连接的碳原子形成碳碳双键后，X为#-CR 5R 6-CR 8＝CR 10-*。
一些实施方案中，R 1为C 6-14芳基或吡啶基；其中，R 1任选地被1、2、3、4或5个选自卤素、羟基、氰基、硝基、氨基、C 1-4烷基、C 2-4烯基、C 2-4炔基、C 1-4烷氧基、C 1-4烷硫基、卤代C 1-4烷基、卤代C 1-4烷氧基、卤代C 1-4烷硫基、C 1-4烷基-C(＝O)-、C 1-4烷基-C(＝O)O-、C 1-4烷氧基-C(＝O)-、-NH-C 1-4烷基、-N(C 1-4烷基) 2、任选地被1、2、3、4或5个选自卤素、羟基、氰基、硝基、C 1-4烷基、C 1-4烷氧基、卤代C 1-4烷基或卤代C 1-4烷氧基取代的苯基或任选地被1、2、3、4或5个选自卤素、羟基、氰基、硝基、C 1-4烷基、C 1-4烷氧基、卤代C 1-4烷基或卤代C 1-4烷氧基取代的苯氧基取代。
另一些实施方案中，R 1为苯基、萘基、蒽基或吡啶-3-基；其中，R 1任选地被1、2、3、4或5个选自卤素、羟基、氰基、硝基、氨基、C 1-4烷基、C 2-4烯基、C 2-4炔基、C 1-4烷氧基、C 1-4烷硫基、卤代C 1-4烷基、卤代C 1-4烷氧基、卤代C 1-4烷硫基、C 1-4烷基-C(＝O)-、C 1-4烷基-C(＝O)O-、C 1-4烷氧基-C(＝O)-、-NH-C 1-4烷基、-N(C 1-4烷基) 2、任选地被1、2、3、4或5个选自卤素、羟基、氰基、硝基、C 1-4烷基、C 1-4烷氧基、卤代C 1-4烷基或卤代C 1-4烷氧基取代的苯基或任选地被1、2、3、4或5个选自卤素、羟基、氰基、硝基、C 1-4烷基、C 1-4烷氧基、卤代C 1-4烷基或卤代C 1-4烷氧基取代的苯氧基取代。
R 1为苯基、萘基、蒽基或吡啶-3-基，所述的苯基为
Figure PCTCN2020093562-appb-000002
所述的萘基包括
Figure PCTCN2020093562-appb-000003
Figure PCTCN2020093562-appb-000004
所述的蒽基包括
Figure PCTCN2020093562-appb-000005
所述的吡啶-3-基为
Figure PCTCN2020093562-appb-000006
表示基团与分子其他部分的连接位置。
又另一些实施方案中，R 1为苯基、萘基、蒽基或吡啶-3-基；其中，R 1任选地被1、2、3、4或5个选自氟、氯、溴、碘、羟基、氰基、硝基、氨基、-CH 3、-CH 2CH 3、-CH 2CH 2CH 3、-CH(CH 3) 2、-CH 2CH 2CH 2CH 3、-CH 2CH(CH 3) 2、-CH(CH 3)CH 2CH 3、-C(CH 3) 3、-CH＝CH 2、-CH 2CH＝CH 2、-C≡CH、-CH 2C≡CH、-OCH 3、-OCH 2CH 3、-OCH 2CH 2CH 3、-OCH(CH 3) 2、-OCH 2CH 2CH 2CH 3、-OCH 2CH(CH 3) 2、-OCH(CH 3)CH 2CH 3、-OC(CH 3) 3、-SCH 3、-SCH 2CH 3、-SCH 2CH 2CH 3、-SCH(CH 3) 2、-CHF 2、-CF 3、-OCHF 2、-OCF 3、-SCF 3、-C(＝O)CH 3、-C(＝O)CH 2CH 3、-C(＝O)CH 2CH 2CH 3、-C(＝O)CH(CH 3) 2、-OC(＝O)CH 3、-OC(＝O)CH 2CH 3、-OC(＝O)CH 2CH 2CH 3、-OC(＝O)CH(CH 3) 2、-C(＝O)OCH 3、-C(＝O)OCH 2CH 3、-C(＝O)OCH 2CH 2CH 3、-C(＝O)OCH(CH 3) 2、-NHCH 3、-NHCH 2CH 3、-N(CH 3) 2、-N(CH 2CH 3) 2、苯基或苯氧基取代。
又另一些实施方案中，R 1为
Figure PCTCN2020093562-appb-000007
Figure PCTCN2020093562-appb-000008
一些实施方案中，X为#-CR 5R 6-CR 7R 8-CR 9R 10-*、#-CR 6＝CR 8-CR 9R 10-*或#-CR 5R 6-CR 8＝CR 10-*；其中，“#”表示的连接端与-NR 2-相连接，“*”表示的连接端与-R 1相连接；
其中，R 5和R 6各自独立地为氢或C 1-6烷基；
R 7和R 8各自独立地为氢或C 1-6烷基；
R 9和R 10各自独立地为氢或C 1-6烷基。
一些实施方案中，X为#-CH 2-CH 2-CH 2-*。
另一些实施方案中，X为#-CR 5R 6-CR 8＝CR 10-*；其中，“#”表示的连接端与-NR 2-相连接，“*”表示的连接端与-R 1相连接；
R 5和R 6各自独立地为氢；
R 8为氢或C 1-6烷基；
R 10为氢或C 1-6烷基。
优选地，一些实施方案中，R 10为氢或C 1-4烷基；更优选地，R 10为氢。
又另一些实施方案中，X为#-CH 2-CR 8＝CR 10-*；其中，“#”表示的连接端与-NR 2-相连接，“*”表示的连接端与-R 1相连接；
R 8为氢、-CH 3、-CH 2CH 3、-CH 2CH 2CH 3、-CH(CH 3) 2、-CH 2CH 2CH 2CH 3、-CH 2CH 2CH 2CH 2CH 3或-CH 2CH 2CH 2CH 2CH 2CH 3；
R 10为氢、-CH 3、-CH 2CH 3、-CH 2CH 2CH 3、-CH(CH 3) 2、-CH 2CH 2CH 2CH 3、-CH 2CH 2CH 2CH 2CH 3或-CH 2CH 2CH 2CH 2CH 2CH 3。
一些实施方案中，R 2为氢、C 1-4烷基、C 2-4烯基、C 2-4炔基、C 3-6环烷基或C 3-6环烷基-C 1-3亚烷基-；其中，R 2任选地被1、2、3、4、5或6个选自卤素、氰基、羟基、硝基、氨基、C 1-4烷基、C 2-4烯基、C 2-4炔基、C 3-6环烷基、C 3-6环烷基-C 1-3亚烷基-、卤代C 1-4烷基、C 1-4烷氧基或卤代C 1-4烷氧基取代。
另一些实施方案中，R 2为氢、-CH 3、-CH 2CH 3、-CH 2CH 2CH 3、-CH(CH 3) 2、-CH 2CH 2CH 2CH 3、环丙基、环丁基、环戊基、环己基或环丙基-CH 2-；其中，R 2任选地被1、2、3、4、5或6个选自氟、氯、溴、碘、氰基、羟基、硝基、氨基、-CH 3、-CH 2CH 3、-CH 2CH 2CH 3、-CH(CH 3) 2、-CH 2CH 2CH 2CH 3、-CH 2CH(CH 3) 2、-CH(CH 3)CH 2CH 3、-C(CH 3) 3、环丙基、环丁基、环戊基、环己基或环丙基-CH 2-取代。
优选地，R 2为C 3-6环烷基；更优选地，R 2为环丙基。
一些实施方案中，R 3和R 4各自独立地为氢、C 1-4烷基、C 2-4烯基、C 2-4炔基、C 3-6环烷基、C 3-6环烷基-C 1-3亚烷基-、苯基或苯基-C 1-3亚烷基-。
另一些实施方案中，R 3和R 4各自独立地为氢、-CH 3、-CH 2CH 3、-CH 2CH 2CH 3、-CH(CH 3) 2、-CH 2CH 2CH 2CH 3、-CH 2CH(CH 3) 2、-CH(CH 3)CH 2CH 3、-CH＝CH 2、-CH 2CH＝CH 2、环丙基、环丙基-CH 2-、苯基或苄基。
优选地，R 3和R 4各自独立地为氢或C 1-4烷基；更优选地，R 3和R 4各自独立地为C 1-4烷基；进一步优选地，R 3和R 4各自独立地为-CH 3。
一些实施方案中，R 3、R 4和与之相连的氮原子一起形成3-6元杂环基或5-10元杂芳基。
另一些实施方案中，R 3、R 4和与之相连的氮原子一起形成的子结构式为：
Figure PCTCN2020093562-appb-000009
一些实施方案中，本发明提供一种化合物，其为具有式(II)所示的化合物或式(II)所示化合物的氮氧化物、盐、(E)型异构体、(Z)型异构体以及(E)型异构体和(Z)型异构体的混合物：
Figure PCTCN2020093562-appb-000010
其中，R 1、R 2、R 3、R 4、R 8和R 10具有本发明所述的含义。
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立体异构体、氮氧化物或其盐：
Figure PCTCN2020093562-appb-000011
Figure PCTCN2020093562-appb-000012
Figure PCTCN2020093562-appb-000013
另一方面，本发明提供一种组合物，所述组合物包含至少一种本发明所述的化合物。
进一步地，本发明所述的组合物包含农药上常用的辅助剂。
又另一方面，本发明提供本发明所述的化合物和/或本发明所述的组合物在防治植物病害中的用途。
进一步地，本发明所述的植物病害是由植物病原性真菌引起的。
所述的植物病害包括黄瓜霜霉病、黄瓜灰霉病、黄瓜白粉病和水稻纹枯病。
本发明的详细说明
定义和一般术语
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。
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。
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。
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。
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。
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。
“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。
“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。
“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。
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。
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。
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。
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。
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。
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。本发明所述的化合物的“立体异构体”主要是指化合物的(E)型异构体、(Z)型异构体。本发明所述的化合物包括(E)型异构体、(Z)型异构体、(E)型异构体和(Z)型异构体的混合物。优选地，本发明所述的化合物的构型为(E)型异构体。
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”和“任选地被…取代基取代”与“取代或非取代的”这个术语可以交换使用。一般而言，“任选取代的”和“任选地被…取代基取代”表示所给结构未被取代或所给结构中一个或多个氢原子被具体取代基所取代。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。
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。
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。
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。
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)，正己基(-CH 2CH 2CH 2CH 2CH 2CH 3)，等等。
术语“烯基”表示含有2-12个碳原子的直链或支链一价烃基，其中至少有一个不饱和位点，即有一个碳-碳sp 2双键，其中，所述烯基基团可以任选地被一个或多个本发明所描述的取代基所取代，其包括“cis”和“tans”的定位，或者“E”和“Z”的定位。在一实施方案中，烯基基团包含2-8个碳原子；在另一实施方案中，烯基基团包含2-6个碳原子；在又一实施方案中，烯基基团包含2-4个碳原子。烯基基团的实例包括，但并不限于，乙烯基(-CH＝CH 2)，烯丙基(-CH 2CH＝CH 2)，丙烯基(CH 3-CH＝CH-)，氧代的丁烯基(CH 3-C(＝O)-CH＝CH-)，等等。
术语“炔基”表示含有2-12个碳原子的直链或支链一价烃基，其中至少有一个碳-碳sp三键，其中，所述炔基基团可以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，炔基基团包含2-10个碳原子；在一实施方案中，炔基基团包含2-8个碳原子；在另一实施方案中，炔基基团包含2-6个碳原子；在又一实施方案中，炔基基团包含2-4个碳原子。炔基基团的实例包括，但并不限于，-C≡CH、-C≡CCH 3、-CH 2-C≡CH、-CH 2-C≡CCH 3、-CH 2CH 2-C≡CH、-CH 2-C≡CCH 2CH 3、-CH 2CH 2-C≡CCH 3，等等。
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。
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，-SCH 3、-SCH 2CH 3、-SCH 2CH 2CH 3、-SCH(CH 3) 2，等等。
术语“环烷基”表示含有3-12个碳原子的，单价或多价的饱和单环、双环或三环体系。在一实施方案中，环烷基包含3-10个碳原子；在另一实施方案中，环烷基包含3-8个碳原子； 在又一实施方案中，环烷基包含3-6个碳原子。所述环烷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。这样的实例包括，但并不限于，环丙基，环丁基，环戊基，环己基，环庚基，环辛基，环壬基，环癸基，环十一烷基，环十二烷基，等等。
术语“环烷基-亚烷基”表示环烷基基团通过亚烷基基团与分子其他部分相连接，其中亚烷基和环烷基基团具有如本发明所述的含义。这样的实例包括，但并不限于，环丙基-CH 2-，环丁基-CH 2-，环戊基-CH 2-，环己基-CH 2-，等等。
在本发明书的各部分，描述了连接取代基。当该结构清楚地需要连接基团时，针对该基团所列举的马库什变量应理解为连接基团。例如，如果该结构需要连接基团并且针对该变量的马库什基团定义列举了“烷基”或“芳基”，则应当理解，该“烷基”或“芳基”分别代表连接的亚烷基基团或亚芳基基团。
术语“亚烷基”表示从饱和的直链或支链烃中去掉两个氢原子所得到的饱和的二价烃基基团。除非另外详细说明，亚烷基基团含有1-12个碳原子。在一实施方案中，亚烷基基团含有1-8个碳原子；在一实施方案中，亚烷基基团含有1-6个碳原子；在另一实施方案中，亚烷基基团含有1-4个碳原子；在又一实施方案中，亚烷基基团含有1-3个碳原子；还在一实施方案中，亚烷基基团含有1-2个碳原子。这样的实例包括亚甲基(-CH 2-)，亚乙基(-CH 2CH 2-)，亚丙基(-CH 2CH 2CH 2-)，-CH(CH 3)CH 2-，-C(CH 3) 2-，-CH 2CH 2CH(CH 3)-，-CH 2CH 2C(CH 3) 2-，等等。
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。
术语“杂环基”和“杂环”在此处可交换使用，都是指包含3-15个环原子的饱和或部分不饱和的单环、双环或三环，其中单环、双环或三环中不包含芳香环，且至少一个环原子选自氮、硫和氧原子。除非另外说明，杂环基可以是碳基或氮基，且-CH 2-基团可以任选地被-C(＝O)-替代。环的硫原子可以任选地被氧化成S-氧化物。环的氮原子可以任选地被氧化成N-氧化合物。杂环基的实例包括，但不限于，环氧乙烷基，氮杂环丁基，氧杂环丁基，硫杂环丁基，吡咯烷基(如2-吡咯烷基)，2-吡咯啉基，3-吡咯啉基，吡唑烷基，咪唑啉基，咪唑烷基，四氢呋喃基，二氢呋喃基，四氢噻吩基，二氢噻吩基，1,3-二氧环戊基，二硫环戊基，四氢吡喃基，二氢吡喃基，2H-吡喃基，4H-吡喃基，四氢噻喃基，哌啶基(2-哌啶基，3-哌啶基，4-哌啶基)，吗啉基，硫代吗啉基，(1-氧代)-硫代吗啉基，(1,1-二氧代)-硫代吗啉基，哌嗪基，二噁烷基，二噻烷基，噻噁烷基，高哌嗪基，高哌啶基，氧杂环庚烷基，硫杂环庚烷基，2-氧杂-5-氮杂双环[2.2.1]庚-5-基，四氢吡啶基。杂环基中-CH 2-基团被-C(＝O)-取代的实例包括，但不限于，2-氧代吡咯烷基，氧代-1,3-噻唑烷基，2-哌啶酮基，3,5-二氧代哌啶基。杂环基中硫原子被氧化的实例包括，但不限于，环丁砜基，1,1-二氧代硫代吗啉基。所述杂环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。
术语“3-12元杂环基”，“3-10元杂环基”，“3-8元杂环基”或“3-6元杂环基”，其中“3-12元”、“3-10元”、“3-8元”或“3-6元”典型地描述分子中成环原子的数目。例如，四氢呋喃基是5元杂环基，哌啶基是6元杂环基。
术语“杂原子”是指O、S、N、P和Si，包括N、S和P任何氧化态的形式；伯、仲、 叔胺和季铵盐的形式；或者杂环中氮原子上的氢被取代的形式，例如，N(像3,4-二氢-2H-吡咯基中的N)，NH(像吡咯烷基中的NH)或NR(像N-取代的吡咯烷基中的NR)。
术语“卤素”是指氟(F)、氯(Cl)、溴(Br)或碘(I)。
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。
杂芳基基团的实例包括，但并不限于，2-呋喃基，3-呋喃基，N-咪唑基，2-咪唑基，4-咪唑基，5-咪唑基，3-异噁唑基，4-异噁唑基，5-异噁唑基，2-噁唑基，4-噁唑基，5-噁唑基，N-吡咯基，2-吡咯基，3-吡咯基，2-吡啶基，3-吡啶基，4-吡啶基，2-嘧啶基，4-嘧啶基，5-嘧啶基，哒嗪基(如3-哒嗪基)，2-噻唑基，4-噻唑基，5-噻唑基，四唑基(如5-四唑基)，三唑基(如2-三唑基和5-三唑基)，2-噻吩基，3-噻吩基，吡唑基，异噻唑基，1,2,3-噁二唑基，1,2,5-噁二唑基，1,2,4-噁二唑基，1,2,3-三唑基，1,2,3-硫代二唑基，1,3,4-硫代二唑基，1,2,5-硫代二唑基，吡嗪基，1,3,5-三嗪基，嘧啶酮基，吡啶酮基；也包括以下的双环，但绝不限于这些双环：苯并咪唑基，苯并呋喃基，苯并四氢呋喃基，苯并噻吩基，吲哚基(如2-吲哚基)，苯并哌啶基，等等。
术语“5-12元杂芳基”，“5-10元杂芳基”或“5-6元杂芳基”，其中“5-12元”、“5-10元”或“5-6元”典型地描述分子中成环原子的数目。例如，吡咯基、吡唑基、咪唑基、噻吩基、异噻唑基、噻唑基、呋喃基、异恶唑基和恶唑基是5元杂芳基，吡啶基、嘧啶基、吡嗪基和哒嗪基是6元杂芳基。
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 2F，-CH 2CH 2Cl，-CH 2CH 2CF 3，等等。
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，等等。
术语“卤代烷硫基”表示烷硫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，二氟甲硫基(-SCHF 2)，三氟甲硫基(-SCF 3)，等等。
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。具有化学式(I)或(II)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)对具有化学式(I)或(II)的化合物进行处理来制备。
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。
本发明化合物的组合物和制剂
本发明的化合物一般可用作组合物或制剂中的杀菌活性成分，通常还包括农药学上常用的辅助剂；所述的农药学上常用的辅助剂包括表面活性剂和/或载体。
上述表面活性剂可以为农药剂型领域所公知的各种表面活性剂，本发明优选为乳化剂、分散剂和润湿剂中的一种或多种。
除上述表面活性剂外的其它载体可以为农药剂型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。
上述乳化剂可以为农药剂型领域所公知的各种乳化剂，具体地，该乳化剂可以为十二烷基苯磺酸钙、三苯乙基酚聚氧乙烯醚磷酸酯、脂肪醇聚氧乙烯醚、烷基酚聚氧乙烯醚、烷基酚聚氧乙烯聚氧丙烯醚、脂肪胺、脂肪酰胺的环氧乙烷加成物、脂肪酸聚氧乙烯酯、松香酸环氧乙烷加成物、多元醇脂肪酸酯及其环氧乙烷加成物、苯乙烯基苯基聚氧乙烯醚、烷基酚甲醛树脂聚氧乙烯醚、端羟基聚氧乙烯聚氧丙烯醚、苯乙烯基苯酚甲醛树脂聚氧乙烯聚氧丙烯醚和蓖麻油聚氧乙烯醚中的一种或多种。
上述分散剂可以为农药剂型领域所公知的各种分散剂，具体地，该分散剂为丙烯酸均聚物钠盐、马来酸二钠盐、萘磺酸甲醛缩合物钠盐、松香嵌段聚氧乙烯醚聚氧丙烯醚磺酸盐、端羟基聚氧乙烯聚氧丙烯醚嵌段共聚物、三苯乙基酚聚氧乙烯醚磷酸酯、脂肪醇聚氧乙烯醚磷酸酯和对羟苯基木质素磺酸钠盐中的一种或多种。
上述润湿剂可以为农药剂型领域所公知的各种润湿剂，具体地，该润湿剂可以为十二烷基硫酸钠、仲烷基硫酸钠、十二烷基苯磺酸钠、脂肪醇聚氧乙烯醚、烷基萘磺酸盐、烷基酚树脂聚氧乙烯醚硫酸盐中的一种或多种。
根据本发明的杀菌组合物，该杀菌组合物还可以含有农药剂型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、防腐剂和粘结剂中的一种或多种。
上述溶剂可以为农药剂型领域所公知的各种溶剂，具体地，该溶剂可以为有机溶剂、植物油、矿物油、溶剂油和水中的一种或多种。
其中，所述有机溶剂包括N-甲基吡咯烷酮、四氢呋喃、二甲基亚砜、N,N-二甲基癸酰胺、N,N-二甲基甲酰胺、三甲苯、四甲苯、二甲苯、甲苯、辛烷、庚烷、甲醇，异丙醇、正丁醇、四氢糠醇、磷酸三丁酯、1,4-二氧六环和环己酮中的一种或多种。
所述植物油包括甲基化植物油，松脂基植物油，松节油，环氧大豆油、大豆油、花生油、菜籽油、蓖麻油、玉米油和松籽油中的一种或多种。
所述矿物油包括液蜡、机油、煤油和润滑油中的一种或多种。
同时，上述溶剂也可以作为助溶剂使用。
上述防冻剂可以为农药剂型领域所公知的各种防冻剂，本发明优选为乙二醇、丙二醇、甘油和尿素中的一种或多种。
上述增稠剂可以为农药剂型领域所公知的各种增稠剂，具体地，该增稠剂可以为黄原胶、聚乙烯醇、聚丙烯醇、聚乙二醇、白炭黑、硅藻土、高岭土、粘土、海藻酸钠、硅酸铝镁、 硅酸铝钠、羧甲基纤维素、羟丙基纤维素钠和有机膨润土中的一种或多种。
上述囊材可以为农药剂型领域所公知的各种囊材，本发明优选为聚氨酯、聚脲和脲醛树脂中的一种或多种。
上述保护剂可以为农药剂型领域所公知的各种保护剂，本发明优选为聚乙烯醇和/或聚乙二醇。
上述消泡剂可以为农药剂型领域所公知的各种消泡剂，本发明优选为有机硅氧烷、磷酸三丁酯和硅酮中的一种或多种。
上述稳定剂选自亚磷酸三苯酯、环氧氯丙烷和醋酐中的一种或多种。
上述防腐剂选自苯甲酸、苯甲酸钠、1,2-苯并异噻唑啉-3-酮(简称BIT)、卡松和山梨酸钾中的一种或多种。
本发明还提供一种由上述杀菌组合物制备得到的制剂，所述制剂的剂型为乳油、水乳剂、微乳剂、可溶性液剂、水悬浮剂、悬乳剂、超低容量喷雾剂、油悬浮剂、微囊悬浮剂、水面展膜油剂、可湿性粉剂、水分散性颗粒剂、干悬浮剂、可溶性粉剂、可溶性粒剂、可乳化粉剂、可乳化颗粒剂、颗粒剂、固体微胶囊制剂、泡腾片剂、泡腾颗粒剂、水漂浮分散颗粒剂或种衣剂。上述剂型均可由本领域的常规方法来制备。
上述乳油制剂的制备方法例如可以包括将各活性组分、溶剂、助溶剂及乳化剂混合搅拌使其形成均匀透明油相，即可得到乳油制剂。
上述水乳剂制备方法例如可以包括将活性成分、乳化剂、助溶剂和溶剂混合，使其成为均匀油相；将水、增稠剂、防冻剂等混合，使其成均一水相。在高速剪切下，将水相加入到油相或将油相加入到水相，形成分散性良好的水乳剂。
上述微乳剂的制备方法例如可以是将活性成分，乳化剂，溶剂混合搅拌成均一透明的油相。在搅拌的条件下，逐渐的加入水，使其形成均一透明的微乳液。
上述水/油悬浮剂的制备方法：例如可以是以水或油为介质，将活性组分、表面活性剂等助剂加入砂磨釜中，进行研磨至一定粒径后，过滤。再将计量好的增稠剂加入到研磨好的母液中，剪切分散均匀。制成油悬浮剂或水悬浮剂。
上述水分散性粒剂及可溶性粒剂的制备方法：例如可以是将各活性组分、分散剂、润湿剂、载体等混合均匀，然后通过气流粉碎至一定粒径，再加入水进行捏合，最后加入造粒机中进行造粒，干燥后即可得到水分散性粒剂或可溶性粒剂。
上述可溶性粉剂及可湿性粉剂的制备方法：例如可以是将各活性组分、各种助剂及其他载体等填料充分混合，用超细粉碎机粉碎。
本发明的杀菌组合物可以以成品制剂形式提供，即组合物中各物质已经混合；也可以以单独制剂形式提供，使用前在桶或罐中自行混合，并根据所需活性物质的浓度选择性地与水混合进行稀释即可。
本发明化合物及组合物的应用
本发明的化合物可用作植物病害防治剂。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。
本发明的杀菌化合物或组合物的使用方法简单，在植物病害萌发之前或萌发之后，向植物、植物部分或植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。
本发明的杀菌化合物或组合物，其杀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。
本发明化合物或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。
一般合成过程
下述方案描述本发明化合物的制备。除非有进一步的说明，本发明的化合物可以通过本发明所描述的方法制备得到。制备本发明的化合物所使用的原料、试剂等等均是可以商购的，或者可以通过本领域常规的方法制备得到。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。
合成方案
合成方案一
Figure PCTCN2020093562-appb-000014
式(I)所示的目标化合物可以通过合成方案一的制备方法制备得到。式(a)所示的化合物与式(b)所示的化合物在碱性条件下(如吡啶、氢化钠、碳酸钾等)，发生亲核取代反应得到式(I)所示的目标化合物；
其中，X、R 1、R 2、R 3和R 4具有本发明所述的含义。
实施例
中间体1:N 3-环丙基-N 1,N 1-二甲基-1H-1,2,4-三唑-1,3-二磺酰胺的合成
Figure PCTCN2020093562-appb-000015
第一步：1,2-二(1H-1,2,4-三唑-3-基)二硫烷的合成
Figure PCTCN2020093562-appb-000016
将3-巯基-1,2,4-三唑(101.0g,1.00mol)溶于二氯甲烷(500mL)中，加入吡啶(79.0g,1.00mol)，在0℃下搅拌，缓慢滴加对甲苯磺酰氯(95.3g,0.50mol)，2小时滴加完毕。加入完毕后25℃下搅拌18小时。用旋转蒸发仪减压蒸去二氯甲烷，剩余物在机械搅拌条件下加入水(500mL)，搅拌1小时。过滤，滤渣分别用水(800mL)和乙酸乙酯(300mL)洗涤，风干，得到黄色粉末95.2g，产率为：95.2％。
LC-MS:(M+1)m/z＝201.2。
第二步：3-((1-(N,N-二甲基胺基磺酰基)-1H-1,2,4-三唑-3-基)二硫烷基)-N,N-二甲基-1H-1,2,4-三唑-1-磺酰胺的合成
Figure PCTCN2020093562-appb-000017
氮气保护下，将1,2-二(1H-1,2,4-三唑-3-基)二硫烷(60.0g,0.30mol)溶于N,N-二甲基甲酰胺(300mL)中，加入碳酸钾(69.0g,0.50mol)，在0℃下搅拌混合。缓慢滴入N,N-二甲胺基磺酰氯(93.3g,0.65mol)，2小时滴加完毕，继续反应6小时。反应完成后，反应液缓慢倒入到水中，搅拌1小时。过滤，风干固体，得到白色粉末107.2g，产率为：86.3％。
LC-MS:(M+1)m/z＝415.0。
第三步：1-(N,N-二甲胺基磺酰基)-1H-1,2,4-三唑-3-磺酰氯的合成
Figure PCTCN2020093562-appb-000018
将3-((1-(N,N-二甲基胺基磺酰基)-1H-1,2,4-三唑-3-基)二硫烷基)-N,N-二甲基-1H-1,2,4-三唑-1-磺酰胺(41.40g,0.10mol)溶于1,2-二氯乙烷(150mL)中，加入水(300mL)，冷却至0℃，加入乙酸(100mL)，控制温度在10℃到25℃，2小时后通入氯气(35.50g,0.50mol)，继续反应半小时。反应完成后，溶液转移至分液漏斗，静置分液，有机相用水(30mL)洗涤三次，用旋转蒸发仪减压蒸去溶剂，得到白色粉末48.11g，产率为：87.8％。
LC-MS:(M+1)m/z＝274.8。
第四步：N 3-环丙基-N 1,N 1-二甲基-1H-1,2,4-三唑-1,3-二磺酰胺的合成
Figure PCTCN2020093562-appb-000019
在氮气保护下，将环丙胺(1.14g,0.02mol)，三乙胺(2.22g,0.022mol)和四氢呋喃(30mL)加入到100mL三口瓶中，在0℃下搅拌，10分钟内滴加1-(N,N-二甲胺基磺酰基)-1H-1,2,4-三唑-3-磺酰氯(6.04g,0.02mol)的四氢呋喃(20mL)溶液，加入完毕后25℃反应2小时。过滤除去固体，滤液用旋转蒸发仪减压除去溶剂，得到淡黄色固体，重结晶[乙酸乙酯/石油醚(v/v)＝5/1]，得到白色固体4.42g，产率为：75.0％。
1H NMR(400MHz,DMSO-d 6)δ(ppm)9.30(s,1H),7.49(s,1H),2.96(s,6H),2.48(m,1H),0.63-0.56(m,2H),0.50-0.43(m,2H).
LC-MS:(M+1)m/z＝296.3.
中间体2：(E)-(3-溴丙-1-烯-1-基)苯的合成
Figure PCTCN2020093562-appb-000020
中间体2的合成方法1：
第一步：(E)-丙-1-烯-1-基苯的合成
Figure PCTCN2020093562-appb-000021
室温下，将苯甲醛(1.06g,10mmol)和1,4-二氧六环(25mL)加入到100mL三口瓶中，搅拌均匀后，依次加入三苯基膦溴乙烷(4.06g,11mmol)和无水碳酸钾(2.07g,15mmol)后，加热至110℃回流8小时。停止加热并减压除去溶剂，残留物中加入正己烷搅拌10分钟，过滤除去固体，滤液用旋转蒸发仪减压除去溶剂得浅黄色液体0.96g，产率77.03％。
LC-MS:(M+1)m/z＝119.1.
第二步：(E)-(3-溴丙-1-烯-1-基)苯的合成
Figure PCTCN2020093562-appb-000022
室温下，将(E)-丙-1-烯-1-基苯(0.83g,7mmol)和四氯化碳(25mL)加入到100mL单口瓶中搅拌均匀后，依次加入N-溴代丁二酰亚胺(0.93g,7mmol)和偶氮二异丁腈(0.15g,1.5mmol)，加热至80℃反应12小时。反应液冷却至室温后，硅胶拌样并柱层析[乙酸乙酯/石油醚(v/v)＝1/3]纯化得浅黄色液体0.56g，产率40.82％。
LC-MS:(M+1)m/z＝197.0.
以相应的物料作为原料，参照中间体2的合成方法1，或者参照现有技术中合成方法，进行反应后，既可得到表1中的中间体化合物。
表1
Figure PCTCN2020093562-appb-000023
Figure PCTCN2020093562-appb-000024
Figure PCTCN2020093562-appb-000025
Figure PCTCN2020093562-appb-000026
Figure PCTCN2020093562-appb-000027
中间体2：(E)-(3-溴丙-1-烯-1-基)苯的合成
Figure PCTCN2020093562-appb-000028
中间体2的合成方法2：
第一步：(E)-3-苯基丙-2-烯-1-醇的合成
Figure PCTCN2020093562-appb-000029
将肉桂醛(1.32g,10mmol)溶于甲醇(25mL)中，于100mL单口瓶中搅拌均匀，0℃下缓慢加入硼氢化钠(0.76g,20mmol)反应3小时。向反应液中缓慢加10mL水淬灭反应，乙酸乙酯(50mL x 3)萃取，有机相用无水硫酸镁干燥，过滤，滤液用旋转蒸发仪减压除去溶剂，得浅黄色液体1.15g，产率85.78％。
LC-MS:(M+1)m/z＝135.0.
第二步：(E)-(3-溴丙-1-烯-1-基)苯的合成
Figure PCTCN2020093562-appb-000030
将(E)-3-苯基丙-2-烯-1-醇(0.94g,7mmol)和二氯甲烷(25mL)加入100mL单口瓶中搅拌均匀，0℃下缓慢滴入三溴化磷(3.79g,14mmol)反应0.5小时。向反应液中缓慢加10mL水淬灭反应，乙酸乙酯(50mL x 3)萃取，有机相用无水硫酸镁干燥，过滤，滤液用旋转蒸发仪减压除去溶剂滤，得浅黄色液体1.21g，产率88.19％。
LC-MS:(M+1)m/z＝197.0.
以相应的物料作为原料，参照中间体2的合成方法2，或者参照现有技术中合成方法，进行反应后，既可得到表2中的中间体化合物。
表2
Figure PCTCN2020093562-appb-000031
Figure PCTCN2020093562-appb-000032
实施例1：N 3-肉桂基-N 3-环丙基-N 1,N 1-二甲基-1H-1,2,4-三唑-1,3-二磺酰胺的合成
Figure PCTCN2020093562-appb-000033
将N 3-环丙基-N 1,N 1-二甲基-1H-1,2,4-三唑-1,3-二磺酰胺(中间体1)(0.59g,2mmol)、无水碳酸钾(0.55g,4mmol)和N,N-二甲基甲酰胺(15mL)加入单口瓶中，25℃搅拌下滴加入(E)-(3-溴丙-1-烯-1-基)苯(中间体2)(0.78g,4mmol)的N,N-二甲基甲酰胺溶液(5mL)，继续搅拌反应12小时。加水150mL淬灭反应，乙酸乙酯(50mL x 3)萃取，有机相用无水硫酸钠干燥，过滤，滤液用旋转蒸发仪减压除去溶剂，残留物经柱层析纯化[乙酸乙酯/石油醚(v/v)＝1/3]得到白色固体0.63g，收率：76.62％。
1H NMR(400MHz,CDCl 3)δ(ppm)8.61(s,1H),7.35-7.31(m,4H),7.28-7.26(m,1H),6.56(d,J＝15.8Hz,1H),6.25(m,1H),4.19(d,J＝6.8Hz,2H),3.03(s,6H),2.68-2.63(m,1H),1.03-0.96(m,2H),0.89-0.81(m,2H).
LC-MS:(M+1)m/z＝412.1.
以中间体1分别和相应的表1或表2中的中间体为反应原料，参照实施例1的合成方法，进行反应后，即可得到表3中的目标化合物。
表3
Figure PCTCN2020093562-appb-000034
Figure PCTCN2020093562-appb-000035
Figure PCTCN2020093562-appb-000036
Figure PCTCN2020093562-appb-000037
Figure PCTCN2020093562-appb-000038
Figure PCTCN2020093562-appb-000039
Figure PCTCN2020093562-appb-000040
Figure PCTCN2020093562-appb-000041
Figure PCTCN2020093562-appb-000042
Figure PCTCN2020093562-appb-000043
Figure PCTCN2020093562-appb-000044
Figure PCTCN2020093562-appb-000045
中间体1分别和相应的物料作为反应原料，参照实施例1的合成方法，进行反应后，即可得到表4中的目标化合物。
表4
Figure PCTCN2020093562-appb-000046
Figure PCTCN2020093562-appb-000047
生测试验
试验靶标：水稻纹枯病菌、黄瓜灰霉病菌、黄瓜霜霉病菌、黄瓜白粉病菌
试验处理：化合物用DMF溶解成1％EC备用。采用活体盆栽法，评价这些化合物在不同剂量(如200mg/L、100mg/L、50mg/L、25mg/L等)下对试验靶标的杀菌活性。
1)黄瓜霜霉病菌测试(Pseudoperonosporacubensis)
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24小时后进行接种，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(2-3x 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，24小时后保持温度21℃左右，相对湿度95％左右保湿诱发，5天后视空白对照发病情况进行分级调查，按病指计算防效。
2)水稻纹枯病菌测试(Rhizoctoniasolani)
选择两叶一心、长势一致的盆栽水稻苗，喷雾处理后自然晾干，24小时左右进行接种，待药剂喷雾晾干后，接菌饼于叶片上。25～26℃暗光保湿24小时后，恢复自然光照保湿培养约3天。待对照充分发病后用卡尺计量每个接种点病斑长度，计算防效。
3)黄瓜灰霉病菌测试(Botrytis cinerea)
采用叶片接菌法。选择二张真叶期长势一致盆栽黄瓜苗，待药剂喷雾晾干后，接菌饼于叶片上。24～26℃暗光保湿24小时后，恢复自然光照保湿培养约3天。待对照充分发病后用卡尺计量每个接种点病斑直径，计算防效。
3)黄瓜白粉病菌测试(Sphaerothecafuliginea)
选择一张真叶期、长势一致黄瓜苗，喷雾处理后阴干24小时。洗取黄瓜叶片上的新鲜白粉病菌孢子，用双层纱布过滤，制成孢子浓度为10万个/mL左右的悬浮液，喷雾接种。接种后的试材移入人工气候内，相对湿度保持在60～70％之间，温度保持21～23℃，10天左右视空白对照发病情况进行分级调查，按病指计算防效。
试验结果为：
在100mg/L剂量下，实施例1、实施例2、实施例3、实施例4、实施例5、实施例6、实施例7、实施例8、实施例9、实施例11、实施例12、实施例13、实施例14、实施例15、实施例16、实施例17、实施例18、实施例19、实施例20、实施例21、实施例22、实施例23、实施例24、实施例25、实施例26、实施例27、实施例28、实施例29、实施例30、实施例31、实施例32、实施例33、实施例34、实施例35、实施例36、实施例37、实施例38、 实施例39、实施例40、实施例41、实施例42、实施例43、实施例44、实施例45、实施例46、实施例47、实施例48、实施例49、实施例50对黄瓜霜霉病的防效在80％以上。
在50mg/L剂量下，实施例1、实施例2、实施例3、实施例4、实施例5、实施例6、实施例7、实施例8、实施例9、实施例11、实施例12、实施例13、实施例14、实施例15、实施例16、实施例17、实施例18、实施例19、实施例21、实施例22、实施例24、实施例27、实施例29、实施例30、实施例31、实施例32、实施例33、实施例34、实施例35、实施例36、实施例37、实施例38、实施例39、实施例40、实施例41、实施例42、实施例43、实施例44、实施例45、实施例46、实施例47、实施例48、实施例49、实施例50对黄瓜霜霉病的防效在70％以上；而实施例51、实施例52、实施例53在50mg/L剂量下，对黄瓜霜霉病的防效分别为10％、40％、50％。
本发明化合物在低剂量下仍然对黄瓜霜霉病有较好的防效，如25mg/L剂量下，实施例4、实施例5、实施例6、实施例8、实施例9、实施例16、实施例18、实施例31、实施例32、实施例33、实施例37、实施例39、实施例47、实施例48、实施例49、实施例50对黄瓜霜霉病的防效在70％以上；而实施例51、实施例52、实施例53在25mg/L剂量下，对黄瓜霜霉病的防效分别为0％、10％、30％。
另外，本发明化合物对其他病害，如对黄瓜白粉病也有较好的防效，如在200mg/L下，实施例2、实施例6、实施例8、实施例9、实施例14、实施例16、实施例18、实施例29、实施例31、实施例32、实施例33、实施例47、实施例48、实施例49、实施例50对黄瓜白粉病的防效在70％以上。
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。

Claims (10)

  1. 一种化合物，其为式(I)所示的化合物，或式(I)所示的化合物的立体异构体、氮氧化物或其盐：
    Figure PCTCN2020093562-appb-100001
    其中，
    R 1为C 6-14芳基或5-6元杂芳基；其中，R 1任选地被1、2、3、4或5个选自卤素、羟基、氰基、硝基、氨基、C 1-4烷基、C 2-4烯基、C 2-4炔基、C 1-4烷氧基、C 1-4烷硫基、卤代C 1-4烷基、卤代C 1-4烷氧基、卤代C 1-4烷硫基、C 1-4烷基-C(＝O)-、C 1-4烷基-C(＝O)O-、C 1-4烷氧基-C(＝O)-、-NH-C 1-4烷基、-N(C 1-4烷基) 2、任选地被1、2、3、4或5个选自卤素、羟基、氰基、硝基、C 1-4烷基、C 1-4烷氧基、卤代C 1-4烷基或卤代C 1-4烷氧基取代的苯基或任选地被1、2、3、4或5个选自卤素、羟基、氰基、硝基、C 1-4烷基、C 1-4烷氧基、卤代C 1-4烷基或卤代C 1-4烷氧基取代的苯氧基取代；
    R 2为氢、C 1-6烷基、C 2-6烯基、C 2-6炔基、C 3-8环烷基或C 3-8环烷基-C 1-3亚烷基-；其中，R 2任选地被1、2、3、4、5或6个选自卤素、氰基、羟基、硝基、氨基、C 1-4烷基、C 2-4烯基、C 2-4炔基、C 3-6环烷基、C 3-6环烷基-C 1-3亚烷基-、卤代C 1-4烷基、C 1-4烷氧基或卤代C 1-4烷氧基取代；
    R 3和R 4各自独立地为氢、C 1-6烷基、C 2-6烯基、C 2-6炔基、C 3-8环烷基、C 3-8环烷基-C 1-3亚烷基-、任选地被1、2、3、4或5个选自卤素取代的苯基或任选地被1、2、3、4或5个选自卤素取代的苯基-C 1-3亚烷基-；
    或R 3、R 4和与之相连的氮原子一起形成3-8元杂环基或5-10元杂芳基；
    X为#-CR 5R 6-CR 7R 8-CR 9R 10-*；其中，“#”表示的连接端与-NR 2-相连接，“*”表示的连接端与-R 1相连接；
    其中，R 5和R 6各自独立地为氢或C 1-6烷基；
    R 7和R 8各自独立地为氢或C 1-6烷基；
    R 9和R 10各自独立地为氢或C 1-6烷基；
    或R 5、R 7和与之相连接的碳原子形成碳碳双键；R 5、R 7和与之相连接的碳原子形成碳碳双键后，X为#-CR 6＝CR 8-CR 9R 10-*；
    或R 7、R 9和与之相连接的碳原子形成碳碳双键；R 7、R 9和与之相连接的碳原子形成碳碳双键后，X为#-CR 5R 6-CR 8＝CR 10-*。
  2. 根据权利要求1所述的化合物，其中：
    R 1为C 6-14芳基或吡啶基；其中，R 1任选地被1、2、3、4或5个选自卤素、羟基、氰基、硝基、氨基、C 1-4烷基、C 2-4烯基、C 2-4炔基、C 1-4烷氧基、C 1-4烷硫基、卤代C 1-4烷基、卤代C 1-4烷氧基、卤代C 1-4烷硫基、C 1-4烷基-C(＝O)-、C 1-4烷基-C(＝O)O-、C 1-4烷氧基-C(＝O)-、-NH-C 1-4烷基、-N(C 1-4烷基) 2、任选地被1、2、3、4或5个选自卤素、羟基、氰基、硝基、C 1- 4烷基、C 1-4烷氧基、卤代C 1-4烷基或卤代C 1-4烷氧基取代的苯基或任选地被1、2、3、4或5个选自卤素、羟基、氰基、硝基、C 1-4烷基、C 1-4烷氧基、卤代C 1-4烷基或卤代C 1-4烷氧基取代的苯氧基取代。
  3. 根据权利要求2所述的化合物，其中：
    R 1为苯基、萘基、蒽基或吡啶-3-基；其中，R 1任选地被1、2、3、4或5个选自氟、氯、溴、碘、羟基、氰基、硝基、氨基、-CH 3、-CH 2CH 3、-CH 2CH 2CH 3、-CH(CH 3) 2、-CH 2CH 2CH 2CH 3、-CH 2CH(CH 3) 2、-CH(CH 3)CH 2CH 3、-C(CH 3) 3、-CH＝CH 2、-CH 2CH＝CH 2、-C≡CH、-CH 2C≡CH、-OCH 3、-OCH 2CH 3、-OCH 2CH 2CH 3、-OCH(CH 3) 2、-OCH 2CH 2CH 2CH 3、-OCH 2CH(CH 3) 2、-OCH(CH 3)CH 2CH 3、-OC(CH 3) 3、-SCH 3、-SCH 2CH 3、-SCH 2CH 2CH 3、-SCH(CH 3) 2、-CHF 2、-CF 3、-OCHF 2、-OCF 3、-SCF 3、-C(＝O)CH 3、-C(＝O)CH 2CH 3、-C(＝O)CH 2CH 2CH 3、-C(＝O)CH(CH 3) 2、-OC(＝O)CH 3、-OC(＝O)CH 2CH 3、-OC(＝O)CH 2CH 2CH 3、-OC(＝O)CH(CH 3) 2、-C(＝O)OCH 3、-C(＝O)OCH 2CH 3、-C(＝O)OCH 2CH 2CH 3、-C(＝O)OCH(CH 3) 2、-NHCH 3、-NHCH 2CH 3、-N(CH 3) 2、-N(CH 2CH 3) 2、苯基或苯氧基取代。
  4. 根据权利要求1所述的化合物，其中：
    X为#-CR 5R 6-CR 8＝CR 10-*；其中，“#”表示的连接端与-NR 2-相连接，“*”表示的连接端与-R 1相连接；
    R 5和R 6各自独立地为氢；
    R 8为氢或C 1-6烷基；
    R 10为氢或C 1-6烷基。
  5. 根据权利要求4所述的化合物，其中：
    X为#-CH 2-CR 8＝CR 10-*；其中，“#”表示的连接端与-NR 2-相连接，“*”表示的连接端与-R 1相连接；
    R 8为氢、-CH 3、-CH 2CH 3、-CH 2CH 2CH 3、-CH(CH 3) 2、-CH 2CH 2CH 2CH 3、-CH 2CH 2CH 2CH 2CH 3或-CH 2CH 2CH 2CH 2CH 2CH 3；
    R 10为氢、-CH 3、-CH 2CH 3、-CH 2CH 2CH 3、-CH(CH 3) 2、-CH 2CH 2CH 2CH 3、-CH 2CH 2CH 2CH 2CH 3或-CH 2CH 2CH 2CH 2CH 2CH 3。
  6. 根据权利要求1所述的化合物，其中：
    R 2为氢、C 1-4烷基、C 2-4烯基、C 2-4炔基、C 3-6环烷基或C 3-6环烷基-C 1-3亚烷基-；其中，R 2任选地被1、2、3、4、5或6个选自卤素、氰基、羟基、硝基、氨基、C 1-4烷基、C 2-4烯基、C 2-4炔基、C 3-6环烷基、C 3-6环烷基-C 1-3亚烷基-、卤代C 1-4烷基、C 1-4烷氧基或卤代C 1-4烷氧基取代；
    R 3和R 4各自独立地为氢、C 1-4烷基、C 2-4烯基、C 2-4炔基、C 3-6环烷基、C 3-6环烷基-C 1-3亚烷基-、苯基或苯基-C 1-3亚烷基-；
    或R 3、R 4和与之相连的氮原子一起形成3-6元杂环基或5-10元杂芳基。
  7. 根据权利要求6所述的化合物，其中：
    R 2为氢、-CH 3、-CH 2CH 3、-CH 2CH 2CH 3、-CH(CH 3) 2、-CH 2CH 2CH 2CH 3、环丙基、环丁基、环戊基、环己基或环丙基-CH 2-；其中，R 2任选地被1、2、3、4、5或6个选自氟、氯、溴、碘、氰基、羟基、硝基、氨基、-CH 3、-CH 2CH 3、-CH 2CH 2CH 3、-CH(CH 3) 2、-CH 2CH 2CH 2CH 3、-CH 2CH(CH 3) 2、-CH(CH 3)CH 2CH 3、-C(CH 3) 3、环丙基、环丁基、环戊基、环己基或环丙基-CH 2-取代；
    R 3和R 4各自独立地为氢、-CH 3、-CH 2CH 3、-CH 2CH 2CH 3、-CH(CH 3) 2、-CH 2CH 2CH 2CH 3、-CH 2CH(CH 3) 2、-CH(CH 3)CH 2CH 3、-CH＝CH 2、-CH 2CH＝CH 2、环丙基、环丙基-CH 2-、苯基或苄基；
    或R 3、R 4和与之相连的氮原子一起形成以下子结构式：
    Figure PCTCN2020093562-appb-100002
  8. 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立体异构体、氮氧化物或其盐：
    Figure PCTCN2020093562-appb-100003
    Figure PCTCN2020093562-appb-100004
    Figure PCTCN2020093562-appb-100005
    Figure PCTCN2020093562-appb-100006
  9. 一种组合物，包含权利要求1-8任意一项所述的化合物和农药学上常用的辅助剂。
  10. 权利要求1-8任意一项所述的化合物或权利要求9所述的组合物在防治植物病害中的用途。
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115093374A (zh) * 2021-06-28 2022-09-23 华中师范大学 三唑磺酰胺类衍生物及其制备方法和应用、杀菌剂及其应用
CN115232081A (zh) * 2021-04-25 2022-10-25 华中师范大学 含突烯片段的三唑磺酰胺类衍生物及其制备方法和应用和一种杀菌剂及其应用

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108689951A (zh) * 2017-04-05 2018-10-23 东莞东阳光科研发有限公司 三氮唑化合物及其在农业中的应用
CN110577498A (zh) * 2018-06-08 2019-12-17 东莞市东阳光农药研发有限公司 三氮唑化合物及其在农业中的应用
CN110734433A (zh) * 2018-07-19 2020-01-31 东莞市东阳光农药研发有限公司 三氮唑化合物及其在农业中的应用
CN110894190A (zh) * 2018-09-13 2020-03-20 东莞市东阳光农药研发有限公司 三氮唑化合物及其在农业中的应用
CN110950812A (zh) * 2018-09-27 2020-04-03 东莞市东阳光农药研发有限公司 三氮唑化合物及其在农业中的应用

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108689951A (zh) * 2017-04-05 2018-10-23 东莞东阳光科研发有限公司 三氮唑化合物及其在农业中的应用
CN110577498A (zh) * 2018-06-08 2019-12-17 东莞市东阳光农药研发有限公司 三氮唑化合物及其在农业中的应用
CN110734433A (zh) * 2018-07-19 2020-01-31 东莞市东阳光农药研发有限公司 三氮唑化合物及其在农业中的应用
CN110894190A (zh) * 2018-09-13 2020-03-20 东莞市东阳光农药研发有限公司 三氮唑化合物及其在农业中的应用
CN110950812A (zh) * 2018-09-27 2020-04-03 东莞市东阳光农药研发有限公司 三氮唑化合物及其在农业中的应用
CN110950810A (zh) * 2018-09-27 2020-04-03 东莞市东阳光农药研发有限公司 三氮唑化合物及其在农业中的应用
CN110950811A (zh) * 2018-09-27 2020-04-03 东莞市东阳光农药研发有限公司 三氮唑化合物及其在农业中的应用

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
LIN JIAN, ZHOU SI, XU JUN-XING, YAO WEN-QIANG, HAO GE-FEI, LI YI-TAO: "Design, Synthesis, and Structure–Activity Relationship of Economical Triazole Sulfonamide Aryl Derivatives with High Fungicidal Activity", JOURNAL OF AGRICULTURAL AND FOOD CHEMISTRY, AMERICAN CHEMICAL SOCIETY, US, vol. 68, no. 25, 24 June 2020 (2020-06-24), US , pages 6792 - 6801, XP055877117, ISSN: 0021-8561, ISBN: 978-4-86233-281-3, DOI: 10.1021/acs.jafc.9b07887 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115232081A (zh) * 2021-04-25 2022-10-25 华中师范大学 含突烯片段的三唑磺酰胺类衍生物及其制备方法和应用和一种杀菌剂及其应用
CN115093374A (zh) * 2021-06-28 2022-09-23 华中师范大学 三唑磺酰胺类衍生物及其制备方法和应用、杀菌剂及其应用
CN115093374B (zh) * 2021-06-28 2023-11-24 武汉智汇农耀科技有限公司 三唑磺酰胺类衍生物及其制备方法和应用、杀菌剂及其应用

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