WO2018214754A1 - 三唑衍生物及其在农业中的应用 - Google Patents

三唑衍生物及其在农业中的应用 Download PDF

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WO2018214754A1
WO2018214754A1 PCT/CN2018/086508 CN2018086508W WO2018214754A1 WO 2018214754 A1 WO2018214754 A1 WO 2018214754A1 CN 2018086508 W CN2018086508 W CN 2018086508W WO 2018214754 A1 WO2018214754 A1 WO 2018214754A1
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alkyl
group
aryl
halo
cycloalkyl
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PCT/CN2018/086508
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English (en)
French (fr)
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李义涛
姚文强
徐俊星
伍阳
刘新烁
林健
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东莞东阳光科研发有限公司
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Priority to CN201880002367.3A priority Critical patent/CN109311853B/zh
Publication of WO2018214754A1 publication Critical patent/WO2018214754A1/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
    • 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
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/84—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms six-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,4
    • 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
    • A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
    • C07D403/06—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
    • C07D403/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
    • C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
    • C07D471/04—Ortho-condensed systems

Definitions

  • the present invention provides a novel triazole derivative, a process for its preparation, a composition containing these compounds and its use in agriculture.
  • Triazole derivatives have been widely used in ornamental crops, vegetable crops, field crops, cereal crops and fruit crops because of their broad spectrum and high efficiency against phytopathogenic fungi.
  • the disease on the crops is resistant to them, so that the control effect of pesticides is significantly reduced, resulting in an increase in consumption costs. Therefore, it is necessary to continuously develop new compounds with better control effects to solve these problems.
  • the present invention provides a novel triazole compound, and compositions and formulations containing the same for controlling phytopathogenic fungi. Specifically:
  • the invention relates to a stereoisomer, an oxynitride and a salt of a compound of formula (I) or a compound of formula (I):
  • R 1 and R 2 are each independently hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, heterocyclyl, aryl, heteroaryl, cycloalkylalkyl, heterocyclylalkyl, arylalkane Or heteroarylalkyl;
  • R 1 , R 2 together with the nitrogen atom to which they are attached form a heterocyclic or heteroaryl group
  • heterocyclic group or heteroaryl group formed by R 1 , R 2 together with the nitrogen atom to which it is attached is optionally substituted by one or more substituents selected from R 5 ;
  • Y is hydrogen, halogen, hydroxy, cyano, nitro, amino, carboxy, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, arylalkyl, halo Aryl or haloarylalkyl;
  • L 1 and L 2 are each independently -(CR 3 R 4 ) n -, -(CR 11 R 22 ) m -O-, -(CR 33 R 44 ) o -NR n - or -(CR 55 R 66 ) p -S(O) q -;
  • R 3 and R 4 are each independently hydrogen, halogen, amino, hydroxy, cyano, nitro, alkyl, alkenyl, alkynyl, haloalkyl, amino-substituted alkyl, hydroxy-substituted alkyl, cyanide a substituted alkyl or a nitro substituted alkyl;
  • R 11 , R 22 , R 33 , R 44 , R 55 and R 66 are each independently hydrogen, alkyl or haloalkyl;
  • R n is hydrogen or an alkyl group
  • n 0, 1, 2, 3, 4 or 5;
  • n, o and p are each independently 0, 1, 2, 3 or 4;
  • q 0, 1 or 2;
  • two R 3 on adjacent carbons may form a cycloalkyl, heterocyclic, aryl or heteroaryl group together with two adjacent carbon atoms; or ii) when m ⁇ 2 , two R 11 on adjacent carbons may form a cycloalkyl group, a heterocyclic group, an aryl group or a heteroaryl group together with two adjacent carbon atoms; or iii) o ⁇ 2, two on adjacent carbons R 33 and two adjacent carbon atoms may together form a cycloalkyl group, a heterocyclic group, an aryl group or a heteroaryl group; or iv) when p ⁇ 2, two R 55 on adjacent carbons are adjacent to each other Two carbon atoms may together form a cycloalkyl, heterocyclic, aryl or heteroaryl group;
  • R 1 and R 2 are each independently hydrogen, C 1-6 alkyl, C 2-6 alkenyl, C 2-6 alkynyl, C 3-8 cycloalkyl, C 2-6 Heterocyclyl, C 6-10 aryl, C 1-6 heteroaryl, C 3-8 cycloalkyl-C 1-6 alkyl-, C 2-6 heterocyclyl-C 1-6 alkyl- , C 6-10 aryl-C 1-6 alkyl- or C 1-6 heteroaryl-C 1-6 alkyl-;
  • R 1 , R 2 together with the nitrogen atom to which they are attached form a C 2-6 heterocyclic group or a 5-12 membered heteroaryl group;
  • Y is hydrogen, F, Cl, Br, I, hydroxy, cyano, nitro, amino, carboxy, C 1-6 alkyl, C 2-6 alkenyl, C 2-6 alkynyl, halogen C 1- 6 alkyl, halogenated C 2-6 alkenyl, halogenated C 2-6 alkynyl, C 6-10 aryl, C 6-10 aryl-C 1-6 alkyl-, halogenated C 6-10 Aryl or halogenated C 6-10 aryl-C 1-6 alkyl-;
  • L 1 and L 2 are each independently -(CR 3 R 4 ) n -, -(CR 11 R 22 ) m -O-, -(CR 33 R 44 ) o -NR n - or -(CR 55 R 66 ) p -S(O) q -;
  • R 3 and R 4 are each independently hydrogen, F, Cl, Br, I, amino, hydroxy, cyano, nitro, C 1-6 alkyl, C 2-6 alkenyl, C 2-6 alkyne , halo C 1-6 alkyl, amino substituted C 1-6 alkyl, hydroxy substituted C 1-6 alkyl, cyano substituted C 1-6 alkyl or nitro substituted C 1-6 alkyl;
  • R 11 , R 22 , R 33 , R 44 , R 55 and R 66 are each independently hydrogen, C 1-6 alkyl or halo C 1-6 alkyl;
  • R n is hydrogen or C 1-6 alkyl
  • n 0, 1, 2, 3, 4 or 5;
  • n, o and p are each independently 0, 1, 2, 3 or 4;
  • q 0, 1 or 2;
  • two R 3 on adjacent carbons and two adjacent carbon atoms may together form a C 3-6 cycloalkyl group, a C 2-6 heterocyclic group, a C 6-10 aryl group. Or 5-10 membered heteroaryl; or ii) m ⁇ 2, two R 11 on adjacent carbons and two adjacent carbon atoms may together form a C 3-6 cycloalkyl group, a C 2-6 hetero a ring group, a C 6-10 aryl group or a 5-10 membered heteroaryl group; or iii) o ⁇ 2, two R 33 on an adjacent carbon and the adjacent two carbon atoms may together form a C 3-6 a cycloalkyl group, a C 2-6 heterocyclic group, a C 6-10 aryl group or a 5-10 membered heteroaryl group; or iv) p ⁇ 2, two R 55 on adjacent carbons and two adjacent The carbon atoms may together form a C 3-6 cycloalkyl group, a C
  • R 1 and R 2 are each independently hydrogen, C 1-4 alkyl, C 2-4 alkenyl, C 2-4 alkynyl, C 3-6 cycloalkyl, C 2-6 Heterocyclyl, C 6-10 aryl, C 1-5 heteroaryl, C 3-6 cycloalkyl-C 1-4 alkyl-, C 2-5 heterocyclyl-C 1-4 alkyl- C 6-10 aryl-C 1-4 alkyl- or C 1-5 heteroaryl-C 1-4 alkyl-.
  • R 1 , R 2 and the nitrogen atom to which they are attached form a C 2-5 heterocyclyl or a 5-10 membered heteroaryl;
  • a C 2-5 heterocyclic group or a 5-10 membered heteroaryl group formed by R 1 , R 2 together with a nitrogen atom to which it is bonded is optionally substituted by one or more substituents selected from R 5 ;
  • R 5 is hydrogen, F, Cl, Br, hydroxy, cyano, nitro, amino, carboxy, C 1-4 alkyl or halo C 1-4 alkyl.
  • Y is hydrogen, F, Cl, Br, hydroxy, cyano, nitro, amino, carboxy, C 1-4 alkyl, C 2-4 alkenyl, C 2-4 alkynyl, halo C 1-4 alkyl, halo C 2-4 alkenyl, halo C 2-4 alkynyl, C 6-10 aryl, C 6-10 aryl-C 1-4 alkyl-, halogenated C 6-10 aryl or halogenated C 6-10 aryl-C 1-4 alkyl-.
  • R 1 and R 2 are each independently hydrogen, -CH 3 , -CH 2 CH 3 , -CH 2 CH 2 CH 3 , -CH(CH 3 ) 2 , cyclopropyl, cyclobutane Base, cyclopentyl, cyclohexyl, benzyl, 4-fluorobenzyl or 4-cyanobenzyl.
  • R 1 , R 2 and the nitrogen atom to which they are attached form the following substructure:
  • Y is hydrogen, F, Cl, Br, hydroxy, cyano, nitro, amino, carboxyl, -CH 3, -CHF 2, -CH 2 F, -CF 3, -CH 2 CH 3 , -CH 2 CH 2 F, -CH 2 CHF 2 , -CH 2 CH 2 CH 3 , -CH(CH 3 ) 2 , -C(CH 3 ) 3 , phenyl, 2-fluorophenyl, 3- Fluorophenyl or 4-fluorophenyl.
  • L 1 and L 2 are each independently -(CR 3 R 4 ) n -;
  • R 3 and R 4 are each independently hydrogen, F, Cl, Br, I, amino, hydroxy, cyano, nitro, C 1-4 alkyl, halo C 1-4 alkyl, amino substituted C 1-4 alkyl, hydroxy substituted C 1-4 alkyl, cyano substituted C 1-4 alkyl or nitro substituted C 1-4 alkyl;
  • n 0, 1, 2, 3, 4 or 5.
  • L 1 and L 2 are each independently -(CR 3 R 4 ) n - or -(CR 11 R 22 ) m -O-;
  • R 11 and R 22 are each independently hydrogen, C 1-4 alkyl or halo C 1-4 alkyl;
  • n 0, 1, 2, 3 or 4;
  • R 3 , R 4 and n have the meanings indicated in the present invention.
  • L 1 and L 2 are each independently -(CR 3 R 4 ) n - or -(CR 33 R 44 ) o -NR n -;
  • R 33 and R 44 are each independently hydrogen, C 1-4 alkyl or halo C 1-4 alkyl;
  • o 0, 1, 2, 3 or 4;
  • R n is hydrogen or C 1-4 alkyl
  • R 3 , R 4 and n have the meanings indicated in the present invention.
  • L 1 and L 2 are each independently -(CR 3 R 4 ) n - or -(CR 55 R 66 ) p -S(O) q -;
  • R 55 and R 66 are each independently hydrogen, C 1-4 alkyl or halo C 1-4 alkyl;
  • p 0, 1, 2, 3 or 4;
  • q 0, 1 or 2;
  • R 3 , R 4 and n have the meanings indicated in the present invention.
  • two R 3 on adjacent carbons and the two adjacent carbon atoms may together form a C 3-6 cycloalkyl group or a C 6-10 aryl group.
  • two R 11 on adjacent carbons may together with two adjacent carbon atoms form a C 3-6 cycloalkyl group or a C 6-10 aryl group.
  • two R 33 on adjacent carbons may together with two adjacent carbon atoms form a C 3-6 cycloalkyl group or a C 6-10 aryl group.
  • two R< 55 > on adjacent carbons and the two adjacent carbon atoms may together form a C3-6 cycloalkyl or C6-10 aryl group.
  • R 7 is hydrogen or C 1-4 alkyl
  • X 1 , X 2 , X 3 , X 4 , X 5 and X 6 are each independently N or CR 8 ;
  • the present invention relates to a compound having a structure of one of the following structures or a stereoisomer, an oxynitride, and a salt having one of the following structural compounds:
  • the invention relates to a composition comprising one or more compounds described herein.
  • compositions of the present invention further comprise a pesticidally acceptable surfactant and/or carrier.
  • the invention relates to the use of a composition comprising a compound of the invention for the control of plant diseases.
  • the articles used herein are used to refer to the articles of one or more than one (ie, at least one).
  • a component refers to one or more components, that is, there may be more than one component contemplated for use or use in embodiments of the embodiments.
  • Stereoisomer refers to a compound that has the same chemical structure but differs in the way the atoms or groups are spatially aligned. Stereoisomers include enantiomers, diastereomers, conformational isomers (rotomers), geometric isomers (cis/trans) isomers, atropisomers, etc. .
  • Enantiomer refers to two isomers of a compound that are not superimposable but are mirror images of each other.
  • Diastereomer refers to a stereoisomer that has 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. The mixture of diastereomers can be separated by high resolution analytical procedures such as electrophoresis and chromatography, such as HPLC.
  • optically active compounds Many organic compounds exist in optically active forms, i.e., they have the ability to rotate a 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 for specifying the rotation of plane polarized light caused by the compound, wherein (-) or l indicates that the compound is left-handed.
  • Compounds prefixed with (+) or d are dextrorotatory.
  • a particular stereoisomer is an enantiomer and a mixture of such isomers is referred to as a mixture of enantiomers.
  • a 50:50 mixture of enantiomers is referred to as a racemic mixture or a racemate, which can occur when there is no stereoselectivity or stereospecificity in a chemical reaction or process.
  • the compounds of the present invention may be optionally substituted with one or more substituents, such as the compounds of the above formula, or specific examples, subclasses, and inclusions of the present invention.
  • substituents such as the compounds of the above formula, or specific examples, subclasses, and inclusions of the present invention.
  • a class of compounds may be used interchangeably.
  • substituted means that one or more hydrogen atoms in a given structure are replaced by a particular substituent. Unless otherwise indicated, an optional substituent group can be substituted at each substitutable position of the group.
  • substituents When more than one position in the given formula can be substituted by one or more substituents selected from a particular group, the substituents may be substituted at the various positions, either identically or differently.
  • the substituents described therein may be, but are not limited to, hydrazine, fluorine, chlorine, bromine, iodine, cyano, hydroxy, nitro, amino, carboxy, alkyl, alkoxy, alkoxyalkyl, alkane.
  • C 1 -C 6 alkyl or “C 1-6 alkyl” refers especially to the independently disclosed methyl, ethyl, C 3 alkyl, C 4 alkyl, C 5 alkyl and C 6 alkane. base.
  • alkyl or "alkyl group” as used herein, denotes a saturated straight or branched chain monovalent hydrocarbon group containing from 1 to 20 carbon atoms; wherein the alkyl group is optionally One or more substituents described herein are substituted. Unless otherwise specified, an alkyl group contains from 1 to 20 carbon atoms. In one embodiment, the alkyl group contains from 1 to 12 carbon atoms; in one embodiment, the alkyl group contains from 1 to 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 one 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 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(CHCH
  • alkenyl denotes a straight or branched chain monovalent hydrocarbon radical containing from 2 to 12 carbon atoms, wherein at least one site of unsaturation, i.e., has a carbon-carbon sp 2 double bond, wherein the alkenyl group
  • the group may be optionally substituted with one or more substituents described herein, including 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 comprises 2 - 4 carbon atoms.
  • alkynyl means a straight or branched chain monovalent hydrocarbon radical containing from 2 to 12 carbon atoms, wherein there is at least one carbon-carbon sp triple bond.
  • alkoxy denotes an alkyl group attached to the remainder of the molecule through an oxygen atom, wherein the alkyl group has the meaning as described herein.
  • alkoxy groups include, but are not limited to, methoxy (MeO, -OCH 3 ), ethoxy (EtO, -OCH 2 CH 3 ), 1-propoxy (n-PrO, n- Propyloxy, -OCH 2 CH 2 CH 3 ), 2-propoxy (i-PrO, i-propoxy, -OCH(CH 3 ) 2 ), and the like.
  • cycloalkyl denotes a monovalent or polyvalent saturated monocyclic, bicyclic or tricyclic system containing from 3 to 12 carbon atoms. In one embodiment, the cycloalkyl contains 3-10 carbon atoms; in another embodiment, the cycloalkyl contains 3-8 carbon atoms; in yet another embodiment, the cycloalkyl contains 3-6 carbon atom.
  • the cycloalkyl group is optionally substituted with one or more substituents described herein.
  • Such examples include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl, cyclodecyl, cycloundecyl, cyclododeyl Alkyl, and so on.
  • cycloalkylalkyl denotes an alkyl group substituted by one or more cycloalkyl groups, wherein the alkyl group and cycloalkyl group have the meanings as described herein.
  • heterocyclyl and “heterocycle” are used interchangeably herein to refer to a saturated or partially unsaturated monocyclic, bicyclic or tricyclic ring containing from 3 to 15 ring atoms, wherein monocyclic, bicyclic or tricyclic
  • the ring does not contain an aromatic ring, and at least one ring atom is selected from the group consisting of nitrogen, sulfur and oxygen atoms.
  • the sulfur atom of the ring can be optionally oxidized to an S-oxide.
  • the nitrogen atom of the ring can be optionally oxidized to an N-oxygen compound.
  • heterocyclic groups include, but are not limited to, oxiranyl, azetidinyl, oxetanyl, thietanyl, pyrrolidinyl (e.g., 2-pyrrolidinyl), 2-pyrrole Polinyl, 3-pyrrolyl, pyrazolidinyl, imidazolinyl, imidazolidinyl, tetrahydrofuranyl, dihydrofuranyl, tetrahydrothiophenyl, dihydrothienyl, 1,3-dioxocyclopentyl, Dithiocyclopentyl, tetrahydropyranyl, dihydropyranyl, 2H-pyranyl, 4H-pyranyl, tetrahydrothiopyranyl, piperidinyl (2-piperidinyl, 3-piperidine) , 4-piperidin
  • Examples of the sulfur atom in the heterocyclic group being oxidized include, but are not limited to, a sulfolane group, a 1,1-dioxothiomorpholinyl group.
  • the heterocyclyl group is optionally substituted with one or more substituents described herein.
  • heterocyclylalkyl means that the alkyl group is substituted by one or more heterocyclyl groups, wherein the alkyl group and the heterocyclyl group have the meanings as described herein.
  • heteroatom refers to O, S, N, P, and Si, including any form of oxidation states of N, S, and P; forms of primary, secondary, tertiary, and quaternary ammonium salts; or nitrogen atoms in heterocycles. a form in which hydrogen is substituted, for example, N (like N in 3,4-dihydro-2H-pyrrolyl), NH (like NH in pyrrolidinyl) or NR (like in N-substituted pyrrolidinyl) NR).
  • halogen means fluorine (F), chlorine (Cl), bromine (Br) or iodine (I).
  • aryl denotes a monocyclic, bicyclic and tricyclic carbocyclic ring system containing from 6 to 14 ring atoms, or from 6 to 12 ring atoms, or from 6 to 10 ring atoms, wherein at least one ring system is aromatic Of the family, wherein each ring system comprises a ring of 3-7 atoms and one or more attachment points are attached to the remainder of the molecule.
  • aryl can be used interchangeably with the term "aromatic ring”. Examples of the aryl group may include a phenyl group, a fluorenyl group, a naphthyl group, and an anthracenyl group. The aryl group is optionally substituted with one or more substituents described herein.
  • arylalkyl denotes an alkyl group substituted with one or more aryl groups, such as benzyl.
  • heteroaryl denotes a monocyclic, bicyclic and tricyclic ring system containing from 5 to 12 ring atoms, or from 5 to 10 ring atoms, or from 5 to 6 ring atoms, wherein at least one ring system is aromatic, And at least one ring system comprises one or more heteroatoms, wherein each ring system comprises a ring of 5-7 atoms and one or more attachment points are attached to the remainder of the molecule.
  • heteroaryl can be used interchangeably with the terms “heteroaryl 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.
  • 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 (eg 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
  • heteroarylalkyl refers to an alkyl group substituted with one or more heteroaryl groups.
  • alkoxyalkyl refers to an alkyl group substituted with one or more alkoxy groups.
  • alkylamino means that the amino group is substituted by one or two alkyl groups.
  • haloalkyl means that the alkyl group is substituted by one or more halogens.
  • haloalkenyl refers to an alkenyl group substituted by one or more halogens.
  • haloalkynyl means that the alkynyl group is substituted by one or more halogens.
  • haloaryl means that the aryl group is substituted by one or more halogens.
  • haloarylalkyl means that the arylalkyl group is substituted by one or more halogens.
  • haloalkoxy means that the alkoxy group is substituted by one or more halogens.
  • 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 of the 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.
  • the salt of the compound of formula (I) can be obtained by using a metal hydroxide such as sodium hydroxide or an amine such as ammonia, trimethylamine, diethanolamine, 2-methylthiopropylamine, bisallylamine, 2-butyl Oxyethylamine, morpholine, cyclododecylamine or benzylamine) are prepared by treating a compound of formula (I).
  • a metal hydroxide such as sodium hydroxide
  • an amine such as ammonia, trimethylamine, diethanolamine, 2-methylthiopropylamine, bisallylamine, 2-butyl Oxyethylamine, morpholine, cyclododecylamine or benzylamine
  • acceptable salts can be formed from organic acids and inorganic acids, such as acetic acid, propionic acid, lactic acid, citric acid, tartaric acid, succinic acid, fumaric acid, maleic acid, and propylene. 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 the like are known. Accepted acid.
  • compositions and formulations of the compounds of the invention are provided.
  • the compounds of the present invention are generally useful as bactericidal active ingredients in compositions, i.e., formulations, and typically also include agrochemically acceptable surfactants and/or carriers.
  • the above surfactants may be various surfactants well known in the field of pesticide formulations, and the present invention is preferably one or more of an emulsifier, a dispersant and a wetting agent.
  • carrier class 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 Mixture of fertilizer, urea and amine fertilizer, glucose, maltose, sucrose, anhydrous potassium carbonate, anhydrous sodium carbonate, anhydrous potassium hydrogencarbonate, anhydrous sodium hydrogencarbonate, attapulgite, anhydrous potassium carbonate and anhydrous hydrogen carbonate A mixture of potassium and one or more of a mixture of anhydrous sodium carbonate and anhydrous sodium hydrogencarbonate.
  • the emulsifier may be various emulsifiers known in the field of pesticide formulations. Specifically, the emulsifier may be calcium dodecylbenzenesulfonate, triphenylethylphenol polyoxyethylene ether phosphate, fatty alcohol polyoxyethylene.
  • alkylphenol ethoxylates alkylphenol polyoxyethylene polyoxypropylene ethers, fatty amines, ethylene oxide adducts of fatty amides, fatty acid polyoxyethylene esters, rosin acid ethylene oxide adducts , polyol fatty acid ester and its ethylene oxide adduct, styryl phenyl polyoxyethylene ether, alkyl phenol 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 dispersing agent may be various dispersing agents known in the field of agricultural pesticide formulations.
  • the dispersing agent is an acrylic acid homopolymer sodium salt, a maleic acid disodium salt, a naphthalenesulfonic acid formaldehyde condensate sodium salt, and a rosin block polymerization.
  • One or more of the sodium lignin sulfonate is an acrylic acid homopolymer sodium salt, a maleic acid disodium salt, a naphthalenesulfonic acid formaldehyde condensate sodium salt, and a rosin block polymerization.
  • the above wetting agent may be various wetting agents known in the field of pesticide formulations.
  • the wetting agent may be sodium lauryl sulfate, sodium secondary alkyl sulfate, sodium dodecylbenzenesulfonate, fat.
  • the bactericidal composition may further contain various auxiliaries for preparations commonly used in the field of pesticide formulations.
  • the auxiliaries for the preparation may be solvents, cosolvents, thickeners, and antifreeze.
  • a agent, a capsule, a protective agent, an antifoaming agent, a disintegrant, a stabilizer, a preservative, and a binder may be solvents, cosolvents, thickeners, and antifreeze.
  • a agent a capsule, a protective agent, an antifoaming agent, a disintegrant, a stabilizer, a preservative, and a binder.
  • the above solvent may be various solvents known in the field of pesticide formulations, and specifically, the solvent may be one or more of an organic solvent, a vegetable oil, a mineral oil, a solvent oil, and water.
  • the organic solvent comprises N-methylpyrrolidone, tetrahydrofuran, dimethyl sulfoxide, N,N-dimethylformamide, 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, rosin-based vegetable oil, turpentine oil, epoxidized soybean oil, soybean oil, peanut oil, rapeseed oil, castor oil, corn oil, and pine nut oil.
  • the mineral oil includes one or more of liquid wax, engine oil, kerosene, and lubricating oil.
  • the above solvent can also be used as a co-solvent.
  • the antifreeze agent may be various antifreeze agents known in the field of pesticide formulations, and the present invention is preferably one or more of ethylene glycol, propylene glycol, glycerin and urea.
  • the thickener may be various thickeners known in the field of pesticide formulations. Specifically, the thickener may be xanthan gum, polyvinyl alcohol, polypropylene alcohol, polyethylene glycol, white carbon, diatom. One or more of soil, kaolin, clay, sodium alginate, magnesium aluminum silicate, sodium aluminum silicate, carboxymethyl cellulose, sodium hydroxypropyl cellulose, and organic bentonite.
  • the above-mentioned capsules may be various kinds of capsules known in the field of pesticide formulations, and the present invention is preferably one or more of polyurethane, polyurea and urea-formaldehyde resins.
  • the above protective agent may be various protective agents known in the field of agricultural chemical formulations, and the present invention is preferably polyvinyl alcohol and/or polyethylene glycol.
  • the above antifoaming agent may be various antifoaming agents known in the field of pesticide formulations, and the present invention is preferably one or more of organosiloxane, tributyl phosphate and silicone.
  • the above stabilizer is selected from one or more of triphenyl phosphite, epichlorohydrin and acetic anhydride.
  • the above preservative is selected from one or more of benzoic acid, sodium benzoate, 1,2-benzisothiazolin-3-one (abbreviated as BIT), carson and potassium sorbate.
  • the invention also provides a preparation prepared from the above bactericidal composition, wherein the dosage form is emulsifiable concentrate, water emulsion, microemulsion, soluble liquid agent, aqueous suspension, suspoemulsion, ultra low volume spray, oil suspension Agent, microcapsule suspension agent, water surface film 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 dispersion granules or seed coating agents.
  • the above dosage forms can all be prepared by conventional methods in the art.
  • the preparation method of the above emulsifiable concentrate preparation may include, for example, mixing and stirring each active component, a solvent, a co-solvent, and an emulsifier to form a uniform transparent oil phase, thereby obtaining an emulsifiable concentrate preparation.
  • the above aqueous emulsion preparation method may, for example, comprise mixing an active ingredient, an emulsifier, a co-solvent and a solvent to form a homogeneous oil phase; mixing water, a thickener, an antifreeze or the like to form a uniform aqueous phase. Under high shear, the aqueous phase is added to the oil phase or the oil phase is added to the aqueous phase to form a water emulsion with good dispersibility.
  • the preparation method of the above microemulsion may be, for example, mixing and stirring an active ingredient, an emulsifier, and a solvent into a uniform transparent oil phase. Under agitation, water was gradually added to form a uniform transparent microemulsion.
  • water or oil may be used as a medium, and an auxiliary agent such as an active component or a surfactant may be added to a sanding kettle, and after grinding to a certain particle size, the mixture may be filtered.
  • the metered thickener is then added to the ground mother liquor and the shear is dispersed evenly. Made into oil suspension or water suspension.
  • the preparation method of the above water-dispersible granules and soluble granules for example, the active components, the dispersing agent, the wetting agent, the carrier, and the like may be uniformly mixed, and then pulverized to a certain particle diameter by a jet stream, and then kneaded by adding water. Finally, it is added to a granulator for granulation, and after drying, a water-dispersible granule or a soluble granule can be obtained.
  • the preparation method of the above-mentioned soluble powder and wettable powder for example, the fillers of the respective active components, various auxiliary agents and other carriers may be thoroughly mixed and pulverized by an ultrafine pulverizer.
  • the bactericidal composition of the present invention may be provided in the form of a finished preparation, that is, each substance in the composition has been mixed; it may also be provided in the form of a separate preparation, which is self-mixed in a bucket or a tank before use, and is selected according to the concentration of the active substance required. It can be diluted with water and diluted.
  • the compounds of the invention are useful as plant disease control agents. Accordingly, the present invention may further comprise a method for controlling a plant disease caused by a phytopathogenic fungus, the method comprising administering to the plant to be protected or a part thereof or to the seed to be protected an effective amount of the compound of the present invention or comprising the A fungicidal composition of a compound.
  • the compounds and/or compositions of the present invention provide control over diseases caused by a broad spectrum of phytopathogenic fungi of the Basidiomycetes, Ascomycetes, Oomycetes, and Deuteromycetes. They are effective in controlling a wide range of plant diseases, especially leaf pathogens of ornamental crops, turf crops, vegetable crops, field crops, cereal crops and fruit crops.
  • pathogens include: Oomycetes, including Phytophthora diseases such as Phytophthora infestans, Phytophthora megasperma, Phytophthora parasitica, Phytophthora Cinnamomi) and Phytophthora capsici disease, Pythium species diseases such as Pythium aphanidermatum, and Peronosporaceae species diseases such as grape downy mildew Plasmopara viticola, Peronospora spp. (including Peronospora tabacina and Peronospora parasitica), Pseudoperonospora spp.
  • Puccinia serrata Puccinia serrata (Puccinia) Recentita
  • Puccinia striiformis Puccinia hordei
  • Puccinia graminis Puccinia arachidis
  • Rhizoctonia spp Other pathogens include Rhizoctonia spp.
  • Fusarium species such as Fusarium roseum, Fusarium graminearum ( Fusarium graminearum) and Fusarium oxysporum; Verticillium dahliae; Sclerotium rolfsii; Rynchosporium secalis; Cercosporidium personatum, black spot (Cercospora arachidicola) and C. cerevisiae (Cercospora beticola); and other classes and species closely related to these pathogens.
  • compositions or combinations also against bacteria such as Erwinia amylovora, Xanthomonas campestris, Pseudomonas syringae and others.
  • the strain has resistance activity.
  • the bactericidal composition of the present invention is simple to use, and is applied to a place where crops and crops are grown before, or after germination, in a conventional manner, such as soil mixing, spraying, spraying, pouring, etc., depending on climatic conditions. Depending on the state of the crop, it is generally applied in an amount of 10-5000 g per acre and diluted to 10-400 mg/L (preferably 100-300 mg/L).
  • the diluent is preferably water.
  • the bactericidal effect of the bactericidal composition of the present invention is usually related to external factors such as climate, but the influence of the climate can be alleviated by using an appropriate dosage form.
  • composition of the present invention can also be used in combination with other compounds having bactericidal, insecticidal or herbicidal activity, or with nematicides, acaricides, arthropodicides, safeners, plant growth regulators, fertilizers or soil conditioners. Mixtures and the like are used.
  • the compounds of the present invention can be prepared by the methods described herein, unless otherwise stated, wherein the substituents are as defined in (I).
  • the following synthetic schemes and Examples 1-11 are used to further illustrate the contents of the present invention.
  • the compound of the formula (I) can be synthesized by the method disclosed in Synthesis Scheme 1, wherein R 1 , R 2 , Y, L 1 , L 2 and Ring A have the meanings as defined in the present invention.
  • the compound of formula (a) is reacted with chlorine gas under acidic conditions to give a compound of formula (b); the compound of formula (b) is reacted with a compound of formula (c) under basic conditions to give a compound of formula (d); a compound of formula (d) in a base Reaction with a compound of formula (e) under neutral conditions affords a compound of formula (I).
  • the compound of the formula (I) can also be synthesized by the method disclosed in Synthesis Scheme 2, wherein R 1 , R 2 , Y, L 1 , L 2 and Ring A have the meanings as defined in the present invention.
  • the compound of formula (f) is reacted with a compound of formula (c) under basic conditions to provide a compound of formula (I).
  • 1,2-Di(1H-1,2,4-triazol-3-yl)disulfide (60.0 g, 0.30 mol) was dissolved in N,N-dimethylformamide (300 mL) under nitrogen. After adding potassium carbonate (69.0 g, 0.50 mol), and stirring and mixing at 0 ° C, N,N-dimethylaminosulfonyl chloride (93.34 g, 0.65 mol) was slowly added dropwise, and the reaction was continued after 2 hours of dropwise addition. 6 hours. The reaction solution was slowly poured into water, stirred for 1 hour, filtered, and the solid was dried to give a white powder, 107.2 g, yield: 86.3%.
  • 4,5,6,7-Tetrahydrothieno[3,2-c]pyridine (3.00 g, 21.6 mmol) was added to a 250 mL single-necked flask, then dichloromethane (80 mL) was added and cooled to -5 °C. After stirring for 10 minutes, a suspension of N-bromosuccinimide (3.89 g, 21.6 mmol) in dichloromethane (20 mL) was slowly added dropwise to the reaction solution through a constant pressure dropping funnel for 1 hour. After completion, stirring was continued at -5 ° C for 12 hours, and the solvent was evaporated under reduced pressure using a rotary evaporator to afford 4.46 g of a yellow solid powder, yield: 95.1%.
  • 4,5,6,7-Tetrahydrothieno[3,2-c]pyridine (3.00 g, 21.6 mmol) was added to a 250 mL single-necked flask, then dichloromethane (80 mL) was added and cooled to -5 °C. After stirring for 10 minutes, a suspension of N-chlorosuccinimide (2.88 g, 21.6 mmol) in dichloromethane (20 mL) was slowly added dropwise to the reaction mixture through a constant pressure dropping funnel for 1 hour. After completion, stirring was continued at a temperature of -5 ° C for 12 hours, and the solvent was evaporated under reduced pressure using a rotary evaporator to yield 3.51 g of a yellow solid powder, yield: 93.8%.
  • 4,5,6,7-Tetrahydrothieno[3,2-c]pyridine (3.00 g, 21.6 mmol) was added to a 250 mL single-necked flask, then tert-butanol (3.70 g, 50.0 mmol) was added and stirred 10
  • 50% dilute sulfuric acid (20 mL) was dropped into the reaction solution through a constant pressure dropping funnel, and after 0.5 hour dropwise, the mixture was heated to 50 ° C and stirred for 1 hour.
  • the organic phase was washed three times with water (30 mL), and the solvent was evaporated under reduced pressure on a rotary evaporator. Yellow solid powder 3.50 g, yield: 82.7%.
  • 3-mercapto-1,2,4,-triazole (12.0 g, 0.12 mol) was dissolved in hydrochloric acid solution (2N, 0.12 L) at room temperature, the mixture was reduced to 0 ° C, and chlorine gas was reacted for 40 minutes. The mixture was allowed to stand at 0 ° C for 30 minutes, and filtered to give a white solid, which was washed with ice water (500 mL ⁇ 3) to yield 14.5 g of white solid.
  • 1,2,3,4-tetrahydroisoquinoline (1.33 g, 9.98 mmol) and triethylamine (1.5 g, 14.82 mmol) were dissolved in tetrahydrofuran (5 mL), stirred at room temperature for 30 min, then slowly dripped A solution of 1H-1,2,4-triazole-3-sulfonyl chloride (1.67 g, 9.96 mmol) in tetrahydrofuran (5 mL) was evaporated. Filtration and concentration of the filtrate were evaporated. EtOAc (EtOAc m.)
  • the third step 3-((3,4-dihydroisoquinolin-2(1H)-yl)sulfonyl)-N,N-dimethyl-1H-1,2,4-triazole-1- Synthesis of sulfonamide
  • 1,2,3,4-tetrahydroquinoline (0.66 g, 5.0 mmol)
  • pyridine (0.48 g, 6.0 mmol
  • tetrahydrofuran 10 mL
  • 1-(N,N-dimethylaminosulfonyl)-1H-1,2,4-triazole-3-sulfonyl chloride (1.38 g, 5.0 mmol) in tetrahydrofuran (10 mL) was added dropwise over 10 min.
  • the solution was reacted at room temperature for 2 hours after completion of the dropwise addition.
  • the solid was removed by filtration, and the solvent was evaporated to dryness crystals crystals crystals crystalsssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssss
  • Example 3 According to the preparation method of Example 3, different materials were used to react with the intermediate 1-(N,N-dimethylaminosulfonyl)-1H-1,2,4-triazole-3-sulfonyl chloride.
  • the target compound in Table 1 was obtained.
  • the inventors examined the efficacy of the compounds of the present invention against harmful fungi by taking a part of the compounds of the present invention as an example.
  • Test target Rhizoctonia solani, Cucumber gray mold, Cucumber downy mildew, Cucumber powdery mildew
  • Test treatment The compound was dissolved in DMF to 1% EC for use. The bactericidal activity of these compounds on four test targets at different doses was evaluated by live potting.
  • the leaf inoculation method is adopted. Two potted cucumber seedlings were selected in the true leaf stage. After the spray was dried, the cake was placed on the leaves. After 24 hours of darkening at 24 to 26 ° C, the natural light is moisturized and cultured for about 3 days. After the control was fully diagnosed, the lesion diameter of each inoculation point was measured with a caliper, and the control effect was calculated.
  • Potted corn seedlings with two leaves and one heart and the same growth are selected. After spraying, they are naturally dried and inoculated for about 24 hours. After the spray of the drug is dried, the cake is placed on the leaves. After immersion in 25 ⁇ 26°C for 24 hours, restore the natural light and moisturize for about 3 days. After the control is fully ill, the length of the lesion at each inoculation point is measured with a caliper, and the control effect is calculated.
  • Test results The test results are shown in Table 2-5.
  • Example number Control effect (%) Example 1 100 Example 2 100 Example 3 100 Example 4 100 Example 5 100 Example 6 98 Example 7 100 Example 8 100 Example 9 100 Example 10 100
  • Example number Control effect (%) Example 2 100 Example 4 85 Example 5 100 Example 6 100 Example 7 80 Example 8 100
  • Example number Control effect (%) Example 2 80 Example 5 80 Example 6 80 Example 8 100
  • the test results show that the compound of the present invention has good control effect against cucumber downy mildew at different dosages, and shows better control effect against cucumber downy mildew at low dose, for example, the dosage of Example 8 at 25 mg/L.
  • the control effect against cucumber downy mildew is 100%, while the control effects of cyazofamid and carbazolam on cucumber downy mildew are 20% and 85%, respectively.
  • the compound of the invention also has a certain control effect on Rhizoctonia solani, Botrytis cinerea, and Cucumber powdery mildew.

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Abstract

本发明提供一种三唑衍生物及其在农业中的应用；具体地，本发明提供一种如式(I)所示的化合物或式(I)所示的化合物的立体异构体、氮氧化物及盐，其制备方法；含有这些化合物的组合物和制剂及其作为防治植物病原性真菌的用途；其中R 1、R 2、Y、L 1、L 2和环A具有如本发明所述的含义。

Description

三唑衍生物及其在农业中的应用 技术领域
本发明提供一种新的三唑衍生物及其制备方法，含有这些化合物的组合物及其在农业中的应用。
背景技术
三唑类衍生物因其对植物病原性真菌的广谱性、高效性等特点，已被广泛应用于观赏作物、蔬菜作物、大田作物、谷类作物和果树作物。现在农业由于农药的长时间地大量使用，使得作物上的病害对其产生了抗性，从而使农药的防治效果明显降低，导致消费成本上升。因此，需要不断开发出具有更好防治效果的新型化合物以解决这些问题。
发明内容
本发明提供一种新型三唑类化合物，以及含有该类化合物的组合物和制剂，用于控制植物病原性真菌。具体地说：
一方面，本发明涉及一种如式(I)所示的化合物或式(I)所示的化合物的立体异构体、氮氧化物及盐：
Figure PCTCN2018086508-appb-000001
其中，
R 1和R 2各自独立地为氢、烷基、烯基、炔基、环烷基、杂环基、芳基、杂芳基、环烷基烷基、杂环基烷基、芳基烷基或杂芳基烷基；
或R 1、R 2和与之相连接的氮原子一起形成杂环基或杂芳基；
其中，由R 1、R 2和与之相连接的氮原子一起形成的杂环基或杂芳基任选地被一个或多个选自R 5的取代基所取代；
Y为氢、卤素、羟基、氰基、硝基、氨基、羧基、烷基、烯基、炔基、卤代烷基、卤代烯基、卤代炔基、芳基、芳基烷基、卤代芳基或卤代芳基烷基；
L 1和L 2各自独立地为-(CR 3R 4) n-、-(CR 11R 22) m-O-、-(CR 33R 44) o-NR n-或-(CR 55R 66) p-S(O) q-；
其中，R 3和R 4各自独立地为氢、卤素、氨基、羟基、氰基、硝基、烷基、烯基、炔基、卤代烷基、氨基取代的烷基、羟基取代的烷基、氰基取代的烷基或硝基取代的烷基；
或R 3、R 4可以与相连接的碳原子形成C＝O；
R 11、R 22、R 33、R 44、R 55和R 66各自独立地为氢、烷基或卤代烷基；
R n为氢或烷基；
其中，n为0、1、2、3、4或5；
m、o和p各自独立地为0、1、2、3或4；
q为0、1或2；
或i)n≥2时，相邻碳上的两个R 3与相邻的两个碳原子可以一起形成环烷基、杂环基、芳基或杂芳基；或ii)m≥2时，相邻碳上的两个R 11与相邻的两个碳原子可以一起形成环烷基、杂环基、芳基或杂芳基；或iii)o≥2时，相邻碳上的两个R 33与相邻的两个碳原子可以一起形成环烷基、杂环基、芳基或杂芳基；或iv)p≥2时，相邻碳上的两个R 55与相邻的两个碳原子可以一起形成环烷基、杂环基、芳基或杂芳基；
Figure PCTCN2018086508-appb-000002
为环烷基、杂环基、芳基或杂芳基；
其中，
Figure PCTCN2018086508-appb-000003
任选地被1、2、3或4个选自R 6的取代基所取代；
其中，R 5和R 6各自独立地为氢、卤素、羟基、氰基、硝基、氨基、羧基、C 1-6烷基、C 2-6烯基、C 2-6炔基、卤代C 1-6烷基、卤代C 2-6烯基、卤代C 2-6炔基、C 1-6烷氧基、卤代C 1-6烷氧基、C 1-6烷氧基-(C＝O)-、C 1-6烷氧基-C 1-6烷基-、C 1-6烷基-(C＝O)-O-、C 1-6烷基-(C＝O)-、C 1-6烷基-SO 2-、C 1-6烷基氨基、C 1-6烷基氨基-(C＝O)-、C 1-6烷基氨基-SO 2-、C 3-6环烷基、C 2-6杂环基、C 6-10芳基或C 1-6杂芳基。
在一些实施方案中，R 1和R 2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 2-6杂环基、C 6-10芳基、C 1-6杂芳基、C 3-8环烷基-C 1-6烷基-、C 2-6杂环基-C 1-6烷基-、C 6-10芳基-C 1-6烷基-或C 1-6杂芳基-C 1-6烷基-；
或R 1、R 2和与之相连接的氮原子一起形成C 2-6杂环基或5-12元杂芳基；
其中，由R 1、R 2和与之相连接的氮原子一起形成的C 2-6杂环基或5-12元杂芳基任选地被一个或多个选自R 5的取代基所取代；
Y为氢、F、Cl、Br、I、羟基、氰基、硝基、氨基、羧基、C 1-6烷基、C 2-6烯基、C 2-6炔基、卤代C 1-6烷基、卤代C 2-6烯基、卤代C 2-6炔基、C 6-10芳基、C 6-10芳基-C 1-6烷基-、卤代C 6-10芳基或卤代C 6-10芳基-C 1-6烷基-；
L 1和L 2各自独立地为-(CR 3R 4) n-、-(CR 11R 22) m-O-、-(CR 33R 44) o-NR n-或-(CR 55R 66) p-S(O) q-；
其中，R 3和R 4各自独立地为氢、F、Cl、Br、I、氨基、羟基、氰基、硝基、C 1-6烷基、C 2-6烯基、C 2-6炔基、卤代C 1-6烷基、氨基取代的C 1-6烷基、羟基取代的C 1-6烷基、氰基取代的C 1-6烷基或硝基取代的C 1-6烷基；
或R 3、R 4可以与相连接的碳原子形成C＝O；
R 11、R 22、R 33、R 44、R 55和R 66各自独立地为氢、C 1-6烷基或卤代C 1-6烷基；
R n为氢或C 1-6烷基；
其中，n为0、1、2、3、4或5；
m、o和p各自独立地为0、1、2、3或4；
q为0、1或2；
或i)n≥2时，相邻碳上的两个R 3与相邻的两个碳原子可以一起形成C 3-6环烷基、C 2-6杂环基、C 6-10芳基或5-10元杂芳基；或ii)m≥2时，相邻碳上的两个R 11与相邻的两个碳原子可以一起形成C 3-6环烷基、C 2-6杂环基、C 6-10芳基或5-10元杂芳基；或iii)o≥2时，相邻碳上的两个R 33与相邻的两个碳原子可以一起形成C 3-6环烷基、C 2-6杂环基、C 6-10芳基或5-10元杂芳基；或iv)p≥2时，相邻碳上的两个R 55与相邻的两个碳原子可以一起形成C 3-6环烷基、C 2-6杂环基、C 6-10芳基或5-10元杂芳基；
Figure PCTCN2018086508-appb-000004
为C 3-8环烷基、C 2-6杂环基、C 6-10芳基或5-12元杂芳基；
其中，
Figure PCTCN2018086508-appb-000005
任选地被1、2、3或4个选自R 6的取代基所取代；
其中，R 5和R 6各自独立地为氢、F、Cl、Br、I、羟基、氰基、硝基、氨基、羧基、C 1-4烷基、C 2-4烯基、C 2-4炔基、卤代C 1-4烷基、卤代C 2-4烯基、卤代C 2-4炔基、C 1-4烷氧基、卤代C 1-4烷氧基、C 1-4烷氧基-(C＝O)-、C 1-4烷氧基-C 1-3烷基-、C 1-4烷基-(C＝O)-O-、C 1-4烷基-(C＝O)-、C 1-4烷基-SO 2-、C 1-4烷基氨基、C 1-4烷基氨基-(C＝O)-、C 1-4烷基氨基-SO 2-、C 3-6环烷基、C 2-6杂环基、C 6-10芳基或C 1-4杂芳基。
在一些实施方案中，R 1和R 2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 2-6杂环基、C 6-10芳基、C 1-5杂芳基、C 3-6环烷基-C 1-4烷基-、C 2-5杂环基-C 1-4烷基-、C 6-10芳基-C 1-4烷基-或C 1-5杂芳基-C 1-4烷基-。
在一些实施方案中，R 1、R 2和与之相连接的氮原子一起形成C 2-5杂环基或5-10元杂芳基；
其中，R 1、R 2和与之相连接的氮原子一起形成的C 2-5杂环基或5-10元杂芳基任选地被一个或多个选自R 5的取代基所取代；
R 5为氢、F、Cl、Br、羟基、氰基、硝基、氨基、羧基、C 1-4烷基或卤代C 1-4烷基。
在一些实施方案中，Y为氢、F、Cl、Br、羟基、氰基、硝基、氨基、羧基、C 1-4烷基、C 2-4烯基、C 2-4炔基、卤代C 1-4烷基、卤代C 2-4烯基、卤代C 2-4炔基、C 6-10芳基、C 6-10芳基-C 1-4烷基-、卤代C 6-10芳基或卤代C 6-10芳基-C 1-4烷基-。
在另一些实施方案中，R 1和R 2各自独立地为氢、-CH 3、-CH 2CH 3、-CH 2CH 2CH 3、-CH(CH 3) 2、环丙基、环丁基、环戊基、环己基、苄基、4-氟苄基或4-氰基苄基。
在另一些实施方案中，R 1、R 2和与之相连接的氮原子一起形成以下子结构式：
Figure PCTCN2018086508-appb-000006
在另一些实施方案中，Y为氢、F、Cl、Br、羟基、氰基、硝基、氨基、羧基、-CH 3、-CHF 2、-CH 2F、-CF 3、-CH 2CH 3、-CH 2CH 2F、-CH 2CHF 2、-CH 2CH 2CH 3、-CH(CH 3) 2、-C(CH 3) 3、苯基、2-氟苯基、3-氟苯基或4-氟苯基。
在一些实施方案中，L 1和L 2各自独立地为-(CR 3R 4) n-；
其中，R 3和R 4各自独立地为氢、F、Cl、Br、I、氨基、羟基、氰基、硝基、C 1-4烷基、卤代C 1-4烷基、氨基取代的C 1-4烷基、羟基取代的C 1-4烷基、氰基取代的C 1-4烷基或硝基取代的C 1-4烷基；
其中，n为0、1、2、3、4或5。
还在另一些实施方案中，R 3、R 4可以与相连接的碳原子形成C＝O。
在另一些实施方案中，L 1和L 2各自独立地为-(CR 3R 4) n-或-(CR 11R 22) m-O-；
R 11和R 22各自独立地为氢、C 1-4烷基或卤代C 1-4烷基；
m为0、1、2、3或4；
其中，R 3、R 4和n具有本发明所述的含义。
还在另一些实施方案中，L 1和L 2各自独立地为-(CR 3R 4) n-或-(CR 33R 44) o-NR n-；
R 33和R 44各自独立地为氢、C 1-4烷基或卤代C 1-4烷基；
o为0、1、2、3或4；
R n为氢或C 1-4烷基；
其中，R 3、R 4和n具有本发明所述的含义。
还在另一些实施方案中，L 1和L 2各自独立地为-(CR 3R 4) n-或-(CR 55R 66) p-S(O) q-；
R 55和R 66各自独立地为氢、C 1-4烷基或卤代C 1-4烷基；
p为0、1、2、3或4；
q为0、1或2；
其中，R 3、R 4和n具有本发明所述的含义。
在一些实施方案中，n≥2时，相邻碳上的两个R 3与相邻的两个碳原子可以一起形成C 3-6环烷基或C 6-10芳基。
还在一些实施方案中，m≥2时，相邻碳上的两个R 11与相邻的两个碳原子可以一起形成C 3-6环烷基或C 6-10芳基。
在另一些实施方案中，o≥2时，相邻碳上的两个R 33与相邻的两个碳原子可以一起形成C 3-6环烷基或C 6-10芳基。
还在另一些实施方案中，p≥2时，相邻碳上的两个R 55与相邻的两个碳原子可以一起形成C 3-6环烷基或C 6-10芳基。
在一些实施方案中，
Figure PCTCN2018086508-appb-000007
为C 3-6环烷基、C 2-5杂环基、C 6-10芳基或5-10元杂芳基；
其中，
Figure PCTCN2018086508-appb-000008
任选地被1、2、3或4个选自R 6的取代基所取代；
R 6为氢、F、Cl、Br、I、氨基、羟基、氰基、硝基、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烷氧基-(C＝O)-或C 1-4烷基-(C＝O)-O-。
还在一些实施方案中，
Figure PCTCN2018086508-appb-000009
为C 3-6环烷基、C 2-5杂环基、C 6-10芳基或5-6元杂芳基；
其中，
Figure PCTCN2018086508-appb-000010
任选地被1、2、3或4个选自R 6的取代基所取代；
R 6为氢、F、Cl、Br、I、氨基、羟基、氰基、硝基、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烷氧基-(C＝O)-或C 1-4烷基-(C＝O)-O-。
在另一些实施方案中，
Figure PCTCN2018086508-appb-000011
为以下子结构式：
Figure PCTCN2018086508-appb-000012
其中，R 7为氢或C 1-4烷基；
X 1、X 2、X 3、X 4、X 5和X 6各自独立地为N或CR 8；
R 8为氢、F、Cl、Br、I、C 1-4烷基、卤代C 1-4烷基或C 1-4烷氧基-(C＝O)-。
还在另一些实施方案中，
Figure PCTCN2018086508-appb-000013
为以下子结构式：
Figure PCTCN2018086508-appb-000014
Figure PCTCN2018086508-appb-000015
在一些实施方案中，
Figure PCTCN2018086508-appb-000016
为以下子结构式：
Figure PCTCN2018086508-appb-000017
还在一些实施方案中，本发明涉及一种化合物，其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、氮氧化物及盐：
Figure PCTCN2018086508-appb-000018
Figure PCTCN2018086508-appb-000019
Figure PCTCN2018086508-appb-000020
Figure PCTCN2018086508-appb-000021
Figure PCTCN2018086508-appb-000022
Figure PCTCN2018086508-appb-000023
一方面，本发明涉及一种组合物，其包含本发明所述的一种或多种化合物。
在一些实施方案中，本发明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。
另一方面，本发明涉及一种包含本发明化合物的组合物在植物病害防治中的应用。
前面所述内容只概述了本发明的某些方面，但并不限于这些方面及其他方面的内容将在下面更加具体完整的描述。
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，本文所使用的冠词“一”、“一个(种)”和“所述”旨在包括“至少一个”或“一个或多个”。因此，本文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。
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。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)，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。
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“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“环烷基烷基”表示烷基基团被一个或多个环烷基基团所取代，其中烷基基团和环烷基基团具有如本发明所述的含义。
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“杂环基烷基”是指烷基基团被一个或多个杂环基基团所取代，其中烷基基团和杂环基基团具有如本发明所述的含义。
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“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“芳基烷基”表示烷基基团被一个或多个芳基基团所取代，如苄基。
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，吲哚基(如2-吲哚基)，3,4-二氢异喹啉-2(1H)-基，6,7-二氢噻吩[3,2-c]并吡啶-5(4H)-基等等。
术语“杂芳基烷基”是指烷基基团被一个或多个杂芳基基团所取代。
术语“烷氧基烷基”是指烷基基团被一个或多个烷氧基基团所取代。
术语“烷基氨基”是指氨基基团被一个或两个烷基基团所取代。
术语“卤代烷基”，是指烷基基团被一个或多个卤素所取代。
术语“卤代烯基”是指烯基基团被一个或多个卤素所取代。
术语“卤代炔基”是指炔基基团被一个或多个卤素所取代。
术语“卤代芳基”是指芳基基团被一个或多个卤素所取代。
术语“卤代芳基烷基”是指芳基烷基基团被一个或多个卤素所取代。
术语“卤代烷氧基”是指烷氧基基团被一个或多个卤素所取代。
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)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)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即制剂中的杀菌剂活性成分，通常还包括农药学上可接受的表面活性剂和/或载体。
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。
根据本发明的杀菌剂组合物，该杀菌剂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剂组合物所制备的制剂，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。
本发明的杀菌剂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。
本发明的杀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。
本发明的杀菌剂组合物，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。
本发明的组合物还可与其它具有杀菌、杀虫或除草活性的化合物混合使用，也可与杀线虫剂、杀螨剂、杀节肢动物剂、安全剂、植物生长调节剂、肥料或土壤调节剂等混合使用。
一般合成过程
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，其中取代基的定义如(I)所示。下面的合成方案和实施例1-11用于进一步举例说明本发明的内容。
下面简写词的使用贯穿本发明：
CDCl 3 氘代氯仿；DMF N,N-二甲基甲酰胺；g 克；mg 毫克；mol 摩尔；mmol 毫摩尔；L 升；mL 毫升。
合成方案
合成方案1
Figure PCTCN2018086508-appb-000024
式(I)所示的化合物可以通过合成方案1所公开的方法合成，其中R 1、R 2、Y、L 1、L 2和环A具有本发明所述的含义。式(a)化合物在酸性条件下与氯气反应得到式(b)化合物；式(b)化合物在碱性条件下与式(c)化合物反应得到式(d)化合物；式(d)化合物在碱性条件下与式(e)化合物反应得到式(I)化合物。
合成方案2
Figure PCTCN2018086508-appb-000025
式(I)所示的化合物还可以通过合成方案2所公开的方法合成，其中R 1、R 2、Y、L 1、L 2和环A具有 本发明所述的含义。式(f)化合物在碱性条件与式(c)化合物反应得到式(I)化合物。
实施例
中间体：1-(N,N-二甲基磺酰基)-1H-1,2,4-三唑-3-磺酰氯的合成
Figure PCTCN2018086508-appb-000026
第一步：1,2-二(1H-1,2,4-三唑-3-基)二硫醚的合成
将3-巯基-1,2,4-三氮唑(101.0g,1.00mol)溶于二氯甲烷(300mL)中，加入吡啶(79.0g,1.00mol)，在0℃下搅拌，缓慢滴加苯磺酰氯(88.30g,0.25mol)，2小时滴加完毕后，室温下搅拌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：95.2％。
MS(ES-API,pos.ion)m/z:201.1[M+1] +。
第二步：3,3'-二硫基双(N,N-二甲基-1H-1,2,4-三唑-1-磺酰胺)的合成
氮气保护下，将1,2-二(1H-1,2,4-三唑-3-基)二硫醚(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℃下搅拌混合后，缓慢滴入N,N-二甲胺基磺酰氯(93.34g,0.65mol)，2小时滴加完毕后继续反应6小时。将反应液缓慢倒入到水中，搅拌1小时，过滤，固体风干，得到白色粉末107.2g，产率：86.3％。
MS(ES-API,pos.ion)m/z:415.0[M+1] +。
第三步：1-(N,N-二甲基磺酰基)-1H-1,2,4-三唑-3-磺酰氯的合成
将3,3'-二硫基双(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(300mL)中，加入水(300mL)，冷却至0℃，加入乙酸(100mL)，控制温度在10℃到25℃，搅拌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：87.8％。
MS(ES-API,pos.ion)m/z:274.8[M+1] +。
中间体：2-溴-4,5,6,7-四氢噻吩并[3,2-c]吡啶的合成
Figure PCTCN2018086508-appb-000027
将4,5,6,7-四氢噻吩并[3,2-c]吡啶(3.00g,21.6mmol)加到250mL单口烧瓶内，然后加入二氯甲烷(80mL)，冷却到-5℃，搅拌10分钟，然后通过恒压滴液漏斗将含有N-溴代丁二酰亚胺(3.89g,21.6mmol)的二氯甲烷(20mL)悬浮液慢慢滴入到反应液中，1小时滴完后，继续在-5℃温度下搅拌12小时，用旋转蒸发仪减压蒸馏除去溶剂，得到黄色固体粉末4.46g，收率：95.1％。
MS(ES-API,pos.ion)m/z:217.9[M+1] +。
中间体：2-氯-4,5,6,7-四氢噻吩并[3,2-c]吡啶的合成
Figure PCTCN2018086508-appb-000028
将4,5,6,7-四氢噻吩并[3,2-c]吡啶(3.00g,21.6mmol)加到250mL单口烧瓶内，然后加入二氯甲烷(80mL)，冷却到-5℃，搅拌10分钟，然后通过恒压滴液漏斗将含有N-氯代丁二酰亚胺(2.88g,21.6mmol)的二氯甲烷(20mL)悬浮液慢慢滴入到反应液中，1小时滴完后，继续在-5℃温度下搅拌12小时，用旋转蒸发仪减压蒸馏除去溶剂，得到黄色固体粉末3.51g，收率：93.8％。
MS(ES-API,pos.ion)m/z:174.0[M+1] +。
中间体：2-(叔丁基)-4,5,6,7-四氢噻吩并[3,2-c]吡啶的合成
Figure PCTCN2018086508-appb-000029
将4,5,6,7-四氢噻吩并[3,2-c]吡啶(3.00g,21.6mmol)加到250mL单口烧瓶内，然后加入叔丁醇(3.70g,50.0mmol)，搅拌10分钟，然后通过恒压滴液漏斗将50％稀硫酸(20mL)滴入到反应液中，0.5小时滴完后，加热到50℃搅拌1小时。冷却至25℃，反应物用氢氧化钠溶液调节pH＝10，乙酸乙酯萃取(50mL)，静置分液，有机相用水(30mL)洗涤三次，用旋转蒸发仪减压蒸馏除去溶剂，得到黄色固体粉末3.50g，收率：82.7％。
MS(ES-API,pos.ion)m/z:196.1[M+1] +。
实施例1：3-((3,4-二氢异喹啉-2(1H)-基)磺酰基)-N,N-二甲基-1H-1,2,4-三唑-1-磺酰胺的合成
Figure PCTCN2018086508-appb-000030
第一步：1H-1,2,4-三唑-3-磺酰氯的合成
在室温下，将3-巯基-1,2,4,-三唑(12.0g,0.12mol)溶于盐酸溶液中(2N,0.12L)，将混合物降至0℃，通入氯气反应40分钟，0℃下静置30分钟，过滤，得到白色固体，冰水洗涤(500mL x 3)，得到白色固体14.5g，收率：72.5％。
第二步：2-((1H-1,2,4-三唑-3-基)磺酰基)-1,2,3,4-四氢异喹啉的合成
将1,2,3,4-四氢异喹啉(1.33g,9.98mmol)和三乙胺(1.5g,14.82mmol)溶于四氢呋喃中(5mL)，室 温下搅拌30分钟后，缓慢滴入1H-1,2,4-三唑-3-磺酰氯(1.67g,9.96mmol)的四氢呋喃溶液(5mL)，滴加完毕后，室温搅拌10小时。过滤，减压浓缩滤液，剩余物中加入稀盐酸(0.5N,10mL)，搅拌30分钟，过滤，滤饼用石油醚洗涤(50mL x 3)，得到白色固体2.1g，收率：79.5％。
第三步：3-((3,4-二氢异喹啉-2(1H)-基)磺酰基)-N,N-二甲基-1H-1,2,4-三唑-1-磺酰胺的合成
将2-((1H-1,2,4-三唑-3-基)磺酰基)-1,2,3,4-四氢异喹啉(0.53g,2.00mmol)溶于吡啶中(20mL)，室温下搅拌30分钟后，缓慢滴入二甲胺基磺酰氯(0.86g,5.99mmol)，滴加完成后，室温搅拌24小时。减压浓缩除去吡啶，饱和碳酸氢钠溶液(10mL)调节pH＝7，乙酸乙酯萃取(50mL x 3)，无水硫酸钠干燥，过滤，减压浓缩滤液，得到黄色固体，用石油醚/乙酸乙酯混合溶液溶解固体[石油醚/乙酸乙酯(v/v)＝5/1,200mL]，过滤，减压浓缩滤液，得到白色粉末0.21g，收率：56.4％。
MS(ES-API,pos.ion)m/z:372.0[M+1] +；
1H NMR(400MHz,CDCl 3)δ(ppm):8.7(s,1H),7.2～7.1(m,4H),4.6(s,2H),3.8(m,2H),3.1(m,2H),2.83(s,6H)。
实施例2：3-((6,7-二氢噻吩[3,2-c]并吡啶-5(4H)-基)磺酰基)-N,N-二甲基-1H-1,2,4-三唑-1-磺酰胺的合成
Figure PCTCN2018086508-appb-000031
第一步：5-((1H-1,2,4-三唑-3-基)磺酰基)-4,5,6,7-四氢噻吩[3,2-c]并吡啶的合成
将4,5,6,7-四氢噻吩[3,2-c]并吡啶(1.39g,10.0mmol)和三乙胺(1.5g,15.0mmol)溶于四氢呋喃中(5mL)，室温下搅拌30分钟后，缓慢滴入1H-1,2,4-三唑-3-磺酰氯(1.67g,10.0mmol)的四氢呋喃溶液(5mL)，滴加完成后，室温搅拌10小时。过滤，减压浓缩滤液，剩余物中加入稀盐酸(0.5N,10mL)，搅拌30分钟，过滤，滤饼用石油醚洗涤(50mL x 3)，得到白色固体2.23g，收率：82.6％。
第二步：3-((6,7-二氢噻吩[3,2-c]并吡啶-5(4H)-基)磺酰基)-N,N-二甲基-1H-1,2,4-三唑-1-磺酰胺的合成
将5-((1H-1,2,4-三唑-3-基)磺酰基)-4,5,6,7-四氢噻吩[3,2-c]并吡啶(0.81g,3.0mmol)溶于吡啶中(10mL)，室温下搅拌30分钟后，缓慢滴入二甲胺基磺酰氯(0.47g,3.3mmol)，滴加完成后，室温搅拌24小时。减压浓缩除去吡啶，饱和碳酸氢钠溶液(10mL)调节pH＝7，乙酸乙酯萃取(50mL x 3)，无水硫酸钠干燥，过滤，减压浓缩滤液，得到黄色固体，用石油醚/乙酸乙酯混合溶液溶解固体[石油醚/乙酸乙酯(v/v)＝5/1,200mL]，过滤，减压浓缩滤液，得到白色粉末0.91g，收率：80.4％。
MS(ES-API,pos.ion)m/z:378.0[M+1] +；
1H NMR(400MHz,CDCl 3)δ(ppm):9.4(s,1H),7.3(d,1H),6.9(d,1H),4.4(s,2H),3.7(t,2H),3.0(t,2H),2.90(s,6H)。
实施例3：3-((3,4-二氢喹啉-1(2H)-基)磺酰基)-N,N-二甲基-1H-1,2,4-三唑-1-磺酰胺的合成
Figure PCTCN2018086508-appb-000032
在氮气保护下，将1,2,3,4-四氢喹啉(0.66g,5.0mmol)，吡啶(0.48g,6.0mmol))和四氢呋喃(10mL)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(1.38g,5.0mmol)的四氢呋喃(10mL)溶液，滴加完毕后室温反应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)＝2/1)，得到白色固体1.27g，产率：69.4％。
MS(ES-API,pos.ion)m/z:372.1[M+1] +；
1H NMR(400MHz,CDCl 3)δ(ppm):8.71(s,1H),7.31-7.16(m,4H),4.24(t,2H),3.69(t,2H),2.91(s,6H),2.02(m,2H)。
按照实施例3的制备方法，使用不同的物料与中间体1-(N,N-二甲胺基磺酰基)-1H-1,2,4-三唑-3-磺酰氯进行反应，即可得到表1中的目标化合物。
表1
Figure PCTCN2018086508-appb-000033
Figure PCTCN2018086508-appb-000034
Figure PCTCN2018086508-appb-000035
活性测试
在以下试验例中，发明人以本发明的部分化合物为例，检测了本发明化合物对有害真菌的防治功效。
试验例1
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下对4个试验靶标的杀菌活性。
1)黄瓜霜霉病菌测试(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)黄瓜白粉病菌测试(Sphaerotheca fuliginea)
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。
3)黄瓜灰霉病菌(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。
4)水稻纹枯病菌(Rhizoctonia solani)
选择两叶一心、长势一致的盆栽玉米苗，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。
试验结果：试验结果如表2-5所示。
表2 本发明化合物在200mg/L剂量下对黄瓜霜霉病的防效(％)
实施例编号 防治效果(％)
实施例1 100
实施例2 100
实施例3 100
实施例4 100
实施例5 100
实施例6 98
实施例7 100
实施例8 100
实施例9 100
实施例10 100
表3 本发明化合物在100mg/L剂量下对黄瓜霜霉病的防效(％)
实施例编号 防治效果(％)
实施例2 100
实施例4 85
实施例5 100
实施例6 100
实施例7 80
实施例8 100
表4 本发明化合物在50mg/L剂量下对黄瓜霜霉病的防效(％)
实施例编号 防治效果(％)
实施例2 80
实施例5 80
实施例6 80
实施例8 100
表5 本发明化合物在25mg/L剂量下对黄瓜霜霉病的防效(％)
实施例编号 防治效果(％)
实施例8 100
氰霜唑 20
吲唑磺菌胺 85
试验结果表明，本发明化合物在不同剂量下对黄瓜霜霉病菌均具有良好的防效，并且在低剂量下对黄瓜霜霉病菌显示出更优的防治效果，例如实施例8在25mg/L剂量下对黄瓜霜霉病的防效为100％，而氰霜唑和吲唑磺菌胺对黄瓜霜霉病的防效分别为20％和85％。另外本发明化合物对水稻纹枯病菌、黄瓜灰霉病菌、和黄瓜白粉病菌也具有一定防治效果。
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 (11)

  1. 一种化合物，其为如式(I)所示的化合物或式(I)所示化合物的立体异构体、氮氧化物及盐：
    Figure PCTCN2018086508-appb-100001
    其中，
    R 1和R 2各自独立地为氢、烷基、烯基、炔基、环烷基、杂环基、芳基、杂芳基、环烷基烷基、杂环基烷基、芳基烷基或杂芳基烷基；
    或R 1、R 2和与之相连接的氮原子一起形成杂环基或杂芳基；
    其中，由R 1、R 2和与之相连接的氮原子一起形成的杂环基或杂芳基任选地被一个或多个选自R 5的取代基所取代；
    Y为氢、卤素、羟基、氰基、硝基、氨基、羧基、烷基、烯基、炔基、卤代烷基、卤代烯基、卤代炔基、芳基、芳基烷基、卤代芳基或卤代芳基烷基；
    L 1和L 2各自独立地为-(CR 3R 4) n-、-(CR 11R 22) m-O-、-(CR 33R 44) o-NR n-或-(CR 55R 66) p-S(O) q-；
    其中，R 3和R 4各自独立地为氢、卤素、氨基、羟基、氰基、硝基、烷基、烯基、炔基、卤代烷基、氨基取代的烷基、羟基取代的烷基、氰基取代的烷基或硝基取代的烷基；
    或R 3、R 4可以与相连接的碳原子形成C＝O；
    R 11、R 22、R 33、R 44、R 55和R 66各自独立地为氢、烷基或卤代烷基；
    R n为氢或烷基；
    其中，n为0、1、2、3、4或5；
    m、o和p各自独立地为0、1、2、3或4；
    q为0、1或2；
    或i)n≥2时，相邻碳上的两个R 3与相邻的两个碳原子可以一起形成环烷基、杂环基、芳基或杂芳基；或ii)m≥2时，相邻碳上的两个R 11与相邻的两个碳原子可以一起形成环烷基、杂环基、芳基或杂芳基；或iii)o≥2时，相邻碳上的两个R 33与相邻的两个碳原子可以一起形成环烷基、杂环基、芳基或杂芳基；或iv)p≥2时，相邻碳上的两个R 55与相邻的两个碳原子可以一起形成环烷基、杂环基、芳基或杂芳基；
    Figure PCTCN2018086508-appb-100002
    为环烷基、杂环基、芳基或杂芳基；
    其中，
    Figure PCTCN2018086508-appb-100003
    任选地被1、2、3或4个选自R 6的取代基所取代；
    其中，R 5和R 6各自独立地为氢、卤素、羟基、氰基、硝基、氨基、羧基、C 1-6烷基、C 2-6烯基、C 2-6 炔基、卤代C 1-6烷基、卤代C 2-6烯基、卤代C 2-6炔基、C 1-6烷氧基、卤代C 1-6烷氧基、C 1-6烷氧基-(C＝O)-、C 1-6烷氧基-C 1-6烷基-、C 1-6烷基-(C＝O)-O-、C 1-6烷基-(C＝O)-、C 1-6烷基-SO 2-、C 1-6烷基氨基、C 1-6烷基氨基-(C＝O)-、C 1-6烷基氨基-SO 2-、C 3-6环烷基、C 2-6杂环基、C 6-10芳基或C 1-6杂芳基。
  2. 根据权利要求1所述的化合物，其中，
    R 1和R 2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 2-6杂环基、C 6-10芳基、C 1-6杂芳基、C 3-8环烷基-C 1-6烷基-、C 2-6杂环基-C 1-6烷基-、C 6-10芳基-C 1-6烷基-或C 1-6杂芳基-C 1-6烷基-；
    或R 1、R 2和与之相连接的氮原子一起形成C 2-6杂环基或5-12元杂芳基；
    其中，由R 1、R 2和与之相连接的氮原子一起形成的C 2-6杂环基或5-12元杂芳基任选地被一个或多个选自R 5的取代基所取代；
    Y为氢、F、Cl、Br、I、羟基、氰基、硝基、氨基、羧基、C 1-6烷基、C 2-6烯基、C 2-6炔基、卤代C 1-6烷基、卤代C 2-6烯基、卤代C 2-6炔基、C 6-10芳基、C 6-10芳基-C 1-6烷基-、卤代C 6-10芳基或卤代C 6-10芳基-C 1-6烷基-；
    L 1和L 2各自独立地为-(CR 3R 4) n-、-(CR 11R 22) m-O-、-(CR 33R 44) o-NR n-或-(CR 55R 66) p-S(O) q-；
    其中，R 3和R 4各自独立地为氢、F、Cl、Br、I、氨基、羟基、氰基、硝基、C 1-6烷基、C 2-6烯基、C 2-6炔基、卤代C 1-6烷基、氨基取代的C 1-6烷基、羟基取代的C 1-6烷基、氰基取代的C 1-6烷基或硝基取代的C 1-6烷基；
    或R 3、R 4可以与相连接的碳原子形成C＝O；
    R 11、R 22、R 33、R 44、R 55和R 66各自独立地为氢、C 1-6烷基或卤代C 1-6烷基；
    R n为氢或C 1-6烷基；
    其中，n为0、1、2、3、4或5；
    m、o和p各自独立地为0、1、2、3或4；
    q为0、1或2；
    或i)n≥2时，相邻碳上的两个R 3与相邻的两个碳原子可以一起形成C 3-6环烷基、C 2-6杂环基、C 6-10芳基或5-10元杂芳基；或ii)m≥2时，相邻碳上的两个R 11与相邻的两个碳原子可以一起形成C 3-6环烷基、C 2-6杂环基、C 6-10芳基或5-10元杂芳基；或iii)o≥2时，相邻碳上的两个R 33与相邻的两个碳原子可以一起形成C 3-6环烷基、C 2-6杂环基、C 6-10芳基或5-10元杂芳基；或iv)p≥2时，相邻碳上的两个R 55与相邻的两个碳原子可以一起形成C 3-6环烷基、C 2-6杂环基、C 6-10芳基或5-10元杂芳基；
    Figure PCTCN2018086508-appb-100004
    为C 3-8环烷基、C 2-6杂环基、C 6-10芳基或5-12元杂芳基；
    其中，
    Figure PCTCN2018086508-appb-100005
    任选地被1、2、3或4个选自R 6的取代基所取代；
    其中，R 5和R 6各自独立地为氢、F、Cl、Br、I、羟基、氰基、硝基、氨基、羧基、C 1-4烷基、C 2-4烯基、C 2-4炔基、卤代C 1-4烷基、卤代C 2-4烯基、卤代C 2-4炔基、C 1-4烷氧基、卤代C 1-4烷氧基、C 1-4烷氧基-(C＝O)-、C 1-4烷氧基-C 1-3烷基-、C 1-4烷基-(C＝O)-O-、C 1-4烷基-(C＝O)-、C 1-4烷基-SO 2-、C 1-4烷基氨基、C 1-4烷基氨基-(C＝O)-、C 1-4烷基氨基-SO 2-、C 3-6环烷基、C 2-6杂环基、C 6-10芳基或C 1-4杂芳基。
  3. 根据权利要求1或2所述的化合物，其中，
    R 1和R 2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 2-6杂环基、C 6-10芳基、C 1-5杂芳基、C 3-6环烷基-C 1-4烷基-、C 2-5杂环基-C 1-4烷基-、C 6-10芳基-C 1-4烷基-或C 1-5杂芳基-C 1-4烷基-；
    或R 1、R 2和与之相连接的氮原子一起形成C 2-5杂环基或5-10元杂芳基；
    其中，R 1、R 2和与之相连接的氮原子一起形成的C 2-5杂环基或5-10元杂芳基任选地被一个或多个选自R 5的取代基所取代；
    Y为氢、F、Cl、Br、羟基、氰基、硝基、氨基、羧基、C 1-4烷基、C 2-4烯基、C 2-4炔基、卤代C 1-4烷基、卤代C 2-4烯基、卤代C 2-4炔基、C 6-10芳基、C 6-10芳基-C 1-4烷基-、卤代C 6-10芳基或卤代C 6-10芳基-C 1-4烷基-；
    R 5为氢、F、Cl、Br、羟基、氰基、硝基、氨基、羧基、C 1-4烷基或卤代C 1-4烷基。
  4. 根据权利3所述的化合物，其中，
    R 1和R 2各自独立地为氢、-CH 3、-CH 2CH 3、-CH 2CH 2CH 3、-CH(CH 3) 2、环丙基、环丁基、环戊基、环己基、苄基、4-氟苄基或4-氰基苄基；
    或R 1、R 2和与之相连接的氮原子一起形成以下子结构式：
    Figure PCTCN2018086508-appb-100006
    Y为氢、F、Cl、Br、羟基、氰基、硝基、氨基、羧基、-CH 3、-CHF 2、-CH 2F、-CF 3、-CH 2CH 3、-CH 2CH 2F、-CH 2CHF 2、-CH 2CH 2CH 3、-CH(CH 3) 2、-C(CH 3) 3、苯基、2-氟苯基、3-氟苯基或4-氟苯基。
  5. 根据权利要求1或2所述的化合物，其中，
    L 1和L 2各自独立地为-(CR 3R 4) n-、-(CR 11R 22) m-O-、-(CR 33R 44) o-NR n-或-(CR 55R 66) p-S(O) q-；
    其中，R 3和R 4各自独立地为氢、F、Cl、Br、I、氨基、羟基、氰基、硝基、C 1-4烷基、卤代C 1-4烷基、氨基取代的C 1-4烷基、羟基取代的C 1-4烷基、氰基取代的C 1-4烷基或硝基取代的C 1-4烷基；
    或R 3、R 4可以与相连接的碳原子形成C＝O；
    R 11、R 22、R 33、R 44、R 55和R 66各自独立地为氢、C 1-4烷基或卤代C 1-4烷基；
    R n为氢或C 1-4烷基；
    其中，n为0、1、2、3、4或5；
    m、o和p各自独立地为0、1、2、3或4；
    q为0、1或2；
    或i)n≥2时，相邻碳上的两个R 3与相邻的两个碳原子可以一起形成C 3-6环烷基或C 6-10芳基；或ii)m≥2时，相邻碳上的两个R 11与相邻的两个碳原子可以一起形成C 3-6环烷基或C 6-10芳基；或iii)o≥2时，相邻碳上的两个R 33与相邻的两个碳原子可以一起形成C 3-6环烷基或C 6-10芳基；或iv)p≥2时，相邻碳上的两个R 55与相邻的两个碳原子可以一起形成C 3-6环烷基或C 6-10芳基；
    Figure PCTCN2018086508-appb-100007
    为C 3-6环烷基、C 2-5杂环基、C 6-10芳基或5-10元杂芳基；
    其中，
    Figure PCTCN2018086508-appb-100008
    任选地被1、2、3或4个选自R 6的取代基所取代；
    R 6为氢、F、Cl、Br、I、氨基、羟基、氰基、硝基、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烷氧基-(C＝O)-或C 1-4烷基-(C＝O)-O-。
  6. 根据权利要求5所述的化合物，其中，
    Figure PCTCN2018086508-appb-100009
    为以下子结构式：
    Figure PCTCN2018086508-appb-100010
    其中，R 7为氢或C 1-4烷基；
    X 1、X 2、X 3、X 4、X 5和X 6各自独立地为N或CR 8；
    R 8为氢、F、Cl、Br、I、C 1-4烷基、卤代C 1-4烷基或C 1-4烷氧基-(C＝O)-。
  7. 根据权利要求6所述的化合物，其中，
    Figure PCTCN2018086508-appb-100011
    为以下子结构式：
    Figure PCTCN2018086508-appb-100012
    Figure PCTCN2018086508-appb-100013
  8. 根据权利要求1所述的化合物，其中，
    Figure PCTCN2018086508-appb-100014
    为以下子结构式：
    Figure PCTCN2018086508-appb-100015
  9. 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、氮氧化物及盐：
    Figure PCTCN2018086508-appb-100016
    Figure PCTCN2018086508-appb-100017
    Figure PCTCN2018086508-appb-100018
    Figure PCTCN2018086508-appb-100019
    Figure PCTCN2018086508-appb-100020
    Figure PCTCN2018086508-appb-100021
  10. 一种组合物，包含权利要求1-9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载体。
  11. 权利要求1-9任意一项所述的化合物或权利要求10所述的组合物在植物病害防治中的应用。
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