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WO2022127564A1 - Composés de pyridine biphényle contenant de l'isoxazoline, leur procédé de préparation et leur utilisation - Google Patents

Composés de pyridine biphényle contenant de l'isoxazoline, leur procédé de préparation et leur utilisation Download PDF

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WO2022127564A1
WO2022127564A1 PCT/CN2021/133602 CN2021133602W WO2022127564A1 WO 2022127564 A1 WO2022127564 A1 WO 2022127564A1 CN 2021133602 W CN2021133602 W CN 2021133602W WO 2022127564 A1 WO2022127564 A1 WO 2022127564A1
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alkyl
hydrogen
formula
independently selected
different
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Chinese (zh)
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唐剑峰
迟会伟
赵宝修
吴建挺
袁雪
赵士胜
刘立龙
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SHANDONG UNITED PESTICIDE INDUSTRY Co Ltd
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SHANDONG UNITED PESTICIDE INDUSTRY Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
    • C07D413/10—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings linked by a carbon chain containing aromatic rings
    • 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
    • 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
    • A01N43/80—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 five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,2
    • 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
    • A01P13/00—Herbicides; Algicides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D261/00—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings
    • C07D261/02—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D261/00—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings
    • C07D261/02—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings
    • C07D261/06—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings having two or more double bonds between ring members or between ring members and non-ring members
    • C07D261/08—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings having two or more double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
    • C07D413/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing three or more hetero rings

Definitions

  • the invention belongs to the technical field of agricultural herbicides, in particular to a pyridine biphenyl compound of isoxazoline and a preparation method and application thereof.
  • Harmful weeds in farmland are the enemy in agricultural production. According to statistics, crops all over the world lose an average of 12% of their output due to weed damage every year. Therefore, weed control is an important link to achieve efficient agriculture. Although there are various types of herbicides on the market, due to the continuous expansion of the market, the increasing resistance of weeds in recent years, and the increasing emphasis on environmental protection, people still need to continuously develop new high-efficiency and safe new varieties of herbicides .
  • Patent document WO2014048827 discloses an isoxazoline-containing compound CK 1 (compound number 1.1.1) as shown below:
  • the present invention provides compounds represented by general formula (I), stereoisomers, racemates, tautomers, isotopic labels, nitrogen oxides, pharmaceutically acceptable salts or esters thereof , a solvate or a solvate of a pharmaceutically acceptable salt,
  • R 1 , R 2 , R 3 , R 4 are the same or different and are independently selected from hydrogen, halogen, C 1 -C 6 alkyl or halogenated C 1 -C 6 alkyl;
  • R 5 , R 6 , R 7 , R 8 are the same or different and are independently selected from hydrogen, halogen, C 1 -C 6 alkyl, halogenated C 1 -C 6 alkyl, C 1 -C 6 alkoxy or halogenated C 1 -C 6 alkoxy;
  • R 9 and R 10 are the same or different, and are independently selected from hydrogen, cyano, C 1 -C 6 alkyl or halogenated C 1 -C 6 alkyl;
  • R 11 and R 12 are the same or different, and are independently selected from hydrogen, cyano, C 1 -C 6 alkyl, halogenated C 1 -C 6 alkyl, COOR 13 or CONR 14 R 15 ;
  • R 13 is selected from hydrogen, C 1 -C 6 alkyl, halogenated C 1 -C 6 alkyl, C 1 -C 3 alkoxy C 1 -C 6 alkyl, C 3 -C 6 alkenyl, C 3 -C 6 alkynyl, unsubstituted or 1-4 Ra substituted C 6 -C 10 aryl C 1 -C 6 alkyl, 5-10 membered heteroaryl C 1 -C 6 alkyl, 3-10 Membered heterocyclyl C 1 -C 6 alkyl; each Ra is the same or different and independently selected from the group consisting of halogen, cyano, nitro, C 1 -C 6 alkyl, halogenated C 1 -C 6 alkyl, C 1 -C 6 alkoxy or halogenated C 1 -C 6 alkoxy;
  • R 14 and R 15 are the same or different and are independently selected from hydrogen, C 1 -C 6 alkyl or C 1 -C 4 alkoxy C 1 -C 6 alkyl.
  • R 1 , R 2 , R 3 , R 4 are the same or different and are independently selected from hydrogen, halogen, C 1 -C 4 alkyl or halogenated C 1 -C 4 alkyl;
  • R 5 , R 6 , R 7 , R 8 are the same or different and are independently selected from hydrogen, halogen, C 1 -C 4 alkyl, halogenated C 1 -C 4 alkyl, C 1 -C 4 alkoxy or halogenated C 1 -C 4 alkoxy;
  • R 9 and R 10 are the same or different and are independently selected from hydrogen, C 1 -C 4 alkyl or halogenated C 1 -C 4 alkyl;
  • R 11 and R 12 are the same or different, and are independently selected from hydrogen, cyano, C 1 -C 6 alkyl, halogenated C 1 -C 6 alkyl, COOR 13 or CONR 14 R 15 ;
  • R 13 is selected from hydrogen, C 1 -C 6 alkyl, halogenated C 1 -C 6 alkyl, C 1 -C 3 alkoxy C 1 -C 3 alkyl, C 3 -C 6 alkenyl, C 3 -C 6 alkynyl, C 6 -C 8 aryl C 1 -C 4 alkyl, unsubstituted or substituted by 1-4 Ra, C 1 -C 4 alkyl, 5-8 membered heteroaryl C 1 -C 4 alkyl, 3-6 Membered heterocyclyl C 1 -C 4 alkyl; each Ra is the same or different and independently selected from the group consisting of halogen, cyano, nitro, C 1 -C 4 alkyl, halogenated C 1 -C 4 alkyl, C 1 -C 4 alkoxy or halogenated C 1 -C 4 alkoxy;
  • R 14 and R 15 are the same or different, and are independently selected from hydrogen, C 1 -C 4 alkyl or C 1 -C 4 alkoxy C 1 -C 6 alkyl.
  • R 1 , R 2 , R 3 , R 4 are the same or different and are independently selected from hydrogen, fluorine, chlorine, bromine, methyl, ethyl, trifluoromethyl or trifluoroethyl;
  • R 5 , R 6 , R 7 , R 8 are the same or different and are independently selected from hydrogen, fluorine, chlorine, bromine, methyl, ethyl, trifluoromethyl, trifluoroethyl, methoxy, ethoxy group, trifluoromethoxy or trifluoroethoxy;
  • R 9 and R 10 are the same or different and are independently selected from hydrogen, C 1 -C 4 alkyl or halogenated C 1 -C 4 alkyl;
  • R 11 and R 12 are the same or different, and are independently selected from hydrogen, cyano, C 1 -C 4 alkyl, halogenated C 1 -C 4 alkyl, COOR 13 or CONR 14 R 15 ;
  • R 13 is selected from hydrogen, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 1 -C 3 alkoxy, C 1 -C 3 alkyl, C 3 -C 6 alkenyl, C 3 -C 6 alkynyl, unsubstituted or benzyl, furylmethyl or tetrahydrofurylmethyl substituted with 1-4 Ra; each Ra is the same or different, independently selected from fluorine, chlorine, cyano, nitro, methyl, ethyl, trifluoromethyl, trifluoroethyl, methoxy, ethoxy, trifluoromethoxy or trifluoroethoxy;
  • R 14 and R 15 are the same or different, and are independently selected from hydrogen, C 1 -C 4 alkyl or C 1 -C 3 alkoxy C 1 -C 3 alkyl.
  • R 1 , R 2 , R 3 , R 4 are the same or different and are independently selected from hydrogen, fluorine, chlorine, bromine, methyl, ethyl, trifluoromethyl or trifluoroethyl;
  • R 5 , R 6 , R 7 , R 8 are the same or different and are independently selected from hydrogen, fluorine, chlorine, bromine, methyl, ethyl, trifluoromethyl, trifluoroethyl, methoxy, ethoxy group, trifluoromethoxy or trifluoroethoxy;
  • R 9 and R 10 are the same or different and are independently selected from hydrogen, C 1 -C 4 alkyl or halogenated C 1 -C 4 alkyl;
  • R 11 and R 12 are the same or different, and are independently selected from hydrogen, cyano, C 1 -C 4 alkyl, halogenated C 1 -C 4 alkyl, COOR 13 or CONR 14 R 15 ;
  • R 13 is selected from hydrogen, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 1 -C 3 alkoxy, C 1 -C 3 alkyl, C 3 -C 6 alkenyl, C 3 -C 6 alkynyl, benzyl, unsubstituted or substituted with 1-4 Ras, furylmethyl, tetrahydrofurylmethyl or 1,3-dioxolaneethyl; each Ra is the same or different, independently of each other selected from fluorine, chlorine, cyano, nitro, methyl, ethyl, trifluoromethyl, trifluoroethyl, methoxy, ethoxy, trifluoromethoxy or trifluoroethoxy;
  • R 14 and R 15 are the same or different, and are independently selected from hydrogen, C 1 -C 4 alkyl or C 1 -C 3 alkoxy C 1 -C 3 alkyl.
  • R 1 , R 2 , R 3 , R 4 are the same or different and are independently selected from hydrogen, fluorine, chlorine, methyl, ethyl, trifluoromethyl or trifluoroethyl;
  • R 5 , R 6 , R 7 , R 8 are the same or different and are independently selected from hydrogen, fluorine, chlorine, methyl, ethyl, trifluoromethyl, trifluoroethyl, methoxy, ethoxy, trifluoromethoxy or trifluoroethoxy;
  • R 9 and R 10 are the same or different, and are independently selected from hydrogen, methyl, ethyl, propyl, butyl, trifluoromethyl or trifluoroethyl;
  • R 11 , R 12 are the same or different, and are independently selected from hydrogen, cyano, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, COOR 13 or CONR 14 R 15 ;
  • R 13 is selected from hydrogen, C 1 -C 6 alkyl, halogenated C 1 -C 6 alkyl, allyl, propargyl, C 1 -C 3 alkoxy C 1 -C 3 alkyl, unsubstituted or benzyl, furylmethyl or tetrahydrofurylmethyl substituted with 1-4 Ra; each Ra is the same or different and independently selected from the group consisting of fluorine, chlorine, cyano, nitro, methyl, ethyl, trifluoromethyl, trifluoroethyl, methoxy, ethoxy, trifluoromethoxy or trifluoroethoxy;
  • R 14 and R 15 are the same or different, and are independently selected from hydrogen, C 1 -C 4 alkyl or C 1 -C 3 alkoxy C 1 -C 3 alkyl.
  • R 1 , R 2 , R 3 , R 4 are the same or different and are independently selected from hydrogen, fluorine, chlorine, methyl, ethyl, trifluoromethyl or trifluoroethyl;
  • R 5 , R 6 , R 7 , R 8 are the same or different and are independently selected from hydrogen, fluorine, chlorine, methyl, ethyl, trifluoromethyl, trifluoroethyl, methoxy, ethoxy, trifluoromethoxy or trifluoroethoxy;
  • R 9 and R 10 are the same or different, and are independently selected from hydrogen, methyl, ethyl, propyl, butyl, trifluoromethyl or trifluoroethyl;
  • R 11 , R 12 are the same or different, and are independently selected from hydrogen, cyano, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, COOR 13 or CONR 14 R 15 ;
  • R 13 is selected from hydrogen, C 1 -C 6 alkyl, halogenated C 1 -C 6 alkyl, allyl, propargyl, C 1 -C 3 alkoxy C 1 -C 3 alkyl, unsubstituted or benzyl, furylmethyl, tetrahydrofuranylmethyl or 1,3-dioxolaneethyl substituted with 1-4 Ras; each Ra is the same or different and independently selected from fluorine, chlorine, cyano, nitro, methyl, ethyl, trifluoromethyl, trifluoroethyl, methoxy, ethoxy, trifluoromethoxy or trifluoroethoxy;
  • R 14 and R 15 are the same or different, and are independently selected from hydrogen, C 1 -C 4 alkyl or C 1 -C 3 alkoxy C 1 -C 3 alkyl.
  • R 1 , R 2 , R 3 , R 4 are the same or different, and are independently selected from hydrogen, fluorine, chlorine, methyl or trifluoromethyl;
  • R 5 , R 6 , R 7 , R 8 are the same or different and are independently selected from hydrogen, fluorine, chlorine, methyl, trifluoromethyl, methoxy or trifluoromethoxy;
  • R 9 and R 10 are the same or different, and are independently selected from hydrogen, methyl, ethyl, propyl or butyl;
  • R 11 and R 12 are the same or different, and are independently selected from hydrogen, methyl, ethyl or COOR 13 ;
  • R 13 is selected from hydrogen, C 1 -C 4 alkyl, halogenated C 1 -C 4 alkyl, allyl, propargyl, C 1 -C 3 alkoxy C 1 -C 3 alkyl, benzyl , furylmethyl or tetrahydrofurylmethyl.
  • R 1 , R 2 , R 3 , R 4 are the same or different, and are independently selected from hydrogen, fluorine, chlorine, methyl or trifluoromethyl;
  • R 5 , R 6 , R 7 , R 8 are the same or different and are independently selected from hydrogen, fluorine, chlorine, methyl, trifluoromethyl, methoxy or trifluoromethoxy;
  • R 9 and R 10 are the same or different, and are independently selected from hydrogen, methyl, ethyl, propyl or butyl;
  • R 11 and R 12 are the same or different, and are independently selected from hydrogen, methyl, ethyl or COOR 13 ;
  • R 13 is selected from hydrogen, C 1 -C 4 alkyl, halogenated C 1 -C 4 alkyl, allyl, propargyl, C 1 -C 3 alkoxy C 1 -C 3 alkyl, benzyl , furylmethyl, tetrahydrofurylmethyl or 1,3-dioxolaneethyl.
  • R 1 , R 2 , R 3 , R 4 are the same or different and are independently selected from hydrogen, fluorine, chlorine or trifluoromethyl;
  • R 5 , R 6 , R 7 , R 8 are the same or different and are independently selected from hydrogen, fluorine, chlorine, methyl or trifluoromethyl;
  • R 9 and R 10 are the same or different, and are independently selected from hydrogen or methyl;
  • R 11 and R 12 are the same or different, and are independently selected from methyl, ethyl or COOR 13 ;
  • R 13 is selected from hydrogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, trifluoromethyl, trifluoroethyl, allyl, propargyl, methoxy ethyl, ethoxyethyl, benzyl, furylmethyl or tetrahydrofurylmethyl.
  • R 1 , R 2 , R 3 , R 4 are the same or different and are independently selected from hydrogen, fluorine, chlorine or trifluoromethyl;
  • R 5 , R 6 , R 7 , R 8 are the same or different and are independently selected from hydrogen, fluorine, chlorine, methyl or trifluoromethyl;
  • R 9 and R 10 are the same or different, and are independently selected from hydrogen or methyl;
  • R 11 and R 12 are the same or different, and are independently selected from methyl, ethyl or COOR 13 ;
  • R 13 is selected from hydrogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, trifluoromethyl, trifluoroethyl, allyl, propargyl, methoxy ethyl, ethoxyethyl, benzyl, furylmethyl, tetrahydrofurylmethyl or 1,3-dioxolaneethyl.
  • the compound represented by formula (I) has the following structure:
  • the present invention also provides the preparation method of the compound shown in the above formula (I), comprising the following steps:
  • the compound represented by the formula (II) is subjected to a cycloaddition reaction with the compound of the formula (III) to obtain the compound of the formula (I);
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 are as defined above.
  • L is selected from leaving groups such as Cl or Br.
  • the reaction may be carried out in the presence of a base, which may be an organic base such as selected from pyridine, triethylamine, 4-(dimethylamino)pyridine (DMAP) or diisopropyl At least one of ethylamine (DIEA);
  • a base which may be an organic base such as selected from pyridine, triethylamine, 4-(dimethylamino)pyridine (DMAP) or diisopropyl At least one of ethylamine (DIEA);
  • the reaction is carried out in a solvent selected from the group consisting of N,N-dimethylacetamide, N,N-dimethylformamide, tetrahydrofuran, dioxane or toluene at least one;
  • the reaction temperature may be -5-120°C, such as 0-50°C, such as 15-50°C.
  • the cycloaddition reaction can be carried out in a one-pot reaction to prepare the dipole precursor II or in the presence of the isolated dipole precursor II.
  • reaction can be referred to literature such as 1,3 dipolar Cycloaddition Chemistry, Padwa (ed.), Wiley, New York, 1984; Heterocycles. 1990, 30, 719; J. Agric. Food. Chem.
  • Optically active isoxazolines can be obtained by chiral HPLC of suitable precursors or final products, and can also be obtained by enantioselective reactions, such as by enzymatic ester or amide cleavage reactions or by obtained using chiral auxiliaries, as described by J. Org. Chem. 1988, 53, 2468.
  • formula (I) in which R 12 is COOH can be prepared by a hydrolysis reaction known to those skilled in the art compounds shown.
  • R 12 COOR 13 , and R 13 is not H
  • the hydrolysis reaction can be carried out in the presence of a base selected from at least one of sodium hydroxide, potassium hydroxide or lithium hydroxide; or an acid such as trichloromethane in dichloromethane Fluoroacetic acid treatment;
  • the temperature of the hydrolysis reaction may be 0-150°C, eg, 15-80°C.
  • the formula (I) in which R 12 is COOR 13 can be prepared through the first step of halogenation reaction and then through the second step of esterification reaction compound of;
  • the halogenating agent in the first step of halogenation reaction is selected from thionyl chloride, oxalyl chloride or thionyl chloride;
  • the temperature of the first-step halogenation reaction may be 0-100°C, such as 0-50°C, such as 0-30°C;
  • the second-step esterification reaction may be carried out in the presence of a base, which may be selected from organic bases or inorganic bases, such as pyridine, triethylamine, 4-(dimethylamino)pyridine (DMAP) ), diisopropylethylamine (DIEA), one, two or more of sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, potassium tert-butoxide or sodium hydride.
  • the preferred solvent can be one or both of N,N-dimethylacetamide, N,N-dimethylformamide, dioxane, toluene, dichloromethane or 1,2-dichloroethane species or more;
  • the temperature of the second-step esterification reaction may be 0-120°C, for example, 0-50°C, such as 15-30°C.
  • the carboxylic acid esterification reaction may be carried out in the presence of a condensing agent selected from the group consisting of N,N'-dicyclohexylcarbodiimide (DCC), N,N'-di Isopropylcarbodiimide (DIC), 1-hydroxybenzotriazole (HOBT), 2-(7-azabenzotriazole)-N,N,N',N'-tetramethylurea at least one of hexafluorophosphate (HATU) or benzotriazol-1-yl-oxytripyrrolidinophosphorus hexafluorophosphate (PyBOP);
  • a condensing agent selected from the group consisting of N,N'-dicyclohexylcarbodiimide (DCC), N,N'-di Isopropylcarbodiimide (DIC), 1-hydroxybenzotriazole (HOBT), 2-(7-azabenzotriazole)-N,N,N',N'
  • the carboxylic acid esterification reaction may be carried out in the presence of a base, which may be an inorganic base such as selected from pyridine, triethylamine, 4-(dimethylamino)pyridine (DMAP) or At least one of diisopropylethylamine (DIEA);
  • a base which may be an inorganic base such as selected from pyridine, triethylamine, 4-(dimethylamino)pyridine (DMAP) or At least one of diisopropylethylamine (DIEA);
  • the carboxylic acid esterification reaction is carried out in a solvent selected from the group consisting of N,N-dimethylacetamide, N,N-dimethylformamide, tetrahydrofuran, 2-methyl At least one of tetrahydrofuran, dioxane, acetonitrile, toluene, dichloromethane or 1,2-dichloroethane;
  • the temperature of the carboxylic acid esterification reaction may be -5-120°C, for example, 0-50°C, such as 15-30°C.
  • R 12 in the compound of formula (I) when R 12 in the compound of formula (I) is COOH, the compound of formula (I) wherein R 12 is CONR 14 R 15 can be prepared through the first step of halogenation reaction and then through the second step of condensation reaction. compound shown;
  • the halogenating agent in the first step of halogenation reaction is selected from thionyl chloride, oxalyl chloride or thionyl chloride;
  • the temperature of the first-step halogenation reaction may be 0-100°C, such as 0-50°C, such as 0-30°C;
  • the second-step condensation reaction may be carried out in the presence of a base, which may be selected from organic or inorganic bases, such as pyridine, triethylamine, 4-(dimethylamino)pyridine (DMAP) , diisopropylethylamine (DIEA), one, two or more of sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, potassium tert-butoxide or sodium hydride.
  • the preferred solvent can be one or both of N,N-dimethylacetamide, N,N-dimethylformamide, dioxane, toluene, dichloromethane or 1,2-dichloroethane species or more;
  • the temperature of the condensation reaction in the second step may be 0-120°C, for example, 0-50°C, such as 15-30°C.
  • carboxylic acid and amine can be directly obtained by condensation reaction.
  • the condensation reaction may be carried out in the presence of a condensing agent selected from N,N'-dicyclohexylcarbodiimide (DCC), N,N'-diisopropyl Carbodiimide (DIC), 1-Hydroxybenzotriazole (HOBT), 2-(7-azabenzotriazole)-N,N,N',N'-tetramethylurea hexafluorophosphoric acid at least one of benzotriazol-1-yl-oxytripyrrolidinophosphorus hexafluorophosphate (HATU) or hexafluorophosphate (PyBOP);
  • DCC N,N'-dicyclohexylcarbodiimide
  • DIC N,N'-diisopropyl Carbodiimide
  • HOBT 1-Hydroxybenzotriazole
  • the condensation reaction may be carried out in the presence of a base, which may be an inorganic base such as selected from pyridine, triethylamine, 4-(dimethylamino)pyridine (DMAP) or diisopropyl At least one of diethylamine (DIEA);
  • a base which may be an inorganic base such as selected from pyridine, triethylamine, 4-(dimethylamino)pyridine (DMAP) or diisopropyl At least one of diethylamine (DIEA);
  • the condensation reaction is carried out in a solvent selected from the group consisting of N,N-dimethylacetamide, N,N-dimethylformamide, tetrahydrofuran, 2-methyltetrahydrofuran, dimethy At least one of oxane, acetonitrile, toluene, dichloromethane or 1,2-dichloroethane;
  • the temperature of the condensation reaction may be -5-120°C, such as 0-50°C, such as 15-30°C.
  • the compound represented by formula (III) can be purchased as a commercial product or prepared by a method known to those skilled in the art.
  • the preparation method of the compound represented by formula (II) comprises the following steps:
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , L are as defined above;
  • L 1 is selected from a leaving group such as Cl, Br, I or F ;
  • L is selected from leaving groups such as Cl or Br.
  • step (1) can be carried out in the presence of a catalyst selected from tetrakis(triphenylphosphine)palladium, palladium acetate or bis(triphenylphosphine)palladium dichloride;
  • a catalyst selected from tetrakis(triphenylphosphine)palladium, palladium acetate or bis(triphenylphosphine)palladium dichloride;
  • step (1) can be carried out in the presence of a base selected from one or both of sodium carbonate, potassium carbonate, pyridine, triethylamine or 4-(dimethylamino)pyridine or more; the solvent is selected from one, two or more of toluene, tetrahydrofuran, N,N-dimethylformamide or water; the temperature of the reaction can be 20-150°C, for example 50 ⁇ 80°C.
  • a base selected from one or both of sodium carbonate, potassium carbonate, pyridine, triethylamine or 4-(dimethylamino)pyridine or more
  • the solvent is selected from one, two or more of toluene, tetrahydrofuran, N,N-dimethylformamide or water
  • the temperature of the reaction can be 20-150°C, for example 50 ⁇ 80°C.
  • step (2) can be carried out in the presence of a base selected from one, two or more of organic bases such as triethylamine, sodium acetate, or inorganic bases such as sodium bicarbonate
  • a base selected from one, two or more of organic bases such as triethylamine, sodium acetate, or inorganic bases such as sodium bicarbonate
  • the reaction solvent is selected from alcohol solvents such as methanol, ethanol, or water or a mixture thereof; the reaction temperature can be 0-100°C, preferably 15-30°C.
  • step (3) may be performed in the presence of a halogenating agent, which may be N-chlorosuccinimide (NCS) or N-bromosuccinimide (NBS);
  • a halogenating agent which may be N-chlorosuccinimide (NCS) or N-bromosuccinimide (NBS);
  • NCS N-chlorosuccinimide
  • step (3) can be carried out in the presence of a base selected from at least one of triethylamine, pyridine, sodium bicarbonate or sodium carbonate; the temperature of the reaction can be 0 ⁇ 100°C, for example, 15 to 30°C.
  • the boronic acid represented by formula (VII) and the halide represented by formula (VI) can be purchased as commercial products or prepared by methods known to those skilled in the art.
  • the reaction can be referred to in WO2014048827 or WO2006090234.
  • the compounds of formula (I) and their starting materials can be prepared herein according to the appropriate reaction conditions and the choice of starting materials in each case, for example, in a one-step reaction by replacing only one substituent with another substituent according to the invention, or it can be carried out in the same Various substituents are replaced in the reaction steps with other substituents according to the present invention.
  • reaction mixture can be worked up in the customary manner, eg by mixing with water, separating the phases and, if appropriate, purifying the crude product by chromatography, eg on alumina or silica gel.
  • the pharmaceutically acceptable salts of the compounds of formula (I) of the present invention can be prepared by known methods. Salts of compounds of formula (I) are obtained, for example, by treatment with a suitable base. Its preparation method is as follows: react the compound of formula (I) with alkali such as sodium hydroxide, potassium hydroxide, calcium hydroxide, zinc hydroxide, etc. in solvents such as water, ether or toluene, and can easily obtain formula (I) A pharmaceutically acceptable salt of the compound.
  • alkali such as sodium hydroxide, potassium hydroxide, calcium hydroxide, zinc hydroxide, etc.
  • solvents such as water, ether or toluene
  • the above preparation method can obtain a mixture of isomers of the compound of formula (I). If pure isomers are required, conventional methods such as crystallization or chromatography can be used for separation.
  • the present invention also provides a pesticide composition, such as a herbicidal composition, comprising as an active ingredient the compound represented by formula (I), its stereoisomer, racemate, tautomer, isotopic label, One, two or more of nitrogen oxides, pharmaceutically acceptable salts or esters, solvates, or solvates of pharmaceutically acceptable salts.
  • a pesticide composition such as a herbicidal composition, comprising as an active ingredient the compound represented by formula (I), its stereoisomer, racemate, tautomer, isotopic label, One, two or more of nitrogen oxides, pharmaceutically acceptable salts or esters, solvates, or solvates of pharmaceutically acceptable salts.
  • the weight percent content of the active ingredient in the composition is 0.1-99.9%, for example, 0.5-99%.
  • one, two or more of agricultural and/or forestry and/or hygienically acceptable carriers are also included in the composition.
  • the composition may be administered in the form of a formulation.
  • the compound of formula (I) can be dissolved or dispersed as an active ingredient in a carrier or formulated so as to be easier to disperse when used as a herbicide.
  • the formulations include but are not limited to the following forms: granules, wettable powders, oil suspensions, water suspensions, water emulsions, water preparations, emulsifiable concentrates or microcapsules and the like.
  • a liquid or solid carrier may also be added to the composition.
  • a surfactant may also be added to the composition.
  • the present invention also provides one, two or more of the compounds represented by formula (I), their stereoisomers, racemates, tautomers, nitrogen oxides or their pharmaceutically acceptable salts
  • pesticides such as herbicides. It has excellent herbicidal efficacy against a wide range of economically important monocotyledonous and dicotyledonous annual harmful plants.
  • the active ingredient also acts effectively on perennial weeds that sprout from rhizomes, rhizomes and other perennial organs and are difficult to control.
  • the present invention also provides compounds represented by formula (I), its stereoisomers, racemates, tautomers, isotopic labels, nitrogen oxides, pharmaceutically acceptable salts or esters, solvates or Use of one, two or more of the solvates of the pharmaceutically acceptable salts in the preparation of pesticides, eg, herbicides.
  • the effective amount is 10 grams to 1000 grams per hectare, preferably the effective amount is 20 grams to 500 grams per hectare.
  • the present invention also provides a method for controlling unwanted plants, comprising adding an effective amount of the compound represented by formula (I), its stereoisomers, racemates, tautomers, isotopic labels, nitrogen oxides drug, a pharmaceutically acceptable salt or ester, a solvate or a solvate of a pharmaceutically acceptable salt, or applying the composition to an unwanted plant (e.g. a harmful plant such as a monocot or dicot grasses or unwanted crop plants), seeds or tubers or other reproductive parts of a desired plant (e.g. grains, seeds or vegetative propagules such as tubers or shoot parts with buds) or growing areas of a desired plant (eg cultivation area).
  • an unwanted plant e.g. a harmful plant such as a monocot or dicot grasses or unwanted crop plants
  • seeds or tubers or other reproductive parts of a desired plant e.g. grains, seeds or vegetative propagules such as tubers or shoot parts with buds
  • growing areas of a desired plant eg cultivation area
  • the compounds according to the invention can be applied, for example, before sowing (if appropriate also by incorporation into the soil), before or after emergence.
  • Some representative specific examples of monocotyledonous and dicotyledonous weed flora that can be controlled by the compounds of the present invention are as follows, but the enumeration is not intended to be limited to a particular species.
  • the method can control Aegilops, Agropyron, Agrostis, Alopecurus, Apera, Avena ), Brachiaria, Bromus, Cenchrus, Commelina, Cynodon, Cyperus, Cynodon Dactyloctenium, Digitaria, Echinochloa, Eleocharis, Eleusine, Eragrostis, Eriochloa, Festuca , Fimbristylis, Imperata, Ischaemum, Heteranthera, Leptochloa, Lolium, Monochoria ), Panicum, Paspalum, Phalaris, Phleum, Poa, Rottboellia, Sagittaria, Scirpus, Setaria, Sorghum and Sphenoclea.
  • the method can control species such as Abutilon, Amaranthus, Ambrosia, Anoda, Anthemis, Aphanes, Artemisia Genus Artemisia, Atriplex, Bellis, Bidens, Capsella, Carduus, Cassia, Centaurea ( Centaurea, Chenopodium, Cirsium, Convolvulus, Datura, Desmodium, Emex, Geranium (Erodium), Erysimum, Euphorbia, Galeopsis, Galinsoga, Galium, Geranium, Hibiscus, Ipomoea, Kochia, Lamium, Lepidium, Lindernia, Matricaria, Mint Mentha, Mercurialis, Mullugo, Myosotis, Papaver, Pharbitis, Plantago, Polygonum, Portulaca Portulaca, Ranunculus, Raphanus, Rorippa, Rotala, Rumex, Salsola, Senecio
  • the active compound combinations according to the invention are applied to the soil surface pre-emergence, the emergence of weed seedlings is completely prevented, or the weeds grow until they reach the cotyledon stage, but then their growth stops and finally dies out completely in three to four weeks .
  • the active compounds are applied to the green parts of the plants post-emergence, the growth stops after the treatment, the harmful plants remain in the growth phase at the point of application, or die completely after a certain time, so that the harmful plants can be eliminated very early and in a lasting manner. Crop plants compete with harmful weeds.
  • the compounds of the present invention have excellent herbicidal activity against monocotyledonous and dicotyledonous weeds, but have negligible, if any, damage to many desirable plants or economically important crops, depending on Structures of specific compounds of the invention and their application rates.
  • Desirable plants or economically important crops herein such as dicotyledonous crops of the following genera: Arachis, Beta, Brassica, Cucumis, Cucurbita ( Cucurbita, Helianthus, Daucus, Glycine, Gossypium, Ipomoea, Lactuca, Linum, Lycopersicon , Miscanthus, Nicotiana, Phaseolus, Pisum, Solanum, Vicia; or monocotyledonous crops of the following genera: Allium , Ananas, Asparagus, Avena, Hordeum, Oryza, Panicum, Saccharum, Secale , Sorghum, Triticale, Triticum and Zea.
  • the compounds of the present invention are very suitable for selectively controlling the growth of unwanted plants in crop plant species, such as agriculturally useful plants or ornamental plants.
  • the compounds of the present invention (depending on their specific chemical structure and the application rates used) also have excellent growth regulating properties on crop plants. They intervene in the plant's own metabolism in a regulatory role and can thus be used to influence plant composition in a targeted manner and facilitate harvesting, for example by inducing dehydration and stunted growth. In addition, they are generally also suitable for general control and inhibition of undesired vegetative growth without killing the plants. Inhibition of vegetative growth plays an important role in many monocotyledonous and dicotyledonous crops by, for example, reducing or completely preventing lodging.
  • transgenic plants are characterized by particularly advantageous properties, such as resistance to certain pesticides, especially certain herbicides, resistance to plant diseases or pathogens of plant diseases, such as certain insects or Microorganisms such as fungi, bacteria or viruses.
  • Other specific properties relate, for example, to the quantity, quality, storability, composition and specific composition of the harvested material.
  • transgenic plants are known that have increased starch content or altered starch quality, or that contain a different fatty acid composition in the harvest.
  • Other specific characteristics may be resistance to abiotic stress factors such as heat, cold, drought, salinity and UV radiation.
  • the compounds of formula (I) according to the invention or their salts are preferably used in transgenic crops of economically important useful plants and ornamental plants such as cereals such as wheat, barley, rye, oats, millet , rice, cassava and corn, or other crops beet, cotton, soybean, rape, potato, tomato, pea and other vegetables.
  • the compounds of the formula (I) according to the invention or their salts are preferably used as herbicides in crops of useful plants which are resistant to the phytotoxic effects of the herbicides or in a recombinant manner to the phytotoxic effects of the herbicides Resistant.
  • nucleic acid molecules that permit mutagenesis or sequence modification by DNA sequence recombination can be added to plasmids.
  • base exchange to remove subsequences or add natural or synthetic sequences can be performed by standard methods.
  • Linkers or linkers can be added to ligate DNA fragments to each other, see, e.g., Sambrook et al., 1989, Molecular Cloning, A Laboratory Manual, 2nd ed., Cold Spring Harbor Laboratory Press, Cold Spring Harbor, NY; or Winnacker "Gene und Klone” [Genes and Clones], VCH Weinheim, 2nd ed., 1996.
  • the above-mentioned genes can be successfully produced with reduced Product active plant cells.
  • a DNA molecule containing all of the coding sequence of the gene product, including any flanking sequences that may be present, can be used first, and a DNA molecule containing only part of the coding sequence, for which parts need to be of sufficient length to cause intracellular reactions righteous effect. It is also possible to use DNA sequences that have a high degree of homology to the coding sequences of gene products that are not identical thereto.
  • the synthesized protein can be located in any compartment of the plant cell.
  • the coding region can for example be linked to a DNA sequence that ensures its location in a specific compartment.
  • Such sequences are known to those skilled in the art (see, eg, Braun et al., EMBO J. 11 (1992), 3219-3227; Wolter et al., Proc. Natl. Acad. Sci. USA 85 (1988) , 846-850; Sonnewald et al., Plant J. 1 (1991), 95-106).
  • Nucleic acid molecules can also be expressed in organelles of plant cells.
  • Transgenic plant cells can be regenerated by known techniques to yield whole plants.
  • transgenic plants can be plants of any desired plant species, ie monocotyledonous and dicotyledonous plants.
  • the compounds of formula (I) according to the invention or their salts can preferably be used in transgenic crops that are tolerant to the compounds used or made tolerant.
  • the compounds of formula (I) of the present invention or their salts can also be used in transgenic crops resistant to growth substances such as dicamba; or inhibition of plant essential enzymes such as acetolactate synthase (ALS), Herbicides against EPSP synthase, glutamine synthase (GS) or hydroxyphenylpyruvate dioxygenase (HPPD); selected from sulfonylurea, glyphosate, glufosinate or benzoylisoxazole and Herbicides with similar active compounds.
  • ALS acetolactate synthase
  • EPSP Epoxyphenylpyruvate dioxygenase
  • HPPD hydroxyphenylpyruvate dioxygenase
  • the present invention also provides - if appropriate, in crops of useful plants, preferably on non-arable land or in cultivated crops - such a method for controlling unwanted plants, wherein a compound of (I), its Stereoisomers, racemates, tautomers, isotopic labels, nitrogen oxides, pharmaceutically acceptable salts or solvates thereof are applied to harmful plants, plant parts or plant seeds thereof, or to a cultivated area.
  • a compound of (I) its Stereoisomers, racemates, tautomers, isotopic labels, nitrogen oxides, pharmaceutically acceptable salts or solvates thereof are applied to harmful plants, plant parts or plant seeds thereof, or to a cultivated area.
  • the present invention also provides the compound represented by formula (I), its stereoisomers, racemates, tautomers, isotope labels, nitrogen oxides, pharmaceutically acceptable salts or solvates thereof for use For the control - if appropriate, in crops of beneficial plants, preferably on non-arable land or in cultivated crops - the use of harmful plants.
  • the compounds of formula (I) can advantageously be used to protect important crops in cultivated and non-cultivated land, as well as the environment frequented by humans, from harmful weeds.
  • the amount of the compound of formula (I) to be used to obtain the desired effect will vary depending on factors such as the compound used, the crop to be pre-protected, the type of noxious weeds, the degree of infection, the climatic conditions, the method of application and the dosage form employed.
  • composition or composition ingredients described herein should be selected in accordance with the physical properties of the active ingredient, the mode of application and environmental factors such as soil type, humidity and temperature.
  • Useful dosage forms include liquids such as solutions (including emulsifiable concentrates), suspensions, emulsions (including microemulsions and/or suspending agents), and the like, which may optionally be viscous to form a gel.
  • Useful dosage forms also include solids such as powders, powders, granules, tablets, pills, films, and the like, which may be water-dispersible ("wettable") or water-soluble.
  • the active ingredient can be microencapsulated and then made into a suspension or solid dosage form; in addition, the entire dosage form of the active ingredient can also be encapsulated. Encapsulation can control or delay the release of the active ingredient.
  • Sprayable formulations can be diluted in a suitable medium using spray volumes of about one hundred to several hundred liters per hectare. Compositions in high concentrations are mainly used as intermediates for further processing.
  • Typical solid diluents are described in Watkins et al., Handbook of Insecticide Dust Diluents and Carriers, 2nd Ed., Dorland Books, Caldwell, New Jersey. Typical liquid diluents are described in Marsden, Solvents Guide, 2nd Ed., Interscience, New York, 1950. McCutcheon's Detergents and Emulsifiers Annual, Allured Publ. Corp., Ridgewood, New Jersey, and Sisely and Wood, Encyclopedia of Surface Active Agents, Chemical Publ. Co., Inc., New York, 1964, Lists Surfactants and recommended apps. All dosage forms may contain small amounts of additives to reduce foaming, coalescence, corrosion, microbial growth, etc., or thickeners to increase viscosity.
  • Surfactants include, for example, polyethoxylated alcohols, polyethoxylated alkylphenols, polyethoxylated sorbitan fatty acid esters, sulfonated dialkyl succinates, alkyl sulfates, Alkylbenzenesulfonates, organosilanes, N,N-dialkyltaurates, lignosulfonates, aldehyde condensates for naphthalenesulfonates, polycarboxylates and polyoxyethylene/polyoxypropylene intercalation segmented copolymer.
  • Solid diluents include, for example, clays such as bentonite, montmorillonite, attapulgite and kaolin, starch, sugar, silica, talc, diatomaceous earth, urea, calcium carbonate, sodium carbonate and bicarbonate, and sulfuric acid Sodium
  • liquid diluents include, for example, water, N,N-dimethylformamide, dimethyl sulfone, N-alkylpyrrolidones, ethylene glycol, polypropylene glycol, paraffin, alkylbenzenes, alkylnaphthalenes , olive oil, castor oil, linseed oil, tung oil, sesame oil, corn oil, peanut oil, cottonseed oil, soybean oil, rapeseed oil and cocoa butter, fatty acid esters, ketones such as cyclohexanone, 2-heptanone, iso phorone and 4-hydroxy-4-methyl-2-pentanone, and alcohols such as
  • Solutions can be prepared by simply mixing the ingredients. Powders and fines can be prepared by mixing and milling, usually in a hammer or liquid energy mill. Suspensions are usually prepared by wet milling; see, for example, U.S. 3060,084, granules and pellets are prepared by spraying the active substance onto a It is prepared on a prepared granular carrier or by a granulation technique. See Browning, "Agglomeration", Chemical Engineering, December 4, 1967, pp147-48, Perry's Chemical Engineer's Handbook, 4TH Ed., McGraw-Hill, New York, 1963, Pages 8-57 and following, and WO 91/ 13546. Preparation of pills as described in U.S.
  • one, two or more other fungicides, insecticides, acaricides, herbicides may be added to the herbicidal composition of the present invention.
  • Growth regulators or fertilizers, etc. thereby producing additional advantages and effects.
  • the compounds of formula (I) described in the present invention have good activity against various harmful weeds in agriculture or other fields. Moreover, these compounds can achieve good control effects at very low doses, so they can be used in the preparation of herbicides.
  • halogen refers to fluorine, chlorine, bromine and iodine.
  • C1- C6 alkyl refers to straight and branched chain alkyl groups having 1 , 2, 3, 4, 5 or 6 carbon atoms.
  • the alkyl group is, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, 2-methylbutyl, 1-methylbutyl, 1-ethylpropyl, 1,2-dimethylpropyl, neopentyl, 1,1-dimethylpropyl, 4-methylpentyl, 3-methylpentyl , 2-methylpentyl, 1-methylpentyl, 2-ethylbutyl, 1-ethylbutyl, 3,3-dimethylbutyl, 2,2-dimethylbutyl, 1,1-dimethylbutyl, 2,3-dimethylbutyl, 1,3-dimethylbutyl or 1,
  • C2 - C6 alkenyl is to be understood to mean preferably a straight-chain or branched monovalent hydrocarbon radical comprising one or more double bonds and having 2, 3, 4, 5 or 6 carbon atoms, for example, Has 2 or 3 carbon atoms (ie, C2 - C3 alkenyl). It is understood that where the alkenyl group contains more than one double bond, the double bonds may be separated from each other or conjugated.
  • the alkenyl group is, for example, vinyl, allyl, (E)-2-methylvinyl, (Z)-2-methylvinyl, (E)-but-2-enyl, (Z)- But-2-enyl, (E)-but-1-enyl, (Z)-but-1-enyl, pent-4-enyl, (E)-pent-3-enyl, (Z) -Pent-3-enyl, (E)-pent-2-enyl, (Z)-pent-2-enyl, (E)-pent-1-enyl, (Z)-pent-1-ene base, hex-5-enyl, (E)-hex-4-enyl, (Z)-hex-4-enyl, (E)-hex-3-enyl, (Z)-hex-3- Alkenyl, (E)-hex-2-enyl, (Z)-hex-2-enyl, (E)-hex-1-eny
  • C2 - C6alkynyl is to be understood as preferably denoting a linear or branched monovalent hydrocarbon group comprising one or more triple bonds and having 2, 3, 4, 5 or 6 carbon atoms, eg , having 2 or 3 carbon atoms ("C2 - C3alkynyl").
  • the alkynyl group is, for example, ethynyl, prop-1-ynyl, prop-2-ynyl, but-1-ynyl, but-2-ynyl, but-3-ynyl, pent-1-ynyl , pent-2-ynyl, pent-3-ynyl, pent-4-ynyl, hex-1-ynyl, hex-2-ynyl, hex-3-ynyl, hex-4-ynyl, Hex-5-ynyl, 1-methylprop-2-ynyl, 2-methylbut-3-ynyl, 1-methylbut-3-ynyl, 1-methylbut-2-ynyl , 3-methylbut-1-ynyl, 1-ethylprop-2-ynyl, 3-methylpent-4-ynyl, 2-methylpent-4-ynyl, 1-methylpentyl -4-alkynyl, 2-methylpent-3-y
  • heterocyclyl means a saturated or unsaturated non-aromatic ring or ring system containing at least one heteroatom selected from O, S and N.
  • the heterocyclyl group can be attached to the remainder of the molecule through any of the carbon atoms or a nitrogen atom, if present.
  • the heterocyclyl group can include fused or bridged rings as well as spirocyclic rings.
  • the heterocyclic group may include, but is not limited to: 4-membered ring, such as azetidinyl, oxetanyl; 5-membered ring, such as tetrahydrofuranyl, dioxolyl, pyrrole Alkyl, imidazolidinyl, pyrazolidinyl, pyrrolinyl, 1,3-dioxolane; or 6-membered ring, such as tetrahydropyranyl, piperidinyl, morpholinyl, dithi Alkyl, thiomorpholinyl, piperazinyl or trithianyl; or a 7-membered ring such as diazepanyl.
  • 4-membered ring such as azetidinyl, oxetanyl
  • 5-membered ring such as tetrahydrofuranyl, dioxolyl, pyrrole Alkyl, imidazolidinyl, pyr
  • the heterocyclyl group can be benzo-fused.
  • the heterocyclyl group may be bicyclic, such as, but not limited to, a 5,5 membered ring, such as a hexahydrocyclopento[c]pyrrole-2(1H)-yl ring, or a 5,6 membered bicyclic ring, such as a hexahydropyrrole The [1,2-a]pyrazin-2(1H)-yl ring.
  • a heterocyclyl group may be partially unsaturated, i.e.
  • it may contain one or more double bonds such as, but not limited to, dihydrofuranyl, dihydropyranyl, 2,5-dihydro-1H-pyrrolyl, 4H- [1,3,4]thiadiazinyl, 4,5-dihydrooxazolyl or 4H-[1,4]thiazinyl, alternatively, it may be benzo-fused such as but not limited to dihydro isoquinolinyl.
  • C6 - C10 aryl is to be understood as preferably denoting a monovalent aromatic or partially aromatic monocyclic, bicyclic or tricyclic hydrocarbon ring having 6, 7, 8, 9 or 10 carbon atoms, in particular A ring of 6 carbon atoms (“C 6 aryl”), such as phenyl; or biphenyl, or a ring of 9 carbon atoms (“C 9 aryl”), such as indanyl or indenyl , or a ring having 10 carbon atoms (“ C10 aryl”), such as tetralinyl, dihydronaphthyl, or naphthyl, such as fluorenyl.
  • C6 - C10 aryl group When the C6 - C10 aryl group is substituted, it may be monosubstituted or polysubstituted.
  • the substitution site is not limited, for example, it may be ortho-, para- or meta-substitution.
  • heteroaryl is understood to include monovalent monocyclic, bicyclic or tricyclic aromatic ring systems having 5, 6, 7, 8, 9 or 10 ring atoms, especially 5 or 6 or 9 or 10 carbon atoms and it contains 1-5, preferably 1-3 heteroatoms each independently selected from N, O and S and, in addition in each case may be benzo-fused .
  • Heteroaryl also refers to groups in which a heteroaromatic ring is fused to one or more aryl, alicyclic or heterocyclyl rings, wherein the root or point of attachment is on the heteroaromatic ring. Non-limiting examples include furyl, indolyl, isoindolyl, indolyl, indazolyl, purinyl.
  • reaction and purification can be carried out using the manufacturer's instructions for use of the kit, or in a manner well known in the art or as described in this application.
  • the techniques and methods described above can generally be carried out according to conventional methods well known in the art from the descriptions in the various general and more specific documents cited and discussed in this specification.
  • groups and their substituents can be selected by those skilled in the art to provide stable moieties and compounds.
  • substituent When a substituent is described by a conventional formula written from left to right, the substituent also includes the chemically equivalent substituent obtained when the structural formula is written from right to left, so long as it conforms to the valence rules.
  • CH2O which is equivalent to OCH2 , may be attached to the substitution position with an oxygen atom or a methylene carbon atom.
  • the term "pharmaceutically acceptable salts” refers to salts that retain the biological potency of the free acid and free base of the designated compound and are not biologically or otherwise adversely affected.
  • the compounds of the present application also include pharmaceutically acceptable salts, such as sodium salts, potassium salts, calcium salts, zinc salts, and the like which are generally used in the fields of agriculture and horticulture.
  • a pharmaceutically acceptable salt refers to a form in which an acid group in the parent compound is converted into a salt.
  • Pharmaceutically acceptable salts include, but are not limited to, inorganic or organic base salts of acid groups such as carboxylic acid (hydro) groups.
  • the pharmaceutically acceptable salts of the present application can be synthesized from the parent compound by reacting an acidic group in the parent compound with 1-4 equivalents of a base in a solvent system. Suitable salts are listed in Remingtong's Pharmaceutical Sciences, 17th ed ., Mack Publishing Company, Easton, Pa., 1985, p. 1418 and Journal of Pharmaceutical Science, 66, 2 (1977), eg, the sodium salt.
  • stereoisomers refer to isomers that result from different arrangements of atoms in a molecule in space.
  • the compounds of formula (I) contain asymmetric or chiral centers and, therefore, exist in different stereoisomeric forms. All stereostructures of formula (I) are the same as mixtures, including racemic mixtures, as part of the present application.
  • Diastereomeric mixtures can be separated into the individual diastereomers on the basis of their different physicochemical properties by well-known means, for example, resolution of enantiomers can be achieved by interaction with appropriate optically active substances (e.g., chiral isomers).
  • the compounds of formula (I) may exist in different tautomeric forms, all of which are included within the scope of this application. For example, compounds in the form of keto-enols and imine-enamines.
  • Detection wavelength 254nm; flow rate: 0.8mL/min; column temperature: 30°C;
  • the first step reaction Preparation of 2-chloro-4-fluoro-5-(5-(trifluoromethyl)pyridin-2-yl)benzaldehyde: under nitrogen protection, 3.03g (0.015mol) (4- Chloro-2-fluoro-5-formylphenyl)boronic acid, 6.21g (0.045mol) potassium carbonate, 0.52g (0.00045mol) tetrakis (triphenylphosphine) palladium, 60ml tetrahydrofuran, 30ml water were added to the there-necked flask and stirred . To the above mixture was added portionwise 3.27 g (0.018 mol) of 2-chloro-5-(trifluoromethyl)pyridine.
  • the second step reaction preparation of 2-chloro-4-fluoro-5-(5-(trifluoromethyl)pyridin-2-yl)benzaldehyde oxime: at room temperature, 2.27g (0.0075mol) of 2-chloro -4-Fluoro-5-(5-(trifluoromethyl)pyridin-2-yl)benzaldehyde, 0.68g (0.0097mol) hydroxylamine hydrochloride, 0.86g (0.01mol) sodium acetate dissolved in 5ml water and mixed with 20ml tetrahydrofuran in solution. The reaction solution was stirred for 4 hours.
  • the reaction mixture was concentrated, diluted with ethyl acetate and aqueous sodium hydroxide (2M), and the phases were separated. The organic layer was washed with saturated brine and dried over anhydrous sodium sulfate. Suction filtration and drying to obtain 2.22 g of the product with a yield of 93%.
  • reaction solution was cooled to room temperature, 0.68g (0.006mol) of ethyl methacrylate, 0.76g (0.0075mol) of triethylamine in 2ml of N,N-dimethylformamide solution were added to the above mixture, and stirred at room temperature for 5 hours .
  • the reaction mixture was diluted with water and ethyl acetate and the phases were separated.
  • the aqueous phase was extracted with ethyl acetate (2*20ml) and the organic phases were combined.
  • the organic phase was washed twice with water and once with saturated brine. Dry over anhydrous sodium sulfate, filter, and concentrate the filtrate under reduced pressure.
  • the residue was subjected to column chromatography (eluent: ethyl acetate: petroleum ether (1:9) to obtain 1.76 g of the product with a yield of 82%.
  • the first step reaction preparation of 2-chloro-5-(3-chloro-5-(trifluoromethyl)pyridin-2-yl)-4-fluorobenzaldehyde: under nitrogen protection, 3.03g (0.015mol ) (4-chloro-2-fluoro-5-formylphenyl)boronic acid, 6.21g (0.045mol) potassium carbonate, 0.52g (0.00045mol) tetrakis(triphenylphosphine)palladium, 60ml tetrahydrofuran, 30ml water were added to the Stir in a three-necked bottle.
  • the second step reaction preparation of 2-chloro-5-(3-chloro-5-trifluoromethyl)pyridin-2-yl)-4-fluorobenzaldehyde oxime: at room temperature, 2.53g (0.0075mol) of 2-Chloro-5-(3-chloro-5-(trifluoromethyl)pyridin-2-yl)-4-fluorobenzaldehyde, 0.68g (0.0097mol) hydroxylamine hydrochloride, 0.86g (0.01mol) sodium acetate In 5ml water and 20ml tetrahydrofuran mixed solution. The reaction solution was stirred for 4 hours.
  • reaction mixture was concentrated, diluted with ethyl acetate and aqueous sodium hydroxide (2M), and the phases were separated. The organic layer was washed with saturated brine and dried over anhydrous sodium sulfate. Suction filtration and drying to obtain 2.38 g of product with a yield of 90%.
  • reaction solution was cooled to room temperature, 2ml N,N-dimethylformamide solution of 0.60g (0.006mol) methyl methacrylate and 0.76g (0.0075mol) triethylamine was added to the above mixture, and stirred at room temperature for 5 hours .
  • the reaction mixture was diluted with water and ethyl acetate and the phases were separated.
  • the aqueous phase was extracted with ethyl acetate (2*20ml) and the organic phases were combined.
  • the organic phase was washed twice with water and once with saturated brine. Dry over anhydrous sodium sulfate, filter, and concentrate the filtrate under reduced pressure.
  • the residue was subjected to column chromatography (eluent: ethyl acetate: petroleum ether (1:9) to obtain 1.92 g of the product with a yield of 85%.
  • the reaction mixture was diluted with water and ethyl acetate and the phases were separated.
  • the aqueous phase was extracted with ethyl acetate (2*20ml) and the organic phases were combined.
  • the organic phase was washed twice with water and once with saturated brine. Dry over anhydrous sodium sulfate, filter, and concentrate the filtrate under reduced pressure.
  • the residue was subjected to column chromatography (eluent: ethyl acetate: petroleum ether (1:9) to obtain 1.83 g of the product with a yield of 79%.
  • the second step reaction 2-(1,3-dioxolan-2-yl)ethyl 3-(2-chloro-5-(3-chloro-5-(trifluoromethyl)pyridin-2-yl) )-4-fluorophenyl)-5-methyl-4,5-dihydroisoxazole-5-carboxylate preparation: 1.05 g (0.0023 mol) of 3-(2-chloro- 5-(3-Chloro-5-(trifluoromethyl)pyridin-2-yl)-4-fluorophenyl)-5-methyl-4,5-dihydroisoxazole-5-acid chloride, 0.46g (0.0046 mol) triethylamine, 0.29 g (0.0025 mol) 2-(1,3-dioxolan-2-yl) ethane-1-ol were dissolved in 15 ml of dichloromethane successively.
  • the present invention has also synthesized the following compounds with reference to the methods in the above examples:
  • the present embodiment uses the compound obtained in the above embodiment to prepare the wettable powder, and specifically adopts the raw material composition of the following proportions to prepare:
  • Compound 3 50.0%, dodecylphenol polyethoxy glycol ether 4.0%, sodium lignosulfonate 6.0%, sodium aluminosilicate 8.0%, montmorillonite (calcined) 32.0%.
  • This embodiment uses the compound obtained in the above embodiment to prepare granules, and specifically adopts the raw material composition of the following proportions to prepare:
  • Compound 121 20.0% other components are sodium lauryl sulfate 2.0%, calcium lignosulfonate 6.0%, potassium chloride 10.0%, polydimethylsiloxane 1.0%, soluble starch is filled to 100%.
  • This embodiment uses the compound obtained in the above embodiment to prepare extruded pellets, and specifically adopts the raw material composition of the following proportions to prepare:
  • the present embodiment uses the compound obtained in the above embodiment to prepare emulsifiable concentrate, and specifically adopts the raw material composition of the following proportions to prepare:
  • the present embodiment uses the compound obtained in the above embodiment to prepare the aqueous suspension, and specifically adopts the raw material composition of the following proportions to prepare:
  • the herbicidal activity of the compounds of the present invention is shown in the following greenhouse tests:
  • the quantitative crop seeds were sown in paper cups with nutrient soil with a diameter of 7cm, covered with soil 1cm after sowing, and cultivated in a greenhouse after suppression and drenching. (2-3 leaf stage of rice), according to the experimental design dose, use a crawler-type crop sprayer (designed and produced by British Engineer Research Ltd.) to spray the stem and leaves (spray pressure 1.95kg/cm2, spray volume 50ml/m2, crawler speed 1.48km/h), the test was repeated three times. After the medicinal liquid was naturally air-dried, it was placed in a greenhouse for management according to conventional methods, the growth and development of the tested crops were observed for each treatment, and the safety of the tested chemicals on the tested crops was regularly inspected visually. Safety grading standard: 0 means no damage to the crop, 100 means the crop is completely killed or severely inhibited. The test results are shown in Table 6.

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Abstract

La présente invention relève du domaine technique des herbicides, et concerne en particulier des composés de pyridine biphényle contenant de l'isoxazoline, leur procédé de préparation et leur utilisation. La présente invention concerne en particulier des composés tels que représentés par la formule (I) suivante ou des sels de ces composés. Les composés représentés par la formule (I) présentent une bonne activité contre diverses mauvaises herbes nuisibles en agriculture ou dans d'autres domaines. En outre, ces composés peuvent obtenir de bons effets de lutte à des doses très faibles, et peuvent par conséquent être utilisés pour préparer des herbicides et ont de meilleures perspectives d'application.
PCT/CN2021/133602 2020-12-17 2021-11-26 Composés de pyridine biphényle contenant de l'isoxazoline, leur procédé de préparation et leur utilisation Ceased WO2022127564A1 (fr)

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WO2024008049A1 (fr) * 2022-07-04 2024-01-11 潍坊中农联合化工有限公司 Composition herbicide contenant un composé pyridylphényl isoxazoline et du glyphosate, et son utilisation

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CN115701430A (zh) * 2021-08-02 2023-02-10 沈阳禧沅峰生物科技有限公司 一种含异恶唑啉的苯基吡啶类化合物及其用途
CN117050068A (zh) * 2022-05-13 2023-11-14 青岛清原化合物有限公司 杂环取代的芳香类化合物及其制备方法、除草组合物和应用
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