WO2020124515A1 - 喹啉衍生物及其制备方法和用途 - Google Patents

喹啉衍生物及其制备方法和用途 Download PDF

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Publication number
WO2020124515A1
WO2020124515A1 PCT/CN2018/122505 CN2018122505W WO2020124515A1 WO 2020124515 A1 WO2020124515 A1 WO 2020124515A1 CN 2018122505 W CN2018122505 W CN 2018122505W WO 2020124515 A1 WO2020124515 A1 WO 2020124515A1
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Prior art keywords
alkyl
halogenated
hydrogen
alkynyl
alkoxy
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PCT/CN2018/122505
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English (en)
French (fr)
Inventor
李义涛
张虎
刘鹏飞
刘倩
林健
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东莞市东阳光农药研发有限公司
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Priority to PCT/CN2018/122505 priority Critical patent/WO2020124515A1/zh
Priority to CN201880087384.1A priority patent/CN111670182A/zh
Publication of WO2020124515A1 publication Critical patent/WO2020124515A1/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
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
    • A01N43/42—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings condensed with carbocyclic 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
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
    • C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
    • C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D215/20—Oxygen atoms
    • C07D215/22—Oxygen atoms attached in position 2 or 4
    • C07D215/233—Oxygen atoms attached in position 2 or 4 only one oxygen atom which is attached in position 4
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/06—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms

Definitions

  • the present invention provides a new quinoline derivative and its preparation method, a composition containing these compounds and its application in agriculture.
  • WO9812180, WO9812192, WO2000014069, CN102249996 disclose that quinoline compounds have certain herbicidal activity, however, the compounds of the present invention described in detail below are not described in these documents.
  • the present invention provides a new quinoline compound with excellent herbicidal effect and excellent selectivity between crops and weeds.
  • the present invention provides a compound represented by formula (I) or a stereoisomer, nitrogen oxide, or salt thereof of a compound represented by formula (I):
  • R is hydrogen, alkyl, alkenyl, alkynyl, alkoxyalkyl, alkylaminoalkyl, alkylthioalkyl, haloalkyl, cycloalkyl, heterocyclyl, aryl, heteroaryl, cycloalkane alkyl, heterocyclylalkyl, arylalkyl or heteroaryl alkyl; R is optionally substituted 5 or 6 substituents selected from R x;
  • n 0, 1, 2 or 3;
  • n 1, 2 or 3;
  • R 8 , R 8a , R 9 , R 10 , R 11 , R 12 , R 13 and R 14 are each independently hydrogen, alkyl, alkoxyalkyl, aryl or heteroaryl; R 8 , R 8a , R 9 , R 10 , R 11 , R 12 , R 13 and R 14 are each independently optionally substituted with 1, 2, 3, 4, 5 or 6 substituents selected from R y ;
  • R 2 , R 3 , R 4 , R 5 , R 6 and R 7 are each independently hydrogen, fluorine, chlorine, bromine, iodine, amino, nitro, cyano, hydroxyl, carboxyl, alkyl, alkoxy, Alkylthio or alkylcarbonyl;
  • R 33 is hydrogen, alkyl, alkenyl, alkynyl or cycloalkyl
  • R 44 is hydrogen, cyano, fluorine, chlorine, bromine, iodine, alkyl, alkenyl, alkynyl, alkoxy, alkylthio or cycloalkyl;
  • R x and R y are each independently fluorine, chlorine, bromine, iodine, amino, nitro, cyano, hydroxyl, carboxyl, C 1-8 alkyl, halogenated C 1-8 alkyl, C 2-8 alkene Group, halogenated C 2-8 alkenyl, C 2-8 alkynyl, halogenated C 2-8 alkynyl, C 1-8 alkoxy, halogenated C 1-8 alkoxy, C 1-8 alkane Amino, C 1-8 alkylthio, halogenated C 1-8 alkylamino, halogenated C 1-8 alkylthio, C 6-10 aryl, C 6-10 aryloxy, C 1-9 heteroaryl Radical or C 1-9 heteroaryloxy.
  • the present invention provides a compound represented by formula (IIa) or a stereoisomer, nitrogen oxide, or salt thereof of a compound represented by formula (IIa):
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R have the meanings as described in the present invention.
  • the present invention provides a compound represented by formula (IIb) or a stereoisomer, nitrogen oxide, or salt thereof of a compound represented by formula (IIb):
  • R 22 , R 33 , R 44 and R have the meaning as described in the present invention.
  • the present invention provides a compound represented by formula (IIIa) or a stereoisomer, nitrogen oxide, or salt thereof of a compound represented by formula (IIIa):
  • R 22 , R 33 and R 44 have the meanings as described in the present invention.
  • the present invention provides a compound represented by formula (IIIb) or a stereoisomer, nitrogen oxide, or salt thereof of a compound represented by formula (IIIb):
  • R 22 , R 33 and R 44 have the meanings as described in the present invention.
  • R m , R n , R v , R w and R z are each independently hydrogen, fluorine, chlorine, bromine, iodine, amino, nitro, cyano, hydroxyl, carboxyl, C 1-6 alkyl, halo C 1-6 alkyl, C 2-6 alkenyl, halo C 2-6 alkenyl, C 2-6 alkynyl, halo C 2-6 alkynyl, C 1-6 alkoxy, halo C 1 -6 alkoxy, C 1-6 alkylamino, C 1-6 alkylthio, halogenated C 1-6 alkylamino, halogenated C 1-6 alkylthio, C 6-10 aryl, C 6- 10 aryloxy, C 1-5 heteroaryl or C 1-5 heteroaryloxy.
  • R is hydrogen, C 1-8 alkyl, C 2-8 alkenyl, C 2-8 alkynyl, C 1-8 alkoxy C 1-8 alkyl, C 1-8 alkyl Amino C 1-8 alkyl, C 1-8 alkylthio C 1-8 alkyl, halogenated C 1-8 alkyl, C 3-8 cycloalkyl, C 2-10 heterocyclyl, C 6- 10 aryl, C 1-9 heteroaryl, C 3-8 cycloalkyl C 1-6 alkyl, C 2-10 heterocyclyl C 1-6 alkyl, C 6-10 aryl C 1-6 Alkyl or C 1-9 heteroaryl C 1-6 alkyl; R is optionally substituted with 1, 2, 3, 4, 5 or 6 substituents selected from R x ; wherein each R x has The meaning of the present invention.
  • R is hydrogen, C 1-6 alkyl, C 2-6 alkenyl, C 2-6 alkynyl, C 1-6 alkoxy C 1-6 alkyl, C 1-6 alkyl Amino C 1-6 alkyl, C 1-6 alkylthio C 1-6 alkyl, halogenated C 1-6 alkyl, C 3-8 cycloalkyl, C 2-8 heterocyclyl, C 6- 10 aryl, C 1-9 heteroaryl, C 3-8 cycloalkyl C 1-6 alkyl, C 2-8 heterocyclyl C 1-6 alkyl, C 6-10 aryl C 1-6 Alkyl or C 1-9 heteroaryl C 1-6 alkyl; R is optionally substituted with 1, 2, 3, 4, 5 or 6 substituents selected from R x ; wherein each R x has The meaning of the present invention.
  • R is hydrogen, C 1-4 alkyl, C 2-4 alkenyl, C 2-4 alkynyl, C 1-3 alkoxy C 1-3 alkyl, C 1-3 alkyl Amino C 1-3 alkyl, C 1-3 alkylthio C 1-3 alkyl, halogenated C 1-4 alkyl, C 3-6 cycloalkyl, C 2-6 heterocyclyl, C 6- 10 aryl, C 1-5 heteroaryl, C 3-6 cycloalkyl C 1-3 alkyl, C 2-6 heterocyclyl C 1-4 alkyl, C 6-10 aryl C 1-3 Alkyl or C 1-5 heteroaryl C 1-3 alkyl; R is optionally substituted with 1, 2, 3, 4, 5 or 6 substituents selected from R x ; wherein each R x has The meaning of the present invention.
  • R is C 1-3 alkyl, C 2-3 alkenyl, C 2-3 alkynyl, C 1-3 alkoxy C 1-3 alkyl, halo C 1-3 alkyl Group, phenyl or C 2-4 heterocyclyl C 1-3 alkyl; R is optionally substituted with 1, 2, 3, 4, 5 or 6 substituents selected from R x ; wherein each R x It has the meaning as described in the present invention.
  • each R x is independently fluorine, chlorine, bromine, iodine, amino, nitro, cyano, hydroxy, carboxy, C 1-6 alkyl, halogenated C 1-6 alkyl, C 2 -6 alkenyl, halogenated C 2-6 alkenyl, C 2-6 alkynyl, halogenated C 2-6 alkynyl, C 1-6 alkoxy, halogenated C 1-6 alkoxy, C 1 -6 alkylamino, C 1-6 alkylthio, halogenated C 1-6 alkylamino, halogenated C 1-6 alkylthio, C 6-10 aryl, C 6-10 aryloxy, C 1- 5 Heteroaryl or C 1-5 heteroaryloxy.
  • each R x is independently fluorine, chlorine, bromine, iodine, amino, nitro, cyano, hydroxy, carboxy, C 1-4 alkyl, halo C 1-4 alkyl, C 2 -4 alkenyl, halo C 2-4 alkenyl, C 2-4 alkynyl, halo C 2-4 alkynyl, C 1-4 alkoxy, halo C 1-4 alkoxy, C 1 -4 alkylamino, C 1-4 alkylthio, halogenated C 1-4 alkylamino, halogenated C 1-4 alkylthio, C 6-10 aryl, C 6-10 aryloxy, C 1- 5 Heteroaryl or C 1-5 heteroaryloxy.
  • each R x is independently fluorine, chlorine, bromine, iodine, amino, nitro, cyano, hydroxy, carboxy, methyl, ethyl, n-propyl, isopropyl, difluoromethyl , Trifluoromethyl, methoxy or trifluoromethoxy.
  • R is hydrogen, -CH 3, -CH 2 CH 3 , -CH 2 CH 2 CH 3, -CH (CH 3) 2, -CF 3, -CH 2 CHF 2, -CH 2 CF 3 , -CH 2 OCH 3 , -CH 2 CH 2 OCH 3 or -CH 2 OCH 2 CH 3 ; or R is the following substructure formula:
  • R 2 , R 3 , R 4 , R 5 , R 6 and R 7 are each independently hydrogen, fluorine, chlorine, bromine, iodine, amino, nitro, cyano, hydroxy, carboxy, C 1-6 alkyl, C 1-6 alkoxy, C 1-6 alkylthio or C 1-6 alkylcarbonyl.
  • R 2 , R 3 , R 4 , R 5 , R 6 and R 7 are each independently hydrogen, fluorine, chlorine, bromine, iodine, amino, nitro, cyano, hydroxy, carboxy, C 1-4 alkyl, C 1-4 alkoxy, C 1-4 alkylthio or C 1-4 alkylcarbonyl.
  • R 2 , R 3 , R 4 , R 5 , R 6 and R 7 are each independently hydrogen, fluorine, chlorine, bromine, iodine, amino, nitro, cyano, hydroxyl, carboxy, methyl Group, ethyl, n-propyl, isopropyl or methoxy.
  • n 0, 1, 2 or 3;
  • n 1, 2 or 3;
  • R 8 , R 8a , R 9 , R 10 , R 11 , R 12 , R 13 and R 14 are each independently hydrogen, C 1-6 alkyl, C 1-6 alkoxy C 1-6 alkyl , C 6-10 aryl or C 1-9 heteroaryl; R 8 , R 8a , R 9 , R 10 , R 11 , R 12 , R 13 and R 14 are each independently optionally 1, 2, 3 , 4, 5 or 6 substituents selected from R y are substituted; wherein each R y has the meaning as described in the present invention.
  • R 33 is hydrogen, C 1-6 alkyl, C 2-6 alkenyl, C 2-6 alkynyl, or C 3-6 cycloalkyl.
  • R 44 is hydrogen, cyano, fluorine, chlorine, bromine, iodine, C 1-6 alkyl, C 2-6 alkenyl, C 2-6 alkynyl, C 1-6 alkoxy , C 1-6 alkylthio or C 3-6 cycloalkyl.
  • n 0, 1, 2 or 3;
  • n 1, 2 or 3;
  • R 8 and R 8a are each independently hydrogen, C 1-4 alkyl, C 1-4 alkoxy C 1-4 alkyl, phenyl or C 2-3 heteroaryl; R 8 and R 8a are each It is independently optionally substituted with 1, 2, 3, 4, 5 or 6 substituents selected from R y ; wherein each R y has the meaning as described in the present invention.
  • R 8 and R 8a are each independently phenyl or pyrazolyl; R 8 and R 8a are each independently selected by 1, 2, 3, 4, 5, or 6 selected from R y Substituted by a substituent; wherein each R y has the meaning as described in the present invention.
  • R 33 is hydrogen, C 1-4 alkyl, C 2-4 alkenyl, C 2-4 alkynyl, or C 3-6 cycloalkyl.
  • R 44 is hydrogen, cyano, fluorine, chlorine, bromine, iodine, C 1-4 alkyl, C 2-4 alkenyl, C 2-4 alkynyl, C 1-4 alkoxy , C 1-4 alkylthio or C 3-6 cycloalkyl.
  • each R y is independently fluorine, chlorine, bromine, iodine, amino, nitro, cyano, hydroxy, carboxy, C 1-6 alkyl, halogenated C 1-6 alkyl, C 2 -6 alkenyl, halogenated C 2-6 alkenyl, C 2-6 alkynyl, halogenated C 2-6 alkynyl, C 1-6 alkoxy, halogenated C 1-6 alkoxy, C 1 -6 alkylamino, C 1-6 alkylthio, halogenated C 1-6 alkylamino, halogenated C 1-6 alkylthio, C 6-10 aryl, C 6-10 aryloxy, C 1- 5 Heteroaryl or C 1-5 heteroaryloxy.
  • each R y is independently fluorine, chlorine, bromine, iodine, amino, nitro, cyano, hydroxy, carboxy, C 1-4 alkyl, halo C 1-4 alkyl, C 2 -4 alkenyl, halo C 2-4 alkenyl, C 2-4 alkynyl, halo C 2-4 alkynyl, C 1-4 alkoxy, halo C 1-4 alkoxy, C 1 -4 alkylamino, C 1-4 alkylthio, halogenated C 1-4 alkylamino, halogenated C 1-4 alkylthio, C 6-10 aryl, C 6-10 aryloxy, C 1- 5 Heteroaryl or C 1-5 heteroaryloxy.
  • each R y is independently fluorine, chlorine, bromine, iodine, amino, nitro, cyano, hydroxy, carboxyl, methyl, ethyl, n-propyl, isopropyl, difluoromethyl , Trifluoromethyl, methoxy or trifluoromethoxy.
  • R 22 is hydrogen
  • R 33 is hydrogen, methyl, ethyl, n-propyl, or isopropyl.
  • R 44 is hydrogen, cyano, fluorine, chlorine, bromine, iodine, methyl, ethyl, n-propyl, isopropyl, or cyclopropyl.
  • R m , R n , R v , R w and R z are each independently hydrogen, fluorine, chlorine, bromine, iodine, amino, nitro, cyano, hydroxy, carboxy, C 1-4 Alkyl, halogenated C 1-4 alkyl, C 2-4 alkenyl, halogenated C 2-4 alkenyl, C 2-4 alkynyl, halogenated C 2-4 alkynyl, C 1-4 alkoxy Group, halogenated C 1-4 alkoxy, C 1-4 alkylamino, C 1-4 alkylthio, halogenated C 1-4 alkylamino, halogenated C 1-4 alkylthio, C 6-10 Aryl, C 6-10 aryloxy, C 1-5 heteroaryl or C 1-5 heteroaryloxy.
  • R m , R n , R v , R w and R z are each independently hydrogen, fluorine, chlorine, bromine, iodine, amino, nitro, cyano, hydroxyl, carboxyl, methyl, ethyl Group, n-propyl, isopropyl, difluoromethyl, trifluoromethyl, methoxy or trifluoromethoxy.
  • the present invention provides a compound which is a compound having one of the following structures or a stereoisomer, nitrogen oxide, or salt thereof having one of the following structures:
  • the invention provides a composition comprising the compound of the invention, optionally further comprising at least one adjuvant.
  • the invention provides the use of the compounds or compositions of the invention in agriculture.
  • the present invention provides the use of the compounds or compositions of the present invention for controlling unwanted plants.
  • the present invention provides the use of the compounds or compositions of the present invention as herbicides.
  • the present invention provides a method for controlling unwanted plants, characterized in that an effective amount of the compound of the present invention is applied to plants, plant seeds, soil in which or on which plants grow, or cultivation areas.
  • the compound provided by the invention is a new compound which is more effective for weeds, lower in cost, less toxic and safe for the environment.
  • the compounds represented by formula (I), formula (IIa), formula (IIb), formula (IIIa) or formula (IIIb) may exist in different stereoisomers or optical isomers or tautomeric forms.
  • the present invention includes all such isomers and tautomers and mixtures thereof in various ratios, as well as isotopic forms such as compounds containing heavy hydrogen.
  • Isotope-enriched compounds have the structure depicted by the general formula given in this invention, except that one or more atoms are replaced with atoms having a selected atomic weight or mass number.
  • Exemplary isotopes that can be incorporated into the compounds of the present invention include isotopes of hydrogen, carbon, nitrogen, oxygen, phosphorus, sulfur, fluorine, and chlorine, such as 2 H, 3 H, 11 C, 13 C, 14 C, 15 N, 17 O , 18 O, 18 F, 31 P, 32 P, 35 S, 36 Cl and 125 I.
  • Any asymmetric atoms (for example, carbon, etc.) of the compounds disclosed in the present invention can exist in racemic or enantiomerically enriched forms, such as (R)-, (S)-, or (R,S)-configuration forms exist.
  • the articles “a”, “an” and “said” as used herein are intended to include “at least one” or “one or more”. Therefore, the articles used herein refer to one or more than one (ie, at least one) object articles.
  • a component refers to one or more components, that is, there may be more than one component that is considered to be employed or used in the implementation of the embodiment.
  • Stereoisomer refers to compounds that have the same chemical structure, but differ in the way the atoms or groups are arranged in space. Stereoisomers include enantiomers, diastereomers, conformational isomers (rotamers), geometric isomers (cis/trans) isomers, atropisomers, etc. .
  • Enantiomer refers to two isomers of a compound that cannot overlap but are mirror images of each other.
  • Diastereomer refers to a stereoisomer that has two or more chiral neutrals and whose molecules are not mirror images of each other. Diastereomers have different physical properties, such as melting point, boiling point, spectral properties and reactivity. Diastereomer mixtures can be separated by high-resolution analytical operations such as electrophoresis and chromatography, for example, by HPLC.
  • optically active compounds that is, they have the ability to rotate the plane of plane polarized light.
  • the prefixes D and L or R and S are used to denote the absolute configuration of the molecule with respect to one or more chiral centers.
  • the prefixes d and l or (+) and (-) are symbols used to specify the rotation of plane polarized light caused by a compound, where (-) or l indicates that the compound is levorotatory.
  • Compounds prefixed with (+) or d are right-handed.
  • a specific stereoisomer is an enantiomer, and a mixture of such isomers is called a mixture of enantiomers.
  • a 50:50 mixture of enantiomers is called a racemic mixture or a racemate, which can occur when there is no stereoselectivity or stereospecificity in a chemical reaction or process.
  • the compounds of the present invention may be optionally substituted with one or more substituents, such as the compounds of the general formula above, or like the specific examples, subclasses, and inclusions of the present invention in the examples.
  • substituents such as the compounds of the general formula above, or like the specific examples, subclasses, and inclusions of the present invention in the examples.
  • a class of compounds such as the compounds of the general formula above, or like the specific examples, subclasses, and inclusions of the present invention in the examples.
  • substituents such as the compounds of the general formula above, or like the specific examples, subclasses, and inclusions of the present invention in the examples.
  • a class of compounds A class of compounds.
  • substituted is used interchangeably with the term “substituted or unsubstituted”.
  • substituted means that one or more hydrogen atoms in a given structure are replaced by specific substituents. Unless otherwise indicated, an optional substituent may be substituted at each substitutable position of the group.
  • substituents When more than one position in the given structural formula can be substituted by one or more substituents selected from specific groups, the substituents may be substituted at the same positions or differently.
  • the substituents described herein may be, but not limited to, deuterium, fluorine, chlorine, bromine, iodine, cyano, hydroxy, nitro, amino, carboxy, alkyl, alkoxy, alkoxyalkyl, alkyl Oxyalkoxy, alkoxyalkylamino, aryloxy, heteroaryloxy, heterocyclyloxy, arylalkoxy, heteroarylalkoxy, heterocyclylalkoxy, cycloalkane Alkoxy, alkylamino, alkylaminoalkyl, alkylaminoalkylamino, cycloalkylamino, cycloalkylalkylamino, alkylthio, haloalkyl, haloalkoxy, hydroxy-substituted alkyl
  • C 1 -C 6 alkyl or "C 1-6 alkyl” particularly refers to independently disclosed methyl, ethyl, C 3 alkyl, C 4 alkyl, C 5 alkyl, and C 6 alkyl base.
  • alkyl or “alkyl group” means a saturated linear or branched monovalent hydrocarbon group containing 1 to 20 carbon atoms; wherein the alkyl group is optionally One or more substituents described in this invention are substituted. Unless otherwise specified, alkyl groups contain 1-20 carbon atoms. In one embodiment, the alkyl group contains 1-12 carbon atoms; in one embodiment, the alkyl group contains 1-10 carbon atoms; in one embodiment, the alkyl group contains 1-8 Carbon atoms; in another embodiment, the alkyl group contains 1-6 carbon atoms; in yet another embodiment, the alkyl group contains 1-4 carbon atoms; in another embodiment, the alkyl group The radical group contains 1-3 carbon atoms.
  • alkyl groups include, but are not limited to, methyl (Me, -CH 3 ), ethyl (Et, -CH 2 CH 3 ), n-propyl (n-Pr, -CH 2 CH 2 CH 3 ), isopropyl (i-Pr, -CH(CH 3 ) 2 ), n-butyl (n-Bu, -CH 2 CH 2 CH 2 CH 3 ), isobutyl (i-Bu, -CH 2 CH (CH 3 ) 2 ), sec-butyl (s-Bu, -CH(CH 3 )CH 2 CH 3 ), tert-butyl (t-Bu, -C(CH 3 ) 3 ), n-pentyl (-CH 2 CH 2 CH 2 CH 3 ), 2-pentyl (-CH(CH 3 )CH 2 CH 2 CH 3 ), 3-pentyl (-CH(CH 2 CH 3 ) 2 ), 2-methyl -2-butyl(-C(CH 3 ) 2
  • alkenyl means a straight-chain or branched monovalent hydrocarbon group containing 2-12 carbon atoms, in which there is at least one unsaturated site, that is, there is a carbon-carbon sp 2 double bond, wherein the alkenyl group
  • the group may be optionally substituted with one or more substituents described in the present invention, which includes the positioning of "cis” and “tans", or the positioning of "E” and "Z”.
  • the alkenyl group contains 2-10 carbon atoms; in one embodiment, the alkenyl group contains 2-8 carbon atoms; in another embodiment, the alkenyl group contains 2- 6 carbon atoms; in yet another embodiment, the alkenyl group contains 2-4 carbon atoms.
  • alkynyl refers to a straight-chain or branched monovalent hydrocarbon group containing 2-12 carbon atoms, in which there is at least one carbon-carbon sp triple bond, wherein the alkynyl group may be optionally substituted by one or more Substituted by the substituents described in this invention.
  • the alkynyl group contains 2-10 carbon atoms; in one embodiment, the alkynyl group contains 2-8 carbon atoms; in another embodiment, the alkynyl group contains 2- 6 carbon atoms; in yet another embodiment, the alkynyl group contains 2-4 carbon atoms.
  • alkynyl groups include, but are not limited to, -C ⁇ CH, -C ⁇ CCH 3 , -CH 2 -C ⁇ CH, -CH 2 -C ⁇ CCH 3 , -CH 2 CH 2 -C ⁇ CH , -CH 2 -C ⁇ CCH 2 CH 3 , -CH 2 CH 2 -C ⁇ CH 2 CH 3, etc.
  • alkoxy means that the alkyl group is connected to the rest of the molecule through an oxygen atom, wherein the alkyl group has the meaning as described in the present invention. Unless otherwise specified, the alkoxy group contains 1-12 carbon atoms. In one embodiment, the alkoxy group contains 1-10 carbon atoms; in one embodiment, the alkoxy group contains 1-8 carbon atoms; in one embodiment, the alkoxy group contains 1-6 carbon atoms; in another embodiment, the alkoxy group contains 1-4 carbon atoms; in yet another embodiment, the alkoxy group contains 1-3 carbon atoms.
  • the alkoxy group can be optionally substituted with one or more substituents 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- Propoxy, -OCH 2 CH 2 CH 3 ), 2-propoxy (i-PrO, i-propoxy, -OCH(CH 3 ) 2 ), 1-butoxy (n-BuO, n- Butoxy, -OCH 2 CH 2 CH 2 CH 3 ), 2-methyl-l-propoxy (i-BuO, i-butoxy, -OCH 2 CH(CH 3 ) 2 ), 2-butan Oxygen (s-BuO, s-butoxy, -OCH(CH 3 )CH 2 CH 3 ), 2-methyl-2-propoxy (t-BuO, t-butoxy, -OC(CH 3 ) 3 ), 1-pentoxy (n-pentoxy, -OCH 2 CH 2 CH 2 CH 2 CH 3 ), 2-pentoxy (
  • alkylamino or “alkylamino” includes “N-alkylamino” and "N,N-dialkylamino” in which the amino groups are each independently substituted with one or two alkyl groups.
  • the alkylamino group is a lower alkylamino group having one or two C 1-6 alkyl groups attached to a nitrogen atom.
  • the alkylamino group is a lower alkylamino group of C 1-3 .
  • Suitable alkylamino groups may be monoalkylamino or dialkylamino, examples of which include, but are not limited to, N-methylamino, N-ethylamino, N,N-dimethylamino, N,N -Diethylamino and so on.
  • alkylthio refers to a linear or branched alkyl group attached to a divalent sulfur atom, where the alkyl group has the meaning as described in the present invention.
  • alkylthio groups include, but are not limited to, -SCH 3 , -SCH 2 CH 3 , -SCH 2 CH 2 CH 3 and the like.
  • halogen refers to fluorine (F), chlorine (Cl), bromine (Br) or iodine (I).
  • haloalkyl means that the alkyl group is substituted with one or more halogen atoms.
  • haloalkyl groups include, but are not limited to, -CH 2 F, -CHF 2 , -CH 2 Cl, -CH 2 Br, -CF 3 , -CH 2 CF 3 , -CH 2 CH 2 F, -CH 2 CH 2 Cl, -CH 2 CH 2 Br, -CH 2 CHF 2 , -CH 2 CH 2 CF 3 , -CH 2 CH 2 CH 2 F, -CH 2 CH 2 CH 2 Cl, -CH 2 CH 2 CH 2 Br, -CHFCH 2 CH 3 , -CHClCH 2 CH 3 , etc.
  • haloalkenyl means that the alkenyl group is substituted with one or more halogen atoms.
  • haloalkynyl means that the alkynyl group is substituted with one or more halogen atoms.
  • haloalkoxy means that the alkoxy group is replaced by one or more halogen atoms.
  • haloalkoxy include, but are not limited to, -OCH 2 F, -OCHF 2 , -OCH 2 Cl, -OCH 2 Br, -OCF 3 , -OCH 2 CF 3 , -OCH 2 CH 2 F, -OCH 2 CH 2 Cl, -OCH 2 CH 2 Br, -OCH 2 CHF 2 , -OCH 2 CH 2 CF 3 , -OCH 2 CH 2 CH 2 F, -OCH 2 CH 2 CH 2 Cl, -OCH 2 CH 2 CH 2 Br, -OCHFCH 2 CH 3 , -OCHClCH 2 CH 3 , etc.
  • haloalkylamino means that the alkylamino group is replaced by one or more halogen atoms.
  • haloalkylthio means that the alkylthio group is substituted with one or more halogen atoms.
  • alkoxyalkyl means that the alkyl group is substituted with one or more alkoxy groups, wherein the alkyl group and the alkoxy group have the meaning as described in the present invention.
  • alkoxyalkyl groups include, but are not limited to, -CH 2 OCH 3 , -CH 2 CH 2 OCH 3 , -CH 2 OCH 2 CH 3 or -CH 2 CH 2 OCH 2 CH 3 .
  • alkylaminoalkyl means that the alkyl group is substituted with one or more alkylamino groups, wherein the alkyl group and the alkylamino group have the meaning as described in the present invention.
  • alkylthioalkyl means that the alkyl group is substituted with one or more alkylthio groups, wherein the alkyl group and the alkylthio group have the meanings as described in the present invention.
  • cycloalkyl denotes a monovalent or polyvalent saturated monocyclic, bicyclic or tricyclic ring system containing 3-15 carbon atoms. In one embodiment, cycloalkyl contains 3-12 carbon atoms; in one embodiment, cycloalkyl contains 3-10 carbon atoms; in another embodiment, cycloalkyl contains 3-8 carbons Atom; in yet another embodiment, the cycloalkyl group contains 3-6 carbon atoms.
  • the cycloalkyl group is optionally substituted with one or more substituents described in the present invention.
  • Such examples include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl, cyclododecyl Alkyl, adamantyl, etc.
  • cycloalkylalkyl means that the alkyl group is substituted with a cycloalkyl group, wherein the alkyl group and the cycloalkyl group have the meaning as described in the present invention.
  • heterocyclyl and “heterocycle” are used interchangeably herein and refer to saturated or partially unsaturated monocyclic, bicyclic or tricyclic rings containing 3-15 ring atoms, of which monocyclic, bicyclic or tricyclic
  • the ring does not contain an aromatic ring, and at least one ring atom is selected from nitrogen, sulfur, and oxygen atoms.
  • the sulfur atom of the ring can optionally be oxidized to an S-oxide.
  • the nitrogen atom of the ring can optionally be oxidized to an N-oxygen compound.
  • heterocyclic groups include, but are not limited to, oxirane, azetidinyl, oxetanyl, thietanyl, pyrrolidinyl (eg 2-pyrrolidinyl), 2-pyrrole Porphyrinyl, 3-pyrrolyl, pyrazolidinyl, imidazolinyl, imidazolidinyl, tetrahydrofuranyl, dihydrofuranyl, tetrahydrothienyl, dihydrothienyl, 1,3-dioxanyl, Dithiocyclopentyl, tetrahydropyranyl, dihydropyranyl, 2H-pyranyl, 4H-pyranyl, tetrahydrothiopyranyl, piperidinyl (2-piperidinyl, 3-piperidinyl , 4-piperidinyl), morpholinyl, thiomorpholinyl, (1-oxo)-thiomorpholinyl,
  • Examples of oxidized sulfur atoms in the heterocyclic group include, but are not limited to, sulfolane, 1,1-dioxothiomorpholinyl.
  • the heterocyclyl group is optionally substituted with one or more substituents described in this invention.
  • heterocyclylalkyl refers to an alkyl group substituted by a heterocyclyl group; wherein the heterocyclyl group and the alkyl group have the meanings as described in the present invention.
  • ring of x atoms typically describes the number of ring-forming atoms in the molecule, and the number of ring-forming atoms in the molecule is x.
  • piperidinyl is a 6-membered heterocyclic group.
  • unsaturated means that the group contains one or more degrees of unsaturation.
  • heteroatom refers to O, S, N, P, and Si, including N, S, and P in any oxidation state; primary, secondary, tertiary amine, and quaternary ammonium salt forms; or heterocyclic nitrogen atoms Forms where 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).
  • aryl refers to monocyclic, bicyclic and tricyclic carbocyclic systems containing 6-14 ring atoms, or 6-12 ring atoms, or 6-10 ring atoms, wherein at least one ring system is aromatic Family, where each ring system contains a ring of 3-7 atoms and one or more attachment points are connected to the rest of the molecule.
  • aryl may be used interchangeably with the term “aromatic ring”. Examples of aryl groups may include phenyl, indenyl, naphthyl and anthracenyl. The aryl group is optionally substituted with one or more substituents described in this invention.
  • arylalkyl or “aralkyl” means that the alkyl group is substituted with one or more aryl groups, wherein the alkyl and aryl groups have the meaning as described in the present invention.
  • arylalkyl groups may include phenylmethyl (ie, benzyl), phenethyl, and the like.
  • aryloxy or "aryloxy” includes an optionally substituted aryl group, as defined in the present invention, is attached to an oxygen atom and is connected to the rest of the molecule by an oxygen atom, wherein the aryl group has The meaning as described in the present invention.
  • heteroaryl refers to monocyclic, bicyclic and tricyclic ring systems containing 5-12 ring atoms, or 5-10 ring atoms, or 5-6 ring atoms, at least one of which is aromatic, And at least one ring system contains one or more heteroatoms, wherein each ring system contains a ring composed of 5-7 atoms, and one or more attachment points are connected to the rest of the molecule.
  • heteroaryl may be used interchangeably with the term “heteroaryl ring” or “heteroaromatic compound”.
  • the heteroaryl group is optionally substituted with one or more substituents described herein.
  • a heteroaryl group consisting of 5-10 atoms contains 1, 2, 3, or 4 heteroatoms independently selected from O, S, and N.
  • the ring atoms of the heteroaryl group contain 1-9 carbon atoms and 1-4 heteroatoms selected from N, O, or S; in another embodiment, the ring atoms of the heteroaryl group contain 1-5 carbon atoms and 1-4 heteroatoms selected from N, O or S.
  • heteroaryl means a 5- or 6-membered heteroaryl containing 1-4 N heteroatoms; in yet another embodiment, heteroaryl means 1-3 are selected from N, O Or a 5-membered heteroaryl group of a heteroatom of S; in yet another embodiment, a heteroaryl group represents a 5-membered heteroaryl group containing 1-3 heteroatoms selected from N or O; in yet another embodiment, Heteroaryl means a 5-membered heteroaryl containing 1-3 heteroatoms selected from N or S.
  • heteroaryl groups include, but are not limited to, 2-furanyl, 3-furanyl, 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 means that the alkyl group is substituted with one or more heteroaryl groups, wherein the alkyl group and the heteroaryl group have the meaning as described in the present invention.
  • heteroaryloxy or “heteroaryloxy” includes an optionally substituted heteroaryl group, as defined in the present invention, is attached to an oxygen atom and is connected to the rest of the molecule by an oxygen atom, wherein the heteroaryl group
  • the radical group has the meaning as described in the present invention.
  • salts of the compound of the present invention include those derived from alkali metals or alkaline earth metals and those derived from ammonia and amines.
  • Preferred cations include sodium, potassium, magnesium and ammonium cations having the chemical formula N + (R a R b R c R d ), where 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 having the compound represented by 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- Butoxyethylamine, morpholine, cyclododecylamine or benzylamine) is prepared by treating the compound represented by formula (I).
  • a metal hydroxide such as sodium hydroxide
  • an amine such as ammonia, trimethylamine, diethanolamine, 2-methylthiopropylamine, bisallylamine, 2- Butoxyethylamine, morpholine, cyclododecylamine or benzylamine
  • acceptable salts can be formed from organic and inorganic acids, such as acetic acid, propionic acid, lactic acid, citric acid, tartaric acid, succinic acid, fumaric acid, maleic acid, propanediol 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.
  • organic and inorganic acids such as acetic acid, propionic acid, lactic acid, citric acid, tartaric acid, succinic acid, fumaric acid, maleic acid, propanediol Acid, mandelic acid, malic acid, phthalic acid, hydrochloric acid, hydrobromic acid, phosphoric acid, nitric acid, sulfuric acid, me
  • compositions and formulations of compounds of the present invention are provided.
  • the compound of the present invention can be generally used as a herbicide active ingredient in a composition or formulation, the composition or formulation further comprising at least one adjuvant selected from surfactants, solid diluents and liquid diluents .
  • the ingredients of the formulation or composition are selected to be consistent with the physical characteristics of the active ingredient, the mode of application and environmental factors such as soil type, humidity and temperature.
  • Liquid compositions include solutions (including emulsifiable concentrates), suspensions, emulsions (including microemulsions and/or suspoemulsions), etc., which can optionally be thickened into gels.
  • aqueous liquid compositions are soluble concentrates, suspension concentrates, capsule suspensions, concentrated emulsions, microemulsions and suspoemulsions.
  • non-aqueous liquid compositions are emulsifiable concentrates, microemulsifiable concentrates, dispersible concentrates and oil dispersions.
  • the general types of solid compositions are powders, powders, granules, pellets, pellets, lozenges, tablets, filled films (including seed coatings), etc., which may be water-dispersible ("wettable") Or water soluble. Films and coatings formed from film-forming solutions or flowable suspensions are particularly useful for seed treatment.
  • the active ingredient may be encapsulated by (micro)capsules and further formed into a suspension or solid preparation; or the entire active ingredient preparation may be encapsulated (or "coated”). Encapsulation can control or delay the release of the active ingredient.
  • Emulsifiable granules combine the advantages of both emulsifiable concentrate formulations and dry granule formulations.
  • the high-concentration composition is mainly used as an intermediate for other preparations.
  • Sprayable formulations are usually dispersed in a suitable medium before spraying. Such liquid preparations and solid preparations are formulated into preparations that are easily diluted in a spray medium (usually water).
  • the spray volume may be in the range of about one liter to several thousand liters per hectare, but more typically in the range of about ten to several hundred liters per hectare.
  • Sprayable formulations can be mixed with water or another suitable medium in a water tank for the treatment of leaves by air or ground application, or applied to the growth medium of plants. Liquid and dry formulations can be dosed directly into the drip irrigation system, or into the furrow during planting.
  • the formulation will usually contain an effective amount of active ingredient, diluent and surfactant, the sum of which is 100% by weight.
  • Solid diluents include, for example, clays such as bentonite, montmorillonite, attapulgite and kaolin, gypsum, cellulose, titanium dioxide, zinc oxide, starch, dextrin, sugar (e.g. lactose, sucrose), silica, talc, mica, diatom Earth, urea, calcium carbonate, sodium carbonate and sodium bicarbonate, and sodium sulfate.
  • Typical solid diluents are described in Watkins et al. Handbook Insecticide Dust Diluents and Carriers, 2nd Edition, Dorland Books, Caldwell, New Jersey.
  • Liquid diluents include, for example, water, N,N-dimethylalkanamide (e.g. N,N-dimethylformamide), limonene, dimethyl sulfoxide, N-alkylpyrrolidone (e.g.
  • N-methylpyrrolidone Ethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, propylene carbonate, butylene carbonate, paraffin (such as white mineral oil, normal paraffins, isoparaffins), alkylbenzene, alkylnaphthalene, Glycerin, triacetin, sorbitol, aromatic hydrocarbons, dearomatized aliphatic compounds, alkylbenzene, alkylnaphthalene, ketones (such as cyclohexanone, 2-heptanone, isophorone and 4-hydroxy-4 -Methyl-2-pentanone), acetate (such as isoamyl acetate, hexyl acetate, heptyl acetate, octyl acetate, nonyl acetate, tridecyl acetate and isobornyl acetate), others Esters (such as alkyl,
  • Liquid diluents also include glycerides of saturated and unsaturated fatty acids (usually C 6 -C 22 ), such as oils of plant seeds and fruits (eg olive oil, castor oil, linseed oil, sesame oil, corn oil, peanut oil , Sunflower oil, grapeseed oil, safflower oil, cottonseed oil, soybean oil, rapeseed oil, coconut oil and palm kernel oil), fats of animal origin (such as tallow, lard, lard, cod liver oil, fish oil), and Their mixture.
  • oils of plant seeds and fruits eg olive oil, castor oil, linseed oil, sesame oil, corn oil, peanut oil , Sunflower oil, grapeseed oil, safflower oil, cottonseed oil, soybean oil, rapeseed oil, coconut oil and palm kernel oil
  • fats of animal origin such as tallow, lard, lard, cod liver oil, fish oil
  • the liquid diluent also includes alkylated (eg, methylated, ethylated, butylated) fatty acids, where the fatty acids can be obtained by hydrolysis of glycerides derived from plants and animals, and can be purified by distillation.
  • alkylated (eg, methylated, ethylated, butylated) fatty acids where the fatty acids can be obtained by hydrolysis of glycerides derived from plants and animals, and can be purified by distillation.
  • Typical liquid diluents are described in Solvents Guide, Marsden, 2nd Edition, Interscience, New York, 1950.
  • the solid and liquid compositions of the present invention generally contain one or more surfactants.
  • surfactants also called “surface-active agents”
  • surface-active agents usually change, most often reducing the surface tension of the liquid.
  • the surfactant can be used as a wetting agent, dispersant, emulsifier or defoamer.
  • Nonionic surfactants can be divided into nonionic surfactants, anionic surfactants or cationic surfactants.
  • Nonionic surfactants that can be used in the composition of the present invention include, but are not limited to: alcohol alkoxylates, such as based on natural alcohols and synthetic alcohols (which are branched or linear) and composed of alcohols and ethylene oxide, Alcohol alkoxylates prepared from propylene oxide, butylene oxide or their mixtures; amine ethoxylation, alkanolamides and ethoxylated alkanolamides; alkoxylated triglycerides, Such as ethoxylated soybean, castor and rapeseed oil; alkylphenol alkoxylates, such as octylphenol ethoxylate, nonylphenol ethoxylate, dinonylphenol ethoxylate and ten Dialkylphenol ethoxylates (prepared from phenol and ethylene oxide, propylene oxide, butylene
  • Useful anionic surfactants include, but are not limited to: alkylarylsulfonic acids and their salts; carboxylated alcohols or alkylphenol ethoxylates; diphenylsulfonate derivatives; lignin and lignin derivatives Substances, such as lignin sulfonates; maleic acid or succinic acid or their anhydrides; olefin sulfonates; phosphate esters, such as phosphate esters of alcohol alkoxylates, phosphate esters of alkylphenol alkoxylates, and benzene Phosphate esters of vinylphenol ethoxylates; protein-based surfactants; sarcosine derivatives; styrylphenol ether sulfates; sulfates and sulfonates of oils and fatty acids; ethoxylated alkylphenols Sulfates and sulfonates; alcohol sulfates; eth
  • Useful cationic surfactants include, but are not limited to: amides and ethoxylated amides; amines, such as N-alkyl propylene diamine, tripropylene triamine and dipropylene tetramine, and ethoxylated amines, Ethoxylated diamines and propoxylated amines (made from amines and ethylene oxide, propylene oxide, butylene oxide or mixtures thereof); amine salts, such as amine acetate and diamine salts; quaternary Ammonium salts, such as quaternary salts, ethoxylated quaternary salts, and diquaternary salts; and amine oxides, such as alkyldimethylamine oxides and di-(2-hydroxyethyl)-alkylamine oxides.
  • amines such as N-alkyl propylene diamine, tripropylene triamine and dipropylene tetramine, and ethoxylated amine
  • composition of the present invention is a mixture of nonionic surfactants and anionic surfactants, or a mixture of nonionic surfactants and cationic surfactants.
  • Non-ionic, anionic and cationic surfactants and their recommended uses are disclosed in a number of published references, including McCutcheon's Emulsifiers and Detergents, published by McCutcheon's Division, The Manufacturing Confectioner Publishing Co., North American and International Yearbooks Edition; Encyclopedia of Surface, Active Agents, Chemical, Publ. Co., Inc., New York, 1964 of Sisely and Wood; and Synthetic Detergents of AS Davidson and B. Milwidsky, seventh edition, John Wiley and Sons, New York, 1987 .
  • compositions of the present invention may also contain formulation aids and additives known to those skilled in the art as auxiliary formulations (some of which may also be considered to function as solid diluents, liquid diluents, or surfactants).
  • formulation aids and additives can be controlled: pH (buffer), foaming during processing (defoamer such as polyorganosiloxane), sedimentation of active ingredients (suspending agent), viscosity (thixotropic thickener) ), microbial growth in the container (antimicrobial agent), product freezing (antifreeze), color (dye/pigment dispersion), elution (film-forming agent or binder), evaporation (anti-evaporation agent), and others Preparation properties.
  • Film-forming agents include, for example, polyvinyl acetate, polyvinyl acetate copolymer, polyvinylpyrrolidone-vinyl acetate copolymer, polyvinyl alcohol, polyvinyl alcohol copolymer, and wax.
  • formulation aids and additives include McCutcheon’s Volume 2: Functional Materials, North American and International Yearbook editions published by McCutcheon’s Division, The Manufacturing, Publishing, Co.; and those listed in PCT Publication WO 03/024222.
  • the compounds of the present invention and any other active ingredients are generally incorporated into the compositions of the present invention by dissolving the active ingredients in a solvent or by grinding the active ingredients in a liquid or dry diluent.
  • Solutions, including emulsifiable concentrates can be prepared by simply mixing the ingredients. If the solvent of the liquid composition used as emulsifiable concentrate is immiscible with water, an emulsifier is usually added to emulsify the solvent containing the active ingredient when it is diluted with water.
  • a media mill can be used to wet grind the active ingredient slurry with a particle size of at most 2,000 ⁇ m to obtain particles with an average diameter below 3 ⁇ m.
  • the aqueous slurry can be prepared as a finished suspension concentrate (see, for example, U.S. 3,060,084) or further processed by spray drying to form water-dispersible particles. Dry formulations usually require a dry grinding step, which produces an average particle size in the range of 2 ⁇ m to 10 ⁇ m. Powders and powders can be prepared by mixing, and usually by grinding (for example with a hammer mill or fluid energy mill). The granules and granules can be prepared by spraying the active substance on a preformed particle carrier or by agglomeration techniques.
  • Granules can be prepared as described in US 4,172,714.
  • Water-dispersible and water-soluble granules can be prepared as proposed in US 4,144,050, US 3,920,442 and DE. 3,246,493.
  • Tablets can be prepared as US 5,180,587, US 5,232,701 and US 5,208,030 are prepared.
  • the membrane can be prepared as proposed in GB 2,095,558 and US 3,299,566.
  • the herbicide of the present invention can be used by spraying plants, applying to soil, and applying to water surfaces.
  • the amount of active component is appropriately determined to meet the application purpose.
  • the content of the active component is appropriately determined according to this purpose.
  • the amount of the compound of the present invention is determined according to the kind of compound used, target weeds, the tendency of weeds appearing, environmental conditions, the type of herbicide, etc.
  • the amount of the active ingredient is appropriately selected to be 1 g-50 kg/1 hectare, preferably 10 g-10 kg/1 hectare.
  • the herbicide of the present invention is used in a liquid form, for example, in the form of an emulsifiable concentrate, a wettable powder, or a flowable preparation, its amount is appropriately selected to be 0.1-50,000 ppm, preferably 10-10,000 ppm.
  • the present invention provides a method for controlling weeds in crops of useful plants, the method comprising applying to the weeds or to the locus of the weeds or to the locus of the useful plants or to the locus of the useful plants.
  • the compound or composition of the invention is administered.
  • the present invention also provides a method for selectively controlling grass and/or weeds in crops of useful plants, the method comprising applying a herbicidal effective amount of formula (I), formula to a useful plant or its locus or to a cultivation area
  • a herbicidal effective amount of formula (I) formula to a useful plant or its locus or to a cultivation area
  • herbicide means a compound that controls or modifies plant growth.
  • herbicidally effective amount means the amount of such a compound or combination of such compounds capable of producing a plant growth control or modification effect.
  • the effects of control or change include all deviations from natural development, such as killing, delaying, leaf burns, albinism, dwarfing disease, etc.
  • plant refers to all tangible parts of a plant, including seeds, seedlings, young plants, roots, tubers, stems, stalks, leaves, and fruits.
  • locus is intended to include soil, seeds, and seedlings, together with established plants (vegetation) and not only include areas where weeds may have grown, but also areas where weeds have not yet appeared, and also include useful plant crops Planted area.
  • Cosmetic area includes land on which crop plants have grown, as well as land intended to be used for growing such crop plants.
  • weeds as used herein means any undesirable plants, and therefore includes not only important agronomic weeds as described below, but also autogenous crop plants.
  • Useful plant crops that may use the composition according to the present invention include, but are not limited to perennial crops such as citrus fruits, vines, nuts, oil palm, olives, pear fruits, stone fruits and rubber, as well as annual arable crops,
  • perennial crops such as citrus fruits, vines, nuts, oil palm, olives, pear fruits, stone fruits and rubber
  • annual arable crops For example, cereals (such as barley and wheat), cotton, rape, corn, rice, soybean, sugar beet, sugar cane, sunflower, ornamental plants, switchgrass, turf, and vegetables, especially cereals, corn, and soybeans.
  • the grasses and weeds to be controlled may be monocotyledonous species, such as Prunus spp., Triticum spp., Oat spp., Brachiaria spp., Brome spp., Tribulus spp., Cyperus spp., Malthus spp., Barnyardgrass, Panicum, Ryegrass, Aegis, Panicum, Bluegrass, Trichosanthes, Citrus, Sclelotium, Setaria, Phellodendron, Sorghum, or Dicotyledon Species, for example, genus Astragalus, Amaranthus, Chenopodium, Chrysanthemum, Euphorbia, Laravine, Ipomoea, Kochia, Nasturtium, Polygonum, Phellodendron, White Mustard, Solanum Genus, Stellaria, Granola, Viola and Xanthium.
  • Prunus spp. Triticum spp., Oat spp.
  • the compounds of the present invention can show tolerance to important crops including, but not limited to, alfalfa, barley, cotton, wheat, canola, sugar beet, corn (maize), sorghum, soybean, rice, oats, peanuts, Vegetables, tomatoes, potatoes, perennial crops including coffee, cocoa, oil palm, rubber, sugar cane, citrus, grapes, fruit trees, nut trees, bananas, plantains, pineapples, hops, tea and forests such as eucalyptus and conifers (e.g. torch Pine), as well as turf species (such as meadow grass, St. Augustine (St. Augustine grass), Kentucky catkins and bermudagrass).
  • important crops including, but not limited to, alfalfa, barley, cotton, wheat, canola, sugar beet, corn (maize), sorghum, soybean, rice, oats, peanuts, Vegetables, tomatoes, potatoes, perennial crops including coffee, cocoa, oil palm, rubber, sugar cane
  • the compounds according to the invention having formula (I), formula (IIa), formula (IIb), formula (IIIa) or formula (IIIb) can also be combined with other active ingredients, for example other herbicides and/or Or insecticides and/or acaricides and/or nematicides and/or molluscicides and/or fungicides and/or plant growth regulators are used in combination. These mixtures and the use of these mixtures to control the growth of weeds and/or undesirable plants form yet other aspects of the invention.
  • the mixture of the present invention also includes a mixture of two or more different compounds having the formula (I), formula (IIa), formula (IIb), formula (IIIa) or formula (IIIb).
  • the present invention also relates to a composition of the present invention, which contains, in addition to the compound represented by formula (I), formula (IIa), formula (IIb), formula (IIIa) or formula (IIIb) At least one additional herbicide.
  • the compounds of the present invention can be prepared by the methods described in the present invention unless otherwise specified.
  • the raw materials, reagents, etc. used for preparing the compound of the present invention are all commercially available, or can be prepared by conventional methods in the art.
  • test conditions of the nuclear magnetic resonance hydrogen spectrum of the present invention are: at room temperature, a Bruker 400MHz or 600MHz nuclear magnetic instrument uses CDC1 3 , d 6 -DMSO, CD 3 OD or d 6 -acetone as the solvent (reported in ppm as Unit), using TMS (0ppm) or chloroform (7.26ppm) as a reference standard.
  • the mass spectrometry method used in the present invention is as follows: the conditions for low-resolution mass spectrometry (MS) data determination are: Agilent 6120 Quadrupole HPLC-MS (column model: Zorbax SB-C18, 2.1x 30mm, 3.5 ⁇ m, 6min, flow rate 0.6mL/min , Mobile phase: 5%-95% (ratio of CH 3 CN with 0.1% formic acid) in (H 2 O with 0.1% formic acid)), UV detection at 210/254 nm, electrospray ionization mode (ESI).
  • MS mass spectrometry
  • Compound E can be prepared by synthetic scheme 1, wherein R has the meaning as described in the present invention. 4-chloroquinoline-6-carboxylic acid methyl ester and alcohol R-OH under alkaline conditions (such as sodium hydride, potassium carbonate, triethylamine, pyridine, etc.), nucleophilic substitution reaction at 80 °C -150 °C, to obtain Compound A; Compound A is hydrolyzed under alkaline conditions (such as lithium hydroxide, potassium hydroxide, sodium hydroxide, etc.) to obtain Compound B; Compound B and dichlorosulfoxide undergo a halogenation reaction at 60°C to 100°C to obtain the compound C; Compound C and 1,3 cyclohexanedione undergo esterification reaction at 0°C-35°C to obtain compound D; Compound D and trimethylcyanosilane undergo Fries rearrangement reaction at 10°C-40°C to obtain the target compound E.
  • alkaline conditions such as sodium hydride, potassium
  • Compound G can be prepared by synthetic scheme two, wherein R, R 33 and R 44 have the meanings as described in the present invention.
  • Compound C and optionally substituted hydroxypyrazole undergo esterification reaction at 0°C-35°C to obtain compound F;
  • Compound F and trimethylcyanosilane undergo Fries rearrangement reaction at 10°C-40°C to obtain target compound G.
  • Step 1 Synthesis of methyl 4-(((4,4-dimethyl-2,6-dioxocyclohexylene)methyl)amino)benzoate
  • Step 2 Synthesis of methyl 4-oxo-1,4-dihydroquinoline-6-carboxylate
  • Step 4 Synthesis of methyl 4-(2,2-difluoroethoxy)quinoline-6-carboxylate
  • Step 8 Synthesis of (4-(2,2-difluoroethoxy)quinolin-6-yl)(5-hydroxy-1,3-dimethyl-1H-pyrazol-4-yl)methanone
  • Step 9 2-((4-(4-(2,2-difluoroethoxy)quinoline-6-carbonyl)-1,3-dimethyl-1H-pyrazol-5-yl)oxy )-1-Synthesis of Acetophenone
  • Compound preparation Weigh a certain quality of the original drug with an analytical balance (0.0001g), dissolve it with an appropriate amount of DMF, and then dilute with a certain volume of distilled water containing 1 ⁇ Tween-80 emulsifier for later use.
  • Test method The test targets are velvetleaf, purslane, barnyard grass and bristlegrass.
  • Stem and leaf spraying method take flower pots with an average length of 7.0 cm and width, fill the soil to 3/4 places, directly sow the pre-treated weed target seeds, cover the soil with about 1.0 cm, and spray the seedlings when they reach the appropriate age. After each compound was applied at a set dose, it was transferred to outdoor cultivation and the activity (%) against weeds was investigated 21 days later.
  • Example 1 95 Example 2 95 Example 3 100 Example 4 90 Example 5 88 Example 6 100 Example 16 95 Example 33 80 Example 34 90 Example 37 80
  • Table A show that the control effect of the compounds of the present invention on purslane at 1000 g.
  • the compound of the present invention has a very good control effect on broad-leaved weeds (such as velvetleaf, Amaranthus retroflexus, and intestine) and gramineous weeds (such as horsetail, barnyard grass, and green foxtail), which are safe for crops.
  • broad-leaved weeds such as velvetleaf, Amaranthus retroflexus, and intestine
  • gramineous weeds such as horsetail, barnyard grass, and green foxtail

Abstract

一种式(I)所示的喹啉衍生物及其制备方法，含有这些化合物的组合物和制剂及其作为除草剂的用途；其中R为氢、烷基、烯基、炔基、烷氧基烷基等；Cy为任选取代的吡唑基等。

Description

喹啉衍生物及其制备方法和用途 技术领域
本发明提供一种新的喹啉衍生物及其制备方法，包含这些化合物的组合物及其在农业中的应用。
背景技术
WO 9812180、WO 9812192、WO 2000014069、CN 102249996揭示了喹啉化合物具有一定的除草活性，然而，在下文中详细描述的本发明化合物没有在这些文献中描述过。
从以上引用的文献中所知的活性成分在使用中具有的不利之处在于，例如(a)对杂草植物没有或者仅具有不足够的除草作用、(b)待防治的杂草植物谱过窄或者(c)在有用植物作物中的选择性过低。
因此，需要提供可有利地用作除草剂或植物生长调节剂的化学活性成分。
发明内容
本发明提供一种新的喹啉化合物，具有优良的除草作用以及在农作物与杂草之间的优良选择性。
一方面，本发明提供式(I)所示的化合物或式(I)所示化合物的立体异构体、氮氧化物或其盐：
Figure PCTCN2018122505-appb-000001
其中：
R为氢、烷基、烯基、炔基、烷氧基烷基、烷氨基烷基、烷硫基烷基、卤代烷基、环烷基、杂环基、芳基、杂芳基、环烷基烷基、杂环基烷基、芳基烷基或者杂芳基烷基；R任选地被1、2、3、4、5或6个选自R x的取代基所取代；
Cy为以下子结构式：
Figure PCTCN2018122505-appb-000002
或者
Figure PCTCN2018122505-appb-000003
R 1和R 22各自独立地为氢、-C(＝O)-(CH 2) n-R 8、-(CH 2) m-C(＝O)-R 8a、-C(＝O)-O-R 9、-C(＝O)-NR 10R 11、-S(＝O) 2-R 12、-S(＝O) 2-NR 13R 14；
n为0、1、2或3；
m为1、2或3；
其中R 8、R 8a、R 9、R 10、R 11、R 12、R 13和R 14各自独立地为氢、烷基、烷氧基烷基、芳基或杂芳基；R 8、R 8a、R 9、R 10、R 11、R 12、R 13和R 14各自独立任选地被1、2、3、4、5或6个选自R y的取代基所取代；
R 2、R 3、R 4、R 5、R 6和R 7各自独立地为氢、氟、氯、溴、碘、氨基、硝基、氰基、羟基、羧基、烷基、烷氧基、烷硫基或烷基羰基；
R 33为氢、烷基、烯基、炔基或环烷基；
R 44为氢、氰基、氟、氯、溴、碘、烷基、烯基、炔基、烷氧基、烷硫基或环烷基；
R x和R y各自独立地为氟、氯、溴、碘、氨基、硝基、氰基、羟基、羧基、C 1-8烷基、卤代C 1-8烷基、C 2-8烯基、卤代C 2-8烯基、C 2-8炔基、卤代C 2-8炔基、C 1-8烷氧基、卤代C 1-8烷氧基、C 1-8烷氨基、C 1-8烷硫基、卤代C 1-8烷氨基、卤代C 1-8烷硫基、C 6-10芳基、C 6-10芳氧基、C 1-9杂芳基或C 1-9杂芳氧基。
其中一些实施方案中，本发明提供式(IIa)所示的化合物或式(IIa)所示化合物的立体异构体、氮氧化物或其盐：
Figure PCTCN2018122505-appb-000004
其中：R 1、R 2、R 3、R 4、R 5、R 6、R 7和R具有如本发明所述的含义。
其中一些实施方案中，本发明提供式(IIb)所示的化合物或式(IIb)所示化合物的立体异构体、氮氧化物或其盐：
Figure PCTCN2018122505-appb-000005
其中：R 22、R 33、R 44和R具有如本发明所述的含义。
另外一些实施方案中，本发明提供式(IIIa)所示的化合物或式(IIIa)所示化合物的立体异构体、氮氧化物或其盐：
Figure PCTCN2018122505-appb-000006
其中：R 22、R 33和R 44具有如本发明所述的含义。
另外一些实施方案中，本发明提供式(IIIb)所示的化合物或式(IIIb)所示化合物的立体异构体、氮氧化物或其盐：
Figure PCTCN2018122505-appb-000007
其中：R 22、R 33和R 44具有如本发明所述的含义；
R m、R n、R v、R w和R z各自独立地为氢、氟、氯、溴、碘、氨基、硝基、氰基、羟基、羧基、C 1-6烷基、卤代C 1-6烷基、C 2-6烯基、卤代C 2-6烯基、C 2-6炔基、卤代C 2-6炔基、C 1-6烷氧基、卤代C 1-6烷氧基、C 1-6烷氨基、C 1-6烷硫基、卤代C 1-6烷氨基、卤代C 1-6烷硫基、C 6-10芳基、C 6-10芳氧基、C 1-5杂芳基或C 1-5杂芳氧基。
其中一些实施方案中，R为氢、C 1-8烷基、C 2-8烯基、C 2-8炔基、C 1-8烷氧基C 1-8烷基、C 1-8烷氨基C 1-8烷基、C 1-8烷硫基C 1-8烷基、卤代C 1-8烷基、C 3-8环烷基、C 2-10杂环基、C 6-10芳基、C 1-9杂芳基、C 3-8环烷基C 1-6烷基、C 2-10杂环基C 1-6烷基、C 6-10芳基C 1-6烷基或者C 1-9杂芳基C 1-6烷基；R任选地被1、2、3、4、5或6个选自R x的取代基所取代；其中各R x具有如本发明所述的含义。
另外一些实施方案中，R为氢、C 1-6烷基、C 2-6烯基、C 2-6炔基、C 1-6烷氧基C 1-6烷基、C 1-6烷氨基C 1-6烷基、C 1-6烷硫基C 1-6烷基、卤代C 1-6烷基、C 3-8环烷基、C 2-8杂环基、C 6-10芳基、C 1-9杂芳基、C 3-8环烷基C 1-6烷基、C 2-8杂环基C 1-6烷基、C 6-10芳基C 1-6烷基或者C 1-9杂芳基C 1-6烷基；R任选地被1、2、3、4、5或6个选自R x的取代基所取代；其中各R x具有如本发明所述的含义。
另外一些实施方案中，R为氢、C 1-4烷基、C 2-4烯基、C 2-4炔基、C 1-3烷氧基C 1-3烷基、C 1-3烷氨基C 1-3烷基、C 1-3烷硫基C 1-3烷基、卤代C 1-4烷基、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 1-3烷基、C 2-6杂环基C 1-4烷基、C 6-10芳基C 1-3烷基或者C 1-5杂芳基C 1-3烷基；R任选地被1、2、3、4、5或6个选自R x的取代基所取代；其中各R x具有如本发明所述的含义。
另外一些实施方案中，R为C 1-3烷基、C 2-3烯基、C 2-3炔基、C 1-3烷氧基C 1-3烷基、卤代C 1-3烷基、苯基或C 2-4杂环基C 1-3烷基；R任选地被1、2、3、4、5或6个选自R x的取代基所取代；其中各R x具有如本发明所述的含义。
其中一些实施方案中，各R x独立地为氟、氯、溴、碘、氨基、硝基、氰基、羟基、羧基、C 1-6烷基、卤代C 1-6烷基、C 2-6烯基、卤代C 2-6烯基、C 2-6炔基、卤代C 2-6炔基、C 1-6烷氧基、卤代C 1-6烷氧基、C 1-6烷氨基、C 1-6烷硫基、卤代C 1-6烷氨基、卤代C 1-6烷硫基、C 6-10芳基、C 6-10芳氧基、C 1-5杂芳基或C 1-5杂芳氧基。
另外一些实施方案中，各R x独立地为氟、氯、溴、碘、氨基、硝基、氰基、羟基、羧基、C 1-4烷基、卤代C 1-4烷基、C 2-4烯基、卤代C 2-4烯基、C 2-4炔基、卤代C 2-4炔基、C 1-4烷氧基、卤代C 1-4烷氧基、C 1-4烷氨基、C 1-4烷硫基、卤代C 1-4烷氨基、卤代C 1-4烷硫基、C 6-10芳基、C 6-10芳氧基、C 1-5杂芳基或C 1-5杂芳氧基。
另外一些实施方案中，各R x独立地为氟、氯、溴、碘、氨基、硝基、氰基、羟基、羧基、甲基、乙基、正丙基、异丙基、二氟甲基、三氟甲基、甲氧基或三氟甲氧基。
另外一些实施方案中，R为氢、-CH 3、-CH 2CH 3、-CH 2CH 2CH 3、-CH(CH 3) 2、-CF 3、-CH 2CHF 2、-CH 2CF 3、-CH 2OCH 3、-CH 2CH 2OCH 3或-CH 2OCH 2CH 3；或者R为以下子结构式：
Figure PCTCN2018122505-appb-000008
其中一些实施方案中，R 2、R 3、R 4、R 5、R 6和R 7各自独立地为氢、氟、氯、溴、碘、氨基、硝基、氰基、羟基、羧基、C 1-6烷基、C 1-6烷氧基、C 1-6烷硫基或C 1-6烷基羰基。
另外一些实施方案中，R 2、R 3、R 4、R 5、R 6和R 7各自独立地为氢、氟、氯、溴、碘、氨基、硝基、氰基、羟基、羧基、C 1-4烷基、C 1-4烷氧基、C 1-4烷硫基或C 1-4烷基羰基。
另外一些实施方案中，R 2、R 3、R 4、R 5、R 6和R 7各自独立地为氢、氟、氯、溴、碘、氨基、硝基、氰基、羟基、羧基、甲基、乙基、正丙基、异丙基或甲氧基。
其中一些实施方案中，R 1和R 22各自独立地为氢、-C(＝O)-(CH 2) n-R 8、-(CH 2) m-C(＝O)-R 8a、-C(＝O)-O-R 9、-C(＝O)-NR 10R 11、-S(＝O) 2-R 12、-S(＝O) 2-NR 13R 14；
n为0、1、2或3；
m为1、2或3；
其中R 8、R 8a、R 9、R 10、R 11、R 12、R 13和R 14各自独立地为氢、C 1-6烷基、C 1-6烷氧基C 1-6烷基、C 6-10芳基或C 1-9杂芳基；R 8、R 8a、R 9、R 10、R 11、R 12、R 13和R 14各自独立任选地被1、2、3、4、5或6个选自R y的取代基所取代；其中各R y具有如本发明所述的含义。
其中一些实施方案中，R 33为氢、C 1-6烷基、C 2-6烯基、C 2-6炔基或C 3-6环烷基。
其中一些实施方案中，R 44为氢、氰基、氟、氯、溴、碘、C 1-6烷基、C 2-6烯基、C 2-6炔基、C 1-6烷氧基、C 1-6烷硫基或C 3-6环烷基。
另外一些实施方案中，R 1和R 22各自独立地为氢、-C(＝O)-(CH 2) n-R 8或-(CH 2) m-C(＝O)-R 8a；
n为0、1、2或3；
m为1、2或3；
其中R 8和R 8a各自独立地为氢、C 1-4烷基、C 1-4烷氧基C 1-4烷基、苯基或C 2-3杂芳基；R 8和R 8a各自独立任选地被1、2、3、4、5或6个选自R y的取代基所取代；其中各R y具有如本发明所述的含义。
另外一些实施方案中，R 8和R 8a各自独立地为苯基或吡唑基；R 8和R 8a各自独立任选地被1、2、3、4、5或6个选自R y的取代基所取代；其中各R y具有如本发明所述的含义。
另外一些实施方案中，R 33为氢、C 1-4烷基、C 2-4烯基、C 2-4炔基或C 3-6环烷基。
另外一些实施方案中，R 44为氢、氰基、氟、氯、溴、碘、C 1-4烷基、C 2-4烯基、C 2-4炔基、C 1-4烷氧基、C 1-4烷硫基或C 3-6环烷基。
其中一些实施方案中，各R y独立地为氟、氯、溴、碘、氨基、硝基、氰基、羟基、羧基、C 1-6烷基、卤代C 1-6烷基、C 2-6烯基、卤代C 2-6烯基、C 2-6炔基、卤代C 2-6炔基、C 1-6烷氧基、卤代C 1-6烷氧基、C 1-6烷氨基、C 1-6烷硫基、卤代C 1-6烷氨基、卤代C 1-6烷硫基、C 6-10芳基、C 6-10芳氧基、C 1-5杂芳基或C 1-5杂芳氧基。
另外一些实施方案中，各R y独立地为氟、氯、溴、碘、氨基、硝基、氰基、羟基、羧基、C 1-4烷基、卤代C 1-4烷基、C 2-4烯基、卤代C 2-4烯基、C 2-4炔基、卤代C 2-4炔基、C 1-4烷氧基、卤代C 1-4烷氧基、C 1-4烷氨基、C 1-4烷硫基、卤代C 1-4烷氨基、卤代C 1-4烷硫基、C 6-10芳基、C 6-10芳氧基、C 1-5杂芳基或C 1-5杂芳氧基。
另外一些实施方案中，各R y独立地为氟、氯、溴、碘、氨基、硝基、氰基、羟基、羧基、甲基、乙基、正丙基、异丙基、二氟甲基、三氟甲基、甲氧基或三氟甲氧基。
另外一些实施方案中，R 22为氢、
Figure PCTCN2018122505-appb-000009
另外一些实施方案中，R 33为氢、甲基、乙基、正丙基或异丙基。
另外一些实施方案中，R 44为氢、氰基、氟、氯、溴、碘、甲基、乙基、正丙基、异丙基或环丙基。
另外一些实施方案中，R m、R n、R v、R w和R z各自独立地为氢、氟、氯、溴、碘、氨基、硝基、氰基、羟基、羧基、C 1-4烷基、卤代C 1-4烷基、C 2-4烯基、卤代C 2-4烯基、C 2-4炔基、卤代C 2-4炔基、C 1-4烷氧基、卤代C 1-4烷氧基、C 1-4烷氨基、C 1-4烷硫基、卤代C 1-4烷氨基、卤代C 1-4烷硫基、C 6-10芳基、C 6-10芳氧基、C 1-5杂芳基或C 1-5杂芳氧基。
另外一些实施方案中，R m、R n、R v、R w和R z各自独立地为氢、氟、氯、溴、碘、氨基、硝基、氰基、羟基、羧基、甲基、乙基、正丙基、异丙基、二氟甲基、三氟甲基、甲氧基或三氟甲氧基。
另外一些实施方案中，本发明提供一种化合物，其为具有下列之一结构的化合物或具有下列之一结构化合物的立体异构体、氮氧化物或其盐：
Figure PCTCN2018122505-appb-000010
Figure PCTCN2018122505-appb-000011
Figure PCTCN2018122505-appb-000012
Figure PCTCN2018122505-appb-000013
Figure PCTCN2018122505-appb-000014
或者
Figure PCTCN2018122505-appb-000015
另一方面，本发明提供一种组合物，包含本发明所述的化合物，任选地进一步包含至少一种辅助剂。
另一方面，本发明提供本发明所述化合物或组合物在农业中的应用。
其中一些实施方案中，本发明提供本发明所述化合物或组合物用于防治不想要的植物的用途。
其中一些实施方案中，本发明提供本发明所述化合物或组合物作为除草剂的用途。
另一方面，本发明提供防治不想要的植物的方法，其特征在于将有效量的本发明所述化合物施用于植物、植物种子、其中或其上生长植物的土壤，或栽培区域。
本发明提供的化合物，是一种对杂草更有效、成本更低、毒性更小、对环境安全的新型化合物。
式(I)、式(IIa)、式(IIb)、式(IIIa)或式(IIIb)所示的化合物可能以不同的立体异构体或光学异构体或互变异构形式存在。本发明包含所有此类异构体和互变异构体及其各种比例的混合物，以及同位素形式例如含重氢的化合物。
同位素富集的化合物具有本发明给出的通式描绘的结构，除了一个或多个原子被具有所选择原子量或质量数的原子替换。可引入本发明化合物中的示例性同位素包括氢、碳、氮、氧、磷、硫、氟和氯的同位素，如 2H， 3H， 11C， 13C， 14C， 15N， 17O， 18O， 18F， 31P， 32P， 35S， 36Cl和 125I。
本发明公开化合物的任何不对称原子(例如，碳等)都可以以外消旋或对映体富集的形式存在，例如(R)-、(S)-或(R,S)-构型形式存在。
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作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，例如可通过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中所描述的立体化学定义和规则。
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1-10个碳原子；在一实施方案中，烷基基团含有1-8个碳原子；在另一实施方案中，烷基基团含有1-6个碳原子；在又一实施方案中，烷基基团含有1-4个碳原子；还在一实施方案中，烷基基团含有1-3个碳原子。
烷基基团的实例包含，但并不限于，甲基(Me、-CH 3)，乙基(Et、-CH 2CH 3)，正丙基(n-Pr、-CH 2CH 2CH 3)，异丙基(i-Pr、-CH(CH 3) 2)，正丁基(n-Bu、-CH 2CH 2CH 2CH 3)，异丁基(i-Bu、-CH 2CH(CH 3) 2)，仲丁基(s-Bu、-CH(CH 3)CH 2CH 3)，叔丁基(t-Bu、-C(CH 3) 3)，正戊基(-CH 2CH 2CH 2CH 2CH 3)，2-戊基(-CH(CH 3)CH 2CH 2CH 3)，3-戊基(-CH(CH 2CH 3) 2)，2-甲基-2-丁基(-C(CH 3) 2CH 2CH 3)，3-甲基-2-丁基(-CH(CH 3)CH(CH 3) 2)，3-甲基-1-丁基(-CH 2CH 2CH(CH 3) 2)，2-甲基-1-丁基(-CH 2CH(CH 3)CH 2CH 3)，正己基(-CH 2CH 2CH 2CH 2CH 2CH 3)，2-己基(-CH(CH 3)CH 2CH 2CH 2CH 3)，3-己基(-CH(CH 2CH 3)(CH 2CH 2CH 3))，2-甲基-2-戊基(-C(CH 3) 2CH 2CH 2CH 3)，3-甲基-2-戊基(-CH(CH 3)CH(CH 3)CH 2CH 3)，4-甲基-2-戊基(-CH(CH 3)CH 2CH(CH 3) 2)，3-甲基-3-戊基(-C(CH 3)(CH 2CH 3) 2)，2-甲基-3-戊基(-CH(CH 2CH 3)CH(CH 3) 2)，2,3-二甲基-2-丁基(-C(CH 3) 2CH(CH 3) 2)，3,3-二甲基-2-丁基(-CH(CH 3)C(CH 3) 3)，正庚基，正辛基，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s p 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2-10个碳原子；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-)，-CH 2CH 2CH＝CH 2、-CH 2CH＝CHCH 3、-CH 2CH 2CH 2CH＝CH 2、-CH 2CH 2CH＝CHCH 3、-CH 2CH 2CH 2CH＝CHCH 3等等。
术语“炔基”表示含有2-12个碳原子的直链或支链一价烃基，其中至少有一个碳-碳sp三键，其中，所述炔基基团可以任选地被一个或多个本发明所描述的取代基所取代。在一实施方案中，炔基基团包含2-10个碳原子；在一实施方案中，炔基基团包含2-8个碳原子；在另一实施方案中，炔基基团包含2-6个碳原子；在又一实施方案中，炔基基团包含2-4个碳原子。炔基基团的实例包括，但并不限于，-C≡CH、-C≡CCH 3、-CH 2-C≡CH、-CH 2-C≡CCH 3、-CH 2CH 2-C≡CH、-CH 2-C≡CCH 2CH 3、-CH 2CH 2-C≡CH 2CH 3等等。
术语“烷氧基”表示烷基基团通过氧原子与分子其余部分相连，其中烷基基团具有如本发明所述的含义。除非另外详细说明，所述烷氧基基团含有1-12个碳原子。在一实施方案中，烷氧基基团含有1-10个碳原子；在一实施方案中，烷氧基基团含有1-8个碳原子；在一实施方案中，烷氧基基团含有1-6个碳原子；在另一实施方案中，烷氧基基团含有1-4个碳原子；在又一实施方案中，烷氧基基团含有1-3个碳原子。所述烷氧基基团可以任选地被一个或多个本发明描述的取代基所取代。
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)，1-丁氧基(n-BuO、n-丁氧基、-OCH 2CH 2CH 2CH 3)，2-甲基-l-丙氧基(i-BuO、i-丁氧基、-OCH 2CH(CH 3) 2)，2-丁氧基(s-BuO、s-丁氧基、-OCH(CH 3)CH 2CH 3)，2-甲基-2-丙氧基(t-BuO、t-丁氧基、-OC(CH 3) 3)，1-戊氧基(n-戊氧基、-OCH 2CH 2CH 2CH 2CH 3)，2-戊氧基(-OCH(CH 3)CH 2CH 2CH 3)，3-戊氧基(-OCH(CH 2CH 3) 2)，2-甲基-2-丁氧基(-OC(CH 3) 2CH 2CH 3)，3-甲基-2-丁氧基(-OCH(CH 3)CH(CH 3) 2)，3-甲基-l-丁氧基(-OCH 2CH 2CH(CH 3) 2)，2-甲基-l-丁氧基(-OCH 2CH(CH 3)CH 2CH 3)，等等。
术语“烷基氨基”或“烷氨基”包括“N-烷基氨基”和“N,N-二烷基氨基”，其中氨基基团分别独立地被一个或两个烷基基团所取代。其中一些实施例是，烷基氨基是一个或两个C 1-6烷基连接到氮原子上的较低级的烷基氨基基团。另外一些实施例是，烷基氨基是C 1-3的较低级的烷基氨基基团。合适的烷基氨基基团可以是单烷基氨基或二烷基氨基，这样的实例包括，但并不限于，N-甲氨基，N-乙氨基，N,N-二甲氨基，N,N-二乙氨基等等。
术语“烷硫基”指直链或支链的烷基连接到二价的硫原子上，其中烷基基团具有如本发明所述的含义。烷硫基基团的实例包括，但并不限于，-SCH 3、-SCH 2CH 3、-SCH 2CH 2CH 3等等。
术语“卤素”是指氟(F)、氯(Cl)、溴(Br)或碘(I)。
术语“卤代烷基”表示烷基基团被一个或多个卤素原子所取代。卤代烷基的实例包括，但并不限于，-CH 2F，-CHF 2，-CH 2Cl，-CH 2Br，-CF 3，-CH 2CF 3，-CH 2CH 2F，-CH 2CH 2Cl，-CH 2CH 2Br，-CH 2CHF 2，-CH 2CH 2CF 3，-CH 2CH 2CH 2F，-CH 2CH 2CH 2Cl，-CH 2CH 2CH 2Br，-CHFCH 2CH 3，-CHClCH 2CH 3，等等。
术语“卤代烯基”表示烯基基团被一个或多个卤素原子所取代。
术语“卤代炔基”表示炔基基团被一个或多个卤素原子所取代。
术语“卤代烷氧基”表示烷氧基基团被一个或多个卤素原子所取代。卤代烷氧基的实例包括，但并不限于，-OCH 2F，-OCHF 2，-OCH 2Cl，-OCH 2Br，-OCF 3，-OCH 2CF 3，-OCH 2CH 2F，-OCH 2CH 2Cl，-OCH 2CH 2Br，-OCH 2CHF 2，-OCH 2CH 2CF 3，-OCH 2CH 2CH 2F，-OCH 2CH 2CH 2Cl，-OCH 2CH 2CH 2Br，-OCHFCH 2CH 3，-OCHClCH 2CH 3，等等。
术语“卤代烷氨基”表示烷氨基基团被一个或多个卤素原子所取代。
术语“卤代烷硫基”表示烷硫基基团被一个或多个卤素原子所取代。
术语“烷氧基烷基”表示烷基基团被一个或多个烷氧基基团所取代，其中烷基基团和烷氧基基团具有如本发明所述的含义。烷氧基烷基的实例包括，但并不限于，-CH 2OCH 3、-CH 2CH 2OCH 3、-CH 2OCH 2CH 3或-CH 2CH 2OCH 2CH 3。
术语“烷氨基烷基”表示烷基基团被一个或多个烷氨基基团所取代，其中烷基基团和烷氨基基团具有如本发明所述的含义。
术语“烷硫基烷基”表示烷基基团被一个或多个烷硫基基团所取代，其中烷基基团和烷硫基基团具有如本发明所述的含义。
术语“环烷基”表示含有3-15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3-12个碳原子；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，金刚烷基，等等。
术语“环烷基烷基”表示烷基基团被环烷基基团取代，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”是指杂环基取代的烷基；其中杂环基和烷基基团具有如本发明所述的含义。
术语“x个原子组成的环”，其中x是整数，典型地描述分子中成环原子的数目，在所述分子中成环原子的数目是x。例如，哌啶基是6个原子组成的杂环基。
在本发明中所使用的术语“不饱和的”表示基团中含有一个或多个不饱和度。
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“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”或“芳烷基”表示烷基被一个或多个芳基基团所取代，其中烷基和芳基基团具有如本发明所述的含义。芳基烷基的实例可以包括苯基甲基(即苄基)、苯乙基等等。
术语“芳氧基”或“芳基氧基”包括任选取代的芳基，如本发明所定义的，连接到氧原子上，并且由氧原子与分子其余部分相连，其中芳基基团具有如本发明所述的含义。
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。
在另一实施方案中，杂芳基的环原子包含1-9个碳原子和1-4个选自N、O或S的杂原子；在另一实施方案中，杂芳基的环原子包含1-5个碳原子和1-4个选自N、O或S的杂原子。
在又一实施方案中，杂芳基表示含1-4个N杂原子的5元或6元杂芳基；在又一实施方案中，杂芳基表示含1-3个选自N、O或S的杂原子的5元杂芳基；在又一实施方案中，杂芳基表示含1-3个选自N或O的杂原子的5元杂芳基；在又一实施方案中，杂芳基表示含1-3个选自N或S的杂原子的5元杂芳基。
杂芳基基团的实例包括，但并不限于，2-呋喃基，3-呋喃基，N-咪唑基，2-咪唑基，4-咪唑基，5-咪唑基，3-异噁唑基，4-异噁唑基，5-异噁唑基，2-噁唑基，4-噁唑基，5-噁唑基，N-吡咯基，2-吡咯基，3-吡咯基，2-吡啶基，3-吡啶基，4-吡啶基，2-嘧啶基，4-嘧啶基，5-嘧啶基，哒嗪基(如3-哒嗪基)，2-噻唑基，4-噻唑基，5-噻唑基，四唑基(如5-四唑基)，三唑基(如2-三唑基和5-三唑基)，2-噻吩基，3-噻吩 基，吡唑基，异噻唑基，1,2,3-噁二唑基，1,2,5-噁二唑基，1,2,4-噁二唑基，1,2,3-三唑基，1,2,3-硫代二唑基，1,3,4-硫代二唑基，1,2,5-硫代二唑基，吡嗪基，1,3,5-三嗪基，嘧啶酮基，吡啶酮基；也包括以下的双环，但绝不限于这些双环：苯并咪唑基，苯并呋喃基，苯并四氢呋喃基，苯并噻吩基，吲哚基(如2-吲哚基)，等等。
术语“杂芳基烷基”表示烷基基团被一个或多个杂芳基基团所取代，其中烷基基团和杂芳基基团具有如本发明所述的含义。
术语“杂芳基氧基”或“杂芳氧基”包括任选取代的杂芳基，如本发明所定义的，连接到氧原子上，并且由氧原子与分子其余部分相连，其中杂芳基基团具有如本发明所述的含义。
当本发明的化合物包含一个酸部分时，本发明所述化合物的盐，包括衍生自碱金属或碱土金属的那些以及衍生自氨和胺的那些。优选的阳离子包括钠、钾、镁以及具有化学式N +(R aR bR cR d)的铵阳离子，其中R a、R b、R c和R d独立地选自氢、C 1-C 6烷基和C 1-C 6羟基烷基。具有式(I)所示化合物的盐可以通过用金属氢氧化物(例如氢氧化钠)或胺(例如氨、三甲胺、二乙醇胺、2-甲硫基丙胺、双烯丙基胺、2-丁氧基乙胺、吗啉、环十二胺或苄胺)对具有式(I)所示的化合物进行处理来制备。
当本发明的化合物包含一个碱部分时，可接受的盐可以由有机酸和无机酸形成，例如乙酸、丙酸、乳酸、柠檬酸、酒石酸、琥珀酸、富马酸、马来酸、丙二酸、扁桃酸、苹果酸、邻苯二甲酸、盐酸、氢溴酸、磷酸、硝酸、硫酸、甲磺酸、萘磺酸、苯磺酸、甲苯磺酸、樟脑磺酸以及类似地已知可接受的酸。
本发明化合物的组合物和制剂
本发明的化合物一般可用作组合物或制剂中的除草剂活性成分，所述组合物或制剂进一步包含至少一种辅助剂，所述辅助剂选自表面活性剂、固体稀释剂和液体稀释剂。选择所述制剂或组合物成分，以与所述活性成分的物理特性、施用方式和环境因素(如土壤类型、湿度和温度)相一致。
有用的制剂包括液体组合物和固体组合物。液体组合物包括溶液(包括乳油)、悬浮液、乳液(包括微乳液和/或悬乳液)等，它们可以任选地被稠化成凝胶。水性液体组合物的一般类型为可溶性浓缩物、悬浮液浓缩物、胶囊悬浮液、浓缩乳液、微乳液和悬乳液。非水性液体组合物的一般类型为乳油、可微乳化的浓缩物、可分散浓缩物和油分散体。
固体组合物的一般类型为粉剂、粉末、颗粒、粒料、球粒、锭剂、片剂、填充薄膜(包括种子包衣)等，它们可以是水分散性的(“可润湿的”)或水溶性的。由成膜溶液或可流动的悬浮液形成的膜和包衣尤其可用于种子处理。活性成分可被(微)胶囊包封，并且进一步形成悬浮液或固体制剂；或者可将整个活性成分制剂胶囊包封(或“包覆”)。胶囊包封可以控制或延迟活性成分的释放。可乳化的颗粒结合了乳油制剂和干颗粒制剂两者的优点。高浓度组合物主要用作其它制剂的中间体。
可喷雾的制剂通常在喷雾之前分散在合适的介质中。将此类液体制剂和固体制剂配制成易于在喷雾介质(通常是水)中稀释的制剂。喷雾体积可以在每公顷约一升至几千升的范围内，但更典型地在每公顷约十升至几百升的范围内。可喷雾的制剂可在水槽中与水或另一种合适的介质混合，用于通过空气或地面施用来处理叶子，或者施用到植物的生长介质中。液体和干制剂可以直接定量加入到滴灌系统中，或者在种植期间定量加入到垄沟中。
所述制剂通常将包含有效量的活性成分、稀释剂和表面活性剂，总和为按重量计100％。
固体稀释剂包括例如粘土例如膨润土、蒙脱石、绿坡缕石和高岭土、石膏、纤维素、二氧化钛、氧化锌、淀粉、糊精、糖(例如乳糖、蔗糖)、硅石、滑石、云母、硅藻土、尿素、碳酸钙、碳酸钠和碳酸氢钠以及硫酸钠。典型的固体稀释剂描述于Watkins等人的Handbook of Insecticide Dust Diluents and Carriers，第2版，Dorland Books，Caldwell，New Jersey中。
液体稀释剂包括例如水、N,N-二甲基烷酰胺(例如N,N-二甲基甲酰胺)、柠檬烯、二甲基亚砜、N-烷 基吡咯烷酮(例如N-甲基吡咯烷酮)、乙二醇、三甘醇、丙二醇、双丙二醇、聚丙二醇、碳酸亚丙酯、碳酸亚丁酯、石蜡(例如白矿物油、正链烷烃、异链烷烃)、烷基苯、烷基萘、甘油、三乙酸甘油酯、山梨醇、芳烃、脱芳构化脂族化合物、烷基苯、烷基萘、酮(如环己酮、2-庚酮、异佛尔酮和4-羟基-4-甲基-2-戊酮)、乙酸酯(如乙酸异戊酯、乙酸己酯、乙酸庚酯、乙酸辛酯、乙酸壬酯、乙酸十三烷基酯和乙酸异冰片酯)、其它酯(如烷基化乳酸酯、二元酯和γ-丁内酯)，并且可以是直链的、支链的、饱和的或不饱和的醇(如甲醇、乙醇、正丙醇、异丙醇、正丁醇、异丁醇、正己醇、2-乙基己醇、正辛醇、癸醇、异癸醇、异十八醇、鲸蜡醇、月桂醇、十三烷醇、油醇、环己醇、四氢糠醇、双丙酮醇和苄醇)。液体稀释剂还包括饱和的和不饱和的脂肪酸(通常为C 6-C 22)的甘油酯，如植物种子和果实的油(例如橄榄油、蓖麻油、亚麻籽油、芝麻油、玉米油、花生油、葵花籽油、葡萄籽油、红花油、棉籽油、豆油、油菜籽油、椰子油和棕榈仁油)、动物源脂肪(例如牛脂、猪脂、猪油、鳕鱼肝油、鱼油)，以及它们的混合物。液体稀释剂还包括烷基化(例如甲基化、乙基化、丁基化)的脂肪酸，其中脂肪酸可以通过源自植物和动物的甘油酯的水解获得，并且可通过蒸馏进行纯化。典型的液体稀释剂描述于Marsden的Solvents Guide，第2版，Interscience，New York，1950中。
本发明的固体组合物和液体组合物通常包含一种或多种表面活性剂。当加进液体中时，表面活性剂(也称为“具有表面活性的试剂”)通常改变，最通常降低液体的表面张力。根据表面活性剂分子中的亲水基团和亲脂基团的性质，表面活性剂可用作润湿剂、分散剂、乳化剂或消泡剂。
表面活性剂可分为非离子表面活性剂、阴离子表面活性剂或阳离子表面活性剂。可用作本发明的组合物的非离子表面活性剂包括但不限于：醇烷氧基化物，如基于天然醇和合成醇(其为支链的或直链的)并且由醇和环氧乙烷、环氧丙烷、环氧丁烷或它们的混合物制备的醇烷氧基化物；胺乙氧基化、链烷醇酰胺和乙氧基化的链烷醇酰胺；烷氧基化的甘油三酯，如乙氧基化的大豆、蓖麻和油菜籽油；烷基苯酚烷氧基化物，如辛基苯酚乙氧基化、壬基苯酚乙氧基化、二壬基苯酚乙氧基化物和十二烷基苯酚乙氧基化物(由苯酚和环氧乙烷、环氧丙烷、环氧丁烷或它们的混合物制备)；由环氧乙烷或环氧丙烷和反向嵌段聚合物制备的嵌段聚合物，其中末端嵌段由环氧丙烷制备；乙氧基化的脂肪酸；乙氧基化的脂肪族酯和油；乙氧基化的甲基酯；乙氧基化的三苯乙烯基苯酚(包括由环氧乙烷、环氧丙烷、环氧丁烷或它们的混合物制备的那些)；脂肪酸酯、甘油酯、羊毛脂基的衍生物、多乙氧基化的酯，如多乙氧基化的脱水山梨糖醇脂肪酸酯、多乙氧基化的山梨醇脂肪酸酯和多乙氧基化甘油脂肪酸酯；其它脱水山梨糖醇衍生物，如脱水山梨糖醇酯；聚合表面活性剂如无规共聚物、嵌段共聚物、醇酸PEG(聚乙二醇)树脂、接枝或梳妆聚合物和星型聚合物；聚乙二醇(PEG)；聚乙二醇脂肪酸酯；硅酮基的表面活性剂；以及糖衍生物，如蔗糖酯、烷基聚葡萄糖苷和烷基多糖。
可用的阴离子表面活性剂包括但不限于：烷基芳基磺酸和它们的盐；羧化的醇或烷基苯酚乙氧基化物；二苯基磺酸酯衍生物；木质素和木质素衍生物，如木质素磺酸盐；马来酸或琥珀酸或它们的酸酐；烯烃磺酸酯；磷酸酯，诸如醇烷氧基化物的磷酸酯、烷基酚烷氧基化物的磷酸酯和苯乙烯基苯酚乙氧基化物的磷酸酯；蛋白质基的表面活性剂；肌氨酸衍生物；苯乙烯基苯酚醚硫酸盐；油和脂肪酸的硫酸盐和磺酸盐；乙氧基化烷基酚的硫酸盐和磺酸盐；醇的硫酸盐；乙氧基化醇的硫酸盐；胺和酰胺的磺酸盐，如N,N-烷基牛磺酸盐；苯、异丙基苯、甲苯、二甲苯以及十二烷基苯和十三烷基苯的磺酸盐；缩聚萘的磺酸盐；萘和烷基萘的磺酸盐；石油馏分的磺酸盐；磺基琥珀酰胺酸盐；以及磺基琥珀酸盐和它们的衍生物，如二烷基磺基琥珀酸盐。
可用的阳离子表面活性剂包括但不限于：酰胺和乙氧基化酰胺；胺，如N-烷基丙二胺、三亚丙基三胺和二亚丙基四胺，以及乙氧基化胺、乙氧基化二胺和丙氧基化胺(由胺和环氧乙烷、环氧丙烷、环氧丁烷或它们的混合物制备)；胺盐，如胺乙酸盐和二胺盐；季铵盐，如季盐、乙氧基化季盐和二季盐；以及胺 氧化物，如烷基二甲基胺氧化物和二-(2-羟基乙基)-烷基胺氧化物。
还可用于本发明的组合物的是非离子表面活性剂和阴离子表面活性剂的混合物，或非离子表面活性剂和阳离子表面活性剂的混合物。非离子、阴离子和阳离子表面活性剂以及它们被推荐的用途公开于多个已公布的参考文献中，包括由McCutcheon’s Division，The Manufacturing Confectioner Publishing Co.出版的McCutcheon′s Emulsifiers and Detergents，北美和国际年鉴版；Sisely和Wood的Encyclopedia of Surface Active Agents，Chemical Publ.Co.，Inc.，New York，1964；以及A.S.Davidson和B.Milwidsky的Synthetic Detergents，第七版，John Wiley and Sons，New York，1987。
本发明的组合物还可包含本领域技术人员已知为辅助制剂的制剂助剂和添加剂(其中一些也可被认为是起到固体稀释剂、液体稀释剂或表面活性剂作用的)。此类制剂助剂和添加剂可控制：pH(缓冲剂)、加工过程中的起泡(消泡剂如聚有机硅氧烷)、活性成分的沉降(悬浮剂)、粘度(触变增稠剂)、容器内的微生物生长(抗微生物剂)、产品冷冻(防冻剂)、颜色(染料/颜料分散体)、洗脱(成膜剂或粘合剂)、蒸发(防蒸发剂)、以及其它制剂属性。成膜剂包括例如聚乙酸乙烯酯、聚乙酸乙烯酯共聚物、聚乙烯吡咯烷酮-乙酸乙烯酯共聚物、聚乙烯醇、聚乙烯醇共聚物和蜡。制剂助剂和添加剂的实例包括由McCutcheon’s Division，The Manufacturing Confectioner Publishing Co.出版的McCutcheon’s Volume 2：Functional Materials，北美和国际年鉴版；以及PCT公布WO03/024222中列出的那些。
通常通过将活性成分溶于溶剂中或通过在液体稀释剂或干稀释剂中研磨活性成分将本发明的化合物和任何其它的活性成分掺入到本发明的组合物中。可通过简单地混合所述成分来制备溶液，包括乳油。如果用作乳油的液体组合物的溶剂是与水不混溶的，则通常加入乳化剂使含有活性成分的溶剂在用水稀释时发生乳化。可使用介质磨来湿研磨粒径为至多2,000μm的活性成分浆液，以获得平均直径低于3μm的颗粒。水性浆液可以制备为成品悬浮液浓缩物(参见例如U.S.3,060,084)或通过喷雾干燥而进一步加工形成水分散性的颗粒。干制剂通常需要干研磨步骤，其产生在2μm至10μm范围内的平均粒径。粉剂和粉末可以通过混合，并且通常通过研磨(例如用锤磨机或流能磨)来制备。可通过将活性物质喷雾在预成形颗粒载体上或通过附聚技术来制备颗粒和粒料。参见Browning的“Agglomeration”(Chemical Engineering，1967年12月4日，第147-48页；Perry的Chemical Engineer’s Handbook，第4版，McGraw-Hill，New York，1963，第8-57页及其后页和WO91/13546。粒料可以如U.S.4,172,714中所述来制备。水分散性的和水溶性的颗粒可以如U.S.4,144,050、U.S.3,920,442和DE.3,246,493中所提出的来制备。片剂可以如U.S.5,180,587、U.S.5,232,701和U.S.5,208,030中所提出的来制备。膜可以如GB2,095,558和U.S.3,299,566中所提出的来制备。
与制剂领域相关的其他信息，参见T.S.Woods的“The Formulator’s Toolbox-Product Forms for Modern Agriculture”，Pesticide Chemistry and Bioscience，The Food-Environment Challenge，T.Brooks和T.R.Roberts编辑，Proceedings of the 9th International Congress on Pesticide Chemistry，The Royal Society of Chemistry，Cambridge，1999，第120-133页。还可参见U.S.3,235,361第6栏，第16行至第7栏，第19行和实施例10-41；U.S3,309,192第5栏，第43行至第7栏，第62行和实施例8、12、15、39、41、52、53、58、132、138-140、162-164、166、167和169-182；U.S.2,891,855第3栏，第66行至第5栏，第17行和实施例1-4；Klingman的Weed Control as a Science，John Wiley and Sons，Inc.，New York，1961，第81-96页；Hance等人的Weed Control Handbook，第8版，Blackwell Scientific Publications，Oxford，1989；以及Developments in formulation technology，PJB Publications，Richmond，UK，2000。
本发明化合物的应用
本发明除草剂可通过给植物喷雾、施加到土壤中、施加到水表面上来使用。适当地确定活性组分的用量以满足应用目的。根据该目的来适当地确定活性组分的含量。
本发明化合物的用量根据所用化合物的种类、目标杂草、杂草出现的趋势、环境条件和除草剂的种类等来确定。当本发明除草剂自身的形式例如以粉末或颗粒的形式使用时，其用量适当地选取为1g-50kg/1公顷、优选10g-10kg/1公顷的活性组分。当本发明的除草剂以液体形式例如以可乳化的浓缩物、可湿性粉剂或可流动制剂的形式使用时，其用量适当地选取为0.1-50,000ppm、优选10-10,000ppm。
本发明提供了一种用于控制有用植物的作物中的杂草的方法，该方法包括向所述杂草或向所述杂草的场所或向所述有用植物或向所述有用植物的场所施用本发明的化合物或组合物。
本发明还提供了一种选择性控制有用植物的作物中的草和/或杂草的方法，该方法包括向有用植物或其场所或向栽培区域施用除草有效量的具有式(I)、式(IIa)、式(IIb)、式(IIIa)或式(IIIb)所示的化合物。
术语“除草剂”意指一种控制或改变植物生长的化合物。术语“除草有效量”意指能够产生控制或改变植物生长效果的这样一种化合物或此类化合物的组合物的量。控制或者改变的效果包括所有自然发展的偏离，例如，杀害、延迟、叶灼伤、白化病、矮化病等。术语“植物”指的是植物的所有有形部分，包括种子、幼苗、幼株、根、块茎、茎、秆、叶和果实。术语“所在地”旨在包括土壤、种子以及幼苗，连同已经建立的植物(established vegetation)并且不仅包括杂草可能已经生长的区域，而且还包括杂草尚未出现的区域，并且还包括关于有用植物作物的种植的区域。“种植的区域”包括作物植物已经在其上生长的土地，以及打算用来种植此类作物植物的土地。如在此使用的术语“杂草”意指任何不希望的植物，并且因此不仅包括如下所述的重要的农艺杂草，而且还包括自生作物植物。
可能使用了根据本发明的组合物的有用植物作物包括但不限于多年生作物，例如柑橘类水果、葡萄树、坚果、油棕榈、橄榄、梨果类水果、核果及橡胶，以及一年生可耕作物，例如谷类(如大麦和小麦)、棉花、油菜、玉米、水稻、大豆、甜菜、甘蔗、向日葵、观赏植物、柳枝稷、草皮以及蔬菜，尤其是谷类、玉米以及大豆。
要控制的草和杂草既可以是单子叶的物种，例如剪股颖属、看麦娘属、燕麦属、臂形草属、雀麦属、蒺藜草属、莎草属、马唐属、稗属、野黍属、黑麦草属、雨久花属、黍属、早熟禾属、筒轴茅属、慈姑属、藨草属、狗尾草属、黄花稔属和高粱属，也可以是双子叶的物种，例如白麻属、苋属、藜属、菊属、大戟属、拉拉藤属、番薯属、地肤属、旱金莲属、蓼属植物、黄花稔属、白芥属、茄属、繁缕属、婆婆纳属、堇菜属和苍耳属。
本发明化合物可示出对重要农作物的耐受性，所述农作物包括但不限于苜蓿、大麦、棉花、小麦、油菜、糖用甜菜、玉米(玉蜀黍)、高粱、大豆、稻、燕麦、花生、蔬菜、番茄、马铃薯、多年生种植作物包括咖啡、可可、油棕、橡胶、甘蔗、柑橘、葡萄、果树、坚果树、香蕉、车前草、菠萝、啤酒花、茶和森林诸如桉树和针叶树(例如火炬松)、以及草皮物类(例如草地早熟禾、圣奥古斯丁草(St.Augustine grass)、Kentucky牛毛草和狗牙根草)。
如果需要的话，根据本发明的具有式(I)、式(IIa)、式(IIb)、式(IIIa)或式(IIIb)所示的化合物也可以与其他活性成分，例如其他除草剂和/或杀昆虫剂和/或杀螨剂和/或杀线虫剂和/或杀软体动物剂和/或杀真菌剂和/或植物生长调节剂组合使用。这些混合物、以及这些混合物的用以控制杂草和/或不希望的植物的生长的用途又形成了本发明的另一些方面。为避免疑问，本发明的混合物也包括两种或更多种不同的具有式(I)、式(IIa)、式(IIb)、式(IIIa)或式(IIIb)所示的化合物的混合物。具体地，本发明还涉及一种本发明的组合物，该组合物除式(I)、式(IIa)、式(IIb)、式(IIIa)或式(IIIb)所示的化合物之外包含至少一种另外的除草剂。
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。制备本发明的化合物所使用的原料、试 剂等等均是可以商购的，或者可以通过本领域常规的方法制备得到。
本发明核磁共振氢谱的测试条件是：室温条件下，布鲁克(Bruker)400MHz或600MHz的核磁仪，以CDC1 3，d 6-DMSO，CD 3OD或d 6-丙酮为溶剂(报导以ppm为单位)，用TMS(0ppm)或氯仿(7.26ppm)作为参照标准。当出现多重峰的时候，将使用下面的缩写：s(singlet，单峰)，d(doublet，双峰)，t(triplet，三重峰)，q(quartet，四重峰)，m(multiplet，多重峰)，br(broadened，宽峰)，dd(doublet of doublets，双二重峰)，dt(doublet of triplets，双三重峰)。偶合常数，用赫兹(Hz)表示。
本发明所用质谱分析方法为：低分辨率质谱(MS)数据测定的条件是：Agilent 6120Quadrupole HPLC-MS(柱子型号：Zorbax SB-C18,2.1x 30mm,3.5μm,6min,流速为0.6mL/min，流动相：5％-95％(含0.1％甲酸的CH 3CN)在(含0.1％甲酸的H 2O)中的比例))，在210/254nm用UV检测，用电喷雾电离模式(ESI)。
下面的简写词释义贯穿本发明：
DCM：二氯甲烷
DMF：N,N-二甲基甲酰胺，二甲基甲酰胺
Et 3N：三乙胺
THF：四氢呋喃
NaH：氢化钠
NaHCO 3：碳酸氢钠
TLC：Thin Layer Chromatography，薄层色谱法
下面的合成方案和实施例用于进一步举例说明本发明的内容。
合成方案一
Figure PCTCN2018122505-appb-000016
化合物E可以通过合成方案一制备得到，其中R具有如本发明所述的含义。4-氯喹啉-6-羧酸甲酯与醇R-OH在碱性条件下(如氢化钠、碳酸钾、三乙胺、吡啶等)，在80℃-150℃发生亲核取代反应，得到化合物A；化合物A在碱性条件下(如氢氧化锂、氢氧化钾、氢氧化钠等)水解得到化合物B；化合物B与二氯亚砜在60℃-100℃发生卤代反应，得到化合物C；化合物C与1,3环己二酮在0℃-35℃发生酯化反应，得到化合物D；化合物D与三甲基氰硅烷在10℃-40℃发生Fries重排反应，得到目标化合物E。
合成方案二
Figure PCTCN2018122505-appb-000017
化合物G可以通过合成方案二制备得到，其中R、R 33和R 44具有如本发明所述的含义。化合物C与任选取代地羟基吡唑在0℃-35℃发生酯化反应，得到化合物F；化合物F与三甲基氰硅烷在10℃-40℃发生Fries重排反应，得到目标化合物G。
合成方案三
Figure PCTCN2018122505-appb-000018
化合物(IIb’)可以通过合成方案三制备得到，其中X为卤素；R 22'为-C(＝O)-(CH 2) n-R 8或-(CH 2) m-C(＝O)-R 8a；R、R 33、R 44、n、m、R 8和R 8a具有如本发明所述的含义。化合物G与化合物R 22'-X在碱性条件下(如Cs 2CO 3、K 2CO 3等)在25℃-50℃下发生亲核取代反应，得到目标化合物(IIb’)。
实施例
实施例1 2-((4-(4-(2,2-二氟乙氧基)喹啉-6-羰基)-1,3-二甲基-1H-吡唑-5-基)氧基)-1-苯乙酮
Figure PCTCN2018122505-appb-000019
步骤1：甲基4-(((4,4-二甲基-2,6-二氧代环己亚基)甲基)氨基)苯甲酸酯的合成
Figure PCTCN2018122505-appb-000020
向单口瓶中依次加入对氨基苯甲酸甲酯(500mg,3.3mmol)，米氏酸(572mg,3.97mmol)和无水乙醇(10mL)，然后缓慢滴加原甲酸三乙酯(586mg,3.97mmol)，缓慢升温至78℃，反应2h，有大量白色固体 析出。TLC监测反应完全，停止反应。冷却至室温，抽滤，冷却的乙醇洗涤滤饼，干燥，得到白色固体990mg，收率98％。
步骤2：甲基4-氧代-1,4-二氢喹啉-6-羧酸酯的合成
Figure PCTCN2018122505-appb-000021
向单口瓶中加入甲基4-(((4,4-二甲基-2,6-二氧代环己亚基)甲基)氨基)苯甲酸酯(10g,33.9mmol)和邻二氯苯(50mL)，然后将体系放入180℃油浴中加热反应7h，TLC跟踪反应进程，体系由不溶解到无色透明，颜色进一步加深至深褐色，反应完成时体系中有固体生成。冷却至室温，抽滤，得到土黄色固体2.5g，收率38％。
MS(ES-API,pos.ion)m/z:204.1[M+H] +。
步骤3：4-氯喹啉-6-羧酸甲酯的合成
Figure PCTCN2018122505-appb-000022
向单口瓶中加入甲基4-氧代-1,4-二氢喹啉-6-羧酸酯(150mg,0.738mmol)，甲苯(3mL)和三氯氧磷(125mg,0.812mmol)，加入到120℃油浴中，搅拌3h，TLC监测反应完全。加入乙酸乙酯(10mL)稀释，用饱和碳酸氢钠溶液(5mL)洗涤，有机相浓缩，柱层析(石油醚/乙酸乙酯(V/V)＝5/1)，得到白色固体141mg，收率86％。
MS(ES-API,pos.ion)m/z:222.0[M+H] +。
步骤4：甲基4-(2,2-二氟乙氧基)喹啉-6-羧酸酯的合成
Figure PCTCN2018122505-appb-000023
向两口瓶中加入NaH(1.0g,24.82mmol,Wt＝60％)，氮气保护，然后加入超干DMF(45mL)，缓慢滴加2,2-二氟乙醇(2.04g,24.82mmol)，室温搅拌30min。然后快速加入4-氯喹啉-6-羧酸甲酯(5.0g,22.56mmol)，升温至80℃反应12h，TLC监测反应完全。将体系倒入水(200mL)中，有大量固体析出，抽滤，滤饼用水(20mL)洗涤，得到黄色固体4g，收率66％。
MS(ES-API,pos.ion)m/z:268.0[M+H] +。
步骤5：4-(2,2-二氟乙氧基)喹啉-6-羧酸的合成
Figure PCTCN2018122505-appb-000024
向单口瓶中加入甲基4-(2,2-二氟乙氧基)喹啉-6-羧酸酯(5.0g,18.71mmol)，THF(35mL)，乙醇(35mL)，水(35mL)和一水合氢氧化锂(1.5g,37.42mmol)，室温搅拌，反应2h。TLC监测反应完全。减压蒸馏除去THF和乙醇，加入适量水溶解，乙酸乙酯萃取(20mL x 2)，收集水相，用浓盐酸(2M,30mL)酸化，有大量固体析出，抽滤，得到白色固体2.2g，收率46％。
MS(ES-API,pos.ion)m/z:254.1[M+H] +。
步骤6：4-(2,2-二氟乙氧基)喹啉-6-酰氯的合成
Figure PCTCN2018122505-appb-000025
向单口瓶中加入4-(2,2-二氟乙氧基)喹啉-6-羧酸(500mg,1.97mmol)和二氯亚砜(4mL)，室温搅拌，然后加入2滴DMF催化，回流反应3h，原料溶解。将体系脱干，加入干燥的DCM(5mL)，得到4-(2,2-二氟乙氧基)喹啉-6-酰氯悬浮液。
步骤7：1,3-二甲基-1H-吡唑-5-基4-(2,2-二氟乙氧基)喹啉-6-羧酸酯的合成
Figure PCTCN2018122505-appb-000026
向单口瓶中加入1,3-二甲基-1H-吡唑-5-醇(265mg,2.39mmol)，干燥的二氯甲烷(20mL)和Et 3N(372mg,3.68mmol)，0℃搅拌，然后加入步骤6中的4-(2,2-二氟乙氧基)喹啉-6-酰氯悬浮液。升温至室温，反应过夜，TLC检测反应完全。用饱和碳酸氢钠溶液(10mL)洗涤，饱和食盐水(10mL)洗涤，浓缩，重结晶，得到黄色固体600mg。
MS(ES-API,pos.ion)m/z:348.0[M+H] +。
步骤8：(4-(2,2-二氟乙氧基)喹啉-6-基)(5-羟基-1,3-二甲基-1H-吡唑-4-基)甲酮的合成
Figure PCTCN2018122505-appb-000027
向单口瓶中加入1,3-二甲基-1H-吡唑-5-基4-(2,2-二氟乙氧基)喹啉-6-羧酸酯(600mg,1.73mmol)，乙腈(25mL)和三乙胺(350mg,3.46mmol)，室温搅拌，然后加入三甲基氰硅烷(25mg,0.26mmol)。室温反应24h，TLC监测反应完全。用冰醋酸(1mL)酸化体系，室温搅拌30min，将体系脱去有机溶剂，加水(15mL)溶解，用二氯甲烷(20mL x 2)萃取，柱层析(二氯甲烷/甲醇(V/V)＝20/1)分离提纯，得到黄色固体300mg，收率50％。
MS(ES-API,pos.ion)m/z:348.1[M+H] +；
1H NMR(400MHz,DMSO-d 6)δ8.85(d,J＝5.2Hz,1H),8.43(s,1H),8.03–7.95(m,2H),7.20(d,J＝5.2Hz,1H),6.57(tt,J＝54.0,3.2Hz,1H),4.67(td,J＝14.6,3.2Hz,2H),3.46(s,3H),2.15(s,3H).
步骤9：2-((4-(4-(2,2-二氟乙氧基)喹啉-6-羰基)-1,3-二甲基-1H-吡唑-5-基)氧基)-1-苯乙酮的合成
Figure PCTCN2018122505-appb-000028
向单口瓶中加入(4-(2,2-二氟乙氧基)喹啉-6-基)(5-羟基-1,3-二甲基-1H-吡唑-4-基)甲酮(95mg,0.274mmol)，干燥DMF(10mL)和碳酸钾(57mg,0.411mmol)，搅拌溶解，然后加入α-溴代苯乙酮(60mg,0.301mmol)。室温反应过夜，TLC监测反应完全。向体系中加入乙酸乙酯(20mL)稀释，用饱和NaHCO 3 溶液洗涤，浓缩有机相，柱层析(二氯甲烷/甲醇(V/V)＝50/1)，得到土黄色固体90mg，收率70％。
MS(ES-API,pos.ion)m/z:466.1[M+H] +；
1H NMR(600MHz,CDCl 3)δ8.85(d,J＝5.1Hz,1H),8.56(d,J＝1.8Hz,1H),8.11(d,J＝8.7Hz,1H),8.03(dd,J＝8.7,1.8Hz,1H),7.72(d,J＝7.2Hz,2H),7.55(t,J＝7.5Hz,1H),7.41(t,J＝7.8Hz,2H),6.79(d,J＝5.1Hz,1H),6.27(tt,J＝54.6,4.2Hz,1H),5.48(s,2H),4.44(td,J＝12.6,4.2Hz,2H),3.88(s,3H),2.02(s,3H).
参考本发明合成方案或具体实施例的合成，采用相应的原料及条件，可得到表1的目标化合物。
表1
Figure PCTCN2018122505-appb-000029
Figure PCTCN2018122505-appb-000030
Figure PCTCN2018122505-appb-000031
Figure PCTCN2018122505-appb-000032
Figure PCTCN2018122505-appb-000033
Figure PCTCN2018122505-appb-000034
Figure PCTCN2018122505-appb-000035
Figure PCTCN2018122505-appb-000036
Figure PCTCN2018122505-appb-000037
Figure PCTCN2018122505-appb-000038
生物实施例
化合物配制：用分析天平(0.0001g)称取一定质量的原药，用适量DMF溶解，然后用一定体积的含1‰吐温-80乳化剂蒸馏水稀释备用。
试验方法：供试靶标为苘麻、马齿苋、稗草、狗尾草。
茎叶喷雾法：取长宽均7.0cm花盆，装土至3/4处，直接播种预处理的杂草靶标种子，覆土约1.0cm，待幼苗长至适龄阶段进行喷雾处理。各化合物按照设定剂量施药后，移入室外培养，21天后调查对杂草的活性(％)。
试验结果示于表A。
表A 剂量为1000g a.i./ha，本发明化合物对马齿苋的防效
实施例 防效(％)
化合物(M) 80
实施例1 95
实施例2 95
实施例3 100
实施例4 90
实施例5 88
实施例6 100
实施例16 95
实施例33 80
实施例34 90
实施例37 80
表A结果显示，本发明化合物在1000g a.i./ha对马齿苋的防效可达80-100％。另外，本发明化合物对阔叶科杂草(如苘麻、反枝苋、鱧肠)和禾本科杂草(如马唐、稗草和狗尾草)均具有很好的防治效果，对作物安全，具有很好的应用前景。

Claims (10)

  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、氮氧化物或盐：
    Figure PCTCN2018122505-appb-100001
    其中：
    R为氢、烷基、烯基、炔基、烷氧基烷基、烷氨基烷基、烷硫基烷基、卤代烷基、环烷基、杂环基、芳基、杂芳基、环烷基烷基、杂环基烷基、芳基烷基或者杂芳基烷基；R任选地被1、2、3、4、5或6个选自R x的取代基所取代；
    Cy为以下子结构式：
    Figure PCTCN2018122505-appb-100002
    或者
    Figure PCTCN2018122505-appb-100003
    R 1和R 22各自独立地为氢、-C(＝O)-(CH 2) n-R 8、-(CH 2) m-C(＝O)-R 8a、-C(＝O)-O-R 9、-C(＝O)-NR 10R 11、-S(＝O) 2-R 12、-S(＝O) 2-NR 13R 14；
    n为0、1、2或3；
    m为1、2或3；
    其中R 8、R 8a、R 9、R 10、R 11、R 12、R 13和R 14各自独立地为氢、烷基、烷氧基烷基、芳基或杂芳基；R 8、R 8a、R 9、R 10、R 11、R 12、R 13和R 14各自独立任选地被1、2、3、4、5或6个选自R y的取代基所取代；
    R 2、R 3、R 4、R 5、R 6和R 7各自独立地为氢、氟、氯、溴、碘、氨基、硝基、氰基、羟基、羧基、烷基、烷氧基、烷硫基或烷基羰基；
    R 33为氢、烷基、烯基、炔基或环烷基；
    R 44为氢、氰基、氟、氯、溴、碘、烷基、烯基、炔基、烷氧基、烷硫基或环烷基；
    R x和R y各自独立地为氟、氯、溴、碘、氨基、硝基、氰基、羟基、羧基、C 1-8烷基、卤代C 1-8烷基、C 2-8烯基、卤代C 2-8烯基、C 2-8炔基、卤代C 2-8炔基、C 1-8烷氧基、卤代C 1-8烷氧基、C 1-8烷氨基、C 1-8烷硫基、卤代C 1-8烷氨基、卤代C 1-8烷硫基、C 6-10芳基、C 6-10芳氧基、C 1-9杂芳基或C 1-9杂芳氧基。
  2. 根据权利要求1所述的化合物，其中
    R为氢、C 1-6烷基、C 2-6烯基、C 2-6炔基、C 1-6烷氧基C 1-6烷基、C 1-6烷氨基C 1-6烷基、C 1-6烷硫基C 1-6烷基、卤代C 1-6烷基、C 3-8环烷基、C 2-8杂环基、C 6-10芳基、C 1-9杂芳基、C 3-8环烷基C 1-6烷基、C 2-8杂环基C 1-6烷基、C 6-10芳基C 1-6烷基或者C 1-9杂芳基C 1-6烷基；R任选地被1、2、3、4、5或6个选自R x的取代基所取代；
    各R x独立地为氟、氯、溴、碘、氨基、硝基、氰基、羟基、羧基、C 1-4烷基、卤代C 1-4烷基、C 2-4烯基、卤代C 2-4烯基、C 2-4炔基、卤代C 2-4炔基、C 1-4烷氧基、卤代C 1-4烷氧基、C 1-4烷氨基、C 1-4烷硫基、卤代C 1-4烷氨基、卤代C 1-4烷硫基、C 6-10芳基、C 6-10芳氧基、C 1-5杂芳基或C 1-5杂芳氧基。
  3. 根据权利要求2所述的化合物，其中
    R为氢、C 1-4烷基、C 2-4烯基、C 2-4炔基、C 1-3烷氧基C 1-3烷基、C 1-3烷氨基C 1-3烷基、C 1-3烷硫基C 1-3烷基、卤代C 1-4烷基、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 1-3烷基、C 2-6杂环基C 1-4烷基、C 6-10芳基C 1-3烷基或者C 1-5杂芳基C 1-3烷基；R任选地被1、2、3、4、5或6个选自R x的取 代基所取代；
    各R x独立地为氟、氯、溴、碘、氨基、硝基、氰基、羟基、羧基、甲基、乙基、正丙基、异丙基、二氟甲基、三氟甲基、甲氧基或三氟甲氧基。
  4. 根据权利要求3所述的化合物，其中
    R为氢、-CH 3、-CH 2CH 3、-CH 2CH 2CH 3、-CH(CH 3) 2、-CF 3、-CH 2CHF 2、-CH 2CF 3、-CH 2OCH 3、-CH 2CH 2OCH 3或-CH 2OCH 2CH 3；
    或者R为以下子结构式：
    Figure PCTCN2018122505-appb-100004
  5. 根据权利要求1所述的化合物，其中
    R 1和R 22各自独立地为氢、-C(＝O)-(CH 2) n-R 8、-(CH 2) m-C(＝O)-R 8a、-C(＝O)-O-R 9、-C(＝O)-NR 10R 11、-S(＝O) 2-R 12、-S(＝O) 2-NR 13R 14；
    n为0、1、2或3；
    m为1、2或3；
    其中R 8、R 8a、R 9、R 10、R 11、R 12、R 13和R 14各自独立地为氢、C 1-6烷基、C 1-6烷氧基C 1-6烷基、C 6-10芳基或C 1-9杂芳基；R 8、R 8a、R 9、R 10、R 11、R 12、R 13和R 14各自独立任选地被1、2、3、4、5或6个选自R y的取代基所取代；
    R 33为氢、C 1-6烷基、C 2-6烯基、C 2-6炔基或C 3-6环烷基；
    R 44为氢、氰基、氟、氯、溴、碘、C 1-6烷基、C 2-6烯基、C 2-6炔基、C 1-6烷氧基、C 1-6烷硫基或C 3-6环烷基；
    各R y独立地为氟、氯、溴、碘、氨基、硝基、氰基、羟基、羧基、C 1-4烷基、卤代C 1-4烷基、C 2-4烯基、卤代C 2-4烯基、C 2-4炔基、卤代C 2-4炔基、C 1-4烷氧基、卤代C 1-4烷氧基、C 1-4烷氨基、C 1-4烷硫基、卤代C 1-4烷氨基、卤代C 1-4烷硫基、C 6-10芳基、C 6-10芳氧基、C 1-5杂芳基或C 1-5杂芳氧基。
  6. 根据权利要求5所述的化合物，其中
    R 1和R 22各自独立地为氢、-C(＝O)-(CH 2) n-R 8或-(CH 2) m-C(＝O)-R 8a；
    n为0、1、2或3；
    m为1、2或3；
    R 33为氢、C 1-4烷基、C 2-4烯基、C 2-4炔基或C 3-6环烷基；
    R 44为氢、氰基、氟、氯、溴、碘、C 1-4烷基、C 2-4烯基、C 2-4炔基、C 1-4烷氧基、C 1-4烷硫基或C 3-6环烷基；
    其中R 8和R 8a各自独立地为氢、C 1-4烷基、C 1-4烷氧基C 1-4烷基、苯基或C 2-3杂芳基；R 8和R 8a各自独立任选地被1、2、3、4、5或6个选自R y的取代基所取代；
    各R y独立地为氟、氯、溴、碘、氨基、硝基、氰基、羟基、羧基、甲基、乙基、正丙基、异丙基、 二氟甲基、三氟甲基、甲氧基或三氟甲氧基。
  7. 根据权利要求6所述的化合物，其中
    R 1和R 22各自独立地为氢、-C(＝O)-(CH 2) n-R 8或-(CH 2) m-C(＝O)-R 8a；
    n为0、1、2或3；
    m为1、2或3；
    R 8和R 8a各自独立地为苯基或吡唑基；R 8和R 8a各自独立任选地被1、2、3、4、5或6个选自R y的取代基所取代；
    各R y独立地为氟、氯、溴、碘、氨基、硝基、氰基、羟基、羧基、甲基、乙基、正丙基、异丙基、二氟甲基、三氟甲基、甲氧基或三氟甲氧基；
    R 33为氢、甲基、乙基、正丙基或异丙基；
    R 44为氢、氰基、氟、氯、溴、碘、甲基、乙基、正丙基、异丙基或环丙基。
  8. 一种化合物，其为具有下列之一结构的化合物或具有下列之一结构化合物的立体异构体、氮氧化物或其盐：
    Figure PCTCN2018122505-appb-100005
    Figure PCTCN2018122505-appb-100006
    Figure PCTCN2018122505-appb-100007
    Figure PCTCN2018122505-appb-100008
    Figure PCTCN2018122505-appb-100009
    或者
    Figure PCTCN2018122505-appb-100010
  9. 一种组合物，包含权利要求1-8任意一项所述的化合物；任选地包含至少一种辅助剂。
  10. 权利要求1-8任意一项所述的化合物或权利要求9所述的组合物在农业中的应用。
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1235600A (zh) * 1996-09-20 1999-11-17 巴斯福股份公司 杂芳酰基衍生物
CA2353572A1 (en) * 1998-12-04 2000-06-15 Basf Aktiengesellschaft Method for producing pyrazolylbenzoyl derivatives and novel pyrazolylbenzoyl derivatives
US7030063B1 (en) * 1998-09-08 2006-04-18 Basf Aktiengesellschaft Cyclohexenonquinolinoyl-derivatives as herbicidal agents

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19638486A1 (de) * 1996-09-20 1998-03-26 Basf Ag Hetaroylderivate

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1235600A (zh) * 1996-09-20 1999-11-17 巴斯福股份公司 杂芳酰基衍生物
US7030063B1 (en) * 1998-09-08 2006-04-18 Basf Aktiengesellschaft Cyclohexenonquinolinoyl-derivatives as herbicidal agents
CA2353572A1 (en) * 1998-12-04 2000-06-15 Basf Aktiengesellschaft Method for producing pyrazolylbenzoyl derivatives and novel pyrazolylbenzoyl derivatives

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