WO2021088856A1 - 一种含取代异恶唑啉的芳香类化合物及其制备方法、除草组合物和应用 - Google Patents

一种含取代异恶唑啉的芳香类化合物及其制备方法、除草组合物和应用 Download PDF

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WO2021088856A1
WO2021088856A1 PCT/CN2020/126434 CN2020126434W WO2021088856A1 WO 2021088856 A1 WO2021088856 A1 WO 2021088856A1 CN 2020126434 W CN2020126434 W CN 2020126434W WO 2021088856 A1 WO2021088856 A1 WO 2021088856A1
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alkyl
cycloalkyl
alkenyl
alkynyl
substituted
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PCT/CN2020/126434
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English (en)
French (fr)
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连磊
彭学岗
华荣保
赵德
崔琦
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青岛清原化合物有限公司
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Priority to CA3160070A priority Critical patent/CA3160070A1/en
Priority to AU2020378483A priority patent/AU2020378483A1/en
Priority to US17/774,814 priority patent/US20230053699A1/en
Priority to EP20884168.4A priority patent/EP4056567A4/en
Priority to BR112022008847A priority patent/BR112022008847A2/pt
Priority to JP2022526303A priority patent/JP2023500353A/ja
Publication of WO2021088856A1 publication Critical patent/WO2021088856A1/zh
Priority to ZA2022/05727A priority patent/ZA202205727B/en

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Classifications

    • 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
    • A01B—SOIL WORKING IN AGRICULTURE OR FORESTRY; PARTS, DETAILS, OR ACCESSORIES OF AGRICULTURAL MACHINES OR IMPLEMENTS, IN GENERAL
    • A01B79/00—Methods for working soil
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01M—CATCHING, TRAPPING OR SCARING OF ANIMALS; APPARATUS FOR THE DESTRUCTION OF NOXIOUS ANIMALS OR NOXIOUS PLANTS
    • A01M21/00—Apparatus for the destruction of unwanted vegetation, e.g. weeds
    • A01M21/04—Apparatus for destruction by steam, chemicals, burning, or electricity
    • A01M21/043—Apparatus for destruction by steam, chemicals, burning, or electricity by chemicals
    • 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
    • A01N43/74—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 1,3
    • 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
    • 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
    • A01P13/02—Herbicides; Algicides selective
    • 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
    • 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 pesticides, and specifically relates to a substituted isoxazoline-containing aromatic compound and a preparation method, herbicidal composition and application thereof.
  • the present invention provides a substituted isoxazoline-containing aromatic compound and a preparation method, herbicidal composition and application thereof.
  • the compound has excellent effects on grass weeds, broadleaf weeds, etc. even at low application rates. It has high herbicidal activity and high selectivity to crops.
  • Y represents halogen, haloalkyl or cyano
  • Z represents halogen
  • Q 1 , Q 2 , Q 3 , Q 4 , Q 5 independently represent O or S;
  • R 1 , R 2 , and R 6 each independently represent hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl or cycloalkylalkyl;
  • R 7 and R 8 each independently represent hydrogen, alkyl, halogen, haloalkyl or amino
  • X 1 and X 2 each independently represent hydrogen, halogen, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkylalkyl, -OR 3 , -(CO)OR 3 or phenyl, wherein the "Alkyl”, “alkenyl”, “alkynyl”, “cycloalkyl” or “cycloalkylalkyl” are each independently unsubstituted or substituted with at least one group selected from halogen;
  • X 3 represents halogen, cyano, formyl, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkylalkyl, -OR 3 , -(CO)OR 3 , -SR 3 , heterocyclyl, hetero Cycloalkyl, aryl, arylalkyl, or amino, and X 3 does not represent a methyl group, wherein,
  • alkyl are each independently unsubstituted or selected from halogen, cyano, -OR 3 , -(CO)R 3 , -SR 3 , -(SO 2 ) R 3 , -O(CO)R 3 , -O-(SO 2 )R 3 , -(CO)OR 3 , -O(CO)OR 3 , -O-alkyl-(CO)OR 3 or -O(CO)(CO)OR 3 substituted by at least one group,
  • cycloalkyl are each independently unsubstituted or Selected from oxo, halogen, cyano, nitro, alkyl, alkenyl, alkynyl, cycloalkyl, haloalkyl, haloalkenyl, haloalkynyl, halocycloalkyl, substituted by alkyl Substituted by at least one of cycloalkyl, -OR 4 , -SR 4 , -(CO)OR 4 , -(SO 2 )R 4 or -N(R 4 ) 2,
  • amino is unsubstituted or substituted with one or two groups selected from -R 3;
  • X 4 each independently represents -COOR 5 or -alkyl-COOR 5 ;
  • R 3 each independently represents hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl or cycloalkylalkyl;
  • R 4 each independently represents hydrogen, alkyl or haloalkyl
  • R 5 each independently represents hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl or cycloalkylalkyl, wherein the "alkyl”, “alkenyl”, “alkynyl”, “cycloalkyl”””Or”cycloalkylalkyl” are each independently unsubstituted or substituted with at least one group selected from halogen.
  • Y represents halogen, halogenated C1-C8 alkyl or cyano
  • R 1 , R 2 , and R 6 each independently represent hydrogen, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 cycloalkyl or C3-C8 cycloalkyl, C1-C8 alkyl ;
  • R 7 and R 8 each independently represent hydrogen, C1-C8 alkyl, halogen, halogenated C1-C8 alkyl or amino;
  • X 1 and X 2 each independently represent hydrogen, halogen, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 cycloalkyl, C3-C8 cycloalkyl, C1-C8 alkyl, -OR 3 , -(CO)OR 3 or phenyl, wherein the "C1-C8 alkyl", “C2-C8 alkenyl”, “C2-C8 alkynyl”, “C3-C8 cycloalkyl” Or "C3-C8 cycloalkyl C1-C8 alkyl" are each independently unsubstituted or substituted with at least one group selected from halogen;
  • X 3 represents halogen, cyano, formyl, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 cycloalkyl, C3-C8 cycloalkyl, C1-C8 alkyl, -OR 3 , -(CO)OR 3 , -SR 3 , heterocyclic group, heterocyclic group C1-C8 alkyl, aryl, aryl C1-C8 alkyl or amino, wherein,
  • C1-C8 alkyl C2-C8 alkenyl or “C2-C8 alkynyl” are each independently unsubstituted or selected from halogen, cyano, -OR 3 , -(CO)R 3 , -SR 3 , -(SO 2 )R 3 , -O(CO)R 3 , -O-(SO 2 )R 3 , -(CO)OR 3 , -O(CO)OR 3 , -O- (C1-C8 alkyl)-(CO)OR 3 or -O(CO)(CO)OR 3 substituted by at least one group,
  • C3-C8 cycloalkyl is each independently unsubstituted or selected from oxo, halogen, cyano, nitro, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 ring Alkyl, halo C1-C8 alkyl, halo C2-C8 alkenyl, halo C2-C8 alkynyl, halo C3-C8 cycloalkyl, C3-C8 cycloalkyl substituted by C1-C8 alkyl , -OR 4 , -SR 4 , -(CO)OR 4 , -(SO 2 )R 4 or -N(
  • amino is unsubstituted or substituted with one or two groups selected from -R 3;
  • X 4 each independently represents -COOR 5 or -(C1-C8 alkyl)-COOR 5 ;
  • R 3 each independently represents hydrogen, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 cycloalkyl or C3-C8 cycloalkyl, C1-C8 alkyl;
  • R 4 each independently represents hydrogen, C1-C8 alkyl or halo C1-C8 alkyl
  • R 5 each independently represents hydrogen, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 cycloalkyl or C3-C8 cycloalkyl C1-C8 alkyl, wherein said " C1-C8 alkyl”, “C2-C8 alkenyl”, “C2-C8 alkynyl”, “C3-C8 cycloalkyl” or “C3-C8 cycloalkyl C1-C8 alkyl” are each independently Substituted or substituted with at least one group selected from halogen.
  • Y represents halogen, halogenated C1-C6 alkyl or cyano
  • R 1 , R 2 , and R 6 each independently represent hydrogen, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl or C3-C6 cycloalkyl, C1-C6 alkyl ;
  • R 7 and R 8 each independently represent hydrogen, C1-C6 alkyl, halogen, halogenated C1-C6 alkyl or amino;
  • X 1 and X 2 each independently represent hydrogen, halogen, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, C3-C6 cycloalkyl, C1-C6 alkyl, -OR 3 , -(CO)OR 3 or phenyl, wherein the "C1-C6 alkyl", “C2-C6 alkenyl”, “C2-C6 alkynyl", “C3-C6 cycloalkyl” Or "C3-C6 cycloalkyl C1-C6 alkyl" are each independently unsubstituted or substituted with at least one group selected from halogen;
  • X 3 represents halogen, cyano, formyl, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, C3-C6 cycloalkyl, C1-C6 alkyl, -OR 3 , -(CO)OR 3 , -SR 3 , heterocyclic group, heterocyclic group C1-C6 alkyl, aryl, aryl C1-C6 alkyl or amino, wherein,
  • C1-C6 alkyl C2-C6 alkenyl or “C2-C6 alkynyl” are each independently unsubstituted or selected from halogen, cyano, -OR 3 , -(CO)R 3 , -SR 3 , -(SO 2 )R 3 , -O(CO)R 3 , -O-(SO 2 )R 3 , -(CO)OR 3 , -O(CO)OR 3 , -O- (C1-C6 alkyl)-(CO)OR 3 or -O(CO)(CO)OR 3 substituted by at least one group,
  • C3-C6 cycloalkyl is each independently unsubstituted or selected from oxo, halogen, cyano, nitro, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 ring Alkyl, halo C1-C6 alkyl, halo C2-C6 alkenyl, halo C2-C6 alkynyl, halo C3-C6 cycloalkyl, C3-C6 cycloalkyl substituted by C1-C6 alkyl , -OR 4 , -SR 4 , -(CO)OR 4 , -(SO 2 )R 4 or -N(
  • amino is unsubstituted or substituted with one or two groups selected from -R 3;
  • X 4 each independently represents -COOR 5 or -(C1-C6 alkyl)-COOR 5 ;
  • R 3 each independently represents hydrogen, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl or C3-C6 cycloalkyl, C1-C6 alkyl;
  • R 4 each independently represents hydrogen, C1-C6 alkyl or halo C1-C6 alkyl
  • R 5 each independently represents hydrogen, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl or C3-C6 cycloalkyl C1-C6 alkyl, wherein said " C1-C6 alkyl”, “C2-C6 alkenyl”, “C2-C6 alkynyl”, “C3-C6 cycloalkyl” or “C3-C6 cycloalkyl C1-C6 alkyl” are each independently Substituted or substituted with at least one group selected from halogen.
  • Y represents halogen
  • R 1 , R 2 , and R 6 each independently represent a C1-C6 alkyl group
  • R 7 and R 8 each independently represent hydrogen or a halogenated C1-C6 alkyl group
  • X 1 and X 2 each independently represent hydrogen
  • X 3 represents halogen, formyl, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, C3-C6 cycloalkyl, C1-C3 alkyl, -OR 3 , benzene Benzyl or benzyl, where
  • C1-C6 alkyl C2-C6 alkenyl
  • C2-C6 alkynyl are each independently unsubstituted or selected from halogen, -OR 3 , -O(CO)R 3 , -(CO)OR 3 , -O-(C1-C3 alkyl)-(CO)OR 3 or -O(CO)(CO)OR 3 substituted by 1, 2, or 3 groups,
  • C3-C6 cycloalkyl is each independently unsubstituted or selected from halogen, C1-C6 Alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, halogenated C1-C6 alkyl, halogenated C2-C6 alkenyl, halogenated C2-C6 alkynyl, halogenated C3- C6 cycloalkyl, C3-C6 cycloalkyl substituted with C1-C6 alkyl, substituted with 1, 2, or 3 groups in -OR 4 or -(CO)OR 4;
  • X 4 independently represents -COOR 5 ;
  • R 3 each independently represents hydrogen, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl or C3-C6 cycloalkyl, C1-C3 alkyl;
  • R 4 each independently represents hydrogen, C1-C6 alkyl or halo C1-C6 alkyl
  • R 5 each independently represents hydrogen, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl or C3-C6 cycloalkyl.
  • Y represents chlorine
  • R 7 represents a halogenated C1-C6 alkyl group
  • R 8 represents hydrogen
  • X 3 represents halogen, formyl, C1-C6 alkyl, C3-C6 cycloalkyl, C3-C6 cycloalkyl, C1-C3 alkyl, -OR 3 , -(C1-C3 alkyl) -OR 3 ,- (C1-C3 alkyl)-O(CO)R 3 , -(C1-C3 alkyl)-(CO)OR 3 , -(C1-C3 alkyl)-O-(C1-C3 alkyl)-( CO)OR 3 , -(C1-C3 alkyl)-O(CO)(CO)OR 3 , phenyl or benzyl, wherein,
  • C1-C6 alkyl is each independently unsubstituted or substituted with 1, 2, or 3 groups selected from halogen;
  • R 3 each independently represents hydrogen or C1-C6 alkyl
  • R 5 each independently represents hydrogen or C1-C6 alkyl.
  • Q represents
  • alkyl groups with more than two carbon atoms can be straight-chain or branched Chained.
  • alkyl group can be -CH 2 -, -CH 2 CH 2 -, -CH(CH 3 )-, -C(CH 3 ) 2 -, etc.
  • Alkyl groups are, for example, C1 alkyl-methyl; C2 alkyl-ethyl; C3 alkyl-propyl such as n-propyl or isopropyl; C4 alkyl-butyl such as n-butyl, isobutyl Alkyl, tert-butyl or 2-butyl; C5 alkyl-pentyl such as n-pentyl; C6 alkyl-hexyl such as n-hexyl, isohexyl and 1,3-dimethylbutyl.
  • alkenyl groups are, for example, vinyl, allyl, 1-methylprop-2-en-1-yl, 2-methylprop-2-en-1-yl, but-2-en-1-yl Group, but-3-en-1-yl, 1-methylbut-3-en-1-yl and 1-methylbut-2-en-1-yl.
  • Alkynyl is, for example, ethynyl, propargyl, but-2-yn-1-yl, but-3-yn-1-yl, 1-methylbut-3-yn-1-yl.
  • the multiple bonds can be in any position of each unsaturated group.
  • Cycloalkyl is a carbocyclic saturated ring system having, for example, three to six carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl, or cyclohexyl.
  • a cycloalkenyl group is a monocyclic alkenyl group having, for example, three to six carbon ring members, such as cyclopropenyl, cyclobutenyl, cyclopentenyl, and cyclohexenyl, where the double bond can be in any position.
  • Halogen is fluorine, chlorine, bromine or iodine.
  • the "aryl” in the present invention includes but is not limited to phenyl, naphthyl,
  • the "heterocyclic group” not only includes but is not limited to saturated or unsaturated non-aromatic cyclic groups Etc., also include, but are not limited to, heteroaryl groups, that is, aromatic cyclic groups containing, for example, 3 to 6 ring atoms and optionally having benzo ring fused, 1 to 4 of the ring atoms ( For example 1, 2, 3 or 4) heteroatoms are selected from oxygen, nitrogen and sulfur, such as
  • a group is substituted by a group, this should be understood to mean that the group is substituted by one or more identical or different groups selected from those mentioned.
  • the same or different substitution characters contained in the same or different substituents are all independently selected and may be the same or different. The same applies to ring systems formed by different atoms and units. At the same time, the scope of the claims will exclude those compounds known to those skilled in the art that are chemically unstable under standard conditions.
  • the "replaced by at least one group" in the present invention means that it is substituted by 1, 2, 3, 4 or 5 groups; groups (including hetero The cyclic group, aryl group, etc.) can be connected at any position, including the position connected to C or N; if it is substituted, the substituent can also be substituted at any position, as long as it conforms to the bonding rules.
  • groups including hetero The cyclic group, aryl group, etc.
  • the substituent can also be substituted at any position, as long as it conforms to the bonding rules.
  • Such as heteroaryl substituted by 1 methyl Can represent Wait.
  • the carbon atom (C*) connected to X 3 and X 4 is a chiral center (that is, when X 3 and X 4 are not the same), it is in R configuration or S configuration, preferably S configuration, based on the In terms of the content of stereoisomers with R and S configurations in position, it has a stereochemical purity of 60-100% (S), preferably 70-100% (S), more preferably 80-100% (S), It is more preferably 90-100% (S), and still more preferably 95-100% (S).
  • stereochemical purity refers to the percentage of the amount of said stereoisomers in the total amount of stereoisomers having chiral centers.
  • the present invention also provides a substituted isoxazoline-containing aromatic compound having an S configuration, as shown in the general formula I':
  • X 3 ′ represents hydrogen, methyl or X 3
  • the definitions of the substituents X 1 , X 2 , X 3 , X 4 , Q, Y, and Z are as described above, and X 3 and X 4 are different.
  • the stereochemical configuration at the position marked with * in formula I and formula I' is determined as the main (S) according to the Cahn-Ingold-Prelog system.
  • the subject of the present invention also relates to formula I and formula All stereoisomers in other positions included in I', and mixtures thereof.
  • the present invention includes pure isomers and mixtures of enriched pure isomers with different degrees, wherein the asymmetric carbon atom at the position marked * is in the S-configuration, or in the mixture,
  • the compound or the compound of the same chemical structure has S-configuration at the position marked *, or exists in a proportion that mainly has the S-configuration compound (at least 60% S-configuration), and other asymmetric carbons Atoms can exist in racemic form, or they can be resolved to varying degrees.
  • the possible stereoisomers defined by the specific spatial form such as enantiomers, diastereomers, Z- and E-
  • the isomers are all included in Formula I and Formula I', and can be obtained from a mixture of stereoisomers by conventional methods, or can also be prepared by a stereoselective reaction in combination with a stereochemically pure starting material.
  • the present invention also includes any ketone and enol tautomeric forms and mixtures and salts thereof.
  • Stereoisomers can be obtained from the mixture obtained in the preparation by optical resolution. It is also possible to selectively prepare stereoisomers by using stereoselective reactions and using optically active starting materials and/or auxiliary agents.
  • optical resolution conventional methods (see Textbooks ofStereochemistry) can usually be used, for example, the following methods used to resolve mixtures into diastereoisomers, such as physical methods, such as crystallization, chromatography, especially Column chromatography and high pressure liquid chromatography, distillation methods carried out under reduced pressure, extraction methods and other methods, usually using chromatographic separation on a chiral solid phase, can separate the residual mixture of enantiomers.
  • Suitable for production quantities or on an industrial scale are methods such as crystalline diastereomeric salts, which can be obtained from compounds using optically active acids, and if acidic groups are present, optically active bases can be used as needed.
  • the preparation method of the aromatic compound containing substituted isoxazoline includes the following steps:
  • L 1 , L 2 , L 3 , L 4 , L 5 , L 6 and L 7 each independently represent a C1-C6 alkyl or aryl group, preferably methyl, ethyl or phenyl; Hal represents halogen, preferably iodo; R 6 'Representative 6 R groups are other than hydrogen; the other substituents R 1, R 2, R 6 , R 7, R 8, X 1, X 2, X 3, X 4, Q 1, Q 2.
  • the definitions of Q 3 , Q 4 , Q 5 , Y and Z are as described above.
  • the steps (1), (2), (4) and (5) are all carried out in the presence of a base and a solvent.
  • the base is selected from inorganic bases (such as K 2 CO 3 , Na 2 CO 3 , Cs 2 CO 3 , NaHCO 3 , KF, CsF, KOAc, AcONa, K 3 PO 4 , t-BuONa, EtONa, NaOH, KOH, At least one of NaOMe, etc.) or organic bases (such as pyrazole, triethylamine, DIEA, etc.).
  • inorganic bases such as K 2 CO 3 , Na 2 CO 3 , Cs 2 CO 3 , NaHCO 3 , KF, CsF, KOAc, AcONa, K 3 PO 4 , t-BuONa, EtONa, NaOH, KOH, At least one of NaOMe, etc.
  • organic bases such as pyrazole, triethylamine, DIEA, etc.
  • the solvent is selected from at least one of DMF, DMA, methanol, ethanol, acetonitrile, dichloroethane, DMSO, Dioxane, dichloromethane or ethyl acetate.
  • the step (3) is carried out in the presence of an acid.
  • the acid is selected from acetic acid, hydrochloric acid or sulfuric acid.
  • Q when at least one of the substituents Q 1 , Q 2 , and Q 3 is S or Q 4 , and at least one of Q 5 is S, it can also be represented by the corresponding Q Lawson reagent Or the conventional sulfur substitution reaction in the presence of phosphorus pentasulfide.
  • the compounds of the present invention are also prepared by referring to related methods described in patents WO00/50409, CN105753853A and the like.
  • a herbicidal composition which comprises a herbicidal effective amount of at least one of the aromatic compounds containing substituted isoxazolines, and preferably, further comprises a formulation adjuvant.
  • a method for controlling weeds which comprises applying a herbicidal effective amount of at least one of the substituted isoxazoline-containing aromatic compounds or the herbicide composition on plants or weed areas.
  • At least one of the aromatic compounds containing substituted isoxazoline or the use of the herbicide composition in controlling weeds preferably, the aromatic compounds containing substituted isoxazoline
  • the compound is used to control weeds in useful crops, which are genetically modified crops or crops processed by genome editing technology.
  • the compounds of formula I and formula I'of the present invention have outstanding herbicidal activity.
  • the active substance of the present invention is also effective against perennial weeds, which grow from rhizomes, rhizomes, or other perennial organs, which are difficult to control. In this regard, it is generally not important whether the substance is used before sowing, before germination or after germination. Special mention is made of representative examples of monocotyledonous and dicotyledonous weed groups that can be controlled by the compounds of the present invention, and there is no limitation to certain species.
  • weed species in which the active substance effectively acts include monocots: annual oats, rye, grass, sylvestris, fararis, barnyard, crabgrass, setaria and cyperus, and perennial ice Grass genus, bermudagrass, cyperus and sorghum, and perennial Cyperus.
  • the active substance of the present invention effectively controls harmful plants such as barnyard, Aquilaria, Alisma, water chestnut, saccharum and Cyperus under the undetermined condition of rice seeding.
  • the seedling of weeds can be prevented completely before the weeds grow, or the growth of the weeds can be stopped when the weeds grow cotyledons, and finally die completely after three to four weeks.
  • the compound of the present invention has particularly excellent activity against the following plants, such as Apilagrass, Small wild sesame seeds, Polygonum vulgare, Chrysanthemum vulgaris, Ivy Leaf Panna, Arabian Panna, Pansy and Amaranth, Asparagus and Kochia .
  • the compound of the present invention has excellent herbicidal activity on monocot and dicot weeds, it has no harm to important economic crop plants such as wheat, barley, rye, rice, corn, sugar beet, cotton and soybean. , Or the damage is trivial. Especially compatible with cereal crops, such as wheat, barley and corn, especially wheat. Therefore, the compound of the present invention is very suitable for the selective control of useless plants in agricultural crops or ornamental plants.
  • Transgenic plants Due to their herbicidal properties, these active substances can be used to control harmful plants in known or upcoming genetic engineering plant cultivation.
  • Transgenic plants usually have superior characteristics, such as resistance to specific insecticides, especially specific herbicides, resistance to plant diseases or pathogenic microorganisms of plant diseases, such as specific insects or fungi, bacteria or virus microorganisms.
  • Other special characteristics are related to the following conditions of the product, such as quantity, quality, storage stability, composition and special ingredients. As such, it is known that the obtained transgenic plant product has an increased starch content or an improved starch quality or a different fatty acid composition.
  • the compounds of formula I and formula I'or their salts of the present invention are preferably used in economically important transgenic crops and ornamental plants, such as cereals, such as wheat, barley, rye, oats, millet, rice, cassava and corn, or It is used for the cultivation of sugar beet, cotton, soybean, rapeseed, potato, tomato, peas and other vegetable plants.
  • the compounds of formula I and formula I' are preferably used as herbicides for the cultivation of useful plants, which are resistant to herbicides or are resistant to the toxic effects of herbicides through genetic engineering.
  • genetic engineering is used to change crop plants (for example, WO 92/11376, WO 92/14827, WO 91/19806);
  • substrates can be exchanged, partial sequences can be removed, or natural or synthetic sequences can be added.
  • substrates can be exchanged, partial sequences can be removed, or natural or synthetic sequences can be added.
  • a binder or linker In order to connect the DNA fragments to each other, it is possible to attach a binder or linker to the fragments.
  • the following methods can be used to prepare plant cells of gene products with reduced activity, for example, by expressing at least one appropriate antisense-RNA, sense-RNA to achieve the co-suppression effect, or by expressing at least one appropriately structured ribozyme, It specifically cleaves the transcription products of the above gene products.
  • DNA molecules that contain the entire coding sequence of the gene product including any flanking sequences that may be present, and use DNA molecules that contain only a portion of the coding sequence, these portions must be long enough to achieve antisense in the cell Effect. It is also possible to use sequences that have a high degree of homology with the coding sequence of the gene product but are not completely identical.
  • the synthesized protein When expressing nucleic acid molecules in plants, the synthesized protein can be localized in any desired plant cell compartment. However, for positioning in a specific chamber, it is possible, for example, to link the coding region and DNA sequence to ensure positioning in a specific location. These sequences are known to those skilled in the art (see, for example, 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).
  • transgenic plant cells can be recombined into whole plants.
  • the active substance of the present invention when used on genetically modified crops, in addition to the effect of inhibiting harmful plants that can be observed on other crops, it often has special effects on the corresponding genetically modified crops, for example, the control can be improved or expanded
  • the compounds of the present invention can significantly regulate the growth of crop plants. By regulating the involvement of plant metabolism, these compounds are used to control plant components and promote harvest, such as drying and stunting growth of plants. And they are also suitable for regulating and inhibiting the growth of undesirable plants without destroying the growth of crops. Inhibiting plant growth plays a very important role in many monocotyledonous and dicotyledonous crops because it can reduce or completely prevent lodging.
  • the present invention also provides herbicidal compositions comprising compounds of formula I and formula I'. According to general biological and/or chemical physical parameters, the compounds of formula I and formula I'can be formulated in a variety of ways.
  • Suitable formulation options are: wettable powder (WP), water-soluble powder (SP), water-soluble concentrate, concentrated emulsion (EC), such as oil-in-water dispersion and water-in-oil dispersion (EW) , Sprayable solution, suspension concentrate (SC), dispersible oil suspension (OD), suspension with oil or water as diluent, miscible oil solution, powder (DP), capsule suspension (CS ), seeddressing composition, granules for broadcasting and soil application, spray granules, coated granules and absorption granules, water dispersible granules (WG), water-soluble granules (SG), ULV (ultra Low-volume) formulations, microcapsules and wax products.
  • WP wettable powder
  • SP water-soluble powder
  • EC concentrated emulsion
  • EW oil-in-water dispersion and water-in-oil dispersion
  • SC suspension concentrate
  • OD dispersible oil suspension
  • DP dispersible
  • Wettable powders can be uniformly dispersed in water.
  • active substances they also include diluents or inert substances, ionic and non-ionic surfactants (wetting agents, dispersants), such as polyethoxyalkylphenols, poly Ethoxylated fatty alcohol, polyoxyethyl aliphatic amine, fatty alcohol polyglycol ether sulfate, alkyl sulfonate, alkyl phenyl sulfonate, sodium lignosulfonate, 2,2'-dinaphthyl methane -6,6'-Sodium disulfonate, sodium dibutyl naphthalene sulfonate or sodium oleoyl methyl taurate.
  • the active substance of the herbicide is finely ground, for example, using commonly used equipment such as a hammer mill, a fan mill and a jet mill, and the additives are mixed in simultaneously or sequentially
  • emulsifiers Dissolve the active substance in an organic solvent to prepare a concentrated emulsion, such as butanol, cyclohexanone, dimethylformamide, xylene, or a mixture of higher boiling aromatic compounds or hydrocarbons or solvents, and add another One or more ionic and/or non-ionic surfactants (emulsifiers).
  • emulsifiers that can be used are calcium alkylarylsulfonates such as calcium dodecylbenzenesulfonate, or nonionic emulsifiers such as fatty acid polyglycol esters, alkyl aromatic polyglycol ethers, and fatty alcohols.
  • Polyglycol ethers propylene oxide-ethylene oxide condensation products, alkyl polyethers, sorbitan esters such as sorbitan fatty acid esters, or polyoxyethylene sorbitans such as polyoxyethylene sorbitan fatty esters Glycan ester.
  • the active material and the finely divided solid material are ground to obtain a powder, such as talc, natural clay such as kaolin, bentonite and pyrophyllite, or diatomaceous earth.
  • a powder such as talc, natural clay such as kaolin, bentonite and pyrophyllite, or diatomaceous earth.
  • the water or oil-based suspension can be prepared by the following method, for example, wet grinding with a commercially available glass bead mill, with or without addition of the above-mentioned other formulation type surfactant.
  • an aqueous organic solvent can be used, a stirrer, a colloid mill, and/or a static mixer can be used, and if necessary, a surfactant of another formulation type as described above can be added.
  • the granules are prepared by the following method.
  • the active substance is sprayed onto the adsorbent, granulated with inert materials, or the active substance is concentrated on the surface of a carrier such as sand or kaolin, and the inert materials are granulated through a binder.
  • Mixtures such as polyvinyl alcohol, sodium polyacrylate or mineral oil.
  • the method of preparing fertilizer granules can be used to granulate suitable active substances, and fertilizers can be mixed if necessary. Use the usual methods to prepare water suspension granules, such as spray-drying, fluidized bed granulation, grinding disc granulation, mixing using a high-speed mixer, and extruding without solid inert materials.
  • Agrochemical preparations usually contain 0.1 to 99% by weight, especially 0.1 to 95% of the active substances of formula I and formula I'.
  • the concentration of the active substance in the wettable powder is, for example, from about 10 to 99% by weight, and the usual formulation components constitute the remaining amount by weight to 100%.
  • the concentration of the active substance in the concentrated emulsion may be about 1 to 90% by weight, preferably 5 to 80%.
  • Powder formulations contain 1 to 30% by weight of active substance, usually preferably 5 to 20% by weight of active substance, while sprayable solutions contain about 0.05 to 80% by weight, preferably 2 to 50% by weight of active substance .
  • the content of active material in water suspended granules is mainly based on whether the active material is liquid or solid, and the additives, fillers, etc. used in granulation.
  • the content of the active substance in the water-suspended granules is, for example, between 1 and 95% by weight, preferably between 10 and 80% by weight.
  • the formulation of the active substance may include thickeners, wetting agents, dispersants, emulsifiers, penetrants, preservatives, antifreeze agents, solvents, fillers, carriers, colorants, defoamers, evaporation inhibitors and PH and viscosity modifiers commonly used in all situations.
  • the mixing method can be It is pre-mixed or filled and mixed.
  • suitable active substances that can be mixed with the active substance of the present invention are, for example, "Encyclopedia of World Pesticide New Variety Technologies", China Agricultural Science and Technology Press, 2010.9 and the literature cited here Known substance.
  • the herbicide active substances mentioned below can be mixed with the mixture of formula I and formula I', (Note: the name of the compound, or the common name according to the International Organization for Standardization (ISO), or the chemical name, with a code when appropriate ): Acetochlor, Butachlor, Alachlor, Propolachlor, Metolachlor, Refined Metolachlor, Pretilachlor, Tetrachlor, Mesochlor, Napropionate, R -Levo-naphthylpropion, propanil, mefenacet, difenacet, diflufenican, chlorfenazone, flubutazone, bromobutyramide, dimethenamid , High-efficiency dimethenamid, ethoxyfenacet, flufenacet, metolachlor, metazachlor, clomazone, high-efficiency methenamid, high-efficiency methenamid, dipropion , Clethachlor, butachlor
  • the commercially available formulations are diluted in a usual manner, for example, in wettable powders, concentrated emulsions, suspensions, and particles suspended in water, diluted with water. Powders, granules used for soil application, or solutions for broadcasting and spraying, generally do not need to be further diluted with inert substances before use.
  • the external conditions change, the required usage amounts of the compounds of formula I and formula I'are also different.
  • the external conditions are, for example, temperature, humidity, the nature of the herbicide used, and so on. It can have a large variation range, for example, between 0.001 and 1.0kg ai/ha, or more active substances, but preferably between 0.005 and 750g ai/ha, especially between 0.005 and 250g ai/ha .
  • Table A has the same structure as Table 1 above, except that there will be a chiral center (where the carbon atom (C*) connected to X 3 and X 4 is the chiral center, that is, when X 3 and X 4 are not the same) racemate compounds (ie, compounds 1-50, 52-90, 92-93, 95-152, 154-192, 194-195 and 197-236) are replaced with the corresponding S configuration and the corresponding position without chiral center is deleted.
  • C* carbon atom
  • the activity level standards for plant destruction (that is, growth control rate) are as follows:
  • Level 5 The growth control rate is above 85%;
  • Level 4 The growth control rate is greater than or equal to 60% and less than 85%;
  • Level 3 The growth control rate is greater than or equal to 40% and less than 60%;
  • Level 2 The growth control rate is greater than or equal to 20% and less than 40%;
  • Level 1 The growth control rate is greater than or equal to 5% and less than 20%;
  • Grade 0 The growth control rate is less than 5%.
  • the above growth control rate is the fresh weight control rate.
  • the monocot and dicot weed seeds (artemisia sowing, shepherd's purse, abutilon, pig stalk, chickweed, Maijiagong, ginseng, Kan Mai Niang, Japanese Kan Mai Niang, gooseberry, calamus, hard Grass, Scabious, candle grass, mother-in-law, brome, japonicum, Phalaris arundinacea, amaranthus, quinoa, Commelina vulgaris, cocory, field bindweed, seaweed, nightshade, amaranth, horse Tang, barnyard grass, green bristlegrass, golden foxtail, stephen's gold, duck's tongue, wild scorpion, firefly, cyperus rotundus, cardamine sedge, alien sedge, fluttering grass, purslane, cocklebur, morning glory, white wine Grass, etc.) and the main crop seeds (wheat, corn, rice, soybean, cotton, rape, millet, sorghum, potato, ses
  • test plants were treated at the 2-3 leaf stage.
  • the tested compounds of the present invention were dissolved in acetone, and then Tween 80 was added at a rate of 1.5 liters/ha.
  • Emulsifiable concentrate of ester is used as a synergist, diluted with a certain amount of water into a certain concentration solution, and sprayed on the plants with a spray tower.
  • the experimental effects of the weeds were counted after 3 weeks of cultivation in the greenhouse.
  • the compound used was 500, 250, 125, 60, 15, 7.5 g a.i./ha, repeated three times, and the average value was taken. Representative data are listed in Table 2-6.
  • N no data
  • control compound A Control compound B:
  • the tested compound of the present invention was dissolved in acetone, then added with Tween 80, diluted with a certain amount of water to a certain concentration solution, and sprayed immediately after sowing. After applying the pesticide, it was cultured in the greenhouse for 4 weeks and the experimental results were observed. It was found that most of the agents of the present invention have an excellent effect under the measurement of 250g ai/ha, especially for weeds such as barnyardgrass, crabgrass, and abutilon. Wheat, rice, soybeans have good selectivity.
  • the compound of the present invention generally has a good weed control effect, especially we have noticed that the ALS inhibitors are resistant to ALS inhibitors, such as wild rushes, rushes, and heteromorphs.
  • Broadleaf weeds such as Cyperus sedge, Artemisia spp, Shepherd's Purse, Maijiagong, Zhushan, Cyperus rotundus, and Cyperus sedge have extremely high activity and have very good commercial value.
  • the three-leaf stage rice (japonica rice) is transplanted at a transplanting depth of 3 cm.
  • the compound of the present invention was treated in the same manner as above on the 5th day after transplantation.

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Abstract

属于农药技术领域，具体涉及一种含取代异恶唑啉的芳香类化合物及其制备方法、除草组合物和应用。所述化合物如通式（I）所示，其中，Q代表式（II）或式（II）；Y代表卤素、卤代烷基或氰基；Z代表卤素；X 1、X 2分别独立地代表氢、卤素、烷基等；X 3代表卤素、氰基等；X 4分别独立地代表-COOR 5或-烷基-COOR 5；R 5分别独立地代表氢、烷基等。所述化合物即使在低施用率下对禾本科杂草、阔叶杂草等也具有优异的除草活性，并对作物具有高选择性。

Description

一种含取代异恶唑啉的芳香类化合物及其制备方法、除草组合物和应用 技术领域
本发明属于农药技术领域，具体涉及一种含取代异恶唑啉的芳香类化合物及其制备方法、除草组合物和应用。
背景技术
杂草的防治是实现高效农业过程中一个至关重要的环节，尽管市场上的除草剂种类多样，比如专利WO00/50409等公开了通式化合物1-芳基-4-硫代三嗪作为除草剂的用途；CN105753853A公开了一种含异恶唑啉的脲嘧啶类化合物及其作为除草剂的用途。然而，这些已知化合物对有害植物的除草性能和对作物的选择性并不完全令人满意。且由于市场的不断扩大、杂草的抗性、药物的使用寿命以及药物的经济性等问题以及人们对环境的日益重视，需要科学家们不断研究进而开发出新的高效、安全、经济以及具有不同作用方式的除草剂品种。
发明内容
本发明提供了一种含取代异恶唑啉的芳香类化合物及其制备方法、除草组合物和应用，所述化合物即使在低施用率下对禾本科杂草、阔叶杂草等也具有优异的除草活性，并对作物具有高选择性。
本发明采用的技术方案如下：
一种含取代异恶唑啉的芳香类化合物，如通式I所示：
Figure PCTCN2020126434-appb-000001
其中，
Q代表
Figure PCTCN2020126434-appb-000002
Y代表卤素、卤代烷基或氰基；
Z代表卤素；
Q 1、Q 2、Q 3、Q 4、Q 5分别独立地代表O或S；
R 1、R 2、R 6分别独立地代表氢、烷基、烯基、炔基、环烷基或环烷基烷基；
R 7、R 8分别独立地代表氢、烷基、卤素、卤代烷基或氨基；
X 1、X 2分别独立地代表氢、卤素、烷基、烯基、炔基、环烷基、环烷基烷基、-OR 3、-(CO)OR 3或苯基，其中，所述“烷基”、“烯基”、“炔基”、“环烷基”或“环烷基烷基”分别独立地是未取代的或被选自卤素中的至少一个基团所取代的；
X 3代表卤素、氰基、甲酰基、烷基、烯基、炔基、环烷基、环烷基烷基、-OR 3、-(CO)OR 3、-SR 3、杂环基、杂环基烷基、芳基、芳基烷基或氨基，且X 3不代表甲基，其中，
所述“烷基”、“烯基”或“炔基”分别独立地是未取代的或被选自卤素、氰基、-OR 3、-(CO)R 3、-SR 3、-(SO 2)R 3、-O(CO)R 3、-O-(SO 2)R 3、-(CO)OR 3、-O(CO)OR 3、-O-烷基-(CO)OR 3或-O(CO)(CO)OR 3中的至少一个基团所取代的，
所述“环烷基”、“环烷基烷基”、“杂环基”、“杂环基烷基”、“芳基”或“芳基烷基”分别独立地是未取代的或被选自氧代、卤素、氰基、硝基、烷基、烯基、炔基、环烷基、卤代烷基、卤代烯基、卤代炔基、卤代环烷基、被烷基取代的环烷基、-OR 4、-SR 4、-(CO)OR 4、-(SO 2)R 4或-N(R 4) 2中的至少一个基团所取代的，
所述“氨基”是未取代的或被选自-R 3中的一个或两个基团所取代的；
X 4分别独立地代表-COOR 5或-烷基-COOR 5；
R 3分别独立地代表氢、烷基、烯基、炔基、环烷基或环烷基烷基；
R 4分别独立地代表氢、烷基或卤代烷基；
R 5分别独立地代表氢、烷基、烯基、炔基、环烷基或环烷基烷基，其中，所述“烷基”、“烯基”、“炔基”、“环烷基”或“环烷基烷基”分别独立地是未取代的或被选自卤素中的至少一个基团所取代的。
优选地，Y代表卤素、卤代C1-C8烷基或氰基；
R 1、R 2、R 6分别独立地代表氢、C1-C8烷基、C2-C8烯基、C2-C8炔基、C3-C8环烷基或C3-C8环烷基C1-C8烷基；
R 7、R 8分别独立地代表氢、C1-C8烷基、卤素、卤代C1-C8烷基或氨基；
X 1、X 2分别独立地代表氢、卤素、C1-C8烷基、C2-C8烯基、C2-C8炔基、C3-C8环烷基、C3-C8环烷基C1-C8烷基、-OR 3、-(CO)OR 3或苯基，其中，所述“C1-C8烷基”、“C2-C8烯基”、“C2-C8炔基”、“C3-C8环烷基”或“C3-C8环烷基C1-C8烷基”分别独立地是未取代的或被选自卤素中的至少一个基团所取代的；
X 3代表卤素、氰基、甲酰基、C1-C8烷基、C2-C8烯基、C2-C8炔基、C3-C8环烷基、C3-C8环烷基C1-C8烷基、-OR 3、-(CO)OR 3、-SR 3、杂环基、杂环基C1-C8烷基、芳基、芳基C1-C8烷基或氨基，其中，
所述“C1-C8烷基”、“C2-C8烯基”或“C2-C8炔基”分别独立地是未取代的或被选自卤素、氰基、-OR 3、-(CO)R 3、-SR 3、-(SO 2)R 3、-O(CO)R 3、-O-(SO 2)R 3、-(CO)OR 3、-O(CO)OR 3、-O-(C1-C8烷基)-(CO)OR 3或-O(CO)(CO)OR 3中的至少一个基团所取代的，
所述“C3-C8环烷基”、“C3-C8环烷基C1-C8烷基”、“杂环基”、“杂环基C1-C8烷基”、“芳基”或“芳基C1-C8烷基”分别独立地是未取代的或被选自氧代、卤素、氰基、硝基、C1-C8烷基、C2-C8烯基、C2-C8炔基、C3-C8环烷基、卤代C1-C8烷基、卤代C2-C8烯基、卤代C2-C8炔基、卤代C3-C8环烷基、被C1-C8烷基取代的C3-C8环烷基、-OR 4、-SR 4、-(CO)OR 4、-(SO 2)R 4或-N(R 4) 2中的至少一个基团所取代的，
所述“氨基”是未取代的或被选自-R 3中的一个或两个基团所取代的；
X 4分别独立地代表-COOR 5或-(C1-C8烷基)-COOR 5；
R 3分别独立地代表氢、C1-C8烷基、C2-C8烯基、C2-C8炔基、C3-C8环烷基或C3-C8环烷基C1-C8烷基；
R 4分别独立地代表氢、C1-C8烷基或卤代C1-C8烷基；
R 5分别独立地代表氢、C1-C8烷基、C2-C8烯基、C2-C8炔基、C3-C8环烷基或C3-C8环烷基C1-C8烷基，其中，所述“C1-C8烷基”、“C2-C8烯基”、“C2-C8炔基”、“C3-C8环烷基”或“C3-C8环烷基C1-C8烷基”分别独立地是未取代的或被选自卤素中的至少一个基团所取代的。
更优选地，Y代表卤素、卤代C1-C6烷基或氰基；
R 1、R 2、R 6分别独立地代表氢、C1-C6烷基、C2-C6烯基、C2-C6炔基、C3-C6环烷基或C3-C6环烷基C1-C6烷基；
R 7、R 8分别独立地代表氢、C1-C6烷基、卤素、卤代C1-C6烷基或氨基；
X 1、X 2分别独立地代表氢、卤素、C1-C6烷基、C2-C6烯基、C2-C6炔基、C3-C6环烷基、C3-C6环烷基C1-C6烷基、-OR 3、-(CO)OR 3或苯基，其中，所述“C1-C6烷基”、“C2-C6烯基”、“C2-C6炔基”、“C3-C6环烷基”或“C3-C6环烷基C1-C6烷基”分别独立地是未取代的或被选自卤素中的至少一个基团所取代的；
X 3代表卤素、氰基、甲酰基、C1-C6烷基、C2-C6烯基、C2-C6炔基、C3-C6环烷基、C3-C6环烷基C1-C6烷基、-OR 3、-(CO)OR 3、-SR 3、杂环基、杂环基C1-C6烷基、芳基、芳基C1-C6烷基或氨基，其中，
所述“C1-C6烷基”、“C2-C6烯基”或“C2-C6炔基”分别独立地是未取代的或被选自卤素、氰基、-OR 3、-(CO)R 3、-SR 3、-(SO 2)R 3、-O(CO)R 3、-O-(SO 2)R 3、-(CO)OR 3、-O(CO)OR 3、-O-(C1-C6烷基)-(CO)OR 3或-O(CO)(CO)OR 3中的至少一个基团所取代的，
所述“C3-C6环烷基”、“C3-C6环烷基C1-C6烷基”、“杂环基”、“杂环基C1-C6烷基”、“芳基”或“芳基C1-C6烷基”分别独立地是未取代的或被选自氧代、卤素、氰基、硝基、C1-C6烷基、C2-C6烯基、C2-C6炔基、C3-C6环烷基、卤代C1-C6烷基、卤代C2-C6烯基、卤代C2-C6炔基、卤代C3-C6环烷基、被C1-C6烷基取代的C3-C6环烷基、-OR 4、-SR 4、-(CO)OR 4、-(SO 2)R 4或-N(R 4) 2中的至少一个基团所取代的，
所述“氨基”是未取代的或被选自-R 3中的一个或两个基团所取代的；
X 4分别独立地代表-COOR 5或-(C1-C6烷基)-COOR 5；
R 3分别独立地代表氢、C1-C6烷基、C2-C6烯基、C2-C6炔基、C3-C6环烷基或C3-C6环烷基C1-C6烷基；
R 4分别独立地代表氢、C1-C6烷基或卤代C1-C6烷基；
R 5分别独立地代表氢、C1-C6烷基、C2-C6烯基、C2-C6炔基、C3-C6环烷基或C3-C6环烷基C1-C6烷基，其中，所述“C1-C6烷基”、“C2-C6烯基”、“C2-C6炔基”、“C3-C6环烷基”或“C3-C6环烷基C1-C6烷基”分别独立地是未取代的或被选自卤素中的至少一个基团所取代的。
进一步优选地，Y代表卤素；
R 1、R 2、R 6分别独立地代表C1-C6烷基；
R 7、R 8分别独立地代表氢或卤代C1-C6烷基；
X 1、X 2分别独立地代表氢；
X 3代表卤素、甲酰基、C1-C6烷基、C2-C6烯基、C2-C6炔基、C3-C6环烷基、C3-C6环烷基C1-C3烷基、-OR 3、苯基或苄基，其中，
所述“C1-C6烷基”、“C2-C6烯基”或“C2-C6炔基”分别独立地是未取代的或被选自卤素、-OR 3、-O(CO)R 3、-(CO)OR 3、-O-(C1-C3烷基)-(CO)OR 3或-O(CO)(CO)OR 3中的1、2或3个基团所取代的，
所述“C3-C6环烷基”、“C3-C6环烷基C1-C3烷基”、“苯基”或“苄基”分别独立地是未取代的或被选自卤素、C1-C6烷基、C2-C6烯基、C2-C6炔基、C3-C6环烷基、卤代C1-C6烷基、卤代C2-C6烯基、卤代C2-C6炔基、卤代C3-C6环烷基、被C1-C6烷基取代的C3-C6环烷基、-OR 4或-(CO)OR 4中的1、2或3个基团所取代的；
X 4分别独立地代表-COOR 5；
R 3分别独立地代表氢、C1-C6烷基、C2-C6烯基、C2-C6炔基、C3-C6环烷基或C3-C6环烷基C1-C3烷基；
R 4分别独立地代表氢、C1-C6烷基或卤代C1-C6烷基；
R 5分别独立地代表氢、C1-C6烷基、C2-C6烯基、C2-C6炔基或C3-C6环烷基。
更进一步优选地，Y代表氯；
Z代表氟；
R 7代表卤代C1-C6烷基；
R 8代表氢；
X 3代表卤素、甲酰基、C1-C6烷基、C3-C6环烷基、C3-C6环烷基C1-C3烷基、-OR 3、-(C1-C3烷基)-OR 3、-(C1-C3烷基)-O(CO)R 3、-(C1-C3烷基)-(CO)OR 3、-(C1-C3烷基)-O-(C1-C3烷基)-(CO)OR 3、-(C1-C3烷基)-O(CO)(CO)OR 3、苯基或苄基，其中，
所述“C1-C6烷基”分别独立地是未取代的或被选自卤素中的1、2或3个基团所取代的；
R 3分别独立地代表氢或C1-C6烷基；
R 5分别独立地代表氢或C1-C6烷基。
再进一步优选地，Q代表
Figure PCTCN2020126434-appb-000003
Figure PCTCN2020126434-appb-000004
在上述通式所示化合物的定义和以下所有结构式中，所用专业术语不论单独使用或者使用在复合词中，代表如下取代基：具有多于两个碳原子的烷基基团可为直链或支链的。如复合词“-烷基-(CO)OR 11”中烷基可为-CH 2-、-CH 2CH 2-、-CH(CH 3)-、-C(CH 3) 2-等。烷基基团为，例如，C1烷基-甲基；C2烷基-乙基；C3烷基-丙基如正丙基或异丙基；C4烷基-丁基如正丁基、异丁基、叔丁基或2-丁基；C5烷基-戊基如正戊基；C6烷基-己基如正己基、异己基和1,3-二甲基丁基。类似地，烯基是例如乙烯基、烯丙基、1-甲基丙-2-烯-1-基、2-甲基丙-2-烯-1-基、丁-2-烯-1-基、丁-3-烯-1-基、1-甲基丁-3-烯-1-基和1-甲基丁-2-烯-1-基。炔基是例如乙炔 基、炔丙基、丁-2-炔-1-基、丁-3-炔-1-基、1-甲基丁-3-炔-1-基。多重键可以在每个不饱和基团的任何位置。环烷基是具有例如三至六个碳原子的碳环饱和环体系，例如环丙基、环丁基、环戊基或环己基。类似地，环烯基是具有例如三至六个碳环成员的单环烯基，例如环丙烯基、环丁烯基、环戊烯基和环己烯基，其中双键可以在任何位置。卤素为氟、氯、溴或碘。
除非有特别说明的，本发明所述“芳基”包括但不限于苯基、萘基、
Figure PCTCN2020126434-appb-000005
Figure PCTCN2020126434-appb-000006
所述“杂环基”不仅包括但不限于饱和或不饱和的非芳族环状基团
Figure PCTCN2020126434-appb-000007
Figure PCTCN2020126434-appb-000008
Figure PCTCN2020126434-appb-000009
等，还包括但不限于杂芳基，即含有例如3至6个环原子且还任选地有苯并环稠合的芳族环状基团，所述环原子中的1至4个(例如1、2、3或4个)杂原子选自氧、氮和硫，例如
Figure PCTCN2020126434-appb-000010
Figure PCTCN2020126434-appb-000011
如果一个基团被基团所取代，则这应理解为意指该基团被一个或多个相同或不同的选自所提及的那些基团的基团取代。另外，相同或不同取代基中含有的相同或不同的取代字符均独立地选择，可相同也可不同。这同样适用于由不同原子和单元形成的环体系。同时，权利要求的范围将排除那些为本领域技术人员知晓的在标准条件下化学不稳定的化合物。
另外，除非特别限定地，本发明所述“至少一个基团所取代的”是指被如1、2、3、4或5个基团所取代；未标注具体连接位置的基团(包括杂环基、芳基等)，可在任意位置连接，包括与C或N相连接的位置；如果其是被取代的，取代基同样可在任何位置取代，只要符合化合键连接规则。如被1个甲基所取代的杂芳基
Figure PCTCN2020126434-appb-000012
可代表
Figure PCTCN2020126434-appb-000013
等。
需要指出的，当通式I
Figure PCTCN2020126434-appb-000014
中与X 3和X 4相连的碳原子(C*)为手性中心(即X 3和X 4不相同时)时，其为R构型或S构型，优选S构型，基于在该位置上具有R和S构型的立体异构体含量而言，其具有60-100％(S)的立体化学纯度，优选70-100％(S)，更优选80-100％(S)，进一步优选90-100％(S)，更进一步优选95-100％(S)。其中，“立体化学纯度”是指所述的立体异构体的量占具有产生手性中心的立体异构体的总量的百分比。
此外，本发明还提供了一种具有S构型的含取代异恶唑啉的芳香类化合物，如通式I’所示：
Figure PCTCN2020126434-appb-000015
其中，X 3’代表氢、甲基或X 3，取代基X 1、X 2、X 3、X 4、Q、Y和Z的定义如前所述且X 3、X 4不相同。
本发明中，式I和式I’中标记为*的位置处的立体化学构型是根据Cahn-Ingold-Prelog系统来确定为主要的(S)，然而本发明的主题也涉及式I和式I’所包括的其它位置的所有立体异构体，及其混合物。这类式I和式I’化合物包含，例如一种或多种附加的不对称碳原子或其它未在式I和式I’中具体说明的双键。应理解的是，本发明包括纯异构体及其程度不同的富集纯异构体的混合物，其中在标记为*的位置处的不对称碳原子是S-构型，或在混合物中，化合物或同样化学构造的化合物在标记为*的位置上具有S-构型，或以主要存在具有S-构型的化合物(至少60％S-构型)的比例存在，同时其它的不对称碳原子可以以外消旋形式存在，或也可以进行程度不同的拆分。只要符合在标记为*的位置上的立体化学构型条件，则由特定的空间形式定义的可能的立体异构体，如对映异构体、非对映异构体、Z-和E-异构体均包括在式I和式I’中，并且可以采用常规方法从立体异构体的混合物中获得，或也可以通过与利用立体化学纯初始物质相结合的立体选择反应加以制备。
若存在各种官能团，本发明还包括任何酮和烯醇互变异构体形式及其混合物和盐。
立体异构体可通过光学拆分从在制备中获得的混合物中获得。同样可通过使用立体选择性反应且使用光学活性的起始原料和/或助剂来选择性地制备立体异构体。对于光学拆分而 言，通常可以利用常规方法(参见Textbooks ofStereochemistry)，例如用于将混合物拆分成非对映异构体的下述方法，例如物理方法，如结晶、层析法，尤其是柱层析和高压液相色谱法，视需要在减压下进行的蒸馏方法，萃取法和其它方法，通常采用在手性固相上的色谱分离，可以分离对映结构体的残余混合物。适用于制备量或用于工业规模的是这样的方法，例如结晶非对映盐，这可以利用光学活性酸从化合物中获得，并且若存在酸性基团，可以视需要利用光学活性碱。
所述含取代异恶唑啉的芳香类化合物的制备方法，包括以下步骤：
当Q代表
Figure PCTCN2020126434-appb-000016
时，(1)将通式Ⅱ-1所示的化合物与通式Ⅲ-1所示的化合物进行环化反应，制得如通式Ⅰ-1所示的化合物，其化学反应方程式如下：
Figure PCTCN2020126434-appb-000017
当Q代表
Figure PCTCN2020126434-appb-000018
时，(2)将通式Ⅱ-2所示的化合物与通式Ⅲ-2所示的化合物进行环化反应，制得如通式Ⅰ-2所示的化合物，其化学反应方程式如下：
Figure PCTCN2020126434-appb-000019
(3)将通式Ⅱ-3所示的化合物与通式Ⅲ-3所示的化合物进行反应得到通式Ⅰ-3所示的化合物；
Figure PCTCN2020126434-appb-000020
(4)将通式Ⅱ-4所示的化合物与通式Ⅲ-4所示的化合物进行反应得到通式Ⅰ-4所示的化合物；
Figure PCTCN2020126434-appb-000021
或者，(5)通式Ⅰ-5所示的化合物与R 6’-Hal经取代反应制得如通式Ⅰ-6所示的化合物；
其化学反应方程式如下：
Figure PCTCN2020126434-appb-000022
其中，L 1、L 2、L 3、L 4、L 5、L 6和L 7分别独立地代表C1-C6烷基或芳基，优选甲基、乙基或苯基；Hal代表卤素，优选碘；R 6’代表R 6中除氢以外的基团；其他取代基R 1、R 2、R 6、R 7、R 8、X 1、X 2、X 3、X 4、Q 1、Q 2、Q 3、Q 4、Q 5、Y和Z的定义如前所述。
优选地，所述步骤(1)、(2)、(4)和(5)均在碱和溶剂的存在下进行。
所述碱选自无机碱(如K 2CO 3、Na 2CO 3、Cs 2CO 3、NaHCO 3、KF、CsF、KOAc、AcONa、K 3PO 4、t-BuONa、EtONa、NaOH、KOH、NaOMe等)或有机碱(如吡唑、三乙胺、DIEA等)中的至少一种。
所述溶剂选自DMF、DMA、甲醇、乙醇、乙腈、二氯乙烷、DMSO、Dioxane、二氯甲烷或乙酸乙酯中的至少一种。
优选地，所述步骤(3)在酸的存在下进行。
所述酸选自醋酸、盐酸或硫酸。
另外，当Q
Figure PCTCN2020126434-appb-000023
中的取代基Q 1、Q 2、Q 3至少一个为S或Q 4、Q 5至少一个为S时，其也可以由相应的Q代表
Figure PCTCN2020126434-appb-000024
时的化合物为原料在劳森试剂
Figure PCTCN2020126434-appb-000025
或五硫化二磷的存在下进行常规的硫取代反应制得。
本发明所述化合物也参照专利WO00/50409、CN105753853A等记载的相关方法制备。
一种除草剂组合物，其包括除草有效量的所述的含取代异恶唑啉的芳香类化合物中的至 少一种，优选地，还包括制剂助剂。
一种控制杂草的方法，其包括将除草有效量的所述的含取代异恶唑啉的芳香类化合物中的至少一种或所述的除草剂组合物使用在植物上或者杂草区域。
所述的含取代异恶唑啉的芳香类化合物中的至少一种或所述的除草剂组合物在控制杂草上的用途，优选地，将所述的含取代异恶唑啉的芳香类化合物用于防除有用作物中的杂草，所述有用作物为转基因作物或者基因组编辑技术处理过的作物。
对于许多经济上重要的单子叶和双子叶有害植物，本发明的式I和式I’化合物具有突出的除莠活性。本发明的活性物质也对于多年生杂草有效，这些杂草从根茎、根状茎、或其它的多年生的器官上生长出来，很难控制。关于这点，是否在播种前、萌发前或萌发后使用该物质一般不重要。特别提及本发明化合物可以控制的单子叶和双子叶杂草群的代表例子，没有限制到的确定的物种。活性物质有效作用的杂草物种的例子包括单子叶植物：一年生燕麦属、黑麦、草属、看麦娘属、法拉里斯、稗、马唐属、狗尾草属和莎草属，和多年生的冰草属、狗牙根属、白茅属和高粱属、以及多年生的莎草属。
关于双子叶杂草物种，其作用可以扩展到的物种例如一年生的猪殃殃属、堇菜属、婆婆纳属、野芝麻属、繁缕属、苋属、白芥属、番薯属、黄花稔属、母菊属和苘麻属，和多年生杂草旋花属、蓟属、酸模属和艾属。本发明活性物质在水稻播种这种待定条件下有效控制有害植物，例如稗、慈姑属、泽泻属、荸荠属、蔗草和莎草属。如果将本发明化合物在萌芽前施用于土壤表面，可以在杂草长出前完全预防杂草的秧苗，或在杂草长出子叶时就停止生长，最后在三到四星期之后完全死亡。本发明化合物特别抗下述植物的活性优良，阿皮拉草、小野芝麻、卷茎蓼、繁缕、长春藤叶婆婆纳、阿拉伯婆婆纳、三色堇和苋、猪殃殃属和地肤。
虽然本发明化合物对于单子叶和双子叶的杂草具有优良的除莠活性，但对于重要的经济类作物植物，例如小麦、大麦、黑麦、稻子、玉米、甜菜、棉花和大豆却根本没有损害，或者是损害是微不足道的。特别是和谷类作物相容得很好，例如小麦、大麦和玉米，特别是小麦。因此，本发明化合物非常适于有选择地控制在农用作物或观赏植物中的无用植物。
由于它们的除莠性质，在已知或将要出现的遗传工程的植物耕种中，这些活性物质可以用于控制有害植物。转基因植物通常具有优越的性状，例如对特定杀虫剂特别是特定除草剂的抵抗力，对植物病害或植物病害的致病微生物的抵抗力，例如特定的昆虫或真菌、细菌或病毒的微生物。其它的特别性状与产品的下述条件有关，例如，数量、质量、贮存稳定性、组分和特殊的成分。如此，已经知道获得的转基因植物产品具有增加的淀粉含量或改进的淀粉质量或不同的脂肪酸成份。
本发明的式I和式I’化合物或其盐优选用于，经济上重要的转基因的作物和观赏植物，例如谷类，例如小麦、大麦、黑麦、燕麦、粟、稻子、木薯和玉米、或用于甜菜、棉花、大豆、油菜籽、马铃薯、番茄、豌豆及其他蔬菜类植物的耕种。式I和式I’化合物优选用于有用植物耕种的除草剂，这些植物具有抗药性或通过遗传工程对除草剂的毒害作用具有抗药性。
传统的繁育具有比已知植物具有改进形状植物的方法包括，例如传统的交配方法和突变株繁育。换句话说，可以借助于遗传工程的方法(参见，例如EP-0221044A，EP-0131624A)来得到具有改进性状的新植物。例如，已经描述了几个方法：
-为了改进植物中的淀粉合成，利用遗传工程改变作物植物(例如WO 92/11376，WO 92/14827，WO 91/19806)；
-对特定的除草剂具有抗性的转基因作物植物，对草丁膦除草剂(例如EP-0242236 A，EP-0242246 A)或对草甘膦类除草剂(WO 92/00377)，或对磺酰脲类除草剂(EP-0257993 A，US-5013659 A)；
-例如棉花的转基因作物植物，它能够产生苏芸金杆菌毒素(Bt毒素)，这种毒素可以防御特定害虫对植物的侵害(EP-0142924 A，EP-0193259 A)；
-具有改进的脂肪酸成份的转基因作物植物(WO91/13972)。
已经知道许多能够制备具有改进性状转基因植物分子生物技术(参见，例如Sambrook等，1989，分子扩增，实验手册第二版，美国冷泉港实验室出版，冷泉港，纽约；或Winnacker“Gene und Klone”[基因和克隆]，VCH Weinheim，第二版1996或Christou，“植物科学的趋势”1(1996)423-431))。为了实现遗传工程的操作，可能将核酸分子引入质粒，通过DNA序列的重组，发生突变或序列改变。利用上述的标准方法，例如可以交换底物、除去部分序列或增加自然的或合成的序列。为了将DNA片段互相连接，有可能在片段上附带有结合体或连接体。
可以用下述方法制备降低活性的基因产品的植物细胞，例如通过表达至少一种适当的反义-RNA、正义-RNA来达到共抑制的效果，或通过表达至少一种适当构造的核糖酶，它特定裂解上述基因产品的转录产物。
为此目的，有可能使用包含基因产物全部编码序列的DNA分子，包括有可能存在的任何旁侧序列，和使用包含仅仅一部分编码序列的DNA分子，这些部分必须足够长以达到在细胞中反义的效果。也可以使用与基因产物编码序列具有高度同源性但不完全相同的序列。
当在植物中表达核酸分子时，合成的蛋白质可以在任何期望的植物细胞室中定位。然而为了在特定的室定位，有可能例如将编码区和DNA序列连接，以确保在特定位置定位。这些序列为本领域所属技术人员已知的(参见，例如Braun等，EMBO J.11(1992)3219-3227；Wolter等，Proc.Natl.Acad.Sci.USA 85(1988)，846-850；Sonnewald等Plant J.1(1991)，95-106)。
利用已知的技术可以将转基因植物细胞重组到整个植物上。转基因植物可以为任何期望的植物品种，即单子叶和双子叶植物。用这样的方式，通过超表达、禁止或抑制同源(＝自然的)基因或基因序列，或通过异种的(＝外部的)基因或者基因序列的表达，有可能获得改进性状的转基因植物。
当在转基因的作物上使用本发明的活性物质时，除了具有在其它作物上可观察到的抑制有害植物的效果外，经常在相应的转基因作物上会有特殊的效果，例如可以改进或扩大控制杂草的范围，改进应用时的施用量，优选转基因作物的抗药性和除草剂的性能很好的结合，并且转基因的作物植物的生长和产率的影响。因此本发明也提供了所述化合物的用途，作为除草剂控制转基因作物植物中的有害植物。
另外本发明化合物可以明显调节作物植物的生长。通过调节参与植物代谢，使用这些化合物定向控制植物的组分和促进收获，例如使植物干化和矮化生长。而且它们也适于调节和 抑制不希望的植物生长，而不破坏作物的生长。抑制植物的生长在许多单子叶植物和双子叶植物作物中起着非常重要的作用，因为这样可以减少或完全预防倒伏。
可以使用一般的制剂来应用本发明的化合物，可使用可湿性粉剂、浓缩乳剂、可喷洒的溶液、粉末或颗粒。这样本发明也提供了包括式I和式I’化合物的除草剂组合物。根据通常的生物学和/或化学的物理参数，可以用多种方式配制式I和式I’化合物。适合的制剂选择实例为：可湿性粉剂(WP)、水溶性的粉末(SP)、水溶性的浓缩物、浓缩乳剂(EC)、例如油在水中分散和水在油中分散的乳剂(EW)、可喷洒溶液、悬浮剂浓缩物(SC)、可分散油悬浮剂(OD)、以油或水为稀释剂的悬浮液、可混溶油的溶液、粉末(DP)、胶囊悬浮液(CS)、包核(seeddressing)组合物、用于撒播和土壤施药的颗粒、喷射颗粒、涂覆颗粒和吸收颗粒，水中可分散的颗粒(WG)、水溶性的颗粒(SG)、ULV(超低容量)配方、微囊和蜡制品。这些单个的制剂类型为已知的，在下述文献中有描述，例如Winnacker-Küchler，“Chemische Techonologie”[化学工艺]，第7卷，C.Hauser Verlag Munich，第4版1986；Wade van Valkenburg，“Pesticide Formulations”，Marcel Dekker，N.Y.，1973；K.Martens，“Spray Drying”手册，第3版1979，G.Goodwin Ltd.London。
必要的制剂助剂，例如惰性物质、表面活性剂、溶剂及其它添加剂同样为已知的，并在下述文件中描述，例如Watkins的“粉末稀释剂杀虫剂和载体手册”，第二版，Darland书Caldwell N.J.；H.v.01phen“粘土胶体化学的入门”，第二版，J.Wiley和Sons，N.Y.；C.Marsden的“溶剂指南”第二版，Interscience，N.Y.1963；McCutcheon的“洗涤剂和乳化剂年报”，MC发行公司，Ridgewood N.J.；Sisley和Wood，“表面活性剂百科全书”，化学出版公司，N.Y.1964；
Figure PCTCN2020126434-appb-000026
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Figure PCTCN2020126434-appb-000027
[环氧乙烷加成物表面活性剂]，Wiss.Verlagagesell.Stuttgart 1976；Winnacker-Küchler的“Chemische Technologie”[化学工艺]，第7卷，C.Hauser Verlag Munich，第4版1986。
可湿性粉剂能均匀地可分散在水中，除了活性物质，还包括稀释剂或惰性物质、离子和非离子型表面活性剂(润湿剂、分散剂)，例如聚乙氧基烷基酚、聚乙氧基脂肪醇、聚氧乙基脂肪族胺、脂肪醇聚二醇醚硫酸盐、烷基磺酸盐、烷基苯基磺酸盐、木质磺酸钠、2,2’-二萘甲烷-6,6’-二磺酸钠、二丁基萘磺酸钠或油酰甲基牛磺酸钠。为了制备可湿性粉剂，将除草剂的活性物质细磨，例如使用常用的仪器，如用锤磨机、风扇磨碎机和喷气式磨碎机，同时或顺序混入助剂。
将活性物质溶解在有机溶剂中制备浓缩乳剂，溶剂例如丁醇、环己酮、二甲基甲酰胺、二甲苯或较高沸点的芳族化合物或碳氢化合物或溶剂的混合物，并再加入一种或多种离子的和/或非离子型表面活性剂(乳化剂)。可以使用的乳化剂的例子为例如十二烷基苯磺酸钙的烷基芳基磺酸钙，或非离子乳化剂，例如脂肪酸聚二醇酯、烷基芳香基聚二醇醚、脂肪醇聚二醇醚、氧化丙烯-环氧乙烷缩合产物、烷基聚醚、例如山梨糖醇酐脂肪酸酯的山梨聚糖酯，或例如聚氧化乙烯山梨糖醇酐脂肪酯的聚氧化乙烯山梨聚糖酯。
将活性物质和细碎的固态物质研磨得到粉末，固态物质例如滑石、如高岭土、皂土和叶蜡石的天然粘土、或硅藻土。以水或油为基底的悬浮液可以通过下述方法制备，例如利用商业上通用的玻珠研磨机进行湿磨，加入或不加入上述另一个制剂类型的表面活性剂。
制备例如水包油乳化剂(EW)的乳剂，可以使用含水的有机溶剂，使用搅拌器、胶体研磨器和/或静态混合器，如果需要，加入如上所述另一个制剂类型的表面活性剂。
用下述方法制备颗粒剂，将活性物质喷到吸附物上，使用惰性物料颗粒化，或将活性物质浓缩到例如沙、高岭石载体的表面，通过粘合剂将惰性物料粒化，粘合剂例如聚乙烯醇、聚丙烯酸钠或矿物油。可以用制备肥料颗粒剂的方法将合适的活性物质粒化，如果需要可以混有肥料。使用通常的方法制备水悬浮颗粒剂，例如喷洒-干燥，流化床造粒、磨盘造粒、使用高速混合机混合，并在无固体惰性物料的情况下挤压。
关于使用磨盘、流化床、挤压机和喷涂颗粒剂的制备方法，参见下述工艺，例如“Spray Drying手册”第三版1979，G.Goodwin有限公司，伦敦；J.E.Browning，“Agglomeration”，化学和工程1967，147ff页；“Perry’s化学的工程师手册”，第五版，McGraw-Hill，纽约1973，8-57页。如果要知道关于作物保护产品的制剂，参见例如，G.C.Klingman,“Weed Control as a Science”，John Wiley和Sons公司，纽约，1961 81-96页和J.D.Freyer，S.A.Evans“杂草防除手册”，第五版，Blackwell Scientific Rublications，牛津大学1968，101-103页。
农用化学品制剂通常包含按重量计0.1到99％，特别是0.1到95％的活性物质式I和式I’。可湿性粉剂中活性物质的浓度为，按重量计例如从大约10到99％，通常的制剂组分构成按重量计剩余量到100％。活性物质在浓缩乳剂中的浓度按重量计可以为大约1到90％，优选5到80％。粉末制剂包含按重量计1到30％的活性物质，通常优选按重量计5到20％的活性物质，然而可喷洒的溶液包含按重量计大约0.05到80％，优选2到50％的活性物质。关于水悬浮颗粒剂中活性物质的含量，主要根据活性物质为液体还是固态，和造粒时使用的助剂、填料等等。水悬浮颗粒剂中活性物质的含量例如按重量计在1到95％之间，优选按重量计在10到80％之间。
另外所述的活性物质的制剂可以包括增粘剂、润湿剂、分散剂、乳化剂、渗透剂、防腐剂、防冻剂、溶剂、填料、载体、着色剂、消泡剂、蒸发抑制剂和通常在所有情况下都常用的pH和粘度调节剂。
以这些制剂为基础，也可能和其他杀虫剂活性物质例如杀虫剂、杀螨剂、除草剂和杀菌剂混合，也可以和安全剂、肥料和/或植物生长调节剂混合，混合方式可以为预先混合好的或灌装混合。
在混配制剂或桶混制剂中，可以和本发明的活性物质混合的合适的活性物质为，例如《世界农药新品种技术大全》，中国农业科学技术出版社，2010.9和这里引用的文献中的已知物质。例如以下提到的除草剂活性物质可以和式I和式I’混合物混合，(备注：化合物的名称，或者为根据国际标准化组织(ISO)的普通名称，或者为化学名称，适当的时候有代号)：乙草胺、丁草胺、甲草胺、异丙草胺、异丙甲草胺、精异丙甲草胺、丙草胺、毒草胺、克草胺、萘丙酰草胺、R-左旋萘丙酰草胺、敌稗、苯噻酰草胺、双苯酰草胺、吡氟酰草胺、杀草胺、氟丁酰草胺、溴丁酰草胺、二甲噻草胺、高效二甲噻草胺、乙氧苯草胺、氟噻草胺、甲氧噻草胺、吡草胺、异恶草胺、高效麦草伏甲酯、高效麦草伏丙酯、二丙烯草胺、烯草胺、丁酰草胺、环丙草胺、氟磺酰草胺、庚酰草胺、异丁草胺、丙炔草胺、特丁草胺、二甲苯草胺、二甲草胺、落草胺、三甲环草胺、氯甲酰草胺、炔苯酰草胺、戊酰苯草胺、卡草胺、新燕灵、 三环赛草胺、丁烯草胺、牧草胺、苄草胺、醌萍胺、苯氟磺胺、萘丙胺、乙酰甲草胺、萘草胺、噻草胺、吡氰草胺、苯草多克死、草克乐、氯酞亚胺、丁脒胺、氟吡草胺、莠去津、西玛津、扑草净、氰草净、西草净、莠灭净、扑灭津、异丙净、氟草净、特丁净、特丁津、三嗪氟草胺、环丙津、甘扑津、草达津、扑灭通、西玛通、叠氮净、敌草净、异戊乙净、环丙青津、灭莠津、另丁津、仲丁通、特丁通、甲氧丙净、氰草净、抑草津、可乐津、莠去通、灭草通、甘草津、三聚氰酸、Indaziflam、绿磺隆、甲磺隆、苄嘧磺隆、氯嘧黄隆、苯磺隆、噻磺隆、吡嘧黄隆、甲基二磺隆、甲基碘磺隆钠盐、甲酰氨基嘧磺隆、醚磺隆、醚苯磺隆、甲嘧磺隆、烟嘧磺隆、胺苯磺隆、酰嘧磺隆、乙氧嘧磺隆、环丙嘧磺隆、砜嘧磺隆、四唑嘧磺隆、啶嘧黄隆、单嘧磺隆、单嘧磺酯、氟唑磺隆、氟啶嘧磺隆、氟吡嘧磺隆、环氧嘧磺隆、唑吡嘧磺隆、氟嘧磺隆、丙苯磺隆、三氟丙磺隆、磺酰磺隆、三氟啶磺隆、氟胺磺隆、三氟甲磺隆、甲磺隆钠盐、氟吡磺隆、甲硫嘧磺隆、嘧苯胺磺隆、Propyrisulfuron(丙嗪嘧磺隆)、嗪吡嘧磺隆、三氟羧草醚、氟磺胺草醚、乳氟禾草灵、乙羧氟草醚、乙氧氟草醚、草枯醚、苯草醚、氯氟草醚乙酯、甲羧除草醚、三氟甲草醚、甲氧除草醚、三氟硝草醚、氟化除草醚、氟呋草醚、除草醚、甲草醚、二甲草醚、氟酯肟草醚、氟草醚酯、Halosafen、绿麦隆、异丙隆、利谷隆、敌草隆、莎扑隆、氟草隆、苯噻隆、甲基苯噻隆、苄草隆、磺噻隆、异恶隆、特丁噻草隆、炔草隆、氯溴隆、甲基杀草隆、酰草隆、甲氧杀草隆、溴谷隆、甲氧隆、绿谷隆、灭草隆、环草隆、非草隆、氟硫隆、草不隆、枯草隆、草完隆、异草完隆、环莠隆、噻氟隆、丁噻隆、枯莠隆、对氟隆、甲胺噻唑隆、隆草特、三甲异脲、恶唑隆、Monisouron、Anisuron、Methiuron、Chloreturon、四氟隆、甜菜宁、甜菜宁-乙酯、甜菜安、磺草灵、特草灵、燕麦灵、苯胺灵、氯苯胺灵、二氯苄草酯、灭草灵、氯炔灵、Carboxazole、Chlorprocarb、Fenasulam、BCPC、CPPC、Carbasulam、丁草特、禾草丹、灭草猛、禾草特、野麦畏、哌草丹、禾草畏、稗草丹、环草敌、燕麦敌、菌达灭、乙硫草特、坪草丹、克草猛、苄草丹、仲草丹、硫烯草丹、草灭散、Isopolinate、Methiobencarb、2,4-滴丁酯、2甲4氯钠、2,4-滴异辛酯、2甲4氯异辛酯、2,4-滴钠盐、2,4-滴二甲胺盐、2甲4氯乙硫酯、2甲4氯、2,4-滴丙酸、高2,4-滴丙酸盐、2,4-滴丁酸、2甲4氯丙酸、2甲4氯丙酸盐、2甲4氯丁酸、2,4,5-涕、2,4,5-涕丙酸、2,4,5-涕丁酸、2甲4氯胺盐、麦草畏、抑草蓬、伐草克、赛松、三氯苯酸、氨二氯苯酸、甲氧三氯苯酸、禾草灵、吡氟禾草灵、精吡氟禾草灵、氟吡甲禾灵、高效吡氟氯禾灵、喹禾灵、精喹禾灵、恶唑禾草灵、精恶唑禾草灵、喔草酯、氰氟草酯、恶唑酰草胺、炔草酯、噻唑禾草灵、炔禾灵、羟戊禾灵、三氟禾草肟、异恶草醚、百草枯、敌草快、安磺灵、乙丁烯氟灵、异丙乐灵、甲磺乐灵、环丙氟灵、氨基丙氟灵、乙丁氟灵、氯乙氟灵、氨基乙氟灵、地乐灵、氯乙地乐灵、Methalpropalin、丙硝酚、草甘膦、莎稗膦、草铵膦、甲基胺草磷、草硫膦、哌草膦、双丙氨膦、地散磷、抑草磷、蔓草磷、伐垅磷、双甲胺草磷、草特磷、咪唑烟酸、咪唑乙烟酸、咪唑喹啉酸、甲氧咪草烟、甲氧咪草烟铵盐、甲咪唑烟酸、咪草酯、氯氟吡氧乙酸、氯氟吡氧乙酸异辛酯、二氯吡啶酸、氨氯吡啶酸、三氯吡氧乙酸、氟硫草定、卤草定、三氯吡啶酚、噻草啶、氟啶草酮、氯氨吡啶酸、氟吡草腙、三氯吡氧乙酸丁氧基乙酯、Cliodinate、稀禾啶、烯草酮、噻草酮、禾草灭、环苯草酮、丁苯草酮、肟草酮、吡喃草酮、Buthidazole、嗪草酮、环嗪酮、苯嗪草酮、乙嗪草酮、Ametridione、Amibuzin、溴苯腈、 辛酰溴苯腈、辛酰碘苯腈、碘苯腈、敌草腈、二苯乙腈、双唑草腈、羟敌草腈、Iodobonil、唑嘧磺草胺、双氟磺草胺、五氟磺草胺、磺草唑胺、氯酯磺草胺、双氯磺草胺、啶磺草胺、氟草黄、双草醚、嘧啶肟草醚、环酯草醚、嘧草醚、嘧硫草醚、双环磺草酮、硝磺草酮、磺草酮、Tembotrione、Tefuryltrione、Bicyclopyrone、Ketodpiradox、异恶唑草酮、异恶氯草酮、Fenoxasulfone、Methiozolin、异丙吡草酯、吡草醚、吡唑特、野燕枯、苄草唑、吡草酮、吡氯草胺、Pyrasulfotole、苯唑草酮、Pyroxasulfone、唑草胺、氟胺草唑、杀草强、胺唑草酮、唑啶草酮、氟唑草酮、甲磺草胺、Bencarbazone、双苯嘧草酮、氟丙嘧草酯、除草定、异草定、环草啶、特草定、Flupropacil、吲哚酮草酯、氟烯草酸、丙炔氟草胺、炔草胺、酞苄醚、Flumezin、五氯酚(钠)、地乐酚、特乐酚、特乐酯、戊硝酚、二硝酚、氯硝酚、地乐施、地乐特、丙炔恶草酮、恶草酮、环戊恶草酮、氟唑草胺、嗪草酸甲酯、四唑酰草胺、氟哒嗪草酯、杀草敏、溴莠敏、二甲达草伏、哒草醚、草哒酮、草哒松、哒草伏、Pyridafol、二氯喹啉酸、氯甲喹啉酸、苯达松、哒草特、恶嗪草酮、草除灵、异恶草酮、环庚草醚、异丙酯草醚、丙酯草醚、茚草酮、氯酸钠、茅草枯、三氯醋酸、一氯醋酸、六氯丙酮、四氟丙酸、牧草快、溴酚肟、三唑磺、灭杀唑、呋草酮、呋草磺、乙呋草磺、嘧草胺、氯酞酸、氟咯草酮、稗草稀、丙烯醛、苯草灭、灭草环、燕麦酯、噻二唑草胺、棉胺宁、羟草酮、甲氧苯酮、苯嘧磺草胺、氯酰草膦、三氯丙酸、Alorac、Diethamquat、Etnipromid、Iprymidam、Ipfencarbazone、Thiencarbazone-methyl、Pyrimisulfan、Chlorflurazole、Tripropindan、Sulglycapin、甲硫磺乐灵、Cambendichlor、环丙嘧啶酸、硫氰苯胺、解草酮、解草啶、解草安、解草唑、解草喹、解草腈、解草烷、解草胺腈、解草烯、吡唑解草酯、呋喃解草唑、肟草安、双苯噁唑酸、二氯丙烯胺、氟氯吡啶酯、DOW氯氟吡啶酯、UBH-509、D489，LS 82-556、KPP-300、NC-324、NC-330、KH-218、DPX-N8189、SC-0744、DOWCO535、DK-8910、V-53482、PP-600、MBH-001、KIH-9201、ET-751、KIH-6127和KIH-2023。
当使用时，如果需要，将市售的制剂以常见的方式稀释，例如在可湿性粉剂、浓缩乳剂、悬浮液和在水中悬浮的颗粒时，使用水稀释。粉末、土壤施药所用的颗粒剂或撒播和喷洒的溶液，一般在使用前不需要进一步用惰性物质稀释。随着外部条件的变化，要求的式I和式I’化合物的使用量也不同，外部条件为，例如温度、湿度、使用的除草剂的性质等等。它可以有大的变化幅度，例如在0.001到1.0kg a.i./ha之间，或更多的活性物质，但优选在0.005到750g a.i./ha之间，特别是在0.005到250g a.i./ha之间。
具体实施方式
以下实施例用于举例说明本发明，不应当视其为以任何方式限制本发明。本发明要求保护的权利范围通过权利要求书进行说明。
鉴于化合物的经济性与多样性，我们优选合成了一些化合物，在合成的诸多化合物中，选取部分列于下表1中。具体的化合物结构及相应的化合物信息如表1所示。表1中的化合物只是为了更好的说明本发明，但并不限定本发明，对于本领域的技术人员而言，不应将此理解为本发明上述主题的范围仅限于以下化合物。
表1化合物结构及其 1HNMR
Figure PCTCN2020126434-appb-000028
Figure PCTCN2020126434-appb-000029
Figure PCTCN2020126434-appb-000030
Figure PCTCN2020126434-appb-000031
Figure PCTCN2020126434-appb-000032
Figure PCTCN2020126434-appb-000033
Figure PCTCN2020126434-appb-000034
Figure PCTCN2020126434-appb-000035
Figure PCTCN2020126434-appb-000036
Figure PCTCN2020126434-appb-000037
Figure PCTCN2020126434-appb-000038
Figure PCTCN2020126434-appb-000039
Figure PCTCN2020126434-appb-000040
Figure PCTCN2020126434-appb-000041
Figure PCTCN2020126434-appb-000042
Figure PCTCN2020126434-appb-000043
Figure PCTCN2020126434-appb-000044
Figure PCTCN2020126434-appb-000045
Figure PCTCN2020126434-appb-000046
Figure PCTCN2020126434-appb-000047
Figure PCTCN2020126434-appb-000048
Figure PCTCN2020126434-appb-000049
Figure PCTCN2020126434-appb-000050
表A如以上表1相同构造，除了将有手性中心(
Figure PCTCN2020126434-appb-000051
中与X 3和X 4相连的碳原子(C*)为手性中心，即X 3和X 4不相同时)的消旋体化合物(即化合物1-50、52-90、92-93、95-152、154-192、194-195和197-236)替换为相应S构型并删除相应位置无手性中心的化合物，且在表A中，“序号”列标题下面的条目依次叙述为“1(S)-50(S)、52(S)-90(S)、92(S)-93(S)、95(S)-152(S)、154(S)-192(S)、194(S)-195(S)和197(S)-236(S)”。例如，“1(S)”对应于表1中化合物“1”的S构型，“119(S)”对应于表1中化合物“119”的S构型。
表B化合物结构及其 1H NMR数据
Figure PCTCN2020126434-appb-000052
Figure PCTCN2020126434-appb-000053
Figure PCTCN2020126434-appb-000054
Figure PCTCN2020126434-appb-000055
Figure PCTCN2020126434-appb-000056
Figure PCTCN2020126434-appb-000057
Figure PCTCN2020126434-appb-000058
Figure PCTCN2020126434-appb-000059
Figure PCTCN2020126434-appb-000060
Figure PCTCN2020126434-appb-000061
Figure PCTCN2020126434-appb-000062
制备本发明化合物的数种方法详解说明于以下方案和实施例中。原料可以经市场购买到或者可以通过文献中已知的方法或者如详解所示进行制备。本领域技术人员应当理解，也可以利用其它合成路线合成本发明的化合物。尽管在下文中已经对合成路线中的具体原料和条件进行了说明，但是，可以很容易地将其替换为其它类似的原料及条件，这些对本发明制备方法的变型或者变体而产生的诸如化合物的各种异构等都包括在本发明范围内。另外，如下所述制备方法可以按照本发明公开内容、使用本领域技术人员熟知的常规化学方法进行进一步修饰。例如，在反应过程中对适当的基团进行保护等等。
以下提供的方法实施例用于促进对本发明的制备方法的进一步了解，使用的具体物质、种类和条件确定为是对本发明的进一步说明，并不是对其合理范围的限制。在下表中表明的合成化合物中使用的试剂或者可以市场购买到，或者可以由本领域普通技术人员轻易制备得到。
代表性化合物的实施例如下，其他化合物的合成方法类似，此处不再详细说明。
1、化合物55的合成
(1)55-1(1.18g,1.0eq.,10mmol)溶于THF(30mL),冰水浴下加入NaH(500mg,1.25eq.,12.5mmol,60％purity),在冰水浴下搅拌30分钟后加入55-2(1.93g，1.0eq，10mmol),缓慢恢复至室温，并在室温下搅拌12h，TLC跟踪至反应完全。反应完全后，反应液缓慢加入水(200mL)中淬灭反应，乙酸乙酯(20mL)萃取三次，合并有机相并用无水硫酸钠干燥，过滤，浓缩得到粗品化合物55-3(1.88g，82％产率，8.2mmol，黄色油状液体)，直接投下一步。
Figure PCTCN2020126434-appb-000063
(2)在150毫升的DMF中加入a(20g,91.5mmol,1.0eq)，然后反应液在35℃条件下慢慢加入NCS(13.4g,100.7mmol,1.1eq)。加入完毕后反应液在35℃条件下搅拌1.5小时，LCMS检测原料基本反应完全。将反应液倒入100毫升HCl(1M)后加入二氯甲烷萃取，有机相用饱和食盐水洗涤(100ml*3)，有机相浓缩后得到粗品55-4(26g,粗品)(黄色油状)，粗品直接投入到下一步。
Figure PCTCN2020126434-appb-000064
(3)在20毫升的DCM中加入55-4(1.6g,6.7mmol,1.0eq)，Et 3N(1.01g,10.05mmol,1.5eq)，然后反应液在0℃条件下加入55-3(1.84g,8mmol,1.2eq)。反应在0℃条件下反应1小时后LCMS检测到产品。向反应液中加入100毫升水，二氯甲烷萃取(100ml*3)，有机相用无水硫酸钠干燥，浓缩，粗品经过柱层析纯化之后得到55-5(1.94,65％产率，4.35mmol，黄色固体)。
Figure PCTCN2020126434-appb-000065
(4)在20毫升的EtOH中依次加入55-5(1.80g,4.0mmol,1.0eq)，Fe粉(672mg,12.0mmol,3eq)，NH 4Cl(530mg,10.0mmol,2.0eq)和水(5ml)。然后反应液在80℃条件下反应2小时后LCMS检测原料消失，主峰为产品峰。反应液用硅藻土过滤后浓缩除去乙醇后加入水(100ml)，乙酸乙酯萃取后浓缩得到黑色粗品。粗品经柱层析分离纯化得到55-6(1.41g,85％产率,3.4mmol，黄色固体)。
Figure PCTCN2020126434-appb-000066
(5)在10ml甲苯中加入55-6(1.2g,2.89mmol,1.0eq)和55-7(0.50g,3.18mmol,1.1eq),反应液在110℃条件下加热1小时。LCMS检测到原料基本反应完毕，主峰为产品。浓缩溶剂后粗品经柱层析分离得到55-8(1.29g，83.4％产率,2.41mmol,黄色固体)。
Figure PCTCN2020126434-appb-000067
(6)在10ml DMF中加入55-9(0.48g,2.1mmol,1.5eq)和AcONa(58mg,0.7mmol,0.5eq)，然后反应液在60℃条件下加入55-8(0.75g,1.4mmol,1.0eq)，之后在60℃条件下反应1小时。LCMS检测到产品。向反应液中加入水(10ml)后用乙酸乙酯萃取，有机相 用饱和食盐水洗涤(20ml*1)，浓缩有机相后粗品经柱层析分离得到55(0.58g，72％产率，1.0mmol,黄色固体)。
Figure PCTCN2020126434-appb-000068
2、化合物119的合成
(1)草酸二乙酯(5.0g,34.2mmol,1.0eq)溶于无水THF(80mL)中，氮气保护下，干冰乙醇浴降温到-60℃，向体系中缓慢滴加环丙基溴化镁(1M in THF)(37.6mL，37.6mmol，1.1eq)。维持低温反应1h，LCMS检测原料基本消失，有新的峰生成。升至室温后，向体系中缓慢滴加饱和氯化铵水溶液淬灭反应，加水100mL稀释，水相用EA(3x 100mL)萃取，合并有机相，无水硫酸钠干燥，减压浓缩除去溶剂，得到粗产品119-1(4.9g，quantitative)。粗产品直接用于下步反应，不用纯化。
Figure PCTCN2020126434-appb-000069
(2)甲基三苯基溴化磷(12.2g，34.2mmol，1.0eq)溶于无水THF(100mL)中，氮气保护下，干冰乙醇浴降温到-60℃，向体系中缓慢加入LiHMDS(1M in THF)(34.2mL，34.2mmol，1.0eq)，维持低温反应1h。然后向体系中缓慢加入上步产品119-1(4.9g，34.2mmol，1.0eq)的四氢呋喃溶液。滴加完毕后，维持低温反应2h。LCMS检测原料消失，有新的峰生成。升至室温，向体系中缓慢滴加饱和氯化铵水溶液淬灭反应。减压浓缩除去大部分溶剂。剩余部分加水100mL稀释，水相用乙醚(2x 100mL)萃取，合并有机相，无水硫酸钠干燥，减压浓缩除去溶剂后得到产品119-2(3.2g，粗产品收率67％)，粗产品直接用于下步反应，不用纯化。
Figure PCTCN2020126434-appb-000070
(3)在60mL的DCM中加入原料55-4(2.8g,11.4mmol,0.5eq)，Et 3N(1.7g,17.1mmol,1.5eq)，然后反应液在0℃条件下加入上步产品119-2(3.2g,22.8mmol,1.0eq)。反应在0℃条件下反应1小时后LCMS检测到产品。向反应液中加入50毫升水，二氯甲烷萃取(50ml*3)，有机相用无水硫酸钠干燥，浓缩，粗品经过柱层析纯化之后得到产品119-3(320mg g,8％收率)(黄色油状)。
Figure PCTCN2020126434-appb-000071
(4)在20毫升的EtOH中依次加入上步产物119-3(320mg,0.9mmol,1.0eq)，Fe粉(151mg,2.7mmol,3eq)，NH 4Cl(95mg,1.8mmol,2eq)和水(5ml)。然后反应液在80℃条件下反应0.5小时后LCMS检测原料消失，主峰为产品峰。反应液用硅藻土过滤后浓缩除去乙醇后加入水(100ml)，乙酸乙酯萃取后经浓缩得到黑色粗品。粗品经柱层析分离纯化之后得到产品119-4(190mg,65％收率)(黄色油状)。
Figure PCTCN2020126434-appb-000072
(5)向50ml圆口烧瓶中加入上步产物119-4(190mg，0.6mml，1.0eq)，醋酸10mL和原料119-5(125mg，0.6mml，1.0eq)。升温到125℃反应20min。LCMS检测有产物生成。冷却到室温，减压浓缩除去醋酸，剩余部分加入硅胶拌样过柱纯化，浓缩后得到产物119-6(160mg，56％收率)(淡黄色油状物)。
Figure PCTCN2020126434-appb-000073
(6)在10mL无水DMF中加入上步产物119-6(160mg，0.33mmol，1.0eq)，碳酸钾(228mg，1.65mmol，5.0eq)和碘甲烷(140mg，0.99mmol，3.0eq)，室温反应3h。LCMS检测原料消失，有产物生成。加EA(60ml)稀释，有机相用水(2x 30mL)洗涤，饱和食盐水30ml洗涤，无水硫酸钠干燥，过滤浓缩，粗品经柱层析分离纯化之后得到产品119(100mg，60％收率)(黄色油状)。
Figure PCTCN2020126434-appb-000074
(7)化合物119通过手性HPLC(色谱柱型号：AD-5H 5μm 21.2x250mm,流动相：正己 烷：乙醇＝7:3,流速：20ml/min,波长：220nm)拆分之后得到119(S)(液质纯度：98％，93％ee)。
Figure PCTCN2020126434-appb-000075
3、化合物206的合成
(1)参照上述化合物119-4的制备方法制得化合物206-1，然后在10ml 1,4-二氧六环中加入206-1(0.6g,2.0mmol,1.0eq)和206-2(0.38g,2.2mmol,1.1eq),反应液在110℃条件下加热1小时。LCMS检测到原料基本反应完毕，主峰为产品。浓缩溶剂后粗品经柱层析分离得到206-3(0.7g，83.4％产率)(白色固体)。
Figure PCTCN2020126434-appb-000076
(2)在10ml DMF中加入206-4(0.47g,2.1mmol,1.5eq)和AcONa(58mg,0.7mmol,0.5eq)，然后反应液在60℃条件下加入206-3(0.6g,1.4mmol,1.0eq)之后在60℃条件下反应1小时。LCMS检测到产品。向反应液中加入水(10ml)后用乙酸乙酯萃取，有机相用饱和食盐水洗涤(20ml*1)，浓缩有机相后粗品经柱层析分离得到206(0.4g，61.4％产率)(白色固体)。
Figure PCTCN2020126434-appb-000077
4、化合物229的合成
(1)在200ml的DCM中加入55-4(2g,7.94mmol,1.0eq)，Et 3N(1.2g,11.88mmol,1.5eq)，然后反应液在0℃条件下加入229-1(1.02g,7.97mmol,1.0eq)。缓慢升温到20℃，反应2-4小时后LCMS检测到产品。向反应液中加入100ml水，二氯甲烷萃取(50ml*3)，有机相用无水硫酸钠干燥，浓缩，粗品经过柱层析纯化之后得到229-2(860mg,32％收率)。
Figure PCTCN2020126434-appb-000078
(2)在50ml的EtOH中依次加入229-2(860mg,2.5mmol,1.0eq)，Fe粉(420mg,7.5mmol,3.0eq)，NH 4Cl(265mg,5.0mmol,2eq)和水(12.5ml)。然后反应液在80℃条件下反应2小时后LCMS检测原料消失，主峰为产物。降温后反应液用硅藻土过滤后浓缩除去乙醇后加 入水，乙酸乙酯萃取后浓缩得到黑色粗品229-3，粗品直接用于下一步(720mg,90％收率)。
Figure PCTCN2020126434-appb-000079
(3)在20ml甲苯中加入229-3(450mg,1.43mmol,1.0eq)，DMAP(17mg,0.14mmol,0.01eq)，三乙胺(217mg,2.15mmol,1.5eq)和硫代羰基二咪唑CDI-S(306mg,1.72mmol,1.2eq)。反应液在室温条件下反应1小时。旋去甲苯后加水，乙酸乙酯萃取，有机相拌样过柱，粗品经过柱层析纯化后得到229-4(270mg,53％收率)。
Figure PCTCN2020126434-appb-000080
(4)在10ml DMF中加入229-4(270mg,0.76mmol,1.0eq)，碳酸铯(739mg,2.27mmol,3.0eq)和229-5(153mg,0.84mmol,1.1eq)。反应液在0℃搅拌2-3h后，LCMS检测原料消失，主峰是产物。向反应液中加水，乙酸乙酯萃取后，饱和食盐水洗涤，有机相拌样过柱，粗品经过柱层析纯化后得到229-6(102mg,27％收率)。
Figure PCTCN2020126434-appb-000081
(5)在10ml DMF中依次加入229-6(102mg,0.21mmol,1.0eq)，碘甲烷(118mg,0.83mmol,4.0eq)和碳酸钾(57mg,0.41mmol,2.0eq)。反应液在25-30℃条件下反应4-6小时，根据LCMS检测反应完为止。加水后用乙酸乙酯萃取，然后用饱和食盐水洗涤，有机相拌样过柱，粗品经过柱层析纯化后得到229(70mg,67％收率)。
Figure PCTCN2020126434-appb-000082
5、化合物1-62的合成
1)参照上述229-3的合成方法制得化合物1-62-1，然后在10ml甲苯中加入1-62-1(0.6g,2.0mmol,1.0eq)和氯甲酸苯酯(0.34g,2.2mmol,1.1eq)，反应液在110℃条件下加热1小时。LCMS检测到原料基本反应完毕，主峰为产品。浓缩溶剂后粗品经柱层析分离后后得到1-62-2(0.7g，83.4％产率)(白色固体)。
Figure PCTCN2020126434-appb-000083
2)在10ml DMF中加入206-4(0.48g,2.1mmol,1.5eq)和AcONa(58mg,0.7mmol,0.5eq)，然后反应液在60℃条件下加入1-62-2(0.6g,1.4mmol,1.0eq)，之后在60℃条件下反应1小时。LCMS检测到产品。向反应液中加入水(10ml)后用乙酸乙酯萃取，有机相用饱和食盐水洗涤(20ml*1)，浓缩有机相后粗品经柱层析分离后得到1-62-消旋体(0.4g，61.4％产率)(白色固体)。
Figure PCTCN2020126434-appb-000084
3)化合物1-62-消旋体(0.5g,98％purity)通过手性HPLC(Column：AD-5H；Column Size：3cm x 25cm,5um；Injection：2.0ml；Mobile phase：Hex：i-PrOH(20％EtOH)＝6：4；Flow rate：20ml/min；Wavelength:UV 254nm；Temperature:25℃；Sample solution：50mg/2ml in EtOH；Run time＝60mins)拆分之后浓缩得到白色固体1-62(0.16g,Rt＝10.51min,100％ee)和1-62-R构型(0.13g,Rt＝30.81min 99.8％ee)。
Figure PCTCN2020126434-appb-000085
生物活性评价：
植物破坏(即生长控制率)的活性级别标准如下：
5级：生长控制率在85％以上；
4级：生长控制率大于等于60％且小于85％；
3级：生长控制率大于等于40％且小于60％；
2级：生长控制率大于等于20％且小于40％；
1级：生长控制率大于等于5％且小于20％；
0级：生长控制率小于5％。
以上生长控制率为鲜重控制率。
苗后测试实验：
将单子叶和双子叶杂草种子(播娘蒿、荠菜、苘麻、猪殃殃、繁缕、麦家公、蔊菜、看 麦娘、日本看麦娘、牛筋草、菵草、硬草、小飞蓬、蜡烛草、婆婆纳、雀麦、节节麦、虉草、反枝苋、藜、鸭跖草、苣荬菜、田旋花、刺儿菜、龙葵、铁苋菜、马唐、稗草、绿狗尾草、金狗尾草、千金子、鸭舌草、野慈姑、萤蔺、香附子、碎米莎草、异型莎草、飘拂草、马齿苋、苍耳、牵牛、白酒草等)以及主要作物种子(小麦、玉米、水稻、大豆、棉花、油菜、谷子、高粱、马铃薯、芝麻、蓖麻等)放置在装有土壤的塑料盆中，然后覆盖0.5-2厘米土壤，使其在良好的温室环境中生长，播种2周后在2-3叶期处理测试植物，分别将供试的本发明化合物用丙酮溶解，然后加入吐温80，以1.5升/公顷油酸甲酯的乳油作为增效剂，用一定的水稀释成一定浓度的溶液，用喷雾塔喷施到植物上。施药后在温室中培养3周后统计杂草的实验效果，所用化合物计量为500,250,125,60,15,7.5g a.i./ha，重复三次，取平均值。代表性数据列于表2-6。
表2苗后杂草试验结果
Figure PCTCN2020126434-appb-000086
表3苗后杂草对比实验结果
Figure PCTCN2020126434-appb-000087
表4苗后杂草试验结果
Figure PCTCN2020126434-appb-000088
Figure PCTCN2020126434-appb-000089
表5苗后杂草对比实验结果
Figure PCTCN2020126434-appb-000090
表6苗后杂草对比实验结果
Figure PCTCN2020126434-appb-000091
Figure PCTCN2020126434-appb-000092
注：N代表无数据；对照化合物A：
Figure PCTCN2020126434-appb-000093
对照化合物B：
Figure PCTCN2020126434-appb-000094
苗前测试实验：
将单子叶和双子叶杂草种子以及主要作物种子(小麦、玉米、水稻、大豆、棉花、油菜、谷子、高粱)放置在装有土壤的塑料盆中，然后覆盖0.5-2厘米土壤，分别将供试的本发明化合物用丙酮溶解，然后加入吐温80，用一定的水稀释成一定浓度的溶液，播种后立即喷施。施药后在温室中培养4周后观察实验结果，发现本发明的药剂多数在250g a.i./ha计量下效果出众，尤其对稗草、马唐、苘麻等杂草，且很多化合物对玉米、小麦、水稻、大豆、有良好的选择性。
同时，我们经过小麦田和水稻田主要杂草测试发现，本发明所述化合物普遍具有较好的杂草防效，尤其是我们注意到对于ALS抑制剂有抗性的野慈姑、萤蔺、异型莎草、播娘蒿、荠菜、麦家公、猪殃殃、香附子等阔叶杂草和莎草有极高的活性，具有非常好的商业价值。
移栽水稻安全性评价与水田杂草防效评价：
在1/1,000,000公顷罐中装入水田土壤后，播种稗草、萤蔺、狼把草的种子，在其上轻轻地覆盖土。其后以蓄水深0.5-1厘米的状态静置于温室内，第二天或者2天后植入野慈姑的块茎。其后保持蓄水深3-4厘米，在稗草、萤蔺、狼把草达到0.5叶，野慈姑达到初生叶期的时间点，将按照通常的制剂方法调制本发明化合物而成的可湿性粉剂或者悬浮剂的水稀释液，用吸液管进行均匀的滴下处理以达到规定的有效成分量。
另外，在1/1,000,000公顷罐中装入水田土壤后，进行平整，使蓄水深3-4厘米，第二天以移栽深度3厘米来移植3叶期的水稻(粳稻)。移植后第5天与上述同样地处理本发明化合物。
分别用肉眼观察药剂处理后第14天稗草、萤蔺、狼把草及野慈姑的生育状态，药剂处理后第21天水稻的生育状态，以上述活性标准级别评价效果，很多化合物表现出了优异的活性和选择性。
注：稗草、萤蔺、狼把草种子均采集自中国黑龙江，经过检测对常规剂量的吡嘧磺隆有抗药性。
同时经过很多测试发现，本发明所述化合物及其组合物很多对结缕草、狗牙根、高羊茅、早熟禾、黑麦草、海滨雀稗等禾本科草坪有很好的选择性，能防除很多关键禾本科杂草以及阔叶杂草。对不同施药方式下的甘蔗、大豆、棉花、油葵、马铃薯、果树、蔬菜等测试也显示出极好的选择性和商业价值。

Claims (10)

  1. 一种含取代异恶唑啉的芳香类化合物，如通式I所示：
    Figure PCTCN2020126434-appb-100001
    其中，
    Q代表
    Figure PCTCN2020126434-appb-100002
    Y代表卤素、卤代烷基或氰基；
    Z代表卤素；
    Q 1、Q 2、Q 3、Q 4、Q 5分别独立地代表O或S；
    R 1、R 2、R 6分别独立地代表氢、烷基、烯基、炔基、环烷基或环烷基烷基；
    R 7、R 8分别独立地代表氢、烷基、卤素、卤代烷基或氨基；
    X 1、X 2分别独立地代表氢、卤素、烷基、烯基、炔基、环烷基、环烷基烷基、-OR 3、-(CO)OR 3或苯基，其中，所述“烷基”、“烯基”、“炔基”、“环烷基”或“环烷基烷基”分别独立地是未取代的或被选自卤素中的至少一个基团所取代的；
    X 3代表卤素、氰基、甲酰基、烷基、烯基、炔基、环烷基、环烷基烷基、-OR 3、-(CO)OR 3、-SR 3、杂环基、杂环基烷基、芳基、芳基烷基或氨基，且X 3不代表甲基，其中，
    所述“烷基”、“烯基”或“炔基”分别独立地是未取代的或被选自卤素、氰基、-OR 3、-(CO)R 3、-SR 3、-(SO 2)R 3、-O(CO)R 3、-O-(SO 2)R 3、-(CO)OR 3、-O(CO)OR 3、-O-烷基-(CO)OR 3或-O(CO)(CO)OR 3中的至少一个基团所取代的，
    所述“环烷基”、“环烷基烷基”、“杂环基”、“杂环基烷基”、“芳基”或“芳基烷基”分别独立地是未取代的或被选自氧代、卤素、氰基、硝基、烷基、烯基、炔基、环烷基、卤代烷基、卤代烯基、卤代炔基、卤代环烷基、被烷基取代的环烷基、-OR 4、-SR 4、-(CO)OR 4、-(SO 2)R 4或-N(R 4) 2中的至少一个基团所取代的，
    所述“氨基”是未取代的或被选自-R 3中的一个或两个基团所取代的；
    X 4分别独立地代表-COOR 5或-烷基-COOR 5；
    R 3分别独立地代表氢、烷基、烯基、炔基、环烷基或环烷基烷基；
    R 4分别独立地代表氢、烷基或卤代烷基；
    R 5分别独立地代表氢、烷基、烯基、炔基、环烷基或环烷基烷基，其中，所述“烷基”、“烯基”、“炔基”、“环烷基”或“环烷基烷基”分别独立地是未取代的或被选自卤素中的至少一个基 团所取代的。
  2. 根据权利要求1所述的一种含取代异恶唑啉的芳香类化合物，其特征在于，
    Y代表卤素、卤代C1-C8烷基或氰基；
    R 1、R 2、R 6分别独立地代表氢、C1-C8烷基、C2-C8烯基、C2-C8炔基、C3-C8环烷基或C3-C8环烷基C1-C8烷基；
    R 7、R 8分别独立地代表氢、C1-C8烷基、卤素、卤代C1-C8烷基或氨基；
    X 1、X 2分别独立地代表氢、卤素、C1-C8烷基、C2-C8烯基、C2-C8炔基、C3-C8环烷基、C3-C8环烷基C1-C8烷基、-OR 3、-(CO)OR 3或苯基，其中，所述“C1-C8烷基”、“C2-C8烯基”、“C2-C8炔基”、“C3-C8环烷基”或“C3-C8环烷基C1-C8烷基”分别独立地是未取代的或被选自卤素中的至少一个基团所取代的；
    X 3代表卤素、氰基、甲酰基、C1-C8烷基、C2-C8烯基、C2-C8炔基、C3-C8环烷基、C3-C8环烷基C1-C8烷基、-OR 3、-(CO)OR 3、-SR 3、杂环基、杂环基C1-C8烷基、芳基、芳基C1-C8烷基或氨基，其中，
    所述“C1-C8烷基”、“C2-C8烯基”或“C2-C8炔基”分别独立地是未取代的或被选自卤素、氰基、-OR 3、-(CO)R 3、-SR 3、-(SO 2)R 3、-O(CO)R 3、-O-(SO 2)R 3、-(CO)OR 3、-O(CO)OR 3、-O-(C1-C8烷基)-(CO)OR 3或-O(CO)(CO)OR 3中的至少一个基团所取代的，
    所述“C3-C8环烷基”、“C3-C8环烷基C1-C8烷基”、“杂环基”、“杂环基C1-C8烷基”、“芳基”或“芳基C1-C8烷基”分别独立地是未取代的或被选自氧代、卤素、氰基、硝基、C1-C8烷基、C2-C8烯基、C2-C8炔基、C3-C8环烷基、卤代C1-C8烷基、卤代C2-C8烯基、卤代C2-C8炔基、卤代C3-C8环烷基、被C1-C8烷基取代的C3-C8环烷基、-OR 4、-SR 4、-(CO)OR 4、-(SO 2)R 4或-N(R 4) 2中的至少一个基团所取代的，
    所述“氨基”是未取代的或被选自-R 3中的一个或两个基团所取代的；
    X 4分别独立地代表-COOR 5或-(C1-C8烷基)-COOR 5；
    R 3分别独立地代表氢、C1-C8烷基、C2-C8烯基、C2-C8炔基、C3-C8环烷基或C3-C8环烷基C1-C8烷基；
    R 4分别独立地代表氢、C1-C8烷基或卤代C1-C8烷基；
    R 5分别独立地代表氢、C1-C8烷基、C2-C8烯基、C2-C8炔基、C3-C8环烷基或C3-C8环烷基C1-C8烷基，其中，所述“C1-C8烷基”、“C2-C8烯基”、“C2-C8炔基”、“C3-C8环烷基”或“C3-C8环烷基C1-C8烷基”分别独立地是未取代的或被选自卤素中的至少一个基团所取代的。
  3. 根据权利要求1或2所述的一种含取代异恶唑啉的芳香类化合物，其特征在于，
    Y代表卤素、卤代C1-C6烷基或氰基；
    R 1、R 2、R 6分别独立地代表氢、C1-C6烷基、C2-C6烯基、C2-C6炔基、C3-C6环烷基或C3-C6环烷基C1-C6烷基；
    R 7、R 8分别独立地代表氢、C1-C6烷基、卤素、卤代C1-C6烷基或氨基；
    X 1、X 2分别独立地代表氢、卤素、C1-C6烷基、C2-C6烯基、C2-C6炔基、C3-C6环烷基、C3-C6环烷基C1-C6烷基、-OR 3、-(CO)OR 3或苯基，其中，所述“C1-C6烷基”、“C2-C6烯基”、“C2-C6炔基”、“C3-C6环烷基”或“C3-C6环烷基C1-C6烷基”分别独立地是未取代的或被选自卤素中的至少一个基团所取代的；
    X 3代表卤素、氰基、甲酰基、C1-C6烷基、C2-C6烯基、C2-C6炔基、C3-C6环烷基、C3-C6环烷基C1-C6烷基、-OR 3、-(CO)OR 3、-SR 3、杂环基、杂环基C1-C6烷基、芳基、芳基C1-C6烷基或氨基，其中，
    所述“C1-C6烷基”、“C2-C6烯基”或“C2-C6炔基”分别独立地是未取代的或被选自卤素、氰基、-OR 3、-(CO)R 3、-SR 3、-(SO 2)R 3、-O(CO)R 3、-O-(SO 2)R 3、-(CO)OR 3、-O(CO)OR 3、-O-(C1-C6烷基)-(CO)OR 3或-O(CO)(CO)OR 3中的至少一个基团所取代的，
    所述“C3-C6环烷基”、“C3-C6环烷基C1-C6烷基”、“杂环基”、“杂环基C1-C6烷基”、“芳基”或“芳基C1-C6烷基”分别独立地是未取代的或被选自氧代、卤素、氰基、硝基、C1-C6烷基、C2-C6烯基、C2-C6炔基、C3-C6环烷基、卤代C1-C6烷基、卤代C2-C6烯基、卤代C2-C6炔基、卤代C3-C6环烷基、被C1-C6烷基取代的C3-C6环烷基、-OR 4、-SR 4、-(CO)OR 4、-(SO 2)R 4或-N(R 4) 2中的至少一个基团所取代的，
    所述“氨基”是未取代的或被选自-R 3中的一个或两个基团所取代的；
    X 4分别独立地代表-COOR 5或-(C1-C6烷基)-COOR 5；
    R 3分别独立地代表氢、C1-C6烷基、C2-C6烯基、C2-C6炔基、C3-C6环烷基或C3-C6环烷基C1-C6烷基；
    R 4分别独立地代表氢、C1-C6烷基或卤代C1-C6烷基；
    R 5分别独立地代表氢、C1-C6烷基、C2-C6烯基、C2-C6炔基、C3-C6环烷基或C3-C6环烷基C1-C6烷基，其中，所述“C1-C6烷基”、“C2-C6烯基”、“C2-C6炔基”、“C3-C6环烷基”或“C3-C6环烷基C1-C6烷基”分别独立地是未取代的或被选自卤素中的至少一个基团所取代的。
  4. 根据权利要求1-3任意一项所述的一种含取代异恶唑啉的芳香类化合物，其特征在于，
    Y代表卤素；
    R 1、R 2、R 6分别独立地代表C1-C6烷基；
    R 7、R 8分别独立地代表氢或卤代C1-C6烷基；
    X 1、X 2分别独立地代表氢；
    X 3代表卤素、甲酰基、C1-C6烷基、C2-C6烯基、C2-C6炔基、C3-C6环烷基、C3-C6环烷基C1-C3烷基、-OR 3、苯基或苄基，其中，
    所述“C1-C6烷基”、“C2-C6烯基”或“C2-C6炔基”分别独立地是未取代的或被选自卤素、-OR 3、-O(CO)R 3、-(CO)OR 3、-O-(C1-C3烷基)-(CO)OR 3或-O(CO)(CO)OR 3中的1、2或3个基团所取代的，
    所述“C3-C6环烷基”、“C3-C6环烷基C1-C3烷基”、“苯基”或“苄基”分别独立地是未取代的或被选自卤素、C1-C6烷基、C2-C6烯基、C2-C6炔基、C3-C6环烷基、卤代C1-C6烷基、卤代C2-C6烯基、卤代C2-C6炔基、卤代C3-C6环烷基、被C1-C6烷基取代的C3-C6环烷基、-OR 4或-(CO)OR 4中的1、2或3个基团所取代的；
    X 4分别独立地代表-COOR 5；
    R 3分别独立地代表氢、C1-C6烷基、C2-C6烯基、C2-C6炔基、C3-C6环烷基或C3-C6环烷基C1-C3烷基；
    R 4分别独立地代表氢、C1-C6烷基或卤代C1-C6烷基；
    R 5分别独立地代表氢、C1-C6烷基、C2-C6烯基、C2-C6炔基或C3-C6环烷基；
    优选地，Y代表氯；
    Z代表氟；
    R 7代表卤代C1-C6烷基；
    R 8代表氢；
    X 3代表卤素、甲酰基、C1-C6烷基、C3-C6环烷基、C3-C6环烷基C1-C3烷基、-OR 3、-(C1-C3烷基)-OR 3、-(C1-C3烷基)-O(CO)R 3、-(C1-C3烷基)-(CO)OR 3、-(C1-C3烷基)-O-(C1-C3烷基)-(CO)OR 3、-(C1-C3烷基)-O(CO)(CO)OR 3、苯基或苄基，其中，
    所述“C1-C6烷基”分别独立地是未取代的或被选自卤素中的1、2或3个基团所取代的；
    R 3分别独立地代表氢或C1-C6烷基；
    R 5分别独立地代表氢或C1-C6烷基；
    更优选地，Q代表
    Figure PCTCN2020126434-appb-100003
    Figure PCTCN2020126434-appb-100004
  5. 一种具有S构型的含取代异恶唑啉的芳香类化合物，如通式I’所示：
    Figure PCTCN2020126434-appb-100005
    其中，X 3’代表氢、甲基或X 3，取代基X 1、X 2、X 3、X 4、Q、Y和Z的定义如权利要求1-4所示且X 3、X 4不相同；基于在该位置上具有R和S构型的立体异构体含量而言，其具有60-100％(S)的立体化学纯度，优选70-100％(S)，更优选80-100％(S)，进一步优选90-100％(S)，更进一步优选95-100％(S)。
  6. 根据权利要求1-5任意一项所述的化合物，其选自以下化合物或其S构型中的任意一个：
    Figure PCTCN2020126434-appb-100006
    Figure PCTCN2020126434-appb-100007
    Figure PCTCN2020126434-appb-100008
    Figure PCTCN2020126434-appb-100009
    Figure PCTCN2020126434-appb-100010
    或者，选自以下化合物中的任意一个：
    Figure PCTCN2020126434-appb-100011
    Figure PCTCN2020126434-appb-100012
    Figure PCTCN2020126434-appb-100013
    Figure PCTCN2020126434-appb-100014
    Figure PCTCN2020126434-appb-100015
  7. 一种如权利要求1-6任意一项所述的含取代异恶唑啉的芳香类化合物的制备方法，其特征在于，包括以下步骤：
    当Q代表
    Figure PCTCN2020126434-appb-100016
    时，(1)将通式Ⅱ-1所示的化合物与通式Ⅲ-1所示的化合物进行环化反应，制得如通式Ⅰ-1所示的化合物，其化学反应方程式如下：
    Figure PCTCN2020126434-appb-100017
    当Q代表
    Figure PCTCN2020126434-appb-100018
    时，(2)将通式Ⅱ-2所示的化合物与通式Ⅲ-2所示的化合物进行环化反应，制得如通式Ⅰ-2所示的化合物，其化学反应方程式如下：
    Figure PCTCN2020126434-appb-100019
    (3)将通式Ⅱ-3所示的化合物与通式Ⅲ-3所示的化合物进行反应得到通式Ⅰ-3所示的化合物；
    Figure PCTCN2020126434-appb-100020
    (4)将通式Ⅱ-4所示的化合物与通式Ⅲ-4所示的化合物进行反应得到通式Ⅰ-4所示的化合物；
    Figure PCTCN2020126434-appb-100021
    或者，(5)通式Ⅰ-5所示的化合物与R 6’-Hal经取代反应制得如通式Ⅰ-6所示的化合物；
    其化学反应方程式如下：
    Figure PCTCN2020126434-appb-100022
    其中，L 1、L 2、L 3、L 4、L 5、L 6和L 7分别独立地代表C1-C6烷基或芳基，优选甲基、乙基或苯基；Hal代表卤素，优选碘；R 6’代表R 6中除氢以外的基团；其他取代基R 1、R 2、R 6、R 7、R 8、X 1、X 2、X 3、X 4、Q 1、Q 2、Q 3、Q 4、Q 5、Y和Z的定义如权利要求1-6所示；
    优选地，所述步骤(1)、(2)、(4)和(5)均在碱和溶剂的存在下进行；更优选地，所述碱选自无机碱或有机碱中的至少一种；更优选地，所述溶剂选自DMF、DMA、甲醇、乙醇、乙腈、二氯乙烷、DMSO、Dioxane、二氯甲烷或乙酸乙酯中的至少一种；
    优选地，所述步骤(3)在酸的存在下进行；更优选地，所述酸选自醋酸、盐酸或硫酸。
  8. 一种除草剂组合物，其特征在于，包括除草有效量的权利要求1-6任意一项所述的含取代异恶唑啉的芳香类化合物中的至少一种，优选地，还包括制剂助剂。
  9. 一种控制杂草的方法，其特征在于，包括将除草有效量的权利要求1-6任意一项所述的含取代异恶唑啉的芳香类化合物中的至少一种或权利要求8所述的除草剂组合物使用在植物上或者杂草区域。
  10. 如权利要求1-6任意一项所述的含取代异恶唑啉的芳香类化合物中的至少一种或权 利要求8所述的除草剂组合物在控制杂草上的用途，优选地，将所述的含取代异恶唑啉的芳香类化合物用于防除有用作物中的杂草，所述有用作物为转基因作物或者基因组编辑技术处理过的作物。
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