WO2020057391A1 - 哒嗪胺类化合物的制备及其应用 - Google Patents

哒嗪胺类化合物的制备及其应用 Download PDF

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WO2020057391A1
WO2020057391A1 PCT/CN2019/104960 CN2019104960W WO2020057391A1 WO 2020057391 A1 WO2020057391 A1 WO 2020057391A1 CN 2019104960 W CN2019104960 W CN 2019104960W WO 2020057391 A1 WO2020057391 A1 WO 2020057391A1
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halo
alkyl
alkoxy
cyano
och
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PCT/CN2019/104960
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English (en)
French (fr)
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周银平
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周银平
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Priority to EP19861455.4A priority Critical patent/EP3854791A4/en
Priority to BR112021005242-9A priority patent/BR112021005242A2/pt
Priority to US17/278,129 priority patent/US20210337797A1/en
Publication of WO2020057391A1 publication Critical patent/WO2020057391A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
    • C07D403/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • 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
    • A01N43/58—1,2-Diazines; Hydrogenated 1,2-diazines
    • 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
    • A01N43/60—1,4-Diazines; Hydrogenated 1,4-diazines
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
    • A01N43/66—1,3,5-Triazines, not hydrogenated and not substituted at the ring nitrogen atoms
    • A01N43/68—1,3,5-Triazines, not hydrogenated and not substituted at the ring nitrogen atoms with two or three nitrogen atoms directly attached to ring carbon atoms
    • A01N43/70—Diamino—1,3,5—triazines with only one oxygen, sulfur or halogen atom or only one cyano, thiocyano (—SCN), cyanato (—OCN) or azido (—N3) group directly attached to a ring carbon atom
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
    • A01N43/707—1,2,3- or 1,2,4-triazines; Hydrogenated 1,2,3- or 1,2,4-triazines
    • 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
    • A01N43/713—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with four or more nitrogen atoms as the only ring hetero atoms
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/84—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms six-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,4
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
    • A01P13/00—Herbicides; Algicides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D237/00—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings
    • C07D237/02—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings not condensed with other rings
    • C07D237/06—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D237/10—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members 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
    • C07D237/20—Nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D237/00—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings
    • C07D237/02—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings not condensed with other rings
    • C07D237/06—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D237/10—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members 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
    • C07D237/22—Nitrogen and oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D237/00—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings
    • C07D237/02—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings not condensed with other rings
    • C07D237/06—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D237/10—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members 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
    • C07D237/24—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
    • C07D403/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
    • C07D413/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings directly linked by a ring-member-to-ring-member bond

Definitions

  • This application belongs to the field of agricultural herbicides.
  • the invention relates to a new type of pyridazamine compounds and compositions, their uses and methods of use.
  • Farmland weeds are an important factor affecting crop production.
  • the area of farmland affected by weeds in China is 43 million hectares, which reduces 17.5 million tons of grain output each year.
  • Weed chemical control is the most important method for weed control in farmland. It has the advantages of labor-saving, time-saving, high-efficiency and quickness.
  • Pyridazine compounds are generally used in medicine for anti-cancer and anti-inflammatory applications.
  • the pyridazamine compounds of the present application have excellent herbicidal activity, and such structures have not been reported in the literature as herbicides. These compounds are agriculturally useful as herbicides.
  • the present application provides a novel pyridazine amine compound, a method for controlling weeds, and an agricultural application of components containing these compounds.
  • R 1 is selected from hydrogen, halogen, cyano, unsubstituted or substituted by 1-4 phenoxy or heteroaryloxy groups independently selected from halogen, nitro, cyano, C 1 -C 12 Alkyl, halo C 1 -C 12 alkyl, C 1 -C 12 alkoxy, halo C 1 -C 12 alkoxy, C 3 -C 12 cycloalkyl, C 1 -C 12 alkylcarbonyl Or C 1 -C 12 alkoxycarbonyl;
  • R 2 is selected from hydrogen, C 1 -C 12 alkyl, halo C 1 -C 12 alkyl, C 1 -C 12 alkoxy, halo C 1 -C 12 alkoxy, C 3 -C 6 ring Alkyl, cyano C 1 -C 12 alkyl, C 1 -C 12 alkylamino, halo C 1 -C 12 alkylamino, C 2 -C 6 dialkylamino, C 2 -C 12 alkenyl , Halogenated C 2 -C 12 alkynyl, C 2 -C 12 alkenyloxy, halogenated C 2 -C 12 alkenyloxy, C 2 -C 12 alkenyl, halogenated C 2 -C 12 alkenyl, C 2- C 12 alkynyloxy, halo C 2 -C 12 alkynyloxy, C 1 -C 12 alkylsulfonyl, C 1 -C 12 alkylcarbonyl,
  • R 3 is selected from unsubstituted or substituted by 1-4 phenyl, benzyl or heteroaryl groups independently selected from the group consisting of halogen, hydroxy, nitro, cyano, CHO, COOH, COONa, C 1- C 12 alkyl, halo C 1 -C 12 alkyl, C 1 -C 12 alkoxy, halo C 1 -C 12 alkoxy, C 3 -C 6 cycloalkyl, cyano C 1 -C 12 alkyl, C 1 -C 12 alkylamino, halogenated C 1 -C 12 alkylamino, C 2 -C 6 dialkylamino, C 2 -C 12 alkenyl, halogenated C 2 -C 12 alkyne , C 2 -C 12 alkenyloxy, halo C 2 -C 12 alkenyloxy, C 2 -C 12 alkynyl, halo C 2 -C 12 alkynyl,
  • R 2 NR 3 may also constitute a five- or six-membered ring substituted or unsubstituted by one to four groups independently selected from the group consisting of halogen, hydroxyl, nitro, cyano CHO, COOH, COONa, C 1 -C 12 alkyl, halo C 1 -C 12 alkyl, C 3 -C 12 cycloalkyl, C 1 -C 12 alkoxy, halo C 1 -C 12 alkoxy, C 1 -C 12 alkylthio, C 1 -C 12 alkylcarbonyl, or C 1 -C 12 alkoxycarbonyl;
  • R 4 is selected from halogen, cyano, CHO, COOH, COONa, C 1 -C 12 alkylsulfonyl, halo C 1 -C 12 alkylsulfonyl or substituted by 1-4 groups independently selected from Unsubstituted arylsulfonyl, the independently substituted group is selected from the group consisting of halogen, hydroxy, nitro, cyano, CHO, COOH, COONa, C 1 -C 12 alkyl, halo C 1 -C 12 alkyl, C 3 -C 12 cycloalkyl, C 1 -C 12 alkoxy, halo C 1 -C 12 alkoxy, C 1 -C 12 alkylthio, C 1 -C 12 alkylcarbonyl Or C 1 -C 12 alkoxycarbonyl;
  • R 1 is selected from hydrogen, Cl, Br, F, I, cyano, unsubstituted or substituted by 1-4 phenoxy or heteroaryloxy groups independently selected from halogen, nitro, cyano , C 1 -C 6 alkyl, halo C 1 -C 6 alkyl, C 1 -C 6 alkoxy, halo C 1 -C 6 alkoxy, C 3 -C 6 cycloalkyl, C 1 -C 6 alkylcarbonyl or C 1 -C 6 alkoxycarbonyl;
  • R 2 is selected from hydrogen, C 1 -C 6 alkyl, halo C 1 -C 6 alkyl, C 1 -C 6 alkoxy, halo C 1 -C 6 alkoxy, C 3 -C 6 ring Alkyl, cyano C 1 -C 6 alkyl, C 1 -C 6 alkylamino, halogenated C 1 -C 6 alkylamino, C 2 -C 6 dialkylamino, C 2 -C 6 alkenyl , Halogenated C 2 -C 6 alkenyl, C 2 -C 6 alkenyloxy, halogenated C 2 -C 6 alkenyloxy, C 2 -C 6 alkynyl, halogenated C 2 -C 6 alkenyl, C 2- C 6 alkynyloxy, halo C 2 -C 6 alkynyloxy, C 1 -C 6 alkylsulfonyl, C 1 -C 6 alkylcarbonyl
  • R 3 is selected from unsubstituted or substituted by 1-4 phenyl, benzyl or heteroaryl groups independently selected from Cl, Br, F, I, hydroxyl, nitro, cyano, CHO, COOH , COONa, C 1 -C 6 alkyl, halo C 1 -C 6 alkyl, C 1 -C 6 alkoxy, halo C 1 -C 6 alkoxy, C 3 -C 6 cycloalkyl, Cyano C 1 -C 6 alkyl, C 1 -C 6 alkylamino, halo C 1 -C 6 alkylamino, C 2 -C 6 dialkylamino, C 2 -C 6 alkenyl, halo C 2 -C 6 alkynyl, C 2 -C 6 alkenyloxy, halo C 2 -C 6 alkenyloxy, C 2 -C 6 alkynyl, halo C 2 -C 6 alkynyl
  • R 2 NR 3 may also constitute a five- or six-membered ring substituted or unsubstituted by one to four groups independently selected from the group consisting of Cl, Br, F, I, Hydroxyl, nitro, cyano, CHO, COOH, COONa, C 1 -C 6 alkyl, halo C 1 -C 6 alkyl, C 3 -C 6 cycloalkyl, C 1 -C 6 alkoxy, Halo C 1 -C 6 alkoxy, C 1 -C 6 alkylthio, C 1 -C 6 alkylcarbonyl or C 1 -C 6 alkoxycarbonyl;
  • R 4 is selected from Cl, Br, F, I, cyano, CHO, COOH, COONa, C 1 -C 6 alkylsulfonyl or halo C 1 -C 6 alkylsulfonyl;
  • a further preferred compound of the present application is: in the general formula (I)
  • R 1 is selected from H, Cl, Br, F, I, CN, CH 3 , CH 2 CH 3 , tert-butyl, cyclopropyl, CF 3 , CH 2 CF 3 , OCH 3 , OCF 3 , OCH 2 CF 3 , SO 2 CH 3 , CO 2 CH 3 , unsubstituted or substituted phenoxy, the substituent is selected from 1-3 groups: Cl, Br, F, I, CN, NO 2 , CHO, COOH, COONa, CH 3 , CH 2 CH 3 , tert-butyl, cyclopropyl, CHF 2 , CF (CF 3 ) 2 , CF 3 , CH 2 CF 3 , OCH 3 , OCHF 2 , OCF 3 , OCH 2 CF 3 or SO 2 CH 3 ;
  • R 2 is selected from H, methyl, ethyl, propyl, isopropyl, t-butyl, n-butyl or methoxy, cyclopropyl, cyanoethyl, methylamino, methanesulfonyl, allyl , Propargyl, methanesulfonyl, p-toluenesulfonyl, ethylcarbonyl or formyl;
  • R 3 is selected from unsubstituted or substituted by 1-3, phenyl, benzyl or heteroaryl groups independently selected from the group consisting of OH, Cl, Br, F, I, CN, NO 2 , CHO, COOH, COONa, CH 3 , CH 2 CH 3 , tert-butyl, cyclopropyl, CHF 2 , CF 3 , CF (CF 3 ) 2 , CH 2 CF 3 , OCH 3 , OCHF 2 , OCF 3 , OCH 2 CF 3 or SO 2 CH 3 ;
  • R 2 NR 3 may also constitute a five- or six-membered ring substituted or unsubstituted by one to three groups independently selected from the group consisting of OH, Cl, Br, F, I, CN, NO 2 , CH 3 , CH 2 CH 3 , tert-butyl, cyclopropyl, CHF 2 , CF (CF 3 ) 2 , CF 3 , CH 2 CF 3 , OCH 3 , OCHF 2 , OCF 3 , OCH 2 CF 3 or SO 2 CH 3 ;
  • R 4 is selected from Cl, Br, F, I, CN, SO 2 CH 3 or SO 2 CH 2 CH 3 ;
  • a further preferred compound of the present application is: in the general formula (I)
  • R 1 is selected from Cl, Br, F, I, 2-methylphenol, 2-isopropylphenol, 2-cyclopropylphenol, 2-methyl-6-cyclopropylphenol, or 2-iodophenol;
  • R 2 is selected from H, CH 3 , CH 2 CH 3 , cyclopropyl, methoxy or methylamino;
  • R 3 is selected from unsubstituted or substituted by 1-3, independently selected from phenyl, pyrimidinyl, pyrazolyl, pyridyl, or pyridazinyl: OH, Cl, Br, F, I, CN, NO 2 , CHO, COOH, COONa, CH 3 , CH 2 CH 3 , tert-butyl, cyclopropyl, CHF 2 , CF 3 , CH 2 CF 3 , OCH 3 , OCHF 2 , OCF 3 , CF (CF 3 ) 2. OCH 2 CF 3 or SO 2 CH 3 ;
  • R 2 NR 3 may also form morpholine, piperazine, piperidine, pyrrole ring, pyrazole ring, triazole ring, pyrimidine ring or Wait;
  • R 4 is selected from Cl, Br, F, I or CN;
  • a further preferred compound of the present application is: in the general formula (I)
  • R 1 is selected from Cl, Br, F or I;
  • R 2 is selected from H, CH 3 or CH 2 CH 3 ;
  • R 3 is selected from unsubstituted or substituted by 1-3, phenyl, pyridyl, or pyridazinyl independently selected from the group: OH, Cl, Br, F, I, CN, NO 2 , CHO, COOH, COONa, CH 3 , CH 2 CH 3 , tert-butyl, CHF 2 , CF 3 , CH 2 CF 3 , CF (CF 3 ) 2 , OCH 3 , OCHF 2 , OCF 3 , OCH 2 CF 3 or SO 2 CH 3 ;
  • R 2 NR 3 can also be composed Ring etc
  • R 4 is selected from Cl, Br, F, I or CN;
  • stereoisomers can be formed because different groups or substituents are attached to a chiral carbon or nitrogen (respectively different configurations are represented by R and S).
  • This application includes the R-isomer and S-isomer and mixtures thereof in any proportion.
  • Halogen refers to fluorine, chlorine, bromine or iodine.
  • Alkyl linear, branched or cyclic alkyl, such as methyl, ethyl, propyl, isopropyl, tert-butyl or cyclopropyl.
  • Haloalkyl A straight or branched chain haloalkyl group.
  • the hydrogen atoms on these alkyl groups may be partially or completely replaced by halogen atoms.
  • haloalkyl groups such as chloromethyl, dichloromethyl, trichloromethyl, and fluoromethyl. Radical, difluoromethyl or trifluoromethyl.
  • Alkoxy linear, branched or cyclic alkoxy, such as methoxy, ethoxy, propoxy, isopropoxy, tert-butoxy or cyclopropoxy.
  • Haloalkoxy linear or branched haloalkoxy.
  • the hydrogen atoms on these alkoxy groups may be partially or completely replaced by halogen atoms.
  • haloalkyl such as chloromethoxy, dichloromethoxy, trichloro Methoxy, fluoromethoxy, difluoromethoxy or trifluoromethoxy.
  • Alkylthio A linear or branched alkyl group attached to the structure via a sulfur atom bond.
  • Haloalkylthio A straight or branched chain alkylthio group.
  • the hydrogen atoms on these alkylthio groups may be partially or completely replaced by halogen atoms.
  • halogen atoms For example, chloromethylthio, dichloromethylthio, trichloromethylthio, fluoromethylthio, difluoromethylthio, trifluoromethylthio, or chlorofluoromethylthio, and the like.
  • Alkenyl straight or branched and may have a double bond at any position, such as vinyl or allyl.
  • Alkynyl straight or branched and may have a triple bond at any position, such as ethynyl or propargyl.
  • the aryl group in the aryl group and the aralkyl group includes a phenyl group or a naphthyl group.
  • the heteroaryl group referred to in this application is a five-membered ring, six-membered ring or fused heterocyclic compound containing one or more N, O, and S heteroatoms.
  • R 1 , R 2 , R 3 and R 4 have the same meanings as defined in the general formula (I).
  • Acids that can be salted with pyridazinamine represented by the general formula (II) in the present application include: carboxylic acids such as acetic acid, propionic acid, butyric acid, oxalic acid, or trifluoroacetic acid; sulfonic acids such as methanesulfonic acid, p-toluene Sulfonic acid or dodecylbenzenesulfonic acid; and inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid or carbonic acid.
  • the bases and metals that can be salted with the pyridazinamine represented by the general formula (II) in the present application include: metals such as sodium, alkali, calcium, or magnesium; organic bases such as sodium methoxide, sodium ethoxide, and sodium tert-butoxide , Potassium methoxide, potassium ethoxide, sodium formate, butyllithium or sodium acetate, etc .; inorganic bases, such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydride or sodium amide;
  • Tables 1 and 2 respectively list specific substituents of the R 1 and R 4 moieties in the general formula I, but they are not limited to these substituents.
  • R 1 represents some specific substituents
  • R 4 represents some specific substituents
  • the compound of general formula (I) of the present application can be obtained from pyridazine compound II by the method described in the literature, such as
  • R 2 NR 3 indicates Groups can be prepared from compound A with reference to the literature, such as: CN105753853A and CN103058933.
  • the reaction is performed in a suitable solvent.
  • the suitable solvent may be selected from benzene, toluene, xylene, acetone, tetrahydrofuran, acetonitrile, N, N-dimethylformamide, N-methylpyrrolidone, dichloromethane, chloroform, Ethyl chloride or ethyl acetate.
  • the reaction can be carried out in the presence or absence of a base. When the reaction is carried out in the presence of a base, the reaction can be accelerated.
  • the base may be selected from: alkali metal hydrides, such as sodium hydride, lithium hydride, or sodium amide; etc .; alkali metal hydroxides, such as sodium hydroxide or potassium hydroxide; alkali metal carbonates, such as sodium carbonate or carbonate Potassium; organic bases, such as pyridine, 4-dimethylaminopyridine, triethylamine, N-methylpyrrole or diisopropylethylamine.
  • the reaction temperature may be between -10 ° C and a suitable solvent boiling temperature selected for the reaction, and is usually 0-100 ° C.
  • the reaction time is 30 minutes to 20 hours, and usually 1 to 10 hours.
  • X and Z are both leaving groups, and X and Z are selected from fluorine, chlorine, bromine, iodine, mesylate or p-toluenesulfonate.
  • Compound I and its agriculturally acceptable salts are suitable for use as herbicides in the form of mixtures of isomers and in the form of pure isomers. They are suitable for direct use or for use in suitably formulated compositions.
  • the herbicidal composition comprising Compound I is very effective in controlling plant growth in non-crop areas, especially at high application rates. They act in crops such as wheat, rice, corn, soybeans and cotton on broadleaf and grass weeds without causing any significant damage to the crop. This effect is mainly observed at low application rates.
  • compounds I or compositions comprising them can be additionally used in many other crops to eliminate unwanted plants.
  • suitable crops are:
  • Compound I or a herbicidal composition comprising compound I may be, for example, ready-to-spray aqueous solutions, powders, suspensions and highly concentrated aqueous, oily or other suspensions or dispersions, emulsions, oil dispersions, pastes, powders, materials for broadcasting or
  • the granular form is used by spraying, atomizing, dusting, sowing, watering or treating the seeds or mixing with the seeds.
  • the use form depends on the intended purpose; in each case, the best possible distribution of the active ingredients of the application should be ensured.
  • the herbicidal composition comprises a herbicidally effective amount of at least one compound of formula I or an agriculturally acceptable salt of I and an adjuvant commonly used in formulating crop protection agents.
  • auxiliaries commonly used in the formulation of crop protection agents are: inert auxiliaries, solid carriers, surfactants (such as dispersants, protective colloids, emulsifiers, wetting agents and tackifiers), organic and inorganic thickeners, Fungicides, antifreezes, and defoamers, if appropriate, colorants and binders for seed formulations.
  • surfactants such as dispersants, protective colloids, emulsifiers, wetting agents and tackifiers
  • organic and inorganic thickeners such as Fungicides, antifreezes, and defoamers, if appropriate, colorants and binders for seed formulations.
  • thickeners i.e. compounds which impart modified flow properties to the formulation, i.e. high viscosity at rest and low viscosity at movement
  • polysaccharides such as xanthan gum
  • organic and inorganic flake minerals are examples of thickeners.
  • defoamers are: polysiloxane emulsions, long-chain alcohols, fatty acids, fatty acid salts, organic fluorine compounds, and mixtures thereof.
  • antifreeze examples include: ethylene glycol, propylene glycol, urea or glycerol.
  • binder examples include polyvinylpyrrolidone, polyvinyl acetate, polyvinyl alcohol, and sodium cellulose acetate.
  • Suitable inert auxiliaries are, for example, the following: medium- to high-boiling mineral oil fractions such as kerosene and diesel, but also coal tar and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons such as paraffin, four Hydrogenated naphthalenes, alkylated naphthalenes and their derivatives, alkylated benzenes and their derivatives, alcohols such as methanol, ethanol, propanol, butanol and cyclohexanol, ketones such as cyclohexanone or strong polar solvents such as Amines such as N-methylpyrrolidone, and water.
  • medium- to high-boiling mineral oil fractions such as kerosene and diesel, but also coal tar and oils of vegetable or animal origin
  • aliphatic, cyclic and aromatic hydrocarbons such as paraffin
  • four Hydrogenated naphthalenes alkylated naphthal
  • the solid carriers are: mineral earth such as silica, silica gel, silicate, talc, kaolin, limestone, lime, chalk, red basalt, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate and magnesium oxide. Crushed synthetic materials, fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate and urea, and products of plant origin such as cereal flour, bark flour, wood flour and nut shell flour, cellulose flour or other solid carriers.
  • mineral earth such as silica, silica gel, silicate, talc, kaolin, limestone, lime, chalk, red basalt, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate and magnesium oxide. Crushed synthetic materials, fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate and urea, and products of plant origin such
  • Suitable surfactants are aromatic sulfonic acids such as lignosulfonic acid (e.g. Borrespers type, Borregaard), phenolsulfonic acid, naphthalenesulfonic acid (Morwet Type, Akzo Nobel) and dibutylnaphthalenesulfonic acid (Nekal type, BASF SE) and alkali metal salts, alkaline earth metal salts and ammonium salts of fatty acids, alkyl- and alkylaryl sulfonates, alkyl sulfates, Lauryl ether sulfates and fatty alcohol sulfates, as well as sulfated cetyl-, hepta- and octadecyl alcohol, and fatty alcohol glycol ether salts, sulfonated naphthalene and its derivatives with formaldehyde.
  • aromatic sulfonic acids such as lignosulfonic acid (e.g. Borre
  • Condensates condensation products of naphthalene or naphthalenesulfonic acid with phenol and formaldehyde, polyoxyethylene octyl phenol ether, ethoxylated isooctyl-, octyl- or nonylphenol, alkylphenyl or tributylbenzene
  • Polyglycol ether alkylaryl polyether alcohol, isotridecanol, fatty alcohol / ethylene oxide condensate, ethoxylated castor oil, polyoxyethylene alkyl ether or polyoxypropylene alkyl ether, Lauryl alcohol polyethylene glycol ether acetate, sorbitol ester, lignin sulfite waste liquid and protein, denatured protein, polysaccharide (such as methyl cellulose) Hydrophobic modified starch, polyvinyl alcohol (Mowiol type, Clariant), polycarboxylates (BASF SE, Sokalan type), polyal
  • Powders, spreading materials and dusts can be prepared by mixing or grinding the active ingredients with a solid carrier.
  • Particles such as coated particles, impregnated particles and homogeneous particles can be prepared by adhering the active ingredient to a solid carrier.
  • Aqueous use forms can be prepared from emulsion concentrates, suspensions, pastes, wettable powders or water-dispersible granules by adding water.
  • the compounds of the formula I or Ia can be homogenized directly or dissolved in oil or solvents with the aid of a wetting agent, tackifier, dispersant or emulsifier.
  • concentrates containing active substances, wetting agents, tackifiers, dispersants or emulsifiers and, if necessary, solvents or oils such concentrates being suitable for dilution with water.
  • the concentration of the compound of formula I in the ready-to-use preparations can be varied within wide limits.
  • the formulations usually contain at least one active compound in an amount of 0.001 to 98% by weight, preferably 0.01 to 95% by weight.
  • the active compound is used in a purity of 90-100%, preferably 95-100% (according to the NMR spectrum).
  • Formulations or ready-to-use preparations may also contain acid, base or buffer systems, suitable examples are: phosphoric acid or sulfuric acid, or urea or ammonia.
  • Compound I of the present application can be formulated, for example, as follows:
  • the active compound 20 parts by weight of the active compound is dissolved in 70 parts by weight of cyclohexanone and 10 parts by weight of a dispersant such as polyvinylpyrrolidone is added. Dilute with water to obtain a dispersion.
  • the active compound content is 20% by weight.
  • the active compound 15 parts by weight of the active compound are dissolved in 75 parts by weight of an organic solvent such as an alkylarene and calcium dodecylbenzenesulfonate and castor oil ethoxylate (in each case 5 parts by weight) are added. Dilute with water to obtain an emulsion.
  • the formulation has an active compound content of 15% by weight.
  • the active compound 25 parts by weight of the active compound are dissolved in 35 parts by weight of an organic solvent such as an alkylarene and calcium dodecylbenzenesulfonate and castor oil ethoxylate (in each case 5 parts by weight) are added.
  • an organic solvent such as an alkylarene and calcium dodecylbenzenesulfonate and castor oil ethoxylate (in each case 5 parts by weight) are added.
  • This mixture was introduced into 30 parts by weight of water by means of an emulsifier (Ultraturrax) and made into a homogeneous emulsion. Dilute with water to obtain an emulsion.
  • the formulation has an active compound content of 25% by weight.
  • the active compound is finely ground and added with 50 parts by weight of a dispersant and a wetting agent, and it is made into water-dispersible or water-soluble particles by means of an industrial device (such as an extruder, a spray tower, a fluidized bed). Dilution with water gives a stable dispersion or solution of the active compound.
  • the formulation has an active compound content of 50% by weight.
  • the active compound 75 parts by weight of the active compound are ground in a rotor-stator mill and 25 parts by weight of a dispersant, a humectant and silica gel are added. Dilution with water gives a stable dispersion or solution of the active compound.
  • the formulation has an active compound content of 75% by weight.
  • 0.5 parts by weight of the active compound are finely ground and combined with 99.5 parts by weight of the carrier.
  • Current methods are extrusion, spray drying or fluidized bed methods. This gives granules with an active compound content of 0.5% by weight applied without dilution.
  • Compounds I or herbicidal compositions comprising them can be applied before or after emergence, or together with the seeds of crops.
  • the herbicidal composition or active compound can also be applied by applying the seeds of a crop plant pretreated with the herbicidal composition or active compound. If the active compounds are not well tolerated by certain crops, it can be used in which the herbicidal composition is sprayed by means of a spraying device so that they do not touch the leaves of sensitive crops as much as possible, while the active ingredients reach the leaves of the unwanted plants growing Or application techniques on bare soil surfaces.
  • the compound of formula I or a herbicidal composition thereof can be applied by treating the seeds.
  • Seed treatment basically includes all procedures well-known to those skilled in the art based on the compound of Formula I or the composition prepared therefrom (seed dressing, seed coating, seed dusting, seed soaking, seed coating, seed multilayer Coating, seed coating, seed dripping and seed granulation).
  • the herbicidal composition can be applied here with or without dilution.
  • seed includes all types of seeds, such as grains, seeds, fruits, tubers, cuttings and similar forms.
  • seed describes grains and seeds.
  • the seeds used may be seeds of the useful plants described above, but may also be seeds of transgenic plants or plants obtained by conventional breeding methods.
  • the application rate of the active compound is 0.001-3.0 kg / ha, preferably 0.01-1.0 kg / ha of active substance (a.s.), depending on the control target, season, target plant and growth stage.
  • Compound I is usually used in an amount of 0.001-10 kg / 100 kg of seeds.
  • Safeners are compounds that prevent or reduce damage to useful plants without significantly affecting the herbicidal effect of compounds of formula I on unwanted plants. They can be used before sowing (for example in seed treatment or on cuttings or seedlings) and before or after emergence of useful plants. The safener and the compound of formula I can be used simultaneously or sequentially.
  • Suitable safeners are, for example, (quinoline-8-oxy) acetic acid, 1-phenyl-5-haloalkyl-1H-1,2,4-triazole-3-carboxylic acid, 1-phenyl-4, 5-dihydro-5-alkyl-1H-pyrazole-3,5-dicarboxylic acid, 4,5-dihydro-5,5-diaryl-3-isoxazolecarboxylic acid, dichloroacetamide Type, ⁇ -oxime phenylacetonitrile, acetophenone oxime, 4,6-dihalo-2-phenylpyrimidine, N-[[4- (aminocarbonyl) phenyl] sulfonyl] -2- Benzamide, 1,8-naphthalenedicarboxylic anhydride, 2-halo-4-haloalkyl-5-thiazolecarboxylic acids, phosphorothioates and O-phenyl N-alkyl carbamates and their applications
  • the compounds of formula I can be mixed with a number of other representative or safeners of herbicidal or growth-regulating active compounds and applied in combination.
  • Suitable mixed pairs are, for example, 1,2,4-thiadiazoles, 1,3,4-thiadiazoles, amides, aminophosphoric acids and their derivatives, aminotriazoles, amidoanilines, aryloxy / Heteroaryloxyalkanoic acid and its derivatives, benzoic acid and its derivatives, benzothiadiazinone, 2-heteroaroyl / aroyl-1,3-cyclohexanedione, hetero Aryl aryl ketones, benzyl isoxazolidinones, m-CF3-phenyl derivatives, carbamates, quinoline carboxylic acids and their derivatives, chloroacetanilides, cyclohexanone oxime ethers Derivatives, diazines, dichloropropi
  • Compound I alone or in combination with other herbicides, or it may also be applied in combination with other crop protection agents, such as in combination with a composition for controlling pests or plant pathogenic fungi or bacteria Compound I.
  • crop protection agents such as in combination with a composition for controlling pests or plant pathogenic fungi or bacteria Compound I.
  • miscibility with inorganic salt solutions used to alleviate nutritional and trace element deficiencies is also of interest.
  • Other additives such as non-phytotoxic oils and oil concentrates can also be added.
  • herbicides that can be used in combination with the pyridine compound of formula I of the present application are:
  • lipid biosynthesis inhibitor selected from the group consisting of clethodim, clodinafop, clodinafop-propargyl, cycloxydim, cyhalofop , Cyhalofop-butyl, diclofop, diclofop-methyl, fenoxaprop-ethyl, fluazifop, fluflufop Fluazifop-butyl, fluazifop-P, fluazifop-P-butyl, haloxyfop, haloxyfop -methyl), haloxyfop-P, haloxyfop-P-methyl, metafop, pinoxaden, cyproben Ketone (profoxydim), propaquizafop, quizalofop, quizalofop-ethyl, quizalofop-tefuryl, quizalofop -P), quizalofop-
  • an ALS inhibitor selected from the group consisting of bensulfuron, bensulfuron-methyl, bispyribac, cinosulfuron, cloransulam , Cloransulam-methyl, cyclosulfamuron, diclosulam, ethametsulfuron, ethametsulfuron-methyl, ethoxysulfuron-methyl ethoxysulfuron, flazasulfuron, florasulam, flucarbazone, flucetosulfuron, flumetsulam, flupyrsulfuron ), Flupyrsulfuron-methyl-sodium, foramsulfuron, halosulfuron, halosulfuron-methyl, imazosulfuron, iodosulfuron (Iodosulfuron), iodosulfuron-methyl-sodium, mesosulfuron, metosulam, metsulfuron, mets, met
  • a photosynthesis inhibitor selected from the group consisting of: ametryn, amidcarbazone, atrazine, bentazone, bentazone-sodium, and bromacil ), Bromofenoxim, bromoxynil and its salts and esters, chlorobromuron, chloridazone, cyanazine, desmedipham, Desmetryn, diquat-dibromide, diuron, fluometuron, hexazinone, ioxynil and its salts and esters, isopropyl Isoproturon, isouron, karbutilate, lenacil, linuron, metamitron, methabenzthiazuron, carbazoxan (paraquat-dimetilsulfate), pentanochlor, phenmedipham, phenmedipham-ethyl, prometon, prometryn, propanil, extinguish Propazine, pyridafol, pyridate, sidur
  • protoporphyrinogen-IX oxidase inhibitors acifluorfen, aciflorfen-sodium, azafenidin, bencarbazone, diflufenazone (benzfendizone), bifenox, butafenacil, carfentrazone, carfentrazone-ethyl, chlomethoxyfen, indoxazone (cinidon-ethyl), iprazol (fuazolate), fufenpyr (flufenpyr), flufenpyr-ethyl (flufenpyr-ethyl), flumiclorac, imidophenoxy Flumiclorac-pentyl, flumioxazin, fluoroglycofen, fluoroglycofen-ethyl, fluthiacet, fluthiacet- methyl), fomesafen, halosafen, lactofen, oxadiargyl,
  • a bleaching herbicide selected from the group consisting of aclofen, amitrol, beflubutamid, benzobicyclon, benzofenap, isopropyl Clomazone, diflufenican, fluridone, flurochloridone, flurtamone, isoxaflutole, mesotrione (mesotrione), norflurazon, picolinafen, pyrasulfutole, pyrazolynate, pyrazoxyfen, sulcotrione, tefuryltrione, tembotrione, topramezone, bixlozone , Trisulcotrione, Ciclotrione, Diflufenazone, 4-Hydroxy-3-[[2-[(2-methoxyethoxy) methyl] -6- (trifluoromethyl ) -3-pyridyl] carbonyl] bicyclo [3.2.1] oct-3-en-2-one (H-7;
  • an EPSP synthetase inhibitor selected from the group consisting of glyphosate, glyphosate-isopropylammonium, and glyphosate-trimesium (sulfosate);
  • a glutamine synthetase inhibitor selected from the group consisting of bilanaphos (bialaphos), bilanaphos-sodium and glufosinate-ammonium;
  • b9) is selected from the following mitotic inhibitors: amiprophos, amiprophos-methyl, benfluralin, butamiphos, butralin, longan Carbamide, chlorpropham, chlorthal, chlorthal-dimethyl, dinitramine, dithiopyr, ethalfluralin ), Fluchloralin, oryzalin, pendimethalin, prodiamine, propham, propyzamide, tebutam ), Thiazopyr and trifluralin;
  • VLCFA inhibitor selected from the group consisting of acetochlor, alachlor, anilofos, butachlor, cafenstrole, and dimethachlor ), Dimethanamid, dimethenamid-P, diphenamid, fentrazamide, flufenacet, mefenacet , Metazachlor, metolachlor, S-metolachlor-S, naproanilide, napropamide, pethoxamid, Piperophos, pretilachlor, propachlor, propisochlor, pyroxasulfone (KIH-485), and thenylchlor );
  • a cellulose biosynthesis inhibitor selected from the group consisting of chlorthiamid, dichlobenil, flupoxam, and isoxaben;
  • a separating agent herbicide selected from the group consisting of dinoseb, dinoterb, and DNOC and salts thereof;
  • auxin herbicide selected from the group consisting of 2,4-D and salts and esters thereof, 2,4-DB and salts and esters thereof, aminopyralid and salts thereof such as ammonium salt ( aminopyralid-tris (2-hydroxypropyl) ammonium) and its esters, benazolin, benazolin-ethyl, chloramben and its salts and esters, clomeprop, diammonium Clopyralid and its salts and esters, dicamba and its salts and esters, 2,4-dichlorprop and its salts and esters, and high 2,4-dipropionic acid ( dichlorprop-P) and its salts and esters, fluroxypyr, fluroxypyr-butometyl, fluroxypyr-meptyl, MCPA and its salts and esters, 2 methyl 4-chloroethyl thiosulfate (MCPA-thioethyl), MCPB and its salts and esters, 2
  • auxin transport inhibitor selected from the group consisting of diflufenzopyr and naptalam;
  • herbicides selected from the group consisting of bromobutide, chlorflurenol, chlorflurenol-methyl, cinmethylin, cumyluron, Thatch, dazomet, difenzoquat, difenzoquat-metilsulfate, dimethipin, sodium formazan (DSMA), dymron, endothal ) And its salts, flamprop, flamprop-M-isopropyl, flamprop-M-methyl, flurenol, flurenol-butyl, Flurprimidol, fosamine, fosamine-ammonium, indanofan, maleic hydrazide, mefluidide, methamphetamine (methyl- dymron), oxaziclomefone, pelargonic acid, piributicarb, and 6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -4- Pyridazinol (H-10;
  • Examples of the preferred safener C are: benoxacor, cloquintocet, cymetrinil, cyprosulfamide, dichlormid, dicyclonone, dietholate, fenchlorazole, Fenclorim, flurazole, fluxofenim, furilazole, isoxadifen, mefenpyr, mephenate, naphthalenedicarboxylic anhydride ( naphthalic anhydride), oxabetrinil, 4- (dichloroacetyl) -1-oxa-4-azaspiro [4.5] decane (H-11; MON4660, CAS 71526-07-3), and 2,2,5-trimethyl-3- (dichloroacetyl) -1,3-oxazolidine (H-12; R-29148, CAS 52836-31-4).
  • the b1) -b15) groups of active compounds and safeners are known herbicides and safeners, see, for example, The Compendium of Pesticide Common Names (http://www.alanwood.net/pesticides/); B. Hock, C. Fedtke, RR Schmidt, Herbizide [herbicide], Georg Thieme Verlag, Stuttgart, 1995.
  • Other herbicidally active compounds are described in WO 96/26202, WO 97/41116, WO 97/41117, WO 97/41118, WO 01/83459, and WO 2008/074991, W. (Edit) "Modern Crop Protection Compounds", Vol. 1, Wiley VCH, 2007 and the literature cited therein are known.
  • the application also relates to a composition in the form of a crop protection composition formulated as a one-component composition comprising at least one pyridazine compound of formula I and at least one preferably selected from the group b1-b15 Active compounds Other active compounds Active compound combinations and at least one solid or liquid carrier and / or one or more surfactants and, if necessary, one or more other adjuvants commonly used in crop protection compositions.
  • the application also relates to a composition in the form of a crop protection composition formulated as a two-component composition comprising at least one pyridazine compound of formula I, a solid or liquid carrier and / or one or A first component of a plurality of surfactants and a second component containing at least one other active compound selected from the group b1 to b15, a solid or liquid carrier, and / or one or more surfactants, wherein These two components may additionally contain other adjuvants commonly used in crop protection compositions.
  • the compound I and the composition of the present application may also have a plant enhancing effect. They are therefore suitable for mobilizing the plant's defense system against attack by unwanted microorganisms such as harmful fungi as well as viruses and bacteria.
  • Plant enhancement (induced resistance) substances are understood in the context of the present application to mean those capable of stimulating the defense system of the treated plants such that the treated plants show significant resistance to these microorganisms when subsequently inoculated with unwanted microorganisms substance.
  • Compound I can be used to protect plants from unwanted microorganisms for a certain period of time after treatment.
  • the period of time for protection is usually 1-28 days, preferably 1-14 days, after treatment of the plant or the seeds with compound I, up to 9 months after sowing.
  • the compounds I and compositions of the present application are also suitable for increasing harvest yield.
  • Compound I-B-1 melting point 140-142 ° C. ⁇ ppm 7.95-8.05 (1H, s), 8.30-8.40 (1H, s), 8.60-8.70 (1H, s), 9.00-9.10 (1H, s).
  • the culture vessel used was a plastic flowerpot containing loamy sand containing about 3.0% humus soil as a substrate. Seeds of the test plants were sown individually for each variety.
  • the active ingredients suspended or emulsified in water are applied directly after sowing by means of fine distribution nozzles.
  • the container is gently irrigated to promote germination and growth, and then covered with a transparent plastic cover until the plant takes root. This coverage results in uniform germination of the test plants unless damaged by the active compound.
  • test plants For post-emergence treatment, the test plants are first grown to a height of 3-15 cm, depending on plant habits, and only treated with active ingredients suspended or emulsified in water at this time. To this end, the test plants are sown directly and grown in the same container, or they are first grown individually as seedlings and transplanted into the test container a few days before treatment.
  • the plants are kept at 10-25 ° C or 20-35 ° C.
  • the test period is 2-4 weeks. Plants were cared for during this period and their response to each treatment was evaluated.
  • Evaluation is performed using a scale of 0-100. 100 means no plant emerges, or at least part of the ground is completely damaged, while 0 means no damage or normal growth. A good herbicidal activity is given a score of at least 70 and a very good herbicidal activity is given a score of at least 85.
  • the plants used in the greenhouse tests belong to the following varieties:
  • the compounds I-A-8, I-I-1, and I-A-19 applied by the post-emergence method showed very good herbicidal activity against Goosegrass.
  • the compound I-I-1 applied by the post-emergence method showed very good herbicidal activity against Yarrow.
  • the compound I-I-1 applied by the post-emergence method showed very good herbicidal activity against Mai Niang.
  • the compound I-I-1 applied by the post-emergence method showed very good herbicidal activity against bluegrass.

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Abstract

提供一种具有广谱除草活性的哒嗪胺化合物，结构如通式（I）所示，式中各取代基定义见说明书。该化合物具有广谱除草活性，对稗草、牛筋草和马唐等都有很好的防效，可以用在小麦、大豆、水稻、果园以及非耕地等使用，防治各种恶性杂草。

Description

哒嗪胺类化合物的制备及其应用
相关申请的交叉引用
本申请要求于2018年09月20日提交中国专利局的申请号为CN201811103367.0、名称为“哒嗪胺类化合物的制备及其应用”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。
技术领域
本申请属于农用除草剂领域。涉及的是一类新型的哒嗪胺类化合物及组合物、它们的用途及使用方法。
背景技术
农田杂草是影响农作物生产的重要因素。我国受杂草危害的农田面积为4300万公顷，每年因此而减产粮食1750万吨。杂草化学防治是农田杂草防治中最重要的手段，具有省工、省时、高效和快捷的优点，是提高劳动生产效率、发展高效与优质农业的重要措施。哒嗪胺类化合物一般在医药中，用于抗癌和消炎等用途。本申请的哒嗪胺类化合物具有优异的除草活性，此类结构作为除草剂使用未见文献报道。这些化合物在农业上可用做除草剂。
发明内容
为了满足农业上的要求，本申请提供了一种新型哒嗪胺类化合物及其防除杂草的使用方法和含有这些化合物的组分在农业上的应用。
本申请的技术方案如下：
本申请提供了一种哒嗪胺类化合物，如通式(Ⅰ)所示：
Figure PCTCN2019104960-appb-000001
式中：
R 1选自氢、卤素、氰基、未取代的或被1-4个独立选自以下基团取代的苯氧基或杂芳氧基：卤素、硝基、氰基、C 1-C 12烷基、卤代C 1-C 12烷基、C 1-C 12烷氧基、卤代C 1-C 12烷氧基、C 3-C 12环烷基、C 1-C 12烷基羰基或C 1-C 12烷氧基羰基；
R 2选自氢、C 1-C 12烷基、卤代C 1-C 12烷基、C 1-C 12烷氧基、卤代C 1-C 12烷氧基、C 3-C 6环烷基、氰基C 1-C 12烷基、C 1-C 12烷基氨基、卤代C 1-C 12烷基氨基、C 2-C 6二烷基氨基、C 2-C 12烯基、卤代C 2-C 12炔基、C 2-C 12烯氧基、卤代C 2-C 12烯氧基、C 2-C 12炔基、卤代C 2-C 12烯基、C 2-C 12炔氧基、卤代C 2-C 12炔氧基、C 1-C 12烷基磺酰基、C 1-C 12烷基羰基、卤代C 1-C 12烷基羰基或卤代C 1-C 12烷磺酰基；
R 3选自未取代的或被1-4个独立选自以下基团取代的苯基、苄基或杂芳基：卤素、羟基、硝基、氰基、CHO、COOH、COONa、C 1-C 12烷基、卤代C 1-C 12烷基、C 1-C 12烷氧基、卤代C 1-C 12烷氧基、C 3-C 6环烷基、氰基C 1-C 12烷基、C 1-C 12烷基氨基、卤代C 1-C 12烷基氨基、C 2-C 6二烷基氨基、C 2-C 12烯基、卤代C 2-C 12炔基、C 2-C 12烯氧基、卤代C 2-C 12烯氧基、C 2-C 12炔基、卤代C 2-C 12炔基、C 2-C 12炔氧基、卤代C 2-C 12炔氧基、C 1-C 12烷硫基、卤代C 1-C 12烷硫基、C 1-C 12烷基磺酰基、C 1-C 12烷基羰基、卤代C 1-C 12烷基羰基或卤代C 1-C 12烷磺酰基；
R 2NR 3也可以组成被1-4个独立选自以下基团取代或未取代的五元或六元环，所述独立取代基团选自以下基团：卤素、羟基、硝基、氰基、CHO、COOH、COONa、C 1-C 12烷基、卤代C 1-C 12烷基、C 3-C 12环烷基、C 1-C 12烷氧基、卤代C 1-C 12烷氧基、C 1-C 12烷硫基、C 1-C 12烷基羰基或C 1-C 12烷氧基羰基；
R 4选自卤素、氰基、CHO、COOH、COONa、C 1-C 12烷基磺酰基、卤代C 1-C 12烷基磺酰基或被1-4个独立选自以下基团取代或未取代的芳基磺酰基，所述独立取代基团选自以下基团：卤素、羟基、硝基、 氰基、CHO、COOH、COONa、C 1-C 12烷基、卤代C 1-C 12烷基、C 3-C 12环烷基、C 1-C 12烷氧基、卤代C 1-C 12烷氧基、C 1-C 12烷硫基、C 1-C 12烷基羰基或C 1-C 12烷氧基羰基；
或通式(I)化合物的N-氧化物或可农用盐；
本申请中较为优选的化合物为：通式(I)中
R 1选自氢、Cl、Br、F、I、氰基、未取代的或被1-4个独立选自以下基团取代的苯氧基或杂芳氧基：卤素、硝基、氰基、C 1-C 6烷基、卤代C 1-C 6烷基、C 1-C 6烷氧基、卤代C 1-C 6烷氧基、C 3-C 6环烷基、C 1-C 6烷基羰基或C 1-C 6烷氧基羰基；
R 2选自氢、C 1-C 6烷基、卤代C 1-C 6烷基、C 1-C 6烷氧基、卤代C 1-C 6烷氧基、C 3-C 6环烷基、氰基C 1-C 6烷基、C 1-C 6烷基氨基、卤代C 1-C 6烷基氨基、C 2-C 6二烷基氨基、C 2-C 6烯基、卤代C 2-C 6烯基、C 2-C 6烯氧基、卤代C 2-C 6烯氧基、C 2-C 6炔基、卤代C 2-C 6炔基、C 2-C 6炔氧基、卤代C 2-C 6炔氧基、C 1-C 6烷基磺酰基、C 1-C 6烷基羰基、卤代C 1-C 6烷基羰基或卤代C 1-C 6烷磺酰基；
R 3选自未取代的或被1-4个独立选自以下基团取代的苯基、苄基或杂芳基：Cl、Br、F、I、羟基、硝基、氰基、CHO、COOH、COONa、C 1-C 6烷基、卤代C 1-C 6烷基、C 1-C 6烷氧基、卤代C 1-C 6烷氧基、C 3-C 6环烷基、氰基C 1-C 6烷基、C 1-C 6烷基氨基、卤代C 1-C 6烷基氨基、C 2-C 6二烷基氨基、C 2-C 6烯基、卤代C 2-C 6炔基、C 2-C 6烯氧基、卤代C 2-C 6烯氧基、C 2-C 6炔基、卤代C 2-C 6炔基、C 2-C 6炔氧基、卤代C 2-C 6炔氧基、C 1-C 6烷硫基、卤代C 1-C 6烷硫基、C 1-C 6烷基磺酰基、C 1-C 6烷基羰基、卤代C 1-C 6烷基羰基或卤代C 1-C 6烷磺酰基；
R 2NR 3也可以组成被1-4个独立选自以下基团取代或未取代的五元或六元环，所述独立取代基团选自以下基团：Cl、Br、F、I、羟基、硝基、氰基、CHO、COOH、COONa、C 1-C 6烷基、卤代C 1-C 6烷基、C 3-C 6环烷基、C 1-C 6烷氧基、卤代C 1-C 6烷氧基、C 1-C 6烷硫基、C 1-C 6烷基羰基或C 1-C 6烷氧基羰基；
R 4选自Cl、Br、F、I、氰基、CHO、COOH、COONa、C 1-C 6烷基磺酰基或卤代C 1-C 6烷基磺酰基；
或通式(I)化合物的N-氧化物或可农用盐；
本申请进一步优选的化合物为：通式(I)中
R 1选自H、Cl、Br、F、I、CN、CH 3、CH 2CH 3、叔丁基、环丙基、CF 3、CH 2CF 3、OCH 3、OCF 3、OCH 2CF 3、SO 2CH 3、CO 2CH 3、未取代或取代的苯氧基，所述的取代基选自1-3个如下基团：Cl、Br、F、I、CN、NO 2、CHO、COOH、COONa、CH 3、CH 2CH 3、叔丁基、环丙基、CHF 2、CF(CF 3) 2、CF 3、CH 2CF 3、OCH 3、OCHF 2、OCF 3、OCH 2CF 3或SO 2CH 3；
R 2选自H、甲基、乙基、丙基、异丙基、叔丁基、正丁基或甲氧基、环丙基、氰基乙基、甲氨基、甲磺酰基、烯丙基、炔丙基、甲磺酰基、对甲苯磺酰基、乙基羰基或甲酰基；
R 3选自未取代的或被1-3个独立选自以下基团取代的苯基、苄基或杂芳基：OH、Cl、Br、F、I、CN、NO 2、CHO、COOH、COONa、CH 3、CH 2CH 3、叔丁基、环丙基、CHF 2、CF 3、CF(CF 3) 2、CH 2CF 3、OCH 3、OCHF 2、OCF 3、OCH 2CF 3或SO 2CH 3；
R 2NR 3也可以组成被1-3个独立选自以下基团取代或未取代的五元或六元环，所述独立取代基团选自以下基团：OH、Cl、Br、F、I、CN、NO 2、CH 3、CH 2CH 3、叔丁基、环丙基、CHF 2、CF(CF 3) 2、CF 3、CH 2CF 3、OCH 3、OCHF 2、OCF 3、OCH 2CF 3或SO 2CH 3；
R 4选自Cl、Br、F、I、CN、SO 2CH 3或SO 2CH 2CH 3；
或通式(I)化合物N-氧化物以及与盐酸、硫酸、磷酸、甲酸、乙酸、草酸、三氟乙酸、甲磺酸、对甲苯磺酸、苹果酸、柠檬酸、锂、钙、钠或者钾形成的盐。
本申请更进一步优选的化合物为：通式(I)中
R 1选自Cl、Br、F、I、2-甲基苯酚、2-异丙基苯酚、2-环丙基苯酚、2-甲基-6-环丙基苯酚或2-碘苯酚；
R 2选自H、CH 3、CH 2CH 3、环丙基、甲氧基或甲氨基；
R 3选自未取代的或被1-3个独立选自以下基团取代的苯基、嘧啶基、吡唑基、吡啶基或哒嗪基：OH、Cl、Br、F、I、CN、NO 2、CHO、COOH、COONa、CH 3、CH 2CH 3、叔丁基、环丙基、CHF 2、CF 3、CH 2CF 3、OCH 3、OCHF 2、OCF 3、CF(CF 3) 2、OCH 2CF 3或SO 2CH 3；
R 2NR 3也可以组成吗啉、哌嗪、哌啶、吡咯环、吡唑环、三唑环、嘧啶环或
Figure PCTCN2019104960-appb-000002
等；
R 4选自Cl、Br、F、I或CN；
或通式(I)化合物与盐酸、硫酸、磷酸、锂、钙、钠或者钾形成的盐。
本申请再进一步优选的化合物为：通式(I)中
R 1选自Cl、Br、F或I；
R 2选自H、CH 3或CH 2CH 3；
R 3选自未取代的或被1-3个独立选自以下基团取代的苯基、吡啶基或哒嗪基：OH、Cl、Br、F、I、CN、NO 2、CHO、COOH、COONa、CH 3、CH 2CH 3、叔丁基、CHF 2、CF 3、CH 2CF 3、CF(CF 3) 2、OCH 3、OCHF 2、OCF 3、OCH 2CF 3或SO 2CH 3；
R 2NR 3也可以组成
Figure PCTCN2019104960-appb-000003
环等；
R 4选自Cl、Br、F、I或CN；
或通式(I)化合物与盐酸、硫酸、磷酸、锂、钙、钠或者钾形成的盐。
在本申请的化合物中，由于手性碳或氮连接不同的基团或取代基而可以形成立体异构体(分别以R和S来表示不同的构型)。本申请包括R型异构体和S型异构体及其任何比例的混合物。
上面给出的通式(I)化合物的定义中，汇集所用术语一般定义如下：
未取代表示所有取代基都为氢。
卤素：指氟、氯、溴或碘。
烷基：直链、支链或环化烷基，例如甲基、乙基、丙基、异丙基、叔丁基或环丙基。
卤代烷基：直链或支链卤代烷基，在这些烷基上的氢原子可部分或全部被卤原子所取代，例如，卤代烷基诸如氯甲基、二氯甲基、三氯甲基、氟甲基、二氟甲基或三氟甲基。
烷氧基：直链、支链或环化烷氧基，例如甲氧基、乙氧基、丙氧基、异丙氧基、叔丁氧基或环丙氧基。
卤代烷氧基：直链或支链卤代烷氧基，在这些烷氧基上的氢原子可部分或全部被卤原子所取代，例如，卤代烷基诸如氯甲氧基、二氯甲氧基、三氯甲氧基、氟甲氧基、二氟甲氧基或三氟甲氧基。
烷硫基：直链或支链烷基，经硫原子键连接到结构上。
卤代烷硫基：直链或支链烷硫基，在这些烷硫基上的氢原子可部分或全部被卤原子所取代。例如，氯甲硫基、二氯甲硫基、三氯甲硫基、氟甲硫基、二氟甲硫基、三氟甲硫基或氯氟甲硫基等。
烯基：直链或支链并可在任何位置上存在有双键，例如乙烯基或烯丙基。
炔基：直链或支链并可在任何位置上存在有三键，例如乙炔基或炔丙基。
芳基以及芳烷基中的芳基部分包括苯基或萘基等。
本申请中所指杂芳基是含1个或多个N、O、S杂原子的五元环、六元环或稠杂环化合物。例如吗啉、哌嗪、哌啶、吡咯、吡啶、呋喃、嘧啶、吡嗪、哒嗪、三嗪、喹啉、异喹啉、吲哚、嘌呤或苯并吡喃酮等。
由以下通式(Ⅱ)表示的哒嗪胺与酸或碱加成的盐：
Figure PCTCN2019104960-appb-000004
其中，R 1、R 2、R 3和R 4与通式(I)所定义的意义相同。
可以与本申请的由通式(Ⅱ)表示的哒嗪胺成盐的酸包括：羧酸，如乙酸、丙酸、丁酸、草酸或三氟乙酸；磺酸，如甲磺酸、对甲苯磺酸或十二烷基苯磺酸；及无机酸，如盐酸、硫酸、硝酸或碳酸。
可以与本申请的由通式(Ⅱ)表示的哒嗪胺成盐的碱及金属包括：金属，如钠、碱、钙或镁等；有机碱，如甲醇钠、乙醇钠、叔丁醇钠、甲醇钾、乙醇钾、甲酸钠、丁基锂或乙酸钠等；无机碱，如氢氧化钠、氢氧化钾、碳酸钠、碳酸钾、氢化钠或氨基钠等；
表1和表2分别列举了通式I中R 1和R 4部分具体取代基，但它们并非仅限于这些取代基。
Figure PCTCN2019104960-appb-000005
R 1表示部分具体取代基
表1
Figure PCTCN2019104960-appb-000006
R 4表示部分具体取代基
表2
R 4 R 4 R 4 R 4 R 4
H F Cl Br I
CHO CN COOH SO 2CH 3 SO 2CH 2CH 3
表3 R 2NR 3组成环状结构时，所表示的取代基
Figure PCTCN2019104960-appb-000007
Figure PCTCN2019104960-appb-000008
表4
(R 6) n (R 6) n (R 6) n
2-F 2-Br 2-CH 3-4-Cl-6-CON(CH 3) 2
2,4-2F 2,6-2Br-4-NO 2 2-CH 3-4-Cl-6-CONHCH(CH 3) 2
2,6-2F 2,6-2Br-4-OCF 3 2-CH 3-4-Cl-6-CONHC(CH 3) 3
2-F-5-CH 3 3-Br-4-CN 2-CH 3-4-Br-6-CO 2CH 3
2-F-5-NO 2 4-Br 2-CH 3-4-Br-6-CONH 2
2-F-4-CN 2-I 2-CH 3-4-Br-6-CON(CH 3) 2
2,3,4-3F 4-I 2-CH 3-4-NO 2-6-F
2-F-4-NO 2 2-NO 2 2-CH 3-4-NO 2-6-Cl
2,6-2F-4-CF 3 2-NO 2-4-Cl 2-CH 3-4-NO 2-6-Br
2,5-2F-4-CO 2C 2CH 5 2-NO 2-4-CN 2-CH 3-4-NO 2-6-CN
2,6-2F-4-NO 2 2-NO 2-5-Cl 2-CH 3-4-NO 2-6-CF 3
2,6-2F-4-OCF 3 2,6-2NO 2-4-Cl 2-CH 3-4-NO 2-6-OCH 3
2-F-4-NO 2-6-Cl 2,6-2NO 2-4-SOCH 3 2-CH 3-4-NO 2-6-SO 2CH 3
2-F-4-CN-5-CO 2CH 3 2,6-2NO 2-4-SO 2CH 5 2-CH 3-4-NO 2-6-CO 2H
2-F-4-CN-5-NO 2 2-NO 2-4,6-2Cl 2-CH 3-4-NO 2-6-CO 2CH 3
2-F-4-CN-6-OCH 3 2-NO 2-4-Cl-6-F 2-CH 3-4,6-2CN
2-F-4-NO 2-6-Cl 2-NO 2-4-CN-6-Cl 2-CH 3-4-CN-6-NO 2
2-F-4-NO 2-6-Br 2-NO 2-3-C 2H 5-6-CO 2H 3 2-CH 3-4-CN-6-CF 3
2-F-4-CN-6-Cl 2-NO 2-4-CO 2H 3-6-SCH 3 4-CH 3
Figure PCTCN2019104960-appb-000009
表5
(R 6)n (R 6)n (R 6)n (R 6)n
3-I 5-CHO 4-I-5-CH 3 3,5-2F-4-CF 3
4-Cl 3-NH 2 4-I-5-CF 3 3,6-2F-4-CF 3
4-Br 4-NH 2 5-I-6-C 2H 5 3-F-5-CN-6-Cl
4-I 5-NH 2 3-NO 2-4-Cl 3-F-5-CO 2CH 3-6-Cl
5-Cl 6-NH 2 3-NO 2-4-CH 3 3-F-5-CONH 2-6-Cl
5-Br 3-CONH 2 3-NO 2-5-Cl 3-F-5-CONHCH(CH 3) 2-6-Cl
5-I 4-CONH 2 3-NO 2-5-Br 3,5-2Cl-4-CH 3
6-Cl 5-CONH 2 3-NO 2-5-I 3,5-2Cl-6-CH 3
6-Br 3-F-5-Cl 3-NO 2-6-Cl 3,5-2Cl-4,6-2CH 3
3-NO 2 3-F-5-CN 3-NO 2-6-CH 3 3,5-2Cl-6-OCH 2CO 2CH 3
4-NO 2 3-F-4-CF 3 3-NO 2-6-OCH 3 3,6-2Cl-5-CF 3
5-NO 2 3-F-5-CF 3 4-NO 2-6-CH 3 3,5,6-3Cl
6-NO 2 3-F-4-CHO 5-NO 2-6-Cl 3-Br-5-CF 3-6-Cl
3-CN 4,6-2F 5-NO 2-6-CH 3 3,5-2Br-4-CH 3
4-CN 5-F-6-CH 3 5-NO 2-6-NHCOCH 3 3,5-2Br-6-CH 3
5-CN 3,5-2Cl 3-CN-6-CH 3 3-Br-5,6-2CH 3
6-CN 4,6-2Cl 3-CN-4-OCH 3 3-NO 2-4-CH 3-5-Br
3-CH 3 3,5-2Br 3-CH 3-5-CN 3,5-2CN-6-Cl
4-CH 3 3-Cl-5-Br 4-CH 3-5-Br 3-CN-5-F-6-Cl
Figure PCTCN2019104960-appb-000010
表6
(R 6)n (R 6)n (R 6)n (R 6)n
H 2-CH 3 2-Cl-5-CH 3 5-CO 2H-6-Cl
2-F 4-CH 3 2-Cl-5-CF 3 5-CO 2CH 3-6-Cl
2-Br 4-CF 3 2-Cl-4-CHO 5-CONH 2-6-Cl
2-Cl 5-CF 3 2-Cl-5-SO 2NH 2 2,5,6-3F
2-I 6-CF 3 5-Cl-6-CN 2,6-2F-5-Cl
Figure PCTCN2019104960-appb-000011
表7
(R 6)n (R 6)n (R 6)n (R 6)n
H 2-CF 3 3,5-2Cl 2,6-2NO 2
2-F 3-CF 3 3,5-2Br 3,5-2CH 3
3-F 5-CF 3 3,5-2I 2,6-2CH 3
2-Cl 2-OCH 3 2-F-5-CH 3 3-CH 3-2-Cl
2-Br 3-OCH 3 2-F-3-CHO 3,6-2Cl-5-CF 3
Figure PCTCN2019104960-appb-000012
表8
(R 6)n (R 6)n (R 6)n (R 6)n
H 5-CO 2C 2H 5 4-Cl-5-NO 2 4-CF 3-5-CO 2C 2H 5
4-F 5-CO 2C(CH 3) 3 4-Cl-5-CN 4-CF 3-5-CONH 2
4-Cl 5-CHO 4-Cl-5-CH 3 4-OCH 3-5-Br
4-CN 5-NH 2 4-Cl-6-CH 3 4,6-2OCH 3
4-NO 2 5-CONH 2 4-Cl-6-CH(CH 3) 2 4-CO 2CH 3-6-Cl
4-CH 3 5-CONHCH 3 4-Cl-5-CF 3 4-CO 2C 2H 5-6-Cl
4-CF 3 5-CONHC 2H 5 4-Cl-5-OCH 3 4-CO 2CH 3-6-CH 3
4-OCH 3 5-CONHCH(CH 3) 2 4-Cl-6-OCH 3 4-CO 2C 2H 5-6-CH 3
Figure PCTCN2019104960-appb-000013
表9
(R 6)n (R 6)n (R 6)n (R 6)n
H 2,5-2Cl 2-CH 3-6-Cl 2-SCH 3-5-CONH 2
2-F 2,6-2Cl 5-CH 3-6-Cl 2-SO 2CH 3-6-Cl
2-Cl 2-Cl-5-Br 2-CH 3-5-CN 2-SO 2CH 3-5-Br
2-OC 2H 5 2-Cl-5-I 2-CH 3-5-C(CH 3) 3 2-SO 2CH 3-6-OCH 3
2-SCH 3 2-Cl-5-NO 2 2-CF 3-5-CO 2C 2H 5 5-CHO-6-Cl
2-SOCH 3 2-Cl-5-CN 2-OCH 3-6-Cl 5-CHO-6-NH 2
2-SO 2CH 3 2-Cl-5-CH 3 2-SCH 3-6-Cl 5-CO 2H-6-Cl
2-NHCH 3 2-Cl-6-CH 3 2-SCH 3-5-Br 2-NH 2-6-CH(CH 3) 2
Figure PCTCN2019104960-appb-000014
表10
(R 6)n (R 6)n (R 6)n (R 6)n
H 4-Cl 2,4-2Br 2-SCH 3-4-CO 2CH 3
2-F 4-Br 4,6-2Br 2-SCH 3-4-CO 2H
2-Cl 2,4-2F 2-OCH 3-4-Cl 2-SCH 3-4-CONH 2
2-Br 4,6-2F 2-OCH 3-4-Br 2-SCH 3-4-CSNH 2
2-I 2,4,6-3F 2,4-2OCH 3 2-SO 2CH 3-4-Cl
2-CN 2,4-2Cl 4,6-2OCH 3 2-CH 3-4,6-2Cl
Figure PCTCN2019104960-appb-000015
表11
(R 6)n (R 6)n (R 6)n (R 6)n
6-Cl 6-CO 2CH 3 6-CON(CH 3) 2 4-Cl-6-CO 2CH 3
6-Br 6-CO 2C 2H 5 6-CON(C 2H 5) 2 4-Cl-6-CONHCH 3
H 6-CO 2C(CH 3) 3 6-CSNH 2 5,6-2Cl
6-CN 6-CO 2H 6-CSNHCH 3 4-Br-6-CN
6-CH 3 6-NH 2 4-F-6-CN 4-Br-6-CO 2CH 3
6-OCH 3 6-N(CH 3) 2 4-F-6-CO 2CH 3 4-Br-6-CONHCH 3
6-SCH 3 6-CONH 2 4-F-6-CONHCH 3 4-CH 3-6-CN
6-SOCH 3 6-CONHCH 3 3-Cl-5-NHCOCH 3 4-CH 3-6-CO 2CH 3
Figure PCTCN2019104960-appb-000016
表12
(R 6)n (R 6)n (R 6)n (R 6)n
H 5,6-2Cl 5-Cl-6-OCH 3 3-Cl-5-NHCOCH 3
3-Cl 3-Cl-6-OCH 3 5-Cl-6-SCH 3 3-Cl-5-NHCO 2CH 3
6-Cl 3-Cl-6-SCH 3 5-Cl-6-SOCH 3 5,6-2OCH 3
3,6-2Cl 5-Cl-6-N(CH 3) 2 5-Cl-6-SO 2CH 3 5,6-2SCH 3
3,6-2F 3,6-2Br 3,6-2I 3-F-6-Cl
3-F-6-Br 3-F-6-I 3-Cl-6-F 3-Cl-6-Br
3-Cl-6-I 3-Br-6-F 3-Br-6-Cl 3-Br-6-I
3-I-6-F 3-I-6-Cl 3-I-6-Br 3-SO 2CH 3-6-Cl
3-SO 2C 2H 5-6-Cl 3-CN-6-Cl 3-Cl-6-CF 3 3-CN-6-CF 3
Figure PCTCN2019104960-appb-000017
表13
(R 6)n (R 6)n (R 6)n (R 6)n
H 6-CO 2CH 3 6-CONHCH 3 4-CH 3-6-CN
6-Cl 6-CO 2C 2H 5 6-CONHC 2H 5 4-F-6-CO 2CH 3
6-Br 6-CO 2C(CH 3) 3 6-CON(CH 3) 2 4-Cl-6-CO 2CH 3
6-CN 6-CO 2H 6-CSNH 2 4-Br-6-CO 2CH 3
6-CH 3 6-CO 2Na 6-CSNHCH 3 4-CH 3-6-CO 2CH 3
6-OCH 3 6-CO 2NH 4 5,6-2Cl 4-F-6-CONHCH 3
6-SCH 3 6-NH 2 4-F-6-CN 4-Cl-6-CONHCH 3
6-SOCH 3 6-N(CH 3) 2 4-Cl-6-CN 4-Br-6-CONHCH 3
6-SO 2CH 3 6-CONH 2 4-Br-6-CN 4-CH 3-6-CONHCH 3
Figure PCTCN2019104960-appb-000018
表14
(R 6)n (R 6)n (R 6)n (R 6)n
4-Cl 4-OCH 3-6-NHCH 3 4-N(CH 3) 2 4-NH-i-Pr-6-NHCOCH 3
4-CN 4,6-2SCH 3 4-NH 2-6-Cl 4-NH-i-Pr-6-NH 2
4-SCH 3 4-SCH 3-6-Cl 4-NH 2-6-OCH 3 4-NH-i-Pr-6-NHCH 3
4-SOCH 3 4-SCH 3-6-NHCH 3 4-NH 2-6-SCH 3 4-NH-t-Bu-6-Cl
4-SO 2CH 3 4-SOCH 3-6-Cl 4-NH 2-6-SOCH 3 4-NH-t-Bu-6-CN
4,6-2Cl 4-SO 2CH 3-6-Cl 4-NH 2-6-SO 2CH 3 4-NH-t-Bu-6-OCH 3
4-CN-6-Cl 4-NHCOH 3-6-Cl 4-NH-i-Pr-6-Cl 4-NH-t-Bu-6-SCH 3
4,6-2CH 3 4-NHCOH 3-6-OCH 3 4-NH-i-Pr-6-CN 4-NH-t-Bu-6-NH 2
4,6-2OCH 3 4-NHCOH 3-6-SCH 3 4-NH-i-Pr-6-OCH 3 4-NH-t-Bu-6-NHCH 3
4-OCH 3-6-Cl 4-NHCOH 3-6-SO 2CH 3 4-NH-i-Pr-6-SCH 3 4-NH-t-Bu-6-NHCOH 3
Figure PCTCN2019104960-appb-000019
表15
(R 6)n (R 6)n (R 6)n (R 6)n
5-F-6-CN 5-Br-6-CO 2CH 3 6-CO 2CH 3 6-CONH(C 2H 5) 2
5-Cl-6-CN 5-F-6-CONCH 3 6-CO 2H 6-CSNH 2
5-Br-6-CN 5-Cl-6-CONCH 3 6-CONH 2 6-CSNHCH 3
5-CH 3-6-CN 5-F-Br-CONCH 3 6-CONHCH 3 6-CSNHC 2H 5
5-F-6-CO 2CH 3 5-CH 3-6-CO 2CH 3 6-CONHC 2H 5 6-CSN(CH 3) 2
5-Cl-6-CO 2CH 3 6-CN 6-CONH(CH 3) 2 6-CSN(C 2H 5) 2
Figure PCTCN2019104960-appb-000020
表16
(R 6)n (R 6)n (R 6)n (R 6)n
3-CN 3-CONHCH 3 3-CSN(CH 3) 2 3-CO 2CH 3-6-Cl
3-CO 2CH 3 3-CONHC 2H 5 3-CSN(C 2H 5) 2 3-CO 2CH 3-6-Br
3-CO 2C 2H 5 3-CON(CH 3) 2 3-CN-6-F 3-CO 2CH 3-6-CH 3
3-CO 2H 3-CON(C 2H 5) 2 3-CN-6-Cl 3-CONHCH 3-6-F
3-CO 2Na 3-CSNH 2 3-CN-6-Br 3-CONHCH 3-6-Cl
3-CO 2NH 4 3-CSNHCH 3 3-CN-6-CH 3 3-CONHCH 3-6-Br
3-CONH 3-CSNHC 2H 5 3-CO 2CH 3-6-F 3-CONHCH 3-6-CH 3
Figure PCTCN2019104960-appb-000021
表17
(R 6)n (R 6)n (R 6)n (R 6)n
3-CN 3-CONH 2 3-CSNHC 2H 5 3-CO 2CH 3-5-Cl
3-CO 2CH 3 3-CONHCH 3 3-CSN(CH 3) 2 3-CO 2CH 3-5-Br
3-CO 2C 2H 5 3-CONHC 2H 5 3-CN-5-F 3-CO 2CH 3-5-CH 3
3-CO 2C(CH 3) 3 3-CON(CH 3) 2 3-CN-5-Cl 3-CONHCH 3-5-F
3-CO 2H 3-CON(C 2H 5) 2 3-CN-5-Br 3-CONHCH 3-5-Cl
3-CO 2Na 3-CSNH 2 3-CN-5-CH 3 3-CONHCH 3-5-Br
3-CO 2NH 4 3-CSNHCH 3 3-CO 2CH 3-5-F 3-CONHCH 3-5-CH 3
本申请的部分化合物可以用表18中列出的具体化合物来说明，但并不限定本申请。
表18
Figure PCTCN2019104960-appb-000022
Figure PCTCN2019104960-appb-000023
Figure PCTCN2019104960-appb-000024
合成方法
本申请的通式(I)化合物可借助文献描述的方法由哒嗪化合物II得到，如
CN102924386B，CN104402828A，CN103058933A和CN101099740等
Figure PCTCN2019104960-appb-000025
当R 2NR 3表示
Figure PCTCN2019104960-appb-000026
基团时，可以借助文献由化合物A制备，参考文献如：CN105753853A和CN103058933等。
Figure PCTCN2019104960-appb-000027
反应在适宜的溶剂中进行，适宜的溶剂可选自苯、甲苯、二甲苯、丙酮、四氢呋喃、乙腈、N,N-二甲基甲酰胺、N-甲基吡咯烷酮、二氯甲烷、氯仿、二氯乙烷或乙酸乙酯等。反应可以在有碱或无碱存在下进行，当在有碱存在下进行反应时，可加速反应进行。所述的碱可以选自：碱金属氢化物，如氢化钠、氢化锂或氨基钠等；碱金属氢氧化物，如氢氧化钠或氢氧化钾；碱金属碳酸盐，如碳酸钠或碳酸钾；有机碱类，如吡啶、4-二甲氨基吡啶、三乙胺、N-甲基吡咯或二异丙基乙基胺等。反应温度可在-10℃至反应中所选用的适宜的溶剂沸点温度之间，通常为0～100℃。反应时间为30分钟至20小时，通常为1～10小时。
文中所述中间体除非另有说明，均为市购。X和Z均为离去基团，X和Z选自氟、氯、溴、碘、甲磺酸酯基或对甲苯磺酸酯等。
化合物I及其可农用盐适合以异构体混合物形式和纯异构体形式用作除草剂。它们适合直接使用或适合以适当配制的组合物使用。包含化合物I的除草组合物非常有效地防治非作物区域的植物生长，尤其是在高施用率下。它们在作物如小麦、稻、玉米、大豆和棉花中作用于阔叶杂草和禾本科杂草而不对农作物引起任何显著的损害。该效果主要在低施用率下观察到。
取决于所述施用方法，化合物I或者包含它们的组合物可以额外用于许多其他农作物以消除不希望的植物。合适的作物实例如下：
洋葱(Allium cepa)、凤梨(Ananas comosus)、落花生(Arachis hypogaea)、石刁柏(Asparagus officinalis)、燕麦(Avena sativa)、甜菜(Beta vulgaris spec.altissima)、甜菜(Beta vulgaris spec.rapa)、欧洲油菜(Brassica napus var.napus)、芜青甘蓝(Brassica napus var.napobrassica)、芜青(Brassica rapavar.silvestris)、羽衣甘蓝(Brassica oleracea)、黑芥(Brassica nigra)、大叶茶(Camellia sinensis)、红花(Carthamus tinctorius)、美国山核桃(Carya illinoinensis)、柠檬(Citrus limon)、甜橙(Citrus sinensis)、小果咖啡(Coffea arabica)(中果咖啡(Coffea canephora)、大果咖啡(Coffea liberica))、黄瓜(Cucumis sativus)、狗牙根(Cynodon dactylon)、胡萝卜(Daucus carota)、油棕(Elaeis guineensis)、欧洲草莓(Fragaria vesca)、大豆(Glycine max)、陆地棉(Gossypium hirsutum)(树棉(Gossypium arboreum)、草棉(Gossypium herbaceum)、Gossypium vitifolium)、 向日葵(Helianthus annuus)、大麦(Hordeum vulgare)、啤酒花(Humulus lupulus)、甘薯(Ipomoea batatas)、核桃(Juglans regia)、兵豆(Lens culinaris)、亚麻(Linum usitatissimum)、番茄(Lycopersicon lycopersicum)、苹果属(Malus spec.)、木薯(Manihot esculenta)、紫苜蓿(Medicago sativa)、芭蕉属(Musa spec.)、烟草(Nicotiana tabacum)(黄花烟草(N.rustica))、油橄榄(Olea europaea)、稻(Oryza sativa)、金甲豆(Phaseolus lunatus)、菜豆(Phaseolus vulgaris)、欧洲云杉(Picea abies)、松属(Pinus spec.)、开心果(Pistacia vera)、Pisum sativum、欧洲甜樱桃(Prunus avium)、Prunuspersica、西洋梨(Pyrus communis)、杏(Prunus armeniaca)、欧洲酸樱桃(Prunus cerasus)、扁桃(Prunus dulcis)和欧洲李(Prunus domestica)、Ribes sylvestre、蓖麻(Ricinuscommunis)、甘蔗(Saccharum officinarum)、黑麦(Secale cereale)、白芥(Sinapisalba)、马铃薯(Solanum tuberosum)、两色蜀黍(Sorghum bicolor)(高粱(S.vulgare))、可可树(Theobroma cacao)、红车轴草(Trifolium pratense)、普通小麦(Triticum aestivum)、小黑麦(Triticale)、硬粒小麦(Triticum durum)、蚕豆(Vicia faba)、葡萄(Vitis vinifera)、玉蜀黍(Zea mays)或水稻等。
化合物I或包含化合物I的除草组合物例如可以以即喷水溶液，粉末，悬浮液以及高度浓缩的水性、油性或其他悬浮液或分散体，乳液，油分散体，糊，粉剂，撒播用材料或颗粒的形式通过喷雾、雾化、撒粉、撒播、浇灌或处理种子或与种子混合而使用。使用形式取决于意欲的目的；在每种情况下都应确保本申请活性成分的最佳可能分布。
除草组合物包含除草有效量的至少一种式I化合物或I的可农用盐和常用于配制作物保护剂的助剂。
常用于配制作物保护剂的助剂实例是：惰性助剂，固体载体，表面活性剂(如分散剂、保护性胶体、乳化剂、润湿剂和增粘剂)，有机和无机增稠剂，杀菌剂，防冻剂，以及消泡剂，合适的话还有着色剂以及用于种子配制剂的粘合剂。
增稠剂(即赋予配制剂以改性的流动性能，即静止状态下的高粘度和运动状态下的低粘度的化合物)的实例是：多糖，如黄原胶，以及有机和无机片状矿物。
消泡剂实例是：聚硅氧烷乳液，长链醇，脂肪酸，脂肪酸盐，有机氟化合物及其混合物。
防冻剂实例是：乙二醇、丙二醇、脲或甘油。
粘合剂的实例是：聚乙烯吡咯烷酮、聚乙酸乙烯酯、聚乙烯醇和纤基乙酸钠。
合适的惰性助剂例如为下列物质：中沸点到高沸点的矿物油馏分如煤油和柴油，此外还有煤焦油和植物或动物来源的油，脂族、环状和芳族烃如石蜡，四氢化萘，烷基化萘及其衍生物，烷基化苯及其衍生物，醇类如甲醇、乙醇、丙醇、丁醇和环己醇，酮类如环己酮或强极性溶剂，例如胺类如N-甲基吡咯烷酮，以及水。
固体载体为：矿土如硅石、硅胶、硅酸盐、滑石、高岭土、石灰石、石灰、白垩、红玄武土、黄土、粘土、白云石、硅藻土、硫酸钙、硫酸镁和氧化镁，磨碎的合成材料，肥料如硫酸铵、磷酸铵、硝酸铵和脲类以及植物来源的产品如谷粉、树皮粉、木粉和坚果壳粉，纤维素粉或其他固体载体。
合适的表面活性剂(助剂、润湿剂、增粘剂、分散剂和乳化剂)是芳族磺酸如木素磺酸(例如Borrespers类型，Borregaard)、苯酚磺酸、萘磺酸(Morwet类型，Akzo Nobel)和二丁基萘磺酸(Nekal类型，BASF SE)以及脂肪酸的碱金属盐、碱土金属盐和铵盐，烷基-和烷基芳基磺酸盐，烷基硫酸盐，月桂基醚硫酸盐和脂肪醇硫酸盐，以及硫酸化十六-、十七-和十八烷醇的盐，还有脂肪醇乙二醇醚的盐，磺化萘及其衍生物与甲醛的缩合物，萘或萘磺酸与苯酚和甲醛的缩合物，聚氧乙烯辛基酚醚，乙氧基化异辛基-、辛基-或壬基酚，烷基苯基或三丁基苯基聚乙二醇醚，烷基芳基聚醚醇，异十三烷醇，脂肪醇/氧化乙烯缩合物，乙氧基化蓖麻油，聚氧乙烯烷基醚或聚氧丙烯烷基醚，月桂醇聚乙二醇醚乙酸酯，山梨糖醇酯，木素亚硫酸盐废液和蛋白质，变性蛋白质，多糖(如甲基纤维素)，疏水改性的淀粉，聚乙烯醇(Mowiol类型，Clariant)，聚羧酸盐类(BASF SE，Sokalan类型)，聚烷氧基化物，聚乙烯胺(BASF SE，Lupamine类型)，聚乙烯亚胺(BASF SE，Lupasol类型)，聚乙烯基吡咯烷酮及其共聚物。
粉末、撒播材料和粉剂可以通过将活性成分与固体载体混合或研磨来制备。
颗粒如包衣颗粒、浸渍颗粒和均质颗粒可以通过使活性成分与固体载体粘附而制备。
含水使用形式可以通过添加水由乳液浓缩物、悬浮液、糊、可湿性粉末或水分散性颗粒制备。为了制备乳液、糊或油分散体，可以借助湿润剂、增粘剂、分散剂或乳化剂将式I或Ia化合物直接或溶于油 或溶剂之后在水中均化。或者还可以制备包含活性物质、湿润剂、增粘剂、分散剂或乳化剂以及需要的话，溶剂或油的浓缩物，该类浓缩物适于用水稀释。
式I化合物在即用制剂中的浓度可以在宽范围内变化。配制剂通常包含0.001-98重量％，优选0.01-95重量％至少一种活性化合物。活性化合物以90-100％，优选95-100％(根据NMR光谱)的纯度使用。
配制剂或即用制剂还可以包含酸、碱或缓冲剂体系，合适的实例是：磷酸或硫酸，或尿素或氨。
本申请化合物I例如可以按如下配制：
1.用水稀释的产品
A 水溶性浓缩物
将10重量份活性化合物溶于90重量份水或水溶性溶剂中。或者，加入湿润剂或其他助剂。活性化合物经水稀释溶解。这得到活性化合物含量为10重量％的配制剂。
B 分散性浓缩物
将20重量份活性化合物溶于70重量份环己酮中并加入10重量份分散剂如聚乙烯基吡咯烷酮。用水稀释得到分散体。活性化合物含量为20重量％。
C 可乳化浓缩物
将15重量份活性化合物溶于75重量份有机溶剂(如烷基芳烃)中并加入十二烷基苯磺酸钙和蓖麻油乙氧基化物(在每种情况下为5重量份)。用水稀释得到乳液。该配制剂的活性化合物含量为15重量％。
D 乳液
将25重量份活性化合物溶于35重量份有机溶剂(如烷基芳烃)中并加入十二烷基苯磺酸钙和蓖麻油乙氧基化物(在每种情况下为5重量份)。借助乳化机(Ultraturrax)将该混合物引入30重量份水中并制成均相乳液。用水稀释得到乳液。该配制剂的活性化合物含量为25重量％。
E 悬浮液
在搅拌的球磨机中，将20重量份活性化合物粉碎并加入10重量份分散剂和湿润剂以及70重量份水或有机溶剂，得到细碎活性化合物悬浮液。用水稀释得到稳定的活性化合物悬浮液。该配制剂中活性化合物含量为20重量％。
F 水分散性颗粒和水溶性颗粒
将50重量份活性化合物细碎研磨并加入50重量份分散剂和湿润剂，借助工业装置(如挤出机、喷雾塔、流化床)将其制成水分散性或水溶性颗粒。用水稀释得到稳定的活性化合物分散体或溶液。该配制剂的活性化合物含量为50重量％。
G 水分散性粉末和水溶性粉末
将75重量份活性化合物在转子-定子磨机中研磨并加入25重量份分散剂、湿润剂和硅胶。用水稀释得到稳定的活性化合物分散体或溶液。该配制剂的活性化合物含量为75重量％。
H 凝胶配制剂
在球磨机中研磨20重量份活性化合物、10重量份分散剂、1重量份胶凝剂和70重量份水或有机溶剂，得到细悬浮液。用水稀释得到活性化合物含量为20重量％的稳定悬浮液。
2.不经稀释而施用的产品
I 粉剂
将5重量份活性化合物细碎研磨并与95重量份细碎高岭土充分混合。这得到活性化合物含量为5重量％的撒粉粉末。
J 颗粒(GR，FG，GG和MG)
将0.5重量份活性化合物细碎研磨并结合99.5重量份载体。现行方法是挤出、喷雾干燥或流化床方法。这得到不经稀释而施用的活性化合物含量为0.5重量％的颗粒。
K ULV溶液(UL)
将10重量份活性化合物溶于90重量份有机溶剂如二甲苯中。这得到不经稀释而施用的活性化合物含量为10重量％的产品。
化合物I或包含它们的除草组合物可以出苗前或出苗后施用，或者与农作物的种子一起施用。还可 以通过施用被除草组合物或活性化合物预处理的农作物的种子而施用除草组合物或活性化合物。若活性化合物不能被某些农作物良好地耐受，则可以使用其中借助喷雾设备喷雾除草组合物以使它们尽可能不接触敏感农作物的叶子，而活性成分到达生长在下面的不希望的植物的叶子或裸露的土壤表面的施用技术。
在另一实施方案中，可以通过处理种子而施用式I化合物或其除草组合物。
种子的处理基本包括所有本领域熟练技术人员熟知的基于本申请式I化合物或由其制备的组合物的程序(拌种、种子包衣、种子撒粉、种子浸泡、种子包膜、种子多层包衣、种子包壳、种子浸滴和种子造粒)。这里可以加以稀释或不加稀释地施用除草组合物。
术语种子包括所有类型的种子，如谷粒、种子、果实、块茎、插条和类似形式。这里优选术语种子描述的是谷粒和种子。
所用种子可以是上述有用植物的种子，但还可以是转基因植物或通过常规育种方法得到的植物的种子。
活性化合物的施用率为0.001-3.0kg/ha，优选0.01-1.0kg/ha活性物质(a.s.)，取决于防治目标、季节、目标植物和生长阶段。为了处理种子，化合物I通常以0.001-10kg/100kg种子的量使用。还可能有利的是将式I化合物与安全剂组合使用。安全剂是防止或降低对有用植物的损害而不显著影响式I化合物对不希望的植物的除草作用的化合物。它们可以在播种之前(例如在种子处理中或在插条或秧苗上)和有用植物出苗之前或之后使用。安全剂和式I化合物可以同时或依次使用。合适的安全剂例如为(喹啉-8-氧基)乙酸、1-苯基-5-卤代烷基-1H-1,2,4-三唑-3-羧酸、1-苯基-4,5-二氢-5-烷基-1H-吡唑-3,5-二羧酸、4,5-二氢-5,5-二芳基-3-异噁唑羧酸、二氯乙酰胺类、α-肟基苯基乙腈类、苯乙酮肟类、4,6-二卤代-2-苯基嘧啶、N-[[4-(氨基羰基)苯基]磺酰基]-2-苯甲酰胺、1,8-萘二甲酸酐、2-卤代-4-卤代烷基-5-噻唑羧酸、硫代磷酸酯类和O-苯基N-烷基氨基甲酸酯及其可农用盐，以及它们的可农用衍生物如酰胺、酯和硫酯，条件是它们具有酸官能团。
为了拓宽活性谱并获得协同增效效果，可以将式I化合物与大量其他除草或生长调节活性化合物的代表或安全剂混合并联合施用。合适的混合配对例如为1,2,4-噻二唑类，1,3,4-噻二唑类，酰胺类，氨基磷酸及其衍生物，氨基三唑类，酰替苯胺类，芳氧基/杂芳氧基链烷酸及其衍生物，苯甲酸及其衍生物，苯并噻二嗪酮类，2-杂芳酰基/芳酰基-1,3-环己烷二酮类，杂芳基芳基酮类，苄基异恶唑烷酮类，间-CF3-苯基衍生物，氨基甲酸酯类，喹啉羧酸及其衍生物，氯代乙酰苯胺类，环己酮肟醚衍生物，二嗪类，二氯丙酸及其衍生物，二氢苯并呋喃类，二氢呋喃-3-酮类，二硝基苯胺类，二硝基苯酚类，二苯基醚类，联吡啶类，卤代羧酸及其衍生物，脲类，3-苯基尿嘧啶类，咪唑类，咪唑啉酮类，N-苯基-3,4,5,6-四氢邻苯二甲酰亚胺类，噁二唑类，环氧乙烷类，酚类，芳氧基-和杂芳氧基苯氧基丙酸酯，苯基乙酸及其衍生物，2-苯基丙酸及其衍生物，吡唑类，苯基吡唑类，哒嗪类，吡啶羧酸及其衍生物，嘧啶基醚类，磺酰胺类，磺酰脲类，三嗪类，三嗪酮类，三唑啉酮类，三唑羧酰胺，尿嘧啶类，苯基吡唑啉类，异噁唑啉类及其衍生物。
此外，可能有用的是单独或与其他除草剂组合施用化合物I，或者还可以与其他作物保护试剂混合而联合施用化合物I，例如与用于防治害虫或植物病原性真菌或细菌的组合物联合施用化合物I。还令人感兴趣的是与无机盐溶液的溶混性，所述盐溶液用于缓解营养和痕量元素缺乏。还可以加入其他添加剂如非植物毒性油和油浓缩物。
可以与本申请的式I的吡啶化合物组合使用的除草剂实例为：
b1)选自如下的类脂生物合成抑制剂：烯草酮(clethodim)、炔草酯(clodinafop)、炔草酯(clodinafop-propargyl)、噻草酮(cycloxydim)、氰氟草酯(cyhalofop)、氰氟草酯(cyhalofop-butyl)、氯甲草(diclofop)、禾草灵(diclofop-methyl)、噁唑禾草灵(fenoxaprop-ethyl)、吡氟禾草灵(fluazifop)、吡氟禾草灵(fluazifop-butyl)、精吡氟禾草灵(fluazifop-P)、精吡氟禾草灵(fluazifop-P-butyl)、吡氟氯禾灵(haloxyfop)、吡氟氯禾灵(haloxyfop-methyl)、精吡氟氯禾灵(haloxyfop-P)、精吡氟氯禾灵(haloxyfop-P-methyl)、噁唑酰草胺(metamifop)、唑啉草酯(pinoxaden)、环苯草酮(profoxydim)、喔草酯(propaquizafop)、喹禾灵(quizalofop)、喹禾灵(quizalofop-ethyl)、喹禾灵(四氢糠基酯)(quizalofop-tefuryl)、精喹禾灵(quizalofop-P)、 精喹禾灵(quizalofop-P-ethyl)、精喹禾灵(四氢糠基酯)(quizalofop-P-tefuryl)、稀禾定(sethoxydim)、醌肟草(tepraloxydim)、肟草酮(tralkoxydim)、呋草黄(benfuresate)、苏达灭(butylate)、草灭特(cycloate)、茅草枯(dalapon)、哌草丹(dimepiperate)、扑草灭(EPTC)、禾草畏(esprocarb)、乙呋草黄(ethofumesate)、四氟丙酸(flupropanate)、草达灭(molinate)、坪草丹(orbencarb)、克草猛(pebulate)、苄草丹(prosulfocarb)、TCA、杀草丹(thiobencarb)、丁草威(tiocarbazil)、野麦畏(triallate)和灭草猛(vernolate)；
b2)选自如下的ALS抑制剂：苄嘧磺隆(bensulfuron)、苄嘧磺隆(bensulfuron-methyl)、双嘧苯甲酸(bispyribac)、醚磺隆(cinosulfuron)、唑嘧磺胺酸(cloransulam)、唑嘧磺胺盐(cloransulam-methyl)、环丙磺隆(cyclosulfamuron)、唑嘧磺胺(diclosulam)、胺苯磺隆(ethametsulfuron)、胺苯磺隆(ethametsulfuron-methyl)、乙氧嘧磺隆(ethoxysulfuron)、啶嘧磺隆(flazasulfuron)、双氟磺草胺(florasulam)、氟酮磺隆(flucarbazone)、氟吡磺隆(flucetosulfuron)、氟唑啶草(flumetsulam)、氟定磺隆(flupyrsulfuron)、氟定磺隆(flupyrsulfuron-methyl-sodium)、甲酰氨磺隆(foramsulfuron)、吡氯磺隆(halosulfuron)、吡氯磺隆(halosulfuron-methyl)、咪草酯(imazosulfuron)、碘磺隆(iodosulfuron)、碘甲磺隆钠(iodosulfuron-methyl-sodium)、甲基二磺隆(mesosulfuron)、唑草磺胺(metosulam)、甲磺隆(metsulfuron)、甲磺隆(metsulfuron-methyl)、烟嘧磺隆(nicosulfuron)、嘧苯胺磺隆(orthosulfamuron)、环丙氧磺隆(oxasulfuron)、五氟磺草胺(penoxsulam)、氟嘧磺隆(primisulfuron)、氟嘧磺隆(primisulfuron-methyl)、丙苯磺隆(propoxycarbazone)、丙苯磺隆(propoxycarbazone-sodium)、氟丙磺隆(prosulfuron)、吡嘧磺隆(pyrazosulfuron)、吡嘧磺隆(pyrazosulfuron-ethyl)、嘧苯草肟(pyribenzoxim)、pyrimisulfan、环酯草醚(pyriftalid)、肟啶草(pyriminobac)、肟啶草(pyriminobac-methyl)、啶磺草胺(pyroxsulam)、噻磺隆(thifensulfuron)、噻磺隆(thifensulfuron-methyl)、醚苯磺隆(triasulfuron)、苯磺隆(tribenuron)、苯磺隆(tribenuron-methyl)、三氟啶磺隆(trifloxysulfuron)、氟胺磺隆(triflusulfuron)、氟胺磺隆(triflusulfuron-methyl)和三氟甲磺隆(tritosulfuron)；(imazamethabenz)、咪草酯(imazamethabenz-methyl)、咪草啶酸(imazamox)、甲基咪草烟(imazapic)、灭草烟(imazapyr)、灭草喹(imazaquin)、咪草烟(imazethapyr)、啶咪磺隆(imazosulfuron)、碘磺隆(iodosulfuron)、碘甲磺隆钠(iodosulfuron-methyl-sodium)、甲基二磺隆(mesosulfuron)、唑草磺胺(metosulam)、甲磺隆(metsulfuron)、甲磺隆(metsulfuron-methyl)、烟嘧磺隆(nicosulfuron)、嘧苯胺磺隆(orthosulfamuron)、环丙氧磺隆(oxasulfuron)、五氟磺草胺(penoxsulam)、氟嘧磺隆(primisulfuron)、氟嘧磺隆(primisulfuron-methyl)、丙苯磺隆(propoxycarbazone)、丙苯磺隆(propoxycarbazone-sodium)、氟丙磺隆(prosulfuron)、吡嘧磺隆(pyrazosulfuron)、吡嘧磺隆(pyrazosulfuron-ethyl)和嘧苯草肟(pyribenzoxim)。
b3)选自如下的光合成抑制剂：莠灭净(ametryn)、胺唑草酮(amicarbazone)、莠去津(atrazine)、噻草平(bentazone)、噻草平(bentazone-sodium)、除草定(bromacil)、杀草全(bromofenoxim)、溴苯腈(bromoxynil)及其盐和酯、氯溴隆(chlorobromuron)、杀草敏(chloridazone)、草净津(cyanazine)、异苯敌草(desmedipham)、敌草净(desmetryn)、敌草快(diquat-dibromide)、敌草隆(diuron)、伏草隆(fluometuron)、六嗪同(hexazinone)、碘苯腈(ioxynil)及其盐和酯、异丙隆(isoproturon)、异恶隆(isouron)、卡草灵(karbutilate)、环草定(lenacil)、利谷隆(linuron)、苯嗪草(metamitron)、噻唑隆(methabenzthiazuron)、对草快(paraquat-dimetilsulfate)、蔬草灭(pentanochlor)、苯敌草(phenmedipham)、乙苯敌草(phenmedipham-ethyl)、扑灭通(prometon)、扑草净(prometryn)、敌稗(propanil)、扑灭津(propazine)、pyridafol、达草止(pyridate)、环草隆(siduron)、西玛津(simazine)、西草净(simetryn)、特草定(terbacil)和特丁津(terbuthylazine)。
b4)选自如下的原卟啉原-IX氧化酶抑制剂：氟锁草醚(acifluorfen)、氟锁草醚(aciflorfen-sodium)、唑啶炔草(azafenidin)、bencarbazone、双苯嘧草酮(benzfendizone)、治草醚(bifenox)、氟丙嘧草酯(butafenacil)、氟酮唑草(carfentrazone)、氟酮唑草(carfentrazone-ethyl)、氯硝醚(chlomethoxyfen)、吲哚酮草酯(cinidon-ethyl)、异丙吡草酯(fuazolate)、氟哒嗪草酯(fufenpyr)、氟哒嗪草酯(flufenpyr-ethyl)、酰亚胺苯氧乙酸(flumiclorac)、酰亚胺苯氧乙酸戊酯(flumiclorac-pentyl)、氟噁嗪酮(flumioxazin)、乙羧氟草醚(fluoroglycofen)、乙羧氟草醚(fluoroglycofen-ethyl)、达草氟(fluthiacet)、达草氟(fluthiacet-methyl)、氟黄胺草醚(fomesafen)、氟硝磺酰胺(halosafen)、乳氟禾草灵(lactofen)、炔丙噁唑草(oxadiargyl)、恶草灵(oxadiazon)、乙氧氟草醚(oxyfluorfen)、戊噁唑草(pentoxazone)、氟唑草胺(profuazol)、双唑草腈(pyraclonil)、 氟唑草酯(pyraflufen)、氟唑草酯(pyraflufen-ethyl)、嘧啶肟草醚(saflufenacil)、磺胺草唑(sulfentrazone)、噻二唑胺(thidiazimin)、2-氯-5-[3,6-二氢-3-甲基-2,6-二氧代-4-三氟甲基-1(2H)-嘧啶基]-4-氟-N-[(异丙基)甲基氨磺酰基]苯甲酰胺(H-1；CAS372137-35-4)、[3-[2-氯-4-氟-5-(1-甲基-6-三氟甲基-2,4-二氧代-1,2,3,4-四氢嘧啶-3-基)苯氧基]-2-吡啶氧基]乙酸乙酯(H-2；CAS 353292-31-6)、N-乙基-3-(2,6-二氯-4-三氟甲基苯氧基)-5-甲基-1H-吡唑-1-甲酰胺(H-3；CAS 452098-92-9)、N-四氢糠基-3-(2,6-二氯-4-三氟甲基苯氧基)-5-甲基-1H-吡唑-1-甲酰胺(H-4；CAS915396-43-9)、N-乙基-3-(2-氯-6-氟-4-三氟甲基苯氧基)-5-甲基-1H-吡唑-1-甲酰胺(H-5；CAS 452099-05-7)、N-四氢糠基-3-(2-氯-6-氟-4-三氟甲基苯氧基)-5-甲基-1H-吡唑-1-甲酰胺(H-6；CAS 45100-03-7)、3-[7-氟-3-氧代-4-(丙-2-炔基)-3,4-二氢-2H-苯并[1,4]噁嗪-6-基]-1,5-二甲基-6-硫代-[1,3,5]三嗪烷(triazinan)-2,4-二酮，1,5-二甲基-6-硫代-3-(2,2,7-三氟-3-氧代-4-(丙-2-炔基)-3,4-二氢-2H-苯并[b][1,4]噁嗪-6-基)-1,3,5-三嗪烷-2,4-二酮和2-(2,2,7-三氟-3-氧代-4-丙-2-炔基-3,4-二氢-2H-苯并[1,4]噁嗪-6-基)-4,5,6,7-四氢异吲哚-1,3-二酮和1-甲基-6-三氟甲基-3-(2,2,7-三氟-3-氧代-4-丙-2-炔基-3,4-二氢-2H-苯并[1,4]噁嗪-6-基)-1H-嘧啶-2,4-二酮；
下述式2表示的化合物：
Figure PCTCN2019104960-appb-000028
b5)选自如下的漂白剂除草剂：苯草醚(aclonifen)、杀草强(amitrol)、氟丁酰草胺(beflubutamid)、苯并双环酮(benzobicyclon)、吡草酮(benzofenap)、异恶草酮(clomazone)、吡氟草胺(diflufenican)、氟草同(fluridone)、氟咯草酮(flurochloridone)、呋草酮(flurtamone)、异噁氟草(isoxaflutole)、甲基磺草酮(mesotrione)、达草灭(norflurazon)、氟吡酰草胺(picolinafen)、pyrasulfutole、吡唑特(pyrazolynate)、苄草唑(pyrazoxyfen)、磺草酮(sulcotrione)、tefuryltrione、tembotrione、topramezone、bixlozone、三唑磺草酮、环吡氟草酮、双唑磺草酮、4-羟基-3-[[2-[(2-甲氧基乙氧基)甲基]-6-(三氟甲基)-3-吡啶基]羰基]双环[3.2.1]辛-3-烯-2-酮(H-7；CAS 352010-68-5)和4-(3-三氟甲基苯氧基)-2-(4-三氟甲基苯基)嘧啶(H-8；CAS 180608-33-7)；
b6)选自如下的EPSP合成酶抑制剂：草甘膦、草甘膦异丙胺盐(glyphosate-isopropylammonium)和草硫膦(glyphosate-trimesium)(sulfosate)；
b7)选自如下的谷氨酰胺合成酶抑制剂：双丙氨酰膦(bilanaphos(bialaphos))、双丙氨酰膦(bilanaphos-sodium)和草铵膦(glufosinate-ammonium)；
b8)选自如下的DHP合成酶抑制剂：黄草灵(asulam)；
b9)选自如下的有丝分裂抑制剂：胺草磷(amiprophos)、甲基胺草磷(amiprophos-methyl)、氟草胺(benfluralin)、草胺磷(butamiphos)、地乐胺(butralin)、长杀草(carbetamide)、氯苯胺灵(chlorpropham)、敌草索(chlorthal)、敌草索(chlorthal-dimethyl)、敌乐胺(dinitramine)、氟硫草定(dithiopyr)、丁氟消草(ethalfluralin)、氟消草(fluchloralin)、黄草消(oryzalin)、胺硝草(pendimethalin)、氨基丙氟灵(prodiamine)、苯胺灵(propham)、拿草特(propyzamide)、丙戊草胺(tebutam)、噻氟啶草(thiazopyr)和氟乐灵(trifluralin)；
b10)选自如下的VLCFA抑制剂：乙草胺(acetochlor)、甲草胺(alachlor)、莎稗磷(anilofos)、丁草胺(butachlor)、唑草胺(cafenstrole)、克草胺(dimethachlor)、噻吩草胺(dimethanamid)、精噻吩草胺(dimethenamid-P)、草乃敌(diphenamid)、四唑酰草胺(fentrazamide)、氟噻草胺(flufenacet)、苯噻草胺(mefenacet)、吡草胺(metazachlor)、异丙甲草胺(metolachlor)、S-异丙甲草胺(metolachlor-S)、萘丙胺(naproanilide)、草萘胺(napropamide)、烯草胺(pethoxamid)、哌草磷(piperophos)、丙草胺(pretilachlor)、扑草胺(propachlor)、异丙草胺(propisochlor)、派罗克杀草砜(pyroxasulfone)(KIH-485)和噻醚草胺(thenylchlor)；
b11)选自如下的纤维素生物合成抑制剂：草克乐(chlorthiamid)、敌草腈(dichlobenil)、胺草唑 (flupoxam)和异恶草胺(isoxaben)；
b12)选自如下的分离剂除草剂：地乐酚(dinoseb)、地乐消酚(dinoterb)以及二硝甲酚(DNOC)及其盐；
b13)选自如下的植物生长素除草剂：2,4-D及其盐和酯、2,4-DB及其盐和酯、氨草啶(aminopyralid)及其盐如氨草啶铵盐(aminopyralid-tris(2-hydroxypropyl)ammonium)和其酯、草除灵(benazolin)、草除灵(benazolin-ethyl)、草灭平(chloramben)及其盐和酯、稗草胺(clomeprop)、二氯皮考啉酸(clopyralid)及其盐和酯、麦草畏(dicamba)及其盐和酯、2,4-滴丙酸(dichlorprop)及其盐和酯、高2,4-滴丙酸(dichlorprop-P)及其盐和酯、氟草烟(fluroxypyr)、氟草烟(fluroxypyr-butometyl)、氟氯胺啶(fluroxypyr-meptyl)、MCPA及其盐和酯、2甲4氯乙硫酯(MCPA-thioethyl)、MCPB及其盐和酯、2甲4氯丙酸(mecoprop)及其盐和酯、高2甲4氯丙酸(mecoprop-P)及其盐和酯、毒莠定(picloram)及其盐和酯、二氯喹啉酸(quinclorac)、喹草酸(quinmerac)、TBA(2,3,6)及其盐和酯、绿草定(triclopyr)及其盐和酯以及5,6-二氯-2-环丙基-4-嘧啶甲酸(H-9；CAS 858956-08-8)及其盐和酯；
b14)选自如下的植物生长素输送抑制剂：二氟吡隆(diflufenzopyr)和抑草生(naptalam)；
b15)选自如下的其他除草剂：溴丁酰草胺(bromobutide)、氯甲丹(chlorflurenol)、氯甲丹(chlorflurenol-methyl)、环庚草醚(cinmethylin)、苄草隆(cumyluron)、茅草枯、棉隆(dazomet)、苯敌快(difenzoquat)、苯敌快(difenzoquat-metilsulfate)、噻节因(dimethipin)、甲胂钠(DSMA)、香草隆(dymron)、敌草腈(endothal)及其盐、氟燕灵(flamprop)、氟燕灵(flamprop-M-isopropyl)、麦草伏(flamprop-M-methyl)、抑草丁(flurenol)、抑草丁(flurenol-butyl)、调嘧醇(flurprimidol)、膦铵素(fosamine)、膦铵素(fosamine-ammonium)、茚草酮(indanofan)、抑芽丹(maleic hydrazide)、氟草磺(mefluidide)、苯丙隆(methyl-dymron)、氯噁嗪草(oxaziclomefone)、壬酸(pelargonic acid)、稗草畏(pyributicarb)、和6-氯-3-(2-环丙基-6-甲基苯氧基)-4-哒嗪醇(H-10；CAS499223-49-3)及其盐和酯。
优选安全剂C的实例为：解草酮(benoxacor)、喹氧乙酸(cloquintocet)、抑害腈(cyometrinil)、cyprosulfamide、抑害胺(dichlormid)、dicyclonone、dietholate、解草唑(fenchlorazole)、解草啶(fenclorim)、解草安(flurazole)、肟草安(fluxofenim)、解草呋(furilazole)、双苯噁唑酸(isoxadifen)、吡咯二酸(mefenpyr)、mephenate、萘二甲酸酐(naphthalic anhydride)、解草腈(oxabetrinil)、4-(二氯乙酰基)-1-氧杂-4-氮杂螺[4.5]癸烷(H-11；MON4660，CAS 71526-07-3)和2,2,5-三甲基-3-(二氯乙酰基)-1,3-噁唑烷(H-12；R-29148，CAS 52836-31-4)。
b1)-b15)组活性化合物和安全剂是已知的除草剂和安全剂，例如参见The Compendium of Pesticide Common Names(http://www.alanwood.net/pesticides/)；B.Hock，C.Fedtke，R.R.Schmidt，Herbizide[除草剂]，Georg Thieme Verlag，Stuttgart，1995。其他除草活性化合物由WO96/26202、WO 97/41116、WO 97/41117、WO 97/41118、WO 01/83459和WO 2008/074991，W.
Figure PCTCN2019104960-appb-000029
等(编辑)"Modern CropProtectionCompounds"，第1卷，Wiley VCH，2007以及其中引用的文献已知。
本申请还涉及配制成单组分组合物的作物保护组合物形式的组合物，所述单组分组合物包含含有至少一种式I的哒嗪化合物和至少一种优选选自b1-b15组活性化合物的其他活性化合物的活性化合物组合以及至少一种固体或液体载体和/或一种或多种表面活性剂和需要的话一种或多种其他常用于作物保护组合物的助剂。
本申请还涉及配制成双组分组合物的作物保护组合物形式的组合物，所述双组分组合物包含含有至少一种式I的哒嗪化合物、固体或液体载体和/或一种或多种表面活性剂的第一组分和含有至少一种选自b1-b15组活性化合物的其他活性化合物、固体或液体载体和/或一种或多种表面活性剂的第二组分，其中这两种组分还可以额外包含其他常用于作物保护组合物的助剂。
本申请化合物I和组合物还可以具有植物增强作用。因此，它们适合调动植物的防御系统以对抗不希望的微生物如有害真菌以及病毒和细菌的侵袭。植物增强(诱发抗性)的物质在本申请上下文中应理解为指能够刺激被处理植物的防御系统以使得当随后被不希望的微生物接种时被处理植物对这些微生物显示出显著抗性的那些物质。
化合物I可以用于在处理之后的一定时间内保护植物免受不希望的微生物侵袭。起保护作用的时间期限通常为用化合物I处理植物之后或处理种子之后的1-28天，优选1-14天，至多在播种之后9个月。
本申请化合物I和组合物还适合提高收获产量。
下面通过实施例说明式I化合物，本申请主题并不限于所示实施例。
具体实施方式
合成实施例
实施例1：化合物I-A-8的制备
Figure PCTCN2019104960-appb-000030
室温搅拌下，将18.3克3,4,6-三氯哒嗪，20.7克2,6-二氯-4-硝基苯胺，15克无水碳酸钾，200ml无水乙腈放入500ml四口烧瓶中，升温至60℃，搅拌反应3小时，反应完毕，脱除溶剂，用300ml乙酸乙酯萃取。柱层析得产物20.1克。
熔点207-209℃。δppm 6.35(1H,s)，8.18-8.23(2H,s)，8.40-8.43(1H,s)。
实施例2 化合物I-B-1的制备
Figure PCTCN2019104960-appb-000031
室温搅拌下，将18.3克3,4,6-三氯哒嗪，19.6克3-氯-5-三氟甲基-2-吡啶胺，18克无水碳酸钾，200ml无水乙腈放入500ml四口烧瓶中，升温至60℃，搅拌反应3小时，反应完毕，脱出溶剂，用300ml乙酸乙酯萃取。柱层析得产物18.3克。
熔点140-142℃。δppm 7.95-8.05(1H,s)，8.30-8.40(1H,s)，8.60-8.70(1H,s)，9.00-9.10(1H,s)。
实施例3 化合物I-I-1的制备
Figure PCTCN2019104960-appb-000032
室温搅拌下，将36.6克3,4,6-三氯哒嗪，33克3,6-二氯-4-氨基哒嗪，35克无水碳酸钾，300ml无水乙腈放入500ml四口烧瓶中，升温至60℃，搅拌反应3小时，反应完毕，脱除溶剂，用500ml乙酸乙酯萃取。柱层析得产物30.6克。
熔点179-181℃。δppm 7.45-7.48(2H,s)。
实施例4 化合物I-O-2的制备
Figure PCTCN2019104960-appb-000033
室温搅拌下，将36.6克3,4,6-三氯哒嗪，41.6克2-二甲氨基-4-三氟甲基-6H-1,3-恶嗪-6-酮，加入到装有200ml乙酸的反应瓶中，升温至回流反应，形成深色溶液，保持该温度下反应6小时，减压脱出溶剂，加入碳酸氢钠水溶液调节pH至中性，乙酸乙酯萃取，脱除溶剂得粗品。柱层析得产品38.5克。
通式(I)的其他化合物可以用本申请提供的制备方法制得。
部分化合物熔点(熔点仪未校正)和核磁数据( 1HNMR，400MHz,内标TMS，溶剂CDCl 3)如下：
化合物I-A-8：熔点207-209℃。δppm 6.35(1H,s)，8.18-8.23(2H,s)，8.40-8.43(1H,s)。
化合物I-B-1：熔点140-142℃。δppm 7.95-8.05(1H,s)，8.30-8.40(1H,s)，8.60-8.70(1H,s)，9.00-9.10(1H,s)。
化合物I-A-17：熔点149-151℃。δppm 6.60-6.66(1H,s)，7.12-7.18(1H,s)。。
化合物I-A-19：δppm 6.70-6.74(1H,s)，8.70-8.72(1H,s)。
化合物I-I-1：熔点179-181℃。δppm 7.45-7.48(2H,s)。
化合物I-I-7：熔点143-147℃。δppm 2.96-2.98(3H,d)，7.26(2H,s)。
II.应用实施例
式I化合物的除草活性通过下列温室试验证实：
所用培养容器为含有含约3.0％腐殖土的壤质砂作为底物的塑料花盆。对每一品种单独播种测试植物的种子。
对于出苗前处理，直接在播种之后借助细分布喷嘴施用悬浮或乳化于水中的活性成分。温和灌溉容器以促进发芽和生长，然后用透明塑料罩覆盖，直到植物生根。该覆盖导致测试植物均匀发芽，除非被活性化合物损坏。
对于出苗后处理，首先使测试植物生长到3-15cm的高度，这取决于植物习性，并仅在此时用悬浮或乳化于水中的活性成分处理。为此，将测试植物直接播种并在相同容器中生长，或者首先使它们作为秧苗单独生长并在处理之前几天移植到测试容器中。
取决于品种，将植物保持在10-25℃或20-35℃。测试期为2-4周。在此期间照料植物并评价它们对各处理的响应。
使用0-100的评分进行评价。100表示没有植物出苗，或者至少地面上部分完全受损，而0表示没有损害，或者生长过程正常。对良好的除草活性给予至少70的分值，而对非常好的除草活性给予至少85的分值。
用于温室试验中的植物属于下列品种：
Figure PCTCN2019104960-appb-000034
在0.5kg/ha的施用率下，通过出苗后方法施用的化合物I-A-8、I-I-1、I-A-19对牛筋草显示出非常好的除草活性。
在0.5kg/ha的施用率下，通过出苗后方法施用的化合物I-I-1对稗草显示出非常好的除草活性。
在0.5kg/ha的施用率下，通过出苗后方法施用的化合物I-I-1对看麦娘显示出非常好的除草活性。
在0.5kg/ha的施用率下，通过出苗后方法施用的化合物I-I-1对早熟禾显示出非常好的除草活性。

Claims (10)

  1. 一种通式I所表示的取代哒嗪胺或其N-氧化物或可农用盐：
    Figure PCTCN2019104960-appb-100001
    式中：
    R 1选自氢、卤素、氰基、未取代的或被1-4个独立选自以下基团取代的苯氧基或杂芳氧基：卤素、硝基、氰基、C 1-C 12烷基、卤代C 1-C 12烷基、C 1-C 12烷氧基、卤代C 1-C 12烷氧基、C 3-C 12环烷基、C 1-C 12烷基羰基或C 1-C 12烷氧基羰基；
    R 2选自氢、C 1-C 12烷基、卤代C 1-C 12烷基、C 1-C 12烷氧基、卤代C 1-C 12烷氧基、C 3-C 6环烷基、氰基C 1-C 12烷基、C 1-C 12烷基氨基、卤代C 1-C 12烷基氨基、C 2-C 6二烷基氨基、C 2-C 12烯基、卤代C 2-C 12炔基、C 2-C 12烯氧基、卤代C 2-C 12烯氧基、C 2-C 12炔基、卤代C 2-C 12烯基、C 2-C 12炔氧基、卤代C 2-C 12炔氧基、C 1-C 12烷基磺酰基、C 1-C 12烷基羰基、卤代C 1-C 12烷基羰基或卤代C 1-C 12烷磺酰基；
    R 3选自未取代的或被1-4个独立选自以下基团取代的苯基、苄基或杂芳基：卤素、羟基、硝基、氰基、CHO、COOH、COONa、C 1-C 12烷基、卤代C 1-C 12烷基、C 1-C 12烷氧基、卤代C 1-C 12烷氧基、C 3-C 6环烷基、氰基C 1-C 12烷基、C 1-C 12烷基氨基、卤代C 1-C 12烷基氨基、C 2-C 6二烷基氨基、C 2-C 12烯基、卤代C 2-C 12炔基、C 2-C 12烯氧基、卤代C 2-C 12烯氧基、C 2-C 12炔基、卤代C 2-C 12炔基、C 2-C 12炔氧基、卤代C 2-C 12炔氧基、C 1-C 12烷硫基、卤代C 1-C 12烷硫基、C 1-C 12烷基磺酰基、C 1-C 12烷基羰基、卤代C 1-C 12烷基羰基或卤代C 1-C 12烷磺酰基；
    R 2NR 3也可以组成被1-4个独立选自以下基团取代或未取代的五元或六元环，所述独立取代基团选自以下基团：卤素、羟基、硝基、氰基、CHO、COOH、COONa、C 1-C 12烷基、卤代C 1-C 12烷基、C 3-C 12环烷基、C 1-C 12烷氧基、卤代C 1-C 12烷氧基、C 1-C 12烷硫基、C 1-C 12烷基羰基或C 1-C 12烷氧基羰基；
    R 4选自卤素、氰基、CHO、COOH、COONa、C 1-C 12烷基磺酰基、卤代C 1-C 12烷基磺酰基或被1-4个独立选自以下基团取代或未取代的芳基磺酰基，所述独立取代基团选自以下基团：卤素、羟基、硝基、氰基、CHO、COOH、COONa、C 1-C 12烷基、卤代C 1-C 12烷基、C 3-C 12环烷基、C 1-C 12烷氧基、卤代C 1-C 12烷氧基、C 1-C 12烷硫基、C 1-C 12烷基羰基或C 1-C 12烷氧基羰基；
    或通式(I)化合物的N-氧化物或可农用盐。
  2. 根据权利要求1所述的哒嗪胺类化合物，其特征在于：通式(I)中
    式中：
    R 1选自氢、Cl、Br、F、I、氰基、未取代的或被1-4个独立选自以下基团取代的苯氧基或杂芳氧基：卤素、硝基、氰基、C 1-C 6烷基、卤代C 1-C 6烷基、C 1-C 6烷氧基、卤代C 1-C 6烷氧基、C 3-C 6环烷基、C 1-C 6烷基羰基或C 1-C 6烷氧基羰基；
    R 2选自氢、C 1-C 6烷基、卤代C 1-C 6烷基、C 1-C 6烷氧基、卤代C 1-C 6烷氧基、C 3-C 6环烷基、氰基C 1-C 6烷基、C 1-C 6烷基氨基、卤代C 1-C 6烷基氨基、C 2-C 6二烷基氨基、C 2-C 6烯基、卤代C 2-C 6烯基、C 2-C 6烯氧基、卤代C 2-C 6烯氧基、C 2-C 6炔基、卤代C 2-C 6炔基、C 2-C 6炔氧基、卤代C 2-C 6炔氧基、C 1-C 6烷基磺酰基、C 1-C 6烷基羰基、卤代C 1-C 6烷基羰基或卤代C 1-C 6烷磺酰基；
    R 3选自未取代的或被1-4个独立选自以下基团取代的苯基、苄基或杂芳基：Cl、Br、F、I、羟基、硝基、氰基、CHO、COOH、COONa、C 1-C 6烷基、卤代C 1-C 6烷基、C 1-C 6烷氧基、卤代C 1-C 6烷氧基、C 3-C 6环烷基、氰基C 1-C 6烷基、C 1-C 6烷基氨基、卤代C 1-C 6烷基氨基、C 2-C 6二烷基氨 基、C 2-C 6烯基、卤代C 2-C 6炔基、C 2-C 6烯氧基、卤代C 2-C 6烯氧基、C 2-C 6炔基、卤代C 2-C 6炔基、C 2-C 6炔氧基、卤代C 2-C 6炔氧基、C 1-C 6烷硫基、卤代C 1-C 6烷硫基、C 1-C 6烷基磺酰基、C 1-C 6烷基羰基、卤代C 1-C 6烷基羰基或卤代C 1-C 6烷磺酰基；
    R 2NR 3也可以组成被1-4个独立选自以下基团取代或未取代的五元或六元环，所述独立取代基团选自以下基团：Cl、Br、F、I、羟基、硝基、氰基、CHO、COOH、COONa、C 1-C 6烷基、卤代C 1-C 6烷基、C 3-C 6环烷基、C 1-C 6烷氧基、卤代C 1-C 6烷氧基、C 1-C 6烷硫基、C 1-C 6烷基羰基或C 1-C 6烷氧基羰基；
    R 4选自Cl、Br、F、I、氰基、CHO、COOH、COONa、C 1-C 6烷基磺酰基或卤代C 1-C 6烷基磺酰基；
    或通式(I)化合物的N-氧化物或可农用盐。
  3. 根据权利要求2所述的化合物，其特征在于：通式(I)中
    R 1选自H、Cl、Br、F、I、CN、CH 3、CH 2CH 3、叔丁基、环丙基、CF 3、CH 2CF 3、OCH 3、OCF 3、OCH 2CF 3、SO 2CH 3、CO 2CH 3、未取代或取代的苯氧基，所述的取代基选自1-3个如下基团：Cl、Br、F、I、CN、NO 2、CHO、COOH、COONa、CH 3、CH 2CH 3、叔丁基、环丙基、CHF 2、CF(CF 3) 2、CF 3、CH 2CF 3、OCH 3、OCHF 2、OCF 3、OCH 2CF 3或SO 2CH 3；
    R 2选自H、甲基、乙基、丙基、异丙基、叔丁基、正丁基、甲氧基、环丙基、氰基乙基、甲氨基、甲磺酰基、烯丙基、炔丙基、甲磺酰基、对甲苯磺酰基、乙基羰基或甲酰基；
    R 3选自未取代的或被1-3个独立选自以下基团取代的苯基、苄基或杂芳基：OH、Cl、Br、F、I、CN、NO 2、CHO、COOH、COONa、CH 3、CH 2CH 3、叔丁基、环丙基、CHF 2、CF 3、CF(CF 3) 2、CH 2CF 3、OCH 3、OCHF 2、OCF 3、OCH 2CF 3或SO 2CH 3；
    R 2NR 3也可以组成被1-3个独立选自以下基团取代或未取代的五元或六元环，所述独立取代基团选自以下基团：OH、Cl、Br、F、I、CN、NO 2、CH 3、CH 2CH 3、叔丁基、环丙基、CHF 2、CF(CF 3) 2、CF 3、CH 2CF 3、OCH 3、OCHF 2、OCF 3、OCH 2CF 3或SO 2CH 3；
    R 4选自Cl、Br、F、I、CN、SO 2CH 3或SO 2CH 2CH 3；
    或通式(I)化合物N-氧化物以及与盐酸、硫酸、磷酸、甲酸、乙酸、草酸、三氟乙酸、甲磺酸、对甲苯磺酸、苹果酸、柠檬酸、锂、钙、钠或者钾形成的盐。
  4. 根据权利要求3所述的化合物，其特征在于：通式(I)中
    R 1选自Cl、Br、F、I、2-甲基苯酚、2-异丙基苯酚、2-环丙基苯酚、2-甲基-6-环丙基苯酚或2-碘苯酚；
    R 2选自H、CH 3、CH 2CH 3、环丙基、甲氧基或甲氨基；
    R 3选自未取代的或被1-3个独立选自以下基团取代的苯基、嘧啶基、吡唑基、吡啶基或哒嗪基：OH、Cl、Br、F、I、CN、NO 2、CHO、COOH、COONa、CH 3、CH 2CH 3、叔丁基、环丙基、CHF 2、CF 3、CH 2CF 3、OCH 3、OCHF 2、OCF 3、CF(CF 3) 2、OCH 2CF 3或SO 2CH 3；
    R 2NR 3也可以组成吗啉、哌嗪、哌啶、吡咯环、吡唑环、三唑环、嘧啶环或
    Figure PCTCN2019104960-appb-100002
    等；
    R 4选自Cl、Br、F、I或CN；
    或通式(I)化合物与盐酸、硫酸、磷酸、锂、钙、钠或者钾形成的盐。
  5. 根据权利要求4所述的化合物，其特征在于：通式(I)中
    R 1选自Cl、Br、F或I；
    R 2选自H、CH 3或CH 2CH 3
    R 3选自未取代的或被1-3个独立选自以下基团取代的苯基、吡啶基或哒嗪基：OH、Cl、Br、F、I、CN、NO 2、CHO、COOH、COONa、CH 3、CH 2CH 3、叔丁基、CHF 2、CF 3、CH 2CF 3、CF(CF 3) 2、 OCH 3、OCHF 2、OCF 3、OCH 2CF 3或SO 2CH 3；
    R 2NR 3也可以组成
    Figure PCTCN2019104960-appb-100003
    环等；
    R 4选自Cl、Br、F、I或CN；
    或通式(I)化合物与盐酸、硫酸、磷酸、锂、钙、钠或者钾形成的盐。
  6. 一种根据权利要求I所述的通式(I)化合物用于苗前或苗后茎叶处理防治杂草的应用。
  7. 根据权利要求I所述的通式I哒嗪胺类化合物用于植物干燥/脱叶的用途。
  8. 一种除草组合物，其特征在于：以权利要求I所述的化合物(I)化合物作为活性组分，组合物中的活性组分的重量百分比含量为0.1-99％。
  9. 根据权利要求8所述的除草组合物用于杂草防治的应用。
  10. 一种如权利要求8所述的除草剂组合物也可以和其他已知的杀虫剂、杀菌剂、植物生长调节剂或肥料(包括除草剂安全剂)等一起混合使用。
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