WO2012059050A1 - Substituted biaryl benzenesulfonamide compound and use - Google Patents

Substituted biaryl benzenesulfonamide compound and use Download PDF

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Publication number
WO2012059050A1
WO2012059050A1 PCT/CN2011/081674 CN2011081674W WO2012059050A1 WO 2012059050 A1 WO2012059050 A1 WO 2012059050A1 CN 2011081674 W CN2011081674 W CN 2011081674W WO 2012059050 A1 WO2012059050 A1 WO 2012059050A1
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alkyl
group
hydrogen
alkoxy
chlorine
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PCT/CN2011/081674
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French (fr)
Chinese (zh)
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刘长令
迟会伟
王正航
张静静
马宏娟
伍强
崔东亮
王立增
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中国中化股份有限公司
沈阳化工研究院有限公司
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Priority to CN201180035252.2A priority Critical patent/CN103003240B/en
Publication of WO2012059050A1 publication Critical patent/WO2012059050A1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D213/26—Radicals substituted by halogen atoms or nitro radicals
    • 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
    • A01N41/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom
    • A01N41/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom containing a sulfur-to-oxygen double bond
    • A01N41/04—Sulfonic acids; Derivatives thereof
    • A01N41/06—Sulfonic acid amides
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
    • 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
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
    • A01N47/12—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing a —O—CO—N< group, or a thio analogue thereof, neither directly attached to a ring nor the nitrogen atom being a member of a heterocyclic ring
    • 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
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
    • A01N47/24—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing the groups, or; Thio analogues thereof
    • 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
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
    • 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
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
    • A01N47/36—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing the group >N—CO—N< directly attached to at least one heterocyclic ring; Thio analogues thereof
    • 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
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/40—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having a double or triple bond to nitrogen, e.g. cyanates, cyanamides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/61—Halogen atoms or nitro radicals
    • 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

Definitions

  • the invention belongs to the field of agricultural herbicides and relates to a substituted biaryl benzene sulfonamide compound and use thereof.
  • R 7 is S0 2 NR 9 R 1 () , R 9 and. Is hydrogen or dC 8 alkyl.
  • An object of the present invention is to provide a herbicidal compound having a novel structure, and it is desired that these compounds have excellent herbicidal activity as compared with the herbicidal compound provided by the prior art, and can be used for purposeful control of harmful plants.
  • the present invention provides a substituted biaryl salt as shown in the general formula (I) -
  • A is selected from CH or N;
  • R4 are each independently selected from the group consisting of hydrogen, fluorine, chlorine, bromine, cyano, nitro, hydroxy, decyl, dC 6 alkyl, dC 6 haloalkyl, C 2 -Q ⁇ 3 ⁇ 4 alkenyl, C 2 - Q ⁇ 3 ⁇ 4 alkynyl, CC 6 alkoxy, dC 6 haloalkoxy, C 2 -C 6 alkenyloxy, C 2 -C 6 3 ⁇ 4 alkenyloxy, ⁇ - alkynyloxy, C 2 -C 6 3 ⁇ 4 alkynyloxy, hydroxycarbonyl, dC 6 alkylcarbonyl, ⁇ -haloalkylcarbonyl, dC 6 alkoxycarbonyl, dC 6 haloalkoxycarbonyl, dC l thio, dC 6 haloalkylthio, dC 6 alkane a sulfin
  • R 5 is selected from the group consisting of hydrogen, fluorine, chlorine, bromine, cyano, nitro, decyl, hydroxy, dC 6 alkyl, CC 6 haloalkyl, C 2 -C 6 alkenyl, C 2 -Q ⁇ 3 ⁇ 4 alkynyl, CC 6 alkoxy, dC 6 3 ⁇ 4 alkoxy, ⁇ -(alkenyloxy), ⁇ -alkynyloxy, hydroxycarbonyl, dC 6 alkylcarbonyl, dC 6 3 ⁇ 4 alkylcarbonyl, dC 6 alkoxy Carbonyl, ⁇ - ⁇ alkoxycarbonyl, dC 6 alkylthio, C 2 -C 6 haloalkylthio, dC 6 alkylsulfinyl, dC 6 haloalkylsulfinyl, dC 6 alkylsulfonyl, dC 6 haloalkylsulf
  • Q is selected from -NR6(CO-XR 7 ), -N3 ⁇ 4, -CN, -N 6 -CH( 8 )-CN, -N3 ⁇ 4, - N 9 (CO-X- 7 ), -N3 ⁇ 4,-NR 9 - CH(R 8 ) -CN, -N 6 - 0-CH 2 (CO-X- 7 ) or -CH(R 8 ) (CO-XR 7 );
  • X is selected from CH 2 , NR 6 , O or S ;
  • R 9 are each independently selected from the group consisting of hydrogen, cyano, CC 6 alkyl, CC 6 alkoxy, CC 6 haloalkyl, CC 6 haloalkoxy or CC 6 alkoxycarbonyl;
  • Preferred compounds of the invention are: in formula (I)
  • A is selected from CH or N;
  • R, R 2 , R 3 , R4 are each independently selected from the group consisting of hydrogen, fluorine, chlorine, bromine, cyano, nitro, dC 6 alkyl, dC 6 haloalkyl, dC 6 alkoxy, dC 6 3 ⁇ 4 alkoxy a hydroxycarbonyl group, a dC 6 alkylcarbonyl group, a dC 6 3 ⁇ 4 alkylcarbonyl group or a dC 6 alkoxycarbonyl group;
  • Q is selected from the group consisting of -NR 6 (CO-XR 7 ), -N3 ⁇ 4, -CN, -NR6-CH( 8 )-CN, - ⁇ -N 9 (CO-X- 7 ), -NR6-NR 9 -CH ( R 8 )-CN, -NR6-0-CH 2 (CO-X- 7 ) or -CH(R 8 ) (CO-X- 7 );
  • X is selected from C3 ⁇ 4, ⁇ , O or S ;
  • R 6 and R 9 are each independently selected from the group consisting of hydrogen, cyano, dC 6 alkyl, dC 6 alkoxy, dC 6 haloalkyl, dC 6 haloalkoxy or dC 6 alkoxycarbonyl;
  • R 7 each independently selected from the group consisting of hydrogen, fluorine, chlorine, bromine, dC 6 alkyl, Ci-C 6 haloalkyl, dC 6 alkoxy dC 6 alkyl, cyano Ci-C6 alkyl, Ci-C6 Base amino-Ci-Cs alkyl, bis-(Ci-C63 ⁇ 43 ⁇ 4S) amino-Ci-C6 alkyl, Ci-C 6 alkoxycarbonyl-dC 6 alkyl, carboxy-dC 6 alkyl, C 3 -C 8 naphthenic a C 2 -Q ⁇ 3 ⁇ 4 alkenyl group, a C 3 -Q ⁇ 3 ⁇ 4 alkynyl group, a phenyl group, a phenyl dC 6 alkyl group or a phenoxy dC 6 alkyl group, on the phenyl or phenoxy ring
  • Each of the hydrogens may be unsubstituted or substituted with from 1 to 4 groups
  • A is selected from CH or N;
  • Q is selected from -NR6(CO-XR 7 ), -NR6.CN, -NR6-CH(R 8 )-CN, -N 6 - NR 9 (CO-XR 7 ), -NR ⁇ - N 9 -CH ( 8 ) -CN, -N 6 - 0-CH 2 (CO-X- 7 ) or -CH(R 8 ) (CO-X-7);
  • X is selected from C3 ⁇ 4, NR6, O or S ;
  • R 6 and R 9 are each independently selected from hydrogen, cyano, CC 4 alkyl, CC 4 alkoxy, CC 4 haloalkyl, CC 4 haloalkoxy or dC 4 alkoxycarbonyl;
  • R 7 each independently selected from the group consisting of hydrogen, chlorine, dC 4 alkyl, CC 4 haloalkyl, CC 4 alkoxy CC 4 alkyl, cyano-Ci-C 4 alkyl, Ci-C 4 alkylamino Ci- C 4 alkyl, bis-(Ci-C 4 alkyl)amino Ci-C 4 alkyl, Ci-C 4 alkoxycarbonyl-dC 4 alkyl, carboxy-dC 4 alkyl, C 3 -C 8 ring An alkyl group, a C 2 -C 6 alkenyl group, a C 3 -C 6 alkynyl group, a phenyl group, a phenyl dC 4 alkyl group or a phenoxy dC 4 alkyl group, said phenyl or phenoxy ring
  • Each of the hydrogens may be unsubstituted or substituted with from 1 to 4 groups: fluorine, chlorine, bromine, nitro
  • A is selected from N;
  • Q is selected from -NR6(CO-XR 7 ), -NR6-CN, -NR6-CH(R 8 )-CN, -N 6 - NR 9 (CO-XR 7 ), - ⁇ - N 9 -CH( 8 ) -CN, -N 6 - 0-CH 2 (CO-X- 7 ) or -CH(R 8 ) (CO-X- 7 );
  • X is selected from C3 ⁇ 4, ⁇ , O or S ;
  • R 6 is selected from the group consisting of hydrogen, cyano, -C4 alkyl, dC 4 alkoxy, Ci-C 4 haloalkyl, Ci-C 4 haloalkoxy or -C 4 alkoxycarbonyl;
  • R 7 is selected from the group consisting of hydrogen, chlorine, Ci-C 4 alkyl, C1-C4 13 ⁇ 4 alkyl, Ci-C 4 alkoxy Ci-C 4 alkyl, cyano Ci-C 4 alkyl, Ci-Ct Base amino dC 4 alkyl, bis-(Ci-Ct alkyl)amino dC 4 alkyl, Ci-Ct alkoxycarbonyl-C 1-4 alkyl, carboxy-dC 4 alkyl, C 3 -C 7 ring An alkyl group, a C 3 -C 6 alkenyl group, a C 3 -C 6 alkynyl group, a phenyl group, a phenyl dC 4 alkyl group or a phenoxy dC 4 alkyl group, said phenyl or phenoxy ring
  • Each of the hydrogens may be unsubstituted or substituted with from 1 to 4 of the following groups: fluorine, chlorine, bromine,
  • Ci-Ct alkyl Selected from hydrogen, chlorine, Ci-Ct alkyl, C1-C4 13 ⁇ 4 alkyl, Ci-Ct alkoxy dC 4 alkyl, cyano Ci-Ct alkyl, Ci-C 4 alkoxycarbonyl-d_ 4 An alkyl or carboxyl dC 4 alkyl group;
  • R 9 is selected from the group consisting of hydrogen, cyano, dC 4 alkyl, dC 4 alkoxy, dC 4 haloalkyl or dC 4 haloalkoxy; or a sodium, potassium or copper salt thereof.
  • Still further preferred compounds are: in formula (I)
  • A is selected from N;
  • Q is selected from -NR6(CO-XR 7 ), -NR 6 -CN, -NR 6 -CH(R 8 )-CN or -CH(R 8 ) (CO-XR 7 );
  • X is selected from C3 ⁇ 4, NH or 0;
  • R 6 is selected from the group consisting of hydrogen, methyl, ethyl, methoxy or CC 4 alkoxycarbonyl;
  • R 7 from S ⁇ , 3 ⁇ 4 ⁇ , Ci-C 4 3 ⁇ 43 ⁇ 4S C1-C4 l3 ⁇ 4 3 ⁇ 43 ⁇ 4l3 ⁇ 4, Ci-C 4 3 ⁇ 43 ⁇ 4ftS Ci-C 4 3 ⁇ 43 ⁇ 4S S Ci-C 4 3 ⁇ 43 ⁇ 4S CC 4 alkylamino CC 4 alkyl, di-(dC 4 Alkyl)aminoCC 4 alkyl, C 3 -Q ⁇ 3 ⁇ 4 alkenyl, C 3 -Q ⁇ 3 ⁇ 4 alkynyl or phenyl, the hydrogen on the phenyl ring may be unsubstituted or 1-4 Substituted by a group: fluorine, chlorine, bromine, cyano, methyl, methoxy, trifluoromethyl, methoxycarbonyl or ethoxycarbonyl;
  • Ri is selected from the group consisting of hydrogen, fluorine or chlorine
  • R 2 selected from hydrogen
  • R 3 is selected from fluorine or chlorine
  • Q is selected from -NR 6 (CO-XR 7 ), -NR6-CN, -NR6-CH(R 8 )-CN or -CH(R 8 ) (CO-XR 7 );
  • X is selected from C3 ⁇ 4, NH or O ;
  • R 6 is selected from the group consisting of hydrogen, methyl or ethyl
  • R 7 is selected from the group consisting of hydrogen, chlorine, CC 4 alkyl, CC 4 alkoxy CC 4 alkyl or phenyl;
  • Halogen refers to fluorine, chlorine, bromine or iodine.
  • Alkyl means a straight or branched alkyl group.
  • Haloalkyl a linear or branched alkyl group in which a hydrogen atom is partially or completely replaced by a halogen atom.
  • Alkoxy A linear or branched alkyl group bonded to a structure via an oxygen atom.
  • Haloalkoxy A hydrogen atom on a straight or branched alkoxy group is partially or completely substituted by a halogen atom.
  • Alkenyl straight or branched and may have at least one carbon-carbon double bond at any position.
  • Alkenyl The hydrogen atom on the linear or branched alkenyl group is partially or completely replaced by a halogen atom.
  • Alkynyl straight or branched and may have at least one carbon-carbon triple bond at any position.
  • Haloalkynyl group A hydrogen atom on a linear or branched alkynyl group is partially or completely substituted by a halogen atom.
  • Cycloalkyl a cyclic alkane having three or more carbon atoms, such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group or the like.
  • Alkylcarbonyl An alkyl group is attached to the structure via a carbonyl group, such as CH 3 CO-, CH 3 CH 2 CO-.
  • Haloalkylcarbonyl The hydrogen atom on the alkyl group of the alkylcarbonyl group may be partially or completely substituted by a halogen atom such as CF 3 CO-.
  • Alkoxycarbonyl The alkoxy group is attached to the structure via a carbonyl group. Such as CH 3 OCO-, CH 3 CH 2 OCO-.
  • Haloalkoxycarbonyl The hydrogen atom on the alkyl group of the alkoxycarbonyl group may be partially or completely substituted by a halogen atom. Such as ClCH 2 CH 2 OCO-.
  • Alkylthio a linear or branched alkyl group bonded to a structure via a sulfur atom bond.
  • Haloalkylthio a linear or branched alkylthio group in which a hydrogen atom may be partially or completely substituted by a halogen atom.
  • Alkylsulfinyl A straight or branched alkyl group is attached to the structure via a sulfinyl group (-SO-), such as a methylsulfinyl group.
  • Alkylsulfonyl A straight or branched alkyl group is attached to the structure via a sulfonyl group (-S0 2 -), such as a methylsulfonyl group.
  • Haloalkylsulfinyl a linear or branched alkylsulfinyl group in which a hydrogen atom on the alkyl group may be partially or completely substituted by a halogen atom.
  • Haloalkylsulfonyl a linear or branched alkylsulfonyl group in which a hydrogen atom on the alkyl group may be partially or completely substituted by a halogen atom.
  • Alkylamino a linear or branched alkyl group bonded to the structure via a nitrogen atom.
  • Alkyl acylamino such as CH 3 CONH-, CH 3 CH 2 CONH alkylsulfonylamino: such as C3 ⁇ 4S0 2 NH-, C3 ⁇ 4C3 ⁇ 4 S0 2 NH -.
  • Hal is chlorine, bromine or iodine
  • R 9 and R 1Q are independently hydrogen or CC 4 alkyl.
  • a palladium catalyst such as tetrakis(triphenylphosphine)-palladium(0) or the like can be used.
  • the solvent may be selected from inert solvents such as toluene, 1,2-dichloroethane or dioxane.
  • the reaction temperature is 80 to 120 °C.
  • the halogenated aromatic compound represented by the formula (II) is commercially available.
  • aromatic boronic acid or ester compound represented by the formula (III) is commercially available or can be produced by a known method, for example, see US 5,783,522.
  • the sulfonating reagent used in the synthesis (V) of (IV) may be concentrated sulfuric acid or chlorosulfonic acid, and the reaction temperature is 60 to 140 °C.
  • the reaction of (V) with the substituted primary amine NH 2 to synthesize (VI) can be carried out in a polar solvent such as dichloromethane, methyl ethyl ketone or tetrahydrofuran, and the acid binding agent used for the reaction is triethylamine, pyridine or potassium carbonate. Etc., the reaction temperature is 20 ⁇ 80 °C.
  • the substituted primary amine NH 2 R 6 is commercially available.
  • each group is as defined above.
  • the solvent, the acid binding agent, and the reaction conditions used in the reaction are the same as those of the (V) synthesis (VI).
  • each group is as defined above.
  • the solvent used for the reaction may be a polar solvent such as acetone or acetonitrile, and the acid binding agent is selected from the group consisting of potassium carbonate, sodium carbonate and the like.
  • the reaction temperature is 20 to 50 °C.
  • the compound represented by the formula (VIII) is partially commercially available, and can also be produced by a known method, as described in detail in Merck & Co. Inc., 1988. 3742.
  • the solvent used for the reaction may be a polar solvent such as methanol, ethanol or acetonitrile. Reaction The temperature is 60 ⁇ 80 °C.
  • (VII) is obtained by a stepwise reaction of (V) at a reaction temperature of 40 to 80 °C.
  • the compound represented by the formula (IX) is partially commercially available, and can also be produced by a known method. For details, see Arch. Pharm. 1962, 295:697.
  • the present invention also includes a salt of the compound of the formula (I) which is produced by the following method:
  • a strong base such as sodium hydride, sodium methoxide or unsalt.
  • a salt of the compound of the formula (I) can be conveniently obtained by reacting sodium butoxide or potassium t-butoxide in a solvent such as methanol, ethanol, tert-butanol, tetrahydrofuran or toluene.
  • Q be -NR6-CH(R 8 )-
  • each group has the same definition as before.
  • the solvent used for the reaction may be a solvent such as methanol or toluene.
  • the reaction temperature is 30 to 80 °C.
  • the compound of the formula (I) of the present invention is suitably used as a herbicide. They are very effective in controlling weeds in crops such as wheat, rice, corn, soybeans and cotton, especially at low application doses. It can be used as a herbicide for herbicides, and can also be used for weeding in transgenic crop fields, and has certain safety to rice and the like. Therefore, the technical scheme of the present invention also includes a general formula.
  • the present invention also provides a herbicidal composition
  • a herbicidal composition comprising the compound of the formula (I) or a salt thereof as an active ingredient and an agriculturally acceptable carrier, the weight of the compound of the formula (I) in the composition The percentage is from 0.1 to 99%.
  • the technical solution of the present invention therefore also includes the use of the composition as a herbicide.
  • composition of the present invention can be prepared according to a conventional method: The compound of the formula (I) is mixed with a carrier.
  • the active ingredient in such compositions may contain a single compound of the invention or a mixture of several compounds.
  • the carrier in the composition of the present invention is a substance which, after being formulated with the active ingredient, is convenient for application to a site to be treated, for example, a plant, seed or soil; or is advantageous for storage, transportation or handling.
  • the carrier may be a solid or a liquid, and includes a material which is usually a gas but which has been compressed into a liquid, and which is usually used in the preparation of the herbicidal composition.
  • Suitable solid carriers include natural and synthetic clays and silicates such as diatomaceous earth, talc, attapulgite, aluminum silicate (kaolin), montmorillonite and mica; calcium carbonate; calcium sulfate; ammonium sulfate; Silicon and synthetic calcium silicate or aluminum silicate; elements such as carbon and sulfur; natural and synthetic resins such as benzofuran resins, polyvinyl chloride and styrene polymers and copolymers; solid polychlorinated phenols; Beeswax, paraffin.
  • natural and synthetic clays and silicates such as diatomaceous earth, talc, attapulgite, aluminum silicate (kaolin), montmorillonite and mica; calcium carbonate; calcium sulfate; ammonium sulfate; Silicon and synthetic calcium silicate or aluminum silicate; elements such as carbon and sulfur; natural and synthetic resins such as benzofuran resins, polyvinyl chloride and styrene polymers and copoly
  • Suitable liquid carriers include water; alcohols such as isopropanol and ethanol; ketones such as acetone, methyl ethyl ketone, methyl isopropyl ketone, cyclohexyl ketone; ethers; aromatic hydrocarbons such as benzene, toluene, xylene; petroleum fractions such as Kerosene and mineral oils; chlorinated hydrocarbons such as carbon tetrachloride, perchloroethylene and trichloroethylene. Usually, mixtures of these liquids are also suitable.
  • the herbicidal compositions are typically processed into a concentrate form and used for transport, which is diluted by the user prior to administration.
  • the presence of a small amount of surfactant carrier aids in the dilution process.
  • at least one carrier in the composition according to the invention Preferred is a surfactant.
  • the composition may contain at least two carriers, at least one of which is a surfactant.
  • the surfactant may be an emulsifier, dispersant or wetting agent; it may be a nonionic or ionic surfactant.
  • suitable surfactants include sodium or calcium salts of polyacrylic acid and lignosulfonic acid; condensation of fatty acids or fatty amines or amides having at least 12 carbon atoms in the molecule with ethylene oxide and/or propylene oxide Things.
  • compositions of the invention are wettable powders, powders, granules and solutions, emulsifiable concentrates, emulsions, suspension concentrates, aerosols and aerosols.
  • Wettable powders usually contain 25%, 50% or 75% by weight of active ingredient, and usually contain 3-10% by weight of dispersing agent in addition to the solid inert carrier, and 0-10% by weight of stabilizer can be added if necessary. And / or other additives such as penetrants or adhesives.
  • the powder may be usually formed into a powder concentrate having a composition similar to that of the wettable powder but without a dispersing agent, and further diluted with a solid carrier to give a composition usually containing 0.5 to 10% by weight of the active ingredient.
  • Granules are typically prepared to have a size of from 10 to 100 mesh (1.676-0.152 mm) and can be prepared by agglomeration or infusion techniques. Usually the granules contain 0.5-75% by weight of active ingredient and 0-10% by weight of additives such as stabilizers, surfactants, sustained release modifiers. The so-called "flowable dry powder" consists of relatively small particles having a relatively high concentration of active ingredient.
  • Emulsifying concentrates in addition to solvents, usually contain a cosolvent, 1-50% W/V active ingredient, 2-20% W/V emulsifier and 0-20% W/V other additives such as stabilizers, infiltration, when needed. Agent and corrosion inhibitor.
  • the suspension concentrate usually contains 10-75% by weight of active ingredient, 0.5-15% by weight of dispersant, 0.1-10% by weight of other additives such as antifoaming agents, corrosion inhibitors, stabilizers, penetrants and adhesives.
  • Aqueous dispersions and emulsions for example compositions obtained by diluting a wettable powder or concentrate according to the invention with water, are also included in the scope of the invention.
  • the emulsion may be of two types, water-in-oil or oil-in-water.
  • herbicides By incorporating additional one or more herbicides into the composition, it has a broader spectrum of activity than the compound of formula (I) alone. Furthermore, other herbicides have a synergistic effect on the herbicidal activity of the compounds of the general formula (I).
  • the reaction mixture was cooled to room temperature, and filtered, EtOAcjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjj 20. 4g, yield: 70%, melting point 72-74 ° C.
  • the residue was evaporated, evaporated, mjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjj
  • the residue was evaporated, evaporated, mjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjj
  • the mixture was cooled to room temperature, and the mixture was evaporated under reduced pressure. The residue was evaporated, evaporated, mjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjj
  • Example 9 2-(2-Chloro-5-(3-chloro-5-(trifluoromethyl)pyridin-2-yl)benzenesulfonyl)ethylacetamide (Compound 64 First step reaction: sodium 2-chloro-5-(3-chloro-5-(trifluoromethyl)pyridin-2-yl)benzenesulfinyl salt
  • the mixture was cooled to room temperature, and the mixture was evaporated under reduced pressure. The residue was evaporated, evaporated, mjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjj
  • the mixture was cooled to room temperature, and the mixture was evaporated under reduced pressure. The residue was evaporated, evaporated, mjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjj
  • Compound 97 an oil. S ppm 0.85(3H,t), 1.25(2H,m), 1.55(2H,m), 4.09(2H,m), 7.75(lH,d), 8.09(2H,m), 8.80(lH,s) .
  • Example 15 60% wettable powder
  • Kaolin is made up to 100%
  • Compound 44 sodium dodecylnaphthalene sulfonate, sodium lignosulfonate and kaolin (both solids) were mixed and pulverized in a pulverizer until the granules reached the standard.
  • Example 16 35% emulsifiable concentrate
  • Compound 7 was pulverized together with 80% of water and sodium laurylnaphthalenesulfonate to be added in a ball mill (1 mm beads). Hemicellulose and propylene oxide were dissolved in the remaining 20% of water, and then the above components were stirred.
  • Example 18 25% water emulsion
  • Alkyl aryl fractions make up to 100%
  • Compound 22 is dissolved in 80% of the solvent to be added (cyclohexanone and alkyl aryl fraction), followed by the addition of an emulsifier (dodecyl alcohol polyethylene glycol phosphate, ethoxy triglyceride and The calcium dodecylbenzenesulfonate) and the dispersant (2.5 parts of ethylene oxide propylene oxide copolymer) were thoroughly stirred. The mixture was comminuted in a ball mill (1 mm beads) and then the remaining 20% solvent was added.
  • the solvent to be added cyclohexanone and alkyl aryl fraction
  • an emulsifier dodecyl alcohol polyethylene glycol phosphate, ethoxy triglyceride and The calcium dodecylbenzenesulfonate
  • dispersant 2.5 parts of ethylene oxide propylene oxide copolymer
  • the herbicidal activity test method of the compound of the present invention is as follows:
  • Quantitative weed seeds were separately planted in a 7cm diameter paper cup filled with nutrient soil, covered with soil lcm after sowing, cultured in the greenhouse after suppression and watering, and pre-emergence treatment was carried out 24 hours after sowing; After the seedlings, planting (grass weeds 10 ⁇ 20 plants / cup, broadleaf weeds 2 ⁇ 4 strains / cup), to the grass weeds 2 ⁇ 3 leaf stage, broadleaf weeds to 2 true leaf stage, The stem and leaf spray treatment (spray pressure 1.95 kg/cm2, spray volume 50 ml/m2, crawler speed 1.48 km/h) was carried out according to the test design dose with a track-type crop sprayer (designed and manufactured by Engineering Research Ltd., UK). The test was repeated 3 times. After the liquid is naturally dried, it is placed in a greenhouse and managed according to conventional methods. The growth and development of the test materials are regularly observed. According to the actual situation, the control effect of the test agents on weeds is investigated visually after treatment.
  • Control effect grading standards 0 is invalid, 100% is to completely kill or severely suppress weeds.
  • the control effect of compound 2, 34, 44, 47, 22, 23, 24, 50 on valerian, foxtail, ramie, and zinnia is 100%; compound 29 on valerian, foxtail, nettle
  • the control effect of Zinnia is higher than 90%; the compound 46, 49 has more than 85% control effect on valerian, foxtail, ramie and zinnia.
  • the compound 34, 44, 47, 22, 23, 24 has 100% control effect against valerian, foxtail, ramie, and zinnia; compound 50 against valerian, foxtail, ramie, zinnia
  • the control effect is higher than 90%.
  • the resistance of compounds 47, 22, 23, 24 to valerian, foxtail, ramie, zinnia is 100%; compound 34, 44 pairs of valerian, foxtail, ramie, zinnia
  • the control effect is higher than 90%; the compound 50 has more than 70% control effect on valerian, foxtail, ramie and zinnia.
  • the activity of controlling valerian, foxtail, ramie and Zinnia is shown in Table 7.
  • the determination method is the same as the above-mentioned t table 7.
  • the compound 44 of the present invention was subjected to an activity control with a commercialized species of saflufenacil (a commercially available original drug, the same hereinafter), and the results are shown in Table 8, and the measurement methods are as described above.
  • Table 8 a commercialized species of saflufenacil (a commercially available original drug, the same hereinafter), and the results are shown in Table 8, and the measurement methods are as described above.
  • the compound 44 of the present invention was subjected to a herbicidal spectrum test and compared with the commercial variety saflufenacil. Table 9, the determination method was as described above.
  • Example 23 Field control of weeds, geranium and Solanum nigrum
  • the experiment was carried out in the rice field of Shenyang City, Liaoning Republic in July 2011.
  • the field weeds were in the 2-4 leaf stage during the experiment.
  • the test is carried out in accordance with the relevant standards for pesticide field efficacy test (1) GB/T17980.40-2000.
  • the treatment concentration of the compound 44 of the present invention was 7.5, 15, 30, 60 g (ai/ha), and the concentration of the control agent 48% bentazon water (commercially available) was 1440 g (ai/ha).
  • the area of the plot is 20 m 2 , which is randomly arranged, repeated twice, and the spray volume is about 450 L/hm 2 .
  • the test results of compound 44 for control of comfrey and sylvestris field are shown in Table 10.
  • the experiment was carried out in June 2011 at the rice field test base in Changchun City, Jilin province.
  • the field weeds were in the 2-4 leaf stage during the test.
  • the test is carried out in accordance with the relevant standards for pesticide field efficacy test guidelines (1) GB/T17980.40-2000.
  • concentration of the original drug of the compound 44 was 7.5, 15, 30, 60, 90 g (ai/ha), and the concentration of the control agent 48% bentazon was 1440 g (a ⁇ /ha).
  • the area of the plot is 40m 2 , randomly arranged, repeated 2 times, and the spray volume is about 450L/hm 2 .
  • the results of the test of compound 44 for control of rice weeds in the field were shown in Table 11.

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Abstract

Disclosed is a substituted biaryl benzenesulfonamide compound or a salt thereof, which has a structure as shown in formula(I): each of the substituents being defined as in the description. The compound of the formula(I)or its salt has a wide spectrum of herbicidal activity, and can be used for preventing and controlling many kinds of broadleaf weeds (such as Chinese jute, Zinnia elegans, etc.), gramineae weeds (such as Echinochloa crusgalli, Setaria viridis, etc.), and also used as a sterilizing herbicide, and as a herbicide for transgenic crop fields, while being relatively safe for use on rice, etc.

Description

取代的联芳香基苯磺酰胺类化合物与用途 技术领域  Substituted biaryl benzene sulfonamides and uses thereof
本发明属农用除草剂领域， 涉及一种取代的联芳香基苯磺酰胺类化合物与用途。  The invention belongs to the field of agricultural herbicides and relates to a substituted biaryl benzene sulfonamide compound and use thereof.
背景技术 Background technique
对于取代的联芳香基苯磺酰胺类化合物， 报道的专利很多， 例如 W09822443、 WO9842700、 WO2001070736、 WO2001074786、 WO2006065646、 WO20081224614、 WO2009148052, WO2009103440、 FR2727413、 FR2749584、 JP61050975等， 主要应用于医 药的研究。  For the substituted biaryl benzene sulfonamides, there are many reported patents, such as W09822443, WO9842700, WO2001070736, WO2001074786, WO2006065646, WO20081224614, WO2009148052, WO2009103440, FR2727413, FR2749584, JP61050975, etc., which are mainly used for medical research.
Peter Schafer等人在 US5783522 化合物具有一定的除草活性：  Peter Schafer et al. have certain herbicidal activity in US5783522:
Figure imgf000003_0001
Figure imgf000003_0001
式中： 为氢、 氟、 氯， R7为 S02NR9R1()， R9和 。为氢或 d-C8烷基。 Where: hydrogen, fluorine, chlorine, R 7 is S0 2 NR 9 R 1 () , R 9 and. Is hydrogen or dC 8 alkyl.
实际上这些已知化合物的除草活性不是总能令人满意。  In fact, the herbicidal activity of these known compounds is not always satisfactory.
发明内容 Summary of the invention
本发明的目的在于提供一种结构新颖的除草化合物，并希望这些化合物与现有技术所提 供的除草化合物相比， 具有优异的除草活性， 可用于有目的的防治有害植物。  SUMMARY OF THE INVENTION An object of the present invention is to provide a herbicidal compound having a novel structure, and it is desired that these compounds have excellent herbicidal activity as compared with the herbicidal compound provided by the prior art, and can be used for purposeful control of harmful plants.
本发明的技术方案如下：  The technical solution of the present invention is as follows:
本发明提供一种取代的联芳 盐， 如通式 (I)所示-  The present invention provides a substituted biaryl salt as shown in the general formula (I) -
Figure imgf000003_0002
Figure imgf000003_0002
式中- Where -
A选自 CH或 N;A is selected from CH or N;
i ^ 、 、 R4各自独立地选自氢、 氟、 氯、 溴、 氰基、 硝基、 羟基、 巯基、 d-C6烷 基、 d-C6卤代烷基、 C2-Q^¾烯基、 C2-Q^¾炔基、 C C6烷氧基、 d-C6卤代烷氧基、 C2-C6 烯氧基、 C2-C6 ¾代烯氧基、 ^-^炔氧基、 C2-C6 ¾代炔氧基、 羟基羰基、 d-C6烷基羰基、 ^-^卤代烷基羰基、 d-C6烷氧基羰基、 d-C6卤代烷氧基羰基、 d-C l硫基、 d-C6卤代 烷硫基、 d-C6烷基亚磺酰基、 d-C6烷基磺酰基、 d-C6卤代烷基亚磺酰基、 d-C6卤代烷基 磺酰基或 d-C6烷基氨基； i ^ , , R4 are each independently selected from the group consisting of hydrogen, fluorine, chlorine, bromine, cyano, nitro, hydroxy, decyl, dC 6 alkyl, dC 6 haloalkyl, C 2 -Q^3⁄4 alkenyl, C 2 - Q^3⁄4 alkynyl, CC 6 alkoxy, dC 6 haloalkoxy, C 2 -C 6 alkenyloxy, C 2 -C 6 3⁄4 alkenyloxy, ^- alkynyloxy, C 2 -C 6 3⁄4 alkynyloxy, hydroxycarbonyl, dC 6 alkylcarbonyl, ^-haloalkylcarbonyl, dC 6 alkoxycarbonyl, dC 6 haloalkoxycarbonyl, dC l thio, dC 6 haloalkylthio, dC 6 alkane a sulfinyl group, a dC 6 alkylsulfonyl group, a dC 6 haloalkylsulfinyl group, a dC 6 haloalkylsulfonyl group or a dC 6 alkylamino group;
R5选自氢、 氟、 氯、 溴、 氰基、 硝基、 巯基、 羟基、 d-C6烷基、 C C6卤代烷基、 C2-C6 链烯基、 C2-Q^¾炔基、 C C6烷氧基、 d-C6 ¾代烷氧基、 ^-^烯氧基、 ^-^炔氧基、 羟 基羰基、 d-C6烷基羰基、 d-C6 ¾代烷基羰基、 d-C6烷氧基羰基、 ^-^ ^代烷氧基羰基、 d-C6烷硫基、 C2-C6卤代烷硫基、 d-C6烷基亚磺酰基、 d-C6卤代烷基亚磺酰基、 d-C6烷 基磺酰基、 d-C6卤代烷基磺酰基、 C C6烷基氨基、 二- ( C C6烷基） 氨基、 C C6烷基酰 基氨基或^-^烷基磺酰基氨基； n=l-4; R 5 is selected from the group consisting of hydrogen, fluorine, chlorine, bromine, cyano, nitro, decyl, hydroxy, dC 6 alkyl, CC 6 haloalkyl, C 2 -C 6 alkenyl, C 2 -Q^3⁄4 alkynyl, CC 6 alkoxy, dC 6 3⁄4 alkoxy, ^-(alkenyloxy), ^-alkynyloxy, hydroxycarbonyl, dC 6 alkylcarbonyl, dC 6 3⁄4 alkylcarbonyl, dC 6 alkoxy Carbonyl, ^-^^ alkoxycarbonyl, dC 6 alkylthio, C 2 -C 6 haloalkylthio, dC 6 alkylsulfinyl, dC 6 haloalkylsulfinyl, dC 6 alkylsulfonyl, dC 6 haloalkylsulfonyl, CC 6 alkylamino, bis-(CC 6 alkyl)amino, CC 6 alkyl acylamino or ^-alkyl sulfonylamino; n = l-4 ;
Q 选自 -NR6(CO-X-R7)、 -N¾,-CN、 -N 6-CH( 8)-CN、 -N¾,- N 9(CO-X- 7)、 -N¾,- NR9-CH(R8) -CN、 -N 6- 0-CH2(CO-X- 7) 或 -CH(R8) (CO-X-R7) ； Q is selected from -NR6(CO-XR 7 ), -N3⁄4, -CN, -N 6 -CH( 8 )-CN, -N3⁄4, - N 9 (CO-X- 7 ), -N3⁄4,-NR 9 - CH(R 8 ) -CN, -N 6 - 0-CH 2 (CO-X- 7 ) or -CH(R 8 ) (CO-XR 7 );
X选自 CH2、 NR6、 O或 S ; 、 R9各自独立地选自氢、 氰基、 C C6烷基、 C C6烷氧基、 C C6卤代烷基、 C C6卤 代烷氧基或 C C6烷氧基羰基；X is selected from CH 2 , NR 6 , O or S ; And R 9 are each independently selected from the group consisting of hydrogen, cyano, CC 6 alkyl, CC 6 alkoxy, CC 6 haloalkyl, CC 6 haloalkoxy or CC 6 alkoxycarbonyl;
7 、 各自独立地选自氢、 氟、 氯、 溴、 C C6烷基、 C C6卤代烷基、 C C6烷氧基7 , each independently selected from the group consisting of hydrogen, fluorine, chlorine, bromine, CC 6 alkyl, CC 6 haloalkyl, CC 6 alkoxy
Ci-C6 S Ci-c6¾¾S Ci-C6¾¾S S Ci-c6¾¾S 二- (Ci-c6¾¾S)氛基 Ci-c^烧基、 C C6烷氧基羰基- C C6烷基、羧基 -d-C6烷基、 C3-C8环烷基、 C2-Q^¾烯基、 C3-Q^¾炔基， 苯基、 苯基 d-C6烷基、 苯氧基 d-C6烷基、 吡啶基、 嘧啶基、 三嗪基、 噁唑基、 噻唑基或 吡唑基， 所述的苯基、 苯氧基、 吡啶基、 嘧啶基、 三嗪基、 噁唑基、 噻唑基或吡唑基环上的 氢各自可未被取代或被 1-4个下述基团所取代： 卤素、羟基、硝基、氰基、 d-C6烷基、 d-C6 烷氧基、 d-Ce^代烷基、 d-Ce^代烷氧基、 羟基羰基或 d-C6烷氧基羰基。 Ci-C 6 S Ci-c 6 3⁄43⁄4S Ci-C63⁄43⁄4S S Ci-c 6 3⁄43⁄4S Di-(Ci-c 6 3⁄43⁄4S) Aromatic Ci-c^alkyl, CC 6 alkoxycarbonyl-CC 6 alkyl, carboxyl -dC 6 alkyl, C 3 -C 8 cycloalkyl, C 2 -Q^ 3⁄4 alkenyl, C 3 -Q^ 3⁄4 alkynyl, phenyl, phenyl dC 6 alkyl, phenoxy dC 6 alkyl , pyridyl, pyrimidinyl, triazinyl, oxazolyl, thiazolyl or pyrazolyl, phenyl, phenoxy, pyridyl, pyrimidinyl, triazinyl, oxazolyl, thiazolyl or pyridyl The hydrogen on the azolyl ring may each be unsubstituted or substituted with from 1 to 4 groups: halogen, hydroxy, nitro, cyano, dC 6 alkyl, dC 6 alkoxy, d-Ce^ Alkyl, d-Ce^ alkoxy, hydroxycarbonyl or dC 6 alkoxycarbonyl.
本发明较为优选的化合物为： 通式 (I)中  Preferred compounds of the invention are: in formula (I)
A选自 CH或 N;  A is selected from CH or N;
R 、 R2、 R3、 R4各自独立地选自氢、 氟、 氯、 溴、 氰基、 硝基、 d-C6烷基、 d-C6卤代 烷基、 d-C6烷氧基、 d-C6¾代烷氧基、 羟基羰基、 d-C6烷基羰基、 d-C6¾代烷基羰基或 d-C6烷氧基羰基； R, R 2 , R 3 , R4 are each independently selected from the group consisting of hydrogen, fluorine, chlorine, bromine, cyano, nitro, dC 6 alkyl, dC 6 haloalkyl, dC 6 alkoxy, dC 6 3⁄4 alkoxy a hydroxycarbonyl group, a dC 6 alkylcarbonyl group, a dC 6 3⁄4 alkylcarbonyl group or a dC 6 alkoxycarbonyl group;
R5选自氢、氟、氯、溴、氰基、硝基、 d-C6烷基、 d-C6卤代烷基、 d-C6烷氧基、 d-C6 卤代烷氧基、 羟基羰基、 d-C6烷基羰基、 d-C6卤代烷基羰基、 d-C6烷氧基羰基； n=l-4; R 5 is selected from the group consisting of hydrogen, fluorine, chlorine, bromine, cyano, nitro, dC 6 alkyl, dC 6 haloalkyl, dC 6 alkoxy, dC 6 haloalkoxy, hydroxycarbonyl, dC 6 alkylcarbonyl, dC 6 haloalkylcarbonyl, dC 6 alkoxycarbonyl; n = l-4 ;
Q 选 自 -NR6(CO-X-R7)、 -N¾,-CN、 -NR6-CH( 8)-CN、 -Ν - N 9(CO-X- 7)、 -NR6-NR9-CH(R8)-CN、 -NR6-0-CH2(CO-X- 7) 或 -CH(R8) (CO-X- 7); Q is selected from the group consisting of -NR 6 (CO-XR 7 ), -N3⁄4, -CN, -NR6-CH( 8 )-CN, -Ν-N 9 (CO-X- 7 ), -NR6-NR 9 -CH ( R 8 )-CN, -NR6-0-CH 2 (CO-X- 7 ) or -CH(R 8 ) (CO-X- 7 );
X选自 C¾、 Ν 、 O或 S; X is selected from C3⁄4, Ν, O or S ;
R6、 R9各自独立地选自氢、 氰基、 d-C6烷基、 d-C6烷氧基、 d-C6卤代烷基、 d-C6 卤代烷氧基或 d-C6烷氧基羰基； R 6 and R 9 are each independently selected from the group consisting of hydrogen, cyano, dC 6 alkyl, dC 6 alkoxy, dC 6 haloalkyl, dC 6 haloalkoxy or dC 6 alkoxycarbonyl;
R7、 各自独立地选自氢、氟、氯、溴、 d-C6烷基、 Ci-C6卤代烷基、 d-C6烷氧基 d-C6 烧基、氰基 Ci-C6烧基、 Ci-C6烧基氨基 Ci-Cs烧基、二- (Ci-C6¾¾S)氨基 Ci-C6烧基、 Ci-C6 烷氧基羰基- d-C6烷基、 羧基 -d-C6烷基、 C3-C8环烷基、 C2-Q^¾烯基、 C3-Q^¾炔基， 苯 基、 苯基 d-C6烷基或苯氧基 d-C6烷基， 所述的苯基或苯氧基环上的氢各自可未被取代或 被 1-4个下述基团所取代： 卤素、 羟基、 硝基、 氰基、 C C6烷基、 d-C ^氧基、 ^-^卤 代烷基、 d-C6¾代烷氧基、 羟基羰基或 d-C6烷氧基羰基； R 7 , each independently selected from the group consisting of hydrogen, fluorine, chlorine, bromine, dC 6 alkyl, Ci-C 6 haloalkyl, dC 6 alkoxy dC 6 alkyl, cyano Ci-C6 alkyl, Ci-C6 Base amino-Ci-Cs alkyl, bis-(Ci-C63⁄43⁄4S) amino-Ci-C6 alkyl, Ci-C 6 alkoxycarbonyl-dC 6 alkyl, carboxy-dC 6 alkyl, C 3 -C 8 naphthenic a C 2 -Q^ 3⁄4 alkenyl group, a C 3 -Q^ 3⁄4 alkynyl group, a phenyl group, a phenyl dC 6 alkyl group or a phenoxy dC 6 alkyl group, on the phenyl or phenoxy ring Each of the hydrogens may be unsubstituted or substituted with from 1 to 4 groups: halogen, hydroxy, nitro, cyano, CC 6 alkyl, dC^oxy, ^-haloalkyl, dC 6 3⁄4 alkane An oxy group, a hydroxycarbonyl group or a dC 6 alkoxycarbonyl group;
或其钠盐、 钾盐或铜盐。  Or its sodium, potassium or copper salt.
进一步优选的化合物为： 通式 (I)中  Further preferred compounds are: in formula (I)
A选自 CH或 N;  A is selected from CH or N;
、 、 、 各自独立地选自氢、 氟、 氯、 溴、 氰基、 硝基、 CrC4烷基、 C C4卤 代烷基、 d-C4烷氧基、 d-C4卤代烷氧基、 羟基羰基、 C C4烷基羰基或 d-C4卤代烷基羰 基； ,,, Are each independently selected from hydrogen, fluoro, chloro, bromo, cyano, nitro, C r C 4 alkyl, CC 4 haloalkyl, dC 4 alkoxy, dC 4 haloalkoxy, hydroxycarbonyl, the CC a 4 -alkylcarbonyl group or a dC 4 haloalkylcarbonyl group;
选自氢、氟、氯、溴、氰基、硝基、 C C4烷基、 C C4卤代烷基、 CrC4烷氧基、 Ci-C4 卤代烷氧基、 羟基羰基、 C C4烷基羰基、 d-C4卤代烷基羰基或 C C4烷氧基羰基； n=l-4; Selected from hydrogen, fluorine, chlorine, bromine, cyano, nitro, CC 4 alkyl, CC 4 haloalkyl, C r C 4 alkoxy, Ci-C 4 haloalkoxy, hydroxycarbonyl, CC 4 alkylcarbonyl , dC 4 haloalkylcarbonyl or CC 4 alkoxycarbonyl; n = l-4;
Q 选自 -NR6(CO-X-R7)、 -NR6.CN、 -NR6-CH(R8)-CN、 -N 6- NR9(CO-X-R7)、 -NR^- N 9-CH( 8) -CN、 -N 6- 0-CH2(CO-X- 7) 或 -CH(R8) (CO-X- 7); Q is selected from -NR6(CO-XR 7 ), -NR6.CN, -NR6-CH(R 8 )-CN, -N 6 - NR 9 (CO-XR 7 ), -NR^- N 9 -CH ( 8 ) -CN, -N 6 - 0-CH 2 (CO-X- 7 ) or -CH(R 8 ) (CO-X-7);
X选自 C¾、 NR6、 O或 S; X is selected from C3⁄4, NR6, O or S ;
R6、 R9各自独立地选自氢、 氰基、 C C4烷基、 C C4烷氧基、 C C4卤代烷基、 C C4 卤代烷氧基或 d-C4烷氧基羰基； R 6 and R 9 are each independently selected from hydrogen, cyano, CC 4 alkyl, CC 4 alkoxy, CC 4 haloalkyl, CC 4 haloalkoxy or dC 4 alkoxycarbonyl;
R7、 各自独立地选自氢、 氯、 d-C4烷基、 C C4卤代烷基、 C C4烷氧基 C C4烷基、 氰基 Ci-C4烧基、 Ci-C4烧基氨基 Ci-C4烧基、 二- (Ci-C4烧基)氨基 Ci-C4烧基、 Ci-C4烧氧 基羰基 -d-C4烷基、 羧基 -d-C4烷基、 C3-C8环烷基、 C2-C6链烯基、 C3-C6链炔基， 苯基、 苯 基 d-C4烷基或苯氧基 d-C4烷基， 所述的苯基或苯氧基环上的氢各自可未被取代或被 1-4 个下述基团所取代： 氟、 氯、 溴、 硝基、 氰基、 d-C4烷基、 d-C4烷氧基、 d-C4卤代烷基、 d-C4 ¾代烷氧基、 羟基羰基或 d-C4烷氧基羰基； R 7 , each independently selected from the group consisting of hydrogen, chlorine, dC 4 alkyl, CC 4 haloalkyl, CC 4 alkoxy CC 4 alkyl, cyano-Ci-C 4 alkyl, Ci-C 4 alkylamino Ci- C 4 alkyl, bis-(Ci-C 4 alkyl)amino Ci-C 4 alkyl, Ci-C 4 alkoxycarbonyl-dC 4 alkyl, carboxy-dC 4 alkyl, C 3 -C 8 ring An alkyl group, a C 2 -C 6 alkenyl group, a C 3 -C 6 alkynyl group, a phenyl group, a phenyl dC 4 alkyl group or a phenoxy dC 4 alkyl group, said phenyl or phenoxy ring Each of the hydrogens may be unsubstituted or substituted with from 1 to 4 groups: fluorine, chlorine, bromine, nitro, cyano, dC 4 alkyl, dC 4 alkoxy, dC 4 haloalkyl, a dC 4 3⁄ alkoxy group, a hydroxycarbonyl group or a dC 4 alkoxycarbonyl group;
或其钠盐、 钾盐或铜盐。  Or its sodium, potassium or copper salt.
更进一步优选的化合物为： 通式 (I)中  Further preferred compounds are: in formula (I)
A选自 N;  A is selected from N;
、 、 各自独立地选自氢、氟、 氯、 溴、氰基、 C C4烷基、 C C4卤代烷基、 C C4 烷氧基或 d-C4卤代烷氧基； , each independently selected from the group consisting of hydrogen, fluorine, chlorine, bromine, cyano, CC 4 alkyl, CC 4 haloalkyl, CC 4 alkoxy or dC 4 haloalkoxy;
选自氟、 氯、 溴、 氰基、 d-C4烷基、 d-C4卤代烷基、 d-C4烷氧基或 d-C4卤代烷 氧基； Selected from fluorine, chlorine, bromine, cyano, dC 4 alkyl, dC 4 haloalkyl, dC 4 alkoxy or dC 4 haloalkoxy;
选自氢、 氟、 氯、 溴、 氰基、 d-C4烷基、 d-C4卤代烷基、 d-C4烷氧基、 d-C4卤 代烷氧基、 羟基羰基或 d-C4烷氧基羰基； n=l-4; Selected from hydrogen, fluorine, chlorine, bromine, cyano, dC 4 alkyl, dC 4 haloalkyl, dC 4 alkoxy, dC 4 haloalkoxy, hydroxycarbonyl or dC 4 alkoxycarbonyl; n=l-4 ;
Q 选自 -NR6(CO-X-R7)、 -NR6-CN、 -NR6-CH(R8)-CN、 -N 6- NR9(CO-X-R7)、 -Ν - N 9-CH( 8) -CN、 -N 6- 0-CH2(CO-X- 7) 或 -CH(R8) (CO-X- 7); Q is selected from -NR6(CO-XR 7 ), -NR6-CN, -NR6-CH(R 8 )-CN, -N 6 - NR 9 (CO-XR 7 ), -Ν - N 9 -CH( 8 ) -CN, -N 6 - 0-CH 2 (CO-X- 7 ) or -CH(R 8 ) (CO-X- 7 );
X选自 C¾、 Ν 、 O或 S; X is selected from C3⁄4, Ν, O or S ;
R6选自氢、氰基、 -C4烷基、 d-C4烷氧基、 Ci-C4卤代烷基、 Ci-C4卤代烷氧基或 -C4 烷氧基羰基； R 6 is selected from the group consisting of hydrogen, cyano, -C4 alkyl, dC 4 alkoxy, Ci-C 4 haloalkyl, Ci-C 4 haloalkoxy or -C 4 alkoxycarbonyl;
R7选自氢、氯、 Ci-C4烧基、 C1-C4 1¾代烧基、 Ci-C4烧氧基 Ci-C4烧基、氰基 Ci-C4烧基、 Ci-Ct烧基氨基 d-C4烧基、 二 -(Ci-Ct烧基)氨基 d-C4烧基、 Ci-Ct烧氧基羰基 -C1-4烧基、羧 基- d-C4烷基、 C3-C7环烷基、 C3-C6链烯基、 C3-C6链炔基， 苯基、 苯基 d-C4烷基或苯氧 基 d-C4烷基， 所述的苯基或苯氧基环上的氢各自可未被取代或被 1-4个下述基团所取代： 氟、 氯、 溴、 氰基、 甲基、 甲氧基、 三氟甲基、 甲氧基羰基或乙氧基羰基； R 7 is selected from the group consisting of hydrogen, chlorine, Ci-C 4 alkyl, C1-C4 13⁄4 alkyl, Ci-C 4 alkoxy Ci-C 4 alkyl, cyano Ci-C 4 alkyl, Ci-Ct Base amino dC 4 alkyl, bis-(Ci-Ct alkyl)amino dC 4 alkyl, Ci-Ct alkoxycarbonyl-C 1-4 alkyl, carboxy-dC 4 alkyl, C 3 -C 7 ring An alkyl group, a C 3 -C 6 alkenyl group, a C 3 -C 6 alkynyl group, a phenyl group, a phenyl dC 4 alkyl group or a phenoxy dC 4 alkyl group, said phenyl or phenoxy ring Each of the hydrogens may be unsubstituted or substituted with from 1 to 4 of the following groups: fluorine, chlorine, bromine, cyano, methyl, methoxy, trifluoromethyl, methoxycarbonyl or ethoxycarbonyl ;
选自氢、氯、 Ci-Ct烧基、 C1-C4 1¾代烧基、 Ci-Ct烧氧基 d-C4烧基、氰基 Ci-Ct烧基、 Ci-C4烷氧基羰基 -d_4烷基或羧基 d-C4烷基； Selected from hydrogen, chlorine, Ci-Ct alkyl, C1-C4 13⁄4 alkyl, Ci-Ct alkoxy dC 4 alkyl, cyano Ci-Ct alkyl, Ci-C 4 alkoxycarbonyl-d_ 4 An alkyl or carboxyl dC 4 alkyl group;
R9选自氢、 氰基、 d-C4烷基、 d-C4烷氧基、 d-C4卤代烷基或 d-C4卤代烷氧基； 或其钠盐、 钾盐或铜盐。 R 9 is selected from the group consisting of hydrogen, cyano, dC 4 alkyl, dC 4 alkoxy, dC 4 haloalkyl or dC 4 haloalkoxy; or a sodium, potassium or copper salt thereof.
再进一步优选的化合物为： 通式 (I) 中  Still further preferred compounds are: in formula (I)
A选自 N;  A is selected from N;
选自氢、 氟、 氯、 甲基或甲氧基；  Selected from hydrogen, fluorine, chlorine, methyl or methoxy;
、 选自氢；  , selected from hydrogen;
选自氟、 氯、 甲基或甲氧基；  Selected from fluorine, chlorine, methyl or methoxy;
选自氢、 氟、 氯、 氰基、 甲基、 甲氧基、 三氟甲基或三氟甲氧基； n=l-4;  Selected from hydrogen, fluorine, chlorine, cyano, methyl, methoxy, trifluoromethyl or trifluoromethoxy; n=l-4;
Q选自 -NR6(CO-X-R7)、 -NR6-CN、 -NR6-CH(R8)-CN或 -CH(R8) (CO-X-R7); Q is selected from -NR6(CO-XR 7 ), -NR 6 -CN, -NR 6 -CH(R 8 )-CN or -CH(R 8 ) (CO-XR 7 );
X选自 C¾、 NH或 0;  X is selected from C3⁄4, NH or 0;
R6选自氢、 甲基、 乙基、 甲氧基或 C C4烷氧基羰基； R 6 is selected from the group consisting of hydrogen, methyl, ethyl, methoxy or CC 4 alkoxycarbonyl;
R7 自 S<、 ¾ί、 Ci-C4¾¾S C1-C4 l¾ ¾¾l¾、 Ci-C4¾¾ftS Ci-C4¾¾S S Ci-C4¾¾S C C4烷基氨基 C C4烷基、 二 -(d-C4烷基)氨基 C C4烷基、 C3-Q^¾烯基、 C3-Q^¾炔基或 苯基， 所述的苯基环上的氢可未被取代或被 1-4个下述基团所取代： 氟、 氯、 溴、 氰基、 甲 基、 甲氧基、 三氟甲基、 甲氧基羰基或乙氧基羰基； R 7 from S<, 3⁄4ί, Ci-C 4 3⁄43⁄4S C1-C4 l3⁄4 3⁄43⁄4l3⁄4, Ci-C 4 3⁄43⁄4ftS Ci-C 4 3⁄43⁄4S S Ci-C 4 3⁄43⁄4S CC 4 alkylamino CC 4 alkyl, di-(dC 4 Alkyl)aminoCC 4 alkyl, C 3 -Q^ 3⁄4 alkenyl, C 3 -Q^ 3⁄4 alkynyl or phenyl, the hydrogen on the phenyl ring may be unsubstituted or 1-4 Substituted by a group: fluorine, chlorine, bromine, cyano, methyl, methoxy, trifluoromethyl, methoxycarbonyl or ethoxycarbonyl;
选自氢或甲基；  Selected from hydrogen or methyl;
或其钠盐、 钾盐或铜盐。  Or its sodium, potassium or copper salt.
更加优选的化合物为： 通式 (I) 中  More preferred compounds are: in formula (I)
A选白 N;  A chooses white N;
Ri选自氢、 氟或氯；  Ri is selected from the group consisting of hydrogen, fluorine or chlorine;
R2、 选自氢； R 2 , selected from hydrogen;
R3选自氟或氯； R 3 is selected from fluorine or chlorine;
选自氢、 氟、 氯或三氟甲基； n=l-4; Q选自 -NR6(CO-X-R7)、 -NR6-CN、 -NR6-CH(R8)-CN或 -CH(R8) (CO-X-R7); X选自 C¾、 NH或 O; Selected from hydrogen, fluorine, chlorine or trifluoromethyl; n=l-4; Q is selected from -NR 6 (CO-XR 7 ), -NR6-CN, -NR6-CH(R 8 )-CN or -CH(R 8 ) (CO-XR 7 ); X is selected from C3⁄4, NH or O ;
R6选自氢、 甲基或乙基； R 6 is selected from the group consisting of hydrogen, methyl or ethyl;
R7选自氢、 氯、 C C4烷基、 C C4烷氧基 C C4烷基或苯基； R 7 is selected from the group consisting of hydrogen, chlorine, CC 4 alkyl, CC 4 alkoxy CC 4 alkyl or phenyl;
选自氢；  Selected from hydrogen;
或其钠盐。  Or its sodium salt.
上面给出的通式 (I)化合物的定义中， 汇集所用术语一般代表如下取代基：  In the definitions of the compounds of the general formula (I) given above, the terms used in the collection generally represent the following substituents:
卤： 指氟、 氯、 溴或碘。 烷基： 指直链或支链烷基。 卤代烷基： 直链或支链烷基， 在 这些烷基上的氢原子部分或全部被卤原子所取代。 烷氧基： 直链或支链烷基， 经氧原子键连 接到结构上。 卤代烷氧基： 直链或支链烷氧基上的氢原子部分或全部被卤原子所取代。 链烯 基： 直链或支链并可在任何位置上至少存在一个碳碳双键。 ¾代链烯基： 直链或支链链烯基 上的氢原子部分或全部被卤原子所取代。链炔基： 直链或支链并可在任何位置上至少存在一 个碳碳三键。 卤代链炔基： 直链或支链链炔基上的氢原子部分或全部被卤原子所取代。 环烷 基： 含三个或以上碳原子的环状烷烃， 例如环丙基、 环丁基、 环戊基等。 烷基羰基： 烷基经 羰基连接到结构上， 如 CH3CO-， CH3CH2CO-。 卤代烷基羰基： 烷基羰基的烷基上的氢原子 可部分或全部被卤原子所取代， 如 CF3CO-。 烷氧基羰基： 烷氧基经羰基连接到结构上。 如 CH3OCO-， CH3CH2OCO-。 卤代烷氧基羰基： 烷氧基羰基的烷基上的氢原子可部分或全部被 卤原子所取代。 如 ClCH2CH2OCO-。 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、 氯氟甲硫 基等。烷基亚磺酰基： 直链或支链烷基经亚磺酰基（-SO-)连接到结构上， 如甲基亚磺酰基。 烷基磺酰基： 直链或支链烷基经磺酰基 （-S02-) 连接到结构上， 如甲基磺酰基。 卤代烷基 亚磺酰基： 直链或支链烷基亚磺酰基， 其烷基上的氢原子可部分或全部被卤原子所取代。 卤 代烷基磺酰基： 直链或支链烷基磺酰基， 其烷基上的氢原子可部分或全部被卤原子所取代。 烷基氨基： 直链或支链烷基， 经氮原子键连接到结构上。 烷基酰基氨基： 如 CH3CONH-， CH3CH2CONH 烷基磺酰基氨基： 如 C¾S02NH-， C¾C¾ S02NH -。 Halogen: Refers to fluorine, chlorine, bromine or iodine. Alkyl: means a straight or branched alkyl group. Haloalkyl: a linear or branched alkyl group in which a hydrogen atom is partially or completely replaced by a halogen atom. Alkoxy: A linear or branched alkyl group bonded to a structure via an oxygen atom. Haloalkoxy: A hydrogen atom on a straight or branched alkoxy group is partially or completely substituted by a halogen atom. Alkenyl: straight or branched and may have at least one carbon-carbon double bond at any position. 3⁄4 Alkenyl: The hydrogen atom on the linear or branched alkenyl group is partially or completely replaced by a halogen atom. Alkynyl: straight or branched and may have at least one carbon-carbon triple bond at any position. Haloalkynyl group: A hydrogen atom on a linear or branched alkynyl group is partially or completely substituted by a halogen atom. Cycloalkyl: a cyclic alkane having three or more carbon atoms, such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group or the like. Alkylcarbonyl: An alkyl group is attached to the structure via a carbonyl group, such as CH 3 CO-, CH 3 CH 2 CO-. Haloalkylcarbonyl: The hydrogen atom on the alkyl group of the alkylcarbonyl group may be partially or completely substituted by a halogen atom such as CF 3 CO-. Alkoxycarbonyl: The alkoxy group is attached to the structure via a carbonyl group. Such as CH 3 OCO-, CH 3 CH 2 OCO-. Haloalkoxycarbonyl: The hydrogen atom on the alkyl group of the alkoxycarbonyl group may be partially or completely substituted by a halogen atom. Such as ClCH 2 CH 2 OCO-. Alkylthio: a linear or branched alkyl group bonded to a structure via a sulfur atom bond. Haloalkylthio: a linear or branched alkylthio group in which a hydrogen atom may be partially or completely substituted by a halogen atom. For example, chloromethylthio, dichloromethylthio, trichloromethylthio, fluoromethylthio, difluoromethylthio, trifluoromethylthio, chlorofluoromethylthio and the like. Alkylsulfinyl: A straight or branched alkyl group is attached to the structure via a sulfinyl group (-SO-), such as a methylsulfinyl group. Alkylsulfonyl: A straight or branched alkyl group is attached to the structure via a sulfonyl group (-S0 2 -), such as a methylsulfonyl group. Haloalkylsulfinyl: a linear or branched alkylsulfinyl group in which a hydrogen atom on the alkyl group may be partially or completely substituted by a halogen atom. Haloalkylsulfonyl: a linear or branched alkylsulfonyl group in which a hydrogen atom on the alkyl group may be partially or completely substituted by a halogen atom. Alkylamino: a linear or branched alkyl group bonded to the structure via a nitrogen atom. Alkyl acylamino: such as CH 3 CONH-, CH 3 CH 2 CONH alkylsulfonylamino: such as C3⁄4S0 2 NH-, C3⁄4C3⁄4 S0 2 NH -.
在本发明优选的通式 (I)化合物中， 部分基团及其取代基见表 1-表 3。  In the preferred compounds of the formula (I) of the present invention, some of the groups and their substituents are shown in Tables 1 to 3.
当通式 (I)化合物中 A=CH 时， 化合物的结构如通式 (1-1)所示， 苯环上的取代基 (R5)n 见表 1。 When A = CH in the compound of the formula (I), the structure of the compound is as shown in the formula (1-1), and the substituent (R 5 )n on the benzene ring is shown in Table 1.
Figure imgf000006_0001
/s/uϋ O s-ssonosld οϊοίAV
Figure imgf000006_0001
/s/uϋ O s-ssonosld οϊοίAV
Figure imgf000007_0001
Figure imgf000007_0001
4-CN-2-CF3 2,6-2CH(CH3)2 2,4,6-3 CH(CH3)2 2-CH3-4-N02-6-Br 4-NO2-2-CI4-CN-2-CF3 2,6-2CH(CH 3 ) 2 2,4,6-3 CH(CH 3 ) 2 2-CH 3 -4-N0 2 -6-Br 4-NO2-2-CI
4-CN-2-C1 3,4-2CH(CH3)2 2,4,6-3C(CH3)3 2-CH3-6-NO2-4-CI 5-NO2-2-CI4-CN-2-C1 3,4-2CH(CH 3 ) 2 2,4,6-3C(CH 3 ) 3 2-CH3-6-NO2-4-CI 5-NO2-2-CI
4-CN-2-NO2 3,5-2CH(CH3)2 2,3-2CH3-6-N02 2-CH3-6-N02-4-Br 5-N02-2-Br4-CN-2-NO2 3,5-2CH(CH 3 ) 2 2,3-2CH 3 -6-N0 2 2-CH 3 -6-N0 2 -4-Br 5-N0 2 -2-Br
5-CH3-2-F 2-NO2-4-OCH3 2,4-20CH3-5-Cl 2,5-20CH3-4-N02 2-OCH3-5-CI5-CH3-2-F 2-NO2-4-OCH3 2,4-20CH 3 -5-Cl 2,5-20CH 3 -4-N0 2 2-OCH3-5-CI
4-CH3-2-NO2 2-N02-4-OC2H5 5-CONH2-2-Cl 2,6-2CH3-4-C(CH3)3 4-OCH3-3-F4-CH3-2-NO2 2-N0 2 -4-OC 2 H 5 5-CONH 2 -2-Cl 2,6-2CH 3 -4-C(CH 3 ) 3 4-OCH3-3-F
4-CH3-3-NO2 2,3-2C(CH3)3 4-N(CH3)2-2-N02 4-CF3-2-NO2-5-CI 4-OCH3-3-CI4-CH3-3-NO2 2,3-2C(CH 3 ) 3 4-N(CH 3 ) 2 -2-N0 2 4-CF3-2-NO2-5-CI 4-OCH3-3-CI
5-CH3-2-CN 2,4-2C(CH3)3 5-N(CH3)2-2-N02 4-CF3-2-NO2-6-CI 3-N02-4-F5-CH3-2-CN 2,4-2C(CH 3 ) 3 5-N(CH 3 ) 2 -2-N0 2 4-CF3-2-NO2-6-CI 3-N02-4-F
5-NO2-2-F 2,5-2C(CH3)3 4,5-2CH3-2-N02 4-CF3-2-N02-6-Br 2-OCF3-4-CN -CF3-4,6-2Cl 2,6-2C(CH3)3 2-N02-4-F-5-C1 5-CH3-2-CONH2 2-OCF3-4-CI -CF3-4,6-2Br 3,4-2C(CH3)3 2-CN-4-N02-6-C1 2-CH3-5-CONH2 2-OCF3-4-Br -CH3-2,6-2Cl 3,5-2C(CH3)3 2-CN-4-N02-6-Br 2,4-2F-6-Cl 2-F-4,6-2Br -CH3-4,6-2Br 4-SO2NH2 2-OCH2CH=CH2 4-0(CH2)2N(CH3)2 4-OCF3-2-CI5-NO2-2-F 2,5-2C(CH 3 ) 3 4,5-2CH 3 -2-N0 2 4-CF 3 -2-N0 2 -6-Br 2-OCF3-4-CN -CF 3 -4,6-2Cl 2,6-2C(CH 3 ) 3 2-N02-4-F-5-C1 5-CH 3 -2-CONH 2 2-OCF3-4-CI -CF 3 -4, 6-2Br 3,4-2C(CH 3 ) 3 2-CN-4-N02-6-C1 2-CH 3 -5-CONH 2 2-OCF 3 -4-Br -CH 3 -2,6-2Cl 3,5-2C(CH 3 ) 3 2-CN-4-N0 2 -6-Br 2,4-2F-6-Cl 2-F-4,6-2Br -CH 3 -4,6-2Br 4 -SO2NH2 2-OCH 2 CH=CH 2 4-0(CH 2 ) 2 N(CH 3 ) 2 4-OCF3-2-CI
2,4,6-30CH3 4-NO2-2-OCH3 3-OCH2CH=CH2 2-CH2C(CH3)=CH2 4-OCF3-2-Br2,4,6-30CH 3 4-NO2-2-OCH3 3-OCH 2 CH=CH 2 2-CH 2 C(CH 3 )=CH 2 4-OCF 3 -2-Br
3,4,5-30CH3 2-CH2CH=CH2 4-OCH2CH=CH2 3-CH2C(CH3)=CH2 2,3,5,6-4F3,4,5-30CH 3 2-CH 2 CH=CH 2 4-OCH 2 CH=CH 2 3-CH 2 C(CH 3 )=CH 2 2,3,5,6-4F
2,4,6-3 SCH3 3-CH2CH=CH2 2-OCH2C≡CH 4-CH2C(CH3)=CH2 2-CN-4,6-2Cl2,4,6-3 SCH 3 3-CH 2 CH=CH 2 2-OCH 2 C≡CH 4-CH 2 C(CH 3 )=CH 2 2-CN-4,6-2Cl
2,4,6-30CF3 4-CH2CH=CH2 3-OCH2C≡CH 4-0(C¾)3CH3-2-N02 2-CN-4,6-2Br2,4,6-30CF 3 4-CH 2 CH=CH 2 3-OCH 2 C≡CH 4-0(C3⁄4) 3 CH 3 -2-N0 2 2-CN-4,6-2Br
2,4,6-3 SCF3 2-C(CH3)=CH2 4-OCH2C≡CH 3-OCH3-4-CO2CH3 4-CN-2,6-2Cl2,4,6-3 SCF 3 2-C(CH 3 )=CH 2 4-OCH 2 C≡CH 3-OCH3-4-CO2CH3 4-CN-2,6-2Cl
2-CH2C≡CH 3-C(CH3)=CH2 5-NO2-2-OCH3 2-CH(CH3)CH2CH(CH3)2 4-CF3-2,6-2Cl2-CH 2 C≡CH 3-C(CH 3 )=CH 2 5-NO2-2-OCH3 2-CH(CH 3 )CH 2 CH(CH 3 ) 2 4-CF 3 -2,6-2Cl
3_CH2C≡CH 4-C(CH3)=CH2 5-CH3-2-OCH3 2,3-(CH2CH2CH2-) 4-CF3-2,6-2Br3_CH 2 C≡CH 4-C(CH 3 )=CH 2 5-CH3-2-OCH3 2,3-(CH 2 CH 2 CH 2 -) 4-CF 3 -2,6-2Br
4-CH2C≡CH 4-F-2,6-2Br 4-N02-2,6-2Cl 2,3-(CH2CH2CH2CH2-) 2,3,4,5,6-5Cl4-CH 2 C≡CH 4-F-2,6-2Br 4-N0 2 -2,6-2Cl 2,3-(CH 2 CH 2 CH 2 CH 2 -) 2,3,4,5,6 -5Cl
2-F-3-C1 2,4-2F-6-Cl 4-OCF3-2-NO2 4-N02-2,5-2Cl 2,3-(OCF20-)2-F-3-C1 2,4-2F-6-Cl 4-OCF3-2-NO2 4-N0 2 -2,5-2Cl 2,3-(OCF 2 0-)
3-CH3-2-C1 2-F-4-Cl-6-Br 6-N02-2,3,4-3F 4-F-3-Cl-2,6-2Br 2,3-(OCH20-) -0(CH2)3CH3 2,3,5,6-4F-4-CF3 4-N02-2,6-2Br 3,4-(OCF20-) 3,4-(OCH20-) 当通式 (I)化合物中 A=N时，化合物结构如通式 (1-2)所示， 吡啶环上的取代基 (R5)n见表 3-CH3-2-C1 2-F-4-Cl-6-Br 6-N0 2 -2,3,4-3F 4-F-3-Cl-2,6-2Br 2,3-(OCH 2 0-) -0(CH 2 ) 3 CH 3 2,3,5,6-4F-4-CF 3 4-N0 2 -2,6-2Br 3,4-(OCF 2 0-) 3,4- (OCH 2 0-) When A=N in the compound of the formula (I), the compound structure is as shown in the formula (1-2), and the substituent (R 5 )n on the pyridine ring is shown in the table.
Figure imgf000008_0001
/s/u O s-ssonosld osoiAV
Figure imgf000008_0001
/s/u O s-ssonosld osoiAV
Figure imgf000009_0001
Figure imgf000009_0001
-CO-OCH3-4-CH3-6-C1 3-CO-OCH3-4-CF3-6-CI 3-COCH3-6-CI 4-COCH3-6-CI 5-COCH3-6-CI-OCH2CH3-4-CH3-5-Cl 3-OCH2CF3-4-CF3-5-Cl 3-OCH2CF3-4-Cl 4-OCH2CF3-3-Cl 6-OCH2CF3-3-Cl-OCH2CH3-5-CH3-6-Cl 3-OCH2CF3-5-CF3-6-Cl 3-OCH2CF3-5-Cl 4-OCH2CF3-5-Cl 6-OCH2CF3-4-Cl-OCH2CH3-4-CH3-6-Cl 3-OCH2CF3-4-CF3-6-Cl 3-OCH2CF3-6-Cl 4-OCH2CF3-6-Cl 6-OCH2CF3-5-Cl 通式 (I)化合物中的取代基 Q选自以下七种结构， 式中 X如前所定义， 选自 CH2、 Ν 、 或 S; -CO-OCH3-4-CH3-6-C1 3-CO-OCH3-4-CF3-6-CI 3-COCH3-6-CI 4-COCH3-6-CI 5-COCH3-6-CI-OCH 2 CH 3 -4-CH 3 -5-Cl 3-OCH 2 CF 3 -4-CF 3 -5-Cl 3-OCH 2 CF 3 -4-Cl 4-OCH 2 CF 3 -3-Cl 6-OCH 2 CF 3 -3-Cl-OCH 2 CH 3 -5-CH 3 -6-Cl 3-OCH 2 CF 3 -5-CF 3 -6-Cl 3-OCH 2 CF 3 -5-Cl 4-OCH 2 CF 3 -5-Cl 6-OCH 2 CF 3 -4-Cl-OCH 2 CH 3 -4-CH 3 -6-Cl 3-OCH 2 CF 3 -4-CF 3 -6-Cl 3-OCH 2 CF 3 - 6-Cl 4-OCH 2 CF 3 -6-Cl 6-OCH 2 CF 3 -5-Cl The substituent Q in the compound of the formula (I) is selected from the following seven structures, wherein X is as defined above, From CH 2 , Ν , or S;
Figure imgf000010_0001
Figure imgf000010_0001
表 3  table 3
Figure imgf000010_0002
Figure imgf000011_0001
Figure imgf000010_0002
Figure imgf000011_0001
Figure imgf000012_0001
Figure imgf000012_0001
Figure imgf000013_0001
Figure imgf000013_0001
()遂12-
Figure imgf000013_0003
Figure imgf000013_0002
()遂12-
Figure imgf000013_0003
Figure imgf000013_0002
/s/u O s-ssonosld osoiAV /s/u O s-ssonosld osoiAV
Figure imgf000014_0003
Figure imgf000014_0001
Figure imgf000014_0002
Figure imgf000014_0003
Figure imgf000014_0001
Figure imgf000014_0002
Figure imgf000015_0001
Figure imgf000015_0001
本发明的通式 (I)化合物的制备方法如下 （除特别注明外， 各基团定义同前所述）： 首先在过渡金属催化剂存在下、 于惰性溶剂中卤代芳香化合物 (II)和芳香硼酸或酯 (III) 反应得到 (IV):  The preparation method of the compound of the formula (I) of the present invention is as follows (unless otherwise specified, each group is as defined above): first halogenating the aromatic compound (II) in an inert solvent in the presence of a transition metal catalyst and Aromatic boronic acid or ester (III) is reacted to give (IV):
Figure imgf000015_0002
Figure imgf000015_0002
(Π) (ΠΙ) (IV)  (Π) (ΠΙ) (IV)
式中： Hal是氯、 溴或碘， R9和 R1Q独立地为氢或 C C4烷基。 过渡金属催化剂可选用 钯催化剂例如四 (三苯基膦) -钯 (0)等。溶剂可选自甲苯、 1,2-二氯乙烷或二氧六环等惰性溶剂。 反应温度为 80~120°C。 通式 (II)所示的卤代芳香化合物有市售。 Wherein: Hal is chlorine, bromine or iodine, and R 9 and R 1Q are independently hydrogen or CC 4 alkyl. As the transition metal catalyst, a palladium catalyst such as tetrakis(triphenylphosphine)-palladium(0) or the like can be used. The solvent may be selected from inert solvents such as toluene, 1,2-dichloroethane or dioxane. The reaction temperature is 80 to 120 °C. The halogenated aromatic compound represented by the formula (II) is commercially available.
通式 (III)所示的芳香硼酸或酯化合物部分有市售， 也可以由已知方法制得， 例如参见 US5783522 o  The aromatic boronic acid or ester compound represented by the formula (III) is commercially available or can be produced by a known method, for example, see US 5,783,522.
(IV)在苯环上进一步发生磺化反应得到 0 ， 与取代一级胺 NH2R5进一步反应可得到 (VI): (IV) further sulfonation reaction on the benzene ring gives 0, and further reacts with the substituted primary amine NH 2 R 5 to obtain (VI):
Figure imgf000016_0001
Figure imgf000016_0001
(IV) (V) (VI) 由 (IV)合成 (V)采用的磺化试剂可以为浓硫酸或氯磺酸， 反应温度为 60~140°C。 由 (V)与 取代一级胺 NH2 合成 (VI)的反应可在在二氯甲烷、丁酮或四氢呋喃等极性溶剂中进行， 反 应所用的缚酸剂为三乙胺、 吡啶或碳酸钾等， 反应温度为 20~80°C。 取代一级胺 NH2R6有市 售。 (IV) (V) (VI) The sulfonating reagent used in the synthesis (V) of (IV) may be concentrated sulfuric acid or chlorosulfonic acid, and the reaction temperature is 60 to 140 °C. The reaction of (V) with the substituted primary amine NH 2 to synthesize (VI) can be carried out in a polar solvent such as dichloromethane, methyl ethyl ketone or tetrahydrofuran, and the acid binding agent used for the reaction is triethylamine, pyridine or potassium carbonate. Etc., the reaction temperature is 20~80 °C. The substituted primary amine NH 2 R 6 is commercially available.
当 Q为 -NR6-CN、 -NR6-CH(R8)-CN、 -N 6- N 9-CH( 8) -CN、 -Ν - 0-C¾(CO-X-R7)或 -Ν¾- NR9(CO-X-R7) 一步反应可得到目标化合物 (I)。When Q is -NR 6 -CN, -NR 6 -CH(R 8 )-CN, -N 6 - N 9 -CH( 8 ) -CN, -Ν - 0-C3⁄4(CO-XR 7 ) or -Ν3⁄4 - NR 9 (CO-XR 7 ) The desired compound (I) can be obtained in one step.
Figure imgf000016_0002
Figure imgf000016_0002
(V) (I)  (V) (I)
式中， 各基团的定义同上。 反应所用的溶剂、 缚酸剂以及反应条件同于由 (V)合成 (VI) 的反应。  In the formula, each group is as defined above. The solvent, the acid binding agent, and the reaction conditions used in the reaction are the same as those of the (V) synthesis (VI).
当 Q为 -NR6(CO-X-R7)时， （VI)与中间体 (VII I)反应得到目标化合物 (I) When Q is -NR 6 (CO-XR 7 ), (VI) is reacted with the intermediate (VII I) to give the target compound (I)
Figure imgf000016_0003
Figure imgf000016_0003
式中， 各基团的定义同上。 反应所用的溶剂可为丙酮或乙腈等极性溶剂， 缚酸剂选自碳 酸钾、 碳酸钠等。 反应温度为 20~50°C。  In the formula, each group is as defined above. The solvent used for the reaction may be a polar solvent such as acetone or acetonitrile, and the acid binding agent is selected from the group consisting of potassium carbonate, sodium carbonate and the like. The reaction temperature is 20 to 50 °C.
通式 (VIII)所示的化合物部分有市售， 也可以由已知方法制得， 具体参见 Merck&Co.Inc., 1988.3742。  The compound represented by the formula (VIII) is partially commercially available, and can also be produced by a known method, as described in detail in Merck & Co. Inc., 1988. 3742.
当 Q  When Q
Figure imgf000016_0004
Figure imgf000016_0004
(VII) (IX) 式中， 各基团的定义同上。 反应所用的溶剂可为甲醇、 乙醇、 乙腈等极性溶剂。 反应 温度为 60~80°C。 (VII) (IX) wherein each group is as defined above. The solvent used for the reaction may be a polar solvent such as methanol, ethanol or acetonitrile. Reaction The temperature is 60~80 °C.
(VII) 是通过 (V)在亚 一步反应得到的， 反应温度为 40~80°C。  (VII) is obtained by a stepwise reaction of (V) at a reaction temperature of 40 to 80 °C.
Figure imgf000017_0001
Figure imgf000017_0001
通式（IX)所示的化合物部分有市售， 也可以由已知方法制得， 具体参见 Arch.Pharm.1962,295 :697。  The compound represented by the formula (IX) is partially commercially available, and can also be produced by a known method. For details, see Arch. Pharm. 1962, 295:697.
本发明还包括通式 (I)化合物的盐， 其制备方法如下： 当通式 (I)化合物的 Q中 为 H时， 将通式 (I)化合物与强碱如氢化钠、 甲醇钠、 叔丁醇钠或叔丁醇钾等在甲醇、 乙醇、 叔丁醇、 四氢呋喃或甲苯等溶剂中反应二 可以很方便地得到通式 (I)化合物的盐。 以 Q 为 -NR6-CH(R8)- 说明： The present invention also includes a salt of the compound of the formula (I) which is produced by the following method: When the Q of the compound of the formula (I) is H, the compound of the formula (I) is mixed with a strong base such as sodium hydride, sodium methoxide or unsalt. A salt of the compound of the formula (I) can be conveniently obtained by reacting sodium butoxide or potassium t-butoxide in a solvent such as methanol, ethanol, tert-butanol, tetrahydrofuran or toluene. Let Q be -NR6-CH(R 8 )-
Figure imgf000017_0002
Figure imgf000017_0002
式中， 各基团的定义同前。 反应所用溶剂可为甲醇或甲苯等溶剂。 反应温度 30〜80°C。 以上制备方法可以获得通式 (I)化合物的异构体混合物， 如需得到纯异构体， 可采用常规 方法如结晶或色谱法进行分离。  In the formula, each group has the same definition as before. The solvent used for the reaction may be a solvent such as methanol or toluene. The reaction temperature is 30 to 80 °C. The above preparation method can obtain a mixture of isomers of the compound of the formula (I), and if a pure isomer is obtained, it can be isolated by a conventional method such as crystallization or chromatography.
除非另外指明， 上述所有反应可便利地在大气压力下或特定反应的自身压力下进行。 本发明的通式 (I)化合物适合用作除草剂。 在如小麦、 水稻、 玉米、 大豆和棉花的作物中 它们能够非常有效地防治杂草，特别在低施用剂量表现出上述效果。可以用做灭生性除草剂， 也可用于转基因作物田除草， 对水稻等有一定的安全性， 因此本发明的技术方案还包括通式 All of the above reactions can conveniently be carried out under atmospheric pressure or under the pressure of the specific reaction, unless otherwise indicated. The compound of the formula (I) of the present invention is suitably used as a herbicide. They are very effective in controlling weeds in crops such as wheat, rice, corn, soybeans and cotton, especially at low application doses. It can be used as a herbicide for herbicides, and can also be used for weeding in transgenic crop fields, and has certain safety to rice and the like. Therefore, the technical scheme of the present invention also includes a general formula.
(I)化合物或其盐作为除草剂的用途。 Use of the compound (I) or a salt thereof as a herbicide.
本发明还提供了一种除草组合物， 该组合物中含有通式 (I)的化合物或其盐作为活性组 分以及农业上可接受的载体，组合物中通式 (I)的化合物的重量百分含量为 0.1-99%。因此本 发明的技术方案还包括该组合物作为除草剂的用途。  The present invention also provides a herbicidal composition comprising the compound of the formula (I) or a salt thereof as an active ingredient and an agriculturally acceptable carrier, the weight of the compound of the formula (I) in the composition The percentage is from 0.1 to 99%. The technical solution of the present invention therefore also includes the use of the composition as a herbicide.
本发明的组合物可以按照常规方法制备： 将通式（I)的化合物与载体混合。 这种组合物 中的活性组分可以含本发明的单一化合物或几种化合物的混合物。  The composition of the present invention can be prepared according to a conventional method: The compound of the formula (I) is mixed with a carrier. The active ingredient in such compositions may contain a single compound of the invention or a mixture of several compounds.
本发明组合物中的载体系满足下述条件的物质：它与活性成分配制后便于施用于待处理 的位点， 例如可以是植物、 种子或土壤； 或者有利于贮存、 运输或操作。 载体可以是固体或 液体， 包括通常为气体但已压缩成液体的物质， 通常在配制除草组合物中所用的载体均可使 用。  The carrier in the composition of the present invention is a substance which, after being formulated with the active ingredient, is convenient for application to a site to be treated, for example, a plant, seed or soil; or is advantageous for storage, transportation or handling. The carrier may be a solid or a liquid, and includes a material which is usually a gas but which has been compressed into a liquid, and which is usually used in the preparation of the herbicidal composition.
合适的固体载体包括天然和合成的粘土和硅酸盐， 例如硅藻土、 滑石、 硅镁土、 硅酸铝 (高岭土)、 蒙脱石和云母； 碳酸钙； 硫酸钙； 硫酸铵； 合成的氧化硅和合成硅酸钙或硅酸铝； 元素如碳和硫； 天然的和合成的树脂如苯并呋喃树脂， 聚氯乙烯和苯乙烯聚合物和共聚物； 固体多氯苯酚； 沥青； 蜡如蜂蜡， 石蜡。  Suitable solid carriers include natural and synthetic clays and silicates such as diatomaceous earth, talc, attapulgite, aluminum silicate (kaolin), montmorillonite and mica; calcium carbonate; calcium sulfate; ammonium sulfate; Silicon and synthetic calcium silicate or aluminum silicate; elements such as carbon and sulfur; natural and synthetic resins such as benzofuran resins, polyvinyl chloride and styrene polymers and copolymers; solid polychlorinated phenols; Beeswax, paraffin.
合适的液体载体包括水； 醇如异丙醇和乙醇； 酮如丙酮、 甲基乙基酮、 甲基异丙基酮、 环已基酮； 醚； 芳烃如苯、 甲苯、 二甲苯； 石油馏分如煤油和矿物油； 氯代烃如四氯化碳、 全氯乙烯和三氯乙烯。 通常， 这些液体的混合物也是合适的。  Suitable liquid carriers include water; alcohols such as isopropanol and ethanol; ketones such as acetone, methyl ethyl ketone, methyl isopropyl ketone, cyclohexyl ketone; ethers; aromatic hydrocarbons such as benzene, toluene, xylene; petroleum fractions such as Kerosene and mineral oils; chlorinated hydrocarbons such as carbon tetrachloride, perchloroethylene and trichloroethylene. Usually, mixtures of these liquids are also suitable.
除草组合物通常加工成浓缩物形式并以此用于运输， 在施用之前由使用者将其稀释。少 量的表面活性剂载体的存在有助于稀释过程。这样， 按照本发明的组合物中至少有一种载体 优选是表面活性剂。 例如组合物可含有至少两种载体， 其中至少一种是表面活性剂。 The herbicidal compositions are typically processed into a concentrate form and used for transport, which is diluted by the user prior to administration. The presence of a small amount of surfactant carrier aids in the dilution process. Thus, at least one carrier in the composition according to the invention Preferred is a surfactant. For example, the composition may contain at least two carriers, at least one of which is a surfactant.
表面活性剂可以是乳化剂、 分散剂或润湿剂； 它可以是非离子的或离子的表面活性剂。 合适的表面活性剂的例子包括聚丙烯酸和木质素磺酸的钠盐或钙盐； 分子中含至少 12个碳 原子的脂肪酸或脂肪胺或酰胺与环氧乙烷和 /或环氧丙烷的缩合物。 甘醇、 山梨醇、 蔗糖或 季戊四醇脂肪酸酯及这些酯与环氧乙烷和 /或环氧丙烷的缩合物 ； 脂肪醇或烷基苯酚如对辛 基苯酚或对辛基甲苯酚与环氧乙烷和 /或环氧丙烷的缩合物； 这些缩合产物的硫酸盐和磺酸 盐； 在分子中至少含有 10个碳原子的硫酸或磺酸酯的碱金属或碱土金属盐， 优选钠盐， 例 如硫酸月桂酸酯钠， 硫酸仲烷基酯钠， 磺化蓖麻油钠盐， 磺酸烷基芳基酯钠， 如十二烷基苯 磺酸钠盐。  The surfactant may be an emulsifier, dispersant or wetting agent; it may be a nonionic or ionic surfactant. Examples of suitable surfactants include sodium or calcium salts of polyacrylic acid and lignosulfonic acid; condensation of fatty acids or fatty amines or amides having at least 12 carbon atoms in the molecule with ethylene oxide and/or propylene oxide Things. Glycol, sorbitol, sucrose or pentaerythritol fatty acid esters and condensates of these esters with ethylene oxide and/or propylene oxide; fatty alcohols or alkylphenols such as p-octylphenol or p-octylcresol with epoxy a condensate of ethane and/or propylene oxide; a sulfate and a sulfonate of these condensation products; an alkali metal or alkaline earth metal salt of a sulfuric acid or a sulfonate having at least 10 carbon atoms in the molecule, preferably a sodium salt, For example, sodium laurate sulfate, sodium secondary alkyl sulfate, sodium sulfonated castor oil, sodium alkyl aryl sulfonate, such as sodium dodecyl benzene sulfonate.
本发明的组合物的实例是可湿性粉剂、 粉剂、 颗粒剂和溶液， 可乳化的浓缩剂、 乳剂、 悬浮浓缩剂、 气雾剂和烟雾剂。 可湿性粉剂通常含 25%， 50%或 75%重量活性成分， 且通常 除固体惰性载体之外， 还含有 3-10%重量的分散剂， 且若需要可加入 0-10%重量的稳定剂和 /或其它添加剂如渗透剂或粘着剂。 粉剂通常可成型为具有与可湿性粉剂相似的组成但没有 分散剂的粉剂浓缩剂， 再进一步用固体载体稀释， 得到通常含 0.5-10%重量活性组分的组合 物。 粒剂通常制备成具有 10至 100目（1.676-0.152mm)大小， 且可用成团或注入技术制备。 通常粒剂含 0.5-75%重量的活性成分和 0-10%重量添加剂如稳定剂、 表面活性剂、 缓释改良 剂。 所谓的 "可流动干粉"由具有相对高浓度活性成分的相对小的颗粒组成。 可乳化浓缩剂 除溶剂外，当需要时通常含有共溶剂， 1-50%W/V活性成分， 2-20%W/V乳化剂和 0-20%W/V 其他添加剂如稳定剂、渗透剂和腐蚀抑制剂。 悬浮浓缩剂通常含有 10-75%重量的活性成分、 0.5-15%重量的分散剂、 0.1-10%重量的其它添加剂如消泡剂、 腐蚀抑制剂、 稳定剂、 渗透剂 和粘着剂。  Examples of compositions of the invention are wettable powders, powders, granules and solutions, emulsifiable concentrates, emulsions, suspension concentrates, aerosols and aerosols. Wettable powders usually contain 25%, 50% or 75% by weight of active ingredient, and usually contain 3-10% by weight of dispersing agent in addition to the solid inert carrier, and 0-10% by weight of stabilizer can be added if necessary. And / or other additives such as penetrants or adhesives. The powder may be usually formed into a powder concentrate having a composition similar to that of the wettable powder but without a dispersing agent, and further diluted with a solid carrier to give a composition usually containing 0.5 to 10% by weight of the active ingredient. Granules are typically prepared to have a size of from 10 to 100 mesh (1.676-0.152 mm) and can be prepared by agglomeration or infusion techniques. Usually the granules contain 0.5-75% by weight of active ingredient and 0-10% by weight of additives such as stabilizers, surfactants, sustained release modifiers. The so-called "flowable dry powder" consists of relatively small particles having a relatively high concentration of active ingredient. Emulsifying concentrates, in addition to solvents, usually contain a cosolvent, 1-50% W/V active ingredient, 2-20% W/V emulsifier and 0-20% W/V other additives such as stabilizers, infiltration, when needed. Agent and corrosion inhibitor. The suspension concentrate usually contains 10-75% by weight of active ingredient, 0.5-15% by weight of dispersant, 0.1-10% by weight of other additives such as antifoaming agents, corrosion inhibitors, stabilizers, penetrants and adhesives.
水分散剂和乳剂， 例如通过用水稀释按照本发明的可湿性粉剂或浓缩物得到的组合物， 也列入本发明范围。 所说的乳剂可具有油包水或水包油两个类型。  Aqueous dispersions and emulsions, for example compositions obtained by diluting a wettable powder or concentrate according to the invention with water, are also included in the scope of the invention. The emulsion may be of two types, water-in-oil or oil-in-water.
通过在组合物中加入其他的一种或多种除草剂， 使其能比单独的通式 (I)化合物具有更 广谱的活性。 此外， 其他除草剂可对通式 (I)化合物的除草活性具有增效作用。  By incorporating additional one or more herbicides into the composition, it has a broader spectrum of activity than the compound of formula (I) alone. Furthermore, other herbicides have a synergistic effect on the herbicidal activity of the compounds of the general formula (I).
具体实施方式 detailed description
以下具体的实例用来进一步说明本发明， 但并不限制本发明。  The following specific examples are intended to further illustrate the invention but are not intended to limit the invention.
合成实施例  Synthesis example
施例 1 : 乙基 2-氯 -5- (3_氯 -5- (三氟甲基）吡啶 -2-基）苯磺酰胺基甲酸酯 (化合物 44)  Example 1 : Ethyl 2-chloro-5-(3-chloro-5-(trifluoromethyl)pyridin-2-yl)benzenesulfonamidocarboxylate (Compound 44)
Figure imgf000018_0001
Figure imgf000018_0001
第一步反应： 3-氯 -2- (4-氯苯基 ) -5-三氟甲基吡啶  First step reaction: 3-chloro-2-(4-chlorophenyl)-5-trifluoromethylpyridine
将 2L 5g (0. 10mol) 2, 3-二氯 -5-三氟甲基吡啶、 14. 04g (0. 09mol) 4-氯苯硼酸、 0. 5g (0. 44mmol)四三苯基膦钯和 41. 4g (0. 30mol)碳酸钾在 100ml甲苯和 50ml水的混合物中 回流反应 6小时， TLC板监测， 原料 4-氯苯硼酸反应完毕。 反应混合物冷却至室温， 过滤， 得滤液， 用 （3x80ml ) 乙酸乙酯萃取， 合并萃取液， 用 （3x60ml ) 水洗， 60ml 饱和食盐水 洗， 无水硫酸镁干燥， 过滤， 减压浓缩， 得乳白色固体 20. 4g， 收率： 70%， 熔点 72-74°C。  2L 5g (0. 10mol) 2, 3-dichloro-5-trifluoromethylpyridine, 14.04g (0. 09mol) 4-chlorophenylboronic acid, 0.5g (0.44mmol) tetratriphenylphosphine Palladium and 41.4 g (0.30 mol) of potassium carbonate were refluxed for 6 hours in a mixture of 100 ml of toluene and 50 ml of water, and the reaction of the starting material 4-chlorophenylboronic acid was monitored by TLC. The reaction mixture was cooled to room temperature, and filtered, EtOAcjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjj 20. 4g, yield: 70%, melting point 72-74 ° C.
核磁数据 (^HNMR, 300MHz, 内标 TMS， 溶剂 CDC13)如下： 5 ppm 7.47(2H,d), 7.73(2H,d), 8.04 (lH,s)， 8.83(lH,s)。 Nuclear magnetic data (^HNMR, 300MHz, internal standard TMS, solvent CDC1 3 ) are as follows: 5 ppm 7.47 (2H, d), 7.73 (2H, d), 8.04 (lH, s), 8.83 (lH, s).
第二步反应： 2-氯 -5- (3-氯 -5- (三氟甲基）吡啶 -2-基）苯 -1-磺酰氯  Step 2: 2-Chloro-5-(3-chloro-5-(trifluoromethyl)pyridin-2-yl)benzene-1-sulfonyl chloride
在 0-5 °C下， 向 9. 5g (0. 033mol) 3_氯 _2_ (4-氯苯基） _5_三氟甲基吡啶中滴加 15g (0. 13mol)氯磺酸， 所得混合物在 130°C下加热 8小时， TLC板监测， 原料 3_氯 _2- (4_氯 苯基） -5-三氟甲基吡啶反应完毕。 反应混合物冷至室温， 将反应混合物倒入碎冰中， 用 ( 3x60ml ) 乙酸乙酯萃取， 合并萃取液， 用 （3x50ml ) 水洗， 50ml 饱和食盐水洗， 无水硫 酸镁干燥， 过滤， 减压浓缩， 得淡黄色液体 11. 6g， 收率： 90%。  15 g (0.113 mol) of chlorosulfonic acid was added dropwise to 9.5 g (0. 033 mol) of 3-chloro-2-(4-chlorophenyl)-5-trifluoromethylpyridine at 0-5 ° C. The mixture was heated at 130 ° C for 8 hours, and the reaction of the TLC plate was followed by completion of the reaction of 3-chloro-2-(4-chlorophenyl)-5-trifluoromethylpyridine. The reaction mixture was cooled to room temperature, and the mixture was evaporated. EtOAcjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjj , a pale yellow liquid 11.6g, yield: 90%.
核磁数据 (^HNMR, 300MHz, 内标 TMS， 溶剂 CDC13)如下： Nuclear magnetic data (^HNMR, 300MHz, internal standard TMS, solvent CDC1 3 ) are as follows:
δ ppm 7.68(lH,d), 7.96(lH,d), 8.08(lH,s), 8.52(lH,s), 8.87(lH,s)。  δ ppm 7.68 (lH, d), 7.96 (lH, d), 8.08 (lH, s), 8.52 (lH, s), 8.87 (lH, s).
第三步反应： 2-氯 -5- (3-氯 -5- (三氟甲基）吡啶 -2-基）苯磺酰胺  Step 3: 2-Chloro-5-(3-chloro-5-(trifluoromethyl)pyridin-2-yl)benzenesulfonamide
将 3. 90§ (0. 01011101) 2-氯-5- (3-氯-5- (三氟甲基）吡啶-2-基）苯-1-磺酰氯溶于 20ml 四 氢呋喃中， 冰浴冷至 0_5°C， 滴加 0. 34g (0. 020mol)氨水， 混合物室温下搅拌 2小时， TLC 板监测， 原料 2-氯 -5- (3_氯 -5- (三氟甲基）吡啶 -2-基）苯 -1-磺酰氯反应完毕。 混合物减压 下蒸馏， 所得残余物溶于 30ml乙酸乙酯中， 用 （3x30ml ) 水洗， 30ml饱和食盐水洗， 有机 层用无水硫酸镁干燥， 过滤， 减压浓缩， 得 3g淡黄色固体， 收率： 81%， 熔点 166-168°C。 3.90 § (0. 010111 0 1) 2-chloro-5-(3-chloro-5-(trifluoromethyl)pyridin-2-yl)benzene-1-sulfonyl chloride dissolved in 20 ml of tetrahydrofuran, ice The mixture was cooled to 0_5 ° C, 0. 34 g (0. 020 mol) of aqueous ammonia was added dropwise, and the mixture was stirred at room temperature for 2 hours, and monitored by TLC plate, starting material 2-chloro-5- (3 chloro-5- (trifluoromethyl) The reaction of pyridin-2-yl)benzene-1-sulfonyl chloride is completed. The mixture was evaporated under reduced pressure. EtOAcjjjjjjjjjjjjjjjjjjjj Rate: 81%, melting point 166-168 °C.
核磁数据 (^HNMR, 300MHz, 内标 TMS， 溶剂 CDC13)如下： Nuclear magnetic data (^HNMR, 300MHz, internal standard TMS, solvent CDC1 3 ) are as follows:
δ ppm 5.17(2H,s),7.69(lH,d), 7.96(lH,d), 8.09(lH,s), 8.57(lH,s), 8.86(lH,s)。  δ ppm 5.17 (2H, s), 7.69 (lH, d), 7.96 (lH, d), 8.09 (lH, s), 8.57 (lH, s), 8.86 (lH, s).
第四步反应： 乙基 2-氯 -5- (3_氯 -5- (三氟甲基）吡啶 -2-基)苯磺酰胺基甲酸酯 室温下， 将 0. 6g (1. 6mmOl) 2-氯 _5_ (3_氯 _5_ (三氟甲基）吡啶 _2_基）苯磺酰胺溶于 15ml 丙酮中， 然后向上述溶液中加入 0. 31g (2. 26mmol)碳酸钾， 后滴加 0. 2g (1. 67mmol)氯甲酸乙 酯， 所得混合物在室温下搅 1小时， 回流 6小时， TLC板监测， 原料 2-氯 -5- (3-氯 -5- (三氟 甲基）吡啶 -2-基）苯磺酰胺反应完毕。混合物冷至室温，混合物减压下蒸馏，残余物溶于 50ml 冰水中， 浓盐酸调 pH2,用 （3x30ml ) 乙酸乙酯萃取， 合并萃取液， 用 （3x30ml )水洗， 30ml 饱和食盐水洗， 无水硫酸镁干燥， 过滤， 减压浓缩， 用乙酸乙酯和石油醚的混合液（1 : 3) 柱层析得到 0. 25g标题化合物， 收率： 35%。 The 6th step (1. 6mm). O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O Potassium, followed by dropwise addition of 0.2 g (1. 67 mmol) of ethyl chloroformate, the mixture was stirred at room temperature for 1 hour, refluxed for 6 hours, and monitored by TLC plate, starting material 2-chloro-5- (3-chloro-5- ( The reaction of trifluoromethyl)pyridin-2-yl)benzenesulfonamide is completed. The mixture was cooled to room temperature, and the mixture was evaporated under reduced pressure. The residue was evaporated, evaporated, mjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjj The title compound was obtained, and the crystals were evaporated.
核磁数据 (^HNMR, 300MHz, 内标 TMS， 溶剂 CDC13)如下： Nuclear magnetic data (^HNMR, 300MHz, internal standard TMS, solvent CDC1 3 ) are as follows:
δ ppm 1.20(3H,t), 4.16(2H,q), 7.68(lH,d), 7.77(lH,s), 8.06(2H,t), 8.74(lH,s), 8.88(lH,s)。 实施例 2: 甲基 2-氯 -5- (3_氯 -5- (三氟甲基）吡啶 -2-基) -4-氟苯磺酰胺基甲酸酯 (化合 物 2  δ ppm 1.20(3H,t), 4.16(2H,q), 7.68(lH,d), 7.77(lH,s), 8.06(2H,t), 8.74(lH,s), 8.88(lH,s) . Example 2: Methyl 2-chloro-5-(3-chloro-5-(trifluoromethyl)pyridin-2-yl)-4-fluorobenzenesulfonamidocarboxylate (Compound 2
Figure imgf000019_0001
Figure imgf000019_0001
第一步反应： 3-氯 -2- (4-氯 -2-氟苯基) -5-三氟甲基吡啶 First step reaction: 3-chloro-2-(4-chloro-2-fluorophenyl)-5-trifluoromethylpyridine
将 21. 5g (0. 10mol) 2, 3-二氯 -5-三氟甲基吡啶、 15. 66g (0. 09mol) 4-氯 -2-氟苯硼酸、 0. 5g (0. 44mmol)四三苯基膦钯和 41. 4g (0. 30mol)碳酸钾在 100ml甲苯和 50ml水的混合物中 回流反应 6小时， TLC板监测， 原料 4-氯 -2-氟苯硼酸反应完毕。 反应混合物冷却至室温， 过滤， 得滤液， 用 （3x80ml ) 乙酸乙酯萃取， 合并萃取液， 用 （3x60ml ) 水洗， 60ml 饱和 食盐水洗， 无水硫酸镁干燥，过滤，减压浓缩，得乳白色固体 18. lg， 收率： 65%， 熔点 34-36 °C。  2克 (0. 44mmol), 21. 5g (0. 10mol) 2, 3-dichloro-5-trifluoromethylpyridine, 15. 66g (0. 09mol) 4-chloro-2-fluorobenzeneboronic acid, 0. 5g (0. 44mmol) Tetrakistriphenylphosphine palladium and 41.4 g (0.30 mol) of potassium carbonate were refluxed for 6 hours in a mixture of 100 ml of toluene and 50 ml of water, and the reaction of the starting material 4-chloro-2-fluorobenzeneboronic acid was monitored by TLC. The reaction mixture was cooled to room temperature, and filtered, EtOAcjjjJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJj 18. lg, yield: 65%, melting point 34-36 °C.
核磁数据 (^HNMR, 300MHz, 内标 TMS， 溶剂 CDC13)如下： 5 ppm 7.32(2H,dd), 7.43(lH,d), 8.05 (lH,s), 8.86(lH,s Nuclear magnetic data (^HNMR, 300MHz, internal standard TMS, solvent CDC1 3 ) are as follows: 5 ppm 7.32(2H,dd), 7.43(lH,d), 8.05 (lH,s), 8.86(lH,s
第二步反应： 2-氯 -5- (3-氯 -5- (三氟甲基）吡啶 -2-基) -4-氟苯 -1-磺酰氯  Step 2: 2-Chloro-5-(3-chloro-5-(trifluoromethyl)pyridine-2-yl)-4-fluorobenzene-1-sulfonyl chloride
在 0-5 °C下， 向 10. 2g (0. 033mol) 3_氯 _2_ (4_氯 -2-氟苯基）_5_三氟甲基吡啶中滴加 15g (0. 13mol)氯磺酸， 所得混合物在 130°C下加热 8小时， TLC板监测， 原料 3_氯 _2- (4_氯 苯基） -5-三氟甲基吡啶反应完毕。 反应混合物冷至室温， 将反应混合物倒入碎冰中， 用 ( 3x60ml ) 乙酸乙酯萃取， 合并萃取液， 用 （3x50ml ) 水洗， 50ml 饱和食盐水洗， 无水硫 酸镁干燥， 过滤， 减压浓缩， 得淡黄色液体 12. lg， 收率： 90%。  15 g (0.13 mol) of chlorine was added dropwise to 10.2 g (0. 033 mol) of 3-chloro-2-(4-chloro-2-fluorophenyl)-5-trifluoromethylpyridine at 0-5 °C. The sulfonic acid was obtained, and the resulting mixture was heated at 130 ° C for 8 hours, and the reaction of the TLC plate was carried out, and the reaction of the starting material 3-chloro-2-(4-chlorophenyl)-5-trifluoromethylpyridine was completed. The reaction mixture was cooled to room temperature, and the mixture was evaporated. EtOAcjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjj , 淡, yellowish liquid 12. lg, yield: 90%.
核磁数据 (^HNMR, 300MHz, 内标 TMS， 溶剂 CDC13)如下： Nuclear magnetic data (^HNMR, 300MHz, internal standard TMS, solvent CDC1 3 ) are as follows:
5 ppm 7.40(lH,d), 8.05(lH,s), 8.25 (lH,d), 8.86(lH,s)。  5 ppm 7.40 (lH, d), 8.05 (lH, s), 8.25 (lH, d), 8.86 (lH, s).
第三步反应： 2-氯 -5- (3-氯 -5- (三氟甲基）吡啶 -2-基) -4-氟苯磺酰胺  Step 3: 2-Chloro-5-(3-chloro-5-(trifluoromethyl)pyridine-2-yl)-4-fluorobenzenesulfonamide
将 4. 08g (0. 01011101) 2-氯-5- (3-氯-5- (三氟甲基）吡啶 -2-基） -4-氟苯 -1-磺酰氯溶于 20ml四氢呋喃中，冰浴冷至 0_5°C， 滴加 0. 34g (0. 020mol)氨水， 混合物室温下搅拌 2小时， TLC板监测， 原料 2-氯 -5- (3-氯 -5- (三氟甲基）吡啶 -2-基) -4-氟苯 -1-磺酰氯反应完毕。 混 合物减压下蒸馏， 所得残余物溶于 30ml乙酸乙酯中， 用 （3x30ml ) 水洗， 30ml饱和食盐水 洗， 有机层用无水硫酸镁干燥， 过滤， 减压浓缩， 得 3. 15g淡黄色固体， 收率： 81%， 熔点 84-86 °C。 4. 08g (0. 010111 0 1) 2-chloro-5-(3-chloro-5-(trifluoromethyl)pyridin-2-yl)-4-fluorobenzene-1-sulfonyl chloride was dissolved in 20 ml of tetrahydrofuran The ice bath was cooled to 0_5 ° C, 0. 34 g (0. 020 mol) of ammonia water was added dropwise, and the mixture was stirred at room temperature for 2 hours, and monitored by TLC plate, starting material 2-chloro-5- (3-chloro-5- (trifluoro) The reaction of methyl)pyridin-2-yl)-4-fluorobenzene-1-sulfonyl chloride is completed. The mixture was evaporated to dryness. EtOAc (EtOAc). , yield: 81%, melting point 84-86 °C.
核磁数据 (^HNMR, 300MHz, 内标 TMS， 溶剂 CDC13)如下： Nuclear magnetic data (^HNMR, 300MHz, internal standard TMS, solvent CDC1 3 ) are as follows:
δ ppm 5.17(2H,s),7.44(lH,d), 8.09(lH,s), 8.29(lH,d), 8.88(lH,s)。  δ ppm 5.17 (2H, s), 7.44 (lH, d), 8.09 (lH, s), 8.29 (lH, d), 8.88 (lH, s).
第四步反应： 甲基 2-氯 -5- (3_氯 -5- (三氟甲基）吡啶 -2-基) -4-氟苯磺酰胺基甲酸酯 室温下， 将 0. 62g a. 6mmol) 2-氯 _5_ (3_氯 _5_ (三氟甲基）吡啶 _2_基) -4-氟苯磺酰胺溶 于 15ml丙酮中， 然后向上述溶液中加入 0. 31g (2. 26mmol)碳酸钾， 后滴加 0. 16g (l. 67 ol) 氯甲酸甲酯， 所得混合物在室温下搅 1小时， 回流 6小时， TLC板监测， 原料 2-氯 -5- (3_ 氯 -5- (三氟甲基)吡啶 -2-基) -4-氟苯磺酰胺反应完毕。混合物冷至室温，混合物减压下蒸馏， 残余物溶于 50ml冰水中，浓盐酸调 pH2,用（3x30ml )乙酸乙酯萃取，合并萃取液，用（3x30ml ) 水洗， 30ml 饱和食盐水洗， 无水硫酸镁干燥， 过滤， 减压浓缩， 用乙酸乙酯和石油醚的混 合液（1 : 3)柱层析得到 0. 23g淡黄色油状物， 收率： 32%。  The reaction of the second step: methyl 2-chloro-5-(3-chloro-5-(trifluoromethyl)pyridin-2-yl)-4-fluorobenzenesulfonylcarbamate at room temperature, 0. 62g Ag. 6g) 2-chloro-5_(3_chloro_5_(trifluoromethyl)pyridine-2-yl)-4-fluorobenzenesulfonamide was dissolved in 15 ml of acetone, and then added to the above solution. 2. 26mmol) potassium carbonate, followed by dropwise addition of 0.16g (l. 67 ol) methyl chloroformate, the resulting mixture was stirred at room temperature for 1 hour, refluxed for 6 hours, TLC plate monitoring, starting material 2-chloro-5- (3_ The reaction of chloro-5-(trifluoromethyl)pyridin-2-yl)-4-fluorobenzenesulfonamide was completed. The mixture was cooled to room temperature, and the mixture was evaporated under reduced pressure. The residue was evaporated, evaporated, mjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjj The residue was dried over MgSO4, EtOAc (EtOAc).
核磁数据 (^HNMR, 300MHz, 内标 TMS， 溶剂 CDC13)如下： Nuclear magnetic data (^HNMR, 300MHz, internal standard TMS, solvent CDC1 3 ) are as follows:
δ ppm 2.15(3Hdt), 7.43(lH,d), 8.10(lH,s), 8.45(lH,d), 8.89(lH,s)。  δ ppm 2.15(3Hdt), 7.43(lH,d), 8.10(lH,s), 8.45(lH,d), 8.89(lH,s).
3 : 2-氯 -5- (3-氯 -5- (三氟甲基）吡啶 -2-基) (氰甲基)苯磺酰胺 (化合物 2)  3 : 2-Chloro-5-(3-chloro-5-(trifluoromethyl)pyridine-2-yl)(cyanomethyl)benzenesulfonamide (Compound 2)
Figure imgf000020_0001
Figure imgf000020_0001
室温下， 将 2-氨基乙腈 0.17g(3mmol) 溶于 15ml四氢呋喃中， 在 0_5°C向上述溶液中滴 加 0. 6g (l. 5mmol) 2-氯 -5- (3-氯 -5- (三氟甲基）吡啶 -2-基）苯 -1-磺酰氯， 然后向上述混合物 中加入三乙胺（0. 4g, 4mmol)， 得到 0. 25g标题化合物， 收率： 40%。  6克(l. 5mmol) 2-chloro-5- (3-chloro-5-). The solution of 2-aminoacetonitrile was dissolved in 15 ml of tetrahydrofuran at 0. 5 g. (trifluoromethyl)pyridin-2-yl)benzene-1-sulfonyl chloride, and then the mixture was added triethylamine (0.4 g, 4 mmol).
核磁数据 (^HNMR, 300MHz, 内标 TMS， 溶剂 CDC13)如下： Nuclear magnetic data (^HNMR, 300MHz, internal standard TMS, solvent CDC1 3 ) are as follows:
δ ppm 3.87(2H,d),5.66(lH,t),7.70(lH,d),7.95(lH,d),8.08(lH,s),8.51(lH,s), 8.86(lH,s)。  δ ppm 3.87(2H,d), 5.66(lH,t), 7.70(lH,d),7.95(lH,d),8.08(lH,s),8.51(lH,s), 8.86(lH,s) .
）吡啶 -2-基)苯磺酰胺-二甲酸酯 (化合物  Pyridin-2-yl)benzenesulfonamide-dicarboxylate (compound)
Figure imgf000020_0002
第一步反应： 2-氯 -5- (3-氯 -5- (三氟甲基）吡啶 -2-基)苯磺酰胺
Figure imgf000020_0002
First step reaction: 2-chloro-5-(3-chloro-5-(trifluoromethyl)pyridin-2-yl)benzenesulfonamide
将 3. 90§ (0. 01011101) 2-氯-5- (3-氯-5- (三氟甲基）吡啶-2-基）苯-1-磺酰氯溶于 20ml 四 氢呋喃中， 冰浴冷至 0_5°C， 滴加 0. 34g (0. 020mol)氨水， 混合物室温下搅拌 2小时， TLC 板监测， 原料 2-氯 -5- (3_氯 -5- (三氟甲基）吡啶 -2-基）苯 -1-磺酰氯反应完毕。 混合物减压 下蒸馏， 所得残余物溶于 30ml乙酸乙酯中， 用 （3x30ml ) 水洗， 30ml饱和食盐水洗， 有机 层用无水硫酸镁干燥， 过滤， 减压浓缩， 得 3g淡黄色固体， 收率： 81%， 熔点 166-168°C。 3.90 § (0. 010111 0 1) 2-chloro-5-(3-chloro-5-(trifluoromethyl)pyridin-2-yl)benzene-1-sulfonyl chloride dissolved in 20 ml of tetrahydrofuran, ice The mixture was cooled to 0_5 ° C, 0. 34 g (0. 020 mol) of aqueous ammonia was added dropwise, and the mixture was stirred at room temperature for 2 hours, and monitored by TLC plate, starting material 2-chloro-5- (3 chloro-5- (trifluoromethyl) The reaction of pyridin-2-yl)benzene-1-sulfonyl chloride is completed. The mixture was evaporated under reduced pressure. EtOAcjjjjjjjjjjjjjjjjjjjj Rate: 81%, melting point 166-168 °C.
核磁数据 (^HNMR, 300MHz, 内标 TMS， 溶剂 CDC13)如下： Nuclear magnetic data (^HNMR, 300MHz, internal standard TMS, solvent CDC1 3 ) are as follows:
δ ppm 5.17(2H,s),7.69(lH,d), 7.96(lH,d), 8.09(lH,s), 8.57(lH,s), 8.86(lH,s)。  δ ppm 5.17 (2H, s), 7.69 (lH, d), 7.96 (lH, d), 8.09 (lH, s), 8.57 (lH, s), 8.86 (lH, s).
第二步反应： 二甲基 2-氯 -5- (3_氯 -5- (三氟甲基）吡啶 -2-基)苯磺酰胺-二甲酸酯 室温下， 将 0. 5g (l. 3mmol) 2-氯 _5_ (3_氯 _5_ (三氟甲基）吡啶 _2_基）苯磺酰胺溶于 15ml 四氢呋喃中， 滴加 0. 38g (4mmol)氯甲酸甲酯， 然后向混合物中滴加 0. 4g (4mmol)三乙胺， 所 得混合物在室温下搅 4小时， TLC板监测， 原料 2-氯 -5- (3-氯 -5- (三氟甲基）吡啶 -2-基）苯 磺酰胺反应完毕。 混合物减压下蒸馏， 得粗品， 用乙酸乙酯和石油醚的混合液（1 : 3)柱层析 得到 0. 37g标题化合物， 收率： 57%， 熔点 168-170°C。  The second step of the reaction: dimethyl 2-chloro-5-(3-chloro-5-(trifluoromethyl)pyridin-2-yl)benzenesulfonamide-dicarboxylate 0. 5g (l 3mmol) 2-Chloro-5-(3-chloro-5-(trifluoromethyl)pyridine-2-yl)benzenesulfonamide was dissolved in 15 ml of tetrahydrofuran, and 0.38 g (4 mmol) of methyl chloroformate was added dropwise, then 0. 4g (4mmol) of triethylamine was added dropwise to the mixture, and the mixture was stirred at room temperature for 4 hours, and was monitored by TLC plate, starting material 2-chloro-5-(3-chloro-5-(trifluoromethyl)pyridine-2 -Base) The reaction of benzenesulfonamide is completed. The mixture was evaporated under reduced pressure to dryness crystals crystals crystals crystalsssssssssssssssssssss
核磁数据 (^HNMR, 300MHz, 内标 TMS， 溶剂 CDC13)如下： Nuclear magnetic data (^HNMR, 300MHz, internal standard TMS, solvent CDC1 3 ) are as follows:
δ ppm 3.50(3H,s), 3.68(3H,s), 7.65(lH,d), 7.98(lH,d), 8.08(lH,s), 8.73(lH,s), 8.87(lH,s  δ ppm 3.50(3H,s), 3.68(3H,s), 7.65(lH,d), 7.98(lH,d), 8.08(lH,s), 8.73(lH,s), 8.87(lH,s
实施例 5: 甲基 2-氯 -5- (3_氯 -5- (三氟甲基）吡啶 -2-基)苯磺酰（甲基)胺基甲酸酯 (化合  Example 5: Methyl 2-chloro-5-(3-chloro-5-(trifluoromethyl)pyridin-2-yl)benzenesulfonyl(meth)carbamate (combination
Figure imgf000021_0001
Figure imgf000021_0001
采用上述实施例 4中制备化合物 8的相似方法。  A similar method for the preparation of compound 8 in the above Example 4 was employed.
第一步反应： 2-氯 -5- (3-氯 -5- (三氟甲基）吡啶 -2-基) 甲基苯磺酰胺  First step reaction: 2-chloro-5-(3-chloro-5-(trifluoromethyl)pyridin-2-yl)methylbenzenesulfonamide
使 3. 90g (0. OlOmol) 2-氯 -5- (3_氯 _5_ (三氟甲基)吡啶 -2-基）苯 +磺酰氯与 0. 62g (0. 020mol)甲胺反应， 得到 2. 54g标题化合物， 收率： 66%。  Reaction of 3. 90 g (0. OlOmol) 2-chloro-5-(3-chloro-5-(trifluoromethyl)pyridin-2-yl)benzene + sulfonyl chloride with 0.62 g (0. 020 mol) of methylamine. 2.54 g of the title compound were obtained, yield: 66%.
核磁数据 (^HNMR, 300MHz, 内标 TMS， 溶剂 CDC13)如下： Nuclear magnetic data (^HNMR, 300MHz, internal standard TMS, solvent CDC1 3 ) are as follows:
δ ppm 2.26(lH,s),5.42(lH,s),7.69(lH,d),7.96(lH,d),8.10(lH,s),8.62(lH,d), 8.86(lH,s)。 第二步反应： 甲基 2-氯 -5- (3_氯 -5- (三氟甲基）吡啶 -2-基)苯磺酰胺（甲基）甲酸酯 使 0. 5g (L 3mmol) 2-氯 _5_ (3_氯 _5_ (三氟甲基）吡啶 _2_基） 甲基苯磺酰胺与 0. 25g (2. 6mmol)氯甲酸甲酯反应， 得到 0. 4g标题化合物， 收率： 70%， 熔点 166_168°C。  δ ppm 2.26 (lH, s), 5.42 (lH, s), 7.69 (lH, d), 7.96 (lH, d), 8.10 (lH, s), 8.62 (lH, d), 8.86 (lH, s) . 5克(L 3mmol) The reaction of the second step: methyl 2-chloro-5-(3-chloro-5-(trifluoromethyl)pyridin-2-yl)benzenesulfonamide (meth)carboxylate 0. 5g (L 3mmol) 2克标题化合物,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,, Yield: 70%, melting point 166_168 °C.
核磁数据 (^HNMR, 300MHz, 内标 TMS， 溶剂 CDC13)如下： Nuclear magnetic data (^HNMR, 300MHz, internal standard TMS, solvent CDC1 3 ) are as follows:
δ ppm 3.50(3H,s), 3.68(3H,s), 7.65(lH,d), 7.98(lH,d), 8.08(lH,s), 8.73(lH,s), 8.87(lH,s)。 实施例 6:乙基 2-氯 -5- (3_氯 -5- (三氟甲基）吡啶 -2-基）苯磺酰（甲基)胺基甲酸酯（化合 物 3  δ ppm 3.50(3H,s), 3.68(3H,s), 7.65(lH,d), 7.98(lH,d), 8.08(lH,s), 8.73(lH,s), 8.87(lH,s) . Example 6: Ethyl 2-chloro-5-(3-chloro-5-(trifluoromethyl)pyridin-2-yl)benzenesulfonyl (meth)carbamate (Compound 3
Figure imgf000021_0002
Figure imgf000021_0002
采用上述实施例 4中制备化合物 8相似方法。  A similar procedure to the preparation of compound 8 in the above Example 4 was employed.
使 0. 5g (L 3mmol) 2-氯 _5_ (3_氯 _5_ (三氟甲基）吡啶 _2_基） 甲基苯磺酰胺与 0. 28g (2. 6 ol)氯甲酸乙酯反应， 得到 0. 38g标题化合物， 收率： 64. 4%， 熔点 164_166°C。  5克 (2. 6 ol) ethyl chloroformate, 0. 5g (L 3mmol) 2-chloro_5_ (3_chloro_5_(trifluoromethyl)pyridine-2-yl)methylbenzenesulfonamide and 0. 28g (2.6 ol) ethyl chloroformate Reaction, the title compound was obtained.
核磁数据 (^HNMR, 300MHz, 内标 TMS， 溶剂 CDC13)如下： Nuclear magnetic data (^HNMR, 300MHz, internal standard TMS, solvent CDC1 3 ) are as follows:
δ ppm l.ll(3H,t), 3.48(3H,s), 4.10(3H,dd), 7.65(lH,d), 7.98(lH,d), 8.08(lH,s), 8.71(lH,s), 8.87(lH,s) o δ ppm l.ll(3H,t), 3.48(3H,s), 4.10(3H,dd), 7.65(lH,d), 7.98(lH,d), 8.08(lH,s), 8.71(lH, s), 8.87(lH,s) o
实施例 7: 异丙基 2-氯 -5- (3_氯 -5- (三氟甲基）吡啶 -2-基)苯磺酰胺基甲酸酯 (化合物  Example 7: Isopropyl 2-chloro-5-(3-chloro-5-(trifluoromethyl)pyridin-2-yl)benzenesulfonamidocarboxylate (compound)
Figure imgf000022_0001
Figure imgf000022_0001
室温下， 将 0. 6g (l. 6mmol) 2-氯 _5_ (3_氯 _5_ (三氟甲基）吡啶 _2_基）苯磺酰胺溶于 15ml 丙酮中， 然后向上述溶液中加入 0. 31g (2. 26mmol)碳酸钾， 后滴加 0. 2g (l. 67mmol)氯甲酸异 丙酯， 所得混合物在室温下搅 1小时， 回流 6小时， TLC板监测， 原料 2-氯 -5- (3-氯 -5- (三 氟甲基）吡啶 -2-基)苯磺酰胺反应完毕。 混合物冷至室温， 混合物减压下蒸馏， 残余物溶于 50ml冰水中， 浓盐酸调 pH2,用 （3x30ml ) 乙酸乙酯萃取， 合并萃取液， 用 （3x30ml ) 水洗， 30ml饱和食盐水洗， 无水硫酸镁干燥， 过滤， 减压浓缩， 用乙酸乙酯和石油醚的混合液（1 : 3)柱层析得到 0. 24g标题化合物， 收率： 33%。  0. 6g (1.6 mmol) 2-chloro-5-(3-chloro-5-(trifluoromethyl)pyridin-2-ylbenzenesulfonamide was dissolved in 15 ml of acetone, and then added to the above solution. 0. 31g (2. 26mmol) of potassium carbonate, followed by dropwise addition of 0. 2g (1.77mmol) of isopropyl chloroformate, the resulting mixture was stirred at room temperature for 1 hour, refluxed for 6 hours, TLC plate monitoring, starting material 2-chloro- The reaction of 5-(3-chloro-5-(trifluoromethyl)pyridin-2-yl)benzenesulfonamide was completed. The mixture was cooled to room temperature, and the mixture was evaporated under reduced pressure. The residue was evaporated, evaporated, mjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjj The title compound was obtained, the title compound was obtained from EtOAc.
核磁数据 (^HNMR, 300MHz, 内标 TMS， 溶剂 CDC13)如下： Nuclear magnetic data (^HNMR, 300MHz, internal standard TMS, solvent CDC1 3 ) are as follows:
δ ppm 1.18(6H,d), 4.89(lH,m), 7.62(lH,s), 7.70(lH,d), 8.08(lH,s), 8.73(lH,s), 8.87(lH,s)。 δ ppm 1.18(6H,d), 4.89(lH,m), 7.62(lH,s), 7.70(lH,d), 8.08(lH,s), 8.73(lH,s), 8.87(lH,s) .
实施例 8: 2-氯 -5- (3-氯 -5- (三氟甲基）吡啶 -2-基) (4， 6_二甲氧基嘧啶 _2_基胺甲 酰 45)  Example 8: 2-Chloro-5-(3-chloro-5-(trifluoromethyl)pyridin-2-yl) (4,6-dimethoxypyrimidine-2-aminocarbamoyl 45)
Figure imgf000022_0002
Figure imgf000022_0002
第一步反应： 2-氯 -5- (3-氯 -5- (三氟甲基)吡啶 -2-基)苯磺酰异氰酸酯  First step reaction: 2-chloro-5-(3-chloro-5-(trifluoromethyl)pyridin-2-yl)benzenesulfonyl isocyanate
将 0. 5g (L 3mmol) 2-氯 _5_ (3_氯 _5_ (三氟甲基）吡啶 _2_基）苯磺酰胺溶于 20ml干燥的 甲苯中， 然后向上述溶液中滴加 0. 26g (2mmol)草酰氯， 混合物加热至回流 10小时， TLC板 监测， 原料 2-氯 -5- (3-氯 -5- (三氟甲基）吡啶 -2-基）苯磺酰胺反应完毕。 混合物冷至室温， 过滤， 将滤液中的溶剂甲苯和未反应完的草酰氯蒸出， 得黄色黏稠液体 0. 53g， 收率： 60%。  0.5 g (L 3 mmol) of 2-chloro-5-(3-chloro-5-(trifluoromethyl)pyridin-2-ylbenzenesulfonamide was dissolved in 20 ml of dry toluene, and then 0 was added to the above solution. 26g (2mmol) of oxalyl chloride, the mixture was heated to reflux for 10 hours, monitored by TLC plate, and the starting material 2-chloro-5-(3-chloro-5-(trifluoromethyl)pyridin-2-ylbenzenesulfonamide was reacted. . The mixture was cooled to room temperature, and filtered, and the solvent toluene and the unreacted oxalyl chloride were distilled off to give a yellow viscous liquid, 0.53 g, yield: 60%.
第二步反应： 2-氯 -5- (3-氯 -5- (三氟甲基）吡啶 -2-基) 6_二甲氧基嘧啶 _2_基胺甲 酰)苯磺酰胺  Step 2: 2-Chloro-5-(3-chloro-5-(trifluoromethyl)pyridin-2-yl) 6-dimethoxypyrimidine-2-ylamine-formyl)benzenesulfonamide
将 0. 5g (1. 25mmOl) 2-氯 -5- (3_氯 -5- (三氟甲基）吡啶 _2_基）苯磺酰异氰酸酯和 0. 4g (2. 5mmol) 4, 6_二甲氧基嘧啶 _2_氨溶于 20ml甲苯中， 混合物加热回流 10小时， TLC板 监测， 原料 2-氯 -5- (3-氯 -5- (三氟甲基)吡啶 -2-基)苯磺酰异氰酸酯反应完毕。 将溶剂甲苯 蒸出，残余物用乙酸乙酯和石油醚的混合液（1 : 3)柱层析得到 0. 28g标题化合物，收率： 40%， 熔点 170_172°C。 5g (2. 5mmol) 4 0. 5g (1. 25mm O l) 2-chloro-5-(3-chloro-5-(trifluoromethyl)pyridine-2-ylbenzenesulfonyl isocyanate and 0. 4g (2.5mmol) 6-Dimethoxypyrimidine_2-ammonia was dissolved in 20 ml of toluene, and the mixture was heated under reflux for 10 hours, and was monitored by TLC plate, starting material 2-chloro-5-(3-chloro-5-(trifluoromethyl)pyridine- The 2-yl)benzenesulfonyl isocyanate is completely reacted. The solvent was evaporated, and the residue was purified mjjjjjjjjjj
核磁数据 (^HNMR, 300MHz, 内标 TMS， 溶剂 CDC13)如下： Nuclear magnetic data (^HNMR, 300MHz, internal standard TMS, solvent CDC1 3 ) are as follows:
δ ppm 3.98(6H,s), 5.82(lH,s), 7.21(lH,s), 7.65(lH,d), 8.02(lH,d), 8.08(lH,s), 8.86(2H,d), δ ppm 3.98(6H,s), 5.82(lH,s), 7.21(lH,s), 7.65(lH,d), 8.02(lH,d), 8.08(lH,s), 8.86(2H,d) ,
13.02(lH,s)。 13.02 (lH, s).
实施例 9: 2- (2-氯 -5- (3-氯 -5- (三氟甲基）吡啶 -2-基）苯磺酰） 乙基乙酰胺（化合 物 64
Figure imgf000022_0003
第一步反应： 钠 2-氯 -5- (3-氯 -5- (三氟甲基）吡啶 -2-基）苯亚磺酰盐 Example 9: 2-(2-Chloro-5-(3-chloro-5-(trifluoromethyl)pyridin-2-yl)benzenesulfonyl)ethylacetamide (Compound 64
Figure imgf000022_0003
First step reaction: sodium 2-chloro-5-(3-chloro-5-(trifluoromethyl)pyridin-2-yl)benzenesulfinyl salt
室温下， 将 1. 03g (0. Olmol)亚硫酸钠和 1. 9g (5 ol) 2-氯 _5_ (3-氯 _5_ (三氟甲基）吡啶 -2-基）苯磺酰氯溶于 10ml水中， 混合物加热至 40°C， 并维持 6小时， TLC板监测， 原料 2- 氯 -5- (3-氯 -5- (三氟甲基）吡啶 -2-基)苯磺酰氯反应完毕。混合物冷至室温， 减压蒸馏除水， 得乳白色体 1. 7g， 收率： 90%。  1. 03 g (0. Olmol) of sodium sulfite and 1. 9 g (5 ol) of 2-chloro-5-(3-chloro-5-(trifluoromethyl)pyridin-2-yl)benzenesulfonyl chloride were dissolved in 10 ml at room temperature. In water, the mixture was heated to 40 ° C and maintained for 6 hours. The TLC plate was monitored and the starting material 2-chloro-5-(3-chloro-5-(trifluoromethyl)pyridin-2-yl)benzenesulfonyl chloride was reacted. The mixture was cooled to room temperature, and water was evaporated under reduced pressure to give a white solid (1 g, yield: 90%).
第二步反应： 2- (2-氯 -5- (3-氯 -5- (三氟甲基）吡啶 -2-基）苯磺酰） 乙基乙酰胺 将 0. 5g (1. 4mmol) 钠 2-氯 _5_ (3-氯 _5_ (三氟甲基）吡啶 _2_基）苯亚磺酰盐和 0. 17g (l. 4mmol) 2-氯 乙基乙酰胺溶于 20ml乙醇中， 混合物加热回流 10小时， TLC板监 测，原料钠 2-氯 -5- (3_氯 -5- (三氟甲基)吡啶 -2-基)苯亚磺酰盐反应完毕。将溶剂乙醇蒸出， 残余物用乙酸乙酯和石油醚的混合液（1 : 3)柱层析得到 0. 18g标题化合物， 收率： （30 熔点 54-56 °C o  The second step reaction: 2-(2-chloro-5-(3-chloro-5-(trifluoromethyl)pyridin-2-yl)benzenesulfonyl)ethylacetamide 0. 5g (1. 4mmol) Sodium 2-chloro-5-(3-chloro-5-(trifluoromethyl)pyridin-2-yl)benzenesulfinyl salt and 0.17 g (1.4 mmol) 2-chloroethylacetamide dissolved in 20 ml of ethanol The mixture was heated under reflux for 10 hours, and was monitored by a TLC plate, and the starting material sodium 2-chloro-5-(3-chloro-5-(trifluoromethyl)pyridin-2-yl)benzenesulfinyl salt was reacted. The solvent was distilled off, and the residue was purified mjjjjjjjjjjjjjj
核磁数据 (^HNMR, 300MHz, 内标 TMS， 溶剂 CDC13)如下： Nuclear magnetic data (^HNMR, 300MHz, internal standard TMS, solvent CDC1 3 ) are as follows:
δ ppm 1.34(3H,t), 1.42(lH,m), 1.60(lH,m), 3.88(lH,m), 4.32(2H,m), 7.58(lH,d),7.92(lH,d), 8.08(lH,s), 8.40(lH,d), 8.86(lH,s  δ ppm 1.34(3H,t), 1.42(lH,m), 1.60(lH,m), 3.88(lH,m), 4.32(2H,m), 7.58(lH,d),7.92(lH,d) , 8.08(lH,s), 8.40(lH,d), 8.86(lH,s
实施例 10:甲基 2-氯 -5_ (3-氯 -5- (三氟甲基）吡啶 -2-基）苯磺酰胺基甲酸酯（化合物 47)  Example 10: methyl 2-chloro-5-(3-chloro-5-(trifluoromethyl)pyridin-2-yl)benzenesulfonamidocarboxylate (Compound 47)
Figure imgf000023_0001
Figure imgf000023_0001
室温下， 将 0. 6g (1. 6mmOl) 2-氯 _5_ (3_氯 _5_ (三氟甲基）吡啶 _2_基）苯磺酰胺溶于 15ml 丙酮中， 然后向上述溶液中加入 0. 31g (2. 26mmol)碳酸钾， 后滴加 0. 16g (l. 67mmol)氯甲酸 甲酯， 所得混合物在室温下搅 1小时， 回流 6小时， TLC板监测， 原料 2-氯 -5- (3-氯 -5- (三 氟甲基）吡啶 -2-基)苯磺酰胺反应完毕。 混合物冷至室温， 混合物减压下蒸馏， 残余物溶于 50ml冰水中， 浓盐酸调 pH2,用 （3x30ml ) 乙酸乙酯萃取， 合并萃取液， 用 （3x30ml ) 水洗， 30ml饱和食盐水洗， 无水硫酸镁干燥， 过滤， 减压浓缩， 用乙酸乙酯和石油醚的混合液（1 : 3)柱层析得到 0. 24g标题化合物， 收率： 35%， 熔点 144-146°C。 0. 6g (1. 6mm O l) 2-chloro_5_(3_chloro-5-(trifluoromethyl)pyridine-2-ylbenzenesulfonamide was dissolved in 15 ml of acetone, and then to the above solution 0. 31g (2. 26mmol) of potassium carbonate was added, followed by dropwise addition of 0.16 g (1.77 mmol) of methyl chloroformate, and the resulting mixture was stirred at room temperature for 1 hour, refluxed for 6 hours, monitored by TLC plate, starting material 2-chloro -5-(3-Chloro-5-(trifluoromethyl)pyridin-2-yl)benzenesulfonamide was completely reacted. The mixture was cooled to room temperature, and the mixture was evaporated under reduced pressure. The residue was evaporated, evaporated, mjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjj The title compound was obtained from EtOAc EtOAc EtOAc.
核磁数据 (^HNMR, 300MHz, 内标 TMS， 溶剂 CDC13)如下： Nuclear magnetic data (^HNMR, 300MHz, internal standard TMS, solvent CDC1 3 ) are as follows:
δ ppm 3.72(3H,s),7.69(lH,d), 7.90(lH,s), 8.03(lH,d),8.09(lH,s), 8.74(lH,s),8.87(lH,s 实施例 11：丁基 2-氯 -5- (3- -5- (三氟甲基）吡啶 -2-基)苯磺酰胺基甲酸酯 (化合物 49)  δ ppm 3.72(3H,s), 7.69(lH,d), 7.90(lH,s), 8.03(lH,d),8.09(lH,s), 8.74(lH,s),8.87(lH,s implementation Example 11: Butyl 2-chloro-5-(3- -5-(trifluoromethyl)pyridin-2-yl)benzenesulfonamidocarboxylate (Compound 49)
Figure imgf000023_0002
Figure imgf000023_0002
室温下， 将 0. 6g (1. 6mmOl) 2-氯 _5_ (3_氯 _5_ (三氟甲基）吡啶 _2_基）苯磺酰胺溶于 15ml 丙酮中， 然后向上述溶液中加入 0. 31g (2. 26mmol)碳酸钾， 后滴加 0. 23g (l. 67mmol)氯甲酸 丁酯， 所得混合物在室温下搅 1小时， 回流 6小时， TLC板监测， 原料 2-氯 -5- (3-氯 -5- (三 氟甲基）吡啶 -2-基)苯磺酰胺反应完毕。 混合物冷至室温， 混合物减压下蒸馏， 残余物溶于 50ml冰水中， 浓盐酸调 pH2,用 （3x30ml ) 乙酸乙酯萃取， 合并萃取液， 用 （3x30ml ) 水洗， 30ml饱和食盐水洗， 无水硫酸镁干燥， 过滤， 减压浓缩， 用乙酸乙酯和石油醚的混合液（1 : 3)柱层析得到 0. 24g标题化合物， 收率： 32%。 0. 6g (1. 6mm O l) 2-chloro_5_(3_chloro-5-(trifluoromethyl)pyridine-2-ylbenzenesulfonamide was dissolved in 15 ml of acetone, and then to the above solution 0. 31g (2. 26mmol) of potassium carbonate was added, followed by dropwise addition of 0.23 g (1.77 mmol) of butyl chloroformate, and the resulting mixture was stirred at room temperature for 1 hour, refluxed for 6 hours, and monitored by TLC plate, starting material 2-chloro -5-(3-Chloro-5-(trifluoromethyl)pyridin-2-yl)benzenesulfonamide was completely reacted. The mixture was cooled to room temperature, and the mixture was evaporated under reduced pressure. The residue was evaporated, evaporated, mjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjj The title compound was obtained, the title compound was obtained from EtOAc.
核磁数据 (^HNMR, 300MHz, 内标 TMS， 溶剂 CDC13)如下： Nuclear magnetic data (^HNMR, 300MHz, internal standard TMS, solvent CDC1 3 ) are as follows:
δ ppm 0.84(3H,t),1.25(2H,t), 1.55(2H,m), 4.09(2H,t), 7.68(lH,d),7.74(lH,s), 8.09(2H,m), 8.73(lH,s), 8.87(lH,s) o 实施例 12:丁基 2-氯 -5- (3- -5- (三氟甲基）吡啶 -2-基)苯磺酰胺基甲酸酯 (化合物 50) δ ppm 0.84(3H,t), 1.25(2H,t), 1.55(2H,m), 4.09(2H,t), 7.68(lH,d),7.74(lH,s), 8.09(2H,m) , 8.73(lH,s), 8.87(lH,s) o Example 12: Butyl 2-chloro-5-(3- -5-(trifluoromethyl)pyridin-2-yl)benzenesulfonamidocarboxylate (Compound 50)
Figure imgf000024_0001
Figure imgf000024_0001
室温下， 将 0. 6g (1. 6mmOl) 2-氯 _5_ (3_氯 _5_ (三氟甲基）吡啶 _2_基）苯磺酰胺溶于 15ml 丙酮中， 然后向上述溶液中加入 0. 31g (2. 26mmol)碳酸钾， 后滴加 0. 23g (l. 67mmol) 2-甲氧 基氯甲酸乙酯， 所得混合物在室温下搅 1小时， 回流 6小时， TLC板监测， 原料 2-氯 -5- (3_ 氯 -5- (三氟甲基）吡啶 -2-基)苯磺酰胺反应完毕。 混合物冷至室温， 混合物减压下蒸馏， 残 余物溶于 50ml冰水中，浓盐酸调 pH2,用（3x30ml )乙酸乙酯萃取，合并萃取液，用（3x30ml ) 水洗， 30ml 饱和食盐水洗， 无水硫酸镁干燥， 过滤， 减压浓缩， 用乙酸乙酯和石油醚的混 合液（1 : 3)柱层析得到 0. 24g标题化合物， 收率： 32%。 0. 6g (1. 6mm O l) 2-chloro_5_(3_chloro-5-(trifluoromethyl)pyridine-2-ylbenzenesulfonamide was dissolved in 15 ml of acetone, and then to the above solution 0. 31g (2. 26mmol) of potassium carbonate was added, followed by dropwise addition of 0.23 g (1.77 mmol) of ethyl 2-methoxychloroformate, and the resulting mixture was stirred at room temperature for 1 hour, refluxed for 6 hours, and monitored by TLC. The reaction of 2-chloro-5-(3-chloro-5-(trifluoromethyl)pyridin-2-yl)benzenesulfonamide is completed. The mixture was cooled to room temperature, and the mixture was evaporated under reduced pressure. The residue was evaporatedEtOAcjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjj The title compound was obtained, the title compound was obtained from EtOAc.
核磁数据 (^HNMR, 300MHz, 内标 TMS， 溶剂 CDC13)如下： Nuclear magnetic data (^HNMR, 300MHz, internal standard TMS, solvent CDC1 3 ) are as follows:
δ ppm 3.30(3H,s),3.52(2H,t),4.23(2H,t), 7.68(lH,d), 8.06(2H,d), 8.75(lH,s), 8.87(lH,s 实施例 13 :乙基 2-氯 -5_ (3-氯 -5- (三氟甲基）吡啶 -2-基）苯磺酰胺基甲酸酯（化合物 24)
Figure imgf000024_0002
δ ppm 3.30(3H,s), 3.52(2H,t), 4.23(2H,t), 7.68(lH,d), 8.06(2H,d), 8.75(lH,s), 8.87(lH,s implementation Example 13: Ethyl 2-chloro-5-(3-chloro-5-(trifluoromethyl)pyridin-2-yl)benzenesulfonamidocarboxylate (Compound 24)
Figure imgf000024_0002
室温下， 将 0. 62g a. 6mmol) 2-氯 _5_ (3_氯 _5_ (三氟甲基）吡啶 _2_基) -4-氟苯磺酰胺溶 于 15ml丙酮中， 然后向上述溶液中加入 0. 31g (2. 26mmol)碳酸钾， 后滴加 0. 18g (l. 67 ol) 氯甲酸乙酯， 所得混合物在室温下搅 1小时， 回流 6小时， TLC板监测， 原料 2-氯 -5- (3_ 氯 -5- (三氟甲基)吡啶 -2-基) -4-氟苯磺酰胺反应完毕。混合物冷至室温，混合物减压下蒸馏， 残余物溶于 50ml冰水中，浓盐酸调 pH2,用（3x30ml )乙酸乙酯萃取，合并萃取液，用（3x30ml ) 水洗， 30ml 饱和食盐水洗， 无水硫酸镁干燥， 过滤， 减压浓缩， 用乙酸乙酯和石油醚的混 合液（1 : 3)柱层析得到 0. 23g目标化合物， 收率： 32%， 熔点 124-126°C。  0. 62g a. 6mmol) 2-chloro-5-(3-chloro-5-(trifluoromethyl)pyridine-2-yl)-4-fluorobenzenesulfonamide was dissolved in 15 ml of acetone at room temperature, and then 0. 31g (2. 26mmol) of potassium carbonate was added to the solution, followed by dropwise addition of 0.18g (1.77 ol) of ethyl chloroformate. The mixture was stirred at room temperature for 1 hour, refluxed for 6 hours, and monitored by TLC plate. -Chloro-5-(3_chloro-5-(trifluoromethyl)pyridin-2-yl)-4-fluorobenzenesulfonamide was reacted. The mixture was cooled to room temperature, and the mixture was evaporated under reduced pressure. The residue was evaporated, evaporated, mjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjj The title compound was obtained from EtOAc (EtOAc m.).
核磁数据 (^HNMR, 300MHz, 内标 TMS， 溶剂 CDC13)如下： Nuclear magnetic data (^HNMR, 300MHz, internal standard TMS, solvent CDC1 3 ) are as follows:
δ ppm 1.22(3H,t),4.16(2H,dd), 7.42(lH,d),8.11(lH,s),8.46(lH,d), 8.89(lH,s  δ ppm 1.22(3H,t), 4.16(2H,dd), 7.42(lH,d),8.11(lH,s),8.46(lH,d), 8.89(lH,s
实施例 14: 2-氯 -5_ (3-氯 -5- (三氟甲基）吡啶 -2-基）苯磺酰胺基甲酸 (化合物 23)  Example 14: 2-Chloro-5-(3-chloro-5-(trifluoromethyl)pyridin-2-yl)benzenesulfonamidocarboxylic acid (Compound 23)
Figure imgf000024_0003
Figure imgf000024_0003
室温下， 将 0. 46g (lmmOl) 乙基 2_氯 _5_ (3_氯 _5_ (三氟甲基）吡啶 _2_基）苯磺酰胺基甲 酸酯溶于 8ml乙醇中， 然后向上述溶液中加入 6ml饱和氢氧化钠水溶液， 所得混合物在室温 下搅 3小时， TLC板监测， 原料乙基 2-氯 -5- (3_氯 -5- (三氟甲基）吡啶 -2-基）苯磺酰胺基甲 酸酯反应完毕。 混合物减压下蒸馏， 残余物溶于 10ml 水中， 浓盐酸调 pH2，过滤， 滤饼用 ( 3x5ml ) 水洗， 干燥， 得 0. 22g目标化合物， 收率： 60%， 熔点 180-182 C。 0. 46g (lmm O l) ethyl 2_chloro_5_(3_chloro_5_(trifluoromethyl)pyridine-2-yl)benzenesulfonamidocarboxylate was dissolved in 8 ml of ethanol at room temperature. Then, 6 ml of a saturated aqueous sodium hydroxide solution was added to the above solution, and the resulting mixture was stirred at room temperature for 3 hours, and was monitored by a TLC plate, starting material ethyl 2-chloro-5-(3-chloro-5-(trifluoromethyl)pyridine- The 2-yl)benzenesulfonamidoformate reaction is completed. The mixture was dissolved under reduced pressure. The residue was dissolved in EtOAc EtOAc (EtOAc).
核磁数据 (^HNMR, 300MHz, 内标 TMS， 溶剂 CDC13)如下： Nuclear magnetic data (^HNMR, 300MHz, internal standard TMS, solvent CDC1 3 ) are as follows:
δ ppm 7.42(lH,d),8.11(lH,s),8.46(lH,d), 8.89(lH,s)。  δ ppm 7.42 (lH, d), 8.11 (lH, s), 8.46 (lH, d), 8.89 (lH, s).
本发明的其他化合物参照上述方法合成。  Other compounds of the invention were synthesized by reference to the above methods.
其他部分通式 I化合物的物性及核磁数据 (1HNMR, 300MHz, 内标 TMS， 溶剂 CDC13) 如下- 化合物 29: 油状物。 5 ppm 2.95(6H,s), 7.66(lH,d), 7.92(lH,d), 8.09(lH,s), 8.52(lH,s), 30: 油状物。 S ppm 2.56(3H,s), 7.66(lH,d), 7.92(lH,d), 8.09(lH,s), 8.52(lH,s),
Figure imgf000025_0001
The physical properties and nuclear magnetic data of other partial compounds of formula I (1H NMR, 300MHz, internal standard TMS, solvent CDC1 3 ) are as follows - Compound 29: an oil. 5 ppm 2.95 (6H, s), 7.66 (lH, d), 7.92 (lH, d), 8.09 (lH, s), 8.52 (lH, s), 30: oil. S ppm 2.56(3H,s), 7.66(lH,d), 7.92(lH,d), 8.09(lH,s), 8.52(lH,s),
Figure imgf000025_0001
化合物 39 : 熔点 92-94。C。 δ ppm 1.06(3H,t), 1.44(3H,t), 4.10(4H,m), 7.62(lH,d),Compound 39: m.p. 92-94. C. δ pp m 1.06(3H,t), 1.44(3H,t), 4.10(4H,m), 7.62(lH,d),
7.98(lH,d), 8.09(lH,s), 8.69(lH，s), 8.87(lH,s)。 7.98 (lH, d), 8.09 (lH, s), 8.69 (lH, s), 8.87 (lH, s).
化合物 46： δ ppm 3.53(3H,s), 3.71(3H,s), 7.70(lH，d)， 7.98(lH,d), 8.09(lH,s), 8.78(lH,s), 8.88(lH,s)。  Compound 46: δ ppm 3.53 (3H, s), 3.71 (3H, s), 7.70 (1H, d), 7.98 (1H, d), 8.09 (lH, s), 8.78 (lH, s), 8.88 (lH) , s).
化合物 48： 熔点 100-102°C o δ ppm 1.05(6H,d), 3.48(3H,s), 4.88(lH,m), 7.77(lH,s), 8.01(lH,d), 8.08(lH,s), 8.69(lH,s), 8.87(lH,s)。  Compound 48: mp 100-102 ° C o δ ppm 1.05 (6H, d), 3.48 (3H, s), 4.88 (lH, m), 7.77 (lH, s), 8.01 (lH, d), 8.08 (lH) , s), 8.69 (lH, s), 8.87 (lH, s).
化合物 49: 油状物。 5 ppm 0.84(3H,t), 1.25(2H,t), 1.55(2H,m), 4.09(2H,t), 7.68(lH,d), 7.74(lH,s), 8.09(2H,m), 8.73(lH,s), 8.87(lH,s)。  Compound 49: Oily. 5 ppm 0.84(3H,t), 1.25(2H,t), 1.55(2H,m), 4.09(2H,t), 7.68(lH,d), 7.74(lH,s), 8.09(2H,m) , 8.73 (lH, s), 8.87 (lH, s).
化合物 53： 油状物。 δ ρρπι 5.18(lH,s), 7.68(lH,d),7.94(lH,d), 8.09(2H,d), 8.56(lH,s),
Figure imgf000025_0002
Compound 53: an oil. δ ρρπι 5.18(lH,s), 7.68(lH,d), 7.94(lH,d), 8.09(2H,d), 8.56(lH,s),
Figure imgf000025_0002
化合物 75 : 熔点 112-114。C。 δ ppm 4.51(2H,s), 7.27(2H,d), 7.42(2H,d), 7.76(lH,d),Compound 75: m.p. 112-114. C. δ ppm 4.51(2H,s), 7.27(2H,d), 7.42(2H,d), 7.76(lH,d),
8.09(2H,m), 8.38(lH,s), 8.60(lH,s), 8.84(lH,s)。 8.09 (2H, m), 8.38 (lH, s), 8.60 (lH, s), 8.84 (lH, s).
化合物 82: δ ppm 3.50(3H,s), 3.69(3H,s), 7.62(1 H,d), 7.95(2H,m), 8.68(lH,s)。  Compound 82: δ ppm 3.50 (3H, s), 3.69 (3H, s), 7.62 (1H, d), 7.95 (2H, m), 8.68 (1H, s).
化合物 84: δ ppm 1.10(3H,t), 1.43(3H,t), 4.08(4H，m), 7.60(1 H,d), 7.95(2H,m), 8.64(lH,s)。 化合物 86 : δ ppm 1.00(6H,d), 1.55(6H,d), 4.93(2H,m), 7.60(lH,d), 7.95(2H,m),
Figure imgf000025_0003
Compound 84: δ ppm 1.10 (3H, t), 1.43 (3H, t), 4.08 (4H, m), 7.60 (1H, d), 7.95 (2H, m), 8.64 (lH, s). Compound 86: δ ppm 1.00 (6H, d), 1.55 (6H, d), 4.93 (2H, m), 7.60 (1H, d), 7.95 (2H, m),
Figure imgf000025_0003
化合物 87: δ ppm 3.50(3H,s), 3.69(3H,s), 7.62(lH,d), 7.95(2H,m), 8.68(lH,s)。  Compound 87: δ ppm 3.50 (3H, s), 3.69 (3H, s), 7.62 (1H, d), 7.95 (2H, m), 8.68 (1H, s).
化合物 88 : 熔点 128-130。C。 δ ppm 1.22(3H,t), 3.63(3H,t), 4.24(2H,d), 7.75(lH,d), 8.09(2H,m), 8.80(lH,s)。 Compound 88: m.p. 128-130. C. δ ppm 1.22(3H,t), 3.63(3H,t), 4.24(2H,d), 7.75(lH,d), 8.09(2H,m), 8.80(lH,s).
化合物 92: 熔点 140-142。C。 δ ppm 1.07(6H,d), 3.47(3H,s), 4.90(lH,m), 7.75(lH,d), 8.09(2H,m), 8.80(lH,s)。 Compound 92: m.p. 140-142. C. δ ppm 1.07(6H,d), 3.47(3H,s), 4.90(lH,m), 7.75(lH,d), 8.09(2H,m), 8.80(lH,s).
化合物 97: 油状物。 S ppm 0.85(3H,t), 1.25(2H,m), 1.55(2H,m), 4.09(2H,m), 7.75(lH,d), 8.09(2H,m), 8.80(lH，s)。  Compound 97: an oil. S ppm 0.85(3H,t), 1.25(2H,m), 1.55(2H,m), 4.09(2H,m), 7.75(lH,d), 8.09(2H,m), 8.80(lH,s) .
化合物 3: 油状物。 5 ppm 3.87(2H,d), 5.66(lH,t), 7.43(lH,d), 8.10(lH,s), 8.45(lH,d), 8.89(lH,s)0 Compound 3: an oily substance. 5 ppm 3.87(2H,d), 5.66(lH,t), 7.43(lH,d), 8.10(lH,s), 8.45(lH,d), 8.89(lH,s) 0
化合物 52 : 熔点 128-130°C。 δ ppm 1.06(6H,t), 3.22(2H,dd), 3.52(4H,t), 4.20(3H,t),Compound 52: m.p. 128-130 °C. δ ppm 1.06(6H,t), 3.22(2H,dd), 3.52(4H,t), 4.20(3H,t),
5.30(lH,s), 7.64(lH,d), 8.04(2H,t), 8.58(lH,s), 8.84(lH,d)。 5.30 (lH, s), 7.64 (lH, d), 8.04 (2H, t), 8.58 (lH, s), 8.84 (lH, d).
化合物 128 : 熔点 158-160。C。 δ ppm 1.18(3H,t), 3.87(2H,d), 4.11(2H,d), 5.56(lH,d), 7.73(lH,d), 7.92(lH,d), 8.05(lH,s), 8.32(lH,d), 8.80(lH,s), 8.99(lH,s)。 Compound 128: mp 158-160. C. δ ppm 1.18(3H,t), 3.87(2H,d), 4.11(2H,d), 5.56(lH,d), 7.73(lH,d), 7.92(lH,d), 8.05(lH,s) , 8.32 (lH, d), 8.80 (lH, s), 8.99 (lH, s).
制剂实施例  Formulation example
(配方中活性组分折百后计量加入， 所示百分数均为重量百分含量）  (The active ingredient in the formula is metered in after the hundred percent, and the percentages shown are all by weight.)
实施例 15: 60%可湿性粉剂  Example 15: 60% wettable powder
化合物 44 (含量 97.2%) 60%  Compound 44 (content 97.2%) 60%
十二烷基萘磺酸钠 2%  Sodium dodecylnaphthalene sulfonate 2%
木质素磺酸钠 9%  Sodium lignosulfonate 9%
高岭土 补足至 100%  Kaolin is made up to 100%
将化合物 44、 十二烷基萘磺酸钠、 木质素磺酸钠及高岭土 （均为固体） 混合在 在粉碎机中粉碎， 直到颗粒达到标准。  Compound 44, sodium dodecylnaphthalene sulfonate, sodium lignosulfonate and kaolin (both solids) were mixed and pulverized in a pulverizer until the granules reached the standard.
实施例 16: 35%乳油  Example 16: 35% emulsifiable concentrate
化合物 34 (含量 98.4%) 35%  Compound 34 (content 98.4%) 35%
亚磷酸 10% 乙氧基化甘油三酸酯 15% 10% phosphorous acid Ethoxylated triglycerides 15%
环已酮 补足至 100%  Cyclohexanone to 100%
亚磷酸溶解在环已酮中，然后加入化合物 34和乙氧基化甘油三酸酯，得到透明的溶液。 实施例 17: 30%悬浮液  Phosphorous acid is dissolved in cyclohexanone, then compound 34 and ethoxylated triglyceride are added to give a clear solution. Example 17: 30% suspension
化合物 47 (含量 96.4%) 30%  Compound 47 (content 96.4%) 30%
十二烷基萘磺酸钠 4%  Sodium dodecyl naphthalene sulfonate 4%
半纤维素 2%  Hemicellulose 2%
环氧丙烷 8%  Propylene oxide 8%
水 补足至 100%  Water to 100%
将化合物 7与应加水量的 80%的水及十二烷基萘磺酸钠在球磨机中 （1mm珠） 中一起 粉碎。 半纤维素和环氧丙烷溶解在其余 20%的水中， 然后搅拌加入上述组分。  Compound 7 was pulverized together with 80% of water and sodium laurylnaphthalenesulfonate to be added in a ball mill (1 mm beads). Hemicellulose and propylene oxide were dissolved in the remaining 20% of water, and then the above components were stirred.
实施例 18: 25%水乳剂  Example 18: 25% water emulsion
化合物 22 (含量 96.2%) 25%  Compound 22 (content 96.2%) 25%
十二烷基醇聚乙二醇磷酸酯 4%  Dodecyl alcohol polyethylene glycol phosphate 4%
乙氧基甘油三酸酯 2%  Ethoxytriglyceride 2%
十二烷基苯磺酸钙 1.5%  Calcium dodecylbenzenesulfonate 1.5%
环氧甲乙烷环氧丙烷共聚物 2.5%  Ethylene oxide propylene oxide copolymer 2.5%
环己酮 30%  Cyclohexanone 30%
烷基芳基馏分 补足至 100%  Alkyl aryl fractions make up to 100%
将化合物 22溶解在 80%的应加入溶剂量中 （环己酮和烷基芳基馏分）， 然后加入乳化 剂 （十二烷基醇聚乙二醇磷酸酯、 乙氧基甘油三酸酯及十二烷基苯磺酸钙） 和分散剂 （2.5 份环氧甲乙烷环氧丙烷共聚物）， 将混合物彻底搅拌。 混合物在球磨机 （1mm珠） 中粉碎， 然后再加入其余 20%的溶剂。  Compound 22 is dissolved in 80% of the solvent to be added (cyclohexanone and alkyl aryl fraction), followed by the addition of an emulsifier (dodecyl alcohol polyethylene glycol phosphate, ethoxy triglyceride and The calcium dodecylbenzenesulfonate) and the dispersant (2.5 parts of ethylene oxide propylene oxide copolymer) were thoroughly stirred. The mixture was comminuted in a ball mill (1 mm beads) and then the remaining 20% solvent was added.
生物活性测定  Biological activity assay
实施例 19: 除草活性测定  Example 19: Determination of herbicidal activity
本发明化合物的除草活性测试方法如下：  The herbicidal activity test method of the compound of the present invention is as follows:
将定量的杂草种子分别播于直径为 7cm的装有营养土的纸杯中， 播后覆土 lcm， 镇压、 淋水后在温室培养， 苗前处理于播种后 24小时进行； 苗后处理需出苗后间苗、 定植（禾本科 杂草 10〜20株 /杯， 阔叶杂草 2〜 4株 /杯） ， 待禾本科杂草 2〜 3叶期， 阔叶杂草长至 2真叶 期， 按试验设计剂量用履带式作物喷雾机（英国 Engineer Research Ltd. 设计生产）进行茎叶 喷雾处理 （喷雾压力 1.95 kg/cm2， 喷液量 50 ml/m2， 履带速度 1.48 km/h) 。 试验设 3次重复。 待药液自然风干后， 置于温室内按常规方法管理， 定期观察试材的生长发育情况， 并根据实 际情况， 于处理后定期目测调查供试药剂对杂草的防除效果。  Quantitative weed seeds were separately planted in a 7cm diameter paper cup filled with nutrient soil, covered with soil lcm after sowing, cultured in the greenhouse after suppression and watering, and pre-emergence treatment was carried out 24 hours after sowing; After the seedlings, planting (grass weeds 10~20 plants / cup, broadleaf weeds 2 ~ 4 strains / cup), to the grass weeds 2 ~ 3 leaf stage, broadleaf weeds to 2 true leaf stage, The stem and leaf spray treatment (spray pressure 1.95 kg/cm2, spray volume 50 ml/m2, crawler speed 1.48 km/h) was carried out according to the test design dose with a track-type crop sprayer (designed and manufactured by Engineering Research Ltd., UK). The test was repeated 3 times. After the liquid is naturally dried, it is placed in a greenhouse and managed according to conventional methods. The growth and development of the test materials are regularly observed. According to the actual situation, the control effect of the test agents on weeds is investigated visually after treatment.
防除效果分级标准： 0为无效， 100%为将杂草完全杀死或严重抑制。  Control effect grading standards: 0 is invalid, 100% is to completely kill or severely suppress weeds.
部分苗后测试结果如下 （所有质量浓度均以有效成分计）：  Some post-emergence test results are as follows (all mass concentrations are based on active ingredients):
600g/ha时， 化合物 2、 34、 44、 47、 22、 23、 24、 50对稗草、 狗尾草、 苘麻、 百日草 的防效为 100%; 化合物 29对稗草、 狗尾草、 苘麻、 百日草的防效高于 90%; 化合物 46、 49 对稗草、 狗尾草、 苘麻、 百日草的防效高于 85%。  At 600g/ha, the control effect of compound 2, 34, 44, 47, 22, 23, 24, 50 on valerian, foxtail, ramie, and zinnia is 100%; compound 29 on valerian, foxtail, nettle The control effect of Zinnia is higher than 90%; the compound 46, 49 has more than 85% control effect on valerian, foxtail, ramie and zinnia.
150g/ha时， 化合物 34、 44、 47、 22、 23、 24对稗草、 狗尾草、 苘麻、 百日草的防效为 100%； 化合物 50对稗草、 狗尾草、 苘麻、 百日草的防效高于 90%。  At 150g/ha, the compound 34, 44, 47, 22, 23, 24 has 100% control effect against valerian, foxtail, ramie, and zinnia; compound 50 against valerian, foxtail, ramie, zinnia The control effect is higher than 90%.
37. 5g/ha时， 化合物 47、 22、 23、 24对稗草、 狗尾草、 苘麻、 百日草的防效为 100%; 化合物 34、 44对稗草、 狗尾草、 苘麻、 百日草的防效高于 90%; 化合物 50对稗草、 狗尾草、 苘麻、 百日草的防效高于 70%。  37. At 5g/ha, the resistance of compounds 47, 22, 23, 24 to valerian, foxtail, ramie, zinnia is 100%; compound 34, 44 pairs of valerian, foxtail, ramie, zinnia The control effect is higher than 90%; the compound 50 has more than 70% control effect on valerian, foxtail, ramie and zinnia.
实施例 20: 除草活性对比试验  Example 20: Comparison test of herbicidal activity
将 US5783522中的化合物 1.051 (对照 A)、 1.052 (对照 B) 、 1.054(对照 C)、 L055(对照 D)、 L061(对照 E) 、 L 179(对照 F)作为对照化合物， 与本发明中的化合物进行活性比较。 对 Compound 1.051 (Control A), 1.052 (Control B), 1.054 (Control C), L055 (control) in US5783522 D), L061 (control E), L 179 (control F) were used as control compounds for comparison with the compounds of the present invention. Correct
Figure imgf000027_0001
Figure imgf000027_0001
对照 D 对照 E 对照 F  Control D control E control F
防治稗草、 狗尾草、 苘麻、 百日草活性 （苗后测试） 结果见表 7， 测定方法同前所述 t 表 7The activity of controlling valerian, foxtail, ramie and Zinnia (post-soyling test) is shown in Table 7. The determination method is the same as the above-mentioned t table 7.
Figure imgf000027_0002
Figure imgf000027_0002
实施例 21 : 除草活性对比试验  Example 21: Comparison Test of Herbicidal Activity
本发明化合物 44与商品化品种苯嘧磺草胺 （市售原药， 下同） 进行了活性对照， 结果 见表 8， 测定方法同前所述。 表 8 The compound 44 of the present invention was subjected to an activity control with a commercialized species of saflufenacil (a commercially available original drug, the same hereinafter), and the results are shown in Table 8, and the measurement methods are as described above. Table 8
Figure imgf000028_0001
Figure imgf000028_0001
实施例 22: 杀草谱试验 （浙江）  Example 22: Killing spectrum test (Zhejiang)
本发明化合物 44进行了杀草谱试验， 同时与商品化品种苯嘧磺草胺进行了对照， 表 9， 测定方法同前所述。  The compound 44 of the present invention was subjected to a herbicidal spectrum test and compared with the commercial variety saflufenacil. Table 9, the determination method was as described above.
表 9  Table 9
Figure imgf000028_0002
Figure imgf000028_0002
实施例 23 : 田间防治杂草鸭跖草、 龙葵试验  Example 23: Field control of weeds, geranium and Solanum nigrum
试验于 2011年 7月在辽宁省沈阳市水稻田进行， 试验时田间杂草处于 2-4叶期。 试验 参照农药田间药效试验准则 （一） GB/T17980.40-2000 的相关标准进行。 本发明化合物 44 原药的处理浓度为 7.5、 15、 30、 60 g(a.i./ha), 对照药剂 48%苯达松水剂 （市售） 的浓度为 1440 g(a.i./ha)。 小区面积 20m2， 随机排列， 2次重复， 喷液量约为 450L/hm2。 化合物 44防 治鸭跖草、 龙葵田间小区试验结果见表 10。 The experiment was carried out in the rice field of Shenyang City, Liaoning Province in July 2011. The field weeds were in the 2-4 leaf stage during the experiment. The test is carried out in accordance with the relevant standards for pesticide field efficacy test (1) GB/T17980.40-2000. The treatment concentration of the compound 44 of the present invention was 7.5, 15, 30, 60 g (ai/ha), and the concentration of the control agent 48% bentazon water (commercially available) was 1440 g (ai/ha). The area of the plot is 20 m 2 , which is randomly arranged, repeated twice, and the spray volume is about 450 L/hm 2 . The test results of compound 44 for control of comfrey and sylvestris field are shown in Table 10.
表 10  Table 10
剂量 7天调查结果 15天调查结果  Dosage 7-day survey results 15-day survey results
化合物  Compound
g(a.i./ha) 综合防效 (％) 水稻药害 (％) 综合防效 (％) 水稻药害 (％) g(a.i./ha) Comprehensive control effect (%) Rice phytotoxicity (%) Comprehensive control effect (%) Rice phytotoxicity (%)
7.5 10 0 10 0 7.5 10 0 10 0
15 10 10 10 0  15 10 10 10 0
44  44
30 40 15 40 0  30 40 15 40 0
60 70 35 60 15 苯达松 1440 70 0 70 0 实施例 24: 田间防治杂草慈姑试验  60 70 35 60 15 Bentazon 1440 70 0 70 0 Example 24: Field control weed test
试验于 2011年 6月在吉林省长春市水稻田试验基地进行， 试验时田间杂草处于 2-4叶 期。 试验参照农药田间药效试验准则 （一） GB/T17980.40-2000的相关标准进行。 本发明化 合物 44原药的处理浓度为 7.5、 15、 30、 60、 90 g(a.i./ha), 对照药剂 48%苯达松水剂的浓度 为 1440 g(a丄 /ha)。 小区面积 40m2， 随机排列， 2次重复， 喷液量约为 450L/hm2。 化合物 44 防治水稻杂草慈姑田间小区试验结果见表 11。 The experiment was carried out in June 2011 at the rice field test base in Changchun City, Jilin Province. The field weeds were in the 2-4 leaf stage during the test. The test is carried out in accordance with the relevant standards for pesticide field efficacy test guidelines (1) GB/T17980.40-2000. Inventive The concentration of the original drug of the compound 44 was 7.5, 15, 30, 60, 90 g (ai/ha), and the concentration of the control agent 48% bentazon was 1440 g (a丄/ha). The area of the plot is 40m 2 , randomly arranged, repeated 2 times, and the spray volume is about 450L/hm 2 . The results of the test of compound 44 for control of rice weeds in the field were shown in Table 11.
表 11  Table 11
剂量 7天调查结果 15天调查结果 化合物  Dosage 7-day investigation results 15-day investigation results Compound
g(a.i./ha) 慈姑防效 (％) 水稻药害 (％) 慈姑防效 (％) 水稻药害 (％) g(a.i./ha) Sage prevention (%) Rice phytotoxicity (%) Sage prevention (%) Rice phytotoxicity (%)
7.5 15 5 10 0 7.5 15 5 10 0
15 35 15 20 5  15 35 15 20 5
44 30 45 25 30 15  44 30 45 25 30 15
60 60 30 40 25  60 60 30 40 25
90 70 50 60 35 苯达松 1440 80 0 80 0 田间试验药效计算方法如下：  90 70 50 60 35 Bentazon 1440 80 0 80 0 The calculation method for field trials is as follows:
(X杂草株数 (鲜重)一 Pt杂草株数 （鲜重）  (Number of X weeds (fresh weight) - Number of Pt weeds (fresh weight)
防效 （％) χ 100%  Control effect (%) χ 100%
杂草株数 （鲜重）  Number of weeds (fresh weight)

Claims

权 利 要 求 书 种取代的联芳香基苯磺酰胺类化合物或其盐， 结构如通式 (I)所示: The claim is to substitute a substituted aryl benzene sulfonamide or a salt thereof, and the structure is as shown in the general formula (I):
Figure imgf000030_0001
Figure imgf000030_0001
式中- Where -
A选自 CH或 N;A is selected from CH or N;
i^ R2、 R3、 R4各自独立地选自氢、 氟、 氯、 溴、 氰基、 硝基、 羟基、 巯基、 d-C6烷 基、 d-C6¾代烷基、 C2-C6链烯基、 C2-C6链炔基、 d-C6烷氧基、 d-C6¾代烷氧基、 C2-C6 烯氧基、 C2-C6¾代烯氧基、 C2-C6炔氧基、 C2-C6¾代炔氧基、 羟基羰基、 d-C6烷基羰基、 d-C6卤代烷基羰基、 d-C6烷氧基羰基、 d-C6卤代烷氧基羰基、 d-C6烷硫基、 d-C6卤代 烷硫基、 d-C6烷基亚磺酰基、 d-C6烷基磺酰基、 d-C6卤代烷基亚磺酰基、 d-C6卤代烷基 磺酰基或 d-C6烷基氨基； i^ R 2 , R 3 , R4 are each independently selected from the group consisting of hydrogen, fluorine, chlorine, bromine, cyano, nitro, hydroxy, decyl, dC 6 alkyl, dC 6 3⁄4 alkyl, C 2 -C 6 chain Alkenyl, C 2 -C 6 alkynyl, dC 6 alkoxy, dC 6 3⁄ alkoxy, C 2 -C 6 alkenyloxy, C 2 -C 6 3⁄4 alkenyloxy, C 2 -C 6 alkynyloxy, C 2 -C 6 3⁄4 alkynyloxy, hydroxycarbonyl, dC 6 alkylcarbonyl, dC 6 haloalkylcarbonyl, dC 6 alkoxycarbonyl, dC 6 haloalkoxycarbonyl, dC 6 alkylthio , dC 6 haloalkylthio, dC 6 alkylsulfinyl, dC 6 alkylsulfonyl, dC 6 haloalkylsulfinyl, dC 6 haloalkylsulfonyl or dC 6 alkylamino;
R5选自氢、 氟、 氯、 溴、 氰基、 硝基、 巯基、 羟基、 d-C6烷基、 d-C6卤代烷基、 C2-C6 链烯基、 C2-C6链炔基、 d-C6烷氧基、 d-C6 ¾代烷氧基、 C2-C6烯氧基、 C2-C6炔氧基、 羟 基羰基、 d-C6烷基羰基、 d-C6¾代烷基羰基、 d-C6烷氧基羰基、 d-C6¾代烷氧基羰基、 d-C6烷硫基、 C2-C6卤代烷硫基、 d-C6烷基亚磺酰基、 d-C6卤代烷基亚磺酰基、 d-C6烷 基磺酰基、 d-C6卤代烷基磺酰基、 d-C6烷基氨基、 二- (d-C6烷基） 氨基、 d-C6烷基酰 基氨基或^-^烷基磺酰基氨基； n=l-4; R 5 is selected from the group consisting of hydrogen, fluorine, chlorine, bromine, cyano, nitro, decyl, hydroxy, dC 6 alkyl, dC 6 haloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, dC 6 alkoxy, dC 6 3⁄4 alkoxy, C 2 -C 6 alkenyloxy, C 2 -C 6 alkynyloxy, hydroxycarbonyl, dC 6 alkylcarbonyl, dC 6 3⁄4 alkylcarbonyl, dC 6 alkoxycarbonyl, dC 6 3⁄ alkoxycarbonyl, dC 6 alkylthio, C 2 -C 6 haloalkylthio, dC 6 alkylsulfinyl, dC 6 haloalkylsulfinyl, dC 6 alkyl Sulfonyl, dC 6 haloalkylsulfonyl, dC 6 alkylamino, bis-(dC 6 alkyl)amino, dC 6 alkylacylamino or ^-alkylsulfonylamino; n=l-4 ;
Q 选自 -NR6(CO-X-R7)、 -NR^-CN、 -N 6-CH( 8)-CN、 -NR<,- N 9(CO-X- 7)、 -NR<,- NR9-CH(R8) -CN、 -N 6- 0-CH2(CO-X- 7) 或 -CH(R8) (CO-X-R7) ； Q is selected from -NR6(CO-XR 7 ), -NR^-CN, -N 6 -CH( 8 )-CN, -NR<, - N 9 (CO-X- 7 ), -NR<,- NR 9 -CH(R 8 ) -CN, -N 6 - 0-CH 2 (CO-X- 7 ) or -CH(R 8 ) (CO-XR 7 );
X选自 CH2、 NR6、 O或 S; X is selected from CH 2 , NR 6 , O or S ;
、 R9各自独立地选自氢、 氰基、 C C6烷基、 C C6烷氧基、 C C6卤代烷基、 C C6卤 代烷氧基或 C C6烷氧基羰基； And R 9 are each independently selected from the group consisting of hydrogen, cyano, CC 6 alkyl, CC 6 alkoxy, CC 6 haloalkyl, CC 6 haloalkoxy or CC 6 alkoxycarbonyl;
R7、 各自独立地选自氢、氟、氯、溴、 C C6烷基、 d-C6卤代烷基、 C C6烷氧基 C C6 烧基、 S Ci-C6¾¾S Ci-C6¾¾S S Ci-Cg烧基、二- (Ci-C6¾¾S)氛基 Ci-C6 Ci-C6 烷氧基羰基- d-C6烷基、 羧基 -d-C6烷基、 C3-C8环烷基、 C2-Q^¾烯基、 C3-Q^¾炔基， 苯 基、 苯基 C C6烷基、 苯氧基 C C6烷基、 吡啶基、 嘧啶基、 三嗪基、 噁唑基、 噻唑基或吡 唑基， 所述的苯基、 苯氧基、 吡啶基、 嘧啶基、 三嗪基、 噁唑基、 噻唑基或吡唑基环上的氢 各自可未被取代或被 1-4个下述基团所取代： 卤素、 羟基、 硝基、 氰基、 C C6烷基、 CrC6 烷氧基、 ^-^^代烷基、 d-C6¾代烷氧基、 羟基羰基或 d-C6烷氧基羰基。 R 7 , each independently selected from the group consisting of hydrogen, fluorine, chlorine, bromine, CC 6 alkyl, dC 6 haloalkyl, CC 6 alkoxy CC 6 alkyl, S Ci-C 6 3⁄43⁄4S Ci-C63⁄43⁄4S S Ci-Cg Base, bis-(Ci-C 6 3⁄43⁄4S) aryl Ci-C 6 Ci-C 6 alkoxycarbonyl-dC 6 alkyl, carboxy-dC 6 alkyl, C 3 -C 8 cycloalkyl, C 2 - Q^ 3⁄4 alkenyl, C 3 -Q^ 3⁄4 alkynyl, phenyl, phenyl CC 6 alkyl, phenoxy CC 6 alkyl, pyridyl, pyrimidinyl, triazinyl, oxazolyl, thiazolyl or Pyrazolyl, each of the phenyl, phenoxy, pyridyl, pyrimidinyl, triazinyl, oxazolyl, thiazolyl or pyrazolyl rings may be unsubstituted or 1-4 under Substituted by a group: halogen, hydroxy, nitro, cyano, CC 6 alkyl, C r C 6 alkoxy, ^-^ alkyl, dC 6 3⁄ alkoxy, hydroxycarbonyl or dC 6 Alkoxycarbonyl.
2、 根据权利要求 1所述的化合物， 其特征在于： 通式 (I)中  2. The compound according to claim 1, wherein: in the formula (I)
A选自 CH或 N;  A is selected from CH or N;
R 、 、 R3、 R4各自独立地选自氢、 氟、 氯、 溴、 氰基、 硝基、 C C6烷基、 C C6卤代 烷基、 d-C l氧基、 d-C6¾代烷氧基、 羟基羰基、 C C6烷基羰基、 d-C6¾代烷基羰基或 C C6烷氧基羰基； R,, R 3, R4 are each independently selected from hydrogen, fluoro, chloro, bromo, cyano, nitro, CC 6 alkyl, CC 6 haloalkyl, dC l group, dC 6 ¾ alkoxy group, a hydroxyl group a carbonyl group, a CC 6 alkylcarbonyl group, a dC 6 3⁄4 alkylcarbonyl group or a CC 6 alkoxycarbonyl group;
R5选自氢、氟、氯、溴、氰基、硝基、 C C6烷基、 d-C6卤代烷基、 C C6烷氧基、 d-C6 卤代烷氧基、 羟基羰基、 d-C6烷基羰基、 d-C6卤代烷基羰基、 d-C6烷氧基羰基； n=l-4; R 5 is selected from the group consisting of hydrogen, fluorine, chlorine, bromine, cyano, nitro, CC 6 alkyl, dC 6 haloalkyl, CC 6 alkoxy, dC 6 haloalkoxy, hydroxycarbonyl, dC 6 alkylcarbonyl, dC 6 haloalkylcarbonyl, dC 6 alkoxycarbonyl; n = l-4 ;
Q 选自 -NR6(CO-X-R7)、 -NR6-CN、 -NR6-CH(R8)-CN、 -N 6- NR9(CO-X-R7)、 -Ν - N 9-CH( 8) -CN、 -N 6- 0-CH2(CO-X- 7) 或 -CH(R8) (CO-X- 7); Q is selected from -NR6(CO-XR 7 ), -NR6-CN, -NR6-CH(R 8 )-CN, -N 6 - NR 9 (CO-XR 7 ), -Ν - N 9 -CH( 8 ) -CN, -N 6 - 0-CH 2 (CO-X- 7 ) or -CH(R 8 ) (CO-X- 7);
X选自 CH2、 Ν 、 O或 S; R6、 R9各自独立地选自氢、 氰基、 C C6烷基、 C C6烷氧基、 C C6卤代烷基、 C C6 卤代烷氧基或 C C6烷氧基羰基； X is selected from CH 2 , Ν, O or S; R 6 and R 9 are each independently selected from hydrogen, cyano, CC 6 alkyl, CC 6 alkoxy, CC 6 haloalkyl, CC 6 haloalkoxy or CC 6 alkoxycarbonyl;
R7、 各自独立地选自氢、氟、氯、溴、 C C6烷基、 d-C6卤代烷基、 C C6烷氧基 C C6 烧基、 基 Ci-C6¾¾S Ci-C6¾¾S S Ci-Cg烧基、二- (Ci-C6¾¾S)氛基 Ci-C6 Ci-C6 烷氧基羰基- C C6烷基、 羧基 -d-C6烷基、 C3-C8环烷基、 C2-Q^¾烯基、 C3-Q^¾炔基， 苯 基、 苯基 d-C6烷基或苯氧基 d-C6烷基， 所述的苯基或苯氧基环上的氢各自可未被取代或 被 1-4个下述基团所取代： 卤素、 羟基、 硝基、 氰基、 d-C6烷基、 d-C6烷氧基、 ^-^卤 代烷基、 d- ^i代烷氧基、 羟基羰基或 d-C6烷氧基羰基； R 7 , each independently selected from the group consisting of hydrogen, fluorine, chlorine, bromine, CC 6 alkyl, dC 6 haloalkyl, CC 6 alkoxy CC 6 alkyl, based on Ci-C 6 3⁄43⁄4S Ci-C63⁄43⁄4S S Ci-Cg Base, bis-(Ci-C 6 3⁄43⁄4S) aryl Ci-C 6 Ci-C 6 alkoxycarbonyl-CC 6 alkyl, carboxy-dC 6 alkyl, C 3 -C 8 cycloalkyl, C 2 - Q^ 3⁄4 alkenyl, C 3 -Q^ 3⁄4 alkynyl, phenyl, phenyl dC 6 alkyl or phenoxy dC 6 alkyl, the hydrogen on the phenyl or phenoxy ring may not be Substituted or substituted by 1-4 groups: halogen, hydroxy, nitro, cyano, dC 6 alkyl, dC 6 alkoxy, ^-haloalkyl, d-^i alkoxy, Hydroxycarbonyl or dC 6 alkoxycarbonyl;
或其钠盐、 钾盐或铜盐。  Or its sodium, potassium or copper salt.
3、 根据权利要求 2所述的化合物， 其特征在于： 通式 (I)中  The compound according to claim 2, wherein: in the formula (I)
A选自 CH或 N;  A is selected from CH or N;
、 R2、 R3、 各自独立地选自氢、 氟、 氯、 溴、 氰基、 硝基、 d-C4烷基、 d-C4卤 代烷基、 d-C4烷氧基、 d-C4卤代烷氧基、 羟基羰基、 d-C4烷基羰基或 d-C4卤代烷基羰 基； , R 2 , R 3 , each independently selected from the group consisting of hydrogen, fluorine, chlorine, bromine, cyano, nitro, dC 4 alkyl, dC 4 haloalkyl, dC 4 alkoxy, dC 4 haloalkoxy, hydroxycarbonyl , dC 4 alkylcarbonyl or dC 4 haloalkylcarbonyl;
选自氢、氟、氯、溴、氰基、硝基、 d-C4烷基、 d-C4卤代烷基、 d-C4烷氧基、 Ci-C4 卤代烷氧基、 羟基羰基、 d-C4烷基羰基、 d-C4卤代烷基羰基或^ 4烷氧基羰基； n=l-4; Selected from hydrogen, fluorine, chlorine, bromine, cyano, nitro, dC 4 alkyl, dC 4 haloalkyl, dC 4 alkoxy, Ci-C 4 haloalkoxy, hydroxycarbonyl, dC 4 alkylcarbonyl, dC 4- haloalkylcarbonyl or ^ 4 alkoxycarbonyl; n = l-4;
Q 选自 -NR6(CO-X-R7)、 -NR6-CN、 -NR6-CH(R8)-CN、 -N 6- NR9(CO-X-R7)、 -Ν - N 9-CH( 8) -CN、 -N 6- 0-CH2(CO-X- 7) 或 -CH(R8) (CO-X- 7); Q is selected from -NR6(CO-XR 7 ), -NR6-CN, -NR6-CH(R 8 )-CN, -N 6 - NR 9 (CO-XR 7 ), -Ν - N 9 -CH( 8 ) -CN, -N 6 - 0-CH 2 (CO-X- 7 ) or -CH(R 8 ) (CO-X- 7 );
X选自 C¾、 Ν 、 O或 S; X is selected from C3⁄4, Ν, O or S ;
R6、 R9各自独立地选自氢、 氰基、 d-C4烷基、 d-C4烷氧基、 d-C4卤代烷基、 d-C4 卤代烷氧基或 d-C4烷氧基羰基； R 6 and R 9 are each independently selected from the group consisting of hydrogen, cyano, dC 4 alkyl, dC 4 alkoxy, dC 4 haloalkyl, dC 4 haloalkoxy or dC 4 alkoxycarbonyl;
R7、 各自独立地选自氢、 氯、 d-C4烷基、 d-C4卤代烷基、 d-C4烷氧基 d-C4烷基、 氰基 Ci-C4烧基、 Ci-C4烧基氨基 Ci-C4烧基、 二- (Ci-C4烧基)氨基 Ci-C4烧基、 Ci-C4烧氧 基羰基 -d-C4烷基、 羧基 -C C4烷基、 C3-C8环烷基、 C2-Q^¾烯基、 C3-Q^¾炔基， 苯基、 苯 基 C C4烷基或苯氧基 C C4烷基， 所述的苯基或苯氧基环上的氢各自可未被取代或被 1-4 个下述基团所取代： 氟、 氯、 溴、 硝基、 氰基、 d-C4烷基、 C C4烷氧基、 C C4卤代烷基、 d-C4¾代烷氧基、 羟基羰基或 d-C4烷氧基羰基； R 7 , each independently selected from the group consisting of hydrogen, chlorine, dC 4 alkyl, dC 4 haloalkyl, dC 4 alkoxy dC 4 alkyl, cyano Ci-C 4 alkyl, Ci-C 4 alkylamino Ci- C 4 alkyl, bis-(Ci-C 4 alkyl) amino Ci-C 4 alkyl, Ci-C 4 alkoxycarbonyl-dC 4 alkyl, carboxy-CC 4 alkyl, C 3 -C 8 ring An alkyl group, C 2 -Q^ 3⁄4 alkenyl group, C 3 -Q^ 3⁄4 alkynyl group, phenyl group, phenyl CC 4 alkyl group or phenoxy CC 4 alkyl group, said phenyl or phenoxy ring Each of the hydrogens may be unsubstituted or substituted with from 1 to 4 of the following groups: fluorine, chlorine, bromine, nitro, cyano, dC 4 alkyl, CC 4 alkoxy, CC 4 haloalkyl, dC 4 3⁄4 alkoxy, hydroxycarbonyl or dC 4 alkoxycarbonyl;
或其钠盐、 钾盐或铜盐。  Or its sodium, potassium or copper salt.
4、 根据权利要求 3所述的化合物， 其特征在于： 通式 (I)中  4. The compound according to claim 3, wherein: in the formula (I)
A选自 N;  A is selected from N;
、 、 各自独立地选自氢、氟、 氯、 溴、氰基、 C C4烷基、 C C4卤代烷基、 C C4 烷氧基或 C C4卤代烷氧基； , each independently selected from the group consisting of hydrogen, fluorine, chlorine, bromine, cyano, CC 4 alkyl, CC 4 haloalkyl, CC 4 alkoxy or CC 4 haloalkoxy;
R3选自氟、 氯、 溴、 氰基、 C C4烷基、 C C4卤代烷基、 C C4烷氧基或 C C4卤代烷 氧基； R 3 is selected from the group consisting of fluorine, chlorine, bromine, cyano, CC 4 alkyl, CC 4 haloalkyl, CC 4 alkoxy or CC 4 haloalkoxy;
选自氢、 氟、 氯、 溴、 氰基、 C C4烷基、 C C4卤代烷基、 C C4烷氧基、 C C4卤 代烷氧基、 羟基羰基或 d-C4烷氧基羰基； n=l-4; Selected from hydrogen, fluorine, chlorine, bromine, cyano, CC 4 alkyl, CC 4 haloalkyl, CC 4 alkoxy, CC 4 haloalkoxy, hydroxycarbonyl or dC 4 alkoxycarbonyl; n=l-4 ;
Q 选自 -NR6(CO-X-R7)、 -NR6.CN、 -NR6-CH(R8)-CN、 -N 6- NR9(CO-X-R7)、 -NR^- N 9-CH( 8) -CN、 -N 6- 0-CH2(CO-X- 7) 或 -CH(R8) (CO-X- 7); Q is selected from -NR6(CO-XR 7 ), -NR6.CN, -NR6-CH(R 8 )-CN, -N 6 - NR 9 (CO-XR 7 ), -NR^- N 9 -CH ( 8 ) -CN, -N 6 - 0-CH 2 (CO-X- 7 ) or -CH(R 8 ) (CO-X-7);
X选自 C¾、 NR6、 O或 S; X is selected from C3⁄4, NR6, O or S ;
R6选自氢、氰基、 d-C4烷基、 C C4烷氧基、 Ci-C4卤代烷基、 Ci-C4卤代烷氧基或 C C4 烷氧基羰基； R 6 is selected from the group consisting of hydrogen, cyano, dC 4 alkyl, CC 4 alkoxy, Ci-C 4 haloalkyl, Ci-C 4 haloalkoxy or CC 4 alkoxycarbonyl;
R7选自氢、氯、 Ci-C4烧基、 C1-C41¾代烧基、 Ci-C4烧氧基 Ci-C4烧基、氰基 Ci-C4烧基、 Ci-Ct烧基氨基 d-C4烧基、 二 -(Ci-Ct烧基)氨基 d-C4烧基、 Ci-Ct烧氧基羰基 -C1-4烧基、羧 基- d-C4烷基、 C3-C7环烷基、 C3-C6链烯基、 C3-C6链炔基， 苯基、 苯基 d-C4烷基或苯氧 基 d-C4烷基， 所述的苯基或苯氧基环上的氢各自可未被取代或被 1-4个下述基团所取代： 氟、 氯、 溴、 氰基、 甲基、 甲氧基、 三氟甲基、 甲氧基羰基或乙氧基羰基； R 7 is selected from the group consisting of hydrogen, chlorine, Ci-C 4 alkyl, C1-C 413 alkyl, Ci-C 4 alkoxy Ci-C 4 alkyl, cyano Ci-C 4 alkyl, Ci-Ct alkyl Amino dC 4 alkyl, bis-(Ci-Ct alkyl)amino dC 4 alkyl, Ci-Ct alkoxycarbonyl-C 1-4 alkyl, carboxy-dC 4 alkyl, C 3 -C 7 naphthenic a C 3 -C 6 alkenyl group, a C 3 -C 6 alkynyl group, a phenyl group, a phenyl dC 4 alkyl group or a phenoxy dC 4 alkyl group, said phenyl or phenoxy ring Each of the hydrogens may be unsubstituted or substituted by one to four of the following groups: Fluorine, chlorine, bromine, cyano, methyl, methoxy, trifluoromethyl, methoxycarbonyl or ethoxycarbonyl;
R8 自 S<、 ¾ί、 Ci-C4¾¾S C1-C4 l¾ ¾¾l¾、 Ci-C4¾¾ftS Ci-C4¾¾S S Ci-C4¾¾S d-C4烷氧基羰基 -d_4烷基或羧基 d-C4烷基； R 8 from S<, 3⁄4ί, Ci-C 4 3⁄43⁄4S C1-C4 l3⁄4 3⁄43⁄4l3⁄4, Ci-C 4 3⁄43⁄4ftS Ci-C 4 3⁄43⁄4S S Ci-C 4 3⁄43⁄4S dC 4 alkoxycarbonyl-d- 4 alkyl or carboxyl dC 4 alkyl;
R9选自氢、 氰基、 C C4烷基、 C C4烷氧基、 d-C4卤代烷基或 C C4卤代烷氧基； 或其钠盐、 钾盐或铜盐。 R 9 is selected from the group consisting of hydrogen, cyano, CC 4 alkyl, CC 4 alkoxy, dC 4 haloalkyl or CC 4 haloalkoxy; or a sodium, potassium or copper salt thereof.
5、 根据权利要求 4所述的化合物， 其特征在于： 通式 (I)中  The compound according to claim 4, wherein: in the formula (I)
A选自 N;  A is selected from N;
选自氢、 氟、 氯、 甲基或甲氧基；  Selected from hydrogen, fluorine, chlorine, methyl or methoxy;
R2、 选自氢； R 2 , selected from hydrogen;
选自氟、 氯、 甲基或甲氧基；  Selected from fluorine, chlorine, methyl or methoxy;
选自氢、 氟、 氯、 氰基、 甲基、 甲氧基、 三氟甲基或三氟甲氧基； n=l-4; Selected from hydrogen, fluorine, chlorine, cyano, methyl, methoxy, trifluoromethyl or trifluoromethoxy; n=l-4 ;
Q选自 -NR6(CO-X-R7)、 -NR6-CN、 -NR6-CH(R8)-CN或 -CH(R8) (CO-X-R7); Q is selected from -NR6(CO-XR 7 ), -NR 6 -CN, -NR 6 -CH(R 8 )-CN or -CH(R 8 ) (CO-XR 7 );
X选自 C¾、 NH或 O;  X is selected from C3⁄4, NH or O;
R6选自氢、 甲基、 乙基、 甲氧基或 4烷氧基羰基； R 6 is selected from hydrogen, methyl, ethyl, methoxy or 4 -alkoxycarbonyl;
R7选自氢、氯、 Ci-C4烧基、 Ci-Ct l^i代烧基、 Ci-C4烧氧基 Ci-C4烧基、氰基 Ci-C4烧基、 d-C4烷基氨基 d-C4烷基、 二 -(d-C4烷基)氨基 d-C4烷基、 C3-C6链烯基、 C3-C6链炔基或 苯基， 所述的苯基环上的氢可未被取代或被 1-4个下述基团所取代： 氟、 氯、 溴、 氰基、 甲 基、 甲氧基、 三氟甲基、 甲氧基羰基或乙氧基羰基； R 7 is selected from the group consisting of hydrogen, chlorine, Ci-C 4 alkyl, Ci-Ct l^i alkyl, Ci-C 4 alkoxy Ci-C 4 alkyl, cyano Ci-C 4 alkyl, dC 4 An alkylamino dC 4 alkyl group, a di-(dC 4 alkyl)amino dC 4 alkyl group, a C 3 -C 6 alkenyl group, a C 3 -C 6 alkynyl group or a phenyl group, said phenyl ring The hydrogen may be unsubstituted or substituted with from 1 to 4 groups: fluorine, chlorine, bromine, cyano, methyl, methoxy, trifluoromethyl, methoxycarbonyl or ethoxycarbonyl;
选自氢或甲基；  Selected from hydrogen or methyl;
或其钠盐、 钾盐或铜盐。  Or its sodium, potassium or copper salt.
6、 根据权利要求 5所述的化合物， 其特征在于： 通式 (I)中  6. The compound according to claim 5, wherein: in the formula (I)
A选白 N;  A chooses white N;
Ri选自氢、 氟或氯；  Ri is selected from the group consisting of hydrogen, fluorine or chlorine;
、 选自氢；  , selected from hydrogen;
R3选自氟或氯； R 3 is selected from fluorine or chlorine;
选自氢、 氟、 氯或三氟甲基； n=l-4; Selected from hydrogen, fluorine, chlorine or trifluoromethyl; n=l-4 ;
Q选自 -NR6(CO-X-R7)、 -NR6-CN、 -NR6-CH(R8)-CN或 -CH(R8) (CO-X-R7); Q is selected from -NR 6 (CO-XR 7 ), -NR6-CN, -NR6-CH(R 8 )-CN or -CH(R 8 ) (CO-XR 7 );
X选自 C¾、 NH或 0;  X is selected from C3⁄4, NH or 0;
R6选自氢、 甲基或乙基； R 6 is selected from the group consisting of hydrogen, methyl or ethyl;
R7选自氢、 氯、 C C4烷基、 C C4烷氧基 C C4烷基或苯基； R 7 is selected from the group consisting of hydrogen, chlorine, CC 4 alkyl, CC 4 alkoxy CC 4 alkyl or phenyl;
选自氢；  Selected from hydrogen;
或其钠盐。  Or its sodium salt.
7、 一种按照权利要求 1所述的通式 (I)化合物或其盐作为除草剂的用途。  7. Use of a compound of the formula (I) according to claim 1 or a salt thereof as a herbicide.
8、 一种除草组合物， 其特征在于： 含有权利要求 1所述的通式 (I)化合物或其盐作为活 性组分以及农业上可接受的载体， 组合物中通式 (I)化合物或其盐的重量百分含量为 A herbicidal composition, comprising: a compound of the formula (I) according to claim 1 or a salt thereof as an active ingredient, and an agriculturally acceptable carrier, a compound of the formula (I) or The weight percentage of the salt is
0.1-99% 。 0.1-99%.
9、 一种按照权利要求 8所述的组合物作为除草剂的用途。  9. Use of a composition according to claim 8 as a herbicide.
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CN105712926B (en) * 2014-12-05 2019-01-04 沈阳中化农药化工研发有限公司 Substituted biaryl perfume base benzenesulfonamides and application thereof
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