WO2016116058A1 - 一种具有杀线虫活性的三嗪杂环化合物及其制法和用途 - Google Patents

一种具有杀线虫活性的三嗪杂环化合物及其制法和用途 Download PDF

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WO2016116058A1
WO2016116058A1 PCT/CN2016/071608 CN2016071608W WO2016116058A1 WO 2016116058 A1 WO2016116058 A1 WO 2016116058A1 CN 2016071608 W CN2016071608 W CN 2016071608W WO 2016116058 A1 WO2016116058 A1 WO 2016116058A1
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徐晓勇
李忠
王高磊
陈修雷
张经纬
邵旭升
须志平
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East China University of Science and Technology
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
    • C07D417/06—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
    • A01N43/707—1,2,3- or 1,2,4-triazines; Hydrogenated 1,2,3- or 1,2,4-triazines
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
    • A01N43/76—1,3-Oxazoles; Hydrogenated 1,3-oxazoles
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/82—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with three ring hetero atoms
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/88—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms six-membered rings with three ring hetero atoms
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system
    • 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<
    • A01N47/34—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing the groups, e.g. biuret; Thio analogues thereof; Urea-aldehyde condensation products
    • 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
    • C07D253/00—Heterocyclic compounds containing six-membered rings having three nitrogen atoms as the only ring hetero atoms, not provided for by group C07D251/00
    • C07D253/08—Heterocyclic compounds containing six-membered rings having three nitrogen atoms as the only ring hetero atoms, not provided for by group C07D251/00 condensed with carbocyclic rings or ring systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
    • C07D403/06—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
    • C07D413/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
    • C07D417/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
    • C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
    • C07D471/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D491/00—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00
    • C07D491/02—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00 in which the condensed system contains two hetero rings
    • C07D491/10—Spiro-condensed systems
    • C07D491/113—Spiro-condensed systems with two or more oxygen atoms as ring hetero atoms in the oxygen-containing ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
    • C07D495/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
    • C07D495/04—Ortho-condensed systems

Definitions

  • the invention belongs to the field of pesticides.
  • the present invention relates to a triazine heterocyclic compound having nematicidal activity, a process for its preparation and use.
  • Plant parasitic nematodes are a class of pathogenic microorganisms that are extremely harmful. They are widely distributed, diverse, and adaptable to the environment. They can be parasitic in the roots, stems, leaves, seeds, shoots and fruits of plants, and can pass feeding activities. Mechanical damage to the host plant and plundering of the host plant's nutrients, especially its esophageal gland secretions, can cause a series of lesions in the host plant, and infect the host plant with other pathogenic microorganisms, causing compound disease and loss of yield. On a global scale, plant parasitic nematodes cause agricultural losses of more than $100 billion annually, severely restricting the development of the agricultural economy.
  • One of the objects of the present invention is to provide a novel chemical nematicide agent with high efficiency, low toxicity and good environmental compatibility, a preparation method and application thereof.
  • X is O or S
  • Q is a carbonyl group Thiocarbonyl-amino Thiocarbonyl-amino-carbonyl Or covalent bond;
  • L is a substituted or unsubstituted C 1-6 alkylene group, a substituted or unsubstituted C 1-6 haloalkylene group, a substituted or unsubstituted C 2-6 alkenylene group, a substituted or unsubstituted C 2-6 haloalkenylene, substituted or unsubstituted C 2-6 alkynylene, substituted or unsubstituted C 2-6 haloalkynylene, substituted or unsubstituted C 3-7 cycloalkylene , substituted or unsubstituted C 5-7 cycloalkenylene, substituted or unsubstituted phenylene, substituted or unsubstituted naphthylene, substituted or unsubstituted 5 or 6 membered heterocyclylene, or substituted Or an unsubstituted 8- to 14-membered heteroarylene ring or a tricyclic ring system, said substitution being substituted by one
  • L is a substituted or unsubstituted C 1-6 alkyl group, a substituted or unsubstituted C 1-6 haloalkyl group, a substituted or unsubstituted C 2-6 alkenyl group, a substituted or unsubstituted C 2-6 halogenated group Alkenyl, substituted or unsubstituted C 2-6 alkynyl, substituted or unsubstituted C 2-6 haloalkynyl, substituted or unsubstituted C 3-7 cycloalkyl, substituted or unsubstituted C 5 7 cycloalkenyl, substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted 5 or 6 membered heterocyclic, or substituted or unsubstituted 8 to 14 membered heteroaryl ring Or a tricyclic ring system, said substitution being substituted by one or more groups
  • A is a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted 5- or 6-membered heterocyclic group, or a substituted or unsubstituted 8 to 14 membered heteroaryl ring or three
  • said substitution is substituted by one or more groups selected from the group consisting of halogen, cyano, nitro, R', OR', Si(R') 3 , NR'R", C(O)R', C(O)OR', C(O)NR'R", SR', S(O) m R 1 , S(O) 2 NR'R", OC(O)R 1 , OC(O)NR'R", OS(O) 2 R 1 , OS(O) 2 NR'R", N(R 2 )C(O)R 1 , N(R 2 )C(O)NR 'R', N(R
  • G represents a substituent at any one or more positions of A, and G is H, C 1-6 alkyl, C 1-6 haloalkyl, C 2-6 alkenyl, C 2-6 haloalkenyl, Substituted or unsubstituted C 2-6 alkynyl, C 2-6 haloalkynyl, or substituted or unsubstituted C 3-7 cycloalkyl, substituted or unsubstituted C 5-7 cycloalkenyl, substituted or Unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted 5 or 6 membered heterocyclic group, or substituted or unsubstituted 8 to 12 membered heteroaryl bicyclic ring system, said substitution being Substituted by one or more groups selected from the group consisting of halogen, cyano, nitro, R', OR', Si(R') 3 , NR'R",
  • R' and R" are each independently H, C1-6 alkyl, C1-6 haloalkyl, C2-6 alkenyl, C2-6 haloalkenyl, C2-6 alkynyl, C 2-6 haloalkynyl, or substituted or unsubstituted C 3-7 cycloalkyl, substituted or unsubstituted C 5-7 cycloalkenyl, substituted or unsubstituted phenyl, substituted or unsubstituted naphthalene a substituted or unsubstituted 5 or 6 membered heterocyclic group, or a substituted or unsubstituted 8 to 12 membered heteroarylbicyclic ring system, said substitution being one or more groups selected from the group consisting of Substituted: halogen, cyano, nitro, C 1-6 alkyl, C 1-6 haloalkyl, C 2-6 alkenyl, C 2-6 haloalkenyl, C
  • R 1 is C 1-6 alkyl, C 1-6 haloalkyl, C 2-6 alkenyl, C 2-6 haloalkenyl, C 2-6 alkynyl, C 2-6 haloalkynyl, or Substituted or unsubstituted C 3-7 cycloalkyl, substituted or unsubstituted C 5-7 cycloalkenyl, substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted 5 or a 6-membered heterocyclic group, or a substituted or unsubstituted 8- to 12-membered heteroaryl bicyclic ring system, said substitution being substituted by one or more groups selected from the group consisting of halogen, cyano, and nitrate , C 1-6 alkyl, C 1-6 haloalkyl, C 2-6 alkenyl, C 2-6 haloalkenyl, C 2-6
  • R 2 is H, C 1-6 alkyl, C 1-6 haloalkyl, C 2-6 alkenyl, C 2-6 haloalkenyl, C 2-6 alkynyl or C 2-6 haloalkynyl , or a substituted or unsubstituted C 3-7 cycloalkyl group, a substituted or unsubstituted C 5-7 cycloalkenyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted 5 a meta or 6-membered heterocyclic group, or a substituted or unsubstituted 8- to 12-membered heteroaryl bicyclic ring system, said substitution being substituted by one or more groups selected from the group consisting of halogen, cyano , nitro, C 1-6 alkyl, C 1-6 haloalkyl, C 2-6 alkenyl, C 2
  • R 3 , R 4 and R 6 are each independently H, C 1-6 alkyl, C 1-6 haloalkyl, C 2-6 alkenyl, C 2-6 haloalkenyl, C 2-6 Alkynyl or C 2-6 haloalkynyl;
  • R 5 is C 1-6 alkyl, C 1-6 haloalkyl, C 2-6 alkenyl, C 2-6 haloalkenyl, C 2-6 alkynyl or C 2-6 haloalkynyl;
  • n 1 or 2;
  • n 0, 1, 2, 3, 4 or 5.
  • the compound is selected from the group consisting of:
  • X is O or S.
  • L is a substituted or unsubstituted C 1-6 alkylene group, a substituted or unsubstituted C 1-6 haloalkylene group, a substituted or unsubstituted C 2-6 alkenylene group, Substituted or unsubstituted C 2-6 haloalkenylene, substituted or unsubstituted C 2-6 alkynylene, substituted or unsubstituted C 3-7 cycloalkylene, substituted or unsubstituted C 5 7 cycloalkenylene, substituted or unsubstituted phenylene, substituted or unsubstituted naphthylene, substituted or unsubstituted 5 or 6 membered heterocyclylene, or substituted or unsubstituted 8 to 12 a heteroarylene bicyclic ring system, said substitution being substituted by one or more groups selected from the group consisting of halogen, cyano, nitro, C 1-4 alkylene group,
  • L is a substituted or unsubstituted C 1-6 alkyl group, a substituted or unsubstituted C 1-6 haloalkyl group, a substituted or unsubstituted C 2-6 alkenyl group, a substituted or unsubstituted C 2-6 haloene A substituted or unsubstituted C 2-6 alkynyl group, a substituted or unsubstituted C 3-7 cycloalkyl group, a substituted or unsubstituted C 5-7 cycloalkenyl group, a substituted or unsubstituted phenyl group, a substituted or An unsubstituted naphthyl group, a substituted or unsubstituted 5- or 6-membered heterocyclic group, or a substituted or unsubstituted 8- to 12-membered heteroaryl bicyclic ring system, said substitution being one selected from the group consisting of Or substituted by a plurality of
  • L is any group shown in the L column of Tables 2 to 6 in the examples.
  • M is none; or M is H, C 1-6 alkyl, C 1-6 haloalkyl, C 2-6 alkenyl, C 2-6 haloalkenyl, C 2-6 Alkynyl, trimethylsilylethynyl, or substituted or unsubstituted C 3-7 cycloalkyl, substituted or unsubstituted C 5-7 cycloalkenyl, substituted or unsubstituted phenyl, substituted or unsubstituted a naphthyl, substituted or unsubstituted 5 or 6 membered heterocyclic group, or a substituted or unsubstituted 8 to 14 membered heteroarylbicyclic or tricyclic ring system, said substitution being selected from the group consisting of Substituted by one or more groups: halogen, cyano, nitro, C 1-4 alkyl, C 1-4 haloalkyl, C 1-4 alkoxy, C 1-4 alky
  • M is any group shown in column M of Tables 2 to 6 in the examples.
  • A is a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted 5- or 6-membered heterocyclic group, or a substituted or unsubstituted 8 to 12 member.
  • a heteroaryl bicyclic ring system said substitution being substituted by one or more groups selected from the group consisting of halogen, cyano, nitro, C 1-4 alkyl, C 1-4 haloalkyl, C 1-4 alkoxy group, C 1-4 haloalkoxy group, phenoxy group, amino sulfonic acid group, amino-carbonyl group, C 1-4 alkyl-carbonyl group, C 1-4 alkoxy group-carbonyl group, C 1-4 alkylamino-carbonyl or phenylamino-carbonyl.
  • G is H, C 1-6 alkyl, C 1-6 haloalkyl, C 2-6 alkenyl, C 2-6 haloalkenyl, C 2-6 alkynyl, trimethyl Silyl ethynyl, or substituted or unsubstituted C 3-7 cycloalkyl, substituted or unsubstituted C 5-7 cycloalkenyl, substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted Or an unsubstituted 5- or 6-membered heterocyclic group or a substituted or unsubstituted 8- to 12-membered heteroaryl bicyclic ring system, said substitution being substituted by one or more groups selected from the group consisting of: Halogen, cyano, nitro, C 1-4 alkyl, C 1-4 haloalkyl, C 1-4 alkoxy, C 1-4 alkyl-carbonyl, C 1-4 alkoxy-
  • the compound is a compound listed in Tables 2 to 6 in the examples.
  • an agricultural composition comprising:
  • the compound according to the first aspect of the invention or the optical isomer, cis-trans isomer or agrochemically acceptable salt of the compound or the agricultural product according to the second aspect of the invention, is provided in a third aspect of the invention.
  • the composition is used for killing or preventing a plant or plant parasitic nematode or for preparing a nematicide composition for killing or preventing a plant or plant parasitic nematode.
  • a method for producing a compound according to the first aspect of the invention, or an optical isomer, a cis-trans isomer or a pesticide-acceptable salt of the compound is provided.
  • X, Y, Q, L, M, A, G, and n are as defined above.
  • a nematicidal and/or nematode-resistant method comprising the steps of: applying the compound of the first aspect of the invention or the agricultural composition of the second aspect to suffering Or plants that may be exposed to nematodes, the soil around them, or the environment.
  • a process for the preparation of the agricultural composition of the second aspect of the invention comprising the steps of: (1) the compound of the first aspect of the invention, optical isomerism thereof The physicochemical, cis-trans isomer or agrochemically acceptable salt, or a combination thereof; is mixed with (2) a pesticidally acceptable carrier and/or excipient to form the agricultural composition.
  • the inventors have unexpectedly discovered and synthesized a series of triazine heterocyclic compounds having novel structures and significant insecticidal activities after long-term and intensive research. On this basis, the inventors completed the present invention.
  • C 1-6 alkyl refers to a straight or branched alkyl group having from 1 to 6 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec. Base, tert-butyl, or the like.
  • C 2-6 alkenyl refers to a straight or branched alkenyl group having 2 to 6 carbon atoms, such as ethenyl, allyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, or a similar group.
  • C 2-6 alkynyl refers to a straight or branched alkynyl group having 2 to 6 carbon atoms, such as an ethynyl group, a propynyl group, or the like.
  • C 3-7 cycloalkyl refers to a cyclic alkyl group having from 3 to 7 carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, or the like.
  • C 5-7 cycloalkenyl refers to a cyclic alkenyl group having from 5 to 7 carbon atoms having one or more double bonds, such as cyclopentenyl, cyclohexenyl, cycloheptenyl, 1 , 3-cyclohexadienyl, 1,4-cyclohexadienyl, or the like.
  • C 1-4 alkoxy refers to a straight or branched alkoxy group having from 1 to 4 carbon atoms, such as methoxy, ethoxy, propoxy, isopropoxy, Butoxy, isobutoxy, sec-butoxy, tert-butoxy, or the like.
  • halogen means fluoro, chloro, bromo, or iodo.
  • halogenated refers to a group substituted with one or more of the above halogen atoms, which may be the same or different, such as trifluoromethyl, pentafluoroethyl, heptafluoroisopropyl, or the like.
  • ring or “ring system” refers to a carbocyclic or heterocyclic ring.
  • heterocycle means that at least one of the atoms forming the heterocyclic backbone is not carbon and is nitrogen, oxygen or sulfur. Typically, the heterocycle contains no more than 4 nitrogens, no more than 2 oxygens, and/or no more than 2 sulfurs. Unless otherwise indicated, a heterocyclic ring can be a saturated, partially unsaturated or fully unsaturated ring.
  • ring system refers to a fused ring in which two or more rings are taken together.
  • the term "5- or 6-membered heterocyclyl” refers to a five- or six-membered ring containing one or more heteroatoms selected from nitrogen, oxygen or sulfur, such as pyridinyl, thiazolyl, isothiazolyl, Thienyl, furyl, pyrrolyl, pyrazolyl, pyrimidinyl, tetrahydrofuranyl, 4,5-dihydrothiazol-2-yl, 2-cyanoimido-4-oxo-1,3-thiazolidine- 3-yl, 2-cyanoimino-4-oxo-1,3-thiazin-3-yl, oxazolyl, isoxazolyl, 1H-tetrazolyl, 1H-1, 2, 3 -triazolyl, 4H-1,2,4-triazolyl, 1,2,3-thiadiazolyl, 1,2,4-thiadiazolyl, 1,3,4-thiadiazolyl, 1,2,4-
  • heterocyclic ring system refers to a ring system in which at least one ring in the ring system is a heterocyclic ring.
  • heteromatic ring system refers to a system in which at least one ring in the ring system is an aromatic ring.
  • the term "8- to 12-membered heteroaryl bicyclic ring system” or “8- to 14-membered heteroaryl bicyclic or tricyclic ring system” may be selected from the group consisting of benzofuran, benzo[b] Thiophene, anthracene, quinoline, isoquinoline, 1H-carbazole, 1H-benzo[d]imidazole, benzo[d]thiazole, benzo[d]oxazole, benzo[d]isoxazole, Benzo[d][1,2,3]thiadiazole, 2,3-dihydroimidazo[1,2-a]pyridine, quinazoline, quinoxaline, porphyrin, pyridazine, 1,8 -naphthyridine, 4,5,6,7-tetrahydrobenzo[b]thiophene, benzo[b]thiophene-1,1-dioxane, 8H-ind
  • alkyl refers to a group in which one hydrogen atom is absent from an alkane molecule; the term “alkylene” refers to a group in which two hydrogen atoms are absent from an alkane molecule.
  • alkenylene alkynylene
  • cycloalkylene cycloalkenylene
  • phenylene naphthylene
  • heterocyclylene or "Asia”
  • heteroaryl or tricyclic ring system is similar.
  • the groups of the present invention may be substituted with a substituent selected from the group consisting of halogen, cyano, nitro, C 1-6 unless otherwise specified as "substituted or unsubstituted".
  • inert solvent a variety of solvents that do not react with the starting materials, including various linear, branched or cyclic alcohols, ethers or ketones, alkyl halides, 1,4-dioxane, acetonitrile, tetrahydrofuran, N, N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), and the like.
  • the compounds of the invention may contain one or more asymmetric centers and thus occur as racemates, racemic mixtures, single enantiomers, diastereomeric compounds and single diastereomers.
  • the asymmetric center that can exist depends on the nature of the various substituents on the molecule. Each such asymmetric center will independently produce two optical isomers, and all Possible optical isomers and diastereomeric mixtures and pure or partially pure compounds are included within the scope of the invention.
  • the invention includes all isomeric forms of the compounds.
  • Y or Q when Y or Q is a covalent bond, it means that the groups on both sides of Y or Q are linked by a covalent bond.
  • active substance of the invention or “active compound of the invention” means a compound of the formula (I), an optical isomer, a cis-trans isomer or a pesticide-acceptable salt thereof. Its heterocyclic structure containing N and S has remarkable nematicidal activity, and the nematicidal spectrum is broad and stable.
  • agrochemically acceptable salt means that the anion of the salt is known and acceptable in forming a pharmaceutically acceptable salt of a nematicide.
  • the salt is water soluble.
  • the acid addition salts formed from the compounds of formula (I) include salts of mineral acids, such as hydrochlorides, phosphates, sulfates, nitrates; and salts comprising organic acids, such as acetates, Benzoate and the like.
  • the active substance of the present invention can be used as a control and elimination of a wide range of agroforestry plant parasitic nematodes.
  • "nematicidal agent” is a collective term for a substance having an action of controlling all plant parasitic nematodes mentioned herein.
  • plant-parasitic nematodes include, but are not limited to, root-knot nematodes, such as Meloidogyne arenaria, Meloidogyne chitwoodi, Meloidogyne exigua, Meloidogyne hapla , Meloidogyne incognita, Meloidogyne javanica, and other genus Meloidogyne; cyst nematodes, such as Globodera rostochiensis, Globodera pallida, Globodera tabacum, and other genus Globodera; heterologous nematodes, such as Heterodera avenae, Heterodera glycines, and Heterodera schachtii ), Heterodera trifolii, and other Heterodera; nematode nematodes, such as Anguina funesta, Anguina tritici, and other genus Anguina );
  • elegans such as Ditylenchus destructor, Ditylenchus dipsaci, Ditylenchus myceliophagus, and other Ditylenchus; Cone nematodes such as Dolichodorus; Nematodes, such as Helicopterchus dihystera, Helicotylenchus multicintus, and other Helicotyllenus; sheath nematodes, such as Hemicycliophora and Hemicriconemoides; Nematodes, such as the collateral nematode (Hoploaimus columbus) And other genus Hoploaimus; pseudo-root nodule nematodes such as Nacobbus aberrans and other genus Nacobbus; needle nematodes such as Longidorus elongatus and other species of the genus Nematode ( N.
  • elegans such as Paratylenchus
  • root rot nematodes such as Pratylenchus brachyurus, Pratylenchus coffee, Pratylenchus zeae, puncture short Nematode (Pratylenchus penetrans), and other genus Pratylenchus
  • perforated nematodes such as Radopholus similis and other genus Radopholus
  • kidney-shaped nematodes such as Rotylenchus robustus And other Rotylenchus
  • Remnant nematodes such as the genus Trichodorus primitivus and other genus Trichodorus
  • dwarf nematodes such as the Tylenchorhynchus claytoni, indefinite dwarf Nematode (Tylenchorhynchus dubius), and other dwarf nematodes (Tylenchorhynchus); citrus nematodes, such as citrus half Tylenchulus semipene
  • the compounds of the present invention have a particularly good control effect against Meloidogyne incognita.
  • the active substance of the present invention can be prepared into a nematicidal composition in a conventional manner.
  • These active compounds can be formulated into conventional preparations such as solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols, natural and synthetic materials impregnated with active substances, in polypolymers Microcapsules, coatings for seeds, and preparations for use with burning devices, such as smoked cartridges, smoked cans and smokers, as well as ULV cold mist and hot fog (Warm Mist) formulation.
  • preparations can be produced by known methods, for example, by mixing the active compound with an extender which is a liquid or liquefied gas or solid diluent or carrier, and optionally a surfactant, an emulsifier and/or A dispersant and/or a foam former.
  • an extender which is a liquid or liquefied gas or solid diluent or carrier
  • a surfactant for example, an organic solvent can also be used as an auxiliary.
  • an organic solvent can also be used as an auxiliary.
  • a liquid solvent When a liquid solvent is used as the diluent or carrier, it is basically suitable, such as: aromatic hydrocarbons such as xylene, toluene or alkylnaphthalene; chlorinated aromatic or chlorinated aliphatic hydrocarbons such as chlorobenzene, vinyl chloride Or methylene chloride; aliphatic hydrocarbons such as cyclohexane or paraffin, such as mineral oil fractions; alcohols such as ethanol or ethylene glycol and their ethers and lipids; ketones such as acetone, methyl ethyl ketone, methyl isobutyl Ketone or cyclohexanone; or less common polar solvents such as dimethylformamide and dimethyl sulfoxide, and water.
  • aromatic hydrocarbons such as xylene, toluene or alkylnaphthalene
  • chlorinated aromatic or chlorinated aliphatic hydrocarbons such as chlorobenzene, vinyl chloride Or
  • the diluent or carrier of the liquefied gas refers to a liquid which will become a gas at normal temperature and pressure, such as an aerosol propellant such as a halogenated hydrocarbon and butane, propane, nitrogen and carbon dioxide.
  • the solid carrier may be ground natural minerals such as kaolin, clay, talc, quartz, activated clay, montmorillonite, or diatomaceous earth; and ground synthetic minerals such as highly dispersed silicic acid, alumina And silicates.
  • the solid carrier for the granules is ground and graded natural zircon, such as calcite, marble, pumice, sepiolite and dolomite, And inorganic and organic coarse powder synthesized particles, and organic materials such as sawdust, coconut shell, corn cobs and tobacco stem particles.
  • Emulsified columns of nonionic and anionic agents can be used as emulsifiers and/or foam formers.
  • polyoxyethylene-fatty acid esters polyoxyethylene-fatty alcohol ethers, such as alkaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, aryl sulfonates, and white Protein hydrolysate.
  • Dispersing agents include lignin sulfite waste liquors and methylcellulose.
  • Binders such as carboxymethylcellulose and natural and synthetic polymers in the form of powders, granules or emulsions, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, may be employed in the formulation.
  • Colorants such as inorganic dyes such as iron oxide, oxidized diamond and Prussian blue; organic dyes such as azo dyes or metal phthalocyanine dyes; and trace nutrients such as iron, manganese, boron, copper, cobalt, aluminum may be used. And zinc salts, etc.
  • the active compounds of the present invention may be formulated as a mixture with other active compounds in their commercial preparations or in the dosage forms prepared from these preparations, these other active compounds being insecticides, bactericides, fungicides, Herbicides, growth control agents, etc.
  • Insecticides include, for example, phosphates, carbamates, chlorinated hydrocarbons, and substances produced by microorganisms such as avermectin, and fungicides including methoxy acrylates, amides, triazoles Wait.
  • the active compounds of the invention may also be formulated as a mixture with synergists in their commercial preparations or in the dosage forms prepared from these preparations, which are compounds which increase the action of the active compound, due to the activity The compound itself is active, and it is not necessary to add a synergist.
  • formulations usually contain from 0.001 to 99.99% by weight, preferably from 0.01 to 99.9% by weight, more preferably from 0.05 to 90% by weight, based on the total weight of the nematicide composition, of the active compound of the invention.
  • concentration of the active compound in the commercial preparation or the dosage form used can vary within a wide range.
  • concentration of active compound in the dosage form used may range from 0.0000001 to 100% (g/v), preferably between 0.0001 and 1% (g/v).
  • the compound of the formula (I) of the present invention can be produced by the following method, however, the conditions of the method, such as the reactant, the solvent, the base, the amount of the compound used, the reaction temperature, the time required for the reaction, and the like are not limited to the following explanations. .
  • the compounds of the present invention may also be conveniently prepared by combining various synthetic methods described in the specification or known in the art, and such combinations are readily made by those skilled in the art to which the present invention pertains.
  • each reaction is usually carried out in an inert solvent at a reaction temperature of -20 to 120 ° C (preferably -10 to 0 ° C or 20 to 30 ° C or 80 to 100 ° C).
  • the reaction time is usually from 2 to 24 hours, preferably from 4 to 18 hours.
  • the base used in the reaction includes, but is not limited to, triethylamine, diisopropylethylamine, diethylamine, piperidine, piperazine, morpholine, N-methylmorpholine, triethylenediamine ( DABCO), 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), 1,5-diazabicyclo[4.3.0]non-5-ene (DBN)
  • potassium carbonate potassium hydrogencarbonate, sodium carbonate, sodium hydrogencarbonate, cesium carbonate, sodium hydroxide, potassium hydroxide, sodium methoxide, sodium ethoxide, or a combination thereof.
  • the starting compound of the formula (d) of the present invention can be synthesized by a method comprising the following steps:
  • a compound of the formula (a) and BTC are reacted in an inert solvent at a constant temperature (e.g., -10 to -5 ° C) to obtain a compound of the formula (b).
  • a constant temperature e.g., -10 to -5 ° C
  • the method comprises the steps of:
  • the compound of the formula (II) of the present invention can be synthesized by the following method:
  • X, Y, L, M, G and A are as defined above, and n is an integer from 0 to 5;
  • the compound of formula (e) and (p1) in the presence of a base (such as potassium carbonate, etc.), an inert solvent (such as DMF or acetone) as a solvent, the compound of formula (e) and (p1)
  • a base such as potassium carbonate, etc.
  • an inert solvent such as DMF or acetone
  • the compound is reacted at a certain temperature (for example, 80 to 90 ° C or reflux) for a certain period of time (for example, 8 to 12 hours). After the reaction is completed, it is cooled to room temperature, and the solvent is distilled off under reduced pressure, and water is added to the residue. The organic phase is washed with saturated brine, dried over anhydrous sodium sulfate, concentrated, and then purified to give the compound of formula (II).
  • a base such as potassium carbonate, etc.
  • an inert solvent such as DMF or acetone
  • the compound of the formula (II) can be synthesized by the following method:
  • X, Y, L, M, G and A are as defined above, and n is an integer from 0 to 5;
  • the compound of the formula (III) of the present invention can be synthesized by the following method:
  • X, L, M, G and A are as defined above, and n is an integer from 0 to 5;
  • the compound of the formula (IV) of the present invention can be synthesized by the following method:
  • X, L, M, G and A are as defined above, and n is an integer from 0 to 5;
  • the compound of the formula (V-VI) of the present invention can be synthesized by the following method:
  • X, L, M, G and A are as defined above, and n is an integer from 0 to 5;
  • the compound of the formula (n1) is reacted with the compound of the formula (o'1) at room temperature for a period of time (for example, 8 to 12 hours). After the reaction is completed, it is suction filtered, and the filter cake is weighed with absolute ethanol. Crystallization gives the compound of formula (V).
  • an inert solvent such as acetonitrile
  • the compound of the formula (n1) is reacted with the compound of the formula (o'2) at room temperature for a period of time (for example, 8 to 12 hours). After the reaction is completed, the filtrate is concentrated by suction, and the filtrate is concentrated. Isolation gives the compound of formula (VI).
  • an inert solvent such as dichloromethane
  • the intermediate product is contained in an amount of 10 to 99.99% by weight; preferably 20 to 90% by weight; more preferably 50 to 80% by weight.
  • the inventors can purify the intermediate product and then carry out the next reaction; of course, the reaction mixture containing the compound can be directly subjected to the next reaction.
  • the synthesis of the target compound was similar to the step 1.4 of Example 1, except that 3-(4-bromobutyl)-7-fluorobenzo[d][1,2,3]triazin-4 (3H) was used. - Ketone instead of 3-(3-bromopropyl)-7-chlorobenzo[d][1,2,3]triazin-4(3H)-one. Yellow solid, yield 53%.
  • the synthesis of the target compound was similar to the step 1.4 of Example 1, except that 3-(5-bromopentyl)-6-methylbenzo[d][1,2,3]triazine-4 (3H) was used.
  • the ketone replaces 3-(3-bromopropyl)-7-chlorobenzo[d][1,2,3]triazin-4(3H)-one. Light yellow solid in 65% yield.
  • the synthesis of the target compound was similar to the step 1.4 of Example 1, except that 3-(6-bromohexyl)-7-methoxybenzo[d][1,2,3]triazine-4 (3H) was used.
  • the ketone replaces 3-(3-bromopropyl)-7-chlorobenzo[d][1,2,3]triazin-4(3H)-one. Light yellow solid, yield 41%.
  • the synthesis of the target compound was similar to the step 1.4 of Example 1, except that 3-(3-bromopropyl)-6-methylthieno[3,2-d][1,2,3]triazine was used. -4(3H)-one instead of 3-(3-bromopropyl)-7-chlorobenzo[d][1,2,3]triazin-4(3H)-one. Yellow solid, yield 18%.
  • the synthesis of the target compound was similar to the step 9.2 of Example 9, except that 3-(4-bromobutyl)-7-vinylbenzo[d][1,2,3]triazine-4 (3H) was used. )-ketone instead of 3-(4-bromobutyl)-7-vinylbenzo[d][1,2,3]triazin-4(3H)-one, with 6-bromospiro[porphyrin- 3,2'-[1,3]dioxan-2-one replaces spiro[porphyrin-3,2'-[1,3]dioxolan-2-one. White solid, yield 88%.
  • Triazine-4(3H)-one, 0.036 g (0.192 mmol) of cuprous iodide and 0.34 ml (2.4 mmol) of triethylamine were added with 5 ml of acetonitrile, and reacted at room temperature for 2 hours. An appropriate amount of silica gel was added to the reaction mixture, and the solvent was evaporated.
  • the preparation method of 7-fluorobenzo[d][1,2,3]triazin-4(3H)-one is similar to the step 1.1 of Example 1, except that 2-amino-4-fluorobenzoic acid is used. Instead of 2-amino-4-chlorobenzoic acid.
  • the synthesis of the target compound was similar to the step 15.3 of Example 15 except that 3-(3-hydroxypropyl)-5-bromobenzo[d][1,2,3]triazin-4 (3H) was used. - Ketone instead of 3-(3-hydroxypropyl)-7-fluorobenzo[d][1,2,3]triazin-4(3H)-one. White solid, yield 26%.
  • the synthesis of the target compound was similar to the step 15.3 of Example 15 except that 3-(3-hydroxypropyl)-6-trifluoromethylbenzo[d][1,2,3]triazine-4 was used. (3H)-ketone instead of 3-(3-hydroxypropyl)-7-fluorobenzo[d][1,2,3]triazin-4(3H)-one. White solid in 16% yield.
  • the preparation of the target compound was similar to the step 23.2 of Example 23, except that 3-(3-aminopropyl)-7-nitrobenzo[d][1,2,3]triazine-4 (3H) was used.
  • )-ketone instead of 3-(3-aminopropyl)benzo[d][1,2,3]triazin-4(3H)-one with 3-(5-ethyl-1,2,4- Oxadiazol-3-yl)benzoyl isothiocyanate replaces 2-(trifluoromethoxy)benzoyl isothiocyanate. Light yellow solid in 65% yield.
  • Root-knot nematode belongs to the genus Nematode, Tylenchida, Suborder, Subspecies, Heteroderidea, Meloidogyninae, Root-knot nematode, which is a serious hazard. Plant parasitic nematodes.
  • the sample to be tested is prepared into a liquid solution at a desired concentration, and a sufficient amount of second-instar larvae of the root-knot nematode is prepared. After planting a one-week old cucumber seedling into a test tube, an appropriate amount of the prepared liquid was added to the test tube, and about 2000 larvae were inserted into each test tube. The tubes were placed at 20-25 ° C for 10 hours under light, and after 20 days, the results were counted and the number of roots on the roots of each plant was counted. Each sample was tested 3 times, and each sample was subjected to 4 replicate treatments per test.
  • Distilled water was used as a blank control, distilled water plus root-knot nematode was used as a negative control, and phenylphosphorus and avermectin solutions were used as positive controls.
  • Inhibition rate (%) (negative control score - test group score) / negative control score ⁇ 100%
  • Y is "-" to indicate that Y is a covalent bond
  • M is "/" to indicate that M is none.
  • Embodiment 26 A composition comprising a nematicidal agent of the compound of the present invention
  • the following components were prepared in proportion: 5.0% by weight, the same as any of the compounds II-1 to VI-36 (Tables 2 to 6); 30.0% polyvinylpyrrolidone-vinyl acetate copolymer; 30.0% Alkyl polyglycosides; 15.0% oleic acid glyceride; 20.0% water.
  • the following components were prepared in proportion: 65.0% of any of the compounds II-1 to VI-36 (Tables 2 to 6); 2.0% of dodecylphenol polyglycol ether; 4.0% of sodium lignosulfonate; 6.0% sodium aluminum silicate; 23.0% montmorillonite (calcined).
  • the following components were prepared in proportion: 20.00% of any of the compounds II-1 to VI-36 (Tables 2 to 6); 5.00% polyvinylpyrrolidone-vinyl acetate copolymer; 5.00% montanic acid wax; 1.00% wood Calcium sulfonate; 1.00% polyoxyethylene/polyoxypropylene block copolymer; 2.00% stearyl alcohol (POE 20); 0.20% polyorganosilicon; 0.05% colorant red dye; 65.75% water.

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Abstract

本发明涉及一种具有杀线虫活性的三嗪杂环化合物及其制法和用途。具体地，本发明公开了具有式(I)化合物或其光学异构体、顺反异构体或农药学上可接受的盐，及其制备方法。本发明还公开了包含上述化合物的农用组合物及其用途。上述化合物具有优异的杀线虫活性。

Description

一种具有杀线虫活性的三嗪杂环化合物及其制法和用途 技术领域
本发明属于农药领域。具体地，本发明涉及一种具有杀线虫活性的三嗪杂环化合物及其制法和用途。
背景技术
植物寄生线虫是一类危害极大的病原微生物，其分布范围广、种类繁多、环境适应能力强，可以寄生在植物的根系、茎、叶、种子、幼芽和果实内，能通过取食活动对寄主植物造成机械损伤，并掠夺寄主植物的营养，尤其是其食道腺分泌物会导致寄主植物发生一系列病变，还会和其它病原微生物共同侵染寄主植物，引起复合病害，造成产量损失。在全球范围内，植物寄生线虫每年造成的农业损失高达1000亿美元以上，严重制约了农业经济的发展。
农业上对线虫的防治手段有很多，目前以化学防治为主。广泛应用的化学杀线虫剂主要为高毒性、高残留的有机磷或氨基甲酸酯类农药，如硫线磷、丙线磷、苯线磷、噻唑磷、涕灭威、杀线威和克百威等，对人类与其它非靶标生物的安全性低，对土壤、水源和农产品也会造成不同程度的污染。另外，由于品种单一，该类杀线虫剂被过量、频繁使用，已经引起了严重的抗药性，使得线虫的防治难度日益增加。因此，寻找高效、低毒和环境相容性好的结构新颖的化学杀线虫剂，成为本领域迫切需要解决的技术问题。
发明内容
本发明的目的之一是提供一种高效、低毒和环境相容性好的结构新颖的化学杀线虫剂及其制备方法和应用。
在本发明的第一方面中，提供了一种具有通式(I)所示结构的化合物，或所述化合物的光学异构体、顺反异构体或农药学上可接受的盐：
Figure PCTCN2016071608-appb-000001
式中：
X为O或S；
Y为O、S、S(＝O)
Figure PCTCN2016071608-appb-000002
S(＝O)2
Figure PCTCN2016071608-appb-000003
NH或共价键；
Q为羰基
Figure PCTCN2016071608-appb-000004
硫羰基-氨基
Figure PCTCN2016071608-appb-000005
硫羰基-氨基-羰基
Figure PCTCN2016071608-appb-000006
或共价键；
当L为取代或未取代的C1-6亚烷基、取代或未取代的C1-6卤代亚烷基、取代或未取 代的C2-6亚烯基、取代或未取代的C2-6卤代亚烯基、取代或未取代的C2-6亚炔基、取代或未取代的C2-6卤代亚炔基、取代或未取代的C3-7亚环烷基、取代或未取代的C5-7亚环烯基、取代或未取代的亚苯基、取代或未取代的亚萘基、取代或未取代的5元或6元亚杂环基、或取代或未取代的8元至14元亚杂芳二环或三环环系，所述取代是指被选自下组的一个或多个基团所取代：卤素、氰基、硝基、R’、OR’、Si(R’)3、NR’R"、C(O)R’、C(O)OR’、C(O)NR’R"、SR’、S(O)mR1、S(O)2NR’R"、OC(O)R1、OC(O)NR’R"、OS(O)2R1、OS(O)2NR’R"、N(R2)C(O)R1、N(R2)C(O)NR’R"、N(R2)S(O)2R1或N(R2)S(O)2NR’R"时；M为H、C1-6烷基、C1-6卤代烷基、C2-6烯基、C2-6卤代烯基、取代或未取代的C2-6炔基、C2-6卤代炔基，或取代或未取代的C3-7环烷基、取代或未取代的C5-7环烯基、取代或未取代的苯基、取代或未取代的萘基、取代或未取代的5元或6元杂环基、或取代或未取代的8元至14元杂芳二环或三环环系，所述取代是指被选自下组的一个或多个基团所取代：卤素、氰基、硝基、R’、OR’、Si(R’)3、NR’R"、C(O)R’、C(O)OR’、C(O)NR’R"、SR’、S(O)mR1、S(O)2NR’R"、OC(O)R1、OC(O)NR’R"、OS(O)2R1、OS(O)2NR’R"、N(R2)C(O)R1、N(R2)C(O)NR’R"、N(R2)S(O)2R1或N(R2)S(O)2NR’R"；或
当L为取代或未取代的C1-6烷基、取代或未取代的C1-6卤代烷基、取代或未取代的C2-6烯基、取代或未取代的C2-6卤代烯基、取代或未取代的C2-6炔基、取代或未取代的C2-6卤代炔基、取代或未取代的C3-7环烷基、取代或未取代的C5-7环烯基、取代或未取代的苯基、取代或未取代的萘基、取代或未取代的5元或6元杂环基、或取代或未取代的8元至14元杂芳二环或三环环系，所述取代是指被选自下组的一个或多个基团所取代：卤素、氰基、硝基、R’、OR’、Si(R’)3、NR’R"、C(O)R’、C(O)OR’、C(O)NR’R"、SR’、S(O)mR1、S(O)2NR’R"、OC(O)R1、OC(O)NR’R"、OS(O)2R1、OS(O)2NR’R"、N(R2)C(O)R1、N(R2)C(O)NR’R"、N(R2)S(O)2R1或N(R2)S(O)2NR’R"时；M为无；
且A为取代或未取代的苯基、取代或未取代的萘基、取代或未取代的5元或6元杂环基、或取代或未取代的8元至14元杂芳二环或三环环系，所述取代是指被选自下组的一个或多个基团所取代：卤素、氰基、硝基、R’、OR’、Si(R’)3、NR’R"、C(O)R’、C(O)OR’、C(O)NR’R"、SR’、S(O)mR1、S(O)2NR’R"、OC(O)R1、OC(O)NR’R"、OS(O)2R1、OS(O)2NR’R"、N(R2)C(O)R1、N(R2)C(O)NR’R"、N(R2)S(O)2R1或N(R2)S(O)2NR’R"；
G表示A的任意一个或多个位置上的取代基，且G为H、C1-6烷基、C1-6卤代烷基、C2-6烯基、C2-6卤代烯基、取代或未取代的C2-6炔基、C2-6卤代炔基，或取代或未取代的C3-7环烷基、取代或未取代的C5-7环烯基、取代或未取代的苯基、取代或未取代的萘基、取代或未取代的5元或6元杂环基、或取代或未取代的8元至12元杂芳二环环系，所述取代是指被选自下组的一个或多个基团所取代：卤素、氰基、硝基、R’、OR’、Si(R’)3、NR’R"、C(O)R’、C(O)OR’、C(O)NR’R"、SR’、S(O)mR1、S(O)2NR’R"、OC(O)R1、OC(O)NR’R"、OS(O)2R1、OS(O)2NR’R"、N(R2)C(O)R1、N(R2)C(O)NR’R"、N(R2)S(O)2R1或N(R2)S(O)2NR’R"；
其中，R’、R"各自独立地为H、C1-6烷基、C1-6卤代烷基、C2-6烯基、C2-6卤代烯基、C2-6炔基、C2-6卤代炔基，或取代或未取代的C3-7环烷基、取代或未取代的C5-7环烯基、取代或未取代的苯基、取代或未取代的萘基、取代或未取代的5元或6元杂环基、或取代或未取代的8元至12元杂芳二环环系，所述取代是指选自下组的一个或多个基团所取代：卤素、氰基、硝基、C1-6烷基、C1-6卤代烷基、C2-6烯基、C2-6卤代烯基、C2-6炔基、C2-6卤代炔基、羟基、羟基C1-4烷基、OR3、NR3R4、C(O)R3、C(O)OR3、C(O)NR3R4、SR3、S(O)mR5、S(O)2NR3R4、OC(O)R5、OC(O)NR3R4、OS(O)2R5、OS(O)2NR3R4、N(R6)C(O)R5、N(R6)C(O)NR3R4、N(R6)S(O)2R5或N(R6)S(O)2NR3R4；
R1为C1-6烷基、C1-6卤代烷基、C2-6烯基、C2-6卤代烯基、C2-6炔基、C2-6卤代炔基，或取代或未取代的C3-7环烷基、取代或未取代的C5-7环烯基、取代或未取代的苯基、取代或未取代的萘基、取代或未取代的5元或6元杂环基、或取代或未取代的8元至12元杂芳二环环系，所述取代是指被选自下组的一个或多个基团所取代：卤素、氰基、硝基、C1-6烷基、C1-6卤代烷基、C2-6烯基、C2-6卤代烯基、C2-6炔基、C2-6卤代炔基、OR3、NR3R4、C(O)R3、C(O)OR3、C(O)NR3R4、SR3、S(O)mR5、S(O)2NR3R4、OC(O)R5、OC(O)NR3R4、OS(O)2R5、OS(O)2NR3R4、N(R6)C(O)R5、N(R6)C(O)NR3R4、N(R6)S(O)2R5或N(R6)S(O)2NR3R4；
R2为H、C1-6烷基、C1-6卤代烷基、C2-6烯基、C2-6卤代烯基、C2-6炔基或C2-6卤代炔基，或取代或未取代的C3-7环烷基、取代或未取代的C5-7环烯基、取代或未取代的苯基、取代或未取代的萘基、取代或未取代的5元或6元杂环基、或取代或未取代的8元至12元杂芳二环环系，所述取代是指被选自下组的一个或多个基团所取代：卤素、氰基、硝基、C1-6烷基、C1-6卤代烷基、C2-6烯基、C2-6卤代烯基、C2-6炔基、C2-6卤代炔基、OR3、NR3R4、C(O)R3、C(O)OR3、C(O)NR3R4、SR3、S(O)mR5、S(O)2NR3R4、OC(O)R5、OC(O)NR3R4、OS(O)2R5、OS(O)2NR3R4、N(R6)C(O)R5、N(R6)C(O)NR3R4、N(R6)S(O)2R5或N(R6)S(O)2NR3R4；
其中，R3、R4、R6各自独立地为H、C1-6烷基、C1-6卤代烷基、C2-6烯基、C2-6卤代烯基、C2-6炔基或C2-6卤代炔基；
R5为C1-6烷基、C1-6卤代烷基、C2-6烯基、C2-6卤代烯基、C2-6炔基或C2-6卤代炔基；
m为1或2；
n为0、1、2、3、4或5。
在另一优选例中，所述化合物选自下组：
Figure PCTCN2016071608-appb-000007
Figure PCTCN2016071608-appb-000008
上述各式中，X、L、G、A、M和n的定义如上所述，Y为O、S、S(＝O)、S(＝O)2或共价键。
在另一优选例中，X为O或S。
在另一优选例中，L为取代或未取代的C1-6亚烷基、取代或未取代的C1-6卤代亚烷基、取代或未取代的C2-6亚烯基、取代或未取代的C2-6卤代亚烯基、取代或未取代的C2-6亚炔基、取代或未取代的C3-7亚环烷基、取代或未取代的C5-7亚环烯基、取代或未取代的亚苯基、取代或未取代的亚萘基、取代或未取代的5元或6元亚杂环基、或取代或未取代的8元至12元亚杂芳二环环系，所述取代是指被选自下组的一个或多个基团所取代：卤素、氰基、硝基、C1-4烷基、C1-4卤代烷基、C1-4烷氧基、C1-4烷基-羰基、C1-4烷氧基-羰基、C1-4烷基胺基-羰基或苯基胺基-羰基；或
L为取代或未取代的C1-6烷基、取代或未取代的C1-6卤代烷基、取代或未取代的C2-6烯基、取代或未取代的C2-6卤代烯基、取代或未取代的C2-6炔基、取代或未取代的C3-7环烷基、取代或未取代的C5-7环烯基、取代或未取代的苯基、取代或未取代的萘基、取代或未取代的5元或6元杂环基、或取代或未取代的8元至12元杂芳二环环系，所述取代是指被选自下组的一个或多个基团所取代：卤素、氰基、硝基、C1-4烷基、C1-4卤代烷基、C1-4烷氧基、C1-4烷基-羰基、C1-4烷氧基-羰基、C1-4烷基胺基-羰基或苯基胺基-羰基。
在另一优选例中，L为实施例中表2～表6中L列中所示的任意基团。
在另一优选例中，M为无；或M为H、C1-6烷基、C1-6卤代烷基、C2-6烯基、C2-6卤代烯基、C2-6炔基、三甲基硅烷基乙炔基，或取代或未取代的C3-7环烷基、取代或未取代的C5-7环烯基、取代或未取代的苯基、取代或未取代的萘基、取代或未取代的5元或6元杂环基、或取代或未取代的8元至14元杂芳二环或三环环系，所述取代是指被选自下组的一个或多个基团所取代：卤素、氰基、硝基、C1-4烷基、C1-4卤代烷基、C1-4烷氧基、C1-4烷基-羰基、C1-4烷氧基-羰基、C1-4烷基胺基-羰基或苯基胺基-羰基。
在另一优选例中，M为实施例中表2～表6中M列中所示的任意基团。
在另一优选例中，A为取代或未取代的苯基、取代或未取代的萘基、取代或未取代的5元或6元杂环基、或取代或未取代的8元至12元杂芳二环环系，所述取代是指被选自下组的一个或多个基团所取代：卤素、氰基、硝基、C1-4烷基、C1-4卤代烷基、C1-4烷氧基、C1-4卤代烷氧基、苯氧基、胺基磺酸基、胺基-羰基、C1-4烷基-羰基、C1-4烷氧基-羰基、C1-4烷基胺基-羰基或苯基胺基-羰基。
在另一优选例中，G为H、C1-6烷基、C1-6卤代烷基、C2-6烯基、C2-6卤代烯基、C2-6炔基、三甲基硅烷基乙炔基，或取代或未取代的C3-7环烷基、取代或未取代的C5-7环烯 基、取代或未取代的苯基、取代或未取代的萘基、取代或未取代的5元或6元杂环基或取代或未取代的8元至12元杂芳二环环系，所述取代是指被选自下组的一个或多个基团所取代：卤素、氰基、硝基、C1-4烷基、C1-4卤代烷基、C1-4烷氧基、C1-4烷基-羰基、C1-4烷氧基-羰基、C1-4烷基胺基-羰基或苯基胺基-羰基。
在另一优选例中，
Figure PCTCN2016071608-appb-000009
为实施例中表2～表6中
Figure PCTCN2016071608-appb-000010
列中所示的任意基团。
在另一优选例中，所述化合物为实施例中表2～表6中所列举的化合物。
本发明第二方面中提供了一种农用组合物，其包含：
(1)0.001-99.99重量％的本发明第一方面所述的化合物、或所述化合物的光学异构体、顺反异构体或农药学上可接受的盐、或者它们的组合；以及
(2)农药学上可接受的载体和/或赋形剂。
本发明第三方面中提供了本发明第一方面所述的化合物、或所述化合物的光学异构体、顺反异构体或农药学上可接受的盐或本发明第二方面所述农用组合物的用途，用于杀灭或预防线虫或用于制备杀线虫剂组合物。
在另一优选例中，用于杀灭或预防农林植物寄生线虫或用于制备杀灭或预防农林植物寄生线虫的杀线虫剂组合物。
本发明第四方面中提供了一种本发明第一方面所述的化合物、或所述化合物的光学异构体、顺反异构体或农药学上可接受的盐的制备方法，
(A)所述方法包括步骤：
(1)在惰性溶剂中，将式(a)化合物与双(三氯甲基)碳酸酯(BTC)进行关环反应，得到式(b)化合物：
(2)在惰性溶剂中，将式(b)化合物与碳酸铵进行开环反应，得到式(c)化合物：
(3)在惰性溶剂中，将式(c)化合物经重氮化反应、关环反应，得式(d)化合物：
Figure PCTCN2016071608-appb-000011
(4)在惰性溶剂中，在碱存在下，式(d)化合物与BrCH2(CH2)nBr反应，得到式(e)化合物；
(5)在惰性溶剂中，将式(e)化合物与式(f)化合物或式(p)化合物(H-Y-Q-L-M)反应，从而得到式(I)化合物：
Figure PCTCN2016071608-appb-000012
或(B)所述方法包括步骤：
(4’)在惰性溶剂中，在碱存在下，式(d)化合物与BrCH2(CH2)nC≡CH反应，得式(g)化合物：
(5’)在惰性溶剂中，将式(g)化合物与式(h)化合物反应，从而得式(I)化合物：
Figure PCTCN2016071608-appb-000013
或(C)所述方法包括步骤：
(4”)在惰性溶剂中，在碱存在下，式(d)化合物与BrCH2(CH2)nYH反应，得式(i)化合物：
(5”)在惰性溶剂中，将式(i)化合物与式(k)化合物反应，从而得到式(I)化合物：
Figure PCTCN2016071608-appb-000014
或(D)所述方法包括步骤：
(5”’)在惰性溶剂中，在碱存在下，将式(e)化合物与式(m)化合物反应，然后经脱保护得式(n)化合物：
(6)在惰性溶剂中，将式(n)化合物与式(o)化合物反应，从而得到式(I)化合物：
Figure PCTCN2016071608-appb-000015
或(E)所述方法包括步骤：
(6’)在惰性溶剂中，式(n)化合物与式(o’)化合物反应，得到式(I)化合物：
Figure PCTCN2016071608-appb-000016
或(F)所述方法包括步骤：
(5””)在惰性溶剂中，在碱存在下，式(e)化合物与式(p)化合物反应，得到式(I)化合物：
Figure PCTCN2016071608-appb-000017
上述各式中，X、Y、Q、L、M、A、G和n的定义如上所述。
在本发明的第五方面中提供了一种杀线虫和/或防线虫方法，所述方法包括步骤：将本发明第一方面所述的化合物或第二方面所述的农用组合物施加于遭受或可能遭受线虫害的植物体、其周围的土壤或环境中。
在本发明的第六方面中，提供了制备本发明第二方面所述农用组合物的方法，所述方法包括步骤：将(1)本发明第一方面中所述的化合物、其光学异构体、顺反异构体或农药学上可接受的盐、或者它们的组合；与(2)农药学上可接受的载体和/或赋形剂进行混合，从而形成所述的农用组合物。
应理解，在本发明范围内中，本发明的上述各技术特征和在下文(如实施例)中具体描述的各技术特征之间都可以互相组合，从而构成新的或优选的技术方案。限于篇幅，在此不再一一累述。
具体实施方式
本发明人经过长期而深入的研究，意外地发现并合成了一系列结构新颖、具有显著杀虫活性的三嗪杂环化合物。在此基础上，发明人完成了本发明。
基团定义
术语“C1-6烷基”是指具有1-6个碳原子的直链或支链烷基，例如甲基、乙基、丙基、异丙基、丁基、异丁基、仲丁基、叔丁基、或类似基团。
术语“C2-6烯基”指具有2-6个碳原子的直链或支链的烯基，例如乙烯基、烯丙基、1-丙烯基、异丙烯基、1-丁烯基、2-丁烯基、或类似基团。
术语“C2-6炔基”是指具有2-6个碳原子的直链或支链的炔基，例如乙炔基、丙炔基、或类似基团。
术语“C3-7环烷基”指具有3-7个碳原子的环状烷基，例如环丙基、环丁基、环戊基、环己基、环庚基、或类似基团。
术语“C5-7环烯基”指具有5-7个碳原子的、具有一个或多个双键的环状烯基，例如环戊烯基、环己烯基、环庚烯基、1,3-环己二烯基、1,4-环己二烯基、或类似基团。
如本文所用，术语“C1-4烷氧基”指具有1-4个碳原子的直链或支链烷氧基，例如甲氧基、乙氧基、丙氧基、异丙氧基、丁氧基、异丁氧基、仲丁氧基、叔丁氧基、或类似基团。
术语“卤素”指氟、氯、溴、或碘。术语“卤代的”指被相同或不同的一个或多个上述卤原子取代的基团，例如三氟甲基、五氟乙基、七氟异丙基、或类似基团。
术语“环”或“环系”指碳环或杂环。
术语“杂环”指形成所述杂环骨架的原子中至少一个原子不是碳，为氮、氧或硫。通常，杂环包含不超过4个氮、不超过2个氧和/或不超过2个硫。除非另外指明，杂环可以是饱和的、部分不饱和的或完全不饱和的环。
术语“环系”指两个或更多个环并在一起的稠环。
如本文所用，术语“5元或6元杂环基”指含一个或多个选自氮、氧或硫的杂原子的五元或六元环，例如吡啶基、噻唑基、异噻唑基、噻吩基、呋喃基、吡咯基、吡唑基、嘧啶基、四氢呋喃基、4,5-二氢噻唑-2-基、2-氰基亚胺基-4-氧-1,3-噻唑烷-3-基、2-氰基亚胺基-4-氧-1,3-噻嗪烷-3-基、噁唑基、异噁唑基、1H-四唑基、1H-1,2,3-三唑基、4H-1,2,4-三唑基、1,2,3-噻二唑基、1,2,4-噻二唑基、1,3,4-噻二唑基、1,2,4-噁二唑基、1,2,5-噁二唑基、1,3,4-噁二唑基或四唑基等。
术语“杂环环系”指环系中的至少一个环是杂环的环系。
术语“杂芳环环系”指环系中的至少一个环为芳族环的体系。
如本文所用，术语“8元至12元杂芳二环环系”或“8元至14元杂芳二环或三环环系”可选自下组：苯并呋喃、苯并[b]噻吩、吲哚、喹啉、异喹啉、1H-吲唑、1H-苯并[d]咪唑、苯并[d]噻唑、苯并[d]噁唑、苯并[d]异噁唑、苯并[d][1,2,3]噻二唑、2,3-二氢咪唑并[1,2-a]吡啶、喹唑啉、喹喔啉、噌啉、酞嗪、1,8-萘啶、4,5,6,7-四氢苯并[b]噻吩、苯并[b]噻吩-1,1-二氧烷、8H-茚并[2,1-b]噻吩、7,8-二氢-6H-环戊[4,5]噻吩并[2,3-d]嘧啶、3,5,6,7-四氢-4H-环戊[4,5]噻吩并[2,3-d]嘧啶-4-酮、螺[吲哚啉-3,2’-[1,3]二氧戊环]-2-酮、螺[吲哚啉-3,2’-[1,3]二氧六环]-2-酮、或吲哚啉-2,3-二酮等。
术语“烷基”是指烷烃分子中少掉一个氢原子而成的基团；术语“亚烷基”是指烷烃分子中少掉两个氢原子而成的基团。类似地，“亚烯基”、“亚炔基”、“亚环烷基”、“亚环烯基”、“亚苯基”、“亚萘基”、“亚杂环基”或“亚杂芳二环或三环环系”的定义类似。
本发明所述的基团除非特别说明是“取代或未取代的”，否则本发明的基团均可被选自下组的取代基所取代：卤素、氰基、硝基、C1-6烷基、C1-6卤代烷基、C2-6烯基、C2-6卤代烯基、C2-6炔基、C2-6卤代炔基、羟基、羟基C1-4烷基、OR3、NR3R4、C(O)R3、C(O)OR3、C(O)NR3R4、SR3、S(O)mR5、S(O)2NR3R4、OC(O)R5、OC(O)NR3R4、OS(O)2R5、OS(O)2NR3R4、N(R6)C(O)R5、N(R6)C(O)NR3R4、N(R6)S(O)2R5或N(R6)S(O)2NR3R4等，其中，所述的R3、R4、R5、R6的定义同前，m为1或2。
惰性溶剂指的是不与原料发生反应的各种溶剂，包括各种直链、支链或环状的醇，醚或酮，卤代烷，1,4-二氧六环，乙腈，四氢呋喃，N,N-二甲基甲酰胺(DMF)，二甲基亚砜(DMSO)等。
本发明的化合物可以含有一个或多个不对称中心，并因此以消旋体、外消旋混合物、单一对映体、非对映异构体化合物和单一非对映体的形式出现。可以存在的不对称中心，取决于分子上各种取代基的性质。每个这种不对称中心将独立地产生两个旋光异构体，并且所有 可能的旋光异构体和非对映体混合物和纯或部分纯的化合物包括在本发明的范围之内。本发明包括化合物的所有异构形式。
本发明的式I化合物中，当Y或Q为共价键时，表示Y或Q两侧的基团通过共价键相连。
本发明活性物质的杀线虫活性
术语“本发明的活性物质”或“本发明的活性化合物”是指通式(I)所示结构的化合物、其光学异构体、顺反异构体或农药学上可接受的盐。其含N、S的杂环结构，具有显著的杀线虫活性，且杀线虫谱广、稳定性强。
术语“农药学上可接受的盐”指该盐的阴离子在形成杀线虫剂药学上可接受的盐时为已了解的和可接受的。较佳地，该盐为水溶性的。合适的，由式(I)的化合物形成的酸加成盐包括无机酸形成的盐，例如盐酸盐、磷酸盐、硫酸盐、硝酸盐；及包括有机酸形成的盐，如醋酸盐，苯甲酸盐等。
本发明的活性物质能用作控制和消灭广泛的农林植物寄生线虫。在本说明书中，“杀线虫剂”是具有防治本文提到的所有植物寄生线虫的作用的物质的统称。
植物寄生线虫的例子包括但不限于：根结线虫，如花生根结线虫(Meloidogyne arenaria)、奇氏根结线虫(Meloidogyne chitwoodi)、短小根结线虫(Meloidogyne exigua)、北方根结线虫(Meloidogyne hapla)、南方根结线虫(Meloidogyne incognita)、爪哇根结线虫(Meloidogyne javanica)，和其它根结线虫属(Meloidogyne)；孢囊线虫，如马铃薯金线虫(Globodera rostochiensis)、马铃薯白线虫(Globodera pallida)、烟草孢囊线虫(Globodera tabacum)，和其它孢囊线虫属(Globodera)；异皮线虫，如禾谷孢囊线虫(Heterodera avenae)、大豆孢囊线虫(Heterodera glycines)、甜菜孢囊线虫(Heterodera schachtii)、三叶草孢囊线虫(Heterodera trifolii)，和其它异皮线虫属(Heterodera)；种瘤线虫，如剪股颖粒线虫(Anguina funesta)、小麦粒线虫(Anguina tritici)和其它粒线虫属(Anguina)；茎和叶芽线虫，如水稻干尖线虫(Aphelenchoides besseyi)、草莓滑刃线虫(Aphelenchoides fragariae)、菊花滑刃线虫(Aphelenchoides ritzemabosi)，和其它滑刃线虫属(Aphelenchoides)；刺线虫，如杂草刺线虫(Belonolaimus longicaudatus)和其它针刺线虫属(Belonolaimus)；松线虫，如松材线虫(Bursaphelenchus xylophilus)和其它伞滑刃线虫属(Bursaphelenchus)；环形线虫，如环纹线虫属(Criconema)、小环线虫属(Criconemella)、轮线虫属(Criconemoides)和中环线虫属(Mesocriconema)；球茎线虫，如腐烂茎线虫(Ditylenchus destructor)、甘薯茎线虫(Ditylenchus dipsaci)、蘑菇茎线虫(Ditylenchus myceliophagus)，和其它茎线虫属(Ditylenchus)；锥线虫，如锥线虫属(Dolichodorus)；螺旋线虫，如双宫螺旋线虫(Helicotylenchus dihystera)、多带螺旋线虫(Helicotylenchus multicintus)，和其它螺旋线虫属(Helicotylenchus)；鞘线虫，如鞘线虫属(Hemicycliophora)和半轮线虫属(Hemicriconemoides)；冠线虫，如哥伦比亚纽带线虫(Hoploaimus columbus) 和其它纽带线虫属(Hoploaimus)；伪根瘤线虫，如异常珍珠线虫(Nacobbus aberrans)和其它珍珠线虫属(Nacobbus)；针线虫，如逸去长针线虫(Longidorus elongatus)和其它长针线虫属(Longidorus)；钉线虫，如钉线虫属(Paratylenchus)；根腐线虫，如最短尾短体线虫(Pratylenchus brachyurus)、咖啡短体线虫(Pratylenchus coffee)、玉米短体线虫(Pratylenchus zeae)、穿刺短体线虫(Pratylenchus penetrans)，和其它短体线虫属(Pratylenchus)；穿孔线虫，如香蕉穿孔线虫(Radopholus similis)和其它穿孔线虫属(Radopholus)；肾形线虫，如肾形肾状线虫(Rotylenchus robustus)和其它肾形线虫属(Rotylenchus)；残根线虫，如原始毛刺线虫(Trichodorus primitivus)和其它毛刺线虫属(Trichodorus)；矮化线虫，如克莱顿矮化线虫(Tylenchorhynchus claytoni)、不定矮化线虫(Tylenchorhynchus dubius)，和其它矮化线虫属(Tylenchorhynchus)；柑桔线虫，如柑桔半穿刺线虫(Tylenchulus semipenetrans)和其它小垫刃线虫属(Tylenchulus)；剑线虫，如美洲剑线虫(Xiphinema americanum)、标准剑线虫(Xiphinema index)、裂尾剑线虫(Xiphinema diversicaudatum)，和其它剑线虫属(Xiphinema)。
本发明涉及的化合物尤其对南方根结线虫(Meloidogyne incognita)有较好的防治效果。
含本发明活性物质的杀线虫剂组合物
可将本发明的活性物质以常规的方法制备成杀线虫剂组合物。这些活性化合物可做成常规的制剂，例如溶液剂、乳剂、混悬剂、粉剂、泡沫剂、糊剂、颗粒剂、气雾剂、用活性物质浸渍的天然的和合成的材料、在多聚物中的微胶囊、用于种子的包衣复方、和与燃烧装置一块使用的制剂，例如烟熏药筒、烟熏罐和烟熏盘，以及ULV冷雾(Cold mist)和热雾(Warm mist)制剂。
这些制剂可用已知的方法生产，例如，将活性化合物与扩充剂混合，这些扩充剂就是液体的或液化气的或固体的稀释剂或载体，并可任意选用表面活性剂即乳化剂和/或分散剂和/或泡沫形成剂。例如在用水作扩充剂时，有机溶剂也可用作助剂。
用液体溶剂作稀释剂或载体时，基本上是合适的，如：芳香烃类，例如二甲苯、甲苯或烷基萘；氯化的芳香或氯化的脂肪烃类，例如氯苯、氯乙烯或二氯甲烷；脂肪烃类，例如环己烷或石蜡，例如矿物油馏分；醇类，例如乙醇或乙二醇以及它们的醚和脂类；酮类，例如丙酮、甲乙酮、甲基异丁基酮或环已酮；或不常用的极性溶剂，例如二甲基甲酰胺和二甲基亚砜，以及水。
液化气的稀释剂或载体，指的是在常温常压下将成为气体的液体，例如气溶胶推进剂，如卤化的烃类以及丁烷、丙烷、氮气和二氧化碳。
固体载体可用磨碎的天然的矿物质，例如高岭土、粘土、滑石、石英、活性白土、蒙脱土、或硅藻土；和磨碎的合成的矿物质，例如高度分散的硅酸、氧化铝和硅酸盐。供颗粒用的固体载体是碾碎的和分级的天然锆石，例如方解石、大理石、浮石、海泡石和白云石，以 及无机和有机粗粉合成的颗粒，和有机材料例如锯木屑、椰子壳、玉米棒子和烟草梗的颗粒等。
非离子的和阴离子的乳化列可用作乳化剂和/或泡沫形成剂。例如聚氧乙烯-脂肪酸酯类，聚氧乙烯-脂肪醇醚类，例如烷芳基聚乙二醇醚类，烷基磺酸酯类，烷基硫酸酯类，芳基磺酸酯类以及白蛋白水解产物。分散剂包括木质素亚硫酸盐废液和甲基纤维素。
在制剂中可以用粘合剂，例如羧甲基纤维素和以粉末、颗粒或乳液形式的天然和合成的多聚物，例如阿拉伯胶、聚乙烯基醇和聚乙烯醋酸酯。
可以用着色剂例如无机染料，如氧化铁、氧化钻和普鲁士蓝；有机染料，如偶氮染料或金属酞菁染料；和用痕量营养剂，如铁、锰、硼、铜、钴、铝和锌的盐等。
本发明的这些活性化合物可与其他活性化合物制成一种混合物存在于它们的商品制剂中或从这些制剂制备的使用剂型中，这些其他的活性化合物为杀虫剂、杀菌剂、杀真菌剂、除草剂、生长控制剂等。杀虫剂包括，例如磷酸酯类、氨基甲酸酯类、氯化烃类以及由微生物产生的物质，如阿维菌素等，杀真菌剂包括甲氧基丙烯酸酯类、酰胺类、三唑类等。
此外，本发明的这些活性化合物也可与增效剂制成一种混合物存在于它们的商品制剂中或从这些制剂制备的使用剂型中，这些增效剂是提高活性化合物作用的化合物，由于活性化合物本身有活性，也可不必加增效剂。
这些制剂通常含有占所述杀线虫剂组合物总重量的0.001-99.99重量％，优选0.01-99.9重量％，更优选0.05-90重量％的本发明的活性化合物。商品制剂或使用剂型中的活性化合物的浓度可在广阔的范围内变动。使用剂型中的活性化合物的浓度可从0.0000001-100％(g/v)，最好在0.0001与1％(g/v)之间。
本发明化合物的制备方法
本发明通式(I)所示化合物可通过如下的方法制得，然而该方法的条件，例如反应物、溶剂、碱、所用化合物的量、反应温度、反应所需时间等不限于下面的解释。本发明化合物还可以任选将在本说明书中描述的或本领域已知的各种合成方法组合起来而方便的制得，这样的组合可由本发明所属领域的技术人员容易的进行。
在本发明的制备方法中，各反应通常在惰性溶剂中，反应温度-20～120℃(优选-10～0℃或20～30℃或80～100℃)下进行。反应时间通常为2～24小时，较佳地为4～18小时。
反应中所用的碱包括(但并不限于)：三乙胺、二异丙基乙基胺、二乙胺、哌啶、哌嗪、吗啉、N-甲基吗啉、三乙烯二胺(DABCO)、1,8-二氮杂二环[5.4.0]十一碳-7-烯(DBU)、1,5-二氮杂二环[4.3.0]壬-5-烯(DBN)、碳酸钾、碳酸氢钾、碳酸钠、碳酸氢钠、碳酸铯、氢氧化钠、氢氧化钾、甲醇钠、乙醇钠，或其组合。
在一优选例中，本发明的原料式(d)化合物可通过包括如下步骤的方法合成：
Figure PCTCN2016071608-appb-000018
上述各式中，X、A、G如上文中所定义；
(1)在惰性溶剂中，在一定温度(如-10～-5℃)下，将式(a)化合物和BTC反应，从而得到式(b)化合物。
(2)在惰性溶剂中，在一定温度(如55～60℃)下，将式(b)化合物和碳酸铵反应，从而得到式(c)化合物。
(3)在惰性溶剂中，在一定温度(如-5～0℃)下，将式(c)化合物与NaNO2的稀盐酸溶液反应，从而得到式(d)化合物。
优选地，所述方法包括步骤：
(1)将式(a)化合物加入适量四氢呋喃中，降至-10℃。控温-10～-5℃，缓慢滴加BTC的四氢呋喃溶液，加毕，置于室温下反应，TLC跟踪反应进程，反应结束后，减压除去溶剂，向残留固体中加入无水乙醚充分搅拌，抽滤，干燥得式(b)化合物。
(2)将式(b)化合物加入适量1,4-二氧六环中，加入碳酸铵，加热至55～60℃反应，TLC跟踪反应进程，反应结束后，冷却至室温，减压除去溶剂，加入适量饱和碳酸氢钠水溶液，乙酸乙酯萃取，有机相用无水硫酸钠干燥，减压除去溶剂，得式(c)化合物。
(3)将NaNO2加入适量0.5M稀盐酸中，降至-5℃。控温-5～0℃，缓慢滴加式(c)化合物的DMF溶液，加毕，置于室温下反应，TLC跟踪反应进程，待(c)反应完全，用氨水调pH＝8～10，后用盐酸调pH＝2～5，抽滤，用大量水冲洗滤饼，干燥得式(d)化合物。
在另一优选例中，本发明通式(II)所示化合物可通过如下的方法合成：
Figure PCTCN2016071608-appb-000019
上述各式中，X、Y、L、M、G和A如上文中所定义，n为0-5的整数；
(1)在碱(如碳酸钾等)存在下，以惰性溶剂(如丙酮)作溶剂，式(d)化合物与BrCH2(CH2)nBr在一定温度(如回流)下反应一段时间(如5～10小时)，反应结束后，冷却至室温，减压蒸除溶剂，向残留物中加水，用二氯甲烷萃取，有机相用无水硫酸钠干燥，浓缩，柱分离，得式(e)化合物。
(2)在碘化钾存在下，以惰性溶剂(如DMF)为溶剂，式(e)化合物与式(f1)化合物在一定温度(如80～90℃)下反应一段时间(如10～15小时)，反应结束后，冷却至室温，减压蒸除溶剂，向残留物中加入稀盐酸，用二氯甲烷萃取，有机相用饱和食盐水洗涤，经无水硫酸钠干燥，浓缩，柱分离，得式(II)化合物；
或者，在碱(如碳酸钾等)存在下，以惰性溶剂(如DMF或丙酮)为溶剂，式(e)化合物与式 (p1)化合物在一定温度(如80～90℃或回流)下反应一段时间(如8～12小时)，反应结束后，冷却至室温，减压蒸除溶剂，向残留物中加水，用二氯甲烷萃取，有机相用饱和食盐水洗涤，经无水硫酸钠干燥，浓缩，柱分离，得式(II)化合物。
或者，通式(II)所示化合物通过如下的方法合成：
Figure PCTCN2016071608-appb-000020
上述各式中，X、Y、L、M、G和A如上文中所定义，n为0-5的整数；
(1)在碱(如碳酸钾等)存在下，以惰性溶剂(如丙酮)作溶剂，式(d)化合物与BrCH2(CH2)nC≡CH在一定温度(如回流)下反应一段时间(如5～8小时)，反应结束后，冷却至室温，减压蒸除溶剂，向残留物中加水，用二氯甲烷萃取，有机相用无水硫酸钠干燥，浓缩，柱分离，得式(g)化合物。
(2)在碱(如三乙胺等)存在下，以惰性溶剂(如乙腈)作溶剂，以CuI为催化剂，式(g)化合物与式(h1)化合物在室温下反应一段时间(如2～4小时)，反应结束后，减压蒸除溶剂，将残留物柱分离，得式(II)化合物。
在另一优选例中，本发明通式(III)所示化合物可通过如下的方法合成：
Figure PCTCN2016071608-appb-000021
上述各式中，X、L、M、G和A如上文中所定义，n为0-5的整数；
(1)在碱(如碳酸钾等)存在下，以惰性溶剂(如丙酮)作溶剂，式(d)化合物与BrCH2(CH2)nOH在一定温度(如回流)下反应一段时间(如5～8小时)，反应结束后，冷却至室温，减压蒸除溶剂，向残留物中加水，用二氯甲烷萃取，有机相用无水硫酸钠干燥，浓缩，柱分离，得式(i1)化合物。
(2)在碱(如三乙胺等)存在下，用惰性溶剂(如二氯甲烷)将式(i1)化合物溶解，室温下滴加加入式(k1)化合物，加毕，继续反应一段时间(如2～4小时)，反应结束后，加入饱和碳酸氢钠水溶液充分搅拌，分出有机相，水相用二氯甲烷再萃取2次，合并所有有机相，经无水硫酸钠干燥，浓缩，柱分离，得式(III)化合物。
在另一优选例中，本发明通式(IV)所示化合物可通过如下的方法合成：
Figure PCTCN2016071608-appb-000022
上述各式中，X、L、M、G和A如上文中所定义，n为0-5的整数；
(1)在碱(如碳酸钾等)存在下，以惰性溶剂(如DMF)为溶剂，式(e)化合物与式(m1)化合物在一定温度(如50～60℃)下反应一段时间(如8～12小时)，反应结束后，向残留物中加水，用二氯甲烷萃取，有机相用无水硫酸钠干燥，浓缩，柱分离，得式(q)化合物。
(2)在惰性溶剂(如乙醇)中，式(q)化合物与水合肼在一定温度(如回流)下反应一段时间(如6～10小时)，反应结束后，抽滤，滤除不溶物，将滤液中的溶剂减压蒸除，向残留物中加入饱和碳酸氢钠水溶液，用二氯甲烷萃取，有机相用无水硫酸钠干燥，减压蒸除溶剂，得黄色油状液体式(n1)化合物。
(3)在碱(如三乙胺等)存在下，用惰性溶剂(如二氯甲烷)将式(n1)化合物溶解，室温下滴加加入式(o1)化合物，加毕，继续反应一段时间(如2～4小时)，反应结束后，加入饱和碳酸氢钠水溶液充分搅拌，分出有机相，水相用二氯甲烷再萃取2次，合并所有有机相，经无水硫酸钠干燥，浓缩，柱分离，得式(IV)化合物。
在另一优选例中，本发明通式(V-VI)所示化合物可通过如下的方法合成：
Figure PCTCN2016071608-appb-000023
上述各式中，X、L、M、G和A如上文中所定义，n为0-5的整数；
在惰性溶剂(如乙腈)中，式(n1)化合物与式(o’1)化合物在室温下反应一段时间(如8～12小时)，反应结束后，抽滤，滤饼用无水乙醇重结晶，得式(V)化合物。
在惰性溶剂(如二氯甲烷)中，式(n1)化合物与式(o’2)化合物在室温下反应一段时间(如8～12小时)，反应结束后，抽滤，将滤液浓缩，柱分离，得式(VI)化合物。
优选地，在所述的反应混合物中，所述的中间产物的含量为10-99.99wt％；较佳地为20-90wt％；更佳地为50-80wt％。
因此，发明人可将该中间产物纯化后，再进行下一步反应；当然也可以将包含该化合物的反应混合物直接进行下一步反应。
下面结合具体实施例，进一步阐述本发明。应理解，这些实施例仅用于说明本发明而不用于限制本发明的范围。下列实施例中未注明具体条件的实验方法，通常按照常规条件，或按照制造厂商所建议的条件。除非另外说明，否则百分比和份数按重量计算。
实施例1  2-氰基亚氨基-3-(N-3-(4-氧-7-氯苯并[d][1,2,3]三嗪-3(4H)-基)丙基))-1,3-噻唑烷-4-酮
1.1制备7-氯苯并[d][1,2,3]三嗪-4(3H)-酮
1.1.1制备7-氯靛红酸酐
Figure PCTCN2016071608-appb-000024
将6.864g(40mmol)2-氨基-4-氯苯甲酸加入100ml四氢呋喃中，搅拌使之成混悬液，降至-10℃，控温-10～-5℃，缓慢滴加11.88g(40mmol)BTC的20ml四氢呋喃溶液，加毕，置于室温下反应，TLC跟踪反应进程。反应结束后，减压蒸除溶剂，向残留固体中加入150ml无水乙醚充分搅拌，抽滤，滤饼用无水乙醚洗涤，干燥得白色固体6.718g，收率85％。1H NMR(400MHz,DMSO-d6)δ11.84(s,1H),7.92(d,J＝8.4Hz,1H),7.30(dd,J1＝8.4Hz,J2＝1.6Hz,1H),7.14(d,J＝1.6Hz,1H)；13C NMR(100MHz,DMSO-d6)δ159.1,146.9,142.5,141.1,130.9,123.6,114.7,109.5.
1.1.2制备2-氨基-4-氯苯甲酰胺
Figure PCTCN2016071608-appb-000025
将5.928g(30mmol)7-氯靛红酸酐加入120ml 1,4-二氧六环中，加入14.40g(150mol)碳酸铵，搅拌使之成混悬液，加热至60℃反应，TLC跟踪反应进程。反应结束后，减压蒸除溶剂，向残留物中加入120ml饱和碳酸氢钠水溶液，用乙酸乙酯萃取(60ml×3)，有机相用无水硫酸钠干燥，减压蒸除溶剂，得浅褐色固体4.197g，收率82％。1H NMR(400MHz,DMSO-d6)δ7.78(br,1H),7.54(d,J＝8.4Hz,1H),7.15(br,1H),6.83(s,2H),6.74(d,J＝2.0Hz,1H),6.49(dd,J1＝8.4Hz,J2＝2.0Hz,1H)；13C NMR(100MHz,DMSO-d6)δ170.4,151.5,136.3,130.6,115.1,114.0,112.4.
1.1.3制备7-氯苯并[d][1,2,3]三嗪-4(3H)-酮
Figure PCTCN2016071608-appb-000026
将3.450g(50mmol)NaNO2溶于200ml 0.5M稀盐酸中，降至-5℃，控温-5～0℃，缓慢滴加4.265g(25mmol)2-氨基-4-氯苯甲酰胺的15ml DMF溶液，加毕，置于室温下反应，TLC跟踪反应进程。反应结束后，用氨水调pH＝10，充分搅拌15分钟，后用盐酸调pH＝2，充分搅拌15分钟，抽滤，用大量水冲洗滤饼，干燥，得白色固体3.860g，收率85％。1H NMR(400MHz,DMSO-d6)δ15.10(s,1H),8.29(d,J＝2.0Hz,1H),8.21(dd,J1＝8.4Hz,J2＝1.6Hz,1H),7.94(dd,J1＝8.4Hz,J2＝2.0Hz,1H)；13C NMR(100MHz,DMSO-d6)δ155.0,145.0,139.9,132.7,127.1,126.6,119.1.
1.2制备3-(3-溴丙基)-7-氯苯并[d][1,2,3]三嗪-4(3H)-酮
Figure PCTCN2016071608-appb-000027
将3.632g(20mmol)7-氯苯并[d][1,2,3]三嗪-4(3H)-酮加入120ml丙酮中，再加入24.24 g(120mmol)1,3-二溴丙烷和5.520g(40mmol)碳酸钾，搅拌使之成混悬液，加热至回流反应，TLC跟踪反应进程。反应结束后，减压蒸除溶剂，向残留物中加入200ml水，用二氯甲烷萃取(80ml×2)，有机相用无水硫酸钠干燥，浓缩，柱分离，得浅黄色固体3.150g，收率52％。1H NMR(400MHz,DMSO-d6)δ8.35–8.30(m,1H),8.25(d,J＝8.4Hz,1H),7.96(ddd,J1＝8.4Hz,J2＝2.0Hz,J3＝0.8Hz,1H),4.50(t,J＝6.8Hz,2H),3.63(t,J＝6.4Hz,2H),2.42-2.33(m,2H)；13C NMR(100MHz,DMSO-d6)δ154.4,144.5,139.7,132.9,127.1,126.8,118.3,48.0,31.6,31.2.
1.3制备2-氰基亚氨基-4-氧-1,3-噻唑烷-3-钾盐
Figure PCTCN2016071608-appb-000028
将11.68g(80mmol)N-氰基二硫代亚胺碳酸二甲酯和4.220g(44mmol)碳酸铵加入120ml乙醇中，搅拌使之成混悬液，加热至60℃反应，TLC跟踪反应进程。待N-氰基二硫代亚胺碳酸二甲酯反应完全，加入7.15ml(80mmol)巯基乙酸甲酯和8.960g(80mmol)50％KOH水溶液，加热至回流反应8小时，冷却至室温，抽滤，滤饼用无水乙醇洗涤，干燥，得浅黄色固体10.12g，收率71％。
1.4制备2-氰基亚氨基-3-(N-(3-(4-氧-7-氯苯并[d][1,2,3]三嗪-3(4H)-基)丙基))-1,3-噻唑烷-4-酮
Figure PCTCN2016071608-appb-000029
将0.606g(2mmol)3-(3-溴丙基)-7-氯苯并[d][1,2,3]三嗪-4(3H)-酮加入10ml DMF中，再加入0.332g(2mmol)碘化钾和0.358g(2mmol)2-氰基亚氨基-4-氧-1,3-噻唑烷-3-钾盐，搅拌使之呈混悬液，加热至90℃反应10小时，减压蒸除溶剂，加入稀盐酸，用二氯甲烷萃取，有机相用饱和食盐水洗涤，经无水硫酸钠干燥，浓缩，柱分离，得浅黄色固体0.305g，收率42％。1H NMR(400MHz,DMSO-d6)δ8.35(d,J＝2.0Hz,1H),8.25(dd,J1＝8.4Hz,J2＝2.0Hz,1H),7.97(dd,J1＝8.4Hz,J2＝2.0Hz,1H),4.40(t,J＝7.2Hz,2H),4.29(s,2H),3.74(t,J＝7.2Hz,2H),2.20-2.09(m,2H)；13C NMR(100MHz,DMSO-d6)δ179.6,172.9,154.8,144.9,140.3,133.6,127.7,127.3,118.6,114.0,47.3,40.8,36.1,26.0.HRMS(ES+)C14H11N6O2NaS35Cl(M+Na)+,计算值：385.0250,实测值：385.0258；C14H11N6O2NaS37Cl(M+Na)+,计算值：387.0221,实测值：387.0232。
实施例2  2-氰基亚氨基-3-(N-(4-(4-氧-7-氟苯并[d][1,2,3]三嗪-3(4H)-基)丁基))-1,3-噻唑烷-4-酮
Figure PCTCN2016071608-appb-000030
目标化合物的合成与实施例1的步骤1.4类似，不同点在于，用3-(4-溴丁基)-7-氟苯并[d][1,2,3]三嗪-4(3H)-酮代替3-(3-溴丙基)-7-氯苯并[d][1,2,3]三嗪-4(3H)-酮。黄色固体，收率53％。1H NMR(400MHz,DMSO-d6)δ8.33(dd,J1＝8.8Hz,J2＝5.6Hz,1H),8.07(dd,J1＝8.8Hz,J2＝2.4Hz,1H),7.81(td,J1＝8.8Hz,J2＝2.4Hz,1H),4.39(t,J＝6.8Hz,2H),4.31(s,2H),3.65(t,J＝6.8Hz,2H),1.90-1.75(m,2H),1.69-1.56(m,2H)；19F NMR(376MHz,DMSO-d6)δ-101.9(td,J1＝8.6Hz,J2＝5.6Hz).HRMS(ES-)C15H12N6O2FS(M-H)–,计算值：359.0726,实测值：359.0723。
实施例3  2-氰基亚氨基-3-(N-(5-(4-氧-6-甲基苯并[d][1,2,3]三嗪-3(4H)-基)戊基))-1,3-噻唑烷-4-酮
Figure PCTCN2016071608-appb-000031
目标化合物的合成与实施例1的步骤1.4类似，不同点在于，用3-(5-溴戊基)-6-甲基苯并[d][1,2,3]三嗪-4(3H)-酮代替3-(3-溴丙基)-7-氯苯并[d][1,2,3]三嗪-4(3H)-酮。浅黄色固体，收率65％。1H NMR(400MHz,DMSO-d6)δ8.09(d,J＝8.0Hz,1H),8.05(s,1H),7.90(d,J＝8.4Hz,1H),4.35(t,J＝6.8Hz,2H),4.31(s,2H),3.59(t,J＝6.8Hz,2H),2.55(s,3H),1.89-1.73(m,2H),1.67-1.50(m,2H),1.41-1.24(m,2H)；13C NMR(100MHz,DMSO-d6)δ179.6,173.0,155.2,144.1,142.5,136.9,128.3,124.2,119.5,114.3,49.2,43.1,36.0,28.3,26.4,23.6,21.8.HRMS(ES-)C17H17N6O2S(M-H)–,计算值：369.1134,实测值：369.1137。
实施例4  2-氰基亚氨基-3-(N-(6-(4-氧-7-甲氧基苯并[d][1,2,3]三嗪-3(4H)-基)己基))-1,3-噻唑烷-4-酮
Figure PCTCN2016071608-appb-000032
目标化合物的合成与实施例1的步骤1.4类似，不同点在于，用3-(6-溴己基)-7-甲氧基苯并[d][1,2,3]三嗪-4(3H)-酮代替3-(3-溴丙基)-7-氯苯并[d][1,2,3]三嗪-4(3H)-酮。浅黄色固体，收率41％。1H NMR(400MHz,DMSO-d6)δ8.15(d,J＝8.8Hz,1H),7.62(d,J＝2.4Hz,1H),7.47(dd,J1＝8.8Hz,J2＝2.4Hz,1H),4.39-4.27(m,4H),3.99(s,3H),3.58(t,J＝7.2Hz,2H),1.86-1.73(m,2H),1.59-1.46(m,2H),1.40-1.24(m,4H)；13C NMR(100MHz,DMSO-d6)δ179.1,172.5,164.3,154.3,145.9,126.3,122.3,113.7,112.7,108.5,56.3, 48.8,42.7,35.5,28.1,26.2,25.6,25.5.HRMS(ES+)C18H21N6O3S(M+H)+,计算值：401.1396,实测值：401.1396。
实施例5  2-氰基亚氨基-3-(N-(3-(4-氧-6-甲基噻吩并[3,2-d][1,2,3]三嗪-3(4H)-基)丙基))-1,3-噻唑烷-4-酮
Figure PCTCN2016071608-appb-000033
目标化合物的合成与实施例1的步骤1.4类似，不同点在于，用3-(3-溴丙基)-6-甲基噻吩并[3,2-d][1,2,3]三嗪-4(3H)-酮代替3-(3-溴丙基)-7-氯苯并[d][1,2,3]三嗪-4(3H)-酮。黄色固体，收率18％。HRMS(ES+)C13H13N6O2S2(M+H)+,计算值：349.0541,实测值：349.0538。
实施例6  2-氰基亚氨基-3-(N-(3-(4-氧-5,6,7,8-四氢苯并[4,5]噻吩[2,3-d][1,2,3]三嗪-3(4H)-基)丙基))-1,3-噻唑烷-4-酮
Figure PCTCN2016071608-appb-000034
目标化合物的合成与实施例1的步骤1.4类似，不同点在于，用3-(3-溴丙基)-5,6,7,8-四氢苯并[4,5]噻吩[2,3-d][1,2,3]三嗪-4(3H)-酮代替3-(3-溴丙基)-7-氯苯并[d][1,2,3]三嗪-4(3H)-酮。浅黄色固体，收率30％。HRMS(ES+)C16H17N6O2S2(M+H)+,计算值：389.0854,实测值：389.0858。
实施例7  2-氰基亚氨基-3-(N-(3-(4-硫-6-硝基苯并[d][1,2,3]三嗪-3(4H)-基)丙基))-1,3-噻唑烷-4-酮
Figure PCTCN2016071608-appb-000035
目标化合物的合成与实施例1的步骤1.4类似，不同点在于，用6-硝基苯并[d][1,2,3]三嗪-4(3H)-硫酮代替3-(3-溴丙基)-7-氯苯并[d][1,2,3]三嗪-4(3H)-酮。黄色固体，收率28％。HRMS(ES-)C14H10N7O3S2(M-H)–,计算值：388.0287,实测值：388.0291。
实施例8  5-氯-1-(4-(4-氧-7-三氟甲氧基苯并[d][1,2,3]三嗪-3(4H)-基)丁基)吲哚啉-2,3-二酮
Figure PCTCN2016071608-appb-000036
3-(4-溴丁基)-7-三氟甲氧基苯并[d][1,2,3]三嗪-4(3H)-酮的制备方法与实施例1中3-(3-溴丙基)-7-氯苯并[d][1,2,3]三嗪-4(3H)-酮的制备类似，不同点在于，用7-三氟甲氧基苯并[d][1,2,3]三嗪-4(3H)-酮代替7-氯苯并[d][1,2,3]三嗪-4(3H)-酮，用1,4-二溴丁烷代替1,3-二溴丙烷。
将0.732g(2mmol)3-(4-溴丁基)-7-三氟甲氧基苯并[d][1,2,3]三嗪-4(3H)-酮加入15mlDMF中，再加入0.399g(2.2mmol)5-氯靛红和0.414g(3mmol)碳酸钾，搅拌使之呈混悬液，加热至80℃反应8小时，减压蒸除溶剂，加水，用二氯甲烷萃取，有机相用饱和食盐水洗涤，经无水硫酸钠干燥，浓缩，柱分离，得黄色固体0.486g，收率52％。HRMS(ES+)C20H15N4O4F3 35Cl(M+H)+,计算值：467.0734,实测值：467.0738；C20H15N4O4F3 37Cl(M+H)+,计算值：469.0704，实测值：469.0768。
实施例9  1-(4-(4-氧-7-硝基苯并[d][1,2,3]三嗪-3(4H)-基)丁基)螺[吲哚啉-3,2’-[1,3]二氧戊环]-2-酮
9.1制备螺[吲哚啉-3,2’-[1,3]二氧戊环]-2-酮
Figure PCTCN2016071608-appb-000037
将2.94g(20mmol)靛红、22ml乙二醇和0.38g(1mmol)对甲基苯磺酸加入160ml甲苯中，加热至回流反应12小时。冷却至室温，减压蒸除溶剂，加入饱和碳酸钠水溶液，用二氯甲烷萃取，有机相用无水硫酸钠干燥，浓缩，柱分离，得浅黄色针状晶体2.636g，收率69％。1H NMR(400MHz,DMSO-d6)δ10.43(s,1H),7.37-7.28(m,2H),7.01(td,J1＝7.6Hz,J2＝0.8Hz,1H),6.83(d,J＝7.6Hz,1H),4.40-4.30(m,2H),4.30-4.20(m,2H)；13C NMR(100MHz,DMSO-d6)δ174.4,142.8,131.6,124.9,124.6,122.3,110.5,101.6,65.4.
9.2制备1-(4-(4-氧-7-硝基苯并[d][1,2,3]三嗪-3(4H)-基)丁基)螺[吲哚啉-3,2’-[1,3]二氧戊环]-2-酮
Figure PCTCN2016071608-appb-000038
3-(4-溴丁基)-7-硝基苯并[d][1,2,3]三嗪-4(3H)-酮的制备方法与实施例1中3-(3-溴丙基)-7-氯苯并[d][1,2,3]三嗪-4(3H)-酮的制备类似，不同点在于，用7-硝基苯并[d][1,2,3]三嗪-4(3H)-酮代替7-氯苯并[d][1,2,3]三嗪-4(3H)-酮，用1,4-二溴丁烷代替1,3-二溴丙烷。
将0.327g(1mmol)3-(4-溴丁基)-7-硝基苯并[d][1,2,3]三嗪-4(3H)-酮加入10ml DMF中，再加入0.210g(1.1mmol)螺[吲哚啉-3,2’-[1,3]二氧戊环]-2-酮和0.207g(1.5mmol)碳酸钾，搅拌使之呈混悬液，加热至80℃反应10小时。冷却至室温，减压蒸除溶剂，加水，用二氯甲烷萃取，有机相用无水硫酸钠干燥，浓缩，柱分离，得黄色固体0.323g， 收率74％。1H NMR(400MHz,DMSO-d6)δ8.90(d,J＝2.0Hz,1H),8.59(dd,J1＝8.8Hz,J2＝2.0Hz,1H),8.46(d,J＝8.8Hz,1H),7.44-7.32(m,2H),7.15-7.03(m,2H),4.44(t,J＝6.8Hz,2H),4.39-4.30(m,2H),4.30-4.22(m,2H),3.66(t,J＝6.8Hz,2H),1.93-1.78(m,2H),1.77-1.61(m,2H)；13C NMR(100MHz,DMSO-d6)δ172.5,153.9,151.3,143.7,143.4,131.7,127.2,126.2,124.6,124.1,123.4,123.2,122.9,109.5,101.4,65.5,49.0,38.5,25.4,23.8.HRMS(ES-)C21H18N5O6(M-H)–,计算值：436.1257,实测值：436.1260。
实施例10  1-(4-(4-氧-7-乙烯基苯并[d][1,2,3]三嗪-3(4H)-基)丁基)-6-溴螺[吲哚啉-3,2’-[1,3]二氧六环]-2-酮
Figure PCTCN2016071608-appb-000039
目标化合物的合成与实施例9的步骤9.2类似，不同点在于，用3-(4-溴丁基)-7-乙烯基苯并[d][1,2,3]三嗪-4(3H)-酮代替3-(4-溴丁基)-7-乙烯基苯并[d][1,2,3]三嗪-4(3H)-酮，用6-溴螺[吲哚啉-3,2’-[1,3]二氧六环]-2-酮代替螺[吲哚啉-3,2’-[1,3]二氧戊环]-2-酮。白色固体，收率88％。HRMS(ES+)C24H24N4O4 79Br(M+H)+,计算值：511.0981,实测值：511.0985；C24H24N4O4 81Br(M+H)+,计算值：513.0960,实测值：513.0958。
实施例11  3-((1-(4-甲氧基苯基)-1H-1,2,3-三唑-4-基)甲基)苯并[d][1,2,3]三嗪-4(3H)-酮
11.1制备3-(2-丙炔-1-基)苯并[d][1,2,3]三嗪-4(3H)-酮
Figure PCTCN2016071608-appb-000040
将7.350g(50mmol)苯并[d][1,2,3]三嗪-4(3H)-酮和8.28g(60mmol)碳酸钾加入200ml丙酮中，搅拌使之呈混悬液，加入8.925g(75mmol)3-溴丙炔，加热至50℃反应8小时。冷却至室温，减压蒸除溶剂，加水，用二氯甲烷萃取，有机相用无水硫酸钠干燥，浓缩，柱分离，得黄色固体6.013g，收率65％。1H NMR(400MHz,DMSO-d6)δ8.28(d,J＝7.6Hz,1H),8.24(d,J＝8.4Hz,1H),8.13(t,J＝7.6Hz,1H),7.97(t,J＝7.6Hz,1H),5.21(d,J＝2.4Hz,2H),3.43(t,J＝2.5Hz,1H)；13C NMR(100MHz,DMSO-d6)δ154.1,143.6,135.7,133.3,128.2,124.6,119.3,78.1,75.6,38.8.
11.2制备3-((1-(4-甲氧基苯基)-1H-1,2,3-三唑-4-基)甲基)苯并[d][1,2,3]三嗪-4(3H)-酮
Figure PCTCN2016071608-appb-000041
将0.295g(2.4mmol)4-甲氧基苯胺加入5ml乙腈中，降至0℃，依次加入0.371g(3.6mmol)亚硝酸特丁酯和0.331g(2.88mmol)叠氮基三甲基硅烷，0℃下搅拌10分钟，后置于室温下继续反应1小时，再依次加入0.296g(1.6mmol)3-(2-丙炔-1-基)苯并[d][1,2,3]三嗪-4(3H)-酮、0.036g(0.192mmol)碘化亚铜和0.34ml(2.4mmol)三乙胺，补加5ml乙腈，室温下反应2小时。向反应液中加入适量硅胶，减压蒸除溶剂，柱分离，得黄色固体0.278g，收率52％。1H NMR(400MHz,CDCl3)δ8.34(dd,J1＝8.0Hz,J2＝0.8Hz,1H),8.16(d,J＝8.0Hz,1H),8.09(s,1H),7.98-7.92(m,1H),7.84-7.77(m,1H),7.63-7.56(m,2H),7.02-6.96(m,2H),5.85(s,2H),3.85(s,3H)；13C NMR(100MHz,CDCl3)δ159.9,155.4,144.4,142.8,135.0,132.5,130.4,128.5,125.0,122.3,122.1,119.9,114.7,55.6,45.4.HRMS(ES+)C17H15N6O2(M+H)+,计算值：335.1256,实测值：335.1251。
实施例12  3-(2-(1-(4-叔丁基)苯基-1H-1,2,3-三唑-4-基)乙基)-7-硝基苯并[d][1,2,3]三嗪-4(3H)-酮
Figure PCTCN2016071608-appb-000042
目标化合物的合成与实施例11的步骤11.2类似，不同点在于，用4-叔丁基苯胺代替4-甲氧基苯胺，用3-(3-丁炔-1-基)-7-硝基苯并[d][1,2,3]三嗪-4(3H)-酮代替3-(2-丙炔-1-基)苯并[d][1,2,3]三嗪-4(3H)-酮。浅黄色固体，收率45％。HRMS(ES-)C21H20N7O3(M-H)–,计算值：418.1628,实测值：418.1631。
实施例13  3-(3-((5-环丙基-1,3,4-噻二唑-2-基)硫)丙基)-7-硝基苯并[d][1,2,3]三嗪-4(3H)-酮
Figure PCTCN2016071608-appb-000043
3-(3-溴丙基)-7-硝基苯并[d][1,2,3]三嗪-4(3H)-酮的制备方法与实施例1中3-(3-溴丙基)-7-氯苯并[d][1,2,3]三嗪-4(3H)-酮的制备类似，不同点在于，用7-硝基苯并[d][1,2,3]三嗪-4(3H)-酮代替7-氯苯并[d][1,2,3]三嗪-4(3H)-酮。
将0.626g(2mmol)3-(3-溴丙基)-7-硝基苯并[d][1,2,3]三嗪-4(3H)-酮、0.474g(3mmol)5-环丙基-2-巯基噻二唑和0.331g(2.4mmol)碳酸钾，加入30ml丙酮中，搅拌使之 呈混悬液，加热至回流反应8小时。冷却至室温，减压蒸除溶剂，加水，用二氯甲烷萃取，有机相用无水硫酸钠干燥，浓缩，柱分离，得黄色固体0.624g，收率80％。HRMS(ES-)C15H13N6O3S2(M-H)–,计算值：389.0491,实测值：389.0496。
实施例14  3-(3-((6-甲氧基苯并[d]噁唑-2-基)硫)丙基)-4-氧-3,4-二氢苯并[d][1,2,3]三嗪-6-磺酰胺
Figure PCTCN2016071608-appb-000044
目标化合物的合成与实施例13的步骤类似，不同点在于，用3-(3-溴丙基)-6-氨基磺酰基苯并[d][1,2,3]三嗪-4(3H)-酮代替7-氯苯并[d][1,2,3]三嗪-4(3H)-酮，不同点在于，用6-氨基磺酰基苯并[d][1,2,3]三嗪-4(3H)-酮代替3-(3-溴丙基)-7-硝基苯并[d][1,2,3]三嗪-4(3H)-酮，用6-甲氧基苯并[d]噁唑-2-硫醇代替5-环丙基-2-巯基噻二唑。黄色固体，收率71％。HRMS(ES+)C18H18N5O5S2(M+H)+,计算值：448.0749,实测值：448.0755。
实施例15  3-(4-氧苯并[d][1,2,3]三嗪-3(4H)-基)丙基苯并[d][1,2,3]噻二唑-7-羧酸酯
15.1制备3-(3-羟丙基)苯并[d][1,2,3]三嗪-4(3H)-酮
Figure PCTCN2016071608-appb-000045
7-氟苯并[d][1,2,3]三嗪-4(3H)-酮的制备方法与实施例1的步骤1.1类似，不同点在于，用2-氨基-4-氟苯甲酸代替2-氨基-4-氯苯甲酸。
将0.330g(2mmol)7-氟苯并[d][1,2,3]三嗪-4(3H)-酮和0.552g(4mmol)碳酸钾，加入30ml丙酮中，搅拌使之呈混悬液，加入0.417g(3mmol)3-溴丙醇，加热至回流反应6小时。冷却至室温，减压蒸除溶剂，加水，用二氯甲烷萃取，有机相用无水硫酸钠干燥，浓缩，柱分离，得米黄色固体0.317g，收率71％。HRMS(ES+)C10H11N3O2F(M+H)+,计算值：224.0835,实测值：224.0841。
15.2制备苯并[d][1,2,3]噻二唑-7-羰基氯
Figure PCTCN2016071608-appb-000046
将3.780g(21mmol)苯并[d][1,2,3]噻二唑-7-羧酸加入40ml氯化亚砜中，加热至回流反应8小时。冷却至室温，减压蒸除未反应完的氯化亚砜，得浅黄色固体3.552g，未经处理直接用于下一步。
15.3制备3-(4-氧-7-氟苯并[d][1,2,3]三嗪-3(4H)-基)丙基苯并[d][1,2,3]噻二唑-7-羧酸酯
Figure PCTCN2016071608-appb-000047
将0.446g(2mmol)3-(3-羟丙基)-7-氟苯并[d][1,2,3]三嗪-4(3H)-酮溶入20ml二氯甲烷，加入0.31ml(2.2mol)三乙胺，室温下滴加加入0.478g(2.4mmol)苯并[d][1,2,3]噻二唑-7-羰基氯的20ml二氯甲烷溶液。加毕，室温下继续反应4小时，向反应液中加入饱和碳酸氢钠水溶液，充分搅拌，分出有机相，水相再用二氯甲烷萃取，合并所有有机相，经无水硫酸钠干燥，浓缩，柱分离，得白色固体0.246g，收率32％。1H NMR(400MHz,DMSO-d6)δ8.98(d,J＝8.4Hz,1H),8.23-8.14(m,2H),7.91(dd,J1＝8.8Hz,J2＝2.0Hz,1H),7.80(t,J＝8.0Hz,1H),7.69(td,J1＝8.8Hz,J2＝2.4Hz,1H),4.63(t,J＝6.0Hz,2H),4.55(t,J＝5.6Hz,2H),2.46-2.35(m,2H)；19F NMR(376MHz,DMSO-d6)δ-102.0(td,J1＝8.6Hz,J2＝5.6Hz).HRMS(ES+)C17H13N5O3FS(M+H)+,计算值：386.0723,实测值：386.0724。
实施例16  3-(4-氧-5-溴苯并[d][1,2,3]三嗪-3(4H)-基)丙基苯并[d][1,2,3]噻二唑-7-羧酸酯
Figure PCTCN2016071608-appb-000048
目标化合物的合成与实施例15的步骤15.3类似，不同点在于，用3-(3-羟丙基)-5-溴苯并[d][1,2,3]三嗪-4(3H)-酮代替3-(3-羟丙基)-7-氟苯并[d][1,2,3]三嗪-4(3H)-酮。白色固体，收率26％。1H NMR(400MHz,DMSO-d6)δ8.99(d,J＝8.4Hz,1H),8.27(s,1H),8.20(d,J＝7.2Hz,1H),8.01(d,J＝8.4Hz,1H),7.95(d,J＝8.8Hz,1H),7.81(t,J＝8.0Hz,1H),4.63(t,J＝6.4Hz,2H),4.56(t,J＝5.6Hz,2H),2.47-2.36(m,2H)；13C NMR(100MHz,DMSO-d6)δ164.0,158.3,154.5,144.4,139.2,135.6,130.7,129.9,128.6,128.1,126.5,122.3,118.3,64.4,47.1,27.0.HRMS(ES+)C17H12N5O3NaS79Br(M+Na)+,计算值：467.9742,实测值：467.9744；C17H12N5O3NaS81Br(M+Na)+,计算值：469.9721,实测值：469.9716。
实施例17  3-(4-氧-6-三氟甲基苯并[d][1,2,3]三嗪-3(4H)-基)丙基苯并[d][1,2,3]噻二唑-7-羧酸酯
Figure PCTCN2016071608-appb-000049
目标化合物的合成与实施例15的步骤15.3类似，不同点在于，用3-(3-羟丙基)-6-三氟甲基苯并[d][1,2,3]三嗪-4(3H)-酮代替3-(3-羟丙基)-7-氟苯并[d][1,2,3]三嗪-4(3H)-酮。白色固体，收率16％。1H NMR(400MHz,DMSO-d6)δ9.19(t,J＝5.2Hz,1H),8.88(d,J＝8.4Hz,1H),8.53-8.42(m,2H),8.42-8.31(m,2H),7.90(t,J＝7.6Hz,1H),4.48(t,J ＝6.8Hz,2H),3.48-3.40(m,2H),2.00-1.90(m,2H),1.78-1.65(m,2H)；19F NMR(376MHz,DMSO-d6)δ-61.5(s).HRMS(ES+)C19H16N6O2F3S(M+H)+,计算值：449.1008,实测值：449.1006。
实施例18  N-(3-(4-氧-7-氟苯并[d][1,2,3]三嗪-3(4H)-基)丙基)苯并[d][1,2,3]噻二唑-7-酰胺
18.1制备2-(3-(4-氧-7-氟苯并[d][1,2,3]三嗪-3(4H)-基)丙基)异吲哚啉-1,3-二酮
Figure PCTCN2016071608-appb-000050
将0.572g(2mmol)3-(3-溴丙基)-7-氟苯并[d][1,2,3]三嗪-4(3H)-酮、0.353g(2.4mmol)邻苯二甲酰亚胺和0.331g(2.4mmol)，加入10ml DMF中，搅拌使之呈混悬液，加热至60℃反应3小时。冷却至室温，减压蒸除溶剂，加水，用二氯甲烷萃取，有机相用无水硫酸钠干燥，浓缩，柱分离，得米白色固体0.598g，收率85％。HRMS(ES+)C18H14N4O3F(M+Na)+,计算值：353.1050,实测值：353.1053。
18.2制备3-(3-氨基丙基)-7-氟苯并[d][1,2,3]三嗪-4(3H)-酮
Figure PCTCN2016071608-appb-000051
将0.352g(1mmol)2-(4-(4-氧苯并[d][1,2,3]三嗪-3(4H)-基)丁基)异吲哚啉-1,3-二酮，加入10ml二氯甲烷和10ml乙醇的混合溶剂中，加热至回流反应12小时。冷却至室温，减压蒸除溶剂，向残留物中加入饱和碳酸钠水溶液，用二氯甲烷萃取，有机相用无水硫酸钠干燥，减压蒸除溶剂，得黄色油状液体0.191g，未经提纯直接用于下一步。
18.3制备N-(3-(4-氧-7-氟苯并[d][1,2,3]三嗪-3(4H)-基)丙基)苯并[d][1,2,3]噻二唑-7-酰胺
Figure PCTCN2016071608-appb-000052
将0.222g(1mmol)3-(3-氨基丙基)-7-氟苯并[d][1,2,3]三嗪-4(3H)-酮溶于10ml二氯甲烷中，加入0.15ml(1.1mmol)三乙胺，室温下滴加加入0.259g(1.3mmol)苯并[d][1,2,3]噻二唑-7-羰基氯的10ml二氯甲烷溶液。加毕，室温下继续反应5小时，向反应液中加入饱和碳酸氢钠水溶液，充分搅拌，分出有机相，水相再用二氯甲烷萃取，合并所有有机相，经无水硫酸钠干燥，浓缩，柱分离，得米白色固体0.131g，收率34％。1H NMR(400MHz,DMSO-d6)δ9.24(t,J＝5.2Hz,1H),8.88(d,J＝8.4Hz,1H),8.42(d,J＝7.2Hz,1H),8.26(dd,J1＝8.8Hz,J2＝5.6Hz,1H),7.97(dd,J1＝8.8Hz,J2＝2.0Hz,1H),7.90(t,J＝7.6Hz,1H),7.74(td,J1＝8.8Hz,J2＝2.0Hz,1H),4.50(t,J＝7.2Hz,2H),3.58-3.48(m,2H),2.27-2.16(m,2H)；19F NMR(376MHz,DMSO-d6)δ-102.0(td,J1＝8.6Hz,J2＝5.6 Hz).HRMS(ES+)C17H14N6O2FS(M+H)+,计算值：385.0883,实测值：385.0885。
实施例19  N-(4-(4-氧-7-溴苯并[d][1,2,3]三嗪-3(4H)-基)丁基)苯并[d][1,2,3]噻二唑-7-酰胺
Figure PCTCN2016071608-appb-000053
目标化合物的合成与实施例18的步骤18.2类似，不同点在于，用3-(4-氨基丁基)-7-溴苯并[d][1,2,3]三嗪-4(3H)-酮代替3-(3-氨基丙基)-7-氟苯并[d][1,2,3]三嗪-4(3H)-酮。米白色固体，收率25％。1H NMR(400MHz,DMSO-d6)δ9.18(t,J＝4.8Hz,1H),8.88(d,J＝8.0Hz,1H),8.44(d,J＝7.2Hz,1H),8.39(s,1H),8.10(d,J＝8.4Hz,1H),8.03(d,J＝8.8Hz,1H),7.89(t,J＝8.0Hz,1H),4.42(t,J＝6.8Hz,2H),3.48-3.39(m,2H),1.98-1.87(m,2H),1.73-1.62(m,2H)；13C NMR(100MHz,DMSO-d6)δ163.5,158.1,154.3,144.5,138.3,135.7,130.1,128.6,127.8,126.7,126.6,126.3,118.3,49.0,25.8,25.6.HRMS(ES+)C18H16N6O2S79Br(M+H)+,计算值：459.0239,实测值：459.0241；C18H16N6O2S81Br(M+H)+,计算值：461.0218,实测值：461.0221。
实施例20  N-(3-(5-氯-4-氧苯并[d][1,2,3]三嗪-3(4H)-基)丙基)-5-甲基-1,2,3-噻二唑-4-酰胺
Figure PCTCN2016071608-appb-000054
目标化合物的合成与实施例18的步骤18.2类似，不同点在于，用3-(3-氨基丙基)-5-氯苯并[d][1,2,3]三嗪-4(3H)-酮代替3-(3-氨基丙基)-7-氟苯并[d][1,2,3]三嗪-4(3H)-酮，用5-甲基-1,2,3-噻二唑-4-羰基氯代替苯并[d][1,2,3]噻二唑-7-羰基氯。白色固体，收率41％。HRMS(ES+)C14H13N6O2NaS35Cl(M+Na)+,计算值：387.0407,实测值：387.0411；C14H13N6O2NaS37Cl(M+Na)+,计算值：389.0377,实测值：389.0380。
实施例21  1-(6-甲氧基苯并[d]噻唑-2-基)-3-(3-(4-氧-7-三氟甲基苯并[d][1,2,3]三嗪-3(4H)-基)丙基)硫脲
Figure PCTCN2016071608-appb-000055
3-(3-氨基丙基)-7-三氟甲基苯并[d][1,2,3]三嗪-4(3H)-酮的制备方法与实施例18中3-(3-氨基丙基)-7-氟苯并[d][1,2,3]三嗪-4(3H)-酮的制备类似，不同点在于，用3-(3-溴丙基)-7-三氟甲基苯并[d][1,2,3]三嗪-4(3H)-酮代替3-(3-溴丙基)-7-氟苯并[d][1,2,3]三嗪 -4(3H)-酮。2-异硫氰酸酯基-6-甲氧基苯并[d]噻唑的制备方法可如“WO 2014117677”中所述，由2-氨基-6-甲氧基苯并[d]噻唑制得。
将0.136g(0.5mmol)3-(3-氨基丙基)-7-三氟甲基苯并[d][1,2,3]三嗪-4(3H)-酮溶于2ml乙腈中，加入0.111g(0.5mmol)2-异硫氰酸酯基-6-甲氧基苯并[d]噻唑，室温下搅拌，TLC跟踪反应进程。反应结束后，抽滤，滤饼用乙醇重结晶，得棕黄色粉末状固体0.191g，收率77％。HRMS(ES+)C20H18N6O2F3S2(M+H)+,计算值：495.0885,实测值：495.0882。
实施例22  1-(苯并[d]异噁唑-3-基)-3-(3-(4-氧-8-甲氧基苯并[d][1,2,3]三嗪-3(4H)-基)丙基)硫脲
Figure PCTCN2016071608-appb-000056
目标化合物的合成与实施例21的步骤类似，不同点在于，用3-(3-氨基丙基)-8-甲氧基苯并[d][1,2,3]三嗪-4(3H)-酮代替3-(3-氨基丙基)-7-三氟甲基苯并[d][1,2,3]三嗪-4(3H)-酮，用3-异硫氰酸酯基苯并[d]异噁唑代替3-(3-氨基丙基)-7-三氟甲基苯并[d][1,2,3]三嗪-4(3H)-酮。黄色粉末状固体，收率71％。HRMS(ES+)C19H18N6O3NaS(M+Na)+,计算值：433.1059,实测值：433.1062。
实施例23  N-((3-(4-氧-8-氯苯并[d][1,2,3]三嗪-3(4H)-基)丙基)氨基硫羰基)-2-(三氟甲氧基)苯甲酰胺
23.1制备2-(三氟甲氧基)苯甲酰基异硫氰酸酯
Figure PCTCN2016071608-appb-000057
2-(三氟甲氧基)苯甲酰氯的制备方法与实施例15的步骤15.2类似，不同点在于，用2-(三氟甲氧基)苯甲酸代替苯并[d][1,2,3]噻二唑-7-羧酸。
将1.8g(8mmol)2-(三氟甲氧基)苯甲酰氯溶于20ml二氯甲烷中，加入0.912g(12mmol)硫氰酸铵，加入0.144g PEG-400，室温下搅拌1小时，抽滤，将滤液浓缩，经闪柱纯化，得黄色油状液体1.581g，直接用于下一步反应。
23.2制备N-((3-(4-氧苯并[d][1,2,3]三嗪-3(4H)-基)丙基)氨基硫羰基)-2-(三氟甲氧基)苯甲酰胺
Figure PCTCN2016071608-appb-000058
3-(3-氨基丙基)苯并[d][1,2,3]三嗪-4(3H)-酮的制备方法与实施例18中3-(3-氨基丙基)-7-氟苯并[d][1,2,3]三嗪-4(3H)-酮的制备类似，不同点在于，用苯并[d][1,2,3]三嗪-4(3H)-酮代替3-(3-溴丙基)-7-氟苯并[d][1,2,3]三嗪-4(3H)-酮。
将0.102g(0.5mmol)3-(3-氨基丙基)苯并[d][1,2,3]三嗪-4(3H)-酮溶于2ml乙腈中，加入0.124g(0.5mmol)2-(三氟甲氧基)苯甲酰基异硫氰酸酯，室温下搅拌，TLC跟踪反应进程。反应结束后，抽滤，将滤液浓缩，柱分离，得浅黄色固体0.153g，收率68％。1H NMR(400Mz,CDCl3)δ10.77(br,1H),9.57(br,1H),8.32(d,J＝7.6Hz,1H),7.92-7.88(m,3H),7.82(t,J＝7.2Hz,1H),7.64(t,J＝7.2Hz,1H),7.46(t,J＝7.2Hz,1H),7.36(d,J＝7.2Hz,1H),4.81(t,J＝6.0Hz,2H),3.92-3.91(m,2H),2.73-2.59(m,2H)；13C NMR(100Mz,CDCl3)δ180.2,167.8,163.9,146.3,146.0,134.5,134.3,133.5,131.6,127.5,126.4,125.4,125.3,124.0,120.2(q,1JCF＝260.0Hz),117.8,67.1,42.27,27.9.HRMS(ES+)C19H17F3N5O3S(M+H)+,计算值：452.1004,实测值：452.1004。
实施例24  3-(5-甲基-1,2,4-噁二唑-3-基)-N-((3-(3-氧-7-硝基苯并[d][1,2,3]三嗪-3(4H)-基)丙基)氨基硫羰基)苯甲酰胺
Figure PCTCN2016071608-appb-000059
目标化合物的制备与实施例23的步骤23.2类似，不同点在于，用3-(3-氨基丙基)-7-硝基苯并[d][1,2,3]三嗪-4(3H)-酮代替3-(3-氨基丙基)苯并[d][1,2,3]三嗪-4(3H)-酮，用3-(5-乙基-1,2,4-噁二唑-3-基)苯甲酰异硫氰酸酯代替2-(三氟甲氧基)苯甲酰基异硫氰酸酯。浅黄色固体，收率65％。HRMS(ES–)C22H19N8O5S(M–H)–,计算值：507.1199,实测值：507.1194。
实施例25本发明化合物的杀线虫活性测试
根结线虫属于线虫门、垫刃目(Tylenchida)、垫刃亚目、异皮总科、异皮科(Heteroderidea)、根结线虫亚科(Meloidogyninae)、根结线虫属，是一种危害严重的植物寄生线虫。
以南方根结线虫(Meloidogyne incognita)为测试对象，以黄瓜苗为供试寄主，采用试管种植法测试。
操作过程：将待试样品按所需浓度配成药液待用，并准备好足量的根结线虫二龄幼虫。将一周龄的黄瓜苗种植到试管中后，向试管中加入适量配好的药液，并向每支试管中接入约2000条幼虫。试管置于20～25℃，10小时光照下培养，20天后调查结果，计数每株植株根系上的根结数。每个样品重复试验3次，每次试验每个样品做4个重复处理。
以蒸馏水为空白对照，蒸馏水加根结线虫为阴性对照，以苯线磷和阿维菌素溶液为阳性对照。
按根结数量进行分级(参见表1)，统计抑制率。统计结果见表2～6。
抑制率(％)＝(阴性对照得分数-试验组得分数)/阴性对照得分数×100％
表1
分级标准：
0：0-5个根结；
5：6-10个根结；
10：11-20个根结；
20：多于20个根结。
表2式(II)化合物的杀线虫活性
Figure PCTCN2016071608-appb-000060
Figure PCTCN2016071608-appb-000061
Figure PCTCN2016071608-appb-000062
Figure PCTCN2016071608-appb-000063
Figure PCTCN2016071608-appb-000064
Figure PCTCN2016071608-appb-000065
Figure PCTCN2016071608-appb-000066
Figure PCTCN2016071608-appb-000067
Figure PCTCN2016071608-appb-000068
Figure PCTCN2016071608-appb-000069
Figure PCTCN2016071608-appb-000070
表3式(III)化合物的杀线虫活性
Figure PCTCN2016071608-appb-000071
Figure PCTCN2016071608-appb-000072
Figure PCTCN2016071608-appb-000073
Figure PCTCN2016071608-appb-000074
表4式(IV)化合物的杀线虫活性
Figure PCTCN2016071608-appb-000075
Figure PCTCN2016071608-appb-000076
Figure PCTCN2016071608-appb-000077
Figure PCTCN2016071608-appb-000078
表5式(V)化合物的杀线虫活性
Figure PCTCN2016071608-appb-000079
Figure PCTCN2016071608-appb-000080
Figure PCTCN2016071608-appb-000081
Figure PCTCN2016071608-appb-000082
Figure PCTCN2016071608-appb-000083
表6式(VI)化合物的杀线虫活性
Figure PCTCN2016071608-appb-000084
Figure PCTCN2016071608-appb-000085
Figure PCTCN2016071608-appb-000086
Figure PCTCN2016071608-appb-000087
上述表格中，Y为“-”表示Y为共价键，M为“/”表示M为无。
实施例26含有本发明化合物杀线虫剂的组合物
(a)微乳剂
按比例准备以下组分：5.0％(重量百分比，下同)化合物II-1～VI-36中任一种化合物(表2～6)；30.0％聚乙烯吡咯烷酮-乙酸乙烯酯共聚物；30.0％烷基多苷；15.0％油酸甘油酯；20.0％水。
(b)可湿性粉剂
按比例准备以下组分：65.0％化合物II-1～VI-36中任一种化合物(表2～6)；2.0％十二烷基苯酚聚乙二醇醚；4.0％木质素磺酸钠；6.0％硅酸铝钠；23.0％蒙脱石(煅烧过的)。
(c)种子处理剂
按比例准备以下组分：20.00％化合物II-1～VI-36中任一种化合物(表2～6)；5.00％聚乙烯吡咯烷酮-乙酸乙烯酯共聚物；5.00％褐煤酸蜡；1.00％木质素磺酸钙；1.00％聚氧乙烯/聚氧丙烯嵌段共聚物；2.00％硬脂醇(POE 20)；0.20％聚有机硅；0.05％着色剂红色染料；65.75％水。
在本发明提及的所有文献都在本申请中引用作为参考，就如同每一篇文献被单独引用作为参考那样。此外应理解，在阅读了本发明的上述讲授内容之后，本领域技术人员可以对本发明作各种改动或修改，这些等价形式同样落于本申请所附权利要求书所限定的范围。

Claims (10)

  1. 一种具有通式(I)所示结构的化合物，或所述化合物的光学异构体、顺反异构体或农药学上可接受的盐：
    Figure PCTCN2016071608-appb-100001
    式中：
    X为O或S；
    Y为O、S、S(＝O)、S(＝O)2、NH或共价键；
    Q为羰基、硫羰基-氨基、硫羰基-氨基-羰基或共价键；
    当L为取代或未取代的C1-6亚烷基、取代或未取代的C1-6卤代亚烷基、取代或未取代的C2-6亚烯基、取代或未取代的C2-6卤代亚烯基、取代或未取代的C2-6亚炔基、取代或未取代的C2-6卤代亚炔基、取代或未取代的C3-7亚环烷基、取代或未取代的C5-7亚环烯基、取代或未取代的亚苯基、取代或未取代的亚萘基、取代或未取代的5元或6元亚杂环基、或取代或未取代的8元至14元亚杂芳二环或三环环系，所述取代是指被选自下组的一个或多个基团所取代：卤素、氰基、硝基、R’、OR’、Si(R’)3、NR’R"、C(O)R’、C(O)OR’、C(O)NR’R"、SR’、S(O)mR1、S(O)2NR’R"、OC(O)R1、OC(O)NR’R"、OS(O)2R1、OS(O)2NR’R"、N(R2)C(O)R1、N(R2)C(O)NR’R"、N(R2)S(O)2R1或N(R2)S(O)2NR’R"时；M为H、C1-6烷基、C1-6卤代烷基、C2-6烯基、C2-6卤代烯基、取代或未取代的C2-6炔基、C2-6卤代炔基，或取代或未取代的C3-7环烷基、取代或未取代的C5-7环烯基、取代或未取代的苯基、取代或未取代的萘基、取代或未取代的5元或6元杂环基、或取代或未取代的8元至14元杂芳二环或三环环系，所述取代是指被选自下组的一个或多个基团所取代：卤素、氰基、硝基、R’、OR’、Si(R’)3、NR’R"、C(O)R’、C(O)OR’、C(O)NR’R"、SR’、S(O)mR1、S(O)2NR’R"、OC(O)R1、OC(O)NR’R"、OS(O)2R1、OS(O)2NR’R"、N(R2)C(O)R1、N(R2)C(O)NR’R"、N(R2)S(O)2R1或N(R2)S(O)2NR’R"；或
    当L为取代或未取代的C1-6烷基、取代或未取代的C1-6卤代烷基、取代或未取代的C2-6烯基、取代或未取代的C2-6卤代烯基、取代或未取代的C2-6炔基、取代或未取代的C2-6卤代炔基、取代或未取代的C3-7环烷基、取代或未取代的C5-7环烯基、取代或未取代的苯基、取代或未取代的萘基、取代或未取代的5元或6元杂环基、或取代或未取代的8元至14元杂芳二环或三环环系，所述取代是指被选自下组的一个或多个基团所取代：卤素、氰基、硝基、R’、OR’、Si(R’)3、NR’R"、C(O)R’、C(O)OR’、C(O)NR’R"、 SR’、S(O)mR1、S(O)2NR’R"、OC(O)R1、OC(O)NR’R"、OS(O)2R1、OS(O)2NR’R"、N(R2)C(O)R1、N(R2)C(O)NR’R"、N(R2)S(O)2R1或N(R2)S(O)2NR’R"时；M为无；
    且A为取代或未取代的苯基、取代或未取代的萘基、取代或未取代的5元或6元杂环基、或取代或未取代的8元至14元杂芳二环或三环环系，所述取代是指被选自下组的一个或多个基团所取代：卤素、氰基、硝基、R’、OR’、Si(R’)3、NR’R"、C(O)R’、C(O)OR’、C(O)NR’R"、SR’、S(O)mR1、S(O)2NR’R"、OC(O)R1、OC(O)NR’R"、OS(O)2R1、OS(O)2NR’R"、N(R2)C(O)R1、N(R2)C(O)NR’R"、N(R2)S(O)2R1或N(R2)S(O)2NR’R"；
    G表示A的任意一个或多个位置上的取代基，且G为H、C1-6烷基、C1-6卤代烷基、C2-6烯基、C2-6卤代烯基、取代或未取代的C2-6炔基、C2-6卤代炔基，或取代或未取代的C3-7环烷基、取代或未取代的C5-7环烯基、取代或未取代的苯基、取代或未取代的萘基、取代或未取代的5元或6元杂环基、或取代或未取代的8元至12元杂芳二环环系，所述取代是指被选自下组的一个或多个基团所取代：卤素、氰基、硝基、R’、OR’、Si(R’)3、NR’R"、C(O)R’、C(O)OR’、C(O)NR’R"、SR’、S(O)mR1、S(O)2NR’R"、OC(O)R1、OC(O)NR’R"、OS(O)2R1、OS(O)2NR’R"、N(R2)C(O)R1、N(R2)C(O)NR’R"、N(R2)S(O)2R1或N(R2)S(O)2NR’R"；
    其中，R’、R"各自独立地为H、C1-6烷基、C1-6卤代烷基、C2-6烯基、C2-6卤代烯基、C2-6炔基、C2-6卤代炔基，或取代或未取代的C3-7环烷基、取代或未取代的C5-7环烯基、取代或未取代的苯基、取代或未取代的萘基、取代或未取代的5元或6元杂环基、或取代或未取代的8元至12元杂芳二环环系，所述取代是指选自下组的一个或多个基团所取代：卤素、氰基、硝基、C1-6烷基、C1-6卤代烷基、C2-6烯基、C2-6卤代烯基、C2-6炔基、C2-6卤代炔基、羟基、羟基C1-4烷基、OR3、NR3R4、C(O)R3、C(O)OR3、C(O)NR3R4、SR3、S(O)mR5、S(O)2NR3R4、OC(O)R5、OC(O)NR3R4、OS(O)2R5、OS(O)2NR3R4、N(R6)C(O)R5、N(R6)C(O)NR3R4、N(R6)S(O)2R5或N(R6)S(O)2NR3R4；
    R1为C1-6烷基、C1-6卤代烷基、C2-6烯基、C2-6卤代烯基、C2-6炔基、C2-6卤代炔基，或取代或未取代的C3-7环烷基、取代或未取代的C5-7环烯基、取代或未取代的苯基、取代或未取代的萘基、取代或未取代的5元或6元杂环基、或取代或未取代的8元至12元杂芳二环环系，所述取代是指被选自下组的一个或多个基团所取代：卤素、氰基、硝基、C1-6烷基、C1-6卤代烷基、C2-6烯基、C2-6卤代烯基、C2-6炔基、C2-6卤代炔基、OR3、NR3R4、C(O)R3、C(O)OR3、C(O)NR3R4、SR3、S(O)mR5、S(O)2NR3R4、OC(O)R5、OC(O)NR3R4、OS(O)2R5、OS(O)2NR3R4、N(R6)C(O)R5、N(R6)C(O)NR3R4、N(R6)S(O)2R5或N(R6)S(O)2NR3R4；
    R2为H、C1-6烷基、C1-6卤代烷基、C2-6烯基、C2-6卤代烯基、C2-6炔基或C2-6卤代炔基，或取代或未取代的C3-7环烷基、取代或未取代的C5-7环烯基、取代或未取代的苯基、取代或未取代的萘基、取代或未取代的5元或6元杂环基、或取代或未取代的8元至12元杂芳二环环系，所述取代是指被选自下组的一个或多个基团所取代：卤素、氰基、硝基、C1-6烷基、C1-6卤代烷基、C2-6烯基、C2-6卤代烯基、C2-6炔基、C2-6卤代炔基、OR3、NR3R4、C(O)R3、C(O)OR3、C(O)NR3R4、SR3、S(O)mR5、S(O)2NR3R4、OC(O)R5、OC(O)NR3R4、OS(O)2R5、OS(O)2NR3R4、N(R6)C(O)R5、N(R6)C(O)NR3R4、N(R6)S(O)2R5或N(R6)S(O)2NR3R4；
    其中，R3、R4、R6各自独立地为H、C1-6烷基、C1-6卤代烷基、C2-6烯基、C2-6卤代烯基、C2-6炔基或C2-6卤代炔基；
    R5为C1-6烷基、C1-6卤代烷基、C2-6烯基、C2-6卤代烯基、C2-6炔基或C2-6卤代炔基；
    m为1或2；
    n为0、1、2、3、4或5。
  2. 如权利要求1所述的化合物，或所述化合物的光学异构体、顺反异构体或农药学上可接受的盐，其特征在于，所述化合物选自下组：
    Figure PCTCN2016071608-appb-100002
    上述各式中，X、L、G、A、M和n的定义如权利要求1中所述，Y为O、S、S(＝O)、S(＝O)2或共价键。
  3. 如权利要求1或2所述的化合物，或所述化合物的光学异构体、顺反异构体或农药学上可接受的盐，其特征在于，X为O或S。
  4. 如权利要求1或2所述的化合物，或所述化合物的光学异构体、顺反异构体或农药学上可接受的盐，其特征在于，
    L为取代或未取代的C1-6亚烷基、取代或未取代的C1-6卤代亚烷基、取代或未取代的C2-6亚烯基、取代或未取代的C2-6卤代亚烯基、取代或未取代的C2-6亚炔基、取代或未取代的C3-7亚环烷基、取代或未取代的C5-7亚环烯基、取代或未取代的亚苯基、取代或未取代的亚萘基、取代或未取代的5元或6元亚杂环基、或取代或未取代的8元至12 元亚杂芳二环环系，所述取代是指被选自下组的一个或多个基团所取代：卤素、氰基、硝基、C1-4烷基、C1-4卤代烷基、C1-4烷氧基、C1-4烷基-羰基、C1-4烷氧基-羰基、C1-4烷基胺基-羰基或苯基胺基-羰基；或
    L为取代或未取代的C1-6烷基、取代或未取代的C1-6卤代烷基、取代或未取代的C2-6烯基、取代或未取代的C2-6卤代烯基、取代或未取代的C2-6炔基、取代或未取代的C3-7环烷基、取代或未取代的C5-7环烯基、取代或未取代的苯基、取代或未取代的萘基、取代或未取代的5元或6元杂环基、或取代或未取代的8元至12元杂芳二环环系，所述取代是指被选自下组的一个或多个基团所取代：卤素、氰基、硝基、C1-4烷基、C1-4卤代烷基、C1-4烷氧基、C1-4烷基-羰基、C1-4烷氧基-羰基、C1-4烷基胺基-羰基或苯基胺基-羰基。
  5. 如权利要求1或2所述的化合物，或所述化合物的光学异构体、顺反异构体或农药学上可接受的盐，其特征在于，M为无；或M为H、C1-6烷基、C1-6卤代烷基、C2-6烯基、C2-6卤代烯基、C2-6炔基、三甲基硅烷基乙炔基，或取代或未取代的C3-7环烷基、取代或未取代的C5-7环烯基、取代或未取代的苯基、取代或未取代的萘基、取代或未取代的5元或6元杂环基、或取代或未取代的8元至14元杂芳二环或三环环系，所述取代是指被选自下组的一个或多个基团所取代：卤素、氰基、硝基、C1-4烷基、C1-4卤代烷基、C1-4烷氧基、C1-4烷基-羰基、C1-4烷氧基-羰基、C1-4烷基胺基-羰基或苯基胺基-羰基。
  6. 如权利要求1或2所述的化合物，或所述化合物的光学异构体、顺反异构体或农药学上可接受的盐，其特征在于，A为取代或未取代的苯基、取代或未取代的萘基、取代或未取代的5元或6元杂环基、或取代或未取代的8元至12元杂芳二环环系，所述取代是指被选自下组的一个或多个基团所取代：卤素、氰基、硝基、C1-4烷基、C1-4卤代烷基、C1-4烷氧基、C1-4卤代烷氧基、苯氧基、胺基磺酸基、胺基-羰基、C1-4烷基-羰基、C1-4烷氧基-羰基、C1-4烷基胺基-羰基或苯基胺基-羰基。
  7. 如权利要求1或2所述的化合物，或所述化合物的光学异构体、顺反异构体或农药学上可接受的盐，其特征在于，G为H、C1-6烷基、C1-6卤代烷基、C2-6烯基、C2-6卤代烯基、C2-6炔基、三甲基硅烷基乙炔基，或取代或未取代的C3-7环烷基、取代或未取代的C5-7环烯基、取代或未取代的苯基、取代或未取代的萘基、取代或未取代的5元或6元杂环基或取代或未取代的8元至12元杂芳二环环系，所述取代是指被选自下组的一个或多个基团所取代：卤素、氰基、硝基、C1-4烷基、C1-4卤代烷基、C1-4烷氧基、C1-4烷基-羰基、C1-4烷氧基-羰基、C1-4烷基胺基-羰基或苯基胺基-羰基。
  8. 一种农用组合物，其特征在于，其包含：
    (1)0.001-99.99重量％的权利要求1-7中任一项所述的化合物、或所述化合物的光学异构体、顺反异构体或农药学上可接受的盐、或者它们的组合；以及
    (2)农药学上可接受的载体和/或赋形剂。
  9. 如权利要求1所述的化合物、或所述化合物的光学异构体、顺反异构体或农药学上可接受的盐或如权利要求8所述农用组合物的用途，其特征在于，用于杀灭或预防线虫或用于制备杀线虫剂组合物。
  10. 一种如权利要求1所述的化合物、或所述化合物的光学异构体、顺反异构体或农药学上可接受的盐的制备方法，其特征在于，
    (A)所述方法包括步骤：
    (1)在惰性溶剂中，将式(a)化合物与双(三氯甲基)碳酸酯(BTC)进行关环反应，得到式(b)化合物：
    (2)在惰性溶剂中，将式(b)化合物与碳酸铵进行开环反应，得到式(c)化合物：
    (3)在惰性溶剂中，将式(c)化合物经重氮化反应、关环反应，得式(d)化合物：
    Figure PCTCN2016071608-appb-100003
    (4)在惰性溶剂中，在碱存在下，式(d)化合物与BrCH2(CH2)nBr反应，得到式(e)化合物；
    (5)在惰性溶剂中，将式(e)化合物与式(f)化合物或式(p)化合物(H-Y-Q-L-M)反应，从而得到式(I)化合物：
    Figure PCTCN2016071608-appb-100004
    或(B)所述方法包括步骤：
    (4’)在惰性溶剂中，在碱存在下，式(d)化合物与BrCH2(CH2)nC≡CH反应，得式(g)化合物：
    (5’)在惰性溶剂中，将式(g)化合物与式(h)化合物反应，从而得式(I)化合物：
    Figure PCTCN2016071608-appb-100005
    或(C)所述方法包括步骤：
    (4”)在惰性溶剂中，在碱存在下，式(d)化合物与BrCH2(CH2)nYH反应，得式(i)化合物：
    (5”)在惰性溶剂中，将式(i)化合物与式(k)化合物反应，从而得到式(I)化合物：
    Figure PCTCN2016071608-appb-100006
    或(D)所述方法包括步骤：
    (5”’)在惰性溶剂中，在碱存在下，将式(e)化合物与式(m)化合物反应，然后经脱保护得式(n)化合物：
    (6)在惰性溶剂中，将式(n)化合物与式(o)化合物反应，从而得到式(I)化合物：
    Figure PCTCN2016071608-appb-100007
    或(E)所述方法包括步骤：
    (6’)在惰性溶剂中，式(n)化合物与式(o’)化合物反应，得到式(I)化合物：
    Figure PCTCN2016071608-appb-100008
    或(F)所述方法包括步骤：
    (5””)在惰性溶剂中，在碱存在下，式(e)化合物与式(p)化合物反应，得到式(I)化合物：
    Figure PCTCN2016071608-appb-100009
    上述各式中，X、Y、Q、L、M、A、G和n的定义如权利要求1中所述。
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