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WO2019086009A1 - 含氮稠合三环化合物及其作为农林业杀虫剂的应用 - Google Patents

含氮稠合三环化合物及其作为农林业杀虫剂的应用 Download PDF

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Publication number
WO2019086009A1
WO2019086009A1 PCT/CN2018/113811 CN2018113811W WO2019086009A1 WO 2019086009 A1 WO2019086009 A1 WO 2019086009A1 CN 2018113811 W CN2018113811 W CN 2018113811W WO 2019086009 A1 WO2019086009 A1 WO 2019086009A1
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cor
alkyl
aryl
substituted
hydrogen
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PCT/CN2018/113811
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English (en)
French (fr)
Inventor
徐汉虹
江薰垣
魏孝义
张志祥
林菲
姚光凯
邓成菊
赵晨
杨帅
赵伟靖
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South China Agricultural University
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South China Agricultural University
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Priority claimed from CN201711069917.7A external-priority patent/CN108003162B/zh
Priority claimed from CN201810219338.4A external-priority patent/CN108129481B/zh
Application filed by South China Agricultural University filed Critical South China Agricultural University
Priority to BR112020008750-5A priority Critical patent/BR112020008750B1/pt
Priority to US16/758,053 priority patent/US11401271B2/en
Priority to EP18873292.9A priority patent/EP3689877A4/en
Priority to JP2020526237A priority patent/JP6933413B2/ja
Publication of WO2019086009A1 publication Critical patent/WO2019086009A1/zh
Anticipated expiration legal-status Critical
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Classifications

    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/90—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
    • A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
    • A01N47/22—O-Aryl or S-Aryl esters 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<
    • A01N47/38—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing the group >N—CO—N< where at least one nitrogen atom is part of a heterocyclic ring; Thio analogues thereof
    • 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
    • C07D471/12—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 three hetero rings
    • C07D471/14—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
    • C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
    • C07D487/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
    • C07D487/12—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains three hetero rings
    • C07D487/14—Ortho-condensed systems

Definitions

  • the invention belongs to the field of heterocyclic compounds, and in particular relates to a class of fused heterocyclic compounds and optical isomers, cis-trans isomers or agrochemically acceptable salts thereof, and to a preparation method and application thereof.
  • the new heterocyclic pesticides represented by nitrogen-containing heterocycles have high insecticidal activity, broad spectrum of insecticides, low toxicity to mammals, and proper field stability. Heterocyclic compounds have become an important hotspot for the creation of new pesticides. .
  • Novel structural molecules with large structural differences from previous pesticide molecules are considered to have no cross-resistance with existing pesticides and can be used to control the development of pest resistance (Pesticide Biochemistry and Physiology, 2015, 121:22).
  • a wide range of fused heterocyclic compounds have been synthesized and reported to have a wide range of biological activities (for example: Computational Biology and Chemistry, 2018, 74: 218; Bioorganic & Medicinal Chemistry Letters, 2017, 27: 3201; Journal of Medicinal Chemistry, 2017 , 60:9691; Journal of Heterocyclic Chemistry, 2017, 54: 2788; Organic & Biomolecular Chemistry, 2016, 14: 8721; Journal of Enzyme Inhibition and Medicinal Chemistry, 2015, 31: 195; New Journal of Chemistry, 2015, 39: 1060; Chemistry-A European Journal, 2015, 21: 16859; Bioorganic & Medicinal Chemistry Letters, 2014, 24: 2693; Journal of Medicinal Chemistry, 2013, 56: 7458; Bioorganic &
  • the fused heterocyclic compound and its optical isomer, cis-trans isomer or agrochemically acceptable salt have high killing activity against agricultural and forestry pests and sanitary pests, and even more surprisingly, It has a delayed effect on pests such as red fire ants and has a better killing effect.
  • Another object of the present invention is to provide a process for producing the fused heterocyclic compound and its optical isomer, cis-trans isomer or agrochemically acceptable salt.
  • Another object of the present invention is to provide the use of the fused heterocyclic compound and its optical isomer, cis-trans isomer or agrochemically acceptable salt in the preparation of an insecticide.
  • R 11 and R 12 are each independently hydrogen, halogen, -NO 2 , -CN, -COR 17 , -CO 2 R 17 , -CONR 17 R 18 , -S(O)R 17 , -S(O 2 R 17 , -N R 17 R 18 , -N R 17 CO R 18 , -N R 17 CON R 18 R 19 , -N R 17 CO 2 R 18 , -N R 17 S(O) 2 R 18 , alkyl, hetero An alkyl, alkenyl, cycloalkyl, cycloalkenyl, aryl, heterocyclyl or heteroaryl group; wherein alkyl, alkenyl, cycloalkyl, cycloalkenyl, aryl, heterocyclyl or heteroaryl Substituted or substituted with one or more substituents R 10 ;
  • R 13 is hydrogen, -COR 7 , -CO 2 R 17 , -S(O) 2 R 17 , -CONR 17 R 18 , alkyl, heteroalkyl, alkenyl, cycloalkyl, cycloalkenyl, aryl Wherein alkyl, alkenyl, cycloalkyl, cycloalkenyl, aryl is unsubstituted or substituted with one or more substituents R 10 ;
  • R 14 and R 15 are each independently hydrogen, halogen, -CN, -OH, -N R 17 R 18 , -O R 17 , -CO R 17 , -CO 2 R 17 , -CONR 17 R 18 , -N R 17 CO R 18 , -NR 17 CON R 18 R 19 , -NR 17 CO 2 R 18 , -NR 17 S(O) 2 R 18 , -S(O)R 17 , -S(O) 2 R 17 , alkyl , heteroalkyl, alkenyl, cycloalkyl, cycloalkenyl, aryl, heterocyclyl or heteroaryl; wherein alkyl, alkenyl, cycloalkyl, cycloalkenyl, aryl, heterocyclyl or heteroaryl; wherein alkyl, alkenyl, cycloalkyl, cycloalkenyl, aryl, heterocyclyl or hetero An aryl group is unsubsti
  • Y is N or CH
  • Z 1, Z 2, Z 3 , Z 4 are each independently C or N, with the proviso that Z 1 to Z 4 are at most two are N, and the ring containing Z 1 to Z 4 are aromatic;
  • R 16 represents a substituent on the ring of Z 1 to Z 4 , and the number of R 16 may be one or more, and each R 16 is independently hydrogen, halogen, -CN, alkyl, heteroalkyl, -CO R 17 , -CO 2 R 17 , -N R 17 R 18 , -CONR 17 R 18 , -N R 17 CO R 18 , -NR 17 CON R 18 R 19 , -NR 17 CO 2 R 18 or -NR 17 S(O) 2 R 18 ;
  • R 17 , R 18 and R 19 are each independently hydrogen, alkyl, heteroalkyl, alkenyl, cycloalkyl, cycloalkenyl, heterocyclyl, aryl or heteroaryl; wherein alkyl, alkenyl, a cycloalkyl, cycloalkenyl, aryl, heterocyclyl or heteroaryl group unsubstituted or substituted with one or more substituents R 10 ;
  • R 10 is halogen, C 1 -C 6 alkyl, C 2 -C 6 alkenyl, substituted or unsubstituted cycloalkyl, cycloalkenyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl , substituted or unsubstituted heterocyclic group, -CN, -NH 2 , -OR"', -NR"'R"", -COR”', -CO 2 R"', -CONR"'R"", -NR"'COR”", -NR"'CONR"'R"", -NR"'CO 2 R"", -S(O) 2 R"' or -NR"'S(O) 2 R"", wherein R"'and R "" are independently hydrogen, C 1 -C 6 alkyl, C 2 -C 6 alkenyl, cycloalkyl, cycloalkenyl, aryl, heteroaryl, hetero
  • Y is N or CH
  • R 11 is halogen, -CN, -COR 17 , -CONR 17 R 18 , -S(O)R 17 , -N R 17 R 18 , -N R 17 CO R 18 , aryl, heterocyclic or heteroaryl; Wherein the aryl, heterocyclic or heteroaryl group is unsubstituted or substituted with one or more substituents R 10 ;
  • R 12 is hydrogen, -COR 17 , -CONR 17 R 18 , -S(O)R 17 , -S(O) 2 R 17 , -N R 17 R 18 , -N R 17 CO R 18 , -NR 17 CONR 18 R 19 , —NR 17 CO 2 R 18 , aryl, heterocyclyl or heteroaryl; wherein the aryl, heterocyclyl or heteroaryl is unsubstituted or substituted by one or more substituents R 10 ;
  • R 13 is hydrogen, -COR 17 , alkyl, heteroalkyl or alkenyl
  • R 14 is halogen, -CN, -N R 17 R 18 , -O R 17 , -CO R 17 , -CO 2 R 17 , -CONR 17 R 18 , -N R 17 CO R 18 , -NR 17 CO 2 R 18 , An alkyl group, a heteroalkyl group or an alkenyl group; wherein the alkyl group, heteroalkyl group or alkenyl group is unsubstituted or substituted with one or more substituents R 10 ;
  • R 15 is hydrogen, halogen, -CN, -N R 17 R 18 , -O R 17 , -CO R 17 , -CO 2 R 17 , -CONR 17 R 18 , -N R 17 CO R 18 , -NR 17 CO 2 R 18 , alkyl, heteroalkyl or alkenyl; wherein the alkyl, heteroalkyl or alkenyl group is unsubstituted or substituted by one or more substituents R 10 .
  • R 16 may be one or more, and each R 16 is independently hydrogen, halogen, alkyl, heteroalkyl, alkenyl, -S(O)R 17 , -S(O) 2 R 17 , -COR 17 , -N R 17 R 18 , -CONR 17 R 18 , -N R 17 CO R 18 or -NR 17 S(O) 2 R 18 ;
  • R 11 is halogen, -CN, -COR 17 , -CONR 17 R 18 , -S(O)R 17 , -N R 17 R 18 , -N R 17 CO R 18 , aryl, heterocyclic or heteroaryl; Wherein the aryl, heterocyclic or heteroaryl group is unsubstituted or substituted with one or more substituents R 10 ;
  • R 12 is -CONR 17 R 18 , -S(O)R 17 , -S(O) 2 R 17 , -N R 17 R 18 , -N R 17 CO R 18 , -N R 17 CON R 18 R 19 , aryl a heterocyclic group or a heteroaryl group; wherein the aryl group, heterocyclic group or heteroaryl group is unsubstituted or substituted with one or more substituents R 10 ;
  • R 13 is hydrogen, -COR 17 , alkyl or alkenyl
  • R 14 and R 15 are each independently halogen, -CN, -N R 17 R 18 , -O R 17 , -CO R 17 , -CO 2 R 17 , -CONR 17 R 18 , -N R 17 CO R 18 , -NR 17 CO 2 R 18 , alkyl, heteroalkyl, alkenyl; wherein alkyl, heteroalkyl, alkenyl is unsubstituted or substituted with one or more substituents R 10 .
  • R 11 is halogen, -CN, -COR 17 , -CONR 17 R 18 , -S(O)R 17 , -N R 17 R 18 , -N R 17 CO R 18 ;
  • R 12 is -S(O)R 17 , -S(O) 2 R 17 , -N R 17 R 18 , -N R 17 CO R 18 , aryl or heteroaryl; wherein the aryl or heteroaryl is unsubstituted Or substituted with one or more substituents R 10 ;
  • R 13 is hydrogen, -COR 17 , alkyl or alkenyl
  • R 14 and R 15 are each independently halogen, -CN, -N R 17 R 18 , -O R 17 , -CO R 17 , -CO 2 R 17 , -CONR 17 R 18 , -N R 17 CO R 18 , -NR 17 CO 2 R 18 , alkyl, heteroalkyl or alkenyl; wherein the alkyl or alkenyl group is unsubstituted or substituted with one or more substituents R 10 ;
  • Z 1 , Z 2 , Z 3 , Z 4 are all C
  • R 16 may be one or more, and each R 16 is independently halogen, alkyl, heteroalkyl, -S(O)R 17 , -S (O) 2 R 17 , -COR 17 , -N R 17 R 18 , -N R 17 CO R 18 or -NR 17 S(O) 2 R 18 .
  • R 11 is halogen, -CN, -COR 17 or -CONR 17 R 18 ;
  • R 12 is -S(O)R 17 , -S(O) 2 R 17 , -NR 17 COR 18 , aryl or heteroaryl; wherein the aryl or heteroaryl is unsubstituted or substituted by one or more Substituent R 10 ;
  • R 13 is hydrogen, -COR 17 or an alkyl group
  • Z 1 , Z 2 , Z 3 , Z 4 are all C
  • R 16 may be one or more, and each R 16 is independently halogen, heteroalkyl, -S(O)R 17 , -NR 17 R 18 Or -NR 17 COR 18 .
  • R 11 is -CN or -COR 17 ;
  • R 12 is -S(O)R 17 or aryl; wherein the aryl group is substituted with one or more substituents R 10 ;
  • R 13 is hydrogen, -COR 17 , methyl or ethyl
  • R 14 and R 15 are each independently halogen, -OR 17 , -COR 17 , -CO 2 R 17 , -CONR 17 R 18 , -NR 17 COR 18 , -NR 17 CO 2 R 18 , alkyl, heterocycloalkane Or an alkenyl group; wherein the alkyl or alkenyl group is unsubstituted or substituted with one or more substituents R 10 ;
  • Z 1 , Z 2 , Z 3 , Z 4 are all C
  • R 16 may be one or more, and each R 16 is independently halogen or heteroalkyl.
  • R 11 is -CN or -COR 17 and R 17 is alkyl or heteroalkyl;
  • R 12 is -S(O)R 17 and R 17 is alkyl or heteroalkyl;
  • R 13 is hydrogen, -COR 17 , methyl or ethyl, and R 17 is alkyl;
  • R 14 and R 15 are each independently halogen, -OR 17 , -COR 17 , -CO 2 R 17 , -CONR 17 R 18 , -NR 17 COR 18 , -NR 17 CO 2 R 18 , alkyl, heterocycloalkane Or an alkenyl group; wherein the alkyl or alkenyl group is unsubstituted or substituted with one or more substituents R 10 ;
  • Z 1 , Z 2 , Z 3 , Z 4 are all C
  • R 16 may be one or more, and each R 16 is independently halogen or heteroalkyl.
  • the invention also discloses a pyrazole ring-containing fused heterocyclic compound and an optical isomer, cis-trans isomer or agrochemically acceptable salt thereof, the pyrazole ring-containing fused heterocyclic compound having Structure shown by formula (II):
  • R 1 is hydrogen, halogen, -CN, alkyl, heteroalkyl, aryl or heteroaryl; wherein the alkyl, aryl or heteroaryl is unsubstituted or substituted by one or more substituents R 9 ;
  • R 2 is hydrogen, halogen, -CN, -S(O)R 7 , -S(O) 2 R 7 , alkyl, heteroalkyl, aryl or heteroaryl; wherein alkyl, aryl or heteroaryl Substituent substituted or substituted with one or more substituents R 9 ;
  • R 3 is hydrogen, -COR 7 , alkyl or heteroalkyl
  • R 4 and R 5 are each independently hydrogen, halogen, -CN, -COR 7 , -CO 2 R 7 , -CH 2 COR 7 , -CH 2 COOR 7 , amino, alkyl, heteroalkyl, aryl or a heteroaryl group; wherein the amino group, alkyl group, aryl group or heteroaryl group is unsubstituted or substituted with one or more substituents R 9 , and R 4 and R 5 are not simultaneously hydrogen;
  • Z 1 and Z 2 are each independently C or N, and are not N at the same time, and the ring containing Z 1 and Z 2 is an aromatic ring;
  • R 6 represents a substituent on the ring of Z 1 and Z 2 , and the number of R 6 may be one or more, and each R 6 is independently hydrogen, halogen, —NO 2 , —CN, alkyl, heteroalkyl, -OR 7 , -COR 7 , -CO 2 R 7 or -NR 7 R 8 ;
  • R 7 and R 8 are each independently hydrogen, hydroxy, amino, C 1 -C 6 alkyl, heteroalkyl, aryl or heteroaryl; wherein alkyl, aryl or heteroaryl is unsubstituted or Or substituted with a plurality of substituents R 9 ;
  • R 9 is halogen, C 1 -C 6 alkyl, heteroalkyl, -CN, -NH 2 , -OH, -COR', -CO 2 R' or -CONR'R", wherein R' and R" are independent It is hydrogen, C 1 -C 6 alkyl or heteroalkyl.
  • R 6 is a 5-substituted-CF 3 monosubstituted pyridine ring, and the compound has the formula of formula (a):
  • R 3 is hydrogen, methyl or chloromethyl
  • R 4 and R 5 are each independently hydrogen, halogen, -CN, -COR 7 , -CO 2 R 7 , -CH 2 COR 7 , -CH 2 COOR
  • R 6 is a monosubstituted chloro ring at the 5-position of the chloro ring, and the compound has the formula of formula (b):
  • R 3 is hydrogen, methyl or chloromethyl
  • R 4 and R 5 are each independently hydrogen, halogen, -CN, -COR 7 , -CO 2 R 7 , -CH 2 COR 7 , -CH 2 COOR
  • R 1 is -CN or -CF 3
  • R 2 is -CN, -CF 3 , -OCF 3 , -SOCF 3 or -SOCH 2 CH 3
  • R 3 is hydrogen, -CH 3 , -Ac or -CH 2 CH 2 Cl
  • the substituent of R 6 at the 3-position of the phenyl ring is -Cl, -Br, -CF 3 , -CH 3 , -CN, -CO 2 CH 3 or -NO 2
  • R 6 is in the benzene ring.
  • R 4 and R 5 are each independently hydrogen, halogen, -CN, -COR 7 , -CO 2 R 7 , -CH 2 COR 7 , —CH 2 COOR 7 , amino, alkyl, heteroalkyl, aryl or heteroaryl; wherein the amino, alkyl, aryl or heteroaryl group is unsubstituted or has one or more substituents R 9 substitution;
  • R 1 is -CN, -CF 3 , -CHO or -CH 2 NH 2
  • R 2 is -OCF 3 , -CF 3 , -CN, -SOCF 3 , -SOCH 3 , -SOCH 2 CH 3 , -SOPh -SOCH 2 Ph, -SOC 6 H 13
  • R 6 is -Cl or -CF 3
  • R 4 and R 5 are each independently hydrogen, halogen, -CN, -COR 7 , -CO 2 R 7 , -CH 2 COR 7 , -CH 2 COOR 7 , amino group, An alkyl, heteroalkyl, aryl or heteroaryl group; wherein the amino, alkyl, aryl or heteroaryl group is unsubstituted or substituted with one or more substituents R 9 ;
  • R 1 is -CN
  • R 2 is -SOCF 3
  • R 6 is -Cl or -CF 3
  • R 4 and R 5 are each independently hydrogen, halogen, -CN, -COR 7 , -CO 2 R 7 , -CH 2 COR 7 , -CH 2 COOR 7 , amino, alkyl, heteroalkyl, aryl or heteroaryl; wherein the amino, alkyl, aryl or heteroaryl group is unsubstituted or substituted by one or more The group R 9 is substituted; and R 4 and R 5 are not simultaneously hydrogen.
  • R 4 and R 5 are each independently hydrogen, halogen, -CN, -COR 7 , -CO 2 R 7 , -CH 2 COR 7 , -CH 2 COOR 7 , amino, alkyl or heteroalkyl;
  • R 7 is hydrogen, halogen, hydroxy, C 1-4 alkyl, C 1-4 haloalkyl, C 1-4 alkenyl, C 1-4 haloalkenyl, amino or substituted amino.
  • R 1 is -CN, R 2 is -SOCF 3 or -OCF 3 ; or R 1 is -CF 3 and R 2 is -SOCF 3 ;
  • R 1 is -CN or -CF 3 ;
  • R 2 is -SOCF 3 , -SOCH 2 CH 3 , -OCF 3 , -CF 3 , -CN or halogen.
  • R 3 is -CH 3 , -Ac or -CH 2 CH 2 Cl, R 2 is -SOCF 3 , R 1 is -CN, R 4 and R 5 are -CO 2 Me;
  • R 3 is hydrogen, when R 2 is -CN, -CF 3 or -SOCH 2 CH 3 , R 1 is -CN or -CF 3 , and R 4 and R 5 are each independently -CO 2 Me or -CH 2 CO 2 Me;
  • R 3 is hydrogen
  • R 2 is -OCF 3 or -SOCF 3
  • R 1 is -CN or -CF 3
  • R 4 and R 5 are each independently hydrogen, halogen, -CN, -COR 7 , -CO 2 R 7 , -CH 2 COR 7 , -CH 2 COOR 7 , amino, alkyl, heteroalkyl, aryl or heteroaryl; wherein the amino, alkyl, aryl or heteroaryl group is unsubstituted or Substituted by one or more substituents R 9 .
  • R 3 is hydrogen
  • R 2 is -CN, -CF 3 , -SOPh, -SOCH 2 Ph, -SOC 6 H 13
  • R 1 is -CN
  • R 4 and R 5 are each independently -CO 2 Me or -CO 2 CH 2 Me;
  • R 3 is hydrogen, R 2 is -SOCF 3 , and when R 1 is -CHO or -CH 2 NH 2 , R 4 and R 5 are each independently -CO 2 Me or -CO 2 CH 2 Me;
  • R 3 is hydrogen, when R 2 is -OCF 3 or -SOCF 3 , R 1 is -CN or -CF 3 , and R 4 and R 5 are each independently hydrogen, halogen, -CN, -COR 7 , - CO 2 R 7 , -CH 2 COR 7 , -CH 2 COOR 7 , amino, alkyl, heteroalkyl, aryl or heteroaryl; wherein the amino, alkyl, aryl or heteroaryl group is unsubstituted or One or more substituents R 9 are substituted.
  • R 6 is 3-Cl and 6-CF 3 , 3-Cl and 4-CF 3 , 4-Cl and 5-CF 3 or 5 on the benzene ring.
  • R 4 and R 5 are each independently -CO 2 Me, -CH 2 CO 2 Me, -CO 2 Et, -CH 2 CO 2 Et, -CH 2 CO 2 CH 2 CF 3 Or -CH 2 CO 2 CH 2 CHF 2 .
  • An agricultural composition comprising:
  • a specific application is to apply the insecticide directly to the pest or to the place where it is in contact (for example, in a plant body that is or may be subject to pests, in the soil surrounding it or in the environment).
  • the present invention has the following beneficial effects:
  • the present invention discloses a novel structure of fused heterocyclic compounds and fused heterocyclic compounds containing pyrazole rings.
  • the fused heterocyclic compound and the pyrazole ring-containing fused heterocyclic compound and optical isomers, cis-trans isomers or agrochemically acceptable salts thereof have high killing of agricultural and forestry pests and sanitary pests and the like.
  • Inactivated, and the compound of the present invention has a deferred effect on invading pests such as red fire ants, so that the pest can carry the drug to the nest, thereby having a better killing effect on the whole red fire ant nest and the queen; in pest control
  • the aspect has a good application prospect.
  • the compound of the invention has lower toxicity to environmental organisms, such as bees, silkworms, etc., and therefore has a good application prospect.
  • the inventors of the present invention have designed, synthesized, and screened a new class of fused heterocyclic compounds based on long-term and in-depth research, based on the existing resistance of heterocyclic pesticides and environmental hazards.
  • a fused heterocyclic compound containing a pyrazole ring which has a markedly enhanced insecticidal activity and an expanded insecticidal spectrum.
  • the invention is further illustrated by the following specific examples, but the specific examples are not intended to limit the invention. Unless otherwise stated, the reagents and methods involved in the examples are all reagents and methods commonly used in the art.
  • halogen refers to fluoro, chloro, bromo and iodo
  • halo refers to fluoro, chloro, bromo and iodo
  • the term "halo" before the radical name means that the radical is partially or completely halogenated, ie, substituted by any combination of F, Cl, Br or I, For example, monofluorodichloromethyl, difluoromethyl, trichloromethyl, pentafluoroethyl, or the like.
  • alkyl refers to a hydrocarbyl group selected from saturated straight or branched chain hydrocarbyl groups. It preferably comprises from 1 to 12 carbon atoms, more preferably from 1 to 6 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, Or a similar group.
  • cycloalkyl refers to a selected cycloalkyl group which includes a monocyclic or polycyclic group.
  • the cycloalkyl group preferably has 3 to 12 carbon atoms.
  • the cycloalkyl group may be a monocyclic group having 3 to 12 carbon atoms, such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclodecyl group, a cyclodecyl group, a cyclodecyl group, and a ring twelve.
  • the cycloalkyl group may also be a bicyclic group having 4 to 12 carbon atoms, such as a bicyclic ring of a [4,5], [5,5], [5,6], and [6,6] ring system selected from a bicyclic ring.
  • a bicyclic ring of a [4,5], [5,5], [5,6], and [6,6] ring system selected from a bicyclic ring selected from a bicyclic ring.
  • the cycloalkenyl group has 3 to 12 carbon atoms.
  • aryl refers to a group selected from the group consisting of: (a) 5- and 6-membered carbocyclic aromatic rings, for example, phenyl, furan or thiophene rings; (b) bicyclic systems such as 7-12 membered bicyclic rings. a system wherein at least one ring is a carbocyclic ring and an aromatic ring, such as naphthalene or 1,2,3,4-tetrahydroquinoline; (c) a tricyclic system such as a 10-15 membered tricyclic ring system, wherein at least one ring is Carbocyclic and aromatic rings, such as hydrazine.
  • the aryl group is selected from the group consisting of a 5- and 6-membered carbocyclic aromatic ring fused to a 5- to 7-membered cycloalkyl group or, optionally, at least one selected from the group consisting of N, O, and S.
  • the heterocyclic ring of the atom the condition is that when the carbocyclic aromatic ring is fused to the heterocyclic ring, the point of attachment is on the carbocyclic aromatic ring, and when the carbocyclic aromatic ring is fused to the cycloalkyl group, the point of attachment can be in the carbon.
  • the ring aromatic ring or on the cycloalkyl group On the ring aromatic ring or on the cycloalkyl group.
  • a divalent group formed of a substituted benzene derivative and having a free valence on a ring atom is referred to as a substituted phenylene group.
  • a naphthyl group having two points of attachment is referred to as a naphthylene group.
  • the aryl group does not include or overlap with a heteroaryl group, which are respectively defined below.
  • the resulting ring system is a heteroaryl group as defined herein, rather than an aryl group.
  • heteroalkyl refers to an alkyl group comprising at least one heteroatom, and heteroatoms refer to a non-C atom.
  • the hetero atom is preferably N, O, S, P or Se or the like.
  • heteroaryl refers to a group selected from the group consisting of:
  • a 5- to 7-membered aromatic monocyclic ring comprising 1, 2, 3 or 4 heteroatoms selected from N, O and S, the remaining ring atoms being carbon;
  • a 11- to 14-membered bicyclic ring comprising 1, 2, 3 or 4 heteroatoms selected from N, O and S, the remaining ring atoms being carbon, and wherein at least one of the rings is aromatic and at least one hetero atom is present In the aromatic ring;
  • a heteroaryl group includes a 5- to 7-membered heterocyclic aromatic ring fused to a 5- to 7-membered cycloalkyl ring.
  • the point of attachment may be on a heteroaromatic or cycloalkyl ring.
  • heterocyclyl refers to a ring selected from the group consisting of 4 to 12 membered monocyclic, bicyclic and tricyclic saturated and partially unsaturated rings, except for 1, 2, selected from oxygen, sulfur and nitrogen.
  • the 3 or 4 heteroatoms contain at least one carbon atom.
  • an aliphatic spiro ring comprising at least one heteroatom selected from the group consisting of N, O and S, provided that the point of attachment is on the heterocyclic ring.
  • the ring may be saturated or contain at least one double bond.
  • the heterocyclic ring can be substituted by oxidation.
  • the point of attachment can be a carbon atom or a heteroatom in the heterocycle.
  • alkoxy refers to a hydrocarbyloxy group selected from the group consisting of saturated straight or branched alkoxy groups. It comprises from 1 to 12 carbon atoms, preferably from 1 to 6 carbon atoms, such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy , tert-butoxy, or the like.
  • R""' and R""' are each independently selected from hydrogen, unsubstituted (C 1 -C 6 )alkyl and heteroalkyl, unsubstituted aryl, aryl having 1 to 3 halogen substitutions, Unsubstituted alkyl, alkoxy or thioalkoxy, or aryl-(C 1 -C 4 )alkyl.
  • R""' and R""" are attached to the same nitrogen atom, they are capable of forming a 5, 6 or 7 membered ring in combination with a nitrogen atom, and therefore, -NR""'R””” includes 1-pyrrolidinyl and 4-morpholinyl.
  • Alkyl includes, for example, trihaloalkyl (e.g., -CF 3 and -CH 2 CF 3).
  • fused heterocyclic ring refers to a polycyclic ring system such as a bicyclic or tricyclic ring system in which two rings share only two ring atoms and one bond, and at least one non-C in the ring atom thereof atom.
  • fused heterocyclic ring may include a fused biheterocycloalkyl group such as those consisting of 7 to 12 ring atoms selected from the above [4, 4], [4, 5], [5, 5], [ a bicyclic heterocycle of the 5,6] and [6,6] ring systems; a fused bicyclic heteroaryl ring, such as the above 8- to 12-membered bicyclic heteroaryl ring; a fused tricyclic heteroaryl ring, such as 11 to 14 membered tricyclic heteroaryl ring, for example, pyrazolo[1,5-a]quinazoline, pyrazolo[1,5-c]quinazoline, pyrrolo[1,2-a] Quinazoline, pyrazolo[1,5-a]pyrido[3,2-e]pyrimidine, pyrazolo[1,5-a]pyrido[3,4-e]pyrimidine, pyrazolo[ 1,5-a]pyrido[2,3
  • the compound may contain an asymmetric center and thus may exist as an enantiomer. When the compound has two or more asymmetric centers, they may additionally exist as diastereomers.
  • Enantiomers and diastereomers are a broader class of stereoisomers. All such possible stereoisomers include substantially pure resolved enantiomers (meaning that the target stereoisomer contains no more than 10% by weight of any other stereoisomer), its racemic mixture and non- A mixture of enantiomers. Unless otherwise stated, one of the isomers mentioned applies to any possible isomer. When all isomer components are not specified, all possible isomers are included.
  • Some compounds may have different hydrogen attachment points and are referred to as tautomers.
  • keto form a compound comprising a carbonyl-CH 2 C(O)- group
  • enol form a compound comprising a carbonyl-CH 2 C(O)- group
  • enol form When applied, separate keto and enol forms as well as mixtures thereof are also included.
  • acceptable salt refers to a salt whose cation or anion is known and which can be used to form a use in the art.
  • Suitable salts having bases for example, salts formed from compounds of formula (I), formula (II) containing a carboxyl group, including alkali metals (such as sodium and potassium), alkaline earth metals (such as calcium and magnesium), ammonium And salts of amines.
  • Suitable salts having acid addition such as salts formed from compounds of formula (I), formula (II) containing an amino group, including salts with inorganic acids, such as hydrochlorides, sulfates, sulfites, phosphoric acid Salts, hydrogen phosphates and nitrates and salts with organic acids such as acetic acid, malic acid, tartaric acid, citric acid, lactic acid, salicylic acid and oxalic acid.
  • inorganic acids such as hydrochlorides, sulfates, sulfites, phosphoric acid Salts, hydrogen phosphates and nitrates and salts with organic acids such as acetic acid, malic acid, tartaric acid, citric acid, lactic acid, salicylic acid and oxalic acid.
  • the free base can be obtained by alkalizing a solution of the acid salt.
  • the addition salt can be prepared by dissolving the free base in a suitable organic solvent and treating the solution with an acid, consistent with conventional procedures for preparing acid addition salts from basic compounds.
  • insects can be used to control and eliminate a wide range of agricultural and forestry pests, sanitary pests, and pests that are harmful to animal health.
  • insecticide is a general term for substances having the action of controlling all the pests mentioned above.
  • pests include, but are not limited to, Coleoptera: for example, Sitophilus zeamais, Tribolium castaneum, Henosepilachna vigintioctomaculata, and Henosepilachna sparsa, fine Agriotes fusciollis, Anomala cupripes, Popillia quadriguttata, Monolepta hieroglyphica, Monochamus alternatus, Echinocnemus squameus, Basiprionota bisignata, Anoplophora chinensis, Apripona germari, Soclytus schevy, or Agriotes fuscicollis;
  • Lepidoptera for example , Lymantria dispar, Malacosoma neustria testacea, Diaphania perspectalis, Clania variegata, Cnidocampa flauescens, Dendrolimus punctatus, ancient moth (Orgyia antiqua), Paranthrene
  • Animals that are harmful to animal health include Boophilus microplus, Haemaphysalis longicornis, Hyalomma anatolicum, Hypoderma spp., Fasciola hepatica, and shellfish. Moniezia blanchard, Ostertagia spp., Trypanosoma enansi, Babesia bigemina, and the like.
  • the compound of the present invention preferably has agricultural and forest pests such as Lepidoptera, Hymenoptera, Hemiptera, Coleoptera, Diptera, and Acarina, animal parasitic mites and/or mites, and sanitary pests.
  • agricultural and forest pests such as Lepidoptera, Hymenoptera, Hemiptera, Coleoptera, Diptera, and Acarina, animal parasitic mites and/or mites, and sanitary pests.
  • High activity more preferably high activity against sucking or chewing mouthparts pests.
  • Insecticide composition containing the active substance of the present invention
  • the active substance of the present invention can be prepared into a pesticide composition in a conventional manner.
  • These active compounds can be combined into conventional preparations such as solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols, natural and synthetic materials impregnated with active substances, in the polymerization.
  • Microcapsules, coatings for seeds, and preparations for use with combustion devices eg, smoked cartridges, smoked cans and smokers
  • UUV ultra low volume
  • cold fog Cloud mist And Warm mist formulations.
  • 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 dispersion. And/or a foam former.
  • an extender which is a liquid or liquefied gas or solid diluent or carrier
  • a surfactant an emulsifier and
  • a liquid solvent as a diluent or carrier
  • aromatic hydrocarbons such as xylene, toluene or alkylnaphthalene
  • chlorinated aromatic or chlorinated aliphatic hydrocarbons such as chlorobenzene, vinyl chloride or Dichloromethane
  • aliphatic hydrocarbons such as cyclohexane, paraffin or mineral oil fraction
  • alcohols such as ethanol or ethylene glycol and their ethers and lipids
  • ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone Or cyclohexanone
  • less common polar solvents such as dimethylformamide and dimethyl sulfoxide, and water.
  • the diluent or carrier for 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.
  • Solid supports can be used on ground natural minerals such as kaolin, clay, talc, quartz, activated clay, montmorillonite, or diatoms, and ground synthetic minerals such as highly dispersed silicic acid, alumina and silicates.
  • Solid supports for granules are ground and graded natural zircons such as calcite, marble, pumice, sepiolite and dolomite, as well as inorganic and organic coarse powder synthetic particles, and organic materials such as sawdust, coconut shell, Corn cobs and granules of tobacco stems.
  • Nonionic and anionic emulsifiers 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, for example, lignin sulfite waste liquid and methyl cellulose.
  • 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 used in the formulation.
  • Coloring agents such as inorganic fuels such as iron oxide, cobalt oxide 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 present in a commercial formulation or in a dosage form prepared from these preparations in combination with other active compounds including, but not limited to, insecticides, baits, bactericides, Acaricides, nematicides, fungicides, growth control agents, etc.
  • Insecticides include, for example, phosphates, carbamates, pyrethrins, chlorinated hydrocarbons, benzamides, silkworm toxins, and substances produced by microorganisms such as avermectin.
  • the active compounds of the invention may also be formulated as a mixture with synergists in their commercial preparations in the dosage form prepared from these preparations.
  • synergists are compounds which increase the action of the active compound. Since the active compound itself is active, 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, of the active compound of the invention, of the insecticidal composition.
  • concentration of the active compound in the dosage form prepared from the commercial preparation can be varied within a wide range.
  • concentration of the active compound in the dosage form used may range from 0.0000001 to 100% (g/v), preferably between 0.0001 and 1%.
  • test methods used in the following examples are conventional methods unless otherwise specified; the materials, reagents and the like used are, if not specified, commercially available reagents and materials.
  • N-(2-(4-Methoxyphenyl)-2-ethoxy)-acetamide (1.0 mmol) was added to 15 ml of ethanol, and malononitrile (2.0 mmol) and ethanol were added thereto. Sodium (1.5 mmol) was heated under reflux for 12 hr.
  • Table 4 Nuclear magnetic resonance spectra and mass spectrometry data of some of the compounds shown in formula (I) of Table 1.
  • 2,3-Dicyanopropionate ethyl ester (1.0 mmol) was added to 20.0 mL of ethanol, and the mixture was stirred vigorously. To the reaction mixture was added hydrazine hydrate (2.0 mmol), and the mixture was heated to reflux. After 3 hours, the heating was stopped and the mixture was cooled to room temperature. The mixture was concentrated in vacuo. EtOAc mjjjjjjj In the next step.
  • the mixture was cooled to room temperature, the mixture was filtered,jjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjj
  • Compounds c-1 to c-349 are carried out by referring to the c-27 method (in which the ring-forming step also has a similar ring-forming method mentioned in WO2007144669 and the like), except that different materials are selected for the reaction according to the target compound, or
  • the synthesized target product is derived by hydrolysis, simple esterification or amidation or reduction oxidation. Specific compounds are shown in Table 9.
  • Plutella xylostella (L.) is a lepidopteran pest with a chewing mouthparts and is a common vegetable pest.
  • the 2nd instar larvae of Plutella xylostella were tested and tested by the leaf-fed feeding method.
  • Spodoptera exigua is a lepidopteran pest with a chewing mouthpart and is a common vegetable pest.
  • the 2nd instar larvae of Spodoptera exigua were used as test subjects and tested by leaf-feeding method.
  • Aphids belong to the Homoptera pest, which has a sucking mouthparts and is a common vegetable pest. Aphid craccivora was used as the test object and tested by dipping method.
  • Red fire ants belong to the Hymenoptera pest, a social insect, and are one of the most destructive invading organisms. Solenopsis invicta was used as the test object and tested by water test tube feeding method.
  • Operation process accurately weigh each sample, add 200 ⁇ l of dimethyl sulfoxide to prepare 10 g / L mother liquor, and use it with a mixed aqueous solution containing 0.5 thousand Tween-80 and 5 percent honey. Dilute to a concentration of 100 ppm.
  • the red fire ant is placed in the ant test tube, and the liquid medicine is injected into the silicone plug of the ant test tube with a syringe, so that the liquid does not ooze out.
  • the ant tube was placed flat in the ant box, and a small amount of ham was added to the tube as a food, and the temperature was raised at 25 ° C.
  • Table 18 Insecticidal activity of some compounds of formula (I) on test pests
  • Table 20 Insecticidal activity of some of the compounds represented by the general formula (a) on test pests
  • Table 21 Insecticidal activity of some compounds represented by formula (b) on test pests
  • the compounds enumerated in the present invention have high killing activity against agricultural and forestry pests, animal parasitic pests and sanitary pests, and are characterized by pests such as Lepidoptera, Homoptera, Hymenoptera, and the like. Very good activity, and has a delayed effect on red fire ants, and has a better killing effect on the entire red fire ant nest and queen.
  • Bombyx mori L. is an important economic insect that is sensitive to pesticides in agro-ecosystems and one of the non-target organisms listed in the pesticide registration in China.
  • the 2nd instar larvae of the silkworm were used as test objects and tested by the leaf-fed feeding method.
  • Apis cernan selected adult worker bees of the same size, were collected from the beekeeping box in the morning of the test and tested by the small beaker method.
  • Operation process put a small amount of absorbent cotton into a small 5 mL beaker, add 5 mL of the test solution (concentration of 500 ppm) to the absorbent cotton, gently stir to make the cotton wool completely wet but no water leaching, then put the small beaker into In a 500 mL large beaker, 15 worker bees were placed and finally sealed with gauze. After treatment, it is placed in the dark chamber of the artificial climate chamber. 48 hours after the drug, the number of live insects and the number of dead insects were investigated. The results are shown in Table 25.
  • Table 25 Toxicity of some compounds of formula (I) in Tables 1 to 3 to environmental non-target organisms
  • the following components were prepared in proportion: 25% by weight, the same as any of the above compounds; 5% polyoxyethylene sorbitol hexaoleate; 70% higher aliphatic hydrocarbon oil.
  • the components were ground together in sanding until the solid particles fell below 5 microns.
  • the resulting viscous suspension can be used as it is, but it can also be used after emulsification in water.
  • the following components were prepared in proportion: 25% of any of the above compounds; 3% hydrated attapulgite; 10% calcium lignin sulfonate; 0.5% sodium dihydrogen phosphate; 61.5% water.
  • the components were milled together in a ball mill until the solid particles fell below about 10 microns. This aqueous suspension can be used directly.
  • the following components are prepared in proportion: 0.1 to 10% of any of the above compounds; 80% wheat flour; and 19.9 to 10% molasses. These components are thoroughly mixed to form a bait shape as needed.
  • the edible baits can be dispersed in places infested by sanitary pests, such as furniture or industrial establishments, such as kitchens, hospitals or shops or outdoor areas, to control pests by oral ingestion.

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Abstract

一种含氮稠合三环化合物及其光学异构体、顺反异构体或农药学上可接受的盐及其在农林业中的杀虫应用。该化合物对入侵红火蚁等害虫的延期起效作用可使害虫将药物携带至巢穴，从而对整个红火蚁蚁巢和蚁后有更好的杀灭效果。

Description

[根据细则37.2由ISA制定的发明名称]　含氮稠合三环化合物及其作为农林业杀虫剂的应用 技术领域
本发明属于杂环化合物领域，特别涉及一类稠合杂环化合物及其光学异构体、顺反异构体或农药学上可接受的盐及其制备方法和应用。
背景技术
以含氮杂环为代表的杂环类新农药因杀虫活性高，杀虫谱广，对哺乳动物毒性低，且有适当的田间稳定性，杂环类化合物成为新农药创制的重要热点领域。近年来，新开发的农药中，Flupyrimin，氟吡呋喃酮，环氧虫啶，氟啶虫胺腈，氟啶虫酰胺，螺虫乙酯，丁氟螨酯，腈吡螨酯，溴氰虫酰胺等无一不属于含氮杂环化合物(参见专利US2013150414、CN103960242、CN103254125、CN102892290、DE102006015467、WO2010069266、WO2007095229、EP580374、WO9805638、WO2002014263、JP2003201280、WO2004067528)。
但是，由于单一农药过量频繁使用，再加上现有的杀虫剂在杀灭害虫的同时对环境也有较高的毒性，造成了严重的抗性及交互抗性问题，导致农药药效降低，农药的应用受到了极大的限制，进而制约了农、林业的发展。因此，如何开发新的、更高效的、环境友好型农药，解决抗性问题就成为本领域迫切需要解决的技术问题。
与以往农药分子具有较大结构差异的新型结构分子，被认为与现有农药不产生交叉抗性，可用来治理害虫抗性的发展(Pesticide Biochemistry and Physiology,2015,121:22)。近年来，多系列的稠合杂环化合物被合成且报道具有广泛的生物活性(例如：Computational Biology and Chemistry,2018,74:218；Bioorganic&Medicinal Chemistry Letters,2017,27:3201；Journal of Medicinal Chemistry,2017,60:9691；Journal of Heterocyclic Chemistry,2017,54:2788；Organic&Biomolecular Chemistry,2016,14:8721；Journal of Enzyme Inhibition and Medicinal Chemistry,2015,31:195；New Journal of Chemistry,2015,39:1060；Chemistry-A European Journal,2015,21:16859；Bioorganic&Medicinal Chemistry Letters,2014,24:2693；Journal of Medicinal Chemistry,2013,56:7458；Bioorganic&Medicinal Chemistry Letters,2009,19:4196；Chemistry&Biology,2007,14:153；Journal of Biological Chemistry,2003,278:25990；Journal of Medicinal Chemistry,2002,45:1035.)，本研究据此设计、合成、筛选了大量新型的稠合杂环化合物，这些结构新颖的化合物对多种害虫，甚至是抗性害虫具有优异的防治效果。
发明内容
本发明的目的在于提供一类稠合杂环化合物及其光学异构体、顺反异构体或农药学上可接受的盐。所述稠合杂环化合物及其光学异构体、顺反异构体或农药学上可接受的盐对农林业害虫和卫生害虫等具有高的杀灭活性，令人更意外的是，其对红火蚁等害虫有延时起效的作用，具有更好的杀灭效果。
本发明的另一目的在于提供所述稠合杂环化合物及其光学异构体、顺反异构体或农药学上可接受的盐的制备方法。
本发明的另一目的在于提供所述稠合杂环化合物及其光学异构体、顺反异构体或农药学上可接受的盐在制备杀虫剂中的应用。
为了实现上述目的，本发明采用了以下技术方案：
稠合杂环化合物及其光学异构体、顺反异构体或农药学上可接受的盐，所述稠合杂环化合物具有式(Ⅰ)所示结构：
Figure PCTCN2018113811-appb-000001
其中，R 11和R 12各自独立地为氢、卤素、-NO 2、-CN、-COR 17、-CO 2R 17、-CONR 17R 18、-S(O)R 17、-S(O) 2R 17、-N R 17R 18、-N R 17CO R 18、-N R 17CON R 18R 19、-N R 17CO 2R 18、-N R 17S(O) 2R 18、烷基、杂烷基、烯基、环烷基、环烯基、芳基、杂环基或杂芳基；其中烷基、烯基、环烷基、环烯基、芳基、杂环基或杂芳基未经取代或经一个或多个取代基R 10取代；
R 13为氢、-COR 7、-CO 2R 17、-S(O) 2R 17、-CONR 17R 18、烷基、杂烷基、烯基、环烷基、环烯基、芳基；其中烷基、烯基、环烷基、环烯基、芳基未经取代或经一个或多个取代基R 10取代；
R 14和R 15各自独立地为氢、卤素、-CN、-OH、-N R 17R 18、-O R 17、-CO R 17、-CO 2R 17、-CONR 17R 18、-N R 17CO R 18、-NR 17CON R 18R 19、-NR 17CO 2R 18、-NR 17S(O) 2R 18、-S(O)R 17、-S(O) 2R 17、烷基、杂烷基、烯基、环烷基、环烯基、芳基、杂环基或杂芳基；其中烷基、烯基、环烷基、环烯基、芳基、杂环基或杂芳基未经取代或经一个或多个取代基R 10取代，且R 14和R 15不同时为氢；
Y为N或CH；
Z 1、Z 2、Z 3、Z 4各自独立地为C或N，条件是Z 1至Z 4中的至多两个是N，且含有Z 1至Z 4的环是芳族的；
R 16表示含有Z 1至Z 4环上的取代基，R 16的数量可以是一个或多个，各R 16独立地为氢、卤素、-CN、烷基、杂烷基、-CO R 17、-CO 2R 17、-N R 17R 18、-CONR 17R 18、-N R 17CO R 18、-NR 17CON R 18R 19、-NR 17CO 2R 18或-NR 17S(O) 2R 18；
R 17、R 18和R 19各自独立地为氢、烷基、杂烷基、烯基、环烷基、环烯基、杂环基、芳基或者杂芳基；其中烷基、烯基、环烷基、环烯基、芳基、杂环基或杂芳基未经取代或经一个或多个取代基R 10取代；
R 10为卤素、C 1-C 6烷基、C 2-C 6烯基、取代或未取代的环烷基、环烯基、取代或未取代的芳基、取代或未取代的杂芳基、取代或未取代的杂环基、-CN、-NH 2、-OR”’、-NR”’R””、-COR”’、-CO 2R”’、-CONR”’R””、-NR”’COR””、-NR”’CONR”’R””、-NR”’CO 2R””、-S(O) 2R”’或者-NR”’S(O) 2R””，其中R”’和R””独立的为氢、C 1-C 6烷基、C 2-C 6烯基、环烷基、环烯基、芳基、杂芳基、杂环基。
优选地，当Y为N或CH时；
R 11为卤素、-CN、-COR 17、-CONR 17R 18、-S(O)R 17、-N R 17R 18、-N R 17CO R 18、芳基、杂环基或杂芳基；其中芳基、杂环基或杂芳基未经取代或经一个或多个取代基R 10取代；
R 12为氢、-COR 17、-CONR 17R 18、-S(O)R 17、-S(O) 2R 17、-N R 17R 18、-N R 17CO R 18、-NR 17CONR 18R 19、-NR 17CO 2R 18、芳基、杂环基或杂芳基；其中芳基、杂环基或杂芳基未经取代或经一个或多个取代基R 10取代；
R 13为氢、-COR 17、烷基、杂烷基或烯基；
R 14为卤素、-CN、-N R 17R 18、-O R 17、-CO R 17、-CO 2R 17、-CONR 17R 18、-N R 17CO R 18、-NR 17CO 2R 18、烷基、杂烷基或烯基；其中烷基、杂烷基或烯基未经取代或经一个或多个取代基R 10取代；
R 15为氢、卤素、-CN、-N R 17R 18、-O R 17、-CO R 17、-CO 2R 17、-CONR 17R 18、-N R 17CO R 18、-NR 17CO 2R 18、烷基、杂烷基或烯基；其中烷基、杂烷基或烯基未经取代或经一个或多个取代基R 10取代。
优选地，当Z 1、Z 2、Z 3、Z 4均为C时，R 16可以是一个或多个，且各R 16独立地为氢、卤素、烷基、杂烷基、烯基、-S(O)R 17、-S(O) 2R 17、-COR 17、-N R 17R 18、-CONR 17R 18、-N R 17CO R 18或-NR 17S(O) 2R 18；
R 11为卤素、-CN、-COR 17、-CONR 17R 18、-S(O)R 17、-N R 17R 18、-N R 17CO R 18、芳基、杂环基或杂芳基；其中芳基、杂环基或杂芳基未经取代或经一个或多个取代基R 10取代；
R 12为-CONR 17R 18、-S(O)R 17、-S(O) 2R 17、-N R 17R 18、-N R 17CO R 18、-N R 17CON R 18R 19、芳基、杂环基或杂芳基；其中芳基、杂环基或杂芳基未经取代或经一个或多个取代基R 10取代；
R 13为氢、-COR 17、烷基或烯基；
R 14和R 15各自独立地为卤素、-CN、-N R 17R 18、-O R 17、-CO R 17、-CO 2R 17、-CONR 17R 18、-N R 17CO R 18、-NR 17CO 2R 18、烷基、杂烷基、烯基；其中烷基、杂烷基、烯基未经取代或经一个或多个取代基R 10取代。
更优选地，
当Y为N或CH时；
R 11为卤素、-CN、-COR 17、-CONR 17R 18、-S(O)R 17、-N R 17R 18、-N R 17CO R 18；
R 12为-S(O)R 17、-S(O) 2R 17、-N R 17R 18、-N R 17CO R 18、芳基或杂芳基；其中芳基或杂芳基未经取代或经一个或多个取代基R 10取代；
R 13为氢、-COR 17、烷基或烯基；
R 14和R 15各自独立地为卤素、-CN、-N R 17R 18、-O R 17、-CO R 17、-CO 2R 17、-CONR 17R 18、-N R 17CO R 18、-NR 17CO 2R 18、烷基、杂烷基或烯基；其中烷基或烯基未经取代或经一个或多个取代基R 10取代；
Z 1、Z 2、Z 3、Z 4均为C，R 16可以是一个或多个，且各R 16独立地为卤素、烷基、杂烷基、-S(O)R 17、-S(O) 2R 17、-COR 17、-N R 17R 18、-N R 17CO R 18或-NR 17S(O) 2R 18。
更优选地，
R 11为卤素、-CN、-COR 17或-CONR 17R 18；
R 12为-S(O)R 17、-S(O) 2R 17、-NR 17COR 18、芳基或杂芳基；其中芳基或杂芳基未经取代或经一个或多个取代基R 10取代；
R 13为氢、-COR 17或烷基；
Z 1、Z 2、Z 3、Z 4均为C，R 16可以是一个或多个，且各R 16独立地为卤素、杂烷基、-S(O)R 17、-NR 17R 18或-NR 17COR 18。
更优选地，
R 11为-CN或-COR 17；
R 12为-S(O)R 17或芳基；其中芳基经一个或多个取代基R 10取代；
R 13为氢、-COR 17、甲基或乙基；
R 14和R 15各自独立地为卤素、-OR 17、-COR 17、-CO 2R 17、-CONR 17R 18、-NR 17COR 18、-NR 17CO 2R 18、烷基、杂烷基或烯基；其中烷基或烯基未经取代或经一个或多个取代基R 10取代；
Z 1、Z 2、Z 3、Z 4均为C，R 16可以是一个或多个，且各R 16独立地为卤素或杂烷基。
更优选地，
R 11为-CN或-COR 17，且R 17为烷基或杂烷基；
R 12为-S(O)R 17，且R 17为烷基或杂烷基；
R 13为氢、-COR 17、甲基或乙基，且R 17为烷基；
R 14和R 15各自独立地为卤素、-OR 17、-COR 17、-CO 2R 17、-CONR 17R 18、-NR 17COR 18、-NR 17CO 2R 18、烷基、杂烷基或烯基；其中烷基或烯基未经取代或经一个或多个取代基R 10取代；
Z 1、Z 2、Z 3、Z 4均为C，R 16可以是一个或多个，且各R 16独立地为卤素或杂烷基。
本发明还公开一类含吡唑环的稠合杂环化合物及其光学异构体、顺反异构体或农药学上可接受的盐，所述含吡唑环的稠合杂环化合物具有式(Ⅱ)所示结构：
Figure PCTCN2018113811-appb-000002
其中，R 1为氢、卤素、-CN、烷基、杂烷基、芳基或杂芳基；其中烷基、芳基或杂芳基未经取代或经一个或多个取代基R 9取代；
R 2为氢、卤素、-CN、-S(O)R 7、-S(O) 2R 7、烷基、杂烷基、芳基或杂芳基；其中烷基、芳基或杂芳基未经取代或经一个或多个取代基R 9取代；
R 3为氢、-COR 7、烷基或杂烷基；
R 4和R 5各自独立地为氢、卤素、-CN、-COR 7、-CO 2R 7、-CH 2COR 7、-CH 2COOR 7、氨基、烷基、杂烷基、芳基或杂芳基；其中氨基、烷基、芳基或杂芳基未经取代或经一个或多个取代基R 9取代，且R 4和R 5不同时为氢；
Z 1和Z 2各自独立地为C或N，不同时为N，且含有Z 1和Z 2的环为芳族环；
R 6表示含有Z 1和Z 2环上的取代基，R 6的数量可以是一个或多个，各R 6独立地为氢、卤素、-NO 2、-CN、烷基、杂烷基、-OR 7、-COR 7、-CO 2R 7或-NR 7R 8；
R 7和R 8各自独立地为氢、羟基、氨基、C 1-C 6烷基、杂烷基、芳基或者杂芳基；其中烷基、芳基或杂芳基未经取代或经一个或多个取代基R 9取代；
R 9为卤素、C 1-C 6烷基、杂烷基、-CN、-NH 2、-OH、-COR’、-CO 2R’或-CONR’R”，其中R’和R”独立的为氢、C 1-C 6烷基或杂烷基。
优选地，当Z 1为N，Z 2为C时，R 6为吡啶环5位-CF 3单取代，所述化合物的通式为式(a)所示：
Figure PCTCN2018113811-appb-000003
其中R 3为氢、甲基或氯代甲基；R 4和R 5各自独立地为氢、卤素、-CN、 -COR 7、-CO 2R 7、-CH 2COR 7、-CH 2COOR 7、氨基、烷基、杂烷基、芳基或杂芳基；其中氨基、烷基、芳基或杂芳基未经取代或经一个或多个取代基R 9取代；
或，
当Z 2为N，Z 1为C时，R 6为吡啶环5位氯单取代，所述化合物的通式为式(b)所示：
Figure PCTCN2018113811-appb-000004
其中R 3为氢、甲基或氯代甲基；R 4和R 5各自独立地为氢、卤素、-CN、-COR 7、-CO 2R 7、-CH 2COR 7、-CH 2COOR 7、氨基、烷基、杂烷基、芳基或杂芳基；其中氨基、烷基、芳基或杂芳基未经取代或经一个或多个取代基R 9取代；
或，
当Z 1和Z 2同为C，R 6为苯环上3位和5位双取代时，所述化合物的通式为式(c)所示：
Figure PCTCN2018113811-appb-000005
其中R 1为-CN或-CF 3，R 2为-CN、-CF 3、-OCF 3、-SOCF 3或-SOCH 2CH 3；R 3为氢、-CH 3、-Ac或-CH 2CH 2Cl；R 6在苯环的3位上的取代基为-Cl、-Br、-CF 3、-CH 3、-CN、-CO 2CH 3或-NO 2，R 6在苯环的5位上的取代基为-Cl、-CF 3、-OCF 3或-NO 2；R 4和R 5各自独立地为氢、卤素、-CN、-COR 7、-CO 2R 7、-CH 2COR 7、-CH 2COOR 7、氨基、烷基、杂烷基、芳基或杂芳基；其中氨基、烷基、芳基或杂芳基未经取代或经一个或多个取代基R 9取代；
或，
当Z 1和Z 2同为C，R 6为苯环上4位和6位双取代，R 3为氢时，所述化合物的通式为式(d)所示：
Figure PCTCN2018113811-appb-000006
其中R 1为-CN、-CF 3、-CHO或-CH 2NH 2，R 2为-OCF 3、-CF 3、-CN、-SOCF 3、-SOCH 3、-SOCH 2CH 3、-SOPh、-SOCH 2Ph、-SOC 6H 13、
Figure PCTCN2018113811-appb-000007
Figure PCTCN2018113811-appb-000008
R 6为-Cl或-CF 3；R 4和R 5各自独立地为氢、卤素、-CN、-COR 7、-CO 2R 7、-CH 2COR 7、-CH 2COOR 7、氨基、烷基、杂烷基、芳基或杂芳基；其中氨基、烷基、芳基或杂芳基未经取代或经一个或多个取代基R 9取代；
或，
当Z 1和Z 2同为C，R 6为苯环上3、6位或者3、4位或者4、5位或者5、6位双取代，R 3为氢时，所述化合物的通式为式(e)所示：
Figure PCTCN2018113811-appb-000009
其中R 1为-CN，R 2为-SOCF 3；R 6为-Cl或-CF 3；R 4和R 5各自独立地为氢、卤素、-CN、-COR 7、-CO 2R 7、-CH 2COR 7、-CH 2COOR 7、氨基、烷基、杂烷基、芳基或杂芳基；其中氨基、烷基、芳基或杂芳基未经取代或经一个或多个取代基R 9取代；且R 4和R 5不同时为氢。
优选地，R 4和R 5各自独立地为氢、卤素、-CN、-COR 7、-CO 2R 7、-CH 2COR 7、-CH 2COOR 7、氨基、烷基或杂烷基；其中R 7为氢、卤素、羟基、C 1～4烷基、C 1～4卤代烷基、C 1～4烯基、C 1～4卤代烯基、氨基或取代氨基。
优选地，当所述化合物为式(a)或式(b)所示，R 4和R 5任一为氢时，R 1为-CN，R 2为-SOCF 3或者-OCF 3；或R 1为-CF 3，R 2为-SOCF 3；
或，R 4和R 5均不为氢时，R 1为-CN或-CF 3；R 2为-SOCF 3、-SOCH 2CH 3、-OCF 3、-CF 3、-CN或卤素。
优选地，当所述化合物为式(c)所示，R 3为-CH 3、-Ac或-CH 2CH 2Cl时，R 2为-SOCF 3，R 1为-CN，R 4和R 5均为-CO 2Me；
或，R 3为氢，R 2为-CN、-CF 3或-SOCH 2CH 3时，R 1为-CN或-CF 3，R 4和R 5各自独立地为-CO 2Me或-CH 2CO 2Me；
或，R 3为氢时，R 2为-OCF 3或-SOCF 3时，R 1为-CN或-CF 3，R 4和R 5各自独立地为氢、卤素、-CN、-COR 7、-CO 2R 7、-CH 2COR 7、-CH 2COOR 7、氨基、烷基、杂烷基、芳基或杂芳基；其中氨基、烷基、芳基或杂芳基未经取代或经一个或多个取代基R 9取代。
优选地，当所述化合物为式(d)所示，R 3为氢，R 2为-CN、-CF 3、-SOPh、-SOCH 2Ph、-SOC 6H 13、
Figure PCTCN2018113811-appb-000010
时，R 1为-CN，R 4和R 5各自独立地为-CO 2Me或-CO 2CH 2Me；
或，R 3为氢，R 2为-SOCF 3，R 1为-CHO或-CH 2NH 2时，R 4和R 5各自独立地为-CO 2Me或-CO 2CH 2Me；
或，R 3为氢，R 2为-OCF 3或-SOCF 3时，R 1为-CN或-CF 3，R 4和R 5各自独立地为氢、卤素、-CN、-COR 7、-CO 2R 7、-CH 2COR 7、-CH 2COOR 7、氨基、烷基、杂烷基、芳基或杂芳基；其中氨基、烷基、芳基或杂芳基未经取代或经一个或多个取代基R 9取代。
优选地，当所述化合物为式(e)所示时，R 6为苯环上3-Cl和6-CF 3、3-Cl和4-CF 3、4-Cl和5-CF 3或5-Cl和6-CF 3；R 4和R 5各自独立地为-CO 2Me、-CH 2CO 2Me、-CO 2Et、-CH 2CO 2Et、-CH 2CO 2CH 2CF 3或-CH 2CO 2CH 2CHF 2。
一种农用组合物，它包含：
(a)0.001～99.99重量％的上述化合物、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；以及
(b)农药上可接受的载体和/或赋形剂。
本发明所述农用组合物在制备用于杀灭或预防农林业害虫、卫生害虫和危害动物健康的害虫的杀虫剂中的应用。
具体的应用方式是，将所述杀虫剂直接施加在害虫身上或其接触的场所(例如遭受或可能遭受虫害的植物体、其周围的土壤或环境中)。
与现有技术相比，本发明具有如下有益效果：
本发明公开一类新结构的稠合杂环化合物及含吡唑环的稠合杂环化合物。所述稠合杂环化合物及含吡唑环的稠合杂环化合物及其光学异构体、顺反异构体或农药学上可接受的盐对农林业害虫和卫生害虫等具有高的杀灭活性，并且本发明化合物对入侵红火蚁等害虫具有延期起效的作用，可以使害虫将药物携带至巢穴，从而对整个红火蚁蚁巢和蚁后有更好的杀灭效果；在害虫防治方面具有很好的应用前景。本发明的化合物对环境生物，如蜜蜂、家蚕等具有更低的毒性，因此具有很好的应用前景。
具体实施方式
本发明的发明人通过长期而深入的研究，基于现有的杂环类农药的抗性日益严重和对环境的危害性等问题，设计、合成、筛选了一类新的稠合杂环化合物及含吡唑环的稠合杂环化合物，该化合物的杀虫活性显著提高，并具有扩大的杀虫谱。下面结合具体实施例对本发明作进一步的解释说明，但具体实施例并不对本发明作任何限定。除非特别说明，实施例中所涉及的试剂、方法均为本领域常用的试剂和方法。
本发明中，除非上下文中另有说明，下面所要用到的单词、短语和符号，要表达的含义有如下规定。以下缩写和术语的含义贯穿整文：
术语“卤素”指氟、氯、溴和碘，在基团名称前的术语“卤”指该基团的部分或完全被卤代，即，以任何组合被F、Cl、Br或I取代，例如一氟二氯甲基、二氟甲基、三氯甲基、五氟乙基、或类似基团。
术语“烷基”是指烃基，所述烃基选自饱和的直链或支链烃基。其优选包括1～12个碳原子，更优选1～6个碳原子，例如甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基、叔丁基、或类似基团。
术语“烯基”是指选自直链或支链的烃基，且其中包括至少一个C＝C双键；其优选包括2～12个碳原子，更优选包括2～6个碳原子，例如乙烯基、丙-1-烯基、丙-2-烯基、2-甲基丙-1-烯基、丁-1,3-二烯基、2-甲基-1,3-丁二烯、己-1,3-二烯基基团、或类似基团。
术语“环烷基”是指选自饱和的环烃基，其包括单环或多环基团。环烷基优选具有3～12个碳原子。例如，环烷基可以是具有3～12个碳原子的单环基团，例如环丙基、环丁基、环戊基、环壬基、环癸基、环十一烷基和环十二烷基、或类似基团。环烷基还可以是具有4～12个碳原子的双环基团，例如[4,5]、[5,5]、[5,6]和[6,6]环体系的双环、选自双环[2.2.1]庚烷、双环[2.2.2]辛烷和双环[3.2.2]壬烷的桥连双环、或类似基团。
术语“环烯基”是指选自不饱和的环烃基，且其含有至少一个C＝C双键，但不是完全的共轭，且不是芳香族的(如本文所定义的芳香族)，其包括单环或多环基团。环烯基中优选有3～12个碳原子。例如环戊烯、环戊二烯、环己烯、环己二烯、环庚烯、环辛烯、并环戊二烯、或类似基团。
术语“芳基”是指选自如下的基团：(a)5元和6元碳环芳族环，例如，苯基、呋喃环或噻吩环；(b)双环体系如7～12元双环体系，其中至少一个环是碳环和芳族环，例如萘或1,2,3,4-四氢喹啉；(c)三环体系如10～15元三环体系，其中至少一个环是碳环和芳族 环，例如芴。
例如，芳基选自5元和6元碳环芳族环，所述碳环芳族环稠合至5～7元环烷基或任选地包含至少一个选自N、O和S的杂原子的杂环上，条件是当所述碳环芳族环稠合至杂环时连接点在碳环芳族环上，当碳环芳族环稠合至环烷基时连接点可在碳环芳族环上或在环烷基上。由取代的苯衍生物形成且在环原子上具有自由价的二价基团被称为取代的亚苯基基团。通过从具有自由价的碳原子移除一个氢原子而衍生自其名称以“基”结尾的单价多环烃的二价基团通过在相应的单价基团的名称中加入“亚基”而命名，如具有两个连接点萘基称作亚萘基。然而，芳基不包括杂环基或与杂芳基重叠，其在下面分别定义。因此，如果一个或多个碳环芳族环与杂环芳族环稠合，所得到的环体系为本文中定义的杂芳基，而非芳基。
术语“杂烷基”是指包括至少一个杂原子的烷基，杂原子是指非C原子。杂原子优选N、O、S、P或Se等。
术语“杂芳基”是指选自如下的基团：
5～7元芳族单环，其包含1、2、3或者4个选自N、O和S的杂原子，其余的环原子为碳；
8～12元双环，其包含1、2、3或者4个选自N、O和S的杂原子，其余的环原子为碳，且其中至少一个环是芳族的，并且至少一个杂原子存在于芳族环中；
11～14元双环，其包含1、2、3或者4个选自N、O和S的杂原子，其余的环原子为碳，且其中至少一个环是芳族的，并且至少一个杂原子存在于芳族环中；
例如，杂芳基包括稠合至5～7元环烷基环上的5～7元杂环芳族环。对于该稠合的双环杂芳基环体系，其中仅一个环包含至少一个杂原子，连接点可以在杂芳族环或环烷基环上。
当杂芳基中的S和O原子的总数超过1时，这些杂原子彼此不相邻。
术语“杂环基”指的是选自如下的环：4～12元的单环、双环和三环的饱和和部分不饱和的环，其除了选自氧、硫和氮的1、2、3或者4个杂原子外包含至少一个碳原子。也指包含至少一个选自N，O和S的杂原子的脂族螺环，条件是连接点在杂环上。所述环可以是饱和的或含有至少一个双键。所述杂环可被氧化取代。连接点可以是杂环中的碳原子或杂原子。
术语“烷氧基”是指烃氧基，所述烃氧基选自饱和的直链或支链烃氧基。其包括1～12个碳原子，优选1～6个碳原子，例如甲氧基、乙氧基、正丙氧基、异丙氧基、正丁氧基、异丁氧基、仲丁氧基、叔丁氧基、或类似基团。
取代基选自：卤素、-R””’、-OR””’、＝O、＝NR””’、＝N-OR””’、-NR””’R”””、-SR””’、-OC(O)R””、-C(O)R””、-CO 2R””、-CONR””’R”””、-OC(O)NR””’R”””、-NR””’C(O)R”””、-NR””’-SO 2NR”””、-NR”””CO 2R””’、-NH-C(NH 2)＝NH、-NR””’C(NH 2)＝NH、-NH-C(NH 2)＝NR””’、-S(O)R””’、-SO 2R””’、-SO 2NR””’R”””、-NR”””SO 2R””’、-CN和-NO 2、-CH(Ph) 2、卤代(C 1-C 4)烷氧基和卤代(C 1-C 4)烷基，取代基个数从0到3，优选具有0、1或者2个取代基。R””’和R””’各自独立地选自氢、未取代的(C 1-C 6)烷基和杂烷基、未取代的芳基、含有1～3个卤素取代的芳基、未取代的烷基、烷氧基或者硫代烷氧基，或者芳基-(C 1-C 4)烷基。当R””’和R”””连接在相同的氮原子时，它们能够结合氮原子形成5、6或者7元环，因此，-NR””’R”””包括1-吡咯烷基和4-吗啉基。“烷基”包括例如三卤代烷基(如-CF 3和-CH 2CF 3)。
优选的取代基选自：卤素、-R””’、-OR””’、＝O、-NR””’R”””、-SR””’、-OC(O)R””’、-C(O)R””’、-CO 2R””’、-CONR””’R”””、-OC(O)NR””’R”””、-NR”””C(O)R””’、-NR”””CO 2R””’、-S(O)R””’、-SO 2R””’、-SO 2NR””’R”””、-NR”””SO 2R””’、-CN和-NO 2、卤代(C 1-C 4)烷氧基和卤代(C 1-C 4)烷基，其中R””’和R”””如上定义。
本文中的术语“稠合杂环”指的是如下的多环体系例如二环或三环体系，其中两个环仅 共享两个环原子和一个键，并且其环原子中包含至少一个非C原子。稠合杂环的实例可以包括稠合的双杂环烷基，如由7～12个环原子排列组成的选自上述[4,4]、[4,5]、[5,5]、[5,6]和[6,6]环体系的双杂环；稠合的双环杂芳基环，例如上述8～12元双环杂芳基环；稠合的三环杂芳基环，例如上述11～14元三环杂芳基环，例如，吡唑并[1,5-a]喹唑啉、吡唑并[1,5-c]喹唑啉、吡咯并[1,2-a]喹唑啉、吡唑并[1,5-a]吡啶并[3,2-e]嘧啶、吡唑并[1,5-a]吡啶并[3,4-e]嘧啶、吡唑并[1,5-a]吡啶并[2,3-e]嘧啶、吡唑并[1,5-a]吡啶并[4,3-e]嘧啶等；以及上述稠合的双环或三环杂环基环。
所述化合物可以含有一个不对称中心，因而可以作为对映异构体存在。当所述化合物具有两个或多个不对称中心，它们另外可以作为非对映异构体存在。对映异构体和非对映异构体从属立体异构体这一更广泛的类型中。所有这些可能的立体异构体包括基本上纯的拆分对映异构体(指目标立体异构体包含不超过10重量％的任何其他的立体异构体)、其外消旋混合物和非对映异构体混合物。除非另作说明，所提及的一个异构体适用于任何可能的异构体。当未具体指明异构体组分时，包括所有可能的异构体。
当化合物包含烯烃双键时，除非另作说明，这些双键指包含E和Z几何异构体。
一些化合物可以存在不同的氢连接点，被称为互变异构体。例如，包含羰基-CH 2C(O)-基团(酮式)的化合物可以经历互变异构形成羟基-CH＝C(OH)-基团(烯醇式)。应用时，也包含单独的酮式和烯醇式以及其混合物。
术语“可接受的盐”指其阳离子或阴离子是已知的，并且可用于在本领域形成用途的盐。
适宜的具有碱基的盐类，例如由含有羧基基团的式(Ⅰ)、式(Ⅱ)化合物形成的盐，包括碱金属(如钠和钾)、碱土金属(如钙和镁)、铵和胺的盐类。
适宜的具有酸根加成的盐类，如由含有氨基的式(Ⅰ)、式(Ⅱ)化合物形成的盐，包括与无机酸形成的盐，例如盐酸盐、硫酸盐、亚硫酸盐、磷酸盐、磷酸氢盐和硝酸盐以及与有机酸如乙酸、苹果酸、酒石酸、柠檬酸、乳酸、水杨酸和草酸等形成的盐。
另外，如果化合物作为酸加成盐获得，则游离碱可以通过碱化酸式盐的溶液而获得。相反地，如果产物是游离碱，加成盐可以通过将游离碱溶于合适的有机溶剂并且用酸处理溶液而制备，与由碱性化合物制备酸加成盐的常规过程一致。本领域技术人员应了解无需过度实验而可用于制备农药上可接受的加成盐的各种合成方法。
本发明的化合物能用作控制和消灭广泛的农林业害虫、卫生害虫和危害动物健康的害虫。在本说明书中，“杀虫剂”是具有防治上述提到的所有害虫的作用的物质的统称。害虫的例子包括但不限于：鞘翅目昆虫：例如，玉米象(Sitophilus zeamais)，赤拟谷盗(Tribolium castaneum)，马铃薯瓢虫(Henosepilachna vigintioctomaculata)，二十八星瓢虫(Henosepilachna sparsa)，细胸叩头虫(Agriotes fusciollis)，红脚绿金龟(Anomala cupripes)，四纹丽金龟(Popillia quadriguttata)，马铃薯叶甲(Monolepta hieroglyphica)，松天牛(Monochamus alternatus)，稻根象(Echinocnemus squameus)，泡桐叶甲(Basiprionota bisignata)，星天牛(Anoplophora chinensis)，桑天牛(Apripona germari)，脐腹小蠹(Soclytus schevy)，或细胸金针虫(Agriotes fuscicollis)等；鳞翅目昆虫：例如，舞毒蛾(Lymantria dispar)，天幕毛虫(Malacosoma neustria testacea)，黄杨绢野螟(Diaphania perspectalis)，大袋蛾(Clania variegata)，黄刺蛾(Cnidocampa flauescens)，马尾松毛虫(Dendrolimus punctatus)，古毒蛾(Orgyia antiqua)，白杨透翅蛾(Paranthrene tabaniformis)，斜纹夜蛾(Spodoptera litura)，二化螟(Chilo suppressalis)，玉米螟(Ostrinia nubilalis)，粉斑螟(Ephestia cautella)，棉卷蛾(Adoxophyes orana)，栗子小卷蛾(laspyresia splendana)，小地老虎(Agrotis fucosa)，大蜡螟(Galleria mellonella)，小菜蛾(Plutella xylostella)，桔潜蛾(Phyllocnistis citrella)，或东方粘虫(Mythimna separata)等；半翅目昆虫：例如，梨斑网蝽(Stephanitis nashi)等；同翅目昆虫：例如，黑尾叶蝉(Nephotettix cincticeps)， 矢尖蚧(Unaspis yanonensis)，桃蚜(Myzus persicae)，棉蚜(Aphis gossydii)，或粉虱(Bemisia tabaci)等；直翅目昆虫：例如非洲蝼蛄(Gryllotalpa africana)，或亚洲飞蝗(Locus migratoria)等；膜翅目昆虫：例如，红火蚁(Solenopsis invicta)，或烟扁角树蜂(Tremex fuscicornis)等；蜚蠊目昆虫：例如，德国小蠊(Blattella germanica)，美洲大蠊(Periplaneta american)，或家白蚁(Copotermes formosamus)等；双翅目昆虫：例如，家蝇(Musca domestica)，埃及伊蚊(Aedes aegypti)，种蝇(Delia platura)，库蚊(Culex sp.)，或中华按蚊(Anopheles sinensis)等；植物寄生性线虫：例如，根结线虫、根腐线虫、稻干尖线虫、松材线虫等。危害动物健康的害虫包括微小牛蜱(Boophilus microplus)，长角血蜱(Haemaphysalis longicornis)，小亚璃眼蜱(Hyalomma anatolicum)，牛皮蝇(Hypoderma spp.)，肝片吸虫(Fasciola hepatica)，贝氏莫尼茨绦虫(Moniezia blanchard)，奥斯特线虫(Ostertagia spp.)，原虫(Trypanosoma enansi)，巴贝斯虫(Babesia bigemina)等。
本发明涉及的化合物优选的对鳞翅目、膜翅目、半翅目、鞘翅目、双翅目、蜚蠊目等农林害虫，动物寄生性的蚤类和/或蜱螨类以及卫生害虫有高的活性，更优选的对刺吸式或咀嚼式口器害虫有高的活性。
含本发明活性物质的杀虫剂组合物
可将本发明的活性物质以常规的方法制备成杀虫剂组合物。这些活性化合物可组合成常规的制剂，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，和与燃烧装置一起使用的制剂(例如烟熏药筒，烟熏罐和烟熏盘)，以及超低容量(ULV)冷雾(Cloud 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，石蜡或矿物油馏分；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是指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。
固体载体可用地面天然的矿物质，例如高岭土，粘土，滑石，石英，活性白土，蒙脱土，或硅藻上，和地面合成的矿物质，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剂可用作乳化剂和/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，例如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，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燃料，如氧化铁，氧化钴和普鲁士蓝；有机染料，如偶氯染料或金属钛菁染料；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它活性化合物制成混合物存在于商品制剂中或从这些制剂制备的使用剂型中，所述其他的活性化合物包括但不限于：杀虫剂，合饵，杀菌剂，杀螨剂，杀线虫剂，杀真菌剂，生长控制剂等。杀虫剂包括，例如磷酸酯类，氨基甲酸酯 类，除虫菊酯类，氯化烃类，苯甲酰胺类，沙蚕毒素类以及由微生物产生的物质，如阿维菌素。
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他们的商品制剂中成从这些制剂制备的使用剂型中。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虫剂组合物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。从商品制剂制成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％之间。
下面结合具体实施例对本发明作出进一步地详细阐述，所述实施例只用于解释本发明，并非用于限定本发明的范围。下述实施例中所使用的试验方法如无特殊说明，均为常规方法；所使用的材料、试剂等，如无特殊说明，为可从商业途径得到的试剂和材料。
合成实施例：
实施例1：采用方法A合成A1～A47化合物
Figure PCTCN2018113811-appb-000011
例如，化合物A1的合成：
S1:5-氨基-1H-吡唑-3-氰基
20.0ml的乙醇中加入2,3-二氰基丙酸乙酯(1.0mmol)，剧烈搅拌，向反应液中加入水合肼(2.0mmol)，加热回流，3小时后停止加热，冷却至室温。混合物真空浓缩，用乙酸乙酯和水萃取混合物，真空浓缩萃取得到的乙酸乙酯，得到白色固体5-氨基-1H-吡唑-3-氰基，所述中间体未经进一步纯化，直接用于下一步。
S2:5,5-二甲基-4,5-二氢吡唑[1,5-α]喹唑啉-2-氰基
氮气保护下，5-氨基-1H-吡唑-3-氰基(1.0mmol)、1-溴-2-(1-溴-1-甲基乙基)苯(1.0mmol)、碘化亚铜(0.2mmol)和碳酸铯(0.5mmol)的DMF混合物在100摄氏度下搅拌24小时。冷却至室温，混合物过滤，真空浓缩，残余物用柱色谱纯化得到目标化合物5,5-二甲基-4,5-二氢吡唑[1,5-α]喹唑啉-2-氰基(两步收率：45％)。
化合物A2～A47参照A1方法进行(其中成环步骤也有Tetrahedron Letters(2015)56:1367；WO2016046404；WO2013174822等文献提到类似的成环方法)，区别在于根据目标化合物的不同，选择不同的原料进行反应，或是由已合成的目标产物衍生得到。具体化合物如表1所示：
表1
Figure PCTCN2018113811-appb-000012
Figure PCTCN2018113811-appb-000013
Figure PCTCN2018113811-appb-000014
Figure PCTCN2018113811-appb-000015
Figure PCTCN2018113811-appb-000016
Figure PCTCN2018113811-appb-000017
Figure PCTCN2018113811-appb-000018
实施例2：采用方法B合成B1～B12化合物
Figure PCTCN2018113811-appb-000019
例如，化合物B1的合成：
S1:2-氨基-4-(4-甲氧基苯)-1H-吡咯-3-氰基
将2-溴-1-(4-甲氧基苯基)-乙酰基(1.0mmol)加入到在15毫升的DMF中，随后向反应液中加入叠氮化钠(10.0mmol)，反应混合物搅拌48小时后，反应混合物过滤，得到的滤液用乙醚多次萃取。真空浓缩，残余物用甲醇溶解，在氢气的氛围下，向其中加入10％的钯碳(0.2mmol)，反应混合物搅拌24小时后，混合物过滤，得到的滤液真空浓缩，残余物用四氢呋喃溶解，向其中加入乙酸酐(2.0mmol)、三乙胺(2.0mmol)，反应混合物搅拌5小时后，混合物真空浓缩，残余物用柱色谱纯化得到N-(2-(4-甲氧基苯基)-2- 乙氧基)-乙酰胺(收率：78％)。
将N-(2-(4-甲氧基苯基)-2-乙氧基)-乙酰胺(1.0mmol)加入到在15毫升的乙醇中，向其中加入丙二腈(2.0mmol)和乙醇钠(1.5mmol)，加热回流12小时，混合物真空浓缩，残余物用柱色谱纯化得到目标化合物(收率：89％)。
S2:2-溴-2-(2-氯-4-硝基苯基)丙二腈
氮气保护下，2-氯-4-硝基-苯甲酰氯(1.0mmol)溶解在10毫升的干燥吡啶中，冷却至0摄氏度，随后向反应液中缓慢滴加三甲基硅基腈(1.1mmol)反应液自然升温至室温。搅拌10小时后，反应混合物重新冷却至0摄氏度，向反应混合物中加入2毫升的三溴氧磷。搅拌12小时后，真空除去溶液后，将残余物用水和乙酸乙酯萃取，真空浓缩萃取得到的乙酸乙酯，残余物通过用柱色谱纯化得到2-溴-2-(2-氯-4-硝基苯基)丙二腈(收率：56％)。
S3:2-(4-甲氧基苯)-8-硝基吡咯[1,2-α]喹唑啉-3,5,5(4H)-三氰基
氮气保护下，2-氨基-4-(4-甲氧基苯)-1H-吡咯-3-氰基(1.0mmol)、2-溴-2-(2-氯-4-硝基苯基)丙二腈(1.1mmol)、碘化亚铜(0.2mmol)和乙醇钠(0.5mmol)的DMF混合物在120摄氏度下搅拌24小时。冷却至室温，混合物过滤，真空浓缩，残余物用柱色谱纯化得到2-(4-甲氧基苯)-8-硝基吡咯[1,2-α]喹唑啉-3,5,5(4H)-三氰基(收率：53％)。
化合物B2～B12参照B1方法进行(Synthetic Communications(2015)45:2426；Tetrahedron Letters(2014)55:4997；WO2007149907等文献提到类似的成环方法)，区别在于根据目标化合物的不同，选择不同的原料进行反应，部分化合物，如化合物B9、B10、B11、B12等可以通过对B7进行修饰获得，具体化合物如表2所示：
表2
Figure PCTCN2018113811-appb-000020
Figure PCTCN2018113811-appb-000021
Figure PCTCN2018113811-appb-000022
实施例3：采用方法C合成C1～C64化合物
Figure PCTCN2018113811-appb-000023
例如，化合物C1的合成：
S1:(2-氨基-3-氯-5-(三氟甲基)苯基)硼酸
氮气保护下，2-溴-6-氯-4-三氟甲基苯胺(1.0mmol)溶于20毫升干燥的四氢呋喃中，冷却至0摄氏度，向反应混合物中缓慢滴加正丁基锂(2.5mmol，1.6M正己烷溶液)，搅拌2小时后，向反应混合物中缓慢滴加三甲基氯硅烷(2.5mmol)，反应自然升温搅拌12小时，真空浓缩除去溶剂，通过减压蒸馏得到目标化合物(2-氨基-3-氯-5-(三氟甲基)苯基)硼酸(收率：87％)。
S2:2-氯-6-(1,2-二氯-3-丁烯-2-基)-4-(三氟甲基)苯胺
氮气保护下，3-溴-3,4-二氯-1-丁烯(1.0mmol)，Pd(dppf)Cl 2(0.15mmol)，碳酸钠(0.15mmol)和(2-氨基-3-氯-5-(三氟甲基)苯基)硼酸(1.5mmol)的DMF(3.0毫升)和水(0.5毫升)的混合物在100摄氏度搅拌10小时。真空除去溶液后，将残余物用水(10毫升)稀释，水层用乙酸乙酯萃取，真空浓缩萃取得到的乙酸乙酯，残余物通过用柱色谱 纯化得到目标化合物2-氯-6-(1,2-二氯-3-丁烯-2-基)-4-(三氟甲基)苯胺(收率：85％)。
S3:2-溴-1-氯-3-(1,2-二氯-3-丁烯-2-基)-5-(三氟甲基)苯基
氮气保护下，2-溴-1-氯-3-(1,2-二氯-3-丁烯-2-基)-5-(三氟甲基)苯基(1.0mmol)和溴化铜(1.5mmol)溶解在10毫升的乙腈中，冷却至-5摄氏度，向其中缓慢加入亚硝酸异戊酯(1.3mmol)，随将反应混合物加热至50摄氏度。3小时后，混合物过滤，滤液真空浓缩，残余物用柱色谱纯化得到目标化合物2-溴-1-氯-3-(1,2-二氯-3-丁烯-2-基)-5-(三氟甲基)苯基(收率：91％)。
S4:9-氯-7-三氟甲基苯基-5-氯甲基-5-乙烯基-4,5-二氢吡咯[1,5-α]喹唑啉-2-氰基
氮气保护下，5-氨基-1H-吡唑-3-氰基(1.0mmol)、2-溴-1-氯-3-(1,2-二氯-3-丁烯-2-基)-5-(三氟甲基)苯基(1.1mmol)、碘化亚铜(0.2mmol)和乙醇钠(0.5mmol)的DMF混合物在120摄氏度下搅拌24小时。冷却至室温，混合物过滤，滤液真空浓缩，残余物用柱色谱纯化得到目标化合物9-氯-7-三氟甲基苯基-5-氯甲基-5-乙烯基-4,5-二氢吡咯[1,5-α]喹唑啉-2-氰基(收率：52％)。
化合物C2～C64参照C1方法进行(WO2007144669等文献提到类似的成环方法)，区别在于根据目标化合物的不同，选择不同的原料进行反应，具体化合物如表3所示：
表3
Figure PCTCN2018113811-appb-000024
Figure PCTCN2018113811-appb-000025
Figure PCTCN2018113811-appb-000026
Figure PCTCN2018113811-appb-000027
Figure PCTCN2018113811-appb-000028
Figure PCTCN2018113811-appb-000029
Figure PCTCN2018113811-appb-000030
Figure PCTCN2018113811-appb-000031
Figure PCTCN2018113811-appb-000032
Figure PCTCN2018113811-appb-000033
Figure PCTCN2018113811-appb-000034
表4：表1式(Ⅰ)所示部分化合物的核磁共振氢谱及质谱数据
Figure PCTCN2018113811-appb-000035
Figure PCTCN2018113811-appb-000036
表5：表2式(Ⅰ)所示部分化合物的核磁共振氢谱及质谱数据
Figure PCTCN2018113811-appb-000037
Figure PCTCN2018113811-appb-000038
表6：表3式(Ⅰ)所示部分化合物的核磁共振氢谱及质谱数据
Figure PCTCN2018113811-appb-000039
实施例4：采用方法D合成a-1～a-138化合物
方法D：
Figure PCTCN2018113811-appb-000040
以化合物a-44为例，其具体的制备过程如下：
S1:5-氨基-1H-吡唑-3-氰基
20.0mL的乙醇中加入2,3-二氰基丙酸乙酯(1.0mmol)，剧烈搅拌，向反应液中加入水合肼(2.0mmol)，加热回流，3小时后停止加热，冷却至室温。混合物真空浓缩，用乙酸乙酯和水萃取混合物，真空浓缩萃取得到的乙酸乙酯，得到白色固体5-氨基-1H-吡唑-3-氰基，所述中间体未经进一步纯化，直接用于下一步。
S2:5,5-二氯-7-三氟甲基-4,5-二氢吡唑[1,5-α]喹唑啉[3,2-e]吡啶-2-氰基
氮气保护下，5-氨基-1H-吡唑-3-氰基(1.0mmol)、2-溴-3-(三氯甲基)-5-三氟甲基吡啶(1.0mmol)、碘化亚铜(0.2mmol)和碳酸铯(0.5mmol)的DMF混合物在120摄氏度下搅拌24小时。冷却至室温，混合物过滤，真空浓缩，残余物用柱色谱纯化得到目标化合物5,5-二氯-7-三氟甲基-4,5-二氢吡唑[1,5-α]喹唑啉[3,2-e]吡啶-2-氰基(两步收率：25％)。
S3:5,5-二氯-7-三氟甲基-3-三氟甲基亚磺酰基-4,5-二氢吡唑[1,5-α]喹唑啉[3,2-e]吡啶-2-氰基
氮气保护下，5,5-二氯-7-三氟甲基-4,5-二氢吡唑[1,5-α]喹唑啉[3,2-e]吡啶-2-氰基(0.2mmol)、三氟甲基亚磺酰氯(0.5mmol)、对甲苯磺酸二甲胺盐的无水甲苯混合物在100摄氏度下搅拌加热24小时。冷却至室温，真空浓缩，残余物用柱色谱纯化得到目标化合物5,5-二氯-7-三氟甲基-3-三氟甲基亚磺酰基-4,5-二氢吡唑[1,5-α]喹唑啉[3,2-e]吡啶-2-氰基，收率：77％。
化合物a-1～a-138参照a-44方法进行(其中成环步骤也有Tetrahedron Letters(2015)56:1367；WO2016046404；WO2013174822等文献提到类似的成环方法)，区别在于根据目标化合物的不同，选择不同的原料进行反应，或是由已合成的目标产物经水解、简单的酯化或酰胺化或还原氧化衍生得到。具体化合物如表7所示。
表7：通式为式(a)所示的化合物结构
Figure PCTCN2018113811-appb-000041
Figure PCTCN2018113811-appb-000042
Figure PCTCN2018113811-appb-000043
Figure PCTCN2018113811-appb-000044
实施例5采用方法E合成b-1～b-138化合物
方法E：
Figure PCTCN2018113811-appb-000045
以化合物b-87为例，其具体的合成过程如下：
S1:5-氨基-1H-吡唑-3-三氟甲基(参考文献Journal of medicinal chemistry(2017)60:5099)
氮气保护下，向0摄氏度的20毫升无水四氢呋喃中加入氢化钠(2.5mmol)，随后向反应液中加入无水乙腈(2.0mmol)、三氟乙酸乙酯(1.0mmol)，加热回流，20小时后停止加热，冷却至室温，混合物真空浓缩。用乙醚和水萃取混合物，加入稀盐酸将pH调至2，乙醚萃取，真空浓缩，得到棕色油状物4,4,4-三氟-3-羰基丁腈，所述中间体未经进一步纯化，直接用于下一步。
向4,4,4-三氟-3-羰基丁腈(1.0mmol)和水合肼(1.0毫升)的混合物中加入甲基磺酸(2.0毫升)，加热至80摄氏度，反应10小时后，加入水和乙酸乙酯萃取，真空浓缩，得到残留物用柱色谱纯化得到目标化合物5-氨基-1H-吡唑-3-三氟甲基为黄色液体(两步收率：15％)，1H NMR(400MHz,DMSO-d6):δ12.15(s,1H),5.53(s,1H),5.35(s,2H)。
S2:6-氯-2-三氟甲基-4,5-二氢吡唑[1,5-α]喹唑啉[4,3-e]吡啶-5-甲酸甲酯
氮气保护下，5-氨基-1H-吡唑-3-三氟甲基(1.0mmol)、2-溴-2-(3-溴-5-氯吡啶-4-基)- 乙酸甲酯(1.0mmol)、碘化亚铜(0.2mmol)和乙醇钠(0.5mmol)的DMF混合物在100摄氏度下搅拌24小时。冷却至室温，真空浓缩，残余物用柱色谱纯化得到目标化合物6-氯-2-三氟甲基-4,5-二氢吡唑[1,5-α]喹唑啉[4,3-e]吡啶-5-甲酸甲酯(收率：35％)。
S3:6-氯-2-三氟甲基-3-三氟甲基亚磺酰基-4,5-二氢吡唑[1,5-α]喹唑啉[4,3-e]吡啶-5-甲酸甲酯
氮气保护下，6-氯-2-三氟甲基-4,5-二氢吡唑[1,5-α]喹唑啉[4,3-e]吡啶-5-甲酸甲酯(0.2mmol)、三氟甲基亚磺酰氯(0.5mmol)、对甲苯磺酸二甲胺盐的无水甲苯混合物在100摄氏度下搅拌加热24小时。冷却至室温，真空浓缩，残余物用柱色谱纯化得到目标化合物6-氯-2-三氟甲基-3-三氟甲基亚磺酰基-4,5-二氢吡唑[1,5-α]喹唑啉[4,3-e]吡啶-5-甲酸甲酯，收率：85％。
化合物b-1～b-138参照b-87方法进行(其中成环步骤也有Synthetic Communications(2015)45:2426；Tetrahedron Letters(2014)55:4997；WO2007149907等文献提到类似的成环方法)，区别在于根据目标化合物的不同，选择不同的原料进行反应，或是由已合成的目标产物经水解、简单的酯化或酰胺化或还原氧化衍生得到。具体化合物如表8所示。
表8：通式为式(b)所示的化合物结构
Figure PCTCN2018113811-appb-000046
Figure PCTCN2018113811-appb-000047
Figure PCTCN2018113811-appb-000048
实施例6：采用方法F合成c-1～c-349化合物
方法F：
Figure PCTCN2018113811-appb-000049
以化合物c-27为例，其具体的合成过程如下：
S1:6-氯-2-氰基-5-(2’2-二乙氧基)-8-三氟甲基-4,5-二氢吡唑[1,5-α]喹唑啉-5-甲酸乙酯
氮气保护下，5-氨基-1H-吡唑-3-氰基(1.0mmol)、2-溴-2-(2-溴-6-氯-4-三氟甲基苯基)苹果酸二乙酯(1.0mmol)、碘化亚铜(0.2mmol)和碳酸铯(0.5mmol)的DMF混合物在100摄氏度下搅拌24小时。冷却至室温，混合物过滤，真空浓缩，残余物用柱色谱纯化得到目标化合物6-氯-2-氰基-5-(2’2-二乙氧基)-8-三氟甲基-4,5-二氢吡唑[1,5-α]喹唑啉-5-甲酸乙酯(收率：30％)。
S2:6-氯-2-氰基-5-(2’2-二乙氧基)-8-三氟甲基-3-三氟甲基亚磺酰基-4,5-二氢吡唑[1,5-α]喹唑啉-5-甲酸乙酯
氮气保护下，6-氯-2-氰基-5-(2’2-二乙氧基)-8-三氟甲基-4,5-二氢吡唑[1,5-α]喹唑啉-5-甲酸乙酯(0.2mmol)、三氟甲基亚磺酰氯(0.5mmol)、对甲苯磺酸二甲胺盐的无水甲苯混合物在100摄氏度下搅拌加热24小时。冷却至室温，真空浓缩，残余物用柱色谱纯化得到目标化合物6-氯-2-氰基-5-(2’2-二乙氧基)-8-三氟甲基-3-三氟甲基亚磺酰基-4,5-二氢吡唑[1,5-α]喹唑啉-5-甲酸乙酯，收率：82％。
S3:2-(6-氯-2-氰基-5-(2’2-二乙氧基)-8-三氟甲基-3-三氟甲基亚磺酰基-4,5-二氢吡唑[1,5-α]喹唑啉-5-基)-乙酸
6-氯-2-氰基-5-(2’2-二乙氧基)-8-三氟甲基-3-三氟甲基亚磺酰基-4,5-二氢吡唑[1,5-α]喹唑啉-5-甲酸乙酯(1.0mmol)溶解在5毫升的二氧六环中，加入10毫升的1N HCl，加热回流5小时，加入乙酸乙酯萃取，真空浓缩，残余物用柱色谱纯化得到目标化合物2-(6-氯-2-氰基-5-(2’2-二乙氧基)-8-三氟甲基-3-三氟甲基亚磺酰基-4,5-二氢吡唑[1,5-α]喹唑啉-5-基)-乙酸，收率：78％。
化合物c-1～c-349参照c-27方法进行(其中成环步骤也有WO2007144669等文献提到类似的成环方法)，区别在于根据目标化合物的不同，选择不同的原料进行反应，或是由已合成的目标产物经水解、简单的酯化或酰胺化或还原氧化衍生得到。具体化合物如表9所示。
表9：通式为式(c)所示的化合物结构
Figure PCTCN2018113811-appb-000050
Figure PCTCN2018113811-appb-000051
Figure PCTCN2018113811-appb-000052
Figure PCTCN2018113811-appb-000053
Figure PCTCN2018113811-appb-000054
Figure PCTCN2018113811-appb-000055
Figure PCTCN2018113811-appb-000056
Figure PCTCN2018113811-appb-000057
实施例7：以方法G合成d-1～d-142化合物
方法G：
Figure PCTCN2018113811-appb-000058
以化合物d-12为例，其具体的合过程如下成：
S1:9-氯-2-氰基-3-环己烷巯基-5-(2’2-二甲氧基)-7-三氟甲基-4,5-二氢吡唑[1,5-α]喹唑啉-5-甲酸甲酯(参考文献synthetic communications(2012)42:3472)
氮气保护下，9-氯-2-氰基-5-(2’2-二甲氧基)-7-三氟甲基-4,5-二氢吡唑[1,5-α]喹唑啉-5-甲酸甲酯(2.0mmol，合成方法同c-27S1类似，产率26％)、二环己基二硫化合物(1.0mmol)、三溴化铁(0.5mmol)和单质碘(0.5mmol)的无水乙腈混合物在85摄氏度下搅拌24小时。冷却至室温，真空浓缩，残余物用柱色谱纯化得到目标化合物9-氯-2-氰基 -3-环己烷巯基-5-(2’2-二甲氧基)-7-三氟甲基-4,5-二氢吡唑[1,5-α]喹唑啉-5-甲酸甲酯(收率：90％)。
S2:9-氯-2-氰基-3-环己烷亚磺酰基-5-(2’2-二甲氧基)-7-三氟甲基-4,5-二氢吡唑[1,5-α]喹唑啉-5-甲酸甲酯
9-氯-2-氰基-3-环己烷巯基-5-(2’2-二甲氧基)-7-三氟甲基-4,5-二氢吡唑[1,5-α]喹唑啉-5-甲酸甲酯(1.0mmol)溶解在无水二氯甲烷中、冷却至负15摄氏度，向其中加入间氯过氧苯甲酸(85％,1.1mmol)，保持低温搅拌反应1小时。放至室温，加入碳酸氢钠水溶液，二氯甲烷萃取，真空浓缩，残余物用柱色谱纯化得到目标化合物9-氯-2-氰基-3-环己烷亚磺酰基-5-(2’2-二甲氧基)-7-三氟甲基-4,5-二氢吡唑[1,5-α]喹唑啉-5-甲酸甲酯，收率：97％。
化合物d-1～d-142参照d-12方法进行(其中成环步骤也有Tetrahedron Letters(2015)56:1367；WO2016046404；WO2013174822；Synthetic Communications(2015)45:2426；Tetrahedron Letters(2014)55:4997；WO2007149907等文献提到类似的成环方法)，区别在于根据目标化合物的不同，选择不同的原料进行反应，或是由已合成的目标产物经水解、简单的酯化或酰胺化或还原氧化衍生得到。具体化合物如表10所示。
表10：通式为式(d)所示的化合物结构
Figure PCTCN2018113811-appb-000059
Figure PCTCN2018113811-appb-000060
Figure PCTCN2018113811-appb-000061
实施例8：采用方法H合成e-1～e-24化合物
方法H：
Figure PCTCN2018113811-appb-000062
化合物e-1～e-24参照c系列和d系列的合成方法进行(其中成环步骤也有WO2016046404；WO2013174822；Synthetic Communications(2015)45:2426；Tetrahedron Letters(2014)55:4997；WO2007149907等文献提到类似的成环方法)，区别在于根据目标化合物的不同，选择不同的原料进行反应，或是由已合成的目标产物经水解、简单的酯化或酰胺化或还原氧化衍生得到。具体化合物如表11所示。
表11：通式为式(e)所示的化合物结构
Figure PCTCN2018113811-appb-000063
表7中通式(a)所示化合物中部分化合物的核磁共振氢谱及质谱数据见表12所示。
表12：通式(a)所示部分化合物的核磁共振氢谱及质谱数据
Figure PCTCN2018113811-appb-000064
Figure PCTCN2018113811-appb-000065
Figure PCTCN2018113811-appb-000066
Figure PCTCN2018113811-appb-000067
表8中通式(b)所示化合物中部分化合物的核磁共振氢谱及质谱数据见表13所示。
表13：通式(b)所示部分化合物的核磁共振氢谱及质谱数据
Figure PCTCN2018113811-appb-000068
Figure PCTCN2018113811-appb-000069
Figure PCTCN2018113811-appb-000070
表9中通式(c)所示化合物中部分化合物的核磁共振氢谱及质谱数据见表14所示。
表14：通式(c)所示部分化合物的核磁共振氢谱及质谱数据
Figure PCTCN2018113811-appb-000071
Figure PCTCN2018113811-appb-000072
Figure PCTCN2018113811-appb-000073
Figure PCTCN2018113811-appb-000074
表10中通式(d)所示化合物中部分化合物的核磁共振氢谱及质谱数据见表15所示。
表15：通式(d)所示部分化合物的核磁共振氢谱及质谱数据
Figure PCTCN2018113811-appb-000075
Figure PCTCN2018113811-appb-000076
Figure PCTCN2018113811-appb-000077
表11中通式(e)所示化合物中部分化合物的核磁共振氢谱及质谱数据见表16所示。
表16：通式(e)所示部分化合物的核磁共振氢谱及质谱数据
Figure PCTCN2018113811-appb-000078
Figure PCTCN2018113811-appb-000079
实施例9：杀虫活性实施例
(1)对小菜蛾2龄幼虫的杀虫活性
小菜蛾Plutella xylostella(L.)属于鳞翅目害虫，具有咀嚼式口器，是一种常见的蔬菜害虫。以小菜蛾2龄幼虫为测试对象，采用浸叶饲喂法测试。
操作过程：准确称量各样品，分别加入200微升的二甲基亚砜配制成10g/L母液，实验时用含千分之0.5吐温-80的水溶液将其稀释至500ppm的浓度。用直径1.0厘米打孔器将洗净甘蓝叶制成叶碟，叶碟浸入药液中，5秒后取出，自然晾干，移入干净器皿中。向器皿中接入35头左右的小菜蛾2龄幼虫，于28摄氏度恒温饲养。每浓度设3次重复，对照组为含千分之0.5吐温-80的水溶液。处理24小时后，统计小菜蛾的死亡虫数，并根据公式计算死亡率(％)：死亡率(％)＝(对照活虫数－处理活虫数)/对照活虫数×100％。结果见表17～表24。
(2)对甜菜夜蛾2龄幼虫的杀虫活性
甜菜夜蛾Spodoptera exigua属于鳞翅目害虫，具有咀嚼式口器，是一种常见的蔬菜害虫。以甜菜夜蛾2龄幼虫为测试对象，采用浸叶饲喂法测试。
操作过程：准确称量各样品，分别加入200微升的二甲基亚砜配制成10g/L母液，实验时用含千分之0.5吐温-80的水溶液将其稀释至500ppm的浓度。用直径1.0厘米打孔器将洗净甘蓝叶制成叶碟，叶碟浸入药液中，5秒后取出，自然晾干，移入干净器皿中。向器皿中接入35头左右的甜菜夜蛾2龄幼虫，于28摄氏度摄摄氏度恒温饲养。每浓度设3次重复，对照组为含千分之0.5吐温-80的水溶液。处理24小时后，统计小菜蛾的死亡虫数，并根据公式计算死亡率(％)：死亡率(％)＝(对照活虫数－处理活虫数)/对照活虫数×100％。结果见表17～表24。
(3)对蚜虫成虫的杀虫活性
蚜虫属于同翅亚目害虫，具有刺吸式口器，是一种常见的蔬菜害虫。以豆蚜(Aphis craccivora)为测试对象，采用浸渍法测试。
操作过程：准确称量各样品，分别加入200微升的二甲基亚砜配制成10g/L母液，实验时用含千分之0.5吐温-80的水溶液将其稀释至500ppm的浓度。待无翅成蚜在豆芽上稳定吸食后，连同豆芽一起浸入浓度为500ppm的药液中，5秒后取出，自然晾干，移入干净器皿中，于23摄氏度恒温饲养。每浓度设3次重复，对照组为含千分之0.5吐温-80的水溶液。处理24小时后，统计蚜虫的死亡虫数，并根据公式计算死亡率(％)：死亡率(％)＝(对照活虫数－处理活虫数)/对照活虫数×100％。结果见表17～表24。
(4)对红火蚁工蚁的杀虫活性
红火蚁属于膜翅目害虫，社会性昆虫，是一种极具破坏力入侵生物之一。以红火蚁工蚁(Solenopsis invicta)为测试对象，采用水试管喂毒法测试。
操作过程：准确称量各样品，分别加入200微升的二甲基亚砜配制成10g/L母液，实验时用含千分之0.5吐温-80和百分之五蜂蜜的混合水溶液将其稀释至100ppm的浓度。取红火蚁置于养蚁试管中，药液用注射器注入养蚁试管的硅胶塞中，以药液不渗出为宜。将养蚁试管平置于养蚁盒内，向试管加入少量火腿肠作为食物，于25摄氏度恒温饲养。处理24h和72h调查活虫数和死虫数，并根据公式计算死亡率(％)：死亡率(％)＝(对照活虫数－处理活虫数)/对照活虫数×100％。结果见表17～表24。
表17：式(Ⅰ)所示化合物对供试害虫的杀虫活性
Figure PCTCN2018113811-appb-000080
Figure PCTCN2018113811-appb-000081
表18：式(Ⅰ)所示部分化合物对供试害虫的杀虫活性
Figure PCTCN2018113811-appb-000082
表19：表3式(Ⅰ)所示化合物对供试害虫的杀虫活性
Figure PCTCN2018113811-appb-000083
Figure PCTCN2018113811-appb-000084
表20：通式(a)所示部分化合物对供试害虫的杀虫活性
Figure PCTCN2018113811-appb-000085
Figure PCTCN2018113811-appb-000086
表21：通式(b)所示部分化合物对供试害虫的杀虫活性
Figure PCTCN2018113811-appb-000087
Figure PCTCN2018113811-appb-000088
表22：通式(c)所示部分化合物对供试害虫的杀虫活性
Figure PCTCN2018113811-appb-000089
Figure PCTCN2018113811-appb-000090
表23：通式(d)所示部分化合物对供试害虫的杀虫活性
Figure PCTCN2018113811-appb-000091
Figure PCTCN2018113811-appb-000092
表24：通式(e)所示部分化合物对供试害虫的杀虫活性
Figure PCTCN2018113811-appb-000093
Figure PCTCN2018113811-appb-000094
从表中可以看出，本发明列举的化合物对农林业害虫、动物寄生性害虫和卫生害虫等具有高的杀灭活性，由其是对鳞翅目、同翅目、膜翅目等害虫具有很好的活性，并且对红火蚁有延时起效的作用，对整个红火蚁蚁巢和蚁后有更好的杀灭效果。
实施例10：环境安全性实施例
本发明部分化合物对环境非靶标生物的毒性测试，结果如下表所示：
(1)对家蚕2龄幼虫的毒性测试
家蚕(Bombyx mori L.)是农业生态系统中对农药十分敏感的重要经济昆虫，也是我国农药登记中所列环境生态的非靶标生物之一。以家蚕2龄幼虫为测试对象，采用浸叶饲喂法测试。
操作过程：准确称量各样品，分别加入200微升的二甲基亚砜配制成10g/L母液，实验时用含千分之0.5吐温-80的水溶液将其稀释至1000ppm的浓度。采集桑树幼嫩子叶冲洗晾干水分后，浸入药液中，5秒后取出，自然晾干，移入干净器皿中。向器皿中接入35头左右的家蚕2龄幼虫，于25摄氏度恒温饲养。每浓度设3次重复，对照组为含千分之0.5吐温-80的水溶液。处理24小时后，统计小菜蛾的死亡虫数，并根据公式计算死亡率(％)：死亡率(％)＝(对照活虫数-处理活虫数)/对照活虫数×100％。结果见表10。
(2)对蜜蜂成年工蜂毒性测试
中华蜜蜂(Apis cernan)，选取大小一致的成年工蜂试验，试验当天晨间从养蜂箱中采集，采用小烧杯法测试。
操作过程：在5mL小烧杯中塞入少量脱脂棉，将供试药液(500ppm的浓度)5mL滴加到脱脂棉中，轻轻搅动，使脱脂棉完全湿润但无明水浸出，然后将小烧杯放入500mL大烧杯中，再放入15头工蜂，最后用纱布封口。处理后置于人工气候箱暗室中。药后48h，调查活虫数和死虫数。结果见表25。
表25：表1至表3中式(Ⅰ)所示部分化合物对环境非靶标生物的毒性
Figure PCTCN2018113811-appb-000095
Figure PCTCN2018113811-appb-000096
实施例11含有本发明化合物的农药组合物的制备
(1)油状悬浮液
按比例准备以下组分：25％(重量百分比，下同)上述化合物中任一种化合物；5％聚氧乙烯山梨醇六油酸酯；70％高级脂肪族烃油。将各组分在沙磨中一起研磨，直到固体颗粒降至5微米以下为止。所得的粘稠悬浮液可直接使用，但也可在水中乳化后使用。
(2)水悬浮液
按比例准备以下组分：25％上述化合物中任一种化合物；3％水合硅镁土；10％木质素 磺酸钙；0.5％磷酸二氢钠；61.5％水。将各组分在球磨机中一起研磨，直到固体颗粒降至约10微米以下为止。该水悬浮液可直接使用。
(3)饵剂
按比例准备以下组分：0.1～10％上述化合物中任一种化合物；80％小麦面粉；19.9～10％糖蜜。将这些组分完全混合，按需要形成饵形状。可食饵可以分散到卫生害虫所侵染的场所，例如家具或工业场所，诸如厨房、医院或商店或户外区域，以通过口服摄入来防治害虫。
最后所应当说明的是，以上实施例仅用以说明本发明的技术方案而非对本发明保护范围的限制，对于本领域的普通技术人员来说，在上述说明及思路的基础上还可以做出其它不同形式的变化或变动，这里无需也无法对所有的实施方式予以穷举。凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等，均应包含在本发明权利要求的保护范围之内。

Claims (17)

  1. 稠合杂环化合物及其光学异构体、顺反异构体或农药学上可接受的盐，其特征在于，所述稠合杂环化合物具有式(Ⅰ)所示结构：
    Figure PCTCN2018113811-appb-100001
    式(Ⅰ)；
    其中，R 11和R 12各自独立地为氢、卤素、-NO 2、-CN、-COR 17、-CO 2R 17、-CONR 17R 18、-S(O)R 17、-S(O) 2R 17、-NR 17R 18、-NR 17COR 18、-NR 17CONR 18R 19、-NR 17CO 2R 18、-NR 17S(O) 2R 18、烷基、杂烷基、烯基、环烷基、环烯基、芳基、杂环基或杂芳基；其中烷基、烯基、环烷基、环烯基、芳基、杂环基或杂芳基未经取代或经一个或多个取代基R 10取代；
    R 13为氢、-COR 7、-CO 2R 17、-S(O) 2R 17、-CONR 17R 18、烷基、杂烷基、烯基、环烷基、环烯基、芳基；其中烷基、烯基、环烷基、环烯基、芳基未经取代或经一个或多个取代基R 10取代；
    R 14和R 15各自独立地为氢、卤素、-CN、-OH、-NR 17R 18、-OR 17、-COR 17、-CO 2R 17、-CONR 17R 18、-NR 17COR 18、-NR 17CONR 18R 19、-NR 17CO 2R 18、-NR 17S(O) 2R 18、-S(O)R 17、-S(O) 2R 17、烷基、杂烷基、烯基、环烷基、环烯基、芳基、杂环基或杂芳基；其中烷基、烯基、环烷基、环烯基、芳基、杂环基或杂芳基未经取代或经一个或多个取代基R 10取代，且R 14和R 15不同时为氢；
    Y为N或CH；
    Z 1、Z 2、Z 3、Z 4各自独立地为C或N，条件是Z 1至Z 4中的至多两个是N，且含有Z 1至Z 4的环是芳族的；
    R 16表示含有Z 1至Z 4环上的取代基，R 16的数量可以是一个或多个，各R 16独立地为氢、卤素、-CN、烷基、杂烷基、-COR 17、-CO 2R 17、-NR 17R 18、-CONR 17R 18、-NR 17COR 18、-NR 17CONR 18R 19、-NR 17CO 2R 18或-NR 17S(O) 2R 18；
    R 17、R 18和R 19各自独立地为氢、烷基、杂烷基、烯基、环烷基、环烯基、杂环基、芳基或者杂芳基；其中烷基、烯基、环烷基、环烯基、芳基、杂环基或杂芳基未经取代或经一个或多个取代基R 10取代；
    R 10为卤素、C 1-C 6烷基、C 2-C 6烯基、取代或未取代的环烷基、环烯基、取代或未取代的芳基、取代或未取代的杂芳基、取代或未取代的杂环基、-CN、-NH 2、-OR”’、-NR”’R””、-COR”’、-CO 2R”’、-CONR”’R””、-NR”’COR””、-NR”’CONR”’R””、-NR”’CO 2R””、-S(O) 2R”’或者-NR”’S(O) 2R””，其中R”’和R””独立的为氢、C 1-C 6烷基、C 2-C 6烯基、环烷基、环烯基、芳基、杂芳基、杂环基。
  2. 根据权利要求1所述化合物、或者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，当Y为N或CH时；
    R 11为卤素、-CN、-COR 17、-CONR 17R 18、-S(O)R 17、-NR 17R 18、-NR 17COR 18、芳基、杂环基或杂芳基；其中芳基、杂环基或杂芳基未经取代或经一个或多个取代基R 10取代；
    R 12为氢、-COR 17、-CONR 17R 18、-S(O)R 17、-S(O) 2R 17、-NR 17R 18、-NR 17COR 18、-NR 17CONR 18R 19、-NR 17CO 2R 18、芳基、杂环基或杂芳基；其中芳基、杂环基或杂芳基未 经取代或经一个或多个取代基R 10取代；
    R 13为氢、-COR 17、烷基、杂烷基或烯基；
    R 14为卤素、-CN、-NR 17R 18、-OR 17、-COR 17、-CO 2R 17、-CONR 17R 18、-NR 17COR 18、-NR 17CO 2R 18、烷基、杂烷基或烯基；其中烷基、杂烷基或烯基未经取代或经一个或多个取代基R 10取代；
    R 15为氢、卤素、-CN、-NR 17R 18、-OR 17、-COR 17、-CO 2R 17、-CONR 17R 18、-NR 17COR 18、-NR 17CO 2R 18、烷基、杂烷基或烯基；其中烷基、杂烷基或烯基未经取代或经一个或多个取代基R 10取代。
  3. 根据权利要求1所述化合物、或者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，当Z 1、Z 2、Z 3、Z 4均为C时，R 16可以是一个或多个，且各R 16独立地为氢、卤素、烷基、杂烷基、烯基、-S(O)R 17、-S(O) 2R 17、-COR 17、-NR 17R 18、-CONR 17R 18、-NR 17COR 18或-NR 17S(O) 2R 18；
    R 11为卤素、-CN、-COR 17、-CONR 17R 18、-S(O)R 17、-NR 17R 18、-NR 17COR 18、芳基、杂环基或杂芳基；其中芳基、杂环基或杂芳基未经取代或经一个或多个取代基R 10取代；
    R 12为-CONR 17R 18、-S(O)R 17、-S(O) 2R 17、-NR 17R 18、-NR 17COR 18、-NR 17CONR 18R 19、芳基、杂环基或杂芳基；其中芳基、杂环基或杂芳基未经取代或经一个或多个取代基R 10取代；
    R 13为氢、-COR 17、烷基或烯基；
    R 14和R 15各自独立地为卤素、-CN、-NR 17R 18、-OR 17、-COR 17、-CO 2R 17、-CONR 17R 18、-NR 17COR 18、-NR 17CO 2R 18、烷基、杂烷基、烯基；其中烷基、杂烷基、烯基未经取代或经一个或多个取代基R 10取代。
  4. 根据权利要求1所述化合物、或者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，
    当Y为N或CH时；
    R 11为卤素、-CN、-COR 17、-CONR 17R 18、-S(O)R 17、-NR 17R 18、-NR 17COR 18；
    R 12为-S(O)R 17、-S(O) 2R 17、-NR 17R 18、-NR 17COR 18、芳基或杂芳基；其中芳基或杂芳基未经取代或经一个或多个取代基R 10取代；
    R 13为氢、-COR 17、烷基或烯基；
    R 14和R 15各自独立地为卤素、-CN、-NR 17R 18、-OR 17、-COR 17、-CO 2R 17、-CONR 17R 18、-NR 17COR 18、-NR 17CO 2R 18、烷基、杂烷基或烯基；其中烷基或烯基未经取代或经一个或多个取代基R 10取代；
    Z 1、Z 2、Z 3、Z 4均为C，R 16可以是一个或多个，且各R 16独立地为卤素、烷基、杂烷基、-S(O)R 17、-S(O) 2R 17、-COR 17、-NR 17R 18、-NR 17COR 18或-NR 17S(O) 2R 18。
  5. 根据权利要求4所述化合物、或者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，
    R 11为卤素、-CN、-COR 17或-CONR 17R 18；
    R 12为-S(O)R 17、-S(O) 2R 17、-NR 17COR 18、芳基或杂芳基；其中芳基或杂芳基未经取代或经一个或多个取代基R 10取代；
    R 13为氢、-COR 17或烷基；
    Z 1、Z 2、Z 3、Z 4均为C，R 16可以是一个或多个，且各R 16独立地为卤素、杂烷基、-S(O)R 17、-NR 17R 18或-NR 17COR 18。
  6. 根据权利要求4所述化合物、或者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，
    R 11为-CN或-COR 17；
    R 12为-S(O)R 17或芳基；其中芳基经一个或多个取代基R 10取代；
    R 13为氢、-COR 17、甲基或乙基；
    R 14和R 15各自独立地为卤素、-OR 17、-COR 17、-CO 2R 17、-CONR 17R 18、-NR 17COR 18、-NR 17CO 2R 18、烷基、杂烷基或烯基；其中烷基或烯基未经取代或经一个或多个取代基R 10取代；
    Z 1、Z 2、Z 3、Z 4均为C，R 16可以是一个或多个，且各R 16独立地为卤素或杂烷基。
  7. 根据权利要求4所述化合物、或者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，
    R 11为-CN或-COR 17，且R 17为烷基或杂烷基；
    R 12为-S(O)R 17，且R 17为烷基或杂烷基；
    R 13为氢、-COR 17、甲基或乙基，且R 17为烷基；
    R 14和R 15各自独立地为卤素、-OR 17、-COR 17、-CO 2R 17、-CONR 17R 18、-NR 17COR 18、-NR 17CO 2R 18、烷基、杂烷基或烯基；其中烷基或烯基未经取代或经一个或多个取代基R 10取代；
    Z 1、Z 2、Z 3、Z 4均为C，R 16可以是一个或多个，且各R 16独立地为卤素或杂烷基。
  8. 一类含吡唑环的稠合杂环化合物及其光学异构体、顺反异构体或农药学上可接受的盐，其特征在于，所述含吡唑环的稠合杂环化合物具有式(Ⅱ)所示结构：
    Figure PCTCN2018113811-appb-100002
    式(Ⅱ)；
    其中，R 1为氢、卤素、-CN、烷基、杂烷基、芳基或杂芳基；其中烷基、芳基或杂芳基未经取代或经一个或多个取代基R 9取代；
    R 2为氢、卤素、-CN、-S(O)R 7、-S(O) 2R 7、烷基、杂烷基、芳基或杂芳基；其中烷基、芳基或杂芳基未经取代或经一个或多个取代基R 9取代；
    R 3为氢、-COR 7、烷基或杂烷基；
    R 4和R 5各自独立地为氢、卤素、-CN、-COR 7、-CO 2R 7、-CH 2COR 7、-CH 2COOR 7、氨基、烷基、杂烷基、芳基或杂芳基；其中氨基、烷基、芳基或杂芳基未经取代或经一个或多个取代基R 9取代，且R 4和R 5不同时为氢；
    Z 1和Z 2各自独立地为C或N，不同时为N，且含有Z 1和Z 2的环为芳族环；
    R 6表示含有Z 1和Z 2环上的取代基，R 6的数量可以是一个或多个，各R 6独立地为氢、卤素、-NO 2、-CN、烷基、杂烷基、-OR 7、-COR 7、-CO 2R 7或-NR 7R 8；
    R 7和R 8各自独立地为氢、羟基、氨基、C 1-C 6烷基、杂烷基、芳基或者杂芳基；其中烷基、芳基或杂芳基未经取代或经一个或多个取代基R 9取代；
    R 9为卤素、C 1-C 6烷基、杂烷基、-CN、-NH 2、-OH、-COR’、-CO 2R’或-CONR’R”，其中R’和R”独立的为氢、C 1-C 6烷基或杂烷基。
  9. 根据权利要求8所述化合物、或者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，
    当Z 1为N，Z 2为C时，R 6为吡啶环5位-CF 3单取代，所述化合物的通式为式(a)所示：
    Figure PCTCN2018113811-appb-100003
    其中R 3为氢、甲基或氯代甲基；R 4和R 5各自独立地为氢、卤素、-CN、-COR 7、-CO 2R 7、-CH 2COR 7、-CH 2COOR 7、氨基、烷基、杂烷基、芳基或杂芳基；其中氨基、烷基、芳基或杂芳基未经取代或经一个或多个取代基R 9取代；
    或，
    当Z 2为N，Z 1为C时，R 6为吡啶环5位氯单取代，所述化合物的通式为式(b)所示：
    Figure PCTCN2018113811-appb-100004
    其中R 3为氢、甲基或氯代甲基；R 4和R 5各自独立地为氢、卤素、-CN、-COR 7、-CO 2R 7、-CH 2COR 7、-CH 2COOR 7、氨基、烷基、杂烷基、芳基或杂芳基；其中氨基、烷基、芳基或杂芳基未经取代或经一个或多个取代基R 9取代；
    或，
    当Z 1和Z 2同为C，R 6为苯环上3位和5位双取代时，所述化合物的通式为式(c)所示：
    Figure PCTCN2018113811-appb-100005
    其中R 1为-CN或-CF 3，R 2为-CN、-CF 3、-OCF 3、-SOCF 3或-SOCH 2CH 3；R 3为氢、-CH 3、-Ac或-CH 2CH 2Cl；R 6在苯环的3位上的取代基为-Cl、-Br、-CF 3、-CH 3、-CN、-CO 2CH 3或-NO 2，R 6在苯环的5位上的取代基为-Cl、-CF 3、-OCF 3或-NO 2；R 4和R 5各自独立地为氢、卤素、-CN、-COR 7、-CO 2R 7、-CH 2COR 7、-CH 2COOR 7、氨基、烷基、杂烷基、芳基或杂芳基；其中氨基、烷基、芳基或杂芳基未经取代或经一个或多个取代基R 9取代；
    或，
    当Z 1和Z 2同为C，R 6为苯环上4位和6位双取代，R 3为氢时，所述化合物的通式为式(d)所示：
    Figure PCTCN2018113811-appb-100006
    其中R 1为-CN、-CF 3、-COCH 3或-CH 2NH 2，R 2为-OCF 3、-CF 3、-CN、-SOCF 3、-SOCH 3、-SOCH 2CH 3、-SOPh、-SOCH 2Ph、-SOC 6H 13、、
    Figure PCTCN2018113811-appb-100007
    Figure PCTCN2018113811-appb-100008
    R 6为-Cl或-CF 3；R 4和R 5各自独立地为氢、卤素、-CN、-COR 7、-CO 2R 7、-CH 2COR 7、-CH 2COOR 7、氨基、烷基、杂烷基、芳基或杂芳基；其中氨基、烷基、芳基或杂芳基未经取代或经一个或多个取代基R 9取代；
    或，
    当Z 1和Z 2同为C，R 6为苯环上3、6位或者3、4位或者4、5位或者5、6位双取代，R 3为氢时，所述化合物的通式为式(e)所示：
    Figure PCTCN2018113811-appb-100009
    其中R 1为-CN，R 2为-SOCF 3；R 6为-Cl或-CF 3；R 4和R 5各自独立地为氢、卤素、-CN、-COR 7、-CO 2R 7、-CH 2COR 7、-CH 2COOR 7、氨基、烷基、杂烷基、芳基或杂芳基；其中氨基、烷基、芳基或杂芳基未经取代或经一个或多个取代基R 9取代；且R 4和R 5不同时为氢。
  10. 根据权利要求9所述化合物、或者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，R 4和R 5各自独立地为氢、卤素、-CN、-COR 7、-CO 2R 7、-CH 2COR 7、-CH 2COOR 7、氨基、烷基或杂烷基；其中R 7为氢、卤素、羟基、C 1～4烷基、C 1～4卤代烷基、C 1～4烯基、C 1～4卤代烯基、氨基或取代氨基。
  11. 根据权利要求9所述化合物、或者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，当所述化合物为式(a)或式(b)所示，R 4和R 5任一为氢时，R 1为-CN，R 2为-SOCF 3或者-OCF 3；或R 1为-CF 3，R 2为-SOCF 3；
    或，R 4和R 5均不为氢时，R 1为-CN或-CF 3；R 2为-SOCF 3、-SOCH 2CH 3、-OCF 3、-CF 3、-CN或卤素。
  12. 根据权利要求9所述化合物、或者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，当所述化合物为式(c)所示，R 3为-CH 3、-Ac或-CH 2CH 2Cl时，R 2为-SOCF 3，R 1为-CN，R 4和R 5均为-CO 2Me；
    或，R 3为氢，R 2为-CN、-CF 3或-SOCH 2CH 3时，R 1为-CN或-CF 3，R 4和R 5各自独立地为-CO 2Me或-CH 2CO 2Me；
    或，R 3为氢时，R 2为-OCF 3或-SOCF 3时，R 1为-CN或-CF 3，R 4和R 5各自独立地为氢、卤素、-CN、-COR 7、-CO 2R 7、-CH 2COR 7、-CH 2COOR 7、氨基、烷基、杂烷基、芳基或杂 芳基；其中氨基、烷基、芳基或杂芳基未经取代或经一个或多个取代基R 9取代。
  13. 根据权利要求9所述化合物、或者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，当所述化合物为式(d)所示，R 3为氢，R 2为-CN、-CF 3、-SOPh、-SOCH 2Ph、-SOC 6H 13、或
    Figure PCTCN2018113811-appb-100010
    Figure PCTCN2018113811-appb-100011
    时，R 1为-CN，R 4和R 5各自独立地为-CO 2Me或-CO 2CH 2Me；
    或，R 3为氢，R 2为-SOCF 3，R 1为-COCH 3或-CH 2NH 2时，R 4和R 5各自独立地为-CO 2Me或-CO 2CH 2Me；
    或，R 3为氢，R 2为-OCF 3或-SOCF 3时，R 1为-CN或-CF 3，R 4和R 5各自独立地为氢、卤素、-CN、-COR 7、-CO 2R 7、-CH 2COR 7、-CH 2COOR 7、氨基、烷基、杂烷基、芳基或杂芳基；其中氨基、烷基、芳基或杂芳基未经取代或经一个或多个取代基R 9取代。
  14. 根据权利要求9所述化合物、或者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，当所述化合物为式(e)所示时，R 6为苯环上3-Cl和6-CF 3、3-Cl和4-CF 3、4-Cl和5-CF 3或5-Cl和6-CF 3；R 4和R 5各自独立地为-CO 2Me、-CH 2CO 2Me、-CO 2Et、-CH 2CO 2Et、-CH 2CO 2CH 2CF 3或-CH 2CO 2CH 2CHF 2。
  15. 一种农用组合物，它包含：
    (a)0.001～99.99重量％的权利要求1～14中任一项所述化合物、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；以及
    (b)农药上可接受的载体和/或赋形剂。
  16. 权利要求15所述农用组合物在制备用于杀灭或预防农林业害虫、卫生害虫和危害动物健康的害虫的杀虫剂中的应用。
  17. 根据权利要求16所述应用，其特征在于，将所述杀虫剂直接施加在害虫身上或其接触的场所。
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TETRAHEDRON LETTERS, vol. 55, 2014, pages 4997
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JP2021508674A (ja) 2021-03-11
BR112020008750A2 (pt) 2020-10-20
US20210188853A1 (en) 2021-06-24
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