CN114369090A - Mesoionic compound and preparation method and application thereof - Google Patents

Mesoionic compound and preparation method and application thereof Download PDF

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Publication number
CN114369090A
CN114369090A CN202111191288.1A CN202111191288A CN114369090A CN 114369090 A CN114369090 A CN 114369090A CN 202111191288 A CN202111191288 A CN 202111191288A CN 114369090 A CN114369090 A CN 114369090A
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alkyl
alkoxy
radical
halo
ring
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李义涛
徐俊星
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Dongguan Hec Pesticides R&d Co ltd
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Dongguan Hec Pesticides R&d Co ltd
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    • 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
    • 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
    • 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

Abstract

The invention relates to a mesoionic compound and a preparation method and application thereof; in particular, the invention relates to a mesoionic compound shown in formula (I) or a stereoisomer, a nitrogen oxide and a salt thereof of the mesoionic compound shown in formula (I), a preparation method of the mesoionic compound, application of the mesoionic compound and a composition containing the mesoionic compound as pesticides in agriculture, and a method for controlling pests by using the compounds or the composition; wherein R is1、R2、R3、R4、R5And R6Have the meaning as described in the present invention.

Description

Mesoionic compound and preparation method and application thereof
Technical Field
The invention relates to the field of pesticides, in particular to a mesoionic compound and a preparation method thereof, and application of the mesoionic compound and a composition containing the mesoionic compound as an insecticide in the field of pesticides.
Background
Damage by invertebrate pests is common in agriculture, forestry, greenhouse crops, ornamentals, nursery crops, stored food, livestock, habitable rooms, turf, wood products, and public health, causing significant losses in economic and health of life. Because of the increasing drug resistance of many current commercial pesticides, the pest can be killed by increasing the dosage, which brings great burden to the environment. Thus, there is a continuing need for new compounds to control invertebrate pests that are more effective, more economical, less toxic, environmentally safer or have different sites of action.
WO2009099929, WO 2011017347 and WO2011017342 disclose the control effect of chain group-substituted mesoionic compounds on various pests, while the compounds related to the present invention are not disclosed.
Disclosure of Invention
The invention provides a mesoionic compound, a preparation method of the compound, application of the compound, a composition containing the compound and a preparation in pest control.
Specifically, in one aspect, the present invention provides a compound which is a compound having formula (I) or a stereoisomer, a nitrogen oxide or a salt thereof of the compound having formula (I):
Figure BDA0003301199890000011
wherein:
R1is hydrogen, C1-8Alkyl, halo C1-8Alkyl radical, C2-8Alkenyl radical, C2-8Alkynyl, C3-8Cycloalkyl radical, C3-8cycloalkyl-C1-3Alkylene-, C3-8Cycloalkenyl or C3-8Cycloalkenyl radical-C1-3Alkylene-; wherein R is1Optionally substituted by 1,2 or 3 substituents selected from halogen, hydroxy, nitro, amino, carboxy, cyano, C1-6Alkyl radical, C1-6Alkoxy, halo C1-6Alkyl or halo C1-6Alkoxy substitution;
or, R1Is C6-14Aryl or 5-10 membered heteroaryl; wherein R is1Optionally substituted by 1,2,3, 4 or 5 substituents selected from halogen, hydroxy, nitro, amino, carboxy, cyano, -CHO, C1-6Alkyl radical, C1-6Alkoxy, halo C1-6Alkyl, halo C1-6Alkoxy radical, C1-6Alkylthio, halo C1-6Alkylthio radical, C2-6Alkenyl radical, C2-6Alkenyloxy radical, C2-6Alkynyl, C2-6Alkynyloxy, C3-8Cycloalkyl radical, C3-8Cycloalkyl oxy, C3-8cycloalkyl-C1-3Alkylene-, -NHC1-6Alkyl, -N (C)1-6Alkyl radical)2、-C(＝O)NHC1-6Alkyl, -C (═ O) N (C)1-6Alkyl radical)2、-NH-C(＝O)-C1-6Alkyl, -N (C)1-6Alkyl) -C (═ O) -C1-6Alkyl, -NH-C (═ O) -C1-6Alkoxy, -N (C)1-6Alkyl) -C (═ O) -C1-6Alkoxy, -NH-S (═ O)2-C1-6Alkyl, -N (C)1-6Alkyl) -S (═ O)2-C1-6Alkyl, -OS (═ O)2-C1-6Alkyl radical, C1-6alkyl-C (═ O) -, C1-6alkoxy-C (═ O) -, C1-6alkyl-C (═ O) -O-, (optionally substituted with 1,2,3, 4 or 5 substituents selected from halogen, hydroxy, nitro, cyano, C1-6Alkyl, halo C1-6Alkyl radical, C1-6Alkoxy or halo C1-6Alkoxy-substituted) phenyl or (optionally substituted by 1,2,3, 4 or 5 substituents selected from halogen, hydroxy, nitro, cyano, C1-6Alkyl, halo C1-6Alkyl radical, C1-6Alkoxy or halo C1-6Alkoxy substituted) phenoxy substituted;
or, R1Is C6-14aryl-C1-3Alkylene-or 5-10 membered heteroaryl-C1-3Alkylene-; wherein R is1Optionally substituted by 1,2,3, 4 or 5 substituents selected from halogen, hydroxy, nitro, amino, carboxy, cyano, C1-6Alkyl radical, C1-6Alkoxy-substituted C1-6Alkyl, hydroxy substituted C1-6Alkyl, cyano-substituted C1-6Alkyl, aryl, heteroaryl, and heteroaryl,Nitro substituted C1-6Alkyl radical, C1-6Alkoxy, halo C1-6Alkyl or halo C1-6Alkoxy substitution;
or, R1Is composed of
Figure BDA0003301199890000021
Wherein, X, X2、X3And X5Each independently is-CR11R12-、-O-、-S-、-S(＝O)-、-S(＝O)2-or-NR13-；X1And X4Each independently is-CR14R15-；R11、R12、R14And R15Each independently is hydrogen, halogen or C1-6An alkyl group; r13Is hydrogen or C1-6An alkyl group;
R2and R3Each independently is hydrogen, halogen or C1-6An alkyl group;
R4is hydrogen, chlorine, bromine, iodine or C1-6An alkyl group;
R5、R6together with the nitrogen and carbon atoms to which they are attached to form
Figure BDA0003301199890000022
Wherein R isa、Rb、RcAnd RdEach independently is hydrogen, cyano, nitro, halogen, C1-6Alkyl or C1-6An alkoxy group;
or, R5、R6And the nitrogen atom and carbon atom to which they are attached, together form the following ring R-1, ring R-2, ring R-3 or ring R-4:
Figure BDA0003301199890000023
wherein ring R-1, ring R-2, ring R-3 and ring R-4 are optionally substituted with 1,2 or 3 substituents selected from cyano, nitro, halogen, C1-6Alkyl or C1-6Alkoxy substitution.
In some embodiments, R1Is hydrogen, C1-6Alkyl, halo C1-6Alkyl radical, C2-6Alkenyl radical, C2-6Alkynyl, C3-6Cycloalkyl radical, C3-6cycloalkyl-C1-3Alkylene-, C3-6Cycloalkenyl or C3-6Cycloalkenyl radical-C1-3Alkylene-; wherein R is1Optionally substituted by 1,2 or 3 substituents selected from halogen, hydroxy, nitro, amino, carboxy, cyano, C1-4Alkyl radical, C1-4Alkoxy, halo C1-4Alkyl or halo C1-4Alkoxy substitution;
or, R1Is C6-14Aryl or 5-10 membered heteroaryl; wherein R is1Optionally substituted by 1,2,3, 4 or 5 substituents selected from halogen, hydroxy, nitro, amino, carboxy, cyano, -CHO, C1-4Alkyl radical, C1-4Alkoxy, halo C1-4Alkyl, halo C1-4Alkoxy radical, C1-4Alkylthio, halo C1-4Alkylthio radical, C2-4Alkenyl radical, C2-4Alkenyloxy radical, C2-4Alkynyl, C2-4Alkynyloxy, C3-6Cycloalkyl radical, C3-6Cycloalkyl oxy, C3-6cycloalkyl-C1-3Alkylene-, -NHC1-4Alkyl, -N (C)1-4Alkyl radical)2、-C(＝O)NHC1-4Alkyl, -C (═ O) N (C)1-4Alkyl radical)2、-NH-C(＝O)-C1-4Alkyl, -N (C)1-4Alkyl) -C (═ O) -C1-4Alkyl, -NH-C (═ O) -C1-4Alkoxy, -N (C)1-4Alkyl) -C (═ O) -C1-4Alkoxy, -NH-S (═ O)2-C1-4Alkyl, -N (C)1-4Alkyl) -S (═ O)2-C1-4Alkyl, -OS (═ O)2-C1-4Alkyl radical, C1-4alkyl-C (═ O) -, C1-4alkoxy-C (═ O) -, C1-4alkyl-C (═ O) O-, (optionally substituted with 1,2,3, 4 or 5 substituents selected from halogen, hydroxy, nitro, cyano, C1-4Alkyl, halo C1-4Alkyl radical, C1-4Alkoxy or halo C1-4Alkoxy-substituted) phenyl or (optionally substituted by 1,2,3, 4 or 5 substituents selected from halogen, hydroxy, nitro, cyano, C1-4Alkyl, halo C1-4Alkyl radical, C1-4Alkoxy or halo C1-4Alkoxy substituted) phenoxy substituted;
or, R1Is C6-14aryl-C1-3Alkylene-or 5-10 membered heteroaryl-C1-3Alkylene-; wherein R is1Optionally substituted by 1,2,3, 4 or 5 substituents selected from halogen, hydroxy, nitro, amino, carboxy, cyano, C1-4Alkyl radical, C1-4Alkoxy-substituted C1-4Alkyl, hydroxy substituted C1-4Alkyl, cyano-substituted C1-4Alkyl, nitro substituted C1-4Alkyl radical, C1-4Alkoxy, halo C1-4Alkyl or halo C1-4Alkoxy substitution;
or, R1Is composed of
Figure BDA0003301199890000024
Wherein, X, X2、X3And X5Each independently is-CR11R12-、-O-、-S-、-S(＝O)-、-S(＝O)2-or-NR13-；X1And X4Each independently is-CR14R15-；R11、R12、R14And R15Each independently is hydrogen, halogen or C1-4An alkyl group; r13Is hydrogen or C1-4An alkyl group.
In other embodiments, R1Is hydrogen, C1-4Alkyl, halo C1-4Alkyl radical, C2-4Alkenyl radical, C2-4Alkynyl, C3-6Cycloalkyl radical, C3-6cycloalkyl-C1-3Alkylene-, C3-6Cycloalkenyl or C3-6Cycloalkenyl radical-C1-3Alkylene-; wherein R is1Optionally substituted by 1,2 or 3 substituents selected from halogen, hydroxy, nitro, amino, carboxy, cyano, C1-4Alkyl radical, C1-4Alkoxy, halo C1-4Alkyl or halo C1-4Alkoxy substitution;
or, R1Is phenyl, naphthyl or thienyl; wherein R is1Optionally substituted by 1,2,3, 4 or 5 substituents selected from halogen, hydroxy, nitro, amino, carboxy, cyano, -CHO, C1-4Alkyl radical, C1-4Alkoxy, halo C1-4Alkyl, halo C1-4Alkoxy radical, C1-4Alkylthio, halo C1-4Alkylthio radical, C2-4Alkenyl radical, C2-4Alkenyloxy radical, C2-4Alkynyl, C2-4Alkynyloxy, C3-6Cycloalkyl radical, C3-6Cycloalkyl oxy, C3-6cycloalkyl-C1-3Alkylene-, -NHC1-4Alkyl, -N (C)1-4Alkyl radical)2、-C(＝O)NHC1-4Alkyl, -C (═ O) N (C)1-4Alkyl radical)2、-NH-C(＝O)-C1-4Alkyl, -N (C)1-4Alkyl) -C (═ O) -C1-4Alkyl, -NH-C (═ O) -C1-4Alkoxy, -N (C)1-4Alkyl) -C (═ O) -C1-4Alkoxy, -NH-S (═ O)2-C1-4Alkyl, -N (C)1-4Alkyl) -S (═ O)2-C1-4Alkyl, -OS (═ O)2-C1-4Alkyl radical, C1-4alkyl-C (═ O) -, C1-4alkoxy-C (═ O) -, C1-4alkyl-C (═ O) -O-, (optionally substituted with 1,2,3, 4 or 5 substituents selected from halogen, hydroxy, nitro, cyano, C1-4Alkyl, halo C1-4Alkyl radical, C1-4Alkoxy or halo C1-4Alkoxy-substituted) phenyl or (optionally substituted by 1,2,3, 4 or 5 substituents selected from halogen, hydroxy, nitro, cyano, C1-4Alkyl, halo C1-4Alkyl radical, C1-4Alkoxy or halo C1-4Alkoxy substituted) phenoxy substituted;
or, R1Is phenyl-C1-3Alkylene-; wherein R is1Optionally substituted by 1,2,3, 4 or 5 substituents selected from halogen, hydroxy, nitro, amino, carboxy, cyano, C1-4Alkyl radical, C1-4Alkoxy-substituted C1-4Alkyl, hydroxy substituted C1-4Alkyl, cyano-substituted C1-4Alkyl, nitro substituted C1-4Alkyl radical, C1-4Alkoxy, halo C1-4Alkyl or halo C1-4Alkoxy substitution;
or, R1Is composed of
Figure BDA0003301199890000031
Wherein, X, X2、X3And X5Each independently is-CR11R12-、-O-、-S-、-S(＝O)-、-S(＝O)2-or-NR13-；X1And X4Each independently is-CR14R15-；R11、R12、R14And R15Each independently hydrogen or halogen; r13Is hydrogen or C1-4An alkyl group.
In still other embodiments, R1Is hydrogen, -CH3、-CH2CH3、-CH2CH2CH3、-CH2CH2CH2CH3、-CH＝CH2、-CH2CH＝CH2、-C≡CH、-CH2C ≡ CH, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropyl-CH2-, cyclobutyl-CH2-, cyclopentyl-CH2-or cyclohexyl-CH2-；
Or, R1Is phenyl, naphthalen-1-yl, naphthalen-2-yl or thiophen-3-yl; wherein R is1Optionally substituted by 1,2,3, 4 or 5 substituents selected from fluoro, chloro, bromo, iodo, hydroxy, nitro, amino, carboxy, cyano, -CHO, -CH3、-CH2CH3、-CH2CH2CH3、-CH2CH2CH2CH3、-C(CH3)3、-OCH3、-OCH2CH3、-OCH2CH2CH3、-CHF2、-CF3、-CH2CF3、-OCHF2、-OCF3、-OCH2CF3、-SCH3、-SCH2CH3、-SCF3、-SCH2CF3Optionally substituted with 1,2,3, 4 or 5 substituents selected from fluoro, chloro, bromo, iodo, hydroxy, nitro, cyano, -CH3、-CF3、-OCH3or-OCF3Substituted) phenyl or (optionally substituted by 1,2,3, 4 or 5 substituents selected from fluoro, chloro, bromo, iodo, hydroxy, nitro, cyano, -CH3、-CF3、-OCH3or-OCF3Substituted) phenoxy substitution;
or, R1Is phenyl-CH2-or phenyl-CH2CH2-; wherein R is1Optionally substituted with 1,2,3, 4 or 5 substituents selected from fluoro, chloro, bromo, iodo, hydroxy, nitro, amino, carboxy, cyano, -CH3、-CH2CH3、-CH2OH、-CH2CN、-CH2NO2、-OCH3、-OCH2CH3、-CF3or-OCF3Substitution;
or, R1Is composed of
Figure BDA0003301199890000032
Wherein, X, X2、X3And X5Each independently is-CR11R12-、-O-、-S-、-S(＝O)-、-S(＝O)2-or-NR13-；X1And X4Each independently is-CR14R15-；R11、R12、R14And R15Each independently is hydrogen or fluorine; r13Is hydrogen or-CH3。
In still other embodiments, R1Is of the sub-structure:
Figure BDA0003301199890000041
in still other embodiments, R1Is of the sub-structure:
Figure BDA0003301199890000042
in still other embodiments, R1Is of the sub-structure:
Figure BDA0003301199890000043
Figure BDA0003301199890000044
representing the position of attachment of the structural formula to the rest of the molecule.
In some embodiments, R2And R3Each independently is hydrogen, halogen or C1-4An alkyl group.
In other embodiments, R2And R3Each independently hydrogen, fluorine, chlorine, bromine, iodine, -CH3or-CH2CH3。
In some embodiments, R4Is hydrogen, chlorine, bromine, iodine or C1-4An alkyl group.
In other embodiments, R4Is hydrogen, chlorine, bromine, iodine, -CH3or-CH2CH3。
In some embodiments, R5、R6Together with the nitrogen and carbon atoms to which they are attached to form
Figure BDA0003301199890000051
Wherein R isa、Rb、RcAnd RdEach independently is hydrogen, cyano, nitro, halogen, C1-4Alkyl or C1-4An alkoxy group;
or, R5、R6And the nitrogen atom and carbon atom to which they are attached, together form the following ring R-1, ring R-2, ring R-3 or ring R-4:
Figure BDA0003301199890000052
wherein ring R-1, ring R-2, ring R-3 and ring R-4 are optionally substituted with 1,2 or 3 substituents selected from cyano, nitro, halogen, C1-4Alkyl or C1-4Alkoxy substitution.
In other embodiments, R5、R6Together with the nitrogen and carbon atoms to which they are attached to form
Figure BDA0003301199890000053
Wherein R isa、Rb、RcAnd RdEach independently is hydrogen, cyano, nitro, fluoro, chloro, bromo, iodo, -CH3or-OCH3；
Or, R5、R6And the nitrogen atom and carbon atom to which they are attached, together form the following ring R-1, ring R-2, ring R-3 or ring R-4:
Figure BDA0003301199890000054
wherein ring R-1, ring R-2, ring R-3 and ring R-4 are optionally substituted with 1,2 or 3 substituents selected from cyano, nitro, fluoro, chloro, bromo, iodo, -CH3or-OCH3And (4) substitution.
In some embodiments, the present invention provides a compound that is a stereoisomer, a nitroxide, or a salt thereof, of a compound having or of formula (I-A):
Figure BDA0003301199890000055
wherein R isa、Rb、Rc、Rd、R1、R2、R3And R4Have the meaning as described in the present invention.
In other embodiments, the present invention provides a compound which is a stereoisomer, a nitrogen oxide or a salt thereof of a compound having formula (I-A-1) or a compound of formula (I-A-1):
Figure BDA0003301199890000061
wherein R is1And R4Have the meaning as described in the present invention.
In still other embodiments, the present invention provides a compound that is a stereoisomer, a nitroxide or a salt thereof of a compound having or represented by formula (I-B); alternatively, the present invention provides a compound which is a compound having the formula (I-C) or a stereoisomer, a nitrogen oxide or a salt thereof of the compound represented by the formula (I-C); alternatively, the present invention provides a compound which is a compound having the formula (I-D) or a stereoisomer, a nitrogen oxide or a salt thereof of the compound represented by the formula (I-D); alternatively, the present invention provides a compound which is a compound having the formula (I-E) or a stereoisomer, a nitrogen oxide or a salt thereof of the compound represented by the formula (I-E);
Figure BDA0003301199890000062
wherein R isa、Rb、RcAnd RdEach independently is cyano, nitro, halogen, C1-6Alkyl or C1-6An alkoxy group;
R1、R2、R3and R4Have the meaning as described in the present invention.
In still other embodiments, the present invention provides a compound that is a stereoisomer, a nitroxide or a salt thereof of a compound having or represented by formula (I-B); alternatively, the present invention provides a compound which is a compound having the formula (I-C) or a stereoisomer, a nitrogen oxide or a salt thereof of the compound represented by the formula (I-C); alternatively, the present invention provides a compound which is a compound having the formula (I-D) or a stereoisomer, a nitrogen oxide or a salt thereof of the compound represented by the formula (I-D); alternatively, the present invention provides a compound which is a compound having the formula (I-E) or a stereoisomer, a nitrogen oxide or a salt thereof of the compound represented by the formula (I-E);
wherein R isa、Rb、RcAnd RdEach independently is cyano, nitro, halogen, C1-4Alkyl or C1-4An alkoxy group;
R1、R2、R3and R4Have the meaning as described in the present invention.
In still other embodiments, the present invention provides a compound that is a stereoisomer, a nitroxide or a salt thereof of a compound having or represented by formula (I-B); alternatively, the present invention provides a compound which is a compound having the formula (I-C) or a stereoisomer, a nitrogen oxide or a salt thereof of the compound represented by the formula (I-C); alternatively, the present invention provides a compound which is a compound having the formula (I-D) or a stereoisomer, a nitrogen oxide or a salt thereof of the compound represented by the formula (I-D); alternatively, the present invention provides a compound which is a compound having the formula (I-E) or a stereoisomer, a nitrogen oxide or a salt thereof of the compound represented by the formula (I-E);
wherein R isa、Rb、RcAnd RdEach independently is cyano, nitro, fluoro, chloro, bromo, iodo, -CH3or-OCH3；
R1、R2、R3And R4Have the meaning as described in the present invention.
In still other embodiments, the present invention provides a compound which is a stereoisomer, a nitrogen oxide or a salt thereof of a compound having formula (I-B-1) or a compound of formula (I-B-1); alternatively, the present invention provides a compound which is a compound having the formula (I-C-1) or a stereoisomer, a nitrogen oxide or a salt thereof of the compound having the formula (I-C-1); alternatively, the present invention provides a compound which is a compound having the formula (I-D-1) or a stereoisomer, a nitrogen oxide or a salt thereof of the compound having the formula (I-D-1); alternatively, the present invention provides a compound which is a compound having the formula (I-E-1) or a stereoisomer, a nitrogen oxide or a salt thereof of the compound having the formula (I-E-1);
Figure BDA0003301199890000071
wherein R isa、Rb、RcAnd RdEach independently is cyano, nitro, halogen, C1-6Alkyl or C1-6An alkoxy group;
R1and R4Have the meaning as described in the present invention.
In still other embodiments, the present invention provides a compound which is a stereoisomer, a nitrogen oxide or a salt thereof of a compound having formula (I-B-1) or a compound of formula (I-B-1); alternatively, the present invention provides a compound which is a compound having the formula (I-C-1) or a stereoisomer, a nitrogen oxide or a salt thereof of the compound having the formula (I-C-1); alternatively, the present invention provides a compound which is a compound having the formula (I-D-1) or a stereoisomer, a nitrogen oxide or a salt thereof of the compound having the formula (I-D-1); alternatively, the present invention provides a compound which is a compound having the formula (I-E-1) or a stereoisomer, a nitrogen oxide or a salt thereof of the compound having the formula (I-E-1);
wherein R isa、Rb、RcAnd RdEach independently is cyano, nitro, halogen, C1-4Alkyl or C1-4An alkoxy group;
R1and R4Have the meaning as described in the present invention.
In still other embodiments, the present invention provides a compound which is a stereoisomer, a nitrogen oxide or a salt thereof of a compound having formula (I-B-1) or a compound of formula (I-B-1); alternatively, the present invention provides a compound which is a compound having the formula (I-C-1) or a stereoisomer, a nitrogen oxide or a salt thereof of the compound having the formula (I-C-1); alternatively, the present invention provides a compound which is a compound having the formula (I-D-1) or a stereoisomer, a nitrogen oxide or a salt thereof of the compound having the formula (I-D-1); alternatively, the present invention provides a compound which is a compound having the formula (I-E-1) or a stereoisomer, a nitrogen oxide or a salt thereof of the compound having the formula (I-E-1);
wherein R isa、Rb、RcAnd RdEach independently is cyano, nitro, fluoro, chloro, bromo, iodo, -CH3or-OCH3；
R1And R4Have the meaning as described in the present invention.
In some embodiments, the present invention provides a compound that is a compound having one of the following structures or a stereoisomer, a nitroxide, or a salt thereof of a compound having one of the following structures:
Figure BDA0003301199890000072
Figure BDA0003301199890000081
Figure BDA0003301199890000091
Figure BDA0003301199890000101
Figure BDA0003301199890000111
in another aspect, the present invention provides a composition comprising a compound according to the invention and at least one agriculturally pharmaceutically acceptable adjuvant.
Further, adjuvants commonly used in agro-pharmaceutical industry include: surfactant and carrier.
In yet another aspect, the invention provides the use of a compound of the invention or a composition of the invention in agriculture, forestry or horticulture.
In yet another aspect, the invention provides the use of a compound according to the invention or a composition according to the invention as a pesticide.
Further, the present invention provides the use of the compound of the present invention or the composition of the present invention as a pesticide in agriculture, forestry or horticulture.
In yet another aspect, the present invention provides the use of a compound according to the present invention or a composition according to the present invention as a pest control agent.
Further, the pest of the present invention is preferably a lepidopteran and/or hemipteran pest.
Further, the pests according to the invention are preferably armyworms, bemisia tabaci, aphids of alfalfa and/or brown planthoppers.
Detailed description of the invention
Definitions and general terms
Reference will now be made in detail to certain embodiments of the invention, examples of which are illustrated by the accompanying structural and chemical formulas. The invention is intended to cover alternatives, modifications and equivalents, which may be included within the scope of the invention as defined by the appended claims. One skilled in the art will recognize that many methods and materials similar or equivalent to those described herein can be used in the practice of the present invention. The present invention is in no way limited to the methods and materials described herein. In the event that one or more of the incorporated documents, patents, and similar materials differ or contradict this application (including but not limited to defined terminology, application of terminology, described techniques, and the like), this application controls.
It will be further appreciated that certain features of the invention, which are, for clarity, described in the context of separate embodiments, may also be provided in combination in a single embodiment. Conversely, various features of the invention which are, for brevity, described in the context of a single embodiment, may also be provided separately or in any suitable subcombination.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. All patents and publications referred to herein are incorporated by reference in their entirety.
The following definitions, as used herein, should be applied unless otherwise indicated. For the purposes of the present invention, the chemical elements are in accordance with the CAS version of the periodic Table of the elements, and the handbook of chemistry and Physics, 75 th edition, 1994. In addition, general principles of Organic Chemistry can be referred to as described in "Organic Chemistry", Thomas Sorrell, University Science Books, Sausaltito: 1999, and "March's Advanced Organic Chemistry" by Michael B.Smith and Jerry March, John Wiley & Sons, New York:2007, the entire contents of which are incorporated herein by reference.
The articles "a," "an," and "the" as used herein are intended to include "at least one" or "one or more" unless otherwise indicated or clearly contradicted by context. Thus, as used herein, the articles refer to one or to more than one (i.e., to at least one) of the objects. For example, "a component" refers to one or more components, i.e., there may be more than one component contemplated for use or use in embodiments of the described embodiments.
The term "comprising" is open-ended, i.e. includes the elements indicated in the present invention, but does not exclude other elements.
"stereoisomers" refers to compounds having the same chemical structure but differing in the arrangement of atoms or groups in space. Stereoisomers include enantiomers, diastereomers, conformers (rotamers), geometric isomers (cis/trans), atropisomers, and the like.
"enantiomer" refers to two isomers of a compound that are not overlapping but are in mirror image relationship to each other.
"diastereomer" refers to a stereoisomer that has two or more chiral neutrals and whose molecules are not mirror images of each other. Diastereomers have different physical properties, such as melting points, boiling points, spectral properties, and reactivities. Mixtures of diastereomers may be separated by high resolution analytical procedures such as electrophoresis and chromatography, e.g., HPLC.
The stereochemical definitions and rules used in the present invention generally follow the general definitions of S.P. Parker, Ed., McGraw-Hill Dictionary of Chemical Terms (1984) McGraw-Hill Book Company, New York; and Eliel, E.and Wilen, S., "Stereochemistry of Organic Compounds", John Wiley & Sons, Inc., New York, 1994.
Many organic compounds exist in an optically active form, i.e., they have the ability to rotate the plane of plane polarized light. In describing optically active compounds, the prefixes D and L or R and S are used to denote the absolute configuration of a molecule with respect to one or more of its chiral centers. The prefixes d and l or (+) and (-) are the symbols used to specify the rotation of plane polarized light by the compound, where (-) or l indicates that the compound is left-handed. Compounds prefixed with (+) or d are dextrorotatory. A particular stereoisomer is an enantiomer and a mixture of such isomers is referred to as an enantiomeric mixture. A50: 50 mixture of enantiomers is referred to as a racemic mixture or racemate, which may occur when there is no stereoselectivity or stereospecificity in the chemical reaction or process.
Any asymmetric atom (e.g., carbon, etc.) of a compound disclosed herein can exist in racemic or enantiomerically enriched forms, such as the (R) -, (S) -or (R, S) -configuration. In certain embodiments, each asymmetric atom has at least 50% enantiomeric excess, at least 60% enantiomeric excess, at least 70% enantiomeric excess, at least 80% enantiomeric excess, at least 90% enantiomeric excess, at least 95% enantiomeric excess, or at least 99% enantiomeric excess in the (R) -or (S) -configuration.
Depending on the choice of starting materials and methods, the compounds of the invention may exist as one of the possible isomers or as mixtures thereof, for example as racemates and mixtures of non-corresponding isomers (depending on the number of asymmetric carbon atoms). Optically active (R) -or (S) -isomers can be prepared using chiral synthons or chiral reagents, or resolved using conventional techniques. If the compound contains a double bond, the substituents may be in the E or Z configuration; if the compound contains a disubstituted cycloalkyl group, the substituents of the cycloalkyl group may have cis or trans configuration.
Any resulting mixture of stereoisomers may be separated into pure or substantially pure geometric isomers, enantiomers, diastereomers, depending on differences in the physicochemical properties of the components, for example, by chromatography and/or fractional crystallization.
The racemates of any of the resulting end products or intermediates can be resolved into the optical enantiomers by known methods using methods familiar to those skilled in the art, e.g., by separation of the diastereomeric salts obtained. The racemic product can also be separated by chiral chromatography, e.g., High Performance Liquid Chromatography (HPLC) using a chiral adsorbent. In particular, enantiomers can be prepared by asymmetric synthesis.
The compounds of the invention may be optionally substituted with one or more substituents, as described herein, in compounds of the general formula above, or as specifically exemplified, sub-classes, and classes of compounds encompassed by the invention. It will be understood that the term "optionally substituted" is used interchangeably with the terms "substituted or unsubstituted" and "optionally substituted with …". In general, the term "substituted" means that one or more hydrogen atoms in a given structure are replaced with a particular substituent. Unless otherwise indicated, an optional substituent group may be substituted at each substitutable position of the group. When more than one position in a given formula can be substituted with one or more substituents selected from a particular group, the substituents may be substituted at each position, identically or differently. Specifically, examples of "one or more" refer to 1,2,3, 4, 5, 6, 7, 8, 9, or 10. Wherein said substituent may be, but is not limited to, deuterium, fluorine, chlorine, bromine, iodine, cyano, hydroxyl, nitro, amino, carboxyl, alkyl, alkoxy, alkoxyalkyl, alkoxyalkoxy, alkoxyalkylamino, aryloxy, heteroaryloxy, heterocyclyloxy, arylalkoxy, heteroarylalkoxy, heterocyclylalkoxy, cycloalkylalkoxy, alkylamino, alkylaminoalkyl, alkylaminoalkylamino, cycloalkylamino, cycloalkylalkylamino, alkylthio, haloalkyl, haloalkoxy, hydroxyl-substituted alkyl, hydroxyl-substituted alkylamino, cyano-substituted alkyl, cyano-substituted alkoxy, cyano-substituted alkylamino, amino-substituted alkyl, alkanoyl, heteroalkyl, cycloalkyl, cycloalkenyl, cycloalkylalkyl, heterocyclyl, heterocyclylalkyl, aryl, arylalkyl, arylamino, heteroaryl, heteroarylalkyl, heteroarylamino, amido, sulfonyl, aminosulfonyl, and the like.
In addition, unless otherwise explicitly indicated, the descriptions of the terms "… independently" and "… independently" and "… independently" used in the present invention are interchangeable and should be understood in a broad sense to mean that the specific items expressed between the same symbols do not affect each other in different groups or that the specific items expressed between the same symbols in the same groups do not affect each other.
In the various parts of this specification, substituents of the disclosed compounds are disclosed in terms of group type or range. It is specifically intended that the invention includes each and every independent subcombination of the various members of these groups and ranges. For example, the term "C1-C6Alkyl "or" C1-6Alkyl "means in particular independently disclosed methyl, ethyl, C3Alkyl radical, C4Alkyl radical, C5Alkyl and C6An alkyl group.
The term "alkyl" or "alkyl group" as used herein, denotes a saturated, straight or branched chain, monovalent hydrocarbon group containing from 1 to 20 carbon atoms; wherein the alkyl group is optionally substituted with one or more substituents described herein. Unless otherwise specified, alkyl groups contain 1-20 carbon atoms. In one embodiment, the alkyl group contains 1 to 12 carbon atoms; in one embodiment, the alkyl group contains 1 to 8 carbon atoms; in another embodiment, the alkyl group contains 1 to 6 carbon atoms; in yet another embodiment, the alkyl group contains 1 to 4 carbon atoms; in yet another embodiment, the alkyl group contains 1 to 3 carbon atoms.
Examples of alkyl groups include, but are not limited to, methyl (Me, -CH)3) Ethyl group (Et, -CH)2CH3) N-propyl (n-Pr, -CH)2CH2CH3) Isopropyl group (i-Pr, -CH (CH)3)2) N-butyl (n-Bu, -CH)2CH2CH2CH3) Isobutyl (i-Bu, -CH)2CH(CH3)2) Sec-butyl (s-Bu, -CH (CH)3)CH2CH3) Tert-butyl (t-Bu, -C)(CH3)3) N-pentyl (-CH)2CH2CH2CH2CH3) 2-pentyl (-CH (CH)3)CH2CH2CH3) 3-pentyl (-CH (CH)2CH3)2) 2-methyl-2-butyl (-C (CH)3)2CH2CH3) 3-methyl-2-butyl (-CH (CH)3)CH(CH3)2) 3-methyl-1-butyl (-CH)2CH2CH(CH3)2) 2-methyl-1-butyl (-CH)2CH(CH3)CH2CH3) And so on.
The term "alkenyl" denotes a straight or branched chain monovalent hydrocarbon radical containing 2 to 12 carbon atoms, wherein there is at least one site of unsaturation, i.e. one carbon-carbon sp2A double bond, wherein the alkenyl group may be optionally substituted with one or more substituents described herein, including the positioning of "cis" and "tans", or the positioning of "E" and "Z". In one embodiment, the alkenyl group contains 2 to 8 carbon atoms; in another embodiment, the alkenyl group contains 2 to 6 carbon atoms; in yet another embodiment, the alkenyl group contains 2 to 4 carbon atoms. Examples of alkenyl groups include, but are not limited to, vinyl (-CH ═ CH)2) Allyl (-CH)2CH＝CH2) Allyl (CH)3-CH ═ CH-), oxo butenyl (CH)3-C (═ O) -CH ═ CH-) and the like.
The term "alkynyl" denotes a straight or branched chain monovalent hydrocarbon radical containing 2 to 12 carbon atoms, wherein there is at least one carbon-carbon sp triple bond, wherein the alkynyl radical may be optionally substituted with one or more substituents as described herein. In one embodiment, alkynyl groups contain 2-10 carbon atoms; in one embodiment, alkynyl groups contain 2-8 carbon atoms; in another embodiment, alkynyl groups contain 2-6 carbon atoms; in yet another embodiment, alkynyl groups contain 2-4 carbon atoms. Examples of alkynyl groups include, but are not limited to, -C.ident.CH, -C.ident.CCH3、-CH2-C≡CH、-CH2-C≡CCH3、-CH2CH2-C≡CH、-CH2-C≡CCH2CH3、-CH2CH2-C≡CCH3And so on.
The term "alkoxy" means an alkyl group attached to the rest of the molecule through an oxygen atom, wherein the alkyl group has the meaning as described herein. Examples of alkoxy groups include, but are not limited to, methoxy (MeO, -OCH)3) Ethoxy (EtO, -OCH)2CH3) 1-propoxy (n-PrO, n-propoxy, -OCH)2CH2CH3) 2-propoxy (i-PrO, i-propoxy, -OCH (CH)3)2) And so on.
The term "alkylthio" means an alkyl group attached to the rest of the molecule through a sulfur atom, wherein the alkyl group has the meaning as described herein. Examples of alkylthio groups include, but are not limited to, -SCH3、-SCH2CH3、-SCH2CH2CH3、-SCH(CH3)2And so on.
The term "cycloalkyl" denotes a monovalent or polyvalent saturated monocyclic, bicyclic or tricyclic ring system containing from 3 to 12 carbon atoms. In one embodiment, the cycloalkyl group contains 3 to 10 carbon atoms; in another embodiment, cycloalkyl contains 3 to 8 carbon atoms; in yet another embodiment, the cycloalkyl group contains 3 to 6 carbon atoms. The cycloalkyl group is optionally substituted with one or more substituents described herein. Examples include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl, cyclododecyl, and the like.
The term "cycloalkyl-alkylene-" means that the cycloalkyl group is attached to the rest of the molecule through an alkylene group, wherein alkylene and cycloalkyl groups have the meaning as described herein.
The term "cycloalkyloxy" denotes a cycloalkyl group attached to the rest of the molecule through an oxygen atom, wherein the cycloalkyl group has the meaning as described herein.
The term "cycloalkenyl" denotes mono-, bi-or tricyclic ring systems containing 3 to 12 carbon atoms, mono-or polyvalent, comprising at least one carbon-carbon double bond, said ring systems being non-aromatic. In one embodiment, cycloalkenyl groups contain 3 to 10 carbon atoms; in another embodiment, cycloalkenyl groups contain 3 to 8 carbon atoms; in yet another embodiment, cycloalkenyl groups contain 3 to 6 carbon atoms. The cycloalkenyl group is optionally substituted with one or more substituents described herein. Examples include, but are not limited to, cyclobutenyl, cyclopentenyl, cyclohexenyl, cyclohexadienyl, and the like.
The term "cycloalkenyl-alkylene-" means that the cycloalkenyl group is attached to the rest of the molecule through an alkylene group, where alkylene and cycloalkenyl groups have the meaning as described herein.
The term "aryl" denotes monocyclic, bicyclic and tricyclic carbon ring systems containing 6 to 14 ring atoms, or 6 to 12 ring atoms, or 6 to 10 ring atoms, wherein at least one ring system is aromatic, wherein each ring system comprises a ring of 3 to 7 atoms with one or more attachment points to the rest of the molecule. The term "aryl" may be used interchangeably with the term "aromatic ring". Examples of the aryl group may include phenyl, indenyl, naphthyl and anthryl. The aryl group is optionally substituted with one or more substituents described herein.
The term "aryl-alkylene-" means that the aryl group is attached to the rest of the molecule through an alkylene group, wherein the aryl group and the alkylene group have the meaning as described herein. Examples include, but are not limited to, benzyl (phenyl-CH)2-, phenylethylene (phenyl-CH)2CH2-) and the like.
The term "alkylene" denotes a saturated divalent hydrocarbon radical resulting from the removal of two hydrogen atoms from a saturated straight or branched chain hydrocarbon. Unless otherwise specified, the alkylene group contains 1 to 12 carbon atoms. In one embodiment, the alkylene group contains 1 to 8 carbon atoms; in one embodiment, the alkylene group contains 1 to 6 carbon atoms; in another embodiment, the alkylene group contains 1 to 4 carbon atoms; in yet another embodiment, an alkylene groupContaining 1 to 3 carbon atoms; in yet another embodiment, the alkylene group contains 1 to 2 carbon atoms. Examples of this include methylene (-CH)2-, ethylene (-CH)2CH2-) and the like.
The term "halogen" refers to fluorine (F), chlorine (Cl), bromine (Br) or iodine (I).
The term "heteroaryl" denotes monocyclic, bicyclic and tricyclic ring systems containing 5 to 12 ring atoms, or 5 to 10 ring atoms, or 5 to 6 ring atoms, wherein at least one ring system is aromatic and at least one ring system contains one or more heteroatoms, wherein each ring system contains a ring of 5 to 7 atoms with one or more attachment points to the rest of the molecule. The term "heteroaryl" may be used interchangeably with the terms "heteroaromatic ring" or "heteroaromatic compound". The heteroaryl group is optionally substituted with one or more substituents described herein. In one embodiment, a heteroaryl group of 5-10 atoms contains 1,2,3, or 4 heteroatoms independently selected from O, S, and N.
Examples of heteroaryl groups include, but are not limited to, 2-furyl, 3-furyl, N-imidazolyl, 2-imidazolyl, 4-imidazolyl, 5-imidazolyl, 3-isoxazolyl, 4-isoxazolyl, 5-isoxazolyl, 2-oxazolyl, 4-oxazolyl, 5-oxazolyl, N-pyrrolyl, 2-pyrrolyl, 3-pyrrolyl, 2-pyridyl, 3-pyridyl, 4-pyridyl, 2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl, pyridazinyl (e.g., 3-pyridazinyl), 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, tetrazolyl (e.g., 5-tetrazolyl), triazolyl (e.g., 2-triazolyl and 5-triazolyl), 2-thienyl, 3-thienyl, pyrazolyl, isothiazolyl, 1,2, 3-oxadiazolyl, 1,2, 5-oxadiazolyl, 1,2, 4-oxadiazolyl, 1,2, 3-triazolyl, 1,2, 3-thiadiazolyl, 1,3, 4-thiadiazolyl, 1,2, 5-thiadiazolyl, pyrazinyl, 1,3, 5-triazinyl, pyrimidinonyl, pyridonyl; the following bicyclic rings are also included, but are in no way limited to these: benzimidazolyl, benzofuranyl, benzotetrahydrofuranyl, benzothienyl, indolyl (e.g., 2-indolyl), benzopiperidinyl, and the like.
The terms "5-12 membered heteroaryl", "5-10 membered heteroaryl" or "5-6 membered heteroaryl", wherein "5-12 membered", "5-10 membered" or "5-6 membered" typically describe the number of ring-forming atoms in the molecule. For example, pyrrolyl, pyrazolyl, imidazolyl, thienyl, isothiazolyl, thiazolyl, furyl, isoxazolyl and oxazolyl are 5 membered heteroaryl and pyridinyl, pyrimidinyl, pyrazinyl and pyridazinyl are 6 membered heteroaryl.
The term "heteroaryl-alkylene-" means that the heteroaryl group is attached to the rest of the molecule through an alkylene group, wherein the alkylene and heteroaryl groups have the meaning as described herein.
The term "haloalkyl" denotes an alkyl group substituted with one or more halogen atoms, examples of which include, but are not limited to, -CF3，-CHF2，-CH2Cl，-CH2CF3，-CH2CHF2，-CH2CH2CF3And the like.
The term "haloalkoxy" denotes an alkoxy group substituted with one or more halogen atoms, examples of which include, but are not limited to, -OCF3，-OCHF2，-OCHCl2，-OCH2CHF2，-OCH2CHCl2，-OCH(CH3)CHF2And the like.
The term "haloalkylthio" denotes an alkylthio group substituted with one or more halogen atoms, examples of which include, but are not limited to, -SCF3，-SCH2CF3And the like.
The term "alkenyloxy" means an alkenyl group attached to the rest of the molecule through an oxygen atom, wherein the alkenyl group has the meaning as described herein.
The term "alkynyloxy" denotes an alkynyl group attached to the rest of the molecule through an oxygen atom, wherein the alkynyl group has the meaning as described herein.
The term "cyano" refers to — CN.
The term "hydroxy" refers to-OH.
The term "nitro" means-NO2。
The term "carboxy" refers to-COOH.
The term "amino" refers to the group-NH2。
The compound related to the invention is a mesoionic inner salt. The "inner salts" known in the art as "zwitterions" are electrically neutral molecules, but according to valence bond theory, carry formal positive and negative charges in each valence bond structure of different atoms. The molecular structure of the compounds of formula (I) can be represented by the six valence bond structures shown below, each bearing formal positive and negative charges on different atoms. Due to this resonance, the compounds of formula (I) are also described as "mesoionic". Although the molecular structure of the compound of formula (I) is described as a single valence structure shown in the present invention for the sake of brevity, this particular valence structure should be understood to be representative of all six valence structures involving intramolecular linkage of the compound of formula (I). Thus, unless otherwise indicated, reference to formula (I) herein refers to all six applicable valence bond structures as well as other (e.g., molecular orbital theory) structures.
Figure BDA0003301199890000161
Salts of the compounds of the present invention include those derived from alkali or alkaline earth metals as well as those derived from ammonia and amines. Preferred cations include sodium, potassium, magnesium and those of formula N+(RAARBBRCCRDD) Ammonium cation of (2), wherein R isAA、RBB、RCCAnd RDDIndependently selected from hydrogen, C1-C6Alkyl and C1-C6A hydroxyalkyl group. Salts of the compounds of the invention may be prepared by treating the compounds of the invention with a metal hydroxide, such as sodium hydroxide, or an amine, such as ammonia, trimethylamine, diethanolamine, 2-methylthiopropylamine, diallylamine, 2-butoxyethylamine, morpholine, cyclododecylamine or benzylamine.
When a compound of the invention comprises a base moiety, acceptable salts can be formed from organic and inorganic acids, such as acetic, propionic, lactic, citric, tartaric, succinic, fumaric, maleic, malonic, mandelic, malic, phthalic, hydrochloric, hydrobromic, phosphoric, nitric, sulfuric, methanesulfonic, napthalenesulfonic, benzenesulfonic, toluenesulfonic, camphorsulfonic, and similarly known acceptable acids.
Compositions and formulations of the compounds of the invention
The compounds of the invention are generally useful as pesticidal active ingredients in compositions, formulations and will generally also include adjuvants conventionally used in agro-pharmaceutical industry, including surfactants and/or carriers.
The surfactant may be any of various surfactants known in the field of pesticide formulation, and one or more of an emulsifier, a dispersant and a wetting agent are preferred in the present invention.
The carrier other than the surfactant may be any of various carriers known in the field of pesticide formulation, including various silicates, carbonates, sulfates, oxides, phosphates, plant carriers, and synthetic carriers. Specifically, for example: white carbon black, kaolin, diatomite, clay, talc, organic bentonite, pumice, titanium dioxide, dextrin, cellulose powder, light calcium carbonate, soluble starch, corn starch, sawdust powder, urea, an amine fertilizer, a mixture of urea and an amine fertilizer, glucose, maltose, sucrose, anhydrous potassium carbonate, anhydrous sodium carbonate, anhydrous potassium bicarbonate, anhydrous sodium bicarbonate, attapulgite, a mixture of anhydrous potassium carbonate and anhydrous potassium bicarbonate, and a mixture of anhydrous sodium carbonate and anhydrous sodium bicarbonate.
The emulsifier may be any emulsifier known in the field of pesticide formulation, and specifically, the emulsifier may be one or more of calcium dodecylbenzenesulfonate, trisethylphenol polyoxyethylene ether phosphate, fatty alcohol polyoxyethylene ether, alkylphenol polyoxyethylene polyoxypropylene ether, fatty amine, ethylene oxide adduct of fatty amide, fatty acid polyoxyethylene ester, rosin acid ethylene oxide adduct, polyol fatty acid ester and ethylene oxide adduct thereof, styrylphenyl polyoxyethylene ether, alkylphenol formaldehyde resin polyoxyethylene ether, hydroxyl-terminated polyoxyethylene polyoxypropylene ether, styrylphenol formaldehyde resin polyoxyethylene polyoxypropylene ether, and castor oil polyoxyethylene ether.
The dispersing agent can be various dispersing agents known in the field of pesticide formulation, and specifically, the dispersing agent is one or more of acrylic acid homopolymer sodium salt, maleic acid disodium salt, naphthalene sulfonic acid formaldehyde condensation product sodium salt, rosin block polyoxyethylene ether polyoxypropylene ether sulfonate, hydroxyl-terminated polyoxyethylene polyoxypropylene ether block copolymer, triphenyl polyoxyethylene phenol phosphate, fatty alcohol polyoxyethylene ether phosphate and p-hydroxyphenyl lignosulfonate sodium salt.
The wetting agent can be various wetting agents known in the field of pesticide formulation, and specifically, the wetting agent can be one or more of sodium dodecyl sulfate, secondary alkyl sodium sulfate, sodium dodecyl benzene sulfonate, fatty alcohol-polyoxyethylene ether, alkyl naphthalene sulfonate and alkylphenol resin polyoxyethylene ether sulfate.
According to the pesticide composition, various preparation auxiliaries commonly used in the field of pesticide formulation can be further contained, and specifically, the preparation auxiliaries can be one or more of a solvent, a cosolvent, a thickening agent, an antifreezing agent, a capsule wall material, a protective agent, an antifoaming agent, a disintegrating agent, a stabilizing agent, a preservative and a binder.
The solvent may be any of various solvents known in the field of pesticide formulation, and specifically, the solvent may be one or more of an organic solvent, a vegetable oil, a mineral oil, a solvent oil and water.
Wherein the organic solvent comprises one or more of N-methylpyrrolidone, tetrahydrofuran, dimethyl sulfoxide, N-dimethyldecanamide, N-dimethylformamide, trimethylbenzene, tetramethylbenzene, dimethylbenzene, methylbenzene, octane, heptane, methanol, isopropanol, N-butanol, tetrahydrofurfuryl alcohol, tributyl phosphate, 1, 4-dioxane and cyclohexanone.
The vegetable oil comprises one or more of methylated vegetable oil, rosin-based vegetable oil, turpentine oil, epoxidized soybean oil, peanut oil, rapeseed oil, castor oil, corn oil and pine seed oil.
The mineral oil comprises one or more of liquid wax, engine oil, kerosene and lubricating oil.
Meanwhile, the solvent can also be used as a cosolvent.
The antifreeze can be various antifreeze agents known in the field of pesticide formulation, and the invention is preferably one or more of ethylene glycol, propylene glycol, glycerol and urea.
The thickener can be various thickeners known in the field of pesticide formulation, and specifically can be one or more of xanthan gum, polyvinyl alcohol, polypropylene alcohol, polyethylene glycol, white carbon black, diatomite, kaolin, clay, sodium alginate, magnesium aluminum silicate, sodium aluminum silicate, carboxymethyl cellulose, sodium hydroxypropyl cellulose and organic bentonite.
The capsule material can be various capsule materials known in the field of pesticide formulation, and the invention is preferably one or more of polyurethane, polyurea and urea-formaldehyde resin.
The protective agent may be any of various protective agents known in the field of pesticide formulation, and polyvinyl alcohol and/or polyethylene glycol is preferred in the present invention.
The defoaming agent may be any of those known in the field of agricultural agent formulation, and in the present invention, one or more of organosiloxane, tributyl phosphate and silicone are preferable.
The stabilizer is one or more selected from triphenyl phosphite, epichlorohydrin and acetic anhydride.
The antiseptic is selected from one or more of benzoic acid, sodium benzoate, 1, 2-benzisothiazolin-3-one (BIT), Kathon and potassium sorbate.
The invention also provides a preparation prepared from the pesticide composition, and the preparation is in the dosage form of missible oil, aqueous emulsion, microemulsion, soluble liquid, aqueous suspension, suspoemulsion, ultra-low volume spray, oil suspension, microcapsule suspension, water surface spreading oil, wettable powder, water dispersible granule, dry suspension, soluble powder, soluble granule, emulsifiable powder, emulsifiable granule, solid microcapsule preparation, effervescent tablet, effervescent granule, water floating dispersion granule or seed coating. The above formulations can be prepared by methods conventional in the art.
The preparation method of the emulsifiable concentrate preparation can comprise, for example, mixing and stirring the active components, the solvent, the cosolvent and the emulsifier to form a uniform transparent oil phase, so as to obtain the emulsifiable concentrate preparation.
The preparation method of the aqueous emulsion can comprise, for example, mixing the active ingredient, the emulsifier, the cosolvent and the solvent to form a uniform oil phase; mixing water, thickener, antifreeze, etc. to obtain uniform water phase. Under high-speed shearing, adding the water phase into the oil phase or adding the oil phase into the water phase to form the aqueous emulsion with good dispersibility.
The microemulsion may be prepared, for example, by mixing and stirring the active ingredient, emulsifier, and solvent to form a uniform transparent oil phase. Under stirring, water is gradually added to form a uniform and transparent microemulsion.
The preparation method of the water/oil suspending agent comprises the following steps: for example, water or oil can be used as a medium, and an auxiliary agent such as an active component and a surfactant is added into a sanding kettle, and after grinding to a certain particle size, filtration is performed. And adding the weighed thickening agent into the ground mother liquor, and uniformly shearing and dispersing. Making into oil suspension or water suspension.
The preparation method of the water dispersible granule and the soluble granule comprises the following steps: for example, the active ingredients, the dispersing agent, the wetting agent, the carrier and the like are uniformly mixed, then are pulverized into a certain particle size through air flow, are added with water for kneading, are finally added into a granulator for granulation, and are dried to obtain the water dispersible granules or the soluble granules.
The preparation method of the soluble powder and the wettable powder comprises the following steps: for example, the active ingredients, various adjuvants and fillers such as other carriers can be thoroughly mixed and pulverized by a micronizer.
The pesticidal composition of the present invention may be provided in the form of a finished formulation, i.e., the substances in the composition have been mixed; or in separate formulations which are self-mixing in a tub or tank prior to use and optionally diluted by mixing with water depending on the concentration of active desired.
For additional information regarding The field of formulation, see "The formulations's Toolbox-Product Forms for model Agriculture" by T.S. woods, The Food-Environment Challenge, T.Brooks and T.R. Roberts eds, Proceedings of The 9th International conformation on Pesticide Chemistry, The Royal Society of Chemistry, Cambridge, 1999, p.120. 133. See also U.S.3,235,361, column 6, line 16 to column 7, line 19 and examples 10-41; U.S. Pat. No. 3,309,192, column 5, column 43 to column 7, column 62 and examples 8, 12, 15, 39, 41, 52, 53, 58, 132, 138, 162, 164, 166, 167 and 169, 182; U.S.2,891,855 at column 3, line 66 to column 5, line 17 and examples 1-4; wed Control as a Science by Klingman, John Wiley and Sons, Inc., New York, 1961, pages 81-96; weed Control Handbook, 8 th edition, Blackwell Scientific Publications, Oxford, 1989, by Hance et al; and Developments in simulation technology, PJB Publications, Richmond, UK, 2000.
Application of the inventive compounds and compositions
The compounds and/or compositions of the present invention are suitable for controlling pests such as arthropods, gastropods and nematodes in useful plants, including but not limited to:
hemiptera (Hemiptera): plant hoppers (Delphacidae) such as brown plant hoppers (Nilaparvata lugens), small brown plant hoppers (Laodelphax striatellus); leafhoppers (deltochalidae) such as green rice leafhopper (Nephotettix cincticeps); aphids (Aphididae)) such as cotton aphid (Aphis gossypii), alfalfa aphid (Aphis cracivora Koch); stinkbug (Pentatomidae) such as lygus lucorum (Nezara antennata); whiteflies (Aleyrodidae) such as greenhouse whitefly (Trialeurodes vaporariorum); scales (Coccidae) such as red mussel scale (Calformia red scale) (Aonidiella aurantii); lace bugs (Tingidae); psyllid (Homoptera, Psyllidea);
lepidoptera (Lepidoptera): snout moth (Pyralidae) such as Chilo suppersalis; noctuids (Noctuidae) such as Spodoptera litura (Spodoptera litura), armyworm (pseudolitea sepata), noctuid (Heliothis spp.) and noctuid (Helicoverpa spp.); pieridae (Pieridae) such as Pieris rapae; tortricid (Tortricidae) such as Trichinella fusca (Adoxophyes); fine moths (Gracillaridae) such as the tea-fine moth (Caloptilia theivora) and apple-fine moth (Phyllonorycter ringer Neella); moth (Carposinidae) such as peach moth (Carposina niponensis); plutella xylostella (lyonetidae) such as the genus plutella (Lyonetia spp.); moths (lymantriadae) such as the genus toxapha (Lymantria spp.) and the genus diaphora (Euproctis spp.); nest moths (Yponomeutidae) such as diamondback moth (Plutella xylostella); wheat moths (Gelechiidae) such as pink bollworm (Pectinophora gossypiella) and potato bollworm (photoria operculella); a fall webworm (arctiaceae) such as fall webworm (hypanthria cunea); and rice moths (Tineidae) such as clothiantus (tinearanspiens) and cottonta guianensis (Tineola bisseliella);
thysanoptera (Thysanoptera): frankliniella occidentalis, Frankliniella palmi (Thrips palmi), Frankliniella flavum (Scirtothrips dorsalis), Frankliniella tabacina (Thrips tabaci), Frankliniella quinquefolia (Frankliniella intonasa), and Frankliniella solani (Frankliniella fusca);
diptera (Diptera): houseflies (Musca domestica), Culex pipiens pallens (Culex pipiens pallens), Tabanus trifoliatus (Tabanus trigonus), allia fistulosa (hymexa annua), phaeophytes cinerea (hymexa platura), Anopheles sinensis (Anopheles sinensis), oryza sativa (agromiza oryzae), oryza sativa (hymeria griseola), oryza sativa (chlospora oryzae), oryza sativa (cucurbita cucurbitae), medfly (Ceratitis capitata), and trematopsis trifoliata (rhizomyza trifolii);
coleoptera (Coleoptera): the plant is selected from the group consisting of coccinella twenty-eight (Epilachna virginiocarpa), Phyllotreta striolata (phylotrita), mud worm of rice (Oulema oryzae), rice elephant (echinococcus squameus), rice water elephant (lissoropterus oryzae), cotton boll elephant (anthomonus grandis), green bean elephant (calorobucus chinensis), parasitic valley elephant (epheophorus ventratus), japanese beetle (Popillia japonica), ancient copper isocoryza turtles (Anomala cuprea), photinus pyralis (atrocerba), leptinotara (Leptinotarsa decemlineata), cottonwood beetle (cottonwood), bark beetle (bark beetle), white beetle (bark beetle) and white beetle (bark beetle) in the like;
orthoptera (Orthoptera): locusta migratoria (Locusta migratoria), mole cricket in africa (Gryllotalpa aficana), rice Locusta norhaii (Oxya yezoensis) and japanese rice Locusta (Oxya japonica);
hymenoptera (Hymenoptera): sinkiang vegetable wasps (Athalia rosae), Anthera incisa (Acromycex spp.) and Termite (Solenopsis spp.);
nematodes (nematodies): aphelenchoides besseyi (Aphelenchoides besseyi), strawberry bud nematode (Nothopylenchus acris), soybean cyst nematode (Heterodera glycines), Meloidogyne incognita (Meloidogyne incognita), Pratylenchus (Praytylenchus penatrans) and Heterodera micrantha (Nacobb aberrans);
blattaria (blattaria): blattella germanica (Blattella germanica), Blattella fuliginosa (Periplaneta fuliginosa), Periplaneta Americana (Periplaneta Americana), Blattella fusca (Periplaneta brunnea), and Blattella orientalis (Blattea orientalis);
acarina (Acarina): tetranyhidae (Tetranyhidae) (e.g., Tetranychus cinnabarinus (Tetranychus cinabaricus), Tetranychus urticae (Tetranychus urticae), Tetranychus citrullus (Pannychus citri) and Tetranychus spp.); gall mites (Eriophyidae) (e.g., citrus piercing gall mites (Aculops pelekassi)); tarsonemudae (Tarsonemidae); finesse family (tenuipipidae); duke mite family (Tuckerellidae); acarus family (Tuckerellidae Acaridae); pymetrophyceae (pyroxylidae) (e.g., dust mites (Dermatophagoides farinae) and house dust mites (Dermatophagoides ptrenyssnus)); carnivora (Cheyletidae), sarcophagidae (Cheyletus malaccensis) and sarcophagidae (Cheyletus moorei); and Dermanysidae (Dermanyssudae).
Within the scope of the present invention, useful plants include the following plant species: cereals (wheat, barley, rye, oats, rice, maize, sorghum and related species); sugar beets (sugar radish and fodder beet); pome, stone fruit and soft fruit (apples, pears, plums, peaches, almonds, cherries, strawberries, raspberries and blackberries); leguminous plants (lentils, binchou, peas, soybeans); oil crops (rape, mustard, olives, sunflowers, coconut, castor oil plants, cocoa beans, groundnuts or soybeans); cucurbits (squash, cucumber, melon); fiber plants (cotton, flax, hemp, jute); citrus fruits (oranges, lemons, grapefruit, mandarins); vegetables (spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes, red peppers); lauraceous plants (avocado, cinnamomum, camphor) or plants, such as tobacco, nuts, coffee, eggplants, sugar cane, tea, pepper, grapevine, hops, bananas and natural rubber plants, as well as turf, ornamental and forest plants, such as flowers, shrubs, broad-leaved trees or evergreens, such as conifers, and plant propagation material.
The term "plant propagation material" should be understood to mean the reproductive parts of the plant, such as seeds, which parts can be used for the propagation of the plant, as well as vegetative material, such as cuttings or tubers (e.g. potatoes).
The compounds and/or compositions of the present invention kill pests by an effective amount of the active substance. Wherein, the effective dose of the compound of the invention is within 10g-5kg per hectare, the effect of controlling pests is better.
The invention also relates to a method for controlling pests by applying the compounds or compositions of the invention to the seed, the plant or parts of the plant, the fruit or the soil in which the plant is growing. The application can be carried out before and after the seed, the plant or the plant part, the fruit or the soil in which the plant is growing is infested with pests.
The term "effective amount" as used herein means an amount of a compound or composition of the present invention sufficient to control pests on cultivated plants or in the protection of materials without causing significant damage to the treated plants. The amount may vary within wide limits and depends on various factors such as the pest species, the cultivated plant or material being treated, the climatic conditions and the particular compound used.
The compound and/or the composition of the invention is simple to use, and the compound and/or the composition of the invention is applied to the pests or the growth medium thereof. The application dose of the compound and/or composition of the present invention varies depending on weather conditions, formulation, application timing, application method, application area, target disease, target crop, and the like.
General synthetic procedure
In this specification, a structure is dominant if there is any difference between the chemical name and the chemical structure. In general, the compounds of the invention may be prepared by the methods described herein, unless otherwise indicated. In the preparation of the compounds of the present invention, the preparation of the compounds is carried out at room temperature unless otherwise specified. By "room temperature" is meant a temperature of about 10 ℃ to 35 ℃ or about 20 ℃ to 30 ℃ or about 23 ℃ to 28 ℃ or about 25 ℃. In the context of the present invention, all numbers disclosed herein are approximate values, regardless of whether the word "about" or "approximately" is used.
The test conditions of the nuclear magnetic resonance hydrogen spectrum of the invention are as follows: brookfield (Bruker) nuclear magnetic instrument at 400MHz or 600MHz in CDC1 at room temperature3，d6-DMSO，CD3OD or d6Acetone as solvent (reported in ppm) with TMS (0ppm) or chloroform (7.26ppm) as reference standard. When multiple peaks occur, the following abbreviations will be used: s (singleton), d (doublet), t (triplet), q (quatet, quartet), m (multiplet ), br (broadpeded, broad), dd (doublet of doublets), dt (doublet of triplets). Coupling constants are expressed in hertz (Hz).
The mass spectrometry method used in the invention comprises the following steps: agilent 1260HPLC was used; agilent 6120 ESI.
Phase A: water (0.1% formic acid); phase B: acetonitrile (0.1% formic acid).
Gradient elution: 0-3min, 5-100% B; 3-6min, 100% B.
Flow rate: 0.6 mL/min.
Detection wavelength: 254 nm.
MS parameters: ESI positive scan, collision induced ionization: 70V.
Drying nitrogen gas: 12L/min, atomizing gas pressure: 40psi, gas temperature: at 350 ℃.
Synthetic schemes
Synthesis scheme I
Figure BDA0003301199890000201
Figure BDA0003301199890000211
The compound of formula (a) may be prepared by synthesis scheme one. Reacting the compound shown in the formula (a) with oxalyl chloride to obtain a compound, and reacting with 2,4, 6-trichlorophenol to obtain a compound shown in a formula (b); the compound shown in the formula (b) and the compound shown in the formula (c) are reacted in toluene at the temperature of 50-150 ℃ to obtain the compound shown in the formula (A).
Synthesis scheme two
Figure BDA0003301199890000212
The compound of formula (a) can also be prepared by synthesis scheme two. The compound represented by the formula (a) and the compound represented by the formula (c) are subjected to a condensation reaction in an inert organic solvent (such as dichloromethane) in the presence of a condensing agent (such as dicyclohexylcarbodiimide) to obtain the compound represented by the formula (A).
In the above synthetic schemes, R1、R2、R3And R4Have the meaning as described in the present invention;
A1、A2、A3and A4Each independently being a nitrogen atom or-CRx-, wherein RxIs hydrogen, cyano, nitro, halogen, C1-6Alkyl or C1-6An alkoxy group.
Examples
Intermediate Z1: preparation of N- (2, 2-difluoroethyl) pyridin-2-amine
Figure BDA0003301199890000213
The first step is as follows: preparation of tert-butyl pyridin-2-ylaminocarboxylic acid ester
Figure BDA0003301199890000214
2-aminopyridine (4.70g,0.05mol), di-tert-butyl dicarbonate (14.17g,0.65mol) and triethylamine (7.55g,0.075mol) were successively added to dichloromethane (45mL), and the reaction was stirred at room temperature for 12 hours. Filtration, concentration of the filtrate under reduced pressure, extraction of the concentrate with ethyl acetate (30mL × 3), washing with saturated brine (30mL × 3), drying over anhydrous sodium sulfate, filtration, concentration of the filtrate under reduced pressure, and separation of the residue by silica gel column chromatography [ petroleum ether/ethyl acetate (v/v) ═ 5/1] gave 4.62g of the title compound as a white solid in yield: 48.0 percent.
The second step is that: preparation of N- (2, 2-difluoroethyl) pyridin-2-amine
Figure BDA0003301199890000221
Pyridine-2-ylamine tert-butyl carboxylate (1.29g,6.64mmol) was added to a 100mL single-neck flask at 0 ℃ to dissolve it by adding tetrahydrofuran (40mL), sodium hydride (60% by mass, 0.4g,9.96mmol) was slowly added to the reaction mixture in portions at 0 ℃ after the addition, the reaction mixture was stirred at 0 ℃ for 30 minutes, the reaction mixture was allowed to cool to room temperature, 1-difluoro-2-iodoethane (1.27g,6.64mmol) was added, and the reaction was continued at room temperature for 12 hours. Ice water (30mL) was added to the reaction solution, and extraction was performed with ethyl acetate (50 mL. times.3), and the organic phases were combined, dried over anhydrous sodium sulfate for 1 hour, filtered under suction, and the filtrate was concentrated by distillation under reduced pressure to give a brown oil.
Methylene chloride (20mL) and trifluoroacetic acid (2.05g,18mmol) were added to the brown oil and reacted at 40 ℃ for 12 hours. The reaction solution was concentrated under reduced pressure, and after concentration, saturated aqueous potassium carbonate solution was added to adjust pH 8, dichloromethane (50mL × 3) was added for extraction, the organic phases were combined, the organic phase was dried over anhydrous sodium sulfate for 1 hour, filtered, and the filtrate was concentrated by distillation under reduced pressure to obtain 0.84g of the title compound as a colorless oil in yield: 80.1 percent.
1H NMR(400MHz,CDCl3)δ(ppm):8.10(d,J＝4.9Hz,1H),7.49–7.32(m,1H),6.69–6.59(m,1H),6.46(d,J＝8.4Hz,1H),5.97(tt,J＝56.6,4.3Hz,1H),4.86(s,1H),3.77(tdd,J＝14.6,6.4,4.3Hz,2H).
MS(ES-API,pos.ion)m/z:158.97[M+1]+.
The intermediate compounds shown in table 1 can be obtained by preparing corresponding starting materials (such as pyrazine-2-amine, pyrimidine-2-amine, 5-methoxypyridine-2-amine, 5-nitropyridine-2-amine, 4-methoxypyridine-2-amine, 4-fluoropyridine-2-amine and 3-methylpyridine-2-amine) by referring to the preparation method of the intermediate Z1.
TABLE 1
Figure BDA0003301199890000222
Figure BDA0003301199890000231
The reaction reagent in the second preparation of intermediate Z1 was replaced with 1, 1-difluoro-2-iodoethane by 1-chloro-1, 1-difluoro-2-iodoethane or 2, 2-difluoro-1-iodopropane, and the intermediate compounds in table 2 were obtained by preparation starting with 2-aminopyridine according to the preparation method of intermediate Z1.
TABLE 2
Figure BDA0003301199890000232
Wherein the corresponding structures of 2-aminopyridine, pyrazin-2-amine, pyrimidin-2-amine, 5-methoxypyridin-2-amine, 5-nitropyridin-2-amine, 4-methoxypyridin-2-amine, 4-fluoropyridin-2-amine, 3-methylpyridin-2-amine, 1-chloro-1, 1-difluoro-2-iodoethane, and 2, 2-difluoro-1-iodopropane are detailed in table 3.
TABLE 3
Figure BDA0003301199890000233
Figure BDA0003301199890000241
Intermediate N1: preparation of bis (2,4, 6-trichlorophenyl) 2- (3- (trifluoromethyl) phenyl) malonate
Figure BDA0003301199890000242
The first step is as follows: preparation of methyl 2- (3- (trifluoromethyl) phenyl) acetate
Figure BDA0003301199890000243
3-Trifluoromethylphenylacetic acid (4.08g,20mmol) was dissolved in methanol (60mL), concentrated sulfuric acid (2mL) was added, and the reaction mixture was heated to 60 ℃ and stirred for reaction for 10 hours. The reaction system was concentrated under reduced pressure, the obtained residue was dissolved in 100mL of ethyl acetate, washed with water (30mL × 3), the organic phase was dried over anhydrous sodium sulfate for 1 hour, filtered, and the filtrate was concentrated, and the residue was separated by silica gel column chromatography [ petroleum ether/ethyl acetate (v/v) ═ 30/1] to obtain 4.0g of the title compound as a colorless liquid, yield: 91.7 percent.
The second step is that: preparation of dimethyl 2- (3- (trifluoromethyl) phenyl) malonate
Figure BDA0003301199890000244
Dissolving 2- (3- (trifluoromethyl) phenyl) methyl acetate (2.9g,13.3mmol) in tetrahydrofuran (40mL) at room temperature, adding sodium hydride (60% by mass, 1.70g,42mmol) in batches, and stirring for reaction at room temperature for 30 minutes after the addition; then, dimethyl carbonate (8.1g,90mmol) was added dropwise to the reaction solution, and after completion of the addition, the reaction system was heated to 60 ℃ for reflux reaction for 18 hours. The reaction was quenched by adding 15mL of a saturated ammonium chloride solution, extracted with ethyl acetate (50mL × 3), the organic phases were combined and dried over anhydrous sodium sulfate for 1 hour, filtered, the filtrate was concentrated under reduced pressure, and the residue was separated by silica gel column chromatography [ petroleum ether/ethyl acetate (v/v) ═ 10/1] to give the title compound 3.0g, which was obtained as a colorless liquid in yield: 75.8 percent.
The third step: preparation of 2- (3- (trifluoromethyl) phenyl) malonic acid
Figure BDA0003301199890000245
Dimethyl 2- (3- (trifluoromethyl) phenyl) malonate (5.52g,20.00mmol) was added to a 100mL reaction flask, an aqueous solution (40mL) of sodium hydroxide (4.00g,100.00mmol) was slowly added, and the resulting mixture was heated to 60 ℃ for reflux reaction for 3 hours. The reaction mixture was transferred to 0 ℃ and stirred, and concentrated hydrochloric acid (10mL) was slowly added to adjust the pH of the solution to 1. Ethyl acetate (50mL × 3) was added for extraction, the organic phases were combined and dried over anhydrous sodium sulfate for 1 hour, filtered, and the filtrate was distilled under reduced pressure to obtain 4.41g of the title compound as a yellow solid in yield: 90 percent.
The fourth step: preparation of bis (2,4, 6-trichlorophenyl) 2- (3- (trifluoromethyl) phenyl) malonate
Figure BDA0003301199890000251
2- (3- (trifluoromethyl) phenyl) malonic acid (4.41g,18.00mmol), N-dimethylformamide (1mL) and dichloromethane (50mL) were charged into a 250mL single-neck flask, oxalyl chloride (8mL,95mmol) was slowly added dropwise to the reaction mixture at 0 ℃ and, after completion of the addition, the reaction mixture was left at room temperature and stirred for 6 hours, 2,4, 6-trichlorophenol (8g,40.00mmol) was added to the reaction mixture, and the reaction was continued at room temperature for 12 hours. The reaction mixture was concentrated under reduced pressure, methanol (40mL) was added, and after standing at room temperature for 3 hours, a large amount of white precipitate precipitated from the reaction mixture, which was filtered and the filter cake was washed with methanol (20mL) to give 6.64g of the title compound as a white solid in yield: 61 percent.
1H NMR(400MHz,CDCl3)δ(ppm):7.94(s,1H),7.87(d,J＝7.8Hz,1H),7.73(d,J＝7.8Hz,1H),7.62(t,J＝7.8Hz,1H),7.49(s,2H),7.41(s,2H),5.40(s,1H).
MS(ES-API,pos.ion)m/z:607.85[M+1]+.
The intermediate compounds in table 4 were obtained after preparation with reference to the preparation method of intermediate N1 using the corresponding phenylacetic acid derivative as the starting material.
TABLE 4
Figure BDA0003301199890000252
Figure BDA0003301199890000261
Figure BDA0003301199890000271
Figure BDA0003301199890000281
Figure BDA0003301199890000291
Figure BDA0003301199890000301
Figure BDA0003301199890000311
Figure BDA0003301199890000321
Figure BDA0003301199890000331
Example 1: preparation of 1- (2, 2-difluoroethyl) -3- (1- (4-fluorophenyl) -2-nitroethyl) -4-oxo-4H-pyrido [1,2-a ] pyrimidin-1-ium-2-ol salt
Figure BDA0003301199890000332
The first step is as follows: (E) preparation of (E) -1-fluoro-4- (2-nitrovinyl) benzene
Figure BDA0003301199890000333
4-fluorobenzaldehyde (6.20g,50mmol) and nitromethane (7.32g,120mmol) are dissolved in methanol (15mL), stirred at-8 ℃, and a solution of sodium hydroxide (4.00g,100mmol) in water (15mL) is added dropwise, the temperature is controlled below 15 ℃, and the reaction is finished for 15 minutes after the dropwise addition. 50mL of ice water was added, the mixture was stirred at 0 ℃ for 20 minutes, the mixture was slowly added to a solution of 6M HCl (30mL) and zinc chloride (1.5g), the dropping rate was controlled to complete 45 minutes, then the mixture was stirred at 0 ℃ for 45 minutes to form a yellow precipitate, the mixture was filtered, after the filter cake was washed with ice water, ethanol (40mL) was added, the precipitate was heated to dissolve, the mixture was cooled to 0 ℃ to crystallize, the filtrate was washed with ice water and dried to obtain 7.02g of the title compound as a yellow solid, yield: 84 percent.
The second step is that: preparation of dimethyl 2- (1- (4-fluorophenyl) -2-nitroethyl) malonate
Figure BDA0003301199890000341
(E) -1-fluoro-4- (2-nitrovinyl) benzene (5.01g,30mmol) and dimethyl malonate (7.92g,60mmol) were dissolved in toluene (35mL), and triethylamine (6.06g,101mmol) was added to react at room temperature for 8 hours. After completion of the reaction, 50mL of water was added to the reaction solution, extracted with ethyl acetate, the organic phases were combined and dried over anhydrous sodium sulfate, filtered, the filtrate was concentrated, and the residue was separated by silica gel column chromatography [ petroleum ether/ethyl acetate (v/v) ═ 4/1] to give the title compound 2.93g, which was obtained as a yellow oil in yield: 58 percent.
The third step: preparation of 2- (1- (4-fluorophenyl) -2-nitroethyl) malonic acid
Starting from the compound dimethyl 2- (1- (4-fluorophenyl) -2-nitroethyl) malonate obtained in the second reaction, the title compound was obtained as a yellow solid after preparation according to the third preparation method of intermediate N1.
Figure BDA0003301199890000342
The fourth step: preparation of bis (2,4, 6-trichlorophenyl) 2- (1- (4-fluorophenyl) -2-nitroethyl) malonate
Figure BDA0003301199890000343
Using the compound 2- (1- (4-fluorophenyl) -2-nitroethyl) malonic acid obtained in the third step as a starting material, the title compound was obtained as a white solid after preparation according to the preparation method in the fourth step of intermediate N1.
MS(ES-API,pos.ion)m/z:630.87[M+1]+.
The fifth step: preparation of 1- (2, 2-difluoroethyl) -3- (1- (4-fluorophenyl) -2-nitroethyl) -4-oxo-4H-pyrido [1,2-a ] pyrimidin-1-ium-2-ol salt
Figure BDA0003301199890000344
Intermediate Z1(N- (2, 2-difluoroethyl) pyridin-2-amine) (0.079g,0.5mmol) and bis (2,4, 6-trichlorophenyl) 2- (1- (4-fluorophenyl) -2-nitroethyl) malonate (0.32g,0.5mmol) were dissolved in 15mL of toluene and reacted at 110 ℃ for 12 hours. After the reaction solution was concentrated, the residue was subjected to silica gel column chromatography [ petroleum ether/ethyl acetate (v/v) ═ 1/3] to give the target compound 87mg, which was obtained as a yellow solid in yield: 37 percent.
MS(ES-API,pos.ion)m/z:394.10[M+1]+.
1H NMR(400MHz,CDCl3)δ(ppm):9.50–9.38(m,1H),8.16(ddd,J＝8.8,7.2,1.6Hz,1H),7.63(t,J＝8.6Hz,1H),7.58(dd,J＝8.6,5.4Hz,2H),7.42(t,J＝6.9Hz,1H),7.06–6.94(m,2H),6.35–5.98(m,1H),5.58(dd,J＝12.4,8.8Hz,1H),5.32–5.24(m,1H),5.16(dd,J＝12.4,7.0Hz,1H),4.61(td,J＝12.7,4.6Hz,2H).
Example 2: preparation of 1- (2, 2-difluoroethyl) -3-methyl-4-oxo-4H-pyrido [1,2-a ] pyrimidin-1-ium-2-ol salt
Figure BDA0003301199890000351
Intermediate Z1(N- (2, 2-difluoroethyl) pyridin-2-amine) (0.079g,0.5mmol) and 2-methylmalonic acid (0.12g,1.0mmol) were dissolved in 20mL of dichloromethane, dicyclohexylcarbodiimide (0.41g,2.0mmol) was added, and the reaction was carried out at room temperature for 24 hours. The filtrate was filtered, the filtrate was concentrated, and the residue was separated by silica gel column chromatography [ petroleum ether/ethyl acetate (v/v) ═ 1/3] to give 0.065g of the objective compound as a yellow solid in yield: 39 percent.
MS(ES-API,pos.ion)m/z:241.07[M+1]+.
1H NMR(400MHz,CDCl3)δ(ppm):9.52(dd,J＝6.8,1.3Hz,1H),8.12(ddd,J＝8.8,7.1,1.6Hz,1H),7.66(d,J＝9.0Hz,1H),7.41(t,J＝6.9Hz,1H),6.40–6.02(m,1H),4.68(td,J＝12.7,4.7Hz,2H),2.16(s,3H).
Example 3: preparation of 1- (2, 2-difluoroethyl) -3- (3-fluoro-5- (trifluoromethyl) phenyl) -4-oxo-4H-pyrido [1,2-a ] pyrimidin-1-ium-2-ol salt
Figure BDA0003301199890000352
Intermediate Z1(N- (2, 2-difluoroethyl) pyridin-2-amine) (0.079g,0.5mmol), intermediate N2 (bis (2,4, 6-trichlorophenyl) 2- (3-fluoro-5- (trifluoromethyl) phenyl) malonate) (0.31g,0.5mmol) and toluene (20mL) were added to a 50mL one-neck flask and heated to 110 deg.C for 12 hours. After the reaction was completed, the solvent was distilled off under reduced pressure, and the residue was separated by silica gel column chromatography [ methanol/dichloromethane (v/v) ═ 1/20] to obtain 0.078g of the objective compound as a yellow oil in yield: 40.2 percent.
MS(ES-API,pos.ion)m/z:389.07[M+1]+.
1H NMR(400MHz,CDCl3)δ(ppm):9.63–9.53(m,1H),8.29–8.18(m,1H),8.03(s,1H),7.85(d,J＝10.5Hz,1H),7.73(d,J＝8.9Hz,1H),7.49(t,J＝7.0Hz,1H),7.21(d,J＝8.4Hz,1H),6.25(tt,J＝56.1,4.7Hz,1H),4.71(td,J＝12.6,4.7Hz,2H).
The objective compounds in table 5 were obtained by carrying out the preparation with reference to the fifth preparation process in example 1 or the preparation process in example 3, using any one of intermediate compounds Z1 through Z8 and any one of intermediate compounds N1 through N43 as reactants.
TABLE 5
Figure BDA0003301199890000353
Figure BDA0003301199890000361
Figure BDA0003301199890000371
Figure BDA0003301199890000381
Figure BDA0003301199890000391
Figure BDA0003301199890000401
Figure BDA0003301199890000411
Figure BDA0003301199890000421
Figure BDA0003301199890000431
Figure BDA0003301199890000441
Figure BDA0003301199890000451
Figure BDA0003301199890000461
Figure BDA0003301199890000471
Figure BDA0003301199890000481
Figure BDA0003301199890000491
Figure BDA0003301199890000501
Figure BDA0003301199890000511
Figure BDA0003301199890000521
Activity assay
The preparation method of the medicament comprises the following steps: weighing a certain mass of original medicine by an analytical balance (0.0001g), dissolving the original medicine into 10000ppm of mother liquor by acetone, and then diluting the mother liquor by a certain volume of distilled water containing 1 per mill of Tween-80 emulsifier for later use.
1) Test methods-test targets: sticky insect
Leaf soaking method: the method comprises the steps of soaking a proper amount of corn leaves in prepared liquid medicine fully, naturally drying in the shade, placing the corn leaves into a culture dish filled with filter paper, inoculating 10 heads/dish of armyworm larvae in the 3-instar middle period, placing the corn leaves into an observation room at 24-27 ℃ for culture, and investigating results after 72 hours. If the body of the insect is touched by a brush pen, no response is regarded as dead insect.
The test results show that: the lethality to armyworms of the examples 3,4, 9, 13, 14, 15, 17, 19, 20, 21, 42, 43, 44, 51, 53, 63 and 76 was not less than 70% at the test concentration of 100 mg/L.
2) Test methods-test targets: bemisia tabaci (Fr.) Kuntze
Spraying method: placing eggplant seedlings with consistent growth vigor into a bemisia tabaci rearing cage, transferring the oviposited plants into an insect-free cage for normal culture after 24 hours, sampling by using a hole puncher with the diameter of 12mm when nymphs grow to 1 year, placing the taken leaf disks into a 9cm culture dish (keeping moisture by agar), counting the total number of insects under a body microscope, then carrying out medicament treatment on prepared liquid medicaments by a potter spray tower from high to low (the concentration of the liquid medicaments can be 200mg/L, 100mg/L, 50mg/L and the like), naturally drying in the shade, placing the liquid medicaments into an artificial climate box, observing under a stereoscopic microscope after 3 days, touching the insects by a writing brush, and counting the total number of the insects and the number of dead insects, wherein the death rate is calculated when the insects are dead.
The test results show that: the mortality rate of the tobacco whitefly is more than or equal to 90 percent under the test concentration of 50mg/L in the examples 3,4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 19, 20, 23, 24, 25, 26, 27, 76 and 78.
3) Test methods-test targets: alfalfa aphid
Spraying method: selecting cowpea leaves with consistent growth, making leaf disks by using a puncher, placing wet sponge blocks in a culture dish, placing the leaf disks on the sponge, and adding water to flush the leaf disks for later use. Inoculating 2-3-year-old alfalfa aphids raised indoors to prepared leaf disks, wherein the number of the leaf disks is more than 15. The spray tower is adopted for treatment, and the amount of the sprayed liquid medicine is 0.5mL per treatment. And (5) placing the test material treated by the medicament in an observation room, and observing the result after 2 d. If the body of the insect is touched by a brush pen, no response is regarded as dead insect.
The test results show that: the test concentration of the sample is 100mg/L, and the lethality of the sample in example 2, example 3, example 4, example 5, example 6, example 7, example 8, example 9, example 10, example 12, example 13, example 14, example 17, example 19, example 20, example 21, example 23, example 24, example 25, example 26, example 27, example 33, example 34, example 40, example 42, example 44, example 45, example 70, example 72 and example 73 to the aphis medicaginis more than or equal to 70%.
The compound of the invention has excellent control effect (lethality) on the aphis medicaginis after the concentration is reduced, and the specific test results are shown in the table 6:
TABLE 6
Figure BDA0003301199890000531
The test results show that the compound of the invention has excellent control effect (lethality) on the alfalfa aphid after the concentration is reduced: under the test concentration of 10mg/L, the fatality rate of the example 4 and the example 9 to the alfalfa aphid is more than or equal to 80 percent.
4) Test methods-test targets: nilaparvata lugens (Nilaparvata lugens)
Spraying method: respectively carrying out spray treatment on rice seedlings connected with the brown planthoppers (15 larvae of 2-3 instars) under a Potter spray tower, culturing the treated brown planthoppers in an observation room at 24-27 ℃, investigating results after 72 hours, touching the bodies with a writing brush, and calculating the death rate if the bodies are immobile.
The test results show that: at a test concentration of 100mg/L, the killing rate of example 1, example 3, example 4, example 5, example 6, example 7, example 8, example 9, example 10, example 11, example 12, example 13, example 14, example 17, example 18, example 19, example 20, example 21, example 22, example 25, example 32, example 35, example 38, example 39, example 40, example 44, example 49, example 50, example 52, example 53, example 59, example 73, example 74, example 76, example 77, example 78 and example 79 to brown planthopper is more than or equal to 70%.
The test results show that: the fatality rate of the examples 4, 5, 8, 9 and 10 to the brown planthopper is more than or equal to 90 percent under the test concentration of 20 mg/L.
The test results show that: the compounds of the invention have excellent control (mortality) against brown planthopper after reducing the concentration: the fatality rate to brown planthopper of example 4, example 5, example 8 and example 10 is more than or equal to 80% at the test concentration of 10mg/L, while the fatality rate to brown planthopper of compound 7 in patent CN101939302A is only 40% at the test concentration of 10 mg/L.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.

Claims (10)

1. A compound which is a stereoisomer, a nitroxide or a salt thereof having or being of formula (I):
Figure FDA0003301199880000011
wherein:
R1is hydrogen, C1-6Alkyl, halo C1-6Alkyl radical, C2-6Alkenyl radical, C2-6Alkynyl, C3-6Cycloalkyl radical, C3-6cycloalkyl-C1-3Alkylene-, C3-6Cycloalkenyl or C3-6Cycloalkenyl radical-C1-3Alkylene-; wherein R is1Optionally substituted by 1,2 or 3 substituents selected from halogen, hydroxy, nitro, amino, carboxy, cyano, C1-4Alkyl radical, C1-4Alkoxy, halo C1-4Alkyl or halo C1-4Alkoxy substitution;
or, R1Is C6-14Aryl or 5-10 membered heteroaryl; wherein R is1Optionally substituted by 1,2,3, 4 or 5 substituents selected from halogen, hydroxy, nitro, amino, carboxy, cyano, -CHO, C1-4Alkyl radical, C1-4Alkoxy, halo C1-4Alkyl, halo C1-4Alkoxy radical, C1-4Alkylthio, halo C1-4Alkylthio radical, C2-4Alkenyl radical, C2-4Alkenyloxy radical, C2-4Alkynyl, C2-4Alkynyloxy, C3-6Cycloalkyl radical, C3-6Cycloalkyl oxy, C3-6cycloalkyl-C1-3Alkylene-, -NHC1-4Alkyl, -N (C)1-4Alkyl radical)2、-C(＝O)NHC1-4Alkyl, -C (═ O) N (C)1-4Alkyl radical)2、-NH-C(＝O)-C1-4Alkyl, -N (C)1-4Alkyl) -C (═ O) -C1-4Alkyl, -NH-C (═ O) -C1-4Alkoxy, -N (C)1-4Alkyl) -C (═ O) -C1-4Alkoxy, -NH-S (═ O)2-C1-4Alkyl, -N (C)1-4Alkyl) -S (═ O)2-C1-4Alkyl, -OS (═ O)2-C1-4Alkyl radical, C1-4alkyl-C (═ O) -, C1-4alkoxy-C (═ O) -, C1-4alkyl-C (═ O) O-, (optionally substituted with 1,2,3, 4 or 5 substituents selected from halogen, hydroxy, nitro, cyano, C1-4Alkyl, halo C1-4Alkyl radical, C1-4Alkoxy or halo C1-4Alkoxy-substituted) phenyl or (optionally substituted by 1,2,3, 4 or 5 substituents selected from halogen, hydroxy, nitro, cyano, C1-4Alkyl, halo C1-4Alkyl radical, C1-4Alkoxy or halo C1-4Alkoxy substituted) phenoxy substituted;
or, R1Is C6-14aryl-C1-3Alkylene-or 5-10 membered heteroaryl-C1-3Alkylene-; wherein R is1Optionally substituted by 1,2,3, 4 or 5 substituents selected from halogen, hydroxy, nitro, amino, carboxy, cyano, C1-4Alkyl radical, C1-4Alkoxy-substituted C1-4Alkyl, hydroxy substituted C1-4Alkyl, cyano-substituted C1-4Alkyl, nitro substituted C1-4Alkyl radical, C1-4Alkoxy, halo C1-4Alkyl or halo C1-4Alkoxy substitution;
or, R1Is composed of
Figure FDA0003301199880000012
Wherein, X, X2、X3And X5Each independently is-CR11R12-、-O-、-S-、-S(＝O)-、-S(＝O)2-or-NR13-；X1And X4Each independently is-CR14R15-；R11、R12、R14And R15Each independently is hydrogen, halogen or C1-6An alkyl group; r13Is hydrogen or C1-6An alkyl group;
R2and R3Each independently is hydrogen, halogen or C1-4An alkyl group;
R4is hydrogen, chlorine, bromine, iodine or C1-4An alkyl group;
R5、R6together with the nitrogen and carbon atoms to which they are attached to form
Figure FDA0003301199880000013
Wherein R isa、Rb、RcAnd RdEach independently is hydrogen, cyano, nitro, halogen, C1-6Alkyl or C1-6An alkoxy group;
or, R5、R6And the nitrogen atom and carbon atom to which they are attached, together form the following ring R-1, ring R-2, ring R-3 or ring R-4:
Figure FDA0003301199880000021
wherein ring R-1, ring R-2, ring R-3 and ring R-4 are optionally substituted with 1,2 or 3 substituents selected from cyano, nitro, halogen, C1-6Alkyl or C1-6Alkoxy substitution.
2. The compound of claim 1, wherein:
R1is hydrogen, C1-4Alkyl, halo C1-4Alkyl radical, C2-4Alkenyl radical, C2-4Alkynyl, C3-6Cycloalkyl radical, C3-6cycloalkyl-C1-3Alkylene-, C3-6Cycloalkenyl or C3-6Cycloalkenyl radical-C1-3Alkylene-; wherein R is1Optionally substituted by 1,2 or 3 substituents selected from halogen, hydroxy, nitro, amino, carboxy, cyano, C1-4Alkyl radical, C1-4Alkoxy, halo C1-4Alkyl or halo C1-4Alkoxy substitution;
or, R1Is phenyl, naphthyl or thienyl; wherein R is1Optionally substituted by 1,2,3, 4 or 5 substituents selected from halogen, hydroxy, nitro, amino, carboxy, cyano, -CHO, C1-4Alkyl radical, C1-4Alkoxy, halo C1-4Alkyl, halo C1-4Alkoxy radical, C1-4Alkylthio, halo C1-4Alkylthio radical, C2-4Alkenyl radical, C2-4Alkenyloxy radical, C2-4Alkynyl, C2-4Alkynyloxy, C3-6Cycloalkyl radical, C3-6Cycloalkyl oxy, C3-6cycloalkyl-C1-3Alkylene-, -NHC1-4Alkyl, -N (C)1-4Alkyl radical)2、-C(＝O)NHC1-4Alkyl, -C (═ O) N (C)1-4Alkyl radical)2、-NH-C(＝O)-C1-4Alkyl, -N (C)1-4Alkyl) -C (═ O) -C1-4Alkyl, -NH-C (═ O) -C1-4Alkoxy, -N (C)1-4Alkyl) -C (═ O) -C1-4Alkoxy, -NH-S (═ O)2-C1-4Alkyl, -N (C)1-4Alkyl) -S (═ O)2-C1-4Alkyl, -OS (═ O)2-C1-4Alkyl radical, C1-4alkyl-C (═ O) -, C1-4alkoxy-C (═ O) -, C1-4alkyl-C (═ O) -O-, (optionally substituted with 1,2,3, 4 or 5 substituents selected from halogen, hydroxy, nitro, cyano, C1-4Alkyl, halo C1-4Alkyl radical, C1-4Alkoxy or halo C1-4Alkoxy-substituted) phenyl or (optionally substituted by 1,2,3, 4 or 5 substituents selected from halogen, hydroxy, nitro, cyano, C1-4Alkyl, halo C1-4Alkyl radical, C1-4Alkoxy or halo C1-4Alkoxy substituted) phenoxy substituted;
or, R1Is phenyl-C1-3Alkylene-; wherein R is1Optionally substituted by 1,2,3, 4 or 5 substituents selected from halogen, hydroxy, nitro, amino, carboxy, cyano, C1-4Alkyl radical, C1-4Alkoxy-substituted C1-4Alkyl, hydroxy substituted C1-4Alkyl, cyano-substituted C1-4Alkyl, nitro substituted C1-4Alkyl radical, C1-4Alkoxy, halo C1-4Alkyl or halo C1-4Alkoxy substitution;
or, R1Is composed of
Figure FDA0003301199880000022
Wherein, X, X2、X3And X5Each independently is-CR11R12-、-O-、-S-、-S(＝O)-、-S(＝O)2-or-NR13-；X1And X4Each independently is-CR14R15-；R11、R12、R14And R15Each independently hydrogen or halogen; r13Is hydrogen or C1-4An alkyl group.
3. A compound according to any one of claims 1 or 2, wherein:
R1is hydrogen, -CH3、-CH2CH3、-CH2CH2CH3、-CH2CH2CH2CH3、-CH＝CH2、-CH2CH＝CH2、-C≡CH、-CH2C ≡ CH, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropyl-CH2-, cyclobutyl-CH2-, cyclopentyl-CH2-or cyclohexyl-CH2-；
Or, R1Is phenyl, naphthalen-1-yl, naphthalen-2-yl or thiophen-3-yl; wherein R is1Optionally substituted by 1,2,3, 4 or 5 substituents selected from fluoro, chloro, bromo, iodo, hydroxy, nitro, amino, carboxy, cyano, -CHO, -CH3、-CH2CH3、-CH2CH2CH3、-CH2CH2CH2CH3、-C(CH3)3、-OCH3、-OCH2CH3、-OCH2CH2CH3、-CHF2、-CF3、-CH2CF3、-OCHF2、-OCF3、-OCH2CF3、-SCH3、-SCH2CH3、-SCF3、-SCH2CF3Optionally substituted with 1,2,3, 4 or 5 substituents selected from fluoro, chloro, bromo, iodo, hydroxy, nitro, cyano, -CH3、-CF3、-OCH3or-OCF3Substituted) phenyl or (optionally substituted by 1,2,3, 4 or 5 substituents selected from fluoro, chloro, bromo, iodo, hydroxy, nitro, cyano, -CH3、-CF3、-OCH3or-OCF3Substituted) phenoxy substitution;
or, R1Is phenyl-CH2-or phenyl-CH2CH2-; wherein R is1Optionally substituted with 1,2,3, 4 or 5 substituents selected from fluoro, chloro, bromo, iodo, hydroxy, nitro, amino, carboxy, cyano, -CH3、-CH2CH3、-CH2OH、-CH2CN、-CH2NO2、-OCH3、-OCH2CH3、-CF3or-OCF3Substitution;
or, R1Is composed of
Figure FDA0003301199880000031
Wherein, X, X2、X3And X5Each independently is-CR11R12-、-O-、-S-、-S(＝O)-、-S(＝O)2-or-NR13-；X1And X4Each independently is-CR14R15-；R11、R12、R14And R15Each independently is hydrogen or fluorine; r13Is hydrogen or-CH3。
4. A compound according to any one of claims 1-3, wherein:
R2and R3Each independently hydrogen, fluorine, chlorine, bromine, iodine, -CH3or-CH2CH3。
5. The compound according to any one of claims 1-4, wherein:
R4is hydrogen, chlorine, bromine, iodine, -CH3or-CH2CH3。
6. The compound according to any one of claims 1-5, wherein:
R5、R6together with the nitrogen and carbon atoms to which they are attached to form
Figure FDA0003301199880000032
Wherein R isa、Rb、RcAnd RdEach independently is hydrogen, cyano, nitro, halogen, C1-4Alkyl or C1-4An alkoxy group;
or, R5、R6And the nitrogen atom and carbon atom to which they are attached, together form the following ring R-1, ring R-2, ring R-3 or ring R-4:
Figure FDA0003301199880000033
wherein ring R-1, ring R-2, ring R-3 and ring R-4 are optionally substituted with 1,2 or 3 substituents selected from cyano, nitro, halogen, C1-4Alkyl or C1-4Alkoxy substitution.
7. The compound according to any one of claims 1-6, wherein:
R5、R6together with the nitrogen and carbon atoms to which they are attached to form
Figure FDA0003301199880000034
Wherein R isa、Rb、RcAnd RdEach independently is hydrogen, cyano, nitro, fluoro, chloro, bromo, iodo, -CH3or-OCH3；
Or, R5、R6And the nitrogen atom and carbon atom to which they are attached, together form the following ring R-1, ring R-2, ring R-3 or ring R-4:
Figure FDA0003301199880000035
wherein ring R-1, ring R-2, ring R-3 and ring R-4 are optionally substituted with 1,2 or 3 substituents selected from cyano, nitro, fluoro, chloro, bromo, iodo, -CH3or-OCH3And (4) substitution.
8. A compound which is a compound having one of the following structures or a stereoisomer, a nitroxide or a salt thereof of a compound having one of the following structures:
Figure FDA0003301199880000041
Figure FDA0003301199880000051
Figure FDA0003301199880000061
Figure FDA0003301199880000071
Figure FDA0003301199880000081
9. a composition comprising a compound according to any one of claims 1 to 8 and at least one agriculturally suitable auxiliary.
10. Use of a compound according to any one of claims 1 to 8 or a composition according to claim 9 as a pesticide in agriculture, forestry or horticulture.
CN202111191288.1A 2020-10-15 2021-10-13 Mesoionic compound and preparation method and application thereof Pending CN114369090A (en)

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