CN112794817A - Quinoline derivative and preparation method and application thereof - Google Patents

Quinoline derivative and preparation method and application thereof Download PDF

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Publication number
CN112794817A
CN112794817A CN201911112210.9A CN201911112210A CN112794817A CN 112794817 A CN112794817 A CN 112794817A CN 201911112210 A CN201911112210 A CN 201911112210A CN 112794817 A CN112794817 A CN 112794817A
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alkyl
phenyl
radical
independently
chlorine
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李义涛
姚文强
王发平
常青
林健
高国良
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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
    • C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
    • C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
    • C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D215/20—Oxygen atoms
    • C07D215/22—Oxygen atoms attached in position 2 or 4
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
    • A01N43/42—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings condensed with carbocyclic rings
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/80—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,2
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having no bond to a nitrogen atom
    • A01N47/06—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having no bond to a nitrogen atom containing —O—CO—O— groups; Thio analogues thereof
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
    • A01N47/18—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing a —O—CO—N< group, or a thio analogue thereof, directly attached to a heterocyclic or cycloaliphatic ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
    • C07D405/12—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
    • C07D409/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
    • C07D413/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
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  • Plural Heterocyclic Compounds (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

The invention relates to a quinoline derivative and a preparation method and application thereof; specifically, the invention relates to a compound shown as a formula (I), and a compound shown as a formula (I)And the application of the composition and/or the preparation containing the compound shown in the formula (I) as a pesticide in agriculture, forestry and/or horticulture; wherein R in the formula (I)1is-C (═ O) R11、‑C(＝O)OR12or-SO2R13；R11Is C6‑10Aryl, 5-6 membered heteroaryl, C3‑6Cycloalkenyl, phenyl-C2‑4Alkenyl-and the like; r12Is C2‑6Alkyl radical, C2‑4Alkenyl radical, C2‑4Alkynyl, C3‑6Cycloalkyl or C6‑10An aryl group; r13Is C2‑6Alkyl radical, C6‑10Aryl or 5-6 membered heteroaryl; r2And R3Each independently is methyl or ethyl; x1、X2And X3Each independently hydrogen or methyl.

Description

Quinoline derivative and preparation method and application thereof
Technical Field
The invention relates to the field of pesticides, in particular to a novel quinoline derivative, a preparation method of the quinoline derivative and application of a composition and/or a preparation containing the quinoline derivative as an insecticide in agriculture, forestry and/or horticulture.
Background
In agriculture, the yield is obviously reduced due to the damage of pests to the growth and storage of crops, the continuous use of pesticides causes the problems of pest resistance, pesticide service life, environmental pollution and the like, and in order to solve various problems existing in the use of current pesticides, novel pesticide compounds which are more efficient, low in toxicity, safe to the environment and have different action modes need to be continuously developed.
Disclosure of Invention
The novel quinoline derivative disclosed by the invention has the advantages of novel structure and simple preparation method, has excellent control effect on pests, particularly armyworm, plutella xylostella, frankliniella occidentalis, asparagus caterpillar and the like, and can be applied as a pesticide in agriculture, forestry and/or horticulture.
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 BDA0002273053240000011
wherein:
R1is-C (═ O) R11、-C(＝O)OR12or-SO2R13；
R11Is C2-6Alkyl radical, C2-4Alkenyl radical, C2-4Alkynyl, C3-6Cycloalkyl, -NR4R5、C6-10Aryl, 5-6 membered heteroaryl, C3-6Cycloalkenyl, phenyl-C2-4Alkenyl-or adamantyl;
R12is C2-6Alkyl radical, C2-4Alkenyl radical, C2-4Alkynyl, C3-6Cycloalkyl or C6-10An aryl group;
R13is C2-6Alkyl radical, C6-10Aryl or 5-6 membered heteroaryl;
wherein R is11、R12And R13Each independently optionally substituted by 1,2, 3,4 or 5 substituents selected from fluoro, chloro, bromo, iodo, hydroxy, cyano, nitro, C1-4Alkyl radical, C1-4Alkoxy, halo C1-4Alkyl, halo C1-4Alkoxy radical, C1-4Alkylthio, halo C1-4Alkylthio, phenyl optionally substituted by 1 or 2 fluorine, chlorine, bromine or iodine, -NH-C1-4Alkyl or-N (C)1-4Alkyl radical)2Substituted with the substituent(s);
R4and R5Each independently is C1-4Alkyl radical, C3-6Cycloalkyl radical, C3-6cycloalkyl-C1-2Alkyl-, phenyl optionally substituted with fluorine, chlorine, bromine or iodine or benzyl optionally substituted with fluorine, chlorine, bromine or iodine;
or R4、R5And the N atom to which it is attached form a 5-6 membered heterocyclic ring; said 5-6 membered heterocyclic ring is optionally substituted by 1,2, 3,4 or 5 substituents selected from fluoro, chloro, bromo, iodo or C1-4Alkyl substituent substitution;
R2and R3Each independently is C1-4Alkyl or halo C1-4An alkyl group;
X1、X2and X3Each independently is hydrogen or-CH3；
The conditions are as follows: when R is11Is C3-6Cycloalkyl or R12Is C3-6When being cycloalkyl, X1And X2Each independently is-CH3，X3Is hydrogen.
In some embodiments, when R11Is C2-6Alkyl or C3-6A cycloalkyl group; or when R is12Is C2-6Alkyl or C3-6When being cycloalkyl, X1And X2Each independently is-CH3，X3Is hydrogen.
The adamantyl group of the invention is:
Figure BDA0002273053240000021
preferably, in some embodiments, R2And R3Each independently is-CH3or-CH2CH3。
More preferably, in some embodiments, R2is-CH3；R3is-CH2CH3。
Preferably, in some embodiments, X1And X3Each independently is hydrogen; x2is-CH3。
Preferably, in other embodiments, X1And X2Each independently is-CH3；X3Is hydrogen.
In some embodiments, R11Is C2-6Alkyl radical, C2-4Alkenyl radical, C2-4Alkynyl, C3-6Cycloalkyl, -NR4R5Phenyl, thienyl, furyl, pyrrolyl, pyridyl, isoxazolyl, isothiazolyl, pyrazolyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, phenyl-vinyl-, phenyl-propenyl-, phenyl-allyl-or adamantyl;
wherein R is11Optionally substituted by 1,2, 3,4 or 5 substituents selected from fluoro, chloro, bromo, iodo, hydroxy, cyano, nitro, C1-4Alkyl radical, C1-4Alkoxy, halo C1-4Alkyl, halo C1-4Alkoxy radical, C1-4Alkylthio, halo C1-4Alkylthio, phenyl optionally substituted by 1 or 2 fluorine, chlorine, bromine or iodine, -NH-C1-4Alkyl or-N (C)1-4Alkyl radical)2Is substituted with the substituent(s).
In some embodiments, R4And R5Each independently is C1-4Alkyl radical, C3-6Cycloalkyl radical, C3-6cycloalkyl-CH2Phenyl optionally substituted by fluorine, chlorine, bromine or iodine or benzyl optionally substituted by fluorine, chlorine, bromine or iodine.
In other embodiments, R4And R5Each independently is-CH3、-CH2CH3Cyclopropyl, cyclopropyl-CH2Phenyl optionally substituted by fluorine, chlorine, bromine or iodine or benzyl optionally substituted by fluorine, chlorine, bromine or iodine.
In still other embodiments, R4、R5And the N atom to which it is attached form a 6-membered heterocyclic ring; said 6-membered heterocycle being optionally substituted by 1,2, 3,4 or 5 substituents selected from fluoro, chloro, bromo, iodo or C1-4Alkyl substituents.
In still other embodiments, R4、R5And the N atom to which it is attached form a morpholine ring or piperidine ring.
The morpholine ring is
Figure BDA0002273053240000022
The piperidine ring is
Figure BDA0002273053240000023
In some embodiments, R11Is C2-6Alkyl radical, C2-4Alkenyl radical, C2-4Alkynyl, C3-6Cycloalkyl, -NR4R5Phenyl, thienyl, furyl, pyrrolyl, pyridyl, isoxazolyl, isothiazolyl, pyrazolyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, phenyl-vinyl-, phenyl-propenePhenyl-allyl-or adamantyl;
wherein R is11Optionally substituted by 1,2, 3,4 or 5 substituents selected from fluoro, chloro, bromo, iodo, hydroxy, cyano, nitro, -CH3、-CH2CH3、-CH2CH2CH3、-CH(CH3)2、-CH2CH2CH2CH3、-C(CH3)3、-OCH3、-OCH2CH3、-OCH2CH2CH3、-OCH(CH3)2、-CHF2、-CF3、-SCH3、-SCF3、-OCF3Phenyl or-N (CH) optionally substituted by 1 or 2 fluorine, chlorine, bromine or iodine3)2Is substituted with the substituent(s).
In some embodiments, R11Is C2-6Alkyl radical, C2-4Alkenyl radical, C2-4Alkynyl or C3-6A cycloalkyl group.
Preferably, in some embodiments, R11is-CH2CH3、-CH2CH2CH3、-CH(CH3)2、-C(CH3)3、-CH2C(CH3)3、CH2＝CH-、CH2＝CHCH2-, cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.
In some embodiments, R11is-NR4R5、C6-10Aryl, 5-6 membered heteroaryl, C3-6Cycloalkenyl, phenyl-C2-4Alkenyl-or adamantyl;
wherein R is11Optionally substituted by 1,2, 3,4 or 5 substituents selected from fluoro, chloro, bromo, iodo, hydroxy, cyano, nitro, C1-4Alkyl radical, C1-4Alkoxy, halo C1-4Alkyl, halo C1-4Alkoxy radical, C1-4Alkylthio, halo C1-4Alkylthio, phenyl optionally substituted by 1 or 2 fluorine, chlorine, bromine or iodine, -NH-C1-4Alkyl or-N (C)1-4Alkyl radical)2Is substituted with the substituent(s).
In yet other embodiments, R11is-NR4R5Phenyl, thienyl, furyl, pyrrolyl, pyridyl, isoxazolyl, isothiazolyl, pyrazolyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, phenyl-vinyl-, phenyl-propenyl-, phenyl-allyl-or adamantyl;
wherein R is11Optionally substituted by 1,2, 3,4 or 5 substituents selected from fluoro, chloro, bromo, iodo, hydroxy, cyano, nitro, C1-4Alkyl radical, C1-4Alkoxy, halo C1-4Alkyl, halo C1-4Alkoxy radical, C1-4Alkylthio, halo C1-4Alkylthio, phenyl optionally substituted by 1 or 2 fluorine, chlorine, bromine or iodine, -NH-C1-4Alkyl or-N (C)1-4Alkyl radical)2Is substituted with the substituent(s).
In other embodiments, R11is-NR4R5Phenyl, thienyl, furyl, pyrrolyl, pyridyl, isoxazolyl, isothiazolyl, pyrazolyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, phenyl-vinyl-, phenyl-propenyl-, phenyl-allyl-or adamantyl;
wherein R is11Optionally substituted by 1,2, 3,4 or 5 substituents selected from fluoro, chloro, bromo, iodo, hydroxy, cyano, nitro, -CH3、-CH2CH3、-CH2CH2CH3、-CH(CH3)2、-CH2CH2CH2CH3、-C(CH3)3、-OCH3、-OCH2CH3、-OCH2CH2CH3、-OCH(CH3)2、-CHF2、-CF3、-SCH3、-SCF3、-OCF3Phenyl or-N (CH) optionally substituted by 1 or 2 fluorine, chlorine, bromine or iodine3)2Is substituted with the substituent(s).
In still other embodiments, R11Is of the sub-structure:
Figure BDA0002273053240000031
wherein R isa、Rb、Rc、RdAnd ReEach independently is hydrogen, fluorine, chlorine, bromine, iodine, hydroxyl, cyano, nitro, C1-4Alkyl radical, C1-4Alkoxy, halo C1-4Alkyl, halo C1-4Alkoxy radical, C1-4Alkylthio, halo C1-4Alkylthio, -NH-C1-4Alkyl or-N (C)1-4Alkyl radical)2；
Ra1、Rb1、Rc1、Rd1And Re1Each independently is hydrogen, fluorine, chlorine, bromine or iodine;
Rf1is hydrogen or C1-4An alkyl group.
In some embodiments, Ra、Rb、Rc、RdAnd ReEach independently is hydrogen, fluorine, chlorine, bromine, iodine, hydroxyl, cyano, nitro, -CH3、-CH2CH3、-CH2CH2CH3、-CH(CH3)2、-CH2CH2CH2CH3、-C(CH3)3、-OCH3、-OCH2CH3、-OCH2CH2CH3、-OCH(CH3)2、-CHF2、-CF3、-SCH3、-SCF3、-OCF3or-N (CH)3)2；
Ra1、Rb1、Rc1、Rd1And Re1Each independently is hydrogen, fluorine, chlorine, bromine or iodine;
Rf1is hydrogen, -CH3or-CH2CH3。
In some embodiments, R11Is of the sub-structure:
Figure BDA0002273053240000032
Figure BDA0002273053240000041
wherein R isa、Rb、Rc、RdAnd ReHave the meaning as described in the present invention.
In some embodiments, R12Is C2-6Alkyl radical, C2-4Alkenyl radical, C2-4Alkynyl, C3-6Cycloalkyl or phenyl.
In other embodiments, R12is-CH2CH3、-CH2CH2CH3、-CH(CH3)2、-C(CH3)3、-CH2C(CH3)3、CH2＝CH-、CH2＝CHCH2-, cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.
In some embodiments, R13Is C2-6Alkyl, phenyl or pyridyl;
wherein R is13Optionally substituted by 1,2, 3,4 or 5 substituents selected from fluoro, chloro, bromo, iodo, hydroxy, cyano, nitro, C1-4Alkyl radical, C1-4Alkoxy, halo C1-4Alkyl, halo C1-4Alkoxy radical, C1-4Alkylthio, halo C1-4Alkylthio, phenyl optionally substituted by 1 or 2 fluorine, chlorine, bromine or iodine, -NH-C1-4Alkyl or-N (C)1-4Alkyl radical)2Is substituted with the substituent(s).
In other embodiments, R13Is C2-6Alkyl, phenyl or pyridyl;
wherein R is13Optionally substituted by 1,2, 3,4 or 5 substituents selected from fluoro, chloro, bromo, iodo, hydroxy, cyano, nitro, -CH3、-CH2CH3、-CH2CH2CH3、-CH(CH3)2、-CH2CH2CH2CH3、-C(CH3)3、-OCH3、-OCH2CH3、-OCH2CH2CH3、-OCH(CH3)2、-CHF2、-CF3、-SCH3、-SCF3、-OCF3Phenyl or-N (CH) optionally substituted by 1 or 2 fluorine, chlorine, bromine or iodine3)2Is substituted with the substituent(s).
In some embodiments, R13Is C2-6An alkyl group.
Preferably, in some embodiments, R13is-CH2CH3、-CH2CH2CH3、-CH(CH3)2or-C (CH)3)3。
In other embodiments, R13Is phenyl or pyridyl;
wherein R is13Optionally substituted by 1,2, 3,4 or 5 substituents selected from fluoro, chloro, bromo, iodo, hydroxy, cyano, nitro, C1-4Alkyl radical, C1-4Alkoxy, halo C1-4Alkyl or halo C1-4Substituent of alkoxy.
In still other embodiments, R13Is phenyl or pyridyl;
wherein R is13Optionally substituted by 1,2, 3,4 or 5 substituents selected from fluoro, chloro, bromo, iodo, hydroxy, cyano, nitro, -CH3、-CH2CH3、-CH2CH2CH3、-CH(CH3)2、-CH2CH2CH2CH3、-C(CH3)3、-OCH3、-OCH2CH3、-OCH2CH2CH3、-OCH(CH3)2、-CHF2、-CF3or-OCF3Is substituted with the substituent(s).
In still other embodiments, R13Is of the sub-structure:
Figure BDA0002273053240000042
Ra2、Rb2、Rc2、Rd2and Re2Each independently of the others is hydrogen, fluorine, chlorine, bromine, iodine, C1-4Alkyl, halo C1-4Alkyl radical, C1-4Alkoxy or halo C1-4An alkoxy group.
In some embodiments, Ra2、Rb2、Rc2、Rd2And Re2Each independently hydrogen, fluorine, chlorine, bromine, iodine, -CH3、-CH2CH3、-CH2CH2CH3、-CH(CH3)2、-CF3or-OCF3。
In some 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 (II):
Figure BDA0002273053240000051
wherein R is13Is optionally substituted by 1,2 or 3 substituents selected from fluorine, chlorine, bromine, iodine, C1-4Alkyl radical, C1-4Alkoxy, halo C1-4Alkyl or halo C1-4Alkoxy-substituted phenyl or pyridine;
R2、R3、X1、X2and X3Have the meanings indicated for the corresponding substituents of the formula (I) according to the invention.
Preferably, R13Is optionally substituted by 1,2 or 3 substituents selected from fluoro, chloro, bromo, iodo, -CH3、-OCH3、-CF3or-OCF3Substituted phenyl or pyridine.
Further preferably, R13Is composed of
Figure BDA0002273053240000052
Figure BDA0002273053240000053
In some 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 (III):
Figure BDA0002273053240000054
wherein R is11、R2、R3、X1、X2And X3Have the meanings indicated for the corresponding substituents of the formula (I) according to the invention;
the conditions are as follows: when R is11Is C2-6Alkyl or C3-6When being cycloalkyl, X1And X2Each independently of the other being methyl, X3Is hydrogen.
In still other embodiments, R11Is of the sub-structure:
Figure BDA0002273053240000055
Figure BDA0002273053240000061
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 (IV):
Figure BDA0002273053240000062
wherein R is12、R2And R3Have the meanings indicated for the corresponding substituents of the formula (I) according to the invention.
In another aspect, the present invention provides a compound which is a compound having one of the following structures or a stereoisomer, a nitroxide or a salt thereof of the compound having one of the following structures:
Figure BDA0002273053240000063
Figure BDA0002273053240000071
Figure BDA0002273053240000081
Figure BDA0002273053240000091
Figure BDA0002273053240000101
in yet another aspect, the present invention provides a composition comprising at least one compound of the present invention and an agriculturally acceptable adjuvant.
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 compound of the present invention or the composition of the present invention is used as a plant pest control agent in agriculture, forestry, and/or horticulture.
In yet another aspect, the present invention provides a method for controlling pests, said method comprising applying a compound according to the present invention or a composition according to the present invention to a plant and/or to a plant growing environment.
Further, the pests comprise diamondback moth, armyworm, Frankliniella occidentalis and/or beet armyworm.
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 is understood that the term "optionally substituted" may be used interchangeably with the term "substituted or unsubstituted". 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 another embodiment, the alkyl group contains 2 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 (CH)3)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) Neopentyl (C (CH)3)3CH2-) and the like.
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 terms "heterocyclyl" and "heterocycle" are used interchangeably herein and refer to a saturated or partially unsaturated monocyclic, bicyclic, or tricyclic ring containing 3 to 15 ring atoms, wherein no aromatic ring is included in the monocyclic, bicyclic, or tricyclic ring, and at least one ring atom is selected from a nitrogen, sulfur, or oxygen atom. Unless otherwise specified, heterocyclyl may be carbon-or nitrogen-based, and-CH2-the group may optionally be replaced by-C (═ O) -. The sulfur atom of the ring may optionally be oxidized to the S-oxide. The nitrogen atom of the ring may optionally be oxidized to an N-oxygen compound. Examples of heterocyclic groups include, but are not limited to, oxirane, azetidinyl, oxacycloButyl, thietanyl, pyrrolidinyl (e.g., 2-pyrrolidinyl), 2-pyrrolinyl, 3-pyrrolinyl, pyrazolidinyl, and the like. In heterocyclic radicals of-CH2Examples of-groups substituted by-C (═ O) -include, but are not limited to, 2-oxopyrrolidinyl, oxo-1, 3-thiazolidinyl, 2-piperidinonyl, 3, 5-dioxopiperidinyl. Examples of sulfur atoms in heterocyclic groups that are oxidized include, but are not limited to, sulfolane, 1, 1-dioxothiomorpholinyl. The heterocyclyl group is optionally substituted with one or more substituents described herein.
In the invention, R4、R5Examples of the 6-membered heterocyclic ring formed with the N atom attached thereto include: morpholine rings, piperidine rings, and the like.
The term "heteroatom" refers to O, S, N, P and Si, including N, S and any oxidation state form of P; primary, secondary, tertiary amines and quaternary ammonium salt forms; or a form in which a hydrogen on a nitrogen atom in the heterocycle is substituted, for example, N (like N in 3, 4-dihydro-2H-pyrrolyl), NH (like NH in pyrrolidinyl) or NR (like NR in N-substituted pyrrolidinyl).
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. 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, 2-thienyl, 4-isoxazolyl, 3-pyridyl, and the like. 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 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.
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 so on.
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 "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 "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≡CH2CH3And so on.
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, the alkylene group contains 1 to 3 carbonsAn atom; in yet another embodiment, the alkylene group contains 1 to 2 carbon atoms. Examples of this include methylene (-CH)2-, ethylene (-CH)2CH2-, propylene (-CH)2CH2CH2-)，-CH(CH3)CH2-，-C(CH3)2-，-CH2CH2CH(CH3)-，-CH2CH2C(CH3)2-, and the like.
In the various parts of this specification, linking substituents are described. Where the structure clearly requires a linking group, the markush variables listed for that group are understood to be linking groups. For example, if the structure requires a linking group and the markush group definition for the variable recites "alkyl" or "alkenyl", it is understood that the "alkyl" or "alkenyl" represents an attached alkylene group or alkenylene group, respectively, such as a "phenyl-alkenyl-" group is understood to be a "phenyl-alkenylene-", a "cycloalkyl-alkyl-" group is understood to be a "cycloalkyl-alkylene-", wherein "alkenylene" represents at least one site of unsaturation, i.e., at least one carbon-carbon sp2Examples of the group obtained by removing two hydrogen atoms from a straight-chain or branched monovalent hydrocarbon group having a double bond include a vinylidene group (-CH-), and the like.
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 having the 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 compounds having formula (I), formula (II), formula (III) and/or formula (IV) may be prepared by treating compounds having formula (I), formula (II), formula (III) and/or formula (IV) 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/or formulations of the compounds of the invention
The compounds of the invention are generally useful as pesticidal active ingredients in compositions and/or formulations, and typically also include agriculturally acceptable adjuvants, which are agriculturally acceptable 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.
Use of the Compounds of the invention and compositions and/or formulations
The compounds, compositions and/or formulations of the present invention are suitable for controlling animal 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, compositions and/or formulations of the present invention kill pests by an effective amount of the active substance. The present invention therefore also relates to a method for controlling pests by applying the compounds, compositions and/or formulations 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, composition and/or formulation 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, the composition and/or the preparation have simple use methods, and the compound, the composition and/or the preparation are applied to the pests or growth media thereof. The application dose of the compound, composition and/or formulation 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
The above scheme describes the preparation of the compounds of the present invention. Unless otherwise indicated, the compounds of the invention may be prepared by the methods described herein. The starting materials, reagents and the like used in the preparation of the compounds of the present invention are commercially available or can be prepared by methods conventional in the art. In this specification, a structure is dominant if there is any difference between the chemical name and the chemical structure. In addition, in some embodiments, unless otherwise specified, the reactions of the present invention are carried out at room temperature, and the term "room temperature" refers to the natural temperature of the environment surrounding the location of the subject, which may vary depending on the location, season, and time of day, and is generally between-20 ℃ and 45 ℃ or between about 18 ℃ and 30 ℃, or between about 20 ℃ and 25 ℃ or about 22 ℃. The term "overnight reaction" generally means 8-20 hours.
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).
Hair brushThe mass spectrometry conditions used were: the conditions for low resolution Mass Spectrometry (MS) data determination were: agilent 6120Quadrupole HPLC-MS (column model: Zorbax SB-C18,2.1X 30mm,3.5 μm,6min, flow rate 0.6mL/min, mobile phase 5% -95% (CH with 0.1% formic acid)3CN) in (H containing 0.1% formic acid)2Proportion in O)), at 210/254nm with UV detection, using electrospray ionization mode (ESI).
Synthetic schemes
Synthesis scheme I
Figure BDA0002273053240000191
The target compound represented by the formula (I-1) or the target compound represented by the formula (I-2) can be prepared by the first synthesis scheme. Carrying out esterification reaction on the intermediate 1 and the intermediate A or the intermediate 1 and the intermediate B under an alkaline condition (such as triethylamine, pyridine and sodium hydride) to obtain a target compound shown in a formula (I-1) or a target compound shown in a formula (I-2);
wherein X is chlorine; r11And R13Have the meaning as described in the present invention.
Synthesis scheme two
Figure BDA0002273053240000192
The target compound represented by the formula (I-3) can be prepared by the second synthesis scheme. Carrying out esterification reaction on the intermediate 2 and the intermediate C under an alkaline condition (such as triethylamine, pyridine and sodium hydride) to obtain a target compound shown as a formula (I-3);
wherein, X1Is chlorine; r12Have the meaning as described in the present invention.
Examples
Intermediate 1: synthesis of 2-ethyl-3, 7-dimethyl-6- (4- (trifluoromethoxy) phenoxy) -1, 4-dihydroquinolin-4-ol
Figure BDA0002273053240000193
Step 1: synthesis of 5-fluoro-4-methyl-2-nitrobenzoic acid
Adding nitric acid (20mL, 65%) and sulfuric acid (50mL, 98%) into a 250mL round-bottom flask, cooling to-10 ℃ by using an ice salt bath, dissolving 3-fluoro-4-methylbenzoic acid (15.00g,97.4mmol) into concentrated sulfuric acid (50mL), slowly dripping into the mixed acid, controlling the temperature in the reaction system to be-10-0 ℃, removing the ice salt bath after dripping is finished, and reacting for 2.5 hours at 25 ℃. The crude product was poured into ice water, the precipitate filtered off, dried and recrystallized from toluene to give 15.91g of a white solid, yield: 82.1 percent.
LC-MS:(M+1)m/z＝200.0.
Step 2: synthesis of isopropyl 5-fluoro-4-methyl-2-nitrobenzoate
5-fluoro-4-methyl-2-nitrobenzoic acid (10g,50.2mmol) was dissolved in isopropanol (60mL), concentrated sulfuric acid (10mL, 98%) was slowly added at 0 deg.C, and after the addition was complete, the temperature was raised to 105 deg.C and heated under reflux for 20 hours. Excess isopropanol was removed under reduced pressure using a rotary evaporator, then extracted with ethyl acetate (60mL x3), the organic phase washed with water (30mL), brine (30mL), dried over anhydrous magnesium sulfate and concentrated using a rotary evaporator to give 9.63g of red liquid, yield: 79.6 percent.
1HNMR(400MHz,CDCl3)δ(ppm):7.81(d,1H),7.33(d,1H),5.26(m,1H),2.39(s,3H),1.35(d,6H).
LC-MS:(M+1)m/z＝242.2.
And step 3: synthesis of 4-methyl-2-nitro-5- (4- (trifluoromethoxy) phenoxy) benzoic acid isopropyl ester
Isopropyl 5-fluoro-4-methyl-2-nitrobenzoate (9.60g,39.8mmol), p-trifluoromethoxyphenol (7.12g,40.0mmol) and potassium carbonate (5.52g,40.0mmol) were added to a 250mL round-bottomed flask, N-dimethylformamide (100mL) was added, and the temperature was rapidly raised to 80 ℃ under nitrogen for 18 hours. Ice water (100mL) was added, extracted with ethyl acetate (60mL x3), the organic phase was washed with saturated aqueous sodium bicarbonate solution (50mL x3), the organic phases were combined, dried over anhydrous magnesium sulfate, filtered, and the filtrate was concentrated on a rotary evaporator to give 12.0g of a yellow oil, yield: 75.6 percent.
LC-MS:(M+1)m/z＝400.3.
And 4, step 4: synthesis of isopropyl 2-amino-4-methyl-5- (4- (trifluoromethoxy) phenoxy) benzoate
Under nitrogen protection, iron powder (5.60g,100.0mmol), ethanol (100mL), water (20mL) and hydrochloric acid (1.0mL, 35%) were added to a 500mL round-bottomed flask, the flask was heated to 90 ℃ and stirred, an ethanol solution (100mL) containing 4-methyl-2-nitro-5- (4- (trifluoromethoxy) phenoxy) benzoic acid isopropyl ester (12.0g,30.0mmol) was slowly added dropwise, and after completion of the addition, the reaction was carried out at 90 ℃ for 12 hours. Solid impurities were removed by filtration, the filtrate was concentrated using a rotary evaporator, ethyl acetate (150mL) was added, washed with brine (30mL × 3), the organic phases were combined and dried over anhydrous magnesium sulfate, filtered, the filtrate was concentrated using a rotary evaporator, and column chromatography [ PE/EtOAc (v/v) ═ 10/1] gave 10.5g of a yellow oil, yield: 94.6 percent.
1HNMR(400MHz,CDCl3)δ(ppm):7.60-7.51(m,1H),7.25-7.15(m,2H),6.91-6.80(m,2H),6.20(s,1H),5.69(s,2H),5.21(m,1H),2.11(s,3H),1.35(d,6H).
19FNMR(100MHz,CDCl3)δ(ppm):-58.4.
LC-MS:(M+1)m/z＝370.3.
And 5: synthesis of 2-ethyl-3, 7-dimethyl-6- (4- (trifluoromethoxy) phenoxy) -1, 4-dihydroquinolin-4-ol
2-amino-4-methyl-5- (4- (trifluoromethoxy) phenoxy) benzoic acid isopropyl ester (10.0g,27.1mmol), 3-pentanone (4.3g,50.0mmol), zinc chloride (6.82g,50.0mmol), and xylene (100mL) were added to a 500mL round-bottomed flask under nitrogen, and the reaction was refluxed at 160 ℃ for 18 hours. After the reaction was complete, the xylene was evaporated using a rotary evaporator to give a tan viscous mass which was cooled to 25 ℃ and stirred with water (50mL) and ethyl acetate (50mL) to form a suspension which was filtered to give an off-white solid 6.76g, yield: 66.2 percent.
1HNMR(400MHz,CDCl3)δ(ppm):11.4(s,1H),7.51(s,1H),7.28(s,1H),7.22(m,2H),7.01(m,2H),2.72(m,2H),2.31(s,3H),2.03(s,3H),1.25(m,3H).
LC-MS:(M+1)m/z＝378.1.
Example 1: synthesis of 2-ethyl-3, 7-dimethyl-6- (4- (trifluoromethoxy) phenoxy) quinolin-4-yl 4-methylbenzenesulfonate
Figure BDA0002273053240000211
2-Ethyl-3, 7-dimethyl-6- (4- (trifluoromethoxy) phenoxy) -1, 4-dihydroquinolin-4-ol (0.19g,0.5mmol) and triethylamine (0.15g,1.5mmol) were added to a 50mL single-necked flask containing dichloromethane (15mL), and 4-toluenesulfonyl chloride (0.42g,0.75mmol) was slowly added to the reaction system and reacted at room temperature for 12 hours. After completion of the reaction, water was added to quench (15mL), the aqueous phase was extracted with dichloromethane (10mL × 3), the organic phases were combined, the organic phase was dried over anhydrous sodium sulfate, 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 0.19g of a white solid, yield: 75.0 percent.
1H NMR(400MHz,CDCl3)δ(ppm):7.78(d,2H),7.59(s,1H),7.53(s,1H),7.39(d,2H),7.34(d,2H),6.78(d,2H),3.56(q,2H),2.38(s,3H),2.31(s,3H),2.43(s,3H),1.39(s,3H).
LC-MS:(M+1)m/z＝532.1.
The intermediate 1 and the corresponding material are reacted by a preparation method similar to that of example 1 or a preparation method of the prior art to obtain the target compound in the table 1.
TABLE 1
Figure BDA0002273053240000212
Figure BDA0002273053240000221
Figure BDA0002273053240000231
Figure BDA0002273053240000241
Figure BDA0002273053240000251
Figure BDA0002273053240000261
Figure BDA0002273053240000271
Figure BDA0002273053240000281
Intermediate 2: synthesis of 2-ethyl-3, 5, 7-trimethyl-6- (4- (trifluoromethoxy) phenoxy) quinolin-4-ol
Figure BDA0002273053240000282
Step 1: synthesis of 1, 3-dimethyl-5-nitro-2- (4- (trifluoromethoxy) phenoxy) benzene
2-fluoro-1, 3-dimethyl-5-nitrobenzene (10.0g,59.2mmol), p-trifluoromethoxyphenol (15.8g,88.7mmol) and potassium carbonate (12.2g,88.7mmol) were charged to a 250mL round bottom flask, N-dimethylformamide (100mL) was added, and the temperature was rapidly raised to 110 ℃ under nitrogen for 24 hours. Ice water (100mL) was added, extracted with ethyl acetate (60mL x3), the organic phase was washed with saturated aqueous sodium bicarbonate solution (50mL x3), the organic phases were combined, dried over anhydrous magnesium sulfate, filtered, and the filtrate was concentrated on a rotary evaporator to give 14.4g of a yellow oil, yield: 75 percent.
LC-MS:(M+1)m/z＝328.2.
Step 2: synthesis of 3, 5-dimethyl-4- (4- (trifluoromethoxy) phenoxy) aniline
Under the protection of nitrogen, iron powder (6.2g, 110.1mmol), ethanol (100mL), water (20mL) and 35% by mass hydrochloric acid (1.0mL) were charged into a 500mL round-bottomed flask, heated to 90 ℃ and stirred, and an ethanol solution (100mL) containing 1, 3-dimethyl-5-nitro-2- (4- (trifluoromethoxy) phenoxy) benzene (12.0g,36.7mmol) was slowly added dropwise, followed by reaction at 90 ℃ for 2 hours. After removing solid impurities by filtration, the filtrate was concentrated by a rotary evaporator, ethyl acetate (150mL) was added, and washed with saturated brine (30mL × 3), the organic phases were combined and dried over anhydrous magnesium sulfate, filtered, and the filtrate was concentrated by a rotary evaporator, and the residue was subjected to column chromatography [ petroleum ether/ethyl acetate (v/v) ═ 10/1] to give 10.0g of a yellow oil, yield: 92 percent.
LC-MS:(M+1)m/z＝298.2.
And step 3: synthesis of 2-ethyl-3, 5, 7-trimethyl-6- (4- (trifluoromethoxy) phenoxy) quinolin-4-ol
3, 5-dimethyl-4- (4- (trifluoromethoxy) phenoxy) aniline (10g,33.7mmol), ethyl 2-methyl-3-oxopentanoate (15.9g,101mmol), glacial acetic acid (0.1g,1.67mmol) and toluene (100mL) were added under nitrogen to a 100mL one-neck flask with a trap, then the reaction temperature was raised to 120 ℃ and the water was partitioned at 120 ℃ under reflux for 18 h. Evaporating the toluene solvent to obtain an oily substance; diphenyl ether (20mL) was added to the oil and the reaction stirred for 30 minutes at 255 ℃. After cooling to room temperature, petroleum ether (100mL) was slowly added, a solid precipitated, the solid was filtered off and washed with a mixed petroleum ether/ethyl acetate solution (v/v. 20/1,10mL × 3) to give 5.9g of a beige solid, yield: 45 percent.
LC-MS:(M+1)m/z＝392.4.
Example 32: synthesis of (2-ethyl-3, 5, 7-trimethyl-6- (4- (trifluoromethoxy) phenoxy) quinolin-4-yl) ethyl carbonate
Figure BDA0002273053240000291
2-Ethyl-3, 5, 7-trimethyl-6- (4- (trifluoromethoxy) phenoxy) quinolin-4-ol (0.80g,2.0mmol), triethylamine (1.0mL,6.0mmol) and dichloromethane (10mL) were charged under nitrogen atmosphere into a 50mL round-bottomed flask, cooled to 0 ℃ with an ice salt bath, added with ethyl chloroformate (0.30g,2.7mmol) and reacted at room temperature for 12 hours. Concentration on a rotary evaporator to remove the solvent, extraction with water (30mL) and ethyl acetate (30mL), drying of the organic phase over magnesium sulfate, and concentration of the filtrate on a rotary evaporator gave 0.78g of a yellow liquid in yield: 82.1 percent.
1H NMR(400MHz,CDCl3)δ7.42(s,1H),7.32(d,2H),6.95(d,2H),4.25(q,2H),3.4(q,2H),2.34(d,6H),2.15(s,3H),1.28(m,J＝7.5Hz,6H).
LC-MS:(M+1)m/z＝464.1.
The intermediate 2 and the corresponding material are reacted by a preparation method similar to that of example 32 or a preparation method in the prior art to obtain the target compound shown in the table 2.
TABLE 2
Figure BDA0002273053240000292
Figure BDA0002273053240000301
Figure BDA0002273053240000311
Examples of Activity test
Test targets: armyworm, diamondback moth, Frankliniella occidentalis, beet armyworm
Leaf soaking method: the method comprises the steps of fully soaking a proper amount of corn leaves/cabbages/cowpeas in prepared liquid medicine, naturally drying in the shade, putting the soaked corn leaves/cabbages/cowpeas in a culture dish padded with filter paper, inoculating 10 heads/dishes of 2-3-instar middle-stage larvae of armyworm/diamond back moth/beet armyworm, culturing in an observation room at 24-27 ℃, and investigating results after 3 days. If the body of the insect is touched by a brush pen, no response is regarded as dead insect. The test concentrations were 100mg/L, 50mg/L, 25mg/L, 12.5mg/L, 6.25mg/L, 3.13mg/L, 1.56 mg/L.
Spraying method: selecting cowpea leaves with consistent growth, making into leaf discs by using a puncher, placing wet degreasing cotton blocks in a culture dish, placing the leaf discs on degreasing cotton, and adding water to flush with the leaf discs for later use. Inoculating 2-3-year-old Frankliniella occidentalis bred indoors to prepared leaf dishes, wherein each dish has more than 15 heads. The treatment was carried out using a Potter spray tower, and the amount of the sprayed solution was 0.5mL per treatment. The blank control was treated first and then the above procedure was repeated in the order of lower to higher test dose, 2 replicates per treatment. The test material after the medicament treatment is placed in an observation room, and the result is observed after 1 d. If the body of the insect is touched by a brush pen, no response is regarded as dead insect. The test concentrations were 20mg/L, 10mg/L, 5.0mg/L, 2.5mg/L, 1.25mg/L, 0.625 mg/L.
The insecticidal activity test result is as follows:
the mortality rate to diamondback moth of the examples 1,2, 3,4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 26, 27, 28, 29, 30 and 31 is more than 80% at a concentration of 25 mg/L;
the lethality to armyworms in the concentration of 25mg/L is more than 90% in the embodiments 1,2, 3,4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 26, 27, 28, 29, 30 and 31;
the fatality rate of example 14, example 15, example 16, example 17, example 18, example 20, example 21, example 23, example 27 and example 29 to frankliniella occidentalis is above 90% at the concentration of 10 mg/L;
the lethality of example 14, example 15, example 16, example 17, example 18, example 20, example 21, example 23, example 27 and example 29 to beet armyworm is more than 90% at a concentration of 50 mg/L;
in addition, after the dosage of the compound is reduced, further activity tests show that the compound still shows excellent control effect on pests at lower concentration, for example, the mortality rate of the compound to plutella xylostella reaches more than 80% at the concentration of 12.5mg/L in example 14, example 15, example 16, example 20, example 21, example 24 and example 27;
under the concentration of 6.25mg/L, the lethality of the diamondback moth in the examples 23 and 29 reaches over 80 percent;
the lethality of example 18 to plutella xylostella is 80% at a concentration of 3.13 mg/L;
the mortality rate of example 32, example 33, example 34, example 35, example 36, example 37, example 38, example 39, example 40, example 41 and example 42 to plutella xylostella is above 70% at a concentration of 1.56 mg/L;
the mortality rate to armyworm of example 1, example 2, example 5, example 6, example 7, example 8, example 9, example 11, example 12, example 13, example 14, example 16, example 17, example 19, example 20, example 21, example 22, example 27 and example 31 is 80-90% at a concentration of 12.5 mg/L;
under the concentration of 6.25mg/L, the lethality of the armyworm in the examples 15 and 29 is 80-90%;
under the concentration of 3.13mg/L, the lethality of the armyworm in the examples 18 and 23 is 80-90%;
the lethality of the armyworm in the embodiment 32, the embodiment 33, the embodiment 34, the embodiment 35, the embodiment 36, the embodiment 37, the embodiment 38, the embodiment 39, the embodiment 40, the embodiment 41 and the embodiment 42 is 80-100% under the concentration of 3.13 mg/L;
under the concentration of 1.56mg/L, the lethality of the example 32 to armyworms is 90-100%;
the fatality rate of example 15, example 16, example 18, example 23 and example 29 to frankliniella occidentalis is 90-100% at the concentration of 5.0 mg/L;
the fatality rate of example 32, example 33, example 34, example 35, example 36, example 37, example 38, example 39, example 40, example 41 and example 42 to frankliniella occidentalis is 70-100% at the concentration of 1.25 mg/L;
the lethality of example 14, example 15, example 16, example 23, example 27 and example 29 to beet armyworm is 80-90% at a concentration of 25 mg/L;
the lethality of example 18 to beet armyworm is 80% at a concentration of 12.5 mg/L;
the lethality of example 32, example 33, example 34, example 35, example 36, example 37, example 38, example 39, example 40, example 41, example 42 to spodoptera exigua is above 85% at a concentration of 3.13 mg/L;
example 32 has 90% lethality to beet armyworm at a concentration of 1.56 mg/L.
The test results show that the compound has obvious control effect on pests, particularly armyworm, plutella xylostella, thrips occidentalis and/or asparagus caterpillar under different concentrations, and can be further developed to be used as a pesticide.
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 (11)

1. A compound having the formula (I), or a stereoisomer, a nitroxide or a salt thereof:
Figure FDA0002273053230000011
wherein:
R1is-C (═ O) R11、-C(＝O)OR12or-SO2R13；
R11Is C2-6Alkyl radical, C2-4Alkenyl radical, C2-4Alkynyl, C3-6Cycloalkyl, -NR4R5、C6-10Aryl, 5-6 membered heteroaryl, C3-6Cycloalkenyl, phenyl-C2-4Alkenyl-or adamantyl;
R12is C2-6Alkyl radical, C2-4Alkenyl radical, C2-4Alkynyl, C3-6Cycloalkyl or C6-10An aryl group;
R13is C2-6Alkyl radical, C6-10Aryl or 5-6 membered heteroaryl;
wherein R is11、R12And R13Each independently optionally substituted by 1,2, 3,4 or 5 substituents selected from fluoro, chloro, bromo, iodo, hydroxy, cyano, nitro, C1-4Alkyl radical, C1-4Alkoxy, halo C1-4Alkyl, halo C1-4Alkoxy radical, C1-4Alkylthio, halo C1-4Alkylthio, phenyl optionally substituted by 1 or 2 fluorine, chlorine, bromine or iodine, -NH-C1-4Alkyl or-N (C)1-4Alkyl radical)2Substituted with the substituent(s);
R4and R5Each independently is C1-4Alkyl radical, C3-6Cycloalkyl radical, C3-6cycloalkyl-C1-2Alkyl-, phenyl optionally substituted with fluorine, chlorine, bromine or iodine or benzyl optionally substituted with fluorine, chlorine, bromine or iodine;
or R4、R5And the N atom to which it is attached form a 5-6 membered heterocyclic ring; said 5-6 membered heterocyclic ring is optionally substituted by 1,2, 3,4 or 5 substituents selected from fluoro, chloro, bromo, iodo or C1-4Alkyl substituent substitution;
R2and R3Each independently is C1-4Alkyl or halo C1-4An alkyl group; preferably, R2And R3Each independently is-CH3or-CH2CH3；
X1、X2And X3Each independently is hydrogen or-CH3；
The conditions are as follows: when R is11Is C3-6Cycloalkyl or R12Is C3-6When being cycloalkyl, X1And X2Each independently is-CH3，X3Is hydrogen.
2. The compound of claim 1, wherein:
R11is C2-6Alkyl radical, C2-4Alkenyl radical, C2-4Alkynyl, C3-6Cycloalkyl, -NR4R5Phenyl, thienyl, furyl, pyrrolyl, pyridyl, isoxazolyl, isothiazolyl, pyrazolyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, phenyl-vinyl-, phenyl-propenyl-, phenyl-allyl-or adamantyl;
R12is C2-6Alkyl radical, C2-4Alkenyl radical, C2-4Alkynyl, C3-6Cycloalkyl or phenyl;
R13is C2-6Alkyl, phenyl or pyridyl;
wherein R is11、R12And R13Each independently optionally substituted by 1,2, 3,4 or 5 substituents selected from fluoro, chloro, bromo, iodo, hydroxy, cyano, nitro, C1-4Alkyl radical, C1-4Alkoxy, halo C1-4Alkyl, halo C1-4Alkoxy radical, C1-4Alkylthio, halo C1-4Alkylthio, phenyl optionally substituted by 1 or 2 fluorine, chlorine, bromine or iodine, -NH-C1-4Alkyl or-N (C)1-4Alkyl radical)2Substituted with the substituent(s);
R4and R5Each independently is C1-4Alkyl radical, C3-6Cycloalkyl radical, C3-6cycloalkyl-CH2Phenyl optionally substituted by fluorine, chlorine, bromine or iodine or benzyl optionally substituted by fluorine, chlorine, bromine or iodine;
or R4、R5And the N atom to which it is attached form a 6-membered heterocyclic ring; said 6-membered heterocycle being optionally substituted by 1,2, 3,4 or 5 substituents selected from fluoro, chloro, bromo, iodo or C1-4Alkyl substituents.
3. The compound of claim 2, wherein:
R11is C2-6Alkyl radical, C2-4Alkenyl radical, C2-4Alkynyl, C3-6Cycloalkyl, -NR4R5Phenyl, thienyl, furyl, pyrrolyl, pyridyl, isoxazolyl, isothiazolyl, pyrazolyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, phenyl-vinyl-, phenyl-propenyl-, phenyl-allyl-or adamantyl;
R12is C2-6Alkyl radical, C2-4Alkenyl radical, C2-4Alkynyl, C3-6Cycloalkyl or phenyl;
R13is C2-6Alkyl, phenyl or pyridyl;
wherein R is11、R12And R13Each independently optionally substituted with 1,2, 3,4 or 5 substituents selected from fluoro, chloro, bromo, iodo, hydroxy, cyano, nitro, -CH3、-CH2CH3、-CH2CH2CH3、-CH(CH3)2、-CH2CH2CH2CH3、-C(CH3)3、-OCH3、-OCH2CH3、-OCH2CH2CH3、-OCH(CH3)2、-CHF2、-CF3、-SCH3、-SCF3、-OCF3Phenyl or-N (CH) optionally substituted by 1 or 2 fluorine, chlorine, bromine or iodine3)2Substituted with the substituent(s);
R4and R5Each independently is-CH3、-CH2CH3Cyclopropyl, cyclopropyl-CH2Phenyl optionally substituted by fluorine, chlorine, bromine or iodine or benzyl optionally substituted by fluorine, chlorine, bromine or iodine;
or R4、R5And the N atom to which it is attached form a morpholine ring or piperidine ring.
4. A compound according to claim 3, wherein:
R11is C2-6Alkyl radical, C2-4Alkenyl radical, C2-4Alkynyl or C3-6A cycloalkyl group; preferably, R11is-CH2CH3、-CH2CH2CH3、-CH(CH3)2、-CH2CH2CH2CH3、-C(CH3)3、-CH2C(CH3)3、CH2＝CH-、CH2＝CHCH2-, cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl;
or R11Is of the sub-structure:
Figure FDA0002273053230000021
wherein R isa、Rb、Rc、RdAnd ReEach independently is hydrogen, fluorine, chlorine, bromine, iodine, hydroxyl, cyano, nitro, C1-4Alkyl radical, C1-4Alkoxy, halo C1-4Alkyl, halo C1-4Alkoxy radical, C1-4Alkylthio, halo C1-4Alkylthio, -NH-C1-4Alkyl or-N (C)1-4Alkyl radical)2；
Ra1、Rb1、Rc1、Rd1And Re1Each independently is hydrogen, fluorine, chlorine, bromine or iodine;
Rf1is hydrogen or C1-4An alkyl group.
5. The compound of claim 4, wherein:
R11is of the sub-structure:
Figure FDA0002273053230000022
Figure FDA0002273053230000031
Ra、Rb、Rc、Rdand ReEach independently is hydrogen, fluorine, chlorine, bromine, iodine, hydroxyl, cyano, nitro, -CH3、-CH2CH3、-CH2CH2CH3、-CH(CH3)2、-CH2CH2CH2CH3、-C(CH3)3、-OCH3、-OCH2CH3、-OCH2CH2CH3、-OCH(CH3)2、-CHF2、-CF3、-N(CH3)2、-SCH3、-SCF3or-OCF3；
Ra1、Rb1、Rc1、Rd1And Re1Each independently is hydrogen, fluorine, chlorine, bromine or iodine;
Rf1is hydrogen, -CH3or-CH2CH3。
6. A compound according to claim 3, wherein:
R12is-CH2CH3、-CH2CH2CH3、-CH(CH3)2、-CH2CH2CH2CH3、-C(CH3)3、-CH2C(CH3)3、CH2＝CH-、CH2＝CHCH2-, cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.
7. A compound according to claim 3, wherein:
R13is C2-6An alkyl group; preferably, R13is-CH2CH3、-CH2CH2CH3、-CH(CH3)2or-C (CH)3)3；
Or R13Is of the sub-structure:
Figure FDA0002273053230000032
Ra2、Rb2、Rc2、Rd2and Re2Each independently of the others is hydrogen, fluorine, chlorine, bromine, iodine, C1-4Alkyl, halo C1-4Alkyl radical, C1-4Alkoxy or halo C1-4An alkoxy group.
8. The compound of claim 7, wherein:
R13is of the sub-structure:
Figure FDA0002273053230000033
Ra2、Rb2、Rc2、Rd2and Re2Each independently hydrogen, fluorine, chlorine, bromine, iodine, -CH3、-CH2CH3、-CH2CH2CH3、-CH(CH3)2、-CF3or-OCF3。
9. 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 FDA0002273053230000034
Figure FDA0002273053230000041
Figure FDA0002273053230000051
Figure FDA0002273053230000061
Figure FDA0002273053230000071
10. a composition comprising a compound according to any one of claims 1 to 9 and an agriculturally acceptable adjuvant.
11. A compound according to any one of claims 1 to 9 or a composition according to claim 10 for use as a pest control agent.
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