WO2025026292A1 - 4-membered cyclic amide compound and use thereof - Google Patents

Abstract

The present invention belongs to the technical field of pesticides, and specifically relates to a 4-membered cyclic amide compound, a stereoisomer/an isomer/an enantiomer/a salt and an N-oxide thereof, and the use thereof. The compound is as shown in general formula I: (I), wherein J₁, J₂, J₃, and J₄ each independently represent N or C-M, and at least one represents N; M represents hydrogen, halogen, cyano, nitro, alkyl, alkenyl, alkynyl, haloalkyl, etc.; and R₁, R₂, R₃, R₄, and R₅ each independently represent hydrogen, halogen, etc. The compound has an excellent effect on preventing and controlling pests and/or fungi (especially nematodes).

Description

Four-membered ring amide compounds and their applications Technical Field

The invention belongs to the technical field of pesticides, and specifically relates to a four-membered ring amide compound, its stereoisomers/isomers/enantiomers/salts and N-oxides and applications thereof.

Background Art

In recent years, due to the long-term use of pest control agents, such as insecticides or fungicides, pests and diseases have acquired drug resistance and become difficult to control with the existing insecticides or fungicides. In addition, some of the known pest control agents are highly toxic, or some of them damage the ecosystem through their long-term residual properties. In this case, although a large number of nematicides are known, such as WO2013143811A1 discloses N-cyclic amide compounds and their use as nematicides, there is still a need to develop new pest control agents with low toxicity and low residual properties.

Summary of the invention

In order to solve the above problems existing in the prior art, the present invention provides a four-membered ring amide compound, its stereoisomers/isomers/enantiomers/salts and N-oxides, wherein the compound has excellent control effect on harmful organisms and/or fungi (especially nematodes).

The technical solution adopted by the present invention is as follows:

A four-membered ring amide compound, its stereoisomers/isomers/enantiomers/salts and N-oxides:

wherein J ₁ , J ₂ , J ₃ , and J ₄ independently represent N or CM, and at least one of them is N;

M represents hydrogen, halogen, cyano, nitro, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, alkoxy, alkylthio, or cycloalkyl or cycloalkylalkyl which is unsubstituted or substituted by alkyl or halogen, or M on two adjacent carbon atoms together form -CH=CH-CH=CH- or -N=CH-CH=CH-;

R ₁ , R ₂ , R ₃ , R ₄ , and R ₅ each independently represent hydrogen, halogen, nitro, cyano, thiocyano, hydroxyl, mercapto, carboxyl, sulfonic acid, formyl, haloformyl, azido, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, heterocyclic, aryl, -N(R ₂₁ ) ₂ , -(CO)N(R ₂₁ ) ₂ , -O(CO)N(R ₂₁ ) ₂ , -O(CS)N(R ₂₁ ) ₂ , -(SO ₂ )N(R ₂₁ ) ₂ , -O(SO ₂ )N(R ₂₁ ) ₂ , -PO(OR ₂₂ ) ₂ , -OR ₂₂ , -(CO)R ₂₂ , -SR ₂₂ , -(SO)R ₂₂ , -(SO ₂ )R ₂₂ , -Si(R ₂₂ ) ₃ , -O(CO)R ₂₂ , -O-(SO ₂ )R ₂₂ , -S(CO)R ₂₂ , -(SO ₂ )OR ₂₂ , -O(CO)OR ₂₂ , -(CO)(CO)OR ₂₂ , -(CO)OR ₂₂ , -ON＝C(R ₂₃ ) ₂ , -CR ₂₃ ＝N-OH or -CR ₂₃ ＝NOR ₂₂ , wherein the “alkyl”, “alkenyl” or “alkynyl” is optionally selected from halogen, nitro, cyano, hydroxyl, thiol, carboxyl, cycloalkyl, cycloalkenyl, heterocyclyl, aryl, -N(R ₂₁ ) ₂ , -(CO)N(R ₂₁ ) ₂ , -O(CO)N(R ₂₁ ) ₂ , -O(CS)N(R ₂₁ ) ₂ , -(SO ₂ )N(R ₂₁ ) ₂ , -O(SO ₂ )N(R ₂₁ ) ₂ , -OR ₂₂ , -(CO)R ₂₂ , -SR ₂₂ , -(SO)R ₂₂ , -(SO ₂ )R ₂₂ , -O(CO)H, -O(CO)R ₂₂ , -O-(SO ₂ )R ₂₂ , -(CO)OR ₂₂ , -O(CO)OR ₂₂ , -Si(R ₂₂ ) ₃ , -O(CO)(CO)OH, -O(CO)(CO)OR ₂₂ , -O-alkylene-(CO)OH or -O-alkylene-(CO)OR ₂₂ ;

R ₂₁ each independently represents hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, aryl, heterocyclyl, -OR ₂₂ , -(CO)R ₂₂ , -(CO)OR ₂₂ , -alkylene-(CO)OR ₂₂ , -(SO ₂ )R ₂₂ , -(SO ₂ )OR ₂₂ , -alkylene-(SO ₂ )R ₂₂ , -(CO)N(R ₂₄ ) ₂ or -(SO ₂ )N(R ₂₄ ) ₂ ;

R ₂₂ each independently represents an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a cycloalkenyl group, an aryl group or a heterocyclyl group, wherein the “alkyl group”, “alkenyl group” or “alkynyl group” is optionally substituted by at least one group selected from halogen, cyano, trialkylsilyl, cycloalkyl group, cycloalkenyl group, aryl group, heterocyclyl group, -OR ₂₅ , -SR ₂₅ , -O(CO)R ₂₅ , -(CO)R ₂₅ , -(CO)OR ₂₅ or -O(CO)OR ₂₅ ;

_R23 each independently represents hydrogen, halogen, alkoxy, alkoxyalkyl, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkylalkyl, cycloalkenyl, cycloalkenylalkyl, aryl, arylalkyl, heterocyclyl or heterocyclylalkyl;

R ₂₄ each independently represents hydrogen, alkyl, alkenyl, alkynyl, alkoxy, alkylsulfonyl, cycloalkyl, cycloalkylalkyl, cycloalkenyl or cycloalkenylalkyl;

or N(R ₂₁ ) ₂ and N(R ₂₄ ) ₂ each independently represent a heterocyclic group with a nitrogen atom at the 1-position;

R ₂₅ each independently represents hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, haloalkyl, haloalkenyl, haloalkynyl, phenyl or phenyl substituted by at least one group selected from the following: halogen, cyano, nitro, alkyl, haloalkyl, alkoxy, haloalkoxy, alkoxycarbonyl, alkylthio, alkylsulfonyl or phenoxy substituted by at least one group selected from the following: halogen, cyano, nitro, alkyl, haloalkyl, alkoxy or haloalkoxy;

The aforementioned “cycloalkyl”, “cycloalkenyl”, “heterocyclyl” or “aryl” is optionally substituted by at least one group selected from oxo, halogen, cyano, nitro, alkyl, alkenyl, alkynyl, cycloalkyl, haloalkyl, haloalkenyl, haloalkynyl, halocycloalkyl, cycloalkyl substituted by alkyl, _-OR10 , _-SR10 , -(CO) _OR10 , -( _SO2 ) _R10 , -N( _R10 ) ₂ or -O-alkylene-(CO) _OR10 , or two adjacent carbon atoms on the ring form a condensed ring with unsubstituted or halogen-substituted _-OCH2CH2- or _{-OCH2O- ;}

_R10 each independently represents hydrogen, alkyl, haloalkyl, phenyl, or phenyl substituted by at least one group selected from halogen, cyano, nitro, alkyl, haloalkyl, alkoxycarbonyl, alkylthio, alkylsulfonyl, alkoxy or haloalkoxy.

In a specific embodiment, M represents hydrogen, halogen, cyano, nitro, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, halogenated C1-C8 alkyl, halogenated C2-C8 alkenyl, halogenated C2-C8 alkynyl, C1-C8 alkoxy, C1-C8 alkylthio, or C3-C8 cycloalkyl or C3-C8 cycloalkylC1-C8 alkyl which is unsubstituted or substituted with C1-C8 alkyl or halogen, or M on two adjacent carbon atoms together form -CH=CH-CH=CH- or -N=CH-CH=CH-;

R ₁ , R ₂ , R ₃ , R ₄ , and R ₅ each independently represent hydrogen, halogen, nitro, cyano, thiocyano, hydroxyl, mercapto, carboxyl, sulfonic acid, formyl, haloformyl, azido, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 cycloalkyl, C3-C8 cycloalkenyl, heterocyclic group, aryl, -N(R ₂₁ ) ₂ , -(CO)N(R ₂₁ ) ₂ , -O(CO)N(R ₂₁ ) ₂ , -O(CS)N(R ₂₁ ) ₂ , -(SO ₂ )N(R ₂₁ ) ₂ , -O(SO ₂ )N(R ₂₁ ) ₂ , -PO(OR ₂₂ ) ₂ , -OR ₂₂ , -(CO)R ₂₂ -SR ₂₂ , -(SO)R ₂₂ , -(SO ₂ )R ₂₂ , -Si(R ₂₂ ) ₃ , -O(CO)R ₂₂ , -O-(SO ₂ )R ₂₂ , -S(CO)R ₂₂ , -(SO ₂ )OR ₂₂ , -O(CO)OR ₂₂ , -(CO)(CO)OR ₂₂ , -(CO)OR ₂₂ , -ON＝C(R ₂₃ ) ₂ , -CR ₂₃ ＝N-OH or -CR ₂₃ ＝NOR ₂₂ , wherein the “C1-C8 alkyl”, “C2-C8 alkenyl” or “C2-C8 alkynyl” is optionally selected from halogen, nitro, cyano, hydroxyl, thiol, carboxyl, C3-C8 cycloalkyl, C3-C8 cycloalkenyl, heterocyclyl, aryl, -N(R 23 ) 2 ₂₁ ) ₂ , -(CO)N(R ₂₁ ) ₂ , -O(CO)N(R ₂₁ ) ₂ , -O(CS)N(R ₂₁ ) ₂ , -(SO ₂ )N(R ₂₁ ) ₂ , -O(SO ₂ )N(R ₂₁ ) ₂ , -OR ₂₂ , -(CO)R ₂₂ , -SR ₂₂ , -(SO)R ₂₂ , -(SO ₂ )R ₂₂ , -O(CO)H, -O(CO)R ₂₂ , -O-(SO ₂ )R ₂₂ , -(CO)OR ₂₂ , -O(CO)OR ₂₂ , -Si(R ₂₂ ) ₃ , -O(CO)(CO)OH, -O(CO)(CO)OR ₂₂ , -O-(C1-C8 alkylene)-(CO)OH or -O-(C1-C8 alkylene)-(CO)OR ₂₂ ;

R ₂₁ each independently represents hydrogen, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 cycloalkyl, C3-C8 cycloalkenyl, aryl, heterocyclyl, -OR ₂₂ , -(CO)R ₂₂ , -(CO)OR ₂₂ , -(C1-C8 alkylene)-(CO)OR ₂₂ , -(SO ₂ )R ₂₂ , -(SO ₂ )OR ₂₂ , -(C1-C8 alkylene)-(SO ₂ )R ₂₂ , -(CO)N(R ₂₄ ) ₂ or -(SO ₂ )N(R ₂₄ ) ₂ ;

R ₂₂ each independently represents a C1-C8 alkyl group, a C2-C8 alkenyl group, a C2-C8 alkynyl group, a C3-C8 cycloalkyl group, a C3-C8 cycloalkenyl group, an aryl group or a heterocyclyl group, wherein the “C1-C8 alkyl group”, “C2-C8 alkenyl group” or “C2-C8 alkynyl group” is optionally substituted by at least one group selected from halogen, cyano, tri-C1-C8 alkylsilyl group, C3-C8 cycloalkyl group, C3-C8 cycloalkenyl group, aryl group, heterocyclyl group, -OR ₂₅ , -SR ₂₅ , -O(CO)R ₂₅ , -(CO)R ₂₅ , -(CO)OR ₂₅ or -O(CO)OR ₂₅ ;

R ₂₃ each independently represents hydrogen, halogen, C1-C8 alkoxy, C1-C8 alkoxyC1-C8 alkyl, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 cycloalkyl, C3-C8 cycloalkylC1-C8 alkyl, C3-C8 cycloalkenyl, C3-C8 cycloalkenylC1-C8 alkyl, aryl, arylC1-C8 alkyl, heterocyclyl or heterocyclylC1-C8 alkyl;

R ₂₄ each independently represents hydrogen, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C1-C8 alkoxy, C1-C8 alkylsulfonyl, C3-C8 cycloalkyl, C3-C8 cycloalkylC1-C8 alkyl, C3-C8 cycloalkenyl or C3-C8 cycloalkenylC1-C8 alkyl;

or N(R ₂₁ ) ₂ and N(R ₂₄ ) ₂ each independently represent a heterocyclic group with a nitrogen atom at the 1-position;

R ₂₅ each independently represents hydrogen, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 cycloalkyl, halogenated C1-C8 alkyl, halogenated C2-C8 alkenyl, halogenated C2-C8 alkynyl, phenyl or phenyl substituted by at least one group selected from the following: halogen, cyano, nitro, C1-C8 alkyl, halogenated C1-C8 alkyl, C1-C8 alkoxy, halogenated C1-C8 alkoxy, C1-C8 alkoxycarbonyl, C1-C8 alkylthio, C1-C8 alkylsulfonyl or phenoxy substituted by at least one group selected from the following: halogen, cyano, nitro, C1-C8 alkyl, halogenated C1-C8 alkyl, C1-C8 alkoxy or halogenated C1-C8 alkoxy;

The aforementioned “C3-C8 cycloalkyl”, “C3-C8 cycloalkenyl”, “heterocyclyl” or “aryl” is optionally substituted by at least one group selected from oxo, halogen, cyano, nitro, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 cycloalkyl, halogenated C1-C8 alkyl, halogenated C2-C8 alkenyl, halogenated C2-C8 alkynyl, halogenated C3-C8 cycloalkyl, C3-C8 cycloalkyl substituted by C1-C8 alkyl, _-OR10 , _-SR10 , -(CO) _OR10 , -( _SO2 ) _R10 , -N( _R10 ) ₂ or -O-(C1-C8 alkylene)-(CO) _OR10 , or two adjacent carbon atoms on the ring form a condensed ring with unsubstituted or _halogen -substituted _-OCH2CH2- or _-OCH2O- ;

_R10 each independently represents hydrogen, C1-C8 alkyl, halogenated C1-C8 alkyl, phenyl, or phenyl substituted by at least one group selected from halogen, cyano, nitro, C1-C8 alkyl, halogenated C1-C8 alkyl, C1-C8 alkoxycarbonyl, C1-C8 alkylthio, C1-C8 alkylsulfonyl, C1-C8 alkoxy or halogenated C1-C8 alkoxy.

In another specific embodiment, M represents hydrogen, halogen, cyano, nitro, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, halogenated C1-C6 alkyl, halogenated C2-C6 alkenyl, halogenated C2-C6 alkynyl, C1-C6 alkoxy, C1-C6 alkylthio, or C3-C6 cycloalkyl or C3-C6 cycloalkylC1-C6 alkyl which is unsubstituted or substituted by C1-C6 alkyl or halogen, or M on two adjacent carbon atoms together form -CH=CH-CH=CH- or -N=CH-CH=CH-;

R ₁ , R ₂ , R ₃ , R ₄ , and R ₅ each independently represent hydrogen, halogen, nitro, cyano, thiocyano, hydroxyl, mercapto, carboxyl, sulfonic acid, formyl, haloformyl, azido, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, C3-C6 cycloalkenyl, heterocyclic group, aryl, -N(R ₂₁ ) ₂ , -(CO)N(R ₂₁ ) ₂ , -O(CO)N(R ₂₁ ) ₂ , -O(CS)N(R ₂₁ ) ₂ , -(SO ₂ )N(R ₂₁ ) ₂ , -O(SO ₂ )N(R ₂₁ ) ₂ , -PO(OR ₂₂ ) ₂ , -OR ₂₂ , -(CO)R ₂₂ -SR ₂₂ , -(SO)R ₂₂ , -(SO ₂ )R ₂₂ , -Si(R ₂₂ ) ₃ , -O(CO)R ₂₂ , -O-(SO ₂ )R ₂₂ , -S(CO)R ₂₂ , -(SO ₂ )OR ₂₂ , -O(CO)OR ₂₂ , -(CO)(CO)OR ₂₂ , -(CO)OR ₂₂ , -ON＝C(R ₂₃ ) ₂ , -CR ₂₃ ＝N-OH or -CR ₂₃ ＝NOR ₂₂ , wherein the “C1-C6 alkyl”, “C2-C6 alkenyl” or “C2-C6 alkynyl” is optionally selected from halogen, nitro, cyano, hydroxyl, thiol, carboxyl, C3-C6 cycloalkyl, C3-C6 cycloalkenyl, heterocyclyl, aryl, -N(R 23 ) 2 ₂₁ ) ₂ , -(CO)N(R ₂₁ ) ₂ , -O(CO)N(R ₂₁ ) ₂ , -O(CS)N(R ₂₁ ) ₂ , -(SO ₂ )N(R ₂₁ ) ₂ , -O(SO ₂ )N(R ₂₁ ) ₂ , -OR ₂₂ , -(CO)R ₂₂ , -SR ₂₂ , -(SO)R ₂₂ , -(SO ₂ )R ₂₂ , -O(CO)H, -O(CO)R ₂₂ , -O-(SO ₂ )R ₂₂ , -(CO)OR ₂₂ , -O(CO)OR ₂₂ , -Si(R ₂₂ ) ₃ , -O(CO)(CO)OH, -O(CO)(CO)OR ₂₂ , -O-(C1-C6 alkylene)-(CO)OH or -O-(C1-C6 alkylene)-(CO)OR ₂₂ ;

R ₂₁ each independently represents hydrogen, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, C3-C6 cycloalkenyl, aryl, heterocyclyl, -OR ₂₂ , -(CO)R ₂₂ , -(CO)OR ₂₂ , -(C1-C6 alkylene)-(CO)OR ₂₂ , -(SO ₂ )R ₂₂ , -(SO ₂ )OR ₂₂ , -(C1-C6 alkylene)-(SO ₂ )R ₂₂ , -(CO)N(R ₂₄ ) ₂ or -(SO ₂ )N(R ₂₄ ) ₂ ;

R ₂₂ each independently represents a C1-C6 alkyl group, a C2-C6 alkenyl group, a C2-C6 alkynyl group, a C3-C6 cycloalkyl group, a C3-C6 cycloalkenyl group, an aryl group or a heterocyclyl group, wherein the “C1-C6 alkyl group”, “C2-C6 alkenyl group” or “C2-C6 alkynyl group” is optionally substituted by at least one group selected from halogen, cyano, tri-C1-C6 alkylsilyl group, C3-C6 cycloalkyl group, C3-C6 cycloalkenyl group, aryl group, heterocyclyl group, -OR ₂₅ , -SR ₂₅ , -O(CO)R ₂₅ , -(CO)R ₂₅ , -(CO)OR ₂₅ or -O(CO)OR ₂₅ ;

R ₂₃ each independently represents hydrogen, halogen, C1-C6 alkoxy, C1-C6 alkoxyC1-C6 alkyl, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, C3-C6 cycloalkylC1-C6 alkyl, C3-C6 cycloalkenyl, C3-C6 cycloalkenylC1-C6 alkyl, aryl, arylC1-C6 alkyl, heterocyclyl or heterocyclylC1-C6 alkyl;

R ₂₄ each independently represents hydrogen, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C1-C6 alkoxy, C1-C6 alkylsulfonyl, C3-C6 cycloalkyl, C3-C6 cycloalkylC1-C6 alkyl, C3-C6 cycloalkenyl or C3-C6 cycloalkenylC1-C6 alkyl;

or N(R ₂₁ ) ₂ and N(R ₂₄ ) ₂ are each independently unsubstituted or substituted by at least one group selected from oxo, C1-C6 alkyl or C1-C6 alkoxycarbonyl.

R ₂₅ each independently represents hydrogen, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, halogenated C1-C6 alkyl, halogenated C2-C6 alkenyl, halogenated C2-C6 alkynyl, phenyl or phenyl substituted by at least one group selected from the following: halogen, cyano, nitro, C1-C6 alkyl, halogenated C1-C6 alkyl, C1-C6 alkoxy, halogenated C1-C6 alkoxy, C1-C6 alkoxycarbonyl, C1-C6 alkylthio, C1-C6 alkylsulfonyl or phenoxy substituted by at least one group selected from the following: halogen, cyano, nitro, C1-C6 alkyl, halogenated C1-C6 alkyl, C1-C6 alkoxy or halogenated C1-C6 alkoxy;

The aforementioned “C3-C6 cycloalkyl”, “C3-C6 cycloalkenyl”, “heterocyclyl” or “aryl” is optionally selected from oxo, halogen, cyano, nitro, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, halogenated C1-C6 alkyl, halogenated C2-C6 alkenyl, halogenated C2-C6 alkynyl, halogenated C3-C6 cycloalkyl, C3-C6 cycloalkyl substituted by C1-C6 alkyl, _{or two adjacent} carbon atoms on the _ring form a condensed ring with _{unsubstituted} or _{halogen-substituted -OCH 2 CH 2 - or -OCH 2 O- ;}

_R10 each independently represents hydrogen, C1-C6 alkyl, halogenated C1-C6 alkyl, phenyl, or phenyl substituted by at least one group selected from halogen, cyano, nitro, C1-C6 alkyl, halogenated C1-C6 alkyl, C1-C6 alkoxycarbonyl, C1-C6 alkylthio, C1-C6 alkylsulfonyl, C1-C6 alkoxy or halogenated C1-C6 alkoxy.

In the definition of the compounds represented by the above general formula and in all the following structural formulae, the technical terms used, whether used alone or in compound words, represent the following substituents: Alkyl groups with more than two carbon atoms may be straight-chain or branched. For example, in the compound word "-O-alkylene-(CO)OH", the alkyl group may be -CH ₂ -, -CH ₂ CH ₂ -, -CH(CH ₃ )-, -C(CH ₃ ) ₂ -, etc. Alkyl groups are, for example, C1 alkyl-methyl; C2 alkyl-ethyl; C3 alkyl-propyl such as n-propyl or isopropyl; C4 alkyl-butyl such as n-butyl, isobutyl, tert-butyl or 2-butyl; C5 alkyl-pentyl such as n-pentyl; C6 alkyl-hexyl such as n-hexyl, isohexyl and 1,3-dimethylbutyl. Similarly, alkenyl is, for example, vinyl, allyl, 1-methylprop-2-ene-1-yl, 2-methylprop-2-ene-1-yl, but-2-ene-1-yl, but-3-ene-1-yl, 1-methylbut-3-ene-1-yl and 1-methylbut-2-ene-1-yl. Alkynyl is, for example, ethynyl, propargyl, but-2-yn-1-yl, but-3-yn-1-yl, 1-methylbut-3-yn-1-yl. Multiple bonds can be at any position of each unsaturated group. Cycloalkyl is a carbocyclic saturated ring system with, for example, three to six carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl. Similarly, cycloalkenyl is a monocyclic alkenyl with, for example, three to six carbocyclic ring members, such as cyclopropenyl, cyclobutenyl, cyclopentenyl and cyclohexenyl, wherein double bonds can be at any position. Halogen is fluorine, chlorine, bromine or iodine.

Unless otherwise specified, the "aryl" mentioned in the present invention includes but is not limited to phenyl, naphthyl, The "heterocyclic group" includes but is not limited to saturated or unsaturated non-aromatic cyclic groups etc., also including but not limited to heteroaryl, i.e. aromatic cyclic groups containing, for example, 3 to 6 ring atoms and optionally fused to a benzo ring, wherein 1 to 4 (e.g. 1, 2, 3 or 4) heteroatoms among the ring atoms are selected from oxygen, nitrogen and sulfur, for example

If a group is substituted by a group, this is understood to mean that the group is substituted by one or more identical or different groups selected from those mentioned. In addition, identical or different substitution characters contained in identical or different substituents are independently selected and may be identical or different. The same applies to ring systems formed by different atoms and units. At the same time, the scope of the claims will exclude compounds that are known to the person skilled in the art to be chemically unstable under standard conditions.

In addition, unless otherwise specified, the term "substituted by at least one group" in the present invention means substituted by 1, 2, 3, 4 or 5 groups; groups (including heterocyclic groups, aryl groups, etc.) without specific connection positions can be connected at any position, including the position connected to C or N; if it is substituted, the substituent can also be substituted at any position as long as it complies with the chemical bond connection rules. For example, a heteroaryl group substituted by 1 methyl group Can represent wait.

The present invention also provides a four-membered ring amide compound having a cis structure as shown in Formula I', and its stereoisomers/isomers/enantiomers/salts and N-oxides:

wherein the substituents J ₁ , J ₂ , J ₃ , J ₄ , R ₁ , R ₂ , R ₃ , R ₄ and R ₅ are as defined above, and They are cis relative to each other on the four-membered ring.

The present invention also provides a four-membered ring amide compound having a chiral center as shown in Formula I", and its stereoisomers/isomers/enantiomers/salts and N-oxides:

Wherein, substituents J ₁ , J ₂ , J ₃ , J ₄ , R ₁ , R ₂ , R ₃ , R ₄ and R ₅ are defined as above; the carbon atoms at positions 1 and 2 on the four-membered ring are both chiral centers, and have a stereochemical purity of 60-100% (R), preferably 70-100% (R), more preferably 80-100% (R), further preferably 90-100% (R), and even more preferably 95-100% (R), based on the contents of stereoisomers with R and S configurations at these positions, respectively.

The present invention also provides a four-membered ring amide compound having a chiral center as shown in Formula I'', and its stereoisomers/isomers/enantiomers/salts and N-oxides:

Wherein, substituents J ₁ , J ₂ , J ₃ , J ₄ , R ₁ , R ₂ , R ₃ , R ₄ and R ₅ are defined as above; the carbon atoms at positions 1 and 2 on the four-membered ring are both chiral centers, and have a stereochemical purity of 60-100% (S), preferably 70-100% (S), more preferably 80-100% (S), further preferably 90-100% (S), and even more preferably 95-100% (S), based on the contents of stereoisomers with R and S configurations at these positions, respectively.

Here, "stereochemical purity" refers to the percentage of the amount of the stereoisomer in question to the total amount of stereoisomers having a chiral center.

The compounds of formula I in each case in free form or in salt form, and where appropriate their tautomers, may be present in the form of one of the possible isomers or as a mixture of these, for example in the form of pure isomers, such as enantiomers and/or diastereomers, or as isomer mixtures, such as enantiomeric mixtures, for example racemates, diastereomeric mixtures or racemic mixtures, depending on the number, absolute and relative configuration of the asymmetric carbon atoms present in the molecule, and/or on the configuration of the non-aromatic double bonds present in the molecule; the present invention relates to these pure isomers and also to all possible isomer mixtures and should be understood in this sense in each case above and below, even if no specific mention is made of stereochemical details in each case. The present invention therefore encompasses all such isomers and tautomers and their mixtures in all proportions, together with isotopic forms, such as deuterated compounds.

The present invention also encompasses salts or N-oxides of each compound of formula I.

Those of ordinary skill in the art also understand that since salts of compounds are in equilibrium with their corresponding non-salt forms in the environment and under physiological conditions, salts also have the biological utility of the non-salt form.

Therefore, various salts of the compounds of the present invention (and active ingredients used in combination with the active ingredients of the present invention) can be used to control invertebrate pests and animal parasites. Agriculturally and/or physiologically acceptable salts include those with the following inorganic acids or organic acids: Acid addition salts formed with organic acids such as hydrobromic acid, hydrochloric acid, nitric acid, phosphoric acid, sulfuric acid, acetic acid, butyric acid, fumaric acid, lactic acid, maleic acid, malonic acid, oxalic acid, propionic acid, salicylic acid, tartaric acid, 4-toluenesulfonic acid or valeric acid.

Suitable among the agriculturally and/or physiologically tolerable salts are also cationic salts which do not adversely affect the pesticidal and/or parasiticidal action of the compounds of formula I. Thus, particularly suitable cations are ions of alkali metals including sodium, potassium and lithium, ions of alkaline earth metals including calcium and magnesium, and ions of transition metals including manganese, copper, iron, zinc, cobalt, lead, silver, nickel; and also ammonium or organoammonium including monoalkylammonium, dialkylammonium, trialkylammonium, tetraalkylammonium, monoalkenylammonium, dialkenylammonium, trialkenylammonium, monoalkynylammonium, dialkynylammonium, monoalkanolammonium, dialkanolammonium, C5-C6-cycloalkylammonium, piperidinium, morpholinium, pyrrolidinium or benzylammonium, furthermore phosphonium ions, sulfonium ions, preferably tri(C1-C4-alkyl)sulfonium and sulfoxonium ions, preferably tri(C1-C4-alkyl)sulfoxonium.

The compounds of formula I can exist in different tautomeric forms. The present invention encompasses all those tautomeric forms and mixtures thereof.

Diastereomeric mixtures or mixtures of racemates of compounds of formula I in free or salt form, which may be obtained depending on the starting materials and procedures chosen, can be separated into the pure diastereomers or racemates by a known method on the basis of the physicochemical differences of the components, for example by fractional crystallization, distillation and/or chromatography.

Enantiomeric mixtures (e.g. racemates) can be obtained by a similar process and they can be resolved into the optical antipodes by known methods, for example by recrystallization from optically active solvents; by chromatography on chiral adsorbents, for example high performance liquid chromatography (HPLC) on acetylcellulose; by cleavage using specific immobilized enzymes with the aid of suitable microorganisms; in the case where only one enantiomer is complexed, via the formation of an inclusion complex, for example using chiral crown ethers; or by conversion into diastereomeric salts, for example by reacting a basic end product racemate with an optically active acid (e.g. a carboxylic acid, for example camphoric acid, tartaric acid or malic acid, or a sulfonic acid, for example camphorsulfonic acid), and separating the diastereomeric mixtures obtainable in this way (e.g. by fractional crystallization according to their different solubilities) to give the diastereoisomers from which the desired enantiomer can be liberated by the action of a suitable reagent (e.g. a basic reagent).

Pure diastereomers or enantiomers can be obtained according to the invention not only by separation of appropriate isomer mixtures but also by generally known diastereoselective or enantioselective synthetic methods, for example by carrying out the method according to the invention using a starting material of an appropriate stereochemistry.

N-oxides can be prepared by reacting a compound of formula I with a suitable oxidizing agent, such as H ₂ O ₂ /urea adducts, in the presence of an anhydride, such as trifluoroacetic anhydride. Such oxidations are known from the literature, for example from J. Med. Chem., 32 (12), 2561-73, 1989 or WO 00/15615 or C. White, Science, vol 318, p. 783, 2007.

If the individual components have different biological activities, it is advantageous to isolate or synthesize the biologically more effective isomer, such as an enantiomer or diastereomer, or isomer mixtures, such as enantiomeric mixtures or diastereomeric mixtures, in each case.

The compounds of the formula I and, where appropriate, their tautomers (in each case in free form or salt form) can, if appropriate, also be obtained in the form of hydrates and/or include further solvents, such as those which can be used for the crystallization of compounds present in solid form.

The present invention also provides a method for preparing a four-membered ring amide compound, its stereoisomers/isomers/enantiomers/salts and N-oxides, comprising the following steps:

The compound represented by the general formula II is reacted with the compound represented by the general formula III to obtain the compound represented by the general formula I, and the reaction equation is as follows:

wherein M represents OH or halogen, and the substituents R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , J ₁ , J ₂ , J ₃ , and J ₄ are as defined above;

In one embodiment, the reaction is carried out in the presence of a solvent.

In another embodiment, a condensing agent and/or a base is added during the reaction.

In a specific embodiment, the solvent is selected from at least one of DMF, DMA, methanol, ethanol, acetonitrile, dichloroethane, DMSO, Dioxane, dichloromethane (DCM) or ethyl acetate.

In a specific embodiment, the base is at least one selected from inorganic bases (such _{as K2CO3} , _{Na2CO3 , Cs2CO3 , NaHCO3} , _KF , CsF, KOAc, AcONa, _K3PO4 , t- _BuONa , EtONa, NaOH, KOH, NaOMe, etc.) or organic bases (such as pyrazole, triethylamine, DIEA, etc.).

In a specific embodiment, the condensing agent is selected from at least one of Py-BOP, Py-AOP, EDCI, HOBT (1-hydroxybenzotriazole), DCC, HBTU or HATU.

In addition, the compound shown in general formula I can also be prepared by referring to the methods shown in WO2015003951 A1, WO2013143811A1, etc.

The present invention also provides a composition for killing pests and/or fungi (especially nematodes), comprising a biologically effective amount of the four-membered ring amide compound, at least one of its stereoisomers/isomers/enantiomers/salts and N-oxides.

In a specific embodiment, the composition further comprises a formulation aid.

In another specific embodiment, the composition further comprises other effective ingredients.

The present invention also provides a method for controlling harmful organisms and/or fungi (especially nematodes), comprising contacting the harmful organisms and/or fungi (especially nematodes) or their environment with a biologically effective amount of the four-membered ring amide compound, its stereoisomers/isomers/enantiomers/salts and N-oxides or the composition.

The present invention also provides the use of the four-membered ring amide compound, its stereoisomer/isomer/enantiomer/salt and N-oxide or the composition in preventing and controlling harmful organisms and/or fungi (especially nematodes).

It has been found that compounds of formula I, I', I" or I'" are useful for controlling damage caused by pests and/or fungi.

In one embodiment, the compound of Formula I, I', I" or I'" can be used in agriculture.

Therefore, the present invention is further directed to a method for controlling damage and/or yield losses caused by pests and/or fungi, which method comprises applying an effective amount of a compound of formula I, I', I" or I'" to the pest, to the locus of the pest, or to a plant susceptible to attack by pests and/or fungi or to plant propagation material.

The compounds according to the invention can be used for controlling, i.e. limiting or destroying, harmful organisms and/or fungi which occur in particular on plants, especially on useful and ornamental plants in agriculture, horticulture and forestry, or on organs of such plants, such as fruits, flowers, leaves, stalks, rhizomes, seeds or roots, and in some cases even on plant organs formed at a later point in time, still protecting against these harmful organisms.

The compounds of the formula I, I', I" or I'" according to the invention are active ingredients of preventive and/or therapeutic value in the field of pest control. They can be used against pests and/or fungi resistant to pesticides even at low application rates. The compounds of the formula I, I', I" or I'" have a very favorable biocidal spectrum and are well tolerated by warm-blooded species, fish and plants.

The compounds according to the invention can act on all or individual developmental stages of normally sensitive and also resistant animal pests, such as insects or representatives of the order Acarina. The insecticidal or acaricidal activity of the compounds according to the invention can manifest itself directly, i.e., for example, by the destruction of the pests during molting, which occurs immediately or after a certain period of time, or indirectly, for example, by reduced egg laying and/or hatching rates, good activity corresponding to a destruction rate (mortality) of at least 50% to 60%.

It has now been found that the compounds of formula I, I', I" or I'" according to the invention have (for practical purposes) a very advantageous spectrum of activity for protecting animals and useful plants against attack and damage by nematodes. The present invention therefore also makes available nematicidal compositions comprising the compounds of the invention, such as formula I, I', I" or I'"

The compounds of formula I, I', I" or I'" are particularly useful for the control of nematodes. In another aspect, the present invention therefore also relates to a method for controlling damage to plants or parts thereof caused by plant-parasitic nematodes (endoparasitic-, semi-endoparasitic- and ectoparasitic nematodes), in particular the following plant-parasitic nematodes, such as root knot nematodes, Meloidogyne hapla, Meloidogyne incognita, Meloidogyne javanica, Meloidogyne arenaria and other Meloidogyne species; cyst-forming nematodes, Globodera rostochiensis and other Globodera species; cereal cyst nematodes, Heterodera avenae, Heterodera glycines, Heterodera schachtii and Heterodera schachtii. schachtii), Heterodera trifolii, and other Heterodera species; Seed gall nematodes, Anguina species; Stem and foliar nematodes, Aphelenchoides species; Sting nematodes, Eelonolaimus longicaudatus, and other Belonolaimus species; Pine nematodes, Bursaphelenchus xylophilus, and other Bursaphelenchus species; Ring nematodes, Criconema species, Criconemella species, Criconemoides species Stem and bulb nematodes, Ditylenchus destructor, Ditylenchus dipsaci, and other Ditylenchus species; Awl nematodes, Dolichodorus species; Spiral nematodes, Heliocotylenchus multicinctus, and other Helicotylenchus species; Sheath and sheathoid nematodes, Hemicycliophora species, and Hemicriconemoides species; Hirshmanniella species; Lance nematodes, Hoploaimus species; false rootknot nematodes, Nacobbus species; Needle nematodes, Longidorus elongatus, and other Longidorus species; Pin nematodes, Pratylenchus species; Lesion nematodes, Pratylenchus neglectus, Pratylenchus penetrans, Pratylenchus curvitatus, Pratylenchus goodeyi, and other Pratylenchus species; Burrowing nematodes nematodes, Radopholus similis and other Radopholus species; Reniform nematodes, Rotylenchus robustus, Rotylenchus reniformis and other Rotylenchus species; Scutellonema species; Stubby root nematodes, Trichodorus primitivus and other Trichodorus species, Paratrichodorus species; Stunt nematodes, Tylenchorhynchus claytoni, Tylenchorhynchus dubius and other Tylenchorhynchus species nematodes; Citrus nematodes, Tylenchulus species; Dagger nematodes, Xiphinema species; and other plant-parasitic nematode species, such as Subanguina spp., Hypsoperine spp., Macroposthonia spp., Melinius spp., Punctodera spp., and Quinisulcius spp.

In particular, the following nematode species can be controlled by the compounds according to the invention: Meloidogyne spp., Heterodera spp., Spirodactyle spp. and Pratylenchus spp.

Examples of animal pests are:

- From the order Acarina, for example,

Acalitus spp., Acalitus spp., Acaricalus spp., Aceria spp., Acarina ...

- From the order Phthinidae, for example,

Haematoptes, Longignathus, Human lice, Pemphigus, and Psyllids;

- from the order Coleoptera, e.g.

Amphimallon majale, Amphimallon majale, Astylus atromaculatus, Ataenius spp., Atomaria linearis, Cerotoma spp., Cerotoma spp., Green beetle, Cerotoma spp., Rhinoceros beetle, Rhinoceros beetle, Diloboderus abderus, Eremnus spp., Black sugar beetle, Coffee berry borer, Lagria vilosa, Potato beetle, Liogenys spp., Maecolaspis spp., chestnut-colored scarab beetles, American leaf beetles (Megascelis spp.), Melighetes aeneus, scarab beetles, Myochrous armatus, saw-saw grain beetles, ear-beaked weevils (Otiorhynchus spp.), branchial-horned scarab beetles, spotted weevils, beautiful scarab beetles, rape flea beetles, Rhyssomatus aubtilis, root-robber beetles, scarab beetles, rice weevils, wheat moths, pseudo-root-cutting beetles, pointed hidden weevils (Sphenophorus spp.), soybean stem weevils, pseudo-walking beetles, pseudo-castanum beetles and trophoderm beetles;

- from the order Diptera, e.g.

Aedes spp., Anopheles spp., Sorghum fly, Bactrocea oleae, Garden fly, Bradysia spp., Red headed blowfly, Bactrocera spp., Chrysophora spp., Culex spp., Yellow fly, Oligobacter spp., Drosophila spp., Drosophila spp., Gastrophora spp., Glossina spp., Dermatophagus spp., Limphia spp., Lymphoma spp., Lymphoma spp., Mushroom spp., Musca spp., Mushroom spp., Sternberg spp., Grass fly, Bactrocera spp., Rivelia quadrifasciata, Scatella spp., Fungi spp., Bitter fly, Taphna spp., Tapon spp., Centrifuge spp., Tapsus spp., Taenia ...

- from the order Hemiptera, e.g.

Acanthocoris scabrator, Amblypelta nitida, Bathycoelia thalassina, Acanthocoeli, Clavigralla tomentosicollis, Creontiades spp., Dichelops furcatus, Edessa spp., Euchystomus spp., Eurydema pulchrum, H. orcias nobilellus), rice-margin stink bugs, grass stink bugs, tropical scale bugs, Murgantia histrionic, Neomegalotomus spp., tobacco blind bugs (Nesidiocoris tenuis), green stink bugs, Nysius simulans, Oebalus insularis, skin stink bugs, wall stink bugs, red assassin bugs, cocoa blind bugs, Scaptocoris castanea, black stink bugs (Scotinophara spp.), Thyanta spp., trypanorrhinae, cassava web bugs (Vatiga illudens);

- from the order Homoptera, e.g.

Aphids, Adalges spp., Agalliana ensigera, Agonascena targionii, Aleurodicus spp., Aleurocanthus spp., Sugarcane hole whitefly, Aleurothrixus floccosus, Aleyrodes brassicae, Amarasca biguttula, Amritodus atkinson, Scale spp., Aphididae, Aphids, Scale spp., Solanum spp., Bactericera cockerelli, Aleurodicus spp., Brachycaudus spp., Cabbage aphid, Cavariella aegopodii Scop.), Lecanus spp., Brown round scale, Webgrass leaf round scale, Cicadella spp., Cofana spectra, Cryptomelania spp., Cicadulina spp., Brown soft scale, Corn yellow-winged leafhopper, Whitefly spp., Citrus psyllid, Wheat two-tailed aphid, Western round tail aphid, Small green leafhopper, Apple aphid, Grape leafhopper spp., Wax clam spp., Red eucalyptus psyllid (Glycaspis brimblecombei), Cabbage aphid, Big tail aphid (Hyalopterus spp.), Super tumor aphid species, Lemon fruit green leafhopper (Idioscopus clypealis), Jacobiasca lybica, Laodelphax spp., Ball-hard scale, Oyster shield scale spp., Turnip aphid (Lopaphis erysimi), Lyogenys maidis, Longitubular aphid spp., Mahanarva spp., Metcalfa pruinosa), wheat aphid, Myndus crudus, aphid, Taiwan leek aphid, black tail leafhopper, brown planthopper (Nilaparvata spp.), pear green aphid, Odonaspis ruthae, parasitic sugarcane aphid, bayberry whitefly, Caulis psyllid, shield scale, gall aphid, corn wax cicada, flat horned planthopper, hop wart aphid, root aphid, Mobilococcus, white shield scale, mealybug, cotton blind bug (Pseudatomoscelis seriatus), psyllid, cotton scale (Pulvinaria aethiopica), round shield scale, Quesada gigas, electric leafhopper (Recilia dorsalis), constriction aphid, black helmet scale, leafhopper, dichotomus, Sitobion spp., white-backed planthopper, Spissistilus festinus, Tarophagus Proserpina, aphids, whitefly, Tridiscus sporoboli, Trionymus spp., African psyllid, orange-arrow scale, Zygina flammigera, Zyginidia scutellaris;

- from the order Hymenoptera, e.g.

Arge spp., ...

- from the order Isoptera, e.g.

Coptotermes, Corniternes cumulans, Coptotermes, Macrotermes, Macrotermes, Microtermes, Reticulitermes; tropical fire ants

- from the order Lepidoptera, e.g.

Long-winged torrefies, brown-banded torrefies, transparent-winged moth, ground moth, cotton leafworm, Amylois spp., bean armyworm, yellow torrefies, silver moth (Argyresthia spp.), banded torrefies, yarrow-shaped torrefies, cotton miner, corn armyworm, powdery moth, peach fruit moth, grass borer, leaf roller, Chrysoteuchia topiaria, grape fruit moth, leaf roller, cloud torrefies, pattern torrefies, sheath moth, lepidoptera, Cosmoph ila flava, grass borer, cabbage borer, apple anomaly, boxwood moth, epinotia, boxwood moth, stem borer, Sudanese bollworm, diamond borer, African stem borer, mealybug, leaf moth (Epinotia spp.), fine-spotted moth, Etiella zinckinella, flower moth, ring-needle moth, yellow tussock moth, root cutworm, Feltia jaculiferia, Grapholita spp., green budworm, noctuidae, cabbage borer , Herpetogramma spp., American white moth, tomato borer, Lasmopalpus lignosellus, spiral leafminer, leafminer, grape flower moth, Loxostege bifidaleis, Lymantria spp., miner, leaf moth, cabbage armyworm, tobacco hornworm, Mythimna spp., Noctuidae, fall geometrid, Orniodes indica, European corn borer, supermole, brown moth, small Eyed armyworm, stem borer, Pectinophora gossypiela, coffee leafminer, armyworm, potato moth, cabbage butterfly, Pieris spp., diamondback moth, bud moth, leaf moth, mint armyworm, Richia albicosta, Scirpophaga spp., stem borer, long-palped roller, Spodoptera, cotton leaf folder, Xingpengwei, Heteropoda, leaf roller, cabbage looper, tomato leafminer, and nest moth;

- from the order Maloca, for example,

Damalina spp. and Trichodesmosis spp.;

- from the order Orthoptera, e.g.

Blatta, Blattella, Gryllotalpa, Madeira cockroach, Locust, American mole cricket (Neocurtilla hexadactyla), Periplaneta, Scapteriscus spp. and Desert Locust;

- From the order of the Rodentia, for example,

Booklice;

- from the order Siphonaptera, for example,

Ceratophyllum, Ctenophora and Xenophyllum;

- from the order Thysanoptera, for example,

Calliothrips phaseoli, Flower Thrips spp., Heliothrips spp., Brown-banded Thrips spp., Parthenothrips spp., Scirtothrips aurantii, Sericothrips variabilis, Banded Thrips spp., Thrips spp.;

- from the order Thysanura, for example,

Silverfish.

In another aspect, the invention also relates to a method for controlling or preventing useful plants from being infested with phytopathogenic microorganisms, wherein a compound of formula I, I', I" or I"' is applied as an active ingredient to the plants, their parts or their locus. The compounds of formula I, I', I" or I"' according to the invention are distinguished by their activity, good plant tolerance and environmental safety. They have very useful therapeutic, preventive and systemic properties and are used to protect a variety of useful plants. The compounds of formula I, I', I" or I"' can be used to inhibit or destroy diseases that occur in plants or plant parts (fruits, flowers, leaves, stems, tubers, roots) of a variety of different useful plants, while also protecting, for example, those plant parts that grow later from phytopathogenic microorganisms. It is also possible to use the compounds of formula I, I', I" or I'" as dressing agents for treating plant propagation material, in particular seeds (fruits, tubers, grains) and plant cuttings (e.g. rice), for protection against fungal infestation as well as against phytopathogenic fungi present in the soil.

Examples of fungi include: Deuteromycetes (e.g., Botrytis, Pyrospora, Helminthosporium, Fusarium, Septoria, Cercospora, and Alternaria); Basidiomycetes (e.g., Rhizoctonia, Puccinia, Puccinia); Ascomycetes (e.g., Venturia and Powdery Mildew, Monocystis, Moniliformis, Uncinaria); Oomycetes (e.g., Phytophthora, Pythium, Monoparacephala); Zygomycetes (e.g., Rhizopus); those of the Pucciniaceae family, particularly those of the genus Puccinia, such as Puccinia pachyrhizi, which is also known as Asian soybean rust, and those of the Pucciniaceae family, particularly those of the genus Puccinia, such as Puccinia graminis, also known as stem rust or black rust, which is a problem disease in cereals, and Puccinia recondita, also known as brown rust.

Among the plants and possible diseases of these plants which can be protected by the method according to the invention, mention may be made of:

-Wheat, for the control of the following seed diseases: Fusarium (Fusarium nivale and Fusarium roseum), black bunt (Tilletia tritici, Tinderella dwarfa or Tilletia indica), Septoria (Septoria glumae) and Ustilago sphaeroides;

- wheat, for the control of the following diseases of the aerial parts of the plant: eyespot (Tapesia yallundae, Tapesia acuiformis), take-all (Tapesia taecii), root blight (F. culmorum, F. graminearum), black spot (Rhizoctonia graminearum), powdery mildew (Erysiphe graminis forma specie tritici), rust (Puccinia striatum and Puccinia reconditatus), and Septoria diseases (Septoria tritici and Septoria glume);

- wheat and barley, for the control of bacterial and viral diseases, such as barley yellow mosaic; - barley, for the control of the following seed diseases: net blotch (Pyrrhizalium trichomoniasis, Pyrrhizalium teres and Cochliobolus graminis), loose smut (loose smut) and fusarium (Fusarium nivale and Fusarium roseum);

- barley, for the control of the following diseases on the aerial parts of the plant: eyespot (Tapesia yallundae), net blotch (Pyrrhiza terrestris and Cochliobolus graminearum), powdery mildew (Erysiphe graminis formas pecie hordei), dwarf leaf rust (Puccinia hordei) and leaf spot (Puccinia hordei);

- Potatoes, for the control of tuber diseases (particularly Phoma tuberosa, Phoma tuberosa, Rhizoctonia solani, Fusarium solani), mildew (Phytophthora infestans) and some viruses (Virus Y);

- Potatoes, for the control of the following foliar diseases: early blight (Alternaria solani), mildew (Phytophthora infestans);

- Cotton, for the control of the following diseases in young plants grown from seed: damping-off and blight (Rhizoctonia solani, Fusarium oxysporum) and black root rot (Tricholoma radix);

- protein-producing plants, such as peas, for the control of the following seed diseases: anthracnose (Psora foetida, Mycosphaeria pisum), fusarium (Fusarium oxysporum), gray mold (Botrytis cinerea) and mildew (Peronospora oleracea);

- Oil-containing plants, such as rapeseed, for the control of the following seed diseases: Stemophyton oleraceus, Alternaria brassicae, and Sclerotinia sclerotiorum;

- Corn, for the control of a variety of seed diseases: (Rhizopus, Penicillium, Trichoderma, Aspergillus, and Gibberella);

- Flax, for controlling the seed diseases: Alternaria linicola;

- Deep forest trees, for controlling damping-off diseases (Fusarium oxysporum, Rhizoctonia solani);

- Rice, for the control of the following diseases on above-ground parts: blast (Pyricularia oryzae), bordered sheath spot (Rhizoctonia solani);

- Leguminosae, for the control of the following diseases on seeds or young plants grown from seeds: damping-off and blight (Fusarium oxysporum, Fusarium roseum, Rhizoctonia solani, Pythium spp.);

- Leguminosae, for the control of the following diseases on aerial parts: gray mold (Botrytis spp.), powdery mildew (especially Erysiphe spp., Erysiphe spp. and Pyricularia spp.), Fusarium spp. (Fusarium oxysporum, Fusarium rosobasidium), leaf spot (Cladosporium spp.), Alternaria leaf spot (Alternaria spp.), anthracnose (Colletotrichum spp.), Septoria leaf spot (Septoria spp.), black spot (Rhizoctonia solani), mildew (e.g. Peronospora spp., Peronospora spp., Pseudocoperonospora spp., Phytophthora spp.);

- fruit trees, for the control of various diseases of the above-ground parts: candidiasis (Monilia fructigenae, M. laxa), scab (Viburnum inermis), powdery mildew (Monosphaeria alba); - vines, for the control of the following foliar diseases: in particular gray mold (Botrytis cinerea), powdery mildew (Uncinaria vitis), black rot (Guignardia biwelli) and mildew (Plasmopara viticola);

- Beetroot, for the following diseases on aerial parts: cercospora blight (brown spot of beet), powdery mildew (Erysiphe beticola), leaf spot (Erysiphe beticola).

The fungicidal compositions according to the invention can also be used to combat fungal diseases that are susceptible to growth on or in wood. The term "wood" refers to all types of wood species, as well as all types of wood intended for construction work, such as solid wood, high-density wood, laminated wood and plywood. The method for treating wood according to the invention essentially comprises contacting one or more compounds according to the invention or compositions according to the invention; this includes, for example, direct application, spraying, immersion, injection or any other suitable means.

When used alone, the compounds of the present invention are effective in controlling nematodes, insects, acarid pests and/or fungal pathogens of growing or harvested agronomic plants, and they can also be used in combination with other biologically active agents used in agriculture, for example, one or more nematicides, insecticides, acaricides, fungicides, bactericides, plant activators, molluscicides and pheromones (chemical or biological). Mixing the compounds of the present invention or their compositions in the form of pesticides with other pesticides often results in a wider spectrum of pesticidal action. For example, the compounds of formula I, I', I" or I"' of the present invention can be effectively combined or used in combination with the following compounds, which are pyrethroids, neonicotinoids, macrocyclic lactones, diamides, phosphates, carbamates, cycloadienes, formamidines, phenolic tin compounds, chlorinated hydrocarbons, benzoylphenyl ureas, pyrroles and the like.

By adding, for example, one or more insecticidal, acaricidal, nematicidal and/or fungicidal active agents, the activity of the compositions according to the invention can be significantly broadened and adapted to the prevailing environment. The combination of a compound of formula I, I', I" or I"' with other insecticidal, acaricidal, nematicidal and/or fungicidal active agents can also have further, unexpected advantages, which can also be described as synergistic activities in a broader sense. For example, plants are better tolerant to them, reduced phytotoxicity, harmful organisms or fungi can be controlled at different stages of their development or behave better during their production (for example, during grinding or mixing, during their storage or during their use).

The following list of pesticides together with the compounds which can be used according to the invention is intended to illustrate the possible combinations by way of example.

The following combination of a compound of formula I, I', I" or I'" with another active compound is preferred (the abbreviation "TX" means "a compound selected from the 72 compounds of each of Table 1, Table A, Table B and Table C of the present invention"):

An adjuvant, the adjuvant is selected from the substances consisting of petroleum + TX,

A miticide, which is selected from the group consisting of the following substances: 1,1-bis(4-chlorophenyl)-2-ethoxyethanol+TX, 2,4-dichlorophenylbenzenesulfonate+TX, 2-fluoro-N-methyl-N-1-naphthylacetamide+TX, 4-chlorophenylphenyl sulfone+TX, avermectin+TX, acetoquinone+TX, acetothrin+TX, flumethrin+TX, aldicarb+TX, aldicarb+TX, α-cypermethrin+TX, thiothion+TX, sulfamethoxam+TX, aminothioate+TX, amitriptyline+TX, amitriptyline hydrogen oxalate+TX, amitraz+TX, cypermethrin+TX, arsenic trioxide+TX, AVI382+TX, AZ60541+TX, azinphos-m ethyl)+TX, azobenzene+TX, azacyclotin+TX, azothoate+TX, benclofen+TX, benoxafos+TX, benzoximate+TX, benzyl benzoate+TX, bifenazate+TX, flumethrin+TX, binachlor+TX, bromethrin+TX, bromocyclene+TX, bromophos+TX, ethyl bromophos+TX, bromopropylate+TX, buprofezin+TX, butanone+TX, butanonesulfonate+TX, butanonesulfonate+TX, butanonesulfonate+TX, calcium sulfur mixture (calcium polysulfide)+TX, campheechlor+TX, carbanolate+TX, carbaryl+TX, carbofuran+TX, carbothion+TX, CGA50'439+TX, chinomethionat+TX, chlorbenside+TX, chlordimeform+TX, chlordimeform hydrochloride+TX, chlorfenapyr+TX, chlorfenson+TX, chlorfensulphide+TX, chlorfenphos+TX, ethyl chlorfenapyr+TX, lorobenzilate + TX, chloromebuform + TX, chloromethiuron + TX, chloropropylate + TX, chlorpyrifos + TX, methyl chlorpyrifos + TX, chlorthiophos + TX, cinerin I + TX, cinerin II + TX, cinerins + TX, clofenac + TX, closantel + TX, kumaphos + TX, crotamiton + TX, crotoxyphos + TX, thiophene + TX, cyan thoate)+TX, cyfluthrin [400882-07-7]+TX, cyhalothrin+TX, cypermethrin+TX, DCPM+TX, DDT+TX, demephion+TX, demephion-O+TX, demephion-S+TX, demeton+TX, methyl demeton+TX, demeton-O+TX, methyl demeton-O+TX, demeton-S+TX, methyl demeton-S+TX, demeton-S-methylsulphon+TX, dimethoate ... Zinaphos + TX, benzylfluanid + TX, dichlorvos + TX, dicliphos + TX, Kailesan + TX, Dicrotophos + TX, Pendimethalin + TX, dimefox + TX, Dimethoate + TX, dinactin + TX, dinex + TX, dinex-diclexine + TX, dinobuton + TX, dinocap + TX, dinocap-4 + TX, dinocap-6 + TX, dinitroester + TX, dinopenton + TX, dinosulfon + TX, nitrobutyl ester (dinoterbon) + TX, dioxophos + TX, diphenyl sulfone + TX, disulfiram + TX, ethiphos + TX, DNOC + TX, dofenapyn + TX, doramectin + TX, endosulfan + TX, endothion + TX, EPN + TX, eprinomectin + TX, ethion + TX, ethoate-methyl + TX, etoxazole + TX, etrimfos + TX, fenazaflor + TX, quinazaquin + TX, fenbutatinoxide + TX, fenothiocarb + TX, cypermethrin + TX, fenpyrad + TX, fenpyroximate + TX, fenson + TX, fentrifanil + TX, cypermethrin + TX, fipronil + TX, fluacrypyrim + TX, fluzolan + TX, flubenzimine + TX, flufenoxuron + TX, flucythrinate + TX, fluenetil + TX, flufenoxuron + TX, flumethrin + TX, fluorbenside + TX, flupy radifurone + TX, fluvalinate + TX, FMC1137 + TX, anti-mite + TX, anti-mite hydrochloride + TX, formothion + TX, formparanate + TX, γ-HCH + TX, glyodin + TX, halfenprox + TX, heptenophos + TX, hexadecyl cyclopropanecarboxylate + TX, hexathiazolin + TX, iodomethane + TX, isocarbophos + TX, isopropyl O-(methoxyaminothiophosphoryl) salicylate + TX, ivermectin + TX, jasmine Jasmolin I + TX, jasmonate II + TX, jodfenphos + TX, lindane + TX, rufenron + TX, malathion + TX, malonoben + TX, mecarbam + TX, mephosfolan + TX, methylthiophene + TX, methacrifos + TX, methamidophos + TX, methamidophos + TX, methidathion + TX, methiocarb + TX, methomyl + TX, methomyl + TX, methyl bromide + TX, metolcarb + TX, metolcarb + TX, mexacarbate + TX, milbemycin + TX, milbemycin oxime oxime)+TX, mipafox+TX, monocrotophos+TX, morphothion+TX, moxidectin+TX, naled+TX, NC-184+TX, NC-152+TX, nifluridide+TX, nikkomycin+TX, nitrilacarb+TX, nitrilacarb 1:1 zinc chloride complex+TX, NNI-0101+TX, NNI-0250+TX, oxydemeton-methyl (oxydemeton-methyl)+TX, oxamyl+TX, oxydeprofos+TX, oxydisulfoton+TX, pp'-DDT+TX, parathion+TX, permethrin+TX, stone Oil + TX, fenthion + TX, fenthion + TX, chlorpyrifos + TX, phosfolan + TX, phosmet + TX, phosphamidon + TX, phoxim + TX, methyl pirimiphos + TX, polychloroterpenes + TX, polynactins + TX, prochloraz + TX, profenofos + TX, promacyl + TX, propetamphos + TX, propoxur + TX, prothidathion + TX, prothoate + TX, pyrethrins + TX, pyridaben + TX, Pyridaphenthion + TX, pyrimidifen + TX, pyrimidifen + TX, quinalphos + TX, quintiofos + TX, R-1492 + TX, RA-17 + TX, rotenone + TX, schradan + TX, sebufos + TX, selamectin + TX, SI-0009 + TX, sophamide + TX, spirodiclofen + TX, spiromesiclofen + TX, SSI-121 + TX, sulfluramid + TX, sulfotep + TX, sulfur + TX, S21-121 + TX, Fluvalinate + TX, tebufenpyrad + TX, TEPP + TX, terbam + TX, stirofos + TX, tetradifon + TX, tetranactin + TX, tetrasul + TX, thiafenox + TX, thiocarboxime + TX, thiofanox + TX, thiometon + TX, thuringiensin + TX, triamiphos + TX, triarathene + TX, triazophos + TX, triazuron + TX, trichlorfon + TX, trifenofos + TX, trinactin + TX, cypermethrin + TX, vaniliprole and YI-5302 + TX,

An algaecide, which is selected from the group consisting of the following substances: 3-benzo[b]thiophene-2-yl-5,6-dihydro-1,4,2-oxathiazine-4-oxide+TX, copper dioctanoate+TX, copper sulfate+TX, cybutryne+TX, dichlone+TX, dichlorophene+TX, endorphin+TX, fentin+TX, slaked lime+TX, nabam+TX, quinoclamine+TX, quinonamid+TX, simazine+TX, fentin acetate and fentin hydroxide+TX,

An anthelmintic selected from the group consisting of avermectin + TX, clefosinate + TX, doramectin + TX, emamectin + TX, emamectin benzoate + TX, eprinomectin + TX, ivermectin + TX, milbemycin + TX, moxidectin + TX, piperazine + TX, selamectin + TX, spinosad and thiophanate + TX,

An avicide, which is selected from the group consisting of chloralose + TX, endrin + TX, fenthion + TX, pyridin-4-amine and strychnine + TX,

A bactericide, which is composed of substances selected from the following group: 1-hydroxy-1H-pyridine-2-thione+TX, 4-(quinoxalin-2-ylamino)benzenesulfonamide+TX, 8-hydroxyquinoline sulfate+TX, bronopol+TX, copper dioctanoate+TX, copper hydroxide+TX, cresol+TX, dichlorophen+TX, dispyrithione+TX, dodesine+TX, fenaminosulf+TX, formaldehyde+TX, mercurophen+TX, kasugamycin+TX, kasugamycin hydrochloride hydrate+TX, nickel di(dimethyldithiocarbamate)+TX, nitrapyrin+TX, octhilinone+TX, oxolinic acid+TX, oxytetracycline+TX, potassium hydroxyquinoline sulfate+TX, probenazole+TX, streptomycin+TX, streptomycin sesquisulfate+TX, chlorphenamine+TX, thimerosal+TX,

A biological agent, which is selected from the group consisting of the following substances: Adoxophyes orana GV+TX, Agrobacterium radiobacterium+TX, Amblyseius spp.+TX, Anagrapha falcifera NPV+TX, Anagrus atomus+TX, Aphelinus abdominalis+TX, Aphidius colemani+TX, Autographa californica NPV+TX, Bacillus firmus+TX, Bacillus firmus+TX, Bacillus sphaericus Neide+TX, Bacillus thuringiensis+TX, Bacillus thuringiensis Berliner+TX, Bacillus thuringiensis.I+TX thuringiensis subsp.aizawai+TX、Bacillus thuringiensis subsp.israelensis、Bacillus thuringiensis subsp.israelensis+TX、Bacillus thuringiensis subsp.kurstaki+TX、Bacillus thuringiensis subsp.tenebrionis+TX、Beauveria bassiana+TX、Beauveria brongniartii+TX、Chrysoperla carnea+TX、Cryptolaemus montrouzieri+TX、Cydia pomonella GV+TX、Dacnusa sibirica+TX, Diglyphus isaea+TX, Encarsia formosa+TX, Eretmoc eruseremicus+TX, Helicoverpa zea+TX, Heterorhabditis bacteriophora and H.megidis+TX, Hippodamia convergens+TX, Leptomastix dactylopii+TX, Macrolophus caliginosus+TX, Mamestra brassicae NPV+TX, Metaphycus helvolus+TX, Metarhizium anisopliae var. acridum+TX、Metarhizium anisopliae var. anisopliae+TX、Neodiprion sertifer nuclear polyhedrosis virus and N. lecontei nuclear polyhedrosis virus+TX、Paraphila parviflora+TX、Paecilomyces fumosoroseus+TX、Pasteuria thornei+TX、Pasteuria nishizawae+TX、Pasteuria ramosa+TX、Phytoseiulus persimilis+TX、Spodopterae xiguamulticapsid nuclear polyhedrosis virus+TX、Steinernema bibionis+TX、Steinernema carinella+TX feltiae)+TX, Steinernema glaseri+TX, Steinernema riobrave+TX, Steinernema riobravis+TX, Steinernema scapterisci+TX, Steinernema spp.+TX, Trichogramma+TX, Typhlodromus occidentalis and Verticillium lecanii+TX,

A soil disinfectant selected from the group consisting of methyl iodide and methyl bromide + TX,

A chemical sterilant, the chemical sterilant is selected from the group consisting of the following substances: apholate + TX, bisazir + TX, busulfan + TX, diflubenzuron + TX, dimatif + TX, hemel + TX, hempa + TX, metepa + TX, methiotepa + TX, methylapholate + TX, morzid + TX, penfluron + TX, tepa + TX, thiohempa + TX, thiotepa + TX, trothamide and urethaneimide + TX,

An insect pheromone, the insect pheromone is selected from the group consisting of the following substances: (E)-dec-5-en-1-yl acetate and (E)-dec-5-en-1-ol + TX, (E)-tridec-4-en-1-yl acetate + TX, (E)-6-methylhept-2-en-4-ol + TX, (E,Z)-tetradec-4,10-dien-1-yl acetate + TX, (Z)-dodec-7 -ene-1-yl acetate + TX, (Z)-hexadec-11-enal + TX, (Z)-hexadec-11-en-1-yl acetate + TX, (Z)-hexadec-13-en-11-yn-1-yl acetate + TX, (Z)-eicos-13-en-10-one + TX, (Z)-tetradec-7-en-1-al + TX, (Z)-tetradec-9-en-1-ol + TX, (Z) -Tetradec-9-en-1-yl acetate + TX, (7E,9Z)-dodec-7,9-dien-1-yl acetate + TX, (9Z,11E)-tetradec-9,11-dien-1-yl acetate + TX, (9Z,12E)-tetradec-9,12-dien-1-yl acetate + TX, 14-methyloctadec-1-ene + TX, 4-methylnonanal-5-ol and 4-methylnonanal-5-ketone + TX, α-multistriatin + TX, western pine beetle gathering pheromone (brevicomin) + TX, codlelure + TX, codlemone + TX, cuelure + TX, disparlure + TX, dodeca-8-en-1-yl Acetate + TX, dodec-9-en-1-yl acetate + TX, dodec-8 + TX, 10-dien-1-yl acetate + TX, dominicalure + TX, 4-methyloctanoic acid ethyl ester + TX, eugenol + TX, southern pine beetle gathering pheromone (frontalin) + TX, gossyplure + TX, grandlure + TX, gossyplure I + TX, gossyplure II + TX, gossyplure III + TX, gossyplure IV + TX, hexalure acetate + TX, ipsdienol + TX, ipsenol + TX, japonilure + TX, lineatin + TX, litlure+TX, looplure+TX, medlure+TX, megatomoicacid+TX, methyleugenol+TX, muscalure+TX, 18-2,13-diene-1-yl acetate+TX, 18-3,13-diene-1-yl acetate+TX, orfralure+TX, oryctalure+TX, ostramone+TX, siglure+TX, sordidin+TX, sulcatol+TX, 14-11-en-1-yl acetate+TX, tert-butyl ketone+TX, tert-butyl ketone A+TX, tert-butyl ketone _B1 +TX, tert-butyl ketone _B2 +TX, tert-butyl ketone C and trunc-call+TX,

An insect repellent, the insect repellent is selected from the group consisting of the following substances: 2-(octylthio)ethanol+TX, butopyronoxyl+TX, butoxy(polypropylene glycol)+TX, dibutyl adipate+TX, dibutyl phthalate+TX, Dibutyl succinate + TX, DEET + TX, DEET + TX, dimethylcarbate + TX, ethyl hexanediol + TX, hexylurea + TX, methoquin-butyl + TX, methyl neodecylamide + TX, oxamate and hydroxyphenoxylate + TX,

An insecticide, the insecticide is selected from the group consisting of the following substances: 1-dichloro-1-nitroethane + TX, 1,1-dichloro-2,2-di(4-ethylphenyl)ethane + TX, 1,2-dichloropropane + TX, 1,2-dichloropropane with 1,3-dichloropropylene + TX, 1-bromo-2-chloroethane + TX, 2,2,2-trichloro-1-(3,4-dichlorophenyl)ethyl acetate + TX, 2,2-dichlorovinyl 2-ethylsulfinylethyl methyl phosphate + TX, 2-(1,3-dithiolan-2-yl)phenyl dimethylcarbamate + TX, 2-(2-butyloxy)thiocyanate + TX. 2-(4,5-dimethyl-1,3-dioxolane-2-yl)phenyl methylcarbamate + TX, 2-(4-chloro-3,5-xylyloxy)ethanol + TX, 2-chlorovinyl diethyl phosphate + TX, 2-imidazolidinone + TX, 2-isovaleryl indan-1,3-dione + TX, 2-methyl (prop-2-ynyl) aminophenyl methylcarbamate + TX, 2-thiocyanatoethyl laurate + TX, 3-bromo-1-chloroprop-1-ene + TX, 3-methyl-1-phenylpyrazol-5-yl dimethylcarbamate + TX, 4-methyl ( 2-propynyl)amino-3,5-dimethylbenzyl ester + TX, dimethylcarbamic acid 5,5-dimethyl-3-oxocyclohex-1-enyl ester + TX, avermectin + TX, acephate + TX, acetamiprid + TX, housefly phosphorus + TX, acetothionil + TX, fluthrin + TX, acrylonitrile + TX, cotton bell carb + TX, aldicarb + TX, aldicarb + TX, chloromethyl naphthalene + TX, allethrin + TX, aloamicin + TX, cypermethrin + TX, α-cypermethrin + TX, α-ecdysone + TX, aluminum phosphide + TX, thiophos + TX, thiocarb + TX, amine absorbent Phosphorus + TX, amine oxalate + TX, amitraz + TX, neonicotinoids + TX, ethyl methidathion + TX, AVI382 + TX, AZ60541 + TX, azadirachtin + TX, methyl pyrifos + TX, azinphos-methyl + TX, azinphos-methyl + TX, azophos + TX, Bacillus thuringiensis δ-endotoxins + TX, barium hexafluorosilicate + TX, barium polysulfide + TX, fumonisin + TX, Bayer22/190 + TX, Bayer22408 + TX, benfuracarb + TX, sulfamethoxam + TX, β-cyfluthrin + TX, β-cypermethrin + TX, bifenthrin + TX, bio-allethrin + TX, bio-allethrin S-cyclopentenyl isomer + TX, bioethanomethrin + TX, bio-permethrin + TX, pyrethrin + TX, di(2-chloroethyl) ether + TX, bistrifluan + TX, borax + TX, bromethrin + TX, bromophenazone + TX, bromothioate + TX, bromo-DDT + TX, bromophos + TX, bromophos-ethyl + TX, hexamethrin + TX, buprofezin + TX, animal insect carb + TX, butathiofos + TX, butanone carb + TX, butyl ester phosphine + TX, butanone carb ... Ketosulfonate + TX, butyl pyridaben + TX, cadusin + TX, calcium arsenate + TX, calcium cyanide + TX, calcium polysulfide + TX, toxaphene + TX, chlormethoxam + TX, carbaryl + TX, carbofuran + TX, carbon disulfide + TX, carbon tetrachloride + TX, trithion + TX, butyral + TX, cartap + TX, cartap hydrochloride + TX, sivaldin + TX, borneol + TX, chlordane + TX, chlorfenapyr + TX, chlorpyrifos + TX, chlordane + TX, chlorfenapyr + TX, chlorfenapyr + TX, chlorpyrifos + TX, chlorfenapyr + TX, chlorfenapyr + TX, chlormethoxam + TX, chlormethoxam + TX, chloroform + TX, chloropicrin + TX, chlorpyrifos + TX, chlorpyrifos + TX, chlorpyrifos-methyl + TX, chlorpyrifos + TX, chloranil + TX, chloranil + TX, chloranil I + TX, chloranil II + TX, chloranil + TX, cis-resmethrin + TX, cis-resmethrin + TX, cypermethrin + TX, chloranil + TX, chloranil + TX, copper acetyl arsenite + TX, copper arsenate + TX, copper oleate + TX, chloranil ... TX, cryolite + TX, CS708 + TX, benzonitrile + TX, cypermethrin + TX, fruit insect + TX, cypermethrin + TX, cyfluthrin + TX, cyhalothrin + TX, cypermethrin + TX, cypermethrin + TX, cypromazine + TX, d-limonene + TX, d-tetramethrin + TX, DAEP + TX, dazomethane + TX, DDT + TX, decarbofuran + TX, cypermethrin + TX, tannic acid + TX, tannic acid-O + TX, tannic acid-S + TX, tetronix + TX, tetronix-methyl + TX, tetronix Phosphorus-O+TX, endophos-O-methyl+TX, endophos-S+TX, endophos-S-methyl+TX, endophos-S-methylsulfone+TX, dithiocarb+TX, chlorfenapyr+TX, diamidophos+TX, diazinon+TX, isochlorophos+TX, dimethoate+TX, dichlorvos+TX, dicliphos+TX, dicresyl+TX, dicrotophos+TX, dicynilide+TX, dieldrin+TX, diethyl 5-methylpyrazol-3-yl phosphate+TX, diflubenzuron+TX, dihydroxypropyltheophylline (dilor)+TX, tetrafluoromethylthiocarb+TX, methylphosphine+TX, dimethoate+TX, dimethoate+TX, pyrethrin+TX, methyltoluene Insecticidal + TX, dimethoate + TX, dimethoate + TX, dimethoate-diclexine + TX, propanol + TX, pentophenol + TX, danosid + TX, dimethoate + TX, benzylpyridin + TX, vegetable and fruit phosphorus + TX, dimethoate + TX, dimethoate + TX, dimethoate + TX, dithiophos + TX, dithiophos + TX, dithiophos + TX, DNOC + TX, doramectin + TX, DSP + TX, ecdysone + TX, EI1642 + TX, methoxyavermectin + TX, methoxyavermectin benzoate + TX, EMPC + TX, fenthrin + TX, endosulfan + TX, endrin + TX, EPBP + TX 、EPN+TX、Bayouether+TX、Eprinomectin+TX、Cypermethrin+TX、Etaphos+TX、Ethiofencarb+TX、Ethiofen+TX、Ethiofen+TX、Ethiofennitrile+TX、Ethiofen-methyl+TX、Ethiofenthion+TX、Ethyl formate+TX、Ethyl-DDD+TX、Ethylene dibromide+TX、Ethylene dichloride+TX、Ethiofenthion+TX、Ethiofenthion+TX、Ethiofennitrile+TX、Ethiofenthion+TX、EXD+TX、Amoxicillin+TX、Fenamiphos+TX、Anti-mectazole+TX、Piperphos+TX、Fenthiocarb+TX、Fenflufen+TX、Fenflufen+TX、Fenoxacrim+TX 、fenoxycarb + TX, cypermethrin + TX, cypermethrin + TX, fenpyrad + TX, fenthion + TX, fenthion-ethyl + TX, cypermethrin + TX, fipronil + TX, flonicamid + TX, flubendiamide [272451-65-7] + TX, flucofuron + TX, flucythrinate + TX, flufenoxam + TX, flucythrinate + TX, fluazifop + TX, flufenoxuron + TX, flumethrin + TX, flumethrin + TX, fluvalinate + TX, FMC1137 + TX, diflubenzuron + TX, flumethrin + TX, flumethrin hydrochloride + TX, anthracene + TX, alcyprodinil ( formparanate)+TX, butylfenthion+TX, forsporafil+TX, thiabendazole+TX, butylthiophos+TX, furathiocarb+TX, pyrethroid+TX, γ-cyhalothrin+TX, γ-HCH+TX, biguanide salt+TX, biguanide acetate+TX, GY-81+TX, benzylfen+TX, chlorfenapyr+TX, HCH+TX, HEOD+TX, febuda+TX, heptenephos+TX, cypermethrin+TX, hexaflumuron+TX, HHDN+TX, hydrazone+TX, hydrocyanic acid+TX, methoprene+TX, hyquincarb+TX, imidacloprid+TX, cypermethrin+TX, indoxacarb+TX, iodine Methane + TX, IPSP + TX, chlorfenthion + TX, carbofuran + TX, isocarb + TX, isothrin + TX, isofenphos + TX, transplanting spirit + TX, isoprocarb + TX, O-(methoxyaminothiophosphoryl) salicylic acid isopropyl ester + TX, rice blast + TX, isothiophos + TX, oxazophos + TX, ivermectin + TX, jasmonate I + TX, jasmonate II + TX, iodine + TX, juvenile hormone I + TX, juvenile hormone II + TX, juvenile hormone III + TX, chlorfenapyr + TX, methoprene + TX, λ-cyhalothrin + TX, lead arsenate + TX, lepidomectin + TX, parabromophos + TX, lindan + TX, lirim fos+TX, lufenuron+TX, thiathion+TX, m-isopropylphenyl methylcarbamate+TX, magnesium phosphide+TX, malathion+TX, tebuconazole+TX, azidophos+TX, cypermethrin+TX, tetramethylphos+TX, cypermethrin+TX, dichlorvos+TX, mercurous chloride+TX, mesulfenfos+TX, metaflumizone+TX, metamifop+TX, metamifop potassium+TX, metamifop sodium+TX, cypermethrin+TX, methylamidophos+TX, methanesulfonyl fluoride+TX, methamidophos+TX, methamidophos+TX, ethylenephos+TX, methomyl+TX, methomyl+TX, methoprene+TX, mequindox+TX, methoxychlor+TX, Anthracene + TX, methyl bromide + TX, methyl isothiocyanate + TX, methyl chloroform + TX, dichloromethane + TX, methoxyfluthrin + TX, mefenacet + TX, mefenphos + TX, zikwei + TX, milbemycin + TX, propylamine fluorophos + TX, anticide + TX, monocrotophos + TX, thiophos + TX, moxidectin + TX, naphthyl phos + TX, dibromophos + TX, naphthalene + TX, NC-170 + TX, NC-184 + TX, nicotine + TX, nicotine sulfate + TX, fluazifop + TX, nitenpyram + TX, nithiazine + TX, pentamethylenediamine + TX, pentamethylenediamine 1:1 chlorinated Zinc complex + TX, NNI-0101 + TX, NNI-0250 + TX, nornicotine + TX, flubendiamide + TX, flubendiamide + TX, O-5-dichloro-4-iodophenyl O-ethylethyl phosphonothioate + TX, O,O-diethyl O-4-methyl-2-oxo-2H-chromen-7-yl phosphonothioate + TX, O,O-diethyl O-6-methyl-2-propylpyrimidin-4-yl phosphonothioate + TX, O,O,O',O'-tetrapropyl dithiodipyrophosphate + TX, oleic acid + TX, omethoate + TX, oxamyl + TX, methyl sulfone + TX, isosulfoxide + TX, sulfone + TX, pp'-DDT + TX, p-dichlorobenzene + TX, parathion + TX, parathion-methyl + TX, flufenthion + TX, pentachlorophenol + TX, pentachlorophenyl laurate + TX, permethrin + TX, petroleum oil + TX, PH60-38 + TX, fenthion + TX, phenthrin + TX, fenthion + TX, phorate + TX, phosphamidon + TX, thiocyanate + TX, phosmet + TX, parathion + TX, phosphamidon + TX, phosphine + TX, phoxim + TX, phoxim-methyl + TX, pirimetaphos + TX, pirimetaphos + TX, cypermethrin + TX, chlorpyrifos + TX, chlorpyrifos-ethyl + TX, cypermethrin-methyl + TX, polychlorodicyclopentadiene isomers + TX, polychloroterpenes + TX, potassium arsenite + TX, potassium thiocyanate + TX, chlorpyrifos + TX 、Precocious element I+TX、Precocious element II+TX、Precocious element III+TX、Primidophos+TX、Profenofos+TX、Profluthrin+TX、Fluthrin+TX、Fluthrin+TX、Fluthrin+TX、Protrifenbute+TX、Pymetrozine+TX、Pyrafluprole+TX、Pyrethrin+TX、Pyresmethrin+TX、Pyrethrin I+TX、Pyrethrin II+TX、Pyrethrins+TX、Pyrethrin+TX、Pyridacloral+TX、Pyrimidine+TX、Pyrethrin ... TX, pyridazinon + TX, pyrimidifen + TX, pyriproxyfen + TX, quassia extract + TX, quinalphos + TX, quinalphos-methyl + TX, quintiofos + TX, R-1492 + TX, rafoniide + TX, resmethrin + TX, rotenone + TX, RU15525 + TX, RU25475 + TX, ryania + TX, lianodine + TX, sabaveratrum + TX, octamethoxam + TX, cadusin + TX, selamectin + TX, SI-0009 + TX, SI-0205 + TX, SI-0404 + TX, S I-0405+TX, flumethrin+TX, SN72129+TX, sodium arsenite+TX, sodium cyanide+TX, sodium fluoride+TX, sodium hexafluorosilicate+TX, sodium pentachlorophenol+TX, sodium selenate+TX, sodium thiocyanate+TX, thion+TX, spinosad+TX, spiromesifen+TX, spirotetramat+TX, sulcofuron+TX, sulcofuron-sodium+TX, sulfluramid+TX, thiophanate+TX, sulfonyl fluoride+TX, sulfamethoxam+TX, thiophanate+TX, tars+TX, τ-fluvalinate+TX, thiamethoxam+TX, TDE+TX, tebufenozide+TX, tebufenpyrad+TX, butylpyrimidophos+TX, tetrabencarb+TX, tefluthrin+TX , bispyribac + TX, TEPP + TX, cyclopentylthrin + TX, terbam + TX, terbuthion + TX, tetrachloroethane + TX, cypermethrin + TX, θ-cypermethrin + TX, thiacloprid + TX, thiafenox + TX, thiamethoxam + TX, thicrofos + TX, cypermethrin + TX, cypermethrin hydrogen oxalate + TX, thiodicarb + TX, long-acting carb + TX, methyl thiosulfate + TX, thiosulfate + TX, thiosultap + TX, thiosultap-sodium + TX, thuringin + TX, tolfenpyrad + TX, tralomethrin + TX, tetrafluthrin + TX, transpermethrin+TX, fenthion+TX, triazophos+TX, fenthion+TX, trichlormetaphos+TX, trichlormetaphos-3+TX, chlorpyrifos+TX, trichlorpropoxyphos+TX, thiocarb+TX, thiocarb+TX, methoxythiocarb+TX, thiocarb+TX, vaniliprole+TX, veratridine+TX, veratridine+TX, XMC+TX, fenthion+TX, YI-5302+TX, ζ-cypermethrin+TX, zetamethrin+TX, zinc phosphide+TX, zolaprofos, and ZXI8901+TX, cyantraniliprole[ 736994-63-19]+TX, chlorantraniliprole [500008-45-7]+TX, cyenopyrafen [560121-52-0]+TX, flufenamidate [400882-07-7]+TX, pyrifluquinazon [337458-27-2]+TX, spinetoram [187166-40-1+187166-15-0]+TX, spirotetramat [203313-25-1]+TX, sulfoxaflor [946578-00-3]+TX, flufiprole [704886-18-0]+TX, chlorfluthrin [915288-13-0]+TX, tetramethylfluthrin [84937-88-2]+TX,

A molluscicide, which is selected from the group consisting of di(tributyltin) oxide + TX, bromoacetamide + TX, calcium arsenate + TX, cloethocarb + TX, copper acetyl arsenite + TX, copper sulfate + TX, triphenyltin + TX, iron phosphate + TX, metaldehyde + TX, methiocarb + TX, niclosamide + TX, niclosamide ethanolamine + TX, pentachlorophenol + TX, sodium pentachlorophenoxide + TX, tazimcarb + TX, thiodicarb + TX, tributyltin oxide + TX, trifenmorph + TX, trimethacarb + TX, triphenyltin acetate and triphenyltin hydroxide + TX, pyriprole + TX,

A nematicide, the nematicide is selected from the group consisting of the following substances: AKD-3088+TX, 1,2-dibromo-3-chloropropane+TX, 1,2-dichloropropane+TX, 1,2-dichloropropane and 1,3-dichloropropylene+TX, 1,3-dichloropropylene+TX, 3,4-dichlorotetrahydrothiophene 1,1-dioxide+TX, 3-(4-chlorophenyl)-5-methylrhodanine+TX, 5-methyl-6-thio-1,3,5-thiadiazinane-3-yl acetic acid+TX, 6-isopentenylaminopurine+TX, avermectin+TX, acetothionil+TX, cotton bell carb+TX, aldicarb+TX, aldoxycarb+TX, AZ60541+TX, benclothiaz+TX, benclothiaz+TX, butylpyridabenz tylpyridaben)+TX, cadusafos+TX, carbofuran+TX, carbon disulfide+TX, carbofuran butysulfide+TX, chloropicrin+TX, chlorpyrifos+TX, cloethocarb+TX, cytokinins+TX, dazomethane+TX, DBCP+TX, DCIP+TX, diamidafos+TX, dichlofenthion+TX, dicliphos+TX, dimethoate+TX, emamectin+TX, emamectin benzoate+TX, eprinomectin+TX, eprinomectin+TX, ethoprophos+TX, dibromoethane+TX, fenamiphos Fenamiphos + TX, fenpyrad + TX, fosthiazate + TX, fosthietan + TX, furfural + TX, GY-81 + TX, heterophos + TX, methyl iodide + TX, isamidofos + TX, isazofos + TX, kinetin + TX, mecarphon + TX, mecarphon + TX, metamizole + TX, metamizole potassium salt + TX, metamizole sodium salt + TX, methyl bromide + TX, methyl isothiocyanate + TX, milbemycin oxime + TX, moxidectin + TX , Myrothecium verrucaria components + TX, NC-184 + TX, oxamyl + TX, phorate + TX, phosphamidon + TX, phosphocarb + TX, sebufos + TX, selamectin + TX, spinosad + TX, terbam + TX, terbufos + TX, tetrachlorothiophene + TX, thiafenox + TX, thionazin + TX, triazophos + TX, triazuron + TX, xylenol + TX, YI-5302 and zeatin + TX, fluensulfone [318290-98-1] + TX,

A nitrification inhibitor, the nitrification inhibitor is selected from the group consisting of potassium ethyl xanthate and nitrapyrin + TX,

A plant activator, the plant activator is selected from the group consisting of: acibenzolar+TX, acibenzolar-S-methyl+TX, probenazole and Reynoutria sachalinensis extract+TX,

A rodenticide, the rodenticide is selected from the group consisting of the following substances: 2-isovaleryl indane-1,3-dione + TX, 4-(quinoxaline-2-ylamino)benzenesulfonamide + TX, α-chlorohydrin + TX, aluminum phosphide + TX, antu + TX, arsenic trioxide + TX, barium carbonate + TX, bifenthrin + TX, brodifacoum + TX, bromodiolone + TX, bromodiolone + TX, calcium cyanide + TX, azodipine + TX, chlorofacitin + TX, vitamin D3 + TX, chlorfenapyr + TX, cypermethrin + TX, cypermethrin + TX, cypermethrin + TX, and cypermethrin +TX, thiazolin +TX, sodium difacoum +TX, vitamin D2 +TX, fludioxaline +TX, fluoroacetamide +TX, strychnine +TX, strychnine hydrochloride +TX, β-HCH +TX, HCH +TX, hydrocyanic acid +TX, iodomethane +TX, lindane +TX, magnesium phosphide +TX, methyl bromide +TX, fosfomycin +TX, phosphine +TX, phosphorus +TX, fosfomycin +TX, potassium arsenite +TX, fosfomycin +TX, strychnine glycoside +TX, sodium arsenite +TX, sodium cyanide +TX, sodium fluoroacetate +TX, strychnine +TX, thallium sulfate +TX, fosfomycin and zinc phosphide +TX,

A synergist, the synergist is selected from the group consisting of the following substances: 2-(2-butoxyethoxy)ethyl piperonyl ester+TX, 5-(1,3-benzodioxol-5-yl)-3-hexylcyclohex-2-enone+TX, farnesol with nerolidol+TX, MB-599+TX, MGK264+TX, piperonyl butoxide+TX, piprotal+TX, propylisomer+TX, S421+TX, sesamex+TX, sesasmolin and sulfoxide+TX,

An animal repellent, which is selected from the group consisting of anthraquinone + TX, chloralose + TX, copper naphthenate + TX, copper oxychloride + TX, diazinon + TX, dicyclopentadiene + TX, guazatine + TX, guazatine acetate + TX, methiocarb + TX, pyridine-4-amine + TX, salam + TX, trimethacarb + TX, zinc naphthenate and ziram + TX,

A virucide selected from the group consisting of imanin and ribavirin+TX,

A wound protection agent, which is selected from the group consisting of mercuric oxide + TX, octhilinone and methyl thiophanate + TX,

and a biologically active compound selected from the group consisting of: azaconazole (60207-31-0] + TX, bifenthrin [70585-36-3] + TX, oxadiazol [116255-48-2] + TX, cyproconazole [94361-06-5] + TX, difenoconazole [119446-68-3] + TX, diniconazole [83657-24-3] + TX, epoxiconazole [106325-08-0] + TX, fenthrin [114369 -43-6]+TX, fluquinconazole [136426-54-5]+TX, flusilazole [85509-19-9]+TX, flutriafol [76674-21-0]+TX, hexaconazole [79983-71-4]+TX, imazalil [35554-44-0]+TX, imipenem [86598-92-7]+TX, cyproconazole [125225-28-7]+TX, metconazole [125116-23-6]+TX, myclobutanil [88671-89 -0]+TX, pyrimethanil [101903-30-4]+TX, penconazole [66246-88-6]+TX, prothioconazole [178928-70-6]+TX, pyrifenox [88283-41-4]+TX, prochloraz [67747-09-5]+TX, propiconazole [60207-90-1]+TX, simeconazole [149508-90-7]+TX, tebuconazole [1075 34-96-3] + TX, fluconazole [112281-77-3] + TX, triadimefon [43121-43-3] + TX, triadimefon [55219-65-3] + TX, triflumizole [99387-89-0] + TX, trichlorfon [131983-72-7] + TX, tricyclamide [12771-68-5] + TX, chlorfenapyr [60168-88-9] + TX, fluchlorfon [63284-71-9] + TX, ethoxysulfone bupirimate [41483-43-6] + TX, dimethirimol [5221-53-4] + TX, ethirimol [23947-60-6] + TX, dodecacyclic morpholine [1593-77-7] + TX, fenpropidine [67306-00-7] + TX, fenpropimorph [67564-91-4] + TX, spiroxafil [118134- 30-8]+TX, tridemorph[81412-43-3]+TX, cyprodinil[121552-61-2]+TX, pyraclostrobin[110235-47-7]+TX, pyrimethanil[53112-28-0]+TX, fenthion[74738-17-3]+TX, fludioxonil[131341-86-1]+TX, benalaxyl[71626-1 1-4]+TX, furalaxyl[57646-30-7]+TX, metalaxyl[57837-19-1]+TX, R-metalaxyl[70630-17-0]+TX, furamide[58810-48-3]+TX, oxadixyl[77732-09-3]+TX, benomyl[17804-35-2]+TX, carbendazim[10605-21-7]+TX, debacarb [62732-91-6]+TX, chloranil[3878-19-1]+TX, thiabendazole[148-79-8]+TX, chlozolinate[84332-86-5]+TX, dichlozoline[24201-58-9]+TX, Iprodione[36734-19-7]+TX, myclozoline[54864-61-8]+TX, procymidone (procymidone) [32809-16-8] + TX, vinclozoline [50471-44-8] + TX, boscalid [188425-85-6] + TX, carboxin [5234-68-4] + TX, furanilide [24691-80-3] + TX, flutolanil [6 6332-96-5]+TX, oxadiazine[55814-41-0]+TX, oxycarboxin[5259-88-1]+TX, penthiopyrad[183675-82-3]+TX, thiopyrad[130000-40-7]+TX, biguanide[108173-90-6]+TX, dodine[2439-10-3]][ 112-65-2] (free bond) + TX, iminoctadine [13516-27-3] + TX, azoxystrobin [131860-33-8] + TX, ethersoxim-1 [149961-52-4] + TX, oxathiocarb {Proc. BCPC, Int. Congr., Glasgow. 2003, 1, 93} + TX, fluoxastrobin [361377- 29-9]+TX methyl ether oxathiocarb [143390-89-0]+TX, oxathiocarb [133408-50-1]+TX, trifloxystrobin [141517-21-7]+TX, trifloxystrobin [248593-16-0]+TX, picoxystrobin [117428-22-5]+TX, pyraclostrobin [175013-18-0]+TX, ferbam [14484-64-1]+TX , mancozeb [8018-01-7] + TX, maneb [12427-38-2] + TX, methocarb [9006-42-2] + TX, propineb [12071-83-9] + TX, salamine [137-26-8] + TX, mancozeb [12122-67-7] + TX, ziram [137-30-4] + TX, captafol )[2425-06-1]+TX, captan[133-06-2]+TX, benzylfluanid[1085-98-9]+TX, fluoroimide[41205-21-4]+TX, foltan[133-07-3]+TX, tolylfluanid[731-27-1]+TX, bordeaux mixture[8011-63-0]+TX, hydrogen Copper oxide (copperhydroxid) [20427-59-2] + TX, copper chloride (copperoxychlorid) [1332-40-7] + TX, copper sulfate (coppersulfat) [7758-98-7] + TX, copper oxide (copperoxid) [1317-39-1] + TX, mancopper (mancopper) [53988-93-5] + TX, oxine-copper [10380-28-6] + TX, dinocap [131-72-6] + TX, nitrothal-isopropyl [10552-74-6] + TX, kewensan [17109-49-8] + TX, isoprene (iprobenphos) [2608 7-47-8]+TX, isoprothiolane[50512-35-1]+TX, phosdiphen[36519-00-3]+TX, pyrazophos[13457-18-6]+TX, tolclofos-methyl[57018-04-9]+TX, acibenzolar-S-methyl[135158-54-2]+TX, difop-butyl[101-05-3]+TX, benzathiapyr[413615-35-7]+TX, blasticidin-S[2079-00-7]+TX, chinomethionat[2439-01-2]+TX, chl oroneb)[2675-77-6]+TX, thiophanate-methyl[1897-45-6]+TX, cyfluthrin[180409-60-3]+TX, cymoxanil[57966-95-7]+TX, dichlone[117-80-6]+TX, diclocymet[139920-32-4]+TX, diclom ezine)[62865-36-5]+TX, dicloran[99-30-9]+TX, diethofencarb[87130-20-9]+TX, oxadimethoxine[110488-70-5]+TX, SYP-LI90(Flumorph)[211867-47-9]+TX, dithianon [3347-22-6]+TX, ethaboxam [162650-77-3]+TX, etridiazole [2593-15-9]+TX, oxathiapiprolin [131807-57-3]+TX, fenamidone [161326-34-7]+TX, fenoxanil [115852-48-7]+TX, fentin [668-34-8]+TX, ferimzone [89269-64-7]+TX, fluazinam [79622-59-6]+TX, fluopicolide [239110-15-7]+TX, flusulfamide [10 6917-52-6]+TX, cyclamic acid [126833-17-8]+TX, fosetyl-aluminium [39148-24-8]+TX, hymexazol [10004-44-1]+TX, propineb [140923-17-7]+TX, IKF-916 (Cyazofamid) [1201 16-88-3]+TX, kasugamycin [6980-18-3]+TX, methasulfocarb [66952-49-6]+TX, mefenamic acid [220899-03-6]+TX, pencycuron [66063-05-6]+TX, phthalide [27355-22-2]+TX, polyoxin (polyoxins) [11113-80-7] + TX, probenazole [27605-76-1] + TX, propamocarb [25606-41-1] + TX, proquinazid [189278-12-4] + TX, pyroquilon [57369-32-1] + TX, quinoxyfen [124495-18-7] + TX, pentachloronitrobenzene [82-68-8] + TX, sulfur [7704-34-9] + TX, thiazolamide [223580-51-6] + TX, triazoxide [ 72459-58-6]+TX, tricyclazole [41814-78-2]+TX, quinazoline [26644-46-2]+TX, validamycin [37248-47-8]+TX, zoxamide (RH7281) [156052-68-5]+TX, mandipropamid [374726-62-2]+TX, isopyrazam [881685-58-1]+TX, sedaxane [874967-67-6]+TX, 3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid (9-dichloromethylene-1,2,3,4-tetrahydro -1,4-dimethano-naphthalen-5-yl)-amide (disclosed in WO2007/048556) + TX, 3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid [2-(2,4-dichlorophenyl)-2-methoxy-1-methyl-ethyl]-amide (disclosed in WO2008/148570) + TX, 1-[4-[4-[(5S)5-(2,6-difluorophenyl)-4,5-dihydro-1,2-oxazol-3-yl]-1,3-thiazol-2-yl]piperidin-1-yl]-2-[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]ethanone + TX, 1-[4-[4-[5-(2,6-difluorophenyl)-4,5-dihydro-1 ,2-oxazol-3-yl]-1,3-thiazol-2-yl]piperidin-1-yl]-2-[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]ethanone [1003318-67-9], both disclosed on page 20 of WO2010/123791, WO2008/013925, WO2008/013622 and WO2011/051243) + TX, 3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid (3',4',5'-trifluoro-diphenyl-2-yl)-amide (disclosed in WO2006/087343) + TX, and 1-methyl-2-(2,4,5-trichloro-thiophen-3-yl)-ethyl] + TX.

References in square brackets after the active ingredient, e.g. [3878-19-1], refer to Chemical Abstracts registration numbers. The mixing pairs described above are known. They are included, for example, in “The Pesticide Manual” [Pesticide Manual-A World Compendium; Thirteenth Edition; Editor: C.D.S. Tom Lin; The British Crop Protection Council] or in the “Compendium of Pesticide Common Names”.

Most of the active ingredients mentioned above are referred to above by a so-called "common name", a related "ISO common name" or, in individual cases, another "common name". If its name is not a "common name", the IUPAC name, IUPAC/Chemical Abstracts name, "chemical name", "traditional name", "compound name", or "development code" is used, or if neither one of these names nor the "common name" is used, an "alternative name" is used.

The mass ratio of any two ingredients in each combination is selected to give the desired, e.g., synergistic effect. In general, the mass ratio will vary depending on the specific ingredients and how much of the ingredient is present in the combination. In general, the mass ratio between the two ingredients in any combination of the present invention is independently from 100:1 to 1:100, including from 99:1, 98:2, 97:3, 96:4, 95:5, 94:6, 93:7, 92:8, 91:9, 90:10, 89:11, 88:12, 87:13, 86:14, 85:15, 84:16, 83:17, 82:18, 81:19, 80:2 0, 79:21, 78:22, 77:23, 76:24, 75:25, 74:26, 73:27, 72:28, 71:29, 70:30, 69:31, 68:32, 67:3 3. 66:34, 65:45, 64:46, 63:47, 62:48, 61:49, 60:40, 59:41, 58:42, 57:43, 56:44, 55:45, 54:4 6. 53:47, 52:48, 51:49, 50:50, 49:51, 48:52, 47:53, 46:54, 45:55, 44:56, 43:57, 42:58, 41: 59, 40:60, 39:61, 38:62, 37:63, 36:64, 35:65, 34:66, 33:67, 32:68, 31:69, 30:70, 29:71, 28: 72, 27:73, 26:74, 25:75, 24:76, 23:77, 22:78, 21:79, 20:80, 19:81, 18:82, 17:83, 16:84, 15:85, 14:86, 13:87, 12:88, 11:89, 10:90, 9:91, 8:92, 7:93, 6:94, 5:95, 4:96, 3:97, 2:98 to 1:99. Any of the present invention The preferred mass ratio between the two components is from 75: 1 to 1: 75, more preferably 50: 1 to 1.50, especially 25: 1 to 1: 25, advantageously 10: 1 to 1: 10, such as 5: 1 to 1: 5, for example 1: 3 to 3: 1. These mixing ratios are understood to include, on the one hand, by mass, and also on the other hand, molar ratios.

Examples of methods of application of the compounds and compositions thereof of the present invention, i.e. methods of controlling pests/fungi in agriculture, are spraying, atomizing, dusting, brushing, seed dressing, broadcasting or pouring - they are selected to suit the intended purpose under the prevailing circumstances.

A preferred method of application in agriculture is application to the leaves of the plants (foliar application), it being possible to choose the frequency and rate of application to correspond to the risk of infection by the pest/fungus in question. Alternatively, the active ingredient can reach the plants via the root system (systemic action), by applying the compound to the locus of the plants, for example, by applying a liquid composition of the compound to the soil (by drenching) or by applying the compound in solid form to the soil in the form of granules (soil application). In the case of rice plants, such granules can be metered into flooded paddy fields.

The application rate per hectare is generally 1 g to 2000 g of active ingredient per hectare, especially 10 g/ha to 1000 g/ha, preferably 10 g/ha to 600 g/ha, such as 50 g/ha to 300 g/ha.

These compounds of the present invention and compositions thereof are also suitable for the protection of plant propagation materials (for example seeds, such as fruits, tubers or grains, or nursery plants) against the harmful organisms of the above type. The propagation material can be treated with the compound before planting, and for example seeds can be treated before sowing. Alternatively, the compound can be applied to seed grains (coating), which is achieved by dipping the grains into a liquid composition or by applying a solid composition layer. When the propagation material is planted in the application site, it is also possible, for example, to apply these compositions to the seed furrow during drilling. These treatment methods for plant propagation materials and the plant propagation materials thus treated are other themes of the present invention. Typically, the treatment rate will depend on the plant to be controlled and the harmful organism/fungus, usually between 1 gram to 200 grams per 100kg seeds, preferably between 5 grams to 150 grams per 100kg seeds, such as between 10 grams to 100 grams per 100kg seeds.

The term seed includes all kinds of seeds and plant propagules including but not limited to true seeds, seed pieces, suckers, kernels, corms, fruits, tubers, grains, rhizomes, cuttings, cuttings and the like and in a preferred embodiment refers to true seeds.

The present invention also includes seeds coated or treated with a compound of formula I, I', I" or I"' or containing a compound of formula I, I', I" or I"'. The term "coated or treated with and/or containing" generally means that in most cases the active ingredient is on the surface of the seed when applied, although a greater or lesser portion of the ingredient may penetrate into the seed material, depending on the method of application. When the seed product is (re)planted, it can absorb the active ingredient. In one embodiment, the present invention makes available a plant propagation material having a compound of formula I, I', I" or I"' adhered thereto. In addition, a composition comprising plant propagation material treated with a compound of formula I, I', I" or I"' is thereby obtainable.

Seed treatment includes all suitable seed treatment techniques known in the art, such as seed dressing, seed coating, seed dusting, seed soaking and seed pelleting. Seed treatment application of the compound of formula I, I', I" or I"' can be achieved by any known method, such as spraying or by dusting before sowing or during sowing/planting of these seeds.

Suitable target plants are, in particular, cereals, such as wheat, barley, rye, oats, rice, corn or sorghum; beets, such as sugar or fodder beets; fruit, such as pome, stone or stoneless fruit, such as apples, pears, plums, peaches, almonds, cherries or berries, such as strawberries, raspberries or blackberries; leguminous plants, such as beans, lentils, peas or soybeans; oilseed plants, such as rapeseed, mustard, chestnuts, olives, sunflowers, coconuts, castor beans, cocoa or groundnuts; melon crops, such as pumpkins, cucumbers or melons; fiber plants such as cotton, flax, hemp or jute; citrus fruits such as oranges, lemons, grapevines or tangerines; vegetables such as spinach, lettuce, asparagus, cabbage, carrots, onions, tomatoes, potatoes or bell peppers; plants of the Lauraceae family such as avocado, Cinnamonium or camphor; and also tobacco, nuts, coffee, eggplant, sugar cane, tea, pepper, grapevines, hops, plantaginaceae, rubber plants and ornamental plants (e.g. flowers and lawn plants or turf).

In one embodiment, the plant is selected from the group consisting of cereals, corn, soybeans, rice, sugar cane, vegetables and oil plants.

The term "plants" is to be understood as also including plants transformed by the use of recombinant DNA techniques and which are able to synthesize one or more selectively acting toxins, such as are known, for example, from toxigenic bacteria, in particular those of the genus Bacillus.

Toxins that can be expressed by such transgenic plants include, for example, insecticidal proteins from Bacillus subtilis or Bacillus japonicus; or insecticidal proteins from Bacillus thuringiensis, such as delta-endotoxins, such as Cry1Ab, Cry1Ac, Cry1F, Cry1Fa2, Cry2Ab, Cry3A, Cry3Bb1, or Cry9C, or vegetative insecticidal proteins (Vips), such as Vip1, Vip2, Vip3, or Vip3A; or insecticidal proteins of nematode symbiotic bacteria, such as Photorhabdus or Xenorhabdus, such as Photorhabdus luminescens, Xenorhabdus nematophilus; toxins produced by animals, such as scorpion toxins, spider toxins, wasp toxins, and other insect-specific neurotoxins; toxins produced by fungi, such as Streptomyces toxins; plant Lectins, such as pea lectin, barley lectin or snowdrop lectin; lectins; protease inhibitors, such as trypsin inhibitors, serine protease inhibitors, potato storage protein (patatin), cysteine protease inhibitors, papain inhibitors; ribosome inactivating proteins (RIP), such as ricin, corn-RIP, abrin, luffa seed toxin protein, saponin or dioscorea toxin protein; steroid metabolizing enzymes, such as 3-hydroxysteroid oxidase, ecdysteroid-UDP-glycosyl-transferase, cholesterol oxidase, ecdysone inhibitor, HMG-COA-reductase, ion channel blockers, such as sodium channel or calcium channel blockers, juvenile hormone esterase, diuretic hormone receptor, stilbene synthase, bibenzyl synthase, chitinase and glucanase.

In the context of the present invention, delta-endotoxins such as Cry1Ab, Cry1Ac, Cry1F, Cry1Fa2, Cry2Ab, Cry3A, Cry3Bb1 or Cry9C, or vegetative insecticidal proteins (Vips), such as Vip1, Vip2, Vip3 or Vip3A, should be understood to obviously also include mixed toxins, truncated toxins and modified toxins. Mixed toxins are produced by new combinations and recombination of different regions of those proteins (see, for example, WO02/15701). Truncated toxins such as truncated Cry1Ab are known. In the case of modified toxins, one or more amino acids of naturally occurring toxins are replaced. In this amino acid replacement, it is preferred that non-naturally occurring protease recognition sequences are inserted into toxins, for example, in the case of Cry3A055, a cathepsin-G-recognition sequence is inserted into Cry3A toxins (see WO03/018810).

Examples of such toxins or transgenic plants capable of synthesizing such toxins are disclosed in, for example, EP-A-0374753, WO93/07278, WO95/34656, EP-A-0427529, EP-A-451878 and WO03/052073.

Methods for preparing such transgenic plants are known to the person skilled in the art and are described, for example, in the publications mentioned above. CryI-type deoxyribonucleic acids and their preparation are known, for example, from WO 95/34656, EP-A-0367474, EP-A-0401979 and WO 90/13651.

The toxins contained in the transgenic plants render the plants tolerant to harmful insects. Such insects may be found in any insect taxonomic group, but are especially commonly found in beetles (Coleoptera), two-winged insects (Diptera) and butterflies (Lepidoptera).

Transgenic plants containing one or more genes encoding insecticide resistance and expressing one or more toxins are known and some are commercially available.

Typically, the compounds of the invention are used in the form of a composition (e.g., a formulation) comprising a carrier. The compounds of the invention and their compositions can be used in different forms, for example, aerosol sprays, capsule suspensions, cold mist concentrates, Dustable powders, emulsifiable concentrates, oil-in-water emulsions, water-in-oil emulsions, encapsulated granules, fine granules, flowable concentrates for seed treatment, gases (under pressure), gas-producing products, granules, thermal atomization concentrates, macrogranules, microgranules, oil-dispersible powders, oil-miscible flowable concentrates, oil-miscible liquids, pastes, vegetable sticks, powders for dry seed treatment, seeds coated with pesticides, soluble concentrates, soluble powders, solutions for seed treatment, suspension concentrates (flowable concentrates), ultra-low volume (ulv) liquids, ultra-low volume suspensions (ulv), water-dispersible granules or tablets, water-dispersible powders for slurry treatment, water-soluble granules or tablets, water-soluble powders for seed treatment and wettable powders.

A formulation typically comprises a liquid or solid carrier and optionally one or more conventional formulation adjuvants which may be solid or liquid adjuvants, for example, non-epoxidized or epoxidized vegetable oils (e.g., epoxidized coconut oil, rapeseed oil or soybean oil), defoamers, such as silicone oils, preservatives, clays, inorganic compounds, viscosity regulators, surfactants, binders and/or tackifiers. The composition may further comprise a fertilizer, micronutrient donor or other preparation that influences plant growth, and includes a combination comprising a compound of the invention and one or more other biologically active agents, such as bactericides, fungicides, nematicides, plant activators, acaricides and insecticides.

The invention therefore also makes available a composition comprising a compound according to the invention together with an agronomically acceptable carrier and optionally one or more customary formulation auxiliaries.

These compositions are prepared in a manner known per se, for example by grinding, sieving and/or squeezing the solid compound of the invention in the absence of an auxiliary agent and for example by intimately mixing and/or grinding the compound of the invention with one or more auxiliary agents in the presence of at least one auxiliary agent. In the case of solid compounds of the invention, the grinding/grinding of the compound is to ensure a specific particle size. The methods for preparing these compositions and the use of the compounds of the invention for preparing these compositions are also a subject of the present invention.

Examples of compositions for use in agriculture are emulsifiable concentrates, suspension concentrates, microemulsions, oil dispersibles, directly sprayable or dilutable solutions, spreadable pastes, diluted emulsions, soluble powders, dispersible powders, wettable powders, dusts, granules or capsules in a polymeric mass, these compositions comprising at least one compound according to the invention and the type of composition being chosen to suit the intended purpose and the prevailing circumstances.

Examples of suitable liquid carriers are: unhydrogenated or partially hydrogenated aromatic hydrocarbons, preferably _C8 to _C12 alkylbenzene moieties, such as xylene mixtures, alkylated naphthalene or tetralin, aliphatic or alicyclic hydrocarbons, such as paraffin or cyclohexane, alcohols such as ethanol, propanol or butanol, ethylene glycol and their ethers and esters such as propylene glycol, dipropylene glycol ether, ethylene glycol or ethylene glycol monomethyl ether or hexanediol monoethyl ether, ketones such as cyclohexanone, isophorone or diacetone alcohol, strongly polar solvents such as N-methylpyrrolidin-2-one, dimethyl sulfoxide or N,N-dimethylformamide, water, unepoxidized or epoxidized vegetable oils, such as unepoxidized or epoxidized rapeseed oil, castor oil, coconut oil or soybean oil and silicone oils.

Examples of solid carriers for example dusts and dispersible powders are generally ground natural minerals such as calcite, talc, kaolin, montmorillonite or attapulgite. In order to improve the physical properties, it is also possible to add highly dispersed silica or highly dispersed absorbent polymers. Suitable granular adsorptive carriers for granules are porous types, such as pumice, gravel, sepiolite or bentonite, and suitable non-absorptive carrier materials are calcite or sand. In addition, a large number of granulated materials of inorganic or organic natural substances can be used, in particular dolomite or crushed plant residues.

Depending on the type of active ingredient to be formulated, suitable surface-active compounds are nonionic, cationic and/or anionic surfactants or surfactant mixtures which have good emulsifying, dispersing and wetting properties. The surfactants of are to be regarded merely as examples; a large number of further surfactants which are conventionally used in the art of formulation and which are suitable according to the invention are described in the relevant literature.

Suitable nonionic surfactants are, in particular, polyglycol ether derivatives of aliphatic or cycloaliphatic alcohols, polyglycol ether derivatives of saturated or unsaturated fatty acids or polyglycol ether derivatives of alkylphenols, which may contain from about 3 to about 30 glycol ether groups and from about 8 to about 20 carbon atoms in the (cyclo)aliphatic hydrocarbon residue or from about 6 to about 18 carbon atoms in the alkyl part of the alkylphenol. Also suitable are water-soluble polyethylene oxide adducts with polypropylene glycol, ethylenediaminopolypropylene glycol or alkylpolypropylene glycols having from 1 to about 10 carbon atoms in the alkyl chain and from about 20 to about 250 glycol ether groups and from about 10 to about 100 propylene glycol ether groups. Typically, the above compounds contain from 1 to about 5 ethylene glycol units per propylene glycol unit. Examples which may be mentioned are nonoxynol ether, castor oil polyglycol ether, polypropylene glycol/polyethylene oxide adducts, tributylphenoxypolyethoxyethanol, polyethylene glycol or octylphenoxypolyethoxyethanol. Also suitable are fatty acid esters of polyoxyethylene sorbitan, such as polyoxyethylene sorbitan trioleate.

These cationic surfactants are in particular quaternary ammonium salts which usually have at least one alkyl residue (from about 8 to about 22 C atoms) as a substituent and (unhalogenated or halogenated) lower alkyl or hydroxyalkyl or benzyl residues as further substituents. These salts are preferably in the form of halides, methyl sulfates or ethyl sulfates. Examples are stearyltrimethylammonium chloride and benzylbis(2-chloroethyl)ethylammonium bromide.

Examples of suitable anionic surfactants are water-soluble soaps or water-soluble synthetic surface-active compounds. Examples of suitable soaps are alkali metal salts, alkaline earth metal salts or (unsubstituted or substituted) ammonium salts of fatty acids having from about 10 to about 22 C atoms, such as the sodium or potassium salts of oleic acid or stearic acid or of natural fatty acid mixtures (obtainable, for example, from coconut oil or tall oil); mention must also be made of the fatty acid methyltaurine. More commonly used, however, are synthetic surfactants, in particular fatty sulfonates, fatty sulfates, sulfonated benzimidazole derivatives or alkylarylsulfonates. Typically, these fatty sulfonates and fatty sulfates are alkali metal salts, alkaline earth metal salts or (substituted or unsubstituted) ammonium salts and they typically have alkyl residues having from about 8 to about 22 C atoms, alkyl also being understood as the alkyl part including the acyl residue; examples which may be mentioned are the sodium or calcium salts of ligninsulfonic acid, the sodium or calcium salts of dodecyl sulfate or the sodium or calcium salts of fatty alcohol sulfate mixtures prepared from natural fatty acids. This group also includes sulfates and sulfonates of fatty alcohol/ethylene oxide adducts. These sulfonated benzimidazole derivatives preferably contain 2 sulfonyl groups and fatty acid residues of about 8 to about 22 C atoms. Examples of alkylarylsulfonates are sodium, calcium or triethanolammonium salts of decylbenzenesulfonic acid, dibutylnaphthalenesulfonic acid or naphthalenesulfonic acid/formaldehyde condensates. In addition, suitable phosphates, such as the phosphate esters of p-nonylphenol/(4-14)ethylene oxide adducts, or phospholipids are also possible.

Typically, these compositions contain 0.1% to 99% (especially 0.1% to 95%) of a compound according to the invention and 1% to 99.9% (especially 5% to 99.9%) of at least one solid or liquid carrier, it being possible in principle that 0% to 25% (especially 0.1% to 20%) of the composition are surfactants (% in each case denotes percentage by weight). For commercial purposes, however, concentrated compositions are generally preferred, the end user in principle using dilute compositions with significantly lower concentrations of active ingredients.

Examples of suitable formulation types for the tank mix composition are solutions, dilute emulsions, suspensions or mixtures thereof, and dusts.

As to the nature of the formulations, the methods according to the invention, such as foliage, drenching, spraying, atomizing, dusting, spreading, applying or pouring, may be chosen according to the intended purposes and the prevailing circumstances.

Such tank-mix compositions are generally prepared by diluting one or more premix compositions containing different pesticides and optionally additional adjuvants with a solvent (eg, water).

Suitable carriers and adjuvants can be solid or liquid and are the substances customary in formulation technology, for example natural or regenerated mineral substances, solvents, dispersants, wetting agents, tackifiers, extenders, binders or fertilizers.

Generally, tank-mix formulations for foliar or soil application comprise 0.1% to 20%, especially 0.1% to 15%, of the desired ingredients, and 99.9% to 80%, especially 99.9% to 85%, of solid or liquid adjuvants (including, for example, a solvent such as water), which adjuvants may be a surfactant, in an amount of 0 to 20%, especially 0.1% to 15%, based on the tank-mix formulation.

Typically, premix formulations for foliar application comprise 0.1% to 99.9%, especially 1% to 95%, of the desired ingredients, and 99.9% to 0.1%, especially 99% to 5%, of solid or liquid adjuvants (including, for example, a solvent such as water), wherein the adjuvants may be a surfactant, in an amount of 0 to 50%, especially 0.5% to 40%, based on the premix formulation.

Typically, tank-mix formulations for seed treatment applications comprise 0.25 to 80%, especially 1 to 75%, of the desired ingredients, and 99.75 to 20%, especially 99 to 25%, of solid or liquid adjuvants (including, for example, a solvent such as water), wherein the adjuvants may be a surfactant, in an amount of 0 to 40%, especially 0.5 to 30%, based on the tank-mix formulation.

Typically, premix formulations for seed treatment applications comprise 0.5% to 99.9%, especially 1% to 95%, of the desired ingredients, and 99.5% to 0.1%, especially 99% to 5%, of solid or liquid adjuvants (including, for example, a solvent such as water), wherein the adjuvants may be a surfactant, in an amount of 0 to 50%, especially 0.5% to 40%, based on the tank mix formulation.

While commercial products are preferably formulated as concentrates (eg, pre-mix compositions (formulations)), end users typically employ diluted formulations (eg, tank mix compositions).

Preferred seed treatment premix formulations are aqueous suspension concentrates. This formulation can be applied to the seed using conventional processing techniques and machines, such as fluidized bed technology, drum grinding methods, rotostatic seed processors, and drum applicators. Other methods, such as spouted beds, can also be useful. These seeds can be pre-coated with glue before coating. After coating, these seeds are typically dried and then transferred to a glue coating machine for coating. Such methods are well known in the art.

Generally, the premix composition of the invention comprises 0.5 to 99.9% by mass, in particular 1 to 95%, advantageously 1 to 50% by mass of the desired ingredients, and 99.5 to 0.1%, in particular 99 to 5% by mass of solid or liquid adjuvants (including, for example, a solvent such as water), wherein the auxiliary agents (or adjuvants) may be a surfactant, in an amount of 0 to 50%, in particular 0.5 to 40%, by mass, based on the premix formulation.

In a preferred embodiment, independent of any other embodiment, the compound of formula I, I', I" or I'" is in the form of a composition for treating (or protecting) plant propagation material, wherein the composition for protecting plant propagation material further comprises a colorant. This composition or mixture for protecting plant propagation material may also include at least one water-soluble and copolymers of water dispersible film-forming polymers which enhance attachment of active ingredients to treated plant propagation materials, the polymers generally having an average molecular weight of at least 10,000 to about 100,000.

The combinations of the invention (ie, those comprising a compound of the invention and one or more additional biologically active agents) may be administered simultaneously or sequentially.

In this case, the components of a combination are administered sequentially (i.e., one by one), and the components are administered sequentially within a reasonable period to achieve the biological effect, such as within a few hours or a few days. The order of administration of the components of the combination, i.e., whether the compound of formula I, I', I" or I"' should be administered first, is not critical for practicing the present invention.

In the case where the ingredients of the combination are applied simultaneously in the present invention, they may be applied as a composition containing the combination, in which case (A) the compound of formula I, I', I" or I'" and one or more ingredients of the combination may be obtained from a separate formulation source and mixed together (referred to as a tank mix, ready-to-use, spray broth or slurry), or (B) the compound of formula I, I', I" or I'" and one or more ingredients of the combination may be sourced as a separate formulation mixture (referred to as a premix, i.e., a mixture, a concentrate or a formulated product).

In one embodiment, independently of other embodiments, a compound according to the invention is administered as a combination. Therefore, the present invention also provides a composition comprising a compound according to the invention as described herein, one or more other bioactive agents and optionally one or more conventional formulation adjuvants; the composition may be in the form of a tank mix or premix composition.

As an alternative to actual synergistic effects with biological activity, the combinations according to the invention may have unexpectedly advantageous properties which may be desirable in a broader sense as synergistic activity. Examples of such advantageous properties that may be mentioned are: advantageous behavior during formulation and/or application (e.g. when grinding, sieving, emulsifying, dissolving or dispersing); increased storage stability, improved light stability; more favorable degradability; improved toxicological and/or ecotoxicological behavior; or other advantages familiar to a person skilled in the art.

The compounds of the invention are preferably used as a nematicide in agriculture.

These compounds of the invention may also find application in other fields, such as one or more of the following: protection of stored goods and storerooms, protection of raw materials (such as wood, textiles), floor coverings and buildings, and in hygiene management - especially protection of humans, livestock and productive livestock against harmful organisms. The invention thus also makes available pesticidal compositions for such uses and methods for the same. The compositions for use in specific uses will need to be modified, and the skilled person will be able to make available such compositions for any specific use.

In the hygiene field, the compositions according to the invention are effective against ectoparasites such as hard ticks, soft ticks, scabies, autumn mites, flies (biting and licking), parasitic fly larvae, lice, hair lice, bird lice and fleas.

The compositions according to the invention are also suitable for protecting materials such as wood, textiles, plastics, adhesives, glues, paints, paper and card, leather, floor coverings and buildings, etc. from attack by insects. The compositions according to the invention can be used, for example, against the following pests: beetles, such as the North American house beetle, the hairy green tiger beetle, the furniture beetle, the death beetle, Ptilinuspecticornis, Dendrobium pertinex, the fine-toothed fork-tailed beetle, Priobium carpini, the brown powder beetle, the African powder beetle, the southern powder beetle, the flat beetle, the soft-haired powder beetle, the flat-legged powder beetle, the scale-haired powder beetle, the wood beetle, the wood beetle, the black beetle, the red-bellied oak beetle, the brown heteroptera beetle, the double-spined beetle and the bamboo beetle, and also the Hymenoptera, such as the blue-black wood beetle, the giant wood beetle, the Taiga wood beetle and Urocerus augu, and termites, such as the yellow-necked wood termite, the hemp-headed sand-mound termite, the Indian and Pakistani structural wood heteroptera Termites, Reticulitermes santerum, Reticulitermes europaeus, Coptotermes dauricus, Coptotermes nevadae and Coptotermes formosanus, as well as wingless insects such as silverfish.

Methods for applying a compound or a combination thereof to stored goods, storerooms, raw materials (such as wood panels and textiles), floor coverings and buildings, and in hygiene management are known in the art.

The present invention also provides a method for treating, controlling, preventing and protecting warm-blooded animals (including humans and fish) against infestations and infections caused by helminths, arachnid species and arthropod endo- and ectoparasites, which method comprises administering or applying orally, topically or parenterally to said animal an anthelmintic, acaricidal or endo- or ectoparasiticidal effective amount of a compound of formula I, I', I" or I'"

The above method is particularly useful for controlling and preventing infestations and infections caused by worms, nematodes, mites and endo- and ectoparasites in warm-blooded animals such as cattle, sheep, pigs, camels, deer, horses, poultry, fish, rabbits, goats, minks, foxes, chinchillas, dogs and cats, as well as humans.

In the context of controlling and preventing infestations and infections in warm-blooded animals, the compounds of the invention are particularly useful for the control of helminths and nematodes. Examples of helminths are members of the class Trematoda, commonly referred to as trematodes or flatworms, particularly members of the genera Fasciola, Pseudomonas, Homodiscus, Diplostomum, Broaddiscus, Ophisthorchis, Fasciola, Echinostoma, and Paragonimus. Nematodes that may be controlled by compounds of formula I, I', I" or I"' include Haemonchus, Osternae, Cooperia, Oesphagastomu, Neck nematodes, Dictyocaulus, Trichuris, Dirofilaria, Ancyclostoma, Ascaris, and the like.

The compounds of the present invention may also control infestations of endoparasitic arthropods such as the larvae of the skin flies and the gastric flies. In addition, mites and arthropod ectoparasitic infestations in warm-blooded animals and fishes including biting lice, sucking lice, flies, biting flies, muscoid flies, flies, myiasitic fly larvae, gnats, mosquitoes, fleas, mites, ticks, nasal bots, sheep tick flies and chiggers may be controlled, prevented or eliminated by the compounds of the present invention. Biting lice include members of the order Trichophagus such as the bovine hair lice, the dog hair lice and the sheep wool lice (Damilina ovis). Sucking lice include members of the order Pseudoptera such as the bovine blood lice, the suid blood lice, the bovine jaw lice and the buffalo blind lice. Biting flies include members of the genus Nigrocera. Ticks include the genera Boophila, Rhipicephalus, Ixodes, Hyalomma, Amblyomma and Cercocephalus. The compounds of the present invention may also be used to control mites that parasitize warm-blooded mammals and poultry, including mites of the orders Acarina and Parasiticus.

For oral administration to warm-blooded animals, the compounds of the present invention can be formulated into animal feeds, animal feed premixes, animal feed concentrates, pills, solutions, pastes, suspensions, drench medications for animals, gels, tablets, boluses and capsules. In addition, the compounds of the present invention can also be administered to animals in their drinking water. For oral administration, the selected dosage form should provide the animals with about 0.01 mg/kg to 100 g/kg of the compound of the present invention per day.

Alternatively, the compounds of the present invention can be administered parenterally, for example, by intraruminal, intramuscular, intravenous or subcutaneous injection to animals. The compounds of the present invention can be dispersed or dissolved in a physiologically acceptable carrier for subcutaneous injection. Alternatively, the compounds of the present invention can be formulated as an implant for subcutaneous administration. In addition, the compounds of the present invention can be administered to animals percutaneously. For parenteral administration, the selected dosage form should provide the animals with a compound of the present invention of about 0.01 mg/kg to 100 mg/kg of animal body weight every day.

The compounds of the invention can also be applied topically to the animals in the form of dips, dusts, powders, collars, medallions, sprays and pour-on formulations. For topical administration, dips and sprays generally contain about 0.5 ppm to 5,000 ppm and preferably about 1 ppm to 3,000 ppm of the compounds of the invention. In addition, the compounds of the invention can be formulated as ear tags for animals, particularly quadrupeds such as cattle and sheep.

The compounds of the present invention may also be combined or used in conjunction with one or more other parasiticidal compounds (thereby broadening the spectrum of activity), including, but not limited to, anthelmintics such as benzimidazoles, piperazines, levamisole, thiophene pyrimidines, praziquantel and the like; endectocides such as avermectins, milbemycins and the like; ectoparasiticides such as arylpyrroles, organophosphates, carbamates, gamma-butyric acid inhibitors including fipronil, pyrethroids, spinosad, imidacloprid and the like; insect growth regulators such as pyriproxyfen, cypromazine and the like; and chitin synthase inhibitors such as benzoyl ureas including flufenoxuron.

The parasiticidal compositions of the present invention include a parasiticidal effective amount of a compound of the present invention or a combination thereof mixed with one or more physiologically tolerable inert solid or liquid carriers, which are known in veterinary practice for oral, percutaneous and topical administration. Such compositions may further include a variety of additives, such as stabilizers, defoamers, viscosity regulators, adhesives and tackifiers, while commercial products will preferably be formulated as concentrates, and end users will generally use diluted formulations.

The compositions according to the invention can also be used for the preparation of compositions for the therapeutic or preventive treatment of fungal diseases in humans and animals, such as, for example, mycoses, dermatoses, tinea and candidiasis or diseases caused by Aspergillus, such as Aspergillus fumigatus.

In one embodiment, independent of any other embodiment, the compound of formula I, I', I" or I'" is an anthelmintic compound.

In one embodiment, independent of any other embodiment, the compound of formula I, I', I" or I'" is a pesticidal compound, preferably a nematicidal compound.

DETAILED DESCRIPTION

The following examples are used to illustrate the present invention and should not be considered to limit the present invention in any way. The scope of the rights required to be protected by the present invention is described by the claims.

In view of the economic efficiency and diversity of the compounds, we preferably synthesized some compounds, and among the many synthesized compounds, some are selected and listed in the following Table 1. The specific compound structures and corresponding compound information are shown in Table 1. The compounds in Table 1 are only for better illustrating the present invention, but not for limiting the present invention. For those skilled in the art, this should not be understood as the scope of the above subject matter of the present invention is limited to the following compounds.

Table 1 Compound structures and ¹ H NMR values

Table A is constructed in the same manner as Table 1 above, except that the general formula I is replaced with a cis structure, such as general formula I' And in Table A, the entries under the "Serial Number" column heading are sequentially described as 1 (cis) to 63 (cis). For example, 1 (cis) corresponds to the compound in Table 1 where Compound 1 is a cis form.

Table B is constructed in the same manner as Table 1 above, except that the general formula I is replaced with the general formula I having a chiral center" In Table B, the entries under the "Serial Number" column heading are sequentially described as 1(RR)-63(RR). For example, 1(RR) corresponds to the compound 1 in Table 1 in which both positions 1 and 2 on the four-membered ring are in R configuration.

Table C is constructed in the same manner as Table 1 above, except that the general formula I is replaced with the general formula I"' having a chiral center In Table C, the entries under the "Serial Number" column heading are sequentially described as 1(SS)-63(SS). For example, 1(SS) corresponds to the compound 1 in Table 1 in which both positions 1 and 2 on the four-membered ring are in S configuration.

Several methods for preparing the compounds of the present invention are described in detail in the following schemes and examples. The starting materials can be purchased commercially or can be prepared by methods known in the literature or as described in detail. It should be understood by those skilled in the art that other synthetic routes can also be used to synthesize the compounds of the present invention. Although specific starting materials and conditions in the synthetic routes have been described below, they can be easily replaced with other similar starting materials and conditions, and these modifications or variations of the preparation methods of the present invention, such as various isomers of the compounds, are included in the scope of the present invention. In addition, the following The preparation method can be further modified according to the disclosure of the present invention using conventional chemical methods well known to those skilled in the art, for example, by protecting appropriate groups during the reaction.

The method examples provided below are used to promote further understanding of the preparation method of the present invention. The specific substances, types and conditions used are determined to further illustrate the present invention and are not intended to limit its reasonable scope. The reagents used in the synthetic compounds shown in the following table can be purchased commercially or can be easily prepared by a person of ordinary skill in the art.

Examples of representative compounds are as follows. The synthesis methods of other compounds are similar and will not be described in detail here.

1. Synthesis of compound 8 (R, R)

To a flask containing 8-1 (1 eq), 3-nitropyridine-2-carboxylic acid (1 eq) was added, followed by dichloromethane, triethylamine (2 eq), and finally HATU (1.2 eq) and the resulting solution was stirred at room temperature for 1 hour. After the intermediate control reaction was completed, the reaction solution was diluted with dichloromethane and the organic phase was washed with dilute hydrochloric acid and saturated brine, respectively. Silica gel was added to the organic phase and the sample was stirred, and normal phase purification was performed to obtain 8 (R, R).

2. Synthesis of Compound 22 (cis)

(1) Under ice bath conditions, AlCl ₃ (1 eq) was added to 22-1 (100 g, 1 eq) in batches, heated to 70 degrees, stirred for 10 min, 22-2 (1 eq) was slowly added dropwise, and stirred at 70 degrees overnight. The residual raw material was controlled to be less than 10%. The reaction solution was poured into ice water and extracted twice with ethyl acetate. The organic phase was washed twice with saturated sodium bicarbonate, dried and concentrated, and purified by normal phase to obtain 22-3 (light yellow oil, 70.0 g, yield 70%).

(2) 22-3 (70 g, 1 eq) was dissolved in 500 mL of methanol. Sodium borohydride (6.9 g, 1 eq) was added in batches under ice bath conditions. The mixture was stirred in an ice bath for 2 h. After the reaction was completed, 500 mL of aqueous ammonium chloride solution was added and stirred for 5 min. The mixture was extracted with ethyl acetate. The organic phase was dried, concentrated, and mixed. Normal phase purification (ethyl acetate: petroleum ether = 1:9) was performed to obtain 22-4 (light yellow oil, 30.0 g, yield 42%).

(3) At room temperature, 22-4 (40 g, 1 eq) and thionyl chloride (3 eq) were added to a solution of lithium chloride (4 eq) in DMF (200 mL) in sequence, and the mixture was stirred at room temperature for 3 h. After the reaction was completed, 100 mL of water was slowly added to the reaction solution, and the mixture was extracted twice with methyl tert-butyl ether. The organic phase was washed twice with saturated brine, and the organic phase was dried, concentrated, and mixed. The mixture was purified by normal phase to obtain 22-5 (light yellow oil, 28.0 g, yield 88%).

(4) At room temperature, to a solution of potassium hydroxide (5 eq) in DMSO (200 mL), 22-5 (28.0 g, 1 eq) and 22-6 (1.1 eq) in DMSO were added in sequence, and the mixture was stirred at room temperature for 3 h. An aqueous solution of potassium hydroxide (5 eq) was slowly added dropwise to the reaction solution, and the mixture was stirred at room temperature for 1 h. The reaction was terminated by mid-control, and the mixture was extracted twice with ethyl acetate. The organic phases were combined, dried, concentrated, and mixed, and purified by normal phase to obtain 22-7 (light yellow solid, 3.2 g, yield 12%).

(5) 22-7 (3.2 g, 1 eq) was dissolved in 50 mL of methanol. Pd/C (0.8 g) was added to the reaction solution at room temperature, replaced with hydrogen three times, heated to 50 degrees, and reacted overnight. After the liquid-to-mass control reaction was completed, the filtrate was collected by diatomaceous earth filtration and concentrated to remove methanol. EA was used for extraction three times, dried, filtered, and concentrated to obtain 22-8 (light yellow oil, 1.2 g, crude product).

(6) 22-8 (1.2 g, 1 eq) was dissolved in 15 mL of ethyl acetate, 6 M HCl-EA solution was added, and the mixture was stirred at room temperature for 1-2 h. The reaction was completed at the mid-control stage, and the reaction solution was directly concentrated to obtain 22-9 (light yellow oil, 1.0 g, crude product).

(7) 22-9 (80 mg, 1 eq) was dissolved in 20 mL of dichloromethane. Under ice bath conditions, 3-nitropyridine-2-carboxylic acid (1 eq), triethylamine (3 eq), and HATU (1.5 eq) were added in sequence. The mixture was stirred at room temperature for 1-2 h. After the reaction was completed, the mixture was extracted with water and dichloromethane. The organic phase was washed three times with dilute hydrochloric acid. The organic phase was dried and concentrated, and the sample was purified by normal phase to obtain compound 22 (cis) (light yellow solid, 55 mg, yield 42%).

Biological activity evaluation (nematode 96-well plate bioassay):

(1) Preparation of test agents

Accurately weigh the test agent, dissolve it in DMSO to prepare a stock solution, and dilute it into different concentration gradient solutions.

(2) Isolation of target nematodes (root-knot nematodes incognita)

When egg masses grow on the root nodes, use tweezers to pick out the egg masses in the root nodes under a dissecting microscope and place them in clean water. Soak them in 0.25% sodium hypochlorite aqueous solution for about 1 minute. After washing and sieving with a 500-mesh sieve, place them in a 90mm culture dish containing an appropriate amount of tap water, put them in a sieving device, and culture them in a 28°C incubator for 3 days. The egg masses will then hatch into second-instar larvae.

(3) Chemical treatment

Add 100 μL of the prepared test agent and nematode suspension to the 96-well culture plate, cover to prevent evaporation, and place in a 28°C incubator. Set up a water control and a drug control for the test; if a solvent is used, set up a solvent control.

(4) Cultivation and observation

The nematodes treated with the drug were cultured under normal conditions, and the mortality of the nematodes was tested for 48 hours and 72 hours: mortality (%) = (number of dead worms/number of worms tested) * 100. The representative test results are shown in Table 2.

Table 2 Nematicidal test results

Note: N means no data; Reference compound A:

At the same time, through many tests, it was found that many of the compounds and compositions of the present invention have good control activity against different types of nematodes, etc., and not only have the characteristics of broad spectrum, high efficiency, strong systemicity, etc., but can effectively control harmful organisms and/or fungi, and have certain commercial value.

Claims (10)

A four-membered ring amide compound, its stereoisomers/isomers/enantiomers/salts and N-oxides:
wherein J ₁ , J ₂ , J ₃ , and J ₄ independently represent N or CM, and at least one of them is N; M represents hydrogen, halogen, cyano, nitro, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, alkoxy, alkylthio, or cycloalkyl or cycloalkylalkyl which is unsubstituted or substituted by alkyl or halogen, or M on two adjacent carbon atoms together form -CH=CH-CH=CH- or -N=CH-CH=CH-; R ₁ , R ₂ , R ₃ , R ₄ , and R ₅ each independently represent hydrogen, halogen, nitro, cyano, thiocyano, hydroxyl, mercapto, carboxyl, sulfonic acid, formyl, haloformyl, azido, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, heterocyclic, aryl, -N(R ₂₁ ) ₂ , -(CO)N(R ₂₁ ) ₂ , -O(CO)N(R ₂₁ ) ₂ , -O(CS)N(R ₂₁ ) ₂ , -(SO ₂ )N(R ₂₁ ) ₂ , -O(SO ₂ )N(R ₂₁ ) ₂ , -PO(OR ₂₂ ) ₂ , -OR ₂₂ , -(CO)R ₂₂ , -SR ₂₂ , -(SO)R ₂₂ , -(SO ₂ )R ₂₂ , -Si(R ₂₂ ) ₃ , -O(CO)R ₂₂ , -O-(SO ₂ )R ₂₂ , -S(CO)R ₂₂ , -(SO ₂ )OR ₂₂ , -O(CO)OR ₂₂ , -(CO)(CO)OR ₂₂ , -(CO)OR ₂₂ , -ON＝C(R ₂₃ ) ₂ , -CR ₂₃ ＝N-OH or -CR ₂₃ ＝NOR ₂₂ , wherein the “alkyl”, “alkenyl” or “alkynyl” is optionally selected from halogen, nitro, cyano, hydroxyl, thiol, carboxyl, cycloalkyl, cycloalkenyl, heterocyclyl, aryl, -N(R ₂₁ ) ₂ , -(CO)N(R ₂₁ ) ₂ , -O(CO)N(R ₂₁ ) ₂ , -O(CS)N(R ₂₁ ) ₂ , -(SO ₂ )N(R ₂₁ ) ₂ , -O(SO ₂ )N(R ₂₁ ) ₂ , -OR ₂₂ , -(CO)R ₂₂ , -SR ₂₂ , -(SO)R ₂₂ , -(SO ₂ )R ₂₂ , -O(CO)H, -O(CO)R ₂₂ , -O-(SO ₂ )R ₂₂ , -(CO)OR ₂₂ , -O(CO)OR ₂₂ , -Si(R ₂₂ ) ₃ , -O(CO)(CO)OH, -O(CO)(CO)OR ₂₂ , -O-alkylene-(CO)OH or -O-alkylene-(CO)OR ₂₂ ; R ₂₁ each independently represents hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, aryl, heterocyclyl, -OR ₂₂ , -(CO)R ₂₂ , -(CO)OR ₂₂ , -alkylene-(CO)OR ₂₂ , -(SO ₂ )R ₂₂ , -(SO ₂ )OR ₂₂ , -alkylene-(SO ₂ )R ₂₂ , -(CO)N(R ₂₄ ) ₂ or -(SO ₂ )N(R ₂₄ ) ₂ ; R ₂₂ each independently represents an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a cycloalkenyl group, an aryl group or a heterocyclyl group, wherein the “alkyl group”, “alkenyl group” or “alkynyl group” is optionally substituted by at least one group selected from halogen, cyano, trialkylsilyl, cycloalkyl group, cycloalkenyl group, aryl group, heterocyclyl group, -OR ₂₅ , -SR ₂₅ , -O(CO)R ₂₅ , -(CO)R ₂₅ , -(CO)OR ₂₅ or -O(CO)OR ₂₅ ; _R23 each independently represents hydrogen, halogen, alkoxy, alkoxyalkyl, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkylalkyl, cycloalkenyl, cycloalkenylalkyl, aryl, arylalkyl, heterocyclyl or heterocyclylalkyl; R ₂₄ each independently represents hydrogen, alkyl, alkenyl, alkynyl, alkoxy, alkylsulfonyl, cycloalkyl, cycloalkylalkyl, cycloalkenyl or cycloalkenylalkyl; or N(R ₂₁ ) ₂ and N(R ₂₄ ) ₂ each independently represent a heterocyclic group with a nitrogen atom at the 1-position; _R25 independently represents hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, haloalkyl, haloalkenyl, haloalkynyl, phenyl or phenyl substituted by at least one group selected from the group consisting of halogen, cyano, nitro, alkyl, haloalkyl, alkoxy, haloalkoxy, alkoxycarbonyl, alkylthio, alkylsulfonyl or halogen, cyano, nitro, alkyl, halo A phenoxy group substituted with at least one of a substituted alkyl group, an alkoxy group or a halogenated alkoxy group; The aforementioned “cycloalkyl”, “cycloalkenyl”, “heterocyclyl” or “aryl” is optionally substituted by at least one group selected from oxo, halogen, cyano, nitro, alkyl, alkenyl, alkynyl, cycloalkyl, haloalkyl, haloalkenyl, haloalkynyl, halocycloalkyl, cycloalkyl substituted by alkyl, _-OR10 , _-SR10 , -(CO) _OR10 , -( _SO2 ) _R10 , -N( _R10 ) ₂ or -O-alkylene-(CO) _OR10 , or two adjacent carbon atoms on the ring form a condensed ring with unsubstituted or halogen-substituted _-OCH2CH2- or _{-OCH2O- ; R10} each independently represents hydrogen, alkyl, haloalkyl, phenyl, or phenyl substituted by at least one group selected from halogen, cyano, nitro, alkyl, haloalkyl, alkoxycarbonyl, alkylthio, alkylsulfonyl, alkoxy or haloalkoxy. The four-membered ring amide compound, its stereoisomers/isomers/enantiomers/salts and N-oxides according to claim 1, characterized in that: M represents hydrogen, halogen, cyano, nitro, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, halogenated C1-C8 alkyl, halogenated C2-C8 alkenyl, halogenated C2-C8 alkynyl, C1-C8 alkoxy, C1-C8 alkylthio, or C3-C8 cycloalkyl or C3-C8 cycloalkylC1-C8 alkyl which is unsubstituted or substituted by C1-C8 alkyl or halogen, or M on two adjacent carbon atoms together form -CH=CH-CH=CH- or -N=CH-CH=CH-; R ₁ , R ₂ , R ₃ , R ₄ , and R ₅ each independently represent hydrogen, halogen, nitro, cyano, thiocyano, hydroxyl, mercapto, carboxyl, sulfonic acid, formyl, haloformyl, azido, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 cycloalkyl, C3-C8 cycloalkenyl, heterocyclic group, aryl, -N(R ₂₁ ) ₂ , -(CO)N(R ₂₁ ) ₂ , -O(CO)N(R ₂₁ ) ₂ , -O(CS)N(R ₂₁ ) ₂ , -(SO ₂ )N(R ₂₁ ) ₂ , -O(SO ₂ )N(R ₂₁ ) ₂ , -PO(OR ₂₂ ) ₂ , -OR ₂₂ , -(CO)R ₂₂ -SR ₂₂ , -(SO)R ₂₂ , -(SO ₂ )R ₂₂ , -Si(R ₂₂ ) ₃ , -O(CO)R ₂₂ , -O-(SO ₂ )R ₂₂ , -S(CO)R ₂₂ , -(SO ₂ )OR ₂₂ , -O(CO)OR ₂₂ , -(CO)(CO)OR ₂₂ , -(CO)OR ₂₂ , -ON＝C(R ₂₃ ) ₂ , -CR ₂₃ ＝N-OH or -CR ₂₃ ＝NOR ₂₂ , wherein the “C1-C8 alkyl”, “C2-C8 alkenyl” or “C2-C8 alkynyl” is optionally selected from halogen, nitro, cyano, hydroxyl, thiol, carboxyl, C3-C8 cycloalkyl, C3-C8 cycloalkenyl, heterocyclyl, aryl, -N(R 23 ) 2 ₂₁ ) ₂ , -(CO)N(R ₂₁ ) ₂ , -O(CO)N(R ₂₁ ) ₂ , -O(CS)N(R ₂₁ ) ₂ , -(SO ₂ )N(R ₂₁ ) ₂ , -O(SO ₂ )N(R ₂₁ ) ₂ , -OR ₂₂ , -(CO)R ₂₂ , -SR ₂₂ , -(SO)R ₂₂ , -(SO ₂ )R ₂₂ , -O(CO)H, -O(CO)R ₂₂ , -O-(SO ₂ )R ₂₂ , -(CO)OR ₂₂ , -O(CO)OR ₂₂ , -Si(R ₂₂ ) ₃ , -O(CO)(CO)OH, -O(CO)(CO)OR ₂₂ , -O-(C1-C8 alkylene)-(CO)OH or -O-(C1-C8 alkylene)-(CO)OR ₂₂ ; R ₂₁ each independently represents hydrogen, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 cycloalkyl, C3-C8 cycloalkenyl, aryl, heterocyclyl, -OR ₂₂ , -(CO)R ₂₂ , -(CO)OR ₂₂ , -(C1-C8 alkylene)-(CO)OR ₂₂ , -(SO ₂ )R ₂₂ , -(SO ₂ )OR ₂₂ , -(C1-C8 alkylene)-(SO ₂ )R ₂₂ , -(CO)N(R ₂₄ ) ₂ or -(SO ₂ )N(R ₂₄ ) ₂ ; R ₂₂ each independently represents a C1-C8 alkyl group, a C2-C8 alkenyl group, a C2-C8 alkynyl group, a C3-C8 cycloalkyl group, a C3-C8 cycloalkenyl group, an aryl group or a heterocyclyl group, wherein the “C1-C8 alkyl group”, “C2-C8 alkenyl group” or “C2-C8 alkynyl group” is optionally substituted by at least one group selected from halogen, cyano, tri-C1-C8 alkylsilyl group, C3-C8 cycloalkyl group, C3-C8 cycloalkenyl group, aryl group, heterocyclyl group, -OR ₂₅ , -SR ₂₅ , -O(CO)R ₂₅ , -(CO)R ₂₅ , -(CO)OR ₂₅ or -O(CO)OR ₂₅ ; R ₂₃ each independently represents hydrogen, halogen, C1-C8 alkoxy, C1-C8 alkoxyC1-C8 alkyl, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 cycloalkyl, C3-C8 cycloalkylC1-C8 alkyl, C3-C8 cycloalkenyl, C3-C8 cycloalkenylC1-C8 alkyl, aryl, arylC1-C8 alkyl, heterocyclyl or heterocyclylC1-C8 alkyl; R ₂₄ each independently represents hydrogen, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C1-C8 alkoxy, C1-C8 alkylsulfonyl, C3-C8 cycloalkyl, C3-C8 cycloalkylC1-C8 alkyl, C3-C8 cycloalkenyl or C3-C8 cycloalkenylC1-C8 alkyl; or N(R ₂₁ ) ₂ and N(R ₂₄ ) ₂ each independently represent a heterocyclic group with a nitrogen atom at the 1-position; R ₂₅ each independently represents hydrogen, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 cycloalkyl, halogenated C1-C8 alkyl, halogenated C2-C8 alkenyl, halogenated C2-C8 alkynyl, phenyl or phenyl substituted by at least one group selected from the following: halogen, cyano, nitro, C1-C8 alkyl, halogenated C1-C8 alkyl, C1-C8 alkoxy, halogenated C1-C8 alkoxy, C1-C8 alkoxycarbonyl, C1-C8 alkylthio, C1-C8 alkylsulfonyl or phenoxy substituted by at least one group selected from the following: halogen, cyano, nitro, C1-C8 alkyl, halogenated C1-C8 alkyl, C1-C8 alkoxy or halogenated C1-C8 alkoxy; The aforementioned “C3-C8 cycloalkyl”, “C3-C8 cycloalkenyl”, “heterocyclyl” or “aryl” is optionally substituted by at least one group selected from oxo, halogen, cyano, nitro, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 cycloalkyl, halogenated C1-C8 alkyl, halogenated C2-C8 alkenyl, halogenated C2-C8 alkynyl, halogenated C3-C8 cycloalkyl, C3-C8 cycloalkyl substituted by C1-C8 alkyl, _-OR10 , _-SR10 , -(CO) _OR10 , -( _SO2 ) _R10 , -N( _R10 ) ₂ or -O-(C1-C8 alkylene)-(CO) _OR10 , or two adjacent carbon atoms on the ring form a condensed ring with unsubstituted or _halogen -substituted _-OCH2CH2- or _-OCH2O- ; _R10 each independently represents hydrogen, C1-C8 alkyl, halogenated C1-C8 alkyl, phenyl, or phenyl substituted by at least one group selected from halogen, cyano, nitro, C1-C8 alkyl, halogenated C1-C8 alkyl, C1-C8 alkoxycarbonyl, C1-C8 alkylthio, C1-C8 alkylsulfonyl, C1-C8 alkoxy or halogenated C1-C8 alkoxy. The four-membered ring amide compound, its stereoisomers/isomers/enantiomers/salts and N-oxides according to claim 1 or 2, characterized in that: M represents hydrogen, halogen, cyano, nitro, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, halogenated C1-C6 alkyl, halogenated C2-C6 alkenyl, halogenated C2-C6 alkynyl, C1-C6 alkoxy, C1-C6 alkylthio, or C3-C6 cycloalkyl or C3-C6 cycloalkylC1-C6 alkyl which is unsubstituted or substituted by C1-C6 alkyl or halogen, or M on two adjacent carbon atoms together form -CH=CH-CH=CH- or -N=CH-CH=CH-; R ₁ , R ₂ , R ₃ , R ₄ , and R ₅ each independently represent hydrogen, halogen, nitro, cyano, thiocyano, hydroxyl, mercapto, carboxyl, sulfonic acid, formyl, haloformyl, azido, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, C3-C6 cycloalkenyl, heterocyclic group, aryl, -N(R ₂₁ ) ₂ , -(CO)N(R ₂₁ ) ₂ , -O(CO)N(R ₂₁ ) ₂ , -O(CS)N(R ₂₁ ) ₂ , -(SO ₂ )N(R ₂₁ ) ₂ , -O(SO ₂ )N(R ₂₁ ) ₂ , -PO(OR ₂₂ ) ₂ , -OR ₂₂ , -(CO)R ₂₂ -SR ₂₂ , -(SO)R ₂₂ , -(SO ₂ )R ₂₂ , -Si(R ₂₂ ) ₃ , -O(CO)R ₂₂ , -O-(SO ₂ )R ₂₂ , -S(CO)R ₂₂ , -(SO ₂ )OR ₂₂ , -O(CO)OR ₂₂ , -(CO)(CO)OR ₂₂ , -(CO)OR ₂₂ , -ON＝C(R ₂₃ ) ₂ , -CR ₂₃ ＝N-OH or -CR ₂₃ ＝NOR ₂₂ , wherein the “C1-C6 alkyl”, “C2-C6 alkenyl” or “C2-C6 alkynyl” is optionally selected from halogen, nitro, cyano, hydroxyl, thiol, carboxyl, C3-C6 cycloalkyl, C3-C6 cycloalkenyl, heterocyclyl, aryl, -N(R 23 ) 2 ₂₁ ) ₂ , -(CO)N(R ₂₁ ) ₂ , -O(CO)N(R ₂₁ ) ₂ , -O(CS)N(R ₂₁ ) ₂ , -(SO ₂ )N(R ₂₁ ) ₂ , -O(SO ₂ )N(R ₂₁ ) ₂ , -OR ₂₂ , -(CO)R ₂₂ , -SR ₂₂ , -(SO)R ₂₂ , -(SO ₂ )R ₂₂ , -O(CO)H, -O(CO)R ₂₂ , -O-(SO ₂ )R ₂₂ , -(CO)OR ₂₂ , -O(CO)OR ₂₂ , -Si(R ₂₂ ) ₃ , -O(CO)(CO)OH, -O(CO)(CO)OR ₂₂ , -O-(C1-C6 alkylene)-(CO)OH or -O-(C1-C6 alkylene)-(CO)OR ₂₂ ; R ₂₁ each independently represents hydrogen, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, C3-C6 cycloalkenyl, aryl, heterocyclyl, -OR ₂₂ , -(CO)R ₂₂ , -(CO)OR ₂₂ , -(C1-C6 alkylene)-(CO)OR ₂₂ , -(SO ₂ )R ₂₂ , -(SO ₂ )OR ₂₂ , -(C1-C6 alkylene)-(SO ₂ )R ₂₂ , -(CO)N(R ₂₄ ) ₂ or -(SO ₂ )N(R ₂₄ ) ₂ ; R ₂₂ each independently represents a C1-C6 alkyl group, a C2-C6 alkenyl group, a C2-C6 alkynyl group, a C3-C6 cycloalkyl group, a C3-C6 cycloalkenyl group, an aryl group or a heterocyclyl group, wherein the “C1-C6 alkyl group”, “C2-C6 alkenyl group” or “C2-C6 alkynyl group” is optionally substituted by at least one group selected from halogen, cyano, tri-C1-C6 alkylsilyl group, C3-C6 cycloalkyl group, C3-C6 cycloalkenyl group, aryl group, heterocyclyl group, -OR ₂₅ , -SR ₂₅ , -O(CO)R ₂₅ , -(CO)R ₂₅ , -(CO)OR ₂₅ or -O(CO)OR ₂₅ ; R ₂₃ each independently represents hydrogen, halogen, C1-C6 alkoxy, C1-C6 alkoxyC1-C6 alkyl, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, C3-C6 cycloalkylC1-C6 alkyl, C3-C6 cycloalkenyl, C3-C6 cycloalkenylC1-C6 alkyl, aryl, arylC1-C6 alkyl, heterocyclyl or heterocyclylC1-C6 alkyl; R ₂₄ each independently represents hydrogen, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C1-C6 alkoxy, C1-C6 alkylsulfonyl, C3-C6 cycloalkyl, C3-C6 cycloalkylC1-C6 alkyl, C3-C6 cycloalkenyl or C3-C6 cycloalkenylC1-C6 alkyl; or N(R ₂₁ ) ₂ and N(R ₂₄ ) ₂ are each independently unsubstituted or substituted by at least one group selected from oxo, C1-C6 alkyl or C1-C6 alkoxycarbonyl. R ₂₅ each independently represents hydrogen, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, halogenated C1-C6 alkyl, halogenated C2-C6 alkenyl, halogenated C2-C6 alkynyl, phenyl or phenyl substituted by at least one group selected from the following: halogen, cyano, nitro, C1-C6 alkyl, halogenated C1-C6 alkyl, C1-C6 alkoxy, halogenated C1-C6 alkoxy, C1-C6 alkoxycarbonyl, C1-C6 alkylthio, C1-C6 alkylsulfonyl or phenoxy substituted by at least one group selected from the following: halogen, cyano, nitro, C1-C6 alkyl, halogenated C1-C6 alkyl, C1-C6 alkoxy or halogenated C1-C6 alkoxy; The aforementioned “C3-C6 cycloalkyl”, “C3-C6 cycloalkenyl”, “heterocyclyl” or “aryl” is optionally substituted by at least one group selected from oxo, halogen, cyano, nitro, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, halogenated C1-C6 alkyl, halogenated C2-C6 alkenyl, halogenated C2-C6 alkynyl, halogenated C3-C6 cycloalkyl, C3-C6 cycloalkyl substituted by C1-C6 alkyl, _-OR10 , _-SR10 , -(CO) _OR10 , -( _SO2 ) _R10 , -N( _R10 ) ₂ or -O-(C1-C6 alkylene)-(CO) _OR10 , or two adjacent carbon atoms on the ring form a condensed ring with unsubstituted or _halogen -substituted _-OCH2CH2- or _-OCH2O- ; _R10 each independently represents hydrogen, C1-C6 alkyl, halogenated C1-C6 alkyl, phenyl, or phenyl substituted by at least one group selected from halogen, cyano, nitro, C1-C6 alkyl, halogenated C1-C6 alkyl, C1-C6 alkoxycarbonyl, C1-C6 alkylthio, C1-C6 alkylsulfonyl, C1-C6 alkoxy or halogenated C1-C6 alkoxy. The four-membered ring amide compound, its stereoisomers/isomers/enantiomers/salts and N-oxides according to any one of claims 1 to 3, characterized in that They are cis relative to each other on the four-membered ring. The four-membered ring amide compound, its stereoisomer/isomer/enantiomer/salt and N-oxide according to any one of claims 1 to 4, characterized in that: The carbon atoms at positions 1 and 2 of the four-membered ring are both chiral centers, and have a stereochemical purity of 60-100% (R), preferably 70-100% (R), more preferably 80-100% (R), further preferably 90-100% (R), and even more preferably 95-100% (R), based on the contents of stereoisomers having R and S configurations at these positions, respectively; or Based on the contents of stereoisomers having R and S configurations at this position, respectively, it has a stereochemical purity of 60-100% (S), preferably 70-100% (S), more preferably 80-100% (S), further preferably 90-100% (S), and even more preferably 95-100% (S). The four-membered ring amide compound, its stereoisomer/isomer/enantiomer/salt and N-oxide according to any one of claims 1 to 5, characterized in that the compound is selected from any one of Table 1, Table A, Table B and Table C. A method for preparing a four-membered ring amide compound, a stereoisomer/isomer/enantiomer/salt and N-oxide thereof as claimed in any one of claims 1 to 6, comprising the following steps: The compound represented by the general formula II is reacted with the compound represented by the general formula III to obtain the compound represented by the general formula I, and the reaction equation is as follows:
wherein M represents OH or halogen, and the substituents R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , J ₁ , J ₂ , J ₃ , and J ₄ are defined as described in any one of claims 1 to 6; Preferably, the reaction is carried out in the presence of a solvent, more preferably, a condensing agent and/or a base is added during the reaction; further preferably, the solvent is selected from at least one of DMF, DMA, methanol, ethanol, acetonitrile, dichloroethane, DMSO, Dioxane, dichloromethane or ethyl acetate, the base is selected from at least one of an inorganic base or an organic base, and the condensing agent is selected from at least one of Py-BOP, Py-AOP, EDCI, HOBT, DCC, HBTU or HATU. A composition for killing pests and/or fungi (especially nematodes), characterized in that it comprises a biologically effective amount of at least one of the four-membered ring amide compound according to any one of claims 1 to 6, its stereoisomers/isomers/enantiomers/salts and N-oxides; preferably, it also includes a formulation adjuvant; more preferably, it also includes other active ingredients. A method for controlling harmful organisms and/or fungi (especially nematodes), characterized in that it comprises contacting the harmful organisms and/or fungi (especially nematodes) or their environment with a biologically effective amount of the four-membered cyclic amide compound according to any one of claims 1 to 6, its stereoisomers/isomers/enantiomers/salts and N-oxides or the composition according to claim 8. Use of the four-membered ring amide compound according to any one of claims 1 to 6, its stereoisomers/isomers/enantiomers/salts and N-oxides, or the composition according to claim 8 in controlling pests and/or fungi (especially nematodes).