R-pyridyloxycarboxylic acid, salt and ester derivative thereof, and preparation method therefor, and herbicidal composition thereof and application thereof

Abstract

To provide an R-pyridyloxycarboxylic acid that has excellent herbicidal activity and high crop safety, demonstrating good selectivity especially for key crops such as rice, and salts and ester derivatives thereof.SOLUTION: An R-pyridyloxycarboxylic acid according to the present invention is represented by formula I, [where A and B independently represent halogen, or alkyl or cycloalkyl with or without halogen, C represents hydrogen, halogen, alkyl or haloalkyl, Q represents halogen, cyano, cyanoalkyl or the like, Y represents nitro or NR1R2], wherein salts thereof include metal salts, amine salts, sulfonium salts, and phosphonium salts.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to the field of agrochemical technology, and in particular to certain R-pyridyloxycarboxylic acids, their salts, their ester derivatives, their preparation methods, their herbicidal compositions and their uses. [Background technology]

[0002] Weed control is one of the most important links in the process of realizing high-efficiency agriculture. Various herbicides are available on the market, such as those described in DE2335349A1, GB1418979A, US3761486, etc., which have the general formula: [ka] and its use as a herbicide, but does not mention the enantiomers of the compounds. Due to challenges such as market expansion, weed resistance, the useful life and economics of pesticides, and increasing public concern about the environment, scientists still need to carry out continuous research and development for new herbicides with high efficacy, safety, economics, and different mechanisms of action. Summary of the Invention

[0003] The present invention provides certain R-pyridyloxycarboxylic acids, their salts, their ester derivatives, their preparation methods, herbicidal compositions, and uses thereof. The compounds have excellent herbicidal activity and high crop safety, and are particularly selective for major crops such as rice.

[0004] The technical solutions adopted by the present invention are as follows:

[0005] The present invention relates to a compound of formula I: [ka] [In the formula, A and B each independently represent a halogen; or an alkyl or cycloalkyl with or without a halogen; C represents hydrogen, halogen, alkyl, or haloalkyl; Q represents halogen, cyano, cyanoalkyl, hydroxyalkyl, amino, nitro, or formyl; alkyl, alkenyl, alkynyl, cycloalkyl, alkoxy, alkylthio, alkylcarbonyl, alkoxycarbonyl, alkylaminoalkyl, or alkoxyalkyl, with or without halogen; or unsubstituted or substituted aryl, heteroaryl, arylalkyl, or heteroarylalkyl; Y represents nitro or NR1R2; R1 is H; 1 to 2 R 11 alkyl, alkenyl or alkynyl, optionally substituted by -COR 12 , Nitro, OR 13 , SO2R 14 , N.R. 15 R 16 , N=CR 17 R 18 , alkylcarbamoyl, dialkylcarbamoyl, trialkylsilyl, or dialkylphosphono; R2 is H; 1 to 2 R 11 alkyl optionally substituted by -COR 12 or NR1R2 represents N=CR 21 NR 22 R 23 Or N=CR 24 OR 25 or a 5- or 6-membered saturated or unsaturated ring which may or may not contain an oxygen atom, a sulfur atom, or a nitrogen atom, and which is unsubstituted or substituted with 1 to 2 groups independently selected from the group consisting of halogen, alkyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio, amino, alkylamino, dialkylamino, and alkoxycarbonyl, R 11independently represent halogen, hydroxy, alkoxy, haloalkoxy, alkylthio, haloalkylthio, amino, alkylamino, dialkylamino, or alkoxycarbonyl; or unsubstituted or substituted aryl or heteroaryl; R 12 represents H, alkyl, haloalkyl, alkoxy, phenyl, phenoxy or benzyloxy; R 13 is H, alkyl, haloalkyl, phenyl, benzyl or CHR 31 C(O)OR 32 represents R 31 represents H, alkyl or alkoxy, R 32 represents H, alkyl or benzyl, R 14 represents alkyl or haloalkyl; R 15 represents H, alkyl, formyl, alkylacyl, haloalkylacyl, alkoxycarbonyl, phenylcarbonyl, phenoxycarbonyl or benzyloxycarbonyl, R 16 represents H or alkyl, R 17 represents H or alkyl; or phenyl unsubstituted or substituted with 1 to 3 groups selected from the group consisting of halogen, alkyl, and alkoxy; R 18 represents H or alkyl, or N=CR 17 R 18 teeth, [ka] represents R 21 and R 24 each independently represents H or alkyl; R 22 and R 23 are each independently H or alkyl, or NR 22 R 23represents a 5- or 6-membered saturated or unsaturated ring with or without an oxygen atom, a sulfur atom, or a nitrogen atom, R 25 represents alkyl.] R-pyridyloxycarboxylic acid, its salt or its ester derivative represented by the formula: the salt is a metal salt, an amine salt, a sulfonium salt or a phosphonium salt, The ester is [ka] [In the formula, X represents O or S; M is alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkylalkyl, -alkyl-Z, with or without halogen; [ka] or unsubstituted or substituted heterocyclyl, aryl or heteroaryl, Z is [ka] cyano or nitro; or unsubstituted or substituted heterocyclyl, aryl or heteroaryl, R3 each independently represents alkyl, alkenyl, alkynyl, cycloalkyl, or cycloalkylalkyl; or unsubstituted or substituted heterocyclyl, aryl, heteroaryl, heterocyclylalkyl, arylalkyl, or heteroarylalkyl; R4, R5, and R6 each independently represent hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkylalkyl, or alkoxycarbonyl; or unsubstituted or substituted heterocyclyl, aryl, heteroaryl, heterocyclylalkyl, arylalkyl, or heteroarylalkyl. The present invention provides an R-pyridyloxycarboxylic acid, a salt thereof, or an ester derivative thereof,

[0006] Preferably, A and B each independently represent halogen; or C1-C8 alkyl or C3-C8 cycloalkyl, with or without halogen; C represents hydrogen, halogen, C-C alkyl or haloC-C alkyl; Q represents halogen, cyano, cyanoC1-C8 alkyl, hydroxyC1-C8 alkyl, amino, nitro, or formyl; C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 cycloalkyl, C1-C8 alkoxy, C1-C8 alkylthio, C1-C8 alkylcarbonyl, C1-C8 alkoxycarbonyl, C1-C8 alkylaminoC1-C8 alkyl, or C1-C8 alkoxyC1-C8 alkyl, with or without halogen; or unsubstituted or substituted aryl, heteroaryl, arylC1-C8 alkyl, or heteroarylC1-C8 alkyl; Y represents nitro or NR1R2; R1 is H; 1 to 2 R 11 C1-C8 alkyl, C2-C8 alkenyl, or C2-C8 alkynyl, optionally substituted by -COR 12 , Nitro, OR 13 , SO2R 14 , N.R. 15 R 16 , N=CR 17 R 18 , C1-C8 alkylcarbamoyl, diC1-C8 alkylcarbamoyl, triC1-C8 alkylsilyl or diC1-C8 alkylphosphono; R2 is H; 1 to 2 R 11 C1-C8 alkyl optionally substituted by COR 12 or NR1R2 represents N=CR 21 NR 22 R 23 Or N=CR 24 OR 25or unsubstituted or substituted with 1 to 2 groups independently selected from the group consisting of halogen, C1-C8 alkyl, C1-C8 alkoxy, haloC1-C8 alkoxy, C1-C8 alkylthio, haloC1-C8 alkylthio, amino, C1-C8 alkylamino, diC1-C8 alkylamino, and C1-C8 alkoxycarbonyl; [ka] represents R 11 are independently halogen, hydroxy, C1-C8 alkoxy, haloC1-C8 alkoxy, C1-C8 alkylthio, haloC1-C8 alkylthio, amino, C1-C8 alkylamino, diC1-C8 alkylamino or C1-C8 alkoxycarbonyl; or phenyl, naphthyl unsubstituted or substituted by 1 to 3 groups selected from the group consisting of halogen, C1-C8 alkyl, haloC1-C8 alkyl, C1-C8 alkoxy and nitro, [ka] represents R 12 represents H, C1-C18 alkyl, haloC1-C8 alkyl, C1-C8 alkoxy, phenyl, phenoxy or benzyloxy; R 13 is H, C1-C8 alkyl, haloC1-C8 alkyl, phenyl, benzyl or CHR 31 C(O)OR 32 represents R 31 represents H, C1-C8 alkyl or C1-C8 alkoxy; R 32 represents H, C1-C8 alkyl or benzyl; R 14 represents C1-C8 alkyl or haloC1-C8 alkyl; R 15represents H, C1-C8 alkyl, formyl, C1-C8 alkylacyl, haloC1-C8 alkylacyl, C1-C8 alkoxycarbonyl, phenylcarbonyl, phenoxycarbonyl or benzyloxycarbonyl; R 16 represents H or C1-C8 alkyl; R 17 represents H or C1-C8 alkyl; or phenyl unsubstituted or substituted with 1 to 3 groups selected from the group consisting of halogen, C1-C8 alkyl, and C1-C8 alkoxy; R 18 represents H or C1-C8 alkyl, or N=CR 17 R 18 but, [ka] represents R 21 and R 24 each independently represents H or C1-C8 alkyl; R 22 and R 23 each independently represents H or C1-C8 alkyl, or NR 22 R 23 but, [ka] represents R 25 represents C1-C8 alkyl; The salt may be a metal salt, an ammonium salt, or + , primary amine salt RNH2, secondary amine salt (R)2NH, tertiary amine salt (R)3N, quaternary amine salt (R)4N + , morpholine salt, piperidine salt, pyridine salt, aminopropylmorpholine salt, Jeffamine D-230 salt, salt of 2,4,6-tri(dimethylaminomethyl)phenol and sodium hydroxide, alkylsulfonium salt, alkylsulfoxonium salt, alkylphosphonium salt or alkanolphosphonium salt, R each independently represent unsubstituted alkyl, alkenyl, alkynyl, cycloalkyl, or phenyl, which are optionally substituted with one or more of the following groups: halogen, hydroxy, alkoxy, alkylthio, hydroxyalkoxy, amino, alkylamino, aminoalkylamino, and phenyl; In formula I-1, X represents O or S; M is C1-C18 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 cycloalkyl, C3-C8 cycloalkylC1-C8 alkyl, -(C1-C8 alkyl)-Z, with or without halogen; [ka] or unsubstituted or substituted heterocyclyl, aryl or heteroaryl, Z, [ka] cyano or nitro; or unsubstituted or substituted heterocyclyl, aryl or heteroaryl, R3 each independently represents C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 cycloalkyl, or C3-C8 cycloalkylC1-C8 alkyl; or unsubstituted or substituted heterocyclyl, aryl, heteroaryl, heterocyclylC1-C8 alkyl, arylC1-C8 alkyl, or heteroarylC1-C8 alkyl; R4, R5 and R6 each independently represent hydrogen, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 cycloalkyl, C3-C8 cycloalkylC1-C8 alkyl or C1-C8 alkoxycarbonyl; or unsubstituted or substituted heterocyclylC1-C8 alkyl, arylC1-C8 alkyl or heteroarylC1-C8 alkyl; The term "heterocyclyl" refers to [ka] wherein these groups contain 0, 1 or 2 oxo groups; The term "aryl" refers to phenyl or naphthyl; The term "heteroaryl" refers to an aromatic ring group containing 3 to 6 ring atoms, optionally fused to a benzo ring, in which 1 to 4 heteroatoms are selected from oxygen, nitrogen and sulfur, e.g., [ka] wherein these groups are selected from the following groups: halogen, nitro, cyano, thiocyano, hydroxy, carboxy, mercapto or formyl; phenyl, benzyl, benzyloxy, or phenoxy, unsubstituted or substituted with at least one group selected from the group consisting of halogen, alkyl, and alkoxy; Alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkylalkyl, OR'', SR'', -alkyl-OR'', -alkyl-SR'', COR'', COOR'', COSR'', SOR'', SOR'', OCOR'', or SCOR'', with or without halogen; and Amino or aminocarbonyl substituted by one or two groups selected from the group consisting of hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkylalkyl, phenyl, benzyl, benzyloxy, phenoxy, COR", COOR", SO2R", and OR". and optionally substituted with at least one group selected from the group consisting of R' each independently represent hydrogen, nitro, hydroxy, or amino; or alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, cycloalkylalkyl, alkoxy, alkenyloxy, alkynyloxy, cycloalkyloxy, alkoxyalkyl, alkoxycarbonyl, alkylthiocarbonyl, alkylsulfonyl, alkylsulfonylalkyl, alkylcarbonyl, alkylcarbonylalkyl, alkylacyloxy, alkylamino, alkylaminocarbonyl, alkoxyaminocarbonyl, alkoxycarbonylalkyl, alkylaminocarbonylalkyl, trialkylsilyl, or dialkylphosphono, with or without halogen; Each R'' independently represents hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, or cycloalkylalkyl.

[0007] More preferably, A and B each independently represent halogen; or C1-C6 alkyl or C3-C6 cycloalkyl, with or without halogen; C represents hydrogen, halogen, C-C alkyl or haloC-C alkyl; Q represents halogen, cyano, cyanoC1-C6 alkyl, hydroxyC1-C6 alkyl, amino, nitro, or formyl; C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, C1-C6 alkoxy, C1-C6 alkylthio, C1-C6 alkylcarbonyl, C1-C6 alkoxycarbonyl, C1-C6 alkylaminoC1-C6 alkyl, or C1-C6 alkoxyC1-C6 alkyl, with or without halogen; or unsubstituted or substituted aryl, heteroaryl, arylC1-C6 alkyl, or heteroarylC1-C6 alkyl; Y represents nitro or NR1R2; R1 is H; 1 to 2 R 11 C1-C6 alkyl, C2-C6 alkenyl, or C2-C6 alkynyl, optionally substituted by -COR 12, Nitro, OR 13 , SO2R 14 , N.R. 15 R 16 , N=CR 17 R 18 , C1-C6 alkylcarbamoyl, diC1-C6 alkylcarbamoyl, triC1-C6 alkylsilyl or diC1-C6 alkylphosphono, R2 is H; 1 to 2 R 11 C1-C6 alkyl optionally substituted by COR 12 or NR1R2 represents N=CR 21 NR 22 R 23 Or N=CR 24 OR 25 or unsubstituted or substituted with 1 to 2 groups independently selected from the group consisting of halogen, C1-C6 alkyl, C1-C6 alkoxy, haloC1-C6 alkoxy, C1-C6 alkylthio, haloC1-C6 alkylthio, amino, C1-C6 alkylamino, diC1-C6 alkylamino, and C1-C6 alkoxycarbonyl; [ka] represents R 11 are independently halogen, hydroxy, C1-C6 alkoxy, haloC1-C6 alkoxy, C1-C6 alkylthio, haloC1-C6 alkylthio, amino, C1-C6 alkylamino, diC1-C6 alkylamino, C1-C6 alkoxycarbonyl; or phenyl, naphthyl, unsubstituted or substituted by 1 to 3 groups selected from the group consisting of halogen, C1-C6 alkyl, haloC1-C6 alkyl, C1-C6 alkoxy, and nitro, [ka] represents R 12 represents H, C1-C14 alkyl, haloC1-C6 alkyl, C1-C6 alkoxy, phenyl, phenoxy or benzyloxy; R 13is H, C1-C6 alkyl, haloC1-C6 alkyl, phenyl, benzyl or CHR 31 C(O)OR 32 represents R 31 represents H, C1-C6 alkyl or C1-C6 alkoxy; R 32 represents H, C1-C6 alkyl or benzyl; R 14 represents C1-C6 alkyl or haloC1-C6 alkyl; R 15 represents H, C1-C6 alkyl, formyl, C1-C6 alkylacyl, haloC1-C6 alkylacyl, C1-C6 alkoxycarbonyl, phenylcarbonyl, phenoxycarbonyl or benzyloxycarbonyl; R 16 represents H or C1-C6 alkyl; R 17 represents H or C1-C6 alkyl; or phenyl unsubstituted or substituted with 1 to 3 groups selected from the group consisting of halogen, C1-C6 alkyl, and C1-C6 alkoxy; R 18 represents H or C1-C6 alkyl, or N=CR 17 R 18 but, [ka] represents R 21 and R 24 each independently represents H or C1-C6 alkyl; R 22 and R 23 each independently represents H or C1-C6 alkyl, or NR 22 R 23 but, [ka] represents R 25 represents C1-C6 alkyl; The salt may be a metal salt, an ammonium salt, or +, primary amine salt RNH2, secondary amine salt (R)2NH, tertiary amine salt (R)3N, quaternary amine salt (R)4N + , morpholine salt, piperidine salt, pyridine salt, aminopropylmorpholine salt, Jeffamine D-230 salt, salt of 2,4,6-tri(dimethylaminomethyl)phenol with sodium hydroxide, C1-C18 alkylsulfonium salt, C1-C18 alkylsulfoxonium salt, C1-C18 alkylphosphonium salt or C1-C18 alkanolphosphonium salt, R each independently represent unsubstituted C1-C18 alkyl, C2-C18 alkenyl, C2-C18 alkynyl, C3-C18 cycloalkyl or phenyl, wherein these groups are optionally substituted by one or more of the following groups: halogen, hydroxy, C1-C8 alkoxy, C1-C8 alkylthio, hydroxyC1-C8 alkoxy, amino, C1-C8 alkylamino, aminoC1-C8 alkylamino, phenyl; In formula I-1, X represents O or S; M is C1-C18 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, C3-C6 cycloalkylC1-C6 alkyl, -(C1-C6 alkyl)-Z, with or without halogen; [ka] or unsubstituted or substituted heterocyclyl, aryl or heteroaryl, Z, [ka] cyano or nitro; or unsubstituted or substituted heterocyclyl, aryl or heteroaryl, R3 each independently represents C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, or C3-C6 cycloalkylC1-C6 alkyl; or unsubstituted or substituted heterocyclyl, aryl, heteroaryl, heterocyclylC1-C6 alkyl, arylC1-C6 alkyl, or heteroarylC1-C6 alkyl; R4, R5, and R6 each independently represent hydrogen, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, C3-C6 cycloalkylC1-C6 alkyl, or C1-C6 alkoxycarbonyl; or unsubstituted or substituted heterocyclylC1-C6 alkyl, arylC1-C6 alkyl, or heteroarylC1-C6 alkyl; The term "heterocyclyl" refers to [ka] wherein these groups contain 0, 1 or 2 oxo groups; The term "aryl" refers to phenyl or naphthyl; The term "heteroaryl" refers to [ka] wherein these groups are selected from the following groups: halogen, nitro, cyano, thiocyano, hydroxy, carboxy, mercapto or formyl; phenyl, benzyl, benzyloxy, or phenoxy, unsubstituted or substituted with at least one group selected from the group consisting of halogen, C1-C6 alkyl, and C1-C6 alkoxy; C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, C3-C6 cycloalkylC1-C6 alkyl, OR'', SR'', -(C1-C6)alkyl-OR'', -(C1-C6)alkyl-SR'', COR'', COOR'', COSR'', SOR'', SOR'', OCOR'', or SCOR'', with or without halogen; and amino or aminocarbonyl substituted by one or two groups selected from the group consisting of hydrogen, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, C3-C6 cycloalkylC1-C6 alkyl, phenyl, benzyl, benzyloxy, phenoxy, COR'', COOR'', SO2R'', and OR''; and is substituted with 0, 1, 2 or 3 groups selected from the group consisting of: R' is each independently hydrogen, nitro, hydroxy, or amino; or C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, C3-C6 cycloalkenyl, C3-C6 cycloalkylC1-C6 alkyl, C1-C6 alkoxy, C2-C6 alkenyloxy, C2-C6 alkynyloxy, C3-C6 cycloalkyloxy, C1-C6 alkoxyC1-C6 alkyl, C1-C6 alkoxycarbonyl, C1-C6 alkyl, with or without fluoro, chloro, or bromo. represents thiocarbonyl, C1-C6 alkylsulfonyl, C1-C6 alkylsulfonylC1-C6 alkyl, C1-C6 alkylcarbonyl, C1-C6 alkylcarbonylC1-C6 alkyl, C1-C6 alkylacyloxy, C1-C6 alkylamino, C1-C6 alkylaminocarbonyl, C1-C6 alkoxyaminocarbonyl, C1-C6 alkoxycarbonylC1-C6 alkyl, C1-C6 alkylaminocarbonylC1-C6 alkyl, tri-C1-C6 alkylsilyl or di-C1-C6 alkylphosphono; Each R'' independently represents hydrogen, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, or C3-C6 cycloalkylC1-C6 alkyl.

[0008] More preferably, A and B each independently represent halogen, C1-C6 alkyl, haloC1-C6 alkyl, or C3-C6 cycloalkyl; C represents hydrogen, halogen, C-C alkyl or haloC-C alkyl; Q is C1-C6 alkyl, haloC1-C6 alkyl, C3-C6 cycloalkyl, C2-C6 alkenyl, C2-C6 alkynyl, halogen, cyano, amino, nitro, formyl, C1-C6 alkoxy, C1-C6 alkylthio, C1-C6 alkoxycarbonyl, hydroxyC1-C6 alkyl, C1-C6 alkoxyC1-C2 alkyl, cyanoC1-C2 alkyl, C1-C6 alkylaminoC1-C2 alkyl, benzyl, naphthyl, furyl, thienyl, thiazolyl, pyridyl or pyrimidinyl; unsubstituted or substituted by C1-C6 alkyl; [ka] or phenyl which is unsubstituted or substituted by at least one group selected from the group consisting of C1-C6 alkyl, haloC1-C6 alkyl, halogen, and C1-C6 alkoxy; Y represents amino, C1-C6 alkylamino, C1-C6 alkylcarbonylamino, phenylcarbonylamino, or benzylamino; or furylmethyleneamino unsubstituted or substituted by haloC1-C6 alkyl; The salt may be a metal salt, an ammonium salt, or + , primary amine salt RNH2, secondary amine salt (R)2NH, tertiary amine salt (R)3N, quaternary amine salt (R)4N + , morpholine salt, piperidine salt, pyridine salt, aminopropylmorpholine salt, Jeffamine D-230 salt, salt of 2,4,6-tri(dimethylaminomethyl)phenol with sodium hydroxide, C1-C14 alkylsulfonium salt, C1-C14 alkylsulfoxonium salt, C1-C14 alkylphosphonium salt or C1-C14 alkanolphosphonium salt, R each independently represent unsubstituted C1-C14 alkyl, C2-C12 alkenyl, C2-C12 alkynyl, C3-C12 cycloalkyl, or phenyl; or C1-C14 alkyl optionally substituted by one or more of the following groups: halogen, hydroxy, C1-C6 alkoxy, C1-C6 alkylthio, hydroxyC1-C6 alkoxy, amino, C1-C6 alkylamino, aminoC1-C6 alkylamino, and phenyl; In formula I-1, X represents O or S; M is C1-C18 alkyl (preferably C1-C12 alkyl, more preferably C1-C8 alkyl, even more preferably C1-C6 alkyl), haloC1-C8 alkyl, C3-C6 cycloalkyl, C2-C6 alkenyl, haloC2-C6 alkenyl, C2-C6 alkynyl, C1-C6 alkoxy, C1-C6 alkoxycarbonyl, C1-C6 alkylsulfonyl, cyanoC1-C6 alkyl (preferably cycloC1-C2 alkyl), nitroC1-C6 alkyl (preferably or nitro C1-C2 alkyl), C1-C6 alkoxy C1-C6 alkyl (preferably C1-C6 alkoxy C1-C2 alkyl), C1-C6 alkoxycarbonyl C1-C6 alkyl (preferably C1-C6 alkoxycarbonyl C1-C2 alkyl), C2-C6 alkenyloxycarbonyl C1-C6 alkyl (preferably C2-C6 alkenyloxycarbonyl C1-C2 alkyl), -(C1-C6 alkyl)-Z (preferably -(C1-C2 alkyl)-Z), [ka] tetrahydrofuryl, pyridyl, naphthyl, furyl, thienyl, [ka] Unsubstituted or substituted with C1-C6 alkyl [ka] or phenyl unsubstituted or substituted with C1-C6 alkyl, haloC1-C6 alkyl, C1-C6 alkylamino, halogen, or C1-C6 alkoxy; Z, [ka] tetrahydrofuryl, pyridyl, [ka] thienyl, furyl, or naphthyl; or phenyl unsubstituted or substituted by at least one group selected from the group consisting of C1-C6 alkyl, C1-C6 alkoxy, haloC1-C6 alkyl, cyano, and halogen; R3 each independently represents C1-C6 alkyl; R4, R5, and R6 each independently represent hydrogen, C1-C6 alkyl, or C1-C6 alkoxycarbonyl; R' represents hydrogen, C1-C6 alkyl or haloC1-C6 alkyl.

[0009] Even more preferably, A and B each independently represent fluoro, chloro, bromo, iodo, methyl, ethyl, propyl, isopropyl, trifluoromethyl, or cyclopropyl; C represents hydrogen, fluoro, chloro, bromo, iodo, methyl or trifluoromethyl; Q is methyl, ethyl, propyl, isopropyl, cyclopropyl, vinyl, ethynyl, fluoro, chloro, bromo, cyano, amino, nitro, formyl, methoxy, methylthio, methoxycarbonyl, monochloromethyl, monofluoromethyl, difluoromethyl, trifluoromethyl, 2-chloroethyl, 2,2,2-trifluoroethyl, hydroxymethyl, [ka] benzyl, naphthyl, furyl, thiazolyl, pyridyl or pyrimidinyl; unsubstituted or substituted by chloro thiazolyl; unsubstituted or substituted by fluoro thienyl; unsubstituted or substituted by methyl or fluoro [ka] or phenyl which is unsubstituted or substituted by at least one group selected from the group consisting of methyl, trifluoromethyl, chloro, and methoxy; Y is NH2, [ka] represents The salt may be a metal salt, an ammonium salt, or + , primary amine salt RNH2, secondary amine salt (R)2NH, tertiary amine salt (R)3N, quaternary amine salt (R)4N + , morpholine salt, piperidine salt, pyridine salt, aminopropylmorpholine salt, Jeffamine D-230 salt, salt of 2,4,6-tri(dimethylaminomethyl)phenol and sodium hydroxide, C1-C6 alkylsulfonium salt, C1-C6 alkylsulfoxonium salt, C1-C6 alkylphosphonium salt or C1-C6 alkanolphosphonium salt, R each independently represent unsubstituted C1-C14 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C12 cycloalkyl, phenyl, or benzyl; or C1-C14 alkyl optionally substituted by one or more of the following groups: hydroxy, C1-C4 alkoxy, C1-C4 alkylthio, hydroxyC1-C4 alkoxy, amino, C1-C4 alkylamino, and aminoC1-C4 alkylamino; The salt is preferably an alkali metal (e.g., sodium, lithium, potassium, cesium, or rubidium) salt, an alkaline earth metal (e.g., calcium, magnesium, barium, or strontium) salt, a heavy metal (e.g., antimony, zinc, bismuth, cadmium, cerium, chromium, cobalt, copper, iron, or other metals with a density of 4 or more) salt, an aluminum salt, an amine salt (e.g., ammonium salt, tetramethylammonium salt, tetraethylammonium salt, tetrapropylammonium salt, tetraisopropylammonium salt, tetrabutylammonium salt, benzyltrimethylammonium salt, benzyltriethylammonium salt, cholineamine salt, monomethylamine salt, dimethylamine salt, trimethylamine salt, monoethylamine salt, diethylamine salt, triethylamine salt, monoisopropylamine salt, diisopropylamine salt, Amine salts, triisopropylamine salts, monoisobutylamine salts, pentylamine salts, hexylamine salts, heptylamine salts, dodecylamine salts, tetradecylamine salts, diallylamine salts, cyclododecylamine salts, benzylamine salts, monoethanolamine salts, diethanolamine salts, triethanolamine salts, tripropanolamine salts, triisopropanolamine salts, tri(2-hydroxypropyl)amine salts, methylmonoethanolamine salts, dimethylmonoethanolamine salts, methyldiethanolamine salts, diethylethanolamine salts, diglycolamine salts, salts of polyamines (e.g., diethylenetriamine salts, dimethylaminopropylamine salts, 1,2-propyldiamine salts, triethylenetetraamine salts, N,N-bis[aminopropyl]methylamine salts), 2-methylthiopropylamine salts, 2-butoxyethylamine salts, [ka] Morpholine salts, piperidine salts, pyridine salts, [ka] or a salt of 2,4,6-tri(dimethylaminomethyl)phenol and sodium hydroxide), a sulfonium salt (for example, an alkylsulfonium salt (for example, a trimethylsulfonium salt, a triethylsulfonium salt), an alkylsulfoxonium salt), a phosphonium salt (for example, an alkylphosphonium salt, an alkanolphosphonium salt), In formula I-1, X represents O or S; M is methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, octadecyl, trifluoromethyl, pentafluoroethyl, 3-chlorobutyl, 2-fluoroethyl, 2-chloroethyl, 2-bromoethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 4,4,4-trifluorobutyl, 2,2,3,3,3-pentafluoropropyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, allyl, 2-propynyl, methoxy, ethoxycarbonyl, methylsulfonyl, [ka] Unsubstituted or methyl substituted [ka] phenyl which is unsubstituted or substituted by methyl, dimethylamino, chloro, methoxy, trifluoromethyl or isopropyl; or benzyl which is unsubstituted or substituted by trifluoromethyl, bromo, chloro, fluoro, methoxy, cyano or methyl, R' represents hydrogen, methyl, ethyl or difluoromethyl.

[0010] In the definitions of the compounds represented by general formula I above and all structural formulas below, the terms, whether used alone or in the compound name, refer to the following substituents: Alkyl groups having 3 or more carbon atoms may be linear or branched. For example, in the compound name "-alkyl-OR"," the alkyl may be -CH-, -CHCH-, -CH(CH)-, -C(CH)-, etc. Examples of alkyl groups include C alkyl: methyl, C alkyl: ethyl, C alkyl: propyl, e.g., n-propyl or isopropyl, C alkyl: butyl, e.g., n-butyl, isobutyl, tert-butyl, or 2-butyl; C alkyl: pentyl, e.g., n-pentyl, C alkyl: hexyl, e.g., n-hexyl, isohexyl, or 1,3-dimethylbutyl. Similarly, examples of alkenyl include allyl, 1-methylprop-2-en-1-yl, 2-methylprop-2-en-1-yl, but-2-en-1-yl, but-3-en-1-yl, 1-methylbut-3-en-1-yl, and 1-methylbut-2-en-1-yl. Examples of alkynyl include propargyl, but-2-yn-1-yl, but-3-yn-1-yl, and 1-methylbut-3-yn-1-yl. The multiple bond may be at any position in each unsaturated group. Examples of cycloalkyl include carbocyclic saturated ring systems having 3 to 6 carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl, or cyclohexyl. Similarly, examples of cycloalkenyl include monocyclic alkenyl systems having 3 to 6 carbon ring members, such as cyclopropenyl, cyclobutenyl, cyclopentenyl, and cyclohexenyl, and the double bond may be at any position. Halogen is fluorine, chlorine, bromine or iodine.

[0011] When a group is substituted with a group, it is understood to mean that the group is substituted with one or more of the same or different groups selected from the groups mentioned above. Furthermore, the same or different substituted characters contained in the same or different substituents are each independently selected and may be the same or different.

[0012] In addition, unless otherwise indicated, in the present invention, a term that appears before or after multiple juxtaposed substituents (separated by "," or "or") has a limiting effect on each subsequent substituent; for example, the term "unsubstituted or substituted" in the expression "unsubstituted or substituted aryl, heteroaryl, arylalkyl, or heteroarylalkyl" has a limiting effect on each subsequent group, "aryl," "heteroaryl," "arylalkyl," or "heteroarylalkyl."

[0013] The method for preparing R-pyridyloxycarboxylic acid, its salt or its ester derivative comprises the following steps:

[0014] reacting a compound of formula III with a compound of formula II to obtain a compound of formula I-1-1; The reaction scheme is: [ka] [In the formula, W represents an alkali metal, preferably K or Na; Hal represents halogen, preferably Br or Cl. As stated above, The reaction is carried out in the presence of a catalyst and a solvent, preferably, the catalyst is TBAB, and the solvent is one or more selected from the group consisting of DCM, DCE, ACN, THF, and DMF.

[0015] reacting said compound of formula I-1-1 in the presence of aqueous lithium hydroxide and a solvent to obtain a compound of formula I; The reaction scheme is: [ka] As stated above, Preferably, the solvent is one or more selected from the group consisting of methanol, ethanol, and isopropanol.

[0016] reacting said compound of formula I with M-SH to give a compound of formula I-1-2; The reaction scheme is: [ka] As stated above, The reaction is carried out in the presence of a dehydrating agent and a solvent, Preferably, the dehydrating agent is DCC, and the solvent is one or more selected from the group consisting of dichloromethane, dichloroethane, acetonitrile, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, tetrahydrofuran, toluene, and xylene.

[0017] Alternatively, when Y represents NR1R2 and R1 and R2 are not both hydrogen, the compound of formula I-2: [ka] or a compound of formula I-1-3: [ka] with the corresponding halide, The halide is preferably chloride or bromide; The reaction is carried out in the presence of a base and a solvent, the base is one or more selected from the group consisting of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, and cesium carbonate; the solvent is one or more selected from the group consisting of THF, 1,4-dioxane, toluene, 1,2-dichloroethane, ethyl acetate, acetonitrile, DMF, acetone, dichloromethane, and chloroform; Optionally, a catalyst, preferably DMAP, is added during the reaction.

[0018] The salts are agriculturally acceptable salts and are preferably prepared by reacting the R-pyridyloxycarboxylic acid compounds of the present invention with a chemically acceptable basic compound.

[0019] For example, in the present application, the diethylamine salt is prepared by reacting the R-pyridyloxycarboxylic acid compound of the present invention with diethylamine.

[0020] As another example, a salt of 2,4,6-tri(dimethylaminomethyl)phenol and sodium hydroxide can be prepared by reacting an R-pyridyloxycarboxylic acid compound of the invention with 2,4,6-tri(dimethylaminomethyl)phenol and sodium hydroxide: [ka] It refers to the salt obtained by reacting with

[0021] The agronomically acceptable salts can be readily isolated and purified by conventional separation methods such as solvent extraction, dilution, recrystallization, column chromatography, and preparative thin layer chromatography.

[0022] The present invention provides a herbicidal composition comprising (i) at least one R-form pyridyloxycarboxylic acid of formula I, its salt, or its ester derivative; preferably, (ii) further comprising one or more additional herbicides and / or safeners; and more preferably, (iii) further comprising an agronomically acceptable formulation adjuvant.

[0023] The present invention provides a method for controlling weeds, comprising the step of applying a herbicidally effective amount of at least one R-pyridyloxycarboxylic acid, its salt, or its ester derivative, or a herbicidal composition to a plant or a weedy area. Preferably, the plant is rice, or the weed is a gramineous weed (e.g., Echinochloa crusgalli (barnyardgrass), Digitaria sanguinalis (crabgrass), Semen Euphorbiae Lathyridis) or a broad-leaved weed (e.g., Monochoria vaginalis (monochoria), Abutilon theophrasti Medic. (velvetleaf), Galium aparine (white spotted weed)).

[0024] The present invention provides use of at least one R-pyridyloxycarboxylic acid, its salt, or its ester derivative, or a herbicidal composition for controlling weeds, preferably wherein the R-pyridyloxycarboxylic acid, its salt, or its ester derivative is used to control weeds in a useful crop, and the useful crop is a genetically modified crop or a crop treated by gene editing technology. Preferably, the crop is rice, or the weed is a grass weed (e.g., Echinochloa crusgalli, Digitaria sanguinalis, Semen Euphorbiae Lathyridis) or a broadleaf weed (e.g., Monochoria vaginalis, Abutilon theophrasti Medic., Galium aparine).

[0025] The compounds of formula I according to the present invention have significant herbicidal activity against a wide range of economically important monocotyledonous and dicotyledonous harmful plants.The active compounds also effectively act against perennial weeds that sprout from rhizomes, rhizomes or other perennial organs and are difficult to control.In this context, it is generally unimportant whether the substance is applied before sowing, before emergence or after emergence.Specifically, some representative examples of monocotyledonous and dicotyledonous weeds that can be controlled by the compounds according to the present invention can be mentioned, but these are not limited to specific species. Examples of weed species on which the active compound has an effective effect include monocotyledonous plants such as Avena spp., Lolium spp., Alopecurus spp., Reed canary grass spp., Barnyardgrass spp., Digitaria spp., Setaria spp., and annual Cyperus spp., as well as perennial plants such as Triticum spp., Cyperus spp., Imperata spp., Sorghum spp., and perennial Cyperus spp.

[0026] In the case of dicotyledonous weed species, the effective range extends, for example, from annual weeds to Cleaver spp., Viola spp., Speedwell spp., Lamium spp., Chickweed spp., Amaranthus spp., White mustard spp., Ipomoea spp., Deer daisy spp., and Abutilon spp., and in the case of perennial weeds, Field mustard spp., Thistle spp., Sorrel spp., and Artemisia spp. The active compounds according to the invention also achieve significant control of harmful plants that occur under the specific conditions of rice cultivation, such as Barnyardgrass, Ardisia spp., Artemisia spp., Cornus spp., Cornus spp., Bulrush spp., and Cyperus spp. When the compounds of the present invention are applied to the soil surface before emergence, the emergence of weed seedlings is completely prevented, or the weeds grow to the cotyledon stage, after which growth stops and they gradually die completely within 3 to 4 weeks. In particular, the compounds of the present invention exhibit excellent activity against common weed, lamb's quarter, dead nettle, bindweed, chickweed (Stellaria media), common burdock, common persimmon, and violet, as well as against Amaranthus species, Cleaver species, and Kochia species.

[0027] The compound of the present invention has excellent herbicidal effect on monocotyledonous and dicotyledonous weeds, but does not damage economically important crops such as wheat, barley, rye, rice, corn, sugar beet, cotton and soybean at all, or the damage is negligible.In particular, they have excellent compatibility with cereals such as wheat, barley, corn, especially wheat.For these reasons, the compound is very suitable for selectively controlling undesirable plant growth in agricultural plantings or ornamental plantings.

[0028] Due to their herbicidal properties, these active compounds may be used to control harmful plants in crops of known or yet to be developed transgenic plants. Transgenic plants generally have particularly significant properties, such as resistance to specific insecticides, particularly to specific herbicides, or resistance to plant diseases or causative organisms of plant diseases (e.g., specific insects or microorganisms, such as fungi, bacteria, or viruses). Other special properties relate, for example, to the quantity, quality, storage stability, composition, and specific components of the harvested product. Thus, transgenic plants with increased starch content, modified starch quality, or different fatty acid compositions in the harvested product are known.

[0029] The use of compounds of formula I according to the invention or salts thereof in economically important transgenic crops of useful plants and ornamental plants is preferred, for example in crops of cereals such as wheat, barley, rye, oats, millet, rice, cassava and corn, or crops of sugar beet, cotton, soybean, rapeseed, potato, tomato, bean and other vegetable species. The compounds of formula I can preferably be used as herbicides in crops of useful plants that are resistant to the phytotoxicity of herbicides or have been genetically engineered to be resistant.

[0030] Conventional methods for producing novel plants with modified properties compared to known plants include, for example, traditional breeding methods and the generation of mutants. Alternatively, novel plants with modified properties can be produced using genetic engineering methods (see, for example, EP-A0221044, EP-A0131624). For example, in some cases: · genetic engineering changes in crop plants to modify the starch synthesized in the plants (e.g. WO92 / 11376, WO92 / 14827, WO91 / 19806); transgenic crops that are resistant to certain herbicides of the glufosinate (glufosinate ammonium) type (see, for example, EP-A 0242236, EP-A 0242246), glyphosate type (WO 92 / 00377) or sulfonylurea type (EP-A 0257993, U.S. Pat. No. 5,013,659 A); Transgenic crops capable of producing Bacillus thuringiensis toxins (Bt toxins) that confer resistance to certain pests on plants, such as cotton (EP-A0142924, EP-A0193259); Transgenic crops with altered fatty acid composition have been described (WO91 / 13972).

[0031] Numerous molecular biology techniques that allow the creation of novel transgenic plants with modified properties are basically known; see, for example, Sambrook et al., 1989, Molecular Cloning, A Laboratory Manual, 2nd ed. Cold Spring Harbor Laboratory Press, Cold Spring Harbor, NY; or Winnacker "Gene und Klone" [Genes and Clones], VCH Weinheim, 2nd edition 1996, or Christou, "Trends in Plant Science" 1 (1996) 423-431). To perform such genetic engineering manipulations, nucleic acid molecules can be introduced into plasmids, which allow DNA sequence recombination to induce mutations or changes in the sequence. Using the standard methods mentioned above, it is possible, for example, to replace bases to remove partial sequences or to add natural or synthetic sequences. To connect DNA fragments to each other, adapters or linkers can be attached to the fragments.

[0032] Plant cells with reduced gene product activity can be produced, for example, by expressing at least one suitable antisense RNA, sense RNA to achieve a co-suppression effect, or by expressing at least one appropriately constructed ribozyme that specifically cleaves the transcript of the above-mentioned gene product.

[0033] For this purpose, it is possible to use both DNA molecules containing the entire coding sequence of the gene product, including any flanking sequences that may be present, and DNA molecules containing only portions of the coding sequence (these portions must be long enough to cause an antisense effect in cells).It is also possible to use DNA sequences that are highly homologous to the coding sequence of the gene product, but not completely identical.

[0034] When expressing nucleic acid molecules in plants, synthesized proteins can be localized in any desired compartment of plant cells.However, to achieve localization in a specific compartment, for example, coding region can be linked with a DNA sequence that ensures localization to a specific compartment.Such sequences are known to those skilled in the art (see, for example, Braun et al., EMBO J. 11 (1992), 3219-3227; Wolter et al., Proc. Natl. Acad. Sci. USA 85 (1988), 846-850; Sonnewald et al., Plant J. 1 (1991), 95-106).

[0035] Transgenic plant cells can be regenerated into whole plants using known techniques. In principle, the transgenic plants can be of any desired plant species, i.e., both monocotyledonous and dicotyledonous plants. In this way, transgenic plants can be obtained that have modified properties due to the overexpression, suppression or inhibition of a homologous (=natural) gene or gene sequence or the expression of a heterologous (=foreign) gene or gene sequence.

[0036] When the active compounds according to the present invention are used in transgenic crops, in addition to the effects on harmful plants that can be observed in other crops, there are many effects specific to the application of each transgenic crop.For example, the range of weeds that can be controlled is changed or clearly expanded, the application rate that can be used for application is improved, the favorable and good compatibility with the herbicides that transgenic crops are resistant to, and the growth and yield of transgenic crops.Therefore, the present invention also provides the use of compounds according to the present invention as herbicides for controlling harmful plants in transgenic crops.

[0037] Furthermore, the substances according to the present invention have significant growth-regulating properties in crops. They are involved in the regulation of plant metabolism, which can be used for the targeted control of plant constituents and the promotion of harvest, for example, by stimulating drought and stunted growth. Furthermore, they are suitable for generally regulating and suppressing undesirable plant growth without destroying the plant in the process. Plant growth suppression plays an important role in monocotyledonous and dicotyledonous crops, because it can reduce or completely prevent lodging.

[0038] The compounds according to the invention can be applied in conventional formulations in the form of wettable powders, emulsifiable concentrates, sprayable solutions, dusts or granules. Thus, the present invention also provides herbicidal compositions comprising a compound of formula I. The compounds of formula I can be formulated by various methods depending on the prevailing biological and / or physicochemical parameters. Examples of suitable formulation options are wettable powders (WP), water-soluble powders (SP), water-soluble concentrates, emulsifiable concentrates (EC), emulsifiable concentrates (EW) (e.g. oil-in-water emulsions and water-in-oil emulsions), sprayable solutions, suspension concentrates (SC), oil dispersants (OD), oil-based or aqueous dispersions, oil-miscible solutions, dusts (DP), capsule suspensions (CS), seed dressing compositions, granules for dusting and soil application, granules for disintegration of fine granules (GR), spray granules, dressing granules and adsorbent granules, water-dispersible granules (WG), water-soluble granules (SG), ULV formulations, microcapsules and waxes. These individual formulation types are known in principle and are described, for example, in Winnacker-Kuchler, "Chemische Technologie" [Chemical Technology], Volume 7, C. Hauser Verlag Munich, 4th Edition 1986; Wade van Valkenburg, "Pesticide Formulations", Marcel Dekker, NY, 1973; K. Martens, "Spray Drying" Handbook, 3rd Edition 1979, G. Goodwin Ltd. London.

[0039] Necessary formulation aids, such as inert materials, surfactants, solvents and other additives, are likewise known and can be found, for example, in Watkins, "Handbook of Insecticide Dust Diluents and Carriers", 2nd Ed., Darland Books, Caldwell NJ; H. v. Olphen, "Introduction to Clay Colloid Chemistry"; 2nd Ed., J. Wiley & Sons, NY; C. Marsden, "Solvents Guide"; 2nd Ed., Interscience, NY 1963; McCutcheon's "Detergents and Emulsifiers Annual", MC Publ. Corp., Ridgewood NJ; Sisley and Wood, "Encyclopedia of Surface Active Agents", Chem. Publ. Co. Inc., NY 1964; Schonfeldt, "Grenzflchenaktive thylenoxidaddukte" [Surface-active ethylene oxide adducts], Wiss. Verlagsgesell., Stuttgart 1976; Winnacker-Kuchler, "Chemische Technologie" [Chemical Technology], Volume 7, C. Hauser Verlag Munich, 4th Edition 1986.

[0040] Wettable powders are formulations that are uniformly dispersible in water and contain, in addition to the active compound and a diluent or inert substance, ionic and / or nonionic surfactants (wetting agents, dispersants), such as polyethoxylated alkylphenols, polyethoxylated fatty alcohols, polyethoxylated fatty amines, fatty alcohol polyglycol ether sulfates, alkanesulfonates, alkylbenzenesulfonates, sodium ligninsulfonate, sodium 2,2'-dinaphthylmethane-6,6'-disulfonate, sodium dibutylnaphthalenesulfonate, or sodium oleoylmethyl taurate. To prepare wettable powders, the herbicidally active compound is finely milled using conventional equipment, such as a hammer mill, a fan mill, or an air jet mill, and mixed simultaneously or subsequently with formulation adjuvants.

[0041] Emulsifiable concentrates are prepared by dissolving the active compound in an organic solvent (e.g., butanol, cyclohexanone, dimethylformamide, xylene, or a relatively high-boiling aromatic compound or hydrocarbon, or a mixture of solvents) with the addition of one or more ionic and / or nonionic surfactants (emulsifiers). Examples of emulsifiers that can be used include calcium alkylarylsulfonates (e.g., calcium dodecylbenzenesulfonate) or nonionic emulsifiers (e.g., fatty acid polyglycol esters, alkylaryl polyglycol ethers, fatty alcohol polyglycol ethers, propylene oxide-ethylene oxide condensates, alkyl polyethers, sorbitan esters (e.g., sorbitan fatty acid esters), or polyoxyethylene sorbitan esters (e.g., polyoxyethylene sorbitan fatty acid esters)).

[0042] Powders are obtained by grinding the active compound with finely divided solid substances, such as talc, natural clays (e.g., kaolin, bentonite, and pyrophyllite) or diatomaceous earth. Suspension concentrates may be aqueous or oil-based. They can be prepared, for example, by wet milling using conventional commercially available bead mills, with or without the addition of surfactants, as in the case of other formulation types, for example, as already mentioned above.

[0043] Emulsions, e.g., oil-in-water emulsions (EW), can be prepared, for example, by means of agitators, colloid mills and / or static mixers using, for example, aqueous organic solvents and, if desired, surfactants as already mentioned above in the case of other formulation types.

[0044] Granules can be prepared by spraying the active compound onto an absorbent granulated inert material, or by applying the active compound to the surface of a carrier, such as sand, kaolinite, or a granulated inert material, using an adhesive binder, such as polyvinyl alcohol, sodium polyacrylate, or mineral oil.Similarly, suitable active compounds can be mixed with fertilizers as needed and granulated by conventional methods for preparing fertilizer granules.Generally, water-dispersible granules are prepared by conventional methods, such as spray drying, fluidized bed granulation, disk granulation, mixing using a high-speed mixer, and extrusion without solid inert materials.

[0045] For the preparation of granules by disk, fluidized bed, extrusion and spraying methods, see, for example, "Spray-Drying Handbook" 3rd ed. 1979, G. Goodwin Ltd., London; J.E. Browning, "Agglomeration", Chemical and Engineering 1967, pp. 147ff.; "Perry's Chemical Engineer's Handbook", 5th Ed., McGraw-Hill, New York 1973, pp. 8-57. For further details on the formulation of crop protection products, see, for example, G.C. Klingman, "Weed Control as a Science", John Wiley and Sons Inc., New York, 1961, pp. 81-96, and J.D. Freyer, S.A. Evans, "Weed Control Handbook", 5th Ed., Blackwell Scientific Publications, Oxford, 1968, pp. 101-103.

[0046] Typically, agricultural chemical formulations contain 0.1 to 99% by weight, specifically 0.1 to 95% by weight, of the active compound of formula I. In wettable powders, the concentration of the active compound is, for example, about 10 to 99% by weight, with the remainder consisting of conventional formulation constituents being up to 100% by weight. In emulsifiable concentrates, the concentration of the active compound may be, for example, about 1 to 90% by weight, preferably 5 to 80% by weight. Powder-form formulations contain 1 to 30% by weight, most commonly 5 to 20% by weight, while sprayable solutions contain about 0.05 to 80% by weight, preferably 2 to 50% by weight, of the active compound. In the case of water-dispersible granules, the content of the active compound depends in part on whether the active compound is in liquid or solid form and on the granulation aids and fillers used. In water-dispersible granules, the content of the active compound is, for example, 1 to 95% by weight, preferably 10 to 80% by weight.

[0047] Furthermore, the above formulations of the active compounds may contain tackifiers, wetting agents, dispersants, emulsifiers, penetrants, preservatives, antifreeze agents, solvents, fillers, carriers, colorants, antifoaming agents, evaporation retardants, pH adjusters and viscosity adjusters, each of which is conventional.

[0048] Based on these formulations, it is also possible to produce combinations with other pesticidal active ingredients, such as insecticides, acaricides, herbicides and fungicides, as well as combinations with safeners, fertilizers and / or growth regulators, for example in ready-to-use or tank-mix form.

[0049] Suitable active compounds that can be combined with the active compounds of the present invention in mixed formulations or tank mixes are known active compounds, for example, as described in World Herbicide New Product Technology Handbook, China Agricultural Science and Farming Techniques Press, 2010.9 and the documents cited therein.For example, as herbicides that can be combined with the compound of formula I, the following active compounds can be mentioned (note: compounds are named by their "trivial names" according to the International Organization for Standardization (ISO) or, where appropriate, by their chemical names, together with their conventional code numbers): acetochlor, butachlor, alachlor, propisochlor, metolachlor, s-metolachlor, pretilachlor, propachlor, ethachlor, napropamide and R-left-handed napropamide (R-left-handed naproxenic acid, propanil, mefenacet, diphenamide, diflufenican, ethaprochlor, beflubutamide, bromobutide, dimethenamid, dimethenamid-P, etobenzanide, flufenacet, thenylchlor, metazachlor, isoxaben, flamprop-M-methyl, flamprop-M-propyl, allidochlor, petoxamide, chloranocryl, ciprazine, mefluidide, monalid, delaclor, prinachlor, terbuchlor, xylachlor, dimethachlor, cisanilide, trimexachlor, clometasone, Prop, propyzamide, pentanochlor, carbetamide, benzoylpropethyl, ciprazole, butenachlor, tebutam, benzipram, mogrton, dichlofluanid, naproanilide, diethathylethyl, naptalam, flufenacet, benzadox, chlorthiamide, chlorophthalimide, isocarbamide, picolinafen, atrazine, simazine, prometryn, cyanatrine, simetryn, ametryn, propazine, dipropetrine, SSH-108, terbutryn, terbuthylazine, triaziflam, ciprazine, proglinadin, trietazine, prometon, simeton, aziprothrine,Desmetrin, dimethametrin, procyazine, mesoprazine, sebutylazine, secbumeton, terbumeton, metoprothrin, cyanatrin, ipazine, chlorazine, atraton, pendimethalin, eglinadine, cyanuric acid, indaziflam, chlorsulfuron, metsulfuron-methyl, bensulfuron-methyl, chlorimuron-ethyl, tribenuron-methyl, thifensulfuron-methyl, pyrazosulfuron-ethyl, mesosulfuron, iodosulfuron-methyl sodium, foramsulfuron, cinosulfuron, triasulfuron, sulfometruron methyl, nicosulfuron, ethametsulfuron methyl, amidosulfuron, ethoxysulfuron, cyclosulfamuron, rimsulfuron, azimsulfuron, flazasulfuron, monosulfuron, monosulfuron ester, flucarbazone sodium, flupyrsulfuron methyl, halosulfuron methyl, oxasulfuron, imazosulfuron, primisulfuron, propoxycarbazone, prosulfuron, sulfosulfuron, trifloxysulfuron, triflusulfuron methyl, tritosulfuron, metsulfuron methyl ... Lucetosulfuron, HNPC-C, orthosulfamuron, propyrisulfuron, metazosulfuron, acifluorfen, fomesafen, lactofen, fluoroglycofen, oxyfluorfen, chlornitrofen, aclonifen, ethoxyfen ethyl, bifenox, nitrofluorfen, chlormethoxyfen, fluorodoifen, fluoronitrofen, freeroxifene, nitrofen, TOPE, DMNP, PPG1013, AKH-7088, halosafen, chlortoluron, isoproturon, linuron, di Uron, daimron, fluometuron, benzthiazuron, methabenzthiazuron, cumyluron, etidimuron, isouron, tebuthiuron, buturon, chlorbromuron, methyldaimron, fenobenzuron, SK-85, metobromuron, metoxuron, afesin, monuron, siduron, fenuron, fluothiuron, nebron, chloroxuron, noruron, isonoruron, 3-cyclooctyl-1, thiazafluron, tebuthiuron, difenoxuron, parafluron, methylamine tribunil,Carbutilate, trimeturon, dimefuron, monisouron, anisuron, methiuron, chloreturon, tetrafluron, phenmedipham, phenmedipham-ethyl, desmedipham, asulam, terbucarb, barban, propham, chlorpropham, rowmate, swep, chlorbufam, carboxazole, chlorprocarb, fenashlam, BCPC, CPPC, carbasulam, butyrate, benthiocarb, vernolate, molinate, triallate, dimepipere ate, esprocarb, pyributicarb, cycloate, avadex, EPTC, ethiolate, orbencarb, pebulate, prosulfocarb, thiocarbazyl, CDEC, dimexano, isoporinate, methiobencarb, 2,4-D butyl ester, MCPA-Na, 2,4-D isooctyl ester, MCPA isooctyl ester, 2,4-D sodium salt, 2,4-D dimethylamine salt, MCPA-thioethyl, MCPA, 2,4-D propionic acid, high 2,4-D propionate, 2,4-D butyric acid, MCPA propionic acid, MCPA propionate, MCPA butyrate, 2,4,5-D, 2,4,5-D propionic acid, 2,4,5-D butyric acid, MCPA amine salt, dicamba, elvon, chlorfenac, saison, TBA, chloramben, methoxy-TBA, diclofop-methyl, fluazifop-butyl, fluazifop-p-butyl, haloxyfop-methyl, haloxyfop-P, quizalofop-ethyl, quizalofop-ethyl, fenoxaprop-ethyl, fenoxaprop-p-ethyl, propaquizafop, cyhalofop-butyl, metamifop, clodinafop propargyl, fenthiaprop-ethyl, chloroazifop-propynyl, poppenate-methyl, trifopsim, isoxapyrifop, paraquat, diquat, oryzalin, ethalfluralin, isoproparin, nitralin, profluralin, prodiamine, benfluralin, fluchloralin, dinitramine, dipropalin, chlornidine, methalproparin, dinoprop,Glyphosate, anilofos, glufosinate ammonium, amiprophos methyl, sulfosate, piperophos, bialaphos sodium, bensulide, butamiphos, focarb, 2,4-DEP, H-9201, zytron, imazapyr, imazethapyr, imazaquin, imazamox, imazamox ammonium salt, imazapic, imazamethabenzmethyl, fluroxypyr, fluroxypyr isooctyl ester, clopyralid, picloram, triclopyr, dithiopyr, haloxydine, 3,5,6-trichloro-2-pyridin Nol, thiazopyr, fluridone, aminopyralid, diflufenzopyr, triclopyr-butotyl, cliodinate, sethoxydim, clethodim, cycloxydim, alloxydim, clefoxydim, butroxydim, tralkoxydim, tepraloxydim, butidazole, metribuzin, hexazinone, metamitron, etiodin, ametridione, amivudine, bromoxynil, bromoxynil octanoate, ioxynil octanoate, ioxynil, dichlobenil, diphenatryl, pyraclonil, chloroxynil, iodobonyl, flumetula , florasulam, penoxsulam, metsullam, cloransulam-methyl, diclosulam, piroxsulam, benfuresate, bispyribac-sodium, pyribenzoxim, pyriftalid, pyriminobac-methyl, pyrithiobac-sodium, benzobisilone, mesotrione, sulcotrione, tembotrione, tefluriltrione, bicyclopyrone, ketodpiradox, isoxaflutole, clomazone, fenoxasulfone, methiozolin, fluazolate, pyraflufen-ethyl, pyrazolinate, difenzo Cort, pyrazoxyfene, benzofenap, nipiraclofen, pyrasulfotole, topramezone, piroxasulfone, cafenstrole, flupoxam, aminotriazole, amicarbazone, azafenidin, carfentrazone ethyl, sulfentrazone, bencarbazone, benzfendizone, butafenacil, bromacil, isocyl, lenacil, terbacil, flupropacil, cinidon ethyl, flumiclorac pentyl, flumioxazin, propyzamide, MK-129, flumezin, pentachlorophenol, dinoseb, dinoterb,Dinoterb acetate, dinosam, DNOC, chloronitrophene, medinoterb acetate, dinofenate, oxadiargyl, oxadiazon, pentoxazone, flufenacet, fluthiacetmethyl, fentrazamide, flufenpyr ethyl, pyrazone, brompyrazone, metoflurane, kusakira, dimidazon, oxapyrazon, norflurazon, pyridafol, quinclorac, Quinmelac, bentazone, pyridate, oxaziclomefone, benazolin, clomazone, cinmethylin, ZJ0702, pyribambenzpropyl, indanofan, sodium chlorate, dalapon, trichloroacetic acid, monochloroacetic acid, hexachloroacetone, flupropanate, cypercort, bromofenoxime, epronaz, methazole, flurtamone, benfuresate, esofumesate, thiochlorim, chlorthal, fluorochloridone, tabron ), acrolein, bentlanil, tridiphane, chlorfenpropmethyl, thidiarizonaimin, phenisofam, busoxinone, methoxyphenone, saflufenacil, clasifos, chloropon, arorac, diethamcort, etonipromide, iprimidam, ipfencarbazone, thiencarbazone methyl, pyrisulfan, chlorflurazole, tripropindan, sulglicapine, prosul Farin, cambendichlor, aminocyclopyrachlor, rodetanil, benoxacor, fenclorim, flurazole, fenchlorazole ethyl, cloquintocet-mexyl, oxabetrinil (MG / 91, cyometrinil, DKA-24, mefenpyr-diethyl, furilazole, fluxofenim, isoxadifen-ethyl, dichlormid, halauxifen-methyl, DOW florpyraxifen, UBH-509, D489, LS 82-556, KPP-300, NC-324, NC-330, KH-218, DPX-N8189, SC-0744, DOWCO535, DK-8910, V-53482, PP-600, MBH-001, KIH-9201, ET-751, KIH-6127 and KIH-2023. ,

[0050] In the present context, when an abbreviation of the generic name of an active compound is used, it in each case includes all conventional derivatives, such as esters and salts, as well as isomers (especially optical isomers), in particular one or more commercially available forms. When a generic name indicates an ester or salt, it also in each case includes all other conventional derivatives, such as other esters, salts, free acids and neutral compounds, as well as isomers (especially optical isomers), in particular one or more commercially available forms. The chemical name given to a compound refers to at least one compound encompassed by the generic name, and usually refers to a preferred compound.

[0051] The formulations used, present in commercial form, are diluted, if appropriate, by customary methods, for example, with water in the case of wettable powders, emulsifiable concentrates, dispersions, and water-dispersible granules. Products in the form of dusts, granules for soil application or scattering, and sprayable solutions are usually not further diluted with other inert substances prior to use. The application rate of the compound of formula I required varies depending on external conditions, such as temperature, humidity, the nature of the herbicide used, etc. It may vary over a wide range, for example, from 0.001 to 1.0 kg ai / ha, preferably from 0.005 to 750 g ai / ha, and in particular from 0.005 to 500 g ai / ha of reactive substance. [Example]

[0052] Specific Modes for Carrying Out the Invention The following examples are intended to illustrate the present invention and should not be construed as limiting the invention in any way. It is intended that the scope of protection sought in the present invention be defined by the claims.

[0053] From the viewpoint of economy and diversity of compounds, we preferably synthesize a plurality of compounds, some of which are shown in Tables 1-2 below. The structures and information of specific compounds are shown in Tables 1-3. The compounds in Tables 1-2 are described to further illustrate the present invention, but are not limited thereby. The subject matter of the present invention should not be construed by those skilled in the art as being limited to the following compounds.

[0054] [Table 1] TIFF2023139056000043.tif255154TIFF2023139056000044.tif255153TIFF20231390560 00045.tif255152TIFF2023139056000046.tif255153TIFF2023139056000047.tif144170

[0055] [Table 2] TIFF2023139056000049.tif244170TIFF2023139056000050.tif243170TIFF2023139056000051.tif243170TIFF2023139056000052.tif243170TIFF2023139056000053.tif243170TIFF2023139056000054.tif244170TIFF2023139056000055.tif244170TIFF2023139056000056.tif242170TIFF2023139056000057.tif243170TIFF2023139056000058.tif242170TIFF2023139056000059.tif243170TIFF2023139056000060.tif243170TIFF2023139056000061.tif245170TIFF2023139056000062.tif242170TIFF2023139056000063.tif242170TIFF2023139056000064.tif241170TIFF2023139056000065.tif244170TIFF2023139056000066.tif244170TIFF2023139056000067.tif242170TIFF2023139056000068.tif242170TIFF2023139056000069.tif243170TIFF2023139056000070.tif244170TIFF2023139056000071.tif243170TIFF2023139056000072.tif243170TIFF2023139056000073.tif240170TIFF2023139056000074.tif241170TIFF2023139056000075.tif244170TIFF2023139056000076.tif244170TIFF2023139056000077.tif241170TIFF2023139056000078.tif242170TIFF2023139056000079.tif244170TIFF2023139056000080.tif242170TIFF2023139056000081.tif242170TIFF2023139056000082.tif243170TIFF2023139056000083.tif92170.

[0056] [Table 3] TIFF2023139056000085.tif242170TIFF2023139056000086.tif252170TIFF2023139056 000087.tif239170TIFF2023139056000088.tif253170TIFF2023139056000089.tif25017 0TIFF2023139056000090.tif246170TIFF2023139056000091.tif255170TIFF2023139056 000092.tif249170TIFF2023139056000093.tif251170TIFF2023139056000094.tif86170

[0057] Several methods for preparing the compounds of the present invention are described in detail in the following schemes and examples. Starting materials can be commercially purchased or prepared according to methods known in the literature or detailed diagrams. Those skilled in the art will understand that other synthetic routes are also available for synthesizing the compounds of the present invention. While specific starting materials and conditions are described below in the synthetic routes, these can be easily replaced with other similar starting materials and conditions, and various isomers of compounds produced by variations or modifications of the preparation methods of the present invention are also within the scope of the present invention. In addition, the preparation methods described below can be further modified in accordance with the present disclosure using conventional chemical methods well known to those skilled in the art. For example, appropriate group protection during the reaction can be used.

[0058] Method examples are provided below to facilitate a further understanding of the preparation methods of the present invention. The specific materials, 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 synthesis of the compounds shown in the following tables are commercially available or can be easily prepared by those skilled in the art.

[0059] Representative examples of compounds are shown below, but the synthesis methods for other compounds are similar and will not be described in detail here.

[0060] 1. Synthesis of Compounds 2-31 and 1-2 (1) Compound 2-31-1 (300 mg, 1.27 mmol), compound b (255 mg, 1.53 mmol), a catalytic amount of TBAB (10 mg), and DMF (20 mL) were placed in a 50 mL round-bottom flask and heated to 85 °C for 12 hours. After the reaction of the starting material was complete as detected by LC-MS, the reaction mixture was cooled to room temperature, concentrated, and then separated by column chromatography to give compound 2-31 (180 mg, 47% yield). [ka]

[0061] (2) Compound 2-31 (0.5 g, 1.77 mmol) and methanol (20 mL) were placed in a 100 mL single-neck flask. Lithium hydroxide (74 mg, 1.77 mmol) was dissolved in 2 mL of water and slowly added dropwise to the single-neck flask at room temperature. The mixture was then stirred at room temperature for 12 hours. After the reaction of the starting material was complete as detected by LC-MS, the reaction mixture was adjusted to pH 5-6 with 0.5 M dilute hydrochloric acid, concentrated, and then extracted with water and ethyl acetate. The organic phase was dried and concentrated to give compound 1-2 (400 mg) as a white solid. [ka]

[0062] 2. Synthesis of Compound 2-45 (1) Compound 2-45-1 (1 g, 8.61 mmol) and phosphorus oxybromide (3.7 g, 12.9 mmol) were placed in a 50 mL round-bottom flask and heated to 60 °C for 5 hours. After the reaction of the starting material was complete as detected by HPLC, the reaction mixture was cooled to room temperature and then slowly poured into an ice-water bath. The temperature was controlled at 0-10 °C during quenching. The aqueous phase was extracted with ethyl acetate (100 mL × 2). The organic phase was dried and concentrated to give compound 2-45-2 (1.5 g, crude product). This compound was used directly in the next step without further purification. [ka]

[0063] (2) Compound a (400 mg, 2.13 mmol), compound 2-45-2 (700 mg), a catalytic amount of TBAB (10 mg), and DMF (10 mL) were placed in a 50 mL round-bottom flask and heated to 85 °C for 12 hours. After the reaction of the starting material was complete as detected by LC-MS, the reaction mixture was cooled to room temperature and extracted with water (100 mL) and methyl tert-butyl ether (50 mL × 2). The organic phase was dried, concentrated, and separated by column chromatography to give compound 2-45 (200 mg, 35% yield) as a white solid. [ka]

[0064] 3. Synthesis of Compound 2-69 Compound a (0.5 g, 2.13 mmol), compound b (313 mg, 2.55 mmol), a catalytic amount of TBAB (10 mg), and DMF (10 mL) were placed in a round-bottom flask and stirred at room temperature (15 °C) for 24 hours. LC-MS detection revealed that a small amount of starting material remained, so further treatment was performed. The reaction mixture was poured into water (50 mL) and extracted twice with methyl tert-butyl ether (50 mL × 2). The organic phase was dried, concentrated, and separated by column chromatography to give compound 2-69 (300 mg, 50% yield) as a white solid. [ka]

[0065] 4. Synthesis of Compound 2-319 Compound 1-26 was prepared by following the synthesis of compound 1-2. Compound 1-26 (400 mg, 1.49 mmol), compound 2-319-1 (219 mg, 1.49 mmol), DCC (459 mg, 2.24 mmol), and anhydrous DCM (20 mL) were added to a 100 mL round-bottom flask and reacted at room temperature for 12 hours. After the reaction of the starting material was complete as detected by LC-MS, the reaction mixture was concentrated and purified by column chromatography to give compound 2-319 (250 mg, 41% yield) as a white solid. [ka]

[0066] 5. Synthesis of Compounds 2-378 and 1-71 (1) Compound 2-69 (200 mg, 0.71 mmol), compound c (145 mg, 0.85 mmol), potassium carbonate (1 equivalent), a catalytic amount of DMAP (10 mg), and acetonitrile (20 mL) were placed in a 50 mL round-bottom flask, heated to 80 °C, and reacted for 12 hours. After the reaction of the starting material was complete as detected by LC-MS, the reaction mixture was cooled to room temperature, concentrated, and separated by column chromatography to give compound 2-378 (150 mg, 50% yield) as a colorless oil. [ka]

[0067] (2) Compound 2-378 (0.15 g, 0.43 mmol) and methanol (20 mL) were placed in a 100 mL single-neck flask. Lithium hydroxide (48 mg, 2 mmol) was dissolved in 2 mL of water and slowly added dropwise to the round-bottom flask at room temperature, followed by stirring for 12 hours. After the reaction of the starting material was complete as detected by LC-MS, the reaction solution was adjusted to pH 5-6 with 0.5 M dilute hydrochloric acid, concentrated, and then extracted with water and ethyl acetate. The organic phase was dried and concentrated to give compound 1-71 (100 mg) as a white solid. [ka]

[0068] Bioactivity evaluation The activity level criteria for plant destruction (=growth inhibition rate) are as follows: Level 5: Growth inhibition rate is 85% or more. Level 4: Growth inhibition rate is 60% or more but less than 85%. Level 3: Growth inhibition rate is between 40% and 60%. Level 2: Growth inhibition rate is 20% or more but less than 40%. Level 1: Growth inhibition rate is 5% or more but less than 20%. Level 0: Growth inhibition rate is less than 5%.

[0069] The growth inhibition rate mentioned above is the fresh weight inhibition rate.

[0070] Post-emergence stage test experiment Monocotyledonous and dicotyledonous weed seeds and seeds of major crops (i.e., wheat, corn, rice, soybean, cotton, oilseeds, millet, sorghum, etc.) were placed in plastic pots filled with soil. They were then covered with 0.5 to 2 cm of soil and grown in a suitable greenhouse environment. Two weeks after sowing, test plants were treated at the 2- to 3-leaf stage. Each test compound of the present invention was dissolved in acetone, followed by the addition of Tween-80. An emulsifiable concentrate of methyl oleate was used as a synergist at 1.5 liters per hectare and diluted with a certain amount of water to a certain concentration. This solution was sprayed onto the plants using a sprayer. The test plants were then cultivated in a greenhouse for 3 weeks. The experimental results of weed control efficacy are shown in Tables 4 and 5.

[0071] [Table 4] TIFF2023139056000104.tif255169TIFF2023139056000105.tif254170TIFF2023139056000106.tif255169TIFF2023139056000107.tif218170

[0072] [Table 5] TIFF2023139056000109.tif253170TIFF2023139056000110.tif255170TIFF2023139056000111.tif164170

[0073] Surprisingly, despite their similar structure to the control compounds, the compounds of the present invention exhibited excellent activity and selectivity against major grass weeds, broadleaf weeds, and Cyperus rotundus (nutsedge) in rice paddies, demonstrating excellent commercial value. In particular, they were also effective in controlling major weeds resistant to the ALS inhibitor bispyribac-sodium and the ACCe inhibitor cyhalofop-butyl. Furthermore, the R-isomers of the present invention exhibited significantly improved activity against grass weeds, such as Echinochloa crusgalli, Digitaria sanguinalis, and Semen Euphorbiae Lathyridis, compared with the racemic and S-isomers, and also exhibited excellent selectivity against rice.

[0074] Experiments on the effects of weeds at the pre-emergence stage Monocotyledonous and dicotyledonous weed seeds and seeds of major crops (e.g., wheat, corn, rice, soybeans, cotton, oilseeds, millet, and sorghum) were placed in plastic pots filled with soil and covered with 0.5 to 2 cm of soil. The test compounds of the present invention were dissolved in acetone, Tween-80 was added, and the solution was diluted with a certain amount of water to a certain concentration. The solution was sprayed immediately after sowing. After spraying, the resulting seeds were cultivated in a greenhouse for 4 weeks, and the test results were observed. At a spray rate of 250 g ai / ha, the herbicides were generally found to be highly effective, particularly against weeds such as Echinochloa crusgalli, Digitaria sanguinalis, and Abutilon theophrasti. Many compounds showed good selectivity against corn, wheat, rice, soybeans, rapeseed, and other crops.

[0075] As a result of experiments, we have found that the compounds of the present invention have generally high weed control effects, especially against major grass weeds that commonly occur in corn, rice, and wheat fields, such as Echinochloa crusgalli, Digitaria sanguinalis, and Setaria viridis (green foxtail), as well as major broadleaf weeds, such as Abutilon theophrasti, Rorippa indica (dog weed), and Bidens pilosa (Bidensis pilosa), and have excellent commercial value. In particular, we have noted that the compounds exhibit extremely high activity against broadleaf weeds that are resistant to ALS inhibitors, such as Rorippa indica, Descurainia sophia, Capsella bursa-pastoris (shepherd's purse), Lithospermum arvense, Galium aparine, and Stellaria media (chickweed).

[0076] Safety evaluation of transplanted rice and weed control effectiveness in rice paddies Rice paddy soil was placed in a 1 / 1,000,000 ha pot. Monochoria vaginalis seeds were sown and gently covered with soil. The pot was then left to stand in a greenhouse with 0.5 to 1 cm of water. Thereafter, the water depth was maintained at 3 to 4 cm. When the Monochoria vaginalis reached the 0.5-leaf stage, a water-diluted solution of WP or SC, prepared according to a general method for preparing the compound of the present invention, was uniformly added dropwise with a pipette to a specific effective dose to treat the weeds.

[0077] The rice paddy soil in the 1 / 1,000,000 ha pot was then leveled and water was retained at a depth of 3-4 cm. The following day, three-leaf stage rice (Japonica rice) was transplanted at a transplanting depth of 3 cm. Five days after transplanting, the compound of the present invention was similarly applied.

[0078] The fertility conditions of barnyardgrass and rice plants were visually inspected 14 days and 21 days after application of the compounds of the present invention, respectively. The weed control effects were evaluated according to the above activity standard levels of 0 to 5, and many of the compounds showed excellent activity and selectivity.

[0079] [Table 6]

[0080] Experiments have shown that the compounds of the present invention have excellent activity against weeds with anti-ALS inhibitory activity that cause serious problems in production, and can solve the increasingly serious problem of resistance.

[0081] At the same time, after several tests, it has been found that the compounds and compositions of the present invention have good selectivity against many grass weeds, such as Zoysia japonica, Cynodon dactylon, Festuca elata, Poa annua, Lolium perenne, Paspalum vaginatum, etc., and can control many important grass weeds and broadleaf weeds. The compounds also show excellent selectivity and commercial value in tests on wheat, corn, rice, sugarcane, soybean, cotton, oil sunflower, potato, fruit trees and vegetables in different herbicide application methods.

Claims

1. Formula I-1: 【Chemical 1】 Wherein A and B each independently represent halogen, C represents halogen or C1-C8 alkyl, Q represents C1-C8 alkyl, Y represents NR １ R ２ and R １ represents H, and R ２ represents H, and X represents O or S, M represents C1-C18 alkyl having halogen; C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 cycloalkyl, -(C1-C8 alkyl)-Z, with or without halogen 【Chemical Formula 2】 or represents unsubstituted or substituted heterocyclyl, aryl or heteroaryl, Z is 【Chemical Formula 3】 cyano or nitro; or represents unsubstituted or substituted heterocyclyl, aryl or heteroaryl, R ３ each independently represents C1-C8 alkyl or C2-C8 alkenyl, R ４ , R ５ and R ６ each independently represents hydrogen, C1-C8 alkyl or C1-C8 alkoxycarbonyl.]] an ester derivative of R-pyridyloxycarboxylic acid represented by The term "heterocyclyl" refers to 【Chemical Formula 4】 and The term "aryl" refers to phenyl or naphthyl, The term "heteroaryl" refers to 【Chemical Formula 5】 wherein these groups are the following groups: halogen and cyano; and C1-C6 alkyl with or without halogen and OR'', and may be substituted by at least one group selected from the group consisting of R' each independently represents C1-C6 alkyl, R'' each independently represents C1-C6 alkyl, the ester derivative of the above-mentioned R-pyridyloxycarboxylic acid.

2. A and B each independently represent halogen, C represents halogen or C1-C6 alkyl, Q represents C1-C6 alkyl, Y represents NR1R2, R1 represents H, R2 represents H, X represents O or S, M represents C1-C18 alkyl having halogen; C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, -(C1-C6 alkyl)-Z, with or without halogen 【Chemical Formula 6】 or represents unsubstituted or substituted heterocyclyl, aryl or heteroaryl, Z is 【Chemical Formula 7】 cyano or nitro; or represents unsubstituted or substituted heterocyclyl, aryl or heteroaryl, R3 each independently represents C1-C6 alkyl or C2-C6 alkenyl, R4, R5 and R6 each independently represent hydrogen, C1-C6 alkyl or C1-C6 alkoxycarbonyl, The term "heterocyclyl" refers to [Chemical Formula 8] and The term "aryl" refers to phenyl or naphthyl, The term "heteroaryl" refers to 【Chemical Formula 9】 and herein these groups are the following groups: halogen and cyano; and 0, 1, 2 or 3 groups selected from the group consisting of C1-C6 alkyl with or without halogen and OR'' substituted, wherein each R' independently represents C1-C6 alkyl, each R'' independently represents C1-C6 alkyl, the ester derivative of R-pyridyloxycarboxylic acid according to claim 1.

3. A and B each independently represent halogen, C represents halogen or C1-C6 alkyl, Q represents C1-C6 alkyl, Y represents amino, X represents O or S, M is halo C1-C8 alkyl, C3-C6 cycloalkyl, C2-C6 alkenyl, halo C2-C6 alkenyl, C2-C6 alkynyl, cyano C1-C2 alkyl, nitro C1-C2 alkyl, C1-C6 alkoxycarbonyl C1-C2 alkyl, C2-C6 alkenyloxycarbonyl C1-C2 alkyl, -(C1-C2 alkyl)-Z, 【Chemical Formula 10】 tetrahydrofuryl, pyridyl, naphthyl, 【Chemical 11】 unsubstituted or substituted by C1-C6 alkyl 【Chemical Formula 12】 or represents phenyl which is unsubstituted or substituted by C1-C6 alkyl, halogen or C1-C6 alkoxy, Z is 【Chemical Formula 13】 tetrahydrofuryl, pyridyl, 【Chemical Formula 14】 thienyl, furyl or naphthyl; or represents phenyl which is unsubstituted or substituted by at least one group selected from the group consisting of C1-C6 alkyl, halo C1-C6 alkyl, cyano and halogen, each R3 independently represents C1-C6 alkyl, each of R4, R5 and R6 independently represents hydrogen, C1-C6 alkyl or C1-C6 alkoxycarbonyl, R' represents C1-C6 alkyl, the ester derivative of R-pyridyloxycarboxylic acid according to claim 2.

4. A and B each independently represent chloro, C represents fluoro, chloro or methyl, Q represents methyl, ethyl, propyl or isopropyl, Y represents NH2, X represents O or S, M is 2-fluoroethyl, 2-chloroethyl, 2-bromoethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 4,4,4-trifluorobutyl, 2,2,3,3,3-pentafluoropropyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, allyl, 2-propynyl, 【Chemical Formula 15】 tetrahydrofuryl, tetrahydrofurylmethylene, pyridyl, pyridylmethylene, naphthyl, naphthylmethylene, furylmethylene, thienylmethylene, 【Chemical 16】 unsubstituted or substituted with methyl 【Chemical 17】 phenyl which is unsubstituted or substituted with methyl, chloro, methoxy or isopropyl; or benzyl which is unsubstituted or substituted with trifluoromethyl, bromo, chloro, fluoro, cyano or methyl, R' represents methyl, an ester derivative of R-pyridyloxycarboxylic acid according to claim 3.

5. The following compound: 【Table 1】 An ester derivative of R-pyridyloxycarboxylic acid according to claim 4, selected from

6. A method for preparing an ester derivative of R-pyridyloxycarboxylic acid according to any one of claims 1 to 5, a step of reacting a compound of formula III with a compound of formula II to obtain a compound of formula I-1-1, wherein the reaction scheme is 【Chemical Formula 18】 [wherein, W represents an alkali metal and Hal represents a halogen.] as follows, said step being carried out in the presence of a catalyst and a solvent, including when X is S, a step of reacting the compound of formula I-1-1 with an aqueous lithium hydroxide solution and a solvent to obtain a compound of formula I, wherein the reaction scheme is 【Chemical 19】 as follows, said step; a step of reacting the compound of formula I with M-SH to obtain a compound of formula I-1-2, wherein the reaction scheme is 【Chemical 20】 as follows, said step being carried out in the presence of a dehydrating agent and a solvent; further including or, when Y represents NR1R2 and R1 and R2 are not hydrogen at the same time, a compound of formula I-2: 【Chemical 21】 or a compound of formula I-1-3: 【Chemical 22】 is obtained by reacting it with a corresponding halide, said reaction being carried out in the presence of a base and a solvent, said base being one or more selected from the group consisting of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate and cesium carbonate, the solvent is one or more selected from the group consisting of THF, 1,4-dioxane, toluene, 1,2-dichloroethane, ethyl acetate, acetonitrile, DMF, acetone, dichloromethane, and chloroform, optionally, a step of adding a catalyst during the reaction the method further comprising the above. **Claim 7**: A herbicidal composition comprising at least one ester derivative of R-pyridyloxycarboxylic acid according to any one of claims 1 to 5. **Claim 8**: A method for controlling weeds, the method comprising applying an herbicidally effective amount of at least one ester derivative of R-pyridyloxycarboxylic acid according to any one of claims 1 to 5 or the herbicidal composition according to claim 7 to a plant or a weed area. **Claim 9**: Use of at least one ester derivative of R-pyridyloxycarboxylic acid according to any one of claims 1 to 5 or the herbicidal composition according to claim 7 for controlling weeds.

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