PYRIDYLOXY CARBOXYLATE DERIVATIVE, PREPARATION METHOD THEREFOR, HERBICIDAL COMPOSITION AND USE THEREOF

Abstract

The invention relates to the field of pesticide technology, and in particular a type of pyridyloxy carboxylate derivative, preparation method, herbicidal composition and application thereof. The pyridyloxy carboxylate derivative is represented by formula I,

##STR00001##

wherein, A, B each independently represent halogen, or alkyl or cycloalkyl with or without halogen; C represents hydrogen, halogen, alkyl or haloalkyl; Q represents halogen, cyano, cyanoalkyl, hydroxyalkyl, amino, nitro, formyl, alkyl or alkenyl with or without halogen or the like; M represents -alkyl-R, -haloalkyl-R or

##STR00002##

X represents nitro or NR.sub.1R.sub.2. The compound has excellent herbicidal activity and higher crop safety, especially good selectivity for key crops such as rice and soybean.

Claims

1. A pyridyloxy carboxylate derivative represented by formula I, ##STR00236## wherein, A, B each independently represent halogen; or alkyl or cycloalkyl with or without halogen; C represents hydrogen, halogen, alkyl or haloalkyl; Q represents halogen, cyano, cyanoalkyl, hydroxyalkyl, amino, nitro, 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; M represents -alkyl-R, -haloalkyl-R or ##STR00237## R represents ##STR00238## R.sub.3 each independently represents hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkylalkyl; or unsubstituted or substituted heterocyclyl, aryl, heteroaryl, heterocyclylalkyl, arylalkyl or heteroarylalkyl; R.sub.4, R.sub.5, and R.sub.6 each independently represent hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkylalkyl, alkoxy, alkoxycarbonyl; or unsubstituted or substituted heterocyclyl, aryl, heteroaryl, heterocyclylalkyl, arylalkyl or heteroarylalkyl; X represents nitro or NR.sub.1R.sub.2, wherein R.sub.1 represents H; alkyl, alkenyl or alkynyl optionally substituted by 1-2 R.sub.11; —COR.sub.12, nitro, OR.sub.13, SO.sub.2R.sub.14, NR.sub.15R.sub.16, N═CR.sub.17R.sub.18, alkylcarbamoyl, dialkylcarbamoyl, trialkylsilyl or dialkylphosphono; R.sub.2 represents H; alkyl optionally substituted by 1-2 R.sub.11; or —COR.sub.12; or NR.sub.1R.sub.2 represents N═CR.sub.21NR.sub.22R.sub.23, N═CR.sub.24OR.sub.25; or a 5- or 6-membered saturated or unsaturated ring with or without oxygen atom, sulfur atom, or other nitrogen atom, which is unsubstituted or substituted by 1-2 groups independently selected from the group consisting of halogen, alkyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio, amino, alkylamino, dialkylamino and alkoxycarbonyl; wherein R.sub.11 independently represents halogen, hydroxy, alkoxy, haloalkoxy, alkylthio, haloalkylthio, amino, alkylamino, dialkylamino, alkoxycarbonyl; or unsubstituted or substituted aryl or heteroaryl; R.sub.12 represents H, alkyl, haloalkyl, alkoxy, phenyl, phenoxy or benzyloxy; R.sub.13 represents H, alkyl, haloalkyl, phenyl, benzyl or CHR.sub.31C(O)OR.sub.32; R.sub.31 represents H, alkyl or alkoxy; R.sub.32 represents H, alkyl or benzyl; R.sub.14 represents alkyl or haloalkyl; R.sub.15 represents H, alkyl, formyl, alkylacyl, haloalkylacyl, alkoxycarbonyl, phenylcarbonyl, phenoxycarbonyl or benzyloxycarbonyl; R.sub.16 represents H or alkyl; R.sub.17 represents H, alkyl; or phenyl that is unsubstituted or substituted by 1-3 groups selected from the group consisting of halogen, alkyl and alkoxy; R.sub.18 represents H or alkyl; or N═CR.sub.17R.sub.18represents ##STR00239## R.sub.21, R.sub.24 each independently represent H or alkyl; R.sub.22, R.sub.23 each independently represent H or alkyl; or NR.sub.22R.sub.23 represents a 5- or 6-membered saturated or unsaturated ring with or without oxygen atom, sulfur atom, or other nitrogen atom; R.sub.25 represents alkyl.

2. The pyridyloxy carboxylate derivative according to claim 1, wherein A, B each independently represent halogen; or C1-C8 alkyl or C3-C8 cycloalkyl with or without halogen; C represents hydrogen, halogen, C1-C8 alkyl or halo C1-C8 alkyl; Q represents halogen, cyano, cyano C1-C8 alkyl, hydroxy C1-C8 alkyl, amino, nitro, 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 alkylamino C1-C8 alkyl or C1-C8 alkoxy C1-C8 alkyl with or without halogen; or unsubstituted or substituted aryl, heteroaryl, aryl C1-C8 alkyl or heteroaryl C1-C8 alkyl; M represents —(C1-C8)alkyl-R, -halo(C1-C8)alkyl-R or ##STR00240## R represents ##STR00241## R.sub.3 each independently represents hydrogen, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 cycloalkyl, C3-C8 cycloalkyl C1-C8 alkyl; or unsubstituted or substituted heterocyclyl, aryl, heteroaryl, heterocyclyl C1-C8 alkyl, aryl C1-C8 alkyl or heteroaryl C1-C8 alkyl; R.sub.4, R.sub.5, and R.sub.6 each independently represent hydrogen, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 cycloalkyl, C3-C8 cycloalkyl C1-C8 alkyl, C1-C8 alkoxy, C1-C8 alkoxycarbonyl; or unsubstituted or substituted heterocyclyl, aryl, heteroaryl, heterocyclyl C1-C8 alkyl, aryl C1-C8 alkyl or heteroaryl C1-C8 alkyl; X represents nitro or NR.sub.1R.sub.2, wherein Ru represents H; C1-C8 alkyl, C2-C8 alkenyl or C2-C8 alkynyl optionally substituted by 1-2 R.sub.11; —COR.sub.12, nitro, OR.sub.13, SO.sub.2R.sub.14, NR.sub.15R.sub.16, N═CR.sub.17R.sub.18, C1-C8 alkylcarbamoyl, di-C1-C8 alkylcarbamoyl, tri-C1-C8 alkylsilyl or di-C1-C8 alkylphosphono; R.sub.2 represents H; C1-C8 alkyl optionally substituted by 1-2 R.sub.11; or —COR.sub.12; or NR.sub.1R.sub.2 represents N═CR.sub.21NR.sub.22R.sub.23, N═CR.sub.24OR.sub.25; or ##STR00242## that is unsubstituted or substituted by 1-2 groups independently selected from the group consisting of halogen, C1-C8 alkyl, C1-C8 alkoxy, halo C1-C8 alkoxy, C1-C8 alkylthio, halo C1-C8 alkylthio, amino, C1-C8 alkylamino, di-C1-C8 alkylamino and C1-C8 alkoxycarbonyl; wherein R.sub.11 independently represents halogen, hydroxy, C1-C8 alkoxy, halo C1-C8 alkoxy, C1-C8 alkylthio, halo C1-C8 alkylthio, amino, C1-C8 alkylamino, di-C1-C8 alkylamino, C1-C8alkoxycarbonyl; or phenyl, naphthyl, ##STR00243## that is unsubstituted or substituted by 1-3 groups selected from the group consisting of halogen, C1-C8 alkyl, halo C1-C8 alkyl, C1-C8 alkoxy and nitro; R.sub.12 represents H, C1-C18 alkyl, halo C1-C8 alkyl, C1-C8 alkoxy, phenyl, phenoxy or benzyloxy; R.sub.13 represents H, C1-C8 alkyl, halo C1-C8 alkyl, phenyl, benzyl or CHR.sub.31C(O)OR.sub.32; R.sub.31 represents H, C1-C8 alkyl or C1-C8 alkoxy; R.sub.32 represents H, C1-C8 alkyl or benzyl; R.sub.14 represents C1-C8 alkyl or halo C1-C8 alkyl; R.sub.15 represents H, C1-C8 alkyl, formyl, C1-C8 alkylacyl, halo C1-C8 alkylacyl, C1-C8 alkoxycarbonyl, phenylcarbonyl, phenoxycarbonyl or benzyloxycarbonyl; R.sub.16 represents H or C1-C8 alkyl; R.sub.17 represents H, C1-C8 alkyl; or phenyl that is unsubstituted or substituted by 1-3 groups selected from the group consisting of halogen, C1-C8 alkyl and C1-C8 alkoxy; R.sub.18 represents H or C1-C8 alkyl; or N═CR.sub.17R.sub.18 represents ##STR00244## R.sub.21, R.sub.24 each independently represent H or C1-C8 alkyl; R.sub.22, R.sub.23 each independently represent H or C1-C8 alkyl; or NR.sub.22R.sub.23 represents ##STR00245## R.sub.25 represents C1-C8 alkyl; the term “heterocyclyl” refers to ##STR00246## with 0, 1 or 2 oxo groups; the term “aryl” refers to phenyl or naphthyl; the term “heteroaryl” refers to ##STR00247## ##STR00248## which is optionally substituted by at least one group selected from the group consisting of halogen, nitro, cyano, thiocyano, hydroxy, carboxy, mercapto, formyl; phenyl, benzyl, benzyloxy, phenoxy that is unsubstituted or substituted by at least one group from the group consisting of halogen, alkyl and alkoxy; alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkylalkyl, OR″, SR″, -alkyl-OR″, -alkyl-SR″, COR″, COOR″, COSR″, SOR″, SO.sub.2R″, 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″, SO.sub.2R″ and OR″; R′ each independently represents hydrogen, nitro, hydroxy, 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; R″ each independently represents hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl or cycloalkylalkyl.

3. The pyridyloxy carboxylate derivative according to claim 2, wherein A, B each independently represent halogen; or C1-C6 alkyl or C3-C6 cycloalkyl with or without halogen; C represents hydrogen, halogen, C1-C6 alkyl or halo C1-C6 alkyl; Q represents halogen, cyano, cyano C1-C6 alkyl, hydroxy C1-C6 alkyl, amino, nitro, 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 alkylamino C1-C6 alkyl or C1-C6 alkoxy C1-C6 alkyl with or without halogen; or unsubstituted or substituted aryl, heteroaryl, aryl C1-C6 alkyl or heteroaryl C1-C6 alkyl; M represents —(C1-C6)alkyl-R, -halo(C1-C6)alkyl-R or ##STR00249## R represents ##STR00250## R.sub.3 each independently represents hydrogen, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, C3-C6 cycloalkyl C1-C6 alkyl; or unsubstituted or substituted heterocyclyl, aryl, heteroaryl, heterocyclyl C1-C6 alkyl, aryl C1-C6 alkyl or heteroaryl C1-C6 alkyl; R.sub.4, R.sub.5, and R.sub.6 each independently represent hydrogen, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, C3-C6 cycloalkyl C1-C6 alkyl, C1-C6 alkoxy, C1-C6 alkoxycarbonyl; or unsubstituted or substituted heterocyclyl, aryl, heteroaryl, heterocyclyl C1-C6 alkyl, aryl C1-C6 alkyl or heteroaryl C1-C6 alkyl; X represents nitro or NR.sub.1R.sub.2, wherein R1 represents H; C1-C6 alkyl, C2-C6 alkenyl or C2-C6 alkynyl optionally substituted by 1-2 R.sub.11; —COR.sub.12, nitro, OR.sub.13, SO.sub.2R.sub.14, NR.sub.15R.sub.16, N═CR.sub.17R.sub.18, C1-C6 alkylcarbamoyl, di-C1-C6 alkylcarbamoyl, tri-C1-C6 alkylsilyl or di-C1-C6 alkylphosphono; R.sub.2 represents H; C1-C6 alkyl optionally substituted by 1-2 R.sub.H; or —COR.sub.12; or NR.sub.1R.sub.2 represents N═CR.sub.21NR.sub.22R.sub.23, N═CR.sub.24OR.sub.25; or ##STR00251## that is unsubstituted or substituted by 1-2 groups independently selected from the group consisting of halogen, C1-C6 alkyl, C1-C6 alkoxy, halo C1-C6 alkoxy, C1-C6 alkylthio, halo C1-C6 alkylthio, amino, C1-C6 alkylamino, di-C1-C6 alkylamino and C1-C6 alkoxycarbonyl; wherein R.sub.H independently represents halogen, hydroxy, C1-C6 alkoxy, halo C1-C6 alkoxy, C1-C6 alkylthio, halo C1-C6 alkylthio, amino, C1-C6 alkylamino, di-C1-C6 alkylamino, C1-C6 alkoxycarbonyl; or phenyl, naphthyl, ##STR00252## that is unsubstituted or substituted by 1-3 groups selected from the group consisting of halogen, C1-C6 alkyl, halo C1-C6 alkyl, C1-C6 alkoxy and nitro; R.sub.12 represents H, C1-C14 alkyl, halo C1-C6 alkyl, C1-C6 alkoxy, phenyl, phenoxy or benzyloxy; R.sub.13 represents H, C1-C6 alkyl, halo C1-C6 alkyl, phenyl, benzyl or CHR.sub.31C(O)OR.sub.32; R.sub.31 represents H, C1-C6 alkyl or C1-C6 alkoxy; R.sub.32 represents H, C1-C6 alkyl or benzyl; R.sub.14 represents C1-C6 alkyl or halo C1-C6 alkyl; R.sub.15 represents H, C1-C6 alkyl, formyl, C1-C6 alkylacyl, halo C1-C6 alkylacyl, C1-C6 alkoxycarbonyl, phenylcarbonyl, phenoxycarbonyl or benzyloxycarbonyl; R.sub.16 represents H or C1-C6 alkyl; R.sub.17 represents H, C1-C6 alkyl; or phenyl that is unsubstituted or substituted by 1-3 groups selected from the group consisting of halogen, C1-C6 alkyl and C1-C6 alkoxy; Rig represents H or C1-C6 alkyl; or N═CR.sub.17R.sub.18 represents ##STR00253## R.sub.21, R.sub.24 each independently represent H or C1-C6 alkyl; R.sub.22, R.sub.23 each independently represent H or C1-C6 alkyl; or NR.sub.22R.sub.23 represents ##STR00254## R.sub.25 represents C1-C6 alkyl; the term “heterocyclyl” refers to ##STR00255## with 0, 1 or 2 oxo groups; the term “aryl” refers to phenyl or naphthyl; the term “heteroaryl” refers to ##STR00256## ##STR00257## which is substituted by 0, 1, 2 or 3 groups selected from the group consisting of halogen, nitro, cyano, thiocyano, hydroxy, carboxy, mercapto, formyl; phenyl, benzyl, benzyloxy, phenoxy that is unsubstituted or substituted by at least one group 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 cycloalkyl C1-C6 alkyl, OR″, SR″, —(C1-C6)alkyl-OR″, —(C1-C6)alkyl-SR″, COR″, COOR″, COSR″, SOR″, SO.sub.2R″, 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 cycloalkyl C1-C6 alkyl, phenyl, benzyl, benzyloxy, phenoxy, COR″, COOR″, SO.sub.2R″ and OR″; R′ each independently represents hydrogen, nitro, hydroxy, amino; or C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, C3-C6 cyclo alkenyl, C3-C6 cycloalkyl C1-C6 alkyl, C1-C6 alkoxy, C2-C6 alkenyloxy, C2-C6 alkynyloxy, C3-C6 cycloalkyloxy, C1-C6 alkoxy C1-C6 alkyl, C1-C6 alkoxycarbonyl, C1-C6 alkylthiocarbonyl, C1-C6 alkylsulfonyl, C1-C6 alkylsulfonyl C1-C6 alkyl, C1-C6 alkylcarbonyl, C1-C6 alkylcarbonyl C1-C6 alkyl, C1-C6 alkylacyloxy, C1-C6 alkylamino, C1-C6 alkylaminocarbonyl, C1-C6 alkoxyaminocarbonyl, C1-C6 alkoxycarbonyl C1-C6 alkyl, C1-C6 alkylaminocarbonyl C1-C6 alkyl, tri-C1-C6 alkylsilyl or di-C1-C6 alkylphosphono with or without fluoro, chloro or bromo; R″ each independently represents hydrogen, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl or C3-C6 cycloalkyl C1-C6 alkyl.

4. The pyridyloxy carboxylate derivative according to claim 3, wherein A, B each independently represent halogen, C1-C6 alkyl, halo C1-C6 alkyl or C3-C6 cycloalkyl; C represents hydrogen, halogen, C1-C6 alkyl or halo C1-C6 alkyl; Q represents C1-C6 alkyl, halo C1-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, hydroxy C1-C6 alkyl, C1-C6 alkoxy C1-C2 alkyl, cyano C1-C2 alkyl, C1-C6 alkylamino C1-C2 alkyl, benzyl, naphthyl, furyl, thienyl, thiazolyl, pyridyl, pyrimidinyl; ##STR00258## that is unsubstituted or substituted by C1-C6 alkyl; or phenyl that is unsubstituted or substituted by at least one group selected from the group consisting of C1-C6 alkyl, halo C1-C6 alkyl, halogen and C1-C6 alkoxy; M represents —(C1-C6)alkyl-R, -halo(C1-C6)alkyl-R or ##STR00259## R represents ##STR00260## R.sub.3 each independently represents hydrogen, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, C3-C6 cycloalkyl C1-C6 alkyl; or phenyl, naphthyl, benzyl, ##STR00261## that is unsubstituted or substituted by at least one group selected from the group consisting of C1-C6 alkyl, C1-C6 alkoxy, halogen and halo C1-C6 alkyl; R.sub.4, R.sub.5, and R.sub.6 each independently represent hydrogen, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, C3-C6 cycloalkyl C1-C6 alkyl, C1-C6 alkoxy, C1-C6 alkoxycarbonyl; or phenyl, naphthyl, benzyl, ##STR00262## that is unsubstituted or substituted by at least one group selected from the group consisting of C1-C6 alkyl, C1-C6 alkoxy, halogen and halo C1-C6 alkyl; R′ represents C1-C6 alkyl or halo C1-C6 alkyl; X represents amino, C1-C6 alkylamino, C1-C6 alkylcarbonylamino, phenylcarbonylamino, benzylamino; or furylmethyleneamino that is unsubstituted or substituted by halo C1-C6 alkyl.

5. The pyridyloxy carboxylate derivative according to claim 4, wherein A, 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 represents 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, ##STR00263## benzyl, naphthyl, furyl, thienyl, thiazolyl, pyridyl, pyrimidinyl; ##STR00264## that is unsubstituted or substituted by methyl; or phenyl that is unsubstituted or substituted by at least one group selected from the group consisting of methyl, trifluoromethyl, chloro and methoxy; R represents methyl, ethyl or difluoromethyl; M represents ##STR00265## ##STR00266## X represents NH.sub.2, ##STR00267##

6. The pyridyloxy carboxylate derivative according to claim 5, which is selected from any one of Table 1.

7. A preparation method of the pyridyloxy carboxylate derivative according to any one of claims 1-6, which comprises the following steps: a compound of formula III is reacted with a compound of formula II to obtain a compound of formula I; the reaction scheme is as follows: ##STR00268## wherein, W represents an alkali metal, preferably K, Na; Hal represents halogen, preferably Br, Cl; 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. or, when X represents NR.sub.1R.sub.2 (R.sub.1, R.sub.2 are not hydrogen at the same time), it is obtained by reacting a compound of formula I-1 ##STR00269## with a corresponding halide; wherein, the halide is preferably chloride or bromide; the reaction is carried out in the presence of a base and a solvent, wherein 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; a catalyst, preferably DMAP, is optionally added during the reaction.

8. A herbicidal composition comprising (i) at least one of pyridyloxy carboxylate derivatives according to any one of claims 1-6; preferably, further comprising (ii) one or more further herbicides and/or safeners; more preferably, further comprising (iii) agrochemically acceptable formulation auxiliaries.

9. A method for controlling a weed comprising applying a herbicidally effective amount of at least one of the pyridyloxy carboxylate derivatives according to any one of claims 1-6 or the herbicidal composition according to claim 8 on a plant or in a weed area. Preferably, the plant is rice (such as japonica rice, indica rice), soybean; or the weed is a gramineous weed (such as Echinochloa crusgalli, Digitaria sanguinalis), a broad-leaved weed (such as Monochoria Vaginalis, Abutilon theophrasti, Galium spurium) or a cyperaceae weed (such as Cyperus iria).

10. Use of at least one of the pyridyloxy carboxylate derivatives according to any one of claims 1-6 or the herbicidal composition according to claim 8 for controlling a weed, preferably, the pyridyloxy carboxylate derivative being used to control a weed in a useful crop, wherein the useful crop is a genetically modified crop or a crop treated by gene editing technology. Preferably, the crop is rice (such as japonica rice, indica rice), soybean, or the weed is a gramineous weed (such as Echinochloa crusgalli, Digitaria sanguinalis), a broad-leaved weed (such as Monochoria Vaginalis, Abutilon theophrasti, Galium spurium) or a cyperaceae weed (such as Cyperus iria).

Description

1. SYNTHESIS OF COMPOUND 2

[0125] (1) Compound 2-1 (300 mg, 3.33 mmol) and TEA (404 mg, 4.00 mmol) were dissolved in dehydrated dichloromethane (20 ml), cooled to 0° C. and compound a (791 mg, 3.66 mmol) was slowly added dropwise. Heated slowly to room temperature and continued to react for 12 hours. The reaction was quenched by pouring the reaction solution into ice water, extracted and the organic phase was washed one time with 50 ml of saturated sodium bicarbonate. The organic phase was dried and then concentrated to obtain compound 2-2 (800 mg, crude product). Without further purification, the compound was directly used in the next step.

##STR00218##

[0126] (2) Compound b (400 mg, 1.59 mmol), compound 2-2 (800 mg, crude product) obtained from step (1), a catalytic amount of TBAB (10 mg) and DMF (10 mL) were added to a 50 ml round-bottom flask, heated to 85° C. and reacted for 12 hours. After completed reaction of the starting materials according to LC-MS detection, the reaction solution was cooled to room temperature, and extracted with water (50 ml) and MTBE (50 ml). The organic phase was dried, concentrated, and separated by column chromatography to obtain compound 2 (300 mg, yield 49%), as a white solid.

##STR00219##

2. SYNTHESIS OF COMPOUND 54

[0127] (1) Compound 54-1 (1 mg, 7.03 mmol) and compound 54-2 (845 mg, 7.03 mmol) were dissolved in 20 ml methanol. Cooled to 0° C., and thionyl chloride (920 mg, 7.74 mmol) was slowly added drop wise. Heated slowly to room temperature and continued to react for 12 hours at room temperature. After basically completed reaction of the starting materials according to HPLC detection, concentrated, washed with ethyl acetate (100 mL×2) and saturated sodium bicarbonate (50 mL). The organic phase was dried and then concentrated to obtain compound (1.5 g, crude product). Without further purification, the compound was directly used in the next step.

##STR00220##

[0128] (2) Compound 54-3 (1.5 g, crude product) obtained from the above operations, NBS (1.09 g, 6.14 mmol), a catalytic amount of AIBN (10 mg) and carbon tetrachloride (100 ml) were added to a 100 ml single mouth flask and agitated for 12 hours at 60° C. After completed reaction of the starting materials according to HPLC detection, the reaction solution was cooled to room temperature. The solid was filtered and the carbon tetrachloride phase was concentrated, to obtain compound 54-4 (1 g, crude product). Without further purification, the compound was directly used in the next step.

##STR00221##

[0129] (3) Compound b (400 mg, 1.70 mmol), compound 54-4 (826 mg, 1.91), a catalytic amount of TBAB (10 mg) and DMF (10 mL) were added to a 50 ml round-bottom flask, heated to 85° C. and reacted for 12 hours. After completed reaction of the starting materials according to LC-MS detection, the reaction solution was cooled to room temperature, and extracted with water (50 ml) and MTBE (50 ml). The organic phase was dried, concentrated, and separated by column chromatography to obtain compound 54 (400 mg, yield 57%).

##STR00222##

3. SYNTHESIS OF COMPOUND 78

[0130] (1) Compound 78-1 (300 mg, 1.46 mmol) and TEA (178 mg, 175 mmol) were dissolved in dehydrated dichloromethane (20 ml), cooled to 0° C. and compound a (347 mg, 1.61 mmol) was slowly added dropwise. Heated slowly to room temperature and continued to react for 12 hours. The reaction was quenched by pouring the reaction solution into ice water, extracted and the organic phase was washed one time with 50 ml of saturated sodium bicarbonate. The organic phase was dried and then concentrated to obtain compound 78-2 (460 mg, crude product). Without further purification, the compound was directly used in the next step.

##STR00223##

[0131] (2) Compound b (400 mg, 1.70 mmol), compound 78-2 (826 mg, 2.56 mmol) obtained from step (1), a catalytic amount of TBAB (10 mg) and DMF (10 mL) were added to a 50 ml round-bottom flask, heated to 85° C. and reacted for 12 hours. After completed reaction of the starting materials according to LC-MS detection, the reaction solution was cooled to room temperature, and extracted with water (50 ml) and MTBE (50 ml). The organic phase was dried, concentrated, and separated by column chromatography to obtain compound 78 (300 mg, yield 38%).

##STR00224##

4. SYNTHESIS OF COMPOUND 79

[0132] (1) Compound 79-1 (300 mg, 4.1 mmol) was dissolved in dehydrated methanol (20 ml), cooled to 0° C. and solid sodium methoxide was added in batches (244 mg, 4.51 mmol). Agitated for 10 min at 0° C. and compound 79-2 (199 mg, 4.51 mmol) was slowly added dropwise at this temperature. Heated slowly to room temperature and continued to react for 12 hours. After basically completed reaction of the starting materials according to HPLC detection, a few drops of acetate solution was added to neutral. The reaction solution was concentrated to remove methanol, extracted with water (100 ml) and ethyl acetate (100 ml×2). The organic phase was dried, concentrated to obtain compound 79-3 (500 mg, crude product). Without further purification, the compound was directly used in the next step.

##STR00225##

[0133] (2) Compound 79-3 (500 mg, crude product) and TEA (518 mg, 5.12 mmol) were dissolved in dehydrated dichloromethane (20 ml), cooled to 0° C. and compound a (1.01 g, 4.69 mmol) was slowly added dropwise. Heated slowly to room temperature and continued to react for 12 hours. The reaction was quenched by pouring the reaction solution into ice water, extracted and the organic phase was washed one time with 50 ml of saturated sodium bicarbonate. The organic phase was dried and then concentrated to obtain compound 79-4 (1 g, crude product). Without further purification, the compound was directly used in the next step.

##STR00226##

[0134] (3) Compound b (400 mg, 2.13 mmol), compound 79-4 (1 g, crude product) obtained from step (2), a catalytic amount of TBAB (10 mg) and DMF (10 mL) were added to a 50 ml round-bottom flask, heated to 85° C. and reacted for 12 hours. After completed reaction of the starting materials according to LC-MS detection, the reaction solution was cooled to room temperature, and extracted with water (100 ml) and MTBE (50 ml×2). The organic phase was dried, concentrated, and separated by column chromatography to obtain compound 79 (240 mg, yield 38%), as a white solid.

##STR00227##

5. SYNTHESIS OF COMPOUNDS 74 AND 128

[0135] (1) Compound 74-1 (300 mg, 2.08 mmol) and TEA (253 mg, 2.50 mmol) were dissolved in dehydrated dichloromethane (20 ml), cooled to 0° C. and compound a (494 mg, 2.29 mmol) was slowly added dropwise. Heated slowly to room temperature and continued to react for 12 hours. The reaction was quenched by pouring the reaction solution into ice water, extracted and the organic phase was washed one time with 50 ml of saturated sodium bicarbonate. The organic phase was dried and then concentrated to obtain compound 74-2 (500 mg, crude product). Without further purification, the compound was directly used in the next step.

##STR00228##

[0136] (2) Compound b (400 mg, 1.70 mmol), compound 74-2 (533 mg, 1.91 mmol) obtained from step (1), a catalytic amount of TBAB (10 mg) and DMF (10 mL) were added to a 50 ml round-bottom flask, heated to 85° C. and reacted for 12 hours. After completed reaction of the starting materials according to LC-MS detection, the reaction solution was cooled to room temperature, and extracted with water (50 ml) and MTBE (50 ml). The organic phase was dried, concentrated, and separated by column chromatography to obtain compound 74 (300 mg, yield 48%).

##STR00229##

[0137] (3) Compound 74 (300 mg, 0.76 mmol), compound 128-1 (195 mg, 1.14 mmol), potassium carbonate (210 mg, 1.52 mmol), a catalytic amount of DMAP (10 mg) and acetonitrile (20 ml) were added to a 50 ml round-bottom flask. Heated to 80° C. and reacted for 12 hours. After completed reaction of the starting materials according to LC-MS detection, the reaction solution was cooled to room temperature, concentrated, and separated by column chromatography to obtain compound 128 (150 mg, yield 44%).

##STR00230##

6. SYNTHESIS OF COMPOUND 130

[0138] (1) Compound 130-1 (300 mg, 3.37 mmol) and TEA (443 mg, 4.38 mmol) were dissolved in dehydrated dichloromethane (20 ml), cooled to 0° C. and compound a (871 mg, 4.04 mmol) was slowly added dropwise. Heated slowly to room temperature and continued to react for 12 hours. The reaction was quenched by pouring the reaction solution into ice water, extracted and the organic phase was washed one time with 50 ml of saturated sodium bicarbonate. The organic phase was dried and then concentrated to obtain compound 130-2 (800 mg, crude product). Without further purification, the compound was directly used in the next step.

##STR00231##

[0139] (2) Compound b (400 mg, 1.70 mmol), compound 130-2 (800 mg, crude product) obtained from step (1), a catalytic amount of TBAB (10 mg) and DMF (10 mL) were added to a 50 ml round-bottom flask, heated to 85° C. and reacted for 12 hours. After completed reaction of the starting materials according to LC-MS detection, the reaction solution was cooled to room temperature, and extracted with water (50 ml) and MTBE (50 ml). The organic phase was dried, concentrated, and separated by column chromatography to obtain compound 130 (300 mg, yield 49%).

##STR00232##

[0140] Biological Activity Evaluation:

[0141] The activity level standard of harmful plants destruction (i. e. growth inhibition rate) is as follows:

[0142] Level 5: the growth inhibition rate is greater than 85%;

[0143] Level 4: the growth inhibition rate is equal to or greater than 60% and less than 85%;

[0144] Level 3: the growth inhibition rate is equal to or greater than 40% and less than 60%;

[0145] Level 2: the growth inhibition rate is equal to or greater than 20% and less than 40%;

[0146] Level 1: the growth inhibition rate is equal to or greater than 5% and less than 20%;

[0147] Level 0: the growth inhibition rate is less than 5%;

[0148] The above described growth inhibition rate is fresh weight inhibition rate.

[0149] Post-emergence test experiment: Monocotyledonous and dicotyledonous weed seeds and main crop seeds (i. e. wheat, corn, rice, soybean, cotton, oilseed, millet and sorghum.) were put into a plastic pot loaded with soil. Then covered with 0.5-2 cm soil, the seeds were allowed to grow in good greenhouse environment. The test plants were treated at 2-3 leaf stage 2 weeks after sowing. The test compounds of the invention were dissolved with acetone respectively, then added with tween-80, and using 1.5 liters per hectare of an amusable concentrate of methyl oleate as a synergist, and diluted by certain amount of water to certain concentration. The solution was sprayed to the plants with a sprayer. Then the plants were cultured for 3 weeks in the greenhouse, and the experiment result of weed controlling effect after 3 weeks was listed in tables 3-4.

TABLE-US-00003 TABLE 3 Activity test results of compounds (1000 g/ha) Echinochloa Digitaria Monochoria Abutilon Galium No. crusgalli sanguinalis Vaginalis theophrasti spurium 1 5 5 5 5 5 2 5 5 5 5 5 3 5 5 5 5 5 4 5 5 5 5 5 5 5 5 5 5 5 6 5 5 5 5 5 7 5 5 5 5 5 8 5 5 5 5 5 9 5 5 5 5 5 10 5 5 5 5 5 11 5 5 5 5 5 12 5 5 5 5 5 13 5 5 5 5 5 14 5 5 5 5 5 15 5 5 5 5 5 16 5 5 5 5 5 17 5 5 5 5 5 18 5 5 5 5 5 19 5 5 5 5 5 20 5 5 5 5 5 21 5 5 5 5 5 22 5 5 5 5 5 23 5 5 5 5 5 24 5 5 5 5 5 25 5 5 5 26 5 5 5 27 5 5 5 28 5 5 5 29 5 5 5 30 5 5 5 31 5 5 5 32 5 5 5 33 5 5 5 34 5 5 5 35 5 5 5 36 5 5 5 37 5 5 5 38 5 5 5 39 5 5 5 40 5 5 5 41 5 5 5 42 5 5 5 43 5 5 5 44 5 5 5 46 5 5 5 47 5 5 5 48 5 5 5 49 5 5 5 50 5 5 5 51 5 5 5 52 5 5 5 53 5 5 5 54 5 5 5 55 5 5 5 56 5 5 5 57 5 5 5 58 5 5 5 59 5 5 5 60 5 5 5 61 5 5 5 62 5 5 5 63 5 5 5 64 5 5 5 65 5 5 5 66 5 5 5 67 5 5 5 5 5 68 5 5 5 5 5 69 5 5 5 5 5 70 5 5 5 5 5 71 5 5 5 5 5 72 5 5 5 5 5 73 5 5 5 5 5 74 5 5 5 5 5 75 5 5 5 5 5 76 5 5 5 5 5 77 5 5 5 5 5 78 5 5 5 5 5 79 5 5 5 5 5 80 5 5 5 5 5 82 5 5 5 5 5 83 5 5 5 5 5 84 5 5 5 5 5 85 5 5 5 5 5 86 5 5 5 5 5 87 5 5 5 5 5 88 5 5 5 5 5 89 5 5 5 5 5 90 5 5 5 5 5 91 5 5 5 5 5 92 5 5 5 5 5 93 5 5 5 5 5 94 5 5 5 5 5 95 5 5 5 5 5 96 5 5 5 5 5 97 5 5 5 5 5 98 5 5 5 5 5 99 5 5 5 5 5 100 5 5 5 5 5 101 5 5 5 5 5 102 5 5 5 5 5 103 5 5 5 5 5 104 5 5 5 5 5 105 5 5 5 5 5 106 5 5 5 5 5 107 5 5 5 5 5 108 5 5 5 5 5 109 5 5 5 5 5 110 5 5 5 5 5 111 5 5 5 5 5 112 5 5 5 5 5 113 5 5 5 5 5 114 5 5 5 5 5 115 5 5 5 5 5 116 5 5 5 5 5 117 5 5 5 5 5 118 5 5 5 5 5 119 5 5 5 5 5 120 5 5 5 5 5 121 5 5 5 5 5 122 5 5 5 5 5 123 5 5 5 5 5 124 5 5 5 5 5 125 5 5 5 5 5 126 5 5 5 5 5 127 5 5 5 5 5 128 5 5 5 5 5 129 5 5 5 5 5 130 5 5 5 5 5 131 5 5 5 5 5 132 5 5 5 5 5

TABLE-US-00004 TABLE 4 Test results of post-emergence weeds Echinochloa No. Japonica rice Indica rice Cyperus iria crusgalli 2 0 0 5 5 3 0 0 5 5 4 0 0 5 5 12 0 0 5 5 69 0 0 5 5 88 0 0 5 5 100 0 0 5 5 104 0 0 5 5 121 0 0 5 5 125 0 0 5 5 126 0 0 5 5 131 0 0 5 5 Control compound A 3 3 5 5 (600 g/ha) Control compound A 2 3 4 4 (300 g/ha) Control compound B 2 2 3 2 (600 g/ha) Bispyribac-sodium 4 2 2 1 (100 g/ha) Note: the application dose was active ingredient 600 g/ha, plus water 450 kg/ha. Echinochloa crusgalli and Cyperus iria were collected from Hunan province of China, and were resistant to ALS inhibitor herbicides. [00233][00234]

[0150] The control compound B is a commercial product which has good effect on broadleaf weeds in wheat and can be used to control certain broadleaf weeds even at low rate. However, it is effective only on a few broadleaf weeds in rice at acceptable crop safety (50-100 g/ha) and its efficacy on key grasses such as Echinochloa crusgalli, Digitaria sanguinalis, Leptochloa chinensis and Setaria viridis in rice is very poor, or even has no effect on these weeds. The control compound A is a known one. Due to poor safety and low selectivity, it is hardly available for commercial application. Unexpectedly, although the structures of the present invention are similar to that of the control compound, the safety of the present invention is greatly improved while retaining the efficacy of the control compound and they have good selectivity to key grasses, broadleaf weeds as well as sedges in rice, thus they have good commercial value, especially for control of ALS resistant weeds considering their outstanding efficacy.

[0151] Experiment on Weed Effect in Pre-Emergence Stage Seeds of monocotyledonous and dicotyledonous weeds and main crops (e. g. wheat, corn, rice, soybean, cotton, oilseed, millet and sorghum) were put into a plastic pot loaded with soil and covered with 0.5-2 cm soil. The test compounds of the present invention was dissolved with acetone, then added with tween-80, diluted by a certain amount of water to reach a certain concentration, and sprayed immediately after sowing. The obtained seeds were incubated for 4 weeks in the greenhouse after spraying and the test results were observed after 3 weeks. It was observed that the herbicide mostly had excellent effect at the application rate of 250 g/ha, especially to weeds such as Echinochloa crusgalli, Digitaria sanguinalis and Abutilon theophrasti, etc. Many compounds had good selectivity for corn, wheat, rice, soybean, oilseed rape, etc.

[0152] Through experiments, we found that the compounds of the present invention generally had better weed control effects, especially for major gramineous weeds such as Echinochloa crusgalli, Digitaria sanguinalis, and Setaria viridis, which are widely occurring in corn fields, rice fields and wheat fields, and major broad-leaved weeds such as Abutilon theophrasti, Rorippa indica and Bidens pilosa, and had excellent commercial value. In particular, we noticed that they had extremely high activity against broad-leaved weeds, such as Rorippa indica, Descurainia sophia, Capsella bursa-pastoris, Lithospermum arvense, Galium spurium and Stellaria media, which were resistant to ALS inhibitors.

[0153] Transplanted rice safety evaluation and weed control effect evaluation in rice field:

[0154] Rice field soil was loaded into a 1/1,000,000 ha pot. The seeds of Monochoria vaginalis were sowed and gently covered with soil, then left to stand still in greenhouse in the state of 0.5-1 cm of water storage. It was kept at 3-4 cm of water storage thereafter. The weeds were treated by dripping the WP or SC water diluents prepared according to the common preparation method of the compounds of the present invention with pipette homogeneously to achieve specified effective amount when Monochoria vaginalis reached 0.5 leaf stage.

[0155] In addition, the rice field soil that loaded into the 1/1,000,000 ha pot was leveled to keep water storage at 3-4 cm depth. The 3-leaf stage rice (japonica rice) was transplanted at 3 cm of transplanting depth the next day. The compound of the present invention was treated by the same way after 5 days of transplantation.

[0156] The fertility condition of Monochoria vaginalis 14 days and rice 21 days after the treatment of the compound of the invention with the naked eye. Evaluate the weed control effect with the aforementioned activity standard level of 0-5, many compounds exhibited excellent activity and selectivity.

TABLE-US-00005 TABLE 5 Test results of activity and safety (1000 g/ha) Monochoria No. Rice Vaginalis 2 0 5 3 0 5 4 0 5 12 0 5 67 0 5 75 0 5 76 0 5 85 0 5 120 0 5 128 0 5 Penoxsulam(50 g/ha) 1 1 Note: The seeds of Monochoria vaginalis were collected from Heilongjing Province of China. Tests indicated that the weeds were resistant to common rate of pyrazosulfuron-ethyl and penoxsulam.

[0157] It can be seen from the experiments that the compounds of the present invention had excellent activity against weeds having an anti-ALS inhibiting activity which cause a serious challenge in production, and can solve the increasingly serious problem of resistance.

[0158] Broadleaf crops are very sensitive to hormonal herbicides, therefore crop injuries are more likely to occur in case of spray drifting. Tests were conducted in gentle breeze for the compounds of the present invention. The formulation of the compounds of the present invention was applied by DJI unmanned gyroplane with application height of 1 m and water volume of 20 kg/ha. The use rate was 600 g/ha. The active ingredient was dissolved by acetone and diluted to aqueous solution of Tween 80. There's a soybean field at 10 meters from the application area and the height of soybean plants were about 15 cm at the application time. The control compound C was applied in the same rate and under same conditions.

TABLE-US-00006 TABLE 6 Test results of activity No. Soybean 1 0 2 0 3 0 4 0 27 0 41 0 43 0 46 0 50 0 53 0 54 0 82 0 83 0 113 0 131 0 Control compound C 3 [00235]

[0159] It can be seen that the compounds of the present invention are not only safe for rice, but also safe for surrounding crops, and will not cause damage to sensitive broad-leaved crops due to drift problems under low wind conditions. Although the structure of the control compound is similar to the compounds of the present invention, it is not safe for rice, and at the same time, it is easy to cause phytotoxicity to the surrounding sensitive broad-leaved crops. With the large-scale promotion of unmanned aerial vehicles, there is a need for the herbicides of the present invention, which are safer to the environment.

[0160] At the same time, it is found after several tests that the compound and the composition of the present invention have good selectivity to many gramineae weeds such as Zoysia Japonica, Cynodon dactylon, Festuca elata, Poa annua, Lolium perenne and Paspalum vaginatum etc, and is able to control many important gramineous weeds and broad-leaved weeds. The compound also shows excellent selectivity and commercial value in the tests on wheat, corn, rice, sugarcane, soybean, cotton, oil sunflower, potato, orchards and vegetables in different herbicide application methods.