CN109400526B

CN109400526B - Pyridyloxy thioester derivative, preparation method thereof, herbicidal composition and application

Info

Publication number: CN109400526B
Application number: CN201811609358.9A
Authority: CN
Inventors: 连磊; 彭学岗; 华荣保; 张景远; 崔琦
Original assignee: Qingdao Kingagroot Chemical Compound Co Ltd
Current assignee: Qingdao Kingagroot Chemical Compound Co Ltd
Priority date: 2018-12-27
Filing date: 2018-12-27
Publication date: 2020-10-16
Anticipated expiration: 2038-12-27
Also published as: CN109400526A

Abstract

The invention belongs to the technical field of pesticides, and particularly relates to a pyridyloxy thioester derivative, a preparation method thereof, a weeding composition and application. The pyridyloxy thioester derivative is shown as a formula I,

wherein A, B each independently represents halogen, alkyl or cycloalkyl with or without halogen; c represents hydrogen, halogen, alkyl, haloalkyl; q represents halogen, cyano, cyanoalkyl, hydroxyalkyl, amino, nitro, formyl, halogen-free or halogen-containing alkyl, etc.; m represents an alkyl group, an alkenyl group or the like containing no or halogen; x represents nitro or NR₁R₂. The compound has excellent herbicidal activity and higher safety to cropsThe method establishes good selectivity for key crops such as rice and the like.

Description

Pyridyloxy thioester derivative, preparation method thereof, herbicidal composition and application

Technical Field

The invention belongs to the technical field of pesticides, and particularly relates to a pyridyloxy thioester derivative, a preparation method thereof, a weeding composition and application.

Background

Weed control is a crucial step in achieving efficient agriculture despite the variety of herbicides available on the market, e.g. DE2335349a1, GB1418979A, US3761486

The compounds shown and their use as herbicides. However, due to the problems of the ever-expanding market, the resistance of weeds, the service life of drugs, the economic efficiency of drugs and the like and the increasing attention of people to the environment, especially with the serious occurrence of the herbicide resistance of grass weeds in paddy fields, which is the mainstream in the market, such as penoxsulam, bispyribac-sodium, pyribenzoxim, cyhalofop-butyl of ACCE inhibition mechanism, metamifop and the like, in the ALS inhibition mechanism, the control of grass weeds in paddy fields, such as barnyard grass, crab grass, green bristlegrass, stephania japonica and the like, meets the serious challenge, and the lack of the medicament for effectively controlling the resistant weeds needs to be continuously researched by scientists so as to develop new herbicide varieties with high efficiency, safety, economy and different action modes.

Disclosure of Invention

The invention provides a pyridyloxy thioester derivative, a preparation method thereof, a weeding composition and application thereof, wherein the pyridyloxy thioester derivative has excellent weeding activity and higher crop safety, and particularly establishes good selectivity for key crops such as rice and the like.

The technical scheme adopted by the invention is as follows:

a pyridyloxy thioester derivative shown as a formula I,

wherein A, B each independently represents halogen, alkyl or cycloalkyl with or without halogen;

c represents hydrogen, halogen, alkyl, haloalkyl;

q represents halogen, cyano, cyanoalkyl, hydroxyalkyl, amino, nitro, formyl, halogen-free or halogen-containing alkyl, alkenyl, alkynyl, cycloalkyl, alkoxy, alkylthio, alkylcarbonyl, alkoxycarbonyl, alkylaminoalkyl or alkoxyalkyl, unsubstituted or substituted aryl, heteroaryl, arylalkyl, heteroarylalkyl;

m represents alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkylalkyl, -alkyl-R, halogen-free or halogen-containing,

And unsubstituted or substituted heterocyclyl, aryl, heteroaryl;

r represents

Cyano, nitro;

R₃each independently represents alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkylalkyl, and optionally substituted heterocyclyl, aryl, heteroaryl, heterocyclylalkyl, arylalkyl, heteroarylalkyl;

R₄、R₅、R₆each independently represents hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkylalkyl, alkoxycarbonyl, and optionally substituted heterocyclyl, aryl, heteroaryl, heterocyclylalkyl, arylalkyl, heteroarylalkyl;

x represents nitro or NR₁R₂Wherein R is₁Represents H, optionally substituted by 1-2R₁₁Substituted alkyl, alkenyl or alkynyl, -COR₁₂Nitro, OR₁₃，SO₂R₁₄，NR₁₅R₁₆，N＝CR₁₇R₁₈An alkylcarbamoyl group, a dialkylcarbamoyl group, a trialkylsilyl group or a dialkylphosphono group; r₂Represents H, optionally substituted by 1-2R₁₁Substituted alkyl or-COR₁₂(ii) a Or NR₁R₂Represents N ═ CR₂₁NR₂₂R₂₃，N＝CR₂₄OR₂₅A 5-or 6-membered saturated or unsaturated ring which is unsubstituted or substituted by 1 to 2 groups independently selected from halogen, alkyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio, amino, alkylamino, dialkylamino, alkoxycarbonyl, which ring contains no or no oxygen, sulfur or other nitrogen atom;

wherein R is₁₁Independently represent halogen, hydroxy, alkoxy, haloalkoxy, alkylthio, haloalkylthio, amino, alkylamino, dialkylamino, alkoxycarbonyl, unsubstituted or substituted aryl, heteroaryl;

R₁₂represents H, alkyl, haloalkyl, alkoxy, phenyl, phenoxy or benzyloxy;

R₁₃represents H, alkyl, haloalkyl, phenyl, benzyl or CHR₃₁C(O)OR₃₂；R₃₁Represents H, alkyl or alkoxy; r₃₂Represents H, alkyl or benzyl;

R₁₄represents alkyl, haloalkyl;

R₁₅represents H, alkyl, formyl, alkanoyl, haloalkylacyl, alkoxycarbonyl, phenylcarbonyl, phenoxycarbonyl or benzyloxycarbonyl; r₁₆Represents H, alkyl;

R₁₇represents H, alkyl, phenyl which is unsubstituted or substituted by 1 to 3 groups of halogen, alkyl and alkoxy; r₁₈Represents H, alkyl; or N ═ CR₁₇R₁₈Represents

R₂₁、R₂₄Each independently represents H or alkyl;

R₂₂、R₂₃each independently represents H or alkyl; or NR₂₂R₂₃Represents a 5-or 6-membered saturated or unsaturated ring which contains no or no oxygen, sulfur or other nitrogen atoms;

R₂₅represents an alkaneAnd (4) a base.

Preferably, A, B independently represent halogen, C1-C8 alkyl with or without halogen or C3-C8 cycloalkyl;

c represents hydrogen, halogen, C1-C8 alkyl, halogenated C1-C8 alkyl;

q represents halogen, cyano C1-C8 alkyl, hydroxy C1-C8 alkyl, amino, nitro, formyl, halogen-free or halogen-containing 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, unsubstituted or substituted aryl, heteroaryl, aryl C1-C8 alkyl, heteroaryl C1-C8 alkyl;

m represents halogen-free or halogen-containing C1-C18 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 cycloalkyl, C3-C8 cycloalkyl C1-C8 alkyl, - (C1-C8 alkyl) -R,

And unsubstituted or substituted heterocyclyl, aryl, heteroaryl;

r represents

Cyano, nitro;

R₃each independently represents C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 cycloalkyl, C3-C8 cycloalkyl C1-C8 alkyl, and unsubstituted or substituted heterocyclyl, aryl, heteroaryl, heterocyclyl C1-C8 alkyl, aryl C1-C8 alkyl, heteroaryl C1-C8 alkyl;

R₄、R₅、R₆each independently represents hydrogen, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 cycloalkyl, C3-C8 cycloalkyl C1-C8 alkyl, C1-C8 alkoxycarbonyl, unsubstituted or substituted heterocyclyl C1-C8 alkyl, aryl C1-C8 alkyl, heteroaryl C1-C8 alkyl;

x represents nitro or NR₁R₂Wherein R is₁Represents H, optionally substituted by 1-2R₁₁Substituted C1-C8 alkyl, C2-C8 alkenyl or C2-C8 alkynyl, -COR₁₂Nitro, OR₁₃，SO₂R₁₄，NR₁₅R₁₆，N＝CR₁₇R₁₈C1-C8 alkylcarbamoyl, di-C1-C8 alkylcarbamoyl, tri-C1-C8 alkylsilyl or di-C1-C8 alkylphosphonyl; r₂Represents H, optionally substituted by 1-2R₁₁Substituted C1-C8 alkyl or-COR₁₂(ii) a Or NR₁R₂Represents N ═ CR₂₁NR₂₂R₂₃，N＝CR₂₄OR₂₅Unsubstituted or substituted by 1 to 2 radicals independently selected from halogen, C1-C8 alkyl, C1-C8 alkoxy, halogenated C1-C8 alkoxy, C1-C8 alkylthio, halogenated C1-C8 alkylthio, amino, C1-C8 alkylamino, di-C1-C8 alkylamino, C1-C8 alkoxycarbonyl

Wherein R is₁₁Independently represent halogen, hydroxy, C1-C8 alkoxy, halogenated C1-C8 alkoxy, C1-C8 alkylthio, halogenated C1-C8 alkylthio, amino, C1-C8 alkylamino, di-C1-C8 alkylamino, C1-C8 alkoxycarbonyl, phenyl, naphthyl, unsubstituted or substituted by 1-3 of halogen, C1-C8 alkyl, halogenated C1-C8 alkyl, C1-C8 alkoxy, nitro,

R₁₂Represents H, C1-C18 alkyl, halogenated C1-C8 alkyl, C1-C8 alkoxy, phenyl, phenoxy or benzyloxy;

R₁₃represents H, C1-C8 alkyl, halogeno-C1-C8 alkyl, phenyl, benzyl or CHR₃₁C(O)OR₃₂；R₃₁Represents H, C1-C8 alkyl or C1-C8 alkoxy; r₃₂Represents H, C1-C8 alkyl or benzyl;

R₁₄represents C1-C8 alkyl, halogenated C1-C8 alkyl;

R₁₅represents H, C1-C8 alkyl, formyl, C1-C8 alkyl acylA halo C1-C8 alkanoyl group, a C1-C8 alkoxycarbonyl group, a phenylcarbonyl group, a phenoxycarbonyl group or a benzyloxycarbonyl group; r₁₆Represents H, C1-C8 alkyl;

R₁₇represents H, C1-C8 alkyl, phenyl which is unsubstituted or substituted by 1-3 of halogen, C1-C8 alkyl and C1-C8 alkoxy; r₁₈Represents H, C1-C8 alkyl; or N ═ CR₁₇R₁₈Represents

R₂₁、R₂₄Each independently represents H or C1-C8 alkyl;

R₂₂、R₂₃each independently represents H or C1-C8 alkyl; or NR₂₂R₂₃Represents

R₂₅Represents a C1-C8 alkyl group;

the "heterocyclic group" means a group having 0, 1 or 2 oxo groups

The "aryl" refers to phenyl, naphthyl; the "heteroaryl" refers to an aromatic cyclic group containing 3 to 6 ring atoms of which 1 to 4 heteroatoms are selected from oxygen, nitrogen and sulfur, and which may also be fused by a benzo ring, for example,

wherein, it is selected from halogen, nitryl, cyano, thiocyanato, hydroxyl, carboxyl, sulfydryl, formyl, phenyl, benzyl, benzyloxy, phenoxy which are unsubstituted OR substituted by at least one group selected from halogen, alkyl and alkoxy, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkylalkyl, OR ', SR ', alkyl-OR ', alkyl-SR ', COR ', COOR ', COSR ', SOR ', SO ', and the like which contain OR do not contain halogen₂R ', OCOR ', SCOR ' and is selected from hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkylalkyl, phenyl, benzyl, benzyloxy, phenoxy, COR ', COOR ', SO₂At least one of amino OR aminocarbonyl substituted with one OR two of R ', OR';

r' independently represent hydrogen, nitro, hydroxyl, amino, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, cycloalkylalkyl, alkoxy, alkenyloxy, alkynyloxy, cycloalkyloxy, alkoxyalkyl, alkoxycarbonyl, alkylthiocarbonyl, alkylsulfonyl, alkylsulfonylalkyl, alkylcarbonyl, alkylcarbonylalkyl, alkanoyloxy, alkylamino, alkylaminocarbonyl, alkoxyaminocarbonyl, alkoxycarbonylalkyl, alkylaminocarbonylalkyl, trialkylsilyl, dialkylphosphono, with or without halogen;

r' represents hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl and cycloalkylalkyl.

More preferably, A, B independently represent halogen, C1-C6 alkyl with or without halogen or C3-C6 cycloalkyl;

c represents hydrogen, halogen, C1-C6 alkyl, halogenated C1-C6 alkyl;

q represents halogen, cyano C1-C6 alkyl, hydroxy C1-C6 alkyl, amino, nitro, formyl, halogen-free or halogen-containing 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, unsubstituted or substituted aryl, heteroaryl, aryl C1-C6 alkyl, heteroaryl C1-C6 alkyl;

m represents halogen-free or halogen-containing C1-C12 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, C3-C6 cycloalkyl C1-C6 alkyl, - (C1-C6 alkyl) -R,

And unsubstituted or substituted heterocyclyl, aryl, heteroaryl;

r represents

Cyano, nitro;

R₃each independently represents C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, C3-C6 cycloalkyl C1-C6 alkyl, and unsubstituted or substituted heterocyclyl, aryl, heteroaryl, heterocyclyl C1-C6 alkyl, aryl C1-C6 alkyl, heteroaryl C1-C6 alkyl;

R₄、R₅、R₆each independently represents hydrogen, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, C3-C6 cycloalkyl C1-C6 alkyl, C1-C6 alkoxycarbonyl, unsubstituted or substituted heterocyclyl C1-C6 alkyl, aryl C1-C6 alkyl, heteroaryl C1-C6 alkyl;

x represents nitro or NR₁R₂Wherein R is₁Represents H, optionally substituted by 1-2R₁₁Substituted C1-C6 alkyl, C2-C6 alkenyl or C2-C6 alkynyl, -COR₁₂Nitro, OR₁₃，SO₂R₁₄，NR₁₅R₁₆，N＝CR₁₇R₁₈C1-C6 alkylcarbamoyl, di-C1-C6 alkylcarbamoyl, tri-C1-C6 alkylsilyl or di-C1-C6 alkylphosphonyl; r₂Represents H, optionally substituted by 1-2R₁₁Substituted C1-C6 alkyl or-COR₁₂(ii) a Or NR₁R₂Represents N ═ CR₂₁NR₂₂R₂₃，N＝CR₂₄OR₂₅Unsubstituted or substituted by 1 to 2 radicals independently selected from halogen, C1-C6 alkyl, C1-C6 alkoxy, halogenated C1-C6 alkoxy, C1-C6 alkylthio, halogenated C1-C6 alkylthio, amino, C1-C6 alkylamino, di-C1-C6 alkylamino, C1-C6 alkoxycarbonyl

Wherein R is₁₁Independently represent halogen, hydroxy, C1-C6 alkoxy, halogenated C1-C6 alkoxy, C1-C6 alkylthio, halogenated C1-C6 alkylthio, amino, C1-C6 alkylamino, di-C1-C6 alkylamino, C1-C6 alkoxycarbonyl, phenyl, naphthyl, unsubstituted or substituted by 1-3 of halogen, C1-C6 alkyl, halogenated C1-C6 alkyl, C1-C6 alkoxy, nitro,

R₁₂Represents H, C1-C14 alkyl, halogenated C1-C6 alkyl, C1-C6 alkoxy, phenyl, phenoxy or benzyloxy;

R₁₃represents H, C1-C6 alkyl, halogeno-C1-C6 alkyl, phenyl, benzyl or CHR₃₁C(O)OR₃₂；R₃₁Represents H, C1-C6 alkyl or C1-C6 alkoxy; r₃₂Represents H, C1-C6 alkyl or benzyl;

R₁₄represents C1-C6 alkyl, halogenated C1-C6 alkyl;

R₁₅represents H, C1-C6 alkyl, formyl, C1-C6 alkanoyl, halogeno-C1-C6 alkanoyl, C1-C6 alkoxycarbonyl, phenylcarbonyl, phenoxycarbonyl or benzyloxycarbonyl; r₁₆Represents H, C1-C6 alkyl;

R₁₇represents H, C1-C6 alkyl, phenyl which is unsubstituted or substituted by 1-3 of halogen, C1-C6 alkyl and C1-C6 alkoxy; r₁₈Represents H, C1-C6 alkyl; or N ═ CR₁₇R₁₈Represents

R₂₁、R₂₄Each independently represents H or C1-C6 alkyl;

R₂₂、R₂₃each independently represents H or C1-C6 alkyl; or NR₂₂R₂₃Represents

R₂₅Represents a C1-C6 alkyl group;

the "heterocyclic group" means a group having 0, 1 or 2 oxo groups

The "aryl" refers to phenyl, naphthyl; the term "heteroaryl" refers to

Wherein, it is selected from halogen, nitryl, cyano, thiocyanato, hydroxyl, carboxyl, sulfydryl, formyl, phenyl, benzyl, benzyloxy, phenoxy which are unsubstituted OR substituted by at least one group selected from halogen, C1-C6 alkyl, 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 ' and SO ' are optionally substituted by at least one group selected from halogen, C1-C6 alkyl, C1-C6 alkoxy₂R ', OCOR ', SCOR ' and substituted by a group selected from 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, and₂amino OR ammonia substituted by one OR two of R ', OR'0, 1,2 or 3 of the alkylcarbonyl groups;

r' independently represents hydrogen, nitro, hydroxyl, amino, C1-C6 alkyl containing or not containing fluorine, chlorine and bromine, C2-C6 alkenyl, C6-C6 alkynyl, C6-C6 cycloalkyl, C6-C6 cycloalkenyl, C6-C6 cycloalkyl C6-C6 alkyl, C6-C6 alkoxy, C6-C6 alkenyloxy, C6-C6 alkynyloxy, C6-C6 cycloalkyloxy, C6-C6 alkoxy C6-C6 alkyl, C6-C6 alkoxycarbonyl, C6-C6 alkylthio carbonyl, C6-C6 alkylsulfonyl C6-C6 alkyl, C6-C6 alkylcarbonyl, C6-C6 alkylcarbonyloxy, C6-C6 alkyl amino, C6-C6 alkyl-C6 alkyl-36, C1-C6 alkoxyaminocarbonyl, C1-C6 alkoxycarbonyl C1-C6 alkyl, C1-C6 alkylaminocarbonyl C1-C6 alkyl, tri-C1-C6 alkylsilyl, di-C1-C6 alkylphosphonyl;

r' independently represents hydrogen, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, C3-C6 cycloalkyl, C1-C6 alkyl.

Further preferably, A, B each independently represents halogen, C1-C6 alkyl, halo C1-C6 alkyl, C3-C6 cycloalkyl;

c represents hydrogen, halogen, C1-C6 alkyl, halogenated C1-C6 alkyl;

q represents C1-C6 alkyl, halogenated 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, hydroxyC 1-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, and also C1-C6 alkyl-unsubstituted or substituted

Phenyl unsubstituted or substituted by at least one of C1-C6 alkyl, halo C1-C6 alkyl, halo, and C1-C6 alkoxy;

m represents C1-C12 alkyl (preferably C1-C8 alkyl, more preferably C1-C6 alkyl), halogenated C1-C8 alkyl, C3-C6 cycloalkyl, C2-C6 alkenyl, halogenated C2-C6 alkenyl, C2-C6 alkynyl, C1-C6 alkoxy, C1-C6 alkoxycarbonyl, C1-C6 alkylsulfonyl, cyano C1-C6 alkyl, nitro C1-C6 alkyl, C1-C6 alkoxy C1-C6 alkyl, C1-C6 alkoxycarbonyl C1-C6 alkyl, C2-C6 alkenyloxycarbonyl C1-C6 alkyl, - (C1-C6 alkyl) -R,

Tetrahydrofuryl, pyridyl, naphthyl, furyl, thienyl,

And unsubstituted or C1-C6 alkyl-substituted

Phenyl unsubstituted or substituted by C1-C6 alkyl, halogenated C1-C6 alkyl, C1-C6 alkylamino, halogen or C1-C6 alkoxy;

r represents

R₃Each independently represents a C1-C6 alkyl group;

R₄、R₅、R₆each independently represents hydrogen, C1-C6 alkyl, C1-C6 alkoxycarbonyl;

r' represents C1-C6 alkyl, halogenated C1-C6 alkyl;

x represents amino, C1-C6 alkylamino, C1-C6 alkylcarbonylamino, phenylcarbonylamino, benzylamino, optionally halogenated C1-C6 alkyl-substituted furanylmethyleneamino.

Still more preferably A, B each independently represents fluoro, chloro, bromo, iodo, methyl, ethyl, propyl, isopropyl, trifluoromethyl, cyclopropyl;

c represents hydrogen, fluorine, chlorine, bromine, iodine, methyl and trifluoromethyl;

q represents methyl, ethyl, propyl, isopropyl, cyclopropyl, vinyl, ethynyl, fluorine, chlorine, bromine, cyano, amino, nitro, formyl, methoxy, methylthio, methoxycarbonyl, chloromethyl, monofluoromethyl, difluoromethyl, trifluoromethyl, 2-chloroethyl, 2-trifluoroethyl, hydroxymethyl,

Benzyl, naphthyl, furyl, thienyl, thiazolyl, pyridyl, pyrimidyl, and unsubstituted or substituted by methyl

Phenyl unsubstituted or substituted with at least one group selected from methyl, trifluoromethyl, chlorine and methoxy;

r' represents methyl, ethyl, difluoromethyl;

m represents methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, 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, methyl-sulfonyl, methyl-propyl, cyclohexyl, 2-chloroethyl, 2-bromoethyl, 2, 2-difluoroethyl, 2,2, 2-trifluoroethyl, 4,4, 4-trifluorobutyl, 2,2,3,3,

Tetrahydrofuryl, pyridyl, naphthyl, furyl, thienyl,

And unsubstituted or methyl-substituted

Phenyl which is unsubstituted or substituted by methyl, dimethylamino, chloro, methoxy, trifluoromethyl or isopropyl;

x represents NH₂、

In the definition of the compounds of the general formula I above and in all the formulae below, the terms used, whether used alone or in compound words, represent the following substituents: alkyl groups having more than two carbon atoms may be straight chain or branched. Such as the compound "-alkyl-OR" ", where alkyl may be-CH₂-、-CH₂CH₂-、-CH(CH₃)-、-C(CH₃)₂-and the like. Alkyl groups are, for example, methyl; an ethyl group; n-propyl or isopropyl; n-butyl, isobutyl, tert-butyl or 2-butyl; a pentyl group; hexyl radicals, such as the n-hexyl radical, the isohexyl radical and the 1, 3-dimethylbutyl radical. Halogen is fluorine, chlorine, bromine or iodine.

If a group is substituted by a group, this is understood to mean that the group is substituted by one or more identical or different radicals selected from those mentioned. The same or different substitution characters contained in the same or different substituents are independently selected and may be the same or different.

Depending on the nature of the substituents and the manner in which they are attached, the compounds of formula I may exist as stereoisomers. For example, enantiomers and diastereomers may occur if one or more asymmetric carbon atoms are present. Stereoisomers may be obtained from the mixtures obtained in the preparation by customary separation methods, for example by chromatographic separation. Stereoisomers can likewise be prepared selectively by using stereoselective reactions and using optically active starting materials and/or auxiliaries. The invention also relates to all stereoisomers contained in formula I but not specifically defined and mixtures thereof.

The preparation method of the pyridyloxy thioester derivative comprises the following steps:

reacting a compound shown in a general formula III with a compound shown in a general formula II to obtain a compound shown in a general formula I; the reaction equation is as follows:

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 combination of DCM, DCE, ACN, THF and DMF.

Or when X represents NR₁R₂(R₁、R₂Not simultaneously hydrogen), the compound shown in the general formula I-1 is added

Reacting with corresponding halide to obtain the product;

among them, 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 than two of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate and cesium carbonate; the solvent is one or more of THF, 1, 4-dioxane, toluene, 1, 2-dichloroethane, ethyl acetate, acetonitrile, DMF, acetone, dichloromethane and chloroform; a catalyst, preferably DMAP, may also be added during the reaction.

A herbicidal composition comprising (I) at least one pyridyloxythioester derivative of formula I; preferably, further comprising (ii) one or more additional herbicides and/or safeners; more preferably, (iii) an agrochemically acceptable formulation auxiliary.

A method for controlling weeds, which comprises applying a herbicidally effective amount of at least one of said pyridyloxythioester derivatives or said herbicidal composition to a plant or to an area of weeds, preferably to the plant (e.g., japonica rice, indica) and the weeds are grasses (e.g., Echinochloa crusgalli, crab grass, Euphorbia lathyris, Setaria viridis), broadleaves (e.g., Abutilon abutilon, Monochoria scandens) and Cyperaceae (e.g., Cyperus brevica).

At least one of the pyridyloxythioester derivatives or the herbicidal composition for controlling weeds, preferably, the pyridyloxythioester derivative is used for controlling weeds in useful crops, such as transgenic crops or crops treated by genome editing technology, more preferably, rice (such as japonica rice and indica rice), and the weeds are gramineae (such as barnyard grass, crab grass, moleplant seed and green bristlegrass), broadleaf weeds (such as abutilon, monochoria vaginalis) and cyperaceae (such as cyperus rotundus).

The compounds of the formula I according to the invention have outstanding herbicidal activity against a large number of economically important monocotyledonous and dicotyledonous harmful plants. The active substances according to the invention are also effective against perennial weeds which grow from rhizomes, or other perennial organs and are difficult to control. In this connection, it is generally immaterial whether the substance is used before sowing, before germination or after germination. Mention is made in particular of representative examples of the monocotyledonous and dicotyledonous weed groups which the compounds of the invention can control, without being restricted to a defined species. Examples of weed species for which the active substance acts effectively include monocotyledons: annual avena, rye, grass, alopecurus, farris, barnyard grass, digitaria, setaria and sedge, and perennial agropyron, bermudagrass, cogongrass and sorghum, and perennial sedge.

With regard to dicotyledonous weed species, the action can be extended to species such as the annual cleavers, viola, veronica, picea, chickweed, amaranthus, sinapis, ipomoea, sida, matricaria and abutilon species, and the perennial weeds cyclocarya, thistle, sorrel and artemisia. The active substances according to the invention are effective in controlling harmful plants, such as barnyard grass, sagittaria, alisma, eleocharis, saccharum and cyperus, in this particular condition of sowing of rice. If the compounds of the present invention are applied to the soil surface before germination, seedlings of weeds can be completely prevented before the weeds grow out, or the weeds stop growing when they grow out of cotyledons and finally die completely after three to four weeks. The compounds of the invention are particularly active against plants such as, for example, alpinia, sesamum indicum, polygonum convolvulus, chickweed, veronica vinifera, veronica albo, viola tricolor and amaranth, cleavers and kochia.

Although the compounds of the invention have excellent herbicidal activity against monocotyledonous and dicotyledonous weeds, they are not at all harmful or only insignificantly harmful to the important economic crop plants, such as wheat, barley, rye, rice, maize, sugar beet, cotton and soybean. Especially good compatibility with cereal crops such as wheat, barley and maize, especially wheat. The compounds according to the invention are therefore very suitable for selectively controlling unwanted vegetation in agricultural crops or ornamental plants.

Due to their herbicidal properties, these active substances can be used for controlling harmful plants in the cultivation of genetically engineered plants which are known or are to occur. Transgenic plants often have advantageous traits, such as resistance to specific insecticides, particularly to specific herbicides, resistance to plant diseases or to microorganisms pathogenic to plant diseases, such as specific insects or microorganisms of fungi, bacteria or viruses. Other specific traits are related to the conditions of the product, such as quantity, quality, storage stability, composition and specific ingredients. Thus, it is known that the resulting transgenic plant products have an increased starch content or an improved starch quality or a different fatty acid composition.

The compounds of the formula I according to the invention or their salts are preferably used for economically important transgenic crops and ornamentals, for example cereals, such as wheat, barley, rye, oats, millet, rice, cassava and maize, or for the cultivation of sugar beet, cotton, soybean, rapeseed, potato, tomato, pea and other vegetable plants. The compounds of the formula I are preferably used as herbicides for cultivating useful plants which are resistant to the action of the herbicide or which are resistant to the toxic action of the herbicide by genetic engineering.

Conventional methods for breeding plants having improved shape over known plants include, for example, conventional mating methods and mutant breeding. In other words, new plants with improved traits may be obtained by means of methods of genetic engineering (see, for example, EP-0221044A, EP-0131624A). For example, several methods have been described:

to improve starch synthesis in plants, crop plants are modified by genetic engineering (e.g. WO 92/11376, WO92/14827, WO 91/19806);

transgenic crop plants which are resistant to particular herbicides, to glufosinate herbicides (e.g. EP-0242236A, EP-0242246A) or to glyphosate-type herbicides (WO 92/00377), or to sulfonylurea-type herbicides (EP-0257993A, US-5013659A);

transgenic crop plants, such as cotton, which produce Bacillus thuringiensis toxins (Bt toxins) which protect against attack on plants by specific pests (EP-0142924A, EP-0193259A);

-transgenic crop plants with improved fatty acid composition (WO 91/13972).

A number of molecular biotechnologies are known which enable the production of transgenic plants with improved traits (see, for example, Sambrook et al, 1989, molecular amplification, second edition of the laboratory Manual, Cold spring harbor laboratory publications in USA, Cold spring harbor, New York; or Winnacker "Gene und Klone" [ genes and clones ], VCH Weinheim, second edition 1996 or Christou, "trends in plant science" 1(1996)423- "431)). In order to carry out the manipulation of genetic engineering, it is possible to introduce nucleic acid molecules into plasmids, which undergo mutations or sequence changes by recombination of DNA sequences. Using standard methods as described above, it is possible, for example, to exchange substrates, remove partial sequences or add natural or synthetic sequences. In order to ligate the DNA fragments to each other, it is possible to attach a binder or a linker to the fragments.

Plant cells of reduced activity gene products can be prepared, for example, by expressing at least one suitable antisense-RNA, sense-RNA to achieve a cosuppression effect, or by expressing at least one suitably configured ribozyme which specifically cleaves transcripts of the gene products.

For this purpose, it is possible to use DNA molecules which contain the entire coding sequence of the gene product, including any flanking sequences which may be present, and to use DNA molecules which contain only a part of the coding sequence which has to be long enough to achieve an antisense effect in the cell. Sequences that are highly homologous but not identical to the coding sequence of the gene product may also be used.

When expressing the nucleic acid molecule in a plant, the synthetic protein can be localized in any desired plant cell compartment. However, for localization in a specific chamber, it is possible, for example, to link the coding region to a DNA sequence in order to ensure localization in a specific location. These 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).

Transgenic plant cells can be recombined into whole plants using known techniques. The transgenic plant may be of any desired plant variety, i.e., monocotyledonous and dicotyledonous plants. In this way, it is possible to obtain transgenic plants with improved traits by overexpressing, inhibiting or suppressing homologous (═ natural) genes or gene sequences, or by expressing heterologous (═ external) genes or gene sequences.

When the active substances according to the invention are used on transgenic crops, in addition to the harmful-plant-inhibiting effects observed on other crops, special effects are often observed on the corresponding transgenic crops, for example an improved or enlarged spectrum of weed control, improved application rates in the application, preferably a good combination of resistance of the transgenic crop and herbicide performance, and an influence on the growth and yield of the transgenic crop plants. The invention therefore also provides for the use of the compounds as herbicides for controlling harmful plants in transgenic crop plants.

In addition, the compound of the invention can obviously regulate the growth of crop plants. These compounds are used to target the control of plant components and to promote harvesting, such as desiccation and stunting of plants, by regulating the metabolism of plants involved. They are also suitable for regulating and inhibiting undesirable vegetation without destroying the growth of the crop plants. Inhibiting plant growth plays a very important role in many monocotyledonous and dicotyledonous crop plants, since this reduces or completely prevents lodging.

The compounds of the present invention can be applied using general formulations, and wettable powders, concentrated emulsions, sprayable solutions, powders or granules can be used. Thus the present invention also provides herbicidal compositions comprising compounds of formula I. The compounds of formula I can be formulated in a variety of ways depending on the usual biological and/or chemical physical parameters. Examples of suitable formulation choices are: wettable Powders (WP), water Soluble Powders (SP), water soluble concentrates, Emulsion Concentrates (EC), emulsions dispersed in water (EW), for example, oil-in-water and water-in-oil (EW), sprayable solutions, Suspension Concentrates (SC), dispersible oil suspensions (OD), suspensions with oil or water as diluent, solutions of miscible oils, powders (DP), Capsule Suspensions (CS), core (cutting) compositions, granules for spreading and soil application, spray granules, coated granules and absorbent granules, water dispersible granules (WG), water Soluble Granules (SG), ULV (ultra low volume) formulations, microcapsules and wax preparations. These individual formulation types are known and described in, for example, Winnacker-Kuchler, "Chemische Techologie" [ Chemicals Process ], Vol.7, C.Hauser Verlag Munich, 4 th edition 1986; wade van Valkenburg, "pest formulations," Marcel Dekker, n.y., 1973; martens, "Spray Drying" handbook, 3 rd edition 1979, g.

The necessary formulation auxiliaries, such as inerts, surfactants, solvents and other additives, are likewise known and are described in the documents mentioned below, for example in Watkins, "handbook of powdered diluents pesticides and carriers", second edition, Darland book Caldwell n.j.; h.v.01phen, "entry to clay colloid chemistry," second edition, j.wiley and Sons, n.y.; marsden, second edition "solvent guide", Interscience, n.y.1963; "annual report of detergents and emulsifiers" by McCutcheon, MC issues, Ridgewood n.j.; sisley and Wood, "surfactant encyclopedia", chemical publishing company, n.y.1964;

is/are as follows

[ ethylene oxide adduct surfactant]，Wiss.Verlagagesell.Stuttgart 1976；Winn"Chemische technology" of acker-K ü chler [ chemical Process]Volume 7, c.hauser Verlag Munich, 4 th edition 1986.

Wettable powders can be uniformly dispersed in water and, in addition to the active substance, include diluents or inert substances, ionic and nonionic surfactants (wetting agents, dispersants), such as polyethoxylated alkylphenols, polyethoxylated fatty alcohols, polyoxyethylated fatty amines, fatty alcohol polyglycol ether sulfates, alkylsulfonates, alkylphenylsulfonates, sodium lignosulfonates, sodium 2,2 '-dinaphthylmethane-6, 6' -disulfonate, sodium dibutylnaphthalenesulfonate or sodium oleoylmethyltaurate. To prepare wettable powders, the active substances of the herbicides are finely ground, for example using customary instruments, such as hammer mills, fan mills and jet mills, with simultaneous or sequential incorporation of the adjuvants.

Emulsions are prepared by dissolving the active substance in an organic solvent, such as butanol, cyclohexanone, dimethylformamide, xylene or higher boiling aromatics or hydrocarbons or mixtures of solvents, and adding one or more ionic and/or nonionic surfactants (emulsifiers). Examples of emulsifiers which may be used are calcium alkylarylsulfonates, for example calcium dodecylbenzenesulfonate, or nonionic emulsifiers, for example polyglycol esters of fatty acids, alkylarylpolyglycol ethers, fatty alcohol polyglycol ethers, propylene oxide-ethylene oxide condensation products, alkyl polyethers, sorbitan esters, for example sorbitan fatty acid esters, or polyoxyethylene sorbitan esters, for example polyoxyethylene sorbitan fatty acid esters.

The active substance and finely divided solid substances, for example talc, natural clays such as kaolin, bentonite and pyrophyllite, or diatomaceous earth, are ground to give a powder. Water or oil based suspensions may be prepared, for example, by wet milling using a commercially available bead mill, with or without the addition of a surfactant of the other formulation type described above.

For preparing emulsions, for example oil-in-water Emulsions (EW), it is possible to use aqueous organic solvents, using stirrers, colloid mills and/or static mixers, and, if desired, to add surfactants of another formulation type as described above.

Granules are prepared by spraying the active substance onto the adsorbate, granulating with inert material, or concentrating the active substance onto the surface of a carrier, for example sand, kaolinite, and granulating the inert material with a binder, for example polyvinyl alcohol, sodium polyacrylate or mineral oil. Suitable active substances can be granulated by the process for preparing fertilizer granules, if desired mixed with fertilizers. The preparation of water-suspendable granules is carried out by customary methods, for example spray-drying, fluidized-bed granulation, millstone granulation, mixing using high-speed mixers and extrusion without solid inert materials.

For the preparation of granules using a millstone, a fluidized bed, an extruder and Spray coating, see the following processes, for example "Spray Drying handbook", third edition 1979, g.goodwin ltd, london; browning, "Agglomeration", chemical and engineering 1967, page 147 ff; "Perry's handbook of Engineers of chemistry", fifth edition, McGraw-Hill, New York 1973, pages 8-57. If preparations for crop protection products are to be known, see, for example, G.C. Klingman, "Weed Control as a Science", John Wiley and Sons, New York, pages 196181-96 and J.D. Freyer, S.A. Evans "Weed Control Manual", fifth edition, Blackwell scientific rules, Oxford university 1968, page 101-.

Agrochemical formulations generally comprise from 0.1 to 99%, in particular from 0.1 to 95% by weight of active substance of formula I. The concentration of active substance in wettable powders is, for example, from about 10 to 99% by weight, with usual formulation components making up the remainder to 100% by weight. The concentration of the active substance in the emulsion concentrate may be about 1 to 90%, preferably 5 to 80% by weight. Powder formulations contain from 1 to 30% by weight of active, usually preferably from 5 to 20% by weight of active, whereas sprayable solutions contain from about 0.05 to 80%, preferably from 2 to 50% by weight of active. The content of active substance in the aqueous suspension granules depends primarily on whether the active substance is liquid or solid, and the auxiliaries, fillers and the like used in granulation. The content of active substance in the water-suspendable granule formulation is, for example, between 1 and 95% by weight, preferably between 10 and 80% by weight.

The active substance formulations mentioned may additionally comprise tackifiers, wetting agents, dispersants, emulsifiers, penetrants, preservatives, antifreezes, solvents, fillers, carriers, colorants, antifoams, evaporation inhibitors and generally customary pH and viscosity regulators in all cases.

On the basis of these formulations, it is also possible to mix them with other insecticide active substances, such as insecticides, acaricides, herbicides and fungicides, and also with safeners, fertilizers and/or plant growth regulators, either premixed or mixed in containers.

Suitable active substances which can be mixed with the active substances according to the invention in a compounded or tank-mixed formulation are, for example, the substances known from "the world Wide Specification of New agricultural chemical products", from the national agricultural science and technology Press, 2010.9 and the documents cited therein. For example, the herbicidal active substances mentioned below may be mixed with the mixtures of the formula I (remarks: name of the compound, either by common name according to the International organization for standardization (ISO), or by chemical name, where appropriate with a code number): acetochlor, butachlor, alachlor, propisochlor, metolachlor, s-metolachlor, pretilachlor, propyzamide, pretilachlor, napropamide, R-levulinyl-propyzamide, propanil, mefenacet, dibenzamide, diflufenican, flumetsulam, bromobutyrolac, dimethenamid, mefenacet, metazachlor, isoxaflutole, ryegrass methyl ester, loflutolane, diacrylamide, pethoxamide, butachlor, propisochlor, cyprosulfamide, flumetsulam, heptanoyl, isobutramine, propyzamide, terbutamid, dimethenamid, larvamide, trimethylcyclam, clofenamid, propyzamide, penoxulamide, carpronide, diflormid, trinitrol, butachlor, butafenacet, butachlor, benfluralin, bencarbzamide, pencyhalonil, metolachlor, bencarbzamide, pencyhalonil, buta, Grazing amine, bensulfuron, quinoxalamine, bensulfuron-methyl, naproxen, acetochlor, naphazel, thiachlor, pyraflufen, bensulfuron-methyl, prochloraz, clofenamide, butamidam, flupiram, atrazine, simazine, prometryn, cyanazine, simetryn, ametryn, prometryn, ipratron, flurazin, terbutryn, triazineone-flumetsulam, ciprofloxacin, glycazine, pradapazine, prometryn, simatong, azidezin, diuron, isopentetryn, cycloprozine, ametryn, terbuthylazine, terbuton, metocloprid, cyanazine, bentazon, clonazine, atrazine, metribuzin, cyanuric acid, indaziflazaflam, chlorsulfuron, meturon, bensulfuron, chlorimuron, tribenuron-methyl, thifensulfuron-methyl, pyrazosulfuron-methyl, sulfosulfuron-methyl, sulfometuron, Cinosulfuron, triasulfuron, sulfometuron-methyl, nicosulfuron, ethametsulfuron, amidosulfuron, ethoxysulfuron, cyclosulfamuron, rimsulfuron, azimsulfuron, primisulfuron-methyl, flusulfuron-methyl, flupyrsulfuron-methyl, epoxysulfuron, imazosulfuron, primisulfuron-methyl, prosulfuron, sulfosulfuron, trifloxysulfuron, triflusulfuron, metsulfuron-methyl sodium, flupyrazosulfuron, methisulfuron-methyl, primisulfuron, propysilfuron (Propyrisulfuron), metribusulfuron, acifluorfen-methyl, fomesafen, lactofen, fluoroglycofen-ethyl, oxyfen, prosulfuron, benfuresafen, trifloxysulfuron, metofen-ethyl, metofen, trifloxysulfuron, fluroxypyr, fluridone, benfop, benfluridone, benfurazolin, benfluridone, benfurbenflur, Dimethofen, oxyfluorfen, clofenflurate, Halosafen, chlortoluron, isoproturon, linuron, diuron, sifenuron, fluometuron, benzthiauron, methabenzuron, prosulfuron, sulfosulfuron, clomauron, clodinafuron, clofensulfuron, metoxuron, bromuron, metoxuron, meturon, fensulfuron, prosulfuron, subtilon, cuarone, metolachlor, cycloaroron, cyclouron, thifluuron, buthiuron, kuron, cumuron, metoxuron, methamidothion, metominosulfuron, trifolium, isoxafluron, isoxauron, moneuronon, aniron, methicuron, chloretron, clotururon, teuron, benuron, pennison, phenmedibensulfuron, bensulfuron, benazolin, propham, buthan, thiuron, buthan, benazolin, buthan, benazolin, buthan, benazol, Thiobencarb, merthiolane, diclofop, triallate, penoxsulam, pyributicarb, dichlorfon, edifenphos, ethiofen, prosulfocarb, clenbuterol, prosulfocarb, dichotomene, thiobencarb, promethazine, Isopolinate, Methiobencarb, 2, 4-d butyl ester, 2 methyl 4-sodium chloride, 2, 4-d isooctyl ester, 2 methyl 4-chloroisooctyl ester, 2, 4-d sodium salt, 2, 4-d dimethylamine salt, 2 methyl 4-chloroethyl thioester, 2 methyl 4 chloride, 2, 4-d propionic acid, 2, 4-d propionate, 2, 4-d butyric acid, 2 methyl 4-chloropropionic acid, 2 methyl 4-chlorobutyric acid, 2,4, 5-d nasal discharge, 2,4, 5-d propionic acid, 2,4, 5-d butyric acid, 2 methyl 4-chloropropionic acid, 2 methyl 4-d propionic acid, 2-d propionic acid, 2-cloroprionic acid, triclocarb, triclopyr, triclop, Aminodiclofenac, metocloprofenac, diclofop-methyl, fluazifop-p-butyl, haloxyfop-methyl, haloxyfop-p-butyl, quizalofop-ethyl, quizalofop-p-ethyl, fenoxaprop-p-ethyl, propaquizafop-ethyl, fenoxaprop-ethyl, clodinafop-ethyl, benazolin, clodinafop-ethyl, haloxyfop-methyl, benazolin, propalaxyl, butyfen-ethyl, chloroethafloxacin, aminofluanid, benazolin, dichlofop-ethyl, methamphetalin, propamocarb-ethyl, benfop-methyl, thiophosphine, pirimiphos-methyl, benfop-ethyl, benazolin, benfop-methyl, imax-methyl, mefenofos, mefeno, Imazamox ammonium salt, imazapic acid, imazamethabenz ester, fluroxypyr, clopyralid, picloram, triclopyr, dithiopyr, haloxydine, triclopyril, thiazopyr, fluridone, aminopyralid, diflufenzopyr, butoxyethyl triclopyr, Clodinate, sethoxydim, clethodim, cycloxydim, clethodim, topramezone, Buthidazole, metribuzin, hexazinone, metamitron, metribuzin, amitridione, Amibuzin, bromoxynil, octanoyl ioxynil, dichlobenitrile, pyraclonil, hydroxybensulam, Iodobonil, flumetsulam, penoxsulam, clofenapyr, pyraclonil, pyraflufen-ethyl, pyraoxystrobin, flumetsulam, pyraclonil, pyraoxystrobin, isoxathion, pyriftalid, pyriminobac-methyl, pyrithiobac-methyl, benzobicylon, mesotrione, sulcotrione, Tembotrione, Tefuryltrione, Bicyclopyrone, ketodradox, isoxaflutole, isoxaclomazone, fenoxasulfofone, methiozoline, isopyrafen, pyraflufen, pyrazote, difenzoquat, pyrazoxazole, pyroxaflutole, pyroxsulam, pyraclofos, pyraclonil, amicarbazone, carfentrazone, flumiclone, sulfentrazone, bencarane, bisphenomezone, butafenacil, isoxaflutole, cyclam, triclopyr, fluroxypyr, flumethazine, parnaprox, flumiclone, flumethol, carfentrazone, carzone, carfentrazone, car, Fluazifop-methyl, pyriminostrobin, bromopicrin, didaphylm, pyridaben, Pyridafol, quinclorac, chloroquine, bentazon, pyridate, oxaziclomefone, benazolin, clomazone, isoprox, isoproxypyrim, propyribac, cumylfen, clomazone, sodium chlorate, thatch, trichloroacetic acid, monochloroacetic acid, hexachloroacetone, tetrafluoropropionic acid, mequat, bromophenol oxime, triazasulam, imazazole, flurtamone, mesotrione, ethofumesate, pyrimethanil, clodinafop-methyl, clodinium, pyributaine, benfurazolin, meton, metamitron, metolachlor, dichlorvofen, triclopyr, aloac, Dietmquat, Etpronil, ipriflam, iprimazam, iprodione, Trizopyr, Thiaclonifen, chlorpyrifos, pyradifquat, chlorpyrifos, propiram, pyradifurone, pyradifon, pyradifurone, pyrazone, thion, pyrazone, clomazone, fenclorim, cloquintocet-mexyl, mefenpyr-diethyl, DOWFAUC, 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.

In the context of the present specification, if the abbreviated forms of the common name of the active compounds are used, all customary derivatives, such as esters and salts, and also isomers, in particular optical isomers, in particular one or more commercially available forms, are included in each case. If the generic name denotes esters or salts, all other customary derivatives, such as other esters and salts, free acids and neutral compounds, and also isomers, in particular optical isomers, in particular one or more commercially available forms, are also included in each case. The chemical name given for a compound means at least one compound covered by the generic name, with compounds generally being preferred.

When used, the commercially available formulations are diluted in the usual manner, if desired, for example in wettable powders, concentrated emulsions, suspensions and granules suspended in water, using water. Powders, granules for soil application or solutions for spreading and spraying generally do not require further dilution with inert substances before use. The required amount of the compound of formula I to be used varies with the external conditions, such as temperature, humidity, the nature of the herbicide used, etc. It may vary widely, for example between 0.001 and 1.0kg/ha, or more of active substance, but preferably between 0.005 and 750g/ha, in particular between 0.005 and 500 g/ha.

Detailed Description

The following examples are intended to illustrate the invention and should not be construed as limiting it in any way. The scope of the invention is indicated by the appended claims.

In view of the economic and diversity of the compounds, we prefer to synthesize some of the compounds, a selection of which are listed in table 1 below. Specific compound structures and corresponding compound information are shown in tables 1 and 2. The compounds in table 1 are only for better illustrating the present invention, but not for limiting the present invention, and it should not be understood to limit the scope of the above-mentioned subject matter of the present invention to the following compounds for those skilled in the art.

Table 1 Structure of Compounds and methods of use thereof¹HNMR data

TABLE 2 Compounds¹HNMR data

Several methods for preparing the compounds of the present invention are illustrated in the schemes and examples below. The starting materials are commercially available or can be prepared by methods known in the literature or as shown in detail. It will be appreciated by those skilled in the art that other synthetic routes may also be utilized to synthesize the compounds of the present invention. Although specific starting materials and conditions for the synthetic route are described below, they can be readily substituted with other similar starting materials and conditions, and variations or modifications of the preparation process of the present invention, such as various isomers of the compounds, are included in the scope of the present invention. In addition, the preparation methods described below may be further modified in accordance with the present disclosure using conventional chemical methods well known to those skilled in the art. For example, protecting the appropriate groups during the reaction, and the like.

The following process examples are provided to facilitate a further understanding of the methods of preparation of the present invention, and the particular materials, species and conditions used are intended to be further illustrative of the invention and are not intended to limit the reasonable scope thereof. The reagents used in the synthesis of the compounds indicated in the following table are either commercially available or can be readily prepared by one of ordinary skill in the art.

Examples of representative compounds are as follows:

1. synthesis of Compound 50

(1) Placing compound 50-1(500mg, 4.16mmol), NBS (741mg, 4.16mmol), catalytic amount of AIBN (10mg) and carbon tetrachloride (20mL) in a 100mL single-neck bottle, stirring at 60 ℃ for 12 hours, detecting the completion of the raw material reaction by high performance liquid chromatography, cooling the reaction solution to room temperature, filtering off solids, and concentrating the carbon tetrachloride phase to obtain compound 50-2(800mg, crude product), which is used in the next step without purification.

(2) Compound a (400mg, 1.7mmol), Compound 50-2 from the above step (800mg, crude), a catalytic amount of TBAB (10mg), DMF (10mL) was placed in a 50mL round bottom flask and heated to 85 ℃ for 12 hours. Liquid chromatography was performed to determine the completion of the starting material reaction, the reaction was cooled to room temperature, extracted with water (100mL) and methyl tert-butyl ether (50mL x2), the organic phase was dried, concentrated, and column-separated to give compound 50(180mg, 33% yield).

2. Synthesis of Compound 66

(1) Compound 66-1(300mg, 4.83mmol), TEA (586mg, 5.79mmol) were dissolved in anhydrous dichloromethane (20mL), cooled to 0 deg.C, and Compound b (1.15g, 5.31mmol) was slowly added dropwise. The temperature was slowly raised to room temperature and the reaction was continued for 12 hours. The reaction was quenched by pouring into ice water, extracted, the organic phase washed once with 50mL saturated sodium bicarbonate, dried, and concentrated to give compound 66-2(1.2g, crude) which was used in the next step without purification.

(2) Compound a (400mg, 2.13mmol), compound 66-2 from step (1) (1.2g, crude), catalytic amount of TBAB (10mg), DMF (10mL) was placed in a 50mL round bottom flask and heated to 85 deg.C for 12 h. After the reaction of the raw materials was completed by liquid chromatography, the reaction was cooled to room temperature, extracted with water (100mL) and methyl tert-butyl ether (50mL × 2), dried and concentrated, and subjected to column separation to obtain compound 66(300mg, yield 56%) as a white solid.

3. Synthesis of Compound 97

(1) Compound 97-1(300mg, 4.1mmol) was dissolved in anhydrous methanol (20mL), cooled to 0 deg.C and solid sodium methoxide (244mg,4.51mmol) was added portionwise. After stirring at 0 ℃ for 10min, compound 97-2(271mg, 4.51mmol) was slowly added dropwise thereto. The temperature was slowly raised to room temperature and the reaction was continued for 12 hours. Detecting that the raw materials are basically reacted completely by high performance liquid chromatography, and dropwise adding a small amount of acetic acid solution to be neutral. The reaction was concentrated to remove methanol, extracted with water (100mL) and ethyl acetate (100mL x2), and the organic phase was dried and concentrated to give compound 97-3(500mg, crude) which was used in the next reaction without purification.

(2) Compound 97-3(500mg, crude), TEA (518mg, 5.12mmol) was dissolved in anhydrous dichloromethane (20mL), cooled to 0 deg.C and compound b (1.01g, 4.69mmol) was added slowly dropwise. The temperature was slowly raised to room temperature and the reaction was continued for 12 hours. The reaction was quenched into ice water, extracted, the organic phase washed once with 50mL saturated sodium bicarbonate, dried, and concentrated to give 97-4(1g, crude) which was used in the next step without purification.

(3) Compound a (400mg, 1.7mmol), compound 97-4 from the above step (1g, crude), a catalytic amount of TBAB (10mg), DMF (10mL) was placed in a 50mL round bottom flask and heated to 85 deg.C for 12 hours. Liquid chromatography and mass spectrometry detection the starting material was reacted completely, the reaction was cooled to room temperature, water (100mL) and methyl tert-butyl ether (50mL x2) were extracted, the organic phase was dried, concentrated, and column separated to give compound 97(240mg, yield 38%) as a white solid, compound 10.

4. Synthesis of Compound 130

Reference compound 66 was prepared by the method of preparing compound 4, then compound 4(200mg, 0.67mmol), potassium carbonate (185mg, 1.34mmol), compound 130-1(161mg, 1.00mmol), a catalytic amount of DMAP (10mg), acetonitrile (20mL) was placed in a 50mL round-bottomed flask and heated to 80 ℃ for 12 hours. After the completion of the reaction of the starting materials for liquid chromatography, the reaction was cooled to room temperature, concentrated and separated by column chromatography to give compound 130(150mg, yield 59%) as a colorless oil.

Evaluation of biological Activity:

the activity level criteria for harmful plant destruction (i.e. growth control rate) are as follows:

and 5, stage: the growth control rate is more than 85 percent;

4, level: the growth control rate is more than or equal to 60 percent and less than 85 percent;

and 3, level: the growth control rate is more than or equal to 40% and less than 60%;

and 2, stage: the growth control rate is more than or equal to 20% and less than 40%;

level 1: the growth control rate is more than or equal to 5% and less than 20%;

level 0: the growth control rate is less than 5%.

The growth control rate is the fresh weight control rate.

Post-emergence test experiments: the method comprises the steps of placing monocotyledonous and dicotyledonous weed seeds and main crop seeds (wheat, corn, rice, soybean, cotton, rape, millet and sorghum) in a plastic basin filled with soil, then covering the plastic basin with 0.5-2 cm of soil to enable the plastic basin to grow in a good greenhouse environment, treating test plants in a 2-3 leaf period after sowing for 2 weeks, respectively dissolving a compound to be tested in the invention with acetone, then adding Tween 80, using missible oil of 1.5L/ha of methyl oleate as a synergist, diluting the mixture with certain water into a solution with certain concentration, and spraying the solution onto the plants by using a spray tower. The weeds were cultured in the greenhouse for 3 weeks after application, and the experimental effects of the weeds after 3 weeks are shown in tables 3-4.

TABLE 3 results of activity test of compounds (1000 g/ha)

TABLE 4 post-emergence weed test results

Note: the application dosage is 600 g/hectare of the active ingredients, and the water adding amount is 450 kg/hectare. Echinochloa crusgalli and Cyperus rotundus L are collected from Ningxia in China and have resistance to ALS herbicides.

Control compound a:

the control compound a is a known compound which is poor in safety to rice, has a low selection index, and is difficult to be commercially used. Besides, the compound has high rice selection index, good safety and good commercial value. And has excellent effect on resisting barnyard grass and cyperus rotundus L of ALS class in paddy fields, and can solve resistant weeds.

Pre-emergence test experiment:

placing the monocotyledon and dicotyledon weed seeds and main crop seeds (wheat, corn, rice, soybean, cotton, rape, millet and sorghum) in a plastic pot filled with soil, then covering the plastic pot with 0.5-2 cm of soil, respectively dissolving the compound of the invention to be tested by acetone, then adding Tween 80, diluting the solution into solution with a certain concentration by using a certain amount of water, and immediately spraying the solution after sowing. After the application, the mixture is cultured in a greenhouse for 4 weeks, and after 3 weeks, experimental results are observed, so that the medicament has a superior effect under the measurement of 250 g/hectare, particularly on weeds such as cockspur grass, kukukuh, piemarker and the like, and a plurality of compounds have good selectivity on corn, wheat, rice, soybean and rape.

Experiments show that the compound has better weed control effect generally, has good effect on main gramineous weeds such as cockspur grass, digitaria sanguinalis and setaria viridis and main broadleaf weeds such as piemarker, rorippa rorifolia and sponish needles herb which are widely generated in corn fields, paddy fields and wheat fields, and has good commercial value. Particularly, the broadleaf weeds such as rorippa rorifolia, descurainia sophia, capsella bursa-pastoris, ophiopogon japonicus, cleavers and chickweed which have resistance to ALS inhibitors have extremely high activity.

Evaluating the safety of transplanted rice and the weed control effect of paddy field:

after filling paddy field soil into a tank of 1/1,000,000 hectare, seeds of monochoria vaginalis are sown, and the monochoria vaginalis seeds are covered with soil lightly and are placed in a greenhouse in a state that the water storage depth is 0.5-1 cm. Thereafter, a water diluted solution of a wettable powder or a suspension prepared by preparing the compound of the present invention by a usual formulation method was dropped uniformly by a pipette to a predetermined amount of an active ingredient while keeping the depth of the accumulated water at 3 to 4 cm and reaching 0.5 leaf in the monochoria vaginalis.

In addition, after filling the 1/1,000,000 hectare pot with paddy field soil, leveling is carried out to ensure that the water storage depth is 3-4 cm, and the rice (japonica rice) at the 3-leaf stage is transplanted with the transplanting depth of 3 cm on the next day. The compound of the present invention was treated on the 5 th day after transplantation in the same manner as described above.

The growth state of the monochoria vaginalis on the 14 th day after the medicament treatment and the growth state of the rice on the 21 st day after the medicament treatment are respectively observed by naked eyes, the weeding effect is evaluated according to the activity standard grade of the grade 0-5, and a plurality of compounds show excellent activity and selectivity.

TABLE 5 results of the Experimental Activity and safety tests (1000 g/hectare)

Number of Compounds	Rice (Oryza sativa L.) with improved resistance to stress	Herba Monochoriae
			3	0	5
4	0	5
			7	0	5
66	0	5
			74	0	5
77	0	5
			79	0	5
82	0	5
			87	0	5
88	0	5
			97	0	5
98	0	5
			130	0	5
Penoxsulam 50 g/hectare	1	1

Note: the monochoria vaginalis seeds are all collected from Heilongjiang in China, and have drug resistance to pyrazosulfuron-ethyl and penoxsulam with conventional doses through detection.

It can be seen from this experiment that the compounds of the present invention have excellent activity against weeds that face a severely challenging mechanism of anti-ALS inhibition in production, and can solve the increasingly serious resistance problem.

Meanwhile, a plurality of tests show that the compound and the composition thereof have good selectivity on gramineous lawns such as zoysia japonica, bermuda grass, festuca arundinacea, bluegrass, ryegrass, seashore paspalum and the like, and can prevent and kill a plurality of key gramineous weeds and broadleaf weeds. Tests on wheat, corn, rice, sugarcane, soybean, cotton, sunflower, potato, fruit trees, vegetables and the like under different application modes also show excellent selectivity and commercial value.

Claims

1. A pyridyloxy thioester derivative shown as a formula I,

A. b independently represents halogen, C1-C8 alkyl with or without halogen or C3-C8 cycloalkyl;

c represents hydrogen, halogen, C1-C8 alkyl or halogenated C1-C8 alkyl;

q represents halogen, cyano C1-C8 alkyl, hydroxy C1-C8 alkyl, amino, nitro, formyl, halogen-free or halogen-containing 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, benzyl, naphthyl,

substituted by 0, 1 or 2 radicals selected from C1-C6 alkyl

Or phenyl substituted by 0, 1,2 or 3 groups selected from C1-C6 alkyl, halo C1-C6 alkyl, halo and C1-C6 alkoxy;

And

a naphthyl group,

substituted by 0, 1 or 2 radicals selected from C1-C6 alkyl

Or phenyl substituted by 0, 1,2 or 3 groups selected from: C1-C6 alkyl, halogenated C1-C6 alkyl, halogen, C1-C6 alkoxy and amino substituted by one or two groups selected from hydrogen, C1-C6 alkyl;

r represents

Cyano or nitro;

R₃each independently represents C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 cycloalkyl or C3-C8 cycloalkyl C1-C8 alkyl;

R₄、R₅、R₆each independently represents hydrogen, C1-C8 alkaneC2-C8 alkenyl, C2-C8 alkynyl, C3-C8 cycloalkyl, C3-C8 cycloalkyl C1-C8 alkyl or C1-C8 alkoxycarbonyl;

x represents NR₁R₂Wherein R is₁Represents H, optionally substituted by 1-2R₁₁Substituted C1-C8 alkyl, C2-C8 alkenyl or C2-C8 alkynyl, -COR₁₂；R₂Represents H;

wherein R is₁₁Independently represent phenyl which is unsubstituted or substituted by 1 to 3 groups of halogen, C1-C8 alkyl, halogeno C1-C8 alkyl or

R₁₂Represents H, C1-C18 alkyl or phenyl;

r' independently represents hydrogen, C1-C6 alkyl, C2-C6 alkenyl or C2-C6 alkynyl with or without fluorine, chlorine or bromine.

2. The pyridyloxythioester derivative according to claim 1,

A. b independently represents halogen, C1-C6 alkyl with or without halogen or C3-C6 cycloalkyl;

c represents hydrogen, halogen, C1-C6 alkyl or halogenated C1-C6 alkyl;

q represents halogen, cyano C1-C6 alkyl, hydroxy C1-C6 alkyl, amino, nitro, formyl, halogen-free or halogen-containing 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, benzyl, naphthyl,

substituted by 0, 1 or 2 radicals selected from C1-C6 alkyl

Or 0, 1,2 or 3 radicals selected from C1-C6 alkyl, halogeno C1-C6 alkyl, halogen and C1-C6 alkoxyPhenyl substituted by a group;

And

a naphthyl group,

substituted by 0, 1 or 2 radicals selected from C1-C6 alkyl

r represents

Cyano or nitro;

R₃each independently represents C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl or C3-C6 cycloalkyl C1-C6 alkyl;

R₄、R₅、R₆each independently represents hydrogen, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, C3-C6 cycloalkyl C1-C6 alkyl or C1-C6 alkoxycarbonyl;

x represents NR₁R₂Wherein R is₁Represents H, optionally substituted by 1-2R₁₁Substituted C1-C6 alkyl, C2-C6 alkenyl or C2-C6 alkynyl, -COR₁₂；R₂Represents H;

wherein R is₁₁Independently represent phenyl which is unsubstituted or substituted by 1 to 3 groups of halogen, C1-C6 alkyl, halogeno C1-C6 alkyl or

R₁₂Represents H, C1-C14 alkyl or phenyl;

3. A pyridyloxy thioester derivative shown as a formula I,

A. b independently represents halogen, C1-C6 alkyl, halogenated C1-C6 alkyl or C3-C6 cycloalkyl;

c represents hydrogen, halogen, C1-C6 alkyl or halogenated C1-C6 alkyl;

q represents C1-C6 alkyl, halogenated 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, hydroxyC 1-C6 alkyl, C1-C6 alkoxy C1-C2 alkyl, cyano C1-C2 alkyl, C1-C6 alkylamino C1-C2 alkyl, benzyl, naphthyl, furyl, thienyl, thiazolyl, pyridyl or pyrimidyl, and also unsubstituted or substituted by C1-C6 alkyl

m represents C1-C12 alkyl, halogenated C1-C8 alkyl, C3-C6 cycloalkyl, C2-C6 alkenyl, halogenated C2-C6 alkenyl, C2-C6 alkynyl, C1-C6 alkoxy, C1-C6 alkoxycarbonyl, C1-C6 alkylsulfonyl, cyano C1-C6 alkyl, nitro C1-C6 alkyl, C1-C6 alkoxy C1-C6 alkyl, C1-C6 alkoxycarbonyl C1-C6 alkyl, C2-C6 alkenyloxycarbonyl C1-C6 alkyl, - (C1-C6 alkyl) -R,

Tetrahydrofuryl, pyridyl, naphthyl, furyl, thienyl,

And unsubstituted or C1-C6 alkyl-substituted

r represents

R₃Each independently represents a C1-C6 alkyl group;

R₄、R₅、R₆each independently represents hydrogen, C1-C6 alkyl, or C1-C6 alkoxycarbonyl;

r' represents C1-C6 alkyl or halogenated C1-C6 alkyl;

4. The pyridyloxythioester derivative according to any one of claims 1 to 3,

A. b independently represents fluorine, chlorine, bromine, iodine, methyl, ethyl, propyl, isopropyl, trifluoromethyl or cyclopropyl;

c represents hydrogen, fluorine, chlorine, bromine, iodine, methyl or trifluoromethyl;

q represents methyl, ethyl, propyl, isopropyl, cyclopropyl, vinyl, ethynyl, fluorine, chlorine, bromine, cyano, amino, nitro, formyl, methoxy, methylthio, methoxycarbonyl, chloromethyl, monofluoromethyl, difluoromethyl, trifluoromethyl, 2-chloroethyl, 2,2, 2-trifluoroethyl, hydroxymethyl, methyl, ethyl, propyl, methyl, ethyl, nitro, formyl, methoxy, methyl, ethyl, propyl,

benzyl, naphthyl, furyl, thienyl, thiazolyl, pyridyl or pyrimidinyl, and unsubstituted or substituted by methyl

r' represents methyl, ethyl or difluoromethyl;

Tetrahydrofuryl, pyridyl, naphthyl, furyl, thienyl,

And unsubstituted or methyl-substituted

x represents NH₂、

5. The pyridyloxy thioester derivative according to any one of claims 1 to 3, selected from any one of the following compounds:

6. a process for producing a pyridyloxythioester derivative according to any one of claims 1 to 5, comprising the steps of:

(1) reacting a compound shown in a general formula II with a compound shown in a general formula III to obtain a compound shown in a general formula I; the reaction equation is as follows:

wherein W represents an alkali metal; hal represents halogen; the reaction is carried out in the presence of a catalyst and a solvent;

or (2) when X represents NR₁R₂And R is₁、R₂When not simultaneously hydrogen, the compound shown as the general formula I-1

Reacting with corresponding halide to obtain the product; the reaction is carried out in the presence of a base and a solvent, and a catalyst may also be added during the reaction.

7. The method according to claim 6, wherein the alkali metal in the step (1) is K or Na, and the halogen is Br or Cl.

8. The preparation method according to claim 6, wherein the catalyst in step (1) is TBAB, and the solvent is one or more of dichloromethane, dichloroethane, acetonitrile, tetrahydrofuran and dimethylformamide.

9. The method according to claim 6, wherein the halide in the step (2) is chloride or bromide.

10. The method according to claim 6, wherein the base in the step (2) 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 of tetrahydrofuran, 1, 4-dioxane, toluene, 1, 2-dichloroethane, ethyl acetate, acetonitrile, dimethylformamide, acetone, dichloromethane and chloroform; the catalyst was DMAP.

11. A herbicidal composition, comprising at least one pyridyloxythioester derivative according to any one of claims 1 to 5 and an agrochemically acceptable formulation auxiliary.

12. A method of controlling weeds, comprising applying a herbicidally effective amount of the herbicidal composition of claim 11 to the weeds or to a locus of the weeds in a useful crop.

13. The method of claim 12, wherein the crop is rice and the weeds are grasses, broadleaf weeds, and sedge weeds.

14. The method according to claim 13, wherein the rice is japonica or indica, the grassy weeds are barnyard grass, large crabgrass, moleplant seed or green bristlegrass, the broad-leaved weeds are piemarker or monochoria japonica, and the cyperaceae weeds are cyperus rotundus.