CN112110852B

CN112110852B - Substituted picolinic acid pyridine methylene ester derivative and preparation method, herbicidal composition and application thereof

Info

Publication number: CN112110852B
Application number: CN202010551468.5A
Authority: CN
Inventors: 连磊; 华荣保; 彭学岗; 赵德
Original assignee: Qingdao Kingagroot Chemical Compound Co Ltd
Current assignee: Qingdao Kingagroot Chemical Compound Co Ltd
Priority date: 2019-06-20
Filing date: 2020-06-17
Publication date: 2022-04-26
Anticipated expiration: 2040-06-17
Also published as: CN112110852A; WO2020253696A1

Abstract

The invention belongs to the technical field of pesticides, and particularly relates to a substituted picolinic acid pyridine methylene ester derivative, a preparation method thereof, a weeding composition and application thereof. The substituted pyridine carboxylic acid pyridine methylene ester derivative is shown as a general formula I:

wherein A represents alkyl, haloalkyl, alkoxy, alkylthio, halogen, cyano, alkenyl or alkynyl; b represents an unsubstituted or substituted phenyl group; c represents hydrogen, halogen, alkoxy, alkyl, haloalkyl, alkenyl or alkynyl; x represents NR₁R₂(ii) a Y represents an unsubstituted or substituted pyridyl group. The compound can solve resistant weeds, has more excellent effects on broadleaf weeds and cyperaceae weeds, and has higher selection index on rice.

Description

Substituted picolinic acid pyridine methylene ester derivative and preparation method, herbicidal composition and application thereof

Technical Field

The invention belongs to the technical field of pesticides, and particularly relates to a substituted picolinic acid pyridine methylene ester derivative, a preparation method thereof, a weeding composition and application thereof.

Background

The prevention and control of weeds are a crucial link in the process of realizing high-efficiency agriculture, wherein broadleaf weeds and sedge weeds are important factors for restricting the yield of paddy fields, ALS inhibitors such as bensulfuron-methyl, pyrazosulfuron-ethyl, cinosulfuron, ethoxysulfuron and the like on the market in the last 80 th century have excellent effects on broadleaf weeds and sedge weeds in the paddy fields, but the ALS inhibitors have serious resistance with continuous repeated use for many years, so that at present, in China, Japan, southeast Asia and other countries, the ALS inhibitors cause the abuse resistance of broadleaf arrowhead, monochoria herb, ludwigia herb, water bamboo leaves and sedge weeds such as heterotypic sedge, iris lactea, scirpus and sedge, the yield of paddy rice is seriously affected, and a new herbicide which has a broad herbicidal spectrum and can solve the resistant weeds is urgently needed. The fluroxypyr meptyl on the market of the Yinong Dow company has better control effect on barnyard grass, but has insufficient effect on part of broadleaf weeds and cyperaceae weeds, has insufficient safety on rice, and needs a herbicide with better selectivity and higher efficiency on the broadleaf weeds and the cyperaceae weeds in the market.

Disclosure of Invention

The invention provides a substituted picolinic acid pyridine methylene ester derivative, a preparation method thereof, a weeding composition and application thereof.

The technical scheme adopted by the invention is as follows:

a substituted pyridine methylene picolinate derivative is shown as a general formula I:

wherein A represents alkyl, haloalkyl, alkoxy, alkylthio, halogen, cyano, alkenyl or alkynyl;

b represents an unsubstituted or substituted phenyl group;

c represents hydrogen, halogen, alkoxy, alkyl, haloalkyl, alkenyl or alkynyl;

x represents NR₁R₂Wherein R is₁Represents H, unsubstituted or optionally substituted by 1-2R₁₁Substituted alkyl, alkenyl, alkynyl, cycloalkyl, aryl or heterocyclyl group, -COR₁₂Nitro, OR₁₃，SO₂R₁₄，NR₁₅R₁₆，N＝CR₁₇R₁₈An alkylcarbamoyl group, a dialkylcarbamoyl group, a trialkylsilyl group or a dialkylphosphono group; r₂Represents H, unsubstituted or 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, haloalkyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio, amino, alkylamino, dialkylamino or alkoxycarbonyl, and which contains no or no oxygen atom, sulfur atom or other nitrogen atom;

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

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 or haloalkyl;

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

R₁₇represents H, alkyl, phenyl unsubstituted or substituted by 1 to 3 groups of halogen, alkyl, haloalkyl or alkoxy; r₁₈Represents H or 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 alkyl group;

y represents an unsubstituted or substituted pyridyl group;

group B, R₁₁And each of the "substituted" in Y independently means an alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, cycloalkylalkyl, cycloalkenylalkyl, alkyl-substituted cycloalkyl, OR ", SR", alkyl-OR ", O-alkyl-OR", alkyl-SR ", COR", alkyl-COR ", O-alkyl-COR", COOR ", alkyl-COOR", O-alkyl-COOR ", COSR", SOR ", SO", and SO ", substituted by a group selected from halogen, nitro, cyano, thiocyanato, cyanoalkyl, mercapto, hydroxy, hydroxyalkyl, carboxy, formyl, azido, trialkylsilyl, dialkylphosphono, unsubstituted OR substituted heterocyclyl, heterocyclylalkyl, aryl OR arylalkyl, with OR without halogen₂R”、-O-SO₂R', -alkyl-SO₂R ', OCOR ', alkyl-OCOR ' or SCOR ', unsubstituted or selected from R ', COR ', COOR ', SO, with or without halogen₂R', -alkyl-SO₂At least one (e.g., 1,2, 3, 4, OR 5) of amino, aminocarbonyl, aminocarbonylalkyl, OR aminosulfonyl substituted with one OR two of R "OR OR", OR any two adjacent carbon atoms in the ring and-CH₂CH₂CH₂-、-OCH₂CH₂-、-OCH₂O-、-OCH₂CH₂O-or-CH-groups are joined to form fused rings;

r' each independently represents alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkylalkyl, cycloalkenyl, cycloalkenylalkyl, and optionally substituted heterocyclyl, heterocyclylalkyl, aryl, or arylalkyl.

Preferably, A represents C1-C8 alkyl, halo C1-C8 alkyl, C1-C8 alkoxy, C1-C8 alkylthio, halogen, cyano, C2-C8 alkenyl or C2-C8 alkynyl;

b represents an unsubstituted or substituted phenyl group;

c represents hydrogen, halogen, C1-C8 alkoxy, C1-C8 alkyl, halogenated C1-C8 alkyl, C2-C8 alkenyl or C2-C8 alkynyl;

x represents NR₁R₂Wherein R is₁Represents H, unsubstituted or optionally substituted by 1-2R₁₁Substituted C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 cycloalkyl or phenyl, -COR₁₂Nitro, OR₁₃，SO₂R₁₄，NR₁₅R₁₆，N＝CR₁₇R₁₈C1-C8 alkylcarbamoyl, di-C1-C8 alkylcarbamoyl, tri-C1-C8 alkylsilyl or di-C1-C8 alkylphosphonyl; r₂Represents H, unsubstituted or 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, halo-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 or C1-C8 alkoxycarbonyl

Wherein R is₁₁Independently represent halogen, hydroxy, C1-C8 alkoxy, halogenated C1-C8 alkyl, halogenated C1-C8 alkoxy, C1-C8 alkylthio, halogenated C1-C8 alkylthio, amino, C1-C8 alkylamino, di-C1-C8 alkylamino, C1-C8 alkoxycarbonyl, unsubstituted or interrupted by halogen, C1-C8 alkyl, halogenated C1-C6 alkyl, C1-C8 alkoxy, nitro or C1-C8 alkoxycarbonylPhenyl, naphthyl, substituted by 1 to 3 groups of,

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 or halogenated C1-C8 alkyl;

R₁₅represents H, C1-C8 alkyl, formyl, C1-C8 alkanoyl, halogeno-C1-C8 alkanoyl, C1-C8 alkoxycarbonyl, phenylcarbonyl, phenoxycarbonyl or benzyloxycarbonyl; r₁₆Represents H or C1-C8 alkyl;

R₁₇represents H, C1-C8 alkyl, phenyl unsubstituted or substituted by 1 to 3 of halogen, C1-C8 alkyl, haloC 1-C8 alkyl or C1-C8 alkoxy; r₁₈Represents H or 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;

y represents an unsubstituted or substituted pyridyl group;

the "substituted" in groups B and Y each independently means a heterocyclic, heterocyclic C-C alkyl, aryl or arylC-C alkyl group, unsubstituted or substituted by 1 to 3 groups selected from halogen, C-C alkyl, haloC-C alkyl, C-C alkoxy or amino, C-C alkyl, C-C alkenyl, C-C alkynyl, C-C cycloalkyl, C-C cycloalkenyl, C-C cycloalkylC-C alkyl, C-C cycloalkenylC-C alkyl, C-C alkenylC-C alkyl, C-C alkoxyC-C alkyl, C-C alkylphosphono, di-C alkylphosphono, heterocyclic C-C alkyl, aryl or arylC-C alkyl groups, with or without halogen, C1-C8 alkyl-substituted C3-C8 cycloalkyl, OR ', SR ', - (C1-C8) alkyl-OR ', -O- (C1-C8) alkyl-OR ', - (C1-C8) alkyl-SR ', COR ', - (C1-C8) alkyl-COR ', -O- (C1-C8) alkyl-COR ', COOR ', - (C1-C8) alkyl-COOR ', -O- (C1-C8) alkyl-COOR ', COSR ', SOR ', SO 8₂R”、-O-SO₂R', - (C1-C8) alkyl-SO₂R ', OCOR ', - (C1-C8) alkyl-OCOR ' or SCOR ', unsubstituted or selected from R ', COR ', COOR ', SO, with or without halogen₂R', - (C1-C8) alkyl-SO₂At least one (e.g., 1,2, 3, 4, OR 5) of amino, aminocarbonyl C1-C8 alkyl, OR aminosulfonyl substituted with one OR two of R "OR OR", OR any two adjacent carbon atoms in the ring with-CH₂CH₂CH₂-、-OCH₂CH₂-、-OCH₂O-、-OCH₂CH₂O-or-CH-groups are joined to form fused rings;

r' each independently represents C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 cycloalkyl, C3-C8 cycloalkyl C1-C8 alkyl, C3-C8 cycloalkenyl, C3-C8 cycloalkenyl C1-C8 alkyl, and heterocyclyl, heterocyclyl C1-C8 alkyl, aryl or aryl C1-C8 alkyl, unsubstituted or substituted by 1 to 3 groups selected from halogen, C1-C8 alkyl, halogenated C1-C8 alkyl, C1-C8 alkoxy or amino.

More preferably, A represents C1-C6 alkyl, halo C1-C6 alkyl, C1-C6 alkoxy, C1-C6 alkylthio, halogen, cyano, C2-C6 alkenyl or C2-C6 alkynyl;

b represents an unsubstituted or substituted phenyl group;

c represents hydrogen, halogen, C1-C6 alkoxy, C1-C6 alkyl, halogenated C1-C6 alkyl, C2-C6 alkenyl or C2-C6 alkynyl;

x represents NR₁R₂Wherein R is₁Represents H, unsubstituted or optionally substituted by 1-2R₁₁Substituted C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl or phenyl, -COR₁₂Nitro, OR₁₃，SO₂R₁₄，NR₁₅R₁₆，N＝CR₁₇R₁₈C1-C6 alkylcarbamoyl, di-C1-C6 alkylcarbamoyl, tri-C1-C6 alkylsilyl or di-C1-C6 alkylphosphonyl; r₂Represents H, unsubstituted or 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, halo-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 or C1-C6 alkoxycarbonyl

Wherein R is₁₁Independently represent halogen, hydroxy, C1-C6 alkoxy, halogenated C1-C6 alkyl, halogenated C1-C6 alkoxy, C1-C6 alkylthio, halogenated C1-C6 alkylthio, amino, C1-C6 alkylamino, di-C1-C6 alkylamino, C1-C6 alkoxycarbonyl, unsubstituted or substituted by halogen, C1-C6 alkyl, halogenated C1-C6 alkyl, C1-C6 alkoxy, nitro or C1-C6 alkoxycarbonyloxyPhenyl, naphthyl, substituted by 1 to 3 groups in the radical,

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 or 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 or C1-C6 alkyl;

R₁₇represents H, C1-C6 alkyl, phenyl unsubstituted or substituted by 1 to 3 of halogen, C1-C6 alkyl, haloC 1-C6 alkyl or C1-C6 alkoxy; r₁₈Represents H or 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;

y represents an unsubstituted or substituted pyridyl group;

the "substituted" in groups B and Y each independently means a heterocyclic, heterocyclic C-C alkyl, aryl or arylC-C alkyl group, unsubstituted or substituted by 1 to 3 groups selected from halogen, C-C alkyl, haloC-C alkyl, C-C alkoxy or amino, C-C alkyl, C-C alkenyl, C-C alkynyl, C-C cycloalkyl, C-C cycloalkenyl, C-C cycloalkylC-C alkyl, C-C cycloalkenylC-C alkyl, C-C alkenylC-C alkyl, C-C alkoxyC-C alkyl, C-C alkylphosphono, di-C alkylphosphono, heterocyclic C-C alkyl, aryl or arylC-C alkyl groups, with or without halogen, C1-C6 alkyl-substituted C3-C6 cycloalkyl, OR ', SR ', - (C1-C6) alkyl-OR ', -O- (C1-C6) alkyl-OR ', - (C1-C6) alkyl-SR ', COR ', - (C1-C6) alkyl-COR ', -O- (C1-C6) alkyl-COR ', COOR ', - (C1-C6) alkyl-COOR ', -O- (C1-C6) alkyl-COOR ', COSR ', SOR ', SO 6₂R”、-O-SO₂R', - (C1-C6) alkyl-SO₂R ', OCOR ', - (C1-C6) alkyl-OCOR ' or SCOR ', unsubstituted or selected from R ', COR ', COOR ', SO, with or without halogen₂R', - (C1-C6) alkyl-SO₂At least one (e.g., 1,2, 3, 4, OR 5) of amino, aminocarbonyl C1-C6 alkyl, OR aminosulfonyl substituted with one OR two of R "OR OR", OR any two adjacent carbon atoms in the ring with-CH₂CH₂CH₂-、-OCH₂CH₂-、-OCH₂O-、-OCH₂CH₂O-or-CH-groups are joined to form fused rings;

r' each independently represents C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, C3-C6 cycloalkyl C1-C6 alkyl, C3-C6 cycloalkenyl, C3-C6 cycloalkenyl C1-C6 alkyl, and heterocyclyl, heterocyclyl C1-C6 alkyl, aryl or aryl C1-C6 alkyl, unsubstituted or substituted by 1 to 3 groups selected from halogen, C1-C6 alkyl, halogenated C1-C6 alkyl, C1-C6 alkoxy or amino.

Further preferably, a represents chloro, bromo, fluoro, methoxy, ethoxy, methylthio, ethylthio, methyl, ethyl, trifluoromethyl, vinyl, propynyl or cyano;

b represents phenyl which is unsubstituted or substituted by 1,2, 3 or 4 substituents selected from fluoro, chloro, bromo, methyl, methoxy, methylthio or dimethylamino;

c represents hydrogen, fluorine, chlorine, methyl, methoxy, allyl or ethynyl;

x represents NR₁R₂，

Wherein R is₁Represents H, unsubstituted or optionally substituted by 1R₁₁Substituted methyl, methylcarbonyl, t-butyloxycarbonyl, cyclopropyl or phenyl;

R₂represents H or methyl;

R₁₁independently of one another represents a phenyl group,

unsubstituted or substituted by trifluoromethyl

Y represents unsubstituted or substituted by 1,2, 3 or 4 substituents selected from fluorine, chlorine, bromine, methyl, trifluoromethyl, vinyl, 2-chloroethenyl, ethynyl, cyclopropyl, cyano, nitro, hydroxy, methoxy, methylthio, ethylthio, methylcarbonyl, methylsulfonyl, amino, monomethylamino, dimethylamino, hydroxymethyl, cyanomethyl, methoxycarbonyl, methylcarbonyloxy or methylcarbonylamino

Even more preferably, B represents

X represents NH₂、NHMe、N(Me)₂、

Unsubstituted or substituted by trifluoromethyl

In the definition of the compounds of the above general formula 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, C1 alkyl-methyl; c2 alkyl-ethyl; c3 alkyl-propyl such as n-propyl or isopropyl; c4 alkyl-butyl such as n-butyl, isobutyl, tert-butyl or 2-butyl; c5 alkyl-pentyl such as n-pentyl; c6 alkyl-hexyl radicals such as the n-hexyl, isohexyl and 1, 3-dimethylbutyl radical. Similarly, alkenyl is, for example, allyl, 1-methylprop-2-en-1-yl, 2-methylprop-2-en-1-yl, but-3-en-1-yl, 1-methylbut-3-en-1-yl and 1-methylbut-2-en-1-yl. Alkynyl is, for example, propargyl, but-2-yn-1-yl, but-3-yn-1-yl, 1-methylbut-3-yn-1-yl. Multiple bonds at least one (e.g., 1,2, 3) multiple bonds may be in any position per unsaturated group. Cycloalkyl is a carbocyclic saturated ring system having, for example, three to six carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl. Similarly, cycloalkenyl is monocyclic alkenyl having, for example, three to six carbocyclic members, such as cyclopropenyl, cyclobutenyl, cyclopentenyl and cyclohexenyl, wherein the double bond can be in any position. Halogen is fluorine, chlorine, bromine or iodine.

Unless otherwise specified, all terms of art used herein, whether used alone or in compound words, are intended to mean "aryl" or "aryl" group "Including phenyl, naphthyl,

The "heterocyclic group" includes not only those having 0, 1 or 2 oxo groups

Also included are heteroaryl groups, i.e. aromatic cyclic groups containing, for example, from 3 to 6 (3, 4,5, 6) ring atoms, of which 1 to 4 (1, 2, 3, 4) heteroatoms are selected from oxygen, nitrogen and sulfur, and which may also be fused via a benzo ring, for example

If a group is substituted by a group, this is understood to mean that the group is substituted by one or more identical or different 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. The same applies to ring systems formed from different atoms and units. Also, the scope of the claims will exclude those compounds known to those skilled in the art to be chemically unstable under standard conditions.

In addition, unless otherwise specified, the foregoing qualifiers for a plurality of juxtaposed substituents (as "or" apart ") in the present invention have a limiting effect on each of the substituents thereafter, such as" unsubstituted or substituted "in" unsubstituted or substituted aryl, heterocyclyl "has a limiting effect on each of the groups" aryl "," heterocyclyl "thereafter; groups not labeled for a particular attachment position (including heterocyclyl, aryl, etc.) may be attached at any position, including the position attached to C or N; if it is substituted, the substituents can likewise be substituted in any position, provided that a bond linkage is satisfiedAnd (4) rules. Heteroaryl as substituted by 1 methyl group

Can represent

And the like.

Depending on the nature of the substituents and the manner in which they are attached, the compounds of formula I and their derivatives 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.

A process for the preparation of said substituted picolinic acid picolyl ester derivative, comprising the steps of: carrying out esterification reaction on the compound shown in the general formula III and the compound shown in the general formula II to obtain a compound shown in the general formula I; the chemical reaction equation is as follows:

preferably, the reaction is carried out in the presence of triethylamine, PyBOP and a solvent selected from one or a combination of more of acetonitrile, DMF, dichloromethane and 1, 2-dichloroethane; the reaction temperature is 0-50 ℃.

A herbicidal composition comprising a herbicidally effective amount of at least one of said substituted picolinic acid pyridylmethylene ester derivatives, preferably together with formulation adjuvants.

A method for controlling weeds, which comprises applying a herbicidally effective amount of at least one of said substituted picolinic acid pyridylmethylene ester derivatives or said herbicidal composition on a plant or a weed region.

The use of at least one of said substituted picolinic acid picolyl ester derivatives or said herbicidal composition for controlling weeds, preferably, said substituted picolinic acid picolyl ester derivatives are used for controlling weeds in crops of useful plants, said crops of useful plants being transgenic or treated by genome editing techniques.

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 altered by genetic engineering (e.g. WO 92/11376, WO 92/14827, 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, "Pesticide 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]Uss.verlagageell.stuttgart 1976; "Chemische technology" by Winnacker-Kuchler [ 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, butachlor, benfluralin-bencarbzachlor, bencarbzamide, bencarb-N-P-N-P-N-P-N-, 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, bensulfuron-methyl, benazol-methyl, bensulfuron-methyl, benazol-methyl, benflurazid, benfluridimethyl, benfluridil, benflurazid, benfluridil, ben, 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, benfurbenfluridone, benfluridone, benfurin, benfluridone, benfurbenfurbenfurin, benfurbenfurbenfurbenfurbenfurbenfurin, benfluridone, benfurbenfurbenfurbenfurbenfurin, benfurin, benfluridone, benfurin, benfurbenfurbenfurin, benfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurin, benfurin, benfurbenfurbenfurbenfurbenfurin, benfurin, benfurbenfurbenfurbenfurbenfurbenfurbenfurin, benfurin, benfurbenfurin, benfurin, benfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurbenfurin, benfurin, benfurbenfurbenfurin, benfurbenfurbenfurbenfurbenfurin, benfurin, benfurbenfurin, benfurin, benfurbenfurbenfurin, benfurbenfurbenfurbenfurbenfurin, benfurin, benfurbenfurbenfurbenfur, 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, benazolin, thiuron, thifenbenazolin, thiuron, thifenbenazolin, thiuron, thifenbenazolin, thiuron, thifenbencarb, thiuron, thifenbencarb, thiuron, thifenbencarb, thiuron, thifenbencarb, 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, clorac, 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, mefenap-ethyl, mefenoxaprop-p-ethyl, mefenofos, mefenoxaprop-p-ethyl, mefenoxaprop-p-ethyl, mefenoxaprop-p-ethyl, mefenoxaprop-p-ethyl, mefenofos, mefenap-p-ethyl, mefenoxaprop-p-ethyl, mefenoxaprop-p-ethyl, mefenoxaprop-p-ethyl, mefenozide, mefenoxaprop-ethyl, mefenoxaprop-p-ethyl, mefenoxaprop-p-ethyl, mefenoxaprop-p-, 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, pyraclonil, pyraoxystrobin, pyraclonil, pyraclostrobin, propyzachlor, pyraclostrobin, flufenapyr-ethyl, pyraclostrobin, flufenapyr-ethyl, pyraclostrobin, 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, tebufenozide, tebufadix, tebufenozide, tebufalin, tebufenozide, tebufalin, 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, thiothifluzone, pyrazone, thiothifluzone, thion, thiothifluzone, thion, thiobenflurazolidone, thion, thifluzone, thion, thifluzone, thidiazuron, thidiaz, 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.

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 250 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 table 1. 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 the CompoundsAnd it¹HNMR 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.

Examples of representative compounds are given below, and the synthesis of other compounds is similar and will not be described in detail herein.

1. Preparation of compound 1:

to 80 mL of DCM were added compounds 1-1(5.0g,17.7mmol,1.0eq), Et in that order₃N (1.97g,19.4mmol,1.1eq) and 1-2(2.12g,19.4mmol,1.1eq), then PyBOP (10.11g,19.4mmol,1.1eq) was added at 20 ℃ and the reaction stirred at 20 ℃ for 5 h. LCMS detection showed the starting material was essentially reacted to completion with a major new peak. The reaction solution was poured into 100ml of water, separated, the aqueous phase was extracted once with 100ml of dichloromethane, the organic phase was washed once with saturated brine (100ml), dried over anhydrous sodium sulfate, and concentrated to give a crude product, which was separated by column chromatography to give compound 1(5.5g, 83.2% yield) (white solid).

2. Preparation of compound 115:

to 10mL of DCM were added the compounds 115-1(0.8g,2.7mmol,1.0eq), Et in that order₃N (0.3g,2.9mmol,1.1eq) and 115-2(0.52g,2.9mmol,1.1eq), followed by PyBOP (1.5g,2.9mmol,1.1eq) at 20 ℃ and the reaction stirred for 5 hours at 20 ℃. LCMS detection showed the starting material was essentially reacted to completion with a major new peak. The reaction solution was poured into water (50mL), and the solution was separated, the aqueous phase was extracted once with dichloromethane (50mL), the organic phase was washed once with saturated brine (50mL), dried over anhydrous sodium sulfate, and concentrated to give a crude product, which was separated by column chromatography to give compound 115(1.0g, 81.6% yield) (white solid).

3. Preparation of compound 149:

to 10mL of DCM were added the compounds 149-1(0.7g,2.0mmol,1.0eq), Et in that order₃N (0.22g,2.2mmol,1.1eq) and 149-2(0.24g,2.2mmol,1.1eq) were added followed by PyBOP (1.15g,2.2mmol,1.1eq) at 20 ℃ and the reaction stirred for 5 hours at 20 ℃. LCMS detection showed the starting material was essentially reacted to completion with a major new peak. The reaction solution was poured into 20ml of water, separated, the aqueous phase was extracted once with 30ml of dichloromethane, the organic phase was washed once with saturated brine (20ml), dried over anhydrous sodium sulfate, and concentrated to give a crude product, which was separated by column chromatography to give compound 149(0.75g, 77.5% yield) (white solid).

4. Preparation of compound 168:

after compound 37 was obtained according to the preparation of compound 1 above, compound 37(500mg,1.34mmol,1.0eq) and NaH (58.8mg, 60% purity,1.47mmol,1.1eq) were added to 10ml of THF in this order, compound 168-1(0.34g,1.47mmol,1.1eq) was added thereto under stirring at 0 ℃ for 0.5 hours, and the reaction mixture was stirred at 20 ℃ for 5 hours. LCMS detection showed the starting material was essentially reacted to completion with a major new peak. The reaction solution was poured into 30ml of water, separated, the aqueous phase was extracted once with 30ml of dichloromethane, the organic phase was washed once with saturated brine (30ml), dried over anhydrous sodium sulfate, and concentrated to give a crude product, which was separated by column chromatography to give compound 168(0.55g, 78.6% yield) (white solid). Or by referring to the above steps, the compound 1-1 is reacted with the compound 168-1 and then reacted with the compound

Esterification occurs to produce compound 168.

5. Preparation of compound 173:

to 10mL of DCM were added the compounds 173-1(0.28g,1mmol,1.0eq), Et in that order₃N (0.11g,1.1mmol,1.1eq) and 1-2(0.12g,1.1mmol,1.1eq), then PyBOP (0.57g,1.1mmol,1.1eq) was added at 20 ℃ and the reaction stirred at 20 ℃ for 5 h. LCMS detection showed the starting material was essentially reacted to completion with a major new peak. The reaction solution was poured into 20ml of water, separated, the aqueous phase was extracted once with 20ml of dichloromethane, the organic phase was washed once with saturated brine (20ml), dried over anhydrous sodium sulfate, and concentrated to give a crude product, which was isolated by column chromatography to give compound 173(0.29g, 78.4% yield) (white solid).

Evaluation of biological Activity:

the rice safety rating standard is:

and 5, stage: rice severely inhibits growth and eventually dies.

4, level: the length of the plant height and the root system is inhibited by more than 40 percent; the new leaves are difficult to extract and the rice is scattered.

And 3, level: the plant height and root length are inhibited by 25-40%; the new leaf is shortened by extraction and has a roll core.

And 2, stage: the plant height and root length are inhibited by 10-25%; the new leaves are extracted and shortened.

Level 1: the plant height and root length are inhibited by 5-10%; the new leaves are normally extracted.

Level 0: the plant height and the root system are normal.

Other plant disruption (i.e. growth control rate) activity level criteria were 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.

(1) Post-emergence test experiments: placing monocotyledonous and dicotyledonous 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 to make the plastic pot grow in a good greenhouse environment, sowing the plastic pot for 2-3 weeks, then treating test plants, respectively dissolving the compound of the invention to be tested by acetone, then adding Tween 80, diluting the solution into a solution with a certain concentration by using a certain amount of water, and spraying the solution onto the plants by using a spray tower. The experimental effects of weeds after 3 weeks of cultivation in the greenhouse after application are listed in tables 2-3.

TABLE 2 post-emergence weed test (weed 3-4 leaf stage, rice 3.5 leaf stage)

Note: the application dosage is 30 g/hectare of the active ingredient, the water adding amount is 450 kg/hectare, and N represents no data.

TABLE 3 post-emergence weed test ED₉₀Measurement result of (2)

Number of Compounds	Flos Caryophylli herba Polygoni Hydropiperis	Special-shaped nutgrass flatsedge	Edible tulip	Rhizoma Cyperi	Acalypha australis	Folium Phyllostachydis Henonis
							1	6	10	4	9	4	3
37	7	12	5	14	5	3
							72	9	15	5	16	4	3
Control Compound D	15	45	8	35	7	6

Note: the application dosage is 1.5, 3, 6, 12, 24 and 48 g/hectare of active ingredients, the weed control effect test result is averaged for three times at the 3-leaf stage, and then the effective dosage of 90 percent of the herbicide inhibiting each weed, namely ED, is respectively calculated according to the linear method of the logarithmic probability value and the probability value₉₀Values (g/ha).

(2) And (4) carrying out spray safety and activity test on stems and leaves of the direct-seeded rice at the 2-3 leaf stage and the barnyard grass at the 3 leaf stage, and averaging the results of the control effect test for three times. The ratio of the average number of the compound doses inhibiting 10% of the average of the two types of rice (Huanghuazhan, Huai rice No. 5) to the average number of the compound doses inhibiting 90% of the average of the ludwigia prostrata, cyperus rotundus, lophatherum gracile and edible tulip is taken as the selection index of the crops, and the result is shown in table 4, wherein the selection index is generally considered to be at least more than 2 which can be used in production, and more than 4 indicates better selectivity, and the higher selection index is better.

TABLE 4 safety and Activity test results

Number of Compounds	Mean selection index
		1	7.2
37	6.4
		72	6.5
106	4.7
		107	4.9
108	5.6
		125	3.2
126	4
		127	3.7
Control Compound A	1.5
		Control Compound B	1.6
Control Compound C	1.9
		Control Compound D	2.1

(3) The compound of the invention also has good activity and selectivity on common broadleaf grass in wheat fields, and the result is shown in table 5.

TABLE 5 safety and Activity test results (application dose of 2 g/ha of active ingredient)

Number of Compounds	Galium aparine	Descurainia sophia	Wheat (Triticum aestivum L.)
				1	5	5	0
37	5	5	0
				72	5	5	0
127	5	5	0
				Control Compound A	4	3	0

(4) And (3) carrying out stem and leaf spraying safety and activity tests on the corns in the 3-leaf stage, the piemarker, the chenopodium quinoa and the cyperus rotundus in the 4-5-leaf stage, and averaging the results of the prevention effect test three times. The average number of compounds that inhibited corn by 10% on average and the average number of compounds that inhibited broadleaf grass and cyperus rotundus by 90% on average were used as the selection index for the crop, and the results are shown in table 6, where a selection index of at least greater than 2 is generally considered to be useful for production, and greater than 4 indicates better selectivity, with higher selection indices being better.

TABLE 6 safety and Activity test results

Note: control compound a:

control compound B:

control compound C:

control compound D:

control compound E:

control compound F:

control compound G:

control compound E, F, G was derived from WO 2019/084353a1, among others.

(5) And (3) field test: the control effect of the plant against main broadleaf weeds and nutgrass flatsedge in the field is respectively tested in Heilongjiang, Jiangsu and Hubei China. And taking an average value in total three. The pesticide application period is 20 days after transplanting rice, the leaf period of direct sowing rice is 3.4, the leaf period of edible tulip is 4-5, the leaf period of monochoria vaginalis is 5, the height of the special-shaped cyperus rotundus is 20 cm, and the length of the stem of the lophatherum gracile is 15-30 cm. The test sample was a 3% emulsifiable concentrate. The sprayer is a knapsack sprayer. The test results are shown in Table 7.

TABLE 7 field test results

Note: through sampling test, the edible tulip, the monochoria vaginalis and the cyperus heterotropoides have resistance to the ALS inhibitor, and resistance sites caused by gene mutation exist.

From the above tables, it can be seen that compared with the control compound, the compound of the present invention significantly improves the safety and herbicidal activity of crops by changing the structure of the mother ring, the type of the substituent, and the type of the carboxyl derivative, and particularly establishes good selectivity for key crops such as corn, rice, wheat, etc., while the control compound has poor selectivity for major crops, which indicates that the present invention achieves excellent unexpected technical effects.

(6) 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. The results of experiments are observed after the application of the herbicide and the cultivation in a greenhouse for 4 weeks, and the finding shows that most of the herbicide has excellent effect under the measurement of 250g/ha, especially on weeds such as cockspur grass, crab grass, piemarker and the like, and a plurality of compounds have good selectivity on corn, wheat, rice, soybean and rape.

Experiments show that the compound generally has a good weed control effect, and particularly, the compound has extremely high activity on broadleaf weeds and nutgrass flatsedge which have resistance to ALS inhibitors and are contained in wild arrowheads, Chinese iris, sedge heterotropoides, descurainia sophia, shepherd's purse, maica, cleavers, cyperus rotundus and the like, and has very good commercial value.

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

after the paddy field soil was filled in a tank of 1/1,000,000 hectare, seeds of barnyard grass, japanese iris, bidens tripartita and edible tulip were sown, and soil was lightly covered thereon. Standing in a state of water storage depth of 0.5-1 cm in a greenhouse, and implanting tuber of Pseudobulbus Cremastrae seu pleiones in the next or 2 days. Thereafter, the water storage depth was maintained at 3 to 4 cm, and an aqueous dilution of a wettable powder or a suspension, which was prepared by a usual formulation method, was dropped uniformly by a pipette at a time point when barnyard grass, japanese iris, or burley reached 0.5 leaf and the bulb reached the primary leaf stage to obtain a predetermined amount of active ingredient.

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 cockspur grass, japanese iris, bidens tripartita and edible tulip on day 14 after the treatment with the chemical agent and the growth state of rice on day 21 after the treatment with the chemical agent were respectively observed by naked eyes, and the effects were evaluated on the above activity standard levels, and many compounds showed excellent activity and selectivity.

Note: the seeds of barnyard grass, Chinese iris, edible tulip and bidens tripartita are all collected from Heilongjiang in China, and are detected to have drug resistance to pyrazosulfuron-ethyl with conventional dosage.

Meanwhile, a plurality of tests show that the compound has good selectivity on gramineous lawns such as zoysia japonica, bermuda grass, tall fescue, blue grass, ryegrass, seashore paspalum and the like, and can prevent and kill a plurality of key gramineous weeds and broadleaf weeds. Tests on 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 substituted pyridine methylene picolinate derivative is shown as a general formula I:

wherein the content of the first and second substances,

a represents C1-C8 alkyl, halo C1-C8 alkyl, C1-C8 alkoxy, C1-C8 alkylthio, halogen, cyano, C2-C8 alkenyl or C2-C8 alkynyl;

b represents an unsubstituted or substituted phenyl group;

x represents NR₁R₂Wherein R is₁Represents H, unsubstituted or optionally substituted by 1R₁₁Substituted C1-C8 alkyl, C3-C8 cycloalkyl, phenyl or-COR₁₂；R₂Represents H or C1-C8 alkyl;

wherein R is₁₁Independently represents phenyl substituted by 1 radical of C1-C8 alkoxycarbonyl

Or unsubstituted or substituted by 1 radical of halogeno-C1-C6 alkyl

R₁₂Represents C1-C18 alkyl or C1-C8 alkoxy;

y represents an unsubstituted or substituted pyridyl group;

the term "substituted" in group B means substituted by at least one group selected from halogen, C1-C8 alkyl, OR ", SR", amino unsubstituted OR substituted by one OR two groups selected from R ";

"substituted" in the radical Y means C3-C8 cycloalkyl, OR ', SR', C1-C8 alkyl-OR ', C1-C8 alkyl-SR', COOR ', COSR', SO-substituted by a group selected from halogen, nitro, cyano C1-C8 alkyl, mercapto, hydroxy C1-C8 alkyl, carboxy, formyl, C1-C8 alkyl with OR without halogen, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 cycloalkyl, C3-C8 cycloalkyl C1-C8 alkyl, C1-C8 alkyl₂R ", OCOR" or SCOR ", unsubstituted or substituted by at least one group selected from amino substituted by one or two groups selected from R" or COR "with or without halogen;

r' independently represents C1-C8 alkyl, C2-C8 alkenyl or C2-C8 alkynyl.

2. A substituted pyridinemethylene picolinate derivative according to claim 1,

a represents C1-C6 alkyl, halo C1-C6 alkyl, C1-C6 alkoxy, C1-C6 alkylthio, halogen, cyano, C2-C6 alkenyl or C2-C6 alkynyl;

b represents an unsubstituted or substituted phenyl group;

x represents NR₁R₂Wherein R is₁Represents H, unsubstituted or optionally substituted by 1R₁₁Substituted C1-C6 alkyl, C3-C6 cycloalkyl, phenyl or-COR₁₂；R₂Represents H or C1-C6 alkyl;

wherein R is₁₁Independently represents phenyl substituted by 1 radical of C1-C6 alkoxycarbonyl

Or unsubstituted or substituted by 1 radical of halogeno-C1-C6 alkyl

R₁₂Represents C1-C14 alkyl or C1-C6 alkoxy;

y represents an unsubstituted or substituted pyridyl group;

the term "substituted" in group B means substituted by at least one group selected from halogen, C1-C6 alkyl, OR ", SR", amino unsubstituted OR substituted by one OR two groups selected from R ";

"substituted" in the radical Y means C3-C6 cycloalkyl, OR ', SR', C1-C6 alkyl-OR ', C1-C6 alkyl-SR', COOR ', COSR', SO-substituted by a group selected from halogen, nitro, cyano C1-C6 alkyl, mercapto, hydroxy C1-C6 alkyl, carboxy, formyl, C1-C6 alkyl with OR without halogen, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, C3-C6 cycloalkyl C1-C6 alkyl, C1-C6 alkyl₂R ", OCOR" or SCOR ", unsubstituted or substituted by at least one group selected from amino substituted by one or two groups selected from R" or COR "with or without halogen;

r' independently represents C1-C6 alkyl, C2-C6 alkenyl or C2-C6 alkynyl.

3. A substituted pyridinemethylene picolinate derivative according to claim 1,

b represents an unsubstituted or substituted phenyl group;

c represents hydrogen, halogen, C1-C6 alkoxy, C1-C6 alkyl, C2-C6 alkenyl or C2-C6 alkynyl;

Or unsubstituted or substituted by 1 radical of halogeno-C1-C6 alkyl

R₁₂Represents C1-C14 alkyl or C1-C6 alkoxy;

y represents an unsubstituted or substituted pyridyl group;

the term "substituted" in the group Y means a group selected from halogen, nitro, cyano-C1-C6 alkyl, hydroxy-C1-C6 alkyl, C1-C6 alkyl with OR without halogen OR C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, OR ", SR", COR ", COOR", SO₂R”、OCOR ", unsubstituted OR substituted with at least one group selected from amino substituted with one OR two groups selected from R" OR COR ";

r' independently represent a C1-C6 alkyl group.

4. A substituted pyridylmethylene picolinate derivative according to any one of claims 1 to 3 wherein,

a represents chlorine, bromine, fluorine, methoxy, ethoxy, methylthio, ethylthio, methyl, ethyl, trifluoromethyl, vinyl, propynyl or cyano;

c represents hydrogen, fluorine, chlorine, methyl, methoxy, allyl or ethynyl;

x represents NR₁R₂，

R₂represents H or methyl;

R₁₁independently of one another represents a phenyl group,

unsubstituted or substituted by trifluoromethyl

5. A substituted pyridinemethylene picolinate derivative according to claim 4,

b represents

X represents NH₂，NHMe，N(Me)₂，

Unsubstituted or not substituted

6. A substituted pyridylmethylene picolinate derivative selected from any one of the following compounds:

7. a process for the preparation of a substituted picolyl picolinate derivative according to any one of claims 1 to 6 comprising the steps of: carrying out esterification reaction on the compound shown in the general formula III and the compound shown in the general formula II to obtain a compound shown in the general formula I; the chemical reaction equation is as follows:

wherein the groups A, B, C, X and Y are as defined in any one of claims 1 to 6.

8. The process according to claim 7, wherein the reaction is carried out in the presence of triethylamine, PyBOP and a solvent selected from one or more combinations of acetonitrile, DMF, dichloromethane and 1, 2-dichloroethane; the reaction temperature is 0-50 ℃.

9. A herbicidal composition comprising a herbicidally effective amount of at least one of the substituted pyridylmethylene picolinate derivatives of any one of claims 1 to 6.

10. A herbicidal composition according to claim 9, further comprising a formulation adjuvant.

11. A method for controlling weeds, which comprises applying a herbicidally effective amount of at least one of the substituted picolinic acid pyridylmethylene ester derivatives of any one of claims 1 to 6 or the herbicidal composition of claim 9 or 10 to a plant or to a weed region.

12. Use of at least one of the substituted pyridylmethylene picolinate derivatives of any one of claims 1 to 6 or the herbicidal composition of claim 9 or 10 for controlling weeds.

13. Use according to claim 12, wherein the substituted pyridinylmethyl picolinate derivative is used for controlling weeds in a useful crop, which is a transgenic crop or a crop treated with genome editing techniques.