WO2020253696A1 - Substituted pyridinemethylene pyridinecarboxylate derivative, preparation method therefor and herbicidal composition and use thereof - Google Patents

Abstract

The invention belongs to the technical field of pesticides, and specifically relates to a substituted pyridinemethylene pyridinecarboxylate derivative, a preparation method therefor and a herbicidal composition and the use thereof. The substituted pyridinemethylene pyridinecarboxylate derivative is as represented by general formula I, wherein A represents an alkyl, a halogenated alkyl, an alkoxy, an alkylthio, halogen, cyano, an alkenyl or an alkynyl; B represents an unsubstituted or substituted phenyl; C represents hydrogen, halogen, an alkoxy, an alkyl, a halogenated alkyl, an alkenyl or an alkynyl; X represents NR₁R₂; and Y represents an unsubstituted or substituted pyridyl. The compound can combat resistant weeds, has a better effect on broadleaf weeds and Cyperaceae weeds, and has a higher selection index with respect to rice.

Description

Substituted pyridine methylene picolinate derivative and preparation method, herbicidal composition and application thereof Technical field

The invention belongs to the technical field of pesticides, and in particular relates to a substituted picolinic acid picolinyl methylene ester derivative and a preparation method, herbicidal composition and application thereof.

Background technique

The prevention and control of weeds is a crucial link in the process of realizing high-efficiency agriculture. Broadleaf weeds and Cyperaceae weeds are important factors that restrict the yield of rice fields. Bensulfuron-methyl and Pyrimsulfuron were listed in the 1980s. ALS inhibitors such as sulfuron, metsulfuron and ethoxysulfuron have excellent effects on broadleaf weeds and Cyperaceae weeds in rice fields. However, they have been repeatedly used for many years, resulting in serious resistance. They are currently used in China, Japan and Southeast Asia. In the country, ALS inhibitor herbicides have caused resistance to broad-leaved grasses such as Aquilaria vulgaris, Apis vulgaris, Polygonum syringae, and water bamboo leaves, as well as Cyperaceae weeds, Cyperus sylvestris, Firefly, Scirpus sylvestris, and Cyperus spp. For rice production, new herbicides with broad weed-killing spectrum and capable of solving resistant weeds are urgently needed. The Dow AgroSciences listed clofluridinate has a good control effect on barnyardgrass, but it has insufficient effect on some broadleaf weeds and Cyperaceae weeds. At the same time, it has insufficient safety on rice, and the market needs a better choice. It is a highly effective herbicide for broadleaf grasses and Cyperaceae weeds.

Summary of the invention

The present invention provides a substituted picolinyl picolinate derivative and a preparation method, herbicidal composition and application thereof. The compound can solve resistant weeds and has a better effect on broadleaf weeds and Cyperaceae weeds. Excellent, and has a higher selection index for rice.

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

A substituted pyridine methylene picolinate derivative, as shown in general formula I:

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

B represents unsubstituted or substituted phenyl;

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

X represents NR ₁ R ₂ , wherein R ₁ represents H, an alkyl, alkenyl, alkynyl, cycloalkyl, aryl or heterocyclic group that is unsubstituted or optionally substituted by 1-2 R ₁₁ , -COR ₁₂ , nitro, OR ₁₃ , SO ₂ R ₁₄ , NR ₁₅ R ₁₆ , N=CR ₁₇ R ₁₈ , alkylcarbamoyl, dialkylcarbamoyl, trialkylsilyl or dialkylphosphono ; R ₂ represents H, an unsubstituted or optionally substituted alkyl group with 1-2 R ₁₁ or -COR ₁₂ ; or NR ₁ R ₂ represents N=CR ₂₁ NR ₂₂ R ₂₃ , N=CR ₂₄ OR ₂₅ , Unsubstituted or by 1-2 independently selected from halogen, alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio, amino, alkylamino, dialkylamino or alkoxycarbonyl The 5- or 6-membered saturated or unsaturated ring that does not contain or contains oxygen, sulfur or other nitrogen atoms substituted by the group in;

Wherein R ₁₁ independently represents halogen, hydroxy, alkoxy, haloalkyl, haloalkoxy, alkylthio, haloalkylthio, amino, alkylamino, dialkylamino, alkoxycarbonyl, unsubstituted or substituted Aryl, heterocyclic group;

R ₁₂ represents H, alkyl, haloalkyl, alkoxy, phenyl, phenoxy or benzyloxy;

R ₁₃ represents H, alkyl, haloalkyl, phenyl, benzyl or CHR ₃₁ C(O)OR ₃₂ ; R ₃₁ represents H, alkyl or alkoxy; R ₃₂ represents H, alkyl or benzyl;

R ₁₄ represents alkyl or haloalkyl;

R ₁₅ represents H, alkyl, formyl, alkyl acyl, haloalkyl acyl, alkoxycarbonyl, phenylcarbonyl, phenoxycarbonyl or benzyloxycarbonyl; R ₁₆ represents H or alkyl;

R ₁₇ represents H, alkyl, unsubstituted or substituted by 1-3 groups of halogen, alkyl, haloalkyl or alkoxy; R ₁₈ represents H or alkyl; or N=CR ₁₇ R ₁₈ stands for

R ₂₁ and R ₂₄ each independently represent H or an alkyl group;

R ₂₂ and R ₂₃ each independently represent H or an alkyl group; or NR ₂₂ R ₂₃ represents a 5- or 6-membered saturated or unsaturated ring that does not contain or contains oxygen, sulfur or other nitrogen atoms;

R ₂₅ represents an alkyl group;

Y represents unsubstituted or substituted pyridyl;

The "substituted" in groups B, R ₁₁ and Y each independently refers to being selected from halogen, nitro, cyano, thiocyano, cyanoalkyl, mercapto, hydroxy, hydroxyalkyl, carboxy, Formyl, azido, trialkylsilyl, dialkylphosphono, unsubstituted or substituted heterocyclyl, heterocyclylalkyl, aryl or arylalkyl, alkyl with or without halogen Group, 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 ₂ R", -O-SO ₂ R", -alkyl-SO ₂ R", OCOR", -alkyl-OCOR" or SCOR", unsubstituted or selected from Amino, aminocarbonyl, aminocarbonylalkane substituted by one or two of R", COR", COOR", SO ₂ R", -alkyl-SO ₂ R" or OR" with or without halogen At least one (for example, 1, 2, 3, 4, or 5) of the group or aminosulfonyl group is substituted, or any two adjacent carbon atoms in the ring are connected to -CH ₂ CH ₂ CH ₂ -, -OCH ₂ CH ₂ -, -OCH ₂ O-, -OCH ₂ CH ₂ O- or -CH=CH-CH=CH- groups are connected to form a fused ring;

R" each independently represents alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkylalkyl, cycloalkenyl, cycloalkenylalkyl, and unsubstituted or substituted heterocyclyl, heterocyclylalkyl , Aryl or arylalkyl.

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

B represents unsubstituted or substituted phenyl;

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

X represents NR ₁ R ₂ , wherein R ₁ represents H, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 ring unsubstituted or optionally substituted with 1-2 R ₁₁ Alkyl or phenyl, -COR ₁₂ , nitro, OR ₁₃ , SO ₂ R ₁₄ , NR ₁₅ R ₁₆ , N=CR ₁₇ R ₁₈ , C1-C8 alkylcarbamoyl, di-C1-C8 alkylcarbamoyl Acyl, tri-C1-C8 alkylsilyl or di-C1-C8 alkylphosphono; R ₂ represents H, unsubstituted or optionally substituted by 1-2 R ₁₁ C1-C8 alkyl or -COR ₁₂ ; Or NR ₁ R ₂ represents N=CR ₂₁ NR ₂₂ R ₂₃ , N=CR ₂₄ OR ₂₅ , unsubstituted or by 1-2 independently selected from halogen, C1-C8 alkyl, halogenated 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 or C1 -C8 alkoxycarbonyl group substituted

Wherein R ₁₁ independently represents halogen, hydroxyl, C1-C8 alkoxy, halogenated C1-C8 alkyl, halogenated C1-C8 alkoxy, C1-C8 alkylthio, halogenated C1-C8 alkylthio, Amino, C1-C8 alkylamino, C1-C8 alkylamino, C1-C8 alkoxycarbonyl, unsubstituted or halogenated, C1-C8 alkyl, halogenated C1-C6 alkyl, C1-C8 alkoxy Group, nitro group or C1-C8 alkoxycarbonyl group substituted by 1-3 groups, phenyl, naphthyl,

R ₁₂ represents H, C1-C18 alkyl, halogenated C1-C8 alkyl, C1-C8 alkoxy, phenyl, phenoxy or benzyloxy;

R ₁₃ represents H, C1-C8 alkyl, halogenated C1-C8 alkyl, phenyl, benzyl or CHR ₃₁ C(O)OR ₃₂ ; R ₃₁ represents H, C1-C8 alkyl or C1-C8 alkoxy R ₃₂ represents H, C1-C8 alkyl or benzyl;

R ₁₄ represents C1-C8 alkyl or halogenated C1-C8 alkyl;

R ₁₅ represents H, C1-C8 alkyl, formyl, C1-C8 alkyl acyl, halogenated C1-C8 alkyl acyl, C1-C8 alkoxycarbonyl, phenylcarbonyl, phenoxycarbonyl or benzyloxy Carbonyl; R ₁₆ represents H or C1-C8 alkyl;

R ₁₇ represents H, C1-C8 alkyl, unsubstituted or phenyl substituted with 1-3 groups of halogen, C1-C8 alkyl, halogenated C1-C8 alkyl or C1-C8 alkoxy ; R ₁₈ represents H or C1-C8 alkyl; or N=CR ₁₇ R ₁₈ represents

R ₂₁ and R ₂₄ each independently represent H or C1-C8 alkyl;

R ₂₂ and R ₂₃ each independently represent H or C1-C8 alkyl; or NR ₂₂ R ₂₃ represents

R ₂₅ represents C1-C8 alkyl;

Y represents unsubstituted or substituted pyridyl;

The "substituted" in groups B and Y each independently refers to being selected from halogen, nitro, cyano, thiocyano, cyano C1-C8 alkyl, mercapto, hydroxyl, hydroxy C1-C8 alkyl , Carboxyl, formyl, azido, tri-C1-C8 alkylsilyl, di-C1-C8 alkylphosphono, unsubstituted or selected from halogen, C1-C8 alkyl, halogenated C1-C8 alkyl , C1-C8 alkoxy or heterocyclic group substituted by 1-3 groups in amino group, heterocyclic group C1-C8 alkyl, aryl or aryl C1-C8 alkyl, with or without halogen C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 cycloalkyl, C3-C8 cycloalkenyl, C3-C8 cycloalkyl, C1-C8 alkyl, C3-C8 cycloalkenyl C1-C8 alkyl, C3-C8 cycloalkyl substituted with C1-C8 alkyl, 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 ₂ R", -O-SO ₂ R", -(C1-C8)alkyl- SO ₂ R", OCOR", -(C1-C8)alkyl-OCOR" or SCOR", unsubstituted or selected from R", COR", COOR", SO ₂ R",- (C1-C8) Alkyl-SO ₂ R" or OR" at least one of amino, aminocarbonyl, aminocarbonyl C1-C8 alkyl or aminosulfonyl substituted by one or two groups (for example, 1, 2, 3, 4, or 5) groups, or any two adjacent carbon atoms in the ring and -CH ₂ CH ₂ CH ₂ -, -OCH ₂ CH ₂ -, -OCH ₂ O-, -OCH ₂ CH ₂ O- or -CH=CH-CH=CH- groups are connected to form a fused ring;

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 1-3 groups that are unsubstituted or selected from halogen, C1-C8 alkyl, halogenated C1-C8 alkyl, C1-C8 alkoxy or amino The heterocyclic group, heterocyclic C1-C8 alkyl, aryl or aryl C1-C8 alkyl substituted by the group.

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

B represents unsubstituted or substituted phenyl;

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

X represents NR ₁ R ₂ , wherein R ₁ represents H, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 ring unsubstituted or optionally substituted with 1-2 R ₁₁ Alkyl or phenyl, -COR ₁₂ , nitro, OR ₁₃ , SO ₂ R ₁₄ , NR ₁₅ R ₁₆ , N=CR ₁₇ R ₁₈ , C1-C6 alkylcarbamoyl, di-C1-C6 alkylcarbamoyl Acyl, tri-C1-C6 alkylsilyl or di-C1-C6 alkylphosphono; R ₂ represents H, unsubstituted or optionally substituted by 1-2 R ₁₁ C1-C6 alkyl or -COR ₁₂ ; Or NR ₁ R ₂ represents N=CR ₂₁ NR ₂₂ R ₂₃ , N=CR ₂₄ OR ₂₅ , unsubstituted or by 1-2 independently selected from halogen, C1-C6 alkyl, halogenated 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 or C1 -C6 alkoxycarbonyl group substituted

Wherein R ₁₁ independently represents halogen, hydroxyl, C1-C6 alkoxy, halogenated C1-C6 alkyl, halogenated C1-C6 alkoxy, C1-C6 alkylthio, halogenated C1-C6 alkylthio, Amino, C1-C6 alkylamino, C1-C6 alkylamino, C1-C6 alkoxycarbonyl, unsubstituted or halogenated, C1-C6 alkyl, halogenated C1-C6 alkyl, C1-C6 alkoxy Group, nitro group or C1-C6 alkoxycarbonyl group substituted by 1-3 groups, phenyl, naphthyl,

R ₁₂ represents H, C1-C14 alkyl, halogenated C1-C6 alkyl, C1-C6 alkoxy, phenyl, phenoxy or benzyloxy;

R ₁₃ represents H, C1-C6 alkyl, halogenated C1-C6 alkyl, phenyl, benzyl or CHR ₃₁ C(O)OR ₃₂ ; R ₃₁ represents H, C1-C6 alkyl or C1-C6 alkoxy R ₃₂ represents H, C1-C6 alkyl or benzyl;

R ₁₄ represents C1-C6 alkyl or halogenated C1-C6 alkyl;

R ₁₅ represents H, C1-C6 alkyl, formyl, C1-C6 alkyl acyl, halogenated C1-C6 alkyl acyl, C1-C6 alkoxycarbonyl, phenylcarbonyl, phenoxycarbonyl or benzyloxy Carbonyl; R ₁₆ represents H or C1-C6 alkyl;

R ₁₇ represents H, C1-C6 alkyl, unsubstituted or phenyl substituted with 1-3 groups of halogen, C1-C6 alkyl, halogenated C1-C6 alkyl or C1-C6 alkoxy ; R ₁₈ represents H or C1-C6 alkyl; or N=CR ₁₇ R ₁₈ represents

R ₂₁ and R ₂₄ each independently represent H or C1-C6 alkyl;

R ₂₂ and R ₂₃ each independently represent H or C1-C6 alkyl; or NR ₂₂ R ₂₃ represents

R ₂₅ represents C1-C6 alkyl;

Y represents unsubstituted or substituted pyridyl;

The "substituted" in groups B and Y each independently refers to being selected from halogen, nitro, cyano, thiocyano, cyano C1-C6 alkyl, mercapto, hydroxyl, hydroxy C1-C6 alkyl , Carboxyl, formyl, azido, tri-C1-C6 alkylsilyl, di-C1-C6 alkylphosphono, unsubstituted or selected from halogen, C1-C6 alkyl, halogenated C1-C6 alkyl , C1-C6 alkoxy or amino group substituted by 1-3 groups of heterocyclic group, heterocyclic group C1-C6 alkyl, aryl or aryl C1-C6 alkyl, with or without halogen C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, C3-C6 cycloalkenyl, C3-C6 cycloalkyl, C1-C6 alkyl, C3-C6 cycloalkenyl C1-C6 alkyl, C3-C6 cycloalkyl substituted with C1-C6 alkyl, 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 ₂ R", -O-SO ₂ R", -(C1-C6)alkyl- SO ₂ R", OCOR", -(C1-C6)alkyl-OCOR" or SCOR", unsubstituted or selected from R", COR", COOR", SO ₂ R",- (C1-C6) Alkyl-SO ₂ R" or OR" at least one of amino, aminocarbonyl, aminocarbonyl C1-C6 alkyl or aminosulfonyl substituted by one or two groups (for example, 1, 2, 3, 4, or 5) groups, or any two adjacent carbon atoms in the ring and -CH ₂ CH ₂ CH ₂ -, -OCH ₂ CH ₂ -, -OCH ₂ O-, -OCH ₂ CH ₂ O- or -CH=CH-CH=CH- groups are connected to form a fused ring;

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 group, and 1-3 groups that are unsubstituted or selected from halogen, C1-C6 alkyl, halogenated C1-C6 alkyl, C1-C6 alkoxy or amino The heterocyclic group, heterocyclic C1-C6 alkyl, aryl or aryl C1-C6 alkyl substituted by the group.

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

B represents unsubstituted or phenyl substituted with 1, 2, 3 or 4 substituents selected from fluorine, chlorine, bromine, methyl, methoxy, methylthio or dimethylamino;

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

X stands for NR ₁ R ₂ ,

Wherein R ₁ represents H, unsubstituted or optionally substituted with 1 R ₁₁ methyl, methylcarbonyl, tert-butyloxycarbonyl, cyclopropyl or phenyl;

R ₂ represents H or methyl;

R ₁₁ independently represents phenyl,

Unsubstituted or substituted by trifluoromethyl

Y represents unsubstituted or selected from fluorine, chlorine, bromine, methyl, trifluoromethyl, vinyl, 2-chlorovinyl, ethynyl, cyclopropyl, cyano, nitro, hydroxyl, methoxy, Methylthio, ethylthio, methylcarbonyl, methylsulfonyl, amino, monomethylamino, dimethylamino, hydroxymethyl, cyanomethyl, methoxycarbonyl, methylcarbonyloxy or methyl Substituted by 1, 2, 3 or 4 substituents in the carbonylamino group

More preferably, B represents

X stands for NH ₂ , NHMe, N(Me) ₂ ,

Unsubstituted or substituted by trifluoromethyl

In the definition of the compound represented by the above general formula and all the following structural formulas, the professional terms used, whether used alone or in compound words, represent the following substituents: alkyl groups with more than two carbon atoms can be straight or branched Chained. For example, in the compound word "-alkyl-OR", the alkyl group can be -CH ₂ -, -CH ₂ CH ₂ -, -CH(CH ₃ )-, -C(CH ₃ ) ₂ -, etc. The alkyl group is , For example, C1 alkyl-methyl; C2 alkyl-ethyl; C3 alkyl-propyl such as n-propyl or isopropyl; C4 alkyl-butyl such as n-butyl, isobutyl, tert-butyl Or 2-butyl; C5 alkyl-pentyl such as n-pentyl; C6 alkyl-hexyl such as n-hexyl, isohexyl and 1,3-dimethylbutyl. Similarly, alkenyl is for example allyl, 1-methylprop-2-en-1-yl, 2-methylprop-2-en-1-yl, but-2-en-1-yl, but-3-en-1-yl, 1- Methylbut-3-en-1-yl and 1-methylbut-2-en-1-yl. Alkynyl groups are, for example, propargyl, but-2-yn-1-yl, but-3-yn- 1-yl, 1-methylbut-3-yn-1-yl. At least one of multiple bonds (for example, 1, 2, 3) can be in any position of each 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, a cycloalkenyl group is a monocyclic ring having, for example, three to six carbon ring members Alkenyl groups, such as cyclopropenyl, cyclobutenyl, cyclopentenyl and cyclohexenyl, where the double bond can be in any position. Halogen is fluorine, chlorine, bromine or iodine.

Unless otherwise specified, the terminology used in the present invention, whether used alone or in compound words, includes phenyl, naphthyl,

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

It also includes heteroaryl groups, that is, aromatic cyclic groups that contain, for example, 3 to 6 (3, 4, 5, 6) ring atoms and can also be fused through a benzo ring, in which 1 to 4 (1, 2, 3, 4) heteroatoms are selected from oxygen, nitrogen and sulfur, for example

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

In addition, unless specifically limited, in the present invention, multiple parallel substituents (separated by "," or "or") the aforementioned qualifiers have a limiting effect on each of the subsequent substituents, such as "unsubstituted or substituted The "unsubstituted or substituted" in "aryl and heterocyclic group" has a limiting effect on each of the subsequent groups "aryl" and "heterocyclic group"; groups that do not indicate specific attachment positions (including heterocyclic groups) , Aryl group, etc.), can be connected at any position, including the position connected to C or N; if it is substituted, the substituent can also be substituted at any position, as long as it meets the bonding rules. Such as heteroaryl substituted by 1 methyl

Can represent

Wait.

Depending on the nature of the substituents and the manner in which they are connected, the compounds of formula I and their derivatives may exist as stereoisomers. For example, if one or more asymmetric carbon atoms are present, enantiomers and diastereomers can occur. Stereoisomers can be obtained from the mixture obtained in the preparation by conventional separation methods, for example by chromatographic separation. It is also possible to selectively prepare stereoisomers by using stereoselective reactions and using optically active starting materials and/or auxiliary agents. The present invention also relates to all stereoisomers included in the general formula I but not specifically defined and their mixtures.

The preparation method of the substituted picolinic acid pyridine methylene ester derivative includes the following steps: the compound represented by general formula III and the compound represented by general formula II undergo an esterification reaction to obtain the compound represented by 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 more combinations of acetonitrile, DMF, dichloromethane and 1,2-dichloroethane; The reaction temperature is 0-50°C.

A herbicidal composition, which comprises a herbicidal effective amount of at least one of the substituted picolinic acid picolinyl methylene ester derivatives, preferably, further comprises a formulation adjuvant.

A method for controlling weeds, which comprises applying a herbicidal effective amount of at least one of the substituted picolinic acid picolinic acid methylene ester derivatives or the herbicide composition on plants or weed areas .

At least one of the substituted picolinic acid picolinic acid ester derivatives or the herbicide composition is used in weed control, preferably, the substituted picolinic acid picolinic acid The ester derivatives are used to control weeds in useful crops, which are transgenic crops or crops processed by genome editing technology.

For many economically important monocotyledonous and dicotyledonous harmful plants, the compound of formula I of the present invention has outstanding herbicidal activity. The active substance of the present invention is also effective against perennial weeds, which grow from rhizomes, rhizomes, or other perennial organs, which are difficult to control. In this regard, it is generally not important whether the substance is used before sowing, before germination or after germination. Special mention is made of representative examples of monocotyledonous and dicotyledonous weed groups that can be controlled by the compounds of the present invention, and there is no limitation to certain species. Examples of weed species in which the active substance is effective include monocots: annual oats, rye, grass, serrata, phalaris, barnyard, crabgrass, setaria and cyperus, and perennial ice Grass, Bermudagrass, Imperata and Sorghum, and perennial Cyperus.

Regarding the species of dicotyledonous weeds, its role can be extended to species such as the annual genus Asparagus, Viola, Pona, Sesamum, Stellaria, Amaranthus, White mustard, Ipomoea, Nimbus Genus, Matricaria and Abutilon, and perennial weeds Convolvulus, Thistle, Rumex and Artemisia. The active substance of the present invention effectively controls harmful plants such as barnyardgrass, Aquilaria, Alisma, water chestnut, sugarcane and cyperus under the undetermined condition of rice sowing. If the compound of the present invention is applied to the soil surface before germination, the seedling of the weed can be prevented completely before the weed grows, or the growth of the weed can be stopped when the cotyledon grows, and finally died completely after three to four weeks. The compounds of the present invention are particularly active against the following plants, such as Apilagrass, Onea sesame, Polygonum vulgaris, Chrysanthemum vulgaris, Ivy Leaf Panna, Arabian Panna, Pansy and Amaranth, Asparagus and Kochia .

Although the compound of the present invention has excellent herbicidal activity against monocot and dicot weeds, it has no harm to important economic crop plants such as wheat, barley, rye, rice, corn, sugar beet, cotton and soybean. , Or the damage is trivial. Especially compatible with cereal crops, such as wheat, barley and corn, especially wheat. Therefore, the compound of the present invention is very suitable for selectively controlling useless plants in agricultural crops or ornamental plants.

Due to their herbicidal properties, these active substances can be used to control harmful plants in known or upcoming genetic engineering plant cultivation. Transgenic plants usually have superior characteristics, such as resistance to specific insecticides, especially specific herbicides, resistance to plant diseases or pathogenic microorganisms of plant diseases, such as specific insects or fungi, bacteria or virus microorganisms. Other special characteristics are related to the following conditions of the product, such as quantity, quality, storage stability, composition and special ingredients. As such, it is known that the obtained transgenic plant products have increased starch content or improved starch quality or different fatty acid composition.

The compound of formula I of the present invention or its salt is preferably used for economically important transgenic crops and ornamental plants, such as cereals, such as wheat, barley, rye, oats, millet, rice, cassava and corn, or for sugar beet, Cultivation of cotton, soybeans, rapeseed, potatoes, tomatoes, peas and other vegetable plants. The compounds of formula I are preferably used as herbicides for the cultivation of useful plants, which are resistant to herbicides or genetically engineered to the toxic effects of herbicides.

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

-In order to improve starch synthesis in plants, genetic engineering is used to change crop plants (for example, WO 92/11376, WO 92/14827, WO 91/19806);

-Transgenic crop plants that are resistant to specific herbicides, to glufosinate herbicides (for example EP-0242236 A, EP-0242246 A) or glyphosate herbicides (WO 92/00377), or to sulfonate Urea herbicides (EP-0257993 A, US-5013659 A);

-Transgenic crop plants such as cotton, which can produce Bacillus thuringiensis toxin (Bt toxin), which can protect plants from specific pests (EP-0142924A, EP-0193259A);

-Transgenic crop plants with improved fatty acid composition (WO91/13972).

Many molecular biotechnologies that can produce genetically modified plants with improved traits are known (see, for example, Sambrook et al., 1989, Molecular Amplification, Second Edition of Laboratory Manual, published by Cold Spring Harbor Laboratory, Cold Spring Harbor, New York; or Winnacker "Gene und Klone "[Genes and Cloning], VCH Weinheim, Second Edition 1996 or Christou, "Trends in Plant Science" 1 (1996) 423-431)). In order to realize the operation of genetic engineering, it is possible to introduce nucleic acid molecules into plasmids, and through the recombination of DNA sequences, mutations or sequence changes occur. Using the standard methods described above, for example, substrates can be exchanged, partial sequences can be removed, or natural or synthetic sequences can be added. In order to connect the DNA fragments to each other, it is possible to attach a binder or linker to the fragments.

The following methods can be used to prepare plant cells of gene products with reduced activity, for example, by expressing at least one appropriate antisense-RNA, sense-RNA to achieve the co-inhibition effect, or by expressing at least one appropriately structured ribozyme, It specifically cleaves the transcription products of the above gene products.

For this purpose, it is possible to use DNA molecules that contain the entire coding sequence of the gene product, including any flanking sequences that may be present, and use DNA molecules that contain only a portion of the coding sequence, which must be long enough to achieve antisense in the cell Effect. It is also possible to use sequences that have a high degree of homology with the coding sequence of the gene product but are not completely identical.

When expressing nucleic acid molecules in plants, the synthesized protein can be located in any desired plant cell compartment. However, for positioning in a specific chamber, it is possible, for example, to link the coding region and the DNA sequence to ensure positioning 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).

Using known techniques, transgenic plant cells can be recombined into whole plants. The transgenic plant can be any desired plant variety, namely 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 substance of the present invention is used on genetically modified crops, in addition to the effect of inhibiting harmful plants that can be observed on other crops, it often has special effects on the corresponding genetically modified crops, such as improving or expanding control The range of weeds, the improved application rate, the combination of the resistance of genetically modified crops and the performance of herbicides, and the influence of the growth and yield of genetically modified crop plants. Therefore, the present invention also provides the use of the compound as a herbicide to control harmful plants in transgenic crop plants.

In addition, the compounds of the present invention can significantly regulate the growth of crop plants. By regulating the participation in plant metabolism, these compounds are used to control plant components and promote harvest, such as drying and stunting plant growth. And they are also suitable for regulating and inhibiting the growth of undesirable plants without destroying the growth of crops. Inhibiting plant growth plays a very important role in many monocot and dicot crops because it can reduce or completely prevent lodging.

General formulations can be used to apply the compounds of the present invention, and wettable powders, concentrated emulsions, sprayable solutions, powders or granules can be used. Thus, the present invention also provides herbicidal compositions comprising the compound of formula I. According to general biological and/or chemical physical parameters, the compound of formula I can be formulated in a variety of ways. Examples of suitable formulation choices are: wettable powder (WP), water-soluble powder (SP), water-soluble concentrate, concentrated emulsion (EC), such as oil-in-water dispersion and water-in-oil dispersion (EW) , Sprayable solution, suspension concentrate (SC), dispersible oil suspension (OD), suspension with oil or water as diluent, miscible oil solution, powder (DP), capsule suspension (CS ), seeddressing composition, particles for broadcast and soil application, spray particles, coated particles and absorption particles, water dispersible particles (WG), water-soluble particles (SG), ULV (ultra Low-volume) formulations, microcapsules and wax products. These individual formulation types are known and described in the following documents, such as Winnacker-Küchler, "Chemische Techonologie" [Chemical Technology], Volume 7, C. Hauser Verlag Munich, 4th Edition 1986; Wade van Valkenburg, "Pesticide Formulations", Marcel Dekker, NY, 1973; K. Martens, "Spray Drying" manual, 3rd edition 1979, G. Goodwin Ltd. London.

Necessary formulation auxiliaries such as inert substances, surfactants, solvents and other additives are also known and described in the following documents, such as "Powder Diluent Insecticide and Carrier Handbook" by Watkins, second edition, Darland book Caldwell NJ; Hv01phen "Introduction to Clay Colloid Chemistry", second edition, J. Wiley and Sons, NY; C. Marsden's "Solvent Guide" second edition, Interscience, NY1963; McCutcheon's "Detergents and Emulsifiers" Annual Report, MC Publishing Company, Ridgewood NJ; Sisley and Wood, "Encyclopedia of Surfactants", Chemical Publishing Company, NY1964;

of

[Ethylene oxide adduct surfactant], Wiss. Verlagagesell. Stuttgart 1976; Winnacker-Küchler's "Chemische Technologie" [Chemical Technology], Vol. 7, C. Hauser Verlag Munich, 4th edition 1986.

Wettable powders can be uniformly dispersed in water. In addition to active substances, they also include diluents or inert substances, ionic and non-ionic surfactants (wetting agents, dispersing agents), such as polyethoxyalkylphenol, poly Ethoxylated fatty alcohol, polyoxyethyl aliphatic amine, fatty alcohol polyglycol ether sulfate, alkyl sulfonate, alkyl phenyl sulfonate, sodium lignosulfonate, 2,2'-dinaphthyl methane -6,6'-Sodium disulfonate, sodium dibutyl naphthalene sulfonate or sodium oleoyl methyl taurate. To prepare a wettable powder, the active substance of the herbicide is finely ground, for example, using commonly used equipment such as a hammer mill, a fan mill and a jet mill, and the additives are mixed in simultaneously or sequentially.

Dissolve the active substance in an organic solvent to prepare a concentrated emulsion, such as butanol, cyclohexanone, dimethylformamide, xylene or a mixture of higher boiling aromatic compounds or hydrocarbons or solvents, and add another One or more ionic and/or non-ionic surfactants (emulsifiers). Examples of emulsifiers that can be used are calcium alkylarylsulfonates such as calcium dodecylbenzenesulfonate, or nonionic emulsifiers such as fatty acid polyglycol esters, alkyl aromatic polyglycol ethers, and fatty alcohols. Polyglycol ethers, propylene oxide-ethylene oxide condensation products, alkyl polyethers, sorbitan esters such as sorbitan fatty acid esters, or polyoxyethylene sorbitans such as polyoxyethylene sorbitan fatty esters Glycan ester.

The active material and the finely divided solid material are ground to obtain a powder, such as talc, natural clay such as kaolin, bentonite and pyrophyllite, or diatomaceous earth. The water or oil-based suspension can be prepared by the following method, for example, wet milling using a commercially available glass bead mill, with or without addition of the above-mentioned other formulation type surfactant.

To prepare an emulsion such as an oil-in-water emulsifier (EW), an aqueous organic solvent can be used, a stirrer, a colloid mill and/or a static mixer, and if necessary, another formulation type surfactant as described above is added.

The granules are prepared by the following method. The active substance is sprayed onto the adsorbent, granulated with an inert material, or the active substance is concentrated on the surface of a carrier such as sand or kaolin, and the inert material is granulated through a binder. Mixtures such as polyvinyl alcohol, sodium polyacrylate or mineral oil. The method of preparing fertilizer granules can be used to granulate suitable active substances, and fertilizers can be mixed if necessary. Use the usual methods to prepare water suspension granules, such as spray-drying, fluidized bed granulation, grinding disc granulation, mixing with a high-speed mixer, and extrusion without solid inert materials.

Regarding the preparation methods of using grinding discs, fluidized beds, extruders and sprayed granules, refer to the following processes, for example, "Spray Drying Manual" Third Edition 1979, G. Goodwin Ltd., London; JEBrowning, "Agglomeration", Chemistry and Engineering 1967, pages 147ff; "Perry's Chemical Engineer's Handbook", Fifth Edition, McGraw-Hill, New York 1973, pages 8-57. If you want to know about the formulation of crop protection products, see, for example, GCKlingman, "Weed Control as a Science", John Wiley and Sons, New York, 1961, pages 81-96 and JDFreyer, SAEvans, "Weed Control Manual", Fifth Edition, Blackwell Scientific Rublications, Oxford University 1968, pages 101-103.

Agrochemical preparations usually contain 0.1 to 99% by weight, in particular 0.1 to 95%, of the active substance of formula I. The concentration of the active substance in the wettable powder is, for example, from about 10 to 99% by weight, and the usual formulation components constitute the remaining amount by weight to 100%. The concentration of the active substance in the concentrated emulsion may be about 1 to 90% by weight, preferably 5 to 80%. Powder formulations contain 1 to 30% by weight of active substance, usually preferably 5 to 20% by weight of active substance, while sprayable solutions contain about 0.05 to 80% by weight, preferably 2 to 50% by weight of active substance . Regarding the content of active material in water suspended granules, it is mainly based on whether the active material is liquid or solid, and the additives and fillers used in granulation. The content of the active substance in the water suspended granules is, for example, between 1 and 95% by weight, preferably between 10 and 80% by weight.

In addition, the formulation of the active substance may include thickeners, wetting agents, dispersants, emulsifiers, penetrants, preservatives, antifreeze agents, solvents, fillers, carriers, colorants, defoamers, evaporation inhibitors and PH and viscosity regulators commonly used in all cases.

Based on these preparations, it can also be mixed with other insecticide active substances such as insecticides, acaricides, herbicides and fungicides. It can also be mixed with safeners, fertilizers and/or plant growth regulators. The mixing method can be It is pre-mixed or filled and mixed.

In a compounding formulation or a tank-mixing formulation, suitable active substances that can be mixed with the active substances of the present invention are, for example, "Encyclopedia of World Pesticide New Variety Technologies", China Agricultural Science and Technology Press, 2010.9 and those in the literature cited here Known substance. For example, the herbicide active substances mentioned below can be mixed with the mixture of formula I, (Note: the name of the compound, or the common name according to the International Organization for Standardization (ISO), or the chemical name, with the code when appropriate): Amine, Butachlor, Alachlor, Propolachlor, Metolachlor, Fine Metolachlor, Pretilachlor, Tetrachlor, Mesochlor, Naprolam, R-Naproxen Mefenacet, propanyl, mefenacet, difenacet, diflufenican, chlorfenazone, flufenacet, bromobutyramide, dimethenamid, high-efficiency dimethyl Thienachlor, ethoxyfen, flufenacet, metolachlor, metazachlor, clomazone, high-efficiency straw voltameth, high-efficiency straw voltaprox, diacrylamide, clematis , Butachlor, cyprofen, fenoxsulam, enantholac, ibutachlor, propitrachlor, terbutachlor, xylene chlor, dimethenamid, chlorpropamide, Trimethochlor, chlorfenacet, propadifen, valerolachlor, carmethochlor, syenyl, tricyclomethan, butenamid, formachlor, promethazine, quinone Pingamine, fenfluramide, naprolamine, acetochlor, naphthachlor, dimethochlor, metamethochlor, promethacin, chlorophthalimide, butamidine, flumipyr Amine, atrazine, simazine, promethazine, cyanochloride, siprogin, atrazine, permethionine, isopropion, fluroxylin, terbutyrin, terbuthine, triazine , Cyproterin, cyproterine, cyproterazine, cyproterone, simaton, azidogen, diquat, isoprene, cyproterene, meton, other dingjin, zhongdingtong, special Dingtong, Methoxyprogrin, Cyanoxypyr, Inhibitor, Colazuine, Atrtoton, Metoxaton, Glycyrrhizin, Cyanuric Acid, Indaziflam, Chlorsulfuron, Metsulfuron, Bensulfuron-methyl, Chlorine Susulfuron, Trisulfuron, Thisulfuron, Pyramsulfuron, Mesosulfuron, Mesosulfuron sodium, Formamisulfuron-methyl, Trisulfuron, Trisulfuron, Mesulfuron Sulfuron-methyl, nicosulfuron, methamsulfuron, sulfimuron-methyl, ethoxysulfuron-methyl, ciprosulfuron-methyl, sulfonsulfuron-methyl, tetrazosulfuron-methyl, flazasulfuron, monosulfuron-methyl, Monosulfuron ester, fluzosulfuron-methyl, flufensulfuron-methyl, flufensulfuron-methyl, epoxysulfuron-methyl, zolapisulfuron-methyl, flufensulfuron-methyl, propasulfuron-methyl, triflufensulfuron-methyl, Sulfosulfuron, triflufensulfuron, fluasulfuron-methyl, trifluoromethylsulfuron, metsulfuron-methyl sodium salt, flufenuron-methyl, metsulfuron-methyl, sulfasulfuron, Propyrisulfuron Sulfuron), pyrazosulfuron, acifluorfen, fomesafen, lactofen-ethyl, fenfluroxyfen, oxyfluorfen, fluroxyfen, aclofen, and flufenopyr Ethyl ethyl, carboxyfluorfen, fluorfenpyr, methoxyfen, fluorine fluoride, fluorine fluoride, flufenapyr, chlorfenazone, chlorfenapyr, dimethyl fluoride, flufenoxazone Fluroxyfen, fluroxyfen-ethyl, Halosafen, chlorotoluron, isoproturon, liururon, diuron, saprolon, fluroxyuron, trithiopyron, methasulfuron, probenuron, sulfenthiazide Methoxuron, Isoxauron, Tebutthiazuron, Clodinafon, Chlorobromuron, Methoxyuron, Methuron, Methoxyuron, Bromosulfuron, Methoxuron, Lutouron, Diazuron Sulfuron, fenuron, fenuron, fluorine Sulfuron, sulfuron, thiazolone, chlorotoluone, clomazone, cyclamate, thifluron, buthirone, chlorsulfuron, p-flufuron, thiazolone, sulfachlor, trimethylisourea, Oxazolone, Monisouron, Anisuron, Methiuron, Chloreturon, Tetrafluron, Betanin, Betanin-ethyl ester, Betalan, Sulfentrazone, Teraline, Oatlanin, Aniline, Chloraniline, Dichlorbenzyl Ester, Diachlor, Chlorinyl, Carboxazole, Chlorprocarb, Fenasulam, BCPC, CPPC, Carbasulam, Butachlor, Pyramid, Diaman, Pyramid, Dicamba, Dimethoprim, Pyram, Barnyard Methiocarb, Methiochloride, Methiobenz, Methiobencarb, Ethion, Pingcao, Kecaomeng, Prosyloxy, Methiobencarb, 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-chloro, 2,4-D propionic acid, high 2,4-D propionate, 2,4-D butyric acid, 2-methyl 4-chloropropionic acid, 2-methyl 4-chloropropionate , 2 methyl 4 chlorobutyric acid, 2,4,5-dichlorobutyric acid, 2,4,5-dichlorobutyric acid, 2,4,5-dichlorobutyric acid, 2 methyl 4 chlorobutyric acid, dicamba, chlorophyll, Valtrox, Saisson, Triclofenac, Diclofenac, Methoxytriclofen, Propoxyfen, Difluoxyfop, Refining diflufenop-p-ethyl, fluoxyfop-p-ethyl, high-efficiency pyrimidine Mehalofop-p-ethyl, quizalofop, quizalofop-p-ethyl, fenoxaprop-p-ethyl, fenoxaprop-p-ethyl, oxapyr-methyl, cyhalofop-ethyl, oxadifen, clodinafop-ethyl, thiazoxypyr , Promethalin, Pendimethalin, Trifluoropropoxime, Clomazone, Paraquat, Diquat, Ansulfanyl, Ethylflurane, Isoprofen, Mesopropan, Cypro Trifluralin, Profluralin, Ebufluralin, Edifluzin, Edifluzin, Dilarin, Chloridilin, Methalpropalin, Pronidol, Glyphosate, Sarephosate, Glufosinate , Methamidophos, Glufosinate, Phosphosate, Bialaphos, Diazan, Phosphos, Trifos, Valonate, Methamidophos, Glyphosate, Imidazolate, Imidazolate , Imazaquin acid, imazamox, imazamox ammonium salt, imazamox, imazamox, fluroxypyr, isooctyl fluroxypyr, diclopyridine, ammonia Clopyralid, Triclopyr, Fluthiopyr, Halodizin, Triclopyridol, Thiazidime, Flupyridone, Clopyridin, Flurpyridin, Triclopyr butoxy Ethyl ethyl ester, Cliodinate, sethoxydim, clethodim, thiadiazin, dimethoprim, cyclofenone, buthidazole, oximetrione, pyratrione, Buthidazole, trimethoprim, cyprozinone , Mefentrazone, Eetazine, Ametridione, Amibuzin, Bromoxynil, Bromoxynil Octanoyl, Iodobenzonitrile Octanoyl, Iodobenzonitrile, Dichlornitrile, Diphenylacetonitrile, Difentrazone, Hydroxydichlor Oxalonitrile, Iodobonil, Triazole Sulfentrazone, Sulfentrazone, Penoxsulam, Sulfentrazone, Sulfentrazone, Sulfentrazone, Flufentrazone, Fluroxypyr, Sulfentrazone, Saflufenacil , Cyfentrazone, sulfentrazone, sulfentrazone, sulcotrione, mesotrione, sulcotrione, Tembotrione, Tefuryltrione, Bicyclopyrone, Ketodpiradox, isoxaflutole, clomazone, Fenoxasulfone , Methiozolin, Spirapyr-methyl, Metazachlor, Pyrazolate, Yeyanquat, Prozac, Metazachlor, Mechlorfenazone, Pyrasulfotole, Mefentrazone, Pyroxasulfone, Carfentrazone, Flufentrazone Azole, chlorfenazone, chlorfenazone, fentrazone, flufentrazone, sulfentrazone, Bencarbazone, difentrazone, fluprofen-ethyl, clomazone, clomazone, cyclopyridine , Terachlor, Flupropacil, indoxalic acid, fluoxalic acid, flumioxazin, clodinafop-propargyl, phthalobenzyl ether, Flumezin, pentachlorophenol (sodium), diazol, telofol, telox Esters, pentnitrophenol, dinitrophenol, chloronitrophenol, dioxal, dilott, oxadiazon, oxadiazon, pentoxazone, flufentrazone, methyl oxalate, tetrazole Apichlor, fluridazin, fluroxyfen, bromoatramine, dimethyl darfen, pyridalfen, chlorpyridone, lindazone, pyridalvo, Pyridafol, quinclorac, chlormequine Linacic acid, Bentasone, pyridachlor, oxazimone, chlorfenazone, clomazone, cyprofen, isoprofen, propylafen, indazol, sodium chlorate, thatch Subtilis, trichloroacetic acid, monochloroacetic acid, hexachloroacetone, tetrafluoropropionic acid, forage fast, bromophenol oxime, triazole sulfonate, metoxazole, dimethoprim, sulfachlor, acetoflufen, sulfentrazone , Chlorophthalic acid, flurochloridone, barnyardzein, acrolein, trichlorfen, fenpyrazone, oatester, thiadifenpyr, mesphenamine, oxytodone, methoxenone, benzenesulfuron Glufosinate, phosphinothricin, trichloropropionic acid, Alorac, Diethamquat, Etnipromid, Iprymidam, Ipfencarbazone, Thiencarbazone-methyl, Pyrimisulfan, Chlorflurazole, Tripropindan, Sulglycapin, Methionine, Cambendichlor, Cipropyridine, Thiocyanamide , Meclofen, Meclofen, Meclofen, Meclofen, Mecloquin, Meclofen, Meclofen, Meclofenac, Meclofen, Mefenclopyr, Furaclofen, Oxime Oxalan, dibenzoxazole acid, dichloropropenylamine, fluclopyridine, DOW fluclopyridine, 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, if necessary, the commercially available formulations are diluted in a common manner, for example, in wettable powders, concentrated emulsions, suspensions and particles suspended in water, diluted with water. Powders, granules used for soil application, or solutions for broadcasting and spraying, generally do not need to be further diluted with inert substances before use. As the external conditions change, the required usage amount of the compound of formula I is also different. The external conditions are, for example, temperature, humidity, and the nature of the herbicide used. It can have a large variation range, for example, between 0.001 and 1.0 kg/ha, or more active substances, but preferably between 0.005 and 750 g/ha, especially between 0.005 and 250 g/ha.

Detailed ways

The following examples are used to illustrate the present invention, and should not be regarded as limiting the present invention in any way. The scope of rights claimed by the present invention is described by the claims.

In view of the economy and diversity of the compounds, we prefer to synthesize some compounds. Among the synthesized compounds, selected parts are listed in Table 1 below. The specific compound structure and corresponding compound information are shown in Table 1. The compounds in Table 1 are only to better illustrate the present invention, but do not limit the present invention. For those skilled in the art, it should not be understood that the scope of the above subject of the present invention is limited to the following compounds.

Table 1 Compound structure and ¹ HNMR data

Several methods for preparing the compounds of the present invention are explained in detail in the following schemes and examples. The raw materials can be purchased on the market or can be prepared by methods known in the literature or as shown in the detailed description. Those skilled in the art should understand that other synthetic routes can also be used to synthesize the compounds of the present invention. Although the specific raw materials and conditions in the synthetic route have been described in the following, they can be easily replaced with other similar raw materials and conditions. These modifications or variations of the preparation method of the present invention produce such compounds as Various isomers etc. are included in the scope of the present invention. In addition, the preparation method described below can be further modified according to the disclosure of the present invention using conventional chemical methods well known to those skilled in the art. For example, protecting appropriate groups during the reaction and so on.

The method examples provided below are used to promote a further understanding of the preparation method of the present invention, and the specific substances, types and conditions used are determined to be a further description of the present invention, and not to limit its reasonable scope.

Examples of representative compounds are as follows, and the synthetic methods of other compounds are similar, and will not be described in detail here.

1. Preparation of compound 1:

In 80 ml of DCM, compound 1-1 (5.0g, 17.7mmol, 1.0eq), Et ₃ N (1.97g, 19.4mmol, 1.1eq) and 1-2 (2.12g, 19.4mmol, 1.1eq) were sequentially added Then, PyBOP (10.11g, 19.4mmol, 1.1eq) was added at 20°C, and the reaction solution was stirred at 20°C for 5 hours. LCMS detection showed that the reaction of the raw materials was basically completed and there was a major new peak. The reaction solution was poured into 100 ml of water and separated. The aqueous phase was extracted once with 100 ml of dichloromethane, the organic phase was washed once with saturated brine (100 ml), dried with anhydrous sodium sulfate, and concentrated to obtain a crude product. The crude product was passed through the column The compound 1 (5.5 g, 83.2% yield) (white solid) was obtained by analysis and separation.

2. Preparation of compound 115:

Compound 115-1 (0.8g, 2.7mmol, 1.0eq), Et ₃ N (0.3g, 2.9mmol, 1.1eq) and 115-2 (0.52g, 2.9mmol, 1.1eq) were sequentially added to 10mL of DCM, Then PyBOP (1.5g, 2.9mmol, 1.1eq) was added at 20°C, and the reaction solution was stirred at 20°C for 5 hours. LCMS detection showed that the reaction of the raw materials was basically completed and there was a major new peak. The reaction solution was poured into water (50ml) and 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 obtain a crude product. The compound 115 (1.0 g, 81.6% yield) (white solid) was isolated by column chromatography.

3. Preparation of compound 149:

In 10 ml of DCM, compound 144-1 (0.7g, 2.0mmol, 1.0eq), Et ₃ N (0.22g, 2.2mmol, 1.1eq) and 149-2 (0.24g, 2.2mmol, 1.1eq) were added sequentially , Then PyBOP (1.15g, 2.2mmol, 1.1eq) was added at 20°C, and the reaction solution was stirred at 20°C for 5 hours. LCMS detection showed that the reaction of the raw materials was basically completed and there was a major new peak. The reaction solution was poured into 20 ml of water and separated. The aqueous phase was extracted once with 30 ml of dichloromethane, the organic phase was washed once with saturated brine (20 ml), dried over anhydrous sodium sulfate, and concentrated to obtain a crude product. The crude product was passed through the column The compound 149 (0.75 g, 77.5% yield) (white solid) was obtained by precipitation and separation.

4. Preparation of compound 168:

Refer to the preparation of compound 1 above to obtain compound 37, and then add compound 37 (500 mg, 1.34 mmol, 1.0 eq), NaH (58.8 mg, 60% purity, 1.47 mmol, 1.1 eq) in 10 ml of THF, and then add it to 0 Compound 168-1 (0.34 g, 1.47 mmol, 1.1 eq) was added after stirring for 0.5 hour at ℃, and the reaction solution was stirred at 20 ℃ for 5 hours. LCMS detection showed that the reaction of the raw materials was basically completed and there was a major new peak. The reaction solution was poured into 30 ml of water and separated. The aqueous phase was extracted once with 30 ml of dichloromethane. The organic phase was washed once with saturated brine (30 ml), dried over anhydrous sodium sulfate, and concentrated to obtain a crude product. The crude product was passed through the column The compound 168 (0.55 g, 78.6% yield) (white solid) was obtained by analysis. Or referring to the above steps, first react compound 1-1 with compound 168-1, and then with compound

The esterification reaction takes place to produce compound 168.

5. Preparation of compound 173:

Compound 173-1 (0.28g, 1mmol, 1.0eq), Et ₃ N (0.11g, 1.1mmol, 1.1eq) and 1-2 (0.12g, 1.1mmol, 1.1eq) were sequentially added to 10ml of DCM, Then PyBOP (0.57g, 1.1mmol, 1.1eq) was added at 20°C, and the reaction solution was stirred at 20°C for 5 hours. LCMS detection showed that the reaction of the raw materials was basically completed and there was a major new peak. The reaction solution was poured into 20 ml of water and separated. The aqueous phase was extracted once with 20 ml of dichloromethane, the organic phase was washed once with saturated brine (20 ml), dried over anhydrous sodium sulfate, and concentrated to obtain a crude product. The crude product was passed through the column Analytical separation gave compound 173 (0.29 g, 78.4% yield) (white solid).

Evaluation of biological activity:

Rice safety rating standards are:

Level 5: Rice severely inhibits growth and will eventually die.

Grade 4: Plant height and root length are inhibited by more than 40%; new leaves are difficult to extract and rice is scattered.

Grade 3: Plant height and root length are inhibited by 25%-40%; new leaves are drawn out and become shorter, and new leaves have cores.

Grade 2: Plant height and root length are inhibited by 10%-25%; new leaves extraction becomes shorter.

Grade 1: Plant height and root length are inhibited by 5%-10%; new leaves are extracted normally.

Grade 0: Plant height and root system are normal.

The activity level standards for other plant damage (ie growth control rate) are as follows:

Level 5: The growth control rate is above 85%;

Level 4: The growth control rate is greater than or equal to 60% and less than 85%;

Level 3: The growth control rate is greater than or equal to 40% and less than 60%;

Level 2: The growth control rate is greater than or equal to 20% and less than 40%;

Level 1: The growth control rate is greater than or equal to 5% and less than 20%;

Grade 0: The growth control rate is less than 5%.

The above growth control rate is the fresh weight control rate.

(1) Post-emergence test experiment: place monocot and dicot weed seeds and main crop seeds (wheat, corn, rice, soybean, cotton, rape, millet, sorghum) in a plastic pot filled with soil, and then cover 0.5-2 cm of soil to make it grow in a good greenhouse environment. After sowing for 2-3 weeks, the test plants were treated. The tested compounds of the present invention were dissolved in acetone, and then added to Tween 80 and diluted with a certain amount of water. A solution of a certain concentration is sprayed on the plants with a spray tower. The experimental effects of weeds after 3 weeks of cultivation in the greenhouse after application are listed in Table 2-3.

Table 2 Post-emergence weed test (weed 3-4 leaf stage, rice 3.5 leaf stage)

Compound number	Duck tongue	Ye Cigu	Firefly	Xiangfuzi	Water bamboo leaves	Rice
1	5	5	5	5	5	0
2	5	5	5	5	5	0
3	5	5	5	5	5	0
4	5	5	5	5	5	0
5	5	5	5	5	5	0
6	5	5	5	5	5	0
7	5	5	5	5	5	0
8	5	5	5	5	5	0
9	5	5	5	5	5	0
10	5	5	5	5	5	0
11	5	5	5	5	5	0
12	5	5	5	5	5	0
13	5	5	5	5	5	0
14	5	5	5	5	5	0
15	5	5	5	5	5	0
16	5	5	5	5	5	0
17	5	5	5	5	5	0
18	5	5	5	5	5	0
19	5	5	5	5	5	0
20	5	5	5	5	5	0
twenty one	5	5	5	5	5	0
twenty two	5	5	5	5	5	0

twenty three	5	5	5	5	5	0
twenty four	5	5	5	5	5	0
25	5	5	5	5	5	0
26	5	5	5	5	5	0
27	5	5	5	5	5	0
28	5	5	5	5	5	0
29	5	5	5	5	5	0
30	5	5	5	5	5	0
31	5	5	5	5	5	0
32	5	5	5	5	5	0
33	5	5	5	5	5	0
34	5	5	5	5	5	0
35	5	5	5	5	5	0
36	5	5	5	5	5	0
37	5	5	5	5	5	0
38	5	5	5	5	5	0
39	5	5	5	5	5	0
40	5	5	5	5	5	0
41	5	5	5	5	5	0
42	5	5	5	5	5	0
43	5	5	5	5	5	0
44	5	5	5	5	5	0
45	5	5	5	5	5	0
46	5	5	5	5	5	0
47	5	5	5	5	5	0
48	5	5	5	5	5	0
49	5	5	5	5	5	0
50	5	5	5	5	5	0
51	5	5	5	5	5	0
52	5	5	5	5	5	0
53	5	5	5	5	5	0

54	5	5	5	5	5	0
55	5	5	5	5	5	0
56	5	5	5	5	5	0
57	5	5	5	5	5	0
58	5	5	5	5	5	0
59	5	5	5	5	5	0
60	5	5	5	5	5	0
61	5	5	5	5	5	0
62	5	5	5	5	5	0
63	5	5	5	5	5	0
64	5	5	5	5	5	0
65	5	5	5	5	5	0
66	5	5	5	5	5	0
67	5	5	5	5	5	0
68	5	5	5	5	5	0
69	5	5	5	5	5	0
70	5	5	5	5	5	0
71	5	5	5	5	5	0
72	5	5	5	5	5	0
73	5	5	5	5	5	0
74	5	5	5	5	5	0
75	5	5	5	5	5	0
76	5	5	5	5	5	0
77	5	5	5	5	5	0
78	5	5	5	5	5	0
79	5	5	5	5	5	0
80	5	5	5	5	5	0
81	5	5	5	5	5	0
82	5	5	5	5	5	0
83	5	5	5	5	5	0
84	5	5	5	5	5	0

85	5	5	5	5	5	0
86	5	5	5	5	5	0
87	5	5	5	5	5	0
88	5	5	5	5	5	0
89	5	5	5	5	5	0
90	5	5	5	5	5	0
91	5	5	5	5	5	0
92	5	5	5	5	5	0
100	5	5	5	5	5	0
101	5	5	5	5	5	0
102	5	5	5	5	5	0
103	5	5	5	5	5	0
104	5	5	5	5	5	0
105	5	5	5	5	5	0
106	5	5	5	5	5	0
107	5	5	5	5	5	0
108	5	5	5	5	5	0
109	5	5	5	5	5	0
110	5	5	5	5	5	0
111	5	5	5	5	5	0
112	5	5	5	5	5	0
113	5	5	5	5	5	0
114	5	5	5	5	5	0
115	5	5	5	5	5	0
116	5	5	5	5	5	0
117	5	5	5	5	5	0
118	5	5	5	5	5	0
122	5	5	5	5	5	0
123	5	5	5	5	5	0
124	5	5	5	5	5	0
125	5	5	5	5	5	0

126	5	5	5	5	5	0
127	5	5	5	5	5	0
128	5	5	5	5	5	0
129	5	5	5	5	5	0
130	5	5	5	5	5	0
131	5	5	5	5	5	0
132	5	5	5	5	5	0
133	5	5	5	5	5	0
134	5	5	5	5	5	0
135	5	5	5	5	5	0
136	5	5	5	5	5	0
137	5	5	5	5	5	0
138	5	5	5	5	5	0
139	5	5	5	5	5	0
140	5	5	5	5	5	0
141	5	5	5	5	5	0
142	5	5	5	5	5	0
143	5	5	5	5	5	0
144	5	5	5	5	5	0
145	5	5	5	5	5	0
146	5	5	5	5	5	0
147	5	5	5	5	5	0
148	5	5	5	5	5	0
149	5	5	5	5	5	0
150	5	5	5	5	5	0
151	5	5	5	5	5	0
152	5	5	5	5	5	0
153	5	5	5	5	5	0
154	5	5	5	5	5	0
155	5	5	5	5	5	0
156	5	5	5	5	5	0

157	5	5	5	5	5	0
158	5	5	5	5	5	0
159	5	5	5	5	5	0
160	5	5	5	5	5	0
161	5	5	5	5	5	0
162	5	5	5	5	5	0
163	5	5	5	5	5	0
164	5	5	5	5	5	0
165	5	5	5	5	5	0
166	5	5	5	5	5	0
167	5	5	5	5	5	0
168	5	5	5	5	5	0
169	5	5	5	5	5	0
170	5	5	5	5	5	0
171	5	5	5	5	5	0
172	5	5	5	5	5	0
173	5	5	5	5	5	0
174	5	5	5	5	5	0
175	5	5	5	5	5	0
176	5	5	5	5	5	0
177	5	5	5	5	5	0
178	5	5	5	5	5	0
179	5	5	5	5	5	0
180	5	5	5	5	5	0
181	5	5	5	5	5	0
182	5	5	5	5	5	0
183	5	5	5	5	5	0
184	5	5	5	5	5	0
186	5	5	N	N	5	0
187	5	5	N	N	5	0
188	5	5	5	5	5	0

189	5	5	5	5	5	0
190	5	5	5	5	5	0
191	5	5	5	5	5	0
192	5	5	5	5	5	0
193	5	5	5	5	5	0
194	5	5	5	5	5	0
195	5	5	5	5	5	0
196	5	5	5	5	5	0
197	5	5	5	5	5	0
198	5	5	5	5	5	0
199	5	5	5	5	5	0
200	5	5	5	5	5	0
201	5	5	5	5	5	0
202	5	5	5	5	5	0
Control compound A	5	5	3	3	5	2
Control compound B	5	5	3	3	5	3
Control compound C	5	5	3	3	5	3
Control compound D	5	5	4	3	5	2
Control compound E	2	2	1	1	2	1
Control compound F	2	2	1	1	2	0
Control compound G	2	2	1	1	2	0

Note: The applied dosage is 30 g/ha of active ingredient and 450 kg/ha of water. N means no data.

Table 3 The results of post-emergence weed test ED ₉₀

Compound number	Polygonum lilac	Alien Cyperus	Ye Cigu	Xiangfuzi	Amaranth	Water bamboo leaves
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, 48 g/ha of active ingredients, the three-leaf stage of weeds, the average of the results of the weed control effect test three times, and then the linear method of logarithm-probability value of measurement, Calculate the effective amount of herbicide to inhibit each weed by 90%, namely ED ₉₀ value (g/ha).

(2) The safety and activity test of direct-seeded rice 2-3 leaf stage and barnyard grass 3 leaf stage stem and leaf spray, and the control effect test results were averaged for three times. Two kinds of rice (Huang Huazhan, Huaidao No. 5) and the average dose of the compound that inhibited an average of 10%, and the average dose of the compound that inhibited an average of 90% from Polygonum syringae, Cyperus rotundus, Amaranthus edulis, Sedge Sedge, Phyllostachys praecox, and A. The ratio is used as the selection index of crops. The results are shown in Table 4. It is generally considered that the selection index is at least greater than 2 and can be used in production, and greater than 4 indicates better selectivity. The higher the selection index, the better.

Table 4 Safety and activity test results

Compound number	Average 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 compounds of the present invention also have good activity and selectivity against broadleaf grasses commonly found in wheat fields. The results are shown in Table 5.

Table 5 Safety and activity test results (application dose is 2 g/ha of active ingredient)

Compound number	Pig sorrow	Artemisia sophia	wheat
1	5	5	0
37	5	5	0
72	5	5	0
127	5	5	0
Control compound A	4	3	0

(4) The safety and activity test of the stalk and leaf sprays at the three-leaf stage of corn and the 4-5 leaf stage of Abutilon, Chenopodium, and Cyperus rotundus. The control effect test results were averaged for three times. The ratio of the average dose of the compound with an average inhibition of 10% by corn to the average dose of the compound with an average inhibition of 90% by broadleaf grass and Cyperus rotundus was used as the crop selection index. The results are shown in Table 6. It is generally considered that the selection index is at least greater than 2 in production It can be used. More than 4 means better selectivity. The higher the selection index, the better.

Table 6 Safety and activity test results

Compound number	Average selection index
1	3.2

37	3
72	4.2
Control compound B	0.8
Control compound C	1.4
Control compound D	1.1

Note: Control compound A:

Control compound B:

Control compound C:

Control compound D:

Control compound E:

Control compound F:

Control compound G:

Among them, the control compounds E, F, G are from WO 2019/084353A1.

(5) Field test: Test the control effect against the main broadleaf grasses and sedges in the field in Heilongjiang, Jiangsu and Hubei of China. A total of three places, take the average. The application period is 20 days after transplanting rice, direct-seeded rice rice 3.4-leaf stage, Ye Cigu 4-5 leaf stage, Agaricus 5 leaf stage, special-shaped sedge 20 cm high, and water bamboo leaf stem length 15-30 cm . The test sample is 3% EC. The sprayer is a knapsack sprayer. The test results are shown in Table 7.

Table 7 Field test results

Note: After sampling and testing in these three places, A. vulgaris, Diffusa, and Cyperus heterophylla are resistant to ALS inhibitors, and there are resistance sites caused by gene mutations.

It can be seen from the above tables 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 parent ring, the substituents and the type of carboxyl derivatives, especially for corn, rice, wheat, etc. The key crops have established good selectivity, but the control compound has poor selectivity to the main crops, which shows that the present invention has achieved excellent unexpected technical effects.

(6) Pre-emergence test experiment:

Place monocot and dicot weed seeds and main crop seeds (wheat, corn, rice, soybean, cotton, rape, millet, sorghum) in a plastic pot filled with soil, and then cover 0.5-2 cm of soil, respectively The tested compound of the present invention was dissolved in acetone, then added to Tween 80, diluted with a certain amount of water to a certain concentration of solution, and sprayed immediately after sowing. After applying the pesticide, it was cultured in the greenhouse for 4 weeks and the experimental results were observed. It was found that most of the agents of the present invention have an excellent effect at a measurement of 250 g/ha, especially for weeds such as barnyardgrass, crabgrass, and abutilon. Wheat, rice, soybean, and rape have good selectivity.

Through experiments, we have found that the compound of the present invention generally has better weed control effects, especially we have noticed that the ALS inhibitors are resistant to ALS Inhibitors, Fructus vulgaris, Alien Cyperus, Artemisia sophia, Shepherd’s Purse, Maijia Broadleaf weeds and sedges such as males, pigs, and Cyperus rotundus have extremely high activity and have very good commercial value.

(7) Evaluation of the safety of transplanted rice and evaluation of the control effect of paddy field weeds:

After filling the 1/1,000,000 hectare pot with paddy soil, sown the seeds of barnyardgrass, firefly, wolfberry, and wild auntia, and lightly cover it with soil. Afterwards, it was placed in a greenhouse with a water storage depth of 0.5-1 cm, and the tubers of Ye Cigu were implanted the next day or two days later. Afterwards, keep the water storage depth 3-4 cm, when barnyardgrass, firefly, wolfgrass reach 0.5 leaf, and the time point when A. wildeae reaches the primary leaf stage, the wettability of the compound of the present invention will be prepared according to the usual preparation method. The water diluent of powder or suspension is evenly dropped with a pipette to reach the prescribed amount of active ingredient.

In addition, after filling the 1/1,000,000 hectare pot with paddy soil, it is leveled so that the water storage depth is 3-4 cm. The next day, the three-leaf stage rice (Japonica rice) is transplanted at a transplanting depth of 3 cm. The compound of the present invention was treated in the same manner as above on the 5th day after transplantation.

Observe the growth status of barnyardgrass, firefly, wolfberry grass and wild scorpion on the 14th day after treatment with the naked eyes, and the growth status of rice on the 21st day after treatment with the medicament. Evaluate the effect according to the above-mentioned activity standard level. Many compounds show Excellent activity and selectivity.

Note: The seeds of Barnyardgrass, Firefly, Ye Cigu, and Langfanggrass were collected from Heilongjiang, China, and tested to be resistant to conventional doses of pyrazosulfuron.

At the same time, after many tests, it has been found that many of the compounds of the present invention have good selectivity for grass lawns such as Zoysia grass, bermudagrass, tall fescue, Poa, ryegrass, seaside paspalum, etc., and can control many key grasses. Weeds and broadleaf weeds. Tests on sugarcane, soybean, cotton, oil sunflower, potato, fruit trees, vegetables, etc. under different application methods also showed excellent selectivity and commercial value.

Claims (10)

1. A substituted pyridine methylene picolinate derivative, as shown in general formula I:

   

   among them,

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

   B represents unsubstituted or substituted phenyl;

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

   X represents NR ₁ R ₂ , wherein R ₁ represents H, an alkyl, alkenyl, alkynyl, cycloalkyl, aryl or heterocyclic group that is unsubstituted or optionally substituted by 1-2 R ₁₁ , -COR ₁₂ , nitro, OR ₁₃ , SO ₂ R ₁₄ , NR ₁₅ R ₁₆ , N=CR ₁₇ R ₁₈ , alkylcarbamoyl, dialkylcarbamoyl, trialkylsilyl or dialkylphosphono ; R ₂ represents H, an unsubstituted or optionally substituted alkyl group with 1-2 R ₁₁ or -COR ₁₂ ; or NR ₁ R ₂ represents N=CR ₂₁ NR ₂₂ R ₂₃ , N=CR ₂₄ OR ₂₅ , Unsubstituted or by 1-2 independently selected from halogen, alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio, amino, alkylamino, dialkylamino or alkoxycarbonyl The 5- or 6-membered saturated or unsaturated ring that does not contain or contains oxygen, sulfur or other nitrogen atoms substituted by the group in;

   Wherein R ₁₁ independently represents halogen, hydroxy, alkoxy, haloalkyl, haloalkoxy, alkylthio, haloalkylthio, amino, alkylamino, dialkylamino, alkoxycarbonyl, unsubstituted or substituted Aryl, heterocyclic group;

   R ₁₂ represents H, alkyl, haloalkyl, alkoxy, phenyl, phenoxy or benzyloxy;

   R ₁₃ represents H, alkyl, haloalkyl, phenyl, benzyl or CHR ₃₁ C(O)OR ₃₂ ; R ₃₁ represents H, alkyl or alkoxy; R ₃₂ represents H, alkyl or benzyl;

   R ₁₄ represents alkyl or haloalkyl;

   R ₁₅ represents H, alkyl, formyl, alkyl acyl, haloalkyl acyl, alkoxycarbonyl, phenylcarbonyl, phenoxycarbonyl or benzyloxycarbonyl; R ₁₆ represents H or alkyl;

   R ₁₇ represents H, alkyl, unsubstituted or substituted by 1-3 groups of halogen, alkyl, haloalkyl or alkoxy; R ₁₈ represents H or alkyl; or N=CR ₁₇ R ₁₈ stands for

   

   R ₂₁ and R ₂₄ each independently represent H or an alkyl group;

   R ₂₂ and R ₂₃ each independently represent H or an alkyl group; or NR ₂₂ R ₂₃ represents a 5- or 6-membered saturated or unsaturated ring that does not contain or contains oxygen, sulfur or other nitrogen atoms;

   R ₂₅ represents an alkyl group;

   Y represents unsubstituted or substituted pyridyl;

   The "substituted" in groups B, R ₁₁ and Y each independently refers to being selected from halogen, nitro, cyano, thiocyano, cyanoalkyl, mercapto, hydroxy, hydroxyalkyl, carboxy, Formyl, azido, trialkylsilyl, dialkylphosphono, unsubstituted or substituted heterocyclyl, heterocyclylalkyl, aryl or arylalkyl, alkyl with or without halogen Group, 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 ₂ R", -O-SO ₂ R", -alkyl-SO ₂ R", OCOR", -alkyl-OCOR" or SCOR", unsubstituted or selected from Amino, aminocarbonyl, aminocarbonylalkane substituted by one or two of R", COR", COOR", SO ₂ R", -alkyl-SO ₂ R" or OR" with or without halogen Is substituted by at least one of the group or aminosulfonyl group, or any two adjacent carbon atoms in the ring are connected to -CH ₂ CH ₂ CH ₂ -, -OCH ₂ CH ₂ -, -OCH ₂ O-, -OCH ₂ CH ₂ O- or -CH=CH-CH=CH- groups are connected to form a fused ring;

   R" each independently represents alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkylalkyl, cycloalkenyl, cycloalkenylalkyl, and unsubstituted or substituted heterocyclyl, heterocyclylalkyl , Aryl or arylalkyl.
2. The substituted pyridine methylene picolinate derivative of claim 1, wherein:

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

   B represents unsubstituted or substituted phenyl;

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

   X represents NR ₁ R ₂ , wherein R ₁ represents H, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 ring unsubstituted or optionally substituted with 1-2 R ₁₁ Alkyl or phenyl, -COR ₁₂ , nitro, OR ₁₃ , SO ₂ R ₁₄ , NR ₁₅ R ₁₆ , N=CR ₁₇ R ₁₈ , C1-C8 alkylcarbamoyl, di-C1-C8 alkylcarbamoyl Acyl, tri-C1-C8 alkylsilyl or di-C1-C8 alkylphosphono; R ₂ represents H, unsubstituted or optionally substituted by 1-2 R ₁₁ C1-C8 alkyl or -COR ₁₂ ; Or NR ₁ R ₂ represents N=CR ₂₁ NR ₂₂ R ₂₃ , N=CR ₂₄ OR ₂₅ , unsubstituted or by 1-2 independently selected from halogen, C1-C8 alkyl, halogenated 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 or C1 -C8 alkoxycarbonyl group substituted

   

   

   Wherein R ₁₁ independently represents halogen, hydroxyl, C1-C8 alkoxy, halogenated C1-C8 alkyl, halogenated C1-C8 alkoxy, C1-C8 alkylthio, halogenated C1-C8 alkylthio, Amino, C1-C8 alkylamino, C1-C8 alkylamino, C1-C8 alkoxycarbonyl, unsubstituted or halogenated, C1-C8 alkyl, halogenated C1-C6 alkyl, C1-C8 alkoxy Group, nitro group or C1-C8 alkoxycarbonyl group substituted by 1-3 groups, phenyl, naphthyl,

   

   

   R ₁₂ represents H, C1-C18 alkyl, halogenated C1-C8 alkyl, C1-C8 alkoxy, phenyl, phenoxy or benzyloxy;

   R ₁₃ represents H, C1-C8 alkyl, halogenated C1-C8 alkyl, phenyl, benzyl or CHR ₃₁ C(O)OR ₃₂ ; R ₃₁ represents H, C1-C8 alkyl or C1-C8 alkoxy R ₃₂ represents H, C1-C8 alkyl or benzyl;

   R ₁₄ represents C1-C8 alkyl or halogenated C1-C8 alkyl;

   R ₁₅ represents H, C1-C8 alkyl, formyl, C1-C8 alkyl acyl, halogenated C1-C8 alkyl acyl, C1-C8 alkoxycarbonyl, phenylcarbonyl, phenoxycarbonyl or benzyloxy Carbonyl; R ₁₆ represents H or C1-C8 alkyl;

   R ₁₇ represents H, C1-C8 alkyl, unsubstituted or phenyl substituted with 1-3 groups of halogen, C1-C8 alkyl, halogenated C1-C8 alkyl or C1-C8 alkoxy ; R ₁₈ represents H or C1-C8 alkyl; or N=CR ₁₇ R ₁₈ represents

   

   

   R ₂₁ and R ₂₄ each independently represent H or C1-C8 alkyl;

   R ₂₂ and R ₂₃ each independently represent H or C1-C8 alkyl; or NR ₂₂ R ₂₃ represents

   

   

   R ₂₅ represents C1-C8 alkyl;

   Y represents unsubstituted or substituted pyridyl;

   The "substituted" in groups B and Y each independently refers to being selected from halogen, nitro, cyano, thiocyano, cyano C1-C8 alkyl, mercapto, hydroxyl, hydroxy C1-C8 alkyl , Carboxyl, formyl, azido, tri-C1-C8 alkylsilyl, di-C1-C8 alkylphosphono, unsubstituted or selected from halogen, C1-C8 alkyl, halogenated C1-C8 alkyl , C1-C8 alkoxy or heterocyclic group substituted by 1-3 groups in amino group, heterocyclic group C1-C8 alkyl, aryl or aryl C1-C8 alkyl, with or without halogen C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 cycloalkyl, C3-C8 cycloalkenyl, C3-C8 cycloalkyl, C1-C8 alkyl, C3-C8 cycloalkenyl C1-C8 alkyl, C3-C8 cycloalkyl substituted with C1-C8 alkyl, 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 ₂ R", -O-SO ₂ R", -(C1-C8)alkyl- SO ₂ R", OCOR", -(C1-C8)alkyl-OCOR" or SCOR", unsubstituted or selected from R", COR", COOR", SO ₂ R",- (C1-C8) Alkyl-SO ₂ R" or OR" substituted by at least one of amino, aminocarbonyl, aminocarbonyl C1-C8 alkyl or aminosulfonyl substituted by one or two groups , Or any two adjacent carbon atoms in the ring and -CH ₂ CH ₂ CH ₂ -, -OCH ₂ CH ₂ -, -OCH ₂ O-, -OCH ₂ CH ₂ O- or -CH=CH-CH= CH- groups are connected to form a fused ring;

   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 1-3 groups that are unsubstituted or selected from halogen, C1-C8 alkyl, halogenated C1-C8 alkyl, C1-C8 alkoxy or amino The heterocyclic group, heterocyclic C1-C8 alkyl, aryl or aryl C1-C8 alkyl substituted by the group.
3. A substituted pyridine methylene picolinate derivative according to claim 1 or 2, wherein A represents C1-C6 alkyl, halogenated C1-C6 alkyl, C1-C6 alkoxy, C1-C6 alkylthio, halogen, cyano, C2-C6 alkenyl or C2-C6 alkynyl;

   B represents unsubstituted or substituted phenyl;

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

   X represents NR ₁ R ₂ , wherein R ₁ represents H, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 ring unsubstituted or optionally substituted with 1-2 R ₁₁ Alkyl or phenyl, -COR ₁₂ , nitro, OR ₁₃ , SO ₂ R ₁₄ , NR ₁₅ R ₁₆ , N=CR ₁₇ R ₁₈ , C1-C6 alkylcarbamoyl, di-C1-C6 alkylcarbamoyl Acyl, tri-C1-C6 alkylsilyl or di-C1-C6 alkylphosphono; R ₂ represents H, unsubstituted or optionally substituted by 1-2 R ₁₁ C1-C6 alkyl or -COR ₁₂ ; Or NR ₁ R ₂ represents N=CR ₂₁ NR ₂₂ R ₂₃ , N=CR ₂₄ OR ₂₅ , unsubstituted or by 1-2 independently selected from halogen, C1-C6 alkyl, halogenated 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 or C1 -C6 alkoxycarbonyl group substituted

   

   

   Wherein R ₁₁ independently represents halogen, hydroxyl, C1-C6 alkoxy, halogenated C1-C6 alkyl, halogenated C1-C6 alkoxy, C1-C6 alkylthio, halogenated C1-C6 alkylthio, Amino, C1-C6 alkylamino, C1-C6 alkylamino, C1-C6 alkoxycarbonyl, unsubstituted or halogenated, C1-C6 alkyl, halogenated C1-C6 alkyl, C1-C6 alkoxy Group, nitro group or C1-C6 alkoxycarbonyl group substituted by 1-3 groups, phenyl, naphthyl,

   

   

   R ₁₂ represents H, C1-C14 alkyl, halogenated C1-C6 alkyl, C1-C6 alkoxy, phenyl, phenoxy or benzyloxy;

   R ₁₃ represents H, C1-C6 alkyl, halogenated C1-C6 alkyl, phenyl, benzyl or CHR ₃₁ C(O)OR ₃₂ ; R ₃₁ represents H, C1-C6 alkyl or C1-C6 alkoxy R ₃₂ represents H, C1-C6 alkyl or benzyl;

   R ₁₄ represents C1-C6 alkyl or halogenated C1-C6 alkyl;

   R ₁₅ represents H, C1-C6 alkyl, formyl, C1-C6 alkyl acyl, halogenated C1-C6 alkyl acyl, C1-C6 alkoxycarbonyl, phenylcarbonyl, phenoxycarbonyl or benzyloxy Carbonyl; R ₁₆ represents H or C1-C6 alkyl;

   R ₁₇ represents H, C1-C6 alkyl, unsubstituted or phenyl substituted with 1-3 groups of halogen, C1-C6 alkyl, halogenated C1-C6 alkyl or C1-C6 alkoxy ; R ₁₈ represents H or C1-C6 alkyl; or N=CR ₁₇ R ₁₈ represents

   

   

   R ₂₁ and R ₂₄ each independently represent H or C1-C6 alkyl;

   R ₂₂ and R ₂₃ each independently represent H or C1-C6 alkyl; or NR ₂₂ R ₂₃ represents

   

   

   R ₂₅ represents C1-C6 alkyl;

   Y represents unsubstituted or substituted pyridyl;

   The "substituted" in groups B and Y each independently refers to being selected from halogen, nitro, cyano, thiocyano, cyano C1-C6 alkyl, mercapto, hydroxyl, hydroxy C1-C6 alkyl , Carboxyl, formyl, azido, tri-C1-C6 alkylsilyl, di-C1-C6 alkylphosphono, unsubstituted or selected from halogen, C1-C6 alkyl, halogenated C1-C6 alkyl , C1-C6 alkoxy or amino group substituted by 1-3 groups of heterocyclic group, heterocyclic group C1-C6 alkyl, aryl or aryl C1-C6 alkyl, with or without halogen C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, C3-C6 cycloalkenyl, C3-C6 cycloalkyl, C1-C6 alkyl, C3-C6 cycloalkenyl C1-C6 alkyl, C3-C6 cycloalkyl substituted with C1-C6 alkyl, 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 ₂ R", -O-SO ₂ R", -(C1-C6)alkyl- SO ₂ R", OCOR", -(C1-C6)alkyl-OCOR" or SCOR", unsubstituted or selected from R", COR", COOR", SO ₂ R",- (C1-C6) Alkyl-SO ₂ R" or OR" substituted by at least one of amino, aminocarbonyl, aminocarbonyl C1-C6 alkyl or aminosulfonyl substituted by one or two groups , Or any two adjacent carbon atoms in the ring and -CH ₂ CH ₂ CH ₂ -, -OCH ₂ CH ₂ -, -OCH ₂ O-, -OCH ₂ CH ₂ O- or -CH=CH-CH= CH- groups are connected to form a fused ring;

   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 1-3 groups that are unsubstituted or selected from halogen, C1-C6 alkyl, halogenated C1-C6 alkyl, C1-C6 alkoxy or amino The heterocyclic group, heterocyclic C1-C6 alkyl, aryl or aryl C1-C6 alkyl substituted by the group.
4. A substituted picolinic acid pyridine methylene ester derivative according to any one of claims 1-3, characterized in that:

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

   B represents unsubstituted or phenyl substituted with 1, 2, 3 or 4 substituents selected from fluorine, chlorine, bromine, methyl, methoxy, methylthio or dimethylamino;

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

   X stands for NR ₁ R ₂ ,

   Wherein R ₁ represents H, unsubstituted or optionally substituted with 1 R ₁₁ methyl, methylcarbonyl, tert-butyloxycarbonyl, cyclopropyl or phenyl;

   R ₂ represents H or methyl;

   R ₁₁ independently represents phenyl,

   

   Unsubstituted or substituted by trifluoromethyl

   

   Y represents unsubstituted or selected from fluorine, chlorine, bromine, methyl, trifluoromethyl, vinyl, 2-chlorovinyl, ethynyl, cyclopropyl, cyano, nitro, hydroxyl, methoxy, Methylthio, ethylthio, methylcarbonyl, methylsulfonyl, amino, monomethylamino, dimethylamino, hydroxymethyl, cyanomethyl, methoxycarbonyl, methylcarbonyloxy or methyl Substituted by 1, 2, 3 or 4 substituents in the carbonylamino group

   
5. A substituted picolinic acid pyridine methylene ester derivative according to claim 4, wherein:

   B stands for

   

   

   X represents NH ₂ , NHMe, N(Me) ₂ ,

   

   Unsubstituted or substituted by trifluoromethyl

   
6. The substituted picolinic acid pyridine methylene ester derivative according to any one of claims 1 to 5, characterized in that it is selected from any one in Table 1.
7. A method for preparing a substituted picolinic acid picolinic acid methylene ester derivative according to any one of claims 1 to 6, characterized in that it comprises the following steps: the compound represented by general formula III and the compound represented by general formula II The compound undergoes an esterification reaction to obtain a compound represented by 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 more combinations of acetonitrile, DMF, dichloromethane and 1,2-dichloroethane; The reaction temperature is 0-50°C.
8. A herbicidal composition, which is characterized in that it comprises a herbicidal effective amount of at least one of the substituted picolinic acid picolinyl methylene ester derivatives according to any one of claims 1 to 6, and preferably, further comprises a formulation Additives.
9. A method for controlling weeds, which is characterized in that it comprises adding a herbicidal effective amount of at least one of the substituted picolinium picolinate derivatives described in any one of claims 1 to 6 or the method described in claim 8. The herbicide composition is used on plants or weed areas.
10. At least one of the substituted picolinic acid picolinic acid methylene ester derivatives according to any one of claims 1 to 6 or the use of the herbicide composition according to claim 8 in controlling weeds, preferably, The substituted picolinium picolinate derivative is used to control weeds in useful crops, which are transgenic crops or crops processed by genome editing technology.