Substituted nitrogen-containing heterocyclic carboxylate ester compound, and preparation method therefor, herbicidal composition and use thereof

Abstract

The present invention belongs to the technical field of pesticides, and particularly relates to a substituted nitrogen-containing heterocyclic carboxylate ester compound, and a preparation method therefor, a herbicidal composition and the use thereof. The compound is as shown in general formula I, / > wherein Q represents CH or C-halogen; X represents heterocyclylalkyl; Y represents halogen, alkoxy or haloalkoxy; Z1 and Z2 each independently represent hydrogen, unsubstituted alkyl or alkyl optionally substituted with 1-2 R11, alkenyl or alkynyl, or -COR12; R1, R2, R3, R4, and R5 each independently represent hydrogen, halogen, etc.; and R6 represents hydrogen, alkyl, etc. The compound is safe to crops, can maintain excellent herbicidal activity, and has high selectivity.

Description

Substituted nitrogen-containing heterocyclic carboxylic acid ester compound, preparation method thereof, herbicidal composition and application thereof Technical Field

[0001] The present invention belongs to the technical field of pesticides, and in particular relates to a substituted nitrogen-containing heterocyclic carboxylic acid ester compound, a preparation method thereof, a herbicidal composition and application thereof. Background Art

[0002] Weed control is a crucial step in achieving efficient agriculture. Despite the diverse range of herbicides on the market, the herbicidal performance and crop selectivity of these known compounds are far from satisfactory. Furthermore, the ever-expanding market, the emergence of weed resistance, the longevity and affordability of these drugs, and the growing concern for the environment necessitate continuous research and development of new, highly effective, safe, and economical herbicides with diverse modes of action.

[0003] Summary of the Invention

[0004] The present invention provides a substituted nitrogen-containing heterocyclic carboxylic acid ester compound, a preparation method thereof, a herbicidal composition and application thereof. The compound is safe to crops, can maintain excellent herbicidal activity and has high selectivity.

[0005] The technical solution adopted in the present invention is as follows:

[0006] A substituted nitrogen-containing heterocyclic carboxylic acid ester compound, as shown in the general formula I:

[0007] wherein Q represents CH or C-halogen;

[0008] X represents a heterocyclylalkyl group;

[0009] Y represents halogen, alkoxy or haloalkoxy;

[0010] Z1 and Z2 are independently hydrogen, unsubstituted or optionally substituted with 1-2 R 11 Substituted alkyl, alkenyl or alkynyl, or -COR 12 ;

[0011] R 11 independently represents halogen, hydroxy, alkoxy, haloalkyl, haloalkoxy, alkylthio, haloalkylthio, amino, alkylamino, dialkylamino, alkoxycarbonyl, aryl or heterocyclic;

[0012] R 12 represents H, alkyl, haloalkyl, alkoxy, phenyl, phenoxy or benzyloxy;

[0013] R1, R2, R3, R4, and R5 independently represent hydrogen, halogen, nitro, cyano, thiocyano, hydroxyl, mercapto, carboxyl, sulfonic acid, formyl, haloformyl, azido, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, heterocyclic, aryl, -N(R 21 )2、-(CO)N(R 21 )2、-O(CO)N(R 21 )2、-O(CS)N(R 21 )2、-(SO2)N(R 21 )2、-O(SO2)N(R 21 )2、-PO(OR 22 )2、-OR 22 、-(CO)R 22 、-SR 22 、-(SO)R 22 、-(SO2)R 22 、-Si(R 22 )3, -O(CO)R 22 、-O-(SO2)R 22 、-S(CO)R 22 、-(SO2)OR 22 、-O(CO)OR 22 、-(CO)(CO)OR 22 、-(CO)OR 22 、-ON=C(R 23 )2. -CR 23 =N-OH or -CR 23 =NOR 22 , wherein the "alkyl", "alkenyl" or "alkynyl" are independently unsubstituted or selected from halogen, nitro, cyano, hydroxyl, mercapto, carboxyl, cycloalkyl, cycloalkenyl, heterocyclyl, aryl, -N(R 21 )2、-(CO)N(R 21 )2、-O(CO)N(R 21 )2、-O(CS)N(R 21 )2、-(SO2)N(R 21 )2、-O(SO2)N(R 21 )2、-OR 22 、-(CO)R 22 、-SR 22 、-(SO)R 22 、-(SO2)R 22 、-O(CO)H、-O(CO)R 22 、-O-(SO2)R 22 、-(CO)OR 22 、-O(CO)OR22 、-Si(R 22 )3, -O(CO)(CO)OH, -O(CO)(CO)OR 22 , -O-alkyl-(CO)OH or -O-alkyl-(CO)OR 22 substituted by at least one group in;

[0014] R6, R 21 Each independently represents hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, aryl, heterocyclic, -OR 22 、-(CO)R 22 、-(CO)OR 22 、-alkyl-(CO)OR 22 、-(SO2)R 22 、-(SO2)OR 22 、-alkyl-(SO2)R 22 、-(CO)N(R 24 )2 or -(SO2)N(R 24 )2;

[0015] R 22 Each independently represents an alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, aryl or heterocyclic group, wherein the "alkyl", "alkenyl" or "alkynyl" are independently unsubstituted or selected from halogen, cyano, trialkylsilyl, cycloalkyl, cycloalkenyl, aryl, heterocyclic group, -OR 25 、-SR 25 、-O(CO)R 25 、-(CO)R 25 、-(CO)OR 25 OR-O(CO)OR 25 substituted by at least one group in;

[0016] R 23 Each independently represents hydrogen, halogen, alkoxy, alkoxyalkyl, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkylalkyl, cycloalkenyl, cycloalkenylalkyl, aryl, arylalkyl, heterocyclyl or heterocyclylalkyl;

[0017] R 24 each independently represents hydrogen, alkyl, alkenyl, alkynyl, alkoxy, alkylsulfonyl, cycloalkyl, cycloalkylalkyl, cycloalkenyl or cycloalkenylalkyl;

[0018] or N(R 21 )2、N(R 24 )2 each independently represents a heterocyclic group wherein the 1-position is a nitrogen atom;

[0019] R 25Each independently represents hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, haloalkyl, haloalkenyl, haloalkynyl, phenyl, or phenyl substituted by at least one group selected from the group consisting of halogen, cyano, nitro, alkyl, haloalkyl, alkoxy, haloalkoxy, alkoxycarbonyl, alkylthio, alkylsulfonyl, or phenoxy substituted by at least one group selected from the group consisting of halogen, cyano, nitro, alkyl, haloalkyl, alkoxy, or haloalkoxy;

[0020] The aforementioned "cycloalkyl", "cycloalkenyl", "heterocyclyl" or "aryl" are independently unsubstituted or selected from oxo, halogen, cyano, nitro, alkyl, alkenyl, alkynyl, cycloalkyl, haloalkyl, haloalkenyl, haloalkynyl, halocycloalkyl, cycloalkyl substituted by alkyl, -OR 10 、-SR 10 、-(CO)OR 10 、-(SO2)R 10 、-N(R 10 )2 or -O-alkyl-(CO)OR 10 or two adjacent carbon atoms on the ring form a fused ring with unsubstituted or halogen-substituted -OCH2CH2- or -OCH2O-;

[0021] R 10 Each independently represents hydrogen, alkyl, haloalkyl, phenyl, or phenyl substituted by at least one group selected from halogen, cyano, nitro, alkyl, haloalkyl, alkoxycarbonyl, alkylthio, alkylsulfonyl, alkoxy or haloalkoxy.

[0022] In one embodiment, X represents a heterocyclyl C1-C8 alkyl group;

[0023] Y represents halogen, C1-C8 alkoxy or halogenated C1-C8 alkoxy;

[0024] Z1 and Z2 are independently hydrogen, unsubstituted or optionally substituted with 1-2 R 11 Substituted C1-C8 alkyl, C2-C8 alkenyl or C2-C8 alkynyl, or -COR 12 ;

[0025] R 11 independently represent halogen, hydroxy, C1-C8 alkoxy, halo-C1-C8 alkyl, halo-C1-C8 alkoxy, C1-C8 alkylthio, halo-C1-C8 alkylthio, amino, C1-C8 alkylamino, di-C1-C8 alkylamino, C1-C8 alkoxycarbonyl, aryl or heterocyclic group;

[0026] R 12represents H, C1-C8 alkyl, halogenated C1-C8 alkyl, C1-C8 alkoxy, phenyl, phenoxy or benzyloxy;

[0027] R1, R2, R3, R4, and R5 independently represent hydrogen, halogen, nitro, cyano, thiocyanato, hydroxyl, mercapto, carboxyl, sulfonic acid, formyl, haloformyl, azido, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 cycloalkyl, C3-C8 cycloalkenyl, heterocyclic, aryl, -N(R 21 )2、-(CO)N(R 21 )2、-O(CO)N(R 21 )2、-O(CS)N(R 21 )2、-(SO2)N(R 21 )2、-O(SO2)N(R 21 )2、-PO(OR 22 )2、-OR 22 、-(CO)R 22 、-SR 22 、-(SO)R 22 、-(SO2)R 22 、-Si(R 22 )3, -O(CO)R 22 、-O-(SO2)R 22 、-S(CO)R 22 、-(SO2)OR 22 、-O(CO)OR 22 、-(CO)(CO)OR 22 、-(CO)OR 22 、-ON=C(R 23 )2. -CR 23 =N-OH or -CR 23 =NOR 22 , wherein the "C1-C8 alkyl", "C2-C8 alkenyl" or "C2-C8 alkynyl" are each independently unsubstituted or selected from halogen, nitro, cyano, hydroxyl, mercapto, carboxyl, C3-C8 cycloalkyl, C3-C8 cycloalkenyl, heterocyclyl, aryl, -N(R 21 )2、-(CO)N(R 21 )2、-O(CO)N(R 21 )2、-O(CS)N(R 21 )2、-(SO2)N(R 21 )2、-O(SO2)N(R 21 )2、-OR 22 、-(CO)R 22 、-SR 22 、-(SO)R22 、-(SO2)R 22 、-O(CO)H、-O(CO)R 22 、-O-(SO2)R 22 、-(CO)OR 22 、-O(CO)OR 22 、-Si(R 22 )3, -O(CO)(CO)OH, -O(CO)(CO)OR 22 , -O-(C1-C8 alkyl)-(CO)OH or -O-(C1-C8 alkyl)-(CO)OR 22 substituted by at least one group in;

[0028] R6, R 21 Each independently represents hydrogen, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 cycloalkyl, C3-C8 cycloalkenyl, aryl, heterocyclic group, -OR 22 、-(CO)R 22 、-(CO)OR 22 、-(C1-C8 alkyl)-(CO)OR 22 、-(SO2)R 22 、-(SO2)OR 22 、-(C1-C8 alkyl)-(SO2)R 22 、-(CO)N(R 24 )2 or -(SO2)N(R 24 )2;

[0029] R 22 Each of the "C1-C8 alkyl", "C2-C8 alkenyl" and "C2-C8 alkynyl" groups is independently unsubstituted or selected from halogen, cyano, tri-C1-C8 alkylsilyl, C3-C8 cycloalkyl, C3-C8 cycloalkenyl, aryl, heterocyclyl, -OR 25 、-SR 25 、-O(CO)R 25 、-(CO)R 25 、-(CO)OR 25 OR-O(CO)OR 25 substituted by at least one group in;

[0030] R 23Each independently represents hydrogen, halogen, C1-C8 alkoxy, C1-C8 alkoxyC1-C8 alkyl, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 cycloalkyl, C3-C8 cycloalkylC1-C8 alkyl, C3-C8 cycloalkenyl, C3-C8 cycloalkenylC1-C8 alkyl, aryl, arylC1-C8 alkyl, heterocyclyl or heterocyclylC1-C8 alkyl;

[0031] R 24 Each independently represents hydrogen, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C1-C8 alkoxy, C1-C8 alkylsulfonyl, C3-C8 cycloalkyl, C3-C8 cycloalkylC1-C8 alkyl, C3-C8 cycloalkenyl or C3-C8 cycloalkenylC1-C8 alkyl;

[0032] or N(R 21 )2、N(R 24 )2 each independently represents a heterocyclic group wherein the 1-position is a nitrogen atom;

[0033] R 25 Each independently represents hydrogen, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 cycloalkyl, halo-C1-C8 alkyl, halo-C2-C8 alkenyl, halo-C2-C8 alkynyl, phenyl or phenyl substituted by at least one group selected from the following: halogen, cyano, nitro, C1-C8 alkyl, halo-C1-C8 alkyl, C1-C8 alkoxy, halo-C1-C8 alkoxy, C1-C8 alkoxycarbonyl, C1-C8 alkylthio, C1-C8 alkylsulfonyl or phenoxy substituted by at least one group selected from the following: halogen, cyano, nitro, C1-C8 alkyl, halo-C1-C8 alkyl, C1-C8 alkoxy or halo-C1-C8 alkoxy;

[0034] The aforementioned "C3-C8 cycloalkyl", "C3-C8 cycloalkenyl", "heterocyclyl" or "aryl" are independently unsubstituted or selected from oxo, halogen, cyano, nitro, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 cycloalkyl, halogenated C1-C8 alkyl, halogenated C2-C8 alkenyl, halogenated C2-C8 alkynyl, halogenated C3-C8 cycloalkyl, C3-C8 cycloalkyl substituted by C1-C8 alkyl, -OR 10 、-SR 10 、-(CO)OR 10 、-(SO2)R 10 、-N(R 10 )2 or -O-(C1-C8 alkyl)-(CO)OR 10or two adjacent carbon atoms on the ring form a fused ring with unsubstituted or halogen-substituted -OCH2CH2- or -OCH2O-;

[0035] R 10 Each independently represents hydrogen, C1-C8 alkyl, halogenated C1-C8 alkyl, phenyl, or phenyl substituted by at least one group selected from halogen, cyano, nitro, C1-C8 alkyl, halogenated C1-C8 alkyl, C1-C8 alkoxycarbonyl, C1-C8 alkylthio, C1-C8 alkylsulfonyl, C1-C8 alkoxy or halogenated C1-C8 alkoxy.

[0036] In another embodiment, X represents a heterocyclyl C1-C6 alkyl group;

[0037] Y represents halogen, C1-C6 alkoxy or halogenated C1-C6 alkoxy;

[0038] Z1 and Z2 are independently hydrogen, unsubstituted or optionally substituted with 1-2 R 11 Substituted C1-C6 alkyl, C2-C6 alkenyl or C2-C6 alkynyl, or -COR 12 ;

[0039] R 11 independently represent halogen, hydroxy, C1-C6 alkoxy, halo-C1-C6 alkyl, halo-C1-C6 alkoxy, C1-C6 alkylthio, halo-C1-C6 alkylthio, amino, C1-C6 alkylamino, di-C1-C6 alkylamino, C1-C6 alkoxycarbonyl, aryl or heterocyclic group;

[0040] R 12 represents H, C1-C6 alkyl, halogenated C1-C6 alkyl, C1-C6 alkoxy, phenyl, phenoxy or benzyloxy;

[0041] R1, R2, R3, R4, and R5 independently represent hydrogen, halogen, nitro, cyano, thiocyanato, hydroxyl, mercapto, carboxyl, sulfonic acid, formyl, haloformyl, azido, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, C3-C6 cycloalkenyl, heterocyclic, aryl, -N(R 21 )2、-(CO)N(R 21 )2、-O(CO)N(R 21 )2、-O(CS)N(R 21 )2、-(SO2)N(R 21 )2、-O(SO2)N(R 21 )2、-PO(OR 22 )2、-OR 22 、-(CO)R22 、-SR 22 、-(SO)R 22 、-(SO2)R 22 、-Si(R 22 )3, -O(CO)R 22 、-O-(SO2)R 22 、-S(CO)R 22 、-(SO2)OR 22 、-O(CO)OR 22 、-(CO)(CO)OR 22 、-(CO)OR 22 、-ON=C(R 23 )2. -CR 23 =N-OH or -CR 23 =NOR 22 , wherein the "C1-C6 alkyl", "C2-C6 alkenyl" or "C2-C6 alkynyl" are each independently unsubstituted or selected from halogen, nitro, cyano, hydroxyl, mercapto, carboxyl, C3-C6 cycloalkyl, C3-C6 cycloalkenyl, heterocyclyl, aryl, -N(R 21 )2、-(CO)N(R 21 )2、-O(CO)N(R 21 )2、-O(CS)N(R 21 )2、-(SO2)N(R 21 )2、-O(SO2)N(R 21 )2、-OR 22 、-(CO)R 22 、-SR 22 、-(SO)R 22 、-(SO2)R 22 、-O(CO)H、-O(CO)R 22 、-O-(SO2)R 22 、-(CO)OR 22 、-O(CO)OR 22 、-Si(R 22 )3, -O(CO)(CO)OH, -O(CO)(CO)OR 22 , -O-(C1-C6 alkyl)-(CO)OH or -O-(C1-C6 alkyl)-(CO)OR 22 substituted by at least one group in;

[0042] R6, R 21 Each independently represents hydrogen, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, C3-C6 cycloalkenyl, aryl, heterocyclic group, -OR 22、-(CO)R 22 、-(CO)OR 22 、-(C1-C6 alkyl)-(CO)OR 22 、-(SO2)R 22 、-(SO2)OR 22 、-(C1-C6 alkyl)-(SO2)R 22 、-(CO)N(R 24 )2 or -(SO2)N(R 24 )2;

[0043] R 22 Each of the "C1-C6 alkyl", "C2-C6 alkenyl" and "C2-C6 alkynyl" is independently unsubstituted or selected from halogen, cyano, tri-C1-C6 alkylsilyl, C3-C6 cycloalkyl, C3-C6 cycloalkenyl, aryl, heterocyclyl, -OR 25 、-SR 25 、-O(CO)R 25 、-(CO)R 25 、-(CO)OR 25 OR-O(CO)OR 25 substituted by at least one group in;

[0044] R 23 Each independently represents hydrogen, halogen, C1-C6 alkoxy, C1-C6 alkoxyC1-C6 alkyl, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, C3-C6 cycloalkylC1-C6 alkyl, C3-C6 cycloalkenyl, C3-C6 cycloalkenylC1-C6 alkyl, aryl, arylC1-C6 alkyl, heterocyclyl or heterocyclylC1-C6 alkyl;

[0045] R 24 Each independently represents hydrogen, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C1-C6 alkoxy, C1-C6 alkylsulfonyl, C3-C6 cycloalkyl, C3-C6 cycloalkylC1-C6 alkyl, C3-C6 cycloalkenyl or C3-C6 cycloalkenylC1-C6 alkyl;

[0046] or N(R 21 )2、N(R 24 ) 2 independently represent unsubstituted or substituted by at least one group selected from oxo, C1-C6 alkyl or C1-C6 alkoxycarbonyl

[0047] R 25Each independently represents hydrogen, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, halo-C1-C6 alkyl, halo-C2-C6 alkenyl, halo-C2-C6 alkynyl, phenyl or phenyl substituted by at least one group selected from the following: halogen, cyano, nitro, C1-C6 alkyl, halo-C1-C6 alkyl, C1-C6 alkoxy, halo-C1-C6 alkoxy, C1-C6 alkoxycarbonyl, C1-C6 alkylthio, C1-C6 alkylsulfonyl or phenoxy substituted by at least one group selected from the following: halogen, cyano, nitro, C1-C6 alkyl, halo-C1-C6 alkyl, C1-C6 alkoxy or halo-C1-C6 alkoxy;

[0048] The aforementioned "C3-C6 cycloalkyl", "C3-C6 cycloalkenyl", "heterocyclyl" or "aryl" are independently unsubstituted or selected from oxo, halogen, cyano, nitro, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, halogenated C1-C6 alkyl, halogenated C2-C6 alkenyl, halogenated C2-C6 alkynyl, halogenated C3-C6 cycloalkyl, C3-C6 cycloalkyl substituted by C1-C6 alkyl, -OR 10 、-SR 10 、-(CO)OR 10 、-(SO2)R 10 、-N(R 10 )2 or -O-(C1-C6 alkyl)-(CO)OR 10 or two adjacent carbon atoms on the ring form a fused ring with unsubstituted or halogen-substituted -OCH2CH2- or -OCH2O-;

[0049] R 10 Each independently represents hydrogen, C1-C6 alkyl, halogenated C1-C6 alkyl, phenyl, or phenyl substituted by at least one group selected from halogen, cyano, nitro, C1-C6 alkyl, halogenated C1-C6 alkyl, C1-C6 alkoxycarbonyl, C1-C6 alkylthio, C1-C6 alkylsulfonyl, C1-C6 alkoxy or halogenated C1-C6 alkoxy.

[0050] In the definition of the compounds represented by the above general formula and in all the following structural formulas, the technical terms used, whether used alone or in compound words, represent the following substituents: Alkyl groups with more than two carbon atoms can be straight-chain or branched. For example, the compound word "-alkyl-(CO)OR 22" " in which the alkyl group can be -CH2-, -CH2CH2-, -CH(CH3)-, -C(CH3)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, vinyl, allyl, 1-methylprop-2-en-1-yl, 2-methylprop-2-en-1-yl, but-2-en-1-yl, but-3-en-1-yl. The alkynyl group is an alkynyl group, such as 1-methylbut-3-ene-1-yl, 1-methylbut-2-ene-1-yl, 1-methylbut-3-ene-1-yl and 1-methylbut-2-ene-1-yl. Alkynyl is, for example, ethynyl, propargyl, but-2-ene-1-yl, but-3-ene-1-yl, 1-methylbut-3-ene-1-yl. Multiple bonds can be in any position of each unsaturated group. Cycloalkyl is a carbocyclic saturated ring system with, for example, three to six carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl. Similarly, cycloalkenyl is a monocyclic alkenyl group with, for example, three to six carbocyclic ring members, such as cyclopropenyl, cyclobutenyl, cyclopentenyl and cyclohexenyl, wherein the double bond can be in any position. Halogen is fluorine, chlorine, bromine or iodine.

[0051] Unless otherwise specified, the "aryl" mentioned in the present invention includes but is not limited to phenyl, naphthyl, The "heterocyclic group" includes but is not limited to saturated or unsaturated non-aromatic cyclic groups etc., and also include but are not limited to heteroaryl, i.e. an aromatic cyclic group containing, for example, 3 to 6 ring atoms and optionally fused to a benzo ring, wherein 1 to 4 (e.g. 1, 2, 3 or 4) heteroatoms in the ring atoms are selected from oxygen, nitrogen and sulfur, for example

[0052] 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 groups selected from the groups mentioned. Furthermore, identical or different substituent characters contained in identical or different substituents are independently selected and may be identical or different. The same applies to ring systems formed from different atoms and units. At the same time, compounds known to those skilled in the art to be chemically unstable under standard conditions are excluded from the scope of the claims.

[0053] In addition, unless otherwise specified, the term "substituted by at least one group" as used herein refers to being substituted by 1, 2, 3, 4 or 5 groups; groups (including heterocyclic groups, aryl groups, etc.) without a specific connection position 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 complies with the chemical bond connection rules. For example, a heteroaryl group substituted by 1 methyl group Can represent wait.

[0054] The preparation method of the substituted nitrogen-containing heterocyclic carboxylic acid ester compound comprises the following steps:

[0055] The compound represented by general formula II is reacted with the compound represented by general formula III to obtain the compound represented by general formula I, and the reaction equation is as follows:

[0056] wherein M represents OH or halogen, and the substituents Q, R1, R2, R3, R4, R5, R6, X, Y, Z1 and Z2 are as defined above.

[0057] In one embodiment, the reaction is carried out in the presence of a solvent.

[0058] In another embodiment, a condensing agent and / or a base is added during the reaction.

[0059] In one embodiment, the solvent is selected from at least one of DMF, DMA, methanol, ethanol, acetonitrile, dichloroethane, DMSO, Dioxane, dichloromethane or ethyl acetate.

[0060] In a specific embodiment, the base is selected from at least one of an inorganic base (such as K2CO3, Na2CO3, Cs2CO3, NaHCO3, KF, CsF, KOAc, AcONa, K3PO4, t-BuONa, EtONa, NaOH, KOH, NaOMe, etc.) or an organic base (such as pyrazole, triethylamine, DIEA, etc.).

[0061] In one embodiment, the condensing agent is selected from at least one of Py-BOP, Py-AOP, EDCI, HOBT, DCC, HBTU or HATU.

[0062] In addition, the compound represented by the general formula I can also be prepared by referring to the method shown in WO20180208582, etc.

[0063] A herbicide composition comprises a herbicidally effective amount of at least one of the substituted nitrogen-containing heterocyclic carboxylic acid ester compounds, and preferably further comprises a formulation adjuvant.

[0064] A method for controlling weeds comprises applying a herbicidally effective amount of at least one of the substituted nitrogen-containing heterocyclic carboxylic acid ester compounds or the herbicide composition on plants or weedy areas.

[0065] The use of at least one of the substituted nitrogen-containing heterocyclic carboxylate compounds or the herbicide composition in controlling weeds, preferably, the substituted nitrogen-containing heterocyclic carboxylate compound is used to control weeds in useful crops, wherein the useful crops are transgenic crops or crops treated with genome editing technology.

[0066] The compounds of formula I of the present invention have outstanding herbicidal activity against many economically important monocotyledonous and dicotyledonous harmful plants. The active substances of the present invention are also effective against perennial weeds that grow from rhizomes, rootstocks, or other perennial organs and are difficult to control. In this regard, it is generally unimportant whether the substance is used before sowing, before germination, or after germination. Representative examples of monocotyledonous and dicotyledonous weed groups that can be controlled by the compounds of the present invention are mentioned in particular, without being limited to specific species. Examples of weed species on which the active substances are effective include monocotyledonous plants: annual Avena, Secale, Grass, Alopecurus, Phalaris, Echinochloa, Digitaria, Setaria, and Cyperus, and perennial Agropyron, Cyperus, Imperata, and Sorghum, as well as perennial Cyperus.

[0067] Regarding dicotyledonous weed species, its activity can be extended to species such as annual Galium, Viola, Veronica, Sesame, Chickweed, Amaranthus, Sinapsis, Ipomoea, Glechoma, Matricaria, and Abutilon, as well as perennial weeds such as Convolvulus, Thistle, Rumex, and Artemisia. The active ingredients of the present invention effectively control harmful plants such as Echinochloa, Sagittaria, Alisma, Eriocheir, Saccharum, and Cyperus under unspecified conditions during rice sowing. If applied to the soil surface before germination, the weed seedlings can be completely prevented from emerging, or growth can be halted as soon as the cotyledons emerge, ultimately resulting in complete death after three to four weeks. The compounds of the present invention are particularly active against Apia, Sesame, Polygonum convolvulus, Chickweed, Ivy-leaved Veronica, Veronica arabicum, Pansy, Amaranthus, Galium, and Kochia.

[0068] While the compounds of the present invention exhibit excellent herbicidal activity against monocotyledonous and dicotyledonous weeds, they cause no damage, or only minimal damage, to economically important crop plants such as wheat, barley, rye, rice, corn, sugar beets, cotton, and soybeans. They are particularly compatible with cereal crops such as wheat, barley, and corn, particularly wheat. Therefore, the compounds of the present invention are well suited for selectively controlling undesirable plants in agricultural or ornamental crops.

[0069] Due to their herbicidal properties, these active substances can be used to control harmful plants in known or upcoming genetically engineered plant cultivation. Transgenic plants often possess superior properties, such as resistance to specific pesticides, especially herbicides, or resistance to plant diseases or their causative microorganisms, such as specific insects or fungal, bacterial, or viral microorganisms. Other specific properties are related to the product's characteristics, such as quantity, quality, storage stability, composition, and specific ingredients. Thus, transgenic plant products are known to be obtained with increased starch content, improved starch quality, or a different fatty acid composition.

[0070] The compounds of formula I according to the present invention or their salts are preferably used in the cultivation of economically important genetically modified crops and ornamental plants, for example cereals such as wheat, barley, rye, oats, millet, rice, cassava and corn, or in the cultivation of sugar beets, cotton, soybeans, rapeseed, potatoes, tomatoes, peas and other vegetable plants. The compounds of formula I are preferably used in the cultivation of useful plants with herbicides which are resistant or have been rendered resistant to the toxic effects of the herbicides by genetic engineering.

[0071] Conventional methods for breeding plants with improved traits compared to known plants include, for example, conventional 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:

[0072] - genetic engineering of crop plants to improve starch synthesis in plants (e.g. WO 92 / 11376, WO 92 / 14827, WO 91 / 19806);

[0073] - transgenic crop plants resistant to specific herbicides, such as glufosinate herbicides (e.g. EP-0242236 A, EP-0242246 A) or glyphosate herbicides (WO 92 / 00377), or sulfonylurea herbicides (EP-0257993 A, US Pat. No. 5,013,659 A);

[0074] - genetically modified crop plants, such as cotton, that produce Bacillus thuringiensis toxins (Bt toxins) that protect against attack by certain pests (EP-0142924 A, EP-0193259 A);

[0075] - Transgenic crop plants with improved fatty acid composition (WO 91 / 13972).

[0076] Numerous molecular biotechniques are known for producing transgenic plants with improved traits (see, for example, Sambrook et al., 1989, Molecular Amplification, A Laboratory Manual, 2nd ed., Cold Spring Harbor Laboratory Press, Cold Spring Harbor, New York; or Winnacker, "Gene und Klone," VCH Weinheim, 2nd ed., 1996, or Christou, "Trends in Plant Science," 1 (1996), 423-431). To carry out genetic engineering operations, nucleic acid molecules can be introduced into plasmids, and mutations or sequence changes can be generated by recombination of DNA sequences. 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. To connect DNA fragments to one another, it is possible to attach binding partners or linkers to the fragments.

[0077] Plant cells in which the activity of a gene product is reduced can be prepared, for example, by expressing at least one appropriate antisense RNA, sense RNA to achieve a cosuppression effect, or by expressing at least one appropriately constructed ribozyme that specifically cleaves the transcript of the gene product.

[0078] For this purpose, it is possible to use a DNA molecule that comprises the entire coding sequence of the gene product, including any flanking sequences that may be present, and to use a DNA molecule that comprises only a portion of the coding sequence, which portion must be long enough to achieve an antisense effect in the cell. Sequences that are highly homologous to the coding sequence of the gene product, but not identical thereto, can also be used.

[0079] When expressing nucleic acid molecules in plants, the synthesized protein can be localized in any desired plant cell compartment. However, in order to localize in a specific compartment, it is possible, for example, to link the coding region to the DNA sequence to ensure localization at a specific position. 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).

[0080] Transgenic plant cells can be incorporated into whole plants using known techniques. Transgenic plants can be of any desired plant variety, i.e., monocotyledons and dicotyledons. 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 (=foreign) genes or gene sequences.

[0081] When the active substances of the present invention are used on genetically modified crops, in addition to the harmful plant growth inhibitory effects observed on other crops, they often exhibit specific effects on the corresponding genetically modified crops, such as improved or expanded weed control, improved application rates, preferably a good combination of the resistance of the genetically modified crop and the performance of the herbicide, and effects on the growth and yield of the genetically modified crop plants. Therefore, the present invention also provides the use of the compounds as herbicides for controlling harmful plants in genetically modified crop plants.

[0082] Furthermore, the compounds of the present invention can significantly regulate the growth of crop plants. By modulating plant metabolism, these compounds can be used to control plant composition and promote harvest, for example by causing plant desiccation and dwarfing. Furthermore, they are suitable for regulating and inhibiting undesirable plant growth without disrupting crop growth. Inhibiting plant growth plays a very important role in many monocotyledonous and dicotyledonous crops because it can reduce or completely prevent lodging.

[0083] The compound of the present invention can be applied using general formulations, and wettable powders, emulsion concentrates, sprayable solutions, powders or granules can be used. Thus, the present invention also provides herbicidal compositions comprising compounds of formula I. According to common biological and / or chemical physical parameters, compounds of formula I can be formulated in a variety of ways. Suitable formulation selection examples are: wettable powders (WP), water-soluble powders (SP), water-soluble concentrates, emulsion concentrates (EC), emulsions such as oil-in-water dispersions and water-in-oil dispersions (EW), sprayable solutions, suspension concentrates (SC), dispersible oil suspensions (OD), suspensions with oil or water as diluents, solutions of miscible oils, powders (DP), capsule suspensions (CS), seeded compositions, granules for broadcasting and soil application, spray granules, coated granules and absorption granules, water-dispersible granules (WG), water-soluble granules (SG), ULV (ultra-low volume) formulations, microcapsules and wax products. These individual formulation types are known and are described, for example, in Winnacker-Küchler, "Chemische Techonologie" [Chemical Technology], Vol. 7, C. Hauser Verlag Munich, 4th edition 1986; Wade van Valkenburg, "Pesticide Formulations", Marcel Dekker, NY, 1973; K. Martens, "Spray Drying" Handbook, 3rd edition 1979, G. Goodwin Ltd. London.

[0084] Necessary formulation auxiliaries, such as inert substances, surfactants, solvents and other additives are likewise known and described in, for example, Watkins, "Handbook of Powder Diluents, Pesticides and Carriers," 2nd ed., Darland, Caldwell, NJ; Hvophen, "Introduction to Clay Colloid Chemistry," 2nd ed., J. Wiley and Sons, NY; C. Marsden, "Solvent Guide," 2nd ed., Interscience, NY 1963; McCutcheon, "Detergents and Emulsifiers Annual," MC Publishing Company, Ridgewood, NJ; Sisley and Wood, "Encyclopedia of Surfactants," Chemical Publishing Company, NY 1964; of [Ethylene oxide adduct surfactants], Wiss. Verlagagesell. Stuttgart 1976; Winnacker-Küchler, “Chemische Technologie” [Chemical Technology], Vol. 7, C. Hauser Verlag Munich, 4th edition 1986.

[0085] Wettable powders are homogeneously dispersible in water and contain, in addition to the active substance, a diluent or inert substance, ionic and nonionic surfactants (wetting agents, dispersants), for example, polyethoxylated alkylphenols, polyethoxylated fatty alcohols, polyoxyethylated fatty amines, fatty alcohol polyglycol ether sulfates, alkylsulfonates, alkylphenylsulfonates, sodium lignosulfonate, sodium 2,2'-dinaphthomethane-6,6'-disulfonate, sodium dibutylnaphthalenesulfonate or sodium oleoylmethyltaurate. To prepare wettable powders, the herbicide active substance is finely ground, for example using conventional apparatus such as hammer mills, fan mills or jet mills, and the adjuvants are mixed in simultaneously or sequentially.

[0086] The concentrated emulsion is prepared by dissolving the active substance in an organic solvent such as butanol, cyclohexanone, dimethylformamide, xylene or a mixture of higher boiling aromatic compounds or hydrocarbons or solvents, and adding one or more ionic and / or nonionic 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, alkylaryl polyglycol ethers, fatty alcohol polyglycol ethers, propylene oxide-ethylene oxide condensation products, alkyl polyethers, sorbitan esters such as sorbitan fatty acid esters, or polyoxyethylene sorbitan esters such as polyoxyethylene sorbitan fatty esters.

[0087] Powders are obtained by grinding the active substance with finely divided solid materials, such as talc, natural clays such as kaolin, bentonite and pyrophyllite, or diatomaceous earth. Suspensions in water or oil can be prepared, for example, by wet grinding using a commercially available bead mill, with or without the addition of a surfactant of the type described above for the other formulations.

[0088] Emulsions such as oil-in-water emulsions (EW) can be prepared using aqueous organic solvents using stirrers, colloid mills and / or static mixers and, if desired, adding surfactants of another formulation type as described above.

[0089] Granules can be prepared by spraying the active substance onto an adsorbent and granulating with an inert material, or by concentrating the active substance onto the surface of a carrier such as sand or kaolinite and granulating the inert material with a binder such as polyvinyl alcohol, sodium polyacrylate, or mineral oil. Suitable active substances can be granulated using methods for preparing fertilizer granules and, if desired, mixed with fertilizers. Aqueous suspension granules can be prepared using conventional methods, such as spray drying, fluidized bed granulation, disc granulation, mixing using a high-speed mixer, and extrusion in the absence of solid inert materials.

[0090] For the preparation of granules using a mill, fluidized bed, extruder, and spraying, see, for example, the following processes: "Spray Drying Handbook," 3rd ed. 1979, G. Goodwin Ltd., London; J. E. Browning, "Agglomeration," Chemistry and Engineering, 1967, pp. 147ff; "Perry's Chemical Engineer's Handbook," 5th ed., McGraw-Hill, New York, 1973, pp. 8-57. For the formulation of crop protection products, see, for example, G. C. Lingman, "Weed Control as a Science," John Wiley & Sons, New York, 1961, pp. 81-96 and J. D. Frieder, S. A. Evans, "Weed Control Handbook," 5th ed., Blackwell Scientific Research, Oxford, 1968, pp. 101-103.

[0091] Agrochemical formulations typically contain 0.1 to 99% by weight, particularly 0.1 to 95% by weight, of the active substance of Formula I. The active substance concentration in wettable powders is, for example, from about 10 to 99% by weight, with the formulation components typically comprising the remainder to 100% by weight. The active substance concentration in emulsifiable concentrates can range from about 1 to 90% by weight, preferably 5 to 80%. Powder formulations contain 1 to 30% by weight of active substance, typically preferably 5 to 20% by weight, while sprayable solutions contain approximately 0.05 to 80% by weight, preferably 2 to 50% by weight. The active substance content in water-suspendable granules depends primarily on whether the active substance is liquid or solid, and on the adjuvants, fillers, etc. used in granulation. The active substance content in water-suspendable granules is, for example, between 1 and 95% by weight, preferably between 10 and 80% by weight.

[0092] The active substance formulations may additionally include tackifiers, wetting agents, dispersants, emulsifiers, penetrants, preservatives, antifreeze agents, solvents, fillers, carriers, colorants, antifoams, evaporation inhibitors and, generally, pH and viscosity regulators which are customary in each case.

[0093] Based on these formulations, it is also possible to mix with other pesticide active substances such as insecticides, acaricides, herbicides and fungicides, as well as with safeners, fertilizers and / or plant growth regulators, either as premixes or as canned mixes.

[0094] In mixed formulations or tank-mixed formulations, suitable active substances that can be mixed with the active substance of the present invention are, for example, known substances described in "World New Pesticide Variety Technology Encyclopedia", China Agricultural Science and Technology Press, September 2010, and the literature cited therein. For example, the following herbicide active substances can be mixed with the mixture of formula I (Note: the name of the compound is either the common name according to the International Organization for Standardization (ISO) or the chemical name, with a code number when appropriate): acetochlor, butachlor, alachlor, isopropyl metolachlor, isopropyl metolachlor, S-isopropyl metolachlor, pretilachlor, acetochlor, acetochlor, naphthiachlor, R-(l-)naphthiachlor, propanil, mefenacet, bisbencarb, fluazifop, flufenacet, cyfluthrin, flumethalin, bromomethalin, dimethathiachlor, high-efficiency dimethathiachlor, ethoxymethalin, flufenacet, methoxymethalin, metazachlor, isopropyltrimonium chloride, high-efficiency cyfluthrin, Dipropylene glycol, pethoxachlor, butyrac, cyproconazole, flumethalin, heptamiprole, isobutachlor, propargyl chloramine, terbutachlor, dimethylaminopropylamine, dimethoate, chlorfenapyr, trimethylcyclohexane, chlorfenapyr, propyracyl chloramine, valeryl chloramine, carbamyl, new Yanling, tricyclic chlorfenapyr, butenesulfonamide, butenesulfonamide, mesotrione, benzylchlor, quinone, benzfluorosulfonamide, naphthamide, acetoacetamide, naphthamide, thiazolin, cypermethrin, benzylchlor, benzylchlor, cypermethrin, benzylchlor, cypermethrin, atrazine, simazine, promethazine, cyanamide, simethazine, ametryn, propazine, isopropylamine, fluroxypyr, terbutylamine, terbutylazine, triazine fluazifone, cyprodinil, gampopazine, thiophanate , Promethazine, Simatolin, Azide, Dichlorvos, Isopropylamine, Cyprodinil, Metazine, Another Butylazine, Second Butylazine, Terbutalone, Methoxypropylamine, Cyanamide, Cyanocyanine, Kolazone, Atrazine, Metazine, Glycyrrhizin, Cyanuric acid, Indaziflam, Chlorsulfuron, Metsulfuron-methyl, Bensulfuron-methyl, Chlorimuron-methyl, Bensulfuron-methyl, Thisulfuron-methyl, Pyrazosulfuron-methyl, Metsulfuron-methyl, Iodosulfuron-methyl sodium salt, Formamidosulfuron-methyl, Ethylsulfuron-methyl, Bensulfuron-methyl, Metsulfuron-methyl, Nicosulfuron, Ethamidosulfuron-methyl, Acesulfuron-methyl, Ethoxysulfuron-methyl, Cyprodinil, Sulfonsulfuron-methyl, Tetrazosulfuron, Fentazuron-methyl, Monosulfuron-methyl, Monosulfuron, Fluazuron-methyl, Flupyrazosulfuron-methyl, Epoxysulfuron Sulfur-methyl, azole pyrazosulfuron, primisulfuron, propensulfuron-methyl, trifloxysulfuron, sulfosulfuron, trifloxysulfuron, trifloxysulfuron, metsulfuron-methyl sodium, primisulfuron, methylthiosulfuron, pyrimidisulfon-methyl, Propyrisulfuron (propyrisulfuron), pyrazosulfuron-methyl, acifluorfen, fomesafen, lactofen, fluazifop-butyl, oxyfluorfen, oxazolidinone, benfibrate, chlorpyrifos ethyl, methylcarboxylic acid butyl, trifluoroacetic acid butyl, methoxy-nitropropane, trifluosuccinate, fluorinated herbicide ether, flutosulfuron, nitropropane, methylpyralid, dimethoate, flutosulfuron, flutosulfuron ester, Halosafen, chlorotoluron, isoproturon, linuron, diuron,Saproron, fluuron, benzylthiocarb, methyl benzylthiocarb, benzylthiocarb, sulfothiocarb, isoxalon, terbuthiuron, clodinafuron, chlorbrom, methylthiocarb, acetylthiocarb, methoxythiocarb, bromothiocarb, methoxythiocarb, greenthiocarb, cyclomethuron, fenothuron, flusulfuron, chlorthiocarb ... Anisuron, Methiuron, Chloreturon, Tetrafluoroethylene, Betaine, Betaine-ethyl ester, Betaine, Sulfur-propyl, Tercloflin, Avenaline, Anipropetrol, Chlorpropam, Dichlorobenzyl, Methiol, Chlorpropam, Carboxazole, Chlorprocarb, Fenasulam, BCPC, CPPC, Carbasulam, Butylcarb, Methiol, Methiol, Methiol, Wild wheat dapoxetine, Piperidin, Methiol, Echinochloacarb, Cyclohexanil, Avenaline, Junda, Ethiocarb, Turpan, Kecao Meng, Bencloflin, Zhongcaodan, Sulfadimethoxam, Methiobencarb, Isopolinate, Methiobencarb, 2,4-D butyl ester, 2-Methyl-4-chloro sodium, 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 propionic acid salt, 2,4-D butyric acid, 2-Methyl-4-chloropropionic acid, 2-Methyl-4-chloropropionic acid salt, 2-Methyl-4-chlorobutyric acid, 2,4,5-T, 2,4,5-T propionic acid, 2,4,5-T butyric acid, 2-Methyl-4-chloramine salt, Mediben, cypermethrin, cypermethrin, Cypermethrin, trichlorobenzoic acid, ammonia dichlorobenzoic acid, methoxytrichlorobenzoic acid, diclofenac , fluazifop-butyl, fluazifop-butyl-P, flupyralid, high-efficiency fluazifop-butyl, quizalofop-butyl, quizalofop-butyl-P, oxazolidinone-butyl, oxazolidinone-butyl, cyhalofop-butyl, oxadiazol-butyl, cyhalofop-butyl, oxadiazol-butyl, cyhalofop-butyl, oxadiazol-butyl, clodinafop-butyl, thiazolinone, clodinafop-butyl, chlorfenapyr, trifloxystrobin, isocyanate, paraquat, diquat, oryzalin, ethylbutylfluanid, isopropylcarbamide, sulfenthralin, cyprodinil, aminopropylfluanid, ethylbutylfluanid, chloroethylfluanid, aminoethylfluanid, diclofenac, diclofenac, glyphosate, phosphine, glufosinate, methylaminophosphine, glufosinate, piperphosphine, bialaphos, dichlorvos, dichlorvos Scattered phosphorus, chlorpyrifos, chlorpyrifos, chlorpyrifos, dimethoate, chlorpyrifos, imazapic, imazapic, imazapic, chlorpyrifos ammonium, imazapic, imazapic, clofopyralid, clofopyralid isooctyl ester, clopyralid, amilcylopyr, triclopyralid, fluthiopyr, halofopyr, triclopyralid, thiopyralid, flupyridamole, chlorpyrifos, flupyridamole, chlorpyrifos, flupyridamole, flupyridamole, triclopyridinol ...Hexazinone, Metamitron, Ethylmetazolin, Ametridione, Amibuzin, Bromoxynil, Octanoyl Bromoxynil, Octanoyl Ioxyl, Ioxyl, Dichlobenil, Diphenylacetonitrile, Dipyridoxal, Hydroxypyridoxal, Iodobonil, Sulfursulfuron, Difluorosulfuron, Penoxsulam, Sulfursulfuron, Chlorosulfuron, Dichlorosulfuron, Pyroxypyramide, Fluorosulfuron, Bispyribac-butyl, Cyclopyramide, Pyroxypyramide, Pyroxypyramide, Bispyribac-butyl, Cyclopyramide, Pyroxypyramide, Bispyribac-butyl, Mesotrione, Sulcotrione, Tembotrione, Tefuryltrione, Bicyclopyrone, Ketodpiradox, Isoxaflutole, Isoxachlorpyrifos, Fenoxasulfone, M Ethiozolin, isopropylpyraclostrobin, pyrasulfobutyl, pyrazoline, wild yanquat, benzylpyrachlor, pyrazoline, pyrasulfotole, benzylpyrazone, pyroxasulfone, pyrazoline, fluazifop, chlorfenapyr, amine pyraclostrobin, pyrazoline, fluazifop, sulfentrazone, Bencarbazone, bispyribac, fluazifop-butyl, bromocriptine, isothiocyanate, cypermethrin, cypermethrin, terclopyralid, Flupropacil, indolone, flumethoxal, fluazifop-butyl, cypermethrin, phthalein, Flumezin, pentachlorophenol (sodium), dinitrophenol, dinitrophenol, dinitrophenol, dioxin, dioxetone, oxadiazol, oxadiazol, cyclopentane Fluazifop, flumethoxam, fluazifop-butyl, tetrazolam, flupyridazone, herbicide-resistant, bromomyxin, dimethylpyridazone, pyridafol, quinclorac, quinmechlor, bentazon, pyridazone, oxaziclomefop, chlorpyrifos, isopropylpyridazone, cyproconazole, isopropylpyridazone, indole, sodium chlorate , dalapon, trichloroacetic acid, monochloroacetic acid, hexachloroacetone, tetrafluoropropionic acid, grass fast, bromophenol oxime, triazole sulfonate, methomyl, furochlor, furochlor, ethyl furochlor, chloranil, chlorthalid, fluchloralidone, barnyard grass, acrolein, benzylpyridinium chloride, benzylpyridinium chloride, avena sativa ester, thiadiazole, cotton amine, hydroxythiocarb, methoxybenzone, benzylpyridinium chloride, chloranil, trichloropropionic acid, Al orac, Diethamquat, Etnipromid, Iprymidam, Ipfencarbazone, Thiencarbazone-methyl, Pyrimisulfan, Chlorflurazole, Tripropindan, Sulglycapin, Methylsulfuron, Cambendichlor, Cyprodinil, Thiencarbazone, Fenthiocyanate ...D489,LS 82-556, KPP-300, NC-324, NC-330, KH-218, DPX-N8189, SC-0744, DOWCO535, D K-8910, V-53482, PP-600, MBH-001, KIH-9201, ET-751, KIH-6127 and KIH-2023. ,

[0095] When used, if necessary, commercially available formulations are diluted in a common manner, for example, in the case of wettable powders, concentrated emulsions, suspensions and granules suspended in water, with water dilution. Powders, granules used for soil application or solutions for broadcasting and spraying generally do not require further dilution with an inert substance before use. The required use amount of the compound of formula I varies with external conditions, such as temperature, humidity, the nature of the herbicide used, etc. It can have a large range of variation, for example between 0.001 and 1.0 kg ai / ha, or more active substance, but preferably between 0.005 and 750 g ai / ha, particularly between 0.005 and 250 g ai / ha. DETAILED DESCRIPTION

[0096] The following examples are provided to illustrate the present invention and should not be considered to limit the present invention in any way. The scope of the rights claimed in the present invention is described in the claims.

[0097] Given the economical efficiency and diversity of the compounds, we have selected and synthesized a number of compounds. A selection of these compounds is listed in Table 1 below. The specific compound structures and corresponding compound information are shown in Table 1. The compounds in Table 1 are intended to better illustrate the present invention but are not intended to limit the present invention. Those skilled in the art should not interpret this as limiting the scope of the present invention to the following compounds.

[0098] Table 1 Compound structures and their 1 H NMR

[0099] Several methods for preparing the compounds of the present invention are described in detail in the following schemes and examples. The starting materials can be purchased commercially or can be prepared by methods known in the literature or as described in detail. It will be understood by those skilled in the art that other synthetic routes can also be used to synthesize the compounds of the present invention. Although the specific starting materials and conditions in the synthetic routes have been described below, they can be easily replaced with other similar starting materials and conditions, and these modifications or variations of the preparation methods of the present invention that result in various isomerizations of the compounds are included within the scope of the present invention. In addition, the preparation methods described below can be further modified according to the present disclosure using conventional chemical methods well known to those skilled in the art. For example, appropriate groups can be protected during the reaction, etc.

[0100] The following process examples are provided to facilitate a further understanding of the preparation methods of the present invention. The specific substances, types, and conditions used are intended to further illustrate the present invention and are not intended to limit its reasonable scope. The reagents used in the synthesis of the compounds shown in the table below are either commercially available or can be readily prepared by one of ordinary skill in the art.

[0101] Examples of representative compounds are shown below. The synthesis methods of other compounds are similar and will not be described in detail here.

[0102] 1. Synthesis of Compound 1

[0103] (1) 7-Fluoro-1H-indole (1-1) (5.0 g, 36.3 mmol, 1 eq) was dissolved in 80 ml of THF and added to a 250 ml single-necked flask. The mixture was cooled to -78°C under N2 protection and n-butyllithium (1.2 eq) was added dropwise. The mixture was stirred for 1 h. A solution of trimethylsilyl chloride (1.3 eq) in THF was added dropwise. The mixture was stirred for 1 h. A solution of trimethyl borate (1.5 eq) in THF was added dropwise. The mixture was stirred for 1 h. The reaction was monitored and the product was the main peak. The mixture was quenched with water and extracted with ethyl acetate. The organic phase was used to recover the raw material. The aqueous phase was adjusted to acidic and extracted with ethyl acetate. The mixture was washed with saturated sodium chloride, dried over anhydrous sodium sulfate, concentrated, and mixed. The mixture was separated by normal phase separation (EA / PE = 1 / 5) to obtain 1-3 (1.7 g).

[0104] (2) Compound 1-3 (1.7 g, 9.5 mmol, 1 eq) obtained above, methyl 4-amino-3,6-dichloro-5-fluoropicolinate (3.41 g, 14.25 mmol, 1.5 eq) and cesium fluoride (2.89 g, 19 mmol, 2 eq) were dissolved in a mixture of 1,4-dioxane (16 ml) and water (2 ml) and added to a 100 ml single-necked bottle. The mixture was ventilated once with nitrogen. 1,1'-bis(diphenylphosphino)ferrocenepalladium (II) dichloromethane complex (76.95 mg, 0.095 mmol, 0.01 eq) was added, and the mixture was ventilated three times. The mixture was heated at 100°C and refluxed for 12 h. After monitoring the completion of the reaction, the solvent was dried by rotary evaporation, and the mixture was extracted with water and ethyl acetate. The organic phase was washed twice with saturated brine and dried over anhydrous sodium sulfate. The sample was mixed and separated by normal phase separation (EA / PE=1 / 8) to obtain 1-4 (2.3 g).

[0105] (3) 1-4 (2.3 g, 6.81 mmol, 1 eq) was dissolved in a mixture of tetrahydrofuran (16 ml) and water (4 ml) and added to a 100 ml single-necked flask. Lithium hydroxide (0.45 g, 20.43 mmol, 3 eq) was added with stirring at room temperature and allowed to react at room temperature for 4 h. The reaction was monitored for completion, the tetrahydrofuran was dried, and diluted hydrochloric acid was added to acidify the mixture. The product was precipitated and filtered to obtain 1-5 (2 g).

[0106] (4) 1-5 (0.1 g, 0.31 mmol, 1 eq), tetrahydrofurfuryl alcohol (37.86 mg, 0.37 mmol, 1.2 eq), and triethylamine (93.79 mg, 0.93 mmol, 3 eq) were dissolved in 10 ml of dichloromethane and added to a 100 ml single-necked flask. 1H-Benzotriazol-1-yloxytripyrrolidinophosphate (192.93 mg, 0.37 mmol, 1.2 eq) was added with stirring at room temperature and allowed to react for 1 h. After monitoring the reaction completion, silica gel was added directly to the sample and the mixture was separated by normal phase separation (EA / PE = 1 / 10) to obtain compound 1 (48 mg, yield 38%).

[0107] Biological activity evaluation:

[0108] The activity level standards for plant damage (i.e., growth control rate) are as follows:

[0109] Level 9: Complete death;

[0110] Level 8: Growth control rate is greater than or equal to 90% and less than 100%;

[0111] Level 7: Growth control rate is greater than or equal to 80% and less than 90%;

[0112] Level 6: Growth control rate is greater than or equal to 70% and less than 80%;

[0113] Level 5: Growth control rate is greater than or equal to 50% and less than 70%;

[0114] Level 4: Growth control rate is greater than or equal to 30% and less than 50%;

[0115] Level 3: Growth control rate is greater than or equal to 20% and less than 30%;

[0116] Level 2: Growth control rate is greater than or equal to 10% and less than 20%;

[0117] Level 1: Growth control rate is less than 10%;

[0118] Level 0: No effect.

[0119] The above growth control rates are fresh weight control rates.

[0120] Post-emergence test experiment:

[0121] Monocotyledonous and dicotyledonous weed seeds (artemisia selengensis, shepherd's purse, velvet, cleaver, chickweed, wheat family, sedge, alopecuroides, Japanese alopecuroides, goosegrass, sedge, hard grass, small fleabane, candle grass, speedwell, brome, knotweed, phragmites, amaranth, quinoa, dayflower, sonchus, field bindweed, prickly lettuce, nightshade, amaranth, crabgrass, barnyard grass, green foxtail, golden foxtail, stephanotis, duck tongue grass, wild arrowhead, firefly rush, cyperus, cardinal sedge, sedge with a different shape, floating grass, purslane, cocklebur, morning glory, white wine grass, etc.) and major crops Seeds (wheat, corn, rice, soybean, cotton, rapeseed, millet, sorghum, potato, sesame, castor, cabbage, radish, etc.) were placed in plastic pots filled with soil, covered with 0.5-2 cm of soil, and grown in a well-maintained greenhouse environment. Two weeks after sowing, at the 2-3 leaf stage, the test plants were treated. The test compound of the invention was dissolved in acetone, Tween 80 was added, and 1.5 L / hectare of methyl oleate emulsifiable concentrate was used as a synergist. The solution was diluted with water to a desired concentration and sprayed onto the plants using a spray tower. After three weeks of incubation in the greenhouse, the weed effects were analyzed. Compound dosages were 120, 60, 30, and 18 g ai / ha, and the average value was calculated for three replicates. Representative data are listed in Table 2.

[0122] Table 2 Post-emergence weed test results

[0123] Note: N stands for no data, reference compound A: Control compound B:

[0124] Pre-emergence test experiment:

[0125] Monocotyledonous and dicotyledonous weed seeds, as well as major crop seeds (wheat, corn, rice, soybean, cotton, rapeseed, millet, and sorghum), were placed in plastic pots filled with soil and covered with 0.5-2 cm of soil. The test compounds of the present invention were dissolved in acetone, then diluted with Tween 80 and water to a desired concentration. The solutions were then sprayed immediately after sowing. Following application, the seeds were incubated in a greenhouse for four weeks and observed for the effects. The results showed that most of the agents of the present invention were highly effective at a dosage of 250 g ai / ha, particularly against weeds such as barnyardgrass, crabgrass, and velvetleaf. Many of the compounds also showed good selectivity against corn, wheat, rice, and soybeans.

[0126] At the same time, through testing on major weeds in wheat and rice fields, we found that the compounds described in the present invention generally have good weed control effects. In particular, we noticed that they have extremely high activity against broad-leaved weeds and sedges that are resistant to ALS inhibitors, such as wild arrowhead, firefly rush, Cyperus diversiformis, Artemisia selengensis, Shepherd's purse, wheat bark, Gallia sinensis, and Cyperus rotundus, and have very good commercial value.

[0127] Safety evaluation of transplanted rice and evaluation of paddy field weed control effectiveness:

[0128] After filling a 1 / 1,000,000-hectare tank with paddy field soil, seeds of barnyard grass, firefly rush, and wolfsbane are sown and lightly covered with soil. The tank is then placed in a greenhouse with water at a depth of 0.5-1 cm. The next day or two days later, tubers of wild arrowhead are implanted. The tank is then maintained at a depth of 3-4 cm. When barnyard grass, firefly rush, and wolfsbane reach the 0.5-leaf stage, and when wild arrowhead reaches the primary leaf stage, a wettable powder or suspension prepared according to conventional formulation methods is evenly applied using a pipette to achieve the desired active ingredient dosage.

[0129] Separately, paddy field soil was filled into 1 / 1,000,000 hectare pots and leveled to a water depth of 3-4 cm. The next day, three-leaf rice (japonica rice) was transplanted at a transplanting depth of 3 cm. Five days after transplanting, the compound of the present invention was treated in the same manner as above.

[0130] The growth status of barnyard grass, firefly rush, wolf grass and wild arrowhead were observed with the naked eye on the 14th day after treatment, and the growth status of rice on the 21st day after treatment. The effects were evaluated based on the above-mentioned activity standard levels. Many compounds showed excellent activity and selectivity.

[0131] Note: Seeds of Echinochloa crusgalli, Echinochloa crusgalli, and Lycopodium album were collected from Heilongjiang, China, and were found to be resistant to conventional doses of pyrazosulfuron-methyl.

[0132] Extensive testing has also revealed that many of the compounds and compositions described herein exhibit excellent selectivity against grassy lawns, including zoysia, bermudagrass, tall fescue, bluegrass, ryegrass, and seashore paspalum, controlling many key grass and broadleaf weeds. Tests on sugarcane, soybeans, cotton, sunflower, potatoes, fruit trees, and vegetables, under different application methods, have also demonstrated excellent selectivity and commercial value.

[0133] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and are not limiting. Although the present invention has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that the technical solutions of the present invention may be modified or replaced by equivalents without departing from the spirit and scope of the technical solutions of the present invention.

Claims

1. A substituted nitrogen-containing heterocyclic carboxylic acid ester compound, as shown in the general formula I: in, Q represents CH or C-halogen; X represents a heterocyclylalkyl group; Y represents halogen, alkoxy or haloalkoxy; Z1 and Z2 are independently hydrogen, unsubstituted or optionally substituted with 1-2 R 11 Substituted alkyl, alkenyl or alkynyl, or -COR 12 ; R 11 independently represent halogen, hydroxy, alkoxy, haloalkyl, haloalkoxy, alkylthio, haloalkylthio, amino, alkylamino, dialkylamino, alkoxycarbonyl, aryl or heterocyclic; R 12 represents H, alkyl, haloalkyl, alkoxy, phenyl, phenoxy or benzyloxy; R1, R2, R3, R4, and R5 independently represent hydrogen, halogen, nitro, cyano, thiocyano, hydroxyl, sulfhydryl, carboxyl, sulfonic acid, formyl, haloformyl, azido, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, heterocyclic, aryl, -N(R 21 )2、-(CO)N(R 21 )2、-O(CO)N(R 21 )2、-O(CS)N(R 21 )2、-(SO2)N(R 21 )2、-O(SO2)N(R 21 )2.-PO(OR 22 )2.-OR 22 、-(CO)R 22 、-SR 22 、-(SO)R 22 、-(SO2)R 22 、-Si(R 22 )3. -O(CO)R 22 、-O-(SO2)R 22 、-S(CO)R 22 、-(SO2)OR 22 、-O(CO)OR 22 、-(CO)(CO)OR 22 、-(CO)OR 22 、-ON=C(R 23 2. -CR 23 =N-OH or -CR 23 =NOR 22 , wherein the "alkyl", "alkenyl" or "alkynyl" are independently unsubstituted or selected from halogen, nitro, cyano, hydroxyl, thiol, carboxyl, cycloalkyl, cycloalkenyl, heterocyclyl, aryl, -N(R 21 )2、-(CO)N(R 21 )2、-O(CO)N(R 21 )2、-O(CS)N(R 21 )2、-(SO2)N(R 21 )2、-O(SO2)N(R 21 )2.-OR 22 、-(CO)R 22 、-SR 22 、-(SO)R 22 、-(SO2)R 22 、-O(CO)H、-O(CO)R 22 、-O-(SO2)R 22 、-(CO)OR 22 、-O(CO)OR 22 、-Si(R 22 )3, -O(CO)(CO)OH, -O(CO)(CO)OR 22 , -O-alkyl-(CO)OH or -O-alkyl-(CO)OR 22 substituted by at least one group in; R6, R 21 Each independently represents hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, aryl, heterocyclic, -OR 22 、-(CO)R 22 、-(CO)OR 22 、-alkyl-(CO)OR 22 、-(SO2)R 22 、-(SO2)OR 22 、-alkyl-(SO2)R 22 、-(CO)N(R 24 )2 or -(SO2)N(R 24 )2; R 22 Each of the above groups independently represents an alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, aryl or heterocyclic group, wherein the "alkyl", "alkenyl" or "alkynyl" are independently unsubstituted or selected from halogen, cyano, trialkylsilyl, cycloalkyl, cycloalkenyl, aryl, heterocyclic group, -OR 25 、-SR 25 、-O(CO)R 25 、-(CO)R 25 、-(CO)OR 25 OR-O(CO)OR 25 substituted by at least one group in; R 23 Each independently represents hydrogen, halogen, alkoxy, alkoxyalkyl, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkylalkyl, cycloalkenyl, cycloalkenylalkyl, aryl, arylalkyl, heterocyclyl or heterocyclylalkyl; R 24 each independently represents hydrogen, alkyl, alkenyl, alkynyl, alkoxy, alkylsulfonyl, cycloalkyl, cycloalkylalkyl, cycloalkenyl or cycloalkenylalkyl; or N(R 21 )2、N(R 24 )2 each independently represents a heterocyclic group with a nitrogen atom at the 1-position; R 25 Each independently represents hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, haloalkyl, haloalkenyl, haloalkynyl, phenyl or phenyl substituted by at least one group selected from the following: halogen, cyano, nitro, alkyl, haloalkyl, alkoxy, haloalkoxy, alkoxycarbonyl, alkylthio, alkylsulfonyl or phenoxy substituted by at least one group selected from the following: halogen, cyano, nitro, alkyl, haloalkyl, alkoxy or haloalkoxy; The aforementioned "cycloalkyl", "cycloalkenyl", "heterocyclyl" or "aryl" are each independently unsubstituted or selected from oxo, halogen, cyano, nitro, alkyl, alkenyl, alkynyl, cycloalkyl, haloalkyl, haloalkenyl, haloalkynyl, halocycloalkyl, cycloalkyl substituted by alkyl, -OR 10 、-SR 10 、-(CO)OR 10 、-(SO2)R 10 、-N(R 10 )2 or -O-alkyl-(CO)OR 10 or two adjacent carbon atoms on the ring form a condensed ring with unsubstituted or halogen-substituted -OCH2CH2- or -OCH2O-; R 10 Each independently represents hydrogen, alkyl, haloalkyl, phenyl, or phenyl substituted by at least one group selected from halogen, cyano, nitro, alkyl, haloalkyl, alkoxycarbonyl, alkylthio, alkylsulfonyl, alkoxy or haloalkoxy.

2. A substituted nitrogen-containing heterocyclic carboxylic acid ester compound according to claim 1, characterized in that: X represents a heterocyclic C1-C8 alkyl group; Y represents halogen, C1-C8 alkoxy or halogenated C1-C8 alkoxy; Z1 and Z2 are independently hydrogen, unsubstituted or optionally substituted with 1-2 R 11 Substituted C1-C8 alkyl, C2-C8 alkenyl or C2-C8 alkynyl, or -COR 12 ; R 11 independently 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, diC1-C8 alkylamino, C1-C8 alkoxycarbonyl, aryl or heterocyclic group; R 12 represents H, C1-C8 alkyl, halogenated C1-C8 alkyl, C1-C8 alkoxy, phenyl, phenoxy or benzyloxy; R1, R2, R3, R4, and R5 independently represent hydrogen, halogen, nitro, cyano, thiocyano, hydroxyl, sulfhydryl, carboxyl, sulfonic acid, formyl, haloformyl, azido, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 cycloalkyl, C3-C8 cycloalkenyl, heterocyclic, aryl, -N(R 21 )2、-(CO)N(R 21 )2、-O(CO)N(R 21 )2、-O(CS)N(R 21 )2、-(SO2)N(R 21 )2、-O(SO2)N(R 21 )2.-PO(OR 22 )2.-OR 22 、-(CO)R 22 、-SR 22 、-(SO)R 22 、-(SO2)R 22 、-Si(R 22 )3. -O(CO)R 22 、-O-(SO2)R 22 、-S(CO)R 22 、-(SO2)OR 22 、-O(CO)OR 22 、-(CO)(CO)OR 22 、-(CO)OR 22 、-ON=C(R 23 2. -CR 23 =N-OH or -CR 23 =NOR 22 , wherein the "C1-C8 alkyl", "C2-C8 alkenyl" or "C2-C8 alkynyl" are independently unsubstituted or selected from halogen, nitro, cyano, hydroxyl, mercapto, carboxyl, C3-C8 cycloalkyl, C3-C8 cycloalkenyl, heterocyclyl, aryl, -N(R 21 )2、-(CO)N(R 21 )2、-O(CO)N(R 21 )2、-O(CS)N(R 21 )2、-(SO2)N(R 21 )2、-O(SO2)N(R 21 )2.-OR 22 、-(CO)R 22 、-SR 22 、-(SO)R 22 、-(SO2)R 22 、-O(CO)H、-O(CO)R 22 、-O-(SO2)R 22 、-(CO)OR 22 、-O(CO)OR 22 、-Si(R 22 )3, -O(CO)(CO)OH, -O(CO)(CO)OR 22 , -O-(C1-C8 alkyl)-(CO)OH or -O-(C1-C8 alkyl)-(CO)OR 22 substituted by at least one group in; R6, R 21 Each independently represents hydrogen, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 cycloalkyl, C3-C8 cycloalkenyl, aryl, heterocyclic group, -OR 22 、-(CO)R 22 、-(CO)OR 22 、-(C1-C8 alkyl)-(CO)OR 22 、-(SO2)R 22 、-(SO2)OR 22 、-(C1-C8 alkyl)-(SO2)R 22 、-(CO)N(R 24 )2 or -(SO2)N(R 24 )2; R 22 Each of the "C1-C8 alkyl", "C2-C8 alkenyl", "C2-C8 alkynyl", "C3-C8 cycloalkyl", "C3-C8 cycloalkenyl", "aryl" or "heterocyclyl" is independently unsubstituted or selected from halogen, cyano, tri-C1-C8 alkylsilyl, C3-C8 cycloalkyl, C3-C8 cycloalkenyl, aryl, heterocyclyl, -OR 25 、-SR 25 、-O(CO)R 25 、-(CO)R 25 、-(CO)OR 25 OR-O(CO)OR 25 substituted by at least one group in; R 23 Each independently represents hydrogen, halogen, C1-C8 alkoxy, C1-C8 alkoxyC1-C8 alkyl, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 cycloalkyl, C3-C8 cycloalkylC1-C8 alkyl, C3-C8 cycloalkenyl, C3-C8 cycloalkenylC1-C8 alkyl, aryl, arylC1-C8 alkyl, heterocyclyl or heterocyclylC1-C8 alkyl; R 24 Each independently represents hydrogen, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C1-C8 alkoxy, C1-C8 alkylsulfonyl, C3-C8 cycloalkyl, C3-C8 cycloalkylC1-C8 alkyl, C3-C8 cycloalkenyl or C3-C8 cycloalkenylC1-C8 alkyl; or N(R 21 )2、N(R 24 )2 each independently represents a heterocyclic group with a nitrogen atom at the 1-position; R 25 Each independently represents hydrogen, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 cycloalkyl, halogenated C1-C8 alkyl, halogenated C2-C8 alkenyl, halogenated C2-C8 alkynyl, phenyl or phenyl substituted by at least one group selected from the following: halogen, cyano, nitro, C1-C8 alkyl, halogenated C1-C8 alkyl, C1-C8 alkoxy, halogenated C1-C8 alkoxy, C1-C8 alkoxycarbonyl, C1-C8 alkylthio, C1-C8 alkylsulfonyl or phenoxy substituted by at least one group selected from the following: halogen, cyano, nitro, C1-C8 alkyl, halogenated C1-C8 alkyl, C1-C8 alkoxy or halogenated C1-C8 alkoxy; The aforementioned "C3-C8 cycloalkyl", "C3-C8 cycloalkenyl", "heterocyclyl" or "aryl" are each independently unsubstituted or selected from oxo, halogen, cyano, nitro, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 cycloalkyl, halogenated C1-C8 alkyl, halogenated C2-C8 alkenyl, halogenated C2-C8 alkynyl, halogenated C3-C8 cycloalkyl, C3-C8 cycloalkyl substituted by C1-C8 alkyl, -OR 10 、-SR 10 、-(CO)OR 10 、-(SO2)R 10 、-N(R 10 )2 or -O-(C1-C8 alkyl)-(CO)OR 10 or two adjacent carbon atoms on the ring form a condensed ring with unsubstituted or halogen-substituted -OCH2CH2- or -OCH2O-; R 10 They independently represent hydrogen, C1-C8 alkyl, halogenated C1-C8 alkyl, phenyl, or phenyl substituted by at least one group selected from halogen, cyano, nitro, C1-C8 alkyl, halogenated C1-C8 alkyl, C1-C8 alkoxycarbonyl, C1-C8 alkylthio, C1-C8 alkylsulfonyl, C1-C8 alkoxy or halogenated C1-C8 alkoxy.

3. A substituted nitrogen-containing heterocyclic carboxylic acid ester compound according to claim 1 or 2, characterized in that: X represents a heterocyclic C1-C6 alkyl group; Y represents halogen, C1-C6 alkoxy or halogenated C1-C6 alkoxy; Z1 and Z2 are independently hydrogen, unsubstituted or optionally substituted with 1-2 R 11 Substituted C1-C6 alkyl, C2-C6 alkenyl or C2-C6 alkynyl, or -COR 12 ; R 11 independently 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, diC1-C6 alkylamino, C1-C6 alkoxycarbonyl, aryl or heterocyclic group; R 12 represents H, C1-C6 alkyl, halogenated C1-C6 alkyl, C1-C6 alkoxy, phenyl, phenoxy or benzyloxy; R1, R2, R3, R4, and R5 independently represent hydrogen, halogen, nitro, cyano, thiocyano, hydroxyl, mercapto, carboxyl, alkyl, sulfonic acid, formyl, haloformyl, azido, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, C3-C6 cycloalkenyl, heterocyclic, aryl, -N(R 21 )2、-(CO)N(R 21 )2、-O(CO)N(R 21 )2、-O(CS)N(R 21 )2、-(SO2)N(R 21 )2、-O(SO2)N(R 21 )2.-PO(OR 22 )2.-OR 22 、-(CO)R 22 、-SR 22 、-(SO)R 22 、-(SO2)R 22 、-Si(R 22 )3. -O(CO)R 22 、-O-(SO2)R 22 、-S(CO)R 22 、-(SO2)OR 22 、-O(CO)OR 22 、-(CO)(CO)OR 22 、-(CO)OR 22 、-ON=C(R 23 2. -CR 23 =N-OH or -CR 23 =NOR 22 , wherein the "C1-C6 alkyl", "C2-C6 alkenyl" or "C2-C6 alkynyl" are each independently unsubstituted or selected from halogen, nitro, cyano, hydroxyl, mercapto, carboxyl, C3-C6 cycloalkyl, C3-C6 cycloalkenyl, heterocyclyl, aryl, -N(R 21 )2、-(CO)N(R 21 )2、-O(CO)N(R 21 )2、-O(CS)N(R 21 )2、-(SO2)N(R 21 )2、-O(SO2)N(R 21 )2.-OR 22 、-(CO)R 22 、-SR 22 、-(SO)R 22 、-(SO2)R 22 、-O(CO)H、-O(CO)R 22 、-O-(SO2)R 22 、-(CO)OR 22 、-O(CO)OR 22 、-Si(R 22 )3, -O(CO)(CO)OH, -O(CO)(CO)OR 22 , -O-(C1-C6 alkyl)-(CO)OH or -O-(C1-C6 alkyl)-(CO)OR 22 substituted by at least one group in; R6, R 21 Each independently represents hydrogen, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, C3-C6 cycloalkenyl, aryl, heterocyclic group, -OR 22 、-(CO)R 22 、-(CO)OR 22 、-(C1-C6 alkyl)-(CO)OR 22 、-(SO2)R 22 、-(SO2)OR 22 、-(C1-C6 alkyl)-(SO2)R 22 、-(CO)N(R 24 )2 or -(SO2)N(R 24 )2; R 22 Each of the "C1-C6 alkyl", "C2-C6 alkenyl", "C2-C6 alkynyl", "C3-C6 cycloalkyl", "C3-C6 cycloalkenyl", "aryl" or "heterocyclyl" independently represents a C1-C6 alkyl, a C2-C6 alkenyl, a C2-C6 alkynyl, a C3-C6 cycloalkyl, a C3-C6 cycloalkenyl, an aryl or a heterocyclyl, wherein each of the "C1-C6 alkyl", "C2-C6 alkenyl" or "C2-C6 alkynyl" independently represents a C1-C6 alkyl, a C2-C6 alkenyl, a C2-C6 alkynyl, a C3-C6 cycloalkyl, a C3-C6 cycloalkenyl, an aryl, a heterocyclyl, a -OR 25 、-SR 25 、-O(CO)R 25 、-(CO)R 25 、-(CO)OR 25 OR-O(CO)OR 25 substituted by at least one group in; R 23 Each independently represents hydrogen, halogen, C1-C6 alkoxy, C1-C6 alkoxyC1-C6 alkyl, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, C3-C6 cycloalkylC1-C6 alkyl, C3-C6 cycloalkenyl, C3-C6 cycloalkenylC1-C6 alkyl, aryl, arylC1-C6 alkyl, heterocyclyl or heterocyclylC1-C6 alkyl; R 24 Each independently represents hydrogen, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C1-C6 alkoxy, C1-C6 alkylsulfonyl, C3-C6 cycloalkyl, C3-C6 cycloalkylC1-C6 alkyl, C3-C6 cycloalkenyl or C3-C6 cycloalkenylC1-C6 alkyl; or N(R 21 )2、N(R 24 )2 independently represent unsubstituted or substituted by at least one group selected from oxo, C1-C6 alkyl or C1-C6 alkoxycarbonyl R 25 Each independently represents hydrogen, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, halo-C1-C6 alkyl, halo-C2-C6 alkenyl, halo-C2-C6 alkynyl, phenyl or phenyl substituted by at least one group selected from the following: halogen, cyano, nitro, C1-C6 alkyl, halo-C1-C6 alkyl, C1-C6 alkoxy, halo-C1-C6 alkoxy, C1-C6 alkoxycarbonyl, C1-C6 alkylthio, C1-C6 alkylsulfonyl or phenoxy substituted by at least one group selected from the following: halogen, cyano, nitro, C1-C6 alkyl, halo-C1-C6 alkyl, C1-C6 alkoxy or halo-C1-C6 alkoxy; The aforementioned "C3-C6 cycloalkyl", "C3-C6 cycloalkenyl", "heterocyclyl" or "aryl" are each independently unsubstituted or selected from oxo, halogen, cyano, nitro, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, halogenated C1-C6 alkyl, halogenated C2-C6 alkenyl, halogenated C2-C6 alkynyl, halogenated C3-C6 cycloalkyl, substituted C1-C6 alkyl, halogenated C2-C6 alkenyl, halogenated C2-C6 alkynyl, halogenated C3-C6 cycloalkyl, substituted C1-C6 alkyl, Substituted C3-C6 cycloalkyl, -OR 10 、-SR 10 、-(CO)OR 10 、-(SO2)R 10 、-N(R 10 )2 or -O-(C1-C6 alkyl)-(CO)OR 10 or two adjacent carbon atoms on the ring form a condensed ring with unsubstituted or halogen-substituted -OCH2CH2- or -OCH2O-; R 10 Each independently represents hydrogen, C1-C6 alkyl, halogenated C1-C6 alkyl, phenyl, or phenyl substituted by at least one group selected from halogen, cyano, nitro, C1-C6 alkyl, halogenated C1-C6 alkyl, C1-C6 alkoxycarbonyl, C1-C6 alkylthio, C1-C6 alkylsulfonyl, C1-C6 alkoxy or halogenated C1-C6 alkoxy.

4. A substituted nitrogen-containing heterocyclic carboxylic acid ester compound according to any one of claims 1 to 3, characterized in that: It is selected from any one in Table 1.

5. A method for preparing a substituted nitrogen-containing heterocyclic carboxylic acid ester compound according to any one of claims 1 to 4, characterized in that: The following steps are involved: The compound represented by the general formula II is reacted with the compound represented by the general formula III to obtain the compound represented by the general formula I, and the reaction equation is as follows: Wherein, M represents OH or halogen, and the substituents Q, R1, R2, R3, R4, R5, R6, X, Y, Z1 and Z2 are defined as in any one of claims 1 to 4; Preferably, the reaction is carried out in the presence of a solvent, more preferably, a condensing agent and / or a base is added during the reaction; further preferably, the solvent is selected from at least one of DMF, DMA, methanol, ethanol, acetonitrile, dichloroethane, DMSO, Dioxane, dichloromethane or ethyl acetate, the base is selected from at least one of an inorganic base or an organic base, and the condensing agent is selected from at least one of Py-BOP, Py-AOP, EDCI, HOBT, DCC, HBTU or HATU.

6. A herbicide composition, characterized in that: The method comprises a herbicidally effective amount of at least one of the substituted nitrogen-containing heterocyclic carboxylic acid ester compounds according to any one of claims 1 to 4, and preferably further comprises a formulation adjuvant.

7. A method for controlling weeds, characterized in that: The method comprises applying a herbicidally effective amount of at least one of the substituted nitrogen-containing heterocyclic carboxylic acid ester compounds according to any one of claims 1 to 4 or the herbicide composition according to claim 6 on plants or weedy areas.

8. Use of at least one of the substituted nitrogen-containing heterocyclic carboxylate compounds according to any one of claims 1 to 4 or the herbicide composition according to claim 6 for controlling weeds, preferably, the substituted nitrogen-containing heterocyclic carboxylate compounds are used to control weeds in useful crops, and the useful crops are transgenic crops or crops treated with genome editing technology.

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