Novel derivatives of non-coded amino acids and their use as herbicides - Patents.com

Abstract

Novel chemical compounds having herbicidal activity, agricultural compositions, processes for their preparation and their use in crop protection are provided.

Description

[Technical field]

[0001] The present invention relates to novel chemical compounds having herbicidal activity, to processes for their preparation and to their use in crop protection. [Background technology]

[0002] Amino acids and their derivatives are involved in many cellular reactions, and therefore they affect many physiological processes, such as plant growth and development, control of intracellular pH, production of metabolic energy or redox power, and resistance to both abiotic and biotic stresses. All pools of amino acids are induced during stress. For example, proline significantly increases the stress response in some plants and is considered as a compatible osmolyte. In addition, branched-chain amino acids are also dramatically induced during various stress conditions.

[0003] The role of amino acids in plant signal transduction has been recently discussed. In this context, the regulation of amino acid content, flux, and transport through the plant is important for plant adaptation to carbon and nitrogen status, development, and defense.

[0004] The mechanisms underlying the regulation of amino acid pools require further elucidation. The local concentration of amino acids depends on the synthesis and degradation rates of proteins as well as amino acids and transport processes. These processes rather modify the total pool size, which is particularly relevant during periods when bulk degradation occurs, such as germination and senescence. Summary of the Invention [Problem to be solved by the invention]

[0005] There is a constant need for new compounds that are effective in controlling undesired vegetation growth. In the most common situations, such compounds are said to selectively control weed growth in useful crops, such as cotton, rice, corn, wheat, and soybeans, to name a few. Weed growth in such crops, if left unchecked, can cause significant losses, reducing farmer profits and increasing consumer costs. In other situations, herbicides that control all vegetation growth are desired. Examples of areas where complete control of all vegetation is desired are areas around railroad tracks, storage tanks, and industrial storage areas. Identifying new compounds with more effective, less expensive, and environmentally safe herbicidal activity remains a long-standing, unmet need. [Means for solving the problem]

[0006] Summary of the Invention The primary object of the present invention is to provide novel, safe and powerful herbicides.

[0007] The present invention relates to a structure

[0008] [ka] [In the formula, A is a cyclopentadiene, benzene, or indene skeleton containing 1 to 4 heteroatoms, each of which is independently selected from the group consisting of N, S, Se, and O, and one or more of the ring carbon atoms is selected from -SO2CF3, -O-SO2CF3, -NR3 + , -SO2R, -C≡N, -CX3, CX2R, -COX, -CHO, -COR, -CO2R, -CONH2, -CONHR, -CONR2, -N=O, -N≡N + , -N=NR, -CR=NR, -N=CR2, -F, -Cl, -Br, and -I, where X is selected from F, Cl, Br, and I; n is 0 to 5; T is unsubstituted or contains one or two halides, oxygen, -SO2CF3, -O-SO2CF3, -NR3 + , -SO2R, -C≡N, -CX3, CX2R-COX, -CHO, -COR, -CO2R, -CONH2, -CONHR, -CONR2, -F, -N=O, -N≡N + , -N=NR, -CR=NR, -N=CR2, and X is selected from -F, -Cl, -Br, and -I; Z is -COOH, COO-, OH, -OR; COOR with a saturated or unsaturated alcohol residue with a linear, branched, cyclic, aromatic or heteroaromatic chain; -O-(CH2CH2O) n R(n≧1);-O-(CHMeCH2O) n R(n≧1)); a sulfonyl group, a carbamoyl group, a primary amine, a secondary amine, a tertiary amine, a carboxamide, -NR-OR, -O-NR2, a hydrazine, -NH-COR, and a methanimidamide moiety or a salt thereof; R is selected from H, substituted or unsubstituted alkyl, and substituted or unsubstituted aryl groups. or a salt thereof, wherein the agricultural composition comprises at least one agriculturally acceptable carrier.

[0009] The present invention relates to a method for controlling undesirable plant growth, comprising the steps of:

[0010] [ka] [In the formula, A is a cyclopentadiene, benzene, or indene skeleton containing 1 to 4 heteroatoms, each of which is independently selected from the group consisting of N, S, Se, and O, and one or more of the ring carbon atoms is selected from -SO2CF3, -O-SO2CF3, -NR3 + , -SO2R, -C≡N, -CX3, CX2R, -COX, -CHO, -COR, -CO2R, -CONH2, -CONHR, -CONR2, -N=O, -N≡N +, -N=NR, -CR=NR, -N=CR2, -F, -Cl, -Br, and -I, where X is selected from F, Cl, Br, and I; n is 0 to 5; T is unsubstituted or contains one or two halides, oxygen, -SO2CF3, -O-SO2CF3, -NR3 + , -SO2R, -C≡N, -CX3, CX2R, -COX, -CHO, -COR, -CO2R, -CONH2, -CONHR, -CONR2, -F, -N=O, -N≡N + , -N=NR, -CR=NR, -N=CR2, and X is selected from F, Cl, Br and I; Z is -COOH, COO-, OH, -OR; COOR with a saturated or unsaturated alcohol residue with a linear, branched, cyclic, aromatic or heteroaromatic chain; -O-(CH2CH2O) n R(n≧1);-O-(CHMeCH2O) n R(n≧1)); a sulfonyl group, a carbamoyl group, a primary amine, a secondary amine, a tertiary amine, a carboxamide, -NR-OR, -O-NR2, a hydrazine, -NH-COR, and a methanimidamide moiety or a salt thereof; R is selected from H, substituted or unsubstituted alkyl, and substituted or unsubstituted aryl groups. or a salt thereof, comprising applying to the locus of unwanted plant growth a herbicidally effective amount of a compound having the formula:

[0011] The present invention relates to a method for controlling unwanted plant growth, comprising administering to a locus of the unwanted plant growth: a. Structure

[0012] [ka] [In the formula, A is a cyclopentadiene, benzene, or indene skeleton containing 1 to 4 heteroatoms, each of which is independently selected from the group consisting of N, S, Se, and O, and one or more of the ring carbon atoms is selected from -SO2CF3, -O-SO2CF3, -NR3 + , -SO2R, -C≡N, -CX3, CX2R-COX, -CHO, -COR, -CO2R, -CONH2, -CONHR, -CONR2, -F, -N=O, -N≡N + , -N=NR, -CR=NR, -N=CR2, -Cl, -Br, and -I, where X is selected from F, Cl, Br, and I; n is 0 to 5; T is unsubstituted or contains one or two halides, oxygen, -SO2CF3, -O-SO2CF3, -NR3 + , -SO2R, -C≡N, -CX3, CX2R, -COX, -CHO, -COR, -CO2R, -CONH2, -CONHR, -CONR2, -F, -N=O, -N≡N + , -N=NR, -CR=NR, -N=CR2, and X is selected from F, Cl, Br and I; Z is -COOH, COO-, OH, -OR; COOR with a saturated or unsaturated alcohol residue with a linear, branched, cyclic, aromatic or heteroaromatic chain; -O-(CH2CH2O) n R(n≧1);-O-(CHMeCH2O) n R(n≧1)); a sulfonyl group, a carbamoyl group, a primary amine, a secondary amine, a tertiary amine, a carboxamide, -NR-OR, -O-NR2, a hydrazine, -NH-COR, and a methanimidamide moiety or a salt thereof; R is selected from H, substituted or unsubstituted alkyl, and substituted or unsubstituted aryl groups. or a salt thereof, b. a second herbicide; and effectively controlling undesirable plant growth by applying

[0013] The present invention provides a composition for controlling unwanted plant growth, comprising: a. Structure

[0014] [ka] [In the formula, A is a cyclopentadiene, benzene, or indene skeleton containing 1 to 4 heteroatoms, each of which is independently selected from the group consisting of N, S, Se, and O, and one or more of the ring carbon atoms is selected from -SO2CF3, -O-SO2CF3, -NR3 + , -SO2R, -C≡N, -CX3, CX2R, -COX, -CHO, -COR, -CO2R, -CONH2, -CONHR, -CONR2, -F, -N=O, -N≡N + , -N=NR, -CR=NR, -N=CR2, -Cl, -Br, and -I, where X is selected from F, Cl, Br, and I; n is 0 to 5; T is unsubstituted or contains one or two halides, oxygen, -SO2CF3, -O-SO2CF3, -NR3 + , -SO2R, -C≡N, -CX3, CX2R-COX, -CHO, -COR, -CO2R, -CONH2, -CONHR, -CONR2, -F, -N=O, -N≡N + , -N=NR, -CR=NR, -N=CR2, and X is selected from F, Cl, Br and I; Z is -COOH, COO-, OH, -OR; COOR with a saturated or unsaturated alcohol residue with a linear, branched, cyclic, aromatic or heteroaromatic chain; -O-(CH2CH2O) n R(n≧1);-O-(CHMeCH2O) n R(n≧1)); a sulfonyl group, a carbamoyl group, a primary amine, a secondary amine, a tertiary amine, a carboxamide, -NR-OR, -O-NR2, a hydrazine, -NH-COR, and a methanimidamide moiety or a salt thereof; R is selected from H, substituted or unsubstituted alkyl, and substituted or unsubstituted aryl groups. or a salt thereof, b. Atrazine, terbuthylazine, (S)-metolachlor, metolachlor, terbutyrin, simazine, dimethenamid, (S)-dimethenamid, flufenacet, acetochlor, alachlor, isoxaflutole, isoxachlorthole, mesotrione, sulcotrione, metosulam, flumetoslam, pendimethalin, bromoxynil, bentazon, caffentrazone-ethyl, clomazone, nicosulfuron, rimsulfuron, halosulfuron-methyl, metribuzin, flumiclorac-pentyl, prosulfuron, primisulfuron-methy , dicamba, fluthiacet-methyl, pyridate, 2,4-D, clopyralid, diflufenzopyr, fluroxypyr, MCPA, MCPB, mecoprop (MCPP), metobenzuron, thifensulfuron-methyl, aclonifen, EPTC, glyphosate, glufosinate, sulfosate, cyanazine, propaquizafop, metamitron, pyramine, phenmedipham, desmedipham, ethofumesate, triasulfuron, chloridazon, lenacil, triallate, fluazifop, sethoxydim, quizalofop, clopyralid, clethodim, Oxasulfuron, Acifluorfen, Benazolin-ethyl, Sulfentrazone, Chlorimuron-ethyl, Cloransulam-methyl, Fomesafen, Imazamox, Imazaquin, Imazethapyr, Imazapyr, Lactofen, Fenoxaprop (P-ethyl), Thiadiazuron, Tribufos, Trifluralin, Dimethachlor, Napropamide, Quinmelac, Metazachlor, Carbetamide, Dimefurone, Propyzamide, Ethamethosulfuron-methyl, Tebutam, Fluometuron, Prometryn, Norflurazon, Pyrithiobac-sodium, MS MA, DSMA, diuron, flurochloridone, dithiopyr, thiazopyr, oxyfluorfen, ethalfluralin, clodinafop, amidosulfuron, diclofop-methyl, diflufenican, ethoxysulfuron, fentrazamide, flazasulfuron, florasulam, fluazolate, flucarbazone, flupyrsulfuron-methyl sodium, flurtamone, iodosulfuron, isoproturon, chlortoluron, chlorsulfuron, metsulfuron-methyl, sulfosulfuron, tribenuron-methyl, 2,4-DB, 2,4-DP, bifenox, flamprop-M, imazamethabenz-methyl, ioxynil, tralkoxydim, fluoroglycofen-ethyl, methabenzthiazuron, isoxaben, prosulfocarb, difenzoquat methyl sulfate, pretilachlor, cinosulfuron, fenclorim, bensulfuron-methyl, imazosulfuron, pyrazosulfuron-ethyl, azimsulfuron, esprocarb, mefenacet, molinate, at least one herbicide selected from the group consisting of propanil, pyrazolate, cyhalofop-butyl, bispyribac-sodium, pyriminobac-methyl, cafenstrole, oxadiargyl, oxadiazon, bromobutide, MY-100, dymron, NB061, MK243, HW-52, AC014, ametryn, hexazinone, asulam, azafenidin, tebuthiuron, ethametsulfuron-methyl, or combinations thereof; and c. at least one agriculturally acceptable carrier The present invention further provides a composition comprising a mixture of:

[0015] The present invention provides a composition for controlling unwanted plant growth, comprising: a. Structure

[0016] [ka] [In the formula, A is a cyclopentadiene, benzene, or indene skeleton containing 1 to 4 heteroatoms, each of which is independently selected from the group consisting of N, S, Se, and O, and one or more of the ring carbon atoms is selected from -SO2CF3, -O-SO2CF3, -NR3 + , -SO2R, -C≡N, -CX3, CX2R-COX, -CHO, -COR, -CO2R, -CONH2, -CONHR, -CONR2, -F, -N=O, -N≡N + , -N=NR, -CR=NR, -N=CR2, -Cl, -Br, and -I, where X is selected from F, Cl, Br, and I; n is 0 to 5; T is unsubstituted or contains one or two halide atoms, oxygen, -SO2CF3, -O-SO2CF3, -NR3 + , -SO2R, -C≡N, -CX3, -COX, -CHO, -COR, -CO2R, -CONH2, -CONHR, -CONR2, -F, -N=O, -N≡N + , -N=NR, -CR=NR, -N=CR2, and X is selected from F, Cl, Br and I; Z is -COOH, COO-, OH, -OR; COOR with a saturated or unsaturated alcohol residue with a linear, branched, cyclic, aromatic or heteroaromatic chain; -O-(CH2CH2O) n R(n≧1);-O-(CHMeCH2O) n R(n≧1)); a sulfonyl group, a carbamoyl group, a primary amine, a secondary amine, a tertiary amine, a carboxamide, -NR-OR, -O-NR2, a hydrazine, -NH-COR, and a methanimidamide moiety or a salt thereof; R is selected from H, substituted or unsubstituted alkyl, and substituted or unsubstituted aryl groups. or a salt thereof, b. at least one plant growth regulator, and c. at least one agriculturally acceptable carrier The present invention further provides a composition comprising a mixture of: DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0017] The present invention will now be described more fully hereinafter with reference to the accompanying examples, in which embodiments of the invention are illustrated. However, the present invention may be embodied in many different forms and should not be construed as being limited to the embodiments set forth herein, but rather these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art.

[0018] In one embodiment, the present invention provides a method for producing a pharmaceutical composition comprising the steps of:

[0019] [ka] [In the formula, A is a cyclopentadiene, benzene, or indene skeleton containing 1 to 4 heteroatoms, each of which is independently selected from the group consisting of N, S, Se, and O, and one or more of the ring carbon atoms is selected from -SO2CF3, -O-SO2CF3, -NR3 + , -SO2R, -C≡N, -CX3, CX2R, -COX, -CHO, -COR, -CO2R, -CONH2, -CONHR, -CONR2, -N=O, -N≡N + , -N=NR, -CR=NR, -N=CR2, -F, -Cl, -Br, and -I, where X is selected from F, Cl, Br, and I; n is 0 to 5; T is unsubstituted or contains one or two halides, oxygen, -SO2CF3, -O-SO2CF3, -NR3 + , -SO2R, -C≡N, -CX3, CX2R-COX, -CHO, -COR, -CO2R, -CONH2, -CONHR, -CONR2, -F, -N=O, -N≡N + , -N=NR, -CR=NR, -N=CR2, and X is selected from -F, -Cl, -Br, and -I; Z is -COOH, COO-, OH, -OR; COOR with a saturated or unsaturated alcohol residue with a linear, branched, cyclic, aromatic or heteroaromatic chain; -O-(CH2CH2O) n R(n≧1);-O-(CHMeCH2O) n R(n≧1)); a sulfonyl group, a carbamoyl group, a primary amine, a secondary amine, a tertiary amine, a carboxamide, -NR-OR, -O-NR2, a hydrazine, -NH-COR, and a methanimidamide moiety or a salt thereof; R is selected from H, substituted or unsubstituted alkyl, and substituted or unsubstituted aryl groups. or a salt thereof, comprising at least one agriculturally acceptable carrier.

[0020] According to some embodiments of the compositions of the present invention, A is a heterocyclic aromatic ring substituted with one or more electron withdrawing groups (EWGs). As used herein, the term "electron withdrawing group" (EWG) refers to an atom or group that withdraws electron density from a neighboring atom or aromatic ring, usually by, but not limited to, resonance and / or inductive effects. In the context of the present invention, a non-limiting list of EWGs of the present invention includes trifluoromethanesulfonyl and triflate groups; substituted ammonium groups, such as, but not limited to, -NR3+ (R is alkyl(s) or H); nitro and nitroso groups, -NO2, -N=O; sulfonic acid and sulfonyl groups (-O)-SOH, -SOR; cyano groups, trihalomethyl groups -CX3 (X is F, Cl, Br, I); haloformyl groups -COX (X is F, Cl, Br, I); formyl and acyl groups -CHO, -COR; (substituted) aminocarbonyl groups -CONH2, -CONHR, -CONR2; halo groups -F, -Cl, -Br, -I; azo groups -N≡N+ or -N=NR; imino groups -CR=NR or -N=CR2.

[0021] According to some embodiments of the above composition, Z can be any of a variety of groups, including but not limited to, carboxyl or its salts, -COOH or COO-, hydroxyl -OH, ether -OR, esters COOR with saturated or unsaturated alcohol groups having linear, branched, cyclic or aromatic / heteroaromatic chains, ethylene- and polyethylene glycol-O-(CH2CHO) n R (n≧1, R is H or alkyl), propylene and polypropylene glycol-O—(CHMeCHO) nR (n≧1, R is H or alkyl), phosphate (substituted and unsubstituted), sulfate / sulfonyl; carbamoyl groups consisting of primary, secondary and tertiary amides substituted with linear, branched, cycloaliphatic, cycloaromatic / heteroaromatic chains, ethylene glycol and polyethylene glycol (as above), propylene glycol, polypropylene glycol (as above), primary amines, secondary amines, tertiary amines, carboxamides, alkoxyamine groups of the -NR-OR and -O-NR2 types, hydrazine, acetamide groups -NH-COR, and methanimidamide moieties, or salts thereof.

[0022] According to some embodiments of the above composition, Z is, but is not limited to,

[0023] [ka] It may be TIFF2024524632000008.tif95161.

[0024] According to some embodiments, the composition has the structure

[0025] [ka] [In the formula, each R 1 and R 2 are independently selected from H, Cl; Br; I; -CF3; and -CN, at least one of which is not H, and R 3 is H, -COH, -CN, O or F, R 4is selected from H, saturated or unsaturated aliphatic, linear, branched, cyclic or aromatic chains; ethylene glycol; polyethylene glycol; propylene glycol, polypropylene glycol, ethylpyridine, ethylbenzene, 1-(bromophenyl)ethan-1-one, 1-(1H-inden-3-yl)ethan-1-one, 1-(2,3-dihydro-1H-inden-1-yl)ethan-1-one; 1-(2,3-dihydro-1H-inden-1-yl)propan-1-one; and 1-(1H-inden-3-yl)propan-1-one. or a salt thereof.

[0026] According to some embodiments, the composition has the structure

[0027] [ka] [In the formula, R 1 and R 2 is selected from H, Cl; Br; I; -CF3; and -CN, at least one of which is not H, and R 3 is H, -COH, -CN, O or F, R 4 is selected from H, saturated or unsaturated aliphatic, linear, branched, cyclic or aromatic chains; ethylene glycol; polyethylene glycol; propylene glycol, polypropylene glycol, ethylpyridine, ethylbenzene, 1-(bromophenyl)ethan-1-one, 1-(1H-inden-3-yl)ethan-1-one, 1-(2,3-dihydro-1H-inden-1-yl)ethan-1-one; 1-(2,3-dihydro-1H-inden-1-yl)propan-1-one; and 1-(1H-inden-3-yl)propan-1-one. The compounds include those having the formula:

[0028] According to some embodiments, the composition has the structure

[0029] [ka] [In the formula, R 1 and R2 is selected from H, Cl; Br; I; -CF3; and -CN, at least one of which is not H, and R 3 is H, -COH, -CN, O or F, R 4 is selected from H, saturated or unsaturated aliphatic, linear, branched, cyclic or aromatic chains; ethylene glycol; polyethylene glycol; propylene glycol, polypropylene glycol, ethylpyridine, ethylbenzene, 1-(bromophenyl)ethan-1-one, 1-(1H-inden-3-yl)ethan-1-one, 1-(2,3-dihydro-1H-inden-1-yl)ethan-1-one; 1-(2,3-dihydro-1H-inden-1-yl)propan-1-one; and 1-(1H-inden-3-yl)propan-1-one. The compounds include those having the formula:

[0030] According to some embodiments, the composition has the structure

[0031] [ka] [In the formula, R 1 is selected from Cl; Br; I; -CF3, R 2 and R 3 is H or F, R 4 is selected from H, saturated or unsaturated aliphatic, linear, branched, cyclic or aromatic chains; ethylene glycol; polyethylene glycol; propylene glycol, polypropylene glycol, ethylpyridine, ethylbenzene, 1-(bromophenyl)ethan-1-one, 1-(1H-inden-3-yl)ethan-1-one, 1-(2,3-dihydro-1H-inden-1-yl)ethan-1-one; 1-(2,3-dihydro-1H-inden-1-yl)propan-1-one; and 1-(1H-inden-3-yl)propan-1-one. The compounds include those having the formula:

[0032] According to some embodiments, the composition comprises: (2-bromo-1,3-thiazol-4-yl)(difluoro)acetic acid; difluoro[2-(trifluoromethyl)-1,3-thiazol-4-yl]acetic acid; (2-cyano-1,3-thiazol-4-yl)(difluoro)acetic acid; (2-chloro-1,3-thiazol-4-yl)(difluoro)acetic acid; 2-[2-(2-ethoxyethoxy)ethoxy]ethyl(2-chloro-1,3-thiazol-4-yl)(difluoro)acetate; 2-(2-bromophenyl)-2-oxoethyl(2-chloro-1,3-thiazol-4-yl) (difluoro)acetate; 2-(2,7-methyl-2,3-dihydro-1H-inden-1-yl)-2-oxoethyl (2-chloro-1,3-thiazol-4-yl)(difluoro)acetate; (2-chloro-1,3-oxazol-4-yl)(difluoro)acetic acid; ethyl (2-chloro-1,3-oxazol-4-yl)(difluoro)acetate; difluoro(1,2,3-thiadiazol-4-yl)acetic acid; (1,2,3-thiadiazol-4-yl)acetic acid; (3-chloro-1,2-thiazol-4-yl)(difluoro)acetic acid.

[0033] According to some embodiments of the above composition, a non-limiting list of compounds or agriculturally acceptable salts are:

[0034] [ka] Includes TIFF2024524632000014.tif163161 and TIFF2024524632000015.tif213166.

[0035] According to some embodiments of the composition, the agricultural composition further comprises at least one crop protection agent. In one embodiment, the at least one crop protection agent is selected from the group consisting of fungicides, insecticides, herbicides, and plant growth regulators. In one embodiment, the crop protection agent is a herbicide. In another embodiment, the crop protection agent is a plant growth regulator. In one embodiment, the at least one crop protection agent is atrazine, terbuthylazine, (S)-metolachlor, metolachlor, terbutyrin, simazine, dimethenamid, (S)-dimethenamid, flufenacet, acetochlor, alachlor, isoxaflutole, isoxachlorthole, mesotrione, sulcotrione, metosulam, flumetosulam, pendimethalin, bromoxynil, bentazon, caffentrazone-ethyl, clomazone, nicosulfuron, rimsulfuron, halosulfuron-methyl, metribuzin, flumiclorac-pentyl, prosulfuron, primisulfuron-methyl, dicamba, fluthiacet-methyl, pyridate, 2,4-D, clopyralid, diflufenzopyr, fluroxypyr, MCPA, MCPB, mecoprop (MCPP), metobenzuron, thifensulfuron-methyl, aclonifen, EPTC, glyphosate, glufosinate, sulfosate, cyanazine, propaquizafop, metamitron, pyramine, phenmedipham, desmedipham, ethofumesate, triasulfuron, chloridazon, lenacil, triallate, fluazifop, sethoxydim, quizalofop, clopyralid, clethodim, oxasulfuron, acifluorfen, benazolin-ethyl, sulfentrazone, chlorimuron-ethyl, chloransulam-methyl, fomesafen, imazamox, imazaquin, imazethapyr, imazapyr, lactofen, fenoxaprop (P-ethyl), thiadiazuron, tribufos, Trifluralin, dimethachlor, napropamide, quinmerac, metazachlor, carbetamide, dimefuron, propyzamide, ethametsulfuron-methyl, tebutam, fluometuron, prometryn, norflurazon, pyrithiobac-sodium, MSMA, DSMA, diuron, flurochloridone, dithiopyr, thiazopyr, oxyfluorfen, ethalfluralin, clodinafop, amidosulfuron, diclofop-methyl, diflufenican, ethoxysulfuron, fentrazamide, flazasulfuron, florasulam, fluazolate, flucarbazone, flupyrsulfuron-methyl sodium, flurtamone, iodosulfuron, isoproturon, chlorotoluron, chlorsulfuron, metsulfuron-methyl, sulfosulfuron, tribenuron-methyl, 2,4-DB, 2,4-DP, Bifenox, Flamprop-M, Imazamethabenz-methyl, Ioxynil, Tralkoxydim, Fluoroglycofen-ethyl, Methabenzthiazuron, Isoxaben, Prosulfocarb, Difenzoquat-methyl sulfate, Pretilachlor, Cinosulfuron, Fenclorim, Bensulfuron-methyl, Imazosulfuron, Pyrazosulfuron-ethyl, Azimsulfuron, Esprocarb, Mefenacet, Moline cate, propanil, pyrazolate, cyhalofop-butyl, bispyribac-sodium, pyriminobac-methyl, cafenstrole, oxadiargyl, oxadiazon, bromobutide, MY-100, dymron, NB061, MK243, HW-52, AC014, ametryn, hexazinone, asulam, azafenidin, tebuthiuron, ethametsulfuron-methyl, or combinations thereof.

[0036] According to some embodiments, the present invention provides a method for controlling unwanted plant growth comprising applying to a locus of said unwanted plant growth an agricultural composition according to one or more of the embodiments of the composition described above.

[0037] According to some embodiments, the present invention provides a method for controlling unwanted plant growth, comprising the steps of:

[0038] [ka] [In the formula, A is a cyclopentadiene, benzene, or indene skeleton containing 1 to 4 heteroatoms, each of which is independently selected from the group consisting of N, S, Se, and O, and one or more of the ring carbon atoms is selected from -SO2CF3, -O-SO2CF3, -NR3 + , -SO2R, -C≡N, -CX3, CX2R, -COX, -CHO, -COR, -CO2R, -CONH2, -CONHR, -CONR2, -N=O, -N≡N +, -N=NR, -CR=NR, -N=CR2, -F, -Cl, -Br, and -I, where X is selected from F, Cl, Br, and I; n is 0 to 5; T is unsubstituted or contains one or two halides, oxygen, -SO2CF3, -O-SO2CF3, -NR3 + , -SO2R, -C≡N, -CX3, CX2R, -COX, -CHO, -COR, -CO2R, -CONH2, -CONHR, -CONR2, -F, -N=O, -N≡N + , -N=NR, -CR=NR, -N=CR2, and X is selected from F, Cl, Br and I; Z is -COOH, COO-, OH, -OR; COOR with a saturated or unsaturated alcohol residue with a linear, branched, cyclic, aromatic or heteroaromatic chain; -O-(CH2CH2O) n R(n≧1);-O-(CHMeCH2O) n R(n≧1)); a sulfonyl group, a carbamoyl group, a primary amine, a secondary amine, a tertiary amine, a carboxamide, -NR-OR, -O-NR2, a hydrazine, -NH-COR, and a methanimidamide moiety or a salt thereof; R is selected from H, substituted or unsubstituted alkyl, and substituted or unsubstituted aryl groups. or a salt thereof to the locus of unwanted plant growth.

[0039] According to some embodiments, Z is, but is not limited to,

[0040] [ka] The compound is selected from the group consisting of:

[0041] According to some embodiments of the above method, the unlimited list of compounds, or agriculturally acceptable salts thereof, include: Includes.

[0042] According to some embodiments of the above composition, the non-limiting list of compounds, or agriculturally acceptable salts thereof, are:

[0043] [ka] Includes TIFF2024524632000019.tif189161TIFF2024524632000020.tif214168.

[0044] According to some embodiments of the method, the method further comprises applying at least one crop protection agent to the locus of undesired plant growth. In one embodiment, the crop protection agent is selected from the group consisting of herbicides, fungicides, insecticides, and plant growth regulators. According to some embodiments of the method, the crop protection agent is a herbicide. In one embodiment, the crop protection agent is an amino acid synthesis inhibitor herbicide. In one embodiment, a non-limiting list of amino acid synthesis inhibitor herbicides of the present invention includes sulfonylurea herbicides, imidazolinone herbicides, sulfonamide herbicides, amino acid derivatives, imazamox, imazapic, imazethapyr, imazaquin, imazapyr and imazamethabenz, chlorimuron, primisulfuron, thifensulfuron, triasulfuron, nicosulfuron, metsulfuron, tribenuron, rimsulfuron, triflusulfuron, glyphosate, or any combination thereof.

[0045] According to some embodiments of the above method, the crop protection agent is a plant growth regulator. In one embodiment, a non-limiting list of plant growth regulators of the present invention includes dicamba, 2,4-D, clopyralid and fluroxypyr.

[0046] According to some embodiments, the present invention provides a method for controlling unwanted plant growth, comprising: a. Structure

[0047] [ka] [In the formula, A is a cyclopentadiene, benzene, or indene skeleton containing 1 to 4 heteroatoms, each of which is independently selected from the group consisting of N, S, Se, and O, and one or more of the ring carbon atoms is selected from -SO2CF3, -O-SO2CF3, -NR3 + , -SO2R, -C≡N, -CX3, CX2R-COX, -CHO, -COR, -CO2R, -CONH2, -CONHR, -CONR2, -F, -N=O, -N≡N + , -N=NR, -CR=NR, -N=CR2, -Cl, -Br, and -I, where X is selected from F, Cl, Br, and I; n is 0 to 5; T is unsubstituted or contains one or two halides, oxygen, -SO2CF3, -O-SO2CF3, -NR3 + , -SO2R, -C≡N, -CX3, CX2R, -COX, -CHO, -COR, -CO2R, -CONH2, -CONHR, -CONR2, -F, -N=O, -N≡N + , -N=NR, -CR=NR, -N=CR2, and X is selected from F, Cl, Br and I; Z is -COOH, COO-, OH, -OR; COOR with a saturated or unsaturated alcohol residue with a linear, branched, cyclic, aromatic or heteroaromatic chain; -O-(CH2CH2O) n R(n≧1);-O-(CHMeCH2O) n R(n≧1)); a sulfonyl group, a carbamoyl group, a primary amine, a secondary amine, a tertiary amine, a carboxamide, -NR-OR, -O-NR2, a hydrazine, -NH-COR, and a methanimidamide moiety or a salt thereof; R is selected from H, substituted or unsubstituted alkyl, and substituted or unsubstituted aryl groups. or a salt thereof, b. a second herbicide to effectively control unwanted plant growth. to the locus of the unwanted plant growth, thereby effectively controlling the unwanted plant growth.

[0048] According to some embodiments of the above method, Z is, but is not limited to,

[0049] [ka] may be also possible.

[0050] According to some embodiments of the above methods, the second herbicide is an amino acid synthesis inhibitor herbicide.

[0051] According to some embodiments of the above method, the second herbicide is selected from the group consisting of a sulfonylurea herbicide, an imidazolinone herbicide, a sulfonamide herbicide, and an amino acid derivative.

[0052] According to some embodiments of the method, a non-limiting list of second herbicides of the invention includes imazamox, imazapic, imazethapyr, imazaquin, imazapyr, imazamethabenz, chlorimuron, primisulfuron, thifensulfuron, triasulfuron, nicosulfuron, metsulfuron, tribenuron, rimsulfuron, triflusulfuron, glyphosate, atrazine, terbuthylazine, (S)-metolachlor, metolachlor, terbutyrin, simazine, dimethenamid, (S)-metolachlor, metolachlor, methaquin ... S)-Dimethenamid, Flufenacet, Acetochlor, Alachlor, Isoxaflutole, Isoxachlorthole, Mesotrione, Sulcotrione, Metosulam, Flumetoslam, Pendimethalin, Bromoxynil, Bentazon, Caffentrazone-ethyl, Clomazone, Nicosulfuron, Rimsulfuron, Halosulfuron-methyl, Metribuzin, Flumiclorac-pentyl, Prosulfuron, Primisulfuron-methyl, Dicamba, Fluthiacet-methyl, Pyridate, 2,4-D, clopyralid, diflufenzopyr, fluroxypyr, MCPA, MCPB, mecoprop (MCPP), metobenzuron, thifensulfuron-methyl, aclonifen, EPTC, glyphosate, glufosinate, sulfosate, cyanazine, propaquizafop, metamitron, pyramine, phenmedipham, desmedipham, ethofumesate, triasulfuron, chloridazon, lenacil, triallate, fluazifop, sethoxydim, quizalofop, clopyralid, clethodim, oxasulfuron, acifluorfen, benazolin-ethyl, sulfentrazone, chlorimuron-ethyl, chloransulam-methyl, fomesafen, imazamox, imazaquin, imazethapyr, imazapyr, lactofen, fenoxaprop (P-ethyl), thiadiazuron, tribufos, Trifluralin, dimethachlor, napropamide, quinmerac, metazachlor, carbetamide, dimefuron, propyzamide, ethametsulfuron-methyl, tebutam, fluometuron, prometryn, norflurazon, pyrithiobac-sodium, MSMA, DSMA, diuron, flurochloridone, dithiopyr, thiazopyr, oxyfluorfen, ethalfluralin, clodinafop, amidosulfuron, diclofop-methyl, diflufenican, ethoxysulfuron, fentrazamide, flazasulfuron, florasulam, fluazolate, flucarbazone, flupyrsulfuron-methyl sodium, flurtamone, iodosulfuron, isoproturon, chlorotoluron, chlorsulfuron, metsulfuron-methyl, sulfosulfuron, tribenuron-methyl, 2,4-DB, 2,4-DP, bifenox, flamprop-M, imazamethabenz-methyl, ioxynil, tralkoxydim, fluoroglycofen-ethyl, methabenzthiazuron, isoxaben, prosulfocarb, difenzoquat methyl sulfate, pretilachlor, cinosulfuron, fenclorim, bensulfuron-methyl, imazosulfuron, pyrazosulfuron-ethyl, azimsulfuron, esprocarb, mefenacet, molinate, propanil, pyrazolate, cyhalofop-butyl, bispyribac-sodium, pyriminobac-methyl, cafenstrole, oxadiargyl, oxadiazon, bromobutide, MY-100, dymron, NB061, MK243, HW-52, AC014, ametryn, hexazinone, asulam, azafenidin, tebuthiuron, and ethametsulfuron-methyl. ,

[0053] According to some embodiments of the above method, the method further comprises applying a third herbicide or plant growth regulator.

[0054] According to some embodiments, the present invention provides a composition for controlling unwanted plant growth, comprising: a. Structure

[0055] [ka] [In the formula, A is a cyclopentadiene, benzene, or indene skeleton containing 1 to 4 heteroatoms, each of which is independently selected from the group consisting of N, S, Se, and O, and one or more of the ring carbon atoms is selected from -SO2CF3, -O-SO2CF3, -NR3 + , -SO2R, -C≡N, -CX3, CX2R-COX, -CHO, -COR, -CO2R, -CONH2, -CONHR, -CONR2, -F, -N=O, -N≡N + , -N=NR, -CR=NR, -N=CR2, -Cl, -Br, and -I, where X is selected from F, Cl, Br, and I; n is 0 to 5; T is unsubstituted or contains one or two halides, oxygen, -SO2CF3, -O-SO2CF3, -NR3 + , -SO2R, -C≡N, -CX3, CX2R, -COX, -CHO, -COR, -CO2R, -CONH2, -CONHR, -CONR2, -F, -N=O, -N≡N + , -N=NR, -CR=NR, -N=CR2, and X is selected from F, Cl, Br and I; Z is -COOH, COO-, OH, -OR; COOR with a saturated or unsaturated alcohol residue with a linear, branched, cyclic, aromatic or heteroaromatic chain; -O-(CH2CH2O) n R(n≧1);-O-(CHMeCH2O) n R(n≧1)); a sulfonyl group, a carbamoyl group, a primary amine, a secondary amine, a tertiary amine, a carboxamide, -NR-OR, -O-NR2, a hydrazine, -NH-COR, and a methanimidamide moiety or a salt thereof; R is selected from H, substituted or unsubstituted alkyl, and substituted or unsubstituted aryl groups. or a salt thereof, b. Atrazine, Terbuthylazine, (S)-metolachlor, metolachlor, terbutyrin, simazine, dimethenamid, (S)-dimethenamid, flufenacet, acetochlor, alachlor, isoxaflutole, isoxachlorthole, mesotrione, sulcotrione, metosulam, flumetosulam, pendimethalin, bromoxynil, bentazon, caffentrazone-ethyl, clomazone, nicosulfuron, rimsulfuron, halosulfuron-methyl, metribuzin, flumiclorac-pentyl, prosulfuron, primisulfuron- Methyl, dicamba, fluthiacet-methyl, pyridate, 2,4-D, clopyralid, diflufenzopyr, fluroxypyr, MCPA, MCPB, mecoprop (MCPP), metobenzuron, thifensulfuron-methyl, aclonifen, EPTC, glyphosate, glufosinate, sulfosate, cyanazine, propaquizafop, metamitron, pyramine, phenmedipham, desmedipham, ethofumesate, triasulfuron, chloridazon, lenacil, triallate, fluazifop, sethoxydim, quizalofop, clopyralid, clenafop ... Thodim, oxasulfuron, acifluorfen, benazolin-ethyl, sulfentrazone, chlorimuron-ethyl, chloransulam-methyl, fomesafen, imazamox, imazaquin, imazethapyr, imazapyr, lactofen, fenoxaprop (P-ethyl), thiadiazuron, tribufos, trifluralin, dimethachlor, napropamide, quinmerac, metazachlor, carbetamide, dimefuron, propyzamide, ethametsulfuron-methyl, tebutam, fluometuron, prometryn, norflurazone, pyrithiobac-sodium um, MSMA, DSMA, diuron, flurochloridone, dithiopyr, thiazopyr, oxyfluorfen, ethalfluralin, clodinafop, amidosulfuron, diclofop-methyl, diflufenican, ethoxysulfuron, fentrazamide, flazasulfuron, florasulam, fluazolate, flucarbazone, flupyrsulfuron-methyl sodium, flurtamone, iodosulfuron, isoproturon, chlorotoluron, chlorsulfuron, metsulfuron-methyl, sulfosulfuron, tribenuron-methyl, 2,4-DB, 2,4-DP, Bifenox, Flamprop-M, Imazamethabenz-methyl, Ioxynil, Tralkoxydim, Fluoroglycofen-ethyl, Methabenzthiazuron, Isoxaben, Prosulfocarb, Difenzoquat-methyl sulfate, Pretilachlor, Cinosulfuron, Fenclorim, Bensulfuron-methyl, Imazosulfuron, Pyrazosulfuron-ethyl, Azimsulfuron, Esprocarb, Mefenacet, Molinate, Propane at least one herbicide selected from the group consisting of tetracycline, pyrazolate, cyhalofop-butyl, bispyribac-sodium, pyriminobac-methyl, cafenstrole, oxadiargyl, oxadiazon, bromobutide, MY-100, dymron, NB061, MK243, HW-52, AC014, ametryn, hexazinone, asulam, azafenidin, tebuthiuron, ethametsulfuron-methyl, or combinations thereof; and c. at least one agriculturally acceptable carrier The present invention provides a composition comprising a mixture of

[0056] According to some embodiments, the present invention provides a composition for controlling unwanted plant growth, comprising: a. Structure

[0057] [ka] [In the formula, A is a cyclopentadiene, benzene, or indene skeleton containing 1 to 4 heteroatoms, each of which is independently selected from the group consisting of N, S, Se, and O, and one or more of the ring carbon atoms is selected from -SO2CF3, -O-SO2CF3, -NR3 + , -SO2R, -C≡N, -CX3, CX2R-COX, -CHO, -COR, -CO2R, -CONH2, -CONHR, -CONR2, -F, -N=O, -N≡N + , -N=NR, -CR=NR, -N=CR2, -Cl, -Br, and -I, where X is selected from F, Cl, Br, and I; n is 0 to 5; T is unsubstituted or contains one or two halides, oxygen, -SO2CF3, -O-SO2CF3, -NR3 + , -SO2R, -C≡N, -CX3, CX2R, -COX, -CHO, -COR, -CO2R, -CONH2, -CONHR, -CONR2, -F, -N=O, -N≡N + , -N=NR, -CR=NR, -N=CR2, and X is selected from F, Cl, Br and I; Z is -COOH, COO-, OH, -OR; COOR with a saturated or unsaturated alcohol residue with a linear, branched, cyclic, aromatic or heteroaromatic chain; -O-(CH2CH2O) n R(n≧1);-O-(CHMeCH2O) n R(n≧1)); a sulfonyl group, a carbamoyl group, a primary amine, a secondary amine, a tertiary amine, a carboxamide, -NR-OR, -O-NR2, a hydrazine, -NH-COR, and a methanimidamide moiety or a salt thereof; R is selected from H, substituted or unsubstituted alkyl, and substituted or unsubstituted aryl groups. or a salt thereof, b. at least one plant growth regulator, and c. at least one agriculturally acceptable carrier The present invention provides a composition comprising a mixture of

[0058] According to some embodiments, there is provided a method for controlling the amino acid content in a plant or part of the plant, comprising applying an effective amount of an agricultural composition according to the above embodiments of the present invention.

[0059] According to some embodiments, the present invention provides a method for controlling the amino acid content in a plant or part of the plant, comprising applying an effective amount of an agricultural composition according to the above embodiments of the present invention.

[0060] According to some embodiments, the present invention provides a method for controlling plant growth, comprising applying to a plant or part of the plant an effective amount of an agricultural composition according to the above embodiments of the present invention.

[0061] According to some embodiments, the present invention provides a method for controlling the growth of a plant that is at least partially resistant to a herbicide selected from HPAC groups 9 (inhibitors of EPSP synthesis), 2 (acetolactate synthase (ALS) inhibitors), and 4 (plant growth regulators or synthetic auxins), comprising applying to the plant or a part of the plant an effective amount of an agricultural composition according to the above embodiments of the present invention.

[0062] According to some embodiments, the present invention provides agricultural compositions comprising one or more compounds listed in Tables 2, 3, 4, and 5, and at least one agriculturally acceptable carrier.

[0063] According to some embodiments, the present invention provides a method of controlling unwanted plant growth comprising applying one or more compounds listed in Tables 2, 3, 4, and 5.

[0064] According to some embodiments, the present invention provides a method of controlling undesirable plant growth comprising applying an agricultural composition comprising one or more compounds listed in Tables 2, 3, 4 and 5 and at least one agriculturally acceptable carrier. EXAMPLES

[0065] In the following examples, if an abbreviation is not defined above, the abbreviation has its generally accepted meaning. Furthermore, all temperatures are in degrees Celsius (unless otherwise indicated). Using the following methods, the compounds set forth below were prepared as indicated.

[0066] [Example 1] Synthesis of N-[2-(2,5-dichloro-1,3-thiazol-4-yl)ethyl]acetamide (IDFP5650)

[0067] [ka]

[0068] Step A: 4-(2-aminoethyl)thiazol-2-amine dihydrochloride (5 g, 23.3 mmol) was suspended in DCM and cooled to 0° C., followed by the dropwise addition of TEA (7 g, 70 mmol) and acetic anhydride (2.4 g, 24 mmol). After the reaction was complete, the mixture was evaporated to dryness and re-evaporated with toluene three times to give the crude product N-(2-(2-aminothiazol-4-yl)ethyl)acetamide (4.5 g, crude), which was used in the next step without purification.

[0069] Step B: N-(2-(2-aminothiazol-4-yl)ethyl)acetamide (4.5 g, 24.2 mmol) was dissolved in CH3CN (50 mL), cooled to 0 °C, and NCS (3.33 g, 25 mmol) was added in one portion. After the reaction was complete (concluded by HNMR), the organic solvent was evaporated to dryness and the crude mixture was partitioned between EtOAc (50 mL) and HO (50 mL). The organic layer was washed with HO and brine, dried over Na2SO4, and evaporated under reduced pressure to give ethyl N-(2-(2-amino-5-chlorothiazol-4-yl)ethyl)acetamide (3.7 g, 17.0 mmol, 70% yield) as a yellow oil.

[0070] Step C: To a solution of N-(2-(2-amino-5-chlorothiazol-4-yl)ethyl)acetamide (3.7 g, 17.0 mmol) in CH3CN (50 mL) pre-cooled to 0 °C, anhydrous CuCl2 (2.3 g, 17 mmol) was added in one portion. After 10 min, tert-butyl nitrite (1.8 g, 17.5 mmol) was added dropwise (the reaction starts after about 10% of the reagents are added. The start can be identified by the onset of vigorous gas evolution). After the reaction was complete (concluded by HNMR), the volume of the reaction mixture was carefully reduced to half under reduced pressure. The resulting crude mixture was dissolved in EtOAc (100 mL) and washed thoroughly with 5% aqueous HCl and brine. The organic layer was dried over Na2SO4 and evaporated under reduced pressure to give the crude product. This was purified by FCC to give N-(2-(2,5-dichlorothiazol-4-yl)ethyl)acetamide (1.22 g, 5.1 mmol, 30% yield). 1 H NMR (500 MHz, DMSO-d6) δ 7.94 (s, 1H), 3.29 (q, J = 6.4 Hz, 2H), 2.76 (t, J = 6.8 Hz, 2H), 1.76 (s, 3H). LCMS 239[M+H] + . MW 239.12; melting point 87°C, purity 90%.

[0071] [Example 2] Synthesis of 2-(2,5-dichloro-1,3-thiazol-4-yl)-2,2-difluoroacetic acid (IDFP5667)

[0072] [ka]

[0073] Step A: Ethyl 2-(2-aminothiazol-4-yl)-2,2-difluoroacetate (350 g, 1.58 mol) was dissolved in CH3CN (3 L), cooled to 0 °C, and NCS (215 g, 1.6 mol) was added in one portion. After the reaction was complete (concluded by HNMR), the organic solvent was evaporated to dryness and the crude mixture was partitioned between EtOAc (3 L) and H2O (1 L). The organic layer was washed with H2O and brine, dried over Na2SO4, and evaporated under reduced pressure to give ethyl 2-(2-amino-5-chlorothiazol-4-yl)-2,2-difluoroacetate as a yellow solid (283 g, 1.1 mol, 70% yield).

[0074] Step B: To a solution of ethyl 2-(2-amino-5-chlorothiazol-4-yl)-2,2-difluoroacetate (283 g, 1.1 mol) in CH3CN (3 L) pre-cooled to 0° C., anhydrous CuCl2 (155 g, 1.15 mol) was added in one portion. After 10 min, tert-butyl nitrite (121 g, 1.16 mol) was added dropwise (the reaction begins after approximately 10% of the reagents have been added. The onset can be identified by the onset of vigorous gas evolution). After the reaction was complete (as concluded by HNMR), the volume of the reaction mixture was carefully reduced to half under reduced pressure. The resulting crude mixture was dissolved in EtOAc (3 L) and washed thoroughly with 5% aqueous HCl and brine. The organic layer was dried over Na2SO4 and evaporated under reduced pressure to give crude ethyl 2-(2,5-dichlorothiazol-4-yl)-2,2-difluoroacetate (210 g, crude) as a dark brown oil, which was used in the next step without purification.

[0075] Step C: The crude ethyl 2-(2,5-dichlorothiazol-4-yl)-2,2-difluoroacetate (210 g, crude product) obtained in the previous step was dissolved in EtOH (2 L) and 20% aqueous K2CO3 (0.5 L) was added in one portion. After the reaction was complete (usually 3 h), the solvent was evaporated to dryness and the crude mixture was dissolved in H2O (0.5 L). The clear solution was washed with CHCl3 (3*200 mL) and MTBE (100 mL). The aqueous layer was acidified to pH=4 with NaHSO4 and extracted with diethyl ether (3*150 mL). The combined organic layers were washed with brine, dried over Na2SO4 and evaporated under reduced pressure to give an oily product. After column chromatography and trituration with pentane, pure 2-(2,5-dichlorothiazol-4-yl)-2,2-difluoroacetic acid was obtained as a yellow solid (113 g, 0.46 mol, 27% yield over three steps). 1H NMR (500 MHz, CDCL3) δ 10.38 (s, 1H). 13C NMR (126 MHz, CDCL3) δ 165.29 (t, J = 33.4 Hz), 149.86 (s), 140.45 (t, J = 29.7 Hz), 129.24 (s), 109.64 (t, J = 253.2 Hz). 19F NMR (470 MHz, CDCL3) δ -102.57 (s). LCMS248[M+H]+. Purity>95%

[0076] [Example 3] Synthesis of 2-chloro-1,3-thiazol-4-yl)-2,2-difluoroacetic acid (IDFP5666)

[0077] [ka]

[0078] Step A: To a solution of ethyl 2-(2-aminothiazol-4-yl)-2,2-difluoroacetate (250 g, 1.12 mol) in CH3CN (3 L) precooled to 0°C, anhydrous CuCl2 (155 g, 1.15 mol) was added in one portion (note that an exothermic effect is observed; heat to 10°C). After 10 min, tert-butyl nitrite (121 g, 1.16 mol) was added dropwise (the reaction begins after approximately 10% of the reagents are added; the onset can be identified by the onset of vigorous gas evolution). After the reaction was complete (as concluded by HNMR), the volume of the reaction mixture was carefully reduced to half under reduced pressure. The resulting crude mixture was dissolved in EtOAc (3 L) and washed thoroughly with 5% aqueous HCl and brine. The organic layer was dried over Na2SO4 and evaporated under reduced pressure to give the crude product ethyl 2-(2-chlorothiazol-4-yl)-2,2-difluoroacetate (205 g, crude), which was used in the next step without purification.

[0079] Step B: The crude product ethyl 2-(2-chlorothiazol-4-yl)-2,2-difluoroacetate (205 g, crude) obtained in the previous step was dissolved in EtOH (1.5 L) and 20% aqueous K2CO3 (0.5 L) was added in one portion. After the reaction was complete (usually 3 h), the solvent was evaporated to dryness and the crude mixture was dissolved in H2O (500 mL). The clear solution was washed with CHCl3 (3*200 mL) and MTBE (100 mL). The aqueous layer was acidified to pH=4 with NaHSO4 and extracted with diethyl ether (3*150 mL). The combined organic layers were washed with brine, dried over Na2SO4 and evaporated under reduced pressure to give an oily product. After column chromatography and trituration with pentane, pure 2-(2-chlorothiazol-4-yl)-2,2-difluoroacetic acid was obtained as a yellow solid (108 g, 0.5 mol, 45% yield over two steps). 1H NMR (400 MHz, CDCl3) δ 11.61 (s, 1H), 7.70 (s, 1H). 13C NMR (101 MHz, CDCl3) δ 165.10 (t, J = 33.6 Hz), 154.53 (s), 145.63 (t, J = 30.9 Hz), 122.62 (t, J = 4.7 Hz), 109.40 (t, J = 251.0 Hz). 19F NMR (376 MHz, CDCl3) δ -103.92 (s). LCMS 214[M+H]+. MP 92℃; Purity>95%

[0080] Example 4: Effects of heterocyclic amino acid derivatives on germination and early plant development.

[0081] Materials: Lettuce R. (Super Jericho, non-sterile) seeds were obtained from Ben Shahar Moshe Ltd. 99% purity. The test compounds listed in Table 2 below were either newly synthesized or purchased from different commercial sources.

[0082] Filter paper bioassay with lettuce seeds: The protocol was followed as described in Bertin et al. 2009 and Movellan et al. 2014 with the modifications specified below.

[0083] Seeds were placed (10 seeds per plate) on Whatman no. 1 filter paper (Whatman, Middlesex, UK) in Petri dishes with 2.0 ml of aqueous solutions of test material ranging in concentration from 0 (control) to 1 mmol / l and arranged in trays tilted at 45°. Trays were kept in darkness for 48 hours and then transferred to a growth chamber with a 6 / 18 dark / light cycle for 4 days. Each experiment was performed in at least two replicates.

[0084] Six days after the start of the test, the development of the plant roots and shoots was visually evaluated to determine the minimum effective concentration (MEC) of the test material. In the context of the present invention, MEC is defined as the lowest concentration level of the test material that causes a deviation from the plant development in the control group (no germination or malformation of the roots or shoots). MEC is expressed as an activity score in arbitrary units, as presented in Table 1:

[0085] [Table 1]

[0086] The herbicidal activity of selected compounds on seed germination and early plant development is summarized in Table 2:

[0087] [Table 2] TIFF2024524632000030.tif230164TIFF2024524632000031.tif234164TIFF2024524632000032.tif226162TIFF20245246320 00033.tif221163TIFF2024524632000034.tif219163TIFF2024524632000035.tif231163TIFF2024524632000036.tif226163 TIFF2024524632000037.tif229164TIFF2024524632000038.tif217164TIFF2024524632000039.tif221163TIFF20245246320 00040.tif231164TIFF2024524632000041.tif228163TIFF2024524632000042.tif236163TIFF2024524632000043.tif231163

[0088] Example 6 Postemergence herbicidal activity of selected derivatives of non-coded amino acids (DNAA).

[0089] Tests were performed on leaves of romaine lettuce (Lactuca sativa L) plants at stage 2-3. Plants were grown in small pots with one plant per small pot of dimensions 2 x 2 x 5 cm packed with soil. Test compounds were dissolved in aqueous solutions of 0.1% aqueous solution of Silwet adjuvant to final concentrations ranging from 0 (control) to 0.0001%. Test compounds were applied to the soil (1 ml per pot) or to the foliage with an airbrush (0.1 ml per pot). Each concentration was tested on 20 plants. Two weeks after treatment, the herbicidal efficacy of each test material was visually evaluated (above ground and roots). The above ground part of the plants was then tightly cut and weighed (wet weight) to evaluate the growth inhibition caused by the test compounds. Growth inhibition (GI) was calculated as follows: GI=1-Mt * 100% / Mc (where Mt and Mc are the average wet masses of treated and control plants, respectively). In the context of the present invention, herbicidal efficacy is evaluated by the concentration of compound that causes growth inhibition (GI) of more than 85% or irreversible damage to the plant (Table 3). The herbicidal activity of selected DHAAs is summarized in Table 4 (soil application) and Table 5 (foliar application).

[0090] [Table 3]

[0091] [Table 4] TIFF2024524632000046.tif221162TIFF2024524632000047.tif187161

[0092] [Table 5] TIFF2024524632000049.tif113165

[0093] Example 7: Herbicidal activity of selected DNAAs against developing weeds.

[0094] Weed seeds were cut in 0.3-liter pots containing medium-heavy clay-loam soil from an organic field (55% clay, 23% silt, 20% sand, 2% organic matter, pH 7.1). The experiment was performed with a fully randomized design. Each treatment was replicated three times (3 pots). Each compound was typically tested on crops (maize, wheat, soybean, cotton, oat, chickpea) and weeds (amaranth, pigweed, lentil, sinapis, silbum).

[0095] Herbicides were applied at doses of 0 (control) to 5 mg / pot. Treatments were performed on the day the seeds were cut (pre-emergence treatments). Then, 24 hours after herbicide application, the pots were transferred to mesh houses and watered with a sprinkler to the field water capacity of the soil. Alternatively, herbicides were applied to grown plants at stage 2-3 true leaves (post-emergence treatments).

[0096] The plants were grown in a mesh house for the entire duration of the experiment. Plant development (DAA) was assessed 6, 12, 19, 26 and 32 days after application on a scale of 0 to 5 (0 representing dead plants and 5 representing healthy plants similar to or not different from the control). In the context of the present invention, herbicidal efficacy is expressed as a score calculated as the average of the assessments of plant vigor, height and leaf color.

[0097] [Table 6] TIFF2024524632000051.tif121167

[0098] [Example 8] Effect of heterocyclic amino acid derivatives on germination Materials: Lettuce R seeds (Super Jericho, non-sterile), 99% purity, obtained from Ben Shahar Moshe Ltd. The test compounds listed in Table 2 below were either synthesized de novo or purchased from different commercial sources.

[0099] Filter paper bioassay with lettuce seeds: The protocol followed Bertin et al. 2009 and Movellan et al. 2014 with the specified modifications described below.

[0100] Seeds were placed (10 seeds per plate) on Whatman no. 1 filter paper (Whatman, Middlesex, UK) in Petri dishes with 2.0 ml of aqueous solutions of test materials ranging in concentration from 0 (control) to 1 mmol / l and arranged in trays tilted at 45°. Trays were kept in the dark for 48 hours and then transferred to a growth chamber with a 6 / 18 dark / light cycle for 4 days. Each experiment was performed in at least two replicates.

[0101] Six days after the start of the test, the development of the plant rootlets and shoots was visually evaluated to determine the Fully Effective Concentration (FEC) of the test material. In the context of this invention, the FED is defined as the lowest concentration level of the test material that nearly prevents seed germination.

[0102] The inhibitory effects of selected compounds on seed germination are summarized in Table 7.

[0103] [Table 7] TIFF2024524632000053.tif221162TIFF2024524632000054.tif197163

[0104] Example 9: Comparison of herbicidal activity of selected derivatives of non-coded amino acids (DNAA) with structurally related non-coded amino acids Tests were performed on leaves of romaine lettuce (Lactuca sativa L) plants at stage 2-3. Plants were grown in small pots with one plant per small pot of dimensions 2 x 2 x 5 cm packed with soil. Test compounds were dissolved in an aqueous solution of 0.1% aqueous solution of Silwet adjuvant. Test materials were applied at rates of 0 (control), 0.01, 0.05, and 0.5 mg / pot. Test compounds were applied to the soil or to the foliage (0.1 ml per pot) with an airbrush. Each concentration was tested on 20 plants. Two weeks after treatment, the herbicidal efficacy of each test material was visually evaluated (above ground and roots). The above ground portion of the plants was then tightly cut and weighed (wet weight) to evaluate the growth inhibition caused by the test compounds. Growth inhibition (GI) was calculated as follows: GI=1-Mt * 100% / Mc (Where Mt and Mc are the average wet weights of treated and control plants, respectively.) The compounds selected for the comparison of inhibitory activity are listed in Table 8. The comparison of herbicidal efficacy of non-coded amino acids (NAA) and their structural analogs DNAA is summarized in Table 9.

[0105] [Table 8]

[0106] [Table 9]

[0107] [Table 10]

[0108] Consideration: It was thus established that aminoacyl-tRNA synthetases capable of acylating tRNA with selected non-coded amino acids facilitated the inclusion of these molecules into nascent peptides. It has also been previously suggested that the herbicidal activity of selected non-coded amino acids is based on their ability to acylate tRNA, and thus alter the 3D structure of cellular proteins.

[0109] The NCAADs of the present invention lack either a carboxy or an amino group. In view of this, aminoacyl-tRNA synthetase cannot acylate tRNA in an NCAAD lacking a carboxyl, nor can it link to a nascent peptide in an NCAAD lacking an amino group. Thus, none of the NCAADs of the present invention can be incorporated into a peptide and exert the predicted effect on the 3D structure of a cellular protein.

[0110] As can be seen from the above experimental data, the NCAADs of the present invention have strong herbicidal activity, which is in contrast to the initial assumption that these compounds can only act as inactive structural analogues of herbicidal non-encoded AA (NCAA). Moreover, surprisingly, the NCAADs of the present invention demonstrate herbicidal activity 10-100 times higher than the corresponding NCAA.

[0111] Many NCAADs show herbicidal activity when applied both foliarly and to soil, suggesting effective uptake by leaves, shoots, and roots, in contrast to the corresponding NCAAs, which show herbicidal activity only when applied to soil.

[0112] Unless otherwise defined, all technical and / or scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. Although methods and materials similar or equivalent to those described herein can be used in the practice or testing of embodiments of the present invention, exemplary methods and / or materials are described below. In case of conflict, the patent specification, including definitions, will control. In addition, the materials, methods, and examples are illustrative only and are not intended to be necessarily limiting.

[0113] As used in this specification, the terms "comprises," "comprising," "includes," "including," "having," and their conjugations mean "including, but not limited to."

[0114] The term "consisting of" means "including and limited to."

[0115] As used herein, the singular forms "a," "an," and "the" include plural references unless the context clearly dictates otherwise. For example, the term "one compound" or "at least one compound" can include a plurality of compounds, including mixtures thereof.

[0116] When an element is referred to as "on," "attached to," "connected to," "coupled to," "in contact with," etc., another element, it is understood that this can be directly on, attached to, connected to, coupled to, and / or in contact with the other element, or that intervening elements may be present. In contrast, when an element is referred to as, for example, "directly on," "directly attached to," "directly connected to," "directly coupled to," or "directly in contact with" another element, there are no intervening elements present. It will be recognized by those skilled in the art that references to structures or features located "adjacent to" another feature can also have overlapping or underlying portions of the adjacent feature.

[0117] It should be understood that, although terms such as first, second, etc. may be used herein to describe various elements, components, regions, layers, and / or sections, these elements, components, regions, layers, and / or sections are not limited to these terms, but rather, these terms are used only to distinguish one element, component, region, layer, and / or section from another element, component, region, layer, and / or section.

[0118] As will be appreciated by those skilled in the art, compounds of various formulas disclosed herein may contain chiral centers, e.g., asymmetric carbon atoms. Thus, the present disclosure relates to the synthesis of both (i) racemic mixtures of active compounds and (ii) enantiomeric forms of active compounds. Separation of racemic enantiomeric forms and racemization of optically active enantiomeric forms can be carried out by procedures known in the art. Geometric isomers of double bonds and the like may also exist in the compounds disclosed herein, and all such stable isomers are included within the present disclosure unless otherwise specified. Tautomers (e.g., tautomers of triazoles and / or imidazoles) and rotational isomers are also included in the compounds disclosed herein. All chains defined in the formulas herein that contain three or more carbons may be saturated or unsaturated unless otherwise indicated.

[0119] It is understood that the substituents and substitution patterns on the compounds used in the methods of the present invention can be selected by one of ordinary skill in the art to result in compounds that are chemically stable and can be readily synthesized from readily available starting materials by techniques known in the art. It is understood that when a substituent is itself substituted with more than one group, these multiple groups can be on the same carbon or on different carbons, so long as a stable structure results.

[0120] An "optionally substituted" group refers to a functional group in which one or more bonds to a hydrogen atom contained therein are replaced with a bond to a non-hydrogen or non-carbon atom, provided that normal valence is maintained and the replacement results in a stable compound. Substituents also include groups in which one or more bonds to a carbon(s) or hydrogen(s) atom are replaced with one or more bonds, including double or triple bonds to a heteroatom. When multiple substituent moieties are disclosed or claimed, the substituted compound may be independently substituted, individually or multiply, with one or more of the disclosed or claimed substituent moieties. Independently substituted means that the (two or more) substituents can be the same or different. In selecting compounds of the present invention, those skilled in the art will recognize that the various substituents will be selected in accordance with well-known principles of chemical structure connectivity.

[0121] As used herein, "H" refers to a hydrogen atom. "C" refers to a carbon atom. "N" refers to a nitrogen atom. "O" refers to an oxygen atom. "Halo" refers to F, Cl, Br, or I. The term "hydroxy" as used herein refers to an -OH moiety. "Br" refers to a bromine atom. "Cl" refers to a chlorine atom. "I" refers to an iodine atom. "F" refers to a fluorine atom. "Acyl group" is intended to mean a -C(O)-R group, where R is a suitable substituent, such as an acetyl group, a propionyl group, a butyroyl group, a benzoyl group, or an alkylbenzoyl group. "Alkyl" as used herein refers to a straight or branched chain hydrocarbon containing from 1 or 2 to 10 or 20 or more carbon atoms (e.g., C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, etc.). In some embodiments, the alkyl can be a lower alkyl. "Lower alkyl" refers to straight or branched chain alkyl having 1 to 3, or 1 to 5, or 1 to 8 carbon atoms. Representative examples of alkyl include, but are not limited to, methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, iso-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, 3-methylhexyl, 2,2-dimethylpentyl, 2,3-dimethylpentyl, n-heptyl, n-octyl, n-nonyl, n-decyl, and the like. As used herein, the specification of a range of carbon numbers, for example, C1-C12 alkyl, is intended to include each of the carbon number portions of the constituents within such range, and thus each intervening carbon number within that stated range and any other stated or intervening carbon number values ​​are included, and thus subranges of carbon numbers within a specified carbon number range may be specified independently.For example, C1-C12 alkyl includes methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, and dodecyl, and is intended to include linear and branched groups as described above, and the carbon number range C1-C12 alkyl may also be more specifically specified as a subrange, such as C1-C4 alkyl, C2-C8 alkyl, C2-C4 alkyl, C3-C5 alkyl, or any other subrange of a broader carbon number range. In addition, carbon number ranges that specifically exclude a carbon number or numbers are also contemplated, such as in the case of subranges that exclude either or both of the carbon numbers at the boundaries of the specified range. As is commonly understood by those skilled in the art, "saturated" refers to a state in which all available valence bonds of an atom (e.g., carbon) are bonded to other atoms. Similarly, "unsaturated" refers to a state in which not all available valence bonds are bonded to other atoms, and in such compounds, the extra bonds usually take the form of double or triple bonds (usually to carbon). For example, a carbon chain is "saturated" if there are no double or triple bonds along the chain or directly connected to the chain (e.g., carbonyl), and is "unsaturated" if there is at least one double or triple bond along the chain or directly connected to the chain (e.g., carbonyl). Furthermore, it is understood by those skilled in the art that the presence or absence of a substituent, depending on the saturation of the chain, depends on the valency requirements of the atom(s) (e.g., carbon) to which the substituent is attached. "Alkenyl," as used herein, refers to a straight or branched chain hydrocarbon containing from 1 or 2 to 10 or 20 or more carbons, e.g., containing at least one carbon-carbon double bond formed structurally by the replacement of two hydrogens. Representative examples of "alkenyl" include, but are not limited to, ethenyl, 2-propenyl, 2-methyl-2-propenyl, 3-butenyl, 4-pentenyl, 5-hexenyl, 2-heptenyl, 2-methyl-1-heptenyl, 3-decenyl, and the like. "Alkynyl," as used herein, refers to a straight or branched chain hydrocarbon group containing from 1 or 2 up to 10 or 20 or more carbon atoms and containing at least one carbon-carbon triple bond.Representative examples of alkynyl include, but are not limited to, acetylenyl, 1-propynyl, 2-propynyl, 3-butynyl, 2-pentynyl, 1-butynyl, etc. The term "cycloalkyl," as used herein, refers to a saturated cyclic hydrocarbon group containing 3 to 8 or more carbons.

[0122] As understood in the art, the term "optionally substituted" indicates that the specified group is either unsubstituted or substituted with one or more suitable substituents. A "substituted" or "substituent" is an atom or group that replaces a hydrogen atom on a parent chain or a ring of an organic molecule. "Heterocycle," as used herein, refers to a monocyclic, bicyclic, or tricyclic ring system. Monocyclic heterocyclic ring systems are exemplified by any 5-9 membered ring containing 1, 2, 3, or 4 heteroatoms independently selected from the group consisting of O, N, and S. "Aryl," as used herein, refers to a ring system having one or more aromatic rings. Representative examples of aryl include azulenyl, indanyl, indenyl, naphthyl, phenyl, tetrahydronaphthyl, and the like. "Heteroaryl" refers to a cyclic, aromatic hydrocarbon in which one or more carbon atoms are replaced with a heteroatom (e.g., N, O, or S). When a heteroaryl group contains more than one heteroatom, the heteroatoms may be the same or different. "Alkoxy," as used herein, refers to an alkyl group, as defined herein, attached to the parent molecular moiety through an oxy group, as defined herein. "Amine" or "amino" is intended to mean the group -NH2. A "primary amine" has one of three hydrogen atoms replaced with an alkyl or aromatic group. A "secondary amine" has two organic substituents attached to the nitrogen along with one hydrogen. A "tertiary amine" has three organic substituents attached to the nitrogen. "Amide," as used herein, refers to a functional group or organic compound containing a carbonyl group (CO) attached to a nitrogen atom (N);

[0123] [ka] where R and R' can independently be any covalently bonded atom(s). The term "oxo" as used herein refers to a =O moiety. The term "oxy" as used herein refers to a -O- moiety. "Nitro" refers to the organic compound functional group -NO2. "Carbonyl" is a functional group in which a carbon atom is double bonded to an oxygen atom (-C=O). "Carboxy" as used herein refers to a -COOH functional group, and is also written as -CO2H or -(CO)-OH.

[0124] It is understood that the compounds, compositions and methods provided herein may, in some embodiments, be further specified by definitions or limitations that exclude particular substituents, groups, moieties, structures, components, steps, or conditions, where appropriate in the context of the various broader specifications and exemplifications set forth herein.

[0125] The "agriculturally acceptable carriers" of the present invention include, but are not limited to, adjuvants, mixers, accelerators, etc., useful for the application of the formula. Suitable carriers must not be phytotoxic and must not chemically react with the compounds of the formulas herein or other composition components at the concentrations utilized to apply the compositions for selective control of weeds in the presence of valuable crops, particularly crops. Such mixtures can be designed to be applied directly to weeds or their locus, or can be concentrates or formulations that are typically diluted with additional carriers and adjuvants before application. They may contain inert or active components and can be solids, such as dusts, granules, water dispersible granules, or wettable powders, or liquids, such as emulsifiable concentrates, solutions, emulsions, or suspensions. Suitable agricultural carriers useful for preparing the agricultural compositions of the present invention are well known to those skilled in the art. For example, liquid carriers that can be utilized include water, toluene, xylene, petroleum naphtha, crop oils, acetone, methyl ethyl ketone, cyclohexanone, trichloroethylene, perchloroethylene, ethyl acetate, amyl acetate, butyl acetate, propylene glycol monomethyl ether and diethylene glycol monomethyl ether, methanol, ethanol, isopropanol, amyl alcohol, ethylene glycol, propylene glycol, glycerin, and the like. Water is generally the carrier of choice for dilution of concentrates. Suitable solid carriers include talc, pyrophyllite clay, silica, attapulgite clay, diatomaceous earth, chalk, diatomaceous earth, lime, calcium carbonate, bentonire clay, fuller's earth, cottonseed hulls, wheat flour, soy flour, pumice, wood flour, walnut shell flour, lignin, and the like.

[0126] It is often desirable to incorporate one or more surfactants into the compositions of the present invention. Such surfactants are advantageously utilized in both solid and liquid compositions, particularly those designed to be diluted with a carrier before application. The surfactants can be anionic, cationic, or nonionic in nature and can be utilized as emulsifiers, wetting agents, suspending agents, or for other purposes. Typical surfactants include alkyl sulfates, such as lauryl diethanol ammonium sulfate; alkylaryl sulfonates, such as calcium dodecylbenzene sulfonate; alkylphenol-alkylene oxide adducts, such as nonylphenol-C; 18 Ethoxylates; Alcohol-alkylene oxide addition products, e.g., tridecyl alcohol-C 16 ethoxylates; soaps such as sodium stearate; alkyl naphthalene sulfonates such as sodium dibutyl naphthalene sulfonate; dialkyl esters of sulfosuccinates such as sodium di(2-ethylhexyl) sulfosuccinate; sorbitol esters such as sorbitol oleate; quaternary amines such as trimethylammonium lauryl chloride; polyethylene glycol esters of fatty acids such as polyethylene glycol stearate; block copolymers of ethylene oxide and propylene oxide; and salts of mono- and dialkyl phosphate esters.

[0127] Other adjuvants commonly utilized in agricultural compositions include antifoaming agents, compatibilizers, sequestering agents, neutralizing agents and buffers, corrosion inhibitors, dyes, odorants, penetration aids, spreading agents, adhesives, dispersants, thickeners, freezing point depressants, antimicrobial agents, etc. The compositions can also contain other compatible components such as other herbicides, plant growth regulators, fungicides, insecticides, etc., and can be formulated with liquid fertilizers or solid particulate fertilizer carriers such as ammonium nitrate, urea, etc.

[0128] "Agriculturally acceptable salt" is intended to mean a salt which retains the biological effectiveness of the free acids and free bases of the specified compound and which is not biologically or otherwise undesirable. Examples of agriculturally acceptable salts include sulfate, pyrosulfate, bisulfate, sulfite, bisulfite, phosphate, monohydrogenphosphate, dihydrogenphosphate, metaphosphate, pyrophosphate, chloride, bromide, iodide, acetate, propionate, decanoate, caprylate, acrylate, formate, isobutyrate, caproate, heptanoate, propiolate, oxalate, malonate, succinate, suberate, sebacate, fumarate, maleate, butyne-1,4-dioate, hexyne-1, These include 6-dioate, benzoate, chlorobenzoate, methylbenzoate, dinitrobenzoate, hydroxybenzoate, methoxybenzoate, phthalate, sulfonate, xylenesulfonate, phenylacetate, phenylpropionate, phenylbutyrate, citrate, lactate, gamma-hydroxybutyrate, cholate, tartrate, methanesulfonate, propanesulfonate, naphthalene-1-sulfonate, naphthalene-2-sulfonate, and mandelate.

[0129] Throughout this application, various embodiments of the invention may be presented in a range format. It should be understood that the description in range format is merely for convenience and brevity and should not be construed as an inflexible limitation on the scope of the invention. Thus, the description of a range should be considered to have all possible subranges as well as individual numerical values ​​within the specifically disclosed range. For example, the description of a range such as 1-6 should be considered to have specifically disclosed subranges, such as 1-3, 1-4, 1-5, 2-4, 2-6, 3-6, etc., as well as individual numbers within that range, such as 1, 2, 3, 4, 5, and 6. This applies regardless of the breadth of the range.

[0130] Whenever a numerical range is given herein, it is intended to include any recited numerical values ​​(fractional or integral) within the given range. The phrases "ranging between" a first given number and a second given number, and the phrases "ranging from" a first given number "to" a second given number, are used interchangeably herein and are intended to include the first and second given numbers and all fractional and integral numerical values ​​therebetween.

[0131] Certain features of the invention that are described for clarity in the context of separate embodiments may also be provided in combination in a single embodiment. Conversely, various features of the invention that are described for clarity in the context of a single embodiment may also be provided separately or in any suitable subcombination or in any other described embodiment of the invention, where appropriate. Certain features that are described in the context of various embodiments are not to be considered essential features of those embodiments, unless the embodiment is inoperable without those elements.

[0132] As used herein, the term "method" refers to methods, means, techniques and procedures for accomplishing a given task, including, but not limited to, methods, means, techniques and procedures known to a practitioner in the chemical, agricultural, biological, and biochemical arts, or readily developed by the practitioner from known methods, means, techniques and procedures.

[0133] As used herein, the term "plant growth regulator" refers to, but is not limited to, a compound, either natural or synthetic, that modifies or controls one or more specific physiological processes in a plant.

[0134] As used herein, the term "plant" refers to whole plants, plant ancestors and progeny, and plant parts including seeds, shoots, stems, roots (including tubers), and plant cells, tissues, and organs. Plants may be in any form, including suspension cultures, embryos, meristematic regions, callus tissue, leaves, gametophytes, sporophytes, pollen, and microspores.

[0135] The term "crop protection agent" as used herein refers to an agent that is, but is not limited to, a pesticide (or a mixture of more than one pesticide) or a plant growth regulator.

[0136] As used herein, the term "pesticide" refers to, but is not limited to, a chemical or biological agent that deters, disables, kills, or otherwise impedes pests.

[0137] The compounds of the present invention are generally used as herbicidal active ingredients in compositions. As used herein, the term "composition" refers to a formulation having at least one additional component selected from the group consisting of, but not limited to, surfactants, solid diluents, and liquid diluents, which serves as a carrier. The formulation or composition components are selected to match the physical properties of the active ingredient, the mode of application, and environmental factors, such as oil type, moisture, and temperature. Useful compositions can include both liquid and solid formulations. Liquid formulations include solutions (including emulsifiable concentrates), suspensions, emulsion formulations (including microemulsion formulations, oil-in-water emulsion formulations, flowable concentrates, and / or suspoemulsion formulations), which can be optionally thickened into gels. Common types of aqueous liquid compositions are soluble concentrates, suspension concentrates, capsule suspensions, concentrated emulsions, microemulsion formulations, oil-in-water emulsion formulations, flowable concentrates, and suspoemulsion formulations. Common types of non-aqueous liquid compositions are emulsifiable concentrates, microemulsifiable concentrates, dispersible concentrates and oil dispersions.

[0138] Common types of solid agents are dusts, powders, granules, pellets, prills, pastilles, tablets, filled films (including seed coatings), etc., which can be water dispersible ("wettable") or water soluble. Films and coatings formed from film-forming solutions or flowable suspensions are particularly useful for seed treatment. The active ingredient can be (micro)encapsulated to further form a suspension or solid agent. Alternatively, the entire formulation of the active ingredient can be encapsulated (or "overcoated"). The encapsulation can provide controlled or delayed release of the active ingredient. Sprayable formulations can usually be stretched in a suitable medium before spraying. Such liquid formulations and solid agents are formulated to be easily diluted with the spray medium (usually water, but sometimes with another suitable medium, e.g., aromatic or paraffinic hydrocarbons or vegetable oils). Spray volumes can range from about one to several thousand liters per hectare, but more typically from about 10 to several hundred liters. Sprayable formulations can be tank mixed with water or another suitable vehicle for foliar treatment by aerial or ground application, or for application to the plant growing medium. Liquid and dry formulations can be metered directly into drip irrigation systems or metered into furrows during planting.

[0139] The formulations typically contain effective amounts of active ingredient, diluent, and surfactant within the following approximate ranges which add to 100 weight percent.

[0140] The compounds of the present invention have herbicidal activity (both pre-emergence and post-emergence). As used herein, the term "controlling undesirable plant growth" refers to killing or damaging or reducing the growth of vegetation.

[0141] The compounds and compositions of the present invention may be usefully applied by a variety of methods, including contacting a herbicidally effective amount of a compound of the present invention, or a composition containing said compound and at least one surfactant, solid diluent or liquid diluent, with the foliage or other parts of the undesirable plants, or with the environment of the undesirable plant growth, such as the soil or water in which the undesirable plants are growing or surrounding seeds or other vegetative propagules of the undesirable plants.

[0142] The herbicidally effective amount of the compounds of the present invention will depend on several factors: the formulation selected, the method of application, the amount and type of undesired plant growth present, growing conditions, etc. In general, the herbicidally effective amount of the compounds of the present invention will be about 0.001-20 kg / ha, with a preferred range being about 0.004-1 kg / ha. One of skill in the art can readily determine the herbicidally effective amount required for the desired level of weed control.

[0143] The compounds of the present invention are typically applied in the form of a formulated composition to a locus containing desired vegetation (e.g., crops) and undesired plant growth (i.e., weeds), both of which may be seeds, seedlings and / or larger plants in contact with a growing medium (e.g., soil).At this locus, a composition containing a compound of the present invention can be applied directly to the plant or any part of the plant, particularly any part of the undesired plant growth, and / or to the growing medium in contact with the plant.

[0144] The compounds of the present invention can also be mixed with herbicides, herbicide antidotes, fungicides, insecticides, nematicides, bactericides, acaricides, plant growth regulators, such as insect molting inhibitors and root stimulants, chemosterilants, semiochemicals, repellents, attractants, pheromones, feeding stimulants, plant nutrients, other biologically active compounds, or one or more other biologically active compounds or agents, including bacteria, viruses or fungi, to form multi-component pesticides that provide broader agricultural protection. Mixtures of the compounds of the present invention with other herbicides can extend the spectrum of activity to additional weed species and suppress the growth of any resistant biotypes.

[0145] Throughout this application, various publications, published patent applications and published patents are referenced. The disclosures of these publications in their entireties are hereby incorporated by reference into this application in order to more fully describe the state of the art to which this invention pertains.

[0146] Certain features of the invention that are described for clarity in the context of separate embodiments may also be provided in combination in a single embodiment. Conversely, various features of the invention that are described for clarity in the context of a single embodiment may also be provided separately or in any suitable subcombination or in any other described embodiment of the invention, where appropriate. Certain features that are described in the context of various embodiments are not to be considered essential features of those embodiments, unless the embodiment is inoperable without those elements.

Claims

1. Structure 【Chemical 1】 [wherein A is a cyclopentadiene skeleton containing 1 to 2 heteroatoms, each of the heteroatoms being independently selected from the group consisting of N and S, and one or more of the carbon atoms of the skeleton being -CX ３ , CX ２ being optionally chemically bonded to at least one of R, -F, -Cl, -Br, and -I, n is from 0 to 5, T is unsubstituted or is a methylene group substituted with one or two halides, -CX ３ , -CX ２ R, -F Z is -COOH, -O-R, -COOR; -O-(CH ２ CH ２ O) ｎ R (n≥1); -O-(CHMeCH ２ O) ｎ R (n≥1); a sulfonyl group, a primary amine, a secondary amine, a tertiary amine, a carboxamide or a salt thereof, X is selected from F, Cl, Br, and I, R is selected from the group consisting of H, substituted or unsubstituted alkyl, and substituted or unsubstituted aryl groups, and when Z is -O-R, R is a substituted or unsubstituted aryl group.] An agricultural composition comprising a compound having the same or a salt thereof and at least one agriculturally acceptable carrier.

2. The composition according to claim 1, wherein Z is selected from 【Chemical Formula 2】

3. Structure The composition according to claim 1, comprising a compound having the same. 【Chemical Formula 3】

4. Structure The composition according to claim 1, comprising a compound having the same. 【Chemical Formula 4】

5. Structure The composition according to claim 1, comprising a compound having the same. 【Chemical Formula 5】

6. Structure The composition according to claim 1, comprising a compound having the same. 【Chemical Formula 6】

7. Structure The composition according to claim 1, comprising a compound having the same. 【Chemical Formula 7】

8. Structure The composition according to claim 1, comprising a compound having the same. 【Chemical 8】

9. Structure The composition according to claim 1, comprising a compound having the same. 【Chemical Formula 9】

10. The composition according to claim 1, further comprising at least one crop protection agent.

11. The composition according to claim 10, wherein the at least one crop protection agent is selected from the group consisting of fungicides, insecticides, herbicides, and plant growth regulators.

12. The agricultural composition according to claim 11, wherein the crop protection agent is a herbicide.

13. The agricultural composition according to claim 11, wherein the crop protection agent is a plant growth regulator.

14.

15. At least one crop protection agent is atrazine, terbuthylazine, (S)-metolachlor, metolachlor, terbuthylin, simazine, dimethenamid, (S)-dimethenamid, flufenacet, acetochlor, alachlor, isoxaflutole, isoxachlortole, mesotrione, sulcotrione, metosulam, flumetosulam, pendimethalin, bromoxynil, bentazone, carfentrazone-ethyl, chromazone, nicosulfuron, rimsulfuron, halosulfuron-methyl, metribuzin, flumiclorac-pentyl, prosulfuron, primisulfuron-methyl, dicamba, fluthiacet-methyl, pyridate, 2,4-D, clopyralid, diflufenican, fluroxypyr, MCPA, MCPB, mecoprop (MCPP), metobenzuron, thifensulfuron-methyl, acifluorfen, EPTC, glyphosate, glufosinate, sulfosate, cyanazine, propaquizafop, metamitron, pyraclonil, fenmedifam, desmedifam, ethofumesate, triasulfuron, chloridazon, lenacil, triallate, fluaquizafop, sethoxydim, quizalofop, clopyralid, clethodim, oxasulfuron, acifluorfen, benazolin-ethyl, sulfentrazone, chlorimuron-ethyl, chloransulam-methyl, homesisafen, imazamox, imazakine, imazethapyr, imazapyr, lactofen, fenoxaprop (P-ethyl), thidiazuron, tribufos, trifluralin, dimethachlor, napropamide, cinmethylin, metazachlor, carbetamide, dimefuron, propyzamide, ethametsulfuron-methyl, tebutam, fluometuron, prometryn, norflurazon, pyrithiobac-sodium, MSMA, DSMA, diuron, flurochloridone, dithiopyr, thiazopyr, oxyfluorfen, ethalfluralin, clodinafop, amidosulfuron, dichlofop-methyl, diflufenican, ethoxysulfuron, fentrazamide, flazasulfuron, florasulam, fluazolate, flucarbazone, flupyrsulfuron-methyl sodium, flurtamon, iodosulfuron, isoproturon, chlorotoluron, chlorosulfuron, metsulfuron-methyl, sulfosulfuron, tribenuron-methyl, 2,The agricultural composition according to claim 11, selected from the group consisting of 4-DB, 2,4-DP, biphenox, flamprop-M, imazamethabenz-methyl, ioxynil, tralkoxydim, fluoroglycofen-ethyl, metobenzthiazuron, isoxaben, prosulfocarb, difenzoquat methyl sulfate, pretilachlor, cinosulfuron, fenclorim, bensulfuron-methyl, imazosulfuron, pyrazosulfuron-ethyl, azimsulfuron, esprocarb, mefenacet, molinate, propanil, pyrazolate, cyhalofop-butyl, bispyribac-sodium, pyriminobac-methyl, cafenstrole, oxadiargyl, oxadiazon, bromobutide, MY-100, dimehypo, NB061, MK243, HW-52, AC014, ametryn, hexazinone, asulam, azafenidin, tebuthiuron, ethametsulfuron-methyl, or a combination thereof. A method for controlling unwanted plant growth, comprising applying the agricultural composition according to any one of claims 1 to 14 to a location of unwanted plant growth.

16. A method for controlling unwanted plant growth, comprising applying a herbicidally effective amount of a compound having the structure [wherein 【Chemical Formula 10】 n is from 0 to 5, A is a cyclopentadiene skeleton containing 1 to 2 heteroatoms, each of the heteroatoms being independently selected from the group consisting of N and S, and one or more of the carbon atoms of the skeleton being -CX ３ , -CX ２ chemically bonded to at least one of the group consisting of R, -F, -Cl, -Br, and -I, X is selected from F, Cl, Br, and I, T is unsubstituted or is a methylene group substituted with one or two halides, -CX ３ , CX ２ R, -F Z is -COOH, -O-R, COOR; -O-(CH ２ CH ２ O) ｎ R (n≥1); -O-(CHMeCH ２ O) ｎ R (n≥1); a sulfonyl group, a primary amine, a secondary amine, a tertiary amine, a carboxamide or a salt thereof, R is selected from the group consisting of H, substituted or unsubstituted alkyl, and substituted or unsubstituted aryl groups, and when Z is -O-R, R is a substituted or unsubstituted aryl group.] or a salt thereof to a location of unwanted plant growth.

17. The method according to claim 16, wherein Z is selected from

18. 【Chemical Formula 11】 Structure The method according to claim 16, comprising applying a herbicidally effective amount of a compound having the same to a location of unwanted plant growth.

19. 【Chemical Formula 12】 Structure ​ ​ 【Chemical Formula 13】 The method according to claim 16, comprising applying a herbicidally effective amount of a compound having [specific structure] to a location of undesired plant growth.

20. Structure 【Chemical 14】 The method according to claim 16, comprising applying a herbicidally effective amount of a compound having [specific structure] to a location of undesired plant growth.

21. Structure 【Chemical Formula 15】 The method according to claim 16, comprising applying a herbicidally effective amount of a compound having [specific structure] to a location of undesired plant growth.

22. Structure 【Chemical 16】 The method according to claim 16, comprising applying a herbicidally effective amount of a compound having [specific structure] to a location of undesired plant growth.

23. Structure 【Chemical 17】 The method according to claim 16, comprising applying a herbicidally effective amount of a compound having [specific structure] to a location of undesired plant growth.

24. Structure 【Chemical 18】 The method according to claim 16, comprising applying a herbicidally effective amount of a compound having [specific structure] to a location of undesired plant growth.

25. The method according to any one of claims 16 to 24, further comprising applying at least one crop protection agent to a location of undesired plant growth.

26. The method according to claim 25, wherein the crop protection agent is selected from the group consisting of herbicides, fungicides, insecticides, and plant growth regulators.

27. The method according to claim 26, wherein the crop protection agent is a herbicide.

28. The method according to claim 26, wherein the crop protection agent is an amino acid synthesis inhibitor herbicide.

29. The method according to claim 28, wherein the amino acid synthesis inhibitor herbicide is selected from the group consisting of sulfonylurea herbicides, imidazolinone herbicides, sulfonamide herbicides, and amino acid derivatives, or combinations thereof.

30. The method according to claim 28, wherein the amino acid synthesis inhibitor herbicide is selected from the group consisting of imazamox, imazapic, imazethapyr, imazakipyr, imazapyr, and imazamethabenz, or combinations thereof.

31. The method according to claim 28, wherein the amino acid synthesis inhibitor herbicide is selected from the group consisting of chlorimuron, primisulfuron, thifensulfuron, triasulfuron,nicosulfuron, metsulfuron, tribenuron, rimsulfuron, and triflusulfuron, or combinations thereof.

32. The method according to claim 28, wherein the amino acid synthesis inhibitor herbicide is glyphosate.

33. The method according to claim 28, wherein the crop protection agent is a plant growth regulator.

34. The method according to claim 33, wherein the plant growth regulator is selected from the group consisting of dicamba, 2,4-D, clopyralid and fluroxypyr.

35. A method for controlling unwanted plant growth, comprising: a. Structure 【Chemical 19】 [Wherein, A is a cyclopentadiene skeleton containing 1 to 2 heteroatoms, each of the heteroatoms being independently selected from the group consisting of N and S, and one or more of the carbon atoms of the skeleton being -CX ３ , CX ２ is optionally chemically bonded to at least one of the group consisting of R, -Cl, -Br, and -I, n is 0 to 5, T is unsubstituted or is a methylene group substituted with one or two halides, -CX ３ , CX ２ R, -F Z is -COOH, -O-R, COOR; -O-(CH ２ CH ２ O) ｎ R (n ≥ 1); -O-(CHMeCH ２ O) ｎ R (n ≥ 1); a sulfonyl group, a primary amine, a secondary amine, a tertiary amine, a carboxamide or a salt thereof, X is selected from F, Cl, Br and I, R is selected from the group consisting of H, substituted or unsubstituted alkyl, and substituted or unsubstituted aryl groups, and when Z is -O-R, R is a substituted or unsubstituted aryl group. ] a first herbicide having the formula or a salt thereof, and b. A second herbicide by applying to a location of unwanted plant growth, effectively controlling unwanted plant growth.

36. The method according to claim 35, wherein Z is selected from 【Chemical 20】

37. The method according to claim 35, wherein the second herbicide is an amino acid synthesis inhibitor herbicide.

38. The method according to claim 37, wherein the second herbicide is selected from the group consisting of sulfonylurea herbicides, imidazolinone herbicides, sulfonamide herbicides and amino acid derivatives.

39. The method according to claim 37, wherein the second herbicide is selected from the group consisting of imazamox, imazapic, imazethapyr, imazakip, imazapyr, imazamethabenz, chlorimuron, primisulfuron, thifensulfuron, triasulfuron,nicosulfuron, metsulfuron, tribenuron, rimsulfuron, triflusulfuron and glyphosate.

40. The second herbicide is atrazine, terbuthylazine, (S)-metolachlor, metolachlor, terbutryn, simazine, dimethenamid, (S)-dimethenamid, flufenacet, acetochlor, alachlor, isoxaflutole, isoxachlortole, mesotrione, sulcotrione, metosulam, flumetosulam, pendimethalin, bromoxynil, bentazone, carfentrazone-ethyl, chromazone, nicosulfuron, rimsulfuron, halosulfuron-methyl, metribuzin, flumiclorac-pentyl, prosulfuron, primisulfuron-methyl, dicamba, fluthiacet-methyl, pyridate, 2,4-D, clopyralid, diflufenican, fluroxypyr, MCPA, MCPB, mecoprop (MCPP), metobenzuron, thifensulfuron-methyl, acifluorfen, EPTC, glyphosate, glufosinate, sulfosate, cyanazine, propaquizafop, metazachlor, pyriminobac, fenmedipham, desmedipham, ethofumesate, triasulfuron, chloridazon, lenacil, triallate, flucarbazone, sethoxydim, quizalofop, clopyralid, clethodim, oxasulfuron, acifluorfen, benazolin-ethyl, sulfentrazone, clomazone-ethyl, chloransulam-methyl, homosafen, imazamox, imazethapyr, imazapic, imazapyr, lactofen, fenoxaprop (P-ethyl), thidiazuron, tribufos, trifluralin, dimethachlor, napropamide, cinmethylin, metazachlor, carbetamide, dimefuron, propyzamide, ethametsulfuron-methyl, tebutam, fluometuron, prometryn, norflurazon, pyrithiobac-sodium, MSMA, DSMA, diuron, flurochloridone, dithiopyr, thiazopyr, oxyfluorfen, ethalfluralin, clodinafop, amidosulfuron, dichlorprop-methyl, diflufenican, ethoxysulfuron, fentrazamide, flazasulfuron, florasulam, flucarbazone, flupyrsulfuron-methylsodium, flurtamone, iodosulfuron, isoproturon, chlorotoluron, chlorosulfuron, metsulfuron-methyl, sulfosulfuron, tribenuron-methyl, 2,4-DB, 2,The method according to claim 37, selected from the group consisting of 4-DP, biphenox, flamprop-M, imazamethabenz-methyl, ioxynil, tralkoxydim, fluoroglycofen-ethyl, metobenzthiazuron, isoxaben, prosulfocarb, difenzoquat methyl sulfate, pretilachlor, cinosulfuron, fenclorim, bensulfuron-methyl, imazosulfuron, pyrazosulfuron-ethyl, azimsulfuron, esprocarb, mefenacet, molinate, propanil, pyrazolate, cyhalofop-butyl, bispyribac-sodium, pyriminobac-methyl, cafenstrole, oxadiargyl, oxadiazon, bromobutide, MY-100, dimehypo, NB061, MK243, HW-52, AC014, ametryn, hexazinone, asulam, azafenidin, tebuthiuron, and ethametsulfuron-methyl.,

41. The method according to claim 35, further comprising applying a third herbicide or a plant growth regulator.

42. A composition for controlling unwanted plant growth, comprising: a. Structure 【Chemical 21】 [Wherein, A is a cyclopentadiene skeleton containing 1 to 2 heteroatoms, each of the heteroatoms being independently selected from the group consisting of N and S, and one or more of the carbon atoms of the skeleton being -CX ３ , -CX ２ optionally chemically bonded to at least one of the group consisting of -R, -F, -Cl, -Br, and -I, n is 0 to 5, T is unsubstituted or is a methylene group substituted with one or two halides, -CX ３ , CX ２ , R, -F Z is -COOH, -O-R, COOR; -O-(CH ２ CH ２ O) ｎ R (n ≥ 1); -O-(CHMeCH ２ O) ｎ R (n ≥ 1); a sulfonyl group, a primary amine, a secondary amine, a tertiary amine, a carboxamide or a salt thereof, X is selected from F, Cl, Br and I, R is selected from the group consisting of H, substituted or unsubstituted alkyl, and substituted or unsubstituted aryl groups, and when Z is -O-R, R is a substituted or unsubstituted aryl group. ] a compound having the formula or a salt thereof, b. Atrazine, Terbuthylazine, (S)-Metolachlor, Metolachlor, Terbutryn, Simazine, Dimethanamid, (S)-Dimethanamid, Flufenacet, Acetochlor, Aclonifen, Isoxafutole, Isoxachlortole, Mesotrione, Sulcotrione, Metosulam, Flumetsulam, Pendimethalin, Bromoxynil, Bentazone, Carfentrazone-ethyl, Chromazone,nicosulfuron, rimsulfuron, halosulfuron-methyl, metribuzin, flumiclorac-pentyl, prosulfuron, primisulfuron-methyl, dicamba, fluthiacet-methyl, pyridate, 2,4-D, clopyralid, diflufenican, fluroxypyr, MCPA, MCPB, mecoprop (MCPP), metobenzuron, thifensulfuron-methyl, acifluorfen, EPTC, glyphosate, glufosinate, sulfosate, cyanazine, propaquizafop, metamitron, pyriminobac, fenmedifam, desmedifam, ethofumesate, triasulfuron, chloridazon, lenacil, triallate, fluaquizafop, sethoxydim, quizalofop, clopyralid, clethodim, oxasulfuron, acifluorfen, bentazone-ethyl, sulfentrazone, chlorimuron-ethyl, chloransulam-methyl, homosafen, imazamox, imazethapyr, imazapic, imazapyr, lactofen, fenoxaprop (P-ethyl), thidiazuron, tribenuron, trifluralin, dimethachlor, napropamide, cinmethylin, metazachlor, carbetamide, dimefuron, propyzamide, ethametsulfuron-methyl, tebutam, flumetsulam, prometryn, norflurazon, pyrithiobac-sodium, MSMA, DSMA, diuron, flurochloridone, dithiopyr, thiazopyr, oxyfluorfen, ethalfluralin, clodinafop, amidosulfuron, dichlofop-methyl, diflufenican, ethoxysulfuron, fentrazamide, flazasulfuron, florasulam, fluazolate, flucarbazone, flupyrsulfuron-methyl-sodium, flurtamone, iodosulfuron, isoproturon, chlorotoluron, chlorosulfuron, metsulfuron-methyl, sulfosulfuron, tribenuron-methyl, 2,4-DB, 2,At least one herbicide selected from the group consisting of 4-DP, biphenox, flamprop-M, imazamethabenz-methyl, ioxynil, tralkoxydim, fluoroglycofen-ethyl, metobenzthiazuron, isoxaben, prosulfocarb, difenzoquat methyl sulfate, pretilachlor, cinosulfuron, fenclorim, bensulfuron-methyl, imazosulfuron, pyrazosulfuron-ethyl, azimsulfuron, esprocarb, mefenacet, molinate, propanil, pyrazolate, cyhalofop-butyl, bispyribac-sodium, pyriminobac-methyl, cafenstrole, oxadiargyl, oxadiazon, bromobutide, MY-100, dimehypo, NB061, MK243, HW-52, AC014, ametryn, hexazinone, asulam, azafenidin, tebuthiuron, ethametsulfuron-methyl, or a combination thereof, and, c. at least one agriculturally acceptable carrier a mixture of.

43. A composition for controlling unwanted plant growth, comprising: a. Structure 【Chemical 22】 [Wherein, A is a cyclopentadiene skeleton containing 1 to 2 heteroatoms, each of the heteroatoms being independently selected from the group consisting of N and S, and one or more of the carbon atoms of the skeleton being -CX ３ , -CX ２ optionally chemically bonded to at least one of the group consisting of -CR, -F, -Cl, -Br, and -I, n is 0 to 5, T is unsubstituted or is a methylene group substituted with one or two halide atoms, -CX ３ , -F Z is -COOH, -O-R, COOR; -O-(CH ２ CH ２ O) ｎ R (n≥1); -O-(CHMeCH ２ O) ｎ R (n≥1); a sulfonyl group, a primary amine, a secondary amine, a tertiary amine, a carboxamide or a salt thereof, X is selected from F, Cl, Br and I, R is selected from the group consisting of H, substituted or unsubstituted alkyl, and substituted or unsubstituted aryl groups, and when Z is -O-R, R is a substituted or unsubstituted aryl group. ] a compound having the formula or a salt thereof b. at least one plant growth regulator, and c. at least one agriculturally acceptable carrier A composition comprising a mixture of.

44. A method for controlling the amino acid content in a plant or a part of the plant, the method comprising applying an effective amount of the herbicidal composition according to any one of claims 1 to 14.

45. A method for controlling plant growth, the method comprising applying an effective amount of the herbicidal composition according to any one of claims 1 to 14 to a plant or a part of the plant.

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