Novel derivatives of non-coded amino acids and their use in crop protection

Abstract

Novel herbicidal compositions and their use in crop protection, specifically in controlling the growth of harmful weeds, are provided.

Description

Technical Field

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

Background Art

[0002] Amino acids and their derivatives play a role as protein components and are also involved in numerous cellular reactions, thereby affecting several physiological processes such as plant growth and development, intracellular pH control, production of metabolic energy or redox power, and resistance to both abiotic and biotic stresses. Furthermore, the role of amino acids in signal transduction in plants has recently been investigated. In this context, the regulation of amino acid content, flux, and transport within the plant is critically important for plant adaptation, growth, and defense to carbon and nitrogen status.

[0003] The pools of all amino acids are highly induced during stress. This suggests that selective amino acids and their metabolites could be considered as scaffolds for the development of new plant protection products. Proline levels are known to increase significantly as part of the stress response in some plants and are thought to be compatible osmotic regulators. Furthermore, branched-chain amino acids are also highly induced during various stresses.

[0004] The mechanisms underlying the regulation of amino acid pools require further elucidation. The local amino acid concentration depends on both the rates of protein and amino acid synthesis and degradation and the transport processes. This process rather changes the total pool size, which is particularly relevant when bulk degradation occurs, such as during germination and senescence.

Summary of the Invention

Problems to be Solved by the Invention

[0005] There is always a need for new compounds that are effective in controlling the growth of undesirable vegetation. In the most common situations, for example, in useful crops such as cotton, rice, corn / maze, wheat and soybeans, selectively controlling the growth of weeds is required of such compounds. If weed growth in such crops is not inhibited, it will result in significant losses, which will harm the interests of farmers and may increase costs to consumers. In other situations, it is also desired that herbicides control the growth of all plants. Examples of areas where complete control of all vegetation is desired are railway lines, areas around storage tanks, and industrial storage areas. There is still a long-term unmet need to identify new compounds with herbicidal activity that are more effective, less expensive, and environmentally safe.

[0006] (Summary of the Invention) A major object of the present invention is to provide a novel, safe and potent herbicide. [Means for Solving the Problems]

[0007] According to some embodiments, the present invention has the structure:

[0008] [Chemical Formula] a compound having the formula or a salt thereof [wherein, A is a cyclopentadiene, benzene or indene skeleton containing 1 to 4 heteroatoms; each of the heteroatoms is independently selected from the group consisting of N, S, Se and O; one or more of the carbon, nitrogen, sulfur or selenium atoms of the ring are optionally chemically bonded to at least one of the group consisting of -CX3, -CX2R, -COX, -CHO, -COR, -CO2R, -CONH2, -CONHR, sulfur = S, oxygen = O, -F, -Cl, -Br and -I, wherein X is selected from F, Cl, Br and I; T is -(CH2) n-, -OR1, -SR1, -SOR1, -CSR1, -CS-, -POHR1, -PO(OR1)R1, -CO-, -C(O)R1 and -COOR1; Z is H, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, -COOH, -COO-, -OH, -O-R, a linear, branched, cyclic, aromatic or heteroaromatic chain; -O-(CH2CH2O) n R (n≥1); -O-(CHMeCH2O) n R having a saturated or unsaturated alcohol residue of (n≥1); a substituted or unsubstituted phosphate group, a sulfonyl group, -SO3H, a sulfo group, a sulfonic acid, a cyanocarbamoyl group, a primary amine, a secondary amine, a tertiary amine, a carboxamide, -NR-O-R, -O-NR, or a salt thereof; wherein R is H, a substituted or unsubstituted alkyl group, and a substituted or unsubstituted aryl group; R1 is -(CH2) n -(n is from 0 to 9.)] There is provided a herbicidal composition comprising the same, comprising at least one agriculturally acceptable carrier.

[0009] According to some embodiments, the present invention provides that Z is

[0010]

Chemical formula

[0011] According to some embodiments, the present invention provides a structure:

[0012]

Chemical formula

[0013] According to some embodiments, the present invention

[0014]

Chem.

[0015] According to some embodiments, the present invention is a herbicidal composition for controlling unwanted plant growth, a. Structure:

[0016]

Chem.

[0017] According to some embodiments, the present invention is a herbicidal composition for controlling unwanted plant growth, a. Structure:

[0018]

Chemical formula

[0019] According to some embodiments, the present invention provides a method for controlling unwanted plant growth, the method comprising applying an agricultural composition according to one or more of the above embodiments to a location of unwanted plant growth.

[0020] According to some embodiments, the present invention provides a method for controlling unwanted plant growth, the method comprising applying to a location of unwanted plant growth a compound having a herbicidally effective amount or a salt thereof of the structure:

[0021]

Chemical formula

[0022] According to some embodiments, the present invention provides a method for selectively controlling the growth of harmful weeds, the method comprising applying to a crop field an effective amount of a herbicidal composition according to one or more of the above embodiments.

Brief Description of the Drawings

[0023]

Figure 1

DETAILED DESCRIPTION OF THE INVENTION

[0024] Herein, the present invention will be more fully described hereinafter with reference to the accompanying examples which illustrate embodiments of the invention. However, the present invention may be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. 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.

[0025] According to some embodiments, the present invention has the structure:

[0026]

Chemical formula

[0027] According to some embodiments of the above composition, A is an electron-withdrawing group (EWG). As used herein, the term "electron-withdrawing group" (EWG) generally refers, without limitation, to an atom or group that withdraws electron density from an adjacent atom or aromatic ring by resonance or inductive effects. Non-limiting examples of EWGs of the present invention include trifluoromethanesulfonyl group and triflate group; substituted ammonium groups, such as, without limitation, -NR3 +(R is alkyl or H); nitro and nitroso groups -NO2, -N=O; sulfonic acid and sulfonyl groups (-O)-SO3H, -SO2R; cyano group, trihalomethyl group -CX3 (X is F, Cl, Br, I); halocarbonyl group -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 group -N≡N + or -N=NR; an imino group -CR=NR or -N=CR2 is included.

[0028] According to some embodiments of the above composition, T may be, without limitation, -(CH2) n -, -OR1, -N=CHR1, -CS(O)2R1, -SR1, -CS-, -CSR1, -CO-, -COR1, -C≡CR1, -C=NR1 and -C=CHR1; wherein R1 is -(CH2) n -(n is from 0 to 9); According to some embodiments of the above composition, Z may be, without limitation, H, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, carboxyl and its salts -COOH or -COO-, hydroxyl -OH, ether -O-R, a linear, branched, cyclic chain, or an aromatic / heteroaromatic chain, ethylene- and polyethylene glycol -O-(CH2CH2O) n R (n≧1, R is H or alkyl), propylene and polypropylene glycol -O-(CHMeCH2O) nAn ester - COOR having a saturated or unsaturated alcohol group having R (n ≧ 1, R is H or alkyl), (substituted and unsubstituted) phosphate, sulfate / sulfonyl, -SO3H, sulfo group, sulfonic acid, linear, branched, cyclic aliphatic chain, cyclic aromatic / heteroaromatic chain, ethylene glycol and polyethylene glycol as described above, propylene glycol, polypropylene glycol as described above, a carbamoyl group consisting of primary, secondary and tertiary amides substituted therewith, primary amine, secondary amine, tertiary amine, carboxamide, alkoxyamine groups of type -NR - O - R and -O - NR2, hydrazine, acetamide group -NH - COR, and methane imidoamide moiety, or salts thereof may also be used.

[0029] According to some embodiments of the above composition, Z is

[0030]

Chemical formula

[0031] According to some embodiments, the above composition

[0032]

Chemical formula

[0033] According to some embodiments, the above composition

[0034]

Chemical formula

[0035] According to some embodiments, the above composition

[0036]

Chemical formula

[0037] According to some embodiments, the above composition

[0038]

Chemical formula

[0039] According to some embodiments, the above composition

[0040]

Chemical formula

[0041] According to some embodiments, the above composition

[0042]

Chemical formula

[0043] According to some embodiments, the above composition

[0044]

Chemical formula

[0045] According to some embodiments, the above composition

[0046]

Chemical formula

[0047] According to some embodiments, the above composition

[0048] [Chemical formula] It contains a compound having a structure selected from the following.

[0049] According to some embodiments, the above composition

[0050] [Chemical formula] It contains a compound having a structure selected from the following.

[0051] According to some embodiments, the above composition

[0052] [Chemical formula] It contains a compound having a structure selected from the following.

[0053] According to some embodiments, the above composition

[0054] [Chemical formula] It contains a compound having a structure selected from the following.

[0055] According to some embodiments, the above composition

[0056] [Chemical formula] It contains a compound having a structure selected from the following.

[0057] According to some embodiments, the above composition

[0058] [Chemical formula] It contains a compound having a structure selected from the following.

[0059] According to some embodiments of the above composition, the herbicidal 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 other embodiments, 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, terbutryn, simazine, dimethenamid, (S)-dimethenamid, flufenacet, acetochlor, alachlor, isoxaflutole, isoxachlortole, mesotrione, sulcotrione, mesotrione, 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, Diflufenzoppil, Fluroxypyr, MCPA, MCPB, Mecoprop (MCPP), Metobenzuron, Thifensulfuron-methyl, Acifluorfen, EPTC, Glyphosate, Glufosinate, Sulfosate, Cyanazine, Propyzamide, Metamitron, Pyraflufen, Fenmedipham, Desmedipham, Ethofumesate, Triasulfuron, Chloridazon, Lenacil, Triallate, Flufenacet, Sethoxydim, Quizalofop, Clopyralid, Clethodim, Oxasulfuron, Aciflurofen, Benazolin-ethyl, Sulfentrazone, Chlorimuron-ethyl, Chloransulam-methyl, Hinosafen, Imazamox, Imazakirin, Imazethapyr, Imazapyr, Lactofen, Fenoxaprop (P-ethyl), Thidiazuron, Tribufos, Trifluralin, Dimethachlor, Napropamide, Cinmethylin, Metazachlor, Carbetamide, Dimefuron, Propyzamide, Ethametsulfuron-methyl, Tebuthiuron, Fluometuron, Prometryn, Norflurazon, Pyrithiobac-sodium, MSMA, DSMA, Diuron, Flurochloridone, Dithiopyr, Thiazopyr, Oxyfluorfen, Etalfluralin, Clodinafop, Amidosulfuron, Dichlofop-methyl, Difluophenican, Ethoxysulfuron, Fentrazamide, Flazasulfuron, Florasulam, Fluazolate, Flucarbazone, Flupyrsulfuron-methylsodium, Flurtamone, Iodosulfuron, Isoproturon, Chlorotoluron, Chlorsulfuron, Metsulfuron-methyl, Sulfosulfuron, Tribenuron-methyl, 2,4-DB, 2,Selected from the group consisting of 4-DP, biphenox, flamprop-M, imazamethabenz-methyl, ioxynil, tralkoxydim, fluoroglycofen-ethyl, metobenzthiazuron, isoxaben, prosulfocarb, difenzoquat-methylsulfate, pretilachlor, cinosulfuron, fenclorim, bensulfuron-methyl, imazosulfuron, pyrazosulfuron-ethyl, azimsulfuron, esprocarb, mefenacet, molinate, propanil, pyrazolate, cyhalofop-butyl, bispyribac-sodium, pyriminobac-methyl, cafenstrole, oxadiargyl, oxadiazone, bromobutide, MY-100, dimehypo, NB061, MK243, HW-52, AC 014, ametryn, hexazinone, asulam, azafenidin, tebuthiuron, ethametsulfuron-methyl, or combinations thereof.,

[0060] According to some embodiments, the present invention provides a method for controlling unwanted plant growth, the method comprising applying a herbicidal composition according to one or more of the above embodiments to a location of unwanted plant growth.,

[0061] According to some embodiments, the present invention provides a method for controlling unwanted plant growth, the method comprising applying to a location of unwanted plant growth a compound having the structure:

[0062]

Chemical formula

[0063] According to some embodiments of the above method, Z is, without limitation,

[0064]

Chemical formula

[0065] According to some embodiments of the above method, a non-limiting listing of the compound, or an agriculturally acceptable salt, includes

[0066]

Chem.

[0067] According to some embodiments, the method further comprises applying at least one crop protection agent to a location of unwanted plant growth. In one embodiment, a non-limiting listing of crop protection agents includes, without limitation, herbicides, fungicides, insecticides, and plant growth regulators.

[0068] According to some embodiments of the above method, the crop protection agent is a herbicide.

[0069] According to some embodiments of the above method, the crop protection agent is an amino acid synthesis inhibitor herbicide. A non-limiting listing of amino acid synthesis inhibitor herbicides includes sulfonylurea herbicides, imidazolinone herbicides, sulfonamide herbicides, amino acid derivatives, imazamox, imazapic, imazethapyr, imazakipyr, imazapyr, and imazamethabenz, chlorimuron, primisulfuron, thifensulfuron, triasulfuron,nicosulfuron, metsulfuron, tribenuron, rimsulfuron, triflusulfuron, glyphosate, or any combination thereof.

[0070] According to some embodiments of the above method, the crop protection agent is a plant growth regulator. A non-limiting listing of plant growth regulators includes dicamba, 2,4-D, clopyralid, and fluroxypyr.

[0071] According to some embodiments, the present invention is a method for controlling unwanted plant growth, comprising at a location of unwanted plant growth a. Structure:

[0072]

Chem.

[0073] According to some embodiments of the above method, Z can be, without limitation,

[0074]

Chemical formula

[0075] According to some embodiments of the above method, the second herbicide is an amino acid synthesis inhibitor herbicide.

[0076] According to some embodiments of the above method, the second herbicide can be, without limitation, selected from sulfonylurea herbicides, imidazolinone herbicides, sulfonamide herbicides, and amino acid derivatives.

[0077] According to some embodiments of the above method, the non-limiting enumeration of the herbicides of the present invention includes imazamox, imazapic, imazethapyr, imazakirin, imazapyr, imazamethabenz, chlorimuron, primisulfuron, thifensulfuron, triasulfuron,nicosulfuron, metsulfuron, tribenuron, rimsulfuron, triflusulfuron, glyphosate, atrazine, terbuthylazine, (S)-metolachlor, metolachlor, terbutryn, simazine, dimethenamid, (S)-dimethenamid, flufenacet, acetochlor, alachlor, isoxaflutole, 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, Diflufenzoppil, Fluroxypyr, MCPA, MCPB, Mecoprop (MCPP), Metobenzuron, Thifensulfuron-methyl, Acifluorfen, EPTC, Glyphosate, Glufosinate, Sulfosate, Cyanazine, Propyzamide, Metamitron, Pyraflufen, Fenmedipham, Desmedipham, Ethofumesate, Triasulfuron, Chloridazon, Lenacil, Triallate, Fluaquizat, Sethoxydim, Quizalofop, Clopyralid, Clethodim, Oxasulfuron, Aciflurofen, Benazolin-ethyl, Sulfentrazone, Chlorimuron-ethyl, Chloransulam-methyl, Homethylsafen, Imazamox, Imazethapyr, Imazapic, Imazapyr, Lactofen, Fenoxaprop (P-ethyl), Thidiazuron, Tribufos, Trifluralin, Dimethachlor, Napropamide, Cinmethylin, Metazachlor, Carbetamide, Dimefuron, Propyzamide, Ethametsulfuron-methyl, Tebuthiuron, Fluometuron, Prometryn, Norflurazon, Pyrithiobac-sodium, MSMA, DSMA, Diuron, Flurochloridone, Dithiopyr, Thiazopyr, Oxyfluorfen, Etridiazol, Ethalfluralin, Clodinafop, Amidosulfuron, Dichlorprop-methyl, Difluenican, Ethoxysulfuron, Fentrazamide, Flazasulfuron, Florasulam, Fluazolate, Flucarbazone, Flupyrsulfuron-methylsodium, Flurtamone, Iodosulfuron, Isoproturon, Chlorotoluron, Chlorsulfuron, Metsulfuron-methyl, Sulfosulfuron, Tribenuron-methyl, 2,4-DB, 2,It includes 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, AC 014, ametryn, hexazinone, asulam, azafenidin, tebuthiuron and ethametsulfuron-methyl.,

[0078] According to some embodiments of the above method, the method for controlling unwanted plant growth further includes applying a third herbicide or plant growth regulator.,

[0079] According to some embodiments, the present invention is a composition for controlling unwanted plant growth, a. Structure:

[0080]

Chemical formula

[0081] According to some embodiments, the present invention is a composition for controlling unwanted plant growth, a. Structure:

[0082]

Chemical formula

[0083] According to some embodiments, the present invention has the structure:

[0084]

Chemical formula

[0085] According to some embodiments, a method of controlling the amino acid content in a plant or a plant part thereof includes applying an herbicidal composition according to one or more of the above embodiments in an effective amount.

[0086] According to some embodiments, the non-limiting listing of the above compounds or their salts includes

[0087]

Chemical formula

[0088] According to some embodiments, the present invention provides a method of controlling plant growth, which includes applying an herbicidal composition or a compound according to one or more of the above embodiments in an effective amount to a plant or a plant part thereof.

[0089] According to some embodiments, the present invention provides a method of controlling the growth of a plant that is at least partially resistant to herbicides selected from the HPAC9 group (inhibitors of EPSP synthesis), group 2 (acetolactate synthase (ALS) inhibitors), and group 4 (plant growth regulators or synthetic auxins), which includes applying an herbicidal composition or a compound according to one or more of the above embodiments in an effective amount to a plant or a plant part thereof.

[0090] According to some embodiments of the above method, the location of unwanted vegetation is a crop field.

[0091] According to some embodiments of the above method, the crop is selected from the group consisting of corn, wheat, rice, barley, sorghum and oats.

[0092] According to some embodiments of the above method, the herbicidal composition is applied pre-emergence.

[0093] According to some embodiments of the above method, the herbicidal composition is applied post-emergence.

[0094] According to some embodiments, the present invention provides a method for selectively controlling the growth of harmful and / or unwanted weeds, the method comprising applying to a crop field an effective amount of a herbicidal composition or compound according to one or more of the above embodiments. As used herein, the term "selectively controlling" refers without limitation to the situation when the growth of harmful and / or unwanted weeds is affected by the composition according to an embodiment of the present invention, and at this time, without limitation, does not affect the growth of desirable vegetation such as crops. According to some embodiments, the weeds are considered to be relevant to the cultivation of corn, wheat, rice, barley, sorghum and / or oats.

[0095] According to some embodiments of the above method, the herbicidal composition is applied pre-emergence.

[0096] According to some embodiments of the above method, the herbicidal composition is applied post-emergence.

[0097] According to some embodiments of the above method, here, the crop is selected from the group consisting of corn, wheat, rice, barley, sorghum and oats.

[0098] According to some embodiments of the above method, the effective amount of the herbicidal composition or compound according to one or more of the above embodiments, when applied pre-emergence, is in the range of 50 gr / Ha to 2000 gr / Ha.

[0099] According to some embodiments of the above method, the effective amount of the herbicidal composition or compound according to one or more of the above embodiments, when applied pre-emergence, is 50 gr / Ha, 100 gr / Ha, 150 gr / Ha, 200 gr / Ha, 250 gr / Ha, 300 gr / Ha, 350 gr / Ha, 400 gr / Ha, 450 gr / Ha, 500 gr / Ha, 550 gr / Ha, 600 gr / Ha, 650 gr / Ha, 700 gr / Ha, 750 gr / Ha, 800 gr / Ha, 850 gr / Ha, 900 gr / Ha, 950 gr / Ha, 1000 gr / Ha, 1050 gr / Ha, 1100 gr / Ha, 1150 gr / Ha, 1200 gr / Ha, 1250 gr / Ha, 1300 gr / Ha, 1350 gr / Ha, 1400 gr / Ha, 1450 gr / Ha, 1500 gr / Ha, 1550 gr / Ha, 1600 gr / Ha, 1650 gr / Ha, 1700 gr / Ha, 1750 gr / Ha, 1800 gr / Ha, 1850 gr / Ha, 1900 gr / Ha, 1950 gr / Ha, 2000 gr / Ha.

[0100] According to some embodiments of the above method, the effective amount of the herbicidal composition or compound according to one or more of the above embodiments, when applied post-emergence, is in the range of 125 gr / Ha to 2000 gr / Ha.

[0101] According to some embodiments of the above method, the effective amount of the herbicidal composition or compound according to one or more of the above embodiments, when applied pre-emergence, is 125 gr / Ha, 150 gr / Ha, 175 gr / Ha, 200 gr / Ha, 225 gr / Ha, 250 gr / Ha, 275 gr / Ha, 300 gr / Ha, 325 gr / Ha, 350 gr / Ha, 375 gr / Ha, 400 gr / Ha, 425 gr / Ha, 450 gr / Ha, 475 gr / Ha, 500 gr / Ha, 525 gr / Ha, 550 gr / Ha, 575 gr / Ha, 600 gr / Ha, 625 gr / Ha, 650 gr / Ha, 675 gr / Ha, 700 gr / Ha, 725 gr / Ha, 750 gr / Ha, 775 gr / Ha, 800 gr / Ha, 825 gr / Ha, 850 gr / Ha, 875 gr / Ha, 900 gr / Ha, 925 gr / Ha, 950 gr / Ha, 975 gr / Ha, 1000 gr / Ha, 1025 gr / Ha, 1050 gr / Ha, 1075 gr / Ha, 1100 gr / Ha, 1125 gr / Ha, 1150 gr / Ha, 1175 gr / Ha, 1200 gr / Ha, 1225 gr / Ha, 1250 gr / Ha, 1275 gr / Ha, 1300 gr / Ha, 1325 gr / Ha, 1350 gr / Ha, 1375 gr / Ha, 1400 gr / Ha, 1425 gr / Ha, 1450 gr / Ha, 1475 gr / Ha, 1500 gr / Ha, 1525 gr / Ha, 1550 gr / Ha, 1575 gr / Ha, 1600 gr / Ha, 1625 gr / Ha, 1650 gr / Ha, 1675 gr / Ha, 1700 gr / Ha, 1725 gr / Ha, 1750 gr / Ha, 1775 gr / Ha, 1800 gr / Ha, 1825 gr / Ha, 1850 gr / Ha, 1875 gr / Ha, 1900 gr / Ha, 1925 gr / Ha, 1950 gr / Ha, 1975 gr / Ha, 2000 gr / Ha.

[0102] Results As can be seen from the experimental data, the NCAADs of the present invention have strong herbicidal activity. This is contrary to the initial hypothesis that these compounds can only act as inactive structural analogs of herbicidal non-coding AAs (NCAAs). Furthermore, surprisingly, the NCAADs of the present invention exhibit herbicidal activity 10 to 100 times higher than the corresponding NCAAs.

[0103] A number of NCAADs showing herbicidal activity in both foliar application and soil application suggest effective absorption by leaves, shoots and roots. On the other hand, the corresponding NCAAs only exhibited herbicidal activity in soil application.

Example

[0104] [Example 1] Derivatives of non-coding amino acids having herbicidal activity All compounds were synthesized from the beginning with a purity ≧ 95%. The structure was confirmed by LCMS and H-NMR. Table 1 includes a non-exclusive listing of derivatives of the claimed scope exemplifying non-coding heterocyclic amino acids.

[0105]

Table 1

[0106] [Example 2] Effects of derivatives of non-coding amino acids on germination and early growth of plants / weeds / dicotyledonous plants Materials: Seeds of Lettuce R. (Super-Jericho, non-stabilized) were obtained from Ben Shahar Moshe Ltd. with a purity of 99%. The test compounds listed in Table 3 below were synthesized from scratch or purchased from different vendors. Bioassay: A filter paper bioassay using lettuce seeds was carried out in accordance with Bertin et al. 2009, including the adjustments described below. The seeds were placed on Whatman no. 1 filter paper (Whatman, Middlesex, U.K.) in Petri dishes at concentrations ranging from 0 (control) to 1 mmol / l together with 2.0 ml of an aqueous solution of the test material (10 seeds per plate). The Petri dishes were arranged in a tray tilted at a 45° angle and kept in the dark for 48 hours. Then, the tray with the plates was transferred to a growth chamber and kept for 4 days with 6 / 18 dark / bright cycles. Each experiment was repeated at least twice.

[0107] The growth of the plant's radicles and new shoots was visually evaluated 6 days after the start of the test to determine the minimum effective concentration (MEC) of the test material. In the context of the present invention, the MEC was set as the lowest concentration level of the test material that caused a deviation (poor formation of radicles or new shoots). The MEC is expressed in arbitrary units as an activity score, as presented in Table 2.

[0108]

Table 2

[0109]

Table 3

[0110] The results presented in Example 2 (Table 3) illustrated the effect of the claimed compounds on the germination and early growth of plants. The effect of the compounds tested in the germination test usually correlated well with the herbicidal activity of the compounds in both pre-emergence and post-emergence applications.

[0111] [Example 3] Herbicidal Activity of Selected Derivatives of Non-Coded Amino Acids against Weed Growth Weed seeds were sown in 0.3-liter pots containing moderately heavy clay-loam soil (55% clay, 23% silt, 20% sand, 2% organic matter, pH 7.1) from an organic field. This experiment was conducted in a completely randomized design. Each treatment was replicated three times (three pots). Each compound was typically tested on a weed panel containing Amaranthus, Abutilon, Xanthium strumarium, Cirsium arvense and Sinapis.

[0112] The herbicide was applied at doses of 0 (control) to 5 mg / pot. The herbicide was applied to the growing plants at the stage of 2-3 true leaves (post-emergence treatment). The plants were grown in a mesh house throughout the experiment. The plant growth at 6, 12, 19, 26 and 32 days after application (DAA) was evaluated on a scale of 0-5, where 0 represents a dead plant and 5 represents a healthy plant similar to or not different from the control. In the context of the present invention, the herbicidal effect was expressed as a score calculated as the average of the evaluations of plant vigor, height and leaf color. The results of the experiment are presented in Table 4 below.

[0113] [Table 4]

[0114] [Example 5] Selectivity of Selected Derivatives of Non-Coded Amino Acids to Cereals The selectivity of the claimed compounds to cereals was exemplified using Compounds 7114, 6693, 5839, 6688. The tests were conducted on cereal crops such as wheat, maize, rice, barley, sorghum and oats (Figure 1). The test plants were grown and treated as described in Example 4 (post-emergence leaf application). The herbicidal effect was evaluated using the Damage Score detailed in Example 4.

[0115] The selectivity of the tested compounds to cereals was observed at a maximum rate of 5 kg a.i. / Ha, at a dose of 0.05%, and at 0.5 kg a.i. / Ha for each of the foliar, drench and soil applications.

[0116] The terms used in this specification are for the purpose of describing particular embodiments only and are not intended to limit the invention. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise. The term "comprises" or "comprising", as used herein, specifies the presence of the described feature, integer, step, operation, element, component and / or group or combinations thereof, but does not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components and / or groups or combinations thereof. As used herein, the terms "comprises", "comprising", "includes", "including", "having" and their conjugates mean "including but not limited to". The term "consisting of" means "including but not limited to".

[0117] As used herein, the term "and / or" is interpreted to include any and all possible combinations, or one or more of the related listed items, as well as the absence of a combination when interpreted in the alternative ("or").

[0118] Unless otherwise defined, all terms (including technical and scientific terms) used in this specification shall have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Terms such as those defined in commonly used dictionaries shall be interpreted to have a meaning that conforms to their meaning in the context of this specification and the "claims", and it should be further understood that they should not be interpreted in an idealized or overly formal sense unless explicitly so defined herein. Well-known functions or structures may not be described in detail for the sake of brevity and / or clarity.

[0119] Terms such as first, second, etc. may be used in this specification to describe various elements, components, regions, layers, and / or sections, but it will be understood that these elements, components, regions, layers, and / or sections should not be limited by these terms. Rather, these terms are used only to distinguish one element, component, region, layer, and / or section from another.

[0120] Throughout this application, various embodiments of the present invention may be presented in a range format. It should be understood that the description in range format is for convenience and brevity only and should not be construed as an inflexible limitation on the scope of the present invention. Accordingly, the description of a range should be considered to have specifically disclosed all possible sub-ranges, as well as the individual numerical values within that range. For example, a description of a range such as 1 - 6 should be considered to have specifically disclosed sub-ranges such as 1 - 3, 1 - 4, 1 - 5, 2 - 4, 2 - 6, 3 - 6, etc., as well as the individual numbers within that range, such as 1, 2, 3, 4, 5, and 6. This applies regardless of the width of the range.

[0121] Whenever a numerical range is indicated in this specification, it is meant to include any cited number (fractional or integral) within the indicated range. The phrases "ranging / ranges between" a first indicated number and a second indicated number, and "ranging / ranges from" a first indicated number "to" a second indicated number are used interchangeably herein and are meant to include the first and second indicated numbers, and all fractional and integral numbers therebetween.

[0122] Whenever the term "about" is used, it is meant to refer to a measurable value such as an amount, period of time, etc., and is meant to encompass variations of ±20%, ±10%, ±5%, ±1% or ±0.1% from a particular value, for the reason that such variations are appropriate for carrying out the disclosed method.

[0123] Certain features of the invention that are described in the context of separate embodiments for clarity may also be provided in combination in a single embodiment. Conversely, various features of the invention that are described in the context of a single embodiment for brevity may also be provided separately, or in any suitable sub-combination, or as suitable in any other described embodiment of the invention. Certain features 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.

[0124] As used herein, the terms "comprises", "comprising", "includes", "including", "having" and their conjugates mean "including but not limited to".

[0125] The term "consisting of" means "consisting of and limited to".

[0126] As used herein, the singular forms "a", "an" and "the" include plural referents unless the context clearly dictates otherwise. For example, the term "a compound" or "at least one compound" may include a plurality of compounds, including mixtures thereof.

[0127] When an element is referred to as being "on" another element, "attached" to another element, "connected" to another element, "coupled" with another element, "in contact" with another element, etc., it can be directly on, directly attached to, directly connected to, directly coupled with, and / or in direct contact with the other element, or intervening elements may also be present. In contrast, when an element is referred to as, for example, being "directly on" another element, "directly attached" to another element, "directly connected" to another element, "directly coupled" with another element, or "in direct contact" with another element, intervening elements are absent. It will also be recognized by those skilled in the art that references to a structure or feature being "proximate" to another feature may have portions that overlap or underlie the proximate feature.

[0128] Terms such as first, second, etc. may be used herein to describe various elements, components, regions, layers, and / or sections, but it will be understood that these elements, components, regions, layers, and / or sections are not to be limited by these terms. Rather, these terms are used only to distinguish one element, component, region, layer, and / or section from another.

[0129] As will be appreciated by those skilled in the art, the compounds of the various formulas disclosed herein may contain chiral centers, such as asymmetric carbon atoms. As such, the present disclosure relates to the synthesis of both (i) racemic mixtures of the active compounds and (ii) enantiomeric forms of the active compounds. The resolution of racemic compounds into their enantiomeric forms, and the racemization of optically active enantiomeric forms, can be carried out in accordance with procedures known in the art. Geometric isomers of double bonds, etc. may also be present in the compounds disclosed herein, and all such stable isomers are included within the present disclosure unless otherwise specified. Also included within the compounds of the present disclosure are tautomers (e.g., tautomers of triazole and / or imidazole), as well as rotamers. All chains defined by formula herein that contain three or more carbons may be saturated or unsaturated unless otherwise specified.

[0130] It will be understood that the substituents and substitution patterns in the compounds used in the methods of the present invention are selected by those skilled in the art to provide compounds that are chemically stable and readily synthesizable from readily available starting materials by techniques known in the art. It will be understood that when a substituent is substituted by more than one group, these multiple groups may be on the same carbon or on different carbons, provided that a stable structure is provided.

[0131] The term "optionally substituted" group refers to a functional group in which one or more bonds to a contained hydrogen atom are replaced by a bond to a non-hydrogen or non-carbon atom, provided that normal valency is maintained and the substitution results in a stable compound. A substituted group also includes a group in which one or more bonds to a carbon atom or hydrogen atom are replaced by one or more bonds to a heteroatom (including double or triple bonds). Where multiple substituent moieties are disclosed or claimed, the substituted compound may be substituted singly or multiply, independently, by one or more of the disclosed or claimed substituent moieties. Being independently substituted means that the (two or more) substituents may be the same or different. In the selection of the compounds of the present invention, one of ordinary skill in the art will recognize that the various substituents will be selected in accordance with well-known rules of chemical structural connectivity.

[0132] 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. An "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 butyryl group, a benzoyl group, or an alkylbenzoyl group. "Alkyl", as used herein, refers to a straight or branched hydrocarbon containing 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 a straight or branched 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, iso-pentyl, neopentyl, n-hexyl, 3-methylhexyl, 2,2-dimethylpentyl, 2,3-dimethylpentyl, n-heptyl, n-octyl, n-nonyl, n-decyl, etc. As used herein, the determination of a carbon number range, such as C1-C12 alkyl, is intended to include each of the intervening carbon numbers within the stated range and any other stated or intervening carbon number values such that sub-ranges of the carbon numbers within the specific carbon number range can be independently specified.For example, C1-C12 alkyl is intended to include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, and dodecyl, which, as noted above, includes straight-chain and branched groups, and the C1-C12 alkyl carbon number range can also be more restrictively specified as a sub-range, such as C1-C4 alkyl, C2-C8 alkyl, C2-C4 alkyl, C3-C5 alkyl, or any other sub-range within a broader carbon number range. Additionally, a carbon number range that specifically excludes carbon numbers is contemplated, such that a sub-range that excludes any one or both of the specified carbon number limits of the range is so. As is generally understood by those skilled in the art, "saturated" refers to a state where all available valence bonds of an atom (e.g., carbon) are bonded to other atoms. Similarly, "unsaturated" refers to a state where not all available valence bonds are bonded to other atoms; in such compounds, the extra bonds typically take the form of double or triple bonds (usually with carbon). For example, a carbon chain is "saturated" when there are no double or triple bonds present along or directly bonded to the chain (e.g., carbonyl), and the carbon chain is "unsaturated" (e.g., carbonyl) when at least one double or triple bond is present along or directly bonded to the chain. Further, the presence or absence of substituents that depend on chain saturation will be understood by those skilled in the art to depend on the valence requirements of the atom (e.g., carbon) to which the substituent is bonded. "Alkenyl", as used herein, refers to a straight-chain or branched hydrocarbon containing one or two to ten or twenty or more carbons and containing at least one carbon-carbon double bond structurally formed, for example, 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-chain or branched hydrocarbon group containing one or two to ten or twenty or more carbon atoms and containing at least one carbon-carbon triple bond.Representative examples of alkynyl include, but are not limited to, ethynyl, 1-propynyl, 2-propynyl, 3-butynyl, 2-pentynyl, 1-butynyl, and the like. The term "cycloalkyl", as used herein, refers to a saturated cyclic hydrocarbon group containing 3 to 8 or more carbon atoms.

[0133] As understood in the art, the term "optionally substituted" indicates that a particular group is either unsubstituted or substituted by one or more suitable substituents. A "substituent" that is "substituted" is an atom or group that takes the place of a hydrogen atom on the parent chain or on the 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- to 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" means a cyclic aromatic hydrocarbon in which one or more carbon atoms are replaced by heteroatoms (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 that is 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 the three hydrogen atoms replaced by an alkyl group or an aromatic group. A "secondary amine" has two organic substituents bonded to nitrogen together with one hydrogen. A "tertiary amine" has three organic substituents bonded to nitrogen. "Amide", as used herein, refers to a functional group having a carbonyl group (C=O) linked to a nitrogen atom (N), or an organic compound containing this group, and generally,

[0134]

Chemical formula

[0135] It will be understood that the compounds, compositions, and methods provided herein may be further specified in some embodiments by provisos or limitations excluding certain substituents, groups, moieties, structures, components, steps, or conditions that are applicable in relation to various broader specifications and the exemplification described herein.

[0136] The "agriculturally acceptable carriers" of the present invention include, but are not limited to, adjuvants, mixers, accelerators, etc. to which the application of chemical formulas is beneficial. Suitable carriers, in particular, should not be phytotoxic to valuable crops at the concentrations used in the application of the composition for selective weed control in the presence of crops, and should not chemically react with the compounds of the chemical formulas within this specification, or with the components of other compositions. Such mixtures can be designed to be applied directly to weeds or to the site, or can be concentrates or formulations that are normally diluted with additional carriers and adjuvants prior to application. They may contain inert or active constituents and may 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 herbicidal compositions of the present invention are well known to those skilled in the art. For example, liquid carriers that can be used 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, etc. Water is generally the carrier selected for dilution of concentration. Suitable solid carriers include talc, pyrophyllite clay, silica, attapulgus clay, kieselguhr, chalk, diatomaceous earth, lime, calcium carbonate, bentonite clay, fuller's earth, cottonseed hulls, wheat flour, soybean flour, pumice, wood flour, walnut flour, lignin, etc.

[0137] 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 and are especially designed to be diluted with a carrier prior to application. Surfactants can be anionic, cationic, nonionic in nature and can be utilized for emulsifying, wetting, suspending or other purposes. Typical surfactants include salts of alkyl sulfates such as diethanolammonium lauryl sulfate; alkylaryl sulfonates such as calcium dodecylbenzene sulfonate; alkylphenol-alkylene oxide adducts such as nonylphenol-C 18 ethoxylate; alcohol-alkylene oxide adducts such as tridecyl alcohol-C 16 ethoxylate; soaps such as sodium stearate; alkylnaphthalene sulfonates such as sodium dibutylnaphthalene sulfonate; dialkyl esters of sulfosuccinates such as sodium di(2-ethylhexyl) sulfosuccinate; sorbitol esters such as sorbitol oleate; quaternary amines such as lauryl trimethylammonium 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 phosphates.

[0138] Other adjuvants commonly utilized in herbicidal compositions include defoamers, compatibilizers, sequestering agents, neutralizing and buffering agents, corrosion inhibitors, dyes, odorants, penetration enhancers, spreading agents, sticking agents, dispersing agents, thickening agents, freezing point depressants, antibacterial 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.

[0139] "Agriculturally acceptable salts" are intended to mean salts that retain the biological effectiveness of the free acids and bases of the specified compounds, as well as salts that are not biologically or otherwise undesirable. Examples of agriculturally acceptable salts include sulfates, pyrosulfates, bisulfates, sulfites, bisulfites, phosphates, monohydrogen phosphates, dihydrogen phosphates, metaphosphates, pyrophosphates, chlorides, bromides, iodides, acetates, propionates, decanoates, caprylates, acrylates, formates, isobutyrates, caproates, heptanoates, propiolates, oxalates, malonates, succinates, suberates, sebacates, fumarates, maleates, butyne-1,4-dioates, hexyne-1,6-dioates, benzoates, chlorobenzoates, methylbenzoates, dinitrobenzoates, hydroxybenzoates, methoxybenzoates, phthalates, sulfonates, xylenesulfonates, phenylacetates, phenylpropionates, phenylbutyrates, citrates, lactates, γ-hydroxybutyrates, glycolates, tartrates, methane-sulfonates, propanesulfonates, naphthalene-1-sulfonates, naphthalene-2-sulfonates and mandelates.

[0140] 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 limiting the scope of the invention in an inflexible manner. Thus, a range description should be considered to have specifically disclosed all the possible sub-ranges and individual numerical values within that range. For example, a range description such as 1 to 6 should be considered to have specifically disclosed sub-ranges such as 1 to 3, 1 to 4, 1 to 5, 2 to 4, 2 to 6, 3 to 6, etc., as well as individual numerical values within that range, such as 1, 2, 3, 4, 5 and 6. This applies regardless of the width of the range.

[0141] Whenever a numerical range is indicated in this specification, it is meant to include any cited number (fraction or integer) within the indicated range. The phrases "ranging / ranges between" a first indicated number and a second indicated number, and "ranging / ranges" from a first indicated number "to" a second indicated number are used interchangeably herein and are meant to include the first and second indicated numbers, and all fractional and integral numbers therebetween.

[0142] Certain features of the invention that are described for clarity in connection with separate embodiments may also be provided in combination in a single embodiment. Conversely, various features of the invention that are described for brevity in connection with a single embodiment may also be provided separately, or in any suitable subcombination, or as suitable in any other described embodiment of the invention. Certain features that are described in connection with various embodiments are not to be considered essential features of those embodiments unless the embodiment is inoperative without those elements.

[0143] As used herein, the term "method" refers to a manner, means, technique and procedure for accomplishing a given task, and includes, but is not limited to, any of the manners, means, techniques and procedures that are either known, or readily developed from known manners, means, techniques and procedures by practitioners of the relevant arts, including chemical, agricultural, biological and biochemical arts.

[0144] As used herein, the term "plant growth regulator" refers to, but is not limited to, any natural or synthetic compound that modifies or controls one or more specific physiological processes within a plant.

[0145] As used herein, the term "plant" refers to, but is not limited to, whole plants, ancestors and progeny of plants and plant parts, and includes seeds, sprouts, stems, roots (including tubers), and plant cells, tissues and organs. The plant may be in any form including suspension cultures, embryos, meristematic regions, callus tissue, leaves, gametophytes, sporophytes, pollen and microspores.

[0146] As used herein, the term "crop protection agent" refers to, but is not limited to, an agent that is a pesticide (or a mixture of more than one pesticide) or a plant growth regulator.

[0147] As used herein, the term "pesticide" refers to, but is not limited to, a chemical or biological agent that inhibits, incapacitates, kills, or otherwise interferes with a pest.

[0148] The compounds of the present invention will generally be used as herbicidal active ingredients in compositions. As used herein, the term "composition" refers to, but is not limited to, a formulation having at least one additional component selected from the group consisting of surfactants, solid diluents, and liquid diluents that act as carriers. The formulation components or composition components are selected to be consistent with the physical properties of the active ingredient, the mode of application, and environmental factors such as the type of oil, moisture and temperature. Useful compositions can include both liquid formulations and solid formulations. Liquid formulations may include solutions (including emulsifiable concentrates), suspensions, emulsions (including microemulsions, oil-in-water emulsions, flowable concentrates and / or suspoemulsions), which may optionally be thickened into gels. Common types of aqueous liquid compositions are soluble concentrates, suspension concentrates, capsule suspensions, concentrated emulsions, microemulsions, oil-in-water emulsions, flowable concentrates and suspoemulsions. Common types of non-aqueous liquid compositions are emulsifiable concentrates, microemulsifiable concentrates, dispersible concentrates and oil dispersions.

[0149] Common types of solid complexes are dusts, powders, granules, pellets, prills, fragments, 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 fluid suspensions are particularly useful for seed treatment. The active ingredient can be (micro)encapsulated and further formed into a suspension or solid complex; alternatively, the entire formulation of the active ingredient can be encapsulated (or "overcoated"). Encapsulation can control or delay the release of the active ingredient. Sprayable formulations are typically extended in a suitable medium prior to spraying. Such liquid and solid formulations are formulated to be readily diluted in a spray medium, which is usually water but often another suitable medium such as an aromatic or paraffinic hydrocarbon or vegetable oil. The spray volume can range from about 1 to several thousand liters per hectare, but more typically is in the range of about 10 to several hundred liters per hectare. Sprayable formulations can be tank-mixed with water or another suitable medium for foliar treatment by aerial or ground application, or for application to the medium in which the plants grow. Liquid formulations and dry formulations can be metered directly into a drip irrigation system or metered into the furrows during planting.

[0150] Formulations will typically contain an effective amount of the active ingredient, a diluent, and a surfactant, within an approximate range that totals 100% by weight.

[0151] The compounds of the present invention have herbicidal activity (both pre-emergence and post-emergence). As used herein, the term "controlling unwanted plant growth" refers to killing or injuring the vegetation or reducing its growth.

[0152] The compounds and compositions of the present invention can 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 the compound, with at least one of a surfactant, a solid diluent or a liquid diluent, to the leaves or other parts of unwanted plants, or to the environment of unwanted plant growth such as soil or water in which unwanted plants are growing or which surrounds the seeds or other vegetative propagules of unwanted plants.

[0153] The herbicidally effective amount of the compound of the present invention is determined by a number of factors including the formulation selected, the method of application, the amount and type of unwanted plant growth present, the growth conditions, etc. Generally, the herbicidally effective amount of the compound of the present invention is from about 0.001 to 20 kg / ha, and the preferred range is from about 0.004 to 1 kg / ha. A person skilled in the art can readily determine the herbicidally effective amount necessary for the desired level of weed control.

[0154] The compounds of the present invention are typically applied in the form of a formulated composition to a location containing desired vegetation (e.g., crops) and unwanted plant growth (i.e., weeds), both of which are in contact with a growth medium (e.g., soil), and can be seeds, seedlings and / or larger plants. At this location, the composition containing the compound of the present invention can be applied directly to the plant, or to any part of the plant that is particularly unwanted plant growth, and / or to the growth medium in contact with the plant.

[0155] The compounds of the present invention may also be mixed with one or more other biologically active compounds or agents, including herbicides, herbicide safeners, fungicides, insecticides, nematicides, bactericides, acaricides, plant growth regulators such as insect molting inhibitors and rooting promoters, sterilizing agents, semiochemicals, repellents, attractants, pheromones, feeding stimulants, phytohormones, other biologically active compounds for forming multi-component pesticides that confer a broader spectrum of agricultural protection, or bacteria, viruses or fungi. Mixtures of the compounds of the present invention with other herbicides can broaden the spectrum of activity against additional weed species and can suppress the growth of any resistant biotypes.

[0156] Throughout this application, various publications, published patent applications, and published patents are referenced. The disclosures of these publications in their entirety are hereby incorporated by reference into this application to more fully describe the state of the art to which this invention pertains.

[0157] Certain features of the invention that are described for clarity in connection with separate embodiments may also be provided in combination in a single embodiment. Conversely, various features of the invention that are described for brevity in connection with a single embodiment may also be provided separately, or in any suitable subcombination, or as suitable in any other described embodiment of the invention. It is not considered that certain features described in connection with various embodiments are essential features of those embodiments unless the embodiment is inoperable without those elements.

Claims

1. A herbicidal composition comprising a compound having the structure: 【Chemical 1】 or a salt thereof [wherein, A is a cyclopentadiene, benzene, and indene skeleton containing 1 to 4 heteroatoms; each of the heteroatoms is independently selected from the group consisting of N, S, Se, and O; one or more of the ring carbon, nitrogen, sulfur, or selenium atoms is -CX ３ , -CX ２ R, -COX, -CHO, -COR, -CO ２ R, -CONH ２ , -CONHR, sulfur = S, oxygen = O, -F, -Cl, -Br, and -I, and is optionally chemically bonded to at least one of the group consisting of; where X is selected from F, Cl, Br, and I; T is -(CH ２ ) ｎ -, -OR １ -, -SR １ -, -SOR １ -, -CSR １ -, -CS-, -POHR １ -, -PO(OR １ )R １ -, -CO-, -C(O)R １ and -COOR １ ; Z is H, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, -COOH, -COO-, -OH, -O-R, a linear, branched, cyclic, aromatic or heteroaromatic chain; -O-(CH ２ CH ２ O) ｎ R (n ≥ 1); -O-(CHMeCH ２ O) ｎ R (n ≥ 1) having a saturated or unsaturated alcohol residue; -COOR having a saturated or unsaturated alcohol residue; a substituted or unsubstituted phosphate group, a sulfonyl group, -SO ３ H, a sulfo group, a sulfonic acid, a cyano group, a carbamoyl group, a primary amine, a secondary amine, a tertiary amine, a carboxamide, -NR-O-R, -O-NR, or a salt thereof; In the formula, R is H, a substituted or unsubstituted alkyl group, and a substituted or unsubstituted aryl group; R １ is -(CH ２ ) ｎ -(n is from 0 to 9)] or a salt thereof and at least one agriculturally acceptable carrier, a herbicidal composition.

2. Z is 【Chemical 2】 selected from, the herbicidal composition according to claim 1.

3. Structure: 【Chemical Formula 3】 【Chem.】 A herbicidal composition according to claim 1, comprising a compound having.

4. The herbicidal composition according to any one of claims 1 to 3, further comprising at least one crop protection agent.

5. The herbicidal composition according to claim 4, wherein the at least one crop protection agent is selected from the group consisting of fungicides, insecticides, herbicides and plant growth regulators.

6. At least one crop protection agent is atrazine, terbuthylazine, (S)-metolachlor, metolachlor, terbutryn, simazine, dimethenamid, (S)-dimethenamid, flufenacet, acetochlor, alachlor, isoxaflutole, 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, pyrimin, fenmedifam, desmedifam, ethofumesate, triasulfuron, chloridazon, lenacil, triallate, fluaquizafop, sethoxydim, quizalofop, clopyralid, clethodim, oxasulfuron, acifluorfen, benazolin-ethyl, sulfentrazone, chlorimuron-ethyl, chloransulam-methyl, homomethosulfan, 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, dichlorprop-methyl, diflufenican, ethoxysulfuron, fentrazamide, flazasulfuron, florasulam, fluazolate, flucarbazone, flupyrsulfuron-methylsodium, flurtamone, iodosulfuron, isoproturon, chlorotoluron, chlorosulfuron, metsulfuron-methyl, sulfosulfuron, tribenuron-methyl, 2,The herbicidal composition according to claim 5, 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, NB 061, MK243, HW-52, AC 014, ametryn, hexazinone, asulam, azafenidin, tebuthiuron, ethametsulfuron-methyl, or a combination thereof.

7. 【Fig. 4】 A herbicidal compound having a structure selected from, or a salt thereof.

8. A herbicidal composition for controlling unwanted plant growth, comprising a. A compound having the structure: [Chemical Formula 5] or a salt thereof [wherein, A is a cyclopentadiene, benzene and indene skeleton containing 1 to 4 heteroatoms, each of the heteroatoms being independently selected from the group consisting of N, S, Se and O; one or more of the carbon, nitrogen, sulfur or selenium atoms of the ring are -CX ３ , -CX ２ R, -COX, -CHO, -COR, -CO ２ R, -CONH ２ , -CONHR, sulfur = S, oxygen = O, -F, -Cl, -Br and -I, optionally chemically bonded to at least one of the group consisting of, wherein X is selected from F, Cl, Br and I; T is -(CH ２ ) ｎ -, -OR １ -, -SR １ -, -SOR １ -, -CSR １ -, -CS-, -POHR １ -, -PO(OR １ )R １ -, -CO-, -COR １ and -COOR １ ; Z is H, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, -COOH, COO-, -OH, -O-R, a linear, branched, cyclic, aromatic or heteroaromatic chain; -O-(CH ２ CH ２ O) ｎ R (n≥1); -O-(CHMeCH ２ O) ｎ R (n≥1) having a saturated or unsaturated alcohol residue of -COOR; a substituted or unsubstituted phosphate group, a sulfonyl group, a sulfo group, a sulfonic acid, -SO ３ H, a carbamoyl group, a primary amine, a secondary amine, a tertiary amine, a carboxamide, a cyano group, -NR-O-R, -O-NR, or a salt thereof; In the formula, R is H, a substituted or unsubstituted alkyl group, and a substituted or unsubstituted aryl group; R １ is -(CH ２ ), ｎ -(n is from 0 to 9); b. At least one plant growth regulator; and c. At least one agriculturally acceptable carrier a herbicidal composition comprising a mixture of.

9. A herbicidal composition for controlling unwanted plant growth, comprising a. A compound having the structure: [[Chemical Formula 6]] or a salt thereof [wherein, A is a cyclopentadiene, benzene, and indene skeleton containing 1 to 4 heteroatoms; each of the heteroatoms is independently selected from the group consisting of N, S, Se, and O; one or more of the carbon, nitrogen, sulfur, or selenium atoms of the ring are -CX ３ , -CX ２ R, -COX, -CHO, -COR, -CO ２ R, -CONH ２ , -CONHR, sulfur = S, oxygen = O, -F, -Cl, -Br, and -I, and is optionally chemically bonded to at least one of the group consisting of; wherein X is selected from F, Cl, Br, and I; T is -(CH ２ ) ｎ -, -OR １ -, -SR １ -, -SOR １ -, -CSR １ -, -CS-, -POHR １ -, -PO(OR １ )R １ -, -CO-, -COR １ , and -COOR １ ; Z is H, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, -COOH, COO-, -OH, -O-R, a linear, branched, cyclic, aromatic or heteroaromatic chain; -O-(CH ２ CH ２ O) ｎ R (n≥1); -O-(CHMeCH ２ O) ｎ R (n≥1) having a saturated or unsaturated alcohol residue; -COOR having a saturated or unsaturated alcohol residue; a substituted or unsubstituted phosphate group, a sulfonyl group, -SO ３ H, a sulfo group, a sulfonic acid, a carbamoyl group, a primary amine, a secondary amine, a tertiary amine, a carboxamide, a cyano group, -NR-O-R, -O-NR, or a salt thereof; In the formula, R is H, a substituted or unsubstituted alkyl group, and a substituted or unsubstituted aryl group; R １ is ２ -(CH ｎ )(n is from 0 to 9); b. Atrazine, Terbuthylazine, (S)-Metolachlor, Metolachlor, Terbutryn, Simazine, Dimethanamid, (S)-Dimethanamid, Flufenacet, Acetochlor, Aclonifen, Isoxaben, Isoxachlortole, Mesotrione, Sultrione, Metosulam, Flumetsulam, Pendimethalin, Bromoxynil, Bentazon, 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, metazoxolon, pyriminobac, fenmedipham, desmedipham, ethofumesate, triasulfuron, chloridazon, lenacil, triallate, fluaquizafop, Sethoxydim, quizalofop, clopyralid, clethodim, oxasulfuron, acifluorfen, benazolin-ethyl, sulfentrazone, chlorimuron-ethyl, chloransulam-methyl, homosafen, imazamox, imazethapyr, imazapic, imazapyr, lactofen, fenoxaprop (P-ethyl), thidiazuron, tribufos, trifluralin, dimethenamid, 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, 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, bifenox, 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, NB 061, MK243, HW-52, AC 014, ametryn, hexazinone, asulam, azafenidin, tebuthiuron, ethametsulfuron-methyl, or a combination thereof; and, c. At least one agriculturally acceptable carrier a herbicidal composition comprising a mixture of.

10. A method for controlling unwanted plant growth, comprising applying the agricultural composition according to any one of claims 1 to 9 to a location of unwanted plant growth, a method for controlling unwanted plant growth.

11. A method for controlling unwanted plant growth, comprising applying, at a location of unwanted plant growth, a herbicidally effective amount of a compound having the structure: [Chemical Formula 7] or a salt thereof [wherein, A is a cyclopentadiene, benzene, and indene backbone containing 1 to 4 heteroatoms; each of the heteroatoms is independently selected from the group consisting of N, S, Se, and O; one or more of the carbon, nitrogen, sulfur, or selenium atoms of the ring are -CX ３ , -CX ２ R, -COX, -CHO, -COR, -CO ２ R, -CONH ２ , -CONHR, -CON(R) ２ , sulfur = S, oxygen = O, -F, -Cl, -Br, and -I are optionally chemically bonded to at least one of the group consisting of; wherein X is selected from F, Cl, Br, and I; T is -(CH ２ ) ｎ -, -OR １ -, -SR １ -, -SOR １ -, -CSR １ -, -CS-, -POHR １ -, -PO(OR １ )R １ -, -CO-, -COR １ and -COOR １ -; Z is H, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, -COOH, -COO-, -OH, -O-R, a linear, branched, cyclic, aromatic or heteroaromatic chain; -O-(CH ２ CH ２ O) ｎ R (n≥1); -O-(CHMeCH ２ O) ｎ R (n≥1) having a saturated or unsaturated alcohol residue of -COOR; a substituted or unsubstituted phosphate group, a sulfonyl group, -SO ３ H, a sulfo group, a sulfonic acid, a carbamoyl group, a primary amine, a secondary amine, a tertiary amine, a carboxamide, a cyano group, -NR-O-R, -O-NR, or a salt thereof; wherein, R is H, a substituted or unsubstituted alkyl group, and a substituted or unsubstituted aryl group; R １ is - (CH ２ ) ｎ - (n is from 0 to 9)] a method comprising applying.

12. The method according to claim 10 or 11, further comprising applying at least one crop protection agent to a location of unwanted plant growth.

13. The method according to claim 12, wherein the crop protection agent is selected from the group consisting of herbicides, fungicides, insecticides and plant growth regulators.

14. The method according to claim 13, wherein the crop protection agent is an amino acid synthesis inhibitor herbicide.

15. The method according to claim 14, 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.

16. The method according to claim 14, wherein the amino acid synthesis inhibitor herbicide is selected from the group consisting of imazamox, imazapic, imazethapyr, imazakirin, imazapyr and imazamethabenz, or a combination thereof.

17. The method according to claim 14, 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 a combination thereof.

18. The method according to claim 14, wherein the amino acid synthesis inhibitor herbicide is glyphosate.

19. The method according to claim 13, wherein the plant growth regulator is selected from the group consisting of dicamba, 2,4-D, clopyralid and fluroxypyr.

20. The method according to any one of claims 10 to 19, further comprising applying a third herbicide or plant growth regulator.

21. The method according to any one of claims 10 to 20, wherein the location of unwanted vegetation is a crop field.

22. The method according to claim 21, wherein the crop is selected from the group consisting of maize, wheat, rice, barley, sorghum and oats.

23. The method according to any one of claims 10 to 22, wherein the herbicidal composition is applied pre-emergence.

24. The method according to any one of claims 10 to 22, wherein the herbicidal composition is applied post-emergence.

25. A method for selectively controlling the growth of harmful weeds, comprising applying an effective amount of the herbicidal composition according to any one of claims 1 to 9 to a crop field.

26. The method according to claim 25, wherein the herbicidal composition is applied pre-emergence.

27. The method according to claim 25, wherein the herbicidal composition is applied post-emergence.

28. The method according to any one of claims 25 to 27, wherein the crop is selected from the group consisting of maize, wheat, rice, barley, sorghum and oats.

Images