Herbicidal pyrimidinone derivatives

Abstract

Compounds of formula (I) which are useful as pesticides, especially as herbicides 【Chemical 1】 JPEG2025523024000022.jpg43155(wherein the substituents are as defined in claim 1) .

Description

Technical Field

[0001] The present invention relates to isoxazoline derivatives that are herbicidally active and to processes and intermediates used in the preparation of such derivatives. The invention further extends to herbicidal compositions containing such derivatives and to the use of such compounds and compositions for controlling unwanted plant growth, in particular for controlling weeds in crops of useful plants.

Summary of the Invention

Means for Solving the Problems

[0002] The present invention is based on the finding that the isoxazoline derivatives of formula (I) as defined herein exhibit surprisingly good herbicidal activity. Accordingly, according to the present invention, formula (I):

Chemical Formula

[0003] According to a second aspect of the present invention, there is provided a pesticidal composition comprising a herbicidally effective amount of a compound of formula (I) and an agrochemically acceptable diluent or carrier. Such agricultural compositions may further comprise at least one additional active ingredient.

[0004] According to a third aspect of the present invention, there is provided a method of controlling or preventing unwanted plant growth, wherein a herbicidally effective amount of a compound of formula (I) or a composition comprising this compound as an active ingredient is applied to a plant, a part thereof or its habitat.

[0005] According to a fourth aspect of the present invention, there is provided the use of a compound of formula (I) as a herbicide.

[0006] According to a fifth aspect of the present invention, there is provided a process for the preparation of a compound of formula (I).

DETAILED DESCRIPTION OF THE INVENTION

[0007] As used herein, the term "halogen" or "halo" refers to fluorine (fluoro), chlorine (chloro), bromine (bromo) or iodine (iodo), preferably fluorine, chlorine or bromine.

[0008] As used herein, cyano means a -CN group.

[0009] As used herein, hydroxy means a -OH group.

[0010] As used herein, nitro means a -NO2 group.

[0011] As used herein, the term "C1-C6 alkyl" refers to a straight-chain or branched-chain hydrocarbon chain group composed of only carbon and hydrogen atoms, containing no unsaturation, having 1 to 6 carbon atoms, and being bonded to the remainder of the molecule by a single bond. C1-C4 alkyl and C1-C2 alkyl should be construed accordingly. Examples of C1-C6 alkyl include, but are not limited to, methyl (Me), ethyl (Et), n-propyl, 1-methylethyl (iso-propyl), n-butyl, and 1,1-dimethylethyl (t-butyl).

[0012] As used herein, the term "C1-C6 alkoxy" refers to a group of the formula -OR a wherein R is a C1-C6 alkyl group as generally defined above. a C1-C4 alkoxy should be construed accordingly. Examples of C 1-4 alkoxy include, but are not limited to, methoxy, ethoxy, propoxy, iso-propoxy, and t-butoxy.

[0013] As used herein, the term "C1-C6 haloalkyl" refers to a C1-C6 alkyl group as generally defined above that is substituted by one or more of the same or different halogen atoms. C1-C4 haloalkyl should be construed accordingly. Examples of C1-C6 haloalkyl include, but are not limited to, chloromethyl, fluoromethyl, fluoroethyl, difluoromethyl, trifluoromethyl, and 2,2,2-trifluoroethyl.

[0014] As used herein, the term "C2-C6 alkenyl" refers to a straight-chain or branched-chain hydrocarbon radical group composed of only carbon and hydrogen atoms, containing at least one double bond that can be in either the (E) or (Z) configuration, having 2 to 6 carbon atoms, and being attached to the remainder of the molecule by a single bond. C2-C4 alkenyl should be construed accordingly. Examples of C2-C6 alkenyl include, but are not limited to, prop-1-enyl, allyl (prop-2-enyl), and but-1-enyl.

[0015] As used herein, the term "C2-C6 haloalkenyl" refers to a C2-C6 alkenyl group as generally defined above, substituted by one or more of the same or different halogen atoms. Examples of C2-C6 haloalkenyl include, but are not limited to, chloroethylene, fluoroethylene, 1,1-difluoroethylene, 1,1-dichloroethylene, and 1,1,2-trichloroethylene.

[0016] As used herein, the term "C2-C6 alkynyl" refers to a straight-chain or branched-chain hydrocarbon radical group composed of only carbon and hydrogen atoms, containing at least one triple bond, having 2 to 6 carbon atoms, and being attached to the remainder of the molecule by a single bond. C2-C4 alkynyl should be construed accordingly. Examples of C2-C6 alkynyl include, but are not limited to, prop-1-ynyl, propargyl (prop-2-ynyl), and but-1-ynyl.

[0017] As used herein, the term "C1-C6 haloalkoxy" refers to a C1-C6 alkoxy group as defined above, substituted by one or more of the same or different halogen atoms. C1-C4 haloalkoxy should be construed accordingly. Examples of C1-C6 haloalkoxy include, but are not limited to, fluoromethoxy, difluoromethoxy, fluoroethoxy, trifluoromethoxy, and trifluoroethoxy.

[0018] As used herein, the term "C1-C3 haloalkoxy C1-C3 alkyl" means R b is a C1-C3 haloalkyl group as generally defined above, and R a is a C1-C3 alkylene group as generally defined above, of the formula R b -O-R a - group.

[0019] As used herein, the term "C1-C3 alkoxy C1-C3 alkyl" means R b is a C1-C3 alkyl group as generally defined above, and R a is a C1-C3 alkylene group as generally defined above, of the formula R b -O-R a - group.

[0020] As used herein, the term "C1-C3 alkoxy C1-C3 alkoxy-" means R b is a C1-C3 alkyl group as generally defined above, and R a is a C1-C3 alkylene group as generally defined above, of the formula R b -O-R a -O- group.

[0021] As used herein, the term "C3-C6 alkenyloxy" means a group of the formula -OR a wherein R is a C3-C6 alkenyl group as generally defined above. a of the group.

[0022] As used herein, the term "C3-C6 alkynyloxy" means a group of the formula -OR a wherein R is a C3-C6 alkynyl group as generally defined above. a of the group.

[0023] As used herein, the term "hydroxy C1-C6 alkyl" refers to a C1-C6 alkyl group as generally defined above that is substituted by one or more hydroxy groups.

[0024] As used herein, the term "C1-C6 alkylcarbonyl" refers to the group of formula -C(O)R where R a is a C1-C6 alkyl group as generally defined above. a

[0025] As used herein, the term "C1-C6 alkoxycarbonyl" refers to the group of formula -C(O)OR where R a is a C1-C6 alkyl group as generally defined above. a

[0026] As used herein, the term "aminocarbonyl" refers to the group of formula -C(O)NH2.

[0027] As used herein, the term "aminothiocarbonyl" refers to the group of formula -C(S)NH2.

[0028] As used herein, the term "C3-C6 cycloalkyl" refers to a stable monocyclic ring group that is saturated or partially unsaturated and contains 3 to 6 carbon atoms. C3-C4 cycloalkyl should be construed accordingly. Examples of C3-C6 cycloalkyl include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl.

[0029] As used herein, the term "C3-C6 halocycloalkyl" refers to a C3-C6 cycloalkyl group as generally defined above that is substituted with one or more of the same or different halogen atoms. C3-C4 halocycloalkyl should be construed accordingly.

[0030] As used herein, the term "C3-C6 cycloalkoxy" refers to the group of formula -OR where R a is a C3-C6 cycloalkyl group as generally defined above. a

[0031] As used herein, the term "N-C3-C6 cycloalkylamino" means R a wherein R is a C3-C6 cycloalkyl group as generally defined above, of the formula -NHR a refers to a group of.

[0032] As used herein, unless otherwise expressly stated, the term "heteroaryl" refers to a 5- or 6-membered monocyclic aromatic ring containing 1, 2, 3 or 4 heteroatoms individually selected from nitrogen, oxygen and sulfur. The heteroaryl group may be attached to the remainder of the molecule via a carbon atom or a heteroatom. Examples of heteroaryl include furyl, pyrrolyl, imidazolyl, thienyl, pyrazolyl, thiazolyl, isothiazolyl, oxazolyl, isoxazolyl, triazolyl, tetrazolyl, pyrazinyl, pyridazinyl, pyrimidinyl or pyridyl.

[0033] As used herein, unless otherwise expressly stated, the term "heterocyclyl" or "heterocyclic" refers to a stable 4- to 6-membered non-aromatic monocyclic ring group containing 1, 2 or 3 heteroatoms individually selected from nitrogen, oxygen and sulfur. The heterocyclyl group may be attached to the remainder of the molecule via a carbon atom or a heteroatom. Examples of heterocyclyl include, but are not limited to, pyrrolinyl, pyrrolidyl, tetrahydrofuryl, tetrahydrothienyl, tetrahydrothiopyranyl, piperidyl, piperazinyl, tetrahydropyranyl, dihydroisoxazolyl, dioxolanyl, morpholinyl or δ-lactamyl.

[0034] The presence of one or more possible asymmetric carbon atoms in the compounds of formula (I) means that the compounds can occur as chiral isomers, i.e., enantiomers or diastereoisomers. As a result of restricted rotation around single bonds, atropisomers are also obtained. Formula (I) is intended to include all those possible isomers and mixtures thereof. The present invention includes all those possible isomers of the compounds of formula (I) and mixtures thereof. Similarly, formula (I) is intended to include all possible tautomers (including lactam-lactim tautomerism and keto-enol tautomerism) when they exist. The present invention includes all possible tautomers of the compounds of formula (I). Similarly, when a disubstituted alkene is present, these can exist in the E or Z form or as a mixture of both in any proportion. The present invention includes all those possible isomers of the compounds of formula (I) and mixtures thereof.

[0035] The compounds of formula (I) will typically be provided in the form of an agriculturally acceptable salt, zwitterion or an agriculturally acceptable salt of a zwitterion. The present invention encompasses all such agriculturally acceptable salts, zwitterions and mixtures thereof in all proportions.

[0036] Suitable agriculturally acceptable salts of the present invention may have cations including, but not limited to, metals, conjugate acids of amines, and organic cations. Examples of suitable metals include aluminum, calcium, cesium, copper, lithium, magnesium, manganese, potassium, sodium, iron, and zinc.Examples of suitable amines include allylamine, ammonia, amylamine, arginine, benethamine, benzathine, butenyl-2-amine, butylamine, butylethanolamine, cyclohexylamine, decylamine, diamylamine, dibutylamine, diethanolamine, diethylamine, diethylenetriamine, diheptylamine, dihexylamine, diisoamylamine, diisopropylamine, dimethylamine, dioctylamine, dipropanolamine, dipropargylamine, dipropylamine, dodecylamine, ethanolamine, ethylamine, ethylbutylamine, ethylenediamine, ethylheptylamine, ethyloctylamine, ethylpropanolamine, heptadecylamine, heptylamine, hexadecylamine, hexenyl-2-amine, hexylamine, hexylheptylamine, hexyl octylamine, histidine, indoline, isoamylamine, isobutanolamine, isobutylamine, isopropanolamine, isopropylamine, lysine, meglumine, methoxyethylamine, methylamine, methylbutylamine, methylethylamine, methylhexylamine, methylisopropylamine, methylnonylamine, methyloctadecylamine, methylpentadecylamine, morpholine, N,N-diethylethanolamine, N-methylpiperazine, nonylamine, octadecylamine, octylamine, oleylamine, pentadecylamine, pentenyl-2-amine, phenoxyethylamine, picoline, piperazine, piperidine, propanolamine, propylamine, propylenediamine, pyridine, pyrrolidine, sec-butylamine, stearylamine, tallow amine, tetradecylamine, tributylamine, tridecylamine, trimethylamine, triheptylamine, trihexylamine, triisobutylamine, triisodecylamine, triisopropylamine, trimethylamine, tripentylamine, tripropylamine, tris(hydroxymethyl)aminomethane, and undecylamine.Examples of suitable organic cations include benzyltributylammonium, benzyltrimethylammonium, benzyltriphenylphosphonium, choline, tetrabutylammonium, tetrabutylphosphonium, tetraethylammonium, tetraethylphosphonium, tetramethylammonium, tetramethylphosphonium, tetrapropylammonium, tetrapropylphosphonium, tributylsulfonium, tributylsulfoxonium, triethylsulfonium, triethylsulfoxonium, trimethylsulfonium, trimethylsulfoxonium, tripropylsulfonium and tripropylsulfoxonium.

[0037] The following list provides definitions, including preferred definitions, for substituents Z, R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 8 、R 9 、R 10 、R 11 、R 12 、R 13 、R 14 、R 15 、R 16 and R 17 in connection with the compounds of formula (I) according to the invention. For any one of these substituents, any of the definitions given below may be combined with any of the definitions of any of the other substituents given elsewhere herein or below.

[0038] Preferably, R 1 is selected from the group consisting of hydrogen and C1-C4 alkyl, more preferably hydrogen and methyl, and most preferably hydrogen.

[0039] Preferably, R 2 is C1-C4 alkyl, more preferably C1-C2 alkyl, and most preferably methyl.

[0040] Preferably, R 3is selected from the group consisting of hydrogen, chlorine and fluorine, more preferably chlorine and fluorine, and even more preferably fluorine.

[0041] Preferably, R 4 is selected from the group consisting of hydrogen, chlorine, bromine, cyano and aminothiocarbonyl, more preferably chlorine, bromine, cyano and aminothiocarbonyl, even more preferably chlorine and bromine, and still more preferably chlorine.

[0042] Preferably, each R 5 and R 6 is independently selected from the group consisting of hydrogen, C1-C4 alkyl, CO2R 9 and CH2OR 12 , more preferably independently selected from the group consisting of hydrogen and C1-C2 alkyl, and most preferably hydrogen.

[0043] Preferably, each R 7 and R 8 is independently selected from the group consisting of hydrogen, C1-C4 alkyl, C1-C6 haloalkyl, CO2R 9 , CONR 10 R 11 and CH2OR 12 . More preferably, R 7 is selected from the group consisting of CO2R 9 , CONR 10 R 11 and CH2OR 12 , and most preferably CO2R 9 . More preferably, R 8 is selected from the group consisting of hydrogen and C1-C4 alkyl, and most preferably methyl.

[0044] Preferably, R 9 is hydrogen, C1-C4 alkyl, C1-C4 haloalkyl, C1-C2 alkoxy C1-C2 alkyl, phenyl C1-C2 alkyl, and phenyl C1-C2 alkyl where R 13Phenyl C1-C2 alkyl substituted by one or two groups represented by, more preferably hydrogen, C1-C4 alkyl, C1-C2 alkoxy C1-C2 alkyl and phenyl C1-C2 alkyl, still more preferably hydrogen, C1-C4 alkyl and phenyl C1-C2 alkyl, still more preferably hydrogen and C1-C2 alkyl, and even more preferably selected from the group consisting of, and even more preferably, R 9 is ethyl.

[0045] Preferably, R 10 is selected from the group consisting of hydrogen and SO2R 14 and more preferably SO2R 14 is.

[0046] Preferably, R 11 is hydrogen.

[0047] Preferably, R 12 is hydrogen, C1-C2 alkyl, C1-C2 alkylsulfonyl, C1-C2 haloalkylsulfonyl, C1-C4 alkylcarbonyl, phenylcarbonyl, phenylcarbonyl substituted by one or two groups represented by R 13 phenylcarbonyl, phenyl C1-C2 alkylcarbonyl, and phenyl C1-C2 alkylcarbonyl substituted by one or two groups represented by R 13 phenyl C1-C2 alkylcarbonyl, more preferably selected from the group consisting of C1-C2 alkylsulfonyl, C1-C2 haloalkylsulfonyl and C1-C4 alkylcarbonyl.

[0048] Preferably, R 13 is selected from the group consisting of halogen, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, cyano and C1-C4 alkylsulfonyl.

[0049] Preferably, R 14is selected from the group consisting of C1-C4 alkyl and C1-C4 alkyl(C1-C4 alkyl)amino, more preferably methyl and isopropyl(methyl)amino.

[0050] Preferably, R 17 is selected from the group consisting of C1-C2 alkyl and C1-C2 haloalkyl, more preferably halomethyl, and most preferably trifluoromethyl.

[0051] A preferred subset of the compounds is R 1 is selected from hydrogen or methyl; R 2 is C1-C2 alkyl; R 3 is selected from hydrogen, chlorine and fluorine; R 4 is selected from chlorine, bromine, cyano and aminothiocarbonyl; Each R 5 and R 6 is independently selected from hydrogen and C1-C2 alkyl; R 7 is CO2R 9 , CONR 10 R 11 and CH2OR 12 selected from; R 8 is selected from hydrogen and C1-C4 alkyl; R 9 is selected from hydrogen, C1-C4 alkyl, C1-C2 alkoxy C1-C2 alkyl and phenyl C1-C2 alkyl; R 10 is SO2R 14 ; R 11 is hydrogen; R 12 is selected from C1-C2 alkylsulfonyl, C1-C2 haloalkylsulfonyl and C1-C4 alkylcarbonyl; R 14 is selected from methyl and isopropyl(methyl)amino; and R 17is selected from methyl and trifluoromethyl.

[0052] A more preferred subset of the compounds is R 1 is hydrogen; R 2 is methyl; R 3 is selected from chlorine and fluorine; R 4 is selected from chlorine and bromine; Each R 5 and R 6 is hydrogen; R 7 is CO2R 9 ; R 8 is methyl; R 9 is selected from hydrogen, C1-C4 alkyl and phenyl C1-C2 alkyl; and R 17 is trifluoromethyl.

[0053] An even more preferred subset of the compounds is R 1 is hydrogen; R 2 is methyl; R 3 is fluorine; R 4 is chlorine; R 5 and R 6 are both hydrogen; R 7 is CO2R 9 ; R 8 is methyl; R 9 is ethyl; and R 17 is trifluoromethyl.

[0054] Table of examples This table shows that R 1 is hydrogen and R 2is methyl, R 5 and R 6 is hydrogen, R 8 is methyl, R 17 is trifluoromethyl, disclose specific compounds of formula (I).

[0055]

Table 1

[0056] Among these, Compound 11 is the most preferred.

[0057] The compounds of the present invention can be prepared by techniques known to those skilled in the art of organic chemistry. A general method for preparing the compounds of formula (I) is described below. Unless otherwise specified in the text, the substituents Z, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 and R 17 are as defined above in this specification. The starting materials used for the preparation of the compounds of the present invention can be purchased from ordinary commercial suppliers or prepared by known methods. The starting materials and intermediates can be purified by methods of conventional techniques such as chromatography, crystallization, distillation, and filtration before use in the next step.

[0058] The compounds of formula (I) can be prepared from the compounds of formula (A) as shown in Reaction Scheme 1. Reaction Scheme 1

Chemical formula

[0059] For example, the compound of formula (A) can be treated with a base such as potassium carbonate and an alkylating agent such as methyl iodide in a suitable solvent such as acetone. The compound of formula (A) can be prepared from the compound of formula (B) and the amine of formula (C) as shown in Reaction Scheme 2. Reaction Scheme 2

Chem.

[0060] For example, the compound of formula (C) can be treated with the oxazinone of formula (B) in a suitable solvent such as acetic acid. The amine of formula (C) can be prepared from the nitro compound of formula (D) as shown in Reaction Scheme 3. Reaction Scheme 3

Chem.

[0061] For example, the compound of formula (D) can be treated with a reducing agent such as iron and ammonium chloride in a suitable solvent such as a mixture of water and ethanol. The nitro compound of formula (D) can be prepared from the oxime of formula (E) and the alkene of formula (F) as shown in Reaction Scheme 4. Reaction Scheme 4

Chem.

[0062] For example, the oxime of formula (E) can be treated with N-chlorosuccinimide in a suitable solvent such as dimethylformamide, and then the resulting intermediate can be treated with the alkene of formula (F) in a suitable solvent such as dichloromethane in the presence of a base such as triethylamine. The alkene of formula (F) is available or can be prepared by methods well known in the literature. The oxime of formula (E) can be prepared from the aldehyde of formula (G) as shown in Reaction Scheme 5. Reaction Scheme 5

Chem.

[0063] For example, the aldehyde of formula (G) can be treated with hydroxylamine hydrochloride in a suitable solvent such as a mixture of water and ethanol. The aldehyde of formula (G) is available or can be prepared by methods known in the literature. R 7 The compound of formula (I-A), which is a compound of formula (I) where R is a carboxylic acid group, can be prepared from the compound of formula (I-B), which is a compound of formula (I) where R 7 is CO2R 9 as shown in Reaction Scheme 6. Reaction Scheme 6

Chemical formula

[0064] For example, the compound of formula (I-B) can be treated with sodium hydroxide in a suitable solvent such as a mixture of water and ethanol. R 7 The compound of formula (I-C), which is a compound of formula (I) where R is a hydroxymethyl group, can be prepared from the compound of formula (I-A or I-B) as shown in Reaction Scheme 7. Reaction Scheme 7

Chemical formula

[0065] For example, the compound of formula (I-A) or (I-B) can be treated with a suitable reducing agent, such as a metal hydride reagent like sodium borohydride or borane, in a suitable solvent such as tetrahydrofuran. R 7 is CH2OR 12 The compound of formula (I-D), which is a compound of formula (I) where R Reaction Scheme 8

Chemical formula

[0066] For example, the compound of formula (I-C) can be treated with a reagent R such as an alkylating agent, an acylating agent or a sulfonylating agent in a suitable solvent such as tetrahydrofuran in the presence of a base such as sodium hydride or triethylamine. 12 -LG (wherein LG is a leaving group such as a halogen). 7 is CONR 10 R 11 The compound of formula (I-E), which is a compound of formula (I) where R is CONR Reaction Scheme 9

Chemical formula

[0067] For example, the compound of formula (I-A) can be treated with a halogenating reagent such as oxalyl chloride in a suitable solvent such as dichloromethane to form an acyl halide, which can be treated with the reagent HNR 10 R 11 in a suitable solvent such as dichloromethane in the presence of a base such as triethylamine. 7 The compound of formula (I-G), which is a compound of formula (I) where R is an oxime group, can be prepared from the compound of formula (I-F), which is a compound of formula (I) where R is a ketone group, as shown in Reaction Scheme 10. 7 Reaction Scheme 10

Chemical formula

[0068] For example, the compound of formula (I-F) can be treated with hydroxylamine H2NOR 16 or a salt thereof in a suitable solvent such as ethanol, optionally in the presence of a base such as triethylamine. 7 The compound of formula (I-H), which is a compound of formula (I) where R is a hydrazone group, can be prepared from the compound of formula (I-F), which is a compound of formula (I) where R is a ketone group, as shown in Reaction Scheme 11. 7 ​​ Reaction Scheme 11

Chem.

[0069] For example, the compound of formula (I-F) can be treated with hydrazine H2NN(R 16 )2 or a salt thereof in a suitable solvent such as ethanol, optionally in the presence of a base such as triethylamine.

[0070] Those skilled in the art will understand that it is often possible to change the order in which the above conversions are carried out or to combine them in alternative ways to prepare a wide range of compounds of formula (I). The multiple steps can also be combined in a single reaction. All such variations are considered to be within the scope of the present invention.

[0071] Those skilled in the art will also recognize that some reagents may not be compatible with certain values or combinations of substituents Z, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 and R 17 as defined herein, and any additional steps such as protection and / or deprotection steps necessary to achieve the desired conversion will be apparent to those skilled in the art.

[0072] The compounds according to the invention can be used as herbicidal agents in their unmodified form, but they are generally formulated into compositions in various ways using formulation adjuvants such as carriers, solvents and surfactants. The formulations can be in various physical forms, such as sprays, gels, wettable powders, water-dispersible granules, water-dispersible tablets, foaming pellets, emulsifiable concentrates, microemulsifiable concentrates, oil-in-water emulsions, oil flowables, aqueous dispersions, oily dispersions, suspoemulsions, capsule suspensions, emulsifiable granules, soluble liquids, water-soluble concentrates (with water or a water-miscible organic solvent as carrier), in the form of impregnated polymer films or in other forms known, for example, from the Manual on Development and Use of FAO and WHO Specifications for Pesticides, United Nations, First Edition, Second Revision (2010). For water-soluble compounds, soluble liquids, water-soluble concentrates or water-soluble granules are preferred. Such formulations can either be used directly or diluted before use. The dilution can be carried out, for example, with water, liquid fertilizers, micronutrients, biological organisms, oils or solvents.

[0073] The formulations can be prepared, for example, by mixing the active ingredient with formulation adjuvants in order to obtain a composition in the form of a micronized solid, a granule, a solution, a dispersion or an emulsion. The active ingredient can also be formulated with other adjuvants such as micronized solids, mineral oils, vegetable or animal oils, vegetable or animal modified oils, organic solvents, water, surfactants or combinations thereof.

[0074] The active ingredient can also be contained in extremely minute microcapsules. The microcapsules contain the active ingredient in a porous carrier. This enables the active ingredient to be released into the environment in a controlled amount (for example, sustained release). The microcapsules usually have a diameter of 0.1 to 500 microns. They contain the active ingredient in an amount of about 25 to 95% by weight of the capsule weight. The active ingredient can be in the form of an integral solid, fine particles in a solid or liquid dispersion, or a suitable solution. The encapsulating film can include, for example, natural or synthetic rubber, cellulose, styrene / butadiene copolymer, polyacrylonitrile, polyacrylate, polyester, polyamide, polyureas, polyurethane, or chemically modified polymers, and xanthan gum starch or other polymers known to those skilled in the art. Alternatively, very fine microcapsules can be formed in which the active ingredient is contained therein in the form of micronized particles in a solid matrix of the base substance, but the microcapsules are not themselves encapsulated.

[0075] The compounding aids suitable for the preparation of the composition according to the present invention are known per se. As the liquid carrier, water, toluene, xylene, petroleum ether, vegetable oil, acetone, methyl ethyl ketone, cyclohexanone, acid anhydride, acetonitrile, acetophenone, amyl acetate, 2-butanone, butylene carbonate, chlorobenzene, cyclohexane, cyclohexanol, alkyl esters of acetic acid, diacetone alcohol, 1,2-dichloropropane, diethanolamine, p-diethylbenzene, diethylene glycol, diethylene glycol abietate, diethylene glycol butyl ether, diethylene glycol ethyl ether, diethylene glycol methyl ether, N,N-dimethylformamide, dimethyl sulfoxide, 1,4-dioxane, dipropylene glycol, dipropylene glycol methyl ether, dipropylene glycol dibenzoate, diproxitol, alkyl pyrrolidone, ethyl acetate, 2-ethylhexanol, ethylene carbonate, 1,1,1-Trichloroethane, 2-heptanone, alpha-pinene, d-limonene, ethyl lactate, ethylene glycol, ethylene glycol butyl ether, ethylene glycol methyl ether, gamma-butyrolactone, glycerol, glycerol acetate, glycerol diacetate, glycerol triacetate, hexadecane, hexylene glycol, isoamyl acetate, isobornyl acetate, isooctane, isophorone, isopropylbenzene, isopropyl myristate, lactic acid, laurylamine, mesityloxide, methoxypropanol, methyl isoamyl ketone, methyl isobutyl ketone, methyl laurate, methyl octanoate, methyl oleate, methylene chloride, m-xylene, n-hexane, n-octylamine, octadecanoic acid, octylamine acetate, oleic acid, oleylamine, o-xylene, phenol, polyethylene glycol, propionic acid, propyl lactate, propylene carbonate, propylene glycol, propylene glycol methyl ether, p-xylene, toluene, triethyl phosphate, triethylene glycol, xylene sulfonic acid, paraffin, mineral oil, trichloroethylene, perchloroethylene, ethyl acetate, amyl acetate, butyl acetate, propylene glycol methyl ether, diethylene glycol methyl ether, methanol, ethanol, isopropanol and amyl alcohol, tetrahydrofurfuryl alcohol, hexanol, octanol and other higher molecular weight alcohols, ethylene glycol, propylene glycol, glycerol, N-methyl-2-pyrrolidone, etc. may be used.,

[0076] Suitable solid carriers are, for example, talc, titanium dioxide, pyrophyllite clay, silica, attapulgite clay, diatomaceous earth, limestone, calcium carbonate, bentonite, calcium montmorillonite, cottonseed meal, wheat flour, soybean flour, pumice, wood flour, powdered walnut meal, lignin and similar substances.,

[0077] A number of surfactants can be advantageously used in both solid and liquid formulations, especially those that can be diluted with a carrier before use. The surfactants can be anionic, cationic, nonionic or polymeric, and they can be used as emulsifiers, wetting agents or suspending agents or for other purposes. Typical surfactants include, for example, salts of alkyl sulfates such as diethanolammonium lauryl sulfate; salts of alkylaryl sulfonates such as calcium dodecylbenzenesulfonate; alkylphenol / alkylene oxide adducts such as nonylphenol ethoxylate; alcohol / alkylene oxide adducts such as tridecyl alcohol ethoxylate; soaps such as sodium stearate; salts of 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 lauryltrimethylammonium 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; and also further substances described, for example, in McCutcheon’s Detergents and Emulsifiers Annual, MC Publishing Corp., Ridgewood New Jersey (1981).

[0078] Further auxiliaries that can be used in pesticidal formulations include crystallization inhibitors, viscosity modifiers, suspending agents, dyes, antioxidants, foaming agents, light absorbers, mixing aids, defoamers, complexing agents, neutralizing or pH-adjusting substances and buffers, corrosion inhibitors, fragrances, wetting agents, absorption enhancers, micronutrients, plasticizers, flow promoters, lubricants, dispersants, thickeners, antifreezes, bactericides and liquid and solid fertilizers.

[0079] The composition according to the invention may contain oils of plant or animal origin, mineral oils, alkyl esters of such oils or mixtures of such oils and additives comprising oil derivatives. The amount of the oil additive in the composition according to the invention is generally from 0.01 to 10% based on the mixture to be applied. For example, the oil additive may be added to the spray tank at the desired concentration after the spray mixture has been prepared. Preferred oil additives include mineral oils or oils of plant origin, such as rapeseed oil, olive oil or sunflower oil, emulsified vegetable oils, alkyl esters of oils of plant origin, such as methyl derivatives, or oils of animal origin, such as fish oil or tallow. Preferred oil additives include alkyl esters of C8-C 22 fatty acids, in particular C 12 -C 18 methyl derivatives of fatty acids, such as methyl laurate, methyl palmitate and methyl oleate (methyl laurate, methyl palmitate and methyl oleate respectively). Many oil derivatives are known from Compendium of Herbicide Adjuvants, 10 th Edition, Southern Illinois University, 2010.

[0080] The herbicide composition generally comprises from 0.1 to 99% by weight, in particular from 0.1 to 95% by weight, of the compound of formula (I) and preferably from 0 to 25% by weight of a surfactant and from 1 to 99.9% by weight of a formulation adjuvant. The composition of the invention generally comprises from 0.1 to 99% by weight, in particular from 0.1 to 95% by weight, of the compound of the invention and preferably from 0 to 25% by weight of a surfactant and from 1 to 99.9% by weight of a formulation adjuvant. Commercially available products may preferably be formulated as concentrates, but the end user will normally use a diluted formulation.

[0081] The application rate varies within a wide range and depends on the nature of the soil, the method of application, the crop plant, the pest to be controlled, the prevailing weather conditions and other factors depending on the method of application, the time of application and the target crop. As a general guideline, the compound may be applied at a rate of 1 to 2000 l / ha, in particular 10 to 1000 l / ha.

[0082] A preferred formulation may have the following composition (by weight).

[0083] Emulsifiable concentrate: Active ingredient: 1 - 95%, preferably 60 - 90% Surfactant: 1 - 30%, preferably 5 - 20% Liquid carrier: 1 - 80%, preferably 1 - 35%

[0084] Powder: Active ingredient: 0.1 - 10%, preferably 0.1 - 5% Solid carrier: 99.9 - 90%, preferably 99.9 - 99%

[0085] Suspension concentrate: Active ingredient: 5 - 75%, preferably 10 - 50% Water: 94 - 24%, preferably 88 - 30% Surfactant: 1 - 40%, preferably 2 - 30%

[0086] Wettable powder: Active ingredient: 0.5 - 90%, preferably 1 - 80% Surfactant 0.5 - 20%, preferably 1 - 15% Solid carrier: 5 - 95%, preferably 15 - 90%

[0087] Granule: Active ingredient: 0.1 - 30%, preferably 0.1 - 15% Solid carrier: 99.5 - 70%, preferably 97 - 85%

[0088] The composition of the present invention may further contain at least one additional pesticidal agent. For example, the compounds according to the invention may also be used in combination with other herbicides or plant growth regulators. In a preferred embodiment, the additional pesticidal agent is a herbicide and / or a herbicide phytotoxicity reducer.

[0089] Therefore, the compounds of formula (I) can be used in combination with one or more other herbicides to provide various herbicide mixtures. The herbicide mixtures have surprising advantages that can be described in a broader sense as synergistic activity. Specific examples of such mixtures (where "I" represents the compound of formula (I)) include: I + acetochlor; I + acifluorfen (including acifluorfen-sodium); I + acronifen; I + alachlor; I + alloxydim; I + ametryn; I + amicarbazone; I + amidosulfuron; I + aminocyclopyrachlor; I + aminopyralid; I + amitrole; I + asulam; I + atrazine; I + bensulfuron (including bensulfuron-methyl); I + bentazone; I + bicyclopyrone; I + bilanafos; I + biphenox; I + bispyribac-sodium; I + bixlozone; I + bromacil; I + bromoxynil; I + butachlor; I + butaphenacil; I + cafenstrole; I + carfentrazone (including carfentrazone-ethyl); chloransulam (including chloransulam-methyl); I + chlormuron (including chlormuron-ethyl); I + chlorotoluron; I + cinosulfuron; I + chlorosulfuron; I + cinmethylin; I + clathrifos; I + clethodim; I + clodinafop (including clodinafop-propargyl); I + chromazone; I + clopyralid; I + cyclopyranil; I + cycloprimoester in millet; I + cyclosulfamuron; I + cyhalofop (including cyhalofop-butyl); I + 2,4-D (including its choline salt and 2-ethylhexyl ester); I + 2,4-DB; I + dimefuron; I + desmedipham; I + dicamba (including its aluminum, aminopropyl, bis-aminopropylmethyl, choline, dichloroprop, diglycolamine, dimethylamine, dimethylammonium, potassium and sodium salts); I + dichlorprop-methyl; I + dichlorsulam; I + diflufenican; I + difenzoquat; I + diflufenican; I + diflufenzoppil; I + dimethachlor; I + dimethenamid-P; I + diquat dibromide; I + diuron; I + esprocarb; I + ethalfluralin; I + ethofumesate; I + fenoxaprop (including fenoxaprop-P-ethyl);I + phenoxysulfone; I + fenquinotrione; I + fentrazamide; I + flazasulfuron; I + florasulam; I + flupirauxifen; I + flufenacet (including flufenacet - P - butyl); I + flucarbazone (including flucarbazone - sodium); I + flumetsulam; I + flumetralin; I + fluazinam; I + flupyrsulfuron (including flupyrsulfuron - methyl - sodium); I + fluroxypyr (including fluroxypyr - meptyl); I + fluthiacet - methyl; I + homesisafen; I + foramsulfuron; I + glufosinate (including its ammonium salt); I + glyphosate (including its diammonium, isopropylammonium and potassium salts); I + haloxyfop (including haloxyfop - methyl); I + halosulfuron - methyl; I + haloxybut (including haloxybut - methyl); I + hexazinone; I + hydantocidin; I + imazamox; I + imazapic; I + imazapyr; I + imazaquin; I + imazethapyr; I + indaziflam; I + iodosulfuron (including iodosulfuron - methyl - sodium); I + iofensulfuron; I + iofensulfuron - sodium; I + ioxynil; I + ifencarbazone; I + isoprothiolane; I + isoxaben; I + isoxaflutole; I + lactofen; I + rankotrione; I + linuron; I + MCPA; I + MCPB; I + mecoprop - P; I + mefenacet; I + mesosulfuron; I + mesosulfuron - methyl; I + mesotrione; I + metazachlor; I + metazachlor; I + methiopyris; I + metobromuron; I + metachlor; I + metosulam; I + metoxuron; I + metribuzin; I + metosulfuron; I + molinate; I + napropamide; I +nicosulfuron; I + norflurazon; I + orthosulfamuron; I + oxadiargyl; I + oxadiazone; I + oxasulfuron; I + oxyfluorfen; I + paraquat dichloride; I + pendimethalin; I + penoxsulam; I + phenmedipham; I + picloram; I + picolinafen; I + pinoxaden; I + pretilachlor; I + primisulfuron - methyl; I + prodiamein; I + promethrin; I + propachlor; I + propanil;I+propisochlor; I+profluralin; I+propisulfuron, I+propizamide; I+prosulfocarb; I+prosulfuron; I+pyraclonil; I+pyraflufen (including pyraflufen-ethyl); I+pyrazosulfotole; I+pyrazolate, I+pyrazosulfuron-ethyl; I+pyribenzoxim; I+pyridate; I+pyriftalid; I+pyrimisulfan, I+pyribac-sodium; I+pyroxasulfone; I+pyroxasulam; I+cinchonazine; I+cinmethylin; I+quizalofop (including quizalofop-P-ethyl and quizalofop-P-tefuryl); I+rimsulfuron; I+sulfofenacil; I+setoxydim; I+simazine; I+S-metolachlor; I+sulcotrione; I+sulfentrazone; I+sulfosulfuron; I+tebuthiuron; I+tefuryltrione; I+tenbotrione; I+terbutylazine; I+terbutryn; I+thiencarbazon; I+thifensulfuron; I+thiafenacil; I+tolpyralate; I+topramezone; I+tralkoxydim; I+triafamone; I+triallate; I+triasulfuron; I+tribenuron (including tribenuron-methyl); I+triclopyr; I+trifloxysulfuron (including trifloxysulfuron-sodium); I+triflumizoxazin; I+trifluralin; I+triflusulfuron; I+tritosulfuron; I+4-hydroxy-1-methoxy-5-methyl-3-[4-(trifluoromethyl)-2-pyridyl]imidazolidin-2-one; I+4-hydroxy-1,5-dimethyl 3-[4-(trifluoromethyl)-2-pyridyl]imidazolidin-2-one; I+5-ethoxy-4-hydroxy-1-methyl-3-[4-(trifluoromethyl)-2-pyridyl]imidazolidin-2-one; I+4-hydroxy-1-methyl-3-[4-(trifluoromethyl)-2-pyridyl]imidazolidin-2-one; I+4-hydroxy-1,5-dimethyl-3-[1-methyl-5-(trifluoromethyl)pyrazol-3-yl]imidazolidin-2-one; I+(4R)1-(5-tert-butylisoxazol-3-yl)-4-ethoxy-5-hydroxy-3-methyl-imidazolidin-2-one;I + 3-[2-(3,4-dimethoxyphenyl)-6-methyl-3-oxo-pyridazine-4-carbonyl]bicyclo[3.2.1]octane-2,4-dione; I + 2-[2-(3,4-dimethoxyphenyl)-6-methyl-3-oxo-pyridazine-4-carbonyl]-5-methyl-cyclohexane-1,3-dione; I + 2-[2-(3,4-dimethoxyphenyl)-6-methyl-3-oxo-pyridazine-4-carbonyl]cyclohexane-1,3-dione; I + 2-[2-(3,4-dimethoxyphenyl)-6-methyl-3-oxo-pyridazine-4-carbonyl]-5,5-dimethyl-cyclohexane-1,3-dione; I + 6-[2-(3,4-dimethoxyphenyl)-6-methyl-3-oxo-pyridazine-4-carbonyl]-2,2,4,4-tetramethyl-cyclohexane-1,3,5-trione; I + 2-[2-(3,4-dimethoxyphenyl)-6-methyl-3-oxo-pyridazine-4-carbonyl]-5-ethyl-cyclohexane-1,3-dione; I + 2-[2-(3,4-dimethoxyphenyl)-6-methyl-3-oxo-pyridazine-4-carbonyl]-4,4,6,6-tetramethyl-cyclohexane-1,3-dione; I + 2-[6-cyclopropyl-2-(3,4-dimethoxyphenyl)-3-oxo-pyridazine-4-carbonyl]-5-methyl-cyclohexane-1,3-dione; I + 3-[6-cyclopropyl-2-(3,4-dimethoxyphenyl)-3-oxo-pyridazine-4-carbonyl]bicyclo[3.2.1]octane-2,4-dione; I + 2-[6-cyclopropyl-2-(3,4-dimethoxyphenyl)-3-oxo-pyridazine-4-carbonyl]-5,5-dimethyl-cyclohexane-1,3-dione; I + 6-[6-cyclopropyl-2-(3,4-dimethoxyphenyl)-3-oxo-pyridazine-4-carbonyl]-2,2,4,4-tetramethyl-cyclohexane-1,3,5-trione; I + 2-[6-cyclopropyl-2-(3,4-dimethoxyphenyl)-3-oxo-pyridazine-4-carbonyl]cyclohexane-1,3-dione;I + 4 - [2-(3,4-dimethoxyphenyl)-6-methyl-3-oxo-pyridazine-4-carbonyl]-2,2,6,6-tetramethyl-tetrahydropyran-3,5-dione and I + 4 - [6-cyclopropyl-2-(3,4-dimethoxyphenyl)-3-oxo-pyridazine-4-carbonyl]-2,2,6,6-tetramethyl-tetrahydropyran-3,5-dione are mentioned.;

[0090] Preferred specific examples of such mixtures having synergistic activity include I + s-metolachlor; I + glufosinate; I + L-glufosinate; I + glyphosate; I + mesotrione; I + bicyclopyrone; and I + metribuzin.

[0091] The mixing partner of the compound of formula (I) can also be in the form of an ester or salt as described, for example, in The Pesticide Manual, Fourteenth Edition, British Crop Protection Council, 2006.

[0092] The compound of formula (I) can also be used in a mixture with other pesticides such as fungicides, nematicides or insecticides, examples of which are shown in The Pesticide Manual.

[0093] The mass ratio of any two components in each combination is selected as desired, for example, to give a synergistic effect. The mixing ratio of the compound of formula (I) to the mixing partner is 1:100 to 1000:1. The preferred mass ratio between any two components of the present invention is 75:1 to 1:75, more preferably 50:1 to 1:50, particularly 25:1 to 1:25, advantageously 10:1 to 1:10, for example 5:1 to 1:5, for example 1:3 to 3:1. The mixing ratio is understood to include the mass ratio on the one hand and the molar ratio on the other hand.

[0094] The mixture can advantageously be used in the above-mentioned formulations (in which case the "active ingredient" relates to each mixture of the compound of formula (I) and the mixing partner).

[0095] The compounds of formula (I) of the present invention can also be combined with herbicide phytotoxicity reducing agents. Preferred combinations (where "I" represents the compound of formula (I)) include I + benoxacor, I + cloquintocet (including cloquintocet - mexyl); I + cyprosulfamide; I + dichlormid; I + fenchlorazole (including fenchlorazole - ethyl); I + fenclorim; I + fluxofenim; I + furilazole; I + isoxadifen (including isoxadifen - ethyl); I + mefenpyr (including mefenpyr - diethyl); I + metcamifene; I + N-(2 - methoxybenzoyl)-4-[(methylaminocarbonyl)amino]benzenesulfonamide and I + oxabetrinil.

[0096] Mixtures of the compounds of formula (I) with cyprosulfamide, isoxadifen (including isoxadifen - ethyl), cloquintocet (including cloquintocet - mexyl) and / or N-(2 - methoxybenzoyl)-4-[(methyl - aminocarbonyl)amino]benzenesulfonamide are particularly preferred.

[0097] The phytotoxicity reducing agent of the compound of formula (I) can also be in the form of an ester or salt as described, for example, in The Pesticide Manual, 14th Edition (BCPC), 2006. The reference to cloquintocet - mexyl also applies to its lithium, sodium, potassium, calcium, magnesium, aluminum, iron, ammonium, quaternary ammonium, sulfonium or phosphonium salts as disclosed in WO 02 / 34048, and the reference to fenchlorazole - ethyl also applies to fenchlorazole and the like.

[0098] Preferably, the mixing ratio of the compound of formula (I) to the phytotoxicity reducing agent is 100:1 to 1:10, particularly 20:1 to 1:1.

[0099] The mixture can be advantageously used in the above formulations (in which case, the "active ingredient" relates to each mixture of the compound of formula (I) and the phytotoxicity reducing agent).

[0100] The compounds of formula (I) of the present invention are useful as herbicides. Therefore, the present invention further includes a method for controlling unwanted plants, which comprises applying an effective amount of the compound of the present invention or a herbicide composition containing said compound to the plants or their habitats. "Control" means killing, reducing or inhibiting growth, or preventing or reducing germination. Generally, the plants to be controlled are unwanted plants (weeds). "Habitat" means an area where plants are growing or will grow.

[0101] The application rate of the compound of formula (I) can vary within wide limits and depends on the nature of the soil, the method of application (pre-emergence; post-emergence; application to furrows; no-till application, etc.), the crop plants, the weeds to be controlled, the prevailing weather conditions, and other factors depending on the method of application, the timing of application and the target crop. The compounds of formula (I) according to the present invention are generally applied in an amount of 10 - 2000 g / ha, especially 50 - 1000 g / ha. The preferred range is 10 - 200 g / ha.

[0102] Application is generally carried out by spraying the composition with a large-area sprayer typically mounted on a tractor, but other methods such as dusting (in the case of powders), dripping or irrigation can also be used.

[0103] Useful plants to which the compositions according to the present invention can be applied include crops such as cereals, for example wheat and barley, cotton, rapeseed, sunflower, maize, rice, soybeans, sugar beet, sugarcane and turf.

[0104] Crop plants can also include trees such as fruit trees, palm trees, coconut trees or other nuts. Vining plants such as grapes, low-growing fruit trees, fruit-bearing plants and vegetables are also included.

[0105] The crops are understood to include crops that have been made resistant to herbicides or classes of herbicides (e.g., ALS, GS, EPSPS, PPO, ACCase, and HPPD inhibitors) by conventional breeding methods or genetic manipulation. An example of a crop that has been made resistant to imidazolinones, such as imazamox, by conventional breeding methods is Clearfield® summer vegetable seeds (canola). Examples of crops that have been made resistant to herbicides by genetic manipulation methods include, for example, glyphosate- and glufosinate-resistant corn varieties marketed under the trade names RoundupReady® and LibertyLink®.

[0106] Crops are also understood to be those that have been made resistant to pests by genetic engineering methods, such as Bt corn (resistant to the European corn borer), Bt cotton (resistant to the cotton bollworm), and also Bt potato (resistant to the Colorado potato beetle). An example of Bt corn is the Bt 176 corn hybrid of NK® (Syngenta Seeds). Bt toxins are proteins that are naturally formed by the soil bacterium Bacillus thuringiensis. Examples of toxins or genetically modified plants capable of synthesizing such toxins are described in European Patent Application Publication No. 451 878, European Patent Application Publication No. 374 753, International Publication No. 93 / 07278, International Publication No. 95 / 34656, International Publication No. 03 / 052073, and European Patent Application Publication No. 427 529. Examples of transgenic plants that encode insecticide resistance and contain one or more genes that express one or more toxins are KnockOut® (corn), Yield Gard® (corn), NuCOTIN33B® (cotton), Bollgard® (cotton), NewLeaf® (potato), NatureGard® and Protexcta®. Plant crops or their seed material can be resistant to herbicides and at the same time resistant to insect feeding (“stacked” transgenic events). For example, the seeds can have the ability to express the insecticidal Cry3 protein while at the same time being tolerant to glyphosate.

[0107] Crops are also understood to include those obtained by conventional breeding methods or genetic engineering and containing so-called output traits (such as improved storage stability, higher nutritional value, and improved flavor).

[0108] Other useful plants include, for example, turfgrass, lawns, turfgrass commercially cultivated for parks and roadside turf or for turf, and ornamental plants such as flowers or shrubs.

[0109] The compounds of the present invention can be used in a method for controlling unwanted vegetation in crop plants that are resistant to protoporphyrinogen oxidase (PPO) inhibitors. Such plants can be obtained, for example, by transforming crop plants with a nucleic acid that encodes a suitable protoporphyrinogen oxidase and that may contain a mutation to render it more resistant to PPO inhibitors. Examples of such nucleic acids and crop plants are disclosed in WO 95 / 34659, WO 97 / 32011, WO 2007 / 024739, WO 2012 / 080975, WO 2013 / 189984, WO 2015 / 022636, WO 2015 / 022640, WO 2015 / 092706, WO 2016 / 099153, WO 2017 / 023778, WO 2017 / 039969, WO 2017 / 217793, WO 2017 / 217794, WO 2018 / 114759, WO 2019 / 117578, WO 2019 / 117579, and WO 2019 / 118726. Accordingly, the present invention also provides a method for controlling unwanted vegetation at a plant cultivation site, the method comprising: a) providing, at the site, a plant comprising at least one nucleic acid comprising a nucleotide sequence encoding a PPO polypeptide that is resistant or tolerant to a protoporphyrinogen oxidase (PPO)-inhibiting herbicide; and b) applying to the site an effective amount of the herbicide, wherein the PPO-inhibiting herbicide is a compound of formula (I) as defined herein.

[0110] The compounds and compositions of formula (I) of the present invention can typically be used to control various monocotyledonous and dicotyledonous weed species. Examples of monocotyledonous species that can typically be controlled include Alopecurus myosuroides, Avena fatua, Brachiaria plantaginea, Bromus tectorum, Cyperus esculentus, Digitaria sanguinalis, Echinochloa crus-galli, Lolium perenne, Lolium multiflorum, Panicum miliaceum, Poa annua, Setaria viridis, Setaria faberi, and Sorghum bicolor. Examples of dicotyledonous species that can be controlled include Abutilon theophrasti, Amaranthus retroflexus, Bidens pilosa, Chenopodium album, Euphorbia heterophylla, Galium aparine, Ipomoea hederacea, Kochia scoparia, Polygonum Convolvulus, Sida spinosa, Sinapis arvensis, Solanum nigrum, Stellaria media, Veronica persica, and Xanthium strumarium. It should be understood that unwanted plants also include those weeds that have been made resistant to herbicides or classes of herbicides (e.g., ALS, GS, EPSPS, PPO, ACCase, and HPPD inhibitors) by evolution, conventional breeding methods, or genetic manipulation.Examples include Amaranthus palmeri that has evolved resistance to glyphosate and / or acetolactate synthase (ALS)-inhibiting herbicides.

[0111] The compounds of the present invention can be used in a method for controlling undesirable plants or weeds that are resistant to protoporphyrinogen oxidase (PPO) inhibitors. For example, Amaranthus palmeri and Amaranthus tuberculatus populations have evolved into PPO-resistant weeds by amino acid substitutions in PPX2L such as those occurring at amino acid R128 (also designated R98) and G399, or a codon (glycine) deletion (Δ210) in PPX2L at codon 210. The compounds of the present invention can be used in a method for controlling Amaranthus palmeri and / or Amaranthus tuberculatus having mutations or deletions in the aforementioned codons, and it will be apparent to attempt this compound for controlling undesirable plants or weeds having other mutations that confer tolerance or resistance to a resulting PPO inhibitor.

[0112] The compounds of formula (I) are also useful for pre-harvest drying of crops such as, but not limited to, potato, soybean, sunflower and cotton. Pre-harvest drying is used to dry the leaves of the crop without significant damage to the crop itself to assist in harvesting.

[0113] The compounds / compositions of the present invention are particularly useful in non-selective burn-down applications and can therefore also be used to control volunteer plants or to defoliate crop plants.

[0114] Here, various aspects and embodiments of the present invention are illustrated in more detail by way of example. It will be understood that detailed modifications can be made without departing from the scope of the present invention.

Examples

[0115] The following examples serve to illustrate the present invention but do not limit the present invention.

[0116] Synthesis Example Example 1 Preparation of Ethyl (5S)-3-[2-chloro-4-fluoro-5-[2-methoxy-6-oxo-4-(trifluoromethyl)pyrimidin-1-yl]phenyl]-5-methyl-4H-isoxazole-5-carboxylate (Compound 11, S-enantiomer) Step 1 Synthesis of Ethyl (5S)-3-[2-chloro-5-[2,4-dioxo-6-(trifluoromethyl)-1H-pyrimidin-3-yl]-4-fluoro-phenyl]-5-methyl-4H-isoxazole-5-carboxylate

Chemical Structure

[0117] Using the same method, ethyl (5R)-3-[2-chloro-5-[2,4-dioxo-6-(trifluoromethyl)-1H-pyrimidin-3-yl]-4-fluoro-phenyl]-5-methyl-4H-isoxazole-5-carboxylate; ethyl 3-[2-chloro-5-[2,4-dioxo-6-(trifluoromethyl)-1H-pyrimidin-3-yl]-4-fluoro-phenyl]-5-methyl-4H-isoxazole-5-carboxylate was also prepared.

[0118] Step 2 Synthesis of ethyl (5S)-3-[2-chloro-4-fluoro-5-[2-methoxy-6-oxo-4-(trifluoromethyl)pyrimidin-1-yl]phenyl]-5-methyl-4H-isoxazole-5-carboxylate (Compound 11, S-enantiomer) [Chemical formula] Potassium carbonate (3.0 g, 21.4 mmol) was then added followed by iodomethane (2.2 ml, 35.7 mmol) to a solution of ethyl (5S)-3-[2-chloro-5-[2,4-dioxo-6-(trifluoromethyl)-1H-pyrimidin-3-yl]-4-fluoro-phenyl]-5-methyl-4H-isoxazole-5-carboxylate (9.2 g, 17.9 mmol) in acetone (89 ml). The resulting mixture was stirred at 36 °C for 16 h. The mixture was evaporated under reduced pressure, ethyl acetate (90 ml) was added and the mixture was filtered. The filtrate was evaporated under reduced pressure and the residue was purified by chromatography to give ethyl (5S)-3-[2-chloro-4-fluoro-5-[2-methoxy-6-oxo-4-(trifluoromethyl)pyrimidin-1-yl]phenyl]-5-methyl-4H-isoxazole-5-carboxylate (Compound 11, S-enantiomer) as a gum (34 mg). 11H NMR (400 MHz, CDCl3) δ 7.65 (dd, 1H), 7.4 (dd, 1H), 6.6 (s, 1H), 4.3 (m, 2H), 4.15 (d, 0.5H), 4.0 (s, 3H), 3.9 (d, 0.5H), 3.5 (d, 0.5H), 3.3 (d, 0.5H), 1.75 (2×s, 3H), 1.35 (2×t, 3H) ppm.

[0119] Using the same method, ethyl (5R)-3-[2-chloro-4-fluoro-5-[2-methoxy-6-oxo-4-(trifluoromethyl)pyrimidin-1-yl]phenyl]-5-methyl-4H-isoxazole-5-carboxylate (Compound 11, R-enantiomer); ethyl 3-[2-chloro-4-fluoro-5-[2-methoxy-6-oxo-4-(trifluoromethyl)pyrimidin-1-yl]phenyl]-5-methyl-4H-isoxazole-5-carboxylate (Compound 11, racemate) was also prepared.

[0120] Formulation Examples

[0121] [Table 2]

[0122] The combination is thoroughly mixed with adjuvants, and the mixture is thoroughly ground in a suitable mill and diluted with water to obtain a wettable powder that can give a suspension of the desired concentration.

[0123] Emulsifiable concentrate Active ingredient 10% Octylphenol polyethylene glycol ether (4 - 5 mol ethylene oxide) 3% Calcium dodecylbenzenesulfonate 3% Castor oil polyglycol ether (35 mol ethylene oxide) 4% Cyclohexanone 30% Xylene mixture 50%

[0124] Emulsions of any required dilution that can be used for plant protection can be obtained from this concentrate by dilution with water.

[0125]

Table 3

[0126] The immediately usable powder is obtained by mixing the combination with a carrier and grinding the mixture in a suitable mill.

[0127] Extruder granules Active ingredient 15% Sodium lignosulfonate 2% Carboxymethyl cellulose 1% Kaolin 82%

[0128] Mix the combination with adjuvants, grind, and moisten the mixture with water. Extrude the mixture and then dry it in an air stream.

[0129] Coated granules Active ingredient 8% Polyethylene glycol (molecular weight 200) 3% Kaolin 89%

[0130] Apply the micronized combination uniformly to kaolin moistened with polyethylene glycol in a mixer. Coated granules that do not generate dust are thus obtained.

[0131] Suspension concentrate Active ingredient 40% Propylene glycol 10% Nonylphenol polyethylene glycol ether (15 mol of ethylene oxide) 6% Sodium lignosulfonate 10% Carboxymethyl cellulose 1% Silicone oil (in the form of a 75% emulsion in water) 1% Water 32%

[0132] The finely ground combination is thoroughly mixed with an adjuvant to obtain a suspension concentrate, from which a suspension of any desired dilution can be obtained by dilution with water.

[0133] Sustained release capsule suspension Mix 28 parts of the combination with 2 parts of an aromatic solvent and 7 parts of a toluene diisocyanate / polymethylene-polyphenyl isocyanate-mixture (8:1). Emulsify this mixture in a mixture of 1.2 parts of polyvinyl alcohol, 0.05 part of an antifoaming agent and 51.6 parts of water until the desired particle size is achieved. Add to this emulsion a mixture of 2.8 parts of 1,6-diaminohexane in 5.3 parts of water. Stir this mixture until the polymerization reaction is complete.

[0134] The resulting capsule suspension is stabilized by adding 0.25 part of a thickening agent and 3 parts of a dispersing agent. The capsule suspension formulation contains 28% of the active ingredient. The median capsule diameter is 8 - 15 microns.

[0135] The resulting formulation is applied to the seeds as an aqueous suspension using an apparatus suitable for that purpose.

[0136] Biological examples Biological efficacy before germination Weed and / or crop seeds were sown in standard soil in pots. After one day of cultivation under controlled conditions in a greenhouse (24 / 19 °C, day / night; 16 hours of light), a spray aqueous solution derived from a formulation of the technical active ingredient in a small amount of acetone and a special solvent and a mixture of emulsifiers called IF50 (11.12% Emulsogen EL360 TM + 44.44% N-methylpyrrolidone + 44.44% Dowanol DPM glycol ether) which results in a 50 g / l solution, which is then diluted using 0.2% Genapol XO80 as a diluent, was sprayed onto the plants to give the desired final dose of the test compound.

[0137] Subsequently, the test plants were grown under controlled conditions in a greenhouse (24 / 18 °C, day / night; 15 hours of light; 50% humidity) and watered twice a day. The test was evaluated after 13 days (100 = total damage to the plant; 0 = no damage to the plant). The results are shown in Table 2 below.

[0138]

Table 4

[0139] Biological efficacy after germination Weed and / or crop seeds were sown in standard soil in pots. After 14 days of cultivation under controlled conditions in a greenhouse (24 / 19 °C, day / night; 16 hours of light), a spray aqueous solution derived from a formulation of the technical active ingredient in a small amount of acetone and a special solvent and a mixture of emulsifiers called IF50 (11.12% Emulsogen EL360 TM + 44.44% N-methylpyrrolidone + 44.44% Dowanol DPM glycol ether) that results in a 50 g / l solution (which is then diluted using 0.2% Genapol XO80 as a diluent) was sprayed onto the plants to give the desired final dose of the test compound.

[0140] Subsequently, the test plants were grown under controlled conditions in a greenhouse (24 / 18 °C, day / night; 15 hours of light; 50% humidity) and watered twice a day. The test was evaluated after 13 days (100 = total damage to the plant; 0 = no damage to the plant). The results are shown in Table 3 below.

[0141]

Table 5

Claims

1. Formula (I): 【Chemical 1】 (wherein R 1 is selected from the group consisting of hydrogen and C 1 to C 6 alkyl; R 2 is selected from the group consisting of C 1 -C 6 alkyl, C 3 -C 6 alkenyl and C 3 -C 6 alkynyl; R 3 is selected from the group consisting of hydrogen, halogen, C 1 to C 4 alkyl, C 1 to C 4 haloalkyl, C 1 to C 4 alkoxy, C 1 to C 4 haloalkoxy and C 1 to C 4 alkylsulfonyl; R 4 is selected from the group consisting of hydrogen, halogen, cyano, aminocarbonyl, aminothiocarbonyl, C 1 to C 4 alkyl, C 1 to C 4 haloalkyl, C 1 to C 4 alkoxy, C 1 to C 4 haloalkoxy and C 1 to C 4 alkylsulfonyl; Each R 5 and R 6 is independently selected from the group consisting of hydrogen, cyano, C 1 to C 6 alkyl, C 1 to C 6 haloalkyl, C 1 to C 4 alkylsulfonyl, CO 2 R 9 , CONR 10 R 11 and CH 2 OR 12 ; and is independently selected from the group consisting of Each R 7 and R 8 is independently selected from the group consisting of hydrogen, cyano, C 1 to C 6 alkyl, C 1 to C 6 haloalkyl, C 1 to C 4 alkoxy, C 1 to C 4 alkylsulfonyl, C(=Z)R 15 , CO 2 R 9 , CONR 10 R 11 and CH 2 OR 12 ; Z is selected from the group consisting of oxygen, NOR 16 and NN(R 16 ) 2 and is selected from the group consisting of; R 9 is hydrogen, C 1 -C 10 alkyl, C 1 -C 10 haloalkyl, C 3 -C 6 alkenyl, C 3 -C 6 haloalkenyl, C 3 -C 6 alkynyl, C 1 -C 4 alkoxy C 1 -C 6 alkyl, C 1 -C 4 haloalkoxy C 1 -C 6 alkyl, C 6 -C 10 aryl C 1 -C 3 alkyl, C 6 -C 10 aryl C 1 -C 3 alkyl, where R 13 is substituted by 1 to 4 groups represented by C 6 -C 10 aryl C 1 -C 3 alkyl, heteroaryl C 1 -C 3 alkyl, and heteroaryl C 1 -C 3 alkyl, where R 13 is substituted by 1 to 3 groups represented by heteroaryl C 1 -C 3 alkyl and is selected from the group consisting of; R 10 is selected from the group consisting of hydrogen, C 1 to C 6 alkyl and SO 2 R 14 ; and is selected from the group consisting of R 11 is selected from the group consisting of hydrogen and C 1 to C 6 alkyl; or R 10 and R 11 together with the nitrogen to which they are attached form a 3- to 6-membered heterocyclyl ring optionally containing an oxygen atom; R 12 is hydrogen, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 alkylsulfonyl, C 1 -C 4 haloalkylsulfonyl, phenylsulfonyl, phenylsulfonyl substituted by one or two groups represented by R 13 ; C 1 -C 4 alkylcarbonyl, C 1 -C 4 haloalkylcarbonyl, C 6 -C 10 arylcarbonyl, C 6 -C 10 arylcarbonyl substituted by one to four groups R 13 ; C 6 -C 10 arylcarbonyl, heteroarylcarbonyl, heteroarylcarbonyl substituted by one to three groups represented by R 13 ; C 6 -C 10 arylC 1 -C 3 alkylcarbonyl, C 6 -C 10 arylC 1 -C 3 alkylcarbonyl substituted by one to four groups represented by R 13 ; C 6 -C 10 arylC 1 -C 3 alkylcarbonyl, heteroarylC 1 -C 3 alkylcarbonyl, and heteroarylC 1 -C 3 alkylcarbonyl substituted by one to three groups represented by R 13 ; heteroarylC 1 -C 3 alkylcarbonyl, and is selected from the group consisting of; Each R 13 is independently selected from the group consisting of halogen, C 1 ~C 4 alkyl, C 1 ~C 4 haloalkyl, C 1 ~C 4 alkoxy, C 1 ~C 4 haloalkoxy, cyano and C 1 ~C 4 alkylsulfonyl; R 14 is selected from the group consisting of C 1 to C 4 alkyl, C 1 to C 4 haloalkyl and C 1 to C 4 alkyl(C 1 to C 4 alkyl)amino; R 15 is selected from the group consisting of hydrogen, C 1 to C 4 alkyl and C 1 to C 4 haloalkyl; Each R 16 is independently selected from the group consisting of hydrogen, C 1 ~C 4 alkyl, C 1 ~C 4 haloalkyl and C 1 ~C 4 alkoxycarbonyl C 1 ~C 4 alkyl; R 17 is selected from the group consisting of hydrogen, C 1 to C 4 alkyl and C 1 to C 4 haloalkyl). a compound of or an agriculturally acceptable salt thereof.

2. R 1 is the compound according to claim 1 selected from the group consisting of hydrogen.

3. R 2 is a compound according to claim 1 or 2, selected from the group consisting of C 1 to C 4 alkyl.

4. Each R 3 and R 4 is independently selected from the group consisting of hydrogen and halogen, the compound according to any one of claims 1 to 3.

5. Each R 5 and R 6 is independently hydrogen, the compound according to any one of claims 1 to 4.

6. Each R 7 and R 8 is independently selected from the group consisting of hydrogen, C 1 to C 4 alkyl, CO 2 R 9 , CONR 10 R 11 and CH 2 OR 12 The compound according to any one of claims 1 to 5, which is independently selected from the group consisting of

7. R 7 is CO 2 R 9 The compound according to any one of claims 1 to 6, selected from the group consisting of

8. R 8 is a compound according to any one of claims 1 to 7, selected from the group consisting of hydrogen and C 1 -C 4 alkyl.

9. R 9 is a compound according to any one of claims 1 to 8, selected from the group consisting of hydrogen and C 1 to C 2 alkyl.

10. R 17 is C 1 -C 2 alkyl and C 1 -C 2 The compound according to any one of claims 1 to 9, selected from the group consisting of haloalkyl.

11. R 1 is selected from the group consisting of hydrogen and methyl; R 2 is C 1 to C 2 alkyl; R 3 is selected from the group consisting of hydrogen, chlorine and fluorine; R 4 is selected from the group consisting of chlorine, bromine, cyano and aminothiocarbonyl; Each R 5 and R 6 are each independently selected from the group consisting of hydrogen and C 1 to C 2 alkyl; R 7 is selected from the group consisting of CO 2 R 9 , CONR 10 R 11 and CH 2 OR 12 ; and is selected from the group consisting of R 8 is selected from the group consisting of hydrogen and C 1 to C 4 alkyl; R 9 is selected from the group consisting of hydrogen, C 1 to C 4 alkyl, C 1 to C 2 alkoxy C 1 to C 2 alkyl and phenyl C 1 to C 2 alkyl; R 10 is SO 2 R 14 and; R 11 is hydrogen, and R 12 is selected from the group consisting of C 1 -C 2 alkylsulfonyl, C 1 -C 2 haloalkylsulfonyl and C 1 -C 4 alkylcarbonyl; R 14 is selected from the group consisting of methyl and isopropyl(methyl)amino; and R 17 is a compound according to any one of claims 1 to 10, selected from the group consisting of methyl and trifluoromethyl.

12. R 1 is hydrogen; R 2 is methyl; R 3 is selected from the group consisting of chlorine and fluorine; R 4 is selected from the group consisting of chlorine and bromine; Each R 5 and R 6 is hydrogen; R 7 is CO 2 R 9 and; R 8 is methyl; R 9 is selected from the group consisting of hydrogen, C 1 -C 4 alkyl and phenyl C 1 -C 2 alkyl; and R 17 is a compound according to any one of claims 1 to 11, wherein R is trifluoromethyl.

13. An agrochemical composition comprising a herbicidally effective amount of a compound of formula (I) according to any one of claims 1 to 12 and an agrochemically acceptable diluent or carrier.

14. A method for controlling or preventing unwanted plant growth, wherein a herbicidally effective amount of a compound of formula (I) according to any one of claims 1 to 12 or a composition according to claim 13 is applied to a plant, a part thereof or its habitat.

15. A method for controlling unwanted vegetation at a plant cultivation site, comprising: a) providing at said site a plant comprising at least one nucleic acid comprising a nucleotide sequence encoding a PPO polypeptide that is resistant or tolerant to a protoporphyrinogen oxidase (PPO) inhibitor herbicide; b) applying to said site an effective amount of said herbicide, wherein said PPO inhibitor herbicide is a compound of formula (I) according to any one of claims 1 to 12.

Images