Herbicidal compounds

Abstract

Compounds of formula (I) which are useful as pesticides, particularly as herbicides [Formula 1] TIFF2022534105000046.tif60160 (wherein the substituents are as defined in claim 1) Compound.

Description

[Technical field]

[0001] The present invention relates to herbicidally active isoxazoline derivatives and to processes and intermediates used in the preparation of such derivatives. The invention further extends to herbicidal compositions containing such derivatives and the use of such compounds and compositions for the control of undesirable plant growth, particularly for the control of weeds in crops of useful plants. Summary of the Invention [Means for solving the problem]

[0002] The present invention is based on the finding that isoxazoline derivatives of formula (I) as defined herein exhibit surprisingly good herbicidal activity. Thus, according to the present invention, isoxazoline derivatives of formula (I): [ka] (In the formula, X is selected from the group consisting of oxygen and sulfur; Y is selected from the group consisting of CH and nitrogen; R 1 is hydrogen and C 1 ~C 6 selected from the group consisting of alkyl; R 2 is hydrogen, amino, C 1 ~C 6 Alkyl, C 3 ~C 6 Alkenyl and C 3 ~C 6 alkynyl; R 3 is hydrogen, halogen, C 1 ~C 4 Alkyl, C 1 ~C 4 Haloalkyl, C 1 ~C 4 Alkoxy, C 1 ~C 4 Haloalkoxy and C 1 ~C 4alkylsulfonyl; R 4 is hydrogen, halogen, cyano, aminocarbonyl, aminothiocarbonyl, C 1 ~C 4 Alkyl, C 1 ~C 4 Haloalkyl, C 1 ~C 4 Alkoxy, C 1 ~C 4 Haloalkoxy and C 1 ~C 4 alkylsulfonyl; Each R 5 and R 6 is hydrogen, cyano, C 1 ~C 6 Alkyl, C 1 ~C 6 Haloalkyl, C 1 ~C 4 Alkyl sulfonyl, CO 2 R 9 ,CONR 10 R 11 and C.H. 2 OR 12 independently selected from the group consisting of: Each R 7 and R 8 is hydrogen, cyano, C 1 ~C 6 Alkyl, C 1 ~C 6 Haloalkyl, C 1 ~C 4 Alkoxy, C 1 ~C 4 Alkylsulfonyl, C(=Z)R 15 , CO 2 R 9 ,CONR 10 R 11 and C.H. 2 OR 12 independently selected from the group consisting of: Z is oxygen, NOR 16 and NN(R 16 ) 2 selected from the group consisting of; R 9 is hydrogen, C 1 ~C10 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, 1 to 4 groups R 13 C replaced by 6 ~C 10 Aryl C 1 ~C 3 Alkyl, Heteroaryl C 1 ~C 3 Alkyl and 1 to 3 groups R 13 Heteroaryl C substituted by 1 ~C 3 selected from the group consisting of alkyl; R 10 is hydrogen, C 1 ~C 6 Alkyl and SO 2 R 14 selected from the group consisting of; R 11 is hydrogen and C 1 ~C 6 is selected from the group consisting of 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 4Alkylsulfonyl, C 1 ~C 4 Haloalkylsulfonyl, phenylsulfonyl, 1-2 groups R 13 Phenylsulfonyl substituted by C 1 ~C 4 Alkyl carbonyl, C 1 ~C 4 Haloalkylcarbonyl, C 6 ~C 10 Arylcarbonyl, 1 to 4 groups R 13 C replaced by 6 ~C 10 Arylcarbonyl, heteroarylcarbonyl, 1 to 3 groups R 13 heteroarylcarbonyl substituted by C 6 ~C 10 Aryl C 1 ~C 3 Alkylcarbonyl, 1 to 4 groups R 13 C replaced by 6 ~C 10 Aryl C 1 ~C 3 Alkylcarbonyl, HeteroarylC 1 ~C 3 Alkylcarbonyl and 1 to 3 groups R 13 Heteroaryl C substituted by 1 ~C 3 alkylcarbonyl; Each R 13 is a 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 independently selected from the group consisting of alkylsulfonyl; R 14 is C 1 ~C 4 Alkyl, C 1 ~C 4 Haloalkyl and C1 ~C 4 Alkyl(C 1 ~C 4 (alkyl)amino; R 15 is hydrogen, C 1 ~C 4 Alkyl and C 1 ~C 4 haloalkyl; Each R 16 is hydrogen, C 1 ~C 4 Alkyl, C 1 ~C 4 Haloalkyl and C 1 ~C 4 Alkoxycarbonyl C 1 ~C 4 alkyl) or an agriculturally acceptable salt thereof.

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

[0004] According to a third aspect of the present invention there is provided a method for controlling or preventing undesired 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 the plant, its part 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 invention there is provided a process for preparing a compound of formula (I). DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[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 refers to the group -CN.

[0009] As used herein, hydroxy refers to an --OH group.

[0010] As used herein, nitro refers to -NO 2 means a group.

[0011] As used herein, "C 1 ~C 6 The term "alkyl" refers to a straight or branched hydrocarbon chain radical consisting solely of carbon and hydrogen atoms, containing no unsaturation, having from 1 to 6 carbon atoms, and attached to the remainder of the molecule by a single bond. 1 ~C 4 Alkyl and C 1 ~C 2 Alkyl should be construed accordingly. 1 ~C 6 Examples of alkyl include, but are not limited to, methyl (Me), ethyl (Et), n-propyl, 1-methylethyl (isopropyl), n-butyl, and 1-dimethylethyl (t-butyl).

[0012] As used herein, "C 1 ~C 6 The term "alkoxy" generally refers to R a C 1 ~C 6 The alkyl group of the formula -OR a C 1 ~C 4 Alkoxy should be construed accordingly. 1-4Examples of alkoxy include, but are not limited to, methoxy, ethoxy, propoxy, isopropoxy, and t-butoxy.

[0013] As used herein, "C 1 ~C 6 The term "haloalkyl" refers generally to any C1, C2, or C3 alkyl group as defined above, which is substituted with one or more of the same or different halogen atoms. 1 ~C 6 Refers to an alkyl group. 1 ~C 4 Haloalkyl should be construed accordingly. 1 ~C 6 Examples of haloalkyl include, but are not limited to, chloromethyl, fluoromethyl, fluoroethyl, difluoromethyl, trifluoromethyl, and 2,2,2-trifluoroethyl.

[0014] As used herein, "C 2 ~C 6 The term "alkenyl" refers to a straight or branched hydrocarbon chain radical group composed solely of carbon and hydrogen atoms, containing at least one double bond which may be in either the (E) or (Z) configuration, having from 2 to 6 carbon atoms and attached to the remainder of the molecule by a single bond. 2 ~C 4 Alkenyl should be construed accordingly. 2 ~C 6 Examples of alkenyl include, but are not limited to, prop-1-enyl, allyl (prop-2-enyl), and but-1-enyl.

[0015] As used herein, "C 2 ~C 6 The term "haloalkenyl" generally refers to any of the C1, C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17, C18, C19, C20, C21, C31, C42, C53, C64, C76, C88, C99, C100, C111 2 ~C 6 Refers to the alkenyl group. 2 ~C 6Examples of haloalkenyls include, but are not limited to, chloroethylene, fluoroethylene, 1,1-difluoroethylene, 1,1-dichloroethylene, and 1,1,2-trichloroethylene.

[0016] As used herein, "C 2 ~C 6 The term "alkynyl" refers to a straight or branched hydrocarbon chain radical group consisting solely of carbon and hydrogen atoms, containing at least one triple bond, having from 2 to 6 carbon atoms, and attached to the remainder of the molecule by a single bond. 2 ~C 4 Alkynyl should be construed accordingly. 2 ~C 6 Examples of alkynyl include, but are not limited to, prop-1-ynyl, propargyl (prop-2-ynyl), and but-1-ynyl.

[0017] As used herein, "C 1 ~C 6 The term "haloalkoxy" refers to any of the C1, C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17, C18, C19, C20, C21, C22, C30, C41, C52, C63, C74, C85, C96, C97, C98 1 ~C 6 Refers to an alkoxy group. 1 ~C 4 Haloalkoxy should be construed accordingly. 1 ~C 6 Examples of haloalkoxy include, but are not limited to, fluoromethoxy, difluoromethoxy, fluoroethoxy, trifluoromethoxy, and trifluoroethoxy.

[0018] As used herein, "C 1 ~C 3 Haloalkoxy C 1 ~C 3 The term "alkyl" generally refers to R b C 1 ~C 3 R is a haloalkyl group and is generally as defined abovea C 1 ~C 3 The alkylene group of formula R b -OR a - refers to the group.

[0019] As used herein, "C 1 ~C 3 Alkoxy C 1 ~C 3 The term "alkyl" generally refers to R b C 1 ~C 3 R is an alkyl group and is generally as defined above a C 1 ~C 3 The alkylene group of formula R b -OR a - refers to the group.

[0020] As used herein, "C 1 ~C 3 Alkoxy C 1 ~C 3 The term "alkoxy-" generally refers to R b C 1 ~C 3 R is an alkyl group and is generally as defined above a C 1 ~C 3 The alkylene group of formula R b -OR a It refers to the -O- group.

[0021] As used herein, "C 3 ~C 6 The term "alkenyloxy" generally refers to any of R, R- ... a C 3 ~C 6 An alkenyl group of the formula -OR a Refers to the group.

[0022] As used herein, "C 3 ~C 6The term "alkynyloxy" generally refers to any of R, R , R , R a C 3 ~C 6 An alkynyl group of the formula -OR a Refers to the group.

[0023] As used herein, "hydroxy C 1 ~C 6 The term "alkyl" refers generally to any C alkyl group as defined above, which is substituted with one or more hydroxy groups. 1 ~C 6 Refers to an alkyl group.

[0024] As used herein, "C 1 ~C 6 The term "alkylcarbonyl" generally refers to R a C 1 ~C 6 Alkyl groups of the formula -C(O)R a Refers to the group.

[0025] As used herein, "C 1 ~C 6 The term "alkoxycarbonyl" generally refers to R a C 1 ~C 6 An alkyl group of the formula -C(O)OR a Refers to the group.

[0026] As used herein, the term "aminocarbonyl" refers to a group of the formula -C(O)NH 2 Refers to the group.

[0027] As used herein, the term "aminothiocarbonyl" refers to a compound of the formula -C(S)NH 2 Refers to the group.

[0028] As used herein, "C 3 ~C 6The term "cycloalkyl" refers to a stable monocyclic ring radical that is saturated or partially saturated and contains 3 to 6 carbon atoms. 3 ~C 4 Cycloalkyl should be construed accordingly. 3 ~C 6 Examples of cycloalkyl include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl.

[0029] As used herein, "C 3 ~C 6 The term "halocycloalkyl" refers generally to a C1-cycloalkyl group as defined above, which is substituted with one or more of the same or different halogen atoms. 3 ~C 6 Refers to a cycloalkyl group. 3 ~C 4 Halocycloalkyl should be construed accordingly.

[0030] As used herein, "C 3 ~C 6 The term "cycloalkoxy" generally refers to R as defined above. a C 3 ~C 6 Cycloalkyl groups of the formula -OR a Refers to the group.

[0031] As used herein, "NC 3 ~C 6 The term "cycloalkylamino" generally refers to R a C 3 ~C 6 A cycloalkyl group of the formula -NHR a Refers to the group.

[0032] As used herein, unless otherwise specified, the term "heteroaryl" refers to a 5- or 6-membered monocyclic aromatic ring containing 1, 2, 3, or 4 heteroatoms independently selected from nitrogen, oxygen, and sulfur. Heteroaryl groups can be bonded to the remainder of the molecule through a carbon atom or a heteroatom. Examples of heteroaryl include furyl, pyrrolyl, imidazolyl, thienyl, pyrazolyl, thiazolyl, isothiazolyl, oxazolyl, isoxazolyl, triazolyl, tetrazolyl, pyrazinyl, pyridazinyl, pyrimidyl, or pyridyl.

[0033] As used herein, unless otherwise specified, the term "heterocyclyl" or "heterocyclic" refers to a stable 4-6 membered non-aromatic monocyclic ring group containing one, two, or three heteroatoms independently selected from nitrogen, oxygen, and sulfur. The heterocyclyl group may be attached to the remainder of the molecule through 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 optionally asymmetric carbon atoms in the compounds of formula (I) means that the compounds can occur in chiral isomeric forms, i.e. enantiomeric or diastereomeric forms. Astrogenic isomers can also occur as a result of restricted rotation about a single bond. Formula (I) is intended to include all these possible isomeric forms and mixtures thereof. The present invention includes all these possible isomeric forms and mixtures thereof for the compounds of formula (I). Similarly, formula (I) is intended to include all possible tautomers, if present, including lactam-lactim tautomerism and keto-enol tautomerism. The present invention includes all possible tautomeric forms for the compounds of formula (I). Similarly, disubstituted alkenes, if present, can exist in E or Z form or as a mixture of both in any proportion. The present invention includes all these possible isomeric forms and mixtures thereof for the compounds of formula (I).

[0035] The compounds of formula (I) are typically provided in the form of an agriculturally acceptable salt, a 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, hexyloctylamine, histidine, indoline, isoamylamine, isobutanolamine, isobutylamine, isopropanolamine, isopropylamine, lysine, Examples of suitable amines include amine, 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, tallowamine, 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 includes the substituents X, Y, Z, R related to the compounds of formula (I) according to the present invention: 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 and R 16 Definitions, including preferred definitions, are provided for: Any of the definitions given below for any one of these substituents may be combined with any definition of any other substituent given below or elsewhere in this specification.

[0038] Preferably, X is sulfur.

[0039] Preferably, Y is CH.

[0040] Preferably, R 1 is hydrogen and C 1 ~C 4 alkyl, more preferably C 1 ~C 2 It is preferably an alkyl group, and most preferably a methyl group.

[0041] Preferably, R 2 is hydrogen, C 1 ~C 4 Alkyl and C 3 ~C 4 alkynyl, more preferably C 1 ~C 2 It is preferably an alkyl group, and most preferably a methyl group.

[0042] Preferably, R 3 is selected from the group consisting of hydrogen, chlorine and fluorine, more preferably chlorine and fluorine.

[0043] Preferably, R 4 is selected from the group consisting of hydrogen, chlorine, cyano and aminothiocarbonyl, more preferably chlorine, cyano and aminothiocarbonyl, and most preferably chlorine.

[0044] Preferably, each R 5 and R 6 is hydrogen, C 1 ~C 4 Alkyl, CO 2 R 9 and C.H. 2 OR 12 , more preferably hydrogen and C 1 ~C 2 Preferably, each is independently selected from the group consisting of alkyl, and most preferably hydrogen.

[0045] Preferably, each R 7 and R 8 is hydrogen, C 1 ~C 4 Alkyl, C 1 ~C 6 Haloalkyl, CO 2 R 9 ,CONR 10 R 11 and C.H. 2 OR 12 More preferably, R 7 CO 2 R 9 ,CONR 10R 11 and C.H. 2 OR 12 and most preferably CO 2 R 9 More preferably, R 8 is hydrogen and C 1 ~C 4 Preferably, the aryl group is selected from the group consisting of alkyl, and most preferably, methyl.

[0046] Preferably, R 9 is hydrogen, C 1 ~C 4 Alkyl, C 1 ~C 4 Haloalkyl, C 1 ~C 2 Alkoxy C 1 ~C 2 Alkyl, Phenyl C 1 ~C 2 Alkyl and 1 to 2 groups R 13 Phenyl C substituted by 1 ~C 2 Alkyl, more preferably hydrogen, C 1 ~C 4 Alkyl, C 1 ~C 2 Alkoxy C 1 ~C 2 Alkyl and Phenyl C 1 ~C 2 Alkyl, most preferably hydrogen, C 1 ~C 4 Alkyl and Phenyl C 1 ~C 2 alkyl.

[0047] Preferably, R 10 is hydrogen and SO 2 R 14 and more preferably selected from the group consisting of SO 2 R 14 It is.

[0048] Preferably, R 11 is hydrogen.

[0049] Preferably, R12 is hydrogen, C 1 ~C 2 Alkyl, C 1 ~C 2 Alkylsulfonyl, C 1 ~C 2 Haloalkylsulfonyl, C 1 ~C 4 Alkylcarbonyl, phenylcarbonyl, 1-2 groups R 13 Phenylcarbonyl, phenylC 1 ~C 2 Alkylcarbonyl and 1-2 groups R 13 Phenyl C substituted by 1 ~C 2 Alkylcarbonyl, more preferably C 1 ~C 2 Alkylsulfonyl, C 1 ~C 2 Haloalkylsulfonyl and C 1 ~C 4 alkylcarbonyl.

[0050] Preferably, R 13 is a 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.

[0051] Preferably, R 14 is C 1 ~C 4 Alkyl and C 1 ~C 4 Alkyl(C 1 ~C 4 More preferably, the aryl group is selected from the group consisting of methyl and isopropyl(methyl)amino.

[0052] A preferred subset of compounds are X is sulfur; Y is CH; R 1 C 1 ~C 2 is alkyl; R 2 C 1 ~C 2 is alkyl; R 3 is selected from the group consisting of hydrogen, chlorine and fluorine; R 4 is selected from the group consisting of chlorine, cyano, and aminothiocarbonyl; Each R 5 and R 6 But hydrogen and C 1 ~C 2 independently selected from the group consisting of alkyl; R 7 But CO 2 R 9 ,CONR 10 R 11 and C.H. 2 OR 12 selected from the group consisting of; R 8 But hydrogen and C 1 ~C 4 selected from the group consisting of alkyl; R 9 But hydrogen, C 1 ~C 4 Alkyl, C 1 ~C 2 Alkoxy C 1 ~C 2 Alkyl and Phenyl C 1 ~C 2 selected from the group consisting of alkyl; R 10 SO 2 R 14 and; R 11 is hydrogen; R 12 But, C 1 ~C 2 Alkylsulfonyl, C 1 ~C 2 Haloalkylsulfonyl and C1 ~C 4 alkylcarbonyl; R 14 is selected from the group consisting of methyl and isopropyl(methyl)amino.

[0053] A more preferred subset of compounds are X is sulfur; Y is CH; R 1 is methyl; R 2 is methyl; R 3 is selected from the group consisting of chlorine and fluorine; R 4 is chlorine; Each R 5 and R 6 is hydrogen; R 7 CO 2 R 9 and; R 8 is methyl; R 9 But hydrogen, C 1 ~C 4 Alkyl and Phenyl C 1 ~C 2 It is selected from the group consisting of alkyl.

[0054] Table of Examples This table is for R 1 and R 2 Specific compounds of formula (I) are disclosed wherein is methyl.

[0055] [Table 1-1] [Table 1-2] [Table 1-3] [Table 1-4] [Table 1-5] [Table 1-6] [Table 1-7] [Table 1-8] [Table 1-9] [Table 1-10]

[0056] 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 X, Y, 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 and R 16 is as defined herein above. 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 conventional techniques, such as chromatography, crystallization, distillation and filtration, prior to use in the next step.

[0057] Compounds of formula (I) can be prepared from compounds of formula (A) and formula (B) as shown in Reaction Scheme 1. Reaction Scheme 1 [ka]

[0058] For example, a mixture of compounds of formula (A) and formula (B) may be treated in a suitable solvent such as toluene with a base such as triethylamine and a carbonyl transfer reagent such as phosgene or carbonyldiimidazole.

[0059] Ureas or thioureas of formula (A) are either available or can be prepared by methods well known in the literature.

[0060] Compounds of formula (B) can be prepared from anilines of formula (C) as shown in Reaction Scheme 2. Reaction Scheme 2 [ka]

[0061] For example, a compound of formula (C) may be treated with a carbonyl transfer reagent, such as diphosgene or triphosgene, in a suitable solvent, such as toluene.

[0062] Anilines of formula (C) can be prepared from nitro compounds of formula (D), as shown in Reaction Scheme 3. Reaction Scheme 3 [ka]

[0063] For example, a 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.

[0064] Nitro compounds of formula (D) can be prepared from oximes of formula (E) and alkenes of formula (F) as shown in Reaction Scheme 4. Reaction Scheme 4 [ka]

[0065] For example, an oxime of formula (E) can be treated with N-chlorosuccinimide in a suitable solvent such as dimethylformamide, and the resulting intermediate is then treated with an alkene of formula (F) in a suitable solvent such as dichloromethane in the presence of a base such as triethylamine.

[0066] Alkenes of formula (F) are either available or can be prepared by methods known in the literature.

[0067] Oximes of formula (E) can be prepared from aldehydes of formula (G) as shown in Reaction Scheme 5. Reaction Scheme 5 [ka]

[0068] For example, an aldehyde of formula (G) may be treated with hydroxylamine hydrochloride in a suitable solvent, such as a mixture of water and ethanol.

[0069] Aldehydes of formula (G) are either available or can be prepared by methods known in the literature.

[0070] R 7 is a carboxylic acid group, the compound of formula (IA) can be prepared by reacting R 7 CO 2 R 9 A compound of formula (I) wherein Reaction Scheme 6 [ka]

[0071] For example, a compound of formula (IB) may be treated with sodium hydroxide in a suitable solvent, such as a mixture of water and ethanol.

[0072] R 7 Compounds of formula (IC), which are compounds of formula (I) where is a hydroxymethyl group, can be prepared from compounds of formula (IA or IB) as shown in Reaction Scheme 7. Reaction Scheme 7 [ka]

[0073] For example, a compound of formula (IA) or (IB) may be treated with a suitable reducing agent, for example a metal hydride reagent such as sodium borohydride or borane, in a suitable solvent such as tetrahydrofuran.

[0074] R 7 CH 2 OR 12 Compounds of formula (ID), which are compounds of formula (I) where: can be prepared from compounds of formula (IC) as shown in Reaction Scheme 8. Reaction Scheme 8 [ka]

[0075] For example, a compound of formula (IC) can be prepared by reacting a reagent R such as an alkylating, acylating or sulfonylating agent with a base such as sodium hydride or triethylamine in a suitable solvent such as tetrahydrofuran. 12 -LG, where LG is a leaving group such as a halogen.

[0076] R 7 CONR 10 R 11 Compounds of formula (I), which are compounds of formula (IE), can be prepared from compounds of formula (IA) as shown in Reaction Scheme 9. Reaction Scheme 9 [ka]

[0077] For example, a compound of formula (IA) may be treated with a halogenating reagent, such as oxalyl chloride, in a suitable solvent, such as dichloromethane, to form an acyl halide, which may be reacted with the reagent HNR 10 R 11 It can be processed with.

[0078] R 7 is an oxime group, the compound of formula (IG) can be prepared by reacting R 7 The compound of formula (I) may be prepared from a compound of formula (IF), wherein is a ketone group. Reaction Scheme 10 [ka]

[0079] For example, a compound of formula (IF) can be prepared by reacting it with hydroxylamine H in a suitable solvent such as ethanol, optionally in the presence of a base such as triethylamine. 2 NOR 16 or a salt thereof.

[0080] R 7 is a hydrazone group, the compound of formula (IH) can be prepared by reacting R 7 The compound of formula (I) may be prepared from a compound of formula (IF), wherein is a ketone group. Reaction Scheme 11 [ka]

[0081] For example, a compound of formula (IF) can be prepared by reacting hydrazine H 2 NN(R 16 ) 2 or a salt thereof.

[0082] Those skilled in the art will appreciate that it is often possible to vary the order in which the transformations described above are carried out or combine them in alternative ways to prepare a wide range of compounds of formula (I). Several steps may also be combined into a single reaction. All such variations are considered to be within the scope of the present invention.

[0083] Those skilled in the art will appreciate that some reagents may be modified with certain values ​​or with the substituents X, Y, Z, R as defined herein. 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 and R 16 and any additional steps, such as protection and / or deprotection steps, that are necessary to achieve the desired transformation will be apparent to one of skill in the art.

[0084] The compounds according to the present invention can be used as herbicides in unmodified form, but are generally formulated into compositions in various ways using formulation auxiliaries such as carriers, solvents and surfactants.The formulations can be in various physical forms, such as dusts, gels, wettable powders, water-dispersible granules, water-dispersible tablets, effervescent pellets, emulsifiable concentrates, microemulsifiable concentrates, oil-in-water emulsions, oil-flowables, aqueous dispersions, oil dispersions, suspoemulsions, capsule suspensions, emulsifiable granules, soluble liquids, water-soluble concentrates (containing water or water-miscible organic solvents as carriers), impregnated polymer films or other forms known, for example, from Manual on Development and Use of FAO and WHO Specifications for Pesticides, United Nations, First Edition, Second Revision (2010).Water-soluble compounds, soluble liquids, water-soluble concentrates or water-soluble granules are preferred.Such formulations can be used directly or can be diluted before use. Dilution can be done, for example, with water, liquid fertilizers, micronutrients, biological organisms, oils or solvents.

[0085] The formulations can be prepared, for example, by mixing the active ingredient with formulation auxiliaries to obtain a composition in the form of a finely divided solid, granules, a solution, a dispersion or an emulsion. The active ingredient can also be formulated with other auxiliaries, such as finely divided solids, mineral oils, oils of vegetable or animal origin, modified oils of vegetable or animal origin, organic solvents, water, surfactants or combinations thereof.

[0086] The active ingredient can also be contained in fine microcapsules. Microcapsules contain the active ingredient in a porous carrier. This allows the active ingredient to be released into the environment in controlled amounts (e.g., sustained release). Microcapsules usually have a diameter of 0.1 to 500 microns. The microcapsules 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 a monolithic solid, in the form of fine particles in a solid or liquid dispersion, or in the form of a suitable solution. The encapsulating membrane can include, for example, natural or synthetic rubber, cellulose, styrene / butadiene copolymer, polyacrylonitrile, polyacrylate, polyester, polyamide, polyurea, polyurethane or chemically modified polymers and starch xanthate or other polymers known to those skilled in the art. Alternatively, fine microcapsules can be formed in which the active ingredient is contained in the form of finely divided particles in a solid matrix of the substrate, but the microcapsules themselves are not encapsulated.

[0087] Formulation auxiliaries suitable for the preparation of the compositions according to the invention are known per se. Liquid carriers include water, toluene, xylene, petroleum ether, vegetable oils, acetone, methyl ethyl ketone, cyclohexanone, acid anhydrides, 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, mesityl oxide, 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 higher alcohols such as amyl alcohol, tetrahydrofurfuryl alcohol, hexanol, octanol, ethylene glycol, propylene glycol, glycerol, N-methyl-2-pyrrolidone, etc. may be used.

[0088] Suitable solid carriers are, for example, talc, titanium dioxide, pyrophyllite clay, silica, attapulgite clay, diatomaceous earth, limestone, calcium carbonate, bentonite, calcium montmorillonite, cottonseed hulls, wheat flour, soybean flour, pumice, wood flour, ground walnut shells, lignin and similar materials.

[0089] Many surface-active substances can be used advantageously in both solid and liquid formulations, especially in formulations which may be diluted with a carrier before use. The surface-active substances can be anionic, cationic, nonionic or polymeric and can be used as emulsifying agents, wetting agents or suspending agents, or for other purposes. Typical surface-active substances include, for example, salts of alkyl sulfates, such as diethanolammonium lauryl sulfate; salts of alkylaryl sulfonic acids, such as calcium dodecylbenzene sulfonate; 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 sulfonic acids, 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 di-alkyl phosphate esters, such as those described in, for example, McCutcheon's Detergents and Emulsifiers Annual, MC Publishing Corp., Ridgewood New York, 1989. Also included are further substances described in Jersey (1981).

[0090] Further auxiliaries which can be used in the agrochemical 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 regulators, lubricants, dispersants, thickeners, antifreeze agents, fungicides and liquid and solid fertilizers.

[0091] The composition according to the invention may contain an additive comprising an oil of vegetable or animal origin, a mineral oil, an alkyl ester of such an oil or a mixture of such oils and oil derivatives. The amount of oil additive in the composition according to the invention is generally 0.01-10% based on the mixture to be applied. For example, the oil additive can be added to the spray tank in the desired concentration after the spray mixture has been prepared. Preferred oil additives include mineral oil or oil of vegetable origin (e.g. rapeseed oil, olive oil or sunflower oil), emulsified vegetable oil, alkyl ester of oil of vegetable origin (e.g. methyl derivatives) or oil of animal origin (e.g. fish oil or beef tallow, etc.). Preferred oil additives are C 8 ~C 22 Alkyl esters of fatty acids, especially C 12 ~C 18 Methyl derivatives of fatty acids, such as the methyl esters of lauric acid, palmitic acid, and oleic acid (methyl laurate, methyl palmitate, and methyl oleate, respectively). Compendium of Herbicide Adjuvants, 10 th A large number of oil derivatives are known from the Journal of Chemical Industry, Vol. 13, No. 1, 2010, Issue 1, Springer-Verlag, 2010.

[0092] The herbicidal compositions generally comprise 0.1 to 99% by weight, in particular 0.1 to 95% by weight, of the compound of formula (I) and 1 to 99.9% by weight of formulation auxiliaries, preferably including 0 to 25% by weight of a surfactant. The compositions of the invention generally comprise 0.1 to 99% by weight, in particular 0.1 to 95% by weight, of the compound of the invention and 1 to 99.9% by weight of formulation auxiliaries, preferably including 0 to 25% by weight of a surfactant. Commercial products may preferably be formulated as concentrates, but end users will usually use dilute formulations.

[0093] Application rates vary within wide limits and depend on the nature of the soil, the method of application, the crop plant, the pests to be controlled, the prevailing climatic conditions and other factors governed by the method of application, the time of application and the target crop. As a general guideline, the compounds may be applied at a rate of 1-2000 l / ha, especially 10-1000 l / ha.

[0094] A preferred formulation may have the following composition (% by weight):

[0095] Emulsifiable concentrate: Active ingredient: 1-95%, preferably 60-90% Surfactant: 1-30%, preferably 5-20% Liquid carrier: 1-80%, preferably 1-35%

[0096] Spraying agent: Active ingredient: 0.1-10%, preferably 0.1-5% Solid carrier: 99.9 to 90%, preferably 99.9 to 99%

[0097] Suspension concentrate: Active ingredient: 5-75%, preferably 10-50% Water: 94-24%, preferably 88-30% Surfactant: 1 to 40%, preferably 2 to 30%

[0098] Wettable powder: Active ingredient: 0.5-90%, preferably 1-80% Surfactant: 0.5 to 20%, preferably 1 to 15% Solid carrier: 5 to 95%, preferably 15 to 90%

[0099] Granules: Active ingredient: 0.1-30%, preferably 0.1-15% Solid carrier: 99.5 to 70%, preferably 97 to 85%

[0100] The composition of the present invention can further comprise at least one additional pesticide.For example, the compound according to the present invention can also be used in combination with other herbicides or plant growth regulators.In a preferred embodiment, the additional pesticide is a herbicide and / or a herbicide safener.

[0101] Thus, the compounds of formula (I) can be used in combination with one or more other herbicides to provide various herbicide mixtures.Specific examples of such mixtures include the following (where "I" represents the compound of formula (I)):-I+acetochlor;I+acifluorfen (including acifluorfen-sodium);I+aclonifen;I+alachlor;I+aloxydim;I+ametryne;I+aminocarbazone;I+amidosulfuron;I+aminocyclopyrachlor;I+aminopyralid;I+amitrole;I+asulam;I+atrazine;I+bensulfuron (including bensulfuron-methyl);I+bentazone;I +Bicyclopyrone;I+Bilanafos;I+Bifenox;I+Bispyribac-sodium;I+Bixlozone;I+Bromacil;I+Bromoxynil;I+Butachlor;I+Butafenacil;I+Cafenstrole;I+Carfentrazone (including carfentrazone-ethyl);Cloransulam (including cloransulam-methyl);I+Chlorimuron (including chlorimuron-ethyl);I+Chlorotoluron;I+Cinosulfuron;I+Chlorsulfuron;I+Cinmethylin;I+Cracifos;I+Clethodim; I+Clodinafop (including clodinafop-propargyl);I+Clomazone;I+Clopyralid;I+Cyclopyranyl;I+Cyclopyrimorate;I+Cyclosulfamuron;I+Cyhalofop (including cyhalofop-butyl);I+2,4-D (including choline salt and its 2-ethylhexyl ester);I+2,4-DB;I+Diamron;I+Desmedipham;I+Dicamba (including its aluminum, aminopropyl, bis-aminopropylmethyl, choline, dichloroprop, diglycolamine, dimethylamine, dimethylammonium, potassium and sodium salts);I+Diclofop-methyl;I+Diclosulam;I+Difluhenican;I+Difenzoquat;I+Difluhenican;I+Diflufenzopyr;I+Dimethachlor;I+Dimethenamid-P;I+Diquat dibromide;I+Diuron;I+Esprocarb;I+Ethalfluralin;I+Ethofumesate;I+Fenoxaprop (including fenoxaprop-P-ethyl);I+Fenoxasulfone;I+Fenquinotrione;I+Fentrazamide;I+Flazasulfuron;I+Florasulam;I+Florpyrauxifen;I+Fluazifop (including fluazifop-p-butyl);I+Flucarbazone (including flucarbazone-sodium);;I+Flufenacet;I+Flumetralin;I+Flumetsulam;I+Flumioxazin;I+Flupyrsulfuron (including flupyrsulfuron-methyl-sodium);;I+Fluroxypyr (including fluroxypyr-meptyl);;I+Fluthiacet-methyl;I+Fomesafen;I+Foramsulfuron;I+Glufosinate (including its anhydride) I+Glyphosate (including its diammonium, isopropylammonium and potassium salts);I+Halosulfuron-methyl;I+Haloxyfop (including haloxyfop-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+Iofen ansulfuron-sodium;I+ioxynil;I+ipfencarbazone;I+isoproturon;I+isoxaben;I+isoxaflutole;I+lactofen;I+lancotrione;I+linuron;I+MCPA;I+MCPB;I+mecoprop-P;I+mefenacet;I+mesosulfuron;I+mesosulfuron-methyl;I+mesotrione;I+metamitron;I+metazachlor;I+methiozoline;I+metobromuron;I+metolachlor;I+methosulam;I+methoxyuron;I+metribuzin;I+methsulfuron; I+Molinate;I+Napropamide;I+Nicosulfuron;I+Norflurazon;I+Orthosulfamuron;I+Oxadiargyl;I+Oxadiazon;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+Prodiamine;I+Prometryn;I+Propachlor;I+Propanil;I+Propaquizafop;I+Propham;I+Propyrisulfuron, I+Propyzamide;I+Prosulfocarb;I+Prosulfuron;I+Pyraclonil;I+Pyraflufen (including pyraflufen-ethyl);I+Pyrasulfotole;I+Pyrazolinate, I+Pyrazosulfuron-ethyl;I+Pyribenzoxime;I+Pyridate;I+Pyriftalid;I+Pyrimisulfan, I+Pyrithiobac-sodium;I+Pyroxasulfone;I+Pyroxsulam;I+Quinclorac;I+Quinmerac;I+Quizalofop (Quizalofop-p-ethyl and Quizalofop (including p-tefuryl);I+rimsulfuron;I+saflufenacil;I+sethoxydim;I+simazine;I+S-metolachlor;I+sulcotrione;I+sulfentrazone;I+sulfosulfuron;I+tebuthiuron;I+tefuryltrione;I+tembotrione;I+terbuthylazine;I+terbutryn;I+thiencarbazone;I+thifensulfuron;I+thiaphenacyl;I+torpyralate;I+topramezone;I+tralkoxydim;I+triafamone;I+trialate;I+trisulfuron; I+Tribenuron (including tribenuron-methyl);I+Triclopyr;I+Trifloxysulfuron (including trifloxysulfuron-sodium);I+Trifludimoxadine;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-Ethyl I+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-t-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]cyclohexane-1,3-dione;I+2-[2-(3,4-dimethoxyphenyl)-6-methyl-3-oxo-pyridazine-4-carbonyl]cyclohexane-1,3-dione phenyl)-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]-5-ethyl-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 ... 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.;

[0102] The mixing partners of the compounds of formula (I) may also be in the form of esters or salts, as mentioned, for example, in The Pesticide Manual, Fourteenth Edition, British Crop Protection Council, 2006.

[0103] The compounds of formula (I) may also be used in mixtures with other agricultural chemicals such as fungicides, nematicides or insecticides (examples of which are given in The Pesticide Manual).

[0104] The mixing ratio of the compound of formula (I) to the mixing partners is preferably 1:100 to 1000:1.

[0105] The mixtures can be advantageously used in the abovementioned formulations (in which case "active ingredient" relates to the respective mixture of the compound of formula (I) with the mixing partner).

[0106] The compound of formula (I) of the present invention can also be combined with herbicide safeners.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+furilazoleI+isoxadifen (including isoxadifen-ethyl);I+mefenpyr (including mefenpyr-diethyl);I+methocamiphen;I+N-(2-methoxybenzoyl)-4-[(methylaminocarbonyl)amino]benzenesulfonamide and I+oxabetrinil.

[0107] Mixtures of 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 especially preferred.

[0108] The safener of the compound of formula (I) is, for example, th Edition (BCPC), 2006. A reference to cloquintocet-mexyl also applies to its lithium, sodium, potassium, calcium, magnesium, aluminum, iron, ammonium, quaternary ammonium, sulfonium or phosphonium salts, and a reference to fenchlorazole-ethyl also applies to fenchlorazole, etc., as disclosed in WO 02 / 34048.

[0109] Preferably, the mixing ratio of the compound of formula (I) to the safener is from 100:1 to 1:10, in particular from 20:1 to 1:1.

[0110] The mixtures may be advantageously used in the formulations described above, where "active ingredient" refers to the respective mixture of compound of formula (I) and safener.

[0111] The compounds of formula (I) of the present invention are useful as herbicides. Thus, the present invention further includes a method for controlling unwanted plants, which comprises applying an effective amount of the compounds of the present invention or a herbicidal composition containing said compounds to said plants or to the habitat containing them. "Control" means killing, reducing or retarding growth, or preventing or reducing germination. Generally, the plants to be controlled are unwanted plants (weeds). "Habitat" means the area where the plants are growing or will grow.

[0112] The application rates of the compounds of formula (I) may vary within a wide range and depend on the nature of the soil, the method of application (pre-emergence; post-emergence; application in the furrow; no-tillage application, etc.), the crop plants, the weeds to be controlled, the prevailing climatic conditions, as well as the application method, time of application and other factors governed by the target crop. The compounds of formula (I) according to the invention are generally applied at a rate of 10 to 2000 g / ha, in particular 50 to 1000 g / ha. A preferred range is 10 to 200 g / ha.

[0113] Application is generally made by spraying the composition, usually with a tractor-mounted sprayer for large areas, although other methods such as dusting (for dusts), dripping or irrigation can also be used.

[0114] Useful plants in which the compositions according to the invention can be used include crops such as cereals, e.g. barley and wheat, cotton, oilseed rape, sunflower, corn, rice, soybeans, sugar beets, sugar cane and turf.

[0115] Crop plants can also include trees such as fruit trees, palm trees, coconut trees or other nuts, as well as vines such as grapes, fruit bushes, fruit plants and vegetables.

[0116] Crops should also be understood to include crops that have been made tolerant to herbicides or classes of herbicides (e.g., ALS-, GS-, EPSPS-, PPO-, ACCase- and HPPD-inhibitors) by conventional breeding methods or genetic engineering. An example of a crop that has been made tolerant to imidazolinones, such as imazamox, by conventional breeding methods is Clearfield® summer rapeseed (canola). Examples of crops that have been made tolerant to herbicides by genetic engineering methods include, for example, glyphosate- and glufosinate-tolerant corn varieties available under the trade names RoundupReady® and LibertyLink®.

[0117] It should also be understood that crops are those that have been made resistant to pests by genetic engineering methods, such as Bt maize (resistant to the European corn borer), Bt cotton (resistant to the cotton weevil) and even Bt potato (resistant to the Colorado potato beetle). An example of Bt maize is the Bt176 maize hybrid from NK® (Syngenta Seeds). Bt toxins are proteins that are naturally formed by the Bacillus thuringiensis soil bacterium. Examples of toxins or transgenic plants capable of synthesizing such toxins are described in EP 451878, EP 374753, WO 93 / 07278, WO 95 / 34656, WO 03 / 052073 and EP 427529. Examples of transgenic plants containing one or more genes encoding insecticide resistance and expressing one or more toxins are KnockOut® (corn), Yield Gard® (corn), NuCOTIN33B® (cotton), Bollgard® (cotton), NewLeaf® (potato), NatureGard® and Protexcta®. Either the plant crop or its seed material can be resistant to herbicides and at the same time resistant to insect ingestion (a "stacked" transgenic event). For example, a seed has the ability to express an insecticidal Cry3 protein and is at the same time resistant to glyphosate.

[0118] It should also be understood that crop plants include those obtained by conventional breeding or genetic engineering methods and contain so-called output traits (e.g. improved storage stability, higher nutritional value and improved flavor).

[0119] Other useful plants include turfgrass grown commercially for turfgrass or lawns, for example, on golf courses, lawns, parks and roadsides, as well as ornamental plants such as flowers or shrubs.

[0120] The compounds and compositions of formula (I) of the present invention can generally be used to control a wide variety of monocotyledonous and dicotyledonous weed species. Examples of monocotyledonous species that can usually be controlled are 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 others. 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 others. persica and Xanthium strumarium.

[0121] The compounds of formula (I) are also useful in pre-harvest drying of crops, such as, but not limited to, potatoes, soybeans, sunflowers and cotton, which are used to dry the leaves of crops to facilitate harvesting without significant damage to the crop itself.

[0122] The compounds / compositions of the present invention are particularly useful in non-selective burn down applications and may therefore also be used to control volunteer vegetation or to ward off crop plants.

[0123] Various aspects and embodiments of the invention will now be described in further detail by way of example. It will be appreciated that modifications of detail may be made without departing from the scope of the invention. EXAMPLES

[0124] The following examples are intended to illustrate, but not limit, the present invention. Yet another aspect of the present invention may be as follows. [1] Formula (I):

change

[10] , selected from the group consisting of: 〔12〕R 11 is hydrogen. 〔13〕R 12 is hydrogen, C 1 ~C 2 Alkyl, C 1 ~C 2 Alkylsulfonyl, C 1 ~C 2 Haloalkylsulfonyl, C 1 ~C 4 Alkylcarbonyl, phenylcarbonyl, 1-2 groups R 13 Phenylcarbonyl, phenylC 1 ~C 2 Alkylcarbonyl and 1-2 groups R 13 Phenyl C substituted by 1 ~C 2 The compound according to any one of the above [1] to

[12] , wherein the compound is selected from the group consisting of alkylcarbonyl. 〔14〕R 13 is a 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 The compound according to any one of the above [1] to

[13] , wherein the compound is selected from the group consisting of alkylsulfonyl. 〔15〕R 14 is C 1 ~C 4 Alkyl and C 1 ~C 4 Alkyl(C 1 ~C 4 The compound according to any one of the above [1] to

[14] , wherein the compound is selected from the group consisting of (alkyl)amino.

[16] An agrochemical composition comprising a herbicidally effective amount of a compound of formula (I) according to any one of [1] to

[15] above, and an agrochemically acceptable diluent or carrier.

[17] A method for controlling or preventing the growth of undesirable plants, comprising applying a herbicidally effective amount of the compound of formula (I) described in any one of [1] to

[15] above or the composition described in

[16] above to a plant, a part thereof or its habitat.

[0125] Synthesis Example Example 1 Synthesis of ethyl 3-[2-chloro-5-(3,5-dimethyl-2,6-dioxo-4-thioxo-1,3,5-triazinan-1-yl)-4-fluoro-phenyl]-5-methyl-4H-isoxazole-5-carboxylate (Compound 47) Step 1. Synthesis of 2-chloro-4-fluoro-5-nitro-benzaldehyde oxime [ka] Hydroxylamine hydrochloride (6.39 g, 92 mmol) was added to a stirred solution of 2-chloro-4-fluoro-5-nitro-benzaldehyde (13 g, 61.3 mmol) in ethanol (65 ml) at room temperature. The resulting solution was stirred at room temperature for a further 60 minutes. Water (125 ml) was added and the resulting mixture was filtered to give 2-chloro-4-fluoro-5-nitro-benzaldehyde oxime as a yellow solid (13.0 g). 1 H NMR (400 MHz, CHCl 3 )δ 8.65(d,1H),8.5(s,1H),8.1(br s,1H),7.4(d,1H)ppm. The following were also prepared by this general method: 2-Chloro-5-nitro-benzaldehyde oxime 1 H NMR (400 MHz, CHCl 3 )δ 8.75(s,1H),8.55(s,1H),8.15(m,1H),7.9(s,1H),7.6(m,1H)ppm. 2,4-Dichloro-5-nitro-benzaldehyde oxime

[0126] Step 2 Synthesis of ethyl 3-(2-chloro-4-fluoro-5-nitro-phenyl)-5-methyl-4H-isoxazole-5-carboxylate [ka] To a stirred solution of 2-chloro-4-fluoro-5-nitro-benzaldehyde oxime (1.2 g, 5.5 mmol) in N,N-dimethylformamide (4.8 ml) at 30° C. was added 1-chloropyrrolidine-2,5-dione (0.6 ml, 6.6 mmol) in portions over 10 minutes. The resulting mixture was stirred at 35° C. for 1 hour, then cooled to room temperature and dichloromethane (50 ml) was added. The mixture was washed with dilute hydrochloric acid (15 ml), dried and cooled to 5° C. To this stirred solution was added a mixture of triethylamine (1.33 ml 9.5 mmol) and ethyl 2-methylprop-2-enoate (1.14 g, 9.5 mmol) in portions. After standing at room temperature for 17 hours, dilute hydrochloric acid (5 ml) was added, the phases were separated, and the organic phase was dried and purified by chromatography to give ethyl 3-(2-chloro-4-fluoro-5-nitro-phenyl)-5-methyl-4H-isoxazole-5-carboxylate (1.0 g). 1 H NMR (400 MHz, CHCl 3 )δ 8.45(d,1H),7.45(d,1H),4.3(q,2H),4.0(d,1H),3.4(d,1H),1.75(s,3H),1.35(t,3H)ppm. The following were also prepared by this general method: Ethyl 3-(2-chloro-5-nitro-phenyl)-5-methyl-4H-isoxazole-5-carboxylate 1 H NMR (400 MHz, CHCl 3 )δ 8.55(d,1H),8.2(d,1H),7.65(d,1H),4.3(q,2H),4.05(d,1H),3.4(d,1H),1.75(s,3H),1.35(t,3H)ppm. Methyl 3-(2-chloro-4-fluoro-5-nitro-phenyl)-5-(trifluoromethyl)-4H-isoxazole-5-carboxylate 1 H NMR (400 MHz, CHCl 3 )δ 8.45(d,1H),7.45(d,1H),4.2(d,1H),3.95(d,1H),3.95(s,3H)ppm. Methyl 3-(2-chloro-4-fluoro-5-nitro-phenyl)-4,5-dimethyl-4H-isoxazole-5-carboxylate 1 H NMR (400 MHz, CHCl 3 )δ 8.3(d,1H),7.45(d,1H),3.9(q,1H),3.8(s,3H),1.75(s,3H),1.1(d,3H)ppm. [3-(2-chloro-4-fluoro-5-nitro-phenyl)-5-methyl-4H-isoxazol-5-yl]methanol 1 H NMR (400 MHz, CHCl 3 )δ 8.45(d,1H),7.45(d,1H),3.8(br d,1H),3.65(d,1H),3.6(br d,1H),3.2(d,1H),2.1(m,1H),1.5(s,3H)ppm. 1-[3-(2-chloro-4-fluoro-5-nitro-phenyl)-5-methyl-4H-isoxazol-5-yl]ethanone 1 H NMR (400 MHz, CHCl 3 )δ 8.4(d,1H),7.45(d,1H),3.95(d,1H),3.2(d,1H),2.35(s,3H),1.65(s,3H)ppm. Ethyl 3-(2,4-dichloro-5-nitro-phenyl)-5-methyl-4H-isoxazole-5-carboxylate 1 H NMR (400 MHz, CHCl 3 )δ 8.35(s,1H),7.7(s,1H),4.3(q,2H),4.05(d,1H),3.4(d,1H),1.75(s,3H),1.35(t,3H)ppm. Methyl 3-(2-chloro-4-fluoro-5-nitro-phenyl)-5-methoxy-4H-isoxazole-5-carboxylate 1 H NMR (400 MHz, CHCl 3)δ 8.55(d,1H),7.45(d,1H),4.0(d,1H),3.9(s,3H),3.6(d,1H),3.5(s,3H)ppm.

[0127] Step 3 Synthesis of ethyl 3-(5-amino-2-chloro-4-fluoro-phenyl)-5-methyl-4H-isoxazole-5-carboxylate [ka] To a stirred solution of ethyl 3-(2-chloro-4-fluoro-5-nitro-phenyl)-5-methyl-4H-isoxazole-5-carboxylate (1.0 g, 3.0 mmol) in ethyl acetate (60 ml) at room temperature was added tin dichloride hydrate (2.3 g, 12.1 mmol). After 5 min the mixture was heated at reflux for 3 h, cooled and evaporated under reduced pressure to give a brown oil which was purified by chromatography to give ethyl 3-(5-amino-2-chloro-4-fluoro-phenyl)-5-methyl-4H-isoxazole-5-carboxylate (800 mg). 1 H NMR (400 MHz, CHCl 3 )δ 7.15(d,1H),7.05(d,1H),4.3(q,2H),3.95(d,1H),3.4(d,1H),1.7(s,3H),1.3(t,3H)ppm(NH 2 was not observed). The following were also prepared by this general method: Ethyl 3-(5-amino-2-chloro-phenyl)-5-methyl-4H-isoxazole-5-carboxylate Methyl 3-(5-amino-2-chloro-4-fluoro-phenyl)-5-(trifluoromethyl)-4H-isoxazole-5-carboxylate 1 H NMR (400 MHz, CHCl 3 )δ 7.15(d,1H),7.1(d,1H),4.2(d,1H),3.95(d,1H),3.9(s,3H),3.85(br s,2H)ppm. Methyl 3-(5-amino-2-chloro-4-fluoro-phenyl)-4,5-dimethyl-4H-isoxazole-5-carboxylate 1 H NMR (400 MHz, CHCl 3 )δ 7.15(d,1H),6.9(d,1H),3.9(q,1H),3.85(br s,2H),3.8(s,3H),1.75(s,3H),1.0(d,3H)ppm. [3-(5-amino-2-chloro-4-fluoro-phenyl)-5-methyl-4H-isoxazol-5-yl]methyl acetate 1-[3-(5-amino-2-chloro-4-fluoro-phenyl)-5-methyl-4H-isoxazol-5-yl]ethanone Ethyl 3-(5-amino-2,4-dichloro-phenyl)-5-methyl-4H-isoxazole-5-carboxylate 1 H NMR (400 MHz, CHCl 3 )δ 7.35(s,1H),7.3(s,1H),4.3(q,2H),4.1(br s,2H),3.95(d,1H),3.4(d,1H),1.75(s,3H),1.35(t,3H)ppm. Methyl 3-(5-amino-2-chloro-4-fluoro-phenyl)-5-methoxy-4H-isoxazole-5-carboxylate 1 H NMR (400 MHz, CHCl 3 )δ 7.15(d,1H),7.1(d,1H),3.95(d,1H),3.9(s,3H),3.85(br s,2H),3.6(d,1H),3.45(s,3H)ppm.

[0128] Step 4 Synthesis of ethyl 3-(2-chloro-4-fluoro-5-isocyanato-phenyl)-5-methyl-4H-isoxazole-5-carboxylate [ka] To stirred diphosgene (0.4 ml, 3.2 mmol) at room temperature was added a solution of ethyl 3-(5-amino-2-chloro-4-fluoro-phenyl)-5-methyl-4H-isoxazole-5-carboxylate (800 mg, 2.66 mmol) in dry toluene (16 ml), then the mixture was heated at reflux for 3 hours, cooled and evaporated under reduced pressure. Toluene (10 ml) was added and the mixture was evaporated under reduced pressure to give ethyl 3-(2-chloro-4-fluoro-5-isocyanato-phenyl)-5-methyl-4H-isoxazole-5-carboxylate as a pale brown liquid (750 mg). 1 H NMR (400 MHz, CHCl 3 )δ 7.45(d,1H),7.25(d,1H),4.3(q,2H),3.9(d,1H),3.35(d,1H),1.75(s,3H),1.35(t,3H)ppm. The following were also prepared by this general method: Ethyl 3-(2-chloro-5-isocyanato-phenyl)-5-methyl-4H-isoxazole-5-carboxylate Methyl 3-(2-chloro-4-fluoro-5-isocyanato-phenyl)-5-(trifluoromethyl)-4H-isoxazole-5-carboxylate 1 H NMR (400 MHz, CHCl 3 )δ 7.45(d,1H),7.3(d,1H),4.15(d,1H),3.95(d,1H),3.95(s,3H)ppm. Methyl 3-(2-chloro-4-fluoro-5-isocyanato-phenyl)-4,5-dimethyl-4H-isoxazole-5-carboxylate 1-[3-(2-chloro-4-fluoro-5-isocyanato-phenyl)-5-methyl-4H-isoxazol-5-yl]methyl acetate 1-[3-(2-chloro-4-fluoro-5-isocyanato-phenyl)-5-methyl-4H-isoxazol-5-yl]ethanone Ethyl 3-(2,4-dichloro-5-isocyanato-phenyl)-5-methyl-4H-isoxazole-5-carboxylate Methyl 3-(2-chloro-4-fluoro-5-isocyanato-phenyl)-5-methoxy-4H-isoxazole-5-carboxylate 1 H NMR (400 MHz, CHCl 3 )δ 7.5(d,1H),7.25(d,1H),3.95(d,1H),3.9(s,3H),3.6(d,1H),3.5(s,3H)ppm.

[0129] Step 5. Preparation of ethyl 3-[2-chloro-5-(3,5-dimethyl-2,6-dioxo-4-thioxo-1,3,5-triazinan-1-yl)-4-fluoro-phenyl]-5-methyl-4H-isoxazole-5-carboxylate (compound 47) [ka] To a stirred solution of ethyl 3-(2-chloro-4-fluoro-5-isocyanato-phenyl)-5-methyl-4H-isoxazole-5-carboxylate (800 mg, 2.45 mmol) in toluene (16 ml) at room temperature was added a solution of 1,3-dimethylthiourea (0.31 g, 2.94 mmol) and triethylamine (0.45 ml, 3.82 mmol) in toluene. The resulting mixture was heated to reflux and carbonyldiimidazole (0.62 g, 3.67 mmol) was added in portions over 15 minutes. The mixture was heated at reflux for 3.5 h, cooled and evaporated under reduced pressure to give a brown oil, which was purified by chromatography to give ethyl 3-[2-chloro-5-(3,5-dimethyl-2,6-dioxo-4-thioxo-1,3,5-triazinan-1-yl)-4-fluoro-phenyl]-5-methyl-4H-isoxazole-5-carboxylate (compound 47) (775 mg). 1 H NMR (400 MHz, CHCl 3)δ 7.75(d,1H),7.35(d,1H),4.25(q,2H),4.0(d,1H),3.75(s,6H),3.4(d,1H),1.7(s,3H),1.3(t,3H)ppm. The individual enantiomers of compound 47 were prepared by chiral chromatography (as described above). 1 1H NMR). The following were also prepared by this general method: Ethyl 3-[2-chloro-5-(3,5-dimethyl-2,6-dioxo-4-thioxo-1,3,5-triazinan-1-yl)phenyl]-5-methyl-4H-isoxazole-5-carboxylate (compound 36) 1 H NMR (400 MHz, CHCl 3 )δ 7.7(d,1H),7.55(d,1H),7.25(m,1H),4.25(q,2H),4.0(d,1H),3.75(s,6H),3.4(d,1H),1.7(s,3H),1.3(t,3H)ppm. Methyl 3-[2-chloro-5-(3,5-dimethyl-2,6-dioxo-4-thioxo-1,3,5-triazinan-1-yl)-4-fluoro-phenyl]-5-trifluoromethyl-4H-isoxazole-5-carboxylate (Compound 262) 1 H NMR (400 MHz, CHCl 3 )δ 7.8(d,1H),7.45(d,1H),4.2(d,1H),4.0(d,1H),3.95(s,3H),3.8(s,6H)ppm. Methyl 3-[2-chloro-5-(3,5-dimethyl-2,6-dioxo-4-thioxo-1,3,5-triazinan-1-yl)-4-fluoro-phenyl]-4,5-dimethyl-4H-isoxazole-5-carboxylate (Compound 145) 1 H NMR (400 MHz, CHCl 3 )δ 7.5(d,1H),7.4(d,1H),3.95(q,1H),3.8(s,3H),3.75(s,6H),1.75(s,3H),1.1(d,3H)ppm. [3-[2-chloro-5-(3,5-dimethyl-2,6-dioxo-4-thioxo-1,3,5-triazinan-1-yl)-4-fluoro-phenyl]-5-methyl-4H-isoxazol-5-yl]methyl acetate (compound 51) 1 H NMR (400 MHz, CHCl 3 )δ 7.75(d,1H),7.35(d,1H),4.2(q,2H),3.75(s,6H),3.5(d,1H),3.25(d,1H),2.1(s,3H),1.5(s,3H)ppm. 3-[5-(5-acetyl-5-methyl-4H-isoxazol-3-yl)-4-chloro-2-fluoro-phenyl]-1,5-dimethyl-6-thioxo-1,3,5-triazinane-2,4-dione (Compound 290) 1 H NMR (400 MHz, CHCl 3 )δ 7.7(d,1H),7.4(d,1H),3.95(d,1H),3.75(s,6H),3.2(d,1H),2.35(s,3H),1.55(s,3H)ppm. Ethyl 3-[2,4-dichloro-5-(3,5-dimethyl-2,6-dioxo-4-thioxo-1,3,5-triazinan-1-yl)phenyl]-5-methyl-4H-isoxazole-5-carboxylate (Compound 58) 1 H NMR (400 MHz, CHCl 3 )δ 7.8(s,1H),7.65(s,1H),4.4(q,2H),4.0(d,1H),3.75(s,6H),3.4(d,1H),1.7(s,3H),1.3(t,3H)ppm. Methyl 3-[2-chloro-5-(3,5-dimethyl-2,6-dioxo-4-thioxo-1,3,5-triazinan-1-yl)-4-fluoro-phenyl]-5-methoxy-4H-isoxazole-5-carboxylate (compound 311) 1 H NMR (400 MHz, CHCl 3)δ 7.8(d,1H),7.4(d,1H),3.95(d,1H),3.9(s,3H),3.8(s,6H),3.6(d,1H),3.45(s,3H)ppm.

[0130] Example 2 Preparation of 3-[2-chloro-5-(3,5-dimethyl-2,6-dioxo-4-thioxo-1,3,5-triazinan-1-yl)-4-fluoro-phenyl]-5-methyl-4H-isoxazole-5-carboxylic acid (compound 45) Step 1. Preparation of 3-[2-chloro-4-fluoro-5-[[methyl(methylcarbamothioyl)carbamoyl]amino]phenyl]-5-methyl-4H-isoxazole-5-carboxylic acid [ka] To a stirred suspension of ethyl 3-[2-chloro-5-(3,5-dimethyl-2,6-dioxo-4-thioxo-1,3,5-triazinan-1-yl)-4-fluoro-phenyl]-5-methyl-4H-isoxazole-5-carboxylate (400 mg, 0.87 mmol) in ethanol (5 ml) at room temperature was added aqueous sodium hydroxide (2N; 0.87 ml, 1.75 mmol). The resulting mixture was stirred for 30 minutes and water (5 ml) was added followed by dilute aqueous hydrochloric acid (2 ml). The mixture was filtered and the solid was dried to give 3-[2-chloro-4-fluoro-5-[[methyl(methylcarbamothioyl)carbamoyl]amino]phenyl]-5-methyl-4H-isoxazole-5-carboxylic acid as a white solid (260 mg). 1 H NMR(400MHz,DMSO)δ 13.3(br s,1H),10.15(s,2H),7.95(d,1H),7.7(d,1H),3.85(d,1H),3.55(s,3H),3.4(d,1H),3.0(s,3H),1.6(s,3H)ppm.

[0131] Step 2. Preparation of 3-[2-chloro-5-(3,5-dimethyl-2,6-dioxo-4-thioxo-1,3,5-triazinan-1-yl)-4-fluoro-phenyl]-5-methyl-4H-isoxazole-5-carboxylic acid (compound 45) [ka] To a stirred solution of 3-[2-chloro-4-fluoro-5-[[methyl(methylcarbamothioyl)carbamoyl]amino]phenyl]-5-methyl-4H-isoxazole-5-carboxylic acid (150 mg, 0.37 mmol) in toluene (3 ml) at room temperature was added triethylamine (0.068 ml, 0.48 mmol) followed by carbonyldi-imidazole (93 mg, 0.56 mmol). The mixture was then heated at reflux for 3 hours, cooled and evaporated under reduced pressure to give a residue which was purified by chromatography to give 3-[2-chloro-5-(3,5-dimethyl-2,6-dioxo-4-thioxo-1,3,5-triazinan-1-yl)-4-fluoro-phenyl]-5-methyl-4H-isoxazole-5-carboxylic acid (compound 45) as a white solid (35 mg). 1 H NMR (400 MHz, CHCl 3 )δ 7.7(d,1H),7.3(d,1H),5.2(br s,1H),3.75(d,1H),3.7(s,6H),3.2(d,1H),1.5(s,3H)ppm.

[0132] Example 3 Preparation of 3-[2,4-dichloro-5-(3,5-dimethyl-2,6-dioxo-4-thioxo-1,3,5-triazinan-1-yl)-phenyl]-5-methyl-4H-isoxazole-5-carboxylic acid (compound 56) [ka] To a stirred solution of ethyl 3-[2,4-dichloro-5-(3,5-dimethyl-2,6-dioxo-4-thioxo-1,3,5-triazinan-1-yl)phenyl]-5-methyl-4H-isoxazole-5-carboxylate (prepared as described in Example 1, step 5; 300 mg, 0.63 mmol) in glacial acetic acid (3 ml) was added concentrated sulfuric acid (0.75 ml, 13 mmol) and the resulting mixture was heated at 100° C. for 1 hour. The mixture was cooled to ambient temperature, poured into water and the resulting mixture was extracted with dichloromethane. The organic extract was dried over magnesium sulfate, filtered, and evaporated under reduced pressure to leave a residue which was purified by chromatography to give 3-[2,4-dichloro-5-(3,5-dimethyl-2,6-dioxo-4-thioxo-1,3,5-triazinan-1-yl)-phenyl]-5-methyl-4H-isoxazole-5-carboxylic acid (compound 56) as an oil (200 mg). 1 H NMR (400 MHz, CHCl 3 )δ 7.75(s,1H),7.65(s,1H),5.75(br s,1H),4.0(d,1H),3.75(s,6H),3.4(d,1H),1.7(s,3H)ppm.

[0133] Example 4 Preparation of [3-(2-chloro-4-fluoro-5-nitro-phenyl)-5-methyl-4H-isoxazol-5-yl]methyl acetate [ka] A mixture of [3-(2-chloro-4-fluoro-5-nitro-phenyl)-5-methyl-4H-isoxazol-5-yl]methanol (prepared as described in Example 1, step 2; 150 mg, 0.52 mmol) and acetic anhydride (60 mg, 0.57 mmol) was heated at 90° C. for 2 h, then allowed to cool and evaporated under reduced pressure to give [3-(2-chloro-4-fluoro-5-nitro-phenyl)-5-methyl-4H-isoxazol-5-yl]methyl acetate as an oil (160 mg). 1 H NMR (400 MHz, CHCl3 )δ 8.45(d,1H),7.45(d,1H),4.3(d,1H),4.15(d,1H),3.5(d,1H),3.25(d,1H),2.1(s,3H),1.5(s,3H)ppm.

[0134] Example 5 Preparation of 3-[4-chloro-2-fluoro-5-[5-(hydroxymethyl)-5-methyl-4H-isoxazol-3-yl]phenyl]-1,5-dimethyl-6-thioxo-1,3,5-triazinane-2,4-dione (Compound 49) [ka] To a stirred solution of [3-[2-chloro-5-(3,5-dimethyl-2,6-dioxo-4-thioxo-1,3,5-triazinan-1-yl)-4-fluoro-phenyl]-5-methyl-4H-isoxazol-5-yl]methyl acetate (prepared as described in Example 1, step 5; 250 mg, 0.55 mmol) in methanol (25 ml) was added saturated aqueous sodium bicarbonate (76 mg, 0.89 mmol). The mixture was stirred at room temperature for 17 hours, concentrated under reduced pressure, and extracted with dichloromethane. The organic extract was dried and evaporated under reduced pressure to leave a residue which was purified by chromatography to give 3-[4-chloro-2-fluoro-5-[5-(hydroxymethyl)-5-methyl-4H-isoxazol-3-yl]phenyl]-1,5-dimethyl-6-thioxo-1,3,5-triazinane-2,4-dione (compound 49) as a glassy solid (138 mg). 1 H NMR (400 MHz, CHCl 3 ) δ 7.75(d,1H), 7.55(d,1H), 3.75(s,6H), 3.65(d,1H), 3.55(d,1H), 3.3(d,1H), 3.2(d,1H), 1.45(s,3H) ppm (no OH observed).

[0135] Example 6 Preparation of [3-[2-chloro-5-(3,5-dimethyl-2,6-dioxo-4-thioxo-1,3,5-triazinan-1-yl)-4-fluoro-phenyl]-5-methyl-4H-isoxazol-5-yl]methyl methanesulfonate (Compound 53) [ka] To a stirred solution of 3-[4-chloro-2-fluoro-5-[5-(hydroxymethyl)-5-methyl-4H-isoxazol-3-yl]phenyl]-1,5-dimethyl-6-thioxo-1,3,5-triazinane-2,4-dione (prepared as described in Example 5; 38 mg, 0.077 mmol) in toluene (3 ml) was added methanesulfonyl chloride (0.1 ml, 1.0 mmol). The resulting solution was stirred at room temperature for 2 hours, evaporated under reduced pressure, and the residue was extracted with dichloromethane. The extract was dried and evaporated under reduced pressure to leave a residue which was purified by chromatography to give [3-[2-chloro-5-(3,5-dimethyl-2,6-dioxo-4-thioxo-1,3,5-triazinan-1-yl)-4-fluoro-phenyl]-5-methyl-4H-isoxazol-5-yl]methyl methanesulfonate (compound 53) as a gum (40 mg). 1 H NMR (400 MHz, CHCl 3 )δ 7.7(d,1H),7.35(d,1H),4.3(q,2H),3.75(s,6H),3.65(d,1H),3.25(d,1H),3.1(s,3H),1.4(s,3H)ppm.

[0136] Example 7 Preparation of 3-[4-chloro-2-fluoro-5-[5-[N-methoxy-C-methyl-carbonimidoyl]-5-methyl-isoxazolidin-3-yl]phenyl]-1,5-dimethyl-6-thioxo-1,3,5-triazinane-2,4-dione (Compound 293) [ka] To a stirred solution of 3-[5-(5-acetyl-5-methyl-4H-isoxazol-3-yl)-4-chloro-2-fluoro-phenyl]-1,5-dimethyl-6-thioxo-1,3,5-triazinane-2,4-dione (prepared as described in Example 1, step 5; 51 mg, 0.12 mmol) in ethanol (2.5 ml) and dichloromethane (2 ml) was added O-methylhydroxylamine hydrochloride (12 mg, 0.14 mmol). The resulting solution was stirred at room temperature for 17 hours, evaporated under reduced pressure, and the residue was partitioned between dichloromethane and water. The phases were separated and the organic phase was dried and evaporated under reduced pressure to leave a residue which was purified by chromatography to give 3-[4-chloro-2-fluoro-5-[5-[N-methoxy-C-methyl-carbonimidoyl]-5-methyl-isoxazolidin-3-yl]phenyl]-1,5-dimethyl-6-thioxo-1,3,5-triazinane-2,4-dione (compound 293) as a fluffy solid (52 mg). 1 H NMR (400 MHz, CHCl 3 )δ 7.7(d,1H),7.35(d,1H),4.1(d,1H),3.85(s,3H),3.8(s,6H),3.2(d,1H),1.95(s,3H),1.6(s,3H)ppm. The following were also prepared by this general method: 3-[4-Chloro-2-fluoro-5-[5-[N-hydroxy-C-methyl-carbonimidoyl]-5-methyl-isoxazolidin-3-yl]phenyl]-1,5-dimethyl-6-thioxo-1,3,5-triazinane-2,4-dione (Compound 296) 1 H NMR (400 MHz, CHCl 3 )δ 7.7(d,1H),7.35(d,1H),5.7(br s,1H),3.9(d,1H),3.75(s,6H),3.3(d,1H),2.0(s,3H),1.65(s,3H)ppm.

[0137] Example 8 Preparation of methyl 2-[1-[3-[2-chloro-5-(3,5-dimethyl-2,6-dioxo-4-thioxo-1,3,5-triazinan-1-yl)-4-fluoro-phenyl]-5-methyl-4H-isoxazol-5-yl]ethylideneamino]oxyacetate (Compound 299) [ka] To a solution of 3-[4-chloro-2-fluoro-5-[5-[N-hydroxy-C-methyl-carbonimidoyl]-5-methyl-isoxazolidin-3-yl]phenyl]-1,5-dimethyl-6-thioxo-1,3,5-triazinane-2,4-dione (prepared as described in Example 7; 40 mg, 0.09 mmol) in 4-methylpentan-2-one (2 ml) was added methyl bromoacetate (0.01 ml, 0.1 mmol), followed by potassium carbonate (12.5 mg, 0.09 mmol) and potassium iodide (catalytic). The resulting mixture was heated in a microwave at 100° C. for 1 h, allowed to cool and the solvent evaporated under reduced pressure to leave a solid which was purified by chromatography to give methyl 2-[1-[3-[2-chloro-5-(3,5-dimethyl-2,6-dioxo-4-thioxo-1,3,5-triazinan-1-yl)-4-fluoro-phenyl]-5-methyl-4H-isoxazol-5-yl]ethylideneamino]oxyacetate (Compound 299) as a gum (20 mg). 1 H NMR (400 MHz, CHCl 3 )δ 7.7(d,1H),7.35(d,1H),4.6(s,2H),4.0(d,1H),3.8(s,6H),3.7(s,3H),3.2(d,1H),2.0(s,3H),1.6(s,3H)ppm.

[0138] Example 9 Preparation of 3-[2-chloro-5-(3,5-dimethyl-2,6-dioxo-4-thioxo-1,3,5-triazinan-1-yl)-4-fluoro-phenyl]-5-methyl-4H-isoxazole-5-carboxamide (Compound 308) Step 1 Preparation of 3-[2-chloro-5-(3,5-dimethyl-2,6-dioxo-4-thioxo-1,3,5-triazinan-1-yl)-4-fluoro-phenyl]-5-methyl-4H-isoxazole-5-carbonyl chloride [ka] To a stirred solution of 3-[2-chloro-5-(3,5-dimethyl-2,6-dioxo-4-thioxo-1,3,5-triazinan-1-yl)-4-fluoro-phenyl]-5-methyl-4H-isoxazole-5-carboxylic acid (prepared as described in Example 3; 42 mg, 0.10 mmol) in dichloromethane (2 ml) at 0° C. was added oxalyl chloride (0.01 ml, 0.11 mmol) followed by dimethylformamide (dropwise). The resulting solution was stirred for 5 minutes and then allowed to warm to ambient temperature and used directly.

[0139] Step 2. Preparation of 3-[2-chloro-5-(3,5-dimethyl-2,6-dioxo-4-thioxo-1,3,5-triazinan-1-yl)-4-fluoro-phenyl]-5-methyl-4H-isoxazole-5-carboxamide (compound 308) [ka] Aqueous concentrated ammonia (0.5 ml, 30 mmol) was added to a stirred solution of 3-[2-chloro-5-(3,5-dimethyl-2,6-dioxo-4-thioxo-1,3,5-triazinan-1-yl)-4-fluoro-phenyl]-5-methyl-4H-isoxazole-5-carbonyl chloride in dichloromethane (2 ml) at 0° C. The resulting solution was stirred for 30 minutes and then evaporated under reduced pressure to leave a white solid which was triturated with water to give 3-[2-chloro-5-(3,5-dimethyl-2,6-dioxo-4-thioxo-1,3,5-triazinan-1-yl)-4-fluoro-phenyl]-5-methyl-4H-isoxazole-5-carboxamide (compound 308) as a white solid (35 mg). 1H NMR (400MHz, d6-DMSO) δ 7.9(m,2H), 7.6(br s,1H), 7.4(br s,1H), 3.8(d,1H), 3.65(s,6H), 1.6(s,3H) ppm (one CH not observed due to water suppression).

[0140] Example 10 Preparation of 3-[2-chloro-5-(3,5-dimethyl-2,6-dioxo-4-thioxo-1,3,5-triazinan-1-yl)-4-fluoro-phenyl]-5-methyl-N-methylsulfonyl-4H-isoxazole-5-carboxamide (Compound 284) Step 1 Preparation of 3-[4-chloro-2-fluoro-5-[5-(imidazole-1-carbonyl)-5-methyl-4H-isoxazol-3-yl]phenyl]-1,5-dimethyl-6-thioxo-1,3,5-triazinane-2,4-dione [ka] To a stirred solution of 3-[2-chloro-5-(3,5-dimethyl-2,6-dioxo-4-thioxo-1,3,5-triazinan-1-yl)-4-fluoro-phenyl]-5-methyl-4H-isoxazole-5-carboxylic acid (prepared as described in Example 3; 400 mg, 0.93 mmol) and triethylamine (0.17 ml, 0.93 mmol) in dichloromethane (5 ml) at ambient temperature was added carbonyldiimidazole (234 mg, 1.4 mmol). The resulting solution was stirred for 45 minutes and then the solvent was evaporated under reduced pressure to give 3-[4-chloro-2-fluoro-5-[5-(imidazole-1-carbonyl)-5-methyl-4H-isoxazol-3-yl]phenyl]-1,5-dimethyl-6-thioxo-1,3,5-triazinan-2,4-dione, which was used directly.

[0141] Step 2. Preparation of 3-[2-chloro-5-(3,5-dimethyl-2,6-dioxo-4-thioxo-1,3,5-triazinan-1-yl)-4-fluoro-phenyl]-5-methyl-N-methylsulfonyl-4H-isoxazole-5-carboxamide (compound 284) [ka] To a stirred solution of 3-[4-chloro-2-fluoro-5-[5-(imidazole-1-carbonyl)-5-methyl-4H-isoxazol-3-yl]phenyl]-1,5-dimethyl-6-thioxo-1,3,5-triazinane-2,4-dione (200 mg, 0.42 mmol) and methanesulfonamide (82 mg, 0.84 mmol) in dichloromethane (5 ml) at ambient temperature was added DBU (0.13 ml, 0.84 mmol). The resulting solution was stirred for 40 hours and then evaporated under reduced pressure to leave a yellow oil, which was purified by chromatography to give 3-[2-chloro-5-(3,5-dimethyl-2,6-dioxo-4-thioxo-1,3,5-triazinan-1-yl)-4-fluoro-phenyl]-5-methyl-N-methylsulfonyl-4H-isoxazole-5-carboxamide (compound 284) as a white solid (52 mg). 1 H NMR (400 MHz, CHCl 3 )δ 9.1(br s,1H),7.7(d,1H),7.4(d,1H),4.0(d,1H),3.75(s,6H),3.45(d,1H),3.3(s,3H),1.75(s,3H)ppm. The following were also prepared by this general method: 3-[2-chloro-5-(3,5-dimethyl-2,6-dioxo-4-thioxo-1,3,5-triazinan-1-yl)-4-fluoro-phenyl]-N-(dimethylsulfamoyl)-5-methyl-4H-isoxazole-5-carboxamide (compound 305) 1 H NMR (400 MHz, CHCl 3 )δ 8.95(br s,1H),7.7(d,1H),7.4(d,1H),4.0(d,1H),3.75(s,6H),3.45(d,1H),2.95(s,6H),1.75(s,3H)ppm.

[0142] Formulation Examples

[0143] Formulation example [Table 2]

[0144] The combination is thoroughly mixed with the adjuvant and the mixture is thoroughly ground in a suitable mill to provide a wettable powder which can be diluted with water to give a suspension of the desired concentration.

[0145] emulsifiable concentrate Active ingredient 10% Octylphenol polyethylene glycol ether 3% (4-5 mol of ethylene oxide) Calcium dodecylbenzenesulfonate 3% Castor oil polyglycol ether (35 mol ethylene oxide) 4% Cyclohexanone 30% Xylene Mixture 50%

[0146] Emulsions of any required dilution that can be used in plant protection can be obtained from this concentrate by dilution with water.

[0147] [Table 3]

[0148] Ready-to-use dusts are obtained by mixing the combination with a carrier and grinding the mixture in a suitable mill.

[0149] Extrusion Granules Active ingredient 15% Sodium Lignosulfonate 2% Carboxymethylcellulose 1% Kaolin 82%

[0150] The combination is mixed with the auxiliaries and ground, the mixture is moistened with water, the mixture is extruded and then dried in a stream of air.

[0151] coated granules Active ingredient: 8% Polyethylene glycol (mol.wt.200) 3% Kaolin 89%

[0152] In a mixer, the finely powdered combination is applied uniformly to the kaolin moistened with polyethylene glycol, which results in a dust-free coated granule.

[0153] Suspension concentrate Active ingredient 40% Propylene glycol 10% Nonylphenol polyethylene glycol ether (15 mol ethylene oxide) 6% Sodium Lignosulfonate 10% Carboxymethylcellulose 1% Silicone oil (in the form of a 75% emulsion in water) 1% water 32%

[0154] The finely ground combination is thoroughly mixed with the adjuvant to give a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water.

[0155] Slow-release capsule suspension 28 parts of the combination are mixed with 2 parts of aromatic solvent and 7 parts of toluene diisocyanate / polymethylene-polyphenylisocyanate-mixture (8:1). The mixture is emulsified in a mixture of 1.2 parts of polyvinyl alcohol, 0.05 parts of defoamer and 51.6 parts of water until the desired particle size is achieved. A mixture of 2.8 parts of 1,6-diaminohexane in 5.3 parts of water is added to the emulsion. The mixture is stirred until the polymerization reaction is complete.

[0156] The resulting capsule suspension is stabilized by adding 0.25 parts of a thickener and 3 parts of a dispersant. The capsule suspension formulation contains 28% active ingredient. The medium capsule diameter is 8-15 microns.

[0157] The resulting formulation is applied to the seeds as an aqueous suspension in a device suitable for the purpose.

[0158] Biological Examples Pre-emergence biological efficacy Weed and / or crop seeds were sown in standard soil in pots. After 1 day of cultivation under controlled conditions in a greenhouse (24 / 16°C, day / night; 14 hours of light; 65% humidity), the plants were sprayed with an aqueous spray solution derived from a formulation of the technical active ingredient in an acetone / water (50:50) solution containing 0.5% Tween 20 (polyoxyethylene sorbitan monolaurate, CAS RN 9005-64-5) to give the desired final dose of the test compound.

[0159] The test plants were then grown under controlled conditions in a greenhouse (24 / 16°C, day / night; 14 hours of light; 65% humidity) and watered twice a day. After 13 days, the tests were evaluated (100 = total damage to the plants; 0 = no damage to the plants). The results are shown in Table 2 below.

[0160] [Table 4]

[0161] Post-germination biological efficacy Weed and / or crop seeds were sown in standard soil in pots. After 8 days of cultivation under controlled conditions in a greenhouse (24 / 16°C, day / night; 14 hours of light; 65% humidity), the plants were sprayed with an aqueous spray solution derived from a formulation of the technical active ingredient in an acetone / water (50:50) solution containing 0.5% Tween 20 (polyoxyethylene sorbitan monolaurate, CAS RN 9005-64-5) to give the desired final dose of the test compound.

[0162] The test plants were then grown under controlled conditions in a greenhouse (24 / 16°C, day / night; 14 hours of light; 65% humidity) and watered twice a day. After 13 days, the tests were evaluated (100 = total damage to the plants; 0 = no damage to the plants). The results are shown in Table 3 below.

[0163] [Table 5]

Claims

1. Formula (I): 【Chemistry 1】 (In the formula, X is selected from the group consisting of oxygen and sulfur; Y is selected from the group consisting of C—H and nitrogen; R 1 is hydrogen and C 1 ~C 6 selected from the group consisting of alkyl; R 2 is hydrogen, amino, 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 and halogen; R 4 is a halogen; Each R 5 and R 6 is hydrogen and C 1 ~C 6 independently selected from the group consisting of alkyl; R 7 is C(=Z)R 15 , CO 2 R 9 , C.O.R. 10 R 11 and C.H. 2 OR 12 selected from the group consisting of: Z is oxygen and NOR 16 selected from the group consisting of: R 8 is selected from the group consisting of hydrogen, C 1 -C 6 alkyl, and C 1 -C 6 haloalkyl; R 9 is hydrogen and C 1 ~C 10 selected from the group consisting of alkyl; R 10 is hydrogen, C 1 ~C 6 Alkyl and SO 2 R 14 selected from the group consisting of: R 11 is hydrogen and C 1 ~C 6 selected from the group consisting of alkyl; R 12 is hydrogen, C 1 ~C 4 Alkyl, and C 1 ~C 4 alkylsulfonyl; R 14 is C 1 ~C 4 Alkyl and C 1 ~C 4 haloalkyl; R 15 is hydrogen and C 1 ~C 4 selected from the group consisting of alkyl; R 16 is hydrogen, C 1 ~C 4 Alkyl, and C 1 ~C 4 Alkoxycarbonyl C 1 ~C 4 alkyl) or an agriculturally acceptable salt thereof.

2. 2. The compound of claim 1, wherein X is sulfur.

3. 3. The compound according to claim 1 or 2, wherein Y is C-H.

4. R 1 is hydrogen and C 1 ~C 4 The compound according to any one of claims 1 to 3, wherein the compound is selected from the group consisting of alkyl.

5. R 2 is hydrogen, C 1 ~C 4 Alkyl and C 3 ~C 4 The compound according to any one of claims 1 to 4, selected from the group consisting of alkynyl.

6. R 3 The compound according to any one of claims 1 to 5, wherein is selected from the group consisting of hydrogen, chlorine and fluorine.

7. R 4 The compound according to any one of claims 1 to 6, wherein is chlorine.

8. Each R 5 and R 6 is hydrogen and C 1 ~C 4 The compound of any one of claims 1 to 7, independently selected from the group consisting of alkyl.

9. R 7 CO 2 R 9 , C.O.R. 10 R 11 and C.H. 2 OR 12 The compound according to any one of claims 1 to 8, selected from the group consisting of:

10. R 9 is hydrogen and C 1 ~C 4 The compound according to any one of claims 1 to 9, wherein the compound is selected from the group consisting of alkyl.

11. R 10 is hydrogen and SO 2 R 14 The compound according to any one of claims 1 to 10, selected from the group consisting of:

12. R 11 The compound according to any one of claims 1 to 11, wherein is hydrogen.

13. R 12 is hydrogen, C 1 ~C 2 Alkyl, and C 1 ~C 2 The compound according to any one of claims 1 to 12, selected from the group consisting of alkylsulfonyl.

14. R 14 is C 1 ~C 4 The compound according to any one of claims 1 to 13, which is alkyl.

15. 15. An agrochemical composition comprising a herbicidally effective amount of a compound of formula (I) as defined in any one of claims 1 to 14 and an agrochemically acceptable diluent or carrier.

16. A method for controlling or preventing the growth of undesirable plants, comprising applying a herbicidally effective amount of a compound of formula (I) as defined in any one of claims 1 to 14 or a composition as defined in claim 15 to the plant, its part or its habitat.

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