Herbicidal compounds

Abstract

Disclosed are compounds of formula (I) wherein the substituents are as defined in claim 1, which are useful as pesticides, in particular as herbicides.

Description

[0001] This invention relates to herbicidal isoxazoline derivatives, and to methods and intermediates for preparing such derivatives. The invention further extends to herbicidal compositions comprising such derivatives, and to the use of such compounds and compositions in crops with beneficial plants for controlling unwanted plant growth: particularly for controlling weeds.

[0002] This invention is based on the discovery that isoxazoline derivatives having formula (I) as defined herein exhibit unexpectedly good herbicidal activity. Therefore, according to the invention, a compound having formula (I) or an agronomically acceptable salt thereof is provided:

[0003] (I)

[0004] in

[0005] A chooses from the following groups: CR 17 and nitrogen;

[0006] B chooses the group consisting of: CR 18 and nitrogen;

[0007] D selects the group consisting of the following: CR 1 Nitrogen and N + -O - ;

[0008] X can be selected from the following groups: CR 19 and nitrogen;

[0009] The premise is that at most two of A, B, D and X are nitrogen, and neither B nor X are nitrogen;

[0010] Y is selected from the following groups: CH and nitrogen;

[0011] R 1Choose from the group consisting of: hydrogen, halogen, cyano, nitro, C1-C4 alkyl, C1-C4 haloalkyl, C3-C6 cycloalkyl, C1-C4 alkoxy, C1-C6 alkyl, C1-C4 haloalkoxy, C1-C4 alkoxy, C1-C4 alkylsulfonyloxy, C1-C4 haloalkylsulfonyloxy, C1-C4 alkylthio, C1-C4 alkylsulfinyl, C1-C 4-alkylsulfonyl, C1-C4 haloalkylthio, C1-C4 haloalkylsulfinyl, C1-C4 haloalkylsulfonyl, amino, C1-C4 alkylamino, di(C1-C4 alkyl)amino, C1-C4 alkylcarbonylamino, C1-C4 alkylcarbonyl(C1-C4 alkyl)amino, C1-C4 alkyloxycarbonylamino, aminocarbonylamino, C1-C4 alkylaminocarbonylamino, C1-C4 alkylsulfonylamino, C1-C4 haloalkylsulfonylamino, CO2R 9 CONR 10 R 11 C(=Z)R 15 ;

[0012] R 2 Choose from the group consisting of: hydrogen, halogen, cyano, nitro, C1-C4 alkyl, C1-C4 haloalkyl, C3-C6 cycloalkyl, C1-C4 alkoxy, C1-C6 alkyl, C1-C4 haloalkoxy, C1-C4 alkoxy, C1-C4 alkylsulfonyloxy, C1-C4 haloalkylsulfonyloxy, C1-C4 alkylthio, C1-C4 alkylsulfinyl, C1-C 4-alkylsulfonyl, C1-C4 haloalkylthio, C1-C4 haloalkylsulfinyl, C1-C4 haloalkylsulfonyl, amino, C1-C4 alkylamino, di(C1-C4 alkyl)amino, C1-C4 alkylcarbonylamino, C1-C4 alkylcarbonyl(C1-C4 alkyl)amino, C1-C4 alkyloxycarbonylamino, aminocarbonylamino, C1-C4 alkylaminocarbonylamino, C1-C4 alkylsulfonylamino, C1-C4 haloalkylsulfonylamino, CO2R 9 CONR 10 R 11 C(=Z)R 15 ;or

[0013] R 1 and R 2 Together with the carbon atoms to which they are attached, they form 5- or 6-membered rings, which may be saturated, partially or fully unsaturated, and may optionally contain one or two heteroatoms selected from the group consisting of nitrogen, oxygen and sulfur, and may be bound by 1-4 R groups. 20Replace; or

[0014] R 2 and R 19 Together with the carbon atoms to which they are attached, they form 5- or 6-membered rings, which may be saturated, partially or fully unsaturated, and may optionally contain one or two heteroatoms selected from the group consisting of nitrogen, oxygen and sulfur, and may be bound by 1-4 R groups. 20 replace;

[0015] R 3 Selected from the group consisting of: hydrogen, halogen, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy and C1-C4 alkylsulfonyl;

[0016] R 4 Select from the group consisting of: hydrogen, halogen, cyano, aminocarbonyl, aminothiocarbonyl, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy and C1-C4 alkylsulfonyl.

[0017] R 5 and R 6 Each is independently selected from the group consisting of: hydrogen, cyano, C1-C6 alkyl, C1-C6 haloalkyl, C1-C4 alkylsulfonyl, CO2R 9 CONR 10 R 11 and CH2OR 12 ;

[0018] R 7 and R 8 Each is independently selected from the group consisting of: hydrogen, cyano, C1-C6 alkyl, C1-C6 haloalkyl, C1-C4 alkoxy, C1-C4 alkylsulfonyl, C(=Z)R 15 CO2R 9 CONR 10 R 11 and CH2OR 12 ;

[0019] Z is selected from the following groups: oxygen, NOR 16 and NN(R) 16 )2;

[0020] R 9 Choose from the following groups: hydrogen, C1-C 10 Alkyl, C1-C 10 Haloalkyl, C3-C6 alkenyl, C3-C6 haloalkenyl, C3-C6 alkynyl, C1-C4 alkoxy-C1-C6 alkyl, C1-C4 haloalkoxy-C1-C6 alkyl, C6-C 10Aryl C1-C3 alkyl, surrounded by 1-4 R groups 13 Replacement C6-C 10 aryl C1-C3 alkyl, heteroaryl C1-C3 alkyl, and those with 1-3 R groups 13 Substituted heteroaryl C1-C3 alkyl groups;

[0021] R 10 Choose from the following groups: hydrogen, C1-C6 alkyl groups, and SO2R. 14 ;

[0022] R 11 Choose from the group consisting of: hydrogen and C1-C6 alkyl groups; or

[0023] R 10 and R 11 Together with the nitrogen atoms attached to them, they form 3- to 6-membered heterocyclic rings, which optionally contain oxygen atoms;

[0024] R 12 Choose from the group consisting of: hydrogen, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkylsulfonyl, C1-C4 haloalkylsulfonyl, phenylsulfonyl, and those with 1-2 R groups. 13 Substituted phenylsulfonyl; C1-C4 alkyl carbonyl, C1-C4 haloalkyl carbonyl, C6-C 10 aryl carbonyl group, surrounded by 1-4 R groups 13 Replacement C6-C 10 aryl carbonyl, heteroaryl carbonyl, with 1-3 R groups 13 Substituted heteroaryl carbonyl, C6-C 10 Aryl C1-C3 alkyl carbonyl, surrounded by 1-4 R groups 13 Replacement C6-C 10 aryl C1-C3 alkyl carbonyl, heteroaryl C1-C3 alkyl carbonyl, and those with 1-3 R groups 13 Substituted heteroaryl C1-C3 alkyl carbonyl;

[0025] Each R 13 Independently selected from the group consisting of: halogen, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, cyano, and C1-C4 alkylsulfonyl; R 14 Selected from the group consisting of: C1-C4 alkyl, C1-C4 haloalkyl, and C1-C4 alkyl(C1-C4 alkyl)amino; R 15 Choose from the group consisting of: hydrogen, C1-C4 alkyl, and C1-C4 haloalkyl; each R 16Independently selected from the group consisting of: hydrogen, C1-C4 alkyl, C1-C4 haloalkyl and C1-C4 alkoxycarbonyl C1-C4 alkyl;

[0026] R 17 Choose from the group consisting of: hydrogen, halogen, cyano, nitro, C1-C4 alkyl, C1-C4 haloalkyl, C3-C6 cycloalkyl, C1-C4 alkoxy, C1-C6 alkyl, C1-C4 haloalkoxy, C1-C4 alkoxy, C1-C4 alkylsulfonyloxy, C1-C4 haloalkylsulfonyloxy, C1-C4 alkylthio, C1-C4 alkylsulfinyl, C1-C 4-alkylsulfonyl, C1-C4 haloalkylthio, C1-C4 haloalkylsulfinyl, C1-C4 haloalkylsulfonyl, amino, C1-C4 alkylamino, di(C1-C4 alkyl)amino, C1-C4 alkylcarbonylamino, C1-C4 alkylcarbonyl(C1-C4 alkyl)amino, C1-C4 alkyloxycarbonylamino, aminocarbonylamino, C1-C4 alkylaminocarbonylamino, C1-C4 alkylsulfonylamino, C1-C4 haloalkylsulfonylamino, CO2R 9 CONR 10 R 11 C(=Z)R 15 ;

[0027] R 18 Choose from the group consisting of: hydrogen, halogen, cyano, nitro, C1-C4 alkyl, C1-C4 haloalkyl, C3-C6 cycloalkyl, C1-C4 alkoxy, C1-C6 alkyl, C1-C4 haloalkoxy, C1-C4 alkoxy, C1-C4 alkylsulfonyloxy, C1-C4 haloalkylsulfonyloxy, C1-C4 alkylthio, C1-C4 alkylsulfinyl, C1-C 4-alkylsulfonyl, C1-C4 haloalkylthio, C1-C4 haloalkylsulfinyl, C1-C4 haloalkylsulfonyl, amino, C1-C4 alkylamino, di(C1-C4 alkyl)amino, C1-C4 alkylcarbonylamino, C1-C4 alkylcarbonyl(C1-C4 alkyl)amino, C1-C4 alkyloxycarbonylamino, aminocarbonylamino, C1-C4 alkylaminocarbonylamino, C1-C4 alkylsulfonylamino, C1-C4 haloalkylsulfonylamino, CO2R 9 CONR 10 R 11 C(=Z)R 15 ;

[0028] R 19Choose from the group consisting of: hydrogen, halogen, cyano, nitro, C1-C4 alkyl, C1-C4 haloalkyl, C3-C6 cycloalkyl, C1-C4 alkoxy, C1-C6 alkyl, C1-C4 haloalkoxy, C1-C4 alkoxy, C1-C4 alkylsulfonyloxy, C1-C4 haloalkylsulfonyloxy, C1-C4 alkylthio, C1-C4 alkylsulfinyl, C1-C 4-alkylsulfonyl, C1-C4 haloalkylthio, C1-C4 haloalkylsulfinyl, C1-C4 haloalkylsulfonyl, amino, C1-C4 alkylamino, di(C1-C4 alkyl)amino, C1-C4 alkylcarbonylamino, C1-C4 alkylcarbonyl(C1-C4 alkyl)amino, C1-C4 alkyloxycarbonylamino, aminocarbonylamino, C1-C4 alkylaminocarbonylamino, C1-C4 alkylsulfonylamino, C1-C4 haloalkylsulfonylamino, CO2R 9 CONR 10 R 11 C(=Z)R 15 ;R 20 Selected from the group consisting of: halogen, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, cyano, and C1-C4 alkylsulfonyl; and

[0029] The premise is that R1, R2, R17, R18, and R19 are not all hydrogen.

[0030] According to a second aspect of the invention, an agricultural chemical composition is provided comprising a herbicidally effective amount of a compound having formula (I) and an agriculturally chemically acceptable diluent or carrier. This agricultural composition may further comprise at least one additional active ingredient.

[0031] According to a third aspect of the invention, a method for controlling or preventing unwanted plant growth is provided, wherein a herbicidal effective amount of a compound having formula (I) or a composition containing such compound as an active ingredient is applied to said plant, its parts or the site thereof.

[0032] According to a fourth aspect of the invention, the use of a compound having formula (I) as a herbicide is provided.

[0033] According to a fifth aspect of the present invention, a method for preparing a compound having formula (I) is provided.

[0034] As used herein, the term "halogen" refers to fluorine (fluoro), chlorine (chloro), bromine (bromo), or iodine (iodo), preferably fluorine, chlorine, or bromine.

[0035] As used in this article, cyano refers to the -CN group.

[0036] As used in this article, hydroxyl refers to the -OH group.

[0037] As used in this article, nitro means -NO2 group.

[0038] As used herein, the term "C1-C6 alkyl" refers to a straight-chain or branched hydrocarbon chain group consisting only of carbon and hydrogen atoms, which is unsaturated, has one to six carbon atoms, and is attached to the rest of the molecule by single bonds. C1-C4 alkyl and C1-C2 alkyl should be interpreted accordingly. Examples of C1-C6 alkyl include, but are not limited to, methyl (Me), ethyl (Et), n-propyl, 1-methylethyl (isopropyl), n-butyl, and 1-dimethylethyl (tert-butyl).

[0039] As used herein, the term "C1-C6 alkoxy" refers to an alkoxy group having the formula -OR a The group, wherein R a It is C as generally defined above. 1- C6 alkyl group. C1-C4 alkoxy groups should be interpreted accordingly. 1-4 Examples of alkoxy groups include, but are not limited to, methoxy, ethoxy, propoxy, isopropoxy, and tert-butoxy.

[0040] As used herein, the term "C1-C6 haloalkyl" refers to a C1-C6 alkyl group as generally defined above, which is substituted with one or more identical or different halogen atoms. C1-C4 haloalkyl should be interpreted accordingly. Examples of C1-C6 haloalkyl include, but are not limited to, chloromethyl, fluoromethyl, fluoroethyl, difluoromethyl, trifluoromethyl, and 2,2,2-trifluoroethyl.

[0041] As used herein, the term "C2-C6 alkenyl" refers to a straight-chain or branched hydrocarbon chain group consisting only of carbon and hydrogen atoms, containing at least one double bond that can have an (E)- or (Z)- configuration, having two to six carbon atoms attached to the rest of the molecule by single bonds. C2-C4 alkenyl should be interpreted accordingly. 2- Examples of C6-alkenyl groups include, but are not limited to, prop-1-alkenyl, allyl (prop-2-alkenyl), and but-1-alkenyl.

[0042] As used herein, the term "C2-C6 haloalkenyl" refers to a C2-C6 haloalkenyl group substituted with one or more of the same or different halogen atoms as generally defined above. 2- C6 alkenyl groups. Examples of C2-C6 haloalkenyl groups include, but are not limited to, vinyl chloride, vinyl fluoride, 1,1-difluoroethylene, 1,1-dichloroethylene, and 1,1,2-trichloroethylene.

[0043] As used herein, the term "C2-C6 ynyl" refers to a straight-chain or branched hydrocarbon chain group consisting only of carbon and hydrogen atoms, containing at least one triple bond, having two to six carbon atoms, and attached to the rest of the molecule by single bonds. C2-C4 ynyl should be interpreted accordingly. Examples of C2-C6 ynyl groups include, but are not limited to, propynyl-1-ynyl, propynyl (propynyl-2-ynyl), and butynyl-1-ynyl.

[0044] As used herein, the term "C1-C6 haloalkoxy" refers to a C1-C6 alkoxy group as defined above, which is substituted with one or more of the same or different halogen atoms. C1-C4 haloalkoxy groups should be interpreted accordingly. Examples of C1-C6 haloalkoxy groups include, but are not limited to, fluoromethoxy, difluoromethoxy, fluoroethoxy, trifluoromethoxy, and trifluoroethoxy.

[0045] As used herein, the term "C1-C3 haloalkoxyC1-C3 alkyl" refers to a C1-C3 alkyl group having the formula R b -OR a - groups, where R b It is a C1-C3 haloalkyl group as generally defined above, and R a It is a C1-C3 alkylene group as generally defined above.

[0046] As used herein, the term "C1-C3 alkoxy-C1-C3 alkyl" refers to a compound having the formula R b -OR a - groups, where R b It is a C1-C3 alkyl group as generally defined above, and R a It is a C1-C3 alkylene group as generally defined above.

[0047] As used herein, the term "C1-C3 alkoxy" refers to a compound with the formula R b -OR a -O- groups, where R b It is a C1-C3 alkyl group as generally defined above, and R a It is a C1-C3 alkylene group as generally defined above.

[0048] As used herein, the term "C3-C6 alkenyloxy group" refers to a group having the formula -OR aThe group, wherein R a It is C as generally defined above. 3- C6 alkenyl group.

[0049] As used herein, the term "C3-C6 alkynyloxy group" refers to a group having the formula -OR a The group, wherein R a It is C as generally defined above. 3- C6 ynyl group.

[0050] As used herein, the term "hydroxy C1-C6 alkyl" refers to a C1-C6 alkyl group as generally defined above, which is substituted with one or more hydroxyl groups.

[0051] As used herein, the term "C1-C6 alkyl carbonyl" refers to an alkyl group having the formula -C(O)R a The group, wherein R a It is a C1-C6 alkyl group as generally defined above.

[0052] As used herein, the term "C1-C6 alkoxycarbonyl" refers to an alkoxycarbonyl group having the formula -C(O)OR a The group, wherein R a It is a C1-C6 alkyl group as generally defined above.

[0053] As used herein, the term "aminocarbonyl" refers to a group having the formula -C(O)NH2.

[0054] As used herein, the term "aminothiocarbonyl" refers to a group having the formula -C(S)NH2.

[0055] As used herein, the term "C3-C6 cycloalkyl" refers to a stable monocyclic group that is saturated or partially unsaturated and contains 3 to 6 carbon atoms. C3-C4 cycloalkyl should be interpreted accordingly. Examples of C3-C6 cycloalkyl groups include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl.

[0056] As used herein, the term "C3-C6 halocycloalkyl" refers to a C3-C6 cycloalkyl group as generally defined above, which is substituted with one or more of the same or different halogen atoms. C3-C4 halocycloalkyl should be interpreted accordingly.

[0057] As used herein, the term "C3-C6 cycloalkoxy" refers to a compound with the formula -OR a The group, wherein R a It is a C3-C6 cycloalkyl group as generally defined above.

[0058] As used in this article, the term "NC" 3- "C6 cycloalkylamino" refers to a compound with the formula -NHR a The group, wherein Ra It is C as generally defined above. 3- C6 cycloalkyl group.

[0059] As used herein, unless otherwise expressly stated, the term "heteroaryl" refers to a 5- or 6-membered monocyclic aromatic ring comprising 1, 2, 3, or 4 heteroatoms individually selected from nitrogen, oxygen, and sulfur. The heteroaryl group may be bonded to the remainder of the molecule via carbon atoms or heteroatoms. Examples of heteroaryl groups include furanyl, pyrroleyl, imidazolyl, thiopheneyl, pyrazolyl, thiazolyl, isothiazolyl, oxazolyl, isoxazolyl, triazolyl, tetrazolyl, pyrazinyl, pyridazinyl, pyrimidinyl, or pyridinyl.

[0060] As used herein, unless otherwise expressly stated, the term "heterocyclic group" or "heterocyclic" refers to a stable 4- to 6-membered non-aromatic monocyclic group comprising one, two, or three heteroatoms individually selected from nitrogen, oxygen, and sulfur. The heterocyclic group may be bonded to the remainder of the molecule via carbon atoms or heteroatoms. Examples of heterocyclic groups include, but are not limited to, pyrrolinyl, pyrrolylalkyl, tetrahydrofuranyl, tetrahydrothiophenyl, tetrahydrothioranyl, piperidinyl, piperazineyl, tetrahydropyranyl, dihydroisoxazolyl, dioxopentyl, morpholinyl, or δ-lactamyl.

[0061] The presence of one or more possible asymmetric carbon atoms in compounds having formula (I) means that these compounds can exist in chiral isomers (i.e., enantiomers or diastereomers). As a result of restricted rotation around the single bond, trans-isomers may also exist. Formula (I) is intended to include all those possible isomers and mixtures thereof. This invention includes all those possible isomers and mixtures thereof of compounds having formula (I). Similarly, Formula (I) is intended to include all possible tautomers (including lactam-lactamimide tautomers and keto-enol tautomers) (when present). This invention includes all possible tautomers of compounds having formula (I). Similarly, in the presence of disubstituted alkenes, these can exist in E or Z form or as a mixture of both in any proportion. This invention includes all these possible isomers and mixtures thereof of compounds having formula (I).

[0062] Compounds having formula (I) are generally provided in the form of agronomically acceptable salts, zwitterions, or agronomically acceptable zwitterionic salts. This invention covers all such agronomically acceptable salts, zwitterions, and mixtures thereof in all proportions.

[0063] Suitable agronomically 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, pentanylamine, arginine, phenethylbenzylamine, benzathine penicillin, butenyl-2-amine, butylamine, butylethanolamine, cyclohexylamine, decylamine, dipentylamine, dibutylamine, diethanolamine, diethylamine, diethylenetriamine, diheptylamine, dihexylamine, diisopentylamine, diisopropylamine, dimethylamine, dioctylamine, dipropanolamine, diacetylacetylamine, dipropylamine, dodecylamine, ethanolamine, ethylamine, ethylbutylamine, ethylenediamine, ethylheptylamine, ethyloctylamine, ethylpropanolamine, heptadecanolamine, heptylamine, hexadecyl-2-amine, hexylamine, hexylheptylamine, hexyloctylamine, histidine, indoline, isopentylamine, isobutanolamine, isobutylamine, isopropanolamine, and isopropylamine. Lysine, meglumine, methoxyethylamine, methylamine, methylbutylamine, methylethylamine, methylhexylamine, methylisopropylamine, methylnonamine, methyloctadecylamine, methylpentadecanamine, morpholine, N,N-diethylethanolamine, N-methylpiperazine, nonamine, octadecylamine, octylamine, oleylamine, pentadecylamine, pentenyl-2-amine, phenoxyethylamine, methylpyridine, piperazine, piperidine, propanolamine, propylamine, propylenediamine, pyridine, pyrrolidine, sec-butylamine, stearamide, tallowamine, tetradecylamine, tributylamine, tridecylamine, trimethylamine, triheptylamine, trihexylamine, triisobutylamine, triisodecylamine, triisopropylamine, trimethylamine, tripentylamine, tripropylamine, tri(hydroxymethyl)aminomethane, and undecylamine. Examples of suitable organic cations include benzyltributylammonium, benzyltrimethylammonium, benzyltriphenylphosphonium, choline, tetrabutylammonium, tetrabutylphosphonium, tetraethylammonium, tetraethylphosphonium, tetramethylammonium, tetramethylphosphonium, tetrapropylammonium, tetrapropylphosphonium, tributylsulfonium, tributylsulfonium oxide, triethylsulfonium, triethylsulfonium oxide, trimethylsulfonium, trimethylsulfonium oxide, tripropylsulfonium, and tripropylsulfonium oxide.

[0064] The following list provides the substituents A, B, D, X, Y, Z, R for compounds having 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 R 16 R 17 R 18 R 19 and R20 The definitions, including preferred definitions, are provided below. For any of these substituents, any definition given below may be combined with any other definition of any substituent given below or elsewhere in this document.

[0065] Preferably, A is selected from the group consisting of: CR 17 And nitrogen, more preferably nitrogen;

[0066] Preferably, B is selected from the group consisting of: CR 18 And nitrogen, more preferably CR 18 ;

[0067] Preferably, D is selected from the group consisting of: CR 1 and N + -O - CR is preferred 1 ;

[0068] Preferably, X is selected from the group consisting of: CR 19 And nitrogen, more preferably CR 19 ;

[0069] The preferred premise is that at most one of A, B and X is nitrogen, the more preferred premise is that one of A, B and X is nitrogen, and even more preferred premise is that one of A, B, D and X is nitrogen;

[0070] Preferably, Y is CH.

[0071] Preferably, R 1 The group consisting of hydrogen, halogen, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, more preferably hydrogen, fluorine, chlorine, C1-C2 alkyl, C1-C2 haloalkyl, and most preferably hydrogen, fluorine, chlorine, methyl and trifluoromethyl.

[0072] Preferably, R 2 The group consisting of the following is preferred: hydrogen, halogen, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, more preferably hydrogen, fluorine, chlorine, C1-C2 alkyl, C1-C2 haloalkyl, and most preferably hydrogen, fluorine, chlorine, methyl, and trifluoromethyl; or

[0073] Preferably, R 2 and R 19 Together with the carbon atoms to which they are attached, they form a 5-membered saturated ring, which optionally contains one or two oxygen atoms and can be bonded by one or two R groups. 20 replace.

[0074] Preferably, R 3Choose from the group consisting of: hydrogen, chlorine and fluorine, more preferably chlorine and fluorine.

[0075] Preferably, R 4 The group consisting of hydrogen, chlorine, cyano and aminothiocarbonyl is selected, more preferably chlorine, cyano and aminothiocarbonyl, and most preferably chlorine.

[0076] Preferably, R 5 and R 6 Each is independently selected from the following groups: hydrogen, C1-C4 alkyl, CO2R 9 and CH2OR 12 More preferably hydrogen and C1-C2 alkyl, with hydrogen being the most preferred.

[0077] Preferably, R 7 and R 8 Each is independently selected from the following groups: hydrogen, C1-C4 alkyl, C1-C6 haloalkyl, CO2R 9 CONR 10 R 11 and CH2OR 12 More preferably, R 7 Choose from the following groups: CO2R 9 CONR 10 R 11 and CH2OR 12 CO2R is the best choice 9 More preferably, R 8 Choose from the group consisting of hydrogen and C1-C4 alkyl groups, with methyl being the most preferred.

[0078] Preferably, R 9 Choose from the group consisting of: hydrogen, C1-C4 alkyl, C1-C4 haloalkyl, C1-C2 alkoxy-C1-C2 alkyl, phenyl-C1-C2 alkyl, and those with 1-2 R groups. 13 The substituted phenyl C1-C2 alkyl group is preferred, more preferably hydrogen, C1-C4 alkyl, C1-C2 alkoxy C1-C2 alkyl and phenyl C1-C2 alkyl, and most preferably hydrogen, C1-C4 alkyl and phenyl C1-C2 alkyl.

[0079] Preferably, R 10 Choose from the following groups: hydrogen and SO2R 14 SO2R is preferred. 14 .

[0080] Preferably, R 11 It is hydrogen.

[0081] Preferably, R 12Choose from the group consisting of: hydrogen, C1-C2 alkyl, C1-C2 alkylsulfonyl, C1-C2 haloalkylsulfonyl, C1-C4 alkylcarbonyl, phenylcarbonyl, and those with 1-2 R groups. 13 Substituted phenyl carbonyl, phenyl C1-C2 alkyl carbonyl, and those with 1-2 R groups 13 The substituted phenyl C1-C2 alkyl carbonyl group, more preferably C1-C2 alkyl sulfonyl group, C1-C2 haloalkyl sulfonyl group and C1-C4 alkyl carbonyl group.

[0082] Preferably, R 13 Selected from the group consisting of: halogen, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, cyano, and C1-C4 alkylsulfonyl.

[0083] Preferably, R 14 The group consisting of C1-C4 alkyl and C1-C4 alkyl (C1-C4 alkyl)amino, more preferably methyl and isopropyl (methyl)amino.

[0084] Preferably, R 17 The group consisting of hydrogen, halogen, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, more preferably hydrogen, fluorine, chlorine, C1-C2 alkyl, C1-C2 haloalkyl, and most preferably hydrogen, fluorine, chlorine, methyl and trifluoromethyl.

[0085] Preferably, R 18 The group consisting of hydrogen, halogen, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, more preferably hydrogen, fluorine, chlorine, C1-C2 alkyl, C1-C2 haloalkyl, and most preferably hydrogen, fluorine, chlorine, methyl and trifluoromethyl.

[0086] Preferably, R 19 The group consisting of hydrogen, halogen, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, more preferably hydrogen, fluorine, chlorine, C1-C2 alkyl, C1-C2 haloalkyl, and most preferably hydrogen, fluorine, chlorine, methyl and trifluoromethyl.

[0087] Preferably, R 20 It is a halogen, and fluorine is a better choice.

[0088] In embodiments where two of A, B, D, and X are nitrogen, B is preferably nitrogen. In embodiments where one of A, B, D, and X is nitrogen, A is preferably nitrogen. A first preferred compound of a subgroup is a compound in which...

[0089] A is nitrogen;

[0090] B is CR 18 ;

[0091] D is CR 1 ;

[0092] X is CR 19 ;

[0093] Y is CH;

[0094] R 1 Select from the group consisting of: hydrogen, fluorine, chlorine, C1-C2 alkyl and C1-C2 haloalkyl;

[0095] R 2 Select from the group consisting of: hydrogen, fluorine, chlorine, C1-C2 alkyl and C1-C2 haloalkyl;

[0096] R 3 Choose from the following groups: hydrogen, chlorine, and fluorine;

[0097] R 4 Choose from the following groups: chlorine, cyano, and aminothiocarbonyl;

[0098] R 5 and R 6 Each is independently selected from the group consisting of: hydrogen and C1-C2 alkyl groups;

[0099] R 7 Choose from the following groups: CO2R 9 CONR 10 R 11 and CH2OR 12 ;

[0100] R 8 Choose from the group consisting of: hydrogen and C1-C4 alkyl groups;

[0101] R 9 Selected from the group consisting of: hydrogen, C1-C4 alkyl, C1-C2 alkoxy-C1-C2 alkyl, and phenyl-C1-C2 alkyl;

[0102] R 10 It is SO2R 14 ;

[0103] R 11 It is hydrogen.

[0104] R 12 Choose from the group consisting of: C1-C2 alkylsulfonyl, C1-C2 haloalkylsulfonyl, and C1-C4 alkylcarbonyl;

[0105] R 14Choose from the group consisting of: methyl and isopropyl (methyl)amino;

[0106] R 18 Select from the group consisting of: hydrogen, fluorine, chlorine, C1-C2 alkyl and C1-C2 haloalkyl;

[0107] R 19 Choose from the group consisting of: hydrogen, fluorine, chlorine, C1-C2 alkyl and C1-C2 haloalkyl.

[0108] The first preferred compound of a subgroup is the following compound, in which...

[0109] A is nitrogen;

[0110] B is CR 18 ;

[0111] D is CR 1 ;

[0112] X is CR 19 ;

[0113] Y is CH;

[0114] R 1 Choose from the following groups: hydrogen, fluorine, chlorine, methyl, and trifluoromethyl;

[0115] R 2 Choose from the following groups: hydrogen, fluorine, chlorine, methyl, and trifluoromethyl;

[0116] R 3 Choose the group consisting of: chlorine and fluorine;

[0117] R 4 It is chlorine;

[0118] R 5 and R 6 Each is hydrogen;

[0119] R 7 It is CO2R 9 ;

[0120] R 8 It is methyl;

[0121] R 9 Choose from the group consisting of: hydrogen, C1-C4 alkyl, and phenyl-C1-C2 alkyl;

[0122] R 18 Choose from the following groups: hydrogen, fluorine, chlorine, methyl, and trifluoromethyl;

[0123] R 19Choose from the following groups: hydrogen, fluorine, chlorine, methyl, and trifluoromethyl.

[0124] A second preferred compound of a subgroup is the following compound, in which...

[0125] A is CR 17 ;

[0126] B is nitrogen;

[0127] D is CR 1 ;

[0128] X is CR 19 ;

[0129] Y is CH;

[0130] R 1 Select from the group consisting of: hydrogen, fluorine, chlorine, C1-C2 alkyl and C1-C2 haloalkyl;

[0131] R 2 and R 19 Together with the carbon atoms to which they are attached, they form 5- or 6-membered rings containing one or two heteroatoms selected from the group consisting of nitrogen, oxygen, and sulfur, and bound by 1-4 R groups. 20 replace;

[0132] R 3 Choose from the following groups: hydrogen, chlorine, and fluorine;

[0133] R 4 Choose from the following groups: chlorine, cyano, and aminothiocarbonyl;

[0134] R 5 and R 6 Each is independently selected from the group consisting of: hydrogen and C1-C2 alkyl groups;

[0135] R 7 Choose from the following groups: CO2R 9 CONR 10 R 11 and CH2OR 12 ;

[0136] R 8 Choose from the group consisting of: hydrogen and C1-C4 alkyl groups;

[0137] R 9 Selected from the group consisting of: hydrogen, C1-C4 alkyl, C1-C2 alkoxy-C1-C2 alkyl, and phenyl-C1-C2 alkyl;

[0138] R 10 It is SO2R 14 ;

[0139] R 11 It is hydrogen.

[0140] R 12 Choose from the group consisting of: C1-C2 alkylsulfonyl, C1-C2 haloalkylsulfonyl, and C1-C4 alkylcarbonyl;

[0141] R 14 Choose from the group consisting of: methyl and isopropyl (methyl)amino;

[0142] R 18 Select from the group consisting of: hydrogen, fluorine, chlorine, C1-C2 alkyl and C1-C2 haloalkyl;

[0143] R 20 Selected from the group consisting of: halogen, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, cyano, and C1-C4 alkylsulfonyl.

[0144] A second preferred compound of a subgroup is the following compound, in which...

[0145] A is CR 17 ;

[0146] B is nitrogen;

[0147] D is CR 1 ;

[0148] X is CR 19 ;

[0149] Y is CH;

[0150] R 1 Choose from the following groups: hydrogen, fluorine, chlorine, methyl, and trifluoromethyl;

[0151] R 2 and R 19 Together with the carbon atoms to which they are attached, they form a saturated 5-membered ring, which contains one or two oxygen atoms and is surrounded by 1-3 R groups. 20 replace;

[0152] R 3 Choose the group consisting of: chlorine and fluorine;

[0153] R 4 It is chlorine;

[0154] R 5 and R 6 Each is hydrogen;

[0155] R 7 It is CO2R9 ;

[0156] R 8 It is methyl;

[0157] R 9 Choose from the group consisting of: hydrogen, C1-C4 alkyl, and phenyl-C1-C2 alkyl;

[0158] R 18 Choose from the following groups: hydrogen, fluorine, chlorine, methyl, and trifluoromethyl;

[0159] R 20 It is halogen.

[0160] The third preferred compound of a subgroup is the following compound, in which...

[0161] A is CR 17 ;

[0162] B is nitrogen;

[0163] D is CR 1 ;

[0164] X is CR 19 ;

[0165] Y is CH;

[0166] R 1 and R 2 Together with the carbon atoms to which they are attached, they form 5- or 6-membered rings containing one or two heteroatoms selected from the group consisting of nitrogen, oxygen, and sulfur, and bound by 1-4 R groups. 20 replace;

[0167] R 3 Choose from the following groups: hydrogen, chlorine, and fluorine;

[0168] R 4 Choose from the following groups: chlorine, cyano, and aminothiocarbonyl;

[0169] R 5 and R 6 Each is independently selected from the group consisting of: hydrogen and C1-C2 alkyl groups;

[0170] R 7 Choose from the following groups: CO2R 9 CONR 10 R 11 and CH2OR 12 ;

[0171] R 8 Choose from the group consisting of: hydrogen and C1-C4 alkyl groups;

[0172] R 9 Selected from the group consisting of: hydrogen, C1-C4 alkyl, C1-C2 alkoxy-C1-C2 alkyl, and phenyl-C1-C2 alkyl;

[0173] R 10 It is SO2R 14 ;

[0174] R 11 It is hydrogen.

[0175] R 12 Choose from the group consisting of: C1-C2 alkylsulfonyl, C1-C2 haloalkylsulfonyl, and C1-C4 alkylcarbonyl;

[0176] R 14 Choose from the group consisting of: methyl and isopropyl (methyl)amino;

[0177] R 18 Choose from the group consisting of: hydrogen, fluorine, chlorine, C1-C2 alkyl and C1-C2 haloalkyl;

[0178] R 19 Choose from the group consisting of: hydrogen, fluorine, chlorine, C1-C2 alkyl and C1-C2 haloalkyl;

[0179] R 20 Selected from the group consisting of: halogen, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, cyano, and C1-C4 alkylsulfonyl.

[0180] A third preferred compound of a subgroup is the following compound, in which...

[0181] A is CR 17 ;

[0182] B is nitrogen;

[0183] D is CR 1 ;

[0184] X is CR 19 ;

[0185] Y is CH;

[0186] R 1 and R 2 Together with the carbon atoms to which they are attached, they form a saturated 5-membered ring containing one or two oxygen atoms and surrounded by 1-3 R groups. 20 replace;

[0187] R 3 Choose the group consisting of: chlorine and fluorine;

[0188] R 4 It is chlorine;

[0189] R 5 and R 6 Each is hydrogen;

[0190] R 7 It is CO2R 9 ;

[0191] R 8 It is methyl;

[0192] R 9 Choose from the group consisting of: hydrogen, C1-C4 alkyl, and phenyl-C1-C2 alkyl;

[0193] R 18 Choose from the following groups: hydrogen, fluorine, chlorine, methyl, and trifluoromethyl;

[0194] R 19 Choose from the following groups: hydrogen, fluorine, chlorine, methyl, and trifluoromethyl;

[0195] R 20 It is halogen.

[0196] Instance table

[0197] Table 1 below discloses 840 specific compounds having formula (I), designated as compound numbers 1-1 to 1-840, where Y is CH, R 4 It is chlorine, R 5 and R 6 It is hydrogen, and R 8 It is a methyl group.

[0198] Table 1

[0199]

[0200]

[0201]

[0202]

[0203]

[0204]

[0205]

[0206]

[0207]

[0208]

[0209]

[0210]

[0211]

[0212]

[0213]

[0214]

[0215]

[0216]

[0217] 840 compounds having formula (I) were designated as compound numbers 2-1 to 2-840, where Y is CH, R is 4 It is cyano, R 5 and R 6 It is hydrogen, R 8 It is a methyl group, and A, B, X, D, R 2 R 3 and R 7 The values ​​are given in Table 1 for compounds 1-1 to 1-840.

[0218] 840 compounds having formula (I) were designated as compound numbers 3-1 to 3-840, where Y is N, R 4 It is chlorine, R 5 and R 6 It is hydrogen, R 8 It is a methyl group, and A, B, X, D, R 2 R 3 and R 7 The values ​​are given in Table 1 for compounds 1-1 to 1-840.

[0219] The compounds of the present invention can be prepared using techniques known to those skilled in the art of organic chemistry. A general method for producing compounds having formula (I) is described below. Unless otherwise stated herein, substituents A, B, D, X, Y, Z, R... 1 R 2 R 3 R 4 R 5 R 6 R 7 R8 R 9 R 10 R 11 R 12 R 13 R 14 R 15 R 16 R 17 R 18 R 19 and R 20 As defined above. Starting materials used to prepare the compounds of the present invention may be purchased from common commercial suppliers or may be prepared by known methods. Starting materials and intermediates may be purified by existing methods (such as chromatography, crystallization, distillation, and filtration) before being used in the next step.

[0220] Compounds having formula (I) can be prepared from compounds having formula (A) and compounds having formula (B), as shown in reaction scheme 1.

[0221] Reaction Scheme 1

[0222]

[0223] For example, a mixture of compounds having formula (A) and compounds having formula (B) (where Hal represents a halogen atom, such as chlorine, bromine, or iodine) can optionally be treated with a metal catalyst (such as palladium acetate) in a suitable solvent (such as dioxane) in the presence of a suitable ligand (such as a phosphine ligand, such as S-Phos) or a pre-formed complex of a metal and ligand (such as dppf palladium dichloride) and a base (such as potassium acetate).

[0224] Boric acid (or the corresponding borate ester) having formula (A) is available or can be prepared by methods well known in the literature.

[0225] Compounds having formula (B) can be prepared from aniline having formula (C), as shown in reaction scheme 2.

[0226] Reaction Scheme 2

[0227]

[0228] For example, compounds having formula (C) can be treated in suitable solvents (such as a mixture of water and acetonitrile) with metal halides (such as potassium iodide) and nitrosating agents (such as sodium nitrite and toluenesulfonic acid).

[0229] Aniline having formula (C) can be prepared from nitro compounds having formula (D), as shown in reaction scheme 3.

[0230] Reaction scheme 3

[0231]

[0232] For example, compounds having formula (D) can be treated in a suitable solvent (such as a mixture of water and ethanol) with a reducing agent (such as iron and ammonium chloride).

[0233] Nitro compounds of formula (D) can be prepared from oximes of formula (E) and olefins of formula (F), as shown in reaction scheme 4.

[0234] Reaction scheme 4

[0235]

[0236] For example, an oxime having formula (E) can be treated with N-chlorosuccinimide in a suitable solvent (such as dimethylformamide), and the resulting intermediate is then treated with an olefin having formula (F) in a suitable solvent (such as dichloromethane) in the presence of a base (such as triethylamine).

[0237] Alkenes having formula (F) are available or can be prepared by methods well known in the literature.

[0238] Oximes having formula (E) can be prepared from aldehydes having formula (G), as shown in reaction scheme 5.

[0239] Reaction scheme 5

[0240]

[0241] For example, aldehydes having formula (G) can be treated with hydroxylamine hydrochloride in a suitable solvent (such as a mixture of water and ethanol).

[0242] Aldehydes having formula (G) are available or can be prepared by methods known in the literature.

[0243] Compounds having formula (IA) (which are compounds having formula (I), wherein R) 7 (It is a formic acid group) can be produced by compounds having formula (IB) (which are compounds having formula (I), where R is a formic acid group) 7 It is CO2R 9 The reaction is prepared as shown in reaction scheme 6.

[0244] Reaction scheme 6

[0245]

[0246] For example, compounds having formula (IB) can be treated with sodium hydroxide in a suitable solvent, such as a mixture of water and ethanol.

[0247] Compounds having formula (IC) (which are compounds having formula (I), wherein R) 7 (Is hydroxymethyl) can be prepared from compounds having the formula (IA or IB), as shown in reaction scheme 7.

[0248] Reaction Scheme 7

[0249]

[0250] For example, compounds having formula (IA) or (IB) can be treated in a suitable solvent (such as tetrahydrofuran) with a suitable reducing agent (such as a metal hydride reagent, such as sodium borohydride or borane).

[0251] Compounds having formula (ID) (which are compounds having formula (I), R) 7 It is CH2OR 12 It can be prepared from a compound having the formula (IC), as shown in reaction scheme 8.

[0252] Reaction Scheme 8

[0253]

[0254] For example, compounds having the formula (IC) can be used in the presence of a base (such as sodium hydride or triethylamine) in a suitable solvent (such as tetrahydrofuran) with reagent R. 12 -LG (where LG is a leaving group, such as halogen) is used for treatment (such as alkylating agents, acylating agents or sulfonating agents).

[0255] Compounds having formula (IE) (which are compounds having formula (I), wherein R) 7 It is CONR 10 R 11 It can be prepared from a compound having formula (IA), as shown in reaction scheme 9.

[0256] Reaction Scheme 9

[0257]

[0258] For example, compounds having formula (IA) can be treated in a suitable solvent (such as dichloromethane) with a halogenating agent (such as oxalyl chloride) to form an acyl halide, which can then be reacted in a suitable solvent (such as dichloromethane) with the reagent HNR in the presence of a base (such as triethylamine). 10 R 11Process it.

[0259] Compounds having formula (IG) (which are compounds having formula (I), wherein R) 7 (It is an oxime group) can be produced by compounds having formula (IF) (which is a compound having formula (I), wherein R is an oxime group) 7 It is prepared by (a ketone group), as shown in reaction scheme 10.

[0260] Reaction Scheme 10

[0261]

[0262] For example, compounds having the formula (IF) can optionally be treated with hydroxylamine H2NOR16 or a salt thereof in a suitable solvent (such as ethanol) in the presence of a base (such as triethylamine).

[0263] A compound having formula (IH) (which is a compound having formula (I) where R7 is a hydrazone group) can be prepared from a compound having formula (IF) (which is a compound having formula (I) where R7 is a ketone group), as shown in reaction scheme 11.

[0264] Reaction Scheme 11

[0265]

[0266] For example, compounds having formula (IF) can optionally be treated with hydrazine H2NN(R16)2 or a salt thereof in a suitable solvent (such as ethanol) in the presence of a base (such as triethylamine).

[0267] Compounds having formula (I) can also be prepared from compounds having formula (H) and compounds having formula (J), as shown in reaction scheme 12.

[0268] Reaction Scheme 12

[0269]

[0270] For example, a mixture of a compound having formula (H) (where Hal represents a halogen atom, such as chlorine, bromine, or iodine) and a compound having formula (J) can optionally be treated with a metal catalyst (such as palladium acetate) in a suitable solvent (such as dioxane) in the presence of a suitable ligand (such as a phosphine ligand, e.g., S-Phos) or a pre-formed complex of a metal and ligand (such as dppf palladium dichloride) and a base (such as potassium acetate).

[0271] Halogenated aromatic compounds having the formula (H) are available or can be prepared by methods well known in the literature.

[0272] Compounds having formula (J) can be prepared from halo-aromatic compounds having formula (B), as shown in reaction scheme 13.

[0273] Reaction Scheme 13

[0274]

[0275] For example, a mixture of a compound having formula (B) (where Hal represents a halogen atom, such as chlorine, bromine, or iodine) and a boron transfer agent (e.g., tetrahydroxydiboron, or, for the preparation of the corresponding borate ester, dipentanoyldiboron) can optionally be treated with a metal catalyst (e.g., palladium acetate) in a suitable solvent (e.g., dioxane) in the presence of a suitable ligand (e.g., a phosphine ligand, such as S-Phos) or a pre-formed complex of the metal and ligand (e.g., dppf palladium dichloride) and a base (e.g., potassium acetate).

[0276] Those skilled in the art will recognize that the order in which the transformations described above are performed can often be altered or they can be combined in alternative ways to prepare various compounds having formula (I). Multiple steps can also be combined in a single reaction. All such variations are contemplated within the scope of this invention.

[0277] Those skilled in the art will also recognize that some reagents are incompatible with certain values ​​or combinations of substituents A, B, D, X, Y, Z, R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, R15, R16, R17, R18, R19, and R20 as defined herein, and any additional steps, such as protection and / or deprotection (required to complete the desired transformation), will be apparent to those skilled in the art.

[0278] The compounds according to the invention can be used as herbicides in their unmodified form, but they are generally formulated into compositions using various formulation adjuvants (such as carriers, solvents, and surfactants). These formulations can be in different physical forms, for example, as powders, gels, wettable powders, water-dispersible granules, water-dispersible tablets, effervescent compressed tablets, emulsifiable concentrates, microemulsifiable concentrates, oil-in-water emulsions, flowable oils, aqueous dispersions, oily dispersions, suspensions, capsule suspensions, emulsifiable granules, soluble liquids, water-soluble concentrates (with water or a water-miscible organic solvent as a carrier), impregnated polymer films, or in other known forms, such as those known from the Manual on Development and Use of FAO and WHO Specifications for Pesticides, United Nations, 1st edition, Second Revision (2010). For water-soluble compounds, soluble liquids, water-soluble concentrates, or water-soluble granules are preferred. These preparations can be used directly or diluted before use. They can be diluted with, for example, water, liquid fertilizer, micronutrients, biological organisms, oils, or solvents.

[0279] These formulations can be prepared, for example, by mixing the active ingredients with formulation aids to obtain compositions in the form of finely dispersed solids, particles, solutions, dispersions, or emulsions. These active ingredients can also be formulated with other aids, such as finely dispersed solids, mineral oils, oils of plant or animal origin, modified oils of plant or animal origin, organic solvents, water, surfactants, or combinations thereof.

[0280] These active ingredients can also be contained in very fine microcapsules. Microcapsules contain the active ingredient within a porous carrier. This allows the active ingredient to be released into the environment in controlled amounts (e.g., slow release). Microcapsules typically have a diameter from 0.1 to 500 micrometers. The amount of active ingredient they contain is approximately 25% to 95% by weight of the capsule. These active ingredients can be in the form of a monolithic solid, fine particles in a solid or liquid dispersion, or in a solution-suitable form. The encapsulating membrane can comprise, for example, natural or synthetic rubber, cellulose, styrene / butadiene copolymers, polyacrylonitrile, polyacrylates, polyesters, polyamides, polyureas, polyurethanes, or chemically modified polymers, as well as starch xanthates, or other polymers known to those skilled in the art. Alternatively, very fine microcapsules can be formed in which the active ingredient is contained in the form of finely dispersed particles within a solid matrix of a base substance, but these microcapsules themselves are not encapsulated.

[0281] Suitable formulation aids for preparing compositions according to the invention are known in themselves. As liquid carriers, the following can be used: water, toluene, xylene, petroleum ether, vegetable oil, acetone, methyl ethyl ketone, cyclohexanone, acid anhydride, acetonitrile, acetophenone, amyl acetate, 2-butanone, butenyl carbonate, chlorobenzene, cyclohexane, cyclohexanol, alkyl acetate, diacetone alcohol, 1,2-dichloropropane, diethanolamine, p-diethylbenzene, diethylene glycol, diethylene glycol, diethylene glycol butyl ether, diethylene glycol ethyl ether, diethylene glycol methyl ether, N,N-dimethyl... Formamide, dimethyl sulfoxide, 1,4-dioxane, dipropylene glycol, dipropylene glycol methyl ether, dipropylene glycol dibenzoate, dipropylene glycol, alkylpyrrolidone, ethyl acetate, 2-ethylhexanol, ethylene carbonate, 1,1,1-trichloroethane, 2-heptanone, α-pinene, d-limonene, ethyl lactate, ethylene glycol, ethylene glycol butyl ether, ethylene glycol methyl ether, γ-butyrolactone, glycerol, glyceryl acetate, glyceryl diacetate, glyceryl triacetate, deca-acetate, etc. Hexadecane, hexanediol, isopentyl acetate, isobornyl acetate, isooctane, isophorone, cumene, isopropyl myristate, lactic acid, laurylamine, isopropyl acetone, methoxypropanol, methyl isopentyl ketone, methyl isobutyl ketone, methyl lauryl ketone, methyl octanoate, methyl oleate, dichloromethane, m-xylene, n-hexane, n-octylamine, octadecanoic acid, octylamine acetate, oleic acid, oleyleneamine, o-xylene, phenol, polyethylene glycol, propionic acid, propyl lactate Propylene carbonate, propylene glycol, propylene glycol methyl ether, p-xylene, toluene, triethyl phosphate, triethylene glycol, xylenesulfonic acid, paraffin, mineral oil, trichloroethylene, perchloroethylene, ethyl acetate, amyl acetate, butyl acetate, propylene glycol methyl ether, diethylene glycol methyl ether, methanol, ethanol, isopropanol, and alcohols with higher molecular weights, such as pentanol, tetrahydrofuranol, hexanol, octanol, ethylene glycol, propylene glycol, glycerol, N-methyl-2-pyrrolidone, etc.

[0282] Suitable solid carriers include, 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 substances.

[0283] Many surfactants can be advantageously used in both solid and liquid formulations, especially those that can be diluted with a carrier before use. Surfactants can be anionic, cationic, nonionic, or polymeric, and they can be used as emulsifiers, wetting agents, suspending agents, or for other purposes. Typical surfactants include, for example, salts of alkyl sulfates, such as diethanolammonium dodecyl sulfate; salts of alkyl aryl sulfonates, such as calcium dodecylbenzenesulfonate; alkylphenol / olefin oxide addition products, such as ethoxylated nonylphenol; alcohol / olefin oxide addition products, such as ethoxylated tridecyl alcohol; soaps, such as sodium stearate; salts of alkyl naphthalene sulfonates, such as sodium dibutylnaphthalene sulfonate; salts of dialkyl sulfosuccinates, such as sodium di(2-ethylhexyl)sulfosuccinate; sorbitol esters, such as sorbitol oleate; quaternary ammonium compounds, such as dodecyltrimethylammonium chloride; polyethylene glycol esters of fatty acids, such as polyethylene glycol stearate; block copolymers of ethylene oxide and propylene oxide; and salts of monoalkyl and dialkyl phosphate esters; and other substances, such as those described in McCutcheon's Detergents and Emulsifiers Annual, MC Publishing. Corp.), Ridgewood, New Jersey (1981).

[0284] Other adjuvants that can be used in formulations for killing pests include crystallization inhibitors, viscosity modifiers, suspending agents, dyes, antioxidants, foaming agents, light absorbers, mixing aids, defoamers, complexing agents, substances that neutralize or change pH and buffer solutions, corrosion inhibitors, fragrances, wetting agents, absorption enhancers, micronutrients, plasticizers, flow aids, lubricants, dispersants, thickeners, antifreeze agents, microbial agents, and liquid and solid fertilizers.

[0285] The compositions according to the invention may include additives comprising oils of plant or animal origin, mineral oils, alkyl esters of such oils, or mixtures of such oils and oil derivatives. The amount of oil additive in the compositions according to the invention is typically from 0.01% to 10% of the mixture to be applied. For example, the oil additive may be added to the spray can at the desired concentration after the spray mixture has been prepared. Preferred oil additives include mineral oils or plant-derived oils, such as rapeseed oil, olive oil, or sunflower oil; emulsified vegetable oils; alkyl esters of plant-derived oils, such as methyl derivatives; or animal-derived oils, such as fish oil or tallow. Preferred oil additives include C8-C... 22 Alkyl esters of fatty acids, especially C 12 -C 18Methyl derivatives of fatty acids, such as lauric acid, palmitic acid, and methyl esters of oleic acid (methyl laurate, methyl palmitate, and methyl oleate, respectively). Many oil derivatives are known in the Compendium of Herbicide Adjuvants, 10th edition, Southern Illinois University, 2010.

[0286] Herbicidal compositions typically comprise from 0.1% to 99%, particularly from 0.1% to 95% by weight, of a compound having formula (I) and from 1% to 99.9% by weight, of a formulation adjuvant, which preferably comprises from 0% to 25% by weight of a surfactant. These compositions of the invention generally comprise from 0.1% to 99%, particularly from 0.1% to 95% by weight, of the compound of the invention and from 1% to 99.9% by weight, of a formulation adjuvant, which preferably comprises from 0% to 25% by weight of a surfactant. Commercial products may preferably be formulated as concentrates, while end users will typically use diluted formulations.

[0287] Application rates vary over a wide range and depend on soil properties, application method, crop, pests to be controlled, primary climatic conditions, and other factors governed by application method, application time, and target crop. Generally, compounds can be applied at rates ranging from 1 l / ha to 2000 l / ha, particularly from 10 l / ha to 1000 l / ha.

[0288] Preferred formulations may have the following composition (by weight%):

[0289] Emulsifiable concentrates:

[0290] Active ingredient: 1% to 95%, preferably 60% to 90%

[0291] Surfactant: 1% to 30%, preferably 5% to 20%

[0292] Liquid carrier: 1% to 80%, preferably 1% to 35%

[0293] Dust agent:

[0294] Active ingredient: 0.1% to 10%, preferably 0.1% to 5%.

[0295] Solid carrier: 99.9% to 90%, preferably 99.9% to 99%.

[0296] Suspension concentrate:

[0297] Active ingredient: 5% to 75%, preferably 10% to 50%

[0298] Water: 94% to 24%, preferably 88% to 30%

[0299] Surfactant: 1% to 40%, preferably 2% to 30%

[0300] Wettable powder:

[0301] Active ingredient: 0.5% to 90%, preferably 1% to 80%

[0302] Surfactant: 0.5% to 20%, preferably 1% to 15%

[0303] Solid carrier: 5% to 95%, preferably 15% to 90%

[0304] Granules:

[0305] Active ingredient: 0.1% to 30%, preferably 0.1% to 15%.

[0306] Solid carrier: 99.5% to 70%, preferably 97% to 85%.

[0307] The compositions of the present invention may further comprise at least one additional pest control 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 pest control agent is a herbicide and / or a herbicide safener.

[0308] Therefore, compounds having formula (I) can be used in combination with one or more other herbicides to provide a variety of weed control mixtures. Specific examples of such mixtures include (where “I” represents a compound having formula (I)): - I + acetochlor; I + trifluralin (including trifluralin-sodium); I + bensulfuron; I + metolachlor; I + quizalofop-P-ethyl; I + atrazine; I + amazolidinone; I + cyprodinil; I + chlorpyrifos; I + chlorpyrifos; I + sulfadiazine; I + atrazine; I + bensulfuron-methyl (including bensulfuron-methyl); I + thiamethoxam; I + bicyclopyranone; I + bispyrazophosphorus; I + cyprodinil; I + bispyrazophosphorus-sodium; I + bixlozone; I + chlorpyrifos; I + bromobenzonitrile; I + butachlor; I + flupropyrazosulfuron; I + pyrazosulfuron; I + chlorpyrifos; I + chlorpyrifos Isosulfuron-methyl (including acesulfuron-ethyl); sulfuron-methyl (including sulfuron-methyl); I + chlorpyrifos (including chlorpyrifos-ethyl); I + chlormequat chloride; I + ethersulfuron-methyl; I + chlorsulfuron-methyl; I + cyclopyranil; I + cyclopyrimorate; I + cyprosulfuron-methyl; I + cyhalofop-butyl (including cyhalofop-butyl); I + 2,4-D (including its choline salt and 2-ethylhexyl ester); I + 2,4-DB; I + chlorpyrifos; I + betaine; I + chlorpyrifos dicamba (including its aluminum, aminopropyl, bis-aminopropylmethyl, choline, dichloropropane, diethylene glycolamine, dimethylamine, dimethylammonium, potassium salt, and sodium salt); I + quizalofop-P-ethyl; I + cyhalofop-P-ethyl; I + pyrifluquinazon; I + cyhalofop-P-ethyl; I + flupyrazole; I + metolachlor; I + fenfluridine; I + diquat dibromide; I + diuron; I + dicamba; I + butachlor; I + ethoxysulfuron; I + quizalofop-P-ethyl (including fenfluridine-P-ethyl); I + fenoxasulfone; I + fenquinotrione; I + tetrazolium; I + pyrimisulfuron; I + cyhalofop-P-ethyl; I + chlorpyrifos; I + chlorpyrifos Pyralid (including quizalofop-butyl); I + flumetsulam (including flumetsulam-sodium); I + fluthiamethoxam; I + flubendiamide; I + pyrimethanil; I + propyzoxystrobin; I + flupyrimisulfuron (including flupyrimisulfuron-methyl-sodium);I + Fluroxypyr-meptyl (including fluroxypyr-meptyl); I + Fluthiamethoxam; I + Flusulfanilamide; I + Formamide-sulfuron; I + Glufosinate (including its ammonium salt); I + Glyphosate (including its hydrazine, isopropylammonium, and potassium salts); I + Halauxifen (including halauxifen-methyl); I + Pyriproxypyr; I + Pyriproxypyr-methyl; I + Cycloazidine; I + Hydantocidin; I + Methoxypyr; I + Methyl Methoxypyr; I + Bentazon; I + Methoxypyr; I + Methoxypyr; I + Indaziflam; I + Iofensulfuron (including Iofensulfuron-methyl-sodium); I + I + Isofensulfuron-sodium; I + iodobenzonitrile; I + ipfencarbazone; I + isoproturon; I + isoxaben; I + isoxaflutole; I + lancotrione; I + linuron; I + MCPA; I + MCPB; I + mecoprop-P; I + benzylsulfuron; I + mesosulfuron-methyl; I + mesosulfuron-methyl; I + mesosulfuron-methyl; I + fenproxetil; I + pyrazosulfuron; I + methiozolin; I + succinylsulfuron; I + metolachlor; I + sulfadiazine; I + methoxyfenozide; I + cyprodinil; I + mesosulfuron-methyl; I + sulfadiazine ... Dabendazole; I + pyrimethanil; I + propyzoxystrobin; I + oxadiazon; I + cyclopyrimethanil; I + ethoxyflufenoxam; I + paraquat dichlorvos; I + pendimethalin; I + penflusulfuron; I + bendimethalin; I + flupyrflupyr; I + clodinafop-propargyl; I + pretilachlor; I + flupyrsulfuron-methyl; I + amfluroxyfen; I + prochloraz; I + chlorpyrifos; I + propyzoxystrobin; I + oxychloride; I + oxychloride; I + oxadiazon; I + fenpropathrin; I + propyrimethanil; I + pendyrflupyr; I + bendisulfuron; I + flusulfuron; I + cyprodinil; I + pyrazosulfuron (including pyrazosulfuron-ethyl); I + pyrazosulfuron; I + pyrazosulfuron-methyl ... Pyrimisulfuron; I + pyrimisulfuron; I + pyrazosulfuron; I + cyclopyrazosulfuron; I + pyriproxyfen, I + pyrimisulfuron; I + pyrrolizamide;I + quinclorac; I + chlorpyrifos; I + quizalofop-P-tefuryl (including quizalofop-ethyl and quizalofop-P-tefuryl); I + sulfadiazine; I + phenazine; I + simazin; I + S-metolachlor; I + sulfadiazine; I + mesosulfuron; I + sulfonylsulfuron; I + terbutaline; I + cyclosulfonyl; I + terbutaline; I + terbutaline; I + thiencarbazone; I + thifensulfuron; I + tiafenacil; I + tolpyralate; I + phenazine; I + triafamone; I + fenpyrazanol; I + fenpyrazanol; I + benzylsulfuron; I + benzylsulfuron (including benzylsulfuron-methyl); I + chlorpyrifos; I + trifludimoxazin (including trifludimoxazin-sodium); I + trifluridine; I + flumethanil; I + triflumethanil; I + 4-hydroxy-1-methoxy-5-methyl-3-[4-(trifluoromethyl)-2-pyridyl]imidazolidine-2-one; I + 4-hydroxy-1,5-dimethyl-3-[4-(trifluoromethyl)-2-pyridyl]imidazolidine-2-one; I + 5-ethoxy-4-hydroxy-1-methyl-3-[4-(trifluoromethyl)-2-pyridyl]imidazolidine-2-one; I + 4-hydroxy-1-methyl-3-[4-(trifluoromethyl)-2-pyridyl]imidazolidine-2-one; I + 4-Hydroxy-1,5-dimethyl-3-[1-methyl-5-(trifluoromethyl)pyrazol-3-yl]imidazolidine-2-one; I + (4R)1-(5-tert-butylisoxazol-3-yl)-4-ethoxy-5-hydroxy-3-methyl-imidazolidine-2-one; I + 3-[2-(3,4-dimethoxyphenyl)-6-methyl-3-oxo-pyridazin-4-carbonyl]bicyclo[3.2.1]octane-2,4-dione; I + 2-[2-(3,4-dimethoxyphenyl)-6-methyl-3-oxo-pyridazin-4-carbonyl]-5-methyl-cyclohexane-1,3-dione; I + 2-[2-(3,4-dimethoxyphenyl)-6-methyl-3-oxo-pyridazin-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-pyridazin-4-carbonyl]-5-ethyl-cyclohexane-1,3-dione; I + 2-[2-(3,4-dimethoxyphenyl)-6-methyl-3-oxo-pyridazin-4-carbonyl]-4,4,6,6-tetramethyl-cyclohexane-1,3-dione; I + 2-[6-cyclopropyl-2-(3,4-dimethoxyphenyl)-3-oxo-pyridazin-4-carbonyl]-5-methyl-cyclohexane-1,3-dione; I + 3-[6-cyclopropyl-2-(3,4-dimethoxyphenyl)-3-oxo-pyridazin-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.

[0309] Mixtures of compounds having formula (I) may also be in the form of esters or salts, as mentioned, for example, in The Pesticide Manual, 14th edition, British Crop Protection Council, 2006.

[0310] Compounds having formula (I) can also be used in combination with other agrochemicals, such as fungicides, nematicides or insecticides, examples of which are given in the Handbook of Pesticides.

[0311] The mixing ratio of the compound having formula (I) to the mixed compatibility is preferably from 1:100 to 1000:1.

[0312] These mixtures can be advantageously used in the formulations mentioned above (in which case "active ingredient" refers to the corresponding mixture of a compound having formula (I) and the mixed formulation).

[0313] The compounds of formula (I) of the present invention can also be combined with herbicide safeners. Preferred combinations (where "I" represents a compound of formula (I)) include: - I + cyprodinil; I + cyprodinil (including cyprodinil); I + cyclopropanesulfonamide; I + dichloropropeneamine; I + cyprodinil (including cyprodinil-ethyl); I + cyprodinil; I + fluroxypyr; I + cyprodinil, I + bis(oxazolyl) acid (including bis(oxazolyl) acid-ethyl); I + pyrazole cyprodinil (including pyrazole cyprodinil); I + metcamifen; I + N-(2-methoxybenzoyl)-4-[(methylaminocarbonyl)amino]benzenesulfonamide and I + cyprodinil.

[0314] Particularly preferred are mixtures of compounds having formula (I) with cyclopropanesulfonamide, bisbenzoxazolic acid (including bisbenzoxazolic acid-ethyl), oxadiazol (including oxadiazol) and / or N-(2-methoxybenzoyl)-4-[(methyl-aminocarbonyl)amino]benzenesulfonamide.

[0315] These safeners having formula (I) can also be in the form of esters or salts, such as those mentioned in the Handbook of Pesticides (14th edition (BCPC), 2006). References to fenchlorazole also apply to lithium, sodium, potassium, calcium, magnesium, aluminum, iron, ammonium, quaternary ammonium, sulfonium, or their phosphonium salts (as disclosed in WO 02 / 34048), and references to fenchlorazole-ethyl also apply to fenchlorazole, etc.

[0316] Preferably, the mixing ratio of the compound having formula (I) to the safener is from 100:1 to 1:10, especially from 20:1 to 1:1.

[0317] These mixtures can be advantageously used in the formulations mentioned above (in which case "active ingredient" refers to a corresponding mixture of a compound having formula (I) and a safener).

[0318] The compounds of formula (I) of the present invention are useful as herbicides. Therefore, the present invention also includes methods for controlling unwanted plants, comprising applying an effective amount of the compound of the present invention or a herbicidal composition containing the compound to said plants or sites containing them. 'Control' means to kill, reduce, or delay growth or prevent or reduce germination. Plants to be controlled are generally unwanted plants (weeds). 'Site' means an area in which plants are growing or will grow.

[0319] Unwanted plants should be understood to also include those weeds that have been conferred tolerance to herbicides or multiple classes of herbicides (e.g., ALS-inhibitors, GS-inhibitors, EPSPS-inhibitors, PPO-inhibitors, ACC enzyme-inhibitors, and HPPD-inhibitors) through evolution, conventional breeding methods, or genetic engineering. Examples include Amaranthus palmeri, which has evolved resistance to glyphosate and / or acetyllactate synthase (ALS) inhibitory herbicides.

[0320] The compounds of this invention can be used in methods for controlling unwanted plants or weeds resistant to protoporphyrinogen oxidase (PPO) inhibitors. For example, populations of *Amaranthus tuberculatus* and *Amaranthus tuberculatus* have evolved as PPO-resistant weeds in many parts of the world, for example, due to amino acid substitutions at position 210 (Δ210) of the PPX2 gene encoding the target enzyme of PPO inhibitor herbicides, such as R128M / G (also known as R98) or G399A, or a deletion of the codon (glycine). The compounds of this invention can be used in methods for controlling *Amaranthus tuberculatus* and / or *Amaranthus tuberculatus* with any of the above mutations, and obviously, it is also possible to attempt to control unwanted plants or weeds with compounds using other mutations conferring tolerance or resistance to possible PPO inhibitors.

[0321] The application rate of compounds having formula (I) can vary within a wide range and depends on soil properties, application method (pre-emergence; post-emergence; application in seed furrows; no-till application, etc.), crop species, one or more weeds to be controlled, prevailing climatic conditions, and other factors governed by the application method, application time, and target crop. Compounds having formula (I) according to the invention are typically applied at rates from 10 g / ha to 2000 g / ha, particularly from 50 g / ha to 1000 g / ha. A preferred range is 10-200 g / ha.

[0322] The composition is typically applied by spraying, usually with a tractor-mounted sprayer for large areas, but other methods such as dusting (for powders), dripping, or wetting can also be used.

[0323] Useful plants that can use the compositions according to the invention include crops such as cereals, such as barley and wheat, cotton, rapeseed, sunflower, corn, rice, soybean, sugar beet, sugarcane and turf.

[0324] Crop plants can also include trees, such as fruit trees, palm trees, coconut trees, or other nut-bearing plants. It also includes vines (such as grapes), shrubs, fruit trees, fruit plants, and vegetables.

[0325] Crops should be understood to include those crops that have been conferred tolerance to herbicides or multiple classes of herbicides (e.g., ALS-inhibitors, GS-inhibitors, EPSPS-inhibitors, PPO-inhibitors, ACC enzyme-inhibitors, and HPPD-inhibitors) through conventional breeding methods or through genetic engineering. An example of a crop conferred tolerance to imidazolinones (e.g., methoxyfenozide) through conventional breeding methods is Clearfield® summer canola. Examples of crops conferred herbicide tolerance through genetic engineering include, for example, glyphosate and glufosinate-resistant maize varieties commercially available under the trademarks RoundupReady® and LibertyLink®.

[0326] The compounds of this invention can be used in methods for controlling undesirable vegetation in crop plants that are resistant to protoporphyrinogen oxidase (PPO) inhibitors. Such plants can be obtained, for example, by transforming crop plants with nucleic acids encoding suitable protoporphyrinogen oxidases, which may contain mutations to make them 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, WO2012 / 080975, WO 2013 / 189984, WO 2015 / 022636, WO 2015 / 022640, WO 2015 / 092706, WO2016 / 099153, WO 2017 / 023778, WO 2017 / 039969, WO 2017 / 217793, WO 2017 / 217794, WO2018 / 114759, WO 2019 / 117578, WO 2019 / 117579 and WO 2019 / 118726.

[0327] Crops should also be understood as those crops that have been genetically engineered to be resistant to harmful insects, such as Bt maize (resistant to the European corn borer), Bt cotton (resistant to the boll weevil), and Bt potato (resistant to the Colorado beetle). An example of Bt maize is NK®'s Bt 176 maize hybrid (Syngenta Seeds). Bt toxins are proteins naturally formed by the soil bacteria Bacillus thuringiensis. Examples of toxins or transgenic plants capable of synthesizing such toxins are described in EP-A-451 878, EP-A-374 753, WO 93 / 07278, WO 95 / 34656, WO 03 / 052073, and EP-A-427 529. Examples of transgenic plants containing one or more genes encoding insecticide resistance and expressing one or more toxins are KnockOut® (maize), Yield Gard® (maize), NuCOTIN33B® (cotton), Bollgard® (cotton), NewLeaf® (potato), NatureGard®, and Protecta®. Plant crops or their seed material can be herbicide-resistant and simultaneously resistant to insect feeding (“superimposed” transgenic results). For example, seeds can have the ability to express the insecticidal Cry3 protein while simultaneously being resistant to glyphosate.

[0328] Crops should also be understood to include those obtained through conventional breeding or genetic engineering methods and that contain so-called output traits (such as improved storage capacity, higher nutritional value, and improved aroma).

[0329] Other useful plants include turfgrass for use in lawns, such as on golf courses, lawns, parks, and roadsides, or commercially, and ornamental plants such as flowers or shrubs.

[0330] The compounds and compositions of formula (I) of the present invention can generally be used to control a variety of monocotyledonous and dicotyledonous weed species. Typical examples of monocotyledonous species that can be controlled include Alopecurus myosuroides, Avena fatua, Brachiaria plantaginea, Bromos tectorum, Cyperus esculentus, Digitaria sanguinalis, Echinochloa crus-galli, Lolium perennium, 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, Spatholobus suberectus, Galium aparine, Ipomoea quamoclit, Kochia scoparia, Polygonum aviculare, Rapeseed simonii, Solanum nigrum, Stellaria media, Veronica persica, and Xanthium sibiricum.

[0331] Compounds having formula (I) can also be used for pre-harvest drying of crops, such as, but not limited to, potatoes, soybeans, sunflowers, and cotton. Pre-harvest drying is used to dry crop leaves without causing significant damage to the crop itself, thus aiding in harvesting.

[0332] The compounds / compositions of the present invention are particularly useful for non-selective burn-down applications, and therefore can also be used to control volunteer or escape crop plants.

[0333] Different aspects and embodiments of the invention will now be described in more detail by way of examples. It should be understood that modifications to the details may be made without departing from the scope of the invention.

[0334] Example

[0335] The following examples are used to illustrate, but do not limit, the present invention.

[0336] Synthesis Example

[0337] Example 1: Preparation of ethyl 3-[2-chloro-4-fluoro-5-(2-fluoro-3-pyridyl)phenyl]-5-methyl-4H-isoxazole-5-carboxylate (compound 1-211)

[0338] Step 1: Synthesis of 5-bromo-2-chloro-4-fluorobenzaldehyde

[0339]

[0340] Pyridinium dichromate (1.7 g, 10 mmol) was added to a stirred solution of (5-bromo-2-chloro-4-fluoro-phenyl)methanol (prepared as described in step 1 of Example 2; 1.2 g, 5.0 mmol) in dichloromethane (60 ml). The resulting mixture was stirred at room temperature for 15 hours, then filtered under reduced pressure and evaporated to leave a residue, which was purified by chromatography to provide 5-bromo-2-chloro-4-fluoro-benzaldehyde (1.2 g) as a white solid.

[0341] 1 H NMR (400 MHz, CDCL3) δ 10.3 (s,1H), 8.15 (d,1H), 7.3 (d,1H) ppm.

[0342] Step 2: Synthesis of 5-bromo-2-chloro-4-fluorobenzaldehyde oxime

[0343]

[0344] Hydroxylamine hydrochloride (1.27 g, 18.4 mmol) was added to a stirred solution of 5-bromo-2-chloro-4-fluorobenzaldehyde (3 g, 12.3 mmol) in tetrahydrofuran (15 ml) at room temperature. Water (3 ml) was added and the resulting solution was stirred at room temperature for 60 min. Water (50 ml) was added and the resulting mixture was extracted with ethyl acetate. The combined organic phases were dried and evaporated under reduced pressure to provide 5-bromo-2-chloro-4-fluorobenzaldehyde oxime (2.5 g) as an off-white solid.

[0345] Also prepared by this general method are:

[0346] 5-Bromo-2-cyano-benzaldehyde oxime

[0347] 1 H NMR (400 MHz, CDCl3) δ 8.4 (s,1H), 8.1 (d,1H), 7.85 (s,1H), 7.6 (dd,1H), 7.55 (d,1H) ppm.

[0348] Step 3: Synthesis of ethyl 3-(5-bromo-2-chloro-4-fluoro-phenyl)-5-methyl-4H-isoxazole-5-carboxylate

[0349]

[0350] 1-Chloroprene-2,5-dione (1.6 g, 12 mmol) was added in portions to a stirred solution of 5-bromo-2-chloro-4-fluorobenzaldehyde oxime (2.5 g, 9.9 mmol) in N,N-dimethylformamide (18 ml) at 30°C. The resulting mixture was stirred at 30°C for 1 hour, then cooled to room temperature and water (20 ml) and dichloromethane (50 ml) were added. The phases were separated and the organic phase was dried and cooled to 5°C. A mixture of triethylamine (1.3 ml, 9.4 mmol) and ethyl 2-methylprop-2-enoate (1.4 g, 10 mmol) was added dropwise to this stirred solution. After standing at room temperature for 1 hour, dilute hydrochloric acid (5 ml) and water (20 ml) were added to separate the phases and the organic phase was dried and purified by chromatography to provide ethyl 3-(5-bromo-2-chloro-4-fluoro-phenyl)-5-methyl-4H-isoxazole-5-carboxylate (2.6 g) as a yellow oil.

[0351] 1 H NMR (400 MHz, CDCl3) δ 7.9 (d,1H), 7.2 (d,1H), 4.3 (q,2H), 3.95 (d,1H), 3.35 (d,1H), 1.7 (s,3H), 1.35 (t,3H) ppm.

[0352] Also prepared by this general method are:

[0353] ethyl 3-(5-bromo-2-cyano-phenyl)-5-methyl-4H-isoxazole-5-carboxylate

[0354] 1 H NMR (400 MHz, CDCl3) δ 8.05 (d,1H), 7.65 (dd,1H), 7.6 (d,1H), 4.3(q,2H), 4.05 (d,1H), 3.45 (d,1H), 1.75 (s,3H), 1.35 (t,3H) ppm.

[0355] Step 4: Synthesis of ethyl 3-[2-chloro-4-fluoro-5-(2-fluoro-3-pyridyl)phenyl]-5-methyl-4H-isoxazole-5-carboxylate (compound 1-211)

[0356]

[0357] Potassium acetate (78 mg, 0.78 mmol) and [1,1'-bis(diphenylphosphino)ferrocene]palladium dichloride (19 mg, 0.03 mmol) were added to a solution of 3-(5-bromo-2-chloro-4-fluoro-phenyl)-5-methyl-4H-isoxazol-5-carboxylate (95 mg, 0.26 mmol) and (2-fluoro-3-pyridyl)boronic acid (57 mg, 0.39 mmol) in dioxane (3.8 ml). The mixture was heated in a microwave oven at 100°C for 45 minutes, cooled, and ethyl acetate (10 ml) was added. The mixture was then filtered and evaporated under reduced pressure. The resulting oil was purified by chromatography to provide ethyl 3-[2-chloro-4-fluoro-5-(2-fluoro-3-pyridyl)phenyl]-5-methyl-4H-isoxazole-5-carboxylate (compound 1-211) (80 mg) as a golden gel.

[0358] 1 H NMR (400 MHz, CD3OD) δ 8.3 (d,1H), 8.05 (dt,1H), 7.75 (d,1H), 7.55(d,1H), 7.45 (m,1H), 4.3 (q,2H), 4.1 (d,1H), 3.45 (d,1H), 1.7 (s,3H), 1.3 (t,3H) ppm.

[0359] Also prepared by this general method are:

[0360] 3-[2-chloro-5-[2-chloro-4-(trifluoromethyl)phenyl]-4-fluoro-phenyl]-5-methyl-4H-isoxazole-5-carboxylic acid ethyl ester (compounds 1-7)

[0361] 1 H NMR (400 MHz, CDCl3) δ 7.75 - 7.55 (m,4H), 7.3 (d,1H), 4.3 (q,2H), 4.0 (d,1H), 3.45 (d,1H), 1.7 (s,3H), 1.3 (t,3H) ppm.

[0362] 3-[2-chloro-5-(2-chlorophenyl)-4-fluoro-phenyl]-5-methyl-4H-isoxazole-5-carboxylic acid ethyl ester (compounds 1-19)

[0363] 1H NMR (400 MHz, CDCl3) δ 7.65 (d,1H), 7.5 (d,1H), 7.45 - 7.3 (m,4H), 4.3 (q,2H), 4.0 (d,1H), 3.4 (d,1H), 1.7 (s,3H), 1.3 (t,3H) ppm.

[0364] 3-[2-chloro-5-(5-chloro-3-pyridyl)-4-fluoro-phenyl]-5-methyl-4H-isoxazole-5-carboxylic acid ethyl ester (compound 1-271)

[0365] 1 H NMR (400 MHz, CDCl3) δ 8.75 - 8.6 (m,2H), 7.9 (m,1H), 7.85 (d,1H),7.35 (d,1H), 4.3 (q,2H), 4.0 (d,1H), 3.45 (d,1H), 1.7 (s,3H), 1.3 (t,3H)ppm.

[0366] 3-[2-chloro-4-fluoro-5-(4-methoxy-3-pyridyl)phenyl]-5-methyl-4H-isoxazole-5-carboxylic acid ethyl ester (compound 1-259)

[0367] 1 H NMR (400 MHz, CDCl3) δ 8.9 (br s,1H), 8.7 (br s,1H), 7.7 (m,1H),7.35 (br d,2H), 4.3 (q,2H), 4.15 (s,3H), 4.1 (d,1H), 3.45 (d,1H), 1.7 (s,3H),1.3 (t,3H) ppm.

[0368] 3-[2-chloro-5-(2-chloro-4-methyl-phenyl)-4-fluoro-phenyl]-5-methyl-4H-isoxazole-5-carboxylic acid ethyl ester (compounds 1-31)

[0369] 1 H NMR (400 MHz, CDCl3) δ 7.65 (d,1H), 7.3 (s,1H), 7.25 (d,1H), 7.15(m,2H), 4.3 (q,2H), 4.1 (d,1H), 3.45 (d,1H), 2.4 (s,3H), 1.7 (s,3H), 1.3 (t,3H) ppm.

[0370] 3-[2-chloro-4-fluoro-5-[2-fluoro-5-(trifluoromethyl)-3-pyridyl]phenyl]-5-methyl-4H-isoxazole-5-carboxylic acid ethyl ester (compound 1-235)

[0371] 1 H NMR (400 MHz, CDCl3) δ 8.7 (s,1H), 8.45 (d,1H), 7.8 (d,1H), 7.6 (d,1H), 4.3 (q,2H), 4.1 (d,1H), 3.45 (d,1H), 1.7 (s,3H), 1.3 (t,3H) ppm.

[0372] 3-[2-chloro-4-fluoro-5-(2-fluoro-5-methyl-3-pyridyl)phenyl]-5-methyl-4H-isoxazole-5-carboxylic acid ethyl ester (compound 1-223)

[0373] 1 H NMR (400 MHz, CDCl3) δ 8.15 (s,1H), 7.85 (d,1H), 7.7 (d,1H), 7.5(d,1H), 4.3 (q,2H), 4.1 (d,1H), 3.45 (d,1H), 2.3 (s,3H), 1.7 (s,3H), 1.3 (t,3H) ppm.

[0374] 3-[2-chloro-4-fluoro-5-(6-methyl-3-pyridyl)phenyl]-5-methyl-4H-isoxazole-5-carboxylic acid ethyl ester (compound 1-283)

[0375] 1 H NMR (400 MHz, CDCl3) δ 9.0 (d,1H), 8.25 (d,1H), 7.8 (d,1H), 7.6 (d,1H), 7.4 (d,1H), 4.3 (q,2H), 4.1 (d,1H), 3.45 (d,1H), 2.85 (s,3H), 1.7 (s,3H), 1.3 (t,3H) ppm.

[0376] 3-[2-chloro-4-fluoro-5-(3-pyridyl)phenyl]-5-methyl-4H-isoxazole-5-carboxylic acid ethyl ester (compound 1-247)

[0377] 1H NMR (400 MHz, CDCl3) δ 8.8 (br s,1H), 8.65 (dd,1H), 7.9 (dq,1H),7.8 (d,1H), 7.45 (dd,1H), 7.3 (d,1H), 4.3 (q,2H), 4.0 (d,1H), 3.45 (d,1H),1.7 (s,3H), 1.3 (t,3H) ppm.

[0378] 3-[2-chloro-5-[6-chloro-4-(trifluoromethyl)-2-pyridyl]-4-fluoro-phenyl]-5-methyl-4H-isoxazole-5-carboxylic acid ethyl ester (compounds 1-67)

[0379] 1 H NMR (400 MHz, CDCl3) δ 8.4 (d,1H), 7.95 (s,1H), 7.6 (s,1H), 7.35(d,1H), 4.3 (q,2H), 4.0 (d,1H), 3.4 (d,1H), 1.75 (s,3H), 1.35 (t,3H) ppm.

[0380] 3-[2-chloro-4-fluoro-5-(2-fluoro-4-pyridyl)phenyl]-5-methyl-4H-isoxazole-5-carboxylic acid ethyl ester (compound 1-295)

[0381] 1 H NMR (400 MHz, CDCl3) δ 8.55 (br s,1H), 7.9 (d,1H), 7.8 (m,1H), 7.4(d,1H), 6.5 (br s,1H), 4.3 (q,2H), 4.1 (d,1H), 3.45 (d,1H), 1.7 (s,3H), 1.3(t,3H) ppm.

[0382] 3-[2-chloro-4-fluoro-5-[6-(trifluoromethyl)-2-pyridyl]phenyl]-5-methyl-4H-isoxazole-5-carboxylic acid ethyl ester (compounds 1-43)

[0383] 1 H NMR (400 MHz, CDCl3) δ 8.35 (d,1H), 7.95 (d,2H), 7.7 (m,1H), 7.35(d,1H), 4.3 (q,2H), 4.1 (d,1H), 3.45 (d,1H), 1.7 (s,3H), 1.3 (t,3H) ppm.

[0384] 3-[2-chloro-4-fluoro-5-(2-pyridyl)phenyl]-5-methyl-4H-isoxazole-5-carboxylic acid ethyl ester (compound 1-139)

[0385] 1 H NMR (400 MHz, CDCl3) δ 8.8 (d,1H), 8.3 (d,1H), 7.8 (d,2H), 7.4 (m,1H), 7.35 (br d,1H), 4.3 (q,2H), 4.1 (d,1H), 3.45 (d,1H), 1.7 (s,3H), 1.3 (t,3H) ppm.

[0386] 3-[2-chloro-5-(5-chloro-2-fluoro-3-pyridyl)-4-fluoro-phenyl]-5-methyl-4H-isoxazole-5-carboxylic acid ethyl ester (compound 1-199)

[0387] 1 H NMR (400 MHz, CDCl3) δ 8.25 (s,1H), 7.85 (m,1H), 7.75 (d,1H), 7.35(d,1H), 4.3 (q,2H), 4.1 (d,1H), 3.45 (d,1H), 1.7 (s,3H), 1.3 (t,3H) ppm.

[0388] 3-[2-chloro-4-fluoro-5-[5-(trifluoromethyl)-2-pyridyl]phenyl]-5-methyl-4H-isoxazole-5-carboxylic acid ethyl ester (compounds 1-79)

[0389] 1 H NMR (400 MHz, CDCl3) δ 9.0 (s,1H), 8.35 (d,1H), 8.05 (d,1H), 7.9(d,1H), 7.35 (d,1H), 4.3 (q,2H), 4.1 (d,1H), 3.45 (d,1H), 1.7 (s,3H), 1.3 (t,3H) ppm.

[0390] 3-[2-chloro-5-(5-chloro-6-fluoro-3-pyridyl)-4-fluoro-phenyl]-5-methyl-4H-isoxazole-5-carboxylic acid ethyl ester (compound 1-403)

[0391] 1H NMR (400 MHz, CDCl3) δ 8.4 (s,1H), 7.85 (d,1H), 7.7 (m,1H), 7.35(d,1H), 4.3 (q,2H), 4.0 (d,1H), 3.45 (d,1H), 1.7 (s,3H), 1.3 (t,3H) ppm.

[0392] 3-[2-chloro-5-(5,6-difluoro-3-pyridyl)-4-fluoro-phenyl]-5-methyl-4H-isoxazole-5-carboxylic acid ethyl ester (compound 1-391)

[0393] 1 H NMR (400 MHz, CDCl3) δ 8.2 (s,1H), 7.8 (d,1H), 7.55 (dt,1H), 7.45(d,1H), 4.3 (q,2H), 4.05 (d,1H), 3.45 (d,1H), 1.7 (s,3H), 1.3 (t,3H) ppm.

[0394] 3-[2-chloro-5-(2,2-difluoro-[1,3]dioxo[4,5-b]pyridin-6-yl)-4-fluoro-phenyl]-5-methyl-4H-isoxazol-5-carboxylic acid ethyl ester (compound 1-451)

[0395] 1 H NMR (500 MHz, CDCl3) δ 8.15 (s,1H), 7.8 (d,1H), 7.5 (s,1H), 7.45(d,1H), 4.3 (q,2H), 4.05 (d,1H), 3.45 (d,1H), 1.7 (s,3H), 1.3 (t,3H) ppm.

[0396] 3-[2-chloro-4-fluoro-5-(3-quinolinyl)-phenyl]-5-methyl-4H-isoxazol-5-carboxylic acid ethyl ester (compound 1-439)

[0397] 1 H NMR (500 MHz, CDCl3) δ 9.1 (s,1H), 8.35 (s,1H), 8.2 (d,1H), 7.90(d,1H), 7.9 (d,1H), 7.75 (m,1H), 7.65 (d,1H), 7.35 (d,1H), 4.3 (q,2H), 4.05(d,1H), 3.45 (d,1H), 1.7 (s,3H), 1.3 (t,3H) ppm.

[0398] 3-[2-chloro-4-fluoro-5-(5-methoxy-3-pyridyl)-phenyl]-5-methyl-4H-isoxazole-5-carboxylic acid ethyl ester (compound 1-379)

[0399] 1 H NMR (500 MHz, CDCl3) δ 8.4 (m,2H), 7.80 (d,1H), 7.3 (m,2H), 4.3 (q,2H), 4.05 (d,1H), 3.9 (s,3H), 3.45 (d,1H), 1.7 (s,3H), 1.3 (t,3H) ppm.

[0400] 3-[2-chloro-5-(2-chloro-5-methoxy-4-pyridyl)-4-fluoro-phenyl]-5-methyl-4H-isoxazole-5-carboxylic acid ethyl ester (compound 1-511)

[0401] 1 H NMR (400 MHz, CDCl3) δ 8.15 (s,1H), 7.7 (d,1H), 7.45 (m,2H), 4.3(q,2H), 4.05 (d,1H), 3.95 (s,3H), 3.45 (d,1H), 1.7 (s,3H), 1.3 (t,3H) ppm.

[0402] 3-[2-chloro-5-(2-chloro-6-methoxy-4-pyridyl)-4-fluoro-phenyl]-5-methyl-4H-isoxazole-5-carboxylic acid ethyl ester (compound 1-523)

[0403] 1 H NMR (400 MHz, CDCl3) δ 7.8 (d,1H), 7.35 (d,1H) 7.15 (s,1H), 6.8 (s,1H), 4.3 (q,2H), 4.05 (d,1H), 4.0 (s,3H), 3.45 (d,1H), 1.7 (s,3H), 1.3 (t,3H)ppm.

[0404] 3-[2-chloro-4-fluoro-5-(2-fluoro-6-methyl-3-pyridyl)-phenyl]-5-methyl-4H-isoxazole-5-carboxylic acid ethyl ester (compound 1-463)

[0405] 1H NMR (400 MHz, CDCl3) δ 7.75 (d,1H), 7.7 (m,1H), 7.35 (d,1H) 7.15(d,1H), 4.3 (q,2H), 4.0 (d,1H), 3.4 (d,1H), 2.6 (s,3H), 1.7 (s,3H), 1.3 (t,3H) ppm.

[0406] 3-[2-chloro-4-fluoro-5-(6-fluoro-5-methoxy-3-pyridyl)-phenyl]-5-methyl-4H-isoxazole-5-carboxylic acid ethyl ester (compound 1-415)

[0407] 1 H NMR (400 MHz, CDCl3) δ 7.95 (t,1H), 7.8 (d,1H), 7.45 (d,1H), 7.35(d,1H) 4.3 (q,2H), 4.05 (d,1H), 3.95 (s,3H), 3.45 (d,1H), 1.7 (s,3H), 1.3 (t,3H) ppm.

[0408] 3-[2-chloro-4-fluoro-5-[2-(trifluoromethyl)-4-pyridyl]-phenyl]-5-methyl-4H-isoxazole-5-carboxylic acid ethyl ester (compound 1-499)

[0409] 1 H NMR (400 MHz, CDCl3) δ 8.5 (d,1H), 7.9 (m,2H), 7.7 (d,1H) 7.4 (d,1H), 4.3 (q,2H), 4.1 (d,1H), 3.45 (d,1H), 1.7 (s,3H), 1.3 (t,3H) ppm.

[0410] 3-[2-chloro-4-fluoro-5-(4-pyridyl)-phenyl]-5-methyl-4H-isoxazole-5-carboxylic acid ethyl ester (compound 1-487)

[0411] 1 H NMR (400 MHz, CDCl3) δ 8.7 (d,2H), 7.85 (d,1H), 7.45 (m,2H), 4.3(q,2H), 4.0 (d,1H), 3.45 (d,1H), 1.75 (s,3H), 1.35 (t,3H) ppm.

[0412] 3-[2-chloro-4-fluoro-5-(6-fluoro-4-methyl-2-pyridyl)-phenyl]-5-methyl-4H-isoxazole-5-carboxylic acid ethyl ester (compound 1-367)

[0413] 1 H NMR (400 MHz, CDCl3) δ 8.3 (d,1H), 7.55 (s,1H), 7.3 (d,1H), 6.75(s,1H), 4.3 (q,2H), 4.0 (d,1H), 3.45 (d,1H), 2.5 (s,3H), 1.7 (s,3H), 1.3 (t,3H) ppm.

[0414] 3-[2-chloro-5-(5,6-dichloro-3-pyridyl)-4-fluoro-phenyl]-5-methyl-4H-isoxazole-5-carboxylic acid ethyl ester (compound 1-427)

[0415] 1 H NMR (400 MHz, CDCl3) δ 8.5 (d,1H), 8.0 (d,1H), 7.8 (d,1H), 7.35 (d,1H), 4.3 (q,2H), 4.1 (d,1H), 3.45 (d,1H), 1.7 (s,3H), 1.3 (t,3H) ppm.

[0416] 20-67045 3-[2-chloro-5-(2,3-dichloro-4-pyridyl)-4-fluoro-phenyl]-5-methyl-4H-isoxazole-5-carboxylic acid ethyl ester (compound 1-535)

[0417] 1 H NMR (400 MHz, CDCl3) δ 8.25 (s,1H), 7.85 (m,1H), 7.75 (d,1H), 7.35(d,1H), 4.3 (q,2H), 4.1 (d,1H), 3.45 (d,1H), 1.7 (s,3H), 1.3 (t,3H) ppm.

[0418] 3-[2-cyano-5-(2,2-difluoro-[1,3]dioxo[4,5-b]pyridin-6-yl)phenyl]-5-methyl-4H-isoxazole-5-carboxylic acid ethyl ester (compound 2-451)

[0419] 1H NMR (400 MHz, CDCl3) δ 8.2 (d,1H), 8.05 (d,1H), 7.85 (d,1H), 7.7(dd,1H), 7.6 (d,1H), 4.3 (q,2H), 4.05 (d,1H), 3.55 (d,1H), 1.8 (s,3H), 1.35(t,3H) ppm.

[0420] Example 2: Preparation of ethyl 3-[2-chloro-5-(3-chloro-5-trifluoromethyl-2-pyridyl)-4-fluoro-phenyl]-5-methyl-4H-isoxazole-5-carboxylate (compound 1-103)

[0421] Step 1: Synthesis of (5-bromo-2-chloro-4-fluoro-phenyl)methanol

[0422]

[0423] A boronane dimethyl sulfide complex (3 ml, 33 mmol) was added dropwise over 10 minutes at 0°C to a stirred solution of 5-bromo-2-chloro-4-fluorobenzoic acid (10 g, 28 mmol) in tetrahydrofuran (300 ml). The resulting mixture was heated to room temperature over 30 minutes and then heated at 70°C for 3 hours. The mixture was cooled to 0°C, and methanol was slowly added until bubbling ceased. The mixture was extracted with ethyl acetate, and the organic phase was washed with an aqueous sodium hydroxide solution (2 M, 10 ml), dried, and evaporated under reduced pressure to provide (5-bromo-2-chloro-4-fluorophenyl)methanol (7.0 g) as a solid.

[0424] 1 ¹H NMR (400 MHz, CDCl₃) δ 7.7 (d, 1H), 7.15 (d, 1H), 4.75 (s, 2H) ppm (OH not observed).

[0425] Step 2: Synthesis of [2-chloro-4-fluoro-5-(4,4,5,5-tetramethyl-1,3,2-dioxacyclopentaborane-2-yl)phenyl]methanol

[0426]

[0427] Potassium acetate (1.8 g, 18 mmol) and [1,1'-bis(diphenylphosphino)ferrocene]palladium dichloride (0.45 g, 0.61 mmol) were added to a solution of (5-bromo-2-chloro-4-fluoro-phenyl)methanol (1.5 g, 6.1 mmol) and dipentanoyl diboron (2.4 ml, 9.1 mmol) in dioxane (30 ml). The mixture was heated at 85°C for 3 hours, then heated under reflux for 17 hours. After cooling, ethyl acetate (100 ml) was added, and the mixture was filtered and evaporated under reduced pressure. The resulting oil was purified by chromatography to yield [2-chloro-4-fluoro-5-(4,4,5,5-tetramethyl-1,3,2-dioxane-2-yl)phenyl]methanol (1.35 g) as a white solid.

[0428] 1 H NMR (400 MHz, CDCl3) δ 7.85 (d,1H), 7.1 (d,1H), 4.75 (s,2H), 1.35(s,12H) ppm.

[0429] Step 3: Synthesis of 2-chloro-4-fluoro-5-(4,4,5,5-tetramethyl-1,3,2-dioxacyclopentaborane-2-yl)benzaldehyde

[0430]

[0431] Pyridinium dichromate (0.83 g, 5.0 mmol) was added to a stirred solution of [2-chloro-4-fluoro-5-(4,4,5,5-tetramethyl-1,3,2-dioxacyclopentaborane-2-yl)phenyl]methanol (750 g, 2.5 mmol) in dichloromethane (37.5 ml). The resulting mixture was stirred at room temperature for 15 hours, then filtered under reduced pressure and evaporated to leave a residue, which was purified by chromatography to provide 2-chloro-4-fluoro-5-(4,4,5,5-tetramethyl-1,3,2-dioxacyclopentaborane-2-yl)benzaldehyde (340 mg) as an oil.

[0432] 1 H NMR (400 MHz, CDCL3) δ 10.7 (s,1H), 8.4 (d,1H), 7.2 (d,1H), 1.35(s,12H) ppm.

[0433] Step 4: Synthesis of 2-chloro-4-fluoro-5-(4,4,5,5-tetramethyl-1,3,2-dioxacyclopentaborane-2-yl)benzaldehyde oxime

[0434]

[0435] Hydroxylamine hydrochloride (0.15 g, 2.1 mmol) was added to a stirred solution of 2-chloro-4-fluoro-5-(4,4,5,5-tetramethyl-1,3,2-dioxacyclopentaborane-2-yl)benzaldehyde (0.4 g, 1.4 mmol) in tetrahydrofuran (6 ml) at room temperature. Water (0.8 ml) was added and the resulting solution was stirred at room temperature for 60 minutes. Water was added and the resulting mixture was extracted with ethyl acetate. The combined organic phases were dried and evaporated under reduced pressure to leave a residue, which was purified by chromatography to provide 2-chloro-4-fluoro-5-(4,4,5,5-tetramethyl-1,3,2-dioxacyclopentaborane-2-yl)benzaldehyde oxime (2.5 g) as an oil.

[0436] 1 H NMR (400 MHz, CDCl3) δ 8.5 (s,1H), 8.25 (d,1H), 7.7 (br s,1H), 7.15(d,1H), 1.35 (s,12H) ppm.

[0437] Step 5: Synthesis of ethyl 3-[2-chloro-4-fluoro-5-(4,4,5,5-tetramethyl-1,3,2-dioxaneborane-2-yl)phenyl]-5-methyl-4H-isoxazole-5-carboxylate

[0438]

[0439] 1-Chloroprene-2,5-dione (93 mg, 0.68 mmol) was added in portions at 35°C to a stirred solution of 2-chloro-4-fluoro-5-(4,4,5,5-tetramethyl-1,3,2-dioxane-2-yl)benzaldehyde oxime (0.17 g, 0.57 mmol) in N,N-dimethylformamide (0.85 ml). The resulting mixture was stirred at 30°C for 1 hour, then cooled to room temperature and water (20 ml) was added. Dichloromethane (50 ml) was added, the phases were separated, and the organic phase was dried and cooled to 5°C. A mixture of triethylamine (0.07 ml, 0.51 mmol) and ethyl 2-methylprop-2-enoate (0.07 ml, 0.56 mmol) was added dropwise to this stirred solution. After stirring at room temperature for 1 hour, dilute hydrochloric acid (5 ml) was added, the phases were separated, and the organic phase was dried and purified by chromatography to provide ethyl 3-[2-chloro-4-fluoro-5-(4,4,5,5-tetramethyl-1,3,2-dioxaneborane-2-yl)phenyl]-5-methyl-4H-isoxazole-5-carboxylate (29 mg) as an oil.

[0440] 1 H NMR (400 MHz, CDCl3) δ 8.0 (d,1H), 7.25 (d,1H), 4.3 (q,2H), 3.95(d,1H), 3.35 (d,1H), 1.75 (s,3H), 1.35 (m,15H) ppm.

[0441] Step 6: Synthesis of ethyl 3-[2-chloro-5-(3-chloro-5-trifluoromethyl-2-pyridyl)-4-fluoro-phenyl]-5-methyl-4H-isoxazole-5-carboxylate (compound 1-103)

[0442]

[0443] Potassium acetate (22 mg, 0.22 mmol) and [1,1'-bis(diphenylphosphino)ferrocene]palladium dichloride (5 mg, 0.007 mmol) were added to a solution of 3-[2-chloro-4-fluoro-5-(4,4,5,5-tetramethyl-1,3,2-dioxacyclopentaborane-2-yl)phenyl]-5-methyl-4H-isooxazol-5-carboxylate (30 mg, 0.07 mmol) and 2,3-dichloro-5-trifluoromethyl-pyridine (24 mg, 0.11 mmol) in dioxane (1.2 ml). The mixture was heated in a microwave oven at 100°C for 45 minutes, cooled, and ethyl acetate (10 ml) was added. The mixture was then filtered and evaporated under reduced pressure. The resulting oil was purified by chromatography to produce ethyl 3-[2-chloro-5-(3-chloro-5-trifluoromethyl-2-pyridyl)-4-fluoro-phenyl]-5-methyl-4H-isoxazole-5-carboxylate (compound 1-103) as a gel.

[0444] 1 H NMR (400 MHz, CDCl3) δ 8.85 (s,1H), 8.1 (s,1H), 7.85 (d,1H), 7.35(d,1H), 4.3 (q,2H), 4.05 (d,1H), 3.4 (d,1H), 1.75 (s,3H), 1.35 (t,3H) ppm.

[0445] Also prepared by this general method are:

[0446] 3-[2-chloro-5-(3-chloro-5-methyl-2-pyridyl)-4-fluoro-phenyl]-5-methyl-4H-isoxazole-5-carboxylic acid ethyl ester (compound 1-175)

[0447] 1H NMR (500 MHz, CDCl3) δ 8.55 (s,1H), 7.80 (s,1H), 7.75 (d,1H), 7.4(d,1H), 4.3 (q,2H), 4.05 (d,1H), 3.45 (d,1H), 2.5 (s,3H), 1.7 (s,3H), 1.3(t,3H) ppm.

[0448] 3-[2-chloro-4-fluoro-5-[4-(trifluoromethyl)-2-pyridyl]-phenyl]-5-methyl-4H-isoxazole-5-carboxylic acid ethyl ester (compound 1-319)

[0449] 1 H NMR (400 MHz, CDCl3) δ 9.0 (d,1H), 8.3 (d,1H), 8.05 (s,1H), 7.65(d,1H), 7.35 (d,1H), 4.3 (q,2H), 4.05 (d,1H), 3.4 (d,1H), 1.75 (s,3H), 1.35(t,3H) ppm.

[0450] 3-[2-chloro-4-fluoro-5-[3-fluoro-5-(trifluoromethyl)-2-pyridyl]-phenyl]-5-methyl-4H-isoxazole-5-carboxylic acid ethyl ester (compounds 1-91)

[0451] 1 H NMR (400 MHz, CDCl3) δ 8.85 (s,1H), 8.05 (d,1H), 7.8 (m,1H), 7.35(d,1H), 4.3 (q,2H), 4.05 (d,1H), 3.4 (d,1H), 1.75 (s,3H), 1.35 (t,3H) ppm.

[0452] 3-[2-chloro-5-[5-chloro-3-(trifluoromethyl)-2-pyridyl]-4-fluoro-phenyl]-5-methyl-4H-isoxazole-5-carboxylic acid ethyl ester (compound 1-343)

[0453] 1 H NMR (400 MHz, CDCl3) δ 8.85 (s,1H), 8.15 (s,1H), 7.7 (d,1H), 7.3(d,1H), 4.3 (q,2H), 3.95 (d,1H), 3.45 (d,1H), 1.75 (s,3H), 1.35 (t,3H) ppm.

[0454] 3-[2-chloro-5-(3,5-difluoro-2-pyridyl)-4-fluoro-phenyl]-5-methyl-4H-isoxazole-5-carboxylic acid ethyl ester (compound 1-551)

[0455] 1 H NMR (400 MHz, CDCl3) δ 8.5 (s,1H), 7.9 (d,1H), 7.35 (td,1H), 7.3(d,1H), 4.3 (q,2H), 4.0 (d,1H), 3.4 (d,1H), 1.7 (s,3H), 1.3 (t,3H) ppm.

[0456] 3-[2-chloro-4-fluoro-5-[3-(trifluoromethyl)pyrazin-2-yl]phenyl]-5-methyl-4H-isoxazole-5-carboxylic acid ethyl ester (compound 1-823)

[0457] 1 H NMR (400 MHz, CDCl3) δ 8.95 (s,1H), 8.8 (s,1H), 7.8 (m,1H), 7.45(d,1H), 4.3 (q,2H), 4.05 (d,1H), 3.4 (d,1H), 1.75 (s,3H), 1.35 (t,3H) ppm.

[0458] 3-[2-chloro-4-fluoro-5-[5-(trifluoromethyl)pyrazin-2-yl]phenyl]-5-methyl-4H-isoxazole-5-carboxylic acid ethyl ester (compound 1-751)

[0459] 1 H NMR (400 MHz, CDCl3) δ 9.25 (s,1H), 9.05 (s,1H), 8.5 (d,1H), 7.4(d,1H), 4.3 (q,2H), 4.05 (d,1H), 3.4 (d,1H), 1.75 (s,3H), 1.35 (t,3H) ppm.

[0460] 3-[2-chloro-4-fluoro-5-[6-(trifluoromethyl)pyrazin-2-yl]phenyl]-5-methyl-4H-isoxazole-5-carboxylic acid ethyl ester (compound 1-727)

[0461] 1H NMR (400 MHz, CDCl3) δ 9.35 (s,1H), 8.95 (s,1H), 8.4 (d,1H), 7.4(d,1H), 4.3 (q,2H), 4.05 (d,1H), 3.4 (d,1H), 1.75 (s,3H), 1.35 (t,3H) ppm.

[0462] 3-[2-chloro-4-fluoro-5-(3-methylpyrazin-2-yl)phenyl]-5-methyl-4H-isoxazole-5-carboxylic acid ethyl ester (compound 1-775)

[0463] 1 H NMR (400 MHz, CDCl3) δ 8.55 (br s,2H), 7.8 (d,1H), 7.35 (d,1H), 4.3(q,2H), 4.0 (d,1H), 3.4 (d,1H), 2.55 (s,3H), 1.7 (s,3H), 1.3 (t,3H) ppm.

[0464] 3-[2-chloro-4-fluoro-5-(5-methylpyrazin-2-yl)phenyl]-5-methyl-4H-isoxazole-5-carboxylic acid ethyl ester (compound 1-739)

[0465] 1 H NMR (400 MHz, CDCl3) δ 8.95 (br s,1H), 8.6 (br s,1H), 8.3 (m,1H),7.35 (d,1H), 4.3 (q,2H), 4.0 (d,1H), 3.4 (d,1H), 2.6 (s,3H), 1.7 (s,3H), 1.3(t,3H) ppm.

[0466] 3-[2-chloro-5-(3,6-dimethylpyrazin-2-yl)-4-fluoro-phenyl]-5-methyl-4H-isoxazole-5-carboxylic acid ethyl ester (compound 1-787)

[0467] 1 H NMR (400 MHz, CDCl3) δ 8.45 (s,1H), 7.85 (m,1H), 7.35 (d,1H), 4.3(q,2H), 4.05 (d,1H), 3.4 (d,1H), 2.6 (s,3H), 2.5 (s,3H), 1.75 (s,3H), 1.35(t,3H) ppm.

[0468] 3-[2-chloro-5-(6-chloropyridazin-3-yl)-4-fluoro-phenyl]-5-methyl-4H-isoxazole-5-carboxylic acid ethyl ester (compound 1-679)

[0469] 1 H NMR (400 MHz, CDCl3) δ 8.9 (s,1H), 8.65 (s,1H), 8.0 (d,1H), 7.4 (d,1H), 4.3 (q,2H), 4.05 (d,1H), 3.4 (d,1H), 1.75 (s,3H), 1.3 (t,3H) ppm.

[0470] 3-[2-chloro-4-fluoro-5-(6-methoxypyridazin-3-yl)phenyl]-5-methyl-4H-isoxazole-5-carboxylic acid ethyl ester (compound 1-703)

[0471] 1 H NMR (400 MHz, CDCl3) δ 8.4 (d,1H), 7.85 (dd,1H), 7.3 (d,1H), 7.05(d,1H), 4.25 (q,2H), 4.2 (s,3H), 4.0 (d,1H), 3.4 (d,1H), 1.7 (s,3H), 1.3 (t,3H) ppm.

[0472] 3-[2-chloro-4-fluoro-5-[7-(trifluoromethyl)quinoxalin-2-yl]phenyl]-5-methyl-4H-isoxazol-5-carboxylic acid ethyl ester (compound 1-763)

[0473] 1 H NMR (400 MHz, CDCl3) δ 9.4 (d,1H), 8.55 (d,1H), 8.5 (m,1H), 8.3 (d,1H), 8.0 (m,1H), 7.4 (d,1H), 4.3 (q,2H), 4.05 (d,1H), 3.4 (d,1H), 1.75 (s,3H), 1.35 (t,3H) ppm.

[0474] 3-[2-chloro-5-[3-chloro-5-(trifluoromethyl)pyrazin-2-yl]-4-fluoro-phenyl]-5-methyl-4H-isoxazole-5-carboxylic acid ethyl ester (1-811)

[0475] 1H NMR (400 MHz, CDCl3) δ 9.0 (s,1H), 7.95 (d,1H), 7.4 (d,1H), 4.3 (q,2H), 4.05 (d,1H), 3.45 (d,1H), 1.75 (s,3H), 1.35 (t,3H) ppm.

[0476] 3-[2-chloro-5-[2-chloro-6-(trifluoromethyl)-3-pyridyl]-4-fluoro-phenyl]-5-methyl-4H-isoxazole-5-carboxylic acid ethyl ester (compound 1-655)

[0477] 1 H NMR (400 MHz, CDCl3) δ 7.85 (d,1H), 7.75 (m,2H), 7.35 (d,1H), 4.3(q,2H), 4.05 (d,1H), 3.45 (d,1H), 1.75 (s,3H), 1.35 (t,3H) ppm.

[0478] 3-[5-(5-bromo-3-chloro-2-pyridyl)-2-chloro-4-fluoro-phenyl]-5-methyl-4H-isoxazole-5-carboxylic acid ethyl ester (compound 1-559)

[0479] 1 H NMR (400 MHz, CDCl3) δ 8.65 (s,1H), 8.0 (s,1H), 7.8 (d,1H), 7.3 (d,1H), 4.3 (q,2H), 4.0 (d,1H), 3.4 (d,1H), 1.75 (s,3H), 1.35 (t,3H) ppm.

[0480] 3-[2-chloro-5-(3-chloro-5-methylsulfonyl-2-pyridyl)-4-fluoro-phenyl]-5-methyl-4H-isoxazole-5-carboxylic acid ethyl ester (compound 1-643)

[0481] 1 H NMR (400 MHz, CDCl3) δ 9.1 (d,1H), 8.35 (d,1H), 7.85 (d,1H), 7.35(d,1H), 4.3 (q,2H), 4.0 (d,1H), 3.4 (d,1H), 3.2 (s,3H), 1.75 (s,3H), 1.35 (t,3H) ppm.

[0482] 3-[2-chloro-5-(3-chloro-5-cyano-2-pyridyl)-4-fluoro-phenyl]-5-methyl-4H-isoxazole-5-carboxylic acid ethyl ester (compound 1-607)

[0483] 1 H NMR (400 MHz, CDCl3) δ 8.9 (d,1H), 8.15 (d,1H), 7.85 (d,1H), 7.35(d,1H), 4.3 (q,2H), 4.05 (d,1H), 3.45 (d,1H), 1.75 (s,3H), 1.35 (t,3H) ppm.

[0484] 3-[5-(5-acetyl-3-chloro-2-pyridyl)-2-chloro-4-fluoro-phenyl]-5-methyl-4H-isoxazole-5-carboxylic acid ethyl ester (compound 1-631)

[0485] 1 H NMR (400 MHz, CDCl3) δ 9.1 (d,1H), 8.35 (d,1H), 7.85 (d,1H), 7.35(d,1H), 4.3 (q,2H), 4.05 (d,1H), 3.45 (d,1H), 2.7 (s,3H), 1.75 (s,3H), 1.35(t,3H) ppm.

[0486] 3-[5-[3-bromo-5-(trifluoromethyl)-2-pyridyl]-2-chloro-4-fluoro-phenyl]-5-methyl-4H-isoxazole-5-carboxylic acid ethyl ester (compound 1-571)

[0487] 1 H NMR (400 MHz, CDCl3) δ 8.9 (d,1H), 8.25 (d,1H), 7.8 (d,1H), 7.35(d,1H), 4.3 (q,2H), 4.05 (d,1H), 3.45 (d,1H), 1.75 (s,3H), 1.35 (t,3H) ppm.

[0488] 3-[5-[2-bromo-5-(trifluoromethyl)-3-pyridyl]-2-chloro-4-fluoro-phenyl]-5-methyl-4H-isoxazole-5-carboxylic acid ethyl ester (compound 1-835)

[0489] 1H NMR (400 MHz, CDCl3) δ 8.7 (s,1H), 7.85 (d,1H), 7.7 (d,1H), 7.35(d,1H), 4.3 (q,2H), 4.05 (d,1H), 3.45 (d,1H), 1.75 (s,3H), 1.35 (t,3H) ppm.

[0490] 3-[2-chloro-5-[3-chloro-5-(difluoromethyl)-2-pyridyl]-4-fluoro-phenyl]-5-methyl-4H-isoxazole-5-carboxylic acid ethyl ester (compound 1-583)

[0491] 1 H NMR (400 MHz, CDCl3) δ 8.75 (d,1H), 8.0 (s,1H), 7.85 (d,1H), 7.35(d,1H), 6.8 (t,1H), 4.3 (q,2H), 4.05 (d,1H), 3.45 (d,1H), 1.75 (s,3H), 1.35(t,3H) ppm.

[0492] 3-[5-(4-amino-6-chloro-pyridazin-3-yl)-2-chloro-4-fluoro-phenyl]-5-methyl-4H-isoxazole-5-carboxylic acid ethyl ester

[0493] 1 ¹H NMR (400 MHz, CDCl₃) δ 7.9 (d, 1H), 7.75 (d, 1H), 7.55 (s, 1H), 4.3 (q, 2H), 4.05 (d, 1H), 3.45 (d, 1H), 1.75 (s, 3H), 1.35 (t, 3H) ppm (NH₂ not observed).

[0494] Example 3: Alternative preparation of ethyl 3-[2-chloro-5-(3-chloro-5-trifluoromethyl-2-pyridyl)-4-fluoro-phenyl]-5-methyl-4H-isoxazole-5-carboxylate (compound 1-103)

[0495] Step 1: Synthesis of [2-chloro-5-[3-chloro-5-(trifluoromethyl)-2-pyridyl]-4-fluoro-phenyl]methanol

[0496]

[0497] Potassium acetate (2.5 g, 25 mmol) and [1,1'-bis(diphenylphosphino)ferrocene]palladium dichloride (0.74 g, 1 mmol) were added to a mixture of 3-[2-chloro-4-fluoro-5-(4,4,5,5-tetramethyl-1,3,2-dioxacyclopentaborane-2-yl)phenyl]-5-methyl-4H-isoxazol-5-carboxylate (prepared as described in step 2 of Example 2; 2.86 mg, 10 mmol) and 2,3-dichloro-5-trifluoromethyl-pyridine (2.83 g, 13 mmol) in toluene (57 ml) and water (29 ml). The mixture was heated under reflux for 17 hours, cooled, and ethyl acetate (50 ml) was added, followed by separation of the phases. The organic phase was dried and evaporated under reduced pressure to leave a red oily substance, which was purified by chromatography to produce ethyl[2-chloro-5-[3-chloro-5-(trifluoromethyl)-2-pyridyl]-4-fluoro-phenyl]methanol (1.0 g) as a white solid.

[0498] 1 H NMR (400 MHz, CDCl3) δ 8.85 (s,1H), 8.1 (s,1H), 7.65 (d,1H), 7.25(d,1H), 4.8 (d,2H), 2.0 (t,1H) ppm.

[0499] Also prepared by this general method are:

[0500] [2-chloro-5-(3-chloro-5-fluoro-2-pyridyl)-4-fluoro-phenyl]-methanol

[0501] [2-chloro-5-(2-chloro-5-fluoro-3-pyridyl)-4-fluoro-phenyl]-methanol

[0502] [2-chloro-5-(3-chloro-5-nitro-2-pyridyl)-4-fluoro-phenyl]-methanol

[0503] [2-chloro-5-(3-chloro-2-pyridyl)-4-fluoro-phenyl]-methanol

[0504] 1 H NMR (400 MHz, CDCl3) δ 8.6 (d,1H), 7.8 (d,1H), 7.6 (d,1H), 7.45(dd,1H), 7.2 (d,1H), 4.75 (s,2H), 2.25 (br s,1H) ppm.

[0505] [2-chloro-5-(3,5-dichloro-2-pyridyl)-4-fluoro-phenyl]-methanol

[0506] 1 H NMR (400 MHz, CDCl3) δ 8.6 (s,1H), 7.85 (d,1H), 7.65 (d,1H), 7.45(dd,1H), 4.8 (d,2H), 1.95 (t,1H) ppm.

[0507] Step 2: Synthesis of 2-chloro-5-[3-chloro-5-(trifluoromethyl)-2-pyridyl]-4-fluorobenzaldehyde

[0508]

[0509] Pyridinium dichromate (0.32 g, 1.9 mmol) was added to a stirred solution of [2-chloro-5-[3-chloro-5-(trifluoromethyl)-2-pyridyl]-4-fluoro-phenyl]methanol (300 mg, 0.88 mmol) in dichloromethane (10 ml). The resulting mixture was stirred at room temperature for 5 hours, then filtered under reduced pressure and evaporated to leave a residue, which was purified by chromatography to provide 2-chloro-5-[3-chloro-5-(trifluoromethyl)-2-pyridyl]-4-fluoro-benzaldehyde (210 mg) as an oil.

[0510] 1 H NMR (400 MHz, CDCl3) δ 10.5 (s,1H), 8.9 (br s,1H), 8.15 (d,1H), 8.1(d,1H), 7.35 (d,1H ppm.

[0511] Also prepared by this general method are:

[0512] 2-Chloro-5-[3-Chloro-5-(trifluoromethyl)-2-pyridyl]-benzaldehyde

[0513] 2-Chloro-5-(3-Chloro-5-fluoro-2-pyridyl)-4-fluoro-benzaldehyde

[0514] 2-Chloro-5-(2-Chloro-5-fluoro-3-pyridyl)-4-fluoro-benzaldehyde

[0515] 2-Chloro-5-(3-Chloro-5-nitro-2-pyridyl)-4-fluoro-benzaldehyde

[0516] 2-Chloro-5-(3-Chloro-2-pyridyl)-4-fluoro-benzaldehyde

[0517] 1H NMR (400 MHz, CDCl3) δ 10.4 (s,1H), 8.65 (d,1H), 8.15 (d,1H), 7.85(d,1H), 7.35 (d,1H), 7.3 (d,1H) ppm.

[0518] 2-Chloro-5-(3,5-dichloro-2-pyridyl)-4-fluorobenzaldehyde

[0519] Step 3: Synthesis of 2-chloro-5-[3-chloro-5-(trifluoromethyl)-2-pyridyl]-4-fluorobenzaldehyde oxime

[0520]

[0521] Hydroxylamine hydrochloride (49 mg, 0.71 mmol) was added to a stirred solution of 2-chloro-5-[3-chloro-5-(trifluoromethyl)-2-pyridyl]-4-fluorobenzaldehyde (0.20 g, 0.47 mmol) in tetrahydrofuran (1 ml) at room temperature. Water (0.2 ml) was added and the resulting solution was stirred at room temperature for 60 minutes. The mixture was concentrated under reduced pressure, and then dichloromethane and water were added and the phases were separated. The organic phase was dried and evaporated under reduced pressure to leave a residue, which was purified by chromatography to provide 2-chloro-5-[3-chloro-5-(trifluoromethyl)-2-pyridyl]-4-fluorobenzaldehyde oxime (170 mg) as a white solid.

[0522] 1 ¹H NMR (400 MHz, CD3OD) δ 8.95 (s, 1H), 8.45 (s, 1H), 8.4 (s, 1H), 8.05 (d, 1H), 7.45 (d, 1H) ppm (OH not observed).

[0523] Also prepared by this general method are:

[0524] 2-Chloro-5-[3-Chloro-5-(trifluoromethyl)-2-pyridyl]-benzaldehyde oxime

[0525] 1 H NMR (400 MHz, CDCl3) δ 8.85 (s,1H), 8.6 (s,1H), 8.3 (s,1H), 8.05(s,1H), 7.85 (br s,1H), 7.7 (d,1H), 7.5 (d,1H) ppm.

[0526] 2-Chloro-5-(3-Chloro-5-fluoro-2-pyridyl)-4-fluoro-benzaldehyde oxime

[0527] 2-Chloro-5-(2-Chloro-5-fluoro-3-pyridyl)-4-fluoro-benzaldehyde oxime

[0528] 2-Chloro-5-(3-Chloro-5-nitro-2-pyridyl)-4-fluoro-benzaldehyde oxime

[0529] 2-Chloro-5-(3-Chloro-2-pyridyl)-4-fluoro-benzaldehyde oxime

[0530] 2-Chloro-5-(3,5-dichloro-2-pyridyl)-4-fluoro-benzaldehyde oxime

[0531] Step 4: Synthesis of ethyl 3-[2-chloro-5-[3-chloro-5-(trifluoromethyl)-2-pyridyl]-4-fluoro-phenyl]-5-methyl-4H-isoxazole-5-carboxylate (compound 1-103)

[0532]

[0533] 1-Chloroprene-2,5-dione (240 mg, 1.7 mmol) was added in portions to a stirred solution of 2-chloro-5-[3-chloro-5-(trifluoromethyl)-2-pyridyl]-4-fluoro-benzaldehyde oxime (0.85 g, 1.4 mmol) in N,N-dimethylformamide (4.3 ml) at 35°C. The resulting mixture was stirred at 30°C for 1 hour, then cooled to room temperature and water (20 ml) was added. Dichloromethane (50 ml) was added, the phases were separated, and the organic phase was dried and cooled to 5°C. A mixture of triethylamine (0.33 ml, 2.3 mmol) and ethyl 2-methylprop-2-enoate (0.34 ml, 2.6 mmol) was added dropwise to this stirred solution. After stirring at room temperature for 1 hour, dilute hydrochloric acid (5 ml) was added, the phases were separated, and the organic phase was dried and purified by chromatography to provide ethyl 3-[2-chloro-5-[3-chloro-5-(trifluoromethyl)-2-pyridyl]-4-fluoro-phenyl]-5-methyl-4H-isoxazole-5-carboxylate (compound 1-103) (550 mg) as an oil.

[0534] 1 H NMR (400 MHz, CDCl3) δ 8.85 (s,1H), 8.1 (s,1H), 7.85 (d,1H), 7.35(d,1H), 4.3 (q,2H), 4.05 (d,1H), 3.4 (d,1H), 1.75 (s,3H), 1.35 (t,3H) ppm.

[0535] By chiral chromatography (as described above) 1 The single enantiomers of compound 1-103 were prepared by ¹H NMR.

[0536] Also prepared by this general method are:

[0537] 3-[2-chloro-5-[3-chloro-5-(trifluoromethyl)-2-pyridyl]-phenyl]-5-methyl-4H-isoxazole-5-carboxylic acid ethyl ester (compound 1-99)

[0538] 1 H NMR (400 MHz, CDCl3) δ 8.85 (s,1H), 8.1 (d,1H), 8.05 (s,1H), 7.8(dd,1H), 7.55 (d,1H), 4.3 (q,2H), 4.0 (d,1H), 3.45 (d,1H), 1.75 (s,3H), 1.35(t,3H) ppm.

[0539] 3-[2-chloro-5-(3-chloro-5-fluoro-2-pyridyl)-4-fluoro-phenyl]-5-methyl-4H-isoxazole-5-carboxylic acid ethyl ester (compound 1-331)

[0540] 1 H NMR (400 MHz, CDCl3) δ 8.5 (s,1H), 7.8 (d,1H), 7.65 (m,1H), 7.3(d,1H), 4.3 (q,2H), 4.05 (d,1H), 3.35 (d,1H), 1.7 (s,3H), 1.3 (t,3H) ppm.

[0541] 3-[2-chloro-5-(2-chloro-5-fluoro-3-pyridyl)-4-fluoro-phenyl]-5-methyl-4H-isoxazole-5-carboxylic acid ethyl ester (compound 1-475)

[0542] 1 H NMR (400 MHz, CDCl3) δ 8.35 (s,1H), 7.7 (d,1H), 7.45 (m,1H), 7.3(d,1H), 4.3 (q,2H), 4.0 (d,1H), 3.4 (d,1H), 1.75 (s,3H), 1.3 (t,3H) ppm.

[0543] 3-[2-chloro-5-(3-chloro-5-nitro-2-pyridyl)-4-fluoro-phenyl]-5-methyl-4H-isoxazole-5-carboxylic acid ethyl ester (compound 1-355)

[0544] 1H NMR (400 MHz, CDCl3) δ 9.45 (s,1H), 8.65 (s,H), 7.9 (d,1H), 7.35(d,1H), 4.3 (q,2H), 4.05 (d,1H), 3.4 (d,1H), 1.75 (s,3H), 1.35 (t,3H) ppm.

[0545] 3-[2-chloro-5-(3-chloro-2-pyridyl)-4-fluoro-phenyl]-5-methyl-4H-isoxazole-5-carboxylic acid ethyl ester (compound 1-127)

[0546] 1 H NMR (400 MHz, CDCl3) δ 8.65 (d,1H), 7.75 (m,2H), 7.35 (m,1H), 7.3(d,1H), 4.3 (q,2H), 4.05 (d,1H), 3.4 (d,1H), 1.75 (s,3H), 1.35 (t,3H) ppm.

[0547] 3-[2-chloro-5-(3,5-dichloro-2-pyridyl)-4-fluoro-phenyl]-5-methyl-4H-isoxazole-5-carboxylic acid ethyl ester (compound 1-115)

[0548] 1 H NMR (400 MHz, CDCl3) δ 8.85 (d,1H), 7.9 (d,1H), 7.85 (d,1H), 7.35(d,1H), 4.3 (q,2H), 4.05 (d,1H), 3.4 (d,1H), 1.75 (s,3H), 1.35 (t,3H) ppm.

[0549] Example 4: Preparation of 3-[2-chloro-5-(3-chloro-5-trifluoromethyl-2-pyridyl)-4-fluoro-phenyl]-5-methyl-4H-isoxazole-5-carboxylic acid (compound 1-101)

[0550]

[0551] Concentrated sulfuric acid (0.5 ml, 9 mmol) was added to a stirred solution of 3-[2-chloro-5-(3-chloro-5-trifluoromethyl-2-pyridyl)-4-fluoro-phenyl]-5-methyl-4H-isoxazole-5-carboxylic acid (prepared as described in step 4 of Example 3; 200 mg, 0.43 mmol) in glacial acetic acid (4 ml), and the resulting mixture was heated at 100°C for 1 hour. The mixture was cooled to ambient temperature, evaporated under reduced pressure, and then toluene (2 x 10 ml) was added and the solution was evaporated under reduced pressure to leave a residue, which was purified by chromatography to provide 3-[2-chloro-5-(3-chloro-5-trifluoromethyl-2-pyridyl)-4-fluoro-phenyl]-5-methyl-4H-isoxazole-5-carboxylic acid (compound 1-101) (160 mg) as a white solid.

[0552] 1 ¹H NMR (400 MHz, CDCl₃) δ 8.9 (s, 1H), 8.15 (s, 1H), 7.8 (d, 1H), 7.35 (s, 1H), 4.0 (d, 1H), 3.5 (d, 1H), 1.7 (s, 3H) ppm (no acid protons observed).

[0553] Example 5: Preparation of [2-chloro-5-(3-chloro-5-trifluoromethyl-2-pyridyl)-phenyl]-methanol

[0554] Step 1: Synthesis of methyl 2-chloro-5-[3-chloro-5-(trifluoromethyl)-2-pyridyl]benzoate

[0555]

[0556] Potassium acetate (0.295 g, 0.86 mmol) and [1,1'-bis(diphenylphosphino)ferrocene]palladium dichloride (73 mg, 0.1 mmol) were added to a mixture of (4-chloro-3-methoxycarbonyl-phenyl)boronic acid (215 mg, 0.98 mmol) and 2,3-dichloro-5-trifluoromethyl-pyridine (320 mg, 1.5 mmol) in dioxane (8.6 ml). The mixture was heated in a microwave oven at 100°C for 45 minutes, cooled, and evaporated under reduced pressure. The residue was dissolved in dichloromethane (10 ml), and the resulting solution was washed with water and evaporated under reduced pressure. The residue was purified by chromatography to yield methyl 2-chloro-5-[3-chloro-5-(trifluoromethyl)-2-pyridyl]benzoate (0.30 g) as a light orange oil.

[0557] 1H NMR (400 MHz, CDCl3) δ 8.9 (s,1H), 8.35 (d,1H), 8.15 (s,1H), 7.9(d,1H), 7.6 (d,1H), 4.0 (s,3H) ppm.

[0558] Step 2: Synthesis of [2-chloro-5-[3-chloro-5-(trifluoromethyl)-2-pyridyl]-phenyl]-methanol

[0559]

[0560] A solution of lithium aluminum hydride (1 M in tetrahydrofuran; 4.8 ml, 4.8 mmol) was added dropwise over 15 minutes at 15°C to a stirred solution of methyl 2-chloro-5-[3-chloro-5-(trifluoromethyl)-2-pyridyl]benzoate (1.4 g, 3.2 mmol) in tetrahydrofuran (10 ml). The resulting mixture was heated to room temperature and stirred for 2 hours. The mixture was cooled to 15°C and water (5 ml) was slowly added. The mixture was stirred for 5 minutes, then an aqueous solution of ammonium chloride (50 ml) was added and the mixture was stirred for 5 minutes. The mixture was extracted with ethyl acetate, and the organic phase was dried and evaporated under reduced pressure to provide a red oil, which was purified by chromatography to provide [2-chloro-5-[3-chloro-5-(trifluoromethyl)-2-pyridyl]-phenyl]-methanol (440 mg) as a yellow oil.

[0561] 1 H NMR (400 MHz, CDCl3) δ 8.85 (d,1H), 8.1 (s,1H), 7.95 (s,1H), 7.7(dd,1H), 7.5 (d,1H), 4.9 (s,2H), 2.0 (br s,1H) ppm.

[0562] Example 6 Preparation of ethyl 3-[2-chloro-5-[3-chloro-5-(1,1-difluoroethyl)-2-pyridyl]-4-fluoro-phenyl]-5-methyl-4H-isoxazole-5-carboxylate (compound 1-595)

[0563]

[0564] 2-methoxy-N-(2-methoxyethyl)-N-(trifluoro- (-Thioalkyl)ethylamine (50% in toluene; 0.93 ml, 2.6 mmol) was added dropwise to ethyl 3-[5-(5-acetyl-3-chloro-2-pyridyl)-2-chloro-4-fluoro-phenyl]-5-methyl-4H-isoxazole-5-carboxylate (prepared as described in step 6 of Example 2; 75 mg, 0.17 mmol), and the resulting mixture was stirred at ambient temperature for 70 hours, and then added dropwise to an ice-cold aqueous solution of sodium bicarbonate. The resulting mixture was extracted with ethyl acetate (2 x 40 ml), and the combined organic extracts were dried and evaporated under reduced pressure to leave a residue, which was purified by chromatography to provide ethyl 3-[2-chloro-5-[3-chloro-5-(1,1-difluoroethyl)-2-pyridyl]-4-fluoro-phenyl]-5-methyl-4H-isoxazole-5-carboxylate (compound 1-595) (29 mg) as an oil.

[0565] 1 H NMR (400 MHz, CDCl3) δ 8.7 (d,1H), 7.95 (d,1H), 7.8 (d,1H), 7.3 (d,1H), 4.25 (q,2H), 4.0 (d,1H), 3.4 (d,1H),2.0 (t,3H), 1.7 (s,3H), 1.3 (t,3H)ppm.

[0566] Example 7 Preparation of ethyl 3-[2-chloro-5-(3-chloro-1-oxo-5-trifluoromethyl-2-pyridyl)-4-fluoro-phenyl]-5-methyl-4H-isoxazole-5-carboxylate (compound 1-667)

[0567]

[0568] A solution of ethyl 3-[2-chloro-5-(3-chloro-5-trifluoromethyl-2-pyridyl)-4-fluoro-phenyl]-5-methyl-4H-isoxazole-5-carboxylate (prepared as described in step 4 of Example 3; 300 mg, 0.64 mmol) and 3-chloroperbenzoic acid (60%; 890 mg, 3.1 mmol) in trifluorotoluene (10 ml) was stirred at ambient temperature for 48 hours. Water (20 ml) and ethyl acetate (60 ml) were added, the phases were separated, and the aqueous phase was extracted with ethyl acetate (4 x 50 ml). The combined organic phases were dried and evaporated under reduced pressure to leave a residue, which was purified by chromatography to provide ethyl 3-[2-chloro-5-(3-chloro-1-oxo-5-trifluoromethyl-2-pyridyl)-4-fluoro-phenyl]-5-methyl-4H-isoxazole-5-carboxylate (compound 1-667) (39 mg) as an oil. 1H NMR (400 MHz, CDCl3) δ 8.55 (s,1H), 7.8 (dd,1H), 7.6 (s,1H), 7.4(d,1H), 4.3 (q,2H), 4.15 (d,0.5H), 3.9 (d,0.5H), 3.55 (d,0.5H), 3.3 (d,0.5H),1.75 (d,3H), 1.35 (td,3H) ppm.

[0569] Also prepared by this general method are:

[0570] 3-[2-chloro-5-(3-chloro-1-oxo-5-trifluoromethyl-2-pyridyl)-phenyl]-5-methyl-4H-isoxazole-5-carboxylic acid ethyl ester (compound 1-663)

[0571] 1 H NMR (400 MHz, CDCl3) δ 8.5 (s,1H), 7.8 (d,1H), 7.6 (d,1H), 7.6 (s,1H), 7.5 (dd,1H), 4.3 (q,2H), 4.05 (d,1H), 3.45 (d,1H), 1.75 (s,3H), 1.35 (t,3H) ppm.

[0572] Example 8 Preparation of ethyl 3-[2-chloro-5-[3-chloro-5-(difluoromethoxy)-2-pyridyl]-4-fluoro-phenyl]-5-methyl-4H-isoxazole-5-carboxylate (compound 1-619)

[0573] Step 1: Synthesis of [5-chloro-6-[4-chloro-5-(5-ethoxycarbonyl-5-methyl-4H-isoxazol-3-yl)-2-fluoro-phenyl]-3-pyridyl]boronic acid

[0574]

[0575] A solution of ethyl 3-[5-(5-bromo-3-chloro-2-pyridyl)-2-chloro-4-fluoro-phenyl]-5-methyl-4H-isoxazole-5-carboxylate (compound 1-559) (prepared as described in Example 2; 330 mg, 0.68 mmol), bis(pinacolato)diboron (0.19 g, 0.75 mmol), potassium acetate (167 mg, 1.7 mmol), palladium diacetoxy (3 mg, 0.014 mmol), and tricyclohexylphosphine (8 mg, 0.028 mmol) in toluene (6.6 ml) was heated at 110°C for 3 hours, then cooled and ethyl acetate (80 ml) was added. The resulting mixture was filtered through diatomaceous earth, and the filtrate was evaporated under reduced pressure to provide [5-chloro-6-[4-chloro-5-(5-ethoxycarbonyl-5-methyl-4H-isoxazol-3-yl)-2-fluoro-phenyl]-3-pyridyl]boronic acid, which was used in the next step without further purification.

[0576] Step 2: Synthesis of ethyl 3-[2-chloro-5-(3-chloro-5-hydroxy-2-pyridyl)-4-fluoro-phenyl]-5-methyl-4H-isoxazole-5-carboxylate

[0577]

[0578] A solution of potassium peroxymonosulfonate (oxone) (0.36 g, 0.58 mmol) in water (2.8 ml) was added to a stirred solution of [5-chloro-6-[4-chloro-5-(5-ethoxycarbonyl-5-methyl-4H-isoxazol-3-yl)-2-fluoro-phenyl]-3-pyridyl]boronic acid (280 mg, 0.57 mmol) in acetone (11 ml). The resulting mixture was stirred for 1 hour, then water and ethyl acetate were added and the phases were separated. The aqueous phase was extracted with ethyl acetate, and the combined organic phases were dried and evaporated under reduced pressure to leave a residue, which was purified by chromatography to provide ethyl 3-[2-chloro-5-(3-chloro-5-hydroxy-2-pyridyl)-4-fluoro-phenyl]-5-methyl-4H-isoxazol-5-carboxylate (190 mg).

[0579] 1 ¹H NMR (400 MHz, CDCl₃) δ 8.2 (d, 1H), 7.75 (d, 1H), 7.3 (d, 1H), 7.25 (s, 1H), 4.3 (q, 2H), 4.0 (d, 1H), 3.4 (d, 1H), 1.75 (s, 3H), 1.35 (t, 3H) ppm (OH not observed).

[0580] Step 3: Synthesis of ethyl 3-[2-chloro-5-[3-chloro-5-(difluoromethoxy)-2-pyridyl]-4-fluoro-phenyl]-5-methyl-4H-isoxazole-5-carboxylate (compound 1-619)

[0581]

[0582] A mixture of 3-[2-chloro-5-(3-chloro-5-hydroxy-2-pyridyl)-4-fluoro-phenyl]-5-methyl-4H-isoxazole-5-carboxylate (90 mg, 0.21 mmol), sodium dichlorofluoroacetate (66 mg, 0.43 mmol), potassium carbonate (35 mg, 0.26 mmol), and dimethylformamide (0.9 ml) was stirred at 80°C for 18 hours, then cooled and tert-butyl methyl ether (60 ml) was added. The mixture was washed with water, dried, and evaporated under reduced pressure to leave a gel, which was purified by chromatography to provide ethyl 3-[2-chloro-5-[3-chloro-5-(difluoromethoxy)-2-pyridyl]-4-fluoro-phenyl]-5-methyl-4H-isoxazole-5-carboxylate (compound 1-619) (35 mg) as the gel.

[0583] 1 H NMR (400 MHz, CDCl3) δ 8.5 (d,1H), 7.8 (d,1H), 7.65 (s, 1H), 7.3(d,1H), 6.65 (t,1H), 4.3 (q,2H), 4.0 (d,1H), 3.4 (d,1H), 1.75 (s,3H), 1.35(t,3H) ppm.

[0584] Example 9 Preparation of ethyl 3-[2-chloro-5-(4,6-dichloropyridazin-3-yl)-4-fluoro-phenyl]-5-methyl-4H-isoxazole-5-carboxylate (compound 1-691)

[0585]

[0586] 0.035 ml (0.4 mmol) of tert-butyl nitrite was added dropwise over 2 minutes to a stirred mixture of copper(II) chloride (54 mg, 0.4 mmol) and acetonitrile (2.2 ml) at 0°C under nitrogen atmosphere. A solution of 3-[5-(4-amino-6-chloro-pyridazin-3-yl)-2-chloro-4-fluoro-phenyl]-5-methyl-4H-isoxazol-5-carboxylate (prepared as described in step 6 of Example 2; 110 mg, 0.27 mmol) in acetonitrile (1.1 ml) was added, and the mixture was stirred at 0°C for 30 minutes, then at ambient temperature for 2 hours. Water (30 ml) was added, and the resulting mixture was extracted with ethyl acetate (2 x 40 ml). The combined organic extracts were dried and evaporated under reduced pressure to leave a residue, which was purified by chromatography to provide ethyl 3-[2-chloro-5-(4,6-dichloropyridazine-3-yl)-4-fluoro-phenyl]-5-methyl-4H-isoxazole-5-carboxylate (compound 1-691) (71 mg).

[0587] 1 H NMR (400 MHz, CDCl3) δ 7.9 (d,1H), 7.7 (s,1H), 7.35 (d, 1H), 4.3(q,2H), 4.05 (d,1H), 3.4 (d,1H), 1.75 (s,3H), 1.35 (t,3H) ppm.

[0588] Examples of preparations

[0589]

[0590] The combination is thoroughly mixed with these adjuvants and the mixture is thoroughly ground in a suitable grinder to obtain a wettable powder that can be diluted with water to give a suspension of the desired concentration.

[0591]

[0592] Emulsions with any required dilution that can be used in plant protection can be obtained by diluting such concentrates with water.

[0593]

[0594] A ready-to-use dust agent is obtained by mixing the combination with a carrier and grinding the mixture in a suitable grinder.

[0595]

[0596] The combination is mixed with these additives and ground, and the mixture is moistened with water. The mixture is extruded and then dried in an air stream.

[0597]

[0598] This finely ground mixture is applied evenly to kaolin moistened with polyethylene glycol in a mixer. This process yields dust-free coated granules.

[0599] suspension concentrate

[0600]

[0601] The finely ground combination is tightly mixed with the auxiliary agent to obtain a suspension concentrate, from which a suspension concentrate can be diluted with water to obtain a suspension of any desired dilution.

[0602] Sustained-release capsule suspension

[0603] 28 parts of the mixture were combined with 2 parts of an aromatic solvent and 7 parts of a toluene diisocyanate / polymethylene-polyphenyl isocyanate mixture (8:1). This mixture was 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 was achieved. 2.8 parts of a 1,6-hexanediamine mixture in 5.3 parts of water was added to this emulsion. The mixture was stirred until polymerization was complete.

[0604] The obtained capsule suspension was stabilized by adding 0.25 parts of thickener and 3 parts of dispersant. The capsule suspension formulation contains 28% active ingredient. The diameter of the media capsules is 8-15 micrometers.

[0605] The resulting formulation is applied to the seeds as an aqueous suspension suitable for this purpose.

[0606] Biological examples

[0607] Pre-emergence biological effects

[0608] Seeds of weeds and / or crops were sown in standard soil in a container. After one day of incubation under controlled conditions in a greenhouse (24°C / 19°C, day / night; 16 hours of light), the plants were sprayed with an aqueous spray solution prepared as follows: the industrial active ingredient was formulated in a small amount of acetone and a special solvent and emulsifier mixture called IF50 (11.12% Emulsogen EL360™ + 44.44% N-methylpyrrolidone + 44.44% Dowanol DPM glycol ether) to produce a 50 g / L solution, which was then diluted with 0.2% Genapol XO80 as a diluent to obtain the desired final dose of the test compound.

[0609] These test plants were then grown in a greenhouse under controlled conditions (24°C / 18°C, day / night; 15 hours of light; 50% humidity) and watered twice daily. After 13 days, the tests were evaluated (100 = all plant damage; 0 = no plant damage). The results are shown in Table 2 below.

[0610] Table 2

[0611]

[0612]

[0613] Biological effects after emergence

[0614] Seeds of weeds and / or crops were sown in standard soil in a container. After culturing for 14 days under controlled conditions in a greenhouse (24°C / 19°C, day / night; 16 hours of light), the plants were sprayed with an aqueous spray solution prepared as follows: The technically active ingredient was formulated in a small amount of acetone and a special solvent and emulsifier mixture called IF50 (11.12% Emulsogen EL360™ + 44.44% N-methylpyrrolidone + 44.44% Dowanol DPM glycol ether) to produce a 50 g / L solution, which was then diluted with 0.2% Genapol XO80 as a diluent to obtain the desired final dose of the test compound.

[0615] These test plants were then grown in a greenhouse under controlled conditions (24°C / 18°C, day / night; 15 hours of light; 50% humidity) and watered twice daily. After 13 days, an evaluation test was conducted (100 = all plant damage; 0 = no plant damage). The results are shown in Table 3 below.

[0616] Table 3

[0617]

[0618]

Claims

1. A compound having formula (I) or an agronomically acceptable salt thereof: (I) in, A is nitrogen; B chooses the group consisting of: CR 18 and nitrogen; D. Choose from the following groups: CR 1 Nitrogen and N + -O - ; X can be selected from the following groups: CR 19 and nitrogen; The premise is that at most two of A, B, D and X are nitrogen, and neither B nor X are nitrogen; Y can choose from the following groups: CH; R 1 Selected from the group consisting of: halogens, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy and C1-C4 haloalkoxy; R 2 Choose from the group consisting of: hydrogen, halogen, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy and C1-C4 haloalkoxy; R 3 Choose from the following groups: hydrogen, chlorine, and fluorine; R 4 Choose the group consisting of: hydrogen and chlorine; R 5 and R 6 Each is hydrogen; R 7 It is CO2R 9 ; R 8 Choose from the group consisting of: hydrogen and C1-C4 alkyl groups; R 9 Choose from the group consisting of: hydrogen and C1-C4 alkyl groups; R 18 Choose from the group consisting of: hydrogen, halogen, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy and C1-C4 haloalkoxy; R 19 Choose from the group consisting of: hydrogen, halogen, C1-C2 alkyl, C1-C2 haloalkyl, nitro, cyano, C1-C2 alkylsulfonyl, C1-C2 alkoxy, and C1-C2 haloalkoxy; and The premise is R 1 R 2 R 18 and R 19 It's not all hydrogen.

2. The compound of claim 1, wherein R 19 Choose from the group consisting of: hydrogen, fluorine, chlorine, C1-C2 alkyl and C1-C2 haloalkyl.

3. The compound according to claim 1 or claim 2, wherein, A is nitrogen, B is CR. 18 D is CR 1 And X is CR 19 .

4. The compound according to claim 1 or claim 2, wherein, B is nitrogen, one of A and D is nitrogen, and X is CR. 19 .

5. The compound of claim 1 or claim 2, wherein... A is nitrogen; B is CR 18 ; D is CR 1 ; X is CR 19 ; Y is CH; R 1 Choose from the group consisting of: fluorine, chloro, methyl, and trifluoromethyl; R 2 Choose from the following groups: hydrogen, fluorine, chlorine, methyl, and trifluoromethyl; R 3 Choose the group consisting of: chlorine and fluorine; R 4 It is chlorine; R 5 and R 6 Each is hydrogen; R 7 It is CO2R 9 ; R 8 It is methyl; R 9 Choose from the group consisting of: hydrogen and C1-C4 alkyl groups; R 18 Choose from the following groups: hydrogen, fluorine, chlorine, methyl, and trifluoromethyl; R 19 Choose from the following groups: hydrogen, fluorine, chlorine, methyl, and trifluoromethyl.

6. An agricultural chemical composition comprising a herbicidal amount of a compound having formula (I) as defined in any one of claims 1 to 5, and an agriculturally chemically acceptable diluent or carrier.

7. A method for controlling or preventing unwanted plant growth, wherein, Apply an effective amount of the herbicidal compound having formula (I) as defined in any one of claims 1 to 5, or the composition as described in claim 6, to the plant, its parts, or its location.

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