EA047159B1 - HERBICIDE COMPOUNDS - Google Patents

Description

The present invention relates to herbicidally active isoxazoline derivatives, as well as to methods and intermediates used to obtain such derivatives. The present invention further extends to herbicidal compositions containing such derivatives, as well as the use of such compounds and compositions for the control of the growth of undesirable plants, in particular, the use for the control of weeds in crops of beneficial plants.

The present invention is based on the discovery that the isoxazoline derivatives of formula (I) defined herein exhibit surprisingly good herbicidal activity. Thus, according to the present invention there is provided a compound of formula (I) or an agronomically acceptable salt thereof

where X is selected from the group consisting of oxygen and sulfur;

Y represents C-H;

R ¹ is selected from the group consisting of hydrogen and C ₁ -C6 alkyl;

R ² is selected from the group consisting of hydrogen, amino, C1-C6 alkyl, C3-C6 alkenyl and C3-C6 alkynyl;

R3 is selected from the group consisting of hydrogen, halogen, C1- _C4 alkyl, C1- _C4 haloalkyl, _C1 - _C4 alkoxy, C1- _C4 haloalkoxy and C1- _C4 alkylsulfonyl;

R ⁴ is selected 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;

each of R ⁵ and R 6 is independently selected from the group consisting of hydrogen, cyano, C1-C6 alkyl, C1-C6 haloalkyl, C1-C ₄ alkylsulfonyl, CO ₂ R ⁹ , CONR ¹⁰ R ¹¹ and CH2OR ¹² ;

each of R ⁷ and R ⁸ 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 , CONR10R ¹¹ and CH2OR ¹² ;

Z is selected from the group consisting of oxygen, NOR ¹⁶ and NN(R ¹⁶ ) ₂ ;

R ⁹ is selected from the group consisting of hydrogen, C1-C10 alkyl, C1-C10 haloalkyl, C3-C6 alkenyl, C3-C6 haloalkenyl, C3-C6 alkynyl, C1-C4 alkoxyC1-C6 alkyl, C1-C4-haloalkoxyC1-C6-alkyl, C6-C10-arylC1-C3-alkyl, C6-C10-arylC1-C3-alkyl substituted with 1-4 ^R13 groups, heteroarylC1-C3alkyl and heteroarylC1- _C3 -alkyl substituted 1-3 R ¹³ groups, where each heteroaryl moiety is a 5- or 6-membered monocyclic aromatic ring which contains 1, 2, 3 or 4 heteroatoms individually selected from nitrogen, oxygen and sulfur;

R ¹⁰ is selected from the group consisting of hydrogen, C1-C ₆ alkyl and SO2R ¹⁴ ;

R ¹¹ is selected from the group consisting of hydrogen and C1-C ₆ -alkyl; or

R ¹⁰ and R ¹¹ together with the nitrogen atom to which they are attached form a 3-6 membered heterocyclyl ring, which optionally contains an oxygen atom;

R ¹² is selected from the group consisting of hydrogen, C1-C4 alkyl, C1-C4 haloalkyl, C1C4 alkylsulfonyl, C1-C4 haloalkylsulfonyl, phenylsulfonyl, phenylsulfonyl substituted with 1-2 R ¹³ groups; C1-C4 alkylcarbonyl, C1-C ₄ haloalkylcarbonyl, C ₆ -C ₁₀ arylcarbonyl, C ₆ -C ₁₀ arylcarbonyl substituted with 1-4 R ¹³ groups, heteroarylcarbonyl, heteroarylcarbonyl substituted with 1-3 R ¹³ groups, C6- C10-arylC1-C3 alkylcarbonyl, C6-C10-arylC1-C3 alkylcarbonyl substituted with 1-4 R ¹³ groups, heteroarylC1-C3 alkylcarbonyl and heteroarylC1-C ₃ alkylcarbonyl substituted with 1-3 R ¹³ groups;

each R ¹³ is independently selected from the group consisting of halogen, C 1 -C ₄ -alkyl, C 1 -C 4 -haloalkyl, C ₁ -C ₄ -alkoxy, C ₁ -C ₄ -haloalkoxy, cyano and C ₁ -C ₄ -alkylsulfonyl, where each heteroaryl moiety is a 5- or 6-membered monocyclic aromatic ring which contains 1,2,3 or 4 heteroatoms selected individually from nitrogen, oxygen and sulfur;

R ¹⁴ is selected from the group consisting of C ₁ -C ₄ -alkyl, C ₁ -C ₄ -haloalkyl and C ₁ -C ₄ -alkyl(C ₁ -C ₄ alkyl)amino;

R ¹⁵ is selected from the group consisting of hydrogen, C1- _C4 alkyl and C1- _C4 haloalkyl;

each R ¹⁶ is independently selected from the group consisting of hydrogen, C1- _C4 alkyl, C1-C4haloalkyl, and _C1 - _{C4 alkoxycarbonylC1} - _C4 alkyl.

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

According to a third aspect of the present invention, there is provided a method for monitoring or preventing

- 1 047159 for preventing the growth of undesirable plants, wherein a herbicidally effective amount of a compound of formula (I) or a composition containing this compound as an active ingredient is applied to plants, parts thereof or where they grow.

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

According to a fifth aspect of the present invention, there is provided a process for preparing compounds of formula (I).

As used herein, the term halogen or halogeno refers to fluorine (fluorine), chlorine (chlorine), bromine (bromine) or iodine (iodine), preferably fluorine, chlorine or bromine.

As used herein, the term cyano means a -CN group.

As used herein, the term hydroxy means a -OH group.

As used herein, the term nitro means the group -NO ₂ .

As used herein, the term C ₁ -C ₆ -alkyl refers to a straight or branched chain hydrocarbon radical consisting solely of carbon and hydrogen atoms, containing no unsaturated bonds, having from one to six carbon atoms, and which is attached to the rest of the molecule single bond. C ₁ -C ₄ -alkyl and C ₁ -C ₂ -alkyl should be interpreted accordingly. Examples of C ₁ -C ₆ -alkyl include, but are not limited to, methyl (Me), ethyl (Et), npropyl, 1-methylethyl (isopropyl), n-butyl and 1-dimethylethyl (tert-butyl).

As used herein, the term C1- _C6 alkoxy refers to a radical of the formula -ORa, where Ra is a C1- _C6 alkyl radical as generally defined above. C1- _C4 -alkoxy should be interpreted accordingly. Examples of C _1-4 alkoxy include, but are not limited to, methoxy, ethoxy, propoxy, isopropoxy and mpem-butoxy.

As used herein, the term C ₁ -C ₆ -haloalkyl refers to a C 1 -C ₆ -alkyl radical, as generally defined above, substituted by one or more identical or different halogen atoms. C1-C4 haloalkyl should be interpreted accordingly. Examples of C ₁ -C ₆ -haloalkyl include, but are not limited to, chloromethyl, fluoromethyl, fluoroethyl, difluoromethyl, trifluoromethyl and 2,2,2-trifluoroethyl.

As used herein, the term C ₂ -C ₆ -alkenyl refers to a group that is a straight or branched chain hydrocarbon radical consisting solely of carbon and hydrogen atoms containing at least one double bond, which can be found either in (E) -, or in the (2)-configuration, having from two to six carbon atoms, which is attached to the rest of the molecule by a single bond. C2-C4 alkenyl should be interpreted accordingly. Examples of C ₂ -C ₆ alkenyl include, but are not limited to, prop-1-enyl, allyl (prop-2-enyl) and but-1enyl.

As used herein, the term C ₂ -C ₆ -haloalkenyl refers to a C ₂ -C ₆ -alkenyl radical, as generally defined above, substituted by one or more identical or different halogen atoms. Examples of C2-C6 haloalkenyl include, but are not limited to, chloroethylene, fluoroethylene, 1,1-difluoroethylene, 1,1-dichloroethylene and 1,1,2-trichloroethylene.

As used herein, the term C ₂ -C ₆ -alkynyl refers to a group that is a straight or branched chain hydrocarbon radical consisting exclusively of carbon and hydrogen atoms, containing at least one triple bond, having from two to six carbon atoms, and which is attached to the rest of the molecule by a single bond. C ₂ -C ₄ -alkynyl should be interpreted accordingly. Examples of C2-C6 alkynyl include, but are not limited to, prop-1-ynyl, propargyl (prop-2-ynyl), and but-1-ynyl.

As used herein, the term C1- _C6 haloalkoxy refers to a C1- _C6 alkoxy group, as defined above, substituted with one or more identical or different halogen atoms. C1-C4 haloalkoxy should be interpreted accordingly. Examples of C1C6 haloalkoxy include, but are not limited to, fluoromethoxy, difluoromethoxy, fluoroethoxy, trifluoromethoxy and trifluoroethoxy.

As used herein, the term C ₁ -C ₃ -haloalkoxyC ₁ -C 3 -alkyl refers to a radical of the formula R _b -O-Ra-, where R _b is a C^C^haloalkyl radical as generally defined above, and Ra is is a C|-C ₃ -alkylene radical, which is generally defined above.

As used herein, the term C ₁ -C ₃ -alkoxyC ₁ -C ₃ -alkyl refers to a radical of the formula R _b -O-Ra-, where R _b represents a C^C^alkyl radical as generally defined above, and Ra is a C1- _C3 alkylene radical as generally defined above.

As used herein, the term C1- _C3 -alkoxyC1- _C3 -alkoxy- refers to a radical of the formula _Rb -O-Ra-O-, wherein _Rb is a C1- _C3 alkyl radical as generally defined above, and Ra is a C ₁ -C ₃ alkylene radical as generally defined above.

As used herein, the term C ₃ -C ₆ -alkenyloxy refers to a radical of the formula -ORa, where Ra is a C 3 -C 6 alkenyl radical as generally defined above.

As used herein, the term C ₃ -C ₆ -alkynyloxy refers to a radical of the formula -OR _a where R _a is a C ₃ -C ₆ -alkynyl radical as generally defined above.

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As used herein, the term hydroxyC1- _C6 -alkyl refers to a _C1 - _C6 -alkyl radical, as generally defined above, substituted by one or more hydroxy groups.

As used herein, the term C1- _C6 alkylcarbonyl refers to a radical of the formula -C(O)R _a where Ra is a _C1 - _C6 alkyl radical as generally defined above.

As used herein, the term C ₁ -C ₆ -alkoxycarbonyl refers to a radical of the formula -C(O)OR _a where R _a is a C ₁ -C ₆ -alkyl radical as generally defined above.

As used herein, the term aminocarbonyl refers to a radical of the formula -C(O)NH2.

As used herein, the term aminothiocarbonyl refers to a radical of the formula -C(S)NH2.

As used herein, the term C3- _C6 -cycloalkyl refers to a stable monocyclic ring radical that is saturated or partially unsaturated and contains from 3 to 6 carbon atoms. C ₃ -C4-cycloalkyl should be interpreted accordingly. Examples of C ₃ -C ₆ -cycloalkyl include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.

As used herein, the term C ₃ -C ₆ halocycloalkyl refers to a C ₃ -C ₆ cycloalkyl radical, as generally defined above, substituted by one or more identical or different halogen atoms. C3-C4 halocycloalkyl should be interpreted accordingly.

As used herein, the term C ₃ -C ₆ -cycloalkoxy refers to a radical of the formula OR _a where R _a represents a C ₃ -C ₆ -cycloalkyl radical as generally defined above.

As used herein, the term #C ₃ -C ₆ -cycloalkylamino refers to a radical of the formula -NHR _a where R _a is a C ₃ -C ₆ -cycloalkyl radical as generally defined above.

Unless otherwise expressly indicated, the term heteroaryl, as used herein, refers to a 5- or 6-membered monocyclic aromatic ring that contains 1, 2, 3, or 4 heteroatoms selected individually from nitrogen, oxygen, and sulfur. The heteroaryl radical may be linked to the rest of the molecule through a carbon atom or a heteroatom. Examples of heteroaryl include furyl, pyrrolyl, imidazolyl, thienyl, pyrazolyl, thiazolyl, isothiazolyl, oxazolyl, isoxazolyl, triazolyl, tetrazolyl, pyrazinyl, pyridazinyl, pyrimidyl or pyridyl.

Except where expressly stated otherwise, the term heterocyclyl or heterocyclic, as used herein, refers to a stable 4-6 membered non-aromatic monocyclic ring radical that contains 1, 2 or 3 heteroatoms selected individually from nitrogen, oxygen and sulfur. The heterocyclyl radical may be linked to the rest of the molecule through a carbon atom or a heteroatom. Examples of heterocyclyl include, but are not limited to, pyrrolinyl, pyrrolidyl, tetrahydrofuryl, tetrahydrothienyl, tetrahydrothiopyranyl, piperidyl, piperazinyl, tetrahydropyranyl, dihydroisoxazolyl, dioxolanyl, morpholinyl, or 5-lactamyl.

The presence of one or more possible asymmetric carbon atoms in a compound of formula (I) means that the compounds may occur in chiral isomeric forms, ie enantiomeric or diastereomeric forms. Atropoisomers can also arise as a result of limited rotation around a single bond. Formula (I) is intended to include all such possible isomeric forms and mixtures thereof. The present invention includes all such possible isomeric forms of the compound of formula (I) and mixtures thereof. Likewise, Formula (I) is intended to include all possible tautomers (including lactam-lactim tautomerism and keto-enol tautomerism), if present. The present invention includes all possible tautomeric forms of the compound of formula (I). Similarly, in the case of disubstituted alkenes, they can be present in the E- or Z-form or as mixtures of both in any proportion. The present invention includes all such possible isomeric forms of the compound of formula (I) and mixtures thereof.

The compounds of formula (I) will generally be present in the form of an agronomically acceptable salt, a zwitterion, or an agronomically acceptable zwitterion salt. The present invention covers all such agronomically acceptable salts, zwitterions and mixtures thereof in all proportions.

Suitable agronomically acceptable salts of the present invention may be with cations, which include, but are not limited to, metals, amine conjugate acids, and organic cations. Examples of suitable metals include aluminum, calcium, cesium, copper, lithium, magnesium, manganese, potassium, sodium, iron and zinc. Examples of suitable amines include allylamine, ammonia, amylamine, arginine, benetamine, benzathine, butenyl-2-amine, butylamine, butylethanolamine, cyclohexylamine, decylamine, diamylamine, dibutylamine, diethanolamine, diethylamine, diethylenetriamine, diheptylamine, dihexylamine, diisopropylamine, min, dimethylamine, dioctylamine, dipropanolamine, dipropargylamine, dipropylamine, dodecylamine, ethanolamine, ethylamine, ethylbutylamine, ethylenediamine, ethylheptylamine, ethyloctylamine, ethylpropanolamine, heptadecylamine, heptylamine, hexadecylamine, hexenyl-2-amine, hexylamine, hexylheptylamine, min, histidine, indoline, isoamylamine, isobutanolamine, isobutylamine, isopropanolamine, isopropylamine, lysine, meglumine, methoxyethylamine, me

- 3 047159 thylamine, methylbutylamine, methylethylamine, methylhexylamine, methylisopropylamine, methylnonylamine, methyloctadecylamine, methylpentadecylamine, morpholine, N,N-diethylethanolamine, N-methylpiperazine, nonylamine, octadecylamine, octylamine, oleylamine, ylamine, pentenyl-2-amine, phenoxyethylamine, picoline , piperazine, piperidine, propanolamine, propylamine, propylenediamine, pyridine, pyrrolidine, sec-butylamine, stearylamine, tallow amine, tetradecylamine, tributylamine, tridecylamine, trimethylamine, triheptylamine, trihexylamine, triisobutylamine, triisodecylamine, triisopropylamine, trimethylamine, amine, tripropylamine, tris( hydroxymethyl)aminomethane and undecylamine. Examples of suitable organic cations include benzyltributylammonium, benzyltrimethylammonium, benzyltriphenylphosphonium, choline, tetrabutylammonium, tetrabutylphosphonium, tetraethylammonium, tetraethylphosphonium, tetramethylammonium, tetramethylphosphonium, tetrapropylammonium, tetrapropylphosphonium, tributylsulfonium, tributylsulfonium, triethylsulfonium, ylsulfoxonium, trimethylsulfonium, trimethylsulfoxonium, tripropylsulfonium and tripropylsulfoxonium.

The following list provides definitions that include preferred definitions for substituents X, Y, Z, ^R1 , ^R2 , ^R3 , ^R4 , ^R5 , ^R6 , ^R7 , ^R8 , ^R9 , ^R10 , ^R11 , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ with reference to compounds of formula (I) in accordance with the present invention. With respect to any of these substituents, any of the definitions given below can be combined with any of the definitions of any other substituent given below or elsewhere in this document. Preferably X is sulfur.

Preferably Y is C-H.

Preferably R ¹ is selected from the group consisting of hydrogen and C1-C4 alkyl, more preferably C1-C2 alkyl, most preferably methyl. Preferably R ² is selected from the group consisting of hydrogen, C 1 -C 4 alkyl and C 3 -C 4 alkynyl, more preferably C ₁ -C ₂ alkyl, most preferably methyl. Preferably R ³ is selected from the group consisting of hydrogen, chlorine and fluorine, more preferably chlorine and fluorine.

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

Preferably, each of R ⁵ and R ⁶ is independently selected from the group consisting of hydrogen, C1-C4 alkyl, CO2R ⁹ and CH2OR ¹² , more preferably hydrogen and C1-C ₂ alkyl, most preferably hydrogen.

Preferably, each of R ⁷ and R ⁸ is independently selected from the group consisting of hydrogen, C ₁ -C ₄ alkyl, C 1 -C ₆ -haloalkyl, CO2R ⁹ , CONR ¹⁰ R ¹¹ and CH2OR ¹² More preferably, R ⁷ is selected from the group consisting of from CO2R ⁹ , CONR ¹⁰ R ¹¹ and CH2OR ¹² , most preferably CO2R ⁹ . More preferably, R ⁸ is selected from the group consisting of hydrogen and C1-C4 alkyl, most preferably methyl.

Preferably R ⁹ is selected from the group consisting of hydrogen, C1-C4 alkyl, C1-C4 haloalkyl, C1-C2 alkoxyyl, phenylC1-C2 alkyl and phenylC1-C2 alkyl substituted with 1-2 R ¹³ groups, more preferably hydrogen, C1-C4 alkyl, _C1 - _{C2 alkoxyC1} - _C2 alkyl and phenylC1- _C2 alkyl, most preferably hydrogen, C1-C4 alkyl and phenylC1-C2 alkyl.

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

Preferably R ¹¹ is hydrogen.

Preferably R ¹² is selected from the group consisting of hydrogen, C1-C2 alkyl, C1-C2 alkylsulfonyl, C1-C2 haloalkylsulfonyl, C1-C4 alkylcarbonyl, phenylcarbonyl, phenylcarbonyl substituted with 1-2 R ¹³ groups, phenylC1-C2 alkylcarbonyl and phenylC1- _C2 alkylcarbonyl substituted with 1-2 R ¹³ groups, more preferably C1- _C2 alkylsulfonyl, _C1 - _C2 haloalkylsulfonyl and C1-C4 alkylcarbonyl.

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

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

A preferred subset of compounds is the subset in which:

X represents sulfur;

Y represents C-H;

R ¹ represents C1- _C2 alkyl;

R ² represents C1-C ₂ alkyl;

R ³ is selected from the group consisting of hydrogen, chlorine and fluorine;

R ⁴ is selected from the group consisting of chlorine, cyano and aminothiocarbonyl;

each of R ⁵ and R ⁶ is independently selected from the group consisting of hydrogen and C1 -C ₂ alkyl;

R ⁷ is selected from the group consisting of CO2R ⁹ , CONR10R ¹¹ and CH2OR ¹² ;

R ⁸ is selected from the group consisting of hydrogen and C1-C4 alkyl;

R ⁹ is selected from the group consisting of hydrogen, C1-C ₄ alkyl, C ₁ -C ₂ alkoxyC ₁ -C ₂ alkyl and phenylC1C ₂ alkyl;

R ¹⁰ is SO2R ¹⁴ ;

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R ¹¹ represents hydrogen.

R ¹² is selected from the group consisting of C ₁ -C ₂ -alkylsulfonyl, C ₁ -C ₂ -haloalkylsulfonyl and C _{1 -C 4} -alkylcarbonyl;

R ¹⁴ is selected from the group consisting of methyl and isopropyl(methyl)amino.

A more preferred subset of compounds is the subset in which:

X represents sulfur;

Y represents C-H;

R ¹ represents methyl;

R ² represents methyl;

R ³ is selected from the group consisting of chlorine and fluorine;

R ⁴ represents chlorine;

R ⁵ and R ⁶ are each hydrogen;

R ⁷ represents CO2R ⁹ ;

R ⁸ represents methyl;

R ⁹ is selected from the group consisting of hydrogen, C1- _C4 alkyl and phenylC1- _C2 alkyl.

Table of examples.

This table discloses specific compounds of formula (I) wherein R ¹ and R ² are methyl.

Connection number X R ^J R ⁴ R ⁵ R ⁶ R ⁷ R ⁸ 1 ABOUT n C1 n n with ₂ n Me 2 ABOUT n C1 n n CO ₂ Me Me 3 ABOUT n C1 n n _CO2Et Me 4 ABOUT n C1 n n CO ₂ CH ₂ Ph Me 5 ABOUT n C1 n n CH ₂ OH Me 6 ABOUT n C1 n n CH ₂ OMe Me 7 ABOUT n C1 n n CH ₂ OCOMe Me 8 ABOUT n C1 n n _CH2OCOPh Me 9 ABOUT n C1 n n _{CH2OSO2Me ​} Me 10 ABOUT n C1 n n CH ₂ OSO ₂ CF ₃ Me AND ABOUT n C1 n n _CH2OSO2 ( _4MePh ) Me 12 ABOUT F C1 n n _CO2H Me 13 ABOUT F C1 n n _CO2Me Me 14 ABOUT F C1 n n _CO2Et Me 15 ABOUT F C1 n n CO ₂ CH ₂ Ph Me 16 ABOUT F C1 n n _CH2OH Me 17 ABOUT F C1 n n _CH2OMe Me 18 ABOUT F C1 n n CH ₂ OCOMe Me 19 ABOUT F C1 n n _CH2OCOPh Me 20 ABOUT F C1 n n _{CH2OSO2Me ​} Me 21 ABOUT F C1 n n CH ₂ OSO ₂ CF ₃ Me

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22 0 F Cl H H _CH2OSO2 ( _4MePh ) Me 23 0 Cl Cl H H _CO2H Me 24 0 Cl Cl H H _CO2Me Me 25 0 Cl Cl H H _CO2Et Me 26 0 Cl Cl H H CO ₂ CH ₂ Ph Me 27 0 Cl Cl H H _CH2OH Me 28 0 Cl Cl H H _CH2OMe Me 29 0 Cl Cl H H CH ₂ OCOMe Me thirty 0 Cl Cl H H _CH2OCOPh Me 31 0 Cl Cl H H _{CH2OSO2Me ​} Me 32 0 Cl Cl H H CH ₂ OSO ₂ CF ₃ Me 33 0 Cl Cl H H _CH2OSO2 ( _4MePh ) Me 34 s H Cl H H _CO2H Me 35 s H Cl H H _CO2Me Me 36 s H Cl H H _CO2Et Me 37 s H Cl H H CO ₂ CH ₂ Ph Me 38 s H Cl H H _CH2OH Me 39 s H Cl H H _CH2OMe Me 40 s H Cl H H CH ₂ OCOMe Me 41 s H Cl H H _CH2OCOPh Me 42 s H Cl H H _{CH2OSO2Me ​} Me 43 s H Cl H H CH ₂ OSO ₂ CF ₃ Me 44 s H Cl H H _CH2OSO2 ( _4MePh ) Me 45 s F Cl H H _CO2H Me 46 s F Cl H H _CO2Me Me 47 s F Cl H H _CO2Et Me 48 s F Cl H H CO ₂ CH ₂ Ph Me 49 s F Cl H H _CH2OH Me 50 s F Cl H H _CH2OMe Me 51 s F Cl H H CH ₂ OCOMe Me

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52 S F Cl H H _CH2OCOPh Me 53 S F Cl H H _{CH2OSO2Me ​} Me 54 S F Cl H H CH ₂ OSO ₂ CF ₃ Me 55 S F Cl H H _CH2OSO2 ( _4MePh ) Me 56 S Cl Cl H H _CO2H Me 57 S Cl Cl H H _CO2Me Me 58 S Cl Cl H H _CO2Et Me 59 S Cl Cl H H CO ₂ CH ₂ Ph Me 60 S Cl Cl H H _CH2OH Me 61 S Cl Cl H H _CH2OMe Me 62 S Cl Cl H H CH ₂ OCOMe Me 63 S Cl Cl H H _CH2OCOPh Me 64 S Cl Cl H H _{CH2OSO2Me ​} Me 65 S Cl Cl H H CH ₂ OSO ₂ CF ₃ Me 66 S Cl Cl H H _CH2OSO2 ( _4MePh ) Me 67 S H CN H H _CO2H Me 68 S H CN H H _CO2Me Me 69 S H CN H H _CO2Et Me 70 S H CN H H CO ₂ CH ₂ Ph Me 71 S H CN H H _CH2OH Me 72 S H CN H H _CH2OMe Me 73 S H CN H H CH ₂ OCOMe Me 74 S H CN H H _CH2OCOPh Me 75 S H CN H H _{CH2OSO2Me ​} Me 76 S H CN H H CH ₂ OSO ₂ CF ₃ Me 77 s H CN H H _CH2OSO2 ( _4MePh ) Me 78 s F CN H H _CO2H Me 79 s F CN H H _CO2Me Me 80 s F CN H H _CO2Et Me 81 s F CN H H CO ₂ CH ₂ Ph Me

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82 S F CN H H _CH2OH Me 83 S F CN H H _CH2OMe Me 84 S F CN H H CH ₂ OCOMe Me 85 S F CN H H _CH2OCOPh Me 86 S F CN H H _{CH2OSO2Me ​} Me 87 S F CN H H CH ₂ OSO ₂ CF ₃ Me 88 S F CN H H _CH2OSO2 ( _4MePh ) Me 89 S Cl CN H H _CO2H Me 90 S Cl CN H H _CO2Me Me 91 S Cl CN H H _CO2Et Me 92 s Cl CN H H CO ₂ CH ₂ Ph Me 93 s Cl CN H H _CH2OH Me 94 s Cl CN H H _CH2OMe Me 95 s Cl CN H H CH ₂ OCOMe Me 96 s Cl CN H H _CH2OCOPh Me 97 s Cl CN H H _{CH2OSO2Me ​} Me 98 s Cl CN H H CH ₂ OSO ₂ CF ₃ Me 99 s Cl CN H H _CH2OSO2 ( _4MePh ) Me 100 s H csnh ₂ H H _CO2H Me 101 s H csnh ₂ H H _CO2Me Me 102 s H csnh ₂ H H _CO2Et Me 103 s H csnh ₂ H H CO ₂ CH ₂ Ph Me 104 s H csnh ₂ H H _CH2OH Me 105 s H csnh ₂ H H _CH2OMe Me 106 s H csnh ₂ H H CH ₂ OCOMe Me 107 s H csnh ₂ H H _CH2OCOPh Me 108 s H csnh ₂ H H _{CH2OSO2Me ​} Me 109 s H csnh ₂ H H CH ₂ OSO ₂ CF ₃ Me 110 s H csnh ₂ H H _CH2OSO2 ( _4MePh ) Me 111 s F csnh ₂ H H _CO2H Me

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112 S F csnh ₂ H H _CO2Me Me FROM S F csnh ₂ H H _CO2Et Me 114 S F csnh ₂ H H CO ₂ CH ₂ Ph Me 115 S F csnh ₂ H H _CH2OH Me 116 S F csnh ₂ H H _CH2OMe Me 117 S F csnh ₂ H H CH ₂ OCOMe Me 118 S F csnh ₂ H H _CH2OCOPh Me 119 S F csnh ₂ H H _{CH2OSO2Me ​} Me 120 S F csnh ₂ H H CH ₂ OSO ₂ CF ₃ Me 121 S F csnh ₂ H H _CH2OSO2 ( _4MePh ) Me 122 S Cl csnh ₂ H H _CO2H Me 123 S Cl csnh ₂ H H _CO2Me Me 124 S Cl csnh ₂ H H _CO2Et Me 125 S Cl csnh ₂ H H CO ₂ CH ₂ Ph Me 126 S Cl csnh ₂ H H _CH2OH Me 127 S Cl csnh ₂ H H _CH2OMe Me 128 s Cl csnh ₂ H H CH ₂ OCOMe Me 129 s Cl csnh ₂ H H _CH2OCOPh Me 130 s Cl csnh ₂ H H _{CH2OSO2Me ​} Me 131 s Cl csnh ₂ H H CH ₂ OSO ₂ CF ₃ Me 132 s Cl csnh ₂ H H _CH2OSO2 ( _4MePh ) Me 133 s H Cl Me H _CO2H Me 134 s H Cl Me H _CO2Me Me 135 s H Cl Me H _CO2Et Me 136 s H Cl Me H CO ₂ CH ₂ Ph Me 137 s H Cl Me H _CH2OH Me 138 s H Cl Me H _CH2OMe Me 139 s H Cl Me H CH ₂ OCOMe Me 140 s H Cl Me H _CH2OCOPh Me 141 s H Cl Me H _{CH2OSO2Me ​} Me

- 9 047159

142 S H Cl Me H CH2OSO2CF3 Me 143 S H Cl Me H _CH2OSO2 ( _4MePh ) Me 144 S F Cl Me H _CO2H Me 145 S F Cl Me H _CO2Me Me 146 S F Cl Me H _CO2Et Me 147 S F Cl Me H CO2CH2PI1 Me 148 S F Cl Me H _CH2OH Me 149 S F Cl Me H _CH2OMe Me 150 S F Cl Me H CH ₂ OCOMe Me 151 S F Cl Me H _CH2OCOPh Me 152 S F Cl Me H _{CH2OSO2Me ​} Me 153 S F Cl Me H CH2OSO2CF3 Me 154 S F Cl Me H _CH2OSO2 ( _4MePh ) Me 155 S Cl Cl Me H _CO2H Me 156 S Cl Cl Me H _CO2Me Me 157 S Cl Cl Me H _CO2Et Me 158 S Cl Cl Me H CO ₂ CH ₂ Ph Me 159 S Cl Cl Me H _CH2OH Me 160 s Cl Cl Me H _CH2OMe Me 161 s Cl Cl Me H CH ₂ OCOMe Me 162 s Cl Cl Me H _CH2OCOPh Me 163 s Cl Cl Me H _{CH2OSO2Me ​} Me 164 s Cl Cl Me H CH2OSO2CF3 Me 165 s Cl Cl Me H _CH2OSO2 ( _4MePh ) Me 166 s H Cl Me Me _CO2H Me 167 s H Cl Me Me _CO2Me Me 168 s H Cl Me Me _CO2Et Me 169 s H Cl Me Me CO2CH2PI1 Me 170 s H Cl Me Me _CH2OH Me 171 s H Cl Me Me _CH2OMe Me

- 10 047159

172 S H Cl Me Me CH ₂ OCOMe Me 173 S H Cl Me Me _CH2OCOPh Me 174 S H Cl Me Me _{CH2OSO2Me ​} Me 175 S H Cl Me Me CH ₂ OSO ₂ CF ₃ Me 176 S H Cl Me Me _CH2OSO2 ( _4MePh ) Me 177 S F Cl Me Me _CO2H Me 178 S F Cl Me Me _CO2Me Me 179 S F Cl Me Me _CO2Et Me 180 S F Cl Me Me CO ₂ CH ₂ Ph Me 181 S F Cl Me Me _CH2OH Me 182 S F Cl Me Me _CH2OMe Me 183 S F Cl Me Me CH ₂ OCOMe Me 184 S F Cl Me Me _CH2OCOPh Me 185 S F Cl Me Me _{CH2OSO2Me ​} Me 186 S F Cl Me Me CH ₂ OSO ₂ CF ₃ Me 187 S F Cl Me Me _CH2OSO2 ( _4MePh ) Me 188 s Cl Cl Me Me _CO2H Me 189 s Cl Cl Me Me _CO2Me Me 190 s Cl Cl Me Me _CO2Et Me 191 s Cl Cl Me Me CO ₂ CH ₂ Ph Me 192 s Cl Cl Me Me _CH2OH Me 193 s Cl Cl Me Me _CH2OMe Me 194 s Cl Cl Me Me CH ₂ OCOMe Me 195 s Cl Cl Me Me _CH2OCOPh Me 196 s Cl Cl Me Me _{CH2OSO2Me ​} Me 197 s Cl Cl Me Me CH ₂ OSO ₂ CF ₃ Me 198 s Cl Cl Me Me _CH2OSO2 ( _4MePh ) Me 199 s H Cl H H _CO2H H 200 s H Cl H H _CO2Me H 201 s H Cl H H _CO2Et H

- 11 047159

202 S H Cl H H CO ₂ CH ₂ Ph H 203 S H Cl H H _CH2OH H 204 S H Cl H H _CH2OMe H 205 S H Cl H H CH ₂ OCOMe H 206 S H Cl H H _CH2OCOPh H 207 S H Cl H H _{CH2OSO2Me ​} H 208 S H Cl H H CH ₂ OSO ₂ CF ₃ H 209 S H Cl H H _CH2OSO2 ( _4MePh ) H 210 S F Cl H H _CO2H H 211 S F Cl H H _CO2Me H 212 S F Cl H H _CO2Et H 213 S F Cl H H CO ₂ CH ₂ Ph H 214 S F Cl H H _CH2OH H 215 S F Cl H H _CH2OMe H 216 S F Cl H H CH ₂ OCOMe H 217 S F Cl H H _CH2OCOPh H 218 S F Cl H H _{CH2OSO2Me ​} H 219 S F Cl H H CH ₂ OSO ₂ CF ₃ H 220 S F Cl H H _CH2OSO2 ( _4MePh ) H 221 S Cl Cl H H _CO2H H 222 S Cl Cl H H _CO2Me H 223 S Cl Cl H H _CO2Et H 224 S Cl Cl H H CO ₂ CH ₂ Ph H 225 S Cl Cl H H _CH2OH H 226 s Cl Cl H H _CH2OMe H 227 s Cl Cl H H CH ₂ OCOMe H 228 s Cl Cl H H _CH2OCOPh H 229 s Cl Cl H H _{CH2OSO2Me ​} H 230 s Cl Cl H H CH ₂ OSO ₂ CF ₃ H 231 s Cl Cl H H _CH2OSO2 ( _4MePh ) H

- 12 047159

232 S H Cl _CO2H Me H H 233 S F Cl _CO2H Me H H 234 S Cl Cl _CO2H Me H H 235 S H Cl _CO2Et Me H H 236 S F Cl _CO2Et Me H H 237 S Cl Cl _CO2Et Me H H 238 S H Cl _CH2OH Me H H 239 S F Cl _CH2OH Me H H 240 S Cl Cl _CH2OH Me H H 241 S H Cl _CO2H Me H Me 242 S F Cl _CO2H Me H Me 243 S Cl Cl _CO2H Me H Me 244 S H Cl _CO2Et Me H Me 245 S F Cl _CO2Et Me H Me 246 S Cl Cl _CO2Et Me H Me 247 S H Cl _CH2OH Me H Me 248 S F Cl _CH2OH Me H Me 249 S Cl Cl _CH2OH Me H Me 250 S H Cl H H _CO2H CF ₃ 251 S H Cl H H _CO2Me CF ₃ 252 S H Cl H H _CO2Et CF ₃ 253 S H Cl H H CO ₂ CH ₂ Ph CF ₃ 254 S H Cl H H _CH2OH CF ₃ 255 S H Cl H H _CH2OMe CF ₃ 256 S H Cl H H CH ₂ OCOMe CF ₃ 257 s H Cl H H _CH2OCOPh CF ₃ 258 s H Cl H H _{CH2OSO2Me ​} CF ₃ 259 s H Cl H H CH ₂ OSO ₂ CF ₃ CF ₃ 260 s H Cl H H _CH2OSO2 ( _4MePh ) CF ₃ 261 s F Cl H H _CO2H CF ₃

- 13 047159

262 S F Cl H H _CO2Me CF ₃ 263 S F Cl H H _CO2Et CF ₃ 264 S F Cl H H CO ₂ CH ₂ Ph CF ₃ 265 S F Cl H H _CH2OH CF ₃ 266 S F Cl H H _CH2OMe CF ₃ 267 S F Cl H H CH ₂ OCOMe CF ₃ 268 S F Cl H H _CH2OCOPh CF ₃ 269 S F Cl H H _{CH2OSO2Me ​} CF ₃ 270 S F Cl H H CH ₂ OSO ₂ CF ₃ CF ₃ 271 S F Cl H H _CH2OSO2 ( _4MePh ) CF ₃ 272 S Cl Cl H H _CO2H CF ₃ 273 S Cl Cl H H _CO2Me CF ₃ 274 S Cl Cl H H _CO2Et CF ₃ 275 S Cl Cl H H CO ₂ CH ₂ Ph CF ₃ 276 S Cl Cl H H _CH2OH CF ₃ 277 S Cl Cl H H _CH2OMe CF ₃ 278 S Cl Cl H H CH ₂ OCOMe CF ₃ 279 S Cl Cl H H _CH2OCOPh CF ₃ 280 S Cl Cl H H _{CH2OSO2Me ​} CF ₃ 281 S Cl Cl H H CH ₂ OSO ₂ CF ₃ CF ₃ 282 S Cl Cl H H _CH2OSO2 ( _4MePh ) CF ₃ 283 S H Cl H H CONHSO ₂ Me Me 284 S F Cl H H CONHSO ₂ Me Me 285 S Cl Cl H H CONHSO ₂ Me Me 286 S H Cl H H CONHSO ₂ N(Me)(CHMe ₂ ) Me 287 S F Cl H H CONHSO ₂ N(Me)(CHMe ₂ ) Me 288 s Cl Cl H H CONHSO ₂ N(Me)(CHMe ₂ ) Me 289 s H Cl H H COMe Me 290 s F Cl H H COME Me 291 s Cl Cl H H COME Me

- 14 047159

292 S n C1 n n C(NOMe)Me Me 293 S F C1 n n C(NOMe)Me Me 294 S C1 C1 n n C(NOMe)Me Me 295 S n C1 n n C(NOH)Me Me 296 S F C1 n n C(NOH)Me Me 297 S C1 C1 n n C(NOH)Me Me 298 S n C1 n n C(NOCH ₂ CO ₂ Me)Me Me 299 S F C1 n n C(NOCH ₂ CO ₂ Me)Me Me 300 S C1 C1 n n C(NOCH ₂ CO ₂ Me)Me Me 301 S n C1 n n C(NNH ₂ )Me Me 302 S F C1 n n C(NNH ₂ )Me Me 303 S C1 C1 n n C(NNH ₂ )Me Me 304 S n C1 n n CONHSO ₂ NMe ₂ Me 305 S F C1 n n CONHSO ₂ NMe ₂ Me 306 S C1 C1 n n CONHSO ₂ NMe ₂ Me 307 S n C1 n n conh ₂ Me 308 S F C1 n n conh ₂ Me 309 S C1 C1 n n conh ₂ Me 310 S n C1 n n _CO2Me Ome 311 S F C1 n n _CO2Me OMe 312 S C1 C1 n n _CO2Me Ome

The compounds of the present invention can be prepared using techniques known to one skilled in the art of organic chemistry. General methods for preparing compounds of formula (I) are described below. Unless otherwise indicated in the text, then substituents X, Y, Z, ^R1 , ^R2 , ^R3 , ^R4 , ^R5 , ^R6 , ^R7 , R8, ^{R9 , R10 , R11} , ^R12 , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are defined above in this document. The starting materials used to prepare the compounds of the present invention can be purchased from conventional commercial suppliers or can be prepared using known methods. The starting materials as well as intermediate products can be purified before use in the next step using techniques known in the art, such as chromatography, crystallization, distillation and filtration.

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

Reaction scheme 1.

(A) (B)

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

Ureas or thioureas of formula (A) are available or can be prepared using methods widely known in the literature.

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

- 15 047159

Reaction scheme 2.

For example, a compound of formula (C) can be treated with a carbonyl transfer reagent such as diphosgene or triphosgene in a suitable solvent such as toluene. Anilines of formula (C) can be prepared from nitro compounds of formula (D), as shown in reaction scheme 3.

Reaction scheme 3.

For example, a compound of formula (D) can be treated with a reducing agent such as iron and ammonium chloride in a suitable solvent such as a mixture of water and ethanol. Nitro compounds of formula (D) can be prepared from oximes of formula (E) and alkenes of formula (F), as shown in reaction scheme 4.

Reaction scheme 4.

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

Alkenes of formula (F) are available or can be prepared using methods widely known in the literature.

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

Reaction scheme 5.

For example, the aldehyde of formula (G) can be treated with hydroxylamine hydrochloride in a suitable solvent such as a mixture of water and ethanol.

Aldehydes of formula (G) are available or can be prepared using methods known in the literature.

Compounds of formula (IA), which are compounds of formula (I) in which R ⁷ is a carboxylic acid group, can be prepared from compounds of formula (IB), which are compounds of formula (I) in which R ⁷ is CO ₂ R ⁹ as shown in reaction scheme 6.

Reaction scheme 6.

For example, a compound of formula (I-B) can be treated with sodium hydroxide in a suitable solvent such as a mixture of water and ethanol.

Compounds of formula (IC), which are compounds of formula (I) in which R ⁷ represents a hydroxymethyl group, can be prepared from compounds of formula (IA or IB) as shown in reaction scheme 7.

Reaction scheme 7.

R ⁹ ) ₂ r .3 .4

Η (I-A or I-B)

For example, a compound of formula (I-A) or (I-B) can be treated with a suitable reducing agent, for example a metal hydride reagent such as sodium borohydride or borane, in a suitable solvent such as tetrahydrofuran.

Compounds of formula (ID), which are compounds of formula (I) in which R ⁷ is CH2OR ¹² , can be prepared from compounds of formula (IC) as shown in reaction scheme 8.

Reaction scheme 8.

For example, a compound of formula (I-C) can be treated with reagent R12-LG, where LG is a leaving group such as a halogen, such as an alkylating agent, an acylating agent or a sulfonylating agent, in the presence of a base such as sodium hydride or triethylamine in a suitable solvent , such as tetrahydrofuran.

Compounds of formula (IE), which are compounds of formula (I) in which R ⁷ is CONR10R ¹¹ , can be prepared from a compound of formula (I-A) as shown in reaction scheme 9.

Reaction scheme 9.

For example, a compound of formula (IA) can be treated with a halogenation reagent such as oxalyl chloride in a suitable solvent such as dichloromethane to form an acyl halide, which can be treated with a reagent HNR ¹⁰ R ¹¹ in the presence of a base such as triethylamine in a suitable solvent such like dichloromethane.

Compounds of formula (IG), which are compounds of formula (I) in which R ⁷ is an oxime group, can be prepared from compounds of formula (IF), which are compounds of formula (I) in which R ⁷ is a ketone group , as shown in reaction scheme 10.

Reaction scheme 10.

For example, a compound of formula (IF) can be treated with hydroxylamine H2NOR ¹⁶ or a salt thereof, optionally in the presence of a base such as triethylamine, in a suitable solvent such as ethanol.

- 17 047159

Compounds of formula (IH), which are compounds of formula (I) in which R ⁷ is a hydrazone group, can be prepared from compounds of formula (IF), which are compounds of formula (I) in which R ⁷ is a ketone group , as shown in reaction scheme 11.

Reaction scheme 11.

(Ι-F) (1-H)

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

One skilled in the art will appreciate that it is often possible to change the order in which the above-described transformations are carried out, or combine them in alternative ways, to produce a wide range of compounds of formula (I). Multiple steps can also be combined into one reaction. All such variations are within the scope of the present invention.

One skilled in the art will also recognize that some reagents will be incompatible with certain values or combinations of substituents X, Y, Z, R1, ^R2 , ^R3 , ^R4 , ^R5 , ^R6 , ^R7 , ^R8 , ^R9 , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ as defined herein, and any additional steps, such as protecting and/or deprotecting steps, that are necessary to achieve the desired transformations will be understandable to a person skilled in the art.

The compounds of the present invention can be used as herbicidal agents in unmodified form, but are typically formulated in various ways using formulation auxiliaries such as carriers, solvents and surfactants. The compositions may be in various physical forms, for example, sprayable powders, gels, wettable powders, water-dispersible granules, water-dispersible tablets, effervescent tablets, emulsifiable concentrates, microemulsion concentrates, oil-in-water emulsions, oil-based fluid formulations, aqueous dispersions, oil dispersions, suspoemulsions, 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 forms known, for example, from the Manual on Development and Use of FAO and WHO Specifications for Pesticides, United Nations, First Edition, Second Revision (2010). For water-soluble compounds, soluble liquids, water-soluble concentrates or water-soluble granules are preferred. Such formulations can either be applied directly or diluted before use. Dilutions can be carried out, for example, with water, liquid fertilizers, micronutrients, biological organisms, oil or solvents.

The compositions can be prepared, for example, by mixing the active ingredient with formulation auxiliaries to obtain compositions in the form of fine solids, granules, solutions, dispersions or emulsions. The active ingredients may also be formulated with other excipients, for example, fine solids, mineral oils, vegetable or animal oils, modified vegetable or animal oils, organic solvents, water, surfactants, or combinations thereof.

The active ingredients may also be contained in very small microcapsules. Microcapsules contain active ingredients in a porous carrier. This allows the active ingredients to be released into the environment in controlled quantities (eg slow release). Microcapsules typically have a diameter ranging from 0.1 to 500 microns. They contain active ingredients in amounts ranging from approximately 25 to 95% by weight of the capsule. The active ingredients may be in the form of a monolithic solid, in the form of fine particles in a solid or liquid dispersion, or in the form of a suitable solution. Encapsulating membranes may contain, for example, natural and synthetic rubbers, cellulose, styrene-butadiene copolymers, polyacrylonitrile, polyacrylate, polyesters, polyamides, polyureas, polyurethane or chemically modified polymers and starch xanthates or other polymers that are known to one skilled in the art. Alternatively, very fine microcapsules may be formed in which the active ingredient is contained in the form of fine particles in a solid matrix of the base material, but the microcapsules are not themselves encapsulated.

Excipients for formulation that are suitable for obtaining

- 18 047159 positions in accordance with the present invention are known per se. Liquid carriers that can be used are water, toluene, xylene, petroleum ether, vegetable oils, acetone, methyl ethyl ketone, cyclohexanone, acid anhydrides, acetonitrile, acetophenone, amyl acetate, 2-butanone, butylene carbonate, chlorobenzene, cyclohexane, cyclohexanol, alkyl esters of acetic acid , diacetone alcohol, 1,2-dichloropropane, diethanolamine, p-diethylbenzene, diethylene glycol, diethylene glycol abietate, diethylene glycol butyl ether, diethylene glycol ethyl ether, diethylene glycol methyl ether, KH-dimethylformamide. dimethyl sulfoxide, 1,4-dioxane, dipropylene glycol, dipropylene glycol methyl ether, dipropylene glycol dibenzoate, diproxitol, alkylpyrrolidone, ethyl acetate, 2-ethylhexanol, ethylene carbonate, 1,1,1-trichloroethane, 2-heptanone, alpha-pinene, d-limonene, ethyl lactate, ethylene glycol , ethylene glycol butyl ether, ethylene glycol methyl ether, gamma-butyrolactone, glycerin, glycerol acetate, glycerol diacetate, glycerol triacetate, hexadecane, hexylene glycol, isoamyl acetate, isobornyl acetate, isooctane, isophorone, isopropylbenzene, isopropyl myristate, lactic acid, ylamine, mesityl oxide, methoxypropanol , methyl isoamyl ketone, methyl isobutyl ketone, methyl laurate, methyl octanoate, methyl oleate, methylene chloride, mxylene, n-hexane, n-octylamine, octadecanoic acid, octylamine acetate, oleic acid, oleylamine, o-xylene, phenol, polyethylene glycol, propionic acid, propylene carbonate, propylene glycol, propylene glycol methyl ether, p-xylene, toluene, triethyl phosphate, triethylene glycol, xylene sulfonic acid, paraffin, mineral oil, trichlorethylene, perchlorethylene, ethyl acetate, amyl acetate, butyl acetate, propylene glycol methyl ether, diethylene glycol methyl ether, methanol, ethanol, propanol and high molecular weight alcohols such as amyl alcohol, tetrahydrofurfuryl alcohol, hexanol, octanol, ethylene glycol, propylene glycol, glycerin, Nmethyl-2-pyrrolidone, etc.

Suitable solid carriers are, for example, talc, titanium dioxide, pyrophyllite clay, silica, attapulgite clay, diatomaceous earth, limestone, calcium carbonate, bentonite, calcium montmorillonite, cottonseed hulls, wheat flour, soya flour, pumice, wood flour, ground shells walnuts, lignin and similar substances.

A large number of surfactants can be used successfully in both solid and liquid formulations, especially in those formulations that can be diluted with a vehicle before use. Surfactants may be anionic, cationic, nonionic, or polymeric, and may be used as emulsifiers, wetting agents or suspending agents, or for other purposes. Typical surfactants include, for example, alkyl sulfate salts such as diethanolammonium lauryl sulfate; alkylaryl sulfonate salts such as calcium dodecylbenzenesulfonate; alkylphenol/alkylene oxide addition products such as nonylphenol ethyloxylate; alcohol/alkylene oxide addition products such as tridecyl alcohol ethoxylate; soaps such as sodium stearate; alkyl naphthalene sulfonate salts such as sodium dibutyl naphthalene sulfonate; dialkyl esters of sulfosuccinate salts such as sodium di(2ethylhexyl)sulfosuccinate; sorbitol esters such as sorbitolate; quaternary amines such as lauryl trimethyl ammonium chloride, polyethylene glycol fatty acid esters such as polyethylene glycol stearate; block copolymers of ethylene oxide and propylene oxide and salts of mono- and dialkyl phosphate esters; as well as additional substances described, for example, in McCutcheon's Detergents and Emulsifiers Annual, MC Publishing Corp., Ridgewood New Jersey (1981).

Additional excipients that may be used in pesticide formulations include crystallization inhibitors, viscosity modifiers, suspending agents, colorants, antioxidants, foaming agents, light absorbers, mixing aids, antifoams, complexing agents, neutralizing or pH-modifying agents, and buffers. corrosion inhibitors, fragrances, wetting agents, absorption enhancers, micronutrients, plasticizers, glidants, lubricants, dispersants, thickeners, antifreeze, microbiocides, and liquid and solid fertilizers.

Compositions in accordance with the present invention may include an additive comprising a vegetable or animal oil, mineral oil, alkyl esters of such oils, or mixtures of such oils and oil derivatives. The amount of oil additive in the composition in accordance with the present invention is usually from 0.01 to 10% based on the mixture to be used. For example, the oil additive can be added to the sprayer reservoir at the required concentration after the spray mixture is prepared. Preferred oil additives include mineral or vegetable oils, such as canola oil, olive oil or sunflower oil, emulsified vegetable oil, alkyl esters of vegetable oils, such as methyl derivatives, or an animal oil, such as fish oil or beef tallow. Preferred oil additives include alkyl esters of C ₈ -C ₂ fatty acids, especially methyl derivatives of C 12 -C 18 fatty acids, for example, methyl esters of lauric acid, palmitic acid and oleic acid (methyl laurate, methyl palmitate and methyl oleate, respectively). Many oil derivatives from

- 19 047159 from Compendium of Herbicide Adjuvants, ^10th Edition, Southern Illinois University, 2010.

Herbicidal compositions typically contain from 0.1 to 99% by weight, in particular from 0.1 to 95% by weight of compounds of formula (I) and from 1 to 99.9% by weight of a formulation aid, which is preferably includes from 0 to 25% by weight of surfactant. The compositions of the present invention generally contain from 0.1 to 99% by weight, in particular from 0.1 to 95% by weight of the compounds of the present invention and from 1 to 99.9% by weight of the formulation excipient which preferably includes from 0 to 25% by weight of surfactant. Since commercial products may preferably be formulated as concentrates, the end user will typically use diluted formulations.

Application rates vary widely and depend on soil properties, method of application, crop plant, pest being controlled, prevailing climatic conditions and other factors determined by application method, time of application and target crop. As a general guide, compounds can be applied at rates of 1 to 2000 l/ha, in particular 10 to 1000 l/ha.

Preferred compositions may be characterized by the following compositions (wt.%).

Emulsifiable concentrates:

active ingredient: 1-95%, preferably 60-90%; surface-active substance: 1-30%, preferably 5-20%; liquid carrier: 1-80%, preferably 1-35%.

Dust preparations:

active ingredient: 0.1-10%, preferably 0.1-5%; solid carrier: 99.9-90%, preferably 99.9-99%.

Suspension concentrates:

active ingredient: 5-75%, preferably 10-50%; water: 94-24%, preferably 88-30%; surface-active substance: 1-40%, preferably 2-30%.

Wettable powders:

active ingredient: 0.5-90%, preferably 1-80%; surface-active substance: 0.5-20%, preferably 1-15%; solid carrier: 5-95%, preferably 15-90%.

Granules:

active ingredient: 0.1-30%, preferably 0.1-15%; solid carrier: 99.5-70%, preferably 97-85%.

The composition of the present invention may further contain at least one additional pesticide. For example, the compounds of the present invention may also be used in combination with other herbicides or plant growth regulators. In a preferred embodiment, the additional pesticide is a herbicide and/or a herbicide antidote.

Thus, the compounds of formula (I) can be used in combination with one or more other herbicides to provide various herbicide mixtures. Specific examples of such mixtures include (wherein I is a compound of formula (I)): I+acetochlor; I+acifluorfen (including acifluorfen sodium); I+aclonifen; I+alachlor; I+alloxydim; I+amethrine; I+amicarbazone; I+amidosulfuron; I+aminocyclopyrachlor; I+aminopyralide; I+amitrol; I+asulam; I+atrazine; I+bensulfuron (including bensulfuron-methyl); I+bentazone; I+bicyclopyrone; I+bilanaphos; I+bifenox; I+bispiribac-sodium; I+bixloson; I+bromacil; I+bromoxynil; I+butachlor; I+butafenacil; I+kafenstrol; I+carfentrazone (including carfentrazone-ethyl); cloransulam (including cloransulam-methyl); I+chlorimuron (including chlorimuron-ethyl); I+chlorotoluron; I+cinosulfuron; I+chlorsulfuron; I+cinmethylin; I+klatsifos; I+clethodim; I+clodinafop (including clodinafop-propargyl); I+clomazone; I+clopyralid; I+cyclopyranil; I+cyclopyrimorate; I+cyclosulfamuron; I+cyhalofop (including cyhalofop-butyl); I+2,4-D (including choline salt and its 2-ethylhexyl ester); I+2,4-DB; I+daimuron; I+desmedipham; I+dicamba (including its salts with aluminum, aminopropyl, bis-aminopropylmethyl, choline, dichlorprop, diglycolamine, dimethylamine, dimethylammonium, potassium and sodium); I+diclofop-methyl; I+diclosulam; I+diflufenican; I+difenzoquat; I+diflufenican; I+diflufenzopyr; I+dimethachlor; I+dimethenamide-P; I+diquat dibromide; I+diuron; I+esprocarb; I+ethalfluralin; I+ethofumesate; I+fenoxaprop (including fenoxaprop-R-ethyl); I+phenoxasulfone; I+phenquinotrione; I+phentrazamide; I+flazasulfuron; I+florasulam; I+florpyrauxifene; I+fluazifop (including fluazifop-R-butyl); I+flucarbazone (including flucarbazone sodium); I+flufenacet; I+flumetralin; I+flumetsulam; I+flumioxazin; I+flupyrsulfuron (including flupyrsulfuron-methyl-sodium); I+fluroxypyr (including fluroxypyr-meptyl); I+flutiacet-methyl; I+fomesafen; I+foramsulfuron; I+glufosinate (including its

- 20 047159 ammonium salt); I+glyphosate (including its diammonium, isopropylammonium and potassium salts); I+galauxifen (including galauxifen-methyl); I+halosulfuron-methyl; I+haloxyfop (including haloxyfop-methyl); I+hexazinone; I+hydantocidin; I+imazamox; I+imazapic; I+imazapir; I+imasaquin; I+imazethapyr; I+indasiflam; I+iodosulfuron (including iodosulfuron-methyl-sodium); I+iophensulfuron; I+iophensulfuron-sodium; I+ioxynil; I+ipfencarbazone; I+isoproturon; I+isoxaben; I+isoxaflutole; I+lactofen; I+lancotrione; I+linuron; I+MSPA; I+MRV; I+mecoprop-P; I+mefenacet; I+mesosulfuron; I+mesosulfuron-methyl; I+mesotrione; I+metamitron; I+metazachlor; I+metiozolin; I+methobromuron; I+metolachlor; I+methosulam; I+methoxuron; I+metribuzin; I+metsulfuron; I+molinate; I+napropamide; I+nicosulfuron; I+norflurazon; I+orthosulfamuron; I+oxadiargyl; I+oxadiazone; I+oxasulfuron; I+oxyfluorfen; I+paraquat dichloride; I+pendimethalin; I+penoxulam; I+phenmedipham; I+pichloram; I+picolinafen; I+pinoxaden; I+pretilachlor; I+primisulfuron-methyl; I+prodiamine; I+prometrin; I+propachlor; I+propanil; I+propaquizafop; I+professional; I+propyrisulfuron, I+propyzamide; I+prosulfocarb; I+prosulfuron; I+pyraclonil; I+pyraflufen (including pyraflufen-ethyl); I+pyrasulfotol; I+pyrazolinate, I+pyrazosulfuronethyl; I+pyribenzoxime; I+pyridate; I+pyrifthalide; I+pyrimisulfan, I+pyrithiobac-sodium; I+pyroxasulfone; I+piroxulam; I+quinclorac; I+quinmerac; I+quizalofop (including quizalofop-Retil and quizalofop-R-tefuryl); I+ rimsulfuron; I+saflufenacil; I+sethoxydim; I+simazine; I+Smetolachlor; I+sulcotrione; I+sulfentrazone; I+sulfosulfuron; I+tebuthiuron; I+tefuryltrione; I+tembotrione; I+terbutylazine; I+terbutryn; I+thienecarbazone; I+thifensulfuron; I+thiaphenacyl; I+tolpyralate; I+topramesone; I+tralkoxydim; I+triafamon; I+triallate; I+triasulfuron; I+tribenuron (including tribenuron-methyl); I+triclopyr; I+trifloxysulfuron (including trifloxysulfuron-sodium); I+trifludimoxazine; I+trifluralin; I+triflusulfuron; I+tritosulfuron; I+4hydroxy-1-methoxy-5-methyl-3-[4-(trifluoromethyl)-2-pyridyl]imidazolidin-2-one; 1+4-hydroxy-1,5dimethyl-3-[4-(trifluoromethyl)-2-pyridyl]imidazolidin-2-one; I+5-ethoxy-4-hydroxy-1-methyl-3-[4(trifluoromethyl)-2-pyridyl]imidazolidin-2-one; I+4-hydroxy-1-methyl-3-[4-(trifluoromethyl)-2pyridyl]imidazolidin-2-one; I+4-hydroxy-1,5-dimethyl-3-[1-methyl-5-(trifluoromethyl)pyrazol-3 yl]imidazolidin-2-one; I+(4R)1-(5-tert-butylisoxazol-3-yl)-4-ethoxy-5-hydroxy-3methylimidazolidin-2-one; I+3-[2-(3,4-dimethoxyphenyl)-6-methyl-3-oxopyridazine-4carbonyl]bicyclo[3.2.1]octane-2,4-dione; I+2-[2-(3,4-dimethoxyphenyl)-6-methyl-3-oxopuridazine-4carbonyl]-5-methylcyclohexane-1,3-dione; I+2-[2-(3,4-dimethoxyphenyl)-6-methyl-3-oxopuridazine-4carbonyl]cyclohexane-1,3-dione; I+2-[2-(3,4-dimethoxyphenyl)-6-methyl-3-oxopuridazine-4-carbonyl]-5,5dimethylcyclohexane-1,3-dione; I+6-[2-(3,4-dimethoxyphenyl)-6-methyl-3-oxopyridazine-4-carbonyl]2,2,4,4-tetramethylcyclohexane-1,3,5-trione; I+2-[2-(3,4-dimethoxyphenyl)-6-methyl-3-oxopyridazine-4carbonyl]-5-ethylcyclohexane-1,3-dione; I+2-[2-(3,4-dimethoxyphenyl)-6-methyl-3-oxopyridazine-4carbonyl]-4,4,6,6-tetramethylcyclohexane-1,3-dione; I+2-[6-cyclopropyl-2-(3,4-dimethoxyphenyl)-3 oxopyridazine-4-carbonyl]-5-methylcyclohexane-1,3-dione; I+3-[6-cyclopropyl-2-(3,4-dimethoxyphenyl)3-oxopyridazine-4-carbonyl]bicyclo[3.2.1]octane-2,4-dione; 1+2-[6-cyclopropyl-2-(3,4dimethoxyphenyl)-3-oxopyridazine-4-carbonyl]-5,5-dimethylcyclohexane-1,3-dione; H6-[6-cyclopropyl2-(3,4-dimethoxyphenyl)-3-oxopyridazine-4-carbonyl]-2,2,4,4-tetramethylcyclohexane-1,3,5-trione; I+2[6-cyclopropyl-2-(3,4-dimethoxyphenyl)-3-oxopyridazine-4-carbonyl]cyclohexane-1,3-dione; I+4-[2-(3,4dimethoxyphenyl)-6-methyl-3-oxopyridazin-4-carbonyl]-2,2,6,6-tetramethyltetrahydropyran-3,5-dione and I+4-[6-cyclopropyl -2-(3,4-dimethoxyphenyl)-3-oxopyridazin-4-carbonyl]-2,2,6,6tetramethyltetrahydropyran-3,5-dione.

The components mixed with the compound of formula (I) may also be in the form of esters or salts, as mentioned, for example, in The Pesticide Manual, Fourteenth Edition, British Crop Protection Council, 2006.

The compound of formula (I) can also be used in mixtures with other agrochemicals, such as fungicides, nematicides or insecticides, examples of which are given in The Pesticide Manual.

The mixture ratio of the compound of formula (I) and the component to be mixed is preferably from 1:100 to 1000:1.

The mixtures can advantageously be used in the above-mentioned formulations (in which case the expression active ingredient refers to the corresponding mixture of the compound of formula (I) with the component to be mixed).

The compounds of formula (I) of the present invention can also be combined with herbicide safeners. Preferred combinations (where I is a compound of formula (I)) include: I+benoxacor, I+cloquintocet (including cloquintocet-mexyl); I+cyprosulfamide; I+dichloromide; I+fenchlorazole (including fenchlorazole-ethyl); I+phenclorim; I+fluxophenim; 1+furilazole I+isoxadifen (including isoxadifen-ethyl); I+mefenpyr (including mefenpyrdiethyl); I+metcamifene; H^C-methoxybenzoyl^-^methylaminocarbonylmino^enzenesulfonamide and I+oxabetrinyl.

Particularly preferred are mixtures of the compound of formula (I) with cyprosulfamide,

- 21 047159 isoxadifen (including isoxadifen-ethyl), cloquintoset (including cloquintosetmexil) and/or N(2-methoxybenzoyl)-4-[(methylaminocarbonyl)amino]benzenesulfonamide.

Antidotes for the compound of formula (I) may also be in the form of esters or salts, as mentioned, for example, in The Pesticide Manual, ^14th Edition (BCPC), 2006. Reference to cloquintocet-mexyl also refers to its lithium, sodium salt , potassium, calcium, magnesium, aluminum, iron, ammonium, quaternary ammonium, sulfonium or phosphonium, as disclosed in WO 02/34048, and reference to fenchlorazole-ethyl also refers to fenchlorazole, etc.

Preferably, the mixture ratio of the compound of formula (I) and the antidote is from 100:1 to 1:10, in particular from 20:1 to 1:1.

The mixtures can advantageously be used in the above-mentioned formulations (in which case the expression active ingredient refers to a corresponding mixture of a compound of formula (I) with an antidote).

The compounds of formula (I) of the present invention are useful as herbicides. Therefore, the present invention further provides a method for controlling unwanted plants, comprising applying to said plants or a growing location containing them an effective amount of a compound of the present invention or a herbicidal composition containing the same. Control means the destruction, reduction or retardation of growth or the prevention or reduction of germination. Typically the plants to be controlled are unwanted plants (weeds). Habitat means the area in which plants grow or will grow.

The rates of application of compounds of formula (I) can vary widely and depend on the properties of the soil, the method of application (pre-emergence; post-emergence; application in relation to the seed furrow; application in no-tillage, etc.), the crop plant , the weed(s) to be controlled, prevailing climatic conditions and other factors determined by the method of application, timing of application and target crop. The compounds of formula (I) according to the present invention are generally used at a rate of 10 to 2000 g/ha, in particular 50 to 1000 g/ha. The preferred range is 10-200 g/ha.

Application is usually carried out by spraying the composition, typically using a tractor-mounted sprayer for large areas, but other methods such as dusting (for powders), drip irrigation or irrigation can also be used.

Beneficial plants to which the composition of the present invention can be applied include agricultural crops such as cereals, for example barley and wheat, cotton, oilseed rape, sunflower, maize, rice, soybeans, sugar beets, sugar cane and turf. cover.

Cultivated plants may also include trees such as fruit trees, palm trees, coconut trees or other nut crops. Also included are climbing plants such as grapes, fruit bushes, fruit plants and vegetables.

It should be understood that crops also include those crops that have been made tolerant of herbicides or classes of herbicides (e.g., ALS, GS, EPSPS, PPO, ACCase, and HPPD inhibitors) through conventional breeding techniques or through genetic engineering. An example of a crop that has been engineered to tolerate imidazolinones, such as imazamox, through traditional breeding techniques is Clearfield® canola. Examples of crops that have been genetically engineered to tolerate herbicides include, for example, glyphosate- and glufosinate-resistant maize varieties commercially available under the trademarks RoundupReady® and LibertyLink®.

Crop crops also include those that have been genetically engineered to be resistant to harmful insects, such as Bt maize (resistant to the corn borer), Bt cotton (resistant to the cotton weevil), and varieties of Bt potatoes ( resistant to the Colorado potato beetle). Examples of Bt maize are the Bt 176 NK® maize hybrids (Syngenta Seeds). Bt toxin is a protein that is naturally produced by the soil bacteria Bacillus thuringiensis. Examples of toxins or transgenic plants capable of synthesizing such toxins are described in EP-A-451878, EP-A-374753, WO 93/07278, WO 95/34656, WO 03/052073 and EP-A-427529. Examples of transgenic plants containing one or more genes encoding insect resistance and expressing one or more toxins include KnockOut® (maize), Yield Gard® (maize), NuCOTIN33B® (cotton), Bollgard® (cotton), NewLeaf® (potato varieties), NatureGard® and Protexcta®. Plant crops or their seed material can be resistant to herbicides and at the same time resistant to eating by insects (transgenic objects with packaged genes). For example, a seed may have the ability to express the insecticidal protein Cry3 while at the same time being tolerant to glyphosate.

It should also be understood that crops include those derived from

- 22 047159 by traditional methods of selection or genetic engineering and have so-called introduced traits (for example, improved storage stability, higher nutritional value and improved taste).

Other useful plants include turf grass, such as on golf courses, lawns, parks and roadsides or commercially grown for lawns, and ornamental plants such as flowers or shrubs.

The compounds of formula (I) and the compositions of the present invention can generally be used to control a wide variety of monocotyledonous and dicotyledonous weed species. Examples of monocot species that can usually be controlled include Alopecurus myosuroides, Avena fatua, Brachiaria plantaginea, Bromus tectorum, Cyperus esculentus, Digitaria sanguinalis, Echinochloa crus-galli, Lolium perenne, Lolium multiflorum, Panicummiliaceum, Poa annua, Setaria viridis, Setaria faberi and Sorghum bicolor. Examples of dicotyledonous species that can be controlled include Abutilon theophrasti, Amaranthus retroflexus, Bidens pilosa, Chenopodium album, Euphorbia heterophylla, Galium aparine, Ipomoea hederacea, Kochia scoparia, Polygonum convolvulus, Sida spinosa, Sinapis arvensis, Solarium nigrum, Stellaria media, Veronica persica and Xanthium strumarium.

The compounds of formula (I) are also suitable for pre-harvest desiccation of agricultural crops, for example, without limitation, potatoes, soybeans, sunflower and cotton varieties. Pre-harvest desiccation is used to dry crop leaves without significantly damaging the crop itself to facilitate harvest.

The compounds/compositions of the present invention are particularly useful in non-selective contact applications with continuous action and, as such, can also be used to control self-seeding or escape crop plants.

Various aspects and embodiments of the present invention will now be illustrated in more detail by way of example. It should be understood that modifications in certain details may be made without departing from the scope of the present invention.

Examples

The following examples serve to illustrate, but not to limit, the present invention.

Synthesis examples

Example 1. Synthesis of ethyl 3-[2-chloro-5-(3,5-dimethyl-2,6-dioxo-4-thioxo-1,3,5-triazinan-1-yl)-4fluorophenyl]-5- methyl 4H-isoxazole-5-carboxylate (compound 47).

Step 1. Synthesis of 2-chloro-4-fluoro-5-nitrobenzaldehyde oxime

Hydroxylamine hydrochloride (6.39 g, 92 mmol) was added to a stirred solution of 2-chloro-4fluoro-5-nitrobenzaldehyde (13 g, 61.3 mmol) in ethanol (65 ml) at room temperature. The resulting solution was stirred at room temperature for an additional 60 minutes. Water (125 ml) was added and the resulting mixture was filtered to obtain 2-chloro-4-fluoro-5nitrobenzaldehyde oxime as a yellow solid (13.0 g).

¹ H NMR (400 MHz, CHCl ₃ ) δ 8.65 (d, 1H), 8.5 (s, 1H), 8.1 (br s, 1H), 7.4 (d, 1H) ppm.

Using this general method the following were also obtained:

2-chloro-5-nitrobenzaldehyde oxime.

1H NMR (400 MHz, СНС1з) δ 8.75 (s, 1H), 8.55 (s, 1H), 8.15 (m, 1H), 7.9 (s, 1H), 7.6 (m , 1H) ppm.

2,4-dichloro-5-nitrobenzaldehyde oxime.

Step 2. Synthesis of ethyl 3-(2-chloro-4-fluoro-5-nitrophenyl)-5-methyl-4H-isoxazole-5-carboxylate

1-Chloropyrrolidine-2,5-dione (0.6 mL, 6.6 mmol) was added portionwise over 10 min to a stirred solution of 2-chloro-4-fluoro-5-nitrobenzaldehyde oxime (1.2 g, 5.5 mmol) in N,Ndimethylformamide (4.8 ml) at 30°C. The resulting mixture was stirred at 35°C for 1 hour, then cooled to room temperature and dichloromethane (50 ml) was added. The mixture was washed with dilute hydrochloric acid (15 ml), dried and cooled to 5°C. To this stirred solution was added dropwise a mixture of triethylamine (1.33 mL, 9.5 mmol) and ethyl 2-methylprop-2-enoate (1.14 g, 9.5 mmol). After standing at room temperature for 17 hours, dilute hydrochloric acid (5 ml) was added, the phases were separated and the organic phase was dried and purified by chromatography to give ethyl 3-(2-chloro-4-fluoro-5-nitrophenyl)-5 -methyl-4H-isoxazole-5

- 23 047159 carboxylate (1.0 g).

1H NMR (400 MHz, СНС1з) δ 8.45 (d, 1H), 7.45 (d, 1H), 4.3 (q, 2H), 4.0 (d, 1H), 3.4 (d , 1H), 1.75 (s, 3H), 1.35 (t, 3H) ppm.

Using this general method the following were also obtained:

ethyl 3-(2-chloro-5-nitrophenyl)-5-methyl-4H-isoxazole-5-carboxylate.

^1H NMR (400 MHz, СНС1з) δ 8.55 (d, 1H), 8.2 (d, 1H), 7.65 (d, 1H), 4.3 (q, 2H), 4.05 ( d, 1H), 3.4 (d, 1H), 1.75 (s, 3H), 1.35 (t, 3H) ppm.

Methyl 3-(2-chloro-4-fluoro-5-nitrophenyl)-5-(trifluoromethyl)-4H-isoxazole-5-carboxylate.

1H NMR (400 MHz, СНС1з) δ 8.45 (d, 1H), 7.45 (d, 1H), 4.2 (d, 1H), 3.95 (d, 1H), 3.95 (s , 3H) ppm.

Methyl 3-(2-chloro-4-fluoro-5-nitrophenyl)-4,5-dimethyl-4H-isoxazole-5-carboxylate.

1H NMR (400 MHz, СНС1з) δ 8.3 (d, 1H), 7.45 (d, 1H), 3.9 (q, 1H), 3.8 (s, 3H), 1.75 (s , 3H), 1.1 (d, 3H) ppm.

[3-(2-Chloro-4-fluoro-5-nitrophenyl)-5-methyl-4H-isoxazol-5-yl]methanol.

^1H NMR (400 MHz, SHC13) δ 8.45 (d, 1H), 7.45 (d, 1H), 3.8 (br d, 1H), 3.65 (d, 1H), 3.6 (br d, 1H), 3.2 (d, 1H), 2.1 (m, 1H), 1.5 (s, 3H) ppm.

1-[3-(2-Chloro-4-fluoro-5-nitrophenyl)-5-methyl-4H-isoxazol-5-yl]ethanone.

1H NMR (400 MHz, СНС1з) δ 8.4 (d, 1H), 7.45 (d, 1H), 3.95 (d, 1H), 3.2 (d, 1H), 2.35 (s , 3H), 1.65 (s, 3H) ppm.

Ethyl 3-(2,4-dichloro-5-nitrophenyl)-5-methyl-4H-isoxazole-5-carboxylate.

1H NMR (400 MHz, СНС1з) δ 8.35 (s, 1H), 7.7 (s, 1H), 4.3 (q, 2H), 4.05 (d, 1H), 3.4 (d , 1H), 1.75 (s, 3H), 1.35 (t, 3H) ppm.

Methyl 3-(2-chloro-4-fluoro-5-nitrophenyl)-5-methoxy-4H-isoxazole-5-carboxylate.

1H NMR (400 MHz, СНС1з) δ 8.55 (d, 1H), 7.45 (d, 1H), 4.0 (d, 1H), 3.9 (s, 3H), 3.6 (d , 1H), 3.5 (s, 3H) ppm.

Step 3. Synthesis of ethyl 3-(5-amino-2-chloro-4-fluorophenyl)-5-methyl-4H-isoxazole-5-carboxylate

Tin dichloride hydrate (2.3 g, 12.1 mmol) was added to a stirred solution of ethyl 3-(2-chloro4-fluoro-5-nitrophenyl)-5-methyl-4H-isoxazole-5-carboxylate (1.0 g , 3.0 mmol) in ethyl acetate (60 ml) at room temperature. After 5 minutes, the mixture was refluxed for 3 hours, cooled and evaporated under reduced pressure to give a brown oil, which was purified by chromatography to give ethyl 3-(5-amino-2-chloro-4-fluorophenyl)-5 -methyl-4H-isoxazole-5carboxylate (800 mg).

1H NMR (400 MHz, СНС1з) δ 7.15 (d, 1H), 7.05 (d, 1H), 4.3 (q, 2H), 3.95 (d, 1H), 3.4 (d , 1H), 1.7 (s, 3H), 1.3 (t, 3H) ppm (NH ₂ not observed).

Using this general method the following were also obtained:

ethyl 3-(5-amino-2-chlorophenyl)-5-methyl-4H-isoxazole-5-carboxylate.

Methyl 3-(5-amino-2-chloro-4-fluorophenyl)-5-(trifluoromethyl)-4H-isoxazole-5-carboxylate.

1H NMR (400 MHz, СНС1з) δ 7.15 (d, 1H), 7.1 (d, 1H), 4.2 (d, 1H), 3.95 (d, 1H), 3.9 (s , 3H), 3.85 (br s, 2H) ppm.

Methyl 3-(5-amino-2-chloro-4-fluorophenyl)-4,5-dimethyl-4H-isoxazole-5-carboxylate.

1H NMR (400 MHz, СНС1з) δ 7.15 (d, 1H), 6.9 (d, 1H), 3.9 (q, 1H), 3.85 (br s, 2H), 3.8 ( s, 3H), 1.75 (s, 3H), 1.0 (d, 3H) ppm.

[3-(5-Amino-2-chloro-4-fluorophenyl)-5-methyl-4H-isoxazol-5-yl]methyl acetate.

1-[3-(5-Amino-2-chloro-4-fluorophenyl)-5-methyl-4H-isoxazol-5-yl]ethanone.

Ethyl 3-(5-amino-2,4-dichlorophenyl)-5-methyl-4H-isoxazole-5-carboxylate.

1H NMR (400 MHz, СНС1з) δ 7.35 (s, 1H), 7.3 (s, 1H), 4.3 (q, 2H), 4.1 (br s, 2H), 3.95 ( d, 1H), 3.4 (d, 1H), 1.75 (s, 3H), 1.35 (t, 3H) ppm.

Methyl 3-(5-amino-2-chloro-4-fluorophenyl)-5-methoxy-4H-isoxazole-5-carboxylate.

1H NMR (400 MHz, СНС1з) δ 7.15 (d, 1H), 7.1 (d, 1H), 3.95 (d, 1H), 3.9 (s, 3H), 3.85 (br s, 2H), 3.6 (d, 1H), 3.45 (s, 3H) ppm.

Step 4. Synthesis of ethyl 3-(2-chloro-4-fluoro-5-isocyanatophenyl)-5-methyl-4H-isoxazole-5-carboxylate

Ethyl 3-(5-amino-2-chloro-4-fluorophenyl)-5-methyl-4H-isoxazole-5-carboxylate solution (800 mg, 2.66

- 24047159 mmol) in dry toluene (16 ml) was added to stirred diphosgene (0.4 ml, 3.2 mmol) at room temperature and the mixture was then refluxed for 3 hours, cooled and evaporated under reduced pressure.

Toluene (10 ml) was added and the mixture was evaporated under reduced pressure to give ethyl 3-(2chloro-4-fluoro-5-isocyanatophenyl)-5-methyl-4H-isoxazole-5-carboxylate as a light brown liquid (750 mg ).

^1H NMR (400 MHz, CHCl ₃ ) δ 7.45 (d, 1H), 7.25 (d, 1H), 4.3 (q, 2H), 3.9 (d, 1H), 3.35 (d, 1H), 1.75 (s, 3H), 1.35 (t, 3H) ppm.

Using this general method the following were also obtained:

ethyl 3-(2-chloro-5-isocyanatophenyl)-5-methyl-4H-isoxazole-5-carboxylate.

Methyl 3-(2-chloro-4-fluoro-5-isocyanatophenyl)-5-(trifluoromethyl)-4H-isoxazole-5-carboxylate.

¹ H NMR (400 MHz, CHCl ₃ ) δ 7.45 (d, 1H), 7.3 (d, 1H), 4.15 (d, 1H), 3.95 (d, 1H), 3.95 (s,3H) ppm.

Methyl 3-(2-chloro-4-fluoro-5-isocyanatophenyl)-4,5-dimethyl-4H-isoxazole-5-carboxylate.

1-[3-(2-Chloro-4-fluoro-5-isocyanatophenyl)-5-methyl-4H-isoxazol-5-yl]methyl acetate.

1-[3-(2-Chloro-4-fluoro-5-isocyanatophenyl)-5-methyl-4H-isoxazol-5-yl]ethanone.

Ethyl 3-(2,4-dichloro-5-isocyanatophenyl)-5-methyl-4H-isoxazole-5-carboxylate.

Methyl 3-(2-chloro-4-fluoro-5-isocyanatophenyl)-5-methoxy-4H-isoxazole-5-carboxylate.

^1H NMR (400 MHz, СНС1з) δ 7.5 (d, 1H), 7.25 (d, 1H), 3.95 (d, 1H), 3.9 (s, 3H), 3.6 ( d, 1H), 3.5 (s, 3H) ppm.

Step 5. Preparation of ethyl-3-[2-chloro-5-(3,5-dimethyl-2,6-dioxo-4-thioxo-1,3,5-triazinan-1-yl)-4fluorophenyl]-5- methyl 4H-isoxazole-5-carboxylate (compound 47)

A solution of 1,3-dimethylthiourea (0.31 g, 2.94 mmol) and triethylamine (0.45 ml, 3.82 mmol) in toluene was added to a stirred solution of ethyl 3-(2-chloro-4-fluoro-5 -isocyanatophenyl)-5-methyl-4Nisoxazole-5-carboxylate (800 mg, 2.45 mmol) in toluene (16 ml) at room temperature. The resulting mixture was heated to reflux and carbonyldiimidazole (0.62 g, 3.67 mmol) was added in portions over 15 minutes. The mixture was refluxed for 3.5 hours, cooled and evaporated under reduced pressure to give a brown oil, which was purified by chromatography to give ethyl 3-[2-chloro-5-(3,5-dimethyl-2, 6-dioxo-4-thioxo-1,3,5triazinan-1-yl)-4-fluorophenyl]-5-methyl-4H-isoxazole-5-carboxylate (compound 47) (775 mg).

^1H NMR (400 MHz, СНС1з) δ 7.75 (d, 1H), 7.35 (d, 1H), 4.25 (q, 2H), 4.0 (d, 1H), 3.75 ( s,6H), 3.4 (d, 1H), 1.7 (s, 3H), 1.3 (t, 3H) ppm.

Individual enantiomers of compound 47 were obtained using chiral chromatography ( ^1H NMR as above).

Using this general method the following were also obtained:

ethyl 3-[2-chloro-5-(3,5-dimethyl-2,6-dioxo-4-thioxo-1,3,5-triazinan-1-yl)phenyl]-5-methyl-4Nizoxazole-5 -carboxylate (compound 36).

¹ H NMR (400 MHz, CHCl ₃ ) δ 7.7 (d, 1H), 7.55 (d, 1H), 7.25 (m, 1H), 4.25 (q, 2H), 4.0 (d, 1H), 3.75 (s,6H), 3.4 (d, 1H), 1.7 (s, 3H), 1.3 (t, 3H) ppm.

Methyl 3-[2-chloro-5-(3,5-dimethyl-2,6-dioxo-4-thioxo-1,3,5-triazinan-1-yl)-4-fluorophenyl]-5trifluoromethyl-4H- isoxazole-5-carboxylate (compound 262).

¹ H NMR (400 MHz, CHCl ₃ ) 5 7.8 (d, 1H), 7.45 (d, 1H), 4.2 (d, 1H), 4.0 (d, 1H), 3.95 (s, 3H), 3.8 (s, 6H), ppm.

Methyl 3-[2-chloro-5-(3,5-dimethyl-2,6-dioxo-4-thioxo-1,3,5-triazinan-1-yl)-4-fluorophenyl]-4,5dimethyl- 4H-isoxazole-5-carboxylate (compound 145).

¹ H NMR (400 MHz, CHCl ₃ ) δ 7.5 (d, 1H), 7.4 (d, 1H), 3.95 (q, 1H), 3.8 (s, 3H), 3.75 (s,6H), 1.75 (s, 3H), 1.1(d, 3H) ppm.

[3-[2-Chloro-5-(3,5-dimethyl-2,6-dioxo-4-thioxo-1,3,5-triazinan-1-yl)-4-fluorophenyl]-5-methyl-4Nizoxazole -5-yl]methyl acetate (compound 51).

^1H NMR (400 MHz, _CHCl3 ) δ 7.75 (d, 1H), 7.35 (d, 1H), 4.2 (q, 2H), 3.75 (s,6H), 3.5 (d, 1H), 3.25 (d, 1H), 2.1 (s, 3H), 1.5 (s, 3H) ppm.

3-[5-(5-Acetyl-5-methyl-4H-isoxazol-3-yl)-4-chloro-2-fluorophenyl]-1,5-dimethyl-6-thioxo-1,3,5triazinan-2, 4-Dione (compound 290).

^1H NMR (400 MHz, СНС1з) δ 7.7 (d, 1H), 7.4 (d, 1H), 3.95 (d, 1H), 3.75 (s,6H), 3.2 ( d, 1H), 2.35 (s, 3H), 1.55 (s, 3H) ppm.

Ethyl 3-[2,4-dichloro-5-(3,5-dimethyl-2,6-dioxo-4-thioxo-1,3,5-triazinan-1-yl)phenyl]-5-methyl-4Nizoxazole -5-carboxylate (compound 58).

- 25 047159

1H NMR (400 MHz, СНС1з) δ 7.8 (s, 1H), 7.65 (s, 1H), 4.4 (q, 2H), 4.0 (d, 1H), 3.75 (s ,6H), 3.4 (d, 1H), 1.7 (s, 3H), 1.3(t, 3H) ppm.

Methyl 3-[2-chloro-5-(3,5-dimethyl-2,6-dioxo-4-thioxo-1,3,5-triazinan-1-yl)-4-fluorophenyl]-5methoxy-4H- isoxazole-5-carboxylate (compound 311).

1H NMR (400 MHz, CHCl ₃ ) δ 7.8 (d, 1H), 7.4 (d, 1H), 3.95 (d, 1H), 3.9 (s, 3H), 3.8 ( s,6H), 3.6 (d, 1H), 3.45 (s, 3H) ppm.

Example 2. Preparation of 3-[2-chloro-5-(3,5-dimethyl-2,6-dioxo-4-thioxo-1,3,5-triazinan-1-yl)-4fluorophenyl]-5-methyl- 4H-isoxazole-5-carboxylic acid (compound 45).

Step 1. Preparation of 3-[2-chloro-4-fluoro-5-[[methyl(methylcarbamothioyl)carbamoyl]amino]phenyl]-5methyl-4H-isoxazole-5-carboxylic acid

Aqueous sodium hydroxide (2 N; 0.87 mL, 1.75 mmol) was added to the stirred suspension of ethyl 3-[2-chloro-5-(3,5-dimethyl-2,6-dioxo-4-thioxo -1,3,5-triazinan-1-yl)-4-fluorophenyl]-5-methyl4H-isoxazole-5-carboxylate (400 mg, 0.87 mmol) in ethanol (5 ml) at room temperature. The resulting mixture was stirred for 30 minutes, water (5 ml) was added, followed by the addition of dilute aqueous hydrochloric acid (2 ml). The mixture was filtered and the solid was dried to obtain 3-[2-chloro-4-fluoro-5-[[methyl(methylcarbamothioyl)carbamoyl]amino]phenyl]-5-methyl4H-isoxazole-5-carboxylic acid as a white solid ( 260 mg).

1H NMR (400 MHz, DMSO) δ 13.3 (br s, 1H), 10.15 (s, 2H), 7.95 (d, 1H), 7.7 (d, 1H), 3.85 ( d, 1H), 3.55 (s, 3H), 3.4 (d, 1H), 3.0 (s, 3H), 1.6 (s, 3H) ppm.

Step 2. Preparation of 3-[2-chloro-5-(3,5-dimethyl-2,6-dioxo-4-thioxo-1,3,5-triazinan-1-yl)-4fluorophenyl]-5-methyl- 4H-isoxazole-5-carboxylic acid (compound 45)

Triethylamine (0.068 ml, 0.48 mmol) then carbonyldiimidazole (93 mg, 0.56 mmol) was added to the stirred solution of 3-[2-chloro-4-fluoro-5-[[methyl(methylcarbamothioyl)carbamoyl]amino]phenyl ]-5methyl-4H-isoxazole-5-carboxylic acid (150 mg, 0.37 mmol) in toluene (3 ml) at room temperature. The mixture was then refluxed for 3 hours, cooled and evaporated under reduced pressure to give a residue, which was purified by chromatography to give 3-[2-chloro-5-(3,5-dimethyl-2,6-dioxo- 4-thioxo-1,3,5-triazinan-1-yl)-4-fluorophenyl]-5-methyl-4Nizoxazole-5-carboxylic acid (compound 45) as a white solid (35 mg).

1H NMR (400 MHz, СНС1з) δ 7.7 (d, 1H), 7.3 (d, 1H), 5.2 (br s, 1H), 3.75 (d, 1H), 3.7 ( s,6H), 3.2 (d, 1H), 1.5 (s, 3H) ppm.

Example 3. Preparation of 3-[2,4-dichloro-5-(3,5-dimethyl-2,6-dioxo-4-thioxo-1,3,5-triazinan-1-yl)phenyl]-5-methyl -4H-isoxazole-5-carboxylic acid (compound 56)

Concentrated sulfuric acid (0.75 ml, 13 mmol) was added to the stirred solution of ethyl 3-[2,4-dichloro-5-(3,5-dimethyl-2,6-dioxo-4-thioxo-1,3, 5-triazinan-1-yl)phenyl]-5-methyl-4Nisoxazole-5-carboxylate (prepared as described in Example 1, Step 5; 300 mg, 0.63 mmol) in glacial acetic acid (3 ml) and the resulting mixture heated at 100°C for 1 hour. The mixture was cooled to ambient temperature, poured into water and the resulting mixture was extracted with dichloromethane. The organic extract was dried over magnesium sulfate, filtered and evaporated under reduced pressure to obtain a residue, which was purified by chromatography to give 3-[2,4-dichloro-5-(3,5-dimethyl-2,6-dioxo-4- thioxo-1,3,5-triazinan-1-yl)-phenyl]-5-methyl-4H-isoxazole-5carboxylic acid (compound 56) as an oil (200 mg).

1H NMR (400 MHz, CHCl ₃ ) δ 7.75 (s, 1H), 7.65 (s, 1H), 5.75 (br s, 1H), 4.0 (d, 1H), 3.75 (s,6H), 3.4(d, 1H), 1.7(s, 3H) ppm.

- 26 047159

Example 4 Preparation of [3-(2-chloro-4-fluoro-5-nitrophenyl)-5-methyl-4H-isoxazol-5-yl]methyl acetate

ABOUT

[3-(2-chloro-4-fluoro-5-nitrophenyl)-5-methyl-4H-isoxazol-5-yl]methanol mixture (prepared as described in Example 1, Step 2; 150 mg, 0.52 mmol) and acetic anhydride (60 mg, 0.57 mmol) was heated at 90°C for 2 hours, then cooled and evaporated under reduced pressure to give [3-(2-chloro-4-fluoro-5-nitrophenyl)-5 -methyl-4H-isoxazol-5-yl]methyl acetate as an oil (160 mg).

^1H NMR (400 MHz, СНС1з) δ 8.45 (d, 1H), 7.45 (d, 1H), 4.3 (d, 1H), 4.15 (d, 1H), 3.5 ( d, 1H), 3.25 (d, 1H), 2.1 (s, 3H), 1.5 (s, 3H) ppm.

Example 5. Preparation of 3-[4-chloro-2-fluoro-5-[5-(hydroxymethyl)-5-methyl-4H-isoxazol-3-yl]phenyl]1,5-dimethyl-6-thioxo-1, 3,5-triazinan-2,4-diones (compounds 49)

A saturated aqueous sodium hydrogen carbonate solution (76 mg, 0.89 mmol) was added to the stirred solution of [3-[2-chloro-5-(3,5-dimethyl-2,6-dioxo-4-thioxo-1,3,5 -triazinan-1-yl)-4-fluorophenyl]-5methyl-4H-isoxazol-5-yl]methyl acetate (prepared as described in Example 1, Step 5; 250 mg, 0.55 mmol) in methanol (25 ml). The mixture was stirred at room temperature for 17 hours, concentrated under reduced pressure and extracted with dichloromethane. The organic extracts were dried and evaporated under reduced pressure to leave a residue, which was purified by chromatography to give 3-[4-chloro-2-fluoro-5-[5-(hydroxymethyl)-5-methyl-4H-isoxazol-3-yl ]phenyl]1,5-dimethyl-6-thioxo-1,3,5-triazinan-2,4-dione (compound 49) as a glassy solid (138 mg).

^1H NMR (400 MHz, CHCl ₃ ) δ5 7.75 (d, 1H), 7.55 (d, 1H), 3.75 (s, 6H), 3.65 (d, 1H), 3.55 (d, 1H), 3.3 (d, 1H), 3.2 (d, 1H), 1.45 (s, 3H) ppm (OH not observed).

Example 6 Preparation of [3-[2-chloro-5-(3,5-dimethyl-2,6-dioxo-4-thioxo-1,3,5-triazinan-1-yl)-4fluorophenyl]-5-methyl -4H-isoxazol-5-yl]methylmethanesulfonate (compound 53)

Methanesulfonyl chloride (0.1 mL, 1.0 mmol) was added to the stirred solution of 3-[4-chloro-2fluoro-5-[5-(hydroxymethyl)-5-methyl-4H-isoxazol-3-yl]phenyl]-1 ,5-dimethyl-6-thioxo-1,3,5-triazinan2,4-dione (prepared as described in Example 5; 38 mg, 0.077 mmol) in toluene (3 ml). The resulting solution was stirred at room temperature for 2 hours, evaporated under reduced pressure and the residue was extracted with dichloromethane. The extracts were dried and evaporated under reduced pressure to obtain a residue, which was purified by chromatography to give [3-[2-chloro-5-(3,5-dimethyl-2,6-dioxo-4-thioxo-1,3,5 -triazinan-1-yl)-4-fluorophenyl]-5-methyl-4Nizoxazol-5-yl]methylmethanesulfonate (compound 53) as a resin (40 mg).

^1H NMR (400 MHz, СНС1з) δ 7.7 (d, 1H), 7.35 (d, 1H), 4.3 (q, 2H), 3.75 (s,6H), 3.65 ( d, 1H), 3.25 (d, 1H), 3.1 (s, 3H), 1.4 (s, 3H) ppm.

Example 7. Preparation of 3-[4-chloro-2-fluoro-5-[5-[N-methoxy-C-methylcarbonimidoyl]-5methylisoxazolidin-3-yl]phenyl]-1,5-dimethyl-6-thioxo-1 ,3,5-triazinan-2,4-dione (compounds 293)

O-methylhydroxylamine hydrochloride (12 mg, 0.14 mmol) was added to the stirred solution of 3-[5-(5-acetyl-5-methyl-4H-isoxazol-3-yl)-4-chloro-2-fluorophenyl]-1 ,5-dimethyl-6-thioxo-1,3,5-triazinan- 27 047159

2,4-dione (prepared as described in Example 1, Step 5; 51 mg, 0.12 mmol) in ethanol (2.5 ml) and dichloromethane (2 ml). The resulting solution was stirred at room temperature for 17 hours, evaporated under reduced pressure, and the residue was partitioned between dichloromethane and water. The phases were separated and the organic phase was dried and evaporated under reduced pressure to give a residue, which was purified by chromatography to give 3-[4-chloro-2-fluoro-5-[5-[N-methoxy-Smethylcarbonimidoyl]-5-methylisoxazolidine- 3-yl]phenyl]-1,5-dimethyl-6-thioxo-1,3,5-triazinan-2,4dione (compound 293) as a fluff solid (52 mg).

^1H NMR (400 MHz, СНС1з) δ 7.7 (d, 1H), 7.35 (d, 1H), 4.1 (d, 1H), 3.85 (s, 3H), 3.8 ( s,6H), 3.2 (d, 1H), 1.95 (s, 3H), 1.6 (s, 3H) ppm.

Using this general method we also obtained:

3-[4-chloro-2-fluoro-5-[5-[N-hydroxy-C-methylcarbonimidoyl]-5-methylisoxazolidin-3-yl]phenyl]1,5-dimethyl-6-thioxo-1,3, 5-triazinan-2,4-dione (compound 296).

^1H NMR (400 MHz, CHCI3) δ 7.7 (d, 1H), 7.35 (d, 1H), 5.7 (br s, 1H), 3.9 (d, 1H), 3.75 (s,6H), 3.3 (d, 1H), 2.0 (s, 3H), 1.65 (s, 3H) ppm.

Example 8. Preparation of methyl 2-[1-[3-[2-chloro-5-(3,5-dimethyl-2,6-dioxo-4-thioxo-1,3,5-triazinan-1yl)-4 -fluorophenyl]-5-methyl-4H-isoxazol-5-yl]ethylideneamino]oxyacetate (compound 299)

Methyl bromoacetate (0.01 ml, 0.1 mmol), then potassium carbonate (12.5 mg, 0.09 mmol) and potassium iodide (catalytic amount) were added to the solution of 3-[4-chloro-2-fluoro-5- [5-[N-Hydroxy-Cmethylcarbonimidoyl]-5-methylisoxazolidin-3-yl]phenyl]-1,5-dimethyl-6-thioxo-1,3,5-triazinan-2,4dione (prepared as described in Example 7 ; 40 mg, 0.09 mmol) in 4-methylpentan-2-one (2 ml). The resulting mixture was heated in a microwave oven for 1 hour at 100°C, cooled and the solvent was evaporated under reduced pressure to give a solid, which was purified by chromatography to give methyl 2-[1-[3-[2-chloro -5-(3,5-dimethyl-2,6-dioxo-4-thioxo-1,3,5triazinan-1-yl)-4-fluorophenyl]-5-methyl-4H-isoxazol-5-yl]ethylideneamino] hydroxyacetate (compound 299) as a resin (20 mg).

1H NMR (400 MHz, CHCI3) δ 7.7 (d, 1H), 7.35 (d, 1H), 4.6 (s, 2H), 4.0 (d, 1H), 3.8 (s ,6H), 3.7 (s, 3H), 3.2 (d, 1H), 2.0 (s, 3H), 1.6 (s, 3H) ppm.

Example 9. Preparation of 3-[2-chloro-5-(3,5-dimethyl-2,6-dioxo-4-thioxo-1,3,5-triazinan-1-yl)-4fluorophenyl]-5-methyl- 4H-isoxazole-5-carboxamide (compound 308).

Step 1. Preparation of 3-[2-chloro-5-(3,5-dimethyl-2,6-dioxo-4-thioxo-1,3,5-triazinan-1-yl)-4fluorophenyl]-5-methyl- 4H-isoxazole-5-carbonyl chloride

Oxalyl chloride (0.01 mL, 0.11 mmol) then dimethylformamide (drop) was added to the stirred solution of 3-[2-chloro-5-(3,5-dimethyl-2,6-dioxo-4-thioxo-1, 3,5-triazinan-1-yl)-4-fluorophenyl]-5methyl-4H-isoxazole-5-carboxylic acid (prepared as described in example 3; 42 mg, 0.10 mmol) in dichloromethane (2 ml) at 0 °C. The resulting solution was stirred for 5 minutes, then warmed to ambient temperature and used directly.

Step 2. Preparation of 3-[2-chloro-5-(3,5-dimethyl-2,6-dioxo-4-thioxo-1,3,5-triazinan-1-yl)-4fluorophenyl]-5-methyl- 4H-isoxazole-5-carboxamide (compound 308)

Concentrated aqueous ammonia (0.5 mL, 30 mmol) was added to the stirred solution of 3[2-chloro-5-(3,5-dimethyl-2,6-dioxo-4-thioxo-1,3,5-triazinan-1 -yl)-4-fluorophenyl]-5-methyl-4H-isoxazole5-carbonyl chloride in dichloromethane (2 ml) at 0°C. The resulting solution was stirred for 30 minutes, then evaporated under reduced pressure to give a white solid, which was triturated with water to give 3-[2-chloro-5-(3,5-dimethyl-2,6-dioxo-4-thioxo -1,3,5-triazinan-1-yl)-4fluorophenyl]-5-methyl-4H-isoxazole-5-carboxamide (compound 308) as a white solid

- 28 047159 (35 mg).

1H NMR (400 MHz, d6-DMSO) δ 7.9 (m, 2H), 7.6 (br s, 1H), 7.4 (br s, 1H), 3.8 (d, 1H), 3 .65 (s,6H), 1.6 (s,3H) ppm (1 CH was not observed due to suppression of the water signal).

Example 10. Preparation of 3-[2-chloro-5-(3,5-dimethyl-2,6-dioxo-4-thioxo-1,3,5-triazinan-1-yl)-4fluorophenyl]-5-methyl- N-methylsulfonyl-4H-isoxazole-5-carboxamide (compound 284).

Step 1. Preparation of 3-[4-chloro-2-fluoro-5-[5-(imidazol-1-carbonyl)-5-methyl-4H-isoxazol-3yl]phenyl]-1,5-dimethyl-6-thioxo -1,3,5-triazinan-2,4-dione

Carbonyldiimidazole (234 mg, 1.4 mmol) was added to a stirred solution of 3-[2-chloro-5-(3,5dimethyl-2,6-dioxo-4-thioxo-1,3,5-triazinan-1-yl) -4-fluorophenyl]-5-methyl-4H-isoxazole-5-carboxylic acid (prepared as described in example 3; 400 mg, 0.93 mmol) and triethylamine (0.17 ml, 0.93 mmol) in dichloromethane ( 5 ml) at ambient temperature. The resulting solution was stirred for 45 minutes, then the solvent was evaporated under reduced pressure to obtain 3-[4-chloro-2fluoro-5-[5-(imidazol-1-carbonyl)-5-methyl-4H-isoxazol-3-yl] phenyl]-1,5-dimethyl-6-thioxo-1,3,5triazinan-2,4-dione, which was used directly.

Step 2. Preparation of 3-[2-chloro-5-(3,5-dimethyl-2,6-dioxo-4-thioxo-1,3,5-triazinan-1-yl)-4fluorophenyl]-5-methyl- N-methylsulfonyl-4H-isoxazole-5-carboxamide (compound 284)

DBU (0.13 mL, 0.84 mmol) was added to a stirred solution of 3-[4-chloro-2-fluoro-5-[5(imidazol-1-carbonyl)-5-methyl-4H-isoxazol-3-yl ]phenyl]-1,5-dimethyl-6-thioxo-1,3,5-triazinan-2,4dione (200 mg, 0.42 mmol) and methanesulfonamide (82 mg, 0.84 mmol) in dichloromethane (5 ml ) at ambient temperature. The resulting solution was stirred for 40 hours, then evaporated under reduced pressure to give a yellow oil, which was purified by chromatography to give 3-[2-chloro-5-(3,5-dimethyl-2,6-dioxo-4-thioxo -1,3,5-triazinan-1-yl)-4-fluorophenyl]-5-methyl-Nmethylsulfonyl-4H-isoxazole-5-carboxamide (compound 284) as a white solid (52 mg).

1H NMR (400 MHz, CHCl ₃ ) δ 9.1 (br s, 1H), 7.7 (d, 1H), 7.4 (d, 1H), 4.0 (d, 1H), 3.75 (s,6H), 3.45 (d, 1H), 3.3 (s, 3H), 1.75 (s, 3H) ppm.

Using this general method we also obtained:

3-[2-chloro-5-(3,5-dimethyl-2,6-dioxo-4-thioxo-1,3,5-triazinan-1-yl)-4-fluorophenyl]-N(dimethylsulfamoyl)-5 -methyl-4H-isoxazole-5-carboxamide (compound 305).

1H NMR (400 MHz, CHCl ₃ ) δ 8.95 (br s, 1H), 7.7 (d, 1H), 7.4 (d, 1H), 4.0 (d, 1H), 3.75 (s,6H), 3.45 (d, 1H), 2.95 (s,6H), 1.75 (s, 3H) ppm.

Examples of compositions

Wettable powders A) b) With) Active Ingredients 25% 50% 75% Sodium lignosulfonate 5% 5% - Sodium lauryl sulfate 3% - 5 % Sodium diisobutyl naphthalene sulfonate - 6% 10% Polyethylene glycol phenolic ether - 2% - (7-8 mol ethylene oxide) Highly dispersed silicic acid 5% 10% 10% Kaolin 62% 27% -

The combination is thoroughly mixed with the excipients and the mixture is thoroughly ground in a suitable mill to obtain wettable powders which can be diluted with water to obtain a suspension of the required concentration.

- 29 047159

Emulsifiable concentrate.

Active ingredients 10%

Polyethylene glycol octylphenol ether 3% (4-5 mol ethylene oxide)

Calcium dodecylbenzenesulfonate 3%

Castor oil polyglycol ether (35 mol 4% ethylene oxide)

Cyclohexanone 30%

Xylene mixture

50%

From this concentrate, by diluting with water, emulsions of any required dilution can be obtained, which can be used to protect plants.

Dust-like preparations a) b) c)

Active ingredients 5% 6% 4%

Talc 95% - Kaolin - 94% Mineral filler - - 96%

Ready-to-use powdered preparations are prepared by mixing the combination with a carrier and grinding the mixture in a suitable mill.

Extruded granules.

Active Ingredients 15% Sodium lignosulfonate 2% Carboxymethylcellulose 1 % Kaolin 82%

The combination is mixed and crushed with excipients and the mixture is moistened with water. The mixture is extruded and then dried in a stream of air.

Coated granules.

Active ingredients 8%

Polyethylene glycol (molecular weight 200) 3%

Kaolin 89%

The finely ground combination in a mixing device is evenly applied to kaolin moistened with polyethylene glycol. In this way, dust-free, coated granules are obtained.

Suspension concentrate.

Active ingredients 40%

Propylene glycol 10%

Polyethylene glycol nonylphenol ether (15 mol 6% ethylene oxide)

Sodium lignosulfonate 10%

Carboxymethylcellulose 1%

Silicone oil (as a 75% emulsion in water) 1%

Water 32%

The finely ground combination is thoroughly mixed with the excipients to obtain a suspension concentrate, from which suspensions of any required dilution can be obtained by dilution with water.

Slow release capsule suspension.

Mix 28 parts of the combination with 2 parts of an aromatic solvent and 7 parts of a mixture of toluene diisocyanate/polymethylene polyphenyl isocyanate (8:1). This mixture is emulsified in a mixture of 1.2 parts polyvinyl alcohol, 0.05 parts defoamer and 51.6 parts water to obtain particles of the required size. To this emulsion is added a mixture of 2.8 parts 1,6-diaminohexane in 5.3 parts water. The mixture is stirred until the polymerization reaction is completed.

The resulting capsule suspension is stabilized by adding 0.25 parts thickener and 3 parts dispersant. The composition of the capsule suspension contains 28% active ingredients. The average diameter of capsules is 8-15 microns.

The resulting composition is applied in the form of an aqueous suspension to seeds in a device suitable

- 30 047159 for this purpose.

Biological examples.

Biological effectiveness before emergence.

Weed and/or crop seeds were sown in standard soil in pots. After cultivation for one day under controlled greenhouse conditions (at 24/16°C, day/night; 14-hour photoperiod; 65% humidity), the plants were sprayed with an aqueous spray solution prepared from the technical active ingredient in an acetone/acetone solution. water (50:50) containing 0.5% Tween 20 (polyoxyethylene sorbitan monolaurate, CAS RN 9005-64-5), to obtain the required final dose of the test compound.

The test plants were then grown under controlled conditions in a greenhouse (24/16°C, day/night; 14-hour photoperiod; 65% humidity) and watered twice daily. After 13 days, the test results were assessed (100=damage to the entire plant; 0=no damage to the plant). The results are shown in table. 2 below.

table 2

Compound Application rate (g/ha) Kinds AMARA LOLPE EPHHL SETFA ECHCG IPOHE 36 250 70 10 70 90 90 40 45 250 100 100 100 100 100 100 47 250 100 70 100 100 100 100 47 (enantiomer A) 250 100 50 100 100 60 90 47 (enantiomer B) 250 100 40 100 100 50 80 49 250 100 90 100 100 90 90 51 250 100 90 100 100 90 80 53 250 100 70 - 100 60 0 56 250 90 10 10 10 0 thirty 58 250 90 0 0 0 0 60 145 250 100 90 100 100 90 100 262 250 - thirty 0 50 thirty 0 284 250 100 40 100 70 thirty 100 290 250 100 90 100 100 90 100 293 250 100 90 100 100 90 50 296 250 100 80 90 100 80 90 299 250 100 60 90 60 0 80 305 250 100 thirty 60 90 thirty 80 308 250 100 60 80 90 10 50 311 250 100 10 50 90 10 70

Biological effectiveness after emergence.

Weed and/or crop seeds were sown in standard soil in pots. After cultivation for 8 days under controlled greenhouse conditions (at 24/16°C, day/night; 14-hour photoperiod; 65% humidity), the plants were sprayed with an aqueous spray solution prepared from the technical active ingredient in an acetone/water solution ( 50:50) containing 0.5% Tween 20 (polyoxyethylene sorbitan monolaurate, CAS RN 9005-64-5), to obtain the required final dose of the test compound.

The test plants were then grown under controlled conditions in a greenhouse (24/16°C, day/night; 14 h photoperiod; 65% humidity) and watered twice daily. After 13 days, the test results were assessed (100=damage to the entire plant; 0=no damage to the plant). The results are shown in table. 3 below.

- 31 047159

Table 3

Compound Application rate (g/ha) Kinds AMAR A CHEA L ERNN L IPOH E ELEI N LOLP E DIGS A SETF A ESNS G 36 250 100 90 90 70 50 50 100 100 100 45 250 100 100 100 100 100 100 100 100 100 47 250 100 100 100 100 100 100 100 100 100 47 (enantiome r A) 250 100 100 90 100 90 70 100 100 100 47 (enantiome rB) 250 100 100 100 100 100 100 100 100 100 49 250 100 100 100 100 90 60 90 100 70 51 250 100 100 100 90 80 50 100 100 thirty 53 250 90 90 90 80 80 40 70 40 thirty 56 250 100 90 80 90 80 thirty 80 90 90 58 250 90 90 70 100 90 thirty 80 90 90 145 250 100 100 100 100 100 100 100 100 100 262 250 40 thirty 60 50 40 0 50 thirty 20 284 250 100 100 90 100 100 80 100 100 100 290 250 100 100 100 100 100 90 100 90 90 293 250 100 100 100 100 90 60 100 90 thirty 296 250 100 100 80 90 90 70 70 80 thirty 299 250 100 100 90 90 90 90 80 100 100 305 250 100 100 100 100 100 100 100 100 100 308 250 100 100 90 100 100 90 100 100 100 311 250 90 90 90 90 90 50 80 100 90

Claims (16)

1. Compound of formula (I) or an agronomically acceptable salt thereof where X is selected from the group consisting of oxygen and sulfur; Y represents C-H; R ¹ is selected from the group consisting of hydrogen and C ₁ -C6 alkyl; R ² is selected from the group consisting of hydrogen, amino, C1- _C6 alkyl, _C3 - _C6 alkenyl and _C3 - _C6 alkynyl; R ³ is selected from the group consisting of hydrogen, halogen, C1- _C4 -alkyl, C1-C4 _- haloalkyl, C1-C4alkoxy, C1-C4 _- haloalkoxy and C1- _C4 -alkylsulfonyl; R ⁴ is selected 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; each of R ⁵ and R ⁶ is independently selected from the group consisting of hydrogen, cyano, C 1 -C ₆ -alkyl, C 1 -C ₆ -haloalkyl, C 1 -C ₄ -alkylsulfonyl, CO ₂ R ⁹ , CONR ¹⁰ R ¹¹ and CH2OR ¹² ; each of R ⁷ and R ⁸ 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 , CONR10R ¹¹ and CH2OR ¹² ; Z is selected from the group consisting of oxygen, NOR ¹⁶ and NN(R ¹⁶ ) ₂ ; R ⁹ is selected from the group consisting of hydrogen, C1-C10 alkyl, C1-C10 haloalkyl, C3-C6 alkenyl, C3-C6 haloalkenyl, C3-C6 alkynyl, C1-C4 alkoxyC1-C6 alkyl, C1-C4-haloalkoxyC1-C6-alkyl, C6-C10-arylC1-C3-alkyl, C6-C10-arylC1-C3-alkyl substituted with 1-4 ^R13 groups, heteroarylC1-C3alkyl and heteroarylC1- _C3 -alkyl substituted 1-3 R ¹³ groups, where each heteroaryl moiety is a 5- or 6-membered monocyclic aromatic ring which contains 1, 2, 3 or 4 heteroatoms individually selected from nitrogen, oxygen and sulfur; R ¹⁰ is selected from the group consisting of hydrogen, C1-C ₆ alkyl and SO2R ¹⁴ ; R ¹¹ is selected from the group consisting of hydrogen and C1-C ₆ -alkyl; or R ¹⁰ and R ¹¹ together with the nitrogen atom to which they are attached form a 3-6 membered heterocyclyl ring, which optionally contains an oxygen atom; R ¹² is selected from the group consisting of hydrogen, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkylsulfonyl, C1-C4 haloalkylsulfonyl, phenylsulfonyl, phenylsulfonyl substituted with 12 R ¹³ groups; C1-C4 alkylcarbonyl, C1-C ₄ haloalkylcarbonyl, C ₆ -C ₁₀ arylcarbonyl, C ₆ -C ₁₀ - 32 047159 arylcarbonyl substituted with 1-4 R ¹³ groups, heteroarylcarbonyl, heteroarylcarbonyl substituted with 1-3 R ¹³ groups, C6-C10-arylC1-C3 alkylcarbonyl, C6-C10-arylC1-C3 alkylcarbonyl substituted with 1-4 groups R ¹³ , heteroarylC1-C3-alkylcarbonyl and heteroarylC1- _C3 -alkylcarbonyl substituted with 1-3 R ¹³ groups; each R ¹³ is 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; wherein each a heteroaryl moiety is a 5- or 6-membered monocyclic aromatic ring that contains 1, 2, 3 or 4 heteroatoms individually selected from nitrogen, oxygen and sulfur; R ¹⁴ is selected from the group consisting of C1- _C4 alkyl, C1- _C4 haloalkyl and _C1 - _C4 alkyl( _C1 - _C4 alkyl)amino; R ¹⁵ is selected from the group consisting of hydrogen, C1- _C4 alkyl and C1- _C4 haloalkyl; R ¹⁶ is selected from the group consisting of hydrogen, C1- _C4- alkyl, C1- _C4- haloalkyl and C1-C4alkoxycarbonylC1- _C4 -alkyl. 2. The compound according to claim 1, wherein X represents sulfur. 3. A compound according to claim 1 or 2, wherein R ¹ is selected from the group consisting of hydrogen and C1- _C4 alkyl. 4. A compound according to any one of claims 1 to 3, wherein R ² is selected from the group consisting of hydrogen, C 1 -C 4 alkyl and C ₃ -C ₄ alkynyl. 5. A compound according to any one of claims 1 to 4, wherein R ³ is selected from the group consisting of hydrogen, chlorine and fluorine. 6. A compound according to any one of claims 1 to 5, wherein R ⁴ is selected from the group consisting of hydrogen, chlorine, cyano and aminothiocarbonyl. 7. A compound according to any one of claims 1 to 6, wherein each of R ⁵ and R ⁶ is independently selected from the group consisting of hydrogen, C 1 -C ₄ alkyl, CO 2 R ⁹ and CH 2 OR ¹² . 8. A compound according to any one of claims 1 to 7, wherein each of R ⁷ and R ⁸ is independently selected from the group consisting of hydrogen, C1- _C4 alkyl, C1- _C6 haloalkyl, ^CO2R9 , ^CONR10R11 and CH2OR ¹² . 9. A compound according to any one of claims 1 to 8, in which R ⁹ is selected from the group consisting of hydrogen, C1-C4 alkyl, C1-C ₄ haloalkyl, C1-C ₂ alkoxyC1-C ₂ alkyl, phenylC1-C ₂ -alkyl and phenylC1-C ₂ -alkyl substituted with 1-2 R ¹³ groups. 10. A compound according to any one of claims 1 to 9, wherein R ¹⁰ is selected from the group consisting of hydrogen and SO2R ¹⁴ . 11. A compound according to any one of claims 1 to 10, wherein R ¹¹ represents hydrogen. 12. A compound according to any one of claims 1 to 11, in which R ¹² is selected from the group consisting of hydrogen, C1C2-alkyl, C1-C2-alkylsulfonyl, C1-C2-haloalkylsulfonyl, C1-C4-alkylcarbonyl, phenylcarbonyl, phenylcarbonyl, substituted with 1-2 R ¹³ groups, phenylC1-C2 alkylcarbonyl and phenylC1-C ₂ alkylcarbonyl substituted with 1-2 R ¹³ groups. 13. A compound according to any one of claims 1 to 12, in which R ¹³ is selected from the group consisting of halogen, C1C ₄ -alkyl, C1-C ₄ -haloalkyl, C1-C ₄ -alkoxy, C1-C ₄ -haloalkoxy, cyano and C1-C ₄ -alkylsulfonyl. 14. A compound according to any one of claims 1 to 13, in which R ¹⁴ is selected from the group consisting of C ₁ -C ₄ -alkyl and C ₁ -C ₄ -alkyl(C ₁ -C ₄ -alkyl)amino. 15. An agrochemical composition containing a herbicidally effective amount of a compound of formula (I) according to any one of claims 1 to 14 and an agrochemically acceptable diluent or carrier. 16. A method for controlling or preventing the growth of undesirable plants, wherein a herbicidally effective amount of a compound of formula (I) according to any one of claims 1 to 14, or a composition according to claim 15, is applied to the plants, their parts or the place where they grow.