Herbicidal pyrimidinone derivatives

Abstract

Disclosed are compounds of formula (I) wherein the substituents are as defined in claim 1, which can be used as pesticidal agents, in particular as herbicides. # imgabs0 #

Description

[0001] The present invention relates to herbicidally active isoxazoline derivatives and to processes and intermediates for the preparation of such derivatives. The invention further extends to herbicidal compositions comprising such derivatives and to the use of such compounds and compositions for controlling unwanted vegetation in crops of useful plants: in particular for controlling weeds.

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

[0003]

[0004] in

[0005] R 1 Selected from the group consisting of: hydrogen and C1-C6 alkyl;

[0006] R 2 Selected from the group consisting of C1-C6 alkyl, C3-C6 alkenyl and C3-C6 alkynyl;

[0007] R 3 Selected from the group consisting of hydrogen, halogen, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy and C1-C4 alkylsulfonyl;

[0008] R 4 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;

[0009] R 5 and R 6 Each is independently selected from the group consisting of hydrogen, cyano, C1-C6 alkyl, C1-C6 haloalkyl, C1-C4 alkylsulfonyl, CO2R 9 ,CONR 10 R 11 and CH2OR 12 ;

[0010] R 7 and R 8 are each independently selected from the group consisting of hydrogen, cyano, C1-C6 alkyl, C1-C6 haloalkyl, C1-C4 alkoxy, C1-C4 alkylsulfonyl, C(=Z)R 15 、CO2R 9 ,CONR 10R 11 and CH2OR 12 ; Z is selected from the group consisting of: oxygen, NOR 16 and NN(R 16 )2;

[0011] R 9 Selected from the group consisting of: hydrogen, C1-C 10 Alkyl, C1-C 10 Halogenated alkyl, C3-C6 alkenyl, C3-C6 haloalkenyl, C3-C6 alkynyl, C1-C4 alkoxy C1-C6 alkyl, C1-C4 haloalkoxy C1-C6 alkyl, C6-C 10 Aryl C1-C3 alkyl, 1 to 4 R 13 The group substituted C6-C 10 Aryl C1-C3 alkyl, heteroaryl C1-C3 alkyl, and 1 to 3 R 13 A group representing a substituted heteroaryl C1-C3 alkyl group;

[0012] R 10 Selected from the group consisting of: hydrogen, C1-C6 alkyl and SO2R 14 ;

[0013] R 11 is selected from the group consisting of: hydrogen and C1-C6 alkyl; or

[0014] R 10 and R 11 Together with the nitrogen to which they are attached, they form a 3- to 6-membered heterocyclyl ring, which optionally contains an oxygen atom;

[0015] R 12 is selected from the group consisting of hydrogen, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkylsulfonyl, C1-C4 haloalkylsulfonyl, phenylsulfonyl, 2 to 3 R 13 substituted phenylsulfonyl; C1-C4 alkylcarbonyl, C1-C4 haloalkylcarbonyl, C6-C 10 Arylcarbonyl, 1-4 groups R 13 Substituted C6-C 10 Arylcarbonyl, heteroarylcarbonyl, 1 to 3 R 13 A heteroarylcarbonyl group substituted with a C6-C 10 Aryl C1-C3 alkylcarbonyl, 1 to 4 R 13 The group substituted C6-C 10 Aryl C1-C3 alkylcarbonyl, heteroaryl C1-C3 alkylcarbonyl, and 1 to 3 R 13The group represented is a substituted heteroaryl C1-C3 alkylcarbonyl;

[0016] Each R 13 independently selected from the group consisting of halogen, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, cyano, and C1-C4 alkylsulfonyl;

[0017] R 14 Selected from the group consisting of C1-C4 alkyl, C1-C4 haloalkyl and C1-C4 alkyl(C1-C4 alkyl)amino;

[0018] R 15 Selected from the group consisting of: hydrogen, C1-C4 alkyl and C1-C4 haloalkyl;

[0019] Each R 16 independently selected from the group consisting of hydrogen, C1-C4 alkyl, C1-C4 haloalkyl and C1-C4 alkoxycarbonylC1-C4 alkyl;

[0020] R 17 Selected from the group consisting of hydrogen, C1-C4 alkyl and C1-C4 haloalkyl.

[0021] According to a second aspect of the present invention, there is provided an agrochemical composition comprising a herbicidally effective amount of a compound of formula (I) and an agrochemically acceptable diluent or carrier. Such an agricultural composition may further comprise at least one additional active ingredient.

[0022] According to a third aspect of the present invention, there is provided a method for controlling or preventing the growth of unwanted plants, wherein a herbicidally effective amount of a compound of formula (I) or a composition comprising such a compound as an active ingredient is applied to the plants, parts thereof or the locus thereof.

[0023] According to a fourth aspect of the present invention, there is provided use of a compound of formula (I) as a herbicide.

[0024] According to a fifth aspect of the present invention, there is provided a method for preparing a compound of formula (I).

[0025] As used herein, the term "halogen" or "halo" refers to fluorine (fluoro), chlorine (chloro), bromine (bromo) or iodine (iodo), preferably fluorine, chlorine or bromine.

[0026] As used herein, cyano refers to a -CN group.

[0027] As used herein, hydroxyl means an -OH group.

[0028] As used herein, nitro refers to a -NO2 group.

[0029] As used herein, the term "C1-C6 alkyl" refers to a straight or branched hydrocarbon chain radical consisting solely of carbon and hydrogen atoms, containing no unsaturation, having from one to six carbon atoms, and attached to the remainder of the molecule by a single bond. C1-C4 alkyl and C1-C2 alkyl should be interpreted accordingly. Examples of C1-C6 alkyl include, but are not limited to, methyl (Me), ethyl (Et), n-propyl, 1-methylethyl (isopropyl), n-butyl, and 1-dimethylethyl (tert-butyl).

[0030] As used herein, the term "C1-C6 alkoxy" refers to a group having the formula -OR a A group in which R a is C1-C6 alkyl as generally defined above. C1-C4 alkoxy should be interpreted accordingly. 1-4 Examples of alkoxy groups include, but are not limited to, methoxy, ethoxy, propoxy, isopropoxy, and tert-butoxy.

[0031] As used herein, the term "C1-C6 haloalkyl" refers to a C1-C6 alkyl group as generally defined above, which is substituted by one or more identical or different halogen atoms. C1-C4 haloalkyl should be interpreted accordingly. Examples of C1-C6 haloalkyl include, but are not limited to, chloromethyl, fluoromethyl, fluoroethyl, difluoromethyl, trifluoromethyl and 2,2,2-trifluoroethyl.

[0032] As used herein, the term "C2-C6 alkenyl" refers to a straight or branched hydrocarbon chain radical consisting solely of carbon atoms and hydrogen atoms, containing at least one double bond which may have an (E)- or (Z)-configuration, having from two to six carbon atoms, attached to the remainder of the molecule by a single bond. C2-C4 alkenyl should be interpreted accordingly. Examples of C2-C6 alkenyl include, but are not limited to, prop-1-enyl, allyl (prop-2-enyl) and but-1-enyl.

[0033] As used herein, the term "C2-C6 haloalkenyl" refers to a C2-C6 alkenyl group as generally defined above that is substituted with one or more halogen atoms that are the same or different. Examples of C2-C6 haloalkenyl include, but are not limited to, vinyl chloride, vinyl fluoride, 1,1-difluoroethylene, 1,1-dichloroethylene, and 1,1,2-trichloroethylene.

[0034] As used herein, the term "C2-C6 alkynyl" refers to a straight or branched hydrocarbon chain radical consisting solely of carbon atoms and hydrogen atoms, containing at least one triple bond, having from two to six carbon atoms, and attached to the remainder of the molecule by a single bond. C2-C4 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.

[0035] As used herein, the term "C1-C6 haloalkoxy" refers to a C1-C6 alkoxy group as defined above that is substituted with one or more identical or different halogen atoms. C1-C4 haloalkoxy should be interpreted accordingly. Examples of C1-C6 haloalkoxy include, but are not limited to, fluoromethoxy, difluoromethoxy, fluoroethoxy, trifluoromethoxy, and trifluoroethoxy.

[0036] As used herein, the term "C1-C3 haloalkoxy C1-C3 alkyl" refers to a b -OR a - a group, wherein R b is a C1-C3 haloalkyl group as generally defined above, and R a is a C1-C3 alkylene group as generally defined above.

[0037] As used herein, the term "C1-C3 alkoxy C1-C3 alkyl" refers to a b -OR a - a group, wherein R b is a C1-C3 alkyl group as generally defined above, and R a is a C1-C3 alkylene group as generally defined above.

[0038] As used herein, the term "C1-C3 alkoxy C1-C3 alkoxy-" refers to a b -OR a -O- group, where R b is a C1-C3 alkyl group as generally defined above, and R a is a C1-C3 alkylene group as generally defined above.

[0039] As used herein, the term "C3-C6 alkenyloxy" refers to a group having the formula -OR a A group in which R a is a C3-C6 alkenyl group as generally defined above.

[0040] As used herein, the term "C3-C6 alkynyloxy" refers to a group having the formula -OR a A group in which R a is a C3-C6 alkynyl group as generally defined above.

[0041] As used herein, the term "hydroxy C1-C6 alkyl" refers to a C1-C6 alkyl group as generally defined above substituted with one or more hydroxy groups.

[0042] As used herein, the term "C1-C6 alkylcarbonyl" refers to a group having the formula -C(O)R a A group in which R a is a C1-C6 alkyl group as generally defined above.

[0043] As used herein, the term "C1-C6 alkoxycarbonyl" refers to a group having the formula -C(O)OR a A group in which R a is a C1-C6 alkyl group as generally defined above.

[0044] As used herein, the term "aminocarbonyl" refers to a group having the formula -C(O)NH2.

[0045] As used herein, the term "aminothiocarbonyl" refers to a group having the formula -C(S)NH2.

[0046] As used herein, the term "C3-C6 cycloalkyl" refers to a stable monocyclic group that is saturated or partially unsaturated and contains 3 to 6 carbon atoms. C3-C4 cycloalkyl should be interpreted accordingly. Examples of C3-C6 cycloalkyl include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.

[0047] As used herein, the term "C3-C6 halocycloalkyl" refers to a C3-C6 cycloalkyl group as generally defined above which is substituted by one or more halogen atoms which may be the same or different. C3-C4 halocycloalkyl should be interpreted accordingly.

[0048] As used herein, the term "C3-C6 cycloalkoxy" refers to a cycloalkyl group having the formula -OR a A group in which R a is a C3-C6 cycloalkyl group as generally defined above.

[0049] As used herein, the term "N-C3-C6 cycloalkylamino" refers to a cycloalkylamino group having the formula -NHR a A group in which R a is a C3-C6 cycloalkyl group as generally defined above.

[0050] As used herein, unless otherwise expressly stated, the term "heteroaryl" refers to a 5- or 6-membered monocyclic aromatic ring containing 1, 2, 3 or 4 heteroatoms selected individually from nitrogen, oxygen and sulfur. The heteroaryl group may be bonded to the remainder of the molecule via a carbon atom or a heteroatom. Examples of heteroaryl groups include furanyl, pyrrolyl, imidazolyl, thienyl, pyrazolyl, thiazolyl, isothiazolyl, oxazolyl, isoxazolyl, triazolyl, tetrazolyl, pyrazinyl, pyridazinyl, pyrimidinyl or pyridyl.

[0051] As used herein, unless otherwise expressly stated, the term "heterocyclyl" or "heterocyclic" refers to a stable 4- to 6-membered non-aromatic monocyclic group containing 1, 2 or 3 heteroatoms individually selected from nitrogen, oxygen and sulfur. The heterocyclyl group may be bonded to the remainder of the molecule via a carbon atom or a heteroatom. Examples of heterocyclyl groups include, but are not limited to, pyrrolinyl, pyrrolidinyl, tetrahydrofuranyl, tetrahydrothienyl, tetrahydrothiopyranyl, piperidinyl, piperazinyl, tetrahydropyranyl, dihydroisoxazolyl, dioxolanyl, morpholinyl or δ-lactamyl.

[0052] The presence of one or more possible asymmetric carbon atoms in a compound with formula (I) means that the compound can exist in the form of chiral isomers, i.e., enantiomers or diastereomers. As a result of restricted rotation around a single bond, atropisomers may also exist. Formula (I) is intended to include all those possible isomeric forms and mixtures thereof. The present invention includes all those possible isomeric forms and mixtures thereof of compounds with formula (I). Similarly, formula (I) is intended to include all possible tautomers (including lactam-lactim tautomerism and keto-enol tautomerism) (when present). The present invention includes all possible tautomeric forms of compounds with formula (I). Similarly, in the presence of disubstituted olefins, these can exist in the form of E or Z or as a mixture of the two in any ratio. The present invention includes all these possible isomeric forms and mixtures thereof of compounds with formula (I).

[0053] The compound of formula (I) is generally provided in the form of an agronomically acceptable salt, zwitterion or an agronomically acceptable zwitterionic salt. The present invention encompasses all such agronomically acceptable salts, zwitterions and mixtures thereof in all ratios.

[0054] Suitable agronomically acceptable salts of the present invention may have cations including, but not limited to, metals, conjugate acids of amines, and organic cations. Examples of suitable metals include aluminum, calcium, cesium, copper, lithium, magnesium, manganese, potassium, sodium, iron, and zinc. Examples of suitable amines include allylamine, ammonia, amylamine, arginine, phenethylbenzylamine, benzathine, butenyl-2-amine, butylamine, butylethanolamine, cyclohexylamine, decylamine, diamylamine, dibutylamine, diethanolamine, diethylamine, diethylenetriamine, diheptylamine, dihexylamine, diisoamylamine, diisopropylamine, dimethylamine, dioctylamine, dipropanolamine, dipropargylamine, dipropylamine, dodecylamine, ethanolamine, ethylamine, ethylbutylamine, ethylenediamine, ethylheptylamine, ethyloctylamine, ethylpropanolamine, heptadecanamine, heptylamine, hexadecylamine, hexenyl-2-amine, hexylamine, hexylheptylamine, hexyloctylamine, histidine, indoline, isoamylamine, isobutanolamine, isobutylamine, isopropanolamine, isopropylamine , lysine, meglumine, methoxyethylamine, methylamine, methylbutylamine, methylethylamine, methylhexylamine, methylisopropylamine, methylnonylamine, methyloctadecylamine, methylpentadecylamine, morpholine, N,N-diethylethanolamine, N-methylpiperazine, nonylamine, octadecylamine, octylamine, oleylamine, pentadecylamine, pentenyl-2-amine, phenoxyethylamine, picoline, piperazine, piperidine, propanolamine, propylamine, propylenediamine, pyridine, pyrrolidine, sec-butylamine, stearamide, tallowamine, tetradecylamine, tributylamine, tridecylamine, trimethylamine, triheptylamine, trihexylamine, triisobutylamine, triisodecylamine, triisopropylamine, trimethylamine, tripentylamine, tripropylamine, tris(hydroxymethyl)aminomethane, and undecylamine. Examples of suitable organic cations include benzyltributylammonium, benzyltrimethylammonium, benzyltriphenylphosphonium, choline, tetrabutylammonium, tetrabutylphosphonium, tetraethylammonium, tetraethylphosphonium, tetramethylammonium, tetramethylphosphonium, tetrapropylammonium, tetrapropylphosphonium, tributylsulfonium, tributylsulfoxide, triethylsulfonium, triethylsulfoxide, trimethylsulfonium, trimethylsulfoxide, tripropylsulfonium, and tripropylsulfoxide.

[0055] The following list provides information on the substituents Z, R and 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 and R 17For any of these substituents, any definition given below may be combined with any definition of any other substituent given below or elsewhere in this document.

[0056] Preferably, R 1 Selected from the group consisting of hydrogen and C1-C4 alkyl, more preferably hydrogen and methyl, most preferably hydrogen.

[0057] Preferably R 2 It is a C1-C4 alkyl group, more preferably a C1-C2 alkyl group, and most preferably a methyl group.

[0058] Preferably, R 3 Selected from the group consisting of hydrogen, chlorine and fluorine, more preferably chlorine and fluorine, and still more preferably fluorine.

[0059] Preferably, R 4 Selected from the group consisting of hydrogen, chlorine, bromine, cyano and aminothiocarbonyl, more preferably chlorine, bromine, cyano and aminothiocarbonyl, still more preferably chlorine and bromine, and even more preferably chlorine.

[0060] Preferably, R 5 and R 6 Each independently selected from the group consisting of: hydrogen, C1-C4 alkyl, CO2R 9 and CH2OR 12 , more preferably hydrogen and C1-C2 alkyl, most preferably hydrogen.

[0061] Preferably, R 7 and R 8 Each independently selected from the group consisting of: hydrogen, C1-C4 alkyl, C1-C6 haloalkyl, CO2R 9 ,CONR 10 R 11 and CH2OR 12 More preferably, R 7 Selected from the group consisting of: CO2R 9 ,CONR 10 R 11 and CH2OR 12 , CO2R is the most preferred 9 More preferably, R 8 Selected from the group consisting of hydrogen and C1-C4 alkyl, most preferably methyl.

[0062] Preferably, R 9 Selected from the group consisting of hydrogen, C1-C4 alkyl, C1-C4 haloalkyl, C1-C2 alkoxy C1-C2 alkyl, phenyl C1-C2 alkyl and 1 to 2 R 13A phenyl C1-C2 alkyl group substituted with a group represented by is more preferably hydrogen, C1-C4 alkyl, C1-C2 alkoxy C1-C2 alkyl and phenyl C1-C2 alkyl, further preferably hydrogen, C1-C4 alkyl and phenyl C1-C2 alkyl, still more preferably hydrogen and C1-C2 alkyl, and even more preferably, R 9 It is ethyl.

[0063] Preferably, R 10 Selected from hydrogen and SO2R 14 The group consisting of, more preferably SO2R 14 .

[0064] Preferably, R 11 It's hydrogen.

[0065] Preferably, R 12 Selected from the group consisting of hydrogen, C1-C2 alkyl, C1-C2 alkylsulfonyl, C1-C2 haloalkylsulfonyl, C1-C4 alkylcarbonyl, phenylcarbonyl, 1 to 2 R 13 Phenylcarbonyl, phenyl C1-C2 alkylcarbonyl, and 1 to 2 groups represented by R 13 The phenyl group substituted with the group represented is C1-C2 alkylcarbonyl, more preferably C1-C2 alkylsulfonyl, C1-C2 haloalkylsulfonyl and C1-C4 alkylcarbonyl.

[0066] Preferably, R 13 Selected from the group consisting of halogen, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, cyano and C1-C4 alkylsulfonyl.

[0067] Preferably, R 14 Selected from the group consisting of C1-C4 alkyl and C1-C4 alkyl(C1-C4 alkyl)amino, more preferably methyl and isopropyl(methyl)amino.

[0068] Preferably, R 17 Selected from the group consisting of C1-C2 alkyl and C1-C2 haloalkyl, more preferably halomethyl, most preferably trifluoromethyl.

[0069] A subgroup of preferred compounds are the following compounds, among which:

[0070] R 1 is selected from hydrogen or methyl;

[0071] R 2 is a C1-C2 alkyl group;

[0072] R 3 is selected from the group consisting of hydrogen, chlorine and fluorine;

[0073] R 4 is selected from chlorine, bromine, cyano and aminothiocarbonyl;

[0074] R 5 and R 6 Each independently selected from hydrogen and C1-C2 alkyl;

[0075] R 7 Selected from CO2R 9 ,CONR 10 R 11 and CH2OR 12 ;

[0076] R 8 is selected from hydrogen and C1-C4 alkyl;

[0077] R 9 Selected from hydrogen, C1-C4 alkyl, C1-C2 alkoxy C1-C2 alkyl and phenyl C1-C2 alkyl;

[0078] R 10 It is SO2R 14 ;

[0079] R 11 It's hydrogen.

[0080] R 12 is selected from C1-C2 alkylsulfonyl, C1-C2 haloalkylsulfonyl and C1-C4 alkylcarbonyl;

[0081] R 14 is selected from methyl and isopropyl(methyl)amino; and

[0082] R 17 Selected from methyl and trifluoromethyl.

[0083] A subgroup of more preferred compounds are the following compounds, among which:

[0084] R 1 It is hydrogen;

[0085] R 2 It is methyl;

[0086] R 3 is selected from chlorine and fluorine;

[0087] R 4 selected from chlorine and bromine;

[0088] R 5 and R 6 Each is hydrogen;

[0089] R 7 It is CO2R 9 ;

[0090] R 8 It is methyl;

[0091] R 9 is selected from hydrogen, C1-C4 alkyl and phenyl C1-C2 alkyl; and

[0092] R 17 It is trifluoromethyl.

[0093] A subgroup of even more preferred compounds are the following compounds, among which:

[0094] R 1 It is hydrogen;

[0095] R 2 It is methyl;

[0096] R 3 It is fluorine;

[0097] R 4 It is chlorine;

[0098] R 5 and R 6 It's all hydrogen;

[0099] R 7 It is CO2R 9 ;

[0100] R 8 It is methyl;

[0101] R 9 is ethyl; and

[0102] R 17 It is trifluoromethyl.

[0103] Instance table

[0104] This table discloses specific compounds of formula (I) wherein R 1 is hydrogen, R 2 is methyl, R 5 and R 6 is hydrogen, R 8 is methyl, R 17 It is trifluoromethyl.

[0105]

[0106] Among them, compound 11 is the most preferred.

[0107] The compounds of the present invention can be prepared by techniques known to those skilled in the art of organic chemistry. A general method for producing compounds of formula (I) is described below. Unless otherwise specified herein, the substituents Z, R1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 and R 17 is as defined above. The starting materials for preparing the compounds of the present invention can be purchased from common commodity suppliers or can be prepared by known methods. The starting materials and intermediates can be purified by prior art methods (such as chromatography, crystallization, distillation and filtration) before being used in the next step.

[0108] Compounds of formula (I) can be prepared from compounds of formula (A) as shown in Reaction Scheme 1.

[0109] Reaction Scheme 1

[0110]

[0111] For example, a compound of formula (A) can be treated with a base such as potassium carbonate and an alkylating agent such as methyl iodide in a suitable solvent such as acetone. A compound of formula (A) can be prepared from a compound of formula (B) and an amine of formula (C) as shown in Reaction Scheme 2.

[0112] Reaction Scheme 2

[0113]

[0114] For example, a compound of formula (C) may be treated with an oxazinone of formula (B) in a suitable solvent such as acetic acid.Amines of formula (C) may be prepared from nitro compounds of formula (D) as shown in Reaction Scheme 3.

[0115] Reaction Scheme 3

[0116]

[0117] 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. A nitro compound of formula (D) can be prepared from an oxime of formula (E) and an olefin of formula (F) as shown in Reaction Scheme 4.

[0118] Reaction Scheme 4

[0119]

[0120] For example, an oxime of formula (E) can be treated with N-chlorosuccinimide in a suitable solvent (such as dimethylformamide), and the resulting intermediate is then treated with an alkene of formula (F) in a suitable solvent (such as dichloromethane) in the presence of a base (such as triethylamine). Alkenes of formula (F) are available or can be prepared by methods well known in the literature. Oxime of formula (E) can be prepared from an aldehyde of formula (G), as shown in reaction scheme 5.

[0121] Reaction Scheme 5

[0122]

[0123] For example, an 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 by methods known in the literature. Compounds of formula (IA) (which are compounds of formula (I) wherein R 7 is a carboxylic acid group) can be obtained by a compound having formula (IB) (which is a compound having formula (I) wherein R 7 It is CO2R 9 ) as shown in Reaction Scheme 6.

[0124] Reaction Scheme 6

[0125]

[0126] For example, a compound of formula (IB) can be treated with sodium hydroxide in a suitable solvent such as a mixture of water and ethanol. A compound of formula (IC) (which is a compound of formula (I) wherein R 7 is hydroxymethyl) can be prepared from compounds having formula (IA or IB) as shown in Reaction Scheme 7.

[0127] Reaction Scheme 7

[0128]

[0129] For example, a compound of formula (IA) or (IB) can be treated with a suitable reducing agent (e.g., a metal hydride reagent such as sodium borohydride or borane) in a suitable solvent such as tetrahydrofuran. A compound of formula (ID) (which is a compound of formula (I), R 7 It is CH2OR 12 ) can be prepared from a compound having formula (IC) as shown in Reaction Scheme 8.

[0130] Reaction Scheme 8

[0131]

[0132] For example, a compound of formula (IC) can be precipitated with a reagent R in the presence of a base such as sodium hydride or triethylamine in a suitable solvent such as tetrahydrofuran. 12 -LG (wherein LG is a leaving group such as a halogen) (such as an alkylating agent, an acylating agent or a sulfonylating agent). A compound of formula (IE) (which is a compound of formula (I) wherein R 7 It is CONR 10 R 11 ) can be prepared from compounds having formula (IA) as shown in Reaction Scheme 9.

[0133] Reaction Scheme 9

[0134]

[0135] For example, a compound of formula (IA) can be treated with a halogenating agent such as oxalyl chloride in a suitable solvent such as dichloromethane to form an acyl halide, which can be catalyzed by reacting the acyl halide with a reagent HNR in the presence of a base such as triethylamine in a suitable solvent such as dichloromethane. 10 R 11 A compound having formula (IG) (which is a compound having formula (I) wherein R 7 is an oxime group) can be obtained from a compound having formula (IF) (which is a compound having formula (I) wherein R 7 is a keto group), as shown in Reaction Scheme 10.

[0136] Reaction Scheme 10

[0137]

[0138] For example, a compound of formula (IF) can be reacted with hydroxylamine H2NOR in the presence of a base such as triethylamine in a suitable solvent such as ethanol. 16 or a salt thereof. A compound of formula (IH) (which is a compound of formula (I) wherein R 7 is a hydrazone group) can be obtained from a compound having formula (IF) (which is a compound having formula (I) wherein R 7 is a keto group), as shown in Reaction Scheme 11.

[0139] Reaction Scheme 11

[0140]

[0141] For example, a compound of formula (IF) can be treated with hydrazine H2NN (R2) in the presence of a base such as triethylamine in a suitable solvent such as ethanol. 16 )2 or its salt.

[0142] Those skilled in the art will recognize that the order in which the above-described transformations are performed can often be changed or combined in an alternative manner to prepare various compounds of formula (I). Multiple steps can also be combined in a single reaction. All such variations are contemplated to be within the scope of the present invention.

[0143] The skilled artisan will also appreciate that some reagents will react with the substituents Z, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 and R 17 Certain values ​​or combinations of are incompatible, and any additional steps, such as protection and / or deprotection steps, required to achieve the desired transformation will be clear to the skilled person.

[0144] The compounds according to the invention can be used as herbicides in unmodified form, but they are usually formulated into compositions in various ways using formulation adjuvants such as carriers, solvents and surface-active substances. These formulations can be in different physical forms, for example in the form of dusting powders, gels, wettable powders, water-dispersible granules, water-dispersible tablets, effervescent compressed tablets, emulsifiable concentrates, microemulsifiable concentrates, oil-in-water emulsions, flowable oils, aqueous dispersions, oily dispersions, suspoemulsions, capsule suspensions, emulsifiable granules, soluble liquids, water-soluble concentrates (with water or water-miscible organic solvents as carriers), impregnated polymer films or in other known forms, for example from Manual on Development and Use of FAO and WHO Specifications for Pesticides, United Nations, 1st edition, second revision (2010). For water-soluble compounds, soluble liquids, water-soluble concentrates or water-soluble granules are preferred. Such formulations can be used directly or can be diluted before use. Dilution can be carried out with, for example, water, liquid fertilizers, micronutrients, biological organisms, oils or solvents.

[0145] These formulations can be prepared, for example, by mixing the active ingredient with a formulation adjuvant in order to obtain a composition in the form of a finely divided solid, granules, solution, dispersion or emulsion. The active ingredients can also be formulated with other adjuvants, for example finely divided solids, mineral oils, oils of plant or animal origin, modified oils of plant or animal origin, organic solvents, water, surface-active substances or combinations thereof.

[0146] These active ingredients can also be contained in very fine microcapsules. Microcapsules contain active ingredients in porous carriers. This allows the active ingredients to be released (e.g., slowly released) to the environment in a controlled amount. Microcapsules typically have a diameter of from 0.1 to 500 microns. The amount of active ingredients they contain is about 25% to 95% of the capsule weight by weight. These active ingredients can be in the form of a holistic solid, in the form of fine particles in a solid or liquid dispersion, or in the form of a suitable solution. The encapsulated film can include, for example, natural or synthetic rubber, cellulose, styrene / butadiene copolymers, polyacrylonitrile, polyacrylate, polyester, polyamide, polyurea, polyurethane or chemically modified polymers and starch xanthate or other polymers known to those skilled in the art. Alternatively, very fine microcapsules can be formed, in which the active ingredients are contained in the form of finely dispersed particles in a solid matrix of a base material, but these microcapsules themselves are not wrapped.

[0147] Formulation adjuvants suitable for preparing the compositions according to the invention are known per se. As liquid carriers there may be used: water, toluene, xylene, petroleum ether, vegetable oils, acetone, methyl ethyl ketone, cyclohexanone, anhydrides, acetonitrile, acetophenone, amyl acetate, 2-butanone, butylene carbonate, chlorobenzene, cyclohexane, cyclohexanol, alkyl acetates, diacetone alcohol, 1,2-dichloropropane, diethanolamine, p-diethylbenzene, diethylene glycol, diethylene glycol rosinate, diethylene glycol butyl ether, diethylene glycol ethyl ether, diethylene glycol methyl ether, N,N-dimethyl methylformamide, dimethyl sulfoxide, 1,4-dioxane, dipropylene glycol, dipropylene glycol methyl ether, dipropylene glycol dibenzoate, dipropylene glycol, alkyl pyrrolidone, ethyl acetate, 2-ethylhexanol, ethylene carbonate, 1,1,1-trichloroethane, 2-heptanone, α-pinene, d-limonene, ethyl lactate, ethylene glycol, ethylene glycol butyl ether, ethylene glycol methyl ether, γ-butyrolactone, glycerol, acetic acid glyceryl, diacetic acid glyceryl, triacetin, Hexadecane, hexanediol, isoamyl acetate, isobornyl acetate, isooctane, isophorone, cumene, isopropyl myristate, lactic acid, laurylamine, mesityl oxide, methoxypropanol, methyl isoamyl ketone, methyl isobutyl ketone, methyl laurate, methyl octanoate, methyl oleate, dichloromethane, m-xylene, n-hexane, n-octylamine, octadecanoic acid, octylamine acetate, oleic acid, oleylamine, o-xylene, phenol, polyethylene glycol, propionic acid, propyl lactate , propylene carbonate, propylene glycol, propylene glycol methyl ether, p-xylene, toluene, triethyl phosphate, triethylene glycol, xylene sulfonic acid, paraffin, mineral oil, trichloroethylene, perchloroethylene, ethyl acetate, amyl acetate, butyl acetate, propylene glycol methyl ether, diethylene glycol methyl ether, methanol, ethanol, isopropanol and higher molecular weight alcohols such as amyl alcohol, tetrahydrofuranol, hexanol, octanol, ethylene glycol, propylene glycol, glycerol, N-methyl-2-pyrrolidone, etc.

[0148] Suitable solid carriers are, for example, talc, titanium dioxide, pyrophyllite clay, silica, attapulgite clay, diatomaceous earth, limestone, calcium carbonate, bentonite, calcium montmorillonite, cottonseed hulls, wheat flour, soybean flour, pumice, wood flour, ground walnut shells, lignin and similar materials.

[0149] Many surface-active substances can be used advantageously in both solid and liquid formulations, especially in those formulations which can be diluted with a carrier before use. Surface-active substances can be anionic, cationic, nonionic or polymeric and they can act as emulsifying agents, wetting agents or suspending agents or for other purposes. Typical surface-active substances include, for example, salts of alkyl sulfates, such as diethanolammonium dodecylsulfate; salts of alkylarylsulfonates, such as calcium dodecylbenzenesulfonate; alkylphenol / alkylene oxide addition products, such as ethoxylated nonylphenol; alcohol / alkylene oxide addition products, such as ethoxylated tridecanol; soaps, such as sodium stearate; salts of alkylnaphthalenesulfonates, such as sodium dibutylnaphthalenesulfonate; salts of dialkylsulfosuccinates, such as sodium di(2-ethylhexyl)sulfosuccinate; sorbitol esters, such as sorbitan oleate; quaternary amines, such as dodecyltrimethylammonium chloride; polyethylene glycol esters of fatty acids, such as polyethylene glycol stearate; block copolymers of ethylene oxide and propylene oxide; and salts of mono- and dialkyl phosphates; and also further substances, such as are described, for example, in McCutcheon's Detergents and Emulsifiers Annual, MC Publishing Company. Corp., Ridgewood New Jersey (1981).

[0150] Additional adjuvants that can be used in pesticidal formulations include crystallization inhibitors, viscosity modifiers, suspending agents, dyes, antioxidants, foaming agents, light absorbers, mixing aids, defoamers, complexing agents, substances and buffers that neutralize or change the pH, corrosion inhibitors, fragrances, wetting agents, absorption enhancers, micronutrients, plasticizers, glidants, lubricants, dispersants, thickeners, antifreeze agents, microbicides, and liquid and solid fertilizers.

[0151] The composition according to the invention may include an additive comprising an oil of plant or animal origin, a mineral oil, an alkyl ester of such an oil or a mixture of such an oil with an oil derivative. The amount of the oil additive in the composition according to the invention is generally from 0.01% to 10% based on the mixture to be applied. For example, the oil additive can be added to the spray tank in the desired concentration after the spray mixture has been prepared. Preferred oil additives include mineral oil or oil of plant origin, such as rapeseed oil, olive oil or sunflower oil; emulsified vegetable oils; alkyl esters of oils of plant origin, such as methyl derivatives; or oils of animal origin, such as fish oil or tallow. Preferred oil additives include C8-C 22 Alkyl esters of fatty acids, especially C 12 -C 18Methyl derivatives of fatty acids, such as the methyl esters of lauric acid, palmitic acid and oleic acid (methyl laurate, methyl palmitate and methyl oleate, respectively). Many oil derivatives are known from the Compendium of Herbicide Adjuvants, 10th edition, Southern Illinois University, 2010.

[0152] The herbicidal composition generally comprises from 0.1% to 99% by weight, especially from 0.1% to 95% by weight of a compound of formula (I) and from 1% to 99.9% by weight of a formulation adjuvant, which preferably includes from 0 to 25% by weight of a surfactant. The composition of the present invention generally comprises from 0.1% to 99% by weight, especially from 0.1% to 95% by weight of a compound of the present invention and from 1% to 99.9% by weight of a formulation adjuvant, which preferably includes from 0 to 25% by weight of a surfactant. While commercial products may preferably be formulated as concentrates, end users will typically use dilute formulations.

[0153] The application rate varies within a wide range and depends on the nature of the soil, the application method, the crop plants, the harmful organisms to be controlled, the prevailing climatic conditions, and other factors governed by the application method, the application time and the target crop. In general, the compound can be applied at a rate of from 1 l / ha to 2000 l / ha, especially from 10 l / ha to 1000 l / ha.

[0154] Preferred formulations may have the following composition (wt%):

[0155] Emulsifiable concentrates :

[0156] Active ingredient: 1% to 95%, preferably 60% to 90%

[0157] Surfactant: 1% to 30%, preferably 5% to 20%

[0158] Liquid carrier: 1% to 80%, preferably 1% to 35%

[0159] Dust Agent :

[0160] Active ingredient: 0.1% to 10%, preferably 0.1% to 5%

[0161] Solid carrier: 99.9% to 90%, preferably 99.9% to 99%

[0162] Suspension concentrate:

[0163] Active ingredient: 5% to 75%, preferably 10% to 50%

[0164] Water: 94% to 24%, preferably 88% to 30%

[0165] Surfactant: 1% to 40%, preferably 2% to 30%

[0166] Wettable powder :

[0167] Active ingredient: 0.5% to 90%, preferably 1% to 80%

[0168] Surfactant: 0.5% to 20%, preferably 1% to 15%

[0169] Solid carrier: 5% to 95%, preferably 15% to 90%

[0170] Granules:

[0171] Active ingredient: 0.1% to 30%, preferably 0.1% to 15%

[0172] Solid carrier: 99.5% to 70%, preferably 97% to 85%

[0173] Compositions of the present invention may further comprise at least one additional pesticide. For example, compounds according to 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 safener.

[0174] Thus, the compounds of formula (I) can be used in combination with one or more other herbicides to provide various herbicidal mixtures. These herbicidal mixtures have unexpected advantages which, in a broader sense, can be described as synergistic activity. Specific examples of such mixtures include (wherein "I" represents a compound having formula (I)): I+acetochlor; I+ acifluorfen (including acifluorfen-sodium); I+ bensulfuron; I+ alachlor; I+ fenthion; I+ chlorfenapyr; I+ azomethin; I+ amitriptyline; I+ cyproconazole; I+ cyproconazole; I+ aminopyralid; I+ cyproconazole; I+ sulfamethoxam; I+ atrazine; I+ benzylsulfuron-methyl (including benzylsulfuron-methyl); I+ thiamethoxam; I+ bicyclopyrone; I+ bialaphos; I+ pyrifos; I+ bispyribac-sodium; I+ bixlozone; I+ bromocriptine; I+ bromoxynil; I+ butachlor; I+ fluazifop-butyl ; I+ mesotrione; I+ mesotrione (including mesotrione-ethyl); ester sulfonamide (including ester sulfonamide-methyl); I+ chlorimuron (including chlorimuron-ethyl); I+ chlorotoluron; I+ ethersulfuron; I+ chlorsulfuron; I+ cyproconazole; I+ clacyfos; I+ clethodim; I+ clodinafop (including clodinafop-propargyl); I+ isocyanate; I+ clopyralid; I+ cyclopyranil; I+ cyclopyrimorate; I+ cyprosulfuron; I+ cyhalofop (including cyhalofop-butyl); I+ 2,4-D (including its choline salt and 2 -ethylhexyl ester); I+2,4-DB; I+dimethuron; I+betamethrin; I+dicamba (including its aluminum, aminopropyl, bis-aminopropylmethyl, choline, dichloropropane, diglycolamine, dimethylamine, dimethylammonium, potassium and sodium salts); I+dimethoate; I+dicloran; I+pyraclostrobin; I+dimethoate; I+dimethoate; I+dimethoate; I+diquat ... quinotrione); I+ tetrazoline; I+ fluazifop-butyl; I+ bispyribac; I+ clofopyridine; I+ fluazifop-butyl (including fluazifop-butyl-butyl); I+ flufenacet (including flufenacet-sodium); I+ flufenacet; I+ flumethalin; I+ flumetamide; I+ flufenacet; I+ fluazifop-butyl; I+ flufenacetyl; I+ flufenacet; I+ flufenacet-methyl; I+ fluroxypyr-meptyl (including fluroxypyr-meptyl); I+ fluthiazol-butyl; I+ foramsulfuron; I+ glufosinate (including its ammonium salt); I+ glyphosate (including its hydrazine, isopropyl ammonium and potassium salt);I+halauxifen (including halauxifen-methyl); I+halauxisulfuron; I+halauxifen (including halauxifen-methyl); I+hexazinone; I+hydantocidin; I+methoxazolidinone; I+methyl imazapyr; I+methazapyr; I+methazapyr; I+methazaquin; I+methazaquin; I+methazaquin; I+imazapyr; I+indaziflam; I+iodosulfuron (including iodosulfuron-methyl-sodium); I+iofensulfuron; I+isofensulfuron-sodium; I+iobenzonitrile; I+ipfencarbazone; I+isoproturon; I+isoxaben; I+isoxaflutole; I+lactosulfuron; I+lancotrione; I+linuron; I+MCPA; I+MCPB; I+mecoprop-P; I+mefenacet; I+methyldisulfuron; I+methyldisulfuron-methyl; I+mesotrione; I+mesotrione; I+metamethoxazole; I+metachlor; I+methiozolin; I+isothiozolin; I+isopropylamine; I+sulfuron; I+sulfuron; I+methoxysulfuron; I+methoxysulfuron; I+methoxysulfuron; I+methoxysulfuron; I+methoxysulfuron; I+methoxysulfuron; I+methoxysulfuron; I+methoxysulfuron; I+methoxysulfuron; I+methoxysulfuron; I+methoxysulfuron; I+methoxysulfuron; I+methoxysulfuron; I+methoxysulfuron; I+methoxysulfuron; I+methoxysulfuron; I+ paraquat dichloride; I+ pendimethalin; I+ penoxsulam; I+ bendichlor; I+ pyraclostrobin; I+ pyraclostrobin; I+ oxazolidinone; I+ pretilachlor; I+ sulfamethoxam-methyl; I+ ammonia fluazifop; I+ promethazine; I+ pyraclostrobin; I+ pyrimisulfan; I+ pyrimisulfuron; I+ pyrazosulfuron; I+ pyrosulfuron; I+ pyrosulfuron; I+ pyrazosulfuron; I+ pyrimisulfan; I+ pyrosulfuron; I+ pyrosulfuron; I+ pyrazo ... pyroxasulfone); I+pyrosulfuron; I+quinclorac; I+quinclorac; I+quizalofop-ethyl (including quizalofop-P-tefuryl); I+sulfonesulfuron; I+bensulfuron; I+sethoxydim; I+simazine; I+S-isopropylmethoate; I+sulfuron; I+sulfuron; I+sulfensulfuron; I+sulfensulfuron; I+sulfuron; I+sulfuron; I+terbuthiazine; I+terbuthiazine; I+thiencarbazone; I+thifensulfuron; I+tiafenacil; I+tolpyralate; I+benpyrazone;I+ trimethylol; I+ triafamone; I+ wild wheat; I+ ether bensulfuron; I+ bensulfuron (including bensulfuron-methyl); I+ triclopyr; I+ trifloxysulfuron (including trifloxysulfuron-sodium); I+ trifludimoxazin; I+ trifluralin; I+ flufenamic acid; I+ trifloxysulfuron; I+ 4-hydroxy-1-methoxy-5-methyl-3-[4-(trifluoromethyl)-2-pyridinyl]imidazolidin-2-one; I+4-hydroxy-1,5-dimethyl-3-[4-(trifluoromethyl)-2-pyridinyl]imidazolidin-2-one; I+ 5-ethoxy-4-hydroxy-1-methyl-3-[4-(trifluoromethyl) )-2-pyridyl]imidazolidin-2-one; I+4-hydroxy-1-methyl-3-[4-(trifluoromethyl)-2-pyridyl]imidazolidin-2-one; I+4-hydroxy-1,5-dimethyl-3-[1-methyl-5-(trifluoromethyl)pyrazol-3-yl]imidazolidin-2-one; I+(4R)1-(5-tert-butylisoxazol-3-yl)-4-ethoxy-5-hydroxy-3-methyl-imidazolidin-2-one; I+3-[2-(3,4-dimethoxyphenyl)-6-methyl-3-oxo-pyridazine-4-carbonyl]bicyclo[3.2.1]octane-2,4-dione; I+2-[2-(3,4-dimethoxyphenyl)-6-methyl-3-oxo-pyridazine-4-carbonyl] 1,3-dione; 1+2-[2-(3,4-dimethoxyphenyl)-6-methyl-3-oxo-pyridazine-4-carbonyl]cyclohexane-1,3-dione; 1+2-[2-(3,4-dimethoxyphenyl)-6-methyl-3-oxo-pyridazine-4-carbonyl]-5,5-dimethyl-cyclohexane-1,3-dione; 1+6-[2-(3,4-dimethoxyphenyl)-6-methyl-3-oxo-pyridazine-4-carbonyl]-2,2,4,4-tetramethyl-cyclohexane-1,3,5-trione; 1+2-[2-(3,4-dimethoxyphenyl)-6-methyl-3-oxo-pyridazine-4-carbonyl]-5-ethyl-cyclohexane-1,3-dione 3-dione; I+2-[2-(3,4-dimethoxyphenyl)-6-methyl-3-oxo-pyridazine-4-carbonyl]-4,4,6,6-tetramethyl-cyclohexane-1,3-dione; I+2-[6-cyclopropyl-2-(3,4-dimethoxyphenyl)-3-oxo-pyridazine-4-carbonyl]-5-methyl-cyclohexane-1,3-dione; I+3-[6-cyclopropyl-2-(3,4-dimethoxyphenyl)-3-oxo-pyridazine-4-carbonyl]bicyclo[3.2.1]octane-2,4-dione; I+2-[6-cyclopropyl-2-(3,4-dimethoxyphenyl)-3-oxo-pyridazine-4-carbonyl]-5,5-dimethyl-cyclohexane-1,3-dione;I+6-[6-cyclopropyl-2-(3,4-dimethoxyphenyl)-3-oxo-pyridazine-4-carbonyl]-2,2,4,4-tetramethyl-cyclohexane-1,3,5-trione; I+2-[6-cyclopropyl-2-(3,4-dimethoxyphenyl)-3-oxo-pyridazine-4-carbonyl]cyclohexane-1,3-dione; I+4-[2-(3,4-dimethoxyphenyl)-6-methyl-3-oxo-pyridazine-4-carbonyl]-2,2,6,6-tetramethyl-tetrahydropyran-3,5-dione and I+4-[6-cyclopropyl-2-(3,4-dimethoxyphenyl)-3-oxo-pyridazine-4-carbonyl]-2,2,6,6-tetramethyl-tetrahydropyran-3,5-dione. ;

[0175] Specific examples of such preferred synergistically active mixtures include: I + S-isopropylamine; I + glufosinate; I + L-glufosinate; I + glyphosate; I + mesotrione; I + bicyclopyrone; and I + metribuzin.

[0176] Mixtures of compounds of formula (I) may also be in the form of esters or salts, as mentioned, for example, in The Pesticide Manual, Fourteenth Edition, British Crop Protection Council, 2006.

[0177] The compounds of formula (I) can also be used in a mixture with other agrochemicals such as fungicides, nematicides or insecticides, examples of which are given in the Pesticide Handbook.

[0178] The mass ratio of any two ingredients in each combination is selected to give the desired, for example, synergistic effect. The mixing ratio of the compound of formula (I) to the mixed partner is from 1:100 to 1000:1. The preferred mass ratio between any two components of the present invention is from 75:1 to 1:75, more preferably 50:1 to 1.50, especially 25:1 to 1:25, advantageously 10:1 to 1:10, such as 5:1 to 1:5, for example 1:3 to 3:1. The mixing ratio is understood to include, on the one hand, the ratio by mass, and also on the other hand, the molar ratio.

[0179] These mixtures can advantageously be used in the formulations mentioned above ("active ingredient" in this case relates to the corresponding mixture of the compound of formula (I) with the mixing partner).

[0180] The compound of formula (I) of the present invention can also be combined with a herbicide safener. Preferred combinations (where "I" represents a compound of formula (I)) include: I+fenoxazolidinone, I+fenoxadiazole (including fenoxadiazole); I+ cyclopropylsulfonamide; I+ dichloropropene; I+fenoxazole (including fenoxadiazole ethyl); I+fenoxadil; I+ fluazifop; I+fenoxadiazole, I+ isoxadiazole (including isoxadiazole ethyl); I+ pyrazoline oxadiazole (including pyrazoline oxadiazole); I+ metcamifen; I+ N-(2-methoxybenzoyl)-4-[(methylaminocarbonyl)amino]benzenesulfonamide and I+ fenoxonitrile.

[0181] Particularly preferred are mixtures of a compound of formula (I) with ciprosulfonamide, isoxadiazole (including isoxadiazole ethyl), cloquintocet-mexyl (including cloquintocet) and / or N-(2-methoxybenzoyl)-4-[(methyl-aminocarbonyl)amino]benzenesulfonamide.

[0182] These safeners of compounds of formula (I) may also be in the form of esters or salts, such as those mentioned in the Pesticide Handbook (14th edition (BCPC), 2006). References to clofosbuvir also apply to its lithium, sodium, potassium, calcium, magnesium, aluminium, iron, ammonium, quaternary ammonium, sulfonium or phosphonium salts (such as disclosed in WO 02 / 34048), and references to fenthiocarb-ethyl also apply to fenthiocarb, etc.

[0183] Preferably, the mixing ratio of compound of formula (I) to safener is from 100:1 to 1:10, in particular from 20:1 to 1:1.

[0184] These mixtures can advantageously be used in the abovementioned formulations ("active ingredient" in this case relates to the corresponding mixture of the compound of formula (I) and the safener).

[0185] The compounds of formula (I) of the present invention are useful as herbicides. Therefore, the present invention further includes a method for controlling unwanted plants, comprising applying an effective amount of a compound of the present invention or a herbicidal composition containing the compound to the plant or a location containing them. 'Control' means killing, reducing or delaying growth or preventing or reducing germination. Usually the plants to be controlled are unwanted plants (weeds). 'Location' means an area where a plant is growing or will grow.

[0186] The application rate of the compound with formula (I) can vary within wide limits and depends on the nature of the soil, the method of application (pre-emergence; post-emergence; application to seed furrows; no-till application, etc.), crop plants, one or more weeds to be controlled, the main climatic conditions and other factors governed by the method of application, the time of application and the target crop. The compound with formula (I) according to the present invention is usually applied at a rate of from 10g / ha to 2000g / ha, especially from 50g / ha to 1000g / ha. The preferred range is 10-200g / ha.

[0187] Application is usually carried out by spraying the composition, typically by means of a tractor-mounted sprayer for large areas, but other methods such as dusting (for powders), dripping or drenching may also be used.

[0188] Useful plants in which the compositions according to the invention can be used include crops such as cereals, for example barley and wheat, cotton, oilseed rape, sunflower, corn, rice, soybeans, sugar beet, sugar cane and turf.

[0189] Crop plants may also include trees, such as fruit trees, palm trees, coconut trees or other nuts. Also included are vines (such as grapes), shrub fruit trees, fruit plants and vegetables.

[0190] Crops are to be understood as also including those crops which have been rendered tolerant to herbicides or classes of herbicides (e.g. ALS-inhibitors, GS-inhibitors, EPSPS-inhibitors, PPO-inhibitors, ACCase-inhibitors and HPPD-inhibitors) by conventional methods of breeding or by genetic engineering. Examples of crops which have been rendered tolerant to imidazolinones (e.g. imazamox) by conventional methods of breeding are Summer rapeseed (canola). Examples of crops that have been rendered tolerant to herbicides by genetic engineering methods include, for example, maize varieties resistant to glyphosate and glufosinate, which are now and It is commercially available under the trademark ANTIQUID®.

[0191] Crops are also to be understood as those crops which have been rendered resistant to harmful insects by genetic engineering methods, such as Bt maize (resistant to the European corn borer), Bt cotton (resistant to the boll weevil) and also Bt potato (resistant to the Colorado beetle). Examples of Bt maize are Bt 176 corn hybrid (Syngenta Seeds). Bt toxins are proteins naturally produced by the soil bacterium Bacillus thuringiensis. Examples of toxins or transgenic plants capable of synthesizing such toxins are described in EP-A-451 878, EP-A-374 753, WO 93 / 07278, WO 95 / 34656, WO 03 / 052073 and EP-A-427 529. Examples of transgenic plants comprising one or more genes encoding insecticide resistance and expressing one or more toxins are (Corn), Yield (corn), (cotton), (cotton), (potato), and Plant crops or their seed material can both be resistant to herbicides and at the same time resistant to insect feeding ("stacked" transgenic results). For example, seeds can have the ability to express insecticidal Cry3 proteins while being tolerant to glyphosate.

[0192] Crops are also to be understood as including those crops which have been obtained by conventional breeding methods or genetic engineering and contain so-called output traits, such as improved storage stability, higher nutritional value and improved flavour.

[0193] Other useful plants include turf grasses such as those grown commercially for lawns on golf courses, lawns, parks and roadsides, and ornamental plants such as flowers or shrubs.

[0194] The compounds of the invention can be used in a method of controlling undesirable vegetation in crop plants that are tolerant to protoporphyrinogen oxidase (PPO) inhibitors. Such plants can be obtained, for example, by transforming crop plants with nucleic acids encoding suitable protoporphyrinogen oxidases, which nucleic acids may contain mutations to render them more resistant to PPO inhibitors. Examples of such nucleic acids and crop plants are disclosed in WO 95 / 34659, WO 97 / 32011, WO 2007 / 024739, WO 2012 / 080975, WO 2013 / 189984, WO 2015 / 022636, WO 2015 / 022640, WO 2015 / 092706、WO 2016 / 099153、WO 2017 / 023778、WO 2017 / 039969、WO 2017 / 217793、WO 2017 / 217794、WO 2018 / 114759、WO 2019 / 117578、WO 2019 / 117579 and WO 2019 / 118726. Therefore, the present invention also provides a method for controlling unwanted vegetation in a plant cultivation locus, the method comprising the steps of: a) providing a plant comprising at least one nucleic acid comprising a nucleotide sequence encoding a protoporphyrinogen oxidase (PPO) polypeptide at said locus, which polypeptide is resistant or tolerant to a PPO-inhibiting herbicide; b) applying to said locus an effective amount of said herbicide, wherein the PPO-inhibiting herbicide is a compound of formula (I) as defined herein.

[0195] The compounds and compositions of formula (I) of the present invention can be used to control a variety of monocotyledonous and dicotyledonous weed species in general. Examples of monocotyledonous species that can be typically controlled include Alopecurus myosuroides, Avena fatua, Brachiaria plantaginea, Bromus tectorum, Cyperus esculentus, Digitaria sanguinalis, Echinochloa crus-galli, Lolium perenne, Lolium multiflorum, Panicum miliaceum, Poa annua, Setaria viridis, Setaria faberi, and Sorghum bicolor. Examples of dicotyledonous species that can be controlled include: Abutilon, Amaranthus retroflexus, Bidens pilosa, Chenopodium album, Glechoma longituba, Glechoma chinensis, Glechoma scoparia, Polygonum convolutum, Prickly Gold Noon Flower, Xinjiang wild rape, Solanum nigrum, Chickweed, Veronica persica and Xanthium sibiricum. Unwanted plants should be understood to also include those weeds that have been given tolerance to herbicides or multiple classes of herbicides (e.g., ALS-inhibitors, GS-inhibitors, EPSPS-inhibitors, PPO-inhibitors, ACCase-inhibitors and HPPD-inhibitors) by evolution, by conventional breeding methods or by genetic engineering. Examples include Amaranthus palmeri that has evolved and has resistance to glyphosate and / or acetolactate synthase (ALS) inhibiting herbicides.

[0196] The compounds of the invention can be used in methods of controlling unwanted plants or weeds that are resistant to protoporphyrinogen oxidase (PPO) inhibitors. For example, due to amino acid substitutions in PPX2L, such as those occurring at amino acids R128 (also known as R98) and G399, or the deletion of a codon (glycine) at codon 210 (Δ210) in PPX2L, populations of Palmer amaranth and Amaranthus sclerosus have evolved to be resistant to PPO weeds. The compounds of the invention can be used in methods of controlling Palmer amaranth and / or Amaranthus sclerosus having mutations or deletions at the aforementioned codons, and it is evident that attempts to use these compounds to control unwanted plants or weeds having other mutations that may occur that confer tolerance or resistance to PPO inhibitors.

[0197] The compounds of formula (I) can also be used for pre-harvest drying of crops, such as, but not limited to, potatoes, soybeans, sunflowers and cotton. Pre-harvest drying is used to dry the leaves of crops without causing significant damage to the crops themselves to aid harvesting.

[0198] The compounds / compositions of the present invention are particularly useful in non-selective burn-down applications and therefore may also be used to control volunteer or escape crop plants.

[0199] Various aspects and embodiments of the invention will now be described in more detail by way of example. It will be appreciated that modifications of detail may be made without departing from the scope of the invention.

[0200] Examples

[0201] The following examples are intended to illustrate but not to limit the present invention.

[0202] Synthesis Example

[0203] Example 1 Preparation of (5S)-3-[2-chloro-4-fluoro-5-[2-methoxy-6-oxo-4-(trifluoromethyl)pyrimidin-1-yl]phenyl]-5-methyl-4H-isoxazole-5-carboxylic acid ethyl ester (Compound 11, S-enantiomer)

[0204] Step 1 Synthesis of (5S)-3-[2-chloro-5-[2,4-dioxo-6-(trifluoromethyl)-1H-pyrimidin-3-yl]-4-fluoro-phenyl]-5-methyl-4H-isoxazole-5-carboxylic acid ethyl ester

[0205]

[0206] 2-(Dimethylamino)-4-(trifluoromethyl)-1,3-oxazin-6-one (4.67 g, 22 mmol) was added to a stirred solution of (5S)-3-(5-amino-2-chloro-4-fluoro-phenyl)-5-methyl-4H-isoxazole-5-carboxylic acid ethyl ester (prepared as described in WO 2020 / 239607, enantiomers separated by chiral chromatography; 5.75 g, 7.9 mmol) in acetic acid (29 ml). The resulting mixture was heated at 90 °C for 4 hours, allowed to cool and evaporated under reduced pressure to leave an amber gum which was purified by chromatography to afford (5S)-3-[2-chloro-5-[2,4-dioxo-6-(trifluoromethyl)-1H-pyrimidin-3-yl]-4-fluoro-phenyl]-5-methyl-4H-isoxazole-5-carboxylic acid ethyl ester (9.2 g) as a pale yellow foam. 1H NMR (400MHz, CDCl3) δ9.45 (br s,1H),7.7(dd,1H),7.35(d,1H),6.25(s,1H),4.3(m,2H),4.1(d,0.5H),3.95(d,0.5H),3.5(d,0.5H),3.35(d,0.5H),1.75(2x s,3H),1.35(2x t,3H)ppm.

[0207] Also prepared using the same method were:

[0208] (5R)-3-[2-Chloro-5-[2,4-dioxo-6-(trifluoromethyl)-1H-pyrimidin-3-yl]-4-fluoro-phenyl]-5-methyl-4H-isoxazole-5-carboxylic acid ethyl ester;

[0209] 3-[2-Chloro-5-[2,4-dioxo-6-(trifluoromethyl)-1H-pyrimidin-3-yl]-4-fluoro-phenyl]-5-methyl-4H-isoxazole-5-carboxylic acid ethyl ester.

[0210] Step 2 Synthesis of (5S)-3-[2-chloro-4-fluoro-5-[2-methoxy-6-oxo-4-(trifluoromethyl)pyrimidin-1-yl]phenyl]-5-methyl-4H-isoxazole-5-carboxylic acid ethyl ester (Compound 11, S-enantiomer)

[0211]

[0212] To a solution of (5S)-3-[2-chloro-5-[2,4-dioxo-6-(trifluoromethyl)-1H-pyrimidin-3-yl]-4-fluoro-phenyl]-5-methyl-4H-isoxazole-5-carboxylic acid ethyl ester (9.2 g, 17.9 mmol) in acetone (89 ml) was added potassium carbonate (3.0 g, 21.4 mmol) and then iodomethane (2.2 ml, 35.7 mmol), and the resulting mixture was stirred at 36° C. for 16 hours. The mixture was evaporated under reduced pressure, ethyl acetate (90 ml) was added, and the mixture was filtered. The filtrate was evaporated under reduced pressure, and the residue was purified by chromatography to afford (5S)-3-[2-chloro-4-fluoro-5-[2-methoxy-6-oxo-4-(trifluoromethyl)pyrimidin-1-yl]phenyl]-5-methyl-4H-isoxazole-5-carboxylic acid ethyl ester (Compound 11, S-enantiomer) (34 mg) as a gum. 1H NMR (400MHz, CDCl3) δ7.65(dd,1H),7.4(dd,1H),6.6(s,1H),4.3(m,2H),4. 15(d,0.5H),4.0(s,3H),3.9(d,0.5H),3.5(d,0.5H),3.3(d,0.5H),1.75(2x s,3H),1.35(2x t,3H)ppm.

[0213] Also prepared using the same method were:

[0214] (5R)-3-[2-chloro-4-fluoro-5-[2-methoxy-6-oxo-4-(trifluoromethyl)pyrimidin-1-yl]phenyl]-5-methyl-4H-isoxazole-5-carboxylic acid ethyl ester (Compound 11, R-enantiomer);

[0215] 3-[2-Chloro-4-fluoro-5-[2-methoxy-6-oxo-4-(trifluoromethyl)pyrimidin-1-yl]phenyl]-5-methyl-4H-isoxazole-5-carboxylic acid ethyl ester (Compound 11, racemate).

[0216] Preparation Examples

[0217]

[0218] The combination is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable grinder to obtain wettable powders which can be diluted with water to give a suspension of the desired concentration.

[0219] Emulsifiable concentrates

[0220]

[0221] Emulsions of any desired dilution which can be used in plant protection can be obtained from these concentrates by dilution with water.

[0222]

[0223] A ready-to-use dust is obtained by mixing the combination with a carrier and grinding the mixture in a suitable grinder.

[0224] Extruder Granules

[0225]

[0226] The combination is mixed and ground with the adjuvants, and the mixture is moistened with water. The mixture is extruded and then dried in an air stream.

[0227] Coated granules

[0228] Active ingredient 8%

[0229] Polyethylene glycol (molecular weight 200) 3%

[0230] Kaolin 89%

[0231] This finely ground combination is applied uniformly in a mixer to the kaolin moistened with polyethylene glycol. In this way, dust-free coated granules are obtained.

[0232] Suspension concentrates

[0233]

[0234] The finely ground combination is intimately mixed with the adjuvants to give a suspension concentrate from which a suspension of any desired dilution can be obtained by dilution with water.

[0235] Extended-release capsule suspension

[0236] 28 parts of the combination are mixed with 2 parts of an aromatic solvent and 7 parts of a toluene diisocyanate / polymethylene-polyphenyl isocyanate mixture (8:1). This mixture is emulsified in a mixture of 1.2 parts of polyvinyl alcohol, 0.05 parts of a defoamer and 51.6 parts of water until the desired particle size is reached. To this emulsion is added a mixture of 2.8 parts of 1,6-hexanediamine in 5.3 parts of water. The mixture is stirred until the polymerization reaction is complete.

[0237] The obtained capsule suspension is stabilized by adding 0.25 parts of thickener and 3 parts of dispersant. The capsule suspension formulation contains 28% of active ingredient. The diameter of the medium capsule is 8-15 microns.

[0238] The resulting formulation is applied to the seeds as an aqueous suspension in an apparatus suitable for this purpose.

[0239] Biological Examples

[0240] Pre-emergence biological efficacy

[0241] Seeds of weeds and / or crops are sown in standard soil in pots. After one day of cultivation in a greenhouse under controlled conditions (at 24°C / 19°C, day / night; 16 hours of light), the plants are sprayed with an aqueous spray solution obtained as follows: the industrial active ingredient is formulated in a small amount of acetone and a special solvent and emulsifier mixture called IF50 (11.12% Emulsogen EL360 TM + 44.44% N-methylpyrrolidone + 44.44% Dowanol DPM glycol ether) to produce a 50 g / l solution, which is then diluted using 0.2% Genapol XO80 as a diluent to obtain the desired final dose of the test compound.

[0242] These test plants were then grown under controlled conditions in a greenhouse (at 24°C / 18°C, day / night; 15 hours of light; 50% humidity) and watered twice a day. After 13 days, the test was evaluated (100 = complete damage to the plant; 0 = no plant damage). The results are shown in Table 2 below.

[0243] Table 2

[0244]

[0245] Biological efficacy after emergence

[0246] Seeds of weeds and / or crops are sown in standard soil in pots. After 14 days of cultivation under controlled conditions in a greenhouse (at 24°C / 19°C, day / night; 16 hours of light), the plants are sprayed with an aqueous spray solution obtained as follows: the technical active ingredient is formulated in a small amount of acetone and a special solvent and emulsifier mixture called IF50 (11.12% Emulsogen EL360 TM + 44.44% N-methylpyrrolidone + 44.44% Dowanol DPM glycol ether) to produce a 50 g / l solution, which is then diluted using 0.2% Genapol XO80 as diluent to obtain the desired final dose of the test compound.

[0247] These test plants were then grown under controlled conditions in a greenhouse (at 24°C / 18°C, day / night; 15 hours of light; 50% humidity) and watered twice a day. After 13 days, the test was evaluated (100 = complete damage to the plant; 0 = no plant damage). The results are shown in Table 3 below.

[0248] Table 3

[0249]

Claims

1. A compound of formula (I) or an agronomically acceptable salt thereof: in R 1 Selected from the group consisting of: hydrogen and C1-C6 alkyl; R 2 Selected from the group consisting of C1-C6 alkyl, C3-C6 alkenyl and C3-C6 alkynyl; R 3 Selected from the group consisting of hydrogen, halogen, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy and C1-C4 alkylsulfonyl; R 4 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; R 5 and R 6 Each is independently selected from the group consisting of hydrogen, cyano, C1-C6 alkyl, C1-C6 haloalkyl, C1-C4 alkylsulfonyl, CO2R 9 ,CONR 10 R 11 and CH2OR 12 ; R 7 and R 8 are each independently selected from the group consisting of hydrogen, cyano, C1-C6 alkyl, C1-C6 haloalkyl, C1-C4 alkoxy, C1-C4 alkylsulfonyl, C(=Z)R 15 、CO2R 9 ,CONR 10 R 11 and CH2OR 12 ; Z is selected from the group consisting of: oxygen, NOR 16 and NN(R 16 )2; R 9 Selected from the group consisting of: hydrogen, C1-C 10 Alkyl, C1-C 10 Halogenated alkyl, C3-C6 alkenyl, C3-C6 haloalkenyl, C3-C6 alkynyl, C1-C4 alkoxy C1-C6 alkyl, C1-C4 haloalkoxy C1-C6 alkyl, C6-C 10 Aryl C1-C3 alkyl, 1 to 4 R 13 The group substituted C6-C 10 Aryl C1-C3 alkyl, heteroaryl C1-C3 alkyl, and 1 to 3 R 13 A group representing a substituted heteroaryl C1-C3 alkyl group; R 10 Selected from the group consisting of: hydrogen, C1-C6 alkyl and SO2R 14 ; R 11 is selected from the group consisting of: hydrogen and C1-C6 alkyl; or R 10 and R 11 Together with the nitrogen to which they are attached, they form a 3- to 6-membered heterocyclyl ring, the heterocyclyl ring optionally containing an oxygen atom; R 12 Selected from the group consisting of hydrogen, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkylsulfonyl, C1-C4 haloalkylsulfonyl, phenylsulfonyl, 1 to 2 R 13 substituted phenylsulfonyl; C1-C4 alkylcarbonyl, C1-C4 haloalkylcarbonyl, C6-C 10 Arylcarbonyl, 1-4 groups R 13 Substituted C6-C 10 Arylcarbonyl, heteroarylcarbonyl, 1 to 3 R 13 A heteroarylcarbonyl group substituted with a C6-C 10 Aryl C1-C3 alkylcarbonyl, 1 to 4 R 13 The group substituted C6-C 10 Aryl C1-C3 alkylcarbonyl, heteroaryl C1-C3 alkylcarbonyl, and 1 to 3 R 13 The group represented is a substituted heteroaryl C1-C3 alkylcarbonyl; Each R 13 independently selected from the group consisting of halogen, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, cyano, and C1-C4 alkylsulfonyl; R 14 Selected from the group consisting of C1-C4 alkyl, C1-C4 haloalkyl and C1-C4 alkyl(C1-C4 alkyl)amino; R 15 Selected from the group consisting of: hydrogen, C1-C4 alkyl and C1-C4 haloalkyl; Each R 16 independently selected from the group consisting of hydrogen, C1-C4 alkyl, C1-C4 haloalkyl and C1-C4 alkoxycarbonylC1-C4 alkyl; R 17 Selected from the group consisting of hydrogen, C1-C4 alkyl and C1-C4 haloalkyl.

2. The compound according to claim 1, wherein R 1 Selected from the group consisting of: hydrogen.

3. The compound according to claim 1 or claim 2, wherein R 2 Selected from the group consisting of: C1-C4 alkyl.

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

5. The compound according to any one of claims 1 to 4, wherein R 5 and R 6 are each independently hydrogen.

6. The compound according to any one of claims 1 to 5, wherein R 7 and R 8 Each independently selected from the group consisting of: hydrogen, C1-C4 alkyl, CO2R 9 ,CONR 10 R 11 and CH2OR 12 .

7. The compound according to any one of claims 1 to 6, wherein R 7 Selected from the group consisting of: CO2R 9 .

8. The compound according to any one of claims 1 to 7, wherein R 8 Selected from the group consisting of hydrogen and C1-C4 alkyl.

9. The compound according to any one of claims 1 to 8, wherein R 9 Selected from the group consisting of: hydrogen and C1-C2 alkyl.

10. The compound according to any one of claims 1 to 9, wherein R 17 Selected from the group consisting of C1-C2 alkyl and C1-C2 haloalkyl.

11. The compound according to any one of claims 1 to 10, wherein R 1 selected from the group consisting of: hydrogen or methyl; R 2 is a C1-C2 alkyl group; R 3 selected from the group consisting of: hydrogen, chlorine and fluorine; R 4 selected from the group consisting of chloro, bromo, cyano and aminothiocarbonyl; R 5 and R 6 Each is independently selected from the group consisting of: hydrogen and C1-C2 alkyl; R 7 Selected from the group consisting of: CO2R 9 ,CONR 10 R 11 and CH2OR 12 ; R 8 selected from the group consisting of: hydrogen and C1-C4 alkyl; R 9 Selected from the group consisting of hydrogen, C1-C4 alkyl, C1-C2 alkoxy C1-C2 alkyl and phenyl C1-C2 alkyl; R 10 It is SO2R 14 ; R 11 It is hydrogen; R 12 Selected from the group consisting of C1-C2 alkylsulfonyl, C1-C2 haloalkylsulfonyl and C1-C4 alkylcarbonyl; R 14 is selected from the group consisting of: methyl and isopropyl(methyl)amino; and R 17 Selected from the group consisting of: methyl and trifluoromethyl.

12. The compound according to any one of claims 1 to 11, wherein R 1 It is hydrogen; R 2 It is methyl; R 3 selected from the group consisting of: chlorine and fluorine; R 4 selected from the group consisting of: chlorine and bromine; R 5 and R 6 Each is hydrogen; R 7 It is CO2R 9 ; R 8 It is methyl; R 9 is selected from the group consisting of: hydrogen, C1-C4 alkyl, and phenyl C1-C2 alkyl; and R 17 It is trifluoromethyl.

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

14. A method of controlling or preventing unwanted vegetation, wherein a herbicidally effective amount of a compound of formula (I) as defined in any one of claims 1 to 12, or a composition as claimed in claim 13, is applied to the plants, parts thereof or the locus thereof.

15. A method for controlling undesirable vegetation in a plant cultivation location, the method comprising the steps of: a) providing at said locus a plant comprising at least one nucleic acid comprising a nucleotide sequence encoding a protoporphyrinogen oxidase (PPO) polypeptide, said polypeptide being resistant or tolerant to a PPO-inhibiting herbicide; b) applying to said locus an effective amount of said herbicide, wherein said PPO-inhibiting herbicide is a compound of formula (I) as defined in any one of claims 1 to 12.

Images