Herbicidal compounds

Abstract

2. A compound of formula (I) or an agriculturally acceptable salt thereof, wherein the substituents are as defined in claim 1, useful as a pesticide, especially as a herbicide. JPEG2025502507000078.jpg46169

Description

[Technical field]

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

[0002] WO 2019 / 121543, WO 2021 / 018664, and WO 2021 / 259224 all disclose herbicidal compounds similar to those of the present invention. Summary of the Invention [Means for solving the problem]

[0003] The present invention is based on the finding that triazine derivatives of formula (I) as defined herein exhibit surprisingly good herbicidal activity. Thus, according to the present invention, a compound of formula (I): [ka] (In the formula, each X 1 , X 2 and X 3 is independently selected from oxygen and sulfur; Y is CH or nitrogen; B is O, S, or NR 5 and; D is (CR 6 R 7 ) n - and; m is an integer from 0 to 2; n is an integer from 1 to 4; R 1 is hydrogen or C1-C6 alkyl; R 2is hydrogen, amino, C1-C6 alkyl, C3-C6 alkenyl, or C3-C6 alkynyl; R 3 is hydrogen, halogen, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C1-C4 alkylthio, or C1-C4 alkylsulfonyl; R 4 is hydrogen, halogen, cyano, nitro, aminocarbonyl, aminothiocarbonyl, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, or C1-C4 alkylsulfonyl; R 5 is hydrogen, hydroxy, C1-C6 alkyl, or C1-C4 alkoxy; Each R 6 and R 7 is hydrogen, halogen, C1-C6 alkyl, C1-C6 haloalkyl, hydroxy, C1-C4 alkoxy, C1-C4 alkoxycarbonyl, or CHOR 12 are independently selected from; 6 and R 7 are not both hydroxyl on the same carbon atom; or two groups R 6 and R 7 may, together with 1 to 3 groups R 15 forming a C1-C5 alkylene chain containing 0, 1 or 2 oxygen atoms, substituted by or two groups R 6 and R 7 form C2 alkenes together with the carbon to which they are attached on the same carbon atom; R 8 OR 9 , S.R. 9 , or NR 10 R 11 and; R 9 is hydrogen, C1-C 10 Alkyl, C1-C 10Haloalkyl, 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, 1-4 groups R 13 C6~C substituted by 10 aryl C1-C3 alkyl, heteroaryl C1-C3 alkyl, or 1-3 groups R 13 heteroaryl C1-C3 alkyl substituted by; R 10 is hydrogen, C1-C6 alkyl, or SO2R 14 and; R 11 is hydrogen or C1-C6 alkyl; or R 10 and R 11 together with the nitrogen to which they are attached form a 3- to 6-membered heterocyclyl ring, optionally containing an oxygen atom; R 12 is hydrogen, C1-C4 alkyl, or C1-C4 alkylcarbonyl; Each R 13 is independently selected from halogen, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, cyano, and C1-C4 alkylsulfonyl; R 14 is C1-C4 alkyl, C1-C4 haloalkyl, or C1-C4 alkyl(C1-C4 alkyl)amino; Each R 15 are independently selected from hydrogen, halogen, C1-C4 alkyl, and C1-C4 haloalkyl; R 16 and R 17 is hydrogen, halogen, C1-C6 alkyl, C1-C6 haloalkyl, C1-C4 alkoxy, and CHOR 12 Are independently selected from; or two groups R 16 and R 17 together with 1 to 3 groups R 15or form a C2-C5 alkylene chain containing 0, 1 or 2 oxygen atoms, substituted by or two groups R 16 and R 17 form C2 alkenes together with the carbon to which they are attached) or an agriculturally acceptable salt thereof, or a salt or N-oxide thereof.

[0004] 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.

[0005] According to a third aspect of the present invention there is provided a method for controlling or preventing undesired plant growth, wherein a herbicidally effective amount of a compound of formula (I) or a composition comprising this compound as an active ingredient is applied to the plant, its part or its habitat.

[0006] According to a fourth aspect of the present invention there is provided the use of a compound of formula (I) as a herbicide.

[0007] According to a fifth aspect of the invention there is provided a process for preparing a compound of formula (I). DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0008] As used herein, the term "halogen" or "halo" refers to fluorine (fluoro), chlorine (chloro), bromine (bromo) or iodine (iodo), preferably fluorine, chlorine or bromine.

[0009] As used herein, cyano refers to the group -CN.

[0010] As used herein, hydroxy refers to an --OH group.

[0011] As used herein, nitro refers to the group --NO.sub.2.

[0012] As used herein, amino refers to the group --NH.

[0013] As used herein, "C1-C 10 The term "alkyl" refers to a straight or branched hydrocarbon chain radical consisting solely of carbon and hydrogen atoms, containing no unsaturation, having from 1 to 10 carbon atoms and attached to the remainder of the molecule by a single bond. C1-C6 alkyl, C1-C4 alkyl and C1-C2 alkyl should be construed accordingly. C1-C 10 Examples of alkyl include, but are not limited to, methyl (Me), ethyl (Et), n-propyl, 1-methylethyl (isopropyl), n-butyl, and 1-dimethylethyl (t-butyl).

[0014] As used herein, the term "C1-C4 alkoxy" refers to any group generally defined as R a is a C1-C4 alkyl group of the formula -OR a C1-C3 alkoxy should be construed accordingly. 1-4 Examples of alkoxy include, but are not limited to, methoxy, ethoxy, propoxy, isopropoxy, and t-butoxy.

[0015] As used herein, "C1-C 10 The term "haloalkyl" refers generally to any C1-C aryl group as defined above, which is substituted with one or more of the same or different halogen atoms. 10 refers to an alkyl group. C1-C6 haloalkyl and C1-C4 haloalkyl should be construed accordingly. 10 Examples of haloalkyl include, but are not limited to, chloromethyl, fluoromethyl, fluoroethyl, difluoromethyl, trifluoromethyl, and 2,2,2-trifluoroethyl.

[0016] As used herein, the term "C2-C6 alkenyl" refers to a straight or branched hydrocarbon chain radical group consisting solely of carbon and hydrogen atoms, containing at least one double bond that may be in either the (E) or (Z) configuration, having 2 to 6 carbon atoms, and attached to the remainder of the molecule by a single bond. C3-C6 alkenyl and C2-C4 alkenyl should be construed accordingly. Examples of C2-C6 alkenyl include, but are not limited to, prop-1-enyl, allyl (prop-2-enyl), and but-1-enyl.

[0017] As used herein, the term "C2-C6 haloalkenyl" refers to a C2-C6 alkenyl group, generally as defined above, substituted by one or more of the same or different halogen atoms. C3-C6 haloalkenyl and C2-C4 haloalkenyl should be interpreted accordingly. Examples of C2-C6 haloalkenyl include, but are not limited to, chloroethylene, fluoroethylene, 1,1-difluoroethylene, 1,1-dichloroethylene, and 1,1,2-trichloroethylene.

[0018] As used herein, the term "C2-C6 alkynyl" refers to a straight or branched hydrocarbon chain radical group consisting solely of carbon and hydrogen atoms, containing at least one triple bond, having 2-6 carbon atoms, and attached to the remainder of the molecule by a single bond. C3-C6 alkynyl and C2-C4 alkynyl should be construed accordingly. Examples of C2-C6 alkynyl include, but are not limited to, prop-1-ynyl, propargyl (prop-2-ynyl), and but-1-ynyl.

[0019] As used herein, the term "C1-C4 haloalkoxy" refers to a C1-C4 alkoxy group as defined above, substituted by one or more of the same or different halogen atoms. C1-C3 haloalkoxy should be interpreted accordingly. Examples of C1-C4 haloalkoxy include, but are not limited to, fluoromethoxy, difluoromethoxy, fluoroethoxy, trifluoromethoxy and trifluoroethoxy.

[0020] As used herein, the term "C1-C4 haloalkoxyC1-C6 alkyl" generally refers to any of R b is a C1-C4 haloalkyl group, and R is generally as defined above a is a C1-C6 alkylene group b -OR a - refers to the group.

[0021] As used herein, the term "C1-C4 alkoxy C1-C6 alkyl" generally refers to R b is a C1-C4 alkyl group, and R is generally as defined above a is a C1-C6 alkylene group b -OR a - refers to the group.

[0022] As used herein, the term "C1-C4 alkylcarbonyl" generally refers to R a is a C1-C4 alkyl group of the formula -C(O)R a C1-C2 alkylcarbonyl should be construed accordingly.

[0023] As used herein, the term "C1-C4 alkoxycarbonyl" generally refers to R a is a C1-C4 alkyl group of the formula -C(O)OR a Refers to the group.

[0024] As used herein, the term "aminocarbonyl" refers to a group of formula -C(O)NH2.

[0025] As used herein, the term "aminothiocarbonyl" refers to a group of formula -C(S)NH2.

[0026] As used herein, the term "C1-C4 alkylthio" generally refers to R a is a C1-C4 alkyl group; a Refers to the group.

[0027] As used herein, the term "C1-C4 alkylsulfonyl" generally refers to a group of the formula -S(O)R, where Ra is a C1-C4 alkyl group as defined above. a The terms "C1-C3 alkylsulfonyl" and "C1-C2 alkylsulfonyl" should be construed accordingly. Examples of C1-C6 alkylsulfonyl include, but are not limited to, methylsulfonyl.

[0028] As used herein, “C6-C 10 The term "aryl" refers to a 6-10 membered aromatic ring system consisting solely of carbon and hydrogen atoms which may be monocyclic, bicyclic or tricyclic. Examples of such ring systems include phenyl, naphthalenyl, or indenyl.

[0029] As used herein, “C6-C 10 The term "aryl C1-C3 alkyl" refers to an aryl moiety, generally as defined above, attached to the remainder of the molecule by a C1-C3 alkylene linker, also as defined above. As used herein, the term "C1-C4 alkyl (C1-C4 alkyl) amino" refers to R a and R b are both C1-C4 alkyl groups as defined above; a (Rb )NH— group.

[0030] As used herein, unless otherwise specified, the term "heteroaryl" refers to a 5- or 6-membered monocyclic aromatic ring containing 1, 2, 3, or 4 heteroatoms independently selected from nitrogen, oxygen, and sulfur. Heteroaryl groups can be bonded to the remainder of the molecule through a carbon atom or a heteroatom. Examples of heteroaryl include furyl, pyrrolyl, imidazolyl, thienyl, pyrazolyl, thiazolyl, isothiazolyl, oxazolyl, isoxazolyl, triazolyl, tetrazolyl, pyrazinyl, pyridazinyl, pyrimidyl, or pyridyl.

[0031] As used herein, unless otherwise specified, the term "heterocyclyl" or "heterocyclic" refers to a stable 4-6 membered non-aromatic monocyclic ring group containing one, two, or three heteroatoms independently selected from nitrogen, oxygen, and sulfur. The heterocyclyl group may be attached to the remainder of the molecule through a carbon atom or a heteroatom. Examples of heterocyclyl include, but are not limited to, pyrrolinyl, pyrrolidyl, tetrahydrofuryl, tetrahydrothienyl, tetrahydrothiopyranyl, piperidyl, piperazinyl, tetrahydropyranyl, dihydroisoxazolyl, dioxolanyl, morpholinyl, or δ-lactamyl.

[0032] The presence of one or more optionally asymmetric carbon atoms in the compounds of formula (I) means that the compounds can occur in chiral isomeric forms, i.e. enantiomeric or diastereomeric forms. Astrogenic isomers can also occur as a result of restricted rotation about a single bond. Formula (I) is intended to include all these possible isomeric forms and mixtures thereof. The present invention includes all these possible isomeric forms and mixtures thereof for the compounds of formula (I). Similarly, formula (I) is intended to include all possible tautomers, if present, including lactam-lactim tautomerism and keto-enol tautomerism. The present invention includes all possible tautomeric forms for the compounds of formula (I). Similarly, disubstituted alkenes, if present, can exist in E or Z form or as a mixture of both in any proportion. The present invention includes all these possible isomeric forms and mixtures thereof for the compounds of formula (I).

[0033] The compounds of formula (I) are typically provided in the form of an agriculturally acceptable salt, a zwitterion, or an agriculturally acceptable salt of a zwitterion. The present invention encompasses all such agriculturally acceptable salts, zwitterions, and mixtures thereof in all proportions.

[0034] Suitable agriculturally acceptable salts of the present invention may have cations including, but not limited to, metals, conjugate acids of amines, and organic cations. Examples of suitable metals include aluminum, calcium, cesium, copper, lithium, magnesium, manganese, potassium, sodium, iron, and zinc.Examples of suitable amines include allylamine, ammonia, amylamine, arginine, benethamine, benzathine, butenyl-2-amine, butylamine, butylethanolamine, cyclohexylamine, decylamine, diamylamine, dibutylamine, diethanolamine, diethylamine, diethylenetriamine, diheptylamine, dihexylamine, diisoamylamine, diisopropylamine, dimethylamine, dioctylamine, dipropanolamine, dipropargylamine, dipropylamine, dodecylamine, ethanolamine, ethylamine, ethylbutylamine, ethylenediamine, ethylheptylamine, ethyloctylamine, ethylpropanolamine, heptadecylamine, heptylamine, hexadecylamine, hexenyl-2-amine, hexylamine, hexylheptylamine, hexyloctylamine, histidine, indoline, isoamylamine, isobutanolamine, isobutylamine, isopropanolamine, isopropylamine, lysine, Examples of suitable amines include amine, meglumine, methoxyethylamine, methylamine, methylbutylamine, methylethylamine, methylhexylamine, methylisopropylamine, methylnonylamine, methyloctadecylamine, methylpentadecylamine, morpholine, N,N-diethylethanolamine, N-methylpiperazine, nonylamine, octadecylamine, octylamine, oleylamine, pentadecylamine, pentenyl-2-amine, phenoxyethylamine, picoline, piperazine, piperidine, propanolamine, propylamine, propylenediamine, pyridine, pyrrolidine, sec-butylamine, stearylamine, tallowamine, tetradecylamine, tributylamine, tridecylamine, trimethylamine, triheptylamine, trihexylamine, triisobutylamine, triisodecylamine, triisopropylamine, trimethylamine, tripentylamine, tripropylamine, tris(hydroxymethyl)aminomethane, and undecylamine.Examples of suitable organic cations include benzyltributylammonium, benzyltrimethylammonium, benzyltriphenylphosphonium, choline, tetrabutylammonium, tetrabutylphosphonium, tetraethylammonium, tetraethylphosphonium, tetramethylammonium, tetramethylphosphonium, tetrapropylammonium, tetrapropylphosphonium, tributylsulfonium, tributylsulfoxonium, triethylsulfonium, triethylsulfoxonium, trimethylsulfonium, trimethylsulfoxonium, tripropylsulfonium and tripropylsulfoxonium.

[0035] The following list includes substituents X related to compounds of formula (I) according to the present invention: 1 , X 2 , X 3 , Y, B, D, m, n, 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 Definitions, including preferred definitions, are provided for: Any of the definitions given below for any one of these substituents may be combined with any definition of any other substituent given below or elsewhere in this specification.

[0036] X 1 is oxygen or sulfur. Preferably, X 1 is sulfur.

[0037] X 2 is oxygen or sulfur. Preferably, X 2 is oxygen.

[0038] X3 is oxygen or sulfur. Preferably, X 3 is oxygen.

[0039] Y is CH or nitrogen. Preferably, Y is CH.

[0040] B is O, S or NR 5 Preferably, B is O, NH, or NMe. More preferably, B is O or NH.

[0041] m is an integer of 0 to 2. Preferably, m is 0 or 2, and more preferably, m is 0.

[0042] n is an integer of 1 to 4. Preferably, n is an integer of 1 to 2, and more preferably, n is 2.

[0043] R 1 is hydrogen or C1-C6 alkyl. 1 is hydrogen or C1-C4 alkyl. More preferably, R 1 is C1-C2 alkyl, and most preferably, R 1 is methyl.

[0044] R 2 is hydrogen, amino, C1-C6 alkyl, C3-C6 alkenyl, or C3-C6 alkynyl. 2 is hydrogen, C1-C4 alkyl, or C3-C4 alkynyl. More preferably, R 2 is C1-C2 alkyl, and most preferably R 2 is methyl.

[0045] R 3 is hydrogen, halogen, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C1-C4 alkylthio, or C1-C4 alkylsulfonyl. 3 is hydrogen, chloro, or fluoro. More preferably, R 3is hydrogen or fluoro. More preferably still, R 3 is fluoro.

[0046] R 4 is hydrogen, halogen, cyano, nitro, aminocarbonyl, aminothiocarbonyl, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, or C1-C4 alkylsulfonyl. 4 is hydrogen, chloro, bromo, cyano, or aminothiocarbonyl. More preferably, R 4 is chloro, bromo, or cyano, most preferably R 4 is chloro.

[0047] R 5 is hydrogen, hydroxy, C1-C6 alkyl, or C1-C4 alkoxy. 5 is hydrogen or C1-C4 alkyl. More preferably, R 5 is hydrogen or C1-C2 alkyl. Even more preferably, R 5 is hydrogen or methyl. In one set of embodiments, R 5 is hydrogen.

[0048] Each R 6 and R 7 is hydrogen, halogen, C1-C6 alkyl, C1-C6 haloalkyl, hydroxy, C1-C4 alkoxy, C1-C4 alkoxycarbonyl, and CHOR 12 are independently selected from; 6 and R 7 are not both hydroxyl on the same carbon atom; or two groups R 6 and R 7 may, together with 1 to 3 groups R 15 forming a C1-C5 alkylene chain containing 0, 1 or 2 oxygen atoms, substituted by or two groups R 6 and R 7form a C2 alkene together with the carbon to which they are attached on the same carbon atom. 6 and R 7 is independently selected from hydrogen, halogen, C1-C4 alkyl, and C1-C4 alkoxycarbonyl. More preferably, each R 6 and R 7 is independently selected from hydrogen, halogen, and C1-C2 alkyl. Most preferably, each R 6 and R 7 is independently selected from hydrogen, chloro, and methyl. 6 and R 7 are both hydrogen.

[0049] R 8 OR 9 , S.R. 9 , or NR 10 R 11 Preferably, R 8 OR 9 In one embodiment, R 8 is methoxy.

[0050] R 9 is hydrogen, C1-C 10 Alkyl, C1-C 10 Haloalkyl, C3-C6 alkenyl, C3-C6 haloalkenyl, C3-C6 alkynyl, C1-C4 alkoxy C1-C6 alkyl, C1-C4 haloalkoxy C1-C6 alkyl, C6-C 10 Aryl C1-C3 alkyl, 1-4 groups R 13 C6~C substituted by 10 It is aryl C1-C3 alkyl, heteroaryl C1-C3 alkyl, or heteroaryl C1-C3 alkyl substituted by 1-3 R13. Preferably, R 9 is hydrogen, C1-C4 alkyl, C1-C4 haloalkyl, C1-C2 alkoxyC1-C2 alkyl, phenylC1-C2 alkyl and 1-2 groups R 13 More preferably, R 9is hydrogen, C1-C4 alkyl, C1-C2 alkoxy C1-C2 alkyl, or phenyl C1-C2 alkyl. 9 is hydrogen, C1-C4 alkyl, or phenylC1-C2 alkyl. Even more preferably, R 9 is C1-C3 alkyl. In a particularly preferred embodiment, R 9 is methyl.

[0051] R 10 is hydrogen, C1-C6 alkyl, or SO2R 14 Preferably, R 10 is hydrogen or SO2R 14 More preferably, R 10 is SO2R 14 It is.

[0052] R 11 is hydrogen or C1-C6 alkyl. 11 is hydrogen.

[0053] R 12 is hydrogen, C1-C4 alkyl, or C1-C4 alkylcarbonyl. 12 is hydrogen, C1-C2 alkyl, or C1-C2 alkylcarbonyl. More preferably, R 12 is hydrogen or methyl.

[0054] Each R 13 is independently selected from halogen, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, cyano, and C1-C4 alkylsulfonyl. 13 is selected from halogen, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, cyano, and C1-C4 alkylsulfonyl.

[0055] R 14 is C1-C4 alkyl, C1-C4 haloalkyl, or C1-C4 alkyl(C1-C4 alkyl)amino.14 is C1-C4 alkyl or C1-C4 alkyl(C1-C4 alkyl)amino. More preferably, R 14 is methyl or isopropyl(methyl)amino.

[0056] Each R 15 is independently selected from hydrogen, halogen, C1-C4 alkyl, and C1-C4 haloalkyl; preferably, each R 15 are independently selected from hydrogen, halogen, and C1-C2 alkyl. More preferably, each R 15 is independently selected from hydrogen and methyl. Most preferably, R 15 is hydrogen.

[0057] R 16 and R 17 is hydrogen, halogen, C1-C6 alkyl, C1-C6 haloalkyl, C1-C4 alkoxy, and CHOR 12 Preferably, R 16 and R 17 are independently selected from hydrogen, C1-C4 alkyl and C1-C2 alkoxy. More preferably, R 16 and R 17 are independently selected from hydrogen and C1-C2 alkyl. Most preferably, R 16 and R 17 is independently selected from hydrogen and methyl.

[0058] A preferred subset of compounds are X 1 is sulfur; X 2 is oxygen or sulfur; X 3 is oxygen; Y is CH; B is O or NH; m is 0; n is 1 or 2; R 1 is C1-C2 alkyl; R 2is C1-C2 alkyl; R 3 is selected from hydrogen, chloro, and fluoro; R 4 is selected from chloro, bromo, and cyano; Each R 6 and R 7 are independently selected from hydrogen, halogen, and C1-C2 alkyl; R 8 OR 9 and; R 9 is selected from hydrogen, C1-C4 alkyl, C1-C2 alkoxyC1-C2 alkyl, and phenylC1-C2 alkyl; R 16 and R 17 are independently selected from hydrogen and C1-C2 alkyl It is something.

[0059] A more preferred subset of compounds are X 1 is sulfur; X 2 is oxygen; X 3 is oxygen; B is NH; m is 0; n is 2; Y is CH; R 1 is methyl; R 2 is methyl; R 3 is selected from hydrogen and fluoro; R 4 is chloro; Each R 6 and R 7 is independently selected from hydrogen and methyl; R 8 OR 9 and; R 9 is selected from hydrogen, C1-C4 alkyl, and phenylC1-C2 alkyl; R 16 and R17 are independently selected from hydrogen and methyl It is something.

[0060] A second more preferred subset of compounds is X 1 is sulfur; X 2 is oxygen; X 3 is oxygen; B is O; m is 0; n is 2; Y is CH; R 1 is methyl; R 2 is methyl; R 3 is selected from hydrogen and fluoro; R 4 is chloro; Each R 6 and R 7 is independently selected from hydrogen and methyl; R 8 OR 9 and; R 9 is selected from hydrogen, C1-C4 alkyl, and phenylC1-C2 alkyl; R 16 and R 17 are independently selected from hydrogen and methyl It is something.

[0061] In one set of preferred embodiments, X 1 is sulfur; X 2 is oxygen; X 3 is oxygen; B is O or NH; m is 0; n is 2; Y is CH; R 1 is methyl; R 2 is methyl; R 3 is fluoro; R 4 is chloro; R 6 and R 7 are both hydrogen; R 8 is methoxy; R 16 and R 17 are each independently selected from hydrogen and methyl.

[0062] Example Table Table 1 below shows compounds of formula (I) (wherein X 1 is sulfur and X 2 and X 3 is oxygen, R 1 and R 2 is methyl, R 4 is chloro and R 16 and R 17 is hydrogen and Y is CH.

[0063] [Table 1] JPEG2025502507000004.jpg249150 JPEG2025502507000005.jpg249154 JPEG2025502507000006.jpg249153 JPEG2025502507000007.jpg248153 JPEG2025502507000008.jpg251154 JPEG2025502507000009.jpg250155 JPEG2025502507000010.jpg249153 JPEG2025502507000011.jpg249152 JPEG2025502507000012.jpg249154 JPEG2025502507000013.jpg249153 JPEG2025502507000014.jpg250153 JPEG2025502507000015.jpg250154 JPEG2025502507000016.jpg250153 JPEG2025502507000017.jpg249152 JPEG2025502507000018.jpg248153 JPEG2025502507000019.jpg248153 JPEG2025502507000020.jpg250154 JPEG2025502507000021.jpg251153 JPEG2025502507000022.jpg250153 JPEG2025502507000023.jpg249152 JPEG2025502507000024.jpg250154 JPEG2025502507000025.jpg250154 JPEG2025502507000026.jpg251154 JPEG2025502507000027.jpg249152 JPEG2025502507000028.jpg250154 JPEG2025502507000029.jpg248152 JPEG2025502507000030.jpg248153 JPEG2025502507000031.jpg250153 JPEG2025502507000032.jpg250154 JPEG2025502507000033.jpg249155 JPEG2025502507000034.jpg250152 JPEG2025502507000035.jpg249155 JPEG2025502507000036.jpg249150 JPEG2025502507000037.jpg248153 JPEG2025502507000038.jpg248151 JPEG2025502507000039.jpg248152 JPEG2025502507000040.jpg249153 JPEG2025502507000041.jpg250154 JPEG2025502507000042.jpg191163

[0064] Formula (I) (wherein, X 1 and X 2 is sulfur and X 3 is oxygen, R 1 and R 2 is methyl, R 4 is chloro and R 16 and R 17 is hydrogen, Y is CH, and the values ​​of m, B, D, R 3 and R 8 The 1230 compounds in the above formula (numbered as shown in Table 1 for compounds 1-1 to 1-1230) are represented as compound numbers 2-1 to 2-1230, respectively.

[0065] Formula (I) (wherein, X 1 is sulfur and X 2 and X 3 is oxygen, R 1 and R 2 is methyl, R 4 is chloro and R 16 and R 17 is hydrogen, Y is N, and the values ​​of m, B, D, R 3 and R 8 The 1230 compounds in the above formula (numbered as shown in Table 1 for compounds 1-1 to 1-1230) are represented as compound numbers 3-1 to 3-1230, respectively.

[0066] Formula (I) (wherein, X 1 and X2 is sulfur and X 3 is oxygen, R 1 and R 2 is methyl, R 4 is chloro and R 16 and R 17 is hydrogen, Y is N, and the values ​​of m, B, D, R 3 and R 8 The 1230 compounds in the above formula (numbered as shown in Table 1 for compounds 1-1 to 1-1230) are represented as compound numbers 4-1 to 4-1230, respectively.

[0067] Formula (I) (wherein, X 1 is sulfur and X 2 and X 3 is oxygen, R 1 and R 2 is methyl, R 4 is CN and R 16 and R 17 is hydrogen, Y is N, and the values ​​of m, B, D, R 3 and R 8 The 1230 compounds in the above formula (the numbers are as shown in Table 1 for compounds 1-1 to 1-1230) are represented as compound numbers 5-1 to 5-1230, respectively.

[0068] Formula (I) (wherein, X 1 and X 2 is sulfur and X 3 is oxygen, R 1 and R 2 is methyl, R 4 is CN and R 16 and R 17 is hydrogen, Y is CH, and the values ​​of m, B, D, R 3 and R 8 The 1230 compounds in the above formula (numbered as shown in Table 1 for compounds 1-1 to 1-1230) are represented as compound numbers 6-1 to 6-1230, respectively.

[0069] Formula (I) (wherein, X 1 is sulfur and X 2 and X 3 is oxygen, R1 and R 2 is methyl, R 4 is bromo and R 16 and R 17 is hydrogen, Y is N, and the values ​​of m, B, D, R 3 and R 8 The 1230 compounds in the above formula (as shown in Table 1 for compounds 1-1 to 1-1230) are represented as compound numbers 7-1 to 7-1230, respectively.

[0070] Formula (I) (wherein, X 1 and X 2 is sulfur and X 3 is oxygen, R 1 and R 2 is methyl, R 4 is bromo and R 16 and R 17 is hydrogen, Y is CH, and the values ​​of m, B, D, R 3 and R 8 The 1230 compounds in the above formula (numbered as shown in Table 1 for compounds 1-1 to 1-1230) are represented as compound numbers 8-1 to 8-1230, respectively.

[0071] Formula (I) (wherein, X 1 is sulfur and X 2 and X 3 is oxygen, R 1 and R 2 is methyl, R 4 is chloro and R 16 is hydrogen, and R 17 is methyl, Y is CH, and the values ​​of m, B, D, R 3 and R 8 The 1230 compounds in the above formula (numbered as shown in Table 1 for compounds 1-1 to 1-1230) are represented as compound numbers 9-1 to 9-1230, respectively.

[0072] Formula (I) (wherein, X 1 and X 2 is sulfur and X 3 is oxygen, R 1 and R 2is methyl, R 4 is chloro and R 16 is hydrogen, and R 17 is methyl, Y is CH, and the values ​​of m, B, D, R 3 and R 8 The 1230 compounds in the above formula (the numbers are as shown in Table 1 for compounds 1-1 to 1-1230) are represented as compound numbers 10-1 to 10-1230, respectively.

[0073] Formula (I) (wherein, X 1 is sulfur and X 2 and X 3 is oxygen, R 1 and R 2 is methyl, R 4 is chloro and R 16 is hydrogen, and R 17 is methyl, Y is N, and the values ​​of m, B, D, R 3 and R 8 The 1230 compounds in the above formula (the numbers are as shown in Table 1 for compounds 1-1 to 1-1230) are represented as compound numbers 11-1 to 11-1230, respectively.

[0074] Formula (I) (wherein, X 1 and X 2 is sulfur and X 3 is oxygen, R 1 and R 2 is methyl, R 4 is chloro and R 16 is hydrogen, and R 17 is methyl, Y is N, and the values ​​of m, B, D, R 3 and R 8 The 1230 compounds in the above formula (the numbers are as shown in Table 1 for compounds 1-1 to 1-1230) are represented as compound numbers 12-1 to 12-1230, respectively.

[0075] Formula (I) (wherein, X 1 is sulfur and X 2 and X 3 is oxygen, R 1 and R 2 is methyl, R4 is CN and R 16 is hydrogen, and R 17 is methyl, Y is N, and the values ​​of m, B, D, R 3 and R 8 The 1230 compounds in the above formula (the numbers are as shown in Table 1 for compounds 1-1 to 1-1230) are represented as compound numbers 13-1 to 13-1230, respectively.

[0076] Formula (I) (wherein, X 1 and X 2 is sulfur and X 3 is oxygen, R 1 and R 2 is methyl, R 4 is CN and R 16 is hydrogen, and R 17 is methyl, Y is CH, and the values ​​of m, B, D, R 3 and R 8 The 1230 compounds in the above formula (the numbers are as shown in Table 1 for compounds 1-1 to 1-1230) are represented as compound numbers 14-1 to 14-1230, respectively.

[0077] Formula (I) (wherein, X 1 is sulfur and X 2 and X 3 is oxygen, R 1 and R 2 is methyl, R 4 is bromo and R 16 is hydrogen, and R 17 is methyl, Y is N, and the values ​​of m, B, D, R 3 and R 8 The 1230 compounds in the above formula (the numbers are as shown in Table 1 for compounds 1-1 to 1-1230) are represented as compound numbers 15-1 to 15-1230, respectively.

[0078] Formula (I) (wherein, X 1 and X 2 is sulfur and X 3 is oxygen, R 1 and R 2 is methyl, R 4is bromo and R 16 is hydrogen, and R 17 is methyl, Y is CH, and the values ​​of m, B, D, R 3 and R 8 The 1230 compounds in the above formula (the numbers are as shown in Table 1 for compounds 1-1 to 1-1230) are represented as compound numbers 16-1 to 16-1230, respectively.

[0079] Formula (I) (wherein, X 1 is sulfur and X 2 and X 3 is oxygen, R 1 and R 2 is methyl, R 4 is chloro and R 16 and R 17 is methyl, Y is CH, and the values ​​of m, B, D, R 3 and R 8 The 1230 compounds in the above sequence (as shown in Table 1 for compounds 1-1 to 1-1230) are represented as compound numbers 17-1 to 17-1230, respectively.

[0080] Formula (I) (wherein, X 1 and X 2 is sulfur and X 3 is oxygen, R 1 and R 2 is methyl, R 4 is chloro and R 16 and R 17 is methyl, Y is CH, and the values ​​of m, B, D, R 3 and R 8 The 1230 compounds in the above formula (the numbers are as shown in Table 1 for compounds 1-1 to 1-1230) are represented as compound numbers 18-1 to 18-1230, respectively.

[0081] Formula (I) (wherein, X 1 is sulfur and X 2 and X 3 is oxygen, R 1 and R 2 is methyl, R 4 is chloro and R 16and R 17 is methyl, Y is N, and the values ​​of m, B, D, R 3 and R 8 The 1230 compounds in the above formula (the numbers are as shown in Table 1 for compounds 1-1 to 1-1230) are represented as compound numbers 19-1 to 19-1230, respectively.

[0082] Formula (I) (wherein, X 1 and X 2 is sulfur and X 3 is oxygen, R 1 and R 2 is methyl, R 4 is chloro and R 16 and R 17 is methyl, Y is N, and the values ​​of m, B, D, R 3 and R 8 The 1230 compounds in the above formula (the numbers are as shown in Table 1 for compounds 1-1 to 1-1230) are represented as compound numbers 20-1 to 20-1230, respectively.

[0083] Formula (I) (wherein, X 1 is sulfur and X 2 and X 3 is oxygen, R 1 and R 2 is methyl, R 4 is CN and R 16 and R 17 is methyl, Y is N, and the values ​​of m, B, D, R 3 and R 8 The 1230 compounds in the above formula (the numbers are as shown in Table 1 for compounds 1-1 to 1-1230) are represented as compound numbers 21-1 to 21-1230, respectively.

[0084] Formula (I) (wherein, X 1 and X 2 is sulfur and X 3 is oxygen, R 1 and R 2 is methyl, R 4 is CN and R 16 and R 17is methyl, Y is CH, and the values ​​of m, B, D, R 3 and R 8 The 1230 compounds in the above formula (numbered as shown in Table 1 for compounds 1-1 to 1-1230) are represented as compound numbers 22-1 to 22-1230, respectively.

[0085] Formula (I) (wherein, X 1 is sulfur and X 2 and X 3 is oxygen, R 1 and R 2 is methyl, R 4 is bromo and R 16 and R 17 is methyl, Y is N, and the values ​​of m, B, D, R 3 and R 8 The 1230 compounds in the above formula (numbers are as shown in Table 1 for compounds 1-1 to 1-1230) are represented as compound numbers 23-1 to 23-1230, respectively.

[0086] Formula (I) (wherein, X 1 and X 2 is sulfur and X 3 is oxygen, R 1 and R 2 is methyl, R 4 is bromo and R 16 and R 17 is methyl, Y is CH, and the values ​​of m, B, D, R 3 and R 8 The 1230 compounds in the above formula (the numbers are as shown in Table 1 for compounds 1-1 to 1-1230) are represented as compound numbers 24-1 to 24-1230, respectively.

[0087] The compounds of the present invention can be prepared by techniques known to those skilled in the art of organic chemistry. A general method for preparing the compounds of formula (I) is described below. Unless otherwise specified in the text, the substituents m, X 1 , X 2 , X 3 , Y, B, D, R 1 , R 2 , R 3 , R4 , 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 herein above. The starting materials used for the preparation of the compounds of the present invention can be purchased from ordinary commercial suppliers or prepared by known methods. The starting materials and intermediates can be purified by conventional techniques, such as chromatography, crystallization, distillation and filtration, prior to use in the next step.

[0088] Compounds of formula (I) can be prepared from compounds of formula (A) and formula (B) as shown in Reaction Scheme 1. Reaction Scheme 1 [ka]

[0089] For example, a mixture of compounds of formula (A) and 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 by methods well known in the literature. Compounds of formula (B) can be prepared from anilines of formula (C) as shown in Reaction Scheme 2. Reaction Scheme 2 [ka]

[0090] For example, a compound of formula (C) can be treated with a carbonyl or thiocarbonyl transfer reagent, such as diphosgene, triphosgene or thiophosgene, 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 [ka]

[0091] 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) where m=0 can be prepared from thiols of formula (E) and compounds of formula (F), where LG represents a leaving group, e.g., a halogen atom, such as a chlorine atom, as shown in Reaction Scheme 4. Reaction Scheme 4 [ka]

[0092] For example, a nitro compound of formula (E) can be treated with a compound of formula (F) in the presence of a base, such as triethylamine, in a suitable solvent, such as acetonitrile. Nitro compounds of formula (E) are available or can be prepared by methods well known in the literature. Compounds of formula (F) can be prepared from an alcohol or amine of formula (G) and an acid of formula (H) as shown in Reaction Scheme 5. Reaction Scheme 5 [ka]

[0093] For example, an acid of formula (H) can be treated with an activating agent such as oxalyl chloride in a suitable solvent such as dichloromethane and dimethylformamide, and the resulting intermediate is then treated with an alcohol or amine of formula (G) in the presence of a base such as triethylamine in a suitable solvent such as dichloromethane. The alcohols and amines of formula (G) and the acids of formula (H) are either available or can be prepared by methods well known in the literature. Alternatively, a compound of formula (I) where m=0, a compound of formula (IA), can be prepared from a compound of formula (F) and a thiol of formula (J) as shown in Reaction Scheme 6. Reaction Scheme 6 [ka]

[0094] For example, a thiol of formula (J) can be treated with a compound of formula (F) in the presence of a base, such as triethylamine, in a suitable solvent, such as acetonitrile. Thiols of formula (J) can be prepared from sulfonyl chlorides of formula (K) as shown in Reaction Scheme 7. Reaction Scheme 7 [ka]

[0095] For example, the sulfonyl chloride of formula (K) can be treated with a reducing agent, such as tin dichloride, in a suitable solvent, such as a mixture of water and acetic acid. The sulfonyl chloride of formula (K) can be prepared from a compound of formula (L) as shown in Reaction Scheme 8. Reaction Scheme 8 [ka]

[0096] For example, a compound of formula (L) can be treated with a sulfonylating agent, such as chlorosulfonic acid. A compound of formula (L) can be prepared from a compound of formula (A) and a compound of formula (M) as shown in Reaction Scheme 9. Reaction Scheme 9 [ka]

[0097] For example, a mixture of a compound of formula (A) and a compound of formula (M) 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. Compounds of formula (M) can be prepared from anilines of formula (N) as shown in Reaction Scheme 10. Reaction Scheme 10 [ka]

[0098] For example, compounds of formula (N) can be treated with a carbonyl or thiocarbonyl transfer reagent, such as diphosgene, triphosgene or thiophosgene, in a suitable solvent, such as toluene. Anilines of formula (N) are available or can be prepared by methods well known in the literature. Compounds of formula (I) can also be prepared from acids of formula (P) and amines of formula (G) as shown in Reaction Scheme 11. Reaction Scheme 11 [ka]

[0099] For example, acids of formula (P) may be treated with an activating agent such as oxalyl chloride in a suitable solvent such as dichloromethane and dimethylformamide, and the resulting intermediate may then be treated with an alcohol or amine of formula (G) in the presence of a base, such as triethylamine, in a suitable solvent such as dichloromethane. Acids of formula (P) may be prepared from esters of formula (Q), where R represents an alkyl or similar group, as shown in Reaction Scheme 12. Reaction Scheme 12 [ka]

[0100] For example, a compound of formula (Q) may be treated with hydrochloric acid in a suitable solvent, such as dioxane. Esters of formula (Q) where m=0 may be prepared from thiols of formula (J) and esters of formula (R), where LG represents a leaving group, e.g. a halogen atom, such as a chlorine atom, and R represents an alkyl or similar group, as shown in Reaction Scheme 13. Reaction Scheme 13 [ka]

[0101] For example, a thiol of formula (J) can be treated with a compound of formula (R) in the presence of a base, such as triethylamine, in a suitable solvent, such as acetonitrile. Esters of formula (R) are available or can be prepared by methods well known in the literature. Compounds of formula (I), where m=1 or 2, compounds of formula (IB), can be prepared from compounds of formula (I), where m=0, compounds of formula (IA), as shown in Reaction Scheme 14. Reaction Scheme 14 [ka]

[0102] For example, a compound of formula (IA) can be treated with an oxidizing agent, such as ozone or metachloroperbenzoic acid, in a suitable solvent, such as acetonitrile or dichloromethane. 8 is an OH group, the compound of formula (IC) can be prepared by reacting R 8 OR 9 A compound of formula (I) wherein Reaction Scheme 15 [ka]

[0103] For example, a compound of formula (ID) can be treated with hydrochloric acid in a suitable solvent, such as dioxane. 8 NR 10R 11 Compounds of formula (I), where: Compounds of formula (IE), can be prepared from compounds of formula (IC) as shown in Reaction Scheme 16. Reaction Scheme 16 [ka]

[0104] For example, a compound of formula (IC) is treated with a halogenating reagent, such as oxalyl chloride, in a suitable solvent, such as dichloromethane, to form an acyl halide, which can be reacted with the reagent HNR in the presence of a base, such as triethylamine, in a suitable solvent, such as dichloromethane. 10 R 11 It can be processed with.

[0105] Those skilled in the art will appreciate that it is often possible to vary the order in which the transformations described above are carried out or combine them in alternative ways to prepare a wide range of compounds of formula (I). Several steps may also be combined into a single reaction. All such variations are considered to be within the scope of the present invention.

[0106] Those skilled in the art will appreciate that some reagents may be modified with certain values ​​or with the substituents m, X as defined herein. 1 , X 2 , X 3 , Y, B, D, 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 17and any additional steps, such as protection and / or deprotection steps, that are necessary to achieve the desired transformation will be apparent to one of skill in the art.

[0107] The compounds according to the present invention can be used as herbicides in unmodified form, but are generally formulated into compositions in various ways using formulation auxiliaries such as carriers, solvents and surfactants.The formulations can be in various physical forms, such as dusts, gels, wettable powders, water-dispersible granules, water-dispersible tablets, effervescent pellets, emulsifiable concentrates, microemulsifiable concentrates, oil-in-water emulsions, oil-flowables, aqueous dispersions, oil dispersions, suspoemulsions, capsule suspensions, emulsifiable granules, soluble liquids, water-soluble concentrates (containing water or water-miscible organic solvents as carriers), impregnated polymer films or other forms known, for example, from Manual on Development and Use of FAO and WHO Specifications for Pesticides, United Nations, First Edition, Second Revision (2010).Water-soluble compounds, soluble liquids, water-soluble concentrates or water-soluble granules are preferred.Such formulations can be used directly or can be diluted before use. Dilution can be done, for example, with water, liquid fertilizers, micronutrients, biological organisms, oils or solvents.

[0108] The formulations can be prepared, for example, by mixing the active ingredient with formulation auxiliaries to obtain a composition in the form of a finely divided solid, granules, a solution, a dispersion or an emulsion. The active ingredient can also be formulated with other auxiliaries, such as finely divided solids, mineral oils, oils of vegetable or animal origin, modified oils of vegetable or animal origin, organic solvents, water, surfactants or combinations thereof.

[0109] The active ingredient can also be contained in fine microcapsules. Microcapsules contain the active ingredient in a porous carrier. This allows the active ingredient to be released into the environment in controlled amounts (e.g., sustained release). Microcapsules usually have a diameter of 0.1 to 500 microns. The microcapsules contain the active ingredient in an amount of about 25 to 95% by weight of the capsule weight. The active ingredient can be in the form of a monolithic solid, in the form of fine particles in a solid or liquid dispersion, or in the form of a suitable solution. The encapsulating membrane can include, for example, natural or synthetic rubber, cellulose, styrene / butadiene copolymer, polyacrylonitrile, polyacrylate, polyester, polyamide, polyurea, polyurethane or chemically modified polymers and starch xanthate or other polymers known to those skilled in the art. Alternatively, fine microcapsules can be formed in which the active ingredient is contained in the form of finely divided particles in a solid matrix of the substrate, but the microcapsules themselves are not encapsulated.

[0110] Formulation auxiliaries suitable for the preparation of the compositions according to the invention are known per se. Liquid carriers include water, toluene, xylene, petroleum ether, vegetable oils, acetone, methyl ethyl ketone, cyclohexanone, acid anhydrides, acetonitrile, acetophenone, amyl acetate, 2-butanone, butylene carbonate, chlorobenzene, cyclohexane, cyclohexanol, alkyl esters of acetic acid, diacetone alcohol, 1,2-dichloropropane, diethanolamine, p-diethylbenzene, diethylene glycol, diethylene glycol abietate, diethylene glycol butyl ether, diethylene glycol ethyl ether, diethylene glycol methyl ether, N,N-dimethylformamide, dimethyl sulfoxide, 1,4-dioxane, dipropylene glycol, dipropylene glycol methyl ether, dipropylene glycol dibenzoate, diproxitol, alkyl pyrrolidone, ethyl acetate, 2-ethylhexanol, ethylene carbonate, 1,1,1-Trichloroethane, 2-Heptanone, alpha-pinene, d-limonene, ethyl lactate, ethylene glycol, ethylene glycol butyl ether, ethylene glycol methyl ether, gamma-butyrolactone, glycerol, glycerol acetate, glycerol diacetate, glycerol triacetate, hexadecane, hexylene glycol, isoamyl acetate, isobornyl acetate, isooctane, isophorone, isopropylbenzene, isopropyl myristate, lactic acid, laurylamine, mesityl oxide, methoxypropanol, methyl isoamyl ketone, methyl isobutyl ketone, methyl laurate, methyl octanoate, methyl oleate, methylene chloride, m-xylene, n-hexane, n-octylamine, octadecanoic acid, octylamine acetate, oleic acid, Oleylamine, o-xylene, phenol, polyethylene glycol, propionic acid, propyl lactate, propylene carbonate, propylene glycol, propylene glycol methyl ether, p-xylene, toluene, triethyl phosphate, triethylene glycol, xylene sulfonic acid, paraffin, mineral oil, trichloroethylene, perchloroethylene, ethyl acetate, amyl acetate, butyl acetate, propylene glycol methyl ether, diethylene glycol methyl ether, methanol, ethanol, isopropanol and higher alcohols such as amyl alcohol, tetrahydrofurfuryl alcohol, hexanol, octanol, ethylene glycol, propylene glycol, glycerol, N-methyl-2-pyrrolidone, etc. may be used.

[0111] 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.

[0112] Many surface-active substances can be used advantageously in both solid and liquid formulations, especially in formulations which may be diluted with a carrier before use. The surface-active substances can be anionic, cationic, nonionic or polymeric and can be used as emulsifying agents, wetting agents or suspending agents, or for other purposes. Typical surface-active substances include, for example, salts of alkyl sulfates, such as diethanolammonium lauryl sulfate; salts of alkylaryl sulfonic acids, such as calcium dodecylbenzene sulfonate; alkylphenol / alkylene oxide adducts, such as nonylphenol ethoxylate; alcohol / alkylene oxide adducts, such as tridecyl alcohol ethoxylate; soaps, such as sodium stearate; salts of alkylnaphthalene sulfonic acids, such as sodium dibutylnaphthalene sulfonate; dialkyl esters of sulfosuccinates, such as sodium di(2-ethylhexyl)sulfosuccinate; sorbitol esters, such as sorbitol oleate; quaternary amines, such as lauryltrimethylammonium chloride, polyethylene glycol esters of fatty acids, such as polyethylene glycol stearate; block copolymers of ethylene oxide and propylene oxide; and salts of mono- and di-alkyl phosphate esters, such as those described in, for example, McCutcheon's Detergents and Emulsifiers Annual, MC Publishing Corp., Ridgewood New York, 1989. Further substances described in Jersey (1981) are also included.

[0113] Further auxiliaries which can be used in the agrochemical formulations include crystallization inhibitors, viscosity modifiers, suspending agents, dyes, antioxidants, foaming agents, light absorbers, mixing aids, defoamers, complexing agents, neutralizing or pH adjusting substances and buffers, corrosion inhibitors, fragrances, wetting agents, absorption enhancers, micronutrients, plasticizers, flow regulators, lubricants, dispersants, thickeners, antifreeze agents, fungicides and liquid and solid fertilizers.

[0114] The composition according to the invention may contain an additive comprising an oil of vegetable or animal origin, a mineral oil, an alkyl ester of such oil or a mixture of such oils and oil derivatives. The amount of oil additive in the composition according to the invention is generally 0.01-10% based on the mixture to be applied. For example, the oil additive can be added to the spray tank in the desired concentration after the spray mixture is prepared. Preferred oil additives include mineral oil or oil of vegetable origin (e.g. rapeseed oil, olive oil or sunflower oil), emulsified vegetable oil, alkyl ester of oil of vegetable origin (e.g. methyl derivatives) or oil of animal origin (e.g. fish oil or beef tallow, etc.). Preferred oil additives are C8-C 22 Alkyl esters of fatty acids, especially C 12 ~C 18 Methyl derivatives of fatty acids, such as the methyl esters of lauric acid, palmitic acid, and oleic acid (methyl laurate, methyl palmitate, and methyl oleate, respectively). Compendium of Herbicide Adjuvants, 10 th A large number of oil derivatives are known from the Journal of Chemical Industry, Vol. 13, No. 1, 2010, Issue 1, Springer-Verlag, 2010.

[0115] The herbicidal compositions generally comprise 0.1 to 99% by weight, in particular 0.1 to 95% by weight, of the compound of formula (I) and 1 to 99.9% by weight of formulation auxiliaries, preferably including 0 to 25% by weight of a surfactant. The compositions of the invention generally comprise 0.1 to 99% by weight, in particular 0.1 to 95% by weight, of the compound of the invention and 1 to 99.9% by weight of formulation auxiliaries, preferably including 0 to 25% by weight of a surfactant. Commercial products may preferably be formulated as concentrates, but end users will usually use dilute formulations.

[0116] Application rates vary within wide limits and depend on the nature of the soil, the method of application, the crop plant, the pests to be controlled, the prevailing climatic conditions and other factors governed by the method of application, the time of application and the target crop. As a general guideline, the compounds may be applied at a rate of 1-2000 l / ha, especially 10-1000 l / ha.

[0117] A preferred formulation may have the following composition (% by weight):

[0118] Emulsifiable concentrate: Active ingredient: 1-95%, preferably 60-90% Surfactant: 1-30%, preferably 5-20% Liquid carrier: 1-80%, preferably 1-35%

[0119] Spraying agent: Active ingredient: 0.1-10%, preferably 0.1-5% Solid carrier: 99.9 to 90%, preferably 99.9 to 99%

[0120] Suspension concentrate: Active ingredient: 5-75%, preferably 10-50% Water: 94-24%, preferably 88-30% Surfactant: 1 to 40%, preferably 2 to 30%

[0121] Wettable powder: Active ingredient: 0.5-90%, preferably 1-80% Surfactant: 0.5 to 20%, preferably 1 to 15% Solid carrier: 5 to 95%, preferably 15 to 90%

[0122] Granules: Active ingredient: 0.1-30%, preferably 0.1-15% Solid carrier: 99.5 to 70%, preferably 97 to 85%

[0123] The composition of the present invention may further comprise at least one additional pesticide.For example, the compound according to the present invention may 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.

[0124] The compounds of the present invention may also be used in mixtures with one or more additional herbicides and / or plant growth regulators. Examples of such additional herbicides or plant growth regulators include acetochlor, acifluorfen (including acifluorfen-sodium), aclonifen, ametryn, amicarbazone, aminopyralid, aminotriazole, atrazine, beflubutamid-M, benquitrione, bensulfuron (including bensulfuron-methyl), bentazone, bicyclopyrone, vilanaphos, bipyrazone, bispyribac-sodium, bixlozone, bromacil, bromoxynil, butacil, tetracycline ... rol, butafenacil, carfentrazone (including carfentrazone-ethyl), cloransulam (including cloransulam-methyl), chlorimuron (including chlorimuron-ethyl), chlorotoluron, chlorsulfuron, cinmethylin, clasifos, clethodim, clodinafop (including clodinafop-propargyl), clomazone, clopyralid, cyclopyranyl, cyclopyrimorate, cyclosulfamuron, cyhalofop (including cyhalofop-butyl), 2,4-D( choline salts and its 2-ethylhexyl ester), 2,4-DB, desmedipham, dicamba (including its aluminum, aminopropyl, bis-aminopropylmethyl, choline, dichloroprop, diglycolamine, dimethylamine, dimethylammonium, potassium and sodium salts), diclosulam, difluhenican, diflufenzopyr, dimethachlor, dimethenamid-P, dioxopyritrion, diquat dibromide, diuron, epirifenacil, ethalflu Larin, Ethofumesate, Fenoxaprop (including Fenoxaprop-P-ethyl), Fenoxasulfone, Fenpyrazone, Fenquinotrione, Fentrazamide, Flazasulfuron, Florasulam, Florpyrauxifen (including Florpyrauxifen-benzyl), Fluazifop (including Fluazifop-P-butyl), Flucarbazone (including Flucarbazone-sodium), Flufenacet, Flumetsulam, Flumioxazin, Fluometuron, Fomesafen Flupyrsulfuron (including Flupyrsulfuron-methyl-sodium), Fluroxypyr (including Fluroxypyr-meptyl), Fomesafen,Foramsulfuron, glufosinate (including L-glufosinate and both ammonium salts), glyphosate (including its diammonium, isopropylammonium and potassium salts), haloxifen (including haloxyfop-methyl), haloxyfop (including haloxyfop-methyl), hexazinone, hydantocidin, imazamox (including R-imazamox), imazapic, imazapyr, imazethapyr, indaziflam, iodosulfuron (including iodosulfuron-sodium), iofensulfuron (including iofensulfuron-sodium), sodium), ioxynil, isoproturon, isoxaflutole, lancotrione, MCPA, MCPB, mecoprop-P, mesosulfuron (including mesosulfuron-methyl), mesotrione, metamitron, metazachlor, methiozoline, metolachlor, metosulam, metribuzin, metsulfuron, napropamide, nicosulfuron, norflurazon, oxadiazon, oxasulfuron, oxyfluorfen, paraquat dichloride, pendimethalin, penoxsulam, phenmedipham, picloram, pinoxaden, pretila Chlor, primisulfuron-methyl, prometryn, propanil, propaquizafop, propyrisulfuron, propyzamide, prosulfocarb, prosulfuron, pyraclonil, pyraflufen (including pyraflufen-ethyl), pyrasulfotole, pyridate, pyriftalid, pyrimisulfan, pyroxasulfone, pyroxsulam, quinclorac, quinmerac, quizalofop (including quizalofop-p-ethyl and quizalofop-p-tefuryl), rimisoxafen, rimsulfuron, saflufenacil, sethoxydim, simazine, S-metra Chlor, sulfentrazone, sulfosulfuron, tebuthiuron, tefuryltrione, tembotrione, terbuthylazine, terbutryn, tetflupyrolimet, thiencarbazone, thifensulfuron, thiaphenacyl, torpiralate, topramezone, tralkoxydim, triafamone, triallate, triasulfuron, tribenuron (including tribenuron-methyl), triclopyr, trifloxysulfuron (including trifloxysulfuron-sodium), trifludimoxazine, trifluralin, triflusulfuron, tripyrasulfone,[(E)-[2-(trifluoromethyl)phenyl]methyleneamino]2,6-bis[(4,6-dimethoxypyrimidin-2-yl)oxy]benzoate, 3-(2-chloro-4-fluoro-5-(3-methyl-2,6-dioxo-4-trifluoromethyl-3,6-dihydropyrimidin-1(2H)-yl)phenyl)-5-methyl-4,5-dihydroisoxazole-5-carboxylic acid ethyl ester, 4-hydroxy-1-methoxy-5-methyl-3-[4-(trifluoromethyl)-2-pyridyl]imidazolidin-2-one, 4-hydroxy-1,5-dimethyl-3-[4-(trifluoromethyl)-2-pyridyl]imidazolidin-2-one, 5-ethoxy-4-hydro 4-hydroxy-1-methyl-3-[4-(trifluoromethyl)-2-pyridyl]imidazolidin-2-one, 4-hydroxy-1-methyl-3-[4-(trifluoromethyl)-2-pyridyl]imidazolidin-2-one, 4-hydroxy-1,5-dimethyl-3-[1-methyl-5-(trifluoromethyl)pyrazol-3-yl]imidazolidin-2-one, (4R)1-(5-tert-butylisoxazol-3-yl)-4-ethoxy-5-hydroxy-3-methyl-imidazolidin-2-one, 4-amino-3-chloro-5-fluoro-6-(7-fluoro-1H-indol-6-yl)pyridine-2-carboxylic acid (or its agrochemically acceptable esters, e.g., methyl 4-Amino-3-chloro-5-fluoro-6-(7-fluoro-1H-indol-6-yl)pyridine-2-carboxylate, prop-2-ynyl 4-Amino-3-chloro-5-fluoro-6-(7-fluoro-1H-indol-6-yl)pyridine-2-carboxylate and cyanomethyl 4-amino-3-chloro-5-fluoro-6-(7-fluoro-1H-indol-6-yl)pyridine-2-carboxylate), 3-ethylsulfanyl-N-(1,3,4-oxadiazol-2-yl)-5-(trifluoromethyl)-[1,2,4]triazolo[4,3-a]pyridine-8-carboxamide, 3-(isopropylsulfanylmethyl)-N-(5-methyl-1,3,4-oxadiazol-2-yl)-5-(trifluoromethyl)-[1,2,4]triazolo[4,3-a]pyridine-8-carboxamide,3-(isopropylsulfonylmethyl)-N-(5-methyl-1,3,4-oxadiazol-2-yl)-5-(trifluoromethyl)-[1,2,4]triazolo[4,3-a]pyridine-8-carboxamide, 3-(ethylsulfonylmethyl)-N-(5-methyl-1,3,4-oxadiazol-2-yl)-5-(trifluoromethyl)-[1,2,4]triazolo[4,3-a]pyridine-8-carboxamide, ethyl-2-[[3-[[3-chloro-5-fluoro-6-[3-methyl-2,6-dioxo-4-(trifluoromethyl)pyrimidin-1-yl]-2-pyridyl]oxy]acetate, 6-chloro-4-(2,7-dimethyl-1-naphthyl)-5-hydroxy-2-methyl-pyridazin-3-one, tetrahydrofuran-2-ylmethyl (2R)-2-[(4-amino-3,5-dichloro-6-fluoro-2-pyridyl)oxy]propanoate, (2R)-2-[(4-amino-3,5-dichloro-6-fluoro-2-pyridyl)oxy]propanoic acid, tetrahydrofuran-2-ylmethyl 2-[(4-amino-3,5-dichloro-6-fluoro-2-pyridyl)oxy]propanoate, 2-[(4-amino-3,5-dichloro-6-fluoro-2-pyridyl)oxy]propanoic acid, 2-fluoro-N-(5-methyl-1,3,4-oxadiazol-2-yl)-3-[(R)-propylsulfinyl]-4-(trifluoromethyl)benzamide, 2-fluoro-N-(5-methyl-1,3,4-oxadiazol-2-yl)-3-propylsulfinyl-4-(trifluoromethyl)benzamide, (2-fluorophenyl)methyl 6-amino-5-chloro-2-(4-chloro-2-fluoro-3-methoxy-phenyl)pyrimidine-4-carboxylate, 6-amino-5-chloro-2-(4-chloro-2-fluoro-3-methoxy-phenyl)pyrimidine-4-carboxylic acid, 3-(3-chlorophenyl)-6-(5-hydroxy-1,3-dimethyl-pyrazole-4-carbonyl)-1,5-dimethyl-quinazoline-2,4-dione and [4-[3-(3-chlorophenyl)-1,5-dimethyl-2,4-dioxo-quinazoline-6-carbonyl]-2,5-dimethyl-pyrazol-3-yl] N,N-diethylcarbamate,Methyl 2-[(E)-[2-chloro-4-fluoro-5-[3-methyl-2,6-dioxo-4-(trifluoromethyl)pyrimidin-1-yl]phenyl]methyleneamino]oxypropanoate and methyl (2R)-2-[(E)-[2-chloro-4-fluoro-5-[3-methyl-2,6-dioxo-4-(trifluoromethyl)pyrimidin-1-yl]phenyl]methyleneamino]oxypropanoate.

[0125] The mixing partners of the compounds of formula (I) may also be in the form of esters or salts, as mentioned, for example, in The Pesticide Manual, Fourteenth Edition, British Crop Protection Council, 2006.

[0126] The compounds of formula (I) may also be used in mixtures with other agricultural chemicals such as fungicides, nematicides or insecticides (examples of which are given in The Pesticide Manual).

[0127] The mixing ratio of the compound of formula (I) to the mixing partners is preferably 1:100 to 1000:1.

[0128] The mixtures can be advantageously used in the abovementioned formulations (in which case "active ingredient" relates to the respective mixture of the compound of formula (I) with the mixing partner).

[0129] The compounds of formula (I) of the present invention may also be combined with herbicide safeners. Preferred combinations are benoxacor, cloquintocet (including cloquintocet-mexyl), cyprosulfamide, dichlormid, fenchlorazole (including fenchlorazole-ethyl), fenclorim, fluxofenim, furilazole, isoxadifen (including isoxadifen-ethyl), mefenpyr (including mefenpyr-diethyl), metcamifen and oxabetrinil.

[0130] Mixtures of compounds of formula (I) with cyprosulfamide, isoxadifen (including isoxadifen-ethyl), cloquintocet (including cloquintocet mexyl) and / or N-(2-methoxybenzoyl)-4-[(methyl-aminocarbonyl)amino]benzenesulfonamide are especially preferred.

[0131] The safener of the compound of formula (I) is, for example, th Edition (BCPC), 2006. A reference to cloquintocet-mexyl also applies to its lithium, sodium, potassium, calcium, magnesium, aluminum, iron, ammonium, quaternary ammonium, sulfonium or phosphonium salts, and a reference to fenchlorazole-ethyl also applies to fenchlorazole, etc., as disclosed in WO 02 / 34048.

[0132] Preferably, the mixing ratio of the compound of formula (I) to the safener is from 100:1 to 1:10, in particular from 20:1 to 1:1.

[0133] The mixtures may be advantageously used in the formulations described above, where "active ingredient" refers to the respective mixture of compound of formula (I) and safener.

[0134] The compounds of formula (I) of the present invention are useful as herbicides. Thus, the present invention further includes a method for controlling unwanted plants, which comprises applying an effective amount of the compounds of the present invention or a herbicidal composition containing said compounds to said plants or to the habitat containing them. "Control" means killing, reducing or retarding growth, or preventing or reducing germination. Generally, the plants to be controlled are unwanted plants (weeds). "Habitat" means the area where the plants are growing or will grow.

[0135] The application rates of the compounds of formula (I) may vary within a wide range and depend on the nature of the soil, the method of application (pre-emergence; post-emergence; application in the furrow; no-tillage application, etc.), the crop plants, the weeds to be controlled, the prevailing climatic conditions, as well as the application method, time of application and other factors governed by the target crop. The compounds of formula (I) according to the invention are generally applied at a rate of 10 to 2000 g / ha, in particular 50 to 1000 g / ha. A preferred range is 10 to 200 g / ha.

[0136] Application is generally made by spraying the composition, usually with a tractor-mounted sprayer for large areas, although other methods such as dusting (for dusts), dripping or irrigation can also be used.

[0137] Useful plants in which the compositions according to the invention can be used include crops such as cereals, e.g. barley and wheat, cotton, oilseed rape, sunflower, corn, rice, soybeans, sugar beets, sugar cane and turf.

[0138] Crop plants can also include trees such as fruit trees, palm trees, coconut trees or other nuts, as well as vines such as grapes, fruit bushes, fruit plants and vegetables.

[0139] Crops should also be understood to include crops that have been made tolerant to herbicides or classes of herbicides (e.g., ALS-, GS-, EPSPS-, PPO-, ACCase- and HPPD-inhibitors) by conventional breeding methods or genetic engineering. An example of a crop that has been made tolerant to imidazolinones, such as imazamox, by conventional breeding methods is Clearfield® summer rapeseed (canola). Examples of crops that have been made tolerant to herbicides by genetic engineering methods include, for example, glyphosate- and glufosinate-tolerant corn varieties available under the trade names RoundupReady® and LibertyLink®.

[0140] It should also be understood that crops are those that have been made resistant to pests by genetic engineering methods, such as Bt maize (resistant to the European corn borer), Bt cotton (resistant to the cotton weevil) and even Bt potato (resistant to the Colorado potato beetle). An example of Bt maize is the Bt176 maize hybrid from NK® (Syngenta Seeds). Bt toxins are proteins that are naturally formed by the Bacillus thuringiensis soil bacterium. Examples of toxins or transgenic plants capable of synthesizing such toxins are described in EP 451878, EP 374753, WO 93 / 07278, WO 95 / 34656, WO 03 / 052073 and EP 427529. Examples of transgenic plants containing one or more genes encoding insecticide resistance and expressing one or more toxins are KnockOut® (corn), Yield Gard® (corn), NuCOTIN33B® (cotton), Bollgard® (cotton), NewLeaf® (potato), NatureGard® and Protexcta®. Either the plant crop or its seed material can be resistant to herbicides and at the same time resistant to insect ingestion (a "stacked" transgenic event). For example, a seed has the ability to express an insecticidal Cry3 protein and is at the same time resistant to glyphosate.

[0141] It should also be understood that crop plants include those obtained by conventional breeding or genetic engineering methods and contain so-called output traits (e.g. improved storage stability, higher nutritional value and improved flavor).

[0142] Other useful plants include turfgrass grown commercially for turfgrass or lawns, for example, on golf courses, lawns, parks and roadsides, as well as ornamental plants such as flowers or shrubs.

[0143] The compounds and compositions of formula (I) of the present invention can generally be used to control a wide variety of monocotyledonous and dicotyledonous weed species. Examples of monocotyledonous species that can usually be controlled are Alopecurus myosuroides, Avena fatua, Brachiaria plantaginea, Bromus tectorum, Cyperus esculentus, Digitaria sanguinalis, Echinochloa crus-galli, Lolium perenne, Lolium multiflorum, Panicum miliaceum, Poa annua, Setaria viridis, Setaria faberi, and others. faberi and Sorghum bicolor.Examples of dicotyledonous species that can be controlled include Abutilon theophrasti, Amaranthus retroflexus, Bidens pilosa, Chenopodium album, Euphorbia heterophylla, Galium aparine, Ipomoea hederacea, Kochia scoparia, Polygonum convolvulus, Sida spinosa, Sinapis arvensis, Solanum nigrum, Stellaria media, Veronica persica, and others. persica and Xanthium strumarium.

[0144] Undesirable plants should also be understood to include those weeds that have been made tolerant to herbicides or classes of herbicides (e.g., ALS-, GS-, EPSPS-, PPO-, ACCase- and HPPD-inhibitors) by evolution, by traditional breeding methods or by genetic engineering. An example is Amaranthus palmeri, which has evolved resistance to glyphosate and / or acetolactate synthase (ALS) inhibitor herbicides.

[0145] The compounds of the present invention can be used in methods for controlling undesirable plants or weeds that are resistant to protoporphyrinogen oxidase (PPO) inhibitors. For example, Amaranthus palmeri and Amaranthus tuberculatus populations have evolved as PPO-resistant weeds due to amino acid substitutions in PPX2L, such as those occurring at amino acids R128 (also referred to as R98) and G399, or a codon (glycine) deletion in PPX2L at codon 210 (Δ210) (codon numbering is based on NCBI reference DQ386114). The compounds of the invention can be used in methods to control Amaranthus palmeri and / or Amaranthus tuberculatus having mutations or deletions in the aforementioned codons or equivalents, and it would be obvious to try the compounds to control undesirable plants or weeds having other mutations that confer tolerance or resistance to PPO inhibitors that may occur.

[0146] The compounds of formula (I) are also useful in pre-harvest drying of crops, such as, but not limited to, potatoes, soybeans, sunflowers and cotton, which are used to dry the leaves of crops to facilitate harvesting without significant damage to the crop itself.

[0147] The compounds / compositions of the present invention are particularly useful in non-selective burn down applications and may therefore also be used to control volunteer vegetation or to ward off crop plants.

[0148] 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. EXAMPLES

[0149] The following examples are intended to illustrate, but not limit, the present invention.

[0150] Synthesis Example Example 1 Preparation of (3-methoxy-3-oxo-propyl) 2-[2-chloro-5-(3,5-dimethyl-2,6-dioxo-4-thioxo-1,3,5-triazinan-1-yl)-4-fluoro-phenyl]sulfanyl propanoate (Compound 9-245) Step 1: Synthesis of 2-chloro-4-fluoro-5-nitro-benzoic acid [ka] Fuming nitric acid (2.8 ml, 43 mmol) was added to a stirred solution of 2-chloro-4-fluoro-benzoic acid (5.0 g, 29 mmol) in concentrated sulfuric acid (20 ml) at 0° C. The mixture was stirred for 20 minutes and then carefully poured into ice water. The resulting mixture was filtered and the solid was washed with acetonitrile to give 2-chloro-4-fluoro-5-nitro-benzoic acid (6.4 g). 1 H NMR(400MHz,CDCl3)δ 8.6(d,1H),7.05(d,1H),5.9(br s,1H)ppm.

[0151] Step 2: Synthesis of ethyl 2-chloro-4-fluoro-5-nitro-benzoate [ka] Oxalyl chloride (0.88 ml, 9.9 mmol) was added dropwise to a solution of 2-chloro-4-fluoro-5-nitro-benzoic acid (1.5 g, 6.6 mmol) in dichloromethane (15 ml). The solution was stirred for 15 minutes, then dimethylformamide (3 drops) was added and stirring was continued until gas evolution ceased. Ethanol (4 ml, 67 mmol) was added and the resulting solution was stirred for 17 hours, then the solvent was evaporated under reduced pressure to give ethyl 2-chloro-4-fluoro-5-nitro-benzoate (1.7 g) as a solid. 1 H NMR(400MHz,CDCl3)δ 8.7(d,1H),7.5(d,1H),4.45(q,2H),1.45(t,3H)ppm.

[0152] Step 3: Synthesis of ethyl 5-amino-2-chloro-4-fluoro-benzoate [ka] Tin dichloride hydrate (4.7 g, 24 mmol) was added to a stirred solution of ethyl 2-chloro-4-fluoro-5-nitro-benzoate (2.1 g, 8.1 mmol) in ethyl acetate (21 ml), then the mixture was heated at reflux for 1.5 h, allowed to cool, and the solvent was evaporated under reduced pressure. The residue was purified by column chromatography to give ethyl 5-amino-2-chloro-4-fluoro-benzoate (1.2 g). 1 H NMR(400MHz,CDCl3)δ 7.3(d,1H),7.1(d,1H),4.35(q,2H),3.35(br s,2H),1.4(t,3H)ppm.

[0153] Step 4: Synthesis of ethyl 2-chloro-4-fluoro-5-isocyanato-benzoate [ka] Diphosgene (0.8 ml, 6.6 mmol) was added to a stirred solution of ethyl 5-amino-2-chloro-4-fluoro-benzoate (1.2 g, 5.5 mmol) in dry toluene (24 ml). The resulting mixture was heated at reflux for 2 hours, allowed to cool, and concentrated under reduced pressure to give ethyl 2-chloro-4-fluoro-5-isocyanato-benzoate.

[0154] Step 5: Synthesis of ethyl 2-chloro-5-(3,5-dimethyl-2,6-dioxo-4-thioxo-1,3,5-triazinan-1-yl)-4-fluoro-benzoate [ka] A solution of 1,3-dimethylthiourea (0.26 g, 2.5 mmol) and triethylamine (0.37 ml, 2.7 mmol) in toluene (10 ml) was added to ethyl 2-chloro-4-fluoro-5-isocyanato-benzoate (500 mg, 2.1 mmol) and the resulting solution was heated to reflux. Carbonyldiimidazole (520 mg, 3.1 mmol) was added portionwise over 15 minutes and the resulting solution was heated at reflux for a further 3 hours, then cooled and the solvent evaporated under reduced pressure. The residue was purified by column chromatography to give ethyl 2-chloro-5-(3,5-dimethyl-2,6-dioxo-4-thioxo-1,3,5-triazinan-1-yl)-4-fluoro-benzoate (550 mg) as a gum. 1 H NMR(400MHz,CDCl3)δ 7.95(d,1H),7.45(d,1H),4.4(q,2H),3.8(s,6H),1.45(t,3H)ppm.

[0155] Step 6: Synthesis of 2-chloro-5-(3,5-dimethyl-2,6-dioxo-4-thioxo-1,3,5-triazinan-1-yl)-4-fluoro-benzoic acid [ka] Concentrated sulfuric acid (2.6 ml, 45 mmol) was added to a stirred solution of ethyl 2-chloro-5-(3,5-dimethyl-2,6-dioxo-4-thioxo-1,3,5-triazinan-1-yl)-4-fluoro-benzoate (1.7 g, 4.5 mmol) in glacial acetic acid (17 ml). The mixture was heated at 110° C. for 6 hours, allowed to cool to ambient temperature, and carefully poured into ice water. The resulting mixture was filtered and the solid was dried to give 2-chloro-5-(3,5-dimethyl-2,6-dioxo-4-thioxo-1,3,5-triazinan-1-yl)-4-fluoro-benzoic acid (1.5 g). 1 H NMR(400MHz,DMSO-d6)δ 8.15(d,1H),7.85(d,1H),3.6(s,6H),3.35(br s,1H)ppm.

[0156] Step 7: Synthesis of tert-butyl N-[2-chloro-5-(3,5-dimethyl-2,6-dioxo-4-thioxo-1,3,5-triazinan-1-yl)-4-fluoro-phenyl]carbamate [ka] A solution of dicyclohexylcarbodiimide (0.64 g, 3.0 mmol) in chlorobenzene (6 ml) was added dropwise to a stirred solution of 2-chloro-5-(3,5-dimethyl-2,6-dioxo-4-thioxo-1,3,5-triazinan-1-yl)-4-fluoro-benzoic acid (1.0 g, 2.9 mmol) and tert-butyl N-hydroxycarbamate (0.37 g, 2.7 mmol) in chlorobenzene (6 ml) at −15° C. The resulting mixture was stirred for 30 minutes, then palladium dichloride triphenylphosphine complex (0.1 g, 0.15 mmol) and cesium carbonate (1.9 g, 5.8 mmol) were added and the mixture was heated at 85° C. for 1 hour. The mixture was cooled, extracted with ethyl acetate and the organic phase was dried and evaporated to leave a residue which was purified by column chromatography to give tert-butyl N-[2-chloro-5-(3,5-dimethyl-2,6-dioxo-4-thioxo-1,3,5-triazinan-1-yl)-4-fluoro-phenyl]carbamate (0.8 g). 1 H NMR (400 MHz, CDCl3) δ 8.3 (d, 1H), 7.3 (d, 1H), 3.8 (s, 6H), 1.5 (s, 9H) ppm (NH not observed).

[0157] Step 8: Synthesis of 3-(5-amino-4-chloro-2-fluoro-phenyl)-1,5-dimethyl-6-thioxo-1,3,5-triazinane-2,4-dione [ka] A mixture of tert-butyl N-[2-chloro-5-(3,5-dimethyl-2,6-dioxo-4-thioxo-1,3,5-triazinan-1-yl)-4-fluoro-phenyl]carbamate (700 mg, 1.7 mmol) and trifluoroacetic acid (10.5 ml) was stirred at ambient temperature for 1 hour and then concentrated under reduced pressure. Saturated aqueous sodium bicarbonate (30 ml) was added and the mixture was extracted with ethyl acetate (2×80 ml). The combined organic phases were dried over sodium sulfate, filtered and evaporated under reduced pressure to give 3-(5-amino-4-chloro-2-fluoro-phenyl)-1,5-dimethyl-6-thioxo-1,3,5-triazinan-2,4-dione (500 mg) as a white solid. 1 H NMR (400 MHz, CDCl3) δ 7.25 (d, 1H), 6.7 (d, 1H), 3.8 (s, 6H) ppm (no NH2 observed).

[0158] Step 9: Synthesis of 2-chloro-5-(3,5-dimethyl-2,6-dioxo-4-thioxo-1,3,5-triazinan-1-yl)-4-fluoro-benzenesulfonyl chloride [ka] A solution of sodium nitrite (0.24 g, 3.3 mmol) in water (12 ml) at 0° C. was added dropwise to a stirred mixture of 3-(5-amino-4-chloro-2-fluoro-phenyl)-1,5-dimethyl-6-thioxo-1,3,5-triazinane-2,4-dione (0.9 g, 2.8 mmol) and hydrochloric acid (24 ml) at −5° C., and the resulting mixture was stirred at 0° C. for 15 minutes. The mixture was added dropwise to a stirred mixture of thionyl chloride (12 ml) and water (48 ml) to which cuprous chloride (I) (6 mg, 0.06 mmol) had been added at −5° C. The resulting mixture was stirred at 0° C. for 30 minutes and at ambient temperature for 1 hour, then water (30 ml) and ethyl acetate (90 ml) were added. The phases were separated and the aqueous was extracted with ethyl acetate (90 ml). The combined organic phases were dried over sodium sulfate, filtered and evaporated under reduced pressure to give 2-chloro-5-(3,5-dimethyl-2,6-dioxo-4-thioxo-1,3,5-triazinan-1-yl)-4-fluoro-benzenesulfonyl chloride (1 g) as a solid. 1 H NMR(400MHz,CDCl3)δ 8.2(d,1H),7.6(d,1H),3.8(s,6H)ppm.

[0159] Step 10: Synthesis of 3-(4-chloro-2-fluoro-5-sulfanyl-phenyl)-1,5-dimethyl-6-thioxo-1,3,5-triazinane-2,4-dione [ka] Triphenylphosphine (0.94 g, 3.5 mmol) was added portionwise to a stirred solution of 2-chloro-5-(3,5-dimethyl-2,6-dioxo-4-thioxo-1,3,5-triazinan-1-yl)-4-fluoro-benzenesulfonyl chloride (0.5 g, 1.0 mmol) in tetrahydrofuran (6 ml). Water (1 ml) was added and the resulting mixture was stirred at ambient temperature for 18 hours. Water (20 ml) and ethyl acetate (50 ml) were added and the phases were separated. The aqueous phase was extracted with ethyl acetate (50 ml) and the combined organic phases were dried over sodium sulfate, filtered and evaporated under reduced pressure to leave a residue which was purified by column chromatography to give 3-(4-chloro-2-fluoro-5-sulfanyl-phenyl)-1,5-dimethyl-6-thioxo-1,3,5-triazinane-2,4-dione (264 mg) as a solid. 1 H NMR(400MHz,CDCl3)δ 7.35(m,2H),3.9(s,1H),3.8(s,6H)ppm.

[0160] Step 11: Synthesis of (3-methoxy-3-oxo-propyl) 2-[2-chloro-5-(3,5-dimethyl-2,6-dioxo-4-thioxo-1,3,5-triazinan-1-yl)-4-fluoro-phenyl]sulfanylpropanoate (compound 9-245) [ka] (3-Methoxy-3-oxo-propyl) 2-bromopropanoate (prepared as described in Example 2; 70 mg, 0.29 mmol) was added to a stirred mixture of 3-(4-chloro-2-fluoro-5-sulfanyl-phenyl)-1,5-dimethyl-6-thioxo-1,3,5-triazinane-2,4-dione (90 mg, 0.26 mmol), cesium carbonate (88 mg, 0.27 mmol) and acetonitrile (1.8 ml) and the resulting mixture was stirred at ambient temperature for 2 hours. Ethyl acetate (40 ml) was added and the resulting mixture was washed with water (2×10 ml), dried over sodium sulfate, filtered and evaporated to leave a residue which was purified by column chromatography to give (3-methoxy-3-oxo-propyl) 2-[2-chloro-5-(3,5-dimethyl-2,6-dioxo-4-thioxo-1,3,5-triazinan-1-yl)-4-fluoro-phenyl]sulfanylpropanoate (compound 9-245) (85 mg) as an oil. 1 H NMR(400MHz,CDCl3)δ 7.55(d,1H),7.4(d,1H),4.3(m,2H),3.9(m,1H),3.75(s,6H),3.65(s,3H),2.6(m,2H),1.55(d,3H)ppm.

[0161] Example 2 Preparation of (3-methoxy-3-oxo-propyl) 2-bromopropanoate [ka] Triethylamine (1.3 ml, 9.1 mmol) and methyl 3-hydroxypropanoate (0.48 ml, 5.0 mmol) were added dropwise to a stirred solution of 2-bromopropanoyl bromide (0.49 ml, 4.5 mmol) in acetonitrile (15 ml) at 0° C. The resulting mixture was stirred at 0° C. for 1 h and then at ambient temperature for 2 h. Water (20 ml) and ethyl acetate (60 ml) were added, the phases were separated and the aqueous phase was extracted with ethyl acetate (60 ml). The combined organic phases were dried over sodium sulfate, filtered and evaporated under reduced pressure to leave an oil which was purified by column chromatography to give (3-methoxy-3-oxo-propyl) 2-bromopropanoate (440 mg) as an oil. 1 H NMR(400MHz,CDCl3)δ 4.45(m,2H),4.35(m,1H),3.75(s,3H),2.7(t,2H),1.8(d,3H)ppm.

[0162] Example 3 Preparation of methyl 3-[2-[2-chloro-5-(3,5-dimethyl-2,6-dioxo-4-thioxo-1,3,5-triazinan-1-yl)-4-fluoro-phenyl]sulfanylpropanoylamino]propanoate (Compound 9-272) Step 1: Synthesis of methyl 3-(2-bromopropanoylamino)propanoate [ka] Triethylamine (2.6 ml, 9.1 mmol) and 2-bromopropanoyl bromide (0.97 ml, 9.1 mmol) were added to a stirred mixture of (3-methoxy-3-oxo-propyl)ammonium chloride (1.42 g, 10 mmol) in acetonitrile (30 ml) at 0° C. The resulting mixture was stirred at 0° C. for 1 h and then at ambient temperature for 2 h. Water (20 ml) and ethyl acetate (60 ml) were added, the phases were separated and the aqueous phase was extracted with ethyl acetate (60 ml). The combined organic phases were dried over sodium sulfate, filtered and evaporated under reduced pressure to leave an oil which was purified by column chromatography to give methyl 3-(2-bromopropanoylamino)propanoate (560 mg) as a solid.1 H NMR(400MHz,CDCl3)δ 6.95(br s,1H),4.4(q,1H),3.75(s,3H),3.55(m,2H),2.6(m,2H),1.85(d,3H)ppm.

[0163] Step 2: Synthesis of methyl 3-[2-[2-chloro-5-(3,5-dimethyl-2,6-dioxo-4-thioxo-1,3,5-triazinan-1-yl)-4-fluoro-phenyl]sulfanylpropanoylamino]propanoate (compound 9-272) [ka] Methyl 3-(2-bromopropanoylamino)propanoate (78 mg, 0.32 mmol) was added to a stirred mixture of 3-(4-chloro-2-fluoro-5-sulfanyl-phenyl)-1,5-dimethyl-6-thioxo-1,3,5-triazinane-2,4-dione (prepared as described in Example 1, Step 10; 100 mg, 0.29 mmol), cesium carbonate (98 mg, 0.30 mmol) and acetonitrile (2 ml) and the resulting mixture was stirred at ambient temperature for 2 hours. Ethyl acetate (50 ml) was added and the resulting mixture was washed with water (2×20 ml), dried over sodium sulfate, filtered and evaporated to leave a residue which was purified by column chromatography to give methyl 3-[2-[2-chloro-5-(3,5-dimethyl-2,6-dioxo-4-thioxo-1,3,5-triazinan-1-yl)-4-fluoro-phenyl]sulfanylpropanoylamino]propanoate (compound 9-272) (36 mg) as a solid. 1 H NMR(400MHz,CDCl3)δ 7.35(d,1H),7.25(d,1H),7.0(br m,1H),3.8(m,2H),3.75(s,6H),3.65(s,3H),3.55(m,1H),3.4(m,1H),2.45(m,2H),1.6(d,3H)ppm.

[0164] Formulation Examples

[0165] [Table 2]

[0166] The combination is thoroughly mixed with the adjuvant and the mixture is thoroughly ground in a suitable mill to give a wettable powder which can be diluted with water to give a suspension of the desired concentration.

[0167] emulsifiable concentrate Active ingredient 10% Octylphenol polyethylene glycol ether 3% (4-5 mol of ethylene oxide) Calcium dodecylbenzenesulfonate 3% Castor oil polyglycol ether (35 mol ethylene oxide) 4% Cyclohexanone 30% Xylene Mixture 50%

[0168] Emulsions of any required dilution rate which can be used for plant protection can be obtained from this concentrate by dilution with water.

[0169] [Table 3]

[0170] Ready-to-use powders are obtained by mixing the combination with a carrier and grinding the mixture in a suitable mill.

[0171] Extrusion Granules Active ingredient 15% Sodium Lignosulfonate 2% Carboxymethylcellulose 1% Kaolin 82%

[0172] The combination is mixed with the auxiliaries and ground, the mixture is moistened with water, the mixture is extruded and then dried in a stream of air.

[0173] Coated Granules Active ingredient: 8% Polyethylene glycol (mol.wt.200) 3% Kaolin 89%

[0174] In a mixer, the finely ground combination is applied uniformly to the kaolin moistened with polyethylene glycol. In this way, dust-free coated granules are obtained.

[0175] Suspension concentrate Active ingredient 40% Propylene glycol 10% Nonylphenol polyethylene glycol ether (15 mol ethylene oxide) 6% Sodium Lignosulfonate 10% Carboxymethylcellulose 1% Silicone oil (in the form of a 75% emulsion in water) 1% water 32%

[0176] The finely ground combination is thoroughly mixed with the adjuvant to give a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water.

[0177] Slow-release capsule suspension 28 parts of the combination are mixed with 2 parts of aromatic solvent and 7 parts of toluene diisocyanate / polymethylene-polyphenylisocyanate-mixture (8:1). The mixture is emulsified in a mixture of 1.2 parts of polyvinyl alcohol, 0.05 parts of defoamer and 51.6 parts of water until the desired particle size is achieved. A mixture of 2.8 parts of 1,6-diaminohexane in 5.3 parts of water is added to the emulsion. The mixture is stirred until the polymerization reaction is complete.

[0178] The resulting capsule suspension is stabilized by adding 0.25 parts of a thickener and 3 parts of a dispersant. The capsule suspension formulation contains 28% active ingredient. The medium capsule diameter is 8-15 microns.

[0179] The resulting formulation is applied to the seeds as an aqueous suspension in a device suitable for the purpose.

[0180] Biological Examples Pre-emergence biological efficacy Weed and / or crop seeds were sown in standard soil in pots (Amaranthus palmeri (AMAPA), Lolium perenne (LOLPE), Euphorbia heterophylla (EPHHL), Ipomoea hederacea (IPOHE), Setaria faberi (SETFA), Echinochloa crus-galli (ECHCG)). After 1 day of cultivation under controlled conditions in a greenhouse (24 / 19°C, day / night; 16 hours of light), the seeds were sowed in a pot in standard soil ...)), The plants were sprayed with an aqueous spray solution derived from a formulation of the technical active ingredient in 0.2% N-methylpyrrolidone + 44.44% Dowanol DPM glycol ether (which was then diluted using 0.2% Genapol XO80 as a diluent) to give the desired final dose of the test compound.

[0181] The test plants were then grown under controlled conditions in a greenhouse (24 / 18°C, day / night; 15 hours of light; 50% humidity) and watered twice a day. After 13 days, the tests were evaluated (100 = total damage to the plants; 0 = no damage to the plants). The results are shown in Table 2 below.

[0182] [Table 4]

[0183] Post-germination biological efficacy Weed and / or crop seeds were sown in standard soil in pots (Amaranthus palmeri (AMAPA), Chenopodium album (CHEAL), Euphorbia heterophylla (EPHHL), Ipomoea hederacea (IPOHE), Eleusine indica (ELEIN), Lolium perenne (LOLPE), Digitaria sanguinalis (DIGSA), Setaria faberi (SETFA), Echinochloa crus-galli (ECHCG)). After 14 days of cultivation under controlled conditions in a greenhouse (24 / 19°C, day / night; 16 hours of light), the plants were sprayed with an aqueous spray solution derived from a formulation of the technical active ingredient 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 yield a 50 g / l solution, which was then diluted using 0.2% Genapol XO80 as a diluent.

[0184] The test plants were then grown under controlled conditions in a greenhouse (24 / 18°C, day / night; 15 hours of light; 50% humidity) and watered twice a day. After 13 days, the tests were evaluated (100 = total damage to the plants; 0 = no damage to the plants). The results are shown in Table 3 below.

[0185] [Table 5]

Claims

1. Formula (I): 【Chemistry 1】 (In the formula, Each X 1 , X 2 and X 3 is independently selected from oxygen and sulfur; Y is C—H or nitrogen; B is O, S, or NR 5 and D is (CR 6 R 7 ) n and m is an integer from 0 to 2; n is an integer from 1 to 4; R 1 is hydrogen or C 1 ~C 6 is alkyl; R 2 is hydrogen, amino, C 1 ~C 6 Alkyl, C 3 ~C 6 Alkenyl, or C 3 ~C 6 alkynyl; R 3 is hydrogen, halogen, C 1 ~C 4 Alkyl, C 1 ~C 4 Haloalkyl, C 1 ~C 4 Alkoxy, C 1 ~C 4 Haloalkoxy, C 1 ~C 4 Alkylthio or C 1 ~C 4 alkylsulfonyl; R 4 is hydrogen, halogen, cyano, nitro, aminocarbonyl, aminothiocarbonyl, C 1 ~C 4 Alkyl, C 1 ~C 4 Haloalkyl, C 1 ~C 4 Alkoxy, C 1 ~C 4 Haloalkoxy, or C 1 ~C 4 alkylsulfonyl; R 5 is hydrogen, hydroxy, C 1 ~C 6 Alkyl, or C 1 ~C 4 is alkoxy; Each R 6 and R 7 is hydrogen, halogen, C 1 ~C 6 Alkyl, C 1 ~C 6 Haloalkyl, Hydroxy, C 1 ~C 4 Alkoxy, C 1 ~C 4 Alkoxycarbonyl, or CH 2 OR 12 where R 6 and R 7 with the proviso that they cannot both be hydroxy on the same carbon atom; or two groups R 6 and R 7 may together represent 1 to 3 groups R 15 C containing 0, 1 or 2 oxygen atoms substituted by 1 ~C 5 Forming an alkylene chain; or two groups R 6 and R 7 on the same carbon atom along with the carbon to which they are attached 2 forming an alkene; R 8 is OR 9 , S.R. 9 , or NR 10 R 11 and R 9 is hydrogen, C 1 ~C 10 Alkyl, C 1 ~C 10 Haloalkyl, C 3 ~C 6 Alkenyl, C 3 ~C 6 Haloalkenyl, C 3 ~C 6 Alkynyl, C 1 ~C 4 Alkoxy C 1 ~C 6 Alkyl, C 1 ~C 4 Haloalkoxy C 1 ~C 6 Alkyl, C 6 ~C 10 Aryl C 1 ~C 3 alkyl, 1 to 4 radicals R 13 C substituted by 6 ~C 10 Aryl C 1 ~C 3 Alkyl, Heteroaryl C 1 ~C 3 alkyl or 1 to 3 groups R 13 Heteroaryl C substituted by 1 ~C 3 is alkyl; R 10 is hydrogen, C 1 ~C 6 Alkyl or SO 2 R 14 and R 11 is hydrogen or C 1 ~C 6 is alkyl; or R 10 and R 11 together with the nitrogen to which they are attached form a 3- to 6-membered heterocyclyl ring, optionally containing an oxygen atom; R 12 is hydrogen, C 1 ~C 4 Alkyl, or C 1 ~C 4 is alkylcarbonyl; Each R 13 is halogen, C 1 ~C 4 Alkyl, C 1 ~C 4 Haloalkyl, C 1 ~C 4 Alkoxy, C 1 ~C 4 Haloalkoxy, cyano, and C 1 ~C 4 independently selected from alkylsulfonyl; R 14 is C 1 ~C 4 Alkyl, C 1 ~C 4 Haloalkyl, or C 1 ~C 4 Alkyl (C 1 ~C 4 alkyl)amino; Each R 15 is hydrogen, halogen, C 1 ~C 4 Alkyl, and C 1 ~C 4 haloalkyl; R 16 and R 17 is hydrogen, halogen, C 1 ~C 6 Alkyl, C 1 ~C 6 Haloalkyl, C 1 ~C 4 Alkoxy, and CH 2 OR 12 are independently selected from; or two groups R 16 and R 17 together represent 1 to 3 groups R 15 C containing 0, 1 or 2 oxygen atoms substituted by 2 ~C 5 Forming an alkylene chain; or two groups R 16 and R 17 C together with the carbon to which they are attached 2 forming an alkene) or an agriculturally acceptable salt thereof, or a salt or N-oxide thereof.

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

3. X 2 The compound according to claim 1 or claim 2, wherein is oxygen.

4. X 3 The compound according to any one of claims 1 to 3, wherein is oxygen.

5. The compound according to any one of claims 1 to 4, wherein Y is C-H.

6. The compound according to any one of claims 1 to 5, wherein B is O, NH, or NMe.

7. The compound according to any one of claims 1 to 6, wherein n is an integer from 1 to 2.

8. The compound of claim 7, wherein n is 2.

9. R 1 is hydrogen or C 1 ~C 4 The compound according to any one of claims 1 to 8, which is alkyl.

10. R 2 is hydrogen, C 1 ~C 4 Alkyl, or C 3 ~C 4 The compound of any one of claims 1 to 9, which is alkynyl.

11. R 3 The compound according to any one of claims 1 to 10, wherein is hydrogen, chloro, or fluoro.

12. R 4 The compound according to any one of claims 1 to 11, wherein is hydrogen, chloro, bromo, cyano, or aminothiocarbonyl.

13. Each R 6 and R 7 is hydrogen, halogen, C 1 ~C 4 Alkyl, and C 1 ~C 4 The compound of any one of claims 1 to 12, independently selected from alkoxycarbonyl.

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

15. 16. A method for controlling or preventing the growth of undesired plants, wherein a herbicidally effective amount of a compound of formula (I) as defined in any one of claims 1 to 13 or a composition as defined in claim 14 is applied to the plant, its part or its habitat.

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