CN120752221A - Herbicidal triazine derivatives - Google Patents

Abstract

Disclosed are compounds of formula (I) wherein the substituents are as defined in claim 1. The invention further relates to herbicidal compositions comprising compounds of formula (I) and to the use of compounds of formula (I) for controlling weeds, in particular in crops of useful plants.

Description

Herbicidal triazine derivatives

The present invention relates to triazine derivatives having herbicidal activity, and to processes and intermediates for preparing such derivatives. The invention further extends to herbicidal compositions comprising such derivatives, and to the use of such compounds and compositions in crops of useful plants for controlling unwanted plant growth, in particular for controlling weeds.

US 6,403,534, WO 2019/121543, WO 2021/018664 and WO 2021/259224 all disclose herbicidal compounds structurally similar to those of the present invention.

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 there is provided a compound having the formula (I):

Wherein the method comprises the steps of

Each X ¹、X² and X ³ is independently selected from oxygen and sulfur;

Y is C-H or nitrogen;

B is O, S or NR ⁵;

D is (CR ⁶R⁷)_n;

n is an integer from 1 to 4;

R ¹ is hydrogen or C ₁-C₆ alkyl;

R ² is hydrogen, amino, C ₁-C₆ alkyl, C ₃-C₆ alkenyl or C ₃-C₆ alkynyl;

R ³ is hydrogen, halogen, C ₁-C₄ alkyl, C ₁-C₄ haloalkyl, C ₁-C₄ alkoxy, C ₁-C₄ haloalkoxy, C ₁-C₄ alkylthio or C ₁-C₄ alkylsulfonyl;

R ⁴ is hydrogen, halogen, cyano, nitro, aminocarbonyl, aminothiocarbonyl, C ₁-C₄ alkyl, C ₁-C₄ haloalkyl, C ₁-C₄ alkoxy, C ₁-C₄ haloalkoxy or C ₁-C₄ alkylsulfonyl;

R ⁵ is hydrogen, hydroxy, C ₁-C₆ alkyl or C ₁-C₄ alkoxy;

Each R ⁶ and R ⁷ is independently selected from hydrogen, halogen, C ₁-C₆ alkyl, C ₁-C₆ haloalkyl, hydroxy, C ₁-C₄ alkoxy, C ₁-C₄ alkoxycarbonyl, or CH ₂OR¹², provided that R ⁶ and R ⁷ are not both hydroxy on the same carbon atom, or

Two R ⁶ and R ⁷ groups on the same or different carbon atoms together with the carbon atom or atoms to which they are attached form a 3-to 6-membered cycloalkyl group containing 0, 1 or 2 oxygen atoms, or

Two R ⁶ and R ⁷ groups on the same or different carbon atoms together with the carbon atom or atoms to which they are attached form a 3-to 6-membered cycloalkyl group containing 0, 1 or 2 oxygen atoms and wherein the resulting 3-to 6-membered cycloalkyl group is substituted by 1 to 3 groups represented by R ¹⁵, or

The two R ⁶ and R ⁷ groups on the same carbon atom together with the carbon atom to which they are attached form a C ₂ alkene group;

R ⁸ is OR ⁹、SR⁹ OR NR ¹⁰R¹¹;

R ⁹ is hydrogen, C ₁-C₁₀ alkyl, C ₁-C₁₀ haloalkyl, C ₃-C₆ alkenyl, C ₃-C₆ haloalkenyl, C ₃-C₆ alkynyl, C ₁-C₄ alkoxyc ₁-C₆ alkyl, C ₁-C₄ haloalkoxy C ₁-C₆ alkyl, C ₆-C₁₀ arylc ₁-C₃ alkyl, C ₆-C₁₀ arylc ₁-C₃ alkyl substituted with 1 to 4 groups represented by R ¹³, heteroaryl C ₁-C₃ alkyl, or heteroaryl C ₁-C₃ alkyl substituted with 1 to 3 groups represented by R ¹³;

R ¹⁰ is hydrogen, C ₁-C₆ alkyl or SO ₂R¹⁴;

r ¹¹ is hydrogen or C ₁-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, C ₁-C₄ alkyl or C ₁-C₄ alkylcarbonyl;

each R ¹³ is independently selected from halogen, C ₁-C₄ alkyl, C ₁-C₄ haloalkyl, C ₁-C₄ alkoxy, C ₁-C₄ haloalkoxy, cyano, and C ₁-C₄ alkylsulfonyl;

R ¹⁴ is C ₁-C₄ alkyl, C ₁-C₄ haloalkyl or C ₁-C₄ alkyl (C ₁-C₄ alkyl) amino;

each R ¹⁵ is independently selected from hydrogen, halogen, C ₁-C₄ alkyl, or C ₁-C₄ haloalkyl;

R ¹⁶ and R ¹⁷ are each independently selected from hydrogen, halogen, C ₁-C₆ alkyl, C ₁-C₆ haloalkyl, C ₁-C₄ alkoxy and CH ₂OR¹², or

The two R ¹⁶ and R ¹⁷ groups together with the carbon to which they are attached form a 3-to 6-membered cycloalkyl group containing 0, 1 or 2 oxygen atoms, or

The two R ¹⁶ and R ¹⁷ groups together with the carbon to which they are attached form a 3-to 6-membered cycloalkyl group containing 0,1 or2 oxygen atoms, wherein the resulting 3-to 6-membered cycloalkyl group is substituted with 1 to 3 groups represented by R ¹⁵, or

The two R ¹⁶ and R ¹⁷ groups together with the carbon atom to which they are attached form a C ₂ alkene group.

A problem with many current herbicides used to control unwanted vegetation before crop planting is that if a subsequent crop is planted shortly after the herbicide is used, damage to the crop may occur. Thus, herbicides that are safe to the crop while providing good control of the weeds that have emerged when applied prior to emergence of the crop are a significant advantage over existing herbicides.

Surprisingly, it has been found that the novel compounds of formula (I) not only have a very advantageous level of herbicidal activity for practical purposes, but they also show no or low levels of damage to several major crops when applied pre-emergence, while providing excellent control of unwanted vegetation (weeds and volunteers) when applied post-emergence, enabling them to be used successfully in a short period of time before planting new crops. In contrast, related compounds reported in the prior art, while exhibiting similar control over unwanted vegetation, can cause unacceptable damage to many crops, thereby impeding their use.

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) according to the present invention. Such agricultural compositions may further comprise at least one additional active ingredient and/or an agrochemically acceptable diluent or carrier.

According to a third aspect of the present invention there is provided a method of controlling weeds at a locus, the method comprising applying to the locus a weed controlling amount of a composition comprising a compound of formula (I).

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

According to a fifth aspect of the present invention there is provided a process for the preparation of a compound having formula (I).

When substituents are denoted as "optionally substituted", this means that they may or may not bear one or more identical or different substituents, for example one, two or three R ¹⁵ substituents. For example, a C ₁-C₆ alkyl substituted with 1,2, or 3 halogens may include, but is not limited to, -CH₂Cl、-CHCl₂、-CCl₃、-CH₂F、-CHF₂、-CF₃、-CH₂CF₃ or-CF ₂CH₃ groups. As another example, C ₁-C₆ alkoxy substituted with 1,2, or 3 halogens may include, but is not limited to, CH₂ClO-、CHCl₂O-、CCl₃O-、CH₂FO-、CHF₂O-、CF₃O-、CF₃CH₂O- or CH ₃CF₂ O-groups.

As used herein, the term "cyano" means a —cn group.

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

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

As used herein, the term "hydroxyl" refers to an-OH group.

As used herein, the term "amino" refers to the-NH ₂ group.

As used herein, the term "acetyl" means a-C (O) CH ₃ group.

As used herein, the term "C ₁-C₁₀ alkyl" refers to a straight or branched hydrocarbon chain group consisting of only carbon and hydrogen atoms, which is free of unsaturation, has from one to ten carbon atoms, and is attached to the remainder of the molecule by a single bond. The terms "C ₁-C₆ alkyl", "C ₁-C₄ alkyl" and "C ₁-C₃ alkyl" are to be construed accordingly. Examples of C ₁-C₁₀ alkyl groups include, but are not limited to, methyl, ethyl, n-propyl, and isomers thereof, e.g., isopropyl. "C ₁-C₆ alkylene" refers to the corresponding definition of C ₁-C₆ alkyl, except that such a group is attached to the rest of the molecule by two single bonds. The terms "C ₁-C₅ alkylene" and "C ₁-C₂ alkylene" should be construed accordingly. Examples of C ₁-C₆ alkylene groups include, but are not limited to, -CH ₂-、-CH₂CH₂ -, and- (CH ₂)₃ -.

As used herein, the term "C ₁-C₁₀ haloalkyl" refers to a C ₁-C₁₀ alkyl group as generally defined above, which is substituted with one or more of the same or different halogen atoms. The terms "C ₁-C₆ haloalkyl", "C ₁-C₄ haloalkyl" and "C ₁-C₃ haloalkyl" are to be construed accordingly. Examples of C ₁-C₁₀ haloalkyl include, but are not limited to, trifluoromethyl.

As used herein, the term "C ₁-C₆ alkoxy" refers to a group having the formula-OR _a, wherein R _a is C ₁-C₆ alkyl as generally defined above. The terms "C ₁-C₄ alkoxy" and "C ₁-C₃ alkoxy" should be construed accordingly. Examples of C ₁-C₆ alkoxy groups include, but are not limited to, methoxy, ethoxy, 1-methylethoxy (isopropoxy), and propoxy.

As used herein, the term "C ₁-C₆ haloalkoxy" refers to a C ₁-C₆ alkoxy group as generally defined above substituted with one or more identical or different halogen atoms. The terms "C ₁-C₄ haloalkoxy" and "C ₁-C₃ haloalkoxy" are to be construed accordingly. Examples of C ₁-C₆ haloalkoxy groups include, but are not limited to, trifluoromethoxy.

As used herein, the term "C ₁-C₄ haloalkoxy C ₁-C₆ alkyl" refers to a group having the formula R _b-O-R_a -wherein R _b is a C ₁-C₄ haloalkyl group as generally defined above and R _a is a C ₁-C₆ alkylene group as generally defined above.

As used herein, the term "C ₂-C₆ alkenyl" refers to a straight or branched hydrocarbon chain group consisting of only carbon and hydrogen atoms, containing at least one double bond that may have the (E) -or (Z) -configuration, having two to six carbon atoms, attached to the remainder of the molecule by single bonds. The terms "C ₃-C₆ alkenyl", "C ₂-C₃ alkenyl" and "C ₂ alkenyl" should be construed accordingly. Examples of C ₂-C₆ alkenyl include, but are not limited to, vinyl (ethyl/vinyl), prop-1-enyl, prop-2-enyl (allyl), but-1-enyl.

As used herein, the term "C ₂-C₆ alkynyl" refers to a straight or branched hydrocarbon chain group consisting of only carbon and hydrogen atoms, containing at least one triple bond, having two to six carbon atoms, and attached to the remainder of the molecule by single bonds. The terms "C ₃-C₆ alkynyl" and "C ₂-C₃ alkynyl" should be construed accordingly. Examples of C ₂-C₆ alkynyl include, but are not limited to, ethynyl, prop-1-ynyl, but-1-ynyl.

As used herein, the term "C ₂-C₆ haloalkenyl" refers to a "C ₂-C₆ alkenyl" as generally defined above substituted with one or more identical or different halogen atoms.

As used herein, the term "C ₁-C₆ alkoxy C ₁-C₆ alkyl" refers to a group having the formula R _bOR_a ", wherein R _b is C ₁-C₆ alkyl as generally defined above and R _a is C ₁-C₆ alkylene as generally defined above. The terms "C ₁-C₄ alkoxy C ₁-C₆ alkyl" and "C ₁-C₄ alkoxy C ₁-C₄ alkyl" should be construed accordingly. Examples of C ₁-C₆ alkoxy C ₁-C₆ alkyl groups include, but are not limited to, ethoxyethyl and methoxymethyl.

As used herein, the term "C ₁-C₄ alkyl (C ₁-C₄ alkyl) amino" refers to a group having the formula R _a(R_b) NH-, wherein R _a and R _b are both C ₁-C₄ alkyl groups as generally defined above.

As used herein, the term "C ₃-C₆ cycloalkyl" refers to a group containing 3 to 6 carbon atoms that is a monocyclic saturated ring system. The terms "C ₃-C₅ cycloalkyl" and "C ₃-C₄ cycloalkyl" should be construed accordingly. Examples of C ₃-C₆ cycloalkyl groups include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl.

As used herein, the term "C ₆-C₁₀ aryl" refers to a 6-to 10-membered aromatic ring system consisting of only carbon and hydrogen atoms, which may be monocyclic, bicyclic or tricyclic. Examples of such ring systems include phenyl, naphthyl, or indenyl.

As used herein, the term "C ₆-C₁₀ aryl C ₁-C₃ alkyl" refers to an aryl moiety as generally defined above attached to the remainder of the molecule through a C ₁-C₃ alkylene linker as defined above.

As used herein, unless otherwise indicated, the term "heterocyclyl" refers to a stable 4-, 5-, or 6-membered non-aromatic monocyclic ring containing 1,2, or 3 heteroatoms selected independently from nitrogen, oxygen, and sulfur. The heterocyclyl group may be bonded to the remainder of the molecule via a carbon atom or heteroatom. Examples of heterocyclyl groups include, but are not limited to, aziridinyl, azetidinyl, oxetanyl, thietanyl, tetrahydrofuranyl, pyrrolidinyl, pyrazolidinyl, imidazolidinyl, piperidinyl, piperazinyl, morpholinyl, dioxolanyl, dithiolanyl, and thiazolidinyl.

As used herein, unless otherwise indicated, the term "heteroaryl" refers to a 5-or 6-membered aromatic monocyclic group containing 1,2, 3, or 4 heteroatoms independently selected from nitrogen, oxygen, and sulfur. Examples of heteroaryl groups include, but are not limited to, furyl, pyrrolyl, thienyl, pyrazolyl, imidazolyl, thiazolyl, isothiazolyl, oxazolyl, isoxazolyl, triazolyl, tetrazolyl, pyrazinyl, pyridazinyl, pyrimidinyl, or pyridyl.

As used herein, unless otherwise indicated, the term "heteroaryl C ₁-C₃ alkyl" refers to a heteroaryl moiety as generally defined above attached to the remainder of the molecule through a C ₁-C₃ alkylene linker as defined above.

As used herein, the term "C ₁-C₆ alkylcarbonyl" refers to a group having the formula-C (O) R _a, wherein R _a is a C ₁-C₆ alkyl group as generally defined above. The terms "C ₁-C₄ alkylcarbonyl" and "C ₁-C₃ alkylcarbonyl" are to be construed accordingly. Examples of C ₁-C₆ alkylcarbonyl include, but are not limited to, acetyl.

As used herein, the term "C ₁-C₆ alkoxycarbonyl" refers to a group having the formula-C (O) OR _a, wherein R _a is a C ₁-C₆ alkyl group as generally defined above. The terms "C ₁-C₄ alkoxycarbonyl" and "C ₁-C₃ alkoxycarbonyl" are to be construed accordingly. Examples of C ₁-C₆ alkoxycarbonyl groups include, but are not limited to, acetyl.

As used herein, the term "C ₁-C₆ alkylthio" refers to a group having the formula-SR _a, wherein R _a is a C ₁-C₆ alkyl group as generally defined above. The terms "C ₁-C₄ alkylthio" and "C ₁-C₃ alkylthio" are to be construed accordingly. Examples of C ₁-C₆ alkylthio include, but are not limited to, methylsulfanyl.

As used herein, the term "C ₁-C₆ alkylsulfonyl" refers to a group having the formula-S (O) ₂R_a, wherein R _a is a C ₁-C₆ alkyl group as generally defined above. The terms "C ₁-C₄ alkylsulfonyl" and "C ₁-C₃ alkylsulfonyl" should be construed accordingly. Examples of C ₁-C₆ alkylsulfonyl include, but are not limited to methylsulfonyl.

As used herein, the term "aminocarbonyl" refers to a group having the formula-C (O) NH ₂.

As used herein, the term "aminothiocarbonyl" refers to a group having the formula-C (S) NH ₂.

The presence of one or more possible asymmetric carbon atoms in the compounds of formula (I) means that these compounds may exist in chiral isomeric forms, i.e. in enantiomeric or diastereoisomeric forms. Atropisomers may also be present as a result of limited rotation about a single bond. Formula (I) is intended to include all those possible isomeric forms and mixtures thereof. The present invention includes all those possible isomeric forms of the compounds having formula (I) and mixtures thereof. Likewise, formula (I) is intended to include all possible tautomers (including lactam-lactam tautomers and keto-enol tautomers), when present. The present invention includes all possible tautomeric forms of the compounds having formula (I). Similarly, where disubstituted olefins are present, these may be present in the E or Z form or as a mixture of both in any ratio. The present invention includes all such possible isomeric forms of the compounds having formula (I) and mixtures thereof.

The compounds having formula (I) will typically be provided in the form of an agronomically acceptable salt, a zwitterionic or an agronomically acceptable salt of a zwitterionic. The present invention encompasses all such agronomically acceptable salts, zwitterions and mixtures thereof in all proportions.

Suitable agronomically acceptable salts of the present invention may have cations including, but not limited to, metal, amine conjugate acid 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 allyl amine, ammonia, pentylamine, arginine, phenethyl-benzylamine, benzathine, butenyl-2-amine, butylamine, butylethanolamine, cyclohexylamine, decylamine, dipentylamine, dibutylamine, diethanolamine, diethylamine, diethylenetriamine, diheptylamine, dihexylamine, diisopentylamine, diisopropylamine, dimethylamine, dioctylamine, dipropylamine, dodecylamine, ethanolamine, ethylamine, ethylbutylamine, ethylenediamine, ethylheptylamine, ethyloctylamine, ethylpropanolamine, seventeen, heptylamine, hexadecylamine, hexenyl-2-amine, hexylamine, hexylheptylamine, hexyloctylamine, histidine, indoline, isopentylamine, isobutylamine, isopropanolamine, isopropylamine, lysine, meglumine, methoxyethylamine, methylamine, methylbutylamine, methylethylamine, 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, tallow amine, dodecylamine, tributylamine, tridecylamine, trimethylamine, triheptylamine, trihexylamine, triisobutylamine, triisodecylamine, triisopropylamine, trimethylamine, tripentylamine, tripropylamine, tris (hydroxymethyl) aminomethane and undecylamine. Examples of suitable organic cations include benzyl tributylammonium, benzyl trimethylammonium, benzyl triphenylphosphonium, choline, tetrabutylammonium, tetrabutylphosphonium, tetraethylammonium, tetraethylphosphonium, tetramethylammonium tetramethyl phosphonium, tetrapropyl ammonium, tetrapropyl phosphonium, tributyl sulfonium, tributyl sulfoxonium, triethyl sulfonium, triethyl sulfoxonium, trimethyl sulfonium, trimethyl sulfoxonium, tripropyl sulfonium, and tripropyl sulfoxonium.

The following list provides definitions, including preferred definitions, for substituents X¹、X²、X³、Y、B、D、R¹、R²、R³、R⁴、R⁵、R⁶、R⁷、R⁸、R⁹、R¹⁰、R¹¹、R¹²、R¹³、R¹⁴、R¹⁵、R¹⁶ and R ¹⁷ of compounds having formula (I). For any of these substituents, any of the definitions set forth below may be combined with any of the definitions of any other substituents set forth below or elsewhere in this document.

X ¹ is oxygen or sulfur. Preferably, X ¹ is sulfur.

X ² is oxygen or sulfur. Preferably, X ² is oxygen.

X ³ is oxygen or sulfur. Preferably, X ³ is oxygen.

Y is C-H or nitrogen. Preferably, Y is C-H.

B is O, S or NR ⁵. Preferably, B is O, NH or NCH ₃. More preferably, B is O or NH. Still more preferably, B is O.

N is an integer from 1 to 4. Preferably, n is an integer from 1 to 2, more preferably n is 1.

R ¹ is hydrogen or C ₁-C₆ alkyl. Preferably, R ¹ is hydrogen or C ₁-C₄ alkyl. More preferably, R ¹ is C ₁-C₂ alkyl, and still more preferably, R ¹ is methyl.

R ² is hydrogen, amino, C ₁-C₆ alkyl, C ₃-C₆ alkenyl or C ₃-C₆ alkynyl. Preferably, R ² is hydrogen, C ₁-C₄ alkyl or C ₃-C₄ alkynyl. More preferably, R ² is C ₁-C₂ alkyl, and still more preferably, R ² is methyl.

In one set of embodiments, R ¹ and R ² are each independently C ₁-C₂ alkyl. Preferably, R ¹ and R ² are both methyl.

R ³ is hydrogen, halogen, C ₁-C₄ alkyl, C ₁-C₄ haloalkyl, C ₁-C₄ alkoxy, C ₁-C₄ haloalkoxy, C ₁-C₄ alkylthio or C ₁-C₄ alkylsulfonyl. Preferably, R ³ is hydrogen, chlorine, or fluorine. More preferably, R ³ is hydrogen or fluorine. Still more preferably, R ³ is fluoro.

R ⁴ is hydrogen, halogen, cyano, nitro, aminocarbonyl, aminothiocarbonyl, C ₁-C₄ alkyl, C ₁-C₄ haloalkyl, C ₁-C₄ alkoxy, C ₁-C₄ haloalkoxy or C ₁-C₄ alkylsulfonyl. Preferably, R ⁴ is chloro, bromo, cyano, or aminothiocarbonyl. More preferably, R ⁴ is chloro, bromo or cyano, and most preferably, R ⁴ is chloro.

In one embodiment, R ³ and R ⁴ are selected from hydrogen, chlorine and fluorine.

R ⁵ is hydrogen, hydroxy, C ₁-C₆ alkyl or C ₁-C₄ alkoxy. Preferably, R ⁵ is hydrogen or C ₁-C₄ alkyl. More preferably, R ⁵ is hydrogen or C ₁-C₂ alkyl. Even more preferably, R ⁵ is hydrogen or methyl. In one set of embodiments, R ⁵ is hydrogen.

Each R ⁶ and R ⁷ is independently selected from hydrogen, halogen, C ₁-C₆ alkyl, C ₁-C₆ haloalkyl, hydroxy, C ₁-C₄ alkoxy, C ₁-C₄ alkoxycarbonyl, or CH ₂OR¹², provided that R ⁶ and R ⁷ are not both hydroxy on the same carbon atom, or

Two R ⁶ and R ⁷ groups on the same or different carbon atoms together with the carbon atom or atoms to which they are attached form a 3-to 6-membered cycloalkyl group containing 0, 1 or 2 oxygen atoms, or

Two R ⁶ and R ⁷ groups on the same or different carbon atoms together with the carbon atom or atoms to which they are attached form a 3-to 6-membered cycloalkyl group containing 0, 1 or 2 oxygen atoms and wherein the resulting 3-to 6-membered cycloalkyl group is substituted by 1 to 3 groups represented by R ¹⁵, or

The two R ⁶ and R ⁷ groups on the same carbon atom together with the carbon atom to which they are attached form a C ₂ alkene group.

Preferably, each R ⁶ and R ⁷ is independently selected from hydrogen, halogen, C ₁-C₄ alkyl, and C ₁-C₄ alkoxycarbonyl. More preferably, each R ⁶ and R ⁷ is independently selected from hydrogen and C ₁-C₂ alkyl. Still more preferably, each R ⁶ and R ⁷ is independently selected from hydrogen and methyl. Even more preferably, R ⁶ and R ⁷ are both hydrogen.

R ⁸ is OR ⁹、SR⁹ OR NR ¹⁰R¹¹. Preferably, R ⁸ is OR ⁹. In one embodiment, R ⁸ is ethoxy.

R ⁹ is hydrogen, C ₁-C₁₀ alkyl, C ₁-C₁₀ haloalkyl, C ₃-C₆ alkenyl, C ₃-C₆ haloalkenyl, C ₃-C₆ alkynyl, C ₁-C₄ alkoxyC ₁-C₆ alkyl, C ₁-C₄ haloalkoxy C ₁-C₆ alkyl, C ₆-C₁₀ ArC ₁-C₃ alkyl, C ₆-C₁₀ ArC ₁-C₃ alkyl substituted with 1 to 4 groups represented by R ¹³, Heteroaryl C ₁-C₃ alkyl, or heteroaryl C ₁-C₃ alkyl substituted with 1 to 3 groups represented by R ¹³. Preferably, R ⁹ is selected from the group consisting of hydrogen, C ₁-C₄ alkyl, C ₁-C₄ haloalkyl, C ₁-C₂ alkoxyC ₁-C₂ alkyl, Phenyl C ₁-C₂ alkyl and phenyl C ₁-C₂ alkyl substituted with 1 to 2 groups represented by R ¹³. More preferably, R ⁹ is hydrogen, C ₁-C₄ alkyl, C ₁-C₂ alkoxyc ₁-C₂ alkyl or phenylc ₁-C₂ alkyl. Still more preferably, R ⁹ is hydrogen, C ₁-C₄ alkyl or phenylc ₁-C₂ alkyl. Even more preferably, R ⁹ is C ₁-C₃ alkyl. in a particularly preferred embodiment, R ⁹ is ethyl.

R ¹⁰ is hydrogen, C ₁-C₆ alkyl or SO ₂R¹⁴. Preferably, R ¹⁰ is hydrogen or SO ₂R¹⁴. More preferably, R ¹⁰ is SO ₂R¹⁴.

R ¹¹ is hydrogen or C ₁-C₆ alkyl. Preferably, R ¹¹ is hydrogen.

R ¹² is hydrogen, C ₁-C₄ alkyl or C ₁-C₄ alkylcarbonyl. Preferably, R ¹² is hydrogen, C ₁-C₂ alkyl or C ₁-C₂ alkylcarbonyl. More preferably, R ¹² is hydrogen or methyl.

Each R ¹³ is independently selected from halogen, C ₁-C₄ alkyl, C ₁-C₄ haloalkyl, C ₁-C₄ alkoxy, C ₁-C₄ haloalkoxy, cyano, and C ₁-C₄ alkylsulfonyl. Preferably, R ¹³ is selected from halogen, C ₁-C₄ alkyl, C ₁-C₄ haloalkyl, C ₁-C₄ alkoxy, C ₁-C₄ haloalkoxy, cyano and C ₁-C₄ alkylsulfonyl.

R ¹⁴ is C ₁-C₄ alkyl, C ₁-C₄ haloalkyl or C ₁-C₄ alkyl (C ₁-C₄ alkyl) amino. Preferably, R ¹⁴ is C ₁-C₄ alkyl or C ₁-C₄ alkyl (C ₁-C₄ alkyl) amino. More preferably, R ¹⁴ is methyl or isopropyl (methyl) amino.

Each R ¹⁵ is independently selected from hydrogen, halogen, C ₁-C₄ alkyl, or C ₁-C₄ haloalkyl. Preferably, each R ¹⁵ is independently selected from hydrogen, halogen, and C ₁-C₂ alkyl. More preferably, each R ¹⁵ is independently selected from hydrogen and methyl. Still more preferably, R ¹⁵ is hydrogen.

R ¹⁶ and R ¹⁷ are each independently selected from hydrogen, halogen, C ₁-C₆ alkyl, C ₁-C₆ haloalkyl, C ₁-C₄ alkoxy and CH ₂OR¹², or

The two R ¹⁶ and R ¹⁷ groups together with the carbon to which they are attached form a 3-to 6-membered cycloalkyl group containing 0, 1 or 2 oxygen atoms, or

The two R ¹⁶ and R ¹⁷ groups together with the carbon to which they are attached form a 3-to 6-membered cycloalkyl group containing 0,1 or2 oxygen atoms, wherein the resulting 3-to 6-membered cycloalkyl group is substituted with 1 to 3 groups represented by R ¹⁵, or

The two R ¹⁶ and R ¹⁷ groups together with the carbon atom to which they are attached form a C ₂ alkene group.

Preferably, R ¹⁶ and R ¹⁷ are independently selected from hydrogen, C ₁-C₄ alkyl and C ₁-C₂ alkoxy, or

The two R ¹⁶ and R ¹⁷ groups together with the carbon to which they are attached form a 3-to 6-membered cycloalkyl.

Still more preferably, the two R ¹⁶ and R ¹⁷ groups together with the carbon to which they are attached form a 3-to 6-membered cycloalkyl. Even more preferably, the two R ¹⁶ and R ¹⁷ groups together with the carbon to which they are attached form a cyclopropyl group.

In one embodiment, in a compound according to the invention having formula (I):

Each X ¹、X² and X ³ is independently selected from oxygen and sulfur;

Y is C-H or nitrogen;

B is O, S or NR ⁵;

D is (CR ⁶R⁷)_n;

n is an integer from 1 to 4;

R ¹ is hydrogen or C ₁-C₆ alkyl;

r ² is amino, C ₃-C₆ alkenyl or C ₃-C₆ alkynyl;

R ³ is C ₁-C₄ alkyl, C ₁-C₄ haloalkyl, C ₁-C₄ alkoxy, C ₁-C₄ haloalkoxy, C ₁-C₄ alkylthio or C ₁-C₄ alkylsulfonyl;

R ⁴ is hydrogen, cyano, nitro, aminocarbonyl, aminothiocarbonyl, C ₁-C₄ alkyl, C ₁-C₄ haloalkyl, C ₁-C₄ alkoxy, C ₁-C₄ haloalkoxy or C ₁-C₄ alkylsulfonyl;

R ⁵ is hydrogen, hydroxy, C ₁-C₆ alkyl or C ₁-C₄ alkoxy;

Each R ⁶ and R ⁷ is independently selected from hydrogen, halogen, C ₁-C₆ alkyl, C ₁-C₆ haloalkyl, hydroxy, C ₁-C₄ alkoxy, C ₁-C₄ alkoxycarbonyl, or CH ₂OR¹², provided that R ⁶ and R ⁷ are not both hydroxy on the same carbon atom, or

Two R ⁶ and R ⁷ groups on the same or different carbon atoms together with the carbon atom or atoms to which they are attached form a 3-to 6-membered cycloalkyl group containing 0, 1 or 2 oxygen atoms, or

Two R ⁶ and R ⁷ groups on the same or different carbon atoms together with the carbon atom or atoms to which they are attached form a 4-to 6-membered cycloalkyl group containing 0, 1 or 2 oxygen atoms and wherein the resulting 4-to 6-membered cycloalkyl group is substituted by 1 to 3 groups represented by R ¹⁵, or

The two R ⁶ and R ⁷ groups on the same carbon atom together with the carbon atom to which they are attached form a C ₂ alkene group;

R ⁸ is OR ⁹、SR⁹ OR NR ¹⁰R¹¹;

R ⁹ is hydrogen, C ₁-C₁₀ alkyl, C ₁-C₁₀ haloalkyl, C ₃-C₆ alkenyl, C ₃-C₆ haloalkenyl, C ₃-C₆ alkynyl, C ₁-C₄ alkoxyc ₁-C₆ alkyl, C ₁-C₄ haloalkoxy C ₁-C₆ alkyl, C ₆-C₁₀ arylc ₁-C₃ alkyl, C ₆-C₁₀ arylc ₁-C₃ alkyl substituted with 1 to 4 groups represented by R ¹³, heteroaryl C ₁-C₃ alkyl, or heteroaryl C ₁-C₃ alkyl substituted with 1 to 3 groups represented by R ¹³;

R ¹⁰ is hydrogen, C ₁-C₆ alkyl or SO ₂R¹⁴;

r ¹¹ is hydrogen or C ₁-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, C ₁-C₄ alkyl or C ₁-C₄ alkylcarbonyl;

each R ¹³ is independently selected from halogen, C ₁-C₄ alkyl, C ₁-C₄ haloalkyl, C ₁-C₄ alkoxy, C ₁-C₄ haloalkoxy, cyano, and C ₁-C₄ alkylsulfonyl;

R ¹⁴ is C ₁-C₄ alkyl, C ₁-C₄ haloalkyl or C ₁-C₄ alkyl (C ₁-C₄ alkyl) amino;

each R ¹⁵ is independently selected from hydrogen, halogen, C ₁-C₄ alkyl, or C ₁-C₄ haloalkyl;

R ¹⁶ and R ¹⁷ are each independently selected from hydrogen, halogen, C ₁-C₆ alkyl, C ₁-C₆ haloalkyl, C ₁-C₄ alkoxy and CH ₂OR¹², or

The two R ¹⁶ and R ¹⁷ groups together with the carbon to which they are attached form a 3-to 6-membered cycloalkyl group containing 0, 1 or 2 oxygen atoms, or

The two R ¹⁶ and R ¹⁷ groups together with the carbon to which they are attached form a 3-to 6-membered cycloalkyl group containing 0,1 or2 oxygen atoms, wherein the resulting 3-to 6-membered cycloalkyl group is substituted with 1 to 3 groups represented by R ¹⁵, or

The two R ¹⁶ and R ¹⁷ groups together with the carbon atom to which they are attached form a C ₂ alkene group.

In a further set of embodiments of the present invention,

X ¹ is sulfur;

X ² is oxygen;

x ³ is oxygen;

y is C-H;

B is O;

n is 1;

r ¹ is C ₁-C₂ alkyl;

R ² is C ₁-C₂ alkyl;

R ³ is hydrogen, chlorine or fluorine;

R ⁴ is chloro, bromo or cyano;

Each R ⁶ and R ⁷ is independently selected from hydrogen, halogen, and C ₁-C₂ alkyl;

R ⁸ is OR ⁹;

R ⁹ is hydrogen, C ₁-C₄ alkyl, C ₁-C₂ alkoxyC ₁-C₂ alkyl or phenylC ₁-C₂ alkyl;

r ¹⁶ and R ¹⁷ are each independently selected from hydrogen, C ₁-C₄ alkyl and C ₁-C₂ alkoxy, or

The two R ¹⁶ and R ¹⁷ groups together with the carbon to which they are attached form a 3-to 6-membered cycloalkyl.

In a further set of embodiments of the present invention,

X ¹ is sulfur;

X ² is oxygen;

x ³ is oxygen;

y is C-H;

B is O;

n is 1;

r ¹ is C ₁-C₂ alkyl;

R ² is C ₁-C₂ alkyl;

R ³ is hydrogen, chlorine or fluorine;

R ⁴ is chloro, bromo or cyano;

R ⁶ and R ⁷ are both hydrogen;

R ⁸ is OR ⁹;

R ⁹ is C ₁-C₄ alkyl;

The two R ¹⁶ and R ¹⁷ groups together with the carbon to which they are attached form a 3-to 6-membered cycloalkyl.

Preferably, the compound of formula (I) is (2-ethoxy-2-oxo-ethyl) 1- [ 2-chloro-5- (3, 5-dimethyl-2, 6-dioxo-4-thioxo-1, 3, 5-triazin-1-yl) -4-fluoro-phenoxy ] -cyclopropanecarboxylic acid ester.

In another aspect, there is provided a herbicidal composition comprising (a) a herbicidally effective amount of a compound of formula (I) and (B) at least one herbicide selected from the group consisting of: glufosinate, L-glufosinate, glyphosate, 2,4-D, clethodim, clodinafop-propargyl, oxazafop-p-ethyl, haloxyfop-butyl, carfentrazone-ethyl, oxazamate, diflufenican, flumetsulam, fluazifop-butyl, propidium, haloxyfop-butyl and other drugs saflufenacil, flumetsulam, carfentrazone-ethyl, flumetsulam, fomesafen, oxyfluorfen, pyriproxyfen-ethyl, sulfentrazone, flumetsulam, trifluoperazone, trifluoperazine 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, ethyl 2- [ [3- [ [ 3-chloro-5-fluoro-6- [ 3-methyl-2, 6-dioxo-4- (trifluoromethyl) pyrimidin-1-yl ] -2-pyridinyl ] oxy ] acetate, topiramate, fluopicolone, prim, mesotrione, metribuzin, clopyralid, dicamba, fluropyridine ester, fluroxypyr, fluropyridine ester-methyl, triclopyr, paraquat, dichlorvos, trichlorfon, quinclorac, dioxopyrithione, fenquidone, isoxazodone, cyclosulfamone, topramezone, 3- (isopropylsulfonylmethyl) -N- (5-methyl-1, 3, 4-oxadiazol-2-yl) -5- (trifluoromethyl) - [1,2,4] triazolo [4,3-a ] pyridine-8-carboxamide and 2-fluoro-N- (5-methyl-1, 3, 4-oxadiazol-2-yl) -3- [ (R) -propylsulfinyl ] -4- (trifluoromethyl) benzamide.

In a further aspect, there is provided a herbicidal composition comprising (A) a herbicidally effective amount of (2-ethoxy-2-oxo-ethyl) 1- [ 2-chloro-5- (3, 5-dimethyl-2, 6-dioxo-4-thioxo-1, 3, 5-triazin-1-yl) -4-fluoro-phenoxy ] -cyclopropanecarboxylate and (B) at least one herbicide selected from the group consisting of glufosinate, L-glufosinate, glyphosate, 2,4-D, clethodim, clodinafop-propargyl, oxazamate, fluazifop-p-butyl, fluazifop-butyl, oxazamate, diflufenican, bensulfuron-methyl, flumetsulam-ethyl, flumetsulam, flufenazamate, fomesafen, oxyfluorfen, pyrifos-ethyl, sulfenazamate, triflumuron-ethyl, trifluoperazone-methyl, trifluoperazone-3-2, 4-dimethyl-3- (2, 5-dimethyl-4-2-fluoro-2-ethyl) -triflumuron 2- [ [3- [ [ 3-chloro-5-fluoro-6- [ 3-methyl-2, 6-dioxo-4- (trifluoromethyl) pyrimidin-1-yl ] -2-pyridinyl ] oxy ] ethyl acetate, fenpyr-diethyl, flupirflux, prim-iprovalicarb, mesotrione, zinone, clopyralid, dicamba, chlorofluoropyridine ester, fluroxypyr-meptyl, triclopyr, paraquat, diquat, quinocetone, dioxopyrithione, fenquidone, isoxazolone, cyclosulfamone, topramen, 3- (isopropyl-sulfonylmethyl) -N- (5-methyl-1, 3, 4-oxadiazol-2-yl) -5- (trifluoromethyl) - [1,2,4] triazolo [4,3-a ] pyridine-8-carboxamide and 2-fluoro-N- (5-methyl-1, 3, 4-oxadiazol-2-yl) -3- [ (R ] -methylsulfonylmethyl) -benzamide.

In still a further aspect, there is provided a herbicidal composition comprising (a) a herbicidally effective amount of (2-ethoxy-2-oxo-ethyl) 1- [ 2-chloro-5- (3, 5-dimethyl-2, 6-dioxo-4-thioxo-1, 3, 5-triazin-1-yl) -4-fluoro-phenoxy ] -cyclopropanecarboxylate and (B) at least one herbicide selected from the group consisting of: glufosinate, L-glufosinate, glyphosate, 2,4-D, clethodim, clodinafop-propargyl, haloxyfop-butyl, pinoxaden, diflufenican, flumetsulam, fomesafen, sulfenamide, flumetsulam, trifluralin, 3- (2-chloro-4-fluoro-5- (3-methyl-2, 6-dioxo-4-trifluoromethyl-3, 6-dihydropyrimidin-1 (2H) -yl) phenyl) -5-methyl-4, 5-dihydro-isoxazole-5-carboxylic acid ethyl ester, 2- [ [ 3-chloro-5-fluoro-6- [ 3-methyl-2, 6-dioxo-4- (trifluoromethyl) pyrimidin-1-yl ] -2-pyridinyl ] oxy ] ethyl acetate, pyrifos-ethyl, fluazifom, fluazifop-butyl, mesotrione, oxaziclomefone, mesotrione dicamba (dicamba) wheat straw aversion to paraquat, diquat isoxazolidinone and cyclosulfones.

In still a further aspect, a herbicidal composition is provided comprising (A) a herbicidally effective amount of (2-ethoxy-2-oxo-ethyl) 1- [ 2-chloro-5- (3, 5-dimethyl-2, 6-dioxo-4-thioxo-1, 3, 5-triazin-1-yl) -4-fluoro-phenoxy ] -cyclopropanecarboxylate and (B) at least one herbicide selected from the group consisting of glufosinate, L-glufosinate, glyphosate, 2,4-D, clethodim, pinoxaden, diflufenican, flumetsulam, saflufenacil, flumetsulam, trifluralin, haloxypyr-sodium, flufenacet, triflumuron, haloxyfop-methyl, flupyr-methyl, mesotrione, oxaziclomefone, dicap-methyl, paraquat and clomazone.

In general, the mixing ratio (by weight) of the compound (A) to the compound of the component (B) is from 0.01:1 to 100:1, more preferably from 0.025:1 to 20:1, even more preferably from 1:30 to 20:1.

The most preferred ratio of A to B is in the range of 0.2:1 to 20:1, especially for example 1:30 or 1:15, or 2:15, 4:15, or 3:10, or 3:5, 5:6, or 1:1 or 16:15, or 6:5 or 5:3, or 12:5, or 10:3 or 20:3 or 12:1.

When applied in the compositions of the present invention, component (a) is typically applied at a rate of 25 to 2000gha, more particularly 25, 50, 75, 100, 125, 150, 200, 250, 300, 400, 500, 750, 800, 1000, 1250, 1500, 1800 or 2000 g/ha. Such a ratio of component (a) is typically used in combination with a component B of 5 to 2000g/ha, and more particularly in combination with a component (B) of 10, 15, 25, 30, 60, 75, 100, 125, 200, 250, 300, 350, 375, 400, 450, 500, 750 or 1000g a.i./ha.

When the active ingredients are combined, for any given active ingredient combination, the expected activity (E) obeys the so-called Colby's formula and can be calculated as follows (Colby, s.r., calculating SYNERGISTIC AND antagonistic responses of herbicide combination [ calculate synergistic and antagonistic reactions of herbicide combinations ], weeds [ Weeds ], stage 15, pages 20-22; 1967):

ppm = milligrams of active ingredient (a.i.) per liter

X =% action of first active ingredient, p ppm of the active ingredient is used

Y =% action on the second active ingredient using q ppm of active ingredient.

The expected effect of active ingredient a+b, using p+q ppm of active ingredient, is expressed by the following formula:

If the actual observed effect (O) is greater than the expected effect E, then the combined effect is superadditive, i.e., there is a synergistic effect. Mathematically, the synergy corresponds to a positive value of the difference of (O-E). In the case of a completely complementary superposition of activities (expected activity), the difference (O-E) is zero. Negative values of the difference (O-E) mark a loss of activity compared to the expected activity.

The compound (B) is called a herbicide. Thus, the combinations of the present invention take advantage of any added herbicidal activity, and certain embodiments may even exhibit synergistic effects. This occurs whenever the effect of the combination of active ingredients is greater than the sum of the effects of the individual components.

The combinations of the invention may also provide an expanded spectrum of activity compared to the activity obtained for each individual component and/or allow for the use of lower ratios of the individual components when used in combination than when used alone, in order to modulate effective herbicidal activity.

Furthermore, it is also possible that the composition of the invention may show increased crop tolerance when compared to the effect of compound a alone. This occurs when the effect of the combination of active ingredients is less damaging to the crop of interest than the effect of one of the active ingredients alone.

In a further aspect, the present invention also relates to a compound or composition according to the present invention, i.e. (2-ethoxy-2-oxo-ethyl) 1- [ 2-chloro-5- (3, 5-dimethyl-2, 6-dioxo-4-thioxo-1, 3, 5-triazin-1-yl) -4-fluoro-phenoxy ] -cyclopropanecarboxylic acid ester or a composition comprising (2-ethoxy-2-oxo-ethyl) 1- [ 2-chloro-5- (3, 5-dimethyl-2, 6-dioxo-4-thioxo-1, 3, 5-triazin-1-yl) -4-fluoro-phenoxy ] -cyclopropanecarboxylic acid ester, for controlling the herbicide such as fluazifop-butyl, fluazifop-p-butyl or other herbicide (e.g. fluazifop-butyl) having the formula (I) in addition to (i.e. 2-ethoxy-2-oxo-ethyl) 1- [ 2-chloro-5- (3, 5-dimethyl-2, 6-dioxo-4-thioxo-1, 3, 5-triazin-1-yl) -4-fluoro-phenoxy ] -cyclopropanecarboxylic acid ester. These weeds may have been rendered tolerant to PPO herbicides by evolution, conventional breeding methods or genetic engineering. Examples include amaranthus longifolius (Amaranthus palmeri) and amaranthus palmosus (Amaranthus tuberculatus) which have evolved to be resistant to PPO herbicides.

In another aspect, there is provided a method for controlling the growth of protoporphyrinogen IX oxidase (PPO) inhibitor herbicide-resistant weeds comprising applying to the weeds, a portion of the weeds, the weed propagation material, or the locus of the weeds an effective amount of a compound or composition according to the invention, i.e., (2-ethoxy-2-oxo-ethyl) 1- [ 2-chloro-5- (3, 5-dimethyl-2, 6-dioxo-4-thioxo-1, 3, 5-triazin-1-yl) -4-fluoro-phenoxy ] -cyclopropanecarboxylate or a composition comprising (2-ethoxy-2-oxo-ethyl) 1- [ 2-chloro-5- (3, 5-dimethyl-2, 6-dioxo-4-thioxo-1, 3, 5-triazin-1-yl) -4-fluoro-phenoxy ] -cyclopropanecarboxylate, wherein the PPO-resistant weeds are weeds that are resistant to at least one o inhibitor herbicide other than the compound having formula (I).

In another aspect, there is provided a method for controlling the growth of PPO-resistant weeds, the method comprising applying to the weeds, a portion of the weeds, the weed propagation material, or the locus of the weeds an effective amount of a compound or composition according to the invention, i.e. (2-ethoxy-2-oxo-ethyl) 1- [ 2-chloro-5- (3, 5-dimethyl-2, 6-dioxo-4-thioxo-1, 3, 5-triazin-1-yl) -4-fluoro-phenoxy ] -cyclopropanecarboxylate or a composition comprising (2-ethoxy-2-oxo-ethyl) 1- [ 2-chloro-5- (3, 5-dimethyl-2, 6-dioxo-4-thioxo-1, 3, 5-triazin-1-yl) -4-fluoro-phenoxy ] -cyclopropanecarboxylate, wherein the PPO-resistant weeds are weeds that are resistant to at least one PPO-inhibiting herbicide in addition to the compound of formula (I), and have an amino acid, 210, an amino acid and/or an amino acid 399 mutation in the gene encoding protooxidase 361.

In another aspect, there is provided a method for controlling the growth of PPO-resistant weeds, the method comprising applying to the weeds, a portion of the weeds, the weed propagation material, or the locus of the weeds, an effective amount of a compound or composition according to the invention, i.e. (2-ethoxy-2-oxo-ethyl) 1- [ 2-chloro-5- (3, 5-dimethyl-2, 6-dioxo-4-thio-1, 3, 5-triazin-1-yl) -4-fluoro-phenoxy ] -cyclopropanecarboxylate or a composition comprising (2-ethoxy-2-oxo-ethyl) 1- [ 2-chloro-5- (3, 5-dimethyl-2, 6-dioxo-4-thio-1, 3, 5-triazin-1-yl) -4-fluoro-phenoxy ] -cyclopropanecarboxylate, wherein the PPO-resistant weeds have mutations at amino acid 98, amino acid 210 and/or amino acid in the gene encoding the protoporphyrinogen oxidase.

In another aspect, there is provided the use of a composition according to the invention on top of a crop plant that is tolerant to PPO inhibitors. As known PPO inhibitors, it is apparent that compounds having the formula (I), i.e. (2-ethoxy-2-oxo-ethyl) 1- [ 2-chloro-5- (3, 5-dimethyl-2, 6-dioxo-4-thio-1, 3, 5-triazin-1-yl) -4-fluoro-phenoxy ] -cyclopropanecarboxylic acid ester, can be used in a method for controlling undesirable vegetation in crop plants which are tolerant to protoporphyrinogen oxidase (PPO) inhibitors. Such plants may be obtained, for example, by transforming crop plants with a nucleic acid encoding a suitable protoporphyrinogen oxidase, which nucleic acid may contain a mutation to render it more resistant to a PPO inhibitor. 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. In a preferred embodiment, crop plants tolerant to PPO inhibitors comprise a gene encoding HemG enzyme h_n90, as disclosed in WO 2017/027778 and WO 2024/015950. In another preferred embodiment, crop plants that are tolerant to PPO inhibitors are cotton, corn and soybean.

In a further aspect, there is provided the use of a compound of formula (I) or a composition comprising a compound of formula (I) in crops of plants that are tolerant to PPO inhibitor herbicides.

The compounds of the present invention may be prepared by techniques known to those skilled in the art of organic chemistry. The general procedure for the production of compounds having formula (I) is described below. Substituents X¹、X²、X³、Y、B、D、R¹、R²、R³、R⁴、R⁵、R⁶、R⁷、R⁸、R⁹、R¹⁰、R¹¹、R¹²、R¹³、R¹⁴、R¹⁵、R¹⁶ and R ¹⁷ are as defined above unless otherwise indicated herein. The starting materials for preparing the compounds of the present invention may be purchased from general commercial suppliers or may be prepared by known methods. The starting materials as well as intermediates may be purified by prior art methods such as chromatography, crystallization, distillation and filtration before use in the next step.

The compound having the formula (I) may be prepared from the compound having the formula (a) and the compound having the formula (B), as shown in reaction scheme 1.

Reaction scheme 1

For example, a mixture of a compound having formula (a) and a compound having formula (B) may be treated with a base (e.g., triethylamine) and a carbonyl transfer agent (e.g., phosgene or carbonyl diimidazole) in a suitable solvent (e.g., acetonitrile).

Urea or thiourea of formula (a) is available or can be prepared by methods well known in the literature.

The compound having formula (B) may be prepared from an aniline having formula (C), as shown in reaction scheme 2.

Reaction scheme 2

For example, the compound of formula (C) may be treated with a carbonyl or thiocarbonyl transfer agent (e.g., carbonyldiimidazole, diphosgene, triphosgene or thiophosgene) in a suitable solvent (e.g., acetonitrile).

Anilines of formula (C) can be prepared from nitro compounds of formula (D), as shown in reaction scheme 3.

Reaction scheme 3

For example, the compound of formula (D) may be treated with a reducing agent (e.g., iron and ammonium chloride) in a suitable solvent (e.g., a mixture of water and ethanol).

The nitro compound of formula (D) can be prepared from a phenol of formula (E) and a compound of formula (F) wherein LG represents a leaving group, e.g., a halogen atom such as a chlorine atom, as shown in reaction scheme 4.

Reaction scheme 4

For example, the nitro compound of formula (E) may be treated with a compound of formula (F) in the presence of a base such as potassium carbonate in a suitable solvent such as acetonitrile.

The nitro compounds of formula (E) are available or can be prepared by methods well known in the literature.

The compound having formula (F) may be prepared from an alcohol or amine having formula (G) and an acid having formula (H), as shown in reaction scheme 5.

Reaction scheme 5

For example, the acid of formula (H) may be treated with an activator (e.g., oxalyl chloride) in a suitable solvent (e.g., dichloromethane and dimethylformamide), and the resulting intermediate then treated with an alcohol or amine of formula (G) in the presence of a base (e.g., triethylamine) in a suitable solvent (e.g., dichloromethane).

Alcohols and amines of formula (G) and acids of formula (H) are available or can be prepared by methods well known in the literature.

Alternatively, the compound of formula (D) may also be prepared from an acid of formula (J) and an alcohol or amine of formula (G), as shown in reaction scheme 6.

Reaction scheme 6

For example, an acid of formula (J) may be treated with an activator (e.g., oxalyl chloride) in a suitable solvent (e.g., dichloromethane and dimethylformamide), and then the resulting intermediate is treated with an alcohol or amine of formula (G) in the presence of a base (e.g., triethylamine) in a suitable solvent (e.g., dichloromethane).

The compound having formula (D) may also be prepared from a compound having formula (K) and an alkylating agent having formula (L) wherein LG represents a leaving group, such as a halogen atom, as shown in reaction scheme 7.

Reaction scheme 7

For example, an acid having formula K (wherein B is oxygen) may be treated with an alkylating agent (L) (e.g., a haloalkyl ester) and a base (e.g., potassium carbonate) in a suitable solvent (e.g., acetonitrile).

The compound having the formula (K) can be prepared from a phenol having the formula (E) and an alkylating agent (M) (wherein LG represents a leaving group, such as a halogen atom), as shown in reaction scheme 8.

Reaction scheme 8

For example, the phenol of formula (E) may be treated with an alkylating agent of formula (M) (e.g., a haloalkyl acid or amide) and a base (e.g., potassium t-butoxide) in a suitable solvent (e.g., tetrahydrofuran).

The phenols of formula (E) and the compounds of formula (M) are available or can be prepared by methods well known in the literature.

The compound having the formula (I-a), which is a compound having the formula (I), wherein R ⁸ is an OH group, can be prepared from a compound having the formula (I-B), which is a compound having the formula (I), wherein R ⁸ is OR ⁹, as shown in reaction scheme 9.

Reaction scheme 9

For example, the compounds of formula (I-B) may be treated with hydrochloric acid in a suitable solvent, such as dioxane.

The compound of formula (I-C), which is a compound of formula (I) wherein R ⁸ is NR ¹⁰R¹¹, can be prepared from a compound of formula (I-a) as shown in reaction scheme 10.

Reaction scheme 10

For example, the compounds of formula (I-A) may be in a suitable solvent (e.g. dichloromethane)

To form an acid halide, which may be treated with the reagent HNR ¹⁰R¹¹ in a suitable solvent (e.g., dichloromethane) in the presence of a base (e.g., triethylamine).

Those skilled in the art will recognize that the order in which the above-described transformations are performed may often be altered or combined in alternative ways to produce various compounds of formula (I). Multiple steps may also be combined in a single reaction. All such variations are contemplated as being within the scope of the present invention.

The skilled artisan will also appreciate that some agents will be incompatible with certain values or combinations of substituents X¹、X²、X³、Y、B、D、R¹、R²、R³、R⁴、R⁵、R⁶、R⁷、R⁸、R⁹、R¹⁰、R¹¹、R¹²、R¹³、R¹⁴、R¹⁵、R¹⁶ and R ¹⁷ as defined herein, and that any additional steps, such as protection and/or deprotection steps (required to achieve the desired transformations) will be apparent to the skilled artisan.

The compounds according to the invention can be used as herbicides in unmodified form, but they are generally formulated into compositions in a variety of ways using formulation aids such as carriers, solvents and surface-active substances. These formulations may be in various physical forms, for example in the form of dust, gels, wettable powders, water dispersible granules, water dispersible tablets, effervescent compressed tablets, emulsifiable concentrates, microemulsifyable 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 a carrier), impregnated polymeric films or in other forms known, for example, from Manualon Development and Use of FAO and WHO Specifications for Pesticides [ handbook of development and use of the FAO and WHO standards for pesticides ], united nations, version 1, second revision (2010). For the water-soluble compound, a soluble liquid, a water-soluble concentrate or a water-soluble granule is preferable. Such formulations may be used directly or may be diluted before use for reuse. Dilution may be performed with, for example, water, liquid fertilizer, micronutrients, biological organisms, oil or solvents.

These formulations can be prepared, for example, by mixing the active ingredient with formulation auxiliaries in order to obtain compositions in the form of finely divided solids, granules, solutions, dispersions or emulsions. These active ingredients may also be formulated with other adjuvants such as finely divided solids, mineral oils, oils of vegetable or animal origin, modified oils of vegetable or animal origin, organic solvents, water, surface-active substances or combinations thereof.

These active ingredients may also be contained in very fine microcapsules. The microcapsules contain the active ingredient in a porous carrier. This enables the active ingredient to be released (e.g., slowly released) into the environment in controlled amounts. The microcapsules typically have a diameter of 0.1 to 500 microns. They contain the active ingredient in an amount of about 25% to 95% by weight of the capsule. These active ingredients may be in the form of monolithic solids, in the form of fine particles in solid or liquid dispersions, or in the form of suitable solutions. The encapsulated film may comprise, for example, natural or synthetic rubber, cellulose, styrene/butadiene copolymers, polyacrylonitrile, polyacrylate, polyester, polyamide, polyurea, polyurethane or chemically modified polymer, or other polymers known to those skilled in the art. Alternatively, very fine microcapsules may be formed in which the active ingredient is contained in the form of finely divided particles in a solid matrix of the base material, but these microcapsules are not themselves encapsulated.

Formulation auxiliaries suitable for preparing the compositions according to the invention are known per se. As the liquid carrier, use can be made of: water, toluene, xylene, petroleum ether, vegetable oil, acetone, methyl ethyl ketone, cyclohexanone, anhydride, acetonitrile, acetophenone, amyl acetate, 2-butanone, butylene carbonate, chlorobenzene, cyclohexane, cyclohexanol, alkyl acetate, diacetone alcohol, 1, 2-dichloropropane, diethanolamine, p-diethylbenzene, diethylene glycol rosin acid ester, diethylene glycol butyl ether, diethylene glycol ethyl ether, diethylene glycol methyl ether, N, N-dimethylformamide, dimethyl sulfoxide, 1, 4-dioxane, dipropylene glycol methyl ether, dipropylene glycol dibenzoate, dipropylene glycol, alkylpyrrolidones, ethyl acetate, 2-ethylhexanol, ethylene carbonate, 1-trichloroethane, 2-heptanone, alpha-pinene, d-limonene, ethyl lactate, ethylene glycol butyl ether, ethylene glycol methyl ether, gamma-butyrolactone, glycerol acetate, glycerol diacetate, glycerol triacetate, hexadecane, hexylene glycol, isoamyl acetate, isobornyl acetate, isooctane, ethylene glycol butyl ether, ethylene glycol methyl ether, gamma-butyrolactone, glycerol acetate, glycerol diacetate, glycerol triacetate, hexadecane, hexylene glycol, isoamyl acetate, isobornyl acetate, isooctane isophorone, isopropylbenzene, isopropyl myristate, lactic acid, laurylamine, isopropylidene acetone, methoxypropanol, methyl isoamyl ketone, methyl isobutyl ketone, methyl laurate, methyl caprylate, methyl oleate, methylene chloride, m-xylene, N-hexane, N-octylamine, stearic acid, octylamine acetate, oleic acid, oleylamine, o-xylene, phenol, polyethylene glycol, propionic acid, propyl lactate, propylene carbonate, 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, and the like.

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 hulls, lignin, and the like.

Many surface-active substances can be advantageously used in both solid and liquid formulations, especially those formulations which can be diluted by a carrier before use. The surface-active substances may be anionic, cationic, nonionic or polymeric and they may be used as emulsifiers, wetting agents or suspending agents or for other purposes. Typical surface-active substances include, for example, salts of alkyl sulfates, such as diethanol ammonium lauryl sulfate, salts of alkylaryl sulfonates, such as calcium dodecylbenzene sulfonate, alkylphenol/alkylene oxide adducts, such as ethoxylated nonylphenol, alcohol/alkylene oxide adducts, such as ethoxylated tridecyl alcohol, soaps, such as sodium stearate, salts of alkyl naphthalene sulfonates, such as sodium dibutylnaphthalene sulfonate, salts of dialkyl sulfosuccinates, such as sodium di (2-ethylhexyl) sulfosuccinate, sorbitol esters, such as sorbitol oleate, quaternary 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 monoalkyl phosphates and dialkyl esters, and also further substances, such as those described in McCutcheon' S DETERGENTS AND Emulsifiers Annual [ Mascin cleaners and emulsifier annual, MC Corp., new Yoshig., ridgewood New Jersey (1981).

Additional adjuvants that may be used in the pesticide formulation include crystallization inhibitors, viscosity modifiers, suspending agents, dyes, antioxidants, foaming agents, light absorbers, mixing aids, defoamers, complexing agents, substances and buffers that neutralize or alter the pH, corrosion inhibitors, fragrances, wetting agents, absorption enhancers, micronutrients, plasticizers, glidants, lubricants, dispersants, thickeners, anti-freezing agents, microbiocides, and liquid and solid fertilizers.

The composition according to the invention may comprise additives comprising oils of vegetable or animal origin, mineral oils, alkyl esters of such oils or mixtures of such oils with oil derivatives. The amount of 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 may be added to the spray can at the desired concentration after the spray mixture has been prepared. Preferred oil additives include mineral or vegetable-derived oils, such as rapeseed oil, olive oil or sunflower oil, emulsified vegetable oils, alkyl esters of vegetable-derived oils, such as methyl derivatives, or animal-derived oils, such as fish oil or tallow. Preferred oil additives include alkyl esters of C ₈-C₂₂ fatty acids, especially methyl derivatives of C ₁₂-C₁₈ fatty acids, such as methyl esters of lauric, palmitic and oleic acids (methyl laurate, methyl palmitate and methyl oleate, respectively). Many oil derivatives are known from Compendium of Herbicide Adjuvants [ herbicide adjuvant outline ], 10 th edition, university of south illinois, 2010.

The herbicidal composition as a whole comprises from 0.1 to 99% by weight, in particular 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 comprises from 0 to 25% by weight of a surface-active substance. The compositions of the invention generally comprise from 0.1 to 99% by weight, in particular from 0.1 to 95% by weight, of a compound of the invention and from 1 to 99.9% by weight of a formulation aid, preferably comprising from 0 to 25% by weight of a surface-active substance. Whereas commercial products may preferably be formulated as concentrates, the end user will typically employ a dilute formulation.

The application rate varies within a wide range and depends on the nature of the soil, the application method, the crop plant, the pest to be controlled, the prevailing climatic conditions, and other factors dictated by the application method, the application time and the target crop. Generally, the compounds may be applied at a rate of 1l/ha to 2000l/ha, especially 10l/ha to 1000 l/ha.

The compounds of formula (I) may be used in unmodified form or, preferably, in conjunction with adjuvants conventionally used in the formulation art to provide herbicidal compositions, formulation adjuvants such as carriers, solvents and Surfactants (SAA) are used. The invention therefore further provides a herbicidal composition comprising at least one compound of formula (I) and an agriculturally acceptable carrier and optionally adjuvants. An agriculturally acceptable carrier is, for example, a carrier suitable for agricultural use. Agricultural vectors are well known in the art.

The herbicidal compositions generally comprise from 0.1 to 99% by weight, in particular from 0.1 to 95% by weight, of a compound of the formula I and from 1 to 99.9% by weight of a formulation auxiliary, which preferably comprises from 0 to 25% by weight of a surface-active substance.

The composition may be selected from a number of formulation types. These include Emulsion Concentrates (EC), suspension Concentrates (SC), suspoemulsions (SE), capsule Suspensions (CS), water-dispersible granules (WG), emulsifiable Granules (EG), water-in-oil Emulsions (EO),

Oil-in-water Emulsions (EW), microemulsions (ME), oil Dispersions (OD), oil suspensions (OF),

Oil-soluble liquid (OL), soluble concentrate (SL), ultra-low volume Suspension (SU), ultra-low volume liquid (UL), parent drug (TK), dispersible Concentrate (DC), soluble Powder (SP), wettable Powder (WP) and Soluble Granule (SG). In any event, the type of formulation selected will depend on the particular purpose envisaged and the physical, chemical and biological properties of the compound of formula (I).

Soluble Powders (SP) may be prepared by mixing a compound having formula (I) with one or more water-soluble inorganic salts (such as sodium bicarbonate, sodium carbonate or magnesium sulphate) or one or more water-soluble organic solids (such as polysaccharides) and optionally one or more wetting agents, one or more dispersing agents or mixtures of said agents to improve water dispersibility/water solubility. The mixture was then ground to a fine powder. Similar compositions may also be granulated to form water Soluble Granules (SG).

Wettable Powders (WP) may be prepared by mixing a compound having formula (I) with one or more solid diluents or carriers, one or more wetting agents and preferably one or more dispersing agents, and optionally one or more suspending agents to facilitate dispersion in a liquid. The mixture was then ground to a fine powder. Similar compositions may also be granulated to form water dispersible granules (WG).

The Granules (GR) may be formed by granulating a mixture of a compound of formula (I) with one or more powdered solid diluents or carriers, or by absorbing a compound of formula (I) (or a solution thereof in a suitable agent) into a porous particulate material such as pumice, attapulgite clay, fuller's earth, kieselguhr (kieselguhr), diatomaceous earth (diatomaceous earth) or corncob powder, or by adsorbing a compound of formula (I) (or a solution thereof in a suitable agent) onto a hard core material such as sand, silicate, mineral carbonate, sulphate or phosphate and drying if necessary. Agents commonly used to aid absorption or adsorption include solvents (such as aliphatic and aromatic petroleum solvents, alcohols, ethers, ketones and esters) and adhesives (such as polyvinyl acetate, polyvinyl alcohol, dextrins, sugars and vegetable oils). One or more other additives (e.g., emulsifiers, wetting agents, or dispersants) may also be included in the granule.

Dispersible Concentrates (DC) may be prepared by dissolving a compound having formula (I) in water or an organic solvent such as a ketone, alcohol or glycol ether. These solutions may contain surfactants (e.g., to improve water dilution or to prevent crystallization in spray tanks).

Emulsifiable Concentrates (EC) or oil-in-water Emulsions (EW) may be prepared by dissolving a compound having formula (I) in an organic solvent, optionally containing one or more wetting agents, one or more emulsifying agents or a mixture of said agents. Suitable organic solvents for use in the EC include aromatic hydrocarbons (such as alkylbenzenes or alkylnaphthalenes, exemplified by SOLVESSO 100, SOLVESSO 150 and SOLVESSO 200; SOLVESSO is a registered trademark), ketones (such as cyclohexanone or methylcyclohexanone) and alcohols (such as benzyl alcohol, furfuryl alcohol or butanol), N-alkylpyrrolidones (such as N-methylpyrrolidone or N-octylpyrrolidone), dimethylamides of fatty acids (such as C ₈-C₁₀ fatty acid dimethylamides), and chlorinated hydrocarbons. The EC product may spontaneously emulsify upon addition to water, thereby producing an emulsion with sufficient stability to allow spray application by appropriate equipment.

The preparation of EW involves obtaining a compound of formula (I) as a liquid (which may be melted at a reasonable temperature, typically below 70 ℃ if it is not a liquid at room temperature) or in the form of a solution (by dissolving it in a suitable solvent), and then emulsifying the resulting liquid or solution into water containing one or more SAAs under high shear to produce an emulsion. Suitable solvents for use in EW include vegetable oils, chlorinated hydrocarbons (e.g., chlorobenzene), aromatic solvents (e.g., alkylbenzenes or alkylnaphthalenes), and other suitable organic solvents having low solubility in water.

Microemulsions (ME) can be prepared by mixing water with a blend of one or more solvents and one or more SAAs to spontaneously produce thermodynamically stable isotropic liquid formulations. The compound of formula (I) is initially present in water or in a solvent/SAA blend. Suitable solvents for use in ME include those described above for use in EC or in EW. The ME may be an oil-in-water system or a water-in-oil system (which system is present can be determined by conductivity measurements) and may be suitable for mixing a water-soluble pesticide and an oil-soluble pesticide in the same formulation. ME is suitable for dilution into water, either to remain as a microemulsion or to form a conventional oil-in-water emulsion.

Suspension Concentrates (SC) may comprise aqueous or non-aqueous suspensions of finely divided insoluble solid particles of a compound of formula (I). The SC may be prepared by ball milling or bead milling a solid compound of formula (I), optionally together with one or more dispersants, in a suitable medium to produce a fine particle suspension of the compound. One or more wetting agents may be included in the composition, and suspending agents may be included to reduce the rate of particle settling. Alternatively, the compound of formula (I) may be dry milled and added to water containing the reagents described above to produce the desired end product.

The aerosol formulation comprises a compound having formula (I) and a suitable propellant (e.g. n-butane). The compound of formula (I) may also be dissolved or dispersed in a suitable medium (e.g., water or a water miscible liquid such as n-propanol) to provide a composition for use in a non-pressurized manual spray pump.

The Capsule Suspension (CS) can be prepared in a similar manner to the preparation of the EW formulation, but with an additional polymerization stage, to obtain an aqueous dispersion of oil droplets, each of which is surrounded by a polymeric shell and contains a compound having formula (I) and optionally a carrier or diluent for the oil droplets. The polymer shell may be produced by interfacial polycondensation reactions or by coacervation procedures. These compositions can provide controlled release of compounds having formula (I) and they can be used for seed treatment. The compounds of formula (I) may also be formulated in biodegradable polymer matrices to provide slow, controlled release of the compounds.

The composition may contain one or more additives to improve the biological properties of the composition, for example by improving the wettability, retention or distribution on the surface, the resistance to rain on the treated surface, or the absorption or mobility of the compound of formula (I). Such additives include Surfactants (SAA), oil-based spray additives such as certain mineral or natural vegetable oils (e.g., soy and rapeseed oils), modified vegetable oils (e.g., methylated rapeseed oil (MRSO)), and blends of these with other bio-enhancing adjuvants (ingredients that can assist or alter the action of compounds having formula (I)).

Wetting agents, dispersants and emulsifiers may be SAA of cationic, anionic, amphoteric or nonionic type.

Suitable cationic types of SAAs include quaternary ammonium compounds (e.g., cetyltrimethylammonium bromide), imidazolines, and amine salts.

Suitable anionic SAAs include alkali metal salts of fatty acids, salts of aliphatic monoesters of sulfuric acid (e.g. sodium lauryl sulfate), salts of sulfonated aromatic compounds (e.g. sodium dodecyl benzene sulfonate, calcium dodecyl benzene sulfonate, butylnaphthalene sulfonate and mixtures of sodium di-isopropyl naphthalene sulfonate and sodium tri-isopropyl naphthalene sulfonate), ether sulfates, alcohol ether sulfates (e.g. sodium laureth-3-sulfate), ether carboxylates (e.g. sodium laureth-3-carboxylate), phosphate esters (products from the reaction between one or more fatty alcohols and phosphoric acid (mainly monoesters) or phosphorus pentoxide (mainly diesters), such as the reaction between lauryl alcohol and tetraphosphoric acid; alternatively, these products may be ethoxylated), sulfosuccinamates, paraffin or olefin sulfonates, taurates, lignin sulfonates and phosphate/sulfates of tristyrylphenols.

Suitable amphoteric types of SAAs include betaines, propionates, and glycinates.

Suitable nonionic SAAs include condensation products of alkylene oxides (such as ethylene oxide, propylene oxide, butylene oxide or mixtures thereof) with fatty alcohols (such as oleyl alcohol or cetyl alcohol) or with alkylphenols (such as octylphenol, nonylphenol or octylcresol), partial esters derived from long chain fatty acids or hexitol anhydrides, condensation products of the partial esters with ethylene oxide, block polymers (comprising ethylene oxide and propylene oxide), alkanolamides, monoesters (such as polyethylene glycol esters of fatty acids), amine oxides (such as lauryl dimethyl amine oxide), lecithins and sorbitan and esters thereof, alkylpolyglycosides and tristyrylphenols.

Suitable suspending agents include hydrocolloids (such as polysaccharides, polyvinylpyrrolidone or sodium carboxymethylcellulose) and swelling clays (such as bentonite or attapulgite).

The compounds of formula (I) are generally used in the form of agrochemical compositions and can be applied simultaneously or sequentially with further compounds to the crop area or plant to be treated. For example, these additional compounds may be fertilizers or micronutrient donors or other formulations that affect plant growth. They may also be selective or nonselective herbicides, together with insecticides, fungicides, bactericides, nematicides, molluscicides or mixtures of several of these preparations, if desired together with further carriers, surfactants or adjuvants which facilitate application, which are customarily used in the art of formulation.

As used herein, the term "locus" means a place in or on which plants are grown, or where seeds of cultivated plants are sown, or where seeds are to be placed in soil. It includes soil, seeds, and seedlings, along with established vegetation.

The term "plant" refers to all the tangible parts of a plant, including seeds, seedlings, saplings, roots, tubers, stems, stalks, leaves, and fruits.

The term "plant propagation material" is understood to mean the reproductive parts of plants, such as seeds, which parts can be used for propagation of plants, as well as nutritional materials (VEGETATIVE MATERIAL), such as cuttings or tubers (e.g. potatoes). Mention may be made, for example, of seeds (in the strict sense), roots, fruits, tubers, bulbs, rhizomes and parts of plants. Germinated plants and young plants to be transplanted after germination or after emergence can also be mentioned. These young plants may be protected prior to transplantation by being treated, either completely or partially, by dipping. Preferably, "plant propagation material" is understood to mean seeds.

The pesticides mentioned herein using their common names are known, for example, from "THE PESTICIDE Manual of pesticides", 15 th edition, british Crop Protection Council, british crop protection committee 2009.

The compounds of formula (I) may be used in unmodified form or, preferably, together with adjuvants conventionally employed in the art of formulation. For this purpose, they can be conveniently formulated in a known manner as emulsifiable concentrates, coatable pastes, directly sprayable or dilutable solutions or suspensions, diluted emulsions, wettable powders, soluble powders, dust powders, granules and also encapsulants, for example in polymeric substances. For the type of composition, the method of application is selected according to the intended purpose and the circumstances at the time, such as spraying, atomizing, dusting, broadcasting, painting or pouring. The composition may also contain further adjuvants, such as stabilizers, defoamers, viscosity modifiers, binders or tackifiers, together with fertilizers, micronutrient donors or other formulations for achieving special effects.

The compound of formula (I) may be the only active ingredient of the composition or it may be admixed with one or more additional active ingredients such as pesticides, fungicides, synergists, herbicides or plant growth regulators, as appropriate. In some cases, additional active ingredients may produce unexpected synergistic activity.

Typically, the formulation comprises from 0.01% to 90% by weight of an active agent, consisting at least of a compound of formula (I) together with components (B) and (C), and optionally other active agents (in particular microbiocides or preservatives or the like), from 0% to 20% of an agriculturally acceptable surfactant and from 10% to 99.99% of a solid or liquid formulation inert agent and one or more adjuvants. The concentrated form of the composition typically contains between about 2% and 80%, preferably between about 5% and 70% by weight of active agent. The formulation may for example contain from 0.01 to 20% by weight, preferably from 0.01 to 5% by weight, of active agent in the form of administration. However, commercial products will preferably be formulated as concentrates and the end user will typically use dilute formulations.

Table of examples

Table 1 below discloses 560 specific compounds of formula (I), labeled compounds 1-1 through 1-560, respectively, wherein X ¹ is sulfur, X ² and X ³ are oxygen, R ¹ and R ² are methyl, R ⁴ is chlorine and Y is C-H.

TABLE 1 Compounds of formula (I) according to the invention alone

560 Compounds of formula (I) wherein X ¹ and X ² are sulfur, X ³ is oxygen, R ¹ and R ² are methyl, R ⁴ is chlorine and Y is C-H, and the values of B, D, R ³、R⁸、R¹⁶ and R ¹⁷ are as given in table 1 for compounds 1-1 to 1-560, respectively labeled compound numbers 2-1 to 2-560.

560 Compounds of formula (I) wherein X ¹ is sulfur, X ² and X ³ are oxygen, R ¹ and R ² are methyl, R ⁴ is bromine and Y is C-H, and the values of B, D, R ³、R⁸、R¹⁶ and R ¹⁷ are as given in table 1 for compounds 1-1 to 1-560, respectively labeled as compound numbers 3-1 to 3-560.

560 Compounds of formula (I) wherein X ¹ and X ² are sulfur, X ³ is oxygen, R ¹ and R ² are methyl, R ⁴ is bromine and Y is C-H, and the values of B, D, R ³、R⁸、R¹⁶ and R ¹⁷ are as given in table 1 for compounds 1-1 to 1-560, respectively, labeled compound numbers 4-1 to 4-1230.

Examples of formulations

The active ingredient is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable mill to provide a wettable powder which can be diluted with water to give a suspension of the desired concentration.

The active ingredient is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable mill to provide a powder that can be used directly for seed treatment.

Emulsifiable concentrate

Emulsions with any desired dilution that can be used in plant protection can be obtained from such concentrates by dilution with water.

The ready-to-use dust agent is obtained by mixing the active ingredient with a carrier and grinding the mixture in a suitable grinder. Such powders may also be used for dry dressing of seeds.

Extruder granule

The active ingredient is mixed with the auxiliary and ground, and the mixture is moistened with water. The mixture is extruded and then dried in an air stream.

Coated granule

Active ingredient [ Compound having formula (I) ] 8%

Polyethylene glycol (molecular weight 200) 3%

Kaolin 89%

The finely ground active ingredient is applied uniformly in a mixer to kaolin wet with polyethylene glycol. In this way dust-free coated granules are obtained.

Suspension concentrate

The finely ground active ingredient is intimately mixed with the adjuvants to give a suspension concentrate from which any desired dilution of the suspension can be obtained by dilution with water. With such dilutions, living plants and plant propagation material can be treated and protected against microbial infection by spraying, watering or dipping.

Flowable concentrate for seed treatment

The finely ground active ingredient is intimately mixed with the adjuvants to give a suspension concentrate from which any desired dilution of the suspension can be obtained by dilution with water. With such dilutions, living plants and plant propagation material can be treated and protected against microbial infection by spraying, watering or dipping.

Sustained release capsule suspension

28 Parts of a combination of compounds of the formula (I) are mixed with 2 parts of an aromatic solvent and 7 parts of toluene diisocyanate/polymethylene-polyphenyl isocyanate-mixture (8:1). This mixture was emulsified in a mixture of 1.2 parts of polyvinyl alcohol, 0.05 parts of defoamer and 51.6 parts of water until the desired particle size was reached. To this emulsion was added 2.8 parts of a1, 6-hexamethylenediamine mixture in 5.3 parts of water. The mixture was stirred until the polymerization was completed. The capsule suspension obtained is stabilized by adding 0.25 parts of thickener and 3 parts of dispersant. The capsule suspension formulation contains 28% active ingredient. The diameter of the media capsule is 8-15 microns. The resulting formulation is applied to the seeds as an aqueous suspension suitable for use in the device for this purpose.

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

The compounds of the invention may also be used in mixtures with one or more further herbicides and/or plant growth regulators. Examples of such additional herbicides or plant growth regulators include acetochlor, acifluorfen (including acifluorfen-sodium), benalafen, ametryn, amicarbazone, aminopyralid, clomazone, atrazine, fluobutamid-M, quinclorac (benquitrione), bensulfuron (including bensulfuron-methyl), bentazone, flupiroxicam, bialaphos, biscarfentrazone, bispyribac-sodium, bispyribac Luo Zong (bixlozone), clomazone (broclozone), triclopyr, bromoxynil, butachlor, flumetsulam, carfentrazone (including carfentrazone-ethyl), Clomazone (including clomazone-methyl), chlorimuron-ethyl (including closulfuron-ethyl), chlormeuron, chlorsulfuron, clomazone-phosphine (clacyfos), clethodim, clodinafop-propargyl (including clodinafop-propargyl), clomazone, clopyralid, ciclopirox (cyclopyranil), ciclopirox (cyclopyrimorate), cyclosulfamuron, cyhalofop-butyl (including cyhalofop-butyl), 2,4-D (including choline salts and 2-ethylhexyl esters thereof), 2,4-DB, betametham, dicamba (including aluminum, aminopropyl thereof), Bis-aminopropyl methyl, choline, dichloroprop, diglycolamine, dimethylamine, dimethylammonium, potassium and sodium salts), diclosulam, diflufenican, diflufenzopyr, dimethenamid-P, dioxopyrithione (dioxopyritrione), dibromodiquat, diuron, flumetsulam, ethaboxam, ethofumesate, oxazachlor (including fenoxaprop-ethyl), benfurazolidone (fenoxasulfone), benfurazolidone (fenpyrazone), fenquidone (fenquinotrione), tebufenpyr, triamcinolone, Flazasulfuron, florasulam, flurbiproflumilast (florpyrauxifen) (including flurbiproflumilast-benzyl), haloxyfop-butyl (including haloxyfop-butyl), flucarbazone-methyl (including flucarbazone-sodium), fluclomazone (fluchloraminopyr) (including fluclomazone (fluchloraminopyr-tefuryl)), flufenacet, fluazifop-butyl (flufenoximacil), flumetsulam, flubenuron, fomesafen, fluflazasulfuron (including fluflazasulfuron-methyl-sodium), fluazifop-methyl, Fluroxypyr (including isooctyl fluroxypyr (fluroxypyr-meptyl)), flumetsulam, fomesafen, foramsulfuron, glufosinate (including L-glufosinate and ammonium salts of both), glyphosate (including its diamine, isopropyl ammonium and potassium salts), fluroxypyr (halauxifen) (including fluroxypyr-meptyl-methyl), haloxyfop (including haloxyfop-methyl), hexazinone, hydantoin (hydantocidin), clomazone (icafolin) (including clomazone-methyl), imazethapyr (including R-imazethapyr), Imazethapyr, indenofloxacin, indoxacarb (indolauxipyr) (including indoxacarb (indolauxipyr-cyanomethyl)), iodosulfuron (including iodometsulfuron-methyl-sodium), iodofensulfuron (iofensulfuron) (including iodofensulfuron-sodium), ioxynil, ipratropium (iptriazopyrid), isoproturon, isoxaflutole, lan Ke San ketone (lancotrione), MCPA, MCPB, hyperbaric acid (mecoprop-P), and, Oxaziclomefone, metsulfuron, dichlormid nicosulfuron, dactylicapnd, and oxaziclomefone, metsulfuron, dichlormid, nicosulfuron, dactylicapnos, and oxadiazon, cyclosulfamuron, oxyfluorfen, paraquat dichloride pendimethalin, penoxsulam, bendiuron, picloram, pinoxaden, pretilachlor, primisulfuron-methyl, prometryn, propanil, oxadiazon, propyrisulfuron (propyrisulfuron), pendinafop-propargyl, prosulfuron, pyraclonil (pyraflufen) (including pyraclonil-ethyl), Pyrazoloquinolate (pyraquinate), sulfonylgrass, pyridate, pyriftalid, fluoropyrimidine (pyriflubenzoxim), pyriproxyfen (pyrimisulfan), haloxyfop-methyl, pyroxsulam, quinclorac, cloquintocet-mexyl (including quizalofop-ethyl and quizalofop-methyl (quizalofop-P-tefuryl)), li Misha Fenne (rimisoxafen), rimsulfuron, saflufenacil, sethoxydim, simazine, S-isopropylmethenal (S-metalochlor), sulfentrazone, Sulfosulfuron, buthiuron, terfuratrione, cyclosulfamuron, terbuthiuron, tebuzin, penoxsulam (tetflupyrolimet), thifensulfuron methyl (thiencarbazone), thifensulfuron methyl, fluoxastrobin (tiafenacil), tobelite (tolpyralate), topramezone, triclopyr, flucarbazone (triafamone), dicamba, cinosulfuron, tribenuron (including tribenuron-methyl), triclopyr, trifloxysulfuron (including trifloxysulfuron-sodium), trifluoperazone (trifludimoxazin), trifloxysulfuron, Trifluralin, flusulfamuron, triazosulfuron, 3- (2-chloro-4-fluoro-5- (3-methyl-2, 6-dioxo-4-trifluoromethyl-3, 6-dihydropyrimidine-1 (2H) -yl) phenyl) -5-methyl-4, 5-dihydroisoxazole-5-carboxylic acid ethyl ester, 4-hydroxy-1-methoxy-5-methyl-3- [4- (trifluoromethyl) -2-pyridinyl ] imidazolidin-2-one, 4-hydroxy-1, 5-dimethyl-3- [4- (trifluoromethyl) -2-pyridinyl ] imidazolidin-2-one, 5-ethoxy-4-hydroxy-1-methyl-3- [4- (trifluoromethyl) -2-pyridinyl ] imidazolidin-2-one, 4-hydroxy-1-methyl-3- [4- (trifluoromethyl) -2-pyridinyl ] 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, (1 RS,5 SR) -3- [ 2-methoxy-4- (prop-1-yn-1-yl) phenyl ] -4-oxobicyclo [3.2.1] oct-2-en-2-yl methyl carbonate, ethyl-2- [ [3- [ [ 3-chloro-5-fluoro-6- [ 3-methyl-2, 6-dioxo-4- (trifluoromethyl) pyrimidin-1-yl ] -2-pyridinyl ] oxy ] acetate, 2- [2- [ 2-bromo-4-fluoro-5- [ 3-methyl-2, 6-dioxo-4- (trifluoromethyl) pyrimidin-1-yl ] phenoxy ] -2-methoxy-acetic acid methyl ester, 6-chloro-4- (2, 7-dimethyl-1-naphthyl) -5-hydroxy-2-methyl-pyridazin-3-one, 6-amino-5-chloro-2- (4-chloro-2-fluoro-3-methoxy-phenyl) pyrimidine-4-carboxylic acid (2-fluorophenyl) methyl ester, 6-amino-5-chloro-2- (4-chloro-2-fluoro-3-methoxy-phenyl) pyrimidine-4-carboxylic acid, 3- [ 2-chloro-5- [3, 6-dihydro-3-methyl-2, 6-dioxo-4- (trifluoromethyl) -1 (2H) -pyrimidinyl ] -4-fluorophenyl ] -3a,4,5, 6-tetrahydro-6-methyl-6 aH-cyclopenta ] isoxazole-6 a-carboxylic acid methyl ester, 2- [ (2-bromo-6-fluoro-phenyl) methoxy ] -4-isopropyl-1-methyl-7-oxabicyclo [2.2.1] heptane and 6-amino-2- (4-chloro-2-fluoro-3-methoxy-phenyl) -5-methoxy-pyrimidine-4-carboxylic acid (isopropylsubunit amino (isopropylideneamino)) ester.

The compounds or mixtures of the present invention may also be used in combination with one or more herbicide safeners. Examples of such safeners include clomazone, clomazone (cloquintocet) (including cloquintocet-mexyl), cyclopropanesulfonamide, dichlorvos, clomazone (including clomazone ethyl), clomazone, trifloxystrobin, clomazone, bisbenzoxazole acid (including bisbenzoxazole acid-ethyl), mefenpyr (mefenpyr) (including mefenpyr), clomazone (metcamifen), and clomazone.

The mixed compatibility 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, british crop protection Committee, 2006.

The compounds of formula (I) can also be used in mixtures with other agrochemicals, such as fungicides, nematicides or insecticides, examples of which are given in the handbook of pesticides.

The mixing ratio of the compound of formula (I) to the mixed compatibilisation is preferably from 1:100 to 1000:1.

These mixtures can be advantageously used in the formulations mentioned above (in which case the "active ingredient" refers to the corresponding mixture of the compound of formula (I) with the mixed compatibility).

The compounds of the invention having formula (I) may also be combined with herbicide safeners. Preferred combinations are clomazone, cloquintocet-mexyl (cloquintocet) (including cloquintocet-mexyl), cyclopropanesulfonamide, dicloxaden, clomazone (including clomazone-ethyl), cyprodinil, fluroxypyr, clomazone, bisbenzoxazole acid (including bisbenzoxazole-ethyl), mefenpyr-acid (mefenpyr-diethyl) (including mefenpyr-diethyl), herbicide safeners (metcamifen), and clomazone.

Particularly preferred are mixtures of compounds of formula (I) with cyclopropanesulfonamide, bisbenzoxazole acid (including ethyl bisbenzoxazolate), cloquintocet-mexyl (including cloquintocet-mexyl) and/or N- (2-methoxybenzoyl) -4- [ (methyl-aminocarbonyl) amino ] benzenesulfonamide.

These safeners of the compounds of the formula (I) may also be in the form of esters or salts, as mentioned, for example, in the handbook of pesticides (14 th edition (BCPC), 2006). Reference to cloquintocet-mexyl also applies to its lithium, sodium, potassium, calcium, magnesium, aluminum, iron, ammonium, quaternary ammonium, sulfonium or phosphonium salts (as disclosed in WO 02/34048), and reference to clomazone-ethyl also applies to clomazone and the like.

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.

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

The compounds of the present invention having formula (I) are useful as herbicides. Thus, the present invention further includes a method for controlling unwanted plants comprising applying to the plants or locus containing them an effective amount of a compound of the invention or a herbicidal composition containing the compound. By 'control' is meant killing, reducing or delaying growth or preventing or reducing germination. Typically, the plants to be controlled are unwanted plants (weeds). By 'locus' is meant the area in which plants are growing or will grow.

The application rate of the compounds of 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-tillage application, etc.), the crop plant, the weed or weeds to be controlled, the prevailing climatic conditions and other factors governed by the application method, the application time and the target crop. The compounds of formula (I) according to the invention are generally applied in a ratio of from 10 to 2000g/ha, in particular from 50 to 1000 g/ha. The preferred range is 10-200g/ha.

Application is usually carried out by spraying the composition, typically by tractor mounted sprayers for large areas, but other methods such as dusting (for powders), dripping or dipping may also be used.

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, maize, rice, soya, sugar beet, sugar cane and turf.

Crop plants may also include trees, if trees, palm trees, coconut trees, or other nuts. Also included are vines (e.g., grapes), shrubs, fruit plants, and vegetables.

Crops are to be understood as also including those crops which have been rendered tolerant to herbicides or classes of herbicides (e.g. ALS-inhibitor, GS-inhibitor, EPSPS-inhibitor, PPO-inhibitor, accase-inhibitor and HPPD-inhibitor) by conventional breeding methods or by genetic engineering. Examples of crops that have been rendered tolerant to imidazolinones (e.g., imazapic) by conventional breeding methods areSummer rape (canola). Examples of crops that have been rendered tolerant to herbicides by genetic engineering methods include, for example, maize varieties with glyphosate and glufosinate resistance, which are under the trade nameAndAre commercially available.

Crops are also understood as those which have been rendered resistant to harmful insects by genetic engineering methods, such as Bt maize (resistant to european corn borer), bt cotton (resistant to boll weevil) and also Bt potato (resistant to corrador beetle). Examples of Bt corn areBt 176 maize hybrid of (first just reaching seed company (SYNGENTA SEEDS)). Bt toxins are proteins naturally formed by bacillus thuringiensis (bacillus thuringiensis) soil bacteria. 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 insecticidal resistance and expression of one or more toxins are(Corn), yield(Corn),(Cotton),(Cotton),(Potato),AndThe plant crop or seed material thereof may be resistant to both herbicides and insect ingestion simultaneously ("stacked" transgenic events). For example, the seed may have the ability to express an insecticidal Cry3 protein while being tolerant to glyphosate.

Crops are also understood to include those obtained by conventional breeding methods or genetic engineering and containing so-called output traits (e.g. improved storage stability, higher nutritional value and improved flavour).

Other useful plants include turf grass for grass, for example, on golf courses, lawns, parks, and roadsides or commercially, and ornamental plants (e.g., flowers or shrubs).

The compounds and compositions of the present invention having formula (I) are typically useful for controlling a variety of monocotyledonous and dicotyledonous weed species. Examples of monocot species that can typically be controlled include physalis alkekengi (Alopecurus myosuroides), avena nuda (Avena fatua), plantain (Brachiaria plantaginea), eclipta alba (Bromustectorum), cyperus esculentus (Cyperus esculentus), crabgrass (DIGITARIA SANGUINALIS), barnyard grass (Echinochloa crus-galli), perennial ryegrass (Lolium perenne), ryegrass (Lolium multiflorum), millet (Panicum miliaceum), annual bluegrass (Poa annua), green bristlegrass (SETARIA VIRIDIS), green bria faberi, and Sorghum bicolor (Sorghum bicolor). Examples of dicotyledonous species that may be controlled include Abutilon (Abutilon theophrasti), amaranthus retroflexus (Amaranthus retroflexus), bidens pilosa (Bidens pilosa), herba chenopodii (Chenopodium album), lespedeza algorita (Euphorbia heterophylla), galium (Galium aparine), calophyllum Inophyllum (Ipomoea hederacea), kochia scoparia (Kochia scoparia), polygonum multiflorum (Polygonum convolvulus), callicarpa Jin Wushi (Sida spinosa), wild rape (SINAPIS ARVENSIS), solanum nigrum (Solanum nigrum), chickweed (STELLARIA MEDIA), pogostemon (Veronica persica) and Xanthium sibiricum (Xanthium strumarium).

Unwanted plants are understood to include also those weeds which have been rendered tolerant to herbicides or classes of herbicides (e.g. ALS-inhibitor, GS-inhibitor, EPSPS-inhibitor, PPO-inhibitor, accase-inhibitor and HPPD-inhibitor) by evolution, by conventional breeding methods or by genetic engineering. Examples include amaranth (Amaranthus palmeri) which has evolved to have resistance to glyphosate and/or acetolactate synthase (ALS) inhibiting herbicides.

The compounds of the invention may be used in methods of controlling unwanted plants or weeds having resistance to protoporphyrinogen oxidase (PPO) inhibitors. For example, amaranth and amaranth populations have been advanced to be resistant to PPO 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), the codon numbering being based on NCBI reference sequence DQ386114. The compounds of the present invention may be used in methods of controlling amaranthus linearis and/or amaranthus linearis having mutations or deletions at the afore-mentioned codons or equivalents, and it is apparent that attempts are made to use these compounds to control unwanted plants or weeds having other mutations that may occur that confer tolerance or resistance to PPO inhibitors.

The compounds of formula (I) may also be used for pre-harvest drying of crops such as, but not limited to, potato, soybean, sunflower and cotton. Pre-harvest drying is used to dry the crop leaves without significant damage to the crop itself to aid in harvesting.

The compounds/compositions of the present invention are particularly useful for non-selective burnout (burn-down) applications and thus are also useful for controlling self-growing (volunteer) or escaping crop (escape crop) plants.

Synthesis example

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

List of abbreviations

Br s=broad single peak, °c=degrees celsius, d=double peak, m=multiple peak, mhz=megahertz, n=nominal, ppm=parts per million, q=quartet, s=singlet, t=triplet.

Example 1 preparation of (2-ethoxy-2-oxo-ethyl) 1- [ 2-chloro-5- (3, 5-dimethyl-2, 6-dioxo-4-thioxo-1, 3, 5-triazin-1-yl) -4-fluoro-phenoxy ] cyclopropanecarboxylic acid ester (Compound 1-430)

Step 12 Synthesis of chloro-4-fluoro-phenol

Ferric chloride (0.16 g,1 mmol) and N-chlorosuccinimide (614 mg,4.5 mmol) were added to a stirred solution of 4-fluorophenol (500 mg,4.5 mmol) in acetonitrile (10 ml). The resulting mixture was stirred for 13 hours, water and ethyl acetate were added and the phases were separated. The organic phase was washed with water and brine, dried and evaporated to afford 2-chloro-4-fluoro-phenol (650 mg). ¹H NMR(400MHz,CDCl₃ ) Delta 7.05 (m, 1H), 6.9 (m, 2H), 6.05 (br s, 1H) ppm.

Step 2 Synthesis of (2-chloro-4-fluoro-phenyl) ethyl carbonate

Ethyl chloroformate (0.56 ml,5.6 mmol) was added dropwise to a stirred solution of 2-chloro-4-fluoro-phenol (690 mg,4.7 mmol) and triethylamine (0.79 ml,5.6 mmol) in tetrahydrofuran (5 ml) at 0 ℃. The solution was warmed to ambient temperature and stirred for 17 hours, then water and ethyl acetate were added and the phases separated. The organic phase was washed with water and brine, dried and evaporated to afford (2-chloro-4-fluoro-phenyl) carbonate ethyl ester (800 mg). ¹H NMR(400MHz,CDCl₃ ) Delta 7.2 (m, 2H), 7.0 (m, 1H), 4.35 (q, 2H), 1.4 (t, 3H) ppm.

Step 3 Synthesis of (2-chloro-4-fluoro-5-nitro-phenyl) carbonate

Concentrated nitric acid (0.26 ml,5.5 mmol) was slowly added to a stirred mixture of (2-chloro-4-fluoro-phenyl) ethyl carbonate (750 mg,3.4 mmol) and concentrated sulfuric acid (1.7 ml) at 0 ℃ and the resulting mixture was stirred for 2 hours, then poured into ice water. The mixture was filtered and the solid was washed with water and dried to afford (2-chloro-4-fluoro-5-nitro-phenyl) carbonate (800 mg). ¹H NMR(400MHz,CDCl₃ ) Delta 8.05 (d, 1H), 7.45 (d, 1H), 4.4 (q, 2H), 1.44 (t, 3H) ppm.

Step 4 2 Synthesis of chloro-4-fluoro-5-nitro-phenol

Sodium bicarbonate (1.38 g,15.6 mmol) was added to a stirred solution of ethyl (2-chloro-4-fluoro-5-nitro-phenyl) carbonate (540 mg,2.1 mmol) in methanol (12.5 ml) and water (0.6 ml). The resulting mixture was stirred at ambient temperature for 17 hours, then concentrated under reduced pressure and water and ethyl acetate were added, and the phases were separated. The organic phase was washed with water and brine, dried and evaporated to afford 2-chloro-4-fluoro-5-nitro-phenol (380 mg). ¹H NMR(400MHz,CDCl₃ ) Delta 7.75 (d, 1H), 7.35 (d, 1H) ppm (OH was not observed).

Step 54 Synthesis of methyl bromo-2- (2-chloro-4-fluoro-5-nitro-phenoxy) -butyrate

Potassium carbonate (0.7 g,5.1 mmol) and methyl 2, 4-dibromobutyrate (0.41 ml,2.8 mmol) were added to a solution of 2-chloro-4-fluoro-5-nitro-phenol (500 mg,2.6 mmol) in acetonitrile (7.5 ml), and the resulting mixture was stirred at ambient temperature for 22 hours. The mixture was filtered, the solid was washed with acetonitrile and the filtrate evaporated under reduced pressure. The residue was purified by column chromatography to give 4-bromo-2- (2-chloro-4-fluoro-5-nitro-phenoxy) -butyric acid methyl ester as a gum (695mg).¹H NMR(400MHz,CDCl₃)δ7.6(d,1H),7.4(d,1H),5.0(m,1H),3.85(s,3H),3.65(m,2H),2.6(m,2H)ppm.

Step 61 Synthesis of methyl- (2-chloro-4-fluoro-5-nitro-phenoxy) -cyclopropanecarboxylate

Potassium tert-butoxide (230 mg,2 mmol) was added in portions to a stirred solution of methyl 4-bromo-2- (2-chloro-4-fluoro-5-nitro-phenoxy) -butyrate (410 mg,1 mmol) in tetrahydrofuran (8 ml) at-78 ℃. The resulting mixture was stirred at-10 ℃ for 30 minutes, then at ambient temperature for 1 hour. 2N hydrochloric acid was added and the mixture was extracted with ethyl acetate. The organic extract was dried and evaporated under reduced pressure to afford methyl 1- (2-chloro-4-fluoro-5-nitro-phenoxy) -cyclopropanecarboxylate as a gum (330mg).¹H NMR(400MHz,CDCl₃)δ7.65(d,1H),7.4(d,1H),3.75(s,3H),1.75(m,2H),1.45(m,2H)ppm.

Step 71 Synthesis of- (2-chloro-4-fluoro-5-nitro-phenoxy) -cyclopropanecarboxylic acid

A mixture of methyl 1- (2-chloro-4-fluoro-5-nitro-phenoxy) -cyclopropanecarboxylate (170 mg,0.47 mmol), lithium hydroxide hydrate (24 mg,0.56 mmol), water (0.5 ml) was stirred at ambient temperature for 5 hours, then water and ethyl acetate were added and the phases separated. The aqueous phase was acidified by addition of 2N hydrochloric acid, extracted with ethyl acetate, and the organic phase was dried and evaporated to afford 1- (2-chloro-4-fluoro-5-nitro-phenoxy) -cyclopropanecarboxylic acid (85 mg). ¹H NMR(400MHz,CDCl₃ ) Delta 7.75 (d, 1H), 7.4 (d, 1H), 1.8 (m, 2H), 1.5 (m, 2H) ppm (OH is not observed).

Step 8 Synthesis of (2-ethoxy-2-oxo-ethyl) 1- (2-chloro-4-fluoro-5-nitro-phenoxy) -cyclopropanecarboxylate

Potassium carbonate (43 mg,0.3 mmol) was added to a solution of 1- (2-chloro-4-fluoro-5-nitro-phenoxy) -cyclopropanecarboxylic acid (80 mg,0.2 mmol) in acetonitrile (2.4 ml), and the resulting mixture was stirred at ambient temperature for 10 min. Ethyl bromoacetate (0.03 ml,0.3 mmol) was added and the resulting mixture was stirred at ambient temperature for 19 hours. Water was added and the mixture was extracted with ethyl acetate. The organic extracts were dried and evaporated under reduced pressure. The residue was purified by column chromatography to provide (2-ethoxy-2-oxo-ethyl) 1- (2-chloro-4-fluoro-5-nitro-phenoxy) -cyclopropanecarboxylic acid ester as a solid (35mg).¹H NMR(400MHz,CDCl₃)δ7.85(d,1H),7.35(d,1H),4.7(s,2H),4.25(q,2H),1.85(m,2H),1.5(m,2H),1.25(t,3H)ppm.

Step 9 Synthesis of (2-ethoxy-2-oxo-ethyl) 1- (5-amino-2-chloro-4-fluoro-phenoxy) -cyclopropanecarboxylate

Iron (0.56 g,10 mmol) was added to a stirred solution of (2-ethoxy-2-oxo-ethyl) 1- (2-chloro-4-fluoro-5-nitro-phenoxy) -cyclopropanecarboxylic acid ester (1.0 g,2.5 mmol) in ethanol (10 ml) at 60 ℃, and the resulting mixture was stirred at 80 ℃ for 5 minutes. A solution of ammonium chloride (0.53 g,10 mmol) in water (3 ml) was added and the resulting mixture was stirred at 80 ℃ for 2 hours, then allowed to cool to ambient temperature and filtered. The filtrate phases were separated and the aqueous phase was extracted with ethyl acetate. The combined organic phases were dried over sodium sulfate, filtered and evaporated under reduced pressure to afford (2-ethoxy-2-oxo-ethyl) 1- (5-amino-2-chloro-4-fluoro-phenoxy) -cyclopropanecarboxylate (700mg).¹H NMR(400MHz,CDCl₃)δ7.0(d,1H),6.8(d,1H),4.7(s,2H),4.25(q,2H),1.7(m,2H),1.45(m,2H),1.3(t,3H)ppm( as a gum, NH ₂ was not observed.

Step 10 preparation of (2-ethoxy-2-oxo-ethyl) 1- [ 2-chloro-5- (3, 5-dimethyl-2, 6-dioxo-4-thioxo-1, 3, 5-triazin-1-yl) -4-fluoro-phenoxy ] -cyclopropanecarboxylic acid ester (Compound 1-430)

Carbonyl diimidazole (180 mg,1.1 mmol) was added to a stirred solution of (2-ethoxy-2-oxo-ethyl) 1- (5-amino-2-chloro-4-fluoro-phenoxy) -cyclopropanecarboxylic acid ester (200 mg,0.54 mmol) in acetonitrile (3 ml), and the resulting solution was heated at 80 ℃ for 2 hours, then allowed to cool to ambient temperature. 1, 3-Dithiosemicarbazide (69 mg,0.65 mmol) was added and the resulting mixture was heated at 80℃for 10 minutes, followed by carbonyldiimidazole (180 mg,1.1 mmol) and the resulting mixture was heated at 80℃for 3 hours. The mixture was cooled, water was added and the resulting mixture was extracted with ethyl acetate. The combined organic extracts were dried and evaporated under reduced pressure. The residue was purified by column chromatography to give (2-ethoxy-2-oxo-ethyl) 1- [ 2-chloro-5- (3, 5-dimethyl-2, 6-dioxo-4-thioxo-1, 3, 5-triazin-1-yl) -4-fluoro-phenoxy ] -cyclopropanecarboxylic acid ester (compound) 1-430)(65mg).¹H NMR(400MHz,CDCl₃)δ7.3(m,2H),4.65(s,2H),4.15(q,2H),3.75(s,6H),1.7(m,2H),1.45(m,2H),1.25(t,3H)ppm.

Biological example

Biological efficacy before emergence of seedlings

Seeds of the test species were sown in standard soil in pots (amaranthus longus (AMAPA)). After one day of cultivation under controlled conditions in a greenhouse (at 24/19; day/night; 16 hours of light), the plants are sprayed with an aqueous spray solution obtained by formulating the technical grade active ingredient in a small amount of acetone and a special solvent and emulsifier mixture called IF50 (11.12% emulgen EL360 TM +44.44% n-methylpyrrolidone +44.44% DowanolDPM glycol ether) to give a 50g/l solution, which is then diluted with 0.2% Genapol XO80 as diluent to give the desired final dose of test compound.

These test plants were then grown under controlled conditions in the greenhouse (at 24/18 ℃, day/night; 15 hours light; 50% humidity) and watered twice daily. After 13 days, the test was evaluated (100=complete damage to the plants; 0=no damage to the plants). The results are shown in table B1 below.

Table B1 biological efficacy before emergence

Biological efficacy after emergence of seedlings

Seeds of various test species were sown in standard soil in pots (amaranthus longus (AMAPA), chenopodium quinoa (CHEAL), gorilla tabacum (EPHHL), phoenix flowers (IPOHE), (ELEIN), perennial ryegrass (LOLPE), crabgrass (DIGSA), barnyard grass (ECHCG)). After 14 days of cultivation under controlled conditions in a greenhouse (24 ℃ C./19 ℃ C.; day/night; 16 hours of light), the plants are sprayed with an aqueous spray solution obtained by formulating the technical grade active ingredient in a small amount of acetone and a special solvent and emulsifier mixture called IF50 (11.12% Emulson EL 360. TM. +44.44% N-methylpyrrolidone+44.44% Dowanol DPM glycol ether) to give a 50g/l solution, which is then diluted with 0.2% Genapol XO80 as diluent to give the desired final dose of test compound.

These test plants were then grown under controlled conditions in the greenhouse (at 24/18 ℃, day/night; 15 hours light; 50% humidity) and watered twice daily. After 13 days, the test was evaluated (100=complete damage to the plants; 0=no damage to the plants). The results are shown in table B2 below.

Table B2 biological efficacy after emergence of seedlings

Comparative data

"Ready-to-use formulations" (referred to as "IF 50") containing 50g/l of "technical grade" (i.e., unformulated) active ingredient are prepared by dissolving the active ingredient in a mixture of organic solvents and emulsifiers, the details of which are provided in the tables. This IF50 is then mixed with a small variable amount of acetone to aid dissolution, after which a 0.2% v/v aqueous solution of the adjuvant Genapol XO80 is added as an aqueous diluent to form an aqueous spray solution containing a predetermined concentration of the active ingredient, which varies depending on the application rate of the active ingredient to the plant.

Composition of the mixture of organic solvent and emulsifier used as matrix for the ready-to-use formulation:

The aqueous spray solution is then sprayed onto plants (winter wheat (TRZAW), winter barley (HORVW), soybean (Glycine max, GLXMA), maize (ZEAMX), rice (ORYSA), wild oat (AVEFA), barley grass (alome), perennial ryegrass (LOLPE), spanishneedles (BIDPI), green bristlegrass (SETFA), chickweed (stem), belvedere fruit (KCHSC), polygonum multiflorum (POLCO), hedyotis (IPOHE), white bract (EPHHL), barnyard grass (ECHCG), amaranth (AMAPA), amaranth (AMARE), grandma (VERPE), chenopodium (CHEAL), digitaria viridis (DIGSA), elegans (elen)) after one day of cultivation (for pre-emergence) or after about 12 days of cultivation (for post-emergence). Plants were grown from seeds sown in standard soil and placed in a greenhouse under controlled conditions (at 24 ℃ C./18 ℃ C., or 20 ℃ C./16 ℃ C., day/night; 16 hours of light; 65% humidity). After spray application, plants were then grown in the greenhouse under the same conditions and watered twice daily. After 15 days (for post emergence) and 20 days (for pre emergence) the test was evaluated (100=complete damage to the plants; 0=no damage to the plants).

Compound C-1 (CAS number 1101020-13-6) of the prior art is known from US 6,403,534:

TABLE B3 comparative data Pre-emergence crop injury

Table B4 comparative data on biological efficacy after emergence

Claims (15)

1. A compound of formula (I) or an agronomically acceptable salt thereof: in Each of 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 ; D is (CR ⁶ R ⁷ ) _n ; n is an integer from 1 to 4; ^R1 is hydrogen or _C1 - _C6 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 alkoxy; each R ⁶ and R ⁷ is independently selected from 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 ; provided that R ⁶ and R ⁷ are not both hydroxy on the same carbon atom; or Two ^R6 and ^R7 groups on the same or different carbon atoms together with the carbon atom or carbon atoms to which they are attached form a 3- to 6-membered cycloalkyl group containing 0, 1 or 2 oxygen atoms; or Two ^R6 and ^R7 groups on the same or different carbon atoms, together with the carbon atom or carbon atoms to which they are attached, form a 3- to 6-membered cycloalkyl group containing 0, 1 or 2 oxygen atoms, and wherein the resulting 3- to 6-membered cycloalkyl group is substituted with 1 to 3 groups represented by ^R15 ; or Two ^R6 and ^R7 groups on the same carbon atom together with the carbon atom to which they are attached form a _C2 alkene group; R ⁸ is OR ⁹ , SR ⁹ or NR ¹⁰ R ¹¹ ; 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, C ₆ -C ₁₀ aryl C ₁ -C ₃ alkyl substituted by 1 to 4 groups represented by R ¹³ , heteroaryl C ₁ -C ₃ alkyl, or heteroaryl C ₁ -C ₃ alkyl substituted by 1 to 3 groups represented by R ¹³ ; R ¹⁰ is hydrogen, C ₁ -C ₆ alkyl or SO ₂ R ¹⁴ ; R ¹¹ is hydrogen or C ₁ -C ₆ alkyl; or R ¹⁰ and R ¹¹ together with the nitrogen to which they are attached form a 3- to 6-membered heterocyclyl ring, which optionally contains an oxygen atom; R ¹² is hydrogen, C ₁ -C ₄ alkyl or C ₁ -C ₄ alkylcarbonyl; each R ¹³ is independently selected from halogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ haloalkoxy, cyano, and C ₁ -C ₄ alkylsulfonyl; 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 independently selected from hydrogen, halogen, C ₁ -C ₄ alkyl or C ₁ -C ₄ haloalkyl; R ¹⁶ and R ¹⁷ are each independently selected from hydrogen, halogen, C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkyl, C ₁ -C ₄ alkoxy and CH ₂ OR ¹² ; or The two R ¹⁶ and R ¹⁷ groups, together with the carbon to which they are attached, form a 3- to 6-membered cycloalkyl group containing 0, 1 or 2 oxygen atoms; or Two R ¹⁶ and R ¹⁷ groups, together with the carbon to which they are attached, form a 3- to 6-membered cycloalkyl group containing 0, 1, or 2 oxygen atoms, wherein the resulting 3- to 6-membered cycloalkyl group is substituted with 1 to 3 groups represented by R ¹⁵ ; or The two R ¹⁶ and R ¹⁷ groups together with the carbon atom to which they are attached form a C ₂ alkene group. 2. The compound according to claim 1, wherein ^X1 is sulfur, and ^X2 and ^X3 are oxygen. 3. A compound according to claim 1 or claim 2, wherein Y is C-H. The compound according to any one of claims 1 to 3, wherein B is O. The compound according to any one of claims 1 to 4, wherein n is 1. The compound according to any one of claims 1 to 5, wherein R ¹ and R ² are both methyl. 7. The compound according to any one of claims 1 to 6, wherein ^R3 and ^R4 are selected from hydrogen, chlorine and fluorine. 8. The compound according to any one of claims 1 to 7, wherein each ^R6 and ^R7 is independently selected from hydrogen, halogen, _C1 - _C4 alkyl and _C1 - _C4 alkoxycarbonyl. 9. The compound according to any one of claims 1 to 8, wherein the two ^R16 and ^R17 groups together with the carbon to which they are attached form a 3- to 6-membered cycloalkyl group. 10. A herbicidal composition comprising (A) a herbicidally effective amount of (2-ethoxy-2-oxo-ethyl) 1-[2-chloro-5-(3,5-dimethyl-2,6-dioxo-4-thioxo-1,3,5-triazin-1-yl)-4-fluoro-phenoxy]-cyclopropanecarboxylate and (B) at least one herbicide selected from the group consisting of glufosinate, L-glufosinate, glyphosate, 2,4-D, clethodim, clodinafop-propargyl, oxadiazine, chlorpyrifos, chloranil ... Fluazifop-butyl, fluazifop-butyl, fluazifop-butyl, pinoxaden, fluazifop-butyl ... 3-(2-chloro-4-fluoro-5-(3-methyl-2,6-dioxo-4-trifluoromethyl-3,6-dihydropyrimid-1(2H)-yl)phenyl) -5-methyl-4,5-dihydroisoxazole-5-carboxylic acid ethyl ester, 2-[[3-[[3-chloro-5-fluoro-6-[3-methyl-2,6-dioxo-4-(trifluoromethyl)pyrimidin-1-yl]-2-pyridyl]oxy]ethyl acetate, sulfonepyraclostrobin, flupyrazone, S-isopropylamine, mesotrione, metribuzin, clopyralid, dicamba, clopyralid, clopyralid, chlorpyrifos, chlorpyrifos-methyl, triclopyr, paraquat, dimethoate Quad, quinclorac, dioxypyrithione, fenquinoxaline, isoxazolidinone, tampoxolone, fenpyraclostrobin, 3-(isopropylsulfonylmethyl)-N-(5-methyl-1,3,4-oxadiazol-2-yl)-5-(trifluoromethyl)-[1,2,4]triazolo[4,3-a]pyridine-8-carboxamide and 2-fluoro-N-(5-methyl-1,3,4-oxadiazol-2-yl)-3-[(R)-propylsulfinyl]-4-(trifluoromethyl)benzamide. 11. An agrochemical composition comprising a herbicidally effective amount of a compound of formula (I) as defined in any one of claims 1 to 9, or the herbicidal composition according to claim 10, further comprising an agrochemically acceptable diluent or carrier. 12. 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 9, or a composition according to claim 10 or 11, is applied to the plants, parts thereof or the locus thereof. 13. The method according to claim 12, wherein the weeds are PPO-resistant weeds resistant to at least one PPO-inhibiting herbicide other than the compound of formula (I). 14. The method according to claim 13, wherein the PPO-resistant weed has a mutation at amino acid 98, amino acid 210, amino acid 361 and/or amino acid 399 in the gene encoding protoporphyrinogen oxidase. 15. Use of a compound of formula (I) according to any one of claims 1 to 9 or a composition according to claim 10 or 11 in crops tolerant to PPO inhibitor herbicides.