EA040763B1 - SPIROCYCLOHEXANEDIONE DERIVATIVES AS HERBICIDES - Google Patents

Description

(57) The invention relates to compounds of formula (I)

G where R ¹ , R ² , R ³ , R ⁴ and G are defined in this document. The invention further relates to herbicidal compositions which contain a compound of formula (I), to their use for weed control, in particular in agricultural crops of useful plants.

The present invention relates to novel herbicidal cyclohexanedione compounds, processes for their preparation, herbicidal compositions containing the novel compounds, and their use in weed control.

Herbicidal cyclic dione compounds substituted with phenyl which has various substituents are disclosed, for example, in WO 2008/110308. The present invention relates to new herbicidal cyclohexanedione derivatives with improved properties.

Thus, according to the present invention, there is provided a compound of formula (I)

G where R ¹ is selected from methyl, phenyl and 5 - or 6-membered heteroaryl, which contains one or two nitrogen heteroatoms, while the specified phenyl and heteroaryl are optionally substituted with one or two substituents R ¹⁵ ;

R ² is methyl or methoxy;

R ³ is methyl or methoxy;

R ⁴ is selected from the group consisting of C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ haloalkyl, -C(=O)C ₁ -C ₄ alkyl, -C( \u003d O) C ₁ -C ₄ -haloalkyl, -S (O) _n C ₁ -C ₆ -alkyl, -S (O) _n C ₁ -C ₆ -haloalkyl, -S (O) n-(CH2) n -C3-C6-cycloalkyl, -S(O)nC(R ¹¹ )R ¹² R ¹³ , -C(O)H, -C(O)-(CH2)n-C3-C6-cycloalkyl, -C(O )C(R11)R ¹² R ¹³ , -C(O)C2-C4-alkenyl, -C(O)(CR ⁹ R ¹⁰ )CN, -C(O)(CR ⁹ R ¹⁰ )(CR ⁹ R ¹⁰ )CN,

-C(O)CH2C(O)-C1-C6-alkyl, -C(O)CH2OC(O)-C1-C6-alkyl, -C(O)OC1-C6-alkyl, -C(O)OC _g C6 haloalkyl, C (O) (CR ⁹ R ¹⁰ ) _n S (O) _n C 1-C ₆ -alkyl, -C (O) C ₁ -C ₃ -alkoxy-C ₁ -C ₆ -alkyl, -C ( O) C1 -C ₃ -alkoxyC ₂ -C ₆ -alkenyl, -C (O) C ₁ -C ₃ -alkoxy-C ₂ -C ₆ -alkynyl, -C (O) C ₁ -C ₃ -alkoxy-C ₁ -C ₆ -haloalkyl,

-C (O) C ₁ -C ₃ -alkoxy-C ₃ -C ₆ -cycloalkyl, -C (O) OS ₁ -C ₃ -alkoxy-C ₁ -C ₆ -alkyl, -C (O) C ₁ - C ₃ -alkoxy-C ₁ -C ₃ alkoxy-C1-C ₆ -alkyl, -C (O) (CH ₂ ) _n NR ⁵ R ⁶ , -C (O) - (CH2) n-NR ⁷ C (O )R ⁸ , -C(O)-(CH2) _n -ON=CR ⁵ R ⁵ , -CN, -(CH ₂ ) _n -phenyl, -C(O)-(CH ₂ ) _n -phenyl, -S (O) _n -(CH ₂ ) _n -phenyl, -heterocyclyl, -C(O)-(CH ₂ ) _n -heterocyclyl, -C(O)(CH ₂ ) _n O-(CH ₂ ) _n- heterocyclyl, -S(O) _n -(CH ₂ ) _n -heterocyclyl, where each heterocyclyl is a 5- or 6-membered heterocyclyl, which may be aromatic, saturated or partially saturated and may contain from 1 to 4 heteroatoms, each of which is independently is selected from the group consisting of oxygen, nitrogen and sulfur, and wherein said heterocyclyl or phenyl groups are optionally substituted with one, two or three substituents independently selected from the group consisting of C1- _C3 alkyl, C1- _C3 haloalkyl, C1 -C ₃ -alkoxy, C ₂ -C ₃ -alkenyl, C ₂ -C ₃ -alkynyl, halogen, cyano and nitro;

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

R ⁶ is selected from the group consisting of hydrogen, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C1-C6 haloalkyl, hydroxyla-, C1-C6-alkoxy, C3-C6-cycloalkyl, - C1-C4-alkoxy-C1-C6-alkyl, -C1-C3-alkoxy-C1-C6-haloalkyl, -(CR ⁹ R ¹⁰ )C1-C ₆ -haloalkyl, -(CR ⁹ R ¹⁰ )C(O) NR ⁵ R ⁵ , phenyl, -pyridyl, wherein phenyl and pyridyl are optionally substituted with one, two or three substituents independently selected from the group consisting of C1- _C3 alkyl, C1- _C3 haloalkyl, C1- _C3 - alkoxy, C ₂ -C ₃ -alkenyl, C ₂ -C ₃ alkynyl, halogen, cyano and nitro; or

R ⁵ and R ⁶ together form -CH2CH2OCH2CH2-;

R ⁷ is selected from the group consisting of hydrogen and C]-C ₆ alkyl;

R ⁸ is selected from the group consisting of hydrogen, C1-C ₆ -alkyl, C1-C ₆ -alkoxy, C ₃ -C ₆ -cycloalkyl, phenyl, -pyridyl, where phenyl and pyridyl are optionally substituted with one, two or three substituents, independently selected from the group consisting of C1- _C3 alkyl, C1- _{C3 haloalkyl, C1-C3 alkoxy , C2} - _C3 alkenyl, _C2 - _C3 alkynyl, halogen, cyano and nitro ;

R ⁹ is hydrogen or methyl;

R ¹⁰ is hydrogen or methyl or

R ⁹ and R ¹⁰ together form -CH ₂ CH ₂ -;

R ¹¹ is hydrogen or methyl;

R ¹² is selected from the group consisting of hydrogen, C1-C ₆ -alkyl, hydroxyl and C1-C ₆ -alkoxy-;

R ¹³ is selected from the group consisting of hydrogen, C1-C ₆ alkyl, hydroxyl and C1-C ₆ alkoxy; or

R ¹² and R ¹³ together form -CH ₂ -X-CH ₂ -;

X is selected from the group consisting of O, S and NR ¹⁴ ;

R ¹⁴ is selected from the group consisting of hydrogen, C1- _C3 alkyl and C1- _C3 alkoxy;

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

G is selected from the group consisting of hydrogen, -(CH ₂ ) _n -R ^a , -C(O)-R ^a , -C(O)-(CR ^c R ^d )nOR ^b , -C(O)-( CR ^c R ^d )nSR ^b , -C(O)NR ^a R ^a , -S(O)2-R ^a and C1-C ₈ -alkoxy-C ₁ -C ₃ -alkyl-;

R ^a is independently selected from the group consisting of hydrogen, C1-C ₈ alkyl, C1-C ₃ haloalkyl, C ₂ -C ₈ alkenyl, C ₂ -C ₈ alkynyl, C ₃ -C ₆ cycloalkyl, heterocyclyl and phenyl, where said heterocycle

- 1 040763 lyl and phenyl groups are optionally substituted with one, two or three substituents independently selected from the group consisting of C ₁ -C ₃ -alkyl, C ₁ -C ₃ -haloalkyl, C ₁ -C ₃ -alkoxy, C ₂ - C ₃ -alkenyl, C ₂ -C ₃ alkynyl, halogen, cyano and nitro;

R ^b is selected from the group consisting of C ₁ -C ₈ alkyl, C ₁ -C ₃ haloalkyl, C ₂ -C ₈ alkenyl, C ₂ -C ₈ alkynyl, C ₃ -C ₆ cycloalkyl, heterocyclyl, and phenyl, where said heterocyclyl and phenyl groups are optionally substituted with one, two or three substituents independently selected from the group consisting of C ₁ -C ₃ alkyl, C ₁ -C ₃ haloalkyl, C ₁ -C ₃ alkoxy, C ₂ -C ₃ -alkenyl, C ₂ -C ₃ alkynyl, halogen, cyano and nitro;

R ^c represents hydrogen or C ₁ -C ₃ -alkyl;

R ^d is hydrogen or C ₁ -C ₃ alkyl; and n is independently 0, 1 or 2;

or its agriculturally acceptable salt.

Alkyl groups (eg C ₁ -C6 alkyl) include, for example, methyl (Me, CH ₃ ), ethyl (Et, C ₂ H ₅ ), n-propyl (n-Pr), isopropyl (i-Pr), n-butyl (n-Bu), isobutyl (i-Bu), sec-butyl (s-Bu) and tert-butyl (t-Bu).

The alkenyl and alkynyl moieties may be in straight or branched chain form, and the alkenyl moieties may be in either the (E)- or (Z)-configuration, if desired. Examples are vinyl, allyl and propargyl. Alkenyl and alkynyl fragments may contain one or more double and/or triple bonds in any combination.

Halogen (or halo) encompasses fluorine, chlorine, bromine, or iodine. The same applies accordingly to halogen in the context of other definitions such as haloalkyl.

Haloalkyl groups (eg C ₁ -C6 haloalkyl) are, for example, fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, 2,2,2-trifluoroethyl, 2-fluoroethyl, 2-chloroethyl, pentafluoroethyl, 1,1 -difluoro-2,2,2-trichloroethyl, 2,2,3,3-tetrafluoroethyl and 2,2,2-trichloroethyl, heptafluoro-n-propyl and perfluoro-n-hexyl.

Alkoxy groups (eg C ₁ -C ₄ -alkoxy-) are, for example, methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy or tert-butoxy, preferably methoxy and ethoxy.

Alkoxyalkyl groups (eg C ₁ -C ₈ -alkoxy-C ₁ -C ₃ -alkyl-) include, for example, methoxymethyl, methoxyethyl, ethoxymethyl, ethoxyethyl, n-propoxymethyl, n-propoxyethyl, isopropoxymethyl or isopropoxyethyl.

Cycloalkyl groups (for example, C ₃ -C ₆ -cycloalkyl-) include, for example, cyclopropyl (c-propyl, c-Pr), cyclobutyl (c-butyl, c-Bu), cyclopentyl (c-pentyl) and cyclohexyl (c -hexyl) and may be substituted or unsubstituted as indicated.

C ₁ -C6-Alkyl-S-(alkylthio) is, for example, methylthio, ethylthio, propylthio, isopropylthio, n-butylthio, isobutylthio, sec-butylthio or tert-butylthio, preferably methylthio or ethylthio.

C ₁ -C ₆ -Alkyl-S(O)-(alkylsulfinyl) is, for example, methylsulfinyl, ethylsulfinyl, propylsulfinyl, isopropylsulfinyl, n-butylsulfinyl, isobutylsulfinyl, sec-butylsulfinyl or tert-butylsulfinyl, preferably methylsulfinyl or ethylsulfinyl.

C ₁ -C ₆ -Alkyl-S(O) ₂ -(alkylsulfonyl) is, for example, methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, n-butylsulfonyl, isobutylsulfonyl, sec-butylsulfonyl or tert-butylsulfonyl, preferably methylsulfonyl or ethylsulfonyl.

Unless otherwise noted, heterocyclyl is a 5- or 6-membered heterocyclyl which may be aromatic, saturated or partially saturated and may contain from 1 to 4 heteroatoms, each independently selected from the group consisting of oxygen, nitrogen and sulfur .

The present invention also relates to agriculturally acceptable salts of the compounds of formula (I). Such salts include salts that are capable of forming with amines, alkali metal and alkaline earth metal bases, or quaternary ammonium bases. Among the hydroxides of alkali metals and alkaline earth metals, the hydroxides of lithium, sodium, potassium, magnesium and calcium, and in particular the hydroxides of sodium and potassium, should be especially noted as salt formers. The compounds of formula (I) in accordance with the present invention also include hydrates, which may be formed during salt formation.

Examples of amines suitable for the formation of ammonium salts include ammonia, as well as primary, secondary and tertiary C ₁ -C ₁₈ -alkylamines, C ₁ -C ₄ -hydroxyalkylamines and C ₂ -C ₄ -alkoxyalkylamines, for example, methylamine, ethylamine, n- propylamine, isopropylamine, four isomers of butylamine, n-amylamine, isoamylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, pentadecylamine, hexadecylamine, heptadecylamine, octadecylamine, methylethylamine, methylisopropylamine, methylhexylamine, methylnonylamine, methylpentadecylamine, methyloctadecylamine, ethylheptylamine, ethylheptylamine, hexylheptylamine, hexyloctylamine, dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, di-n-amylamine, diisoamylamine, dihexylamine, diheptylamine, dioctylamine, ethanolamine, n-propanolamine, isopropanolamine, K,K-diethanolamine,

- 2 040763

N-ethylpropanolamine, N-butylethanolamine, allylamine, n-but-2-enylamine, n-pent-2-enylamine, 2,3-dimethylbut-2-enylamine, dibut-2-enylamine, n-hex-2-enylamine, propylenediamine, trimethylamine, triethylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, triisobutylamine, tri-sec-butylamine, tri-n-amylamine, methoxyethylamine and ethoxyethylamine; heterocyclic amines such as pyridine, quinoline, isoquinoline, morpholine, piperidine, pyrrolidine, indoline, quinuclidine and azepine; primary arylamines, for example anilines, methoxyanilines, ethoxyanilines, o-, m- and p-toluidines, phenylenediamines, benzidines, naphthylamines and o-, m- and p-chloroanilines; but especially triethylamine, isopropylamine and diisopropylamine.

In one embodiment of the present invention, R ¹ is methyl.

In another embodiment of the present invention, R ¹ is phenyl optionally substituted with one or two R ¹⁵ substituents, for example selected from the group consisting of cyano, chlorine and fluorine.

In another embodiment of the present invention, R ¹ is a 5- or 6-membered heteroaryl which contains one or two nitrogen heteroatoms, wherein said heteroaryl is optionally substituted with one or two R ¹⁵ substituents, for example selected from the group consisting of cyano, chlorine and fluorine. In a preferred embodiment, said heteroaryl is selected from the group consisting of pyridyl, pyrimidinyl and pyrazolyl.

In one embodiment of the present invention, R ² is methyl.

In one embodiment of the present invention, R ³ is methyl.

In another embodiment of the present invention, R ³ is methoxy.

In one embodiment of the present invention, R ² is methyl and R ³ is methyl.

In one embodiment of the present invention, R ² is methyl and R ³ is methoxy.

In one embodiment of the present invention, R ² is methoxy and R ³ is methoxy.

In one embodiment of the present invention, R ⁴ is selected from the group consisting of C1-C4 alkyl, C1-C4 alkoxy, C1-C4 haloalkyl, -C(=O)C1-C4 alkyl, -C(=O )C1-C4-haloalkyl, -S(O)nC1-C6-alkyl, -S(O)nC1-C6-haloalkyl, -S(O)n-(cH2)n-C3-C6-cycloalkyl, -S( O)nC(R ¹¹ )R ¹² R ¹³ , -C(O)H, -C(O)-(CH2)n-C3-C6-Cycloalkyl, -C(O)C(R ¹¹ )R ¹² R ¹³ , -C(O)C2-C4-alkenyl, -C(O)(CR ⁹ R ¹⁰ )CN, -C(o)oC1-C ₆ -alkyl, -C(O)OC ₁ -C ₆ -haloalkyl, -C (O) (CH ₂ ) _n S (O) _n C ₁ -C ₆ -alkyl, -C (O) C ₁ -C ₃ -alkoxy-C ₁ C6-alkyl, -C (O) NR ⁵ R ⁶ , -C(O)-(CH2)n-NR ⁷ C(O)R ⁸ , -CN, -(CH2)n-phenyl, -C(O)-(CH2)n-phenyl,

- S(O) _n -(CH ₂ ) _n -phenyl, -heterocyclyl, -C(O)-(CH ₂ ) _n -heterocyclyl, -S(O) _n -(CH ₂ ) _n -heterocyclyl, where each heterocyclyl is a 5- or 6-membered heterocyclyl which may be aromatic, saturated or partially saturated and may contain from 1 to 4 heteroatoms each independently selected from the group consisting of oxygen, nitrogen and sulfur, and wherein said heterocyclyl or phenyl the groups are optionally substituted with one, two or three substituents independently selected from the group consisting of C ₁ -C ₃ alkyl, C ₁ -C ₃ haloalkyl, C ₁ -C ₃ alkoxy, C ₂ -C ₃ alkenyl, C ₂ -C ₃ alkynyl, halogen, cyano and nitro.

In one embodiment of the present invention, R ⁴ is C ₁ -C ₂ alkoxy (eg, methoxy or ethoxy).

In another embodiment of the present invention, R ⁴ is

- C(=O)C ₁ -C ₃ -alkyl (eg -C(C=O)methyl, -C(C=O)ethyl, -C(C=O)isopropyl).

In another embodiment of the present invention, R ⁴ is

- C(=O)C ₁ -C ₃ haloalkyl, more preferably -C(=O)C ₁ -C ₂ -fluoroalkyl, for example -C(=O)CH ₂ F, -C(=O)CHF2, - C(=O)CF ₃ ).

In one embodiment of the present invention, R ⁴ is -S(O) _n C ₁ -C ₆ -alkyl, in particular -S(O) ₂ -methyl or -S(O) ₂ -ethyl.

In another embodiment, R ⁴ is -S(O) _n C ₁ -C ₆ haloalkyl, eg -S(O) ₂ -chloromethyl.

In another embodiment, R ⁴ is -S(O) _n -(CH ₂ ) _n -C ₃ -C ₆ cycloalkyl, eg -S(O) ₂ -(CH ₂ )-c-propyl.

In another embodiment of the present invention, R ⁴ is

- C(O)OC ₁ -C ₆ -alkyl, in particular -C(O)-O-methyl.

In another embodiment of the present invention, R ⁴ is

- S(O) _n C(R ¹¹ )R ¹² R ¹³ or -C(O)C(R ¹¹ )R ¹² R ¹³ where R ¹¹ is hydrogen or methyl and R ¹² and R ¹³ taken together are -CH ₂ OCH ₂ -(oxetan-3-yl).

In another embodiment of the present invention, R ⁴ is -C(O)-(CH ₂ ) _n -C ₃ -C ₆ -cycloalkyl, for example -C(O)-c-propyl or -C(O)-(CH ₂ )-s-propyl.

In another embodiment of the present invention, R ⁴ is

- C(O)(CR ⁹ R ¹⁰ )CN, for example -C(O)CH2CN, -C(O)CH(CH3)CN or -C(O)C(CH ₃ )2CN.

In another embodiment of the present invention, R ⁴ is

- 3 040763

-C(O)(CH ₂ ) _n S(O) _n C ₁ -C ₆ -alkyl, for example -C(O)CH ₂ S(O) ₂ -methyl.

In another embodiment of the present invention, R ⁴ is -C(O)C ₁ -C ₃ -alkoxy-C ₁ -C ₆ -alkyl, for example -C(O)CH ₂ CH ₂ -O-CH ₃ or -C( 0) CH (CH ₃ ) -0-CH ₃ .

In another embodiment of the present invention, R ⁴ is -C(O)NR ⁵ R ⁶ , in particular where R ⁵ is hydrogen and R ⁶ is C ₁ -C ₆ alkyl, eg tert-butyl.

In another embodiment of the present invention, R ⁴ is -C(O)-(CH2)n-NR ⁷ C(O)R ⁸ , for example -C(O)-(CH2)-NR ⁷ C(O)R ⁸ or -C(O)NR ⁷ C(O)R ⁸ , for example -C(o)NHC(O)-tert-butyl.

In another embodiment of the present invention, R ⁴ is selected from the group consisting of -phenyl, -C(O)-phenyl, -S(O) _n -phenyl, where each phenyl is optionally substituted as previously defined.

In another embodiment of the present invention, R ⁴ is heterocyclyl, -C(O)-heterocyclyl, or -S(O) _n -heterocyclyl. In another embodiment, each of the above heterocyclyl is an aromatic heterocyclyl (i.e., heteroaryl), more preferably selected from the group consisting of furanyl, pyrrolyl, thiophenyl, imidazolyl, pyrazolyl, oxazolyl, isoxazolyl, thiazolyl, pyranyl, pyridyl, pyrazinyl, pyrimidinyl , pyridazinyl and triazolyl, more preferably selected from the group consisting of pyridyl, pyridazinyl, pyrimidinyl and pyrazinyl, each of which is optionally substituted as previously defined. In another embodiment, each of the above heterocyclyl is a partially saturated heterocyclyl, more preferably selected from the group consisting of imidazolinyl, isoxazolinyl and thiazolinyl, each of which is optionally substituted as previously defined. In another embodiment, each of the above heterocyclyl is a saturated heterocyclyl, more preferably selected from the group consisting of morpholinyl, tetrahydrofuryl and tetrahydropyranyl, each of which is optionally substituted as previously defined.

In one embodiment of the present invention, G is selected from the group consisting of hydrogen, C ₁ -C ₈ -alkyl (for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, -C ₂ -C ₈ - alkenyl (eg vinyl), C ₂ -C ₈ alkynyl (eg propargyl), -C(O)C ₁ -C ₈ alkyl (more preferably -C(O)C ₁ -C ₆ alkyl, eg - C(O)-isopropyl and -C(O)-tert-butyl) and -C(O)-O-C ₁ -C ₈ -alkyl (more preferably -C(O)-O-C ₁ -C ₆ - alkyl, eg -C(O)-O-methyl) In a preferred embodiment, G is hydrogen.

Depending on the nature of the substituents, the compounds of formula (I) may exist in various isomeric forms. If G is, for example, hydrogen, the compounds of formula (I) may exist in various tautomeric forms.

The present invention embraces all such isomers and tautomers and mixtures thereof in all proportions. In addition, if the substituents contain double bonds, there may be cis and trans isomers. These isomers are also within the scope of the claimed compounds of formula (I). The compounds of formula (I) may contain asymmetric centers and may be present as a single enantiomer, pairs of enantiomers in any proportion or, if more than one asymmetric center is present, contain diastereoisomers in all possible ratios. As a rule, one of the enantiomers is characterized by increased biological activity compared to other options.

The compounds of formula (I) according to the present invention can be used alone as herbicides, but are usually formulated into herbicidal compositions using formulation aids such as carriers, solvents and surface active agents (SFAs). Thus, the present invention further provides a herbicidal composition comprising a herbicidal compound according to any one of the claims and an agriculturally acceptable formulation aid. The composition may be presented in the form of concentrates which are diluted prior to use, although ready-to-use compositions may also be obtained. Final dilution is usually performed using water, but it can also be performed using liquid fertilizers, micronutrients, biological organisms, oils or solvents instead of water or in addition to water.

Herbicidal compositions generally contain from 0.1 to 99% by weight, in particular from 0.1 to 95% by weight of the compounds of formula (I) and from 1 to 99.9% by weight of a formulation aid, which is preferably includes from 0 to 25% by weight of a surfactant.

Compositions can be selected from a variety of formulation types, many of which are known from the Manual on Development and Use of FAO Specifications for Plant Protection Products, ^5th Edition, 1999. These include sprayable powders (DP), soluble powders (SP), water soluble granules (SG), water dispersible granules (WG), wettable powders (WP), granules (GR) (slow or fast release), soluble concentrates (SL ), oil-miscible fluids (OL), ultra-low volume fluids (UL), emulsifiable concentrates (EC), dispersible concentrates (DC), emulsions (both oil-in-water (EW) and water-in-oil ( EO)), microemulsions

- 4 040763 (ME), suspension concentrates (SC), aerosols, capsule suspensions (CS) and seed treatment formulations. The type of composition chosen will in any event depend on the particular intended use and the physical, chemical and biological properties of the compound of formula (I).

Sprayable powders (DP) can be obtained by mixing a compound of formula (I) with one or more solid diluents (for example, natural clays, kaolin, pyrophyllite, bentonite, alumina, montmorillonite, kieselguhr, chalk, diatomaceous earth, calcium phosphates, calcium and magnesium carbonates , sulfur, lime, fine powders, talc and other organic and inorganic solid carriers) and mechanical grinding of the mixture to a fine powder.

Soluble powders (SP) can be prepared by mixing a compound of formula (I) with one or more water-soluble inorganic salts (such as sodium bicarbonate, sodium carbonate or magnesium sulfate) or with one or more water-soluble organic solids (such as a polysaccharide ) and optionally with one or more wetting agents, one or more dispersing agents, or a mixture of these agents to improve water dispersibility/solubility. The mixture is then ground to a fine powder. Such compositions can also be granulated to form water soluble granules (SG).

Wettable powders (WP) can be prepared by mixing a compound of 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 liquids. . The mixture is then ground to a fine powder. Such compositions can also be granulated to form water-dispersible granules (WG).

Granules (GR) may be formed either by granulating a mixture of a compound of formula (I) and one or more powdery solid diluents or carriers, or from previously formed empty granules by absorbing a compound of formula (I) (or a solution thereof in a suitable vehicle) into a porous granular material (such as pumice, attapulgite clays, fuller's earth, diatomaceous earth, diatomaceous earth or crushed corn cobs) or by adsorption of the compound of formula (I) (or its solution in a suitable medium) on a hard granular material (such as sands, silicates, mineral carbonates , sulfates or phosphates) and drying if necessary. Agents commonly used to facilitate absorption or adsorption include solvents (such as aliphatic and aromatic petroleum solvents, alcohols, ethers, ketones, and esters) and caking agents (such as polyvinyl acetates, polyvinyl alcohols, dextrins, sugars, and vegetable oils). ). One or more other additives (eg, an emulsifying agent, wetting agent, or dispersing agent) may also be included in the granules.

Dispersible concentrates (DC) can be prepared by dissolving a compound of formula (I) in water or an organic solvent such as a ketone, alcohol or glycol ether. These solutions may contain a surfactant (for example, to improve dilution with water or prevent crystallization in the spray tank).

Emulsifiable concentrates (EC) or oil-in-water (EW) emulsions can be prepared by dissolving a compound of formula (I) in an organic solvent (optionally containing one or more wetting agents, one or more emulsifying agents, or a mixture of these agents). Suitable organic solvents for use in the EU include aromatic hydrocarbons (such as alkylbenzenes or alkylnaphthalenes, such as SOLVES SO 100, SOLVESSO 150 and SOLVESSO 200; SOLVESSO being 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), fatty acid dimethylamides (such as C ₈ -C ₁₀ fatty acid dimethylamide), and chlorinated hydrocarbons. The EC product may spontaneously emulsify when added to water to provide an emulsion that is stable enough to allow application by spraying with suitable equipment.

The preparation of EW involves the preparation of a compound of formula (I) either as a liquid (if it is not a liquid at room temperature, it can be melted at an acceptable temperature, typically below 70°C) or in solution (by dissolving it in an appropriate solvent) and then emulsifying the resulting liquid or solution in water containing one or more SFAs with high shear to form an emulsion. Suitable solvents for use in EW include vegetable oils, chlorinated hydrocarbons (such as chlorobenzenes), aromatic solvents (such as alkylbenzenes or alkylnaphthalenes), and other suitable organic solvents that have low water solubility.

Microemulsions (ME) can be prepared by mixing water with a mixture of one or more solvents with one or more SFAs to spontaneously form thermodynamically

- 5 040763 stable isotropic liquid composition. The compound of formula (I) is initially present either in water or in a solvent/SFA mixture. Suitable solvents for use in ME include the solvents described herein above for use in the EU or EW. The ME may be either an oil-in-water or a water-in-oil system (whereby the system may be determined by electrical conductivity measurements) and may be suitable for mixing water-soluble and oil-soluble pesticides in the same formulation. ME is suitable for dilution in water, while it either remains in the form of a microemulsion or forms a conventional oil-in-water emulsion.

Suspension concentrates (SC) may contain aqueous or non-aqueous suspensions of finely divided insoluble solid particles of the compound of formula (I). SC can be obtained by grinding in a ball or bead mill a solid compound of formula (I) in a suitable medium, optionally with one or more dispersants, to obtain a fine suspension of the compound. One or more wetting agents may be included in the composition, and a suspending agent may also be included to reduce the settling rate of the particles. Alternatively, a compound of formula (I) may be dry-milled and added to water containing the agents described herein above to obtain the desired end product.

Aerosol formulations contain a compound of formula (I) and a suitable propellant (eg n-butane). The compound of formula (I) can also be dissolved or dispersed in a suitable medium (eg water or a water-miscible liquid such as n-propanol) to provide compositions for use in non-pressurized manual spray pumps.

Capsule suspensions (CS) can be prepared similarly to the preparation of EW formulations, but with an additional polymerization step to obtain an aqueous dispersion of oil droplets, in which each oil droplet is encapsulated by a polymer shell and contains a compound of formula (I) and optionally its carrier or diluent.

The polymer shell can be obtained either by carrying out an interfacial polycondensation reaction or by using a coacervation procedure. The compositions may provide a controlled release of a compound of formula (I) and may be used for seed treatment. The compound of formula (I) may also be formulated in a biodegradable polymer matrix to provide a slow controlled release of the compound.

The composition may include one or more additives to improve the biological performance of the composition, for example, by improving wetting, retention on surfaces or distribution on surfaces; resistance to being washed off by rain from treated surfaces; or the absorption or mobility of the compound of formula (I). Such additives include surface active agents (SFAs), oil-based spray additives such as certain mineral oils or natural vegetable oils (such as soybean and rapeseed oils), and mixtures thereof with other bioenhancing adjuvants (ingredients that may contribute to the action of the compound of formula (I) or modify this action).

Wetting agents, dispersing agents and emulsifying agents may be SFAs of the cationic, anionic, amphoteric or nonionic type.

Suitable cationic type SFAs include quaternary ammonium compounds (eg, cetyltrimethylammonium bromide), imidazolines, and amine salts.

Suitable anionic SFAs include alkali metal fatty acid salts, salts of aliphatic sulfuric acid monoesters (e.g. sodium lauryl sulfate), salts of sulfonated aromatics (e.g. sodium dodecylbenzenesulfonate, calcium dodecylbenzenesulfonate, butylnaphthalenesulfonate and mixtures of sodium diisopropyl and triisopropylnaphthalenesulfonates), ethersulfates, ethersulfates alcohols (e.g. sodium laureth-3-sulphate), ether carboxylates (e.g. sodium laureth-3-carboxylate), phosphoric acid esters (reaction products between one or more fatty alcohols and phosphoric acid (predominantly monoesters) or phosphorus pentoxide (predominantly diesters), for example, in the reaction between lauryl alcohol and tetraphosphoric acid; in addition, these products can be ethoxylated), sulfosuccinamates, paraffin or olefin sulfonates, taurates and lignosulfonates.

Suitable amphoteric type SFAs include betaines, propionates and glycinates.

Suitable SFAs of the nonionic type include condensates 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 alkylphenols (such as octylphenol, nonylphenol or octylcresol); partial esters derived from long chain fatty acids or hexitol anhydrides; condensation products of said partial esters with ethylene oxide; block copolymers (containing ethylene oxide and propylene oxide); alkanolamides; esters with a simple structure (for example, fatty acid esters and polyethylene glycol); amine oxides (eg lauryl dimethylamine oxide) and lecithins.

Suitable suspending agents include hydrophilic colloids (such as polysaccharides

- 6 040763 dy, polyvinylpyrrolidone or sodium carboxymethyl cellulose) and swelling clays (such as bentonite or attapulgite).

The composition of the present invention may further contain at least one additional pesticide. For example, the compounds of the present invention may also be used in combination with other herbicides or plant growth regulators. In a preferred embodiment, the additional pesticide is a herbicide and/or herbicide safener. Examples of such mixtures (in which I is a compound of formula (I)) are: I + acetochlor, I + acifluorfen, I + acifluorfen sodium, I + aclonifen, I + acrolein, I + alachlor, I + alloxydim, I + ametrin, I + amicarbazone, I + amidosulfuron, I + amidosulfuron, I + aminopyralid, I + amitrol, I + anilofos, I + asulam, I + atrazine, I + azaphenidine, I + azimsulfuron, I + BCRS, I + beflubutamide, I + benazoline, I + bencarbazone, I + benfluralin, I + benfuresate, I + bensulfuron, I + bensulfuron-methyl, I + bensulide, I + bentazone, I + benzfendison, I + benzobicyclone, I + benzofenap, I + bicyclopyrone, I + bifenox, I + bilanaphos, I + bispyribac, I + bispyribac sodium, I + borax, I + bromacyl, I + bromobutide, I + bromoxynil, I + butachlor, I + butamiphos, I + butralin, I + butroxydim, I + butylate, I + cacodylic acid, I + calcium chlorate, I + cafenstrol, I + carbetamide, I + carfentrazone, I + carfentrazone-ethyl, I + chlorflurenol, I + chloroflurenol-methyl, I + chloridazone, I + chlorimuron, I + chlorim damage-ethyl, I + chloroacetic acid, I + chlorotoluron, I + chlorprofam, I + chlorsulfuron, I + chlorthal, I + chlorthal-dimethyl, I + cynidone-ethyl, I + cinmethylin, I + cinosulfuron, I + cisanilide, I + cletodim, I + clodinafop, I + clodinafop-propargyl, I + clomazone, I + clomeprop, I + clopyralide, I + cloransulam, I + cloransulam-methyl, I + cyanazine, I + cycloate, I + cyclopyranil, I + cyclosulfamurone , I + cycloxidim, I + cyhalofop, I + cyhalofop-butyl, I + 2,4-D, I + daimuron, I + dalapon, I + dazomet, I + 2,4-DB, I + I + desmedifam, I + dicamba, I + dichlobenil, I + dichlorprop, I + dichlorprop-R, I + diclofop, I + diclofop-methyl, I + diclosulam, I + diphenzoquat, I + diphenzoquat methyl sulfate, I + diflufenican, I + diflufenzopyr, I + dimefuron, I + dimepiperate, I + dimethachlor, I + dimethamethrin, I + dimethenamid, I + dimethenamid-P, I + dimethipine, I + dimethylarsinic acid, I + dinitramine, I + dinoterb, I + diphenamide, I + dipropetrin, I + diquat, I + diquat dibromide, I + dithiopyr, I + diuron, I + Endothal, I + EPTC, I + Esprocarb, I + Etalfluralin, I + Etametsulfuron, I + Etametsulfuron-methyl, I + Ethephon, I + Ethofumesate, I + Ethoxifen, I + Ethoxysulfuron, I + Etobenzanide, I + Fenoxaprop- P, I + fenoxaprop-P-ethyl, I + fenquinotrion, I + fentrazamide, I + ferrous sulfate, I + flamprop-M, I + flazasulfuron, I + florpyrauxifen, I + florasulam, I + fluazifop, I + fluazifop-butyl , I + fluazifop-P, I + fluazifop-P-butyl, I + fluazolate, I + flucarbazone, I + flucarbazone sodium, I + flusetosulfuron, I + fluchloralin, I + fluphenacet, I + flufenpyr, I + flufenpyr-ethyl , I + flumetraline, I + flumetsulam, I + flumiclorac, I + flumiclorac-pentyl, I + flumioxazine, I + flumipropine, I + fluometuron, I + fluoroglycofen, I + fluoroglycofen-ethyl, I + fluoxaprop, I + flupoxam, I + flupropacil, I + flupropanate, I + flupyrsulfuron, I + flupyrsulfuron-methyl-sodium, I + flurenol, I + fluridone, I + flurochloridone, I + fluroxypyr, I + flurtamone, I + flutiacet, I + flutiacet-methyl, I + fomesafe n, I + foramsulfuron, I + fosamine, I + glufosinate, I + ammonium glufosinate, I + glyphosate, I + galauxifen, I + halosulfuron, I + halosulfuron-methyl, I + haloxyfop, I + haloxyfop-R, I + hexazinon, I + imazamethabenz, I + imazametabenz-methyl, I + imazamox, I + imazapic, I + imazapir, I + imazaquin, I + imazetapir, I + imazosulfuron, I + indanophane, I + indaziflam, I + iodomethane, I + iodosulfuron, I + iodosulfuron-methyl-sodium, I + ioxynil, I + isoproturon, I + isouron, I + isoxaben, I + isoxachlorotol, I + isoxaflutol, I + isoxapyrifop, I + carbutylate, I + lactofen, I + lenacil, I + linuron, I + mecoprop, I + mecoprop-R, I + mefenacet, I + mefluidide, I + mesosulfuron, I + mesosulfuron-methyl, I + mesotrione, I + metam, I + methamifop, I + metamitron, I + metazachlor, I + metabenzthiazuron, I + methazol, I + methylarsonic acid, I + methyldymron, I + methylisothiocyanate, I + metolachlor, I + S-metolachlor, I + methosulam, I + methoxuron, I + metribuzin, I + metsulfuron, I + metsulfuro n-methyl, I + molinate, I + monolinuron, I + naproanilide, I + napropamide, I + napropamide-M, I + naptalam, I + neburon, I + nicosulfuron, I + n-methylglyphosate, I + nonanoic acid, I + norflurazon, I + oleic acid (fatty acids), I + orbencarb, I + orthosulfamuron, I + oryzalin, I + oxadiargyl, I + oxadiazon, I + oxasulfuron, I + oxaziclomefon, I + oxyfluorfen, I + paraquat, I + paraquat dichloride, I + pebulate, I + pendimethalin, I + penoxulam, I + pentachlorophenol, I + pentanochlor, I + pentoxazone, I + petoxamide, I + phenmedifam, I + picloram, I + picolinafen, I + pinoxaden, I + piperophos , I + pretilachlor, I + primisulfuron, I + primisulfuron-methyl, I + prodiamine, I + profoxidim, I + prohexadione-calcium, I + promethone, I + promethrin, I + propachlor, I + propanil, I + propaquizafop, I + propazine, I + profam, I + propisochlor, I + propoxycarbazone, I + propoxycarbazone sodium, I + propizamide, I + prosulfocarb, I + prosulfuron, I + pyraclonil, I + pyraflufen, I + pyraflufen -ethyl, I + pyrasulfotol, I + pyrazolinate, I + pyrazosulfuron, I + pyrazosulfuron-ethyl, I + pyrazoxifene, I + pyribenzoxime, I + pyributicarb, I + pyridafol, I + pyridate, I + pyrifthalide, I + pyriminobac, I + pyriminobac-methyl, I + pyrimisulfan,

- 7 040763

I + pyrithiobac, I + pyrithiobac sodium, I + pyroxasulfone, I + pyroxulam, I + quinclorac, I + quinmerac, I + quinoclamin, I + quizalofop, I + quizalofop-P, I + rimsulfuron, I + saflufenacil, I + setoxydim, I + sidurone, I + simazine, I + simetrin, I + sodium chlorate, I + sulcotrione, I + sulfentrazone, I + sulfometuron, I + sulfometuron-methyl, I + sulfosate, I + sulfosulfuron, I + sulfuric acid, I + tebuthiuron, I + tefuryltrione, I + tembotrione, I + tepraloxydim, I + terbacil, I + terbumetone, I + terbutylazine, I + terbutrin, I + tenylchlor, I + thiazopyr, I + thifensulfuron, I + thiencarbazone, I + thifensulfuron-methyl, I + thiobencarb, I + tolpyralate, I + topramesone, I + tralkoxydim, I + triallate, I + triasulfuron, I + triaziflam, I + tribenuron, I + tribenuron-methyl, I + triclopyr, I + trietazine, I + trifloxysulfuron, I + trifloxysulfuron-sodium, I + trifludimoxazine, I + trifluralin, I + triflusulfuron, I + triflusulfuron-methyl, I + trihydroxytriazine, I + trinexapak-ethyl, I + tritosulfuron, I + ethyl ester [3-[2-chloro-4-fluoro-5-(1-methyl-6-trifluoromethyl-2,4-dioxo-1,2,3,4tetrahydropyrimidin-3-yl) phenoxy]-2-pyridyloxy]acetic acid (CAS RN 353292-31-6).

The compounds of the present invention can also be combined with the herbicidal compounds disclosed in WO 06/024820 and/or WO 07/096576.

Miscible components for the compound of formula (I) may also be in the form of esters or salts, as mentioned, for example, in The Pesticide Manual, Sixteenth Edition, British Crop Protection Council, 2012.

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

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

Mixtures can advantageously be used in the formulations mentioned above (in which case the active ingredient refers to an appropriate mixture of a compound of formula (I) with the component to be mixed).

The compounds of formula (I) according to the present invention may also be used in combination with one or more safeners. Similarly, mixtures of a compound of formula (I) according to the present invention with one or more additional herbicides can also be used in combination with one or more safeners. Antidotes can be AD 67 (MON 4660), benoxacor, cloquintoset-mexil, cyprosulfamide (CASRN 221667-31-8), dichlormide, fenchlorazole-ethyl, fenclorim, fluxofenim, furilazole and the corresponding R-isomer, isoxadifenethyl, mefenpyr-diethyl, oxabethrinyl , N-isopropyl-4-(2-methoxybenzoylsulfamoyl)benzamide (CAS RN 221668-34-4). Other options include safener compounds as disclosed in EP 0365484, for example N-(2-methoxybenzoyl)-4-[(methylaminocarbonyl)amino]benzenesulfonamide. Especially preferred are mixtures of a compound of formula (I) with cyprosulfamide, isoxadifenethyl, cloquintoset-mexyl and/or N-(2-methoxybenzoyl)-4-[(methylaminocarbonyl)amino]benzenesulfonamide.

Antidotes for a compound of formula (I) may also be in the form of esters or salts, as mentioned, for example, in The Pesticide Manual, ^16th Edition (BCPC), 2012. Reference to cloquintoset-mexil also refers to its salt with lithium, sodium , potassium, calcium, magnesium, aluminium, iron, ammonium, quaternary ammonium, sulfonium or phosphonium as disclosed in WO 02/34048, and the reference to fenchlorazole-ethyl also refers to fenchlorazole, etc.

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

Mixtures can advantageously be used in the aforementioned formulations (in which case the expression active ingredient refers to the appropriate mixture of a compound of formula (I) with an antidote).

In addition, the present invention further provides a method for controlling weeds in a locus where crop plants and weeds grow, the method comprising applying to the locus an amount of a composition according to the present invention sufficient to control weeds. Control means the destruction, reduction or retardation of growth or the prevention or reduction of germination. Typically, the plants to be controlled are unwanted plants (weeds). Place of growth means the area in which plants grow or will grow.

The application rates of the compounds of formula (I) may vary widely and depend on the nature of the soil, the method of application (before or after emergence of seedlings; seed dressing; application in a seed furrow; no-tillage application, etc.), cultivated plant, the weed(s) to be controlled, the prevailing climatic conditions and other factors determined by the method of application, the time of application and the target crop. The compounds of formula (I) according to the present invention are generally used at a rate of 10 to 2000 g/ha, in particular 50 to 1000 g/ha.

The application is usually carried out by spraying the composition, usually by means of

- 8 040763 tractor-mounted sprayer for large areas, but other methods such as dusting (for powders), drip irrigation or irrigation can also be used.

Useful plants to which the composition of the present invention may be applied include crops such as cereals such as barley and wheat, cotton, oilseed rape, sunflower, maize, rice, soybean varieties, sugar beet, sugar cane and sod cover.

Crop plants may also include trees such as fruit trees, palm trees, coconut trees or other nut crops. Also included are climbing plants such as vines, fruit bushes, orchards and vegetable crops.

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

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

It should also be understood that crops include those obtained by traditional breeding or genetic engineering methods and possessing so-called added traits (eg, improved storage stability, higher nutritional value, and improved taste).

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

The compositions can be used to control unwanted plants (generally weeds). The weeds to be controlled can be either monocotyledonous species such as Agrostis, Alopecurus, Avena, Brachiaria, Bromus, Cenchrus, Cyperus, Digitaria, Echinochloa, Eleusine, Lolium, Monochoria, Rottboellia, Sagittaria, Scirpus, Setaria and Sorghum, or dicot species such as Abutilon, Amaranthus, Ambrosia, Chenopodium, Chrysanthemum, Conyza, Galium, Ipomoea, Nasturtium, Sida, Sinapis, Solarium, Stellaria, Veronica, Viola and Xanthium. The compounds of the present invention have been shown to have particularly good activity against certain types of grassy weeds, in particular Lolium Perenne. Weeds can also include plants that can be considered crop plants but that grow outside of the cultivated area (runaways), or that grow from seeds left over from a previous planting of another crop (self-sowing plants). Such self-seeding or runaway plants may be tolerant of certain other herbicides.

Compounds of the present invention can be obtained in accordance with the following schemes.

Compounds of formula (I) wherein G is other than hydrogen can be prepared by treating a compound of formula (I) wherein G is hydrogen with a G-Z reagent, where G-Z is an alkylating agent such as an alkyl halide, an acylating agent such as an acid chloride, or an acid anhydride, a sulfonylating agent such as sulfonyl chloride, a carbaming agent such as carbamoyl chloride, or a carbonizing agent such as chloroformate using known methods.

Scheme 1

yourself N)

Compounds of formula (I) can be prepared by reacting an iodonium ylide of formula (A), where Ar is an optionally substituted phenyl group, and an arylboronic acid of formula (B) in the presence of a suitable palladium catalyst, base and in a suitable solvent.

Scheme 2

(A) (B) ^G (l,G=H)

Suitable palladium catalysts are typically palladium(H) or palladium(0) complexes, e.g. palladium(H) dihalides, palladium(H) acetate, palladium(H) sulfate, bis-(triphenylphosphine)palladium(P) dichloride, bis-(tricyclopentylphosphine)palladium(P) dichloride, bis-(tricyclohexylphosphine)palladium(P) dichloride, bis-(dibenzylideneacetone)palladium(0) or tetrakis(triphenylphosphine)palladium(0). The palladium catalyst can also be prepared in situ from palladium(P) or palladium(0) compounds by complexing with the desired ligands, for example by combining a palladium(P) salt to be complexed, such as palladium(P) dichloride (PdCl ₂ ) or palladium(II) acetate (Pd(OAc)2 ₎ , together with the necessary ligand, e.g. ,4',6'-triisopropylbiphenyl, and a solvent of choice, with a compound of formula (N), an arylboronic acid of formula (O) and a base. Also suitable are bidentate ligands, for example 1,1'-bis-(diphenylphosphino)ferrocene or 1,2-bis-(diphenylphosphino)ethane. By heating the reaction medium, the palladium(II) complex or palladium(0) complex required for the C-C coupling reaction is thus formed in situ and then initiates the C-C coupling reaction.

Palladium catalysts are used in an amount of from 0.001 to 50 mol.%, preferably in an amount of from 0.1 to 15 mol.%, based on the compound of formula (N). The reaction can also be carried out in the presence of other additives such as tetraalkyl ammonium salts, for example tetrabutylammonium bromide. Preferably, the palladium catalyst is palladium acetate, the base is lithium hydroxide, and the solvent is aqueous 1,2-dimethoxyethane.

A compound of formula (A) can be prepared from a 1,3-dione compound of formula (C) by treatment with a hypervalent iodine reagent such as (diacetoxy)iodobenzene or iodosylbenzene and a base such as aqueous sodium carbonate, lithium hydroxide or sodium hydroxide , in a solvent such as water or an aqueous alcohol solution such as an aqueous ethanol solution using known procedures.

Scheme 3

Alternatively, the R ¹ group may be added later in the synthetic sequence via a Suzuki or Stille coupling reaction to the appropriate boronic acid or stannan, respectively, as in Step 2 below, Scheme 4a, or iridium-catalyzed borylation of an E2-type intermediate may provide a boronate which, after a Suzuki coupling may provide Type I compounds, Scheme 4b, or the halogen in compound E may be converted to a boronate, and then a Suzuki coupling may provide a product, Scheme 4c.

Alternatively, copper-catalyzed coupling of pyrazole with type E intermediates can provide compounds where R ¹ is an appropriately substituted pyrazole.

- 10 040763

Scheme 4a

Scheme 4b

Scheme 4c

Boronic acids can be prepared using methods such as those in Scheme 5 below. For example, a compound of formula (B) or (D) can be prepared from an aryl halide of formula (F) or (H) using known methods. For example, an aryl halide of formula (F) or (H) may be treated with an alkyllithium or alkylmagnesium halide in a suitable solvent, preferably diethyl ether or tetrahydrofuran, at -80 to 30°C, and the resulting arylmagnesium or aryllithium reagent may then be introduced into reaction with a trialkyl borate (preferably trimethyl borate) to give an aryl dialkyl boronate which can be hydrolysed to give a boronic acid of formula (B) or (D) under acidic conditions.

Scheme 5

Compounds of formula (I) can also be prepared by coupling with Pb as shown in the scheme below by reacting a compound of formula (D) to form an organolead reagent of formula (J) and then reacting with 1,3-dione (C) in conditions described, for example, in J. Pinhey, Pure and Appl. Chem., (1996), 68(4), 819 and in M. Moloney et al., Tetrahedron Lett., (2002), 43, 3407. Suitable triaryl bismuth compounds under the conditions described, for example, in A. Yu. Fedorov and

- 11 040763 al., Russ. Chem. Bull. Int. Ed., (2005), 54(11), 2602, and in P. Koech and M. Krische, J. Am. Chem. soc. (2004), 126(17), 5350 and references therein, may be used as related procedures.

Scheme 6

Type (I) compounds can also be prepared by a palladium coupling reaction as shown in the scheme below, where type (B) boronic acid is coupled to a suitably protected type (K) haloalkene in a Suzuki type coupling reaction.

Scheme 7

Under suitable conditions, a suitable 1,3-dione can also be coupled directly to a halogen-containing compound (eg formula (L)) in palladium catalysis. Arylation of intermediate (M) as previously described provides compounds of type (I). Alternatively, the L1 type compound can be coupled, borylated as previously described, and coupled again to give the desired product, Scheme 8b.

Scheme 8a

Diagram 8b

A compound of formula (I, G=H) can be prepared by cyclization of a compound of formula (N) where R is hydrogen or an alkyl group, preferably in the presence of an acid or base, and optionally in the presence of a suitable solvent, using methods analogous to those described in T Wheeler, US 4209532 Compounds of formula (N) have been particularly developed as intermediates in the synthesis of compounds of formula (I). A compound of formula (N) wherein R is hydrogen may be cyclized under acidic conditions, preferably in the presence of a strong acid such as sulfuric acid, polyphosphoric acid or Eaton's reagent, optionally in the presence of a suitable solvent such as acetic acid, toluene or dichloromethane. .

- 12 040763

Scheme 9

Compounds of type (I) can also be obtained by functionalization at a later stage using a suitable protecting group, as shown in the scheme below. Compound (Q) can be converted to intermediate (R) using the methods described, and then the protecting group (such as the BOC group shown) can be removed (under acidic conditions in this example). The intermediate (S) can then be directly converted to compounds (eg (U)) or subjected to a double reaction at both oxygen and nitrogen atoms to give compounds of type (T). Compounds of type (T) can be easily converted to any compound of type (I) - for example, an enol ester (T) can be selectively hydrolyzed to give a compound (U where G=H) which can then be converted to a compound (U where G is other than H) using the methods described previously.

Scheme 10

Alternatively, the sequence may be performed by sulfonylation rather than acylation, as is known to those skilled in the art.

Scheme 11

Ureas, acylureas, N-heteroaryl compounds, and N-cyano compounds can be prepared from intermediate (S), also by standard methods known in the literature to those skilled in the art, such as in Scheme 12.

Scheme 12

(a) 2-isocyanato-2-methylpropane, NEt ₃ , DCM;

(b) 2,2-dimethylpropanoylisocyanate, NEt ₃ , DCM;

(c) 2-fluoropyrimidine, NEt ₃ , DMSO, 180°C, microwave;

(d) cyanogen bromide, DIPEA, DCM.

1,3-Diones such as data can be produced using methods, such as methods, as long as

- 13 040763 listed below. Thus, commercially available ketones (e.g., type (V)) can be converted to intermediate (Y) and then converted to intermediate (Z), and finally decarboxylation provides intermediate (Q) (these methods are described in WO 2008/110308).

Scheme 13

The following non-limiting examples provide specific synthesis methods for exemplary compounds of the present invention listed in table. 1 and 2.

Example 1 Synthesis of 9-[4-(5-Fluoropyrimidin-2-yl)-2,6-dimethylphenyl]-3-methoxy-3-azaspiro[5.5]undecane-8,10-dione (compound A2)

Stage 1. Synthesis of 1-(1-methoxy-4-piperidylidene)propan-2-one o

To a stirred solution of KOH (30.4 g, 542 mmol) in ethanol (440.0 ml) and water (115.0 ml) was added 1-dimethoxyphosphorylpropan-2-one (75.0 ml , 542 mmol). 1-Methoxypiperidin-4-one (50.0 g, 387 mmol) was then added portionwise while maintaining a constant internal temperature. The reaction mixture was stirred at room temperature overnight. Most of the solvent was evaporated under reduced pressure. The residue was diluted with DCM and water and the aqueous layer was extracted twice with DCM. The combined organic layers were washed with brine, dried over Na ₂ SO ₄ , filtered and evaporated under reduced pressure to give a crude residue which was subjected to flash column chromatography to give 1-(1-methoxy-4-piperidylidene)propan-2-one ( 60 g).

¹ H NMR (CDCl ₃ ) δ 6.02 (s, 1H), 3.53 (s, 3H), 3.44-3.16 (m, 3H), 2.69-2.62 (m, 3H ), 2.36-2.35 (m, 2H), 2.17 (s, 3H).

Stage 2. Synthesis of ethyl 3-methoxy-8,10-dioxo-3-azaspiro[5.5]undecane-11-carboxylate

O

To a stirred solution of 1-(1-methoxy-4-piperidylidene)propan-2-one (20.0 g, 118 mmol) in dry ethanol (164.0 ml) was added diethyl propanedioate (18.0 ml, 118 mmol) at room temperature. temperature followed by the dropwise addition of sodium ethoxide (21.0%, 49.8 g, 275 ml, 154 mmol). The reaction mixture was stirred at room temperature for 3h, then refluxed for 2h, then kept at room temperature overnight. The solvent was then evaporated off under reduced pressure, the crude product was diluted with water and washed with ethyl acetate. The aqueous layer was then acidified with aqueous citric acid (10%), saturated with solid NaCl and extracted with ethyl acetate. The combined organic layers were washed with brine and dried over Na ₂ SO ₄ , filtered, concentrated to give a crude residue which was triturated with n-hexane, decanted and the resulting residue was dried to give a brown gum which was carried crude to the next step.

Stage 3. Synthesis of 3-methoxy-3-azaspiro[5.5]undecane-8,10-dione

Ethyl 3-methoxy-8,10-dioxo-3-azaspiro[5.5]undecane-11-carboxylate (27.8 g, 98.1 mmol) was taken up in ethanol (70.0 ml). Sodium hydroxide (12.0 M, 140 ml, 1685 mol) was added at room temperature and the reaction mixture was stirred at room temperature over the weekend. The reaction mixture was then evaporated and acidified with 10% citric acid solution at 0°C to pH 5-6, washed with saturated NaCl solution, extracted several times with ethyl acetate. The combined organic layers were washed with brine and dried over Na ₂ SO ₄ , filtered, concentrated to give a brown sticky solid. It was triturated with n-hexane, after decantation of the hexane, the resulting solid was dried under reduced pressure.

- 14 040763 to give 3-methoxy-3-azaspiro[5.5]undecan-8,10-dione as a light brown solid (16 g).

1H NMR (DMSO-D6) δ 11.06 (bs, 1H), 5.17 (s, 1H), 3.39 (s, 3H), 3.05 (bs, 4H), 2.31-2, 13 (m, 4H), 1.63 (bs, 2H), 1.40 (bs, 2H).

Stage 4. Synthesis of 9-(4-bromo-2,6-dimethylphenyl)-3-methoxy-3-azaspiro[5.5]undecane-8,10-dione

4-dimethylaminopyridine (21.3 g, 174 mmol). The reaction mixture was stirred for 15 min at room temperature, then toluene (99.0 mL) was added followed by [diacetoxy-(4-bromo-2,6-dimethylphenyl)plumbyl]acetate (19.8 g, 34.8 mmol ) in chloroform (130 ml). The reaction mixture was stirred at 80°C for 3 h and then left to settle overnight at room temperature. The reaction mixture was acidified with 10% citric acid and the mixture was filtered through celite. Celite was washed with chloroform and the aqueous layer was extracted twice with chloroform. The combined organic layers were washed with brine, dried over Na ₂ SO ₄ , filtered and evaporated to give a brown gum. This was purified by flash column chromatography to give 9-(4-bromo-2,6-dimethylphenyl)-3methoxy-3-azaspiro[5.5]undecane-8,10-dione as a white solid (7.5 g) .

¹ H NMR (DMSO-D6): δ 10.53 (bs, 1H), 7.18 (s, 2H), 3.41 (s, 3H), 3.11-3.02 (m, 2H), 2.67 (m, 2H), 2.332.28 (m, 4H), 1.95 (s, 6H), 1.79 (bs, 2H), 1.50 (bs, 2H).

Stage 5. Synthesis of 9-[2,6-dimethyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl]-3-methoxy3-azaspiro[5.5]undecane -8,10-dione

9-(4-Bromo-2,6-dimethylphenyl)-8-hydroxy-3-methoxy-3-azaspiro[5.5]undec-8-en-10-one (1.00 g, 2.54 mmol) was combined with 4,4,5,5-tetramethyl-2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1,3,2dioxaborolan (1.93 g, 7.61 mmol), potassium acetate (0.747 g, 7.61 mmol), Pd ₂ dba ₃ (0.232 g, 0.254 mmol) and S-Phos ligand (0.208 g, 0.507 mmol) in 1,4-dioxane (20 ml). The mixture was degassed by stirring with nitrogen bubbling for 15 min, then heated in an oil bath at 120° C. for 4 h. Workup and purification by flash column chromatography gave 9-[2,6-dimethyl-4-(4 ,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl]-3-methoxy-3-zaspiro[5.5]undecane-8,10-dione (LC-MS: M+H= 442).

Stage 6. Synthesis of 9-[4-(5-fluoropyrimidin-2-yl)-2,6-dimethylphenyl]-3-methoxy-3-azaspiro[5.5]undecan-8,10-dione (compound A2)

9-[2,6-Dimethyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl]-3-methoxy-3-azaspiro[5.5]undecan-8 ,10-dione (3.60 g, 6.48 mmol), 2-bromo-5-fluoropyrimidine (1.15 g, 6.48 mmol), PdCl ₂ (dppf)-DCM (1.06 g, 1, 30 mmol) and K ₃ PO ₄ (5.50 g, 25.9 mmol) were taken up in 1,2-dimethoxyethane (50.0 ml). Water (25.0 ml) was then added. The solution was degassed with nitrogen for 30 minutes. The reaction mixture was refluxed at 100° C. for 3 hours. The reaction mixture was filtered and evaporated to give a crude residue, which was purified by flash column chromatography, followed by trituration and metal removal (propanethiol resin on silicon support) to give 9 -[4-(5-Fluoropyrimidin-2-yl)-2,6-dimethylphenyl]-3-methoxy-3-azaspiro[5.5]undecan-8,10-dione as a white solid.

1H NMR (400 MHz, methanol-0 ₄ ) δ 8.77-8.68 (m, 2H), 8.07-8.00 (m, 2H), 3.56-3.46 (m, 3H) , 3.25-3.11 (m, 2H), 2.77-2.60 (m, 4H), 2.57-2.39 (m, 2H), 2.17-2.08 (m, 6H), 2.04-1.92 (m, 2H), 1.75-1.58 (m, 2H).

Example 2 Synthesis of 3-acetyl-9-[4-(5-fluoropyrimidin-2-yl)-2,6-dimethylphenyl]-3-azaspiro[5.5]undecane-8,10-dione (compound A13)

Stage 1. Synthesis of О ³ -tert-butyl-О ¹¹ -ethyl-8,10-dioxo-3-azaspiro[5.5]undecan-3,11-dicarboxylate

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tert-Butyl-4-acetonylidene-piperidine-1-carboxylate (12.9 g, 54.0 mmol) was dissolved in ethanol (100 ml) and diethyl propanedioate (54.12 mmol) was added. The reaction mixture was treated with a solution of sodium ethoxide, which was obtained by adding sodium (54.1 mmol) in ethanol (30 ml) at room temperature. The reaction mixture was stirred at room temperature for 3 h, then heated under reflux for 1 h. After cooling, the reaction mixture was concentrated in vacuo to give O ³ -tert-butyl-O ¹¹ -ethyl-8,10-dioxo-3- azaspiro[5.5]undecan-3,11dicarboxylate as an oil, which was used in the next step without further purification.

Stage 2. Synthesis of tert-butyl-8,10-dioxo-3-azaspiro[5.5]undecane-3-carboxylate

The crude O ³ -tert-butyl-O ¹¹ -ethyl-8,10-dioxo-3-azaspiro[5.5]undecane-3,11-dicarboxylate from step 1 was dissolved in aqueous NaOH solution (12 M, 5 ml) and stirred in for 5 hours. The reaction mixture was acidified to pH 6 by adding conc. HCl at 0° C. and extracted with EtOAc. The organics were dried and concentrated in vacuo to give a yellow solid which, when triturated, gave a pale pink powder of tert-butyl 8,10-dioxo-3azaspiro[5.5]undecane-3-carboxylate. The aqueous layer was further acidified to pH 2 by adding conc. HCl and extracted with EtOAc. The organic layers were dried and concentrated in vacuo to give a pale yellow solid which, when triturated with ether, gave an additional batch of pale yellow powder of tert-butyl 8,10-dioxo-3azaspiro[5.5]undecane-3-carboxylate (3.914 g , 13.91 mmol).

1H NMR (400 MHz, CDCl ₃ ) δ 3.51-3.25 (m, 4H), 2.69-2.54 (m, 4H), 1.47-1.43 (m, 9H), 1 .44-1.39 (m, 4H).

Step 3. Synthesis of tert-butyl 9-(4-bromo-2,6-dimethylphenyl)-8,10-dioxo-3-azaspiro[5.5]undecane-3carboxylate

tert-Butyl 8,10-dioxo-3-azaspiro[5.5]undecane-3-carboxylate (0.5 g, 1.8 mmol) and DMAP (1.1 g, 8.9 mmol) were dissolved in chloroform (20 ml). The reaction mixture was stirred under nitrogen for 10 min and toluene (5 mL) was added followed by [diacetoxy-(4-bromo-2,6dimethylphenyl)plumbyl]acetate (1.2 g, 2.1 mmol). The resulting suspension was heated under nitrogen at 75° C. for 3 hours and then allowed to cool to room temperature. The reaction mixture was treated with 2M HCl (50 ml) and a white precipitate formed with stirring. The mixture was filtered, the organic phase was separated and the aqueous layer was extracted with DCM. The combined organics were dried (MgSO ₄ ), evaporated and purified by flash column chromatography (gradient elution: 5-100% EtOc:isohexane) to give tert-butyl-9-(4-bromo-2,6-dimethylphenyl)- 8,10-dioxo-3-azaspiro[5.5]undecane-3-carboxylate (0.51 g, 1.1 mmol).

1H NMR (400 MHz, methanol-d ₄ ) δ 7.25-7.10 (m, 2H), 3.54-3.43 (m, 4H), 2.61-2.52 (m, 4H) , 2.05-1.98 (m, 6H), 1.72-1.56 (m, 4H), 1.48-1.39 (m, 9H).

Step 4. Synthesis of tert-butyl 9-(4-bromo-2,6-dimethylphenyl)-8-methoxy-10-oxo-3-azaspiro[5.5]undec-8-ene-3-carboxylate

tert-Butyl 9-(4-bromo-2,6-dimethylphenyl)-8,10-dioxo-3-azaspiro[5.5]undecane-3-carboxylate (1.150 g, 2.476 mmol) was suspended in acetone (50 ml), then potassium carbonate (1.500 eq., 3.714 mmol) was added followed by iodomethane (5 eq., 12.38 mmol). The reaction mixture was stirred at room temperature for 24 hours. The reaction mixture was then concentrated in vacuo, then quenched by careful dilution in 2 M HCl solution (bubbling) and extracted twice with EtOAc. The organic layers were dried and concentrated in vacuo

- 16 040763 to give tert-butyl 9-(4-bromo-2,6-dimethylphenyl)-8-methoxy-10-oxo-3-azaspiro[5.5]undec-8-en-3carboxylate (1.180 g, 2.467 mmol , 99%) as an orange foam.

1H NMR (500 MHz, CDCl ₃ ) δ 7.20-7.13 (m, 2H), 3.64-3.53 (m, 5H), 3.38-3.28 (m, 2H), 2 .64-2.49 (m, 4H), 2.05-2.01 (m, 6H), 1.72-1.63 (m, 4H), 1.48-1.43 (m, 9H) .

Stage 5. Synthesis of tert-butyl-9-[2,6-dimethyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2yl)phenyl]-8-methoxy-10-oxo -3-azaspiro[5.5]undec-8-ene-3-carboxylate

tert-Butyl 9-(4-bromo-2,6-dimethylphenyl)-8-methoxy-10-oxo-3-azaspiro[5.5]undec-8-en-3carboxylate was combined with 4,4,5,5-tetramethyl -2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1,3,2dioxaborolan (1.500 eq., 3.700 mmol), potassium acetate (1.500 eq., 3.700 mmol ), (1E,4E)-1,5-diphenylpenta-1,4-dien-3-one-palladium (0.04 eq., 0.09866 mmol) and dicyclohexyl-[2-(2,6dimethoxyphenyl)phenyl] phosphane (0.08 eq., 0.1973 mmol) in 1,4-dioxane (21 ml) and the flask was purged with two vacuum/N ₂ cycles. The mixture was heated at 100° C. overnight. Then 4,4,5,5-tetramethyl-2(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1,3,2-dioxaborolane (1.500 eq., 3.700 mmol), (1E,4E)-1,5diphenylpenta-1,4-dien-3-one-palladium (0.04 eq., 0.09866 mmol) and dicyclohexyl-[2-(2,6dimethoxyphenyl)phenyl]phosphane (0.08 eq., 0.1973 mmol) and the reaction mixture was heated for another 6 h. Then 4,4,5,5-tetramethyl-2-(4,4,5,5-tetramethyl-1,3 ,2-dioxaborolan-2-yl)-1,3,2dioxaborolane (1.500 eq., 3.700 mmol), (1E,4E)-1,5-diphenylpenta-1,4-dien-3-one-palladium (0, 04 eq., 0.09866 mmol) and dicyclohexyl-[2-(2,6-dimethoxyphenyl)phenyl]phosphane (0.08 eq., 0.1973 mmol) and the reaction mixture was heated overnight. Then 4,4,5,5-tetramethyl-2-(4,4,5,5-tetramethyl1,3,2-dioxaborolan-2-yl)-1,3,2-dioxaborolane (1.500 eq., 3.700 mmol) was added ), (1E,4E)-1,5-diphenylpenta-1,4dien-3-one-palladium (0.04 eq., 0.09866 mmol) and dicyclohexyl-[2-(2,6-dimethoxyphenyl)phenyl] phosphane (0.08 eq., 0.1973 mmol) and the reaction mixture was heated over the weekend. After cooling, the reaction mixture was diluted with 2M HCl and extracted twice with EtOAc. The organic layers were dried and concentrated in vacuo to give an orange solid which was purified by flash column chromatography (gradient elution: 5-60% EtOc:isohexane) to give t-butyl-9-[2,6-dimethyl-4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl]-8-methoxy-10oxo-3-azaspiro[5.5]undec-8-en-3-carboxylate (0.133 g , 0.253 mmol) as an orange gum.

¹ H NMR (400 MHz, CDCl ₃ ) δ 7.53-7.46 (m, 2H), 3.62-3.56 (m, 2H), 3.56-3.47 (m, 3H), 3.42-3.28(m, 2H), 2.62-2.53(m, 4H), 2.10-2.05(m, 6H), 1.74-1.62(m, 4H ), 1.49-1.44 (m, 9H), 1.28-1.25 (m, 12H).

Stage 6. Synthesis of tert-butyl-9-[4-(5-fluoropyrimidin-2-yl)-2,6-dimethylphenyl]-8-methoxy-10-oxo-3azaspiro[5.5]undec-8-en-3- carboxylate

tert-Butyl-9-[2,6-dimethyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl]-8-methoxy-10oxo-3-azaspiro [5.5]undec-8-en-3-carboxylate (0.460 g, 0.875 mmol) and 2-chloro-5-fluoropyrimidine (1.2 eq., 1.05 mmol) were taken up in 1,2-dimethoxyethane (6.15 ml/mmol) in a microwave vial. PdCl ₂ (dppf)-DCM (0.2 eq., 0.175 mmol) was added, followed by tripotassium phosphate solution (4.0 eq., 3.50 mmol) dissolved in water (1.54 ml/mmol, 75 mmol ). The mixture was heated to 100° C. for 45 minutes with microwaves. After cooling, the reaction mixture was diluted with water and extracted twice with EtOc. The organic layers were separated then dried over magnesium sulfate and concentrated in vacuo to give a dark brown gum which was purified by flash column chromatography to give t-butyl-9-[4-(5-fluoropyrimidin-2-yl)-2 ,6-dimethylphenyl]-8methoxy-10-oxo-3-azaspiro[5.5]undec-8-ene-3-carboxylate (0.214 g, 0.432 mmol).

1H NMR (400 MHz, CDCl3) δ 8.68-8.52 (m, 2H), 8.10-7.96 (m, 2H), 3.68-3.53 (m, 5H), 3, 42-3.30 (m, 2H), 2.68-2.49 (m, 4H), 2.19-2.00 (m, 6H), 1.76-1.60 (m, 4H), 1.51-1.41 (m, 9H).

Stage 7. Synthesis of 3-acetyl-9-[4-(5-fluoropyrimidin-2-yl)-2,6-dimethylphenyl]-3-azaspiro[5.5]undecane-8,10-dione (compound A13)

tert-Butyl 9-[4-(5-fluoropyrimidin-2-yl)-2,6-dimethylphenyl]-8-methoxy-10-oxo-3-azaspiro[5.5]undec-8-ene-3-carboxylate ( 0.187 g, 0.377 mmol) was stirred for 1 h at room temperature in hydrogen chloride (4 M in 1,4-dioxane, 5 ml, 20 mmol), after which the reaction mixture was concentrated in vacuo to give a pale yellow solid. This material was suspended in dichloromethane (5 ml). K,N-diethylethanamine (2 eq., 0.754 mmol) was added followed by acetyl chloride (2.5 eq.,

- 17 040763

0.942 mmol), after which all solids went into solution, and the reaction mixture was stirred at room temperature for 1.5 hours. The reaction mixture was diluted with 2 M HCl and extracted twice with DCM. The organic layers were concentrated in vacuo to give a yellow solid which was taken up in acetone (5.89 ml/mmol). HCl (2 M solution) (5.89 ml/mmol, 4.44 mmol) was added and the reaction mixture was heated at 60° C. for 3 h, during which time a pale solid precipitated from solution. By cooling the reaction mixture, filtering and drying on the sintered material, 3-acetyl-9-[4-(5-fluoropyrimidin-2-yl)-2,6-dimethylphenyl]-3azaspiro[5.5]undecan-8,10-dione ( 0.1100 g, 0.2597 mmol) as a cream powder.

1H NMR (400 MHz, methanol-d ₄ ) δ 8.78-8.68 (m, 2H), 8.08-8.03 (m, 2H), 3.68-3.55 (m, 4H) , 2.70-2.57 (m, 4H), 2.17-2.14 (m, 6H), 2.13-2.11 (m, 3H), 1.83-1.64 (m, 4H).

Examples of herbicidal compounds of the present invention.

SO1D

Structure

Table 1 NMR

1HDMSO-D6: 8.94 (s, 2H), 7.92 (s, 2H), 3.41 (s, 3H), 3.32 (bs, 2H), 3.10 (bs, 2H), 2 .39 (bs, 2H), 2.19 (bs, 2H), 2.06 (s, 6H), 1.81 (bs, 2H), 1.45 (bs, 2H)

1H NMR (400 MHz, Methanol-04) δ = 8.77 - 8.68 (m, 2H), 8.07 - 8.00 (m, 2H), 3.56 3.46 (m, 3H), 3.25 - 3.11 (m, 2H), 2.77 - 2.60 (m, 4H), 2.57 - 2.39 (m, 2H), 2.172.08 (m, 6H), 2, 04 - 1.92 (m, 2H),

1.75 - 1.58 (m, 2H) 1H NMR (400

MHz, Methanol-04) δ = 8.95 - 8.84 (m, 1H), 8.19 - 8.12 (m, 1H), 8.07 7.95 (m, 1H), 7.81 - 7.60 (m, 2H), 3.57 - 3.46 (m, 3H), 3.26 - 3.07 (m, 2H), 2.77 2.59 (m, 4H), 2.56 - 2.36 (m, 2H), 2.18-2.05 (m, 6H), 2.02 - 1.87 (m, 2H), 1.73 1.54 (m, 2H)

- 18 040763

- 19 040763

1HNMR: (400 MHz Methanol-04) δ 8.78 (s, 2H), 7.71 (s, 2H), 3.80 (s, 6H), 3.60 (s, 3H), 3.30 ( bs, 2H) 2.82 (m, 2H), 2.63 (bs, 2H), 2.46 (bs, 2H), 2.03 (m, 2H), 1.66 (m, 2H)

1H NMR (400 MHz DMSO-D6) δ 10.23 (s, 1H), 7.737.69 (m, 2H), 7.307.26 (m, 2H), 7.03 (s, 1H), 6.96 ( s, 1H), 3.68 (s, 3H), 3.42 (s, 3H), 3.12 (bs, 2H), 2.69-2.67 (m, 2H), 2.33-2 .18 (m, 2H), 2.02 (s, 3H), 1.94-1.92 (bs, 2H), 1.78 (bs, 2H), 1.49 (bs, 2H). 1HNMR: (400 MHz, Methanol-04) δ 8.75 (s, 2H), 7.89 (s, 1H), 7.81 (s, 1H), 3.78 (s, 3H), 3.52 (s, 3H), 3.19 (m, 2H), 2.65-2.63 (m, 4H), 2.46-2.43 (m, 2H), 2.14 (s, 3H), 2.06 (1H), 1.89 (1H), 1.63 _H_ 1H NMR (400 MHz, Methanol-04) δ = 7.63 - 7.54 (m,

2H), 7.30 - 7.24 (m, 2H), 7.177.05 (m, 2H), 3.52

- 3.43 (m, 5H), 2.63 - 2.59 (m, 4H), 2.15-2.07 (m, 6H), 1.71 1.60 (m, 4H), 1, 51

- 1.40 (m, 9H)

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A12 About X \dulctr ABOUT \ / \-/ ' ABOUT / 1H NMR (400 MHz, Methanol-04) δ = 7.63 - 7.54 (m, 2H), 7.29 - 7.24 (m, 2H), 7.177.05 (m, 2H), 3.69 - 3.53 (m, 4H), 2.65-2.61 (m, 4H), 2.15-2.08 (m, 9H), 1.81 1.74 (m, 2H), 1, 70 - 1.65 (m, 2H) A13 /OK cyA/o ^z^ 1H NMR (400 MHz, Methanol-04) δ = 8.78 - 8.68 (m, 2H), 8.08 - 8.03 (m, 2H), 3.68 3.55 (m, 4H), 2.70 - 2.57 (m, 4H), 2.17 - 2.14 (m, 6H), 2.13 - 2.11 (m, 3H), 1.83 1.64 (m, 4H) A14 O x YYy^Ayyy^ O ⁷ '---''---Zy---' N-o ⁷ 1H NMR (400 MHz, Methanol-04) δ = 8.97 - 8.89 (m, 1H), 8.23 - 8.13 (m, 1H), 8.08 7.99 (m, 1H), 7.82 - 7.68 (m, 2H), 3.67 - 3.59 (m, 4H), 2.68 - 2.61 (m, 4H), 2.172.15 (m, 6H), 2, 13 -2.11 (m, 3H), 1.83 - 1.66 (m, 4H) A15 / O O U<X^CH>O O \ 1HNMR (400 MHz, Methanol-04): δ 8.77 (s, 2H), 7.71 (s, 2H), 3.81 (s, 6H), 3.63 (t, 2H), 3.57 (t, 2H), 2.57 (s, 4H), 2.11 (s, 3H), 1.77 (t, 2H), 1.68 (t, 2H)

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1HNMR (400 MHz, Methanol-44): 8.94 (d, 1H), 8.218.18 (m, 1H), 8.11 (d, 1H), 7.37 (s, 2H), 3.81 ( s, 6H), 3.62 (t, 2H), 3.57 (t, 2H), 2.55 (s, 4H), 2.11 (s, 3H), 1.77 (t, 2H), 1.68 __ 1HNMR (400 MHz, Methanol-44): 8.76 (s, 2H), 7.89 (s, 1H), 7.82 (s, 1H), 3.79 (s, 3H), 3.63 (t, 2H), 3.58 (t, 2H), 2.61 (s, 4H), 2.15-2.11 (6H), 1.83-1.65 (m, 4H) . 1HNMR (400 MHz, Methanol-44): δ 8.94 (d, 1H), 8.198.17 (m, 1H), 8.08 (d, 1H), 7.56 (s, 2H), 3.80 (s, 3H), 3.63 (t, 2H), 3.58 (t, 2H), 2.61 (s, 4H), 2.16-2.11 (6H), 1.83-1, 65(m, 4H)

1H NMR (400 MHz, Methanol-44) δ = 8.36 - 8.32 (m, 1H), 7.68 - 7.64 (m, 1H), 7.46 7.39 (m, 2H), 3.87

- 3.76 (m, 1H), 3.69 - 3.61 (m, 1H), 3.59-3.54 (m, 1H), 3.53 3.44 (m, 1H), 2, 91

- 2.86 (m, 2H), 2.69 - 2.64 (m, 2H), 2.14-2.12 (m, 6H), 2.12 2.11 (m, 3H), 1, 91

- 1.87 (m, 4H)

- 22 040763

A20 / 0 0 ^~ ^N \ χ~5——O ^F 0 0 \ 1H NMR (400 MHz, Methanol-04) δ = 7.67-7.64 (m, 2H), 7.18-7.14 (m, 2H), 6.81 (s, 2H), 3.78 (s, 6H), 3.623.57 (m, 4H), 2.57 (s, 4H), 2.11 (s, 3H), 1.76-1.68 (m, 4H) A21 O V ^~ ^N \ x~5——€> ^f 0 0 \ 1H NMR (400 MHz, Methanol-<14) δ = 7.67-7.59 (m, 2H), 7.19-7.10 (m, 2H), 7.06 (m, 1H), 6, 97 (m, 1H), 3.77 (s, 3H), 3.64 3.57 (m, 4H), 2.60 (s, 4H), 2.12 (m, 6H), 1.86- 1.61 (m, 4H) A22 z III 0 XX ΟχΛ>Ο ⁴ z^ Ο=ώ^ o 1HNMR (DMSOD6, 400 MHz): δ = 9.06 (s, 1H), 8.36-8.33 (m, 1H), 8.15 (d, 1H), 7.79 (s, 2H), 3.23 (t, 4H), 3.11-3.05 (m, 2H), 2.08 (s, 6H), 1.68 (t, 4H), 1.22 (t, 3H) A23 ⁰ \ vi/ y 5——HH—= ⁿ 1H NMR (400 MHz, Methanol-44) δ = 8.91 (s, 1H), 8.17-8.14 (m, 1H), 8.02 (d, 1H), 7.76 (s, 2H ), 7.48-7.42 (m, 5H), 3.82 (t, 2H), 3.49 (t, 2H), 2.65 (s, 4H), 2.172.13 (6H), 1 .83- 1.70(m, 4H) A24 ° y Vn ^z V 5 - - ^N N4 - '^N ) = ^ N = / C / ° ^z 1H NMR (400 MHz, Methanol-44) δ = 8.90 (d, 1H), 8.60 (d, 1H), 8.168.14 (m, 1H), 8.02 (d, 1H), 7, 98-7.94 (m, 1H), 7.77-7.76

- 23 040763

(2H), 7.59 (d, 1H), 7.52-7.49 (m, 1H), 3.85 (t, 2H), 3.48 (t, 2H), 2.71-2, 61 (m, 4H), 2.17 (s, 3H), 2.12 (s, 3H), 1.85 (t, 2H), 1.75 (t, 2H). A25 О V Vn ^z —A= ^N < ^λ )=/ N=/ 0 О / / 1H NMR (400 MHz, Methanol-d4) δ = 8.91 (d, 1H), 8.17-8.14 (m, 1H), 8.03 (d, 1H), 7.77 (s, 2H ), 4.17 (s, 2H), 3.65 (t, 2H), 3.52 (t, 2H), 3.40 (s, 3H), 2.61 (s, 4H), 2.16 (s, 6H), 1.76 (t, 2H), 1.71 (t, 2H). A26 O V 0 /--V /--4 \--Ά r.--Λ ^n ^z Y )——St ^- HN ^X —'^4 )=/ ^N=/ q— 1H NMR (400 MHz, MeTaHon-d4) δ = 8.91 (d, 1H), 8.17-8.14 (m, 1H), 8.03 (d, 1H), 7.77 (s, 2H ), 3.41 (t, 4H), 2.59 (s, 4H), 2.16 (s, 6H), 1.69 (t, 4H), 1.33 (s, 9H). A27 O V θ /—K i 4 Λ—λ Λ—λ n ^z γ )——= ^N HN —''—)=/ N=/ Y-r o / 0 \ ^x 1H NMR (400 MHz, MeTaHon-d4) δ = 8.91 (d, 1H), 8.17-8.14 (m, 1H), 8.03 (d, 1H), 7.77 (s, 2H ), 3.55 (t, 4H), 2.62 (s, 4H), 2.16 (s, 6H), 1.77 (t, 4H), 1.24 (s, 9H), A28 ° \ Vn ^z V —A—— ^N Y \—/^4 Ά ^N=/ <4 O / 1H NMR (400 MHz, MeTaHon-d4) δ = 8.91 (d, 1H), 8.17-8.14 (m, 1H), 8.03 (d, 1H), 7.77 (s, 2H ), 3.83 (t, 2H), 3.65 (t, 2H), 2.63 (s, 4H), 2.17 (s, 6H), 1.99-1.96

- 24 040763

(m, 1H), 1.80 (t, 2H), 1.69 (t, 2H), 0.88-0.79 (m, 4H) A29 ° \ Vn ^Z V —= ^N F--( ^N= / F O ⁷ 1HNMR (DMS0D6, 400 MHz): δ = 9.06 (d, 1H), 8.368.33 (m, 1H), 8.14 (d, 1H), 7.79 (s, 2H), 6.73 ( t, 1H), 3.54 (t, 4H), 2.52 (s, 4H), 2.08 (s, 6H), 1.66-1.61 (m, 4H). AZO ° \ Vn ^? V^N -7\ N=/ / \ o / 1H NMR (400 MHz, MeTaHon-d4) δ = 8.91 (d, 1H), 8.17-8.14 (m, 1H), 8.03 (d, 1H), 7.77 (s, 2H ), 3.71 (t, 4H), 2.62 (s, 4H), 2.17 (s, 6H), 1.72 (t, 4H), 1.29 (s, 9H), A31 ^O \ O ^/ —< / ^—f 1HNMR (DMSOD6, 400 MHz): δ = 9.03 (d, 1H), 8.70 (d, 1H), 8.33-8.29 (m, 1H), 8.13-8.04 (m , 3H), 7.75 (s, 2H), 7.70-7.67 (m, 1H), 3.49 (t, 4H), 2.41 (s, 4H), 2.08 (s, 6H), 1.65 (t, 4H). A32 o J' / \/ \ \ \ ^S-N Y )-C V-^ y-F < ^M)=/^=/ \ ABOUT / 1H NMR (400 MHz, MeTaHon-d4) δ = 8.74 (s, 2H), 8.06 (s, 2H), 3.37 (t, 4H), 3.09-3.04 (m, 2H ), 2.63 (s, 4H), 2.14 (s, 6H), 1.81 (t, 4H), 1.33 (t, 3H). AZZ o \ O /"A a Ν N-^ Vn Y )—/—f W )= ⁷ N=/ \ / ^{0 7} 1H NMR (400 MHz, MeTaHoa-d4) δ = 8.73 (s, 2H), 8.04 (s, 2H), 7.487.42 (m, 5H), 3.83 (bs, 2H), 3, 49 (bs,

- 25 040763

2H), 2.65 (s, 4H), 2.16-2.12 (6H), 1.83 (bs, 2H), 1.71 (bs, 2H). A34 ⁰ \ Vn X )—P /—f N-/ —'^* )=/ N=/ ( / ° ' 1H NMR (400 MHz, Methanol-04) δ = 8.72 (s, 2H), 8.59 (d, 1H), 8.048.02 (2H), 7.977.94 (m, 1H), 7.59 ( d, 1H), 7.51-7.48 (m, 1H), 3.85 (t, 2H), 3.47 (t, 2H), 2.68-2.59 (m, 4H), 2 .17 (s, 3H), 2.12 (s, 3H), 1.84 (t, 2H), 1.74 (t, 2H). AZ 5 ⁰ \ Vn V )—/ χ —(/ /~F < ^x —/^ χ ^N= / 0 0 / / 1HNMR (DMSOD6, 400 MHz): δ = 10.55 (bs, 1H), 8.95 (s, 2H), 7.96 (s, 2H), 4.08 (s, 2H), 3.48 ( 2H), 3.39(2H), 3.29(s, 3H), 2.54(4H), 2.07(s, 6H), 1.62(t, 2H), 1.56(t, 2H). AZ 6 ^ζf ΗΝ \—/^4 / ⁼ / ^Ν= / Λ~ ⁰ 1H NMR (400 MHz, MeTaHon-d4) δ = 8.74 (s, 2H), 8.05 (s, 2H), 3.42 (t, 4H), 2.59 (s, 4H), 2, 15 (s, 6H), 1.69 (t, 4H), 1.33 (s, 9H). AZ 7 ° \ Ο /—4 γΛ \—λ Ν-λ V ^n/ Υ )—chL—( ^ζF ΗΝ \—/^4 /=/ ^Ν=/ Г ο / ο \ ^χ 1H NMR (400 MHz, MeTaHon-d4) δ = 8.73 (s, 2H), 8.05 (s, 2H), 3.55 (t, 4H), 2.62 (s, 4H), 2, 15 (s, 6H), 1.77 (t, 4H), 1.24 (s, 9H). AZ 8 Ο \ O rA Y\ Vn Υ )—Ρ / ^- F V ⁴ —/^4 /=/ ν=/ Ο / 1H NMR (400 MHz, MeTaHon-d4) δ = 8.74 (s, 2H), 8.05 (s, 2H), 3.83 (t, 2H), 3.66 (t,

- 26 040763

2H), 2.64 (s, 4H), 2.15 (s, 6H), 2, ΟΙ, 96 (m, 1H), 1.81 (t, 2H), 1.69 (t, 2H), 0.89-0.84 (m, 2H), 0.83-0.79 (m, 2H). AZ 9 1HNMR (DMSOD6, 400 MHz): δ = 10.61 (bs, 1H), 8.95 (s, 2H), 7.96 (s, 2H), 6.74 (t, 1H), 3.54 ( t, 4H), 2.56 (s, 4H), 2.08 (s, 6H), 1.67-1.62 (m, 4H). A40 1H NMR (400 MHz, Methanol-04) δ = 8.72 (s, 2H), 8.04 (s, 2H), 3.71 (t, 4H), 2.56 (s, 4H), 2, 16 (s, 6H), 1.71 (t, 4H), 1.29 (s, 9H). A41 ⁰ \ ⁰ /-k GL O Vn X )—V \/ ^- F Vn \—>=/ ⁴ N=/ ⁰ 1H NMR (400 MHz, Methanol-04) δ = 8.73 (s, 2H), 8.68 (d, 1H), 8.19 (d, 1H), 8.05 (s, 2H), 8, 01 (d, 1H), 7.65-7.62 (m, 1H), 3.67 (t, 4H), 2.64 (s, 4H), 2.16 (s, 6H), 1.83 (t, 4H). A42 ° \ ACX/lA o \—/ \—Ζ \=/ O / 1H NMR (400 MHz, MeTaHon-d4) δ = 6.90 - 6.78 (m, 2H), 3.70 - 3.47 (m, 4H), 2.92 2.80 (m, 2H), 2.69-2.61 (m, 2H), 2.30-2.20 (m, 3H), 2.14-2.08 (m, 3H), 2.04 1.96 (m, 6H) , 1.90 - 1.83 (m, 3H), 1.81 - 1.55 (m, 4H)

- 27 040763

A43 1HNMR (DMS0D6, 400 MHz): δ = 8.94 (s, 2H), 7.96 (s, 2H), 4.03 (s, 2H), 3.51 (bs, 2H), 3.37 ( bs, 2H), 2.54 (s, 4H), 2.07 (s, 6H), 1.65 (t, 2H), 1.57 (t, 2H). A44 O y Vn ^z Y^$—=n / \—\=/ N=/ \ θ' N 1H NMR (400 MHz, Methanol-04) δ = 8.91 (d, 1H), 8.17-8.14 (m, 1H), 8.02 (d, 1H), 7.77 (s, 2H ), 3.89-3.88 (2H), 3.66 (t, 2H), 3.51 (t, 2H), 2.62 (s, 4H), 2.16 (s, 6H), 1 .79 (t, 2H), 1.72 (t, 2H). A45 ° \ Y —h—( ^Z A—a 0 '-4 \—/ \=/ \=/ 0 / 1H NMR (400 MHz, Methanol Al4) δ = 8.62 (d, J=2.0 Hz, 1H), 8.01 7.95 (m, 1H), 7.94 - 7.88 (m, 1H) , 7.64 (s, 2H), 3.70 3.52 (m, 4H), 2.65 (s, 4H), 2.16 (s, 6H), 2.12 (s, 3H), 1 .82 - 1.63 (m, 4H). A46 ⁰ \ . .____ _/ --U \--- _h N—L y _N Qfy^yv/^ _F o' \—/ \ \=/ '' O / 1H NMR (400 MHz, Methanol A4) δ = 8.54 (d, J=2.9 Hz, 1H), 7.95 (dd, J=4.5, 8.8 Hz, 1H), 7.77 ( dt, J=2.9, 8.6 Hz, 1H), 7.61 (s, 2H), 3.70 - 3.53 (m, 4H), 2.65 (s, 4H), 2.16 (s, 6H), 2.12 (s, 3H), 1.85 1.62 (m, 4H).

- 28 040763

A47

A48

A49

A50

1H NMR (400 MHz, Methanol-04) δ = 8.17 (d, J=4.5 Hz, 1H), 7.59 (d, >3.7 Hz, 1H), 7.38 (s, 2H) , 3.71-3.49 (m, 4H), 2.64 (s, 4H), 2.13 (s, 6H), 2.12 (s, 3H), 1.821.65 (m, 4H) 1H NMR (400 MHz, Methanol^4) δ = 8.43 (d, J=2.3 Hz, 1H), 7.63 (br ddd, J=2.3, 8.4, 10.7 Hz, 1H ), 7.54 (s, 2H), 3.70 - 3.55 (m, 4H), 2.69 2.60 (m, 4H), 2.15 (s, 6H), 2.12 (s , 3H), 1.83 - 1.66 (m, 4H).

1H NMR (400 MHz, MeTaHon-d4) 6 = 7.61 - 7.57 (m, 2H), 7.44 - 7.38 (m, 2H), 7.32 7.26 (m, 2H), 3.68 - 3.56 (m, 4H), 2.66 - 2.62 (m, 4H), 2.14 - 2.12 (m, 6H), 2.12 2.11 (m, 3H) , 1.81 - 1.75 (m, 2H), 1.73 - 1.65 (m, 2H)

1H NMR (400 MHz, Methanol-d4) δ = 8.47 (d, J=l,l Hz, 1H), 7.80 (dd, J=2.0, 10.6 Hz, 1H), 7, 59 (s, 2H), 3.72 - 3.53 (m, 4H), 2.70 - 2.60 (m, 4H), 2.15 (s, 6H), 2.13 (s, 3H) , 1.83 - 1.66 (m, 4H).

- 29 040763

A51 O \ —\Λ—( Ύ Cl o '—' \=/ _N =/ O / 1H NMR (400 MHz, Methanol-04) δ = 8.80 (s, 2H), 8.12-8.07 (m, 2H), 3.70-3.55 (m, 4H), 2.68 2.61 (m, 4H), 2.17 (s, 6H), 2.13 (s, 3H), 1.83 - 1.68 (m, 4H). A52 ⁰ \ —\A—{—= ⁿ 0 '' λ—N=/ o / 1H NMR (400 MHz, Methanol-44) δ = 9.13 (s, 2H), 8.20 (s, 2H), 3.74 3.54 (m, 4H), 2.65 (s, 4H) , 2.17 (s, 6H), 2.12 (s, 3H), 1.85 - 1.64 (m, 4H) A53 ό ζχ °=/^ ABOUT 1H NMR (400 MHz, Methanol-44) δ = 7.60-7.59 (m, 2H), 7.25 (s, 2H), 7.13 (t, 2H), 3.36 (t, 4H ), 3.07-3.05 (t, 2H), 2.62 (s, 4H), 2.11 (s, 6H), 1.81 (t, 4H), 1.33 (t, 3H) . A54 O v ^~ ^Ν \ X~~5—\—^—F Ο θ / ^_ 1H NMR (400 MHz, Methanol-04) δ = 7.61-7.57 (br, 2H), 7.48-7.42 (br, 5H), 7.24 (s, 2H), 7.12 (t, 2H), 3.82 (bs, 2H), 2.49 (bs, 2H), 2.65 (s, 4H), 2.13-2.09 (6H), 1.82 (bs, 2H), 1.70 (bs, 2H). A55 Vn ^z \λΛ——Λ~Vf _Ν _/ \=/ \=/ ⁰ ' 1H NMR (400 MHz, Methanol-04) δ = 8.60 (d, 1H), 7.95 (t, 1H), 7.597.55 (m, 3H), 7.517.48 (m, 1H), 7.217, 20(2H), 7.10(t, 2H), 3.84(t, 2H), 3.46(t, 2H), 2.552.54(m, 4H), 2.15

- 30 040763

(s, 3H), 2.10 (s, 3H), 1.84 (t, 2H), 1.75 (t, 2H). A56 ° \ ^~ ^N \ X~5——€> O O / / 1H NMR (400 MHz, Methanol-44) δ = 7.60-7.57 (m, 2H), 7.23 (s, 2H), 7.11 (t, 2H), 4.17 (s, 2H ), 3.65 (t, 2H), 3.52 (t, 2H), 3.40 (s, 3H), 2.57 (s, 4H), 2.12 (s, 6H), 1.74 (t, 2H), 1.70 (t, 2H). A57 °\Vn ^? —O—V ^-f λ 1H NMR (400 MHz, Methanol-44) δ = 7.61-7.58 (m, 2H), 7.25 (s, 2H), 7.12 (t, 2H), 3.40 (t, 4H ), 2.59 (S, 4H), 2.12 (s, 6H), 1.68 (t, 4H), 1.33 (s, 9H). A58 ° \ Λν ⁷ Y $—V ^{- f} HN \—/^S HN ⁰ 0 \ ^x 1H NMR (400 MHz, Methanol-44) δ = 7.62-7.58 (m, 2H), 7.25 (s, 2H), 7.13 (t, 2H), 3.55 (t, 4H ), 2.63 (s, 4H), 2.12 (s, 6H), 1.77 (t, 4H), 1.24 (s, 9H). A59 Ο X x~~5——o <4 <E / 1H NMR (400 MHz, Methanol-44) δ = 7.61-7.58 (m, 2H), 7.25 (s, 2H), 7.12 (t, 2H), 3.82 (t, 2H ), 3.66 (t, 2H), 2.63 (s, 4H), 2.12 (s, 6H), 1.991.96 (m, 1H), 1.80 (t, 2H), 1.69 (t, 2H), 0.88-0.79 (m, 4H). A60 O ^{4 W} 1H NMR (400 MHz, Methanol-44) δ = 7.62-7.58 (m, 2H), 7.26 (s, 2H), 7.13 (t, 2H), 6.48

- 31 040763

(t, 1H), 3.72-3.65 (m, 4H), 2.64 (s, 4H), 2.12 (s, 6H), 1.81-1.74 (m, 4H). A61 °\l-zb— ^f /\o' 1HNMR (MeOD, 400 MHz): 5 7.627.58 (m, 2H), 7.25 (s, 2H), 7.13 (t, 2H), 3.70 (t, 4H), 2.63 (s , 4H), 2.12 (s, 6H), 1.72 (t, 4H), 1.29 (s, 9H). A62 ° \ ° Xn ^z —to V- ^f Xn )=/ \=/ ° 1H NMR (400 MHz, Methanol-04) 5 = 8.68 (d, 1H), 8.19 (d, 1H), 8.037.99 (m, 1H), 7.647.61 (m, 1H), 7.597, 55 (m, 2H), 7.20 (s, 2H), 7.10 (t, 2H), 3.67 (t, 4H), 2.52 (s, 4H). 2.14 (s, 6H), 1.81 (t, 4H). A63 x^ x~~5——сз v ° / N 1H NMR (400 MHz, Methanol-54) 5 = 7.62-7.58 (m, 2H), 7.26 (s, 2H), 7.13 (t, 2H), 3.893.87 (2H), 3.66 (t, 2H), 3.51 (t, 2H), 2.63 (s, 4H), 2.12 (s, 6H), 1.79 (t, 2H), 1.72 (t , 2H) A64 θ \ 0 ,----V )----< y----V Q=S-N^^2-F 0 O \ 1H NMR (400 MHz, Methanol-54) 5 = 7.64-7.61 (m, 2H), 7.14 (t, 2H), 7.04 (s, 1H), 6.96 (s, 1H ), 3.75 (s, 3H), 3.36-3.34 (m, 4H), 3.08-3.03 (q, 2H), 2.57 (s, 4H), 2.11 ( s, 3H), 1.84 (t, 2H), 1.76 (t, 2H), 1.33 (t, 3H).

- 32 040763

A65 ° \ -O PM o o \=/ X 1H NMR (400 MHz, Methanol-04) δ = 7.64-7.60 (m, 2H), 7.47-7.42 (m, 5H), 7.13 (t, 2H), 7.04 (s, 1H), 6.96 (s, 1H), 3.81-3.71 (5H), 3.48 (m, 2H), 2.62 (s, 4H), 2.12-2, 09 (3H), 1.86-1.67 (m, 4H). A66 ⁰ \ y _N ^H_>y_fyF nA ^^4 /=, (/ \ o o \=/ \ 1H NMR (400 MHz, Methanol-44) δ = 8.60-8.59 (d, 1H), 7.95 (t, 1H), 7.63-7.58 (m, 3H), 7.50 (t, 1H), 7.13 (t, 2H), 7.04-7.03 (1H), 6.96-6.94 ( 1H), 3.84 (m, 2H), 3.77 ( s, 3H), 3.46 (m, 2H), 2.662.57 (m, 4H), 2.122.08 ( 3H), 1.89 (t, 1H), 1.82-1.76 (m, 2H ), 1.71 (t, 1H). A67 0 to Vn ^z 1= o-/ \-^= ⁷ / OO X 1H NMR (400 MHz, Methanol-44) δ = 7.64-7.60 (m, 2H), 7.13 (t, 2H), 7.04 (s, 1H), 6.96 (s, 1H), 4.16 (s, 2H), 3.75 (s, 3H), 3.64 (m, 2H), 3.51 (m, 2H), 3.39 (s, 3H) , 2.57 (s, 4H), 2.12 (s, 3H), 1.811.79 (m, 1H), 1.751.72 (m, 2H), 1.67 (t, 1H). A68 ⁰ \ Um^yChAy-gur —4—N ^V ^ ^V 4 )= ^{7 4=7} / ⁿ O 0 X 1H NMR (400 MHz, Methanol-44) δ = 7.64-7.61 (m, 2H), 7.14 (t, 2H), 7.04 (s, 1H), 6.96 (s, 1H ), 3.76 (s, 3H), 3.40-3.39 (m, 4H), 2.55 (s, 4H), 2.11 (s, 3H), 1.72

- 33 040763

(t, 2H), 1.65 (t, 2H), 1.32 (s, 9H). A69 ⁰ \ o / X / ^—A ~ ^λ 0 ^o /\ \ 1H NMR (400 MHz, Methanol-04) δ = 7.64-7.60 (m, 2H), 7.14 (t, 2H), 7.04 (s, 1H), 6.96 (s, 1H ), 3.75 (s, 3H), 3.53 (t, 4H), 2.58 (s, 4H), 2.11 (s, 3H), 1.80 (t, 2H), 1.73 (t, 2H), 1.23 (s, 9H). A70 O V V- |/ Y ^F <1 O o \ 1H NMR (400 MHz, Methanol-04) 6 = 7.64-7.61 (t, 2H), 7.14 (t, 2H), 7.05-6.96 (2H), 3.81 (t , 2H), 3.76 (s, 3H), 3.64 (br, 2H), 2.60 (s, 4H), 2.12 (s, 3H), 1.98 (br, 1H), 1 .83 (w, 1H), 1.76-1.72 (w, 2H), 1.65 (w, 1H), 0.89-0.85 (m, 2H), 0.82-0.79 (m, 2H). A71 ⁰ \ Vn ^Z y ^F F—( \—/^F /=/ ^=/ F OO \ 1H NMR (400 MHz, Methanol-s14) 6 = 7.64-7.61 (br, 2H), 7.14 (t, 2H), 7.05 (s, 1H), 6.96 (s, 1H ), 6.48-6.47 (br, 1H), 3.76 (s, 3H), 3.69-3.65 (br, 4H), 2.60 (s, 4H), 2.12 ( s, 3H), 1.851.70 (m, 4H). A72 ⁰ \ N ^Z Y _F /\ <3 0 \ 1H NMR (400 MHz, Methanol-s14) 6 = 7.64-7.61 (br, 2H), 7.14 (t, 2H), 7.05 (s, 1H), 6.96 (s, 1H ), 3.76 (s, 3H), 3.69 (br, 4H), 2.59 (s, 4H), 2.12 (s, 3H), 1.75 (t, 2H), 1.68 (m, 2H), 1.28 (s, 9H).

- 34 040763

A73

A74

A75

A76

1H NMR (400 MHz, Methanol-04) δ = 8.68-8.67 (d, 1H), 8.20-8.18 (d, 1H), 8.02 (t, 1H), 7.64 -7.61(m, 3H), 7.14(t, 2H), 7.05(s, 1H), 6.96(s, 1H), 3.76(s, 3H), 3.66( m, 4H), 2.62 (s, 4H), 2.12 (s, 3H), 1.86 (t, 2H), 1.79 (t, 2H)

1H NMR (400 MHz, Methanol-44) 5= 7.64-7.61 (m, 2H), 7.14 (t, 2H), 7.05 (s, 1H), 6.96 (s, 1H ), 3.89-3.87 (m, 1H), 3.76 (s, 3H), 3.66 (m, 2H), 3.50 (t, 2H), 2.59 (s, 4H) , 2.11 (s, 3H), 1.83 (t, 1H), 1.77 (t, 1H), 1.68 (t,

1H).

1H NMR (400 MHz, MeTaHon-d4) 5= 7.64-7.60 (2H), 7.15-7.11 (2H), 7.04 (1H), 6.95 (1H), 4, 59 4.57 (1H),

3.75 - 3.70 (4H), 3.62 - 3.58 (3H), 2.59 - 2.57 (4H), 2.11 (3H), 1.801.67 (4H), 1.32 1.30 (3H).

1H NMR (400 MHz, MeTaHon-d4) δ = 9.22 (1H), 8.94 - 8.93 (1H), 7.67 7.65 (1H), 7.63 7.60 (2H), 7.157.11(2H), 7.04(1H), 6.98-6.94(1H), 3.83(2H), 3.77-3.71(3H),

- 35 040763

3.49 (2H), 2.64 2.62 (4H), 2.122.09 (3H), 1.88-1.74 (4H). A77 o \—/ \—/ \=/ o o \ 1H NMR (400 MHz, Methanol-d4) δ = 7.64 - 7.60 (2H), 7.15 - 7.11 (2H), 7.04 (1H), 6.95 (1H), 4, 85 4.82 (4H), 4.21 4.17 (1H), 3.75 (s, 3H), 3.66 (2H), 3.30 (2H), 2.56 (4H), 2, 11 (3N), 1.74 (2N), 1.68 - 1.65 (2H) A78 0% Z TU 0 1H NMR (400 MHz, Methanol-d4) δ = 7.65-7.62 (m, 2H), 7.17-7.12 (m, 2H), 7.05 (s, 1H), 6.97 (s, 1H), 3.76 (m, 3H), 3.74 - 3.44 (m, 6H), 2.60 (s, 4H), 2.24 (d, 3H), 2.12 ( s, 3H), 1.85 - 1.65 (m, 4H)

table 2

SO1D Structure NMR pl 0 X 0 / A 1HNMR (500 MHz, CDC1 ₃ ) δ = 7.56-7.51 (m, 2H), 7.23 - 7.20 (m, 2H), 7.147.06 (m, 2H), 3.80 - 3 .70 (m, 1H), 3.63 - 3.48 (m, 3H), 2.79 - 2.60 (m, 4H), 2.152.02 (m, 9H), 1.93 - 1.88 (m, 3H), 1.87 - 1.65 (m, 4H) P2 ⁰ \ x ^- S—— 0 \=/ O / 04 0- 1H NMR (400 MHz, Methanold4) δ = 6.85 - 6.81 (m, 2H), 3.85 3.75 (m, 1H), 3.64 - 3.42 (m, 3H), 2, 86 - 2.83 (m, 2H), 2.64 - 2.60 (m, 2H), 2.27 2.22 (m, 3H), 2.12 - 2.09 (m, 3H), 2 .02 - 1.97 (m, 6H), 1.86 - 1.83 (m, 3H), 1.82 - 1.55(m, 4H) P3 0 ΥΎ Y 1HNMR (MeOD 400 MHz): δ = 7.65-7.61 (m, 2H), 7.15 (t, 2H), 7.03 (s, 1H), 6.96 (s, 1H), 3 .75 (4H), 3.69 (s, 3H), 3.613.47 (m, 3H), 2.92 (s, 2H), 2.62 (s, 2H), 2.11-2.09 ( 6H), 2.00-1.93(m, 1H), 1.87-1.83(m, 1H), 1.74-1.62(m, 2H).

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Table 3 Comparative Compound of the Prior Art

Compound Structure S1 T-26 ABOUT O X uuu WO2008/110308 O /

biological examples.

Seeds of a number of tested species were sown in standard potting soil (Lolium perenne (LOLPE), Setaria faberi (SETFA), Alopecurus myosuroides (ALOMY), Echinochloa crus-galli (ECHCG), Avena fatua (AVEFA)). After cultivation for 1 day (pre-emergence) or after 8 days of cultivation (post-emergence) under controlled conditions in a greenhouse (at 24/16°C, day/night; 14 h photoperiod; 65% humidity), the plants were sprayed with water a spray solution obtained from a formulation with a technical active ingredient in an acetone/water (50:50) solution containing 0.5% Tween 20 (polyoxyethylene sorbitan monolaurate, CASRN 9005-64-5). Compounds were applied at 250 g/ha. The test plants were then grown in a greenhouse under controlled greenhouse conditions (at 24/16°C, day/night; 14 h photoperiod; 65% humidity) and watered twice a day. After 13 days, for pre-emergence and post-emergence applications, the test plant was evaluated for the degree of damage to the plant in percent. The values of biological activity are shown in table. B1 on a five-point scale (5 = 80-100%; 4 = 60-79%; 3 = 40-59%; 2 = 20-39%; 1 = 019%).

Table B1

Compound lolpe SETFA ALOMY ECHCG AVEFA BEFORE AFTER BEFORE AFTER BEFORE AFTER BEFORE AFTER BEFORE AFTER A1 5 5 5 5 5 5 5 5 5 5 A2 5 5 5 5 5 5 5 5 5 5 AZ 5 5 5 5 5 5 5 5 5 5 A4 5 5 5 5 5 5 5 5 5 5 A5 5 5 5 5 5 5 5 5 5 5 Ab 5 5 5 5 5 5 5 5 5 5 A7 5 5 5 5 5 5 5 5 5 5 A8 5 5 5 5 5 5 5 5 5 5 A9 5 5 5 5 5 5 5 5 5 5 AYu 5 5 5 5 5 5 5 5 5 5 AP 5 5 5 5 5 5 5 5 4 4 A12 5 5 5 5 5 5 5 5 4 5 A13 5 5 5 5 5 5 5 And. T. 5 5 A14 5 5 5 5 5 5 5 And. T. 5 5 A15 5 5 5 5 5 5 5 5 5 5 A16 3 4 4 5 1 5 5 And. T. 4 5 A17 5 5 5 5 5 5 5 5 5 5 A18 5 5 5 5 4 5 5 5 5 5 A19 4 5 3 5 2 5 1 4 5 5 A20 5 5 5 5 5 5 5 5 5 5 A21 5 5 5 5 5 5 5 5 5 5 A22 5 5 5 5 5 5 5 And. T. 5 5 A23 5 5 5 5 5 5 5 5 5 5 A24 5 5 5 5 5 5 5 5 5 5 A25 5 5 5 5 5 5 5 5 5 5

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A26 5 5 5 5 5 5 5 n. T. 4 2 A27 4 5 5 5 4 5 5 n. T. 2 1 A28 5 5 5 5 5 5 5 5 5 5 A29 1 5 5 5 n. T. 5 1 4 5 5 AZO 5 5 5 5 5 5 5 5 3 5 A31 1 5 1 5 1 5 3 5 n. T. 5 A32 5 5 5 5 5 5 5 5 5 5 AZZ 5 5 5 5 5 5 5 5 5 5 A34 5 5 5 5 5 5 5 5 5 5 AZ 5 5 5 5 5 5 5 5 5 5 5 A36 5 5 5 5 5 5 5 n. T. 5 5 A37 5 5 5 5 5 5 5 n. T. 5 5 AZ 8 5 5 5 5 5 5 5 5 5 5 AZ 9 5 5 5 5 5 5 5 5 5 5 A40 5 5 5 5 5 5 5 5 5 5 A41 3 5 5 5 3 5 4 5 3 5 A42 5 5 5 5 5 5 3 1 5 5 A43 5 5 5 5 5 5 5 5 5 5 A44 3 5 5 5 5 5 5 4 3 5 A45 5 5 5 5 5 5 5 5 5 5 A46 5 5 5 5 5 5 5 5 5 5 A47 4 5 4 5 2 5 3 1 4 5 A48 5 5 5 5 5 5 5 5 5 5 A49 5 5 5 5 5 5 5 5 5 5 A50 5 5 5 5 5 5 5 5 5 5 A51 5 5 5 5 5 5 5 5 5 5 A52 5 5 5 5 5 5 5 5 5 5 A53 5 5 5 5 5 n. T. 5 3 4 5 A54 5 5 5 5 5 n. T. 5 5 5 5 A55 5 5 5 5 5 n. T. 5 5 5 5 A56 5 5 5 5 5 n. T. 5 5 5 5 A57 5 5 5 5 n. T. n. T. 5 5 1 4 A58 5 5 5 5 5 n. T. 5 5 4 5 A59 5 5 5 5 5 n. T. 5 5 5 5 A60 5 5 5 5 5 n. T. 5 5 5 5 A61 5 5 5 5 5 n. T. 5 5 2 4 A62 2 2 3 5 n. T. n. T. 1 3 2 5 A63 5 5 5 5 5 n. T. 5 4 5 5 A64 5 5 5 5 n. T. n. T. 5 5 5 5 A66 5 5 5 5 n. T. n. T. 5 5 5 5 A67 5 5 5 5 n. T. n. T. 5 5 5 5 A68 4 5 5 5 n. T. n. T. 5 5 4 5 A69 4 5 5 5 n. T. n. T. 5 5 2 5 A70 5 5 5 5 n. T. n. T. 5 5 5 5 A71 5 5 5 5 n. T. n. T. 5 5 5 5 A72 5 5 5 5 n. T. n. T. 5 5 1 5 A73 1 5 5 5 5 n. T. 4 5 1 5 A74 5 5 5 5 n. T. n. T. 5 5 5 5 A75 5 5 5 5 5 5 5 5 5 5 P1 5 5 5 5 5 5 5 5 5 5

n. t. = not tested.

Using the procedures outlined above, weed species ALOMY, AVEFA and LOLPE were treated post-emergence with Compound A4 of the present invention or Comparative Compound C1 (Compound T-26 of WO 2008/110308) at the indicated application rates. The test assessed the percentage of damage that was caused to the plant.

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Table B2

Compound Norm, g/ha ALOMY AVEFA lolpe C1 63 80 70 60 16 20 20 thirty A4 63 90 90 90 16 40 40 70 A7 63 100 100 100 16 80 100 90 A13 63 100 100 90 16 90 90 70

These results demonstrate that the compounds of the present invention, illustrated using compounds A4, A7 and A13, have an improved level of weed control compared to the structurally similar compound C1 of the prior art.

Claims (15)

1. Compound of formula (I) G where R ¹ is selected from methyl, phenyl and 5 - or 6-membered heteroaryl, which contains one or two nitrogen heteroatoms, while the specified phenyl and heteroaryl are optionally substituted with one or two substituents R ¹⁵ ; R ² is methyl or methoxy; R ³ is methyl or methoxy; R ⁴ is selected from the group consisting of C1-C4 alkyl, C1-C4 alkoxy, C1-C4 haloalkyl, -C(=O)C1-C4 alkyl, -C(=O)C1-C4 haloalkyl, -S(O)nC1-C6-alkyl, -S(O)nC1-C6-haloalkyl, -S(O)n-(CH2)n-C3-C6-cycloalkyl, -S(O)nC(R ¹¹ ) R ¹² R ¹³ , -C(O)H, -C(O)-(CH2)n-C3-C6-cycloalkyl, -C(O)C(R ¹¹ )R ¹² R ¹³ , -C(O)C2 -C4-alkenyl, -C(O)(CR ⁹ R ¹⁰ )CN, -C(O)(CR ⁹ R ¹⁰ )(CR ⁹ R ¹⁰ )CN, -C(O)CH2C(O)-CiC6-alkyl , -C (O) CH ₂ OC (O) -C ₁ -C ₆ -alkyl, -C (O) OC ₁ -C ₆ -alkyl, -C (O) OC ₁ -C ₆ -haloalkyl, -C (O) (CH ₂ ) _n S (O) _n C ₁ -C ₆ -alkyl ₁ -C (O) C ₁ -C ₃ -alkoxy-C ₁ -C ₆ -alkyl, -C (O) C ₁ -C ₃ -alkoxy-C ₂ -C ₆ -alkenyl, -C (O) C ₁ -C ₃ -alkoxy-C ₂ -C ₆ -alkynyl, -C (O) C ₁ -C ₃ -alkoxy-C ₁ -C ₆ -haloalkyl, -C (O) C ₁ -C ₃ -alkoxy-C ₃ C ₆ -cycloalkyl, -C (O) OC ₁ -C ₃ -alkoxy-C ₁ -C ₆ -alkyl, -C (O)C ₁ -C ₃ -alkoxy-C ₁ -C ₃ -alkoxy-C ₁ -C ₆ -alkyl, -C (O) (CH2) nNR ⁵ R ⁶ , -C (O) - (CH2) n -NR ⁷ C(O)R ⁸ , -C(O)-(CH2)nON=CR ⁵ R ⁵ , -CN, -(CH2)n-phenyl, C(O)-(CH ₂ ) _n -phenyl, -S(O) _n -(CH ₂ ) _n -phenyl, -heterocyclyl, -C(O)-(CH ₂ ) _n- heterocyclyl, -C(O)(CH ₂ ) _n O-(CH ₂ ) _n -heterocyclyl, -S(O) _n -(CH ₂ ) _n -heterocyclyl, where each heterocyclyl is a 5- or 6-membered heterocyclyl which can be aromatic, saturated or partially saturated and may contain from 1 to 4 heteroatoms each independently selected from the group consisting of oxygen, nitrogen and sulfur, and where these heterocyclyl or phenyl groups are optionally substituted with one, two or three substituents independently selected from the group consisting of C ₁ -C ₃ alkyl, C ₁ -C ₃ haloalkyl, C ₁ -C ₃ alkoxy, C ₂ -C ₃ alkenyl, C ₂ -C ₃ alkynyl, halogen, cyano and nitro ; R ⁵ is selected from the group consisting of hydrogen and C ₁ -C ₆ -alkyl; R ⁶ is selected from the group consisting of hydrogen, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C1-C6 haloalkyl, hydroxyl, C1-C6 alkoxy, C3-C6 cycloalkyl, - C1-C4-alkoxy-C1-C6-alkyl, -C1-C3-alkoxy-C1-C6-haloalkyl, -(CR ⁹ R ¹⁰ )C1-C ₆ -haloalkyl, -(CR ⁹ R ¹⁰ )C(O) NR ⁵ R ⁵ , phenyl, pyridyl, where phenyl and pyridyl are optionally substituted with one, two or three substituents independently selected from the group consisting of C ₁ -C ₃ alkyl, C ₁ -C ₃ haloalkyl, C ₁ -C ₃ -alkoxy, C ₂ -C ₃ -alkenyl, C ₂ -C ₃ alkynyl, halogen, cyano and nitro; or R ⁵ and R ⁶ together form -CH2CH2OCH2CH2-; R ⁷ is selected from the group consisting of hydrogen and C ₁ -C ₆ -αkyl; R ⁸ is selected from the group consisting of hydrogen, C ₁ -C ₆ -alkyl, C ₁ -C ₆ -alkoxy, C ₃ -C ₆ -cycloalkyl, phenyl, pyridyl, where phenyl and pyridyl are optionally substituted with one, two or three substituents independently selected from the group consisting of C ₁ -C ₃ alkyl, C ₁ -C ₃ haloalkyl, C ₁ -C ₃ alkoxy, C ₂ -C ₃ alkenyl, C ₂ -C ₃ alkynyl, halogen, cyano and nitro; R ⁹ is hydrogen or methyl; R ¹⁰ is hydrogen or methyl or R ⁹ and R ¹⁰ together form -CH2CH2-; - 39 040763 R ¹¹ is hydrogen or methyl; R ¹² is selected from the group consisting of hydrogen, Ci-Ce-alkyl, hydroxyl and Ci-Ce-alkoxy; R ¹³ is selected from the group consisting of hydrogen, C1-C ₆ alkyl, hydroxyl and C1-C ₆ alkoxy; or R ¹² and R ¹³ together form -CH ₂ -X-CH ₂ -; X is selected from the group consisting of O, S and NR ¹⁴ ; R ¹⁴ is selected from the group consisting of hydrogen, C ₃ -C ₃ alkyl and C 1 -C ₃ alkoxy; R ¹⁵ is independently selected from the group consisting of C ₃ -C ₄ alkyl, C 1 -C ₄ haloalkyl, cyano and halogen; G is selected from the group consisting of hydrogen, -(CH ₂ ) _n -R ^a , -C(O)-R ^a , -C(O)-(CR ^c R ^d )nOR ^b , -C(O)-( CR ^c R ^d )nSR ^b , -C(O)NR ^a R ^a , -S(O)2-R ^a and C1-C8-alkoxy-C1-C ₃ -alkyl-; R ^a is independently selected from the group consisting of hydrogen, C ₃ -C ₈ alkyl, C 1 -C ₃ haloalkyl, C ₂ -C ₈ alkenyl, C ₂ -C ₈ alkynyl, C ₃ -Ce cycloalkyl and phenyl where said phenyl group is optionally substituted with one, two or three substituents independently selected from the group consisting of C1- _C3 alkyl, C1- _C3 haloalkyl, Ci- _C3 alkoxy, _C2 - _C3 alkenyl, C ₂ -C ₃ alkynyl, halogen, cyano and nitro; R ^b is selected from the group consisting of C 1 -C ₈ -alkyl, C 1 -C ₃ -haloalkyl, C ₂ -C ₈ -alkenyl, C ₂ -C ₈ alkynyl, C ₃ -C ₆ -cycloalkyl and phenyl, where the specified the phenyl group is optionally substituted with one, two or three substituents independently selected from the group consisting of C] _-C3 alkyl, C1- _C3 haloalkyl, C1- _C3 alkoxy, _C2 - _C3 alkenyl, _C2 -C ₃ alkynyl, halogen, cyano and nitro; R ^c is hydrogen or C1- _C3 alkyl; R ^d is hydrogen or C1- _C3 alkyl; η is independently 0, 1, or 2, or its agriculturally acceptable salt. 2. A compound according to claim 1, wherein R ² is methyl. 3. A compound according to any one of the preceding claims, wherein R ³ is methyl. 4. The compound according to any one of the previous paragraphs 1, 2, where R ³ represents methoxy. 5. A compound according to any one of the preceding paragraphs, wherein R ⁴ is C]-C ₄ -alkoxy. 6. A compound according to any one of claims 1 to 4, wherein R ⁴ is -C(=O)C1- _C4 alkyl. 7. A compound according to any one of claims 1 to 4, wherein R ⁴ is —C(O)OC1- _C6 alkyl. 8. A compound according to any one of the preceding claims, wherein G is hydrogen. 9. A compound according to any one of claims 1 to 7, wherein G is -C(O)C1- _C6 alkyl. 10. A compound according to any one of claims 1 to 7, wherein G is -C(O)-O-C1-C6-alkyl. 11. A herbicidal composition comprising a compound of formula (I) according to any one of the preceding claims and an agriculturally acceptable adjuvant. 12. The herbicidal composition of claim 11 further comprising at least one additional pesticide. 13. The herbicidal composition of claim 12, wherein the additional pesticide is a herbicide or herbicide safener. 14. A method for controlling weeds in a locus, comprising applying to the locus an amount of a composition according to any one of claims 11-13 sufficient to control weeds. 15. Use of a compound of formula (I) according to claim 1 as a herbicide.