WO 2020/074489
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`!
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`PCT/EP2019/077185
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`HERBICIDAL 2-AZASPIRO[3-5JNONANE COMPOUNDS
`
`The present
`
`invention
`
`relates
`
`to
`
`novel
`
`herbicidal
`
`cyclohexanedione
`
`compounds,
`
`to processes for their preparation,
`
`to herbicidal compositions which
`
`comprise the novel compounds, and to their use for controlling weeds.
`
`Herbicidal cyclic dione compounds substituted by a phenyl which has an
`
`alkynyl-containing substituent are disclosed in, for example, WO2014/096289 and
`
`W02015/197468. The present invention relates to novel herbicidal cyclohexanedione
`
`10
`
`derivatives with improved properties.
`
`Thus, according to the present invention there is provided a compound of
`
`Formula (1)
`
`OR
`
`XD
`OR
`(I)
`
`3
`
`G
`
`15
`
`wherein
`
`R' is selected from the group consisting of methyl, ethynyl, 1-propynyl, phenyl
`
`20
`
`and a 5 or 6 membered heteroaryl which comprises one or two nitrogen
`
`heteroatoms, said phenyl and heteroaryl optionally substituted by one or two
`
`R'® substituents;
`
`25
`
`30
`
`R? is selected from the group consisting of methyl, ethyl, methoxy and chloro;
`
`R? is selected from the group consisting of methyl, ethyl, methoxy and chloro;
`
`R* is selected from the group consisting of C1-Cyalkyl, C1-Caalkoxy-, Ci-
`
`Cahaloalkyl, -C(O)C1-Caalkyl, -C(O0)C1-Cahaloalkyl, -S(O)nCi1-Cealkyl, -S(O)nCi-
`Cehaloalkyl, -S(O)n-(CH2)n-Ca-Cecycloalkyl, -S(O)nC(R™)R'7R*%, -C(O)H, -C(O)-
`(CH2)n-Ca-Cecycloalkyl,
`-C(O)C(R")R'2R'S,
`-C(O)C2-Caalkenyl,
`-
`C(O)(CR®R™)CN,
`-C(O)(CRER)(CRER™)CN,
`-C(O)CH2C(O)-Ci-Cealkyl,
` -
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`
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`C(O)CH20C(O)-C1-Cealkyl, -C(OQ)OC1-Cehaloalkyl,=--C(OQ)OC1-Cealkyl,
`
`
`
`C(O)(CH2)nS(O)nC1-Cealkyl, -C(O)C1-CsalkoxyC1-Cealkyl, -C(O)C1-CsalkoxyC2-
`
`Cealkenyl,
`
`-C(OQ)C1-C3alkoxyC2-Cealkynyl, -C(O)C1-C3alkoxyC1-Cehaloalkyl,
`
`-
`
`C(O)C1-C3alkoxyC3-Cecycloalkyl,
`-C(O)OC1-CsalkoxyCi-Cealkyl,
`-C(O)C1-
`CaalkoxyC1-CsalkoxyC1-Cealkyl, -C(O)(CH2),NR®R®, -C(O)-(CH2)n-NR’C(O)R9,
`-C(O)-(CH2)n-O-N=CR®R?,
`-CN,
`-S(O),NR'R™,
`-S(O)(=NR')RY,
` —
`C(O)C(O)R”°, —C(O)C(R*2)=N-O-R**, —C(O)C(R79)=N-NR*°R*S,-(CH2),—phenyl,
`
`-C(O)-(CH2)n-phenyl,
`
`-S(O)n-(CH2)n-phenyl,
`
`-heterocyclyl,
`
`-C(O)-(CH2)n-
`
`heterocyclyl, -S(O)n-(CH2)n-heterocyclyl, wherein each heterocyclyl is a 5- or 6-
`
`10
`
`membered heterocyclyl which may be aromatic, saturated or partially saturated
`
`and can contain from 1 to 4 heteroatoms each independently selected from the
`
`group consisting of oxygen, nitrogen and sulphur,
`
`and wherein said
`
`heterocyclyl or phenyl groups are optionally substituted by one, two or three
`
`substituents independently selected from the group consisting of C:-Csalkyl,
`
`15
`
`C1-Cs3haloalkyl, Ci-C3alkoxy, C2-C3alkenyl, C2-Csaalkynyl, halogen, cyano and
`
`nitro;
`
`R°is selected from the group consisting of hydrogen and C1-Cealkyl;
`
`20
`
`R® is selected from the group consisting of hydrogen, C1-Cealkyl, C2-Cealkenyl,
`
`C2-Cealkynyl, C1-Cehaloalkyl, hydroxyl-, Ci-Cealkoxy, C3-Ce cycloalkyl,
`, -C1-
`CaalkoxyC1-Cealkyl,
`-C1-CsalkoxyC1-Cehaloalkyl,
`-(CR9R')C1-Cehaloalkyl,
`-
`(CR°R'°)C(O)NRPER®S, phenyl,
`-pyridyl, wherein the phenyl and pyridyl are
`
`optionally substituted by one, two or three substituents independently selected
`
`25
`
`from the group consisting of C1-C3 alkyl, C1-C3 haloalkyl, C1-C3 alkoxy, C2-C3
`
`alkenyl, C2-C3 alkynyl, halogen, cyano and nitro; or
`
`R® and R® together form —CH2zCH2zOCH2CH>z-; and
`
`30
`
`R’is selected from the group consisting of hydrogen and C1-Ce¢alkyl;
`
`R® is selected from the group consisting of hydrogen, C1-C¢ alkyl, C1-Ce alkoxy,
`
`C3-Ce cycloalkyl, phenyl, -pyridyl, wherein the phenyl and pyridyl are optionally
`
`substituted by one, two or three substituents independently selected from the
`
`35
`
`group consisting of Ci-C3 alkyl, Ci-C3 haloalkyl, C1-C3 alkoxy, C2-C3 alkenyl,
`
`C2-C3 alkynyl, halogen, cyano and nitro;
`
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`R° is hydrogen or methyl;
`
`R'° is hydrogen or methyl; or
`
`R° and R" together form —CH2CH2-; and
`
`R"' is hydrogen or methyl;
`
`R' is selected from the group consisting of hydrogen, C1-Ce alkyl, hydroxyl and
`
`10
`
`C1-Ce alkoxy-;
`
`R'is selected from the group consisting of hydrogen, C1-Ceé alkyl, hydroxyl and
`
`C1-Cg¢ alkoxy; or
`
`15
`
`R' and R‘° together form —CH2-X-CH2-; and
`
`X is selected from the group consisting of O, S and N-R™;
`
`R"™ is selected from the group consisting of hydrogen, C:-Czalkyl and C1-Cs
`
`20
`
`alkoxy-;
`
`R' is independently selected from the group consisting of C1-C4 alkyl, C1-C4
`
`haloalkyl, cyano and halogen;
`
`25
`
`R'® is hydrogen or C1-Cealkyl; and
`
`R'’
`
`is selected from the group consisting of hydrogen, C1-Cealkyl, Cs-
`
`Cecycloalkyl, C1-Cg alkoxy-C1-Caalkyl-,-C(O)C1-Cealkyl, -C(O)OC1-Cealkyl and
`
`CH2CN; or
`
`30
`
`R'® and R‘ together form —CH2CH20CH2CH2-, -CH2CH2S(O)2CH2CH>2-;
`
`R'is hydrogen or C1-Cealkyl;
`
`35
`
`R'° is selected from the group consisting of hydrogen, C1-Ce alkyl, C1-Ce alkoxy,
`
`C3-Cecycloalkyl, phenyl, -pyridyl, wherein the phenyl and pyridyl are optionally
`
`substituted by one, two or three substituents independently selected from the
`
`

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`group consisting of Ci-C3 alkyl, Ci-C3 haloalkyl, C1-C3 alkoxy, C2-C3 alkenyl,
`
`C2-C3 alkynyl, halogen, cyano and nitro;
`
`R?° is selected from the group consisting of C1-Cealkyl, C1-Cehaloalkyl, C1-
`Cealkoxy-, C1-Cehaloalkoxy, -NR2'R??, phenyl and -pyridyl, wherein the phenyl
`
`and pyridyl are optionally substituted by one,
`
`two or three substituents
`
`independently selected from the group consisting of C1-C3 alkyl, Ci-C3
`
`haloalkyl, C1-C3 alkoxy, C2-C3 alkenyl, Co-C3 alkynyl, halogen, cyano and nitro;
`
`10
`
`R?' is selected from the group consisting of hydrogen, C1-Ce alkyl, C1-Ce alkoxy,
`
`C1-CealkoxyC1-Caalkyl-, C3-Ce cycloalkyl, C1-Cehaloalkyl- and C1-Ceghaloalkoxy-
`
`, -C(O)C1-Cealkyl, phenyl, -pyridyl, wherein the phenyl and pyridyl are optionally
`
`substituted by one, two or three substituents independently selected from the
`
`group consisting of C1-C3 alkyl, C1-C3 haloalkyl, C1-C3 alkoxy, C2-C3 alkenyl,
`
`15
`
`C2-C3 alkynyl, halogen, cyano and nitro;
`
`R?* is hydrogen or C1-Cealkyl; or
`
`R21 and R?? together form -CH2zCH2OCH2CH>2-;
`
`20
`
`R35 is selected from the group consisting of hydrogen, C1-Cealkyl, C1-
`
`Cehaloalkyl, C1-Cealkoxy- and C1-Cehaloalkoxy-;
`
`R*™ is selected from the group consisting of hydrogen, Ci-Cealkyl, C1-
`
`25
`
`CealkoxyC.i-Caalkyl-, C3-Cecycloalkyl, -CH2CN, tetrahydropyranyl-, phenyl and
`
`-pyridyl, wherein the phenyl and pyridyl are optionally substituted by one, two
`
`or three substituents independently selected from the group consisting of C1-
`
`Caalkyl, Ci-Cshaloalkyl, Ci-Csalkoxy, C2-Caalkenyl, C2-Csalkynyl, halogen,
`
`30
`
`35
`
`cyano and nitro;
`
`R?° is hydrogen or C1-Ce alkyl;
`
`R*° is hydrogen or C1-Ce alkyl;
`
`G is selected from the group consisting of hydrogen, -(CH2)n-R°, -C(O)-R°, -
`C(O)-(CR°R*)n-O-R®, -C(O)NR@R2, -S(O)2-R? and C1-Cgalkoxy-C1-Cgalkyl-;
`
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`R* is independently selected from the group consisting of hydrogen, C1-Cealkyl,
`
`C1-Cshaloalkyl, C2-Cgalkenyl, Co-Csalkynyl, C3-Cecycloalkyl, heterocyclyl and
`
`phenyl wherein said heterocyclyl and phenyl groups are optionally substituted
`
`by one,
`
`two or three substituents independently selected from the group
`
`consisting of Cu.i-Caalkyl, C:-Cshaloalkyl, C.i-Csalkoxy, C2-Csalkenyl, C2-
`
`Csalkynyl, halogen, cyano and nitro;
`
`R> is selected from the group consisting of Ci-Csalkyl, C:i-Cshaloalkyl, C2-
`
`10
`
`Caalkenyl, C2-Cgalkynyl, C3-Ce cycloalkyl, heterocyclyl and phenyl wherein said
`
`heterocyclyl and phenyl groups are optionally substituted by one, two or three
`
`substituents independently selected from the group consisting of C1-Csalkyl,
`
`C.1-Cshaloalkyl, Ci-C3alkoxy, C2-Csalkenyl, C2-Csalkynyl, halogen, cyano and
`
`nitro;
`
`15
`
`R° is hydrogen or C1-C3 alkyl;
`
`R* is hydrogen or C1-C3 alkyl; and
`
`20
`
`n is independently 0, 1 or 2;
`
`or an agriculturally acceptable salt thereof.
`
`25
`
`Alkyl groups (e.g C1i-Cealkyl) include, for example, methyl (Me, CH3), ethyl (Et,
`
`Ce2Hs), n-propyl (n-Pr), isopropyl (/-Pr), n-butyl (n-Bu), isobutyl (+Bu), sec-butyl (s-Bu)
`
`and tert-butyl (f-Bu).
`
`Alkenyl and alkynyl moieties can be in the form of straight or branched chains,
`
`30
`
`and the alkenyl moieties, where appropriate,
`
`can be of either
`
`the (E&)- or
`
`(Z)-configuration. Examples are vinyl, allyl and propargyl. Alkenyl and alkynyl moieties
`
`can contain one or more double and/ortriple bonds in any combination.
`
`Halogen (or halo) encompassesfluorine, chlorine, bromine or iodine. The same
`
`35
`
`correspondingly applies to halogen in the context of other definitions, such as haloalkyl.
`
`Haloalkyl groups
`
`(e.g C1-Cyhaloalkyl) are,
`
`for example,
`
`fluoromethy|l,
`
`

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`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.
`
`Alkoxy groups (e.g C1-Csalkoxy-) are, for example, methoxy, ethoxy, propoxy,
`
`isopropoxy, n-butoxy, isobutoxy, sec-butoxy or tert-butoxy, preferably methoxy and
`
`ethoxy.
`
`Alkoxyalkyl groups
`
`(¢€.g
`
`Cu1-Cealkoxy-Ci-Csalkyl-)
`
`includes,
`
`for example,
`
`10
`
`methoxymethyl, methoxyethyl,
`
`ethoxymethyl,
`
`ethoxyethyl,
`
`n-propoxymethyl,
`
`n-
`
`propoxyethyl, isopropoxymethyl or isopropoxyethyl.
`
`Cycloalkyl groups (e.g C3-Cecycloalkyl-) include, for example cyclopropyl (c-
`
`propyl, c-Pr), cyclobutyl (c-butyl, c-Bu), cyclopentyl (c-pentyl) and cyclohexyl (c-hexyl)
`
`15
`
`and may be substituted or unsubstituted as indicated.
`
`C.i-Cealkyl-S-
`
`(alkylthio)
`
`is,
`
`for example, methylthio, ethylthio, propylthio,
`
`isopropylthio, n-butylthio,
`
`isobutylthio,
`
`sec-butylthio or
`
`tert-butylthio, preferably
`
`methylthio or ethylthio.
`
`20
`
`C1-Cealkyl-S(O)-
`
`(alkylsulfinyl)
`
`is, for example, methylsulfinyl, ethylsulfinyl,
`
`propylsulfinyl, isopropylsulfinyl, n-butylsulfinyl, isobutylsulfinyl, sec-butylsulfinyl or tert-
`
`butylsulfinyl, preferably methylsulfinyl or ethylsulfinyl.
`
`25
`
`C1-Cealkyl-S(O)2- (alkylsulfonyl) is, for example, methylsulfonyl, ethylsulfonyl,
`
`propylsulfonyl, isopropylsulfonyl, n-butylsulfonyl, isobutylsulfonyl, sec-butylsulfonyl or
`
`tert-butylsulfonyl, preferably methylsulfonyl or ethylsulfonyl.
`
`Heterocyclyl
`
`is a 5- or 6- membered heterocyclyl which may be aromatic,
`
`30
`
`saturated or partially saturated and can contain from 1
`
`to 4 heteroatoms each
`
`independently selected from the group consisting of oxygen, nitrogen and sulphur.
`
`The invention also relates agriculturally acceptable salts of the compounds of
`
`Formula (I). Such salts include those which are able to form with amines, alkali metal
`
`35
`
`and alkaline earth metal bases or quaternary ammonium bases. Among the alkali
`
`metal and alkaline earth metal hydroxides as salt formers, special mention should be
`
`made of the hydroxides of lithium, sodium, potassium, magnesium and calcium, but
`
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`especially the hydroxides of sodium and potassium. The compounds of Formula (Il)
`
`according to the invention also include hydrates which may be formed during the salt
`
`formation.
`
`Examples of amines suitable for ammonium salt formation include ammonia as
`
`well as primary, secondary and tertiary C1-Cisalkylamines, C1-Cahydroxyalkylamines
`
`and C2-Cy4alkoxyalkylamines, for example methylamine, ethylamine, n-propylamine,
`
`isopropylamine,
`
`the
`
`four
`
`butylamine
`
`isomers,
`
`n-amylamine,
`
`isoamylamine,
`
`hexylamine, heptylamine, octylamine, nonylamine, decylamine, pentadecylamine,
`
`10
`
`hexadecylamine,
`
`heptadecylamine,
`
`octadecylamine,
`
`methylethylamine,
`
`methylisopropylamine,
`
`methylhexylamine,
`
`methylnonylamine,
`
`methylpentadecylamine, methyloctadecylamine, ethylbutylamine, ethylheptylamine,
`
`ethyloctylamine, hexylheptylamine, hexyloctylamine, dimethylamine, diethylamine, di-
`
`n-propylamine, diisopropylamine, di-n-butylamine, di-n-amylamine, diisoamylamine,
`
`15
`
`dihexylamine,
`
`diheptylamine,
`
`dioctylamine,
`
`ethanolamine,
`
`n-propanolamine,
`
`isopropanolamine, N,N-diethanolamine, 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,
`
`20
`
`tri-sec-butylamine,_tri-n-amylamine, methoxyethylamine and_ethoxyethylamine;
`
`heterocyclic amines,
`
`for example pyridine, quinoline,
`
`isoquinoline, morpholine,
`
`piperidine, pyrrolidine,
`
`indoline, quinuclidine and azepine; primary arylamines, for
`
`example anilines, methoxyanilines, ethoxyanilines, o-, m- and p-toluidines, phenylene-
`
`diamines, benzidines, naphthylamines and o-, m- and p-chloroanilines; but especially
`
`25
`
`triethylamine, isopropylamine and diisopropylamine.
`
`In one embodiment of the present invention R'
`
`is selected from the group
`
`consisting 1-propynyl, phenyl, pyridyl, pyrimidinyl and pyridazinyl wherein the phenyl,
`pyridyl, pyrimidinyl and pyridazinyl are optionally substituted by one or two R‘
`
`30
`
`substituents each independently selected from the group consisting of C1-C4 alkyl, C1-
`
`C4 haloalkyl, cyano and halogen (preferably fluoro or chloro).
`embodiment R' is 1-propynyl.
`
`In a preferred
`
`In one embodimentof the present invention, there is provided a compound of
`
`35
`
`Formula (la)
`
`

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`
`wherein
`
`R? is methyl or methoxy;
`
`R? is methyl or methoxy;
`
`10
`
`15
`
`R* is selected from the group consisting of C1-Caalkyl, C1-Csalkoxy-, C1-
`
`Cahaloalkyl, -C(O)C1-Caalkyl, -C(O)C1-Cahaloalkyl, -S(O)nC1-Cealkyl, -S(O)nC1-
`Cehaloalkyl, -S(O)n-(CH2)n-C3-Cecycloalkyl, -S(O)nC(R™)R'7R", -C(O)H, -C(O)-
`(CH2)n-C3-Cecycloalkyl,
`-C(O)C(R")R'2R'S,
`-C(O)C2-Caalkenyl,
`-
`C(O)(CR®R)CN,
`-C(O)OC1-Cealkyl,
`-C(O)OC1-Cehaloalkyl,
`-
`C(O)(CH2)nS(O)nC1-Cealkyl, -C(O)C1-C3alkoxyC1-Cealkyl, -C(O)NR®°R®, -C(O)-
`(CH2)n-NR’C(O)R8, -CN, -(CH2)n-phenyl, -C(O)-(CH2)n-phenyl, -S(O)n-(CH2)n-
`
`phenyl,
`
`-heterocyclyl,
`
`-C(O)-(CH2),-heterocyclyl,
`
`-S(OQ)n-(CH2),-heterocyclyl,
`
`wherein each heterocyclyl is a 5- or 6- membered heterocyclyl which may be
`
`aromatic, saturated or partially saturated and can contain from 1
`
`to 4
`
`heteroatoms each independently selected from the group consisting of oxygen,
`
`20
`
`nitrogen and sulphur, and wherein said heterocyclyl or phenyl groups are
`
`optionally substituted by one, two or three substituents independently selected
`
`from the group consisting of Ci-Cgalkyl, Ci-Cshaloalkyl, Ci-C3alkoxy, C2-
`
`Csalkenyl, C2-Czalkynyl, halogen, cyano and nitro;
`
`25
`
`R°is selected from the group consisting of hydrogen and C1-C¢alkyl;
`
`R® is selected from the group consisting of hydrogen, C1-Ce alkyl, C1-Ce alkoxy,
`
`C3-Ce cycloalkyl, phenyl, -pyridyl, wherein the phenyl and pyridyl are optionally
`
`substituted by one, two or three substituents independently selected from the
`
`30
`
`group consisting of C1-Cz alkyl, C1-C3 haloalkyl, Ci-C3 alkoxy, C2-C3 alkenyl,
`
`C2-C3 alkynyl, halogen, cyano and nitro; or
`
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`R®° and R® together form —CH2zCH2zOCH2CH--; and
`
`R’ is selected from the group consisting of hydrogen and C1-Ce alkyl;
`
`R® is selected from the group consisting of hydrogen, C1-Ce alkyl, C1-Ce alkoxy,
`
`C3-Ce cycloalkyl, phenyl, -pyridyl, wherein the phenyl and pyridyl are optionally
`
`substituted by 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;
`
`10
`
`R° is hydrogen or methyl;
`
`R'° is hydrogen or methyl; or
`
`15
`
`R° and R"° together form —CH2CHz2-; and
`
`R"' is hydrogen or methyl;
`
`R' and R‘? together form —CH2-X-CH>2-;
`
`20
`
`25
`
`X is selected from the group consisting of O, S and N-R";
`
`R' is selected from the group consisting of hydrogen, C1-Csalkyl and C1-Cs
`
`alkoxy-;
`
`G is selected from the group consisting of hydrogen, -(CH2)n-R*, -C(O)-R*, -
`C(O)-(CR°R*)n-O-R®, -C(O)NR?R?, -S(O)2-R* and C1-Cgalkoxy-C1-Caalkyl-;
`
`R* is independently selected from the group consisting of hydrogen, C:-Cealkyl,
`
`30
`
`C1-Cs3haloalkyl, C2-Cgalkenyl, C2-Cgalkynyl, C3-Cecycloalkyl, heterocyclyl and
`
`phenyl wherein said heterocyclyl and phenyl groups are optionally substituted
`
`by one,
`
`two or three substituents independently selected from the group
`
`consisting of Cui-Caalkyl, Ci-Cshaloalkyl, C1-Csalkoxy, C2-Csalkenyl, C2-
`
`Caalkynyl, halogen, cyano and nitro;
`
`35
`
`R? is selected from the group consisting of C1-Cealkyl, Ci-Cshaloalkyl, C2-
`
`Cgalkenyl, C2-Csalkynyl, C3-Ce cycloalkyl, heterocyclyl and phenyl wherein said
`
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`heterocyclyl and phenyl groups are optionally substituted by one, two or three
`
`substituents independently selected from the group consisting of C1-Casalkyl,
`
`C1-Cshaloalkyl, C1-C3zalkoxy, C2-Csaalkenyl, C2-Csalkynyl, halogen, cyano and
`
`nitro;
`
`R° is hydrogen or Ci-C3 alkyl;
`
`R* is hydrogen or C1-Csz alkyl; and
`
`10
`
`nis independently 0, 1 or 2;
`
`or an agriculturally acceptable salt thereof.
`
`In one embodimentof the present invention R? is methyl.
`
`15
`
`In one embodimentof the present invention R? is methyl.
`
`In another embodiment of the present invention R? is methoxy.
`
`20
`
`In one embodiment of the present invention R? is methyl and R? is methyl.
`
`In one embodimentof the present invention R? is methyl and R* is methoxy.
`
`In one embodimentof the present invention R? is methoxy and R® is methoxy.
`
`25
`
`In one embodimentof the present invention, R* is C1-Czalkoxy- (e.g methoxy
`
`or ethoxy).
`
`In another embodiment of the present invention R* is -C(O)Ci-Caalkyl (e.g —
`
`30
`
`C(O)methyl, —C(O)ethyl, —C(O)+propyl) or —C(O)ft-butyl).
`
`In another embodiment of the present invention, R* is -C(O)C1-Cs3haloalkyl,
`
`more preferably -C(O)C1-C2fluoroalkyl e.g -C(O)CHaF, -C(O)CHFa, -C(O)CF:3).
`
`35
`
`In one embodiment of the present invention, R*is -S(O),C1-Cealkyl especially —
`
`S(O)emethyl or —S(O)zethyl
`
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`

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`PCT/EP2019/077185
`
`In
`
`another
`
`embodiment
`
`R*
`
`is
`
`-S(O),Ci-Cehaloalkyl,
`
`for
`
`example
`
`-
`
`S(O)echloromethyl.
`
`In another embodiment R‘is -S(O)n-(CH2)n-C3-Cecycloalkyl, for example -S(O)2-
`
`(CH2)-c-propyl or, where n is 0, -C3-Cecycloalkyl (for example cyclopropyl).
`
`In another embodiment of the present
`
`invention, R* is -C(O)OC1-Cealkyl,
`
`especially -C(O)-O-methyl.
`
`10
`
`In another embodiment of the present invention, R* is -S(O),hC(R™)R'2R*® or -
`C(O)C(R")R**R*® wherein R" is hydrogen or methyl and R'?R*S taken together are —
`
`CH2OCH>- (oxetan-3-yl).
`
`In another embodiment of
`
`the present
`
`invention, R* is
`
`-C(O)-(CH2)n-C3-
`
`15
`
`Cecycloalkyl, for example -C(O)-c-propyl or -C(O)-(CHz2)-c-propyl.
`
`In another embodiment of the present invention, R* is -C(O)(CR°R")CN, for
`
`example -C(O)CH2CN, -C(O)CH(CHa3)CN or -C(O)C(CH3)2CN.
`
`20
`
`In another embodiment of the present invention, R* is -C(O)(CH2)nS(O)nC1-
`
`Cealkyl, for example -C(O)CH2S(O)2methyl.
`
`In another embodiment of the present invention, R* is -C(O)C1-CsalkoxyC1-
`
`Cealkyl, for example -C(O)CH2-O-CHs, -C(O)CH2CH2-O-CH3 or -C(O)CH(CHs3)-O-CHs3.
`
`25
`
`In another embodiment of the present invention, R*is -C(O)NR®°R®, especially
`wherein R® is hydrogen and R®is C1-Ce alkyl e.g t-butyl.
`
`In another embodimentof the present invention, R*is -C(O)-(CH2)n-NR’C(O)R®,
`for example -C(O)-(CH2)-NR’C(O)R® or -C(O)NR’C(O)R®, for example -C(O)NHC(O)-
`
`30
`
`t-butyl or -C(O)NHC(O)pyrid-2-yl.
`
`In another embodiment of the present invention, R* is selected from the group
`
`consisting of —phenyl, -C(O)-phenyl, -S(O),aphenyl wherein each phenyl is optionally
`
`35
`
`substituted as defined previously.
`
`In another embodiment of the present invention R* is heterocyclyl, -C(O)-
`
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`

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`
`PCT/EP2019/077185
`
`heterocyclyl or -S(O)n-heterocyclyl.
`
`In another embodiment, each aforementioned
`
`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 defined previously. In another
`
`embodiment, each aforementioned 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 defined previously.
`
`In another
`
`10
`
`embodiment, each aforementioned heterocyclyl
`
`is a saturated heterocyclyl more
`
`preferably selected from the group consisting of morpholinyl,
`
`tetrahydrofuryl and
`
`tetrahydropyranyl each of which is optionally substituted as defined previously.
`
`In one embodiment of the present invention, G is selected from the group
`
`15
`
`consisting of hydrogen, Ci-Cgalkyl (e.g methyl, ethyl, n-propyl, Hpropyl, n-butyl, Hbutyl,
`
`-C2-Cgalkenyl
`
`(e.g vinyl), Ce-Csalkynyl
`
`(e.g propargyl),
`
`-C(OQ)C1-Csalkyl
`
`(more
`
`preferably -C(O)C1-Cealkyl e.g -C(O)i-propyl and -C(O)t-butyl) and -C(O)-O-C1-Cealky|
`
`(more preferably -C(O)-O-C1-Cealkyl e.g -C(O)-O-methyl). In a preferred embodiment,
`
`G is hydrogen.
`
`20
`
`Depending on the nature of the substituents, compounds of Formula (I) may
`
`exist in different isomeric forms. When G is hydrogen, for example, compounds of
`
`Formula (I) may exist in different tautomeric forms.
`
`25
`
`This invention covers all such isomers and tautomers and mixtures thereof in
`
`all proportions. Also, when substituents contain double bonds, cis- and trans-isomers
`
`can exist. These isomers, too, are within the scope of the claimed compounds of the
`
`Formula (I). Compounds of Formula (1) may contain asymmetric centres and may be
`
`present as a single enantiomer, pairs of enantiomers in any proportion or, where more
`
`30
`
`than one asymmetric centre are present, contain diastereoisomers in all possible
`
`ratios. Typically one of the enantiomers has enhanced biological activity compared to
`
`the other possibilities.
`
`The compounds of Formula (I) according to the invention can be used as
`
`35
`
`herbicides by themselves, but
`
`they are generally formulated into herbicidal
`
`compositions using formulation adjuvants, such as carriers, solvents and surface-
`
`active agents (SFAs). Thus,
`
`the present
`
`invention further provides a_ herbicidal
`
`

`

`WO 2020/074489
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`PCT/EP2019/077185
`
`composition comprising a herbicidal compound according to any one of the previous
`
`claims and an agriculturally acceptable formulation adjuvant. The composition can be
`
`in the form of concentrates which are diluted prior to use, although ready-to-use
`
`compositions can also be made. The final dilution is usually made with water, but can
`
`be made instead of, or in addition to, water, with, for example,
`
`liquid fertilisers,
`
`micronutrients, biological organisms, oil or solvents.
`
`The herbicidal compositions generally comprise from 0.1 to 99 % by weight,
`
`especially from 0.1 to 95 % by weight, compounds of Formula (I) and from 1 to 99.9 %
`
`10
`
`by weight of a formulation adjuvant which preferably includes from 0 to 25 % by weight
`
`of a surface-active substance.
`
`The compositions can be chosen from a number of formulation types, many of
`
`which are known from the Manual on Development and Use of FAO Specifications for
`
`15
`
`Plant Protection Products, 5th Edition, 1999. These include dustable 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 liquids (OL), ultra low volume liquids (UL), emulsifiable concentrates
`
`(EC), dispersible concentrates (DC), emulsions (both oil in water (EW) and water in oil
`
`20
`
`(EO)), micro-emulsions (ME), suspension concentrates (SC), aerosols, capsule
`
`suspensions (CS) and seed treatment formulations. The formulation type chosen in
`
`any instance will depend upon the particular purpose envisaged and the physical,
`
`chemical and biological properties of the compound of Formula (1).
`
`Dustable powders (DP) may be prepared by mixing a compound of Formula (I)
`
`25
`
`with one or more solid diluents (for example natural clays, Kaolin, pyrophyllite,
`
`bentonite, alumina, montmorillonite, kieselguhr, chalk, diatomaceous earths, calcium
`
`phosphates, calcium and magnesium carbonates, sulphur, lime, flours, talc and other
`
`organic and inorganic solid carriers) and mechanically grinding the mixture to a fine
`
`powder.
`
`30
`
`Soluble powders (SP) may 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 sulphate) or one or more water-soluble organic solids (such
`
`as a polysaccharide) and, optionally, one or more wetting agents, one or more
`
`dispersing agents or a mixture of said agents to improve waterdispersibility/solubility.
`
`35
`
`The mixture is then ground to a fine powder. Similar compositions may also be
`
`granulated to form water soluble granules (SG).
`
`

`

`WO 2020/074489
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`
`Wettable powders (WP) may be prepared by mixing a compound of Formula
`
`(1) 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 the dispersion in liquids. The mixture is then ground to a fine
`
`powder.
`
`Similar compositions may also be granulated to form water dispersible
`
`granules (WG).
`
`Granules (GR) may be formed either by granulating a mixture of a compound
`
`of Formula (1) and one or more powdered solid diluents or carriers, or from pre-formed
`
`blank granules by absorbing a compound of Formula (I) (or a solution thereof,
`
`in a
`
`10
`
`suitable agent) in a porous granular material (such as pumice, attapulgite clays, fuller's
`
`earth, kieselguhr, diatomaceous earths or ground corn cobs) or by adsorbing a
`
`compound of Formula (I) (or a solution thereof, in a suitable agent) on to a hard core
`
`material (such as sands, silicates, mineral carbonates, sulphates or phosphates) and
`
`drying if necessary. Agents which are commonly usedto aid absorption or adsorption
`
`15
`
`include solvents (such as aliphatic and aromatic petroleum solvents, alcohols, ethers,
`
`ketones and esters) and sticking agents (such as polyvinyl acetates, polyvinyl alcohols,
`
`dextrins, sugars and vegetable oils). One or more other additives may also be included
`
`in granules (for example an emulsifying agent, wetting agent or dispersing agent).
`
`Dispersible Concentrates (DC) may be prepared by dissolving a compound of
`
`20
`
`Formula (Il) in water or an organic solvent, such as a Ketone, alcohol or glycol ether.
`
`These solutions may contain a surface active agent (for example to improve water
`
`dilution or prevent crystallisation in a spray tank).
`
`Emulsifiable concentrates (EC) or oil-in-water emulsions (EW) may be
`
`prepared by dissolving a compound of Formula (I) in an organic solvent (optionally
`
`25
`
`containing one or more wetting agents, one or more emulsifying agents or a mixture of
`
`said agents). Suitable organic solvents for use in ECs include aromatic hydrocarbons
`
`(such as alkylbenzenes or alkylnaphthalenes, exemplified by SOLVESSO 100,
`
`SOLVESSO 150 and SOLVESSO 200; SOLVESSO is a Registered Trade Mark),
`
`ketones (such as cyclohexanone or methylcyclohexanone) and alcohols (such as
`
`30
`
`benzyl
`
`alcohol,
`
`furfuryl
`
`alcohol or butanol), N-alkylpyrrolidones
`
`(such as N-
`
`methylpyrrolidone or N-octylpyrrolidone), dimethyl amides of fatty acids (such as Cez-
`
`Cio fatty acid dimethylamide) and chlorinated hydrocarbons. An EC product may
`
`spontaneously emulsify on addition to water, to produce an emulsion with sufficient
`
`stability to allow spray application through appropriate equipment.
`
`35
`
`Preparation of an EW involves obtaining a compound of Formula (I) either as a
`
`

`

`WO 2020/074489
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`
`PCT/EP2019/077185
`
`liquid (if it
`
`is not a liquid at room temperature,
`
`it may be melted at a reasonable
`
`temperature, typically below 70°C) or in solution (by dissolving it
`
`in an appropriate
`
`solvent) and then emulsifying the resultant liquid or solution into water containing one
`
`or more SFAs, under high shear, to produce an emulsion. Suitable solvents for use in
`
`EWs include vegetable oils, chlorinated hydrocarbons (such as chlorobenzenes),
`
`aromatic solvents (such as alkylbenzenesor alkylnaphthalenes) and other appropriate
`
`organic solvents which have a low solubility in water.
`
`Microemulsions (ME) may be prepared by mixing water with a blend of one or
`
`more solvents with one or more SFAs, to produce spontaneously a thermodynamically
`
`10
`
`stable isotropic liquid formulation. A compound of Formula (I) is presentinitially in
`
`either the water or the solvent/SFA blend. Suitable solvents for use in MEs include
`
`those hereinbefore described for use in in ECs or in EWs. An ME maybeeither an
`
`oil-in-water or a water-in-oil system (which system is present may be determined by
`
`conductivity measurements) and may be suitable for mixing water-soluble and oil-
`
`15
`
`soluble pesticides in the same formulation. An ME is suitable for dilution into water,
`
`either remaining as a microemulsion or forming a conventional oil-in-water emulsion.
`
`Suspension concentrates (SC) may comprise aqueous or non-aqueous
`
`suspensions of finely divided insoluble solid particles of a compound of Formula (I).
`
`SCs may be prepared by ball or bead milling the solid compound of Formula (I) in a
`
`20
`
`suitable medium, optionally with one or more dispersing agents, to produce a fine
`
`particle suspension of the compound. One or more wetting agents maybeincludedin
`
`the composition and a suspending agent maybe included to reduce the rate at which
`
`the particles settle. Alternatively, a compound of Formula (I) may be dry milled and
`
`added to water, containing agents hereinbefore described, to produce the desired end
`
`25
`
`product.
`
`Aerosol formulations comprise a compound of Formula (1) and a suitable
`
`propellant (for example n-butane). A compound of Formula (I) may also be dissolved
`
`or dispersed in a suitable medium (for example water or a water miscible liquid, such
`
`as n-propanol) to provide compositions for use in non-pressurised, hand-actuated
`
`30
`
`spray pumps.
`
`Capsule suspensions (CS) may be prepared in a manner similar to the
`
`preparation of EW formulations but with an additional polymerisation stage such that
`
`an aqueous dispersion of oil droplets is obtained,
`
`in which each oil droplet
`
`is
`
`encapsulated by a polymeric shell and contains a compound of Formula (I) and,
`
`35
`
`optionally, a carrier or diluent therefor. The polymeric shell may be produced by either
`
`

`

`WO 2020/074489
`
`16
`
`PCT/EP2019/077185
`
`an interfacial polycondensation reaction or by a coacervation procedure.
`
`The
`
`compositions may provide for controlled release of the compound of Formula (1) and
`
`they may be used for seed treatment. A compound of Formula (Il) may also be
`
`formulated in a biodegradable polymeric 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 or
`
`distribution on surfaces; resistance to rain on treated surfaces; or uptake or mobility of
`
`a compound of Formula (I). Such additives include surface active agents (SFAs), spray
`
`10
`
`additives based on oils, for example certain mineral oils or natural plant oils (such as
`
`soy bean and rape seedoil), and blends of these with other bio-enhancing adjuvants
`
`(ingredients which may aid or modify the action of a compound of Formula (I).
`
`Wetting agents, dispersing agents and emulsifying agents may be SFAsof the
`
`cationic, anionic, amphoteric or non-ionic type.
`
`15
`
`Suitable SFAs of the cationic type include quaternary ammonium compounds
`
`(for example cetyltrimethyl ammonium bromide), imidazolines and amine salts.
`
`Suitable anionic SFAs include alkali metals salts of fatty acids, salts of aliphatic
`
`monoesters of sulphuric acid (for example sodium lauryl
`
`sulphate),
`
`salts of
`
`sulphonated aromatic compounds (for example sodium dodecylbenzenesulphonate,
`
`20
`
`calcium dodecylbenzenesulphonate, butylnaphthalene sulphonate and mixtures of
`
`sodium di-isopropyl- and tri-isopropyl-naphthalene sulphonates), ether sulphates,
`
`alcohol ether sulphates (for example sodium laureth-3-sulphate), ether carboxylates
`
`(for example sodium laureth-3-carboxylate), phosphate esters (products from the
`
`reaction between one or more fatty alcohols and phosphoric acid (predominately
`
`25
`
`mono-esters) or phosphorus pentoxide (predominately di-esters), for example the
`
`reaction between lauryl alcohol an