(12) INTERNATIONAL APPLICATION PUBLISHED UNDER THE PATENT COOPERATION TREATY (PCT)
`
`(ARYATA
`
`(10) International Publication Number
`WO 2020/074489 Al
`
`= =
`
`WIPO! PCT
`
`(19) World Intellectual Property
`Organization
`International Bureau
`
`(43) International Publication Date
`16 April 2020 (16.04.2020)
`
`PCT/EP2019/077185
`
`(84)
`
`CA, CH, CL, CN, CO, CR, CU, CZ, DE, DJ, DK, DM, DO,
`DZ, EC, EE, EG, ES, FL, GB, GD, GE, GH, GM,GT, HN,
`HR, HU, ID, IL, IN,IR, IS, JO, JP, KE, KG, KH, KN,KP,
`KR, KW, KZ, LA, LC, LK, LR, LS, LU, LY, MA, MD, ME,
`MG, MK, MN, MW, MX, MY, MZ, NA, NG, NL, NO, NZ,
`OM,PA, PE, PG, PH, PL, PT, QA, RO, RS, RU, RW, SA,
`SC, SD, SE, SG, SK, SL, SM, ST, SV, SY, TH, TJ, TM, TN,
`TR, TT, TZ, UA, UG, US, UZ, VC, VN, ZA, ZM, ZW.
`
`Designated States (unless otherwise indicated, for every
`kind of regional protection available): ARIPO (BW, GH,
`GM, KE, LR, LS, MW, MZ, NA, RW, SD, SL, ST, SZ, TZ,
`UG, ZM, ZW), Eurasian (AM, AZ, BY, KG, KZ, RU, TJ,
`TM), European (AL, AT, BE, BG, CH, CY, CZ, DE, DK,
`
`EELEs. TLER, GB. GR, HR, HU,IE, IS, IT, LT, LU, LV,
`
`MC, MK, MT, NL, NO, PL, PT, RO, RS, SE, SI, SK, SM,
`TR), OAPI (BF, BJ, CF, CG, CI, CM, GA, GN, GQ, GW,
`KM,ML, MR, NE, SN, TD, TG).
`
`Declarations under Rule 4.17:
`
`as to applicant's entitlement to apply for and be granted a
`patent (Rule 4.17(ii))
`of inventorship (Rule 4.17(iv))
`Published:
`
`with international search report (Art. 21(3))
`
`(6)
`
`International Patent Classification:
`CO7D 205/04 (2006.01)
`CO7D 403/10 (2006.01)
`CO7D 401/06 (2006.01)
`CO07D 405/06 (2006.01)
`CO7D 401/10 (2006.01)
`CO7D 413/06 (2006.01)
`CO7D 401/14 (2006.01)
`CO7D 417/06 (2006.01)
`CO7D 403/06 (2006.01)
`AOIN 35/06 (2006.01)
`
`(21)
`
`International Application Number:
`
`(22)
`
`International Filing Date:
`
`(25) Filing Language:
`.
`
`(26) Publication Language:
`
`08 October 2019 (08.10.2019)
`
`English
`.
`
`English
`
`(30) Priority Data:
`1816459.0
`.
`(71) Applicant: SYNGENTA CROP PROTECTION AG
`[CH/CH]; Schwarzwaldallee 215, 4058 Basel (CH).
`
`09 October 2018 (09.10.2018)
`
`GB
`
`(72)
`
`Inventors: HENNESSY, Alan, Joseph; Syngenta Lim-
`ited Syngenta, Jcalott's Hill International Rescarch Ccn-
`tre, Bracknell Berkshire RG42 6EY (GB). JONES, Eliz-
`abeth, Pearl; Syngenia Limited Syngenta, Jealott's Hill
`International Rescarch Centre, Bracknell Berkshire RG42
`6GEY (GB). DALE, Suzanna; Syngenta Limited Syngen-
`ta, Jealoit’s Hill Tnternational Research Centre, Brack-
`nell Berkshire RG42 6EY (GB). GREGORY,Alexander,
`William; Syngenta Limited Syngenta, Jealott’s Hill Inter-
`national Research Centre, Bracknell Berkshire RG42 6EY
`(GB). HOULSBY, Ian, Thomas, Tinmouth; Syngenta
`Limited Syngenta, Jealott's Hill International Research Cen-
`tre, Bracknell Berkshire RG42 6EY (GB). BHONOAH,
`Yunas; Syngenta Limited Syngenta, Jcalott's Hill Intcrna-
`tional Research Centre, Bracknell Berkshire RG42 6EY
`(GB). COMAS-BARCELO,Julia; Syngenta Limited Syn-
`genta, Jcalott's Hill International Rescarch Centre, Brack-
`nell Berkshire RG42 6EY (GB). ELVES, Philip, Michael;
`Syngenta Limited Syngenta, Jealott’s Hill International Re-
`scarch Centre, Bracknell Berkshire RG42 6EY (GB).
`
`(74)
`
`(81)
`
`Agent: SYNGENTAIP; Rosentalstrasse 67, 4058 Basel
`(CH).
`
`Designated States (unless otherwise indicated, for every
`kind of national protection available): AE, AG, AL, AM,
`AO, AT, AU, AZ, BA, BB, BG, BH, BN, BR, BW, BY, BZ,
`
`(64) Title: HERBICIDAL 2-AZASPIRO[3-5JNONANE COMPOUNDS
`O Re
`(57) Abstract: The present invention relates to compoundsof Formula (1), wherein R!R?,
`R*, R* and G are as defined herein. The invention furtherrelates to herbicidal compositions
`XL“0
`which comprise a compoundof Formula (1), to their use for controlling weeds, in particular
`in crops of useful plants.
`pr
`
`G
`
`
`
`
`
`wo2020/074489A.ITNIMINIINIUKITTYCRAYEMMAAA
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`

`

`WO 2020/074489
`
`1
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`PCT/EP2019/077185
`
`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
`
`W0O2015/197468. 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 (I)
`
`OR.
`
`XQ
`OR
`(!)
`
`3
`
`G
`
`15
`
`wherein
`
`R'is selected from the group consisting of methyl, ethynyl, 1-propynyl, pheny!
`
`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 C:-Csalkyl, C1-Cualkoxy-, C1-
`
`Cahaloalkyl, -C(O)C1-Caalkyl, -C(O)C1-Cahaloalkyl, -S(O)nC1-Cealkyl, -S(O)nC1-
`Cehaloalkyl, -S(O)n-(CH2)n-Ca-Cecycloalkyl, -S(O)nC(R™)R'7R', -C(O)H, -C(O)-
`(CH2)n-C3-Cecycloalkyl,
`-C(O)C(R™")R'R*,
`-C(O)C2-Caalkenyl,
`-
`C(O)(CR®R™)CN,
`-C(O)CRER™®)(CRER™)CN,
`-C(O)CH2C(O)-C1-Cealkyl,
`-
`
`

`

`WO 2020/074489
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`PCT/EP2019/077185
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`
`
`C(O)CH20C(O)-C1-Cealkyl, -C(O)OC1-Cehaloalkyl,=--C(O)OC1-Cealkyl,
`
`
`
`C(O)(CH2)nS(O )nC1-Cealkyl, -C(O)C1-CsalkoxyC1-Cealkyl, -C(O)C1-CsalkoxyC2-
`
`Cealkenyl, -C(O)C1-CsalkoxyC2-Cealkynyl, -C(O)C1-CsalkoxyC1-Cehaloalkyl,
`
`-
`
`C(O)C1-CsalkoxyC3-Cecycloalkyl,
`-C(O)OC1-CsalkoxyC1-Cealkyl,
`-C(O)Ci-
`CzalkoxyC1-C3alkoxyC1-Cealkyl, -C(O)(CH2)nNR®°RS, -C(O)-(CH2)n-NR’C(O)R®,
`-C(O)-(CH2)n-O-N=CR®R®,
`-CN,
`-S(O)NRTR'’,
`-S(O)=NR®)RY,
` —
`C(O)C(O)R”°, —C(O)C(R?3)=N-O-R”4, —C(O)C(R*3)=N-NR*R”“,-(CH2)n—phenyl,
`
`-C(O)-(CH2)n-phenyl,
`
`-S(O)n-(CHz2)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 C1-Caalkyl,
`
`15
`
`C1-Cs3haloalkyl, C1-C3alkoxy, C2-C3alkenyl, C2-C3alkynyl, halogen, cyano and
`
`nitro;
`
`R°is selected from the group consisting of hydrogen and C1-C¢alkyl;
`
`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,
`-(CR°R')C1-Cehaloalkyl,
`-
`(CR°R'°)C(O)NR®R®, 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 —CHzCH2zOCH2CH?2-; and
`
`30
`
`R’ is selected from the group consisting of hydrogen and C:-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
`
`35
`
`group consisting of C1-C3 alkyl, Ci-C3 haloalkyl, C1-C3 alkoxy, C2-C3 alkenyl,
`
`C2-C3 alkynyl, halogen, cyano and nitro;
`
`

`

`WO 2020/074489
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`PCT/EP2019/077185
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`R° is hydrogen or methyl;
`
`R'° is hydrogen or methyl; or
`
`R® and R" together form —CH2CH>2-; 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-Ce alkyl, hydroxyl and
`
`C1-Cez 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, Ci-Csalkyl and C1-Cs
`
`20
`
`alkoxy-;
`
`R'® is independently selected from the group consisting of C1-C,4 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-C;-Csalkyl-,-C(O)C1-Cealkyl, -C(O0)OC1-Cealkyl and
`
`CH2CN; or
`
`30
`
`R'® and R' together form —CH2zCH20CH2CH2-, -CH2CH2S(O)2CH2CH2-;
`
`R'8is 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
`
`

`

`WO 2020/074489
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`PCT/EP2019/077185
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`group consisting of C1-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'R22, phenyl and -pyridyl, wherein the pheny!
`
`and pyridyl are optionally substituted by one,
`
`two or three substituents
`
`independently selected from the group consisting of C1-C3 alkyl, Ci-C3
`
`haloalkyl, Ci-C3 alkoxy, C2-C3 alkenyl, C2-C3 alkynyl, halogen, cyano and nitro;
`
`10
`
`R?" is selected from the group consisting of hydrogen, C1-Ce alkyl, C1-Ce¢ alkoxy,
`
`C.1-CealkoxyC.1-Caalkyl-, Ca-Ce cycloalkyl, Ci-Cehaloalkyl- and C1-Cehaloalkoxy-
`
`, -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 Ci-Cs alkyl, C:-C3 haloalkyl, C:-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 -CH2CH2OCH2CH>-;
`
`20
`
`R*3 is selected from the group consisting of hydrogen, C:i-Cealkyl, Cu1-
`
`Cehaloalkyl, C1-Cealkoxy- and C1-Cehaloalkoxy-;
`
`R* is selected from the group consisting of hydrogen, Ci-Cealkyl, C1-
`
`25
`
`CealkoxyC1-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 C:-
`
`Csalkyl, C1-Cs3haloalkyl, Ci-Csalkoxy, Cz2-Csalkenyl, C2-Csalkynyl, halogen,
`
`30
`
`35
`
`cyano and nitro;
`
`R*> is hydrogen or C1-Ce alkyl;
`
`R*6 is hydrogen or C1-Ce alkyl;
`
`G is selected from the group consisting of hydrogen, -(CH2),-R?, -C(O)-R?, -
`C(O)-(CRSR")n-O-R®, -C(O)NR&R2, -S(O)2-R? and C1-Csalkoxy-C1-Caalkyl-;
`
`

`

`WO 2020/074489
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`PCT/EP2019/077185
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`R? is independently selected from the group consisting of hydrogen, Ci-Cealkyl,
`
`C1-Cshaloalkyl, C2-Cealkenyl, 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 Cu1-Csalkyl, C1-Cshaloalkyl, C1-Csalkoxy, C2-Csalkenyl,
`
`Co2-
`
`Cz3alkynyl, halogen, cyano and nitro;
`
`R° is selected from the group consisting of Ci-Csalkyl, C1-Cshaloalkyl, C2-
`
`10
`
`Cealkenyl, Co-Csalkynyl, 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 Ci-Csalkyl,
`
`C1-Cs3haloalkyl, Ci1-Cgalkoxy, C2-C3alkenyl, Co-Caalkynyl, halogen, cyano and
`
`nitro;
`
`15
`
`R° is hydrogen or C1-C3 alkyl;
`
`R* is hydrogen or C1-Cz3 alkyl; and
`
`20
`
`n is independently 0, 1 or 2;
`
`or an agriculturally acceptable salt thereof.
`
`25
`
`Alkyl groups (e.g C1-Cealkyl) include, for example, methyl (Me, CHs3), ethyl (Et,
`
`Ce2Hs), n-propyl (n-Pr), isopropyl (/-Pr), n-butyl (n-Bu), isobutyl (/-Bu), sec-butyl (s-Bu)
`
`and tert-butyl (t-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 (&)- or
`
`(Z)-configuration. Examples are vinyl, allyland 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 halogenin the context of other definitions, such as haloalkyl.
`
`Haloalkyl groups
`
`(e.g Ci-C,shaloalkyl) are,
`
`for example,
`
`fluoromethyl,
`
`

`

`WO 2020/074489
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`6
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`PCT/EP2019/077185
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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-Cyalkoxy-) are, for example, methoxy, ethoxy, propoxy,
`
`isopropoxy, n-butoxy,
`
`isobutoxy, sec-butoxy or tert-butoxy, preferably methoxy and
`
`ethoxy.
`
`Alkoxyalkyl groups
`
`(e.g C1-Cealkoxy-C1-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.1-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
`
`C.1-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 (1). 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
`
`

`

`WO 2020/074489
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`7
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`PCT/EP2019/077185
`
`especially the hydroxides of sodium and potassium. The compounds of Formula (I)
`
`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 C:-Cisalkylamines, Ci-Cahydroxyalkylamines
`
`and C2-Caalkoxyalkylamines, 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-Ca 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
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`R? is methyl or methoxy;
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`R? is methyl or methoxy;
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`R* is selected from the group consisting of C1-Csalkyl, C1-Caalkoxy-, C1-
`
`C,ahaloalkyl, -C(OQ)C1-Caalkyl, -C(Q)C1-C4haloalkyl, -S(OQ)nC1-Cealkyl, -S(O)nC1-
`Cehaloalkyl, -S(O)n-(CH2)n-Ca-Cecycloalkyl, -S(O)nC(R™)R'2R'3, -C(O)H, -C(O)-
`(CH2)n-C3-Cecycloalkyl,
`-C(O)C(R™")R'?R*,
`-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-CzalkoxyC1-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-
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`phenyl,
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`-heterocyclyl,
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`-C(O)-(CH2),-heterocyclyl,
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`-S(O),n-(CH2),-heterocyclyl,
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`wherein each heterocyclyl is a 5- or 6- membered heterocyclyl which may be
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`aromatic, saturated or partially saturated and can contain from 1
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`to 4
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`heteroatoms each independently selected from the group consisting of oxygen,
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`nitrogen and sulphur, and wherein said heterocyclyl or phenyl groups are
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`optionally substituted by one, two or three substituents independently selected
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`from the group consisting of C1-Csalkyl, Ci-C3haloalkyl, C1-Csalkoxy, Co-
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`Czalkenyl, C2-C3alkynyl, halogen, cyano and nitro;
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`R°is selected from the group consisting of hydrogen and C1-C¢alkyl;
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`R®° is selected from the group consisting of hydrogen, C1-Ce¢alkyl, C1-Ce alkoxy,
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`C3-Ce cycloalkyl, phenyl, -pyridyl, wherein the phenyl and pyridyl are optionally
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`substituted by one, two or three substituents independently selected from the
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`group consisting of C1-C3 alkyl, Ci-C3 haloalkyl, C1-C3 alkoxy, C2-C3 alkenyl,
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`C2-C3 alkynyl, halogen, cyano and nitro; or
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`R® and R® together form —CH2zCH2zOCH2CH>2-; and
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`R’is selected from the group consisting of hydrogen and C1-Cealkyl;
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`R® is selected from the group consisting of hydrogen, C1-Ce¢alkyl, C1-Ce alkoxy,
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`C3-Cez cycloalkyl, phenyl, -pyridyl, wherein the phenyl and pyridyl are optionally
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`substituted by one, two or three substituents independently selected from the
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`group consisting of C1-C3 alkyl, Ci-C3 haloalkyl, Ci-Cz3 alkoxy, C2-C3 alkenyl,
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`C2-C3 alkynyl, halogen, cyano and nitro;
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`R° is hydrogen or methyl;
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`R'° is hydrogen or methyl; or
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`R° and R" together form —CH2CH2-; and
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`R"' is hydrogen or methyl;
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`R' and R‘ together form —CH2-X-CH>-;
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`X is selected from the group consisting of O, S and N-R™;
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`R" is selected from the group consisting of hydrogen, C:-Csaalkyl and C1-C3
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`alkoxy-;
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`G is selected from the group consisting of hydrogen, -(CH2)n-R?, -C(O)-R?, -
`C(O)-(CRER®)n-O-R®, -C(O)NRfR2, -S(O)2-R? and C1-Csalkoxy-C1-Csalkyl-;
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`R? is independently selected from the group consisting of hydrogen, C1-Cealkyl,
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`C1-Cshaloalkyl, C2-Cgalkenyl, C2-Cealkynyl, Cs-Cecycloalkyl, heterocyclyl and
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`phenyl wherein said heterocyclyl and phenyl groups are optionally substituted
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`by one,
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`two or three substituents independently selected from the group
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`consisting of Cu1-Csalkyl, C1-Cshaloalkyl, C1-C3alkoxy, C2-C3alkenyl,
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`Co2-
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`Cz3alkynyl, halogen, cyano and nitro;
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`R° is selected from the group consisting of C1-Cgalkyl, C1-Cshaloalkyl, C2-
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`Csalkenyl, C2-Cgalkynyl, C3-Ce cycloalkyl, heterocyclyl and phenyl wherein said
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`heterocyclyl and phenyl groups are optionally substituted by one, two or three
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`substituents independently selected from the group consisting of C1-Cs3alkyl,
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`C1-Cs3haloalkyl, Ci-Csalkoxy, C2-C3alkenyl, C2-Cs3alkynyl, halogen, cyano and
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`nitro;
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`R° is hydrogen or C4-Cz3alkyl;
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`R* is hydrogen or C1-Cz alkyl; and
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`n is independently 0, 1 or 2;
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`or an agriculturally acceptable salt thereof.
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`In one embodimentof the present invention R? is methyl.
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`In one embodimentof the present invention R® is methyl.
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`In another embodimentof the present invention R° is methoxy.
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`In one embodimentof the present invention R? is methyl and R* is methyl.
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`In one embodimentof the present invention R? is methyl and R* is methoxy.
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`In one embodiment of the present invention R? is methoxy and R* is methoxy.
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`In one embodiment of the present invention, R* is C1-Czalkoxy- (e.g methoxy
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`or ethoxy).
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`In another embodiment of the present invention R* is -C(O)C1-Caalkyl (e.g —
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`C(O)methyl, —C(O)ethyl, —C(O)/-propyl) or —-C(O)t-butyl).
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`In another embodiment of the present invention, R* is -C(OQ)C1-Cghaloalkyl,
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`more preferably -C(O)C1-Cofluoroalkyl e.g -C(O)CHaF, -C(O)CGHFa, -C(O)CF:3).
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`In one embodimentof the present invention, R*is -S(O),C1-Cealkyl especially —
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`S(O)emethyl or —S(O)zethyl
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`In|
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`another
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`embodiment
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`R*
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`is
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`-S(O)nC1-Cehaloalkyl,
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`for
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`example
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`-
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`S(O)2chloromethyl.
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`In another embodiment R*is -S(O)n-(CH2)n-C3-Cecycloalkyl, for example -S(O)2-
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`(CHz2)-c-propyl or, where n is 0, -C3-Cecycloalkyl (for example cyclopropyl).
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`In another embodiment of the present
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`invention, R* is -C(O)OC1-Cealkyl,
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`especially -C(O)-O-methyl.
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`In another embodiment of the present invention, R* is -S(O),C(R™)R'?R* or -
`C(O)C(R"™")R'R'3 wherein R" is hydrogen or methyl and R'?R‘3 taken together are —
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`CGH2O0CH?2- (oxetan-3-yl).
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`In another embodiment of
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`the present
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`invention, R* is
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`-C(O)-(CH2)n-Cs-
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`Cecycloalkyl, for example -C(O)-c-propyl or -C(O)-(CHz2)-c-propyl.
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`In another embodiment of the present invention, R* is -C(O)(CR°R")CN, for
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`example -C(O)CH2CN, -C(O)CH(CHs3)CN or -C(O)C(CH3)2CN.
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`In another embodiment of the present invention, R* is -C(O)(CH2)nS(O)nC1-
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`Gealkyl, for example -C(O)CH2S(O)2methyl.
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`In another embodiment of the present invention, R* is -C(O)C1-CsalkoxyC.-
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`Cealkyl, for example -C(O)CH2-O-CHs, -C(O)CH2CH2-O-CHs3 or -C(O)CH(CH3)-O-CHs3.
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`In another embodiment of the present invention, R*is -C(O)NR°R®, especially
`wherein R® is hydrogen and R® is C1i-Ce¢ alkyl e.g t-butyl.
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`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)-
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`t-butyl or -C(O)NHC(O)pyrid-2-yl.
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`In another embodiment of the present invention, R* is selected from the group
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`consisting of —phenyl, -C(O)-phenyl, -S(O)nphenyl wherein each phenyl is optionally
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`substituted as defined previously.
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`In another embodiment of the present invention R* is heterocyclyl, -C(O)-
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`heterocyclyl or -S(O),-heterocyclyl.
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`In another embodiment, each aforementioned
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`heterocyclyl is an aromatic heterocyclyl (i.e heteroaryl), more preferably selected from
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`the group consisting of furanyl, pyrrolyl, thiophenyl,
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`imidazolyl, pyrazolyl, oxazolyl,
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`isoxazolyl, thiazolyl, pyranyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, and triazolyl
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`more preferably selected from the group consisting of pyridyl, pyridazinyl, pyrimidinyl
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`and pyrazinyl each of which is optionally substituted as defined previously. In another
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`embodiment, each aforementioned heterocyclyl is a partially saturated heterocyclyl,
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`more preferably selected from the group consisting of imidazolinyl, isoxazolinyl and
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`thiazolinyl each of which is optionally substituted as defined previously.
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`In another
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`embodiment, each aforementioned heterocyclyl
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`is a saturated heterocyclyl more
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`preferably selected from the group consisting of morpholinyl,
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`tetrahydrofuryl and
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`tetrahydropyranyl each of which is optionally substituted as defined previously.
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`In one embodiment of the present invention, G is selected from the group
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`consisting of hydrogen, C1-Cgalkyl (e.g methyl, ethyl, n-propyl, Hpropyl, n-butyl, butyl,
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`-C2-Cealkenyl
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`(e.g vinyl), C2-Cgalkynyl
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`(e.g propargyl),
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`-C(OQ)Ci-Csalkyl
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`(more
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`preferably -C(O)C.1-Cealkyl e.g -C(O)i-propyl and -C(O)tbutyl) and -C(O)-O-C.1-Cegalky|
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`(more preferably -C(O)-O-C1-Cealkyl e.g -C(O)-O-methyl). In a preferred embodiment,
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`G is hydrogen.
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`Depending on the nature of the substituents, compounds of Formula (I) may
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`exist in different isomeric forms. When G is hydrogen, for example, compounds of
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`Formula (I) may exist in different tautomeric forms.
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`This invention covers all such isomers and tautomers and mixtures thereof in
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`all proportions. Also, when substituents contain double bonds, cis- and trans-isomers
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`can exist. These isomers, too, are within the scope of the claimed compounds of the
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`Formula (I). Compounds of Formula (1) may contain asymmetric centres and may be
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`present as a single enantiomer, pairs of enantiomers in any proportion or, where more
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`than one asymmetric centre are present, contain diastereoisomers in all possible
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`ratios. Typically one of the enantiomers has enhancedbiological activity compared to
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`the other possibilities.
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`The compounds of Formula (I) according to the invention can be used as
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`herbicides by themselves, but
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`they are generally formulated into herbicidal
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`compositions using formulation adjuvants, such as carriers, solvents and surface-
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`active agents (SFAs). Thus,
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`the present
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`invention further provides a herbicidal
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`composition comprising a herbicidal compound according to any one of the previous
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`claims and an agriculturally acceptable formulation adjuvant. The composition can be
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`in the form of concentrates which are diluted prior to use, although ready-to-use
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`compositions can also be made. The final dilution is usually made with water, but can
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`be made instead of, or in addition to, water, with, for example,
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`liquid fertilisers,
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`micronutrients, biological organisms, oil or solvents.
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`The herbicidal compositions generally comprise from 0.1 to 99 % by weight,
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`especially from 0.1 to 95 % by weight, compounds of Formula (1) and from 1 to 99.9 %
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`by weight of a formulation adjuvant which preferably includes from 0 to 25 % by weight
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`of a surface-active substance.
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`The compositions can be chosen from a number of formulation types, many of
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`which are known from the Manual on Development and Use of FAO Specifications for
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`Plant Protection Products, 5th Edition, 1999. These include dustable powders (DP),
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`soluble powders (SP), water soluble granules (SG), water dispersible granules (WG),
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`wettable powders (WP), granules (GR) (slow or fast release), soluble concentrates
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`(SL), oil miscible liquids (OL), ultra low volume liquids (UL), emulsifiable concentrates
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`(EC), dispersible concentrates (DC), emulsions (both oil in water (EW) and water in oil
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`(EO)), micro-emulsions (ME), suspension concentrates (SC), aerosols, capsule
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`suspensions (CS) and seed treatment formulations. The formulation type chosen in
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`any instance will depend upon the particular purpose envisaged and the physical,
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`chemical and biological properties of the compound of Formula (1).
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`Dustable powders (DP) may be prepared by mixing a compound of Formula (I)
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`with one or more solid diluents (for example natural clays, kaolin, pyrophyllite,
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`bentonite, alumina, montmorillonite, kieselguhr, chalk, diatomaceous earths, calcium
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`phosphates, calcium and magnesium carbonates, sulphur, lime, flours, talc and other
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`organic and inorganic solid carriers) and mechanically grinding the mixture to a fine
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`powder.
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`Soluble powders (SP) may be prepared by mixing a compound of Formula (1)
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`with one or more water-soluble inorganic salts (such as sodium bicarbonate, sodium
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`carbonate or magnesium sulphate) or one or more water-soluble organic solids (such
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`as a polysaccharide) and, optionally, one or more wetting agents, one or more
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`dispersing agents or a mixture of said agents to improve water dispersibility/solubility.
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`The mixture is then ground to a fine powder. Similar compositions may also be
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`granulated to form water soluble granules (SG).
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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,
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`preferably, one or more dispersing agents and, optionally, one or more suspending
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`agents to facilitate the dispersion in liquids. The mixture is then ground to a fine
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`powder.
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`Similar compositions may also be granulated to form water dispersible
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`granules (WG).
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`Granules (GR) may be formed either by granulating a mixture of a compound
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`of Formula (1) and one or more powderedsolid diluents or carriers, or from pre-formed
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`blank granules by absorbing a compound of Formula (I) (or a solution thereof,
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`in a
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`suitable agent) in a porous granular material (such as pumice, attapulgite clays, fuller’s
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`earth, kieselguhr, diatomaceous earths or ground corn cobs) or by adsorbing a
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`compound of Formula (I) (or a solution thereof, in a suitable agent) on to a hard core
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`material (such as sands, silicates, mineral carbonates, sulphates or phosphates) and
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`drying if necessary. Agents which are commonly used to aid absorption or adsorption
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`include solvents (such as aliphatic and aromatic petroleum solvents, alcohols, ethers,
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`ketones and esters) and sticking agents (such as polyvinyl acetates, polyvinyl alcohols,
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`dextrins, sugars and vegetable oils). One or more other additives may also be included
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`in granules (for example an emulsifying agent, wetting agent or dispersing agent).
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`Dispersible Concentrates (DC) may be prepared by dissolving a compound of
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`Formula (I) in water or an organic solvent, such as a ketone, alcohol or glycol ether.
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`These solutions may contain a surface active agent (for example to improve water
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`dilution or prevent crystallisation in a spray tank).
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`Emulsifiable concentrates (EC) or oil-in-water emulsions
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`(EW) may be
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`prepared by dissolving a compound of Formula (I) in an organic solvent (optionally
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`containing one or more wetting agents, one or more emulsifying agents or a mixture of
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`said agents). Suitable organic solvents for use in ECs include aromatic hydrocarbons
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`(such as alkylbenzenes or alkylnaphthalenes, exemplified by SOLVESSO 100,
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`SOLVESSO 150 and SOLVESSO 200; SOLVESSO is a Registered Trade Mark),
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`ketones (such as cyclohexanone or methylcyclohexanone) and alcohols (such as
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`benzyl
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`alcohol,
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`furfuryl
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`alcohol or butanol), N-alkylpyrrolidones
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`(such as N-
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`methylpyrrolidone or N-octylpyrrolidone), dimethyl amides of fatty acids (such as Ce-
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`Cio fatty acid dimethylamide) and chlorinated hydrocarbons. An EC product may
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`spontaneously emulsify on addition to water, to produce an emulsion with sufficient
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`stability to allow spray application through appropriate equipment.
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`Preparation of an EW involves obtaining a compound of Formula (I) either as a
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`liquid (if it
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`is not a liquid at room temperature,
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`it may be melted at a reasonable
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`temperature, typically below 70°C) or in solution (by dissolving it
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`in an appropriate
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`solvent) and then emulsifying the resultant liquid or solution into water containing one
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`or more SFAs, under high shear, to produce an emulsion. Suitable solvents for use in
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`EWs include vegetable oils, chlorinated hydrocarbons (such as chlorobenzenes),
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`aromatic solvents (such as alkylbenzenesor alkylnaphthalenes) and other appropriate
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`organic solvents which have a low solubility in water.
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`Microemulsions (ME) may be prepared by mixing water with a blend of one or
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`more solvents with one or more SFAs, to produce spontaneously a thermodynamically
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`stable isotropic liquid formulation. A compound of Formula (I) is present initially in
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`either the water or the solvent/SFA blend. Suitable solvents for use in MEs include
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`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 presen