(12) INTERNATIONAL APPLICATION PUBLISHED UNDER THE PATENT COOPERATION TREATY (PCT)
`(19) World Intellectual Property
`Organization
`International Bureau
`
`UDAATTAAA ARA
`
`(43) International Publication Date
`26 June 2014 (26.06.2014)
`
`WIPO!IPCT
`
`\=
`
`(10) International Publication Number
`WO 2014/096289 A2
`
`GD)
`
`International Patent Classification:
`C07D 309/06 (2006.01)
`
`(21)
`
`International Application Number:
`
`PCT/EP2013/077541
`
`(22)
`
`International Filing Date:
`
`19 December 2013 (19.12.2013)
`
`(25)
`
`(26)
`
`(30)
`
`(71)
`
`(72)
`
`Filing Language:
`
`Publication Language:
`
`Priority Data:
`1223429.0
`21 December 2012 (21.12.2012)
`1309728.2
`31 May 2013 (31.05.2013)
`1321553.8
`4 December 2013 (04.12.2013)
`
`English
`
`English
`
`GB
`GB
`GB
`
`Applicant: SYNGENTA LIMITED [GB/GB]; European
`Regional Centre, Priestley Road, Surrey Research Park,
`Guildford Surrey GU2 7YH (GB).
`
`Inventors: MOUND, William Roderick; Syngenta Lim-
`ited, Jealott's Hill International Research Centre, Bracknell
`Berkshire RG42 6EY (GB). SCUTT, James Nicholas;
`Syngenta Limited, Jealott's Hill
`International Research
`Centre, Bracknell Berkshire RG42 6EY (GB). SLATER,
`Mark; Syngenta Limited, Jealott's Hill International Re-
`search Centre, Bracknell Berkshire RG42 6EY (GB). WIL-
`LETTS, Nigel James; Syngenta Limited, Jealott's Hill In-
`ternational Research Centre, Bracknell Berkshire RG42
`6EY (GB).
`
`(74)
`
`(81)
`
`Agents: SYNGENTA LIMITEDet al.; Intellectual Prop-
`erty Department, Syngenta Limited, PO Box 3538, Jealott's
`Hill International Research Centre, Bracknell Berkshire
`RG42 6YA (GB).
`
`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, CA, CH, CL, CN, CO, CR, CU, CZ, DE, DK, DM,
`DO, DZ, EC, EE, EG, ES, FI, GB, GD, GE, GH, GM, GT,
`HN, HR, HU,ID,IL, IN, IR, IS, JP, KE, KG, KN, KP, KR,
`KZ, LA, LC, LK, LR, LS, LT, LU, LY, MA, MD, ME,
`MG, MK, MN, MW, MX, MY, MZ, NA, NG, NI, NO, NZ,
`OM,PA, PF, 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.
`
`(84)
`
`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, SZ, TZ,
`UG, ZM, ZW), Eurasian (AM, AZ, BY, KG, KZ, RU,TJ,
`TM), European (AL, AT, BE, BG, CH, CY, CZ, DE, DK,
`EE, ES, FI, FR, GB, GR, HR, HU,IE,IS, IT, LT, LU, LV,
`MC, MK, MT, NL, NO, PL, PT, RO, RS, SE, SIL 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))
`
`[Continued on next page]
`
`(34) Title: HERBICIDALLY ACTIVE CYCLIC DIONE COMPOUNDS, OR DERIVATIVES THEREOF, SUBSTITUTED BY A
`PHENYL WHICH HAS AN ALKYNYL-CONTAINING SUBSTITUENT
`
` (I)
`
`(57) Abstract: The present invention relates to a compound of formula (1), wherein: X is methyl or chlorine; R’ is methyl or chlor-
`ine;
`R’® is hydrogen, methyl, ethyl, z-propyl, cyclopropyl, vinyl, ethynyl,
`fluorine, chlorine, bromine, Ci-Csalkoxy, C.-C2-
`tluoroalkoxy, Ci-Czalkoxy-Ci-Csalkoxy- or Cithioroalkoxy-Ci-Csalkoxy-; and Y is O, S, S(O), S(O)2, N(Ci-Coralkyl), N¢Ci-
`Coalkoxy), C(O), CR*R® or -CR”“R'CRVR™-; and and G, R*, R*, R* and R° are as defined herein; wherein the compound of formula
`(D is optionally present as an agrochemically acceptable salt thereof. These compoundsare suitable for use as herbicides. The inven-
`tion therefore also relates to a method of controlling weeds, especially grassy monocotyledonous weeds, in crops of useful plants,
`comprising applying a compoundof formula (1), or a herbicidal composition comprising such a compound,to the plants or to the
`locus thereof.
`
`2014/096289A2IIITNITANIATIAAMCTAIRAA
`
`©=
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`

`

`WO 2014/096289 A2 IfMTIMN THAINTOUT TATE MTAAY ATAAA
`
`—_ofinventorship (Rule 4.17(iv)) Published:
`
`—_without international search report and to be republished
`upon receipt of that report (Rule 48. 2(g))
`
`

`

`WO 2014/096289
`
`PCT/EP2013/077541
`
`Herbicidally active cyclic dione compounds, or derivatives thereof, substituted by a
`
`phenyl which has an alkynyl-containing substituent
`
`The present invention relates to herbicidally active cyclic diones, in particular pyrandione,
`
`thiopyrandione, cyclohexanedione, alkanediyl-bridged cyclohexanedione, cyclohexanetrione
`
`or cycloheptanedione compounds, or derivatives thereof (e.g. enol ketone tautomer
`
`derivatives thereof), to processesfor their preparation, to herbicidal compositions comprising
`
`those compounds, and to their use in controlling weeds such as grassy monocotyledonous
`
`weeds, especially in crops of useful plants, or in inhibiting undesired plant growth.
`
`In
`
`10
`
`particular, the present invention relates to herbicidally active cyclic dione compounds, or
`
`derivatives thereof (e.g. enol ketone tautomerderivatives thereof), which are substituted by a
`
`phenyl which has an alkynyl-containing substituent.
`
`WO 01/17972 A2 (Syngenta Participations AG) discloses phenyl-substituted (such as
`
`15
`
`4-methyl-2,6-diethyl-phenyl- substituted) heterocycles suitable for use as herbicides.
`
`WO 03/013249 A1 (Bayer AG) and its equivalent US 2005/0054535 A1 disclose selective
`
`herbicidal compositions comprising (a) a (substituted-phenyl)-substituted cyclic ketoenol and
`
`(b) a compound which improves crop plant compatibility, in particular cloquintocet-mexyl or
`
`20
`
`mefenpyr-diethyl.
`
`WO 2007/068427 A2 (Bayer CropScience AG) and its equivalent US 2009/0227563 A1
`
`disclose a composition comprising (a) a (substituted-phenyl)-substituted cyclic ketoenol as a
`
`herbicide, and (b) an ammonium or phosphonium salt to boostactivity.
`
`WO 2008/071405 A1 and WO 2009/074314 A1 (both Syngenta Limited and Syngenta
`
`Participations AG) each disclose herbicidally active pyran-3,5-diones, thiopyran-3,5-diones
`
`and cyclohexane-1,3,5-triones, each substituted at the 4-position of the cyclic dione or trione
`
`by an aryl-substituted-phenyl or by a heteroaryl-substituted-phenyl.
`
`WO 2010/081755 A1 and WO 2010/089211 A1 (both Syngenta Limited) each disclose
`
`herbicidally active pyran-3,5-diones, thiopyran-3,5-diones, cyclohexanediones,
`
`cycloheptanediones and cyclohexanetriones, each substituted by an aryloxy-substituted-
`
`phenyl or by a heteroaryloxy-substituted-phenyl.
`
`25
`
`30
`
`35
`
`

`

`WO 2014/096289
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`PCT/EP2013/077541
`
`WO 2008/110308 A1 (Syngenta Participations AG) discloses 2-(substituted-phenyl)-
`cyclohexane-1 ,3-dione compounds and derivatives, containing a R®-X-(CR®R’),- substituent
`(wherein X is O, S, S(O) or S(O),) or a heteroatom-containing-spirocyle at the 5-position of
`
`the cyclohexane-1,3-dione, and having herbicidal properties. WO 2008/110307 A1
`
`(Syngenta Participations AG) discloses 2-(substituted-phenyl)-5-heterocyclyl-cyclohexane-
`
`1,3-dione compounds andderivatives, and their use as herbicides. WO 2010/046194 A1
`
`(Syngenta Limited) discloses 2-(substituted-phenyl)-cyclohexane-1 ,3-dione compounds and
`derivatives, containing a Q-CR®R’- substituent at the 5-position of the cyclohexane-1,3-dione
`(wherein Q is a saturated or mono-unsaturated heterocycle), and having herbicidal
`
`10
`
`properties.
`
`WO 2008/145336 A1 and A8 (Syngenta Limited) disclose herbicidally active phenyl-
`
`substituted bicyclic (carbon-bridged, e.g. alkanediyl-bridged) 1,3-dione compounds, such as
`
`3-(substituted-phenyl)-bicyclo[3.2.1]octane-2,4-diones.
`
`Copending PCT application PCT/EP201 2/0741 18, filed on 30 November 2012 and published
`
`on 6 June 2013 as WO 2013/079672 A1 (Syngenta Limited and Syngenta Participations AG)
`
`discloses that certain substituted spiroheterocyclic pyrrolidine dione compounds, having an
`
`alkynyl-phenyl- headgroup, have herbicidal properties.
`
`15
`
`20
`
`Copending PCT application PCT/EP201 2/0741 72, filed on 30 November 2012 and published
`
`on 6 June 2013 as WO 2013/079708 A1 (Syngenta Limited and Syngenta Participations AG)
`
`discloses cyclopentane-1,3-dione compounds and derivatives (e.g. fused and/or spirocyclic
`
`bicyclic derivatives) thereof, which are substituted at the 2-position of the cyclopentane-1 ,3-
`
`25
`
`dione by a phenyl whichitself is substituted at the 4-position by (specifically) either
`
`prop-1-ynyl or chloroethynyl, and derivatives of the enol ketone tautomer of such
`
`cyclopentanediones, which have herbicidal activity and/or plant-growth-inhibiting properties,
`
`especially in the control of grassy monocotyledonous weeds and/or when used post-
`
`emergence.
`
`30
`
`Cyclic dione compounds have now been found, in particular pyran-3,5-dione, thiopyran-3,5-
`
`dione, cyclohexane-1 ,3-dione, alkanediyl-bridged cyclohexane-1 ,3-dione, cyclohexane-1,3,5-
`
`trione or cycloheptane-1,3-dione compounds, which are substituted, at the ring-carbon atom
`
`of the cyclic dione which is between the two oxo-substituted ring-carbons of the cyclic dione,
`
`35
`
`by a phenyl whichitself is substituted at the 4-position by (specifically) either prop-1-ynyl or
`
`chloroethynyl and at the 2-position by (specifically) methyl or chlorine, or derivatives of the
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`

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`WO 2014/096289
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`PCT/EP2013/077541
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`enol ketone tautomer of such cyclic diones, which have herbicidal activity and/or plant-
`
`growth-inhibiting properties, in particular in the control of grassy monocotyledonous weeds.
`
`The herbicidal data available, as shownin the Biological Examples hereinafter, suggests that
`
`these 4-(prop-1-ynyl)-2-(methyl or chloro)-phenyl or 4-(chloroethynyl)-2-(methyl or chloro)-
`
`phenyl cyclic dione compounds are more potent herbicides against grassy
`
`monocotyledonous weeds (e.g. when applied post-emergence)than the corresponding 4-
`
`ethynyl-2-(methyl or chloro)-phenyl cyclic dione compounds. The herbicidal activity against
`
`“warm-season” (warm climate) grassy monocotyledonous weeds of most of the compounds
`
`of the invention which have been exemplified and tested herein (compounds A-1 to A-17,
`
`10
`
`A-18 to A-24, P-1 to P-5, or P-7) appears to be potent, in particular after post-emergence
`
`application of the compounds at an application rate of about 250 g/ha. Also, many of the
`
`exemplified compounds exhibit a reasonably low phytotoxicity against wheat and/or certain
`
`docotyledonous crops, in particular soybean and/or sugar beet (see Biological Examples 1B
`
`and 3 hereinafter).
`
`15
`
`Therefore, in a first aspect of the present invention, there is provided a compound of formula
`
`(I):
`
`
`
`20
`
`wherein:
`
`X is methyl or chlorine;
`R' is methyl or chlorine;
`R’ is hydrogen, methyl, ethyl, n-propyl, cyclopropyl, vinyl, ethynyl, fluorine, chlorine, bromine,
`
`25
`
`C,-Czalkoxy, C,-C2fluoroalkoxy, C,-Cz,alkoxy-C,-Czalkoxy-, or C,fluoroalkoxy-C,-Czalkoxy-;
`
`and
`
`R*, R*, R® and R®, independently of each other, are hydrogen, C,-Cezalkyl (in particular C,-
`
`Caalkyl, e.g. C1-Caalkyl), C2-Caalkenyl (in particular C2-Csalkenyl-CH2-, e.g. ethenyl-CH2-),
`
`30
`
`Co-Cyalkynyl (in particular C2-Caalkynyl-CH2-, e.g. ethynyl-CH2-), C,-C2fluoroalkyl,
`
`

`

`WO 2014/096289
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`PCT/EP2013/077541
`
`C,-CzalkoxyC,-Cgalkyl, C;-CsalkylthioC,-Czalkyl, C;-CaalkylsulfinylC ;-Czalkyl,
`
`C,-CzalkylsulfonylC,-Cgalkyl; Cz-C4cycloalkyl (in particular cyclopropyl); or an unsubstituted
`
`4,5 or6 (e.g. 4 or 5) membered monocyclic heterocyclyl having one ring heteroatom
`
`independently selected from oxygen, sulfur and nitrogen, and attached at a ring carbon atom
`
`within the heterocyclyl (in particular tetrahydrofuranyl such as tetrahydrofuran-3-yl, or
`
`tetrahydropyranyl such as tetrahydropyran-4-yl);
`provided that no more than one(in particular none) of R®, R*, R® and R*°is alkenyl, alkynyl,
`
`alkoxyalkyl, alkylthioalkyl, alkylsulfinylalkyl, alkylsulfonylalkyl, cycloalkyl or heterocyclyl;
`
`10
`
`or R® and R* taken together are -(CH2)q1- or -(CH2)n2-X'-(CH2)n3- and R® and R® are as
`defined herein (e.g. hereinabove), or R°® and R® taken together
`are -(CH2)q1- Or -(CH2)po-X'-~(CHo)n3- and R® and R* are as defined herein (e.g. hereinabove);
`wherein X" is O, S, S(O), S(O)2, NH, N(C,-Czalkyl), N(C,-Czalkoxy), C(H)(C,-Czalkyl),
`
`C(C,1-Czalkyl)2 or C(H)(C1-Czalkoxy);
`
`15
`
`n1 is 2, 3, 4 or 5 (in particular 4 or 5); and
`
`n2 and n3 are independently 1, 2 or 3 provided that n2 + n3 is 2, 3 or 4 (in particular 3 or 4);
`
`or R* and R® taken together are -(CH2),4- or -(CH2)ns-C(R™)(R”)-(CH2)n6- or -C(R™)=C(R”™)-;
`wherein R” is C,-Czalkyl or C1-Czalkoxy; and R”is hydrogen or C,-Czalkyl provided that R”
`is hydrogen when R”is C,-Czalkoxy;
`
`20
`
`n4 is 1, 2 or 3; and
`
`1 or 2 provided that n5 + n6 is 0, 1 or 2;
`nd5 and n6 are independently O,
`and R” and R™independently are hydrogen or C,-C,alkyl; and
`
`25
`
`Y is O, S, S(O), S(O), N(C1-Czalkyl), N(C4-Czalkoxy), C(O), CR®R® or -CR®R™CR”?R™-; and
`
`R® and R® are, independently of each other:
`
`hydrogen, C,-Cealkyl (in particular Cy-Cyalkyl, e.g. C1-Caalkyl), Co-Cyalkenyl(in
`
`particular C2-Czalkenyl-CH>-, e.g. ethenyl-CH>-), C2-Caalkynyl (in particular
`
`30
`
`C2-Csalkynyl-CH2-, e.g. ethynyl-CH2-), C4-C2fluoroalkyl, C,-CsalkoxyC,-Czalkyl,
`
`C,-CzalkylthioC,-Czalkyl, C;-CaalkylsulfinylC,;-Czalkyl, or C;-CaalkylsulfonylC,-Czalkyl;
`
`C3-Cecycloalkyl or C3-Cecycloalkyl substituted by one or two substituents which
`
`independently are C,-Czalkyl (in particular methyl or ethyl) or C,-C2fluoroalkyl; and in which
`
`one ring CH2 moiety of a C4-Cecycloalkyl is optionally (e.g. preferably) replaced by an oxygen
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`

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`WO 2014/096289
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`PCT/EP2013/077541
`
`or sulfur atom or by a S(O), S(O)s, NH, N(C4-Cgalkyl), N(C,-C2fluoroalkyl), N[C(Q)C,-Czalkyl],
`
`N[C(O)C,-C2fluoroalkyl] or N(C,-Czalkoxy) moiety;
`
`C3-Cecycloalkyl substituted by one substituent being C,-Csalkoxy (in particular
`
`C,-Czalkoxy) and optionally further substituted by one substituent being C,-Czalkyl (in
`
`particular methyl);
`
`Cs5-Cecycloalkenyl or Cs5-Cecycloalkenyl substituted by one or two C,-Caalkyl(in
`
`particular methyl) substituents;
`
`C2-CecycloalkylC,-Czalkyl- (in particular C3-Cgcycloalkylmethyl-) or Cs-CegcycloalkylC,-
`
`Caalkyl- (in particular C3-Cecycloalkylmethyl-) substituted by one or two ring substituents
`
`10
`
`which independently are C,-Csgalkyl or C;-Czfluoroalkyl; and in which one ring CH2 moiety of a
`
`C,4-C,cycloalkylC,-Calkyl- (in particular C,-Cgcycloalkylmethyl-) is optionally (e.g. preferably)
`
`replaced by an oxygen or sulfur atom or by a S(O), S(O)2, NH, N(C4-Caalkyl), N(C4-
`
`Cefluoroalkyl), N[C(O)C,-Csalkyl], N[C(O)C,-C-fluoroalkyl] or N(C;-Czalkoxy) moiety;
`
`C.-CecycloalkylC,-Czalkyl- (in particular C3-Cgcycloalkylmethyl-) substituted by one ring
`
`15
`
`substituent being C,-Cgalkoxy (in particular C,-Czalkoxy) and optionally further substituted by
`
`one ring substituent being C,-Czalkyl (in particular methyl); or
`
`Het or Het-CH,-, wherein Het is a heteroaryl, attached at a ring-carbon, which is
`
`optionally substituted by 1, 2 or 3 (in particular 1 or 2, e.g. 1) ring-carbon substituents
`
`independently being C,-Caalkyl (e.g. C1-Czalkyl), C1-C2fluoroalkyl, C,-Cgalkyl-C(O)-,
`
`20
`
`C,-C2fluoroalkyl-C(O)-, hydroxy (including any oxo tautomer), C2-Czalkenyl (e.g. ethenyl or
`
`prop-1-enyl), C2-Czalkynyl (e.g. ethynyl or prop-1-ynyl), C;-Czsalkoxy (e.g. C;-C2alkoxy), C,-
`
`C.fluoroalkoxy, halogen (e.g. fluorine or chlorine), cyano or nitro, provided that any non-
`
`fluorine halogen, alkoxyor fluoroalkoxy is not substituted at any ring-carbon bondeddirectly
`
`to a ring-nitrogen of the heteroaryl; and/or, in the case of a 5-membered heteroaryl ring
`
`25
`
`containing a ring-nitrogen atom not partaking in a C=N ring double bond, the heteroarylis
`
`optionally substituted on the ring-nitrogen atom not partaking in a C=N ring double bond by
`
`one C,-Cagalkyl, C,-C2fluoroalkyl, C;-C3alkyl-C(O)-, C,-C2fluoroalkyl-C(O)- or
`
`C,-Czalkyl-S(O)2- substituent;
`
`30
`
`provided that no more than one of R® and R°is an optionally substituted cycloalkyl; an
`optionally substituted cycloalkyl in which one ring CH, moiety has been replaced by an
`
`oxygen or sulfur atom or by a S(O), S(O)2, NH, N(C,-Csalkyl), N(C;-C2fluoroalkyl),
`
`N[C(O)C,-Cgalkyl], N[C(O)C,-Cfluoroalkyl] or N(C,-Czalkoxy) moiety; an optionally
`
`substituted cycloalkenyl; an optionally substituted cycloalkyl-alkyl-; an optionally substituted
`
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`WO 2014/096289
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`PCT/EP2013/077541
`
`cycloalkyl-alkyl- in which one ring CH2 moiety has been replaced by an oxygen or sulfur atom
`
`or by a S(O), S(O)s, NH, N(C,-Caalkyl), N(C4-C-fluoroalkyl), N[C(O)C,-Cgalkyl],
`
`N[C(O)C,-C2fluoroalkyl] or N(C,-Czalkoxy) moiety; or Het or Het-CH--;
`
`or R® is hydrogen or C,-Czalkyl (in particular H or Me), and R® is C1-Czalkoxy (in particular
`methoxy);
`
`10
`
`15
`
`or R® and R® taken together are -(CH2)n7- or -(CH2)ne-X*-(CH2)no“
`wherein X? is O, S, S(O), S(Q)2, NH, N(C1-Caalkyl), N(C1-Czfluoroalkyl), N[C(OQ)C,-Csalkyl],
`N[C(O)C,-Cofluoroalkyl], N(C1-Czalkoxy), C(H)(C1-Czalkyl), C(C1-Czalkyl)s or
`
`C(H)(C1-Czalkoxy);
`
`n7 is 2, 3, 4, 5 or 6 (in particular 4 or 5); and
`
`n8 and n9 are independently 0, 1, 2 or 3 provided that n8 + nQ is 2, 3, 4 or 5 (in particular 3
`
`or 4); and
`
`R'®, R"™',R" and R"™ are independently of each other hydrogen or C;-Cgalkyl (in particular
`C,-Czalkyl) provided that no more than one of R'°, R'', R' and R"™ is Cs-Cyalkyl; and
`
`and wherein:
`
`20
`
`G is hydrogen; an agriculturally acceptable metal, or an agriculturally acceptable sulfonium or
`
`ammonium group; or
`
`G is -C(X*)-R?, -C(X°)-X°-R®, -C(X°)-N(R°)-R%, -SO.-R®, -P(X°)(R‘)-R9, -CH-X'-R"; or
`
`phenyl-CH>- or phenyl-CH(C,-Czalkyl)- (in each of which the phenyl is optionally substituted
`
`25
`
`by 1, 2 or 3 of, independently, C,-Czalkyl, C,fluoroalkyl, C;-Czalkoxy, C,fluoroalkoxy,fluorine,
`
`chlorine, bromine, cyano or nitro), or heteroaryl-CH>2- or heteroaryl-CH(C1-Caalkyl)- (in each
`
`of which the heteroaryl is optionally substituted by 1, 2 or 3 of, independently, C,-Czalkyl,
`
`C,fluoroalkyl, C;-Czalkoxy, C,fluoroalkoxy, fluorine, chlorine, bromine, cyano or nitro), or
`
`phenyl-C(O)-CH2- (wherein the phenyl is optionally substituted by 1, 2 or 3 of, independently,
`
`30
`
`C,-Caalkyl, C,fluoroalkyl, C,-Czalkoxy, C,fluoroalkoxy,fluorine, chlorine, bromine, cyano or
`
`nitro); or C1-Cgalkoxy-C(O)-CH2-, C1-Cgalkoxy-C(O)-CH=CH-, C2-C7alken-1-yl-CH2-,
`
`C2-Czalken-1-yl-CH(C,-Czalkyl)-, C2-C,fluoroalken-1-yl-CH2-, C2-Czalkyn-1-yl-CH>2-, or
`
`C2-Czalkyn-1-yl-CH(C,-Coalkyl)-;
`
`

`

`WO 2014/096289
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`PCT/EP2013/077541
`
`wherein X?, X°, X°, X°, X° and X' are independently of each other oxygen or sulfur (in
`
`particular oxygen); and wherein
`
`R* is H, C1-Ca,alkyl, C2-C2,alkenyl, C2-Cigalkynyl, C1-Cjofluoroalkyl, C;-Ci9cyanoalkyl, C4-
`
`Cyonitroalkyl, C1-C,9aminoalkyl, C1-Csalkylamino(C,-Cs)alkyl, Co-Cedialkylamino(C,-Cs)alkyl,
`
`C3-C7cycloalkyl(C1-Cs)alkyl, C;-Csalkoxy(C,-Cs)alkyl, C3-Csalkenyloxy(C,-Cs)alkyl, Cs-
`
`Csalkynyloxy (C4-Cs)alkyl, C;-Csalkylthio(C,-Cs)alkyl, C;-Csalkylsulfinyl(C,-Cs)alkyl, C4-
`
`Csalkylsulfonyl(C,-Cs)alkyl, Co-Cealkylideneaminoxy(C,-Cs)alkyl, C,-Csalkylcarbonyl(C,-
`
`Cs)alkyl, C1-Csalkoxycarbonyl(C,-Cs)alkyl, aminocarbonyl(C1-Cs)alkyl, C4-
`
`10
`
`Csalkylaminocarbonyl(C,-Cs)alkyl, C2-Cgdialkylaminocarbonyl(C1-Cs)alkyl, C,-
`
`Czalkylcarbonylamino(C,-Cs)alkyl, N-(C,-C;)alkylcarbonyl-N-(C,-C;)alkylamino(C,-C;)alkyl,
`
`C,-Cetrialkylsilyl(C,-Cs)alkyl, phenyl(C,-C;)alkyl (wherein the phenyl is optionally substituted
`
`by 1,2 or 3 of, independently, C,-Caalkyl, C;-C3fluoroalkyl, C;-C3alkoxy, C,-Czfluoroalkoxy,
`
`C,-Cazalkylthio, C,-Cgalkylsulfinyl, C,-C3alkylsulfonyl, halogen, cyano, or nitro), heteroaryl(C,-
`
`15
`
`Cs)alkyl (wherein the heteroaryl is optionally substituted by 1, 2 or 3 of, independently, C,-
`
`Cgalkyl, C,-Csfluoroalkyl, C,-Csalkoxy, C)-Csfluoroalkoxy, C,-Cs3alkylthio, C;-Czalkylsulfinyl,
`
`C,-Czalkylsulfonyl, halogen, cyano, or nitro), C2-C.fluoroalkenyl, C3-Cgcycloalkyl; phenyl or
`
`phenyl substituted by 1, 2 or 3 of, independently, C;-Csalkyl, C4-Cafluoroalkyl, C1-Czalkoxy,
`
`C,-Csfluoroalkoxy, halogen, cyano ornitro; or heteroaryl or heteroaryl substituted by 1, 2 or 3
`
`20
`
`of, independently, C,-Cz alkyl, C;-Csfluoroalkyl, C;-C3alkoxy, C,-Csfluoroalkoxy, halogen,
`
`cyano ornitro;
`
`R?is C,-Cigalkyl, C3-C,galkenyl, C3-Cigalkynyl, C2-C, fluoroalkyl, C;-C;9cyanoalkyl, C,-
`
`Cyonitroalkyl, C2-C,9aminoalkyl, C;-Csalkylamino(C,-Cs)alkyl, C2-Cgdialkylamino(C,-C5)alkyl,
`
`25
`
`C3-C7cycloalkyl(C,-Cs)alkyl, C;-Csalkoxy(C,-Cs)alkyl, C3-Csalkenyloxy(C,-Cs)alkyl, Cs-
`
`Csalkynyloxy(C,-Cs)alkyl, C;-Csalkylthio(C;-Cs)alkyl, C,-Csalkylsulfinyl(C,-C;)alkyl, C,-
`
`Czalkylsulfonyl(C;-C;)alkyl, C2-Cgalkylideneaminoxy(C,-Cs)alkyl, C,-Csalkylcarbonyl(C,-
`
`Cs)alkyl, C;-Csalkoxycarbonyl(C,-Cs)alkyl, aminocarbonyl(C4-Cs)alkyl, C4-
`
`Csalkylaminocarbonyl(C,-Cs)alkyl, C2-Cgdialkylaminocarbonyl(C,1-Cs)alkyl, C.-
`
`30
`
`Csalkylcarbonylamino(C,-Cs)alkyl, N-(C,-Cs)alkylcarbonyl-N-(C,-Cs)alkylamino(C,-Cs)alkyl,
`
`C3-Cetrialkylsilyl(C;-Cs)alkyl, phenyl(C1-Cs)alkyl (wherein the phenyl is optionally substituted
`
`by 1, 2 or 3 of, independently, C,-Csalkyl, C;-C3fluoroalkyl, C;-Csaalkoxy, C1-Cafluoroalkoxy,
`
`C,-Caalkylthio, C;-Czalkylsulfinyl, C;-C3alkylsulfonyl, halogen, cyano, or nitro), heteroarylC,-
`
`Csalkyl (wherein the heteroaryl is optionally substituted by 1, 2 or 3 of, independently, C,-
`
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`Caalkyl, C,-C3fluoroalkyl, C;-Csalkoxy, C,-Csfluoroalkoxy, C,-Cs3alkyl-thio, C,-Czalkylsulfinyl,
`
`C,-Czalkylsulfonyl, halogen, cyano, or nitro), Cz-Csfluoroalkenyl, Cs-Cecycloalkyl; phenyl or
`
`phenyl substituted by 1, 2 or 3 of, independently, C,-Csalkyl, C;-Cafluoroalkyl, C;-Czalkoxy,
`
`C,-C3fluoroalkoxy, halogen, cyano ornitro; or heteroaryl or heteroaryl substituted by 1, 2 or 3
`
`of, independently, C,-Cz alkyl, C,-Czfluoroalkyl, C;-Cz3alkoxy, C,-Czfluoroalkoxy, halogen,
`
`cyano or nitro; and
`
`R° and R° are each independently of each other hydrogen, C1-Calkyl, C3-Cyoalkenyl, C3-
`
`Cioalkynyl, C2-Ciofluoroalkyl, C1-Ciocyanoalkyl, C1-Cionitroalkyl, C1-C19aminoalkyl, C.-
`
`10
`
`Csalkylamino(C,-Cs)alkyl, C2-Cgdialkylamino(C,-Cs)alkyl, C3-C7cycloalkyl(C1-Cs)alkyl, C4-
`
`Csalkoxy(C,-C;)alkyl, C3-C;alkenyloxy(C,-Cs)alkyl, C3-Csalkynyloxy(C4-Cs)alkyl, C4-
`
`Czalkylthio(C,-Cs)alkyl, C;-Csalkylsulfinyl(C,-C;)alkyl, C;-Csalkylsulfonyl(C4-Cs)alkyl, Co-
`
`Cgalkylideneaminoxy(C,-Cs)alkyl, C;-Csalkylcarbonyl(C,-Cs)alkyl, C;-Csalkoxycarbonyl(C,-
`
`Cs)alkyl, aminocarbonyl(C,-Cs)alkyl, C,-Csalkylaminocarbonyl(C,-Cs)alkyl, C2-
`
`15
`
`Cedialkylaminocarbonyl(C,-Cs)alkyl, C,-Csalkylcarbonylamino(C,-Cs)alkyl, N-(C,-
`
`Cs)alkylcarbonyl-N-(C2-C;)alkylaminoalkyl, C3-Cetrialkylsilyl(C,-Cs)alkyl, phenyl(C,-Cs)alkyl
`
`(wherein the phenyl is optionally substituted by 1, 2 or 3 of, independently, C,-Csalkyl, C,-
`
`C2flucroalkyl, C,-Cgalkoxy, C,-C2fluoroalkoxy, C;-Csalkylthio, C;-Caalkylsulfinyl, C,-
`
`Czalkylsulfonyl, halogen, cyano, or nitro), heteroaryl(C.-Cs)alkyl (wherein the heteroaryl is
`
`20
`
`optionally substituted by 1, 2 or 3 of, independently, C,-Czalkyl, C;-C3fluoroalkyl, C,-
`
`Caalkoxy, C,-C3fluoroalkoxy, C,-Czalkylthio, C;-Czalkylsulfinyl, C;-Czalkylsulfonyl, halogen,
`
`cyano, or nitro), C2-Csfluoroalkenyl, C3-Cgcycloalkyl; phenyl or phenyl substituted by 1, 2 or 3
`
`of, independently, C,-Czalkyl, C,-C3fluoroalkyl, C;-C3alkoxy, C,-C3fluorcalkoxy, halogen,
`
`cyano or nitro; heteroaryl or heteroaryl substituted by 1, 2 or 3 of, independently, C,-Csalkyl,
`
`25
`
`C,-C3fluoroalkyl, C,-C3alkoxy, C,-Czfluoroalkoxy, halogen, cyano or nitro; heteroarylamino or
`
`heteroarylamino substituted by 1, 2 or 3 of, independently, C,-Czalkyl, C;-C3fluoroalkyl, C,-
`
`Cy3alkoxy, C,-C3fluoroalkoxy, halogen, cyano or nitro; diheteroarylamino or diheteroarylamino
`
`substituted by 1, 2 or 3 of, independently, C,-Czalkyl, C,-Csfluoroalkyl, C;-Csalkoxy, C.-
`
`C3fluoroalkoxy, halogen, cyano or nitro; phenylamino or phenylamino substituted by 1, 2 or 3
`
`30
`
`of, independently, C;-Csalkyl, C,-Csfluoroalkyl, C;-C3alkoxy, C;-C3fluoroalkoxy, halogen,
`
`cyano orby nitro; diphenylamino or diphenylamino substituted by 1, 2 or 3 of, independently,
`
`C,-Caalkyl, C;-Csfluoroalkyl, C;-Csalkoxy, C.-Cafluoroalkoxy, halogen, cyano ornitro; or Cs-
`
`C7cycloalkylamino, di(C3-C7cycloalkyljamino or C3-C7cycloalkoxy;
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`
`or R° and R‘, togetherwith the nitrogen to which they are bonded, to form an unsubstituted 4,
`
`5, 6 or 7 (e.g. 5 or 6) memberedring, optionally containing one heteroatom selected from O
`
`or S; and
`
`R® is Cy-Cyoalkyl, Co-Cyoalkenyl, Co-Ci alkynyl, C1-C.ofluoroalkyl, C;-C;9cyanoalkyl, C4-
`
`Cionitroalkyl, C1-C,oaminoalkyl, C.-Csalkylamino(C,-Cs)alkyl, C2-Csdialkylamino(C,-Cs)alkyl,
`
`C3-C;cycloalkyl(C4-Cs)alkyl, C;-Csalkoxy(C,-Cs)alkyl, C3-Csalkenyloxy(C,-Cs)alkyl, Cz-
`
`Csalkynyloxy(C1-Cs)alkyl, C;-Csalkylthio(C4-Cs)alkyl, C1-Csalkylsulfinyl(C,-Cs)alkyl, C4-
`
`Csalkylsulfonyl(C1-Cs)alkyl, Co-Cgalkylideneaminoxy(C1-Cs)alkyl, C1-Csalkylcarbonyl(C.-
`
`10
`
`Cs)alkyl, C;-Csalkoxycarbonyl(C,-Cs)alkyl, aminocarbonyl(C,-Cs)alkyl, Cy-
`
`Czsalkylaminocarbonyl(C,-C;)alkyl, C2-Cgdialkylaminocarbonyl(C,-C;)alkyl, C,-
`
`Csalkylcarbonylamino(C,-C;)alkyl, N-(C,-Cs)alkylcarbonyl-N-(C,-Cs)alkylamino(C,-Cs)alkyl,
`
`C3-Cetrialkylsilyl(C,-Cs)alkyl, phenyl(C,-Cs)alkyl (wherein the phenyl is optionally substituted
`
`by 1, 2 or 3 of, independently, C,-Cs3alkyl, C,-C3fluoroalkyl, C;-C3alkoxy, C,-C3fluoroalkoxy,
`
`15
`
`C,-Czalkylthio, C,-Czalkylsulfinyl, C;-Czalkylsulfonyl, halogen, cyano, or nitro), heteroaryl(C,-
`
`Cs)alkyl (wherein the heteroaryl is optionally substituted by 1, 2 or 3 of, independently, C,-
`
`Cgalkyl, C,-C2fluoroalkyl, C,-C3alkoxy, C)-C3fluoroalkoxy, C,-Cs3alkylthio, C;-Czalkylsulfinyl,
`
`C,-Czalkylsulfonyl, halogen, cyano, or nitro), C2-Csfluoroalkenyl, Cs-Cgcycloalkyl; phenyl or
`
`phenyl substituted by 1, 2 or 3 of, independently, C,-Csalkyl, C;-Cafluoroalkyl, C;-Czalkoxy,
`
`20
`
`C,-C3fluoroalkoxy, halogen, cyano or nitro; heteroaryl or heteroaryl substituted by 1, 2 or 3 of,
`
`independently, C,-Caalkyl, C,-C3fluoroalkyl, C;-Czalkoxy, C,-C3fluoroalkoxy, halogen, cyano
`
`or nitro; heteroarylamino or heteroarylamino substituted by 1, 2 or 3 of, independently, C,-C3
`
`alkyl, C,-C3fluoroalkyl, C;-C3alkoxy, C,-C3fluorcalkoxy, halogen, cyano ornitro;
`
`diheteroarylamino or diheteroarylamino substituted by 1, 2 or 3 of, independently, C,-Caalkyl,
`
`25
`
`C,-C3fluoroalkyl, C;-C3alkoxy, C,-C3fluoroalkoxy, halogen, cyano or nitro; phenylamino or
`
`phenylamino substituted by 1, 2 or 3 of, independently, C,-C3alkyl, C,-Csfluoroalkyl, C,-
`
`Cy3alkoxy, C;-C3fluoroalkoxy, halogen, cyano or nitro; diphenylamino or diphenylamino
`
`substituted by 1, 2 or 3 of, independently, C,-Czalkyl, C,-Csfluoroalkyl, C;-Csalkoxy, C.-
`
`C3fluoroalkoxy, halogen, cyano or nitro; or C3-C;cycloalkylamino, di(C3-C;cycloalkyl)amino,
`
`30
`
`C3-C;cycloalkoxy, C1-Cipalkoxy, C1-Cyiofluoroalkoxy, C;-Csalkylamino or di(C,-C,zalkyl)amino;
`
`R' and RY are are each independently of each other Cy-Cyoalkyl, C2-Cioalkenyl, C2-Cyoalkynyl,
`
`C1-Cipalkoxy, Cy-Ciofluoroalkyl, C;-C1.>cyanoalkyl, Cy-Cyonitroalkyl, C;-C,,aminoalkyl, C4-
`
`Csalkylamino(C,-Cs)alkyl, C2-Cedialkylamino(C,-Cs)alkyl, Cs-C7cycloalkyl(C4-Cs)alkyl, C4-
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`
`Csalkoxy(C,-Cs)alkyl, C3-Csalkenyloxy(C,-Cs)alkyl, C3-Csalkynyloxy(C,-Cs)alkyl, C1-
`
`Csalkylthio(C,-Cs)alkyl, C1-Csalkylsulfinyl(C,-Cs)alkyl, C;-Csalkylsulfonyl(C4-Cs)alkyl, Co-
`
`Cgalkylideneaminoxy(C,-Cs)alkyl, C;-Csalkylcarbonyl(C,-Cs)alkyl, Ci-Csalkoxycarbonyl(C.-
`
`Cs)alkyl, aminocarbonyl(C;-Cs)alkyl, C;-Csalkylaminocarbonyl(C1-Cs)alkyl, C2-
`
`Cedialkylaminocarbonyl(C,-Cs)alkyl, C1-Csalkylcarbonylamino(C,-Cs)alkyl, N-(C4-
`
`Cs)alkylcarbonyl-N-(C2-Cs)alkylaminoalkyl, C3-Cetrialkylsilyl(C;-Cs)alkyl, phenyl(C1-Cs)alkyl
`
`(wherein the phenyl is optionally substituted by 1, 2 or 3 of, independently, C;-Csalkyl, C,-
`
`C2flucroalkyl, C,-Cgalkoxy, C,-C2fluoroalkoxy, C;-Csalkylthio, C;-Czalkylsulfinyl, C,-
`
`Caalkylsulfonyl, halogen, cyano, or nitro), heteroaryl(C.1-Cs)alkyl (wherein the heteroaryl is
`
`10
`
`optionally substituted by 1, 2 or 3 of, independently, C;-Cgalkyl, C,-C3fluoroalkyl, C,-
`
`Czalkoxy, C,-C3fluoroalkoxy, C,-Cgalkylthio, C;-C3alkylsulfinyl, C;-C3alkylsulfonyl, halogen,
`
`cyano, or nitro), C2-Csfluoroalkenyl, C3-Cgcycloalkyl; phenyl or phenyl substituted by 1, 2 or 3
`
`of, independently, C,-Csaalkyl, C,-Csfluoroalkyl, C,-C3alkoxy, C,-Cfluorcalkoxy, halogen,
`
`cyano or nitro; heteroaryl or heteroaryl substituted by 1, 2 or 3 of, independently, C;-C3 alkyl,
`
`15
`
`C,-Cefluoroalkyl, Cy-Czalkoxy, C,-Czfluoroalkoxy, halogen, cyano or nitro; heteroarylamino or
`
`heteroarylamino substituted by 1, 2 or 3 of, independently, C,-C3 alkyl, C,-Csfluoroalkyl, C,-
`
`C3alkoxy, C,-C3fluoroalkoxy, halogen, cyano or nitro; diheteroarylamino or diheteroarylamino
`
`substituted by 1, 2 or 3 of, independently, C,-Cz alkyl, C,-Csfluoroalkyl, C1-Csalkoxy, C,-
`
`C3fluoroalkoxy, halogen, cyano or nitro; phenylamino or phenylamino substituted by 1, 2 or 3
`
`20
`
`of, independently, C,-Cazalkyl, C,-C3fluoroalkyl, C;-C3alkoxy, C,-C3fluorcalkoxy, halogen,
`
`cyano or nitro; diphenylamino or diphenylamino substituted by 1, 2 or 3 of, independently, C,-
`
`Cgalkyl, C,-Csfluoroalkyl, C;-Cgalkoxy, C,-C3fluoroalkoxy, halogen, cyano or nitro; or Cs-
`
`C,cycloalkylamino, di(C3-C7cycloalkylamino, C3-C7zcycloalkoxy, C1-Cjofluoroalkoxy, C,-
`
`Csalkylamino or di(C,-Cyalkyl)amino; or benzyloxy or phenoxy, wherein the benzyl and
`
`25
`
`phenyl groups are in turn optionally substituted by 1, 2 or 3 of, independently, C,-Csalkyl, C,-
`
`C3fluoroalkyl, C;-C3alkoxy, C,-Csfluoroalkoxy, halogen, cyano or nitro; and
`
`R" is Cy-Cyoalkyl, Cs-Cyoalkenyl, C3-Cioalkynyl, C1-Ciofluoroalkyl, C-Cyocyanoalkyl, Cy-
`
`Cionitroalkyl, C2-C,oaminoalkyl, C.-Csalkylamino(C,-Cs)alkyl, C2-Csdialkylamino(C,-Cs)alkyl,
`
`30
`
`C3-C7cycloalkyl(C,-Cs)alkyl, C;-Csalkoxy(C,-Cs)alkyl, C3-Csalkenyloxy(C,-Cs)alkyl, C3-
`
`Csalkynyloxy(C1-Cs)alkyl, C;-Csalkylthio(C4-Cs)alkyl, C,-Csalkylsulfinyl(C,-Cs)alkyl, C4-
`
`Csalkylsulfonyl(C1-Cs)alkyl, C2-Csalkylideneaminoxy(C1-Cs)alkyl, C1-Csalkylcarbonyl(C.-
`
`Cs)alkyl, C;-Csalkoxycarbonyl(C,-Cs)alkyl, aminocarbonyl(C,-Cs)alkyl, Cy-
`
`Csalkylaminocarbonyl(C,-Cs)alkyl, Co-Cegdialkylaminocarbonyl(C1-Cs)alkyl, C1-
`
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`
`Csalkylcarbonylamino(C,-C;s)alkyl, N-(C,-Cs)alkylcarbonyl-N-(C,-Cs)alkylamino(C,-Cs)alkyl,
`
`C3-Cetrialkylsilyl(C;-Cs)alkyl, phenyl(C,-Cs)alkyl (wherein the phenyl is optionally substituted
`
`by 1, 2 or 3 of, independently, C,-Csalkyl, C;-Csfluoroalkyl, C;-Csalkoxy, C,-Cafluoroalkoxy,
`
`C,-Caalkylthio, C;-Cgalkylsulfinyl, C;-C3 alkylsulfonyl, halogen, cyano or nitro), heteroaryl(C4-
`
`Cs)alkyl (wherein the heteroaryl is optionally substituted by 1, 2 or 3 of, independently, C,-
`
`Czalkyl, C,-Csfluoroalkyl, C,-Csalkoxy, C1-Cafluoroalkoxy, C.-Csalkylthio, C;-Czalkylsulfinyl,
`
`C,-C3 alkylsulfonyl, halogen, cyano or nitro), phenoxy(C,-Cs)alkyl (wherein the phenyl is
`
`optionally substituted by 1, 2 or 3 of, independently, C,-Czalkyl, C,-Cefluoroalkyl, C,-
`
`Czaalkoxy, C,-C2fluoroalkoxy, C1-Czalkylthio, C;-C3alkylsulfinyl, C1-Cz alkylsulfonyl, halogen,
`
`10
`
`cyano ornitro), heteroaryloxy(C1-Cs)alkyl (wherein the heteroaryl is optionally substituted by
`
`1,2 or 3 of, independently, C)-Czalkyl, C,-C3fluoroalkyl, C;-C3alkoxy, C;-C3fluoroalkoxy, C,-
`
`Caalkylthio, C;-Caalkylsulfinyl, C;-C3 alkylsulfonyl, halogen, cyano or nitro), C3-
`
`Csfluoroalkenyl, C3-Cgcycloalkyl; phenyl or phenyl substituted by 1, 2 or 3 of, independently,
`
`C,-Czalkyl, C,-Csfluoroalkyl, C;-C3alkoxy, C,-C3fluoroalkoxy, halogen, cyano or nitro;
`
`15
`
`heteroaryl or heteroaryl substituted by 1, 2 or 3 of, independently, C,-Cgalkyl, C,-
`
`C2fluoroalkyl, C,-C3alkoxy, C,-C3fluoroalkoxy, halogen, cyano or nitro; C;-Cgalkyl-C(O)-; or
`
`phenyl-C(O)- wherein the phenyl is optionally substituted by 1 or 2 of, independently, C,-
`
`Coalkyl, C,fluoroalkyl, C;-Czalkoxy, C,fluoroalkoxy, fluorine, chlorine, bromine, cyano or nitro;
`
`20
`
`wherein “heteroaryl” means an aromatic ring system containing at least one ring heteroatom
`
`and consisting either of a single ring or of two fused rings;
`
`and wherein the compound of formula (I) is optionally present (e.g. where chemically
`
`possible) as an agrochemically acceptable salt thereof.
`
`25
`
`In the substituent definitions of the compounds of the formula |, each alkyl moiety either
`
`alone or as part of a larger group (such as alkoxy, alkylthio, alkoxycarbonyl, alkylcarbonyl,
`
`30
`
`alkylaminocarbonyl, or dialkylaminocarbonyl, et al.) can be straight-chained or branched.
`
`Typically, the alkyl is, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl,
`
`isobutyl, tert-butyl, n-pentyl, neopentyl, or n-hexyl. The alkyl groups can e.g. be C,-Cealkyl
`
`groups (except where already defined more narrowly), but are preferably C,-C,alkyl or C,-
`
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`
`Czalkyl groups (except where already defined more narrowly), and, more preferably, are
`
`C,-Czalkyl groups such as methyl.
`
`Alkenyl and alkynyl moieties can be in the form of straight