WO2015032702A1 - Herbicidally active 2-halogen-4-alkynyl- phenyl-pyrazolidine-dione or pyrrolidine-dione derivatives - Google Patents

Herbicidally active 2-halogen-4-alkynyl- phenyl-pyrazolidine-dione or pyrrolidine-dione derivatives Download PDF

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WO2015032702A1
WO2015032702A1 PCT/EP2014/068435 EP2014068435W WO2015032702A1 WO 2015032702 A1 WO2015032702 A1 WO 2015032702A1 EP 2014068435 W EP2014068435 W EP 2014068435W WO 2015032702 A1 WO2015032702 A1 WO 2015032702A1
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alkyl
compound
formula
crc
independently
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PCT/EP2014/068435
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French (fr)
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Shuji Hachisu
James Nicholas Scutt
Nigel James Willetts
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Syngenta Limited
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Priority claimed from GB201315947A external-priority patent/GB201315947D0/en
Priority claimed from GB201321554A external-priority patent/GB201321554D0/en
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Publication of WO2015032702A1 publication Critical patent/WO2015032702A1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D498/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D498/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
    • C07D498/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D207/30—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members
    • C07D207/34—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D207/36—Oxygen or sulfur atoms
    • C07D207/38—2-Pyrrolones
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
    • C07D209/54—Spiro-condensed
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D231/28—Two oxygen or sulfur atoms
    • C07D231/30—Two oxygen or sulfur atoms attached in positions 3 and 5
    • C07D231/32—Oxygen atoms
    • C07D231/36—Oxygen atoms with hydrocarbon radicals, substituted by hetero atoms, attached in position 4
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/06—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
    • C07D403/06—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
    • C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
    • C07D487/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D498/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D498/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
    • C07D498/10—Spiro-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D498/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D498/12—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms in which the condensed system contains three hetero rings
    • C07D498/20—Spiro-condensed systems

Definitions

  • the present invention relates to herbicidally active heterocyclic diones, in particular herbicidally active pyrazolidine-dione (more particularly pyrazolidine-3,5-dione) compounds or herbicidally active pyrrolidine-dione (more particularly pyrrolidine-2,4-dione) compounds, or derivatives thereof (e.g. enol ketone tautomer derivatives thereof), to processes for 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.
  • herbicidally active heterocyclic diones in particular herbicidally active pyrazolidine-dione (more particularly pyrazolidine-3,5-dione) compounds or herbicidally active pyrrolidine-dione (more particularly pyrrolidine-2,4-dione) compounds, or derivatives thereof (e.g. eno
  • EP 0 456 063 A2 (Bayer AG) discloses 3-(substituted-phenyl)-pyrrolidine-2,4-dione derivatives, and their use as insecticides, acaricides and herbicides.
  • EP 0 355 599 A1 (Bayer AG) diascloses fused 3-(substituted-phenyl)-pyrrolidin-2,4-dione derivatives, and their use as herbicides, fungicides, antimycotics, insecticides and acaricides.
  • WO 98/05638 A2 (Bayer AG) discloses phenyl-substituted heterocyclic keto-enols or derivatives thereof, for example 3-(2- or 2,5- substituted-phenyl)-pyrrolidin-2,4-dione derivatives, and their use as pesticides.
  • Bayer's commercial insecticide spirotetramat (Bayer AG) discloses phenyl-substituted heterocyclic keto-enols or derivatives thereof, for example 3-(2- or 2,5- substituted-phenyl)-pyrrolidin-2,4-dione derivatives, and their use as pesticides.
  • Bayer's commercial insecticide spirotetramat (Bayer AG) discloses phenyl-substituted heterocyclic keto-enols or derivatives thereof, for example 3-(2- or 2,5- substituted-phenyl)-pyrrolidin-2,4-dione derivatives, and their use as pesticides.
  • ACCase is covered by WO 98/05638 A2.
  • Spirotetramat is disclosed in non-stereospecific form as compound 1-1-0-4 on page 95 of WO 98/05638 A2.
  • ACCase is acetyl CoA carboxylase.
  • WO 92/16510 A1 (Ciba-Geigy AG) discloses 4-aryl-pyrazolidine-3,5-dione herbicides, and their use as herbicides, acaricides and insecticides.
  • EP 0 508 126 A1 (Bayer AG) discloses 3-hydroxy-4-aryl-5-oxo-pyrazoline derivatives, and their use as insecticides, acaricides and herbicides.
  • WO 96/21652 A1 (Ciba-Geigy AG) discloses 4-aryl- and 4-heteroaryl- 5- oxopyrazoline derivatives having pesticidal properties.
  • WO 99/47525 A1 discloses herbicidally active 3-hydroxy-4-aryl-5-oxo- pyrazoline derivatives.
  • the 3-hydroxy-5-oxo-pyrazoline ring system is fused, through the two ring-nitrogens of the pyrazole, to a further ring which also contains a ring-oxygen atom. See also WO 00/47585 A (Novartis AG).
  • WO 01/17972 A2 (Syngenta Participations AG) discloses (4-methyl-phenyl)-substituted (such as 4-methyl-2,6-diethyl-phenyl- substituted) carbocycles or heterocycles, in particular carbocyclic or heterocyclic diones, suitable for use as herbicides.
  • WO 01/74770 A (Bayer AG), and its equivalent US 2003/0216260 A1 , disclose C 2 -phenyl- substituted cyclic ketoenols and their use as pesticides and 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 mefenpyr-diethyl.
  • the cyclic ketoenol (whose tautomer is a cyclic dione) can in particular be a 3-(substituted-phenyl)-pyrrolidine- 2,4-dione, a 3-(substituted-phenyl)-tetrahydrofuran-2,4-dione, a 3-(substituted-phenyl)-pyran- 2,4-dione derivative, a 2-(substituted-phenyl)-cyclopentane-1 ,3-dione, or a 2-(substituted- phenyl)-cyclohexane-1 ,3-dione, et al., or a derivative (e.g.
  • 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 and/or phosphonium salt allegedly to boost activity.
  • the cyclic ketoenol (whose tautomer is a cyclic dione) can in particular be a 3-(substituted-phenyl)-pyrrolidine-2,4-dione, a 3-(substituted- phenyl)-tetrahydrofuran-2,4-dione, a 3-(substituted-phenyl)-pyran-2,4-dione derivative, a 2- (substituted-phenyl)-cyclopentane-l ,3-dione, or a 2-(substituted-phenyl)-cyclohexane-1 ,3- dione, a 4-(substituted-phenyl)-pyrazolidine-3,5-dione, et al., or a derivative (e.g. ester or carbonate derivative) of these cyclic ketoenols / cyclic
  • WO 2006/089633 A2 (Bayer CropScience AG) and its equivalent US 2008/0305955 A1 discloses spiroketal-substituted heterocyclic ketoenols, more particularly 5-spirocyclic-3- (substituted-phenyl)- pyrrolidine-2,4-diones or tetrahydrofuran-2,4-diones, or derivatives thereof, and their use as pesticides, microbicides and/or herbicides.
  • WO 2007/121868 A1 (Bayer CropScience AG) and its equivalent US 2009/0239906 A1 discloses 5-[alkoxyalkyl- or heterocyclyl(alkyl)-]-substituted-3-(substituted-phenyl)- pyrrolidine-2,4-diones, or derivatives thereof, and their use as pesticides, microbicides and/or herbicides. See also WO 2007/140881 A1 (Bayer CropScience AG).
  • WO 2012/175666 A1 (Syngenta Participations AG) discloses certain substituted N-oxy pyrazolo-triazepine-dione derivatives having pesticidal and herbicidal properties.
  • WO 201 1/151 199 A1 discloses new 5-spiroheterocyclic-3- (substituted-phenyl)-pyrrolidine-2,4-dione compounds, or derivatives, in which the phenyl has at least one C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, -CHO, C Cealkylcarbonyl or d-Cealkoxycarbonyl substituent, and their use as insecticides, acaricides, molluscicides and nematicides.
  • 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.
  • WO 2013/079708 A1 (Syngenta Limited and Syngenta Participations AG) discloses cyclopentane-1 ,3-dione compounds and derivatives (e.g.
  • Heterocyclic dione compounds have now been discovered, in particular pyrazolidine-dione (more particularly pyrazolidine-3,5-dione) compounds or pyrrolidine-dione (more particularly pyrrolidine-2,4-dione) compounds or fused bicyclic derivatives of such diones, which are substituted, at the ring-carbon atom of the heterocyclic dione which is between the two oxo- substituted ring-carbons of the heterocyclic dione, by a phenyl which itself is substituted (a) at the 4-position of the phenyl by (specifically) prop-1 -ynyl and (b) at a 2-position of the phenyl by (specifically) fluorine or chlorine; or derivatives of the enol ketone tautomer of such heterocyclic diones.
  • These compounds of the present invention appear to exhibit potent herbicidal activity and/or plant-growth-inhibiting properties in the control of grassy monocotyledonous weeds, e.g. after post-emergence application of the compounds in particular at an application rate of 250 g/ha - see the post-emergence herbicidal activity results for compounds A2, A6, A8, A9, A14, A24, A26, A29, A30, P1 , P2, P3, P4 and P5 of the present invention in Biological Example 1 hereinafter.
  • Certain compounds of the present invention when applied post-emergence, appear to be selective for warm-climate grassy monocotyledonous weed control in certain
  • CKE is of sub-formula (A) and/or (B):
  • R 1 is fluorine or chlorine
  • R 2 is hydrogen, methyl, ethyl, n-propyl, n-butyl, cyclopropyl, ethynyl, cyano, fluorine, chlorine, bromine, CrC 3 alkoxy, CrC 2 fluoroalkoxy, (difluoro)vinyloxy, Ci-C 2 alkoxy-Ci-C 3 alkoxy-, or C 1 f I u oroa I koxy-C i - C 3 a I koxy- ;
  • X is NR 4 or CR 5 R 6 ; wherein:
  • R 3 , R 4 , and R 5 independently of each other, are:
  • Ci-C 3 alkylthioCi-C 3 alkyl in particular C 1 -C 2 alkylthioC 1 -C 2 alkyl such as MeSCH 2 CH 2 -
  • C C 4 alkoxy in particular methoxy
  • R 9 -C ⁇ C-C(R 7 )(R 8 )-
  • benzyl optionally substituted on its phenyl ring by 1 or 2 substituents independently being halogen (preferably fluorine, chlorine or bromine), C-
  • -C 2 alkyl (preferably methyl), C-ifluoroalkyl (preferably trifluoromethyl), C 1 -C 2 alkoxy (preferably methoxy), C-ifluoroalkoxy (preferably trifluoromethoxy or difluoromethoxy), -C ⁇ C-R 13 , -C(R 14 ) C(R 15 )(R 16 ), -C(0)Me, -C(0)-Cifluoroalkyl, -S(0) n 4-Me, -S(0) n4 -Cifluoroalkyl, -NR 19 R 20 , or cyano; or
  • R 3 and R 4 are hydrogen or CrC 3 alkyl; and provided that when X is CR 5 R 6 , then at least one of R 3 and R 5 (preferably R 3 ) is hydrogen or Ci-C 3 alkyl; or R 3 and R 4 are taken together, and/or R 3 and R 5 are taken together, to form a chain which is (a), (b), (c), (d), (e), (f) or (g), as shown below:
  • R 29 is O or NR 4U ; and R 6 is hydrogen or CrC 3 alkyl; or R 5 and R 6 taken together are -(CH 2 ) n i- or -(CH 2 ) n2 -X 1 -(CH 2 ) n3 -, in which case R 3 is as defined herein (preferably hereinabove) provided that R 3 and R 5 are not taken together; wherein X 1 is O, C(H)(C C 2 alkyl), C(C C 2 alkyl) 2 or C(H)(C C 2 alkoxy);
  • n1 is 2, 3, 4 or 5 (preferably n1 is 4 or 5);
  • R 7 and R 8 independently of each other, are hydrogen or methyl
  • R 9 is hydrogen, methyl, ethyl or chlorine
  • R 10 , R 11 and R 12 independently of each other, are hydrogen, methyl or ethyl, provided that R 10 , R 11 and R 12 in total contain no more than three carbon atoms;
  • R 13 is hydrogen, methyl, Cifluoroalkyl (in particular trifluoromethyl), fluorine or chlorine;
  • R 14 , R 15 and R 16 independently are hydrogen, methyl, Cifluoroalkyl (in particular trifluoromethyl), fluorine or chlorine; provided that R 14 , R 15 and R 16 in total contain no more than one carbon atom, and R 14 , R 15 and R 16 in total comprise no more than one chlorine; and
  • n4 is 0, 1 or 2;
  • n5 is 0, 1 or 2;
  • R 17 and R 18 independently are C C 3 alkyl, Cifluoroalkyl, or -NR 19A R 20A ;
  • n18 is 0, 1 or 2;
  • R 19 is -C(0)-CrC 2 alkyl, -C(0)-Cifluoroalkyl, -S(0) 2 -C C 2 alkyl, -S(0) 2 -Cifluoroalkyl, Ci-C 2 alkyl, or Cifluoroalkyl;
  • R 20 and R 20A independently are hydrogen, methyl or Cifluoroalkyl
  • R 19A is hydrogen, C C 2 alkyl or Cifluoroalkyl; and wherein: R , R , R and R are independently hydrogen or methyl; provided that two, three or all of R 21 , R 22 , R 27 and R 28 are hydrogen; and
  • R 21A and R 22A are independently hydrogen or methyl
  • R 23 , R 24 , R 25 , and R 26 are independently hydrogen, methyl, ethyl or methoxymethyl; provided that two, three or all of R 23 , R 24 , R 25 and R 26 are hydrogen;
  • R 23 and R 25 are taken together and form a -CH 2 - or -CH 2 CH 2 - bridge, and R 24 and R 26 are hydrogen;
  • R 29 and R 32 are independently hydrogen or methyl
  • R 30 is hydrogen, d-C 3 alkyl, CrC 2 fluoroalkyl, CrC 3 alkoxy (preferably methoxy),
  • CrC 3 fluoroalkoxy in particular CF 3 CH 2 0-
  • Ci-C 2 alkoxyCrC 2 alkyl in particular methoxymethyl
  • Ci-C 2 alkylthioCrC 2 alkyl preferably R 30 is hydrogen or methoxy, more preferably hydrogen
  • n30 is 0, 1 or 2 (preferably 0);
  • R 31 is hydrogen, methyl or ethyl (preferably R 31 is hydrogen);
  • G is hydrogen; an agriculturally acceptable metal, or an agriculturally acceptable sulfonium or ammonium group; or G is -C(X a )-R a , -C(X b )-X c -R b , -C(X d )-N(R c )-R d , -S0 2 -R e , -P(X e )(R )-R 9 , -CH 2 -X f -R h ; or phenyl-CH 2 - or phenyl-CH(Ci-C 2 alkyl)- (in each of which the phenyl is optionally substituted by 1 , 2 or 3 of, independently, Ci-C 2 alkyl, CifluoroalkyI, Ci-C 2 alkoxy, Cifluoroalkoxy, fluorine, chlorine, bromine, cyano or nitro), or heteroaryl-CH 2 - or heteroaryl-CH(Ci
  • R a is H, Ci-C 2 ialkyl, C 2 -C 2 ialkenyl, C 2 -Ci 8 alkynyl, Ci-Ci 0 fluoroalkyl, Ci-Ci 0 cyanoalkyl, C Ci 0 nitroalkyl, Ci-Ci 0 aminoalkyl, Ci-C 5 alkylamino(Ci-C 5 )alkyl, C 2 -C 8 dialkylamino(Ci-C 5 )alkyl, C 3 -C 7 cycloalkyl(Ci-C 5 )alkyl, Ci-C 5 alkoxy(Ci-C 5 )alkyl, C 3 -C 5 alkenyloxy(Ci-C 5 )alkyl, C 3 - C 5 alkynyloxy (C C 5 )alkyl, Ci-C 5 alkylthio(Ci-C 5 )alkyl, Ci-C 5 alkylsulfiny
  • R c and R d are each independently of each other hydrogen, d-C 10 alkyl, C 3 -d 0 alkenyl, d- d 0 alkynyl, C 2 -d 0 fluoroalkyl, d-d 0 cyanoalkyl, d-d 0 nitroalkyl, d-d 0 aminoalkyl, d- dalkylamino(C 1 -d)alkyl, d-ddialkylamino(C 1 -C 5 )alkyl, d-dcycloalkyl(d-d)alkyl, d- dalkoxy(d-d)alkyl, d-dalkenyloxy(d-d)alkyl, C 3 -dalkynyloxy(d-d)alkyl, C dalkylthio(d-d)alkyl, C 1 -dalkylsulfinyl(C 1 -C 5
  • R c and R d together with the nitrogen to which they are bonded, to form an unsubstituted 4, 5, 6 or 7 (e.g. 5 or 6) membered ring, optionally containing one heteroatom selected from O or S; and
  • R e is d-C 10 alkyl, C 2 -C 10 alkenyl, C 2 -C 10 alkynyl, d-C 10 fluoroalkyl, d-C 10 cyanoalkyl, d- C 10 nitroalkyl, d-C 10 aminoalkyl, C 1 -C 5 alkylamino(C 1 -C 5 )alkyl, C 2 -C 8 dialkylamino(C 1 -C 5 )alkyl, C 3 -C 7 cycloalkyl(Ci-C 5 )alkyl, Ci-C 5 alkoxy(Ci-C 5 )alkyl, C 3 -C 5 alkenyloxy(Ci-C 5 )alkyl, C 3 - C 5 alkynyloxy(Ci-C 5 )alkyl, Ci-C 5 alkylthio(Ci-C 5 )alkyl, Ci-C 5 alkylsulfinyl(
  • R and R 9 are are each independently of each other CrCi 0 alkyl, C 2 -Ci 0 alkenyl, C 2 -Ci 0 alkynyl, Ci-Ci 0 alkoxy, Ci-Ci 0 fluoroalkyl, Ci-Ciocyanoalkyl, CrCi 0 nitroalkyl, Ci-Ci 0 aminoalkyl, d- C 5 alkylamino(C 1 -C 5 )alkyl, C 2 -C 8 dialkylamino(C 1 -C 5 )alkyl, C 3 -C 7 cycloalkyl(C 1 -C 5 )alkyl, d- C 5 alkoxy(C 1 -C 5 )alkyl, C 3 -C 5 alkenyloxy(C 1 -C 5 )alkyl, C 3 -C 5 alkynyloxy(C 1 -C 5 )alkyl, C
  • R h is Ci-Ci 0 alkyl, C 3 -Ci 0 alkenyl, C 3 -Ci 0 alkynyl, Ci-Ciofluoroalkyl, Ci-Ciocyanoalkyl, d- Ci 0 nitroalkyl, C 2 -Ci 0 aminoalkyl, Ci-C 5 alkylamino(Ci-C 5 )alkyl, C2-C 8 dialkylamino(Ci-C 5 )alkyl, C 3 -C 7 cycloalkyl(Ci-C 5 )alkyl, Ci-C 5 alkoxy(Ci-C 5 )alkyl, C 3 -C 5 alkenyloxy(Ci-C 5 )alkyl, C 3 - C 5 alkynyloxy(Ci-C 5 )alkyl, Ci-C 5 alkylthio(Ci-C 5 )alkyl, Ci-C 5 alkylsulfiny
  • each alkyl moiety either alone or as part of a larger group can be straight-chained or branched.
  • the alkyl is, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, ierf-butyl, n-pentyl, neopentyl, or n-hexyl.
  • the alkyl groups can e.g.
  • C Cealkyl groups except where already defined more narrowly
  • C 1 -C 4 alkyl or C C 3 alkyl groups except where already defined more narrowly
  • C 1 -C 2 alkyl groups such as methyl
  • Alkenyl and alkynyl moieties can be in the form of straight or branched chains, and the alkenyl moieties, where appropriate, can be of either the (£)- or (Z)-configuration.
  • the alkenyl or alkynyl are typically C 2 -C 3 alkenyl or C 2 -C 3 alkynyl such as vinyl, allyl, ethynyl, propargyl or prop-1-ynyl.
  • Alkenyl and alkynyl moieties can contain one or more double and/or triple bonds in any combination; but preferably contain only one double bond (for alkenyl) or only one triple bond (for alkynyl).
  • Halogen is fluorine, chlorine, bromine or iodine. Preferred halogens are fluorine, chlorine or bromine.
  • FluoroalkyI groups are alkyl groups which are substituted with one or more (e.g. 1 , 2, 3, 4 or 5; in particular 1 , 2 or 3; e.g. 1 or 2) fluorine atoms.
  • FluoroalkyI is typically CrC 3 fluoroalkyl or C C 2 fluoroalkyl (preferably Cifluoroalkyl), such as CF 3 , CHF 2 , CH 2 F, CH 3 CHF-, CF 3 CH 2 -, CHF 2 CH 2 -, CH 2 FCH 2 -, CHF 2 CF 2 - or (CH 3 ) 2 CF-.
  • Fluoroalkoxy is typically C C 3 fluoroalkoxy or Ci-C 2 fluoroalkoxy (preferably Cifluoroalkoxy), such as CF 3 0, CHF 2 0, CH 2 FO, CH 3 CHFO-, CF 3 CH 2 0-, CHF 2 CH 2 0- or CH 2 FCH 2 0-.
  • aryl means phenyl or naphthyl.
  • a preferred aryl group is phenyl.
  • heteroaryl as used herein means an aromatic ring system containing at least one ring heteroatom and consisting either of a single ring or of two fused rings. Preferably, single rings will contain 1 , 2 or 3 ring heteroatoms and bicyclic systems 1 , 2, 3 or 4 ring
  • heteroatoms which will preferably be selected from nitrogen, oxygen and sulfur.
  • a "heteroaryl” is furyl, thienyl, pyrrolyl, pyrazolyl, imidazolyl, 1 ,2,3-triazolyl, 1 ,2,4-triazolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, 1 ,2,4-oxadiazolyl, 1 ,3,4-oxadiazolyl,
  • heterocyclyl as used herein, except where explicitly stated otherwise, means a 4, 5, 6 or 7 (in particular 5, 6 or 7) membered monocyclic organic ring or a 8, 9, 10 or 1 1 (in particular 8, 9 or 10) membered fused bicyclic organic ring system, which is fully saturated, and which has one or two (preferably one) ring heteroatoms independently selected from oxygen, sulfur and nitrogen.
  • the heterocyclyl has two ring heteroatoms, preferably, the two ring heteroatoms are separated by at least two ring carbon atoms.
  • the heterocyclyl is attached at a ring carbon atom within the heterocyclyl.
  • the heterocyclyl can be tetrahydrofuranyl, tetrahydropyranyl, tetrahydrothiophenyl, 1 ,4-dioxanyl, 1 ,4-dithianyl, morpholinyl, thiomorpholinyl, pyrrolidinyl, piperidinyl or piperazinyl; more particularly tetrahydrofuranyl (e.g. tetrahydrofuran-2-yl or particularly tetrahydrofuran-3-yl), tetrahydropyranyl (e.g. tetrahydropyran-2-yl, tetrahydropyran-3-yl or particularly
  • heterocyclyl when optionally substituted, is optionally substituted by 1 or 2 (e.g. 1 ) ring-carbon substituents independently being CrC 3 alkyl (e.g.
  • a cycloalkyi is cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.
  • (Cycloalkyl)alkyl is preferably (cycloalkyl)methyl such as (C 3 -C 6 cycloalkyl)methyl in particular
  • cyclopropylmethyl Preferably, cycloalkenyl is cyclopentenyl or cyclohexenyl.
  • the invention relates also to the agriculturally acceptable salts which the compounds of formula I are able to form with transition metal, alkali metal and alkaline earth metal bases, amines, quaternary ammonium bases or tertiary sulfonium bases.
  • transition metal alkali metal and alkaline earth metal salt formers
  • hydroxides of copper, iron, lithium, sodium, potassium, magnesium and calcium special mention should be made of the hydroxides of copper, iron, lithium, sodium, potassium, magnesium and calcium, and preferably the hydroxides, bicarbonates and carbonates of sodium and potassium.
  • amines suitable for ammonium salt formation include ammonia as well as primary, secondary and tertiary C-i-C-isalkylamines, C 1 -C 4 hydroxyalkylamines and
  • C 2 -C 4 alkoxyalkyl-amines for example methylamine, ethylamine, n-propylamine,
  • isopropylamine the four butylamine isomers, n-amylamine, isoamylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, pentadecylamine, hexadecylamine, heptadecylamine, octadecylamine, methylethylamine, methylisopropylamine,
  • Preferred quaternary ammonium bases suitable for salt formation correspond, for example, to the formula [N(R a R b R c R d )]OH, wherein R a , R b , R c and R d are each independently of the others hydrogen, CrC 4 alkyl.
  • Further suitable tetraalkylammonium bases with other anions can be obtained, for example, by anion exchange reactions.
  • Preferred tertiary sulfonium bases suitable for salt formation correspond, for example, to the formula [SR e R f R g ]OH, wherein R e , R f and R g are each independently of the others C C 4 alkyl. Trimethylsulfonium hydroxide is especially preferred.
  • Suitable sulfonium bases may be obtained from the reaction of thioethers, in particular dialkylsulfides, with alkylhalides, followed by conversion to a suitable base, for example a hydroxide, by anion exchange reactions.
  • the compounds of formula I according to the invention also include hydrates which may be formed during the salt formation.
  • the latentiating groups i.e. leaving or removeable groups
  • G for example, without limitation, the latentiating groups where G is -C(X a )-R a or -C(X b )-X c -R b , et al.
  • G is H
  • these processes include enzymatic cleavage or other in/on-plant cleavage (e.g.
  • Some compounds bearing such groups G occasionally offer certain advantages or different technical properties, such as improved and/or more consistent and/or different penetration of the cuticula of the plants treated, increased and/or different tolerance of certain crops, improved and/or different compatibility or stability in formulated mixtures containing other herbicides, herbicide safeners, plant growth regulators, fungicides or insecticides, or reduced and/or different leaching properties in soils.
  • G is hydrogen; an agriculturally acceptable metal (e.g. an agriculturally acceptable alkali metal or alkaline earth metal), or an agriculturally acceptable sulfonium or ammonium group; or G is -C(X a )-R a or -C(X b )-X c -R b , wherein X a , R a , X b , X c and R b are as defined herein.
  • an agriculturally acceptable metal e.g. an agriculturally acceptable alkali metal or alkaline earth metal
  • G is -C(X a )-R a or -C(X b )-X c -R b , wherein X a , R a , X b , X c and R b are as defined herein.
  • G is a group -C(X a )-R a or -C(X b )-X c -R b , wherein X a , R a , X b , X c and R b are as defined herein.
  • X a , X b , X c , X d , X e and/or X f are oxygen. More preferably, X a , X b , X c , X d , X e and X f are oxygen.
  • R a is CrCi 0 alkyl (e.g. CrC 6 alkyl), C 2 -C 6 alkenyl (e.g. C 2 -C 4 alkenyl), C 2 -C 6 alkynyl (e.g. C 2 -C 4 alkynyl), C 3 -C 6 cycloalkyl or Ci-C 4 alkoxyCi-C 4 alkyl.
  • R b is C C 10 alkyl (e.g. C C 6 alkyl), C 2 -C 5 alkenyl-CH 2 - (e.g.
  • R a is C Ci 0 alkyl (e.g. CrC 6 alkyl), C 2 -C 6 alkenyl (e.g. C 2 -C 4 alkenyl), C 2 -C 6 alkynyl (e.g. C 2 -C 4 alkynyl), C 3 -C 6 cycloalkyl or Ci-C 4 alkoxyCi-C 4 alkyl; and R b is CrCi 0 alkyl (e.g. CrC 6 alkyl),
  • C 2 -C 5 alkenyl-CH 2 - e.g. C 2 -C 3 alkenyl-CH 2 -
  • C 2 -C 4 alkenyl-CH(Me)- e.g.
  • C 2 -C 4 alkynyl-CH(Me)- e.g. C 2 -C 3 alkynyl-CH(Me)-
  • C 3 -C 6 cycloalkyl e.g. Ci-C 4 alkoxyCi-C 4 alkyl.
  • G is hydrogen, or an agriculturally acceptable alkali metal or alkaline earth metal, or an agriculturally acceptable sulfonium or ammonium group. More preferably, G is hydrogen, or an agriculturally acceptable alkali metal or alkaline earth metal.
  • G is hydrogen, -C(X a )-R a or -C(X b )-X c -R b .
  • G is hydrogen
  • R 1 is fluorine
  • R 1 is chlorine
  • Ci-C 3 alkoxy e.g. methoxy, ethoxy, n-propoxy or isoprop
  • R 2 is Ci-C 2 alkoxy-CrC 3 alkoxy- or Cifluoroalkoxy-CrC 3 alkoxy-
  • R 2 is R 2A 0-CH(R 2B )-CH(R 2C )-0-; wherein R is C 1 -C 2 alkyl (in particular methyl) or C-ifluoroalkyl;
  • R 2B and R 2C are independently hydrogen or methyl, provided that one or both of R 2B and R 2C are hydrogen.
  • R 2A is methyl or C-ifluoroalkyl, more preferably methyl.
  • both of R 2B and R 2C are hydrogen.
  • R 2 is Ci-C 2 alkoxy-Ci-C 3 alkoxy- or Cifluoroalkoxy-Ci-C 3 alkoxy- (in particular when R 2 is R 2A 0-CH(R 2B )-CH(R 2C )-0-), then R 2 is MeO-CH 2 -CH 2 -0-.
  • R 2 is methyl, ethyl, n- propyl, cyclopropyl, ethynyl, cyano, fluorine, chlorine, bromine, methoxy, ethoxy,
  • Cifluoroalkoxy Cifluoroalkylmethoxy (in particular CF 3 CH 2 0-), (difluoro)vinyloxy (i.e.
  • CF 2 CH-0-), or MeO-CH 2 -CH 2 -0-.
  • R 2 is hydrogen, methyl, ethyl, ethynyl, chlorine, methoxy, ethoxy, Cifluoroalkoxy (e.g. monofluoromethoxy, difluoromethoxy or trifluoromethoxy), Cifluoroalkylmethoxy (in particular CF 3 CH 2 0-), or MeO-CH 2 -CH 2 -0-.
  • Cifluoroalkoxy e.g. monofluoromethoxy, difluoromethoxy or trifluoromethoxy
  • Cifluoroalkylmethoxy in particular CF 3 CH 2 0-
  • MeO-CH 2 -CH 2 -0- MeO-CH 2 -CH 2 -0-.
  • R 2 is not hydrogen
  • R 2 is methyl, ethyl, ethynyl, chlorine, methoxy, ethoxy, Cifluoroalkoxy (e.g. monofluoromethoxy,
  • R 2 is methyl, chlorine, methoxy or ethoxy.
  • R 2 is chlorine, methoxy or ethoxy.
  • R 2 is methoxy
  • R 1 is fluorine
  • R 2 is methyl, ethyl, ethynyl, chlorine, methoxy, ethoxy, Cifluoroalkoxy, Cifluoroalkylmethoxy, or MeO-CH 2 -CH 2 -0-; still more preferably chlorine, methoxy or ethoxy; most preferably methoxy.
  • R 1 is chlorine
  • R 2 is methyl, ethyl, ethynyl, chlorine, methoxy, ethoxy, Cifluoroalkoxy, Cifluoroalkylmethoxy, or MeO-CH 2 -CH 2 -0-; still more preferably chlorine, methoxy or ethoxy; most preferably methoxy.
  • X is NR 4 .
  • R 5 and R 6 are not taken together to be -(CH 2 ) n or -(CH 2 ) n2 -X 1 -(CH 2 ) n3 -. Therefore, preferably, R 6 is hydrogen or d-C 6 alkyl.
  • R 6 is hydrogen or methyl. Most preferably, R 6 is hydrogen.
  • R 3 is hydrogen
  • R 3 is hydrogen, C 1 -C 2 fluoroalkyl (in particular C-ifluoroalkyl), or Ci-C 3 alkyl; or R 3 and R 4 are taken together, and/or R 3 and R 5 are taken together, to form a chain which is (a), (b), (c), (d), (e), (f) or (g), as defined herein.
  • R 4 and/or R 5 are preferably, e.g. in all aspects and/or embodiments of the invention.
  • benzyl optionally substituted on its phenyl ring by 1 or 2 substituents independently being fluorine, chlorine, bromine, C-
  • R 3 and R 4 are hydrogen or CrC 3 alkyl; and provided that when X is CR 5 R 6 , then at least one of R 3 and R 5 (preferably R 3 ) is hydrogen or CrC 3 alkyl; or R 3 and R 4 are taken together, and/or R 3 and R 5 are taken together, to form a chain which is (a), (b), (c), (d), (e), (f) or (g), as defined herein.
  • R 4 and/or R 5 independently of each other, is or are:
  • -C 3 alkyl in particular methyl or ethyl
  • -C 2 fluoroalkyl in particular Cifluoroalkyl
  • MeOCH 2 CH 2 - MeSCH 2 CH 2 -
  • C C 2 alkoxy in particular methoxy
  • benzyl optionally substituted on its phenyl ring by 1 or 2 substituents independently being fluorine, chlorine, methyl, Cifluoroalkyl (preferably trifluoromethyl), methoxy,
  • C-ifluoroalkoxy (preferably trifluoromethoxy or difluoromethoxy), -C ⁇ C-R 13 , or cyano; provided that when X is NR 4 , then at least one of R 3 and R 4 (preferably R 3 ) is hydrogen or CrC 3 alkyl; and provided that when X is CR 5 R 6 , then at least one of R 3 and R 5 (preferably R 3 ) is hydrogen or CrC 3 alkyl; or R 3 and R 4 are taken together, and/or R 3 and R 5 are taken together, to form a chain which is (a), (b), (c), (d), (e), (f) or (g), as defined herein.
  • R 4 and/or R 5 independently of each other, is or are: hydrogen, CrC 3 alkyl (in particular methyl or ethyl), R 9 -C ⁇ C-C(R 7 )(R 8 )-, or Het-CH 2 -;
  • R 3 and R 4 are hydrogen or C Csalkyl; and provided that when X is CR 5 R 6 , then at least one of R 3 and R 5 (preferably R 3 ) is hydrogen or d-C 3 alkyl; or R 3 and R 4 are taken together, and/or R 3 and R 5 are taken together, to form a chain which is (a), (b), (c), (d), (e), (f) or (g), as defined herein.
  • R 3 is not hydrogen; and/or, preferably, R 4 and/or R 5 is or are not hydrogen.
  • R 3 is C Csalkyl (preferably methyl or ethyl) or CrC 2 fluoroalkyl (in particular C-ifluoroalkyl); and/or
  • R 4 and/or R 5 is or are, independently, CrC 3 alkyl (preferably methyl or ethyl) or
  • Het is a heteroaryl (in particular monocyclic heteroaryl), attached at a ring-carbon, which is optionally substituted by 1 , 2 or 3 (in particular 1 or 2, e.g.
  • ring-carbon substituents independently being Ci-C 2 alkyl, Cifluoroalkyl, CrC 2 alkyl-C(0)-, Cifluoroalkyl-CiO)-, ethynyl, prop-1-ynyl, CrC 2 alkoxy, C-ifluoroalkoxy, fluorine, chlorine, bromine, cyano or nitro, provided that any chlorine, bromine, alkoxy or fluoroalkoxy is not substituted at any ring-carbon bonded directly to a ring-nitrogen of the heteroaryl;
  • Het is a heteroaryl (in particular monocyclic heteroaryl), attached at a ring-carbon, which is optionally substituted by 1 or 2 (in particular 1 ) ring-carbon substituents independently being Ci-C 2 alkyl (in particular methyl), Cifluoroalkyl (in particular CF 3 ), C C 2 alkyl-C(0)- (in particular Me-C(O)-), Cifluoroalkyl-C(O)-, ethynyl, prop-1 -ynyl, fluorine or cyano;
  • CrC 2 alkyl e.g. methyl
  • Cifluoroalkyl methyl-C(O)- or Cifluoroalkyl-C(O)- substituent.
  • Het is a heteroaryl (in particular monocyclic heteroaryl), attached at a ring-carbon, which is optionally substituted by 1 or 2 (in particular 1 ) ring-carbon substituents independently being C-
  • Het is an optionally substituted monocyclic heteroaryl, attached at a ring-carbon.
  • monocyclic heteroaryl can be 5-membered or 6-membered monocyclic heteroaryl.
  • Het is an optionally substituted monocyclic heteroaryl, attached at a ring-carbon, which is:
  • pyridinyl preferably pyridin-3-yl or most preferably pyridin-2-yl
  • pyrazolyl preferably pyrazol- 5-yl or pyrazol-4-yl, or most preferably pyrazol-3-yl
  • imidazolyl preferably imidazol-2-yl
  • pyrazinyl preferably pyrimidinyl (preferably pyrimidin-4-yl)
  • pyridazinyl preferably pyridazin-3-yl
  • triazolyl e.g. 1 ,2,3-triazolyl
  • tetrazol-5-yl oxazolyl, thiazolyl, isoxazolyl, isothiazolyl or oxadiazolyl.
  • Het is an optionally substituted monocyclic heteroaryl, attached at a ring-carbon, which is:
  • pyridinyl preferably pyridin-3-yl or most preferably pyridin-2-yl
  • pyrazolyl preferably pyrazol- 5-yl or pyrazol-4-yl, or most preferably pyrazol-3-yl
  • imidazolyl preferably imidazol-2-yl
  • pyrazinyl preferably pyrimidinyl (preferably pyrimidin-4-yl)
  • pyridazinyl preferably pyridazin-3-yl
  • triazolyl e.g. 1 ,2,3-triazolyl
  • Het is an optionally substituted monocyclic heteroaryl, attached at a ring-carbon, which is:
  • pyridinyl preferably pyridin-3-yl or most preferably pyridin-2-yl
  • pyrazolyl preferably pyrazol- 5-yl or pyrazol-4-yl, or most preferably pyrazol-3-yl
  • imidazolyl preferably imidazol-2-yl
  • pyrazinyl preferably pyrimidinyl (preferably pyrimidin-4-yl)
  • pyridazinyl preferably pyridazin-3-yl
  • Het is an optionally substituted monocyclic heteroaryl, attached at a ring-carbon, which is:
  • pyridin-3-yl pyridin-2-yl, pyrazinyl, or pyrazolyl (preferably pyrazol-5-yl or pyrazol-4-yl, or most preferably pyrazol-3-yl).
  • Het is an optionally substituted monocyclic heteroaryl, attached at a ring-carbon, which is: optionally substituted pyridin-2-yl, optionally substituted pyrazinyl or optionally substituted pyrazol-3-yl.
  • Het or Het-CH 2 - is present in the compound of formula (I) and Het is a basic heteroaryl group (e.g. pyridinyl, e.g. pyridin-2-yl, or another basic heteroaryl group), then the compound of formula (I) can be optionally present as an agrochemically acceptable salt thereof (and preferably can be present as an agrochemically acceptable acid addition salt thereof such as a hydrohalide, e.g. hydrochloride, salt thereof).
  • a basic heteroaryl group e.g. pyridinyl, e.g. pyridin-2-yl, or another basic heteroaryl group
  • the compound of formula (I) can be optionally present as an agrochemically acceptable salt thereof (and preferably can be present as an agrochemically acceptable acid addition salt thereof such as a hydrohalide, e.g. hydrochloride, salt thereof).
  • Het is one of the heteroaryls illustrated below:
  • Het is one of the heteroaryls illustrated below:
  • Het is one of the heteroaryls illustrated below:
  • R 7 and R 8 are both hydrogen.
  • R 9 is hydrogen or methyl, more preferably hydrogen.
  • R 10 is hydrogen
  • R 11 and R 12 are preferably, e.g. in all aspects and/or embodiments of the invention.
  • R 11 and R 12 independently of each other, are hydrogen or methyl. More preferably, one or both of R 11 and R 12 is or are hydrogen.
  • R 13 is hydrogen or methyl, more preferably hydrogen.
  • R 14 is hydrogen; and/or, preferably, R 15 is hydrogen or fluorine; and/or, preferably, R 16 is hydrogen, methyl or fluorine; provided that, in each case, R 14 , R 15 and R 16 in total contain no more than one carbon atom, and R 14 , R 15 and R 16 in total comprise no more than one chlorine.
  • n4 is 2.
  • n5 is 2.
  • R 17 and/or R 18 independently are C 1 -C 2 alkyl (in particular methyl), CifluoroalkyI (in particular trifluoromethyl), or -NR 19A R : More preferably, R 17 and/or R 18 independently are methyl or dfluoroalkyl (in particular methyl or trifluoromethyl).
  • n18 is 2.
  • R 19 is -C(0)-methyl, - C(0)-dfluoroalkyl (in particular -C(O)-trifluoromethyl), -S(0) 2 -methyl, -S(0) 2 -C 1 fluoroalkyl (in particular -S(0) 2 -trifluoromethyl), methyl, or C-ifluoroalkyl (in particular trifluoromethyl).
  • R 20 and R 20A are preferably, e.g. in all aspects and/or embodiments of the invention.
  • R 19A is hydrogen, methyl or trifluoromethyl.
  • R 3 and R 4 are taken together, and/or R 3 and R 5 are taken together, to form a chain which is (a), (b), (c), (d), (e), (f) or (g), as shown below:
  • R 3 and R 4 being taken together, and/or R 3 and R 5 being taken together, to form a chain is a preferred embodiment of the invention (i.e. is preferred in all aspects and/or embodiments of the invention).
  • the chain is (a), (d), (e), (f) or (g), more preferably (a), (e), (f) or (g), more preferably (a), (e) or (g), most preferably (a) or (e), as defined herein.
  • Y is O; and/or R is CrC 3 alkoxy such as methoxy.
  • R 21 , R 22 , R 27 and R 28 are hydrogen.
  • more preferably Y is O and/or R 40 is CrC 3 alkoxy; and/or more preferably R 3 and R 4 are taken together, and/or R 3 and R 5 are taken together, to form a chain which is (a), (d), (e), (f) or (g), more preferably (a), (e), (f) or (g), more preferably (a), (e) or (g), most preferably (a) or (e), as defined herein.
  • R 21A and R 22A are both hydrogen.
  • more preferably Y is O and/or R 40 is CrC 3 alkoxy; and/or more preferably R 3 and R 4 are taken together, and/or R 3 and R 5 are taken together, to form a chain which is (a), (d), (e), (f) or (g), more preferably (a), (e), (f) or (g), more preferably (a), (e) or (g), most preferably (a) or (e), as defined herein.
  • R 29 and R 32 are both hydrogen.
  • more preferably Y is O and/or R 40 is CrC 3 alkoxy; and/or more preferably R 3 and R 4 are taken together, and/or R 3 and R 5 are taken together, to form a chain which is (a), (d), (e), (f) or (g), more preferably (a), (e), (f) or (g), more preferably (a), (e) or (g), most preferably (a) or (e), as defined herein.
  • R 30 is hydrogen or methoxy, more preferably hydrogen.
  • R 31 is hydrogen.
  • more preferably Y is O and/or R 40 is C-i-C 3 alkoxy; and/or more preferably R 3 and R 4 are taken together, and/or R 3 and R 5 are taken together, to form a chain which is (a), (d), (e), (f) or (g), more preferably (a), (e), (f) or (g), more preferably (a), (e) or (g), most preferably (a) or (e), as defined herein.
  • R 23 , R 24 , R 25 and R 26 are hydrogen.
  • more preferably Y is O and/or R 40 is C-i-C 3 alkoxy; and/or more preferably R 3 and R 4 are taken together, and/or R 3 and R 5 are taken together, to form a chain which is (a), (d), (e), (f) or (g), more preferably (a), (e), (f) or (g), more preferably (a), (e) or (g), most preferably (a) or (e), as defined herein. More preferably, e.g.
  • R 21 , R 22 , R 27 and R 28 are hydrogen
  • R 21A and R 22A are both hydrogen
  • R 29 and R 32 are both hydrogen.
  • Y is O and/or R 40 is CrC 3 alkoxy; and/or even more preferably R 3 and R 4 are taken together, and/or R 3 and R 5 are taken together, to form a chain which is (a), (d), (e), (f) or (g), more preferably (a), (e), (f) or (g), more preferably (a), (e) or (g), most preferably (a) or (e), as defined herein.
  • R 21 , R 21A , R 22 , R 22A , R 23 , R 24 , R 25 , R 26 , R 27 , R 28 , R 29 , R 30 , R 31 and R 32 are hydrogen.
  • Y is O and/or R 40 is CrC 3 alkoxy; and/or even more preferably R 3 and R 4 are taken together, and/or R 3 and R 5 are taken together, to form a chain which is (a), (d), (e), (f) or (g), more preferably (a), (e), (f) or (g), more preferably (a), (e) or (g), most preferably (a) or (e), as defined herein.
  • R is CrC 3 alkoxy. More preferably, R 40 is methoxy.
  • the compound of formula (I) is one of compounds A1 to A141 , as described and/or illustrated herein, optionally present (e.g. where chemically possible) as an agrochemically acceptable salt thereof.
  • the compound of formula (I) is one of compounds A142 to A149, or P1 to P12, or A150 or A151 , as described and/or illustrated herein, optionally present (e.g. where chemically possible) as an agrochemically acceptable salt thereof.
  • the compound of formula (I) is one of compounds A1 to A1 1 1 , as described and/or illustrated herein, optionally present (e.g. where chemically possible) as an agrochemically acceptable salt thereof.
  • the compound of formula (I) is one of compounds P1 to P12 (preferably one of compounds P1 to P5), or one of compounds A142 to A149, or compound A150 or A151 , as described and/or illustrated herein, optionally present (e.g. where chemically possible) as an agrochemically acceptable salt thereof.
  • the compound of formula (I) is one of compounds A1 to A12 (preferably compound A2, A6, A8 or A9, more preferably compound A2 or A8), as described and/or illustrated herein, optionally present (e.g. where chemically possible) as an agrochemically acceptable salt thereof.
  • the compound of formula (I) is compound A13, A14 or A15 (more preferably compound A14), as described and/or illustrated herein, optionally present (e.g. where chemically possible) as an agrochemically acceptable salt thereof.
  • the compound of formula (I) is compound A22, A23 or A24 (more preferably compound A23 or A24), as described and/or illustrated herein, optionally present (e.g. where chemically possible) as an agrochemically acceptable salt thereof.
  • the compound of formula (I) is one of compounds A25 to A39 (or more preferably one of compounds A25 to A36, or even more preferably compound A25, A26, A27, A28, A29, A29A, A30, A30A, A31 , A32, A32A, A33 or A33A, or yet more preferably compound A25, A26, A27, A28, A29, A29A, A30 or A30A, or further more preferably compound A26, A28, A29 or A29A, or particularly preferably compound A26 or A29, or most preferably compound A29), as described and/or illustrated herein, optionally present (e.g. where chemically possible) as an agrochemically acceptable salt thereof.
  • the compound of formula (I) is one of compounds A40 to A84, as described and/or illustrated herein, optionally present (e.g. where chemically possible) as an agrochemically acceptable salt thereof.
  • the compound of formula (I) is one of compounds A85 to A99, as described and/or illustrated herein, optionally present (e.g. where chemically possible) as an agrochemically acceptable salt thereof.
  • the compound of formula (I) is one of compounds P1 to P12 (or more preferably one of compounds P1 to P5, or most preferably compound P3 or P5), as described and/or illustrated herein, optionally present (e.g. where chemically possible) as an agrochemically acceptable salt thereof.
  • the compound of formula (I) is one of compounds A142 to A149 (or more preferably compound A142, A144, A146 or A148), or compound A150 or A151 , as described and/or illustrated herein, optionally present (e.g. where chemically possible) as an agrochemically acceptable salt thereof.
  • the compound of formula (I) is one of compounds A1 to A12 (e.g. A2, A6, A8 or A9),
  • A13, A14, A15, A22, A23 or A24 e.g. A14, A23 or A24
  • A25 to A36 e.g. A25, A26, A27, A28, A29, A29A, A30, A30A, A31 , A32, A32A, A33 or A33A, e.g. A26, A28, A29 or A29A
  • A25 to A36 e.g. A25, A26, A27, A28, A29, A29A, A30, A30A, A31 , A32, A32A, A33 or A33A, e.g. A26, A28, A29 or A29A
  • A142 to A149 e.g. A142, A144, A146 or A148
  • A150 or A151 e.g. A142, A144, A146 or A148
  • P1 to P12 e.g. P1 to P5
  • the compound of formula (I) is one of compounds A1 to A12 (e.g. A2, A6, A8 or A9), or A13, A14, A15, A22, A23 or A24 (e.g. A14, A23 or A24),
  • A25, A26, A27, A28, A29, A29A, A30, A30A, A31 , A32, A32A, A33 or A33A e.g. A26, A28, A29 or A29A
  • A142 to A149 e.g. A142, A144, A146 or A148
  • A150 or A151 e.g. A142, A144, A146 or A148
  • P1 to P12 e.g. P1 to P5
  • the compound of formula (I) is one of compounds A1 to A12 (e.g. A2, A6, A8 or A9),
  • A13, A14, A15, A22, A23 or A24 e.g. A14, A23 or A24
  • A25, A26, A27, A28, A29, A29A, A30, A30A, A31 , A32, A32A, A33 or A33A e.g. A26, A28, A29 or A29A
  • A142 to A149 e.g. A142, A144, A146 or A148
  • P1 to P12 e.g. P1 to P5
  • compounds of formula (I) may exist in different isomeric forms.
  • G is hydrogen
  • compounds of formula (I) may exist in different tautomeric forms (A), (AA), and/or (B):
  • the present invention covers a compound of formula (I) (which optionally agrochemically acceptable salt thereof :
  • CKE is a mixture of sub-formulae (A) and (B) e.g. in any molar ratio.
  • phenyl-CH 2 - or phenyl-CH(C 1 -C 2 alkyl)- in each of which the phenyl is optionally substituted by 1 , 2 or 3 of, independently, d-C 2 alkyl, dfluoroalkyl, CrC 2 alkoxy, Cifluoroalkoxy, fluorine, chlorine, bromine, cyano or nitro
  • heteroaryl-CH 2 - or heteroaryl-CH(C 1 -C 2 alkyl)- in each of which the heteroaryl is optionally substituted by 1 , 2 or 3 of, independently, C-
  • phenyl-C(0)-CH 2 - wherein the phenyl is optionally substituted by 1 , 2 or 3 of, independently, C-
  • C 2 -C 7 alken-1 -yl-CH(C C 2 alkyl)-, C 2 -C 4 fluoroalken-1 -yl-CH 2 -, C 2 -C 7 alkyn-1-yl-CH 2 -, or C 2 -C 7 alkyn-1 -yl-CH(C C 2 alkyl)-; may be prepared:
  • a suitable alkenyl or alkynyl halide e.g. chloride
  • a suitable alkenyl or alkynyl halide such as C 2 -C 7 alken-1 -yl-CH 2 -[halogen e.g. CI] or C 2 -C 7 alkyn-1 -yl-CH 2 -[halogen e.g. CI]
  • another organic halide suitable for preparing a (non-carbonyl, non-thiocarbonyl carbon)-linked G (or G1 ) group; or (b) [e.g.
  • a phosphorylating agent such as a phosphoryl chloride, CI-P(X e )(R )-R 9 ; or
  • O-acylation of cyclic 1 ,3-diones may be effected e.g. by procedures similar to those described, for example, by R. Haines, US4175135, and by T. Wheeler, US4422870,
  • diones of formula (A) may be treated with an acylating agent preferably in the presence of at least one equivalent of a suitable base, and optionally in the presence of a suitable solvent.
  • the base may be inorganic, such as an alkali metal carbonate or hydroxide, or a metal hydride, or an organic base such as a tertiary amine or metal alkoxide.
  • suitable inorganic bases include sodium carbonate, sodium or potassium hydroxide, sodium hydride
  • suitable organic bases include trialkylamines, such as trimethylamine and triethylamine, pyridines or other amine bases such as 1 ,4-diazobicyclo[2.2.2]-octane and 1 ,8-diazabicyclo[5.4.0]undec-7-ene.
  • Preferred bases include triethylamine and pyridine.
  • Suitable solvents for this reaction are selected to be compatible with the reagents and include ethers such as tetrahydrofuran and 1 ,2- dimethoxyethane and halogenated solvents such as dichloromethane and chloroform.
  • acylating agent is a carboxylic acid
  • acylation is preferably effected in the presence of a known coupling agent such as 2-chloro-1- methylpyridinium iodide, ⁇ /, ⁇ /'-dicyclohexylcarbodiimide, 1-(3-dimethylaminopropyl)-3- ethylcarbodiimide and ⁇ /, ⁇ /'-carbodiimidazole, and optionally in the presence of a base such as triethylamine or pyridine in a suitable solvent such as tetrahydrofuran, dichloromethane or acetonitrile.
  • a base such as triethylamine or pyridine in a suitable solvent such as tetrahydrofuran, dichloromethane or acetonitrile.
  • Phosphorylation of cyclic 1 ,3-diones may be effected e.g. using a phosphoryl halide or thiophosphoryl halide and a base e.g. by procedures analogous to those described by L. Hodakowski, US4409153.
  • Sulfonylation of a compound of formula (A) may be achieved e.g. using an alkyl or aryl sulfonyl halide, preferably in the presence of at least one equivalent of base, for example by the procedure of C. Kowalski and K. Fields, J. Org. Chem., (1981 ), 46, 197-201.
  • a compound of formula (C) can be prepared by reacting a compound of formula (D) with propyne, preferably in the presence of a suitable catalyst, optionally in the presence of a suitable additive, optionally in a suitable solvent e.g. at a suitable temperature.
  • suitable catalysts include transition metal salts or complexes of transition metal salts (for example palladium acetate, bis(triphenylphosphine) palladium(ll) dichloride,
  • Suitable additives include copper salts (for example copper(l) iodide in an amount typically 0.001 -50% with respect to a compound of formula (D)), and tetraalkyl ammonium salts.
  • Suitable bases include diethylamine, triethylamine, piperidine and pyrrolidine, and suitable solvents include 1 ,4-dioxane, ⁇ /,/V-dimethylacetamide or N,N- dimethylformamide.
  • the reaction is carried out using 0.05-10%
  • a compound of formula (C) may be prepared from a compound of formula (D) by reaction with a propynyl transfer reagent such as 1 - propynyllithium, 1 -propynylmagnesium bromide, 1 -propynylmagnesium chloride, 1- propynylmagnesium iodide, 1 -propynylzinc chloride, 1-propynylzinc bromide, 1-propynylzinc iodide, tributylpropynylstannane, 1 -propyne-1-boronic acid (or ester thereof), 2-butynoic acid or 1-(trimethylsilyl)propyne, with a transition metal catalyst system under suitable conditions (see for example P.
  • a propynyl transfer reagent such as 1 - propynyllithium, 1 -propynylmagnesium bromide, 1 -propynylmagnesium chloride,
  • a compound of formula (D) is reacted with 1-propynylmagnesium bromide in the presence of 0.05-10% bis(triphenylphosphine) palladium(ll) dichloride (with respect to a compound of formula (D)), in tetrahydrofuran at a temperature between 25°C and 100°C, as described by J. H. Chaplin, G. S. Gill, D. W. Grobelny, B. L. Flynn, G. Kremmidiotis, WO 07087684.
  • a compound of formula (D) can be prepared by reacting a compound of formula (E), wherein each R E is independently CrC 6 alkyl (preferably independently methyl or ethyl), and a hydrazine of formula (F), preferably by treatment in a suitable solvent, e.g. at a suitable temperature (including microwave heating), with or without the addition of a suitable base.
  • suitable solvents include alcohols, such as methanol or ethanol, tetrahydrofuran, or high boiling solvents such as toluene or xylene.
  • Suitable bases in greater than or sub- stoichiometric amounts, can be metal alkoxides, such as sodium methoxide, potassium methoxide, sodium ethoxide, potassium ethoxide, sodium tert-butoxide or potassium tert- butoxide, or organic amine bases such as 1 ,8-diazabicyclo[5.4.0]-undec-7-ene, triethylamine or diisopropylethylamine.
  • Suitable temperatures can be from cooled below 0°C up to the boiling point of the solvent used. Similar reactions are known in the literature (see for example M.
  • Hydrazines of formula (F) are known in the literature or can be prepared from known reagents using known methods.
  • a compound of formula (D) can alternatively be prepared by reacting a compound of formula (G) and a hydrazine of formula (F), preferably by treatment in a suitable solvent, e.g. at a suitable temperature (including microwave heating), preferably with a suitable base.
  • suitable solvents include high boiling solvents such as toluene or xylene.
  • Suitable bases in greater than or sub-stoichiometric amounts, can be organic amine bases such as 1 ,8- diazabicyclo[5.4.0]-undec-7-ene, triethylamine or diisopropylethylamine. Suitable
  • temperatures can be from cooled below 0°C up to the boiling point of the solvent used.
  • a compound of formula (E) can be prepared by reacting a compound of formula (H), wherein R E is CrC 6 alkyl (preferably methyl or ethyl), and a carboxylic acid or ester equivalent, preferably by treatment in a suitable solvent, e.g. at a suitable temperature, preferably with a suitable base.
  • Suitable solvents include, for example, 1 ,2-dimethoxyethane, tetrahydrofuran, 1 ,4-dioxane, diethyl ether, dibutyl ether, acetonitrile, dimethyl sulfoxide, N, N- dimethylformamide, benzene, toluene, methanol, ethanol, isopropanol or ie f-butanol, and is chosen to be compatible with the base under the reaction conditions.
  • Suitable bases include metal alkoxides, such as sodium methoxide, sodium ethoxide, potassium tert-butoxide or sodium ie f-butoxide, metal hydrides, such as sodium hydride or potassium hydride, alkyl metals, such as n-butyl lithium, or metal amides, such as lithium diisopropylamide, lithium diisopropylamide, lithium hexamethyldisilazide or lithium 2,2,6,6-tetramethylpiperidide.
  • metal alkoxides such as sodium methoxide, sodium ethoxide, potassium tert-butoxide or sodium ie f-butoxide
  • metal hydrides such as sodium hydride or potassium hydride
  • alkyl metals such as n-butyl lithium
  • metal amides such as lithium diisopropylamide, lithium diisopropylamide, lithium hexamethyldisilazide or lithium 2,2,6,6-te
  • Suitable temperatures can be in a temperature range of -100°C up to the boiling point of the solvent used.
  • Suitable carboxylic acid or ester equivalents are known or can be prepared from from known reagents using known methods (see for example Behera, Manoranjan et al, Tetrahedron Letters (2009) 53(9), 1060, Volonterio, Alessandro and Zanda, Matteo, Organic Letters (2007), 9(5) 841 , Levene, P.A. and Meyer, G.M., Organic Syntheses (1936) No.16, Shintani, Ryo et al, Organic Letters (2009) 1 1 (2), 457, Matulenko, Mark A. et al, Bioorganic and Medicinal Chemistry (2007), 15(4), 1586) and may include carbon dioxide,
  • chloroformates for example methyl chloroformate or ethyl chloroformate
  • cyanoformates such as methyl cyanoformate or ethyl cyanoformate
  • carbonates for example dimethyl carbonate or diethyl carbonate
  • oxalates such as diethyloxalate or dimethyloxalate
  • other equivalents include, for example, ethyl-1-imidazole carbamate.
  • Compounds of formula (H) are known in the literature or can be prepared from known reagents using known methods.
  • -C 6 alkyl (preferably independently methyl or ethyl), can alternatively be prepared by reacting a compound of formula (J) and a compound of formula (K), wherein each R E is independently C-
  • Suitable solvents include, for example, 1 ,2-dimethoxyethane, tetrahydrofuran, 1 ,4-dioxane, acetonitrile, dimethyl sulfoxide, N, /V-dimethylformamide, benzene, toluene, 1 -methyl-2-pyrrolidone or N, N- dimethylacetamide.
  • Suitable bases in greater than or sub-stoichiometric amounts, can be metal carbonates, such as potassium carbonate and cesium carbonate, metal hydroxides, such as barium hydroxide, metal hydrides, such as sodium hydride, or metal phosphates, such as tripotassium phosphate.
  • Suitable catalyst systems include using metal salts and complexes of metal salts, such as copper (I) iodide, ferric acetylacetonate, palladium acetate, palladium (II) chloride, bis(triphenylphosphine) palladium(ll) dichloride,
  • organo phosphines such as triphenyl phosphine or t-butylphosphine and salts thereof, copper (II) oxide or organic carboxylates, such as (S)-proline or 2-pyridine carboxylic acid.
  • a compound of formula (G) can be prepared by treatment of a compound of formula (L) with an acid (e.g a suitable acid), preferably in a suitable solvent, e.g. at a suitable temperature.
  • suitable solvents include water.
  • Suitable acids are mineral acids, for example concentrated sulfuric acid. Suitable temperatures can be from cooled below 0°C up to the boiling point of the solvent used. Similar reactions are known in the literature (see for example Maetzke, Thomas et al, WO00/078881 ).
  • a compound of formula (L) can be prepared by reacting a compound of formula (J) and malononitrile (CAS Reg. No. 109-77-3), for example using methods similar to those previously described. Similar reactions are known in the literature (see for example Zeller, Martin, WO2004/050607; Schnyder, Anita et al, Synlett (2006), 18, 3167; Gao, Chengwei et al, Synlett (2003) 1 1 , 1716; Makosza, Mieczyslaw and Chesnokov, Alexey, Tetrahedron (2008), 64(25), 5925).
  • Compounds of formula (C) can also be prepared by reacting compounds of formula (M), wherein each R E is independently C-
  • Compounds of formula (M) can be prepared from compounds of formula (E), e.g. under conditions as previously described e.g. in the preparation of a compound of formula (C) from a compound of formula (D).
  • Compounds of formula (N) can be prepared from compounds of formula (L), e.g. under conditions as previously described e.g. in the preparation of a compound of formula (C) from a compound of formula (D).
  • Compounds of formula (O) can be prepared from compounds of formula (G), e.g. under conditions as previously described e.g. in the preparation of a compound of formula (C) from a compound of formula (D).
  • a compound of formula (Q) can be prepared by treatment of a compound of formula (R), wherein R R is C-
  • the base may be inorganic such as an alkali metal carbonate or hydroxide or a metal hydride, or an organic base such as metal alkoxide.
  • Suitable solvents for this reaction are selected to be compatible with the reagents and include toluene, ethers, such as tetrahydrofuran and 1 ,2-dimethoxyethane and halogenated solvents, such as dichloromethane and chloroform. Similar reactions are known in the literature (see for example WO2009/049851 ).
  • a compound of formula (R) can be prepared by reacting a compound of formula (S), wherein R R is CrC 6 alkyl (preferably methyl or ethyl), and a compound of formula (T) in the presence of base (e.g. triethylamine), preferably in a suitable solvent.
  • Suitable solvents for this reaction are selected to be compatible with the reagents and include ethers, such as tetrahydrofuran and 1 ,2-dimethoxyethane, and halogenated solvents, such as dichloromethane and chloroform. Similar reactions are known in the literature (see for example WO2013/079672).
  • a compound of formula (P) can be prepared by reacting a compound of formula (U) with reagent R3-LG, where in LG represents a leaving group (e.g. halogen), in the presence of base in a suitable solvent.
  • the base may be inorganic, such as a metal hydride, or an organic base, such as metal alkoxide.
  • Suitable solvents for this reaction are selected to be compatible with the reagents and include toluene, ethers, such as tetrahydrofuran and 1 ,2- dimethoxyethane, and halogenated solvents, such as dichloromethane and chloroform.
  • a compound of formula (T) can be prepared by reacting a compound of formula (V) with a suitable halogenating reagent (preferably phosphorous oxychloride, thionyl chloride or oxalyl chloride), preferably in a suitable solvent (e.g. dichloromethane).
  • a suitable halogenating reagent preferably phosphorous oxychloride, thionyl chloride or oxalyl chloride
  • a suitable solvent e.g. dichloromethane
  • Compounds of formula (P) can be prepared from a compound of formula (W), wherein R R is CrC 6 alkyl (preferably methyl or ethyl), in particular under conditions as previously described.
  • Compounds of formula (W) can be prepared from a compound of formula (S) and a compound of formula (X), wherein Hal is a halogen (preferably chlorine), in particular under conditions as previously described.
  • Hal is a halogen (preferably chlorine), in particular under conditions as previously described.
  • Compounds of formula (Y) can be prepared: either (i) from a compound of formula (H) (by replacing the halogen group on the phenyl with a prop-1-ynyl group, in particular under conditions as previously described, and then hydrolysing the ester to the carboxylic acid e.g. under conventional ester hydrolysis conditions), or (ii) from a compound of formula (V), in particular under conditions as previously described.
  • a compound of formula (C) can be prepared by treatment of a compound of formula (Z), wherein R z is CrC 6 alkyl (preferably methyl or ethyl), with a base (e.g. a suitable base), preferably in a suitable solvent, e.g. at a suitable temperature and/or as described previously.
  • a base e.g. a suitable base
  • a compound of formula (Z) can be prepared by treatment of a compound of formula (AA), wherein R z is C-
  • Compounds of formula (AA) are known in the literature or can be prepared from known reagents using known methods.
  • a compound of formula (D) can be prepared by treatment of a compound of formula (AB), wherein R z is CrC 6 alkyl (preferably methyl or ethyl), with a base (e.g. a suitable base), preferably in a suitable solvent, e.g. at a suitable temperature and/or as described previously.
  • a base e.g. a suitable base
  • a compound of formula (AB) can be prepared by treatment of a compound of formula (AA), wherein R z is C-
  • Herbicidal compositions are described by treatment of a compound of formula (AA), wherein R z is C-
  • the present invention provides a herbicidal composition, e.g. for use in a method of controlling weeds (preferably monocotyledonous weeds such as more preferably grassy monocotyledonous weeds) in crops of useful plants, which composition comprises a compound of formula (I) as defined herein (e.g. a herbicidally effective amount thereof), and a substantially-inert agrochemically acceptable substance (e.g. an agrochemically acceptable carrier, diluent and/or solvent, an agrochemically acceptable adjuvant, an an agrochemically acceptable emulsifier / surfactant / surface-active substance, and/or another agrochemically acceptable additive).
  • a herbicidal composition e.g. for use in a method of controlling weeds (preferably monocotyledonous weeds such as more preferably grassy monocotyledonous weeds) in crops of useful plants, which composition comprises a compound of formula (I) as defined herein (e
  • the present invention provides a herbicidal composition, e.g. for use in a method of controlling weeds (preferably monocotyledonous such as more preferably grassy monocotyledonous weeds) in crops of useful plants, comprising a compound of formula (I) as defined herein (e.g. a herbicidally effective amount thereof), and an agrochemically acceptable carrier, diluent and/or solvent.
  • weeds preferably monocotyledonous such as more preferably grassy monocotyledonous weeds
  • the compound of the formula (I) is optionally present (e.g. where chemically possible) as an agrochemically acceptable salt thereof.
  • the compounds of formula (I) according to the invention can be used as crop protection agents in unmodified form, as obtained by synthesis, but, for use as herbicides, they are generally formulated into herbicidal compositions (formulations), e.g. in a variety of ways, containing one or more substantially-inert agrochemically acceptable substances (e.g. an agrochemically acceptable carrier, diluent and/or solvent, an agrochemically acceptable adjuvant, an an agrochemically acceptable emulsifier / surfactant / surface-active substance, and/or another agrochemically acceptable additive).
  • agrochemically acceptable substances e.g. an agrochemically acceptable carrier, diluent and/or solvent, an agrochemically acceptable adjuvant, an an agrochemically acceptable emulsifier / surfactant / surface-active substance, and/or another agrochemically acceptable additive.
  • the formulations can be in various physical forms, for example in the form of dusting powders, gels, wettable powders, coated or impregnated granules for manual or mechanical distribution on target sites, water-dispersible granules, water-soluble granules, emulsifiable granules, water-dispersible tablets, effervescent compressed tablets, water-soluble tapes, emulsifiable concentrates, microemulsifiable concentrates, oil-in-water (EW) or water-in-oil (WO) emulsions, other multiphase systems such as oil/water/oil and water/oil/water products, oil flowables, aqueous dispersions, oily dispersions, suspoemulsions, capsule suspensions, soluble liquids, water-soluble concentrates (with water or a water-miscible organic solvent as carrier), impregnated polymer films or in other forms known, for example, from the Manual
  • Such formulations can either be used directly or are diluted prior to use. They can then be applied through suitable ground or aerial application spray equipment or other ground application equipment such as central pivot irrigation systems or drip/trickle irrigation means. Diluted formulations can be prepared, for example, with water, liquid fertilisers, micronutrients, biological organisms, oil or solvents.
  • the formulations can be prepared, for example, by mixing the active ingredient with formulation adjuvants in order to obtain compositions in the form of finely divided solids, granules, solutions, dispersions or emulsions.
  • the active ingredients can also be contained in fine microcapsules consisting of a core and a polymeric shell. Microcapsules usually have a diameter of from 0.1 to 500 microns. They contain active ingredients in an amount of about from 25 to 95 % by weight of the capsule weight.
  • the active ingredients can be present in the form of liquid technical material, in the form of a suitable solution, in the form of fine particles in solid or liquid dispersion or as a monolithic solid.
  • the encapsulating membranes comprise, for example, natural and synthetic gums, cellulose, styrene-butadiene copolymers or other similar suitable membrane forming material, polyacrylonitrile, polyacrylate, polyester, polyamides, polyureas, polyurethane, aminoplast resins or chemically modified starch or other polymers that are known to the person skilled in the art in this connection.
  • microcapsules it is possible for fine so called “microcapsules” to be formed wherein the active ingredient is present in the form of finely divided particles in a solid matrix of a base substance, but in that case the microcapsule is not encapsulated with a diffusion limiting membrane as outlined in the preceding paragraph.
  • the active ingredients may be adsorbed on a porous carrier. This may enable the active ingredients to be released into their surroundings in controlled amounts (e.g. slow release).
  • Other forms of controlled release formulations are granules or powders in which the active ingredient is dispersed or dissolved in a solid matrix consisting of a polymer, a wax or a suitable solid substance of lower molecular weight.
  • Suitable polymers are polyvinyl acetates, polystyrenes, polyolefins, polyvinyl alcohols, polyvinyl pyrrolidones, alkylated polyvinyl pyrrolidones, copolymers of polyvinyl pyrrolidones and maleic anhydride and esters and half- esters thereof, chemically modified cellulose esters like carboxymethyl cellulose, methyl cellulose, hydroxyethyl cellulose, examples of suitable waxes are polyethylene wax, oxidized polyethylene wax, ester waxes like montan waxes, waxes of natural origin like carnauba wax, candelilla wax, bees wax etc. Other suitable matrix materials for slow release formulations are starch, stearin, or lignin.
  • formulation ingredients suitable for the preparation of the compositions according to the invention are generally known per se.
  • liquid carrier and/or solvent e.g. organic solvent
  • a liquid carrier and/or solvent e.g. organic solvent
  • an aromatic solvent such as toluene, m-xylene, o-xylene, p-xylene or a mixture thereof
  • cumene an aromatic hydrocarbon blend with a boiling range between 140 and 320 °C (e.g.
  • an alcoholic solvent or diluent such as methanol, ethanol, propanol, n- or iso- butanol, n- or iso- pentanol, 2-ethyl hexanol, n-octanol, tetrahydrofurfuryl alcohol, 2-methyl-2,4- pentanediol, 4-hydroxy-4-methyl-2-pentanone, cyclohexanol, benzyl alcohol, ethylene glycol, ethylene glycol butyl ether, ethylene glycol methyl ether, diethylene glycol, diethylene glycol butyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether, propylene glycol, dipropylene glycol, dipropylene glycol monomethyl ether, or another similar glycol monoether solvent based on a ethylene glycol, propylene glycol or butylene glycol feedstock, triethylene glycol, polyethylene glycol (e.g
  • rapeseed oil or soybean oil a fatty acid such as oleic acid, linoleic acid, or linolenic acid; or an ester of phosphoric or phosphonic acid such as triethyl phosphate, a C 3 -C 18 -tris-alkyl phosphate, an alkylaryl phosphate, or bis-octyl-octyl phosphonate.
  • a fatty acid such as oleic acid, linoleic acid, or linolenic acid
  • an ester of phosphoric or phosphonic acid such as triethyl phosphate, a C 3 -C 18 -tris-alkyl phosphate, an alkylaryl phosphate, or bis-octyl-octyl phosphonate.
  • Water is generally the liquid carrier of choice for the dilution of the concentrates.
  • Suitable solid carriers are, for example, talc, titanium dioxide, pyrophyllite clay, silica (fumed or precipated silica and optionally functionalised or treated, for instance silanised), attapulgite clay, kieselguhr, limestone, calcium carbonate, bentonite, calcium montomorillonite, cottonseed husks, wheatmeal, soybean flour, pumice, wood flour, ground walnut shells, lignin and similar materials, as described, for example, in the EPA CFR 180.1001 . (c) & (d). Powdered or granulated fertilisers can also be used as solid carriers.
  • a large number of surface-active substances can advantageously be used both in solid and in liquid formulations (herbicidal compositions), especially in those formulations (herbicidal compositions) which can be diluted with a carrier prior to use.
  • Surface-active substances may be anionic, cationic, amphoteric, non-ionic or polymeric and they may be used as emulsifiying, wetting, dispersing or suspending agents or for other purposes.
  • Typical surface- active substances include, for example, salts of alkyl sulfates, such as diethanolammonium lauryl sulfate or sodium lauryl sulfate; salts of alkylarylsulfonates, such as calcium or sodium dodecylbenzenesulfonate; alkylphenol-alkylene oxide addition products, such as nonylphenol ethoxylates; alcohol-alkylene oxide addition products, such as tridecyl alcohol ethoxylate; soaps, such as sodium stearate; salts of alkylnaphthalenesulfonat.es, such as sodium dibutylnaphthalenesulfonate; dialkyl esters of sulfosuccinate salts, such as sodium di(2- ethylhexyl)sulfosuccinate; sorbitol esters, such as sorbitol oleate; quaternary amines, such as lauryl trimethyl
  • compositions which can typically be used in formulations (herbicidal compositions) include crystallisation inhibitors, viscosity-modifying substances, suspending agents, dyes, anti-oxidants, foaming agents, light absorbers, mixing aids, anti-foams, complexing agents, neutralising or pH-modifying substances and/or buffers, corrosion-inhibitors, fragrances, wetting agents, absorption improvers, micronutrients, plasticisers, glidants, lubricants, dispersants, thickeners, anti-freezes, microbiocides, compatibility agents and. or solubilisers; and/or also liquid and/or solid fertilisers.
  • inert ingredients include crystallisation inhibitors, viscosity-modifying substances, suspending agents, dyes, anti-oxidants, foaming agents, light absorbers, mixing aids, anti-foams, complexing agents, neutralising or pH-modifying substances and/or buffers, corrosion-inhibitors, fragrances, wetting agents, absorption improvers, micronutri
  • compositions may also comprise additional active substances, for example further herbicides, herbicide safeners, plant growth regulators, fungicides or insecticides.
  • compositions according to the invention can additionally include an additive (commonly referred to as an adjuvant), comprising a mineral oil, an oil of vegetable or animal origin, alkyl (e.g. CrC 6 alkyl) esters of such oils or mixtures of such oils and oil derivatives / oil esters.
  • an additive commonly referred to as an adjuvant
  • the amount of oil additive (oil adjuvant) used in the composition according to the invention is generally from 0.01 to 10 %, based on the spray mixture.
  • the oil additive (oil adjuvant) can be added to the spray tank in the desired concentration after the spray mixture has been prepared.
  • oil additives comprise mineral oils or an oil of vegetable origin, for example rapeseed oil, olive oil or sunflower oil, emulsifiable vegetable oil, such as AMIGO® (Loveland Products Inc.), CrC 6 alkyl esters of oils of vegetable origin, for example the methyl esters, or an oil of animal origin, such as fish oil or beef tallow.
  • a preferred oil additive (oil adjuvant) contains methylated rapeseed oil
  • oil adjuvant contains, for example, as active components essentially 80 % by weight alkyl esters of fish oils and 15 % by weight methylated rapeseed oil (rapeseed oil methyl ester), and also 5 % by weight of customary emulsifiers and pH modifiers.
  • oil adjuvants comprise CrC 6 alkyl ester(s) of C 8 -C 2 2 fatty acid(s), especially the methyl ester(s) of C 8 -C 2 2 (especially Ci 2 -Ci 8 ) fatty acid(s); preferably the methyl ester of lauric acid, of palmitic acid, or of oleic acid.
  • esters are known as methyl laurate (CAS-1 1 1-82-0), methyl palmitate (CAS-1 12-39-0) and methyl oleate (CAS-1 12-62-9) respectively.
  • a preferred fatty acid methyl ester derivative is AGNIQUE ME 18 RD-F® (e.g. available from Cognis).
  • Those and other oil derivatives are also known from the Compendium of Herbicide Adjuvants, 5th Edition, Southern Illinois University, 2000.
  • oil adjuvants can be further improved by combining them with surface-active substances, such as non-ionic, anionic, cationic or amphoteric surfactants.
  • surface-active substances such as non-ionic, anionic, cationic or amphoteric surfactants.
  • suitable anionic, non-ionic, cationic or amphoteric surfactants are listed on pages 7 and 8 of W097/34485.
  • Preferred surface-active substances are anionic surfactants of the dodecylbenzylsulfonate type, especially the calcium salts thereof, and also non-ionic surfactants of the fatty alcohol ethoxylate type.
  • non-ionic sufactants special preference is given to ethoxylated C 12 -C 2 2 fatty alcohols preferably having a degree of ethoxylation of from 5 to 40.
  • surfactants are the GenapolTM types (Clariant).
  • silicone surfactants especially polyalkyl-oxide-modified heptamethyltrisiloxanes, which are commercially available e.g. as SILWET L-77®, and also perfluorinated surfactants.
  • concentration of surface-active substances in relation to the total oil additive (oil adjuvant) is generally from 1 to 50 % by weight of the oil additive (oil adjuvant).
  • oil additives that consist of mixtures of oils and/or mineral oils and/or derivatives thereof with surfactants
  • TURBOCHARGE® both (Syngenta Crop Protection AG), ACTIPRON® (BP Oil UK Limited), or AGRI-DEX® (Helena Chemical Company).
  • ADIGOR® both (Syngenta Crop Protection AG), ACTIPRON® (BP Oil UK Limited), or AGRI-DEX® (Helena Chemical Company).
  • the above-mentioned surface-active substances may also be used in the formulations alone, that is to say without oil additives (oil adjuvants).
  • oil additive oil adjuvant
  • surfactant mixture can contribute to a further enhancement of action.
  • Suitable solvents are, for example, heavy aromatic hydrocarbon solvents such as SOLVESSO® or AROMATIC® solvents (Exxon Corporation).
  • concentration of such solvents can typically be from 10 to 80 % by weight of the oil additive (oil adjuvant).
  • oil additives (oil adjuvants) which may be in admixture with solvents, are described, for example, in US 4 834 908.
  • a commercially available oil additive disclosed therein is known by the name MERGE® (BASF).
  • oil additives (oil adjuvants) that are preferred according to the invention are SCORE® or ADIGOR® (both Syngenta Crop Protection AG).
  • oil additives oil adjuvants listed above
  • oil adjuvants oil adjuvants
  • alkylpyrrolidones e.g. AGRIMAX® from ISP
  • alkylpyrrolidones e.g. AGRIMAX® from ISP
  • Formulations of synthetic latices such as, for example, polyacrylamide, polyvinyl compounds or poly-1 -p- menthene (e.g. BOND®, COURIER® or EMERALD®) can also be used.
  • a particularly preferred oil adjuvant (oil additive), e.g. for use in the herbicidal compositionas of the invention, is an emulsifiable concentrate which consists of:
  • ethoxylated alcohols which preferably includes ethoxylated C12-C22 fatty alcohols
  • a mixture of heavy aromatic hydrocarbons which preferably includes (or more preferably includes 50% or more by weight of the heavy aromatic hydrocarbons of) a mixture of naphthalenes each of which is substituted by one or more alkyls wherein the alkyl(s) in total have 1 -4 carbon atoms per naphthalene molecule (e.g. Solvesso 200 NDTM); and
  • methylated rapeseed oil rapeseed oil methyl ester
  • emulsifiable concentrate oil adjuvant
  • ADIGORTM emulsifiable concentrate oil adjuvant
  • the above emulsifiable concentrate oil adjuvant is used, it is preferably added to the herbicidal composition after dilution (e.g. with water and/or in a spray tank), typically before application to weeds and/or to crops of useful plants and/or to the locus thereof.
  • the herbicidal composition e.g. after dilution (e.g. with water and/or in a spray tank), contains the above emulsifiable concentrate oil adjuvant, and additionally ammonium sulphate and/or isopropyl alcohol.
  • Such adjuvant oils as described in the preceding paragraphs may be employed as the carrier liquid in which an active compound is dissolved, emulsified or dispersed as appropriate to the physical form of the active compound.
  • the herbicidal composition of the invention comprises an agrochemically acceptable adjuvant comprising 1 ,2-cyclohexane dicarboxylic acid di-isononyl ester (e.g. CAS Registry no. 166412-78-8), e.g. as available from BASF as HexamollTM DINCHTM.
  • "Isononyl” in this context is thought to mean one or more, preferably a mixture of two or more, branched isomers of C 9 H 19 .
  • the herbicidal composition e.g. after dilution (e.g. with water and/or in a spray tank), contains 1 ,2-cyclohexane dicarboxylic acid di-isononyl ester, and additionally ammonium sulphate and/or isopropyl alcohol.
  • the herbicidal composition of the invention comprises an agrochemically acceptable adjuvant comprising an organic phosphate and/or organic phosphonate adjuvant.
  • the phosphate adjuvant is a tris-[C 4 -C 12 alkyl or 2-(C 2 -C 6 alkoxy)ethyl-] ester of phosphoric acid, or more preferably is tris-(2-ethylhexyl) phosphate, tris-n-octyl phosphate and/or tris-[2-(n-butoxy)ethyl] phosphate, or most preferably is tris-(2-ethylhexyl) phosphate.
  • the phosphonate adjuvant is a bis- (C 3 -Ci 2 alkyl) ester of a C 3 -Ci 2 alkyl-phosphonic acid, or more preferably is bis-(2-ethylhexyl) (2-ethylhexyl)phosphonate, bis-(2-ethylhexyl) (n-octyl)phosphonate and/or di-n-butyl (n-butyl)phosphonate.
  • the formulations generally contain from 0.1 to 99 % by weight, especially from 0.1 to 95 % by weight, of a compound of formula I, and from 1 to 99.9 % by weight of a substantially-inert agrochemically acceptable substance, which preferably includes a formulation adjuvant and/or from 0 to 30 % or from 0 to 25 % (in particular from 0.5 to 30 % or from 0.5 to 25 %) by weight of a surface-active substance.
  • a substantially-inert agrochemically acceptable substance which preferably includes a formulation adjuvant and/or from 0 to 30 % or from 0 to 25 % (in particular from 0.5 to 30 % or from 0.5 to 25 %) by weight of a surface-active substance.
  • a formulation adjuvant and/or e.g. formulations (compositions) diluted with water, in particular when applying the herbicidal composition to weeds and/or to crops of useful plants and/or to the locus thereof.
  • the rate of application of the compounds of formula I may vary within wide limits and depends upon the nature of the soil, the method of application (pre- or post-emergence; seed dressing; application to the seed furrow; no tillage application etc.), the crop plant, the weed or grass to be controlled, the prevailing climatic conditions, and other factors governed by the method of application, the time of application and the target crop.
  • the compounds of formula I according to the invention are generally applied (preferably post-emergence) at a rate of from 1 to 2000 g/ha, preferably from 1 to 1000 g / ha and most preferably at from 1 to 500 g / ha or from 5 to 500 g/ha.
  • compositions have especially the following representative compositions:
  • Emulsifiable concentrates are:
  • active ingredient 0.3 to 95 %, preferably 0.5 to 60 % such as 1 to 40 % surface-active agents: 1 to 30 %, preferably 3 to 20% such as 5 to 15 % solvents as liquid carrier: 1 to 80 %, preferably 1 to 60% such as 1 to 40 %
  • active ingredient 0.1 to 10 %, preferably 0.1 to 5 %
  • solid carriers 99.9 to 90 %, preferably 99.9 to 99 %
  • active ingredient 1 to 75 %, preferably 3 to 50 % or 10 to 50 %
  • water 98 to 24 %, preferably 95 to 30 % or 88 to 30 %
  • surface-active agents 1 to 40 %, preferably 2 to 30 %
  • active ingredient 0.5 to 90 %, preferably 1 to 80 %
  • surface-active agents 0.5 to 20 %, preferably 1 to 15 %
  • solid carriers 5 to 95 %, preferably 15 to 90 %
  • active ingredient 0.1 to 30 %, preferably 0.1 to 15 %
  • Solid carriers 99.5 to 70 %, preferably 97 to 85 %
  • Waterdispersible granules 99.5 to 70 %, preferably 97 to 85 %
  • active ingredient 1 to 90 %, preferably 10 to 80 %
  • surface-active agents 0.5 to 80 %, preferably 5 to 30 %
  • solid carriers 90 to 10 %, preferably 70 to 30 %
  • Emulsifiable concentrates a) b) c) d)
  • NMP N-methyl-2-pyrrolidone
  • Emulsions of any desired concentration can be prepared from such concentrates by dilution with water.
  • NMP N-methyl-2-pyrrolidone
  • Wettable powders a) b) c) d) active ingredient 5 % 25 % 50 % 80 %
  • the active ingredient is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable mill, yielding wettable powders which can be diluted with water to give suspensions of any desired concentration.
  • the active ingredient is dissolved in methylene chloride, the solution is sprayed onto the carrier and the solvent is subsequently evaporated off in vacuo.
  • the active ingredient is mixed and ground with the adjuvants and the mixture is moistened with water.
  • the resulting mixture is extruded and then dried in a stream of air.
  • active ingredient 5% 10 % 40 % 90 %
  • the active ingredient is mixed and ground with the adjuvants and the mixture is moistened with water.
  • the resulting mixture is extruded and then dried in a stream of air.
  • Ready-to-use dusts are obtained by mixing the active ingredient with the carriers and grinding the mixture in a suitable mill.
  • heteropolysacharide 0.2 % 0.2 % 0.2 % 0.2 % 0.2 % 0.2 %
  • the finely ground active ingredient is intimately mixed with the adjuvants, yielding a suspension concentrate from which suspensions of any desired concentration can be prepared by dilution with water.
  • Herbicidal uses - crops of useful plants, weeds, application rates, et al.
  • the present invention provides a method of controlling weeds (preferably monocotyledonous such as more preferably grassy monocotyledonous weeds) in crops of useful plants, which comprises applying a compound of the formula (I), or a herbicidal composition comprising such a compound, to the weeds and/or to the plants and/or to the locus thereof.
  • weeds preferably monocotyledonous such as more preferably grassy monocotyledonous weeds
  • the herbicidal composition can be as described hereinabove or hereinbelow, e.g. as described in the "Herbicidal compositions", “Herbicidal uses", “Combinations and mixtures" and/or Claims sections hereinabove or hereinbelow.
  • the present invention provides a herbicidal composition, in particular for use in a method of controlling weeds (preferably monocotyledonous weeds such as more preferably grassy monocotyledonous weeds) in crops of useful plants, comprising a compound of formula (I) as defined herein (e.g. a herbicidally effective amount thereof), and an agrochemically acceptable carrier, diluent and/or solvent.
  • weeds preferably monocotyledonous weeds such as more preferably grassy monocotyledonous weeds
  • the compound of the formula (I) is optionally present (e.g. where chemically possible) as an agrochemically acceptable salt thereof (e.g. agrochemically acceptable metal, sulfonium or ammonium salt).
  • an agrochemically acceptable salt thereof e.g. agrochemically acceptable metal, sulfonium or ammonium salt.
  • the herbicidal composition also comprises one or more further herbicides, e.g. as mixture partner(s) for the compound of formula (I), and/or a safener. See the combinations and mixtures section herein for more details of examples of these.
  • crops of useful plants comprise (e.g. are), in particular: cereals (e.g. non-oat cereals, in particular non-oat non-sorghum non-millet cereals, more particularly wheat, barley, rye and/or triticale), rice, corn (maize), sugarcane, leguminous crops [preferably soybean, peanut, and/or pulse crops; more preferably soybean; wherein typically the pulse crops comprise dry beans (e.g.
  • blackeye bean i.e. black-eyed pea, Vigna unguiculata
  • lentil dry broad
  • the crops of useful plants comprise (e.g. are): cereals (in particular non-oat cereals, more particularly non-oat non- sorghum non-millet cereals, even more particularly wheat, barley, rye and/or triticale), rice, sugarcane, leguminous crops [preferably soybean, peanut, and/or pulse crops (more preferably soybean)], cotton, rape (in particular oilseed rape or canola), sunflower, linseed, sugarbeet, fodder beet, potato, and/or vegetables (preferably dicotyledonous vegetables).
  • cereals in particular non-oat cereals, more particularly non-oat non- sorghum non-millet cereals, even more particularly wheat, barley, rye and/or triticale
  • rice sugarcane
  • leguminous crops preferably soybean, peanut, and/or pulse crops (more preferably soybean)]
  • cotton, rape in particular oilseed rape or canola
  • sunflower linseed
  • the crops of useful plants comprise (e.g. are): wheat (e.g. winter wheat, spring wheat, or durum wheat), barley (e.g. winter or spring barley), rye, triticale, rice, sugarcane, leguminous crops [preferably soybean, peanut, and/or pulse crops (more preferably soybean)], cotton, rape (in particular oilseed rape or canola), sunflower, linseed, sugarbeet, fodder beet, potato, and/or vegetables (preferably dicotyledonous vegetables).
  • wheat e.g. winter wheat, spring wheat, or durum wheat
  • barley e.g. winter or spring barley
  • rye triticale
  • rice e.g. winter wheat, spring wheat, or durum wheat
  • sugarcane e.g. winter or spring barley
  • leguminous crops preferably soybean, peanut, and/or pulse crops (more preferably soybean)]
  • cotton, rape in particular oilseed rape or canola
  • sunflower
  • the crops of useful plants comprise (e.g. are): leguminous crops [preferably soybean, peanut, and/or pulse crops; more preferably soybean; wherein typically the pulse crops comprise dry beans (e.g. kidney or haricot or pinto bean which is Phaseolus vulgaris, or mung bean which is Vigna radiata), chickpea, blackeye bean (i.e.
  • black-eyed pea Vigna unguiculata
  • lentil dry broad beans
  • dry peas such as garden peas
  • cotton rape (in particular oilseed rape or canola), sunflower, sugarbeet, fodder beet, potato, and/or vegetables (preferably
  • crops is to be understood as also including crops that have been rendered tolerant to herbicides or classes of herbicides (for example ALS, GS, EPSPS, PPO and HPPD inhibitors, and/or 2,4-D or dicamba) as a result of conventional methods of breeding or genetic engineering.
  • herbicides or classes of herbicides for example ALS, GS, EPSPS, PPO and HPPD inhibitors, and/or 2,4-D or dicamba
  • crops that have been rendered tolerant e.g. to imid- azolinones (which are ALS inhibitors), such as imazamox
  • crops that have been rendered tolerant e.g. to imid- azolinones (which are ALS inhibitors), such as imazamox
  • crops that have been rendered tolerant e.g. to imid- azolinones (which are ALS inhibitors), such as imazamox
  • canola Clearfield® summer rape
  • Clearfield® wheat for example ALS
  • Clearfield® rice (all from BASF).
  • crops that have been rendered tolerant to herbicides by genetic engineering methods include e.g. glyphosate-resistant (glyphosate- tolerant) or glufosinate-resistant (glufosinate-tolerant) maize or soybean varieties, in particular those commercially available under the trade name RoundupReady® or
  • RoundupReady® 2 (both from Monsanto, both glyphosate-resistant) or LibertyLink® (from Bayer, glufosinate-resistant).
  • Glufosinate-resistant (glufosinate-tolerant) rice (LibertyLink®) also has been published.
  • 2,4-D-tolerant soybean e.g. soybean genetically- modified to be tolerant to the herbicide 2,4-D
  • dicamba-tolerant soybean e.g. soybean genetically-modified to be tolerant to the herbicide dicamba.
  • Such 2,4-D-tolerant or dicamba- tolerant soybean crops can also, in particular, be tolerant to glyphosate or glufosinate.
  • crops of useful plants include soybeans containing a dicamba-tolerance trait combined (stacked) with a glyphosate-tolerance trait, such that these soybeans have tolerance to the herbicides glyphosate and dicamba (for example Genuity® Roundup Ready® 2 Xtend soybeans, currently under development by Monsanto).
  • Crops are also to be understood as being those which have been rendered resistant to harmful insects by genetic engineering methods, for example Bt maize (resistant to
  • Bt maize are the Bt-176 maize hybrids of NK® (Syngenta Seeds).
  • the Bt toxin is a protein that is formed naturally by Bacillus thunngiensis soil bacteria. Examples of toxins and transgenic plants able to synthesise such toxins are described in EP-A-451 878, EP-A-374 753, WO 93/07278, WO 95/34656, WO 03/052073 and EP-A-427 529.
  • transgenic plants that contain one or more genes which code for an insecticidal resistance and express one or more toxins are KnockOut® (maize), Yield Gard® (maize), NuCOTIN33B® (cotton), Bollgard® (cotton), NewLeaf® (potatoes), NatureGard® and Protexcta®.
  • Plant crops and their seed material can be resistant to herbicides and at the same time also to insect feeding ("stacked" transgenic events). Seed can, for example, have the ability to express an insecticidally active Cry3 protein and at the same time be glyphosate-tolerant.
  • the term "crops" is to be understood as also including crops obtained as a result of conventional methods of breeding or genetic engineering which contain so-called output traits (e.g. improved flavour, storage stability, nutritional content).
  • the weeds may be either monocotyledonous (e.g. grassy) and/or dicotyledonous weeds.
  • the weeds e.g. to be controlled and/or growth-inhibited, comprise or are monocotyledonous weeds, more preferably grassy monocotyledonous weeds.
  • the monocotyledonous (preferably grassy) weeds comprise (e.g. are) weeds from the genus Agrostis, Alopecurus, Apera, Avena, Brachiaria, Bromus, Cenchrus, Cyperus (a genus of sedges), Digitaria, Echinochloa, Eleusine, Eriochloa, Fimbristylis (a genus of sedges), Juncus (a genus of rushes), Leptochloa, Lolium, Monochoria, Ottochloa, Panicum,
  • the monocotyledonous weeds are grassy monocotyledonous weeds; in which case they typically comprise (e.g. are) weeds from the genus Agrostis, Alopecurus, Apera, Avena, Brachiaria, Bromus, Cenchrus, Digitaria, Echinochloa, Eleusine, Eriochloa,
  • Leptochloa Lolium, Ottochloa, Panicum, Pennisetum, Phalaris, Poa, Rottboellia, Setaria and/or Sorghum; in particular: weeds from the genus Agrostis, Alopecurus, Apera, Avena, Brachiaria, Bromus, Digitaria, Echinochloa, Eriochloa, Leptochloa, Lolium, Panicum, Phalaris, Poa, Rottboellia, Setaria and/or Sorghum.
  • the monocotyledonous (preferably grassy monocotyledonous) weeds e.g. to be controlled and/or growth-inhibited, comprise volunteer corn (volunteer maize) weeds.
  • the grassy monocotyledonous weeds e.g. to be controlled and/or growth-inhibited, are "warm-season" (warm climate) grassy weeds; in which case they preferably comprise (e.g.
  • the grassy monocotyledonous weeds comprise volunteer corn (volunteer maize) weeds.
  • the grassy monocotyledonous weeds are "warm-season" (warm climate) grassy weeds comprising (e.g. being) weeds from the genus Brachiaria, Cenchrus, Digitaria, Echinochloa, Eleusine, Eriochloa, Panicum, Setaria and/or Sorghum; and/or the grassy monocotyledonous weeds, e.g. to be controlled and/or growth-inhibited, comprise volunteer corn (volunteer maize) weeds.
  • monocotyledonous weeds e.g. to be controlled and/or growth-inhibited
  • ln non-oat cereal crops such as wheat and/or barley
  • control and/or growth inhibition of weeds from the genus Alopecurus, Apera, Avena, especially Avena fatua, Bromus, Lolium, Phalaris, and/or Setaria is preferred; in particular Alopecurus, Avena (especially Avena fatua), Lolium and/or Setaria (especially Setaria viridis, Setaria lutescens, Setaria faberi and/or Setaria glauca).
  • the weeds e.g. to be controlled and/or growth-inhibited e.g. by applying a compound of formula (I)
  • ACCase acetyl- coenzyme A carboxylase
  • ACCase acetyl- coenzyme A carboxylase
  • ALS acetolactate synthase
  • sulfonyl urea herbicides e.g. iodosulfuron-methyl, mesosulfuron-methyl, tribenuron-methyl, triasulfuron, prosulfuron, sulfosulfuron,
  • pyrazosulfuron-ethyl bensulfuron-methyl, nicosulfuron, flazasulfuron, iofensulfuron, metsulfuron-methyl, or any other sulfonyl urea herbicide disclosed in The Pesticide Manual, 15th edition (2009) or 16th Edition (2012), ed. C.D.S. Tomlin, British Crop Protection Council) and/or one or more triazolopyrimidine herbicides (e.g. florasulam, pyroxsulam or
  • penoxsulam and/or one or more pyrimidinyl-(thio or oxy)-benzoate herbicides (e.g.
  • bispyribac-sodium or pyriftalid bispyribac-sodium or pyriftalid
  • one or more sulfonylamino-carbonyl-triazolinone herbicides e.g. thiencarbazone-methyl, propoxycarbazone-sodium or flucarbazone-sodium
  • one or more imidazolinone herbicides e.g. imazamox
  • Such resistant grassy weeds can more particularly comprise Alopecurus myosuroides, Apera spica-venti, Avena fatua, Avena sterilis, Brachiaria decumbens, Brachiaria
  • the compound of formula (I) can be applied to grassy monocotyledonous weeds (e.g. selected from one of the above-mentioned list(s) of grassy weeds):
  • ACCase inhibitor herbicides e.g. selected from the above-mentioned list of ACCase inhibitor herbicides
  • mutation e.g. substitution
  • amino acids on the ACCase target site in the weed
  • S.B. Powles and Qin Yu "Evolution in Action: Plants Resistant to Herbicides", Annu. Rev. Plant Biol. , 2010, 61 , pp. 317-347, e.g. see pages 325-327 therein in particular Table 3, incorporated herein by reference, for examples of such resistant weeds and/or amino acid substitutions
  • amino acid substitutions e.g. see S.B. Powles and Qin Yu, "Evolution in Action: Plants Resistant to Herbicides", Annu. Rev. Plant Biol. , 2010, 61 , pp. 317-347, e.g. see pages 325-327 therein in particular Table 3, incorporated herein by reference, for examples of such resistant weeds and/or amino
  • ALS inhibitor herbicides e.g. selected from the above-mentioned list of ALS inhibitor herbicides
  • mutation e.g. substitution
  • amino acids amino acids on the ALS target site in the weed
  • dicotyledonous weeds e.g. to be controlled, comprise (e.g. are)
  • Nasturtium Nasturtium, Polygonum, Sida, Sinapsis, Solanum, Stellaria, Viola, Veronica and/or Xanthium.
  • Areas under cultivation, and/or the locus are to be understood as including land where the crop plants are already growing as well as land intended for the cultivation of those crop plants.
  • the rate of application (typically to the weeds and/or to the crops of useful plants and/or to the locus thereof) of the compound of formula (I) is generally from 1 to 2000 g of the compound of formula (I) per hectare (ha) (measured as the salt-free compound, i.e.
  • the above rates of application are for post-emergence application of the compound of formula (I) (which optionally may be an agrochemically acceptable salt thereof).
  • the compound of formula (I) can be applied (typically to the weeds and/or to the crops of useful plants and/or to the locus thereof) pre- and/or post- emergence, but preferably is applied post-emergence.
  • the main use and purpose of the compounds of formula (I) according to the invention is their herbicidal use.
  • at least some of the compounds of formula (I) may have activity against one or more types of pest (in particular pests associated with agriculture and/or food storage).
  • at least some of the compounds of formula (I) may have at least some insecticidal, acaricidal, molluscicidal and/or nematicidal activity.
  • At least some of the compounds of formula (I) may have activity against (and/or may help to control and/or combat) insect pests, such as one or more of: Coleoptera, Dictyoptera, Diptera, Hemiptera (including Homoptera), Hymenoptera, Isoptera, Lepidoptera, Orthoptera, Siphonaptera and/or Thysanoptera.
  • insect pests such as one or more of: Coleoptera, Dictyoptera, Diptera, Hemiptera (including Homoptera), Hymenoptera, Isoptera, Lepidoptera, Orthoptera, Siphonaptera and/or Thysanoptera.
  • At least some of the compounds of formula (I) may have activity against (and/or may help to control and/or combat) acarine pests and/or pests from the order Acarina, such as one or more of: Acalitus spp, Aculus spp, Acaricalus spp, Aceria spp, Acarus siro, Amblyomma spp., Argas spp., Boophilus spp., Brevipalpus spp., Bryobia spp, Calipitrimerus spp., Chorioptes spp., Dermanyssus gallinae, Dermatophagoides spp, Eotetranychus spp, Eriophyes spp., Hemitarsonemus spp, Hyalomma spp., Ixodes spp., Olygonychus spp, Ornithodoros spp., Polyphagotarsone latus, Pan
  • Rhizoglyphus spp. Sarcoptes spp., Steneotarsonemus spp, Tarsonemus spp. and/or Tetranychus spp.
  • At least some of the compounds of formula (I) may have activity against (and/or may help to control and/or combat) other (i.e. non-insect, non-acarine) invertebrate pests, for example, nematode and/or mollusc pests.
  • other invertebrate pests for example, nematode and/or mollusc pests.
  • pests Insects, acarines, nematodes and/or molluscs are hereinafter collectively referred to as pests.
  • Examples of pest species, on and/or to which the compounds of formula (I) can be tried and/or applied, include one or more of: Myzus spp. such as Myzus persicae (aphid), Aphis spp. such as Aphis gossypii (aphid) or Aphis fabae (aphid), Lygus spp. (capsids), Dysdercus spp. (capsids), Nilaparvata lugens (planthopper), Nephotettixc incticeps (leafhopper), Nezara spp. (stinkbugs), Euschistus spp. (stinkbugs), Leptocorisa spp.
  • Myzus spp. such as Myzus persicae (aphid)
  • Aphis spp. such as Aphis gossypii (aphid) or Aphis fabae (aphid)
  • Anopheles spp. (mosquitoes), Culex spp. (mosquitoes), Lucillia spp. (blowflies), Blattella germanica (cockroach), Periplaneta americana (cockroach), Blatta orientalis (cockroach), termites of the Mastotermitidae (for example Mastotermes spp.), of the Kalotermitidae (for example Neotermes spp.), of the Rhinotermitidae (for example Coptotermes formosanus, Reticulitermes flavipes, R. speratu, R. virgin icus, R. hesperus, or R. santonensis) or of the Termitidae (for example Globitermes sulphureus), Solenopsis geminata (fire ant),
  • Monomorium pharaonis pharaoh's ant
  • Damalinia spp. or Linognathus spp. biting lice or sucking lice
  • Meloidogyne spp. root knot nematodes
  • Globodera spp. Heterodera spp.
  • Pratylenchus spp. lesion nematodes
  • Rhodopholus spp. banana burrowing nematodes
  • the present invention provides a herbicidal composition, e.g. for use in a method of controlling weeds (preferably monocotyledonous weeds such as more preferably grassy monocotyledonous weeds) in crops of useful plants, comprising a compound of formula (I) as defined herein (e.g. a herbicidally effective amount thereof), and an
  • agrochemically acceptable carrier diluent and/or solvent, and also comprising one or more further herbicides, and/or a safener.
  • the compound of the formula (I) is optionally present (e.g. where chemically possible) as an agrochemically acceptable salt thereof.
  • the compounds of formula (I) according to the invention can be used in combination with one or more further herbicides, e.g. as mixture partner(s) for the compound of formula (I).
  • the compound of the formula (I) is one of the exemplified compounds (in particular one of compounds A1 to A151 or P1 to P12, more particularly one of compounds A1 to A1 1 1 , or A142 to A149, or A150 or A151 , or P1 to P12) disclosed herein e.g. hereinbelow, optionally present (e.g. where chemically possible) as an agrochemically acceptable salt thereof.
  • the following mixtures of the compound of formula (I) with one or more further herbicides are particularly disclosed: compound of formula I + acetochlor, compound of formula I + acifluorfen, compound of formula I + acifluorfen-sodium, compound of formula I + aclonifen, compound of formula I + acrolein, compound of formula I + alachlor, compound of formula I + alloxydim, compound of formula I + allyl alcohol, compound of formula I + ametryn, compound of formula I + amicarbazone, compound of formula I + amidosulfuron, compound of formula I +
  • compound of formula (I) + one of the specific herbicidal compounds disclosed in WO 2010/059680 (Dow, e.g. as defined in one of the examples therein and/or e.g. can be plus cloquintocet-mexyl or another safener) these parts of which are incorporated herein by reference
  • compound of formula (I) + one of the specific herbicidal compounds disclosed in WO 2010/059671 (Dow, e.g. as defined in one of the examples therein and/or e.g.
  • compound of formula I + halauxifen which is 4-amino-3-chloro-6-(4-chloro-2-fluoro-3- methoxyphenyl)pyridine-2-carboxylic acid, CAS Reg. No. 943832-60-8
  • compound of formula I + halauxifen-methyl which is methyl 4-amino-3-chloro-6-(4-chloro-2-fluoro-3- methoxyphenyl)pyridine-2-carboxylate, CAS Reg. No.
  • compound of formula I + aminocyclopyrachlor which is 6-amino-5-chloro-2-cyclopropylpyrimidine-4-carboxylic acid, CAS Reg. No. 858956-08-8
  • compound of formula I + aminocyclopyrachlor-methyl which is methyl 6-amino-5-chloro-2-cyclopropylpyrimidine-4-carboxylate, CAS Reg. No. 858954-83- 3
  • compound of formula I + aminocyclopyrachlor-potassium which is potassium 6-amino-5- chloro-2-cyclopropylpyrimidine-4-carboxylate, CAS Reg. No.
  • compound of formula I + cyclopyrimorate which is 6-chloro-3-(2-cyclopropyl-6-methylphenoxy)pyridazin-4-yl morpholine-4-carboxylate, CAS Reg. No. 499231 -24-2
  • compound of formula I + triafamone which is /V-[2-[(4,6-dimethoxy-1 ,3,5-triazin-2-yl)carbonyl]-6-fluorophenyl]-/V- methyl-1 ,1 -difluoromethanesulfonamide, CAS Reg. No. 874195-61 -6).
  • the mixture partners for the compound of formula (I) are optionally in the form of an ester (in particular an agrochemically acceptable ester) or a salt (in particular an agrochemically acceptable salt) thereof (e.g. where chemically possible).
  • the above-mentioned mixture partners for the compound of formula (I) are generally mentioned e.g. in The Pesticide Manual, 15th Edition (2009) or 16th Edition (2012), ed. C.D.S. Tomlin, British Crop
  • compound of formula I + aclonifen compound of formula I + amidosulfuron, compound of formula I + aminopyralid, compound of formula I + beflubutamid, compound of formula I + benfluralin, compound of formula I + bifenox, compound of formula I + bromoxynil, compound of formula I + bromoxynil heptanoate, compound of formula I + bromoxynil octanoate, compound of formula I + bromoxynil heptanoate + bromoxynil octanoate, compound of formula I + butafenacil, compound of formula I + carbetamide, compound of formula I + carfentrazone, compound of formula I + carfentrazone-ethyl, compound of formula I + chlorotoluron, compound of formula I + chlorpropham, compound of formula I + chlorsulfuron, compound of formula I + cinidon- ethyl, compound of formula I
  • mixture partners for the compound of formula (I) may optionally be in the form of an ester (in particular an agrochemically acceptable ester) or a salt (in particular an agrochemically acceptable salt) thereof (e.g. where chemically possible).
  • a mixture comprising: a compound of formula (I) + amidosulfuron, compound of formula (I) + aminopyralid, compound of formula (I) + beflubutamid, compound of formula (I) + bromoxynil, compound of formula (I) + bromoxynil heptanoate, compound of formula (I) + bromoxynil octanoate, compound of formula (I) + bromoxynil heptanoate + bromoxynil octanoate, compound of formula (I) + carfentrazone, compound of formula (I) + carfentrazone-ethyl, compound of formula (I) + chlorotoluron, compound of formula (I) + chlorsulfuron, compound of formula (I) + clodinafop, compound of formula (I) + clodinafop-propargyl, compound of formula (I) + clopyralid, compound of formula (I) + 2,4-
  • compound of formula (I) + one of the specific herbicidal compounds disclosed in WO 2010/059676 (Dow, e.g. as defined in one of the examples therein and/or e.g. can be plus cloquintocet-mexyl as safener) these parts of which are incorporated herein by reference
  • compound of formula (I) + one of the specific herbicidal compounds disclosed in WO 2010/059680 (Dow, e.g. as defined in one of the examples therein and/or e.g.
  • compound of formula I + halauxifen which is 4-amino- 3-chloro-6-(4-chloro-2-fluoro-3-methoxyphenyl)pyridine-2-carboxylic acid, CAS Reg. No. 943832-60-8
  • compound of formula I + halauxifen-methyl which is methyl 4-amino-3-chloro- 6-(4-chloro-2-fluoro-3-methoxyphenyl)pyridine-2-carboxylate, CAS Reg. No.
  • mixture partners for the compound of formula (I) may optionally be in the form of an ester (in particular an agrochemically acceptable ester) or a salt (in particular an agrochemically acceptable salt) thereof (e.g. where chemically possible).
  • mixture partners for the compound of formula (I) may optionally be in the form of an ester (in particular an agrochemically acceptable ester) or a salt (in particular an agrochemically acceptable salt) thereof (e.g. where chemically possible).
  • a mixture comprising: a compound of formula (I) + azimsulfuron, compound of formula (I) + bensulfuron, compound of formula (I) + bensulfuron- methyl, compound of formula (I) + benzobicyclon, compound of formula (I) + benzofenap, compound of formula (I) + bispyribac, compound of formula (I) + bispyribac-sodium, compound of formula (I) + clomazone, compound of formula (I) + clomeprop, compound of formula (I) + cyhalofop, compound of formula (I) + cyhalofop-butyl, compound of formula (I) + 2,4-D, compound of formula (I) + 2,4-D-dimethylammonium, compound of formula (I) + 2,4-D-2-ethylhexyl, compound of formula (I) + a choline salt of 2,4-D (see e.g.
  • pretilachlor compound of formula I + propyrisulfuron (TH-547, CAS Reg. No. 570415-88-2), compound of formula (I) + pyrazolynate, compound of formula (I) + pyrazosulfuron, compound of formula (I) + pyrazosulfuron-ethyl, compound of formula (I) + pyrazoxyfen, compound of formula (I) + pyribenzoxim, compound of formula (I) + pyriftalid, compound of formula (I) + pyriminobac, compound of formula (I) + pyriminobac-methyl, compound of formula (I) + pyrimisulfan, compound of formula (I) + quinclorac, compound of formula (I) + tefuryltrione, compound of formula (I) + triasulfuron and compound of formula (I) + trinexapac-ethyl, compound of formula (I) + 4-(4'-chloro-4-cyclopropyl-2'-
  • compound of formula I + halauxifen which is 4-amino-3-chloro-6-(4-chloro-2-fluoro-3- methoxyphenyl)pyridine-2-carboxylic acid, CAS Reg. No. 943832-60-8
  • compound of formula I + halauxifen-methyl which is methyl 4-amino-3-chloro-6-(4-chloro-2-fluoro-3- methoxyphenyl)pyridine-2-carboxylate, CAS Reg. No.
  • mixture partners for the compound of formula (I) may optionally be in the form of an ester (in particular an agrochemically acceptable ester) or a salt (in particular an agrochemically acceptable salt) thereof (e.g. where chemically possible).
  • compound of formula (I) + acifluorfen compound of formula (I) + acifluorfen-sodium, compound of formula (I) + ametryn, compound of formula (I) + atrazine, compound of formula (I) + bentazone, compound of formula (I) + bicyclopyrone, compound of formula (I) + bromoxynil, compound of formula (I) + bromoxynil heptanoate, compound of formula (I) + bromoxynil octanoate, compound of formula (I) + bromoxynil heptanoate + bromoxynil octanoate, compound of formula (I) + carfentrazone, compound of formula (I) +
  • compound of formula (I) + 2,4-D + glyphosate especially for applications to 2,4-D-tolerant and/or glyphosate-tolerant soybean, e.g. genetically-modified
  • compound of formula (I) + 2,4-D-dimethylammonium + glyphosate especially for applications to 2,4-D-tolerant and/or glyphosate-tolerant soybean, e.g. genetically-modified
  • compound of formula (I) + 2,4-D-2-ethylhexyl + glyphosate especially for applications to 2,4-D-tolerant and/or glyphosate-tolerant soybean, e.g.
  • compound of formula I + a choline salt of 2,4-D + glyphosate see e.g. Examples 2 and 3 of WO2010/123871 A1 ) (especially for applications to dicamba-tolerant and/or glyphosate-tolerant soybean, e.g. genetically-modified), compound of formula (I) + dicamba (especially for applications to dicamba-tolerant soybean, e.g. genetically-modified), compound of formula (I) + dicamba-dimethylammonium (especially for applications to dicamba-tolerant soybean, e.g. genetically-modified), compound of formula (I) + dicamba- potassium (especially for applications to dicamba-tolerant soybean, e.g.
  • compound of formula (I) + dicamba + glyphosate especially for applications to dicamba-tolerant and/or glyphosate-tolerant soybean, e.g. genetically- modified
  • compound of formula (I) + dicamba-dimethylammonium + glyphosate especially for applications to dicamba-tolerant and/or glyphosate-tolerant soybean, e.g. genetically- modified
  • compound of formula (I) + dicamba-potassium + glyphosate especially for applications to dicamba-tolerant and/or glyphosate-tolerant soybean, e.g.
  • compound of formula (I) + dicamba-sodium + glyphosate especially for applications to dicamba-tolerant and/or glyphosate-tolerant soybean, e.g. genetically- modified
  • compound of formula (I) + dicamba-diglycolamine + glyphosate especially for applications to dicamba-tolerant and/or glyphosate-tolerant soybean, e.g. genetically- modified
  • compound of formula (I) + a /V,/V-bis-[aminopropyl]methylamine salt of dicamba + glyphosate especially for applications to dicamba-tolerant and/or glyphosate-tolerant soybean, e.g.
  • mixture partners for the compound of formula (I) may optionally be in the form of an ester (in particular an agrochemically acceptable ester) or a salt (in particular an agrochemically acceptable salt) thereof (e.g. where chemically possible).
  • compositions or mixtures comprising a compound of formula (I) (in particular one of the specific compounds disclosed herein, in particular one of compounds A1 to A151 or P1 to P12 disclosed herein, more particularly one of compounds A1 to A1 1 1 , or A142 to A149, or A150 or A151 , or P1 to P12 disclosed herein, present either as a free compound and/or as an agrochemically acceptable salt thereof) and one or more further herbicides
  • the weight ratio of the compound of formula (I) to each further herbicide can vary over a large range and is, typically, from 300:1 to 1 :500, especially from 150:1 to 1 :200, more especially from 100:1 to 1 :100, even more especially from 30:1 to 1 :30.
  • these weight ratios are measured as the free compound(s), i.e. excluding the weight of any associated salt counterion(s).
  • the compounds of formula I according to the invention can also be used in combination with a safener.
  • the compound of the formula I is one of the exemplified compounds (in particular one of compounds A1 to A151 or P1 to P12, more particularly one of compounds A1 to A1 1 1 , or A142 to A149, or A150 or A151 , or P1 to P12) disclosed herein e.g. hereinbelow, present either as a free compound and/or as an agrochemically acceptable salt thereof.
  • a composition or mixture comprising a compound of formula (I) (in particular one of the specific compounds disclosed herein, in particular one of compounds A1 to A151 or P1 to P12 disclosed herein, or more particularly one of compounds A1 to A1 1 1 , or A142 to A149, or A150 or A151 , or P1 to P12 disclosed herein, present either as a free compound and/or as an agrochemically acceptable salt thereof) and a safener
  • the safener comprises (e.g.
  • the safener comprises (e.g.
  • Cloquintocet-mexyl is) cloquintocet-mexyl, cloquintocet acid or an agrochemically acceptable salt thereof, mefenpyr-diethyl and/or isoxadifen-ethyl; in particular for use on non-oat cereals such as wheat, barley, rye and/or triticale.
  • Cloquintocet-mexyl is particularly valuable and is the most preferred safener, especially for use on non-oat cereals such as wheat, barley, rye and/or triticale.
  • compositions or mixtures comprising a compound of formula (I) (in particular, one of the specific compounds disclosed herein, in particular one of compounds A1 to A151 or P1 to P12 disclosed herein, or more particularly one of compounds A1 to A1 1 1 , or A142 to A149, or A150 or A151 , or P1 to P12 disclosed herein, present either as a free compound and/or as an agrochemically acceptable salt thereof) with a safener
  • the weight ratio of the compound of formula (I) to the safener can vary over a large range and is, typically, from 200:1 to 1 :200, especially from 50:1 to 1 :50 such as from 50:1 to 1 :20, more especially from 20:1 to 1 :20, even more especially from 20:1 to 1 :10.
  • the safener comprises (e.g. is) benoxacor, cloquintocet-mexyl, cloquintocet acid or an agrochemically acceptable salt thereof, cyprosulfamide, mefenpyr-diethyl, isoxadifen-ethyl and/or ⁇ /-(2- methoxybenzoyl)-4-[(methylaminocarbonyl)amino]-benzenesulfonamide, and the weight ratio of the compound of formula (I) to the safener is from 50:1 to 1 :20 or from 20:1 to 1 :10, more preferably from 15:1 to 1 :2.
  • these weight ratios are measured as the free compound(s), i.e. excluding the weight of any associated salt counterion(s).
  • Application rates of herbicide (e.g. compound of formula (I)) and/or safener The rate of application of safener relative to the compound of formula (I) is largely dependent upon the mode of application. In the case of field and/or soil and/or plant treatment (e.g.
  • the compounds and/or herbicidal compositions according to the invention are suitable for all methods of application customary in agriculture, such as, for example, pre-emergence application, post-emergence application and seed dressing. Post-emergence application is preferred.
  • the safeners can be used for pretreating the seed material of the crop plant (dressing the seed or seedlings) or introduced into the soil before or after sowing, followed by the application of the (unsafened) compound of the formula (I), optionally in combination with a co-herbicide. It can, however, also be applied alone or together with the herbicide before or after emergence of the plants. The treatment of the plants or the seed material with the safener can therefore take place in principle independently of the time of application of the herbicide.
  • the treatment of the plant by simultaneous application of herbicide and safener is generally preferred.
  • the rate of application of safener relative to herbicide is largely dependent upon the mode of application.
  • In the case of field and/or soil and/or plant treatment e.g. in a field or glasshouse, generally from 0.001 to 5.0 kg of safener/ha, preferably from 0.001 to 0.5 kg of safener/ha, are applied.
  • seed dressing generally from 0.001 to 10 g of safener/kg of seed, preferably from 0.05 to 2 g of safener/kg of seed, are applied.
  • safener solutions which contain the active ingredient in a concentration of from 1 to 10 000 ppm, preferably from 100 to 1000 ppm.
  • a safener in the case of field and/or soil and/or plant treatment (e.g. post-emergence application), generally from 1 to 2000 g of herbicide (in particular compound of formula (I)) / ha, but preferably from 5 to 1000 g of herbicide (in particular compound of formula (I)) / ha, more preferably from 10 to 400 g of herbicide (in particular compound of formula (I)) / ha, is applied.
  • a safener in the case of field and/or soil and/or plant treatment (e.g. post- emergence application), generally from 0.5 to 1000 g of safener/ha, preferably from 2 to 500 g of safener/ha, more preferably from 5 to 200 g of safener/ha, is applied.
  • composition or mixture comprising the compound of formula (I) and one or more further herbicides (e.g. as mentioned hereinabove) can be applied together with one of the safeners mentioned herein, e.g. hereinabove.
  • the present invention provides a herbicidal composition, e.g. for use in a method of controlling weeds (in particular monocotyledonous such as grassy
  • a compound of formula (I) as defined herein in particular, one of the specific compounds disclosed herein, in particular one of compounds A1 to A151 or P1 to P12 disclosed herein, or more particularly one of compounds A1 to A1 1 1 , or A142 to A149, or A150 or A151 , or P1 to P12 disclosed herein, present either as a free compound and/or as an agrochemically acceptable salt thereof) (e.g. a herbicidally effective amount thereof), and an agrochemically acceptable carrier, diluent and/or solvent, and also comprising a plant growth regulator, and optionally one or more further herbicides (e.g. as described herein, e.g. glyphosate and/or dicamba and/or 2,4-D) and optionally a safener (e.g. as described herein).
  • a plant growth regulator e.g. as described herein, e.g. glyphosate and/or dicamba and/or 2,4-D
  • the plant growth regulator is: abscisic acid, acibenzolar-S-methyl, a
  • brassinosteroid plant growth regulator 24-epi brassinolide, 28-homobrassinolide, chlormequat, a cytokinin plant growth regulator, ethephon, ethylene, flurprimidol, gibberellic acid, a gibberellin plant growth regulator (in particular gibberellin A3, gibberellin A4, or gibberellin A7, or gibberellin A4 and gibberellin A7), GR24, indole-3-acetic acid (IAA), indole- 3-butyric acid (IBA), jasmonic acid, methyl jasmonate, a karrikin plant growth regulator, maleic hydrazide, mefluidide, mepiquat, methylcyclopropene such as 1 -methylcyclopropene, 1 -naphthaleneacetic acid (NAA), paclobutrazol, prohexadione, prohexadione-calcium, salicylic acid, a strigolac
  • the plant growth regulator is: gibberellic acid, or a gibberellin plant growth regulator (in particular gibberellin A3, gibberellin A4, or gibberellin A7, or gibberellin A4 and gibberellin A7), or an
  • the plant growth regulator is gibberellic acid or an agrochemically acceptable salt e.g. metal or ammonium salt e.g. alkali metal salt thereof.
  • Gibberellic acid is preferred because WO 2014/071 1 10 A1 (Valent USA Corp.) discloses that gibberelic acid, when mixed with clethodim, increased clethodim's control and/or speed of control of
  • Johnsongrass Sorghum halepense
  • volunteer corn increased the control of glyphosate-tolerant (Roundup-ReadyTM) volunteer corn at 21 days after the application of a mixture of clethodim + dicamba-glycolamine + glyphosate + gibberellic acid (compared to clethodim + dicamba-glycolamine + glyphosate + ammonium sulfate).
  • compositions comprising a compound of formula (I), an agrochemically acceptable carrier, diluent and/or solvent, and a plant growth regulator (e.g. gibberellic acid or a salt thereof), and optionally one or more further herbicides and optionally a safener, the weight ratio of the compound of formula (I) to the plant growth regulator (e.g. gibberellic acid or an agrochemically acceptable salt e.g. metal salt e.g.
  • a plant growth regulator e.g. gibberellic acid or an agrochemically acceptable salt e.g. metal salt
  • alkali metal salt thereof can vary over a large range and is, typically, from 500:1 to 1 :500, especially from 200:1 to 1 :200, more especially from 100:1 to 1 :100, even more especially from 30:1 to 1 :30.
  • these weight ratios are measured as the free compound(s), i.e. excluding the weight of any associated salt counterion(s).
  • room (ambient) temperature is typically about 15-30 °C (e.g. 15-25 °C).
  • reaction mixture was partitioned between ethyl acetate and saturated aqueous ammonium chloride solution.
  • the phases were separated and the aqueous phase extracted with further ethyl acetate (x2).
  • the combined organic phases were washed with water (x2), brine, dried over magnesium sulfate and concentrated and purified by chromatography on silica eluting with ethyl acetate in iso-hexane to give dimethyl 2-(4-bromo-2-chloro-6- methoxy-phenyl)propanedioate (2.0334 g) as a colourless oil.
  • reaction mixture was cooled, concentrated and purified by chromatography on silica eluting with ethyl acetate in iso-hexane to give dimethyl 2-(2-chloro-6-methoxy-4-prop-1-ynyl- phenyl)propanedioate (1.347 g) as an orange gum.
  • Step 4 Preparation of 8-(2-chloro-6-methoxy-4-prop-1-ynyl-phenyl)-1 ,2,4,5- tetrahydropyrazolo[1 ,2-d][1 ,4,5]oxadiazepine-7,9-dione (compound A29)
  • the reaction mixture was poured into water (40 ml) and made alkaline by the addition of 2 M aqueous sodium hydroxide (10 ml).
  • the aqueous layer was extracted twice with ethyl acetate.
  • the combined organic layers were extracted twice with further 2 M aqueous sodium hydroxide.
  • the combined aqueous alkaline phases were acidified to pH 2-3 by addition of 2 M hydrochloric acid and extracted with dichloromethane (x2).
  • Step 1 Preparation of 5-bromo-1 -fluoro-2-iodo-3-methoxy-benzene
  • reaction solution was allowed to cool and concentrated to afford a white solid. This was partitioned between dichloromethane and water. The aqueous phase was extracted with further dichloromethane (x2) and the combined organic phases were washed with brine, dried over magnesium sulfate, concentrated and purified by chromatography on silica eluting with ethyl acetate in iso-hexane to give 5-bromo-1 -fluoro-2-iodo-3-methoxy-benzene (1 .5926 g) as a white solid.
  • reaction mixture was partitioned between ethyl acetate and saturated aqueous ammonium chloride solution. The phases were separated and the aqueous phase was extracted with further ethyl acetate (x2). The combined organic phases were washed with water (x2), brine, dried over magnesium sulfate, concentrated and purified by
  • reaction mixture was cooled, concentrated and purified by chromatography on silica eluting with ethyl acetate in iso-hexane to give dimethyl 2-(2-fluoro-6-methoxy-4-prop-1-ynyl- phenyl)propanedioate (1.47 g) as a yellow gum that solidified on standing.
  • Step 4 Preparation of methyl 2-(2-fluoro-6-methoxy-4-prop-1-ynyl-phenyl)acetate
  • Step 6 Preparation of ethyl 1 ,4,5-oxadiazepane-4-carboxylate
  • Oxalyl dichloride (0.43 mL) was added drop wise to a stirred suspension of 2-(2-fluoro-6- methoxy-4-prop-1-ynyl-phenyl)acetic acid (1.0 g) and one drop of /V,/V-dimethylformamide in dichloromethane (90 mL). The mixture was stirred at room temperature until gas evolution had ceased (about 2 hours). A further portion of oxalyl dichloride (0.43 mL) was added and the reaction stirred at room temperature for a further 2 hours. The reaction was concentrated to give 2-(2-fluoro-6-methoxy-4-prop-1-ynyl-phenyl)acetyl chloride as an off-white solid, which was used crude in the next step.
  • Step 8 Preparation of 8-(2-fluoro-6-methoxy-4-prop-1 -ynyl-phenyl)-1 ,2,4,5- tetrahydropyrazolo[1 ,2-d][1 ,4,5]oxadiazepine-7,9-dione
  • reaction mixture was partitioned between water and dichloromethane.
  • the aqueous layer was extracted twice more with dichloromethane.
  • the combined organic extracts were washed with 2 M hydrochloric acid, dried over magnesium sulfate, concentrated and purified by chromatography on silica eluting with ethyl acetate in iso-hexane to give 8-(2-fluoro-6- methoxy-4-prop-1-ynyl-phenyl)-1 ,2,4,5-tetrahydropyrazolo[1 ,2-d][1 ,4,5]oxadiazepine-7,9- dione (245 mg) as a yellow gum.
  • Step 9 Preparation of 8-(2-fluoro-6-methoxy-4-prop-1 -ynyl-phenyl)-1 ,2,4,5- tetrahydropyrazolo[1 ,2-d][1 ,4,5]oxadiazepine-7,9-dione (compound A30)
  • Step 1 Preparation of methyl 2-(4-bromo-2-fluoro-6-methoxy-phenyl)acetate
  • Oxalyl dichloride (0.49 ml.) was added dropwise to a stirred suspension of 2-(4-bromo-2- fluoro-6-methoxy-phenyl)acetic acid (1 .35 g) and one drop of ⁇ /,/V-dimethylformamide in dichloromethane (103 ml_). The mixture was stirred at room temperature until gas evolution had ceased (about 3 hours). The reaction was concentrated to give 2-(2-fluoro-6-methoxy-4- prop-1-ynyl-phenyl)acetyl chloride as an off-white solid, which was used crude in the next step.
  • Step 4 Preparation of ethyl 2-[2-(4-bromo-2-fluoro-6-methoxy- phenyl)acetyl]hexahydropyridazine-1 -carboxylate
  • reaction mixture was partitioned between water and dichloromethane.
  • the aqueous layer was extracted twice more with dichloromethane.
  • the combined organic extracts were washed with 2 M hydrochloric acid, dried over magnesium sulfate, concentrated and purified by chromatography on silica eluting with ethyl acetate in iso-hexane to give ethyl 2-[2-(4- bromo-2-fluoro-6-methoxy-phenyl)acetyl]hexahydropyridazine-1-carboxylate (960 mg) as a yellow gum.
  • Step 5 Preparation of 2-(4-bromo-2-fluoro-6-methoxy-phenyl)-5, 6,7,8- tetrahydropyrazolo[1 ,2-a]pyridazine-1 ,3-dione
  • Step 6 Preparation of 2-(2-fluoro-6-methoxy-4-prop-1 -ynyl-phenyl)-5,6,7,8- tetrahydropyrazolo[1 ,2-a]pyridazine-1 ,3-dione (compound A24)
  • the reaction was cooled to room temperature and partitioned between 2 M aqueous hydrochloric acid (20 ml) and ethyl acetate.
  • the aqueous phase was extracted with further ethyl acetate (x2).
  • the combined organic phases were washed with brine, dried over magnesium sulfate, concentrated and purified by chromatography on silica eluting with ethyl acetate in iso-hexane to give impure desired compound.
  • This mixture was dissolved in ethyl acetate and extracted with 2 M aqueous sodium hydroxide.
  • the aqueous phase was acidified with 2 M aqueous hydrochloric acid and extracted with ethyl acetate (x2) and dichloromethane (x2).
  • the combined organic extracts were dried over magnesium sulfate, and concentrated to give 2-(2-fluoro-6-methoxy-4-prop-1 -ynyl-phenyl)-5, 6,7,8- tetrahydropyrazolo[1 ,2-a]pyridazine-1 ,3-dione (1 1 mg) as a yellow solid.
  • Pivaloyl chloride (0.021 mL) was added to a mixture of 8-(2-chloro-6-methoxy-4-prop-1-ynyl- phenyl)-1 ,2,4,5-tetrahydropyrazolo[1 ,2-d][1 ,4,5]oxadiazepine-7,9-dione (0.050 g) and pyridine (0.014 mL) in dichloromethane (4.3 mL) and the reaction mixture was stirred at room temperature for 2 hours.
  • reaction mixture was quenched with water and extracted with dichloromethane.
  • organic extract was dried over magnesium sulfate, concentrated and purified by
  • Test 1 Glasshouse assay for herbicidal activity
  • Seeds of a variety of test species are sown in standard soil ** in pots. After cultivation for one day (pre-emergence) or after 8 days cultivation (post-emergence) under controlled conditions in a glasshouse (at 24/16°C, day/night; 14 hours light; 65 % humidity), the plants were sprayed with an aqueous spray solution derived from the formulation of the technical active ingredient (the test herbicide) in acetone / water (50:50) solution containing 0.5% Tween 20 TM (polyoxyethylene sorbitan monolaurate, CAS Reg. No. 9005-64-5).
  • Test plants / weeds in the table below are:
  • Alopecurus myosuroides (ALOMY), Setaria faberi (SETFA), Echinochloa crus-galli (ECHCG), Zea mays (ZEAMX, corn, maize, e.g. volunteer corn), Lolium perenne (LOLPE), Amaranthus retroflexus (AMARE), and Abutilon theophasti Medik. (ABUTH, common English name "velvetleaf”).
  • Alopecurus myosuroides (ALOMY), Setaria faberi (SETFA)
  • Echinochloa crus-galli EHCG
  • Zea mays ZEAMX, corn, maize, e.g. volunteer corn
  • LELPE Lolium perenne
  • Test plants / weeds in the table below are:
  • Alopecurus myosuroides (ALOMY), Setaria faberi (SETFA), Echinochloa crus-galli (ECHCG), Zea mays (ZEAMX, corn, maize, e.g. volunteer corn), Lolium perenne (LOLPE), Amaranthus retroflexus (AMARE), and Abutilon theophasti Medik. (ABUTH, common English name "velvetleaf”).
  • Alopecurus myosuroides (ALOMY), Setaria faberi (SETFA)
  • Echinochloa crus-galli EHCG
  • Zea mays ZEAMX, corn, maize, e.g. volunteer corn
  • LELPE Lolium perenne
  • Test plants / weeds in the table below are:
  • Lolium perenne LPE
  • Alopecurus myosuroides ALOMY
  • Echinochloa crus-galli Echinochloa crus-galli
  • AVEFA Avena fatua
  • Herbicide Application Post-emergence foliar spray application, 200 L/ha, usually one or two replicates for the weeds (depending on application rate), and two replicates for soybean.
  • climate Standard warm conditions (tropical), in glasshouse. Specifically, the glasshouse bay conditions are 24 °C / 18 °C day/night; 16/8 hours light/dark; 65% humidity.
  • Plants The herbicidal application takes place at the following growth stages for plants which include inter alia one or more (usually all seven) of the following plants:
  • Brachiaria decumbens (BRADC) - growth stage 12 or 13 - or, if BRADC is not used, then usually Brachiaria platyphylla (BRAPP) - growth stage 12 or 13
  • Digitaria sanguinalis DIGSA- growth stage 12 or 13
  • Setaria faberi (SETFA) - growth stage 12 or 13
  • Zea mays (ZEAMX, maize/corn, e.g. can occur as volunteer corn) cultivar "Garland" - growth stage 12 or 13
  • Glycine max (GLXMA, soybean) cultivar "Nikko" - growth stage: 1 st trifoliate
  • Glycine max (GLXMA, soybean) cultivar "TMG133" - which is Roundup ReadyTM
  • glyphosate-tolerant soybean cultivar TMG133 typically available from Monsanto in Brazil
  • - growth stage 1 st trifoliate.
  • test Compound is applied with the following adjuvant system (all percentages are final concentrations in the aqueous spray mixture):
  • Adjuvant system 1 0.5% v/v AdigorTM * , 1 .0% v/v AMS (ammonium sulphate) and 12.5% v/v I PA (isopropyl alcohol).
  • AdigorTM (currently available in many countries from Syngenta) is an emulsifiable concentrate which consists of:
  • ethoxylated alcohols which typically includes ethoxylated higher alkanols
  • a mixture of heavy aromatic hydrocarbons which typically includes (e.g. includes 50% or more by weight of) a mixture of naphthalenes each of which is substituted by one or more alkyls wherein the alkyl(s) in total have 1-4 carbon atoms per naphthalene molecule (e.g. Solvesso 200 NDTM); and
  • methylated rapeseed oil rapeseed oil methyl ester
  • e.g. Agnique ME 18 RD-FTM methylated rapeseed oil
  • Seeds of the weed (including volunteer) plants are sown in seed trays (troughs) containing clay loam soil (pH 7.0, 2.2% organic matter, "Trough Mix A”); and soybean seed is sown in pots containing the same soil with 3 soybean seedlings per pot. The plants are sprayed with the test herbicide when they reach the growth stages mentioned above.
  • test herbicidal solutions are prepared by mixing the appropriate aliquots of the test substance(s) and the adjuvant system indicated above *** in deionised water to give the desired treatment concentration.
  • the herbicidal application is made as a foliar spray, using a tracksprayer. Following the herbicidal application, the plants are watered twice per day for the duration of the test.
  • Adjuvant system AdigorTM at 0.5% v/v, and 12.5% v/v I PA (isopropyl alcohol), and 1 .0% v/v AMS (ammonium sulphate); all percentages are final concentrations in the aqueous spray mixture.
  • BRADC Brachiaria decumbens
  • BRAPP Brachiaria platyphylla
  • Compound A2 showed percentage control of (a percentage phytotoxicity on) or Brachiaria platyphylla (BRAPP) of 98%, when applied post-emergence at an application rate of 8g/ha.
  • Compound A14 showed percentage control of (a percentage phytotoxicity on) Brachiaria decumbens (BRADC) of 90%, when applied post-emergence at an application rate of 8g/ha.
  • BRADC Brachiaria decumbens
  • Compound A26 showed percentage control of (a percentage phytotoxicity on) Brachiaria decumbens (BRADC) of 80%, when applied post-emergence at an application rate of 8g/ha.
  • BRADC Brachiaria decumbens
  • Compound A29 showed percentage control of (a percentage phytotoxicity on) Brachiaria decumbens (BRADC) of 98%, when applied post-emergence at an application rate of 8g/ha.
  • DIGSA Digitaria sanguinalis
  • DIGSA Digitaria sanguinalis
  • DIGSA Digitaria sanguinalis
  • Eleusine indica a warm-climate (warm-season) grassy weed
  • certain test compounds namely, Compound A2, A14 or A29
  • Compound A26 showed a percentage control of (a percentage phytotoxicity on) Eleusine indica (ELEIN) of 80%, when applied post-emergence at an application rate of 8g/ha.
  • Compound A2 showed a percentage control of (a percentage phytotoxicity on) Setaria faberi (SETFA) of 90%, when applied post-emergence at an application rate of 8g/ha.
  • SETFA Setaria faberi
  • ZEAMX Zea mays
  • corn a warm-climate (warm-season) grassy plant
  • Zea mays (ZEAMX, maize/corn) is often present as a "volunteer” weed ("volunteer” corn), in fields where it was planted as a crop in preceding growing season(s) and where the present field crop is not corn.
  • Compound A2 showed a percentage control of (a percentage phytotoxicity on) Zea mays (ZEAMX, corn) of 95%, when applied post-emergence at an application rate of 8g/ha.
  • test compounds namely, Compound A14 or A26
  • ZEAMX Zea mays
  • Compound A29 showed a percentage control of (a percentage phytotoxicity on) Zea mays (ZEAMX, corn) of 100%, when applied post-emergence at an application rate of 8g/ha.
  • Compound A2 showed a percentage phytotoxicity on Glycine max (GLXMA, soybean) cultivar "Nikko" of 80%, when applied post-emergence at an application rate of 120g/ha.
  • test compounds namely, Compound A14 or A26
  • Glycine max GLXMA, soybean
  • Nikko 85%
  • Compound A29 showed a percentage phytotoxicity on Glycine max (GLXMA, soybean) cultivar "Nikko" of 90%, when applied post-emergence at an application rate of 120g/ha.
  • Glycine max (GLXMA, soybean) cultivar "TMG133” is Roundup ReadyTM glyphosate-tolerant soybean cultivar TMG133, and is typically available from Monsanto in Brazil.
  • Compound A2 showed a percentage phytotoxicity on Glycine max (GLXMA, soybean) cultivar "TMG133" of 85%, when applied post-emergence at an application rate of 120g/ha.
  • Compound A14 showed percentage phytotoxicities on Glycine max (GLXMA, soybean) cultivar "TMG133" in the range of from 70% to 80%, when applied post-emergence at an application rate of 120g/ha.
  • Compound A26 showed percentage phytotoxicities on Glycine max (GLXMA, soybean) cultivar "TMG133" in the range of from 80% to 85%, when applied post-emergence at an application rate of 120g/ha.
  • Test 3 Glasshouse assay for herbicidal activity
  • An “instant formulation”, known as the "IF50”, containing 50 g/litre (i.e. 5% w/v) of the “technical” (i.e. unformulated) active ingredient is prepared by dissolving the active ingredient in a mixture of organic solvents and emulsifier, details of which are provided in the Table below.
  • This IF50 is then mixed with a small, variable amount of acetone to aid dissolution, before addition of a 0.2% v/v aqueous solution of the adjuvant X-77 (which is a mixture of alkyl aryl polyoxyethylene glycols and free fatty acids in isopropanol, CAS Registry number 1 1097-66-8), as the aqueous diluent, to form an aqueous spray solution which contains a predetermined concentration of the active ingredient (which varies depending on the application rate of the active ingredient to the plants) and 0.2% v/v of the adjuvant X-77.
  • Table Composition of the mixture of organic solvents and emulsifier to be used as a base for the instant formulation (IF50).
  • Cool climate crop plants Triticum aestivum (TRZAW, winter wheat), Hordeum vulgare (HORVW, barley), Brassica napus (BRSNN, rape, also called oilseed rape or rapeseed), Beta vulgaris (BEAVA, sugar beet).
  • TRZAW Triticum aestivum
  • HORVW Hordeum vulgare
  • BRSNN Brassica napus
  • rape also called oilseed rape or rapeseed
  • Beta vulgaris BEAVA, sugar beet.
  • Warm climate crop plants Glycine max (GLXMA, soybean), Oryza sativa (ORYSA, rice).
  • Cool climate (“cool season") grassy monocotyledonous weeds Alopecurus myosuroides (ALOMY), Lolium perenne (LOLPE), and Poa annua (POAAN).
  • compounds A2, A26, A29, P2 and P5 exhibited 20%, 40%, 40%, 10% and 20% phytotoxicity on Oryza sativa (ORYSA, rice), respectively, when applied at 8 g/ha post- emergence, in Biological Example 3.
  • compounds A2, A26, A29, P2 and P5 exhibited 60%, 10%, 40%, 10% and 60% phytotoxicity on Hordeum vulgare (HORVW, barley), respectively, when applied at 30 g/ha post-emergence, in Biological Example 3.
  • compounds A2, A26, A29, P2 and P5 exhibited 0%, 0%, 0%, 10% and 0% phytotoxicity on Hordeum vulgare (HORVW, barley), respectively, when applied at 8 g/ha post- emergence, in Biological Example 3.
  • HORVW Hordeum vulgare

Abstract

Herbicidally active pyrazolidine-dione or pyrrolidine-dione compounds or derivatives thereof The present invention relates to a compoundof formula (I): wherein CKE is of sub-formula (A) and/or (B): wherein: R1 is fluorine or chlorine; R 2 is hydrogen, methyl, ethyl, n-propyl, cyclopropyl, ethynyl, cyano, fluorine, chlorine, bromine, C 1-C 3 alkoxy, C1 -C 2 fluoroalkoxy, C1 -C 2 alkoxy-C1 -C 3 alkoxy-, or C1 fluoroalkoxy-C1 -C 3 alkoxy-; and X is NR 4 or CR5 R 6; wherein R 3, R 4, R5 and R 6 are as defined herein; wherein the compound of formula (I) is optionally present as an agrochemically acceptable salt thereof. These compounds are suitable for use as herbicides. The invention therefore also relates to a method of controlling weeds, especially grassy monocotyledonous weeds, in crops of useful plants, comprising applying a compound of formula (I), or a herbicidal composition comprising such a compound, to the plants or to the locus thereof.

Description

HERBICIDALLY ACTIVE 2-HALOGEN-4-ALKYNYL- PHENYL-PYRAZOLIDINE-DIONE
OR PYRROLIDINE-DIONE DERIVATIVES
The present invention relates to herbicidally active heterocyclic diones, in particular herbicidally active pyrazolidine-dione (more particularly pyrazolidine-3,5-dione) compounds or herbicidally active pyrrolidine-dione (more particularly pyrrolidine-2,4-dione) compounds, or derivatives thereof (e.g. enol ketone tautomer derivatives thereof), to processes for 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.
EP 0 456 063 A2 (Bayer AG) discloses 3-(substituted-phenyl)-pyrrolidine-2,4-dione derivatives, and their use as insecticides, acaricides and herbicides. EP 0 355 599 A1 (Bayer AG) diascloses fused 3-(substituted-phenyl)-pyrrolidin-2,4-dione derivatives, and their use as herbicides, fungicides, antimycotics, insecticides and acaricides.
WO 98/05638 A2 (Bayer AG) discloses phenyl-substituted heterocyclic keto-enols or derivatives thereof, for example 3-(2- or 2,5- substituted-phenyl)-pyrrolidin-2,4-dione derivatives, and their use as pesticides. Bayer's commercial insecticide spirotetramat (
Figure imgf000003_0001
), which works by inhibiting lipid biosynthesis via inhibition of
ACCase, is covered by WO 98/05638 A2. Spirotetramat is disclosed in non-stereospecific form as compound 1-1-0-4 on page 95 of WO 98/05638 A2. ("ACCase" is acetyl CoA carboxylase.)
WO 92/16510 A1 (Ciba-Geigy AG) discloses 4-aryl-pyrazolidine-3,5-dione herbicides, and their use as herbicides, acaricides and insecticides. EP 0 508 126 A1 (Bayer AG) discloses 3-hydroxy-4-aryl-5-oxo-pyrazoline derivatives, and their use as insecticides, acaricides and herbicides. WO 96/21652 A1 (Ciba-Geigy AG) discloses 4-aryl- and 4-heteroaryl- 5- oxopyrazoline derivatives having pesticidal properties. WO 99/47525 A1 (Novartis AG) discloses herbicidally active 3-hydroxy-4-aryl-5-oxo- pyrazoline derivatives. In WO 99/47525 A1 , the 3-hydroxy-5-oxo-pyrazoline ring system is fused, through the two ring-nitrogens of the pyrazole, to a further ring which also contains a ring-oxygen atom. See also WO 00/47585 A (Novartis AG).
M. Muehlebach et al., Bioorganic and Medicinal Chemistry, 2009, 17, 4241 -4256, discloses a class of 3-hydroxy-4-phenyl-5-oxo-pyrazolines, in particular aryl (here, phenyl) diones incorporating a [1 ,4,5]oxadiazepane ring, and most particularly discloses the cereal herbicide pinoxaden, which is an ACCas llowing structure:
Figure imgf000004_0001
pinoxaden
WO 01/17972 A2 (Syngenta Participations AG) discloses (4-methyl-phenyl)-substituted (such as 4-methyl-2,6-diethyl-phenyl- substituted) carbocycles or heterocycles, in particular carbocyclic or heterocyclic diones, suitable for use as herbicides.
WO 01/74770 A (Bayer AG), and its equivalent US 2003/0216260 A1 , disclose C2-phenyl- substituted cyclic ketoenols and their use as pesticides and 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 mefenpyr-diethyl. In WO 03/013249 A1 and US 2005/0054535 A1 , the cyclic ketoenol (whose tautomer is a cyclic dione) can in particular be a 3-(substituted-phenyl)-pyrrolidine- 2,4-dione, a 3-(substituted-phenyl)-tetrahydrofuran-2,4-dione, a 3-(substituted-phenyl)-pyran- 2,4-dione derivative, a 2-(substituted-phenyl)-cyclopentane-1 ,3-dione, or a 2-(substituted- phenyl)-cyclohexane-1 ,3-dione, et al., or a derivative (e.g. ester or carbonate derivative) of these cyclic ketoenols / cyclic diones. 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 and/or phosphonium salt allegedly to boost activity. In WO 2007/068427 A2 and US 2009/0227563 A1 , the cyclic ketoenol (whose tautomer is a cyclic dione) can in particular be a 3-(substituted-phenyl)-pyrrolidine-2,4-dione, a 3-(substituted- phenyl)-tetrahydrofuran-2,4-dione, a 3-(substituted-phenyl)-pyran-2,4-dione derivative, a 2- (substituted-phenyl)-cyclopentane-l ,3-dione, or a 2-(substituted-phenyl)-cyclohexane-1 ,3- dione, a 4-(substituted-phenyl)-pyrazolidine-3,5-dione, et al., or a derivative (e.g. ester or carbonate derivative) of these cyclic ketoenols / cyclic diones. See also WO 2007/068428 A (Bayer CropScience AG) and its equivalent US2009/0209513A1 .
WO 2006/089633 A2 (Bayer CropScience AG) and its equivalent US 2008/0305955 A1 discloses spiroketal-substituted heterocyclic ketoenols, more particularly 5-spirocyclic-3- (substituted-phenyl)- pyrrolidine-2,4-diones or tetrahydrofuran-2,4-diones, or derivatives thereof, and their use as pesticides, microbicides and/or herbicides.
WO 2007/121868 A1 (Bayer CropScience AG) and its equivalent US 2009/0239906 A1 discloses 5-[alkoxyalkyl- or heterocyclyl(alkyl)-]-substituted-3-(substituted-phenyl)- pyrrolidine-2,4-diones, or derivatives thereof, and their use as pesticides, microbicides and/or herbicides. See also WO 2007/140881 A1 (Bayer CropScience AG).
WO 2012/175666 A1 (Syngenta Participations AG) discloses certain substituted N-oxy pyrazolo-triazepine-dione derivatives having pesticidal and herbicidal properties.
WO 201 1/151 199 A1 (Syngenta Participations AG) discloses new 5-spiroheterocyclic-3- (substituted-phenyl)-pyrrolidine-2,4-dione compounds, or derivatives, in which the phenyl has at least one C2-C6alkenyl, C2-C6alkynyl, -CHO, C Cealkylcarbonyl or d-Cealkoxycarbonyl substituent, and their use as insecticides, acaricides, molluscicides and nematicides.
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. 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-dione by a phenyl which itself is substituted at the 4-position by (specifically) either prop-1 -ynyl or chloroethynyl and at the 2-position by (specifically) either methyl or chlorine, 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.
Heterocyclic dione compounds have now been discovered, in particular pyrazolidine-dione (more particularly pyrazolidine-3,5-dione) compounds or pyrrolidine-dione (more particularly pyrrolidine-2,4-dione) compounds or fused bicyclic derivatives of such diones, which are substituted, at the ring-carbon atom of the heterocyclic dione which is between the two oxo- substituted ring-carbons of the heterocyclic dione, by a phenyl which itself is substituted (a) at the 4-position of the phenyl by (specifically) prop-1 -ynyl and (b) at a 2-position of the phenyl by (specifically) fluorine or chlorine; or derivatives of the enol ketone tautomer of such heterocyclic diones.
These compounds of the present invention appear to exhibit potent herbicidal activity and/or plant-growth-inhibiting properties in the control of grassy monocotyledonous weeds, e.g. after post-emergence application of the compounds in particular at an application rate of 250 g/ha - see the post-emergence herbicidal activity results for compounds A2, A6, A8, A9, A14, A24, A26, A29, A30, P1 , P2, P3, P4 and P5 of the present invention in Biological Example 1 hereinafter.
Certain compounds of the present invention (particularly exemplified compounds A2, A26, A29, P2, P5, and probably also compound A14), when applied post-emergence, appear to be selective for warm-climate grassy monocotyledonous weed control in certain
dicotyledonous crops, in particular in one or more of Glycine max (soybean), Brassica napus (rape, also called oilseed rape or rapeseed), and/or Beta vulgaris (sugar beet) (e.g. see Biological Examples 2 and 3 herein). Exemplified compounds A2, A26, A29, P2 and P5 of the present invention, when applied post-emergence, appear to be selective for warm- climate grassy monocotyledonous weed control in crops of Triticum aestivum (winter wheat) and/or Hordeum vulgare (barley) (e.g. see Biological Example 3 herein). Therefore, in a first aspect of the present invention, there is provided a compound of formula (I):
Figure imgf000007_0001
wherein CKE is of sub-formula (A) and/or (B):
Figure imgf000007_0002
(A) (B)
wherein:
R1 is fluorine or chlorine;
R2 is hydrogen, methyl, ethyl, n-propyl, n-butyl, cyclopropyl, ethynyl, cyano, fluorine, chlorine, bromine, CrC3alkoxy, CrC2fluoroalkoxy, (difluoro)vinyloxy, Ci-C2alkoxy-Ci-C3alkoxy-, or C 1 f I u oroa I koxy-C i - C3a I koxy- ;
X is NR4 or CR5R6; wherein:
R3, R4, and R5, independently of each other, are:
hydrogen, CrC4alkyl (in particular CrC3alkyl, more particularly methyl or ethyl), C1-C2fluoroalkyl, d-CsalkoxyC Csalkyl (in particular C1-C2alkoxyC1-C2alkyl such as
MeOCH2CH2-), Ci-C3alkylthioCi-C3alkyl (in particular C1-C2alkylthioC1-C2alkyl such as MeSCH2CH2-), C C4alkoxy (in particular methoxy), R9-C≡C-C(R7)(R8)-,
(R11)(R12)C=C(R10)-C(R7)(R8)-, Het-CH2-, or Het; or
benzyl optionally substituted on its phenyl ring by 1 or 2 substituents independently being halogen (preferably fluorine, chlorine or bromine), C-|-C2alkyl (preferably methyl), C-ifluoroalkyl (preferably trifluoromethyl), C1-C2alkoxy (preferably methoxy), C-ifluoroalkoxy (preferably trifluoromethoxy or difluoromethoxy), -C≡C-R13, -C(R14)=C(R15)(R16), -C(0)Me, -C(0)-Cifluoroalkyl, -S(0)n4-Me, -S(0)n4-Cifluoroalkyl, -NR19R20, or cyano; or
phenyl optionally substituted by 1 or 2 substituents independently being halogen (preferably fluorine, chlorine or bromine), CrC2alkyl (preferably methyl), dfluoroalkyl (preferably trifluoromethyl), -C≡C-R13, -C(R14)=C(R15)(R16), C C2alkoxy (preferably methoxy), Cifluoroalkoxy (preferably trifluoromethoxy or difluoromethoxy), -C(0)Me,
-C(0)-Cifluoroalkyl, -S(0)n5-Me, -S(0)n5-Cifluoroalkyl, -NR19R20, or cyano;
provided that when X is NR4, then at least one of R3 and R4 (preferably R3) is hydrogen or CrC3alkyl; and provided that when X is CR5R6, then at least one of R3 and R5 (preferably R3) is hydrogen or Ci-C3alkyl; or R3 and R4 are taken together, and/or R3 and R5 are taken together, to form a chain which is (a), (b), (c), (d), (e), (f) or (g), as shown below:
-C(R21)(R22)-C(R23)(R24)-Y-C(R25)(R26)-C(R27)(R28)- (a)
-C(R21)(R22)-Y-C(R21A)(R22A)-C(R21A)(R22A)-C(R27)(R28)- (b)
-CH(R29)-Y-C(R21A)(R22A)-CH(R32)- (c)
-CH(R29)-Y-CH(R32)- (d)
-C(R21)(R22)-C(R23)(R24)-C(R30)(R31)-C(R25)(R26)-C(R27)(R28)- (e)
-C(R21)(R22)-C(R21A)(R22A)-C(R30)(R31)-C(R27)(R28)- (f)
-CH(R29)-C(R30)(R31)-CH(R32)- (g) wherein Y is O or NR4U; and R6 is hydrogen or CrC3alkyl; or R5 and R6 taken together are -(CH2)ni- or -(CH2)n2-X1-(CH2)n3-, in which case R3 is as defined herein (preferably hereinabove) provided that R3 and R5 are not taken together; wherein X1 is O, C(H)(C C2alkyl), C(C C2alkyl)2 or C(H)(C C2alkoxy);
n1 is 2, 3, 4 or 5 (preferably n1 is 4 or 5); and
n2 and n3 are independently 1 , 2 or 3 provided that n2 + n3 is 2, 3 or 4 (preferably n2 + n3 is 3 or 4); and wherein: Het is a heteroaryl, attached at a ring-carbon, which is optionally substituted by 1 , 2 or 3 (preferably 1 or 2, more preferably 1 ) ring-carbon substituents independently being halogen (preferably fluorine or chlorine), CrC3alkyl (preferably CrC2alkyl), CrC2fluoroalkyl (preferably Cifluoroalkyl), -C≡C-R13 (preferably ethynyl or prop-1-ynyl), -C(R14)=C(R15)(R16) (preferably ethenyl or prop-1 -enyl), d-C3alkoxy (preferably CrC2alkoxy such as methoxy), CrC2fluoroalkoxy (preferably Cifluoroalkoxy), cyclopropyloxy, CH2=CH-CH2-0-,
HC≡C-CH2-0-, -C(0)-R17, -S(0)ni8-R18, -NR19R20, cyano or nitro; provided that any non- fluorine halogen, alkoxy, fluoroalkoxy, cyclopropyloxy, CH2=CH-CH2-0- or HC≡C-CH2-0- is not substituted at any ring-carbon bonded directly to a ring-nitrogen of the heteroaryl; and/or, when Het is a 5-membered heteroaryl ring containing a ring-nitrogen atom not partaking in a C=N ring double bond, the heteroaryl is optionally substituted on the ring- nitrogen atom not partaking in a C=N ring double bond by one C Csalkyl, C-|-C2fluoroalkyl, C C3alkyl-C(0)-, C C2fluoroalkyl-C(0)- or C C2alkyl-S(0)2- substituent; and wherein:
R7 and R8, independently of each other, are hydrogen or methyl;
R9 is hydrogen, methyl, ethyl or chlorine; and
R10, R11 and R12, independently of each other, are hydrogen, methyl or ethyl, provided that R10, R11 and R12 in total contain no more than three carbon atoms;
R13 is hydrogen, methyl, Cifluoroalkyl (in particular trifluoromethyl), fluorine or chlorine; R14, R15 and R16 independently are hydrogen, methyl, Cifluoroalkyl (in particular trifluoromethyl), fluorine or chlorine; provided that R14, R15 and R16 in total contain no more than one carbon atom, and R14, R15 and R16 in total comprise no more than one chlorine; and
n4 is 0, 1 or 2;
n5 is 0, 1 or 2;
R17 and R18 independently are C C3alkyl, Cifluoroalkyl, or -NR19AR20A;
n18 is 0, 1 or 2;
R19 is -C(0)-CrC2alkyl, -C(0)-Cifluoroalkyl, -S(0)2-C C2alkyl, -S(0)2-Cifluoroalkyl, Ci-C2alkyl, or Cifluoroalkyl;
R20 and R20A independently are hydrogen, methyl or Cifluoroalkyl; and
R19A is hydrogen, C C2alkyl or Cifluoroalkyl; and wherein: R , R , R and R are independently hydrogen or methyl; provided that two, three or all of R21, R22, R27 and R28 are hydrogen; and
R21A and R22A are independently hydrogen or methyl; and
R23, R24, R25, and R26 are independently hydrogen, methyl, ethyl or methoxymethyl; provided that two, three or all of R23, R24, R25 and R26 are hydrogen;
or R23 and R25 are taken together and form a -CH2- or -CH2CH2- bridge, and R24 and R26 are hydrogen; and
R29 and R32 are independently hydrogen or methyl; and
R30 is hydrogen, d-C3alkyl, CrC2fluoroalkyl, CrC3alkoxy (preferably methoxy),
CrC3fluoroalkoxy (in particular CF3CH20-), CrC3alkyl-S(0)n3o-, Ci-C2alkoxyCrC2alkyl (in particular methoxymethyl), or Ci-C2alkylthioCrC2alkyl (preferably R30 is hydrogen or methoxy, more preferably hydrogen);
wherein n30 is 0, 1 or 2 (preferably 0); and
R31 is hydrogen, methyl or ethyl (preferably R31 is hydrogen);
or R30 and R31 taken together are oxo (=0), =N-0-H, or =N-0-(C C3alkyl); provided that, in all cases wherein R3 and R4 are taken together, and/or R3 and R5 are taken together, to form a chain which is (a), (b), (c), (d), (e), (f) or (g), then the chain contains a total of no more than three substituents (preferably a total of none, one or two substituents) on carbon in the ring which is formed by NR3, X, and the chain (a), (b), (c), (d), (e), (f) or (g); wherein if a bridge is formed by R23 and R25 being taken together then this bridge is counted as two ring-carbon-substituents; and wherein R40 is C-|-C3alkoxy, C-|-C2fluoroalkoxy (in particular C-ifluoroalkoxy or CF3CH2-), cyclopropyloxy, CH2=CH-CH2-0-, HC≡C-CH2-0-, N≡C-CH20-, CH3OCH20-,
CH3OCH2CH20-, CH3CH2OCH20-, C C3alkyl or dfluoroalkyl ;
and wherein:
G is hydrogen; an agriculturally acceptable metal, or an agriculturally acceptable sulfonium or ammonium group; or G is -C(Xa)-Ra, -C(Xb)-Xc-Rb, -C(Xd)-N(Rc)-Rd, -S02-Re, -P(Xe)(R )-R9, -CH2-Xf-Rh; or phenyl-CH2- or phenyl-CH(Ci-C2alkyl)- (in each of which the phenyl is optionally substituted by 1 , 2 or 3 of, independently, Ci-C2alkyl, CifluoroalkyI, Ci-C2alkoxy, Cifluoroalkoxy, fluorine, chlorine, bromine, cyano or nitro), or heteroaryl-CH2- or heteroaryl-CH(Ci-C2alkyl)- (in each of which the heteroaryl is optionally substituted by 1 , 2 or 3 of, independently, Ci-C2alkyl, CifluoroalkyI, Ci-C2alkoxy, Cifluoroalkoxy, fluorine, chlorine, bromine, cyano or nitro), or phenyl-C(0)-CH2- (wherein the phenyl is optionally substituted by 1 , 2 or 3 of, independently, CrC2alkyl, CifluoroalkyI, Ci-C2alkoxy, Cifluoroalkoxy, fluorine, chlorine, bromine, cyano or nitro); or CrC6alkoxy-C(0)-CH2-, CrC6alkoxy-C(0)-CH=CH-, C2-C7alken-1-yl-CH2-,
C2-C7alken-1 -yl-CH(C C2alkyl)-, C2-C4fluoroalken-1 -yl-CH2-, C2-C7alkyn-1-yl-CH2-, or C2-C7alkyn-1 -yl-CH(Ci-C2alkyl)-; wherein Xa, Xb, Xc, Xd, Xe and X are independently of each other oxygen or sulfur (preferably oxygen); and wherein
Ra is H, Ci-C2ialkyl, C2-C2ialkenyl, C2-Ci8alkynyl, Ci-Ci0fluoroalkyl, Ci-Ci0cyanoalkyl, C Ci0nitroalkyl, Ci-Ci0aminoalkyl, Ci-C5alkylamino(Ci-C5)alkyl, C2-C8dialkylamino(Ci-C5)alkyl, C3-C7cycloalkyl(Ci-C5)alkyl, Ci-C5alkoxy(Ci-C5)alkyl, C3-C5alkenyloxy(Ci-C5)alkyl, C3- C5alkynyloxy (C C5)alkyl, Ci-C5alkylthio(Ci-C5)alkyl, Ci-C5alkylsulfinyl(Ci-C5)alkyl, C
C5alkylsulfonyl(Ci-C5)alkyl, C2-C8alkylideneaminoxy(Ci-C5)alkyl, Ci-C5alkylcarbonyl(d- C5)alkyl, Ci-C5alkoxycarbonyl(Ci-C5)alkyl, aminocarbonyl(Ci-C5)alkyl, C
C5alkylaminocarbonyl(Ci-C5)alkyl, C2-C8dialkylaminocarbonyl(Ci-C5)alkyl, C
C5alkylcarbonylamino(Ci-C5)alkyl, /V-(Ci-C5)alkylcarbonyl-/V-(Ci-C5)alkylamino(Ci-C5)alkyl, C3-C6trialkylsilyl(Ci-C5)alkyl, phenyl(Ci-C5)alkyl (wherein the phenyl is optionally substituted by 1 , 2 or 3 of, independently, Ci-C3alkyl, Ci-C3fluoroalkyl, Ci-C3alkoxy, Ci-C3fluoroalkoxy, Ci-C3alkylthio, Ci-C3alkylsulfinyl, Ci-C3alkylsulfonyl, halogen, cyano, or nitro), heteroaryl(Cr C5)alkyl (wherein the heteroaryl is optionally substituted by 1 , 2 or 3 of, independently, C C3alkyl, Ci-C3fluoroalkyl, Ci-C3alkoxy, Ci-C3fluoroalkoxy, Ci-C3alkylthio, CrC3alkylsulfinyl, CrC3alkylsulfonyl, halogen, cyano, or nitro), C2-C5fluoroalkenyl, C3-C8cycloalkyl; phenyl or phenyl substituted by 1 , 2 or 3 of, independently, Ci-C3alkyl, Ci-C3fluoroalkyl, Ci-C3alkoxy, CrC3fluoroalkoxy, halogen, cyano or nitro; or heteroaryl or heteroaryl substituted by 1 , 2 or 3 of, independently, Ci-C3 alkyl, CrC3fluoroalkyl, Ci-C3alkoxy, Ci-C3fluoroalkoxy, halogen, cyano or nitro; Rb is Ci-Ci8alkyl, C3-C18alkenyl, C3-C18alkynyl, C2-C10fluoroalkyl, d-docyanoalkyl, C Cionitroalkyl, d-doaminoalkyl, d-C5alkylamino(d-C5)alkyl, d-ddialkylamino(d-d)alkyl, d-dcycloalkyl(Ci-d)alkyl, Ci-C5alkoxy(Ci-C5)alkyl, d-dalkenyloxy(d-d)alkyl, C3- dalkynyloxy(Ci-d)alkyl, Ci-C5alkylthio(Ci-C5)alkyl, Ci-C5alkylsulfinyl(Ci-C5)alkyl, d- dalkylsulfonyl(d-d)alkyl, d-dalkylideneaminoxy(d-d)alkyl, d-dalkylcarbonyl(d- d)alkyl, Ci-dalkoxycarbonyl(d-d)alkyl, aminocarbonyl(d-d)alkyl, d- dalkylaminocarbonyl(Ci-d)alkyl, d-ddialkylaminocarbonyl(d-d)alkyl, d- dalkylcarbonylamino(d-d)alkyl, /V-(d-d)alkylcarbonyl-/V-(Ci-d)alkylamino(Ci-d)alkyl, d-dtrialkylsilyl(d-d)alkyl, phenyl(d-d)alkyl (wherein the phenyl is optionally substituted by 1 , 2 or 3 of, independently, d-dalkyl, d-dfluoroalkyl, d-dalkoxy, d-dfluoroalkoxy, d-dalkylthio, Ci-C3alkylsulfinyl, d-dalkylsulfonyl, halogen, cyano, or nitro), heteroaryld- dalkyl (wherein the heteroaryl is optionally substituted by 1 , 2 or 3 of, independently, d- dalkyl, d-dfluoroalkyl, d-dalkoxy, d-dfluoroalkoxy, d-dalkyl-thio, d-dalkylsulfinyl, Crdalkylsulfonyl, halogen, cyano, or nitro), d-dfluoroalkenyl, d-dcycloalkyl; phenyl or phenyl substituted by 1 , 2 or 3 of, independently, d-dalkyl, d-dfluoroalkyl, d-dalkoxy, d-dfluoroalkoxy, halogen, cyano or nitro; or heteroaryl or heteroaryl substituted by 1 , 2 or 3 of, independently, d-d alkyl, d-dfluoroalkyl, d-dalkoxy, d-dfluoroalkoxy, halogen, cyano or nitro; and
Rc and Rd are each independently of each other hydrogen, d-C10alkyl, C3-d0alkenyl, d- d0alkynyl, C2-d0fluoroalkyl, d-d0cyanoalkyl, d-d0nitroalkyl, d-d0aminoalkyl, d- dalkylamino(C1-d)alkyl, d-ddialkylamino(C1-C5)alkyl, d-dcycloalkyl(d-d)alkyl, d- dalkoxy(d-d)alkyl, d-dalkenyloxy(d-d)alkyl, C3-dalkynyloxy(d-d)alkyl, C dalkylthio(d-d)alkyl, C1-dalkylsulfinyl(C1-C5)alkyl, C1-dalkylsulfonyl(C1-d)alkyl, d- dalkylideneaminoxy(C1-d)alkyl, C1-dalkylcarbonyl(C1-C5)alkyl, d-dalkoxycarbonyl(d- d)alkyl, aminocarbonyl(d-d)alkyl, C1-dalkylaminocarbonyl(C1-d)alkyl, C2- ddialkylaminocarbonyl(C1-d)alkyl, C1-dalkylcarbonylamino(C1-d)alkyl, /V-(d- d)alkylcarbonyl-/V-(C2-d)alkylaminoalkyl, d-dtrialkylsilyl(d-d)alkyl, phenyl(d-C5)alkyl (wherein the phenyl is optionally substituted by 1 , 2 or 3 of, independently, d-dalkyl, d- dfluoroalkyl, d-dalkoxy, d-dfluoroalkoxy, d-dalkylthio, d-dalkylsulfinyl, d- dalkylsulfonyl, halogen, cyano, or nitro), heteroaryl(d-C5)alkyl (wherein the heteroaryl is optionally substituted by 1 , 2 or 3 of, independently, d-dalkyl, d-dfluoroalkyl, d- dalkoxy, d-dfluoroalkoxy, d-dalkylthio, d-dalkylsulfinyl, d-dalkylsulfonyl, halogen, cyano, or nitro), d-dfluoroalkenyl, d-dcycloalkyl; phenyl or phenyl substituted by 1 , 2 or 3 of, independently, d-C3alkyl, d-C3fluoroalkyl, d-C3alkoxy, CrCsfluoroalkoxy, halogen, cyano or nitro; heteroaryl or heteroaryl substituted by 1 , 2 or 3 of, independently, CrC3alkyl, CrC3fluoroalkyl, CrC3alkoxy, CrC3fluoroalkoxy, halogen, cyano or nitro; heteroarylamino or heteroarylamino substituted by 1 , 2 or 3 of, independently, Ci-C3alkyl, Ci-C3fluoroalkyl, d- C3alkoxy, CrC3fluoroalkoxy, halogen, cyano or nitro; diheteroarylamino or diheteroarylamino substituted by 1 , 2 or 3 of, independently, Ci-C3alkyl, Ci-C3fluoroalkyl, Ci-C3alkoxy, d- C3fluoroalkoxy, halogen, cyano or nitro; phenylamino or phenylamino substituted by 1 , 2 or 3 of, independently, Ci-C3alkyl, Ci-C3fluoroalkyl, Ci-C3alkoxy, Ci-C3fluoroalkoxy, halogen, cyano or by nitro; diphenylamino or diphenylamino substituted by 1 , 2 or 3 of, independently, d-dalkyl, Ci-C3fluoroalkyl, Ci-C3alkoxy, Ci-C3fluoroalkoxy, halogen, cyano or nitro; or C3- dcycloalkylamino, di(C3-C7cycloalkyl)amino or C3-C7cycloalkoxy;
or Rc and Rd, together with the nitrogen to which they are bonded, to form an unsubstituted 4, 5, 6 or 7 (e.g. 5 or 6) membered ring, optionally containing one heteroatom selected from O or S; and
Re is d-C10alkyl, C2-C10alkenyl, C2-C10alkynyl, d-C10fluoroalkyl, d-C10cyanoalkyl, d- C10nitroalkyl, d-C10aminoalkyl, C1-C5alkylamino(C1-C5)alkyl, C2-C8dialkylamino(C1-C5)alkyl, C3-C7cycloalkyl(Ci-C5)alkyl, Ci-C5alkoxy(Ci-C5)alkyl, C3-C5alkenyloxy(Ci-C5)alkyl, C3- C5alkynyloxy(Ci-C5)alkyl, Ci-C5alkylthio(Ci-C5)alkyl, Ci-C5alkylsulfinyl(Ci-C5)alkyl, d- C5alkylsulfonyl(d-C5)alkyl, C2-C8alkylideneaminoxy(C1-C5)alkyl, CrC5alkylcarbonyl(Cr C5)alkyl, C1-C5alkoxycarbonyl(C1-C5)alkyl, aminocarbonyl(d-C5)alkyl, d- C5alkylaminocarbonyl(d-C5)alkyl, C2-C8dialkylaminocarbonyl(d-C5)alkyl, d- C5alkylcarbonylamino(C1-C5)alkyl, /V-(C1-C5)alkylcarbonyl-/V-(C1-C5)alkylamino(C1-C5)alkyl, C3-C6trialkylsilyl(C1-C5)alkyl, phenyl(C1-C5)alkyl (wherein the phenyl is optionally substituted by 1 , 2 or 3 of, independently, d-C3alkyl, d-C3fluoroalkyl, d-C3alkoxy, CrCsfluoroalkoxy, CrC3alkylthio, CrC3alkylsulfinyl, CrC3alkylsulfonyl, halogen, cyano, or nitro), heteroaryl(d- C5)alkyl (wherein the heteroaryl is optionally substituted by 1 , 2 or 3 of, independently, d- C3alkyl, Ci-C3fluoroalkyl, Ci-C3alkoxy, Ci-C3fluoroalkoxy, Ci-C3alkylthio, Ci-C3alkylsulfinyl, Ci-C3alkylsulfonyl, halogen, cyano, or nitro), C2-C5fluoroalkenyl, C3-C8cycloalkyl; phenyl or phenyl substituted by 1 , 2 or 3 of, independently, Ci-C3alkyl, Ci-C3fluoroalkyl, Ci-C3alkoxy, CrC3fluoroalkoxy, halogen, cyano or nitro; heteroaryl or heteroaryl substituted by 1 , 2 or 3 of, independently, Ci-C3alkyl, Ci-C3fluoroalkyl, Ci-C3alkoxy, Ci-C3fluoroalkoxy, halogen, cyano or nitro; heteroarylamino or heteroarylamino substituted by 1 , 2 or 3 of, independently, CrC3 alkyl, Ci-C3fluoroalkyl, Ci-C3alkoxy, Ci-C3fluoroalkoxy, halogen, cyano or nitro; diheteroarylamino or diheteroarylamino substituted by 1 , 2 or 3 of, independently, Ci-C3alkyl, CrC3fluoroalkyl, CrC3alkoxy, CrC3fluoroalkoxy, halogen, cyano or nitro; phenylamino or phenylamino substituted by 1 , 2 or 3 of, independently, Ci-C3alkyl, CrC3fluoroalkyl, d- C3alkoxy, CrC3fluoroalkoxy, halogen, cyano or nitro; diphenylamino or diphenylamino substituted by 1 , 2 or 3 of, independently, Ci-C3alkyl, Ci-C3fluoroalkyl, Ci-C3alkoxy, d- C3fluoroalkoxy, halogen, cyano or nitro; or C3-C7cycloalkylamino, di(C3-C7cycloalkyl)amino, C3-C7cycloalkoxy, CrCi0alkoxy, Ci-Ci0fluoroalkoxy, Ci-C5alkylamino or di(Ci-C4alkyl)amino;
R and R9 are are each independently of each other CrCi0alkyl, C2-Ci0alkenyl, C2-Ci0alkynyl, Ci-Ci0alkoxy, Ci-Ci0fluoroalkyl, Ci-Ciocyanoalkyl, CrCi0nitroalkyl, Ci-Ci0aminoalkyl, d- C5alkylamino(C1-C5)alkyl, C2-C8dialkylamino(C1-C5)alkyl, C3-C7cycloalkyl(C1-C5)alkyl, d- C5alkoxy(C1-C5)alkyl, C3-C5alkenyloxy(C1-C5)alkyl, C3-C5alkynyloxy(C1-C5)alkyl, C
C5alkylthio(C1-C5)alkyl, C1-C5alkylsulfinyl(C1-C5)alkyl, C1-C5alkylsulfonyl(C1-C5)alkyl, C2- C8alkylideneaminoxy(C1-C5)alkyl, C1-C5alkylcarbonyl(C1-C5)alkyl, CrC5alkoxycarbonyl(Cr d)alkyl, aminocarbonyl(d-d)alkyl, C1-dalkylaminocarbonyl(C1-d)alkyl, C2- ddialkylaminocarbonyl(C1-d)alkyl, d-C5alkylcarbonylamino(d-C5)alkyl, /V-(d- d)alkylcarbonyl-/V-(C2-d)alkylaminoalkyl, C3-C6trialkylsilyl(C -C5)alkyl, phenyl(d-C5)alkyl (wherein the phenyl is optionally substituted by 1 , 2 or 3 of, independently, d-C3alkyl, d- dfluoroalkyl, d-dalkoxy, d-dfluoroalkoxy, d-dalkylthio, d-C3alkylsulfinyl, d- dalkylsulfonyl, halogen, cyano, or nitro), heteroaryl(C1-d)alkyl (wherein the heteroaryl is optionally substituted by 1 , 2 or 3 of, independently, d-dalkyl, d-dfluoroalkyl, d- dalkoxy, Crdfluoroalkoxy, d-dalkylthio, d-dalkylsulfinyl, d-dalkylsulfonyl, halogen, cyano, or nitro), C2-dfluoroalkenyl, C3-C8cycloalkyl; phenyl or phenyl substituted by 1 , 2 or 3 of, independently, d-dalkyl, d-dfluoroalkyl, d-dalkoxy, Crdfluoroalkoxy, halogen, cyano or nitro; heteroaryl or heteroaryl substituted by 1 , 2 or 3 of, independently, d-d alkyl, d-dfluoroalkyl, d-dalkoxy, Crdfluoroalkoxy, halogen, cyano or nitro; heteroarylamino or heteroarylamino substituted by 1 , 2 or 3 of, independently, d-C3 alkyl, d-C3fluoroalkyl, d- dalkoxy, Crdfluoroalkoxy, halogen, cyano or nitro; diheteroarylamino or diheteroarylamino substituted by 1 , 2 or 3 of, independently, Ci-C3 alkyl, d-C3fluoroalkyl, d-C3alkoxy, d- dfluoroalkoxy, halogen, cyano or nitro; phenylamino or phenylamino substituted by 1 , 2 or 3 of, independently, d-C3alkyl, d-C3fluoroalkyl, d-C3alkoxy, Crdfluoroalkoxy, halogen, cyano or nitro; diphenylamino or diphenylamino substituted by 1 , 2 or 3 of, independently, d- dalkyl, d-C3fluoroalkyl, d-C3alkoxy, Crdfluoroalkoxy, halogen, cyano or nitro; or C3- dcycloalkylamino, di(C3-C7cycloalkyl)amino, C3-C7cycloalkoxy, d-Ciofluoroalkoxy, d- C5alkylamino or di(C1-C4alkyl)amino; or benzyloxy or phenoxy, wherein the benzyl and phenyl groups are in turn optionally substituted by 1 , 2 or 3 of, independently, d-C3alkyl, d- C3fluoroalkyl, CrC3alkoxy, CrC3fluoroalkoxy, halogen, cyano or nitro; and
Rh is Ci-Ci0alkyl, C3-Ci0alkenyl, C3-Ci0alkynyl, Ci-Ciofluoroalkyl, Ci-Ciocyanoalkyl, d- Ci0nitroalkyl, C2-Ci0aminoalkyl, Ci-C5alkylamino(Ci-C5)alkyl, C2-C8dialkylamino(Ci-C5)alkyl, C3-C7cycloalkyl(Ci-C5)alkyl, Ci-C5alkoxy(Ci-C5)alkyl, C3-C5alkenyloxy(Ci-C5)alkyl, C3- C5alkynyloxy(Ci-C5)alkyl, Ci-C5alkylthio(Ci-C5)alkyl, Ci-C5alkylsulfinyl(Ci-C5)alkyl, d- C5alkylsulfonyl(Ci-C5)alkyl, C2-C8alkylideneaminoxy(Ci-C5)alkyl, CrC5alkylcarbonyl(Cr C5)alkyl, Ci-C5alkoxycarbonyl(Ci-C5)alkyl, aminocarbonyl(Ci-C5)alkyl, d- dalkylaminocarbonyl(d-d)alkyl, d-ddialkylaminocarbonyl(d-d)alkyl, d- dalkylcarbonylamino(C1-d)alkyl, /V-(C1-d)alkylcarbonyl-/V-(C1-d)alkylamino(C1-d)alkyl, C3-C6trialkylsilyl(Ci-C5)alkyl, phenyl(d-C5)alkyl (wherein the phenyl is optionally substituted by 1 , 2 or 3 of, independently, d-C3alkyl, d-C3fluoroalkyl, d-dalkoxy, Crdfluoroalkoxy, Crdalkylthio, Ci-C3alkylsulfinyl, d-d alkylsulfonyl, halogen, cyano or nitro), heteroaryl(d- d)alkyl (wherein the heteroaryl is optionally substituted by 1 , 2 or 3 of, independently, d- dalkyl, d-C3fluoroalkyl, d-dalkoxy, Crdfluoroalkoxy, Crdalkylthio, Ci-C3alkylsulfinyl, C alkylsulfonyl, halogen, cyano or nitro), phenoxy(d-C5)alkyl (wherein the phenyl is optionally substituted by 1 , 2 or 3 of, independently, d-dalkyl, d-C3fluoroalkyl, d- dalkoxy, Crdfluoroalkoxy, Crdalkylthio, d-C3alkylsulfinyl, d-C3 alkylsulfonyl, halogen, cyano or nitro), heteroaryloxy(CrC5)alkyl (wherein the heteroaryl is optionally substituted by 1 , 2 or 3 of, independently, d-C3alkyl, d-C3fluoroalkyl, Crdalkoxy, Crdfluoroalkoxy, Cr C3alkylthio, CrC3alkylsulfinyl, d-C3 alkylsulfonyl, halogen, cyano or nitro), C3- C5fluoroalkenyl, C3-C8cycloalkyl; phenyl or phenyl substituted by 1 , 2 or 3 of, independently, d-dalkyl, d-C3fluoroalkyl, d-C3alkoxy, CrC3fluoroalkoxy, halogen, cyano or nitro;
heteroaryl or heteroaryl substituted by 1 , 2 or 3 of, independently, d-C3alkyl, d- dfluoroalkyl, d-C3alkoxy, Crdfluoroalkoxy, halogen, cyano or nitro; CrC6alkyl-C(0)-; or phenyl-C(O)- wherein the phenyl is optionally substituted by 1 or 2 of, independently, d- dalkyl, CifluoroalkyI, d-dalkoxy, Cifluoroalkoxy, fluorine, chlorine, bromine, cyano or nitro; 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.
In the substituent definitions of the compounds of the formula I, each alkyl moiety either alone or as part of a larger group (such as alkoxy, alkylthio, alkoxycarbonyl, alkylcarbonyl, 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, ierf-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 C1-C4alkyl or C C3alkyl groups (except where already defined more narrowly), and, more preferably, are C1-C2alkyl groups such as methyl.
Alkenyl and alkynyl moieties can be in the form of straight or branched chains, and the alkenyl moieties, where appropriate, can be of either the (£)- or (Z)-configuration. The alkenyl or alkynyl are typically C2-C3alkenyl or C2-C3alkynyl such as vinyl, allyl, ethynyl, propargyl or prop-1-ynyl. Alkenyl and alkynyl moieties can contain one or more double and/or triple bonds in any combination; but preferably contain only one double bond (for alkenyl) or only one triple bond (for alkynyl).
Halogen is fluorine, chlorine, bromine or iodine. Preferred halogens are fluorine, chlorine or bromine.
FluoroalkyI groups are alkyl groups which are substituted with one or more (e.g. 1 , 2, 3, 4 or 5; in particular 1 , 2 or 3; e.g. 1 or 2) fluorine atoms. FluoroalkyI is typically CrC3fluoroalkyl or C C2fluoroalkyl (preferably Cifluoroalkyl), such as CF3, CHF2, CH2F, CH3CHF-, CF3CH2-, CHF2CH2-, CH2FCH2-, CHF2CF2- or (CH3)2CF-. Fluoroalkoxy is typically C C3fluoroalkoxy or Ci-C2fluoroalkoxy (preferably Cifluoroalkoxy), such as CF30, CHF20, CH2FO, CH3CHFO-, CF3CH20-, CHF2CH20- or CH2FCH20-.
In the context of the present specification the term "aryl" means phenyl or naphthyl. A preferred aryl group is phenyl. The term "heteroaryl" as used herein means an aromatic ring system containing at least one ring heteroatom and consisting either of a single ring or of two fused rings. Preferably, single rings will contain 1 , 2 or 3 ring heteroatoms and bicyclic systems 1 , 2, 3 or 4 ring
heteroatoms which will preferably be selected from nitrogen, oxygen and sulfur. Typically, a "heteroaryl" is furyl, thienyl, pyrrolyl, pyrazolyl, imidazolyl, 1 ,2,3-triazolyl, 1 ,2,4-triazolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, 1 ,2,4-oxadiazolyl, 1 ,3,4-oxadiazolyl,
1 ,2,5-oxadiazolyl, 1 ,2,3-thiadiazolyl, 1 ,2,4-thiadiazolyl, 1 ,3,4-thiadiazolyl, 1 ,2,5-thiadiazolyl, pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl, 1 ,2,3-triazinyl, 1 ,2,4-triazinyl, 1 ,3,5-triazinyl, benzofuryl, benzisofuryl, benzothienyl, benzisothienyl, indolyl, isoindolyl, indazolyl, benzothiazolyl, benzisothiazolyl, benzoxazolyl, benzisoxazolyl, benzimidazolyl, 2,1 ,3- benzoxadiazole, quinolinyl, isoquinolinyl, cinnolinyl, phthalazinyl, quinazolinyl, quinoxalinyl, naphthyridinyl, benzotriazinyl, purinyl, pteridinyl or indolizinyl; optionally present, where chemically possible, as an agrochemically acceptable salt thereof.
The term "heterocyclyl" as used herein, except where explicitly stated otherwise, means a 4, 5, 6 or 7 (in particular 5, 6 or 7) membered monocyclic organic ring or a 8, 9, 10 or 1 1 (in particular 8, 9 or 10) membered fused bicyclic organic ring system, which is fully saturated, and which has one or two (preferably one) ring heteroatoms independently selected from oxygen, sulfur and nitrogen. Where the heterocyclyl has two ring heteroatoms, preferably, the two ring heteroatoms are separated by at least two ring carbon atoms. Preferably, the heterocyclyl is attached at a ring carbon atom within the heterocyclyl. In particular, the heterocyclyl can be tetrahydrofuranyl, tetrahydropyranyl, tetrahydrothiophenyl, 1 ,4-dioxanyl, 1 ,4-dithianyl, morpholinyl, thiomorpholinyl, pyrrolidinyl, piperidinyl or piperazinyl; more particularly tetrahydrofuranyl (e.g. tetrahydrofuran-2-yl or particularly tetrahydrofuran-3-yl), tetrahydropyranyl (e.g. tetrahydropyran-2-yl, tetrahydropyran-3-yl or particularly
tetrahydropyran-4-yl), morpholinyl, pyrrolidinyl (e.g. pyrrolidin-2-yl or particularly pyrrolidin-3- yl), piperidinyl (e.g. piperidin-2-yl, piperidin-3-yl or particularly piperidin-4-yl) or piperazinyl. In a particular embodiment, the heterocyclyl, when optionally substituted, is optionally substituted by 1 or 2 (e.g. 1 ) ring-carbon substituents independently being CrC3alkyl (e.g. CrC2alkyl), CrC2fluoroalkyl or oxo (=0), and/or is optionally substituted by one CrC3alkyl (e.g. CrC2alkyl), CrC2fluoroalkyl or d-C3alkoxy (e.g. Ci-C2alkyl or Ci-C2fluoroalkyl) substituent on a ring nitrogen if present, and/or is optionally substituted by one or two oxo (=0) substituents on a ring sulfur if present. Preferably, a cycloalkyi is cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl. (Cycloalkyl)alkyl is preferably (cycloalkyl)methyl such as (C3-C6cycloalkyl)methyl in particular
cyclopropylmethyl. Preferably, cycloalkenyl is cyclopentenyl or cyclohexenyl.
The invention relates also to the agriculturally acceptable salts which the compounds of formula I are able to form with transition metal, alkali metal and alkaline earth metal bases, amines, quaternary ammonium bases or tertiary sulfonium bases.
Among the transition metal, alkali metal and alkaline earth metal salt formers, special mention should be made of the hydroxides of copper, iron, lithium, sodium, potassium, magnesium and calcium, and preferably the hydroxides, bicarbonates and carbonates of sodium and potassium.
Examples of amines suitable for ammonium salt formation include ammonia as well as primary, secondary and tertiary C-i-C-isalkylamines, C1-C4hydroxyalkylamines and
C2-C4alkoxyalkyl-amines, for example methylamine, ethylamine, n-propylamine,
isopropylamine, the four butylamine isomers, n-amylamine, isoamylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, pentadecylamine, hexadecylamine, heptadecylamine, octadecylamine, methylethylamine, methylisopropylamine,
methylhexylamine, methylnonylamine, methylpentadecylamine, methyloctadecylamine, ethylbutylamine, ethylheptylamine, ethyloctylamine, hexylheptylamine, hexyloctylamine, dimethylamine, diethylamine, di-n-propylamine, di-isopropylamine, di-n-butylamine, di-n- amylamine, di-isoamylamine, dihexylamine, diheptylamine, dioctylamine, ethanolamine, n- propanolamine, isopropanolamine, Λ/,/V-diethanolamine, /V-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, tri-isopropylamine, tri-n-butylamine, tri-isobutylamine, 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, phenylenediamines, benzidines, naphthylamines and 0-, m- and p-chloroanilines; but especially triethylamine,
isopropylamine and di-isopropylamine. Preferred quaternary ammonium bases suitable for salt formation correspond, for example, to the formula [N(Ra Rb Rc Rd)]OH, wherein Ra, Rb, Rc and Rd are each independently of the others hydrogen, CrC4alkyl. Further suitable tetraalkylammonium bases with other anions can be obtained, for example, by anion exchange reactions.
Preferred tertiary sulfonium bases suitable for salt formation correspond, for example, to the formula [SReRfRg]OH, wherein Re, Rf and Rg are each independently of the others C C4 alkyl. Trimethylsulfonium hydroxide is especially preferred. Suitable sulfonium bases may be obtained from the reaction of thioethers, in particular dialkylsulfides, with alkylhalides, followed by conversion to a suitable base, for example a hydroxide, by anion exchange reactions.
It should be understood that in those compounds of formula I , where G is a metal, ammonium or sulfonium as mentioned above and as such represents a cation, the corresponding negative charge is largely delocalised across the 0-C=C-C=0 unit.
The compounds of formula I according to the invention also include hydrates which may be formed during the salt formation.
The latentiating groups (i.e. leaving or removeable groups) within G (for example, without limitation, the latentiating groups where G is -C(Xa)-Ra or -C(Xb)-Xc-Rb, et al.) are generally selected to allow their removal, typically by one or a combination of biochemical, chemical or physical processes, to afford the corresponding compound of formula (I) where G is H , before, during or following (preferably during or following) application of the compound of formula (I) to the treated area (e.g. field) or to plants. Examples of these processes include enzymatic cleavage or other in/on-plant cleavage (e.g. cleavage of ester and/or carbonate moieties), chemical hydrolysis, and/or photoloysis. Some compounds bearing such groups G occasionally offer certain advantages or different technical properties, such as improved and/or more consistent and/or different penetration of the cuticula of the plants treated, increased and/or different tolerance of certain crops, improved and/or different compatibility or stability in formulated mixtures containing other herbicides, herbicide safeners, plant growth regulators, fungicides or insecticides, or reduced and/or different leaching properties in soils. The preferred (including more or most preferred et al.), particular, suitable, alternative and/or optional values of the substituents in, or other features of, the compound of formula (I), in particular G, X, X1, Y, R1, R2, R2A, R2B, R2C, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R p15 p16 p17 p18 p19 p20 p21 p21A p22 p22A p23 p24 p25 p26 p27 p28 p29 p30 p31 D:
R33, R40, Ra, Rb, Rc, Rd, Re, Rf, R9, Rh, Xa, Xb, Xc, Xd, Xe, Xf, Het, n1 , n2, n3, and/or n30, and/or all other features of or within the compound of formula (I), are set out below (and/or in some cases generally herein e.g. hereinabove), and can be either taken alone or taken together with one or more of any other preferred, particular, suitable, alternative and/or optional features in any combination(s) thereof.
When X is NR4 and CKE is of sub-formula (A), which is the generally preferred option when X is NR4, then the compound of formula I) is a compound of formula (I-A1 ):
Figure imgf000020_0001
When X is NR4 and CKE is of sub-formula (B), then the compound of formula (I) is a compound of formula (I-B1 :
Figure imgf000020_0002
When X is CR5R6 and CKE is of sub-formula (A), then the compound of formula (I) is a compound of formula (I-A2):
Figure imgf000021_0001
When X is CR5R6 and CKE is of sub-formula (B), which is the preferred option when X is CR5R6, then the compound of formula I) is a compound of formula (I-B2):
Figure imgf000021_0002
In the compounds of the invention (e.g. in the compounds of formula (I), in one preferred embodiment, G is hydrogen; an agriculturally acceptable metal (e.g. an agriculturally acceptable alkali metal or alkaline earth metal), or an agriculturally acceptable sulfonium or ammonium group; or G is -C(Xa)-Ra or -C(Xb)-Xc-Rb, wherein Xa, Ra, Xb, Xc and Rb are as defined herein.
In a particular embodiment, G is a group -C(Xa)-Ra or -C(Xb)-Xc-Rb, wherein Xa, Ra, Xb, Xc and Rb are as defined herein.
Preferably, Xa, Xb, Xc, Xd, Xe and/or Xf are oxygen. More preferably, Xa, Xb, Xc, Xd, Xe and Xf are oxygen.
Preferably, Ra is CrCi0alkyl (e.g. CrC6alkyl), C2-C6alkenyl (e.g. C2-C4alkenyl), C2-C6alkynyl (e.g. C2-C4alkynyl), C3-C6cycloalkyl or Ci-C4alkoxyCi-C4alkyl. Preferably, Rb is C C10alkyl (e.g. C C6alkyl), C2-C5alkenyl-CH2- (e.g. C2-C3alkenyl-CH2-), C2-C4alkenyl-CH(Me)- (e.g. C2-C3alkenyl-CH(Me)-), C2-C5alkynyl-CH2- (e.g.
C2-C3alkynyl-CH2-), C2-C4alkynyl-CH(Me)- (e.g. C2-C3alkynyl-CH(Me)-), C3-C6cycloalkyl or Ci-C4alkoxyCi-C4alkyl.
When G is -C(Xa)-Ra or -C(Xb)-Xc-Rb, then preferably Xa, Xb and Xc are oxygen, Ra is C Ci0alkyl (e.g. CrC6alkyl), C2-C6alkenyl (e.g. C2-C4alkenyl), C2-C6alkynyl (e.g. C2-C4alkynyl), C3-C6cycloalkyl or Ci-C4alkoxyCi-C4alkyl; and Rb is CrCi0alkyl (e.g. CrC6alkyl),
C2-C5alkenyl-CH2- (e.g. C2-C3alkenyl-CH2-), C2-C4alkenyl-CH(Me)- (e.g.
C2-C3alkenyl-CH(Me)-), C2-C5alkynyl-CH2- (e.g. C2-C3alkynyl-CH2-),
C2-C4alkynyl-CH(Me)- (e.g. C2-C3alkynyl-CH(Me)-), C3-C6cycloalkyl or Ci-C4alkoxyCi-C4alkyl.
In a preferable embodiment, G is hydrogen, or an agriculturally acceptable alkali metal or alkaline earth metal, or an agriculturally acceptable sulfonium or ammonium group. More preferably, G is hydrogen, or an agriculturally acceptable alkali metal or alkaline earth metal.
In a preferable embodiment, G is hydrogen, -C(Xa)-Ra or -C(Xb)-Xc-Rb.
Most preferably G is hydrogen.
In one preferred embodiment of the invention, R1 is fluorine.
However, in the most preferred embodiment of the invention, R1 is chlorine.
In the invention, R2 is hydrogen, methyl, ethyl, n-propyl, n-butyl, cyclopropyl, ethynyl, cyano, fluorine, chlorine, bromine, Ci-C3alkoxy (e.g. methoxy, ethoxy, n-propoxy or isopropoxy), CrC2fluoroalkoxy (e.g. C2fluoroalkoxy such as Cifluoroalkylmethoxy e.g. CF3CH20-, or C-ifluoroalkoxy such as difluoromethoxy or trifluoromethoxy), (difluoro)vinyloxy (i.e. CF2=CH- 0-), Ci-C2alkoxy-CrC3alkoxy-, or Cifluoroalkoxy-Ci-C3alkoxy-.
Preferably, when R2 is Ci-C2alkoxy-CrC3alkoxy- or Cifluoroalkoxy-CrC3alkoxy-, then R2 is R2A0-CH(R2B)-CH(R2C)-0-; wherein R is C1-C2alkyl (in particular methyl) or C-ifluoroalkyl; and
R2B and R2C are independently hydrogen or methyl, provided that one or both of R2B and R2C are hydrogen.
Preferably, R2A is methyl or C-ifluoroalkyl, more preferably methyl. Preferably, both of R2B and R2C are hydrogen.
More preferably, when R2 is Ci-C2alkoxy-Ci-C3alkoxy- or Cifluoroalkoxy-Ci-C3alkoxy- (in particular when R2 is R2A0-CH(R2B)-CH(R2C)-0-), then R2 is MeO-CH2-CH2-0-.
Preferably, e.g. in all aspects and/or embodiments of the invention, R2 is hydrogen, methyl, ethyl, n-propyl, n-butyl, cyclopropyl, ethynyl, cyano, fluorine, chlorine, bromine, methoxy, ethoxy, Cifluoroalkoxy, Cifluoroalkylmethoxy (in particular CF3CH20-), (difluoro)vinyloxy (i.e. CF2=CH-0-), or MeO-CH2-CH2-0-.
Preferably, e.g. in all aspects and/or embodiments of the invention, R2 is methyl, ethyl, n- propyl, cyclopropyl, ethynyl, cyano, fluorine, chlorine, bromine, methoxy, ethoxy,
Cifluoroalkoxy, Cifluoroalkylmethoxy (in particular CF3CH20-), (difluoro)vinyloxy (i.e.
CF2=CH-0-), or MeO-CH2-CH2-0-.
Alternatively or additionally, preferably, e.g. in all aspects and/or embodiments of the invention, R2 is hydrogen, methyl, ethyl, ethynyl, chlorine, methoxy, ethoxy, Cifluoroalkoxy (e.g. monofluoromethoxy, difluoromethoxy or trifluoromethoxy), Cifluoroalkylmethoxy (in particular CF3CH20-), or MeO-CH2-CH2-0-.
More preferably, e.g. in all aspects and/or embodiments of the invention, R2 is not hydrogen.
More preferably, e.g. in all aspects and/or embodiments of the invention, R2 is methyl, ethyl, ethynyl, chlorine, methoxy, ethoxy, Cifluoroalkoxy (e.g. monofluoromethoxy,
difluoromethoxy or trifluoromethoxy), Cifluoroalkylmethoxy (in particular CF3CH20-), or MeO-CH2-CH2-0-. Even more preferably, e.g. in all aspects and/or embodiments of the invention, R2 is methyl, chlorine, methoxy or ethoxy.
Still more preferably, e.g. in all aspects and/or embodiments of the invention, R2 is chlorine, methoxy or ethoxy.
Most preferably, e.g. in all aspects and/or embodiments of the invention, R2 is methoxy.
Therefore, more preferably, e.g. in all aspects and/or embodiments of the invention:
R1 is fluorine, and
R2 is methyl, ethyl, ethynyl, chlorine, methoxy, ethoxy, Cifluoroalkoxy, Cifluoroalkylmethoxy, or MeO-CH2-CH2-0-; still more preferably chlorine, methoxy or ethoxy; most preferably methoxy.
Most preferably, e.g. in all aspects and/or embodiments of the invention:
R1 is chlorine, and
R2 is methyl, ethyl, ethynyl, chlorine, methoxy, ethoxy, Cifluoroalkoxy, Cifluoroalkylmethoxy, or MeO-CH2-CH2-0-; still more preferably chlorine, methoxy or ethoxy; most preferably methoxy.
Particularly preferably, e.g. in all aspects and/or embodiments of the invention, X is NR4.
It is particularly preferable, e.g. in all aspects and/or embodiments of the invention, that R5 and R6 are not taken together to be -(CH2)n or -(CH2)n2-X1-(CH2)n3-. Therefore, preferably, R6 is hydrogen or d-C6alkyl.
More preferably, e.g. in all aspects and/or embodiments of the invention, R6 is hydrogen or methyl. Most preferably, R6 is hydrogen.
Preferably, e.g. in all aspects and/or embodiments of the invention, R3 is hydrogen,
Ci-C3alkyl, Ci-C2fluoroalkyl (in particular Cifluoroalkyl), or Het-CH2-; or R3 and R4 are taken together, and/or R3 and R5 are taken together, to form a chain which is (a), (b), (c), (d), (e), (f) or (g), as defined herein.
More preferably, R3 is hydrogen, C1-C2fluoroalkyl (in particular C-ifluoroalkyl), or Ci-C3alkyl; or R3 and R4 are taken together, and/or R3 and R5 are taken together, to form a chain which is (a), (b), (c), (d), (e), (f) or (g), as defined herein.
Preferably, e.g. in all aspects and/or embodiments of the invention, R4 and/or R5,
independently of each other, is or are:
hydrogen, CrC3alkyl (in particular methyl or ethyl), CrC2fluoroalkyl (in particular Cifluoroalkyl), Ci-C2alkoxyCi-C2alkyl (in particular MeOCH2CH2-), Ci-C2alkylthioC C2alkyl (in particular MeSCH2CH2-), C C2alkoxy (in particular methoxy), R9-C≡C-C(R7)(R8)-, or Het-CH2-; or
benzyl optionally substituted on its phenyl ring by 1 or 2 substituents independently being fluorine, chlorine, bromine, C-|-C2alkyl (preferably methyl), Cifluoroalkyl (preferably trifluoromethyl), C-i-C2alkoxy (preferably methoxy), C-ifluoroalkoxy (preferably
trifluoromethoxy or difluoromethoxy), -C≡C-R13, -C(R14)=C(R15)(R16), -C(0)Me,
-C(0)-Cifluoroalkyl, -S(0)n4-Me, -S(0)n4-Cifluoroalkyl, -NR19R20, or cyano;
provided that when X is NR4, then at least one of R3 and R4 (preferably R3) is hydrogen or CrC3alkyl; and provided that when X is CR5R6, then at least one of R3 and R5 (preferably R3) is hydrogen or CrC3alkyl; or R3 and R4 are taken together, and/or R3 and R5 are taken together, to form a chain which is (a), (b), (c), (d), (e), (f) or (g), as defined herein.
More preferably, e.g. in all aspects and/or embodiments of the invention, R4 and/or R5, independently of each other, is or are:
hydrogen, C-|-C3alkyl (in particular methyl or ethyl), C-|-C2fluoroalkyl (in particular Cifluoroalkyl), MeOCH2CH2-, MeSCH2CH2-, C C2alkoxy (in particular methoxy),
R9-C≡C-C(R7)(R8)-, or Het-CH2-; or
benzyl optionally substituted on its phenyl ring by 1 or 2 substituents independently being fluorine, chlorine, methyl, Cifluoroalkyl (preferably trifluoromethyl), methoxy,
C-ifluoroalkoxy (preferably trifluoromethoxy or difluoromethoxy), -C≡C-R13, or cyano; provided that when X is NR4, then at least one of R3 and R4 (preferably R3) is hydrogen or CrC3alkyl; and provided that when X is CR5R6, then at least one of R3 and R5 (preferably R3) is hydrogen or CrC3alkyl; or R3 and R4 are taken together, and/or R3 and R5 are taken together, to form a chain which is (a), (b), (c), (d), (e), (f) or (g), as defined herein.
Even more preferably, e.g. in all aspects and/or embodiments of the invention, R4 and/or R5, independently of each other, is or are: hydrogen, CrC3alkyl (in particular methyl or ethyl), R9-C≡C-C(R7)(R8)-, or Het-CH2-;
provided that when X is NR4, then at least one of R3 and R4 (preferably R3) is hydrogen or C Csalkyl; and provided that when X is CR5R6, then at least one of R3 and R5 (preferably R3) is hydrogen or d-C3alkyl; or R3 and R4 are taken together, and/or R3 and R5 are taken together, to form a chain which is (a), (b), (c), (d), (e), (f) or (g), as defined herein.
Preferably, e.g. in all aspects and/or embodiments of the invention, R3 is not hydrogen; and/or, preferably, R4 and/or R5 is or are not hydrogen.
In one particularly preferred embodiment of the invention:
R3 is C Csalkyl (preferably methyl or ethyl) or CrC2fluoroalkyl (in particular C-ifluoroalkyl); and/or
R4 and/or R5 is or are, independently, CrC3alkyl (preferably methyl or ethyl) or
CrC2fluoroalkyl (in particular C-ifluoroalkyl).
Preferably, e.g. in all aspects and/or embodiments of the invention, Het is a heteroaryl (in particular monocyclic 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 Ci-C2alkyl, Cifluoroalkyl, CrC2alkyl-C(0)-, Cifluoroalkyl-CiO)-, ethynyl, prop-1-ynyl, CrC2alkoxy, C-ifluoroalkoxy, fluorine, chlorine, bromine, cyano or nitro, provided that any chlorine, bromine, alkoxy or fluoroalkoxy is not substituted at any ring-carbon bonded directly to a ring-nitrogen of the heteroaryl;
and/or, in the case of a 5-membered heteroaryl ring containing a ring-nitrogen atom not partaking in a C=N ring double bond, the heteroaryl is optionally substituted on the ring- nitrogen atom not partaking in a C=N ring double bond by one CrC3alkyl, CrC2fluoroalkyl, C C3alkyl-C(0)-, C C2fluoroalkyl-C(0)- or Ci-C2alkyl-S(0)2- substituent.
More preferably, e.g. in all aspects and/or embodiments of the invention, Het is a heteroaryl (in particular monocyclic heteroaryl), attached at a ring-carbon, which is optionally substituted by 1 or 2 (in particular 1 ) ring-carbon substituents independently being Ci-C2alkyl (in particular methyl), Cifluoroalkyl (in particular CF3), C C2alkyl-C(0)- (in particular Me-C(O)-), Cifluoroalkyl-C(O)-, ethynyl, prop-1 -ynyl, fluorine or cyano;
and/or, in the case of a 5-membered heteroaryl ring containing a ring-nitrogen atom not partaking in a C=N ring double bond, the heteroaryl is optionally substituted on the ring- nitrogen atom not partaking in a C=N ring double bond by one CrC2alkyl (e.g. methyl), Cifluoroalkyl, methyl-C(O)- or Cifluoroalkyl-C(O)- substituent.
More preferably, e.g. in all aspects and/or embodiments of the invention, Het is a heteroaryl (in particular monocyclic heteroaryl), attached at a ring-carbon, which is optionally substituted by 1 or 2 (in particular 1 ) ring-carbon substituents independently being C-|-C2alkyl (in particular methyl), Cifluoroalkyl (in particular CF3), fluorine or cyano;
and/or, in the case of a 5-membered heteroaryl ring containing a ring-nitrogen atom not partaking in a C=N ring double bond, the heteroaryl is optionally substituted on the ring- nitrogen atom not partaking in a C=N ring double bond by one methyl substituent.
Preferably, e.g. in all aspects and/or embodiments of the invention, Het is an optionally substituted monocyclic heteroaryl, attached at a ring-carbon. Such as monocyclic heteroaryl can be 5-membered or 6-membered monocyclic heteroaryl.
More preferably, e.g. in all aspects and/or embodiments of the invention, Het is an optionally substituted monocyclic heteroaryl, attached at a ring-carbon, which is:
pyridinyl (preferably pyridin-3-yl or most preferably pyridin-2-yl), pyrazolyl (preferably pyrazol- 5-yl or pyrazol-4-yl, or most preferably pyrazol-3-yl), imidazolyl (preferably imidazol-2-yl), pyrazinyl, pyrimidinyl (preferably pyrimidin-4-yl), pyridazinyl (preferably pyridazin-3-yl), triazolyl (e.g. 1 ,2,3-triazolyl), tetrazol-5-yl, oxazolyl, thiazolyl, isoxazolyl, isothiazolyl or oxadiazolyl.
Even more preferably, e.g. in all aspects and/or embodiments of the invention, Het is an optionally substituted monocyclic heteroaryl, attached at a ring-carbon, which is:
pyridinyl (preferably pyridin-3-yl or most preferably pyridin-2-yl), pyrazolyl (preferably pyrazol- 5-yl or pyrazol-4-yl, or most preferably pyrazol-3-yl), imidazolyl (preferably imidazol-2-yl), pyrazinyl, pyrimidinyl (preferably pyrimidin-4-yl), pyridazinyl (preferably pyridazin-3-yl), triazolyl (e.g. 1 ,2,3-triazolyl), or tetrazol-5-yl.
Still more preferably, e.g. in all aspects and/or embodiments of the invention, Het is an optionally substituted monocyclic heteroaryl, attached at a ring-carbon, which is:
pyridinyl (preferably pyridin-3-yl or most preferably pyridin-2-yl), pyrazolyl (preferably pyrazol- 5-yl or pyrazol-4-yl, or most preferably pyrazol-3-yl), imidazolyl (preferably imidazol-2-yl), pyrazinyl, pyrimidinyl (preferably pyrimidin-4-yl), or pyridazinyl (preferably pyridazin-3-yl).
Yet more preferably, e.g. in all aspects and/or embodiments of the invention, Het is an optionally substituted monocyclic heteroaryl, attached at a ring-carbon, which is:
pyridin-3-yl, pyridin-2-yl, pyrazinyl, or pyrazolyl (preferably pyrazol-5-yl or pyrazol-4-yl, or most preferably pyrazol-3-yl).
Most preferably, e.g. in all aspects and/or embodiments of the invention, Het is an optionally substituted monocyclic heteroaryl, attached at a ring-carbon, which is: optionally substituted pyridin-2-yl, optionally substituted pyrazinyl or optionally substituted pyrazol-3-yl.
When Het or Het-CH2- is present in the compound of formula (I) and Het is a basic heteroaryl group (e.g. pyridinyl, e.g. pyridin-2-yl, or another basic heteroaryl group), then the compound of formula (I) can be optionally present as an agrochemically acceptable salt thereof (and preferably can be present as an agrochemically acceptable acid addition salt thereof such as a hydrohalide, e.g. hydrochloride, salt thereof).
It is particularly preferred (e.g. in all aspects and/or embodiments of the invention) that, in Het, any ring-carbon atom, which is directly bonded to the ring-carbon atom which is the point of attachment (e.g. or i.e. which is the point of attachment to the central carbon atom within the Y = CR8R9 moiety (for Het), or which is the point of attachment to the -CH2- moiety (for Het-CH2-), is unsubstituted. Therefore, for example, preferably, when Het is an optionally substituted pyridin-2-yl (optionally present as an agrochemically acceptable salt thereof), then the ring-carbon atom at the 3-position of the ring (calculated with respect to the pyridine ring nitrogen atom) is unsubstituted.
Preferably, e.g. in all aspects and/or embodiments of the invention, Het is one of the heteroaryls illustrated below:
Figure imgf000029_0001
Particularly preferably, e.g. in all aspects and/or embodiments of the invention, Het is one of the heteroaryls illustrated below:
Figure imgf000029_0002
Most preferably, e.g. in all aspects and/or embodiments of the invention, Het is one of the heteroaryls illustrated below:
Figure imgf000030_0001
Preferably, e.g. in all aspects and/or embodiments of the invention, R7 and R8 are both hydrogen.
Preferably, e.g. in all aspects and/or embodiments of the invention, R9 is hydrogen or methyl, more preferably hydrogen.
Preferably, e.g. in all aspects and/or embodiments of the invention, R10 is hydrogen.
Preferably, e.g. in all aspects and/or embodiments of the invention, R11 and R12,
independently of each other, are hydrogen or methyl. More preferably, one or both of R11 and R12 is or are hydrogen.
Preferably, e.g. in all aspects and/or embodiments of the invention, R13 is hydrogen or methyl, more preferably hydrogen.
Preferably, e.g. in all aspects and/or embodiments of the invention, R14 is hydrogen; and/or, preferably, R15 is hydrogen or fluorine; and/or, preferably, R16 is hydrogen, methyl or fluorine; provided that, in each case, R14, R15 and R16 in total contain no more than one carbon atom, and R14, R15 and R16 in total comprise no more than one chlorine.
Preferably, e.g. in all aspects and/or embodiments of the invention, n4 is 2.
Preferably, e.g. in all aspects and/or embodiments of the invention, n5 is 2.
Preferably, e.g. in all aspects and/or embodiments of the invention, R17 and/or R18 independently are C1-C2alkyl (in particular methyl), CifluoroalkyI (in particular trifluoromethyl), or -NR19AR: More preferably, R17 and/or R18 independently are methyl or dfluoroalkyl (in particular methyl or trifluoromethyl).
Preferably, e.g. in all aspects and/or embodiments of the invention, n18 is 2.
Preferably, e.g. in all aspects and/or embodiments of the invention, R19 is -C(0)-methyl, - C(0)-dfluoroalkyl (in particular -C(O)-trifluoromethyl), -S(0)2-methyl, -S(0)2-C1fluoroalkyl (in particular -S(0)2-trifluoromethyl), methyl, or C-ifluoroalkyl (in particular trifluoromethyl).
Preferably, e.g. in all aspects and/or embodiments of the invention, R20 and R20A
independently are hydrogen, methyl or trifluoromethyl.
Preferably, e.g. in all aspects and/or embodiments of the invention, R19A is hydrogen, methyl or trifluoromethyl.
In one preferred embodiment of the invention, R3 and R4 are taken together, and/or R3 and R5 are taken together, to form a chain which is (a), (b), (c), (d), (e), (f) or (g), as shown below:
-C(R^)(R^)-C(R^)(R^4)-Y-C(R^)(R^)-C(R^)(R )- (a)
-C(R21)(R22)-Y-C(R21A)(R22A)-C(R21A)(R22A)-C(R27)(R28)- (b)
-CH(R29)-Y-C(R21A)(R22A)-CH(R32)- (c)
-CH(R29)-Y-CH(R32)- (d)
-C(R21)(R22)-C(R23)(R24)-C(R30)(R31)-C(R25)(R26)-C(R27)(R28)- (e)
-C(R21)(R22)-C(R21A)(R22A)-C(R30)(R31)-C(R27)(R28)- (f)
-CH(R29)-C(R30)(R31)-CH(R32)- (g) wherein Y is O or NR4U.
R3 and R4 being taken together, and/or R3 and R5 being taken together, to form a chain is a preferred embodiment of the invention (i.e. is preferred in all aspects and/or embodiments of the invention).
Preferably, when R3 and R4 are taken together, and/or R3 and R5 are taken together, to form a chain, then the chain is (a), (d), (e), (f) or (g), more preferably (a), (e), (f) or (g), more preferably (a), (e) or (g), most preferably (a) or (e), as defined herein. Preferably, e.g. in all aspects and/or embodiments of the invention, Y is O; and/or R is CrC3alkoxy such as methoxy.
Preferably, e.g. in all aspects and/or embodiments of the invention, all of R21, R22, R27 and R28 are hydrogen. In this preferred embodiment, more preferably Y is O and/or R40 is CrC3alkoxy; and/or more preferably R3 and R4 are taken together, and/or R3 and R5 are taken together, to form a chain which is (a), (d), (e), (f) or (g), more preferably (a), (e), (f) or (g), more preferably (a), (e) or (g), most preferably (a) or (e), as defined herein.
Preferably, e.g. in all aspects and/or embodiments of the invention, R21A and R22A are both hydrogen. In this preferred embodiment, more preferably Y is O and/or R40 is CrC3alkoxy; and/or more preferably R3 and R4 are taken together, and/or R3 and R5 are taken together, to form a chain which is (a), (d), (e), (f) or (g), more preferably (a), (e), (f) or (g), more preferably (a), (e) or (g), most preferably (a) or (e), as defined herein.
Preferably, e.g. in all aspects and/or embodiments of the invention, R29 and R32 are both hydrogen. In this preferred embodiment, more preferably Y is O and/or R40 is CrC3alkoxy; and/or more preferably R3 and R4 are taken together, and/or R3 and R5 are taken together, to form a chain which is (a), (d), (e), (f) or (g), more preferably (a), (e), (f) or (g), more preferably (a), (e) or (g), most preferably (a) or (e), as defined herein.
Preferably, e.g. in all aspects and/or embodiments of the invention, R30 is hydrogen or methoxy, more preferably hydrogen. Preferably, e.g. in all aspects and/or embodiments of the invention, R31 is hydrogen. In these preferred embodiments of R30 and/or R31, more preferably Y is O and/or R40 is C-i-C3alkoxy; and/or more preferably R3 and R4 are taken together, and/or R3 and R5 are taken together, to form a chain which is (a), (d), (e), (f) or (g), more preferably (a), (e), (f) or (g), more preferably (a), (e) or (g), most preferably (a) or (e), as defined herein.
Preferably, e.g. in all aspects and/or embodiments of the invention, all of R23, R24, R25 and R26 are hydrogen. In this preferred embodiment, more preferably Y is O and/or R40 is C-i-C3alkoxy; and/or more preferably R3 and R4 are taken together, and/or R3 and R5 are taken together, to form a chain which is (a), (d), (e), (f) or (g), more preferably (a), (e), (f) or (g), more preferably (a), (e) or (g), most preferably (a) or (e), as defined herein. More preferably, e.g. in all aspects and/or embodiments of the invention, all of R21, R22, R27 and R28 are hydrogen, R21A and R22A are both hydrogen, and R29 and R32 are both hydrogen. In this more preferred embodiment, even more preferably, Y is O and/or R40 is CrC3alkoxy; and/or even more preferably R3 and R4 are taken together, and/or R3 and R5 are taken together, to form a chain which is (a), (d), (e), (f) or (g), more preferably (a), (e), (f) or (g), more preferably (a), (e) or (g), most preferably (a) or (e), as defined herein.
Most preferably, e.g. in all aspects and/or embodiments of the invention, all of R21, R21A, R22, R22A, R23, R24, R25, R26, R27, R28, R29, R30, R31 and R32 are hydrogen. In this most preferred embodiment, even more preferably, Y is O and/or R40 is CrC3alkoxy; and/or even more preferably R3 and R4 are taken together, and/or R3 and R5 are taken together, to form a chain which is (a), (d), (e), (f) or (g), more preferably (a), (e), (f) or (g), more preferably (a), (e) or (g), most preferably (a) or (e), as defined herein.
Preferably, e.g. in all aspects and/or embodiments of the invention, R is CrC3alkoxy. More preferably, R40 is methoxy.
In a particularly preferable embodiment of the invention (which e.g. can apply to all aspects and/or embodiments of the invention), the compound of formula (I) is one of compounds A1 to A141 , as described and/or illustrated herein, optionally present (e.g. where chemically possible) as an agrochemically acceptable salt thereof. In an alternative particularly preferable embodiment of the invention (which e.g. can apply to all aspects and/or embodiments of the invention), the compound of formula (I) is one of compounds A142 to A149, or P1 to P12, or A150 or A151 , as described and/or illustrated herein, optionally present (e.g. where chemically possible) as an agrochemically acceptable salt thereof.
In a more particularly preferable embodiment of the invention (which e.g. can apply to all aspects and/or embodiments of the invention), the compound of formula (I) is one of compounds A1 to A1 1 1 , as described and/or illustrated herein, optionally present (e.g. where chemically possible) as an agrochemically acceptable salt thereof. In an alternative more particularly preferable embodiment of the invention (which e.g. can apply to all aspects and/or embodiments of the invention), the compound of formula (I) is one of compounds P1 to P12 (preferably one of compounds P1 to P5), or one of compounds A142 to A149, or compound A150 or A151 , as described and/or illustrated herein, optionally present (e.g. where chemically possible) as an agrochemically acceptable salt thereof.
In one yet more particularly preferable embodiment of the invention (which e.g. can apply to all aspects and/or embodiments of the invention), the compound of formula (I) is one of compounds A1 to A12 (preferably compound A2, A6, A8 or A9, more preferably compound A2 or A8), as described and/or illustrated herein, optionally present (e.g. where chemically possible) as an agrochemically acceptable salt thereof.
In another yet more particularly preferable embodiment of the invention (which e.g. can apply to all aspects and/or embodiments of the invention), the compound of formula (I) is compound A13, A14 or A15 (more preferably compound A14), as described and/or illustrated herein, optionally present (e.g. where chemically possible) as an agrochemically acceptable salt thereof.
In another yet more particularly preferable embodiment of the invention (which e.g. can apply to all aspects and/or embodiments of the invention), the compound of formula (I) is compound A22, A23 or A24 (more preferably compound A23 or A24), as described and/or illustrated herein, optionally present (e.g. where chemically possible) as an agrochemically acceptable salt thereof.
In another yet more particularly preferable embodiment of the invention (which e.g. can apply to all aspects and/or embodiments of the invention), the compound of formula (I) is one of compounds A25 to A39 (or more preferably one of compounds A25 to A36, or even more preferably compound A25, A26, A27, A28, A29, A29A, A30, A30A, A31 , A32, A32A, A33 or A33A, or yet more preferably compound A25, A26, A27, A28, A29, A29A, A30 or A30A, or further more preferably compound A26, A28, A29 or A29A, or particularly preferably compound A26 or A29, or most preferably compound A29), as described and/or illustrated herein, optionally present (e.g. where chemically possible) as an agrochemically acceptable salt thereof.
In another particularly preferable embodiment of the invention (which e.g. can apply to all aspects and/or embodiments of the invention), the compound of formula (I) is one of compounds A40 to A84, as described and/or illustrated herein, optionally present (e.g. where chemically possible) as an agrochemically acceptable salt thereof.
In another particularly preferable embodiment of the invention (which e.g. can apply to all aspects and/or embodiments of the invention), the compound of formula (I) is one of compounds A85 to A99, as described and/or illustrated herein, optionally present (e.g. where chemically possible) as an agrochemically acceptable salt thereof.
In another yet more particularly preferable embodiment of the invention (which e.g. can apply to all aspects and/or embodiments of the invention), the compound of formula (I) is one of compounds P1 to P12 (or more preferably one of compounds P1 to P5, or most preferably compound P3 or P5), as described and/or illustrated herein, optionally present (e.g. where chemically possible) as an agrochemically acceptable salt thereof.
In another yet more particularly preferable embodiment of the invention (which e.g. can apply to all aspects and/or embodiments of the invention), the compound of formula (I) is one of compounds A142 to A149 (or more preferably compound A142, A144, A146 or A148), or compound A150 or A151 , as described and/or illustrated herein, optionally present (e.g. where chemically possible) as an agrochemically acceptable salt thereof.
In another yet more particularly preferable embodiment of the invention (which e.g. can apply to all aspects and/or embodiments of the invention), the compound of formula (I) is one of compounds A1 to A12 (e.g. A2, A6, A8 or A9),
or A13, A14, A15, A22, A23 or A24 (e.g. A14, A23 or A24),
or A25 to A36 (e.g. A25, A26, A27, A28, A29, A29A, A30, A30A, A31 , A32, A32A, A33 or A33A, e.g. A26, A28, A29 or A29A),
or A142 to A149 (e.g. A142, A144, A146 or A148), or A150 or A151 ,
or P1 to P12 (e.g. P1 to P5),
as described and/or illustrated herein, optionally present as an agrochemically acceptable salt thereof.
In another yet more particularly preferable embodiment of the invention (which e.g. can apply to all aspects and/or embodiments of the invention), the compound of formula (I) is one of compounds A1 to A12 (e.g. A2, A6, A8 or A9), or A13, A14, A15, A22, A23 or A24 (e.g. A14, A23 or A24),
or A25, A26, A27, A28, A29, A29A, A30, A30A, A31 , A32, A32A, A33 or A33A (e.g. A26, A28, A29 or A29A),
or A142 to A149 (e.g. A142, A144, A146 or A148), or A150 or A151 ,
or P1 to P12 (e.g. P1 to P5),
as described and/or illustrated herein, optionally present as an agrochemically acceptable salt thereof.
In another yet more particularly preferable embodiment of the invention (which e.g. can apply to all aspects and/or embodiments of the invention), the compound of formula (I) is one of compounds A1 to A12 (e.g. A2, A6, A8 or A9),
or A13, A14, A15, A22, A23 or A24 (e.g. A14, A23 or A24),
or A25, A26, A27, A28, A29, A29A, A30, A30A, A31 , A32, A32A, A33 or A33A (e.g. A26, A28, A29 or A29A),
or A142 to A149 (e.g. A142, A144, A146 or A148),
or P1 to P12 (e.g. P1 to P5),
as described and/or illustrated herein, optionally present as an agrochemically acceptable salt thereof.
Depending on the nature of the substituents G, R1, R2, R3, X, R4, R5, and R6, 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 (A), (AA), and/or (B):
Figure imgf000036_0001
Also, when substituents contain double bonds, cis- and trans-isomers can exist. The compounds of formula (I) of the present invention cover all such tautomers and/or isomers, and mixtures thereof, in all proportions. Processes for preparation of compounds, e.g. compounds of formula (I)
The present invention covers a compound of formula (I) (which optionally agrochemically acceptable salt thereof :
wherein CKE is either
Figure imgf000037_0001
, or wherein CKE is a mixture of sub-formulae (A) and (B) e.g. in any molar ratio.
Processes for preparation of a compound of formula (I) (which optionally can be an agrochemically acceptable salt thereof), are now described, and these processes form further aspects of the present invention.
Figure imgf000037_0002
A compound of formula (I), in particular a compound of formula (I-A1 ) and/or (I-B1 ) or a compound of formula (I-A2) and/or (I-B2), wherein G is:
-C(Xa)-Ra, -C(Xb)-Xc-Rb, -C(Xd)-N(Rc)-Rd, -S02-Re, -P(Xe)(R )-R9, -CH2-Xf-Rh; or
phenyl-CH2- or phenyl-CH(C1-C2alkyl)- (in each of which the phenyl is optionally substituted by 1 , 2 or 3 of, independently, d-C2alkyl, dfluoroalkyl, CrC2alkoxy, Cifluoroalkoxy, fluorine, chlorine, bromine, cyano or nitro), or heteroaryl-CH2- or heteroaryl-CH(C1-C2alkyl)- (in each of which the heteroaryl is optionally substituted by 1 , 2 or 3 of, independently, C-|-C2alkyl, C-ifluoroalkyl, C-|-C2alkoxy, C-ifluoroalkoxy, fluorine, chlorine, bromine, cyano or nitro), or phenyl-C(0)-CH2- (wherein the phenyl is optionally substituted by 1 , 2 or 3 of, independently, C-|-C2alkyl, C-ifluoroalkyl, C-|-C2alkoxy, C-ifluoroalkoxy, fluorine, chlorine, bromine, cyano or nitro); or CrC6alkoxy-C(0)-CH2-, CrC6alkoxy-C(0)-CH=CH-, C2-C7alken-1-yl-CH2-,
C2-C7alken-1 -yl-CH(C C2alkyl)-, C2-C4fluoroalken-1 -yl-CH2-, C2-C7alkyn-1-yl-CH2-, or C2-C7alkyn-1 -yl-CH(C C2alkyl)-; may be prepared:
- (to prepare a compound of formula (I-A1 ) and/or (I-B1 )) either by treating a compound of formula (C), which is a compound of formula (I-A1 ) or (I-B1 ) wherein G is H, or
- (to prepare a compound of formula (I-A2) and/or (I-B2)) by treating a compound of formula (P), which is a compound of formula (I-A2) or (I-B2) wherein G is H,
(a) with a reagent G1-Z, wherein G1-Z is an alkylating agent (wherein G1 is an organic group according to G within the compound of formula (I) and which is linked by a non-carbonyl, non-thiocarbonyl carbon atom) such as an organic halide (in which Z = halogen such as chlorine, bromine or iodine); wherein the organic halide (e.g. chloride) can typically be a substituted alkyl halide (e.g. chloride) such as a chloromethyl alkyl ether CI— CH2-X -Rh wherein X is oxygen, a chloromethyl alkyl sulfide CI— CH2-X -Rh wherein X is sulphur, a suitable optionally substituted benzyl halide (e.g. chloride) su ch as CI-CH2-[optionally substituted phenyl], [optionally substituted phenyl]-C(0)-CH2-[halogen e.g. CI], C C6alkoxy-C(0)-CH2-[halogen e.g. CI], C C6alkoxy-C(0)-CH=CH-[halogen e.g. CI], a suitable alkenyl or alkynyl halide (e.g. chloride) such as C2-C7alken-1 -yl-CH2-[halogen e.g. CI] or C2-C7alkyn-1 -yl-CH2-[halogen e.g. CI], or another organic halide suitable for preparing a (non-carbonyl, non-thiocarbonyl carbon)-linked G (or G1 ) group; or (b) [e.g. to prepare carbonyl-carbon-linked or thiocarbonyl-carbon-linked G groups] with an acylating agent such as a carboxylic acid, HO-C(Xa)Ra, wherein Xa is oxygen, an acid chloride, CI-C(Xa)Ra, wherein Xa is oxygen, or an acid anhydride, [RaC(Xa)]20, wherein Xa is oxygen, or an isocyanate, RcN=C=0, or a carbamoyl chloride, CI-C(Xd)-N(Rc)-Rd (wherein Xd is oxygen and with the proviso that neither Rc or Rd is hydrogen), or a thiocarbamoyi chloride CI-(Xd)-N(Rc)-Rd (wherein Xd is sulfur and with the proviso that neither Rc or Rd is hydrogen), or a chloroformate, CI-C(Xb)-Xc-Rb (wherein Xb and Xc are oxygen), or a chlorothioformate Cl- C(Xb)-Xc-Rb (wherein Xb is oxygen and Xc is sulfur), or a chlorodithioformate CI-C(Xb)-Xc-Rb (wherein Xb and Xc are sulfur), or an isothiocyanate, RCN=C=S; or
(c) by sequential treatment with carbon disulfide and an alkylating agent; or
(d) with a phosphorylating agent such as a phosphoryl chloride, CI-P(Xe)(R )-R9; or
(e) with a sulfonylating agent such as a sulfonyl chloride Cl-S02— Re, preferably in the presence of at least one equivalent of base.
The O-alkylation of cyclic 1 ,3-diones is known; suitable methods are described, for example, by T. Wheeler, US4436666. Alternative procedures have been reported by M. Pizzorno and S. Albonico, Chem. Ind. (London), (1972), 425-426; H. Born et al., J. Chem. Soc, (1953), 1779-1782; M. G. Constantino et al., Synth. Commun., (1992), 22 (19), 2859-2864; Y. Tian et al., Synth. Commun., (1997), 27 (9), 1577-1582; S. Chandra Roy et al., Chem. Letters, (2006), 35 (1 ), 16-17; P. K. Zubaidha et al., Tetrahedron Lett., (2004), 45, 7187-7188.
The O-acylation of cyclic 1 ,3-diones may be effected e.g. by procedures similar to those described, for example, by R. Haines, US4175135, and by T. Wheeler, US4422870,
US4659372 and US4436666. Typically diones of formula (A) may be treated with an acylating agent preferably in the presence of at least one equivalent of a suitable base, and optionally in the presence of a suitable solvent. The base may be inorganic, such as an alkali metal carbonate or hydroxide, or a metal hydride, or an organic base such as a tertiary amine or metal alkoxide. Examples of suitable inorganic bases include sodium carbonate, sodium or potassium hydroxide, sodium hydride, and suitable organic bases include trialkylamines, such as trimethylamine and triethylamine, pyridines or other amine bases such as 1 ,4-diazobicyclo[2.2.2]-octane and 1 ,8-diazabicyclo[5.4.0]undec-7-ene. Preferred bases include triethylamine and pyridine. Suitable solvents for this reaction are selected to be compatible with the reagents and include ethers such as tetrahydrofuran and 1 ,2- dimethoxyethane and halogenated solvents such as dichloromethane and chloroform.
Certain bases, such as pyridine and triethylamine, may be employed successfully as both base and solvent. For cases where the acylating agent is a carboxylic acid, acylation is preferably effected in the presence of a known coupling agent such as 2-chloro-1- methylpyridinium iodide, Λ/,Λ/'-dicyclohexylcarbodiimide, 1-(3-dimethylaminopropyl)-3- ethylcarbodiimide and Λ/,Λ/'-carbodiimidazole, and optionally in the presence of a base such as triethylamine or pyridine in a suitable solvent such as tetrahydrofuran, dichloromethane or acetonitrile. Suitable procedures are described, for example, by W. Zhang and G. Pugh, Tetrahedron Lett., (1999), 40 (43), 7595-7598; T. Isobe and T. Ishikawa, J. Org. Chem., (1999), 64 (19), 6984-6988 and K. Nicolaou, T. Montagnon, G. Vassilikogiannakis, C.
Mathison, J. Am. Chem. Soc, (2005), 127(24), 8872-8888.
Phosphorylation of cyclic 1 ,3-diones may be effected e.g. using a phosphoryl halide or thiophosphoryl halide and a base e.g. by procedures analogous to those described by L. Hodakowski, US4409153.
Sulfonylation of a compound of formula (A) may be achieved e.g. using an alkyl or aryl sulfonyl halide, preferably in the presence of at least one equivalent of base, for example by the procedure of C. Kowalski and K. Fields, J. Org. Chem., (1981 ), 46, 197-201.
Processes for the preparation of compounds of formula (I) in which X = NR4, such as a compound of formula (C)
Figure imgf000040_0001
(D) (C)
A compound of formula (C) can be prepared by reacting a compound of formula (D) with propyne, preferably in the presence of a suitable catalyst, optionally in the presence of a suitable additive, optionally in a suitable solvent e.g. at a suitable temperature. Suitable catalysts include transition metal salts or complexes of transition metal salts (for example palladium acetate, bis(triphenylphosphine) palladium(ll) dichloride,
tetrakis(triphenylphosphine)palladium(0), bis(triphenylphosphine) nickel(ll) dichloride and tris(acetylacetonato) iron(lll)), in an amount typically 0.001 -25% with respect to a compound of formula (D). Suitable additives include copper salts (for example copper(l) iodide in an amount typically 0.001 -50% with respect to a compound of formula (D)), and tetraalkyl ammonium salts. Suitable bases include diethylamine, triethylamine, piperidine and pyrrolidine, and suitable solvents include 1 ,4-dioxane, Λ/,/V-dimethylacetamide or N,N- dimethylformamide. Preferably the reaction is carried out using 0.05-10%
bis(triphenylphosphine) palladium(ll) dichloride (with respect to a compound of formula (D)), 0.05-10% triphenylphosphine (with respect to a compound of formula (D)), 0.05-25% copper(l) iodide (with respect to a compound of formula (D)), 5-200% tetrabutyl ammonium iodide (with respect to a compound of formula (D)), triethylamine and N,N- dimethylformamide at a temperature between 25°C to 150°C. Such a reaction is an example of a Sonogashira coupling and similar reactions are known in the literature (see for example F. Labrie, S. Gauthier, J. Cloutier, J. Mailhot, S. Potvin, S. Dion, J-Y. Sanceau, WO
2008124922; M. S. Viciu, S. P. Nolan, Modern Arylation Methods (2009), 183-220; R.
Chinchilla, C. Najera, Chemical Reviews (2007), 107(3), 874-922; I. P. Beletskaya, G. V. Latyshev, A. V. Tsvetkov, N. V. Lukashev, Tetrahedron Letters (2003), 44(27), 501 1 -5013 and J. Mao, G. Xie, M. Wu, J. Guo, S. Ji, Advanced Synthesis & Catalysis (2008), 350(16), 2477-2482). In an alternative approach a compound of formula (C) may be prepared from a compound of formula (D) by reaction with a propynyl transfer reagent such as 1 - propynyllithium, 1 -propynylmagnesium bromide, 1 -propynylmagnesium chloride, 1- propynylmagnesium iodide, 1 -propynylzinc chloride, 1-propynylzinc bromide, 1-propynylzinc iodide, tributylpropynylstannane, 1 -propyne-1-boronic acid (or ester thereof), 2-butynoic acid or 1-(trimethylsilyl)propyne, with a transition metal catalyst system under suitable conditions (see for example P. Wessig, G. Mueller, C. Pick, A. Matthes, Synthesis (2007), (3), 464-477; J. H. Chaplin, G. S. Gill, D. W. Grobelny, B. L. Flynn, G. Kremmidiotis, WO07087684; A. Akao, T. Tsuritani, S. Kii, K. Sato, N. Nonoyama, T. Mase, N. Yasuda, Synlett (2007), (1 ), 31 -36. A. Coelho Coton, E. Sotelo Perez, F. Guitian Rivera, A. Gil Gonzalez, WO
201 1048247; C. H. Oh, S. H. Jung, Tetrahedron Letters (2000), 41 (44), 8513-8516; D. Zhao, C. Gao, X. Su, Y. He, J. You, Y. Xue, Chemical Communications (2010), 46(47), 9049-9051 ; C. Yang, S. P. Nolan, Organometallics (2002), 21 (6), 1020-1022). In another set of preferred conditions a compound of formula (D) is reacted with 1-propynylmagnesium bromide in the presence of 0.05-10% bis(triphenylphosphine) palladium(ll) dichloride (with respect to a compound of formula (D)), in tetrahydrofuran at a temperature between 25°C and 100°C, as described by J. H. Chaplin, G. S. Gill, D. W. Grobelny, B. L. Flynn, G. Kremmidiotis, WO 07087684.
Figure imgf000042_0001
A compound of formula (D) can be prepared by reacting a compound of formula (E), wherein each RE is independently CrC6alkyl (preferably independently methyl or ethyl), and a hydrazine of formula (F), preferably by treatment in a suitable solvent, e.g. at a suitable temperature (including microwave heating), with or without the addition of a suitable base. Suitable solvents include alcohols, such as methanol or ethanol, tetrahydrofuran, or high boiling solvents such as toluene or xylene. Suitable bases, in greater than or sub- stoichiometric amounts, can be metal alkoxides, such as sodium methoxide, potassium methoxide, sodium ethoxide, potassium ethoxide, sodium tert-butoxide or potassium tert- butoxide, or organic amine bases such as 1 ,8-diazabicyclo[5.4.0]-undec-7-ene, triethylamine or diisopropylethylamine. Suitable temperatures can be from cooled below 0°C up to the boiling point of the solvent used. Similar reactions are known in the literature (see for example M. Muehlebach et al, Bioorganic and Medicinal Chemistry 2009, 17(12), 4241 , Sherif A.F. Rostom, Bioorganic and Medicinal Chemistry 2010, 18(7), 2767, K.H. Dudley et al, Journal of Heterocyclic Chemistry 1978, 15(6), 923). Hydrazines of formula (F) are known in the literature or can be prepared from known reagents using known methods.
Figure imgf000042_0002
A compound of formula (D) can alternatively be prepared by reacting a compound of formula (G) and a hydrazine of formula (F), preferably by treatment in a suitable solvent, e.g. at a suitable temperature (including microwave heating), preferably with a suitable base. Suitable solvents include high boiling solvents such as toluene or xylene. Suitable bases, in greater than or sub-stoichiometric amounts, can be organic amine bases such as 1 ,8- diazabicyclo[5.4.0]-undec-7-ene, triethylamine or diisopropylethylamine. Suitable
temperatures can be from cooled below 0°C up to the boiling point of the solvent used.
Similar reactions are known in the literature (see for example Maetzke, Thomas et al, WO00/078881 ).
Figure imgf000043_0001
A compound of formula (E) can be prepared by reacting a compound of formula (H), wherein RE is CrC6alkyl (preferably methyl or ethyl), and a carboxylic acid or ester equivalent, preferably by treatment in a suitable solvent, e.g. at a suitable temperature, preferably with a suitable base. Suitable solvents include, for example, 1 ,2-dimethoxyethane, tetrahydrofuran, 1 ,4-dioxane, diethyl ether, dibutyl ether, acetonitrile, dimethyl sulfoxide, N, N- dimethylformamide, benzene, toluene, methanol, ethanol, isopropanol or ie f-butanol, and is chosen to be compatible with the base under the reaction conditions. Suitable bases include metal alkoxides, such as sodium methoxide, sodium ethoxide, potassium tert-butoxide or sodium ie f-butoxide, metal hydrides, such as sodium hydride or potassium hydride, alkyl metals, such as n-butyl lithium, or metal amides, such as lithium diisopropylamide, lithium diisopropylamide, lithium hexamethyldisilazide or lithium 2,2,6,6-tetramethylpiperidide.
Suitable temperatures can be in a temperature range of -100°C up to the boiling point of the solvent used. Suitable carboxylic acid or ester equivalents are known or can be prepared from from known reagents using known methods (see for example Behera, Manoranjan et al, Tetrahedron Letters (2009) 53(9), 1060, Volonterio, Alessandro and Zanda, Matteo, Organic Letters (2007), 9(5) 841 , Levene, P.A. and Meyer, G.M., Organic Syntheses (1936) No.16, Shintani, Ryo et al, Organic Letters (2009) 1 1 (2), 457, Matulenko, Mark A. et al, Bioorganic and Medicinal Chemistry (2007), 15(4), 1586) and may include carbon dioxide,
chloroformates, for example methyl chloroformate or ethyl chloroformate, cyanoformates, such as methyl cyanoformate or ethyl cyanoformate, carbonates, for example dimethyl carbonate or diethyl carbonate, oxalates, such as diethyloxalate or dimethyloxalate, other equivalents include, for example, ethyl-1-imidazole carbamate. Compounds of formula (H) are known in the literature or can be prepared from known reagents using known methods.
Figure imgf000044_0001
(J) (K) (E)
A compound of formula (E), wherein each RE is independently C-|-C6alkyl (preferably independently methyl or ethyl), can alternatively be prepared by reacting a compound of formula (J) and a compound of formula (K), wherein each RE is independently C-|-C6alkyl (preferably independently methyl or ethyl), preferably by treatment in a suitable solvent, e.g. at a suitable temperature (including microwave heating), optionally with a suitable base, and preferably in the presence of a suitable catayst system. Suitable solvents include, for example, 1 ,2-dimethoxyethane, tetrahydrofuran, 1 ,4-dioxane, acetonitrile, dimethyl sulfoxide, N, /V-dimethylformamide, benzene, toluene, 1 -methyl-2-pyrrolidone or N, N- dimethylacetamide. Suitable bases, in greater than or sub-stoichiometric amounts, can be metal carbonates, such as potassium carbonate and cesium carbonate, metal hydroxides, such as barium hydroxide, metal hydrides, such as sodium hydride, or metal phosphates, such as tripotassium phosphate. Suitable catalyst systems include using metal salts and complexes of metal salts, such as copper (I) iodide, ferric acetylacetonate, palladium acetate, palladium (II) chloride, bis(triphenylphosphine) palladium(ll) dichloride,
tetrakis(triphenylphosphine)palladium(0), sodium tetrachloropalladate, with or without additives, such as organo phosphines, such as triphenyl phosphine or t-butylphosphine and salts thereof, copper (II) oxide or organic carboxylates, such as (S)-proline or 2-pyridine carboxylic acid. Similar reactions are known in the literature ( for example Reddy Chidipudi, Suresh et al, Angewandte Chemie International Edition (2012) 51 (48) 121 15, Breslow, Ronald et al, WO201 1 146855, Yip, Sau Fan et al, Organic Letters (2007), 9(17), 3469, Aramaendia, Maria A. et al, Tetrahedron Letters (2002), 43(15), 2847, Taillefer, Marc et al, WO2008004088. Compounds of formula (J) are known or can be prepared from known reagents using known methods. Compounds of formula (K) are known, for example dimethyl malonate or diethyl malonate, or can be prepared from from known reagents using known methods.
Figure imgf000045_0001
A compound of formula (G) can be prepared by treatment of a compound of formula (L) with an acid (e.g a suitable acid), preferably in a suitable solvent, e.g. at a suitable temperature. Suitable solvents include water. Suitable acids are mineral acids, for example concentrated sulfuric acid. Suitable temperatures can be from cooled below 0°C up to the boiling point of the solvent used. Similar reactions are known in the literature (see for example Maetzke, Thomas et al, WO00/078881 ).
Figure imgf000045_0002
A compound of formula (L) can be prepared by reacting a compound of formula (J) and malononitrile (CAS Reg. No. 109-77-3), for example using methods similar to those previously described. Similar reactions are known in the literature (see for example Zeller, Martin, WO2004/050607; Schnyder, Anita et al, Synlett (2006), 18, 3167; Gao, Chengwei et al, Synlett (2003) 1 1 , 1716; Makosza, Mieczyslaw and Chesnokov, Alexey, Tetrahedron (2008), 64(25), 5925).
Figure imgf000045_0003
Compounds of formula (C) can also be prepared by reacting compounds of formula (M), wherein each RE is independently C-|-C6alkyl (preferably independently methyl or ethyl), with hydrazines of formula (F), for example under conditions as previously described.
Figure imgf000046_0001
(E) (M)
Compounds of formula (M) can be prepared from compounds of formula (E), e.g. under conditions as previously described e.g. in the preparation of a compound of formula (C) from a compound of formula (D).
Figure imgf000046_0002
(N)
Compounds of formula (N) can be prepared from compounds of formula (L), e.g. under conditions as previously described e.g. in the preparation of a compound of formula (C) from a compound of formula (D).
Figure imgf000046_0003
Compounds of formula (O) can be prepared from compounds of formula (G), e.g. under conditions as previously described e.g. in the preparation of a compound of formula (C) from a compound of formula (D).
Figure imgf000046_0004
Compounds of formula (O) can alternatively be prepared from compounds of formula (N), e.g. under conditions as previously described.
Processes for the preparation of compounds of formula (I) in which X = CR5R6, such as a compound of formula (P)
Figure imgf000047_0001
A compound of formula (P) can be prepared from a compound of formula (Q), in particular under conditions as previously described (i.e. as described in the section entitled "Processes for the preparation of compounds of formula (I) in which X = NR4, such as a compound of formula (C)").
Figure imgf000047_0002
A compound of formula (Q) can be prepared by treatment of a compound of formula (R), wherein RR is C-|-C6alkyl (preferably methyl or ethyl), with a base (e.g. a suitable base), preferably in a suitable solvent, e.g. at a suitable temperature. The base may be inorganic such as an alkali metal carbonate or hydroxide or a metal hydride, or an organic base such as metal alkoxide. Suitable solvents for this reaction are selected to be compatible with the reagents and include toluene, ethers, such as tetrahydrofuran and 1 ,2-dimethoxyethane and halogenated solvents, such as dichloromethane and chloroform. Similar reactions are known in the literature (see for example WO2009/049851 ).
Figure imgf000048_0001
A compound of formula (R) can be prepared by reacting a compound of formula (S), wherein RR is CrC6alkyl (preferably methyl or ethyl), and a compound of formula (T) in the presence of base (e.g. triethylamine), preferably in a suitable solvent. Suitable solvents for this reaction are selected to be compatible with the reagents and include ethers, such as tetrahydrofuran and 1 ,2-dimethoxyethane, and halogenated solvents, such as dichloromethane and chloroform. Similar reactions are known in the literature (see for example WO2013/079672).
Figure imgf000048_0002
A compound of formula (P) can be prepared by reacting a compound of formula (U) with reagent R3-LG, where in LG represents a leaving group (e.g. halogen), in the presence of base in a suitable solvent. The base may be inorganic, such as a metal hydride, or an organic base, such as metal alkoxide. Suitable solvents for this reaction are selected to be compatible with the reagents and include toluene, ethers, such as tetrahydrofuran and 1 ,2- dimethoxyethane, and halogenated solvents, such as dichloromethane and chloroform.
Figure imgf000048_0003
(V) (T)
A compound of formula (T) can be prepared by reacting a compound of formula (V) with a suitable halogenating reagent (preferably phosphorous oxychloride, thionyl chloride or oxalyl chloride), preferably in a suitable solvent (e.g. dichloromethane). Compounds of formula (V) are known in the literature or can be prepared from known reagents using known methods.
Figure imgf000049_0001
Compounds of formula (P) can be prepared from a compound of formula (W), wherein RR is CrC6alkyl (preferably methyl or ethyl), in particular under conditions as previously described.
Figure imgf000049_0002
(S) (X) (W)
Compounds of formula (W) can be prepared from a compound of formula (S) and a compound of formula (X), wherein Hal is a halogen (preferably chlorine), in particular under conditions as previously described.
Figure imgf000049_0003
Compounds of formula (X) can be prepared from a compound of formula (Y), in particular under conditions as previously described.
Figure imgf000049_0004
(H) (V) (Y)
Compounds of formula (Y) can be prepared: either (i) from a compound of formula (H) (by replacing the halogen group on the phenyl with a prop-1-ynyl group, in particular under conditions as previously described, and then hydrolysing the ester to the carboxylic acid e.g. under conventional ester hydrolysis conditions), or (ii) from a compound of formula (V), in particular under conditions as previously described.
Figure imgf000050_0001
Compounds of formula (W) can be prepared from a compound of formula (R), in particular under conditions as previously described.
Further Processes for the preparation of compounds of formula (I) in which X = NR4, such as a compound of formula (C)
Figure imgf000050_0002
A compound of formula (C) can be prepared by treatment of a compound of formula (Z), wherein Rz is CrC6alkyl (preferably methyl or ethyl), with a base (e.g. a suitable base), preferably in a suitable solvent, e.g. at a suitable temperature and/or as described previously.
Figure imgf000051_0001
A compound of formula (Z) can be prepared by treatment of a compound of formula (AA), wherein Rz is C-|-C6alkyl (preferably methyl or ethyl), with a compound of formula (X), wherein Hal is a halogen (preferably chlorine), e.g. using conditions previously described. Compounds of formula (AA) are known in the literature or can be prepared from known reagents using known methods.
Figure imgf000051_0002
(AB) (D)
A compound of formula (D) can be prepared by treatment of a compound of formula (AB), wherein Rz is CrC6alkyl (preferably methyl or ethyl), with a base (e.g. a suitable base), preferably in a suitable solvent, e.g. at a suitable temperature and/or as described previously.
Figure imgf000051_0003
A compound of formula (AB) can be prepared by treatment of a compound of formula (AA), wherein Rz is C-|-C6alkyl (preferably methyl or ethyl), with a compound of formula (T), wherein Hal is a halogen (preferably chlorine), e.g. using conditions previously described. Herbicidal compositions
In another aspect, the present invention provides a herbicidal composition, e.g. for use in a method of controlling weeds (preferably monocotyledonous weeds such as more preferably grassy monocotyledonous weeds) in crops of useful plants, which composition comprises a compound of formula (I) as defined herein (e.g. a herbicidally effective amount thereof), and a substantially-inert agrochemically acceptable substance (e.g. an agrochemically acceptable carrier, diluent and/or solvent, an agrochemically acceptable adjuvant, an an agrochemically acceptable emulsifier / surfactant / surface-active substance, and/or another agrochemically acceptable additive).
In a further aspect, the present invention provides a herbicidal composition, e.g. for use in a method of controlling weeds (preferably monocotyledonous such as more preferably grassy monocotyledonous weeds) in crops of useful plants, comprising a compound of formula (I) as defined herein (e.g. a herbicidally effective amount thereof), and an agrochemically acceptable carrier, diluent and/or solvent.
In all aspects of the invention, the compound of the formula (I) is optionally present (e.g. where chemically possible) as an agrochemically acceptable salt thereof.
The compounds of formula (I) according to the invention can be used as crop protection agents in unmodified form, as obtained by synthesis, but, for use as herbicides, they are generally formulated into herbicidal compositions (formulations), e.g. in a variety of ways, containing one or more substantially-inert agrochemically acceptable substances (e.g. an agrochemically acceptable carrier, diluent and/or solvent, an agrochemically acceptable adjuvant, an an agrochemically acceptable emulsifier / surfactant / surface-active substance, and/or another agrochemically acceptable additive).
The formulations (herbicidal compositions) can be in various physical forms, for example in the form of dusting powders, gels, wettable powders, coated or impregnated granules for manual or mechanical distribution on target sites, water-dispersible granules, water-soluble granules, emulsifiable granules, water-dispersible tablets, effervescent compressed tablets, water-soluble tapes, emulsifiable concentrates, microemulsifiable concentrates, oil-in-water (EW) or water-in-oil (WO) emulsions, other multiphase systems such as oil/water/oil and water/oil/water products, oil flowables, aqueous dispersions, oily dispersions, suspoemulsions, capsule suspensions, soluble liquids, water-soluble concentrates (with water or a water-miscible organic solvent as carrier), impregnated polymer films or in other forms known, for example, from the Manual on Development and Use of FAO Specifications for Plant Protection Products, 5th Edition, 1999. The active ingredient may be incorporated into microfibers or micro-rods formed of polymers or polymerizable monomers and having diameter of about 0.1 to about 50 microns and aspect ratio of between about 10 and about 1000.
Such formulations (herbicidal compositions) can either be used directly or are diluted prior to use. They can then be applied through suitable ground or aerial application spray equipment or other ground application equipment such as central pivot irrigation systems or drip/trickle irrigation means. Diluted formulations can be prepared, for example, with water, liquid fertilisers, micronutrients, biological organisms, oil or solvents.
The formulations (herbicidal compositions) can be prepared, for example, by mixing the active ingredient with formulation adjuvants in order to obtain compositions in the form of finely divided solids, granules, solutions, dispersions or emulsions. The active ingredients can also be contained in fine microcapsules consisting of a core and a polymeric shell. Microcapsules usually have a diameter of from 0.1 to 500 microns. They contain active ingredients in an amount of about from 25 to 95 % by weight of the capsule weight. The active ingredients can be present in the form of liquid technical material, in the form of a suitable solution, in the form of fine particles in solid or liquid dispersion or as a monolithic solid. The encapsulating membranes comprise, for example, natural and synthetic gums, cellulose, styrene-butadiene copolymers or other similar suitable membrane forming material, polyacrylonitrile, polyacrylate, polyester, polyamides, polyureas, polyurethane, aminoplast resins or chemically modified starch or other polymers that are known to the person skilled in the art in this connection.
Alternatively it is possible for fine so called "microcapsules" to be formed wherein the active ingredient is present in the form of finely divided particles in a solid matrix of a base substance, but in that case the microcapsule is not encapsulated with a diffusion limiting membrane as outlined in the preceding paragraph. The active ingredients may be adsorbed on a porous carrier. This may enable the active ingredients to be released into their surroundings in controlled amounts (e.g. slow release). Other forms of controlled release formulations are granules or powders in which the active ingredient is dispersed or dissolved in a solid matrix consisting of a polymer, a wax or a suitable solid substance of lower molecular weight. Suitable polymers are polyvinyl acetates, polystyrenes, polyolefins, polyvinyl alcohols, polyvinyl pyrrolidones, alkylated polyvinyl pyrrolidones, copolymers of polyvinyl pyrrolidones and maleic anhydride and esters and half- esters thereof, chemically modified cellulose esters like carboxymethyl cellulose, methyl cellulose, hydroxyethyl cellulose, examples of suitable waxes are polyethylene wax, oxidized polyethylene wax, ester waxes like montan waxes, waxes of natural origin like carnauba wax, candelilla wax, bees wax etc. Other suitable matrix materials for slow release formulations are starch, stearin, or lignin.
The formulation ingredients (e.g. inert ingredients) suitable for the preparation of the compositions according to the invention are generally known per se.
As a liquid carrier and/or solvent (e.g. organic solvent), e.g. for use in the herbicidal composition(s) according to the invention, there may be used: water, an aromatic solvent such as toluene, m-xylene, o-xylene, p-xylene or a mixture thereof, cumene, an aromatic hydrocarbon blend with a boiling range between 140 and 320 °C (e.g. known under various trademarks such as Solvesso®, Shellsol A®, Caromax®, Hydrosol®), a paraffinic or isoparaffinic carrier such as paraffin oil, mineral oil, a de-aromatized hydrocarbon solvent with a boiling range between 50 and 320 °C (e.g. known for instance under the trademark Exxsol®), a non-dearomatized hydrocarbon solvent with a boiling range between 100 and 320 °C (e.g. known under the tradename Varsol®), an isoparaffinic solvent with a boiling range between 100 and 320 °C (e.g. known known under tradenames like Isopar® or Shellsol T®), a hydrocarbon such as cyclohexane, tetrahydronaphthalene (tetralin),
decahydronaphthalene, alpha-pinene, d-limonene, hexadecane, isooctane; an ester solvent such as ethyl acetate, n- or iso- butyl acetate, amyl acetate, /'-bornyl acetate, 2-ethylhexyl acetate, a C6 - Ci8 alkyl ester of acetic acid (e.g. known under the tradename Exxate®), lactic acid ethylester, lactic acid propylester, lactic acid butylester, benzyl benzoate, benzyl lactate, dipropyleneglycol dibenzoate, or a dialkyl ester of succinic, maleic or fumaric acid; a polar solvent such as /V-methyl pyrrolidone, /V-ethyl pyrrolidone, C3-Ci8-alkyl pyrrolidones, gamma- butyrolactone, dimethylsulfoxide, /V,/V-dimethylformamide, Λ/,/V-dimethylacetamide, N,N- dimethyllactamide, a C4-C18 fatty acid dimethylamide, benzoic acid dimethylamide, acetonitrile, acetone, methyl ethyl ketone, methyl-isobutyl ketone, isoamyl ketone, 2- heptanone, cyclohexanone, isophorone, methyl isobutenyl ketone (mesityl oxide), acetophenone, ethylene carbonate, propylene carbonate, or butylene carbonate;
an alcoholic solvent or diluent such as methanol, ethanol, propanol, n- or iso- butanol, n- or iso- pentanol, 2-ethyl hexanol, n-octanol, tetrahydrofurfuryl alcohol, 2-methyl-2,4- pentanediol, 4-hydroxy-4-methyl-2-pentanone, cyclohexanol, benzyl alcohol, ethylene glycol, ethylene glycol butyl ether, ethylene glycol methyl ether, diethylene glycol, diethylene glycol butyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether, propylene glycol, dipropylene glycol, dipropylene glycol monomethyl ether, or another similar glycol monoether solvent based on a ethylene glycol, propylene glycol or butylene glycol feedstock, triethylene glycol, polyethylene glycol (e.g. PEG 400), a polypropylenglycol with a molecular mass of 400 - 4000, or glycerol;
glycerol acetate, glycerol diacetate, glycerol triacetate, 1 ,4-dioxane, diethylene glycol abietate, chlorobenzene, chlorotoluene; a fatty acid ester such as methyl octanoate, isopropyl myristate, methyl laurate, methyl oleate, a mixture of C8-C10 fatty acid methyl esters, rapeseed oil methyl ester, rapeseed oil ethyl ester, soybean oil methyl ester, soybean oil ethyl ester; a vegetable oil (e.g. rapeseed oil or soybean oil); a fatty acid such as oleic acid, linoleic acid, or linolenic acid; or an ester of phosphoric or phosphonic acid such as triethyl phosphate, a C3-C18-tris-alkyl phosphate, an alkylaryl phosphate, or bis-octyl-octyl phosphonate.
Water is generally the liquid carrier of choice for the dilution of the concentrates.
Suitable solid carriers are, for example, talc, titanium dioxide, pyrophyllite clay, silica (fumed or precipated silica and optionally functionalised or treated, for instance silanised), attapulgite clay, kieselguhr, limestone, calcium carbonate, bentonite, calcium montomorillonite, cottonseed husks, wheatmeal, soybean flour, pumice, wood flour, ground walnut shells, lignin and similar materials, as described, for example, in the EPA CFR 180.1001 . (c) & (d). Powdered or granulated fertilisers can also be used as solid carriers.
A large number of surface-active substances can advantageously be used both in solid and in liquid formulations (herbicidal compositions), especially in those formulations (herbicidal compositions) which can be diluted with a carrier prior to use. Surface-active substances may be anionic, cationic, amphoteric, non-ionic or polymeric and they may be used as emulsifiying, wetting, dispersing or suspending agents or for other purposes. Typical surface- active substances include, for example, salts of alkyl sulfates, such as diethanolammonium lauryl sulfate or sodium lauryl sulfate; salts of alkylarylsulfonates, such as calcium or sodium dodecylbenzenesulfonate; alkylphenol-alkylene oxide addition products, such as nonylphenol ethoxylates; alcohol-alkylene oxide addition products, such as tridecyl alcohol ethoxylate; soaps, such as sodium stearate; salts of alkylnaphthalenesulfonat.es, such as sodium dibutylnaphthalenesulfonate; dialkyl esters of sulfosuccinate salts, such as sodium di(2- ethylhexyl)sulfosuccinate; sorbitol esters, such as sorbitol oleate; quaternary amines, such as lauryl trimethylammonium chloride; polyethylene glycol esters of fatty acids, such as polyethylene glycol stearate; block copolymers of ethylene oxide and propylene oxide; and salts of mono- and di-alkyl phosphate esters; and also further substances described e.g. in "McCutcheon's Detergents and Emulsifiers Annual", MC Publishing Corp., Ridgewood, New Jersey, 1981.
Further formulation ingredients (e.g. inert ingredients) which can typically be used in formulations (herbicidal compositions) include crystallisation inhibitors, viscosity-modifying substances, suspending agents, dyes, anti-oxidants, foaming agents, light absorbers, mixing aids, anti-foams, complexing agents, neutralising or pH-modifying substances and/or buffers, corrosion-inhibitors, fragrances, wetting agents, absorption improvers, micronutrients, plasticisers, glidants, lubricants, dispersants, thickeners, anti-freezes, microbiocides, compatibility agents and. or solubilisers; and/or also liquid and/or solid fertilisers.
The compositions (formulations) may also comprise additional active substances, for example further herbicides, herbicide safeners, plant growth regulators, fungicides or insecticides.
The compositions according to the invention can additionally include an additive (commonly referred to as an adjuvant), comprising a mineral oil, an oil of vegetable or animal origin, alkyl (e.g. CrC6alkyl) esters of such oils or mixtures of such oils and oil derivatives / oil esters. The amount of oil additive (oil adjuvant) used in the composition according to the invention is generally from 0.01 to 10 %, based on the spray mixture. For example, the oil additive (oil adjuvant) can be added to the spray tank in the desired concentration after the spray mixture has been prepared. Preferred oil additives (oil adjuvants) comprise mineral oils or an oil of vegetable origin, for example rapeseed oil, olive oil or sunflower oil, emulsifiable vegetable oil, such as AMIGO® (Loveland Products Inc.), CrC6alkyl esters of oils of vegetable origin, for example the methyl esters, or an oil of animal origin, such as fish oil or beef tallow. A preferred oil additive (oil adjuvant) contains methylated rapeseed oil
(rapeseed oil methyl ester). Another preferred oil additive (oil adjuvant) contains, for example, as active components essentially 80 % by weight alkyl esters of fish oils and 15 % by weight methylated rapeseed oil (rapeseed oil methyl ester), and also 5 % by weight of customary emulsifiers and pH modifiers. Especially preferred oil additives (oil adjuvants) comprise CrC6alkyl ester(s) of C8-C22 fatty acid(s), especially the methyl ester(s) of C8-C22 (especially Ci2-Ci8) fatty acid(s); preferably the methyl ester of lauric acid, of palmitic acid, or of oleic acid. Those esters are known as methyl laurate (CAS-1 1 1-82-0), methyl palmitate (CAS-1 12-39-0) and methyl oleate (CAS-1 12-62-9) respectively. A preferred fatty acid methyl ester derivative is AGNIQUE ME 18 RD-F® (e.g. available from Cognis). Those and other oil derivatives are also known from the Compendium of Herbicide Adjuvants, 5th Edition, Southern Illinois University, 2000.
The application and action of the above-mentioned oil additives (oil adjuvants) can be further improved by combining them with surface-active substances, such as non-ionic, anionic, cationic or amphoteric surfactants. Examples of suitable anionic, non-ionic, cationic or amphoteric surfactants, e.g. for this purpose, are listed on pages 7 and 8 of W097/34485. Preferred surface-active substances are anionic surfactants of the dodecylbenzylsulfonate type, especially the calcium salts thereof, and also non-ionic surfactants of the fatty alcohol ethoxylate type. As non-ionic sufactants, special preference is given to ethoxylated C12-C22 fatty alcohols preferably having a degree of ethoxylation of from 5 to 40. Examples of commercially available surfactants are the Genapol™ types (Clariant). Also preferred are silicone surfactants, especially polyalkyl-oxide-modified heptamethyltrisiloxanes, which are commercially available e.g. as SILWET L-77®, and also perfluorinated surfactants. The concentration of surface-active substances in relation to the total oil additive (oil adjuvant) is generally from 1 to 50 % by weight of the oil additive (oil adjuvant). Examples of oil additives (oil adjuvants) that consist of mixtures of oils and/or mineral oils and/or derivatives thereof with surfactants are TURBOCHARGE®, ADIGOR® (both (Syngenta Crop Protection AG), ACTIPRON® (BP Oil UK Limited), or AGRI-DEX® (Helena Chemical Company). The above-mentioned surface-active substances may also be used in the formulations alone, that is to say without oil additives (oil adjuvants).
Furthermore, the addition of an organic solvent to the oil additive (oil adjuvant) / surfactant mixture can contribute to a further enhancement of action. Suitable solvents are, for example, heavy aromatic hydrocarbon solvents such as SOLVESSO® or AROMATIC® solvents (Exxon Corporation). The concentration of such solvents can typically be from 10 to 80 % by weight of the oil additive (oil adjuvant). Such oil additives (oil adjuvants), which may be in admixture with solvents, are described, for example, in US 4 834 908. A commercially available oil additive disclosed therein is known by the name MERGE® (BASF). Further such oil additives (oil adjuvants) that are preferred according to the invention are SCORE® or ADIGOR® (both Syngenta Crop Protection AG).
In addition to the oil additives (oil adjuvants) listed above, in order to enhance the activity of the compositions according to the invention it is also possible for formulations of
alkylpyrrolidones, (e.g. AGRIMAX® from ISP) to be added to the spray mixture. Formulations of synthetic latices, such as, for example, polyacrylamide, polyvinyl compounds or poly-1 -p- menthene (e.g. BOND®, COURIER® or EMERALD®) can also be used.
A particularly preferred oil adjuvant (oil additive), e.g. for use in the herbicidal compositionas of the invention, is an emulsifiable concentrate which consists of:
(i) ethoxylated alcohols, which preferably includes ethoxylated C12-C22 fatty alcohols
(preferably having a degree of ethoxylation of from 5 to 40); and
(ii) a mixture of heavy aromatic hydrocarbons, which preferably includes (or more preferably includes 50% or more by weight of the heavy aromatic hydrocarbons of) a mixture of naphthalenes each of which is substituted by one or more alkyls wherein the alkyl(s) in total have 1 -4 carbon atoms per naphthalene molecule (e.g. Solvesso 200 ND™); and
(iii) methylated rapeseed oil (rapeseed oil methyl ester) (e.g. Agnique ME 18 RD-F™), as an adjuvant; preferably present at about 47% w/w and/or about 45% w/v of the oil adjuvant / oil additive / emulsifiable concentrate. One example of such a emulsifiable concentrate oil adjuvant (oil additive) is ADIGOR™, currently available in many countries from Syngenta.
When the above emulsifiable concentrate oil adjuvant is used, it is preferably added to the herbicidal composition after dilution (e.g. with water and/or in a spray tank), typically before application to weeds and/or to crops of useful plants and/or to the locus thereof. In one particular embodiment, the herbicidal composition, e.g. after dilution (e.g. with water and/or in a spray tank), contains the above emulsifiable concentrate oil adjuvant, and additionally ammonium sulphate and/or isopropyl alcohol.
Such adjuvant oils as described in the preceding paragraphs may be employed as the carrier liquid in which an active compound is dissolved, emulsified or dispersed as appropriate to the physical form of the active compound.
In an alternative particular embodiment, the herbicidal composition of the invention comprises an agrochemically acceptable adjuvant comprising 1 ,2-cyclohexane dicarboxylic acid di-isononyl ester (e.g. CAS Registry no. 166412-78-8), e.g. as available from BASF as Hexamoll™ DINCH™. "Isononyl" in this context is thought to mean one or more, preferably a mixture of two or more, branched isomers of C9H19. In one particular embodiment, the herbicidal composition, e.g. after dilution (e.g. with water and/or in a spray tank), contains 1 ,2-cyclohexane dicarboxylic acid di-isononyl ester, and additionally ammonium sulphate and/or isopropyl alcohol.
In an alternative particular embodiment, the herbicidal composition of the invention comprises an agrochemically acceptable adjuvant comprising an organic phosphate and/or organic phosphonate adjuvant. Preferably, the phosphate adjuvant is a tris-[C4-C12alkyl or 2-(C2-C6alkoxy)ethyl-] ester of phosphoric acid, or more preferably is tris-(2-ethylhexyl) phosphate, tris-n-octyl phosphate and/or tris-[2-(n-butoxy)ethyl] phosphate, or most preferably is tris-(2-ethylhexyl) phosphate. Preferably, the phosphonate adjuvant is a bis- (C3-Ci2alkyl) ester of a C3-Ci2alkyl-phosphonic acid, or more preferably is bis-(2-ethylhexyl) (2-ethylhexyl)phosphonate, bis-(2-ethylhexyl) (n-octyl)phosphonate and/or di-n-butyl (n-butyl)phosphonate.
The formulations (herbicidal compositions) generally contain from 0.1 to 99 % by weight, especially from 0.1 to 95 % by weight, of a compound of formula I, and from 1 to 99.9 % by weight of a substantially-inert agrochemically acceptable substance, which preferably includes a formulation adjuvant and/or from 0 to 30 % or from 0 to 25 % (in particular from 0.5 to 30 % or from 0.5 to 25 %) by weight of a surface-active substance. Whereas herbicidal compositions (especially commercial products) will preferably be formulated as concentrates, the end user will normally employ dilute formulations (compositions), e.g. formulations (compositions) diluted with water, in particular when applying the herbicidal composition to weeds and/or to crops of useful plants and/or to the locus thereof.
The rate of application of the compounds of formula I may vary within wide limits and depends upon the nature of the soil, the method of application (pre- or post-emergence; seed dressing; application to the seed furrow; no tillage application etc.), the crop plant, the weed or grass to be controlled, the prevailing climatic conditions, and other factors governed by the method of application, the time of application and the target crop. The compounds of formula I according to the invention are generally applied (preferably post-emergence) at a rate of from 1 to 2000 g/ha, preferably from 1 to 1000 g / ha and most preferably at from 1 to 500 g / ha or from 5 to 500 g/ha.
Preferred formulations / compositions have especially the following representative compositions:
(% = percent by weight of the composition):
Emulsifiable concentrates:
active ingredient: 0.3 to 95 %, preferably 0.5 to 60 % such as 1 to 40 % surface-active agents: 1 to 30 %, preferably 3 to 20% such as 5 to 15 % solvents as liquid carrier: 1 to 80 %, preferably 1 to 60% such as 1 to 40 %
Dusts:
active ingredient: 0.1 to 10 %, preferably 0.1 to 5 %
solid carriers: 99.9 to 90 %, preferably 99.9 to 99 %
Suspension concentrates
active ingredient: 1 to 75 %, preferably 3 to 50 % or 10 to 50 %
water: 98 to 24 %, preferably 95 to 30 % or 88 to 30 %
surface-active agents: 1 to 40 %, preferably 2 to 30 %
Wettable powders:
active ingredient: 0.5 to 90 %, preferably 1 to 80 %
surface-active agents: 0.5 to 20 %, preferably 1 to 15 %
solid carriers: 5 to 95 %, preferably 15 to 90 %
Granules:
active ingredient: 0.1 to 30 %, preferably 0.1 to 15 %
solid carriers: 99.5 to 70 %, preferably 97 to 85 % Waterdispersible granules:
active ingredient: 1 to 90 %, preferably 10 to 80 %
surface-active agents: 0.5 to 80 %, preferably 5 to 30 %
solid carriers: 90 to 10 %, preferably 70 to 30 %
The following Composition (Formulation) Examples further illustrate, but do not limit, the invention.
F1. Emulsifiable concentrates a) b) c) d)
active ingredient 5 % 10 % 25 % 50 %
calcium dodecylbenzene- sulfonate 6 % 8 % 6 % 8 %
castor oil polyglycol ether 4 % - 4 % 4 %
(36 mol of ethylene oxide)
octylphenol polyglycol ether - 4 % - 2 %
(7-8 mol of ethylene oxide)
NMP (N-methyl-2-pyrrolidone) - 10 % - 20 %
aromatic hydrocarbon 85 % 68 % 65 % 16 %
mixture C9-C12
Emulsions of any desired concentration can be prepared from such concentrates by dilution with water.
F2. Solutions a) b) c) d)
active ingredient 5 % 10 % 50 % 90 %
1 -methoxy-3-(3-methoxy- propoxy)-propane 40 % 50 %
polyethylene glycol MW 400 20 % 10 %
NMP (N-methyl-2-pyrrolidone) - - 50 % 10 %
aromatic hydrocarbon 35 % 30 %
mixture C9-C12
The solutions are suitable for application undiluted or after dilution with water. F3. Wettable powders a) b) c) d) active ingredient 5 % 25 % 50 % 80 %
sodium lignosulfonate 4 % - 3 %
sodium lauryl sulfate 2 % 3 % - 4 %
sodium diisobutylnaphthalene- sulfonate - 6 % 5 % 6 %
octylphenol polyglycol ether - 1 % 2 %
(7-8 mol of ethylene oxide)
highly disperse silicic acid 1 % 3 % 5 % 10 %
kaolin 88 % 62 % 35 %
The active ingredient is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable mill, yielding wettable powders which can be diluted with water to give suspensions of any desired concentration.
F4. Coated granules a) b) c)
active ingredient 0.1 % 5 % 15 %
highly dispersed silica 0.9 % 2 % 2 %
inorganic carrier 99.0 % 93 % 83 %
(diameter 0.1 - 1 mm)
e.g. CaC03 or Si02
The active ingredient is dissolved in methylene chloride, the solution is sprayed onto the carrier and the solvent is subsequently evaporated off in vacuo.
F5. Coated granules a) b) c)
active ingredient 0.1 % 5 % 15 %
polyethylene glycol MW 200 1 .0 % 2 % 3 %
highly dispersed silica 0.9 % 1 % 2 %
inorganic carrier 98.0 % 92 % 80 %
(diameter 0.1 - 1 mm)
e.g. CaC03 or Si02
The finely ground active ingredient is applied uniformly, in a mixer, to the carrier moistened with polyethylene glycol. Non-dusty coated granules are obtained in this manner. F6. Extruded granules a) b) c) d)
active ingredient 0.1 % 3% 5% 15%
sodium lignosulfonate 1.5 % 2% 3% 4%
carboxymethylcellulose 1.4 % 2% 2% 2%
kaolin 97.0 % 93 % 90 % 79 %
The active ingredient is mixed and ground with the adjuvants and the mixture is moistened with water. The resulting mixture is extruded and then dried in a stream of air.
F7. Water-dispersible qranules a) b) c) d)
active ingredient 5% 10 % 40 % 90 %
sodium lignosulfonate 20 % 20 % 15% 7 %
dibutyl naphthalene sulfonate 5% 5% 4% 2%
Gum arabic 2% 1 % 1 % 1 %
Diatomaceous earth 20 % 30 % 5% -
Sodium sulfate - 4% 5% - kaolin 48 % 30 % 30 %
The active ingredient is mixed and ground with the adjuvants and the mixture is moistened with water. The resulting mixture is extruded and then dried in a stream of air.
F8. Dusts a) b) c)
active ingredient 0.1 % 1 % 5%
talcum 39.9 % 49 % 35%
kaolin 60.0 % 50 % 60 %
Ready-to-use dusts are obtained by mixing the active ingredient with the carriers and grinding the mixture in a suitable mill.
F9. Suspension concentrates a) b) c) d)
active ingredient 3 % 10 % 25% 50%
propylene glycol 5% 5% 5% 5%
nonylphenol polyglycol ether - 1 % 2% -
(15 mol of ethylene oxide)
sodium lignosulfonate 3 % 3% 7 % 6 %
heteropolysacharide (Xanthan) 0.2 % 0.2 % 0.2 % 0.2 %
1 ,2-benzisothiazolin-3-one 0.1 % 0.1 % 0.1 % 0.1 % silicone oil emulsion 0.7 % 0.7 % 0.7 % 0.7 % water 88 % 80 % 60 % 38 %
The finely ground active ingredient is intimately mixed with the adjuvants, yielding a suspension concentrate from which suspensions of any desired concentration can be prepared by dilution with water.
Herbicidal uses - crops of useful plants, weeds, application rates, et al.
In a further aspect, the present invention provides a method of controlling weeds (preferably monocotyledonous such as more preferably grassy monocotyledonous weeds) in crops of useful plants, which comprises applying a compound of the formula (I), or a herbicidal composition comprising such a compound, to the weeds and/or to the plants and/or to the locus thereof. (Preferably, in this further aspect, the herbicidal composition can be as described hereinabove or hereinbelow, e.g. as described in the "Herbicidal compositions", "Herbicidal uses", "Combinations and mixtures" and/or Claims sections hereinabove or hereinbelow.)
In a further aspect, the present invention provides a herbicidal composition, in particular for use in a method of controlling weeds (preferably monocotyledonous weeds such as more preferably grassy monocotyledonous weeds) in crops of useful plants, comprising a compound of formula (I) as defined herein (e.g. a herbicidally effective amount thereof), and an agrochemically acceptable carrier, diluent and/or solvent.
In all aspects of the invention, the compound of the formula (I) is optionally present (e.g. where chemically possible) as an agrochemically acceptable salt thereof (e.g. agrochemically acceptable metal, sulfonium or ammonium salt).
In one embodiment, the herbicidal composition also comprises one or more further herbicides, e.g. as mixture partner(s) for the compound of formula (I), and/or a safener. See the combinations and mixtures section herein for more details of examples of these.
In all aspects of the invention (e.g. the methods of use of the invention), crops of useful plants, e.g. on or in which or at the locus of which the compounds or compositions according to the invention can be used, comprise (e.g. are), in particular: cereals (e.g. non-oat cereals, in particular non-oat non-sorghum non-millet cereals, more particularly wheat, barley, rye and/or triticale), rice, corn (maize), sugarcane, leguminous crops [preferably soybean, peanut, and/or pulse crops; more preferably soybean; wherein typically the pulse crops comprise dry beans (e.g. kidney or haricot or pinto bean which is Phaseolus vulgaris, or mung bean which is Vigna radiata), chickpea, blackeye bean (i.e. black-eyed pea, Vigna unguiculata), lentil, dry broad beans, and/or dry peas such as garden peas], cotton, rape (in particular oilseed rape or canola), sunflower, linseed, sugarbeet, fodder beet, potato, vegetables (preferably dicotyledonous vegetables), flax, tobacco, plantation crops (such as conifer trees, olives and/or olive trees, oil palms, coffee, or vines), and/or fruit crops (in particular dicotyledonous and/or broadleaved fruit, and/or in particular pome fruit, stone fruit, bush fruit, citrus fruit, pineapple, banana, and/or strawberry); and/or turf and/or pastureland grass.
Preferably, in all aspects of the invention, the crops of useful plants, e.g. on or in which or at the locus of which the compounds or compositions according to the invention can be used, comprise (e.g. are): cereals (in particular non-oat cereals, more particularly non-oat non- sorghum non-millet cereals, even more particularly wheat, barley, rye and/or triticale), rice, sugarcane, leguminous crops [preferably soybean, peanut, and/or pulse crops (more preferably soybean)], cotton, rape (in particular oilseed rape or canola), sunflower, linseed, sugarbeet, fodder beet, potato, and/or vegetables (preferably dicotyledonous vegetables).
More preferably, in all aspects of the invention, the crops of useful plants, e.g. on or in which or at the locus of which the compounds or compositions according to the invention can be used, comprise (e.g. are): wheat (e.g. winter wheat, spring wheat, or durum wheat), barley (e.g. winter or spring barley), rye, triticale, rice, sugarcane, leguminous crops [preferably soybean, peanut, and/or pulse crops (more preferably soybean)], cotton, rape (in particular oilseed rape or canola), sunflower, linseed, sugarbeet, fodder beet, potato, and/or vegetables (preferably dicotyledonous vegetables).
Even more preferably, in all aspects of the invention, the crops of useful plants, e.g. on or in which or at the locus of which the compounds or compositions according to the invention can be used, comprise (e.g. are): leguminous crops [preferably soybean, peanut, and/or pulse crops; more preferably soybean; wherein typically the pulse crops comprise dry beans (e.g. kidney or haricot or pinto bean which is Phaseolus vulgaris, or mung bean which is Vigna radiata), chickpea, blackeye bean (i.e. black-eyed pea, Vigna unguiculata), lentil, dry broad beans, and/or dry peas such as garden peas], cotton, rape (in particular oilseed rape or canola), sunflower, sugarbeet, fodder beet, potato, and/or vegetables (preferably
dicotyledonous vegetables).
The term "crops" is to be understood as also including crops that have been rendered tolerant to herbicides or classes of herbicides (for example ALS, GS, EPSPS, PPO and HPPD inhibitors, and/or 2,4-D or dicamba) as a result of conventional methods of breeding or genetic engineering. Examples of crops that have been rendered tolerant e.g. to imid- azolinones (which are ALS inhibitors), such as imazamox, by conventional methods of breeding include Clearfield® summer rape (canola) and/or Clearfield® wheat and/or
Clearfield® rice (all from BASF). Examples of crops that have been rendered tolerant to herbicides by genetic engineering methods include e.g. glyphosate-resistant (glyphosate- tolerant) or glufosinate-resistant (glufosinate-tolerant) maize or soybean varieties, in particular those commercially available under the trade name RoundupReady® or
RoundupReady® 2 (both from Monsanto, both glyphosate-resistant) or LibertyLink® (from Bayer, glufosinate-resistant). Glufosinate-resistant (glufosinate-tolerant) rice (LibertyLink®) also has been published.
Other crops of useful plants include 2,4-D-tolerant soybean, e.g. soybean genetically- modified to be tolerant to the herbicide 2,4-D, or dicamba-tolerant soybean, e.g. soybean genetically-modified to be tolerant to the herbicide dicamba. Such 2,4-D-tolerant or dicamba- tolerant soybean crops can also, in particular, be tolerant to glyphosate or glufosinate. For example, crops of useful plants include soybeans containing a dicamba-tolerance trait combined (stacked) with a glyphosate-tolerance trait, such that these soybeans have tolerance to the herbicides glyphosate and dicamba (for example Genuity® Roundup Ready® 2 Xtend soybeans, currently under development by Monsanto).
Crops are also to be understood as being those which have been rendered resistant to harmful insects by genetic engineering methods, for example Bt maize (resistant to
European corn borer), Bt cotton (resistant to cotton boll weevil) and also Bt potatoes
(resistant to Colorado beetle). Examples of Bt maize are the Bt-176 maize hybrids of NK® (Syngenta Seeds). The Bt toxin is a protein that is formed naturally by Bacillus thunngiensis soil bacteria. Examples of toxins and transgenic plants able to synthesise such toxins are described in EP-A-451 878, EP-A-374 753, WO 93/07278, WO 95/34656, WO 03/052073 and EP-A-427 529. Examples of transgenic plants that contain one or more genes which code for an insecticidal resistance and express one or more toxins are KnockOut® (maize), Yield Gard® (maize), NuCOTIN33B® (cotton), Bollgard® (cotton), NewLeaf® (potatoes), NatureGard® and Protexcta®. Plant crops and their seed material can be resistant to herbicides and at the same time also to insect feeding ("stacked" transgenic events). Seed can, for example, have the ability to express an insecticidally active Cry3 protein and at the same time be glyphosate-tolerant. The term "crops" is to be understood as also including crops obtained as a result of conventional methods of breeding or genetic engineering which contain so-called output traits (e.g. improved flavour, storage stability, nutritional content).
In all aspects of the invention, the weeds, e.g. to be controlled and/or growth-inhibited, may be either monocotyledonous (e.g. grassy) and/or dicotyledonous weeds. Preferably the weeds, e.g. to be controlled and/or growth-inhibited, comprise or are monocotyledonous weeds, more preferably grassy monocotyledonous weeds.
In all aspects of the invention, typically, the monocotyledonous (preferably grassy) weeds, e.g. to be controlled and/or growth-inhibited, comprise (e.g. are) weeds from the genus Agrostis, Alopecurus, Apera, Avena, Brachiaria, Bromus, Cenchrus, Cyperus (a genus of sedges), Digitaria, Echinochloa, Eleusine, Eriochloa, Fimbristylis (a genus of sedges), Juncus (a genus of rushes), Leptochloa, Lolium, Monochoria, Ottochloa, Panicum,
Pennisetum, Phalaris, Poa, Rottboellia, Sagittaria, Scirpus (a genus of sedges), Setaria and/or Sorghum; in particular: Alopecurus myosuroides (ALOMY, English name
"blackgrass"), Apera spica-venti, Avena fatua (AVEFA, English name "wild oats"), Avena ludoviciana, Avena sterilis, Avena sativa (English name "oats" (volunteer)), Brachiaria decumbens, Brachiaria plantaginea, Bromus tectorum, Digitaria horizontalis, Digitaria insularis, Digitaria sanguinalis (DIGSA), Echinochloa crus-galli (English name "common barnyard grass", ECHCG), Echinochloa oryzoides, Echinochloa colona or colonum, Eleusine indica, Eriochloa villosa (English name "woolly cupgrass"), Leptochloa chinensis, Leptochloa panicoides, Lolium perenne (LOLPE, English name "perennial ryegrass"), Lolium multiflorum (LOLMU, English name "Italian ryegrass"), Lolium persicum (English name "Persian darnel"), Lolium rigidum, Panicum miliaceum (English name "wild proso millet"), Phalaris minor, Phalaris paradoxa, Poa annua (POAAN, English name "annual bluegrass"), Scirpus maritimus, Scirpus juncoides, Setaria viridis (SETVI, English name "green foxtail"), Setaria faberi (SETFA, English name "giant foxtail"), Setaria glauca, Setaria lutescens (English name "yellow foxtail"), Sorghum bicolor, and/or Sorghum halepense (English name "Johnson grass"); and/or in particular: Brachiaria platyphylla (BRAPP), Panicum dichotomiflorum (PANDI), and/or Sorghum vulgare. Alternatively or additionally, the monocotyledonous (preferably grassy monocotyledonous) weeds, e.g. to be controlled and/or growth-inhibited, comprise volunteer corn (volunteer maize) weeds.
In one preferred embodiment of all aspects of the invention, the monocotyledonous weeds, e.g. to be controlled and/or growth-inhibited, are grassy monocotyledonous weeds; in which case they typically comprise (e.g. are) weeds from the genus Agrostis, Alopecurus, Apera, Avena, Brachiaria, Bromus, Cenchrus, Digitaria, Echinochloa, Eleusine, Eriochloa,
Leptochloa, Lolium, Ottochloa, Panicum, Pennisetum, Phalaris, Poa, Rottboellia, Setaria and/or Sorghum; in particular: weeds from the genus Agrostis, Alopecurus, Apera, Avena, Brachiaria, Bromus, Digitaria, Echinochloa, Eriochloa, Leptochloa, Lolium, Panicum, Phalaris, Poa, Rottboellia, Setaria and/or Sorghum. Alternatively or additionally, the monocotyledonous (preferably grassy monocotyledonous) weeds, e.g. to be controlled and/or growth-inhibited, comprise volunteer corn (volunteer maize) weeds.
In one preferred embodiment of all aspects of the invention, the grassy monocotyledonous weeds, e.g. to be controlled and/or growth-inhibited, are "warm-season" (warm climate) grassy weeds; in which case they preferably comprise (e.g. are) weeds from the genus Brachiaria, Cenchrus, Digitaria, Echinochloa, Eleusine, Eriochloa, Leptochloa, Ottochloa, Panicum, Pennisetum, Phalaris, Rottboellia, Setaria and/or Sorghum; more particularly: weeds from the genus Brachiaria, Digitaria, Echinochloa, Eriochloa, Leptochloa, Panicum, Setaria and/or Sorghum. Alternatively or additionally, the grassy monocotyledonous weeds, e.g. to be controlled and/or growth-inhibited, comprise volunteer corn (volunteer maize) weeds. More preferably, the grassy monocotyledonous weeds, e.g. to be controlled and/or growth-inhibited, are "warm-season" (warm climate) grassy weeds comprising (e.g. being) weeds from the genus Brachiaria, Cenchrus, Digitaria, Echinochloa, Eleusine, Eriochloa, Panicum, Setaria and/or Sorghum; and/or the grassy monocotyledonous weeds, e.g. to be controlled and/or growth-inhibited, comprise volunteer corn (volunteer maize) weeds.
In another particular embodiment of all aspects of the invention, the grassy
monocotyledonous weeds, e.g. to be controlled and/or growth-inhibited, are "cool-season" (cool climate) grassy weeds; in which case they typically comprise (e.g. are) weeds from the genus Agrostis, Alopecurus, Apera, Avena, Bromus, Lolium and/or Poa. ln non-oat cereal crops such as wheat and/or barley, control and/or growth inhibition of weeds from the genus Alopecurus, Apera, Avena, especially Avena fatua, Bromus, Lolium, Phalaris, and/or Setaria is preferred; in particular Alopecurus, Avena (especially Avena fatua), Lolium and/or Setaria (especially Setaria viridis, Setaria lutescens, Setaria faberi and/or Setaria glauca).
In all aspects of the invention, in a particular embodiment, the weeds, e.g. to be controlled and/or growth-inhibited e.g. by applying a compound of formula (I), may be grassy monocotyledonous weeds (e.g. Agrostis, Alopecurus, Apera, Avena, Brachiaria, Bromus, Cenchrus, Digitaria, Echinochloa, Eleusine, Eriochloa, Leptochloa, Lolium, Ottochloa, Panicum, Pennisetum, Phalaris, Poa, Rottboellia, Setaria and/or Sorghum weeds; more particularly Alopecurus, Apera, Avena, Brachiaria, Bromus, Digitaria, Echinochloa, Eriochloa, Lolium, Panicum, Phalaris, Poa, Setaria and/or Sorghum weeds),
- which are resistant to one or more ACCase inhibitor herbicides (ACCase = acetyl- coenzyme A carboxylase) selected from the group consisting of pinoxaden, clodinafop- propargyl, fenoxaprop-P-ethyl, diclofop-methyl, fluazifop-P-butyl, haloxyfop-P-methyl, quizalofop-P-ethyl, propaquizafop, cyhalofop-butyl, clethodim, sethoxydim, cycloxydim, tralkoxydim and butroxydim;
- and/or which are resistant to glyphosate;
- and/or which are resistant to one or more ALS inhibitor herbicides (ALS = acetolactate synthase), such as one or more sulfonyl urea herbicides (e.g. iodosulfuron-methyl, mesosulfuron-methyl, tribenuron-methyl, triasulfuron, prosulfuron, sulfosulfuron,
pyrazosulfuron-ethyl, bensulfuron-methyl, nicosulfuron, flazasulfuron, iofensulfuron, metsulfuron-methyl, or any other sulfonyl urea herbicide disclosed in The Pesticide Manual, 15th edition (2009) or 16th Edition (2012), ed. C.D.S. Tomlin, British Crop Protection Council) and/or one or more triazolopyrimidine herbicides (e.g. florasulam, pyroxsulam or
penoxsulam) and/or one or more pyrimidinyl-(thio or oxy)-benzoate herbicides (e.g.
bispyribac-sodium or pyriftalid) and/or one or more sulfonylamino-carbonyl-triazolinone herbicides (e.g. thiencarbazone-methyl, propoxycarbazone-sodium or flucarbazone-sodium) and/or one or more imidazolinone herbicides (e.g. imazamox).
Such resistant (in particular ACCase-inhibitor-resistant, glyphosate-resistant, and/or ALS- inhibitor-resistant) grassy weeds can more particularly comprise Alopecurus myosuroides, Apera spica-venti, Avena fatua, Avena sterilis, Brachiaria decumbens, Brachiaria
plantaginea, Digitaria horizontalis, Digitaria insularis, Digitaria sanguinalis, Echinochloa colona, Echinochloa crus-galli, Eleusine indica, Lolium multiflorum, Lolium rigidum, Lolium perenne, Phalaris minor, Phalaris paradoxa, Setaria viridis, Setaria faberi, Setaria glauca, and/or Sorghum halepense; or can more particularly comprise Alopecurus myosuroides, Apera spica-venti, Avena fatua, Avena sterilis, Digitaria sanguinalis, Echinochloa colona, Echinochloa crus-galli, Lolium multiflorum, Lolium rigidum, Lolium perenne, Phalaris minor, Phalaris paradoxa, Setaria viridis, Setaria faberi and/or Sorghum halapense.
In an even more particular embodiment of the invention, the compound of formula (I) can be applied to grassy monocotyledonous weeds (e.g. selected from one of the above-mentioned list(s) of grassy weeds):
(a1 ) which are resistant to one or more ACCase inhibitor herbicides (e.g. selected from the above-mentioned list of ACCase inhibitor herbicides) at least partly by means of mutation (e.g. substitution) of one or more amino acids on the ACCase target site in the weed (e.g. see S.B. Powles and Qin Yu, "Evolution in Action: Plants Resistant to Herbicides", Annu. Rev. Plant Biol. , 2010, 61 , pp. 317-347, e.g. see pages 325-327 therein in particular Table 3, incorporated herein by reference, for examples of such resistant weeds and/or amino acid substitutions); and/or
(a2) which are resistant to glyphosate at least partly by means of mutation (e.g. substitution) of one or more amino acids on the EPSPS target site in the weed targeted by glyphosate (e.g. see above-mentioned S.B. Powles and Qin Yu article, pp. 327-329); and/or
(a3) which are resistant to one or more ALS inhibitor herbicides (e.g. selected from the above-mentioned list of ALS inhibitor herbicides) at least partly by mutation (e.g. substitution) of one or more amino acids on the ALS target site in the weed (e.g. see S.B. Powles and Qin Yu, "Evolution in Action: Plants Resistant to Herbicides", Annu. Rev. Plant Biol., 2010, 61 , pp. 317-347, e.g. see pages 322-324 therein in particular Table 2, incorporated herein by reference, for examples of such resistant weeds and/or amino acid substitutions); and/or (b) which are resistant to: one or more ACCase inhibitor herbicides (e.g. selected from the above-mentioned list), and/or glyphosate, and/or one or more ALS inhibitor herbicides (e.g. selected from the above-mentioned list); at least partly by metabolic-type herbicidal resistance e.g. at least partly by cytochrome P450-mediated herbicide metabolism (e.g. see S.B. Powles and Qin Yu, "Evolution in Action: Plants Resistant to Herbicides", Annu. Rev. Plant Biol. , 2010, 61 , pp. 317-347, e.g. see Table 4 on page 328 therein, incorporated herein by reference, for examples of such resistant weeds). ln one embodiment, dicotyledonous weeds, e.g. to be controlled, comprise (e.g. are)
Abutilon, Amaranthus, Chenopodium, Chrysanthemum, Galium, Ipomoea, Kochia,
Nasturtium, Polygonum, Sida, Sinapsis, Solanum, Stellaria, Viola, Veronica and/or Xanthium.
Areas under cultivation, and/or the locus (e.g. of weeds and/or of crops of useful plants), are to be understood as including land where the crop plants are already growing as well as land intended for the cultivation of those crop plants.
In all aspects of the invention, the rate of application (typically to the weeds and/or to the crops of useful plants and/or to the locus thereof) of the compound of formula (I) (which optionally may be an agrochemically acceptable salt thereof) is generally from 1 to 2000 g of the compound of formula (I) per hectare (ha) (measured as the salt-free compound, i.e.
excluding the weight of any associated salt counterion(s)), in particular from 5 to 1000 g/ha or from 5 to 500 g/ha or from 10 to 500 g/ha, preferably from 10 to 400 g/ha or from 20 to 300 g/ha, of the compound of formula (I) (measured as the salt-free compound, i.e. excluding the weight of any associated salt counterion(s)). In a preferred embodiment, the above rates of application are for post-emergence application of the compound of formula (I) (which optionally may be an agrochemically acceptable salt thereof).
In all aspects of the invention, the compound of formula (I) can be applied (typically to the weeds and/or to the crops of useful plants and/or to the locus thereof) pre- and/or post- emergence, but preferably is applied post-emergence.
Other possible uses - e.g. possible insecticidal and/or acaricidal uses
The main use and purpose of the compounds of formula (I) according to the invention is their herbicidal use. However, at least some of the compounds of formula (I) may have activity against one or more types of pest (in particular pests associated with agriculture and/or food storage). For example, at least some of the compounds of formula (I) may have at least some insecticidal, acaricidal, molluscicidal and/or nematicidal activity.
At least some of the compounds of formula (I) may have activity against (and/or may help to control and/or combat) insect pests, such as one or more of: Coleoptera, Dictyoptera, Diptera, Hemiptera (including Homoptera), Hymenoptera, Isoptera, Lepidoptera, Orthoptera, Siphonaptera and/or Thysanoptera.
At least some of the compounds of formula (I) may have activity against (and/or may help to control and/or combat) acarine pests and/or pests from the order Acarina, such as one or more of: Acalitus spp, Aculus spp, Acaricalus spp, Aceria spp, Acarus siro, Amblyomma spp., Argas spp., Boophilus spp., Brevipalpus spp., Bryobia spp, Calipitrimerus spp., Chorioptes spp., Dermanyssus gallinae, Dermatophagoides spp, Eotetranychus spp, Eriophyes spp., Hemitarsonemus spp, Hyalomma spp., Ixodes spp., Olygonychus spp, Ornithodoros spp., Polyphagotarsone latus, Panonychus spp., Phyllocoptruta oleivora, Phytonemus spp, Polyphagotarsonemus spp, Psoroptes spp., Rhipicephalus spp.,
Rhizoglyphus spp., Sarcoptes spp., Steneotarsonemus spp, Tarsonemus spp. and/or Tetranychus spp.
At least some of the compounds of formula (I) may have activity against (and/or may help to control and/or combat) other (i.e. non-insect, non-acarine) invertebrate pests, for example, nematode and/or mollusc pests.
Insects, acarines, nematodes and/or molluscs are hereinafter collectively referred to as pests.
Examples of pest species, on and/or to which the compounds of formula (I) can be tried and/or applied, include one or more of: Myzus spp. such as Myzus persicae (aphid), Aphis spp. such as Aphis gossypii (aphid) or Aphis fabae (aphid), Lygus spp. (capsids), Dysdercus spp. (capsids), Nilaparvata lugens (planthopper), Nephotettixc incticeps (leafhopper), Nezara spp. (stinkbugs), Euschistus spp. (stinkbugs), Leptocorisa spp. (stinkbugs), Frankliniella occidentalis (thrip), Thrips spp. (thrips), Leptinotarsa decemlineata (Colorado potato beetle), Anthonomus grandis (boll weevil), Aonidiella spp. (scale insects), Trialeurodes spp. (white flies), Bemisia tabaci (white fly), Ostrinia nubilalis (European corn borer), Spodoptera littoralis (cotton leafworm), Heliothis virescens (tobacco budworm), Helicoverpa armigera (cotton bollworm), Helicoverpa zea (cotton bollworm), Sylepta derogata (cotton leaf roller), Pieris brassicae (white butterfly), Plutella xylostella (diamond back moth), Agrotis spp. (cutworms), Chilo suppressalis (rice stem borer), Locustajnigratoria (locust), Chortiocetes terminifera (locust), Diabrotica spp. (rootworms), Panonychus ulmi (European red mite), Panonychus citri (citrus red mite), Tetranychus spp. such as Tetranychus urticae (two-spotted spider mite) or Tetranychus cinnabarinus (carmine spider mite), Phyllocoptruta oleivora (citrus rust mite), Polyphagotarsonemus latus (broad mite), Brevipalpus spp. (flat mites), Boophilus microplus (cattle tick), Dermacentor variabilis (American dog tick), Ctenocephalides felis (cat flea), Liriomyza spp. (leafminer), Musca domestica (housefly), Aedes aegypti (mosquito),
Anopheles spp. (mosquitoes), Culex spp. (mosquitoes), Lucillia spp. (blowflies), Blattella germanica (cockroach), Periplaneta americana (cockroach), Blatta orientalis (cockroach), termites of the Mastotermitidae (for example Mastotermes spp.), of the Kalotermitidae (for example Neotermes spp.), of the Rhinotermitidae (for example Coptotermes formosanus, Reticulitermes flavipes, R. speratu, R. virgin icus, R. hesperus, or R. santonensis) or of the Termitidae (for example Globitermes sulphureus), Solenopsis geminata (fire ant),
Monomorium pharaonis (pharaoh's ant), Damalinia spp. or Linognathus spp. (biting lice or sucking lice), Meloidogyne spp. (root knot nematodes), Globodera spp. or Heterodera spp. (cyst nematodes), Pratylenchus spp. (lesion nematodes), Rhodopholus spp. (banana burrowing nematodes), Tylenchulus spp. (citrus nematodes), Haemonchus contortus (barber pole worm), Caenorhabditis elegans 'megar eelworm), Trichostrongylus spp. (gastro intestinal nematodes) and/or Deroceras reticulatum (slug).
Combinations and mixtures
In a further aspect, the present invention provides a herbicidal composition, e.g. for use in a method of controlling weeds (preferably monocotyledonous weeds such as more preferably grassy monocotyledonous weeds) in crops of useful plants, comprising a compound of formula (I) as defined herein (e.g. a herbicidally effective amount thereof), and an
agrochemically acceptable carrier, diluent and/or solvent, and also comprising one or more further herbicides, and/or a safener.
In all aspects of the invention, the compound of the formula (I) is optionally present (e.g. where chemically possible) as an agrochemically acceptable salt thereof.
Examples of these mixtures / compositions, comprising one or more further herbicides and/or a safener, follow.
The compounds of formula (I) according to the invention can be used in combination with one or more further herbicides, e.g. as mixture partner(s) for the compound of formula (I). Preferably, in these mixtures (in particular in the specific mixtures disclosed hereinbelow), the compound of the formula (I) is one of the exemplified compounds (in particular one of compounds A1 to A151 or P1 to P12, more particularly one of compounds A1 to A1 1 1 , or A142 to A149, or A150 or A151 , or P1 to P12) disclosed herein e.g. hereinbelow, optionally present (e.g. where chemically possible) as an agrochemically acceptable salt thereof.
In particular, the following mixtures of the compound of formula (I) with one or more further herbicides are particularly disclosed: compound of formula I + acetochlor, compound of formula I + acifluorfen, compound of formula I + acifluorfen-sodium, compound of formula I + aclonifen, compound of formula I + acrolein, compound of formula I + alachlor, compound of formula I + alloxydim, compound of formula I + allyl alcohol, compound of formula I + ametryn, compound of formula I + amicarbazone, compound of formula I + amidosulfuron, compound of formula I +
aminopyralid, compound of formula I + amitrole, compound of formula I + ammonium sulfamate, compound of formula I + anilofos, compound of formula I + asulam, compound of formula I + atraton, compound of formula I + atrazine, compound of formula I + azimsulfuron, compound of formula I + BCPC, compound of formula I + beflubutamid, compound of formula I + benazolin, compound of formula I + benfluralin, compound of formula I + benfuresate, compound of formula I + bensulfuron, compound of formula I + bensulfuron-methyl, compound of formula I + bensulide, compound of formula I + bentazone, compound of formula I + benzfendizone, compound of formula I + benzobicyclon, compound of formula I + benzofenap, compound of formula I + bifenox, compound of formula I + bilanafos, compound of formula I + bispyribac, compound of formula I + bispyribac-sodium, compound of formula I + borax, compound of formula I + bromacil, compound of formula I + bromobutide, compound of formula I + bromoxynil, compound of formula I + bromoxynil heptanoate, compound of formula I + bromoxynil octanoate, compound of formula I + bromoxynil heptanoate + bromoxynil octanoate, compound of formula I + butachlor, compound of formula I + butafenacil, compound of formula I + butamifos, compound of formula I + butralin, compound of formula I + butroxydim, compound of formula I + butylate, compound of formula I + cacodylic acid, compound of formula I + calcium chlorate, compound of formula I + cafenstrole, compound of formula I + carbetamide, compound of formula I + carfentrazone, compound of formula I + carfentrazone-ethyl, compound of formula I + CDEA, compound of formula I + CEPC, compound of formula I + chloransulam, compound of formula I + chloransulam-methyl, compound of formula I + chlorflurenol, compound of formula I + chlorflurenol-methyl, compound of formula I + chloridazon, compound of formula I + chlorimuron, compound of formula I + chlorimuron-ethyl, compound of formula I +
chloroacetic acid, compound of formula I + chlorotoluron, compound of formula I +
chlorpropham, compound of formula I + chlorsulfuron, compound of formula I + chlorthal, compound of formula I + chlorthal-dimethyl, compound of formula I + cinidon-ethyl, compound of formula I + cinmethylin, compound of formula I + cinosulfuron, compound of formula I + cisanilide, compound of formula I + clethodim, compound of formula I + clodinafop, compound of formula I + clodinafop-propargyl, compound of formula I + clomazone, compound of formula I + clomeprop, compound of formula I + clopyralid, compound of formula I + cloransulam, compound of formula I + cloransulam-methyl, compound of formula I + CMA, compound of formula I + 4-CPB, compound of formula I + CPMF, compound of formula I + 4-CPP, compound of formula I + CPPC, compound of formula I + cresol, compound of formula I + cumyluron, compound of formula I + cyanamide, compound of formula I + cyanazine, compound of formula I + cycloate, compound of formula I + cyclosulfamuron, compound of formula I + cycloxydim, compound of formula I + cyhalofop, compound of formula I + cyhalofop-butyl, compound of formula I + 2,4-D, compound of formula I + 2,4-D-dimethylammonium, compound of formula I +
2,4-D-2-ethylhexyl, compound of formula I + a choline salt of 2,4-D (see e.g. Examples 2 and 3 of WO2010/123871 A1 ), compound of formula I + 2,4-D + glyphosate, compound of formula
1 + 2,4-D-dimethylammonium + glyphosate, compound of formula I + 2,4-D-2-ethylhexyl + glyphosate, compound of formula I + a choline salt of 2,4-D + glyphosate (see e.g. Examples
2 and 3 of WO2010/123871A1 ), compound of formula I + 3,4-DA, compound of formula I + daimuron, compound of formula I + dalapon, compound of formula I + dazomet, compound of formula I + 2,4-DB, compound of formula I + 3,4-DB, compound of formula I + 2,4-DEB, compound of formula I + desmedipham, compound of formula I + dicamba, compound of formula I + dicamba-dimethylammonium, compound of formula I + dicamba-potassium, compound of formula I + dicamba-sodium, compound of formula I + dicamba-diglycolamine, compound of formula I + a /V,/V-bis-[aminopropyl]methylamine salt of dicamba (see e.g.
US2012/0184434A1 ), compound of formula I + dicamba + glyphosate, compound of formula
I + dicamba-dimethylammonium + glyphosate, compound of formula I + dicamba-potassium + glyphosate, compound of formula I + dicamba-sodium + glyphosate, compound of formula I + dicamba-diglycolamine + glyphosate (see e.g. US2012/0184434A1 ), compound of formula I + a /V,/V-bis-[aminopropyl]methylamine salt of dicamba + glyphosate, compound of formula I + dichlobenil, compound of formula I + ortho-dichlorobenzene, compound of formula I + para- dichlorobenzene, compound of formula I + dichlorprop, compound of formula I + dichlorprop- P, compound of formula I + diclofop, compound of formula I + diclofop-methyl, compound of formula I + diclosulam, compound of formula I + difenzoquat, compound of formula I + difenzoquat metilsulfate, compound of formula I + diflufenican, compound of formula I + diflufenzopyr, compound of formula I + dimefuron, compound of formula I + dimepiperate, compound of formula I + dimethachlor, compound of formula I + dimethametryn, compound of formula I + dimethenamid, compound of formula I + dimethenamid-P, compound of formula I + dimethipin, compound of formula I + dimethylarsinic acid, compound of formula I + dinitramine, compound of formula I + dinoterb, compound of formula I + diphenamid, compound of formula I + diquat, compound of formula I + diquat dibromide, compound of formula I + dithiopyr, compound of formula I + diuron, compound of formula I + DNOC, compound of formula I + 3,4-DP, compound of formula I + DSMA, compound of formula I + EBEP, compound of formula I + endothal, compound of formula I + EPTC, compound of formula I + esprocarb, compound of formula I + ethalfluralin, compound of formula I + ethametsulfuron, compound of formula I + ethametsulfuron-methyl, compound of formula I + ethofumesate, compound of formula I + ethoxyfen, compound of formula I + ethoxysulfuron, compound of formula I + etobenzanid, compound of formula (I) + fenoxaprop, compound of formula (I) + fenoxaprop-ethyl, compound of formula I + fenoxaprop-P, compound of formula I + fenoxaprop-P-ethyl, compound of formula I + fenoxasulfone (CAS Reg. No. 639826-16-7), compound of formula I + fentrazamide, compound of formula I + ferrous sulfate, compound of formula I + flamprop-M, compound of formula I + flazasulfuron, compound of formula I + florasulam, compound of formula I + fluazifop, compound of formula I + fluazifop-butyl, compound of formula I + fluazifop-P, compound of formula I + fluazifop-P-butyl, compound of formula I + flucarbazone, compound of formula I + flucarbazone-sodium, compound of formula I + flucetosulfuron, compound of formula I + fluchloralin, compound of formula I + flufenacet, compound of formula I + flufenpyr, compound of formula I + flufenpyr-ethyl, compound of formula I + flumetsulam, compound of formula I + flumiclorac, compound of formula I + flumiclorac-pentyl, compound of formula I + flumioxazin, compound of formula I + fluometuron, compound of formula I + fluoroglycofen, compound of formula I +
fluoroglycofen-ethyl, compound of formula I + flupropanate, compound of formula I + flupyrsulfuron, compound of formula I + flupyrsulfuron-methyl-sodium, compound of formula I + flurenol, compound of formula I + fluridone, compound of formula I + flurochloridone, compound of formula I + fluroxypyr, compound of formula I + fluroxypyr-meptyl, compound of formula I + fluroxypyr-butometyl, compound of formula I + flurtamone, compound of formula I + fluthiacet, compound of formula I + fluthiacet-methyl, compound of formula I + fomesafen, compound of formula I + foramsulfuron, compound of formula I + fosamine, compound of formula I + glufosinate, compound of formula I + glufosinate-ammonium, compound of formula I + glufosinate-P, compound of formula I + glyphosate, compound of formula I + glyphosate-diammonium, compound of formula I + glyphosate-isopropylammonium, compound of formula I + glyphosate-potassium, compound of formula I + halosulfuron, compound of formula I + halosulfuron-methyl, compound of formula I + haloxyfop, compound of formula I + haloxyfop-P, compound of formula (I) + haloxyfop-methyl, compound of formula (I) + haloxyfop-P-methyl, compound of formula I + HC-252, compound of formula I + hexazinone, compound of formula I + imazamethabenz, compound of formula I +
imazamethabenz-methyl, compound of formula I + imazamox, compound of formula I + imazapic, compound of formula I + imazapyr, compound of formula I + imazaquin, compound of formula I + imazethapyr, compound of formula I + imazosulfuron, compound of formula I + indanofan, compound of formula I + iodomethane, compound of formula I + iodosulfuron, compound of formula I + iodosulfuron-methyl-sodium, compound of formula I + ioxynil, compound of formula I + ipfencarbazone (CAS Reg. No. 212201-70-2), compound of formula I + isoproturon, compound of formula I + isouron, compound of formula I + isoxaben, compound of formula I + isoxachlortole, compound of formula I + isoxaflutole, compound of formula I + karbutilate, compound of formula I + lactofen, compound of formula I + lenacil, compound of formula I + linuron, compound of formula I + MAA, compound of formula I + MAMA, compound of formula I + MCPA, compound of formula I + MCPA-thioethyl, compound of formula I + MCPB, compound of formula I + mecoprop, compound of formula I + mecoprop-P, compound of formula I + mefenacet, compound of formula I + mefluidide, compound of formula I + mesosulfuron, compound of formula I + mesosulfuron-methyl, compound of formula I + mesotrione, compound of formula I + metam, compound of formula I + metamifop, compound of formula I + metamitron, compound of formula I + metazachlor, compound of formula I + metazosulfuron (NC-620, CAS Reg. No. 868680-84-6), compound of formula I + methabenzthiazuron, compound of formula I + methylarsonic acid, compound of formula I + methyldymron, compound of formula I + methyl isothiocyanate, compound of formula I + metobenzuron, compound of formula I + metolachlor, compound of formula I + S- metolachlor, compound of formula I + metosulam, compound of formula I + metoxuron, compound of formula I + metribuzin, compound of formula I + metsulfuron, compound of formula I + metsulfuron-methyl, compound of formula I + MK-616, compound of formula I + molinate, compound of formula I + monolinuron, compound of formula I + MSMA, compound of formula I + naproanilide, compound of formula I + napropamide, compound of formula I + naptalam, compound of formula I + neburon, compound of formula I + nicosulfuron, compound of formula I + nonanoic acid, compound of formula I + norflurazon, compound of formula I + oleic acid (fatty acids), compound of formula I + orbencarb, compound of formula I + orthosulfamuron, compound of formula I + oryzalin, compound of formula I + oxadiargyl, compound of formula I + oxadiazon, compound of formula I + oxasulfuron, compound of formula I + oxaziclomefone, compound of formula I + oxyfluorfen, compound of formula I + paraquat, compound of formula I + paraquat dichloride, compound of formula I + pebulate, compound of formula I + pendimethalin, compound of formula I + penoxsulam, compound of formula I + pentachlorophenol, compound of formula I + pentanochlor, compound of formula I + pentoxazone, compound of formula I + pethoxamid, compound of formula I + petrolium oils, compound of formula I + phenmedipham, compound of formula I + phenmedipham-ethyl, compound of formula I + picloram, compound of formula I + picolinafen, compound of formula I + pinoxaden, compound of formula I + piperophos, compound of formula I + potassium arsenite, compound of formula I + potassium azide, compound of formula I + pretilachlor, compound of formula I + primisulfuron, compound of formula I + primisulfuron- methyl, compound of formula I + prodiamine, compound of formula I + profluazol, compound of formula I + profoxydim, compound of formula I + prometon, compound of formula I + prometryn, compound of formula I + propachlor, compound of formula I + propanil, compound of formula I + propaquizafop, compound of formula I + propazine, compound of formula I + propham, compound of formula I + propisochlor, compound of formula I + propoxycarbazone, compound of formula I + propoxycarbazone-sodium, compound of formula I + propyrisulfuron (TH-547, CAS Reg. No. 570415-88-2), compound of formula I + propyzamide, compound of formula I + prosulfocarb, compound of formula I + prosulfuron, compound of formula I + pyraclonil, compound of formula I + pyraflufen, compound of formula I + pyraflufen-ethyl, compound of formula I + pyrazolynate, compound of formula I + pyrazosulfuron, compound of formula I + pyrazosulfuron-ethyl, compound of formula I + pyrazoxyfen, compound of formula I + pyribenzoxim, compound of formula I + pyributicarb, compound of formula I + pyridafol, compound of formula I + pyridate, compound of formula I + pyriftalid, compound of formula I + pyriminobac, compound of formula I + pyriminobac- methyl, compound of formula I + pyrimisulfan, compound of formula I + pyrithiobac, compound of formula I + pyrithiobac-sodium, compound of formula I + quinclorac, compound of formula I + quinmerac, compound of formula I + quinoclamine, compound of formula I + quizalofop, compound of formula I + quizalofop-ethyl, compound of formula I + quizalofop-P, compound of formula I + quizalofop-P-ethyl, compound of formula I + quizalofop-P-tefuryl, compound of formula I + rimsulfuron, compound of formula I + sethoxydim, compound of formula I + siduron, compound of formula I + simazine, compound of formula I + simetryn, compound of formula I + SMA, compound of formula I + sodium arsenite, compound of formula I + sodium azide, compound of formula I + sodium chlorate, compound of formula I + sulcotrione, compound of formula I + sulfentrazone, compound of formula I + sulfometuron, compound of formula I + sulfometuron-methyl, compound of formula I + sulfosate, compound of formula I + sulfosulfuron, compound of formula I + sulfuric acid, compound of formula I + tar oils, compound of formula I + 2,3,6-TBA, compound of formula I + TCA, compound of formula I + TCA-sodium, compound of formula I + tebuthiuron, compound of formula I + tepraloxydim, compound of formula I + terbacil, compound of formula I + terbumeton, compound of formula I + terbuthylazine, compound of formula I + terbutryn, compound of formula I + thenylchlor, compound of formula I + thiazopyr, compound of formula I + thifensulfuron, compound of formula I + thifensulfuron-methyl, compound of formula I + thiobencarb, compound of formula I + tiocarbazil, compound of formula I + topramezone, compound of formula I + tralkoxydim, compound of formula I + tri-allate, compound of formula I + triasulfuron, compound of formula I + triaziflam, compound of formula I + tribenuron, compound of formula I + tribenuron-methyl, compound of formula I + tricamba, compound of formula I + triclopyr, compound of formula I + trietazine, compound of formula I + trifloxysulfuron, compound of formula I + trifloxysulfuron-sodium, compound of formula I + trifluralin, compound of formula I + triflusulfuron, compound of formula I + triflusulfuron- methyl, compound of formula I + trihydroxytriazine, compound of formula I + tritosulfuron, compound of formula I + [3-[2-chloro-4-fluoro-5-(1 -methyl-6-trifluoromethyl-2,4-dioxo-1 ,2,3,4- tetrahydropyrimidin-3-yl)phenoxy]-2-pyridyloxy]acetic acid ethyl ester (CAS Reg. No.
353292-31 -6), compound of formula I + 4-[(4,5-dihydro-3-methoxy-4-methyl-5-oxo)-1 H-1 ,2,4- triazol-1-ylcarbonylsulfamoyl]-5-methylthiophene-3-carboxylic acid (BAY636), compound of formula I + BAY747 (CAS Reg. No. 335104-84-2), compound of formula I + topramezone (CAS Reg. No. 210631-68-8), compound of formula I + 4-hydroxy-3-[[2-[(2-methoxyethoxy)- methyl]-6-(trifluoromethyl)-3-pyridinyl]carbonyl]-bicyclo[3.2.1 ]oct-3-en-2-one (which is bicyclopyrone, CAS Reg. No. 352010-68-5), compound of formula I + 4-hydroxy-3-[[2-(3- methoxypropyl)-6-(difluoromethyl)-3-pyridinyl]carbonyl]-bicyclo[3.2.1 ]oct-3-en-2-one, compound of formula (I) + 4-(4'-chloro-4-cyclopropyl-2'-fluorobiphenyl-3-yl)-2,2,6,6- tetramethyl-2/-/-pyran-3,5(4/-/,6/-/)-dione (which is the compound of Example P8 disclosed on pages 31 -32 and 35-36 of WO 2010/136431 A9 (Syngenta Limited), and which is also compound A-13 disclosed in pages 4, 5, 7 and 1 1 of WO 201 1/073616 A2 (Syngenta Limited), these parts of these publications being incorporated herein by reference), compound of formula (I) + 4-(2',4'-dichloro-4-cyclopropylbiphenyl-3-yl)-2,2,6,6-tetramethyl- 2/-/-pyran-3,5(4/-/,6/-/)-dione (which is the compound of Example P9 disclosed on pages 36- 37 and 40-41 of WO 2010/136431 A9 (Syngenta Limited), and which is also compound A-12 disclosed in page 10 of WO 201 1/073616 A2 (Syngenta Limited), these parts of these publications being incorporated herein by reference), compound of formula (I) + 4-(4'-chloro- 4-ethyl-2'-fluorobiphenyl-3-yl)-2,2,6,6-tetramethyl-2H-pyran-3,5(4H,6H)-dione (which is compound A-66 disclosed on page 95 of WO 2008/071405 A1 (Syngenta Participations AG and Syngenta Limited), and which is also compound A-4 disclosed on page 7 of WO
201 1/073615 A2 (Syngenta Limited), these parts of these publications being incorporated herein by reference), compound of formula (I) + 4-(2',4'-dichloro-4-ethylbiphenyl-3-yl)-2,2,6,6- tetramethyl-2/-/-pyran-3,5(4/-/,6/-/)-dione (which is compound A-45 disclosed on page 93 of WO 2008/071405 A1 (Syngenta Participations AG and Syngenta Limited), and which is also the compound of Example P10 disclosed on pages 41 and 45 of WO 2010/136431 A9 (Syngenta Limited), and which is also compound A-7 disclosed on page 7 of WO
201 1/073615 A2 (Syngenta Limited), these parts of these publications being incorporated herein by reference), compound of formula (I) + 4-(2',4'-dichloro-4-ethylbiphenyl-3-yl)-5- (methoxycarbonyloxy)-2,2,6,6-tetramethyl-2/-/-pyran-3(6/-/)-one (which is compound D-26 disclosed on page 231 of WO 2008/071405 A1 (Syngenta Participations AG and Syngenta Limited), and which is also compound A-9 disclosed on page 8 of WO 201 1/073615 A2 (Syngenta Limited), these parts of these publications being incorporated herein by reference), compound of formula (I) + one of the specific herbicidal compounds disclosed in WO 2010/059676 (Dow, e.g. as defined in one of the examples therein and/or e.g. can be plus cloquintocet-mexyl as safener) these parts of which are incorporated herein by reference, compound of formula (I) + one of the specific herbicidal compounds disclosed in WO 2010/059680 (Dow, e.g. as defined in one of the examples therein and/or e.g. can be plus cloquintocet-mexyl or another safener) these parts of which are incorporated herein by reference, and compound of formula (I) + one of the specific herbicidal compounds disclosed in WO 2010/059671 (Dow, e.g. as defined in one of the examples therein and/or e.g. can be plus a safener) these parts of which are incorporated herein by reference, compound of formula I + halauxifen (which is 4-amino-3-chloro-6-(4-chloro-2-fluoro-3- methoxyphenyl)pyridine-2-carboxylic acid, CAS Reg. No. 943832-60-8), compound of formula I + halauxifen-methyl (which is methyl 4-amino-3-chloro-6-(4-chloro-2-fluoro-3- methoxyphenyl)pyridine-2-carboxylate, CAS Reg. No. 943831 -98-9), compound of formula I + aminocyclopyrachlor (which is 6-amino-5-chloro-2-cyclopropylpyrimidine-4-carboxylic acid, CAS Reg. No. 858956-08-8), compound of formula I + aminocyclopyrachlor-methyl (which is methyl 6-amino-5-chloro-2-cyclopropylpyrimidine-4-carboxylate, CAS Reg. No. 858954-83- 3), compound of formula I + aminocyclopyrachlor-potassium (which is potassium 6-amino-5- chloro-2-cyclopropylpyrimidine-4-carboxylate, CAS Reg. No. 858956-35-1 ), compound of formula I + saflufenacil (which is /\/'-{2-chloro-4-fluoro-5-[1 ,2,3,6-tetrahydro-3-methyl-2,6- dioxo-4-(trifluoromethyl)pyrimidin-1-yl]benzoyl}-/V-isopropyl-/V-methylsulfamide, CAS Reg. No. 372137-35-4), compound of formula I + iofensulfuron (which is 1 -(2-iodophenylsulfonyl)- 3-(4-methoxy-6-methyl-1 ,3,5-triazin-2-yl)urea, CAS Reg. No. 1 144097-22-2), compound of formula I + iofensulfuron-sodium (which is sodium /V-(2-iodophenylsulfonyl)-/V'-(4-methoxy-6- methyl-1 ,3,5-triazin-2-yl)carbamimidate, CAS Reg. No. 1 144097-30-2), compound of formula I + clacyfos (which is dimethyl [(1 RS)-1-(2,4-dichlorophenoxyacetoxy)ethyl]phosphonate, also named Ivxiancaolin or luxiancaolin, CAS Reg. No. 215655-76-8), compound of formula I + cyclopyrimorate (which is 6-chloro-3-(2-cyclopropyl-6-methylphenoxy)pyridazin-4-yl morpholine-4-carboxylate, CAS Reg. No. 499231 -24-2), or compound of formula I + triafamone (which is /V-[2-[(4,6-dimethoxy-1 ,3,5-triazin-2-yl)carbonyl]-6-fluorophenyl]-/V- methyl-1 ,1 -difluoromethanesulfonamide, CAS Reg. No. 874195-61 -6).
The mixture partners for the compound of formula (I) are optionally in the form of an ester (in particular an agrochemically acceptable ester) or a salt (in particular an agrochemically acceptable salt) thereof (e.g. where chemically possible). The above-mentioned mixture partners for the compound of formula (I), are generally mentioned e.g. in The Pesticide Manual, 15th Edition (2009) or 16th Edition (2012), ed. C.D.S. Tomlin, British Crop
Production Council.
In the present patent specification, "CAS Reg. No." or "CAS RN" means the Chemical Abstracts Service Registry Number of the stated compound.
For applications in cereals, the following mixtures are preferred: compound of formula I + aclonifen, compound of formula I + amidosulfuron, compound of formula I + aminopyralid, compound of formula I + beflubutamid, compound of formula I + benfluralin, compound of formula I + bifenox, compound of formula I + bromoxynil, compound of formula I + bromoxynil heptanoate, compound of formula I + bromoxynil octanoate, compound of formula I + bromoxynil heptanoate + bromoxynil octanoate, compound of formula I + butafenacil, compound of formula I + carbetamide, compound of formula I + carfentrazone, compound of formula I + carfentrazone-ethyl, compound of formula I + chlorotoluron, compound of formula I + chlorpropham, compound of formula I + chlorsulfuron, compound of formula I + cinidon- ethyl, compound of formula I + clodinafop, compound of formula I + clodinafop-propargyl, compound of formula I + clopyralid, compound of formula I + 2,4-D, compound of formula I + 2,4-D-dimethylammonium, compound of formula I + 2,4-D-2-ethylhexyl, compound of formula I + a choline salt of 2,4-D (see e.g. Examples 2 and 3 of WO2010/123871 A1 ), compound of formula I + dicamba, compound of formula I + dicamba-dimethylammonium, compound of formula I + dicamba-potassium, compound of formula I + dicamba-sodium, compound of formula I + dicamba-diglycolamine, compound of formula I + a Λ/,/V-bis- [aminopropyl]methylamine salt of dicamba (see e.g. US2012/0184434A1 ), compound of formula I + dichlobenil, compound of formula I + dichlorprop, compound of formula I + diclofop, compound of formula I + diclofop-methyl, compound of formula I + difenzoquat, compound of formula I + difenzoquat metilsulfate, compound of formula I + diflufenican, compound of formula I + diquat, compound of formula I + diquat dibromide, compound of formula (I) + fenoxaprop, compound of formula (I) + fenoxaprop-ethyl, compound of formula I + fenoxaprop-P, compound of formula I + fenoxaprop-P-ethyl, compound of formula I + flamprop-M, compound of formula I + florasulam, compound of formula I + fluazifop-P-butyl, compound of formula I + flucarbazone, compound of formula I + flucarbazone-sodium, compound of formula I + flufenacet, compound of formula I + flupyrsulfuron, compound of formula I + flupyrsulfuron-methyl-sodium, compound of formula I + flurochloridone, compound of formula I + fluroxypyr, compound of formula I + fluroxypyr-meptyl, compound of formula I + fluroxypyr-butometyl, compound of formula I + flurtamone, compound of formula I + imazamethabenz-methyl, compound of formula I + imazamox, compound of formula I + iodosulfuron, compound of formula I + iodosulfuron-methyl-sodium, compound of formula I + ioxynil, compound of formula I + isoproturon, compound of formula I + linuron, compound of formula I + MCPA, compound of formula I + mecoprop, compound of formula I + mecoprop- P, compound of formula I + mesosulfuron, compound of formula I + mesosulfuron-methyl, compound of formula I + mesotrione, compound of formula I + metribuzin, compound of formula I + metsulfuron, compound of formula I + metsulfuron-methyl, compound of formula I + pendimethalin, compound of formula I + picolinafen, compound of formula I + pinoxaden, compound of formula I + prodiamine, compound of formula I + propanil, compound of formula I + propoxycarbazone, compound of formula I + propoxycarbazone-sodium, compound of formula I + prosulfocarb, compound of formula I + pyrasulfotole, compound of formula I + pyridate, compound of formula I + pyroxasulfone (KIH-485), compound of formula I + pyroxsulam compound of formula I + sulfosulfuron, compound of formula 1 + tembotrione, compound of formula I + terbutryn, compound of formula I + thifensulfuron, compound of formula I + thiencarbazone, compound of formula I + thifensulfuron-methyl, compound of formula I + topramezone, compound of formula I + tralkoxydim, compound of formula I + tri- allate, compound of formula I + triasulfuron, compound of formula I + tribenuron, compound of formula I + tribenuron-methyl, compound of formula I + trifluralin, compound of formula I + trinexapac-ethyl and compound of formula I + tritosulfuron, compound of formula I + 4- hydroxy-3-[[2-[(2-methoxyethoxy)methyl]-6-(trifluoromethyl)-3-pyridinyl]carbonyl]- bicyclo[3.2.1 ]oct-3-en-2-one (which is bicyclopyrone, CAS Reg. No. 352010-68-5), compound of formula (I) + one of the specific herbicidal compounds disclosed in WO
2010/059676 (Dow, e.g. as defined in one of the examples therein and/or e.g. can be plus cloquintocet-mexyl as safener) these parts of which are incorporated herein by reference, compound of formula (I) + one of the specific herbicidal compounds disclosed in WO
2010/059680 (Dow, e.g. as defined in one of the examples therein and/or e.g. can be plus cloquintocet-mexyl or another safener) these parts of which are incorporated herein by reference, compound of formula I + halauxifen (which is 4-amino-3-chloro-6-(4-chloro-2- fluoro-3-methoxyphenyl)pyridine-2-carboxylic acid, CAS Reg. No. 943832-60-8), compound of formula I + halauxifen-methyl (which is methyl 4-amino-3-chloro-6-(4-chloro-2-fluoro-3- methoxyphenyl)pyridine-2-carboxylate, CAS Reg. No. 943831 -98-9), compound of formula I + iofensulfuron (which is 1-(2-iodophenylsulfonyl)-3-(4-methoxy-6-methyl-1 ,3,5-triazin-2- yl)urea, CAS Reg. No. 1 144097-22-2), or compound of formula I + iofensulfuron-sodium (which is sodium /V-(2-iodophenylsulfonyl)-/V'-(4-methoxy-6-methyl-1 ,3,5-triazin-2- yl)carbamimidate, CAS Reg. No. 1 144097-30-2);
wherein the mixture partners for the compound of formula (I) may optionally be in the form of an ester (in particular an agrochemically acceptable ester) or a salt (in particular an agrochemically acceptable salt) thereof (e.g. where chemically possible).
For applications in cereals, more preferred is a mixture comprising: a compound of formula (I) + amidosulfuron, compound of formula (I) + aminopyralid, compound of formula (I) + beflubutamid, compound of formula (I) + bromoxynil, compound of formula (I) + bromoxynil heptanoate, compound of formula (I) + bromoxynil octanoate, compound of formula (I) + bromoxynil heptanoate + bromoxynil octanoate, compound of formula (I) + carfentrazone, compound of formula (I) + carfentrazone-ethyl, compound of formula (I) + chlorotoluron, compound of formula (I) + chlorsulfuron, compound of formula (I) + clodinafop, compound of formula (I) + clodinafop-propargyl, compound of formula (I) + clopyralid, compound of formula (I) + 2,4-D, compound of formula (I) + 2,4-D-dimethylammonium, compound of formula (I) + 2,4-D-2-ethylhexyl, compound of formula (I) + a choline salt of 2,4-D (see e.g. Examples 2 and 3 of WO2010/123871 A1 ), compound of formula (I) + dicamba, compound of formula (I) + dicamba-dimethylammonium, compound of formula (I) + dicamba-potassium, compound of formula (I) + dicamba-sodium, compound of formula (I) + dicamba- diglycolamine, compound of formula (I) + a /V,/V-bis-[aminopropyl]methylamine salt of dicamba (see e.g. US2012/0184434A1 ), compound of formula (I) + difenzoquat, compound of formula (I) + difenzoquat metilsulfate, compound of formula (I) + diflufenican, compound of formula (I) + fenoxaprop-P, compound of formula (I) + fenoxaprop-P-ethyl, compound of formula (I) + florasulam, compound of formula (I) + flucarbazone, compound of formula (I) + flucarbazone-sodium, compound of formula (I) + flufenacet, compound of formula (I) + flupyrsulfuron, compound of formula (I) + flupyrsulfuron-methyl-sodium, compound of formula (I) + fluroxypyr, compound of formula I + fluroxypyr-meptyl, compound of formula I + fluroxypyr-butometyl, compound of formula (I) + flurtamone, compound of formula (I) + iodosulfuron, compound of formula (I) + iodosulfuron-methyl-sodium, compound of formula (I) + MCPA, compound of formula (I) + mesosulfuron, compound of formula (I) + mesosulfuron- methyl, compound of formula (I) + metsulfuron, compound of formula (I) + metsulfuron- methyl, compound of formula (I) + pendimethalin, compound of formula (I) + picolinafen, compound of formula (I) + pinoxaden, compound of formula (I) + prosulfocarb, compound of formula (I) + pyrasulfotole, compound of formula (I) + pyroxasulfone (KIH-485), compound of formula (I) + pyroxsulam, compound of formula (I) + sulfosulfuron, compound of formula (I) + thifensulfuron, compound of formula (I) + thifensulfuron-methyl, compound of formula I + topramezone, compound of formula (I) + tralkoxydim, compound of formula (I) + triasulfuron, compound of formula (I) + tribenuron, compound of formula (I) + tribenuron-methyl, compound of formula (I) + trifluralin, compound of formula (I) + trinexapac-ethyl, compound of formula (I) + tritosulfuron, compound of formula I + 4-hydroxy-3-[[2-[(2-methoxyethoxy)- methyl]-6-(trifluoromethyl)-3-pyridinyl]carbonyl]-bicyclo[3.2.1 ]oct-3-en-2-one (which is bicyclopyrone, CAS Reg. No. 352010-68-5), compound of formula (I) + one of the specific herbicidal compounds disclosed in WO 2010/059676 (Dow, e.g. as defined in one of the examples therein and/or e.g. can be plus cloquintocet-mexyl as safener) these parts of which are incorporated herein by reference, compound of formula (I) + one of the specific herbicidal compounds disclosed in WO 2010/059680 (Dow, e.g. as defined in one of the examples therein and/or e.g. can be plus cloquintocet-mexyl or another safener) these parts of which are incorporated herein by reference, compound of formula I + halauxifen (which is 4-amino- 3-chloro-6-(4-chloro-2-fluoro-3-methoxyphenyl)pyridine-2-carboxylic acid, CAS Reg. No. 943832-60-8), compound of formula I + halauxifen-methyl (which is methyl 4-amino-3-chloro- 6-(4-chloro-2-fluoro-3-methoxyphenyl)pyridine-2-carboxylate, CAS Reg. No. 943831 -98-9), compound of formula I + iofensulfuron (which is 1-(2-iodophenylsulfonyl)-3-(4-methoxy-6- methyl-1 ,3,5-triazin-2-yl)urea, CAS Reg. No. 1 144097-22-2), or compound of formula I + iofensulfuron-sodium (which is sodium /V-(2-iodophenylsulfonyl)-/V'-(4-methoxy-6-methyl- 1 ,3,5-triazin-2-yl)carbamimidate, CAS Reg. No. 1 144097-30-2);
wherein the mixture partners for the compound of formula (I) may optionally be in the form of an ester (in particular an agrochemically acceptable ester) or a salt (in particular an agrochemically acceptable salt) thereof (e.g. where chemically possible).
For applications in rice, the following mixtures are preferred: compound of formula (I) + azimsulfuron, compound of formula (I) + bensulfuron, compound of formula (I) + bensulfuron- methyl, compound of formula (I) + benzobicyclon, compound of formula (I) + benzofenap, compound of formula (I) + bispyribac, compound of formula (I) + bispyribac-sodium, compound of formula (I) + butachlor, compound of formula (I) + cafenstrole, compound of formula (I) + cinosulfuron, compound of formula (I) + clomazone, compound of formula (I) + clomeprop, compound of formula (I) + cyclosulfamuron, compound of formula (I) + cyhalofop, compound of formula (I) + cyhalofop-butyl, compound of formula (I) + 2,4-D, compound of formula (I) + 2,4-D-dimethylammonium, compound of formula (I) + 2,4-D-2-ethylhexyl, compound of formula (I) + a choline salt of 2,4-D (see e.g. Examples 2 and 3 of
WO2010/123871 A1 ), compound of formula (I) + daimuron, compound of formula (I) + dicamba, compound of formula (I) + dicamba-dimethylammonium, compound of formula (I) + dicamba-potassium, compound of formula (I) + dicamba-sodium, compound of formula (I) + dicamba-diglycolamine, compound of formula (I) + a /V,/V-bis-[aminopropyl]methylamine salt of dicamba (see e.g. US2012/0184434A1 ), compound of formula (I) + diquat, compound of formula (I) + diquat dibromide, compound of formula (I) + esprocarb, compound of formula (I) + ethoxysulfuron, compound of formula (I) + fenoxaprop, compound of formula (I) + fenoxaprop-ethyl, compound of formula (I) + fenoxaprop-P, compound of formula (I) + fenoxaprop-P-ethyl, compound of formula I + fenoxasulfone (CAS Reg. No. 639826-16-7), compound of formula (I) + fentrazamide, compound of formula (I) + florasulam, compound of formula (I) + glufosinate-ammonium, compound of formula (I) + glyphosate, compound of formula (I) + glyphosate-diammonium, compound of formula (I) + glyphosate- isopropylammonium, compound of formula (I) + glyphosate-potassium, compound of formula (I) + halosulfuron, compound of formula (I) + halosulfuron-methyl, compound of formula (I) + imazosulfuron, compound of formula I + ipfencarbazone (CAS Reg. No. 212201-70-2), compound of formula (I) + MCPA, compound of formula (I) + mefenacet, compound of formula (I) + mesotrione, compound of formula (I) + metamifop, compound of formula I + metazosulfuron (NC-620, CAS Reg. No. 868680-84-6), compound of formula (I) + metsulfuron, compound of formula (I) + metsulfuron-methyl, compound of formula (I) + n- methyl glyphosate, compound of formula (I) + orthosulfamuron, compound of formula (I) + oryzalin, compound of formula (I) + oxadiargyl, compound of formula (I) + oxadiazon, compound of formula (I) + paraquat dichloride, compound of formula (I) + pendimethalin, compound of formula (I) + penoxsulam, compound of formula (I) + pretilachlor, compound of formula (I) + profoxydim, compound of formula (I) + propanil, compound of formula I + propyrisulfuron (TH-547, CAS Reg. No. 570415-88-2), compound of formula (I) +
pyrazolynate, compound of formula (I) + pyrazosulfuron, compound of formula (I) + pyrazosulfuron-ethyl, compound of formula (I) + pyrazoxyfen, compound of formula (I) + pyribenzoxim, compound of formula (I) + pyriftalid, compound of formula (I) + pyriminobac, compound of formula (I) + pyriminobac-methyl, compound of formula (I) + pyrimisulfan, compound of formula (I) + quinclorac, compound of formula (I) + tefuryltrione, compound of formula (I) + triasulfuron and compound of formula (I) + trinexapac-ethyl, compound of formula (I) + 4-(4'-chloro-4-cyclopropyl-2'-fluorobiphenyl-3-yl)-2,2,6,6-tetramethyl-2/-/-pyran- 3,5(4/-/,6/-/)-dione (which is the compound of Example P8 disclosed on pages 31 -32 and 35- 36 of WO 2010/136431 A9 (Syngenta Limited), and which is also compound A-13 disclosed in pages 4, 5, 7 and 1 1 of WO 201 1/073616 A2 (Syngenta Limited), these parts of these publications being incorporated herein by reference), compound of formula (I) + 4-(2',4'- dichloro-4-cyclopropylbiphenyl-3-yl)-2,2,6,6-tetramethyl-2/-/-pyran-3,5(4/-/,6/-/)-dione (which is the compound of Example P9 disclosed on pages 36-37 and 40-41 of WO 2010/136431 A9 (Syngenta Limited), and which is also compound A-12 disclosed in page 10 of WO
201 1/073616 A2 (Syngenta Limited), these parts of these publications being incorporated herein by reference), compound of formula (I) + 4-(4'-chloro-4-ethyl-2'-fluorobiphenyl-3-yl)- 2,2,6,6-tetramethyl-2H-pyran-3,5(4/-/,6/-/)-dione (which is compound A-66 disclosed on page 95 of WO 2008/071405 A1 (Syngenta Participations AG and Syngenta Limited), and which is also compound A-4 disclosed on page 7 of WO 201 1/073615 A2 (Syngenta Limited), these parts of these publications being incorporated herein by reference), compound of formula (I) + 4-(2\4,-dichloro-4-ethylbiphenyl-3-yl)-2,2,6,6-tetramethyl-2H-pyran-3,5(4H,6H)-dione (which is compound A-45 disclosed on page 93 of WO 2008/071405 A1 (Syngenta
Participations AG and Syngenta Limited), and which is also the compound of Example P10 disclosed on pages 41 and 45 of WO 2010/136431 A9 (Syngenta Limited), and which is also compound A-7 disclosed on page 7 of WO 201 1/073615 A2 (Syngenta Limited), these parts of these publications being incorporated herein by reference), compound of formula (I) + 4- (2',4'-dichloro-4-ethylbiphenyl-3-yl)-5-(methoxycarbonyloxy)-2,2,6,6-tetramethyl-2/-/-pyran- 3(6H)-one (which is compound D-26 disclosed on page 231 of WO 2008/071405 A1
(Syngenta Participations AG and Syngenta Limited), and which is also compound A-9 disclosed on page 8 of WO 201 1/073615 A2 (Syngenta Limited), these parts of these publications being incorporated herein by reference), compound of formula (I) + one of the specific herbicidal compounds disclosed in WO 2010/059671 (Dow, e.g. as defined in one of the examples therein and/or e.g. can be plus a safener) these parts of which are
incorporated herein by reference, compound of formula I + halauxifen (which is 4-amino-3- chloro-6-(4-chloro-2-fluoro-3-methoxyphenyl)pyridine-2-carboxylic acid, CAS Reg. No.
943832-60-8), compound of formula I + halauxifen-methyl (which is methyl 4-amino-3-chloro- 6-(4-chloro-2-fluoro-3-methoxyphenyl)pyridine-2-carboxylate, CAS Reg. No. 943831 -98-9), compound of formula I + iofensulfuron (which is 1-(2-iodophenylsulfonyl)-3-(4-methoxy-6- methyl-1 ,3,5-triazin-2-yl)urea, CAS Reg. No. 1 144097-22-2), compound of formula I + iofensulfuron-sodium (which is sodium /V-(2-iodophenylsulfonyl)-/V'-(4-methoxy-6-methyl- 1 ,3,5-triazin-2-yl)carbamimidate, CAS Reg. No. 1 144097-30-2), or compound of formula I + triafamone (which is /V-[2-[(4,6-dimethoxy-1 ,3,5-triazin-2-yl)carbonyl]-6-fluorophenyl]-/V- methyl-1 ,1 -difluoromethanesulfonamide, CAS Reg. No. 874195-61 -6);
wherein the mixture partners for the compound of formula (I) may optionally be in the form of an ester (in particular an agrochemically acceptable ester) or a salt (in particular an agrochemically acceptable salt) thereof (e.g. where chemically possible).
For applications in rice, more preferred is a mixture comprising: a compound of formula (I) + azimsulfuron, compound of formula (I) + bensulfuron, compound of formula (I) + bensulfuron- methyl, compound of formula (I) + benzobicyclon, compound of formula (I) + benzofenap, compound of formula (I) + bispyribac, compound of formula (I) + bispyribac-sodium, compound of formula (I) + clomazone, compound of formula (I) + clomeprop, compound of formula (I) + cyhalofop, compound of formula (I) + cyhalofop-butyl, compound of formula (I) + 2,4-D, compound of formula (I) + 2,4-D-dimethylammonium, compound of formula (I) + 2,4-D-2-ethylhexyl, compound of formula (I) + a choline salt of 2,4-D (see e.g. Examples 2 and 3 of WO2010/123871A1 ), compound of formula (I) + daimuron, compound of formula (I) + dicamba, compound of formula (I) + dicamba-dimethylammonium, compound of formula (I) + dicamba-potassium, compound of formula (I) + dicamba-sodium, compound of formula (I) + dicamba-diglycolamine, compound of formula (I) + a /V,/V-bis-[aminopropyl]methylamine salt of dicamba (see e.g. US2012/0184434A1 ), compound of formula (I) + esprocarb, compound of formula (I) + ethoxysulfuron, compound of formula (I) + fenoxaprop-P, compound of formula (I) + fenoxaprop-P-ethyl, compound of formula I + fenoxasulfone (CAS Reg. No. 639826-16-7), compound of formula (I) + fentrazamide, compound of formula (I) + florasulam, compound of formula (I) + halosulfuron, compound of formula (I) + halosulfuron- methyl, compound of formula (I) + imazosulfuron, compound of formula I + ipfencarbazone (CAS Reg. No. 212201-70-2), compound of formula (I) + MCPA, compound of formula (I) + mefenacet, compound of formula (I) + mesotrione, compound of formula I + metazosulfuron (NC-620, CAS Reg. No. 868680-84-6), compound of formula (I) + metsulfuron, compound of formula (I) + metsulfuron-methyl, compound of formula (I) + orthosulfamuron, compound of formula (I) + oxadiargyl, compound of formula (I) + oxadiazon, compound of formula (I) + pendimethalin, compound of formula (I) + penoxsulam, compound of formula (I) +
pretilachlor, compound of formula I + propyrisulfuron (TH-547, CAS Reg. No. 570415-88-2), compound of formula (I) + pyrazolynate, compound of formula (I) + pyrazosulfuron, compound of formula (I) + pyrazosulfuron-ethyl, compound of formula (I) + pyrazoxyfen, compound of formula (I) + pyribenzoxim, compound of formula (I) + pyriftalid, compound of formula (I) + pyriminobac, compound of formula (I) + pyriminobac-methyl, compound of formula (I) + pyrimisulfan, compound of formula (I) + quinclorac, compound of formula (I) + tefuryltrione, compound of formula (I) + triasulfuron and compound of formula (I) + trinexapac-ethyl, compound of formula (I) + 4-(4'-chloro-4-cyclopropyl-2'-fluorobiphenyl-3-yl)- 2,2,6,6-tetramethyl-2H-pyran-3,5(4/-/,6/-/)-dione (which is the compound of Example P8 disclosed on pages 31 -32 and 35-36 of WO 2010/136431 A9 (Syngenta Limited), and which is also compound A-13 disclosed in pages 4, 5, 7 and 1 1 of WO 201 1/073616 A2 (Syngenta Limited), these parts of these publications being incorporated herein by reference), compound of formula (I) + 4-(2',4'-dichloro-4-cyclopropylbiphenyl-3-yl)-2,2,6,6-tetramethyl- 2/-/-pyran-3,5(4/-/,6/-/)-dione (which is the compound of Example P9 disclosed on pages 36- 37 and 40-41 of WO 2010/136431 A9 (Syngenta Limited), and which is also compound A-12 disclosed in page 10 of WO 201 1/073616 A2 (Syngenta Limited), these parts of these publications being incorporated herein by reference), compound of formula (I) + 4-(4'-chloro- 4-ethyl-2'-fluorobiphenyl-3-yl)-2!2!6!6-tetramethyl-2H-pyran-3!5(4H,6H)-dione (which is compound A-66 disclosed on page 95 of WO 2008/071405 A1 (Syngenta Participations AG and Syngenta Limited), and which is also compound A-4 disclosed on page 7 of WO
201 1/073615 A2 (Syngenta Limited), these parts of these publications being incorporated herein by reference), compound of formula (I) + 4-(2',4'-dichloro-4-ethylbiphenyl-3-yl)-2,2,6,6- tetramethyl-2/-/-pyran-3,5(4/-/,6/-/)-dione (which is compound A-45 disclosed on page 93 of WO 2008/071405 A1 (Syngenta Participations AG and Syngenta Limited), and which is also the compound of Example P10 disclosed on pages 41 and 45 of WO 2010/136431 A9 (Syngenta Limited), and which is also compound A-7 disclosed on page 7 of WO
201 1/073615 A2 (Syngenta Limited), these parts of these publications being incorporated herein by reference), compound of formula (I) + 4-(2',4'-dichloro-4-ethylbiphenyl-3-yl)-5- (methoxycarbonyloxy)-2,2,6,6-tetramethyl-2/-/-pyran-3(6/-/)-one (which is compound D-26 disclosed on page 231 of WO 2008/071405 A1 (Syngenta Participations AG and Syngenta Limited), and which is also compound A-9 disclosed on page 8 of WO 201 1/073615 A2 (Syngenta Limited), these parts of these publications being incorporated herein by reference), compound of formula (I) + one of the specific herbicidal compounds disclosed in WO 2010/059671 (Dow, e.g. as defined in one of the examples therein and/or e.g. can be plus a safener) these parts of which are incorporated herein by reference, compound of formula I + halauxifen (which is 4-amino-3-chloro-6-(4-chloro-2-fluoro-3- methoxyphenyl)pyridine-2-carboxylic acid, CAS Reg. No. 943832-60-8), compound of formula I + halauxifen-methyl (which is methyl 4-amino-3-chloro-6-(4-chloro-2-fluoro-3- methoxyphenyl)pyridine-2-carboxylate, CAS Reg. No. 943831 -98-9), compound of formula I + iofensulfuron (which is 1-(2-iodophenylsulfonyl)-3-(4-methoxy-6-methyl-1 ,3,5-triazin-2- yl)urea, CAS Reg. No. 1 144097-22-2), compound of formula I + iofensulfuron-sodium (which is sodium /V-(2-iodophenylsulfonyl)-/V'-(4-methoxy-6-methyl-1 ,3,5-triazin-2-yl)carbamimidate, CAS Reg. No. 1 144097-30-2), or compound of formula I + triafamone (which is Λ/-[2-[(4,6- dimethoxy-1 ,3,5-triazin-2-yl)carbonyl]-6-fluorophenyl]-/V-methyl-1 ,1- difluoromethanesulfonamide, CAS Reg. No. 874195-61 -6);
wherein the mixture partners for the compound of formula (I) may optionally be in the form of an ester (in particular an agrochemically acceptable ester) or a salt (in particular an agrochemically acceptable salt) thereof (e.g. where chemically possible).
For applications in soybean, the following mixtures are preferred: compound of formula (I) + acifluorfen, compound of formula (I) + acifluorfen-sodium, compound of formula (I) + ametryn, compound of formula (I) + atrazine, compound of formula (I) + bentazone, compound of formula (I) + bicyclopyrone, compound of formula (I) + bromoxynil, compound of formula (I) + bromoxynil heptanoate, compound of formula (I) + bromoxynil octanoate, compound of formula (I) + bromoxynil heptanoate + bromoxynil octanoate, compound of formula (I) + carfentrazone, compound of formula (I) +
carfentrazone-ethyl, compound of formula (I) + chloransulam, compound of formula (I) + chloransulam-methyl, compound of formula (I) + chlorimuron, compound of formula (I) + chlorimuron-ethyl, compound of formula (I) + clethodim, compound of formula (I) + clomazone, compound of formula (I) + cyanazine, compound of formula (I) + 2,4-D
(especially for applications to 2,4-D-tolerant soybean, e.g. genetically-modified), compound of formula (I) + 2,4-D-dimethylammonium (especially for applications to 2,4-D-tolerant soybean, e.g. genetically-modified), compound of formula (I) + 2,4-D-2-ethylhexyl (especially for applications to 2,4-D-tolerant soybean, e.g. genetically-modified), compound of formula (I) + a choline salt of 2,4-D (see e.g. Examples 2 and 3 of WO2010/123871 A1 ) (especially for applications to 2,4-D-tolerant soybean, e.g. genetically-modified), compound of formula (I) + 2,4-D + glyphosate (especially for applications to 2,4-D-tolerant and/or glyphosate-tolerant soybean, e.g. genetically-modified), compound of formula (I) + 2,4-D-dimethylammonium + glyphosate (especially for applications to 2,4-D-tolerant and/or glyphosate-tolerant soybean, e.g. genetically-modified), compound of formula (I) + 2,4-D-2-ethylhexyl + glyphosate (especially for applications to 2,4-D-tolerant and/or glyphosate-tolerant soybean, e.g.
genetically-modified), compound of formula I + a choline salt of 2,4-D + glyphosate (see e.g. Examples 2 and 3 of WO2010/123871 A1 ) (especially for applications to dicamba-tolerant and/or glyphosate-tolerant soybean, e.g. genetically-modified), compound of formula (I) + dicamba (especially for applications to dicamba-tolerant soybean, e.g. genetically-modified), compound of formula (I) + dicamba-dimethylammonium (especially for applications to dicamba-tolerant soybean, e.g. genetically-modified), compound of formula (I) + dicamba- potassium (especially for applications to dicamba-tolerant soybean, e.g. genetically- modified), compound of formula (I) + dicamba-sodium (especially for applications to dicamba-tolerant soybean, e.g. genetically-modified), compound of formula (I) + dicamba- diglycolamine (especially for applications to dicamba-tolerant soybean, e.g. genetically- modified), compound of formula (I) + a /V,/V-bis-[aminopropyl]methylamine salt of dicamba (see e.g. US2012/0184434A1 ) (especially for applications to dicamba-tolerant soybean, e.g. genetically-modified), compound of formula (I) + dicamba + glyphosate (especially for applications to dicamba-tolerant and/or glyphosate-tolerant soybean, e.g. genetically- modified), compound of formula (I) + dicamba-dimethylammonium + glyphosate (especially for applications to dicamba-tolerant and/or glyphosate-tolerant soybean, e.g. genetically- modified), compound of formula (I) + dicamba-potassium + glyphosate (especially for applications to dicamba-tolerant and/or glyphosate-tolerant soybean, e.g. genetically- modified), compound of formula (I) + dicamba-sodium + glyphosate (especially for applications to dicamba-tolerant and/or glyphosate-tolerant soybean, e.g. genetically- modified), compound of formula (I) + dicamba-diglycolamine + glyphosate (especially for applications to dicamba-tolerant and/or glyphosate-tolerant soybean, e.g. genetically- modified), compound of formula (I) + a /V,/V-bis-[aminopropyl]methylamine salt of dicamba + glyphosate (especially for applications to dicamba-tolerant and/or glyphosate-tolerant soybean, e.g. genetically-modified), compound of formula (I) + diclosulam, compound of formula (I) + dimethenamid, compound of formula (I) + dimethenamid-P, compound of formula (I) + diquat, compound of formula (I) + diquat dibromide, compound of formula (I) + diuron, compound of formula (I) + fenoxaprop, compound of formula (I) + fenoxaprop-ethyl, compound of formula (I) + fenoxaprop-P, compound of formula (I) + fenoxaprop-P-ethyl, compound of formula (I) + fluazifop, compound of formula (I) + fluazifop-butyl, compound of formula (I) + fluazifop-P, compound of formula (I) + fluazifop-P-butyl, compound of formula (I) + flufenacet, compound of formula (I) + flumetsulam, compound of formula (I) + flumioxazin, compound of formula (I) + fluthiacet, compound of formula (I) + fluthiacet-methyl, compound of formula (I) + fomesafen, compound of formula (I) + glufosinate, compound of formula (I) + glufosinate-ammonium, compound of formula (I) + glyphosate, compound of formula (I) + glyphosate-diammonium, compound of formula (I) + glyphosate-isopropylammonium, compound of formula (I) + glyphosate-potassium, compound of formula (I) + imazethapyr, compound of formula (I) + lactofen, compound of formula (I) + mesotrione, compound of formula (I) + metolachlor, compound of formula (I) + S-metolachlor, compound of formula (I) + metribuzin, compound of formula (I) + oxyfluorfen, compound of formula (I) + paraquat, compound of formula (I) + paraquat dichloride, compound of formula (I) + pendimethalin, compound of formula (I) + pyroxasulfone, compound of formula I + quizalofop, compound of formula I + quizalofop-ethyl, compound of formula I + quizalofop-P, compound of formula I + quizalofop-P-ethyl, compound of formula I + quizalofop-P-tefuryl, compound of formula (I) + saflufenacil, compound of formula (I) + sethoxydim, compound of formula (I) + sulfentrazone, compound of formula (I) + thifensulfuron, compound of formula (I) + thifensulfuron-methyl, compound of formula (I) + tribenuron, compound of formula (I) + tribenuron-methyl, compound of formula (I) + trifluralin, compound of formula (I) + 4-(4'-chloro-4-cyclopropyl-2'- fluorobiphenyl-3-yl)-2,2,6,6-tetramethyl-2/-/-pyran-3,5(4/-/,6/-/)-dione (which is the compound of Example P8 disclosed on pages 31 -32 and 35-36 of WO 2010/136431 A9 (Syngenta Limited), and which is also compound A-13 disclosed in pages 4, 5, 7 and 1 1 of WO
201 1/073616 A2 (Syngenta Limited), these parts of these publications being incorporated herein by reference), compound of formula (I) + 4-(2',4'-dichloro-4-cyclopropylbiphenyl-3-yl)- 2,2,6,6-tetramethyl-2H-pyran-3,5(4H,6/-/)-dione (which is the compound of Example P9 disclosed on pages 36-37 and 40-41 of WO 2010/136431 A9 (Syngenta Limited), and which is also compound A-12 disclosed in page 10 of WO 201 1/073616 A2 (Syngenta Limited), these parts of these publications being incorporated herein by reference), compound of formula (I) + 4-(4'-chloro-4-ethyl-2'-fluorobiphenyl-3-yl)-2,2,6,6-tetramethyl-2H-pyran- 3,5(4H,6A7)-dione (which is compound A-66 disclosed on page 95 of WO 2008/071405 A1 (Syngenta Participations AG and Syngenta Limited), and which is also compound A-4 disclosed on page 7 of WO 201 1/073615 A2 (Syngenta Limited), these parts of these publications being incorporated herein by reference), compound of formula (I) + 4-(2',4'- dichloro-4-ethylbiphenyl-3-yl)-2,2,6,6-tetramethyl-2H-pyran-3,5(4H,6H)-dione (which is compound A-45 disclosed on page 93 of WO 2008/071405 A1 (Syngenta Participations AG and Syngenta Limited), and which is also the compound of Example P10 disclosed on pages 41 and 45 of WO 2010/136431 A9 (Syngenta Limited), and which is also compound A-7 disclosed on page 7 of WO 201 1/073615 A2 (Syngenta Limited), these parts of these publications being incorporated herein by reference), or compound of formula (I) + 4-(2',4'- dichloro-4-ethylbiphenyl-3-yl)-5-(methoxycarbonyloxy)-2,2,6,6-tetramethyl-2/-/-pyran-3(6/-/)- one (which is compound D-26 disclosed on page 231 of WO 2008/071405 A1 (Syngenta Participations AG and Syngenta Limited), and which is also compound A-9 disclosed on page 8 of WO 201 1/073615 A2 (Syngenta Limited), these parts of these publications being incorporated herein by reference);
wherein the mixture partners for the compound of formula (I) may optionally be in the form of an ester (in particular an agrochemically acceptable ester) or a salt (in particular an agrochemically acceptable salt) thereof (e.g. where chemically possible).
In the above-mentioned compositions or mixtures comprising a compound of formula (I) (in particular one of the specific compounds disclosed herein, in particular one of compounds A1 to A151 or P1 to P12 disclosed herein, more particularly one of compounds A1 to A1 1 1 , or A142 to A149, or A150 or A151 , or P1 to P12 disclosed herein, present either as a free compound and/or as an agrochemically acceptable salt thereof) and one or more further herbicides, the weight ratio of the compound of formula (I) to each further herbicide can vary over a large range and is, typically, from 300:1 to 1 :500, especially from 150:1 to 1 :200, more especially from 100:1 to 1 :100, even more especially from 30:1 to 1 :30. Typically, these weight ratios are measured as the free compound(s), i.e. excluding the weight of any associated salt counterion(s).
The compounds of formula I according to the invention can also be used in combination with a safener. Preferably, in these mixtures, the compound of the formula I is one of the exemplified compounds (in particular one of compounds A1 to A151 or P1 to P12, more particularly one of compounds A1 to A1 1 1 , or A142 to A149, or A150 or A151 , or P1 to P12) disclosed herein e.g. hereinbelow, present either as a free compound and/or as an agrochemically acceptable salt thereof. The following mixtures with safeners, especially, come into consideration: compound of formula I + cloquintocet-mexyl, compound of formula I + cloquintocet acid or an agrochemically acceptable salt thereof, compound of formula I + fenchlorazole-ethyl, compound of formula I + fenchlorazole acid or an agrochemically acceptable salt thereof, compound of formula I + mefenpyr-diethyl, compound of formula I + mefenpyr diacid, compound of formula I + isoxadifen-ethyl, compound of formula I + isoxadifen acid, compound of formula I + furilazole, compound of formula I + furilazole R isomer, compound of formula (I) + N-(2-methoxybenzoyl)-4-[(methylaminocarbonyl)amino]benzenesulfonamide, compound of formula I + benoxacor, compound of formula I + dichlormid, compound of formula I + AD-67, compound of formula I + oxabetrinil, compound of formula I + cyometrinil, compound of formula I + cyometrinil Z-isomer, compound of formula I + fenclorim, compound of formula I + cyprosulfamide, compound of formula I + naphthalic anhydride, compound of formula I + flurazole, compound of formula I + CL 304,415, compound of formula I + dicyclonon, compound of formula I + fluxofenim, compound of formula I + DKA-24, compound of formula I + R-29148 and compound of formula I + PPG-1292.
The above-mentioned safeners and herbicides are described, for example, in the Pesticide Manual, 14th Edition, British Crop Protection Council, 2006; or The Pesticide Manual, 15th edition (2009) or 16th Edition (2012), ed. C.D.S. Tomlin, British Crop Production Council. R-29148 is described, for example by P.B. Goldsbrough et al., Plant Physiology, (2002), Vol. 130 pp. 1497-1505 and references therein. PPG-1292 is known from WO 2009/21 1761 . N- (2-methoxybenzoyl)-4-[(methylaminocarbonyl)amino]benzenesulfonamide is known from EP365484.
Especially preferably, in a composition or mixture comprising a compound of formula (I) (in particular one of the specific compounds disclosed herein, in particular one of compounds A1 to A151 or P1 to P12 disclosed herein, or more particularly one of compounds A1 to A1 1 1 , or A142 to A149, or A150 or A151 , or P1 to P12 disclosed herein, present either as a free compound and/or as an agrochemically acceptable salt thereof) and a safener, the safener comprises (e.g. is) benoxacor, cloquintocet-mexyl, cloquintocet acid or an agrochemically acceptable salt thereof, cyprosulfamide, mefenpyr-diethyl, isoxadifen-ethyl and/or Λ/-(2- methoxybenzoyl)-4-[(methylaminocarbonyl)amino]-benzenesulfonamide. In one particular embodiment, the safener comprises (e.g. is) cloquintocet-mexyl, cloquintocet acid or an agrochemically acceptable salt thereof, mefenpyr-diethyl and/or isoxadifen-ethyl; in particular for use on non-oat cereals such as wheat, barley, rye and/or triticale. Cloquintocet-mexyl is particularly valuable and is the most preferred safener, especially for use on non-oat cereals such as wheat, barley, rye and/or triticale.
In the above-mentioned compositions or mixtures comprising a compound of formula (I) (in particular, one of the specific compounds disclosed herein, in particular one of compounds A1 to A151 or P1 to P12 disclosed herein, or more particularly one of compounds A1 to A1 1 1 , or A142 to A149, or A150 or A151 , or P1 to P12 disclosed herein, present either as a free compound and/or as an agrochemically acceptable salt thereof) with a safener, the weight ratio of the compound of formula (I) to the safener can vary over a large range and is, typically, from 200:1 to 1 :200, especially from 50:1 to 1 :50 such as from 50:1 to 1 :20, more especially from 20:1 to 1 :20, even more especially from 20:1 to 1 :10. Preferably, the safener comprises (e.g. is) benoxacor, cloquintocet-mexyl, cloquintocet acid or an agrochemically acceptable salt thereof, cyprosulfamide, mefenpyr-diethyl, isoxadifen-ethyl and/or Λ/-(2- methoxybenzoyl)-4-[(methylaminocarbonyl)amino]-benzenesulfonamide, and the weight ratio of the compound of formula (I) to the safener is from 50:1 to 1 :20 or from 20:1 to 1 :10, more preferably from 15:1 to 1 :2. Typically, these weight ratios are measured as the free compound(s), i.e. excluding the weight of any associated salt counterion(s). Application rates of herbicide (e.g. compound of formula (I)) and/or safener: The rate of application of safener relative to the compound of formula (I) is largely dependent upon the mode of application. In the case of field and/or soil and/or plant treatment (e.g. in a field or glasshouse): for example from 0.5 to 1000 g of safener per ha, or preferably from 1 to 250 g or from 2 to 200 g of safener per ha, are applied; and/or generally from 1 to 2000 g of compound of formula (I) per ha, or preferably from 5 to 500 g or from 10 to 400 g of compound of formula (I) per ha, are applied, ha = hectare. Typically, these application rates are measured as the free compound, i.e. excluding the weight of any associated salt counterion(s). In field treatment, the application of the compound of formula (I) is preferably post-emergence.
The compounds and/or herbicidal compositions according to the invention are suitable for all methods of application customary in agriculture, such as, for example, pre-emergence application, post-emergence application and seed dressing. Post-emergence application is preferred. Depending upon the intended use, the safeners can be used for pretreating the seed material of the crop plant (dressing the seed or seedlings) or introduced into the soil before or after sowing, followed by the application of the (unsafened) compound of the formula (I), optionally in combination with a co-herbicide. It can, however, also be applied alone or together with the herbicide before or after emergence of the plants. The treatment of the plants or the seed material with the safener can therefore take place in principle independently of the time of application of the herbicide. The treatment of the plant by simultaneous application of herbicide and safener (e.g. in the form of a tank mixture) is generally preferred. The rate of application of safener relative to herbicide is largely dependent upon the mode of application. In the case of field and/or soil and/or plant treatment (e.g. in a field or glasshouse), generally from 0.001 to 5.0 kg of safener/ha, preferably from 0.001 to 0.5 kg of safener/ha, are applied. In the case of seed dressing, generally from 0.001 to 10 g of safener/kg of seed, preferably from 0.05 to 2 g of safener/kg of seed, are applied. When the safener is applied in liquid form, with seed soaking, shortly before sowing, it is advantageous to use safener solutions which contain the active ingredient in a concentration of from 1 to 10 000 ppm, preferably from 100 to 1000 ppm.
In the invention, in the case of field and/or soil and/or plant treatment (e.g. post-emergence application), generally from 1 to 2000 g of herbicide (in particular compound of formula (I)) / ha, but preferably from 5 to 1000 g of herbicide (in particular compound of formula (I)) / ha, more preferably from 10 to 400 g of herbicide (in particular compound of formula (I)) / ha, is applied. If a safener is used, in the case of field and/or soil and/or plant treatment (e.g. post- emergence application), generally from 0.5 to 1000 g of safener/ha, preferably from 2 to 500 g of safener/ha, more preferably from 5 to 200 g of safener/ha, is applied.
In one particular embodiment, the composition or mixture comprising the compound of formula (I) and one or more further herbicides (e.g. as mentioned hereinabove) can be applied together with one of the safeners mentioned herein, e.g. hereinabove.
In a further aspect, the present invention provides a herbicidal composition, e.g. for use in a method of controlling weeds (in particular monocotyledonous such as grassy
monocotyledonous weeds) in crops of useful plants, comprising a compound of formula (I) as defined herein (in particular, one of the specific compounds disclosed herein, in particular one of compounds A1 to A151 or P1 to P12 disclosed herein, or more particularly one of compounds A1 to A1 1 1 , or A142 to A149, or A150 or A151 , or P1 to P12 disclosed herein, present either as a free compound and/or as an agrochemically acceptable salt thereof) (e.g. a herbicidally effective amount thereof), and an agrochemically acceptable carrier, diluent and/or solvent, and also comprising a plant growth regulator, and optionally one or more further herbicides (e.g. as described herein, e.g. glyphosate and/or dicamba and/or 2,4-D) and optionally a safener (e.g. as described herein).
Preferably, the plant growth regulator is: abscisic acid, acibenzolar-S-methyl, a
brassinosteroid plant growth regulator, 24-epi brassinolide, 28-homobrassinolide, chlormequat, a cytokinin plant growth regulator, ethephon, ethylene, flurprimidol, gibberellic acid, a gibberellin plant growth regulator (in particular gibberellin A3, gibberellin A4, or gibberellin A7, or gibberellin A4 and gibberellin A7), GR24, indole-3-acetic acid (IAA), indole- 3-butyric acid (IBA), jasmonic acid, methyl jasmonate, a karrikin plant growth regulator, maleic hydrazide, mefluidide, mepiquat, methylcyclopropene such as 1 -methylcyclopropene, 1 -naphthaleneacetic acid (NAA), paclobutrazol, prohexadione, prohexadione-calcium, salicylic acid, a strigolactone plant growth regulator (such as strigol or orobanchol or a derivative of one of these, or the synthetic strigolactone GR-24) (see e.g. K. Yoneyma et al, „Strigolactones as a new plant growth regulator", http://www.niaes.affrc.go.jp/marco/ marco2009/english/program/W3-04_Yoneyama_Koichi.pdf), trinexapac-ethyl and/or uniconzole, or an agrochemically acceptable salt e.g. acid addition salt or metal or ammonium salt e.g. alkali metal salt of any of these. More preferably, the plant growth regulator is: gibberellic acid, or a gibberellin plant growth regulator (in particular gibberellin A3, gibberellin A4, or gibberellin A7, or gibberellin A4 and gibberellin A7), or an
agrochemically acceptable salt e.g. metal or ammonium salt e.g. alkali metal salt of any of these. Most preferably, the plant growth regulator is gibberellic acid or an agrochemically acceptable salt e.g. metal or ammonium salt e.g. alkali metal salt thereof. Gibberellic acid is preferred because WO 2014/071 1 10 A1 (Valent USA Corp.) discloses that gibberelic acid, when mixed with clethodim, increased clethodim's control and/or speed of control of
Johnsongrass (Sorghum halepense) and volunteer corn; and increased the control of glyphosate-tolerant (Roundup-Ready™) volunteer corn at 21 days after the application of a mixture of clethodim + dicamba-glycolamine + glyphosate + gibberellic acid (compared to clethodim + dicamba-glycolamine + glyphosate + ammonium sulfate).
In the above-mentioned herbicidal compositions comprising a compound of formula (I), an agrochemically acceptable carrier, diluent and/or solvent, and a plant growth regulator (e.g. gibberellic acid or a salt thereof), and optionally one or more further herbicides and optionally a safener, the weight ratio of the compound of formula (I) to the plant growth regulator (e.g. gibberellic acid or an agrochemically acceptable salt e.g. metal salt e.g. alkali metal salt thereof) can vary over a large range and is, typically, from 500:1 to 1 :500, especially from 200:1 to 1 :200, more especially from 100:1 to 1 :100, even more especially from 30:1 to 1 :30. Typically, these weight ratios are measured as the free compound(s), i.e. excluding the weight of any associated salt counterion(s).
The following Examples illustrate the invention further but do not limit the invention.
PREPARATION EXAMPLES
Those skilled in the art will appreciate that certain compounds described below are mostly beta-ketoenols, and as such may exist as a single tautomer or as a mixture of keto-enol and diketone tautomers, as described and/or shown in the description hereinabove, and/or as described for example by J. March, Advanced Organic Chemistry, third edition, John Wiley and Sons,. The compounds shown below, and/or in Table T1 , are drawn as an arbitrary single diketone (cyclic dione) tautomer, but it should be inferred that this description covers both the diketone (cyclic dione) form and any possible enols / keto-enols which could arise through tautomerism. Where more than one tautomer is observed in proton (1H) NMR, the data shown are for the mixture of tautomers. Furthermore, some of the compounds shown below may be drawn as single enantiomers for the purposes of simplicity, but unless specified as single enantiomers, these structures should be construed as representing a mixture of enantiomers. Additionally, some of the compounds can exist as diastereoisomers, and it should be inferred that these can be present as a mixture of diastereoisomers or as any possible single diastereoisomer. Within the detailed experimental section the diketone tautomer is chosen for naming purposes, even if the predominant tautomer is the enol form.
Abbreviations
As used herein, room (ambient) temperature is typically about 15-30 °C (e.g. 15-25 °C).
NMR = nuclear magnetic resonance; in which: s = singlet, d = doublet, t = triplet, q = quartet, dd = doublet of doublets, brs = broad singlet, m = multiplet, etc.
d4 MeOD = tetradeutero-methanol (CD3OD)
Example 1 : Preparation of 8-(2-chloro-6-methoxy-4-prop-1 -ynyl-phenyl)-1 ,2,4,5- tetrahydropyrazolo[1 ,2-d][1 ,4,5]oxadiazepine-7,9-dione (compound A29)
Figure imgf000098_0001
tep 1 : Preparation of 5-bromo-1 -chloro-2-iodo-3-methoxy-benzene
Figure imgf000099_0001
Dry methanol (160ml_) was cooled to 10 °C and potassium hydroxide (14.9g) was added portionwise over 25 minutes. Once dissolved, this solution was added over 15 minutes to a refluxing solution of 5-bromo-1-chloro-3-fluoro-2-iodo-benzene (CAS Reg. No. 83027-73-0, 40.0 g) in dry methanol (320ml_). After 46 hours refluxing the reaction mixture was concentrated and partitioned between water (500ml_) and ethyl acetate (500ml_). The aqueous phase was extracted with further ethyl acetate (2 x 200ml_). The combined organic layers were washed with brine (400ml_), dried over magnesium sulfate, concentrated and purified by chromatography on silica eluting with ethyl acetate in iso-hexane to give 5-bromo- 1 -chloro-2-iodo-3-methoxy-benzene (37.767g) as a pale pink solid.
1H NMR (500 MHz, CDCI3) δ (delta) 7.28 (d, 1 H), 6.82 (d, 1 H), 3.90 (s, 3H)
Step 2: Preparation of dimethyl 2-(4-bromo-2-chloro-6-methoxy-phenyl)propanedioate
Figure imgf000099_0002
A mixture of 5-bromo-1-chloro-2-iodo-3-methoxy-benzene (3.00 g), pyridine-2-carboxylic acid (0.425 g), copper (I) iodide (0.329 g) and cesium carbonate (8.49 g) was purged with nitrogen. 1 ,4-dioxane (38 mL) was added followed by dimethyl propanedioate (2.28 g) and the resulting mixture was stirred at 1 10 °C for 22 hours.
The reaction mixture was partitioned between ethyl acetate and saturated aqueous ammonium chloride solution. The phases were separated and the aqueous phase extracted with further ethyl acetate (x2). The combined organic phases were washed with water (x2), brine, dried over magnesium sulfate and concentrated and purified by chromatography on silica eluting with ethyl acetate in iso-hexane to give dimethyl 2-(4-bromo-2-chloro-6- methoxy-phenyl)propanedioate (2.0334 g) as a colourless oil.
1H NMR (500 MHz, CDCI3) δ (delta) 7.22 (d, 1 H), 6.99 (d, 1 H), 5.18 (s, 1 H), 3.82 (s, 3H), 3.76 (s, 6H)
Step 3: Preparation of dimethyl 2-(2-chloro-6-methoxy-4-prop-1-ynyl-phenyl)propanedioate
Figure imgf000100_0001
To a solution of dimethyl 2-(4-bromo-2-chloro-6-methoxy-phenyl)propanedioate (1.99 g) in 1 ,4-dioxane (29.9 mL) under nitrogen atmosphere was added tributyl(prop-1-ynyl)stannane (CAS Reg. No. 64099-82-7, 1 .97 g) and palladium (0) tetrakis(triphenylphosphine) (0.231 g). The reaction mixture was heated to 100 °C with stirring under nitrogen for 2.5 hours. The reaction mixture was cooled, concentrated and purified by chromatography on silica eluting with ethyl acetate in iso-hexane to give dimethyl 2-(2-chloro-6-methoxy-4-prop-1-ynyl- phenyl)propanedioate (1.347 g) as an orange gum.
1H NMR (500 MHz, CDCI3) δ (delta) 7.08 (d, 1 H), 6.86 (d, 1 H), 5.20 (s, 1 H), 3.81 (s, 3H), 3.76 (s, 6H), 2.05 (s, 3H)
Step 4: Preparation of 8-(2-chloro-6-methoxy-4-prop-1-ynyl-phenyl)-1 ,2,4,5- tetrahydropyrazolo[1 ,2-d][1 ,4,5]oxadiazepine-7,9-dione (compound A29)
Figure imgf000100_0002
A degassed suspension of 1 ,4,5-oxadiazepane hydrochloride (CAS Reg. No. 329704-29-2, 0.669 g) and triethylamine (3.36 mL) in xylenes (13.5 mL) was stirred under nitrogen at 60 °C for 2.5 hours. Dimethyl 2-(2-chloro-6-methoxy-4-prop-1 -ynyl-phenyl)propanedioate (0.300 g) was added and the reaction mixture was heated to 150 °C for a further 6 hours. The reaction mixture was cooled to room temperature and allowed to stand overnight.
The reaction mixture was poured into water (40 ml) and made alkaline by the addition of 2 M aqueous sodium hydroxide (10 ml). The aqueous layer was extracted twice with ethyl acetate. The combined organic layers were extracted twice with further 2 M aqueous sodium hydroxide. The combined aqueous alkaline phases were acidified to pH 2-3 by addition of 2 M hydrochloric acid and extracted with dichloromethane (x2). The combined organic extracts were dried over magnesium sulfate, concentrated and purified by chromatography on silica eluting with methanol in dichloromethane to give 8-(2-chloro-6-methoxy-4-prop-1-ynyl- phenyl)-1 ,2,4,5-tetrahydropyrazolo[1 ,2-d][1 ,4,5]oxadiazepine-7,9-dione (147 mg) as a pale yellow solid.
1H N MR (400 MHz, CDCI3) δ (delta) 7.02-7.13 (m, 1 H), 6.72-6.89 (m, 1 H), 4.90-5.24 (m, 1 H), 3.62-4.36 (m, 1 1 H), 2.04-2.10 (m, 3H)
Example 2: Preparation of 8-(2-fluoro-6-methoxy-4-prop-1 -ynyl-phenyl)-1 ,2,4,5- tetrahydropyrazolo[1 ,2-d][1 ,4,5]oxadiazepine-7,9-dione (compound A30)
Figure imgf000101_0001
Step 1 : Preparation of 5-bromo-1 -fluoro-2-iodo-3-methoxy-benzene
\
Figure imgf000101_0002
To 5-bromo-1 ,3-difluoro-2-iodo-benzene (2.00 g) under nitrogen atmosphere was added sodium methoxide (0.5 M in methanol, 17.0 ml_). The solution was heated to 60 °C for 17 hours. A further aliquot of sodium methoxide (0.5 M in methanol, 4.56 ml.) was added and heating continued for a further 25 hours.
The reaction solution was allowed to cool and concentrated to afford a white solid. This was partitioned between dichloromethane and water. The aqueous phase was extracted with further dichloromethane (x2) and the combined organic phases were washed with brine, dried over magnesium sulfate, concentrated and purified by chromatography on silica eluting with ethyl acetate in iso-hexane to give 5-bromo-1 -fluoro-2-iodo-3-methoxy-benzene (1 .5926 g) as a white solid.
1H NMR (400 MHz, CDCI3) δ (delta) 6.91 (dd, 1 H), 6.60-6.82 (m, 1 H), 3.91 (s, 3H) Step 2: Preparation of dimethyl 2-(4-bromo-2-fluoro-6-methoxy-phenyl)propanedioate
Figure imgf000102_0001
A mixture of 5-bromo-1-fluoro-2-iodo-3-methoxy-benzene (1.576 g), pyridine-2-carboxylic acid (0.2345 g), copper (I) iodide (0.1814 g) and cesium carbonate (4.684 g) was purged with nitrogen. 1 ,4-dioxane (36.67 mL) was added followed by dimethyl propanedioate (1.089 mL) and the resulting mixture was stirred at 1 10 °C for 22 hours.
The reaction mixture was partitioned between ethyl acetate and saturated aqueous ammonium chloride solution. The phases were separated and the aqueous phase was extracted with further ethyl acetate (x2). The combined organic phases were washed with water (x2), brine, dried over magnesium sulfate, concentrated and purified by
chromatography on silica eluting with ethyl acetate in iso-hexane to give dimethyl 2-(4- bromo-2-fluoro-6-methoxy-phenyl)propanedioate (1 .1 17 g) as a colourless gum.
1H NMR (400 MHz, CDCI3) δ (delta) 6.95 (dd, 1 H), 6.84 (brs, 1 H), 5.02 (s, 1 H), 3.84 (s, 3H), 3.77 (s, 6H)
Step 3: Preparation of dimethyl 2-(2-fluoro-6-methoxy-4-prop-1-ynyl-phenyl)propanedioate
Figure imgf000102_0002
To a solution of dimethyl 2-(4-bromo-2-fluoro-6-methoxy-phenyl)propanedioate (2.72 g) in 1 ,4-dioxane (40.6 mL) under nitrogen atmosphere was added tributyl(prop-1-ynyl)stannane (CAS Reg. No. 64099-82-7, 2.96 mL) and palladium (0) tetrakis(triphenylphosphine) (0.375 g). The reaction mixture was heated to 100 °C with stirring under nitrogen atmosphere for 2.5 hours.
The reaction mixture was cooled, concentrated and purified by chromatography on silica eluting with ethyl acetate in iso-hexane to give dimethyl 2-(2-fluoro-6-methoxy-4-prop-1-ynyl- phenyl)propanedioate (1.47 g) as a yellow gum that solidified on standing.
1H NMR (400 MHz, CDCI3) δ (delta) 6.76 (dd, 1 H), 6.67-6.73 (m, 1 H), 5.01-5.05 (m, 1 H), 3.81 (s, 3H), 3.76 (s, 6H), 2.03 (s, 3H)
Step 4: Preparation of methyl 2-(2-fluoro-6-methoxy-4-prop-1-ynyl-phenyl)acetate
Figure imgf000103_0001
A mixture of dimethyl 2-(2-fluoro-6-methoxy-4-prop-1 -ynyl-phenyl)propanedioate (1.46 g), dimethylsulfoxide (6.25 ml_), lithium chloride (0.231 g) and water (0.124 mL) was heated to 120 °C for 4 hours. The reaction mixture was cooled and allowed to stand overnight. The reaction mixture was partitioned between water and diethyl ether. The organic extract was dried over magnesium sulfate, concentrated and purified by chromatography on silica eluting with ethyl acetate in iso-hexane to give methyl 2-(2-fluoro-6-methoxy-4-prop-1 -ynyl- phenyl)acetate (220 mg) as a white solid.
1H NMR (400 MHz, CDCI3) δ (delta) 6.72-6.80 (m, 1 H), 6.62-6.71 (m, 1 H), 3.79 (s, 3H), 3.69 (s, 3H), 3.65 (d, 2H) 2.04 (s, 3H) fluoro-6-methoxy-4-prop-1 -ynyl-phenyl)acetic acid
Figure imgf000103_0002
To a mixture of methyl 2-(2-fluoro-6-methoxy-4-prop-1-ynyl-phenyl)acetate (1.13 g) in tetrahydrofuran (57.4 mL) was added a solution of potassium hydroxide (0.537 g) in water (18.2 mL) and the mixture stirred at room temperature for 17 hours. Further potassium hydroxide (0.537 g) was added and the mixture was stirred at room temperature for a further 8 hours and allowed to stand at room temperature over the weekend. The reaction mixture was concentrated to remove the organic solvent and the residue quenched with 2 M hydrochloric acid. The resulting precipitate was collected by filtration to give 2-(2-fluoro-6- methoxy-4-prop-1-ynyl-phenyl)acetic acid (1 g) as a white solid.
1H NMR (400 MHz, CDCI3) δ (delta) 6.75 (dd, 1 H), 6.70 (s, 1 H), 3.81 (s, 3H), 3.69 (d, 2H), 2.03 (s, 3H)
Step 6: Preparation of ethyl 1 ,4,5-oxadiazepane-4-carboxylate
Figure imgf000104_0001
Ethyl chloroformate (3.1 g) was added drop wise to a cooled suspension of 1 ,4,5- oxadiazepane dihydrochloride (CAS Reg. No. 405281-14-3, 5.0 g) in pyridine (29 mL). The reaction mixture was stirred at room temperature for 30 minutes and at 70 °C for 3 hours, then cooled to room temperature and allowed to stand overnight.
After quenching with water (100 ml) the reaction mixture was extracted with dichloromethane (3 x 100 ml). The combined organic extracts were dried over magnesium sulfate, concentrated and azeotroped with toluene to remove any residual pyridine. The resulting liquid was purified by vacuum distillation (Kugelrohr oven, house vacuum, collected fraction that came off at 200 °C) to give ethyl 1 ,4,5-oxadiazepane-4-carboxylate (1 .49 g) as a colourless liquid.
1H NMR (400 MHz, CDCI3) δ (delta) 4.19 (q, 2H), 3.89 (t, 2H), 3.72-3.77 (m, 2H), 3.60-3.68 (m, 2H), 2.92-3.07 (m, 2H), 1 .29 (t, 3H)
S -6-methoxy-4-prop-1 -ynyl-phenyl)acetyl chloride
Figure imgf000104_0002
Oxalyl dichloride (0.43 mL) was added drop wise to a stirred suspension of 2-(2-fluoro-6- methoxy-4-prop-1-ynyl-phenyl)acetic acid (1.0 g) and one drop of /V,/V-dimethylformamide in dichloromethane (90 mL). The mixture was stirred at room temperature until gas evolution had ceased (about 2 hours). A further portion of oxalyl dichloride (0.43 mL) was added and the reaction stirred at room temperature for a further 2 hours. The reaction was concentrated to give 2-(2-fluoro-6-methoxy-4-prop-1-ynyl-phenyl)acetyl chloride as an off-white solid, which was used crude in the next step.
Step 8: Preparation of 8-(2-fluoro-6-methoxy-4-prop-1 -ynyl-phenyl)-1 ,2,4,5- tetrahydropyrazolo[1 ,2-d][1 ,4,5]oxadiazepine-7,9-dione
Figure imgf000105_0001
A solution of 2-(2-fluoro-6-methoxy-4-prop-1-ynyl-phenyl)acetyl chloride (0.366 g) in dichloromethane (18.3 mL) was added portionwise to a solution of ethyl 1 ,4,5-oxadiazepane- 4-carboxylate (0.265 g) and triethylamine (0.466 mL) in dichloromethane (0.912 mL) and stirred at room temperature for 2 hours, then allowed to stand at room temperature over the weekend.
The reaction mixture was partitioned between water and dichloromethane. The aqueous layer was extracted twice more with dichloromethane. The combined organic extracts were washed with 2 M hydrochloric acid, dried over magnesium sulfate, concentrated and purified by chromatography on silica eluting with ethyl acetate in iso-hexane to give 8-(2-fluoro-6- methoxy-4-prop-1-ynyl-phenyl)-1 ,2,4,5-tetrahydropyrazolo[1 ,2-d][1 ,4,5]oxadiazepine-7,9- dione (245 mg) as a yellow gum.
1H NMR (400 MHz, CDCI3) δ (delta) 6.71-6.78 (m, 1 H), 6.65-6.71 (m, 1 H), 2.92-4.41 (m, 15H), 2.05 (s, 3H), 1 .19-1.36 (m, 3H)
Step 9: Preparation of 8-(2-fluoro-6-methoxy-4-prop-1 -ynyl-phenyl)-1 ,2,4,5- tetrahydropyrazolo[1 ,2-d][1 ,4,5]oxadiazepine-7,9-dione (compound A30)
Figure imgf000106_0001
To a solution of ethyl 5-[2-(2-fluoro-6-methoxy-4-prop-1-ynyl-phenyl)acetyl]-1 ,4,5- oxadiazepane-4-carboxylate (0.235 g) in tetrahydrofuran (3.1 1 mL) under nitrogen atmosphere was added dropwise lithium hexamethyldisilazide (1 M in tetrahydrofuran, 1 .55 mL) and the mixture stirred at room temperature for 3 hours. The reaction was concentrated then partitioned between 2 M hydrochloric acid and dichloromethane. The aqueous layer was extracted with further dichloromethane (x2). The combined organic extracts were dried over magnesium sulfate, concentrated and purified by chromatography on silica eluting with ethyl acetate in iso-hexane to give 8-(2-fluoro-6-methoxy-4-prop-1-ynyl-phenyl)-1 ,2,4,5- tetrahydropyrazolo[1 ,2-d][1 ,4,5]oxadiazepine-7,9-dione (13mg) as a brown gum.
1H NMR (400 MHz, CDCI3) δ (delta) 6.64-6.87 (m, 2H), 4.60-4.99 (m, 1 H), 4.27-4.42 (m, 2H), 3.97-4.08 (m, 2H), 3.79-3.92 (m, 3H), 3.70-3.79 (m, 4H), 2.02-2.06 (m, 3H)
Example 3: Preparation of 2-(2-fluoro-6-methoxy-4-prop-1 -ynyl-phenyl)-5,6,7,8- tetrahydropyrazolo[1 ,2-a]pyridazine-1 ,3-dione (compound A24)
Figure imgf000106_0002
Step 1 : Preparation of methyl 2-(4-bromo-2-fluoro-6-methoxy-phenyl)acetate
Figure imgf000107_0001
A mixture of dimethyl 2-(4-bromo-2-fluoro-6-methoxy-phenyl)propanedioate (5.00 g), dimethyl sulfoxide (18.8 mL), lithium chloride (0.696 g) and water (0.373 mL) was heated to 120 °C for 5 hours. The reaction mixture was cooled and allowed to stand overnight. The reaction mixture was partitioned between water and diethyl ether. The organic extract was dried over magnesium sulfate, concentrated and purified by chromatography on silica eluting with ethyl acetate in iso-hexane to give methyl 2-(4-bromo-2-fluoro-6-methoxy- phenyl)acetate (2.57 g) as a white solid.
1H NMR (400 MHz, CDCI3) δ (delta) 6.91 (dd, 1 H), 6.82 (s, 1 H), 3.81 (s, 3H), 3.68 (s, 3H), 3.62 (d, 2H)
Step 2: Preparation of 2-(4-bromo-2-fluoro-6-methoxy-phenyl)acetic acid
Figure imgf000107_0002
To a solution of methyl 2-(4-bromo-2-fluoro-6-methoxy-phenyl)acetate (2.57 g) in tetrahydrofuran (55.7 mL) was added a solution of potassium hydroxide (2.08 g) in water (35.2 mL) and the mixture stirred at room temperature for 17 hours. The reaction mixture was concentrated to remove the organic solvent, and the residue was quenched with 2 M hydrochloric acid. The resulting precipitate was collected by filtration to give 2-(4-bromo-2- fluoro-6-methoxy-phenyl)acetic acid (2.4 g) as a white solid.
1H NMR (400 MHz, CDCI3) δ (delta) 6.91 (dd, 1 H), 6.81-6.84 (m, 1 H), 3.82 (s, 3H), 3.66 (d, 2H)
Step 3: Preparation of 2-(4-bromo-2-fluoro-6-methoxy-phenyl)acetyl chloride
Figure imgf000108_0001
Oxalyl dichloride (0.49 ml.) was added dropwise to a stirred suspension of 2-(4-bromo-2- fluoro-6-methoxy-phenyl)acetic acid (1 .35 g) and one drop of Λ/,/V-dimethylformamide in dichloromethane (103 ml_). The mixture was stirred at room temperature until gas evolution had ceased (about 3 hours). The reaction was concentrated to give 2-(2-fluoro-6-methoxy-4- prop-1-ynyl-phenyl)acetyl chloride as an off-white solid, which was used crude in the next step.
Step 4: Preparation of ethyl 2-[2-(4-bromo-2-fluoro-6-methoxy- phenyl)acetyl]hexahydropyridazine-1 -carboxylate
Figure imgf000108_0002
A solution of 2-(4-bromo-2-fluoro-6-methoxy-phenyl)acetyl chloride in dichloromethane (61.6 mL) was added portion wise to a stirred solution of ethyl hexahydropyridazine-1-carboxylate (CAS Reg. No. 5740-50-1 , 0.812 g) and triethylamine (1.57 mL) in dichloromethane (3.08 mL) and stirred for 2 hours, then allowed to stand overnight.
The reaction mixture was partitioned between water and dichloromethane. The aqueous layer was extracted twice more with dichloromethane. The combined organic extracts were washed with 2 M hydrochloric acid, dried over magnesium sulfate, concentrated and purified by chromatography on silica eluting with ethyl acetate in iso-hexane to give ethyl 2-[2-(4- bromo-2-fluoro-6-methoxy-phenyl)acetyl]hexahydropyridazine-1-carboxylate (960 mg) as a yellow gum.
1H NMR (400 MHz, CDCI3) δ (delta) 6.89 (dd, 1 H), 6.81 (s, 1 H), 4.42-4.58 (m, 1 H), 4.13-4.32 (m, 3H), 3.82 (s, 3H), 3.48-3.76 (m, 2H), 2.60-2.94 (m, 2H), 1.53-1 .79 (m, 4H), 1 .32 (t, 3H)
Step 5: Preparation of 2-(4-bromo-2-fluoro-6-methoxy-phenyl)-5, 6,7,8- tetrahydropyrazolo[1 ,2-a]pyridazine-1 ,3-dione
Figure imgf000109_0001
To a solution of ethyl 2-[2-(4-bromo-2-fluoro-6-methoxy-phenyl)acetyl]hexahydropyridazine- 1 -carboxylate (0.760 g) in tetrahydrofuran (9.42 mL) under nitrogen atmosphere was added, dropwise, lithium hexamethyldisilazide (1 M in tetrahydrofuran, 4.71 mL) and the mixture stirred at room temperature for 3 hours. The reaction was concentrated then partitioned between 2 M hydrochloric acid and dichloromethane. The aqueous layer was extracted with further dichloromethane (x2). The combined organic extracts were dried over magnesium sulfate, concentrated and purified by chromatography on silica eluting with ethyl acetate in iso-hexane to give 2-(4-bromo-2-fluoro-6-methoxy-phenyl)-5,6,7,8-tetrahydropyrazolo[1 ,2- a]pyridazine-1 ,3-dione (570 mg) as an orange solid.
Step 6: Preparation of 2-(2-fluoro-6-methoxy-4-prop-1 -ynyl-phenyl)-5,6,7,8- tetrahydropyrazolo[1 ,2-a]pyridazine-1 ,3-dione (compound A24)
Figure imgf000109_0002
To a mixture of 2-(4-bromo-2-fluoro-6-methoxy-phenyl)-5,6,7,8-tetrahydropyrazolo[1 ,2- a]pyridazine-1 ,3-dione (0.200 g), dichloropalladium; triphenylphosphane (0.0197 g), 4- diphenylphosphanylbutyl(diphenyl)phosphane (0.0239 g) and but-2-ynoic acid (0.0565 g) under a nitrogen atmosphere was added dimethyl sulfoxide (6.72 mL) followed by tetrabutylammonium fluoride (1 M in tetrahydrofuran, 1.68 mL). This mixture was heated at 1 10 °C for 90 minutes.
The reaction was cooled to room temperature and partitioned between 2 M aqueous hydrochloric acid (20 ml) and ethyl acetate. The aqueous phase was extracted with further ethyl acetate (x2). The combined organic phases were washed with brine, dried over magnesium sulfate, concentrated and purified by chromatography on silica eluting with ethyl acetate in iso-hexane to give impure desired compound. This mixture was dissolved in ethyl acetate and extracted with 2 M aqueous sodium hydroxide. The aqueous phase was acidified with 2 M aqueous hydrochloric acid and extracted with ethyl acetate (x2) and dichloromethane (x2). The combined organic extracts were dried over magnesium sulfate, and concentrated to give 2-(2-fluoro-6-methoxy-4-prop-1 -ynyl-phenyl)-5, 6,7,8- tetrahydropyrazolo[1 ,2-a]pyridazine-1 ,3-dione (1 1 mg) as a yellow solid.
1H NMR (400 MHz, CDCI3) δ (delta) 6.65-6.84 (m, 2H), 4.49-4.88 (m, 1 H), 3.74-3.86 (m, 3H), 3.58-3.69 (m, 4H), 2.03-2.09 (m, 3H), 1 .73-1.88 (m, 4H)
Example 4: Preparation of [8-(2-chloro-6-methoxy-4-prop-1 -ynyl-phenyl)-9-oxo-1 ,2,4,5- tetrahydropyrazolo[1 ,2-d][1 ,4,5]oxadiazepin-7-yl] 2,2-dimethylpropanoate (compound P5)
Figure imgf000110_0001
Pivaloyl chloride (0.021 mL) was added to a mixture of 8-(2-chloro-6-methoxy-4-prop-1-ynyl- phenyl)-1 ,2,4,5-tetrahydropyrazolo[1 ,2-d][1 ,4,5]oxadiazepine-7,9-dione (0.050 g) and pyridine (0.014 mL) in dichloromethane (4.3 mL) and the reaction mixture was stirred at room temperature for 2 hours.
The reaction mixture was quenched with water and extracted with dichloromethane. The organic extract was dried over magnesium sulfate, concentrated and purified by
chromatography on silica eluting with methanol in dichloromethane to give [8-(2-chloro-6- methoxy-4-prop-1-ynyl-phenyl)-9-oxo-1 ,2,4,5-tetrahydropyrazolo[1 ,2-d][1 ,4,5]oxadiazepin-7- yl] 2,2-dimethylpropanoate (40 mg) as an off-white solid.
1H NMR (500 MHz, CDCI3) δ (delta) 7.05-7.10 (m, 1 H), 6.80 (d, 1 H), 4.17-4.33 (m, 2H), 3.82- 3.99 (m, 6H), 3.74 (s, 3H), 2.06 (s, 3H), 1 .17 (s, 9H) The compounds in Tables T1 and P1 below illustrate the present invention, and are particular embodiments of the compounds of formula (I) according to the present invention. For the most part, these compounds are thought to be capable of being prepared by methods disclosed in and/or similar to those described herein, e.g. in the process section hereinabove and/or in the Examples hereinabove, using appropriate starting materials.
Table T1
Figure imgf000111_0001
Figure imgf000112_0001
Figure imgf000113_0001
Figure imgf000114_0001
Figure imgf000115_0001
Figure imgf000116_0001
Figure imgf000117_0001
Figure imgf000118_0001
Figure imgf000119_0001
Figure imgf000120_0001
Figure imgf000121_0001
Figure imgf000122_0001
Figure imgf000123_0001
Figure imgf000124_0001
Figure imgf000125_0001
Figure imgf000126_0001
Figure imgf000127_0001
A86
0 o
\
A87
0 o
\
A88
O CI
o CI
A89
o o
\
A90
O 0
\
0 CI
A91 O CI
Figure imgf000129_0001
O CI
A98
o o
\
A99
O 0
\
0 CI
A100 O CI
0 CI
A101
O 0
\
A102
O 0
\
0 CI
A103 0 CI
Figure imgf000131_0001
0 CI
A110
O 0
\
0 F
A111
O 0
\
0 CI
A112 O CI
0 CI
A113
O 0
\
0 F
A114
o o
\
O CI
A115 O CI O CI
A116
0 o
\
0 F
A117
0 o
\
0 CI
A118 0 CI
0 CI
A119
O 0
\
0 F
A120
o o
\
0 CI
A121 0 CI
Figure imgf000134_0001
Figure imgf000135_0001
Figure imgf000136_0001
Figure imgf000137_0001
Figure imgf000138_0001
Table P1
Figure imgf000139_0001
Figure imgf000140_0001
Figure imgf000141_0001
BIOLOGICAL EXAMPLES BIOLOGICAL EXAMPLE 1
Test 1 - Glasshouse assay for herbicidal activity
Seeds of a variety of test species are sown in standard soil ** in pots. After cultivation for one day (pre-emergence) or after 8 days cultivation (post-emergence) under controlled conditions in a glasshouse (at 24/16°C, day/night; 14 hours light; 65 % humidity), the plants were sprayed with an aqueous spray solution derived from the formulation of the technical active ingredient (the test herbicide) in acetone / water (50:50) solution containing 0.5% Tween 20 ™ (polyoxyethylene sorbitan monolaurate, CAS Reg. No. 9005-64-5). The test plants were then grown on in a glasshouse under controlled conditions in a glasshouse (at 24/16°C, day/night; 14 hours light; 65 % humidity) and watered twice daily. 13 Days after application of the test herbicide, for pre and post-emergence, the test was evaluated visually for percentage phytotoxicity to each plant (where 100% = total damage to plant; 0% = no damage to plant). Generally, each test herbicide is only tested on 1 plant per plant species for each application rate tested and for each application timing.
** The "standard soil" in Biological Example 1 is usually a "sand" or "sandy loam" type of soil.
Biological Example 1 - Pre-Emergence application - Herbicidal Activity results
(percentage phytotoxicity)
Test plants / weeds in the table below are:
Alopecurus myosuroides (ALOMY), Setaria faberi (SETFA), Echinochloa crus-galli (ECHCG), Zea mays (ZEAMX, corn, maize, e.g. volunteer corn), Lolium perenne (LOLPE), Amaranthus retroflexus (AMARE), and Abutilon theophasti Medik. (ABUTH, common English name "velvetleaf"). Of these, Alopecurus myosuroides (ALOMY), Setaria faberi (SETFA),
Echinochloa crus-galli (ECHCG), Zea mays (ZEAMX, corn, maize, e.g. volunteer corn) and Lolium perenne (LOLPE) are grassy monocotyledonous plants / weeds.
Figure imgf000143_0001
Note: A [ - ] in the table above indicates that that compound was not tested on that plant. Biological Example 1 - Post-Emergence application - Herbicidal Activity results
(percentage phytotoxicity)
Test plants / weeds in the table below are:
Alopecurus myosuroides (ALOMY), Setaria faberi (SETFA), Echinochloa crus-galli (ECHCG), Zea mays (ZEAMX, corn, maize, e.g. volunteer corn), Lolium perenne (LOLPE), Amaranthus retroflexus (AMARE), and Abutilon theophasti Medik. (ABUTH, common English name "velvetleaf"). Of these, Alopecurus myosuroides (ALOMY), Setaria faberi (SETFA),
Echinochloa crus-galli (ECHCG), Zea mays (ZEAMX, corn, maize, e.g. volunteer corn) and Lolium perenne (LOLPE) are grassy monocotyledonous plants / weeds.
Figure imgf000144_0001
O LLPE O ALMY CCG EH
AVEFA
Figure imgf000145_0001
Note: A [ - ] in the table above indicates that that compound was not tested on that plant. Test plants / weeds in the table below are:
Lolium perenne (LOLPE), Alopecurus myosuroides (ALOMY), Echinochloa crus-galli (ECHCG) and Avena fatua (AVEFA), all of which are grassy monocotyledonous weeds.
Post-
Compound emergence
Number Application
Rate
(g / ha)
Figure imgf000146_0001
BIOLOGICAL EXAMPLE 2
Assay for Biological Example 2 - Glasshouse assay for herbicidal activity, using various adjuvant systems
Materials and Methods
Herbicide Application: Post-emergence foliar spray application, 200 L/ha, usually one or two replicates for the weeds (depending on application rate), and two replicates for soybean. Climate: Standard warm conditions (tropical), in glasshouse. Specifically, the glasshouse bay conditions are 24 °C / 18 °C day/night; 16/8 hours light/dark; 65% humidity. Plants: The herbicidal application takes place at the following growth stages for plants which include inter alia one or more (usually all seven) of the following plants:
Brachiaria decumbens (BRADC) - growth stage 12 or 13 - or, if BRADC is not used, then usually Brachiaria platyphylla (BRAPP) - growth stage 12 or 13
Digitaria sanguinalis (DIGSA) - growth stage 12 or 13
Eleusine indica (ELEIN) - growth stage 12 or 13
Setaria faberi (SETFA) - growth stage 12 or 13
Zea mays (ZEAMX, maize/corn, e.g. can occur as volunteer corn) cultivar "Garland" - growth stage 12 or 13
Glycine max (GLXMA, soybean) cultivar "Nikko" - growth stage: 1 st trifoliate
Glycine max (GLXMA, soybean) cultivar "TMG133" - which is Roundup Ready™
glyphosate-tolerant soybean cultivar TMG133 (typically available from Monsanto in Brazil) - growth stage: 1st trifoliate.
Herbicidal compositions tested:
Each test Compound is applied with the following adjuvant system (all percentages are final concentrations in the aqueous spray mixture):
Adjuvant system 1 : 0.5% v/v Adigor™ *, 1 .0% v/v AMS (ammonium sulphate) and 12.5% v/v I PA (isopropyl alcohol).
* Adigor™ (currently available in many countries from Syngenta) is an emulsifiable concentrate which consists of:
(i) ethoxylated alcohols, which typically includes ethoxylated higher alkanols; and (ii) a mixture of heavy aromatic hydrocarbons, which typically includes (e.g. includes 50% or more by weight of) a mixture of naphthalenes each of which is substituted by one or more alkyls wherein the alkyl(s) in total have 1-4 carbon atoms per naphthalene molecule (e.g. Solvesso 200 ND™); and
(iii) about 47% w/w (and/or about 45% w/v) of methylated rapeseed oil (rapeseed oil methyl ester) (e.g. Agnique ME 18 RD-F™), as an adjuvant.
Method:
Seeds of the weed (including volunteer) plants, typically including inter alia [either Brachiaria decumbens (BRADC) or Brachiaria platyphylla (BRAPP)], Digitaria sanguinalis (DIGSA), Eleusine indica (ELEIN), Setaria faberi (SETFA) and Zea mays (ZEAMX, corn), are sown in seed trays (troughs) containing clay loam soil (pH 7.0, 2.2% organic matter, "Trough Mix A"); and soybean seed is sown in pots containing the same soil with 3 soybean seedlings per pot. The plants are sprayed with the test herbicide when they reach the growth stages mentioned above.
The test herbicidal solutions are prepared by mixing the appropriate aliquots of the test substance(s) and the adjuvant system indicated above *** in deionised water to give the desired treatment concentration.
The herbicidal application is made as a foliar spray, using a tracksprayer. Following the herbicidal application, the plants are watered twice per day for the duration of the test.
A visual assessment of the % herbicidal damage is made 7 and 14 Days After herbicide Application (DAA), and the results are recorded as % visual herbicidal damage (phytotoxicity) where 0% = no damage to plants and 100% = plant totally killed.
*** Adjuvant system = Adigor™ at 0.5% v/v, and 12.5% v/v I PA (isopropyl alcohol), and 1 .0% v/v AMS (ammonium sulphate); all percentages are final concentrations in the aqueous spray mixture.
Biological Example 2 - Post-Emergence Activity - Results at 14 Days After herbicide Application
Compounds A2, A14, A26, and A29, which are compounds of formula (I) according to the present invention, were tested in a test method substantially as described above.
Compounds A2, A14, A26, and A29 were tested using the 0.5% v/v Adigor™ + 1 .0% v/v AMS + 12.5% v/v I PA adjuvant system. The percentages of herbicidal damage / plant control, at about 14 Days After herbicide Application (DAA), for the Compounds tested and for some of the plants tested, were in the following percentage ranges.
Control of Brachiaria decumbens (BRADC) or Brachiaria platyphylla (BRAPP), warm-climate (warm-season) grassy weeds
At 14DAA, Compound A2 showed percentage control of (a percentage phytotoxicity on) or Brachiaria platyphylla (BRAPP) of 98%, when applied post-emergence at an application rate of 8g/ha.
At 14DAA, Compound A14 showed percentage control of (a percentage phytotoxicity on) Brachiaria decumbens (BRADC) of 90%, when applied post-emergence at an application rate of 8g/ha.
At 14DAA, Compound A26 showed percentage control of (a percentage phytotoxicity on) Brachiaria decumbens (BRADC) of 80%, when applied post-emergence at an application rate of 8g/ha.
At 14DAA, Compound A29 showed percentage control of (a percentage phytotoxicity on) Brachiaria decumbens (BRADC) of 98%, when applied post-emergence at an application rate of 8g/ha.
Control of Digitaria sanguinalis (DIGSA), a warm-climate (warm-season) grassy weed
At 14DAA, certain test compounds (namely, Compound A2, A14 or A29) showed percentage control of (percentage phytotoxicities on) Digitaria sanguinalis (DIGSA) in the range of from 90% to 95%, when applied post-emergence at an application rate of 8g/ha.
At 14DAA, Compound A26 showed a percentage control of Digitaria sanguinalis (DIGSA) of 80%, when applied post-emergence at an application rate of 8g/ha.
Control of Eleusine indica (ELEIN), a warm-climate (warm-season) grassy weed At 14DAA, certain test compounds (namely, Compound A2, A14 or A29) showed percentage control of (percentage phytotoxicities on) Eleusine indica (ELEIN) in the range of from 95% to 98%, when applied post-emergence at an application rate of 8g/ha.
At 14DAA, Compound A26 showed a percentage control of (a percentage phytotoxicity on) Eleusine indica (ELEIN) of 80%, when applied post-emergence at an application rate of 8g/ha.
Control of Setaria faberi (SETFA), a warm-climate (warm-season) grassy weed
At 14DAA, Compound A2 showed a percentage control of (a percentage phytotoxicity on) Setaria faberi (SETFA) of 90%, when applied post-emergence at an application rate of 8g/ha.
At 14DAA, certain test compounds (namely, Compound A14, A26 or A29) showed
percentage control of (percentage phytotoxicities on) Setaria faberi (SETFA) of 95%, when applied post-emergence at an application rate of 8g/ha.
Control of Zea mays (ZEAMX, corn), a warm-climate (warm-season) grassy plant
Zea mays (ZEAMX, maize/corn) is often present as a "volunteer" weed ("volunteer" corn), in fields where it was planted as a crop in preceding growing season(s) and where the present field crop is not corn.
At 14 DAA, Compound A2 showed a percentage control of (a percentage phytotoxicity on) Zea mays (ZEAMX, corn) of 95%, when applied post-emergence at an application rate of 8g/ha.
At 14 DAA, certain test compounds (namely, Compound A14 or A26) showed a percentage control of (percentage phytotoxicities on) Zea mays (ZEAMX, corn) of 90%, when applied post-emergence at an application rate of 8g/ha.
At 14 DAA, Compound A29 showed a percentage control of (a percentage phytotoxicity on) Zea mays (ZEAMX, corn) of 100%, when applied post-emergence at an application rate of 8g/ha. Phytotoxicity on Glycine max (GLXMA, soybean) cultivar "Nikko"
At 14DAA, Compound A2 showed a percentage phytotoxicity on Glycine max (GLXMA, soybean) cultivar "Nikko" of 80%, when applied post-emergence at an application rate of 120g/ha.
At 14DAA, certain test compounds (namely, Compound A14 or A26) showed percentage phytotoxicities on Glycine max (GLXMA, soybean) cultivar "Nikko" of 85%, when applied post-emergence at an application rate of 120g/ha.
At 14DAA, Compound A29 showed a percentage phytotoxicity on Glycine max (GLXMA, soybean) cultivar "Nikko" of 90%, when applied post-emergence at an application rate of 120g/ha.
Phytotoxicity on Glycine max (GLXMA, soybean) cultivar "TMG133"
Glycine max (GLXMA, soybean) cultivar "TMG133" is Roundup Ready™ glyphosate-tolerant soybean cultivar TMG133, and is typically available from Monsanto in Brazil.
At 14DAA, Compound A2 showed a percentage phytotoxicity on Glycine max (GLXMA, soybean) cultivar "TMG133" of 85%, when applied post-emergence at an application rate of 120g/ha.
At 14DAA, Compound A14 showed percentage phytotoxicities on Glycine max (GLXMA, soybean) cultivar "TMG133" in the range of from 70% to 80%, when applied post-emergence at an application rate of 120g/ha.
At 14DAA, Compound A26 showed percentage phytotoxicities on Glycine max (GLXMA, soybean) cultivar "TMG133" in the range of from 80% to 85%, when applied post-emergence at an application rate of 120g/ha.
At 14DAA, Compound A29 showed a percentage phytotoxicity on Glycine max (GLXMA, soybean) cultivar "TMG133" of 90%, when applied post-emergence at an application rate of 120g/ha. BIOLOGICAL EXAMPLE 3
Test 3 - Glasshouse assay for herbicidal activity
Seeds of a variety of monocotyledonous and dicotyledonous test plants are sown in standard soil in pots. The plants are cultivated for one day (for pre-emergence) or for about 12 days (range = 10-13 days) (for post-emergence) under controlled conditions in a glasshouse (warm climate species at 24/18°C, cool climate species at 20/16°C, both at day/night; 16 hours light; 65 % humidity).
An "instant formulation", known as the "IF50", containing 50 g/litre (i.e. 5% w/v) of the "technical" (i.e. unformulated) active ingredient is prepared by dissolving the active ingredient in a mixture of organic solvents and emulsifier, details of which are provided in the Table below. This IF50 is then mixed with a small, variable amount of acetone to aid dissolution, before addition of a 0.2% v/v aqueous solution of the adjuvant X-77 (which is a mixture of alkyl aryl polyoxyethylene glycols and free fatty acids in isopropanol, CAS Registry number 1 1097-66-8), as the aqueous diluent, to form an aqueous spray solution which contains a predetermined concentration of the active ingredient (which varies depending on the application rate of the active ingredient to the plants) and 0.2% v/v of the adjuvant X-77. This aqueous spray solution is then sprayed onto the plants, after one day's cultivation (for pre- emergence) or after about 12 days' cultivation (range = 10-13 days) (for post-emergence).
Table: Composition of the mixture of organic solvents and emulsifier to be used as a base for the instant formulation (IF50).
Figure imgf000152_0001
The test plants are then grown on, in a glasshouse (greenhouse) under controlled conditions (warm climate species at 24/18°C, cool climate species at 20/16°C, both at day/night, 16 hours light; 65 % humidity; as mentioned above) and are watered twice daily. Either 15 days after application of the herbicide (15 DAA) (for post-emergence), or 20 days after application of the herbicide (20 DAA) (for pre-emergence), the test plants are evaluated visually, and an assessed percentage phytotoxicity score is given for each herbicidal application on each plant species (where 100% = total damage to plant; 0% = no damage to plant).
Some of the typical test plants are as follows:
Cool climate crop plants: Triticum aestivum (TRZAW, winter wheat), Hordeum vulgare (HORVW, barley), Brassica napus (BRSNN, rape, also called oilseed rape or rapeseed), Beta vulgaris (BEAVA, sugar beet).
Warm climate crop plants: Glycine max (GLXMA, soybean), Oryza sativa (ORYSA, rice). Cool climate ("cool season") grassy monocotyledonous weeds: Alopecurus myosuroides (ALOMY), Lolium perenne (LOLPE), and Poa annua (POAAN).
Warm climate ("warm season") grassy monocotyledonous weeds: Setaria faberi (SETFA), SORVU (Sorghum bicoior (L.) Moench ssp. Bicoior, or Sorghum vulgare Pers.), Digitaria sanguinalis (DIGSA), Echinochloa crus-galli (ECHCG), Brachiaria plantaginea (BRAPL), and Zea mays (ZEAMX, corn, maize, e.g. volunteer corn).
Biological Example 3 - Table of Post-emergence herbicidal activity (percentage phytotoxicity)
Figure imgf000153_0001
Figure imgf000154_0001
ber
* In addition to the above-shown data, Compound P2 exhibited 60% phytotoxicity on (control of) POAAN when applied at 250 g/ha post-emergence, in Biological Example 3.
Also, compounds A2, A26, A29, P2 and P5 exhibited 20%, 40%, 40%, 10% and 20% phytotoxicity on Oryza sativa (ORYSA, rice), respectively, when applied at 8 g/ha post- emergence, in Biological Example 3.
Also, compounds A2, A26, A29, P2 and P5 exhibited 60%, 10%, 40%, 10% and 60% phytotoxicity on Hordeum vulgare (HORVW, barley), respectively, when applied at 30 g/ha post-emergence, in Biological Example 3.
Also, compounds A2, A26, A29, P2 and P5 exhibited 0%, 0%, 0%, 10% and 0% phytotoxicity on Hordeum vulgare (HORVW, barley), respectively, when applied at 8 g/ha post- emergence, in Biological Example 3.

Claims

1 . A compound of formula (I):
Figure imgf000155_0001
wherein CKE is of sub-formula (A) and/or (B):
Figure imgf000155_0002
(A) (B)
wherein:
R1 is fluorine or chlorine;
R2 is hydrogen, methyl, ethyl, n-propyl, n-butyl, cyclopropyl, ethynyl, cyano, fluorine, chlorine, bromine, C Csalkoxy, C1-C2fluoroalkoxy, (difluoro)vinyloxy, C1-C2alkoxy-C1-C3alkoxy-, or C f I u oroa I koxy-C ^ - C3a I koxy- ;
X is NR4 or CR5R6; wherein:
R3, R4, and R5, independently of each other, are:
hydrogen, d-C4alkyl, CrC2fluoroalkyl, Ci-C3alkoxyCi-C3alkyl, Ci-C3alkylthioCrC3alkyl, CrC4alkoxy, R9-C≡C-C(R7)(R8)-, (R11)(R12)C=C(R10)-C(R7)(R8)-, Het-CH2-, or Het; or
benzyl optionally substituted on its phenyl ring by 1 or 2 substituents independently being halogen, Ci-C2alkyl, Cifluoroalkyl, Ci-C2alkoxy, Cifluoroalkoxy, -C≡C-R13, - C(R14)=C(R15)(R16), -C(0)Me,
-C(0)-Cifluoroalkyl, -S(0)n4-Me, -S(0)n4-Cifluoroalkyl, -NR19R20, or cyano; or phenyl optionally substituted by 1 or 2 substituents independently being halogen, CrC2alkyl, Cifluoroalkyl, -C≡C-R13, -C(R14)=C(R15)(R16), C C2alkoxy,
Cifluoroalkoxy, -C(0)Me,
-C(0)-Cifluoroalkyl, -S(0)n5-Me, -S(0)n5-Cifluoroalkyl, -NR19R20, or cyano;
provided that when X is NR4, then at least one of R3 and R4 is hydrogen or CrC3alkyl; and provided that when X is CR5R6, then at least one of R3 and R5 is hydrogen or CrC3alkyl; or R3 and R4 are taken together, and/or R3 and R5 are taken together, to form a chain which is (a), (b), (c), (d), (e), (f) or (g), as shown below:
-C(R21)(R22)-C(R23)(R24)-Y-C(R25)(R26)-C(R27)(R28)- (a)
-C(R21)(R22)-Y-C(R21A)(R22A)-C(R21A)(R22A)-C(R27)(R28)- (b)
-CH(R29)-Y-C(R21A)(R22A)-CH(R32)- (c)
-CH(R29)-Y-CH(R32)- (d)
-C(R21)(R22)-C(R23)(R24)-C(R30)(R31)-C(R25)(R26)-C(R27)(R28)- (e)
-C(R21)(R22)-C(R21A)(R22A)-C(R30)(R31)-C(R27)(R28)- (f)
-CH(R29)-C(R30)(R31)-CH(R32)- (g) wherein Y is O or NR4U; and R6 is hydrogen or CrC3alkyl; or R5 and R6 taken together are -(CH2)ni- or -(CH2)n2-X1-(CH2)n3-, in which case R3 is as defined above provided that R3 and R5 are not taken together;
wherein X1 is O, C(H)(C C2alkyl), C(Ci-C2alkyl)2 or C(H)(C C2alkoxy);
n1 is 2, 3, 4 or 5; and
n2 and n3 are independently 1 , 2 or 3 provided that n2 + n3 is 2, 3 or 4; and wherein:
Het is a heteroaryl, attached at a ring-carbon, which is optionally substituted by 1 , 2 or 3 ring- carbon substituents independently being halogen, Ci-C3alkyl, C-|-C2fluoroalkyl, -C≡C-R13, - C(R14)=C(R15)(R16), C C3alkoxy, C C2fluoroalkoxy, cyclopropyloxy, CH2=CH-CH2-0-, HC≡C-CH2-0-, -C(0)-R17, -S(0)n18-R18, -NR19R20, cyano or nitro; provided that any non- fluorine halogen, alkoxy, fluoroalkoxy, cyclopropyloxy, CH2=CH-CH2-0- or HC≡C-CH2-0- is not substituted at any ring-carbon bonded directly to a ring-nitrogen of the heteroaryl; and/or, when Het is a 5-membered heteroaryl ring containing a ring-nitrogen atom not partaking in a C=N ring double bond, the heteroaryl is optionally substituted on the ring- nitrogen atom not partaking in a C=N ring double bond by one CrC3alkyl, CrC2fluoroalkyl, C C3alkyl-C(0)-, C C2fluoroalkyl-C(0)- or Ci-C2alkyl-S(0)2- substituent; and wherein:
R7 and R8, independently of each other, are hydrogen or methyl;
R9 is hydrogen, methyl, ethyl or chlorine; and
R10, R11 and R12, independently of each other, are hydrogen, methyl or ethyl, provided that R10, R11 and R12 in total contain no more than three carbon atoms;
R13 is hydrogen, methyl, dfluoroalkyl, fluorine or chlorine;
R14, R15 and R16 independently are hydrogen, methyl, Cifluoroalkyl, fluorine or chlorine; provided that R14, R15 and R16 in total contain no more than one carbon atom, and R14, R15 and R16 in total comprise no more than one chlorine;
and
n4 is 0, 1 or 2;
n5 is 0, 1 or 2;
R17 and R18 independently are C C3alkyl, Cifluoroalkyl, or -NR19AR20A;
n18 is 0, 1 or 2;
R19 is -C(0)-C C2alkyl, -C(0)-dfluoroalkyl, -S(0)2-C C2alkyl, -S(0)2-dfluoroalkyl, d-C2alkyl, or dfluoroalkyl;
R20 and R20A independently are hydrogen, methyl or Cifluoroalkyl; and
R19A is hydrogen, d-C2alkyl or dfluoroalkyl; and wherein:
R21, R22, R27 and R28 are independently hydrogen or methyl; provided that two, three or all of R21, R22, R27 and R28 are hydrogen; and
R21A and R22A are independently hydrogen or methyl; and
R23, R24, R25, and R26 are independently hydrogen, methyl, ethyl or methoxymethyl; provided that two, three or all of R23, R24, R25 and R26 are hydrogen;
or R23 and R25 are taken together and form a -CH2- or -CH2CH2- bridge, and R24 and R26 are hydrogen; and R and R are independently hydrogen or methyl; and
R30 is hydrogen, d-C3alkyl, CrC2fluoroalkyl, CrC3alkoxy, CrC3fluoroalkoxy,
Ci-C3alkyl-S(0)n3o-, Ci-C2alkoxyCi-C2alkyl, or Ci-C2alkylthioCi-C2alkyl;
wherein n30 is 0, 1 or 2; and
R31 is hydrogen, methyl or ethyl;
or R30 and R31 taken together are oxo (=0), =N-0-H, or =N-0-(C C3alkyl); provided that, in all cases wherein R3 and R4 are taken together, and/or R3 and R5 are taken together, to form a chain which is (a), (b), (c), (d), (e), (f) or (g), then the chain contains a total of no more than three substituents on carbon in the ring which is formed by NR3, X, and the chain (a), (b), (c), (d), (e), (f) or (g); wherein if a bridge is formed by R23 and R25 being taken together then this bridge is counted as two ring-carbon-substituents; and wherein R40 is Ci-C3alkoxy, CrC2fluoroalkoxy, cyclopropyloxy, CH2=CH-CH2-0-, HC≡C-CH2-0-, N≡C-CH20-, CH3OCH20-, CH3OCH2CH20-, CH3CH2OCH20-, C C3alkyl or CifluoroalkyI;
and wherein:
G is hydrogen; an agriculturally acceptable metal, or an agriculturally acceptable sulfonium or ammonium group; or
G is -C(Xa)-Ra, -C(Xb)-Xc-Rb, -C(Xd)-N(Rc)-Rd, -S02-Re, -P(Xe)(Rf)-R9, -CH2-Xf-Rh; or phenyl-CH2- or phenyl-CH(CrC2alkyl)- (in each of which the phenyl is optionally substituted by 1 , 2 or 3 of, independently, Ci-C2alkyl, CifluoroalkyI, Ci-C2alkoxy, Cifluoroalkoxy, fluorine, chlorine, bromine, cyano or nitro), or heteroaryl-CH2- or heteroaryl-CH(Ci-C2alkyl)- (in each of which the heteroaryl is optionally substituted by 1 , 2 or 3 of, independently, Ci-C2alkyl, CifluoroalkyI, Ci-C2alkoxy, Cifluoroalkoxy, fluorine, chlorine, bromine, cyano or nitro), or phenyl-C(0)-CH2- (wherein the phenyl is optionally substituted by 1 , 2 or 3 of, independently, CrC2alkyl, CifluoroalkyI, Ci-C2alkoxy, Cifluoroalkoxy, fluorine, chlorine, bromine, cyano or nitro); or Ci-C6alkoxy-C(0)-CH2-, C C6alkoxy-C(0)-CH=CH-, C2-C7alken-1-yl-CH2-,
C2-C7alken-1 -yl-CH(Ci-C2alkyl)-, C2-C4fluoroalken-1 -yl-CH2-, C2-C7alkyn-1-yl-CH2-, or C2-C7alkyn-1 -yl-CH(Ci-C2alkyl)-; wherein Xa, Xb, Xc, Xd, Xe and X are independently of each other oxygen or sulfur; and wherein
Ra is H, Ci-C2ialkyl, C2-C2ialkenyl, C2-Ci8alkynyl, Ci-Ciofluoroalkyl, Ci-Ciocyanoalkyl, d- Ci0nitroalkyl, Ci-Ci0aminoalkyl, Ci-C5alkylamino(Ci-C5)alkyl, C2-C8dialkylamino(Ci-C5)alkyl, C3-C7cycloalkyl(Ci-C5)alkyl, Ci-C5alkoxy(Ci-C5)alkyl, C3-C5alkenyloxy(Ci-C5)alkyl, C3- C5alkynyloxy (CrC5)alkyl, Ci-C5alkylthio(Ci-C5)alkyl, Ci-C5alkylsulfinyl(Ci-C5)alkyl, Cr C5alkylsulfonyl(Ci-C5)alkyl, C2-C8alkylideneaminoxy(Ci-C5)alkyl, CrC5alkylcarbonyl(Cr C5)alkyl, Ci-C5alkoxycarbonyl(Ci-C5)alkyl, aminocarbonyl(Ci-C5)alkyl, d- C5alkylaminocarbonyl(Ci-C5)alkyl, C2-C8dialkylaminocarbonyl(Ci-C5)alkyl, d- C5alkylcarbonylamino(d-C5)alkyl, /V-(C1-d)alkylcarbonyl-/V-(C1-d)alkylamino(C1-d)alkyl, d-dtrialkylsilyl(C1-d)alkyl, phenyl(C1-d)alkyl (wherein the phenyl is optionally substituted by 1 , 2 or 3 of, independently, d-dalkyl, d-C3fluoroalkyl, d-dalkoxy, Crdfluoroalkoxy, d-C3alkylthio, d-dalkylsulfinyl, Crdalkylsulfonyl, halogen, cyano, or nitro), heteroaryl(d- d)alkyl (wherein the heteroaryl is optionally substituted by 1 , 2 or 3 of, independently, d- dalkyl, d-C3fluoroalkyl, Crdalkoxy, Crdfluoroalkoxy, CrC3alkylthio, d-dalkylsulfinyl, CrC3alkylsulfonyl, halogen, cyano, or nitro), C2-C5fluoroalkenyl, C3-C8cycloalkyl; phenyl or phenyl substituted by 1 , 2 or 3 of, independently, d-C3alkyl, d-C3fluoroalkyl, Ci-C3alkoxy, CrC3fluoroalkoxy, halogen, cyano or nitro; or heteroaryl or heteroaryl substituted by 1 , 2 or 3 of, independently, d-C3 alkyl, d-C3fluoroalkyl, Crdalkoxy, Crdfluoroalkoxy, halogen, cyano or nitro;
Rb is d-C18alkyl, C3-C18alkenyl, C3-C18alkynyl, C2-C10fluoroalkyl, d-C10cyanoalkyl, d- C10nitroalkyl, C2-C10aminoalkyl, CrC5alkylamino(CrC5)alkyl, C2-C8dialkylamino(Crd)alkyl, C3-C7cycloalkyl(CrC5)alkyl, Ci-C5alkoxy(Ci-C5)alkyl, C3-C5alkenyloxy(CrC5)alkyl, C3- C5alkynyloxy(Ci-C5)alkyl, Ci-C5alkylthio(Ci-C5)alkyl, Ci-C5alkylsulfinyl(Ci-C5)alkyl, d- C5alkylsulfonyl(CrC5)alkyl, C2-C8alkylideneaminoxy(CrC5)alkyl, CrC5alkylcarbonyl(Cr C5)alkyl, Ci-C5alkoxycarbonyl(CrC5)alkyl, aminocarbonyl(CrC5)alkyl, d- C5alkylaminocarbonyl(CrC5)alkyl, C2-C8dialkylaminocarbonyl(CrC5)alkyl, d- C5alkylcarbonylamino(CrC5)alkyl, /V-(Ci-C5)alkylcarbonyl-/\/-(CrC5)alkylamino(CrC5)alkyl, C3-C6trialkylsilyl(CrC5)alkyl, phenyl(d-C5)alkyl (wherein the phenyl is optionally substituted by 1 , 2 or 3 of, independently, d-C3alkyl, d-C3fluoroalkyl, Ci-C3alkoxy, Crdfluoroalkoxy, d-dalkylthio, d-dalkylsulfinyl, Crdalkylsulfonyl, halogen, cyano, or nitro), heteroaryld- dalkyl (wherein the heteroaryl is optionally substituted by 1 , 2 or 3 of, independently, d- C3alkyl, Crdfluoroalkyl, d-dalkoxy, CrCsfluoroalkoxy, d-C3alkyl-thio, d-dalkylsulfinyl, CrC3alkylsulfonyl, halogen, cyano, or nitro), C3-C5fluoroalkenyl, C3-C8cycloalkyl; phenyl or phenyl substituted by 1 , 2 or 3 of, independently, CrC3alkyl, Ci-C3fluoroalkyl, Ci-C3alkoxy, CrC3fluoroalkoxy, halogen, cyano or nitro; or heteroaryl or heteroaryl substituted by 1 , 2 or 3 of, independently, C C3 alkyl, CrC3fluoroalkyl, Ci-C3alkoxy, Ci-C3fluoroalkoxy, halogen, cyano or nitro; and
Rc and Rd are each independently of each other hydrogen, CrCi0alkyl, C3-Ci0alkenyl, C3- Ci0alkynyl, C2-Ci0fluoroalkyl, Ci-Ciocyanoalkyl, Ci-Ci0nitroalkyl, Ci-Ci0aminoalkyl, d- C5alkylamino(Ci-C5)alkyl, C2-C8dialkylamino(Ci-C5)alkyl, C3-C7cycloalkyl(Ci-C5)alkyl, d- C5alkoxy(d-C5)alkyl, C3-C5alkenyloxy(d-C5)alkyl, C3-C5alkynyloxy(d-C5)alkyl, C
C5alkylthio(d-C5)alkyl, C1-C5alkylsulfinyl(C1-C5)alkyl, C1-C5alkylsulfonyl(C1-C5)alkyl, C2- C8alkylideneaminoxy(C1-C5)alkyl, C1-C5alkylcarbonyl(C1-C5)alkyl, CrC5alkoxycarbonyl(Cr C5)alkyl, aminocarbonyl(d-C5)alkyl, C1-C5alkylaminocarbonyl(C1-C5)alkyl, C2- C8dialkylaminocarbonyl(C1-C5)alkyl, C1-C5alkylcarbonylamino(C1-C5)alkyl, /V-(d- C5)alkylcarbonyl-/V-(C2-C5)alkylaminoalkyl, C3-C6trialkylsilyl(C1-C5)alkyl, phenyl(d-C5)alkyl (wherein the phenyl is optionally substituted by 1 , 2 or 3 of, independently, d-C3alkyl, d- dfluoroalkyl, Ci-C3alkoxy, Ci-C3fluoroalkoxy, Ci-C3alkylthio, Ci-C3alkylsulfinyl, d- C3alkylsulfonyl, halogen, cyano, or nitro), heteroaryl(Ci-C5)alkyl (wherein the heteroaryl is optionally substituted by 1 , 2 or 3 of, independently, d-C3alkyl, d-C3fluoroalkyl, d- C3alkoxy, CrCsfluoroalkoxy, d-C3alkylthio, d-C3alkylsulfinyl, CrC3alkylsulfonyl, halogen, cyano, or nitro), C2-C5fluoroalkenyl, C3-C8cycloalkyl; phenyl or phenyl substituted by 1 , 2 or 3 of, independently, d-C3alkyl, d-C3fluoroalkyl, d-C3alkoxy, d-C3fluoroalkoxy, halogen, cyano or nitro; heteroaryl or heteroaryl substituted by 1 , 2 or 3 of, independently, d-C3alkyl, Crdfluoroalkyl, d-C3alkoxy, d-C3fluoroalkoxy, halogen, cyano or nitro; heteroarylamino or heteroarylamino substituted by 1 , 2 or 3 of, independently, d-C3alkyl, Crdfluoroalkyl, d- dalkoxy, CrC3fluoroalkoxy, halogen, cyano or nitro; diheteroarylamino or diheteroarylamino substituted by 1 , 2 or 3 of, independently, d-C3alkyl, Crdfluoroalkyl, d-C3alkoxy, d- C3fluoroalkoxy, halogen, cyano or nitro; phenylamino or phenylamino substituted by 1 , 2 or 3 of, independently, d-C3alkyl, Crdfluoroalkyl, d-C3alkoxy, d-C3fluoroalkoxy, halogen, cyano or by nitro; diphenylamino or diphenylamino substituted by 1 , 2 or 3 of, independently, d-dalkyl, Crdfluoroalkyl, d-C3alkoxy, d-C3fluoroalkoxy, halogen, cyano or nitro; or C3- dcycloalkylamino, di(C3-C7cycloalkyl)amino or C3-C7cycloalkoxy; or Rc and Rd, together with the nitrogen to which they are bonded, to form an unsubstituted 4, 5, 6 or 7 membered ring, optionally containing one heteroatom selected from O or S; and
Re is Ci-Ci0alkyl, C2-Ci0alkenyl, C2-Ci0alkynyl, Ci-Ciofluoroalkyl, Ci-Ciocyanoalkyl, d- Ci0nitroalkyl, Ci-Ci0aminoalkyl, Ci-C5alkylamino(Ci-C5)alkyl, C2-C8dialkylamino(Ci-C5)alkyl, C3-C7cycloalkyl(Ci-C5)alkyl, Ci-C5alkoxy(Ci-C5)alkyl, C3-C5alkenyloxy(Ci-C5)alkyl, C3- C5alkynyloxy(Ci-C5)alkyl, Ci-C5alkylthio(Ci-C5)alkyl, Ci-C5alkylsulfinyl(Ci-C5)alkyl, Cr C5alkylsulfonyl(Ci-C5)alkyl, C2-C8alkylideneaminoxy(Ci-C5)alkyl, CrC5alkylcarbonyl(Cr C5)alkyl, Ci-C5alkoxycarbonyl(Ci-C5)alkyl, aminocarbonyl(Ci-C5)alkyl, d- C5alkylaminocarbonyl(Ci-C5)alkyl, C2-C8dialkylaminocarbonyl(Ci-C5)alkyl, d- C5alkylcarbonylamino(C1-C5)alkyl, /V-(C1-C5)alkylcarbonyl-/V-(C1-C5)alkylamino(C1-C5)alkyl, C3-C6trialkylsilyl(C1-C5)alkyl, phenyl(C1-C5)alkyl (wherein the phenyl is optionally substituted by 1 , 2 or 3 of, independently, d-dalkyl, d-C3fluoroalkyl, d-C3alkoxy, Crdfluoroalkoxy, d-C3alkylthio, d-dalkylsulfinyl, d-C3alkylsulfonyl, halogen, cyano, or nitro), heteroaryl(d- d)alkyl (wherein the heteroaryl is optionally substituted by 1 , 2 or 3 of, independently, d- C3alkyl, d-C3fluoroalkyl, d-dalkoxy, Crdfluoroalkoxy, d-C3alkylthio, d-dalkylsulfinyl, d-C3alkylsulfonyl, halogen, cyano, or nitro), C2-C5fluoroalkenyl, C3-C8cycloalkyl; phenyl or phenyl substituted by 1 , 2 or 3 of, independently, d-C3alkyl, d-C3fluoroalkyl, d-C3alkoxy, Crdfluoroalkoxy, halogen, cyano or nitro; heteroaryl or heteroaryl substituted by 1 , 2 or 3 of, independently, d-C3alkyl, d-C3fluoroalkyl, d-C3alkoxy, d-C3fluoroalkoxy, halogen, cyano or nitro; heteroarylamino or heteroarylamino substituted by 1 , 2 or 3 of, independently, d-d alkyl, d-dfluoroalkyl, d-dalkoxy, Crdfluoroalkoxy, halogen, cyano or nitro;
diheteroarylamino or diheteroarylamino substituted by 1 , 2 or 3 of, independently, d-C3alkyl, d-C3fluoroalkyl, d-dalkoxy, Crdfluoroalkoxy, halogen, cyano or nitro; phenylamino or phenylamino substituted by 1 , 2 or 3 of, independently, d-dalkyl, d-dfluoroalkyl, d- dalkoxy, Crdfluoroalkoxy, halogen, cyano or nitro; diphenylamino or diphenylamino substituted by 1 , 2 or 3 of, independently, d-C3alkyl, d-C3fluoroalkyl, d-C3alkoxy, d- dfluoroalkoxy, halogen, cyano or nitro; or d-dcycloalkylamino, di(C3-C7cycloalkyl)amino, C3-C7cycloalkoxy, d-Ci0alkoxy, d-Ciofluoroalkoxy, d-C5alkylamino or di(Ci-C4alkyl)amino;
R and R9 are are each independently of each other Ci-Cioalkyl, C2-Ci0alkenyl, C2-Ci0alkynyl, d-Cioalkoxy, Ci-Ciofluoroalkyl, Ci-Ciocyanoalkyl, d-Ci0nitroalkyl, d-Cioaminoalkyl, d- C5alkylamino(CrC5)alkyl, C2-C8dialkylamino(CrC5)alkyl, C3-C7cycloalkyl(CrC5)alkyl, Cr C5alkoxy(CrC5)alkyl, C3-C5alkenyloxy(CrC5)alkyl, C3-C5alkynyloxy(CrC5)alkyl, Cr C5alkylthio(C1-C5)alkyl, C1-C5alkylsulfinyl(C1-C5)alkyl, C1-C5alkylsulfonyl(C1-C5)alkyl, C2- C8alkylideneaminoxy(Ci-C5)alkyl, Ci-C5alkylcarbonyl(Ci-C5)alkyl, CrC5alkoxycarbonyl(Cr C5)alkyl, aminocarbonyl(CrC5)alkyl, Ci-C5alkylaminocarbonyl(Ci-C5)alkyl, C2- C8dialkylaminocarbonyl(Ci-C5)alkyl, Ci-C5alkylcarbonylamino(Ci-C5)alkyl, /V-(d- C5)alkylcarbonyl-/V-(C2-C5)alkylaminoalkyl, C3-C6trialkylsilyl(Ci-C5)alkyl, phenyl(C C5)alkyl (wherein the phenyl is optionally substituted by 1 , 2 or 3 of, independently, CrC3alkyl, d- C3fluoroalkyl, CrC3alkoxy, Ci-C3fluoroalkoxy, Ci-C3alkylthio, CrC3alkylsulfinyl, d- C3alkylsulfonyl, halogen, cyano, or nitro), heteroaryl(Ci-C5)alkyl (wherein the heteroaryl is optionally substituted by 1 , 2 or 3 of, independently, Ci-C3alkyl, Ci-C3fluoroalkyl, d- dalkoxy, d-dfluoroalkoxy, d-dalkylthio, d-dalkylsulfinyl, d-dalkylsulfonyl, halogen, cyano, or nitro), C2-dfluoroalkenyl, C3-C8cycloalkyl; phenyl or phenyl substituted by 1 , 2 or 3 of, independently, d-dalkyl, d-dfluoroalkyl, d-dalkoxy, d-dfluoroalkoxy, halogen, cyano or nitro; heteroaryl or heteroaryl substituted by 1 , 2 or 3 of, independently, d- alkyl, d-dfluoroalkyl, d-dalkoxy, Crdfluoroalkoxy, halogen, cyano or nitro; heteroarylamino or heteroarylamino substituted by 1 , 2 or 3 of, independently, d-d alkyl, d-dfluoroalkyl, d- dalkoxy, Crdfluoroalkoxy, halogen, cyano or nitro; diheteroarylamino or diheteroarylamino substituted by 1 , 2 or 3 of, independently, d-C3 alkyl, d-C3fluoroalkyl, d-C3alkoxy, Ci- Csfluoroalkoxy, halogen, cyano or nitro; phenylamino or phenylamino substituted by 1 , 2 or 3 of, independently, d-C3alkyl, d-C3fluoroalkyl, d-C3alkoxy, Crdfluoroalkoxy, halogen, cyano or nitro; diphenylamino or diphenylamino substituted by 1 , 2 or 3 of, independently, d- dalkyl, d-C3fluoroalkyl, d-C3alkoxy, d-dfluoroalkoxy, halogen, cyano or nitro; or C3- dcycloalkylamino, di(C3-C7cycloalkyl)amino, C3-C7cycloalkoxy, d-C10fluoroalkoxy, d- C5alkylamino or di(CrC4alkyl)amino; or benzyloxy or phenoxy, wherein the benzyl and phenyl groups are in turn optionally substituted by 1 , 2 or 3 of, independently, d-C3alkyl, d- dfluoroalkyl, d-C3alkoxy, CrC3fluoroalkoxy, halogen, cyano or nitro; and
Rh is d-C10alkyl, C3-C10alkenyl, C3-C10alkynyl, d-C10fluoroalkyl, d-C10cyanoalkyl, d- Cionitroalkyl, C2-Ci0aminoalkyl, Ci-C5alkylamino(CrC5)alkyl, C2-C8dialkylamino(CrC5)alkyl, C3-C7cycloalkyl(CrC5)alkyl, Ci-C5alkoxy(CrC5)alkyl, C3-C5alkenyloxy(CrC5)alkyl, C3- C5alkynyloxy(CrC5)alkyl, Ci-C5alkylthio(CrC5)alkyl, Ci-C5alkylsulfinyl(CrC5)alkyl, Cr C5alkylsulfonyl(CrC5)alkyl, C2-C8alkylideneaminoxy(CrC5)alkyl, CrC5alkylcarbonyl(Cr C5)alkyl, Ci-C5alkoxycarbonyl(CrC5)alkyl, aminocarbonyl(Ci-C5)alkyl, d- C5alkylaminocarbonyl(CrC5)alkyl, C2-C8dialkylaminocarbonyl(Ci-C5)alkyl, d- C5alkylcarbonylamino(CrC5)alkyl, /V-(Ci-C5)alkylcarbonyl-/\/-(CrC5)alkylamino(CrC5)alkyl, C3-C6trialkylsilyl(C -C5)alkyl, phenyl(C1-C5)alkyl (wherein the phenyl is optionally substituted by 1 , 2 or 3 of, independently, d-C3alkyl, CrC3fluoroalkyl, CrC3alkoxy, CrC3fluoroalkoxy, Ci-C3alkylthio, CrC3alkylsulfinyl, C C3 alkylsulfonyl, halogen, cyano or nitro), heteroaryl(Ci- C5)alkyl (wherein the heteroaryl is optionally substituted by 1 , 2 or 3 of, independently, d- C3alkyl, Ci-C3fluoroalkyl, Ci-C3alkoxy, Ci-C3fluoroalkoxy, Ci-C3alkylthio, CrC3alkylsulfinyl, Ci-C3 alkylsulfonyl, halogen, cyano or nitro), phenoxy(CrC5)alkyl (wherein the phenyl is optionally substituted by 1 , 2 or 3 of, independently, Ci-C3alkyl, Ci-C3fluoroalkyl, d- C3alkoxy, Ci-C3fluoroalkoxy, Ci-C3alkylthio, CrC3alkylsulfinyl, C C3 alkylsulfonyl, halogen, cyano or nitro), heteroaryloxy(Ci-C5)alkyl (wherein the heteroaryl is optionally substituted by
1 . 2 or 3 of, independently, Ci-C3alkyl, Ci-C3fluoroalkyl, Ci-C3alkoxy, Ci-C3fluoroalkoxy, d- C3alkylthio, Ci-C3alkylsulfinyl, d-C3 alkylsulfonyl, halogen, cyano or nitro), C3- C5fluoroalkenyl, C3-C8cycloalkyl; phenyl or phenyl substituted by 1 , 2 or 3 of, independently, d-C3alkyl, d-C3fluoroalkyl, d-C3alkoxy, d-C3fluoroalkoxy, halogen, cyano or nitro;
heteroaryl or heteroaryl substituted by 1 , 2 or 3 of, independently, d-C3alkyl, d- C3fluoroalkyl, d-C3alkoxy, d-C3fluoroalkoxy, halogen, cyano or nitro; d-C6alkyl-C(0)-; or phenyl-C(O)- wherein the phenyl is optionally substituted by 1 or 2 of, independently, d- C2alkyl, CifluoroalkyI, d-C2alkoxy, Cifluoroalkoxy, fluorine, chlorine, bromine, cyano or nitro; 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 as an agrochemically acceptable salt thereof.
2. A compound as claimed in claim 1 , wherein G is hydrogen; an agriculturally acceptable metal, or an agriculturally acceptable sulfonium or ammonium group; or G is -C(Xa)-Ra or -C(Xb)-Xc-Rb, wherein Xa, Ra, Xb, Xc and Rb are as defined in claim 1.
3. A compound as claimed in claim 1 or 2, wherein, when G is -C(Xa)-Ra or -C(Xb)-Xc-Rb, then Xa, Xb and Xc are oxygen, Ra is d-C10alkyl, C2-C6alkenyl, C2-C6alkynyl, C3-C6cycloalkyl or d-dalkoxyd-dalkyl; and Rb is Ci-Cioalkyl, C2-C5alkenyl-CH2- , C2-C4alkenyl-CH(Me)-, C2-C5alkynyl-CH2-, C2-C4alkynyl-CH(Me)-, C3-C6cycloalkyl or Ci-C4alkoxyC C4alkyl.
4. A compound as claimed in claim 1 , 2 or 3, wherein R1 is fluorine.
5. A compound as claimed in claim 1 , 2 or 3, wherein R1 is chlorine.
6. A compound as claimed in claim 1 , 2, 3, 4 or 5, wherein, when R2 is
Ci-C2alkoxy-Ci-C3alkoxy- or Cifluoroalkoxy-CrC3alkoxy-, then R2 is
R2A0-CH(R2B)-CH(R2C)-0-;
wherein R2A is CrC2alkyl or Cifluoroalkyl; and
R2B and R2C are independently hydrogen or methyl, provided that one or both of R2B and R2C are hydrogen.
7. A compound as claimed in claim 1 , 2, 3, 4 or 5, wherein R2 is hydrogen, methyl, ethyl, n- propyl, n-butyl, cyclopropyl, ethynyl, cyano, fluorine, chlorine, bromine, methoxy, ethoxy, C-ifluoroalkoxy, C-ifluoroalkylmethoxy, (difluoro)vinyloxy, or MeO-CH2-CH2-0-.
8. A compound as claimed in claim 1 , 2, 3, 4 or 5, wherein R2 is methyl, ethyl, ethynyl, chlorine, methoxy, ethoxy or Cifluoroalkoxy.
9. A compound as claimed in claim 1 , 2, 3, 4 or 5, wherein R2 is chlorine, methoxy or ethoxy.
10. A compound as claimed in claim 1 , 2, 3, 4 or 5, wherein R2 is methoxy.
1 1 . A compound as claimed in claim 1 , 2, 3, 4, 6, 7, 8, 9 or 10, wherein:
R1 is fluorine, and R2 is chlorine, methoxy or ethoxy.
12. A compound as claimed in claim 1 , 2, 3, 5, 6, 7, 8, 9 or 10, wherein:
R1 is chlorine, and R2 is chlorine, methoxy or ethoxy.
13. A compound as claimed in claim 1 , 2, 3, 5, 6, 7, 8, 9 or 10, wherein:
R1 is chlorine, and R2 is methoxy.
14. A compound as claimed in any of claims 1 to 13, wherein R5 and R6 are not taken together to be -(CH2)n1- or -(CH2)n2-X1-(CH2)n3-.
15. A compound as claimed in any of claims 1 to 14, wherein R3 is hydrogen, CrC3alkyl, CrC2fluoroalkyl, or Het-CH2-; or R3 and R4 are taken together, and/or R3 and R5 are taken together, to form a chain which is (a), (b), (c), (d), (e), (f) or (g), as defined in any preceding claim.
16. A compound as claimed in any of claims 1 to 15, wherein R4 and R5, independently of each other, are: hydrogen, C C3alkyl, R9-C≡C-C(R7)(R8)-, or Het-CH2-;
provided that when X is NR4, then at least one of R3 and R4 is hydrogen or CrC3alkyl; and provided that when X is CR5R6, then at least one of R3 and R5 is hydrogen or CrC3alkyl; or R3 and R4 are taken together, and/or R3 and R5 are taken together, to form a chain which is (a), (b), (c), (d), (e), (f) or (g), as defined in any preceding claim.
17. A compound as claimed in one or more of claims 1 , 2, 3, 4, 5, 6, 7, 8, 9, 10, 1 1 , 12, 13, 14, 15 or 16, wherein R3 and R4 are taken together, and/or R3 and R5 are taken together, to form the chain which is (a), (e), (f) or (g), as shown below:
-C(R^)(R^)-C(R^)(R^4)-Y-C(R^)(R^)-C(R^)(R )- (a)
-C(R21)(R22)-C(R23)(R24)-C(R30)(R31)-C(R25)(R26)-C(R27)(R28)- (e)
-C(R21)(R22)-C(R21A)(R22A)-C(R30)(R31)-C(R27)(R28)- (f)
-CH(R29)-C(R30)(R31)-CH(R32)- (g); and wherein:
all of R21, R22, R27 and R28 are hydrogen,
R21A and R22A are both hydrogen, and
R29 and R32 are both hydrogen; and wherein R40 is C-i-C3alkoxy.
18. A compound as claimed in one or more of claims 1 , 2, 3, 4, 5, 6, 7, 8, 9, 10, 1 1 , 12, 13, 14, 15, 16 or 17, wherein:
Figure imgf000165_0001
A compound as claimed in any of claims 1 to 16, or claim 17 or 18, wherein X is NR4
20. A compound as claimed in any of claims 1 to 19, which is one of compounds A1 to A1 1 1 , or A142 to A149, or P1 to P12, as described and/or illustrated herein, optionally present as an agrochemically acceptable salt thereof.
21 . A compound as claimed in any of claims 1 to 19, which is one of compounds
A1 to A12, or A13, A14, A15, A22, A23, A24, A25, A26, A27, A28, A29, A29A, A30, A30A, A31 , A32, A32A, A33 or A33A, or A142 to A149, or P1 to P12, as described and/or illustrated herein, optionally present as an agrochemically acceptable salt thereof.
22. A herbicidal composition which comprises a compound of formula (I), as defined in any of claims 1 to 21 , and an agrochemically acceptable carrier, diluent and/or solvent.
23. A herbicidal composition as claimed in claim 22, which comprises one or more further herbicides and/or a safener.
24. A method of controlling grassy monocotyledonous weeds in crops of useful plants, comprising applying a compound of formula (I), as defined in any of claims 1 to 21 , or a herbicidal composition comprising such a compound as defined in claim 22 or 23, to the weeds and/or to the plants and/or to the locus thereof.
25. A method as claimed in claim 24, wherein the crops of useful plants comprise wheat, barley, rye, triticale, rice, sugarcane, soybean, peanut, pulse crops, cotton, rape, sunflower, linseed, sugarbeet, fodder beet, potato, and/or dicotyledonous vegetables.
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