WO2016207083A1 - Herbicidal compounds - Google Patents

Herbicidal compounds Download PDF

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WO2016207083A1
WO2016207083A1 PCT/EP2016/064090 EP2016064090W WO2016207083A1 WO 2016207083 A1 WO2016207083 A1 WO 2016207083A1 EP 2016064090 W EP2016064090 W EP 2016064090W WO 2016207083 A1 WO2016207083 A1 WO 2016207083A1
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alkyl
groups
optionally substituted
compound
formula
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PCT/EP2016/064090
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French (fr)
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William Guy Whittingham
Mangala Phadte
Guruprasad Narashimh SAWANT
Anne Jacqueline Dalencon
Katharine Mary INGRAM
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Syngenta Participations Ag
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Publication of WO2016207083A1 publication Critical patent/WO2016207083A1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
    • C07D409/06—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/36—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom five-membered rings
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
    • A01N43/42—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings condensed with carbocyclic rings
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/46—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom rings with more than six members
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having no bond to a nitrogen atom
    • 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
    • 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
    • C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
    • C07D211/04—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D211/80—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings 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
    • C07D211/84—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings 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 directly attached to ring carbon atoms
    • C07D211/86—Oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D221/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00
    • C07D221/02—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00 condensed with carbocyclic rings or ring systems
    • C07D221/20—Spiro-condensed ring systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D407/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00
    • C07D407/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00 containing two hetero rings
    • C07D407/06—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00 containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms

Definitions

  • the present invention relates to certain haloalkylsulphonamide derivatives, to processes for their preparation, herbicidal compositions comprising them, and their use in controlling plants or inhibiting plant growth.
  • the invention provides compounds of the formula (I)
  • W is selected from oxygen and sulphur
  • X is selected from oxygen and CR 9 R 10 ; m is 0, 1 or 2; n is 1 , 2, 3 or 4; - - p is 0, 1 , 2 or 3; with the proviso that 2 ⁇ n + p ⁇ 4; R is Ci- 6 haloalkyl;
  • R is selected from H, C 1 _ 4 alkyl, C 3 . 5 alkenyl, propargyl, Ci. 4 alkoxyCi_
  • each R 20 is, independently, selected from halogen, Ci_ 4 alkyl, Ci_ 4 haloalkyl, Ci_ 4 alkoxy, Ci_ 4 haloalkoxy, Ci_ 2 alkoxyCi_ 2 alkoxy, hydroxy, phenyl and phenoxy; each R 2 is, independently, selected from halogen, nitrile, Ci_ 4 alkyl, Ci_ 4 haloalkyl, C 3 .
  • Ci_ 6 cycloalkyl, C 2 . 4 alkenyl, C 2 . 4 alkynyl, Ci_ 4 alkoxy, Ci_ 4 haloalkoxy, Ci_ 2 alkoxyCi_ 2 alkoxy, hydroxy, Ci_
  • each R 3 is, independently, selected from halogen, nitrile, Ci_ 4 alkyl, Ci_ 4 haloalkyl, C 3 . 6 cycloalkyl, C 2 . 4 alkenyl, C 2 . 4 alkynyl, Ci_ 4 alkoxy, Ci_ 4 haloalkoxy, Ci_ 2 alkoxyCi_ 2 alkoxy, hydroxy, d.
  • each R 5 and R 6 are, independently, selected from H, halogen, cyano, hydroxy, Ci_ 4 alkyl, d. 4 haloalkyl, C 3 . 6 cycloalkyl, Ci_ 2 alkoxyCi_ 2 alkyl, C 2 . 5 alkenyl, C 2 .
  • each R is, independently, selected from halogen, cyano, C 1 _ 4 alkyl, Ci_ 4 haloalkyl, Ci_ 4 alkoxy, Ci_ 4 haloalkoxy, hydroxy, phenyl and phenoxy; each R 7 and R 8 are, independently, selected from H, d- 5 alkyl, Ci_ 4 haloalkyl, C 3 . 6 cycloalkyl optionally substituted with 1-3 groups selected from halogen, Ci_ 4 alkyl and phenyl, Ci_ 4 alkoxyCi_ 4 alkyl, Ci. 4 alkoxycarbonylaminoCi_ 4 alkyl, Ci. 4 alkylcarbonyloxyCi.
  • arylCi_ 2 alkyl optionally substituted by 1-3 groups R 2
  • aryloxyCi_ 2 alkyl optionally substituted by 1-3 groups R 2
  • arylCi. 2 alkoxyCi. 2 alkyl optionally substituted by 1-3 groups R 2 ,C 2 .
  • each R 2 is, independently, selected from halogen, cyano, Ci_ 4 alkyl, Ci_ 4 haloalkyl, Ci_ 4 alkoxy, d. 4 haloalkoxy, Ci_ 2 alkoxyCi_ 2 alkoxy, hydroxy, phenyl and phenoxy or two R 2 groups together form -OCH 2 0- or -OCH 2 CH 2 0-;
  • R 9 is selected from H, Ci_ 6 alkyl, Ci_ 6 haloalkyl, C 3 . 6 cycloalkylCi. 2 alkyl, C 3 . 6 cycloalkyl, Ci_ 4 alkoxy, Ci_ 4 alkylthio, Ci_ 4 alkylamino, aryl optionally substituted by 1-3 groups R 22 , arylCi_ 2 alkyl optionally substituted by 1-3 groups R 22 and heteroaryl optionally substituted by 1-3 groups R 22 and each R 22 is, independently, selected from halogen, nitro, cyano, Ci_ 4 alkyl, Ci_ 4 haloalkyl, Ci_ 4 alkoxy, d.
  • R 0 is selected from H, Ci_ 6 alkyl, Ci_ 4 alkylcarbonyl, Ci_ 4 alkoxycarbonyl, Ci_ 4 alkoxy, Ci_ 4 alkylthio, Ci_ 4 alkylamino and Ci_ 4 alkylsulphonyl, or R 0 and R 5 or R 8 together form a C 2 . 4 alkylene chain; or an N-oxide or salt form thereof.
  • the preferred groups for A, W, X, m, n, p, R 1 , R 2 , R 3 , R 5 , R 6 , R 7 , R 8 , R 9 , R 0 , R 20 , R 21 , R 22 and R 24 in any combination thereof, are as set out below:
  • W is oxygen
  • m is 0 or 1.
  • n 0.
  • n is 2, 3 or 4.
  • p is 0.
  • R is Ci_ 2 haloalkyl. More preferably, R is trifluoromethyl.
  • R is selected from H, Ci- 4 alkoxyCi- 2 alkoxyCi- 2 alkyl, d- 4 haloalkoxyCi. 2 alkyl, arylCi_ 2 alkyl optionally substituted by 1-3 groups R 20 , arylCi- 2 alkoxyCi- 2 alkyl optionally substituted by 1-3 groups R 20 , rylcarbonyloxyCi_ 2 alkyl optionally substituted by 1-3 groups R 20 , Ci_ 8 alkylcarbonyl, d- 4 haloalkylcarbonyl, Ci_i 0 alkoxycarbonyl; Ci_ 4 haloalkoxycarbonyl, d- 4 alkoxyCi.
  • R is selected from H, Ci_ 5 alkylcarbonyl, Ci_ 4 haloalkylcarbonyl, d- 5 alkoxycarbonyl, Ci. 4 haloalkoxycarbonyl and Ci. 4 haloalkylsulphonyl.
  • R is selected from H, d. 5 alkylcarbonyl and d. 5 alkoxycarbonyl.
  • R 2 is selected from halogen, C 1 _ 4 alkyl, C-
  • R 2 is selected from halogen and methyl.
  • R 3 is selected from halogen, C 1 _ 4 alkyl, C-
  • R 5 and R 6 are, independently, selected from H, halogen, C 1 _ 4 alkyl, d_ 4 haloalkyl, Ci. 4 alkoxy, Ci. 4 alkylthio, aryl optionally substituted by 1-3 groups R 24 , aryloxy optionally substituted by 1-3 groups R 24 and arylthio optionally substituted by 1-3 groups R 24 .
  • R 5 and R 6 are, independently, selected from H, halogen, C 1 _ 4 alkyl, d_ 4 haloalkyl, d_ 4 alkoxy, Ci_ 4 alkylthio and aryl optionally substituted by 1-2 groups R 24 .
  • R 5 and R 6 are, independently, selected from H, halogen, d. 3 alkyl, d- 3 alkoxy and d. 3 alkylthio.
  • R 7 and R 8 are, independently, selected from H, d. 5 alkyl, d_ 4 haloalkyl, d- 6 cycloalkyl, Ci. 4 alkoxyCi. 4 alkyl, aryld. 2 alkyl optionally substituted by 1-3 groups R 2 , d- 4 alkenyl, Ci_ 4 alkoxy, Ci. 4 alkylthio, aryl optionally substituted by 1-3 groups R 2 , aryloxy optionally substituted by 1-3 groups R 2 , arylthio optionally substituted by 1-3 groups R 2 and heteroaryl optionally substituted by 1-3 groups R 2 , or R 7 and R 8 on the same carbon atom together form a - -
  • R 7 and R 8 are, independently, selected from H, C 1 _ 4 alkyl, C-
  • R 7 and R 8 are, independently, selected from H, Ci_ 3 alkyl, trifluoromethyl, cyclopropyl, methoxymethyl, Ci_ 3 alkoxy and aryl optionally substituted by 1-2 groups R 2 , or R 7 and R 8 together form a C 3 . 5 alkylene chain optionally containing an oxygen atom, or R 7 and R 8 on adjacent carbon atoms together form a CH 2 group.
  • R 9 is selected from H, C 1 _ 4 alkyl, C 3 . 6 cycloalkyl and aryl optionally substituted by 1-3 groups R 22 . More preferably, R 9 is selected from H, Ci_ 2 alkyl and aryl optionally substituted by 1-3 groups R 22 .
  • R 0 is selected from H, C 1 _ 4 alkyl, C-i_ 2 alkoxy and Ci_ 2 alkylthio. More preferably, R 0 is selected from H and C 1 _ 4 alkyl.
  • R 20 is selected from halogen, d_ 4 alkyl, C-
  • R 2 is selected from halogen, cyano, d_ 4 alkyl, C-
  • R 2 is selected from halogen, methyl and methoxy.
  • R 22 is selected from halogen, cyano, Ci_ 2 alkyl, Ci_ 2 haloalkyl, Ci_ 2 alkoxy and d. 2 haloalkoxy.
  • R 22 is selected from halogen, Ci_ 2 alkyl, Ci_ 2 haloalkyl, Ci_ 2 alkoxy and Ci_ 2 haloalkoxy.
  • R 24 is selected from halogen, cyano, d_ 4 alkyl, C-
  • 422 compounds are described, designated compounds 3-1 to 3-422 respectively, of formula (la), wherein R is H, A is S and the values of R 7 , R 8 , R 7 , R 8 and X are as defined in Table 1.
  • 662 compounds are described, designated compounds 15-1 to 15-662 respectively, of formula (lc), wherein R is H, A is S and the values of R 7 , R 8 , R 7' , R 8' , R 7" , R 8" and X are as defined in Table 3.
  • 41 1 compounds are described, designated compounds 33-1 to 33-41 1 respectively, of formula (If), wherein R is H, A is S and the values of R 7 , R 8 , R 7' , R 8' , R 7" , R 8" , R 7 "' , R 8" and X are as defined in Table 6.
  • 143 compounds are described, designated compounds 39-1 to 39-143 respectively, of formula (Ig), wherein R is H, A is S and the values of R 5 , R 6 , R 7 , R 8 , R 7' , R 8' , R 7" , R 8" and X are as defined in Table 7.
  • 142 compounds are described, designated compounds 51-1 to 51-142 respectively, of formula (li), wherein R is H, A is S and the values of R 5 , R 6 , R 5' , R 6 , R 5" , R 6" , R 7 , R 8 and X are as defined in Table 9.
  • the compounds of formula (I) may exist as different geometric isomers, or in different tautomeric forms. This invention covers all such isomers and tautomers, and mixtures thereof in all proportions, as well as isotopic forms such as deuterated compounds.
  • the compounds of this invention may contain one or more asymmetric centers and may thus give rise to optical isomers and diastereomers. While shown without respect to
  • the present invention includes all such optical isomers and diastereomers as well as the racemic and resolved, enantiomerically pure R and S stereoisomers and other mixtures of the R and S stereoisomers and agrochemically acceptable salts thereof. It is recognized that certain optical isomers, or diastereomers may have favorable properties over the other. Thus when disclosing and claiming the invention, when a racemic mixture is disclosed, it is clearly contemplated that both optical isomers, including diastereomers substantially free of the other are disclosed and claimed as well.
  • Alkyl as used herein, means an aliphatic hydrocarbon chain and includes straight and branched chains e. g. of 1 to 8 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, n-pentyl, isopentyl, neo-pentyl, n-hexyl, and isohexyl.
  • Cycloalkyl as used herein, means a cyclic, saturated hydrocarbon group having from 3 to 6 ring carbon atoms.
  • Examples of cycloalkyl groups are cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.
  • Cycloalkylalkyl as used herein, means a radical -R-cycloalkyl, wherein R is alkyl as defined above.
  • Alkenyl means an aliphatic hydrocarbon chain having at least one double bond, and preferably one double bond, and includes straight and branched chains e. g. of 2 to 8 carbon atoms such as ethenyl (vinyl), prop-1-enyl, prop-2-enyl (allyl), isopropenyl, but-1-enyl, but- 2-enyl, but-3-enyl, 2-methypropenyl.
  • Alkynyl as used herein, means an aliphatic hydrocarbon chain having at least one triple bond, and preferably one triple bond, and includes straight and branched chains e. g. of 2 to 8 carbon atoms such as ethynyl, prop-1-ynyl, prop-2-ynyl (propargyl), but-1-ynyl, but-2-ynyl and but-3-ynyl.
  • Alkylene as used herein, means a linear saturated divalent hydrocarbon radical of one to six carbon atoms or a branched saturated divalent hydrocarbon radical of three to six carbon atoms, e.g. methylene, ethylene, propylene, 2-methylpropylene and the like.
  • Alkoxy as used herein, means a radical -OR, wherein R is alkyl as defined above.
  • alkoxy groups include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, t-butoxy, n-pentoxy, isopentoxy, neo-pentoxy, n-hexyloxy, and isohexyloxy.
  • Alkoxyalkyl as used herein, means a radical -ROR, wherein each R is, independently, an alkyl group as defined above.
  • Alkoxyalkoxy as used herein, means a radical -OROR, wherein each R is, independently, alkyl as defined above.
  • Alkoxyalkoxyalkyl as used herein, means a radical -ROROR, wherein each R is, independently, alkyl as defined above.
  • Cyanoalkyl as used herein, means an alkyl group as defined above substituted with one or more cyano groups.
  • Alkylthio as used herein, means a radical -SR, wherein R is alkyl as defined above.
  • Alkylthio groups include, but are not limited to, methylthio, ethylthio, propylthio, tert-butylthio, and the like.
  • Alkylthioalkyl as used herein, means a radical -RSR, wherein each R is, independently, alkyl as defined above.
  • Halogen, halide and halo refer to iodine, bromine, chlorine and fluorine. - -
  • Haloalkyi means an alkyl group as defined above wherein at least one hydrogen atom has been replaced with a halogen atom as defined above.
  • haloalkyi groups include chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl and trifluoromethyl.
  • Preferred haloalkyi groups are fluoroalkyi groups ⁇ i.e. haloalkyi groups, containing fluorine as the only halogen). More highly preferred haloalkyi groups are perfluoroalkyi groups, i.e. alkyl groups wherein all the hydrogen atoms are replaced with fluorine atoms.
  • Haloalkoxy as used herein, means a radical -OR, wherein R is haloalkyi as defined above.
  • Haloalkoxyalkyl as used herein, means a radical -ROR', wherein R is alkyl as defined above and R' is haloalkyi as defined above.
  • Haloalkylthio as used herein, means a radical -SR, wherein R is haloalkyi as defined above.
  • Alkylcarbonyl as used herein, means a radical -C(0)R, wherein R is alkyl as defined above.
  • Alkenylcarbonyl as used herein, means a radical -C(0)R, wherein R is alkenyl as defined above.
  • Cycloalkylcarbonyl as used herein, means a radical -C(0)R, wherein R is cycloalkyl as defined above.
  • Alkoxycarbonyl as used herein, means a radical -C(0)OR, wherein R is alkyl as defined above.
  • Alkoxyalkoxycarbonyl as used herein, means a radical -C(0)OROR, wherein each R is, independently, alkyl as defined above.
  • Alkenyloxycarbonyl as used herein, means a radical -C(0)OR, wherein R is alkenyl as defined above.
  • Propargyloxycarbonyl as used herein, means a radical -C(0)OR, wherein R is propargyl.
  • Alkylcarbonylalkyl as used herein, means a radical -RC(0)R, wherein each R is, independently, alkyl as defined above.
  • Alkoxycarbonylalkyl means a radical -RC(0)OR, wherein each R is, independently, alkyl as defined above.
  • Alkoxyalkylcarbonyl means a radical -C(0)ROR, wherein each R is, independently, alkyl as defined above. - -
  • Alkoxycarbonylalkylcarbonyl as used herein, means a radical -C(0)RC(0)OR, wherein each R is, independently, alkyl as defined above.
  • Alkylthiocarbonyl as used herein, means a radical -C(0)SR, wherein R is alkyl as defined above.
  • Haloalkylcarbonyl as used herein means a radical -C(0)R, wherein R is haloalkyi as defined above.
  • Haloalkoxycarbonyl as used herein, means a radical -C(0)OR, wherein R is haloalkyi as defined above.
  • Alkylcarbonyloxy as used herein, means a radical -OC(0)R, wherein R is an alkyl group as defined above.
  • Alkylcarbonyloxyalkyl as used herein, means a radical -ROC(0)R, wherein each R is, independently, alkyl as defined above.
  • Alkoxycarbonyloxyalkyl as used herein, means a radical -ROC(0)OR, wherein each R is, independently, alkyl as defined above.
  • Alkylsulphonyl as used herein, means a radical -S(0) 2 R, wherein R is alkyl as defined above.
  • Haloalkylsulphonyl as used herein, means a radical -S(0) 2 R, wherein R is haloalkyi as defined above.
  • Alkylsulphonylalkyl as used herein, means a radical -RS(0) 2 R, wherein each R is, independently, alkyl as defined above.
  • Hydroxy or hydroxyl as used herein, means the group -OH.
  • Nitro as used herein, means the group -N0 2 .
  • Cyano, or nitrile as used herein, means the group -CN.
  • Aryl as used herein, means an unsaturated aromatic carbocyclic group of from 6 to 10 carbon atoms having a single ring (e.g., phenyl) or multiple condensed (fused) rings, at least one of which is aromatic (e.g., indanyl, naphthyl).
  • Preferred aryl groups include phenyl, naphthyl and the like. Most preferably, an aryl group is a phenyl group.
  • Aryloxy as used herein, means a radical -O-Aryl, wherein Aryl is as defined above.
  • Preferred aryloxy groups include phenoxy, naphthyloxy and the like.
  • Arylalkyl as used herein, means a radical -R-Aryl, wherin R is alkyl as defined above. - -
  • Arylalkoxyalkyl as used herein, means a radical -ROR-Aryl, wherein each R is, independently, alkyl as defined above.
  • Aryloxyalkyl means a radical -RO-Aryl, wherein R is alkyl as defined above.
  • Arylthio as used herein, means a radical -S-Aryl.
  • Arylthioalkyl as used herein, means a radical -RS-Aryl, wherein R is alkyl as defined above.
  • Arylalkylthioalkyl means a radical -RSR-Aryl, wherein each R is, independently, alkyl as defined above.
  • Arylcarbonyl means a radical -C(0)-Aryl.
  • Arylcarbonylalkyl as used herein, means a radical -RC(0)-Aryl, wherein R is alkyl as defined above.
  • Aryloxycarbonyl as used herein, means a radical -C(0)0-Aryl.
  • Arylalkoxycarbonyl as used herein, means a radical -C(0)OR-Aryl, wherein R is alkyl as defined above.
  • Aryloxyalkylcarbonyl as used herein, means a radical -C(0)RO-Aryl, wherein R is alkyl as defined above.
  • Arylcarbonyloxyalkyl means a radical -ROC(0)-Aryl, wherein R is alkyl as defined above.
  • Aryloxycarbonyloxyalkyl means a radical -ROC(0)OAryl, wherein R is alkyl as defined above.
  • Arylsulphonyl as used herein, means a radical -S(0) 2 Aryl.
  • Heteroaryl as used herein, means a ring system containing 5 to 10 ring atoms, 1 to 4 ring heteroatoms and consisting either of a single aromatic ring or of two or more fused rings, at least one of which is aromatic.
  • single rings will contain up to three and bicyclic systems up to four heteroatoms which will preferably be independently chosen from nitrogen, oxygen and sulfur.
  • Examples of such groups include pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, furanyl, thiophenyl, oxazolyl, isoxazolyl, oxadiazolyl, thiazolyl, isothiazolyl, thiadiazolyl, pyrrolyl, pyrazolyl, imidazolyl, triazolyl and tetrazolyl.
  • bicyclic groups are benzothiophenyl, benzimidazolyl, benzothiadiazolyl, quinolinyl, cinnolinyl, quinoxalinyl and pyrazolo[1 ,5- a] pyrimidinyl. - -
  • Heteroarylalkyl as used herein, means a radical -R-Het, wherein R is alkyl as defined above and Het is heteroaryl as defined above.
  • Heterocyclyl as used herein, means a non-aromatic ring system containing 3 to 10 ring atoms, at least one ring heteroatom and consisting either of a single ring or of two or more fused rings.
  • single rings will contain up to three and bicyclic systems up to four heteroatoms which will preferably be chosen from nitrogen, oxygen and sulfur.
  • Examples of such groups include pyrrolidinyl, imidazolinyl, pyrazolidinyl, piperidyl, piperazinyl, quinuclidinyl, morpholinyl, tetrahydrofuranyl, together with unsaturated or partially unsaturated analogues such as 4,5,6,7- tetrahydro-benzothiophenyl, chromen-4-onyl, 9H-fluorenyl, 3,4-dihydro-2H-benzo-1 ,4-dioxepinyl, 2,3-dihydro-benzofuranyl, piperidinyl, 1 ,3-dioxolanyl, 1 ,3-dioxanyl and 4,5-dihydro-isoxazolyl.
  • unsaturated or partially unsaturated analogues such as 4,5,6,7- tetrahydro-benzothiophenyl, chromen-4-onyl, 9H-flu
  • Aminocarbonyl as used herein, means a radical -C(0)NH 2 .
  • Alkylaminocarbonyl as used herein, means a radical -C(0)NRH, wherein R is alkyl as defined above.
  • Dialkylaminocarbonyl as used herein, means a radical -C(0)NRR, wherein each R is, independently, alkyl as defined above.
  • Alkoxycarbonylaminoalkyl as used herein, means a radical -RNHC(0)OR, wherein each R is, independently, alkyl as defined above.
  • Optionally substituted' as used herein means the group referred to can be substituted at one or more positions by any one or any combination of the radicals listed thereafter.
  • one or more hydrogen atoms are replaced by the radicals listed thereafter.
  • halogenated groups for example, haloalkyl groups, one or more halogen atoms are replaced by the radicals listed thereafter.
  • Suitable salts include those derived from alkali or alkaline earth metals and those derived from ammonia and amines.
  • Preferred cations include sodium, potassium, magnesium, and ammonium cations of the formula N + (R 29 R 30 R 3 R 32 ) wherein R 29 , R 30 , R 3 and R 32 are independently selected from hydrogen, Ci-C 6 alkyl and Ci-C 6 hydroxyalkyl.
  • Salts of the compounds of formula (I) can be prepared by treatment of compounds of formula (I) with a metal hydroxide, such as sodium hydroxide, or an amine, such as ammonia, trimethylamine, diethanolamine, 2-methylthiopropylamine, bisallylamine, 2-butoxyethylamine, morpholine, cyclododecylamine, or benzylamine.
  • a metal hydroxide such as sodium hydroxide
  • an amine such as ammonia, trimethylamine, diethanolamine, 2-methylthiopropylamine, bisallylamine, 2-butoxyethylamine, morpholine, cyclododecylamine, or benzylamine.
  • Amine salts are often preferred forms of the compounds of formula (I) because they are water-soluble and lend themselves to the preparation of desirable aqueous based herbicidal compositions.
  • Acceptable salts can also be formed from organic and inorganic acids, for example, acetic, propionic, lactic, citric, tartaric, succinic, fumaric, maleic, malonic, mandelic, malic, phthalic, hydrochloric, hydrobromic, phosphoric, nitric, sulfuric, methanesulfonic, naphthalenesulfonic, - - benzenesulfonic, toluenesulfonic, camphorsulfonic, and similarly known acceptable acids when a compound of this invention contains a basic moiety.
  • organic and inorganic acids for example, acetic, propionic, lactic, citric, tartaric, succinic, fumaric, maleic, malonic, mandelic, malic, phthalic, hydrochloric, hydrobromic, phosphoric, nitric, sulfuric, methanesulfonic, naphthalenesulfonic, - - benzenes
  • the starting materials used for the preparation of the compounds of the invention may be purchased from usual commercial suppliers or may be prepared by known methods.
  • the starting materials as well as the intermediates may be purified before use in the next step by state of the art methodologies such as chromatography, crystallization, distillation and filtration.
  • a compound of formula (A) may be heated with a compound of formula (B) in the presence of a catalyst, for example an acid, such as para-toluene sulphonic acid, in a suitable solvent, for example toluene or chlorobenzene.
  • a catalyst for example an acid, such as para-toluene sulphonic acid
  • a suitable solvent for example toluene or chlorobenzene.
  • the process may conveniently be carried out using microwave heating or conventional heating in an apparatus for the removal of water, for example a Dean-Stark trap.
  • Compounds of formula (A) may be prepared from compounds of formula (C) as shown in reaction scheme 2.
  • a compound of formula (C) may be treated with a reducing agent such as lithium aluminium hydride in a suitable solvent such as tetrahydrofuran.
  • a reducing agent such as lithium aluminium hydride
  • a suitable solvent such as tetrahydrofuran.
  • a compound of formula (D) may be treated with a sulphonylating reagent, for example a sulphonic anhydride such as trifluoromethanesulphonic anhydride or a sulphonyl halide such as trifluoromethanesulphonyl chloride, in the presence of a base, for example an organic base such as triethylamine, in a suitable solvent, for example dichloromethane.
  • a sulphonylating reagent for example a sulphonic anhydride such as trifluoromethanesulphonic anhydride or a sulphonyl halide such as trifluoromethanesulphonyl chloride
  • a base for example an organic base such as triethylamine
  • a suitable solvent for example dichloromethane.
  • a compound of formula (E) in which LG' is a halogen, for example a bromine atom may be treated with a sulphonamide RS0 2 NH 2 in the presence of a base, for example an inorganic base such as caesium carbonate or sodium hydride, in a suitable solvent such as dioxane.
  • a suitable catalyst for example a metal catalyst such as a palladium dibenzylidene acetone complex, and optionally a ligand, for example a phosphine ligand such as XantPhos.
  • a metal catalyst such as a palladium dibenzylidene acetone complex
  • a ligand for example a phosphine ligand such as XantPhos.
  • Compounds of formula (E) may be prepared from compounds of formula (F) and compounds of formula (B) as shown in reaction scheme 5.
  • a compound of formula (F) in which LG and LG' are halogens, for example chlorine atoms may be reacted with a compound of formula (B) in the presence of a base, for example an inorganic base such as sodium hydride, in a suitable solvent, for example tetrahydrofuran.
  • a base for example an inorganic base such as sodium hydride
  • a suitable solvent for example tetrahydrofuran.
  • a compound of formula (G) may be treated with a halogenating agent, for example /V-bromosuccinimide, in a suitable solvent, for example carbon tetrachloride, optionally in the presence of a reaction initiator, for example a radical initiator such as azobisisobutyronitrile or irradiation with UV or visible light.
  • a halogenating agent for example /V-bromosuccinimide
  • a suitable solvent for example carbon tetrachloride
  • a reaction initiator for example a radical initiator such as azobisisobutyronitrile or irradiation with UV or visible light.
  • a compound of formula (H) may be treated with a halogenating agent, for example, thionyl chloride, in a suitable solvent, for example dichloromethane.
  • a halogenating agent for example, thionyl chloride
  • a compound of formula (J) in which LG is a halogen, for example a chlorine atom may be reacted with a compound of formula (B) in the presence of a base, for example an inorganic base such as potassium t-butoxide, in a suitable solvent, for example tetrahydrofuran.
  • a base for example an inorganic base such as potassium t-butoxide
  • a suitable solvent for example tetrahydrofuran.
  • a compound of formula (A) may be treated with a halogenating agent, for example, thionyl chloride, in a suitable solvent, for example dichloromethane.
  • a halogenating agent for example, thionyl chloride
  • a compound of formula (K) may be reacted with an aldehyde, for example aqueous formaldehyde, in the presence of an acid, for example an organic acid such as para- toluene sulphonic acid, in a suitable solvent, for example dioxane.
  • an aldehyde for example aqueous formaldehyde
  • an acid for example an organic acid such as para- toluene sulphonic acid
  • a suitable solvent for example dioxane.
  • a compound of formula (L) may be treated with a base, for example a strong base such as sodium hexamethyldisilazide, and a nitrosylating agent, for example isopentyl nitrite, in a suitable solvent, for example tetrahydrofuran.
  • a base for example a strong base such as sodium hexamethyldisilazide
  • a nitrosylating agent for example isopentyl nitrite
  • suitable solvent for example tetrahydrofuran.
  • a compound of formula (M) may be treated with a sulphonylating reagent, for example a sulphonic anhydride such as trifluoromethanesulphonic anhydride, in the presence of a base, for example an organic base such as triethylamine, in a suitable solvent, for example dichloromethane.
  • a sulphonylating reagent for example a sulphonic anhydride such as trifluoromethanesulphonic anhydride
  • a base for example an organic base such as triethylamine
  • a suitable solvent for example dichloromethane.
  • a compound of formula (N) may be treated with a reducing agent, for example a dissolving metal such as iron and ammonium chloride, in a suitable solvent, for example a mixture of water and ethanol.
  • a reducing agent for example a dissolving metal such as iron and ammonium chloride
  • a suitable solvent for example a mixture of water and ethanol.
  • a compound of formula (O) in which LG is a halogen, for example a bromine atom may be reacted with a compound of formula (B) in the presence of a base, for example an inorganic base such as sodium hydride or caesium carbonate, in a suitable solvent, for example dimethylformamide.
  • a base for example an inorganic base such as sodium hydride or caesium carbonate
  • a suitable solvent for example dimethylformamide.
  • a compound of formula (B) in which X is oxygen may be treated with an olefinating reagent, for example a phosphonium salt, in the presence of a base, for example a strong base such as sodium hydride, in a suitable solvent, for example tetrahydrofuran.
  • an olefinating reagent for example a phosphonium salt
  • a base for example a strong base such as sodium hydride
  • a suitable solvent for example tetrahydrofuran.
  • a compound (P) may be treated with an oxidising agent, for example a hypervalent iodine compound such as the Dess-Martin periodinane, in a suitable solvent, for example dichloromethane.
  • an oxidising agent for example a hypervalent iodine compound such as the Dess-Martin periodinane
  • a suitable solvent for example dichloromethane.
  • a compound of formula (Q) may be reacted with a base, for example an inorganic base such as potassium carbonate, in a suitable solvent, for example an alcoholic solvent such as methanol.
  • a base for example an inorganic base such as potassium carbonate
  • a suitable solvent for example an alcoholic solvent such as methanol.
  • a compound of formula (R) in which LG is a bromine atom may be reacted with a suitable nucleophile, for example potassium acetate, optionally in the presence of an additive such as 18-crown-6, in a suitable solvent, for example acetonitrile.
  • a suitable nucleophile for example potassium acetate
  • an additive such as 18-crown-6
  • a compound of formula (S) may be treated with a halogenation reagent, for example a brominating reagent such as phenyltrimethylammonium tribromide, optionally in the - - presence of a base, for example an organic base such as triethylamine, and a suitable additive, for example a silylating agent such as trimethylsilyl trifluoromethanesulphonate, in a suitable solvent, for example dichloromethane.
  • a halogenation reagent for example a brominating reagent such as phenyltrimethylammonium tribromide
  • a base for example an organic base such as triethylamine
  • a suitable additive for example a silylating agent such as trimethylsilyl trifluoromethanesulphonate
  • a compound of formula (T) may be reacted with a Lewis acid, for example, boron tribromide, in a suitable solvent, for example dichloromethane.
  • a Lewis acid for example, boron tribromide
  • a suitable solvent for example dichloromethane
  • Compounds of formula (T) may be prepared from compounds of formula (U), as shown in reaction scheme 21.
  • a compound of formula (U) may be treated with a reducing agent, for example a metal hydride reducing agent such sodium borohydride, optionally in the presence of an additive, for example a metal salt such as cobalt chloride, in a suitable solvent, for example tetrahydrofuran.
  • a reducing agent for example a metal hydride reducing agent such sodium borohydride
  • an additive for example a metal salt such as cobalt chloride
  • a suitable solvent for example tetrahydrofuran.
  • a compound of formula (V) may be heated with a suitable additive, for example a metal salt such as lithium chloride, in a suitable solvent, for example dimethyl sulphoxide.
  • a suitable additive for example a metal salt such as lithium chloride
  • a suitable solvent for example dimethyl sulphoxide.
  • Compounds of formula (V) may be prepared from compounds of formula (W) and compounds of formula (X), as shown in reaction scheme 23.
  • a mixture of a compound of formula (W) and a compound of formula (X) maybe treated with a base, for example a strong base such as lithium hexamethyldisilazide, in a suitable solvent, such as tetrahydrofuran.
  • a base for example a strong base such as lithium hexamethyldisilazide
  • a suitable solvent such as tetrahydrofuran.
  • Compounds of formula (X) may be prepared from compounds of formula (Y) and compounds of formula (Z), as shown in reaction scheme 24.
  • a mixture of a compound of formula (Y) and a compound of formula (Z) may be treated with a base, for example an organic base such as piperidine, optionally in the presence of a suitable solvent, for example tetrahydrofuran.
  • a base for example an organic base such as piperidine
  • a suitable solvent for example tetrahydrofuran.
  • a compound of formula (AA) may be heated in the presence of a catalyst, for example an acid, such as para-toluene sulphonic acid, in a suitable solvent, for example dioxane.
  • a catalyst for example an acid, such as para-toluene sulphonic acid, in a suitable solvent, for example dioxane.
  • Compounds of formula (AA) may be prepared from compounds of formula (BB), as shown in reaction scheme 26.
  • a compound of formula (BB) may be heated with morpholine.
  • Compounds of formula (BB) may be prepared from compounds of formula (S), as shown in reaction scheme 27.
  • a compound of formula (S) may be treated with a chlorinating reagent, for example phosphorus pentachloride, in a suitable solvent, for example chloroform.
  • a chlorinating reagent for example phosphorus pentachloride
  • a compound of formula (CC) may be treated with a dehydrating agent, for example a carbodiimide such as dicyclohexyl carbodiimide, optionally in the presence of a catalyst, for example a metal salt such as copper (I) iodide, in a suitable solvent, for example toluene.
  • a dehydrating agent for example a carbodiimide such as dicyclohexyl carbodiimide
  • a catalyst for example a metal salt such as copper (I) iodide
  • a suitable solvent for example toluene.
  • Compounds of formula (CC) may be prepared from compounds of formula (DD) as shown in reaction scheme 29.
  • a compound of formula (DD) may be treated with a reducing agent, for example a metal hydride reducing agent such as sodium borohydride, in a suitable solvent, for example methanol.
  • a reducing agent for example a metal hydride reducing agent such as sodium borohydride
  • a suitable solvent for example methanol.
  • a compound of formula (S) may be treated with a base, for example a strong base such as butyl lithium, and a ketone or aldehyde of formula (EE) in a suitable solvent, for example tetrahydrofuran.
  • a base for example a strong base such as butyl lithium
  • a ketone or aldehyde of formula (EE) in a suitable solvent, for example tetrahydrofuran.
  • a compound of formula (I) in which X is oxygen may be treated with an olefinating reagent, for example a phosphonium salt, in the presence of a base, for example a strong base such as sodium hydride, in a suitable solvent, for example tetrahydrofuran.
  • an olefinating reagent for example a phosphonium salt
  • a base for example a strong base such as sodium hydride
  • a suitable solvent for example tetrahydrofuran.
  • a compound of formula (I) in which R is H may be treated with a base, for example an inorganic base such as sodium hydride or an organic base such as triethylamine, and an electrophilic reagent LG-R , in a suitable solvent, for example dichloromethane.
  • a base for example an inorganic base such as sodium hydride or an organic base such as triethylamine, and an electrophilic reagent LG-R , in a suitable solvent, for example dichloromethane.
  • a compound of formula (I) in which R is not H may be prepared from compounds of formula (FF) as shown in reaction scheme 33.
  • a compound of formula (FF) may be treated with a sulphonylating reagent, for example a sulphonyl halide such as trifluoromethanesulphonyl chloride, in the presence of a base, for example an inorganic base such as sodium hydride, in a suitable solvent, for example dimethoxyethane.
  • a sulphonylating reagent for example a sulphonyl halide such as trifluoromethanesulphonyl chloride
  • a base for example an inorganic base such as sodium hydride
  • a suitable solvent for example dimethoxyethane.
  • a compound of formula (M) may be treated with a base, for example an inorganic base such as sodium bicarbonate or an organic base such as triethylamine, and an electrophilic reagent LG-R , for example a chloroformate, in a suitable solvent, for example acetonitrile.
  • a base for example an inorganic base such as sodium bicarbonate or an organic base such as triethylamine
  • LG-R for example a chloroformate
  • a compound of formula (I) in which R is H may be treated with a suitable electrophilic reagent, for example a halogenating agent such as /V-bromosuccinimide, optionally in the presence of an additive, such as a radical initiator such as AIBN, in a suitable solvent, for example carbon tetrachloride.
  • a suitable electrophilic reagent for example a halogenating agent such as /V-bromosuccinimide
  • an additive such as a radical initiator such as AIBN
  • a suitable solvent for example carbon tetrachloride.
  • the compounds of formula (I) according to the invention can be used as herbicides in unmodified form, as obtained in the synthesis, but they are generally formulated into herbicidal compositions in various ways using formulation adjuvants, such as carriers, solvents and surface- active substances. Therefore, the invention also relates to a herbicidal composition which comprises a herbicidally effective amount of a compound of formula (I) in addition to formulation adjuvants.
  • the compounds according to the invention are generally formulated in various ways using formulation adjuvants, such as carriers, solvents and surface-active substances.
  • formulation adjuvants such as carriers, solvents and surface-active substances.
  • formulations can be in various physical forms, e.g. in the form of dusting powders, gels, wettable powders, water-dispersible granules, water-dispersible tablets, effervescent pellets, emulsifiable - - concentrates, microemulsifiable concentrates, oil-in-water emulsions, oil-flowables, aqueous dispersions, oily dispersions, suspo-emulsions, capsule suspensions, emulsifiable granules, soluble liquids, water-soluble concentrates (with water or a water-miscible organic solvent as carrier), impregnated polymer films or in other forms known e.g. from the Manual on
  • Such formulations can either be used directly or diluted prior to use.
  • the dilutions can be made, for example, with water, liquid fertilisers, micronutrients, biological organisms, oil or solvents.
  • the formulations can be prepared e.g. by mixing the active ingredient with the 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 formulated with other adjuvants, such as finely divided solids, mineral oils, oils of vegetable or animal origin, modified oils of vegetable or animal origin, organic solvents, water, surface-active substances or combinations thereof.
  • the active ingredients can also be contained in very fine microcapsules. Microcapsules contain the active ingredients in a porous carrier. This enables the active ingredients to be released into the environment in controlled amounts (e.g. slow-release). Microcapsules usually have a diameter of from 0.1 to 500 microns.
  • the active ingredients contain active ingredients in an amount of about from 25 to 95 % by weight of the capsule weight.
  • the active ingredients can be in the form of a monolithic solid, in the form of fine particles in solid or liquid dispersion or in the form of a suitable solution.
  • the encapsulating membranes can comprise, for example, natural or synthetic rubbers, cellulose, styrene/butadiene copolymers, polyacrylonitrile, polyacrylate, polyesters, polyamides, polyureas, polyurethane or chemically modified polymers and starch xanthates or other polymers that are known to the person skilled in the art.
  • microcapsules can be formed in which the active ingredient is contained in the form of finely divided particles in a solid matrix of base substance, but the microcapsules are not themselves encapsulated.
  • liquid carriers there may be used: water, toluene, xylene, petroleum ether, vegetable oils, acetone, methyl ethyl ketone, cyclohexanone, acid anhydrides, acetonitrile, acetophenone, amyl acetate, 2-butanone, butylene carbonate, chlorobenzene, cyclohexane, cyclohexanol, alkyl esters of acetic acid, diacetone alcohol, 1 ,2- dichloropropane, diethanolamine, p-diethylbenzene, diethylene glycol, diethylene glycol abietate, diethylene glycol butyl ether, diethylene glycol ethyl ether, diethylene glycol methyl ether, N,N- dimethylformamide, dimethyl sulfoxide, 1 ,4-dioxane, dipropylene
  • Suitable solid carriers are, for example, talc, titanium dioxide, pyrophyllite clay, silica, attapulgite clay, kieselguhr, limestone, calcium carbonate, bentonite, calcium montmorillonite, cottonseed husks, wheat flour, soybean flour, pumice, wood flour, ground walnut shells, lignin and similar substances.
  • surface-active substances can advantageously be used in both solid and liquid formulations, especially in those formulations which can be diluted with a carrier prior to use.
  • Surface-active substances may be anionic, cationic, non-ionic or polymeric and they can be used as emulsifiers, wetting agents or suspending agents or for other purposes.
  • Typical surface-active substances include, for example, salts of alkyl sulfates, such as
  • alkylarylsulfonates such as calcium dodecyl- benzenesulfonate
  • alkylphenol/alkylene oxide addition products such as nonylphenol ethoxylate
  • alcohol/alkylene oxide addition products such as tridecylalcohol 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 lauryltrimethylammonium 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-alkylphosphate esters; and also further substances described e.g. in McCutcheon's Detergents and Emulsifiers Annual, MC Publishing Corp., Ridgewood New Jersey (1981 ).
  • Further adjuvants that can be used in pesticidal formulations include crystallisation inhibitors, viscosity modifiers, suspending agents, dyes, anti-oxidants, foaming agents, light absorbers, mixing auxiliaries, antifoams, complexing agents, neutralising or pH-modifying substances and buffers, corrosion inhibitors, fragrances, wetting agents, take-up enhancers, micronutrients, plasticisers, glidants, lubricants, dispersants, thickeners, antifreezes,
  • microbicides and liquid and solid fertilisers.
  • the formulations according to the invention can include an additive comprising an oil of vegetable or animal origin, a mineral oil, alkyl esters of such oils or mixtures of such oils and oil - - derivatives.
  • the amount of oil additive in the composition according to the invention is generally from 0.01 to 10 %, based on the mixture to be applied.
  • the oil additive can be added to a spray tank in the desired concentration after a spray mixture has been prepared.
  • Preferred oil additives comprise mineral oils or an oil of vegetable origin, for example rapeseed oil, olive oil or sunflower oil, emulsified vegetable oil, alkyl esters of oils of vegetable origin, for example the methyl derivatives, or an oil of animal origin, such as fish oil or beef tallow.
  • Preferred oil additives comprise alkyl esters of C 8 -C 2 2 fatty acids, especially the methyl derivatives of d 2 - C-I8 fatty acids, for example the methyl esters of lauric acid, palmitic acid and oleic acid (methyl laurate, methyl palmitate and methyl oleate, respectively).
  • Many oil derivatives are known from the Compendium of Herbicide Adjuvants, 10 th Edition, Southern Illinois University, 2010.
  • the formulations generally comprise from 0.1 to 99 % by weight, especially from 0.1 to 95 % by weight, of the compound of formula (I) and from 1 to 99.9 % by weight of a formulation adjuvant which preferably includes from 0 to 25 % by weight of a surface-active substance.
  • a formulation adjuvant which preferably includes from 0 to 25 % by weight of a surface-active substance.
  • the rates of application vary within wide limits and depend on the nature of the soil, the method of application, the crop plant, the pest to be controlled, the prevailing climatic conditions, and other factors governed by the method of application, the time of application and the target crop.
  • a general guideline compounds may be applied at a rate of from 1 to 2000 l/ha, especially from 10 to 1000 l/ha.
  • Preferred formulations can have the following compositions (weight %):
  • Emulsifiable concentrates active ingredient: 1 to 95 %, preferably 60 to 90 %
  • liquid carrier 1 to 80 %, preferably 1 to 35 %
  • Dusts active ingredient: 0.1 to 10 %, preferably 0.1 to 5 %
  • solid carrier 99.9 to 90 %, preferably 99.9 to 99 %
  • Suspension concentrates active ingredient: 5 to 75 %, preferably 10 to 50 %
  • Wettable powders active ingredient: 0.5 to 90 %, preferably 1 to 80 % - - surface-active agent: 0.5 to 20 %, preferably 1 to 15 %
  • solid carrier 5 to 95 %, preferably 15 to 90 %
  • Granules active ingredient: 0.1 to 30 %, preferably 0.1 to 15 %
  • solid carrier 99.5 to 70 %, preferably 97 to 85 %
  • the combination is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable mill, affording wettable powders that can be diluted with water to give suspensions of the desired concentration.
  • the combination is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable mill, affording powders that can be used directly for seed treatment.
  • Emulsions of any required dilution which can be used in plant protection, can be obtained from this concentrate by dilution with water.
  • Ready-for-use dusts are obtained by mixing the combination with the carrier and grinding the mixture in a suitable mill. Such powders can also be used for dry dressings for seed.
  • the combination is mixed and ground with the adjuvants, and the mixture is moistened with water.
  • the mixture is extruded and then dried in a stream of air.
  • the finely ground combination is uniformly applied, in a mixer, to the kaolin moistened with polyethylene glycol.
  • Non-dusty coated granules are obtained in this manner.
  • nonylphenol polyethylene glycol ether (15 mol of ethylene oxide) 6 %
  • the finely ground combination is intimately mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water.
  • a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water.
  • living plants as well as plant propagation material can be treated and protected against infestation by microorganisms, by spraying, pouring or immersion.
  • the finely ground combination is intimately mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water.
  • a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water.
  • living plants as well as plant propagation material can be treated and protected against infestation by microorganisms, by spraying, pouring or immersion.
  • 28 parts of the combination are mixed with 2 parts of an aromatic solvent and 7 parts of toluene diisocyanate/polymethylene-polyphenylisocyanate-mixture (8: 1 ).
  • This mixture is emulsified in a mixture of 1.2 parts of polyvinylalcohol, 0.05 parts of a defoamer and 51 .6 parts of water until the desired particle size is achieved.
  • To this emulsion a mixture of 2.8 parts 1 ,6-diaminohexane in 5.3 parts of water is added. The mixture is agitated until the polymerization reaction is completed.
  • the obtained capsule suspension is stabilized by adding 0.25 parts of a thickener and 3 parts of a dispersing agent.
  • the capsule suspension formulation contains 28% of the active ingredients.
  • the medium capsule diameter is 8-15 microns.
  • the resulting formulation is applied to seeds as an aqueous suspension in an apparatus suitable for that purpose.
  • the invention also provides a method of controlling plants which comprises applying to the plants or to the locus thereof a herbicidally effective amount of a compound of formula (I) or a composition according to the invention. - -
  • the invention also provides a method of inhibiting plant growth which comprises applying to the plants or to the locus thereof a herbicidally effective amount of a compound of formula (I) or a composition according to the invention.
  • the invention also provides a method of controlling weeds in crops of useful plants, comprising applying to said weeds or to the locus of said weeds, or to said useful plants or to the locus of said useful plants, a compound of formula (I) or a composition according to the invention.
  • the invention also provides a method of selectively controlling grasses and/or weeds in crops of useful plants which comprises applying to the useful plants or locus thereof or to the area of cultivation a herbicidally effective amount of a compound of formula (I) or a composition according to the invention.
  • herbicide as used herein means a compound that controls or modifies the growth of plants.
  • herbicidally effective amount means the quantity of such a compound or combination of such compounds that is capable of producing a controlling or modifying effect on the growth of plants. Controlling or modifying effects include all deviation from natural development, for example killing, retardation, leaf burn, albinism, dwarfing and the like.
  • locus means fields in or on which plants are growing, or where seeds of cultivated plants are sown, or where seed will be placed into the soil. It includes soil, seeds, and seedlings, as well as established vegetation.
  • plants refers to all physical parts of a plant, including seeds, seedlings, saplings, roots, tubers, stems, stalks, foliage, and fruits.
  • plant propagation material denotes all generative parts of a plant, for example seeds or vegetative parts of plants such as cuttings and tubers. It includes seeds in the strict sense, as well as roots, fruits, tubers, bulbs, rhizomes, and parts of plants.
  • Crops of useful plants in which the compounds and composition according to the invention can be used include perennial and annual crops, such as berry plants for example blackberries, blueberries, cranberries, raspberries and strawberries; cereals for example barley, maize (corn), millet, oats, rice, rye, sorghum triticale and wheat; fibre plants for example cotton, flax, hemp, jute and sisal; field crops for example sugar and fodder beet, coffee, hops, mustard, oilseed rape (canola), poppy, sugar cane, sunflower, tea and tobacco; fruit trees for example apple, apricot, avocado, banana, cherry, citrus, nectarine, peach, pear and plum; grasses for example Bermuda grass, bluegrass, bentgrass, centipede grass, fescue, ryegrass, St.
  • perennial and annual crops such as berry plants for example blackberries, blueberries, cranberries, raspberries and strawberries
  • cereals for example barley, maize (corn),
  • Augustine grass and Zoysia grass herbs such as basil, borage, chives, coriander, lavender, lovage, mint, oregano, parsley, rosemary, sage and thyme; legumes for example beans, lentils, peas and soya beans; nuts for example almond, cashew, ground nut, hazelnut, peanut, pecan, pistachio and walnut; palms for example oil palm; ornamentals for example flowers, shrubs and trees; other trees, for example cacao, coconut, olive and rubber; vegetables for example asparagus, aubergine, broccoli, - - cabbage, carrot, cucumber, garlic, lettuce, marrow, melon, okra, onion, pepper, potato, pumpkin, rhubarb, spinach and tomato; and vines for example grapes.
  • herbs such as basil, borage, chives, coriander, lavender, lovage, mint, oregano, parsley, rosemary, sage and thyme
  • legumes for example beans, lentils, peas and
  • Crops are to be understood as being those which are naturally occurring, obtained by conventional methods of breeding, or obtained by genetic engineering. They include crops which contain so-called output traits (e.g. improved storage stability, higher nutritional value and improved flavour).
  • output traits e.g. improved storage stability, higher nutritional value and improved flavour.
  • Crops are to be understood as also including those crops which have been rendered tolerant to herbicides like bromoxynil or classes of herbicides such as ALS-, EPSPS-, GS-, HPPD- and PPO-inhibitors.
  • herbicides like bromoxynil or classes of herbicides such as ALS-, EPSPS-, GS-, HPPD- and PPO-inhibitors.
  • imidazolinones e.g. imazamox
  • Clearfield® summer canola examples of crops that have been rendered tolerant to herbicides by genetic engineering methods include e.g. glyphosate- and glufosinate-resistant maize varieties commercially available under the trade names Round upReady®, Herculex I® and LibertyLink®.
  • Crops are also to be understood as being those which naturally are or have been rendered resistant to harmful insects. This includes plants transformed by the use of recombinant DNA techniques, for example, to be capable of synthesising one or more selectively acting toxins, such as are known, for example, from toxin-producing bacteria. Examples of toxins which can be expressed include ⁇ -endotoxins, vegetative insecticidal proteins (Vip), insecticidal proteins of bacteria colonising nematodes, and toxins produced by scorpions, arachnids, wasps and fungi. An example of a crop that has been modified to express the Bacillus thuringiensis toxin is the Bt maize KnockOut® (Syngenta Seeds).
  • VipCot® Surgera Seeds
  • Crops or seed material thereof can also be resistant to multiple types of pests (so-called stacked transgenic events when created by genetic modification).
  • a plant can have the ability to express an insecticidal protein while at the same time being herbicide tolerant, for example Herculex I® (Dow AgroSciences, Pioneer Hi-Bred International).
  • Compounds and compositions of the invention can typically be used to control a wide variety of monocotyledonous and dicotyledonous weed species.
  • monocotyledonous species that can typically be controlled include Alopecurus myosuroides, Avena fatua, Brachiaria plantaginea, Bromus tectorum, Cyperus esculentus, Digitaria sanguinalis, Echinochloa crus-galli, Lolium perenne, Lolium multiflorum, Panicum miliaceum, Poa annua, Setaria viridis, Setaria faberi and Sorghum bicolor.
  • dicotyledonous species that can be controlled include Abutilon theophrasti, Amaranthus retroflexus, Bidens pilosa, Chenopodium album, Euphorbia heterophylla, Galium aparine, Ipomoea hederacea, Kochia scoparia, Polygonum convolvulus, Sida spinosa, Sinapis arvensis, Solanum nigrum, Stellaria media, Veronica persica and Xanthium strumarium. - -
  • the compounds of the invention can be applied before or after planting of the crops, before weeds emerge (pre-emergence application) or after weeds emerge (post-emergence
  • Any method of application to weeds/crop of useful plant, or locus thereof, which is routinely used in agriculture may be used, for example application by spray or broadcast method typically after suitable dilution of a compound of formula (I) (whether said compound is formulated and/or in combination with one or more further active ingredients and/or safeners, as described herein).
  • the compounds of formula (I) according to the invention can also be used in combination with other active ingredients, e.g. other herbicides, and/or insecticides, and/or acaricides, and/or nematocides, and/or molluscicides, and/or fungicides, and/or plant growth regulators.
  • other active ingredients e.g. other herbicides, and/or insecticides, and/or acaricides, and/or nematocides, and/or molluscicides, and/or fungicides, and/or plant growth regulators.
  • mixtures of invention also include mixtures of two or more different compounds of formula (I).
  • the present invention also relates to a composition of the invention which comprises at least one further herbicide in addition to the compound of formula (I).
  • Compounds of formula I can be used in combination with one or more other herbicides to provide various herbicidal mixtures.
  • Specific examples of such mixtures include (wherein ⁇ " represents a compound of formula I):- 1 + acetochlor, I + acifluorfen, I + acifluorfen-sodium, I + aclonifen, I + acrolein, I + alachlor, I + alloxydim, I + allyl alcohol, I + ametryn, I +
  • amicarbazone I + amidosulfuron, I + aminocyclopyrachlor, I + aminopyralid, I + amitrole, I + ammonium sulfamate, I + anilofos, I + asulam, I + atrazine, I + aviglycine, I + azafenidin, I + azimsulfuron, I + BCPC, I + beflubutamid, I + benazolin, I + bencarbazone, I + benfluralin, I + benfuresate, I + bensulfuron, I + bensulfuron-methyl, I + bensulide, I + bentazone, I + benzfendizone, I + benzobicyclon, I + benzofenap, I + bicyclopyrone, I + bifenox, I + bilanafos, I + bispyribac, I + bispyribac-sodium, I + borax, I + bromacil, I + bro
  • bromophenoxim I + bromoxynil, I + butachlor, I + butafenacil, I + butamifos, I + butralin, I + butroxydim, I + butylate, I + cacodylic acid, I + calcium chlorate, I + cafenstrole, l + carbetamide, I + carfentrazone, I + carfentrazone-ethyl, I + CDEA, I + CEPC, I + chlorflurenol, I + chlorflurenol-methyl, I + chloridazon, I + chlorimuron, I + chlorimuron-ethyl, I + chloroacetic acid, I + chlorotoluron, I + chlorpropham, I + chlorsulfuron, I + chlorthal, I + chlorthal-dimethyl, I + cinidon-ethyl, I + cinmethylin, I + cinosulfuron, I + cisanilide, I + clethodim, I
  • I + iodomethane I + iodosulfuron, I + iodosulfuron-methyl-sodium, I + ioxynil, I + ipfencarbazone, I + isoproturon, I + isouron, I + isoxaben, I + isoxachlortole, I + isoxaflutole, I + isoxapyrifop, I + karbutilate, I + lactofen, I + lenacil, I + linuron, I + MAA, I + MAMA, I + MCPA, I + MCPA- thioethyl, I + MCPB, I + mecoprop, I + mecoprop-P, I + mefenacet, I + mefluidide, I + mesosulfuron, I + mesosulfuron-methyl, I + mesotrione, I + metam, I + metamifop, I + metamitron,
  • Mixtures of a compound of the formula (I) with a triazine e.g. I + ametryn, I + atrazine, I + cyanazine, I + dimethametryn, I + metribuzin, I + prometon, I + prometryn, I + propazine, I + simazine, I + simetryn, I + terbumeton, I + terbuthylazine, I + terbutryn, I + trietazine).
  • a triazine e.g. I + ametryn, I + atrazine, I + cyanazine, I + dimethametryn, I + metribuzin, I + prometon, I + prometryn, I + propazine, I + simazine, I + simetryn, I + terbumeton, I + terbuthylazine, I + terbutryn, I + trietazine.
  • HPPD inhibitor e.g. I + isoxaflutole, I + mesotrione, I + pyrasulfotole, I + sulcotrione, I + tembotrione, I + topramezone, I + bicyclopyrone, I + benzobicyclon or I + 2-[[8-chloro-3,4-dihydro-4-(4-methoxyphenyl)-3-oxo-2- quinoxalinyl]carbonyl]1 ,3-cyclohexanedione (CAS RN 1342891-70-6)).
  • HPPD inhibitor e.g. I + isoxaflutole, I + mesotrione, I + pyrasulfotole, I + sulcotrione, I + tembotrione, I + topramezone, I + bicyclopyrone, I + benzobicyclon or I + 2-[[8-chloro-3,4-dihydro-4-(4-meth
  • Mixtures of a compound of formula (I) with an auxin e.g. I + dicamba, I + 2,4-D, I + 2,4- DB, I + MCPA, I + fluroxypyr, I + picloram, I + triclopyr, I + quinclorac, I + clopyralid, I + aminopyralid, I + aminocyclopyrachlor, I + halauxifen, I + halauxifen-methyl).
  • an auxin e.g. I + dicamba, I + 2,4-D, I + 2,4- DB, I + MCPA, I + fluroxypyr, I + picloram, I + triclopyr, I + quinclorac, I + clopyralid, I + aminopyralid, I + aminocyclopyrachlor, I + halauxifen, I + halauxifen-methyl).
  • VLCFA inhibitor e.g.
  • a compound of formula (I) with an ALS inhibitor e.g. I + chlorsulfuron, I + cinosulfuron, I + cloransulam, I + ethametsulfuron, I + flazasulfuron, I + foramsulfuron, I + flumetsulam, I + imazamethabenz, I + imazamox, I + imazapic, I + imazapyr, I + imazethapyr, I + iodosulfuron, I + iofensulfuron, I + metsulfuron, I + nicosulfuron, I + oxasulfuron, I + primisulfuron, - -
  • an ALS inhibitor e.g. I + chlorsulfuron, I + cinosulfuron, I + cloransulam, I + ethametsulfuron, I + flazasulfuron, I + foramsulfuron, I + flumet
  • a PPO inhibitor e.g. I + fomesafen, I + flumioxazin, I + sulfentrazone, I + acifluorfen-sodium, I + lactofen, I + oxyfluorfen, I + oxadiazon, I + butafenacil, I + carfentrazone-ethyl, 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).
  • a PPO inhibitor e.g. I + fomesafen, I + flumioxazin, I + sulfentrazone, I + acifluorfen-sodium, I + lactofen, I + oxyfluorfen, I + oxadiazon, I + but
  • I + glyphosate I + glufosinate, I + paraquat, I + diquat, I + pendimethalin, I + trifluralin, I + metamitron, I + clomazone, I + prodiamine, I + saflufenacil, I + prosulfocarb, I + diflufenican, I + isoxaben, I + beflubutamide, I + flurtamone, I + benfluralin, I + chlorotoluron, I + linuron, I + isoproturon, I + triallate, I + hexazinone, I + diuron, I + propanil, I + indaziflam.
  • the following mixtures are preferred: I + ametryn, I + atrazine, I + cyanazine, I + dimethametryn, I + metribuzin, I + prometon, I + prometryn, I + propazine, I + simazine, I + simetryn, I + terbumeton, I + terbuthylazine, I + terbutryn, I + trietazine, I + isoxaflutole, I + mesotrione, I + pyrasulfotole, I + sulcotrione, I + tembotrione, I + topramezone, I + bicyclopyrone, I + benzobicyclon, I + 2-[[8-chloro-3,4-dihydro-4-(4-methoxyphenyl)-3-oxo-2- quinoxalinyl]carbonyl]1 ,3-cyclohexanedione (CAS RN 1342891-70-6
  • the present invention also includes three-way mixtures of a compound of formula (1 ), a herbicide as defined above and a further herbicide.
  • the present invention also includes four-way mixtures of a compound of formula (I), a herbicide as defined above and two further herbicides.
  • the following four-way mixture is preferred: I + atrazine + mesotrione + S-metolachlor.
  • the mixing partners of the compound of formula (I) may also be in the form of esters or salts, as mentioned e.g. in The Pesticide Manual, 14th Edition (BCPC), 2006.
  • BCPC The Pesticide Manual, 14th Edition
  • the reference to acifluorfen-sodium also applies to acifluorfen
  • the reference to dimethenamid also applies to dimethenamid-P
  • the reference to glufosinate-ammonium also applies to glufosinate
  • the reference to bensulfuron-methyl also applies to bensulfuron
  • the reference to cloransulam- methyl also applies to cloransulam
  • the reference to flamprop-M also applies to flamprop
  • the reference to pyrithiobac-sodium also applies to pyrithiobac, etc.
  • the mixing ratio of the compound of formula (I) to the mixing partner is preferably from 1 : 100 to 1000: 1.
  • mixtures can advantageously be used in the above-mentioned formulations (in which case "active ingredient” relates to the respective mixture of compound of formula (I) with the mixing partner).
  • Compounds of formula (I) may also be combined with herbicide safeners.
  • ⁇ " represents a compound of formula (I)
  • I + AD-67 I + benoxacor, I + cloquintocet-mexyl, I + cyomerinil, I + dichlormid, I + dicyclonone, I + cyprosulfamide, I + diethorate, I + DKA-24, I + dymron, I + fenclorazole ethyl, I + fenclorim, I + HEXIM, I + flurazole, I + fluxofenim, I + furilazole, I + isoxadifen, I + isoxadifen ethyl, I + MCPA, I + mecoprop, I + mefenpyr, I + mefenpyr ethyl, I + mefenpyr diethyl, I + mephenate, I + MG-191 , I + NA (naphthalic anhydride),
  • [(methylaminocarbonyl)amino]benzenesulfonamide and the like are mentioned. These components can be used alone or by mixing 2 or more types, and the ratio when they are mixed can also be freely selected. In particular, the following compound/safener combinations are preferred: I + cloquintocet- mexyl, I + cyprosulfamide, I + N-(2-methoxybenzoyl)-4-
  • the safeners of the compound of formula (I) may also be in the form of esters or salts, as mentioned e.g. in The Pesticide Manual, 14th Edition (BCPC), 2006.
  • BCPC The Pesticide Manual, 14th Edition
  • the reference to cloquintocet-mexyl also applies to cloquintocet and to a lithium, sodium, potassium, calcium, magnesium, aluminium, iron, ammonium, quaternary ammonium, sulfonium or phosphonium salt thereof as disclosed in WO02/34048 and the reference to fenchlorazole-ethyl also applies to fenchlorazole, etc.
  • the mixing ratio of compound of formula (I) to safener is from 100: 1 to 1 :10, especially from 20: 1 to 1 : 1.
  • the mixtures can advantageously be used in the above-mentioned formulations (in which case "active ingredient” relates to the respective mixture of compound of formula (I) and any further active ingredient, in particular a further herbicide, with the safener).
  • active ingredient relates to the respective mixture of compound of formula (I) and any further active ingredient, in particular a further herbicide, with the safener.
  • the safener and a compound of formula (I) and one or more additional herbicide(s), if any are applied simultaneously.
  • the safener, a compound of formula (I) and one or more additional herbicide(s), if any might be applied to the locus pre-emergence or might be applied to the crop post-emergence.
  • the safener and a compound of formula (I) and one or more additional herbicide(s), if any are applied sequentially.
  • the safener might be applied before sowing the seeds as a seed treatment and a compound of formula (I) and one or more additional herbicides, if any, might be applied to the locus pre-
  • dichloromethane (6 ml) maintaining the temperature below -70 °C. The mixture was stirred for 30 minutes, allowed to warm to room temperature and stirred for 2 hours. Aqueous sodium bicarbonate solution was added until the mixture reached pH 7 and the mixture extracted with dichloromethane (3 x 30 ml). The combined organic extracts were washed with water, dried over sodium sulfate and concentrated under reduced pressure to provide 10-hydroxy-8- azaspiro[4.5]decan-9-one (130 mg, 97 %), which was used without further purification.
  • Dess-Martin periodinane (0.39 g, 0.92 mmol) was added to a stirred solution of 10-hydroxy-8- azaspiro[4.5]decan-9-one (130 mg, 0.76 mmol) in dichloromethane (2.6 ml) under nitrogen and the resulting mixture stirred for 2 hours at room temperature.
  • Dichloromethane 50 ml was added, followed by 2% aqueous sodium thiosulfate (5 ml) and saturated aqueous sodium bicarbonate (15 ml). The organic layer was separated, dried over sodium sulfate and concentrated under reduced pressure to provide 8-azaspiro[4.5]decane-9, 10-dione (125 mg, 97 %), which was used without further purification.
  • Step 1.8 Synthesis of 1 ,1 , 1-trifluoro-A/- ⁇ 2-[(10-methoxyimino-9-oxo-8-azaspiro[4.5ldecan-8- vDmethyllphenvDmethanesulfonamide
  • Step 1 9 Synthesis of ⁇ /- ⁇ 2-[(9 , 10-dioxo-8-azaspiro[4.5ldecan-8-yl)methvnphenyl)-1 , 1 , 1-trifluoro- methanesulfonamide (Compound 13-38)
  • Step 2.2 Synthesis of 1 ,1 , 1-trifluoro-A/- ⁇ 2-[(9-hydroxy-8-oxo-7-azaspiro[3.5lnonan-7- vDmethvUphenvDmethanesulfonaiTiide
  • Dess-Martin periodinane (2.4 g, 5.6 mmol) was added to a stirred solution of 1 , 1 , 1 -trifluoro- V- ⁇ 2- [(9-hydroxy-8-oxo-7-azaspiro[3.5]nonan-7-yl)methyl]phenyl ⁇ methanesulfonamide (1 .7 g, 4.3 mmol) in dichloromethane (34 ml) under nitrogen and the resulting mixture stirred for 9 hours at room temperature.
  • Dichloromethane 150 ml was added, followed by 2% aqueous sodium thiosulfate (40 ml) and saturated aqueous sodium bicarbonate (50 ml).
  • n-Butyl lithium (2M in cyclohexane; 15 ml, 30 mmol) was added to a solution of piperidin-2-one (1.0 g, 10.1 mmol) in tetrahydrofuran (15 ml) at 0 °C and the resulting mixture stirred for 60 minutes, then cooled to -78 °C and a solution of cyclopentane carboxaldehyde (1.43 g, 12.1 mmol) in tetrahydrofuran (5 ml) added.
  • the mixture was warmed to room temperature and stirred for 5 hours, then saturated aqueous ammonium chloride added and the mixture extracted with ethyl acetate (3 x 100 ml).
  • Potassium carbonate (65 mg, 0.45 mmol) was added to a solution of A/- ⁇ 2-[(3-benzylidene-4- methyl-2-oxo-1-piperidyl)methyl]phenyl ⁇ -1 , 1 ,1-trifluoro-methanesulfonamide (100 mg, 0.22 mmol) in acetone (1 ml) and the mixture stirred at room temperature for 20 minutes.
  • Ethyl chloroformate (98 mg, 0.91 mmol) was added and the mixture stirred for 2 hours and then concentrated under reduced pressure. Water was added and the resulting mixture extracted with ethyl acetate (3 x 40 ml).
  • Characteristic data is melting point (°C) and/or 1 H nmr data (400 MHz, CDCI 3 unless otherwise stated) ⁇ ⁇ ppm.
  • ZEAMX Zea mays
  • SETFA Setaria faberi
  • EHCG Echinochloa crus-galli
  • LLOLPE Lolium perenne
  • Alopecurus myosuroides Alopecurus myosuroides
  • AMARE Amaranthus retroflexus
  • ABUTH Abutilon theophrasti
  • aqueous spray solution derived from the formulation of the technical active ingredient in acetone / water (50:50) solution containing 0.5% Tween 20 (polyoxyethylene sorbitan monolaurate, CAS RN 9005-64-5) to give a final dose of 250 or 1000 g/ha of test compound.
  • ZEAMX Zea mays
  • SETFA Setaria faberi
  • EHCG Echinochloa crus-galli
  • LLOLPE Lolium perenne
  • Alopecurus myosuroides Alopecurus myosuroides
  • AMARE Amaranthus retroflexus
  • ABUTH Abutilon theophrasti

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Abstract

The invention relates to haloalkylsulphonamide derivatives of the formula (I) wherein A, W, X, m, n, p, R, R1, R2, R5, R6, R7 and R8 are as defined in the specification. Furthermore, the present invention relates to processes for making compounds of formula (I), to herbicidal compositions comprising these compounds and to methods of using these compounds to control or inhibit plant growth.

Description

HERBICIDAL COMPOUNDS
The present invention relates to certain haloalkylsulphonamide derivatives, to processes for their preparation, herbicidal compositions comprising them, and their use in controlling plants or inhibiting plant growth.
Herbicidal haloalkylsulphonamide derivatives of the formula (i)
Figure imgf000003_0001
are taught in WO 2010/026989. Similar compounds are taught in WO 2010/1 19906.
However, new haloalkylsulphonamide derivatives with an improved efficacy and/or spectrum of activity and/or improved crop tolerance with respect to the known derivatives have now been identified.
Accordingly, in a first aspect, the invention provides compounds of the formula (I)
Figure imgf000003_0002
(I)
wherein
A is selected from CH=CH, CR3=CH, CH=CR3, CR3=CR3 and S;
W is selected from oxygen and sulphur;
X is selected from oxygen and CR9R10; m is 0, 1 or 2; n is 1 , 2, 3 or 4; - - p is 0, 1 , 2 or 3; with the proviso that 2 < n + p < 4; R is Ci-6haloalkyl;
R is selected from H, C1_4alkyl, C3.5alkenyl, propargyl,
Figure imgf000004_0001
Ci.4alkoxyCi_
2alkoxyCi-2alkyl,
Figure imgf000004_0002
cyanoCi_2alkyl, Ci_
4alkylcarbonylCi-2alkyl,
Figure imgf000004_0003
arylCi_2alkyl optionally substituted by 1-3 groups R20, heteroarylCi_2alkyl optionally substituted by 1-3 groups R20, arylthioCi_2alkyl optionally substituted by 1-3 groups R20, arylCi_2alkoxyCi_2alkyl optionally substituted by 1-3 groups R20, arylCi_2alkylthioCi_2alkyl optionally substituted by 1-3 groups R20, arylcarbonylCi_2alkyl optionally substituted by 1-3 groups R20, Ci.4alkylcarbonyloxyCi_2alkyl, arylcarbonyloxyCi_2alkyl optionally substituted by 1-3 groups R20, Ci_4alkoxycarbonyloxyCi_2alkyl, aryloxycarbonyloxyCi-2alkyl optionally substituted by 1-3 groups R20,Ci_8alkylcarbonyl, C2.
5alkenylcarbonyl, Ci_4haloalkylcarbonyl, Ci_4alkoxyCi_2alkylcarbonyl, C3.6cycloalkylcarbonyl, Ci_ 4alkoxycarbonylCi_2alkylcarbonyl, arylcarbonyl optionally substituted by 1-3 groups R20, aryloxyCi-2alkylcarbonyl optionally substituted by 1-3 groups R20, Ci_i0alkoxycarbonyl; Ci_ 4haloalkoxycarbonyl, C3.5alkenyloxycarbonyl, propargyloxycarbonyl, Ci_4alkoxyCi_
2alkoxycarbonyl, Ci_4alkylthiocarbonyl, aryloxycarbonyl optionally substituted by 1-3 groups R20, arylCi_2alkoxycarbonyl optionally substituted by 1-3 groups R20, aminocarbonyl, Ci_
4alkylaminocarbonyl, di(Ci_4alkyl)aminocarbonyl, Ci_6alkylsulphonyl, Ci_6haloalkylsulphonyl and arylsulphonyl optionally substituted by 1-3 groups R20, and each R20 is, independently, selected from halogen, Ci_4alkyl, Ci_4haloalkyl, Ci_4alkoxy, Ci_4haloalkoxy, Ci_2alkoxyCi_2alkoxy, hydroxy, phenyl and phenoxy; each R2 is, independently, selected from halogen, nitrile, Ci_4alkyl, Ci_4haloalkyl, C3.6cycloalkyl, C2.4alkenyl, C2.4alkynyl, Ci_4alkoxy, Ci_4haloalkoxy, Ci_2alkoxyCi_2alkoxy, hydroxy, Ci_
4alkylcarbonyl, Ci_4alkylsulphonyl and phenyl, or two R2 groups together form -OCH20- or - OCH2CH20-; each R3 is, independently, selected from halogen, nitrile, Ci_4alkyl, Ci_4haloalkyl, C3.6cycloalkyl, C2.4alkenyl, C2.4alkynyl, Ci_4alkoxy, Ci_4haloalkoxy, Ci_2alkoxyCi_2alkoxy, hydroxy, d.
4alkylcarbonyl, Ci_4alkylsulphonyl and phenyl, or two R3 groups together form -OCH20- or - OCH2CH20-; each R5 and R6 are, independently, selected from H, halogen, cyano, hydroxy, Ci_4alkyl, d. 4haloalkyl, C3.6cycloalkyl, Ci_2alkoxyCi_2alkyl, C2.5alkenyl, C2.5alkynyl, Ci_4alkoxy, Ci_4alkylthio, Ci_ 4alkoxycarbonyl, aryl optionally substituted by 1-3 groups R24, aryloxy optionally substituted by 1- 3 groups R24 and arylthio optionally substituted by 1-3 groups R24 or R5 and R6 on the same carbon atom together form a C2.5alkylene chain optionally containing an oxygen atom, or R5 and R6 on different carbon atoms together form a Ci_4alkylene chain, or R5 and R 0 together form a - -
C2-4alkylene chain and each R is, independently, selected from halogen, cyano, C1_4alkyl, Ci_ 4haloalkyl, Ci_4alkoxy, Ci_4haloalkoxy,
Figure imgf000005_0001
hydroxy, phenyl and phenoxy; each R7 and R8 are, independently, selected from H, d-5alkyl, Ci_4haloalkyl, C3.6cycloalkyl optionally substituted with 1-3 groups selected from halogen, Ci_4alkyl and phenyl, Ci_4alkoxyCi_ 4alkyl, Ci.4alkoxycarbonylaminoCi_4alkyl, Ci.4alkylcarbonyloxyCi.2alkyl, arylCi_2alkyl optionally substituted by 1-3 groups R2 , aryloxyCi_2alkyl optionally substituted by 1-3 groups R2 , arylCi. 2alkoxyCi.2alkyl optionally substituted by 1-3 groups R2 ,C2.4alkenyl, hydroxyl, Ci_4alkoxy, Ci_ 4alkylthio, Ci_4alkylcarbonyloxy,aryl optionally substituted by 1-3 groups R2 , aryloxy optionally substituted by 1-3 groups R2 , arylthio optionally substituted by 1-3 groups R2 and heteroaryl optionally substituted by 1-3 groups R2 , or R7 and R8 on the same carbon atom together form a C2.6alkylene chain optionally containing an oxygen or sulphur atom and optionally substituted by 1-3 groups selected from halogen, Ci_2alkyl and an oxo group, or R7 and R8 on different carbon atoms together form a Ci_4alkylene chain, or R8 and R 0 together form a C2.4alkylene chain and each R2 is, independently, selected from halogen, cyano, Ci_4alkyl, Ci_4haloalkyl, Ci_4alkoxy, d. 4haloalkoxy, Ci_2alkoxyCi_2alkoxy, hydroxy, phenyl and phenoxy or two R2 groups together form -OCH20- or -OCH2CH20-;
R9 is selected from H, Ci_6alkyl, Ci_6haloalkyl, C3.6cycloalkylCi.2alkyl, C3.6cycloalkyl, Ci_4alkoxy, Ci_4alkylthio, Ci_4alkylamino, aryl optionally substituted by 1-3 groups R22, arylCi_2alkyl optionally substituted by 1-3 groups R22 and heteroaryl optionally substituted by 1-3 groups R22 and each R22 is, independently, selected from halogen, nitro, cyano, Ci_4alkyl, Ci_4haloalkyl, Ci_4alkoxy, d. 4haloalkoxy, Ci_2alkoxyCi_2alkoxy, hydroxy, Ci_4alkylthio, Ci_4haloalkylthio, Ci_4alkylsulphonyl, Ci_ 4alkoxycarbonyl, phenyl and phenoxy;
R 0 is selected from H, Ci_6alkyl, Ci_4alkylcarbonyl, Ci_4alkoxycarbonyl, Ci_4alkoxy, Ci_4alkylthio, Ci_4alkylamino and Ci_4alkylsulphonyl, or R 0 and R5 or R8 together form a C2.4alkylene chain; or an N-oxide or salt form thereof.
In particularly preferred embodiments of the invention, the preferred groups for A, W, X, m, n, p, R1, R2, R3, R5, R6, R7, R8, R9, R 0, R20, R21, R22 and R24 in any combination thereof, are as set out below:
Preferably, A is selected from CH=CH and CR3=CH. Most preferably, A is CH=CH.
Preferably, W is oxygen.
Preferably, m is 0 or 1.
Most preferably, m is 0.
Preferably, n is 2, 3 or 4. - -
Preferably, p is 0.
Preferably, R is Ci_2haloalkyl. More preferably, R is trifluoromethyl.
Preferably, R is selected from H,
Figure imgf000006_0001
Ci-4alkoxyCi-2alkoxyCi-2alkyl, d- 4haloalkoxyCi.2alkyl, arylCi_2alkyl optionally substituted by 1-3 groups R20, arylCi-2alkoxyCi-2alkyl optionally substituted by 1-3 groups R20, rylcarbonyloxyCi_2alkyl optionally substituted by 1-3 groups R20,
Figure imgf000006_0002
Ci_8alkylcarbonyl, d- 4haloalkylcarbonyl,
Figure imgf000006_0003
Ci_i0alkoxycarbonyl; Ci_4haloalkoxycarbonyl, d- 4alkoxyCi.2alkoxycarbonyl, aryloxycarbonyl optionally substituted by 1-3 groups R20, arylCi. 2alkoxycarbonyl optionally substituted by 1-3 groups R20, Ci_6alkylsulphonyl and Ci_
6haloalkylsulphonyl.
More preferably, R is selected from H, Ci_5alkylcarbonyl, Ci_4haloalkylcarbonyl, d- 5alkoxycarbonyl, Ci.4haloalkoxycarbonyl and Ci.4haloalkylsulphonyl.
Most preferably, R is selected from H, d.5alkylcarbonyl and d.5alkoxycarbonyl. Preferably, R2 is selected from halogen, C1_4alkyl, C-|.4haloalkyl, Ci.4alkoxy and d-
4alkylsulphonyl.
Most preferably, R2 is selected from halogen and methyl.
Preferably, R3 is selected from halogen, C1_4alkyl, C-|.4haloalkyl, d_4alkoxy and d- 4alkylsulphonyl. Most preferably, R3 is selected from halogen and methyl.
Preferably, R5 and R6 are, independently, selected from H, halogen, C1_4alkyl, d_ 4haloalkyl, Ci.4alkoxy, Ci.4alkylthio, aryl optionally substituted by 1-3 groups R24, aryloxy optionally substituted by 1-3 groups R24 and arylthio optionally substituted by 1-3 groups R24.
More preferably, R5 and R6 are, independently, selected from H, halogen, C1_4alkyl, d_ 4haloalkyl, d_4alkoxy, Ci_4alkylthio and aryl optionally substituted by 1-2 groups R24.
Most preferably, R5 and R6 are, independently, selected from H, halogen, d.3alkyl, d- 3alkoxy and d.3alkylthio.
Preferably, R7 and R8 are, independently, selected from H, d.5alkyl, d_4haloalkyl, d- 6cycloalkyl, Ci.4alkoxyCi.4alkyl, aryld.2alkyl optionally substituted by 1-3 groups R2 , d-4alkenyl, Ci_4alkoxy, Ci.4alkylthio, aryl optionally substituted by 1-3 groups R2 , aryloxy optionally substituted by 1-3 groups R2 , arylthio optionally substituted by 1-3 groups R2 and heteroaryl optionally substituted by 1-3 groups R2 , or R7 and R8 on the same carbon atom together form a - -
C2-5alkylene chain optionally containing an oxygen atom, or R7 and R8 on adjacent carbon atoms together form a d-4alkylene chain.
More preferably, R7 and R8 are, independently, selected from H, C1_4alkyl, C-|.3haloalkyl, cyclopropyl, Ci.2alkoxyCi.2alkyl,Ci.3alkoxy, Ci_3alkylthio, aryl optionally substituted by 1-3 groups R2 , aryloxy optionally substituted by 1-3 groups R2 , arylthio optionally substituted by 1-3 groups R2 and heteroaryl optionally substituted by 1-3 groups R2 , or R7 and R8 on the same carbon atom together form a C3.5alkylene chain optionally containing an oxygen atom, or R7 and R8 on adjacent carbon atoms together form a Ci_4alkylene chain.
Most preferably, R7 and R8 are, independently, selected from H, Ci_3alkyl, trifluoromethyl, cyclopropyl, methoxymethyl, Ci_3alkoxy and aryl optionally substituted by 1-2 groups R2 , or R7 and R8 together form a C3.5alkylene chain optionally containing an oxygen atom, or R7 and R8 on adjacent carbon atoms together form a CH2 group.
Preferably, R9 is selected from H, C1_4alkyl, C3.6cycloalkyl and aryl optionally substituted by 1-3 groups R22. More preferably, R9 is selected from H, Ci_2alkyl and aryl optionally substituted by 1-3 groups R22.
Preferably, R 0 is selected from H, C1_4alkyl, C-i_2alkoxy and Ci_2alkylthio. More preferably, R 0 is selected from H and C1_4alkyl.
Preferably, R20 is selected from halogen, d_4alkyl, C-|.4haloalkyl, Ci_4alkoxy and Ci_ 4haloalkoxy.
Preferably, R2 is selected from halogen, cyano, d_4alkyl, C-|.4haloalkyl, Ci_4alkoxy and Ci_ 4haloalkoxy.
Most preferably, R2 is selected from halogen, methyl and methoxy.
Preferably, R22 is selected from halogen, cyano, Ci_2alkyl, Ci_2haloalkyl, Ci_2alkoxy and d. 2haloalkoxy.
More preferably, R22 is selected from halogen, Ci_2alkyl, Ci_2haloalkyl, Ci_2alkoxy and Ci_ 2haloalkoxy.
Preferably, R24 is selected from halogen, cyano, d_4alkyl, C-|.4haloalkyl, Ci_4alkoxy and Ci_ 4haloalkoxy. More preferably, R24 is selected from halogen, methyl and methoxy.
Table 1 below provides 422 compounds, designated compounds 1-1 to 1-422 respectively, of formula (la), wherein R is H and A is CH=CH. - -
Figure imgf000008_0001
(la) TABLE 1
Figure imgf000008_0002
- -
Figure imgf000009_0001
- -
Figure imgf000010_0001
- -
Figure imgf000011_0001
- -
Figure imgf000012_0001
- -
Figure imgf000013_0001
- -
Figure imgf000014_0001
- -
Figure imgf000015_0001
422 compounds are described, designated compounds 2-1 to 2-422 respectively, of formula (la), wherein R is H, m is 0, A is CF=CH and the values of R7, R8, R7 , R8 and X are as defined in Table 1. 422 compounds are described, designated compounds 3-1 to 3-422 respectively, of formula (la), wherein R is H, A is S and the values of R7, R8, R7 , R8 and X are as defined in Table 1.
422 compounds are described, designated compounds 4-1 to 4-422 respectively, of formula (la), wherein R is C02Et, A is CH=CH and the values of R7, R8, R7', R8' and X are as defined in Table 1.
422 compounds are described, designated compounds 5-1 to 5-422 respectively, of formula (la), wherein R is C02Et, A is CF=CH and the values of R7, R8, R7 , R8 and X are as defined in Table 1.
422 compounds are described, designated compounds 6-1 to 6-422 respectively, of formula (la), wherein R is C02Et, A is S and the values of R7, R8, R7 , R8 and X are as defined in Table 1. - -
Table 2 below provides 52 compounds, designated compounds 7-1 to 7-52 respectively, of formula (lb), wherein R is H and A is CH=CH.
Figure imgf000016_0001
(lb)
TABLE 2
Figure imgf000016_0002
- -
Figure imgf000017_0002
52 compounds are described, designated compounds 8-1 to 8-52 respectively, of formula (lb), wherein R is H, A is CF=CH and the values of R5, R6, R7, R8 and X are as defined in Table 52 compounds are described, designated compounds 9-1 to 9-52 respectively, of formula
(lb), wherein R is H, A is S and the values of R5, R6, R7, R8 and X are as defined in Table 2.
52 compounds are described, designated compounds 10-1 to 10-52 respectively, of formula (lb), wherein R is C02Et, A is CH=CH and the values of R5, R6, R7, R8 and X are as defined in Table 2. 52 compounds are described, designated compounds 11-1 to 11-52 respectively, of formula (lb), wherein R is C02Et, A is CF=CH and the values of R5, R6, R7, R8 and X are as defined in Table 2.
52 compounds are described, designated compounds 12-1 to 12-52 respectively, of formula (lb), wherein R is C02Et, A is S and the values of R5, R6, R7, R8 and X are as defined in Table 2.
Table 3 below provides 662 compounds, designated compounds 13-1 to 13-662 respectively, of formula (lc), wherein R is H and A is CH=CH.
Figure imgf000017_0001
(Ic)
TABLE 3 - -
Figure imgf000018_0001
- -
Figure imgf000019_0001
- -
Figure imgf000020_0001
- -
Figure imgf000021_0001
- -
231 H H -(CH2)2- H H Ch Pent
232 H H -(CH2)3- H H Ch Pent
233 H H -(CH2)4- H H Ch Pent
234 H H -(CH2)5- H H Ch Pent
235 H -(CH2)4- H H H Ch Pent
236 H H H H Me H Ch Pent
237 H H H H Et H Ch Pent
238 H H H H 'Pr H Ch Pent
239 H H H H nPr H Ch Pent
240 H H H H cPr H Ch Pent
241 H H H H -CH2CH— CH2 H Ch Pent
242 H H H H CH2F H Ch Pent
243 H H H H CH2CI H Ch Pent
244 H H H H CH2OMe H Ch Pent
245 H H H H (CH2)2CI H Ch Pent
246 H H H H CF3 H Ch Pent
247 H H H H C02Et H Ch Pent
248 H H H H Ph H Ch Pent
249 H H H H 4-FPh H Ch Pent
250 H H H H Me Me Ch Pent
251 H H H H Me Et Ch Pent
252 H H H H CF3 Me Ch Pent
253 H H H H CF3 Et Ch Pent
254 H H H H cPr Me Ch Pent
255 H H H H Et Et Ch Pent
256 H H H H -(CH2)2- Ch Pent
257 H H H H -(CH2)3- Ch Pent
258 H H H H -(CH2)4- Ch Pent
259 H H H H -(CH2)5- Ch Pent
260 H H H H -(CH2)0(CH2)- Ch Pent
261 H H H H -(CH2)0(CH2)2- Ch Pent
262 H H H H -(CH2)20(CH2)2- Ch Pent
263 H H H -CH2- H Ch Pent
264 Me H H -CH2- 'Pr Ch Pent
265 H H H H H H CHcHex
266 Me H H H H H CHcHex
267 Et H H H H H CHcHex
268 H H Me H H H CHcHex
269 H H Et H H H CHcHex
270 H H 'Pr H H H CHcHex
271 H H CH2OMe H H H CHcHex
272 H H OMe H H H CHcHex
273 H H Me Me H H CHcHex
274 H H Et Me H H CHcHex
275 H H -(CH2)2- H H CHcHex
276 H H -(CH2)3- H H CHcHex
277 H H -(CH2)4- H H CHcHex
278 H H -(CH2)5- H H CHcHex
279 H -(CH2)4- H H H CHcHex
280 H H H H Me H CHcHex
281 H H H H Et H CHcHex
282 H H H H 'Pr H CHcHex
283 H H H H nPr H CHcHex
284 H H H H cPr H CHcHex
285 H H H H -CH2CH— CH2 H CHcHex
286 H H H H CH2F H CHcHex
287 H H H H CH2CI H CHcHex
288 H H H H CH2OMe H CHcHex - -
Figure imgf000023_0001
- -
Figure imgf000024_0001
- -
Figure imgf000025_0001
- -
Figure imgf000026_0001
- -
521 H H H H -(CH2)3- CH(2-thienyl)
522 H H H H -(CH2)4- CH(2-thienyl)
523 H H H H -(CH2)5- CH(2-thienyl)
524 H H H H -(CH2)0(CH2)- CH(2-thienyl)
525 H H H H -(CH2)0(CH2)2- CH(2-thienyl)
526 H H H H -(CH2)20(CH2)2- CH(2-thienyl)
527 H H H -CH2- H CH(2-thienyl)
528 Me H H -CH2- 'Pr CH(2-thienyl)
529 H H H H H H CH(3-furyl)
530 Me H H H H H CH(3-furyl)
531 Et H H H H H CH(3-furyl)
532 H H Me H H H CH(3-furyl)
533 H H Et H H H CH(3-furyl)
534 H H 'Pr H H H CH(3-furyl)
535 H H CH2OMe H H H CH(3-furyl)
536 H H OMe H H H CH(3-furyl)
537 H H Me Me H H CH(3-furyl)
538 H H Et Me H H CH(3-furyl)
539 H H -(CH2)2- H H CH(3-furyl)
540 H H -(CH2)3- H H CH(3-furyl)
541 H H -(CH2)4- H H CH(3-furyl)
542 H H -(CH2)5- H H CH(3-furyl)
543 H -(CH2)4- H H H CH(3-furyl)
544 H H H H Me H CH(3-furyl)
545 H H H H Et H CH(3-furyl)
546 H H H H 'Pr H CH(3-furyl)
547 H H H H nPr H CH(3-furyl)
548 H H H H cPr H CH(3-furyl)
549 H H H H -CH2CH— CH2 H CH(3-furyl)
550 H H H H CH2F H CH(3-furyl)
551 H H H H CH2CI H CH(3-furyl)
552 H H H H CH2OMe H CH(3-furyl)
553 H H H H (CH2)2CI H CH(3-furyl)
554 H H H H CF3 H CH(3-furyl)
555 H H H H C02Et H CH(3-furyl)
556 H H H H Ph H CH(3-furyl)
557 H H H H 4-FPh H CH(3-furyl)
558 H H H H Me Me CH(3-furyl)
559 H H H H Me Et CH(3-furyl)
560 H H H H CF3 Me CH(3-furyl)
561 H H H H CF3 Et CH(3-furyl)
562 H H H H cPr Me CH(3-furyl)
563 H H H H Et Et CH(3-furyl)
564 H H H H -(CH2)2- CH(3-furyl)
565 H H H H -(CH2)3- CH(3-furyl)
566 H H H H -(CH2)4- CH(3-furyl)
567 H H H H -(CH2)5- CH(3-furyl)
568 H H H H -(CH2)0(CH2)- CH(3-furyl)
569 H H H H -(CH2)0(CH2)2- CH(3-furyl)
570 H H H H -(CH2)20(CH2)2- CH(3-furyl)
571 H H H -CH2- H CH(3-furyl)
572 Me H H -CH2- 'Pr CH(3-furyl)
573 H H H H H H CMe2
574 Me H H H H H CMe2
575 Et H H H H H CMe2
576 H H Me H H H CMe2
577 H H Et H H H CMe2
578 H H 'Pr H H H CMe2 - -
Figure imgf000028_0001
- -
Figure imgf000029_0001
662 compounds are described, designated compounds 14-1 to 14-662 respectively, of formula (lc), wherein R is H, A is CF=CH and the values of R7, R8, R7', R8', R7", R8" and X are as defined in Table 3. 662 compounds are described, designated compounds 15-1 to 15-662 respectively, of formula (lc), wherein R is H, A is S and the values of R7, R8, R7', R8', R7", R8" and X are as defined in Table 3.
662 compounds are described, designated compounds 16-1 to 16-662 respectively, of formula (lc), wherein R is C02Et, A is CH=CH and the values of R7, R8, R7', R8', R7", R8" and X are as defined in Table 3.
662 compounds are described, designated compounds 17-1 to 17-662 respectively, of formula (lc), wherein R is C02Et, A is CF=CH and the values of R7, R8, R7', R8', R7", R8" and X are as defined in Table 3.
662 compounds are described, designated compounds 18-1 to 18-662 respectively, of formula (lc), wherein R is C02Et, A is S and the values of R7, R8, R7', R8', R7", R8" and X are as defined in Table 3.
Table 4 below provides 115 compounds, designated compounds 19-1 to 19-115 respectively, of formula (Id), wherein R is H and A is CH=CH. - -
Figure imgf000030_0001
(Id) TABLE 4
Figure imgf000030_0002
- -
Figure imgf000031_0001
- -
Figure imgf000032_0002
115 compounds are described, designated compounds 20-1 to 20-115 respectively, of formula (Id), wherein R is H, A is CF=CH and the values of R5, R6, R7, R8, R7', R8' and X are as defined in Table 4.
115 compounds are described, designated compounds 21-1 to 21-115 respectively, of formula (Id), wherein R is H, A is S and the values of R5, R6, R7, R8, R7', R8' and X are as defined in Table 4.
115 compounds are described, designated compounds 22-1 to 22-115 respectively, of formula (Id), wherein R is C02Et, A is CH=CH and the values of R5, R6, R7, R8, R7', R8' and X are as defined in Table 4.
115 compounds are described, designated compounds 23-1 to 23-115 respectively, of formula (Id), wherein R is C02Et, A is CF=CH and the values of R5, R6, R7, R8, R7', R8' and X are as defined in Table 4.
115 compounds are described, designated compounds 24-1 to 24-115 respectively, of formula (Id), wherein R is C02Et, A is S and the values of R5, R6, R7, R8, R7', R8' and X are as defined in Table 4.
Table 5 below provides 124 compounds, designated compounds 25-1 to 25-124 respectively, of formula (le), wherein R is H and A is CH=CH.
Figure imgf000032_0001
(le) - -
TABLE 5
Figure imgf000033_0001
- -
Figure imgf000034_0001
- -
Figure imgf000035_0002
124 compounds are described, designated compounds 26-1 to 26-124 respectively, of formula (le), wherein R is H, A is CF=CH and the values of R5, R6, R5', R6 , R7, R8 and X are as defined in Table 5.
124 compounds are described, designated compounds 27-1 to 27-124 respectively, of formula (le), wherein R is H, A is S and the values of R5, R6, R5 , R6 , R7, R8 and X are as defined in Table 5.
124 compounds are described, designated compounds 28-1 to 28-124 respectively, of formula (le), wherein R is C02Et, A is CH=CH and the values of R5, R6, R5', R6 , R7, R8 and X are as defined in Table 5.
124 compounds are described, designated compounds 29-1 to 29-124 respectively, of formula (le), wherein R is C02Et, A is CF=CH and the values of R5, R6, R5', R6 , R7, R8 and X are as defined in Table 5.
124 compounds are described, designated compounds 30-1 to 30-124 respectively, of formula (le), wherein R is C02Et, A is S and the values of R5, R6, R5 , R6 , R7, R8 and X are as defined in Table 5.
Table 6 below provides 41 1 compounds, designated compounds 31-1 to 31-41 1 respectively, of formula (If), wherein R is H and A is CH=CH.
Figure imgf000035_0001
(if)
TABLE 6 - -
Figure imgf000036_0001
- -
Figure imgf000037_0001
- -
Figure imgf000038_0001
- -
Figure imgf000039_0001
- -
Figure imgf000040_0001
- -
289 H H H H Et Et H H CH(4-CNPh)
290 H H H H -(CH2)2- H H CH(4-CNPh)
291 H H H H -(CH2)3- H H CH(4-CNPh)
292 H H H H -(CH2)4- H H CH(4-CNPh)
293 H H H H -(CH2)5- H H CH(4-CNPh)
294 H H H H -(CH2)0(CH2)- H H CH(4-CNPh)
295 H H H H -(CH2)0(CH2)2- H H CH(4-CNPh)
296 H H H H -(CH2)20(CH2)2- H H CH(4-CNPh)
297 H H H H H H Me H CH(4-CNPh)
298 H H H H H H H H CH(2-thienyl)
299 Me H H H H H H H CH(2-thienyl)
300 H H Me H H H H H CH(2-thienyl)
301 H H H H Me H H H CH(2-thienyl)
302 H H H H Et H H H CH(2-thienyl)
303 H H H H 'Pr H H H CH(2-thienyl)
304 H H H H nPr H H H CH(2-thienyl)
305 H H H H cPr H H H CH(2-thienyl)
306 H H H H ¾u H H H CH(2-thienyl)
307 H H H H CH2OMe H H H CH(2-thienyl)
308 H H H H CI H H H CH(2-thienyl)
309 H H H H CF3 H H H CH(2-thienyl)
310 H H H H Ph H H H CH(2-thienyl)
311 H H H H Me Me H H CH(2-thienyl)
312 H H H H Me Et H H CH(2-thienyl)
313 H H H H CF3 Me H H CH(2-thienyl)
314 H H H H CF3 Et H H CH(2-thienyl)
315 H H H H cPr Me H H CH(2-thienyl)
316 H H H H Et Et H H CH(2-thienyl)
317 H H H H -(CH2)2- H H CH(2-thienyl)
318 H H H H -(CH2)3- H H CH(2-thienyl)
319 H H H H -(CH2)4- H H CH(2-thienyl)
320 H H H H -(CH2)5- H H CH(2-thienyl)
321 H H H H -(CH2)0(CH2)- H H CH(2-thienyl)
322 H H H H -(CH2)0(CH2)2- H H CH(2-thienyl)
323 H H H H -(CH2)20(CH2)2- H H CH(2-thienyl)
324 H H H H H H Me H CH(2-thienyl)
325 H H H H H H H H CH(3-furyl)
326 Me H H H H H H H CH(3-furyl)
327 H H Me H H H H H CH(3-furyl)
328 H H H H Me H H H CH(3-furyl)
329 H H H H Et H H H CH(3-furyl)
330 H H H H 'Pr H H H CH(3-furyl)
331 H H H H nPr H H H CH(3-furyl)
332 H H H H cPr H H H CH(3-furyl)
333 H H H H ¾u H H H CH(3-furyl)
334 H H H H CH2OMe H H H CH(3-furyl)
335 H H H H CI H H H CH(3-furyl)
336 H H H H CF3 H H H CH(3-furyl)
337 H H H H Ph H H H CH(3-furyl)
338 H H H H Me Me H H CH(3-furyl)
339 H H H H Me Et H H CH(3-furyl)
340 H H H H CF3 Me H H CH(3-furyl)
341 H H H H CF3 Et H H CH(3-furyl)
342 H H H H cPr Me H H CH(3-furyl)
343 H H H H Et Et H H CH(3-furyl)
344 H H H H -(CH2)2- H H CH(3-furyl)
345 H H H H -(CH2)3- H H CH(3-furyl)
346 H H H H -(CH2)4- H H CH(3-furyl) - -
Figure imgf000042_0001
- -
Figure imgf000043_0002
41 1 compounds are described, designated compounds 32-1 to 32-41 1 respectively, of formula (If), wherein R is H, A is CF=CH and the values of R7, R8, R7', R8', R7", R8", R7 ', R8" and X are as defined in Table 6. 41 1 compounds are described, designated compounds 33-1 to 33-41 1 respectively, of formula (If), wherein R is H, A is S and the values of R7, R8, R7', R8', R7", R8", R7 "', R8" and X are as defined in Table 6.
41 1 compounds are described, designated compounds 34-1 to 34-41 1 respectively, of formula (If), wherein R is C02Et, A is CH=CH and the values of R7, R8, R7', R8', R7", R8", R7 "', R8" and X are as defined in Table 6.
41 1 compounds are described, designated compounds 35-1 to 35-41 1 respectively, of formula (If), wherein R is C02Et, A is CF=CH and the values of R7, R8, R7', R8', R7", R8", R7 "', R8" and X are as defined in Table 6.
41 1 compounds are described, designated compounds 36-1 to 36-41 1 respectively, of formula (If), wherein R is C02Et, A is S and the values of R7, R8, R7', R8', R7", R8", R7 "', R8" and X are as defined in Table 6.
Table 7 below provides 143 compounds, designated compounds 37-1 to 37-143 respectively, of formula (Ig), wherein R is H and A is CH=CH.
Figure imgf000043_0001
(ig)
TABLE 7
Cpd
R7 R8 R7' R8' R7" R8" X R5 R6 No
1 H H H H H H 0 H H
2 Me H H H H H 0 H H - -
Figure imgf000044_0001
- -
Figure imgf000045_0001
- -
Figure imgf000046_0001
143 compounds are described, designated compounds 38-1 to 38-143 respectively, of formula (Ig), wherein R is H, A is CF=CH and the values of R5, R6, R7, R8, R7', R8', R7", R8" and X are as defined in Table 7. 143 compounds are described, designated compounds 39-1 to 39-143 respectively, of formula (Ig), wherein R is H, A is S and the values of R5, R6, R7, R8, R7', R8', R7", R8" and X are as defined in Table 7.
143 compounds are described, designated compounds 40-1 to 40-143 respectively, of formula (Ig), wherein R is C02Et, A is CH=CH and the values of R5, R6, R7, R8, R7', R8', R7", R8" and X are as defined in Table 7.
143 compounds are described, designated compounds 41-1 to 41-143 respectively, of formula (Ig), wherein R is C02Et, A is CF=CH and the values of R5, R6, R7, R8, R7', R8', R7", R8" and X are as defined in Table 7.
143 compounds are described, designated compounds 42-1 to 42-143 respectively, of formula (Ig), wherein R is C02Et, A is S and the values of R5, R6, R7, R8, R7', R8', R7", R8" and X are as defined in Table 7.
Table 8 below provides 31 compounds, designated compounds 43-1 to 43-31 respectively, of formula (Ih), wherein R is H and A is CH=CH. - -
Figure imgf000047_0001
(Ih)
TABLE 8
Figure imgf000047_0002
31 compounds are described, designated compounds 44-1 to 44-31 respectively, of formula (Ih), wherein R is H, A is CF=CH and the values of R5, R6, R5', R6 , R7, R8, R7', R8' and X are as defined in Table 8.
31 compounds are described, designated compounds 45-1 to 45-31 respectively, of formula (Ih), wherein R is H, A is S and the values of R5, R6, R5', R6 , R7, R8, R7', R8' and X are as defined in Table 8. - -
31 compounds are described, designated compounds 46-1 to 46-31 respectively, of formula (Ih), wherein R is C02Et, A is CH=CH and the values of R5, R6, R5', R6 , R7, R8, R7', R8' and X are as defined in Table 8.
31 compounds are described, designated compounds 47-1 to 47-31 respectively, of formula (Ih), wherein R is C02Et, A is CF=CH and the values of R5, R6, R5', R6 , R7, R8, R7', R8' and X are as defined in Table 8.
31 compounds are described, designated compounds 48-1 to 48-31 respectively, of formula (Ih), wherein R is C02Et, A is S and the values of R5, R6, R5', R6 , R7, R8, R7', R8' and X are as defined in Table 8. Table 9 below provides 142 compounds, designated compounds 49-1 to 49-142 respectively, of formula (li), wherein R is H and A is CH=CH.
Figure imgf000048_0001
(li)
TABLE 9
Figure imgf000048_0002
- -
Figure imgf000049_0001
- -
Figure imgf000050_0001
- -
Figure imgf000051_0001
142 compounds are described, designated compounds 50-1 to 50-142 respectively, of formula (li), wherein R is H, A is CF=CH and the values of R5, R6, R5', R6 , R5", R6", R7, R8 and X are as defined in Table 9. 142 compounds are described, designated compounds 51-1 to 51-142 respectively, of formula (li), wherein R is H, A is S and the values of R5, R6, R5', R6 , R5", R6", R7, R8 and X are as defined in Table 9.
142 compounds are described, designated compounds 52-1 to 52-142 respectively, of formula (li), wherein R is C02Et, A is CH=CH and the values of R5, R6, R5', R6 , R5", R6", R7, R8 and X are as defined in Table 9.
142 compounds are described, designated compounds 53-1 to 53-142 respectively, of formula (li), wherein R is C02Et, A is CF=CH and the values of R5, R6, R5', R6 , R5", R6", R7, R8 and X are as defined in Table 9.
142 compounds are described, designated compounds 54-1 to 54-142 respectively, of formula (li), wherein R is C02Et, A is S and the values of R5, R6, R5', R6 , R5", R6", R7, R8 and X are as defined in Table 9.
The compounds of formula (I) may exist as different geometric isomers, or in different tautomeric forms. This invention covers all such isomers and tautomers, and mixtures thereof in all proportions, as well as isotopic forms such as deuterated compounds. The compounds of this invention may contain one or more asymmetric centers and may thus give rise to optical isomers and diastereomers. While shown without respect to
stereochemistry, the present invention includes all such optical isomers and diastereomers as well as the racemic and resolved, enantiomerically pure R and S stereoisomers and other mixtures of the R and S stereoisomers and agrochemically acceptable salts thereof. It is recognized that certain optical isomers, or diastereomers may have favorable properties over the other. Thus when disclosing and claiming the invention, when a racemic mixture is disclosed, it is clearly contemplated that both optical isomers, including diastereomers substantially free of the other are disclosed and claimed as well.
Alkyl, as used herein, means an aliphatic hydrocarbon chain and includes straight and branched chains e. g. of 1 to 8 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, n-pentyl, isopentyl, neo-pentyl, n-hexyl, and isohexyl. - -
Cycloalkyl, as used herein, means a cyclic, saturated hydrocarbon group having from 3 to 6 ring carbon atoms. Examples of cycloalkyl groups are cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.
Cycloalkylalkyl, as used herein, means a radical -R-cycloalkyl, wherein R is alkyl as defined above.
Alkenyl, as used herein, means an aliphatic hydrocarbon chain having at least one double bond, and preferably one double bond, and includes straight and branched chains e. g. of 2 to 8 carbon atoms such as ethenyl (vinyl), prop-1-enyl, prop-2-enyl (allyl), isopropenyl, but-1-enyl, but- 2-enyl, but-3-enyl, 2-methypropenyl. Alkynyl, as used herein, means an aliphatic hydrocarbon chain having at least one triple bond, and preferably one triple bond, and includes straight and branched chains e. g. of 2 to 8 carbon atoms such as ethynyl, prop-1-ynyl, prop-2-ynyl (propargyl), but-1-ynyl, but-2-ynyl and but-3-ynyl.
Alkylene, as used herein, means a linear saturated divalent hydrocarbon radical of one to six carbon atoms or a branched saturated divalent hydrocarbon radical of three to six carbon atoms, e.g. methylene, ethylene, propylene, 2-methylpropylene and the like.
Alkoxy, as used herein, means a radical -OR, wherein R is alkyl as defined above.
Examples of alkoxy groups include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, t-butoxy, n-pentoxy, isopentoxy, neo-pentoxy, n-hexyloxy, and isohexyloxy. Alkoxyalkyl, as used herein, means a radical -ROR, wherein each R is, independently, an alkyl group as defined above.
Alkoxyalkoxy, as used herein, means a radical -OROR, wherein each R is, independently, alkyl as defined above.
Alkoxyalkoxyalkyl, as used herein, means a radical -ROROR, wherein each R is, independently, alkyl as defined above.
Cyanoalkyl, as used herein, means an alkyl group as defined above substituted with one or more cyano groups.
Alkylthio, as used herein, means a radical -SR, wherein R is alkyl as defined above.
Alkylthio groups include, but are not limited to, methylthio, ethylthio, propylthio, tert-butylthio, and the like.
Alkylthioalkyl, as used herein, means a radical -RSR, wherein each R is, independently, alkyl as defined above.
Halogen, halide and halo refer to iodine, bromine, chlorine and fluorine. - -
Haloalkyi, as used herein, means an alkyl group as defined above wherein at least one hydrogen atom has been replaced with a halogen atom as defined above. Examples of haloalkyi groups include chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl and trifluoromethyl. Preferred haloalkyi groups are fluoroalkyi groups {i.e. haloalkyi groups, containing fluorine as the only halogen). More highly preferred haloalkyi groups are perfluoroalkyi groups, i.e. alkyl groups wherein all the hydrogen atoms are replaced with fluorine atoms.
Haloalkoxy, as used herein, means a radical -OR, wherein R is haloalkyi as defined above.
Haloalkoxyalkyl, as used herein, means a radical -ROR', wherein R is alkyl as defined above and R' is haloalkyi as defined above.
Haloalkylthio, as used herein, means a radical -SR, wherein R is haloalkyi as defined above.
Alkylcarbonyl, as used herein, means a radical -C(0)R, wherein R is alkyl as defined above. Alkenylcarbonyl, as used herein, means a radical -C(0)R, wherein R is alkenyl as defined above.
Cycloalkylcarbonyl, as used herein, means a radical -C(0)R, wherein R is cycloalkyl as defined above.
Alkoxycarbonyl, as used herein, means a radical -C(0)OR, wherein R is alkyl as defined above.
Alkoxyalkoxycarbonyl, as used herein, means a radical -C(0)OROR, wherein each R is, independently, alkyl as defined above.
Alkenyloxycarbonyl, as used herein, means a radical -C(0)OR, wherein R is alkenyl as defined above. Propargyloxycarbonyl, as used herein, means a radical -C(0)OR, wherein R is propargyl.
Alkylcarbonylalkyl, as used herein, means a radical -RC(0)R, wherein each R is, independently, alkyl as defined above.
Alkoxycarbonylalkyl, as used herein, means a radical -RC(0)OR, wherein each R is, independently, alkyl as defined above. Alkoxyalkylcarbonyl, as used herein, means a radical -C(0)ROR, wherein each R is, independently, alkyl as defined above. - -
Alkoxycarbonylalkylcarbonyl, as used herein, means a radical -C(0)RC(0)OR, wherein each R is, independently, alkyl as defined above.
Alkylthiocarbonyl, as used herein, means a radical -C(0)SR, wherein R is alkyl as defined above. Haloalkylcarbonyl, as used herein means a radical -C(0)R, wherein R is haloalkyi as defined above.
Haloalkoxycarbonyl, as used herein, means a radical -C(0)OR, wherein R is haloalkyi as defined above.
Alkylcarbonyloxy, as used herein, means a radical -OC(0)R, wherein R is an alkyl group as defined above.
Alkylcarbonyloxyalkyl, as used herein, means a radical -ROC(0)R, wherein each R is, independently, alkyl as defined above.
Alkoxycarbonyloxyalkyl, as used herein, means a radical -ROC(0)OR, wherein each R is, independently, alkyl as defined above. Alkylsulphonyl, as used herein, means a radical -S(0)2R, wherein R is alkyl as defined above.
Haloalkylsulphonyl, as used herein, means a radical -S(0)2R, wherein R is haloalkyi as defined above.
Alkylsulphonylalkyl, as used herein, means a radical -RS(0)2R, wherein each R is, independently, alkyl as defined above.
Hydroxy or hydroxyl, as used herein, means the group -OH.
Nitro, as used herein, means the group -N02.
Cyano, or nitrile, as used herein, means the group -CN.
Oxo, as used herein, means the group =0. Aryl, as used herein, means an unsaturated aromatic carbocyclic group of from 6 to 10 carbon atoms having a single ring (e.g., phenyl) or multiple condensed (fused) rings, at least one of which is aromatic (e.g., indanyl, naphthyl). Preferred aryl groups include phenyl, naphthyl and the like. Most preferably, an aryl group is a phenyl group.
Aryloxy, as used herein, means a radical -O-Aryl, wherein Aryl is as defined above.
Preferred aryloxy groups include phenoxy, naphthyloxy and the like.
Arylalkyl, as used herein, means a radical -R-Aryl, wherin R is alkyl as defined above. - -
Arylalkoxyalkyl, as used herein, means a radical -ROR-Aryl, wherein each R is, independently, alkyl as defined above.
Aryloxyalkyl, as used herein, means a radical -RO-Aryl, wherein R is alkyl as defined above. Arylthio, as used herein, means a radical -S-Aryl.
Arylthioalkyl, as used herein, means a radical -RS-Aryl, wherein R is alkyl as defined above.
Arylalkylthioalkyl, as used herein, means a radical -RSR-Aryl, wherein each R is, independently, alkyl as defined above. Arylcarbonyl, as used herein, means a radical -C(0)-Aryl.
Arylcarbonylalkyl, as used herein, means a radical -RC(0)-Aryl, wherein R is alkyl as defined above.
Aryloxycarbonyl, as used herein, means a radical -C(0)0-Aryl.
Arylalkoxycarbonyl, as used herein, means a radical -C(0)OR-Aryl, wherein R is alkyl as defined above.
Aryloxyalkylcarbonyl, as used herein, means a radical -C(0)RO-Aryl, wherein R is alkyl as defined above.
Arylcarbonyloxyalkyl, as used herein, means a radical -ROC(0)-Aryl, wherein R is alkyl as defined above. Aryloxycarbonyloxyalkyl, as used herein, means a radical -ROC(0)OAryl, wherein R is alkyl as defined above.
Arylsulphonyl, as used herein, means a radical -S(0)2Aryl.
Heteroaryl, as used herein, means a ring system containing 5 to 10 ring atoms, 1 to 4 ring heteroatoms and consisting either of a single aromatic ring or of two or more fused rings, at least one of which is aromatic. Preferably, single rings will contain up to three and bicyclic systems up to four heteroatoms which will preferably be independently chosen from nitrogen, oxygen and sulfur. Examples of such groups include pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, furanyl, thiophenyl, oxazolyl, isoxazolyl, oxadiazolyl, thiazolyl, isothiazolyl, thiadiazolyl, pyrrolyl, pyrazolyl, imidazolyl, triazolyl and tetrazolyl. Examples of bicyclic groups are benzothiophenyl, benzimidazolyl, benzothiadiazolyl, quinolinyl, cinnolinyl, quinoxalinyl and pyrazolo[1 ,5- a] pyrimidinyl. - -
Heteroarylalkyl, as used herein, means a radical -R-Het, wherein R is alkyl as defined above and Het is heteroaryl as defined above.
Heterocyclyl, as used herein, means a non-aromatic ring system containing 3 to 10 ring atoms, at least one ring heteroatom and consisting either of a single ring or of two or more fused rings. Preferably, single rings will contain up to three and bicyclic systems up to four heteroatoms which will preferably be chosen from nitrogen, oxygen and sulfur. Examples of such groups include pyrrolidinyl, imidazolinyl, pyrazolidinyl, piperidyl, piperazinyl, quinuclidinyl, morpholinyl, tetrahydrofuranyl, together with unsaturated or partially unsaturated analogues such as 4,5,6,7- tetrahydro-benzothiophenyl, chromen-4-onyl, 9H-fluorenyl, 3,4-dihydro-2H-benzo-1 ,4-dioxepinyl, 2,3-dihydro-benzofuranyl, piperidinyl, 1 ,3-dioxolanyl, 1 ,3-dioxanyl and 4,5-dihydro-isoxazolyl.
Aminocarbonyl, as used herein, means a radical -C(0)NH2.
Alkylaminocarbonyl, as used herein, means a radical -C(0)NRH, wherein R is alkyl as defined above.
Dialkylaminocarbonyl, as used herein, means a radical -C(0)NRR, wherein each R is, independently, alkyl as defined above.
Alkoxycarbonylaminoalkyl, as used herein, means a radical -RNHC(0)OR, wherein each R is, independently, alkyl as defined above.
Optionally substituted' as used herein means the group referred to can be substituted at one or more positions by any one or any combination of the radicals listed thereafter. For most groups, one or more hydrogen atoms are replaced by the radicals listed thereafter. For halogenated groups, for example, haloalkyl groups, one or more halogen atoms are replaced by the radicals listed thereafter.
Suitable salts include those derived from alkali or alkaline earth metals and those derived from ammonia and amines. Preferred cations include sodium, potassium, magnesium, and ammonium cations of the formula N+(R29R30R3 R32) wherein R29, R30, R3 and R32 are independently selected from hydrogen, Ci-C6 alkyl and Ci-C6 hydroxyalkyl. Salts of the compounds of formula (I) can be prepared by treatment of compounds of formula (I) with a metal hydroxide, such as sodium hydroxide, or an amine, such as ammonia, trimethylamine, diethanolamine, 2-methylthiopropylamine, bisallylamine, 2-butoxyethylamine, morpholine, cyclododecylamine, or benzylamine. Amine salts are often preferred forms of the compounds of formula (I) because they are water-soluble and lend themselves to the preparation of desirable aqueous based herbicidal compositions.
Acceptable salts can also be formed from organic and inorganic acids, for example, acetic, propionic, lactic, citric, tartaric, succinic, fumaric, maleic, malonic, mandelic, malic, phthalic, hydrochloric, hydrobromic, phosphoric, nitric, sulfuric, methanesulfonic, naphthalenesulfonic, - - benzenesulfonic, toluenesulfonic, camphorsulfonic, and similarly known acceptable acids when a compound of this invention contains a basic moiety.
Compounds of the invention may be prepared by techniques known to the person skilled in the art of organic chemistry. General methods for the production of compounds of formula (I) are described below. Unless otherwise stated in the text, the substituents R, R , R2, R5, R6, R7, R8, R9, R 0, m, n, p, A, W and X are as defined hereinbefore. The abbreviations LG and LG' as used herein refer to any suitable leaving group, and includes halogen and sulphonate groups. The abbreviation R' as used herein refers to an alkyl group, typically a methyl or ethyl group. The starting materials used for the preparation of the compounds of the invention may be purchased from usual commercial suppliers or may be prepared by known methods. The starting materials as well as the intermediates may be purified before use in the next step by state of the art methodologies such as chromatography, crystallization, distillation and filtration.
Compounds of formula (I) in which R is H may be prepared from compounds of formula (A) and compounds of formula (B) as shown in reaction scheme 1.
Reaction scheme 1
Figure imgf000057_0001
For example, A compound of formula (A) may be heated with a compound of formula (B) in the presence of a catalyst, for example an acid, such as para-toluene sulphonic acid, in a suitable solvent, for example toluene or chlorobenzene. The process may conveniently be carried out using microwave heating or conventional heating in an apparatus for the removal of water, for example a Dean-Stark trap.
Compounds of formula (A) may be prepared from compounds of formula (C) as shown in reaction scheme 2.
Reaction scheme 2
Figure imgf000057_0002
- -
For example, a compound of formula (C) may be treated with a reducing agent such as lithium aluminium hydride in a suitable solvent such as tetrahydrofuran.
Compounds of formula (C) may be prepared from compounds of formula (D) as shown in reaction scheme 3. Reaction scheme 3
Figure imgf000058_0001
(D) (C)
For example, a compound of formula (D) may be treated with a sulphonylating reagent, for example a sulphonic anhydride such as trifluoromethanesulphonic anhydride or a sulphonyl halide such as trifluoromethanesulphonyl chloride, in the presence of a base, for example an organic base such as triethylamine, in a suitable solvent, for example dichloromethane.
Compounds of formula (D) are commercially available or can be made by standard methods well known in the chemical literature.
Compounds of formula (I) in which R is H may alternatively be prepared from compounds of formula (E) as shown in reaction scheme 4.
Reaction scheme 4
Figure imgf000058_0002
For example, a compound of formula (E) in which LG' is a halogen, for example a bromine atom, may be treated with a sulphonamide RS02NH2 in the presence of a base, for example an inorganic base such as caesium carbonate or sodium hydride, in a suitable solvent such as dioxane. Optionally the reaction may be performed in the presence of a suitable catalyst, for example a metal catalyst such as a palladium dibenzylidene acetone complex, and optionally a ligand, for example a phosphine ligand such as XantPhos. - -
Compounds of formula (E) may be prepared from compounds of formula (F) and compounds of formula (B) as shown in reaction scheme 5.
Reaction scheme 5
Figure imgf000059_0001
(B) (E) For example, a compound of formula (F) in which LG and LG' are halogens, for example chlorine atoms, may be reacted with a compound of formula (B) in the presence of a base, for example an inorganic base such as sodium hydride, in a suitable solvent, for example tetrahydrofuran.
Compounds of formula (F) are commercially available or can be made by standard methods well known in the chemical literature. For example, compounds of formula (F) may be prepared from compounds of formula (G) as shown in reaction scheme 6.
Reaction scheme 6
Figure imgf000059_0002
For example, a compound of formula (G) may be treated with a halogenating agent, for example /V-bromosuccinimide, in a suitable solvent, for example carbon tetrachloride, optionally in the presence of a reaction initiator, for example a radical initiator such as azobisisobutyronitrile or irradiation with UV or visible light.
Compounds of formula (G) are commercially available or can be made by standard methods well known in the chemical literature. Alternatively, compounds of formula (F) may be prepared from compounds of formula (H) as shown in reaction scheme 7.
Reaction scheme 7 - -
Figure imgf000060_0001
For example, a compound of formula (H) may be treated with a halogenating agent, for example, thionyl chloride, in a suitable solvent, for example dichloromethane.
Compounds of formula (H) are commercially available or can be made by standard methods well known in the chemical literature.
Compounds of formula (I) in which R is H may alternatively be prepared from compounds of formula (J) and compounds of formula (B) as shown in reaction scheme 8.
Reaction scheme 8
Figure imgf000060_0002
(B) (I)
For example, a compound of formula (J) in which LG is a halogen, for example a chlorine atom, may be reacted with a compound of formula (B) in the presence of a base, for example an inorganic base such as potassium t-butoxide, in a suitable solvent, for example tetrahydrofuran.
Compounds of formula (J) may be prepared from compounds of formula (A) as shown in reaction scheme 9. Reaction scheme 9
Figure imgf000060_0003
For example, a compound of formula (A) may be treated with a halogenating agent, for example, thionyl chloride, in a suitable solvent, for example dichloromethane. - -
Alternatively, compounds of formula (I) in which X = oxygen may be prepared from compounds of formula (K) as shown in reaction scheme 10.
Reaction scheme 10
Figure imgf000061_0001
(K) (I)
For example, a compound of formula (K) may be reacted with an aldehyde, for example aqueous formaldehyde, in the presence of an acid, for example an organic acid such as para- toluene sulphonic acid, in a suitable solvent, for example dioxane.
Compounds of formula (K) in which p = 0 may be prepared from compounds of formula (L) in as shown in reaction scheme 1 1.
Reaction scheme 1 1
Figure imgf000061_0002
(L) (K)
For example, a compound of formula (L) may be treated with a base, for example a strong base such as sodium hexamethyldisilazide, and a nitrosylating agent, for example isopentyl nitrite, in a suitable solvent, for example tetrahydrofuran. Compounds of formula (L) may be prepared by methods known in the literature, for example as described in WO2010/026989 and WO2015/004282.
Compounds of formula (I) in which R is H may be prepared from compounds of formula (M) as shown in reaction scheme 12.
Reaction scheme 12 - -
Figure imgf000062_0001
(I)
For example, a compound of formula (M) may be treated with a sulphonylating reagent, for example a sulphonic anhydride such as trifluoromethanesulphonic anhydride, in the presence of a base, for example an organic base such as triethylamine, in a suitable solvent, for example dichloromethane.
Compounds of formula (M) may be prepared from compounds of formula (N) as shown in reaction scheme 13.
Reaction scheme 13
Figure imgf000062_0002
For example, a compound of formula (N) may be treated with a reducing agent, for example a dissolving metal such as iron and ammonium chloride, in a suitable solvent, for example a mixture of water and ethanol.
Compounds of formula (N) may be made from compounds of formula (O) and compounds of formula (B), as shown in reaction scheme 14. Reaction scheme 14
Figure imgf000062_0003
(O) (B) (N)
For example, a compound of formula (O) in which LG is a halogen, for example a bromine atom, may be reacted with a compound of formula (B) in the presence of a base, for example an inorganic base such as sodium hydride or caesium carbonate, in a suitable solvent, for example dimethylformamide. - -
Compounds of formula (O) are commercially available or can be made by standard methods well known in the chemical literature.
Compounds of formula (B) are commercially available or may be made by methods well known in the literature. For example compounds of formula (B) in which X = CR9R10 may be made from compounds of formula (B) in which X is oxygen as shown in reaction scheme 15.
Reaction scheme 15
Figure imgf000063_0001
(B) (B)
For example, a compound of formula (B) in which X is oxygen may be treated with an olefinating reagent, for example a phosphonium salt, in the presence of a base, for example a strong base such as sodium hydride, in a suitable solvent, for example tetrahydrofuran.
Compounds of formula (B) in which X is oxygen are commercially available or can be made by standard methods well known in the chemical literature. For example, compounds of formula (B) in which X is oxygen may be prepared from compounds of formula (P) as shown in reaction scheme 16. Reaction scheme 16
Figure imgf000063_0002
(P) (B)
For example, a compound (P) may be treated with an oxidising agent, for example a hypervalent iodine compound such as the Dess-Martin periodinane, in a suitable solvent, for example dichloromethane.
Compounds of formula (P) may be prepared from compounds of formula (Q) as shown reaction scheme 17.
Reaction scheme 17 - -
Figure imgf000064_0001
(Q) (P)
For example, a compound of formula (Q) may be reacted with a base, for example an inorganic base such as potassium carbonate, in a suitable solvent, for example an alcoholic solvent such as methanol.
Compounds of formula (Q) may be prepared from compounds of formula (R), as shown reaction scheme 18.
Reaction scheme 18
Figure imgf000064_0002
For example, a compound of formula (R) in which LG is a bromine atom may be reacted with a suitable nucleophile, for example potassium acetate, optionally in the presence of an additive such as 18-crown-6, in a suitable solvent, for example acetonitrile.
Compounds of formula (R) may be prepared from compounds of formula (S), as shown in reaction scheme 19.
Reaction scheme 19
Figure imgf000064_0003
(S) (R)
For example, a compound of formula (S) may be treated with a halogenation reagent, for example a brominating reagent such as phenyltrimethylammonium tribromide, optionally in the - - presence of a base, for example an organic base such as triethylamine, and a suitable additive, for example a silylating agent such as trimethylsilyl trifluoromethanesulphonate, in a suitable solvent, for example dichloromethane.
Compounds of formula (S) are commercially available or can be made by standard methods well known in the chemical literature.
Alternatively compounds of formula (P) may be prepared from compounds of formula (T), as shown in reaction scheme 20.
Reaction scheme 20
Figure imgf000065_0001
(T) (P)
For example, a compound of formula (T) may be reacted with a Lewis acid, for example, boron tribromide, in a suitable solvent, for example dichloromethane.
Compounds of formula (T) may be prepared from compounds of formula (U), as shown in reaction scheme 21.
Reaction scheme 21
Figure imgf000065_0002
(U) (T)
For example, a compound of formula (U) may be treated with a reducing agent, for example a metal hydride reducing agent such sodium borohydride, optionally in the presence of an additive, for example a metal salt such as cobalt chloride, in a suitable solvent, for example tetrahydrofuran. Compounds of formula (U) in which p = 0 can be prepared from compounds of formula (V), as shown in reaction scheme 22.
Reaction scheme 22 - -
Figure imgf000066_0001
For example, a compound of formula (V) may be heated with a suitable additive, for example a metal salt such as lithium chloride, in a suitable solvent, for example dimethyl sulphoxide.
Compounds of formula (V) may be prepared from compounds of formula (W) and compounds of formula (X), as shown in reaction scheme 23.
Reaction scheme 23
Figure imgf000066_0002
For example, a mixture of a compound of formula (W) and a compound of formula (X) maybe treated with a base, for example a strong base such as lithium hexamethyldisilazide, in a suitable solvent, such as tetrahydrofuran.
Compounds of formula (W) are commercially available or can be made by standard methods well known in the chemical literature.
Compounds of formula (X) may be prepared from compounds of formula (Y) and compounds of formula (Z), as shown in reaction scheme 24.
Reaction scheme 24
Figure imgf000066_0003
- -
For example, a mixture of a compound of formula (Y) and a compound of formula (Z) may be treated with a base, for example an organic base such as piperidine, optionally in the presence of a suitable solvent, for example tetrahydrofuran.
Compounds of formula (Y) and compounds of formula (Z) are commercially available or can be made by standard methods well known in the chemical literature.
Alternatively, compounds of formula (B) in which p = 0 and X is oxygen may be prepared from compounds of formula (AA), as shown in reaction scheme 25.
Reaction scheme 25
Figure imgf000067_0001
For example, a compound of formula (AA) may be heated in the presence of a catalyst, for example an acid, such as para-toluene sulphonic acid, in a suitable solvent, for example dioxane.
Compounds of formula (AA) may be prepared from compounds of formula (BB), as shown in reaction scheme 26.
Reaction scheme 26
Figure imgf000067_0002
(BB) (AA)
For example, a compound of formula (BB) may be heated with morpholine.
Compounds of formula (BB) may be prepared from compounds of formula (S), as shown in reaction scheme 27.
Reaction scheme 27 - -
Figure imgf000068_0001
For example, a compound of formula (S) may be treated with a chlorinating reagent, for example phosphorus pentachloride, in a suitable solvent, for example chloroform.
Alternatively, compounds of formula (B) in which p = 0 and X = CR9R10 may be prepared from compounds of formula (CC), as shown in reaction scheme 28.
Reaction scheme 28
Figure imgf000068_0002
(CC) (B)
For example, a compound of formula (CC) may be treated with a dehydrating agent, for example a carbodiimide such as dicyclohexyl carbodiimide, optionally in the presence of a catalyst, for example a metal salt such as copper (I) iodide, in a suitable solvent, for example toluene.
Compounds of formula (CC) may be prepared from compounds of formula (DD) as shown in reaction scheme 29.
Reaction scheme 29
Figure imgf000068_0003
(DD) (CC)
For example, a compound of formula (DD) may be treated with a reducing agent, for example a metal hydride reducing agent such as sodium borohydride, in a suitable solvent, for example methanol. - -
Compounds of formula (DD) are commercially available or can be made by standard methods well known in the chemical literature.
Alternatively, compounds of formula (B) in which p = 0 and X = CR9R10 may be prepared from compounds of formula (S) in which p = 0 and compounds of formula (EE), as shown in reaction scheme 30.
Reaction scheme 30
Figure imgf000069_0001
(S) (EE) (B)
For example, a compound of formula (S) may be treated with a base, for example a strong base such as butyl lithium, and a ketone or aldehyde of formula (EE) in a suitable solvent, for example tetrahydrofuran.
Compounds of formula (EE) are commercially available or can be made by standard methods well known in the chemical literature.
Compounds of formula (I) in which X = CR9R10 may alternatively be prepared from compounds of formula (I) in which X is oxygen as shown in reaction scheme 31.
Reaction scheme 31
Figure imgf000069_0002
For example, a compound of formula (I) in which X is oxygen may be treated with an olefinating reagent, for example a phosphonium salt, in the presence of a base, for example a strong base such as sodium hydride, in a suitable solvent, for example tetrahydrofuran. Compounds of formula (I) in which R is not H may be prepared from compounds of formula (I) in which R is H as shown in reaction scheme 32.
Reaction scheme 32 - -
Figure imgf000070_0001
For example, a compound of formula (I) in which R is H may be treated with a base, for example an inorganic base such as sodium hydride or an organic base such as triethylamine, and an electrophilic reagent LG-R , in a suitable solvent, for example dichloromethane.
Alternatively, a compound of formula (I) in which R is not H may be prepared from compounds of formula (FF) as shown in reaction scheme 33.
Reaction scheme 33
Figure imgf000070_0002
For example, a compound of formula (FF) may be treated with a sulphonylating reagent, for example a sulphonyl halide such as trifluoromethanesulphonyl chloride, in the presence of a base, for example an inorganic base such as sodium hydride, in a suitable solvent, for example dimethoxyethane.
Compounds of formula (FF) may be prepared from compounds of formula (M), as shown in reaction scheme 34. Reaction scheme 34
Figure imgf000070_0003
- -
For example, a compound of formula (M) may be treated with a base, for example an inorganic base such as sodium bicarbonate or an organic base such as triethylamine, and an electrophilic reagent LG-R , for example a chloroformate, in a suitable solvent, for example acetonitrile.
Compounds of formula (I) in which m is not 0 may be prepared from compounds of formula (I), as shown in reaction scheme 35.
Reaction scheme 35
Figure imgf000071_0001
(I) (I)
For example, a compound of formula (I) in which R is H may be treated with a suitable electrophilic reagent, for example a halogenating agent such as /V-bromosuccinimide, optionally in the presence of an additive, such as a radical initiator such as AIBN, in a suitable solvent, for example carbon tetrachloride.
One skilled in the art will realise that it is often possible to alter the order in which the transformations described above are conducted, or to combine them in alternative ways to prepare a wide range of compounds of formula (I). Multiple steps may also be combined in a single reaction. All such variations are contemplated within the scope of the invention.
The skilled man will also be aware that some reagents will be incompatible with certain values or combinations of the substituents R, R , R2, R5, R6, R7, R8, R9, R 0, m, n, p, A, W and X as defined herein, and any additional steps, such as protection and/or deprotection steps, which are necessary to achieve the desired transformation will be clear to the skilled man.
The compounds of formula (I) according to the invention can be used as herbicides in unmodified form, as obtained in the synthesis, but they are generally formulated into herbicidal compositions in various ways using formulation adjuvants, such as carriers, solvents and surface- active substances. Therefore, the invention also relates to a herbicidal composition which comprises a herbicidally effective amount of a compound of formula (I) in addition to formulation adjuvants.
The compounds according to the invention are generally formulated in various ways using formulation adjuvants, such as carriers, solvents and surface-active substances. The
formulations can be in various physical forms, e.g. in the form of dusting powders, gels, wettable powders, water-dispersible granules, water-dispersible tablets, effervescent pellets, emulsifiable - - concentrates, microemulsifiable concentrates, oil-in-water emulsions, oil-flowables, aqueous dispersions, oily dispersions, suspo-emulsions, capsule suspensions, emulsifiable granules, soluble liquids, water-soluble concentrates (with water or a water-miscible organic solvent as carrier), impregnated polymer films or in other forms known e.g. from the Manual on
Development and Use of FAO and WHO Specifications for Pesticides, United Nations, First
Edition, Second Revision (2010). Such formulations can either be used directly or diluted prior to use. The dilutions can be made, for example, with water, liquid fertilisers, micronutrients, biological organisms, oil or solvents.
The formulations can be prepared e.g. by mixing the active ingredient with the 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 formulated with other adjuvants, such as finely divided solids, mineral oils, oils of vegetable or animal origin, modified oils of vegetable or animal origin, organic solvents, water, surface-active substances or combinations thereof. The active ingredients can also be contained in very fine microcapsules. Microcapsules contain the active ingredients in a porous carrier. This enables the active ingredients to be released into the environment in controlled amounts (e.g. slow-release). 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 in the form of a monolithic solid, in the form of fine particles in solid or liquid dispersion or in the form of a suitable solution. The encapsulating membranes can comprise, for example, natural or synthetic rubbers, cellulose, styrene/butadiene copolymers, polyacrylonitrile, polyacrylate, polyesters, polyamides, polyureas, polyurethane or chemically modified polymers and starch xanthates or other polymers that are known to the person skilled in the art. Alternatively, very fine
microcapsules can be formed in which the active ingredient is contained in the form of finely divided particles in a solid matrix of base substance, but the microcapsules are not themselves encapsulated.
The formulation adjuvants that are suitable for the preparation of the formulations according to the invention are known per se. As liquid carriers there may be used: water, toluene, xylene, petroleum ether, vegetable oils, acetone, methyl ethyl ketone, cyclohexanone, acid anhydrides, acetonitrile, acetophenone, amyl acetate, 2-butanone, butylene carbonate, chlorobenzene, cyclohexane, cyclohexanol, alkyl esters of acetic acid, diacetone alcohol, 1 ,2- dichloropropane, diethanolamine, p-diethylbenzene, diethylene glycol, diethylene glycol abietate, diethylene glycol butyl ether, diethylene glycol ethyl ether, diethylene glycol methyl ether, N,N- dimethylformamide, dimethyl sulfoxide, 1 ,4-dioxane, dipropylene glycol, dipropylene glycol methyl ether, dipropylene glycol dibenzoate, diproxitol, alkylpyrrolidone, ethyl acetate, 2-ethylhexanol, ethylene carbonate, 1 ,1 , 1-trichloroethane, 2-heptanone, alpha-pinene, d-limonene, ethyl lactate, ethylene glycol, ethylene glycol butyl ether, ethylene glycol methyl ether, gamma-butyrolactone, glycerol, glycerol acetate, glycerol diacetate, glycerol triacetate, hexadecane, hexylene glycol, - - isoamyl acetate, isobornyl acetate, isooctane, isophorone, isopropylbenzene, isopropyl myristate, lactic acid, laurylamine, mesityl oxide, methoxypropanol, methyl isoamyl ketone, methyl isobutyl ketone, methyl laurate, methyl octanoate, methyl oleate, methylene chloride, m-xylene, n-hexane, n-octylamine, octadecanoic acid, octylamine acetate, oleic acid, oleylamine, o-xylene, phenol, polyethylene glycol, propionic acid, propyl lactate, propylene carbonate, propylene glycol, propylene glycol methyl ether, p-xylene, toluene, triethyl phosphate, triethylene glycol, xylenesu Ifonic acid, paraffin, mineral oil, trichloroethylene, perchloroethylene, ethyl acetate, amyl acetate, butyl acetate, propylene glycol methyl ether, diethylene glycol methyl ether, methanol, ethanol, isopropanol, and alcohols of higher molecular weight, such as amyl alcohol, tetrahydro- furfuryl alcohol, hexanol, octanol, ethylene glycol, propylene glycol, glycerol, N-methyl-2- pyrrolidone and the like.
Suitable solid carriers are, for example, talc, titanium dioxide, pyrophyllite clay, silica, attapulgite clay, kieselguhr, limestone, calcium carbonate, bentonite, calcium montmorillonite, cottonseed husks, wheat flour, soybean flour, pumice, wood flour, ground walnut shells, lignin and similar substances.
A large number of surface-active substances can advantageously be used in both solid and liquid formulations, especially in those formulations which can be diluted with a carrier prior to use. Surface-active substances may be anionic, cationic, non-ionic or polymeric and they can be used as emulsifiers, wetting agents or suspending agents or for other purposes. Typical surface-active substances include, for example, salts of alkyl sulfates, such as
diethanolammonium lauryl sulfate; salts of alkylarylsulfonates, such as calcium dodecyl- benzenesulfonate; alkylphenol/alkylene oxide addition products, such as nonylphenol ethoxylate; alcohol/alkylene oxide addition products, such as tridecylalcohol 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 lauryltrimethylammonium 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-alkylphosphate esters; and also further substances described e.g. in McCutcheon's Detergents and Emulsifiers Annual, MC Publishing Corp., Ridgewood New Jersey (1981 ).
Further adjuvants that can be used in pesticidal formulations include crystallisation inhibitors, viscosity modifiers, suspending agents, dyes, anti-oxidants, foaming agents, light absorbers, mixing auxiliaries, antifoams, complexing agents, neutralising or pH-modifying substances and buffers, corrosion inhibitors, fragrances, wetting agents, take-up enhancers, micronutrients, plasticisers, glidants, lubricants, dispersants, thickeners, antifreezes,
microbicides, and liquid and solid fertilisers.
The formulations according to the invention can include an additive comprising an oil of vegetable or animal origin, a mineral oil, alkyl esters of such oils or mixtures of such oils and oil - - derivatives. The amount of oil additive in the composition according to the invention is generally from 0.01 to 10 %, based on the mixture to be applied. For example, the oil additive can be added to a spray tank in the desired concentration after a spray mixture has been prepared. Preferred oil additives comprise mineral oils or an oil of vegetable origin, for example rapeseed oil, olive oil or sunflower oil, emulsified vegetable oil, alkyl esters of oils of vegetable origin, for example the methyl derivatives, or an oil of animal origin, such as fish oil or beef tallow. Preferred oil additives comprise alkyl esters of C8-C22 fatty acids, especially the methyl derivatives of d2- C-I8 fatty acids, for example the methyl esters of lauric acid, palmitic acid and oleic acid (methyl laurate, methyl palmitate and methyl oleate, respectively). Many oil derivatives are known from the Compendium of Herbicide Adjuvants, 10th Edition, Southern Illinois University, 2010.
The formulations generally comprise from 0.1 to 99 % by weight, especially from 0.1 to 95 % by weight, of the compound of formula (I) and from 1 to 99.9 % by weight of a formulation adjuvant which preferably includes from 0 to 25 % by weight of a surface-active substance. Whereas commercial products may preferably be formulated as concentrates, the end user will normally employ dilute formulations.
The rates of application vary within wide limits and depend on the nature of the soil, the method of application, the crop plant, the pest to be controlled, the prevailing climatic conditions, and other factors governed by the method of application, the time of application and the target crop. As a general guideline compounds may be applied at a rate of from 1 to 2000 l/ha, especially from 10 to 1000 l/ha.
Preferred formulations can have the following compositions (weight %):
Emulsifiable concentrates: active ingredient: 1 to 95 %, preferably 60 to 90 %
surface-active agent 1 to 30 %, preferably 5 to 20 %
liquid carrier: 1 to 80 %, preferably 1 to 35 %
Dusts: active ingredient: 0.1 to 10 %, preferably 0.1 to 5 %
solid carrier: 99.9 to 90 %, preferably 99.9 to 99 %
Suspension concentrates: active ingredient: 5 to 75 %, preferably 10 to 50 %
water: 94 to 24 %, preferably 88 to 30 %
surface-active agent 1 to 40 %, preferably 2 to 30 % Wettable powders: active ingredient: 0.5 to 90 %, preferably 1 to 80 % - - surface-active agent: 0.5 to 20 %, preferably 1 to 15 %
solid carrier: 5 to 95 %, preferably 15 to 90 %
Granules: active ingredient: 0.1 to 30 %, preferably 0.1 to 15 %
solid carrier: 99.5 to 70 %, preferably 97 to 85 %
The following Examples further illustrate, but do not limit, the invention.
Figure imgf000075_0001
The combination is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable mill, affording wettable powders that can be diluted with water to give suspensions of the desired concentration.
Figure imgf000075_0002
The combination is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable mill, affording powders that can be used directly for seed treatment.
Emulsifiable concentrate
active ingredients 10 %
octylphenol polyethylene glycol ether 3 %
(4-5 mol of ethylene oxide)
calcium dodecylbenzenesulfonate 3 %
castor oil polyglycol ether (35 mol of ethylene oxide) 4 % - -
Figure imgf000076_0001
Emulsions of any required dilution, which can be used in plant protection, can be obtained from this concentrate by dilution with water.
Figure imgf000076_0002
Ready-for-use dusts are obtained by mixing the combination with the carrier and grinding the mixture in a suitable mill. Such powders can also be used for dry dressings for seed.
Figure imgf000076_0003
The combination is mixed and ground with the adjuvants, and the mixture is moistened with water. The mixture is extruded and then dried in a stream of air.
Figure imgf000076_0004
The finely ground combination is uniformly applied, in a mixer, to the kaolin moistened with polyethylene glycol. Non-dusty coated granules are obtained in this manner.
Suspension concentrate active ingredients 40 %
propylene glycol 10 %
nonylphenol polyethylene glycol ether (15 mol of ethylene oxide) 6 %
Sodium lignosulfonate 10 %
Carboxymethylcellulose 1 % - -
Figure imgf000077_0001
The finely ground combination is intimately mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water. Using such dilutions, living plants as well as plant propagation material can be treated and protected against infestation by microorganisms, by spraying, pouring or immersion.
Flowable concentrate for seed treatment
Figure imgf000077_0002
The finely ground combination is intimately mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water. Using such dilutions, living plants as well as plant propagation material can be treated and protected against infestation by microorganisms, by spraying, pouring or immersion.
Slow Release Capsule Suspension
28 parts of the combination are mixed with 2 parts of an aromatic solvent and 7 parts of toluene diisocyanate/polymethylene-polyphenylisocyanate-mixture (8: 1 ). This mixture is emulsified in a mixture of 1.2 parts of polyvinylalcohol, 0.05 parts of a defoamer and 51 .6 parts of water until the desired particle size is achieved. To this emulsion a mixture of 2.8 parts 1 ,6-diaminohexane in 5.3 parts of water is added. The mixture is agitated until the polymerization reaction is completed. The obtained capsule suspension is stabilized by adding 0.25 parts of a thickener and 3 parts of a dispersing agent. The capsule suspension formulation contains 28% of the active ingredients. The medium capsule diameter is 8-15 microns. The resulting formulation is applied to seeds as an aqueous suspension in an apparatus suitable for that purpose.
The invention also provides a method of controlling plants which comprises applying to the plants or to the locus thereof a herbicidally effective amount of a compound of formula (I) or a composition according to the invention. - -
The invention also provides a method of inhibiting plant growth which comprises applying to the plants or to the locus thereof a herbicidally effective amount of a compound of formula (I) or a composition according to the invention.
The invention also provides a method of controlling weeds in crops of useful plants, comprising applying to said weeds or to the locus of said weeds, or to said useful plants or to the locus of said useful plants, a compound of formula (I) or a composition according to the invention.
The invention also provides a method of selectively controlling grasses and/or weeds in crops of useful plants which comprises applying to the useful plants or locus thereof or to the area of cultivation a herbicidally effective amount of a compound of formula (I) or a composition according to the invention.
The term "herbicide" as used herein means a compound that controls or modifies the growth of plants. The term "herbicidally effective amount" means the quantity of such a compound or combination of such compounds that is capable of producing a controlling or modifying effect on the growth of plants. Controlling or modifying effects include all deviation from natural development, for example killing, retardation, leaf burn, albinism, dwarfing and the like.
The term "locus" as used herein means fields in or on which plants are growing, or where seeds of cultivated plants are sown, or where seed will be placed into the soil. It includes soil, seeds, and seedlings, as well as established vegetation.
The term "plants" refers to all physical parts of a plant, including seeds, seedlings, saplings, roots, tubers, stems, stalks, foliage, and fruits.
The term "plant propagation material" denotes all generative parts of a plant, for example seeds or vegetative parts of plants such as cuttings and tubers. It includes seeds in the strict sense, as well as roots, fruits, tubers, bulbs, rhizomes, and parts of plants.
Crops of useful plants in which the compounds and composition according to the invention can be used include perennial and annual crops, such as berry plants for example blackberries, blueberries, cranberries, raspberries and strawberries; cereals for example barley, maize (corn), millet, oats, rice, rye, sorghum triticale and wheat; fibre plants for example cotton, flax, hemp, jute and sisal; field crops for example sugar and fodder beet, coffee, hops, mustard, oilseed rape (canola), poppy, sugar cane, sunflower, tea and tobacco; fruit trees for example apple, apricot, avocado, banana, cherry, citrus, nectarine, peach, pear and plum; grasses for example Bermuda grass, bluegrass, bentgrass, centipede grass, fescue, ryegrass, St. Augustine grass and Zoysia grass; herbs such as basil, borage, chives, coriander, lavender, lovage, mint, oregano, parsley, rosemary, sage and thyme; legumes for example beans, lentils, peas and soya beans; nuts for example almond, cashew, ground nut, hazelnut, peanut, pecan, pistachio and walnut; palms for example oil palm; ornamentals for example flowers, shrubs and trees; other trees, for example cacao, coconut, olive and rubber; vegetables for example asparagus, aubergine, broccoli, - - cabbage, carrot, cucumber, garlic, lettuce, marrow, melon, okra, onion, pepper, potato, pumpkin, rhubarb, spinach and tomato; and vines for example grapes.
Crops are to be understood as being those which are naturally occurring, obtained by conventional methods of breeding, or obtained by genetic engineering. They include crops which contain so-called output traits (e.g. improved storage stability, higher nutritional value and improved flavour).
Crops are to be understood as also including those crops which have been rendered tolerant to herbicides like bromoxynil or classes of herbicides such as ALS-, EPSPS-, GS-, HPPD- and PPO-inhibitors. An example of a crop that has been rendered tolerant to
imidazolinones, e.g. imazamox, by conventional methods of breeding is Clearfield® summer canola. Examples of crops that have been rendered tolerant to herbicides by genetic engineering methods include e.g. glyphosate- and glufosinate-resistant maize varieties commercially available under the trade names Round upReady®, Herculex I® and LibertyLink®.
Crops are also to be understood as being those which naturally are or have been rendered resistant to harmful insects. This includes plants transformed by the use of recombinant DNA techniques, for example, to be capable of synthesising one or more selectively acting toxins, such as are known, for example, from toxin-producing bacteria. Examples of toxins which can be expressed include δ-endotoxins, vegetative insecticidal proteins (Vip), insecticidal proteins of bacteria colonising nematodes, and toxins produced by scorpions, arachnids, wasps and fungi. An example of a crop that has been modified to express the Bacillus thuringiensis toxin is the Bt maize KnockOut® (Syngenta Seeds). An example of a crop comprising more than one gene that codes for insecticidal resistance and thus expresses more than one toxin is VipCot® (Syngenta Seeds). Crops or seed material thereof can also be resistant to multiple types of pests (so-called stacked transgenic events when created by genetic modification). For example, a plant can have the ability to express an insecticidal protein while at the same time being herbicide tolerant, for example Herculex I® (Dow AgroSciences, Pioneer Hi-Bred International).
Compounds and compositions of the invention can typically be used to control a wide variety of monocotyledonous and dicotyledonous weed species. Examples of monocotyledonous species that can typically be controlled include Alopecurus myosuroides, Avena fatua, Brachiaria plantaginea, Bromus tectorum, Cyperus esculentus, Digitaria sanguinalis, Echinochloa crus-galli, Lolium perenne, Lolium multiflorum, Panicum miliaceum, Poa annua, Setaria viridis, Setaria faberi and Sorghum bicolor. Examples of dicotyledonous species that can be controlled include Abutilon theophrasti, Amaranthus retroflexus, Bidens pilosa, Chenopodium album, Euphorbia heterophylla, Galium aparine, Ipomoea hederacea, Kochia scoparia, Polygonum convolvulus, Sida spinosa, Sinapis arvensis, Solanum nigrum, Stellaria media, Veronica persica and Xanthium strumarium. - -
The compounds of the invention can be applied before or after planting of the crops, before weeds emerge (pre-emergence application) or after weeds emerge (post-emergence
application), and are particularly effective when applied pre-emergence to the weeds.
Any method of application to weeds/crop of useful plant, or locus thereof, which is routinely used in agriculture may be used, for example application by spray or broadcast method typically after suitable dilution of a compound of formula (I) (whether said compound is formulated and/or in combination with one or more further active ingredients and/or safeners, as described herein).
The compounds of formula (I) according to the invention can also be used in combination with other active ingredients, e.g. other herbicides, and/or insecticides, and/or acaricides, and/or nematocides, and/or molluscicides, and/or fungicides, and/or plant growth regulators. Such mixtures, and the use of such mixtures to control weeds and/or undesired plant growth, form yet further aspects of the invention. For the avoidance of doubt, mixtures of invention also include mixtures of two or more different compounds of formula (I). In particular, the present invention also relates to a composition of the invention which comprises at least one further herbicide in addition to the compound of formula (I).
Compounds of formula I can be used in combination with one or more other herbicides to provide various herbicidal mixtures. Specific examples of such mixtures include (wherein Ί" represents a compound of formula I):- 1 + acetochlor, I + acifluorfen, I + acifluorfen-sodium, I + aclonifen, I + acrolein, I + alachlor, I + alloxydim, I + allyl alcohol, I + ametryn, I +
amicarbazone, I + amidosulfuron, I + aminocyclopyrachlor, I + aminopyralid, I + amitrole, I + ammonium sulfamate, I + anilofos, I + asulam, I + atrazine, I + aviglycine, I + azafenidin, I + azimsulfuron, I + BCPC, I + beflubutamid, I + benazolin, I + bencarbazone, I + benfluralin, I + benfuresate, I + bensulfuron, I + bensulfuron-methyl, I + bensulide, I + bentazone, I + benzfendizone, I + benzobicyclon, I + benzofenap, I + bicyclopyrone, I + bifenox, I + bilanafos, I + bispyribac, I + bispyribac-sodium, I + borax, I + bromacil, I + bromobutide, I +
bromophenoxim, I + bromoxynil, I + butachlor, I + butafenacil, I + butamifos, I + butralin, I + butroxydim, I + butylate, I + cacodylic acid, I + calcium chlorate, I + cafenstrole, l + carbetamide, I + carfentrazone, I + carfentrazone-ethyl, I + CDEA, I + CEPC, I + chlorflurenol, I + chlorflurenol-methyl, I + chloridazon, I + chlorimuron, I + chlorimuron-ethyl, I + chloroacetic acid, I + chlorotoluron, I + chlorpropham, I + chlorsulfuron, I + chlorthal, I + chlorthal-dimethyl, I + cinidon-ethyl, I + cinmethylin, I + cinosulfuron, I + cisanilide, I + clethodim, I + clodinafop, I + clodinafop-propargyl, I + clomazone, I + clomeprop, I + clopyralid, I + cloransulam, I + cloransulam-methyl, I + CMA, I + 4-CPB, I + CPMF, I + 4-CPP, I + CPPC, I + cresol, I + cumyluron, I + cyanamide, I + cyanazine, I + cycloate, I + cyclosulfamuron, I + cycloxydim, I + cyhalofop, I + cyhalofop-butyl, I + 2,4-D, I + 3,4-DA, I + daimuron, I + dalapon, I + dazomet, I + 2,4-DB, I + 3,4-DB, I + 2,4-DEB, I + desmedipham, I + desmetryn, I + dicamba, I + dichlobenil, I + ortho-dichlorobenzene, I + para-dichlorobenzene, I + dichlorprop, I + dichlorprop-P, I + diclofop, I + diclofop-methyl, I + diclosulam, I + difenzoquat, I + difenzoquat metilsulfate, I + diflufenican, I + diflufenzopyr, I + dimefuron, I + dimepiperate, I + - - dimethachlor, I + dimethametryn, I + dimethenamid, I + dimethenamid-P, I + dimethipin, I + dimethylarsinic acid, I + dinitramine, I + dinoterb, I + diphenamid, I + dipropetryn, I + diquat, I + diquat dibromide, I + dithiopyr, I + diuron, I + DNOC, I + 3,4-DP, I + DSMA, I + EBEP, I + endothal, I + EPTC, I + esprocarb, I + ethalfluralin, I + ethametsulfuron, I + ethametsulfuron- methyl, I + ethephon, I + ethofumesate, I + ethoxyfen, I + ethoxysulfuron, I + etobenzanid, I + fenoxaprop, I + fenoxaprop-P, I + fenoxaprop-ethyl, I + fenoxaprop-P-ethyl, I + fentrazamide, I + ferrous sulfate, I + flamprop-M, I + flazasulfuron, I + florasulam, I + fluazifop, I + fluazifop- butyl, I + fluazifop-P, I + fluazifop-P-butyl, I + fluazolate, I + flucarbazone, I + flucarbazone- sodium, I + flucetosulfuron, I + fluchloralin, I + flufenacet, I + flufenpyr, I + flufenpyr-ethyl, I + flumetralin, I + flumetsulam, I + flumiclorac, I + flumiclorac-pentyl, I + flumioxazin, I + flumipropin, I + fluometuron, I + fluoroglycofen, I + f I uoroglycof en-ethyl, I + fluoxaprop, I + flupoxam, I + flupropacil, I + flupropanate, I + flupyrsulfuron, I + flupyrsulfuron-methyl-sodium, I + flurenol, I + fluridone, I + flurochloridone, I + fluroxypyr, I + flurtamone, I + fluthiacet, I + fluthiacet-methyl, I + fomesafen, I + foramsulfuron, I + fosamine, I + glufosinate, I + glufosinate-ammonium, I + glyphosate, I + halauxifen, I + halauxifen-methyl, I + halosulfuron, I + halosulfuron-methyl, I + haloxyfop, I + haloxyfop-P, I + HC-252, I + hexazinone, I + imazamethabenz, I + imazamethabenz-methyl, I + imazamox, I + imazapic, I + imazapyr, I + imazaquin, I + imazethapyr, I + imazosulfuron, I + indanofan, I and indaziflam, I +
iodomethane, I + iodosulfuron, I + iodosulfuron-methyl-sodium, I + ioxynil, I + ipfencarbazone, I + isoproturon, I + isouron, I + isoxaben, I + isoxachlortole, I + isoxaflutole, I + isoxapyrifop, I + karbutilate, I + lactofen, I + lenacil, I + linuron, I + MAA, I + MAMA, I + MCPA, I + MCPA- thioethyl, I + MCPB, I + mecoprop, I + mecoprop-P, I + mefenacet, I + mefluidide, I + mesosulfuron, I + mesosulfuron-methyl, I + mesotrione, I + metam, I + metamifop, I + metamitron, I + metazachlor, I + metazosulfuron, I + methabenzthiazuron, I + methazole, I + methiozolin, I + methylarsonic acid, I + methyldymron, I + methyl isothiocyanate, l + metobenzuron, I + metobromuron, I + metolachlor, I + S-metolachlor, I + metosulam, I + metoxuron, I + metribuzin, I + metsulfuron, I + metsulfuron-methyl, I + MK-616, I + molinate, I + monolinuron, I + monosulfuron, I + monosulfuron-ester I + MSMA, I + naproanilide, I + napropamide, I + naptalam, I + NDA-402989, I + neburon, I + nicosulfuron, I + nipyraclofen, I + n-methyl glyphosate, I + nonanoic acid, I + norflurazon, I + oleic acid (fatty acids), I + orbencarb, I + orthosulfamuron, I + oryzalin, I + oxadiargyl, I + oxadiazon, I + oxasulfuron, I + oxaziclomefone, I + oxyfluorfen, I + paraquat, I + paraquat dichloride, I + pebulate, l + pendimethalin, I + penoxsulam, I + pentachlorophenol, I + pentanochlor, I + pentoxazone, I + pethoxamid, I + petrolium oils, I + phenmedipham, I + phenmedipham-ethyl, I + picloram, I + picolinafen, I + pinoxaden, I + piperophos, I + potassium arsenite, I + potassium azide, I + pretilachlor, I + primisulfuron, I + primisulfuron-methyl, I + prodiamine, I + profluazol, I + profoxydim, I + prohexadione-calcium, I + prometon, I + prometryn, I + propachlor, I + propanil, I + propaquizafop, I + propazine, I + propham, I + propisochlor, I + propoxycarbazone, I + propoxycarbazone-sodium, I + propyzamide, I + prosulfocarb, I + prosulfuron, I + pyraclonil, I + pyraflufen, I + pyraflufen-ethyl, I + pyrasulfotole, I + pyrazolynate, I + pyrazosulfuron, I + pyrazosulfuron-ethyl, I + pyrazoxyfen, I + pyribenzoxim, I + pyributicarb, I + pyridafol, I + - - pyridate, I + pyriftalid, I + pyriminobac, I + pyriminobac-methyl, I + pyrimisulfan, I + pyrithiobac, I + pyrithiobac-sodium, I + pyroxasulfone, I + pyroxulam, I + quinclorac, I + quinmerac, I + quinoclamine, I + quizalofop, I + quizalofop-P, I + quizalofop-ethyl, I + quizalofop-P-ethyl, I + rimsulfuron, I + saflufenacil, I + sethoxydim, I + siduron, I + simazine, I + simetryn, I + SMA, I + sodium arsenite, I + sodium azide, I + sodium chlorate, I + sulcotrione, I + sulfentrazone, I + sulfometuron, I + sulfometuron-methyl, I + sulfosate, I + sulfosulfuron, I + sulfuric acid, I + tar oils, I + 2,3,6-TBA, I + TCA, I + TCA-sodium, I + tebutam, I + tebuthiuron, I + tefuryltrione, I + tembotrione, I + tepraloxydim, I + terbacil, I + terbumeton, I + terbuthylazine, I + terbutryn, I + thenylchlor, I + thiazafluron, I + thiazopyr, I + thifensulfuron, I + thiencarbazone, I + thifensulfuron-methyl, I + thiobencarb, I + tiocarbazil, I + topramezone, I + tralkoxydim, I + triafamone I + tri-allate, I + triasulfuron, I + triaziflam, I + tribenuron, I + tribenuron-methyl, I + tricamba, I + triclopyr, I + trietazine, I + trifloxysulfuron, I + trifloxysulfuron-sodium, I + trifluralin, I + triflusulfuron, I + triflusulfuron-methyl, I + trifop, I + trifop-methyl, I +
trihydroxytriazine, I + trinexapac-ethyl, I + tritosulfuron, 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 RN 353292-31-6), I + 2-[[8-chloro-3,4-dihydro-4-(4-methoxyphenyl)-3-oxo-2- quinoxalinyl]carbonyl-1 ,3-cyclohexanedione, I + 4-amino-3-chloro-6-(4-chloro-2-fluoro-3- methoxyphenyl)-5-fluoropyridine-2-carboxylate and I + VX-573.
In particular, the following mixtures are important: Mixtures of a compound of the formula (I) with a triazine (e.g. I + ametryn, I + atrazine, I + cyanazine, I + dimethametryn, I + metribuzin, I + prometon, I + prometryn, I + propazine, I + simazine, I + simetryn, I + terbumeton, I + terbuthylazine, I + terbutryn, I + trietazine).
Mixtures of a compound of formula (I) with an HPPD inhibitor (e.g. I + isoxaflutole, I + mesotrione, I + pyrasulfotole, I + sulcotrione, I + tembotrione, I + topramezone, I + bicyclopyrone, I + benzobicyclon or I + 2-[[8-chloro-3,4-dihydro-4-(4-methoxyphenyl)-3-oxo-2- quinoxalinyl]carbonyl]1 ,3-cyclohexanedione (CAS RN 1342891-70-6)).
Mixtures of a compound of formula (I) with an auxin (e.g. I + dicamba, I + 2,4-D, I + 2,4- DB, I + MCPA, I + fluroxypyr, I + picloram, I + triclopyr, I + quinclorac, I + clopyralid, I + aminopyralid, I + aminocyclopyrachlor, I + halauxifen, I + halauxifen-methyl). Mixtures of a compound of formula (I) with a VLCFA inhibitor (e.g. I + metolachlor, I + S- metolachlor, I + acetochlor, I + dimethenamid-P, I + pyroxasulfone, I + dimethachlor, I + flufenacet, I + metazachlor, I + napropamide, I + pretilachlor).
Mixtures of a compound of formula (I) with a triazolinone (e.g. I + amicarbazone).
Mixtures of a compound of formula (I) with an ALS inhibitor (e.g. I + chlorsulfuron, I + cinosulfuron, I + cloransulam, I + ethametsulfuron, I + flazasulfuron, I + foramsulfuron, I + flumetsulam, I + imazamethabenz, I + imazamox, I + imazapic, I + imazapyr, I + imazethapyr, I + iodosulfuron, I + iofensulfuron, I + metsulfuron, I + nicosulfuron, I + oxasulfuron, I + primisulfuron, - -
I + prosulfuron, I + pyrithiobac, I + pyroxsulam, I + rimsulfuron, I + sulfosulfuron, I +
thifensulfuron, I + triasulfuron, I + tribenuron, I + trifloxysulfuron, I + thiencarbazone, I + tritosulfuron, I + bispyribac-sodium, I + pyribenzoxim, I + pyriftalid, I +flucarbazone-sodium, I +bensulfuron-methyl, I + chlorimuron-ethyl, I + sulfometuron-methyl, I + diclosulam, I + florasulam, I + penoxsulam).
Mixtures of a compound of formula (I) with a PPO inhibitor (e.g. I + fomesafen, I + flumioxazin, I + sulfentrazone, I + acifluorfen-sodium, I + lactofen, I + oxyfluorfen, I + oxadiazon, I + butafenacil, I + carfentrazone-ethyl, 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). Mixtures of a compound of formula (I) with and ACCase inhibitor (i.e. I + clodinafop, I + fluazifop, I + fenoxaprop, I + clethodim, I + quizalofop, I + haloxyfop, I + pinoxaden, I + cycloxydim, I + sethoxydim).
In addition, the following mixtures are also preferred: I + glyphosate, I + glufosinate, I + paraquat, I + diquat, I + pendimethalin, I + trifluralin, I + metamitron, I + clomazone, I + prodiamine, I + saflufenacil, I + prosulfocarb, I + diflufenican, I + isoxaben, I + beflubutamide, I + flurtamone, I + benfluralin, I + chlorotoluron, I + linuron, I + isoproturon, I + triallate, I + hexazinone, I + diuron, I + propanil, I + indaziflam.
Thus, in particular, the following mixtures are preferred: I + ametryn, I + atrazine, I + cyanazine, I + dimethametryn, I + metribuzin, I + prometon, I + prometryn, I + propazine, I + simazine, I + simetryn, I + terbumeton, I + terbuthylazine, I + terbutryn, I + trietazine, I + isoxaflutole, I + mesotrione, I + pyrasulfotole, I + sulcotrione, I + tembotrione, I + topramezone, I + bicyclopyrone, I + benzobicyclon, I + 2-[[8-chloro-3,4-dihydro-4-(4-methoxyphenyl)-3-oxo-2- quinoxalinyl]carbonyl]1 ,3-cyclohexanedione (CAS RN 1342891-70-6), I + dicamba, I + 2,4-D, I + 2,4-DB, I + MCPA, I + fluroxypyr, I + picloram, I + triclopyr, I + quinclorac, I + clopyralid, I + aminopyralid, I + aminocyclopyrachlor, I + halauxifen, I + halauxifen-methyl, I + metolachlor, I + S-metolachlor, I + acetochlor, I + dimethenamid-P, I + pyroxasulfone, I + dimethachlor, I + flufenacet, I + metazachlor, I + napropamide, I + pretilachlor, I + amicarbazone, I + chlorsulfuron, I + cinosulfuron, I + cloransulam, I + ethametsulfuron, I + flazasulfuron, I + foramsulfuron, I + flumetsulam, I + imazamethabenz, I + imazamox, I + imazapic, I + imazapyr, I + imazethapyr, I + iodosulfuron, I + iofensulfuron, I + metsulfuron, I + nicosulfuron, I + oxasulfuron, I + primisulfuron, I + prosulfuron, I + pyrithiobac, I + pyroxsulam, I + rimsulfuron, I + sulfosulfuron, I +
thifensulfuron, I + triasulfuron, I + tribenuron, I + trifloxysulfuron, I + thiencarbazone, I + tritosulfuron, I + bispyribac-sodium, I + pyribenzoxim, I + pyriftalid, I +flucarbazone-sodium, I +bensulfuron-methyl, I + chlorimuron-ethyl, I + sulfometuron-methyl, I + diclosulam, I + florasulam, I + penoxsulam, I + fomesafen, I + flumioxazin, I + sulfentrazone, I + acifluorfen- sodium, I + lactofen, I + oxyfluorfen, I + oxadiazon, I + butafenacil, I + carfentrazone-ethyl, 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, I + clodinafop, I + fluazifop, I + fenoxaprop, I + - - clethodim, I + quizalofop, I + haloxyfop, I + pinoxaden, I + cycloxydim, I + sethoxydim, I + glyphosate, I + glufosinate, I + paraquat, I + diquat, I + pendimethalin, I + trifluralin, I + metamitron, I + clomazone, I + prodiamine, I + saflufenacil, I + prosulfocarb, I + diflufenican, I + isoxaben, I + beflubutamide, I + flurtamone, I + benfluralin, I + chlorotoluron, I +linuron, I + isoproturon, I + triallate, I + hexazinone, I + diuron, I + propanil, I + indaziflam.
The following mixtures are particularly preferred: I + atrazine, I + terbuthylazine, I + isoxaflutole, I + mesotrione, I + S-metolachlor, I + acetochlor, I + pyroxasulfone, I + dimethachlor, I + flufenacet, I + nicosulfuron, I + fomesafen, I + glyphosate, I + glufosinate, I + paraquat, I + saflufenacil, I + prosulfocarb. For the avoidance of doubt, the present invention also includes three-way mixtures of a compound of formula (1 ), a herbicide as defined above and a further herbicide. In particular, the following three-way mixtures are preferred: I + atrazine + mesotrione, I + atrazine + S- metolachlor, I + S-metolachlor + mesotrione, I + glyphosate + mesotrione, I + glufosinate + mesotrione, I + atrazine + isoxaflutole, I + S-metolachlor + isoxaflutole, I + glyphosate + isoxaflutole, I + glufosinate + isoxaflutole, I + glyphosate + fomesafen.
In addition, the present invention also includes four-way mixtures of a compound of formula (I), a herbicide as defined above and two further herbicides. In particular, the following four-way mixture is preferred: I + atrazine + mesotrione + S-metolachlor.
The mixing partners of the compound of formula (I) may also be in the form of esters or salts, as mentioned e.g. in The Pesticide Manual, 14th Edition (BCPC), 2006. For example, the reference to acifluorfen-sodium also applies to acifluorfen, the reference to dimethenamid also applies to dimethenamid-P, the reference to glufosinate-ammonium also applies to glufosinate, the reference to bensulfuron-methyl also applies to bensulfuron, the reference to cloransulam- methyl also applies to cloransulam, the reference to flamprop-M also applies to flamprop, and the reference to pyrithiobac-sodium also applies to pyrithiobac, etc.
The mixing ratio of the compound of formula (I) to the mixing partner is preferably from 1 : 100 to 1000: 1.
The mixtures can advantageously be used in the above-mentioned formulations (in which case "active ingredient" relates to the respective mixture of compound of formula (I) with the mixing partner).
Compounds of formula (I) may also be combined with herbicide safeners. As
combinations with safeners, are preferred, for example, (wherein Ί" represents a compound of formula (I)) I + AD-67, I + benoxacor, I + cloquintocet-mexyl, I + cyomerinil, I + dichlormid, I + dicyclonone, I + cyprosulfamide, I + diethorate, I + DKA-24, I + dymron, I + fenclorazole ethyl, I + fenclorim, I + HEXIM, I + flurazole, I + fluxofenim, I + furilazole, I + isoxadifen, I + isoxadifen ethyl, I + MCPA, I + mecoprop, I + mefenpyr, I + mefenpyr ethyl, I + mefenpyr diethyl, I + mephenate, I + MG-191 , I + NA (naphthalic anhydride), I + OM (octamethylene diamine), I + oxabetrinil, I + - -
PPG-1292, I + R-29148, I + N-(2-methoxybenzoyl)-4-
[(methylaminocarbonyl)amino]benzenesulfonamide and the like are mentioned. These components can be used alone or by mixing 2 or more types, and the ratio when they are mixed can also be freely selected. In particular, the following compound/safener combinations are preferred: I + cloquintocet- mexyl, I + cyprosulfamide, I + N-(2-methoxybenzoyl)-4-
[(methylaminocarbonyl)amino]benzenesulfonamide, I + isoxad if en-ethyl, I + benoxacor, I + dichlormid and I + fluxofenim.
The safeners of the compound of formula (I) may also be in the form of esters or salts, as mentioned e.g. in The Pesticide Manual, 14th Edition (BCPC), 2006. For example, the reference to cloquintocet-mexyl also applies to cloquintocet and to a lithium, sodium, potassium, calcium, magnesium, aluminium, iron, ammonium, quaternary ammonium, sulfonium or phosphonium salt thereof as disclosed in WO02/34048 and the reference to fenchlorazole-ethyl also applies to fenchlorazole, etc. Preferably the mixing ratio of compound of formula (I) to safener is from 100: 1 to 1 :10, especially from 20: 1 to 1 : 1.
The mixtures can advantageously be used in the above-mentioned formulations (in which case "active ingredient" relates to the respective mixture of compound of formula (I) and any further active ingredient, in particular a further herbicide, with the safener). It is possible that the safener and a compound of formula (I) and one or more additional herbicide(s), if any, are applied simultaneously. For example, the safener, a compound of formula (I) and one or more additional herbicide(s), if any, might be applied to the locus pre-emergence or might be applied to the crop post-emergence. It is also possible that the safener and a compound of formula (I) and one or more additional herbicide(s), if any, are applied sequentially. For example, the safener might be applied before sowing the seeds as a seed treatment and a compound of formula (I) and one or more additional herbicides, if any, might be applied to the locus pre-emergence or might be applied to the crop post-emergence.
Various aspects and embodiments of the present invention will now be illustrated in more detail by way of example. It will be appreciated that modification of detail may be made without departing from the scope of the invention.
For the avoidance of doubt, where a literary reference, patent application, or patent, is cited within the text of this application, the entire text of said citation is herein incorporated by reference. - -
Examples
Example 1 Synthesis of Preparation of A -{2-[(9,10-dioxo-8-azaspiro[4.5]decan-8- yl)methyl]phenyl}-1,1,1 -trifluoro-methanesulfonamide (Compound 13-38)
Step 1.1 Synthesis of 2-cvano-2-cvclopentylidene-acetic acid
Figure imgf000086_0001
Piperidine (0.18 g, 2.12 mmol) was added to a stirred mixture of ethyl 2-cyanoacetate (6g, 53 mmol) and cyclopentanone (4.4 g, 53 mmol) at room temperature and stirring continued for 2 hours. The reaction mixture was diluted with water (100 ml) and extracted with ethyl acetate (3 x 100 ml). The combined organic extracts were washed with water, dried over sodium sulfate and concentrated under reduced pressure to leave a residue which was purified by silica gel chromatography to provide 2-cyano-2-cyclopentylidene-acetic acid (8.27 g, 87%). H NMR (400 MHz, CDCI3) δ 4.27 (m, 2H), 3.00 (t, 2H), 2.81 (t, 2H), 1.90-1.70 (m, 4H), 1.34 (t, 3H) ppm.
Step 1.2 Synthesis of 2-cvano-2-[1-(2-hvdroxy-1-methoxy-2-oxo-ethyl)cvclopentyllacetic acid
Figure imgf000086_0002
Ethyl-2-methoxyacetate (2.9 g, 24.5 mmol) was slowly added to a stirred solution of lithium hexamethyldisilazide (1 M in THF; 30 ml, 30 mmol) in tetrahydrofuran (40 ml) at -78 °C. After stirring for 40 minutes at -78 °C a solution of 2-cyano-2-cyclopentylidene-acetic acid (4 g, 22 mmol) in tetrahydrofuran (20 ml) was added. The resulting mixture was stirred for 1 hour at -78 °C, allowed to warm to room temperature over 30 minutes, stirred for 2 hours, then water (60 ml) added. The mixture was extracted with ethyl acetate (3 x 150 ml) and the combined organic extracts washed with water, dried over sodium sulfate and concentrated under reduced pressure to leave a residue which was then purified by silica gel chromatography to provide 2-cyano-2-[1- (2-hydroxy-1-methoxy-2-oxo-ethyl)cyclopentyl]acetic acid (5.4 g, 90 %). H NMR (400 MHz, CDCI3) δ 4.28 (m, 4H), 3.93 (m, 2H), 3.34 (s, 3H), 2.17-1.36 (m, 8H), 1.37- 1.33 (m, 6H) ppm.
Step 1.3 Synthesis of 2-[1-(cyanomethyl)cvclopentyll-2-methoxy-acetic acid - -
Figure imgf000087_0001
A solution of lithium chloride (2.49 g, 58.8 mmol) in water (35 ml) was added to a stirred solution of 2-cyano-2-[1-(2-hydroxy-1-methoxy-2-oxo-ethyl)cyclopentyl] acetic acid (7 g, 24 mmol) in dimethyl sulfoxide (70 ml) at room temperature. The resulting mixture was heated at 1 10 °C for 45 hours, then allowed to cool to room temperature, water added and extracted with ethyl acetate (3 x 100 ml). The combined organic extracts were washed with water, dried over sodium sulfate and concentrated under reduced pressure to leave a residue which was purified by silica gel chromatography to provide 2-[1-(cyanomethyl)cyclopentyl]-2-methoxy-acetic acid (4.6 g, 87%). H NMR (400 MHz, CDCI3) δ 4.26 (m, 2H), 3.69 (s, 1 H), 3.38 (s, 3H), 2.69-2.45 (m, 2H), 1.89- 1.69 (m, 2H), 1.70-1.64 (m, 5H), 1.63 (m, 1 H), 1.33 (t, 3H) ppm.
Step 1 .4 Synthesis of 10-methoxy-8-azaspiro[4.5ldecan-9-one
Figure imgf000087_0002
A solution of cobalt (II) chloride hexahydrate (2.56 g, 19.8 mmol) in water (44.5 ml) was added to a solution of 2-[1-(cyanomethyl)cyclopentyl]-2-methoxy-acetic acid (4.45 g, 19.8 mmol) in tetrahydrofuran (89 ml). Sodium borohydride (3.81 g, 98.8 mmol) was added portionwise over 15 minutes to this stirred mixture at room temperature and stirring continued for 18. The resulting mixture was diluted with 20% isopropyl alcohol in chloroform (40 ml) and filtered through a bed of Celite®. The filtrate was washed with water (30 ml), dried over sodium sulfate and concentrated under reduced pressure to provide 10-methoxy-8-azaspiro[4.5]decan-9-one (3.2 g, 88%). H NMR (400 MHz, CDCI3) δ 6.01 (s, 1 H), 3.59 (s, 3H), 3.39-3.28 (m, 2H), 3.24 (s, 1 H), 2.04-1.69 (m, 1 H), 1.78 (m, 1 H), 1.66 (m, 4H), 1.56-1.36 (m, 4H) ppm.
Step 1 .5 Synthesis of 10-hydroxy-8-azaspiro[4.5ldecan-9-one - -
Figure imgf000088_0001
Boron tribromide (1 M solution in dichloromethane; 1.06 ml, 1.06 mmol) was added dropwise to a stirred solution of 10-methoxy-8-azaspiro[4.5]decan-9-one (150 mg, 0.81 mmol) in
dichloromethane (6 ml) maintaining the temperature below -70 °C. The mixture was stirred for 30 minutes, allowed to warm to room temperature and stirred for 2 hours. Aqueous sodium bicarbonate solution was added until the mixture reached pH 7 and the mixture extracted with dichloromethane (3 x 30 ml). The combined organic extracts were washed with water, dried over sodium sulfate and concentrated under reduced pressure to provide 10-hydroxy-8- azaspiro[4.5]decan-9-one (130 mg, 97 %), which was used without further purification. H NMR (400 MHz, CDCI3) 5 5.85 (br s, 1 H), 3.95 (s, 1 H), 3.39-3.26 (m, 2H), 2.01-1.86 (m, 1 H), 1.85-1.70 (m, 1 H), 1.74-1.54 (m, 6H), 1.71-1.34 (m, 2H) ppm.
Step 1.6 Synthesis of 8-azaspiro[4.5ldecane-9, 10-dione
Figure imgf000088_0002
Dess-Martin periodinane (0.39 g, 0.92 mmol) was added to a stirred solution of 10-hydroxy-8- azaspiro[4.5]decan-9-one (130 mg, 0.76 mmol) in dichloromethane (2.6 ml) under nitrogen and the resulting mixture stirred for 2 hours at room temperature. Dichloromethane (50 ml) was added, followed by 2% aqueous sodium thiosulfate (5 ml) and saturated aqueous sodium bicarbonate (15 ml). The organic layer was separated, dried over sodium sulfate and concentrated under reduced pressure to provide 8-azaspiro[4.5]decane-9, 10-dione (125 mg, 97 %), which was used without further purification. H NMR (400 MHz, CDCI3) δ 8.06 (s, 1 H), 3.50-3.42 (m, 2H), 2.12-2.04 (m, 4H), 1.73-1.68 (m, 4H), 1.52-1.48 (m, 2H) ppm.
Step 1 .7 Synthesis of 10-methoxyimino-8-azaspiro[4.5ldecan-9-one - -
Figure imgf000089_0001
Sodium acetate (59 mg, 0.71 mmol) and O-methoxylamine hydrochloride (59 mg, 0.71 mmol) were added to a stirred solution of 8-azaspiro[4.5]decane-9, 10-dione (100 mg, 0.59 mmol) in methanol (1 ml) at room temperature. The resulting mixture was heated at reflux for 2 hours, allowed to cool to room temperature and concentrated under reduced pressure. Water was added to the residue and the resulting mixture extracted with ethyl acetate (3 x 30 ml). The combined organic extracts were washed with water, dried over sodium sulfate and concentrated under reduced pressure to leave a residue which was purified by silica gel chromatography to provide 10-methoxyimino-8-azaspiro[4.5]decan-9-one (62 mg, 53 %). H NMR (400 MHz, CDCI3) δ 7.80 (s, 1 H), 4.06 (s, 3H), 3.34-3.25 (m, 2H), 2.31-2.26 (m, 2H), 1.88-1.84 (m, 2H), 1.77-1.72 (m, 2H), 1.65-1.62 (m, 2H), 1.58-1.43 (m, 2H) ppm.
Step 1.8 Synthesis of 1 ,1 , 1-trifluoro-A/-{2-[(10-methoxyimino-9-oxo-8-azaspiro[4.5ldecan-8- vDmethyllphenvDmethanesulfonamide
Figure imgf000089_0002
Potassium tertiary butoxide (1 M in tetrahydrofuran; 0.64 ml, 0.64 mmol) was added to a stirred solution of 10-methoxyimino-8-azaspiro[4.5]decan-9-one (50 mg, 0.25 mmol) in tetrahydrofuran (1 ml) at room temperature and stirring continued for 15 minutes. A/-[2-(Chloromethyl)phenyl]- 1 , 1 , 1-trifluoro-methanesulfonamide (77 mg, 28 mmol) was added and the resulting mixture stirred for 3 hours. Saturated aqueous ammonium chloride was added and the mixture extracted with ethyl acetate (3 x 30 ml ). The combined organic extracts were washed with water, dried over sodium sulfate and concentrated under reduced pressure to leave a residue which was purified by silica gel chromatography to provide 1 ,1 ,1-trifluoro-A/-{2-[(10-methoxyimino-9-oxo-8- azaspiro[4.5]decan-8-yl)methyl]phenyl}methanesulfonamide (35 mg, 32 %).
Melting point 213-215 °C; H NMR (400 MHz, CDCI3) 5 1 1 .12 (s, 1 H), 7.60 (d, 1 H), 7.39 (m, 1 H), 7.32 (m, 1 H), 7.24 (m, 1 H), 4.56 (s, 2H), 4.08 (s, 3H), 3.57 (m, 2H), 2.27 (m, 2H), 1.85 (m, 2H), 1 .75 (m, 2H), 1.66 (m, 2H), 1 .41 (m, 2H) ppm. - -
Step 1 .9 Synthesis of Λ/-{2-[(9 , 10-dioxo-8-azaspiro[4.5ldecan-8-yl)methvnphenyl)-1 , 1 , 1-trifluoro- methanesulfonamide (Compound 13-38)
Figure imgf000090_0001
p-Toluenesulfonic acid monohydrate (8.7 g, 46 mmol), formalin (37% aq.; 18 ml, 230 mmol) and water (1 1 ml) were added to a stirred solution of 1 , 1 , 1-trifluoro-A/-{2-[(10-methoxyimino-9-oxo-8- azaspiro[4.5]decan-8-yl)methyl]phenyl}methanesulfonamide (10 g, 23.07 mmol) in dioxane (100 ml) at room temperature. The resulting mixture was heated at 100 °C for 30 minutes, allowed to cool and concentrated under reduced pressure. Water was added and the resulting mixture extracted with ethyl acetate (3 x 300 ml). The combined organic extracts were washed with water, dried over sodium sulfate and concentrated under reduced pressure to leave a residue which was purified by silica gel chromatography to provide A/-{2-[(9, 10-dioxo-8- azaspiro[4.5]decan-8-yl)methyl]phenyl}-1 , 1 ,1-trifluoro-methanesulfonamide (6.23 g, 67 %). H NMR (400 MHz, CDCI3) δ 10.71 (s, 1 H), 7.60 (d, 1 H), 7.43 (t, 1 H), 7.35-7.28 (m, 2H), 4.58 (s, 2H), 3.75 (t, 2H), 2.14-2.05 (m, 4H), 1.72-1.48 (m, 6H) ppm. Example 2 Preparation of A -{2-[(8,9-dioxo-7-azaspiro[3.5]nonan-7-yl)methyl]phenyl}-1,1,1 - trifluoro-methanesulfonamide (Compound 13-37)
Step 2.1 Synthesis of 1 ,1 , 1-trifluoro-A/-{2-[(9-methoxy-8-oxo-7-azaspiro[3.5lnonan-7- vDmethyllphenvDmethanesulfonamide
Figure imgf000090_0002
Potassium tertiary butoxide (1 M in tetrahydrofuran; 25 ml, 25 mmol) was added to a stirred solution of 9-methoxy-7-azaspiro[3.5]nonan-8-one (1.7 g, 10 mmol) in tetrahydrofuran (17 ml) at 0 °C and stirring continued for 30 minutes. A solution of A/-[2-(chloromethyl)phenyl]-1 , 1 , 1-trifluoro- methanesulfonamide (2.7 g, 10 mmol) in tetrahydrofuran (8.5 ml) was added and the resulting mixture stirred 0 °C for 1 hour, then allowed to warm and stirred at room temperature for 2 hours. Saturated aqueous ammonium chloride was added and the mixture extracted with ethyl acetate (3 x 50 ml). The combined organic extracts were washed with water, dried over sodium sulfate - - and concentrated under reduced pressure to leave a residue which was purified by silica gel chromatography to provide 1 ,1 ,1-trifluoro-A/-{2-[(9-methoxy-8-oxo-7-azaspiro[3.5]nonan-7- yl)methyl]phenyl}methanesulfonamide (2.8 g, 69 %). H NMR (400 MHz, CDCI3) δ 1 1 .70 (s, 1 H), 7.62 (d, 1 H), 7.38 (t, 1 H), 7.26-7.17 (m, 2H), 4.55- 4.37 (m, 2H), 3.62 (s, 3H), 3.49 (s, 1 H), 3.42-3.33 (m, 2H), 2.13-2.08 (m, 2H), 1.94-1.86 (m, 2H), 1.86-1.70 (m, 4H) ppm.
Step 2.2 Synthesis of 1 ,1 , 1-trifluoro-A/-{2-[(9-hydroxy-8-oxo-7-azaspiro[3.5lnonan-7- vDmethvUphenvDmethanesulfonaiTiide
Figure imgf000091_0001
Boron tribromide (1 M solution in dichloromethane; 8.3 ml, 8.3 mmol) was added dropwise to a stirred solution of 1 ,1 , 1-trifluoro-A/-{2-[(9-methoxy-8-oxo-7-azaspiro[3.5]nonan-7- yl)methyl]phenyl}methanesulfonamide (2.8 g, 6.9 mmol) in dichloromethane (8.3 ml) maintaining the temperature below -70 °C. The mixture was stirred for 30 minutes, allowed to warm to room temperature and stirred for 2 hours. Aqueous sodium bicarbonate solution was added until the mixture reached pH 7 and the mixture extracted with dichloromethane (3 x 150 ml). The combined organic extracts were washed with water, dried over sodium sulfate and concentrated under reduced pressure to leave a residue which was purified by silica gel chromatography to provide 1 , 1 , 1-trifluoro-A/-{2-[(9-hydroxy-8-oxo-7-azaspiro[3.5]nonan-7- yl)methyl]phenyl}methanesulfonamide (1.7 g, 63 %). H NMR (400 MHz, CDCI3) 5 1 1 .14 (s, 1 H), 7.62 (d, 1 H), 7.40 (t, 1 H), 7.38-7.28 (m, 2H), 4.51- 4.38 (m, 2H), 3.81 (s, 1 H), 3.58 (s, 1 H), 3.51-3.39 (m, 2H), 2.36-2.12 (m, 1 H), 2.10-1.91 (m, 2H), 1.91-1.88 (m, 3H), 1.82-1.70 (m, 1 H), 1.70-1.52 (m, 1 H) ppm.
Step 2.3 Synthesis of A/-{2-[(8,9-dioxo-7-azaspiro[3.5lnonan-7-yl)methyllphenyl)-1 , 1 , 1-trifluoro- methanesulfonamide (Compound 13-37)
Figure imgf000091_0002
- -
Dess-Martin periodinane (2.4 g, 5.6 mmol) was added to a stirred solution of 1 , 1 , 1 -trifluoro- V-{2- [(9-hydroxy-8-oxo-7-azaspiro[3.5]nonan-7-yl)methyl]phenyl}methanesulfonamide (1 .7 g, 4.3 mmol) in dichloromethane (34 ml) under nitrogen and the resulting mixture stirred for 9 hours at room temperature. Dichloromethane (150 ml) was added, followed by 2% aqueous sodium thiosulfate (40 ml) and saturated aqueous sodium bicarbonate (50 ml). The organic layer was separated, dried over sodium sulfate and concentrated under reduced pressure to leave a residue which was purified by silica gel chromatography to provide A/-{2-[(8,9-dioxo-7- azaspiro[3.5]nonan-7-yl)methyl]phenyl}-1 , 1 , 1-trifluoro-methanesulfonamide (1 .3 g, 57 %). H NMR (400 MHz, CDCI3) δ 7.57 (d, 1 H), 7.41 (t, 1 H), 7.33 (d, 1 H), 7.29-7.23 (m, 1 H), 4.57 (s, 2H), 3.73 (t, 2H), 2.46-2.39 (m, 2H), 2.26 (t, 2H), 2.03-1.88 (m, 4H) ppm.
Example 3 Preparation of 1,1,1-trifluoro-A -(2-{[(1S,2 ?,6S)-6-isopropyl-2-methyl-4,5-dioxo- 3-azabicyclo[4.1.0]heptan-3-yl]methyl}phenyl)methanesulfonamide (Compound 13-44)
Step 3.1 Synthesis of (1 2 5S)-5-isopropyl-2-methyl-bicyclo[3.1.0lhexan-3-one E-oxime
Figure imgf000092_0001
A solution of sodium hydroxide (2.40 g, 60.0 mmol) in water (45 ml) was added slowly to a stirred solution of (1 R,2R,5S)-5-isopropyl-2-methyl-bicyclo[3.1.0]hexan-3-one (5 ml, 30 mmol) and hydroxylamine hydrochloride (2.09 g, 30.0 mmol) in ethanol (15 ml) and water (15 ml) at 0 °C under nitrogen, maintaining the temperature below 30 °C. The resulting mixture was stirred at room temperature for 24 hours and then extracted with ethyl acetate. The combined organic extracts were washed with brine, dried over magnesium sulphate, filtered and concentrated under reduced pressure to leave a residue which was purified by silica gel chromatography to provide (1 R,2R,5S)-5-isopropyl-2-methyl-bicyclo[3.1.0]hexan-3-one E-oxime (2.93 g, 58%). H NMR (400 MHz, CDCI3) 5 7.71 (br s, 1 H), 2.71 (d, 1 H), 2.68-2.59 (dq, 1 H), 2.40 (td, 1 H), 1.36 (quintet, 1 H), 1.16 (d, 3H), 1.01-0.91 (m, 7H), 0.55 (ddd, 1 H), 0.04 (dd, 1 H) ppm. Step 3.2 Synthesis of (1 S,2 6S)-6-isopropyl-2-methyl-3-azabicyclo[4.1.0lheptan-4-one - -
Figure imgf000093_0001
A solution of sodium hydroxide (2.77 g, 69.4 mmol) in water (17 ml) was added slowly to a stirred solution of (1 R,2R,5S)-5-isopropyl-2-methyl-bicyclo[3.1.0]hexan-3-one E-oxime (2.90 g, 17.3 mmol) in acetone (52 ml). A solution of 4-methylbenzenesulfonyl chloride (5.95 g, 31 .2 mmol) in acetone (52 ml) was added and the resulting mixture stirred at room temperature for 24 hours. Hydrochloric acid was added to bring the mixture to neutral pH and it was then extracted with dichloromethane. The combined organic extracts were dried over magnesium sulphate, filtered and concentrated under reduced pressure to leave a residue which was purified by silica gel chromatography to provide (1 S,2R,6S)-6-isopropyl-2-methyl-3-azabicyclo[4.1.0]heptan-4-one (2.43 g, 88%). H NMR (400 MHz, CDCI3) δ 3.76-3.68 (m, 1 H), 2.49 (br d, 2H), 2.20 (br s, 1 H), 1 .33 (d, 3H), 1.17-1.06 (m, 1 H), 0.99 (d, 3H), 0.95 (d, 3H), 0.91-0.78 (m, 1 H), 0.60 (t, 1 H), 0.50 (dd, 1 H) ppm.
Step 3.3 Synthesis of 1 , 1 , 1 -trifluoro-A/-(2-{[(1 S,2 6S)-6-isopropyl-2-methyl-4-oxo-3- azabicvclo[4.1.01heptan-3-yllmethyl)phenyl)methanesulfonamide
Figure imgf000093_0002
Potassium tertiary butoxide (1 M in tetrahydrofuran; 30.2 ml, 30.2 mmol) was added to a stirred solution of provide (1 S,2R,6S)-6-isopropyl-2-methyl-3-azabicyclo[4.1.0]heptan-4-one (2.42 g, 14.5 mmol) in tetrahydrofuran (30 ml) at room temperature and stirring continued for 15 minutes. A solution of A/-[2-(chloromethyl)phenyl]-1 , 1 ,1 -trifluoro-methanesulfonamide (3.31 g, 12.1 mmol) in tetrahydrofuran (18 ml) was added and the resulting mixture stirred for 16 hours. Hydrochloric acid was added and the mixture extracted with ethyl acetate. The combined organic extracts were washed with water, dried over magnesium sulfate and concentrated under reduced pressure to leave a residue which was purified by silica gel chromatography to provide 1 , 1 ,1- trifluoro-A/-(2-{[(1 S,2R,6S)-6-isopropyl-2-methyl-4-oxo-3-azabicyclo[4.1.0]heptan-3- yl]methyl}phenyl)methanesulfonamide (3.91 g, 80 %). - - H NMR(400 MHz, CDCI3) δ 11.64 (br s, 1H), 7.61 (dd, 1H), 7.37 (t, 1H), 7.27 (dd, 1H), 7.23- 7.16 (m, 1H), 4.65 (d, 1H), 4.17 (d, 1H), 3.90 (dd, 1H), 2.63 (dd, 1H), 2.52-2.44 (m, 1H), 1.31 (d, 3H), 1.16-1.04 (m, 1H), 1.02-0.88 (m, 7H), 0.32 (ddd, 1H), 0.13 (t, 1H) ppm.
Step 3.4 Synthesis of 1,1,1 -trifluoro-/V-(2-{[(1S,2 6S,Z)-5-hvdroxyimino-6-isopropyl-2-methyl-4- oxo-3-azabicyclo[4.1.01heptan-3-yllmethyl)phenyl)methanesulfonamide
Figure imgf000094_0001
Sodium hexamethyldisilazide (1M in tetrahydrofuran; 7.4 ml, 7.4 mmol) was added to a stirred solution of 1 , 1 , 1 -trifluoro-A/-(2-{[(1 S,2R,6S)-6-isopropyl-2-methyl-4-oxo-3- azabicyclo[4.1.0]heptan-3-yl]methyl}phenyl)methanesulfonamide (0.86 g, 2.1 mmol) in tetrahydrofuran (10.6 ml). The resulting mixture was stirred at room temperature for 30 minutes, then isopentyl nitrite (0.43 ml, 3.2 mmol) was added and stirring continued. Further sodium hexamethyldisilazide (1M in tetrahydrofuran; 3.7 ml, 3.7 mmol) and isopentyl nitrite (0.43 ml, 3.2 mmol) were added and stirring continued for 17 hours. Hydrochloric acid was added and the mixture extracted with ethyl acetate. The combined organic extracts were washed with brine, dried over magnesium sulphate, filtered and concentrated under reduced pressure to leave a residue which was purified by silica gel chromatography to provide 1,1,1-trifluoro-A/-(2- {[(1S,2R,6S,Z)-5-hydroxyimino-6-isopropyl-2-methyl-4-oxo-3-azabicyclo[4.1.0]heptan-3- yl]methyl}phenyl)methanesulfonamide (0.29 g, 31%). H NMR(400 MHz, CDCI3) δ 13.26 (br s, 1H), 10.00 (br s, 1H), 7.59 (d, 1H), 7.42 (dt, 1H), 7.32- 7.24 (m, 2H), 4.81 (d, 1H), 4.13 (d, 1H), 4.08-4.01 (m, 1H), 2.19 (m, 1H), 1.41-1.35 (m, 4H), 1.01 (d, 3H), 0.96-0.90 (m, 1H), 0.89 (d, 3H), 0.42 (t, 1H) ppm.
Step 3.5 Synthesis of 1,1,1 -trifluoro-A/-(2-{[(1S,2 6S)-6-isopropyl-2-methyl-4,5-dioxo-3- azabicyclo[4.1.01heptan-3-yllmethyl)phenyl)methanesulfonamide (Compound 13-44)
Figure imgf000094_0002
p-Toluenesulfonic acid monohydrate (0.19 g, 0.50 mmol), formalin (37% aq.; 0.37 ml, 5.0 mmol) and water (0.25 ml) were added to a stirred solution of 1,1,1-trifluoro-A/-(2-{[(1S,2R,6S,Z)-5- hyd roxyi mi no-6-isopropyl-2-m ethyl-4-oxo-3-azabicyclo[4.1.0] heptan-3- - - yl]methyl}phenyl)methanesulfonamide (0.215 g, 0.496 mmol) in tetrahydrofuran (2.2 ml) at room temperature. The resulting mixture was heated at 100 °C for 90 minutes in a microwave reactor, then allowed to cool. Water was added and the resulting mixture extracted with ethyl acetate. The combined organic extracts were washed with brine, dried over magnesium sulfate, filtered and concentrated under reduced pressure to leave a residue which was purified by silica gel chromatog raphy to provide 1 , 1 , 1 -trif I uoro-A/-(2-{[( 1 S,2R, 6S)-6-isopropyl-2-m ethyl-4 ,5-d ioxo-3- azabicyclo[4.1.0]heptan-3-yl]methyl}phenyl)methanesulfonamide (147 mg, 71 %). H NMR (400 MHz, CDCI3) δ 7.58 (d, 1 H), 7.43-7.24 (m, 3H), 4.81 (d, 1 H), 4.18-4.05 (m, 2H), 1.92 (heptet, 1 H), 1.76 (ddd, 1 H), 1.44 (d, 3H), 1.19 (dd, 1 H), 1.05-0.94 (m, 7H) ppm. Example 4 Preparation of A -(2-{[3-(cyclopentylmethylene)-2-oxo-1 - piperidyl]methyl}phenyl)-1,1,1 -trifluoro-methanesulfonamide (Compound 13-221)
Step 4.1 Synthesis of 3-(cvclopentylmethylene)piperidin-2-one
Figure imgf000095_0001
n-Butyl lithium (2M in cyclohexane; 15 ml, 30 mmol) was added to a solution of piperidin-2-one (1.0 g, 10.1 mmol) in tetrahydrofuran (15 ml) at 0 °C and the resulting mixture stirred for 60 minutes, then cooled to -78 °C and a solution of cyclopentane carboxaldehyde (1.43 g, 12.1 mmol) in tetrahydrofuran (5 ml) added. The mixture was warmed to room temperature and stirred for 5 hours, then saturated aqueous ammonium chloride added and the mixture extracted with ethyl acetate (3 x 100 ml). The combined organic extracts were washed with water, dried over sodium sulfate and concentrated under reduced pressure to leave a residue which was purified by silica gel chromatography to provide 3-(cyclopentylmethylene)piperidin-2-one (0.7 g, 39 %). H NMR (400 MHz, CDCI3) δ 6.20 (br s, 1 H), 3.80-3.75 (m, 1 H), 3.30- 3.27 (m, 2H), 2.32-1.80 (m, 4H), 1.80-1.45 (m, 9H) ppm.
Step 4.2 synthesis of A/-(2-{[3-(cvclopentylmethylene)-2-oxo-1-piperidyllmethyl)phenyl)-1 , 1 ,1- trifluoro-methanesulfonamide (Compound 13-221 )
Figure imgf000095_0002
Potassium tertiary butoxide (1 M in tetrahydrofuran; 9.8 ml, 9.8 mmol,) was added to a stirred solution of 3-(cyclopentylmethylene)piperidin-2-one (700 mg, 3.9 mmol) in tetrahydrofuran (7 ml) - - at 0 °C and stirring continued for 30 minutes. A solution of A/-[2-(chloromethyl)phenyl]-1 , 1 ,1- trifluoro-methanesulfonamide (1.17 g, 4.29 mmol) in tetrahydrofuran (3.5 ml) was added and the resulting mixture allowed to warm to room temperature and stirred for 3 hours. Saturated aqueous ammonium chloride was added and the mixture extracted with ethyl acetate (3 x 100 ml). The combined organic extracts were washed with water, dried over sodium sulfate and concentrated under reduced pressure to leave a residue which was purified by silica gel chromatography to provide A/-(2-{[3-(cyclopentylmethylene)-2-oxo-1-piperidyl]methyl}phenyl)- 1 , 1 , 1-trifluoro-methanesulfonamide (190 mg, 12 %).
Melting point 106-108 °C; H NMR (400 MHz, CDCI3) δ 12.30 (s, 1 H), 7.64 (d, 1 H), 7.35 (t, 1 H), 7.3 (s, 1 H), 7.21 (m, 1 H), 6.95 (d, 1 H), 4.54 (s, 2H), 3.50 (t, 2H), 2.68-2.63 (m, 1 H), 2.50-2.46 (m, 2H), 1.86-1.75 (m, 6H), 1.68-1.60 (m, 2H), 1.40-1.35 (m, 2H) ppm.
Example 5 Preparation of A -{2-[(3-benzylidene-4-methyl-2-oxo-1 -piperidyl)methyl]phenyl}- 1,1,1 -trifluoro-methanesulfonamide (Compound 13-324) Step 5.1 Synthesis of tert-butyl 4-methyl-2-oxo-piperidine-1-carboxylate
Figure imgf000096_0001
Di-tertiary-butyl carbonate (4.2 g, 24 mmol) and 4-dimethylaminopyridine (3 g, 24 mmol) were added to a stirred solution of 4-methylpiperidin-2-one (2.5 g, 22 mmol) in dichloromethane (25 ml) at room temperature and the resulting mixture stirred for 16 hours. Water was added and the resulting mixture extracted with dichloromethane (3 x 400 ml). The combined organic extracts were washed with 1 N hydrochloric acid (40 ml) and water, dried over sodium sulfate and concentrated under reduced pressure to provide tert-butyl 4-methyl-2-oxo-piperidine-1- carboxylate (2 g, 42 %). H NMR (400 MHz, CDCI3) δ 3.82-3.75 (m, 1 H), 3.52-3.46 (m, 1 H), 2.62-2.56 (m, 1 H), 2.15-2.07 (m, 1 H), 1.94-1.90 (m, 2H), 1.52 (s, 9H), 1.48-1.42 (m, 1 H), 1.02 (d, 3H) ppm.
Step 5.2 Synthesis of 3-benzylidene-4-methyl-piperidin-2-one
Figure imgf000096_0002
- -
A solution of tert-butyl 4-methyl-2-oxo-piperidine-1-carboxylate (900 mg, 4.22 mmol) and benzaldehyde (630 mg, 5.06 mmol) in tetrahydrofuran (10 ml) was added to a stirred suspension of sodium hydride (220 mg, 5.48 mmol) in tetrahydrofuran (5 ml) at 0 °C and the resulting mixture stirred for 2 hours. 2N Hydrochloric acid was added and the resulting mixture extracted with ethyl acetate (3 x 100 ml). The combined organic extracts were washed with water, dried over sodium sulfate and concentrated under reduced pressure to leave a residue which was purified by silica gel chromatography to provide 3-benzylidene-4-methyl-piperidin-2-one (394 mg, 43 %).
LC-MS: (positive ES MH+) 202.
Step 5.3 Synthesis of A/-{2-[(3-benzylidene-4-methyl-2-oxo-1-piperidyl)methyllphenyl)-1 , 1 ,1- trifluoro-methanesulfonamide (Compound 13-324)
Figure imgf000097_0001
Potassium tertiary butoxide (1 M in tetrahydrofuran; 1 .6 ml, 1.6 mmol) was added to a stirred solution of 3-benzylidene-4-methyl-piperidin-2-one (130 mg, 0.64 mmol) in tetrahydrofuran (2.5 ml) at 0 °C and stirring continued for 30 minutes. A solution of A/-[2-(chloromethyl)phenyl]-1 , 1 ,1- trifluoro-methanesulfonamide (195 mg, 0.71 mmol) in tetrahydrofuran (2.5 ml) was added and the resulting mixture stirred at 0 °C for 30 minutes, then allowed to warm to room temperature and stirred for 2 hours. Saturated aqueous ammonium chloride was added and the mixture extracted with ethyl acetate (3 x 40 ml). The combined organic extracts were washed with water, dried over sodium sulfate and concentrated under reduced pressure to leave a residue which was purified by silica gel chromatography to provide A/-{2-[(3-benzylidene-4-methyl-2-oxo-1- piperidyl)methyl]phenyl}-1 , 1 ,1-trifluoro-methanesulfonamide (270 mg, 95 %).
Melting point 138-140 °C; H NMR (400 MHz, CDCI3) δ 12.22 (s, 1 H), 7.82 (s, 1 H), 7.67 (d, 1 H), 7.46-7.29 (m, 7H), 7.25- 7.17 (m, 1 H), 4.93 (d, 1 H), 4.28 (d, 1 H), 3.73 (m, 1 H), 3.53 (m, 1 H), 3.31 (m, 1 H), 1.92 (m, 1 H), 1.77 (m, 1 H), 1.23 (d, 3H) ppm.
Example 6 Preparation of ethyl A -{2-[(3-benzylidene-4-methyl-2-oxo-1-piperidyl)methyl] phenyl}-A -(trifluoromethylsulfonyl)carbamate (Compound 16-324)
Figure imgf000097_0002
- -
Potassium carbonate (65 mg, 0.45 mmol) was added to a solution of A/-{2-[(3-benzylidene-4- methyl-2-oxo-1-piperidyl)methyl]phenyl}-1 , 1 ,1-trifluoro-methanesulfonamide (100 mg, 0.22 mmol) in acetone (1 ml) and the mixture stirred at room temperature for 20 minutes. Ethyl chloroformate (98 mg, 0.91 mmol) was added and the mixture stirred for 2 hours and then concentrated under reduced pressure. Water was added and the resulting mixture extracted with ethyl acetate (3 x 40 ml). The combined organic extracts were washed with water, dried over sodium sulfate, filtered and concentrated under reduced pressure. The residue was purified by silica gel chromatography to provide A/-{2-[(3-benzylidene-4-methyl-2-oxo-1-piperidyl)methyl]phenyl}-/V- (trifluoromethylsulfonyl)carbamate (80 mg, 68%). Melting point 126-128 °C; H NMR (400 MHz, CDCI3) δ 7.81 (s, 1 H), 7.36-7.51 (m, 8H), 7.23 (d, 1 H), 5.20 (d, 1 H), 4.78-4.91 (m, 1 H), 4.41 (m, 2H), 3.53 (m, 1 H), 3.39 (m, 1 H), 3.21 (m, 1 H), 1 .99 (m, 1 H), 1.74 (m, 1 H), 1.34 (d, 3H), 1.29 (t, 3H) ppm.
Example 7 Preparation of 1,1,1 -trifluoro-A -{2-[(3-methylene-2-oxo-1 -piperidyl)methyl] phenyljmethanesulfonamide (Compound 13-45)
Step 7.1 Synthesis of 3-(hvdroxymethyl) piperidin-2-one
Figure imgf000098_0001
Sodium borohydride (2.56 g, 67.2 mmol) was added to a stirred suspension of ethyl 2- oxopiperidine-3-carboxylate (5 g, 29 mmol) and anhydrous calcium chloride (3.6 g, 32.1 mmol) in methanol (60 ml) at 0 °C and the resulting mixture stirred for 2 hours, allowed to warm to room temperature and stirring continued for 18 hours. The reaction mixture was concentrated under reduced pressure, water added and the mixture adjusted to pH 2-3 with 3N aqueous citric acid and extracted with dichloromethane (3 x 150 ml). The combined organic extracts were washed with water, dried over sodium sulfate and concentrated under reduced pressure to leave a residue which was purified by silica gel chromatography to provide 3-(hydroxymethyl) piperidin-2- one (1.99 g, 46 %). H NMR (400 MHz, CDCI3) δ 6.30 (br s, 1 H), 3.86-3.61 (m, 2H), 3.41-3.22 (m, 2H), 2.53-2.40 (m, 1 H), 2.00-1.70 (m, 3H), 1.59-1.39 (m, 1 H) ppm.
Step 7.2 Synthesis of 3-methylenepiperidin-2-one - -
Figure imgf000099_0001
Dicyclohexyl carbodiimide (1.0 g, 4.8 mmol) and cuprous iodide (60 mg, 0.3 mmol) were added to a stirred solution of 3-(hydroxymethyl) piperidin-2-one (500 mg, 3.87 mmol) in toluene and the resulting mixture heated at reflux for 1 hour, allowed to cool to room temperature and stirred for 18 hours. Water was added and the mixture extracted with ethyl acetate (3 x 250 ml). The combined organic extracts were washed with water, dried over sodium sulfate and concentrated under reduced pressure to leave a residue which was purified by silica gel chromatography to provide 3-methylenepiperidin-2-one (230 mg, 53 %). H NMR (400 MHz, CDCI3) δ 7.30 (s, 1 H), 6.20 (s, 1 H), 5.30 (s, 1 H), 3.40 (m, 2H), 2.55 (m, 2H), 1.70 (m, 2H) ppm.
Step 7.3 Synthesis of 1 ,1 , 1-trifluoro-A/-{2-[(3-methylene-2-oxo-1-piperidyl)methyll
phenvDmethanesulfonamide (Compound 13-45)
Figure imgf000099_0002
Potassium tertiary butoxide (1 M in tetrahydrofuran; 13 ml, 13 mmol) was added to a stirred solution of 3-methylenepiperidin-2-one (570 mg, 5.12 mmol) in tetrahydrofuran (12 ml) at 0 °C and stirring continued for 30 minutes. A solution of A/-[2-(chloromethyl)phenyl]-1 , 1 ,1-trifluoro- methanesulfonamide (1.54 g, 5.64 mmol) in tetrahydrofuran (6 ml) was added and the resulting mixture stirred at 0 °C for 30 minutes, then allowed to warm to room temperature and stirred for 2 hours. Saturated aqueous ammonium chloride (50 ml) was added and the mixture extracted with ethyl acetate (3 x 100 ml). The combined organic extracts were washed with water, dried over sodium sulfate and concentrated under reduced pressure to leave a residue which was purified by silica gel chromatography to provide A/-{2-[(3-benzylidene-4-methyl-2-oxo-1- piperidyl)methyl]phenyl}-1 , 1 ,1-trifluoro-methanesulfonamide (700 mg, 39 %).
Melting point 130-132 °C; H NMR (400 MHz, CDCI3) δ 12.00 (s, 1 H), 7.64 (d, 1 H), 7.38 (m, 1 H), 7.29 (m, 1 H), 7.22 (m, 1 H), 6.34 (s, 1 H), 5.40 (s, 1 H), 4.55 (s, 2H), 3.55 (t, 2H). 2.55 (t, 2H), 1 .89 (m, 2H) ppm.
Compounds made using the general methods described are listed in Table 10 below. - -
TABLE 10 Compounds made according to the general methods described.
Characteristic data is melting point (°C) and/or 1H nmr data (400 MHz, CDCI3 unless otherwise stated) δ Η ppm.
Figure imgf000100_0001
- -
Figure imgf000101_0001
- -
2.68-
2.47
(d, (s,
(m,
2H)
(m,
Figure imgf000102_0001
- -
Figure imgf000103_0001
- -
Figure imgf000104_0001
- -
Figure imgf000105_0001
Example 8 - Herbicidal action
EXAMPLE 8a Pre-emergence biological efficacy
Seeds of Zea mays (ZEAMX), Setaria faberi (SETFA), Echinochloa crus-galli (ECHCG), Lolium perenne (LOLPE), Alopecurus myosuroides (ALOMY), Amaranthus retroflexus (AMARE) and Abutilon theophrasti (ABUTH) were sown in standard soil in pots. After cultivation for one day 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 in acetone / water (50:50) solution containing 0.5% Tween 20 (polyoxyethylene sorbitan monolaurate, CAS RN 9005-64-5) to give a final dose of 250 or 1000 g/ha of test compound.
The test plants were then grown under controlled conditions in the glasshouse (at 24/16°C, day/night; 14 hours light; 65 % humidity) and watered twice daily. After 13 days the test was evaluated (100 = total damage to plant; 0 = no damage to plant). Results are shown below in Table 1 1.
TABLE 11 Percentage damage caused to weed species by compounds of the invention when applied pre-emergence.
Cpd No Rate Species
(g/ha) ZEAMX SETFA ECHCG LOLPE ALOMY AMARE ABUTH
1-13 1000 80 90 90 90 - 80 70
1-197 1000 40 90 90 - 80 100 80
1-198(E) 1000 20 70 60 50 - 30 50
4-198(E) 1000 0 40 70 30 - 30 10
13-31 1000 80 100 90 90 - 70 80 - -
Figure imgf000106_0001
EXAMPLE 8b Post-emergence biological efficacy
Seeds of Zea mays (ZEAMX), Setaria faberi (SETFA), Echinochloa crus-galli (ECHCG), Lolium perenne (LOLPE), Alopecurus myosuroides (ALOMY), Amaranthus retroflexus (AMARE) and Abutilon theophrasti (ABUTH) were sown in standard soil in pots. After cultivation for 8 days 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 in acetone / water (50:50) solution containing 0.5% Tween 20 (polyoxyethylene sorbitan monolaurate, CAS RN 9005-64-5) to give a final dose of 1000 g/ha of test compound.
The test plants were then grown on under controlled conditions in a glasshouse (at 24/16°C, day/night; 14 hours light; 65 % humidity) and watered twice daily. After 13 days the test was evaluated (100 = total damage to plant; 0 = no damage to plant). Results are shown below in Table 12. TABLE 12 Percentage damage caused to weed species by compounds of the invention when applied post-emergence
Cpd No Species - -
ZEAMX SETFA ECHCG LOLPE ALOMY AMARE ABUTH
1-13 60 80 60 60 - 80 60
1-197 70 70 80 - 50 80 80-198(E) 60 30 60 30 - 30 30-198(E) 80 40 60 20 - 40 40
13-31 70 70 70 60 - 70 80
13-37 70 70 60 60 - 80 80
13-38 70 80 70 70 - 90 80
13-44 80 70 70 70 - 90 80
13-45 60 70 60 50 - 20 70
13-221 60 70 70 60 - 70 80
13-265 40 60 50 60 - 40 60
13-309 30 50 30 - 20 50 70
13-324 50 70 50 20 - 90 80
13-353 20 60 70 60 - 80 80
13-397 20 70 80 30 - 80 80
13-412 30 30 60 30 - 80 80
13-441 70 70 80 60 - 90 90 -485(E) 60 60 80 60 - 80 70 -485(Z) 30 30 70 40 - 60 40
13-529 60 50 80 60 - 60 70
16-38 70 80 70 70 - 80 80
16-44 80 70 60 60 - 80 80
16-221 60 70 30 40 - 80 70
16-265 50 50 60 30 - 40 30
16-324 60 70 70 60 - 70 80
16-529 60 40 70 40 - 70 70 1-190 20 60 40 - 40 70 50

Claims

Claims
1. A compound of formula (I)
Figure imgf000108_0001
(I)
wherein
A is selected from CH=CH, CR3=CH, CH=CR3, CR3=CR3 and S;
W is selected from oxygen and sulphur;
X is selected from oxygen and CR9R10; m is 0, 1 or 2; n is 1 , 2, 3 or 4; p is 0, 1 , 2 or 3; with the proviso that 2 < n + p < 4; R is Ci-6haloalkyl;
R is selected from H, C1_4alkyl, C3.5alkenyl, propargyl,
Figure imgf000108_0002
Ci.4alkoxyCi_ 2alkoxyCi-2alkyl, Ci-4haloalkoxyCi-2alkyl,
Figure imgf000108_0003
cyanoCi_2alkyl, d.
4alkylcarbonylCi.2alkyl,
Figure imgf000108_0004
arylCi_2alkyl optionally substituted by 1-3 groups R20, heteroarylCi_2alkyl optionally substituted by 1-3 groups R20, arylthioCi_2alkyl optionally substituted by 1-3 groups R20, arylCi_2alkoxyCi_ 2alkyl optionally substituted by 1-3 groups R20, arylCi_2alkylthioCi_2alkyl optionally substituted by 1-3 groups R20, arylcarbonylCi_2alkyl optionally substituted by 1-3 groups R20, Ci-4alkylcarbonyloxyCi.2alkyl, arylcarbonyloxyCi_2alkyl optionally substituted by 1-3 groups R20, Ci_4alkoxycarbonyloxyCi_2alkyl, aryloxycarbonyloxyCi_2alkyl optionally substituted by 1-3 groups R20,Ci_8alkylcarbonyl, C2.5alkenylcarbonyl, Ci_4haloalkylcarbonyl, Ci-4alkoxyCi-2alkylcarbonyl, C3.6cycloalkylcarbonyl, Ci_4alkoxycarbonylCi_2alkylcarbonyl, arylcarbonyl optionally substituted by 1-3 groups R , aryloxyd-2alkylcarbonyl optionally substituted by 1-3 groups R20, Ci_i0alkoxycarbonyl; Ci_4haloalkoxycarbonyl, C3.
5alkenyloxycarbonyl, propargyloxycarbonyl,
Figure imgf000109_0001
Ci_
4alkylthiocarbonyl, aryloxycarbonyl optionally substituted by 1-3 groups R20, arylCi.
2alkoxycarbonyl optionally substituted by 1-3 groups R20, aminocarbonyl, d-
4alkylaminocarbonyl, di(Ci.4alkyl)anriinocarbonyl, Ci_6alkylsulphonyl, Ci_6haloalkylsulphonyl and arylsulphonyl optionally substituted by 1-3 groups R20, and each R20 is, independently, selected from halogen, C1_4alkyl, C-|.4haloalkyl, Ci_4alkoxy, Ci_4haloalkoxy,
Figure imgf000109_0002
2alkoxy, hydroxy, phenyl and phenoxy; each R2 is, independently, selected from halogen, nitrile, C1_4alkyl, C-|.4haloalkyl, C3.
6cycloalkyl, C2-4alkenyl, C2-4alkynyl, Ci_4alkoxy, Ci_4haloalkoxy,
Figure imgf000109_0003
hydroxy, Ci_4alkylcarbonyl, Ci_4alkylsulphonyl and phenyl, or two R2 groups together form - OCH20- or -OCH2CH2O-; each R3 is, independently, selected from halogen, nitrile, C1_4alkyl, C-|.4haloalkyl, C3.
6cycloalkyl, C2-4alkenyl, C2-4alkynyl, Ci_4alkoxy, Ci_4haloalkoxy,
Figure imgf000109_0004
hydroxy, Ci_4alkylcarbonyl, Ci_4alkylsulphonyl and phenyl, or two R3 groups together form - OCH2O- or -OCH2CH2O-; each R5 and R6 are, independently, selected from H, halogen, cyano, hydroxy, C1_4alkyl, Ci-4haloalkyl, C3.6cycloalkyl,
Figure imgf000109_0005
C2-5alkenyl, C2-5alkynyl, Ci_4alkoxy, Ci_ 4alkylthio, Ci_4alkoxycarbonyl, aryl optionally substituted by 1-3 groups R24, aryloxy optionally substituted by 1-3 groups R24 and arylthio optionally substituted by 1-3 groups R24 or R5 and R6 on the same carbon atom together form a C2-5alkylene chain optionally containing an oxygen atom, or R5 and R6 on different carbon atoms together form a d- 4alkylene chain, or R5 and R 0 together form a C2-4alkylene chain and each R24 is, independently, selected from halogen, cyano, d_4alkyl, C-|.4haloalkyl, Ci_4alkoxy, Ci_ 4haloalkoxy,
Figure imgf000109_0006
hydroxy, phenyl and phenoxy; each R7 and R8 are, independently, selected from H, Ci_5alkyl, Ci_4haloalkyl, C3.6cycloalkyl optionally substituted with 1-3 groups selected from halogen, Ci_4alkyl and phenyl, d- 4alkoxyd_4alkyl, Ci_4alkoxycarbonylaminoCi.4alkyl, Ci.4alkylcarbonyloxyCi.2alkyl, arylCi. 2alkyl optionally substituted by 1-3 groups R2 , aryloxyd-2alkyl optionally substituted by 1-3 groups R2 ,
Figure imgf000109_0007
optionally substituted by 1-3 groups R2 ,d-4alkenyl, hydroxyl, d_4alkoxy, Ci_4alkylthio, Ci.4alkylcarbonyloxy,aryl optionally substituted by 1-3 groups R2 , aryloxy optionally substituted by 1-3 groups R2 , arylthio optionally substituted by 1-3 groups R2 and heteroaryl optionally substituted by 1-3 groups R2 , or R7 and R8 on the same carbon atom together form a d^alkylene chain optionally containing an oxygen or sulphur atom and optionally substituted by 1-3 groups selected from halogen, d.2alkyl and an oxo group, or R7 and R8 on different carbon atoms together form a d_4alkylene chain, or R8 and R 0 together form a C2-4alkylene chain and each R2 is, independently, selected from halogen, cyano, C1_4alkyl, C-|.4haloalkyl, Ci_4alkoxy, Ci_4haloalkoxy, Ci_ 2alkoxyCi.2alkoxy, hydroxy, phenyl and phenoxy or two R2 groups together form -OCH20- or -OCH2CH2O-;
R is selected from H, d-6alkyl, Ci_6haloalkyl, C3-6cycloalkylCi-2alkyl, C3.6cycloalkyl, Ci_ 4alkoxy, Ci_4alkylthio, Ci_4alkylamino, aryl optionally substituted by 1-3 groups R22, arylCi. 2alkyl optionally substituted by 1-3 groups R22 and heteroaryl optionally substituted by 1-3 groups R22 and each R22 is, independently, selected from halogen, nitro, cyano, Ci_4alkyl, Ci-4haloalkyl, Ci_4alkoxy, Ci_4haloalkoxy,
Figure imgf000110_0001
hydroxy, Ci_4alkylthio, Ci_ 4haloalkylthio, Ci_4alkylsulphonyl, Ci_4alkoxycarbonyl, phenyl and phenoxy;
R 0 is selected from H, Ci_6alkyl, Ci_4alkylcarbonyl, Ci_4alkoxycarbonyl, Ci_4alkoxy, d- 4alkylthio, Ci_4alkylamino and Ci_4alkylsulphonyl, or R 0 and R5 or R8 together form a C2- 4alkylene chain; or an N-oxide or salt form thereof.
The compound as claimed in claim 1 , wherein A is selected from CH=CH and CR3=CH.
The compound as claimed in claim 2, wherein A is CH=CH.
The compound as claimed in any one of claims 1 to 3, wherein W is oxygen.
The compound as claimed in any one of claims 1 to 4, wherein m is 0 or 1.
The compound as claimed in claim 5, wherein m is 0.
The compound as claimed in any one of claims 1 to 6, wherein n is 2, 3 or 4.
The compound as claimed in any one of claims 1 to 7, wherein p is 0.
The compound as claimed in any one of claims 1 to 8, wherein R is Ci_2haloalkyl.
The compound as claimed in claim 9, wherein R is trifluoromethyl.
The compound as claimed in any one of claims 1 to 10, wherein R is selected from H, d- 4alkoxyCi-2alkyl, Ci-4alkoxyCi-2alkoxyCi-2alkyl, Ci.4haloalkoxyCi.2alkyl, arylCi_2alkyl optionally substituted by 1-3 groups R20, arylCi-2alkoxyCi-2alkyl optionally substituted by 1- 3 groups R20, Ci.4alkylcarbonyloxyCi.2alkyl, arylcarbonyloxyCi_2alkyl optionally substituted by 1-3 groups R20, Ci.4alkoxycarbonyloxyCi.2alkyl, Ci_8alkylcarbonyl, Ci_4haloalkylcarbonyl, Ci-4alkoxyCi-2alkylcarbonyl, Ci_i0alkoxycarbonyl; Ci_4haloalkoxycarbonyl, Ci_4alkoxyCi_ 2alkoxycarbonyl, aryloxycarbonyl optionally substituted by 1-3 groups R20, aryld- 2alkoxycarbonyl optionally substituted by 1-3 groups R20, Ci_6alkylsulphonyl and d- 6haloalkylsulphonyl.
12. The compound as claimed in claim 11 , wherein R is selected from H, Ci_5alkylcarbonyl, Ci-4haloalkylcarbonyl, d-5alkoxycarbonyl, Ci_4haloalkoxycarbonyl and d- 4haloalkylsulphonyl.
13. The compound as claimed in claim 12, wherein R is selected from H, Ci_5alkylcarbonyl and Ci_5alkoxycarbonyl.
14. The compound as claimed in any one of claims 1 to 13, wherein R7 and R8 are,
independently, selected from H, Ci_5alkyl, Ci_4haloalkyl, C3.6cycloalkyl, Ci_4alkoxyCi_4alkyl, arylCi-2alkyl optionally substituted by 1-3 groups R2 , C2-4alkenyl, Ci_4alkoxy, Ci_4alkylthio, aryl optionally substituted by 1-3 groups R2 , aryloxy optionally substituted by 1-3 groups R2 , arylthio optionally substituted by 1-3 groups R2 and heteroaryl optionally substituted by 1-3 groups R2 , or R7 and R8 on the same carbon atom together form a C2-5alkylene chain optionally containing an oxygen atom, or R7 and R8 on adjacent carbon atoms together form a Ci_4alkylene chain.
15. The compound as claimed in claim 14, wherein R7 and R8 are, independently, selected from H, C1_4alkyl, C-|.3haloalkyl, cyclopropyl, Ci-2alkoxyCi-2alkyl,Ci-3alkoxy, Ci_3alkylthio, aryl optionally substituted by 1-3 groups R2 , aryloxy optionally substituted by 1-3 groups R2 , arylthio optionally substituted by 1-3 groups R2 and heteroaryl optionally substituted by 1-3 groups R2 , or R7 and R8 on the same carbon atom together form a C3.5alkylene chain optionally containing an oxygen atom, or R7 and R8 on adjacent carbon atoms together form a Ci_4alkylene chain.
16. The compound as claimed in claim 15, wherein R7 and R8 are, independently, selected from H, Ci-3alkyl, trifluoromethyl, cyclopropyl, methoxymethyl, Ci_3alkoxy and aryl optionally substituted by 1-2 groups R2 , or R7 and R8 together form a C3.5alkylene chain optionally containing an oxygen atom, or R7 and R8 on adjacent carbon atoms together form a -CH2- group.
17. The compound as claimed in any one of claims 1 to 16, wherein R9 is selected from H, d- 4alkyl, C3.6cycloalkyl and aryl optionally substituted by 1-3 groups R22.
18. The compound as claimed in claim 17, wherein R9 is selected from H, Ci_2alkyl and aryl optionally substituted by 1-3 groups R22. 19. The compound as claimed in any one of claims 1 to 18, wherein R 0 is selected from H, d- 4alkyl, d.2alkoxy and d_2alkylthio.
20. The compound as claimed in claim 19, wherein R 0 is selected from H and C1_4alkyl.
21. A herbicidal composition comprising a compound of formula (I) as defined in any one of claims 1 to 20 together with at least one agriculturally acceptable adjuvant or diluent.
22. A composition according to claim 21 which comprises a further herbicide in addition to the compound of formula (I).
23. A composition according to claim 21 or 22 which comprises a safener.
24. Use of a compound of formula (I) as defined in any one of claims 1 to 20 or a composition as defined in any one of claims 21 to 23 as a herbicide.
25. A method of controlling weeds in crops of useful plants, comprising applying to said weeds or to the locus of said weeds, or to said useful plants or to the locus of said useful plants, a compound of formula (I) as defined in any one of claims 1 to 20 or a composition as claimed in any one of claims 21 to 23.
PCT/EP2016/064090 2015-06-23 2016-06-17 Herbicidal compounds WO2016207083A1 (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2336104A1 (en) * 2008-09-02 2011-06-22 Nissan Chemical Industries, Ltd. Ortho-substituted haloalkylsulfonanilide derivative and herbicide
WO2013061973A1 (en) * 2011-10-25 2013-05-02 石原産業株式会社 Heteroaryl sulfonamide compound or salt thereof
WO2014184070A1 (en) * 2013-05-14 2014-11-20 Syngenta Limited Mixtures of haloalkylsulfonanilide derivatives and herbicides

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2336104A1 (en) * 2008-09-02 2011-06-22 Nissan Chemical Industries, Ltd. Ortho-substituted haloalkylsulfonanilide derivative and herbicide
WO2013061973A1 (en) * 2011-10-25 2013-05-02 石原産業株式会社 Heteroaryl sulfonamide compound or salt thereof
WO2014184070A1 (en) * 2013-05-14 2014-11-20 Syngenta Limited Mixtures of haloalkylsulfonanilide derivatives and herbicides

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