WO2008074991A1 - Nouveaux herbicides - Google Patents

Nouveaux herbicides Download PDF

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Publication number
WO2008074991A1
WO2008074991A1 PCT/GB2007/004735 GB2007004735W WO2008074991A1 WO 2008074991 A1 WO2008074991 A1 WO 2008074991A1 GB 2007004735 W GB2007004735 W GB 2007004735W WO 2008074991 A1 WO2008074991 A1 WO 2008074991A1
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formula
compound
methyl
dimethyl
triazole
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PCT/GB2007/004735
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English (en)
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Jutta Elisabeth Boehmer
Matthew Murdoch Woodhead Mclachlan
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Syngenta Limited
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Publication of WO2008074991A1 publication Critical patent/WO2008074991A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
    • C07D413/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links
    • 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
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/80—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,2

Definitions

  • the present invention relates to novel, herbicidal isoxazoline compounds, to processes for their preparation, to intermediates used in the preparation of these compounds, to compositions comprising these compounds, and to methods of using these compounds to control plants or to inhibit plant growth.
  • Isoxazoline compounds which display herbicidal action are described, for example, in WO 01/012613, WO 02/062770, WO 03/000686, WO 04/010165, JP 2005/035924, JP 2005/213168, WO 06/024820 and WO 07/003294.
  • the preparation of these compounds is also described in WO 04/013106, WO 05/095352 and WO 07/003295.
  • the present invention accordingly relates to compounds of formula (I)
  • R 1 and R 2 are each independently of the other hydrogen, C 1 -C 1O aIlCyI, Ci-Ciohaloalkyl,
  • R 1 and R 2 together with the carbon atom to which they are bonded form a C 3 -C 7 ring, R 3 and R 4 are each independently of the other hydrogen, C 1 -C 1O aHCyI, Q-Qohaloalkyl,
  • C 3 -C 8 cycloalkyl Ca-Cscycloalkyl-d-C ⁇ alkyl or C 1 -C 6 alkoxy-C 1 -C 1 oalkyl, or
  • R 3 and R 4 together with the carbon atom to which they are bonded form a C 3 -C 7 ring, or
  • R 5 is halogen or Ci-C 6 haloalkyl
  • R 6 is hydrogen, cyano, Ci-C ⁇ alkyl, CrQalkoxycarbonyl, halogen or d-C 6 haloalkyl; m is 0, 1 or 2; n is 1, 2 or 3; and
  • Y is one of the following groups wherein
  • R 7 is hydrogen, Q-Cioalkyl, C ⁇ -CjQalkylcarbonyl, Cj-Qohaloalkylcarbonyl, C 1 - C 10 alkoxycarbonyl, CrQohaloalkyl, C 2 -Ci 0 alkenyl, C 2 -Ci O alkynyl, C 3 -C 10 cycloalkyl, C 3 - Ciocycloalkyl-Cj-Cioalkyl, CrCioalkylcarbonyl-Ci-C t Qalkyl, CrC ⁇ alkylsulfonyl, C 1 - C 10 haloalkylsulfonyl or Ci-Qoalkoxy-Q-Cioalkyl;
  • R 8 is hydrogen, Ci-C 10 alkyl, Ci-Cioalkylcarbonyl, Ci-Qohaloalkylcarbonyl, C 1 - Cioalkoxycarbonyl, CrC ⁇ haloalkyl, C 2 -Ci 0 alkenyl, C 2 -C 10 alkynyl, C 3 -C 1 O cycloalkyl, C 3 - Ciocycloalkyl-Ci-C ⁇ oalkyl, halogen, thiol, hydroxy,, cyano, Crdoalkylsulfanyl, C 1 - Cjohaloallcylsulfanyl, Q-CiQalkylsulfinyl, d-Ciohaloalkylsulflnyl, CrC ⁇ alkylsulfonyl, Ci-dohaloalkylsulfonyl, Ci-C 10 alkoxy, Ci-C 10 haloalkoxy, or
  • the compounds of the invention may contain one or more 'asymmetric carbon atoms, for example, in the -CR 5 R 6 - group or in the -CR 3 R 4 -group and may exist as enantiomers (or as pairs of diastereoisomers) or as mixtures of such. Further, when m is 1, the compounds of the invention are sulfoxides, which can exist in two enantiomeric forms, the adjacent carbon can also exist in two enantiomeric forms and the -CR 3 R 4 - group can also exist in two enantiomeric forms.
  • Alkyl groups, haloalkyl groups, hydroxyalkyl groups, alkoxy groups, haloalkoxy groups and alkylene groups can be straight or branched chain.
  • Preferred alkyl groups, haloalkyl groups, hydroxyalkyl groups, alkoxy groups, haloalkoxy groups and alkylene groups each independently contain 1 to 4 carbons.
  • alkyl groups are methyl, ethyl, n-and ⁇ o-propyl and n-, sec-, iso- and tert-bvAy ⁇ , hexyl, nonyl and decyl.
  • Examples of haloalkyl groups are difluoromethyl and 2,2,2-trifluoroethyl.
  • Examples of hydroxy- alkyl groups are 1,2-dihydroxyethyl and 3-hydroxypropyl.
  • alkoxy groups are methoxy, etlioxy, propoxy, butoxy, hexyloxy, nonyloxy and decyloxy.
  • Examples of haloalkoxy groups are difluoromethoxy and 2,2,2-trifiuoroethoxy.
  • alkylene groups are methylene, ethylene, «-and wo-propylene and n ⁇ , sec-, iso- and tert-butylene.
  • Cycloalkyl groups can be in mono-, bi- or tri-cyclic form.
  • Preferred cycloalkyl giOups independently contain 3 to 8 carbons.
  • Examples of monocyclic cycloalkyl groups are cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl.
  • Alkenyl and alkynyl groups and haloalkenyl groups and haloalkynyl groups can be straight or branched chain.
  • alkenyl and alkynyl groups are allyl, but-2- enyl, 3-methylbut-2-enyl, ethynyl, propargyl and but-2-ynyl.
  • haloalkenyl and haloalkynyl groups are trifluoroallyl and l-chloroprop-l-yn-3-yl.
  • Halogen means fluoro, chloro, bromo and iodo, preferably fluoro, chloro or bromo, more preferably fluoro or chloro.
  • the invention relates likewise to the salts which the compounds of formula (I) are able to form with amines, alkali metal and alkaline earth metal bases and quarternary ammonium bases.
  • alkali metal and alkaline earth metal hydroxides as salt formers, special mention should be made of the hydroxides of lithium, sodium, potassium, magnesium and calcium, but especially the hydroxides of sodium and potassium.
  • the compounds of formula (I) according to the invention also include hydrates which may be formed during the salt formation.
  • amines suitable for ammonium salt formation include ammonia as well as primary, secondary and tertiary Q-Qsalkylamines, Q-Qhydroxyalkylamines and C 2 -C 4 alkoxyalkylamines, for example methylamine, ethylamine, n -propylamine, isopropylamine, the four butylamine isomers, R-amylamine, isoamylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, pentadecylamine, hexadecylamine, heptadecylamine, octadecylamine, methylethylamine, methylisopropylamine, methylhexylamine, methylnonylamine, methylpentadecylamine, methyloctadecylamine, ethylbutylamine,
  • Preferred quarternary ammonium bases suitable for salt formation correspond, for example, to the formula [N(R 3 R b R 0 R d )]OH wherein R a , R b , R 0 and Ra are each independently of the others C 1 -C 4 OIlCyI.
  • R a , R b , R 0 and Ra are each independently of the others C 1 -C 4 OIlCyI.
  • Other suitable tetraalkylammonium bases with other anions can be obtained, for example, by anion exchange reactions.
  • 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 bum, albinism, dwarfing and the like.
  • plants refers to all physical parts of a plant, including seeds, seedlings, saplings, roots, tubers, stems, stalks, foliage, and fruits.
  • locus is intended to include soil, seeds, and seedlings, as well as established vegetation.
  • R 1 , R 3 , R 4 , R 5 , R 6 , m, n, Y, R 7 and R 8 are, in any combination, as set out below.
  • R 1 and R 2 are independently Ci-C 10 alkyl or d-CiQhaloalkyl, more preferably Ci-C 6 alkyl or d-C ⁇ haloalkyl, even more preferably d-C ⁇ alkyl, yet even more preferably methyl or ethyl, most preferably methyl.
  • Li a preferred embodiment R 1 and R 2 are both methyl. hi a preferred embodiment R 1 is methyl and R 2 is ethyl.
  • R 3 and R 4 are independently hydrogen, d-C ⁇ alkyl or d-C 10 haloalkyl, more preferably hydrogen, d-C 6 alkyl or Ci-C 6 haloalkyl, most preferably hydrogen.
  • R 5 is halogen or trifluoromethyl, more preferably fluoro or chloro, most preferably fluoro.
  • R 6 is hydrogen, methoxycarbonyl, d-C 6 alkyl or halogen, more preferably hydrogen, fluoro or chloro, most preferably hydrogen or fluoro.
  • R 5 is fluoro and R 6 is hydrogen.
  • R 5 and R 6 are both fluoro.
  • R 5 is chloro and R 6 is hydrogen.
  • R 5 and R 6 are both chloro.
  • R 5 is fluoro and R 6 is chloro.
  • m is 1 or 2, more preferably 2.
  • n 1
  • Y is one of the following groups
  • R 7 is hydrogen, Ci-C 10 alkyl, Ci-C 10 haloalkyl, C 3 -docycloalkyl or C 3 -
  • Ciocycloalkyl-Ci-Cioalkyl more preferably hydrogen, methyl, ethyl, monofluoromethyl, difluoromethyl, trifluoromethyl, cyclopropyl or cyclopropylmethyl, even more preferably methyl, ethyl or cyclopropyl, most preferably methyl or cyclopropyl.
  • R 8 is hydrogen, Ci-C 10 alkyl, C 3 -C 10 cycloalkyl, C 3 - Ciocycloalkyl-Ci-Cioalkyl, halogen, cyano, C 1 -C 1 QaIkOXy or Q-C ⁇ haloalkoxy, more preferably hydrogen, methyl, ethyl, monofluoromethyl, difluoromethyl, trifluoromethyl, cyclopropyl, cyclopropylmethyl, chloro, cyano, methoxy, monofluoromethoxy, difluoro- methoxy or trifluoromethoxy, even more preferably hydrogen, methyl, ethyl, trifluoromethyl or chloro, most preferably hydrogen, methyl, ethyl or trifluoromethyl.
  • a group of preferred compounds of formula (I) comprises those wherein Y is
  • 1,2,4-triazolyl which is optionally substituted by one to two substituents independently selected from Ci-C 6 alkyl, d-Cehaloalkyl, C 3 -C 6 cycloalkyl, C 3 -C 6 cycloalkyl-Ci-C 6 -alkyl, halogen, cyano, Ci-C 6 alkoxy or Ci-C 6 haloalkoxy, more preferably wherein Y is 1,2,4- triazolyl which is optionally substituted by one to two substituents independently selected from methyl, ethyl, monofluoromethyl, difluoromethyl, trifluoromethyl, cyclopropyl, cyclopropylmethyl, chloro, cyano, methoxy, monofluoromethoxy, difluoromethoxy or trifluoromethoxy, even more preferably wherein Y is 1,2,4-triazolyl which is optionally substituted by one to two substituents independently selected from methyl, ethyl
  • a group of especially preferred compounds of formula (I) comprises those wherein Y is l,2,4-triazol-3-yl which is optionally substituted by one to two substituents independently selected from Q-dsalkyl, Ci-C 6 haloalkyl, C 3 -C 6 cycloalkyl, C 3 -C 6 cyclo- alkyl-Ci-C 6 -alkyl, halogen, cyano, Ci-C 6 alkoxy or Q-C f jhaloalkoxy, more preferably methyl, ethyl, monofluoromethyl, difluoromethyl, trifluoromethyl, cyclopropyl, cyclopropylmethyl, chloro, cyano, methoxy, monofluoromethoxy, difiuoromethoxy or trifluoromethoxy, even more preferably methyl, ethyl, trifluoromethyl, cyclopropyl or chloro, most preferably methyl, ethyl,
  • a group of especially preferred compounds of formula (I) comprises those wherein Y is
  • a group of especially preferred compounds of formula (I) comprises those wherein Y is
  • a group of especially preferred compounds of formula (I) comprises those wherein Y is l-methyl-l,2,4-triazol-3-yl.
  • a group of especially preferred compounds of formula (I) comprises those wherein Y is l,5-dimethyl-l,2,4-triazol-3-yl.
  • a group of especially preferred compounds of formula (I) comprises those wherein Y is 1 -methyl- 5 -trifluoromethyl- 1 ,2,4-triazol-3-yl.
  • a group of especially preferred compounds of formula (I) comprises those wherein Y is 5-chloro-l-methyl-l,2,4-triazol-3-yl.
  • a group of especially preferred compounds of formula (I) comprises those wherein Y is 1 -ethyl- l,2,4-triazol-3-yl.
  • a group of especially preferred compounds of formula (I) comprises those wherein Y is l-ethyl-5-methyl-l,2,4-triazol-3-yl.
  • a group of especially preferred compounds of formula (I) comprises those wherein Y is 4-methyl-l,2,4-triazol-3-yl.
  • a group of especially preferred compounds of formula (I) comprises those wherein Y is 4,5-dimethyl-l,2,4-triazol-3-yl.
  • a group of especially preferred compounds of formula (I) comprises those wherein Y is 4-methyl-5-trifluoromethyl-l,2,4-triazol-3-yl.
  • a group of especially preferred compounds of formula (I) comprises those wherein Y is 5-chloro-4-methyl-l,2,4-triazol-3-yl.
  • a group of especially preferred compounds of formula (I) comprises those wherein Y is 5-ethyl-4-methyl-l,2,4-triazol-3-yl.
  • a group of especially preferred compounds of formula (I) comprises those wherein Y is 4-cyclopropyl-5-ethyl-l,2,4-triazol-3-yl.
  • a group of especially preferred compounds of formula (I) comprises those wherein Y is l,2,4-triazol-5-yl which is optionally substituted by one to two substituents independently selected from Q-Qalkyl, Ci-C 6 haloalkyl, C 3 -C ⁇ cycloalkyl, C 3 -C 6 cyclo- alkyl-Q-Ce-alkyl, halogen, cyano, Q-Qalkoxy or Q-C ⁇ haloalkoxy, more preferably methyl, ethyl, monofiuoromethyl, difluoromethyl, trifluoromethyl, cyclopropyl, cyclo- propylmethyl, chloro, cyano, methoxy, monofluoromethoxy, difluoromethoxy or trifmoromethoxy, even more preferably methyl, ethyl, trifluoromethyl or chloro, yet even more preferably methyl, trifluoromethyl or chloro, most preferably methyl or
  • a group of especially preferred compounds of formula (I) comprises those wherein Y is l-methyl-l,2,4-triazol-5-yl.
  • a group of especially preferred compounds of formula (I) comprises those wherein Y is l,3-dimethyl-l,2,4-triazol-5-yl.
  • a group of especially preferred compounds of formula (I) comprises those wherein Y is l-methyl-3-trifluoromethyl-l,2,4-triazol-5-yl.
  • a group of especially preferred compounds of formula (I) comprises those wherein Y is 3-chloro- 1 -methyl- 1 ,2,4-triazol-5-yl.
  • a group of especially preferred compounds of formula (I) comprises those wherein Y is 1 -ethyl- l,2,4-triazol-5-yl.
  • a group of especially preferred compounds of formula (I) comprises those wherein Y is l-ethyl-3-methyl-l,2,4-triazol-5-yl.
  • the compounds of the invention may be made by a variety of methods, for example by the methods described in the Schemes below.
  • R 1 , R 2 , R 3 , R 4 and Y are as defined above and m is 1 or 2, in a single step or stepwise in succession with a compound of formula R 5 -X and/or R 6 -X, wherein R 5 and R 6 are as defined above and X is a suitable leaving group e.g.
  • halide such as bromide or iodide
  • a carboxylate such as acetate
  • an alkylsulfonate such as methylsulfonate
  • an arylsulfonate such as p-toluenesulfonate
  • a haloalkylsulfonate such as trifluoromethyl- sulfonate
  • an imide such as succinimide, a sulfonimide, such as bis(phenylsulfonyl)- imide, or an arylsulfmate, such as p-toluenesulfinate, in the presence of a base, e.g.
  • an alkyl-lithium compound such as methyl-lithium, n-butyl-lithium or tert-butyl-lithium, a lithium dialkylamide, such as lithium diisopropylamide
  • a metal hydride preferably an alkali metal hydride, such as sodium hydride, or an alkali metal amide, such as sodium amide, a metal bis(tri(C 1 -C 6 alkyl)silyl)amide, such as lithium bis(trimethylsilyl)amide, a metal alkoxide, such as potassium tert-butoxide, or a phosphazene base, such as N r -tert- butyl-JV,N,N',N',iV",N"-hexamethylphosphorimidic triamide (“Pi-t-Bu”), 1-tert-butyl- 2,2,4,4,4-pentakis(dimethylamino)-2-lambda 5 ,41ambda 5
  • a hydrocarbon such as a hydrocarbon, an ether, such as tetrahydrofuran, an amide, such as N,N-dimethylformamide, or a halogenated hydrocarbon, such as dichloromethane, or mixtures thereof and optionally in the presence of a complexing agent, such as hexamethylphosphoramide or tetramethylethylenediamine in a temperature range of from -120 0 C to 100 0 C, preferably from -8O 0 C to 5O 0 C.
  • complexing agent such as hexamethylphosphoramide or tetramethylethylenediamine in a temperature range of from -120 0 C to 100 0 C, preferably from -8O 0 C to 5O 0 C.
  • R 1 , R 2 , R 3 , R 4 , R 6 and Y are as defined above and m is 1 or 2, with a compound of formula R 5 -X, wherein R 5 is halogen and X is a suitable leaving group as defined in 1), in the presence of a base as defined in 1), optionally in the presence of a diluent as defined in 1), preferably an inert solvent, and optionally in the presence of a complexing agent as defined in 1) in a temperature range of from -12O 0 C to 100 0 C, preferably from -8O 0 C to 5O 0 C.
  • R 1 , R 2 , R 3 , R 4 , R 5 and Y are as defined above and m is 1 or 2, with a compound of formula R 6 -X, wherein R 6 is cyano, Ci-C 6 alkyl, Ci-C ⁇ alkoxycarbonyl or halogen and X is a suitable leaving group as defined in 1), in the presence of a base as defined in 1), optionally in the presence of a diluent as defined in 1) and optionally in the presence of a complexing agent as defined in 1) in a temperature range of from -12O 0 C to 100 0 C, preferably from -8O 0 C to 5O 0 C.
  • a peroxy acid such as 3-chloro- peroxybenzoic acid, peracetic acid or hydrogen peroxide, an alkoxyperoxide or a periodate, such as sodium periodate, optionally in the presence of a catalyst, such as ruthenium(III) chloride, optionally in the presence of a diluent, such as a halogenated hydrocarbon, e.g. dichloromethane, 1,2-dichloroethane or carbon tetrachloride, an alcohol, e.g. methanol, a polar solvent, e.g. ⁇ Af-dimethylformamide, acetonitrile, water or acetic acid, or a mixture thereof.
  • a diluent such as a halogenated hydrocarbon, e.g. dichloromethane, 1,2-dichloroethane or carbon tetrachloride, an alcohol, e.g. methanol, a polar solvent, e.g. ⁇
  • the reactions are usually carried out in a temperature range of from -8O 0 C to 15O 0 C, preferably from -2O 0 C to 12O 0 C.
  • Such processes are known in the literature and are described e.g. in J. Org. Chem., 2003 (68) 3849-3859; J. Med. Chem., 2003 (46) 3021-3032; J. Org. Chem., 2003 (68) 500-511; Bioorg. Med. Chem., 1999 (9) 1837-1844.
  • One equivalent of oxidizing agent is required to convert a sulfide to the corresponding sulfoxide.
  • Two equivalents of oxidizing agent are required to convert a sulfide to the corresponding sulfone.
  • halogenating agent e.g. bromine or an N-halo- succinimide, such as N-chlorosuccinimide or N-bromosuccinimide
  • X c is halogen
  • a diluent e.g. acetic acid or a halogenated hydrocarbon, such as carbon tetrachloride or dichloromethane, in a temperature range of from -8O 0 C to 12O 0 C, preferably from -2O 0 C to 6O 0 C.
  • R 5 is fluoro and M-R 5 is a suitable salt or an organometal compound in which M is e.g. Li, MgBr, Na, K, Ag or tetraalkylammonium, optionally in the presence of a Lewis acid, e.g. SnCl 4 , optionally in the presence of a complexing agent, e.g. hexa- methylphosphoramide (“HMPA”) or l,3-dimethyl-3,4,5,6-tetrahydro-2(lH)- pyrimidinone (“DMPU”), and optionally in the presence of a diluent, e.g.
  • M e.g. Li, MgBr, Na, K, Ag or tetraalkylammonium
  • a Lewis acid e.g. SnCl 4
  • a complexing agent e.g. hexa- methylphosphoramide (“HMPA") or l,3-dimethyl-3,4,5,6-t
  • halogenating agent e.g. bromine or an iV-halo- succinimide, such as TV-chlorosuccinimide or N-bromosuccinimide
  • a halogenating agent e.g. bromine or an iV-halo- succinimide, such as TV-chlorosuccinimide or N-bromosuccinimide
  • X c is halogen
  • a diluent e.g. acetic acid or a halogenated hydrocarbon, such as carbon tetrachloride or dichloromethane, in a temperature range of from -80 0 C to 12O 0 C, preferably from -2O 0 C to 6O 0 C.
  • R 5 and / or R 6 are fluoro and M-R 5 and / or M-R 6 are a suitable salt or an organometal compound in which M is e.g. Li, MgBr, Na, K, Ag or tetraalkylammonium, optionally in the presence of a Lewis acid, e.g. SnCl 4 , optionally in the presence of a complexing agent, e.g. hexamethylphosphoramide (“HMPA”) or l,3-dimethyl-3 ,4,5,6- tetrahydro-2(lH)-pyrimidinone (“DMPU”), and optionally in the presence of a diluent, e.g.
  • HMPA hexamethylphosphoramide
  • DMPU l,3-dimethyl-3 ,4,5,6- tetrahydro-2(lH)-pyrimidinone
  • the compounds of formula (Id) as defined in 4) can be prepared by reacting a compound of formula (II) wherein R 5 , R 6 and Y are as defined above and X A is a leaving group such as halide e.g. bromide or chloride, an alkylsulfonate, e.g. methylsulfonate, an arylsulfonate, e.g. p-toluenesulfonate, or a halo alkylsulfonate, e.g. trifluoromethyl- sulfonate, with thiourea, optionally in the presence of a diluent e.g.
  • a diluent e.g.
  • R 1 , R 2 , R 3 and R 4 are as defined above, and X B is a suitable leaving group such as halogen, e.g. chloro, an alkylsulfinyl group, an arylsulfmyl group, a haloalkylsulfinyl group, an alkylsulfonyl group, e.g. methylsulfonyl, an arylsulfonyl group, e.g. p-toluene- sulfonyl, a haloalkylsulfonyl group, e.g.
  • halogen e.g. chloro
  • an alkylsulfinyl group an arylsulfmyl group
  • a haloalkylsulfinyl group an alkylsulfonyl group, e.g. methylsulfonyl, an arylsulfonyl group, e
  • a base such as a carbonate, e.g. potassium carbonate, sodium carbonate or potassium hydro gencarbonate, or a hydroxide, e.g. potassium hydroxide, or an alkoxide, e.g. sodium alkoxide, optionally in the presence of an alkali iodide, e.g. sodium iodide or sodium bromide, optionally in the presence of a diluent, such as an alcohol, e.g. ethanol, an ether, e.g. 1,4-dioxane or tetrahydrofuran, a polar solvent, e.g.
  • a base such as a carbonate, e.g. potassium carbonate, sodium carbonate or potassium hydro gencarbonate, or a hydroxide, e.g. potassium hydroxide, or an alkoxide, e.g. sodium alkoxide, optionally in the presence of an alkali iodide, e.g. sodium
  • a further method of preparing intermediates of formula (IV), wherein R 5 , R 6 and Y are as defined above, is to react a compound of formula (III), wherein R 5 , R and Y are as defined above, with thiourea in the presence of an acid, for example a mineral acid, such as hydrochloric acid or hydrobromic acid, or sulfuric acid, or an organic acid, such as trifluoroacetic acid, and optionally in the presence of a diluent, such as an ether, e.g. 1,4-dioxane or tetrahydrofuran, a polar solvent, e.g.
  • an acid for example a mineral acid, such as hydrochloric acid or hydrobromic acid, or sulfuric acid, or an organic acid, such as trifluoroacetic acid
  • a diluent such as an ether, e.g. 1,4-dioxane or tetrahydrofuran, a polar solvent, e
  • a further method of preparing the compounds of formula (Id) as defined in 4) is to react a compound of formula (VI) wherein R 5 , R 6 and Y are as defined above
  • the compounds of formula (Id) as defined in 4) can be prepared by reacting a compound of formula (V) as defined in 7) with thiourea, optionally in the presence of a diluent e.g. an alcohol, e.g. ethanol, in a temperature range of from -3O 0 C to 15O 0 C, preferably from 0 0 C to 80 0 C, to give an isothiourea intermediate of formula (VII),
  • a diluent e.g. an alcohol, e.g. ethanol
  • abase such as a carbonate, e.g. potassium carbonate, sodium carbonate or potassium hydrogencarbonate, or a hydroxide, e.g. potassium hydroxide, or an alkoxide, e.g. sodium alkoxide, optionally in the presence of a diluent, such as an alcohol, e.g. ethanol, a polar solvent, e.g. water or N,N-dimethylformamide, or a mixture of solvents, in a temperature range of from O 0 C to 200 0 C, preferably from O 0 C to 100 0 C.
  • a base such as a carbonate, e.g. potassium carbonate, sodium carbonate or potassium hydrogencarbonate, or a hydroxide, e.g. potassium hydroxide, or an alkoxide, e.g. sodium alkoxide, optionally in the presence of a diluent, such as an alcohol, e.g. ethanol, a polar solvent, e.g.
  • a further method of preparing the compounds of formula (Id) as defined in 4) is to react an organometal reagent of formula (VIII) wherein R 5 , R 6 and Y are as defined above and M B is a group such as MgCl, MgBr, ZnBr or Li,
  • a further method of preparing the compounds of formula (Id) as defined in 4) is to react a compound of formula (Ha) wherein R 5 , R 6 and Y are as defined above, and X D is functional group that may be cleaved as a radical, e.g. a halogen, such as bromo or chloro,
  • % phosphate such as disodium hydrogenphosphate, a carbonate, e.g. potassium carbonate, sodium carbonate or potassium hydrogencarbonate, optionally in the presence of a diluent, e.g. a polar solvent, such as water or ⁇ N-dimethylformamide, or mixtures thereof, in a temperature range of from -5O 0 C to 18O 0 C, preferably from -20 0 C to 50 0 C, and optionally under an inert atmosphere, e.g. nitrogen.
  • radical initiator or precursors can be used e.g. sodium dithionite or sodium hydroxymethanesulfinate.
  • a further method of preparing the compounds of formula (Id) as defined in 4) is to react a compound of formula (II) as defined in 7),
  • a reducing agent e.g. a hydride, such as sodium borohydride, a metal, such as zinc, or a hydrosulfite, such as sodium hydrosulfite, optionally in the presence of a base, e.g. a hydroxide, such as sodium hydroxide, a phosphate or hydrogen phosphate, such as disodium hydrogen phosphate, or an amine, such as triethylamine, optionally in the presence of a diluent, e.g.
  • R 8 is as defined above and R 12 is hydrogen, Cj-Cioalkyl, d-Qoalkoxycarbonyl, formyl, or the group Q, with a compound of formula R 7 -X E wherein R 7 is as defined above and X E is a suitable leaving group e.g.
  • halide such as bromide or iodide
  • a carboxylate such as acetate
  • an alkylsulfonate such as methylsulfonate
  • an arylsulfonate such as p-toluenesulfonate
  • a haloalkylsulfonate such as trifluoromethylsulfonate
  • a base e.g. a carbonate, such as potassium carbonate, a hydroxide, such as potassium hydroxide, a metal hydride, such as sodium hydride, optionally in the presence of a diluent, e.g.
  • an ether such as tetrahydrofuran
  • an amide such as iV,iV-dimethyl- formamide
  • an alcohol such as methanol, acetonitrile or acetone or mixtures thereof
  • a phase transfer catalyst such as trimethylammonium bromide
  • compounds of formula (XIIa), (XIIb) and (XIIc) are obtained exclusively or as mixtures in varying ratios.
  • the reaction can be carried out using chlorine, in the presence of a diluent such as a halogenated hydrocarbon, e.g. chloroform and in a temperature range from O 0 C to 150 0 C, preferably from 20 0 C to 80 0 C.
  • a diluent such as a halogenated hydrocarbon, e.g. chloroform
  • Similar processes are known in the literature and are described in, e.g. Ind. J. Chem., 1975 (13) 851, Synthetic Commun. 2001 (31) 2447-2456.
  • a nucleophilic halogen source e.g. hydrochloric acid or hydrobromic acid
  • a diluent such as water or an alcohol, e.g.
  • the reactions are usually carried out in a temperature range from -2O 0 C to 150 0 C, preferably from 0 0 C to 100 0 C. Similar processes are known in the literature and are described in, e.g. J. Med. Chem., 1996 (39) 3019-3029, Tetrahedron 1990 (46) 3211-3232.
  • X F is amino
  • the starting material is usually reacted with a diazotisation reagent e.g. sodium nitrite/hydrochloric acid, in the presence of a nucleophilic halogen source, e.g.
  • R 8 is a halide e.g. iodide or fluoride, an alkyl, alkenyl, alkynyl or haloalkyl, such as methyl, allyl, propynyl or trifluoropropyl, cyanide, an alkoxy, such as methoxide, an alkylsulfanyl, such as thiomethoxide, and M A is a suitable counterion such as sodium, potassium or ammonium.
  • R 8 is a halide e.g. iodide or fluoride, an alkyl, alkenyl, alkynyl or haloalkyl, such as methyl, allyl, propynyl or trifluoropropyl, cyanide, an alkoxy, such as methoxide, an alkylsulfanyl, such as thiomethoxide, and M A is a suitable counterion such as sodium, potassium or ammonium.
  • R 8
  • reaction can be carried out using H-R 8 , wherein R 8 is as defined above or NR 9 R 10 , such as morpholine, optionally in the presence of a base as defined in 1), optionally in the presence of a diluent such as a halogenated hydrocarbon, e.g. 1,2-dichloroethane or carbon tetrachloride, an ether, e.g. tetrahydrofuran or 1,4-dioxane, an aromatic compound, e.g. toluene, an alcohol, e.g. methanol, an amide, e.g. ⁇ N-dimethyl- formamide, water or a mixture thereof.
  • a diluent such as a halogenated hydrocarbon, e.g. 1,2-dichloroethane or carbon tetrachloride, an ether, e.g. tetrahydrofuran or 1,4-dioxane, an aromatic compound
  • the reactions are usually carried out in a temperature range from -5O 0 C to 200 0 C, preferably from 0 0 C to 150 0 C to give a compound of formula (XIIb).
  • the compounds of formula (XIIc) can similarly be prepared from a compound of formula (XIVc). Similar processes are known in the literature and are described in, e.g. Synthesis, 2006 496, Synthesis 1998 (9) 1357-1361, Journal of Medicinal Chemistry, 33(4), 1230-41; 1990; Bulletin de Ia Societe Chimique de France, (7-8, Pt.
  • the reactions are usually carried out in a temperature range from -5O 0 C to 200 0 C, preferably from 0 0 C to 150 0 C. Similar processes are known in the literature and are described in, e.g. Synthesis, (1), 156-160; 2006, Tetrahedron 2004 (60) 851-860, Bioorganic & Medicinal Chemistry, 13(2), 363- 386; 2004.
  • X G is amino
  • the starting material is usually reacted with a diazotisation reagent e.g. sodium nitrite/hydrochloric acid, in the presence of water or an alcohol, e.g.
  • a base e.g. an alkyl-lithium compound, such as methyl-lithium, H-butyl-lithium or tert-butyl-lithium, a lithium dialkylamide, such as lithium diisopropylamide, a metal hydride, preferably an alkali metal hydride, such as sodium hydride, or a metal bis(tri(Ci- C 6 alkyl)silyl)amide, such as lithium bis(trimethylsilyl)amide, followed by a compound of formula R 8 -X E , wherein R 8 is as defined above and X E is as defined in 14), optionally in the presence of a metal chelator e.g.
  • a metal chelator e.g.
  • hexamethylphosphoryl triamide, 18-crown-6 optionally in the presence of a diluent such as a halogenated hydrocarbon, e.g. 1,2- dichloroethane or carbon tetrachloride, an ether, e.g. tetrahydrofuran or 1,4-dioxane, an aromatic compound, e.g. toluene, an amide, e.g. ⁇ iV-dimethylformamide, water or a mixture thereof.
  • a diluent such as a halogenated hydrocarbon, e.g. 1,2- dichloroethane or carbon tetrachloride, an ether, e.g. tetrahydrofuran or 1,4-dioxane, an aromatic compound, e.g. toluene, an amide, e.g. ⁇ iV-dimethylformamide, water or a mixture thereof.
  • the reactions are usually carried out
  • the compounds of formula (XIIb) can similarly be prepared from a compound (XVIb) and the compounds of formula (XIIc) can similarly be prepared from a compound of formula (XVIc). Similar processes are known in the literature and are described in, e.g. Heterocycles 1985 (23) 1645-9, Heterocycles 2003 (60) 351-363, Synthesis, 2006 (1) 156-160; U.S., 4481360, Chemische Berichte, 1983, 116(10), 3513-15, Journal of Heterocyclic Chemistry, 15(3), 439-44; 1978.
  • halogenating agent such as hydrogen chloride, hydrogen bromide, phosphorous tribromide, phosphorous trichloride or thionyl chloride, or with an alkyl-, aryl- or halo- alkylsulfonyl chloride, such as methanesulfonyl chloride, p-toluenesulfonyl chloride or trifluoromethylsulfonyl chloride, or with a combination of carbon tetrabromide and triphenyl phosphine, optionally in the presence of an inert solvent, e.g.
  • an inert solvent e.g.
  • halogenated hydrocarbon such as dichloromethane, 1,2-dichloroethane or carbon tetrachloride
  • an ether such as diethyl ether or tetrahydrofuran
  • an acid such as acetic acid
  • a base e.g. an amine, such as triethyl amine
  • Such processes are known in the literature and are described, for example, in J. Med. Chem.2005 (48) 3438-3442, J. Org. Chem., 2005 (70) 2274-2284, Org. and Biomolecular Chem., 2005 (3) 1013-1024, Bioorg. Med. Chem. 2004 (13) 363-384, Tetrahedron Asymmetry 2004 (15) 3719-3722.
  • XVII (Ha) by reacting a compound of formula (XVII) wherein R 5 , R 6 and Y are as defined above, with a compound of formula R 1 l -X c , wherein X c is a leaving group such as halogen, e.g. bromo or chloro, and R is a functional group that may be cleaved to generate X as a radical, optionally in the presence of a diluent such as a halogenated hydrocarbon, e.g. dichloromethane, 1,2-dichloroethane or carbon tetrachloride, an ether, e.g. tetrahydro- furan, an aromatic compound, e.g. toluene, a polar solvent, e.g. acetonitrile,
  • a diluent such as a halogenated hydrocarbon, e.g. dichloromethane, 1,2-dichloroethane or
  • N, JV-dimethylformamide or water or a mixture thereof.
  • the reactions are usually carried out in a temperature range from -50°C to 12O 0 C, preferably from -5°C to 100 0 C.
  • the reactions maybe carried out optionally in the presence of light and or a radical initiator such as a peroxide, e.g. dibenzoylperoxide, or an azo compound, e.g. N,N'-azobis-
  • Suitable compounds of formula R -X include compounds in which R 11 is a succinimido group, e.g. N-chlorosuccinimide and iV-bromosuccinimide. Similar processes are known in the literature and are described, e.g. Tetrahedron, 1988 (44) 461- 469; Journal of Organic Chemistry, 1981 (46) 679-686; J. Chem. So ⁇ , Perkin Trans 1, 1985 (6), 1167-1170.
  • a reducing agent e.g. a metal hydride, such as diisobutyl aluminium hydride, lithium aluminium hydride, sodium borohydride, lithium boro- hydride, or diborane, optionally in the presence of an inert solvent, e.g. an ether, such as diethyl ether, 1,4-dioxane or tetrahydrofuran, an alcohol, such as methanol or ethanol, or an aromatic hydrocarbon, such as toluene.
  • a metal hydride such as diisobutyl aluminium hydride, lithium aluminium hydride, sodium borohydride, lithium boro- hydride, or diborane
  • an inert solvent e.g. an ether, such as diethyl ether, 1,4-dioxane or tetrahydrofuran, an alcohol, such as methanol or ethanol, or an aromatic hydrocarbon, such as toluene.
  • Such reactions are usually carried out in a temperature range from -50°C to 100°C, preferably from 0 0 C to 8O 0 C.
  • Such processes are known in the literature and are described, for example, in Tetrahedron Asymmetry, 2004 (15) 363-386; J. Med. Chem., 2002 (45) 19-31; Justus Liebigs Annalen der Chemie, 1978 (8) 1241-49.
  • the compounds of formula (HIb), wherein Y is as defined above can be prepared by reacting a compound of formula (XX),
  • a reducing agent e.g. a metal hydride, such as diisobutyl aluminium hydride, lithium aluminium hydride, sodium borohydride, lithium borohydride, or diborane
  • a metal hydride such as diisobutyl aluminium hydride, lithium aluminium hydride, sodium borohydride, lithium borohydride, or diborane
  • an inert solvent e.g. an ether, such as diethyl ether, 1,4-dioxane or tetrahydrofuran
  • an alcohol such as methanol or ethanol
  • aromatic hydrocarbon such as toluene.
  • Such reactions are usually carried out in a temperature range from -50°C to 100°C, preferably from O 0 C to 8O 0 C.
  • Such processes are known in the literature and are described, for example, in Tetrahedron Asymmetry 2004 (15) 3719-3722, J. Med. Chem., 2004 (47) 2176-2179, Heterocyclic Communications 2002 (8) 385-390, J. Antibiotics, 1995 (48) 1320-1329.
  • XXi (Hc) by reacting with a reagent of formula (XXII) wherein X D is halogen, such as bromo or chloro, in the presence of a diluent such as a halogenated hydrocarbon such as dichloromethane, a hydrocarbon such as hexane, an alcohol such as ethanol, N 1 N- dimethylformamide, tetrahydrofuran or a mixture thereof.
  • a diluent such as a halogenated hydrocarbon such as dichloromethane, a hydrocarbon such as hexane, an alcohol such as ethanol, N 1 N- dimethylformamide, tetrahydrofuran or a mixture thereof.
  • a diluent such as a halogenated hydrocarbon such as dichloromethane, a hydrocarbon such as hexane, an alcohol such as ethanol, N 1 N- dimethylformamide, tetrahydrofuran or a mixture thereof.
  • 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.
  • 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.
  • Such formulations can either be used directly or they are 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 consisting of a polymer. 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 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 in this connection.
  • 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.
  • 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, ⁇ iV-dimethylformamide, dimethyl sulfoxide, 1,4-dioxane, dipropylene glyco
  • Water is generally the carrier of choice for diluting the concentrates.
  • 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, as described, for example, in CFR 180.1001. (c) & (d).
  • 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 dodecylbenzenesulfonate; 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 alkylnaphthalenesulfonates, 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
  • 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 also liquid and solid fertilisers.
  • compositions according to the invention can additionally 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 spray mixture.
  • the oil additive can be added to the spray tank in the desired concentration after the 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, such as AMIGO® (Rhone-Poulenc Canada Inc.), 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.
  • a preferred additive contains, for example, as active components essentially 80 % by weight alkyl esters offish oils and 15 % by weight methylated rapeseed oil, and also 5 % by weight of customary emulsifiers and pH modifiers.
  • Especially preferred oil additives comprise alkyl esters Of C 8 -C 22 fatty acids, especially the methyl derivatives OfC 12 -C 18 fatty acids, for example the methyl esters of lauric acid, palmitic acid and oleic acid, being of importance.
  • Those esters are known as methyl laurate (CAS-111-82-0), methyl palmitate (CAS-112-39-0) and methyl oleate (CAS-112-62-9).
  • a preferred fatty acid methyl ester derivative is Emery® 2230 and 2231 (Cognis GmbH).
  • Those and other oil derivatives are also known from the Compendium of Herbicide Adjuvants, 5th Edition, Southern Illinois University, 2000.
  • the application and action of the oil additives can be further improved by combination with surface-active substances, such as non-ionic, anionic or cationic surfactants.
  • surface-active substances such as non-ionic, anionic or cationic surfactants.
  • suitable anionic, non-ionic and cationic surfactants are listed on pages 7 and 8 of WO 97/34485.
  • Preferred surface-active substances are anionic surfactants of the dodecylbenzylsulfonate type, especially the calcium salts thereof, and also non-ionic surfactants of the fatty alcohol ethoxylate type. Special preference is given to ethoxylated Ci 2 -C 22 fatty alcohols having a degree of ethoxylation of from 5 to 40.
  • Examples of commercially available surfactants are the Genapol types (Clariant AG).
  • silicone surfactants especially polyalkyl-oxide-modified heptamethyltriloxanes which are commercially available e.g. as Silwet L-77®, and also perfluorinated surfactants.
  • concentration of the surface-active substances in relation to the total additive is generally from 1 to 30 % by weight.
  • oil additives consisting of mixtures of oil or mineral oils or derivatives thereof with surfactants are Edenof ME SU®, Turbocharge® (Syngenta AG, CH) or ActipronC (BP Oil UK Limited, GB).
  • an organic solvent may contribute to an additional enhancement of action.
  • Suitable solvents are, for .example, Solvesso® (ESSO) or Aromatic Solvent® (Exxon Corporation).
  • the concentration of such solvents can be from 10 to 80 % by weight of the total weight.
  • Oil additives that are present in admixture with solvents are described, for example, in US-A- 4,834,908.
  • a commercially available oil additive disclosed therein is known by the name MERGE® (BASF Corporation).
  • a further oil additive that is preferred according to the invention is SCORE® (Syngenta Crop Protection Canada).
  • alkylpyrrolidones e.g. Agrimax®
  • formulations of alkylpyrrolidones e.g. Agrimax®
  • synthetic lattices e.g. polyacrylamide, polyvinyl compounds or poly-1-p-menthene (e.g. Bond®, Courier® or Emerald®)
  • propionic acid for example Eurogkem Pen-e-trate®
  • the herbicidal compositions generally comprise from 0.1 to 99 % by weight, especially from 0.1 to 95 % by weight, compounds of formula (I) and from 1 to 99.9 % 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.
  • commercial products will preferably be formulated as concentrates, the end user will normally employ dilute formulations.
  • the rates of application of compounds of formula (I) may vary within wide limits and depend on the nature of the soil, the method of application (pre- or post-emergence; seed dressing; application to the seed furrow; no tillage application etc.), the crop plant, the grass or weed to be controlled, the prevailing climatic conditions, and other factors governed by the method of application, the time of application and the target crop.
  • the compounds of formula (I) according to the invention are generally applied at a rate of from 10 to 2000 g/ha, especially from 50 to 1000 g/ha.
  • 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 %
  • Emulsifiable concentrates a) b) c) d) active ingredient 5% 10% 25% 50% calcium dodecylbenzenesulfonate 6% 8% 6% 8% castor oil polyglycol ether 4% - 4% 4%
  • Emulsions of any desired concentration can be obtained from such concentrates by dilution with water.
  • the solutions are suitable for use in the form of microdrops.
  • F3. Wettable powders a) b) c) ⁇ active ingredient 5% 25% 50% 80% sodium lignosulfonate 4% - 3% - sodium lauryl sulfate 2% 3% - 4% sodium diisobutylnaphthalene- sulfonate - 6% 5% 6% octylphenol polyglycol ether - 1% 2% -
  • the active ingredient is mixed thoroughly with the adjuvants and the mixture is thoroughly ground in a suitable mill, affording wettable powders which can be diluted with water to give suspensions of any desired concentration.
  • the active ingredient is dissolved in methylene chloride and applied to the carrier by spraying, and the solvent is then evaporated off in vacuo.
  • the active ingredient 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.
  • Ready-to-use dusts are obtained by mixing the active ingredient with the carriers and grinding the mixture in a suitable mill.
  • Suspension concentrates a) b) c) d) active ingredient 3% 10% 25% 50% ethylene glycol 5% 5% 5% 5% nonylphenol polyglycol ether - 1 % 2 % (15 mol of ethylene oxide) sodium lignosulfonate 3 % 3 % 4 % 5 % carboxymethylcellulose 1 % 1 % 1 % 1 %
  • the finely ground active ingredient is intimately mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired concentration can be obtained by dilution with water.
  • the invention also relates to 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).
  • the invention also relates to 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) .
  • the invention also relates to a method of selectively controlling grasses and 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).
  • Crops of useful plants in which the composition according to the invention can be used include cereals, for example barley and wheat, cotton, oilseed rape, maize, rice, soy beans, sugar beet and sugar cane, especially cereals and maize.
  • Crops can also include trees, such as palm trees, coconut trees or other nuts, and vines such as grapes.
  • the grasses and weeds to be controlled may be both monocotyledonous species, for example Agrostis, Alopecurus, Avena, Bromus, Cyperus, Digitaria, Echinochloa, Lolium, Monochoria, Rottboellia, Sagittaria, Scirpus, Setaria, Sida and Sorghum, and dicotyledonous species, for example Abutilon, Amaranthus, Chenopodium, Chrysanthemum, Galium, Ipomoea, Nasturtium, Sinapis, Solanum, Stellaria, Veronica, Viola and Xanthium.
  • monocotyledonous species for example Agrostis, Alopecurus, Avena, Bromus, Cyperus, Digitaria, Echinochloa, Lolium, Monochoria, Rottboellia, Sagittaria, Scirpus, Setaria, Sida and Sorghum
  • dicotyledonous species for example Abutilon,
  • Crops are to be understood as also including those crops which have been rendered tolerant to herbicides or classes of herbicides (e.g. ALS-, GS-, EPSPS-, PPO- and HPPD-inhibitors) by conventional methods of breeding or by genetic engineering.
  • herbicides or classes of herbicides e.g. ALS-, GS-, EPSPS-, PPO- and HPPD-inhibitors
  • An example of a crop that has been rendered tolerant to imidazolinones, e.g. imazamox, by conventional methods of breeding is Clearfield® summer rape (canola).
  • 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 RoundupReady® and LibertyLink®.
  • Crops are also to be understood as being those which have been rendered resistant to harmful insects by genetic engineering methods, for example Bt maize (resistant to European corn borer), Bt cotton (resistant to cotton boll weevil) and also Bt potatoes (resistant to Colorado beetle).
  • Bt maize are the Bt 176 maize hybrids of NK® (Syngenta Seeds).
  • the Bt toxin is a protein that is formed naturally by Bacillus thuringiensis soil bacteria.
  • Examples of toxins, or transgenic plants able to synthesise such toxins are described in EP-A-451 878, EP-A-374 753, WO 93/07278, WO 95/34656, WO 03/052073 and EP-A-427 529.
  • transgenic plants comprising one or more genes that code for an insecticidal resistance and express one or more toxins are KnockOut® (maize), Yield Gard® (maize), NuCOTIN33B® (cotton), Bollgard® (cotton), NewLeaf® (potatoes), NatureGard® and Protexcta®.
  • Plant crops or seed material thereof can be both resistant to herbicides and, at the same time, resistant to insect feeding ("stacked" transgenic events).
  • seed can have the ability to express an insecticidal Cry3 protein while at the same time being tolerant to glyphosate.
  • Crops are also to be understood as being those which are obtained by conventional methods of breeding or genetic engineering and 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.
  • Areas under cultivation include land on which the crop plants are already growing and land intended for cultivation with those crop plants.
  • the compounds of formula (I) according to the invention can also be used in combination with one or more further herbicides.
  • the following mixtures of the compound of formula (I) are important: Mixtures of a compound of formula (I) with S-metolachlor (549) or a compound of formula (I) with metolachlor (548).
  • Mixtures of a compound of formula (I) with an HPPD inhibitor and a triazine Mixtures of a compound of formula (I) with glyphosate (419). Mixtures of a compound of formula (I) with glyphosate and an HPPD inhibitor
  • 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, 13 th Edition (BCPC), 2003.
  • the reference to glufosinate-ammonium also applies to glufosinate
  • the reference to cloransulam-methyl also applies to cloransulam
  • 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).
  • herbicides can be used in combination with a compound of formula (I) according to the invention or in combination with a mixture as described above: compound of formula (I) + acetochlor (5), compound of formula (I) + acifluorfen-sodium (7), compound of formula (I) + aclonifen (8), compound of formula (I) + acrolein (10), compound of formula (I) + alachl ⁇ r (14), compound of formula (I) + alloxydim (18), compound of formula (I) + allyl alcohol (CAS RN 107-18-6), compound of formula (I) + amidosulfuron (22), compound of formula (I) + aminopyralid (CAS RN 150114-71-9), compound of formula (I) 4- amitrole (aminotriazole) (25), compound of formula (I) + ammonium sulfamate (26), compound of formula (I) + anilofos (31), compound of formula (I) + asulam
  • 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, 13 th Edition (BCPC), 2003.
  • the reference to acifluorfen-sodium also applies to acifluorfen, and the reference to bensulfuron-methyl also applies to bensulfuron, 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).
  • the compounds of formula (I) according to the invention can also be used in combination with one or more safeners.
  • mixtures of a compound of formula (I) according to the invention with one or more further herbicides can also be used in combination with one or more safeners.
  • safener as used herein means a chemical that when used in combination with a herbicide reduces the undesirable effects of the herbicide on non-target organisms, for example, a safener protects crops from injury by herbicides but does not prevent the herbicide from killing the weeds.
  • the safeners can be AD 67 (MON 4660) (11), benoxacor (63), cloquintocet-mexyl (163), cyometrinil (CAS RN 78370-21-5) and the corresponding (Z) isomer, cyprosulfamide (CAS RN 221667-31-8), dichlormid (231), fenchlorazole-ethyl (331), fenclorim (332), flurazole (386), fluxofenim (399), furilazole (413) and the corresponding R isomer, isoxadifen- ethyl (478), mefenpyr-diethyl (506), oxabetrinil (598), naphthalic anhydride (CAS RN 81-84-5), N-isopropyl-4-(2-methoxy-benzoylsulfamoyl)-benzamide (CAS RN 221668-34-4), 2-methoxy-N-[[4-[[
  • mixtures of a compound of formula (I) with benoxacor are mixtures of a compound of formula (I) with benoxacor.
  • 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, 13 th Edition (BCPC), 2003.
  • the reference to cloquintocet-mexyl also applies to a lithium, sodium, potassium, calcium, magnesium, aluminium, iron, ammonium, quaternary ammonium, sulfonium or phos- phonium salt thereof as disclosed in WO 02/34048, 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) with the safener).
  • active ingredient relates to the respective mixture of compound of formula (I) 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- emergence or might be applied to the crop post-emergence.
  • Preferred mixtures of a compound of formula (I) with further herbicides and safeners include:
  • Mixtures of a compound of formula (I) with glufosinate and a safener Mixtures of a compound of formula (I) with isoxaflutole and a safener.
  • Mixtures of a compound of formula (I) with sulcotrione and glyphosate and a safener Mixtures of a compound of formula (I) with sulcotrione and glufosinate and a safener.
  • Mixtures of a compound of formula (I) with tembotrione and a triazine and a safener Mixtures of a compound of formula (I) with tembotrione and glyphosate and a safener.
  • Example 1.1 420 mg, 2.54 mmol was dissolved in carbon tetrachloride (5 ml). N-Bromosuccinimide (“NBS”) (573 mg, 3.2 mmol) and azobisisobutyronitrile (“AIBN”) (64 mg, 0.4 mmol) were added and the reaction mixture illuminated with a halogen lamp under a nitrogen atmosphere. The heat of the lamp soon caused the reaction mixture reflux. After 2 hours the reaction mixture was allowed to cool to ambient temperature and filtered through silica gel. The silica gel was washed with dichloromethane.
  • NBS N-Bromosuccinimide
  • AIBN azobisisobutyronitrile
  • JV-Methyl-acetamidine (preparation according to DE 3118258) (158 mg, 1.28 mmol) was dissolved in trifiuoroacetic acid (1 ml, 12.8 mmol) under a nitrogen atmosphere. The reaction mixture was heated to reflux for 3 hours and then stored at ambient temperature for 16 hours. The reaction mixture was cooled to 0 0 C and diluted with water before addition of aqueous sodium hydroxide (5N). The mixture was extracted with dichloromethane. The combined organic extracts were concentrated carefully as the product is volatile to give l,3-dimethyl-5-trifluoromethyl-lH-[l,2,4]- triazole as a liquid (115 mg, 54% yield). 1 H-NMR (400 MHz, CDCl 3 ): 2.41 (s, 3H), 3.98 (s, 3H) ppm.
  • Example 1.9 Preparation of S-chloro-S-fS ⁇ -dimethyl ⁇ -dihydro-isoxazol-S-yl- sulfanylmethviyi -methyl- lH-[L2,41triazole, 3-chloro-5-(5,5-dimethyl-4,5-dihydro- isoxazol-S-ylsulfanyhnethyD-l-methyl-lH-fl ⁇ itriazole and S-chloro-S-fS ⁇ -dimethyl- 4,5-dihydro-isoxazol-3-ylsulfanylmethyl)-4-methyl-4H-[l,2,4]triazole
  • Example 1.10 Preparation of l-ethyl-lH-[l,2,,4 ⁇
  • Example 1.11 Preparation of ri-ethyl-lH-[l,2,41triazol-3-ylVmethanol and (1-ethyl-lH- [1 ,2,41triazol-5-yl)-methanol
  • LiAIH A mixture of l-ethyl-lH-[l,2,4]triazole-3-carboxylic acid methyl ester and 1- ethyl-lH-[l,2,4]triazole-5-carboxylic acid methyl ester (Example 1.10) (42 g) was suspended in dry tetrahydrofuran (200 ml) with stirring under an atmosphere of nitrogen at O 0 C. Pellets of lithium aluminium hydride (7 g) were added over a period of 1 hour at 0 0 C. The cooling bath was removed allowing the temperature of the reaction mixture to rise gradually until it began to reflux.
  • 5-(5,5-Dimethyl-4,5-dihydro-isoxazol-3-ylsulfanylmethyl)-l,3-dimethyl-lJJ- [l,2,4]triazole from 5-chloromethyl- 1,3 -dimethyl- IH-[1, 2,4]triazole as starting material.
  • 5-(5,5-Dimethyl-4,5-dihydroisoxazol-3-ylsulfanylmethyl)-l-ethyl-3-methyl-lH- [l,2,4]triazole was prepared from 5-chloromethyl-l-ethyl-3-methyl-lH-[l,2,4]triazole as 25 starting material.
  • 5-(5,5-Dimethyl-4,5-dihydroisoxazol-3-ylsulfanylmethyl)-l-ethyl-lH-[l,2,4]- triazole was prepared from 5-chloromethyl-l-ethyl-lH-[l,2,4]triazole as starting material.
  • 5-(5,5-Dimethyl-4,5-dihydro-isoxazol-3-ylsulfanylmethyl)-2,4-dihydro-[l,2,4]- triazol-3-one from 5-chloromethyl-2,4-dihydro-[l,2,4]triazol-3-one as starting material.
  • reaction mixture was diluted with more dichloromethane and aqueous sodium hydrogen carbonate (saturated) and the biphasic mixture stirred vigorously for 15 minutes. The phases were separated and the organic phase was concentrated. The residue was purified by column chromatography on silica gel (eluent: ethyl acetate / hexane) to give 5-(5,5-dimethyl-4,5-dihydro-isoxazole-3- sulfmylmethyl)-l-methyl-3-trifluoromethyl-lH " -[l,2,4]triazole as a colourless oil (139 mg, 77% yield).
  • [l,2,4]triazole from 3-(5,5-dimethyl-4,5-dihydro-isoxazole-3-sulfanylmethyl)-l,5- dimethyl- lH-[ 1 ,2,4]triazole.
  • Example 3.1 Preparation of 5-r(5,5-dimethyl-4,5-dihvdro-isoxazole-3-sulfonyl)-fluoro- methyll-l-methyl-3-trifluoromethyl-lH-ri,2,41triazole (Compound No. 1.08 of Table 1) and 5-[r5.5-dimethyl-4,5-dihydro-isoxazole-3-sulfonyl)-difluoro-methyl]-l-methyl-3- trifluoromethyl-lH-ri,2,41triazole (Compound No. 1.07 of Table 1)
  • Example 3.2 Preparation of 5-[chloro-(5,5-dimethyl-4,5-dihydro-isoxazole-3-sulfonyl) ⁇ methyl14-metfayl-3-trifluorometfavl-l/f-flJ2.41triazole (Compound No. 1.11 of Table 1) ' and 5-
  • N-fluorobenzenesulfonimide (123 mg, 0.39 mmol) was added in one portion at 0 0 C.
  • the reaction mixture was allowed to warm to ambient temperature and stirred at ambient temperature for 30 minutes.
  • the reaction mixture was concentrated and the residue purified by column chromatography on silica gel (eluent: ethyl acetate / hexane) to give a residue which was further purified by column chromatography on silica get (eluent: dichloromethane / hexane) to give Compound No. 1.09 of Table 1 as a clear oil (42 mg, 28% yield).
  • Lithium hexamethyldisilazide (IM in T ⁇ F) (0.625 ml, 0.62 mmol) was added dropwise at -78°C and the reaction mixture allowed to slowly warm to O 0 C over a period of 5 hours.
  • the reaction mixture was quenched by addition of aqueous ammonium chloride (saturated) at 0 0 C and the mixture extracted with ethyl acetate.
  • the aqueous layer was saturated with sodium chloride and extracted with ethyl acetate.
  • the combined organic extracts were concentrated and the residue partitioned between dichloromethane and water.
  • SOLNI Solanum nigrum
  • AMARE Amaranthus retroflexus
  • SETFA Setaria faberi
  • ALOMY Alopecurus myosuroides
  • ECHCG Echinochloa crusgalli.
  • AMARE Amaranthus retroflexus
  • DIGSA Digitaria sanguinalis
  • ALOMY Digitaria sanguinalis

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  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
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  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Nitrogen And Oxygen Or Sulfur-Condensed Heterocyclic Ring Systems (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

La présente invention porte sur de nouveaux composés de formule (I) : dans laquelle R1, R2, R3, R4, m, R5, R6, n et Y sont tels que définis dans la revendication 1 ; ou des N-oxydes, sels et isomères optiques de ceux-ci. De plus, la présente invention porte sur des procédés de préparation des composés de formule (I) sur des intermédiaires utilisés dans la préparation des composés de formule (I), sur des compositions herbicides comprenant des composés de formule (I) et sur des procédés d'utilisation des composés de formule (I) pour détruire les plantes ou pour inhiber la croissance des plantes.
PCT/GB2007/004735 2006-12-21 2007-12-10 Nouveaux herbicides WO2008074991A1 (fr)

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