WO1996000219A1 - Pyrimidinyl- and triazinyl-oxy and thio-3-haloalkyl-propionic acid derivatives as herbicides - Google Patents

Pyrimidinyl- and triazinyl-oxy and thio-3-haloalkyl-propionic acid derivatives as herbicides Download PDF

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Publication number
WO1996000219A1
WO1996000219A1 PCT/EP1995/002295 EP9502295W WO9600219A1 WO 1996000219 A1 WO1996000219 A1 WO 1996000219A1 EP 9502295 W EP9502295 W EP 9502295W WO 9600219 A1 WO9600219 A1 WO 9600219A1
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alkyl
formula
compound
methyl
phenyl
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PCT/EP1995/002295
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French (fr)
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Christoph Lüthy
William Lutz
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Ciba-Geigy Ag
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Priority to AU28821/95A priority Critical patent/AU2882195A/en
Publication of WO1996000219A1 publication Critical patent/WO1996000219A1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/12—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring 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
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/54—1,3-Diazines; Hydrogenated 1,3-diazines
    • 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
    • A01N43/84—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 six-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,4
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more 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
    • C07D239/46—Two or more oxygen, sulphur or nitrogen atoms
    • C07D239/60—Three or more oxygen or sulfur atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
    • C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
    • C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
    • C07D405/12—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a chain containing hetero atoms as chain links
    • 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
    • C07D409/12—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 chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D491/00—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00
    • C07D491/02—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00 in which the condensed system contains two hetero rings
    • C07D491/04—Ortho-condensed systems

Definitions

  • the present invention relates to novel herbicidally active pyrimidinyl- and triazinyl-oxy- and -thio-3-haloalkyl-propionic acid derivatives, to processes for the preparation thereof, to compositions comprising those compounds and to the use thereof in the control of weeds, especially in crops of useful plants or in the inhibition of plant growth.
  • the present invention therefore relates to compounds of formula I
  • R is hydrogen, C 1 -C 6 alkyl, C 1 -C 4 haloalkyl, C 1 - or C 2 -alkyl substituted by C 1 - or
  • R 1 is C 1 -C 7 haloalkyl
  • R 2 is hydrogen, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 2 -C 6 alkenyl, C 3 -C 6 cycloalkyl, phenyl, phenyl substituted by fluorine, chlorine, bromine, trifluoromethyl or methoxy, 2-, 3- or 4-pyridyl, or 2- or 3-thienyl;
  • R 3 is methyl, ethyl, methoxy, ethoxy, trifluoromethyl, difluoromethoxy or 2,2,2-tri- fluoroethoxy;
  • Z is nitrogen, methine or methine substituted by fluorine, chlorine, bromine or methyl;
  • R 4 is fluorine, chlorine, methyl, ethyl, isopropyl, cyclopropyl, methoxy, ethoxy, methyl- thio, ethylthio, methylamino, dimethylamino, ethylamino, methoxymethyl, trifluoromethyl, chloromethyl, trichloromethyl or difluoromethoxy; or, if Z is methine, R 4 forms a -O(CH 2 ) m - bridge to Z, the linkage to Z being via the carbon atom;
  • Y is nitrogen, or, if Z is nitrogen, Y is nitrogen, methine or methine substituted by fluorine, chlorine or bromine;
  • X is oxygen or sulfur
  • A is hydroxy, -OR 5 , -SR 6 , imidazolyl, triazolyl, 2-thionothiazolidin-3-yl, cyanamino, hydroxyamino, C 1 -C 6 alkoxyamino, C 1 -C 3 alkoxy(C 1 -C 3 alkyl)amino or a group of
  • R 5 is C 1 -C 6 alkyl, C 3 -C 6 alkenyl, C 3 -C 6 alkynyl, C 1 -C 4 alkoxy-C 1 -C 4 alkyl, C 1 - or
  • R 6 is C 1 -C 6 alkyl, C 2 -C 4 dialkylamino-C 1 -C 4 alkyl, C 1 -C 4 alkoxycarbonyl-C 1 -C 4 alkyl, phenyl, or phenyl substituted by fluorine, chlorine, bromine, methyl, methoxy or nitro;
  • R 7 is hydrogen or methyl
  • R 9 is hydrogen, trifluoromethyl, C 1 -C 4 alkyl, C 1 -C 4 alkyl substituted by hydroxy,
  • R 7 and R 9 together are -(CH 2 ) q -, -CH 2 CH(OH)CH 2 -, -CH 2 SCH 2 - or -CH 2 CH 2 SCH 2 -;
  • R 8 is hydroxymethyl, formyl, cyano, phosphono, phosphino, methylphosphino or a -COL group;
  • R 10 is hydrogen or methyl
  • R 9 and R 10 together are -(CH 2 ) n -;
  • R 11 is C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 haloalkenyl, C 2 -C 6 alkynyl, C 2 -C 6 haloalkynyl, C 3 -C 6 cycloalkyl, C 3 -C 6 cycloalkylmethyl, C 1 -C 4 alkylamino, di-C 1 -C 4 alkylamino, C 1 -C 3 alkoxy-C 1 -C 3 alkylamino, C 3 -C 6 alkenylamino,
  • R 12 is hydrogen or methyl
  • R 13 is hydrogen, C 1 -C 6 alkyl, phenyl or phenyl substituted by fluorine, chlorine, bromine, iodine, C 1 -C 4 alkyl, trifluoromethyl, C 1 -C 3 alkoxy, difluoromethoxy, cyano, nitro or C 1 -C 4 alkoxycarbonyl, pyridyl or pyridyl mono- or di-substituted by fluorine, chlorine, methyl, methoxy or trifluoromethyl;
  • n 2 or 3;
  • n 2, 3, 4 or 5;
  • q 2 or 3
  • W is oxygen or sulfur
  • L is hydroxy, C 1 -C 4 alkoxy, C 3 - or C 4 -alkenyloxy, amino, C 1 -C 4 alkylamino, C 1 -C 4 di- alkylamino, benzyloxy or a group of the formula (L*,) or
  • R 14 is hydroxy, C 1 -C 4 alkoxy, 2-propenyloxy, benzyloxy, amino or a further group of the
  • R 140 is hydroxy, C 1 -C 4 alkoxy, 2-propenyloxy, benzyloxy or amino;
  • R 15 is hydrogen, C 1 -C 4 alkyl or benzyl
  • R 17 is hydrogen
  • R 15 and R 17 together are -(CH 2 ) 3 -;
  • R 16 is hydrogen or methyl
  • Formula I thus includes all the possible stereoisomers present in the form of . enantiomers, diastereoisomers, E/Z isomers or mixtures thereof.
  • the alkyl radicals may be straight-chained or branched.
  • alkyl moiety of alkoxy, alkylthio, alkylsulfinyl, alkylsulfonyloxy, alkylamino, dialkylamino, alkylsilyl, alkoxycarbonyl, alkylcarbonyloxy, haloalkyl groups and other alkyl-containing groups.
  • C 1 -C 6 alkyl is, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl or the isomers of pentyl, and hexyl or the isomers of hexyl.
  • alkoxy-, cyano- or phenyl-substituted alkyl group is, for example, methoxyethyl, ethoxyethyl, cyanoethyl or benzyl.
  • Alkoxyethoxy-substituted alkyl groups in the definition of R 5 are, for example, methoxy- ethoxy methyl.
  • the C 2 -C 6 alkenyl, C 2 -C 6 haloalkenyl and C 3 -C 6 alkynyl radicals occurring in the substituents may likewise be straight-chained or branched, such as vinyl, allyl, methallyl, 1-methylvinyl, but-2-en-1-yl, 3-chloro-2-propenyl, 3-chloro-2-methyl-2-propenyl, 2,3-dichloro-2-propenyl, 2-propyn-1-yl, 1-methyl-2-propyn-1-yl and but-2-yn-1-yl.
  • Alkoxy is, for example, methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, sec- butoxy or tert-butoxy.
  • Alkenyloxy is, for example, allyloxy, methallyloxy or but-2-en-1-yloxy.
  • Alkynyloxy is, for example, 2-propyn-1-yloxy, 2-butyn-1-yloxy or 3-butyn-1-yloxy.
  • Alkylamino is, for example, methylamino, ethylamino, n-propylamino, isopropylamino, n-butylamino or sec-butylamino.
  • Dialkylamino is, for example, dimethylamino or diethylamino.
  • Alkoxy(alkyl)amino is, for example, N-methoxy(methyl)amino.
  • Alkenylamino is, for example, 2-propenylamino.
  • Alkynylamino is, for example, 2-propynylamino.
  • Cycloalkylamino is, for example, cyclopropylamino.
  • Alkylthio or alkylmercapto is, for example, methylthio, ethylthio, n-propylthio, isopropyl- thio, n-butylthio, sec-butylthio or tert-butylthio.
  • Alkylideneimino is, for example, 2-propylideneimino or 2-butylideneimino.
  • Alkoxycarbonyl is, for example, methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, isopropoxycarbonyl, n-butoxycarbonyl or tert-butoxycarbonyl.
  • a haloalkyl group may contain one or more halogen atoms, such as fluorine, chlorine or bromine, for example fluoromethyl, difluoromethyl, chloromethyl, dichloromethyl, dibromomethyl, 2-fluoroethyl, 2,2,2-trifluoroethyl, 2-chloroethyl or 2,2,2-trichloroethyl.
  • halogen atoms such as fluorine, chlorine or bromine
  • Cycloalkyl radicals that are suitable as substituents are, for example, cyclopropyl, cyclo- butyl, cyclopentyl and cyclohexyl.
  • Cycloalkyl-C 1 -C 3 alkyl radicals that are suitable as substituents are, for example, cyclo- propyl-methyl, cyclopropyl-ethyl, cyclopropyl-propyl, cyclobutyl-methyl, cyclobutyl- ethyl, cyclobutyl-propyl, cyclopentyl-methyl, cyclopentyl-ethyl, cyclopentyl-propyl, cyclohexyl-methyl and cyclohexyl-ethyl.
  • Cycloalkyl-C 1 - or -C 2 -alkoxy radicals that are suitable as substituents are, for example, cyclopropyl-methoxy, cyclopropyl-ethoxy, cyclobutyl-methoxy, cyclobutyl-ethoxy, cyclo- pentyl-methoxy, cyclopentyl-ethoxy, cyclohexyl-methoxy and cyclohexyl-ethoxy.
  • Oxacycloalkyl radicals that are suitable as substituents are, for example, oxacyclobutyl, oxacyclopentyl, oxacyclohexyl and oxacycloheptyl, especially oxetan-3-yl, 3-methyl- oxetan-3-yl, 3-ethyl-oxetan-3-yl and 2-methyl-oxetan-3-yl.
  • Oxacycloalkyl-C 1 -C 3 alkyl radicals that are suitable as substituents are, for example, oxiran-2-yl-methyl, oxacyclobutyl-methyl, oxacyclobutyl-ethyl, oxacyclobutyl-propyl, oxacyclopentyl-methyl, oxacyclopentyl-ethyl, oxacyclopentyl-propyl, oxacyclohexyl- methyl, oxacyclohexyl-ethyl, oxacyclohexyl-propyl, oxacycloheptyl-methyl and oxacyclo- heptyl-propyl.
  • Dioxacycloalkyl radicals that are suitable as substituents are, for example, dioxacyclo- pentyl, dioxacyclohexyl, dioxacycloheptyl, methyldioxacyclopentyl, dimethyldioxacyclo- pentyl and dimethyldioxacyclohexyl.
  • Dioxacycloalkyl-C 1 -C 3 alkyl radicals that are suitable as substituents are, for example, dioxacyclopentyl-methyl, dioxacyclopentyl-ethyl, dioxacyclopentyl-propyl, dioxacyclo- hexyl-methyl, dioxacyclohexyl-ethyl, dioxacyclohexyl-propyl and dioxacycloheptyl- methyl, especially (1,3-dioxolan-2-yl)-methyl, (1,3-dioxolan-2-yl)-ethyl, (1,3-dioxan- 2-yl)-ethyl and [1,3-(2,2-dimethyl)-dioxolan-5-yl]-methyl.
  • the invention also includes the salts that the compounds of formula I are capable of forming with amines, alkali metal and alkaline earth metal bases or quaternary ammonium bases.
  • Suitable salts of the free carboxy groups are especially salts of alkali metals, such as lithium, sodium and potassium, salts of alkaline earth metals, such as magnesium and calcium, or salts of organic ammonium bases, such as ammonia and primary, secondary and tertiary alkylamines.
  • 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 those of sodium and potassium.
  • Examples of amines that are suitable for the formation of ammonium salts include both ammonia and primary, secondary and tertiary C 1 -C 18 alkylamines, C 1 -C 4 hydroxy alkylamines and C 2 -C 4 alkoxyalkylamines, for example methylamine, ethylamine, n-propyl- amine, isopropylamine, the four isomers of butylamine, n-amylamine, isoamylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, pentadecylamine, hexa- decylamine, heptadecylamine, octadecylamine, methyl-ethylamine, methyl-isopropyl- amine, methyl-hexylamine, methyl-nonylamine, methyl-pentadecylamine,
  • R 2 is hydrogen, methyl, methyl substituted by fluorine, chlorine or bromine, ethyl, pentafluoroethyl, phenyl, phenyl mono- to penta- substituted by fluorine and mono- or di-substituted by chlorine, bromine, trifluoromethyl or methoxy, pyridyl or thienyl.
  • R 2 is hydrogen, methyl, trifluoromethyl, chlorodifluoromethyl, dichlorofluoromethyl, dichloromethyl, tri- chloromethyl, dibromomethyl, ethyl, pentafluoroethyl, phenyl, phenyl mono-substituted by fluorine, chlorine, trifluoromethyl or methoxy, 2- or 3-pyridyl or 2-thienyl.
  • R 2 is methyl, trifluoromethyl, chlorodifluoromethyl, dichlorofluoromethyl, dichloromethyl or trichloro- methyl.
  • R 1 is trifluoromethyl, chlorodifluoromethyl, dichlorofluoromethyl, trichloromethyl, tribromo- methyl, pentafluoroethyl or heptafluoropropyl.
  • R 1 is trifluoromethyl.
  • R 3 is methoxy; and R 4 is methyl, trifluoromethyl, chlorine, methoxy, difluoromethoxy, ethoxy or dimethylamino; or R 4 forms an -OCH 2 CH 2 - bridge to Z.
  • Suitable compounds are also those wherein R is hydrogen.
  • A is hydroxy, C 1 -C 4 alkoxy, 2-propenyloxy, 2-propynyloxy, benzyloxy, C 1 -C 4 alkyl- carbonyloxy-C 1 - or -C 2 -alkoxy, N,N-dimethylhydroxyamino, N-methoxyamino, cyanamino, or a group of the formula A 1 , A 2 , A 3 or A 4 , wherein
  • R 8 is a -COL group
  • R 7 is hydrogen
  • R 9 is hydrogen or C 1 -C 4 alkyl
  • R 7 and R 9 together are -(CH 2 ) 3 -;
  • R 10 is hydrogen
  • R 11 is C 1 -C 4 alkyl, cyclopropylmethyl, C 3 - or C 4 -alkenyl, C 3 - or C 4 -haloalkenyl, cyclopropyl, cyclobutyl, trifluoromethyl, ethylamino, n-propylamino, 2-propynylamino, di-C 1 -C 4 alkylamino, morpholino, pyridyl or pyridyl substituted by halogen or by methoxycarbonyl, N-methoxy-methylamino, phenyl or phenyl mono- or di- substituted by fluorine, chlorine, bromine or methoxy; and
  • R 13 is hydrogen, C 1 -C 4 alkyl, phenyl or phenyl mono- or di-substituted by fluorine, chlorine, methyl, trifluoromethyl, methoxy, methoxycarbonyl or nitro.
  • A is a group of the formula (A 3 ) wherein R 1 1 is methyl, ethyl, trifluoromethyl, 2-methyl-
  • A is a group of the formula (A 4 ) wherein R 12 is hydrogen; and R 13 is methyl, tert-butyl, phenyl,
  • A is a group of the formula (A 1 *) of (S)-configuration; R 7 is hydrogen; R 9 is C 1 -C 4 alkyl; or R 7
  • R 9 together are -(CH 2 ) 3 -; and R 8 is a -COL group wherein L is as defined for formula I.
  • R is hydrogen, methyl, ethyl, difluoromethyl, 2-fluoroethyl, 2-chloroethyl, 2-cyano- ethyl, 2-methoxyethyl, 2-ethoxyethyl, n-propyl, 2-propenyl, 2-propynyl or benzyl;
  • R 1 is trifluoromethyl, chlorodifluoromethyl, trichloromethyl, tribromomethyl, pentafluoroethyl or heptafluoropropyl;
  • R 2 is hydrogen, methyl, trifluoromethyl, chlorodifluoromethyl, dichlorofluoromethyl, dichloromethyl, trichloromethyl, dibromomethyl, ethyl, pentafluoroethyl, phenyl, phenyl mono-substituted by fluorine, chlorine, trifluoromethyl or methoxy, 2- or 3-pyridyl or 2-thienyl.
  • R is methyl, ethyl, difluoromethyl, 2-fluoroethyl, 2-chloroethyl, 2-methoxyethyl, 2-ethoxyethyl, n-propyl, 2-propenyl, 2-propynyl, 2-cyanoethyl or benzyl;
  • R 3 is methoxy or ethoxy
  • R 4 is methyl, trifluoromethyl, trichloromethyl, methoxy, difluoromethoxy, methyl- amino, dimethylamino, methylthio or cyclopropyl;
  • Y is nitrogen, methine or chloromethine
  • Z is nitrogen or methine
  • R 4 forms a -O(CH 2 ) 2 - bridge to Z.
  • R is hydrogen, methyl, ethyl, difluoromethyl, 2-fluoroethyl, 2-chloroethyl, 2-cyano- ethyl, 2-methoxyethyl, 2-ethoxyethyl, n-propyl, 2-propenyl, 2-propynyl or benzyl;
  • R 2 is methyl, trifluoromethyl or phenyl;
  • A is methoxy, ethoxy, tert-butoxy, 2-propenyloxy, 2-propylideneiminoethoxy, N,N-di- methylaminooxy, methoxyamino, cyanamino, imidazolyl or a group of the formula
  • R 7 is hydrogen
  • R 9 is hydrogen, C 1 -C 4 alkyl or C 1 -C 4 alkyl substituted by carboxy, phenyl, methylphosphino or methylthio; or R 7 and R 9 together are -(CH 2 ) 3 -;
  • R 8 is methylphosphino or a -COL group, and L is hydroxy or C 1 -C 4 alkoxy;
  • R 10 is hydrogen
  • R is hydrogen, methyl, ethyl, difluoromethyl, 2-fluoroethyl, 2-chloroethyl, 2-cyano- ethyl, 2-methoxyethyl, 2-ethoxyethyl, n-propyl, 2-propenyl, 2-propynyl or benzyl;
  • R 2 is methyl or trifluoromethyl
  • R ⁇ is methyl, ethyl, trifluoromethyl, 2-methyl-2-propenyl, 3-chloro-2-propenyl, cyclopropyl, dimethylamino, diethylamino, morpholino, phenyl, 2-chlorophenyl, 2-methoxycarbonylphenyl, 2-pyridyl, 3-fluoro-2-pyridyl or 2-fluoro-3-pyridyl.
  • R is hydrogen, methyl, ethyl, difluoromethyl, 2-fluoroethyl, 2-chloroethyl, 2-methoxy- ethyl, 2-ethoxyethyl, n-propyl, 2-propenyl, 2-propynyl, 2-cyanoethyl or benzyl;
  • R 2 is methyl, trifluoromethyl or phenyl
  • R 12 is hydrogen or methyl
  • R 13 is methyl, tert-butyl, phenyl, 2-chlorophenyl, 2-fluorophenyl, 2-tolyl, 2,4-difluoro- phenyl, 4-chlorophenyl, 3-trifluoromethylphenyl or 4-methoxyphenyl.
  • X is oxygen or sulfur
  • R 1 is trifluoromethyl, pentafluoroethyl or heptafluoropropyl
  • R 2 is methyl, ethyl, trifluoromethyl or phenyl.
  • R 2 to R 4 , X, Y and Z are as defined for formula I and R 1 is C 1 -C 7 alkyl, or
  • R 1 together with R 2 is -(CH 2 ) 4 - or -(CH 2 ) 5 -.
  • R 1 to R 4 , X, Y and Z are as defined for formula I and R is C 1 -C 6 alkyl, C 1 -C 4 halo- alkyl, C 1 - or C 2 -alkyl substituted by C 1 - or C 2 -alkoxy, cyano, phenyl or phenyl substituted by halogen, methyl, methoxy or trifluoromethyl, C 3 -C 6 alkenyl, C 3 -C 6 alkynyl,
  • R 1 to R 4 , X, Y, Z and R 20 are as defined, and then alkylating, acylating or s ⁇ lfon- ylating the compound of formula lb with a compound of formula IX
  • R 1 to R 4 , X, Y and Z are as defined for formula I, R is C 1 -C 6 alkyl, C 1 -C 4 halo- alkyl, C 1 - or C 2 -alkyl substimted by C 1 - or C 2 -alkoxy, cyano, phenyl or phenyl substituted by halogen, methyl, methoxy or trifluoromethyl, C 3 -C 6 alkenyl, C 3 -C 6 alkynyl,
  • a a is a leaving group, especially chlorine, bromine, 2,4,6-triisopropylphenyl-sulfonyl, imidazolyl, triazolyl, 2-thionothiazolidin-3-yl or N,N'-dicyclohexyl-isoureidyl
  • L 3 is -S(O)Cl, -C(O)Cl, -C(O)-C(O)Cl, -PCl 4 , -P(O)Cl 2 , -P(O)Br 2 , 2,4,6-triisopropyl- phenyl-sulfonyl, imidazolyl, triazolyl, N-carbonylimidazole or N-carbonyltriazole, into the compound of formula Id
  • R 1 to R 4 , X, Y and Z are as defined for formula I and R and A a are as defined above, and then reacting the compound of formula Id with a compound of formula V
  • A-H (V) wherein A is -OR 5 , -SR 6 , cyanamino, hydroxyamino, C 1 -C 6 alkoxyamino, C 1 -C 3 alkoxy- (C 1 -C 3 alkyl)amino or a group A 1 to A 4 , where appropriate in the presence of a base and a solvent.
  • R 2 to R 4 , X, Y, Z and A are as defined for formula I and R 1 is C 1 -C 7 alkyl or C 1 -C 7 haloalkyl, or R 1 together with R 2 is -(CH 2 ) 4 - or -(CH 2 ) 5 -, comprises converting a compound of formula Iq
  • R 1 to R 4 , X, Y and Z are as defined, by treatment with a water-removing reagent, such as phosphorus oxychloride, phosphorus trichloride, phosphorus pentachloride, phosphorus oxybromide, thionyl chloride, oxalyl chloride, acetic anhydride, sulfuric acid, dimethyl- or diethyl-aminosulfur trifluoride, into the compound of formula Ir
  • a water-removing reagent such as phosphorus oxychloride, phosphorus trichloride, phosphorus pentachloride, phosphorus oxybromide, thionyl chloride, oxalyl chloride, acetic anhydride, sulfuric acid, dimethyl- or diethyl-aminosulfur trifluoride, into the compound of formula Ir
  • R 2 to R 4 , X, Y and Z are as defined for formula I and R 1 is C 1 -C 7 alkyl or C 1 -C 7 haloalkyl, or R 1 together with R 2 is -(CH 2 ) 4 - or -(CH 2 ) 5 -, and then reacting the compound of formula Ir with a compound of formula V
  • A-H (V) wherein A is hydroxy, -OR 5 , -SR 6 , cyanamino, hydroxyamino, C 1 -C 6 alkoxyamino, C 1 -C 3 -alkoxy-C 1 -C 6 alkylamino or a group A 1 to A 4 , where appropriate in the presence of a base and a solvent.
  • R 3 , R 4 , X, Y and Z are as defined for formula I can be prepared by a) reacting a compound of formula IV or IVa
  • M ⁇ is a cation, such as a sodium, calcium, lithium, magnesium, dimethyl- ammonium or triethylammonium ion, with bromo- or chloro-acetic acid tert-butyl ester in the presence of a base and a suitable solvent; or b) reacting a compound of formula VI with hydroxy- or mercapto-acetic acid teft-butyl ester (VIII) in the presence of a base and a suitable solvent; in the compounds of formulae IV and VI the radicals R 3 , R 4 , X, Y and Z are as defined for formula I and L 4 is a leaving group, such as fluorine, chlorine, methyl- sulfonyl or benzylsulfonyl.
  • the condensation reaction of the compounds of formulae III and IIla with compounds of formula II in accordance with Reaction scheme 1 can advantageously be carried out in the presence of a strong base, such as lithium diisopropylamide, a potassium, sodium or lithium salt of hexamethyldisilazane, n-butyllithium, sec-butyllithium, tert-butyllithium or phenyllithium in hexane, heptane, diethoxymethane, isooctane, diethyl ether or tetrahydrofuran, especially with bis(trimethylsilyl)lithium amide in hexane and/or tetrahydrofuran, in accordance with processes known per se at temperatures of from -78°C to 0°C, preferably at temperatures of from -70°C to -50°C, in one of the solvents mentioned above and analogously to EP-A-0409 368, EP-A-0517215, Japanese Patent 0434
  • Compounds of formula In or lo wherein R has the meaning given above, with the exception of hydrogen, can be prepared by reacting the intermediate of formula lb or Ic with the corresponding electrophilic compound of formula IX in the presence of a base, such as sodium hydride, potassium hydride, lithium diisopropylamide, tetramethylethylene- diamine, triethylamine, 4-dimethylaminopyridine or diisopropylethylamine, in the presence of a suitable solvent, such as the solvents indicated above, or N,N-dimethyl- formamide, N-methylpyrrolidone, acetonitrile, toluene, dimethyl sulfoxide or a mixture thereof.
  • a base such as sodium hydride, potassium hydride, lithium diisopropylamide, tetramethylethylene- diamine, triethylamine, 4-dimethylaminopyridine or diisopropylethylamine
  • a suitable solvent such as the
  • the reaction is carried out at from -50°C to the boiling temperature of the reaction mixture, preferably from 0°C to 80°C.
  • Suitable alkylating agents of formula IX are, especially for the preparation of compounds of formula I wherein R is methyl or ethyl, dimethyl sulfate and diethyl sulfate.
  • the reaction of IIl to In or IIla to lo can be carried out directly in situ without isolation of the intermediates of formula lb or Ic, respectively.
  • the lithium, sodium or potassium salt obtained as intermediate at temperatures of from -78°C to 0°C during the reaction of IIl to lb or IIla to Ic is combined directly at temperatures of from -50°C to 0°C with the electrophilic compound of formula IX and then, if necessary, the reaction mixture can be heated until the reaction is complete.
  • the resulting isomeric mixture of formula In or lo can be separated by known methods, such as column chromatography or fractional crystallisation.
  • 2-propenyloxy, and hydrogen in the presence of a palladium/carbon catalyst is suitable as hydrolysing agent where R 20 is benzyloxy.
  • Suitable solvents for the hydrolysis are, for example, water or mixtures of methanol/water, ethanol/water, tetrahydrofuran/water, diethoxymethane/water, dioxane/water or N,N-dimethylformamide/water.
  • Suitable solvents for the hydrogenolysis are especially methanol, ethanol, ethyl acetate, acetic acid, trifluoroacetic acid, dioxane and water, and mixtures thereof.
  • Compounds of formula Im wherein A is -OR 5 , -SR 6 , cyanamino, hydroxy, C 1 -C 6 alkoxy- amino, C 1 -C 3 alkoxy(C 1 -C 3 alkyl)amino or a group A 1 to A 4 can be prepared, for example, by reacting an acid of formula la with a chlorinating agent A a -L 3 (VII), such as phosphorus oxychloride, thionyl chloride, oxalyl chloride or phosgene, phosphorus pentachloride or phosphorus oxybromide, especially phosphorus oxychloride, in the presence of a base, such as triethylamine, N,N-dimethylaniline or pyridine, and where appropriate in a solvent, such as a hydrocarbon, for example toluene, a chlorinated hydrocarbon, for example methylene chloride, or an ether, for example tetrahydrofur
  • the base can be used in a catalytic amount or in a stoichiometric amount or in excess, preferably in a stoichiometric amount or a slight excess. It is also possible to use as the base a slight excess, such as 2 equivalents, of the substrate of formula V used.
  • the reaction is preferably carried out also in the presence of a suitable solvent, for example a hydrocarbon, such as toluene; a halogenated hydrocarbon, such as dichloro- methane, 1,2-dichloroethane or chlorobenzene; an ether, such as diethyl ether, diethoxy- methane or tert-butyl methyl ether, an ester, such as ethyl acetate; an aprotic solvent, such as acetonitrile; a protic solvent, such as ethanol or water, or a two-phase system, such as a mixture of dichloromethane/water, toluene/water, ethyl acetate/water or tert-butyl methyl ether/water.
  • a suitable solvent for example a hydrocarbon, such as toluene; a halogenated hydrocarbon, such as dichloro- methane, 1,2-dichloroethane or chlorobenzene
  • the reaction temperatures may be varied within a wide range of approximately from -40°C to the boiling temperature of the solvent used.
  • the reaction is preferably carried out, however, at temperatures of from -20°C to approx. +30°C, especially from -10°C to +10°C.
  • the reaction times may, however, vary widely according to the temperature of the reaction mixture and the base used.
  • a a is a leaving group, such as 2,4,6-triisopropyl- phenyl-sulfonyl, imidazolyl, triazolyl, 2-thiono-thiazolidin-3-yl or N,N'-dicyclohexyl-iso- ureidyl, can likewise be prepared from compounds of formula la in accordance with known conversion processes using 1-(2,4,6-triisopropylphenyl-sulfonyl)-imidazole as described in Tetrahedron Lett.
  • the acid of formula Iq is then convened using from 0.50 to approx. 2 equivalents, preferably approx. 1 equivalent, of a water-removing agent, such as phosphorus oxychloride, and a slight excess of from 2.0 to 3.0 equivalents of triethylamine, into the corresponding oxetanone of formula Ir in accordance with Reaction scheme 3 and then reacted with the corresponding nucleophilic compound of formula V as described for Reaction scheme 2.
  • a water-removing agent such as phosphorus oxychloride
  • novel compounds of formula IIla can be prepared analogously to known processes, for example by a) reacting a hydroxy- or mercapto-pyrimidine or -triazine of formula IV, or a corresponding salt of formula IVa, which may be prepared in situ,
  • M ⁇ is a cation, such as a sodium, calcium, lithium, magnesium, dimethyl- ammonium or triethylammonium ion, with bromo- or chloro-acetic acid tert-butyl ester in the presence of a base, such as sodium hydrogen carbonate, potassium carbonate, sodium hydride, triethylamine or pyridine, in a suitable solvent, such as acetone, acetonitrile, tetrahydrofuran, ethyl acetate, methyl Cellosolve, dimethoxyethane, toluene, N-methyl- pyrrolidone, N,N-dimethylformamide, methanoi, water or a suitable mixture of the mentioned solvents, in accordance with Reaction scheme 4, Route a); or b) reacting a corresponding fluoro- or chloro-pyrimidine or -triazine or methyl- or benzyl- sulfonylpyrimidine
  • compounds of formula IIl wherein X is sulfur can advantageously be prepared by first converting a compound of formula VI wherein L 4 is methylsulfonyl with sodium hydrogen sulfide into the compound of formula IVa, which is then reacted in situ with bromo- or chloro-acetic acid tert-butyl ester.
  • bromoacetic acid tert-butyl ester it has proved advantageous to use bromoacetic acid tert-butyl ester and, where appropriate, to carry out the reaction in the presence of iodide ions.
  • the addition of crown ethers can accelerate the reaction.
  • the compounds of formula I can be used in unmodified form, i.e. as obtained during synthesis, but are preferably formulated in customary manner together with the adjuvants conventionally employed in formulation technology, e.g. into emulsifiable concentrates, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granules or microcapsules.
  • the methods of application such as spraying, atomising, dusting, wetting, scattering or pouring, are chosen in accordance with the intended objectives and the prevailing circumstances.
  • compositions, preparations or mixtures comprising the compound (active ingredient) of formula I or at least one compound of formula I and, where appropriate, one or more solid or liquid formulation adjuvants, are prepared in known manner, e.g. by homogeneously mixing and/or grinding the active ingredients with the adjuvants, e.g. solvents or solid carriers.
  • surface-active compounds surfactants may additionally be used in the preparation of the formulations.
  • Suitable solvents are: aromatic hydrocarbons, preferably the fractions containing 8 to 12 carbon atoms, such as mixtures of alkylbenzenes, e.g. xylene mixtures or alkylated naphthalenes; aliphatic and cycloaliphatic hydrocarbons such as paraffins, cyclohexane or tetrahydronaphthalene; alcohols, such as ethanol, propanol or butanol; glycols and their ethers and esters, such as propylene glycol or dipropylene glycol ether, ketones such as cyclohexanone, isophorone or diacetone alcohol, strongly polar solvents such as
  • N-methyl-2-pyrrolidone dimethyl sulfoxide or water
  • vegetable oils and their esters such as rape oil, castor oil or soybean oil
  • silicone oils such as rape oil, castor oil or soybean oil
  • the solid carriers used e.g. for dusts and dispersible powders are normally natural mineral fillers, such as calcite, talcum, kaolin, montmorillonite or attapulgite.
  • Suitable granulated adsorptive carriers are porous types, for example pumice, broken brick, sepiolite or bentonite; and suitable non-sorbent carriers are, for example, calcite or sand.
  • a great number of pregranulated materials of inorganic or organic nature can be used, such as especially dolomite or pulverised plant residues.
  • suitable surface- active compounds are non-ionic, cationic and/or anionic surfactants having good emulsifying, dispersing and wetting properties.
  • surfactants will also be understood as comprising mixtures of surfactants.
  • Suitable soaps are the alkali metal salts, alkaline earth metal salts or unsubstituted or substituted ammonium salts of higher fatty acids (C 10 -C 22 ), e.g. the sodium or potassium salts of oleic or stearic acid, or of natural fatty acid mixtures which can be obtained e.g. from coconut oil or tallow oil; mention may also be made of fatty acid methyltaurin salts.
  • fatty alcohol sulfonates especially fatty alcohol sulfonates, fatty alcohol sulfates, sulfonated benzimidazole derivatives or alkylarylsulfon- ates.
  • the fatty alcohol sulfonates or sulfates are usually in the form of alkali metal salts, alkaline earth metal salts or unsubstimted or substimted ammonium salts and contain a C 8 -C 22 alkyl radical, which also includes the alkyl moiety of acyl radicals, for example the sodium or calcium salt of lignosulfonic acid, of dodecyl sulfate or of a mixture of fatty alcohol sulfates obtained from natural fatty acids.
  • These compounds also comprise the salts of sulfated and sulfonated fatty alcohol/ethylene oxide adducts.
  • the sulfonated benzimidazole derivatives preferably contain 2 sulfonic acid groups and one fatty acid radical containing 8 to 22 carbon atoms.
  • alkylarylsulfonates are the sodium, calcium or triethanolamine salts of dodecylbenzenesulfonic acid, dibutylnaphthalenesulfonic acid or of a condensate of naphthalenesulfonic acid and formaldehyde.
  • corresponding phosphates e.g. salts of the phosphoric acid ester of an adduct of p-nonylphenol with 4 to 14 mol of ethylene oxide, or phospholipids.
  • Non-ionic surfactants are preferably polyglycol ether derivatives of aliphatic or cyclo- aliphatic alcohols, saturated or unsaturated fatty acids and alkylphenols, it being possible for said derivatives to contain 3 to 30 glycol ether groups and 8 to 20 carbon atoms in the (aliphatic) hydrocarbon moiety and 6 to 18 carbon atoms in the alkyl moiety of the alkylphenols.
  • non-ionic surfactants are water-soluble adducts of polyethylene oxide with polypropylene glycol, ethylenediaminopolypropylene glycol and alkylpolypropylene glycol containing 1 to 10 carbon atoms in the alkyl chain, which adducts contain 20 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups. These compounds usually contain 1 to 5 ethylene glycol units per propylene glycol unit.
  • non-ionic surfactants are nonylphenol polyethoxyethanols, castor oil polyglycol ethers, polypropylene/polyethylene oxide adducts, tributylphenoxy- polyethoxyethanol, polyethylene glycol and octylphenoxypolyethoxyethanol.
  • Fatty acid esters of polyoxyethylene sorbitan e.g. polyoxyethylene sorbitan trioleate, are also suitable non-ionic surfactants.
  • Cationic surfactants are preferably quaternary ammonium salts which contain, as
  • N-substituent at least one C 8 -C 22 alkyl radical and, as further substiments, unsubstituted or halogenated lower alkyl, benzyl or hydroxy-lower alkyl radicals.
  • the salts are preferably in the form of halides, methyl sulfates or ethyl sulfates, for example stearyltrimethyl- ammonium chloride or benzyldi(2-chloroethyl)ethylammonium bromide.
  • the herbicidal compositions usually comprise 0.1 to 99 %, preferably 0.1 to 95 %, of a compound of formula 1, 1 to 99 % of a solid or liquid adjuvant, and 0 to 25 %, preferably 0.1 to 25 %, of a surfactant.
  • compositions may also comprise further ingredients such as stabilisers, e.g. vegetable oils and epoxidised vegetable oils (epoxidised coconut oil, rape oil or soybean oil), anti- foams, e.g. silicone oil, preservatives, viscosity regulators, binders and tackifiers, as well as fertilisers or other active ingredients for obtaining special effects.
  • stabilisers e.g. vegetable oils and epoxidised vegetable oils (epoxidised coconut oil, rape oil or soybean oil)
  • anti- foams e.g. silicone oil, preservatives, viscosity regulators, binders and tackifiers, as well as fertilisers or other active ingredients for obtaining special effects.
  • Preferred formulations have especially the following composition (throughout, percentages are by weight)
  • Emulsifiable concentrates are:
  • active ingredient 1 to 90%, preferably 5 to 50%
  • surfactant 5 to 30%, preferably 10 to 20%
  • active ingredient 0.1 to 50%, preferably 0.1 to 1%
  • solid carrier 99.9 to 90%, preferably 99.9 to 99%
  • active ingredient 5 to 75%, preferably 10 to 50%
  • surfactant 1 to 40%, preferably 2 to 30%
  • active ingredient 0.5 to 90%, preferably 1 to 80%
  • surfactant 0.5 to 20%, preferably 1 to 15%
  • solid carrier 5 to 95%, preferably 15 to 90%
  • active ingredient 0.1 to 30%, preferably 0.1 to 15%
  • solid carrier 99.5 to 70%, preferably 97 to 85%
  • the compounds of formula I are generally used successfully at rates of application of from 0.001 to 2 kg/ha, especially from 0.005 to 1 kg/ha.
  • concentration required to achieve the desired effect can be determined by experiment. It is dependent upon the type of action, the stage of development of the crop plant and of the weed, and also upon the application (place, time, method) and, in dependence on those parameters, can vary within wide limits.
  • the compounds of formula I are distinguished by growth-inhibiting and herbicidal properties that make them outstandingly suitable for use in crops of useful plants, especially in cereals, cotton, soybeans, rape, maize and rice.
  • Crops are also to be understood as being those which have been rendered tolerant to herbicides or classes of herbicide by conventional methods of breeding or by genetic techniques.
  • the reaction mixture is taken up in diethyl ether and washed 3 times with water and the organic phase is dried over magnesium sulfate.
  • the diethyl ether solution is filtered off and concentrated by evaporation and the residue is dried under a high vacuum.
  • reaction mixture is then extracted with ethyl acetate and the organic phases are combined, washed with dilute hydrochloric acid and saturated sodium chloride solution, dried over magnesium sulfate and concentrated by evaporation using a Rotovap. The residue that remains is filtered over silica gel.
  • Example P7 are added in 40 ml of absolute tetrahydrofuran at a temperature below -73°C to a prepared solution of 16.7 g of lithium bis(trimethylsilyl)amide in 100 ml of hexane and 40 ml of absolute tetrahydrofuran.
  • the reaction mixture is stirred for 20 minutes and then, at a temperature below -70°C, 11.5 ml of 1,1,1-trifluoromethylacetone are added.
  • the temperature of the reaction mixture is allowed to rise slowly to room temperature and then 8.7 ml of dimethyl sulfate are added. That reaction mixture is then heated at the reflux temperature for 3 hours (internal temperature of reaction vessel 60°C).
  • reaction mixture is cooled, taken up in diethyl ether, washed in succession with water, sodium hydrogen carbonate solution, dilute hydrochloric acid and saturated sodium chloride solution, dried over magnesium sulfate and concentrated by evaporation in vacuo.
  • the residue that remains is purified on silica gel with 5-10 % diethyl ether in hexane as eluant.
  • Vacuum distillation at 130°C/1x10 -2 torr yields the desired product, 2-[(4,6-dimethoxy-pyrimidin- 2-yl)-thio]-acetic acid tert-butyl ester, in the form of a slightly yellowish liquid which changes to a wax-like state when left to stand.
  • the resulting oily product is the isomeric mixture of 2-[(4,6-dimethoxy-pyrimidin-2-yl)-thio]-3-methoxy-3-trifluoro- methyl-butyric acid imidazolide; 1 H-NMR (300 MHz, CDCl 3 ): 8.42 and 8.35 ppm (1H), 7.64 and 7.61 ppm (1H), 7.10 and 7.08 ppm (1H), 5.92 and 5.85 ppm (2s, 1H), 5.81 and 5.80 ppm (2s, 1H), 3.90 and 3.86 ppm (2s, 6H), 3.48 and 3.38 ppm (2s, 3H), 1.84 and 1.75 ppm (2s, 3H).
  • the resulting amorphous residue is an isomeric mixture of 2-[(4,6-dimethoxy-pyrimidin-2-yl)-oxy]- 3-phenyl-3-trifluoromethylpropiolactone; m.p. 100-106°C.
  • Example P11 Preparation of the isomers of 2-[(4,6-dimethoxy-pyrimidin-2-yl)-oxy]-3- hydroxy-3-phenyl-3-trifluoromethyl-propionic acid 2-chlorophenyl hydrazide
  • 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.
  • Monocotyledonous and dicotyledonous test plants are sown in plastic pots containing standard soil and, immediately after sowing, are sprayed with an aqueous suspension of the test compounds, prepared from a 25 % wettable powder formulation (Formulation example F3 b)), corresponding to a rate of application of 2 kg of active ingredient/hectare (5001 of water/ha).
  • Test plants Setaria, Cyperus, Sinapis, Stellaria, Solanum, Ipomoea.
  • Monocotyledonous and dicotyledonous test plants are raised in a greenhouse in plastic pots containing standard soil and in the 4- to 6-leaf stage are sprayed with an aqueous suspension of the test compounds of formula I, prepared from a 25 % wettable powder formulation (Formulation example F3 b)), corresponding to a rate of application of 2 kg of active ingredient/hectare (5001 of water/ha).
  • Test plants Setaria, Sinapis, Stellaria, Solanum, Ipomoea.

Abstract

Compounds of formula (I), wherein R1 is C1-C7 haloalkyl; X is oxygen or sulfur; and salts of compounds of formula (I) that contain a carboxy or sulfonamide group, and stereoisomers of the compounds of formula (I), are suitable as active ingredients in compositions for controlling weeds.

Description

PYRIMIDINYL- AND TRIAZINYL-OXY AND THIO-3-HALOALKYL-PROPIONIC ACID DERIVATIVES AS HERBICIDES
The present invention relates to novel herbicidally active pyrimidinyl- and triazinyl-oxy- and -thio-3-haloalkyl-propionic acid derivatives, to processes for the preparation thereof, to compositions comprising those compounds and to the use thereof in the control of weeds, especially in crops of useful plants or in the inhibition of plant growth.
2- and 4-pyrimidinyl- and triazinyl-oxy- and -thio-propionic acid derivatives having herbicidal activity are known and are described, for example, in EP-A-0347 811,
EP-A-0400741, EP-B-0409 368, EP-B-0411 706, EP-A-0481 512, EP-A-0517215, EP-A-0541 041, EP-A-0549079, EP-A-0567014, EP-A-0562510, EP-A-0581 184, DE-A-3 807532, WO 93/25540 and WO 94/25442.
Novel pyrimidinyl- and triazinyl-oxy- and -thio-3-haloalkyl-propionic acid derivatives having herbicidal and growth-inhibiting properties have now been found.
The present invention therefore relates to compounds of formula I
Figure imgf000003_0001
wherein
R is hydrogen, C1-C6 alkyl, C1-C4 haloalkyl, C1- or C2-alkyl substituted by C1- or
C2-alkoxy, cyano, phenyl or phenyl substituted by halogen, methyl, methoxy or trifluoromethyl, C3-C6alkenyl, C3-C6alkynyl, C3-C6cycloalkyl-C1- or -C2-alkyl,
C4-C6cycloalkyl, C1-C4alkylcarbonyl or C1-C4alkylsulfonyl;
R1 is C1-C7haloalkyl;
R2 is hydrogen, C1-C6alkyl, C1-C6haloalkyl, C2-C6alkenyl, C3-C6cycloalkyl, phenyl, phenyl substituted by fluorine, chlorine, bromine, trifluoromethyl or methoxy, 2-, 3- or 4-pyridyl, or 2- or 3-thienyl;
R3 is methyl, ethyl, methoxy, ethoxy, trifluoromethyl, difluoromethoxy or 2,2,2-tri- fluoroethoxy;
Z is nitrogen, methine or methine substituted by fluorine, chlorine, bromine or methyl;
R4 is fluorine, chlorine, methyl, ethyl, isopropyl, cyclopropyl, methoxy, ethoxy, methyl- thio, ethylthio, methylamino, dimethylamino, ethylamino, methoxymethyl, trifluoromethyl, chloromethyl, trichloromethyl or difluoromethoxy; or, if Z is methine, R4 forms a -O(CH2)m- bridge to Z, the linkage to Z being via the carbon atom;
Y is nitrogen, or, if Z is nitrogen, Y is nitrogen, methine or methine substituted by fluorine, chlorine or bromine;
X is oxygen or sulfur;
A is hydroxy, -OR5, -SR6, imidazolyl, triazolyl, 2-thionothiazolidin-3-yl, cyanamino, hydroxyamino, C1-C6alkoxyamino, C1-C3alkoxy(C1-C3alkyl)amino or a group of
Figure imgf000004_0001
A and R together form a bond;
R5 is C1-C6alkyl, C3-C6alkenyl, C3-C6alkynyl, C1-C4alkoxy-C1-C4alkyl, C1- or
C2-alkoxy-ethoxy-C1- or -C2-alkyl, C3- or C4-alkenyloxy-C1-C4alkyl, C3- or C4-alkynyloxy-C1-C4alkyl, C1-C4 alkylthio-C1-C4alkyl. C1-C4alkylsulfinyl- C1-C4alkyl, C2-C4dialkylamino-C1-C4alkyl, tri-C1-C6alkyl-silyl-C1-C4 alkyl, C1-C4alkylcarbonyloxy-C1- or -C2-alkyl, C1-C4alkoxycarbonyl-C1-C6alkyl, C3- or C4-alkenyloxycarbonyl-C1-C6alkyl, C3- or C4-alkynyloxycarbonyl-C1-C6alkyl, C1-C4alkylthiocarbonyl-C1-C4alkyl, benzyloxycarbonyl-C1-C6alkyl, C1-C4alkoxy- carbonylmethyl-carbonylmethyl, C3-C6cycloalkyl, C3-C6cycloalkyl-C1-C3alkyl, C3-C6oxacycloalkyl, C3-C6oxacycloalkyl substituted by C1-C3alkyl, C2-C6oxacyclo- alkyl-C1-C3alkyl, C3-C5dioxacycloalkyl, C3-C5dioxacycloalkyl substituted by C1-C3alkyl, C3-C5dioxacycloalkyl-C1-C3alkyl, benzyl, pyridylmethyl, C1- or C2-di- alkyl-phosphinyl, C1-C4alkylamino, dimethylamino, C2-C6alkylideneimino, (C2-C6alkylideneimino)-oxy- C1- or -C2-alkyl, phenyl, or phenyl substituted by fluorine, chlorine, bromine, methyl, methoxy or nitro;
R6 is C1-C6alkyl, C2-C4dialkylamino-C1-C4alkyl, C1-C4alkoxycarbonyl-C1-C4alkyl, phenyl, or phenyl substituted by fluorine, chlorine, bromine, methyl, methoxy or nitro;
R7 is hydrogen or methyl;
R9 is hydrogen, trifluoromethyl, C1-C4alkyl, C1-C4alkyl substituted by hydroxy,
C1-C4alkoxy, mercapto, C1-C4alkylmercapto, phenyl, 4-hydroxyphenyl, 4-imidazol- yl, 3-indolyl, carboxy, C1-C4alkoxycarbonyl, C3- or C4-alkenyloxycarbonyl, cyano, carbamoyl, methylphosphino or methylsulfoximino, C2-C6alkenyl, C2-C6alkenyl substituted by chlorine, methyl or methoxy, ethynyl, cyclopropyl, phenyl or phenyl substituted by chlorine, methyl or methoxy; or
R7 and R9 together are -(CH2)q-, -CH2CH(OH)CH2-, -CH2SCH2- or -CH2CH2SCH2-;
R8 is hydroxymethyl, formyl, cyano, phosphono, phosphino, methylphosphino or a -COL group;
R10 is hydrogen or methyl; or
R9 and R10 together are -(CH2)n-;
R11 is C1-C6alkyl, C1-C6haloalkyl, C2-C6alkenyl, C2-C6haloalkenyl, C2-C6alkynyl, C2-C6haloalkynyl, C3-C6cycloalkyl, C3-C6cycloalkylmethyl, C1-C4alkylamino, di-C1-C4alkylamino, C1-C3alkoxy-C1-C3alkylamino, C3-C6alkenylamino,
C3-C6alkynylamino, C3-C6cycloalkylamino, morpholino, piperazino, piperidino, arylamino, arylamino substituted by fluorine, chlorine, methyl, trifluoromethyl, methoxy or benzylamino, pyridyl, pyridyl substituted by fluorine, chlorine, methyl, ethyl, methoxy, memylamino, C1-C3alkoxycarbonyl, difluoromethoxy or trifluoromethyl, benzyl, phenyl or phenyl substituted by fluorine, chlorine, bromine, methyl, ethyl, trifluoromethyl, methoxy, difluoromethoxy, ethoxy, nitro, cyano or
C1-C3alkoxycarbonyl;
R12 is hydrogen or methyl; R13 is hydrogen, C1-C6alkyl, phenyl or phenyl substituted by fluorine, chlorine, bromine, iodine, C1-C4alkyl, trifluoromethyl, C1-C3alkoxy, difluoromethoxy, cyano, nitro or C1-C4alkoxycarbonyl, pyridyl or pyridyl mono- or di-substituted by fluorine, chlorine, methyl, methoxy or trifluoromethyl;
m is 2 or 3;
n is 2, 3, 4 or 5;
q is 2 or 3;
W is oxygen or sulfur;
L is hydroxy, C1-C4alkoxy, C3- or C4-alkenyloxy, amino, C1-C4alkylamino, C1-C4di- alkylamino, benzyloxy or a group of the formula (L*,) or
Figure imgf000006_0001
Figure imgf000006_0002
R14 is hydroxy, C1-C4alkoxy, 2-propenyloxy, benzyloxy, amino or a further group of the
Figure imgf000006_0003
R140 is hydroxy, C1-C4alkoxy, 2-propenyloxy, benzyloxy or amino;
R15 is hydrogen, C1-C4alkyl or benzyl;
R17 is hydrogen; or
R15 and R17 together are -(CH2)3-; and
R16 is hydrogen or methyl;
and salts of compounds of formula I that contain a carboxy or sulfonamide group, and stereoisomers of the compounds of formula I.
The compounds of formula I contain at least one asymmetric carbon atom. That means that the compounds can occur in optically isomeric forms. If an aliphatic C=C double bond is present, geometric isomerism (E or Z form) can also occur. That applies especially in the case of those compounds of formula I wherein the radicals R, R2, R5, R9 and R11 are alkenyl. Formula I thus includes all the possible stereoisomers present in the form of . enantiomers, diastereoisomers, E/Z isomers or mixtures thereof. In formula I the alkyl radicals may be straight-chained or branched. The same applies also to the/each alkyl moiety of alkoxy, alkylthio, alkylsulfinyl, alkylsulfonyloxy, alkylamino, dialkylamino, alkylsilyl, alkoxycarbonyl, alkylcarbonyloxy, haloalkyl groups and other alkyl-containing groups.
In the definitions, C1-C6alkyl is, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl or the isomers of pentyl, and hexyl or the isomers of hexyl.
An alkoxy-, cyano- or phenyl-substituted alkyl group is, for example, methoxyethyl, ethoxyethyl, cyanoethyl or benzyl.
Alkoxyethoxy-substituted alkyl groups in the definition of R5 are, for example, methoxy- ethoxy methyl.
The C2-C6alkenyl, C2-C6haloalkenyl and C3-C6alkynyl radicals occurring in the substituents may likewise be straight-chained or branched, such as vinyl, allyl, methallyl, 1-methylvinyl, but-2-en-1-yl, 3-chloro-2-propenyl, 3-chloro-2-methyl-2-propenyl, 2,3-dichloro-2-propenyl, 2-propyn-1-yl, 1-methyl-2-propyn-1-yl and but-2-yn-1-yl.
Alkoxy is, for example, methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, sec- butoxy or tert-butoxy.
Alkenyloxy is, for example, allyloxy, methallyloxy or but-2-en-1-yloxy.
Alkynyloxy is, for example, 2-propyn-1-yloxy, 2-butyn-1-yloxy or 3-butyn-1-yloxy.
Alkylamino is, for example, methylamino, ethylamino, n-propylamino, isopropylamino, n-butylamino or sec-butylamino.
Dialkylamino is, for example, dimethylamino or diethylamino.
Alkoxy(alkyl)amino is, for example, N-methoxy(methyl)amino.
Alkenylamino is, for example, 2-propenylamino. Alkynylamino is, for example, 2-propynylamino.
Cycloalkylamino is, for example, cyclopropylamino.
Alkylthio or alkylmercapto is, for example, methylthio, ethylthio, n-propylthio, isopropyl- thio, n-butylthio, sec-butylthio or tert-butylthio.
Alkylideneimino is, for example, 2-propylideneimino or 2-butylideneimino.
Alkoxycarbonyl is, for example, methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, isopropoxycarbonyl, n-butoxycarbonyl or tert-butoxycarbonyl.
A haloalkyl group may contain one or more halogen atoms, such as fluorine, chlorine or bromine, for example fluoromethyl, difluoromethyl, chloromethyl, dichloromethyl, dibromomethyl, 2-fluoroethyl, 2,2,2-trifluoroethyl, 2-chloroethyl or 2,2,2-trichloroethyl. There may be mentioned as examples of a polyhalogenated alkyl group trifluoromethyl, chlorodifluoromethyl, dichlorofluoromethyl, trichloromethyl, tribromomethyl, penta- fluoroethyl and heptafluoropropyl.
Cycloalkyl radicals that are suitable as substituents are, for example, cyclopropyl, cyclo- butyl, cyclopentyl and cyclohexyl.
Cycloalkyl-C1-C3alkyl radicals that are suitable as substituents are, for example, cyclo- propyl-methyl, cyclopropyl-ethyl, cyclopropyl-propyl, cyclobutyl-methyl, cyclobutyl- ethyl, cyclobutyl-propyl, cyclopentyl-methyl, cyclopentyl-ethyl, cyclopentyl-propyl, cyclohexyl-methyl and cyclohexyl-ethyl.
Cycloalkyl-C1- or -C2-alkoxy radicals that are suitable as substituents are, for example, cyclopropyl-methoxy, cyclopropyl-ethoxy, cyclobutyl-methoxy, cyclobutyl-ethoxy, cyclo- pentyl-methoxy, cyclopentyl-ethoxy, cyclohexyl-methoxy and cyclohexyl-ethoxy.
Oxacycloalkyl radicals that are suitable as substituents are, for example, oxacyclobutyl, oxacyclopentyl, oxacyclohexyl and oxacycloheptyl, especially oxetan-3-yl, 3-methyl- oxetan-3-yl, 3-ethyl-oxetan-3-yl and 2-methyl-oxetan-3-yl. Oxacycloalkyl-C1-C3alkyl radicals that are suitable as substituents are, for example, oxiran-2-yl-methyl, oxacyclobutyl-methyl, oxacyclobutyl-ethyl, oxacyclobutyl-propyl, oxacyclopentyl-methyl, oxacyclopentyl-ethyl, oxacyclopentyl-propyl, oxacyclohexyl- methyl, oxacyclohexyl-ethyl, oxacyclohexyl-propyl, oxacycloheptyl-methyl and oxacyclo- heptyl-propyl.
Dioxacycloalkyl radicals that are suitable as substituents are, for example, dioxacyclo- pentyl, dioxacyclohexyl, dioxacycloheptyl, methyldioxacyclopentyl, dimethyldioxacyclo- pentyl and dimethyldioxacyclohexyl.
Dioxacycloalkyl-C1-C3alkyl radicals that are suitable as substituents are, for example, dioxacyclopentyl-methyl, dioxacyclopentyl-ethyl, dioxacyclopentyl-propyl, dioxacyclo- hexyl-methyl, dioxacyclohexyl-ethyl, dioxacyclohexyl-propyl and dioxacycloheptyl- methyl, especially (1,3-dioxolan-2-yl)-methyl, (1,3-dioxolan-2-yl)-ethyl, (1,3-dioxan- 2-yl)-ethyl and [1,3-(2,2-dimethyl)-dioxolan-5-yl]-methyl.
The invention also includes the salts that the compounds of formula I are capable of forming with amines, alkali metal and alkaline earth metal bases or quaternary ammonium bases.
Suitable salts of the free carboxy groups are especially salts of alkali metals, such as lithium, sodium and potassium, salts of alkaline earth metals, such as magnesium and calcium, or salts of organic ammonium bases, such as ammonia and primary, secondary and tertiary alkylamines.
Of the alkali metal and alkaline earth metal hydroxides, as salt formers, special mention should be made of the hydroxides of lithium, sodium, potassium, magnesium and calcium, but especially those of sodium and potassium.
Examples of amines that are suitable for the formation of ammonium salts include both ammonia and primary, secondary and tertiary C1-C18alkylamines, C1-C4hydroxy alkylamines and C2-C4alkoxyalkylamines, for example methylamine, ethylamine, n-propyl- amine, isopropylamine, the four isomers of butylamine, n-amylamine, isoamylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, pentadecylamine, hexa- decylamine, heptadecylamine, octadecylamine, methyl-ethylamine, methyl-isopropyl- amine, methyl-hexylamine, methyl-nonylamine, methyl-pentadecylamine, methyl-octa- decylamine, ethyl-butylamine, ethyl-heptylamine, ethyl-octylamine, hexyl-heptylamine, hexyl-octylamine, dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, di-n-amylamine, diisoamylamine, dihexylamine, diheptylamine, dioctyl- amine, ethanolamine, n-propanolamine, isopropanolamine, N,N-diethanolamine, N-ethyl- propanolamine, N-butylethanolamine, allylamine, n-butenyl-2-amine, n-pentenyl-2-amine, 2,3-dimethylbutenyl-2-amine, di-butenyl-2-amine, n-hexenyl-2-amine, propylenediamine, trimethylamine, triethylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, tri- isobutylamine, tri-sec-butylamine, tri-n-amylamine, methoxyethylamine and ethoxyethyl- amine; heterocyclic amines, such as pyridine, quinoline, isoquinoline, morpholine, piper- idine, pyrrolidine, indoline, quinuclidine, azepine and imidazole; primary arylamines, such as anilines, methoxyanilines, ethoxyanilines, o,m,p-toluidines, phenylenediamines, benzidines, naphthylamines and o,m,p-chloroanilines; but especially triethylamine, iso- propylamine and diisopropylamine.
When A and R together form a bond, a lactone structure as shown in compounds of formula Ir is obtained.
In preferred compounds of formula I, R2 is hydrogen, methyl, methyl substituted by fluorine, chlorine or bromine, ethyl, pentafluoroethyl, phenyl, phenyl mono- to penta- substituted by fluorine and mono- or di-substituted by chlorine, bromine, trifluoromethyl or methoxy, pyridyl or thienyl.
Of those compounds, especially suitable are those compounds wherein R2 is hydrogen, methyl, trifluoromethyl, chlorodifluoromethyl, dichlorofluoromethyl, dichloromethyl, tri- chloromethyl, dibromomethyl, ethyl, pentafluoroethyl, phenyl, phenyl mono-substituted by fluorine, chlorine, trifluoromethyl or methoxy, 2- or 3-pyridyl or 2-thienyl. Of those compounds of formula I very special preference is given to those wherein R2 is methyl, trifluoromethyl, chlorodifluoromethyl, dichlorofluoromethyl, dichloromethyl or trichloro- methyl.
Preference is given also to compounds of formula I wherein R1 is C1-C3perhaloalkyl.
Of those compounds, preference is given especially to compounds of formula I wherein R1 is trifluoromethyl, chlorodifluoromethyl, dichlorofluoromethyl, trichloromethyl, tribromo- methyl, pentafluoroethyl or heptafluoropropyl. Of those compounds of formula I very special preference is given to those wherein R1 is trifluoromethyl. Preference is given likewise to compounds of formula I wherein R3 is methoxy; and R4 is methyl, trifluoromethyl, chlorine, methoxy, difluoromethoxy, ethoxy or dimethylamino; or R4 forms an -OCH2CH2- bridge to Z.
Of those compounds, compounds of formula I wherein R3 and R4 are methoxy are especially important.
Also preferred are those compounds of formula I wherein Z is methine.
Also suitable are compounds of formula I wherein R3 and R4 are methoxy; and Z is methine.
Also important are compounds of formula I wherein R is C1-C4alkyl, 2-propenyl,
2-propynyl, 2-fluoroethyl, 2-chloroethyl, 2-methoxyethyl, 2-cyanoethyl or benzyl.
Of those compounds, compounds of formula I wherein R is methyl or ethyl are especially important.
Suitable compounds are also those wherein R is hydrogen.
Also suitable are compounds wherein A and R together form a bond.
Also suitable are compounds of formula I wherein
A is hydroxy, C1-C4alkoxy, 2-propenyloxy, 2-propynyloxy, benzyloxy, C1-C4alkyl- carbonyloxy-C1- or -C2-alkoxy, N,N-dimethylhydroxyamino, N-methoxyamino, cyanamino, or a group of the formula A1, A2, A3 or A4, wherein
R8 is a -COL group and
L is as defined for formula I;
R7 is hydrogen;
R9 is hydrogen or C1-C4alkyl; or
R7 and R9 together are -(CH2)3-;
R10 is hydrogen;
R11 is C1-C4alkyl, cyclopropylmethyl, C3- or C4-alkenyl, C3- or C4-haloalkenyl, cyclopropyl, cyclobutyl, trifluoromethyl, ethylamino, n-propylamino, 2-propynylamino, di-C1-C4alkylamino, morpholino, pyridyl or pyridyl substituted by halogen or by methoxycarbonyl, N-methoxy-methylamino, phenyl or phenyl mono- or di- substituted by fluorine, chlorine, bromine or methoxy; and
R13 is hydrogen, C1-C4alkyl, phenyl or phenyl mono- or di-substituted by fluorine, chlorine, methyl, trifluoromethyl, methoxy, methoxycarbonyl or nitro.
Especially suitable are compounds of formula I wherein A is hydroxy or a group of the formula (A4) wherein R11 to R13 are as
Figure imgf000012_0001
defined for formula I.
Especially important are compounds of formula I wherein A is hydroxy.
Also especially suitable are compounds of formula I wherein A is a group of the formula (A3) wherein R1 1 is methyl, ethyl, trifluoromethyl, 2-methyl-
Figure imgf000012_0002
2-propenyl, 3-chloro-2-propenyl, cyclopropyl, cyclopropylmethyl, dimethylamino, diethylamino, morpholino, phenyl, 2-chlorophenyl, 2-methoxycarbonylphenyl, 2-pyridyl, 3-fluoro-2-pyridyl or 3-methoxycarbonyl-2-pyridyl.
Also especially suitable are compounds of formula I wherein A is a group of the formula (A4) wherein R12 is hydrogen; and R13 is methyl, tert-butyl, phenyl,
Figure imgf000012_0003
2-chlorophenyl, 2-fluorophenyl, 2,4-difluorophenyl, 2-tolyl, 4-methoxyphenyl, 4-chloro- phenyl or 3-trifluoromethylphenyl.
Also suitable are compounds of formula I wherein A is a group of the formula (A1*) of (S)-configuration; R7 is hydrogen; R9 is C1-C4alkyl; or R7
Figure imgf000012_0004
and R9 together are -(CH2)3-; and R8 is a -COL group wherein L is as defined for formula I.
Importance is attached to those compounds of formula If
Figure imgf000013_0001
wherein
R is hydrogen, methyl, ethyl, difluoromethyl, 2-fluoroethyl, 2-chloroethyl, 2-cyano- ethyl, 2-methoxyethyl, 2-ethoxyethyl, n-propyl, 2-propenyl, 2-propynyl or benzyl;
R1 is trifluoromethyl, chlorodifluoromethyl, trichloromethyl, tribromomethyl, pentafluoroethyl or heptafluoropropyl; and
R2 is hydrogen, methyl, trifluoromethyl, chlorodifluoromethyl, dichlorofluoromethyl, dichloromethyl, trichloromethyl, dibromomethyl, ethyl, pentafluoroethyl, phenyl, phenyl mono-substituted by fluorine, chlorine, trifluoromethyl or methoxy, 2- or 3-pyridyl or 2-thienyl.
Also important are those compounds of formula Ig
Figure imgf000013_0002
wherein R is methyl, ethyl, difluoromethyl, 2-fluoroethyl, 2-chloroethyl, 2-methoxyethyl, 2-ethoxyethyl, n-propyl, 2-propenyl, 2-propynyl, 2-cyanoethyl or benzyl;
R3 is methoxy or ethoxy;
R4 is methyl, trifluoromethyl, trichloromethyl, methoxy, difluoromethoxy, methyl- amino, dimethylamino, methylthio or cyclopropyl;
Y is nitrogen, methine or chloromethine; and
Z is nitrogen or methine; or
R4 forms a -O(CH2)2- bridge to Z.
Also suitable are those compounds of formulae Ih and Ip
Figure imgf000014_0001
wherein
R is hydrogen, methyl, ethyl, difluoromethyl, 2-fluoroethyl, 2-chloroethyl, 2-cyano- ethyl, 2-methoxyethyl, 2-ethoxyethyl, n-propyl, 2-propenyl, 2-propynyl or benzyl; R2 is methyl, trifluoromethyl or phenyl;
A is methoxy, ethoxy, tert-butoxy, 2-propenyloxy, 2-propylideneiminoethoxy, N,N-di- methylaminooxy, methoxyamino, cyanamino, imidazolyl or a group of the formula
Figure imgf000014_0002
wherein
R7 is hydrogen;
R9 is hydrogen, C1-C4alkyl or C1-C4alkyl substituted by carboxy, phenyl, methylphosphino or methylthio; or R7 and R9 together are -(CH2)3-;
R8 is methylphosphino or a -COL group, and L is hydroxy or C1-C4alkoxy; and
R10 is hydrogen.
Preference is given also to compounds of formula Ii
Figure imgf000015_0001
wherein
R is hydrogen, methyl, ethyl, difluoromethyl, 2-fluoroethyl, 2-chloroethyl, 2-cyano- ethyl, 2-methoxyethyl, 2-ethoxyethyl, n-propyl, 2-propenyl, 2-propynyl or benzyl;
R2 is methyl or trifluoromethyl; and
Rπ is methyl, ethyl, trifluoromethyl, 2-methyl-2-propenyl, 3-chloro-2-propenyl, cyclopropyl, dimethylamino, diethylamino, morpholino, phenyl, 2-chlorophenyl, 2-methoxycarbonylphenyl, 2-pyridyl, 3-fluoro-2-pyridyl or 2-fluoro-3-pyridyl.
Preference is given also to those compounds of formula Ij
Figure imgf000015_0002
wherein R is hydrogen, methyl, ethyl, difluoromethyl, 2-fluoroethyl, 2-chloroethyl, 2-methoxy- ethyl, 2-ethoxyethyl, n-propyl, 2-propenyl, 2-propynyl, 2-cyanoethyl or benzyl;
R2 is methyl, trifluoromethyl or phenyl;
R12 is hydrogen or methyl; and
R13 is methyl, tert-butyl, phenyl, 2-chlorophenyl, 2-fluorophenyl, 2-tolyl, 2,4-difluoro- phenyl, 4-chlorophenyl, 3-trifluoromethylphenyl or 4-methoxyphenyl.
Preference is given also to those compounds of formula It
Figure imgf000016_0001
wherein
X is oxygen or sulfur;
R1 is trifluoromethyl, pentafluoroethyl or heptafluoropropyl; and
R2 is methyl, ethyl, trifluoromethyl or phenyl.
Preference is likewise given to compounds of formula Ir
Figure imgf000016_0002
wherein
R2 to R4, X, Y and Z are as defined for formula I and R1 is C1-C7alkyl, or
R1 together with R2 is -(CH2)4- or -(CH2)5-.
There may be mentioned as very especially preferred individual compounds within the scope of formula I, in the form of a mixture of stereoisomers or in the form of pure isomers:
2-[(4,6-dimethoxy-pyrimidin-2-yl)-thio]-3-methoxy-3-trifluoromethylbutyric acid;
2-[(4,6-dimethoxy -pyrimidin-2-yl)-thio]-3-hydroxy-3-trifluoromethylbutyric acid;
2-[(4,6-dimethoxy -pyrimidm-2-yl)-thio]-3-ethoxy-3-trifluoromethylbutyric acid;
2-[(4,6-dimethoxy-pyrimidin-2-yl)-thio]-3-methyl-3-trifluoromethyl-oxetanone;
2-[(4,6-dimethoxy-pyrimidin-2-yl)-oxy]-3-methoxy-3-trifluoromethylbutyric acid;
2-[(4,6-dimethoxy -pyrimidin-2-yl)-oxy]-3-ethoxy-3-trifluoromethylbutyric acid;
2-[(4,6-dimethoxy-pyrimidin-2-yl)-thio]-3-methoxy-3,3-bis-trifluoromethylpropionic acid; and
2-[(4,6-dimethoxy-pyrimidin-2-yl)-thio]-3-hydroxy-3,3-bis-trifluoromemylpropionic acid.
The process according to the invention for the preparation of the compounds of formula I is carried out analogously to known processes and comprises, for the preparation of the acid derivatives of formula la
Figure imgf000017_0001
wherein R1 to R4, X, Y and Z are as defined for formula I and R is C1-C6alkyl, C1-C4halo- alkyl, C1- or C2-alkyl substituted by C1- or C2-alkoxy, cyano, phenyl or phenyl substituted by halogen, methyl, methoxy or trifluoromethyl, C3-C6alkenyl, C3-C6alkynyl,
C3-C6cycloalkyl-C1- or -C2-alkyl, C4-C6cycloalkyl, C1-C4alkylcarbonyl or
C1-C4alkylsulfonyl, a) converting a compound of formula III
Figure imgf000018_0001
wherein R3, R4, X, Y and Z are as defined and R20 is C1-C6alkoxy, chloroethoxy, 2-tri- methylsilylethoxy, 2-propenyloxy, benzyloxy or benzyloxy substituted by methoxy, with a compound of formula π
Figure imgf000018_0002
wherein R1 and R2 are as defined, in the presence of a suitable base into a compound of formula lb
Figure imgf000018_0003
wherein R1 to R4, X, Y, Z and R20 are as defined, and then alkylating, acylating or sμlfon- ylating the compound of formula lb with a compound of formula IX
R-L5 (IX), wherein R is as defined and L5 is a leaving group, especially chlorine, bromine, iodine or a methylsulfonyloxy, p-toluenesulfonyloxy, methoxysulfonyloxy or ethoxysulfonyloxy group, to form the compound of formula In
Figure imgf000019_0001
OR wherein R, R1 to R4, R20, X, Y and Z are as defined, where appropriate in the presence of a base and a suitable solvent, and then reacting that compound of formula In further under hydrolytic or hydrogenolytic conditions or, when R20 is the tert-C4H9-O- group, under acid-catalysed conditions; or b) reacting a compound of formula IIIa
Figure imgf000019_0002
with a compound of formula II
Figure imgf000019_0003
in the presence of a suitable base, to form a compound of formula Ic
Figure imgf000020_0001
wherein in the compounds of formulae IIla, II and Ic the radicals R1 to R4, X, Y and Z are as defined for formula I, and then alkylating, acylating or sulfonylating the compound of formula Ic with a compound of formula IX
R-L5 (IX), wherein R is as defined and L5 is a leaving group, especially chlorine, bromine, iodine or a methylsulfonyloxy, p-toluenesulfonyloxy, methoxysulfonyloxy or ethoxysulfonyloxy group, where appropriate in the presence of a base and a suitable solvent, to form a compound of formula lo
Figure imgf000020_0002
and then hydrolysing the compound of formula lo with trifluoroacetic acid, sulfuric acid or a mixture of sulfuric acid and acetic acid, where appropriate in the presence of an additional solvent.
The process according to the invention for the preparation of the acid derivatives of formula Iq
Figure imgf000021_0001
wherein R2 to R4, X, Y and Z are as defined for formula I and R1 is C1-C7alkyl or C1-C7haloalkyl, or R1 together with R2 is -(CH2)4- or -(CH2)5-, comprises reacting a compound of formula IIla
Figure imgf000021_0002
with a compound of formula II
Figure imgf000021_0003
in the presence of a suitable base, to form a compound of formula Ic
Figure imgf000022_0001
wherein in the compounds of formulae IlIa, II and Ic the radicals R2 to R4, X, Y and Z are as defined for formula I and R1 is C1-C7alkyl or C1-C7haloalkyl, or R1 together with R2 is -(CH2)4- or -(CH2)5-, and then hydrolysing the compound of formula Ic with trifluoroacetic acid, sulfuric acid, phosphoric acid or a mixture of sulfuric acid and acetic acid, where appropriate in the presence of an additional solvent.
The process according to the invention for the preparation of the compounds of formula Im
Figure imgf000022_0002
wherein R1 to R4, X, Y and Z are as defined for formula I, R is C1-C6alkyl, C1-C4halo- alkyl, C1- or C2-alkyl substimted by C1- or C2-alkoxy, cyano, phenyl or phenyl substituted by halogen, methyl, methoxy or trifluoromethyl, C3-C6alkenyl, C3-C6alkynyl,
C3-C6cycloalkyl-C1- or -C2-alkyl, C4-C6cycloalkyl, C1-C4alkylcarbonyl or C1-C4alkyl- sulfonyl and A is -OR5, -SR6, cyanamino or a group A1 to A4, comprises converting a compound of formula la
Figure imgf000023_0001
wherein R, R1 to R4, X, Y and Z are as defined, a) by reaction with a compound of formula VII
Aa-L3 (VII), wherein
Aa is a leaving group, especially chlorine, bromine, 2,4,6-triisopropylphenyl-sulfonyl, imidazolyl, triazolyl, 2-thionothiazolidin-3-yl or N,N'-dicyclohexyl-isoureidyl, and L3 is -S(O)Cl, -C(O)Cl, -C(O)-C(O)Cl, -PCl4, -P(O)Cl2, -P(O)Br2, 2,4,6-triisopropyl- phenyl-sulfonyl, imidazolyl, triazolyl, N-carbonylimidazole or N-carbonyltriazole, into the compound of formula Id
Figure imgf000023_0002
wherein R1 to R4, X, Y and Z are as defined for formula I and R and Aa are as defined above, and then reacting the compound of formula Id with a compound of formula V
A-H (V), wherein A is -OR5, -SR6, cyanamino or a group A1 to A4, where appropriate in the presence of a base and a solvent; or b) by treatment with a water-removing reagent, such as phosphorus oxychloride, into the compound of formula Ie
Figure imgf000024_0001
wherein R1 to R4, X, Y and Z are as defined for formula I and R is as defined above, and then reacting the compound of formula Ie with a compound of formula V
A-H (V), wherein A is -OR5, -SR6, cyanamino, hydroxyamino, C1-C6alkoxyamino, C1-C3alkoxy- (C1-C3alkyl)amino or a group A1 to A4, where appropriate in the presence of a base and a solvent.
The process according to the invention for the preparation of the compounds of formulae Ir and Is
Figure imgf000025_0003
wherein R2 to R4, X, Y, Z and A are as defined for formula I and R1 is C1-C7alkyl or C1-C7haloalkyl, or R1 together with R2 is -(CH2)4- or -(CH2)5-, comprises converting a compound of formula Iq
Figure imgf000025_0002
wherein R1 to R4, X, Y and Z are as defined, by treatment with a water-removing reagent, such as phosphorus oxychloride, phosphorus trichloride, phosphorus pentachloride, phosphorus oxybromide, thionyl chloride, oxalyl chloride, acetic anhydride, sulfuric acid, dimethyl- or diethyl-aminosulfur trifluoride, into the compound of formula Ir
Figure imgf000025_0001
wherein R2 to R4, X, Y and Z are as defined for formula I and R1 is C1-C7alkyl or C1-C7haloalkyl, or R1 together with R2 is -(CH2)4- or -(CH2)5-, and then reacting the compound of formula Ir with a compound of formula V
A-H (V), wherein A is hydroxy, -OR5, -SR6, cyanamino, hydroxyamino, C1-C6alkoxyamino, C1-C3-alkoxy-C1-C6alkylamino or a group A1 to A4 , where appropriate in the presence of a base and a solvent.
Compounds of formula IIIa
Figure imgf000026_0001
wherein R3, R4, X, Y and Z are as defined for formula I can be prepared by a) reacting a compound of formula IV or IVa
Figure imgf000026_0002
wherein M⊕ is a cation, such as a sodium, calcium, lithium, magnesium, dimethyl- ammonium or triethylammonium ion, with bromo- or chloro-acetic acid tert-butyl ester in the presence of a base and a suitable solvent; or b) reacting a compound of formula VI
Figure imgf000027_0001
with hydroxy- or mercapto-acetic acid teft-butyl ester (VIII) in the presence of a base and a suitable solvent; in the compounds of formulae IV and VI the radicals R3, R4, X, Y and Z are as defined for formula I and L4 is a leaving group, such as fluorine, chlorine, methyl- sulfonyl or benzylsulfonyl.
The process variants for the preparation of the acid derivatives of formula la wherein R is C1-C6alkyl, C1-C4haloalkyl, C1- or C2-alkyl substimted by C1- or C2-alkoxy, cyano, phenyl or phenyl substimted by halogen, methyl, methoxy or trifluoromethyl,
C3-C6alkenyl, C3-C6alkynyl, C3-C6cycloalkyl-C1- or -C2-alkyl, C4-C6cycloalkyl,
C1-C4alkylcarbonyl or C1-C4alkylsulfonyl, follow Reaction scheme 1, the preparation of acid derivatives of formulae la and Iq wherein R is hydrogen advantageously being effected using Process variant lb) via the acid-catalysed removal of isobutylene (see Reaction scheme 3). The process variant for the preparation of the compounds of formula Im wherein A is -OR5, -SR6, cyanamino, hydroxyamino, C1-C6alkoxyamino,
C1-C3alkoxy-C1-C3alkylamino or a group A1 to A4, and R has the meanings given, with the exception of hydrogen, follows Reaction scheme 2; the process variant for the preparation of compounds of formulae Iq, Ir and Is (and Im wherein R is hydrogen) wherein the radical R1 is C1-C7alkyl or C1-C7haloalkyl, or R1 together with R2 is -(CH2)4- or -(CH2)5-, and the radicals R2 to R4, X, Y, Z and A are as defined, follows Reaction scheme 3, and the process variants for the preparation of the novel intermediates of formula IIla follow Reaction scheme 4.
Figure imgf000028_0001
Figure imgf000029_0001
Figure imgf000030_0001
Figure imgf000031_0001
Reaction scheme 4:
Route a):
Figure imgf000032_0001
The condensation reaction of the compounds of formulae III and IIla with compounds of formula II in accordance with Reaction scheme 1 can advantageously be carried out in the presence of a strong base, such as lithium diisopropylamide, a potassium, sodium or lithium salt of hexamethyldisilazane, n-butyllithium, sec-butyllithium, tert-butyllithium or phenyllithium in hexane, heptane, diethoxymethane, isooctane, diethyl ether or tetrahydrofuran, especially with bis(trimethylsilyl)lithium amide in hexane and/or tetrahydrofuran, in accordance with processes known per se at temperatures of from -78°C to 0°C, preferably at temperatures of from -70°C to -50°C, in one of the solvents mentioned above and analogously to EP-A-0409 368, EP-A-0517215, Japanese Patent 04342573 and J. Org. Chem. 54, 1543 (1989). There may be obtained an isomeric mixture of compounds of formula lb or Ic or alternatively, depending upon the substituents R1, R2, X, R20 and -OC(CH3)3 and the reaction conditions used, a concentration of one or other isomeric form may be obtained preferentially. The isomeric mixture of compounds of formula lb or Ic can be separated by known methods, for example by means of column chromatography or by fractional crystallisation with the aid of a suitable solvent. Compounds of formula In or lo wherein R has the meaning given above, with the exception of hydrogen, can be prepared by reacting the intermediate of formula lb or Ic with the corresponding electrophilic compound of formula IX in the presence of a base, such as sodium hydride, potassium hydride, lithium diisopropylamide, tetramethylethylene- diamine, triethylamine, 4-dimethylaminopyridine or diisopropylethylamine, in the presence of a suitable solvent, such as the solvents indicated above, or N,N-dimethyl- formamide, N-methylpyrrolidone, acetonitrile, toluene, dimethyl sulfoxide or a mixture thereof. The reaction is carried out at from -50°C to the boiling temperature of the reaction mixture, preferably from 0°C to 80°C. Suitable alkylating agents of formula IX are, especially for the preparation of compounds of formula I wherein R is methyl or ethyl, dimethyl sulfate and diethyl sulfate.
Advantageously, the reaction of IIl to In or IIla to lo can be carried out directly in situ without isolation of the intermediates of formula lb or Ic, respectively. In that case, the lithium, sodium or potassium salt obtained as intermediate at temperatures of from -78°C to 0°C during the reaction of IIl to lb or IIla to Ic is combined directly at temperatures of from -50°C to 0°C with the electrophilic compound of formula IX and then, if necessary, the reaction mixture can be heated until the reaction is complete. The resulting isomeric mixture of formula In or lo can be separated by known methods, such as column chromatography or fractional crystallisation.
Compounds of formula In wherein R20 is C1-C6alkoxy, chloroethoxy, 2-trimethylsilyl- ethoxy, 2-propenyloxy, benzyloxy or benzyloxy substimted by methoxy, can be converted analogously to known processes, such as those described, for example, in EP-A-0347 811, EP-A-0400741, EP-A-0409 368, EP-A-0481 512 and EP-A-0517 215, by hydrolysis or hydrogenolysis into the acids of formula la in accordance with Reaction scheme 1, Route a). Suitable hydrolysing agents are, for example, sodium and potassium hydroxide or sodium and potassium carbonate. Tris(triphenylphosphine)-rhodium(I) chloride
(Wilkinson catalyst) is suitable as hydrolysing agent, for example, where R20 is
2-propenyloxy, and hydrogen in the presence of a palladium/carbon catalyst is suitable as hydrolysing agent where R20 is benzyloxy. Suitable solvents for the hydrolysis are, for example, water or mixtures of methanol/water, ethanol/water, tetrahydrofuran/water, diethoxymethane/water, dioxane/water or N,N-dimethylformamide/water. Suitable solvents for the hydrogenolysis are especially methanol, ethanol, ethyl acetate, acetic acid, trifluoroacetic acid, dioxane and water, and mixtures thereof. Some of those known hydrolysis and hydrogenolysis processes, however, yield the acid of formula la, if at all, only in poor yields and with an insufficient degree of purity.
It has been found that hydrolysis of the compounds of formula lo (wherein R20 is
-OC(CH3)3) produces the desired acid of formula la very readily in a good yield and with a high degree of purity with trifluoroacetic acid, phosphoric acid, sulfuric acid or a mixture of sulfuric acid and acetic acid and, where appropriate, in the presence of an additional solvent, such as dichloromethane, n-hexane, toluene or dioxane, in accordance with Reaction scheme 1, Route b). In that process it is advantageous to work with a slight excess of trifluoroacetic acid and without an additional solvent at mild temperatures of approx. from 0°C to 25°C or at slightly elevated temperatures of up to approx. 70°C. When trifluoroacetic acid is used as reaction medium, the excess trifluoroacetic acid can subsequently be evaporated off in vacua.
Compounds of formula Im wherein A is -OR5, -SR6, cyanamino, hydroxy, C1-C6alkoxy- amino, C1-C3alkoxy(C1-C3alkyl)amino or a group A1 to A4 can be prepared, for example, by reacting an acid of formula la with a chlorinating agent Aa-L 3 (VII), such as phosphorus oxychloride, thionyl chloride, oxalyl chloride or phosgene, phosphorus pentachloride or phosphorus oxybromide, especially phosphorus oxychloride, in the presence of a base, such as triethylamine, N,N-dimethylaniline or pyridine, and where appropriate in a solvent, such as a hydrocarbon, for example toluene, a chlorinated hydrocarbon, for example methylene chloride, or an ether, for example tetrahydrofuran, in a temperature range of from -20°C to the reflux temperature of the reaction mixture, preferably at from -5°C to 25°C, to form a compound of formula Id wherein Aa is chlorine or bromine, and reacting the corresponding acid chloride (wherein Aa is chlorine), also without isolation, directly with the corresponding nucleophilic compound of formula V, where appropriate in the presence of an additional base, especially a tertiary amine, such as triethylamine, N,N-dimethylaniline, 1,8-diazabicyclo[5.4.0]undec-7-ene, imidazole, pyridine or 2,5-di- methylpyridine, in accordance with Reaction scheme 2. The base can be used in a catalytic amount or in a stoichiometric amount or in excess, preferably in a stoichiometric amount or a slight excess. It is also possible to use as the base a slight excess, such as 2 equivalents, of the substrate of formula V used.
The reaction is preferably carried out also in the presence of a suitable solvent, for example a hydrocarbon, such as toluene; a halogenated hydrocarbon, such as dichloro- methane, 1,2-dichloroethane or chlorobenzene; an ether, such as diethyl ether, diethoxy- methane or tert-butyl methyl ether, an ester, such as ethyl acetate; an aprotic solvent, such as acetonitrile; a protic solvent, such as ethanol or water, or a two-phase system, such as a mixture of dichloromethane/water, toluene/water, ethyl acetate/water or tert-butyl methyl ether/water. The reaction temperatures may be varied within a wide range of approximately from -40°C to the boiling temperature of the solvent used. The reaction is preferably carried out, however, at temperatures of from -20°C to approx. +30°C, especially from -10°C to +10°C. The reaction times may, however, vary widely according to the temperature of the reaction mixture and the base used.
Compounds of formula Id wherein Aa is a leaving group, such as 2,4,6-triisopropyl- phenyl-sulfonyl, imidazolyl, triazolyl, 2-thiono-thiazolidin-3-yl or N,N'-dicyclohexyl-iso- ureidyl, can likewise be prepared from compounds of formula la in accordance with known conversion processes using 1-(2,4,6-triisopropylphenyl-sulfonyl)-imidazole as described in Tetrahedron Lett. 1973, 1353, using 1-(2,4,6-triisopropylphenyl-sulfonyl)- 1H-1,2,4-triazole as described in Chem. Commun. 1974, 325, using 1,1'-carbonyl-diimid- azole or 1,1'-carbonyl-di(1,2,4-triazole) as described in Angew. Chem.74, 407 (1962), using thiazolidine-2-thione as described in Tetrahedron Lett.21, 841 (1980), or using dicyclohexylcarbodiimide. In those cases also, the intermediates of formula Id can be reacted directly with the nucleophilic compound of formula V without being isolated.
It has now been found that the hydrolysis of the compounds of formula Ic (wherein R20 is -OC(CH3)3) produces the desired acid of formula Iq very readily in a good yield and with a high degree of purity with trifluoroacetic acid, sulfuric acid, phosphoric acid or a mixture of sulfuric acid and acetic acid, where appropriate in the presence of an additional solvent, such as dichloromethane, n-hexane, toluene or dioxane, in accordance with Reaction scheme 3. In that process it is advantageous to work with a slight excess of trifluoroacetic acid and without an additional solvent at mild temperatures of approx. from 0°C to 25°C or at slightly elevated temperatures of up to approx. 70°C. When trifluoroacetic acid is used as reaction medium, the excess trifluoroacetic acid is subsequently evaporated off in vacua.
The acid of formula Iq is then convened using from 0.50 to approx. 2 equivalents, preferably approx. 1 equivalent, of a water-removing agent, such as phosphorus oxychloride, and a slight excess of from 2.0 to 3.0 equivalents of triethylamine, into the corresponding oxetanone of formula Ir in accordance with Reaction scheme 3 and then reacted with the corresponding nucleophilic compound of formula V as described for Reaction scheme 2. The novel compounds of formula Ir can either be isolated or, if desired, converted directly into the compounds of formula Is or, in the case of hydrolysis, into the compounds of formula Iq.
The novel compounds of formula IIla can be prepared analogously to known processes, for example by a) reacting a hydroxy- or mercapto-pyrimidine or -triazine of formula IV, or a corresponding salt of formula IVa, which may be prepared in situ,
Figure imgf000036_0001
wherein M⊕ is a cation, such as a sodium, calcium, lithium, magnesium, dimethyl- ammonium or triethylammonium ion, with bromo- or chloro-acetic acid tert-butyl ester in the presence of a base, such as sodium hydrogen carbonate, potassium carbonate, sodium hydride, triethylamine or pyridine, in a suitable solvent, such as acetone, acetonitrile, tetrahydrofuran, ethyl acetate, methyl Cellosolve, dimethoxyethane, toluene, N-methyl- pyrrolidone, N,N-dimethylformamide, methanoi, water or a suitable mixture of the mentioned solvents, in accordance with Reaction scheme 4, Route a); or b) reacting a corresponding fluoro- or chloro-pyrimidine or -triazine or methyl- or benzyl- sulfonylpyrimidine of formula VI under the reaction conditions mentioned under a) with hydroxy- or mercapto-acetic acid tert-butyl ester (VIII) in accordance with Reaction scheme 4, Route b).
In particular, compounds of formula IIl wherein X is sulfur can advantageously be prepared by first converting a compound of formula VI wherein L4 is methylsulfonyl with sodium hydrogen sulfide into the compound of formula IVa, which is then reacted in situ with bromo- or chloro-acetic acid tert-butyl ester. For the preparation of compounds of formula III wherein X is oxygen, it has proved advantageous to use bromoacetic acid tert-butyl ester and, where appropriate, to carry out the reaction in the presence of iodide ions. In addition, both in process a) and in process b), the addition of crown ethers can accelerate the reaction.
Compounds of formulae IV, V, VI, VII, VIII and IX wherein R, R3, R4, X, Y, Z, A, Aa, L3, L4 and L5 are as defined above are known and can be prepared in accordance with processes known in the literature.
(Per-)haloketones of formula II wherein R1 and R2 are as defined above are for the most part known or can be prepared in accordance with known processes, for example analogously to Houben-Weyl 1977, Vol. VII/2c, 2145-2170.
For the use according to the invention of the compounds of formula I, or compositions comprising them, there come into consideration all the methods of application customary in agriculture, such as preemergence application, postemergence application and seed dressing, as well as various methods and techniques, such as the controlled release of active ingredient. For that purpose a solution of the active ingredient is applied to mineral granule carriers or polymerised granules (urea/formaldehyde) and dried. If required, it is also possible to apply a coating (coated granules) which allows the active ingredient to be released in metered amounts over a specific period of time.
The compounds of formula I can be used in unmodified form, i.e. as obtained during synthesis, but are preferably formulated in customary manner together with the adjuvants conventionally employed in formulation technology, e.g. into emulsifiable concentrates, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granules or microcapsules. As with the nature of the compositions, the methods of application, such as spraying, atomising, dusting, wetting, scattering or pouring, are chosen in accordance with the intended objectives and the prevailing circumstances.
The formulations, i.e. the compositions, preparations or mixtures comprising the compound (active ingredient) of formula I or at least one compound of formula I and, where appropriate, one or more solid or liquid formulation adjuvants, are prepared in known manner, e.g. by homogeneously mixing and/or grinding the active ingredients with the adjuvants, e.g. solvents or solid carriers. Surface-active compounds (surfactants) may additionally be used in the preparation of the formulations.
Suitable solvents are: aromatic hydrocarbons, preferably the fractions containing 8 to 12 carbon atoms, such as mixtures of alkylbenzenes, e.g. xylene mixtures or alkylated naphthalenes; aliphatic and cycloaliphatic hydrocarbons such as paraffins, cyclohexane or tetrahydronaphthalene; alcohols, such as ethanol, propanol or butanol; glycols and their ethers and esters, such as propylene glycol or dipropylene glycol ether, ketones such as cyclohexanone, isophorone or diacetone alcohol, strongly polar solvents such as
N-methyl-2-pyrrolidone, dimethyl sulfoxide or water; vegetable oils and their esters, such as rape oil, castor oil or soybean oil; and optionally also silicone oils.
The solid carriers used e.g. for dusts and dispersible powders are normally natural mineral fillers, such as calcite, talcum, kaolin, montmorillonite or attapulgite. In order to improve the physical properties it is also possible to add highly dispersed silicic acid or highly dispersed absorbent polymers. Suitable granulated adsorptive carriers are porous types, for example pumice, broken brick, sepiolite or bentonite; and suitable non-sorbent carriers are, for example, calcite or sand. In addition, a great number of pregranulated materials of inorganic or organic nature can be used, such as especially dolomite or pulverised plant residues.
Depending on the nature of the compound of formula I to be formulated, suitable surface- active compounds are non-ionic, cationic and/or anionic surfactants having good emulsifying, dispersing and wetting properties. The term "surfactants" will also be understood as comprising mixtures of surfactants.
Both so-called water-soluble soaps and water-soluble synthetic surface-active compounds are suitable anionic surfactants.
Suitable soaps are the alkali metal salts, alkaline earth metal salts or unsubstituted or substituted ammonium salts of higher fatty acids (C10-C22), e.g. the sodium or potassium salts of oleic or stearic acid, or of natural fatty acid mixtures which can be obtained e.g. from coconut oil or tallow oil; mention may also be made of fatty acid methyltaurin salts.
More frequently, however, so-called synthetic surfactants are used, especially fatty alcohol sulfonates, fatty alcohol sulfates, sulfonated benzimidazole derivatives or alkylarylsulfon- ates. The fatty alcohol sulfonates or sulfates are usually in the form of alkali metal salts, alkaline earth metal salts or unsubstimted or substimted ammonium salts and contain a C8-C22alkyl radical, which also includes the alkyl moiety of acyl radicals, for example the sodium or calcium salt of lignosulfonic acid, of dodecyl sulfate or of a mixture of fatty alcohol sulfates obtained from natural fatty acids. These compounds also comprise the salts of sulfated and sulfonated fatty alcohol/ethylene oxide adducts. The sulfonated benzimidazole derivatives preferably contain 2 sulfonic acid groups and one fatty acid radical containing 8 to 22 carbon atoms. Examples of alkylarylsulfonates are the sodium, calcium or triethanolamine salts of dodecylbenzenesulfonic acid, dibutylnaphthalenesulfonic acid or of a condensate of naphthalenesulfonic acid and formaldehyde.
Also suitable are corresponding phosphates, e.g. salts of the phosphoric acid ester of an adduct of p-nonylphenol with 4 to 14 mol of ethylene oxide, or phospholipids.
Non-ionic surfactants are preferably polyglycol ether derivatives of aliphatic or cyclo- aliphatic alcohols, saturated or unsaturated fatty acids and alkylphenols, it being possible for said derivatives to contain 3 to 30 glycol ether groups and 8 to 20 carbon atoms in the (aliphatic) hydrocarbon moiety and 6 to 18 carbon atoms in the alkyl moiety of the alkylphenols.
Further suitable non-ionic surfactants are water-soluble adducts of polyethylene oxide with polypropylene glycol, ethylenediaminopolypropylene glycol and alkylpolypropylene glycol containing 1 to 10 carbon atoms in the alkyl chain, which adducts contain 20 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups. These compounds usually contain 1 to 5 ethylene glycol units per propylene glycol unit.
Representative examples of non-ionic surfactants are nonylphenol polyethoxyethanols, castor oil polyglycol ethers, polypropylene/polyethylene oxide adducts, tributylphenoxy- polyethoxyethanol, polyethylene glycol and octylphenoxypolyethoxyethanol.
Fatty acid esters of polyoxyethylene sorbitan, e.g. polyoxyethylene sorbitan trioleate, are also suitable non-ionic surfactants.
Cationic surfactants are preferably quaternary ammonium salts which contain, as
N-substituent, at least one C8-C22alkyl radical and, as further substiments, unsubstituted or halogenated lower alkyl, benzyl or hydroxy-lower alkyl radicals. The salts are preferably in the form of halides, methyl sulfates or ethyl sulfates, for example stearyltrimethyl- ammonium chloride or benzyldi(2-chloroethyl)ethylammonium bromide.
The surfactants customarily employed in formulation technology, which can also be used in the compositions according to the invention, are described inter alia in the following publications:
- "Mc Cutcheon's Detergents and Emulsifiers Annual", Mc Publishing Corp., Glen Rock, New Jersey, 1988.
- M. and J. Ash, "Encyclopedia of Surfactants", Vol. I-III, Chemical Publishing Co., New York, 1980-1981.
- Dr. Helmut Stache "Tensid-Taschenbuch" (Surfactant Handbook), Carl Hanser Verlag, Munich/Vienna 1981.
The herbicidal compositions usually comprise 0.1 to 99 %, preferably 0.1 to 95 %, of a compound of formula 1, 1 to 99 % of a solid or liquid adjuvant, and 0 to 25 %, preferably 0.1 to 25 %, of a surfactant.
Whereas commercial products are preferably formulated as concentrates, the end user will normally employ dilute formulations.
The compositions may also comprise further ingredients such as stabilisers, e.g. vegetable oils and epoxidised vegetable oils (epoxidised coconut oil, rape oil or soybean oil), anti- foams, e.g. silicone oil, preservatives, viscosity regulators, binders and tackifiers, as well as fertilisers or other active ingredients for obtaining special effects.
Preferred formulations have especially the following composition (throughout, percentages are by weight)
Emulsifiable concentrates:
active ingredient: 1 to 90%, preferably 5 to 50%
surfactant: 5 to 30%, preferably 10 to 20%
solvent: 15 to 94%, preferably 70 to 85% Dusts:
active ingredient: 0.1 to 50%, preferably 0.1 to 1%
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%
surfactant: 1 to 40%, preferably 2 to 30%
Wettable powders:
active ingredient: 0.5 to 90%, preferably 1 to 80%
surfactant: 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 compounds of formula I are generally used successfully at rates of application of from 0.001 to 2 kg/ha, especially from 0.005 to 1 kg/ha. The concentration required to achieve the desired effect can be determined by experiment. It is dependent upon the type of action, the stage of development of the crop plant and of the weed, and also upon the application (place, time, method) and, in dependence on those parameters, can vary within wide limits.
The compounds of formula I are distinguished by growth-inhibiting and herbicidal properties that make them outstandingly suitable for use in crops of useful plants, especially in cereals, cotton, soybeans, rape, maize and rice.
Crops are also to be understood as being those which have been rendered tolerant to herbicides or classes of herbicide by conventional methods of breeding or by genetic techniques.
The Examples that follow further illustrate, but do not limit, the invention. Preparation examples:
Example P1: Preparation of 2-[(4,6-dimethoxy-pyrimidin-2-yl)-oxy]-acetic acid tert-butyl ester (intermediate)
Figure imgf000042_0002
A mixture of 66.0 g of 4,6-dimethoxy-2-hydroxypyrimidine, 64.0 g of bromoacetic acid tert-butyl ester, 51.0 g of potassium carbonate, 0.5 g of potassium iodide and 0.5 g of 18-crown-6 in 300 ml of dimethylformamide is thoroughly stirred for 80 minutes at 50°C. When the reaction mixture has cooled, it is taken up in diethyl ether and washed 3 times with water and the organic phase is dried over magnesium sulfate. The diethyl ether solution is filtered off and concentrated by evaporation and the residue is dried under a high vacuum. Subsequent distillation in a bulb tube at 125°C/0.2 torr yields the desired product, 2-[(4,6-dimethoxy-pyrimidin-2-yl)-oxy]-acetic acid tert-butyl ester; m.p.:
63-64.5°C.
Example P2: Preparation of 2-[(4,6-dimethoxy-pyrimidin-2-yl)-oxy]-3-hydroxy-3-tri- fluoromethylbutyric acid tert-butyl ester
Figure imgf000042_0001
At -78°C (acetone/dry ice bath), 40 ml of a 1.5 molar solution of the lithium diisopropyl- amide-mono-tetrahydrofuran complex in cyclohexane is placed in a reaction vessel. Then, with thorough stirring, a solution of 15.4 g of 2-[(4,6-dimethoxy-pyrimidin-2-yl)-oxy]- acetic acid tert-butyl ester (Example P1) in 20 ml of tetrahydrofuran is added. After 45 minutes, at a temperature below -70°C 7.5 ml of trifluoroacetone are added dropwise and the reaction mixture is then stirred for 10 minutes at -70°C and for 10 minutes at -50°C and then allowed to warm to 0°C. 100 ml of 5 % aqueous ammonium chloride solution are added to that reaction mixture which is then extracted by shaking with diethyl ether. The organic phase is separated off, washed with dilute hydrochloric acid solution and sodium chloride solution and then concentrated by evaporation. By means of crystallisation from ethyl acetate/hexane 1/30, isomer I can be obtained in the form of white crystals having a melting point of 135-137°C. 1H-NMR (300 MHz, CDCl3): 5.77 ppm (s, 1H), 5.30 ppm (s, 1H), 3.95 ppm (s, 6H), 3.72 ppm (s, 1H), 1.62 ppm (s, 3H), 1.41 ppm (s, 9H). From the mother liquor consisting of an approx. 1 :7 mixture of isomer I and isomer II there is obtained by means of column chromatography (eluant diethyl ether/- hexane = 1/4) the pure isomer II of the desired 2-[(4,6-dimethoxy-pyrimidin-2-yl)-oxy]- 3-hydroxy-3-trifluoromethylbutyric acid tert-butyl ester having a melting point
of 69-70°C.
1H-NMR (300 MHz, CDCl3): 5.77 ppm (s, 1H), 5.22 ppm (s, 1H), 3.95 ppm (s, 6H), 3.68 ppm (s, 1H), 1.54 ppm (s, 3H), 1.40 ppm (s, 9H).
Example P3: Preparation of 2-[(4,6-dimethoxy-pyrimidin-2-yl)-oxy]-3-mesyloxy- 3-phenyl-3-trifluoromethyl-propionic acid tert-butyl ester
Figure imgf000043_0001
7.0 g of the isomeric mixture of 2-[(4,6-dimethoxy-pyrimidin-2-yl)-oxy]-3-hydroxy- 3-phenyl-3-trifluoromethyl-propionic acid tert-butyl ester (Comp. No. 8.006) are heated at reflux temperature in the presence of 6.4 g of triethylamine and 0.24 g of diazabicyclo- undecene (DBU) with 3.6 g of methanesulfonic acid chloride in 20 ml of toluene. After 5 hours, the reaction mixture is washed once each with aqueous sodium hydrogen carbonate solution, dilute hydrochloric acid and saturated sodium chloride solution and concentrated by evaporation using a Rotovap. The resulting crude product is separated by chromatography on silica gel (eluant diethyl ether/hexane 3/7). There is obtained as first fraction isomer I of 2-[(4,6-dimethoxy-pyrimidin-2-yl)-oxy]-3-mesyloxy-3-phenyl-3-tri- fluoromethyl-propionic acid tert-butyl ester: 1H-NMR (300 MHz, CDCl3): 7.94 ppm (m, 2H), 7.45 ppm (m, 3H), 6.81 ppm (s, 1H), 5.78 ppm (s, 1H), 3.93 ppm (s, 6H), 3.40 ppm (s, 3H), 1.18 ppm (s, 9H).
There is obtained as second fraction isomer II of 2-[(4,6-dimethoxy-pyrimidin-2-yl)-oxy]- 3-mesyloxy-3-phenyl-3-trifluoromethyl-propionic acid tert-butyl ester: 1H-NMR
(300 MHz, CDCl3): 7.75 ppm (m, 2H), 7.47 ppm (m, 3H), 6.20 ppm (s, 1H), 5.78 ppm (s, 1H), 3.91 ppm (s, 6H), 3.34 ppm (s, 3H), 1.28 ppm (s, 9H).
Example P4: Preparation of 2-[(4,6-dimethoxy-pyrimidin-2-yl)-thio]-3-methoxy-3-tri- fluoromethyl-butyric acid tert-butyl ester
Figure imgf000044_0001
3.0 g of 2-[(4,6-dimethoxy-pyrimidin-2-yl)-thio]-3-hydroxy-3-trifluoromethyl-butyric acid tert-butyl ester (Comp. No. 8.001) are added at 0°C to 0.32 g of a 60 % dispersion of sodium hydride in oil and the mixture is then stirred for 5 minutes at 25°C; 1.32 ml of methyl iodide are added thereto and the reaction mixture is heated slowly to 40°C. The reaction mixture is then extracted with ethyl acetate and the organic phases are combined, washed with dilute hydrochloric acid and saturated sodium chloride solution, dried over magnesium sulfate and concentrated by evaporation using a Rotovap. The residue that remains is filtered over silica gel. There is obtained as pure isomer 12-[(4,6-dimethoxy- pyrimidin-2-yl)-thio]-3-methoxy-3-trifluoromethyl-butyric acid tert-butyl ester: 1H-NMR (300 MHz, CDCl3): 5.78 ppm (s, 1H), 5.24 ppm (s, 1H), 3.94 ppm (s, 6H), 3.50 ppm (s, 3H), 1.45 ppm (s, 9H). Example P5: Preparation of 2-[(4,6-dimethoxy-pyrimidin-2-yl)-thio]-3-methoxy-3-tri- fluoromethyl-butyric acid tert-butyl ester (in situ method)
Figure imgf000045_0001
26.0 g of 2-[4,6-dimethoxy-pyrimidin-2-yl)-thio]-acetic acid tert-butyl ester (Comp.
No. 9.001, Example P7) are added in 40 ml of absolute tetrahydrofuran at a temperature below -73°C to a prepared solution of 16.7 g of lithium bis(trimethylsilyl)amide in 100 ml of hexane and 40 ml of absolute tetrahydrofuran. When the addition is complete, the reaction mixture is stirred for 20 minutes and then, at a temperature below -70°C, 11.5 ml of 1,1,1-trifluoromethylacetone are added. The temperature of the reaction mixture is allowed to rise slowly to room temperature and then 8.7 ml of dimethyl sulfate are added. That reaction mixture is then heated at the reflux temperature for 3 hours (internal temperature of reaction vessel 60°C). The reaction mixture is cooled, taken up in diethyl ether, washed in succession with water, sodium hydrogen carbonate solution, dilute hydrochloric acid and saturated sodium chloride solution, dried over magnesium sulfate and concentrated by evaporation in vacuo. The residue that remains is purified on silica gel with 5-10 % diethyl ether in hexane as eluant. There is obtained as first fraction 2-[(4,6-di- methoxy-pyrimidin-2-yl)-thio]-3-methoxy-3-trifluoromethyl-butyric acid tert-butyl ester in the form of an isomeric mixture in a ratio of 84/16. 1H-NMR (300 MHz, CDCl3): 5.78 and 5.76 ppm (2s, 1H), 5.24 and 5.16 ppm (2s, 1H), 3.94 ppm (s, 6H), 3.50 and 3.45 ppm (2s, 3H), 1.71 and 1.62 ppm (2s, 3H), 1.45 and 1.43 ppm (2s, 9H).
Further elution with 10-20% diethyl ether in hexane yields as further extracts the isomers of 2-[4,6-dimethoxy-pyrimidin-2-yl)-thio]-3-hydroxy-3-trifluoromethyl-butyric acid tert- butyl ester (Comp. No. 8.001 and 8.002); 1H-NMR (300 MHz, CDCl3): isomer I:
5.80 ppm (s, 1H), 5.23 ppm (s, 1H), 5.04 ppm (s, 1H), 3.95 ppm (s, 6H), 1.48 ppm
(s, 12H); isomer II: 5.84 ppm (s, 1H), 5.66 ppm (s, 1H), 4.71 ppm (s, 1H), 3.95 ppm (s, 6H), 1.58 ppm (s, 3H), 1.46 ppm (s, 9H). Example P6: Preparation of 2-[(4,6-dimethoxy-pyrimidin-2-yl)-thio]-3-methoxy-3-tri- fluoromethyl-butyric acid
Figure imgf000046_0001
12.1 g of an isomeric mixture of 2-[(4,6-dimethoxy-pyrimidin-2-yl)-thio]-3-methoxy- 3-trifluoromethyl-butyric acid tert-butyl ester (Example P5) are left to stand for 3 hours in 20 ml of trifluoroacetic acid at room temperature. The reaction mixture is then concentrated by evaporation in vacuo and, for purification, taken up in diethyl ether and extracted with ice-cold sodium hydroxide solution. The aqueous phase is adjusted to pH 3 and the product is extracted with ethyl acetate. The organic phase is washed with samrated sodium chloride solution and then dried over sodium sulfate and concentrated by evaporation in vacuo. There is obtained by means of crystallisation from chloroform/hexane 1/5, in the form of white crystals, an 88/12 isomeric mixmre of 2-[(4,6-dimethoxy-pyrimidin-2-yl)- thio]-3-methoxy-3-trifluoromethyl-butyric acid having a melting point of 124.5-125.5°C; 1H-NMR (300 MHz, CDCl3): isomer I: 5.81 ppm (s, 1H), 5.22 ppm (s, 1H), 3.94 ppm (s, 6H), 3.52 ppm (s, 3H), 1.73 ppm (s, 3H); isomer II: 5.78 ppm (s, 1H), 5.08 ppm (s, 1H), 3.92 ppm (s, 6H), 3.48 ppm (s, 3H), 1.66 ppm (s, 3H).
Example P7: Preparation of 2-[(4,6-dimethoxy-pyrimidin-2-yl)-thio]-acetic acid tert-butyl ester (intermediate)
Figure imgf000046_0002
58.5 g of 95 % sodium hydrogen sulfide-monohydrate and 76.4 g of 4,6-dimethoxy- pyrimidine-2-methylsulfone in a mixture of 350 ml of tetrahydrofuran and 500 ml of methanoi are heated with vigorous stirring for 25 minutes at 60°C. The reaction mixture is then cooled to room temperamre and 78.0 g of bromoacetic acid tert-butyl ester are added dropwise thereto. After brief heating at 45°C, most of the solvent is distilled off and the residue is taken up in diethyl ether. The organic phase is washed with dilute sodium hydroxide solution and then with sodium chloride solution and evaporated. Vacuum distillation at 130°C/1x10-2 torr yields the desired product, 2-[(4,6-dimethoxy-pyrimidin- 2-yl)-thio]-acetic acid tert-butyl ester, in the form of a slightly yellowish liquid which changes to a wax-like state when left to stand.
Example P8: Preparation of 2-[(4,6-dimethoxy-pyrimidin-2-yl)-thio]-3-hydroxy-3-tri- fluoromethylbutyric acid
Figure imgf000047_0001
1.2 g of 2-[(4,6-dimethoxy-pyrimidin-2-yl)-thio]-3-hydroxy-3-trifluoromethylbutyric acid tert-butyl ester (Compound No. 8.002) are left to stand for 2 hours in 3 ml of trifluoroacetic acid at room temperamre. The reaction mixture is then concentrated by evaporation in vacuo, the residue is dissolved in diethyl ether and extraction is carried out with dilute sodium hydroxide solution. The alkaline/aqueous phase is separated off, adjusted to pH 2.5 and extracted again with diethyl ether. The organic phase is concentrated by evaporation and the desired product, 2-[(4,6-dimethoxy-pyrimidin-2-yl)-thio]-3-hydroxy- 3-trifluoromethylbutyric acid, is obtained in the form of crystals; m.p.: 123-124°C. Example P9: Preparation of 2-[(4,6-dimethoxy-pyrimidin-2-yl)-thio]-3-methoxy-3-tri- fluoromethyl-butyric acid imidazolide
Figure imgf000048_0001
3.75 g of 1,1-carbonyldiimidazole are placed in 22 ml of dichloromethane. At a temperature below 5°C, 6.53 g of the isomeric mixture of 2-[(4,6-dimethoxy-pyrimidin-2-yl)- thio]-3-methoxy-3-trifluoromethyl-butyric acid (Example P6) dissolved in 12 ml of dimethylformamide are added dropwise thereto. The mixture is heated to room temperamre and then stirred for 1 hour and the resulting reaction mixture is extracted with dichloromethane, washed with ice-cold 5 % sodium chloride solution, dried over magnesium sulfate and concentrated by evaporation in vacuo. The resulting oily product is the isomeric mixture of 2-[(4,6-dimethoxy-pyrimidin-2-yl)-thio]-3-methoxy-3-trifluoro- methyl-butyric acid imidazolide; 1H-NMR (300 MHz, CDCl3): 8.42 and 8.35 ppm (1H), 7.64 and 7.61 ppm (1H), 7.10 and 7.08 ppm (1H), 5.92 and 5.85 ppm (2s, 1H), 5.81 and 5.80 ppm (2s, 1H), 3.90 and 3.86 ppm (2s, 6H), 3.48 and 3.38 ppm (2s, 3H), 1.84 and 1.75 ppm (2s, 3H).
Example P10: Preparation of the isomers of 2-[(4,6-dimethoxy-pyrimidin-2-yl)-oxy]-3- phenyl-3-trifluoromethyl-propiolactone
Figure imgf000048_0002
3.0 g of the isomeric mixture of 2-[(4,6-dimethoxy-pyrimidin-2-yl)-oxy]-3-hydroxy-3- phenyl-3-trifluoromethyl-propionic acid (Compound Nos. 1.092 and 1.093) are dissolved in 30 ml of dichloromethane and at -10°C first 2.7 ml of triethylamine and then 0.38 ml of phosphorus oxychloride are added and the mixture is stirred for 10 minutes at -5°C. The resulting reaction mixture is washed twice with a small amount of ice-cold water and the organic phase is separated off, dried and concentrated by evaporation. The resulting amorphous residue is an isomeric mixture of 2-[(4,6-dimethoxy-pyrimidin-2-yl)-oxy]- 3-phenyl-3-trifluoromethylpropiolactone; m.p. 100-106°C.
Example P11: Preparation of the isomers of 2-[(4,6-dimethoxy-pyrimidin-2-yl)-oxy]-3- hydroxy-3-phenyl-3-trifluoromethyl-propionic acid 2-chlorophenyl hydrazide
Figure imgf000049_0001
1.5 g of the propiolactone from Example P10 are again dissolved in 10 ml of dichloromethane and at 20°C first 0.37 g of ortho-chlorophenylhydrazine-hydrochloride and then 0.57 ml of triethylamine are added thereto and the mixture is stirred for 30 minutes.
Diethyl ether is added to the resulting reaction mixmre which is then extracted twice with sodium carbonate solution to regenerate 2-[(4,6-dimethoxy-pyrimidin-2-yl)-oxy]- 3-hydroxy-3-phenyl-3-trifluoromethyl-propionic acid (Compound Nos. 1.092 and 1.093). The organic phase is then separated off, washed with dilute hydrochloric acid and then with aqueous sodium chloride solution, dried and concentrated by evaporation. The resulting residue is separated by column chromatography (eluant hexane/diethyl ether = 3/2) into the two isomers of 2-[(4,6-dimethoxy-pyrimidin-2-yl)-oxy]-3-hydroxy-3-phenyl- 3-trifluoromethylpropionic acid 2-chlorophenyl hydrazide.
isomer I: 1H-NMR (300 MHz, CDCl3): 8.21 ppm (d, 1H), 7.96 ppm (broad signal, 2H), 7.50 ppm (broad signal, 3H), 7.18 ppm (m, 1H), 6.75 ppm (m, 2H), 6.52 ppm (s, 1H), 6.08 ppm (d, 1H), 5.90 ppm (s, 1H), 5.88 ppm (s, 1H), 5.00 ppm (m, 1H), 3.99 ppm (s, 6H).
isomer II: 1H-NMR (300 MHz, CDCl3): 8.20 ppm (d, 1H), 7.71 ppm (broad signal, 2H),
7.36 ppm (broad signal, 3H), 7.19 ppm (d, 1H), 6.96 ppm (t, 1H), 6.78 ppm (t, 1H),
6.26 ppm (d, 1H), 6.22 ppm (d, 1H), 6.12 ppm (s, 1H), 5.76 ppm (s, 1H), 5.32 ppm (s, 1H),
3.85 ppm (s, 6H).
Example P12: Preparation of 2-[4,6-dimethoxy-pyrimidin-2-yl)-thiol-3-methoxy-3-tri- fluoromethylbutyric acid 2-methyl-2-propenylsulfonamide
Figure imgf000050_0001
0.54 g of methyl-2-propenylsulfonamide is added at 0-5°C to a suspension of 0.17 g of sodium hydride, in the form of a 60 % dispersion in oil, and the reaction mixture is then stirred at room temperamre until the evolution of hydrogen is complete. After 30 minutes, at 0-5°C 1.63 g of 2-[4,6-dimethoxy-pyrimidin-2-yl)-thio]-3-methoxy-3-trifluoromethyl- butyric acid imidazolide (Example P9) dissolved in 5 ml of N,N-dimethylformamide are added dropwise. Stirring is then continued for 4 hours at room temperamre and the reaction mixture is then extracted with ethyl acetate. The combined organic phases are washed in succession with water, dilute hydrochloric acid and sodium chloride solution, dried over magnesium sulfate and concentrated by evaporation in vacuo. Purification by column chromatography (eluant 15 % acetone/hexane) yields the concentrated isomers of 2-[4,6-dimethoxy-pyrimidin-2-yl)-thio]-3-methoxy-3-trifluoromethylbutyric acid
2-methyl-2-propenylsulfonamide.
isomer I: 1H-NMR (300 MHz, CDCl3): 8.98 ppm (broad signal, 1H), 5.73 ppm (s, 1H), 5.14 and 5.08 ppm (2xs, 2H), 4.95 ppm (s, 1H), 4.05 ppm (broad signal, 2H), 3.94 ppm (s, 6H), 3.54 ppm (s, 3H), 1.94 ppm (s, 3H), 1.72 ppm (s, 3H);
isomer II: 1H-NMR (300 MHz, CDCl3): 9.00 ppm (broad signal), 5.71 ppm (s, 1H), 5.02 and 4.96 ppm (2xd, 2H), 4.70 ppm (s, 1H), 4.10 ppm (broad signal, 2H), 3.94 ppm (s, 6H), 1.85 ppm (s, 3H), 1.68 ppm (s, 3H). Example P13: Preparation of 2-[(4,6-dimethoxypyrimidin-2-yl)-thio]-3,3-bis-trifluoro- methyl-propiolactone (Compound No. 7.014)
Figure imgf000051_0001
3.5 g of 2-[(4,6-dimethoxypyrimidin-2-yl)-thio]-3-hydroxy-3,3-bis-trifluoromethylbutyric acid (Compound No. 1.094) are placed at 0°C in 20 ml of dichloromethane and treated in the presence of 0.12 ml of triethylamine with 1.9 g of N,N-dicyclohexylcarbodiimide. The reaction mixture is then stirred for approx. 30 minutes at 22°C and the N,N'-dicyclohexyl- urea that has precipitated is filtered off. The filtrate is concentrated to dryness by evaporation. The crude desired product is obtained; 1H-NMR (300 MHz, CDCl3): 7.10 ppm (s, 1H), 5.88 ppm (s, 1H), 3.92 ppm (s, 6H).
Example P14: Preparation of 2-[(4,6-dimethoxypyrimidin-2-yl)-thio]-3-hydroxy-3.3-bis- trifluoromethyl-butyric acid tert-butyl hydrazide (Compound No. 5.042)
Figure imgf000051_0002
3.0 g of the 2-[(4,6-dimethoxypyrimidin-2-yl)-thio]-3,3-bis-trifluoromethyl-propiolactone (Compound No. 7.014) prepared in Example P13 are dissolved in tetrahydrofuran and the solution is treated in succession at 0°C with 1.0 g of tert-butyl hydrazide hydrochloride and 1.14 ml of triethylamine. After stirring for one hour at 22°C, the reaction mixture is diluted with diethyl ether and washed in succession with 1N hydrochloric acid, 5 % sodium hydrogen carbonate solution and 30 % sodium chloride solution. The residue is concentrated to dryness by evaporation and purified by chromatography on silica gel with ethyl acetate/hexane 1/9 to 1/3 as eluant. The desired compound is obtained as an amorphous product. 1H-NMR (300 MHz, CDCl3): 8.55 ppm (broad signal, NH), 8.16 ppm (broad signal, OH), 5.86 ppm (s, 1H), 5.25 ppm (s, 1H), 4.63 ppm (broad signal, NH), 3.92 ppm (s, 6H), 1.03 ppm (s, 9H).
The compounds listed in Tables 1 to 8 and the intermediates of Table 9 can be prepared in analogous manner.
Figure imgf000052_0001
Figure imgf000053_0001
Figure imgf000054_0001
Figure imgf000055_0001
Figure imgf000056_0001
Figure imgf000057_0001
Figure imgf000058_0001
Figure imgf000059_0001
Figure imgf000060_0001
Figure imgf000061_0001
Figure imgf000062_0001
Figure imgf000063_0001
Figure imgf000064_0001
Figure imgf000065_0001
Figure imgf000066_0001
Figure imgf000067_0001
Figure imgf000068_0001
Figure imgf000069_0001
Figure imgf000070_0001
Figure imgf000071_0001
Figure imgf000072_0001
Figure imgf000073_0001
Figure imgf000074_0001
Figure imgf000075_0001
Figure imgf000076_0001
Figure imgf000077_0001
Figure imgf000078_0001
Figure imgf000079_0001
Figure imgf000080_0001
Figure imgf000081_0001
Figure imgf000082_0001
Figure imgf000083_0001
Figure imgf000084_0001
Figure imgf000085_0001
Figure imgf000086_0001
Figure imgf000087_0001
Figure imgf000088_0001
Figure imgf000089_0001
Figure imgf000090_0001
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.
Biological Examples:
Example B1: Preemergence herbicidal action
Monocotyledonous and dicotyledonous test plants are sown in plastic pots containing standard soil and, immediately after sowing, are sprayed with an aqueous suspension of the test compounds, prepared from a 25 % wettable powder formulation (Formulation example F3 b)), corresponding to a rate of application of 2 kg of active ingredient/hectare (5001 of water/ha). The test plants are then cultivated in a greenhouse under optimum conditions. After 3 weeks, the test is evaluated in accordance with a scale of nine ratings (1 = total damage, 9 = no action). Ratings of 1 to 4 (especially 1 to 3) indicate good to very good herbicidal action.
Test plants: Setaria, Cyperus, Sinapis, Stellaria, Solanum, Ipomoea.
The compounds of Tables 1 to 8 exhibit pronounced herbicidal action in this test.
Examples of the good herbicidal action are listed in Table B1.
Figure imgf000091_0001
Figure imgf000092_0001
Example B2: Post-emergence herbicidal action (contact herbicide)
Monocotyledonous and dicotyledonous test plants are raised in a greenhouse in plastic pots containing standard soil and in the 4- to 6-leaf stage are sprayed with an aqueous suspension of the test compounds of formula I, prepared from a 25 % wettable powder formulation (Formulation example F3 b)), corresponding to a rate of application of 2 kg of active ingredient/hectare (5001 of water/ha). The test plants are then grown on in the greenhouse under optimum conditions. After about 18 days the test is evaluated in accordance with a scale of nine ratings (1 = total damage, 9 = no action). Ratings of 1 to 4 (especially 1 to 3) indicate good to very good herbicidal action.
Test plants: Setaria, Sinapis, Stellaria, Solanum, Ipomoea.
The compounds of Tables 1 to 8 exhibit pronounced herbicidal action in this test.
Figure imgf000093_0001

Claims

What is claimed is:
1. A compound of formula I
Figure imgf000094_0001
wherein
R is hydrogen, C1-C6alkyl, C1-C4haloalkyl, C1- or C2-alkyl substimted by C1- or
C2-alkoxy, cyano, phenyl or phenyl substimted by halogen, methyl, methoxy or trifluoromemyl, C3-C6alkenyl, C3-C6alkynyl, C3-C6cycloalkyl-C1- or - C2-alkyl, C4-C6cycloalkyl, C1-C4alkylcarbonyl or C1-C4alkylsulfonyl;
R1 is C1-C7haloalkyl;
R2 is hydrogen, C1-C6alkyl, C1-C6haloalkyl, C2-C6alkenyl, C3-C6cycloalkyl, phenyl, phenyl substimted by fluorine, chlorine, bromine, trifluoromethyl or methoxy, 2-, 3- or 4-pyridyl, or 2- or 3-thienyl;
R3 is methyl, ethyl, methoxy, ethoxy, trifluoromethyl, difluoromethoxy or 2,2,2-tri- fluoroethoxy;
Z is nitrogen, methine or methine substituted by fluorine, chlorine, bromine or methyl;
R4 is fluorine, chlorine, methyl, ethyl, isopropyl, cyclopropyl, methoxy, ethoxy, methylthio, ethylthio, memylamino, dimethylamino, ethylamino, methoxymemyl, trifluoromethyl, chloromethyl, trichloromethyl or difluoromethoxy; or, if Z is methine, R4 forms a -O(CH2)m- bridge to Z, the linkage to Z being via the carbon atom;
Y is nitrogen, or, if Z is nitrogen, Y is nitrogen, methine or methine substituted by fluorine, chlorine or bromine;
X is oxygen or sulfur,
A is hydroxy, -OR5, -SR6, imidazolyl, triazolyl, 2-thionothiazolidin-3-yl, cyanamino, hydroxyamino, C1-C6alkoxyamino, C1-C3alkoxy(C1-C3alkyl)amino or a group of
Figure imgf000095_0001
A and R togetiier form a bond;
R5 is C1-C6alkyl, C3-C6alkenyl, C3-C6alkynyl, C1-C4alkoxy-C1-C4alkyl, C1- or
C2-alkoxy-ethoxy-C1- or -C2-alkyl, C3- or C4-alkenyloxy-C1-C4alkyl, C3- or C4-alkynyloxy-C1-C4alkyl, C1-C4alkylthio-C1-C4alkyl, C1-C4alkylsulfinyl- C1-C4alkyl, C2-C4dialkylamino-C1-C4alkyl, tri-C1-C6alkyl-silyl-C1-C4alkyl, C1-C4 alkylcarbonyloxy-C1- or -C2-alkyl, C1-C4alkoxycarbonyl-C1-C6alkyl, C3- or C4-alkenyloxycarbonyl-C1-C6alkyl, C3- or C4-alkynyloxycarbonyl-C1-C6alkyl, C1-C4alkylthiocarbonyl-C1-C4alkyl, benzyloxycarbonyl-C1-C6alkyl, C1-C4alkoxy- carbonylmethyl-carbonylmethyl, C3-C6cycloalkyl, C3-C6cycloalkyl-C1-C3alkyl, C3-C6oxacycloalkyl, C3-C6oxacycloalkyl substituted by C1-C3alkyl, C2-C6oxacyclo- alkyl-C!-C3alkyl, C3-C5dioxacycloalkyl, C3-C5dioxacycloalkyl substimted by C1-C3alkyl, C3-C5dioxacycloalkyl-C1-C3alkyl, benzyl, pyridylmethyl, C1- or C2-di- alkyl-phosphinyl, C1-C4alkylamino, dimethylamino, C2-C6alkylideneimino, (C2-C6alkylideneimino)-oxy-C1- or -C2-alkyl, phenyl, or phenyl substimted by fluorine, chlorine, bromine, methyl, methoxy or nitro;
R6 is C1-C6alkyl, C2-C6dialkylamino-C1-C4alkyl, C1-C4alkoxycarbonyl-C1-C4alkyl, phenyl, or phenyl substimted by fluorine, chlorine, bromine, methyl, methoxy or nitro; R7 is hydrogen or methyl;
R9 is hydrogen, trifluoromethyl, C1-C4alkyl, C1-C4alkyl substimted by hydroxy,
C1-C4alkoxy, mercapto, C1-C4alkylmercapto, phenyl, 4-hydroxyphenyl, 4-imidazol- yl, 3-indolyl, carboxy, C1-C4alkoxycarbonyl, C3- or C4-alkenyloxycarbonyl, cyano, carbamoyl, methylphosphino or methylsulfoximino, C2-C6alkenyl, C2-C6alkenyl substituted by chlorine, methyl or methoxy, ethynyl, cyclopropyl, phenyl or phenyl substimted by chlorine, methyl or methoxy; or
R7 and R9 together are -(CH2)q-, -CH2CH(OH)CH2-, -CH2SCH2- or -CH2CH2SCH2-;
R8 is hydroxymethyl, formyl, cyano, phosphono, phosphino, methylphosphino or a
-COL group;
R10 is hydrogen or methyl; or
R9 and R10 together are -(CH2)n-;
R11 is C1-C6alkyl, C1-C6haloalkyl, C2-C6alkenyl, C2-C6haloalkenyl, C2-C6alkynyl,
C2-C6haloalkynyl, C3-C6cycloalkyl, C3-C6cycloalkylmethyl, C1-C4alkylamino, di-C1-C4alkylamino, C1-C3alkoxy-C1-C3alkylamino, C3-C6alkenylamino,
C3-C6alkynylamino, C3-C6cycloalkylamino, morpholino, piperazino, piperidino, arylamino, arylamino substimted by fluorine, chlorine, methyl, trifluoromethyl, methoxy or benzylamino, pyridyl, pyridyl substimted by fluorine, chlorine, methyl, ethyl, methoxy, difluoromethoxy, trifluoromethyl, methylamino or C1-C3alkoxy- carbonyl, benzyl, phenyl or phenyl substimted by fluorine, chlorine, bromine, methyl, ethyl, trifluoromethyl, methoxy, difluoromethoxy, ethoxy, nitro, cyano or C1-C3alkoxycarbonyl;
R12 is hydrogen or methyl;
R13 is hydrogen, C1-C6alkyl, phenyl or phenyl substimted by fluorine, chlorine, bromine, iodine, C1-C4alkyl, trifluoromethyl, C1-C3alkoxy, difluoromethoxy, cyano, nitro or C1-C4alkoxycarbonyl, pyridyl or pyridyl mono- or di-substituted by fluorine, chlorine, methyl, methoxy or trifluoromethyl;
m is 2 or 3;
n is 2, 3, 4 or 5;
q is 2 or 3;
W is oxygen or sulfur;
L is hydroxy, C1-C4alkoxy, C3- or C4-alkenyloxy, amino, C1-C4alkylamino, C1-C4di- alkylamino, benzyloxy or a group of the formula (Lj) or
"
Figure imgf000096_0001
Figure imgf000097_0001
R14 is hydroxy, C1-C4alkoxy, 2-propenyloxy, benzyloxy, amino or a further group of the formula
Figure imgf000097_0002
R140 is hydroxy, C1-C4alkoxy, 2-propenyloxy, benzyloxy or amino;
R15 is hydrogen, C1-C4alkyl or benzyl;
R17 is hydrogen; or
R15 and R17 together are -(CH2)3-; and
R16 is hydrogen or methyl;
or a salt of a compound of formula I that contains a carboxy or sulfonamide group, or a stereoisomer of a compound of formula I.
2. A compound according to claim 1, wherein R2 is hydrogen, methyl, methyl substimted by fluorine, chlorine or bromine, ethyl, pentafluoroethyl, phenyl, phenyl mono- to penta- substituted by fluorine or mono- to di-substimted by chlorine, bromine, trifluoromethyl or methoxy, pyridyl or thienyl.
3. A compound according to claim 2, wherein R2 is hydrogen, metiiyl, trifluoromethyl, chlorodifluoromethyl, dichlorofluoromemyl, dichloromethyl, trichloromethyl, dibromo- methyl, ethyl, pentafluoroethyl, phenyl, phenyl mono-substituted by fluorine, chlorine, trifluoromethyl or methoxy, 2- or 3-pyridyl or 2-thienyl.
4. A compound according to claim 3, wherein R2 is methyl, trifluoromethyl, chlorodifluoromethyl, dichlorofluoromethyl, dichloromethyl or trichloromethyl.
5. A compound according to claim 1, wherein R1 is C1-C3perhaloalkyl.
6. A compound according to claim 5, wherein R1 is trifluoromethyl, chlorodifluoromethyl, dichlorofluoromethyl, trichloromethyl, tribromomethyl, pentafluoroethyl or heptafluoropropyl.
7. A compound according to claim 6, wherein R1 is trifluoromethyl.
8. A compound according to claim 1, wherein R3 is methoxy; and R4 is methyl, trifluoromethyl, chlorine, methoxy, difluoromethoxy, ethoxy or dimethylamino; or R4 forms a -OCH2CH2- bridge to Z.
9. A compound according to claim 8, wherein R3 and R4 are methoxy.
10. A compound according to claim 1, wherein Z is methine.
11. A compound according to claim 1, wherein R3 and R4 are methoxy; and Z is methine.
12. A compound according to claim 1, wherein R is C1-C4 alkyl, 2-propenyl, 2-propynyl, 2-fluoroethyl, 2-chloroethyl, 2-methoxyethyl, 2-cyanoethyl or benzyl.
13. A compound according to claim 12, wherein R is methyl or ethyl.
14. A compound according to claim 1, wherein R is hydrogen.
15. A compound according to claim 1, wherein A and R together form a bond.
16. A compound according to claim 1, wherein
A is hydroxy, C1-C4 alkoxy, 2-propenyloxy, 2-propynyloxy, benzyloxy, C1-C4alkyl- carbonyloxy-C1- or -C2-alkoxy, N,N-dimethylhydroxyamino, N-methoxyamino, cyanamino, or a group of the formula A1, A2, A3 or A4, wherein
R8 is a -COL group and
L is as defined in claim 1 ;
R7 is hydrogen;
R9 is hydrogen or C1-C4alkyl; or
R7 and R9 together are -(CH2)3-;
R10 is hydrogen;
R11 is C1-C4alkyl, cyclopropyl, cyclopropylmethyl, C3- or C4-alkenyl, C3- or C4-halo- alkenyl, cyclobutyl, trifluoromethyl, ethylamino, n-propylamino, 2-propynylamino, di-C1-C4alkylamino, N-methoxy-methylamino, morpholino, pyridyl or pyridyl substimted by halogen or by methoxycarbonyl, phenyl or phenyl mono- or di- substimted by fluorine, chlorine, bromine or methoxy; and R13 is hydrogen, C1-C4alkyl, phenyl or phenyl mono- or di-substituted by fluorine, chlorine, methyl, trifluoromethyl, methoxy, methoxycarbonyl or nitro.
17. A compound according to claim 16, wherein A is hydroxy or a group of the formula (A4) wherein R1 1 to R13 are as defined in
Figure imgf000099_0001
claim 1.
18. A compound according to claim 17, wherein A is hydroxy.
19. A compound according to claim 16, wherein A is a group of the formula 11 (A3) wherein R11 is methyl, ethyl, trifluoromethyl, 2-methyl-
Figure imgf000099_0002
2-propenyl, 3-chloro-2-propenyl, cyclopropyl, cyclopropylmethyl, dimethylamino, diemylamino, morpholino, phenyl, 2-chlorophenyl, 2-methoxycarbonylphenyl, 2-pyridyl, 3-fluoro-2-pyridyl or 3-methoxycarbonyl-2-pyridyl.
20. A compound according to claim 16, wherein A is a group of the formula (A4) wherein R12 is hydrogen; and R13 is methyl, tert-butyl, phenyl,
Figure imgf000099_0004
2-chlorophenyl, 2-fluorophenyl, 2,4-difluorophenyl, 2-tolyl, 4-chlorophenyl, 4-methoxy- phenyl or 3-trifluoromethylphenyl.
21. A compound according to claim 16, wherein A is a group of the formula (A1 *) of (S)-configuration; R7 is hydrogen; R9 is C1-C4alkyl; or R7
Figure imgf000099_0003
and R9 together are -(CH2)3-; and R8 is a -COL group wherein L is as defined in claim 1.
22. A compound according to claim 1 of formula If v
Figure imgf000100_0001
wherein
R is hydrogen, methyl, ethyl, difluoromethyl, 2-fluoroethyl, 2-chloroethyl, 2-cyano- ethyl, 2-methoxyethyl, 2-ethoxyethyl, n-propyl, 2-propenyl, 2-propynyl or benzyl;
R1 is trifluoromethyl, chlorodifluoromethyl, trichloromethyl, tribromomethyl, pentafluoroethyl or heptafluoropropyl; and
R2 is hydrogen, methyl, trifluoromethyl, chlorodifluoromethyl, dichlorofluoromethyl, dichloromethyl, trichloromethyl, dibromomethyl, ethyl, pentafluoroethyl, phenyl, phenyl mono-substituted by fluorine, chlorine, trifluoromethyl or methoxy, 2- or 3-pyridyl or 2-thienyl.
23. A compound according to claim 1 of formula Ig
Figure imgf000100_0002
wherein
R is methyl, ethyl, difluoromethyl, 2-fluoroethyl, 2-chloroethyl, 2-cyanoethyl, 2-methoxyethyl, 2-ethoxyethyl, n-propyl, 2-propenyl, 2-propynyl or benzyl; R3 is methoxy or ethoxy; R4 is methyl, trifluoromethyl, trichloromethyl, methoxy, difluoromethoxy, methyl- amino, dimethylamino, methylthio or cyclopropyl;
Y is nitrogen, methine or chloromethine; and
Z is nitrogen or methine; or
R4 forms a -O(CH2)2- bridge to Z.
24. A compound according to claim 1 of formula Ih or Ip
Figure imgf000101_0001
wherein
R is hydrogen, methyl, ethyl, difluoromethyl, 2-fluoroethyl, 2-chloroethyl, 2-cyano- ethyl, 2-methoxyethyl, 2-ethoxyethyl, n-propyl, 2-propenyl, 2-propynyl or benzyl; R2 is methyl, phenyl or trifluoromethyl;
A is methoxy, ethoxy, tert-butoxy, 2-propenyloxy, 2-propylideneiminoethoxy, N,N-di- methylaminooxy, cyanamino, methoxyamino, imidazolyl or a group of the formula
Figure imgf000101_0002
wherein
R7 is hydrogen;
R9 is hydrogen, C1-C4alkyl or C1-C4alkyl substimted by carboxy, phenyl, methylphosphino or methylthio; or
R7 and R9 together are -(CH2)3-;
R8 is methylphosphino or a -COL group, and L is hydroxy or C1-C4alkoxy; and R10 is hydrogen.
25. A compound according to claim 1 of formula Ii
Figure imgf000102_0001
wherein
R is hydrogen, methyl, ethyl, difluoromethyl, 2-fluoroethyl, 2-chloroethyl, 2-cyano- ediyl, 2-methoxyethyl, 2-ethoxyethyl, n-propyl, 2-propenyl, 2-propynyl or benzyl;
R2 is methyl or trifluoromethyl; and
R11 is methyl, ethyl, trifluoromethyl, 2-methyl-2-propenyl, 3-chloro-2-propenyl, cyclopropyl, dimethylamino, diemylamino, morpholino, phenyl, 2-chlorophenyl, 2-methoxycarbonylphenyl, 2-pyridyl, 2-fluoro-3-pyridyl or 3-fluoro-2-pyridyl.
26. A compound according to claim 1 of formula Ij
Figure imgf000102_0002
wherein
R is hydrogen, methyl, ethyl, difluoromethyl, 2-fluoroethyl, 2-chloroethyl, 2-cyano- ethyl, 2-methoxyethyl, 2-ethoxyethyl, n-propyl, 2-propenyl, 2-propynyl or benzyl; R2 is methyl, trifluoromethyl or phenyl; R12 is hydrogen or methyl; and
R13 is metiiyl, tert-butyl, phenyl, 2-chlorophenyl, 2-fluorophenyl, 2-tolyl, 2,4-difluoro- phenyl, 4-chlorophenyl, 3-trifluoromethylphenyl or 4-methoxyphenyl.
27. A compound according to claim 1 of formula It
Figure imgf000103_0001
wherein
X is oxygen or sulfur;
R1 is trifluoromethyl, pentafluoroethyl or heptafluoropropyl; and
R2 is methyl, ethyl, trifluoromethyl or phenyl.
28. A compound in the form of a mixmre of stereoisomers or in the form of the pure isomer according to claim 1, selected from:
2-[(4,6-dimethoxy-pyrimidin-2-yl)-thio]-3-methoxy-3-trifluoromethylbutyric acid;
2-[(4,6-dimemoxy-pyrimidin-2-yl)-thio]-3-hydroxy-3-trifluoromethylbutyric acid;
2-[(4,6-dimethoxy-pyrirnidin-2-yl)-thio]-3-ethoxy-3-trifluoromethylbutyric acid;
2-[(4,6-dimemoxy-pyrimidin-2-yl)-thio]-3-methyl-3-trifluoromethyl-oxetanone;
2-[(4,6-dimethoxy-pyrimidin-2-yl)-oxy]-3-methoxy-3-trifluoromethylbutyric acid;
2-[(4,6-dimemoxy-pyrimidin-2-yl)-oxy]-3-ethoxy-3-trifluoromethylbutyric acid;
2-[(4,6-dimemoxy-pyrimidin-2-yl)-thio]-3-memoxy-3,3-bis-trifluoromethylpropionic acid; and
2-[(4,6-dimethoxy-pyrimidin-2-yl)-thio]-3-hydroxy-3,3-bis-trifluoromethylpropionic acid.
29. A process for the preparation of a compound of formula la
Figure imgf000104_0001
wherein R1 to R4, X, Y and Z are as defined in claim 1 and R is C1-C6alkyl, C1-C4halo- alkyl, C1- or C2-alkyl substimted by C1- or C2-alkoxy, cyano, phenyl or phenyl substituted by halogen, methyl, methoxy or trifluoromethyl, C3-C6alkenyl, C3-C6alkynyl,
C3-C6cycloalkyl-C1- or -C2-alkyl, C4-C6cycloalkyl, C1-C4alkylcarbonyl or
C1-C4alkylsulfonyl, according to claim 1, which process comprises reacting a compound of formula III
Figure imgf000104_0002
with a compound of formula II
Figure imgf000104_0003
in the presence of a suitable base, to form a compound of formula lb wherein in the compounds of formulae III, II and lb the radicals R1 to R4, X, Y and Z are as defined in claim 1 and R20 is C1-C6alkoxy, chloroethoxy, 2-trimethylsilylethoxy, 2-propenyloxy, benzyloxy or benzyloxy substimted by methoxy, and tiien alkylating, acylating or sulf onylating the compound of formula lb with a compound of formula IX
R-L5 (IX), wherein R is as defined and L5 is a leaving group, where appropriate in the presence of a base and a suitable solvent, to form the compound of formula In
Figure imgf000105_0002
and tiien reacting that compound of formula In further under hydrolytic or hydrogenolytic conditions or, when R20 is the tert-C4H9-O- group, under acid-catalysed conditions.
30. A process for the preparation of a compound of formula Iq
Figure imgf000106_0001
wherein R2 to R4, X, Y and Z are as defined in claim 1 and R1 is C1-C7alkyl or C1-C7halo- alkyl, or R1 together with R2 is -(CH2)4- or -(CH2)5-, according to claim 1, which process comprises reacting a compound of formula IIla
Figure imgf000106_0002
with a compound of formula II
Figure imgf000106_0003
in the presence of a suitable base, to form a compound of formula Ic
Figure imgf000107_0001
wherein in the compounds of formulae IIla, II and Ic the radicals R2 to R4, X, Y and Z are as defined and R1 is C1-C7alkyl or C1-C7haloalkyl, or R1 together with R2 is -(CH2)4- or -(CH2)5-, and then hydrolysing me compound of formula Ic with trifluoroacetic acid, sulfuric acid, phosphoric acid or a mixture of sulfuric acid and acetic acid, where appropriate in the presence of an additional solvent.
31. A process for the preparation of a compound of formula Im
Figure imgf000107_0002
wherein R1 to R4, X, Y and Z are as defined in claim 1, R is C1-C6alkyl, C1-C4haloalkyl, C1- or C2-alkyl substimted by C1- or C2-alkoxy, cyano, phenyl or phenyl substituted by halogen, methyl, methoxy or trifluoromethyl, C3-C6alkenyl, C3-C6alkynyl,
C3-C6cycloalkyl-C1- or -C2-alkyl, C4-C6cycloalkyl, C1-C4alkylcarbonyl or C1-C4alkyl- sulfonyl and A is -OR5, -SR6, cyanamino or a group A1 to A4, according to claim 1, which process comprises converting a compound of formula la
Figure imgf000108_0001
wherein R, R1 to R4, X, Y and Z are as defined, a) by reaction with a compound of formula VII
Aa-L3 (VII), wherein
Aa is a leaving group, especially chlorine, bromine, 2,4,6-triisopropylphenyl-sulfonyl, imidazolyl, triazolyl, 2-thionothiazolidin-3-yl or N,N'-dicyclohexyl-isoureidyl, and L3 is -S(O)Cl, -C(O)Cl, -C(O)-C(O)Cl, -PCl4, -P(O)Cl2, -P(O)Br2, 2,4,6-triisopropyl- phenyl-sulfonyl, imidazolyl, triazolyl, N-carbonylimidazole or N-carbonyltriazole, into the compound of formula Id
Figure imgf000108_0002
wherein R1 to R4, X, Y and Z are as defined in claim 1 and R and Aa are as defined above, and then reacting the compound of formula Id with a compound of formula V
A-H (V), wherein A is -OR5, -SR6, cyanamino or a group A1 to A4, where appropriate in the presence of a base and a solvent; or b) by treatment with a water-removing reagent, such as phosphorus oxychloride, into the compound of formula Ie
Figure imgf000109_0001
wherein R1 to R4, X, Y and Z are as defined in claim 1 and R is as defined above, and then reacting the compound of formula Ie with a compound of formula V
A-H (V), wherein A is -OR5, -SR6, cyanamino, hydroxyamino, C1-C6alkoxyamino, C1-C3alkoxy- (C1-C3alkyl)amino or a group A1 to A4, where appropriate in the presence of a base and a solvent.
32. A process for the preparation of a compound of formula Ir or Is
Figure imgf000110_0001
wherein R2 to R4, X, Y, Z and A are as defined in claim 1 and R1 is C1-C7 alkyl or
C1-C7haloalkyl, or R1 together with R2 is -(CH2)4- or -(CH2)5-, according to claim 1, which process comprises converting a compound of formula Iq
wherein R1 to R4, X, Y and Z are as defined, by treatment with a water-removing reagent, such as phosphorus oxychloride, into the compound of formula Ir
Figure imgf000110_0003
wherein R2 to R4, X, Y and Z are as defined in claim 1 and R1 is C1-C7alkyl or C1-C7halo- alkyl, or R1 together with R2 is -(CH2)4- or -(CH2)5-, and then reacting the compound of formula Ir with a compound of formula V
A-H (V), wherein A is hydroxy, -OR5, -SR6, cyanamino, hydroxyamino, C1-C6alkoxyamino, C1-C3alkoxy-C1-C6alkylamino or a group A1 to A4 , where appropriate in the presence of a base and a solvent.
33. A process for the preparation of a compound of formula ϋla
Figure imgf000111_0001
wherein R3, R4, X, Y and Z are as defined in claim 1, which process comprises a) reacting a compound of formula IV or IVa
Figure imgf000111_0002
wherein M⊕ is a cation, with bromo- or chloro-acetic acid tert-butyl ester in the presence of a base and a suitable solvent; or b) reacting a compound of formula VI
Figure imgf000112_0001
with hydroxy- or mercapto-acetic acid tert-butyl ester (VIII) in the presence of a base and a suitable solvent; in the compounds of formulae IV and VI the radicals R3, R4, X, Y and Z are as defined in claim 1 and L4 is a leaving group, preferably fluorine, chlorine, methylsulfonyl or benzylsulfonyl.
34. A compound of formula IIla
Figure imgf000112_0002
o
wherein R3, R4, Z, Y and X are as defined in claim 1.
35. A compound of formula Ir
Figure imgf000112_0003
wherein R2 to R4, X, Y and Z are as defined in claim 1 and R1 is C1-C7alkyl, or R1 together with R2 is -(CH2)4- or -(CH2)5-.
36. A herbicidal and plant-growth-inhibiting composition, which comprises one or more compounds of formula I, according to claim 1.
37. A composition according to claim 36, which comprises from 0.1 % to 95 % of compound of formula I according to claim 1.
38. A method of controlling undesired plant growth, which comprises applying an effective amount of a compound of formula I, according to claim 1, or of a composition comprising that compound, to the plants or to the locus thereof.
39. A method according to claim 38, which comprises applying a compound of formula I in an amount of from 0.001 to 2 kg per hectare.
40. A method of inhibiting plant growth, which comprises applying an effective amount of a compound of formula I, according to claim 1, or of a composition comprising that compound, to the plants or to the locus thereof.
41. A method according to claim 38 for the selective pre- or post-emergence control of weeds in crops of useful plants, especially cereals, maize, rice, soybeans, rape and cotton.
42. The use of a composition according to claim 36 in the selective pre- or post-emergence control of weeds in crops of useful plants, especially cereals, maize, rice, soybeans, rape and cotton.
PCT/EP1995/002295 1994-06-27 1995-06-13 Pyrimidinyl- and triazinyl-oxy and thio-3-haloalkyl-propionic acid derivatives as herbicides WO1996000219A1 (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1997038982A1 (en) * 1996-04-12 1997-10-23 Basf Aktiengesellschaft Novel carboxylic acid derivatives, their production and use
US7109205B2 (en) 1994-10-14 2006-09-19 Abbott Gmbh & Co. Kg Carboxylic acid derivatives, their preparation and use

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0347811A1 (en) * 1988-06-20 1989-12-27 Kumiai Chemical Industry Co., Ltd. Alkanoic acid derivatives and herbicidal compositions
EP0481512A1 (en) * 1990-10-19 1992-04-22 Ube Industries, Ltd. 3-Alkoxyalkanoic acid derivative, process for preparing the same and herbicide using the same
EP0517215A1 (en) * 1991-06-07 1992-12-09 Ube Industries, Ltd. Pyrimidine or triazine derivative, process for preparing the same and herbicide using the same
EP0567014A1 (en) * 1992-04-17 1993-10-27 Ube Industries, Ltd. Sulfonamide derivative, process for preparing the same and herbicide using the same
WO1993025540A1 (en) * 1992-06-17 1993-12-23 Ciba-Geigy Ag Pyrimidinyl-and triazinyl compounds with herbicidal activity
EP0581184A1 (en) * 1992-07-21 1994-02-02 Ube Industries, Ltd. 3-Alkoxy-N-cycloalkylsulfonylalkanoic amide derivative, process for preparing the same and herbicide using the same
WO1994025442A1 (en) * 1993-04-23 1994-11-10 Basf Aktiengesellschaft 3-(hetero)aryl carboxylic acid derivatives, methods of preparing them and intermediates used in their preparation

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0347811A1 (en) * 1988-06-20 1989-12-27 Kumiai Chemical Industry Co., Ltd. Alkanoic acid derivatives and herbicidal compositions
EP0481512A1 (en) * 1990-10-19 1992-04-22 Ube Industries, Ltd. 3-Alkoxyalkanoic acid derivative, process for preparing the same and herbicide using the same
EP0517215A1 (en) * 1991-06-07 1992-12-09 Ube Industries, Ltd. Pyrimidine or triazine derivative, process for preparing the same and herbicide using the same
EP0567014A1 (en) * 1992-04-17 1993-10-27 Ube Industries, Ltd. Sulfonamide derivative, process for preparing the same and herbicide using the same
WO1993025540A1 (en) * 1992-06-17 1993-12-23 Ciba-Geigy Ag Pyrimidinyl-and triazinyl compounds with herbicidal activity
EP0581184A1 (en) * 1992-07-21 1994-02-02 Ube Industries, Ltd. 3-Alkoxy-N-cycloalkylsulfonylalkanoic amide derivative, process for preparing the same and herbicide using the same
WO1994025442A1 (en) * 1993-04-23 1994-11-10 Basf Aktiengesellschaft 3-(hetero)aryl carboxylic acid derivatives, methods of preparing them and intermediates used in their preparation

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7109205B2 (en) 1994-10-14 2006-09-19 Abbott Gmbh & Co. Kg Carboxylic acid derivatives, their preparation and use
US7119097B2 (en) 1994-10-14 2006-10-10 Abbott Gmbh & Co. Kg Carboxylic acid derivatives, their preparation and their use
US7582647B2 (en) 1994-10-14 2009-09-01 Abbott Gmbh & Co. Kg Carboxylic acid derivatives, their preparation and use
US7601730B2 (en) 1994-10-14 2009-10-13 Abbott Gmbh & Co. Kg Carboxylic acid derivatives, their preparation and use
US7863445B2 (en) 1994-10-14 2011-01-04 Abbott Gmbh & Co. Kg Carboxylic acid derivatives, their preparation and use
USRE42462E1 (en) 1994-10-14 2011-06-14 Abbott Gmbh & Co. Kg Carboxylic acid derivatives, their preparation and use
USRE42477E1 (en) 1994-10-14 2011-06-21 Abbott Gmbh & Co. Kg Carboxylic acid derivatives, their preparation and use
US8349843B2 (en) 1994-10-14 2013-01-08 Abbott Gmbh & Co. Kg Carboxylic acid derivatives, their preparation and use
WO1997038982A1 (en) * 1996-04-12 1997-10-23 Basf Aktiengesellschaft Novel carboxylic acid derivatives, their production and use
US6103732A (en) * 1996-04-12 2000-08-15 Basf Aktiengesellschaft Carboxylic acid derivatives, their production and use

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