WO1994020490A1 - Pyrimidine derivatives useful as pesticides - Google Patents

Pyrimidine derivatives useful as pesticides Download PDF

Info

Publication number
WO1994020490A1
WO1994020490A1 PCT/EP1994/000455 EP9400455W WO9420490A1 WO 1994020490 A1 WO1994020490 A1 WO 1994020490A1 EP 9400455 W EP9400455 W EP 9400455W WO 9420490 A1 WO9420490 A1 WO 9420490A1
Authority
WO
WIPO (PCT)
Prior art keywords
alkyl
hydrogen
halogen
cyano
unsubstituted
Prior art date
Application number
PCT/EP1994/000455
Other languages
French (fr)
Inventor
Harald Walter
Original Assignee
Ciba-Geigy Ag
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ciba-Geigy Ag filed Critical Ciba-Geigy Ag
Priority to EP94908333A priority Critical patent/EP0687262A1/en
Priority to JP6519509A priority patent/JPH08507500A/en
Priority to AU61412/94A priority patent/AU6141294A/en
Publication of WO1994020490A1 publication Critical patent/WO1994020490A1/en

Links

Classifications

    • 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
    • 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
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/62—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms three- or four-membered rings or rings with more than six members
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • 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
    • 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
    • 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
    • C07D401/14—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 three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
    • C07D403/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing three or more hetero rings
    • 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
    • C07D405/14—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 three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
    • C07D413/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
    • C07D417/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/0803—Compounds with Si-C or Si-Si linkages
    • C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
    • C07F7/0812—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring

Definitions

  • the invention relates to novel pesticidally active compounds of the formula I
  • R 1 is hydrogen, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, halo-C 1 -C 4 alkyl having 1, 2 or 3 halogen atoms or C 1 -C 4 alkylthio;
  • R 2 and R 3 independently of one another are hydrogen, C 1 -C 4 alkyl, halo-C 1 -C 4 alkyl having 1, 2 or 3 halogen atoms, C 1 -C 2 alkoxy-C 1 -C 4 alkyl, nitro-C 1 -C 4 alkyl, cyano-C 1 -C 4 alkyl, C 1 -C 4 alkanoyl-C 1 -C 4 alkyl, C 1 -C 4 alkoxycarbonyl-C 1 -C 4 alkyl, C 1 -C 2 alkylthio-C 1 -C 4 alkyl, C 1 -C 2 alkanesulfinyl-C 1 -C 4 alkyl, C 1 -C 2 alkanesulfonyl-C 1 -C 4 alkyl, C 2 -C 4 alkenyl, halo- C 2 -C 4 alkenyl having 1, 2 or 3 halogen atoms, C 2 -
  • R 4 is hydrogen, C 1 -C 4 alkyl, halo-C 1 -C 4 alkyl having 1, 2 or 3 halogen atoms,
  • R 5 and R 6 independently of one another are hydrogen, C 1 -C 4 alkyl, halo-C 1 -C 4 alkyl having 1, 2 or 3 halogen atoms, C 1 -C 2 alkoxy-C 1 -C 4 alkyl, nitro-C 1 -C 4 alkyl, cyano- C 1 -C 4 alkyl, C 1 -C 4 alkoxycarbonyl-C 1 -C 4 alkyl or C 3 -C 6 cycloalkyl, which is unsubstituted or substituted by one or two substituents chosen from the group comprising halogen and C 1 -C 2 alkyl;
  • R 7 , R 8 and R 9 independently of one another are hydrogen, halogen, C 1 -C 4 alkyl, halo-C 1 -C 4 alkyl having 1, 2 or 3 halogen atoms, C 1 -C 2 alkoxy-C 1 -C 4 alkyl,
  • X is OR 10 , SR 10 or N(R 11 )R 12 ;
  • Y is a group -CH(R 13 )-, oxygen, sulfur or a group -N(R 14 )-;
  • R 10 is hydrogen, an unsubstituted or substituted, open-chain, saturated or unsaturated hydrocarbon radical containing up to 12 carbon atoms, an unsubstituted or substituted cyclic saturated or unsaturated hydrocarbon radical containing up to 10 carbon atoms or unsubstituted or substituted benzyl; or an unsubstituted or substituted heterocyclyl radical;
  • R 11 is hydrogen, an open-chain saturated or unsaturated hydrocarbon radical which contains up to 8 carbon atoms and is unsubstituted or substituted by 1-5 halogen atoms, C 1 -C 2 alkoxy, hydroxyl, nitro, cyano, C 1 -C 4 alkanoyl, halo- C 1 -C 4 alkanoyl or
  • C 1 -C 4 alkoxycarbonyl a cyclic saturated or unsaturated hydrocarbon radical containing up to 10 carbon atoms or benzyl, in which the carbocyclic radical is unsubstituted or mono- to disubstituted by halogen, C 1 -C 2 alkyl, halomethyl, nitro or cyano, or heterocyclyl, which is unsubstituted or mono- to trisubstituted by identical or different substituents from the group comprising C 1 -C 2 alkyl, halogen, halomethyl, nitro and cyano;
  • R 12 is hydrogen or C 1 -C 4 alkyl
  • R 11 and R 12 together with the nitrogen atom to which they are bonded, are a heterocyclic radical which is unsubstituted or mono- to trisubstituted by identical or different substituents from the group comprising halogen, C 1 -C 2 alkyl, halomethyl and nitro;
  • R 13 is hydrogen or C 1 -C 4 alkyl
  • R 14 is hydrogen, C 1 -C 4 alkyl, C 1 -C 4 alkanoyl, benzoyl, the phenyl group of which is unsubstituted or substituted by one, two or three substituents chosen from the group comprising halogen, C 1 -C 2 alkyl, nitro and cyano, C 1 -C 4 alkylsulfonyl, or aminosulfonyl, the nitrogen atom of which is unsubstituted or mono- or disubstituted by C 1 -C 4 alkyl; n is 1 or 2;
  • the invention furthermore relates to the preparation of these compounds, agrochemical compositions which comprise at least one of these compounds as the active compound, and the use of the active compounds or compositions for pest control, in particular as microbicides in agriculture and in horticulture.
  • the compounds I and, where appropriate, their tautomers can be in the form of salts. Since the compounds I have at least one basic centre, they can form, for example, acid addition salts. These are formed, for example, with mineral acids, for example sulfuric acid, a phosphoric acid or a hydrogen halide, with organic carboxylic acids, for example acetic acid or oxalic, malonic, maleic, fumaric or phthalic acid, with hydroxycarboxylic acids, for example ascorbic, lactic, malic, tartaric or citric acid, or with benzoic acid, or with organic sulfonic acids, for example methane- or p-toluenesulfonic acid.
  • mineral acids for example sulfuric acid, a phosphoric acid or a hydrogen halide
  • organic carboxylic acids for example acetic acid or oxalic, malonic, maleic, fumaric or phthalic acid
  • hydroxycarboxylic acids for example ascorbic, lactic, mal
  • Suitable salts with bases are, for example, metal salts, such as alkali metal or alkaline earth metal salts, for example sodium salts, potassium salts or magnesium salts, or salts with ammonia or an organic amine, such as morpholine, piperidine, pyrrolidine, a mono-, di- or tri-lower alkylamine, for example ethyl-, diethyl-, triethyl- or
  • Alkyl groups are straight-chain or branched, depending on the number of carbon atoms, and are, for example, methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec -butyl, iso-butyl, tert-butyl, sec-amyl, tert-amyl, 1-hexyl or 3-hexyl.
  • Alkenyl is to be understood as meaning straight-chain or branched alkenyl, for example allyl, methallyl, 1-methylvinyl or but-2-en-1-yl. Alkenyl radicals having a chain length of 3 to 4 carbon atoms are preferred.
  • Alkynyl can likewise be straight-chain or branched, depending on the number of carbon atoms, for example propargyl, but-1-yn-1-yl and but-1-yn-3-yl. Propargyl is preferred.
  • Unsaturated hydrocarbon radicals are alkenyl, alkynyl or alkenynyl groups having not more than 3 multiple bonds, for example butadienyl, hexatrienyl or 2-penten-4-ynyl.
  • Halogen and halo are fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine.
  • Haloalkyl can contain identical or different halogen atoms, and examples would be fluoromethyl, difluoromethyl, difluorochloromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, 2,2,2-trifluoroethyl, 2-fluoroethyl, 2-chloroethyl, 2,2,2-trichloroethyl and 3,3,3-trifluoropropyl.
  • Alkoxy is, for example, methoxy, ethoxy, propyloxy, i-propyloxy, n-butyloxy, iso-butyloxy, sec-butyloxy and tert-butyloxy; preferably methoxy and ethoxy.
  • Haloalkoxy is, for example, difluoromethoxy, trifluoromethoxy, 2,2,2-trifluoroethoxy, 1,1,2,2-tetrafluoroethoxy, 2-fluoroethoxy, 2-chloroethoxy and 2,2-difluoroethoxy.
  • Cycloalkyl is cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl or cycloheptyl, depending on the ring size.
  • Cyclic unsaturated hydrocarbon radicals can be aromatic, for example phenyl and naphthyl, or non-aromatic, for example cyclopentenyl, cyclohexenyl, cycloheptenyl and cyclooctadienyl, or partly aromatic, for example tetrahydronaphthyl and indanyl.
  • Alkanoyl is either straight-chain or branched, in each case taking into account the number of carbon atoms it contains from case to case, and examples would be formyl, acetyl, propionyl, butyryl, pivaloyl or octanoyl.
  • alkoxy-, alkylthio-, alkanesulfinyl-, alkanesulfonyl-, nitro- or cyano-substituted carbon-containing groups and compounds such as alkoxyalkyl, alkylthioalkyl, alkanesulfinylalkyl, alkanesulfonylalkyl, nitroalkyl, cyanoalkyl and cyanoalkanesulfonyl, one of the hydrogen atoms present in the unsubstituted basic structure on which they are based is replaced by alkoxy, alkylthio, alkanesulfinyl, alkanesulfonyl, nitro or, respectively, cyano.
  • a heterocyclyl radical is understood as meaning a 5- or 6-membered aromatic or non-aromatic ring having the hetero atoms N, O and/or S.
  • An unsubstituted or substituted benzo group furthermore can be fused onto such a heterocyclyl radical bonded to the remainder of the molecule.
  • heterocyclyl groups are pyridyl, pyrimidinyl, imidazolyl, thiazolyl, 1,3,4-thiadiazolyl, triazolyl, thienyl, furanyl, pyrrolyl, morpholinyl, oxazolyl and the corresponding partly or totally hydrogenated rings.
  • heterocyclyl groups with a fused-on benzo group examples include quinolyl, isoquinolyl, benzoxazolyl, quinoxalinyl, benzothiazolyl, benzimidazolyl, indolyl, indolinyl.
  • R 10 is an open-chain saturated or unsaturated hydrocarbon radical which contains up to 8 carbon atoms and is unsubstituted or substituted by 1-5 halogen atoms, C 1 -C 2 alkoxy, hydroxyl, nitro, cyano, C 1 -C 4 alkanoyl, halo-C 1 -C 4 alkanoyl or C 1 -C 4 alkoxycarbonyl, a cyclic saturated or unsaturated hydrocarbon radical containing up to 10 carbon atoms or benzyl, in which the carbocyclic radical is unsubstituted or mono- to disubstituted by halogen, C 1 -C 2 alkyl, halomethyl, nitro or cyano, or heterocyclyl, which is unsubstituted or mono- to trisubstituted by identical or different substituents from the group comprising halogen, C 1 -C 2 alkyl, halomethyl, nitro and cyano, or a 5- to
  • R 10 is hydrogen, an open-chain saturated or unsaturated hydrocarbon radical which contains up to 12 carbon atoms and is unsubstituted or substituted by tri-(C 1 -C 4 alkyl)-silyl or an epoxy group; or the group
  • U is hydrogen, C 1 -C 4 alkyl, cyano, or C 1 -C 6 alkoxycarbonyl
  • W is C 1 -C 6 alkoxy, C 3 -C 6 cycloalkoxy, or the group -N(T 1 )T 2 ;
  • n 0, 1 or 2 and
  • T 1 and T 2 independently of one another are hydrogen, C 1 -C 6 alkyl, which is unsubstituted or substituted by 1-3 halogen atoms, C 1 -C 2 alkoxy, hydroxyl, nitro, cyano, C 1 -C 4 alkanoyl, halo-C 1 - C4 alkanoyl or C 1 -C 4 alkoxycarbonyl, C 1 -C 6 alkenyl which is unsubstituted or substituted by 1-3 halogen atoms, C 1 -C 6 alkynyl which is unsubstituted or substituted by
  • halogen atoms a cyclic saturated or unsaturated hydrocarbon radical containing up to
  • T 1 and T 2 together with the nitrogen atom to which they are bonded, form a 5- to
  • 7-membered heterocyclic radical which can additionally also contain O, S and/or N as ring atoms, in which the additional nitrogen is unsubstituted or substituted by C 1 -C 4 alkyl, phenyl, C 1 -C 4 alkanoyl, benzoyl or benzyl, and in which the carbon atoms of the heterocyclic radical are unsubstituted or mono- to trisubstituted by identical or different substituents from the group comprising halogen, C 1 -C 2 alkyl, halomethyl and nitro;
  • R 10 is hydrogen, an open-chain saturated or unsaturated hydrocarbon radical containing up to 6 carbon atoms, which is unsubstituted or substituted by tri-(C 1 -C 4 alkyl)-silyl or an epoxy group; or the group
  • W is C1-C 6 alkoxy, C 3 -C 6 cycloalkoxy or the group -N(T 1 )T 2 ;
  • T 1 and T 2 independently of one another are hydrogen, C 1 -C 6 alkyl, halo-C 1 -C 6 alkyl having
  • halogen atoms C 3 -C 6 cycloalkyl, phenyl, halophenyl having 1-3 halogen atoms, pyridyl or naphthyl, or
  • T 1 and T 2 together with the nitrogen atom to which they are bonded, are piperidine, piperazine, morpholine or 2,6-dimethylmorpholine.
  • R 1 is hydrogen, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, halo-C 1 -C 4 alkyl having 1, 2 or 3 halogen atoms or C 1 -C 4 alkylthio;
  • R 2 and R 3 independently of one another are hydrogen, C 1 -C 4 alkyl, halo-C 1 -C 4 alkyl having 1, 2 or 3 halogen atoms, C 1 -C 2 alkoxy-C 1 -C 4 alkyl, nitro- C 1 -C 4 alkyl, cyano-C 1 -C 4 alkyl, C 1 -C 4 alkanoyl-C 1 -C 4 alkyl, C 1 -C 4 alkoxycarbonyl-C 1 -C 4 alkyl, C 1 -C 2 alkylthio-C 1 -C 4 alkyl, C 1 -C 2 alkanesulf ⁇ nyl-C 1 -C 4 alkyl, C 1 -C 2 alkanesulfonyl-C 1 -C 4 alkyl, C 2 -C 4 alkenyl, halo- C 2 -C 4 alkenyl having 1, 2 or 3 halogen atoms, C 2
  • R 4 is hydrogen, C 1 -C 4 alkyl, halo-C 1 -C 4 alkyl having 1, 2 or 3 halogen atoms,
  • R 5 and R 6 independently of one another are hydrogen, C 1 -C 4 alkyl, halo-C 1 -C 4 alkyl having 1, 2 or 3 halogen atoms, C 1 -C 2 alkoxy-C 1 -C 4 alkyl, nitro-C 1 -C 4 alkyl, cyano-C 1 -C 4 alkyl, C 1 -C 4 alkoxycarbonyl-C 1 -C 4 alkyl or C 3 -C 6 cycloalkyl, which is unsubstituted or substituted by one or two substituents chosen from the group comprising halogen and C 1 -C 2 alkyl;
  • R 7 , R 8 and R 9 independently of one another are hydrogen, halogen, C 1 -C 4 alkyl, halo-C 1 -C 4 alkyl having 1, 2 or 3 halogen atoms, C 1 -C 2 alkoxy-C 1 -C 4 alkyl,
  • X is OR 10 , SR 10 or N(R 11 )R 12 ;
  • Y is a group -CH(R 13 )-, oxygen, sulfur or a group -N(R 14 )-;
  • R 10 is C 1 -C 8 alkyl, halo- C 1 -C 8 -alkyl having 1 to 5 halogen atoms, C 1 -C 2 alkoxy- C 1 -C 8 alkyl, hydroxy-C 1 -C 8 alkyl, nitro-C 1 -C 8 alkyl, cyano- C 1 -C 8 alkyl, C 1 -C 4 alkanoyl- C 1 -C 8 alkyl, halo-C 1 -C 4 alkanoyl-C 1 -C 8 alkyl, C 1 -C 4 alkoxycarbonyl-C 1 -C 8 alkyl,
  • C 3 -C 5 cycloalkyl benzyl, phenyl, which is unsubstituted or mono- to disubstituted by halogen, C 1 -C 2 alkyl, halomethyl, nitro or cyano, or heterocyclyl, which is unsubstituted or mono- to trisubstituted by identical or different substituents from the group comprising halogen, C 1 -C 2 alkyl, halomethyl, nitro and cyano, or a 5- to 7-membered lactone ring;
  • R 11 is hydrogen, C 1 -C 4 alkyl, halo-C 1 -C 4 -alkyl having 1, 2 or 3 halogen atoms,
  • R 12 is hydrogen or C 1 -C 4 alkyl
  • R 11 and R 12 together with the nitrogen atom to which they are bonded are a heterocyclic radical, which is unsubstituted or mono- to trisubstituted by identical or different substituents from the group comprising halogen, C 1 -C 2 alkyl, halomethyl and nitro;
  • R 13 is hydrogen or C 1 -C 4 alkyl
  • R 14 is hydrogen, C 1 -C 4 alkyl, C 1 -C 4 alkanoyl, benzoyl, the phenyl group of which is unsubstituted or substituted by one, two or three substituents chosen from the group comprising halogen, C 1 -C 2 alkyl, nitro and cyano, C 1 -C 4 alkylsulfonyl or aminosulfonyl, the nitrogen atom of which is unsubstituted or mono- or disubstituted by C 1 -C 4 alkyl; n is 1 or 2;
  • R 1 is hydrogen or C 1 -C 4 alkyl
  • R 2 and R 3 independently of one another are hydrogen, C 1 -C 4 alkyl, halo-C 1 -C 4 -alkyl having 1, 2 or 3 halogen atoms, C 1 -C 2 alkoxy-C 1 -C 4 alkyl, C 2 -C 4 alkynyl, C 3 -C 5 cycloalkyl, hydroxyl or halogen;
  • R 4 is hydrogen, C 1 -C 4 alkyl, C 3 -C 5 cycloalkyl or benzyl;
  • R 5 and R 6 independently of one another are hydrogen, C 1 -C 4 alkyl, halo-C 1 -C 4 alkyl having
  • R 7 , R 8 and R 9 independently of one another are hydrogen, halogen or C 1 -C 4 alkyl
  • X is OR 10 , SR 10 or N(R 11 )R 12 ;
  • Y is a group -CH(R 13 )-, oxygen, sulfur or a group -N(R 14 )-;
  • R 10 is C 1 -C 4 alkyl, halo-C 1 -C 4 -alkyl having 1, 2 or 3 halogen atoms, C 1 -C 2 alkoxy- C 1 -C 4 alkyl, hydroxy-C 1 -C 4 alkyl, nitro-C 1 -C 4 alkyl, cyano-C 1 -C 4 alkyl, C 1 -C 4 alkanoyl- C 1 -C 4 alkyl, C 1 -C 4 alkoxycarbonyl-C 1 -C 4 alkyl, C 3 -C 5 cycloalkyl, benzyl, phenyl, which is unsubstituted or mono- to disubstituted by halogen, C 1 -C 2 alkyl, halomethyl, nitro or cyano, heterocyclyl, which is unsubstituted or mono- to trisubstituted by identical or different substituents from the group comprising halogen, C 1
  • R 11 is hydrogen, C 1 -C 4 alkyl, halo- C 1 -C 4 -alkyl having 1, 2 or 3 halogen atoms,
  • R 12 is hydrogen orC 1 -C 4 alkyl
  • R 11 and R 12 together with the nitrogen atom to which they are bonded, are a heterocyclyl radical, which is unsubstituted or mono- to trisubstituted by identical or different substituents from the group comprising halogen, C 1 -C 2 alkyl, halomethyl and nitro;
  • R 13 is hydrogen;
  • R 14 is hydrogen, C 1 -C 4 alkyl, C 1 -C 4 alkanoyl, benzoyl, the phenyl group of which is unsubstituted or substituted by one, two or three substituents chosen from the group comprising halogen, C 1 -C 2 alkyl, nitro and cyano, C 1 -C 4 alkylsulfonyl or aminosulfonyl, the nitrogen atom of which is unsubstituted or mono- or disubstituted by C 1 -C 4 alkyl;
  • n 1 or 2;
  • R 1 is hydrogen; or C 1 -C 4 alkyl
  • R 2 is hydrogen, C 1 -C 4 alkyl, halo-C 1 -C 4 -alkyl having 1, 2 or 3 halogen atoms,
  • R 3 is fluorine or chlorine
  • R 4 is hydrogen or C 1 -C 4 alkyl
  • R 5 is C 1 -C 4 alkyl
  • R6 is hydrogen
  • R 7 , R 8 and R 9 independently of one another are hydrogen or halogen
  • X is OR 10 ' SR 10 or N(R 11 )R 12 ;
  • Y is a group -CH(R 13 )-, oxygen, sulfur or a group -N(R 14 )-;
  • R 10 is C 1 -C 4 alkyl, halo-C 1 -C 4 -alkyl having 1, 2 or 3 halogen atoms, C 1 -C 2 alkoxy- C 1 -C 4 alkyl, hydroxy-C 1 -C 4 alkyl, nitro-C 1 -C 4 alkyl, cyano-C 1 -C 4 alkyl, C 1 -C 4 alkanoyl- C 1 -C 4 alkyl, C 1 -C 4 alkoxycarbonyl-C 1 -C 4 alkyl, C 2 -C 4 alkenyl, which is unsubstituted or mono- to trisubstituted by halogen, C 2 -C 4 alkynyl, C 3 -C 7 cycloalkyl, C 4 -C 8 cycloalkenyl, benzyl or phenyl, which is unsubstituted or mono- to disubstituted by halogen, C 1
  • R 11 is hydrogen, C 1 -C 4 alkyl, halo-C 1 -C 4 -alkyl having 1, 2 or 3 halogen atoms,
  • R 12 is hydrogen or C 1 -C 4 alkyl
  • R 11 and R 12 together with the nitrogen atom to which they are bonded, are pyrrolidine, piperidine, piperazine, morpholine or 2,6-dimethylmorpholine;
  • R 13 is hydrogen;
  • R 14 is hydrogen, C 1 -C 4 alkyl, C 1 -C 4 alkanoyl or benzoyl, the phenyl group of which is unsubstituted or substituted by one, two or three substituents chosen from the group comprising halogen, C 1 -C 2 alkyl, nitro and cyano;
  • n 1 or 2.
  • R 1 is hydrogen; or C 1 -C 4 alkyl
  • R 2 is hydrogen, C 1 -C 4 alkyl, halo-C 1 -C 4 -alkyl having 1, 2 or 3 halogen atoms,
  • R 3 is chlorine
  • R 4 is hydrogen or C 1 -C 4 alkyl
  • R 5 is C 1 -C 4 alkyl
  • R 6 is hydrogen
  • R 7 , R 8 and R 9 independently of one another are hydrogen or halogen
  • X is OR 10 , SR 10 or N(R 11 )R 12 ;
  • Y is a group -CH(R 13 )-, oxygen, sulfur or a group -N(R 14 )-;
  • R 10 is C 1 -C 4 alkyl, halo-C 1 -C 4 -alkyl having 1, 2 or 3 halogen atoms, C 1 -C 2 alkoxy- C 1 -C 4 alkyl, hydroxy-C 1 -C 4 alkyl, nitro-C 1 -C 4 alkyl, cyano-C 1 -C 4 alkyl, C 1 -C 4 alkanoyl- C 1 -C 4 alkyl, C 1 -C 4 alkoxycarbonyl-C 1 -C 4 alkyl, C 3 -C 5 cycloalkyl, benzyl, phenyl, which is unsubstituted or mono- to disubstituted by halogen, C 1 -C 2 alkyl, nitro or cyano, pyridine, pyrimidine or triazine, in which these heterocyclic radicals in each case are unsubstituted or mono- to trisubstituted by identical or different
  • R 11 is hydrogen, C 1 -C 4 alkyl, halo-C 1 -C 4 -alkyl having 1, 2 or 3 halogen atoms,
  • R 12 is hydrogen or C 1 -C 4 alkyl
  • R 11 and R 12 together with the nitrogen atom to which they are bonded, are pyrrolidine, piperidine, piperazine, morpholine or 2,6-dimethylmorpholine;
  • R 13 is hydrogen
  • R 14 is hydrogen, C 1 -C 4 alkyl, C 1 -C 4 alkanoyl or benzoyl, the phenyl group of which is unsubstituted or substituted by one, two or three substituents chosen from the group comprising halogen, C 1 -C 2 alkyl, nitro and cyano; n is 1 or 2.
  • X is S R 10 ;
  • R 10 is C 1 -C 2 alkyl, halo-C 1 -C 2 -alkyl having 1, 2 or 3 halogen atoms, C 1 -C 2 alkoxy- C 1 -C 2 alkyl, hydroxy- C 1 -C 2 alkyl, acetyl-C 1 -C 2 alkyl, tert-butyloxycarbonyl-C 1 -C 2 alkyl, benzyl, phenyl, which is unsubstituted or mono- to disubstituted by halogen, C 1 -C 2 alkyl, nitro or cyano, pyridine, pyrimidine or triazine, in which these heterocyclic radicals in each case are unsubstituted or mono- to trisubstituted by identical or different substituents from the group comprising halogen, C 1 -C 2 alkyl, trifluoromethyl and cyano, or a
  • X is N(R 11 )R 12 ;
  • R 11 is hydrogen, C 1 -C 4 alkyl, halo- C 1 -C 2 alkyl having 1, 2 or 3 halogen atoms,
  • R 11 and R 12 together with the nitrogen atom to which they are bonded, are pyrrolidine, piperidine, piperazine, morpholine or 2,6-dimethylmorpholine.
  • R 2 is hydrogen, methyl or ethyl
  • R 3 is fluorine or chlorine
  • R 5 is methyl or ethyl
  • R 8 and R 9 independently of one another are hydrogen or fluorine;
  • X is OR 10' SR 10 or N(R 11 ) R 12 ;
  • R 10 is methyl, ethyl, difluoromethyl, trifluoromethyl, 2,2,2-trifluoroethyl, cyanomethyl, tert-butyloxycarbonylmethyl, allyl, 2-propynyl, cyclohexyl, cyclohexenyl, pyridine, pyrimidine or triazine, in which these heterocyclic radicals in each case are unsubstituted or mono- to trisubstituted by identical or different substituents from the group comprising halogen, C 1 -C 2 alkyl, trifluoromethyl and cyano;
  • R 11 is hydrogen, C 1 -C 4 alkyl, halo-C 1 -C 4 -alkyl having 1, 2 or 3 halogen atoms, hydroxy- C 1 -C 4 alkyl, cyano-C 1 -C 4 alkyl, allyl, 2-propynyl, cyclohexyl, cyclohexenyl, cyclopropyl, benzyl or phenyl;
  • R 12 is hydrogen
  • R 11 and R 12 together with the nitrogen atom to which they are bonded, are pyrrolidine, piperidine, piperazine, morpholine or 2,6-dimethylmorpholine.
  • R 2 is hydrogen, methyl or ethyl
  • R 3 is fluorine or chlorine
  • R 5 is methyl or ethyl
  • R 8 and R 9 independendy of one another are hydrogen or fluorine
  • X is OR 10 , SR 10 or N(R 11 )R 12 ;
  • R 10 is methyl, ethyl, difluoromethyl, trifluoromethyl, 2,2,2-trifluoroethyl,
  • cyanomethyl,tert-butyloxycarbonylmethyl allyl, 2-propynyl, cyclohexyl, cyclohexenyl, pyridine, pyrimidine or triazine, in which these heterocyclic compounds in each case are unsubstituted or mono- to trisubstituted by identical or different substituents from the group comprising halogen, C 1 -C 2 alkyl, trifluoromethyl and cyano;
  • R 11 is hydrogen, C 1 -C 4 alkyl, halo-C 1 -C 4 -alkyl having 1, 2 or 3 halogen atoms, hydroxy- C 1 -C 4 alkyl, cyano-C 1 -C 4 alkyl, allyl, 2-propynyl, cyclohexyl, cyclohexenyl, cyclopropyl, benzyl or phenyl;
  • R 12 is hydrogen; or R 11 and R 12 , together with the nitrogen atom to which they are bonded, are pyrrolidine, piperidine, piperazine, morpholine or 2,6-dimethylmorpholine.
  • R 2 is hydrogen, methyl or ethyl
  • R 3 is fluorine or chlorine
  • R 5 is methyl or ethyl
  • R 8 and R 9 independently of one another are hydrogen or fluorine
  • X is OR 10 , SR 10 or N(R 11 )R 12 ;
  • R 10 is methyl, ethyl, difluoromethyl, trifluoromethyl, 2,2,2-trifluoroethyl,
  • cyanomethyl.tert-butyloxycarbonylmethyl allyl, 2-propynyl, cyclohexyl, cyclohexenyl, pyridine, pyrimidine or triazine, in which these heterocyclic radicals in each case are unsubstituted or mono- to trisubstituted by identical or different substituents from the group comprising halogen, C 1 -C 2 alkyl, trifluoromethyl and cyano;
  • R 11 is hydrogen, C 1 -C 4 alkyl, halo-C 1 -C 4 -alkyl having 1, 2 or 3 halogen atoms, hydroxy- C 1 -C 4 alkyl, cyano-C 1 -C 4 alkyl, allyl, 2-propynyl, cyclohexyl, cyclohexenyl, cyclopropyl, benzyl or phenyl;
  • R 12 is hydrogen
  • R 11 and R 12 together with the nitrogen atom to which they are bonded, are pyrrolidine, piperidine, piperazine, morpholine or 2,6-dimethylmorpholine.
  • R 2 is hydrogen, methyl or ethyl
  • R 3 is fluorine or chlorine
  • R 5 is methyl or ethyl
  • R 8 and R 9 independently of one another are hydrogen or fluorine
  • X is OR 10 , SR 10 or N(R 11 )R 12 ;
  • R 10 is methyl, ethyl, difluoromethyl, trifluoromethyl, 2,2,2-trifluoroethyl,
  • cyanomethyl.tert-butyloxycarbonylmethyl allyl, 2-propynyl, cyclohexyl, cyclohexenyl, pyridine, pyrimidine or triazine, in which these heterocyclic radicals in each case are unsubstituted or mono- to trisubstituted by identical or different substituents from the group comprising halogen, C 1 -C 2 alkyl, trifluoromethyl and cyano;
  • R 11 is hydrogen, C 1 -C 4 alkyl, halo-C 1 -C 4 -alkyl having 1, 2 or 3 halogen atoms, hydroxy- C 1 -C 4 alkyl, cyano-C 1 -C 4 alkyl, allyl, 2-propynyl, cyclohexyl, cyclohexenyl, cyclopropyl, benzyl or phenyl;
  • R 12 is hydrogen
  • R 11 and R 12 together with the nitrogen atom to which they are bonded, are pyrrolidine, piperidine, piperazine, morpholine or 2,6-dimethylmorpholine.
  • R 2 is hydrogen, methyl or ethyl
  • R 3 is fluorine or chlorine;
  • R 5 is methyl or ethyl;
  • R 8 and R 9 independendy of one another are hydrogen or fluorine
  • X is OR 10 , SR 10 or N(R 11 )R 12 ;
  • R 10 is methyl, ethyl, difluoromethyl, trifluoromethyl, 2,2,2-trifluoroethyl,
  • cyanomethyl,tert-butyloxycarbonylmethyl allyl, 2-propynyl, cyclohexyl, cyclohexenyl, pyridine, pyrimidine or triazine, in which these heterocyclic radicals in each case are unsubstituted or mono- to trisubstituted by identical or different substituents from the group comprising halogen, C 1 -C 2 alkyl, trifluoromethyl and cyano;
  • R 11 is hydrogen, C 1 -C 4 alkyl, halo-C 1 -C 4 -alkyl having 1, 2 or 3 halogen atoms, hydroxy- C 1 -C 4 alkyl, cyano- C 1 -C 4 alkyl, allyl, 2-propynyl, cyclohexyl, cyclohexenyl, cyclopropyl, benzyl or phenyl;
  • R 12 is hydrogen
  • R 11 and R 12 together with the nitrogen atom to which they are bonded, are pyrrolidine, piperidine, piperazine, morpholine or 2,6-dimethylmorpholine.
  • R 2 is hydrogen, methyl or ethyl
  • R 3 is fluorine or chlorine
  • R 5 is methyl or ethyl
  • R 8 and R 9 independently of one another are hydrogen or fluorine
  • X is OR 10 , SR 10 or N(R 11 ) R 12 ;
  • R 10 is methyl, ethyl, difluoromethyl, trifluoromethyl, 2,2,2-trifluoroethyl,
  • cyanomethyl.tert-butyloxycarbonylmethyl allyl, 2-propynyl, cyclohexyl, cyclohexenyl, pyridine, pyrimidine or triazine, in which these heterocyclic radicals in each case are unsubstituted or mono- to trisubstituted by identical or different substituents from the group comprising halogen, C 1 -C 2 alkyl, trifluoromethyl and cyano;
  • R 11 is hydrogen, C 1 -C 4 alkyl, halo-C 1 -C 4 -alkyl having 1, 2 or 3 halogen atoms, hydroxy- C 1 -C 4 alkyl, cyano-C 1 -C 4 alkyl, allyl, 2-propynyl, cyclohexyl, cyclohexenyl, cyclopropyl, benzyl or phenyl;
  • R 12 is hydrogen
  • R 11 and R 12 together with the nitrogen atom to which they are bonded, are pyrrolidine, piperidine, piperazine, morpholine or 2,6-dimethylmorpholine.
  • R 2 is methyl or ethyl
  • X is OR 10 or SR 10 ;
  • R 10 is C 1 -C 6 alkyl, halo- C 1 -C 6 alkyl having 1-3 halogen atoms,
  • W is C 1 -C 6 alkoxy, C 3 -C 6 cycloalkoxy, or the group -N(T 1 )T 2 ;
  • T 1 and T 2 independently of one another are hydrogen, C 1 -C 6 alkyl, halo- C 1 -C 6 alkyl having 1-3 halogen atoms, C 3 -C 6 cycloalkyl, phenyl, halophenyl having 1-3 halogen atoms, pyridyl or naphthyl, or
  • T 1 and T 2 together with the nitrogen atom to which they are bonded, are piperidine, piperazine, morpholine or 2,6-dimethylmorpholine.
  • R 2 is methyl or ethyl
  • X is OR 10 or SR 10 ;
  • R 10 is C 1 -C 6 alkyl, halo- C 1 -C 6 alkyl having 1-3 halogen atoms,
  • W is C 1 -C 6 alkoxy, C 3 -C 6 cycloalkoxy, or the group -N(T 1 )T 2 ;
  • T 1 and T 2 independently of one another are hydrogen, C 1 -C 6 alkyl, halo-C 1 -C 6 alkyl having
  • halogen atoms C 3 -C 6 cycloalkyl, phenyl, halophenyl having 1-3 halogen atoms, pyridyl or naphthyl, or
  • T 1 and T 2 together with the nitrogen atom to which they are bonded, are piperidine, piperazine, morpholine or 2,6-dimethylmorpholine.
  • R 2 is methyl or ethyl
  • X is OR 10 or SR 10 ;
  • R 10 is C 1 -C 6 alkyl, halo- C 1 -C 6 alkyl having 1-3 halogen atoms,
  • W is C 1 -C 6 alkoxy, C 3 -C 6 cycloalkoxy, or the group -N(T 1 )T 2 ;
  • T 1 and T 2 independently of one another are hydrogen, C 1 -C 6 alkyl, halo-C 1 -C 6 alkyl having
  • halogen atoms C 3 -C 6 cycloalkyl, phenyl, halophenyl having 1-3 halogen atoms, pyridyl or naphthyl, or
  • T 1 and T 2 together with the nitrogen atom to which they are bonded, are piperidine, piperazine, morpholine or 2,6-dimethylmorpholine.
  • a particular group of compounds are furthermore those in which, in formula I, X is SR 10 .
  • the invention furthermore relates to a process for the preparation of compounds of the formula I and, where appropriate, their tautomers, in each case in the free form or in salt form, for example, which comprises reacting: a) for the preparation of a compound of the formula I in which X is SR 10 :
  • M is hydrogen, Li + , Na + , K + , 1/2Mg 2+ or a quaternary ammonium ion;
  • X is OR 10 or N(R 11 )R 12 , and wherein
  • R 10 , R 11 and R 12 are as defined for formula I; if appropriate in the presence of a base; or c) for the preparation of a compound of the formula I in which R 4 and R 14 are as defined for formula I but are other than hydrogen:
  • R 4 and R 14 are hydrogen with a compound of the formula R 4 '-Z' or R 14 '-Z', in which R 4 ' and R 14 ' are as defined in formula I for R 4 and R 14 , but are other than hydrogen, and Z' is a nucleofugic radical which can easily be split off;
  • Another process for the preparation of a compound of the formula I comprises reacting a compound of the formula VII
  • M is hydrogen, Li + , Na + , K + , 1/2Mg 2+ or a quaternary ammonium ion;
  • X' is OR 10 , SR 10 or N(R 11 )R 12 , and in which R 10 , R 11 and R 12 are as defined for formula I; if appropriate in the presence of a base.
  • reaction medium for example in a temperature range from about -80°C up to the boiling point of the reaction medium, preferably from about -20°C up to about +150°C, and, if necessary, in a closed vessel, under pressure, in an inert gas atmosphere and/or under anhydrous conditions.
  • Typical reaction conditions can be found in the examples.
  • Nucleofugic radicals Z and Z' are, for example: fluorine, chlorine, bromine, iodine, C 1 -C 8 alkylthio, such as methylthio, ethylthio or propylthio, C 1 -C 8 alkanoyloxy, such as acetoxy, (halo) C 1 -C 8 alkanesulfonyloxy, such as methanesulfonyloxy, ethanesulfonyloxy or trifluoromethanesulfonyloxy, or unsubstituted or substituted phenylsulfonyloxy, such as benzenesulfonyloxy or p-toluenesulfonyloxy, and furthermore also hydroxyl.
  • C 1 -C 8 alkylthio such as methylthio, ethylthio or propylthio
  • C 1 -C 8 alkanoyloxy such as
  • Suitable bases are, for example, alkali metal or alkaline earth metal hydroxides, hydrides, amides, alkanolates, carbonates, dialkylamides or alkylsilylamides, alkylamines, alkylenediamines, non-alkylated or N-alkylated, saturated or unsaturated
  • cycloalkylamines basic heterocyclic compounds, ammonium hydroxides and carbocyclic amines.
  • Examples are sodium hydroxide, hydride, amide, methanolate and carbonate, potassium tert-butanolate and carbonate, lithium diisopropylamide, potassium
  • cyclohexylamine N-cyclohexyl-N,N-dimethylamine, N,N-diethylaniline, pyridine, 4-(N,N-dimethylamino)pyridine, N-methylmorpholine, benzyl-trimethyl-ammonium hydroxide and 1,8-diazabicyclo[5.4.0]undec-5-ene (DBU).
  • reaction partners can be reacted with one another as such, i.e. without addition of a solvent or diluent, for example in the melt.
  • a solvent or diluent for example in the melt.
  • an inert solvent or diluent or a mixture thereof is usually advantageous.
  • solvents or diluents which may be mentioned are: aromatic, aliphatic and alicyclic hydrocarbons and halogenated hydrocarbons, such as benzene, toluene, xylene, chlorobenzene,
  • bromobenzene petroleum ether, hexane, cyclohexane, methylene chloride, chloroform, dichloroethane or trichloroethane; ethers, such as diethyl ether, ten-butyl methyl ether, tetrahydrofuran or dioxane; ketones, such as acetone or methyl ethyl ketone; alcohols, such as methanol, ethanol, propanol, butanol, ethylene glycol or glycerol; esters, such as ethyl acetate or butyl acetate; amides, such as N,N-dimethylformamide,
  • Bases employed in excess, such as triethylamine, pyridine, N-methylmorpholine or N,N-diethylaniline, can also serve as solvent or diluent.
  • the reaction is advantageously ca ⁇ ied out in a temperature range of about 0°C to about +180°C, preferably about +20°C to about +130°C, in many cases at the reflux temperature of the solvent used.
  • reaction can be ca ⁇ ied out under phase transfer catalysis in an organic solvent, for example methylene chloride or toluene, in the presence of an aqueous basic solution, for example sodium hydroxide solution, and a phase transfer catalyst, for example tetrabutylammonium hydrogen sulfate.
  • organic solvent for example methylene chloride or toluene
  • a phase transfer catalyst for example tetrabutylammonium hydrogen sulfate.
  • a compound I obtainable according to the process or in another manner or, where appropriate, a tautomer thereof can be converted into another compound I in a manner known per se by replacing one or more substituents of the starting compound I by another substituent in the customary manner.
  • heteroaromatic ring part structures can be halogenated to halo-containing substituents or halogenated aromatic or heteroaromatic ring part structures;
  • - halogen substituents can be replaced by other substituents, such as cyano, alkylthio or alkoxy substituents;
  • N- N-hydrogen can be replaced by N-alkyl, N-benzyl, N-aryl, N-heteroaryl, N-alkanoyl, N-benzoyl or N-sulfonyl;
  • - sulfides can be oxidized to sulfoxides and sulfones
  • - carbonyl groups can be sulfated to thiocarbonyl groups.
  • Salts of compounds I can be prepared in a manner known per se.
  • acid addition salts of compounds I are obtained by treatment with a suitable acid or a suitable ion exchanger reagent
  • salts with bases can be obtained by treatment with a suitable base or a suitable ion exchanger reagent.
  • Salts of compounds I can be converted into the free compounds I in the customary manner, acid addition salts for example by treatment with a suitable basic agent or a suitable ion exchanger reagent and salts with bases for example by treatment with a suitable acid or a suitable ion exchanger reagent
  • Some of the compounds I can be in the form of one of the possible isomers or as mixtures thereof, for example as pure isomers or as isomer mixtures, such as enantiomer mixtures, for example racemates, diastereomer mixtures or racemate mixtures, depending on the number of and absolute relative configuration of the asymmetric carbon atoms; the invention relates both to the pure isomers and to all the possible isomer mixtures and is in each case to be understood accordingly above and below, although stereochemical details are not mentioned specifically in each case.
  • Diastereomer mixtures and racemate mixtures of compounds I obtainable according to the process or by another means can be separated into the pure diastereomers or racemates in a known manner on the basis of the physico-chemical differences of the constituents, for example by fractional crystallization, distillation and/or chromatography.
  • the invention likewise relates to novel starting substances and intermediates used for the preparation of the compounds of the formula I, their use and processes for their preparation.
  • the compounds of the formula II can be prepared, for example, by reacting a compound of the formula V
  • R 1' R 2 and R 3 have the meanings given for formula I and Z is a nucleofugic radical which can easily be split off, with a compound of the formula VI or a salt thereof, preferably in the presence of a base, in which R 4 to R 9 , Y and n are as defined for the formula I.
  • Another possibility for the preparation of compounds of the formula II comprises reacting a compound of the formula VII with a thionating agent, preferably with phosphorus pentasulfide or with 4-methoxyphenylthiophosphonic acid cyclodithioanhydride
  • Pyrimidines which are amino-substituted in the 4-position are already known, for example from the Patent Application WO 92/08704.
  • the compounds I of the present invention differ from these known compounds structurally in a characteristic manner; furthermore, the compounds of the formula I of the present invention show an unexpectedly high microbicidal, insecticidal, nematicidal and acaricidal activity. Protection of plants can occur here either by direction action on the pests or by activation and stimulation of the plant's own defence system (immunization).
  • the compounds of the formula I of the present invention are stable at room temperature to slightly elevated temperature and can easily be stored. They can be used in the agricultural sector and related fields preventively and/or curatively as active compounds for control of plant pests.
  • the active compounds of the formula I according to the invention are distinguished not only by an outstanding action - even at low use concentrations - but also by a good agricultural acceptability. They have very good advantageous properties, in particular systemic properties, and can be used for protection of numerous crop plants.
  • the pests which occur on plants or parts of plants (fruit, blossom, foliage, stems, tubers, roots) of various crops of useful plants can be checked or destroyed with the active compounds of formula I, parts of plants which grow later also remaining spared, for example from phytopathogenic microorganisms.
  • the compounds I are active, for example, against phytopathogenic fungi belonging to the following classes: Fungi imperfecti (for example Botrytis, Pyricularia, Helminthosporium, Fusarium, Septoria, Cercospora and Altemaria) and Basidiomycetes (for example
  • Rhizoctonia Hemileia, Puccinia
  • They furthermore have an action against the classes of Ascomycetes (for example Venturia and Erysiphe, Podosphaera, Monilinia, Uncinula) and Oomycetes (for example Phytophthora, Pythium, Plasmopara).
  • Ascomycetes for example Venturia and Erysiphe, Podosphaera, Monilinia, Uncinula
  • Oomycetes for example Phytophthora, Pythium, Plasmopara
  • the compounds I furthermore can be used as dressing agents for the treatment of seed (fruit, tubers, grains) and plant seedlings for protection from fungal infections and against phytopathogenic fungi which occur in the soil.
  • the compounds I according to the invention are also useful active compounds in the control of pests of the order Acarina and of the insects and nematode classes on crop and ornamental plants in agriculture, in particular in cotton, vegetable and fruit plantations, in forestry, in the field of protection of stored products and materials, and in the hygiene sector for control of animal pests, in particular on domestic animals and productive livestock. They are active against various stages of development. They can display tiieir action here in the immediate mortality of the pests or only after some time, for example during moulting, or in a significantly reduced oviposition and/or hatching rate.
  • the order of the Acarina includes, for example, Boophilus spp. and Tetranychus Spp.; this list is not limiting.
  • the invention also relates to the compositions which comprise compounds of the formula I, as the active compound, together with a carrier material, in particular crop protection compositions, and to their use in the agricultural sector and related fields.
  • the invention furthermore also includes the preparation of these compositions, which comprises intimately mixing the active substance with one or more of the extenders and distributing agents described below.
  • the invention also includes a method for the treatment of plants, which comprises application of the novel compounds I or of the novel compositions.
  • Target crops for the crop protection use in the context of the invention are, for example, the following plant species: cereals (wheat, barley, rye, oats, rice, maize, sorghum and related species); beet (sugar-beet and feed beet); pome, stone and soft fruit (apples, pears, plums, peaches, almonds, cherries, strawberries, raspberries and blackberries); leguminous plants (beans, lentils, peas, soya); oil crops (rape, mustard, poppy, olive, sunflower, coconut, castor, cacao, groundnut); Cucurbitaceae (squash, cucumbers, melons); fibre plants (cotton, flax, hemp, jute); citrus fruits (oranges, lemons, grapefruit, mandarins); vegetable varieties (spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes, paprika); laurel plants (avocado, cinnamonium, camphor) and plants such as tobacco, nuts,
  • Active compounds I are usually used in the form of compositions and can be applied to the area or plants to be treated at the same time as or successively with other active
  • These other active compounds can be, for example, fertilizers, trace element mediators or other preparations which influence plant growth.
  • Selective herbicides and insecticides, fungicides, bactericides, nematicides, molluscicides or mixtures of several of these preparations together with, where appropriate, further carriers, surfactants or other application-promoting additives customary in formulation technology can also be used here.
  • Suitable carriers and additives can be solid or liquid and are the substances used for this purpose in formulation technology, for example naturally occurring or regenerated mineral substances, solvents, dispersants, wetting agents, tackifying agents, thickeners, binders or fertilizers.
  • a preferred process for application of an active compound of the formula I or of an agrochemical composition which comprises at least one of these active compounds is application to the foliage (foliar application).
  • the application frequency and rate of application depend here on the risk of infection by the pathogen in question.
  • the active compounds I can also enter the plant through the root system via the soil (systemic action), by soaking the locus of the plant with a liquid composition or incorporating the substances into the soil in solid form, for example in the form of granules (soil
  • the compounds I can also be applied to seed grains (coating) by either soaking the grains in a liquid composition of the active compound or coating them with a solid formulation.
  • the compounds I are employed here in unchanged form or, preferably, together with the auxiliaries customary in formulation technology. For this purpose, they are
  • emulsion concentrates for example, to emulsion concentrates, spreadable pastes, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts or granules, for example by encapsulation in, for example, polymeric substances.
  • the methods of application such as spraying, atomizing, dusting, scattering, coating or pouring, like the nature of the compositions, are chosen according to the intended aims and the given circumstances.
  • Favourable rates of application are in general 5 g to 2 kg of active substance (AS) per hectare (ha), preferably 10 g to 1 kg of AS/ha, in particular 20 g to 600 g of AS/ha.
  • Dosages of 10 mg to 1 g of active substance per kg of seed are advantageously employed for use as seed dressing compositions.
  • compositions, formulations or preparations comprising the active compound of the formula I and, where appropriate, a solid or liquid additive
  • extenders such as solvents, solid carriers and, if appropriate
  • surfactants are surface-active compounds (surfactants).
  • Solvents are: aromatic hydrocarbons, preferably C 8 to C 12 fractions, such as xylene mixtures or substituted naphthalenes, phthalic acid esters, such as dibutyl or dioctyl phthalate, aliphatic hydrocarbons, such as cyclohexane or paraffins, alcohols and glycols and ethers and esters thereof, such as ethanol, ethylene glycol and ethylene glycol monomethyl or -ethyl ether, ketones, such as cyclohexanone, strongly polar solvents, such as N-methyl-2-pyrrolidone, dimediyl sulfoxide or dimethylformamide, and, if appropriate, epoxidized vegetable oils, such as epoxidized coconut oil or soya oil, and water.
  • aromatic hydrocarbons preferably C 8 to C 12 fractions, such as xylene mixtures or substituted naphthalenes, phthalic acid esters, such as dibutyl or
  • the solid carriers used are as a rule naturally occurring rock powders, such as calcite, talc, kaolin, montmorillonite or attapulgite. Highly disperse silicic acid or highly disperse absorbent polymers can also be added to improve the physical properties.
  • Granular, adsorptive granule carriers are porous types, such as pumice, broken bricks, sepiolite or bentonite, and non-sorptive carrier materials are, for example, calcite or sand.
  • Surface-active compounds are nonionic, canonic and/or anionic surfactants having good emulsifying, dispersing and wetting properties, depending on the nature of the active compound of the formula I to be formulated.
  • Surfactants are also to be understood as meaning surfactant mixtures.
  • Suitable anionic surfactants can be either so-called water-soluble soaps or water-soluble synthetic surface-active compounds.
  • nonionic surfactants are nonylphenolpolyethoxyethanols, castor oil polyglycol ethers, polypropylene/polyethylene oxide adducts, tributyphenoxypolyethylene-ethanol, polyethylene glycol and octylphenoxypolyethoxyethanol.
  • surfactants are also fatty acid esters of polyoxyethylene-sorbitan, such as polyoxyethylene-sorbitan trioleate.
  • the cationic surfactants are, in particular, quaternary ammonium salts which contain at least one alkyl radical having 8 to 22 C atoms as N substituents and contain lower, optionally halogenated alkyl, benzyl or lower hydroxyalkyl radicals as further substituents.
  • the agrochemical compositions as a rule comprise 0.1 to 99 per cent by weight, in particular 0.1 to 95 per cent by weight, of active compound of the formula 1, 99.9 to 1 per cent by weight, in particular 99.8 to 5 per cent by weight, of a solid or liquid additive and 0 to 25 per cent by weight, in particular 0.1 to 25 per cent by weight, of a surfactant.
  • compositions tend to be preferred as commercial goods, the end user as a rule uses dilute compositions.
  • compositions can also comprise further additives, such as stabilizers, foam suppressants, viscosity regulators, binders or tackifiers, as well as fertilizers or other active compounds, in order to achieve specific effects.
  • further additives such as stabilizers, foam suppressants, viscosity regulators, binders or tackifiers, as well as fertilizers or other active compounds, in order to achieve specific effects.
  • Example H-1a 0.96 g of NaH in oil ( ⁇ 55%) in 15 ml of anhydrous tetrahydrofuran is initially introduced into a sulfonating flask at room temperature.
  • a solution of 6.97 g of 6-[1-(5-chloro-6-ethylpyrimidin-4-ylamino)ethyl]-2H-1,4-benzoxazine-3-thione in 35 ml of absolute tetrahydrofuran is tiien added dropwise under an N2 atmosphere in the course of about 10 minutes.
  • 3.12 g of methyl iodide are added at room temperature and the mixture is then stirred at about 25°C for 4 hours.
  • Example H-1b 1.0 g of 6-[1-(5-chloro-6-ethylpyrimidin-4-ylamino)ethyl]-3-methylthio- 2H-1,4-benzoxazine (H-1a) and 1.5 g of sodium methylate (30% solution in methanol) in 15 ml of absolute methanol are initially introduced into a sulfonating flask at room temperature. The mixture is kept under reflux for 3 hours and the solvent is then stripped off under a water pump vacuum. The residue is purified by column chromatography over silica gel (mobile phase: n-hexane/ethyl acetate 2:1). 0.9 g of
  • 6-[1-(5-chloro-6-ed ⁇ ylpyrimidin-4-yl-amino)ethyl]-3-methoxy-2H -1,4-benzoxazine is obtained in the form of a white powder (m.p. 104-105°C).
  • Example H-1c 0.14 g of NaH in oil ( ⁇ 55%) in 5 ml of anhydrous tetrahydrofuran is initially introduced into a sulfonating flask at room temperature. Thereafter, a solution of 1.05 g of 6-[1-(5-chloro-6-ethylpyrimidin-4-ylamino)ethyl]-2H-1,4-benzoxazine-3-thione in 25 ml of absolute tetrahydrofuran is added dropwise under an N2 atmosphere in the course of about 10 minutes. The mixture is stirred at 60-65°C for 15 minutes for complete salt formation, and 0.45 g of allyl bromide is then added. The mixture is kept under reflux for about 2 hours.
  • Emulsions of any desired dilution can be prepared from these emulsion concentrates with water.
  • Example F-2 Emulsion concentrate ______________________________________________
  • Emulsions of any desired dilution can be prepared from this emulsion concentrate with water.
  • the solutions are suitable for use in the form of tiny drops.
  • wheat plants are sprayed to drip point with an aqueous spray liquor prepared from a wettable powder of the active compound (0.02% of active substance), and 24 hours later are infected with a uredosporc suspension of the fungus. After an incubation time of 48 hours (conditions: 95 to 100 per cent relative atmospheric humidity at 20°), the plants are placed in a greenhouse at 22°. Evaluation of the development of rust pustules 12 days after infection leads to the assessment of the action of the active substance. b) Systemic action
  • the wheat plants are watered with an aqueous spray liquor prepared from a wettable powder of the active compound (0.006% of active substance, based on the soil volume). Care is taken that the spray liquor does not come into contact with the parts of plants above the ground. 48 hours later, the plants are infected with a uredosporc suspension of the fungus. After an incubation time of 48 hours (conditions: 95 to 100 per cent relative atmospheric humidity at 20°), the plants are placed in a greenhouse at 22°. Evaluation of the development of rust pustules 12 days after infection gives the assessment of the action of the active substance.
  • Example B-2 Action against Phytophthora infestans on tomatoes
  • aqueous spray liquor prepared from a wettable powder of the active compound (0.006% of active substance, based on the soil volume). Care is taken that the spray liquor does not come into contact with the parts of plants above the ground.
  • the plants are infected with a sporangia suspension of the fungus. Evaluation of the fungal attack 5 days after infection, during which 90 to 100 per cent relative atmospheric humidity and a temperature of 20° are maintained, gives the assessment of the action of active substance.
  • Compounds from Tables 1-8 show a good action; in particular, compounds 1.2, 1.3, 1.6, 3.3, 3.5, 3.11, 3.42, 5.2, 5.3 and 5.5 reduce fungal attack to 0-20%.
  • untreated, infected control plants show a fungal attack of 100%.
  • Example B-3 Residual protective action against Cercospora arachidicola on groundnuts
  • Groundnut plants 10 to 15 cm high are sprayed to drip point with an aqueous spray liquor prepared from a wettable powder of the active compound (0.02% of active substance), and 48 hours later are infected with a conidia suspension of the fungus.
  • the plants are incubated at 21° under a high atmospheric humidity for 72 hours and then placed in a greenhouse until the typical leaf spots occur.
  • the action of the active substance is evaluated 12 days after infection on the basis of the number and size of the leaf spots.
  • Example B-4 Action against Plasmopara viticola on vines
  • Vine seedlings in the 4 to 5 leaf stage are sprayed to drip point with an aqueous spray liquor prepared from a wettable powder of the active compound (0.02% of active substance), and 24 hours later are infected with a sporangia suspension of the fungus.
  • Active compounds from Tables 1-8 show a good action against Plasmopara viticola on vines.
  • compounds 1.2, 1.3, 1.6, 3.3, 3.5, 3.11, 3.42, 5.2, 5.3, 5.5, 5.13, 5.52, 5.104, 5.107, 5.108, 5.110, 5.142 and 5.237 reduce fungal attack to 0-20%.
  • untreated, infected control plants show a fungal attack of 100%.
  • Example B-5 Action against Colletotrichum lagenarium on cucumbers
  • cucumber plants After growing for 2 weeks, cucumber plants are sprayed with a spray liquor prepared from a wettable powder of the active compound (concentration 0.002%). After 2 days, the plants are infected with a spore suspension (1.5x105 spores/ml) of the fungus and incubated at 23°C under high atmospheric humidity for 36 hours. The incubation is then continued under normal atmospheric humidity at about 22°C. The fungal attack which has occurred is evaluated 8 days after the infection.
  • Example B-6 Residual protective action against Venturia inaequalis on apples
  • Apple seedlings with fresh shoots 10 to 20 cm long are sprayed to drip point with an aqueous spray liquor prepared from a wettable powder of the active compound (0.02% of active substance), and 24 hours later are infected with a conidia suspension of the fungus.
  • the plants are incubated at 90 to 100 per cent relative atmospheric humidity for 5 days and are placed in a greenhouse at 20 to 24° for a further 10 days. Evaluation of the scab attack 15 days after infection gives the assessment of the action of the active substance.
  • Active compounds from Tables 2, 5 and 6 show a good residual protective action against Venturia inaequalis on apples.
  • Example B-7 Action against Erysiphe graminis on barley
  • Barley plants approximately 8 cm high are watered with an aqueous spray liquor prepared from a wettable powder of the active compound (0.002% of active substance, based on the soil volume). Care is taken that the spray liquor does not come into contact with the parts of plants above the ground. 48 hours later, the plants are dusted with conidia of the fungus. The infected plants are placed in a greenhouse at 22°. Evalution of the fungal attack 10 days after infection gives the assessment of the action of the active substance.
  • Example B-8 Action against Podosphaera leucotricha on apple shoots
  • Apple seedlings with fresh shoots about 15 cm long are sprayed with a spray liquor (0.06% of active substance). After 24 hours, the treated plants are infected with a conidia suspension of the fungus and placed in a climatically controlled chamber at 70 % relative atmospheric humidity and 20°C. The fungal attack is evaluated 12 days after infection. Active compounds from Tables 1-8, for example compounds 3.42, 5.2, 5.3, 5.5 and 5.61, show a good action against apple mildew.
  • Young bean plants are populated with a mixed population of Tetranychus urticae, and one day later are sprayed with an aqueous emulsion spray liquor which comprises 400 ppm of the active compound. The plants are then incubated at 25°C for 6 days and subsequently evaluated. The percentage reduction in the population (% action) is determined by comparison of the number of dead eggs, larvae and adults on the treated plants with respect to those on the untreated plants.
  • the compounds of Tables 1, 3 and 5 show a good action against Tetranychus urticae in this test.
  • compounds 1.2, 1.3, 1.6, 3.3, 3.5, 3.11, 3.42, 5.2, 5.3, 5.5, 5.13, 5.52, 5.104, 5.107, 5.108, 5.110, 5.142 and 5.237 show an action of above 90%.
  • Rice plants are treated with an aqueous emulsion spray liquor which comprises 400 ppm of the active compound. After the spray coating has dried on, the rice plants are populated with cicada larvae of the 2nd and 3rd stage. They are evaluated 21 days later. The percentage reduction in population (% action) is determined by comparing the number of surviving cicadas on the treated plants with respect to those on the untreated plants.
  • Dwarf beans in the 2-leaf stage are populated with a mixed population (eggs,
  • Compounds of Tables 1 to 8 show a mortality of more than 70% in dilutions of up to 50 mg AS/litre.
  • Rice plants are treated with an aqueous emulsion spray liquor which comprises 400 ppm of the active compound. After the spray coating has dried on, the rice plants are populated with cicada larvae of the 2nd and 3rd stage. They are evaluated 21 days later. The percentage reduction in population (% action) is determined by comparing the number of surviving cicadas on the treated plants with respect to those on the untreated plants.
  • Young cabbage plants are sprayed with an aqueous emulsion spray mixture which comprises 400 ppm of the active compound. After the spray coating has dried on, the cabbage plants are populated with 10 caterpillars of the 3rd stage of Plutella xylostella and placed in a plastic container. They are evaluated 3 days later. The percentage reduction in population or the percentage reduction in feeding damage (% action) is determined by comparison of the number of dead caterpillars and the eating damage on the trcated plants with respect to those on the untreated plants.
  • Example B-14 Action against Musca domestica
  • a sugar cube is treated with a solution of the test substance such that the concentration of the test substance, after drying overnight, in the sugar is 250 ppm.
  • This treated cube is placed with a wet cotton-wool pad and 10 adult Musca domestica of an OP-resistant strain on an aluminium dish, covered with a glass beaker and incubated at 25°C. The mortality rate is determined after 24 hours.

Abstract

Compounds of formula (I) in which the substituent A is in the β or η-position, and in which: X is OR10, SR10 or N(R11)R12; Y is a group -CH(R13)-, oxygen, sulfur or a group -N(R14)-; n is 1 or 2; and in which R1 to R14 are as defined herein, both in the free form and in salt form. Such compounds can be used as agrochemical active compounds for pest control.

Description

PYRIMIDINE DERIVATIVES USEFUL AS PESTICIDES
The invention relates to novel pesticidally active compounds of the formula I
Figure imgf000003_0001
in which the substituent A is in the β or γ-position, and in which:
R1 is hydrogen, C1-C4alkyl, C1-C4alkoxy, halo-C1-C4alkyl having 1, 2 or 3 halogen atoms or C1-C4alkylthio;
R2 and R3 independently of one another are hydrogen, C1-C4alkyl, halo-C1-C4alkyl having 1, 2 or 3 halogen atoms, C1-C2alkoxy-C1-C4alkyl, nitro-C1-C4alkyl, cyano-C1-C4alkyl, C1-C4alkanoyl-C1-C4alkyl, C1-C4alkoxycarbonyl-C1-C4alkyl, C1-C2alkylthio-C1-C4alkyl, C1-C2alkanesulfinyl-C1-C4alkyl, C1-C2alkanesulfonyl-C1-C4alkyl, C2-C4alkenyl, halo- C2-C4alkenyl having 1, 2 or 3 halogen atoms, C2-C4alkynyl, C3-C7cycloalkyl,
C1-C4alkoxy, halo-C1-C4alkoxy, C1-C4alkylthio, halo-C1-C4alkylthio, C1-C4alkylsulfιnyl, C1-C4alkylsulfonyl, amino, C1-C4acylamino, nitro, cyano, hydroxyl or halogen;
R4 is hydrogen, C1-C4alkyl, halo-C1-C4alkyl having 1, 2 or 3 halogen atoms,
C1-C2alkoxy-C1-C4alkyl, nitro-C1-C4alkyl, cyano-C1-C4alkyl, C3-C5cycloalkyl, benzyl, C1-C4alkanoyl or benzoyl, the phenyl group of which is unsubstituted or substituted by one, two or three substituents chosen from the group comprising halogen, C1-C2alkyl, nitro and cyano;
R5 and R6 independently of one another are hydrogen, C1-C4alkyl, halo-C1-C4alkyl having 1, 2 or 3 halogen atoms, C1-C2alkoxy-C1-C4alkyl, nitro-C1-C4alkyl, cyano- C1-C4alkyl, C1-C4alkoxycarbonyl-C1-C4alkyl or C3-C6cycloalkyl, which is unsubstituted or substituted by one or two substituents chosen from the group comprising halogen and C1-C2alkyl;
R7, R8 and R9 independently of one another are hydrogen, halogen, C1-C4alkyl, halo-C1-C4alkyl having 1, 2 or 3 halogen atoms, C1-C2alkoxy-C1-C4alkyl,
C3-C6cycloalkyl, C1-C4alkoxy, halo-C1-C4alkoxy having 1, 2 or 3 halogen atoms,
C3-C7cycloalkoxy, C1-C4alkylthio, halo-C1-C4alkylthio having one, two or three halogen atoms, cyano, nitro, phenyl, phenoxy and phenylthio, the phenyl groups in phenyl, phenoxy and phenylthio being unsubstituted or substituted by one, two or three substituents chosen from the group comprising halogen, C1-C2alkyl and C1-C2 alkoxy, with the proviso that nnt more than one of the substituents R7, R8 or R9 is unsubstituted or substituted phenyl, substituted phenoxy or substituted phenylthio;
X is OR10, SR10 or N(R11)R12;
Y is a group -CH(R13)-, oxygen, sulfur or a group -N(R14)-;
R10 is hydrogen, an unsubstituted or substituted, open-chain, saturated or unsaturated hydrocarbon radical containing up to 12 carbon atoms, an unsubstituted or substituted cyclic saturated or unsaturated hydrocarbon radical containing up to 10 carbon atoms or unsubstituted or substituted benzyl; or an unsubstituted or substituted heterocyclyl radical;R11 is hydrogen, an open-chain saturated or unsaturated hydrocarbon radical which contains up to 8 carbon atoms and is unsubstituted or substituted by 1-5 halogen atoms, C1-C2alkoxy, hydroxyl, nitro, cyano, C1-C4alkanoyl, halo- C1-C4alkanoyl or
C1-C4alkoxycarbonyl, a cyclic saturated or unsaturated hydrocarbon radical containing up to 10 carbon atoms or benzyl, in which the carbocyclic radical is unsubstituted or mono- to disubstituted by halogen, C1-C2alkyl, halomethyl, nitro or cyano, or heterocyclyl, which is unsubstituted or mono- to trisubstituted by identical or different substituents from the group comprising C1-C2alkyl, halogen, halomethyl, nitro and cyano;
R12 is hydrogen or C1-C4alkyl; or
R11 and R12, together with the nitrogen atom to which they are bonded, are a heterocyclic radical which is unsubstituted or mono- to trisubstituted by identical or different substituents from the group comprising halogen, C1-C2alkyl, halomethyl and nitro;
R13 is hydrogen or C1-C4alkyl;
R14 is hydrogen, C1-C4alkyl, C1-C4alkanoyl, benzoyl, the phenyl group of which is unsubstituted or substituted by one, two or three substituents chosen from the group comprising halogen, C1-C2alkyl, nitro and cyano, C1-C4alkylsulfonyl, or aminosulfonyl, the nitrogen atom of which is unsubstituted or mono- or disubstituted by C1-C4alkyl; n is 1 or 2;
or, where appropriate, a tautomer thereof, in each case in the free form or in salt form. The invention furthermore relates to the preparation of these compounds, agrochemical compositions which comprise at least one of these compounds as the active compound, and the use of the active compounds or compositions for pest control, in particular as microbicides in agriculture and in horticulture.
The compounds I and, where appropriate, their tautomers can be in the form of salts. Since the compounds I have at least one basic centre, they can form, for example, acid addition salts. These are formed, for example, with mineral acids, for example sulfuric acid, a phosphoric acid or a hydrogen halide, with organic carboxylic acids, for example acetic acid or oxalic, malonic, maleic, fumaric or phthalic acid, with hydroxycarboxylic acids, for example ascorbic, lactic, malic, tartaric or citric acid, or with benzoic acid, or with organic sulfonic acids, for example methane- or p-toluenesulfonic acid.
Compounds of the formula I having at least one acid group furthermore can form salts with bases. Suitable salts with bases are, for example, metal salts, such as alkali metal or alkaline earth metal salts, for example sodium salts, potassium salts or magnesium salts, or salts with ammonia or an organic amine, such as morpholine, piperidine, pyrrolidine, a mono-, di- or tri-lower alkylamine, for example ethyl-, diethyl-, triethyl- or
dimethyl-propyl-amine, or a mono-, di- or trihydroxy-lower alkylamine, for example mono-, di- or triethanolamine. Corresponding internal salts furthermore may be formed, where appropriate. Agrochemically advantageous salts are preferred in the context of the invention.
The general terms used above and below are as defined below, unless defined otherwise.
Alkyl groups are straight-chain or branched, depending on the number of carbon atoms, and are, for example, methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec -butyl, iso-butyl, tert-butyl, sec-amyl, tert-amyl, 1-hexyl or 3-hexyl.
Alkenyl is to be understood as meaning straight-chain or branched alkenyl, for example allyl, methallyl, 1-methylvinyl or but-2-en-1-yl. Alkenyl radicals having a chain length of 3 to 4 carbon atoms are preferred.
Alkynyl can likewise be straight-chain or branched, depending on the number of carbon atoms, for example propargyl, but-1-yn-1-yl and but-1-yn-3-yl. Propargyl is preferred. Unsaturated hydrocarbon radicals are alkenyl, alkynyl or alkenynyl groups having not more than 3 multiple bonds, for example butadienyl, hexatrienyl or 2-penten-4-ynyl.
Halogen and halo are fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine.
Haloalkyl can contain identical or different halogen atoms, and examples would be fluoromethyl, difluoromethyl, difluorochloromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, 2,2,2-trifluoroethyl, 2-fluoroethyl, 2-chloroethyl, 2,2,2-trichloroethyl and 3,3,3-trifluoropropyl.
Alkoxy is, for example, methoxy, ethoxy, propyloxy, i-propyloxy, n-butyloxy, iso-butyloxy, sec-butyloxy and tert-butyloxy; preferably methoxy and ethoxy.
Haloalkoxy is, for example, difluoromethoxy, trifluoromethoxy, 2,2,2-trifluoroethoxy, 1,1,2,2-tetrafluoroethoxy, 2-fluoroethoxy, 2-chloroethoxy and 2,2-difluoroethoxy.
Cycloalkyl is cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl or cycloheptyl, depending on the ring size.
Cyclic unsaturated hydrocarbon radicals can be aromatic, for example phenyl and naphthyl, or non-aromatic, for example cyclopentenyl, cyclohexenyl, cycloheptenyl and cyclooctadienyl, or partly aromatic, for example tetrahydronaphthyl and indanyl.
Alkanoyl is either straight-chain or branched, in each case taking into account the number of carbon atoms it contains from case to case, and examples would be formyl, acetyl, propionyl, butyryl, pivaloyl or octanoyl.
In alkoxy-, alkylthio-, alkanesulfinyl-, alkanesulfonyl-, nitro- or cyano-substituted carbon-containing groups and compounds, such as alkoxyalkyl, alkylthioalkyl, alkanesulfinylalkyl, alkanesulfonylalkyl, nitroalkyl, cyanoalkyl and cyanoalkanesulfonyl, one of the hydrogen atoms present in the unsubstituted basic structure on which they are based is replaced by alkoxy, alkylthio, alkanesulfinyl, alkanesulfonyl, nitro or, respectively, cyano.
A heterocyclyl radical is understood as meaning a 5- or 6-membered aromatic or non-aromatic ring having the hetero atoms N, O and/or S. An unsubstituted or substituted benzo group furthermore can be fused onto such a heterocyclyl radical bonded to the remainder of the molecule. Examples of heterocyclyl groups are pyridyl, pyrimidinyl, imidazolyl, thiazolyl, 1,3,4-thiadiazolyl, triazolyl, thienyl, furanyl, pyrrolyl, morpholinyl, oxazolyl and the corresponding partly or totally hydrogenated rings. Examples of heterocyclyl groups with a fused-on benzo group are quinolyl, isoquinolyl, benzoxazolyl, quinoxalinyl, benzothiazolyl, benzimidazolyl, indolyl, indolinyl.
Preferred compounds in the context of the invention are:
(1) Compounds of the formula I in which:
R10 is an open-chain saturated or unsaturated hydrocarbon radical which contains up to 8 carbon atoms and is unsubstituted or substituted by 1-5 halogen atoms, C1-C2alkoxy, hydroxyl, nitro, cyano, C1-C4alkanoyl, halo-C1-C4alkanoyl or C1-C4alkoxycarbonyl, a cyclic saturated or unsaturated hydrocarbon radical containing up to 10 carbon atoms or benzyl, in which the carbocyclic radical is unsubstituted or mono- to disubstituted by halogen, C1-C2 alkyl, halomethyl, nitro or cyano, or heterocyclyl, which is unsubstituted or mono- to trisubstituted by identical or different substituents from the group comprising halogen, C1-C2alkyl, halomethyl, nitro and cyano, or a 5- to 7-membered lactone ring; and in which the other substituents are as defined for formula I.
(2) Compounds of the formula I in which:
R10 is hydrogen, an open-chain saturated or unsaturated hydrocarbon radical which contains up to 12 carbon atoms and is unsubstituted or substituted by tri-(C1-C4alkyl)-silyl or an epoxy group; or the group
-CH(U)(CH2)mCO-W,
in which:
U is hydrogen, C1-C4alkyl, cyano, or C1-C6alkoxycarbonyl;
W is C1-C6alkoxy, C3-C6cycloalkoxy, or the group -N(T1)T2;
m is 0, 1 or 2 and
T1 and T2 independently of one another are hydrogen, C1-C6alkyl, which is unsubstituted or substituted by 1-3 halogen atoms, C1-C2alkoxy, hydroxyl, nitro, cyano, C1-C4alkanoyl, halo-C1-C4alkanoyl or C1-C4alkoxycarbonyl, C1-C6alkenyl which is unsubstituted or substituted by 1-3 halogen atoms, C1-C6alkynyl which is unsubstituted or substituted by
1-3 halogen atoms, a cyclic saturated or unsaturated hydrocarbon radical containing up to
10 carbon atoms or benzyl, in which the carbocyclic radical is unsubstituted or mono- to disubstituted by halogen, C1-C2alkyl, halomethyl, nitro or cyano, or heterocyclyl, which is unsubstituted or mono- to trisubstituted by identical or different substituents from the group comprising C1-C2alkyl, halogen, halomethyl, nitro and cyano; or
T1 and T2, together with the nitrogen atom to which they are bonded, form a 5- to
7-membered heterocyclic radical, which can additionally also contain O, S and/or N as ring atoms, in which the additional nitrogen is unsubstituted or substituted by C1-C4alkyl, phenyl, C1-C4alkanoyl, benzoyl or benzyl, and in which the carbon atoms of the heterocyclic radical are unsubstituted or mono- to trisubstituted by identical or different substituents from the group comprising halogen, C1-C2alkyl, halomethyl and nitro;
and in which the other substituents are as defined for formula I.
(3) Of the compounds of the formula I mentioned under (2), those in which:
R10 is hydrogen, an open-chain saturated or unsaturated hydrocarbon radical containing up to 6 carbon atoms, which is unsubstituted or substituted by tri-(C1-C4alkyl)-silyl or an epoxy group; or the group
-CH2-CO-W,
in which:
W is C1-C6alkoxy, C3-C6cycloalkoxy or the group -N(T1)T2;
T1 and T2 independently of one another are hydrogen, C1-C6alkyl, halo-C1-C6alkyl having
1-3 halogen atoms, C3-C6cycloalkyl, phenyl, halophenyl having 1-3 halogen atoms, pyridyl or naphthyl, or
T1 and T2, together with the nitrogen atom to which they are bonded, are piperidine, piperazine, morpholine or 2,6-dimethylmorpholine.
(4) Compounds of the formula I in which:
R1 is hydrogen, C1-C4alkyl, C1-C4alkoxy, halo-C1-C4alkyl having 1, 2 or 3 halogen atoms or C1-C4alkylthio;
R2 and R3 independently of one another are hydrogen, C1-C4alkyl, halo-C1-C4alkyl having 1, 2 or 3 halogen atoms, C1-C2alkoxy-C1-C4alkyl, nitro- C1-C4alkyl, cyano-C1-C4alkyl, C1-C4alkanoyl-C1-C4alkyl, C1-C4alkoxycarbonyl-C1-C4alkyl, C1-C2alkylthio-C1-C4alkyl, C1-C2alkanesulfιnyl-C1-C4alkyl, C1-C2alkanesulfonyl-C1-C4alkyl, C2-C4alkenyl, halo- C2-C4alkenyl having 1, 2 or 3 halogen atoms, C2-C4alkynyl, C3-C7cycloalkyl,
C1-C4alkoxy, halo-C1-C4alkoxy, C1-C4alkylthio, halo-C1-C4alkylthio, C1-C4alkylsulfinyl, C1-C4alkylsulfonyl, amino, C1-C4acylamino, nitro, cyano, hydroxyl or halogen;
R4 is hydrogen, C1-C4alkyl, halo-C1-C4alkyl having 1, 2 or 3 halogen atoms,
C1-C2alkoxy-C1-C4alkyl, nitro-C1-C4alkyl, cyano-C1-C4alkyl, C3-C5cycloalkyl, benzyl, C1-C4alkanoyl or benzoyl, the phenyl group of which is unsubstituted or substituted by one, two or three substituents chosen from the group comprising halogen, C1-C2alkyl, nitro and cyano;
R5 and R6 independently of one another are hydrogen, C1-C4alkyl, halo-C1-C4alkyl having 1, 2 or 3 halogen atoms, C1-C2alkoxy-C1-C4alkyl, nitro-C1-C4alkyl, cyano-C1-C4alkyl, C1-C4alkoxycarbonyl-C1-C4alkyl or C3-C6cycloalkyl, which is unsubstituted or substituted by one or two substituents chosen from the group comprising halogen and C1-C2alkyl;
R7, R8 and R9 independently of one another are hydrogen, halogen, C1-C4alkyl, halo-C1-C4alkyl having 1, 2 or 3 halogen atoms, C1-C2alkoxy-C1-C4alkyl,
C3-C6cycloalkyl, C1-C4alkoxy, halo-C1-C4alkoxy with 1, 2 or 3 halogen atoms,
C3-C7cycloalkoxy, C1-C4alkylthio, halo-C1-C4alkylthio having 1, 2 or 3 halogen atoms, cyano, nitro, phenyl, phenoxy and phenylthio, the phenyl groups in phenyl, phenoxy and phenylthio being unsubstituted or substituted by one, two or three substituents chosen from the group comprising halogen, C1-C2alkyl and C1-C2alkoxy, with the proviso that not more than one of the substituents R7, R8 or R9 is unsubstituted or substituted phenyl, substituted phenoxy or substituted phenylthio;
X is OR10, SR10 or N(R11)R12;
Y is a group -CH(R13)-, oxygen, sulfur or a group -N(R14)-;
R10 is C1-C8alkyl, halo- C1-C8-alkyl having 1 to 5 halogen atoms, C1-C2alkoxy- C1-C8alkyl, hydroxy-C1-C8alkyl, nitro-C1-C8alkyl, cyano- C1-C8alkyl, C1-C4alkanoyl- C1-C8alkyl, halo-C1-C4alkanoyl-C1-C8alkyl, C1-C4alkoxycarbonyl-C1-C8alkyl,
C3-C5cycloalkyl, benzyl, phenyl, which is unsubstituted or mono- to disubstituted by halogen, C1-C2alkyl, halomethyl, nitro or cyano, or heterocyclyl, which is unsubstituted or mono- to trisubstituted by identical or different substituents from the group comprising halogen, C1-C2alkyl, halomethyl, nitro and cyano, or a 5- to 7-membered lactone ring; R11 is hydrogen, C1-C4alkyl, halo-C1-C4-alkyl having 1, 2 or 3 halogen atoms,
C1-C2alkoxy-C1-C4alkyl, hydroxy-C1-C4alkyl, nitro-C1-C4alkyl, cyano- C1-C4alkyl, C1-C4alkanoyl-C1-C4alkyl, C1-C4alkoxycarbonyl-C1-C4alkyl, C3-C5cycloalkyl, benzyl, phenyl, which is unsubstituted or mono- to disubstituted by halogen, C1-C2alkyl, halomethyl, nitro or cyano, or heterocyclyl, which is unsubstituted or mono- to trisubstituted by identical or different substituents from the group comprising C1-C2alkyl, halogen, halomethyl, nitro and cyano;
R12 is hydrogen or C1-C4alkyl; or
R11 and R12 together with the nitrogen atom to which they are bonded are a heterocyclic radical, which is unsubstituted or mono- to trisubstituted by identical or different substituents from the group comprising halogen, C1-C2alkyl, halomethyl and nitro;
R13 is hydrogen or C1-C4alkyl;
R14 is hydrogen, C1-C4alkyl, C1-C4alkanoyl, benzoyl, the phenyl group of which is unsubstituted or substituted by one, two or three substituents chosen from the group comprising halogen, C1-C2alkyl, nitro and cyano, C1-C4alkylsulfonyl or aminosulfonyl, the nitrogen atom of which is unsubstituted or mono- or disubstituted by C1-C4alkyl; n is 1 or 2;
or, where appropriate, a tautomer thereof, in each case in the free form or in salt form.
(5) Compounds of the formula I in which:
R1 is hydrogen or C1-C4alkyl;
R2 and R3 independently of one another are hydrogen, C1-C4alkyl, halo-C1-C4-alkyl having 1, 2 or 3 halogen atoms, C1-C2alkoxy-C1-C4alkyl, C2-C4alkynyl, C3-C5cycloalkyl, hydroxyl or halogen;
R4 is hydrogen, C1-C4alkyl, C3-C5cycloalkyl or benzyl;
R5 and R6 independently of one another are hydrogen, C1-C4alkyl, halo-C1-C4alkyl having
1, 2 or 3 halogen atoms, C1-C2alkoxy-C1-C4alkyl or C3-C6cycloalkyl;
R7, R8 and R9 independently of one another are hydrogen, halogen or C1-C4alkyl;
X is OR10, SR10 or N(R11)R12;
Y is a group -CH(R13)-, oxygen, sulfur or a group -N(R14)-;
R10 is C1-C4alkyl, halo-C1-C4-alkyl having 1, 2 or 3 halogen atoms, C1-C2alkoxy- C1-C4alkyl, hydroxy-C1-C4alkyl, nitro-C1-C4alkyl, cyano-C1-C4alkyl, C1-C4alkanoyl- C1-C4alkyl, C1-C4alkoxycarbonyl-C1-C4alkyl, C3-C5cycloalkyl, benzyl, phenyl, which is unsubstituted or mono- to disubstituted by halogen, C1-C2alkyl, halomethyl, nitro or cyano, heterocyclyl, which is unsubstituted or mono- to trisubstituted by identical or different substituents from the group comprising halogen, C1-C2alkyl, halomethyl, nitro and cyano, or a 5- to 7-membered lactone ring;
R11 is hydrogen, C1-C4alkyl, halo- C1-C4-alkyl having 1, 2 or 3 halogen atoms,
C1-C2alkoxy-C1-C4alkyl, hydroxy-C1-C4alkyl, nitro-C1-C4alkyl, cyano-C1-C4alkyl, C1-C4alkanoyl-C1-C4alkyl, C1-C4alkoxycarbonyl-C1-C4alkyl, C3-C5cycloalkyl, benzyl or phenyl, which is unsubstituted or mono- to disubstituted by halogen, C1-C2alkyl, nitro or cyano;
R12 is hydrogen orC1-C4alkyl; or
R11 and R12, together with the nitrogen atom to which they are bonded, are a heterocyclyl radical, which is unsubstituted or mono- to trisubstituted by identical or different substituents from the group comprising halogen, C1-C2alkyl, halomethyl and nitro; R13 is hydrogen;
R14 is hydrogen, C1-C4alkyl, C1-C4alkanoyl, benzoyl, the phenyl group of which is unsubstituted or substituted by one, two or three substituents chosen from the group comprising halogen, C1-C2alkyl, nitro and cyano, C1-C4 alkylsulfonyl or aminosulfonyl, the nitrogen atom of which is unsubstituted or mono- or disubstituted by C1-C4alkyl;
n is 1 or 2;
(6) Compounds of the formula I, in which:
R1 is hydrogen; or C1-C4alkyl;
R2 is hydrogen, C1-C4alkyl, halo-C1-C4-alkyl having 1, 2 or 3 halogen atoms,
C1-C2alkoxy-C1-C4alkyl, cyclopropyl, ethynyl or halogen;
R3 is fluorine or chlorine;
R4 is hydrogen or C1-C4alkyl;
R5 is C1-C4alkyl;
R6 is hydrogen;
R7, R8 and R9 independently of one another are hydrogen or halogen;
X is OR10 ' SR10 or N(R11)R12;
Y is a group -CH(R13)-, oxygen, sulfur or a group -N(R14)-;
R10 is C1-C4alkyl, halo-C1-C4-alkyl having 1, 2 or 3 halogen atoms, C1-C2alkoxy- C1-C4alkyl, hydroxy-C1-C4alkyl, nitro-C1-C4alkyl, cyano-C1-C4alkyl, C1-C4alkanoyl- C1-C4alkyl, C1-C4alkoxycarbonyl-C1-C4alkyl, C2-C4alkenyl, which is unsubstituted or mono- to trisubstituted by halogen, C2-C4alkynyl, C3-C7cycloalkyl, C4-C8cycloalkenyl, benzyl or phenyl, which is unsubstituted or mono- to disubstituted by halogen, C1-C2alkyl, nitro or cyano, pyridine, pyrimidine or triazine, in which these heterocyclic radicals in each case are unsubstituted or mono- to trisubstituted by identical or different substituents from the group comprising halogen, C1-C2alkyl, trifluoromethyl and cyano, or a
5-membered lactone ring;
R11 is hydrogen, C1-C4alkyl, halo-C1-C4-alkyl having 1, 2 or 3 halogen atoms,
C1-C2alkoxy-C1-C4alkyl, hydroxy-C1-C4alkyl, nitro-C1-C4alkyl, cyano-C1-C4alkyl, C1-C4alkanoyl-C1-C4alkyl, C1-C4alkoxycarbonyl-C1-C4alkyl, C2-C4alkenyl, which is unsubstituted or mono- to trisubstituted by halogen, C2-C4alkynyl, C3-C7cycloalkyl, C4-C8cycloalkenyl, benzyl or phenyl, which is unsubstituted or mono- to disubstituted by halogen, C1-C2alkyl, nitro or cyano,
R12 is hydrogen or C1-C4alkyl; or
R11 and R12, together with the nitrogen atom to which they are bonded, are pyrrolidine, piperidine, piperazine, morpholine or 2,6-dimethylmorpholine; R13 is hydrogen;
R14 is hydrogen, C1-C4alkyl, C1-C4alkanoyl or benzoyl, the phenyl group of which is unsubstituted or substituted by one, two or three substituents chosen from the group comprising halogen, C1-C2alkyl, nitro and cyano;
n is 1 or 2.
(7) Compounds of the formula I, in which
R1 is hydrogen; or C1-C4alkyl;
R2 is hydrogen, C1-C4alkyl, halo-C1-C4-alkyl having 1, 2 or 3 halogen atoms,
C1-C2alkoxy-C1-C4alkyl, cyclopropyl, ethynyl or halogen;
R3 is chlorine;
R4 is hydrogen or C1-C4alkyl;
R5 is C1-C4alkyl;
R6 is hydrogen;
R7, R8 and R9 independently of one another are hydrogen or halogen;
X is OR10, SR10 or N(R11)R12;
Y is a group -CH(R13)-, oxygen, sulfur or a group -N(R14)-;
R10 is C1-C4alkyl, halo-C1-C4-alkyl having 1, 2 or 3 halogen atoms, C1-C2alkoxy- C1-C4alkyl, hydroxy-C1-C4alkyl, nitro-C1-C4alkyl, cyano-C1-C4alkyl, C1-C4alkanoyl- C1-C4alkyl, C1-C4alkoxycarbonyl-C1-C4alkyl, C3-C5cycloalkyl, benzyl, phenyl, which is unsubstituted or mono- to disubstituted by halogen, C1-C2alkyl, nitro or cyano, pyridine, pyrimidine or triazine, in which these heterocyclic radicals in each case are unsubstituted or mono- to trisubstituted by identical or different substituents from the group comprising halogen, C1-C2alkyl, trifluoromethyl and cyano, or a 5-membered lactone ring;
R11 is hydrogen, C1-C4alkyl, halo-C1-C4-alkyl having 1, 2 or 3 halogen atoms,
C1-C2alkoxy-C1-C4alkyl, hydroxy-C1-C4alkyl, nitro-C1-C4alkyl, cyano-C1-C4alkyl, C1-C4alkanoyl-C1-C4alkyl, C1-C4alkoxycarbonyl-C1-C4alkyl, C3-C5Cycloalkyl, benzyl or phenyl, which is unsubstituted or mono- to disubstituted by halogen, C1-C2alkyl, nitro or cyano,
R12 is hydrogen or C1-C4alkyl; or
R11 and R12, together with the nitrogen atom to which they are bonded, are pyrrolidine, piperidine, piperazine, morpholine or 2,6-dimethylmorpholine;
R13 is hydrogen;
R14 is hydrogen, C1-C4alkyl, C1-C4alkanoyl or benzoyl, the phenyl group of which is unsubstituted or substituted by one, two or three substituents chosen from the group comprising halogen, C1-C2alkyl, nitro and cyano; n is 1 or 2.
(8) Of the compounds mentioned under (7), those in which:
X is S R10;
R10 is C1-C2alkyl, halo-C1-C2-alkyl having 1, 2 or 3 halogen atoms, C1-C2alkoxy- C1-C2alkyl, hydroxy- C1-C2alkyl, acetyl-C1-C2alkyl, tert-butyloxycarbonyl-C1-C2alkyl, benzyl, phenyl, which is unsubstituted or mono- to disubstituted by halogen, C1-C2alkyl, nitro or cyano, pyridine, pyrimidine or triazine, in which these heterocyclic radicals in each case are unsubstituted or mono- to trisubstituted by identical or different substituents from the group comprising halogen, C1-C2alkyl, trifluoromethyl and cyano, or a
5-membered lactone ring.
(9) Of the compounds mentioned under (7), furthermore those in which:
X is N(R11)R12;
R11 is hydrogen, C1-C4alkyl, halo- C1-C2 alkyl having 1, 2 or 3 halogen atoms,
C1-C2alkoxy- C1-C2alkyl, hydroxy-C1-C2alkyl, nitro-C1-C4alkyl, cyano-C1-C2alkyl, acetyl-C1-C2alkyl, tert-butyloxycarbonyl- C1-C2alkyl, C3-C5cycloalkyl, benzyl or phenyl, which is unsubstituted or mono- to disubstituted by halogen, C1-C2alkyl, nitro or cyano, R12 is hydrogen or C1-C4alkyl; or
R11 and R12, together with the nitrogen atom to which they are bonded, are pyrrolidine, piperidine, piperazine, morpholine or 2,6-dimethylmorpholine.
(10) Of the compounds mentioned under (7), those of the formula I.1
Figure imgf000013_0001
and of these especially those in which:
R2 is hydrogen, methyl or ethyl;
R3 is fluorine or chlorine;
R5 is methyl or ethyl;
R8 and R9 independently of one another are hydrogen or fluorine; X is OR10' SR10 or N(R11) R12;
R10 is methyl, ethyl, difluoromethyl, trifluoromethyl, 2,2,2-trifluoroethyl, cyanomethyl, tert-butyloxycarbonylmethyl, allyl, 2-propynyl, cyclohexyl, cyclohexenyl, pyridine, pyrimidine or triazine, in which these heterocyclic radicals in each case are unsubstituted or mono- to trisubstituted by identical or different substituents from the group comprising halogen, C1-C2alkyl, trifluoromethyl and cyano;
R11 is hydrogen, C1-C4alkyl, halo-C1-C4-alkyl having 1, 2 or 3 halogen atoms, hydroxy- C1-C4alkyl, cyano-C1-C4alkyl, allyl, 2-propynyl, cyclohexyl, cyclohexenyl, cyclopropyl, benzyl or phenyl;
R12 is hydrogen; or
R11 and R12, together with the nitrogen atom to which they are bonded, are pyrrolidine, piperidine, piperazine, morpholine or 2,6-dimethylmorpholine.
(11) Of the compounds mentioned under (7), those of the formula I.2
Figure imgf000014_0001
and of these, especially those in which:
R2 is hydrogen, methyl or ethyl;
R3 is fluorine or chlorine;
R5 is methyl or ethyl;
R8 and R9 independendy of one another are hydrogen or fluorine;
X is OR10, SR10 or N(R11)R12;
R10 is methyl, ethyl, difluoromethyl, trifluoromethyl, 2,2,2-trifluoroethyl,
cyanomethyl,tert-butyloxycarbonylmethyl, allyl, 2-propynyl, cyclohexyl, cyclohexenyl, pyridine, pyrimidine or triazine, in which these heterocyclic compounds in each case are unsubstituted or mono- to trisubstituted by identical or different substituents from the group comprising halogen, C1-C2alkyl, trifluoromethyl and cyano;
R11 is hydrogen, C1-C4alkyl, halo-C1-C4-alkyl having 1, 2 or 3 halogen atoms, hydroxy- C1-C4alkyl, cyano-C1-C4alkyl, allyl, 2-propynyl, cyclohexyl, cyclohexenyl, cyclopropyl, benzyl or phenyl;
R12 is hydrogen; or R11 and R12, together with the nitrogen atom to which they are bonded, are pyrrolidine, piperidine, piperazine, morpholine or 2,6-dimethylmorpholine.
(12) Of the compounds mentioned under (7), those of the formula I.3
Figure imgf000015_0001
and of these, especially those in which:
R2 is hydrogen, methyl or ethyl;
R3 is fluorine or chlorine;
R5 is methyl or ethyl;
R8 and R9 independently of one another are hydrogen or fluorine;
X is OR10, SR10 or N(R11)R12;
R10 is methyl, ethyl, difluoromethyl, trifluoromethyl, 2,2,2-trifluoroethyl,
cyanomethyl.tert-butyloxycarbonylmethyl, allyl, 2-propynyl, cyclohexyl, cyclohexenyl, pyridine, pyrimidine or triazine, in which these heterocyclic radicals in each case are unsubstituted or mono- to trisubstituted by identical or different substituents from the group comprising halogen, C1-C2alkyl, trifluoromethyl and cyano;
R11 is hydrogen, C1-C4alkyl, halo-C1-C4-alkyl having 1, 2 or 3 halogen atoms, hydroxy- C1-C4alkyl, cyano-C1-C4alkyl, allyl, 2-propynyl, cyclohexyl, cyclohexenyl, cyclopropyl, benzyl or phenyl;
R12 is hydrogen; or
R11 and R12, together with the nitrogen atom to which they are bonded, are pyrrolidine, piperidine, piperazine, morpholine or 2,6-dimethylmorpholine.
(13) Of the compounds mentioned under (7), those of the formula I.4
Figure imgf000016_0001
and of these, especially those in which:
R2 is hydrogen, methyl or ethyl;
R3 is fluorine or chlorine;
R5 is methyl or ethyl;
R8 and R9 independently of one another are hydrogen or fluorine;
X is OR10, SR10 or N(R11)R12;
R10 is methyl, ethyl, difluoromethyl, trifluoromethyl, 2,2,2-trifluoroethyl,
cyanomethyl.tert-butyloxycarbonylmethyl, allyl, 2-propynyl, cyclohexyl, cyclohexenyl, pyridine, pyrimidine or triazine, in which these heterocyclic radicals in each case are unsubstituted or mono- to trisubstituted by identical or different substituents from the group comprising halogen, C1-C2alkyl, trifluoromethyl and cyano;
R11 is hydrogen, C1-C4alkyl, halo-C1-C4-alkyl having 1, 2 or 3 halogen atoms, hydroxy- C1-C4alkyl, cyano-C1-C4alkyl, allyl, 2-propynyl, cyclohexyl, cyclohexenyl, cyclopropyl, benzyl or phenyl;
R12 is hydrogen; or
R11 and R12, together with the nitrogen atom to which they are bonded, are pyrrolidine, piperidine, piperazine, morpholine or 2,6-dimethylmorpholine.
(14) Of the compounds mentioned under (7), those of the formula I.5
Figure imgf000016_0002
and of these, especially those in which:
R2 is hydrogen, methyl or ethyl;
R3 is fluorine or chlorine; R5 is methyl or ethyl;
R8 and R9 independendy of one another are hydrogen or fluorine;
X is OR10, SR10 or N(R11)R12;
R10 is methyl, ethyl, difluoromethyl, trifluoromethyl, 2,2,2-trifluoroethyl,
cyanomethyl,tert-butyloxycarbonylmethyl, allyl, 2-propynyl, cyclohexyl, cyclohexenyl, pyridine, pyrimidine or triazine, in which these heterocyclic radicals in each case are unsubstituted or mono- to trisubstituted by identical or different substituents from the group comprising halogen, C1-C2alkyl, trifluoromethyl and cyano;
R11 is hydrogen, C1-C4alkyl, halo-C1-C4-alkyl having 1, 2 or 3 halogen atoms, hydroxy- C1-C4alkyl, cyano- C1-C4alkyl, allyl, 2-propynyl, cyclohexyl, cyclohexenyl, cyclopropyl, benzyl or phenyl;
R12 is hydrogen; or
R11 and R12, together with the nitrogen atom to which they are bonded, are pyrrolidine, piperidine, piperazine, morpholine or 2,6-dimethylmorpholine.
(15) Of the compounds mentioned under (7), those of the formula I.6
Figure imgf000017_0001
and of these, especially those in which:
R2 is hydrogen, methyl or ethyl;
R3 is fluorine or chlorine;
R5 is methyl or ethyl;
R8 and R9 independently of one another are hydrogen or fluorine;
X is OR10, SR10 or N(R11) R12;
R10 is methyl, ethyl, difluoromethyl, trifluoromethyl, 2,2,2-trifluoroethyl,
cyanomethyl.tert-butyloxycarbonylmethyl, allyl, 2-propynyl, cyclohexyl, cyclohexenyl, pyridine, pyrimidine or triazine, in which these heterocyclic radicals in each case are unsubstituted or mono- to trisubstituted by identical or different substituents from the group comprising halogen, C1-C2alkyl, trifluoromethyl and cyano;
R11 is hydrogen, C1-C4alkyl, halo-C1-C4-alkyl having 1, 2 or 3 halogen atoms, hydroxy- C1-C4alkyl, cyano-C1-C4alkyl, allyl, 2-propynyl, cyclohexyl, cyclohexenyl, cyclopropyl, benzyl or phenyl;
R12 is hydrogen; or
R11 and R12, together with the nitrogen atom to which they are bonded, are pyrrolidine, piperidine, piperazine, morpholine or 2,6-dimethylmorpholine.
(16) Compounds of the formula I.9
in which:
Figure imgf000018_0001
R2 is methyl or ethyl;
X is OR10 or SR10 ;
R10 is C1-C6alkyl, halo- C1-C6alkyl having 1-3 halogen atoms,
C1-C4alkoxycarbonyl-C1-C4alkyl, C2-C6alkenyl, C2-C6alkynyl, C3-C6cycloalkyl, or the group
-CH2-CO-W,
in which:
W is C1-C6alkoxy, C3-C6cycloalkoxy, or the group -N(T1)T2;
T1 and T2 independently of one another are hydrogen, C1-C6alkyl, halo- C1-C6alkyl having 1-3 halogen atoms, C3-C6cycloalkyl, phenyl, halophenyl having 1-3 halogen atoms, pyridyl or naphthyl, or
T1 and T2, together with the nitrogen atom to which they are bonded, are piperidine, piperazine, morpholine or 2,6-dimethylmorpholine.
(17) Compounds of the formula I.10
Figure imgf000018_0002
in which:
R2 is methyl or ethyl; X is OR10 or SR10 ;
R10 is C1-C6alkyl, halo- C1-C6alkyl having 1-3 halogen atoms,
C1-C4alkoxycarbonyl-C1-C4alkyl, C2-C6alkenyl, C2-C6alkynyl, or C3-C6cycloalkyl, or the group
-CH2-CO-W,
in which:
W is C1-C6alkoxy, C3-C6cycloalkoxy, or the group -N(T1)T2;
T1 and T2 independently of one another are hydrogen, C1-C6alkyl, halo-C1-C6alkyl having
1-3 halogen atoms, C3-C6cycloalkyl, phenyl, halophenyl having 1-3 halogen atoms, pyridyl or naphthyl, or
T1 and T2, together with the nitrogen atom to which they are bonded, are piperidine, piperazine, morpholine or 2,6-dimethylmorpholine.
(18) Compounds of the formula I.11
Figure imgf000019_0001
in which:
R2 is methyl or ethyl;
X is OR10 or SR10 ;
R10 is C1-C6alkyl, halo- C1-C6alkyl having 1-3 halogen atoms,
C1-C4alkoxycarbonyl-C1-C4alkyl, C2-C6alkenyl, C2-C6alkynyl, C3-C6cycloalkyl, or the group
-CH2-CO-W,
in which:
W is C1-C6alkoxy, C3-C6cycloalkoxy, or the group -N(T1)T2;
T1 and T2 independently of one another are hydrogen, C1-C6alkyl, halo-C1-C6alkyl having
1-3 halogen atoms, C3-C6cycloalkyl, phenyl, halophenyl having 1-3 halogen atoms, pyridyl or naphthyl, or
T1 and T2, together with the nitrogen atom to which they are bonded, are piperidine, piperazine, morpholine or 2,6-dimethylmorpholine. (19) A particular group of compounds are furthermore those in which, in formula I, X is SR10.
The invention furthermore relates to a process for the preparation of compounds of the formula I and, where appropriate, their tautomers, in each case in the free form or in salt form, for example, which comprises reacting: a) for the preparation of a compound of the formula I in which X is SR10:
a compound of the formula II
Figure imgf000020_0001
in which the substituent A is in the β- or γ-position, and in which R1 to R9, Y and n are as defined for formula I, with a compound of the formula III R10-z (III), in which R10 is as defined for formula I and Z is a nucleofugic radical which can easily be split off; preferably in the presence of a base, particularly preferably by first reacting a compound of the formula II with a base and then reacting a compound of the formula III; or b) for the preparation of a compound of the formula I in which X is OR10 or N(R11)R12: a compound of the formula I in which X is SR10 with a compound of the formula IV
M-X (IV), in which:
M is hydrogen, Li+, Na+, K+, 1/2Mg2+ or a quaternary ammonium ion;
X is OR10 or N(R11)R12, and wherein
R10, R11 and R12 are as defined for formula I; if appropriate in the presence of a base; or c) for the preparation of a compound of the formula I in which R4 and R14 are as defined for formula I but are other than hydrogen:
a compound of the formula I in which R4 and R14 are hydrogen with a compound of the formula R4'-Z' or R14'-Z', in which R4' and R14' are as defined in formula I for R4 and R14, but are other than hydrogen, and Z' is a nucleofugic radical which can easily be split off;
preferably in the presence of a base.
Another process for the preparation of a compound of the formula I comprises reacting a compound of the formula VII
Figure imgf000021_0001
in which the substituent A is in the β- or γ-position, and in which R1 to R9, Y and n are as defined for formula I, with phosphorus oxychloride or with sulfuryl chloride to give a compound of the formula VIII
Figure imgf000021_0002
and then reacting this compound with a compound of the formula IV'
M-X' (IV'), in which:
M is hydrogen, Li+, Na+, K+, 1/2Mg2+ or a quaternary ammonium ion; X' is OR10, SR10 or N(R11)R12, and in which R10, R11 and R12 are as defined for formula I; if appropriate in the presence of a base.
The reactions described above and below are carried out in a manner known per se, for example in the absence or usually in the presence of a suitable solvent or diluent or a mixture thereof, the reaction being carried out, as required, by cooling, at room
temperature or by heating, for example in a temperature range from about -80°C up to the boiling point of the reaction medium, preferably from about -20°C up to about +150°C, and, if necessary, in a closed vessel, under pressure, in an inert gas atmosphere and/or under anhydrous conditions. Typical reaction conditions can be found in the examples.
Nucleofugic radicals Z and Z' are, for example: fluorine, chlorine, bromine, iodine, C1-C8alkylthio, such as methylthio, ethylthio or propylthio, C1-C8alkanoyloxy, such as acetoxy, (halo) C1-C8alkanesulfonyloxy, such as methanesulfonyloxy, ethanesulfonyloxy or trifluoromethanesulfonyloxy, or unsubstituted or substituted phenylsulfonyloxy, such as benzenesulfonyloxy or p-toluenesulfonyloxy, and furthermore also hydroxyl.
Suitable bases are, for example, alkali metal or alkaline earth metal hydroxides, hydrides, amides, alkanolates, carbonates, dialkylamides or alkylsilylamides, alkylamines, alkylenediamines, non-alkylated or N-alkylated, saturated or unsaturated
cycloalkylamines, basic heterocyclic compounds, ammonium hydroxides and carbocyclic amines. Examples are sodium hydroxide, hydride, amide, methanolate and carbonate, potassium tert-butanolate and carbonate, lithium diisopropylamide, potassium
bis(trimethylsilyl)amide, calcium hydride, triethylamine, triethylenediamine,
cyclohexylamine, N-cyclohexyl-N,N-dimethylamine, N,N-diethylaniline, pyridine, 4-(N,N-dimethylamino)pyridine, N-methylmorpholine, benzyl-trimethyl-ammonium hydroxide and 1,8-diazabicyclo[5.4.0]undec-5-ene (DBU).
The reaction partners can be reacted with one another as such, i.e. without addition of a solvent or diluent, for example in the melt. However, the addition of an inert solvent or diluent or a mixture thereof is usually advantageous. Examples of such solvents or diluents which may be mentioned are: aromatic, aliphatic and alicyclic hydrocarbons and halogenated hydrocarbons, such as benzene, toluene, xylene, chlorobenzene,
bromobenzene, petroleum ether, hexane, cyclohexane, methylene chloride, chloroform, dichloroethane or trichloroethane; ethers, such as diethyl ether, ten-butyl methyl ether, tetrahydrofuran or dioxane; ketones, such as acetone or methyl ethyl ketone; alcohols, such as methanol, ethanol, propanol, butanol, ethylene glycol or glycerol; esters, such as ethyl acetate or butyl acetate; amides, such as N,N-dimethylformamide,
N,N-dimethylacetamide, N-methylpyrrolidone or hexamethylphosphoric acid triamide; nitriles, such as acetonitrile; and sulfoxides, such as dimethyl sulfoxide. Bases employed in excess, such as triethylamine, pyridine, N-methylmorpholine or N,N-diethylaniline, can also serve as solvent or diluent.
The reaction is advantageously caπied out in a temperature range of about 0°C to about +180°C, preferably about +20°C to about +130°C, in many cases at the reflux temperature of the solvent used.
As an alternative, the reaction can be caπied out under phase transfer catalysis in an organic solvent, for example methylene chloride or toluene, in the presence of an aqueous basic solution, for example sodium hydroxide solution, and a phase transfer catalyst, for example tetrabutylammonium hydrogen sulfate.
A compound I obtainable according to the process or in another manner or, where appropriate, a tautomer thereof can be converted into another compound I in a manner known per se by replacing one or more substituents of the starting compound I by another substituent in the customary manner.
For example:
- substituents which do not contain halogen or non-halogenated aromatic or
heteroaromatic ring part structures can be halogenated to halo-containing substituents or halogenated aromatic or heteroaromatic ring part structures;
- halogen substituents can be replaced by other substituents, such as cyano, alkylthio or alkoxy substituents;
- alkanoyl, benzoyl or sulfonyl substituents can be replaced by hydrogen which is easy to replace or
- N-hydrogen can be replaced by N-alkyl, N-benzyl, N-aryl, N-heteroaryl, N-alkanoyl, N-benzoyl or N-sulfonyl;
- sulfides can be oxidized to sulfoxides and sulfones;
- carbonyl groups can be sulfated to thiocarbonyl groups.
Salts of compounds I can be prepared in a manner known per se. Thus, for example, acid addition salts of compounds I are obtained by treatment with a suitable acid or a suitable ion exchanger reagent, and salts with bases can be obtained by treatment with a suitable base or a suitable ion exchanger reagent.
Salts of compounds I can be converted into the free compounds I in the customary manner, acid addition salts for example by treatment with a suitable basic agent or a suitable ion exchanger reagent and salts with bases for example by treatment with a suitable acid or a suitable ion exchanger reagent
Some of the compounds I can be in the form of one of the possible isomers or as mixtures thereof, for example as pure isomers or as isomer mixtures, such as enantiomer mixtures, for example racemates, diastereomer mixtures or racemate mixtures, depending on the number of and absolute relative configuration of the asymmetric carbon atoms; the invention relates both to the pure isomers and to all the possible isomer mixtures and is in each case to be understood accordingly above and below, although stereochemical details are not mentioned specifically in each case.
Diastereomer mixtures and racemate mixtures of compounds I obtainable according to the process or by another means can be separated into the pure diastereomers or racemates in a known manner on the basis of the physico-chemical differences of the constituents, for example by fractional crystallization, distillation and/or chromatography.
The invention likewise relates to novel starting substances and intermediates used for the preparation of the compounds of the formula I, their use and processes for their preparation.
The compounds of the formula II can be prepared, for example, by reacting a compound of the formula V
Figure imgf000024_0001
in which R1' R2 and R3 have the meanings given for formula I and Z is a nucleofugic radical which can easily be split off, with a compound of the formula VI
Figure imgf000025_0001
or a salt thereof, preferably in the presence of a base, in which R4 to R9, Y and n are as defined for the formula I.
Another possibility for the preparation of compounds of the formula II comprises reacting a compound of the formula VII with a thionating agent, preferably with phosphorus pentasulfide or with 4-methoxyphenylthiophosphonic acid cyclodithioanhydride
("Lawesson reagent"), if appropriate in a solvent.
The compounds of the formulae III, IV and V are known or can be prepared analogously to known compounds.
The preparation of compounds of the formula V is described, for example, in: D.J. Brown, "The Pyrimidines", in "Heterocyclic Compounds" and in European Patent Application EP-A-0470 600.
Reference may be made to Patent Application No. 509/93-0 filed in Switzerland on 18th February 1993 for the preparation of compounds of the formula VI.
Pyrimidines which are amino-substituted in the 4-position are already known, for example from the Patent Application WO 92/08704. The compounds I of the present invention differ from these known compounds structurally in a characteristic manner; furthermore, the compounds of the formula I of the present invention show an unexpectedly high microbicidal, insecticidal, nematicidal and acaricidal activity. Protection of plants can occur here either by direction action on the pests or by activation and stimulation of the plant's own defence system (immunization).
The compounds of the formula I of the present invention are stable at room temperature to slightly elevated temperature and can easily be stored. They can be used in the agricultural sector and related fields preventively and/or curatively as active compounds for control of plant pests. The active compounds of the formula I according to the invention are distinguished not only by an outstanding action - even at low use concentrations - but also by a good agricultural acceptability. They have very good advantageous properties, in particular systemic properties, and can be used for protection of numerous crop plants. The pests which occur on plants or parts of plants (fruit, blossom, foliage, stems, tubers, roots) of various crops of useful plants can be checked or destroyed with the active compounds of formula I, parts of plants which grow later also remaining spared, for example from phytopathogenic microorganisms.
The compounds I are active, for example, against phytopathogenic fungi belonging to the following classes: Fungi imperfecti (for example Botrytis, Pyricularia, Helminthosporium, Fusarium, Septoria, Cercospora and Altemaria) and Basidiomycetes (for example
Rhizoctonia, Hemileia, Puccinia). They furthermore have an action against the classes of Ascomycetes (for example Venturia and Erysiphe, Podosphaera, Monilinia, Uncinula) and Oomycetes (for example Phytophthora, Pythium, Plasmopara).
The compounds I furthermore can be used as dressing agents for the treatment of seed (fruit, tubers, grains) and plant seedlings for protection from fungal infections and against phytopathogenic fungi which occur in the soil.
The compounds I according to the invention are also useful active compounds in the control of pests of the order Acarina and of the insects and nematode classes on crop and ornamental plants in agriculture, in particular in cotton, vegetable and fruit plantations, in forestry, in the field of protection of stored products and materials, and in the hygiene sector for control of animal pests, in particular on domestic animals and productive livestock. They are active against various stages of development. They can display tiieir action here in the immediate mortality of the pests or only after some time, for example during moulting, or in a significantly reduced oviposition and/or hatching rate. The order of the Acarina includes, for example, Boophilus spp. and Tetranychus Spp.; this list is not limiting.
The invention also relates to the compositions which comprise compounds of the formula I, as the active compound, together with a carrier material, in particular crop protection compositions, and to their use in the agricultural sector and related fields. The invention furthermore also includes the preparation of these compositions, which comprises intimately mixing the active substance with one or more of the extenders and distributing agents described below. The invention also includes a method for the treatment of plants, which comprises application of the novel compounds I or of the novel compositions.
Target crops for the crop protection use in the context of the invention are, for example, the following plant species: cereals (wheat, barley, rye, oats, rice, maize, sorghum and related species); beet (sugar-beet and feed beet); pome, stone and soft fruit (apples, pears, plums, peaches, almonds, cherries, strawberries, raspberries and blackberries); leguminous plants (beans, lentils, peas, soya); oil crops (rape, mustard, poppy, olive, sunflower, coconut, castor, cacao, groundnut); Cucurbitaceae (squash, cucumbers, melons); fibre plants (cotton, flax, hemp, jute); citrus fruits (oranges, lemons, grapefruit, mandarins); vegetable varieties (spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes, paprika); laurel plants (avocado, cinnamonium, camphor) and plants such as tobacco, nuts, coffee, aubergines, sugar cane, tea, pepper, vines, hops, banana and natural rubber plants and ornamentals.
Active compounds I are usually used in the form of compositions and can be applied to the area or plants to be treated at the same time as or successively with other active
compounds. These other active compounds can be, for example, fertilizers, trace element mediators or other preparations which influence plant growth. Selective herbicides and insecticides, fungicides, bactericides, nematicides, molluscicides or mixtures of several of these preparations together with, where appropriate, further carriers, surfactants or other application-promoting additives customary in formulation technology can also be used here.
Suitable carriers and additives can be solid or liquid and are the substances used for this purpose in formulation technology, for example naturally occurring or regenerated mineral substances, solvents, dispersants, wetting agents, tackifying agents, thickeners, binders or fertilizers.
A preferred process for application of an active compound of the formula I or of an agrochemical composition which comprises at least one of these active compounds is application to the foliage (foliar application). The application frequency and rate of application depend here on the risk of infection by the pathogen in question. However, the active compounds I can also enter the plant through the root system via the soil (systemic action), by soaking the locus of the plant with a liquid composition or incorporating the substances into the soil in solid form, for example in the form of granules (soil
application). In the case of paddy rice crops, such granules can be metered into the flooded rice field. However, the compounds I can also be applied to seed grains (coating) by either soaking the grains in a liquid composition of the active compound or coating them with a solid formulation.
The compounds I are employed here in unchanged form or, preferably, together with the auxiliaries customary in formulation technology. For this purpose, they are
advantageously processed in a known manner, for example, to emulsion concentrates, spreadable pastes, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts or granules, for example by encapsulation in, for example, polymeric substances. The methods of application, such as spraying, atomizing, dusting, scattering, coating or pouring, like the nature of the compositions, are chosen according to the intended aims and the given circumstances.
Favourable rates of application are in general 5 g to 2 kg of active substance (AS) per hectare (ha), preferably 10 g to 1 kg of AS/ha, in particular 20 g to 600 g of AS/ha.
Dosages of 10 mg to 1 g of active substance per kg of seed are advantageously employed for use as seed dressing compositions.
The formulations, i.e. the compositions, formulations or preparations comprising the active compound of the formula I and, where appropriate, a solid or liquid additive, are prepared in a known manner, for example by intimate mixing and/or grinding of the active compound with extenders, such as solvents, solid carriers and, if appropriate,
surface-active compounds (surfactants).
Solvents are: aromatic hydrocarbons, preferably C8 to C12 fractions, such as xylene mixtures or substituted naphthalenes, phthalic acid esters, such as dibutyl or dioctyl phthalate, aliphatic hydrocarbons, such as cyclohexane or paraffins, alcohols and glycols and ethers and esters thereof, such as ethanol, ethylene glycol and ethylene glycol monomethyl or -ethyl ether, ketones, such as cyclohexanone, strongly polar solvents, such as N-methyl-2-pyrrolidone, dimediyl sulfoxide or dimethylformamide, and, if appropriate, epoxidized vegetable oils, such as epoxidized coconut oil or soya oil, and water.
The solid carriers used, for example for dusts and dispersible powders, are as a rule naturally occurring rock powders, such as calcite, talc, kaolin, montmorillonite or attapulgite. Highly disperse silicic acid or highly disperse absorbent polymers can also be added to improve the physical properties. Granular, adsorptive granule carriers are porous types, such as pumice, broken bricks, sepiolite or bentonite, and non-sorptive carrier materials are, for example, calcite or sand. A large number of pregranulated materials of inorganic or organic nature, such as dolomite or comminuted plant residues, furthermore can be used.
Surface-active compounds are nonionic, canonic and/or anionic surfactants having good emulsifying, dispersing and wetting properties, depending on the nature of the active compound of the formula I to be formulated. Surfactants are also to be understood as meaning surfactant mixtures.
Suitable anionic surfactants can be either so-called water-soluble soaps or water-soluble synthetic surface-active compounds.
Examples of nonionic surfactants are nonylphenolpolyethoxyethanols, castor oil polyglycol ethers, polypropylene/polyethylene oxide adducts, tributyphenoxypolyethylene-ethanol, polyethylene glycol and octylphenoxypolyethoxyethanol.
Further surfactants are also fatty acid esters of polyoxyethylene-sorbitan, such as polyoxyethylene-sorbitan trioleate.
The cationic surfactants are, in particular, quaternary ammonium salts which contain at least one alkyl radical having 8 to 22 C atoms as N substituents and contain lower, optionally halogenated alkyl, benzyl or lower hydroxyalkyl radicals as further substituents.
Other surfactants customary in formulation technology are known to the expert or can be taken from the relevant technical literature.
The agrochemical compositions as a rule comprise 0.1 to 99 per cent by weight, in particular 0.1 to 95 per cent by weight, of active compound of the formula 1, 99.9 to 1 per cent by weight, in particular 99.8 to 5 per cent by weight, of a solid or liquid additive and 0 to 25 per cent by weight, in particular 0.1 to 25 per cent by weight, of a surfactant.
While concentrated compositions tend to be preferred as commercial goods, the end user as a rule uses dilute compositions.
The compositions can also comprise further additives, such as stabilizers, foam suppressants, viscosity regulators, binders or tackifiers, as well as fertilizers or other active compounds, in order to achieve specific effects.
The following examples illustrate the invention described above, without limiting it in its scope. Temperatures are stated in degrees Celcius. The following abbreviations are used: Ac = acetyl; Et = ethyl; Iso-Pr = isopropyl; Me = methyl; Ph = phenyl; Pr = n-propyl; Bu = butyl; m.p. = melting point. DS = diastereomer, reg = regioisomer. "NMR" means "nuclear magnetic resonance spectrum". MS = mass spectrum. "%" means "per cent by weight", if corresponding concentrations are not stated in another unit. The term "active compound according to the invention" is in each case to be understood as meaning a compound I or its tautomer, in the free form or in the form of a salt.
Examples for the preparation of the compounds according to the invention
Example H-1a: 0.96 g of NaH in oil (~55%) in 15 ml of anhydrous tetrahydrofuran is initially introduced into a sulfonating flask at room temperature. A solution of 6.97 g of 6-[1-(5-chloro-6-ethylpyrimidin-4-ylamino)ethyl]-2H-1,4-benzoxazine-3-thione in 35 ml of absolute tetrahydrofuran is tiien added dropwise under an N2 atmosphere in the course of about 10 minutes. After brief subsequent stirring, 3.12 g of methyl iodide are added at room temperature and the mixture is then stirred at about 25°C for 4 hours. After the solvent has been stripped off under a water pump vacuum, the residue is purified by column chromatography over silica gel (mobile phase: n-hexane/ethyl acetate 2:1). 6.4 g of 6-[1-(5-chloro-6-ethylpyrimidin-4-ylamino)ethyl]-3-methylthio-2H-1,4-benzoxazine are obtained in the form of a yellow powder (m.p. 73-74°C).
Figure imgf000030_0001
Example H-1b: 1.0 g of 6-[1-(5-chloro-6-ethylpyrimidin-4-ylamino)ethyl]-3-methylthio- 2H-1,4-benzoxazine (H-1a) and 1.5 g of sodium methylate (30% solution in methanol) in 15 ml of absolute methanol are initially introduced into a sulfonating flask at room temperature. The mixture is kept under reflux for 3 hours and the solvent is then stripped off under a water pump vacuum. The residue is purified by column chromatography over silica gel (mobile phase: n-hexane/ethyl acetate 2:1). 0.9 g of
6-[1-(5-chloro-6-edιylpyrimidin-4-yl-amino)ethyl]-3-methoxy-2H -1,4-benzoxazine is obtained in the form of a white powder (m.p. 104-105°C).
Figure imgf000031_0001
Example H-1c: 0.14 g of NaH in oil (~55%) in 5 ml of anhydrous tetrahydrofuran is initially introduced into a sulfonating flask at room temperature. Thereafter, a solution of 1.05 g of 6-[1-(5-chloro-6-ethylpyrimidin-4-ylamino)ethyl]-2H-1,4-benzoxazine-3-thione in 25 ml of absolute tetrahydrofuran is added dropwise under an N2 atmosphere in the course of about 10 minutes. The mixture is stirred at 60-65°C for 15 minutes for complete salt formation, and 0.45 g of allyl bromide is then added. The mixture is kept under reflux for about 2 hours. After the solvent has been stripped off under a water pump vacuum, the residue is taken up in ether/water, the aqueous phase is extracted with ether and the organic phase is dried over sodium sulfate and purified by column chromatography over silica gel (mobile phase: n-hexane/diethyl ether 1:1). 1.05 g of 6-[1-(5-chloro-6- ethylpyrimidin-4-ylamino)ethyl]-3-allylthio- 2H-1,4-benzoxazine are obtained in the form of a yellow resin (1H-NMR).
Figure imgf000031_0002
The compounds listed in the following tables can also be prepared in a manner analogous to mat described in Examples H-1a to H-1c or by means of another of the corresponding procedures described above.
Figure imgf000032_0001
Figure imgf000033_0001
Figure imgf000034_0001
Figure imgf000035_0001
Figure imgf000036_0001
Figure imgf000037_0001
Figure imgf000038_0001
Figure imgf000039_0001
Figure imgf000040_0001
Figure imgf000041_0001
Figure imgf000042_0001
Figure imgf000043_0001
Figure imgf000044_0001
I
I
Figure imgf000045_0001
Figure imgf000046_0001
Figure imgf000047_0001
Figure imgf000048_0001
Figure imgf000049_0001
Figure imgf000050_0001
Figure imgf000051_0001
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
Figure imgf000091_0001
Figure imgf000092_0001
Figure imgf000093_0001
Figure imgf000094_0001
Figure imgf000095_0001
Figure imgf000096_0001
Figure imgf000097_0001
Figure imgf000098_0001
Figure imgf000099_0001
Figure imgf000100_0001
Figure imgf000101_0001
Figure imgf000102_0001
Figure imgf000103_0001
Figure imgf000104_0001
Figure imgf000105_0001
Figure imgf000106_0001
Figure imgf000107_0001
Figure imgf000108_0001
Figure imgf000109_0001
Figure imgf000110_0001
Figure imgf000111_0001
Figure imgf000112_0001
Figure imgf000113_0001
Figure imgf000114_0001
Figure imgf000115_0001
Table 9
Example 1H-NMR data (ppm/multiplicity/number of protons)
Solvent: CDCl3
______________________________________________________________________
1.13 1.26/t/3H; 1.59/d/3H; 2.52/t/2H; 2.78/m/4H; 3.98/s/2H;
5.32/m/1H; 5.58/d/1H; 7.10/s/1H; 7.26-7.30/m/2H;
8.39/s/1H
1.2 1.28/t/3H; 1.59/d/3H; 2.49/t/2H; 2.50/s/3H; 2.79/m/4H;
5.32/m/1H; 5.59/d/1H; 7.09/s/1H; 7.21/s/1H; 7.25/d/1H; 8.40/s/1H
1.41 1.28/t/3H; 1.59/d/3H; 2.46/t/2H; 2.75-2.90/m/4H;
3.90/s/3H; 5.32/m/1H; 5.58/d/1H; 7.09-7.21/m/3H;
8.40/s/1H
1.57 1.26/t/3H; 1.58/d/3H; 2.47/t/2H; 2.78/m/4H; 3.82/d/2H;
5.11/d/1H; 5.25-5.34/m/2H; 5.57/d/1H; 5.89-6.01/m/1H; 7.07/s/1H; 7.21-7.26/m/2H; 8.40/s/1H
1.6 0.94/t/3H; 1.26/t/3H; 1.34/t/3H; 1.93/m/2H; 2.47/do1/2H;
2.78/m/4H; 3.13/q/2H; 5.09/q/1H; 5.60/d/1H; 7.03/s/1H; 7.18-7.22/m/2H; 8.38/s/1H
1.89 1.25/t/3H; 1.59/d/3H; 2.52/t/2H; 2.75-2.84/m/4H;
3.99/q/2H; 5.31/m/1H; 5.57/d/1H; 7.09/s/1H;
7.23-7.26/m/2H; 8.39/s/1H
1.91 1.26/t/3H; 1.58/d/3H; 2.48/t/2H; 2.75-2.83/m/4H;
3.43/t/1H; 3.50/t/1H; 4.56/t/1H; 4.72/t/1H; 5.32/m/1H; 5.57/d/1H; 7.08/s/1H; 7.17-7.21/m/2H; 8.40/s/1H
1.93 1.03/t/3H; 1.25/t/3H; 1.58/d/3H; 1.72/m/2H; 2.43-2.49/t/2H; 2.73-2.83/m/4H; 3.12/t/2H; 5.32/m/1H;
5.56/d/1H; 7.06/s/1H; 7.20-7.26/m/2H; 8.40/s/1H
1.95 1.23/t/3H; 1.34/d/6H; 1.58/d/3H; 2.42/t/2H;
2.73-2.83/m/4H; 4.06/m/1H; 5.32/m/1H; 5.57/d/1H; 7.07/s/1H; 7.187.24/m/2H; 8.40/s/1H
1.97 1.26/t/3H; 1.57/d/3H; 2.44-2.61/m/4H; 2.74-2.83/m/4H;
3.27/t/2H; 5.32/m/1H; 5.57/d/1H; 7.08/s/1H;
7.19-7.22/m/2H; 8.39/s/1H
2.16 1.23/t/3H; 1.58/d/3H; 2.51/t/2H; 2.75-2.82/m/4H;
3.76/s/3H; 3.98/s/2H; 5.33/m/1H; 5.59/d/1H;
7.04-7.11/m/2H; 7.19/s/1H; 8.39/s/1H
2.19 1.25/t/3H; 1.46/s/9H; 1.58/d/3H; 2.50/t/2H;
2.74-2.80/m/4H; 3.86/s/2H; 5.33/m/1H; 5.60/d/1H; 7.06-7.08/m/2H; 7.21/s/1H; 8.39/s/1H
2.194 1.25/t/3H; 1.59/d/3H; 2.60/t/2H; 2.73-2.87/m/4H;
3.86/s/2H; 5.37/m/1H; 5.62/d/1H; 7.00-7.54/m/8H; 8.40/s/1H; 10.10/s/1H
2.57 1.25/t/3H; 1.60/d/3H; 2.47/dd/2H, 2.73-2.82/m/4H;
3.84/dd/2H; 5.13/d/1H; 5.27-5.36/m/2H; 5.60/d/1H; 5.90-6.04/m/1H; 7.04-7.11/m/2H; 7.25/d/1H; 8.40/s/1H
2.61 1.25/t/3H; 1.60/d/3H; 2.09/m/1H; 2.48/dd/2H;
2.75-2.83/m/4H; 3.99/d/2H; 5.34/m/1H; 5.60/d/1H; 7.04-7.12/m/2H; 7.26/d/1H; 8.40/s/1H
2.69 1.25/t/3H; 1.60/d/3H; 1.72-2.08/m/6H; 2.44/t/2H;
2.72-2.83/m/4H; 4.71/m/1H; 5.34/m/1H; 5.59/d/1H; 5.81-5.90/m/2H; 7.06/m/2H; 7.24/s/1H; 8.40/s/1H
2.89 1.25/t/3H; 1.60/d/3H; 2.51/t/2H; 2.74-2.82/m/4H; 3.95-4.07/m/2H; 5.34/m/1H; 5.59/d/1H; 7.06-7.14/m/2H;
8.40/s/1H
2.91 1.25/t/3H; 1.60/d/3H; 2.48/t/2H; 2.74-2.83/m/4H;
3.43-3.54/m/2H; 4.58/t/1H; 4.74/t/1H; 5.39/m/1H;
5.60/d/1H; 7.04-7.11/m/2H; 7.23/s/1H; 8.40/s/1H
2.93 1.04/t/3H; 1.25/t/3H; 1.59/d/3H; 1.67-1.80/m/2H;
2.46/m/2H; 2.72-2.82/m/4H; 3.11-3.17/m/2H; 5.34/m/1H; 5.60/d/1H; 7.03-7.09/m/2H; 7.24/s/1H; 8.40/s/1H
2.95 1.25/t/3H; 1.39/d/6H; 1.59/d/3H; 2.43/m/2H;
2.71-2.82/m/4H; 4.07/m/1H; 5.34/m/1H; 5.60/d/1H; 7.03-7.09/m/2H; 7.23/s/1H; 8.40/s/1H
2.97 1.22/t/3H; 1.59/d/3H; 2.46/m/2H; 2.54-2.63/m/2H;
2.74-2.82/m/4H; 3.28/m/2H; 5.34/m/1H; 5.61/d/1H; 7.04-7.12/m/2H; 7.23/s/1H; 8.40/s/1H
2.99 0.95/t/3H; 1.25/t/3H; 1.42- 1.51/m/2H; 1.59/d/3H;
1.59-1.71/m/2H; 2.46/m/2H; 2.72-2.82/m/4H; 3.16/t/2H; 5.34/m/1H; 5.60/d/1H; 7.04-7.08/m/2H; 7.24/s/1H;
8.40/s/1H
3.5 1.26/t/3H; 1.39/t/3H; 1.59/d/3H; 2.78/q/2H; 3.20/q/2H;
4.45/s/2H; 5.31/m/1H; 5.57/m/1H; 6.84/d/1H;
7.07/dd/1H; 7.26/s/1H; 8.41/s/1H
3.6 0.95/t/3H; 1.26/t/3H; 1.39/t/3H; 1.93/m/2H; 2.79/q/2H;
3.20/m/2H; 4.45/s/1H; 5.07/q/1H; 5.59/d/2H; 6.82/d/1H; 7.04/dd/1H; 7.23/d/1H; 8.38/s/1H
3.8 1.26/t/3H; 1.59/d/3H; 2.79/q/2H; 4.51/s/2H; 5.31/m/1H;
5.55/d/1H; 6.85/d/1H; 7.14/dd/1H; 7.28/d/1H; 7.80/t/1H; 8.40/s/1H 3.9 0.95/t/3H; 1.25/t/3H; 1.93/m/2H; 2.78/q/2H; 4.51/s/2H;
5.06/q/1H; 5.58/d/1H; 6.84/d/1H; 7.11/dd/1H; 7.24/d/1H; 7.80/t/1H; 8.38/s/1H
3.11 1.26/t/3H; 1.60/d/3H; 2.79/q/2H; 3.78/s/2H; 4.55/s/2H;
5.32/m/1H; 5.57/d/1H; 6.87/d/1H; 7.13/dd/1H;
7.33/d/1H; 8.40/s/1H
3.13 1.25/t/3H; 1.58/d/3H; 2.78/q/2H; 3.77/s/3H; 4.02/s/2H;
4.53/s/2H; 5.30/m/1H; 5.55/d/1H; 6.84/d/1H; 7.08/dd/1H; 7.22/d/1H; 8.40/s/1H
3.25 0.60/m/2H; 0.86/m/2H; 1.25/t/3H; 1.57/d/3H; 2.77/q/2H;
4.69/s/2H; 5.29/m/1H; 5.57/d/1H; 6.81/d/1H; 6.91/dd/1H; 7.15/s/1H; 8.39/s/1H
3.27 1.26/t/3H; 1.59/d/3H; 2.79/q/2H; 3.63/m/2H; 3.85/t/2H;
4.47/s/2H; 5.0/s/1H; 5.29/m/1H; 5.59/d/1H; 6.82/d/1H; 6.95/dd/1H; 7.12/d/1H; 8.41/s/1H
3.32 1.23/t/3H; 1.57/d/3H; 1.60- 1.75/m/6H; 2.77/q/2H;
3.50/m/4H; 4.63/s/1H; 5.28/m/1H; 5.57/d/1H; 6.79/d/1H; 6.87/dd/1H; 7.08/d/1H; 8.40/s/1H
3.34 1.25/t/3H; 1.57/d/3H; 2.77/q/2H; 3.54/m/4H; 3.76/t/4H;
4.63/s22H; 5.28/m/1H; 5.56/d/1H; 6.81/d/1H; 6.91/dd/1H; 8.40/s/1H
3.36 1.20-1.28/m/9H; 1.57/d/3H; 2.64/m/2H; 2.77/q/2H;
3.64/m/2H; 3.96/m/2H; 4.63/s/2H; 5.28/m/1H; 5.56/d/1H; 6.80/d/1H; 6.91/dd/1H; 7.09/d/1H; 8.39/s/1H
3.39 1.18-1.28/m/9H; 1.57/d/3H; 2.79/q/2H; 3.17/m/2H;
3.72/m/2H; 4.08/m/2H; 4.60/s/1H; 5.28/m/1H; 5.56/d/1H; 6.80/d/1H; 6.90/dd/1H; 7.09/d/1H; 8.40/s/1H 3.63 1.26/t/3H; 1.59/d/3H; 2.78/q/2H; 3.86/d/2H; 5.16/d/1H;
5.29-5.36/m/2H; 5.56/d/1H; 5.89-6.02/m/1H; 6.84/d/1H; 7.07/dd/1H; 7.27/d/1H; 8.40/s/1H
3.84 0.95/t/3H; 1.25/t/3H; 1.89-2.0/m/2H; 2.78/q/2H;
3.87/d/2H; 5.12/m/1H; 5.22/d/1H; 5.38/dd/1H;
5.90-6.03/m/1H; 7.09/d/1H; 7.23/dd/1H; 7.46/d/1H; 8.37/s/1H
4.2 1.23/t/3H; 1.60/d/3H; 2.59/s/3H; 2.79/q/2H; 3.23/s/2H;
5.33/m/1H; 5.60/d/1H; 7.07/d/1H; 7.20-7.31/m/2H; 8.39/s/1H
4.5 1.26/t/3H; 1.38/t/3H; 1.60/d/3H; 2.77/q/2H; 3.18/q/2H;
3.20/s/2H; 5.33/m/1H; 5.58/d/1H; 7.06/dd/1H;
7.20-7.28/m/2H; 8.40/s/1H
4.57 1.26/t/3H; 1.60/d/3H; 2.78/q/2H; 3.22/s/2H; 3.87/d/2H;
5.16/d/1H; 5.29-5.35/m/2H; 5.90/d/1H; 7.07/dd/1H; 7.21/d/1H; 7.28/d/1H; 8.40/s/1H
4.61 1.26/t/3H, 1.60/d/3H; 2.23/m/1H; 2.78/q/2H; 3.24/s/2H;
4.0/d/1H; 5.32/m/1H; 5.58/d/1H; 7.08/dd/1H; 7.21/d/1H; 7.31/d/1H; 8.39/s/1H
5.11 1.26/t/3H; 1.60/d/3H; 2.25-2.40/m/4H; 2.55/t/2H;
2.79/q/2H; 3.90/s/2H; 5.34/m/1H; 5.57/d/1H; 7.04/d/1H; 7.14/d/1H; 7.26/dd/1H; 8.41/s/1H
5.13 1.26/t/3H; 1.59/d/3H; 2.25-2.40/m/4H; 2.50/t/2H;
2.79/q/2H; 3.75/s/3H; 3.90/s/2H; 5.33/m/1H; 5.57/d/1H; 6.93/d/1H; 7.11/d/1H; 7.22/dd/1H; 8.41/s/1H
5.15 1.26/t/3H; 1.46/s/9H; 2.25-2.40/m/4H; 2.52/t/2H; 2.79/q/2H; 3.80/s/2H; 5.34/m/1H; 5.57/d/1H; 6.94/d/1H;
7.09/d/1H; 7.21/dd/1H; 8.42/s/1H
5.2 1.28/t/3H; 1.60/d/3H; 2.20-2.40/m/4H; 2.49/s/3H;
2.53/t/2H; 2.80/q/2H; 5.35/m/1H; 5.57/d/1H; 7.0/d/1H; 7.11/d/1H; 7.25/dd/1H; 8.42/s/1H
5.21 1.23-1.29/2xt/6H (DS1 + DS2); 1.59/d/6H (DS 1 + DS2);
2.25-2.40/m/4H (DS1 + DS2); 2.54/m/4H (DS1 + DS2); 2.79/q/4HZ(DSl + DS2); 4.30-4.60/m/4H (DS1 +DS2); 5.33/m/2H/ (DS1 + DS2); 5.59/D/2H (DS 1 + DS2);
6.97/d/2H (DS1 + DS2); 7.12/d/2H (DS1 + DS2);
7.24/dd/2H (DS1 + DS2); 8.40/s/1H (DS1 + DS2);
8.42/s/1H (DSl or DS2)
5.26 0.93/t/3H; 1.03/t/3H; 1.27/t/3H; 1.69/m/2H; 1.92/m/2H;
2.79/q/2H; 2.89/t/2H; 5.10/q/1H; 5.59/d/1H; 6.97/d/1H; 7.05/d/1H; 7.15/dd/1H; 8.39/s/1H
5.29 0.63/m/2H; 0.85/m/2H; 1.29/t/3H; 1.93/m/2H;
2.22/m/4H; 2.60/t/2H; 2.78/q/2H; 5.11/q/1H; 5.60/d/1H; 6.99/d/1H; 7.08/d/1H; 7.17/dd/1H; 8.39/s/1H
5.3 0.95/t/3H; 1.26/t/3H; 1.93/m/2H; 2.20-2.39/m/4H;
2.48/s/3H; 2.52/t/2H; 2.79/q/2H; 5.11/q/1H; 5.60/d/1H; 6.99/d/1H; 7.09/d/1H; 7.20/dd/1H; 8.40/s/1H
5.34 1.26/t/3H; 1.58/d/3H; 2.15/t/2H; 2.30/t/2H; 2.78/q/2H;
3.41-3.65/m/4H; 5.31/m/1H; 5.56/d/1H; 6.94/d/1H;
7.06/d/1H; 7.17/dd/1H; 8.42/s/1H
5.38 1.26/t/3H; 1.58/d/3H; 2.11/t/2H; 2.31/t/2H; 2.51/t/2H;
2.78/q/2H; 3.57/m/2H; 3.76/m/2H; 5.32/m/1H;
5.56/d/1H; 6.89/d/1H; 7.07/dd/1H; 7.19/dd/1H; 8.42/s/1H
5.40 1.25/m/9H; 1.59/d/3H; 2.11/t/2H; 2.30/m/2H; 2.52/m/2H; 2.77/q/2H; 3.63-3.70/m/2H; 4.11/m/2H; 5.31/m/1H;
5.56/d/1H; 6.90/d/1H; 7.07/dd/1H; 7.18/dd/1H; 8.42/s/1H
5.47 0.94/t/3H; 1.29/t/3H; 1.95/m/2H; 2.25/m/4H; 2.55/t/2H;
2.79/q/2H; 3.86/s/3H; 5.10/q/1H; 5.60/d/1H; 6.98/d/1H; 7.09/d/1H; 7.18/dd/1H; 8.40/s/1H
5.5 1.29/t/3H; 1.39/t/3H; 1.60/d/3H; 2.20-2.40/m/4H;
2.55/t/2H; 2.80/q/2H; 3.09/q/2H; 5.35/m/1H; 5.58/d/1H; 6.99/d/1H; 7.11/d/1H; 7.24/dd/1H; 8.42/s/1H
5.6 0.95/t/3H; 1.29/t/3H; 1.39/t/3H; 1.95/m/2H;
2.20-2.38/m/4H; 2.55/t/2H; 2.80/q/2H; 3.10/q/2H;
5.10/q/1H; 5.60/d/1H; 6.99/d/1H; 7.08/d/1H; 7.21/dd/1H; 8.40/s/1H
5.66 1.26/t/3H; 1.59/d/3H; 2.26-2.32/m/4H; 2.52/t/2H;
2.78/q/2H; 3.75/d/2H; 5.12/d/1H; 5.25-5.36/m/2H;
5.56/d/1H; 5.98/m/1H; 6.97/d/1H; 7.11/d/1H;
7.23/dd/1H; 8.42/s/1H
5.70 1.26/t/3H; 1.59/t/3H; 2.19/s/1H; 2.31/m/4H; 2.53/t/2H;
2.78/q/2H; 3.88/d/2H; 5.33/m/1H; 5.56/d/1H; 6.99/d/1H; 7.11/d/1H; 7.23/dd/1H; 8.41/s/1H
5.78 1.26/t/3H; 1.59/d/3H; 1.73-2.07/m/6H; 2.27/m/2H;
2.51/t/2H; 2.78/q/2H; 4.55/m/1H; 5.33/m/1H; 5.56/d/1H; 5.83/m/2H; 6.97/d/1H; 7.10/d/1H; 7.23/dd/1H; 8.41/s/1H
5.84 1.26/t/3H; 1.35-1.85/m/9H; 1.90-2.20/m/4H; 2.27/m/4H;
2.52/t/2H; 2.78/q/2H; 3.82/s/1H; 5.32/s/1H; 5.56/d/1H; 6.97/d/1H; 7.10/d/1H; 7.23/dd/1H; 8.42/s/1H
5.98 1.26/t/3H; 1.59/d/3H; 2.32/m/4H; 2.51/t/2H; 2.78/q/2H;
3.92/q/2H; 5.33/m/1H; 5.57/d/1H; 6.98/d/1H; 7.19/d/1H; 7.24/dd/1H; 8.41/s/1H
5.100 1.26/t/3H; 1.59/d/3H; 2.30/m/4H; 2.52/t/2H; 2.79/q/2H;
3.37/t/1H; 3.44/t/1H; 4.58/t/1H; 4.73/t/1H; 5.31/m/1H; 5.56/d/1H; 6.96/d/1H; 7.12/d/1H; 7.24/dd/1H; 8.41/s/1H
5.102 1.03/t/3H; 1.23/t/3H; 1.59/d/3H; 1.73/q/2H; 2.29/m/4H;
2.52/t/3H; 2.77/q/2H; 3.06/t/2H; 5.33/m/1H; 5.56/d/1H; 6.96/d/1H; 7.10/d/1H; 7.23/dd/1H; 8.41/s/1H
5.104 1.26/t/3H; 1.39/d/6H; 1.59/d/3H; 2.27/m/4H; 2.53/t/2H;
2.79/q/2H; 3.93/m/1H; 5.33/m/1H; 5.56/d/1H; 6.97/d/1H; 7.10/d/1H; 7.23/dd/1H; 8.41/s/1H
5.106 1.26/t/3H; 1.59/d/3H; 2.25-2.35/m/4H; 2.50-2.67/m/4H;
2.79/q/2H; 3.22/m/2H; 5.33/m/1H; 5.57/d/1H; 6.98/d/1H; 7.12/d/1H; 7.23/dd/1H; 8.41/s/1H
5.108 0.94/t/3H; 1.26/t/3H; 1.45/m/2H; 1.59/d/3H; 1.67/m/2H;
2.29/m/4H; 2.52/t/2H; 2.79/q/2H; 3.08/t/2H; 5.33/m/1H; 5.57/d/1H; 6.97/d/1H; 7.10/d/1H; 7.23/dd/1H; 8.41/s/1H
5.110 1.02/t/3H; 1.26/t/3H; 1.38/d/3H; 1.59/d/3H; 1.70/m/2H;
2.28/m/4H; 2.53/t/2H; 2.79/q/2H; 3.83/m/1H; 5.33/m/1H; 5.57/d/1H; 6.96/d/1H; 7.10/d/1H; 7.23/dd/1H; 8.41/s/1H
5.112 1.03/d/6H; 1.26/t/3H; 1.59/d/3H; 1.97/m/1H; 2.28/m/4H;
2.51/t/2H; 2.78/q/2H; 3.01/d/2H; 5.32/m/1H; 5.56/d/1H; 6.96/d/1H; 7.10/d/1H; 7.23/dd/1H; 8.41/s/1H
5.114 0.91/t/3H; 1.26/t/3H; 1.38/m/4H; 1.59/d/3H; 1.68/m/2H;
2.29/m/4H; 2.52/t/2H; 2.79/q/2H; 3.07/t/2H; 5.33/m/1H; 5.56/d/1H; 6.96/d/1H; 7.10/d/1H; 7.23/dd/1H; 8.41/s/1H
5.115 0.93/t/3H; 1.26/t/3H; 1.47/d/3H; 1.51/m/2H; 1.58/d/3H;
1.68/m/2H; 2.28/m/4H; 2.79/q/2H; 3.89/m/1H; 5.33/m/1H; 5.56/d/1H; 6.96/d/1H; 7.10/d/1H;
7.23/dd/1H; 8.41/s/1H
5.120 0.93/d/6H; 1.26/t/3H; 1.59/d/3H; 1.58-1.70/m/3H;
2.29/m/1H; 2.52/t/2H; 2.79/q/2H; 3.08/t/2H; 5.33/m/1H; 5.56/d/1H; 6.97/d/1H; 7.10/d/1H; 7.23/dd/1H; 8.41/s/1H
5.122 1.04/s/9H; 1.26/t/3H; 1.59/d/3H; 2.28/m/4H; 2.51/t/2H;
2.79/q/2H; 3.10/s/2H; 5.32/m/1H; 5.56/d/1H; 6.96/d/1H; 7.10/d/1H; 7.23/dd/1H; 8.41/s/1H
5.124 0.00/s/9H; 1.11/t/3H; 1.43/d/3H; 2.11/q/2H; 2.19/m/2H;
2.36/t/2H; 2.63/q/2H; 5.18/m/1H; 5.42/d/1H; 6.83/d/1H; 6.95/d/1H; 7.08/dd/1H; 8.26/s/1H
5.126 1.26/t/3H; 1.59/d/3H; 1.69-1.88/m/4H; 2.29/m/4H;
2.52/t/2H; 2.79/9/2H; 3.08/t/2H; 3.55/t/2H; 5.33/m/1H; 5.56/d/1H; 6.96/d/1H; 7.10/d/1H; 7.23/dd/1H; 8.41/s/1H
5.128 0.88/t/3H; 1.26/t/3H; 1.28-1.45/m/6H; 1.59/d/3H;
1.67/m/2H; 2.29/m/4H; 2.79/q/2H; 3.07/t/2H; 5.33/m/1H; 5.56/d/1H; 6.96/d/1H; 7.10/d/1H; 7.23/dd/1H; 8.41/s/1H
5.134 0.93/d/6H; 1.26/t/3H; 1.40/d/3H; 1.43/m/1H; 1.59/d/3H;
1.79/m/2H; 2.27/m/4H; 2.52/t/2H; 2.78/q/2H; 3.93/m/1H; 5.33/m/1H; 5.57/d/1H; 6.96/d/1H; 7.10/d/1H;
7.23/dd/1H; 8.41/s/1H
5.137 0.87/t/3H; 1.20-1.45/m/15H; 1.58/d/3H; 1.60-1.85/m/3H;
2.29/m/4H; 2.79/q/2H; 3.07/t/2H; 5.33/m/1H; 7.10/d/1H; 7.23/dd/1H; 8.41/s/1H
5.139 1.26/t/3H; 1.59/d/3H; 1.86/s/3H; 2.24-2.34/m/4H;
2.52/t/2H; 2.79/q/2H; 3.80/s/2H; 4.86/d/1H; 5.02/d/1H; 5.33/m/1H; 5.57/d/1H; 6.97/d/1H; 7.11/d/1H; 7.23/dd/1H; 8.41/s/1H
5.140 1.26/t/6H (E- and Z-isomer); 1.59/d/6H; (E- and
Z-isomer); 1.68/d/3H (E- or Z-isomer); 1.71/d/3H (E- or Z-isomer); 2.29/m/8H (E- and Z-isomer); 2.52/t/4H (E- and Z-isomer); 2.78/q/4H (E- and Z-isomer);
3.70/d/2H (E- or Z-isomer); 3.78/d/2H (E- or Z-isomer); 5.33/m/2H (E- and Z-isomer); 5.56/d/2H E- and
Z-isomer); 5.55-5.79/m/4H (E- and Z-isomer); 6.97/d/2H (E- and Z-isomer); 7.11/d/2H (E- and Z-isomer);
7.23/dd/2H (E- and Z-isomer); 8.41/s/2H (E- and Z-isomer)
5.142 1.26/t/3H; 1.59/d/3H; 2.29/m/4H; 2.40-2.58/m/4H;
2.78/q/2H; 3.15/t/2H; 5.04-5.14/m/2H; 5.33/m/1H;
5.56/d/1H; 5.80-5.91/m/1H; 6.97/d/1H; 7.11/d/1H;
7.23/dd/1H; 8.41/s/1H
5.146 0.99/t/3H; 1.26/t/3H; 1.59/d/3H; 2.10-2.35/m/6H;
2.53/t/2H; 2.78/q/2H; 3.76/d/2H; 5.33/m/1H; 5.54/m/3H; 6.98/d/1H; 7.11/d/1H; 7.23/dd/1H; 8.41/s/1H
5.148 1.26/t/3H; 1.59/d/3H; 1.73/d/6H; 2.29/m/4H; 2.53/t/2H;
2.78/q/2H; 3.73/d/2H; 5.33/m/1H; 5.57/d/1H; 6.98/d/1H; 7.11/d/1H; 7.23/dd/1H; 8.41/s/1H
5.151 1.25/t/3H; 1.59/d/3H; 1.81/m/2H; 2.16-2.35/m/6H;
2.52/t/2H; 2.78/q/2H; 3.08/t/2H; 4.97-5.08/m/2H;
5.33/m/1H; 5.56/d/1H; 5.75-5.87/m/1H; 6,97/d/1H; 7.10/d/1H; 7.23/dd/1H; 8.41/s/1H
5.162 1.26/t/3H; 1.59/d/3H; 1.65/s/3H; 1.71/s/3H;
2.20-2.46/m/6H; 2.52/t/3H; 2.79/q/2H; 5.19/m/1H;
5.33/m/1H; 5.56/d/1H; 6.97/d/1H; 7.11/d/1H;
7.23/dd/1H; 8.41/s/1H 5.164 1.26/t/3H; 1.59/d/3H; 1.46-1.79/m/4H; 2.08/m/2H;
2.29/m/4H; 2.52/t/2H; 2.78/q/2H; 3.08/t/2H;
4.93-5.05/m/2H; 5.33/m/1H; 5.56/d/1H; 5.73-5.86/m/1H; 6.96/d/1H; 7.11/d/1H; 7.23/dd/1H; 8.41/s/1H
5.171 1.26/t/3H; 1.59/d/3H; 1.68/s/3H; 1.72/s/3H; 2.05/m/4H;
2.29/m/4H; 2.53/t/2H; 2.78/q/2H; 3.74/d/2H; 5.08/m/1H; 5.33/m/2H; 5.56/d/1H; 6.98/d/1H; 7.11/d/1H;
7.23/dd/1H; 8.41/s/1H
5.173 1.26/t/3H; 1.59/d/3H; 1.83/t/3H; 2.28/m/4H; 2.53/t/2H;
2.78/q/2H; 3.85/m/2H; 5.33/m/1H; 5.56/d/1H; 6.98/d/1H; 7.11/d/1H; 7.23/dd/1H; 8.41/s/1H
5.175 1.26/t/3H; 1.59/d/3H; 2.03/t/1H; 2.30/m/4H; 2.52/t/2H;
2.65/m/2H; 2.78/q/2H; 3.23/t/2H; 5.33/m/1H; 5.56/d/1H; 6.969d/1H; 7.11/d/1H; 7.23/dd/1H; 8.41/s/1H
5.177 1.21/s/9H; 1.26/t/3H; 1.59/d/3H; 2.30/m/4H; 2.52/t/2H;
2.78/q/2H; 3.85/s/2H; 5.33/m/1H; 5.56/d/1H; 6.97/d/1H; 7.11/d/1H; 7.23/dd/1H; 8.41/s/1H
5.179 0.00/s/9H; 1.09/t/3H; 1.42/d/3H; 2.12/m/2H; 2.36/t/2H;
2.61/q/2H; 3.75/s/2H; 5.17/m/1H; 5.40/d/1H; 6.81/d/1H; 6.94/d/1H; 7.07/dd/1H; 8.25/s/1H
5.182 1.26/t/3H; 1.59/d/3H; 2.29/m/4H; 2.54/t/2H; 2.79/q/2H;
2.88/d/1H; 3.77/d/2H; 5.33/m/1H; 5.56/d/1H; 5.71/d/1H; 6.28-6.37/m/1H; 6.97/d/1H; 7.11/d/1H; 7.23/dd/1H; 8.41/s/1H
5.186 1.23/s/9H; 1.26/t/3H, 1.58/d/3H; 2.29/m/4H; 2.52/t/2H;
2.78/q/2H; 3.76/d/2H; 5.33/m/1H; 5.59/d/1H; 5.71/d/1H; 6.05-6.19/m/1H; 6.98/d/1H; 7.11/d/1H; 7.23/dd/1H; 8.41/s/1H 5.192 1.26/t/3H; 1.57-1.60/dd/6H; 2.28/m/4H; 2.52/t/2H;
2.78/q/2H; 3.75/s/3H; 4.54/q/1H; 5.32/m/1H; 5.56/d/1H; 6.93/d/1H; 7.11/d/1H; 7.23/dd/1H; 8.41/s/1H
5.194 1.23-1.28/m/6H; 1.57-1.62/m/6H; 2.29/m/4H; 2.50/t/2H;
2.78/q/2H; 4.07-4.24/m/2H; 4.53/q/1H; 5.32/m/1H;
5.56/d/1H; 6.93/d/1H; 7.10/d/1H; 7.23/dd/1H; 8.41/s/1H
5.196 1.06/t/3H; 1.23-1.33/m/6H; 1.56-1.60/m/3H; 1.96/m/2H;
2.30/m/4H; 2.51/t/2H; 2.78/q/2H; 4.18/q/2H; 4.49/t/1H; 5.32/m/1H; 5.56/d/1H; 6.93/d/1H; 7.10/d/1H;
7.22/dd/1H; 8.41/s/1H
5.198 0.82/t/3H; 1.21-1.29/m/9H; 1.46/m/2H; 1.60/d/3H;
2.35/m/4H; 2.52/t/2H; 2.79/q/2H; 3.22/q/2H; 3.69/s/2H; 5.35/m/1H; 5.57/d/1H; 6.95/d/1H; 7.14/d/1H;
7.26/dd/1H; 7.39/t/1H; 8.41/s/1H
5.212 1.26/t/3H; 1.62/d/3H; 2.30/m/4H; 2.51/t/2H; 2.99/s/3H;
3.14/s/3H; 4.05/s/2H; 5.33/m/1H; 5.57/d/1H; 6.93/d/1H; 7.12/d/1H; 7.23/dd/1H; 8.41/s/1H
5.214 1.13/t/3H; 1.26/m/6H; 1.60/d/3H; 2.32/m/4H; 2.51/t/2H;
2.79/q/2H; 3.36-3.50/m/4H; 4.04/s/2H; 5.33/m/1H;
5.55/d/1H; 6.92/d/1H; 7.11/d/1H; 7.23/dd/1H; 8.41/s/1H
5.217 1.26/t/3H; 1.60/d/3H; 1.80-1.99/m/4H; 2.29/m/4H;
2.51/t/2H; 2.78/q/2H; 3.50/t/2H; 3.62/t/2H; 3.95/s/2H; 5.33/m/1H; 5.56/d/1H; 6.89/d/1H; 7.11/d/1H;
7.23/dd/1H; 8.41/s/1H
5.219 1.26/t/3H; 1.52-1.70/m/9H; 2.32/m/4H; 2.51/t/2H;
2.78/q/2H; 3.57/m/4H; 4.08/s/2H; 5.33/m/1H; 5.56/d/1H; 6.94/d/1H; 7.12/d/1H; 7.23/dd/1H; 8.41/s/1H 5.221 1.26/t/3H; 1.59/d/3H; 2.32/m/4H; 2.50/t/2H; 2.78/q/2H;
3.66/m/8H; 4.04/s/2H; 5.34/m/1H; 5.56/d/1H; 6.91/d/1H; 7.12/d/1H; 7.22/dd/1H; 8.41/s/1H
5.223 1.13-1.29/m/9H; 1.59/d/3H; 2.32/m/4H; 2.51/t/2H;
2.74-2.88/m/3H; 3.52/m/2H; 3.90/d/1H; 4.08/s/2H;
4.44/d/1H; 5.33/m/1H; 5.56/d/1H; 6.93/d/1H; 7.11/d/1H; 7.23/dd/1H; 8.41/s/1H
5.229 1.08/t/3H; 1.26/t/3H; 1.58/d/3H; 2.32/m/4H; 2.50/t/2H;
2.66/q/2H; 2.78/q/2H; 3.89/s/2H; 5.33/m/1H; 5.56/d/1H; 6.89/d/1H; 7.11/d/1H; 7.23/dd/1H; 8.41/s/1H
5.231 1.23/s/9H; 1.26/t/3H; 1.58/d/3H; 2.32/m/4H; 2.50/t/2H;
2.79/q/2H; 4.14/s/2H
5.237 1.26/t/3H; 1.52-1.80/m/7H; 2.15-2.32/m/6H; 2.53/t/2H;
2.79/q/2H; 3.99/m/1H; 5.33/m/1H; 5.56/d/1H; 6.97/d/1H; 7.11/d/1H; 7.23/dd/1H; 8.41/s/1H
6.2 1.25/t/3H; 1.59/d/3H; 2.25/q/2H; 2.32/q/2H; 2.47/s/3H;
2.51/t/2H; 2.78/q/2H; 5.35/m/1H; 5.59/d/1H;
7.0-7.11/m/3H; 8.40/s/1H
6.5 1.25/t/3H; 1.37/t/3H; 1.59/d/3H; 2.24-2.33/m/4H;
2.51/t/2H; 2.78/q/2H; 3.08/q/2H; 5.35/m/1H; 5.58/d/1H; 6.99-7.11/m/3H; 8.40/s/1H
6.69 1.26/t/3H; 1.59/d/3H; 2.20/t/1H; 2.28/m/4H; 2.52/t/2H;
2.78/q/2H; 3.89/d/2H; 5.35/m/1H; 5.59/d/1H;
7.01-7.12/m/3H; 8.40/s/1H
6.98 1.25/t/3H; 1.59/d/3H; 2.30/m/4H; 2.50/t/2H; 2.78/q/2H;
3.93/q/2H; 5.36/m/1H; 5.59/d/1H; 7.01-7.13/m/3H;
8.40/s/1H 6.100 1.25/t/3H; 1.59/d/3H; 2.28/m/4H; 2.50/t/2H; 2.79/q/2H;
3.39/t/1H; 3.46/t/1H; 4.59/t/1H; 4.75/t/1H; 5.35/m/1H; 5.59/d/1H; 6.99-7.12/m/3H; 8.40/s/1H
6.102 1.04/t/3H; 1.25/t/3H; 1.60/d/3H; 1.73/m/2H; 2.29/m/4H;
2.51/t/2H; 2.78/q/2H; 3.08/t/2H; 5.35/m/1H; 5.59/d/1H; 6.99-7.10/m/3H; 8.40/s/1H
6.104 1.25/t/3H; 1.40/d/6H; 1.59/d/3H; 2.25/m/4H; 2.52/t/2H;
2.78/q/2H; 3.94/m/1H; 5.35/m/1H; 5.59/d/1H;
6.99-7.10/m/3H; 8.40/s/1H
6.108 0.95/t/3H; 1.40-1.54/m/2H; 1.59/d/3H; 1.62-1.78/m/2H;
2.26/m/4H; 2.51/t/2H; 2.78/q/2H; 3.09/t/2H; 5.35/m/1H; 5.59/d/1H; 6.99-7.10/m/3H; 8.40/s/1H
6.140 1.25/t/6H (E- and Z-isomer); 1.59/d/6H; (E- and
Z-isomer); 1.69-1.74/dd/6H (E- and Z-isomer);
2.26/m/8H (E- and Z-isomer); 2.51/m/4H (E- and
Z-isomer); 2.78/q/4H (E- and Z-isomer); 3.71/d/2H (E- or Z-isomer); 3.79/d/2H (E- or Z-isomer); 5.35/m/2H (E- and Z-isomer); 5.58-5.78/m/6H E- and Z-isomer);
7.00-7.11/m/6H (E- and Z-isomer); 8.40/s/2H (E- and Z-isomer)
7.3 1.26/t/3H; 1.40/t/3H; 1.58/d/3H; 2.60/t/3H; 2.78/q/2H;
3.53/t/2H; 5.35/m/1H; 5.59/d/1H; 7.00/dd/1H; 7.05/d/1H; 7.46/d/1H; 8.39/s/1H
7.4 1.26/t/3H; 1.59/d/3H; 2.67/t/2H; 2.78/q/2H; 3.55/t/2H;
3.93/q/2H; 5.34/m/1H; 5.57/d/1H; 7.04/m/2H; 7.47/d/1H; 8.39/s/1H
7.6 1.26/t/3H; 1.42/d/6H; 1.60/d/3H; 2.57/t/2H; 2.78/q/2H;
3.53/t/2H; 3.95/m/1H; 5.34/m/1H; 5.58/d/1H; 6.99/dd/1H; 7.04/d/1H; 7.45/d/1H; 8.39/s/1H
7.10 1.26/t/3H; 1.58/d/3H; 2.62/t/2H; 2.78/q/2H; 3.54/t/2H;
5.16/d/1H; 5.28-5.37/m/2H; 5.57/d/1H; 5.95-6.08/m/1H; 7.00/dd/1H; 7.05/d/1H; 7.46/d/1H; 8.39/s/1H
Formulation examples for active compounds of the formula I Examples F-1.1 to F-1.3: Emulsion concentrates _________________________________________________________________
Constituents F-1.1 F-1.2 F-1.3
__________________________________________________________________
Active compound from Table 1-8 25% 40% 50%
Calcium dodecylbenzenesulfonate 5% 8% 6%
Castor oil polyethylene glycol
ether (36 mol ethylenoxy units) 5% - -
Tributylphenol. polyethylene glycol
ether (30 mol ethylenoxy units) - 12% 4%
Cyclohexanone - 15% 20%
Xylene mixture 65% 25% 20%
_________________________________________________________________
Emulsions of any desired dilution can be prepared from these emulsion concentrates with water.
Example F-2: Emulsion concentrate __________________________________________________________________
Constituents F-2
_________________________________________________________________
Acrive compound from Table 1-8 10%
Octylphenol polyethylene glycolether
(4 to 5 mol ethylenoxy units) 3%
Calcium dodecylbenzenesulfonate 3%
Castor oil polyglycolether
(36 mol ethylenoxy units) 4%
Cyclohexanone 30%
Xylene mixture 50%
_________________________________________________________________
Emulsions of any desired dilution can be prepared from this emulsion concentrate with water.
Examples F-3.1 to F-3.4: Solutions _________________________________________________________________
Constituents F-3.1 F-3.2 F-3.3 F-3.4_________________________________________________________________
Active compound from Table 1-8 80% 10% 5% 95% Propylene glycol monomethyl ether 20% - - - Polyethylene glycol (relative molecular
weight: 400 atomic mass units) - 70% - - N-Methylpyrrolid-2-one - 20% - - Epoxidized coconut oil - - 1% 5% Benzine (boiling limit: 160-190°) - - 94% -_________________________________________________________________
The solutions are suitable for use in the form of tiny drops.
Examples F-4.1 to F-4.4: Granules _________________________________________________________________
Constituents F-4.1 F-4.2 F-4.3 F-4.4_________________________________________________________________
Active compound according to
the invention 5% 10% 8% 21%
Kaolin 94% - 79% 54%
Highly disperse silicic acid 1% - 13% 7%
Attapulgite - 90% - 18%_________________________________________________________________
The active compound according to the invention is dissolved in methylene chloride, the solution is sprayed onto the carrier and the solvent is then evaporated off in vacuo. Examples F-5.1 and F-5.2: Dusts _________________________________________________________________
Constituents F-5.1 F-5.2
_________________________________________________________________
Active compound from Table 1-8 2% 5%
Highly disperse silicic acid 1% 5%
Talc 97% -
Kaolin - 90%
_________________________________________________________________
Ready-to-use dusts are obtained by intimate mixing of all the constituents. Examples F-6.1 to F-6.3: Wettable powders _________________________________________________________________
Constituents F-6.1 F-6.2 F-6.3
_________________________________________________________________
Active compound from Table 1-8 25% 50% 75%
Sodium lignin-sulfonate 5% 5%
Sodium lauryl sulfate 3% - 5%
Sodium diisobutylnaphthalenesulfonate - 6% 10%
Octylphenol polyethylene glycol ether
(7 to 8 mol ethyleneoxy units) - 2% -
Highly disperse silicic acid 5% 10% 10%
Kaolin 62% 27% -_________________________________________________________________
All the constituents are mixed and the mixture is ground thoroughly in a suitable mill. Wettable powders which can be diluted with water to give suspensions of any desired concentration are obtained. Biological examples: A. Microbicidal actions
B-1: Action against Puccinia graminis on wheat
a) Residual protective action
6 days after sowing, wheat plants are sprayed to drip point with an aqueous spray liquor prepared from a wettable powder of the active compound (0.02% of active substance), and 24 hours later are infected with a uredosporc suspension of the fungus. After an incubation time of 48 hours (conditions: 95 to 100 per cent relative atmospheric humidity at 20°), the plants are placed in a greenhouse at 22°. Evaluation of the development of rust pustules 12 days after infection leads to the assessment of the action of the active substance. b) Systemic action
5 days after sowing, the wheat plants are watered with an aqueous spray liquor prepared from a wettable powder of the active compound (0.006% of active substance, based on the soil volume). Care is taken that the spray liquor does not come into contact with the parts of plants above the ground. 48 hours later, the plants are infected with a uredosporc suspension of the fungus. After an incubation time of 48 hours (conditions: 95 to 100 per cent relative atmospheric humidity at 20°), the plants are placed in a greenhouse at 22°. Evaluation of the development of rust pustules 12 days after infection gives the assessment of the action of the active substance.
Compounds from Tables 1-8 show a good action against Puccinia fungi. Thus, for example, compounds 1.2, 1.3, 1.6, 3.3, 3.5, 3.11, 3.42, 5.2, 5.3, 5.5, 5.13, 5.52, 5.104, 5.107, 5.108, 5.110, 5.142 and 5.237 reduce fungal attack to 0-20%. In contrast, untreated, infected control plants show a fungal attack of 100%.
Example B-2: Action against Phytophthora infestans on tomatoes
a) Residual protective action
After being grown for three weeks, tomato plants are sprayed to drip point with an aqueous spray liquor prepared from a wettable powder of the active compound (0.02% of active substance), and 24 hours later are infected with a sporangia suspension of the fungus. Evaluation of the fungal attack 5 days after infection, during which 90 to 100 per cent relative atmospheric humidity and a temperature of 20° are maintained, gives me assessment of the action of the active substance. Thus, for example, compounds 1.2, 1.3, 1.6, 3.3, 3.5, 3.11, 3.42, 5.2, 5.3, 5.5, 5.13, 5.52, 5.104, 5.107, 5.108, 5.110, 5.142 and 5.237 reduce fungal attack to 0-20%. In contrast, untreated, infected control plants show a fungal attack of 100%. b) Systemic action
After growing for three weeks, tomato plants are watered with an aqueous spray liquor prepared from a wettable powder of the active compound (0.006% of active substance, based on the soil volume). Care is taken that the spray liquor does not come into contact with the parts of plants above the ground. After 48 hours, the plants are infected with a sporangia suspension of the fungus. Evaluation of the fungal attack 5 days after infection, during which 90 to 100 per cent relative atmospheric humidity and a temperature of 20° are maintained, gives the assessment of the action of active substance. Compounds from Tables 1-8 show a good action; in particular, compounds 1.2, 1.3, 1.6, 3.3, 3.5, 3.11, 3.42, 5.2, 5.3 and 5.5 reduce fungal attack to 0-20%. In contrast, untreated, infected control plants show a fungal attack of 100%.
Example B-3: Residual protective action against Cercospora arachidicola on groundnuts Groundnut plants 10 to 15 cm high are sprayed to drip point with an aqueous spray liquor prepared from a wettable powder of the active compound (0.02% of active substance), and 48 hours later are infected with a conidia suspension of the fungus. The plants are incubated at 21° under a high atmospheric humidity for 72 hours and then placed in a greenhouse until the typical leaf spots occur. The action of the active substance is evaluated 12 days after infection on the basis of the number and size of the leaf spots.
Compounds from Tables 1-8 show a good action. Thus, for example, compounds 1.2, 1.3, 1.6, 3.3, 3.5, 3.11, 5.2, 5.3 and 5.5 reduce fungal attack to 0-20%. In contrast, untreated, infected control plants show a fungal attack of 100%.
Example B-4: Action against Plasmopara viticola on vines
Vine seedlings in the 4 to 5 leaf stage are sprayed to drip point with an aqueous spray liquor prepared from a wettable powder of the active compound (0.02% of active substance), and 24 hours later are infected with a sporangia suspension of the fungus. Evaluation of the fungal attack 6 days after infection, during which 95 to 10 per cent relative atmospheric humidity and a temperature of 20° are maintained, gives the assessment of the action of the active substance.
Active compounds from Tables 1-8 show a good action against Plasmopara viticola on vines. Thus, for example, compounds 1.2, 1.3, 1.6, 3.3, 3.5, 3.11, 3.42, 5.2, 5.3, 5.5, 5.13, 5.52, 5.104, 5.107, 5.108, 5.110, 5.142 and 5.237 reduce fungal attack to 0-20%. In contrast, untreated, infected control plants show a fungal attack of 100%.
Example B-5: Action against Colletotrichum lagenarium on cucumbers
After growing for 2 weeks, cucumber plants are sprayed with a spray liquor prepared from a wettable powder of the active compound (concentration 0.002%). After 2 days, the plants are infected with a spore suspension (1.5x105 spores/ml) of the fungus and incubated at 23°C under high atmospheric humidity for 36 hours. The incubation is then continued under normal atmospheric humidity at about 22°C. The fungal attack which has occurred is evaluated 8 days after the infection.
Compounds from Tables 1, 3, 5 and 6 reduce fungal attack to 0-20%. In contrast, untreated, infected control plants show a fungal attack of 100%.
Example B-6: Residual protective action against Venturia inaequalis on apples
Apple seedlings with fresh shoots 10 to 20 cm long are sprayed to drip point with an aqueous spray liquor prepared from a wettable powder of the active compound (0.02% of active substance), and 24 hours later are infected with a conidia suspension of the fungus. The plants are incubated at 90 to 100 per cent relative atmospheric humidity for 5 days and are placed in a greenhouse at 20 to 24° for a further 10 days. Evaluation of the scab attack 15 days after infection gives the assessment of the action of the active substance.
Active compounds from Tables 2, 5 and 6 show a good residual protective action against Venturia inaequalis on apples.
Example B-7: Action against Erysiphe graminis on barley
a) Residual protective action
Barley plants approximately 8 cm high are sprayed to drip point with an aqueous spray liquor prepared from a wettable powder of the active compound (0.02% of active substance), and 3 to 4 hours later are dusted with conidia of the fungus. The infected plants are placed in a greenhouse at 22°. Evaluation of the fungal attack 10 days after infection gives the assessment of the action of the active substance. b) Systemic action
Barley plants approximately 8 cm high are watered with an aqueous spray liquor prepared from a wettable powder of the active compound (0.002% of active substance, based on the soil volume). Care is taken that the spray liquor does not come into contact with the parts of plants above the ground. 48 hours later, the plants are dusted with conidia of the fungus. The infected plants are placed in a greenhouse at 22°. Evalution of the fungal attack 10 days after infection gives the assessment of the action of the active substance.
Compounds from Tables 1-8 show a good action. Thus, for example, compounds 1.2, 1.3, 1.6, 3.3, 3.5, 3.11, 3.42, 5.2, 5.3, 5.5, 5.13, 5.52, 5.104, 5.107, 5.108, 5.110, 5.142 and 5.237 reduce fungal attack to 0-20%. In contrast, untreated, infected control plants show a fungal attack of 100%.
Example B-8: Action against Podosphaera leucotricha on apple shoots
Apple seedlings with fresh shoots about 15 cm long are sprayed with a spray liquor (0.06% of active substance). After 24 hours, the treated plants are infected with a conidia suspension of the fungus and placed in a climatically controlled chamber at 70 % relative atmospheric humidity and 20°C. The fungal attack is evaluated 12 days after infection. Active compounds from Tables 1-8, for example compounds 3.42, 5.2, 5.3, 5.5 and 5.61, show a good action against apple mildew.
Biological examples: B. Acaricidal/insecticidal actions
B-9: Action against Tetranychus urticae
Young bean plants are populated with a mixed population of Tetranychus urticae, and one day later are sprayed with an aqueous emulsion spray liquor which comprises 400 ppm of the active compound. The plants are then incubated at 25°C for 6 days and subsequently evaluated. The percentage reduction in the population (% action) is determined by comparison of the number of dead eggs, larvae and adults on the treated plants with respect to those on the untreated plants.
The compounds of Tables 1, 3 and 5 show a good action against Tetranychus urticae in this test. In particular, compounds 1.2, 1.3, 1.6, 3.3, 3.5, 3.11, 3.42, 5.2, 5.3, 5.5, 5.13, 5.52, 5.104, 5.107, 5.108, 5.110, 5.142 and 5.237 show an action of above 90%.
B-10: Action against Nilaparvata lugens
Rice plants are treated with an aqueous emulsion spray liquor which comprises 400 ppm of the active compound. After the spray coating has dried on, the rice plants are populated with cicada larvae of the 2nd and 3rd stage. They are evaluated 21 days later. The percentage reduction in population (% action) is determined by comparing the number of surviving cicadas on the treated plants with respect to those on the untreated plants.
The compounds of Tables 1-8 show an action of above 90%.
B-11: Action on a mixed population of Tetranychus cinnabarinus.
Dilution series.
Dwarf beans in the 2-leaf stage are populated with a mixed population (eggs,
larvae/nymphs, adults) of an OP-tolerant Tetranychus cinnabarinus strain. 24 hours after the infection, the products are applied to the plants in dosages of 200, 100 and 50 mg of
AS/l in an automatic spray cabin. The substances are formulated and are diluted to the corresponding dosages with water. The test is evaluated 2 and 7 days after the application for percentage mortality of
- eggs
Compounds of Tables 1 to 8 show a mortality of more than 70% in dilutions of up to 50 mg AS/litre.
B-12: Action against Nilaparvata lugens
Rice plants are treated with an aqueous emulsion spray liquor which comprises 400 ppm of the active compound. After the spray coating has dried on, the rice plants are populated with cicada larvae of the 2nd and 3rd stage. They are evaluated 21 days later. The percentage reduction in population (% action) is determined by comparing the number of surviving cicadas on the treated plants with respect to those on the untreated plants.
The compounds of Table 3 show a good action in this test. In particular, compounds 3.3, 3.5 and 3.11 show an action of above 80%.
B-13: Action against Plutella xylostella caterpillars
Young cabbage plants are sprayed with an aqueous emulsion spray mixture which comprises 400 ppm of the active compound. After the spray coating has dried on, the cabbage plants are populated with 10 caterpillars of the 3rd stage of Plutella xylostella and placed in a plastic container. They are evaluated 3 days later. The percentage reduction in population or the percentage reduction in feeding damage (% action) is determined by comparison of the number of dead caterpillars and the eating damage on the trcated plants with respect to those on the untreated plants.
The compounds of Tables 3 and 5 show a good action in this test. In particular, compounds 3.3, 3.5 and 3.11 show an action of above 90%.
Example B-14: Action against Musca domestica
A sugar cube is treated with a solution of the test substance such that the concentration of the test substance, after drying overnight, in the sugar is 250 ppm. This treated cube is placed with a wet cotton-wool pad and 10 adult Musca domestica of an OP-resistant strain on an aluminium dish, covered with a glass beaker and incubated at 25°C. The mortality rate is determined after 24 hours.
In this test, the compounds of Tables 1-8 show a good action against Musca domestica. In particular, compounds 1.57, 1.61, 3.3, 3.5, 3.65, 4.57, 4.61, 5.66 and 6.65 show an action of more than 80%.

Claims

WHAT IS CLAIMED IS:
1. A compound of the formula I
Figure imgf000140_0001
in which the substituent A is in the β or γ-position, and in which:
R1 is hydrogen, C1-C4alkyl, C1-C4alkoxy, halo-C1-C4alkyl having 1, 2 or 3 halogen atoms or C1-C4alkylthio;
R2 and R3 independently of one another are hydrogen, C1-C4alkyl, halo-C1-C4alkyl having 1, 2 or 3 halogen atoms, C1-C2alkoxy- C1-C4alkyl, nitro-C1-C4alkyl, cyano-C1-C4alkyl, C1-C4alkanoyl-C1-C4alkyl, C1-C4alkoxycarbonyl-C1-C4alkyl, C1-C2alkylthio-C1-C4alkyl, C1-C2alkanesulfinyl-C1-C4alkyl, C1-C2alkanesulfonyl-C1-C4alkyl, C2-C4alkenyl, halo- C2-C4alkenyl having 1, 2 or 3 halogen atoms, C2-C4alkynyl, C3-C7cycloalkyl,
C1-C4alkoxy, halo-C1-C4alkoxy, C1-C4alkylthio, halo-C1-C4alkylthio, C1-C4alkylsulfιnyl, C1-C4alkylsulfonyl, amino, C1-C4acylamino, nitro, cyano, hydroxyl or halogen;
R4 is hydrogen, C1-C4alkyl, halo-C1-C4alkyl having 1, 2 or 3 halogen atoms,
C1-C2alkoxy-C1-C4alkyl, nitro-C1-C4alkyl, cyano-C1-C4alkyl, C3-C5cycloalkyl, benzyl, C1-C4alkanoyl or benzoyl, the phenyl group of which is unsubstituted or substituted by one, two or three substituents chosen from the group comprising halogen, C1-C2alkyl, nitro and cyano;
R5 and R6 independently of one another are hydrogen, C1-C4alkyl, halo-C1-C4alkyl having 1, 2 or 3 halogen atoms, C1-C2alkoxy-C1-C4alkyl, nitro-C1-C4alkyl, cyano-C1-C4alkyl, C1-C4alkoxycarbonyl-C1-C4alkyl or C3-C6cycloalkyl, which is unsubstituted or substituted by one or two substituents chosen from the group comprising halogen and C1-C2alkyl;
R7, R8 and R9 independently of one another are hydrogen, halogen, C1-C4alkyl, halo-C1-C4alkyl having one, two or three halogen atoms, C1-C2alkoxy-C1-C4alkyl, C3-C6cycloalkyl, C1-C4alkoxy, halo-C1-C4alkoxy having 1, 2 or 3 halogen atoms, C3-C7cycloalkoxy, C1-C4alkylthio, halo-C1-C4alkylthio having 1, 2 or 3 halogen atoms, cyano, nitro, phenyl, phenoxy and phenylthio, the phenyl groups in phenyl, phenoxy and phenylthio being unsubstituted or substituted by one, two or three substituents chosen from the group comprising halogen, C1-C2alkyl and C1-C2alkoxy, with the proviso that not more than one of the substituents R7, R8 or R9 is unsubstituted or substituted phenyl, substituted phenoxy or substituted phenyltiiio;
X is OR10, SR10 or N(R11)R12;
Y is a group -CH(R13)-, oxygen, sulfur or a group -N(R14)-;
R10 is hydrogen, an unsubstituted or substituted, open-chain, saturated or unsaturated hydrocarbon radical containing up to 12 carbon atoms, an unsubstituted or substituted cyclic saturated or unsaturated hydrocarbon radical containing up to 10 carbon atoms or unsubstituted or substituted benzyl; or an unsubstituted or substituted heterocyclyl radical;R11 is hydrogen, an open-chain saturated or unsaturated hydrocarbon radical which contains up to 8 carbon atoms and is unsubstituted or substituted by 1-5 halogen atoms, C1-C2alkoxy, hydroxyl, nitro, cyano, C1-C4alkanoyl, halo-C1-C4alkanoyl or
C1-C4alkoxycarbonyl, a cyclic saturated or unsaturated hydrocarbon radical containing up to 10 carbon atoms or benzyl, in which the carbocyclic radical is unsubstituted or mono- to disubstituted by halogen, C1-C2alkyl, halomethyl, nitro or cyano, or heterocyclyl, which is unsubstituted or mono- to trisubstituted by identical or different substituents from the group comprising C1-C2alkyl, halogen, halomethyl, nitro and cyano;
R12 is hydrogen or C1-C4alkyl; or
R11 and R12, together with the nitrogen atom to which they are bonded, are a heterocyclic radical which is unsubstituted or mono- to trisubstituted by identical or different substituents from the group comprising halogen, C1-C2alkyl, halomethyl and nitro;
R13 is hydrogen or C1-C4alkyl;
R14 is hydrogen, C1-C4alkyl, C1-C4alkanoyl, benzoyl, the phenyl group of which is unsubstituted or substituted by one, two or three substituents chosen from the group comprising halogen, C1-C2alkyl, nitro and cyano, C1-C4alkylsulfonyl, or aminosulfonyl, the nitrogen atom of which is unsubstituted or mono- or disubstituted by C1-C4alkyl; n is 1 or 2;
or, where appropriate, a tautomer thereof, in each case in the free form or in salt form.
2. A compound of the formula I according to claim 1, in which:
R10 is an open-chain saturated or unsaturated hydrocarbon radical which contains up to 8 carbon atoms and is unsubstituted or substituted by 1-5 halogen atoms, C1-C2alkoxy, hydroxyl, nitro, cyano, C1-C4alkanoyl, halo-C1-C4alkanoyl or C1-C4alkoxycarbonyl, a cyclic saturated or unsaturated hydrocarbon radical containing up to 10 carbon atoms or benzyl, in which the carbocyclic radical is unsubstituted or mono- to disubstituted by halogen, C1-C2alkyl, halomethyl, nitro or cyano, or heterocyclyl, which is unsubstituted or mono- to trisubstituted by identical or different substituents from the group comprising halogen, C1-C2alkyl, halomediyl, nitro and cyano, or a 5- to 7-membered lactone ring.
3. A compound of the formula I according to claim 1, in which:
R10 is hydrogen, an open-chain saturated or unsaturated hydrocarbon radical which contains up to 12 carbon atoms and is unsubstituted or substituted by tri-(C1-C4alkyl)-silyl or an epoxy group; or the group
-CH(U)(CH2)mCO-W,
in which:
U is hydrogen, C1-C4alkyl, cyano, or C1-C6alkoxycarbonyl;
W is C1-C6alkoxy, C3-C6cycloalkoxy, or the group -N(T1)T2;
m is 0, 1 or 2 and
T1 and T2 independently of one another are hydrogen, C1-C4alkyl, which is unsubstituted or substituted by 1-3 halogen atoms, C1-C2alkoxy, hydroxyl, nitro, cyano, C1-C4alkanoyl, halo-C1-C4alkanoyl or C1-C4alkoxycarbonyl, C1-C6alkenyl which is unsubstituted or substituted by 1-3 halogen atoms, C1-C6alkynyl which is unsubstituted or substituted by
1-3 halogen atoms, a cyclic saturated or unsaturated hydrocarbon radical containing up to
10 carbon atoms or benzyl, in which the carbocyclic radical is unsubstituted or mono- to disubstituted by halogen, C1-C2alkyl, halomethyl, nitro or cyano, or heterocyclyl, which is unsubstituted or mono- to trisubstituted by identical or different substituents from the group comprising C1-C2alkyl, halogen, halomethyl, nitro and cyano; or
T1 and T2, together with the nitrogen atom to which they are bonded, form a 5- to
7-membered heterocyclic radical, which can additionally also contain O, S and/or N as ring atoms, in which the additional nitrogen is unsubstituted or substituted by C1-C4alkyl, phenyl, C1-C4 alkanoyl, benzoyl or benzyl, and in which the carbon atoms of the heterocyclic radical are unsubstituted or mono- to trisubstituted by identical or different substituents from the group comprising halogen, C1-C2alkyl, halomethyl and nitro.
4. A compound of the formula I according to claim 3, in which:
R10 is hydrogen, an open-chain saturated or unsaturated hydrocarbon radical containing up to 6 carbon atoms, which is unsubstituted or substituted by tri-(C1-C4alkyl)-silyl or an epoxy group; or the group
-CH2-CO-W,
in which:
W is C1-C6alkoxy, C3-C6cycloalkoxy or the group -N(T1)T2;
T1 and T2 independently of one another are hydrogen, C1-C6alkyl, halo-C1-C6alkyl having
1-3 halogen atoms, C3-C6cycloalkyl, phenyl, halophenyl having 1-3 halogen atoms, pyridyl or naphtiiyl, or
T1 and T2, together with the nitrogen atom to which they are bonded, are piperidine, piperazine, morpholine or 2,6-dimethylmorpholine.
5. A compound of the formula I according to claim 1, in which:
R1 is hydrogen, C1-C4alkyl, C1-C4alkoxy, halo-C1-C4alkyl having 1, 2 or 3 halogen atoms or C1-C4alkylthio;
R2 and R3 independently of one another are hydrogen, C1-C4alkyl, halo-C1-C4alkyl having
1, 2 or 3 halogen atoms, C1-C2alkoxy-C1-C4alkyl, nitro-C1-C4alkyl, cyano-C1-C4alkyl, C1-C4alkanoyl-C1-C4alkyl, C1-C4a lkoxycarbonyl- C1-C4alkyl, C1-C2alkylthio- C1-C4a lkyl, C1-C2alkanesulfinyl-C1-C4alkyl, C1-C2alkanesulfonyl-C1-C4alkyl, C2-C4alkenyl, halo- C2-C4alkenyl having 1, 2 or 3 halogen atoms, C2-C4alkynyl, C3-C7cycloalkyl,
C1-C4alkoxy, halo-C1-C4alkoxy, C1-C4alkylthio, halo-C1-C4alkylthio, C1-C4alkylsulfinyl, C1-C4alkylsulfonyl, amino, C1-C4acylamino, nitro, cyano, hydroxyl or halogen;
R4 is hydrogen, C1-C4alkyl, halo-C1-C4alkyl having 1, 2 or 3 halogen atoms,
C1-C2alkoxy-C1-C4alkyl, nitro-C1-C4alkyl, cyano-C1-C4alkyl, C3-C5cycloalkyl, benzyl, C1-C4alkanoyl or benzoyl, the phenyl group of which is unsubstituted or substituted by one, two or three substituents chosen from the group comprising halogen, C1-C2alkyl, nitro and cyano;
R5 and R6 independently of one another are hydrogen, C1-C4alkyl, halo- C1-C4alkyl having
1, 2 or 3 halogen atoms, C1-C2alkoxy-C1-C4alkyl, nitro-C1-C4 alkyl, cyano-C1-C4alkyl, C1-C4alkoxycarbonyl-C1-C4alkyl or C3-C6cycloalkyl, which is unsubstituted or substituted by one or two substituents chosen from the group comprising halogen and C1-C2alkyl;
R7, R8 and R9 independently of one another are hydrogen, halogen, C1-C4alkyl, halo-C1-C4alkyl having 1, 2 or 3 halogen atoms, C1-C2alkoxy-C1-C4alkyl,
C3-C6cycloalkyl, C1-C4alkoxy, halo-C1-C4alkoxy with 1, 2 or 3 halogen atoms,
C3-C7cycloalkoxy, C1-C4alkylthio, halo-C1-C4 alkylthio having 1, 2 or 3 halogen atoms, cyano, nitro, phenyl, phenoxy and phenylthio, the phenyl groups in phenyl, phenoxy and phenylthio being unsubstituted or substituted by one, two or three substituents chosen from the group comprising halogen, C1-C2alkyl and C1-C2alkoxy, with the proviso that not more than one of the substituents R7, R8 or R9 is unsubstituted or substituted phenyl, substituted phenoxy or substituted phenyltiiio;
X is OR10, SR10 or N(R11)R12;
Y is a group -CH(R13)-, oxygen, sulfur or a group -N(R14)-;
R10 is C1-C8alkyl, halo- C1-C8-alkyl having 1 to 5 halogen atoms, C1-C2alkoxy- C1-C8alkyl, hydroxy-C1-C8alkyl, nitro-C1-C8alkyl, cyano-C1-C8alkyl, C1-C4alkanoyl- C1-C8alkyl, halo-C1-C4alkanoyl-C1-C8alkyl, C1-C4alkoxycarbonyl-C1-C8alkyl,
C3-C5cycloalkyl, benzyl, phenyl, which is unsubstituted or mono- to disubstituted by halogen, C1-C2alkyl, halomethyl, nitro or cyano, or heterocyclyl, which is unsubstituted or mono- to trisubstituted by identical or different substituents from the group comprising halogen, C1-C2alkyl, halomethyl, nitro and cyano, or a 5- to 7-membered lactone ring; R11 is hydrogen, C1-C4alkyl, halo-C1-C4-alkyl having 1, 2 or 3 halogen atoms,
C1-C2alkoxy-C1-C4alkyl, hydroxy-C1-C4alkyl, nitro-C1-C4alkyl, cyano-C1-C4alkyl, C1-C4alkanoyl-C1-C4alkyl, C1-C4alkoxycarbonyl-C1-C4alkyl, C3-C5cycloalkyl, benzyl, phenyl, which is unsubstituted or mono- to disubstituted by halogen, C1-C2alkyl, halomethyl, nitro or cyano, or heterocyclyl, which is unsubstituted or mono- to trisubstituted by identical or different substituents from the group comprising C1-C2alkyl, halogen, halomethyl, nitro and cyano;
R12 is hydrogen or C1-C4alkyl; or
R11 and R12 together with the nitrogen atom to which they are bonded are a heterocyclic radical, which is unsubstituted or mono- to trisubstituted by identical or different substituents from the group comprising halogen, C1-C2alkyl, halomethyl and nitro;
R13 is hydrogen or C1-C4alkyl;
R14 is hydrogen, C1-C4alkyl, C1-C4alkanoyl, benzoyl, the phenyl group of which is unsubstituted or substituted by one, two or three substituents chosen from the group comprising halogen, C1-C2alkyl, nitro and cyano, C1-C4alkylsulfonyl or aminosulfonyl, the nitrogen atom of which is unsubstituted or mono- or disubstituted by C1-C4alkyl; n is 1 or 2;
or, where appropriate, a tautomer thereof, in each case in the free form or in salt form.
6. A compound of the formula I according to claim 2, in which:
R1 is hydrogen or C1-C4alkyl;
R2 and R3 independently of one another are hydrogen, C1-C4alkyl, halo-C1-C4-alkyl having 1, 2 or 3 halogen atoms, C1-C2alkoxy-C1-C4alkyl, C2-C4alkynyl, C3-C5cycloalkyl, hydroxyl or halogen;
R4 is hydrogen, C1-C4alkyl, C3-C5cycloalkyl or benzyl;
R5 and R6 independently of one another are hydrogen, C1-C4alkyl, halo-C1-C4alkyl having
1, 2 or 3 halogen atoms, C1-C2alkoxy-C1-C4alkyl or C3-C6cycloalkyl;
R7, R8 and R9 independently of one another are hydrogen, halogen or C1-C4alkyl;
X is OR10, SR10 or N(R11)R12;
Y is a group -CH(R13)-, oxygen, sulfur or a group -N(R14)-;
R10 is C1-C4alkyl, halo-C1-C4-alkyl having 1, 2 or 3 halogen atoms, C1-C2alkoxy- C1-C4alkyl, hydroxy-C1-C4alkyl, nitro-C1-C4alkyl, cyano-C1-C4alkyl, C1-C4alkanoyl- C1-C4alkyl, C1-C4alkoxycarbonyl-C1-C4alkyl, C3-C5cycloalkyl, benzyl, phenyl, which is unsubstituted or mono- to disubstituted by halogen, C1-C2alkyl, halomethyl, nitro or cyano, heterocyclyl, which is unsubstituted or mono- to trisubstituted by identical or different substituents from the group comprising halogen, C1-C2alkyl, halomethyl, nitro and cyano, and a 5- to 7-membered lactone ring;
R11 is hydrogen, C1-C4alkyl, halo-C1-C4-alkyl having 1, 2 or 3 halogen atoms,
C1-C2alkoxy-C1-C4alkyl, hydroxy-C1-C4alkyl, nitro-C1-C4alkyl, cyano-C1-C4alkyl, C1-C4alkanoyl-C1-C4alkyl, C1-C4alkoxycarbonyl-C1-C4alkyl, C3-C5cycloalkyl, benzyl or phenyl, which is unsubstituted or mono- to disubstituted by halogen, C1-C2alkyl, nitro or cyano;
R12 is hydrogen or C1-C4alkyl; or
R11 and R12, together with the nitrogen atom to which they are bonded, are a heterocyclyl radical, which is unsubstituted or mono- to trisubstituted by identical or different substituents from the group comprising halogen, C1-C2alkyl, halomethyl and nitro;
R13 is hydrogen;
R14 is hydrogen, C1-C4alkyl, C1-C4alkanoyl, benzoyl, the phenyl group of which is unsubstituted or substituted by one, two or three substituents chosen from the group comprising halogen, C1-C2alkyl, nitro and cyano, C1-C4 alkylsulfonyl or aminosulfonyl, the nitrogen atom of which is unsubstituted or mono- or disubstituted by C1-C4alkyl; n is 1 or 2.
7. A compound of the formula I according to claim 1, in which:
R1 is hydrogen; or C1-C4alkyl;
R2 is hydrogen, C1-C4alkyl, halo-C1-C4-alkyl having 1, 2 or 3 halogen atoms,
C1-C2alkoxy-C1-C4alkyl, cyclopropyl, ethynyl or halogen;
R3 is fluorine or chlorine;
R4 is hydrogen or C1-C4 alkyl; R5 is C1-C4alkyl;
R6 is hydrogen;
R7, R8 and R9 independently of one another are hydrogen or halogen;
X is OR10, SR10 or N(R11)R12;
Y is a group -CH(R13)-, oxygen, sulfur or a group -N(R14)-;
R10 is C1-C4alkyl, halo-C1-C4-alkyl having 1, 2 or 3 halogen atoms, C1-C2alkoxy- C1-C4alkyl, hydroxy-C1-C4alkyl, nitro-C1-C4alkyl, cyano-C1-C4alkyl, C1-C4 alkanoyl - C1-C4alkyl, C1-C4alkoxycarbonyl-C1-C4alkyl, C2-C4alkenyl, which is unsubstituted or mono- to trisubstituted by halogen, C2-C4alkynyl, C3-C7cycloalkyl, C4-C8cycloalkenyl, benzyl or phenyl, which is unsubstituted or mono- to disubstituted by halogen, C1-C2alkyl, nitro or cyano, pyridine, pyrimidine or triazine, in which these heterocyclic radicals in each case are unsubstituted or mono- to trisubstituted by identical or different substituents from the group comprising halogen, C1-C2alkyl, trifluoromethyl and cyano, or a
5-membered lactone ring;
R11 is hydrogen, C1-C4alkyl, halo-C1-C4-alkyl having 1, 2 or 3 halogen atoms,
C1-C2alkoxy-C1-C4alkyl, hydroxy-C1-C4alkyl, nitro-C1-C4alkyl, cyano-C1-C4 alkyl, C1-C4alkanoyl-C1-C4alkyl, C1-C4alkoxycarbonyl-C1-C4alkyl, C2-C4alkenyl, which is unsubstituted or mono- to trisubstituted by halogen, C2-C4alkynyl, C3-C7cycloalkyl,
C4-C8cycloalkenyl, benzyl or phenyl, which is unsubstituted or mono- to disubstituted by halogen, C1-C2alkyl, nitro or cyano,
R12 is hydrogen or C1-C4alkyl; or
R11 and R12, together with the nitrogen atom to which they are bonded, are pyrrolidine, piperidine, piperazine, morpholine or 2,6-dimethylmorpholine;
R13 is hydrogen;
R14 is hydrogen, C1-C4alkyl, C1-C4alkanoyl or benzoyl, the phenyl group of which is unsubstituted or substituted by one, two or three substituents chosen from the group comprising halogen, C1-C2alkyl, nitro and cyano;
n is 1 or 2.
8. A compound of the formula I according to claim 5, in which:
R1 is hydrogen; or C1-C4alkyl;
R2 is hydrogen, C1-C4alkyl, halo-C1-C4- alkyl having 1, 2 or 3 halogen atoms,
C1-C2alkoxy-C1-C4alkyl, cyclopropyl, ethynyl or halogen;
R3 is chlorine;
R4 is hydrogen or C1-C4alkyl; R5 is C1-C4alkyl;
R6 is hydrogen;
R7, R8 and R9 independently of one another are hydrogen or halogen;
X is OR10, SR10 or N(R11)R12;
Y is a group -CH(R13)-, oxygen, sulfur or a group -N(R14)-;
R10 is C1-C4alkyl, halo-C1-C4-alkyl having 1, 2 or 3 halogen atoms, C1-C2alkoxy- C1-C4alkyl, hydroxy-C1-C4alkyl, nitro-C1-C4alkyl, cyano-C1-C4alkyl, C1-C4alkanoyl- C1-C4alkyl, C1-C4alkoxycarbonyl-C1-C4alkyl, C3-C5cycloalkyl, benzyl, phenyl, which is unsubstituted or mono- to disubstituted by halogen, C1-C2alkyl, nitro or cyano, pyridine, pyrimidine or diazine, in which these heterocyclic radicals in each case are unsubstituted or mono- to trisubstituted by identical or different substituents from the group comprising halogen, C1-C2alkyl, trifluoromethyl and cyano, or a 5-membered lactone ring;
R11 is hydrogen, C1-C4alkyl, halo-C1-C4-alkyl having 1, 2 or 3 halogen atoms,
C1-C2alkoxy-C1-C4alkyl, hydroxy-C1-C4alkyl, nitro-C1-C4alkyl, cyano-C1-C4alkyl, C1-C4alkanoyl-C1-C4alkyl, C1-C4alkoxycarbonyl-C1-C4alkyl, C3-C5cycloalkyl, benzyl or phenyl, which is unsubstituted or mono- to disubstituted by halogen, C1-C2alkyl, nitro or cyano,
R12 is hydrogen or C1-C4alkyl; or
R11 and R12, together with the nitrogen atom to which they are bonded, are pyrrolidine, piperidine, piperazine, morpholine or 2,6-dimethylmorpholine;
R13 is hydrogen;
R14 is hydrogen, C1-C4alkyl, C1-C4alkanoyl or benzoyl, the phenyl group of which is unsubstituted or substituted by one, two or three substituents chosen from the group comprising halogen, C1-C2alkyl, nitro and cyano;
n is 1 or 2.
9. A compound of the formula I according to claim 8, in which:
X is SR10;
R10 is C1-C2alkyl, halo-C1-C2-alkyl having 1, 2 or 3 halogen atoms, C1-C2alkoxy- C1-C2alkyl, hydroxy-C1-C2alkyl, acetyl-C1-C2alkyl, tert-butyloxycarbonyl-C1-C2alkyl, benzyl, phenyl, which is unsubstituted or mono- to disubstituted by halogen, C1-C2alkyl, nitro or cyano, pyridine, pyrimidine or triazine, in which these heterocyclic radicals in each case are unsubstituted or mono- to trisubstituted by identical or different substituents from the group comprising halogen, C1-C2alkyl, trifluoromethyl and cyano, or a
5-membered lactone ring.
10. A compound of the formula I according to claim 8, in which:
X is N(R11)R12;
R11 is hydrogen, C1-C4alkyl, halo-C1-C2-alkyl having 1, 2 or 3 halogen atoms,
C1-C2alkoxy-C1-C2alkyl, hydroxy-C1-C2alkyl, nitro-C1-C4alkyl, cyano-C1-C2alkyl, acetyl-C1-C2alkyl, tert-butyloxycarbonyl-C1-C2alkyl, C3-C5cycloalkyl, benzyl or phenyl, which is unsubstituted or mono- to disubstituted by halogen, C1-C2alkyl, nitro or cyano, R12 is hydrogen or C1-C4alkyl; or
R11 and R12, together with the nitrogen atom to which they are bonded, are pyrrolidine, piperidine, piperazine, morpholine or 2,6-dimethylmorpholine.
11. A compound according to claim 1 of the formula I.1
Figure imgf000148_0001
12. A compound according to claim 11, in which:
R2 is hydrogen, methyl or ethyl;
R3 is fluorine or chlorine;
R5 is methyl or ethyl;
R8 and R9 independently of one another are hydrogen or fluorine;
X is OR10, SR10 or N(R11)R12;
R10 is methyl, ethyl, difluoromethyl, trifluoromethyl, 2,2,2-trifluoroethyl, cyanomethyl, tert-butyloxycarbonylmethyl, allyl, 2-propynyl, cyclohexyl, cyclohexenyl, pyridine, pyrimidine or triazine, in which these heterocyclic radicals in each case are unsubstituted or mono- to trisubstituted by identical or different substituents from the group comprising halogen, C1-C2alkyl, trifluoromethyl and cyano;
R11 is hydrogen, C1-C4alkyl, halo-C1-C4-alkyl having 1, 2 or 3 halogen atoms, hydroxy- C1-C4alkyl, cyano-C1-C4alkyl, allyl, 2-propynyl, cyclohexyl, cyclohexenyl, cyclopropyl, benzyl or phenyl;
R12 is hydrogen; or R11 and R12, together with the nitrogen atom to which they are bonded, are pyrrolidine, piperidine, piperazine, morpholine or 2,6-dimethylmorpholine.
13. A compound according to claim 1, of the formula I.2
Figure imgf000149_0001
14. A compound according to claim 13, in which:
R2 is hydrogen, methiyl or ethyl;
R3 is fluorine or chlorine;
R5 is methyl or ethyl;
R8 and R9 independently of one another are hydrogen or florine;
X is OR10, SR10 or N(R11)R12;
R10 is methyl, ethyl, difluoromethyl, trifluoromethyl, 2,2,2-trifluoroethyl,
cyanomethyl, tert-butyloxycarbonylmethyl, allyl, 2-propynyl, cyclohexyl, cyclohexenyl, pyridine, pyrimidine or triazine, in which these heterocyclic compounds in each case are unsubstituted or mono- to trisubstituted by identical or different substituents from the group comprising halogen, C1-C2alkyl, trifluoromethyl and cyano;
R11 is hydrogen, C1-C4alkyl, halo-C1-C4-alkyl having 1, 2 or 3 halogen atoms, hydroxy- C1-C4alkyl, cyano-C1-C4alkyl, allyl, 2-propynyl, cyclohexyl, cyclohexenyl, cyclopropyl, benzyl or phenyl;
R12 is hydrogen; or
R11 and R12, together with the nitrogen atom to which they are bonded, are pyrrolidine, piperidine, piperazine, morpholine or 2,6-dimethylmorpholine.
15. A compound according to claim 1, of the formula I.3
Figure imgf000150_0001
16. A compound according to claim 15, in which:
R2 is hydrogen, methyl or ethyl;
R3 is fluorine or chlorine;
R5 is methyl or ethyl;
R8 and R9 independently of one another are hydrogen or fluorine;
X is OR10, SR10 or N(R11)R12;
R10 is methyl, ethyl, difluoromethyl, trifluoromethyl, 2,2,2-trifluoroethyl,
cyanomethyl, tert-butyloxycarbonylmethyl, allyl, 2-propynyl, cyclohexyl, cyclohexenyl, pyridine, pyrimidine or triazine, in which these heterocyclic radicals in each case are unsubstituted or mono- to trisubstituted by identical or different substituents from the group comprising halogen, C1-C2alkyl, trifluoromethyl and cyano;
R11 is hydrogen, C1-C4alkyl, halo-C1-C4-alkyl having 1, 2 or 3 halogen atoms, hydroxy- C1-C4alkyl, cyano-C1-C4alkyl, allyl, 2-propynyl, cyclohexyl, cyclohexenyl, cyclopropyl, benzyl or phenyl;
R12 is hydrogen; or
R11 and R12, together with the nitrogen atom to which they are bonded, are pyrrolidine, piperidine, piperazine, morpholine or 2,6-dimetiιylmorpholine.
17. A compound according to claim 1, of the formula I.4
Figure imgf000150_0002
18. A compound according to claim 17, in which:
R2 is hydrogen, methyl or ethyl;
R3 is fluorine or chlorine;
R5 is methyl or ethyl;
R8 and R9 independently of one another are hydrogen or fluorine;
X is OR10, SR10 or N(R11)R12;
R10 is methyl, ethyl, difluoromethyl, trifluoromethyl, 2,2,2-trifluoroethyl,
cyanomethyl, tert-butyloxycarbonylmethyl, allyl, 2-propynyl, cyclohexyl, cyclohexenyl, pyridine, pyrimidine or triazine, in which these heterocyclic radicals in each case are unsubstituted or mono- to trisubstituted by identical or different substituents from the group comprising halogen, C1-C2alkyl, trifluoromethyl and cyano;
R11 is hydrogen, C1-C4alkyl, halo-C1-C4-alkyl having 1, 2 or 3 halogen atoms, hydroxy- C1-C4alkyl, cyano-C1-C4alkyl, allyl, 2-propynyl, cyclohexyl, cyclohexenyl, cyclopropyl, benzyl or phenyl;
R12 is hydrogen; or
R11 and R12, together with the nitrogen atom to which they are bonded, are pyrrolidine, piperidine, piperazine, morpholine or 2,6-dimethylmorpholine.
19. A compound according to claim 1, of the formula I.5
Figure imgf000151_0001
20. A compound according to claim 17, in which:
R2 is hydrogen, methyl or ethyl;
R3 is fluorine or chlorine;
R5 is methyl or ethyl;
R8 and R9 independently of one another are hydrogen or fluorine;
X is OR10, SR10 or N(R11)R12;
R10 is methyl, ethyl, difluoromethyl, trifluoromethyl, 2,2,2-trifluoroethyl, cyanomethyl,tert-butyloxycarbonylmethyl, allyl, 2-propynyl, cyclohexyl, cyclohexenyl, pyridine, pyrimidine or triazine, in which these heterocyclic radicals in each case are unsubstituted or mono- to trisubstituted by identical or different substituents from the group comprising halogen, C1-C2alkyl, trifluoromethyl and cyano;
R11 is hydrogen, C1-C4alkyl, halo-C1-C4-alkyl having 1, 2 or 3 halogen atoms, hydroxy- C1-C4alkyl, cyano-C1-C4alkyl, allyl, 2-propynyl, cyclohexyl, cyclohexenyl, cyclopropyl, benzyl or phenyl;
R12 is hydrogen; or
R11 and R12, together with the nitrogen atom to which they are bonded, are pyrrolidine, piperidine, piperazine, morpholine or 2,6-dimethylmorpholine.
21. A compound according to claim 1, of the formula I.6
Figure imgf000152_0001
22. A compound according to claim 21, in which:
R2 is hydrogen, methyl or ethyl;
R3 is fluorine or chlorine;
R5 is methyl or ethyl;
R8 and R9 independently of one another are hydrogen or fluorine;
X is OR10, SR10 or N(R11)R12;
R10 is methyl, ethyl, difluoromethyl, trifluoromethyl, 2,2,2-trifluoroethyl,
cyanomethyl.tert-butyloxycarbonylmethyl, allyl, 2-propynyl, cyclohexyl, cyclohexenyl, pyridine, pyrimidine or triazine, in which these heterocyclic radicals in each case are unsubstituted or mono- to trisubstituted by identical or different substituents from the group comprising halogen, C1-C2alkyl, trifluoromethyl and cyano;
R11 is hydrogen, C1-C4alkyl, halo-C1-C4-alkyl having 1, 2 or 3 halogen atoms, hydroxy- C1-C4alkyl, cyano-C1-C4alkyl, allyl, 2-propynyl, cyclohexyl, cyclohexenyl, cyclopropyl, benzyl or phenyl; R12 is hydrogen; or
R11 and R12, together with the nitrogen atom to which they are bonded, are pyrrolidine, piperidine, piperazine, morpholine or 2,6-dimethylmorpholine.
23. A compound according to claim 1, of the formula I.9
Figure imgf000153_0001
in which:
R2 is methyl or ethyl;
X is OR10 or SR10 ;
R10 is C1-C6alkyl, halo- C1-C6alkyl having 1-3 halogen atoms,
C1-C4alkoxycarbonyl-C1-C4alkyl, C2-C6alkenyl, C2-C6alkynyl, C3-C6cycloalkyl, or the group
-CH2-CO-W,
in which:
W is C1-C6alkoxy, C3-C6cycloalkoxy, or the group -N(T1)T2;
T1 and T2 independently of one another are hydrogen, C1-C6alkyl, halo- C1-C6alkyl having
1-3 halogen atoms, C3-C6cycloalkyl, phenyl, halophenyl having 1-3 halogen atoms, pyridyl or naphthyl, or
T1 and T2, together with the nitrogen atom to which they are bonded, are piperidine, piperazine, morpholine or 2,6-dimethylmorpholine.
24. A compound according to claim 1, of the formula I.10
Figure imgf000154_0001
in which:
R2 is methyl or ethyl;
X is OR10 or SR10 ;
R10 is C1-C6alkyl, halo-C1-C6alkyl having 1-3 halogen atoms,
C1-C4alkoxycarbonyl-C1-C4alkyl, C2-C6alkenyl, C2-C6alkynyl, or C3-C6cycloalkyl, or the group
-CH2-CO-W,
in which:
W is C1-C6alkoxy, C3-C6cycloalkoxy, or the group -N(T1)T2;
T1 and T2 independently of one another are hydrogen, C1-C6alkyl, halo- C1-C6alkyl having
1-3 halogen atoms, C3-C6cycloalkyl, phenyl, halophenyl having 1-3 halogen atoms, pyridyl or naphthyl, or
T1 and T2, together with the nitrogen atom to which they are bonded, are piperidine, piperazine, morpholine or 2,6-dimethylmorpholine.
25. A compound according to claim 1, of the formula I.11
Figure imgf000154_0002
in which:
R2 is methyl or ethyl;
X is OR10 or SR10 ;
R10 is C1-C6alkyl, halo- C1-C6alkyl having 1-3 halogen atoms, C1-C4alkoxycarbonyl-C1-C4alkyl, C2-C6alkenyl, C2-C6alkynyl, C3-C6cycloalkyl, or the group
-CH2-CO-W,
in which:
W is C1-C6alkoxy, C3-C6cycloalkoxy, or the group -N(T1)T2;
T1 and T2 independently of one anotiier are hydrogen, C1-C6alkyl, halo-C1-C6alkyl having
1-3 halogen atoms, C3-C6cycloalkyl, phenyl, halophenyl having 1-3 halogen atoms, pyridyl or naphthyl, or
T1 and T2, together with the nitrogen atom to which they are bonded, are piperidine, piperazine, morpholine or 2,6-dimethylmorpholine.
26. A compound according to one of claims 1-25, in which
X is SR10.
27. A process for the preparation of a compound of the formula I according to claim 1, which comprises reacting: a) for the preparation of a compound of the formula I in which X is SR10:
a compound of the formula II
Figure imgf000155_0001
in which the substituent A is in the β- or γ-position, and in which
R1 to R9, Y and n are as defined for formula I, with a compound of the formula III
R10-Z (III), in which R10 is as defined for formula I and Z is a nucleofugic radical which can easily be split off;
preferably in the presence of a base, particularly preferably by first reacting a compound of the formula II with a base and then reacting a compound of the formula III; or b) for the preparation of a compound of the formula I in which X is OR10 or N(R11)R12: a compound of the formula I in which X is SR10 with a compound of the formula IV
M-X (IV), in which:
M is hydrogen, Li+, Na+, K+, 1/2Mg2+ or a quaternary ammonium ion;
X is OR10 or N(R11)R12, and wherein R10, R11 and R12 are as defined for formula I; if appropriate in the presence of a base; or c) for the preparation of a compound of the formula I in which R4 and R14 are as defined for formula I but are other than hydrogen:
a compound of the formula I in which R4 and R14 are hydrogen with a compound of the formula R4'-Z' or R14'-Z', in which R4' and R14' are as defined in formula I for R4 and R14, but are other than hydrogen, and Z' is a nucleofugic radical which can easily be split off;
preferably in the presence of a base.
28. A process for the preparation of a compound of the formula I according to claim 1, which comprises reacting:
a compound of the formula VII
Figure imgf000156_0001
in which the substituent A is in the β- or γ-position, and in which
R1 to R9, Y and n are as defined for formula I, with phosphorus oxychloride or with sulfuryl chloride to give a compound of the formula VIII
Figure imgf000157_0001
and then reacting this compound with a compound of the formula IV'
M-X' (IV'), in which:
M is hydrogen, Li+, Na+, K+, 1/2Mg2+ or a quaternary ammonium ion;
X' is OR10, SR10 or N(R11)R12, and in which R10, R11 and R12 are as defined for formula I; if appropriate in the presence of a base.
29. A composition for the protection of plants against attack by pests, which comprises at least one compound according to claim 1 as the active compound, together with a carrier material.
30. A composition according to claim 29, wherein the pests are phytopathogenic microorganisms.
31. A composition according to claim 29, wherein the pests are arachnids, insects and nematodes.
32. A composition for the protection of plants against attack by pests, which comprises at least one compound according to claim 2 as the active compound, together with a carrier material.
33. A composition according to claim 32, wherein the pests are phytopathogenic microorganisms.
34. A composition according to claim 32, wherein the pests are arachnids, insects and nematodes.
35. A process for the preparation of a composition according to claim 29, which comprises intimately mixing the active compound with the extender and/or distributing agent.
36. The use of a compound of the formula I according to claim 1 for the protection of plants against attack by pests.
37. The use of a compound of the formula I according to claim 2 for the protection of plants against attack by pests.
38. A method for the protection of plants against attack by pests, which comprises applying a compound according to claim 1, as the active compound, to the plants, to parts of the plants and/or to the locus of the plants.
39. The method according to claim 38, wherein the pests are phytopathogenic
microorganisms.
40. The method according to claim 38, wherein the pests are arachnids, insects and nematodes.
41. A method for the protection of plants against attack by pests, which comprises applying a compound according to claim 2, as the active compound, to the plants, to parts of the plants and/or to the locus of the plants.
42. The method according to claim 41, wherein the pests are phytopathogenic
microorganisms.
43. The method according to claim 41, wherein the pests are arachnids, insects and nematodes.
PCT/EP1994/000455 1993-03-02 1994-02-17 Pyrimidine derivatives useful as pesticides WO1994020490A1 (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
EP94908333A EP0687262A1 (en) 1993-03-02 1994-02-17 Pyrimidine derivatives useful as pesticides
JP6519509A JPH08507500A (en) 1993-03-02 1994-02-17 Pyrimidine derivatives useful as pest control agents
AU61412/94A AU6141294A (en) 1993-03-02 1994-02-17 Pyrimidine derivatives useful as pesticides

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
CH61793 1993-03-02
CH617/93-3 1993-03-02
CH178893 1993-06-16
CH1788/93-2 1993-06-16

Publications (1)

Publication Number Publication Date
WO1994020490A1 true WO1994020490A1 (en) 1994-09-15

Family

ID=25685132

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1994/000455 WO1994020490A1 (en) 1993-03-02 1994-02-17 Pyrimidine derivatives useful as pesticides

Country Status (5)

Country Link
EP (1) EP0687262A1 (en)
JP (1) JPH08507500A (en)
AU (1) AU6141294A (en)
IL (1) IL108817A0 (en)
WO (1) WO1994020490A1 (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999031072A1 (en) * 1997-12-18 1999-06-24 E.I. Du Pont De Nemours And Company Cyclohexylamine arthropodicides and fungicides
US8785470B2 (en) 2011-08-29 2014-07-22 Infinity Pharmaceuticals, Inc. Heterocyclic compounds and uses thereof
US9181221B2 (en) 2010-05-21 2015-11-10 Infinity Pharmaceuticals, Inc. Chemical compounds, compositions and methods for kinase modulation
US9481667B2 (en) 2013-03-15 2016-11-01 Infinity Pharmaceuticals, Inc. Salts and solid forms of isoquinolinones and composition comprising and methods of using the same

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0264217A2 (en) * 1986-10-08 1988-04-20 Ube Industries, Ltd. Aralkylaminopyrimidine derivative, process for producing thereof and insecticide, acaricide and fungicide containing said derivative as active ingredient
EP0323757A2 (en) * 1988-01-07 1989-07-12 Ube Industries, Ltd. Alkylaminopyrimidine derivative, process for producing the same, and insecticide, acaricide and fungicide containing the same as active ingredient
EP0470600A1 (en) * 1990-08-10 1992-02-12 Ciba-Geigy Ag Naphthylalkylaminopyrimidine derivatives, process for their preparation and pesticides containing them
WO1992008704A1 (en) * 1990-11-19 1992-05-29 E.I. Du Pont De Nemours And Company Insecticidal, acaricidal and fungicidal aminopyrimidines
EP0519211A1 (en) * 1991-05-17 1992-12-23 Hoechst Schering AgrEvo GmbH Substituted 4-aminopyrimidine, process for their preparation and their use as parasiticide
EP0555183A1 (en) * 1992-02-07 1993-08-11 Ciba-Geigy Ag Pesticides
WO1993019050A1 (en) * 1992-03-14 1993-09-30 Hoechst Schering Agrevo Gmbh Substituted pyrimidines and their use as pesticides

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0264217A2 (en) * 1986-10-08 1988-04-20 Ube Industries, Ltd. Aralkylaminopyrimidine derivative, process for producing thereof and insecticide, acaricide and fungicide containing said derivative as active ingredient
EP0323757A2 (en) * 1988-01-07 1989-07-12 Ube Industries, Ltd. Alkylaminopyrimidine derivative, process for producing the same, and insecticide, acaricide and fungicide containing the same as active ingredient
EP0470600A1 (en) * 1990-08-10 1992-02-12 Ciba-Geigy Ag Naphthylalkylaminopyrimidine derivatives, process for their preparation and pesticides containing them
WO1992008704A1 (en) * 1990-11-19 1992-05-29 E.I. Du Pont De Nemours And Company Insecticidal, acaricidal and fungicidal aminopyrimidines
EP0519211A1 (en) * 1991-05-17 1992-12-23 Hoechst Schering AgrEvo GmbH Substituted 4-aminopyrimidine, process for their preparation and their use as parasiticide
EP0555183A1 (en) * 1992-02-07 1993-08-11 Ciba-Geigy Ag Pesticides
WO1993019050A1 (en) * 1992-03-14 1993-09-30 Hoechst Schering Agrevo Gmbh Substituted pyrimidines and their use as pesticides

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999031072A1 (en) * 1997-12-18 1999-06-24 E.I. Du Pont De Nemours And Company Cyclohexylamine arthropodicides and fungicides
US9181221B2 (en) 2010-05-21 2015-11-10 Infinity Pharmaceuticals, Inc. Chemical compounds, compositions and methods for kinase modulation
US9738644B2 (en) 2010-05-21 2017-08-22 Infinity Pharmaceuticals, Inc. Chemical compounds, compositions and methods for kinase modulation
US8785470B2 (en) 2011-08-29 2014-07-22 Infinity Pharmaceuticals, Inc. Heterocyclic compounds and uses thereof
US9546180B2 (en) 2011-08-29 2017-01-17 Infinity Pharmaceuticals, Inc. Heterocyclic compounds and uses thereof
US9481667B2 (en) 2013-03-15 2016-11-01 Infinity Pharmaceuticals, Inc. Salts and solid forms of isoquinolinones and composition comprising and methods of using the same

Also Published As

Publication number Publication date
JPH08507500A (en) 1996-08-13
EP0687262A1 (en) 1995-12-20
IL108817A0 (en) 1994-06-24
AU6141294A (en) 1994-09-26

Similar Documents

Publication Publication Date Title
KR960002556B1 (en) Imidazole compounds and biocidal composition comprising the same for controlling harmful organisms
EP0651737B1 (en) O-benzyl oxime ether derivatives and their use as pesticides
JPS6115877A (en) N-(2-nitrophenyl)-2-aminopyrimidine derivative, manufacture and composition
EP0784611B1 (en) N-(ortho-substituted benzyloxy)imine derivatives and their use as fungicides, acaricides or insecticides
EP0837856B1 (en) Pesticidal tris-oximino heterocyclic compounds
JPH06172348A (en) Noxious life controlling agent
EP0836595B1 (en) Triazoline and isoxazoline bis-oxime derivatives and their use as pesticides
WO1996008475A1 (en) Pesticidal pyridine derivatives
WO1994020490A1 (en) Pyrimidine derivatives useful as pesticides
WO1994019340A1 (en) Pyrimidine derivatives and their use as pesticides
WO1996016026A1 (en) O-benzyl oxime ether derivatives and their use as pesticides
WO1996014301A1 (en) Pesticidal pyridine thioamides
US5814629A (en) Microbicides
US6288071B1 (en) 1-ethylene-2-alkylene-1,4-cyclohexadiene pesticides
WO1995001975A1 (en) Pyrimidin-4-ylaminomethylquinoline derivatives as pesticides
BG61035B1 (en) Thiazolyl-5-carbonamide derivatives and plant control preparations
EP0907634B1 (en) Pesticides
US20020111273A1 (en) Dihydrobenzene pesticides
EP0621864A1 (en) 2-(2-BENZO(b)THIENYL)-3-METHOXYACRYLATE AND -2-IMINOACETATE DERIVATIVES TO BE USED AS PESTICIDES.
KR20010012997A (en) O-Benzyl oxime ether derivatives and their use as pesticides

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AU BG BR BY CA CN CZ FI HU JP KR KZ LV NZ PL RO RU SK UA US UZ

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FR GB GR IE IT LU MC NL PT SE

DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
121 Ep: the epo has been informed by wipo that ep was designated in this application
WWE Wipo information: entry into national phase

Ref document number: 1994908333

Country of ref document: EP

ENP Entry into the national phase

Ref country code: US

Ref document number: 1995 513795

Date of ref document: 19950831

Kind code of ref document: A

Format of ref document f/p: F

WWP Wipo information: published in national office

Ref document number: 1994908333

Country of ref document: EP

NENP Non-entry into the national phase

Ref country code: CA

WWR Wipo information: refused in national office

Ref document number: 1994908333

Country of ref document: EP

WWW Wipo information: withdrawn in national office

Ref document number: 1994908333

Country of ref document: EP