WO1994019340A1 - Derives de pyrimidine et leur utilisation comme pesticides - Google Patents

Derives de pyrimidine et leur utilisation comme pesticides Download PDF

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WO1994019340A1
WO1994019340A1 PCT/EP1994/000337 EP9400337W WO9419340A1 WO 1994019340 A1 WO1994019340 A1 WO 1994019340A1 EP 9400337 W EP9400337 W EP 9400337W WO 9419340 A1 WO9419340 A1 WO 9419340A1
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alkyl
hydrogen
substituted
unsubstituted
group
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PCT/EP1994/000337
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English (en)
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Harald Walter
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Ciba-Geigy Ag
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Priority to AU60392/94A priority Critical patent/AU6039294A/en
Priority to JP6518602A priority patent/JPH08507053A/ja
Priority to EP94906911A priority patent/EP0694034A1/fr
Publication of WO1994019340A1 publication Critical patent/WO1994019340A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
    • C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
    • C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D215/20—Oxygen atoms
    • C07D215/22—Oxygen atoms attached in position 2 or 4
    • C07D215/227—Oxygen atoms attached in position 2 or 4 only one oxygen atom which is attached in position 2
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/54—1,3-Diazines; Hydrogenated 1,3-diazines
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • 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
    • C07D223/00—Heterocyclic compounds containing seven-membered rings having one nitrogen atom as the only ring hetero atom
    • C07D223/14—Heterocyclic compounds containing seven-membered rings having one nitrogen atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
    • C07D223/16—Benzazepines; Hydrogenated benzazepines
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D241/00—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings
    • C07D241/36—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings condensed with carbocyclic rings or ring systems
    • C07D241/38—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings condensed with carbocyclic rings or ring systems with only hydrogen or carbon atoms directly attached to the ring nitrogen atoms
    • C07D241/40—Benzopyrazines
    • C07D241/44—Benzopyrazines with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to carbon atoms of the hetero ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D265/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom and one oxygen atom as the only ring hetero atoms
    • C07D265/28—1,4-Oxazines; Hydrogenated 1,4-oxazines
    • C07D265/34—1,4-Oxazines; Hydrogenated 1,4-oxazines condensed with carbocyclic rings
    • C07D265/36—1,4-Oxazines; Hydrogenated 1,4-oxazines condensed with carbocyclic rings condensed with one six-membered ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D279/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom and one sulfur atom as the only ring hetero atoms
    • C07D279/10—1,4-Thiazines; Hydrogenated 1,4-thiazines
    • C07D279/14—1,4-Thiazines; Hydrogenated 1,4-thiazines condensed with carbocyclic rings or ring systems
    • C07D279/16—1,4-Thiazines; Hydrogenated 1,4-thiazines condensed with carbocyclic rings or ring systems condensed with one six-membered ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • 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
    • 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
    • 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

Definitions

  • the invention relates to novel pesticidally active compounds of formula I
  • substituent A is in the ⁇ -, ⁇ -, ⁇ - or ⁇ -position and wherein:
  • 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 are each independently of the other hydrogen, C 1 -C 4 alkyl, 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, alkanoyl-C 1 -C 4 alkyl, alkoxycarbonyl- C 1 -C 4 alkyl, C 1 -C 2 alkylthio-C 1 -C 4 alkyl,
  • N C(R 13 )R 14 ;
  • R 4 is 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 3 -C 5 cycloalkyl, benzyl, C 1 -C 4 - alkanoyl, or benzoyl, the phenyl group of which is unsubstituted or substituted by one, two or three substituents selected from the group consisting of halogen, C 1 -C 2 alkyl, nitro and cyano;
  • R 5 and R 6 are each independently of the other 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, alkoxycarbonyl-C 1 -C 4 alkyl or C 3 -C 6 cycloalkyl that is unsubstituted or substituted by one or two substituents selected from the group consisting of halogen and C 1 -C 2 alkyl;
  • R 7 is hydrogen, an unsubstituted or substituted open-chain, saturated or unsaturated hydrocarbon radical containing up to 8 carbon atoms, an unsubstituted or substituted cyclic, saturated or unsaturated hydrocarbon radical containing up to 10 carbon atoms, unsubstituted or substituted benzyl, an unsubsti
  • R 8 , R 9 , R 10 and R 11 are each independently of the others 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, C 3 -C 6 cyclo- alkyl, C 1 -C 4 alkoxy, halo-C 1 -C 4 alkoxy having 1, 2 or 3 halogen atoms, C 3 -C 7 cycloalkoxy, C 1 -C 4 alkylthio, halo- C 1 -C 4 alkylthio having 1, 2 or 3 halogen atoms, cyano, nitro, phenyl, phenoxy or phenylthio, the phenyl groups in phenyl, phenoxy and phenylthio being unsubstituted or substituted by one, two or three substituents selected from the group consisting of hal
  • R 12 is C 1 -C 4 alkyl, benzyl, C 1 -C 4 alkanoyl, benzoyl, the phenyl group of which is unsubstituted or substituted by one, two or three substituents selected from the group consisting of halogen and C 1 -C 2 alkyl, C 1 -C 4 alkylthio, halo-C 1 -C 4 alkylthio having 1, 2 or 3 halogen atoms, cyano-C 1 -C 4 alkylthio, phenylthio or benzylthio, the phenyl groups in phenylthio and benzylthio being unsubstituted or substituted by one or two substituents selected from the group consisting of halogen, C 1 -C 2 alkyl, nitro and cyano;
  • R 13 is C 1 -C 4 alkyl
  • R 14 is hydrogen or C 1 -C 4 alkyl
  • X is oxygen or sulfur
  • Y is a group -CH(R 15 )-, oxygen, sulfur or a group -N(R 16 )-;
  • R 15 is hydrogen or C 1 -C 4 alkyl
  • R 16 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 selected from the group consisting of 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 di-substituted by C 1 -C 4 alkyl; and n is 1 or 2;
  • the invention relates also to the preparation of those compounds, to agrochemical compositions that comprise at least one of those compounds as active ingredient, and to the use of the compounds or the compositions in pest control, especially as microbicides in agriculture and horticulture.
  • the compounds I and, where appropriate,, their tautomers, may be in the form of salts. Since the compounds I have at least one basic centre, they can form, for example, acid addition salts.
  • the acid addition salts are formed, for example, with mineral acids, for example sulfuric acid, a phosphoric acid or a hydrohalic acid, with organic carboxylic acids, such as, for example, acetic, 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, such as, for example, methane- or p-toluene- sulfonic acid.
  • mineral acids for example sulfuric acid, a phosphoric acid or a hydrohalic acid
  • organic carboxylic acids such as, for example, acetic, oxalic, malonic, maleic, fumaric or phthalic
  • compounds of formula I having at least one acid group can form salts with bases.
  • Suitable salts with bases are, for example, metal salts, such as alkali or alkaline earth metal salts, for example sodium, potassium 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 tri-hydroxy-lower alkylamine, for example mono-, di- or tri-ethanolamine.
  • corresponding internal salts may also be formed.
  • Agro- chemically advantageous salts are preferred within the scope of the invention, but salts that have drawbacks as regards agrochemical use, for example salts that are toxic to bees or fish, are also included and are used, for example, for the isolation or purification of free compounds I or the agrochemically acceptable salts thereof.
  • alkyl groups are straight-chained or branched and are, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert- butyl, sec-amyl, tert-amyl, 1-hexyl or 3-hexyl.
  • Unsaturated hydrocarbon radicals are alkenyl, alkynyl or alkenynyl groups having a maximum of 3 multiple bonds, such as, for example, butadienyl, hexatrienyl and 2- penten-4-ynyl.
  • Alkenyl is to be understood as being straight-chain or branched alkenyl, such as, for example, allyl, methallyl, 1-methylvinyl or but-2-en-1-yl.
  • Alkenyl radicals having a chain length of 3 or 4 carbon atoms are preferred.
  • alkynyl may likewise be straight-chained or branched, and is, for example, propargyl, but-1-yn-1-yl and but-1-yn-3-yl. Propargyl is preferred.
  • Halogen or halo is fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine.
  • Haloalkyl may contain identical or different halogen atoms and is, for example, fluoro- methyl, difluoromethyl, difluorochloromethyl, trifluoromethyl, chloromethyl, dichloro- methyl, trichloromethyl, 2,2,2-trifluoroethyl, 2-fluoroethyl, 2-chloroethyl, 2,2,2-trichloro- ethyl and 3,3,3-trifluoropropyl.
  • Alkoxy is, for example, methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, sec- butoxy and tert-butoxy; 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.
  • Cyclic unsaturated hydrocarbon radicals may be aromatic, such as, for example, phenyl and naphthyl, or non-aromatic, such as, for example, cyclopentenyl, cyclohexenyl, cyclo- heptenyl and cyclooctadienyl, or partially aromatic, such as, for example, tetrahydro- naphthyl and indanyl.
  • cycloalkyl is cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl or cycloheptyl.
  • Acyl may be saturated or unsaturated, open-chained or cyclic, isocyclic or heterocyclic. Examples are acetyl, propionyl, acryloyl, crotonoyl, cyclohexanoyl, benzoyl, naphthoyl, furoyl or nicotinoyl.
  • alkanoyl is either straight- chained or branched, and is, for example, formyl, acetyl, propionyl, butyryl, pivaloyl or octanoyl.
  • alkoxy-, alkylthio-, alkanesulfinyl-, alkanesulfonyl- nitro- and cyano-substituted carbon-containing groups and compounds such as alkoxyalkyl, alkylthioalkyl, alkane- sulfinylalkyl, alkanesulfonylalkyl, nitroalkyl, cyanoalkyl and cyanoalkanesulfonyl, one of the hydrogen atoms present in the initial unsubstituted basic structure has been replaced by alkoxy, alkylthio, alkanesulfinyl, alkanesulfonyl, nitro and cyano, respectively.
  • a heterocyclyl radical is to be understood as being a 5- or 6-membered, aromatic or non- aromatic ring having hetero atoms N, O and/or S. Furthermore, an unsubstituted or substituted benzo group may have been fused onto such a heterocyclyl radical, which is 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 partially or totally hydrogenated rings.
  • heterocyclyl groups having a fused benzo group examples include quinolyl, isoquinolyl, benzoxazolyl, quinoxalinyl, benzothiazolyl, benzimidazolyl, indolyl and indolinyl.
  • R 7 is 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, alkanoyl- C 1 -C 4 alkyl, alkoxy- carbonyl-C 1 -C 4 alkyl, C 3 -C 5 cycloalkyl, benzyl, phenyl that is unsubstituted or mono- to tri-substituted by the same or different substituents selected from the group consisting of C 1 -C 2 alkyl, halomethyl, halogen, nitro and amino, C 1 -C 4 alkanoyl that is unsubstituted or substituted by halogen or by C 1 -C 2 alkoxy, C 1 -C 4 thioalkanoy
  • R 7 is hydrogen, an open-chain, saturated or unsaturated hydrocarbon radical containing up to 8 carbon atoms that is unsubstituted or substituted by from 1 to 5 halogen atoms, tri- (C 1 -C 4 alkyl)silyl or by an epoxy group, C 1 -C 4 alkanoyl that is unsubstituted or substituted by from 1 to 3 halogen atoms, C 1 -C 2 alkoxy, phenoxy, amino or by dimethylamino, or a group
  • T 1 and T 2 are each independently of the other hydrogen, an open-chain, saturated or unsaturated hydrocarbon radical containing up to 8 carbon atoms that is unsubstituted or substituted by from 1 to 3 halogen atoms, C 1 -C 2 alkoxy, hydroxy, nitro, cyano, C 1 -C 4 - alkanoyl, halo-C 1 -C 4 alkanoyl or by C 1 -C 4 alkoxycarbonyl, a cyclic, saturated or unsaturated hydrocarbon radical containing up to 10 carbon atoms or benzyl, wherein the carbocycle is unsubstituted or mono- or di-substituted by halogen, C 1 -C 2 alkyl, halomethyl, nitro or by cyano, or heterocyclyl that is unsubstituted or mono- to tri-substituted by the same or different substituents selected from the group consisting of C 1 -C 2 alkyl, hal
  • T 1 and T 2 together with the nitrogen atom to which they are bonded, form a 5- to 7- membered heterocycle which may additionally contain O, S and/or N as ring atoms, wherein additional nitrogen is unsubstituted or substituted by C 1 -C 4 alkyl, phenyl, C 1 -C 4 - alkanoyl, benzoyl or by benzyl and wherein the carbon atoms of the heterocycle are unsubstituted or mono- to tri-substituted by the same or different substituents selected from the group consisting of halogen, C 1 -C 2 alkyl, halomethyl and nitro;
  • R 7 is hydrogen, an open-chain, saturated or unsaturated hydrocarbon radical containing up to 4 carbon atoms that is unsubstituted or substituted by from 1 to 3 halogen atoms or by tri(C 1 -C 4 alkyl)silyl, C 1 -C 4 alkanoyl that is unsubstituted or substituted by from 1 to 3 halogen atoms, C 1 -C 2 alkoxy, phenoxy, amino or by dimethylamino,
  • T 1 and T 2 each independently of the other hydrogen, C 1 -C 4 alkyl, phenyl or halophenyl, or T 1 and T 2 , together with the nitrogen atom to which they are bonded, form piperidine or morpholine;
  • R 1 is hydrogen or C 1 -C 4 alkyl
  • R 2 and R 3 are each independently of the other 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, hydroxy or halogen;
  • R 4 is hydrogen, C 1 -C 4 alkyl, C 3 -C 5 cycloalkyl or benzyl;
  • R 5 and R 6 are each independently of the other 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 or C 3 -C 6 cycloalkyl;
  • R 7 is 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, cyano- C 1 -C 4 alkyl, benzyl, phenyl that is unsubstituted or mono- to tri-substituted by the same or different substituents selected from the group consisting of C 1 -C 2 alkyl, halomethyl, halogen, nitro and amino, C 1 -C 4 alkanoyl that is unsubstituted or substituted by halogen or by C 1 -C 2 alkoxy, C 1 -C 4 thioalkanoyl, benzoyl, the phenyl group of which is unsubstituted or substituted by one or two substituents selected from the group consisting of halogen and C 1 -C 2 alkyl; thiobenzoyl
  • R 8 , R 9 , R 10 and R 11 are each independently of the other hydrogen, halogen or C 1 -C 4 alkyl; X is oxygen or sulfur;
  • Y is a group -CH(R 15 )-, oxygen, sulfur or a group -N(R 16 )-;
  • R 15 is hydrogen or C 1 -C 4 alkyl
  • R 16 is hydrogen, C 1 -C 4 alkanoyl, benzoyl, the phenyl group of which is unsubstituted or substituted by one, two or three substituents selected from the group consisting of 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 di-substituted by C 1 -C 4 alkyl; and
  • 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, C 1 -C 2 - alkoxy-C 1 -C 4 alkyl, cyclopropyl, ethynyl or halogen;
  • R 3 is hydrogen, fluorine, chlorine or bromine
  • R 4 is hydrogen or C 1 -C 4 alkyl
  • R 5 is C 1 -C 4 alkyl
  • R 6 is hydrogen
  • R 7 is hydrogen, C 1 -C 4 alkyl, C 1 -C 2 alkoxy-C 1 -C 4 alkyl, cyano- C 1 -C 4 alkyl, C 1 -C 4 alkanoyl that is unsubstituted or substituted by halogen or by C 1 -C 4 alkoxy, C 1 -C 4 thioalkanoyl, benzoyl, the phenyl group of which is unsubstituted or substituted by one or two substituents selected from the group consisting of halogen and C 1 -C 2 alkyl; thiobenzoyl, the phenyl group of which is unsubstituted or substituted by one or two substituents selected from the group consisting of halogen and C 1 -C 2 alkyl, C 1 -C 4 alkylsulfonyl, halo- C 1 -C 4 - alkylsulfonyl having 1, 2 or 3 halogen atom
  • R 8 and R 9 are each independently of the other hydrogen, fluorine, chlorine or bromine; R 10 and R 11 are hydrogen;
  • X is oxygen or sulfur
  • Y is a group -CH(R 15 )-, oxygen, sulfur or a group -N(R 16 )-;
  • R 15 is hydrogen or C 1 -C 4 alkyl
  • R 16 is hydrogen, C 1 -C 4 alkanoyl, benzoyl, the phenyl group of which is unsubstituted or substituted by one, two or three substituents selected from the group consisting of 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 di-substituted by C 1 -C 4 alkyl; and
  • n 1 or 2.
  • R 7 is hydrogen, methyl, ethyl or cyanomethyl
  • R 8 and R 9 are each independently of the other hydrogen or fluorine; R 10 and R 11 are hydrogen;
  • X is oxygen or sulfur
  • Y is the group -CH 2 -, oxygen, sulfur or the group -NH-;
  • n 1 or 2.
  • Y is the group -CH 2 -;
  • 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, C 1 -C 2 - alkoxy- C 1 -C 4 alkyl, cyclopropyl, ethynyl or halogen;
  • R 3 is hydrogen, fluorine, chlorine or bromine
  • R 4 is hydrogen or C 1 -C 4 alkyl
  • R 5 is C 1 -C 4 alkyl
  • R 6 is hydrogen
  • R 7 is hydrogen, methyl, ethyl or cyanomethyl
  • R 8 and R 9 are each independently of the other hydrogen or fluorine
  • R 10 and R 11 are hydrogen
  • X is oxygen or sulfur
  • Y is the group -CH 2 -;
  • n 1 or 2.
  • R 2 is hydrogen, methyl or ethyl
  • R 3 is fluorine or chlorine
  • R 5 is methyl or ethyl
  • R 7 is hydrogen, methyl, ethyl or cyanomethyl
  • R 8 and R 9 are each independently of the other hydrogen or fluorine
  • X is oxygen or sulfur.
  • R 2 is hydrogen, methyl or ethyl
  • R 3 is fluorine or chlorine
  • R 5 is methyl or ethyl
  • R 7 is hydrogen, methyl, ethyl or cyanomethyl
  • R 8 and R 9 are each independently of the other hydrogen or fluorine
  • X is oxygen or sulfur.
  • Y is oxygen or sulfur
  • n 1;
  • R 2 is hydrogen, methyl or ethyl
  • R 3 is fluorine or chlorine
  • R 5 is methyl or ethyl
  • R 7 is hydrogen, methyl, ethyl or cyanomethyl
  • R 8 and R 9 are each independently of the other hydrogen or fluorine
  • X is oxygen or sulfur.
  • R 2 is hydrogen, methyl or ethyl
  • R 3 is fluorine or chlorine
  • R 5 is methyl or ethyl
  • R 7 is hydrogen, methyl, ethyl or cyanomethyl
  • R 8 and R 9 are each independently of the other hydrogen or fluorine
  • X is oxygen or sulfur.
  • R 2 is hydrogen, methyl or ethyl
  • R 3 is fluorine or chlorine
  • R 5 is methyl or ethyl
  • R 7 is hydrogen, methyl, ethyl or cyanomethyl
  • R 8 and R 9 are each independently of the other hydrogen or fluorine
  • X is oxygen or sulfur.
  • R 2 is hydrogen, methyl or ethyl
  • R 3 is fluorine or chlorine
  • R 5 is methyl or ethyl
  • R 7 is hydrogen, methyl, ethyl or cyanomethyl
  • R 8 and R 9 are each independently of the other hydrogen or fluorine
  • X is oxygen or sulfur.
  • R 1 is hydrogen
  • R 2 is methyl or ethyl
  • R 3 is chlorine; R 4 is hydrogen;
  • R 5 is methyl, ethyl or cyclopropyl
  • R 6 is hydrogen
  • R 7 is hydrogen, methyl, ethyl, cyanomethyl or methylsulfonyl
  • R 8 , R 9 , R 10 and R 11 are each hydrogen
  • X is oxygen or sulfur
  • Y is oxygen or the group -CH 2 -;
  • n 1 or 2.
  • substituent A is either in the ⁇ -position or in the ⁇ -position, and wherein: R 5 is methyl or ethyl;
  • R 7 is C 1 -C 4 alkyl that is unsubstituted or substituted by from 1 to 3 halogen atoms or by cyano, C 2 -C 4 alkenyl, C 2 -C 4 alkynyl, or acetyl that is unsubstituted or substituted by C 1 -C 4 - alkoxy, phenoxy or by halogen.
  • R 5 is methyl or ethyl
  • R 7 is C 1 -C 4 alkyl, C 2 -C 4 alkenyl, C 2 -C 4 alkynyl, or acetyl that is unsubstituted or substituted by C 1 -C 4 alkoxy, phenoxy or by halogen.
  • R 5 is methyl or ethyl
  • R 7 is C 1 -C 4 alkyl, C 2 -C 4 alkenyl, C 2 -C 4 alkynyl, or acetyl that is unsubstituted or substituted by C 1 -C 4 alkoxy, phenoxy or by halogen.
  • the invention relates also to a process for the preparation of the compounds of formula I and, where appropriate, the tautomers thereof, in each case in free form or in salt form, which process is carried out, for example, as follows: a) for the preparation of a compound of formula I wherein R 1 -R 11 , X, Y and n are as defined for formula I, a compound of formula II
  • R 1 , R 2 and R 3 are as defined for formula I and Z is a readily removable nucleo- fugal radical, is reacted, preferably in the presence of a base, with a compound of formula
  • R 4 to R 11 , X, Y and n are as defined for formula I; or b) for the preparation of a compound of formula I wherein R 4 , R 7 and R 16 are as defined for formula I but are other than hydrogen, a compound of formula I wherein R 4 , R 7 and R 16 are hydrogen is reacted in the presence of a base, for example sodium hydride, potassium hydride, alkyllithium or potassium tert-butanolate, with a compound of the formula R 4 '-Z', R 7 '-Z' or R 16 '-Z' wherein R 4 ', R 7 ' and R 16 ' are as defined in formula I for R 4 , R 7 and R 16 , respectively, but are other than hydrogen and Z' is a readily removable nucleofugal radical; or c) for the preparation of a compound of formula I wherein X is sulfur, a compound of formula I wherein X is oxygen is reacted with a th
  • the reactions described hereinbefore and hereinafter are carried out in a manner known per se, for example in the absence or, generally, in the presence of a suitable solvent or diluent or a mixture thereof, the operation being carried out, as required, with cooling, at room temperature or with heating, for example in a temperature range of approximately from -80°C up to the boiling temperature of the reaction medium, preferably from approximately -20°C to approximately +150°C, and, if necessary, in a closed vessel, under pressure, in an inert gas atmosphere and/or under anhydrous conditions.
  • a suitable solvent or diluent or a mixture thereof for example in a temperature range of approximately from -80°C up to the boiling temperature of the reaction medium, preferably from approximately -20°C to approximately +150°C, and, if necessary, in a closed vessel, under pressure, in an inert gas atmosphere and/or under anhydrous conditions.
  • Especially advantageous reaction conditions can be found in the Examples.
  • Suitable as nucleofugal 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, ethane- sulfonyloxy or trifluoromethanesulfonyloxy, or unsubstituted or substituted phenylsulfon- yloxy, such as benzenesulfonyloxy or p-toluenesulfonyloxy, and also hydroxy.
  • C 1 -C 8 alkylthio such as methylthio, ethylthio or propylthio
  • Suitable bases for facilitating the removal of HZ are, for example, alkali metal or alkaline earth metal hydroxides, hydrides, amides, alkanolates, carbonates, dialkylamides or alkyl- silylamides; alkylamines, alkylenediamines, unsubstituted or N-alkylated, saturated or unsaturated cycloalkylamines, basic heterocycles, ammonium hydroxides and carbocyclic amines.
  • DBU 1,8-diazabicyclo[5.4.0]undec-5-ene
  • the reactants may be reacted with one another as such, that is to say, without the addition of a solvent or diluent, for example in the melt. In most cases, however, the addition of an inert solvent or diluent or a mixture thereof is advantageous.
  • solvents and diluents aromatic, aliphatic and alicyclic hydrocarbons and halogenated hydrocarbons, such as benzene, toluene, xylene, chlorobenzene, bromo- benzene, petroleum ether, hexane, cyclohexane, dichloromethane, trichloromethane, dichloroethane or trichloroethane; ethers, such as diethyl ether, tert-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-dimethylformamide, N
  • the reaction is advantageously carried out in a temperature range of from approximately 0°C to approximately +180°C, preferably from approximately +20°C to approximately +130°C, in many cases at the reflux temperature of the solvent used.
  • a compound II wherein Z is halogen, preferably chlorine, is reacted with a compound III at reflux temperature in an alcohol, preferably in isopropanol, or in dimethylformamide or in dimethyl sulfoxide, or in a mixture thereof, and in the presence of an alkylamine, preferably in the presence of triethylamine.
  • the optional subsequent N-alkylation and N-benzylation for the introduction of the substituents R 4 , R 7 and/or R 16 is carried out in customary manner using a corresponding alkyl or benzyl halide, preferably the corresponding bromide, or using the corresponding alkyl sulfate.
  • the optional subsequent N-acylation, N-benzoylation or N-sulfonylation for the introduction of the substituents R 4 , R 7 and/or R 16 is carried out in customary manner using a corresponding acyl, benzoyl or sulfonyl halide, respectively, preferably the corresponding chloride, or using a corresponding anhydride.
  • the optional subsequent N-arylation or N-heteroarylation for the introduction of the substituent R 7 is carried out in customary manner using an activated, corresponding aryl halide or heteroaryl halide.
  • a compound I obtainable in accordance with the process or by another method, or, where appropriate, a tautomer thereof, can be converted in a manner known per se into a different compound I by replacing one or more substituents of the starting compound I in customary manner with a different substituent
  • non-halogen-containing substituents and non-halogenated aromatic or heteroaromatic ring partial structures can be halogenated to form halogen-containing substituents and halogenated aromatic or heteroaromatic ring partial structures, respectively;
  • - 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 oxidised to sulfoxides and sulfones
  • - carbonyl groups can be sulfated to form thiocarbonyl groups.
  • Salts of compounds I can be prepared in a manner known per se. For example, acid addition salts of compounds I are obtained by treatment with a suitable acid or with a suitable ion exchange reagent, and salts with bases are obtained by treatment with a suitable base or with a suitable ion exchange reagent
  • Salts of compounds I can be converted in customary manner into the free compounds I: acid addition salts, for example, by treatment with a suitable basic agent or with a suitable ion exchange reagent, and salts with bases, for example, by treatment with a suitable acid or with a suitable ion exchange reagent.
  • Some of the compounds I may be in the form of one of the possible isomers or in the form of a mixture thereof; for example, depending on the number and the absolute and relative configuration of the asymmetric carbon atoms, they may be in the form of pure isomers or in the form of mixtures of isomers, such as mixtures of enantiomers, for example racemates, mixtures of diastereoisomers or racemic mixtures; the invention relates both to the pure isomers and to all the possible mixtures of isomers and is to be understood thus hereinbefore and hereinafter, even though stereochemical details are not specifically mentioned in every case.
  • Mixtures of diastereoisomers and racemic mixtures of compounds I obtainable in accordance with the process or by other methods can be separated in known manner into the pure diastereoisomers or racemates on the basis of the physico-chemical differences between the constituents, for example by fractional crystallisation, distillation and/or by chromatography.
  • the invention relates also to novel starting materials and intermediates used for the preparation of the compounds of formula I, to their use and to processes for the preparation thereof.
  • the compounds II are known in free form or in salt form or can be prepared analogously to known compounds; appropriate details are provided, for example, on the one hand by D. J. Brown, "The Pyrimidines", in “Heterocyclic Compounds” and, on the other hand, in European Patent Application EP-A-0470600.
  • the compounds of formula III are novel and the present invention relates also to them. They can be prepared analogously to known compounds, for example as described below: a) For example, ammonia or an amine of the formula H 2 NR 4 can be reacted in customary manner in the presence of a reducing agent with a ketone of formula IV.
  • Suitable reducing agents are, for example, hydrogen (in the presence of a hydrogenation catalyst), zinc/hydrochloric acid, sodium cyanoborohydride, sodium borohydride, iron pentacarbonyl/alcoholic potassium hydroxide or formic acid. Compounds III wherein R 6 is hydrogen are thus obtained.
  • a compound of formula IV can also be converted in customary manner, using an unsubstituted or substituted hydroxylamine, into an unsubstituted or substituted oxime, which can be reduced to the corresponding amine III, the reducing agents used being, for example, complex metal hydrides, such as LiAlH 4 , zinc/acetic acid or hydrogen (in the presence of a hydrogenation catalyst, for example in the presence of Raney nickel or palladium-on-carbon).
  • complex metal hydrides such as LiAlH 4
  • zinc/acetic acid or hydrogen in the presence of a hydrogenation catalyst, for example in the presence of Raney nickel or palladium-on-carbon.
  • ketones of formula IV are in some cases known or can be prepared by reaction steps known per se: a) Compounds of formulae IVa and IVb are described, for example, in J. Med. Chem. 1992, vol. 35, p. 620 (IVa) and in German Patent Specification DE 3 107 601 (IVb).
  • the ring-closure reaction is carried out in a solvent and, when R is hydrogen, preferably in the presence of an agent promoting the removal of the elements of water, for example N,N'-dicyclohexylcarbodiimide, or, when R is C 1 -C 4 alkyl, preferably in the presence of an acid, for example sulfuric acid or p-toluenesulfonic acid.
  • R is hydrogen
  • an agent promoting the removal of the elements of water for example N,N'-dicyclohexylcarbodiimide
  • R is C 1 -C 4 alkyl
  • an acid for example sulfuric acid or p-toluenesulfonic acid.
  • Pyrimidines amino-substituted in the 4-position are already known, for example from patent application WO 92/08704.
  • the compounds I of the present invention differ structurally from those known compounds in characteristic manner; furthermore, the compounds of formula I of the present invention exhibit an unexpectedly high degree of microbicidal, insecticidal, nematicidal and acaricidal activity. Plants can be protected both by direct action on the pests and by activation and stimulation of their own defence system
  • the compounds of formula I of the present invention are oils, resins or solids that are stable at room temperature. In the agricultural sector and related fields they can be used preventively and/or curatively as active ingredients for controlling pests of plants. Even at low rates of concentration, the compounds of formula I according to the invention are not only distinguished by outstanding action but are also well tolerated by plants. They exhibit very advantageous, especially systemic, properties and can be used for protecting numerous cultivated plants. With the compounds of formula I, it is possible to inhibit or destroy the pests that occur in plants or in parts of plants (fruit, blossoms, leaves, stems, tubers, roots) in various crops of useful plants, while at the same time the parts of plants which grow later are also protected from attack by, e.g., phytopathogenic microorganisms.
  • Compounds I are effective, for example, against the phytopathogenic fungi belonging to the following classes: Fungi imperfecti (e.g. Botrytis, Pyricularia, Helminthosporium, Fusarium, Septoria, Cercospora and Alternaria) and Basidiomycetes (e.g. Rhizoctonia, Hemileia, Puccinia). They are also effective against the classes of the Ascomycetes (e.g. Venturia and Erysiphe, Podosphaera, Monilinia, Uncinula) and of the Oomycetes (e.g. Phytophthora, Pythium, Plasmopara).
  • Fungi imperfecti e.g. Botrytis, Pyricularia, Helminthosporium, Fusarium, Septoria, Cercospora and Alternaria
  • Basidiomycetes e.g. Rhizoctonia, Hemileia, Puccinia
  • They are also effective against
  • the compounds I can also be used as dressing agents for protecting seeds (fruit, tubers, grains) and plant cuttings against fungus infections as well as against phytopathogenic fungi that occur in the soil.
  • the compounds I according to the invention are also valuable active ingredients in the control of pests of the order Acarina and of the classes Insecta and Nematoda on useful plants and ornamentals in agriculture, especially in cotton, vegetable and fruit crops, in forestry, in the area of the protection of stored goods and materials, and, in the hygiene sector, in the control of animal pests, especially on domestic animals and productive livestock. They are effective against various stages of development. Their action may cause the pests to die immediately or only at a later date, for example at moulting, or it may manifest itself in a markedly reduced oviposition and/or hatching rate.
  • the order Acarina includes, for example, Boophilus spp. and Tetranychus spp.; this list does not constitute a limitation.
  • the invention relates also to the compositions that comprise as active ingredient compounds of formula I together with a carrier, especially crop-protecting compositions, and to their use in the agricultural sector and related fields.
  • the invention relates to the preparation of those compositions, which comprises homogeneously mixing the active ingredient with one or more of the extenders and dispersants described hereinafter.
  • the invention relates also to a method of treating plants which comprises applying thereto the novel compounds I or the novel compositions.
  • Target crops to be protected within the scope of the invention comprise, e.g., the following species of plants: cereals (wheat, barley, rye, oats, rice, maize, sorghum and related species); beet crops (sugar beet and fodder beet); pomes, stone fruit and soft fruit (apples, pears, plums, peaches, almonds, cherries, strawberries, raspberries and blackberries); leguminous plants (beans, lentils, peas, soybeans); oil plants (rape, mustard, poppy, olives, sunflowers, coconut, castor oil plants, cocoa beans, groundnuts); cucumber plants
  • Compounds I are normally applied in the form of compositions and can be applied to the crop area or plant to be treated, simultaneously or in succession, with further compounds.
  • These other compounds may be, for example, fertilisers, micronutrient donors or other preparations that influence plant growth. It is also possible to use selective herbicides and also insecticides, fungicides, bactericides, nematicides, molluscicides or mixtures of several of those preparations, if desired together with further carriers, surfactants or application-promoting adjuvants customarily employed in formulation technology.
  • Suitable carriers and adjuvants may be solid or liquid and are substances ordinarily employed in formulation technology, for example natural or regenerated mineral substances, solvents, dispersants, wetting agents, tackifiers, thickeners, binders or fertilisers.
  • a preferred method of applying a compound of formula I, or an agrochemical composition that comprises at least one of those compounds, is foliar application.
  • the frequency and rate of application depend on the risk of infestation by the co ⁇ esponding pathogen.
  • the compounds I can, however, also penetrate the plants through the roots via the soil
  • the compounds I may, however, also be applied to seeds (coating) either by impregnating the seeds with a liquid formulation comprising the compound or by coating them with a solid formulation.
  • the compounds I are used in unmodified form or preferably together with the adjuvants conventionally employed in formulation technology, and are therefore advantageously formulated in known manner, e.g. into emulsifiable concentrates, coatable pastes, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts or granules, for example by encapsulation in e.g. polymer substances.
  • the methods of application such as spraying, atomising, dusting, scattering, coating or pouring, are chosen in accordance with the intended objectives and the prevailing circumstances.
  • Advantageous rates of application are generally from 5 g to 2 kg of active ingredient (a.i.) per hectare (ha), preferably from 10 g to 1 kg a.i./ha, most preferably from 20 g to 600 g a.i./ha.
  • concentrations of from 10 mg to 1 g of active substance per kg of seed are advantageously used.
  • compositions, preparations or mixtures comprising the compound (active ingredient) of formula I and, where appropriate, a solid or liquid adjuvant are prepared in known manner, e.g. by homogeneously mixing and/or grinding the active ingredient with extenders, e.g. solvents, solid carriers and, where appropriate, surface-active compounds (surfactants).
  • extenders e.g. solvents, solid carriers and, where appropriate, surface-active compounds (surfactants).
  • Suitable solvents are: aromatic hydrocarbons, preferably the fractions containing 8 to 12 carbon atoms, such as xylene mixtures or substituted naphthalenes, phthalates, such as dibutyl or dioctyl phthalate, aliphatic hydrocarbons, such as cyclohexane, or paraffins, alcohols and glycols and their ethers and esters, such as ethanol, ethylene glycol, ethylene glycol monomethyl or monoethyl ether, ketones, such as cyclohexanone, strongly polar solvents, such as N-methyl-2-pyrrolidone, dimethyl sulfoxide or dimethylformamide, and vegetable oils or epoxidised vegetable oils, such as epoxidised coconut oil or soybean oil, and water.
  • aromatic hydrocarbons preferably the fractions containing 8 to 12 carbon atoms, such as xylene mixtures or substituted naphthalenes, phthalates, such as dibutyl or di
  • the solid carriers used are normally natural mineral fillers such as calcite, talcum, kaolin, montmorillonite or attapulgite.
  • Suitable granulated adsorptive carriers are porous types, for example pumice, broken brick, sepiolite or bentonite; and suitable nonsorbent carriers are e.g. calcite or sand.
  • a great number of pregranulated materials of inorganic or organic nature can be used, such as dolomite or pulverised plant residues.
  • suitable surface- active compounds are non-ionic, cationic and/or anionic surfactants having good emulsifying, dispersing and wetting properties.
  • surfactants will also be understood as comprising mixtures of surfactants.
  • non-ionic surfactants are nonylphenolpolyethoxyethanols, castor oil polyglycol ethers, polypropylene/polyethylene oxide adducts, tributylphenoxy- polyethoxyethanol, polyethylene glycol and octylphenoxypolyethoxyethanol.
  • Fatty acid esters of polyoxyethylene sorbitan e.g. polyoxyethylene sorbitan trioleate, are also suitable non-ionic surfactants.
  • Cationic surfactants are preferably quaternary ammonium salts which contain, as
  • N-substituent at least one C 8 -C 22 alkyl radical and, as further substituents, unsubstituted or halogenated lower alkyl, benzyl or hydroxy-lower alkyl radicals.
  • the agrochemical compositions generally comprise 0.1 to 99 % by weight, preferably 0.1 to 95 % by weight, of a compound of formula I, 99.9 to 1 % by weight, preferably 99.8 to 5 % by weight, of a solid or liquid adjuvant and 0 to 25 % by weight, preferably 0.1 to 25 % by weight, of a surfactant.
  • compositions may also comprise other adjuvants, such as stabilisers, antifoams, viscosity regulators, binders or tackifiers, and also fertilisers or other active ingredients for obtaining special effects.
  • adjuvants such as stabilisers, antifoams, viscosity regulators, binders or tackifiers, and also fertilisers or other active ingredients for obtaining special effects.
  • Example P- 1a At room temperature, 36.9 g of 6-(1-aminoethyl)-2H-1,4-benzoxazin-3-one, 32.3 g of 4,5-dichloro-6-ethylpyrimidine and 21.8 g of triethylamine are placed in a mixture of 800 ml of isopropanol and 100 ml of dimethylformamide in a sulfonating flask and then the reaction mixture is stirred for 12 hours at approximately 80°. The solvent is then removed under a water-jet vacuum and the residue is stirred well in 250 ml of water. The mixture is then filtered with suction and the dried crude product is introduced into 200 ml of ether.
  • Example P- 1b Under N 2 , 0.44 g of NaH ( ⁇ 55 % in oil) is placed in 10 ml of absolute THF in a sulfonating flask. A solution of 3.33 g of 6-[1-(5-chloro-6-ethylpyrimidin-4-ylamino)- ethyl]-2H-1,4-benzoxazin-3-one and 50 ml of THF is then added dropwise over the course of approximately 10 minutes in such a manner that the internal temperature does not exceed 15°. 1.7 g of methyl iodide are then added dropwise at room temperature over the course of approximately 15 minutes. Reflux is maintained for 4 hours and then the solvent is removed under a water-jet vacuum.
  • Example P-1c 10 g of 6-[1-(5-chloro-6-ethylpyrimidin-4-ylamino)ethyl]-2H-1,4-benz- oxazin-3-one and 10 g of phosphorus pentasulfide are placed in a mixture of 100 ml of toluene and 40 ml of dioxane in a sulfonating flask and then the reaction mixture is stirred for 5 hours at approximately 85°. It is then filtered while hot and the solvent is removed under a water-jet vacuum. The residue is taken up in ethyl acetate/water and the organic phase is washed twice with water and once with 2 % aqueous sodium hydrogen carbonate solution.
  • glycol ether (30 mol of ethylene- oxy units) - 12% 4%
  • Emulsions of any desired dilution can be produced from such emulsifiable concentrates using water.
  • Example F-2 Emulsifiable concentrate
  • N-methylpyrrolid-2-one 20% - - epoxidised coconut oil - - 1% 5% petroleum fraction
  • Wheat plants are sprayed to drip point 6 days after sowing with an aqueous spray mixture (0.02% active ingredient) prepared from a wettable powder formulation of the test compound. After 24 hours the treated plants are infected with a uredospore suspension of the fungus. The infected plants are incubated for 48 hours (conditions: 95 to 100 % relative humidity at 20°) and then stood in a greenhouse at 22°. The action of the test compound is assessed by evaluating rust pustule development 12 days after infection. b) Systemic action
  • Wheat plants are watered 5 days after sowing with an aqueous spray mixture (0.006% active ingredient, based on the volume of the soil) prepared from a wettable powder formulation of the test compound. Care is taken that the spray mixture does not come into contact with the parts of the plants above the soil. After 48 hours the treated plants are infected with a uredospore suspension of the fungus. The infected plants are incubated for 48 hours (conditions: 95 to 100 % relative humidity at 20°) and then stood in a greenhouse at 22°. The action of the test compound is assessed by evaluating rust pustule development 12 days after infection.
  • Compounds of Tables 1-8 exhibit good activity against Puccinia fungi.
  • compounds P-1a, P-1b, P-1c, 1.4, 2.11, 3.4, 3.48, 3.58, 5.11, 5.13, 5.16, 5.35, 5.38 and 5.67 reduce fungus attack to 0-20%.
  • fungus attack is 100 % on untreated and infected control plants.
  • Example B-2 Action against Phytophthora infestans on tomatoes
  • aqueous spray mixture (0.02% active ingredient) prepared from a wettable powder formulation of the test compound. After 24 hours the treated plants are infected with a sporangia suspension of the fungus. The action of the test compound is assessed by evaluating the fungus attack 5 days after infection, during which time 90 to 100 % relative humidity and a temperature of 20° are maintained.
  • tomato plants are watered with an aqueous spray mixture (0.006% active ingredient, based on the volume of the soil) prepared from a wettable powder formulation of the test compound. Care is taken that the spray mixture does not come into contact with the parts of the plants above the soil. After 48 hours the treated plants are infected with a sporangia suspension of the fungus. The action of the test compound is assessed by evaluating the fungus attack 5 days after infection, during which time 90 to 100 % relative humidity and a temperature of 20° are maintained.
  • Compounds of Tables 1-8 exhibit good activity.
  • compounds P-1a, P-1b, P-1c, 1.4, 2.11, 3.4, 3.48, 3.58, 5.11, 5.13, 5.16, 5.35, 5.38 and 5.67 reduce fungus attack to 0-20 %.
  • fungus attack is 100 % on untreated and infected control plants.
  • Example B-3 Residual-protective action against Cercospora arachidicola on groundnuts
  • Groundnut plants 10 to 15 cm in height are sprayed to drip point with an aqueous spray mixture (0.02% active ingredient) prepared from a wettable powder formulation of the test compound.
  • an aqueous spray mixture (0.02% active ingredient) prepared from a wettable powder formulation of the test compound.
  • the treated plants are infected with a conidia suspension of the fungus.
  • the infected plants are incubated for 72 hours at 21° and high humidity and then stood in a greenhouse until the typical leaf specks occur. Evaluation of the action of the test compound is made 12 days after infection and is based on the number and size of the specks.
  • Compounds of Tables 1-8 exhibit good activity.
  • compounds P-1a, P-1b, P-1c, 1.4, 2.11, 3.4, 3.48, 3.58, 5.11, 5.13, 5.16, 5.35, 5.38 and 5.67 reduce fungus attack to 0-20 %.
  • fungus attack is 100 % on untreated and infected control plants.
  • Example B-4 Action against Plasmopara viticola on vines
  • fungus attack is 100 % on untreated and infected control plants.
  • Example B-5 Action against Colletotrichum lagenarium on cucumbers
  • cucumber plants are sprayed with a spray mixture (concentration 0.002 %) prepared from a wettable powder formulation of the test compound. After 2 days the treated plants are infected with a spore suspension (1.5x10 5 spores/ml) of the fungus. The infected plants are incubated for 36 hours at 23° and high humidity.
  • Example B-6 Residual-protective action against Venturia inaequalis on apples
  • Apple cuttings with 10 to 20 cm long fresh shoots are sprayed to drip point with an aqueous spray mixture (0.02 % active ingredient) prepared from a wettable powder formulation of the test compound.
  • an aqueous spray mixture (0.02 % active ingredient) prepared from a wettable powder formulation of the test compound.
  • the treated plants are infected with a conidia suspension of the fungus.
  • the infected plants are incubated for 5 days at 90 to 100 % relative humidity and stood in a greenhouse for a further 10 days at 20 to 24°.
  • the action of the test compound is assessed by evaluating scab infestation 15 days after infection.
  • Example B-7 Action against Erysiphe graminis on barley
  • Barley plants about 8 cm in height are sprayed to drip point with an aqueous spray mixture
  • Barley plants about 8 cm in height are watered with an aqueous spray mixture (0.002 % active ingredient, based on the volume of the soil) prepared from a wettable powder formulation of the test compound. Care is taken that the spray mixture does not come into contact with the parts of the plants above the soil. After 48 hours the treated plants are dusted with conidia of the fungus. The infected plants are then stood in a greenhouse at 22°. The action of the test compound is assessed by evaluating the fungus attack 10 days after infection.
  • Compounds of Tables 1-8 exhibit good activity.
  • compounds P-1a, P-1b, P-1c, 1.4, 2.11. 3.4, 3.48, 3.58, 5.11, 5.13, 5.16, 5.35, 5.38 and 5.67 reduce fungus attack to 0-20 %.
  • fungus attack is 100 % on untreated and infected control plants.
  • Example B-8 Action against Podosphaera leucotricha on apple shoots
  • Apple cuttings with fresh shoots about 15 cm long are sprayed with a spray mixture (0.06 % active ingredient). After 24 hours the treated plants are infected with a conidia suspension of the fungus. The infected plants are stood in a climatic chamber at 70 % relative humidity and 20°. Evaluation of the fungus attack is made 12 days after infection.
  • Young bean plants are populated with a mixed population of Tetranychus urticae and one day later are sprayed with an aqueous emulsion comprising 400 ppm of the test compound. The plants are then incubated for 6 days at 25° and then evaluation is made. The percentage reduction in the population (% activity) is determined by comparing the number of dead eggs, larvae and adults on the treated plants with that on the untreated plants.
  • Rice plants are treated with an aqueous emulsion comprising 400 ppm of the test compound. After the spray coating has dried, the rice plants are populated with larvae of plant- hoppers in the L 2 and L 3 stages. Evaluation is made after 21 days. The percentage reduction in the population (% activity) is determined by comparing the number of surviving hoppers on the treated plants with that on the untreated plants.
  • the compounds of Tables 1-8 are more than 70 % effective.
  • Dwarf bean plants 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 infection the products are applied to the plants in concentrations of 200, 100, 50 mg a.i./L using an automatic spray cabin.
  • the test compounds are in the form of formulations and are diluted with water to the appropriate concentrations. The test is evaluated 2 and 7 days after application for percentage mortality in respect of
  • Rice plants are treated with an aqueous emulsion comprising 400 ppm of the test compound. After the spray coating has dried, the rice plants are populated with larvae of plant-hoppers in the L 2 and L 3 stages. Evaluation is made after 21 days. The percentage reduction in the population (% activity) is determined by comparing the number of surviving hoppers on the treated plants with that on the untreated plants.
  • the compounds of Table 3 exhibit good activity in this test.
  • compounds 3.4, 3.8, 3.11 and 3.20 are more than 80 % effective.
  • Young cabbage plants are sprayed with an aqueous emulsion comprising 400 ppm of the test compound. After the spray coating has dried, each cabbage plant is populated with 10 caterpillars in the third stage of Plutella xylostella and placed in a plastics container. Evaluation is made after 3 days. The percentage reduction in the population and the percentage reduction in feeding damage (% activity) are determined by comparing the number of dead caterpillars and the feeding damage on the treated plants with that on the untreated plants.

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  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

Composés de la formule (I), dans lesquels le substituant A se trouve en position α-, β-, η- ou δ- et dans lesquels X représente oxygène ou soufre; Y représente un groupe -CH(R15)-, oxygène, soufre ou un groupe -N(R16)-, n vaut 1 ou 2; et R1 à R16 sont tels que définis dans le descriptif, ces composés pouvant être utilisés à la fois sous leur forme libre ou sous forme d'un sel. Ils se prêtent à une utilisation comme principes actifs agrochimiques dans la lutte contre les nuisibles.
PCT/EP1994/000337 1993-02-18 1994-02-07 Derives de pyrimidine et leur utilisation comme pesticides WO1994019340A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
AU60392/94A AU6039294A (en) 1993-02-18 1994-02-07 Pyrimidine derivatives and their use as pesticides
JP6518602A JPH08507053A (ja) 1993-02-18 1994-02-07 ピリミジン誘導体および有害生物防除剤としてのそれらの使用方法
EP94906911A EP0694034A1 (fr) 1993-02-18 1994-02-07 Derives de pyrimidine et leur utilisation comme pesticides

Applications Claiming Priority (2)

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CH509/93-0 1993-02-18
CH50993 1993-02-18

Publications (1)

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WO1994019340A1 true WO1994019340A1 (fr) 1994-09-01

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EP (1) EP0694034A1 (fr)
JP (1) JPH08507053A (fr)
AU (1) AU6039294A (fr)
IL (1) IL108664A0 (fr)
MX (1) MX9401223A (fr)
TW (1) TW242557B (fr)
WO (1) WO1994019340A1 (fr)
ZA (1) ZA941081B (fr)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6015800A (en) * 1997-09-03 2000-01-18 Warner-Lambert Company Substituted quinoxaline-2-ones as glutamate receptor antagonists
EP1229913A1 (fr) * 1999-11-18 2002-08-14 Antexpharma, Inc. 1-benzazepines substituees et leurs derives
EP1283199A1 (fr) * 2000-05-16 2003-02-12 Takeda Chemical Industries, Ltd. Antagoniste de l'hormone de concentration de la melanine
EP1392317A2 (fr) * 2001-05-16 2004-03-03 Antexpharma, Inc. 1-benzazepines substituees et leurs derives
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 (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1992008704A1 (fr) * 1990-11-19 1992-05-29 E.I. Du Pont De Nemours And Company Aminopyrimidines insecticides, acaricides et fongicides
EP0555183A1 (fr) * 1992-02-07 1993-08-11 Ciba-Geigy Ag Pesticides

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1992008704A1 (fr) * 1990-11-19 1992-05-29 E.I. Du Pont De Nemours And Company Aminopyrimidines insecticides, acaricides et fongicides
EP0555183A1 (fr) * 1992-02-07 1993-08-11 Ciba-Geigy Ag Pesticides

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, Columbus, Ohio, US; *

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6015800A (en) * 1997-09-03 2000-01-18 Warner-Lambert Company Substituted quinoxaline-2-ones as glutamate receptor antagonists
EP1229913A1 (fr) * 1999-11-18 2002-08-14 Antexpharma, Inc. 1-benzazepines substituees et leurs derives
EP1229913A4 (fr) * 1999-11-18 2005-01-19 Antexpharma Inc 1-benzazepines substituees et leurs derives
EP1283199A1 (fr) * 2000-05-16 2003-02-12 Takeda Chemical Industries, Ltd. Antagoniste de l'hormone de concentration de la melanine
EP1283199A4 (fr) * 2000-05-16 2003-12-17 Takeda Chemical Industries Ltd Antagoniste de l'hormone de concentration de la melanine
EP1392317A2 (fr) * 2001-05-16 2004-03-03 Antexpharma, Inc. 1-benzazepines substituees et leurs derives
EP1392317A4 (fr) * 2001-05-16 2005-10-19 Antexpharma Inc 1-benzazepines substituees et leurs derives
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
JPH08507053A (ja) 1996-07-30
TW242557B (fr) 1995-03-11
IL108664A0 (en) 1994-05-30
EP0694034A1 (fr) 1996-01-31
AU6039294A (en) 1994-09-14
ZA941081B (en) 1994-08-18
MX9401223A (es) 1994-08-31

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