EP0694034A1 - Pyrimidine derivatives and their use as pesticides - Google Patents

Pyrimidine derivatives and their use as pesticides

Info

Publication number
EP0694034A1
EP0694034A1 EP94906911A EP94906911A EP0694034A1 EP 0694034 A1 EP0694034 A1 EP 0694034A1 EP 94906911 A EP94906911 A EP 94906911A EP 94906911 A EP94906911 A EP 94906911A EP 0694034 A1 EP0694034 A1 EP 0694034A1
Authority
EP
European Patent Office
Prior art keywords
alkyl
hydrogen
substituted
unsubstituted
group
Prior art date
Legal status (The legal status 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 status listed.)
Withdrawn
Application number
EP94906911A
Other languages
German (de)
French (fr)
Inventor
Harald Walter
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Novartis AG
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
Publication of EP0694034A1 publication Critical patent/EP0694034A1/en
Withdrawn legal-status Critical Current

Links

Classifications

    • 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:
  • Ri is hydrogen, C r C 4 alkyl, C ⁇ -C 4 alkoxy, halo-C 1 -C 4 alkyl having 1, 2 or 3 halogen atoms, or C ⁇ -C 4 alkylthio;
  • R 2 and R 3 are each independently of the other hydrogen, C C 4 alkyl, halo-C r C 4 alkyl having 1, 2 or 3 halogen atoms, C 1 -C 2 alkoxy-C 1 -C 4 alkyl, nitro-C ⁇ -C 4 alkyl, cyano-C r C 4 - alkyl, alkanoyl-C 1 -C 4 alkyl, alkoxycarbonyl-Ci- alkyl, C 1 -C 2 alkylthio-C 1 -C 4 alkyl,
  • N C(R 13 )R 14 ;
  • R 4 is hydrogen, C r C 4 alkyl, halo-C r C 4 alkyl having 1, 2 or 3 halogen atoms, C ⁇ -C 2 - alkoxy-C r C 4 alkyl, nitro-C r C 4 alkyl, cyano-C r C 4 alkyl, C 3 -C 5 cycloalkyl, benzyl, C r 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 r C 2 alkyl, nitro and cyano;
  • R 5 and R 6 are each independently of the other hydrogen, C,-C 4 alkyl, halo-C r C 4 alkyl having 1, 2 or 3 halogen atoms, C 1 -C 2 alkoxy-C I -C 4 alkyl, nitro-C 1 -C 4 alkyl, cyano-C r C 4 - alkyl, alkoxycarbonyl-C ⁇ -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 hydro ⁇ carbon radical containing up to 8 carbon atoms, an unsubstituted or substituted cyclic, saturated or unsaturated hydrocarbon radical containing up to 10 carbon atoms, unsubstit ⁇ uted or substituted benzyl, an unsubstit
  • Rg, R 9 , R 10 and R ⁇ are each independently of the others hydrogen, halogen, C ⁇ -C 4 alkyl, halo-C ⁇ -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 r C alkoxy, halo-C j -C 4 alkoxy having 1, 2 or 3 halogen atoms, C 3 -C- ⁇ cycloalkoxy, C r C alkylthio, halo-C r 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 unsub ⁇ stituted or substituted by one, two or three substituents selected from the group consisting of halogen, C
  • R 12 is C r C 4 alkyl, benzyl, C C 4 alkanoyl, benzoyl, the phenyl group of which is unsubstit ⁇ uted or substituted by one, two or three substituents selected from the group consisting of halogen and C 1 -C 2 alkyl, C r C 4 alkylthio, halo-C r C 4 alkylthio having 1, 2 or 3 halogen atoms, cyano-Cj-C-ialkylthio, 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 r C 2 alkyl, nitro and cyano; R 13 is C r C 4 alkyl; R 1 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-*-C 4 alkyl;
  • R 16 is hydrogen, C ⁇ -C 4 alkyl, C alkanoyl, benzoyl, the phenyl group of which is unsub ⁇ stituted or substituted by one, two or three substituents selected from the group consisting of halogen, C ⁇ -C 2 alkyl, nitro and cyano, C ⁇ -C 4 alkylsulfonyl, or aminosulfonyl, the nitrogen atom of which is unsubstituted or mono- or di-substituted by C ⁇ -C 4 alkyl; and n is 1 or 2; or a tautomer thereof, in each case in free form or in salt form.
  • 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.
  • 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-l-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-l-yl and but-l-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 substit ⁇ uted benzo group may have been fused onto such a heterocyclyl radical, which is bonded to the remainder of the molecule.
  • heterocyclyl groups are pyridyl, pyrimid- inyl, imidazolyl, thiazolyl, 1,3,4-thiadiazolyl, triazolyl, thienyl, furanyl, pyrrolyl, morpho- linyl, 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 ⁇ -C 4 alkyl, halo-C 1 -C 4 alkyl having 1, 2 or 3 halogen atoms, C ⁇ -C 2 - alkoxy-C 1 -C 4 alkyl, nitro-C 1 -C 4 alkyl, cyano-C alkyl, alkanoyl-Ci-Qalkyl, alkoxy- carbonyl-C ⁇ -C 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 r C 2 alkyl, halomethyl, halogen, nitro and amino, C r C 4 alkanoyl that is unsubstituted or substituted by halogen or by C 1 -C 2 alkoxy, C r C 4 thioalkanoyl, benzoyl, the phenyl group of
  • 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 alkyl)silyl or by an epoxy group, C-cQalkanoyl that is unsubstituted or substituted by from 1 to 3 halogen atoms, C r C 2 alkoxy, phenoxy, amino or by dimethylamino, or a group
  • Tj 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 ⁇ -C 2 alkoxy, hydroxy, nitro, cyano, C r C 4 - alkanoyl, halo-C ⁇ -C 4 alkanoyl or by C ⁇ -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, halogen, hal
  • 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 ⁇ -C 4 alkyl)silyl, C j - alkanoyl that is unsubstituted or substituted by from 1 to 3 halogen atoms, C ⁇ -C 2 alkoxy, phenoxy, amino or by dimethylamino, or a group wherein
  • Ti and T 2 each independently of the other hydrogen, C r C 4 alkyl, phenyl or halophenyl, or Tj and T 2 , together with the nitrogen atom to which they are bonded, form piperidine or morpholine; and wherein the other substituents are as defined for formula I.
  • R 2 and R 3 are each independently of the other hydrogen, C r C 4 alkyl, halo-C 1 -C 4 alkyl having 1, 2 or 3 halogen atoms, C 2 -C 4 alkynyl, C 3 -C 5 Cycloalkyl, hydroxy or halogen;
  • R 4 is hydrogen, C ⁇ -C alkyl, C 3 -C 5 cycloalkyl or benzyl;
  • R 5 and R 6 are each independently of the other hydrogen, C r C 4 alkyl, halo-C r C 4 alkyl having 1, 2 or 3 halogen atoms, C r C 2 alkoxy-C ⁇ -C 4 alkyl or C 3 -C 6 cycloalkyl;
  • R 7 is hydrogen, C r C 4 alkyl, halo-C r C alkyl having 1, 2 or 3 halogen atoms, Cj-C alkoxy-C r C 4 alkyl, cyano-C r 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 ⁇ -C 2 alkyl, halomethyl, halogen, nitro and amino, C ⁇ -C alkanoyl that is unsubstituted or substituted by halogen or by C j - ⁇ alkoxy, C r C 4
  • R 8 , Rp, R 10 and R ⁇ 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 ⁇ -C alkyl;
  • R 16 is hydrogen, Cj- 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 r C 2 alkyl, nitro and cyano, C ⁇ -C 4 alkylsulfonyl, or aminosulfonyl, the nitrogen atom of which is unsubstituted or mono- or di-substituted by Cj-C 4 alkyl; and n is 1 or 2.
  • R 2 is hydrogen, C ⁇ -C 4 alkyl, halo-C r C 4 alkyl having 1, 2 or 3 halogen atoms, C C 2 - alkoxy-C ⁇ -C 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 r C 4 alkyl
  • R 6 is hydrogen; and wherein the other substituents are as defined for formula I.
  • R 7 is hydrogen, C r C 4 alkyl, C 1 -C 2 alkoxy-C 1 -C 4 alkyl, cyano-C r C 4 alkyl, C r C 4 alkanoyl that is unsubstituted or substituted by halogen or by C r C 2 alkoxy, C r C 4 thioalkanoyl, benzoyl, the phenyl group of which is unsubstituted or substituted by one or two substit ⁇ uents selected from the group consisting of halogen and C r 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 ⁇ -C 2 alkyl, C C 4 alkylsulfonyl, halo-C - alkylsulfonyl having 1, 2 or 3 halogen atoms, phenylsulfon
  • R 8 and R 9 are each independently of the other hydrogen, fluorine, chlorine or bromine;
  • R 10 and R ⁇ 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 r C 4 alkyl;
  • R 16 is hydrogen, C r 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 ⁇ -C 2 alkyl, nitro and cyano, - alkylsulfonyl, or aminosulfonyl, the nitrogen atom of which is unsubstituted or mono- or di-substituted by C ⁇ -C 4 alkyl; and n is 1 or 2.
  • R 8 and R 9 are each independently of the other hydrogen or fluorine;
  • R 10 and R ⁇ are hydrogen;
  • X is oxygen or sulfur;
  • Y is the group -CH 2 -, oxygen, sulfur or the group -NH-; and n is 1 or 2.
  • Y is the group -CH 2 s n is 1 or 2; and wherein the other substituents are as defined for formula I.
  • Ri is hydrogen or C r C alkyl
  • R 2 is hydrogen, C r C 4 alkyl, halo-C r C 4 alkyl having 1, 2 or 3 halogen atoms, C r C 2 - alkoxy-Cj- alkyl, cyclopropyl, ethynyl or halogen;
  • R 3 is hydrogen, fluorine, chlorine or bromine
  • R 4 is hydrogen or C r C 4 alkyl
  • R 5 is C r 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 ⁇ are hydrogen
  • X is oxygen or sulfur
  • Y is the group -CH 2 -; and n is 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
  • Rg 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 Rg 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 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
  • Rg, R 9 , R 10 and R ⁇ are each hydrogen
  • X is oxygen or sulfur
  • Y is oxygen or the group -CH 2 -; and n is 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 ⁇ -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 alkynyl, or acetyl that is unsubstituted or substituted by C r C 4 - alkoxy, phenoxy or by halogen.
  • R 5 is methyl or ethyl
  • R 7 is C j -C- j alkyl, C 2 -C alkenyl, C 2 -C alkynyl, or acetyl that is unsubstituted or substituted by C ⁇ -C 4 alkoxy, phenoxy or by halogen.
  • R 5 is methyl or ethyl
  • R 7 is C,-C 4 alkyl, C 2 -C 4 alkenyl, C 2 -C 4 alkynyl, or acetyl that is unsubstituted or substituted by C r 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:
  • R j , 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 m
  • R 4 to R ⁇ , 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 '-Z', R 7 '-Z' or R ⁇ '-Z' wherein R ⁇ 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
  • 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 approx ⁇ imately -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 approx ⁇ imately -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, Cj-Cgalkylthio, such as methylthio, ethylthio or propylthio, C r 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.
  • 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.
  • 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 melL 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 HI 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 intro ⁇ duction 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:
  • 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 IN 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 HI, 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.
  • a compound of formula IN is reacted with an amine of the formula H 2 ⁇ R 4 and formic acid or formamide and formic acid according to Leuckart and Wallach and the corresponding N-formyl derivative is hydrolysed.
  • ketones of formula IN are in some cases known or can be prepared by reaction steps known per se:
  • IVa R 5 - C in ⁇ -position
  • IVb R 5 - C in ⁇ -position
  • Reaction (I) is described, for example, in J. Chem. Soc. 1964, 3709.
  • 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'-dicyclohexylcarbod ⁇ mide, or, when R is C ⁇ -C 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'-dicyclohexylcarbod ⁇ mide
  • R is C ⁇ -C 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 structur ⁇ ally 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 (immunisation).
  • 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 micro ⁇ organisms.
  • 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 herein ⁇ after.
  • 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 (cucumber, marrows, melons); fibre plants (cotton, flax, hemp, jute); citrus fruit (oranges, lemons, grapefruit, mandarins); vegetables (spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes, paprika); lauraceae (avocado, cinnamon, camphor) and 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 fertil ⁇ isers.
  • 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 (systemic action) if the locus of the plant is impregnated with a liquid formulation, or if the compounds are applied in solid form to the soil, e.g. in granular form (soil application). In paddy rice crops, such granules may be applied in metered amounts to the flooded rice field.
  • 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.i7ha, most preferably from 20 g to 600 g a.iJha.
  • 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 emuls ⁇ ifying, 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 Cg-C 22 alkyl radical and, as further substituents, unsubstituted or halogenated lower alkyl, benzyl or hydroxy-lower alkyl radicals.
  • Other surfactants customarily used in formulation technology are known to the person skilled in the art and can be found in the relevant literature.
  • the agrochemical compositions generally comprise 0.1 to 99 % by weight, preferably 0.1 to 95 % by weight, of a compound of formula 1, 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- la At room temperature, 36.9 g of 6-(l-aminoethyl)-2H-l,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-lc 10 g of 6-[l-(5-chloro-6-ethylpyrimidin-4-ylamino)ethyl]-2H-l,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.
  • Emulsions of any desired dilution can be produced from such emulsifiable concentrates using water.
  • Example F-2 Emulsifiable concentrate
  • Emulsions of any desired dilution can be produced from this emulsifiable concentrate using water.
  • Ready-for-use dusts are obtained by intimately mixing all of the constituents.
  • 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.
  • an aqueous spray mixture 0.02% active ingredient
  • 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-la, P-lb, P-lc, 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 a) Residual-protective action
  • 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-la, P-lb, P-lc, 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-la, P-lb, P-lc, 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
  • 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 6 days after infection, during which time 95 to 100 % relative humidity and a temperature of 20° are maintained.
  • Compounds of Tables 1-8 exhibit good activity against Plasmopara viticola on vines. For example, compounds 1.2, 1.4, 1.33, 1.35, 3.4, 3.11, 3.20 and 3.58 reduce fungus attack to 0-20 %. On the other hand, fungus attack is 100 % on untreated and infected control plants.
  • Example B-5 Action against Colletotrichum lagenarium on cucumbers After two weeks' growth, cucumber plants are sprayed with a spray mixture (concen ⁇ tration 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 spores/ml) of the fungus. The infected plants are incubated for 36 hours at 23° and high humidity. Incubation is then continued at normal humidity and about 22°. The fungus attack which occurs is evaluated 8 days after infection.
  • a spray mixture (concen ⁇ tration 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 spores/ml) of the fungus. The infected plants are incubated for 36 hours at 23° and high humidity. Incubation is then continued at normal humidity and about 22°. The fungus attack which occurs is evaluated 8 days after
  • 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. After 24 hours 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 Ervsiphe graminis on barley a) Residual-protective action
  • 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.
  • 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 percen ⁇ tage 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 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 ⁇ 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.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

Compounds of formula (I), wherein the substituent A is in the α-, β-, η- or δ-position, and wherein: X is oxygen or sulfur; Y is a group -CH(R15)-, oxygen, sulfur or a group -N(R16)-; n is 1 or 2; and wherein R1 to R16 are as defined herein, both in free form and in salt form. Such compounds can be used as agrochemical active ingredients in pest control.

Description

PYRIMIDINE DERIVATIVES AND THEIR USE AS PESTICIDES
The invention relates to novel pesticidally active compounds of formula I
wherein the substituent A is in the α-, β-, γ- or δ-position and wherein:
Ri is hydrogen, CrC4alkyl, Cι-C4alkoxy, halo-C1-C4alkyl having 1, 2 or 3 halogen atoms, or Cι-C4alkylthio;
R2 and R3 are each independently of the other hydrogen, C C4alkyl, halo-CrC4alkyl having 1, 2 or 3 halogen atoms, C1-C2alkoxy-C1-C4alkyl, nitro-Cι-C4alkyl, cyano-CrC4- alkyl, alkanoyl-C1-C4alkyl, alkoxycarbonyl-Ci- alkyl, C1-C2alkylthio-C1-C4alkyl,
Cι-C2alkanesulfinyl-Cι-C4alkyl, Cι-C2alkanesulfonyl-Cι-C4alkyl, C2-C4alkenyl, halo-
C2-C4alkenyl having 1, 2 or 3 halogen atoms, C2-C4alkynyl, C3-C7cycloalkyl, CrC4- alkoxy, halo-C1-C4alkoxy, Ci- alkylthio, halo-Cι-C alkylthio, C1-C4alkylsulfinyl,
Cι-C alkylsulfonyl, amino, C1-C4acylamino, nitro, cyano, hydroxy or halogen, a group of the formula N(H)R12ι a group of the formula N(R12)R13 or a group of the formula
N=C(R13)R14;
R4 is hydrogen, CrC4alkyl, halo-CrC4alkyl having 1, 2 or 3 halogen atoms, Cι-C2- alkoxy-CrC4alkyl, nitro-CrC4alkyl, cyano-CrC4alkyl, C3-C5cycloalkyl, benzyl, CrC4- 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, CrC2alkyl, nitro and cyano;
R5 and R6 are each independently of the other hydrogen, C,-C4alkyl, halo-CrC4alkyl having 1, 2 or 3 halogen atoms, C1-C2alkoxy-CI-C4alkyl, nitro-C1-C4alkyl, cyano-CrC4- alkyl, alkoxycarbonyl-Cι-C4alkyl or C3-C6cycloalkyl that is unsubstituted or substituted by one or two substituents selected from the group consisting of halogen and C1-C2alkyl; R7 is hydrogen, an unsubstituted or substituted open-chain, saturated or unsaturated hydro¬ carbon radical containing up to 8 carbon atoms, an unsubstituted or substituted cyclic, saturated or unsaturated hydrocarbon radical containing up to 10 carbon atoms, unsubstit¬ uted or substituted benzyl, an unsubstituted or substituted acyl or thioacyl group containing up to 12 carbon atoms, an unsubstituted or substituted Cι-C alkylsulfonyl, phenylsulfonyl or aminosulfonyl group, or an unsubstituted or substituted heterocyclyl radical;
Rg, R9, R10 and Rπ are each independently of the others hydrogen, halogen, Cι-C4alkyl, halo-Cι-C4alkyl having 1, 2 or 3 halogen atoms, C1-C2alkoxy-C1-C4alkyl, C3-C6cyclo- alkyl, CrC alkoxy, halo-Cj-C4alkoxy having 1, 2 or 3 halogen atoms, C3-C-τcycloalkoxy, CrC alkylthio, halo-CrC4alkylthio having 1, 2 or 3 halogen atoms, cyano, nitro, phenyl, phenoxy or phenylthio, the phenyl groups in phenyl, phenoxy and phenylthio being unsub¬ stituted or substituted by one, two or three substituents selected from the group consisting of halogen, CrC2alkyl and CrC2alkoxy, with the proviso that no more than one of those substituents R8, R9, R10 and Ru is unsubstituted or substituted phenyl, substituted phenoxy or substituted phenylthio;
R12 is CrC4alkyl, benzyl, C C4alkanoyl, benzoyl, the phenyl group of which is unsubstit¬ uted or substituted by one, two or three substituents selected from the group consisting of halogen and C1-C2alkyl, CrC4alkylthio, halo-CrC4alkylthio having 1, 2 or 3 halogen atoms, cyano-Cj-C-ialkylthio, 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, CrC2alkyl, nitro and cyano; R13 is CrC4alkyl; R1 is hydrogen or C1-C4alkyl; X is oxygen or sulfur;
Y is a group -CH(R15)-, oxygen, sulfur or a group -N(R16)-; R15 is hydrogen or C-*-C4alkyl;
R16 is hydrogen, Cι-C4alkyl, C alkanoyl, benzoyl, the phenyl group of which is unsub¬ stituted or substituted by one, two or three substituents selected from the group consisting of halogen, Cι-C2alkyl, nitro and cyano, Cι-C4alkylsulfonyl, or aminosulfonyl, the nitrogen atom of which is unsubstituted or mono- or di-substituted by Cι-C4alkyl; and n is 1 or 2; or a tautomer thereof, in each case in free form or in salt form.
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.
In addition, 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. Furthermore, where appropriate, 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.
Unless otherwise defined, the general terms used hereinbefore and hereinafter have the meanings listed below:
Depending on the number of carbon atoms, 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-l-yl. Alkenyl radicals having a chain length of 3 or 4 carbon atoms are preferred.
Depending on the number of carbon atoms, alkynyl may likewise be straight-chained or branched, and is, for example, propargyl, but-1-yn-l-yl and but-l-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.
Depending on the size of the ring, 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.
In accordance with the number of carbon atoms in each case, alkanoyl is either straight- chained or branched, and is, for example, formyl, acetyl, propionyl, butyryl, pivaloyl or octanoyl.
In 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 substit¬ uted benzo group may have been fused onto such a heterocyclyl radical, which is bonded to the remainder of the molecule. Examples of heterocyclyl groups are pyridyl, pyrimid- inyl, imidazolyl, thiazolyl, 1,3,4-thiadiazolyl, triazolyl, thienyl, furanyl, pyrrolyl, morpho- linyl, oxazolyl and the corresponding partially or totally hydrogenated rings. Examples of heterocyclyl groups having a fused benzo group are quinolyl, isoquinolyl, benzoxazolyl, quinoxalinyl, benzothiazolyl, benzimidazolyl, indolyl and indolinyl.
Preferred within the scope of the invention are:
(1) Compounds of formula I wherein:
R7 is hydrogen, Cι-C4alkyl, halo-C1-C4alkyl having 1, 2 or 3 halogen atoms, Cι-C2- alkoxy-C1-C4alkyl, nitro-C1-C4alkyl, cyano-C alkyl, alkanoyl-Ci-Qalkyl, alkoxy- carbonyl-Cι-C alkyl, C3-C5cycloalkyl, benzyl, phenyl that is unsubstituted or mono- to tri-substituted by the same or different substituents selected from the group consisting of CrC2alkyl, halomethyl, halogen, nitro and amino, CrC4alkanoyl that is unsubstituted or substituted by halogen or by C1-C2alkoxy, CrC4thioalkanoyl, benzoyl, the phenyl group of which is unsubstituted or substituted by one or two substituents selected from the group consisting of halogen, C1-C2alkyl, nitro and cyano; thiobenzoyl, the phenyl group of which is unsubstituted or substituted by one or two substituents selected from the group consisting of halogen, CrC2alkyl, nitro, cyano, amino, Cι-C acylamino and CrC4aIkoxy- carbonyl, C C4alkylsulfonyl, halo-CrC4alkylsulfonyl having 1, 2 or 3 halogen atoms, cyano-Cι-C alkylsulfonyl, phenylsulfonyl, the phenyl group of which is unsubstituted or substituted by one or two substituents selected from the group consisting of halogen, Cι-C2alkyl, nitro and cyano, aminosulfonyl, the nitrogen atom of which is unsubstituted or mono- or di-substituted by CrC alkyl, or heterocyclyl that is unsubstituted or mono- to tri-substituted by the same or different substituents selected from the group consisting of CrC2alkyl, halomethyl, halogen, nitro and amino; or a tautomer thereof, in each case in free form or in salt form; and wherein the other substituents are as defined for formula I.
(2) Compounds of formula I wherein:
R7 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- (C1-C alkyl)silyl or by an epoxy group, C-cQalkanoyl that is unsubstituted or substituted by from 1 to 3 halogen atoms, CrC2alkoxy, phenoxy, amino or by dimethylamino, or a group
-CH2CO-N(T,)(T2) or -CHjCHjCO-NCT.rø. wherein
Tj and T2 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, Cι-C2alkoxy, hydroxy, nitro, cyano, CrC4- alkanoyl, halo-Cι-C4alkanoyl or by Cι-C4alkoxycarbonyl, 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, C1-C2alkyl, 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 C1-C2alkyl, halogen, halomethyl, nitro and cyano; or
Ti and T2, 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 CrC4alkyl, phenyl, C-(-C4- 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, halomethyl and nitro; and wherein the other substituents are as defined for formula I.
(3) Compounds of formula I wherein:
R7 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(Cι-C4alkyl)silyl, Cj- alkanoyl that is unsubstituted or substituted by from 1 to 3 halogen atoms, Cι-C2alkoxy, phenoxy, amino or by dimethylamino, or a group wherein
Ti and T2 each independently of the other hydrogen, CrC4alkyl, phenyl or halophenyl, or Tj and T2, together with the nitrogen atom to which they are bonded, form piperidine or morpholine; and wherein the other substituents are as defined for formula I.
(4) Compounds of formula I wherein: Ri is hydrogen or Cι-C alkyl;
R2 and R3 are each independently of the other hydrogen, CrC4alkyl, halo-C1-C4alkyl having 1, 2 or 3 halogen atoms, C2-C4alkynyl, C3-C5Cycloalkyl, hydroxy or halogen;
R4 is hydrogen, Cι-C alkyl, C3-C5cycloalkyl or benzyl;
R5 and R6 are each independently of the other hydrogen, CrC4alkyl, halo-CrC4alkyl having 1, 2 or 3 halogen atoms, CrC2alkoxy-Cι-C4alkyl or C3-C6cycloalkyl; R7 is hydrogen, CrC4alkyl, halo-CrC alkyl having 1, 2 or 3 halogen atoms, Cj-C alkoxy-CrC4alkyl, cyano-CrC4alkyl, benzyl, phenyl that is unsubstituted or mono- to tri-substituted by the same or different substituents selected from the group consisting of Cι-C2alkyl, halomethyl, halogen, nitro and amino, Cι-C alkanoyl that is unsubstituted or substituted by halogen or by Cj-^alkoxy, CrC4thioalkanoyl, benzoyl, the phenyl group of which is unsubstituted or substituted by one or two substituents selected from the group consisting of halogen and C1-C2alkyl; thiobenzoyl, the phenyl group of which is unsubstit¬ uted or substituted by one or two substituents selected from the group consisting of halogen and CrC4alkylsulfonyl, halo-CrC4alkylsulfonyl having 1, 2 or 3 halogen atoms, phenylsulfonyl, the phenyl group of which is unsubstituted or substituted by one or two substituents selected from the group consisting of halogen and C1-C alkyl, or aminosulfonyl, the nitrogen atom of which is unsubstituted or mono- or di-substituted by CrC4alkyl;
R8, Rp, R10 and Rπ are each independently of the other hydrogen, halogen or C1-C4alkyl; X is oxygen or sulfur;
Y is a group -CH(R15)-, oxygen, sulfur or a group -N(R16)-; R15 is hydrogen or Cι-C alkyl;
R16 is hydrogen, Cj- alkanoyl, benzoyl, the phenyl group of which is unsubstituted or substituted by one, two or three substituents selected from the group consisting of halogen, CrC2alkyl, nitro and cyano, Cι-C4alkylsulfonyl, or aminosulfonyl, the nitrogen atom of which is unsubstituted or mono- or di-substituted by Cj-C4alkyl; and n is 1 or 2.
(5) Compounds of formula I wherein the substituent A is in the β- or γ-position. (6) Compounds of formula I wherein: Rt is hydrogen or CrC4alkyl;
R2 is hydrogen, Cι-C4alkyl, halo-CrC4alkyl having 1, 2 or 3 halogen atoms, C C2- alkoxy-Cι-C alkyl, cyclopropyl, ethynyl or halogen;
R3 is hydrogen, fluorine, chlorine or bromine;
R4 is hydrogen or C1-C4alkyl;
R5 is CrC4alkyl;
R6 is hydrogen; and wherein the other substituents are as defined for formula I.
(7) Compounds of formula I wherein Rι-R$ are as defined in (6) and wherein:
R7 is hydrogen, CrC4alkyl, C1-C2alkoxy-C1-C4alkyl, cyano-CrC4alkyl, CrC4alkanoyl that is unsubstituted or substituted by halogen or by CrC2alkoxy, CrC4thioalkanoyl, benzoyl, the phenyl group of which is unsubstituted or substituted by one or two substit¬ uents selected from the group consisting of halogen and CrC2alkyl; thiobenzoyl, the phenyl group of which is unsubstituted or substituted by one or two substituents selected from the group consisting of halogen and Cι-C2alkyl, C C4alkylsulfonyl, halo-C - alkylsulfonyl having 1, 2 or 3 halogen atoms, phenylsulfonyl, the phenyl group of which is unsubstituted or substituted by one or two substituents selected from the group consisting of halogen and C C2alkyl, or aminosulfonyl, the nitrogen atom of which is unsubstituted or mono- or di-substituted by CrC4alkyl;
R8 and R9 are each independently of the other hydrogen, fluorine, chlorine or bromine; R10 and Rπ are hydrogen; X is oxygen or sulfur;
Y is a group -CH(R15)-, oxygen, sulfur or a group -N(R16)-; R15 is hydrogen or CrC4alkyl;
R16 is hydrogen, CrC4alkanoyl, benzoyl, the phenyl group of which is unsubstituted or substituted by one, two or three substituents selected from the group consisting of halogen, Cι-C2alkyl, nitro and cyano, - alkylsulfonyl, or aminosulfonyl, the nitrogen atom of which is unsubstituted or mono- or di-substituted by Cι-C4alkyl; and n is 1 or 2.
(8) Compounds of formula I wherein Ri-Rβ are as defined under (6) and wherein: R7 is hydrogen, methyl, ethyl or cyanomethyl;
R8 and R9 are each independently of the other hydrogen or fluorine; R10 and Rπ are hydrogen; X is oxygen or sulfur;
Y is the group -CH2-, oxygen, sulfur or the group -NH-; and n is 1 or 2.
(9) Compounds of formula I wherein the substituent A is either in the β-position or in the γ-position, and wherein:
Y is the group -CH2s n is 1 or 2; and wherein the other substituents are as defined for formula I.
(10) Compounds of formula I wherein the substituent A is either in the β-position or in the γ-position, and wherein:
Ri is hydrogen or CrC alkyl;
R2 is hydrogen, CrC4alkyl, halo-CrC4alkyl having 1, 2 or 3 halogen atoms, CrC2- alkoxy-Cj- alkyl, cyclopropyl, ethynyl or halogen;
R3 is hydrogen, fluorine, chlorine or bromine;
R4 is hydrogen or CrC4alkyl;
R5 is CrC4alkyl;
R6 is hydrogen;
R7 is hydrogen, methyl, ethyl or cyanomethyl;
R8 and R9 are each independently of the other hydrogen or fluorine;
R10 and Rπ are hydrogen;
X is oxygen or sulfur;
Y is the group -CH2-; and n is 1 or 2.
wherein: R2 is hydrogen, methyl or ethyl;
R3 is fluorine or chlorine;
R5 is methyl or ethyl;
R7 is hydrogen, methyl, ethyl or cyanomethyl;
R8 and R9 are each independently of the other hydrogen or fluorine; and
X is oxygen or sulfur.
(12) Compounds of formula 1.2,
wherein:
R2 is hydrogen, methyl or ethyl;
R3 is fluorine or chlorine;
R5 is methyl or ethyl;
R7 is hydrogen, methyl, ethyl or cyanomethyl;
Rg and R9 are each independently of the other hydrogen or fluorine; and
X is oxygen or sulfur.
(13) Compounds of formula I wherein the substituent A is either in the β-position or in the γ-position, and wherein:
Y is oxygen or sulfur; n is 1; and wherein the other substituents are as defined for formula I.
(14) Compounds of formula 1.3, wherein:
R2 is hydrogen, methyl or ethyl;
R3 is fluorine or chlorine;
R5 is methyl or ethyl;
R7 is hydrogen, methyl, ethyl or cyanomethyl;
R8 and Rg are each independently of the other hydrogen or fluorine; and
X is oxygen or sulfur.
(15) Compounds of formula 1.4,
wherein:
R2 is hydrogen, methyl or ethyl;
R3 is fluorine or chlorine;
R5 is methyl or ethyl;
R7 is hydrogen, methyl, ethyl or cyanomethyl;
R8 and R9 are each independently of the other hydrogen or fluorine; and
X is oxygen or sulfur.
(16) Compounds of formula 1.5, wherein:
R2 is hydrogen, methyl or ethyl;
R3 is fluorine or chlorine;
R5 is methyl or ethyl;
R7 is hydrogen, methyl, ethyl or cyanomethyl;
R8 and R9 are each independently of the other hydrogen or fluorine; and
X is oxygen or sulfur.
(17) Compounds of formula 1.6,
wherein:
R2 is hydrogen, methyl or ethyl;
R3 is fluorine or chlorine;
R5 is methyl or ethyl;
R7 is hydrogen, methyl, ethyl or cyanomethyl;
R8 and R9 are each independently of the other hydrogen or fluorine; and
X is oxygen or sulfur.
(18) Compounds of formula I wherein the substituent A is either in the β-position or in the γ-position, and wherein:
Ri is hydrogen;
R2 is methyl or ethyl;
R3 is chlorine; R4 is hydrogen;
R5 is methyl, ethyl or cyclopropyl;
R6 is hydrogen;
R7 is hydrogen, methyl, ethyl, cyanomethyl or methylsulfonyl;
Rg, R9, R10 and Rπ are each hydrogen;
X is oxygen or sulfur;
Y is oxygen or the group -CH2-; and n is 1 or 2.
(19) Compounds of formula 1.7,
wherein the substituent A is either in the β-position or in the γ-position, and wherein: R5 is methyl or ethyl; and
R7 is Cι-C4alkyl that is unsubstituted or substituted by from 1 to 3 halogen atoms or by cyano, C2-C4alkenyl, C2-C alkynyl, or acetyl that is unsubstituted or substituted by CrC4- alkoxy, phenoxy or by halogen.
(20) Compounds of formula 1.8,
wherein:
R5 is methyl or ethyl; and
R7 is Cj-C-jalkyl, C2-C alkenyl, C2-C alkynyl, or acetyl that is unsubstituted or substituted by Cι-C4alkoxy, phenoxy or by halogen. (21) Compounds of formula 1.9,
wherein:
R5 is methyl or ethyl; and
R7 is C,-C4alkyl, C2-C4alkenyl, C2-C4alkynyl, or acetyl that is unsubstituted or substituted by CrC4alkoxy, 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 Ri-Rπ, X» Y nd n are as defined for formula I, a compound of formula π
wherein Rj, R2 and R3 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 m
or with a salt thereof, wherein R4 to Rπ, X, Y and n are as defined for formula I; or b) for the preparation of a compound of formula I wherein R4, R7 and R16 are as defined for formula I but are other than hydrogen, a compound of formula I wherein R4, R7 and R16 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 '-Z', R7'-Z' or R^'-Z' wherein R \ R7' and R16' are as defined in formula I for R4, R7 and R16, 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 thionating agent, preferably with phosphorus pentasulfide or 4-methoxyphenylthiophosphonic acid cyclodithioanhydride (Lawesson's reagent).
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 approx¬ imately -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, Cj-Cgalkylthio, such as methylthio, ethylthio or propylthio, CrC8alkanoyloxy, such as acetoxy, (halo-)C1-C8alkanesulfonyloxy, such as methanesulfonyloxy, ethane- sulfonyloxy or trifluoromethanesulfonyloxy, or unsubstituted or substituted phenylsulfon- yloxy, such as benzenesulfonyloxy or p-toluenesulfonyloxy, and also hydroxy.
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. There may be mentioned by way of example sodium hydroxide, hydride, amide, methanolate and carbonate, potassium tert-butanolate and carbonate, lithium dϋsopropyl- amide, potassium bis(trimethylsilyl)amide, calcium hydride, triethylamine, triethylene- diamine, cyclohexylamine, N-cyclohexyl-N,N-dimethylamine, N,N-diethylaniline, pyridine, 4-(N,N-dimethylamino)pyridine, N-methylmorpholine, benzyltrimethyl- ammonium hydroxide and l,8-diazabicyclo[5.4.0]undec-5-ene (DBU).
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 melL In most cases, however the addition of an inert solvent or diluent or a mixture thereof is advantageous. There may be mentioned as examples of such 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-dimethyl- acetamide, N-methylpyrrolidone or hexamethylphosphoric acid triamide; nitriles, such as acetonitrile; and sulfoxides, such as dimethyl sulfoxide. Bases used in excess, such as triethylamine, pyridine, N-methylmorpholine or N,N-diethylaniline, may also be used as solvents or diluents.
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.
In a preferred form of the process a compound II wherein Z is halogen, preferably chlorine, is reacted with a compound HI 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 R4, R7 and/or R16 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 intro¬ duction of the substituents R4, R7 and/or R16 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 R7 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
For example:
- 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;
- alkanoyl, benzoyl or sulfonyl substituents can be replaced by readily replaceable hydrogen 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 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 H2NR4 can be reacted in customary manner in the presence of a reducing agent with a ketone of formula IV.
IN m'
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 R6 is hydrogen are thus obtained. b) A compound of formula IN 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 HI, the reducing agents used being, for example, complex metal hydrides, such as LiAlH4, zinc/acetic acid or hydrogen (in the presence of a hydrogenation catalyst, for example in the presence of Raney nickel or palladium-on-carbon).
OR Ν' ΝH2OR || H2cat ► R5-C — ►
Compounds of formula III wherein R6 is hydrogen are thus obtained.
c) According to another variant, a compound of formula IN is reacted with an amine of the formula H2ΝR4 and formic acid or formamide and formic acid according to Leuckart and Wallach and the corresponding N-formyl derivative is hydrolysed.
d) Compounds of formula HI wherein X is sulfur can be prepared by reacting compounds of formula III wherein X is oxygen with a thionating agent, preferably with phosphorus pentasulfide or 4-methoxyphenylthiophosphonic acid cyclodi-thioanhydride (Lawesson' s reagent).
The ketones of formula IN 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).
O O II II
IVa: R5- C in β-position IVb: R5- C in γ-position
b) Compounds of formulae IVe and IVd
o O
II II IVe: R5- C in β-position IVd: R5- C in γ-position
Reaction (I) is described, for example, in J. Chem. Soc. 1964, 3709.
c) The compounds of formulae IVe and IVf are described, for example, in Ann. Chim. (Rome) 1955. vol. 45, p. 172 (IVe) and Indian J. Chem. 1983. 22B, p. 1236 (IVf).
O II
IVe: R5- C in β-position IVf: R5-C in γ-position
d) Compounds of formulae IVg and IVh can be prepared, for example, as follows:
O II IVg: R5- C in β-position
O II IVh: R5-C in γ-position
This reaction is described, for example, in J. Heterocycl. Chem. 1992. vol. 29, p. 129.
e) Compounds of formula INi are described, for example, in J. Org. Chem. 1969. vol. 34, p. 1070.
f) Compounds of formula IVj can be prepared, for example, as follows:
IVj g) In addition, compounds of the general formula IVk, wherein R5, Y and n are as defined for formula I, can be prepared by reductive cyclisation of a corresponding nitro compound wherein R is hydrogen or Cι-C4alkyl, in accordance with the following reaction scheme:
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'-dicyclohexylcarbodϋmide, or, when R is Cι-C alkyl, preferably in the presence of 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 structur¬ ally 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 (immunisation).
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 micro¬ organisms.
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).
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. In addition, 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 herein¬ after. 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 (cucumber, marrows, melons); fibre plants (cotton, flax, hemp, jute); citrus fruit (oranges, lemons, grapefruit, mandarins); vegetables (spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes, paprika); lauraceae (avocado, cinnamon, camphor) and plants such as tobacco, nuts, coffee, aubergines, sugar cane, tea, pepper, vines, hops, bananas and natural rubber plants and also ornamentals.
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 fertil¬ isers.
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 coπesponding pathogen. The compounds I can, however, also penetrate the plants through the roots via the soil (systemic action) if the locus of the plant is impregnated with a liquid formulation, or if the compounds are applied in solid form to the soil, e.g. in granular form (soil application). In paddy rice crops, such granules may be applied in metered amounts to the flooded rice field. 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. As with the nature of the compositions, 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.i7ha, most preferably from 20 g to 600 g a.iJha. In the case of seed-dressing compositions, concentrations of from 10 mg to 1 g of active substance per kg of seed are advantageously used.
The formulations, i.e. the 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).
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.
The solid carriers used, e.g. for dusts and dispersible powders, are normally natural mineral fillers such as calcite, talcum, kaolin, montmorillonite or attapulgite. In order to improve the physical properties it is also possible to add highly dispersed silicic acid or highly dispersed absorbent polymers. Suitable granulated adsorptive carriers are porous types, for example pumice, broken brick, sepiolite or bentonite; and suitable nonsorbent carriers are e.g. calcite or sand. In addition, a great number of pregranulated materials of inorganic or organic nature can be used, such as dolomite or pulverised plant residues. Depending on the nature of the compound of formula I to be formulated, suitable surface- active compounds are non-ionic, cationic and or anionic surfactants having good emuls¬ ifying, dispersing and wetting properties. The term "surfactants" will also be understood as comprising mixtures of surfactants.
Both so-called water-soluble soaps and water-soluble synthetic surface-active compounds are suitable anionic surfactants.
Representative examples of 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 Cg-C22alkyl radical and, as further substituents, unsubstituted or halogenated lower alkyl, benzyl or hydroxy-lower alkyl radicals. Other surfactants customarily used in formulation technology are known to the person skilled in the art and can be found in the relevant literature.
The agrochemical compositions generally comprise 0.1 to 99 % by weight, preferably 0.1 to 95 % by weight, of a compound of formula 1, 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.
Whereas commercial products will preferably be formulated as concentrates, the end user will normally employ dilute formulations.
The 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.
The following Examples illustrate the invention described above, without limiting the scope thereof in any way. Temperatures are given in degrees Celsius. The following abbreviations are used: Ac = acetyl; Et = ethyl; isopr = isopropyl; Me = methyl; Ph = phenyl; Pr = n-propyl; Bu = butyl; m.p. = melting point. DS = diastereoisomer; reg = regioisomer. "NMR" represents "nuclear magnetic resonance spectrum". MS = mass spectrum. "%" represents "% by weight" unless corresponding concentrations are indicated in a different unit. The expression "compound according to the invention" is to , be understood as meaning a compound I or its tautomer, in free form or in the form of an agrochemically acceptable salt
Preparation Examples for compounds according to the invention
Example P- la At room temperature, 36.9 g of 6-(l-aminoethyl)-2H-l,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. The batch is stirred well and then filtered to give 44.4 g of 6-[l- (5-chloro-6-ethylpyrimidin-4-ylamino)ethyl]-2H-l,4-benzoxazin-3-one in the form of a light-brown solid (m.p.: 172-174°).
Example P- lb Under N2, 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-[l-(5-chloro-6-ethylpyrimidin-4-ylamino)- ethyl]-2H-l,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. The residue is stirred in approximately 50 ml of water and then the batch is filtered with suction. The dried crude product can be further purified by digestion in ether. 3.1 g of 6-[l-(5-chloro-6-ethylpyrimidin-4-ylamino)- ethyl]-4-methyl-2H-l,4-benzoxazin-3-one are obtained in the form of a brownish solid (m.p.: 154-156°).
Example P-lc 10 g of 6-[l-(5-chloro-6-ethylpyrimidin-4-ylamino)ethyl]-2H-l,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. After drying over sodium sulfate and removing the ethyl acetate under a water- jet vacuum, 5.9 g of 6-[l-(5-chloro-6-ethylpyrimidin-4-ylamino)ethyl]-2H-l,4-benz- oxazin-3-thione are obtained in the form of an orange-red solid (m.p.: 166-168°),
It is also possible to prepare the compounds listed in the following Tables in a manner analogous to that described in Examples P-la, P-lb and P-lc or in accordance with another of the procedures indicated above.
Table 1: Compounds of the general formula 1.1
Ex. R, R3 R5 R7 R8 R9 X phys. data
Ex. R, Ro Rς R-l Rg R9 X phys. data
Ex. Rπ R R« R^ R8 R9 X phys. data
Table 2: Compounds of the general formula 1.2
Ex. R, R3 R« R^
Ex. R, R-i Rς R7 R8 R9 X phys. data
Ex. R, Ro R< R-*. R8 Rg X phys. data
Ex. Ro Ro R« R7 R8 R9 X phys. data
2.78 Et Cl Me CH2CO-
l Me CH2CO- oN ) H H O
2.79 Et C N O H H O
N t
Table 3 Compounds of the general formula 1.3
Ex. R Ro Re -i R8 R9 X phys. data
Ex. R, Ro Re R-i Rg Rξ, X phys. data
H H O H H O resin^H-NMR Ex. R, R. Rς R7 Rg R9 X phys. data
Ex. R Ro Re R R8 R9 X phys. data
Table 4 Compounds of the general formula 1.4
Ex. R Ro Re Ro R8 R9 X phys. data
Ex. R Ro Re Rπ R8 R9 X phys. data
Ex. Ro Ro Re R-i R8 R9 X phys. data
Ex. Ro Ro Re Ro R8 Rg X phys. data
H H O
4.86 Et Cl Me F H H O resin^H-NMR
4.88 Et Cl Me CH2CONHCH2CH3 H H O
4.89 Et Cl Me CH2CON(CH3)2 H H O
4.90 Et Cl Me CH2CO-N \ H H O
4.91 Et Cl Me CH2CO-N O H H O
4.92 Et
4.93 Et
4.94 Et
4.95 Me
4.96 Et
4.97 Et
4.98 Et
4.99 Et
4.100 Et Ex. Ro Ro Re Ro R8 R9 X phys. data
Table 5 Compounds of the general formula 1.5
Ex. Ro Ro Re Ro R8 Rg X phys. data
5.35 Et Cl Me m.p.78-80°C
Ex. Ro Ro Re Ro Rg Rg X phys. data
Ex. Ro Ro Re Ro Rg R9 X phys. data
5.76 Et Cl Me CO- \- F H H O m.p. 76°C
5.77 Et Cl Me H H O m.p. 68-70°C
5.78 Et Cl Me CH2CONHCH2CH3 H H O
5.79 Et Cl Me CH2CON(CH3)2 H H O
5.80 Et Cl Me CH2CO-N \ H H O
5.81 Et Cl Me CH2CO-N O H H O
5.82 Et Cl Me CH2CONHPh
5.83 Et Cl Me CH2CONHPh-(p)-Cl
5.84 Et Cl Me CH2CONHPh-(p)-F
5.85 Me Cl Me CH2CH2F
5.86 Et Cl Me CH2CH2F
5.87 Et Cl Me CH2CH2CH3
5.88 Et Cl Me CH(CH3)2
5.89 Et Cl Me (CH2)3CH3
5.90 Et Cl Me CH2CH=CH2
5.91 Et Cl Me CH2CH=CHCH3 Ex. Ro R, Re R7 Rg Rg X phys. data
5.96 Et Cl Me CH2C≡C-Si(CH3)3 H H
Table 6 Compounds of the general formula 1.6
Ex. Ro Ro Re R-l Rg R9 X phys. data
Ex. Ro Ro, Re Ro R8 Rg X phys. data
Ex. Ro Ro Re Ro R8 R9 X phys. data
Table 7: Compounds of the general formula 1.7
Ex. R7 phys. data
m.p.185-187°C m.p.125°C
m.p.113-115°C
Ex. Ro Ro Re R-j Ra R9 X phys. data
Table 8: Compounds of the general formula 1.8
Ex. Ro phys. data
resin
Ex. Ro Ro Re Ro Rg Rg X phys. data
Preparation Examples for intermediates
Example P-9:
In a hydrogenation autoclave, 84.6 g of 6-acetyl-2H-l,4-benzoxazin-3-one oxime are dissolved in 1.2 litres of absolute CH3OH. After the addition of 25 g of Raney nickel and 70 g of dry ammonia, the temperature is increased to 40° and the mixture is hydrogenated for 30 hours under a pressure of 30 bar. After cooling, the catalyst is filtered off and the solvent is evaporated off under a water-jet vacuum to give 75 g of 6-(l-aminoethyl)- 2H-l,4-benzoxazin-3-one in the form of a grey powder, m.p. 132-133°.
In an analogous manner or by means of another, corresponding procedure selected from those indicated above it is also possible to prepare the compounds listed in the following Tables.
Table 9: Compounds of the general formula III.9
Example R5 Ro Rg Rg phys. data
Table 10: Compounds of the general formula III.10
Example R5 Ro Rg Rg phys. data
m.p. 125°C
Table 11: Compounds of the general formula III.11
Example R5 R7 R8 R9 phys. data
Table 12: Compounds of the general formula in.12
Example R5 R7 R8 R9 phys. data
Table 13: Compounds of the general formula HI.13
Example R5 Ro R8 Rg phys. data
Table 14: Compounds of the general formula III.14
Example R5 Ro Rg R9 phys. data
Table 15: Compounds of the general formula UI.15
Example R5 R7 R8 R9 phys. data
resin
Table 17
Example -1H-NMR data (ppm/multiplicity/number of protons)
1.25 1.26Λ/3H; 1.59/d/3H; 2.67/s/3H; 2.68-2.92/m/6H; 5.33/m/lH; 5.56/d/lH; 7.19-7.26/m/2H; 7.39/d/lH; 8.39/s lH
1.42 1.26/1 3H; 1.59/d/3H; 2.74-2.84/m/4H; 3.19/1/2H; 3.89/S/3H; 5.32/m/lH; 5.56/d/lH; 7.10/d/lH; 7.16/d/lH; 7.27/dd/lH; 8.39/s/lH
1.56 0.95Λ/3H; 1.26/t/3H; 1.59/d/3H; 1.64/m/2H; 2.63/t 2H; 2.74-2.92/m/4H; 3.87/t/2H; 5.32/m/lH; 5.55/d/lH; 6.94/d lH; 7.16/d/lH; 7.18/dd lH; 8.40/s lH
1.59 1.25/1/3H; 1.60/d/3H; 2.66-2.7 l/m/4H; 2.92/t 2H; 4.54/m/2H; 5.11-5.21/m/2H; 5.34/m/lH; 5.82-5.94/m/lH; 6.95/d/lH; 7.16/d/lH; 7.20/dd/lH; 8.40/s lH
1.74 1.25/1 3H; 1.57/d/3H; 2.75-2.83/m/4H; 3.08/m/2H; 5.31/m/lH; 5.55/d/lH; 6.77/d/lH; 6.98/s lH; 7.10-7.16/m 3H; 7.25/dd/lH; 7.90/m/2H; 8.39/s lH
1.85 0.99/t 3H; 1.23/t/3H; 1.60/d/3H; 1.83/m/2H; 2.74-2.84/m/4H; 3.17/dd/2H; 4.45/m/2H; 5.32/m/lH; 5.56/d/lH; 7.10/d/lH; 7.15/d/lH; 7.27/dd/lH; 8.39/s lH
2.25 1.25/1/3H; 1.59/d/3H; 2.67/s/3H; 2.69-2.90/m/6H; 4.31/m/lH; 5.59/d/lH; 7.12-7.19/m/2H; 7.44/d/lH, 8.38/s/lH
2.44 1.25Λ/3H; 1.38/1/3H; 1.62/d/3H; 2.73-2.84/m/4H; 3.16/dd/2H; 4.60/q/2H; 5.35/m/lH; 5.59/d/lH; 7.08-7.16/m/3H; 6.39/s/lH
2.53 1.25/1/3H; 1.63/d/3H; 2.68-2.83/m/4H; 2.92/t/3H;
4.82/s lH; 4.86/s/lH; 5.35/m/lH; 5.61/d/lH; 7.05/s/lH; 7.09/d/lH; 7.19/d/lH; 8.39/s lH
2.56 0.93Λ/3H; 1.25/t/3H; 1.61/d/3H; 1.59-1.66/m 2H;
2.62/I/2H; 2.65-2.89/m/4H; 3.88/dd/2H; 5.33/m/lH; 5.59/d lH; 6.97/s/lH; 6.98/d/lH; 7.13/d/lH; 8.39/s/lH
2.59 1.25/t/3H; 1.59/d/3H; 2.61-2.93/m/6H; 1.54 m 2H;
5.06-5.15/m/2H; 5.31/m/lH; 5.55/d lH; 5.78-5.89/m lH; 6.98/s/lH; 6.99/d lH; 7.13/d/lH; 8.38/s/lH
2.61 1.25/t/3H; 1.62/d/3H; 2.15/t/lH; 2.63-2.93/m/6H;
4.69/m 2H; 5.37/m/lH; 5.61/d/lH; 7.04/dd/lH; 7.15/d/lH; 7.22/d/lH; 8.39/s/lH
2.84 1.25/t/3H; 1.61/d/3H; 2.74-2.8 l/m/4H; 3.20/dd/2H;
4.75-4.84/m/3H; 5.03/t/lH; 5.35/m/lH; 5.60/d lH; 7.13/m/2H; 7.41/d/lH; 8.38/s/lH
2.85 0.96/1/3H; 1.25/t/3H; 1.62/d/3H; 1.70-1.89/m 2H;
2.71-2.84/m/4H; 3.16/dd/2H; 4.46/m/2H; 5.35/m/lH; 5.59/d/lH; 7.10-7.17/m/3H; 8.39/s/lH
3.20 1.23/1/3H; 1.62/d 3H; 2.76/q/2H; 4.66/s/2H; 4.84/d/2H;
5.32/m/lH; 5.59/d/lH; 7.0-7.12/m/3H; 8.39/s lH
3.22 1.23/t/3H; 1.57/d/3H; 2.79/q/2H; 3.78/s/3H; 4.65/d/2H;
4.66/S/2H; 5.29/m lH; 5.53/d/lH; 6.77/d/lH; 6.97-7.05/m 2H; 8.39/s/lH
3.28 0.99/1/3H; 1.25/1/3H; 1.96/m/2H; 2.78/q/2H; 4.93/s lH;
4.97/s/lH; 5.10/q/lH; 5.63/d/lH; 7.15-7.26/m/3H; 8.35/s/lH
3.52 1.27Λ/3H; 1.61/d 3H; 2.84/q/2H; 5.32/m/lH; 5.62/d/lH;
7.04/d lH; 7.17/m/2H; 8.41/s/lH
3.58 0.98Λ/3H; 1.25/t/3H; 1.97/m/2H; 2.78/q/2H; 3.86/s 3H;
4.90/s/lH; 5.06/m/lH; 5.58/d/lH; 6.97/d/lH; 7.06/dd/lH; 7.11/d/lH; 8.37/s/lH
3.69 1.25/1/3H; 1.59/d/3H; 2.78/q/2H; 4.18/t/lH; 4.26/t/lH;
4.60/S/2H; 4.62/t/lH; 4.78/t/lH; 5.31/m/lH; 5.55/d/lH; 6.94-7.04/m 2H; 7.15/d/lH; 8.39/s/lH
3.79 (DMSO-d6) 1.14/1/3H; 1.52/d/3H; 3.36/s/3H; 4.59/s/2H; 4.67/S 2H;
5.33/m lH; 7.07/d/lH; 7.23/dd/lH; 7.51/d/lH; 7.68/d/lH; 8.27/s/lH
3.88 1.25Λ/3H; 1.49/d/3H; 2.78/m/2H; 4.65/s/2H;
5.17/m/lH; 5.42/d/lH; 6.97/d/lH; 7.08-7.15/m/5H; 7.86-7.90/m/2H; 8.29/s/lH
4.20 1.25/1/3H; 1.63/d/3H; 2.79/q/2H; 3.46/s 2H; 4.82/s/lH;
4.84/s/lH; 5.33/m lH; 5.60/d/lH; 7.12/dd/lH; 7.20/d/lH; 7.37/d/lH; 8.38/s/lH
4.55 1.26/t/3H; 1.61/d/3H; 2.79/q/2H; 3.90/S 2H; 3.92 s 3H;
5.31/m/lH; 5.57/d/lH; 7.09/dd/lH; 7.20/d/lH; 7.33/d/lH; 8.38/s/lH
4.67 1.25/1/3H; 1.60/d 3H; 2.79/q/2H; 3.40/s 2H; 4.17/t/lH;
4.25/t lH; 4.66/t/lH; 4.81/t/lH; 5.32/m/lH; 5.57/d/lH; 6.98/d lH; 7.04/dd/lH; 7.32/d/lH; 8.38/s lH
4.86 1.25Λ/3H; 1.57/d/3H; 2.75/q/2H; 3.50/s 2H; 5.12/m/lH;
5.40/d lH; 6.8-7.10/m/5H; 7.42/d/lH; 7.79-7.85/m/2H; 8.20/s/lH 5.10 1.26/t 3H; 1.60/d/3H; 2.17/m/2H; 2.29/m/2H;
2.69-2.85/m/4H; 3.32/s/3H; 5.36/m/lH; 5.57/d/lH; 7.12/d/lH; 7.17/d lH; 7.28/dd/lH; 8.41/s/lH
5.11 0.97/1/3H; 1.26/t/3H; 1.93/m/2H; 2.20/m/2H;
2.30/m 2H; 2.68-2.85/m/4H; 3.32/s/3H; 5.13/q/lH; 5.60/d/lH; 7.10-7.17/m/2H; 7.26/dd/lH; 8.39/s lH
5.12 1.13/t/3H; 1.26/t/3H; 1.61/d/3H; 2.08-2.28/m/4H;
2.70/m/2H; 2.79/q/2H, 3.89/m/2H; 5.37/m/lH; 5.58/d/lH; 7.14-7.18/m/2H; 7.27/dd/lH; 8.41/s/lH
5.13 0.95Λ/3H; 1.13/t/3H; 1.26/1/3H; 1.93/m/2H;
1.88-2.05/m/4H; 2.69/m/2H; 2.79/q/2H; 5.13/m/lH; 5.60/d/lH; 7.12-7.18/m/2H; 7.25/dd/lH; 8.39/s lH
5.22 1.27/t 3H; 1.61/d 3H; 2.12/m/2H; 2.32/t/2H; 2.69/s 3H;
2.70-2.8 l/m/4H; 5.40/m/lH; 5.58/d/lH; 7.12/d lH; 7.22-7.29/m/2H; 8.40/s lH
5.24 1.28/1 3H; 1.62/d/3H; 2.21/m/2H; 2.38/t/2H; 2.79/q/2H;
2.95/m/2H; 3.75/s/3H; 4.49/S/2H; 5.37/m/lH; 5.58/d/lH; 7.09/d/lH; 7.18-7.29/m/2H; 8.40/s/lH
5.30 1.27/t/3H; 1.62/d/3H; 2.20/m/2H; 2.38/t/2H; 2.79/q/2H;
2.93/m/2H; 3.75/s/3H; 4.50/s/2H; 5.36/m/2H; 5.58/d/lH; 7.10/d/lH; 7.20/s/lH; 7.27/d/lH; 8.41/s/lH
5.46 1.26/1/3H; i.61/d 3H; 2.42-2.75/m/4H; 2.79/q/2H;
3.05/m/2H; 3.78/s/3H; 5.36/m/lH; 5.57/d/lH; 7.14-7.16/m 2H; 7.30/dd/lH; 8.40/s/lH
5.47 0.98/1/3H; 1.26/1/3H; 1.93/m/2H; 2.40-2.75/m 5H;
2.78/q/2H; 3.07/m lH; 3.77/s/3H; 5.13/q/lH; 5.60/d/lH; 7.10-7.20/m/2H; 7.28/d lH; 8.38/s/lH 5.48 1.21-1.29/2xt/6H; 1.61/d 3H; 2.40-3.05/m/8H;
3.88/m/lH; 5.01/m lH; 5.38/m/lH; 5.59/d/lH; 7.18/d/lH; 7.20/d/lH; 7.31/dd/lH; 8.41/s/lH
5.50 0.96/t/3H; 1.21-1.29/2xt/6H; 1.94/m/2H;
2.40-2.62/m/4H; 2.68-2.85/m/3H; 2.98/m/lH; 3.90/m/lH; 5.0/m/lH; 5.16/m/lH; 5.60/d/lH; 7.14/s/lH; 7.18/d/lH; 7.25/d/lH; 8.39/s/lH
5.57 1.26/1/3H; 1.61/d/3H; 2.10-2.32 m/4H; 2.68-2.88/m/4H;
3.95-4.12/m/2H; 4.56/t/lH; 4.71/t 3H; 5.37/m/lH; 5.57/d/lH; 7.18/d lH; 7.22/d lH; 7.28/dd/lH; 8.41/s lH
5.67 1.27/t/3H; 1.60/d/3H; 3.10/m 2H; 2.31/t/2H;
2.72-2.85/m/4H; 3.50/s/3H; 4.73/s/2H; 5.41/m/lH; 5.59/d/lH; 7.17/d/lH; 7.23/d/lH; 7.31/dd/lH; 8.40/s/lH
6.10 1.26/1/3H; 1.60/d/3H; 2.15/m 2H; 2.30/t/3H; 2.69/t 2H;
2.79/q/2H; 3.34/s/3H; 5.35/m/lH; 5.57/d/lH; 7.16/m/3H; 6.39/s/lH
6.46 1.26/t 3H; 1.61/d/3H; 2.45-3.05/m/8H; 3.80/s 3H;
5.35/m/lH; 5.57/d/lH; 7.15-7.25/m/3H; 8.38/s lH
6.66 1.25/1 3H; 1.61/d/3H; 2.15/m/2H; 2.29/m/2H;
2.70-2.83/m/4H; 3.51/s/3H; 4.74/s/2H; 5.36/m/lH; 5.58/d lH; 7.20-7.33/m/3H; 8.38/s/lH
7.2 0.89/1/3H; 1.60-1.72/m/2H; 2.65/1/2H; 2.98/t/2H;
3.74/m/lH; 6.75/d/lH; 7.08-7.15/m/2H; 8.57/s/lH
9.10 (DMSO-d6) 1.25/d/3H; 3.40/s/2H; 4.02/q/lH; 7.05-7, 13/m 2H;
7.19/d/lH
11.2 0.90/1/3H; 2.25/m 2H; 2.38/m 2H; 2.80/t 2H; 3.80/m/lH; 6.90/s/lH; 7.10-7.22/m/2H; 7.29/2/1H
12.2 0.90/t3H; 1.70/1/2H; 2.20-2.49/m/4H; 2.75/s2H;
3.60-3.90/m/3H; 6.90/slH; 7.08/d/lH; 7.18/d/lH; 7.42/slH
15.1 (DMSO-d6) 1.21/d/3H; 1.90/s/2H; 2.40/t2H; 3.95/m/lH; 7.09/s/lH;
7.14/d/lH;7.44/d/lH
Examples of formulations of compounds according to the invention
Examples F-1.1 to F-1.3: Emulsifiable concentrates
Constituents F-1.1 F-1.2 F-1.3
a compound of Tab. 1-8 25% 40% 50% calcium dodecylbenzenesulfonate 5% 8% 6% castor oil polyethylene glycol ether (36 mol of ethylene- oxy units) 5% - tributylphenol polyethylene glycol ether (30 mol of ethylene- oxy units) - 12% 4% cyclohexanone - 15% 20% xylene mixture 65% 25% 20%
Emulsions of any desired dilution can be produced from such emulsifiable concentrates using water.
Example F-2: Emulsifiable concentrate
Constituents F-2
Emulsions of any desired dilution can be produced from this emulsifiable concentrate using water.
Examples F-3.1 to F-3.4: Solutions
Constituents F-3.1 F-3.2 F-3.3 F-3.4
These solutions are suitable for application in the form of micro-drops.
Examples F-4.1 to F-4.4: Granules
Constituents F-4.1 F-4.2 F-4.3 F-4.4
a compound of the invention kaolin highly dispersed silicic acid attapulgite
The compound of the invention is dissolved in dichloromethane, the solution is sprayed onto the carrier, and the solvent is subsequently evaporated off in vacuo. Examples F-5.1 and F-5.2: Dusts
Constituents F-5.1 F-5.2
a compound of Tab. 1-8 2% 5% highly dispersed silicic acid 1% 5% talcum 97% kaolin - 90%
Ready-for-use dusts are obtained by intimately mixing all of the constituents.
Examples F-6.1 to F-6.3: Wettable powders
Constituents F-6.1 F-6.2 F-6.3
a compound of Tab. 1-8 25% 50% 75% sodium lignosulfonate 5% 5% sodium laurylsulfate 3% - 5% sodium diisobutylnaphthalene- sulfonate - 6% 10% octylphenol polyethylene glycol ether (7 to 8 mol of ethylene- oxy units) - 2% - highly dispersed silicic acid 5% 10% 10% kaolin 62% 27%
All of the constituents are thoroughly mixed and the mixture is thoroughly ground in a suitable mill, affording wettable powders which can be diluted with water to give suspensions of the desired concentration. Biological Examples: A. Microbicidal actions.
B-l: Action against Puccinia graminis on wheat a) Residual-protective action
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. For example, compounds P-la, P-lb, P-lc, 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%. On the other hand, fungus attack is 100 % on untreated and infected control plants.
Example B-2: Action against Phytophthora infestans on tomatoes a) Residual-protective action
After three weeks' growth, tomato plants are sprayed to drip point 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 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. b) Systemic action
After three weeks' growth, 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. For example, compounds P-la, P-lb, P-lc, 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 %. On the other hand, 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. After 48 hours 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. For example, compounds P-la, P-lb, P-lc, 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 %. On the other hand, fungus attack is 100 % on untreated and infected control plants.
Example B-4: Action against Plasmopara viticola on vines Nine seedlings in the 4-5 leaf stage are sprayed to drip point 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 sporangia suspension of the fungus. The action of the test compound is assessed by evaluating the fungus attack 6 days after infection, during which time 95 to 100 % relative humidity and a temperature of 20° are maintained. Compounds of Tables 1-8 exhibit good activity against Plasmopara viticola on vines. For example, compounds 1.2, 1.4, 1.33, 1.35, 3.4, 3.11, 3.20 and 3.58 reduce fungus attack to 0-20 %. On the other hand, fungus attack is 100 % on untreated and infected control plants.
Example B-5: Action against Colletotrichum lagenarium on cucumbers After two weeks' growth, cucumber plants are sprayed with a spray mixture (concen¬ tration 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 spores/ml) of the fungus. The infected plants are incubated for 36 hours at 23° and high humidity. Incubation is then continued at normal humidity and about 22°. The fungus attack which occurs is evaluated 8 days after infection.
Compounds of Tables 1-8, for example compounds P-la, P-lb, P-lc, 1.33, 1.35, 3.4, 3.8, 3.11 and 3.22 reduce fungus attack to 0-20%. On the other hand, fungus attack is 100 % on untreated and infected control plants.
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. After 24 hours 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.
Compounds of Tables 2, 5 and 6, 7 and 8 exhibit good residual-protective action against Venturia inaequalis on apples.
Example B-7: Action against Ervsiphe graminis on barley a) Residual-protective action
Barley plants about 8 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. After 3 to 4 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. b) Systemic action
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. For example, compounds P-la, P-lb, P-lc, 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 %. On the other hand, 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.
Compounds of Tables 1-8, for example compounds P-la, P-lc, 1.33, 1.35, 3.4, 3.8 and 3.11 exhibit good activity 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 comprising 400 ppm of the test compound. The plants are then incubated for 6 days at 25° and then evaluation is made. The percen¬ tage 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.
The compounds of Table 3 exhibit good activity against Tetranychus urticae in this test In particular, compounds P-lc, 3.4, 3.8, 3.11 and 3.20 are more than 70 % effective. B-10: Action against Nilaparvata lugens
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 L2 and 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.
B-U: Action on mixed population of Tetranychus cinnabarinus.
Dilution series
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
- eggs
- larvae/nymphs
- adults.
Compounds of Tables 1-8 cause more than 70 % mortality at dilutions of down to 50 mg a.iJlitre.
B-12: Action against Nilaparvata lugens
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^ and L3 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. In particular, compounds 3.4, 3.8, 3.11 and 3.20 are more than 80 % effective.
B-13: Action against Plutella xylostella caterpillars
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.
The compounds of Tables 3, 5, 6 and 8 exhibit good activity in this test In particular, compounds 3.4, 3.8, 3.11 and 3.20, 5.2, 5.5, 5.11, 5.22, 5.35 and 5.49 are more than 80 % effective.

Claims

What is claimed is:
1. A compound of formula I
wherein the substituent A is in the α-, β-, γ- or δ-position and wherein:
R1 is hydrogen, C1-C4alkyl, C1-C4alkoxy, halo- C1-C4alkyl having 1, 2 or 3 halogen atoms, or C1-C4alkylthio;
R2 and R3 are each independently of the other hydrogen, C1-C4alkyl, halo-C1-C4alkyl having 1, 2 or 3 halogen atoms, C1-C2alkoxy-C1-C4alkyl, nitro-C1-C4alkyl, cyano- C1-C4- alkyl, alkanoyl-C1-C4alkyl, alkoxycarbonyl- 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-C4- alkoxy, halo-C1-C4alkoxy, C1-C4alkylthio, halo-C1-C4alkylthio, C1-C4alkylsulfinyl, C1-C4alkylsulfonyl, amino, C1-C4acylamino, nitro, cyano, hydroxy or halogen, a group of the formula N(H)R12 a group of the formula N(R12)R13 or a group of the formula
N=C(R13)R14;
R4 is hydrogen, C1-C4alkyl, halo- C1-C4alkyl having 1, 2 or 3 halogen atoms, C1-C2- alkoxy- C1-C4alkyl, nitro-C1-C4alkyl, cyano- C1-C4alkyl, C3-C5cycloalkyl, benzyl, C1-C4- 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, C1-C2alkyl, nitro and cyano;
R5 and R6 are each independently of the other hydrogen, C1-C4alkyl, halo- C1-C4alkyl having 1, 2 or 3 halogen atoms, C1-C2alkoxy- C1-C4alkyl, nitro-C1-C4alkyl, cyano- C1-C4- alkyl, alkoxycarbonyl-C1-C4alkyl or C3-C6cycloalkyl that is unsubstituted or substituted by one or two substituents selected from the group consisting of halogen and C1-C2alkyl; R7 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, unsubstit- uted or substituted benzyl, an unsubstituted or substituted acyl or thioacyl group containing up to 12 carbon atoms, an unsubstituted or substituted C1-C4alkylsulfonyl, phenylsulfonyl or aminosulfonyl group, or an unsubstituted or substituted heterocyclyl radical;
R8, R9, R10 and R11 are each independently of the others hydrogen, halogen, C1-C4alkyl, halo-C1-C4alkyl having 1, 2 or 3 halogen atoms, C1-C2alkoxy-C1-C4alkyl, C3-C6cyclo- alkyl, C1-C4alkoxy, halo- C1-C4alkoxy having 1, 2 or 3 halogen atoms, C3-C7 cycloalkoxy, C1-C4alkylthio, halo- C1-C4alkylthio 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 halogen, C1-C2alkyl and C1-C2alkoxy, with the proviso that no more than one of those substituents R8, R9, R10 and R11 is unsubstituted or substituted phenyl, substituted phenoxy or substituted phenylthio;
R12is C1-C4alkyl, benzyl, C1-C4alkanoyl, benzoyl, the phenyl group of which is unsubstituted or substituted by one, two or three substituents selected from the group consisting of halogen and C1-C2alkyl, C1-C4alkylthio, halo-C1-C4alkylthio having 1, 2 or 3 halogen atoms, cyano- C1-C4alkylthio, 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, C1-C2alkyl, nitro and cyano;
R13 is C1-C4alkyl;
R14 is hydrogen or C1-C4alkyl;
X is oxygen or sulfur;
Y is a group -CH(R15)-, oxygen, sulfur or a group -N(R16)-;
R15 is hydrogen or C1-C4alkyl;
R16 is hydrogen, C1-C4alkyl, C1-C4alkanoyl, benzoyl, the phenyl group of which is unsubstituted or substituted by one, two or three substituents selected from the group consisting of halogen, C1-C4alkyl, nitro and cyano, C1-C4alkylsulfonyl, or aminosulfonyl, the nitrogen atom of which is unsubstituted or mono- or di-substituted by C1-C4alkyl; and n is 1 or 2;
or a tautomer thereof, in each case in free form or in salt form.
2. A compound of formula I according to claim 1, wherein:
R7 is hydrogen, C1-C4alkyl, halo- C1-C4alkyl having 1, 2 or 3 halogen atoms, C1-C2- alkoxy- C1-C4alkyl, nitro- C1-C4alkyl, cyano-C1-C4alkyl, alkanoyl- C1-C4alkyl, alkoxy- carbonyl- C1-C4alkyl, C3-C5cycloalkyl, benzyl, phenyl that is unsubstituted or mono- to tri-substituted by the same or different substituents selected from the group consisting of C1-C2alkyl, halomethyl, halogen, nitro and amino, C1-C4alkanoyl that is unsubstituted or substituted by halogen or by C1-C2alkoxy, C1-C4thioalkanoyl, benzoyl, the phenyl group of which is unsubstituted or substituted by one or two substituents selected from the group consisting of halogen, C1-C2alkyl, nitro and cyano; thiobenzoyl, the phenyl group of which is unsubstituted or substituted by one or two substituents selected from the group consisting of halogen, C1-C2alkyl, nitro, cyano, amino, C1-C4acylamino and C1-C4alkoxy- carbonyl, C1-C4alkylsulfonyl, halo-C1-C4alkylsulfonyl having 1, 2 or 3 halogen atoms, cyano-C1-C4alkylsulfonyl, phenylsulfonyl, the phenyl group of which is unsubstituted or substituted by one or two substituents selected from the group consisting of halogen, C1-C2alkyl, nitro and cyano, aminosulfonyl, the nitrogen atom of which is unsubstituted or mono- or di-substituted by C1-C4alkyl, or heterocyclyl that is unsubstituted or mono- to tri-substituted by the same or different substituents selected from the group consisting of C1-C2alkyl, halomethyl, halogen, nitro and amino;
or a tautomer thereof, in each case in free form or in salt form.
3. A compound of formula I according to claim 1, wherein:
R7 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-
(C1-C4alkyl)silyl or by an epoxy group, C1-C4alkanoyl that is unsubstituted or substituted by from 1 to 3 halogen atoms, C1-C2alkoxy, phenoxy, amino or by dimethylamino, or a group
-CH2CO-N(T1)(T 2) or -CH2CH2CO-N(T1)(T2), wherein
T1 and T2 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, C1-C2alkoxy, hydroxy, nitro, cyano, C1-C4- alkanoyl, halo-C1-C4alkanoyl or by C1-C4alkoxycarbonyl, 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, C1-C2alkyl, 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 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 heterocycle which may additionally contain O, S and/or N as ring atoms, wherein additional nitrogen is unsubstituted or substituted by C1-C4alkyl, phenyl, C1-C4- 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, C1-C2alkyl, halomethyl and nitro.
4. A compound of formula I according to claim 3, wherein:
R7 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(C1-C4alkyl)silyl, C1-C4alkanoyl that is unsubstituted or substituted by from 1 to 3 halogen atoms, C1-C2alkoxy, phenoxy, amino or by dimethylamino,
or a group
-CH2CO-N(T1)(T2), wherein
T1 and T2 are each independently of the other hydrogen, C1-C4alkyl, phenyl or halo- phenyl, or
T1 and T2, together with the nitrogen atom to which they are bonded, form piperidine or morpholine.
5. A compound of formula I according to claim 1, wherein:
R1 is hydrogen or C1-C4alkyl;
R2 and R3 are each independently of the other hydrogen, C1-C4alkyl, halo- C1-C4alkyl having 1, 2 or 3 halogen atoms, C1-C2alkoxy-C1-C4alkyl, C2-C4alkynyl, C3-C5cycloalkyl, hydroxy or halogen;
R4 is hydrogen, C1-C4alkyl, C3-C5cycloalkyl or benzyl;
R5 and R6 are each independently of the other hydrogen, C1-C4alkyl, halo- C1-C4alkyl having 1, 2 or 3 halogen atoms, C1-C2alkoxy-C1-C4alkyl or C3-C6cycloalkyl;
R7 is hydrogen, C1-C4alkyl, halo- C1-C4alkyl having 1, 2 or 3 halogen atoms, C1-C2- alkoxy-C1-C4alkyl, cyano-C1-C4alkyl, benzyl, phenyl that is unsubstituted or mono- to tri-substituted by the same or different substituents selected from the group consisting of C1-C2alkyl, halomethyl, halogen, nitro and amino, C1-C4alkanoyl that is unsubstituted or substituted by halogen or by C1-C2alkoxy, C1-C4thioalkanoyl, benzoyl, the phenyl group of which is unsubstituted or substituted by one or two substituents selected from the group consisting of halogen and C1-C2alkyl; thiobenzoyl, the phenyl group of which is unsubstituted or substituted by one or two substituents selected from the group consisting of halogen and C1-C2alkyl, C1-C4alkylsulfonyl, halo- C1-C4alkylsulfonyl having 1, 2 or 3 halogen atoms, phenylsulfonyl, the phenyl group of which is unsubstituted or substituted by one or two substituents selected from the group consisting of halogen and C1-C2alkyl, or aminosulfonyl, the nitrogen atom of which is unsubstituted or mono- or di-substituted by C1-C4alkyl;
R8, Rg, R10 and R11 are each independently of the other hydrogen, halogen or C1-C4alkyl; X is oxygen or sulfur;
Y is a group -CH(R15)-, oxygen, sulfur or a group -N(R16)-;
R15 is hydrogen or C1-C4alkyl;
R16 is hydrogen, C1-C4alkanoyl, benzoyl, the phenyl group of which is unsubstituted or substituted by one, two or three substituents selected from the group consisting of halogen, C1-C2alkyl, nitro and cyano, C1-C4alkylsulfonyl, or aminosulfonyl, the nitrogen atom of which is unsubstituted or mono- or di-substituted by C1-C4alkyl; and
n is 1 or 2.
6. A compound of formula I according to claim 1, wherein the substituent A is in the β- or γ-position.
7. A compound of formula I according to claim 1, wherein:
R1 is hydrogen or C1-C4alkyl;
R2 is hydrogen, C1-C4alkyl, halo- C1-C4alkyl having 1, 2 or 3 halogen atoms, C1-C2- alkoxy-C1-C4alkyl, cyclopropyl, ethynyl or halogen;
R3 is hydrogen, fluorine, chlorine or bromine;
R4 is hydrogen or C1-C4alkyl;
R5 is C1-C4alkyl; and
R6 is hydrogen.
8. A compound of formula I according to claim 7, wherein:
R7 is hydrogen, C1-C4alkyl, C1-C2alkoxy- C1-C4alkyl, cyano- C1-C4alkyl, C1-C4alkanoyl that is unsubstituted or substituted by halogen or by C1-C2alkoxy, C1-C4thioalkanoyl, benzoyl, the phenyl group of which is unsubstituted or substituted by one or two substituents selected from the group consisting of halogen and C1-C2alkyl; thiobenzoyl, the phenyl group of which is unsubstituted or substituted by one or two substituents selected from the group consisting of halogen and C1-C2alkyl, C1-C4alkylsulfonyl, halo- C1-C4- alkylsulfonyl having 1, 2 or 3 halogen atoms, phenylsulfonyl, the phenyl group of which is unsubstituted or substituted by one or two substituents selected from the group consisting of halogen and C1-C2alkyl, or aminosulfonyl, the nitrogen atom of which is unsubstituted or mono- or di-substituted by C1-C4alkyl;
R8 and R9 are each independently of the other hydrogen, fluorine, chlorine or bromine; R10 and R11 are hydrogen;
X is oxygen or sulfur;
Y is a group -CH(R15)-, oxygen, sulfur or a group -N(R16)-; R15 is hydrogen or C1-C4alkyl;
R16 is hydrogen, C1-C4alkanoyl, benzoyl, the phenyl group of which is unsubstituted or substituted by one, two or three substituents selected from the group consisting of halogen,
C1-C2alkyl, nitro and cyano, C1-C4alkylsulfonyl, or aminosulfonyl, the nitrogen atom of which is unsubstituted or mono- or di-substituted by C1-C4alkyl; and
n is 1 or 2.
9. A compound of formula I according to claim 8, wherein:
R7 is hydrogen, methyl, ethyl or cyanomethyl;
R8 and R9 are each independently of the other hydrogen or fluorine;
R10 and R11 are hydrogen;
X is oxygen or sulfur;
Y is the group -CH2-, oxygen, sulfur or the group -NH-; and
n is 1 or 2.
10. A compound of formula I according to claim 1, wherein the substituent A is either in the β-position or in the γ-position, and wherein:
Y is the group -CH2-; and
n is 1 or 2.
11. A compound of formula I according to claim 10, wherein:
R1 is hydrogen or C1-C4alkyl;
R2 is hydrogen, C1-C4alkyl, halo- C1-C4alkyl having 1, 2 or 3 halogen atoms, C1-C2- alkoxy- C1-C4alkyl, cyclopropyl, ethynyl or halogen;
R3 is hydrogen, fluorine, chlorine or bromine;
R4 is hydrogen or C1-C4alkyl;
R5 is C1-C4alkyl;
R6 is hydrogen;
R7 is hydrogen, methyl, ethyl or cyanomethyl;
R8 and R9 are each independently of the other hydrogen or fluorine;
R10 and R11 are hydrogen;
X is oxygen or sulfur;
Y is the group -CH2-; and
n is 1 or 2.
12. A compound according to claim 1 of formula I.1
wherein:
R2 is hydrogen, methyl or ethyl;
R3 is fluorine or chlorine;
R5 is methyl or ethyl;
R7 is hydrogen, methyl, ethyl or cyanomethyl;
R8 and R9 are each independently of the other hydrogen or fluorine; and
X is oxygen or sulfur.
13. A compound according to claim 1 of formula I.2
wherein:
R2 is hydrogen, methyl or ethyl;
R3 is fluorine or chlorine;
R5 is methyl or ethyl;
R7 is hydrogen, methyl, ethyl or cyanomethyl;
R8 and R9 are each independently of the other hydrogen or fluorine; and
X is oxygen or sulfur.
14. A compound according to claim 1, wherein the substituent A is either in the β-position or in the γ-position, and wherein:
Y is oxygen or sulfur; and
n is 1.
15. A compound according to claim 1 of formula I.3
wherein:
R2 is hydrogen, methyl or ethyl;
R3 is fluorine or chlorine;
R5 is methyl or ethyl;
R7 is hydrogen, methyl, ethyl or cyanomethyl;
R8 and R9 are each independently of the other hydrogen or fluorine; and
X is oxygen or sulfur .
16. A compound according to claim 1 of formula I.4
wherein:
R2 is hydrogen, methyl or ethyl;
R3 is fluorine or chlorine;
R5 is methyl or ethyl;
R7 is hydrogen, methyl, ethyl or cyanomethyl;
R8 and R9 are each independently of the other hydrogen or fluorine; and
X is oxygen or sulfur.
17. A compound according to claim 1 of formula I.5
wherein:
R2 is hydrogen, methyl or ethyl;
R3 is fluorine or chlorine;
R5 is methyl or ethyl;
R7 is hydrogen, methyl, ethyl or cyanomethyl;
R8 and R9 are each independently of the other hydrogen or fluorine; and
X is oxygen or sulfur.
18. A compound according to claim 1 of formula I.6
wherein:
R2 is hydrogen, methyl or ethyl;
R3 is fluorine or chlorine;
R5 is methyl or ethyl;
R7 is hydrogen, methyl, ethyl or cyanomethyl;
R8 and R9 are each independently of the other hydrogen or fluorine; and
X is oxygen or sulfur.
19. A compound according to claim 1, wherein the substituent A is either in the β-position or in the γ-position, and wherein:
R1 is hydrogen;
R2 is methyl or ethyl;
R3 is chlorine; R4 is hydrogen;
R5 is methyl, ethyl or cyclopropyl;
R6 is hydrogen;
R7 is hydrogen, methyl, ethyl, cyanomethyl or methylsulfonyl;
R8, R9, R10 and R11 are each hydrogen;
X is oxygen or sulfur;
Y is oxygen or the group -CH2-; and
n is 1 or 2.
20. A compound according to claim 1 of formula I.7
wherein the substituent A is either in the β-position or in the γ-position, and wherein: R5 is methyl or ethyl; and
R7 is C1-C4alkyl that is unsubstituted or substituted by from 1 to 3 halogen atoms or by cyano, C2-C4alkenyl, C2-C4alkynyl, or acetyl that is unsubstituted or substituted by C1-C4- alkoxy, phenoxy or by halogen.
21. A compound according to claim 1 of formula I.8
wherein:
R5 is methyl or ethyl; and
R7 is C1-C4alkyl, C2-C4alkenyl, C2-C4alkynyl, or acetyl that is unsubstituted or substituted by C1-C4alkoxy, phenoxy or by halogen.
22. A compound according to claim 1 of formula I.9
wherein:
R5 is methyl or ethyl; and
R7 is C1-C4alkyl, C2-C4alkenyl, C2-C4alkynyl, or acetyl that is unsubstituted or substituted by C1-C4alkoxy, phenoxy or by halogen.
23. A process for the preparation of a compound of formula I according to claim 1, wherein a) for the preparation of a compound of formula I wherein R1-R11, X, Y and n are as defined in claim 1, a compound of formula II
wherein R1, R2 and R3 are as defined for formula I and Z is a readily removable nucleofugal radical, is reacted, preferably in the presence of a base, with a compound of formula
III
HR4N- C(R5)(R6)
7
or with a salt thereof, wherein R4 to R11, X, Y and n are as defined for formula I; or b) for the preparation of a compound of formula I wherein R4, R7 and R16 are as defined in claim 1 but are other than hydrogen, a compound of formula I wherein R4, R7 and R16 are hydrogen is reacted in the presence of a base with a compound of the formula R4'-Z', R7'-Z' or R16'-Z' wherein R4', R7' and R16' are as defined in claim 1 for R4, R7 and R16, 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 thionating agent, preferably with phosphorus pentasulfide or 4-methoxyphenylthiophosphonic acid cyclodithioanhydride (Lawesson's reagent).
24. A composition for protecting plants against attack by pests, which comprises as active ingredient at least one compound of formula I according to claim 1, together with a carrier.
25. A composition according to claim 24, the pests being phytopathogenic microorganisms.
26. A composition according to claim 24, the pests belonging to the order Acarina and to the classes Insecta and Nematoda.
27. A composition for protecting plants against attack by pests, which comprises as active ingredient at least one compound of formula I according to claim 2, together with a carrier.
28. A composition according to claim 27, the pests being phytopathogenic microorganisms.
29. A composition according to claim 27, the pests belonging to the order Acarina and to the classes Insecta and Nematoda.
30. A process for the preparation of a composition according to claims 24 to 29, wherein the active ingredient is mixed homogeneously with the extender and/or the dispersant.
31. The use of a compound of formula I according to claim 1 for the protection of plants against attack by pests.
32. The use of a compound of formula I according to claim 2 for the protection of plants against attack by pests.
33. A method of protecting plants against attack by pests, wherein a compound of formula I according to claim 1 is applied as active ingredient to the plants, to parts of the plants and/or to the locus of the plants.
34. A method according to claim 33, the pests being phytopathogenic micro-organisms.
35. A method according to claim 33, the pests belonging to the order Acarina and to the classes Insecta and Nematoda.
36. A method of protecting plants against attack by pests, wherein a compound of formula I according to claim 2 is applied as active ingredient to the plants, to parts of the plants and/or to the locus of the plants.
37. A method according to claim 36, the pests being phytopathogenic micro-organisms.
38. A method according to claim 36, the pests belonging to the order Acarina and to the classes Insecta and Nematoda.
39. A compound of formula III HR4N- C(R5)(R6)
7 wherein the substituent HR4N-C(R5)(R6)- is in the β- or γ-position and wherein R4 to R11, X, Y and n are as defined for formula I in claim 1, in free form or in salt form.
EP94906911A 1993-02-18 1994-02-07 Pyrimidine derivatives and their use as pesticides Withdrawn EP0694034A1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
CH509/93 1993-02-18
CH50993 1993-02-18
PCT/EP1994/000337 WO1994019340A1 (en) 1993-02-18 1994-02-07 Pyrimidine derivatives and their use as pesticides

Publications (1)

Publication Number Publication Date
EP0694034A1 true EP0694034A1 (en) 1996-01-31

Family

ID=4188637

Family Applications (1)

Application Number Title Priority Date Filing Date
EP94906911A Withdrawn EP0694034A1 (en) 1993-02-18 1994-02-07 Pyrimidine derivatives and their use as pesticides

Country Status (8)

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

Families Citing this family (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
WO2001035964A1 (en) * 1999-11-18 2001-05-25 Antexpharma, Inc. Substituted 1-benzazepines and derivatives thereof
US7229986B2 (en) * 2000-05-16 2007-06-12 Takeda Pharmaceutical Company Ltd. Melanin-concentrating hormone antagonist
US20050234041A1 (en) * 2001-05-16 2005-10-20 Alenka Tomazic Substituted 1-benzazepines and derivatives thereof
AU2011255218B2 (en) 2010-05-21 2015-03-12 Infinity Pharmaceuticals, Inc. Chemical compounds, compositions and methods for kinase modulation
AR091790A1 (en) 2011-08-29 2015-03-04 Infinity Pharmaceuticals Inc DERIVATIVES OF ISOQUINOLIN-1-ONA AND ITS USES
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

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3049093B2 (en) * 1990-11-19 2000-06-05 ペン・ステイト・リサーチ・フアウンデーション Insecticidal, acaricidal and fungicidal and fungicidal aminopyrimidines
EP0555183A1 (en) * 1992-02-07 1993-08-11 Ciba-Geigy Ag Pesticides

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9419340A1 *

Also Published As

Publication number Publication date
TW242557B (en) 1995-03-11
JPH08507053A (en) 1996-07-30
ZA941081B (en) 1994-08-18
MX9401223A (en) 1994-08-31
IL108664A0 (en) 1994-05-30
AU6039294A (en) 1994-09-14
WO1994019340A1 (en) 1994-09-01

Similar Documents

Publication Publication Date Title
CA1339571C (en) Process and a composition for immunizing plants against diseases
US6262058B1 (en) Pyrimidin-4-one derivatives as pesticide
JP4836383B2 (en) Pyrrole carboxamides and pyrrole thioamides as fungicides
US4966908A (en) Isonicotinic acid amides for protecting plants against disease
EP0784611B1 (en) N-(ortho-substituted benzyloxy)imine derivatives and their use as fungicides, acaricides or insecticides
NZ208972A (en) N-aminomethyl-3-phenyl-4-cyanopyrrole derivatives and microbicidal compositions
AU657558B2 (en) Pesticides
US5616590A (en) Plant microbicides
AU666700B2 (en) Pesticides
EP0694034A1 (en) Pyrimidine derivatives and their use as pesticides
EP0836595B1 (en) Triazoline and isoxazoline bis-oxime derivatives and their use as pesticides
WO1996008475A1 (en) Pesticidal pyridine derivatives
AU616176B2 (en) Substituted isonicotinoylpyridinylhydrazine derivatives, the preparation thereof, compositions containing them and their use in the protection of plants against attack by harmful microorganisms
US5814629A (en) Microbicides
EP0790983A1 (en) Pesticidal pyridine thioamides
DE69709112T2 (en) PESTICIDES
WO1994020490A1 (en) Pyrimidine derivatives useful as pesticides
EP0707582A1 (en) Pyrimidin-4-ylaminomethylquinoline derivatives as pesticides
WO1998017631A2 (en) Substituted oxime-ethers and their use as pesticides
JPS63166871A (en) Aminomethylisoxazolidine
IE912134A1 (en) Microbicides
EP0621864A1 (en) 2-(2-BENZO(b)THIENYL)-3-METHOXYACRYLATE AND -2-IMINOACETATE DERIVATIVES TO BE USED AS PESTICIDES.

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 19950707

AK Designated contracting states

Kind code of ref document: A1

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

17Q First examination report despatched

Effective date: 19960513

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 19960924