WO1998054125A1 - O-benzyl oxime ethers and their use as pesticides - Google Patents

O-benzyl oxime ethers and their use as pesticides Download PDF

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Publication number
WO1998054125A1
WO1998054125A1 PCT/EP1998/003073 EP9803073W WO9854125A1 WO 1998054125 A1 WO1998054125 A1 WO 1998054125A1 EP 9803073 W EP9803073 W EP 9803073W WO 9854125 A1 WO9854125 A1 WO 9854125A1
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Prior art keywords
alkyl
formula
compound
halo
aryl
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PCT/EP1998/003073
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French (fr)
Inventor
Stephan Trah
Henry Szczepanski
Ottmar Franz HÜTER
Roger Graham Hall
Saleem Farooq
Alfons Pascual
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Novartis Ag
Novartis-Erfindungen Verwaltungsgesellschaft M.B.H.
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Priority to EP98932081A priority Critical patent/EP0984923A1/en
Priority to AU82102/98A priority patent/AU8210298A/en
Priority to JP50021699A priority patent/JP2002501515A/en
Publication of WO1998054125A1 publication Critical patent/WO1998054125A1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/38—Phosphonic acids RP(=O)(OH)2; Thiophosphonic acids, i.e. RP(=X)(XH)2 (X = S, Se)
    • C07F9/40—Esters thereof
    • C07F9/4003—Esters thereof the acid moiety containing a substituent or a structure which is considered as characteristic
    • C07F9/4021—Esters of aromatic acids (P-C aromatic linkage)
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
    • C07C251/32—Oximes
    • C07C251/50—Oximes having oxygen atoms of oxyimino groups bound to carbon atoms of substituted hydrocarbon radicals
    • C07C251/60—Oximes having oxygen atoms of oxyimino groups bound to carbon atoms of substituted hydrocarbon radicals of hydrocarbon radicals substituted by carboxyl groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D261/00—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings
    • C07D261/02—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings
    • C07D261/06—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings having two or more double bonds between ring members or between ring members and non-ring members
    • C07D261/08—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings having two or more double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D261/00—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings
    • C07D261/20—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings condensed with carbocyclic rings or ring systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/30—Phosphinic acids R2P(=O)(OH); Thiophosphinic acids, i.e. R2P(=X)(XH) (X = S, Se)
    • C07F9/32—Esters thereof
    • C07F9/3205—Esters thereof the acid moiety containing a substituent or a structure which is considered as characteristic
    • C07F9/3229—Esters of aromatic acids (P-C aromatic linkage)
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/50—Organo-phosphines
    • C07F9/53—Organo-phosphine oxides; Organo-phosphine thioxides
    • C07F9/5325—Aromatic phosphine oxides or thioxides (P-C aromatic linkage)

Definitions

  • the invention relates to compounds of formula
  • X is CH or N
  • Y is OR.
  • Z is O, or
  • Rt is hydrogen or C . -C 4 alkyl; Re is hydrogen or C ⁇ -C alkyl; R 2 is H, C C 4 alkyl, halo-C 1 -C 4 alkyl, C 3 -C 6 cycloalkyl, CrC 4 alkoxymethyl, C ⁇ -C 4 alkoxy, halo-C 1 -C alkoxy, d-C alkylthio, halo-C ⁇ -C 4 alkylthio or CN;
  • n is 0, 1 , 2, 3 or, if either a or b is 0, 4;
  • R 9 is methyl, fluoromethyl or difluoromethyl
  • R 7 is a radical R 10 ;
  • R 10 is H, C . -C 6 alkyl, C 2 -C 8 alkenyl, C 2 -C 8 alkynyl or C 3 -C 6 cycloalkyl, or d-C 6 alkyl, C 2 -C 8 - alkenyl, C 2 -C 8 alkynyl or C 3 -C 6 cycloalkyl each mono- or poly-substituted by substitu- ents from the group consisting of halogen; -Si(C C 4 alkyl) 3 , the alkyl groups being the same or different; d-Cealkoxycarbonyl or an aryl or heterocyclyl group that is unsubstituted or mono- or poly-substituted by substituents selected from the group consisting of halogen, d-C alkyl and halo-C ⁇ -C 4 alkyl; and
  • G is d-C 8 alkylene
  • R 6 is d-dalkyl, aryl or heteroaryl; or aryl or heteroaryl each of which - depending on the substitution possibilities on the ring structure - is mono- to penta-substituted by substituents selected independently of one another from the group consisting of (R 5 ) s ; s is, depending on the substitution possibilities on the ring, 0, 1 , 2, 3, 4 or 5, the substituents R 5 being independent of one another when s is greater than 1 ;
  • a T and R are as defined above for A and R 7 ; a is 0 or 1 ;
  • L is U-R. ⁇ , P(O) v RnR 12 , P(S) w RnR ⁇ 2 or N(aryl)R 13 , the aryl radical being either unsubstituted or mono- to penta-substituted by substituents selected independently of one another from the group consisting of R 5 ; v and w are 0 or 1 ;
  • p is from 0 to 4.
  • Rn and R 12 are each independently of the other C ⁇ -C 6 alkyl, halo-C ⁇ -C 6 alkyl, C 3 -C 6 cyclo- alkyl, halo-C 3 -C 6 cycloalkyl, C C 6 alkoxy, halo-C C 6 alkoxy, d-C ⁇ alkylthio, halo- C r C 6 alkylthio, aryl, heteroaryl, aryloxy, arylthio, heteroaryioxy or heteroarylthio; or aryl, heteroaryl, aryloxy, arylthio, heteroaryioxy or heteroarylthio each mono- to penta- substituted by R 5 , the substituents R 5 being independent of one another; b is 0 or 1 , but a and b are not simultaneously 0;
  • R- I3 is hydrogen, C . -C 6 alkyl, halo-d-C 6 alkyl, C 3 -C 6 cycloalkyl, halo-C 3 -C 6 cycloalkyl,
  • halo-d-C ⁇ alkoxydicarbonyl C ⁇ -C 6 alkylaminodicarbonyl, di(C ⁇ -C 6 alkyl)aminodicarbonyl, the alkyl groups being the same or different; C C 6 alkylaminodithiocarbonyl, d d-Cealky aminodithiocarbonyl, the alkyl groups being the same or different; aryl, arylsulfinyl, aryl-C 1 -C 6 alkylsulfinyl, arylsulfonyl, aryl- C C 6 alkyl-sulfonyl, aryloxy-d-C ⁇ alkyl, arylthio-C C 6 alkyl, aryl-C C 6 alkylsulfinyl- C C 6 alkyl, aryl-d-C ⁇ alkylsulfonyl-Ci-Cealkyl, arylcarbonyl,
  • R i4 and R i5 are each independently of the other d-C alkyl
  • R ⁇ e and R 7 are each independently of the other hydrogen, C ⁇ -C 4 alkyl or halogen and
  • the compounds may occur in the E and Z isomeric forms.
  • Atropisomers of the compounds may also occur.
  • the corresponding formulae are intended to include all those possible isomeric forms and also mixtures thereof, for example racemates or mixtures of E Z isomers, and also, where applicable, salts thereof, even if this is not specifically mentioned every time.
  • carbon-containing groups and compounds each contain from 1 up to and including 8, especially from 1 up to and including 6, more especially from 1 up to and including 4, very especially 1 or 2, carbon atoms.
  • Alkyl as a group perse and also as a structural unit of other groups and compounds, such as of haloalkyl, alkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl, alkylcarbonyl, alkoxycarbonyl, alkylamino, alkoxyiminomethyl, alkylaminocarbonyl and alkylaminothiocarbonyl, is, in each individual case giving due consideration to the number of carbon atoms contained in the group or compound in question, either straight-chain, that is to say methyl, ethyl, propyl, butyl, pentyl or hexyl, or branched, e.g. isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl or isohexyl.
  • Alkenyl as a group perse and also as a structural unit of other groups and compounds, such as of haloalkenyl, is, in each individual case giving due consideration to the number of carbon atoms contained in the group or compound in question, either straight-chain, for example vinyl, 1-methylvinyl, allyl, 1-butenyl or 2-hexenyl, or branched, for example isopro- penyl.
  • Alkynyl as a group perse and also as a structural unit of other groups and compounds, such as of haloalkynyl, is, in each individual case giving due consideration to the number of carbon atoms contained in the group or compound in question, either straight-chain, for example propargyl, 2-butynyl or 5-hexynyl, or branched, for example 2-ethynylpropyl or 2-propargylisopropyl.
  • Cycloalkyl is cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.
  • Alkylene as a group perse and also as a structural unit of other groups and compounds, such as of haloalkylene, is, in each individual case giving due consideration to the number of carbon atoms contained in the group or compound in question, either straight-chain, for example -CH 2 CH 2 -, -CH 2 CH 2 CH 2 - or -CH 2 CH 2 CH 2 CH 2 -, or branched, for example -CH(CH 3 )-, -CH(C 2 H 5 )-, -C(CH 3 ) 2 -, -CH(CH 3 )CH 2 - or -CH(CH 3 )CH(CH 3 )-.
  • Preference is given to - CH 2 CH 2 -, -CH(CH 3 )-, -CH(C 2 H 5 )-, and -CH 2 CH 2 CH 2 -.
  • Aryl is phenyi or naphthyl, especially phenyi.
  • Heterocyclyl is a 5- to 7-membered aromatic or nonaromatic ring having from one to three hetero atoms selected from the group consisting of N, O and S. Preference is given to aromatic 5- and 6-membered rings having a nitrogen atom as hetero atom and optionally a further hetero atom, preferably nitrogen or sulfur, especially nitrogen.
  • Preferred heteroaryl moieties are pyrazinyl, 3'-pyridyl, 2'-pyridyl, 4'-pyridyl, 2'-pyrimidinyl, 4'-pyrimidinyl, 5'-pyrim- idinyl, 2'-thiazolyl, 2'-oxazolyl, 2'-thienyl, 3'-thienyl and 2'-thiazolyl.
  • Halogen as a group perse and also as a structural unit of other groups and compounds, such as of haloalkyl, haloalkenyl and haloalkynyl, is fluorine, chlorine, bromine or iodine, especially fluorine, chlorine or bromine, more especially fluorine or chlorine, very especially fluorine.
  • Halo-substituted carbon-containing groups and compounds, such as haloalkyl, haloalkenyl or haloalkynyl may be partially halogenated or per-halogenated, it being possible in the case of poly-halogenation for the halogen substituents to be the same or different.
  • haloalkyl as a group perse and also as a structural unit of other groups and compounds, such as of haloalkenyl, are methyl that is mono- to tri-substituted by fluorine, chlorine and/or by bromine, such as CHF 2 or CF 3 ; ethyl that is mono- to penta-substituted by fluorine, chlorine and/or by bromine, such as CH 2 CF 3> CF 2 CF 3 , CF 2 CCI 3 , CF 2 CHCI 2 , CF 2 CHF 2 , CF 2 CFCI 2 , CF 2 CHBr 2 , CF 2 CHCIF, CF 2 CHBrF or CCIFCHCIF; propyl or isopropyl that is mono- to hepta-substituted by fluorine, chlorine and/or by bromine, such as CH 2 CHBrCH 2 Br, CF 2 CHFCF 3 , CH 2 CF 2 CF 3
  • a number of compounds of formula (I), and of the formulae (III) to (XXIV) given hereinafter, may, as is known to the person skilled in the art, be present in the form of tautomers, especially when R 7 is H.
  • any reference to these compounds should therefore be understood as including also corresponding tautomers, even when the latter are not specifically mentioned in each case.
  • Compounds of formula (I), and of the formulae (III) to (XXIV) given hereinafter, that have at least one basic centre may, for example, form acid addition salts.
  • Such salts are formed, for example, with strong inorganic acids, such as mineral acids, e.g. perchloric acid, sulfuric acid, nitric acid, nitrous acid, a phosphoric acid or a hydrohalic acid, with strong organic carboxylic acids, such as unsubstituted or substituted, for example halo-substituted, d-dalkanecarboxylic acids, e.g. acetic acid, saturated or unsaturated dicarboxylic acids, e.g.
  • oxalic acid malonic acid, succinic acid, maleic acid, fumaric acid or phthalic acid, hy- droxycarboxyiic acids, e.g. ascorbic acid, lactic acid, malic acid, tartaric acid or citric acid, or benzoic acid, or with organic sulfonic acids, such as unsubstituted or substituted, for example halo-substituted, C ⁇ -C alkane- or aryl-sulfonic acids, e.g. methane- or p-toluene-sulfonic acid.
  • compounds of formula (I) having at least one acid group may form salts with bases.
  • Suitable salts with bases are, for example, metal salts, such as alkali metal or alkaline earth metal salts, e.g. sodium, potassium or magnesium salts, or salts with ammonia or an organic amine, such as mo ⁇ holine, piperidine, pyrrolidine, a mono-, di- or tri-lower alkylamine, e.g. ethyl-, diethyl-, triethyl- or dimethyl-propyl-amine, or a mono-, di- or tri- hydroxy-lower alkylamine, e.g. mono-, di- or tri-ethanolamine. It may also be possible for corresponding internal salts to be formed.
  • metal salts such as alkali metal or alkaline earth metal salts, e.g. sodium, potassium or magnesium salts, or salts with ammonia or an organic amine, such as mo ⁇ holine, piperidine, pyrrolidine, a mono-, di- or tri-lower alkylamine,
  • agrochemically advantageous salts also included, however, are salts which cannot be agrochemically used, which are used however, for example, for isolating and/or purifying free compounds of formula (I) or agrochemically acceptable salts thereof.
  • any reference to the compounds of formula (I) in free form is to be under-stood as including also the salts of compounds of formula (I), and any reference to the salts is to be understood as including also the corresponding free compounds of formula (I), as appropriate and expedient.
  • tautomers of compounds of formulae (I) and (III) to (XXIV) and salts thereof In each case the free form is generally preferred.
  • R 2 is H, d-C 4 alkyl, halo-d-C 4 alkyl or C 3 -C 6 cycloalkyl, preferably d-dalkyl or halo-C ⁇ -C 4 alkyl, especially C 1 -C 2 alkyl, more especially methyl;
  • R 3 is H, d-dalkyl, d-C 4 alkoxy, OH, CN, NO 2 , halogen, halo-d-C 4 alkyl or halo- d-dalkoxy, preferably H, d-dalkyl, d-C 4 alkoxy or halogen, especially H, methyl, methoxy, chlorine or fluorine, more especially H; (6) a compound of formula (I) wherein
  • R 4 is H, d-dalkyl, d-C alkoxy, OH, CN, NO 2 , halogen, halo-C ⁇ -C alkyl or halo- Ci-dalkoxy, preferably H, C C alkyl, d-C 4 alkoxy or halogen, especially H, methyl, methoxy, chlorine or fluorine, more especially H;
  • R 8 is H or C ⁇ -C 2 alkyl, preferably C ⁇ -C 2 alkyl, especially methyl;
  • A is a direct bond, Ci-Cioalkylene or halo-d-C ⁇ 0 alkylene, preferably a direct bond or C dalkylene, especially a direct bond or methylene, and R 7 is a radical R 10 ;
  • Rn and R ⁇ 2 are each independently of the other C C 6 alkoxy, halo-C C 6 alkoxy, d-C 6 alkylthio, halo-C.-C 6 alkylthio, aryl, aryloxy or arylthio; or aryl, heteroaryl, aryloxy, arylthio, heteroaryioxy or heteroarylthio each mono- to tri- substituted by R 5 , the substituents R 5 being independent of one another;
  • R 6 being especially phenyi that is unsubstituted or mono- or di-substituted, especially mono- substituted, by halogen, d-C 4 alkyl, halo-C ⁇ -C alkyl or by halo-C ⁇ -C 4 alkoxy, especially mono-substituted by fluorine, chlorine, d-dalkyl, trifluoromethyl or by trifluoromethoxy.
  • the invention relates also to a process for the preparation of the compounds of formula (I) and, where applicable, their E Z isomers, mixtures of E Z isomers and/or tautomers, in each case in free form or in salt form, which process comprises, for example, either a1) reacting a compound of formula (I) and, where applicable, their E Z isomers, mixtures of E Z isomers and/or tautomers, in each case in free form or in salt form, which process comprises, for example, either a1) reacting a compound of formula (I) and, where applicable, their E Z isomers, mixtures of E Z isomers and/or tautomers, in each case in free form or in salt form, which process comprises, for example, either a1) reacting a compound of formula (I) and, where applicable, their E Z isomers, mixtures of E Z isomers and/or tautomers, in each case in free form or in salt form, which process comprises, for example, either a1) reacting a
  • the invention relates also to a process for the preparation of compounds of formula (III), in each case in free form or in salt form, which process comprises, for example,
  • R ⁇ ONH, (VII) which is known or can be prepared according to methods known perse and wherein A and R 7 are as defined for formula (I) and, in each case, if desired, converting a compound of formula (III) obtainable according to the process or by a different method, or an E/Z isomer or tautomer thereof, in each case in free form or in salt form, into a different compound of formula (III) or an E/Z isomer or tautomer thereof, in each case in free form or in salt form, separating a mixture of E/Z isomers obtainable according to the process and isolating the desired isomer and/or converting a free compound of formula (III) obtainable according to the process or by a different method, or an E/Z isomer or tautomer thereof, into a salt, or converting a salt of a compound of formula (III), or of an E/Z isomer or tautomer thereof, obtainable according to the process or by a different method into the free
  • the invention relates also to a process for the preparation of a compound of formula
  • Hal is a halogen atom, preferably fluorine, with a compound of formula
  • T in the case where, in a compound of formula (Vlll), T is -C ⁇ C-, reacting a compound of formula wherein R 2 , R 5 , L, D, G, n and b are as defined above for formula (I), with a compound of the formula Hal-Re, which is known or can be prepared in accordance with methods known perse, and wherein Hal is halogen, preferably bromine or iodine, especially iodine, and R ⁇ 8 is as defined for formula (I); or
  • H-N(aryl)R 13 (XXI), which are known or can be prepared in accordance with methods known per se, and wherein v, w, Rn, R ⁇ 2 , R 1 3 and aryl are as defined for fomnula (I), preferably in the presence of a base and a catalyst, especially a transition metal catalyst, more especially a palladium catalyst or a ferrocene derivative;
  • R 2 , R 5 , R 6 , L, D, G, T, a, b and n are as defined in formula (I), in each case in free form or in salt form, which process comprises reacting a compound of the formula (Vlll) with a nitrite;
  • R 5 , R 6 , L, D, G, T, a, b and n are as defined in formula (I), with a nitroalkane;
  • the reactions described hereinbefore and hereinafter are carried out in a manner known per se, for example in the absence or usually in the presence of a suitable solvent or diluent or of a mixture thereof, the reactions being carried out, as required, with cooling, at room temperature or with heating, for example in a temperature range from approximately 0°C to the boiling temperature of the reaction medium, preferably from approximately 20°C to approximately +120°C, especially from 60°C to 80°C, and, if required, in a closed vessel, under pressure, in an inert gas atmosphere and/or under anhydrous conditions.
  • Especially advantageous reaction conditions may be found in the Examples.
  • the reactants may be reacted with one another without the addition of a solvent or diluent, for example in molten form.
  • a solvent or diluent for example in molten form.
  • the addition of an inert solvent or diluent or a mixture thereof is advantageous.
  • the products are isolated in accordance with customary methods, for example by filtration, crystallisation, distillation or chromatography, or any suitable combination of those methods.
  • Suitable leaving groups Xi in the compounds of formula (II) are, for example, hydroxy, d-C 8 alkoxy, haio-d-C 8 alkoxy, C ⁇ -C 8 alkanoyloxy, mercapto, d-C 8 alkylthio, halo-C ⁇ -C 8 alkylthio, d-C 8 alkanesulfonyloxy, halo-C ⁇ -C 8 alkanesulfonyloxy, benzene- sulfonyloxy, toluenesulfonyloxy and halogen, preferably toluenesulfonyloxy, trifluoro- methanesulfonyloxy and halogen, especially halogen.
  • Suitable bases for facilitating the reaction are, for example, alkali metal or alkaline earth metal hydroxides, hydrides, amides, alkanolates, acetates, carbonates, dialkylamides or al- kylsilylamides, alkylamines, alkylenediamines, unsubstituted or N-alkylated, saturated or unsaturated cycloalkylamines, basic heterocycles, ammonium hydroxides and carbocyclic amines.
  • solvents or diluents include: aromatic, aliphatic and alicyclic hydrocarbons and halogenated hydrocarbons, such as benzene, toluene, xylene, mesitylene, Tetralin, chloro- benzene, dichlorobenzene, bromobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, trichloromethane, tetrachloromethane, dichloroethane, trichloroethene and tetrachloroethene; esters, such as ethyl acetate; ethers, such as diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, tert-butyl methyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, dimethoxydiethy
  • bases used in excess such as triethylamine, pyridine, N-methylmo ⁇ holine or N,N-diethylaniline, may also serve as solvents or diluents.
  • the reaction is carried out advantageously in a temperature range from approximately 0°C to approximately 180°C, especially from approximately 10°C to approximately 80°C, in many cases in the range from room temperature to the reflux temperature of the reaction mixture.
  • reaction duration of from approximately 0.1 to approximately 24 hours, especially from approximately 0.5 to approximately 2 hours.
  • a compound of formula (II) is reacted with a compound of formula (III) at from 0°C to 80°C, preferably from 10°C to 30°C, in an inert solvent, preferably an amide, especially N,N-dimethylformamide, in the presence of a metal hydride, preferably sodium hydride.
  • Variant b) examples include those mentioned in variant a1/a2).
  • the reaction is carried out advantageously in a temperature range from approximately 0°C to approximately 180°C, especially from approximately 10°C to approximately 80°C, in many cases in the range from room temperature to the reflux temperature of the reaction mixture. Preference is given to a reaction duration of from approximately 0.1 to approximately 24 hours, especially from approximately 0.5 to approximately 2 hours.
  • solvents or diluents include: aromatic, aliphatic and alicyclic hydrocarbons and halogenated hydrocarbons, such as benzene, toluene, xylene, mesitylene, Tetralin, chlorobenzene, dichlorobenzene, bromobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, trichloromethane, tetrachloromethane, dichloroethane, trichloro- ethene and tetrachloroethene; ethers, such as diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, tert-butyl methyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, dimethoxydiethyl ether, tetra
  • the reaction is carried out advantageously in a temperature range from approximately 0°C to approximately +120°C, preferably from approximately 80°C to approximately +120°C.
  • reaction duration of from approximately 0.1 to approximately 24 hours, especially from approximately 0.5 to approximately 2 hours.
  • Suitable oxidising agents are, for example, inorganic peroxides, such as sodium perborate, or hydrogen peroxide, or organic peracids, such as perbenzoic acid or peracetic acid, or mixtures of organic acids and hydrogen peroxide, for example acetic acid/hydrogen peroxide.
  • solvents or diluents include: aromatic, aliphatic and alicyclic hydrocarbons and halogenated hydrocarbons, such as benzene, toluene, xylene, mesitylene, Tetralin, chloro- benzene, dichlorobenzene, bromobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, trichloromethane, tetrachloromethane, dichloroethane, trichloroethene and tetrachloroethene; esters, such as ethyl acetate; ethers, such as diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, tert-butyl methyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, dimethoxydiethy
  • reaction is carried out in the presence of an organic acid or peracid
  • acids used in excess for example strong organic carboxylic acids, such as unsubstituted or substituted, for example halo-substituted, d-C alkanecarboxylic acids, e.g. formic acid, acetic acid or propionic acid, may also serve as solvent or diluent.
  • the reaction is carried out advantageously in a temperature range from approximately 0°C to approximately +120°C, preferably from approximately 0°C to approximately +40°C.
  • reaction duration of from approximately 0.1 to approximately 24 hours, especially from approximately 0.5 to approximately 2 hours.
  • Suitable bases for facilitating the reaction are, for example, those mentioned in variant a1/a2).
  • solvents or diluents examples include those mentioned in variant a1/a2).
  • the reaction is carried out advantageously in a temperature range from approximately 0°C to approximately 180°C, especially from approximately 10°C to approximately 80°C, in many cases in the range from room temperature to the reflux temperature of the reaction mixture.
  • reaction duration of from approximately 0.1 to approximately 24 hours, especially from approximately 0.5 to approximately 2 hours.
  • Example P3 e Especially preferred conditions may be found in Example P3 e).
  • Variant f Suitable bases for facilitating the reaction are, for example, those mentioned in variant a1/a2).
  • solvents or diluents examples include those mentioned in variant a1/a2).
  • the reaction is carried out advantageously in a temperature range from approximately 0°C to approximately 180°C, especially from approximately 10°C to approximately 80°C, in many cases in the range from room temperature to the reflux temperature of the reaction mixture.
  • a compound of formula (VI) is reacted with a co m- pound of formula (VII) at from 0°C to 120°C, preferably from 60°C to 120°C, in an inert solvent, preferably an amine, especially pyridine.
  • an inert solvent preferably an amine, especially pyridine.
  • Especially preferred conditions may be found in Example P1-1c) and also in the analogous reaction described in Example P3 e).
  • Especially preferred conditions for process variants g), h), i), k), I) and m) may be found in the Examples.
  • the conditions for the process according to variant g) may be found in Examples P9-1 and P9-2; according to variant h) in Example P6-1 ; according to variant i) in Example P1-1a); according to variant k) in Examples P3b) and P5b); according to variant I) in Example P7-1; and according to variant m) in Examples P10-1 and P12-1 or applied analogously to those processes.
  • Some of the compounds of formulae (I) and (III) to (XXIV) may be in the form of one of the possible isomers or in the form of a mixture thereof, for example according to the number of asymmetric carbon atoms and the absolute and relative configuration thereof in the form of pure isomers, such as antipodes and/or diastereoisomers, or in the form of mixtures of isomers, such as mixtures of enantiomers, for example racemates, mixtures of diastereoisomers or mixtures of racemates; the invention relates both to the pure isomers and to all possible mixtures of isomers and this is to be understood accordingly hereinbefore and hereinafter, even if stereochemical details are not specifically mentioned in each case.
  • enantiomers such as racemates
  • optical antipodes can be separated into the optical antipodes by known methods, for example by recrystaliisation from an optically active solvent, by chromatography on chiral adsorbents, for example high-pressure liquid chromatography (HPLC) on acetyl cellulose, with the aid of suitable microorganisms, by cleav- age with specific immobilised enzymes, and via the formation of inclusion compounds, for example using chiral crown ethers, in which case only one enantiomer is complexed.
  • HPLC high-pressure liquid chromatography
  • Some of the compounds (I) and (III) to (XXIV) can also be obtained in the form of their hydrates and/or may include other solvents, for example solvents that may have been used for the crystallisation of compounds in solid form.
  • the invention relates to all those embodiments of the process according to which a compound obtainable as starting material or intermediate at any stage of the process is used as starting material and all or some of the remaining steps are carried out, or a starting material is used in the form of a derivative or a salt and/or its racemates or antipodes, or, especially, is formed under the reaction conditions.
  • the invention relates especially to the preparation processes described in Examples P1 to P12.
  • the invention relates also to starting materials and intermediates used according to the i n- vention in the preparation of compounds of formula (I), especially the compounds of form u- lae (III), (IV), (VI), (Vlll), (IX), (XII), (XIII), (XV), (XVII), (XVIII), (XXII), (XXIII) and (XXIV), which are novel, to their use and to processes for the preparation thereof.
  • the compounds of formulae (III) and (VI) can be prepared analogously to Examples P1 c) and P1 b), respectively.
  • the compounds of formula (I) according to the invention are valuable preventive and/or curative active ingredients having a very advantageous biocidal spectrum even at low rates of concentration, while being well tolerated by warm-blooded animals, fish and plants.
  • the compounds of the invention are effective against all or individual development stages of normally sensitive animal pests, but also of resistant animal pests, such as insects and representatives of the order Acarina, and phytopathogenic fungi.
  • the insecticidal, ovicidal and/or acaricidal action of the compounds of the invention may manifest itself directly, i.e. in the mortality of the pests, which occurs immediately or only after some time, for example during moulting, or of their eggs, or indirectly, for example in reduced oviposition and/or hatching rate, good activity corresponding to a mortality of at least 50 to 60 %.
  • the mentioned animal pests include, for example, those mentioned in European Patent Application EP-A-736 252. Accordingly, the said pests mentioned in EP-A-736 252 are included by reference in the subject matter of the present invention.
  • the mentioned phytopathogenic fungi include, for example: of the class of the Fungi imperfecti, for example,
  • Botrytis spp. Pyricularia spp., Helminthosporium spp., Fusarium spp., Septoria spp., Cerco- spora spp. and Alternaria spp.; of the class of the Basidiomycetes, for example,
  • Rhizoctonia spp. Hemileia spp. and Puccinia spp.; of the class of the Ascomycetes, for example,
  • Venturia spp. Erysiphe spp., Podosphaera spp., Monilinia spp. and Uncinula spp.; and of the class of the Oomycetes, for example,
  • Target crops are especially cereals, such as wheat, barley, rye, oats, rice, maize and sorghum; beet, such as sugar beet and fodder beet; fruit, such as pomes, stone fruit and soft fruit, such as apples, pears, plums, peaches, almonds, cherries, or berries, for example strawberries, raspberries and blackberries; leguminous plants, such as beans, lentils, peas and soybeans; oil plants, such as rape, mustard, poppy, olives, sunflowers, coconut, castor oil plants, cocoa beans and groundnuts; cucurbitaceae, such as marrows, cucumber and melons; fibre plants, such as cotton, flax, hemp and jute; citrus fruit, such as oranges, lemons, grapefruit and mandarins; vegetables, such as spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes and paprika; lauraceae, such as avocados, cinnamon and camphor; and tobacco, nuts, coffee
  • the compounds according to the invention are especially suitable for controlling insects and representatives of the order Acarina, especially plant-destructive feeding insects, such as Anthonomus grandis, Diabrotica balteata, Heliothis virescens larvae, Plutella xylostella and Spodoptera littoralis larvae, and spider mites, such as Tetranychus spp., in cotton, fruit, maize, soybean, rape and vegetable crops.
  • plant-destructive feeding insects such as Anthonomus grandis, Diabrotica balteata, Heliothis virescens larvae, Plutella xylostella and Spodoptera littoralis larvae
  • spider mites such as Tetranychus spp., in cotton, fruit, maize, soybean, rape and vegetable crops.
  • the invention therefore relates also to pesticides, such as emulsifiabie concentrates, suspension concentrates, directly sprayable or dilutable solutions, coatable pastes, dilute emulsions, wettable powders, soluble powders, dispersible powders, wettable powders, dusts, granules or encapsulations in polymer substances, comprising - at least - one of the compounds of the invention, the type of formulation being chosen in accordance with the intended objectives and prevailing circumstances.
  • pesticides such as emulsifiabie concentrates, suspension concentrates, directly sprayable or dilutable solutions, coatable pastes, dilute emulsions, wettable powders, soluble powders, dispersible powders, wettable powders, dusts, granules or encapsulations in polymer substances, comprising - at least - one of the compounds of the invention, the type of formulation being chosen in accordance with the intended objectives and prevailing circumstances.
  • the active ingredient is used in those compositions in pure form: a solid active ingredient, for example, in a specific particle size, or preferably together with - at least - one of the adjuvants customary in formulation technology, such as extenders, for example solvents or solid carriers, or surface-active compounds (surfactants).
  • a solid active ingredient for example, in a specific particle size, or preferably together with - at least - one of the adjuvants customary in formulation technology, such as extenders, for example solvents or solid carriers, or surface-active compounds (surfactants).
  • Formulation adjuvants used are, e.g., solid carriers, solvents, stabilisers, "slow release” adjuvants, colorants and optionally surface-active substances (surfactants).
  • Suitable carriers and adjuvants include any substances customarily used in plant protection compositions, especially in compositions for controlling slugs and snails.
  • Suitable adjuvants, such as solvents, solid carriers, surface-active compounds, non-ionic surfactants, cationic surfactants, anionic surfactants and other adjuvants in the compositions used according to the invention include, for example, the same substances as those described in EP-A-736252. Accordingly, the said adjuvants mentioned in EP-A-736252 are included by reference in the subject matter of the present invention.
  • compositions usually comprise 0.1 to 99%, preferably 0.1 to 95%, of active ingredient, and 1 to 99.9%, preferably 5 to 99.9%, of - at least - one solid or liquid adjuvant, it generally being possible for 0 to 25%, preferably 0.1 to 20%, of the composition to be surfactants (in each case percentages are by weight).
  • surfactants in each case percentages are by weight.
  • Emulsifiable concentrates active ingredient: 1 to 90 %, preferably 5 to 20 % surfactant: 1 to 30 %, preferably 10 to 20 % solvent: 5 to 98 %, preferably 70 to 85 %
  • Dusts active ingredient: 0.1 to 10 %, preferably 0.1 to 1 % solid carrier: 99.9 to 90 %, preferably 99.9 to 99 %
  • Suspension concentrates active ingredient: 5 to 75 %, preferably 10 to 50 % water: 94 to 24 %, preferably 88 to 30 % surfactant: 1 to 40 %, preferably 2 to 30 %
  • Wettable powders active ingredient: 0.5 to 90 %, preferably 1 to 80 % surfactant: 0.5 to 20 %, preferably 1 to 15 % solid carrier: 5 to 99 %, preferably 15 to 98 %
  • Granules active ingredient: 0.5 to 30 %, preferably 3 to 15 % solid carrier: 99.5 to 70 %, preferably 97 to 85 %
  • compositions according to the invention can be substantially broadened and adapted to prevailing circumstances by the addition of other insecticidal, acaricidal and/or f ungicidal active ingredients.
  • suitable additional active ingredients include representatives of the following classes of compounds: organophosphorus compounds, nitrophenols and derivatives, formamidines, ureas, carbamates, pyrethroids, chlorinated hydrocarbons and Bacillus thuringiensis preparations.
  • the compositions according to the invention may also comprise further solid or liquid adjuvants, such as stabilisers, for example vegetable oils or epoxidised vegetable oils (e.g.
  • epoxidised coconut oil, rape oil or soybean oil epoxidised coconut oil, rape oil or soybean oil
  • antifoams for example silicone oil, preservatives, viscosity regulators, binders and/or tackifiers, as well as fertilisers or other active ingredients for obtaining special effects, for example bactericides, nematicides, molluscicides or selective herbicides.
  • compositions according to the invention are prepared in known manner, in the absence of adjuvants, for example by grinding and/or sieving a solid active ingredient or mixture of active ingredients, for example to a specific particle size, or in the presence of at least one adjuvant, for example by intimately mixing and/or grinding the active ingredient or mixture of active ingredients with the adjuvant(s).
  • the invention relates also to those processes for the preparation of the compositions according to the invention and to the use of the compounds of formula (I) in the preparation of those compositions.
  • the invention relates also to the methods of application of the compositions, i.e.
  • Typical rates of concentration are from 0.1 to 1000 ppm, preferably from 0.1 to 500 ppm, of active ingredient.
  • the rates of application per hectare are generally from 1 to 2000 g of active ingredient per hectare, especially from 10 to 1000 g/ha, preferably from 20 to 600 g/ha.
  • a preferred method of application in the area of plant protection is application to the foliage of the plants (foliar application), the number of applications and the rate of application depending on the risk of infestation by the pest in question.
  • the active ingredient can also penetrate the plants through the roots (systemic action) if the locus of the plants is impregnated with a liquid formulation or if the active ingredient is inco ⁇ orated in solid form into the locus of the plants, for example into 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.
  • compositions according to the invention are also suitable for protecting plant propagation material, e.g. seed, such as fruit, tubers or grains, or plant cuttings, from fungal infections and animal pests.
  • the propagation material can be treated with the formulation before planting: seed, for example, can be dressed before being sown.
  • the compounds of the invention can also be applied to grains (coating), either by impregnating the grains with a liquid formulation or by coating them with a solid formulation.
  • the formulation can also be applied to the planting site when the propagation material is being planted, for example to the seed furrow during sowing.
  • the invention relates also to those methods of treating plant propagation material and to the plant propagation material thus treated.
  • Example P1-1 2-[[[(1 -Methyl-2-(4-(1 - ⁇ 4-chlorophenyl ⁇ -ethoxy)-phenyl)-[ethoxyimino]- ethylidene)amino]oxy]methyl]- ⁇ -(methoxymethylene)-phenylacetic acid methyl ester a) 1 -[4-(1 - ⁇ 4-Chlorophenyl ⁇ -ethoxy)-phenyl]-propan-1 -one
  • Dry HCI gas is introduced into 200 ml of diethyl ether over a period of 0.5 minutes and 43.2 g of 1-[4-(1- ⁇ 4-chlorophenyl ⁇ -ethoxy)-phenyl]-propan-1-one are then added. 21.0 g of isopentyl nitrite are then added dropwise and the reaction mixture is then stirred for 3 hours at room temperature. The reaction mixture is concentrated by evaporation in vacuo and the crude product is purified by chromatography on silica gel using ethyl acetate/hexane (1:3), yielding the title compound having a melting point of 88-90°C.
  • Example P1-2 2-[[[(1 -Methyl-2-(4-(1 - ⁇ 4-chlorophenyl ⁇ -ethoxy)-phenyl)-[ethoxyimino]ethyl- idene)amino]oxy]methyl]- ⁇ -(methoxyimino)-phenylacetic acid methyl ester
  • 1 -[4-(1 - ⁇ 4-chlorophenyl ⁇ - ethoxy)-phenyl]-1 ,2-propanedione-[ethyloxime]-2-oxime and 2-(bromomethyl)- ⁇ -(methoxy- imino)-phenylacetic acid methyl ester yield the title compound having a melting point of 111 -113°C (compound 2.4-2).
  • Example P1-3 2-[[[(1 -Methyl-2-(4-(1 - ⁇ 4-chlorophenyl ⁇ -ethoxy)-phenyl)-[ethoxyimino]ethyl- idene)amino]oxy]methyl]- ⁇ -(methoxyimino)-phenylacetic acid methylamide
  • Example P2 It is also possible to prepare the other compounds listed in Tables 1.1 to 3.26 in a manner analogous to that described in Example P1; c.propyl denotes cyclopropyl.
  • Table 1 -2 Compounds of general formula (1.1) wherein (R 5 ) s is 3-CF 3 and the substituent A-R 7 corresponds in each case to a line of Table A.
  • Table 1 -3 Compounds of general formula (1.1) wherein (R 5 ) s is 2-CF 3 and the substituent A-R 7 corresponds in each case to a line of Table A.
  • Table 1 -4 Compounds of general formula (1.1) wherein (R 5 )s is 4-CI and the substituent A-R 7 corresponds in each case to a line of Table A.
  • Table 1 -5 Compounds of general formula (1.1) wherein (R 5 ) s is 3-CI and the substituent A-R 7 corresponds in each case to a line of Table A.
  • Table 1-6 Compounds of general formula (1.1) wherein (R 5 )s is 2-CI and the substituent A-R 7 corresponds in each case to a line of Table A.
  • Table 1 -7 Compounds of general formula (1.1) wherein (R 5 ) s is 4-Br and the substituent A-R 7 corresponds in each case to a line of Table A.
  • Table 1 -8 Compounds of general formula (1.1) wherein (R 5 )s is 3-Br and the substituent A-R 7 corresponds in each case to a line of Table A.
  • Table 1-9 Compounds of general formula (1.1) wherein (R 5 ) s is 2-Br and the substituent A-R 7 corresponds in each case to a line of Table A.
  • Table 1-10 Compounds of general formula (1.1) wherein (R 5 ) s is 4-F and the substituent A-R 7 corresponds in each case to a line of Table A.
  • Table 1-11 Compounds of general formula (1.1) wherein (R 5 ) s is 3-F and the substituent A-R 7 corresponds in each case to a line of Table A.
  • Table 1-12 Compounds of general formula (1.1) wherein (R 5 ) s is 2-F and the substituent A-R 7 corresponds in each case to a line of Table A.
  • Table 1-13 Compounds of general formula (1.1) wherein (R 5 ) s is 2,4-CI 2 and the substituent A-R 7 corresponds in each case to a line of Table A.
  • Table 1-14 Compounds of general formula (1.1) wherein (R 5 ) s is 3,4-CI 2 and the substituent A-R 7 corresponds in each case to a line of Table A.
  • Table 1-15 Compounds of general formula (1.1) wherein (R 5 ) s is 4-O-CF 3 and the substituent A-R 7 corresponds in each case to a line of Table A.
  • Table 1-16 Compounds of general formula (1.1) wherein (R 5 ) s is 4-CH 3 and the substituent A-R 7 corresponds in each case to a line of Table A.
  • Table 1-17 Compounds of general formula (1.1) wherein (R 5 ) s is 4-C 2 H 5 and the substituent A-R 7 corresponds in each case to a line of Table A.
  • Table 1-18 Compounds of general formula (1.1) wherein (R 5 ) s is 4-n-C 3 H 7 and the substituent A-R 7 corresponds in each case to a line of Table A.
  • Table 1-19 Compounds of general formula (1.1) wherein (R 5 ) s is 4-iso-C 3 H 7 and the substituent A-R 7 corresponds in each case to a line of Table A.
  • Table 1 -20 Compounds of general formula (1.1) wherein (R 5 ) s is 4-n-C H 9 and the substituent A-R 7 corresponds in each case to a line of Table A.
  • Table 1 -21 Compounds of general formula (1.1) wherein (R 5 ) s is 4-isobutyl and the substituent A-R 7 corresponds in each case to a line of Table A.
  • Table 1-22 Compounds of general formula (1.1) wherein (R 5 )s is 4-sec-butyl and the substituent A-R 7 corresponds in each case to a line of Table A.
  • Table 1 -23 Compounds of general formula (1.1) wherein (R 5 )s is 4-tert-butyl and the substituent A-R 7 corresponds in each case to a line of Table A.
  • Table 1-24 Compounds of general formula (1.1) wherein (R 5 ) s is 4-CN and the substituent A-R 7 corresponds in each case to a line of Table A.
  • Table 1-25 Compounds of general formula (1.1) wherein (R 5 ) s is 4-O-CH 3 and the substituent A-R 7 corresponds in each case to a line of Table A.
  • Table 1-26 Compounds of general formula (1.1) wherein (R 5 ) s is 2,4-F 2 and the substituent A-R 7 corresponds in each case to a line of Table A.
  • Table 2-2 Compounds of general formula (I.2) wherein (R 5 ) s is 3-CF 3 and the substituent A-R 7 corresponds in each case to a line of Table A.
  • Table 2-3 Compounds of general formula (I.2) wherein (R 5 ) s is 2-CF 3 and the substituent A-R 7 corresponds in each case to a line of Table A.
  • Table 2-4 Compounds of general formula (I.2) wherein (R 5 ) s is 4-CI and the substituent A-R 7 corresponds in each case to a line of Table A.
  • Table 2-5 Compounds of general formula (I.2) wherein (R 5 ) s is 3-CI and the substituent A-R 7 corresponds in each case to a line of Table A.
  • Table 2-6 Compounds of general formula (1.2) wherein (R 5 ) s is 2-CI and the substituent A-R 7 corresponds in each case to a line of Table A.
  • Table 2-7 Compounds of general formula (1.2) wherein (R 5 ) s is 4-Br and the substituent A-R 7 corresponds in each case to a line of Table A.
  • Table 2-8 Compounds of general formula (1.2) wherein (R 5 ) s is 3-Br and the substituent A-R corresponds in each case to a line of Table A.
  • Table 2-9 Compounds of general formula (1.2) wherein (R 5 ) s is 2-Br and the substituent A-R 7 corresponds in each case to a line of Table A.
  • Table 2-10 Compounds of general formula (I.2) wherein (R 5 ) s is 4-F and the substituent A-R 7 corresponds in each case to a line of Table A.
  • Table 2-11 Compounds of general formula (I.2) wherein (R 5 ) s is 3-F and the substituent A-R 7 corresponds in each case to a line of Table A.
  • Table 2-12 Compounds of general formula (I.2) wherein (R 5 ) s is 2-F and the substituent A-R corresponds in each case to a line of Table A.
  • Table 2-13 Compounds of general formula (I.2) wherein (R 5 ) s is 2,4-CI 2 and the substituent A-R 7 corresponds in each case to a line of Table A.
  • Table 2-14 Compounds of general formula (I.2) wherein (R 5 ) s is 3,4-CI 2 and the substituent A-R 7 corresponds in each case to a line of Table A.
  • Table 2-15 Compounds of general formula (I.2) wherein (R 5 ) s is 4-O-CF 3 and the substituent A-R 7 corresponds in each case to a line of Table A.
  • Table 2-16 Compounds of general formula (I.2) wherein (R 5 ) s is 4-CH 3 and the substituent A-R 7 corresponds in each case to a line of Table A.
  • Table 2-17 Compounds of general formula (I.2) wherein (R 5 ) s is 4-C 2 H 5 and the substituent A-R 7 corresponds in each case to a line of Table A.
  • Table 2-18 Compounds of general formula (I.2) wherein (R 5 ) s is 4-n-C 3 H 7 and the substituent A-R corresponds in each case to a line of Table A.
  • Table 2-19 Compounds of general formula (I.2) wherein (R 5 ) s is 4-iso-C 3 H 7 and the substituent A-R 7 corresponds in each case to a line of Table A.
  • Table 2-20 Compounds of general formula (1.2) wherein (R 5 ) s is 4-n-C H 9 and the substituent A-R 7 corresponds in each case to a line of Table A.
  • Table 2-21 Compounds of general formula (I.2) wherein (R 5 )s is 4-isobutyl and the substituent A-R 7 corresponds in each case to a line of Table A.
  • Table 2-22 Compounds of general formula (I.2) wherein (R 5 ) s is 4-sec-butyl and the substituent A-R 7 corresponds in each case to a line of Table A.
  • Table 2-23 Compounds of general formula (I.2) wherein (R 5 ) s is 4-tert-butyl and the substituent A-R 7 corresponds in each case to a line of Table A.
  • Table 2-24 Compounds of general formula (I.2) wherein (R 5 ) s is 4-CN and the substituent A-R 7 corresponds in each case to a line of Table A.
  • Table 2-25 Compounds of general formula (I.2) wherein (R 5 ) s is 4-O-CH 3 and the substituent A-R 7 corresponds in each case to a line of Table A.
  • Table 2-26 Compounds of general formula (I.2) wherein (R 5 ) s is 2,4-F 2 and the substituent A-R 7 corresponds in each case to a line of Table A.
  • Table 3-2 Compounds of general formula (I.3) wherein (R 5 ) s is 3-CF 3 and the substituent A-R 7 corresponds in each case to a line of Table A.
  • Table 3-3 Compounds of general formula (I.3) wherein (R 5 ) s is 2-CF 3 and the substituent A-R 7 corresponds in each case to a line of Table A.
  • Table 3-4 Compounds of general formula (I.3) wherein (R 5 ) s is 4-CI and the substituent A-R 7 corresponds in each case to a line of Table A.
  • Table 3-5 Compounds of general formula (1.3) wherein (R 5 )s is 3-CI and the substituent A-R 7 corresponds in each case to a line of Table A.
  • Table 3-6 Compounds of general formula (1.3) wherein (R 5 )s is 2-CI and the substituent A-R 7 corresponds in each case to a line of Table A.
  • Table 3-7 Compounds of general formula (1.3) wherein (R 5 ) s is 4-Br and the substituent A-R 7 corresponds in each case to a line of Table A.
  • Table 3-8 Compounds of general formula (1.3) wherein (R 5 ) s is 3-Br and the substituent A-R 7 corresponds in each case to a line of Table A.
  • Table 3-9 Compounds of general formula (1.3) wherein (R 5 ) s is 2-Br and the substituent A-R 7 corresponds in each case to a line of Table A.
  • Table 3-10 Compounds of general formula (I.3) wherein (R 5 ) s is 4-F and the substituent A-R 7 corresponds in each case to a line of Table A.
  • Table 3-11 Compounds of general formula (I.3) wherein (R 5 ) s is 3-F and the substituent A-R 7 corresponds in each case to a line of Table A.
  • Table 3-12 Compounds of general formula (I.3) wherein (R 5 ) s is 2-F and the substituent A-R 7 corresponds in each case to a line of Table A.
  • Table 3-13 Compounds of general formula (I.3) wherein (R 5 ) s is 2,4-CI 2 and the substituent A-R 7 corresponds in each case to a line of Table A.
  • Table 3-14 Compounds of general formula (I.3) wherein (R 5 ) s is 3,4-CI 2 and the substituent A-R 7 corresponds in each case to a line of Table A.
  • Table 3-15 Compounds of general formula (I.3) wherein (R 5 ) s is 4-O-CF 3 and the substituent A-R 7 corresponds in each case to a line of Table A.
  • Table 3-16 Compounds of general formula (I.3) wherein (R 5 )s is 4-CH 3 and the substituent A-R 7 corresponds in each case to a line of Table A.
  • Table 3-17 Compounds of general formula (I.3) wherein (R 5 ) s is 4-C 2 H 5 and the substituent A-R corresponds in each case to a line of Table A.
  • Table 3-18 Compounds of general formula (I.3) wherein (R 5 ) s is 4-n-C 3 H 7 and the substituent A-R 7 corresponds in each case to a line of Table A.
  • Table 3-19 Compounds of general formula (I.3) wherein (R s ) s is 4-iso-C 3 H 7 and the substituent A-R 7 corresponds in each case to a line of Table A.
  • Table 3-20 Compounds of general formula (I.3) wherein (R 5 ) s is 4-n-C 4 H 9 and the substituent A-R 7 corresponds in each case to a line of Table A.
  • Table 3-21 Compounds of general formula (I.3) wherein (R 5 ) s is 4-isobutyl and the substituent A-R 7 corresponds in each case to a line of Table A.
  • Table 3-22 Compounds of general formula (I.3) wherein (R 5 ) s is 4-sec-butyl and the substituent A-R 7 corresponds in each case to a line of Table A.
  • Table 3-23 Compounds of general formula (I.3) wherein (R 5 ) s is 4-tert-butyl and the substituent A-R 7 corresponds in each case to a line of Table A.
  • Table 3-24 Compounds of general formula (I.3) wherein (R 5 )s is 4-CN and the substituent A-R 7 corresponds in each case to a line of Table A.
  • Table 3-25 Compounds of general formula (I.3) wherein (R 5 ) s is 4-O-CH 3 and the substituent A-R 7 corresponds in each case to a line of Table A.
  • Table 3-26 Compounds of general formula (I.3) wherein (R 5 ) s is 2,4-F 2 and the substituent A-R 7 corresponds in each case to a line of Table A.
  • 35 g of a compound obtainable according to process P3b) are placed in 200 ml of methanol and 18 ml of isopentyl nitrite. At 0°C, 30 ml of a 30 % solution of sodium methanolate in methanol are added dropwise and the mixture is stirred for 2 hours at room temperature. The solvent is evaporated off, and 200 ml of ethyl acetate and 200 ml of water are added; the aqueous phase is separated off and the organic phase is then washed several times with water. Evaporating off the solvent and recrystallisation of the residue from di- chloromethane/hexane yield the title product having a melting point of 131-133°C.
  • Example P4 It is also possible to prepare the other compounds listed in Table 4 in a manner analogous to that described in Example P3.
  • the figures given in the column "Phys. data” denote melting points in °C.
  • Table 4-1 Compounds of general formula
  • Example P5-1 2-ITf (1 -Methvl-2-(4-f(dimethyl-(4-f luorophenvh-silvllmethoxvlphenvl ⁇ - [ethoxyimino]ethylidene)amino]oxy]methyl]- ⁇ -(methoxyimino)-phenylacetic acid methyl ester and 2-[[[(1-methyl-2-(4-[ ⁇ dimethyl-(4-fluorophenyl)-silyl ⁇ methoxy]phenyl)-[ethoxyimino]ethyl- idene)amino]oxy]methyl]- ⁇ -(methoxyimino)-phenylacetic acid methylamide a) Chloromethyl-dimethyl-(4-fluorophenyl)-silane
  • reaction mixture is poured onto 200 ml of ice, and 300 ml of diethyl ether are added; the mixture is washed with water and saturated sodium chloride solution and dried over sodium sulfate; the solvent is evaporated off in vacuo. Distillation of the residue at 97- 105°C (21 mbar) yields the title product.
  • Example P5-2 It is also possible to prepare the other compounds listed in Table 5 in a manner analogous to that described in Example P5-1.
  • the figures given in the column "Phys. data” denote melting points in °C.
  • Example P6-2 It is also possible to prepare the other compounds listed in Table 6 in a manner analogous to that described in Example P6-1.
  • the figures given in the column "Phys. data” denote melting points in °C.
  • Example P7-2 It is also possible to prepare the other compounds listed in Table 7 in a manner analogous to that described in Example P7-1.
  • the figures given in the column "Phys. data” denote melting points in °C.
  • Example P8-1 2-[[[(1-Meth yl-2-(4- ⁇ 3-(3-trifl ⁇ loromethylph
  • Example P8-2 It is also possible to prepare the other compounds listed in Table 8 in a manner analogous to that described in Example P8-1.
  • Example P9-3 It is also possible to prepare the other compounds listed in Tables 9-1 and 9-2 in a manner analogous to that described in Examples P9-1 and P9-2.
  • the figures given in the column "Phys. data” denote melting points in °C.
  • reaction mixture is cooled, filtered over silica gel and diluted with ethyl acetate; the organic phase is extracted by shaking with water and saturated NaCl solution. After drying over MgSO 4 and evaporating off the solvent, a sticky residue is obtained, which is purified by means of column chromatography (ethyl acetate/hexane 1 :5), yielding the title compound having a melting point of 109-110°C.
  • Isopentyl nitrite (3.0 g) is slowly added dropwise at 20°C to 7.2 g of 6-chloro-3-(4'-(2-oxo- propyl)phenyl)benzisoxazole in methanol (37 ml). After the addition of 30 % sodium methanolate (5.7 g), stirring is carried out overnight at room temperature. The reaction mixture is concentrated by evaporation at 50°C; the residue is dissolved in water and rendered acidic with 10 % hydrochloric acid at 10°C. Ethyl acetate is added, the water phase separated and the organic phase washed with water. Drying over MgSO 4 and concentration by evaporation yield a solid, which is stirred together with hexane, filtered off with suction and dried in air to yield the title compound having a melting point of 224-226°C.
  • Ethyl iodide (5.45 g) is added to 6-chloro-3-(4'-(1-hydroxyimino-2-oxo)propyl)benzisoxazole (7.01 g), acetonitrile (44 ml) and potassium carbonate (4.3 g).
  • the batch is heated for 3 hours under reflux, cooled to room temperature and filtered, the filter being rinsed with acetonitrile.
  • the filtrate is concentrated by evaporation using a rotary evaporator; the residue is taken up in ethyl acetate and washed with water and brine. Drying of the organic phase over Na 2 SO and concentration by evaporation yield the title compound having a melting point of 106-107°C.
  • compounds 9-3.1 to 9-3.3 can be prepared analogously to the process variants a1), a2) and b).
  • Example P9-5 It is also possible to prepare the intermediates required for the other compounds listed in Table 9-3 in a manner analogous to that described in Example P9-4.
  • the figures given in the column "Phys. data” denote melting points in °C.
  • Example P11 It is also possible to prepare the other compounds listed in Tables 10 and 11 in a manner analogous to that described in Example P10-1.
  • Table B Compounds of general formula
  • Table 10-1 Compounds of general formula (1.10) wherein AR 7 is CH 3 and the combination of substituents X, Y, (W) w , Rn and R. 2 for each compound corresponds to a line of Table B.
  • Table 10-2 Compounds of formula (1.10) wherein AR 7 is CH 2 CH 3 and the combination of substituents X, Y, (W) w , Rn and R ⁇ 2 for each compound corresponds to a line of Table B.
  • Table 10-4 Compounds of formula (1.10) wherein AR 7 is CH 2 C ⁇ CH and the combination of substituents X, Y, (W) w , Rn and R-
  • Table 10-5 Compounds of formula (1.10) wherein AR 7 is CH 2 CH 2 CH 3 and the combination of substituents X, Y, (W) w , Rn and R 12 for each compound corresponds to a line of Table B.
  • Table 10-6 Compounds of formula (1.10) wherein AR 7 is CH(CH 3 ) 2 and the combination of substituents X, Y, (W) w , Rn and R 12 for each compound corresponds to a line of Table B.
  • Table 10-7 Compounds of formula (1.10) wherein AR 7 is CH 2 CH 2 CH 2 CH 3 and the combination of substituents X, Y, (W) w , Rn and R 12 for each compound corresponds to a line of Table B.
  • Table 10-8 Compounds of formula (1.10) wherein AR 7 is CH(CH 3 )(CH 2 CH 3 ) and the combination of substituents X, Y, (W) w , Rn and R 12 for each compound corresponds to a line of Table B.
  • Table 10-9 Compounds of formula (1.10) wherein AR 7 is C(CH 3 ) 3 and the combination of substituents X, Y, (W) w , Rn and R 12 for each compound corresponds to a line of Table B.
  • Table 10-10 Compounds of formula (1.10) wherein AR 7 is CH 2 CF 3 and the combination of substituents X, Y, (W) w , R and R 12 for each compound corresponds to a line of Table B.
  • Table 10-13 Compounds of formula (1.10) wherein AR 7 is CH 2 Si(CH 3 ) 3 and the combination of substituents X, Y, (W) w , Rn and R 12 for each compound corresponds to a line of Table B.
  • Table 10-14 Compounds of formula (1.10) wherein AR 7 is CH 2 -c.propyl-2,2-CI 2 and the combination of substituents X, Y, (W) w , Rn and R 12 for each compound corresponds to a line of Table B.
  • Table 10-15 Compounds of formula (1.10) wherein AR 7 is CH 2 CN and the combination of substituents X, Y, (W) WI Rn and R 12 for each compound corresponds to a line of Table B.
  • Table 10-16 Compounds of formula (1.10) wherein AR 7 is CH 2 COOCH 3 and the combination of substituents X, Y, (W) w , Rn and R-
  • Table 10-17 Compounds of formula (1.10) wherein AR 7 is CH 2 COO-iso-C 3 H 7 and the combination of substituents X, Y, (W) w , Rn and R 12 for each compound corresponds to a line of Table B.
  • Table 10-21 Compounds of formula (1.10) wherein AR is CH 2 C 6 H 5 and the combination of substituents X, Y, (W) w , Rn and R 12 for each compound corresponds to a line of Table B.
  • Table 10-22 Compounds of formula (1.10) wherein AR 7 is CH 2 C 6 H 4 -2-F and the combination of substituents X, Y and (W) w , Rn and R 12 for each compound corresponds to a line of Table B.
  • Table 10-23 Compounds of formula (1.10) wherein AR 7 is CH 2 C 6 H 4 -3-CI and the combination of substituents X, Y, (W) w , Rn and R 2 for each compound corresponds to a line of Table B.
  • Table 10-24 Compounds of formula (1.10) wherein AR 7 is CH 2 C 6 H 4 -4-Br and the combination of substituents X, Y, (W) w , Rn and R 12 for each compound corresponds to a line of Table B.
  • Table 10-25 Compounds of formula (1.10) wherein AR 7 is CH 2 C 6 H 4 -3-CF 3 and the combination of substituents X, Y, (W) w , Rn and R ⁇ 2 for each compound corresponds to a line of Table B.
  • Table 10-26 Compounds of formula (1.10) wherein AR is CH 2 C 6 H 4 -4-CF 3 and the combination of substituents X, Y, (W) w , Rn and R ⁇ 2 for each compound corresponds to a line of Table B.
  • Table 11-1 Compounds of formula
  • AR 7 is CH 3 and the combination of substituents X, Y, (W) w , Rn and R 12 for each compound corresponds to a line of Table B.
  • Table 11 -2 Compounds of formula (1.11) wherein AR 7 is CH 2 CH 3 and the combination of substituents X, Y, (W) w , Rn and R-
  • Table 11-5 Compounds of formula (1.11 ) wherein AR is CH 2 CH 2 CH 3 and the combination of substituents X, Y, (W) w , Rn and R ⁇ 2 for each compound corresponds to a line of Table B.
  • Table 11 -6 Compounds of formula (1.11) wherein AR 7 is CH(CH 3 ) 2 and the combination of substituents X, Y, (W) w , Rn and R- ⁇ 2 for each compound corresponds to a line of Table B.
  • Table 11 -7 Compounds of formula (1.11) wherein AR 7 is CH 2 CH 2 CH 2 CH 3 and the combination of substituents X, Y, (W) w , Rn and R-
  • Table 11 -8 Compounds of formula (1.11) wherein AR 7 is CH(CH 3 )(CH 2 CH 3 ) and the combination of substituents X, Y, (W) w , Rn and R-
  • Table 11-9 Compounds of formula (1.11) wherein AR 7 is C(CH 3 ) 3 and the combination of substituents X, Y, (W) w , Rn and R-
  • Table 11-10 Compounds of formula (1.11) wherein AR 7 is CH 2 CF 3 and the combination of substituents X, Y, (W) w , Rn and R 12 for each compound corresponds to a line of Table B.
  • Table 11-13 Compounds of formula (1.11 ) wherein AR 7 is CH 2 Si(CH 3 ) 3 and the combination of substituents X, Y, (W) w , Rn and R ⁇ 2 for each compound corresponds to a line of Table B.
  • Table 11-14 Compounds of formula (1.11) wherein AR 7 is CH 2 -c.propyl-2,2-CI 2 and the combination of substituents X, Y, (W) w , Rn and R-
  • Table 11-15 Compounds of formula (1.11) wherein AR 7 is CH 2 CN and the combination of substituents X, Y, (W) w , Rn and R-
  • Table 11-16 Compounds of formula (1.11) wherein AR 7 is CH 2 COOCH 3 and the combination of substituents X, Y, (W) w , Rn and R- ⁇ 2 for each compound corresponds to a line of Table B.
  • Table 11-17 Compounds of formula (1.11) wherein AR 7 is CH 2 COO-iso-C 3 H 7 and the combination of substituents X, Y, (W) w , Rn and R ⁇ 2 for each compound corresponds to a line of Table B.
  • Table 11-21 Compounds of formula (1.11) wherein AR 7 is CH 2 C 6 H 5 and the combination of substituents X, Y, (W) w , Rn and R 12 for each compound corresponds to a line of Table B.
  • Table 11-22 Compounds of formula (1.11 ) wherein AR 7 is CH 2 C 6 H 4 -2-F and the combination of substituents X, Y and (W) w , Rn and R 12 for each compound corresponds to a line of Table B.
  • Table 11 -23 Compounds of formula (1.11) wherein AR 7 is CH 2 C 6 H 4 -4-Br and the combination of substituents X, Y, (W) w , Rn and R 12 for each compound corresponds to a line of Table B.
  • Table 11 -24 Compounds of formula (1.11) wherein AR 7 is CH 2 C 6 H 4 -3-CF 3 and the combination of substituents X, Y, (W) w , Rn and R ⁇ 2 for each compound corresponds to a line of Table B.
  • Table 11-25 Compounds of formula (1.11) wherein AR 7 is CH 2 C 6 H 4 -4-CF 3 and the combination of substituents X, Y, (W) w , R and R 12 for each compound corresponds to a line of Table B.
  • Table 12-2 Compounds of formula (1.12) wherein AR 7 is CH 2 CH 3 and the combination of substituents X, Y, (R 5 ) s , (RssJn and R-
  • Table 12-4 Compounds of formula (1.12) wherein AR 7 is CH 2 C ⁇ CH and the combination of substituents X, Y, (R 5 ) s , (Rss)n and R 13 for each compound corresponds to a line of Table 2.
  • Table 12-5 Compounds of formula (1.12) wherein AR 7 is CH 2 CH 2 CH 3 and the combination of substituents X, Y, (R 5 ) s , (Rss)n and R 13 for each compound corresponds to a line of Table 2.
  • Table 12-6 Compounds of formula (1.12) wherein AR 7 is CH(CH 3 ) 2 and the combination of substituents X, Y, (Rs) s . (Rss)n and R 13 for each compound corresponds to a line of Table C.
  • Table 12-7 Compounds of formula (1.12) wherein AR 7 is CH 2 CH 2 CH 2 CH 3 and the combination of substituents X, Y, (R 5 ) s , (Rss)n and R 13 for each compound corresponds to a line of Table C.
  • Table 12-8 Compounds of formula (1.12) wherein AR 7 is CH(CH 3 )(CH 2 CH 3 ) and the combination of substituents X, Y, (R 5 ) s , (Rss)n and R 13 for each compound corresponds to a line of Table C.
  • Table 12-9 Compounds of formula (1.12) wherein AR 7 is C(CH 3 ) 3 and the combination of substituents X, Y, (R 5 ) s , (Rss) n and R 13 for each compound corresponds to a line of Table C.
  • Table 12-10 Compounds of formula (1.12) wherein AR 7 is CH 2 CF 3 and the combination of substituents X, Y, (Rs) s , (RssJn and R 13 for each compound corresponds to a line of Table C.
  • Table 12-13 Compounds of formula (1.12) wherein AR 7 is CH 2 Si(CH 3 ) 3 and the combination of substituents X, Y, (R 5 ) s , (Rss)n and R 13 for each compound corresponds to a line of Table C.
  • Table 12-14 Compounds of formula (1.12) wherein AR 7 is CH 2 -c.propyl-2,2-CI 2 and the combination of substituents X, Y, (R 5 ) s , (Rss)n and R 13 for each compound corresponds to a line of Table C.
  • Table 12-15 Compounds of formula (1.12) wherein AR 7 is CH 2 CN and the combination of substituents X, Y, (R 5 ) s , (Rss)n and R 13 for each compound corresponds to a line of Table C.
  • Table 12-16 Compounds of formula (1.12) wherein AR 7 is CH 2 COOCH 3 and the combination of substituents X, Y, (R 5 ) s , (Rssin and R-
  • Table 12-17 Compounds of formula (1.12) wherein AR 7 is CH 2 COO-iso-C 3 H 7 and the combination of substituents X, Y, (R 5 ) s , (Rss)n and R-
  • Table 12-21 Compounds of formula (1.12) wherein AR is CH 2 C 6 H 5 and the combination of substituents X, Y, (R 5 ) s , (Rss)n and R 13 for each compound corresponds to a line of Table C.
  • Table 12-22 Compounds of formula (1.12) wherein AR is CH 2 C 6 H 4 -2-F and the combination of substituents X, Y, (R 5 ) s , (Rss)n and R 13 for each compound corresponds to a line of Table C.
  • Table 12-23 Compounds of formula (1.12) wherein AR 7 is CH 2 C 6 H 4 -3-CI and the combination of substituents X, Y, (Rs) s , (Rss) n and R 13 for each compound corresponds to a line of Table C.
  • Table 12-24 Compounds of formula (1.12) wherein AR 7 is CH 2 C 6 H 4 -4-Br and the combination of substituents X, Y, (R 5 ) s , (Rss) n and R 13 for each compound corresponds to a line of Table C.
  • Table 12-25 Compounds of formula (1.12) wherein AR 7 is CH 2 C 6 H 4 -3-CF 3 and the combination of substituents X, Y, (R 5 ) s , (Rss)n and R 13 for each compound corresponds to a line of Table C.
  • Table 12-26 Compounds of formula (1.12) wherein AR 7 is CH 2 C 6 H 4 -4-CF 3 and the combination of substituents X, Y, (R 5 ) s , (R 5 s)n and R-
  • Table 13-1 Compounds of formula (1.13) wherein AR 7 is CH 3 and the combination of substituents X, Y, (Rs) s . (Rss)n and R13 for each compound corresponds to a line of Table C.
  • Table 13-2 Compounds of formula (1.13) wherein AR 7 is CH 2 CH 3 and the combination of substituents X, Y, (Rs) s , (Rss) n and R 13 for each compound corresponds to a line of Table C.
  • Table 13-4 Compounds of formula (1.13) wherein AR 7 is CH 2 C ⁇ CH and the combination of substituents X, Y, (R 5 ) s , (Rss) n and R 13 for each compound corresponds to a line of Table C.
  • Table 13-5 Compounds of formula (1.13) wherein AR 7 is CH 2 CH 2 CH 3 and the combination of substituents X, Y, (R 5 ) s , (Rss)n and R-
  • Table 13-6 Compounds of formula (1.13) wherein AR 7 is CH(CH ) 2 and the combination of substituents X, Y, (Rs) s . (Rss)n and R1 3 for each compound corresponds to a line of Table C.
  • Table 13-7 Compounds of formula (1.13) wherein AR 7 is CH 2 CH 2 CH 2 CH 3 and the combination of substituents X, Y, (R 5 ) s , (Rss)n and R 13 for each compound corresponds to a line of Table C.
  • Table 13-8 Compounds of formula (1.13) wherein AR 7 is CH(CH 3 )(CH 2 CH 3 ) and the combination of substituents X, Y, (R 5 ) s , (Rss)n and R 13 for each compound corresponds to a line of Table C.
  • Table 13-9 Compounds of formula (1.13) wherein AR 7 is C(CH 3 ) 3 and the combination of substituents X, Y, (Rs) s , (RssJn and R 13 for each compound corresponds to a line of Table C.
  • Table 14 Compounds of formula (1.13) wherein AR 7 is C(CH 3 ) 3 and the combination of substituents X, Y, (Rs) s , (RssJn and R 13 for each compound corresponds to a line of Table C.
  • Table 14 Compounds of formula (1.13) wherein AR 7 is C(CH 3 ) 3 and the combination of substituents X, Y, (Rs) s , (RssJn and R 13 for each compound corresponds to a line of Table C.
  • Table 14 Compounds of formula (1.13) wherein AR 7 is C(CH 3 ) 3 and the combination of substituents X, Y, (Rs) s , (RssJn and R 13
  • Formulations such as emulsifiable concentrates, solutions granules, dusts, wettable powders, emulsifiable concentrates, extruder granules, coated granules and suspension concentrates are of the same kind as mentioned in EP-A-736 252, examples F1 to F10. Accordingly, the said formulations mentioned in EP-A-736252 are included by reference in the subject matter of the present invention.
  • Example B1 Action against Phytophthora infestans on tomatoes a) Curative action
  • tomato plants of the "Red Gnome" variety are sprayed with a zoospore suspension of the fungus and incubated in a humidity chamber at 18 to 20°C and saturated humidity. Humidifying is discontinued after 24 hours.
  • the plants have dried off, they are sprayed with a mixture containing a wettable powder formulation of the test compound at a concentration of 200 ppm.
  • the plants are again placed in the humidity chamber for 4 days. The number and size of the typical leaf blotches that have appeared after that time serve as a measure for evaluating the effectiveness of the test compounds.
  • a wettable powder formulation of the test compound at a concentration of 60 ppm (based on the volume of soil) is used to water the surface of the soil in which three-week-old tomato plants of the "Red Gnome" variety have been potted. After a waiting period of three days, the undersides of the leaves of the plants are sprayed with a zoospore suspension of Phytophthora infestans. The treated plants are then placed in a spraying cabinet for 5 days at 18 to 20°C and saturated humidity. After that period, typical leaf blotches appear, the number and size of which are used to evaluate the effectiveness of the test compounds.
  • Example B2 Action against Plasmopara viticola (Bert, et Curt.) (Berl. et DeToni) on vines Vine cuttings of the "Chasselas" variety are cultivated in a greenhouse and are infected at the 10-leaf stage, on the undersides of the leaves, with a spore suspension of Plasmopara viticola. After being kept in a humidity chamber for 24 hours, the plants are sprayed with mixtures comprising the active ingredient in concentrations of 200 ppm, 60 ppm and 20 ppm. The plants are then kept in the humidity chamber for a further 7 days. After that time, the disease symptoms appear in the control plants. The number and size of the infection sites on the treated plants serve as a measure for evaluating the effectiveness of the test compounds.
  • the plants treated with compounds of Tables 1 to 15 exhibit an infestation of 20 % or less.
  • the compounds 1-4.2, 3-4.2, 4-1.2, 6.3, 8.10 and 9-2.2 complete curative action is still obtained even at a concentration of 20 ppm of the test compound.
  • Example B3 Action against Puccinia graminis on wheat a) Residual-protective action
  • wheat plants are sprayed to drip point with an aqueous spray mixture (0.02 % active ingredient), and infected 24 hours later with a uredospore suspension of the fungus. After an incubation period of 48 hours (conditions: 95 to 100 % relative humidity at 20°C), the plants are placed in a greenhouse at 22°C. Evaluation of rust pustule development is made 12 days after infection.
  • Wheat plants are watered 5 days after sowing with an aqueous spray mixture (0.006 % active ingredient, based on the volume of soil). Care is taken that the spray mixture does not come into contact with the parts of the plants above the soil.
  • the treated plants are infected 48 hours later with a uredospore suspension of the fungus. After an incubation period of 48 hours (conditions: 95 to 100 % relative humidity at 20°C), the plants are placed in a greenhouse at 22°C. Evaluation of rust pustule development is made 12 days after infection.
  • the compounds of Tables 1 to 15 bring about a distinct reduction in the fungus infestation, in some cases to from 10 to 0 %.
  • the compounds 3-4.2, 4.1-1 , 5.4, 8.10, 12-1.3, 10-1.16 and 12-1.4 the disease is suppressed completely (0-5 % infestation).
  • Example B4 Action against Pyricularia oryzae on rice plants a) Residual-protective action
  • rice plants are sprayed to drip point with an aqueous spray mixture (0.02 % active ingredient), and are infected 48 hours later with a conidia sus- pension of the fungus. Evaluation of fungus infestation is made 5 days after infection, du r- ing which period 95 to 100 % relative humidity and a temperature of 22°C are maintained.
  • 2-week-old rice plants are watered with an aqueous spray mixture (0.006 % active ingredient, based on the volume of soil). Care is taken that the spray mixture does not come into contact with the parts of the plant above the soil.
  • the pots are then filled with water so that the lowermost parts of the stems of the rice plants stand in water. After 96 hours, the plants are infected with a conidia suspension of the fungus and kept for 5 days at 95 to 100 % relative humidity and a temperature of 24°C.
  • the compounds of Tables 1 to 15 largely prevent the disease from breaking out on the i n- fected plants.
  • Example B5 Action against Erysiphe graminis on barlev 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) and dusted 3 to 4 hours later with conidia of the fungus.
  • the infected plants are placed in a greenhouse at 22°C.
  • the fungus infestation is evaluated 10 days after infection.
  • Barley plants about 8 cm in height are watered with an aqueous spray mixture (0.002 % active ingredient, based on the volume of soil). Care is taken that the spray mixture does not come into contact with the parts of the plants above the soil.
  • the treated plants are dusted 48 hours later with conidia of the fungus.
  • the infected plants are placed in a greenhouse at 22°C.
  • the fungus infestation is evaluated 10 days after infection.
  • the compounds of Tables 1 to 15 in general are able to suppress infestation with the disease to less than 20 % and, in some cases, to suppress it completely.
  • Example B6 Action against Botrytis cinerea on apple fruits. Residual -protective action Artificially damaged apples are treated by applying drops of a spray mixture (0.02 % active ingredient) onto the damage sites. The treated fruits are then inoculated with a spore su s- pension of the fungus and incubated for one week at high humidity and about 20°C. The fungicidal action of the test compound is derived from the number of rotted damage sites. Compounds of Tables 1 to 15 are able to prevent the rot from spreading, in some cases completely.
  • Example B7 Action against Aphis craccivora
  • Maize seedlings are sprayed with an aqueous emulsion spray mixture comprising 100 ppm of the test compound. After the spray-coating has dried, the maize seedlings are populated with 10 Diabrotica balteata larvae in the second stage and then placed in a plastics container. 6 days later, the percentage reduction in population (% activity) is determined by comparing the number of dead larvae on the treated plants with that on untreated plants.
  • the compounds of Tables 1 to 15 exhibit good activity in this test. In particular, compounds 1-4.2, 2-4.2, 4-1.2, 4-1.8, 5.5, 9-2.2, 12-1.3, 10-1.16 and 12-1.4 are more than 80 % effective in this test.
  • Example B9 Action against Heliothis virescens
  • Young soybean plants are sprayed with an aqueous emulsion spray mixture comprising 100 ppm of the test compound. After the spray-coating has dried, the plants are populated with 10 Spodoptera littoralis caterpillars in the third stage and then placed in a plastics* container. 3 days later, the percentage reduction in 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 untreated plants. The compounds of Tables 1 to 15 exhibit good activity in this test.
  • Example B11 Action against Tetranvchus urticae
  • Young bean plants are populated with a mixed population of Tetranychus urticae and sprayed one day later with an aqueous emulsion spray mixture comprising 100 ppm of the test compound. The plants are then incubated for 6 days at 25°C and subsequently evaluated. The percentage reduction in population (% activity) is determined by comparing the number of dead eggs, larvae and adults on the treated plants with that on untreated plants.
  • the compounds of Tables 1 to 15 generally exhibit good activity in this test. In particular, compounds 1-4.2, 2-4.2, 3-4.2, 4-1.1 , 5.5, 6.3, 8.10, 9-2.2, 12-1.3, 10-1.16 and 12-1.4 are more than 80 % effective in this test.

Abstract

Compounds of formula (I), wherein either X is CH or N, Y is OR1 and Z is O, or X is N, Y is NHR8 and Z is O, S or S (=O); R1, R2 and R3 are as defined according to the specification; m is 0, 1 or 2; R5 is, for example, halogen, C1-C6alkyl, halo-C1-C6alkyl or C3-C6cycloalkyl; n is 0, 1, 2, 3 or 4; R9 is methyl, fluoromethyl or difluoromethyl; A and R7 are as defined according to the specification; D is O, S, -S(=O) or S(=O)2; G is C1-C8alkylene; T-R6 is R6, -C(=N-O-A1-R77)-R6; -SiR14(R15)-R6; -C(=O)-R6; -C(R16)=C(R17)-R6, -C≡C-R6 or -D-R6; R6 is C1-C4alkyl or unsubstituted or substituted aryl or heteroaryl; A1 and R77 are as defined above for A and R7; L is U-R18, P(O)vR11R12, P(S)wR11R12 or N(aryl)R13; v and w are 0 or 1; U-R18 is -C(=O)-C(=O)-R18; -C(OH)-C(OH)-R18; -C(=N-O-A1-R7)-R18; (i) or (ii); a is 0 or 1; b is 0 or 1; R11, R12 and R13 are, for example, C1-C6alkyl, halo-C1-C6alkyl or C3-C6cycloalkyl; R14 and R15 are each independently of the other C1-C4alkyl; R16 and R17 are each independently of the other hydrogen, C1-C4alkyl or halogen and R18 is R5; and, where applicable, their possible E/Z isomers, mixtures of E/Z isomers and/or tautomers, in each case in free form or in salt form, a method of controlling pests, a process for the preparation of those compounds and their use are described.

Description

O-BENZYL OXIME ETHERS AND THEIR USE AS PESTICIDES
The invention relates to compounds of formula
Figure imgf000003_0001
wherein either
X is CH or N, Y is OR. and Z is O, or
X is N, Y is NHR8 and Z is O, S or S(=O);
Rt is hydrogen or C.-C4alkyl; Re is hydrogen or Cι-C alkyl; R2 is H, C C4alkyl, halo-C1-C4alkyl, C3-C6cycloalkyl, CrC4alkoxymethyl, Cι-C4alkoxy, halo-C1-C alkoxy, d-C alkylthio, halo-Cι-C4alkylthio or CN;
R3 and R4 are each independently of the other H, C.-C4alkyl, Cι-C4alkoxy, OH, CN, NO2, a (Cι-C4alkyl)3-Si group, the alkyl groups being the same or different, halogen, (C.-C alkyl)S(=O)m, (halo-C.-C4alkyl)S(=O)mi halo-C.-C alkyl or halo-C.-C alkoxy; m is 0, 1 or 2; R5 independently of any other is halogen, C.-C6alkyl, halo-C.-C6alkyl, C3-C6cycloalkyl, halo-C3-C6cycloalkyl, d-C6alkoxy, halo-d-C6alkoxy, d-C6alkylthio, halo-C.-C6alkyl- thio, C C6alkylsulfinyl, halo-C.-C6alkylsulfinyl, d-Cealkylsulfonyl, halo-C C6alkyl- sulfonyl, Cι-C6alkylsulfonyloxy, halo-d-Cβalkylsulfonyloxy, Cι-C6alkoxy-Cι-C6alkyl, halo-d-Cealkoxy-Ci-Cealkyl, Ci-Cealkylthio-d-Cealkyl. halo-Ci-Cβalkylthio-d-Cealkyl, d-Cealkylsulfinyl-CrCealkyl, halo-Cι-C6alkylsulfinyl-Cι-C6alkyl, C.-C6alkylsulfonyl- Cι-C6alkyl, halo-Ci-Cβalkylsulfonyl-Ci-CβalkyI, CrCealkylcarbonyl, halo-C Cealkyl- carbonyl, d-C6alkoxycarbonyl, halo-Ci-Cealkoxycarbonyl, CrC6alkylaminocarbonyl, Cι-C4alkoxyiminomethyl, di(C.-C6alkyl)aminocarbonyl, the alkyl groups being the same or different; d-Cβalkylaminothiocarbonyl, d d-Cβalty aminothiocarbonyl, the alkyl groups being the same or different; d-Cealkylamino, di(Cι-C6alkyl)amino, the alkyl groups being the same or different; NO2, CN, SF5, thioamido, thiocyanatomethyl, trimethylsilyl; d-C4alkylenedioxy or -CH=CH-CH=CH- each of which is unsubstituted or, depending on its substitution possibilities, mono- to tetra-substituted, the substit- uents of the C.-C4alkylenedioxy or -CH=CH-CH=CH- group being selected from the group consisting of C.-C alkyl and halogen; aryl-Q-, heterocyclyl-Q-, aryl-Q-d-C6alkyl, aryl-Q-C2-C6alkenyl, heterocyclyl-Q-C C6alkyl or heterocyclyl-Q-C2-C6alkenyl, or aryl-Q-, heterocyclyl-Q-, aryl-Q-C.-C6alkyl, aryl-Q-C2-C6alkenyl, heterocyclyl-Q-d-C6- alkyl or heterocyclyl-Q-C2-C6alkenyl each of which is, depending on its substitution possibilities, mono- to penta-substituted in the aryl or heterocyclyl ring, the substit- uents being selected independently of one another from the group consisting of halogen, Cι-C6alkyl, halo-d-C6alkyl, C3-C6cycloalkyl, halo-C3-C6cycloalkyl, C.-C6alkoxy, halo-Cι-C6alkoxy, CN, nitro and C.-C6alkoxycarbonyl; and, when n is greater than 1 , the radicals R5 are the same or different; n is 0, 1 , 2, 3 or, if either a or b is 0, 4;
Q is a direct bond, -CH(OH)-, -C(=O)-, -S-, -S(=O) or -S(=O)2;
R9 is methyl, fluoromethyl or difluoromethyl; either
A is a direct bond, CrCι0alkylene, -C(=O)-, -C(=S)- or halo-d-C.0alkylene and
R7 is a radical R10; or
A is d-C.oalkylene, -C(=O)-, -C(=S)- or halo-d-C.oalkylene and
R7 is -CN, ORio, N(R10)2, the radicals R10 being the same or different, -SR10) -S(=O)R.0 or -S(=O)2Rι0;
R10 is H, C.-C6alkyl, C2-C8alkenyl, C2-C8alkynyl or C3-C6cycloalkyl, or d-C6alkyl, C2-C8- alkenyl, C2-C8alkynyl or C3-C6cycloalkyl each mono- or poly-substituted by substitu- ents from the group consisting of halogen; -Si(C C4alkyl)3, the alkyl groups being the same or different; d-Cealkoxycarbonyl or an aryl or heterocyclyl group that is unsubstituted or mono- or poly-substituted by substituents selected from the group consisting of halogen, d-C alkyl and halo-Cι-C4alkyl; and
D is O, S, -S(=O) or S(=O)2;
G is d-C8alkylene;
T-R6 is R6; -C(=N-O-A1-R77)-R6; -SiR.4(R.5)-R6; -C(=O)-R6; -C(R16)=C(R17)«R6; -C≡C-R6 or -D-R6;
R6 is d-dalkyl, aryl or heteroaryl; or aryl or heteroaryl each of which - depending on the substitution possibilities on the ring structure - is mono- to penta-substituted by substituents selected independently of one another from the group consisting of (R5)s; s is, depending on the substitution possibilities on the ring, 0, 1 , 2, 3, 4 or 5, the substituents R5 being independent of one another when s is greater than 1 ; AT and R are as defined above for A and R7; a is 0 or 1 ;
L is U-R.β, P(O)vRnR12, P(S)wRnRι2 or N(aryl)R13, the aryl radical being either unsubstituted or mono- to penta-substituted by substituents selected independently of one another from the group consisting of R5; v and w are 0 or 1 ;
U-R.β is -C(=O)-C(=O)-R18; -C(OH)-C(OH)-R18; -C(=N-O-A.-R7)-R.8;
Figure imgf000005_0001
p is from 0 to 4;
Rn and R12 are each independently of the other Cι-C6alkyl, halo-Cι-C6alkyl, C3-C6cyclo- alkyl, halo-C3-C6cycloalkyl, C C6alkoxy, halo-C C6alkoxy, d-Cβalkylthio, halo- CrC6alkylthio, aryl, heteroaryl, aryloxy, arylthio, heteroaryioxy or heteroarylthio; or aryl, heteroaryl, aryloxy, arylthio, heteroaryioxy or heteroarylthio each mono- to penta- substituted by R5, the substituents R5 being independent of one another; b is 0 or 1 , but a and b are not simultaneously 0;
R-I3 is hydrogen, C.-C6alkyl, halo-d-C6alkyl, C3-C6cycloalkyl, halo-C3-C6cycloalkyl,
C C6alkylsulfinyl, halo-CrC6alkylsulfinyl, C C6alkylsulfonyl, halo-Cι-C6alkylsulfonyl, C Cealkoxy-CrCealkyl, halo-d-Cβalkoxy-CrCβalkyl, d-Cβalkylthio-C Cβalkyl, halo- CrC6alkylthio-C C6alkyl, CrCβalkylsulfinyl-Ci-CealkyI, halo-Cι-C6alkylsulfinyl- C C6alkyl, d-Cealkylsulfonyl-d-Cβalkyl, halo-CrCealkylsulfonyl-CrCβalkyl, formyl, C C6alkylcarbonyl, C1-C6alkyl-C(=S)-, C C6alkylthio-C(=S)-, halo-C C6alkylcarbonyl, C C6alkoxycarbonyl, halo-C C6alkoxycarbonyl, d-Cβalkylaminocarbonyl, C C - alkoxyiminomethyl, di(Cι-C6alkyl)aminocarbonyl, the alkyl groups being the same or different; C.-C6alkylaminothiocarbonyl, di(C C6alkyl)aminothiocarbonyl, the alkyl groups being the same or different; d-Cealkyldicarbonyl, halo-d-Cβalkyldicarbonyl, CrC6alkoxydicarbonyl. halo-d-Cβalkoxydicarbonyl, Cι-C6alkylaminodicarbonyl, di(Cι-C6alkyl)aminodicarbonyl, the alkyl groups being the same or different; C C6alkylaminodithiocarbonyl, d d-Cealky aminodithiocarbonyl, the alkyl groups being the same or different; aryl, arylsulfinyl, aryl-C1-C6alkylsulfinyl, arylsulfonyl, aryl- C C6alkyl-sulfonyl, aryloxy-d-Cβalkyl, arylthio-C C6alkyl, aryl-C C6alkylsulfinyl- C C6alkyl, aryl-d-Cβalkylsulfonyl-Ci-Cealkyl, arylcarbonyl, arylalkylcarbonyl, aryloxy- carbonyl, arylalkoxycarbonyl, arylaminocarbonyl, aryloxyiminomethyl, di(aryl)amino- carbonyl, the aryl groups being the same or different; arylaminothiocarbonyl, di(aryl)aminothiocarbonyl, the aryl groups being the same or different; aryldicarbonyl, aryl-Cι-C6alkyldicarbonyl, aryloxydicarbonyl, aryl-Cι-C6alkoxydicarbonyl, arylamino- dicarbonyl, di(aryl)aminodicarbonyl, the aryl groups being the same or different; ary- laminodithiocarbonyl, di(aryl)aminodithiocarbonyl, the aryl groups being the same or different; and the aryl groups in the afore-mentioned substituents being unsubstituted or mono- to penta-substituted by substituents R5, the substituents R5 being independent of one another; unsubstituted or substituted heteroaryl, unsubstituted or substituted heteroarylcarbonyl, unsubstituted or substituted heteroarylsulfinyl, or unsubstituted or substituted heteroarylsulfonyl;
Ri4 and Ri5 are each independently of the other d-C alkyl;
Rιe and R 7 are each independently of the other hydrogen, Cι-C4alkyl or halogen and
and, where applicable, their possible E/Z isomers, mixtures of E Z isomers and/or tautomers, in each case in free form or in salt form, with the proviso (P1) that G is not -CH2- when R2 is methyl, R3 and R4 are hydrogen, D is oxygen, a is 1 , b is 0, and either' the group -SiRι4(Rι5)-R6 the radicals Ru, Rι5 and R6 are methyl, or in the group -C(Rι6)=C(Rι7)-R6 the radical R6 is methyl and the radical Ri7 is hydrogen or methyl; with the proviso (P2) that G is not d-C3alkylene when a is 1 , b is 0, T is a direct bond and R6 is d-dalkyl; and with the further proviso (P3) that G is not -CH2- when D is oxygen, a is 1 , b is 0, R2 is d-C6alkyl or C3-C6cycloalkyl, T is a direct bond and R6 is unsubstituted or substituted phenyi; to pesticidal compositions, the active ingredient of which is selected from those compounds, E/Z isomers and tautomers, in each case in free form or in salt form; to a process for the preparation of those compositions and to the use thereof; to intermediates and, where applicable, their possible E/Z isomers, mixtures of E/Z isomers and/or tautomers, in free form or in salt form, for the preparation of those compounds, where applicable tautomers, in free form or in salt form, of those intermediates; and to a process for the preparation of those intermediates and their tautomers and to the use thereof. In the literature a number of methoxyacrylic acid derivatives are proposed as active ingredients in pesticides. The biological properties of those known compounds are not, however, entirely satisfactory in the field of pest control and there is therefore a need to provide further compounds having pesticidal properties, especially for controlling insects and representatives of the order Acarina and especially for controlling phytopathogenic microorganisms. That problem is solved according to the invention by the provision of the present compounds of formula (I).
A number of compounds of formula (I), and of the formulae (III), (IV), (VI), (VIII), (IX), (XII), (XIII), (XV), (XVIII), (XXII), (XXIII) and (XXIV) given hereinafter, contain asymmetrical carbon atoms, as a result of which the compounds may occur in optically active form. By virtue of the presence of the C=X and oximino double bonds, the compounds may occur in the E and Z isomeric forms. Atropisomers of the compounds may also occur. The corresponding formulae are intended to include all those possible isomeric forms and also mixtures thereof, for example racemates or mixtures of E Z isomers, and also, where applicable, salts thereof, even if this is not specifically mentioned every time.
Unless indicated to the contrary, the general terms used hereinbefore and hereinafter have the following meanings.
Unless indicated to the contrary, carbon-containing groups and compounds each contain from 1 up to and including 8, especially from 1 up to and including 6, more especially from 1 up to and including 4, very especially 1 or 2, carbon atoms.
Alkyl, as a group perse and also as a structural unit of other groups and compounds, such as of haloalkyl, alkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl, alkylcarbonyl, alkoxycarbonyl, alkylamino, alkoxyiminomethyl, alkylaminocarbonyl and alkylaminothiocarbonyl, is, in each individual case giving due consideration to the number of carbon atoms contained in the group or compound in question, either straight-chain, that is to say methyl, ethyl, propyl, butyl, pentyl or hexyl, or branched, e.g. isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl or isohexyl.
Alkenyl, as a group perse and also as a structural unit of other groups and compounds, such as of haloalkenyl, is, in each individual case giving due consideration to the number of carbon atoms contained in the group or compound in question, either straight-chain, for example vinyl, 1-methylvinyl, allyl, 1-butenyl or 2-hexenyl, or branched, for example isopro- penyl.
Alkynyl, as a group perse and also as a structural unit of other groups and compounds, such as of haloalkynyl, is, in each individual case giving due consideration to the number of carbon atoms contained in the group or compound in question, either straight-chain, for example propargyl, 2-butynyl or 5-hexynyl, or branched, for example 2-ethynylpropyl or 2-propargylisopropyl.
C3-C6Cycloalkyl is cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.
Alkylene, as a group perse and also as a structural unit of other groups and compounds, such as of haloalkylene, is, in each individual case giving due consideration to the number of carbon atoms contained in the group or compound in question, either straight-chain, for example -CH2CH2-, -CH2CH2CH2- or -CH2CH2CH2CH2-, or branched, for example -CH(CH3)-, -CH(C2H5)-, -C(CH3)2-, -CH(CH3)CH2- or -CH(CH3)CH(CH3)-. Preference is given to - CH2CH2-, -CH(CH3)-, -CH(C2H5)-, and -CH2CH2CH2-.
Aryl is phenyi or naphthyl, especially phenyi.
Heterocyclyl is a 5- to 7-membered aromatic or nonaromatic ring having from one to three hetero atoms selected from the group consisting of N, O and S. Preference is given to aromatic 5- and 6-membered rings having a nitrogen atom as hetero atom and optionally a further hetero atom, preferably nitrogen or sulfur, especially nitrogen. Preferred heteroaryl moieties are pyrazinyl, 3'-pyridyl, 2'-pyridyl, 4'-pyridyl, 2'-pyrimidinyl, 4'-pyrimidinyl, 5'-pyrim- idinyl, 2'-thiazolyl, 2'-oxazolyl, 2'-thienyl, 3'-thienyl and 2'-thiazolyl.
Halogen, as a group perse and also as a structural unit of other groups and compounds, such as of haloalkyl, haloalkenyl and haloalkynyl, is fluorine, chlorine, bromine or iodine, especially fluorine, chlorine or bromine, more especially fluorine or chlorine, very especially fluorine. Halo-substituted carbon-containing groups and compounds, such as haloalkyl, haloalkenyl or haloalkynyl, may be partially halogenated or per-halogenated, it being possible in the case of poly-halogenation for the halogen substituents to be the same or different. Examples of haloalkyl, as a group perse and also as a structural unit of other groups and compounds, such as of haloalkenyl, are methyl that is mono- to tri-substituted by fluorine, chlorine and/or by bromine, such as CHF2 or CF3; ethyl that is mono- to penta-substituted by fluorine, chlorine and/or by bromine, such as CH2CF3> CF2CF3, CF2CCI3, CF2CHCI2, CF2CHF2, CF2CFCI2, CF2CHBr2, CF2CHCIF, CF2CHBrF or CCIFCHCIF; propyl or isopropyl that is mono- to hepta-substituted by fluorine, chlorine and/or by bromine, such as CH2CHBrCH2Br, CF2CHFCF3, CH2CF2CF3 or CH(CF3)2; and butyl, or an isomer thereof, that is mono- to nona-substituted by fluorine, chlorine and/or by bromine, such as CF(CF3)CHFCF3or CH2(CF2) 2CF3. Haloalkenyl is, for example, CH2CH=CHCI, CH2CH=CCI2, CH2CF=CF2 or CH2CH=CHCH2Br. Haloalkynyl is, for example, CH2C≡CF, CH2C=CCH2CI or CF2CF2C≡CCH2F.
A number of compounds of formula (I), and of the formulae (III) to (XXIV) given hereinafter, may, as is known to the person skilled in the art, be present in the form of tautomers, especially when R7 is H. Hereinbefore and hereinafter any reference to these compounds should therefore be understood as including also corresponding tautomers, even when the latter are not specifically mentioned in each case.
Compounds of formula (I), and of the formulae (III) to (XXIV) given hereinafter, that have at least one basic centre may, for example, form acid addition salts. Such salts are formed, for example, with strong inorganic acids, such as mineral acids, e.g. perchloric acid, sulfuric acid, nitric acid, nitrous acid, a phosphoric acid or a hydrohalic acid, with strong organic carboxylic acids, such as unsubstituted or substituted, for example halo-substituted, d-dalkanecarboxylic acids, e.g. acetic acid, saturated or unsaturated dicarboxylic acids, e.g. oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid or phthalic acid, hy- droxycarboxyiic acids, e.g. ascorbic acid, lactic acid, malic acid, tartaric acid or citric acid, or benzoic acid, or with organic sulfonic acids, such as unsubstituted or substituted, for example halo-substituted, Cι-C alkane- or aryl-sulfonic acids, e.g. methane- or p-toluene-sulfonic acid. Furthermore, compounds of formula (I) having at least one acid group may form salts with bases. Suitable salts with bases are, for example, metal salts, such as alkali metal or alkaline earth metal salts, e.g. sodium, potassium or magnesium salts, or salts with ammonia or an organic amine, such as moφholine, piperidine, pyrrolidine, a mono-, di- or tri-lower alkylamine, e.g. ethyl-, diethyl-, triethyl- or dimethyl-propyl-amine, or a mono-, di- or tri- hydroxy-lower alkylamine, e.g. mono-, di- or tri-ethanolamine. It may also be possible for corresponding internal salts to be formed. Within the context of the invention, preference is given to agrochemically advantageous salts; also included, however, are salts which cannot be agrochemically used, which are used however, for example, for isolating and/or purifying free compounds of formula (I) or agrochemically acceptable salts thereof. Hereinbefore and hereinafter any reference to the compounds of formula (I) in free form is to be under-stood as including also the salts of compounds of formula (I), and any reference to the salts is to be understood as including also the corresponding free compounds of formula (I), as appropriate and expedient. The same applies also to tautomers of compounds of formulae (I) and (III) to (XXIV) and salts thereof. In each case the free form is generally preferred.
Preferred embodiments within the context of the invention, in each case taking into consideration the provisos mentioned hereinbefore, are:
(1 ) a compound of formula (I) wherein X is CH and Z is O; especially wherein X is CH, Z is O and Y is -OCH3;
(2) a compound of formula (I) wherein X is N and Z is O; especially wherein X is N, Z is O and Y is NHCH3;
(3) a compound of formula (I) wherein Y is OCrC4alkyl, preferably Cι-C2alkoxy, especially methoxy;
(4) a compound of formula (I) wherein
R2 is H, d-C4alkyl, halo-d-C4alkyl or C3-C6cycloalkyl, preferably d-dalkyl or halo-Cι-C4alkyl, especially C1-C2alkyl, more especially methyl;
(5) a compound of formula (I) wherein
R3 is H, d-dalkyl, d-C4alkoxy, OH, CN, NO2, halogen, halo-d-C4alkyl or halo- d-dalkoxy, preferably H, d-dalkyl, d-C4alkoxy or halogen, especially H, methyl, methoxy, chlorine or fluorine, more especially H; (6) a compound of formula (I) wherein
R4 is H, d-dalkyl, d-C alkoxy, OH, CN, NO2, halogen, halo-Cι-C alkyl or halo- Ci-dalkoxy, preferably H, C C alkyl, d-C4alkoxy or halogen, especially H, methyl, methoxy, chlorine or fluorine, more especially H;
(7) a compound of formula (I) wherein
R8 is H or Cι-C2alkyl, preferably Cι-C2alkyl, especially methyl;
(8) a compound of formula (I) wherein R9 is methyl or fluoromethyl, preferably methyl;
(9) a compound of formula (I) wherein
A is a direct bond, Ci-Cioalkylene or halo-d-Cι0alkylene, preferably a direct bond or C dalkylene, especially a direct bond or methylene, and R7 is a radical R10;
(10) a compound of formula (I) wherein AR is methyl or ethyl, especially ethyl;
(11 ) a compound of formula (I) wherein n is 0;
(12) a compound of formula (I) wherein a is 0, b is 1 and L is -C(=O)-C(=O)-R18,
Figure imgf000011_0001
(13) a compound of formula (I) wherein R 8 is unsubstituted or substituted phenyi;
(14) a compound of formula (I) wherein a is 0, n is 0, b is 1 and L is PORιιR 2;
(15) a compound of formula (I) wherein Rn and Rι2 are each independently of the other C C6alkoxy, halo-C C6alkoxy, d-C6alkylthio, halo-C.-C6alkylthio, aryl, aryloxy or arylthio; or aryl, heteroaryl, aryloxy, arylthio, heteroaryioxy or heteroarylthio each mono- to tri- substituted by R5, the substituents R5 being independent of one another;
(16) a compound of formula (I) wherein a is 0, n is 0, b is 1 , L is N(aryl)R13 and R13 is H, methyl, ethyl or formyl, especially H;
(17) a compound of formula (I) wherein a is 1 , n is 0, b is 0 and D is oxygen;
(18) a compound of formula (I) wherein a is 1 and G is d-dalkylene, especially -CH2-CH2- or -CH(CH3)-; (19) a compound of formula (I) wherein a is 1 , b is 0 and T is a direct bond, -C(=N-O-Aι-R7)-, -SiRι4(Rι5)-or -C≡C-, especially -SiRι4(R15)-;
(20) a compound of formula (I) wherein R6 is d-dalkyl, aryl, or aryl mono- to penta-substituted by substituents selected independently of one another from the group consisting of R5;
R6 being especially phenyi that is unsubstituted or mono- or di-substituted, especially mono- substituted, by halogen, d-C4alkyl, halo-Cι-C alkyl or by halo-Cι-C4alkoxy, especially mono-substituted by fluorine, chlorine, d-dalkyl, trifluoromethyl or by trifluoromethoxy.
Special preference is given to the compounds of Tables 1 to 15.
The invention relates also to a process for the preparation of the compounds of formula (I) and, where applicable, their E Z isomers, mixtures of E Z isomers and/or tautomers, in each case in free form or in salt form, which process comprises, for example, either a1) reacting a compound of formula
Figure imgf000012_0001
which is known or can be prepared in accordance with methods known per se and wherein X, Y, Z, R3, R and R9are as defined for formula (I) and ^ is a leaving group, preferably in the presence of a base, with a compound of formula
Figure imgf000012_0002
wherein a, b, n, A, D, G, T, L, R2, R5, R6 and R7 are as defined for formula (I) and wherein the provisos mentioned above for the compounds of formula (I) apply, or
a2) reacting a compound of formula
Figure imgf000013_0001
wherein a, b, n, A, D, G, T, L, R2, Rs, R6 and R7 are as defined for formula (I) and wherein the provisos mentioned above for the compounds of formula (I) apply, optionally in the presence of a base, with a compound of formula
Figure imgf000013_0002
which is known or can be prepared in accordance with methods known perse and wherein X, Y, Z, R3, R4 and R9 are as defined for formula (I), or
b) to prepare a compound of formula (I) wherein Y is NHR8 and Z is O, reacting a compound of formula (I) wherein Y is OR1 with a compound of the formula R8NH2, which is known or can be prepared in accordance with methods known perse and wherein R8 is as defined for formula (I), or
c) to prepare a compound of formula (I) wherein Y is NHR8 and Z is S, reacting a compound of formula (I) wherein Y is R8NH2 and Z is O with P S10 or Lawesson's reagent (2,4-bis- (methoxyphenyl)-l ,3-dithia-2,4-diphosphetane-2,4-disulfide), or
d) to prepare a compound of formula (I) wherein Z is SO, reacting a compound of formula (I) wherein Z is S with an oxidising agent,
and, in each case, if desired, converting a compound of formula (I) obtainable according to the process or by a different method, or an E/Z isomer or tautomer thereof, in each case in free form or in salt form, into a different compound of formula (I) or an E/Z isomer or tautomer thereof, in each case in free form or in salt form, separating a mixture of E/Z iso- mers obtainable according to the process and isolating the desired isomer and/or converting a free compound of formula (I) obtainable according to the process or by a different method, or an E/Z isomer or tautomer thereof, into a salt, or converting a salt of a compound of formula (I), or of an E/Z isomer or tautomer thereof, obtainable according to the process or by a different method into the free compound of formula (I), or an E/Z isomer or tautomer thereof, or into a different salt.
The invention relates also to a process for the preparation of compounds of formula (III), in each case in free form or in salt form, which process comprises, for example,
e) reacting a compound of formula (IV) wherein a, b, n, A, D, G, T, L, R2, R5, R6 and R7 are as defined for formula (I) and wherein the provisos mentioned above for the compounds of formula (I) apply, optionally in the presence of a base, with H2NOH or with a salt thereof, or
f) reacting a compound of formula
Figure imgf000014_0001
wherein a, b, n, A, D, G, T, L, R2, R5, R6 and R7 are as defined for formula (I) and wherein the provisos mentioned above for the compounds of formula (I) apply, optionally in the presence of a base, with a compound of formula
R^ONH, (VII), which is known or can be prepared according to methods known perse and wherein A and R7 are as defined for formula (I) and, in each case, if desired, converting a compound of formula (III) obtainable according to the process or by a different method, or an E/Z isomer or tautomer thereof, in each case in free form or in salt form, into a different compound of formula (III) or an E/Z isomer or tautomer thereof, in each case in free form or in salt form, separating a mixture of E/Z isomers obtainable according to the process and isolating the desired isomer and/or converting a free compound of formula (III) obtainable according to the process or by a different method, or an E/Z isomer or tautomer thereof, into a salt, or converting a salt of a compound of formula (III), or of an E/Z isomer or tautomer thereof, obtainable according to the process or by a different method into the free compound of formula (III), or an E/Z isomer or tautomer thereof, or into a different salt.
The invention relates also to a process for the preparation of a compound of formula
Figure imgf000015_0001
wherein a, b, n, D, G, T, L, R2, R5 and R6 are as defined for formula (I), which process comprises
g) in the case where L in formula (Vlll) is a radical
Figure imgf000015_0002
wherein Rι8 is as defined above for formula (I), reacting a compound of formula
Figure imgf000015_0003
wherein a, n, D, G, T and R5 are as defined for formula (I), with a compound of formula
O2N-CH2-R18 (X), wherein Rι8 is as defined for formula (I), in the presence of an isocyanate, especially a phenyi isocyanate; or reacting a compound of formula (IX) with a compound of formula
HO-N=C(Hal)-C(=O)-Rι8 (XI), wherein Rι8 is as defined for formula (I) and Hal is a halogen atom, preferably chlorine; or
h) when L in the compound of formula (Vlll) is a radical -C(=O)-C(=O)-R18, oxidising a compound of formula
Figure imgf000016_0001
wherein a, n, D, G, T, R5 and R6 are as defined for formula (I); or
i) reacting a compound of formula
Figure imgf000016_0002
wherein b, n, L, R2 and R5are as defined for formula (I) and Hal is a halogen atom, preferably fluorine, with a compound of formula
R6-T-(d-Cθalkylene)-D-H (XIV), wherein R6 and T are as defined for formula (I); or
k) reacting a compound of formula
Figure imgf000016_0003
wherein b, n, D, G, R2 and R5are as defined for formula (I), with a compound of formula
R6-T-(d-C8alkylene)-Hal (XVI), wherein R6 and T are as defined above for formula (I) and Hal is a halogen atom, preferably chlorine or bromine; or
I) in the case where, in a compound of formula (Vlll), T is -C≡C-, reacting a compound of formula
Figure imgf000017_0001
wherein R2, R5, L, D, G, n and b are as defined above for formula (I), with a compound of the formula Hal-Re, which is known or can be prepared in accordance with methods known perse, and wherein Hal is halogen, preferably bromine or iodine, especially iodine, and Rι8 is as defined for formula (I); or
m) if L in the compound of formula (Vlll) is P(O)vRιιR12, P(S)wRnR12 or N(aryl)R13, reacting a compound of formula
(XVIII),
Figure imgf000017_0002
which is known or can be prepared in accordance with methods known per se, and wherein a, n, D, G, T, R2, R5 and R6 are as defined for formula (I) and Hal is a halogen atom, preferably bromine or iodine, with a compound of formula
H-P(0)vRιιRi2 (XIX). of formula
H-P(S)WR. ,R12 (XX), or of formula
H-N(aryl)R13 (XXI), which are known or can be prepared in accordance with methods known per se, and wherein v, w, Rn, Rι2, R13 and aryl are as defined for fomnula (I), preferably in the presence of a base and a catalyst, especially a transition metal catalyst, more especially a palladium catalyst or a ferrocene derivative;
and, in each case, if desired, converting a compound of formula (Vlll) obtainable according to the process or by a different method, or an E/Z isomer or tautomer thereof, in each case in free form or in salt form, into a different compound of formula (Vlll) or an E/Z isomer or tautomer thereof, in each case in free form or in salt form, separating a mixture of E/Z isomers obtainable according to the process and isolating the desired isomer and/or converting a free compound of formula (Vlll) obtainable according to the process or by a different method, or an E/Z isomer or tautomer thereof, into a salt, or converting a salt of a compound of formula (Vlll), or of an E/Z isomer or tautomer thereof, obtainable according to the process or by a different method into the free compound of formula (Vlll), or an E/Z isomer or tautomer thereof, or into a different salt.
The other compounds of formula (Vlll) are known or can be prepared in accordance with methods known perse; for example a compound of formula (Vlll) wherein T-R6 is -C(Rιe)=C(Rι )- is obtained by partial hydrogenation of a compound of formula (Vlll) wherein T-R6 is -C≡C-R6; a compound of formula (Vlll) wherein T is a direct bond is obtained by complete hydrogenation of a compound of formula (Vlll) wherein T-R6 is -C≡C-R6 or -C(Ri6)=C(Rι7)-R6, as described in analogous manner in Example P8-1 ; and a compound of formula (Vlll) wherein T-R6 is -C(=N-O-A R7)-R6 is obtained by reacting a compound of formula (Vlll) wherein T-R6 is -C(=O)-R6 with a compound of formula H-N-O-Aι-R7. R6, R7, Aι and RM to R , are as defined above for formula (I) and Hal is halogen, especially chlorine.
Further aspects of the invention are o) a process for the preparation of compound of formula
Figure imgf000018_0001
wherein R2, R5, R6, L, D, G, T, a, b and n are as defined in formula (I), in each case in free form or in salt form, which process comprises reacting a compound of the formula (Vlll) with a nitrite;
p) a process for the preparation of a compound of the formula (IV), which comprises r e- acting a compound of the formula (XXII) with a compound of the formula X ,-A-R7, wherein X, is a leaving group such as toluenesulfonyloxy, trifluoromethanesulfonyloxy and halogen;
q) a process for the preparation of a compound of the formula (III), which comprises reacting a compound of the formula (IV) with hydroxylamine; r) a process for the preparation of a compound of the formula
(XXIII),
Figure imgf000019_0001
wherein R2, R5, R6, L, D, G, T, a, b and n are as defined in forfnula (I), which comprises reacting a compound of the formula
Figure imgf000019_0002
wehrein R5, R6, L, D, G, T, a, b and n are as defined in formula (I), with a nitroalkane;
s) a process for the preparation of a compound of the formula (Vlll), which comprises r e- acting a compound of the formula (XXIII) with Fe/FeCI 3 in the presence of an acid, prefe r- rably hydrochloric acid.
The observations made above in respect of E/Z isomers and tautomers of compounds (I) apply analogously also in respect of the E/Z isomers and tautomers of starting materials mentioned hereinbefore and hereinafter.
The reactions described hereinbefore and hereinafter are carried out in a manner known per se, for example in the absence or usually in the presence of a suitable solvent or diluent or of a mixture thereof, the reactions being carried out, as required, with cooling, at room temperature or with heating, for example in a temperature range from approximately 0°C to the boiling temperature of the reaction medium, preferably from approximately 20°C to approximately +120°C, especially from 60°C to 80°C, and, if required, in a closed vessel, under pressure, in an inert gas atmosphere and/or under anhydrous conditions. Especially advantageous reaction conditions may be found in the Examples.
In the various reactions, the reactants may be reacted with one another without the addition of a solvent or diluent, for example in molten form. Generally, however, the addition of an inert solvent or diluent or a mixture thereof is advantageous. The products are isolated in accordance with customary methods, for example by filtration, crystallisation, distillation or chromatography, or any suitable combination of those methods.
Variant a1/a2): Suitable leaving groups Xi in the compounds of formula (II) are, for example, hydroxy, d-C8alkoxy, haio-d-C8alkoxy, Cι-C8alkanoyloxy, mercapto, d-C8alkylthio, halo-Cι-C8alkylthio, d-C8alkanesulfonyloxy, halo-Cι-C8alkanesulfonyloxy, benzene- sulfonyloxy, toluenesulfonyloxy and halogen, preferably toluenesulfonyloxy, trifluoro- methanesulfonyloxy and halogen, especially halogen.
Suitable bases for facilitating the reaction are, for example, alkali metal or alkaline earth metal hydroxides, hydrides, amides, alkanolates, acetates, carbonates, dialkylamides or al- kylsilylamides, 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, acetate and carbonate, potassium tert-butanolate, hydroxide, carbonate and hydride, lithium diisopropylamide, potassium bis(trimethylsilyl)amide, calcium hydride, triethylamine, diisopropylethylamine, triethylenediamine, cyciohexylamine, N-cyclohexyl- N,N-dimethylamine, N.N-diethylaniline, pyridine, 4-(N,N-dimethylamino)pyridine, quin- uclidine, N-methylmoφholine, benzyltrimethylammonium hydroxide and 1 ,5-diazabicyclo- [5.4.0]undec-5-ene (DBU).
Examples of solvents or diluents include: aromatic, aliphatic and alicyclic hydrocarbons and halogenated hydrocarbons, such as benzene, toluene, xylene, mesitylene, Tetralin, chloro- benzene, dichlorobenzene, bromobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, trichloromethane, tetrachloromethane, dichloroethane, trichloroethene and tetrachloroethene; esters, such as ethyl acetate; ethers, such as diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, tert-butyl methyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, dimethoxydiethyl ether, tetrahydrofuran and dioxane; ketones, such as acetone, methyl ethyl ketone and methyl isobutyl ketone; alcohols, such as methanol, ethanol, propanol, isopropanol, butanol, ethylene glycol and glycerol; amides, such as N,N-dimethylformamide, N,N-diethyl- formamide, N,N-dimethylacetamide, N-methylpyrrolidone and hexamethyiphosphoric acid triamide; nitrites, such as acetonitrile and propionitrile; and sulfoxides, such as dimethyl sulfoxide. If the reaction is carried out in the presence of a base, bases used in excess, such as triethylamine, pyridine, N-methylmoφholine or N,N-diethylaniline, may also serve as solvents or diluents.
The reaction is carried out advantageously in a temperature range from approximately 0°C to approximately 180°C, especially from approximately 10°C to approximately 80°C, in many cases in the range from room temperature to the reflux temperature of the reaction mixture.
Preference is given to a reaction duration of from approximately 0.1 to approximately 24 hours, especially from approximately 0.5 to approximately 2 hours.
In a preferred embodiment of variant a1/a2), a compound of formula (II) is reacted with a compound of formula (III) at from 0°C to 80°C, preferably from 10°C to 30°C, in an inert solvent, preferably an amide, especially N,N-dimethylformamide, in the presence of a metal hydride, preferably sodium hydride.
Especially preferred conditions for the reaction are described in Examples P1-1d), P1-2, P3f) and P5f).
Variant b): Examples of solvents or diluents include those mentioned in variant a1/a2).
The reaction is carried out advantageously in a temperature range from approximately 0°C to approximately 180°C, especially from approximately 10°C to approximately 80°C, in many cases in the range from room temperature to the reflux temperature of the reaction mixture. Preference is given to a reaction duration of from approximately 0.1 to approximately 24 hours, especially from approximately 0.5 to approximately 2 hours.
Especially preferred conditions for the reaction are described in Examples P1-3 and P5-1g).
Variant c): Examples of solvents or diluents include: aromatic, aliphatic and alicyclic hydrocarbons and halogenated hydrocarbons, such as benzene, toluene, xylene, mesitylene, Tetralin, chlorobenzene, dichlorobenzene, bromobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, trichloromethane, tetrachloromethane, dichloroethane, trichloro- ethene and tetrachloroethene; ethers, such as diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, tert-butyl methyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, dimethoxydiethyl ether, tetrahydrofuran and dioxane; and sulfoxides, such as dimethyl sulfoxide.
The reaction is carried out advantageously in a temperature range from approximately 0°C to approximately +120°C, preferably from approximately 80°C to approximately +120°C.
Preference is given to a reaction duration of from approximately 0.1 to approximately 24 hours, especially from approximately 0.5 to approximately 2 hours.
Variant d): Suitable oxidising agents are, for example, inorganic peroxides, such as sodium perborate, or hydrogen peroxide, or organic peracids, such as perbenzoic acid or peracetic acid, or mixtures of organic acids and hydrogen peroxide, for example acetic acid/hydrogen peroxide.
Examples of solvents or diluents include: aromatic, aliphatic and alicyclic hydrocarbons and halogenated hydrocarbons, such as benzene, toluene, xylene, mesitylene, Tetralin, chloro- benzene, dichlorobenzene, bromobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, trichloromethane, tetrachloromethane, dichloroethane, trichloroethene and tetrachloroethene; esters, such as ethyl acetate; ethers, such as diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, tert-butyl methyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, dimethoxydiethyl ether, tetrahydrofuran and dioxane; ketones, such as acetone, methyl ethyl ketone and methyl isobutyl ketone; alcohols, such as methanol, ethanol and propanol; amides, such as N,N-dimethylformamide, N,N-diethylformamide, N,N-dimethylacetamide, N-methyl- pyrroiidone and hexamethylphosphoric acid triamide; nitriles, such as acetonitrile and propi- onitrile; and sulfoxides, such as dimethyl sulfoxide. If the reaction is carried out in the presence of an organic acid or peracid, acids used in excess, for example strong organic carboxylic acids, such as unsubstituted or substituted, for example halo-substituted, d-C alkanecarboxylic acids, e.g. formic acid, acetic acid or propionic acid, may also serve as solvent or diluent. The reaction is carried out advantageously in a temperature range from approximately 0°C to approximately +120°C, preferably from approximately 0°C to approximately +40°C.
Preference is given to a reaction duration of from approximately 0.1 to approximately 24 hours, especially from approximately 0.5 to approximately 2 hours.
Variant e): Suitable bases for facilitating the reaction are, for example, those mentioned in variant a1/a2).
Examples of solvents or diluents include those mentioned in variant a1/a2).
The reaction is carried out advantageously in a temperature range from approximately 0°C to approximately 180°C, especially from approximately 10°C to approximately 80°C, in many cases in the range from room temperature to the reflux temperature of the reaction mixture.
Preference is given to a reaction duration of from approximately 0.1 to approximately 24 hours, especially from approximately 0.5 to approximately 2 hours.
Especially preferred conditions may be found in Example P3 e).
Variant f): Suitable bases for facilitating the reaction are, for example, those mentioned in variant a1/a2).
Examples of solvents or diluents include those mentioned in variant a1/a2).
The reaction is carried out advantageously in a temperature range from approximately 0°C to approximately 180°C, especially from approximately 10°C to approximately 80°C, in many cases in the range from room temperature to the reflux temperature of the reaction mixture.
Preference is given to a reaction duration of from approximately 0.1 to approximately 24 hours, especially from approximately 0.5 to approximately 2 hours. ln a preferred embodiment of variant f), a compound of formula (VI) is reacted with a co m- pound of formula (VII) at from 0°C to 120°C, preferably from 60°C to 120°C, in an inert solvent, preferably an amine, especially pyridine. Especially preferred conditions may be found in Example P1-1c) and also in the analogous reaction described in Example P3 e).
Especially preferred conditions for process variants g), h), i), k), I) and m) may be found in the Examples. In particular, the conditions for the process according to variant g) may be found in Examples P9-1 and P9-2; according to variant h) in Example P6-1 ; according to variant i) in Example P1-1a); according to variant k) in Examples P3b) and P5b); according to variant I) in Example P7-1; and according to variant m) in Examples P10-1 and P12-1 or applied analogously to those processes.
Some of the compounds of formulae (I) and (III) to (XXIV) may be in the form of one of the possible isomers or in the form of a mixture thereof, for example according to the number of asymmetric carbon atoms and the absolute and relative configuration thereof in the form of pure isomers, such as antipodes and/or diastereoisomers, or in the form of mixtures of isomers, such as mixtures of enantiomers, for example racemates, mixtures of diastereoisomers or mixtures of racemates; the invention relates both to the pure isomers and to all possible mixtures of isomers and this is to be understood accordingly hereinbefore and hereinafter, even if stereochemical details are not specifically mentioned in each case.
Mixtures of diastereoisomers and mixtures of racemates of compounds of formulae (I) and some of the compounds (III) to (XXIV) that are obtainable in accordance with the process depending upon the starting materials and procedures chosen, or by other means, can be separated into the pure diastereoisomers or racemates in known manner on the basis of the physico-chemical differences between the constituents, for example by fractional crystallisation, distillation and/or chromatography.
Mixtures of enantiomers, such as racemates, so obtainable can be separated into the optical antipodes by known methods, for example by recrystaliisation from an optically active solvent, by chromatography on chiral adsorbents, for example high-pressure liquid chromatography (HPLC) on acetyl cellulose, with the aid of suitable microorganisms, by cleav- age with specific immobilised enzymes, and via the formation of inclusion compounds, for example using chiral crown ethers, in which case only one enantiomer is complexed.
Apart from by the separation of corresponding mixtures of isomers, it is possible according to the invention to obtain pure diastereoisomers or enantiomers also by generally known methods of diastereoselective or enantioselective synthesis, for example by carrying out the process according to the invention with starting materials having appropriate stereochemistry.
It is advantageous to isolate or synthesise the biologically more active isomer, for example enantiomer, or mixture of isomers, for example mixture of enantiomers, insofar as the individual components have different biological activity.
Some of the compounds (I) and (III) to (XXIV) can also be obtained in the form of their hydrates and/or may include other solvents, for example solvents that may have been used for the crystallisation of compounds in solid form.
The invention relates to all those embodiments of the process according to which a compound obtainable as starting material or intermediate at any stage of the process is used as starting material and all or some of the remaining steps are carried out, or a starting material is used in the form of a derivative or a salt and/or its racemates or antipodes, or, especially, is formed under the reaction conditions.
In the process of the present invention there are preferably used those starting materials and intermediates which result in the compounds of formula (I) described at the beginning as being especially valuable.
The invention relates especially to the preparation processes described in Examples P1 to P12.
The invention relates also to starting materials and intermediates used according to the i n- vention in the preparation of compounds of formula (I), especially the compounds of form u- lae (III), (IV), (VI), (Vlll), (IX), (XII), (XIII), (XV), (XVII), (XVIII), (XXII), (XXIII) and (XXIV), which are novel, to their use and to processes for the preparation thereof. In particular, the compounds of formulae (III) and (VI) can be prepared analogously to Examples P1 c) and P1 b), respectively.
The compounds of formulae (II), (V), (VII), (X), (XI), (XIV), (XVI) and (XIX) to (XXI) are known or can be prepared in accordance with methods known perse.
In the area of pest control, the compounds of formula (I) according to the invention are valuable preventive and/or curative active ingredients having a very advantageous biocidal spectrum even at low rates of concentration, while being well tolerated by warm-blooded animals, fish and plants. The compounds of the invention are effective against all or individual development stages of normally sensitive animal pests, but also of resistant animal pests, such as insects and representatives of the order Acarina, and phytopathogenic fungi. The insecticidal, ovicidal and/or acaricidal action of the compounds of the invention may manifest itself directly, i.e. in the mortality of the pests, which occurs immediately or only after some time, for example during moulting, or of their eggs, or indirectly, for example in reduced oviposition and/or hatching rate, good activity corresponding to a mortality of at least 50 to 60 %.
The mentioned animal pests include, for example, those mentioned in European Patent Application EP-A-736 252. Accordingly, the said pests mentioned in EP-A-736 252 are included by reference in the subject matter of the present invention.
The mentioned phytopathogenic fungi include, for example: of the class of the Fungi imperfecti, for example,
Botrytis spp., Pyricularia spp., Helminthosporium spp., Fusarium spp., Septoria spp., Cerco- spora spp. and Alternaria spp.; of the class of the Basidiomycetes, for example,
Rhizoctonia spp., Hemileia spp. and Puccinia spp.; of the class of the Ascomycetes, for example,
Venturia spp., Erysiphe spp., Podosphaera spp., Monilinia spp. and Uncinula spp.; and of the class of the Oomycetes, for example,
Phytophthora spp., Pythium spp. and Plasmopara spp.. With the compounds according to the invention it is possible to control, i.e. to inhibit or destroy, pests of the mentioned type occurring especially on plants, more especially on useful plants and ornamentals in agriculture, in horticulture and in forestry, or on parts of such plants, such as the fruit, blossom, leaves, stems, tubers or roots, while in some cases parts of the plants that grow later are also protected against those pests.
Target crops are especially cereals, such as wheat, barley, rye, oats, rice, maize and sorghum; beet, such as sugar beet and fodder beet; fruit, such as pomes, stone fruit and soft fruit, such as apples, pears, plums, peaches, almonds, cherries, or berries, for example strawberries, raspberries and blackberries; leguminous plants, such as beans, lentils, peas and soybeans; oil plants, such as rape, mustard, poppy, olives, sunflowers, coconut, castor oil plants, cocoa beans and groundnuts; cucurbitaceae, such as marrows, cucumber and melons; fibre plants, such as cotton, flax, hemp and jute; citrus fruit, such as oranges, lemons, grapefruit and mandarins; vegetables, such as spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes and paprika; lauraceae, such as avocados, cinnamon and camphor; and tobacco, nuts, coffee, aubergines, sugar cane, tea, pepper, vines, hops, bananas and natural rubber plants, as well as ornamentals.
The compounds according to the invention are especially suitable for controlling insects and representatives of the order Acarina, especially plant-destructive feeding insects, such as Anthonomus grandis, Diabrotica balteata, Heliothis virescens larvae, Plutella xylostella and Spodoptera littoralis larvae, and spider mites, such as Tetranychus spp., in cotton, fruit, maize, soybean, rape and vegetable crops.
Further areas of use of the compounds according to the invention are the protection of stored goods and stocks and materials, and also in the hygiene sector, especially the protection of domestic animals and productive livestock against pests of the mentioned type.
The invention therefore relates also to pesticides, such as emulsifiabie concentrates, suspension concentrates, directly sprayable or dilutable solutions, coatable pastes, dilute emulsions, wettable powders, soluble powders, dispersible powders, wettable powders, dusts, granules or encapsulations in polymer substances, comprising - at least - one of the compounds of the invention, the type of formulation being chosen in accordance with the intended objectives and prevailing circumstances. The active ingredient is used in those compositions in pure form: a solid active ingredient, for example, in a specific particle size, or preferably together with - at least - one of the adjuvants customary in formulation technology, such as extenders, for example solvents or solid carriers, or surface-active compounds (surfactants).
Formulation adjuvants used are, e.g., solid carriers, solvents, stabilisers, "slow release" adjuvants, colorants and optionally surface-active substances (surfactants). Suitable carriers and adjuvants include any substances customarily used in plant protection compositions, especially in compositions for controlling slugs and snails. Suitable adjuvants, such as solvents, solid carriers, surface-active compounds, non-ionic surfactants, cationic surfactants, anionic surfactants and other adjuvants in the compositions used according to the invention include, for example, the same substances as those described in EP-A-736252. Accordingly, the said adjuvants mentioned in EP-A-736252 are included by reference in the subject matter of the present invention.
The compositions usually comprise 0.1 to 99%, preferably 0.1 to 95%, of active ingredient, and 1 to 99.9%, preferably 5 to 99.9%, of - at least - one solid or liquid adjuvant, it generally being possible for 0 to 25%, preferably 0.1 to 20%, of the composition to be surfactants (in each case percentages are by weight). Whereas commercial products will preferably be formulated as concentrates, the end user will normally employ dilute formulations which have substantially lower active ingredient concentrations. Preferred formulations have especially the following composition (% = percent by weight):
Emulsifiable concentrates: active ingredient: 1 to 90 %, preferably 5 to 20 % surfactant: 1 to 30 %, preferably 10 to 20 % solvent: 5 to 98 %, preferably 70 to 85 %
Dusts: active ingredient: 0.1 to 10 %, preferably 0.1 to 1 % solid carrier: 99.9 to 90 %, preferably 99.9 to 99 % Suspension concentrates: active ingredient: 5 to 75 %, preferably 10 to 50 % water: 94 to 24 %, preferably 88 to 30 % surfactant: 1 to 40 %, preferably 2 to 30 %
Wettable powders: active ingredient: 0.5 to 90 %, preferably 1 to 80 % surfactant: 0.5 to 20 %, preferably 1 to 15 % solid carrier: 5 to 99 %, preferably 15 to 98 %
Granules: active ingredient: 0.5 to 30 %, preferably 3 to 15 % solid carrier: 99.5 to 70 %, preferably 97 to 85 %
The activity of the compositions according to the invention can be substantially broadened and adapted to prevailing circumstances by the addition of other insecticidal, acaricidal and/or f ungicidal active ingredients. Examples of suitable additional active ingredients include representatives of the following classes of compounds: organophosphorus compounds, nitrophenols and derivatives, formamidines, ureas, carbamates, pyrethroids, chlorinated hydrocarbons and Bacillus thuringiensis preparations. The compositions according to the invention may also comprise further solid or liquid adjuvants, such as stabilisers, for example vegetable oils or epoxidised vegetable oils (e.g. epoxidised coconut oil, rape oil or soybean oil), antifoams, for example silicone oil, preservatives, viscosity regulators, binders and/or tackifiers, as well as fertilisers or other active ingredients for obtaining special effects, for example bactericides, nematicides, molluscicides or selective herbicides.
The compositions according to the invention are prepared in known manner, in the absence of adjuvants, for example by grinding and/or sieving a solid active ingredient or mixture of active ingredients, for example to a specific particle size, or in the presence of at least one adjuvant, for example by intimately mixing and/or grinding the active ingredient or mixture of active ingredients with the adjuvant(s). The invention relates also to those processes for the preparation of the compositions according to the invention and to the use of the compounds of formula (I) in the preparation of those compositions. The invention relates also to the methods of application of the compositions, i.e. the methods of controlling pests of the mentioned type, such as spraying, atomising, dusting, coating, dressing, scattering or pouring, which are selected in accordance with the intended objectives and prevailing circumstances, and to the use of the compositions for controlling pests of the mentioned type. Typical rates of concentration are from 0.1 to 1000 ppm, preferably from 0.1 to 500 ppm, of active ingredient. The rates of application per hectare are generally from 1 to 2000 g of active ingredient per hectare, especially from 10 to 1000 g/ha, preferably from 20 to 600 g/ha.
A preferred method of application in the area of plant protection is application to the foliage of the plants (foliar application), the number of applications and the rate of application depending on the risk of infestation by the pest in question. However, the active ingredient can also penetrate the plants through the roots (systemic action) if the locus of the plants is impregnated with a liquid formulation or if the active ingredient is incoφorated in solid form into the locus of the plants, for example into 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 compositions according to the invention are also suitable for protecting plant propagation material, e.g. seed, such as fruit, tubers or grains, or plant cuttings, from fungal infections and animal pests. The propagation material can be treated with the formulation before planting: seed, for example, can be dressed before being sown. The compounds of the invention can also be applied to grains (coating), either by impregnating the grains with a liquid formulation or by coating them with a solid formulation. The formulation can also be applied to the planting site when the propagation material is being planted, for example to the seed furrow during sowing. The invention relates also to those methods of treating plant propagation material and to the plant propagation material thus treated.
The following Examples are intended to illustrate the invention. They do not limit the invention. Temperatures are given in degrees Celsius. Preparation Examples
Example P1-1 : 2-[[[(1 -Methyl-2-(4-(1 -{4-chlorophenyl}-ethoxy)-phenyl)-[ethoxyimino]- ethylidene)amino]oxy]methyl]-α-(methoxymethylene)-phenylacetic acid methyl ester a) 1 -[4-(1 -{4-Chlorophenyl}-ethoxy)-phenyl]-propan-1 -one
26.5 g of 1 -(4-chlorophenyl)-ethanol are added dropwise to 7.9 g of sodium hydride (55 % in oil) in 250 ml of dimethylacetamide and the mixture is stirred at room temperature for 30 minutes. 25.7 g of 4-fluoropropiophenone are then added dropwise; the mixture is heated to 100°C and stirred for 90 minutes. After cooling, the reaction mixture is concentrated in vacuo; the residue is taken up in ethyl acetate, washed twice with water and once with saturated sodium chloride solution and dried over sodium sulfate. The solvent is evaporated off in vacuo and the residue is purified by recrystallisation from hexane to yield the title compound having a melting point 70-71 °C.
b) 1 -(4-(1 -{4-Chlorophenyl}-ethoxy)-phenyl)-1 ,2-propanedione-2-oxime
Dry HCI gas is introduced into 200 ml of diethyl ether over a period of 0.5 minutes and 43.2 g of 1-[4-(1-{4-chlorophenyl}-ethoxy)-phenyl]-propan-1-one are then added. 21.0 g of isopentyl nitrite are then added dropwise and the reaction mixture is then stirred for 3 hours at room temperature. The reaction mixture is concentrated by evaporation in vacuo and the crude product is purified by chromatography on silica gel using ethyl acetate/hexane (1:3), yielding the title compound having a melting point of 88-90°C.
c) 1 -[4-(1 -{4-Chlorophenyl}-ethoxy)-phenyl]-1 ,2-propanedione-[ethyloxime]-2-oxime
A mixture of 29.0 g of 1-(4-(1-{4-chlorophenyl}-ethoxy)-phenyl)-1,2-propanedione-2-oxime and 9.4 g of O-ethylhydroxylamine hydrochloride in 150 ml of pyridine is boiled at reflux for 1 hour. After cooling, the reaction mixture is concentrated by evaporation in vacuo. The residue is dissolved in ethyl acetate; the organic phase is washed twice with water and once with saturated sodium chloride solution, dried with sodium sulfate and concentrated by evaporation. The crude product is stirred together with hexane; filtration is carried out and the filter residue is dried, yielding the title product having a melting point of 132-134°C. d) 2-[[[(1 -Methyl-2-(4-(1 -{4-chlorophenyl}-ethoxy)-phenyl)-[ethoxyimino]ethylidene)- amino]oxy]methyl]-α-(methoxymethylene)-phenylacetic acid methyl ester 7 g of 1 -[4-(1 -{4-chlorophenyl}-ethoxy)-phenyl]-1 ,2-propanedione-[ethyloxime]-2-oxime dissolved in 25 ml of N,N-dimethylformamide are added dropwise to a suspension of 0.9 g of sodium hydride (55 % in oil) in 40 ml of N,N-dimethylformamide and the reaction mixture is then stirred for 10 minutes at room temperature. 5.5 g of 2-(bromomethyl)-α-(methoxy- methylene)-phenylacetic acid methyl ester in 20 ml of N,N-dimethylformamide are then added dropwise and the reaction mixture is stirred for a further 1 hour at room temperature. The mixture is then rendered acidic with acetic acid and concentrated by evaporation in vacuo. The residue is dissolved in ethyl acetate and the solution is washed three times with water and once with saturated sodium chloride solution, dried with sodium sulfate and concentrated by evaporation in vacuo. Purification by flash chromatography (silica gel, ethyl acetate/hexane 1 :3) yields the E isomer of the title compound having a melting point of 107-109°C (compound 1-4.2).
Example P1-2: 2-[[[(1 -Methyl-2-(4-(1 -{4-chlorophenyl}-ethoxy)-phenyl)-[ethoxyimino]ethyl- idene)amino]oxy]methyl]-α-(methoxyimino)-phenylacetic acid methyl ester In a manner analogous to that described in Example P1-1 d), 1 -[4-(1 -{4-chlorophenyl}- ethoxy)-phenyl]-1 ,2-propanedione-[ethyloxime]-2-oxime and 2-(bromomethyl)-α-(methoxy- imino)-phenylacetic acid methyl ester yield the title compound having a melting point of 111 -113°C (compound 2.4-2).
Example P1-3: 2-[[[(1 -Methyl-2-(4-(1 -{4-chlorophenyl}-ethoxy)-phenyl)-[ethoxyimino]ethyl- idene)amino]oxy]methyl]-α-(methoxyimino)-phenylacetic acid methylamide A mixture of 4.0 g of 2-[[[(1-methyl-2-(4-(1-{4-chlorophenyl}-ethoxy)-phenyl)-2-E-[ethoxy- imino]ethylidene)amino]oxy]methyl]-α-(methoxyimino)-phenylacetic acid methyl ester and 5.3 ml of a 8M solution of methylamine in ethanol is left to stand at room temperature for 4 days. The mixture is then concentrated by evaporation in vacuo. The residue is taken up with methyl acetate; the solution is washed with water and saturated sodium chloride solution, dried over sodium sulfate and concentrated by evaporation in vacuo. The residue is recrystallised from methyl acetate/hexane 1 :1 to yield the title compound having a melting point of 81-83°C (compound 3-4.2). Example P2: It is also possible to prepare the other compounds listed in Tables 1.1 to 3.26 in a manner analogous to that described in Example P1; c.propyl denotes cyclopropyl.
Table A: Compounds of general formula (I) wherein A-R7 is defined as follows Number A-R7
A.1 CH3
A.2 C2H5
A.3 n-C3H7
A.4 iso-C3H7
A.5 n-C4H9
Figure imgf000033_0001
A.7 CH2F
A.8 CHF2
A.9 CH2CF3
A.10 CH2CH=CH2
A.11 GH2GH=GHGH3
A.12 CH2CH=C(CH3)2
A.13 CH2CH=CHCI
A.14 CH2CH=CCI2
A.15 CH2C(CH3)=CH2
A.16 CH2C≡CH
A.17 CH2Si(CH3)3
A.18 CH2-c.propyl-2,2-CI2
A.19 CH2-c.propyl
A.20 CH2CN
A.21 CH2COOCH3
A.22 CH2COOC2H5
A.23 CH2COO-iso-C3H7
A.24 CH(CH3)COOC2H5
A.25 C(=O)OC2H5
A.26 C(=O)NHCH3
A.27 C(=O)C(=O)OC2H6 A.28 CH2CeHs
A.29 CH2CeH -2-F
A.30 CH2C8H -3-F
A.31 CH2C6H4-4-F
A.32 CH2C6H4-2-CI
Figure imgf000034_0001
A.34 CH2C6H4-4-CI
A.35 CH2C6H4-2-Br
A.36 CH2CeH -3-Br
A.37 CH2C6H4-4-Br
A.38 CH2C8H -2-CF3
A.39 CH2CeH -3-CF3
A.40 CH2C6H4-4-CF3
Table 1 -1 : Compounds of general formula
Figure imgf000034_0002
wherein (R5)s is 4-CF3 and the substituent A-R7 corresponds in each case to a line of Table A.
Table 1 -2: Compounds of general formula (1.1) wherein (R5)s is 3-CF3 and the substituent A-R7 corresponds in each case to a line of Table A.
Table 1 -3: Compounds of general formula (1.1) wherein (R5)s is 2-CF3 and the substituent A-R7 corresponds in each case to a line of Table A.
Table 1 -4: Compounds of general formula (1.1) wherein (R5)s is 4-CI and the substituent A-R7 corresponds in each case to a line of Table A.
Table 1 -5: Compounds of general formula (1.1) wherein (R5)s is 3-CI and the substituent A-R7 corresponds in each case to a line of Table A.
Table 1-6: Compounds of general formula (1.1) wherein (R5)s is 2-CI and the substituent A-R7 corresponds in each case to a line of Table A. Table 1 -7: Compounds of general formula (1.1) wherein (R5)s is 4-Br and the substituent A-R7 corresponds in each case to a line of Table A.
Table 1 -8: Compounds of general formula (1.1) wherein (R5)s is 3-Br and the substituent A-R7 corresponds in each case to a line of Table A.
Table 1-9: Compounds of general formula (1.1) wherein (R5)s is 2-Br and the substituent A-R7 corresponds in each case to a line of Table A.
Table 1-10: Compounds of general formula (1.1) wherein (R5)s is 4-F and the substituent A-R7 corresponds in each case to a line of Table A.
Table 1-11 : Compounds of general formula (1.1) wherein (R5)s is 3-F and the substituent A-R7 corresponds in each case to a line of Table A.
Table 1-12: Compounds of general formula (1.1) wherein (R5)s is 2-F and the substituent A-R7 corresponds in each case to a line of Table A.
Table 1-13: Compounds of general formula (1.1) wherein (R5)s is 2,4-CI2 and the substituent A-R7 corresponds in each case to a line of Table A.
Table 1-14: Compounds of general formula (1.1) wherein (R5)s is 3,4-CI2 and the substituent A-R7 corresponds in each case to a line of Table A.
Table 1-15: Compounds of general formula (1.1) wherein (R5)s is 4-O-CF3 and the substituent A-R7 corresponds in each case to a line of Table A.
Table 1-16: Compounds of general formula (1.1) wherein (R5)s is 4-CH3 and the substituent A-R7 corresponds in each case to a line of Table A.
Table 1-17: Compounds of general formula (1.1) wherein (R5)s is 4-C2H5 and the substituent A-R7 corresponds in each case to a line of Table A.
Table 1-18: Compounds of general formula (1.1) wherein (R5)s is 4-n-C3H7and the substituent A-R7 corresponds in each case to a line of Table A.
Table 1-19: Compounds of general formula (1.1) wherein (R5)s is 4-iso-C3H7 and the substituent A-R7 corresponds in each case to a line of Table A.
Table 1 -20: Compounds of general formula (1.1) wherein (R5)s is 4-n-C H9 and the substituent A-R7 corresponds in each case to a line of Table A. Table 1 -21 : Compounds of general formula (1.1) wherein (R5)s is 4-isobutyl and the substituent A-R7 corresponds in each case to a line of Table A.
Table 1-22: Compounds of general formula (1.1) wherein (R5)s is 4-sec-butyl and the substituent A-R7 corresponds in each case to a line of Table A.
Table 1 -23: Compounds of general formula (1.1) wherein (R5)s is 4-tert-butyl and the substituent A-R7 corresponds in each case to a line of Table A.
Table 1-24: Compounds of general formula (1.1) wherein (R5)s is 4-CN and the substituent A-R7 corresponds in each case to a line of Table A.
Table 1-25: Compounds of general formula (1.1) wherein (R5)s is 4-O-CH3 and the substituent A-R7 corresponds in each case to a line of Table A.
Table 1-26: Compounds of general formula (1.1) wherein (R5)s is 2,4-F2 and the substituent A-R7 corresponds in each case to a line of Table A.
Compound of formula (1.1) wherein A-R is ethyl and (R5)s is 4-chlorine: m.p.: 107-109°C (compound 1-4.2).
Table 2-1 : Compounds of general formula
Figure imgf000036_0001
wherein (R5)s is 4-CF3 and the substituent A-R7 corresponds in each case to a line of Table A.
Table 2-2: Compounds of general formula (I.2) wherein (R5)s is 3-CF3 and the substituent A-R7 corresponds in each case to a line of Table A.
Table 2-3: Compounds of general formula (I.2) wherein (R5)s is 2-CF3 and the substituent A-R7 corresponds in each case to a line of Table A.
Table 2-4: Compounds of general formula (I.2) wherein (R5)s is 4-CI and the substituent A-R7 corresponds in each case to a line of Table A.
Table 2-5: Compounds of general formula (I.2) wherein (R5)s is 3-CI and the substituent A-R7 corresponds in each case to a line of Table A. Table 2-6: Compounds of general formula (1.2) wherein (R5)s is 2-CI and the substituent A-R7 corresponds in each case to a line of Table A.
Table 2-7: Compounds of general formula (1.2) wherein (R5)s is 4-Br and the substituent A-R7 corresponds in each case to a line of Table A.
Table 2-8: Compounds of general formula (1.2) wherein (R5)s is 3-Br and the substituent A-R corresponds in each case to a line of Table A.
Table 2-9: Compounds of general formula (1.2) wherein (R5)s is 2-Br and the substituent A-R7 corresponds in each case to a line of Table A.
Table 2-10: Compounds of general formula (I.2) wherein (R5)s is 4-F and the substituent A-R7 corresponds in each case to a line of Table A.
Table 2-11 : Compounds of general formula (I.2) wherein (R5)s is 3-F and the substituent A-R7 corresponds in each case to a line of Table A.
Table 2-12: Compounds of general formula (I.2) wherein (R5)s is 2-F and the substituent A-R corresponds in each case to a line of Table A.
Table 2-13: Compounds of general formula (I.2) wherein (R5)s is 2,4-CI2 and the substituent A-R7 corresponds in each case to a line of Table A.
Table 2-14: Compounds of general formula (I.2) wherein (R5)s is 3,4-CI2 and the substituent A-R7 corresponds in each case to a line of Table A.
Table 2-15: Compounds of general formula (I.2) wherein (R5)s is 4-O-CF3 and the substituent A-R7 corresponds in each case to a line of Table A.
Table 2-16: Compounds of general formula (I.2) wherein (R5)s is 4-CH3 and the substituent A-R7 corresponds in each case to a line of Table A.
Table 2-17: Compounds of general formula (I.2) wherein (R5)s is 4-C2H5 and the substituent A-R7 corresponds in each case to a line of Table A.
Table 2-18: Compounds of general formula (I.2) wherein (R5)s is 4-n-C3H7and the substituent A-R corresponds in each case to a line of Table A.
Table 2-19: Compounds of general formula (I.2) wherein (R5)s is 4-iso-C3H7 and the substituent A-R7 corresponds in each case to a line of Table A. Table 2-20: Compounds of general formula (1.2) wherein (R5)s is 4-n-C H9 and the substituent A-R7 corresponds in each case to a line of Table A.
Table 2-21 : Compounds of general formula (I.2) wherein (R5)s is 4-isobutyl and the substituent A-R7 corresponds in each case to a line of Table A.
Table 2-22: Compounds of general formula (I.2) wherein (R5)s is 4-sec-butyl and the substituent A-R7 corresponds in each case to a line of Table A.
Table 2-23: Compounds of general formula (I.2) wherein (R5)s is 4-tert-butyl and the substituent A-R7 corresponds in each case to a line of Table A.
Table 2-24: Compounds of general formula (I.2) wherein (R5)s is 4-CN and the substituent A-R7 corresponds in each case to a line of Table A.
Table 2-25: Compounds of general formula (I.2) wherein (R5)s is 4-O-CH3 and the substituent A-R7 corresponds in each case to a line of Table A.
Table 2-26: Compounds of general formula (I.2) wherein (R5)s is 2,4-F2 and the substituent A-R7 corresponds in each case to a line of Table A.
Compound of formula (I.2) wherein A-R7 is ethyl and (R5)s is 4-chlorine: m.p.: 111-113°C (compound 2-4.2).
Table 3-1 : Compounds of general formula
Figure imgf000038_0001
wherein (R5)s is 4-CF3 and the substituent A-R7 corresponds in each case to a line of Table A.
Table 3-2: Compounds of general formula (I.3) wherein (R5)s is 3-CF3 and the substituent A-R7 corresponds in each case to a line of Table A.
Table 3-3: Compounds of general formula (I.3) wherein (R5)s is 2-CF3 and the substituent A-R7 corresponds in each case to a line of Table A.
Table 3-4: Compounds of general formula (I.3) wherein (R5)s is 4-CI and the substituent A-R7 corresponds in each case to a line of Table A. Table 3-5: Compounds of general formula (1.3) wherein (R5)s is 3-CI and the substituent A-R7 corresponds in each case to a line of Table A.
Table 3-6: Compounds of general formula (1.3) wherein (R5)s is 2-CI and the substituent A-R7 corresponds in each case to a line of Table A.
Table 3-7: Compounds of general formula (1.3) wherein (R5)s is 4-Br and the substituent A-R7 corresponds in each case to a line of Table A.
Table 3-8: Compounds of general formula (1.3) wherein (R5)s is 3-Br and the substituent A-R7 corresponds in each case to a line of Table A.
Table 3-9: Compounds of general formula (1.3) wherein (R5)s is 2-Br and the substituent A-R7 corresponds in each case to a line of Table A.
Table 3-10: Compounds of general formula (I.3) wherein (R5)s is 4-F and the substituent A-R7 corresponds in each case to a line of Table A.
Table 3-11 : Compounds of general formula (I.3) wherein (R5)s is 3-F and the substituent A-R7 corresponds in each case to a line of Table A.
Table 3-12: Compounds of general formula (I.3) wherein (R5)s is 2-F and the substituent A-R7 corresponds in each case to a line of Table A.
Table 3-13: Compounds of general formula (I.3) wherein (R5)s is 2,4-CI2 and the substituent A-R7 corresponds in each case to a line of Table A.
Table 3-14: Compounds of general formula (I.3) wherein (R5)s is 3,4-CI2 and the substituent A-R7 corresponds in each case to a line of Table A.
Table 3-15: Compounds of general formula (I.3) wherein (R5)s is 4-O-CF3 and the substituent A-R7 corresponds in each case to a line of Table A.
Table 3-16: Compounds of general formula (I.3) wherein (R5)s is 4-CH3 and the substituent A-R7 corresponds in each case to a line of Table A.
Table 3-17: Compounds of general formula (I.3) wherein (R5)s is 4-C2H5 and the substituent A-R corresponds in each case to a line of Table A.
Table 3-18: Compounds of general formula (I.3) wherein (R5)s is 4-n-C3H7and the substituent A-R7 corresponds in each case to a line of Table A. Table 3-19: Compounds of general formula (I.3) wherein (Rs)s is 4-iso-C3H7 and the substituent A-R7 corresponds in each case to a line of Table A.
Table 3-20: Compounds of general formula (I.3) wherein (R5)s is 4-n-C4H9 and the substituent A-R7 corresponds in each case to a line of Table A.
Table 3-21 : Compounds of general formula (I.3) wherein (R5)s is 4-isobutyl and the substituent A-R7 corresponds in each case to a line of Table A.
Table 3-22: Compounds of general formula (I.3) wherein (R5)s is 4-sec-butyl and the substituent A-R7 corresponds in each case to a line of Table A.
Table 3-23: Compounds of general formula (I.3) wherein (R5)s is 4-tert-butyl and the substituent A-R7 corresponds in each case to a line of Table A.
Table 3-24: Compounds of general formula (I.3) wherein (R5)s is 4-CN and the substituent A-R7 corresponds in each case to a line of Table A.
Table 3-25: Compounds of general formula (I.3) wherein (R5)s is 4-O-CH3 and the substituent A-R7 corresponds in each case to a line of Table A.
Table 3-26: Compounds of general formula (I.3) wherein (R5)s is 2,4-F2 and the substituent A-R7 corresponds in each case to a line of Table A.
Compound of formula (I.3) wherein A-R7 is ethyl and (R5)s is 4-chlorine: m.p.: 81-83°C (compound 3-4.2).
Compounds of formula
Figure imgf000040_0001
The figures given in the column "Phys. data" denote melting points in °C. X Y AR7 R R5 Phys. data
CH O-CH3 CH3 CH3 4-CI 128-130
CH O-CH3 CH3 CH3 4-CF3 116-118
CH O-CH3 CH2CH3 CH3 4-CF3 98-100
CH O-CH3 CH3 CH2CH3 4-CI 105-107
CH O-CH3 CH2CH3 CH2CH3 4-F resin
CH O-CH3 CH2CH3 CH2CH3 4-CI 89-91
CH O-CH3 CH3 CH2CH3 4-F 101-103
CH O-CH3 CH3 CH2CH3 4-tert-butyl 101-102
CH O-CH3 CH3 CH2CH3 4-CF3 124-126
CH O-CH3 CH2CH3 CH2CH3 4-CF3 112-114
N O-CH3 CH3 CH3 4-CI 121-123
N O-CH3 CH3 CH3 4-CF3 116-118
N O-CH3 CH2CH3 CH3 4-CF3 112-114
N O-CH3 CH3 CH2CH3 4-CI 100-102
N O-CH3 CH2CH3 CH2CH3 4-F 102-104
N O-CH3 CH CH3 CH2CH3 4-CI 103-105
N O-CH3 CH3 CH2CH3 4-F 116-118
N O-CH3 CH2CH3 CH2CH3 4-tert-butyl resin
N O-CH3 CH3 CH2CH3 4-tert-butyl 106-107
N O-CH3 CH3 CH2CH3 4-CF3 114-116
N O-CH3 CH2CH3 CH2CH3 4-CF3 72-74
N NHCH3 CH3 CH3 4-CI 146-148
N NHCH3 CH3 CH3 4-CF3 130-132
N NHCH3 CH2CH3 CH3 4-CF3 148-150
N NHCH3 CH3 CH2CH3 4-CI 139-141
N NHCH3 CH2CH3 CH2CH3 4-F 112-114
N NHCH3 CH2CH3 CH2CH3 4-CI 131-133
N NHCH3 CH3 CH2CH3 4-F 124-126
N NHCH3 CH3 CH2CH3 4-CF3 149-151
N NHCH3 CH2CH3 CH2CH3 4-CF3 134-136 Example P3: Preparation of 2-[2-(2-{4-[2-(4-chlorophenyl)-2-methoxyimino-ethoxy]-phenyl}- 2-ethoxyimino-1 -methyl-ethylideneaminooxymethyl)-phenyl]-3-methoxy-acrylic acid methyl
ester of the formula
Figure imgf000042_0001
a) 4-Chlorophenacyl bromide O-methyloxime
50.3 g of 4-chlorophenacyl bromide in 300 ml of glacial acetic acid are stirred with 23 g of sodium acetate and 21.6 g O-methylhydroxylamine hydrochloride for 2 hours at 70°C. 150 ml of ethyl acetate are added to the mixture, which is then extracted by washing several times with water and saturated sodium chloride solution. The organic phase is dried over sodium sulfate and concentrated by evaporation in vacuo. Crystallisation from hexane yields 4-chlorophenacyl bromide O-methyloxime having a melting point of 57 to 60°C.
b) Compound of the formula
Figure imgf000042_0002
19.7 g of 1 -(4-hydroxyphenyl)-propan-2-one, 34.4 g of 4-chlorophenacyl bromide O-methyloxime and 36 g of potassium carbonate are stirred in 200 ml of dimethylformamide for 2 hours at 80°C. 200 ml of ethyl acetate are added to the reaction mixture, which is then washed several times with water and saturated sodium chloride solution, dried over sodium sulfate and concentrated by evaporation in vacuo. The crude product is chromatographed on silica gel using tert-butyl methyl ether/hexane (1 :19) to yield the title compound in the form of an oil. c) Compound of the formula
Figure imgf000043_0001
35 g of a compound obtainable according to process P3b) are placed in 200 ml of methanol and 18 ml of isopentyl nitrite. At 0°C, 30 ml of a 30 % solution of sodium methanolate in methanol are added dropwise and the mixture is stirred for 2 hours at room temperature. The solvent is evaporated off, and 200 ml of ethyl acetate and 200 ml of water are added; the aqueous phase is separated off and the organic phase is then washed several times with water. Evaporating off the solvent and recrystallisation of the residue from di- chloromethane/hexane yield the title product having a melting point of 131-133°C.
d) 1-{4-[2-(4-Chlorophenyl)-2-methoxyimino-ethoxy]-phenyl}-propane-1 ,2-dione 1-(O-ethyl- oxime) of the formula
Figure imgf000043_0002
16.7 g of a compound obtainable according to process P3c) are stirred together with 5 ml of ethyl bromide and 10 g of potassium carbonate in 150 ml of dimethylf ormamide for 2 hours at room temperature. 300 ml of diethyl ether are added to the reaction mixture, which is then washed several times with water and saturated sodium chloride solution and the ether phase is concentrated to dryness by evaporation. Recrystallisation of the residue from diethyl ether/hexane yields the title product having a melting point of 76-81 °C. e) 1 -{4-[2-(4-Chlorophenyl)-2-methoxyimino-ethoxy]-phenyl}-propane-1 ,2-dione 1 -(O-ethyl- oxime) 2-oxime of the formula
Figure imgf000044_0001
14.5 g of a compound obtainable according to process P3d) are stirred together with 3.1 g of hydroxylammonium chloride in 50 ml of pyridine for a period of 2 hours at 70°C. The reaction mixture is concentrated and 200 ml of ethyl acetate are added; the mixture is washed several times with water and saturated sodium chloride solution and the organic phase is concentrated to dryness by evaporation. Recrystallisation of the residue from dichloro- methane/hexane yields the title product having a melting point of 136-137°C.
f) 2-[2-(2-{4-[2-(4-Chlorophenyl)-2-methoxyimino-ethoxy]-phenyl}-2-ethoxyimino-1-methyl- ethylideneaminooxymethyl)-phenyl]-3-methoxy-acrylic acid methyl ester 2.9 g of a compound obtainable according to process P3e) in 30 ml of dimethylformamide are combined with 0.34 g of sodium hydride under an argon atmosphere. After evolution of hydrogen has ceased, 2 g of 2-(bromomethyl)-α-(methoxymethylene)-phenylacetic acid methyl ester are added and the mixture is stirred for one hour at room temperature. The mixture is rendered acidic with acetic acid and 150 ml of ethyl acetate are added; the mixture is washed several times with water and saturated sodium chloride solution and dried over sodium sulfate; the solvent is evaporated off. Chromatography of the residue on silica gel using tert-butyl methyl ether/hexane (1 :9) yields the title compound in the form of a resin (compound 4-1.7).
Example P4: It is also possible to prepare the other compounds listed in Table 4 in a manner analogous to that described in Example P3. The figures given in the column "Phys. data" denote melting points in °C. Table 4-1 : Compounds of general formula
Figure imgf000045_0001
Compd. X AR7 Phys. data
4-1.1 CH OCH3 CH2CH3 4-F resin
4-1.2 N O-CH3 CH2CH3 4-F resin
4-1.3 N NH-CH3 CH2CH3 4-F 87-89
4-1.4 CH OCH3 CH3 4-F foam
4-1.5 N O-CH3 CH3 4-F resin
4-1.6 N NH-CH3 CH3 4-F 106-108
4-1.7 CH OCH3 CH2CH3 4-CI resin
4-1.8 N O-CH3 CH2CH3 4-CI resin
4-1.9 N NH-CH3 CH2CH3 4-CI 108-111
4-1.10 CH OCH3 CH3 4-CI resin
4-1.11 N O-CH3 CH3 4-CI resin
4-1.12 N NH-CH3 CH3 4-CI 104-107
4-1.13 CH OCH3 CH2CH3 4-CF3 oil
4-1.14 N O-CH3 CH2CH3 4-CF3 106-109
4-1.15 N NH-CH3 CH2CH3 4-CF3 116-118
4-1.16 CH OCH3 CH3 4-CF3 resin
4-1.17 N O-CH3 CH3 4-CF3 resin
4-1.18 N NH-CH3 CH3 4-CF3 126-129
4-1.19 CH OCH3 CH2CH3 H resin
4-1.20 N O-CH3 CH2CH3 H resin
4-1.21 N NH-CH3 CH2CH3 H 124-126
4-1.22 CH OCH3 CH3 H resin
4-1.23 N O-CH3 CH3 H resin Compd. X Y AR7 Rs Phys. data
4-1.24 N NH-CH3 CH3 H 116-119
4-1.25 CH OCH3 CH3 4-CH3 resin
4-1.26 N O-CH3 CH3 4-CH3 resin
4-1.27 N NH-CH3 CH3 4-CH3 92-96
4-1.28 CH OCH3 CH2CH3 4-CH3 resin
4-1.29 N O-CH3 CH2CH3 4-CH3 resin
4-1.30 N NH-CH3 CH2CH3 4-CH3 117-119
4-1.31 CH OCH3 CH2-CsCH 4-CH3 resin
4-1.32 N O-CH3 CH2-C≡CH 4-CH3 resin
4-1.33 N NH-CH3 CH2-OCH 4-CH3 103-105
Table 4-2: Compounds of formula
Figure imgf000046_0001
No. X Y Re AR7 AιRτ7 Phys. data
4-2.1 CH OCH3 CH3 C2H5 CH3 oil
4-2.2 N OCH3 CH3 C2Hs CH3 oil
4-2.3 N NHCH3 CH3 C2H5 CH3 121-123
4-2.4 CH OCH3 p-tolyl CH3 benzyl 123-125
4-2.5 N OCH3 p-tolyl CH3 benzyl resin
4-2.6 N NHCH3 p-tolyl CH3 benzyl 129-132
4-2.7 CH OCH3 CH3 C2H5 benzyl oil
4-2.8 N OCH3 CH3 C2H5 benzyl oil
4-2.9 N NHCH3 CH3 C2H5 benzyl resin
4-2.10 CH OCH3 CH3 CH3 benzyl oil
4-2.11 N OCH3 CH3 CH3 benzyl oil
4-2.12 N NHCH3 CH3 CH3 benzyl 83-85 4-2.13 CH OCH3 CH3 CH2C≡CH benzyl oil
4-2.14 N OCH3 CH3 CH2CsCH benzyl oil
4-2.15 N NHCH3 CH3 CH2CsCH benzyl resin
4-2.16 N OCH3 CH3 C2H5 4-CF3-benzyl oil
Example P5-1 : 2-ITf (1 -Methvl-2-(4-f(dimethyl-(4-f luorophenvh-silvllmethoxvlphenvlϊ- [ethoxyimino]ethylidene)amino]oxy]methyl]-α-(methoxyimino)-phenylacetic acid methyl ester and 2-[[[(1-methyl-2-(4-[{dimethyl-(4-fluorophenyl)-silyl}methoxy]phenyl)-[ethoxyimino]ethyl- idene)amino]oxy]methyl]-α-(methoxyimino)-phenylacetic acid methylamide a) Chloromethyl-dimethyl-(4-fluorophenyl)-silane
250 ml of n-butyl lithium (1.6M in hexane) are added to 39 ml of 4-bromo-fluoro-benzene in 400 ml of tetrahydrofuran within a period of 45 minutes with stirring at -70°C. The mixture is stirred for a further 30 minutes and then 53 ml of chloromethyl-dimethyl-chlorosilane dissolved in 50 ml of tetrahydrofuran are added dropwise. The mixture is stirred at -70°C for a further 30 minutes and the temperature of the reaction mixture is then allowed to rise to 0°C. The reaction mixture is poured onto 200 ml of ice, and 300 ml of diethyl ether are added; the mixture is washed with water and saturated sodium chloride solution and dried over sodium sulfate; the solvent is evaporated off in vacuo. Distillation of the residue at 97- 105°C (21 mbar) yields the title product.
b) 1-(4-[{Dimethyl-(4-fluorophenyl)-silyl}methoxy]phenyl)-propan-2-one
30 g of 1 -(4-hydroxyphenyl)-propan-2-one and 45.5 g of chloromethyl-dimethyl-(4-f luoro- phenyl)-silane in 400 ml of dimethyl sulfoxide are stirred with 42 g of potassium carbonate and 2 g of potassium iodide for 12 hours at 70°C. The reaction mixture is poured into 1.6 litres of ice water and 500 ml of diethyl ether are added; the ether phase is extracted by washing several times with water and saturated sodium chloride solution and dried over sodium sulfate; the solvent is evaporated off. Distillation at 150°C (0.01 mbar) yields the title product.
c) 1 -(4-[{Dimethyl-(4-f luorophenyl)-silyl}methoxy]phenyl)-propane-1 ,2-dione-1 -oxime
28 ml of a 30 % solution of sodium methanolate in methanol are added at room temperature to 31.6 g of 1-(4-[{dimethyl-(4-fluorophenyl)-silyl}methoxy]phenyl)-propan-2-one in 300 ml of methanol, and 27 ml of isopentyl nitrite are then added dropwise. The reaction mixture is stirred for a further hour and rendered neutral with acetic acid; the solvent is evaporated off in vacuo. 200 ml of ethyl acetate are added to the residue; the organic phase is washed with water and saturated sodium chloride solution and dried over sodium sulfate; the solvent is evaporated off in vacuo. Recrystallisation from diethyl ether/hexane yields the title product having a melting point of 115-117°C.
d) 1 -(4-[{Dimethyl-(4-f luorophenyl)-silyl}methoxy]phenyl)-propane-1 ,2-dione-1 -ethyloxime
13.8 g of 1 -(4-[{dimethyl-(4-f luorophenyl)-silyl}methoxy]phenyl)-propane-1 ,2-dione-1 -oxime, 4 ml of ethyl bromide and 9 g of potassium carbonate are stirred in 150 ml of dimethyl- formamide for 2 hours at room temperature. 200 ml of diethyl ether are added to the reaction mixture, which is then washed with water and saturated sodium chloride solution; the organic phase is dried and the solvent is evaporated off to yield the title product in the form of an oil.
e) 1 -(4-[{Dimethyl-(4-f luorophenyl)-silyl}methoxy]phenyl)-propane-1 ,2-dione-1 -ethyloxime-2- oxime
14.3 g of 1-(4-[{dimethyl-(4-fluorophenyl)-silyl}methoxy]phenyl)-propane-1,2-dione-1 -ethyloxime in 50 ml of pyridine are stirred with 3.5 g of hydroxylammonium chloride for 2 hours at 70°C. The reaction mixture is concentrated in vacuo and ethyl acetate is added to the residue; the organic phase is washed with water and saturated sodium chloride solution and dried over sodium sulfate; the solvent is evaporated off. Recrystallisation from hexane yields the title product having a melting point of 100-102°C.
^) 2-[[[(1-Methyl-2-(4-[{dimethyl-(4-fluorophenyl)-silyl}methoxy]phenyl)-[ethoxyimino]- ethyiidene)amino]oxy]methyl]-α-(methoxyimino)-phenylacetic acid methyl ester 3.9 g of 1 -(4-[{dimethyl-(4-f luorophenyl)-silyl}methoxy]phenyl)-propane-1 ,2-dione-1 -ethyl- oxime-2-oxime are added at room temperature to 0.31 g of sodium hydride in 60 ml of di- methylformamide. After evolution of hydrogen has ceased, 2.9 g of 2-(bromomethyl)-α- (methoxyimino)-phenylacetic acid methyl ester are added and stirring is carried out for 1 hour at room temperature. The mixture is rendered neutral with acetic acid and 100 ml of ethyl acetate are added; the mixture is washed with water and saturated sodium chloride solution and dried over sodium sulfate; the solvent is evaporated off. Chromatography on silica gel using tert-butyl methyl ether/hexane (1:3) yields the title product in the form of an oil (compound 5.22).
g) 2-[[[(1-Methyl-2-(4-[{dimethyl-(4-fluorophenyl)-silyl}methoxy]phenyl)-[ethoxyimino]- ethylidene)amino]oxy]methyl]-α-(methoxyimino)-phenylacetic acid methylamide 3 ml of a 8M solution of methylamine in ethanol are added to 2.9 g of 2-[[[(1 -methyl-2-(4- [{dimethyl-(4-fluorophenyl)-silyl}methoxy]phenyI)-[ethoxyimino]ethylidene)amino]oxy]- methyl]-α-(methoxyimino)-phenylacetic acid methyl ester in 30 ml of methanol and stirring is carried out for 2 days at room temperature. The reaction mixture is concentrated to dryness by evaporation. Recrystallisation of the residue from hexane yields the title compound having a melting point of 88-90°C (compound 5.23).
Example P5-2: It is also possible to prepare the other compounds listed in Table 5 in a manner analogous to that described in Example P5-1. The figures given in the column "Phys. data" denote melting points in °C.
Table 5: Compounds of general formula
Compd. X Y AR7 R5 Phys. data
5.1 CH OCH3 CH3 H oil
5.2 N OCH3 CH3 H oil
5.3 N NH-CH3 CH3 H 128-130
5.4 CH OCH3 CH2CH3 H oil
5.5 N OCH3 CH2CH3 H oil
5.6 N NH-CH3 CH2CH3 H oil
5.7 CH OCH3 CH2CH3 3-CF3 oil
5.8 N OCH3 CH2CH3 3-CF3 oil
5.9 CH OCH3 CH3 3-CF3 oil
5.10 N OCH3 CH3 3-CF3 oil
5.11 N NH-CH3 CH3 3-CF3 resin
5.12 CH OCH3 CH2CH3 4-CF3 resin
5.13 N OCH3 CH2CH3 4-CF3 85-87
5.14 N NH-CH3 CH2CH3 4-CF3 129-131
5.15 CH OCH3 CH2CH3 4-CI oil
Figure imgf000050_0001
Compd. X AR7 Phys. data
5.47 N NH-CH3 CH2CH3 2-OCF3
Examβle_P6J.: 2-[[[(1-Methyl-2-(4-{2-(3-methylphenyl)-ethanedione}-phenyl)- [methoxyimino]ethylidene)amino]oxy]methyl]-α-(methoxyimino)-phenylacetic acid methyla- mide
2.2 g of 2-[[[(1 -methyl-2-(4-(3-methylphenyl-ethynyl)-phenyl)-2-E-[ethoxyimino]ethylidene)- amino]oxy]methyl]-α-(methoxyimino)-phenylacetic acid methylamide in 12 ml of dimethyl sulfoxide are stirred with 0.7 g of iodine for a period of 6 hours at 150°C. After cooling, the reaction mixture is purified on silica gel using ether/hexane (3:1), yielding the title compound in the form of a resin (compound 6.3).
Example P6-2: It is also possible to prepare the other compounds listed in Table 6 in a manner analogous to that described in Example P6-1. The figures given in the column "Phys. data" denote melting points in °C.
Table 6: Compounds of general formula
Figure imgf000051_0001
Compd. X AR7 Phys. data
6.1 CH OCH3 CH3 2-CH3
6.2 N O-CH3 CH3 4-CH3
6.3 N NH-CH3 CH3 3-CH3 resin
6.4 CH OCH3 CH2CH3 2-CI
Figure imgf000051_0002
6.6 N NH-CH3 CH2CH3 3-CI
Figure imgf000051_0003
Compd. X AR7 Rs Phys. data
6.8 N O-CH3 CH2CH3 4-F
6.9 CH OCH3 CH3 3-F
6.10 N O-CH3 CH3 2-CF3
6.11 N NH-CH3 CH3 4-CF3
6.12 CH OCH3 CH2CH3 3-CF3
6.13 N O-CH3 CH2CH3 2-OCF3
6.14 N NH-CH3 CH2CH3 4-OCF3
6.15 CH OCH3 CH2CH3 3-OCF3
Example P7-1 : 2-[[[(1 -Methyl-2-(4-{3-(3-trif lu loromethylph
[methoxyimino]ethylidene)amino]oxy]methyl]-α-(methoxymethylene)-phenylacetic acid methyl ester
1.5 ml of 3-iodobenzotrifluoride and 0.1 g of bis(triphenylphosphine)palladium(ll) chloride are added to a solution of 2.2 g of 2-[[[(1-methyl-2-({4-propargyloxy}-phenyl)- [methoxyimino]ethylidene)amino]oxy]methyl]-α-(methoxymethylene)-phenylacetic acid methyl ester in 100 ml of triethylamine and 40 ml of tetrahydrofuran. The mixture is stirred for 3 hours at 60°C and filtered, and the filtrate is concentrated by evaporation. The residue is purified on silica gel using ethyl acetate/hexane (1 :2) to yield the title compound in the form of a resin (compound 7.10).
Example P7-2: It is also possible to prepare the other compounds listed in Table 7 in a manner analogous to that described in Example P7-1. The figures given in the column "Phys. data" denote melting points in °C.
Table 7: Compounds of general formula
Figure imgf000053_0001
Compd. X AR7 Phys. data
7.1 CH OCH3 CH3 2-CH3
7.2 N O-CH3 CH3 4-CH3
7.3 N NH-CH3 CH3 3-CH3
Figure imgf000053_0002
7.6 N NH-CH3 CH2CH3 3-CI
7.7 CH OCH3 CH2CH3 2-F
7.8 N O-CH3 CH2CH3 4-F
7.9 CH OCH3 CH3 3-F
7.10 CH O-CH3 CH3 3-CF3 resin
Figure imgf000053_0003
7.12 CH OCH3 CH2CH3 2-CF3
7.13 N O-CH3 CH2CH3 2-OCF3
7.14 N NH-CH3 CH2CH3 4-OCF3
7.15 CH OCH3 CH2CH3 3-OCF3
Example P8-1 : 2-[[[(1-Meth yl-2-(4-{3-(3-triflι loromethylph
[methoxyimino]ethylidene)amino]oxy]methyl]-α-(methoxymethylene)-phenylacetic acid methyl ester
100 mg of palladium on carbon (5 % Pd) are added to 1.8 g of 2-[[[(1 -methyl-2-(4-{3-(3- trifluoromethylphenyl)-propyn-2-yl-oxy}-phenyl)-[methoxyimino]ethylidene)amino]oxy]- methyl]-α-(methoxymethylene)-phenylacetic acid methyl ester in 30 ml of tetrahydrofuran. Hydrogen is introduced at normal pressure until one equivalent has been used. The reac- tion mixture is then filtered and the filtrate is concentrated to dryness by evaporation. The residue is purified on silica gel using ethyl acetate/hexane (1 :2) to yield the title compound in the form of an oil (compound 8.10).
Example P8-2: It is also possible to prepare the other compounds listed in Table 8 in a manner analogous to that described in Example P8-1.
Table 8: Compounds of general formula
Figure imgf000054_0001
Compd. X AR7 Rs Phys. data
8.1 CH OCH3 CH3 2-CH3
Figure imgf000054_0002
8.4 CH OCH3 CH2CH3 2-CI
8.5 N O-CH3 CH2CH3 4-CI
8.6 N NH-CH3 CH2CH3 3-CI
Figure imgf000054_0003
8.9 CH OCH3 CH3 3-F
8.10 CH O-CH3 CH3 3-CF3 oil
Figure imgf000054_0004
8.12 CH OCH3 CH2CH3 2-CF3
8.13 N O-CH3 CH2CH3 2-OCF3
8.14 N NH-CH3 CH2CH3 4-COF3
8.15 CH OCH3 CH2CH3 3-OCF3 Example P9-1 : Compound of the formula
Figure imgf000055_0001
1.1 g of phenyi isocyanate, 0.45 ml of nitroethane and 0.5 ml of triethylamine are added to 2.1 g of 2-[[[(1-methyl-2-(4-ethynyl-phenyl)-[methoxyimino]ethylidene)amino]oxy]methyl]- α-(methoxymethylene)-phenylacetic acid methyl ester in 40 ml of toluene. Stirring is carried out for a period of 5 hours at 80°C, the reaction mixture is filtered and the filtrate is concentrated by evaporation. Purification on silica gel using ethyl acetate/hexane 1 :2 yields the title product having a melting point of 116-118°C (compound 9-1.1).
Example P9-2: Preparation of the compound of formula
Figure imgf000055_0002
1.8 g of the compound of formula
Figure imgf000055_0003
and 2 ml of triethylamine are added to 1.2 g of 2-[[[(1-methyl-2-(4-ethynyl-phenyl)-[methoxy- imino]ethylidene)amino]oxy]methyl]-α-(methoxyimino)-phenylacetic acid methyl ester in toluene. Stirring is carried out for 4 hours at 65°C, the reaction mixture is filtered and the filtrate is concentrated by evaporation. Purification on silica gel using toluene/diisopropyl ether/hexane (1 :1 :2) yields the title compound having a melting point of 127-129°C (compound 9-2.2).
Example P9-3: It is also possible to prepare the other compounds listed in Tables 9-1 and 9-2 in a manner analogous to that described in Examples P9-1 and P9-2. The figures given in the column "Phys. data" denote melting points in °C.
Table 9-1 : Compounds of general formula
Figure imgf000056_0001
Compd. X AR7 118 Phys. data
9-1.1 CH OCH3 CH3 CH3 116-118 °C
9-1.2 N O-CH3 CH3 CH3
9-1.3 N NH-CH3 CH3 CH3
9-1.4 CH OCH3 CH2CH3 CH3
9-1.5 N O-CH3 CH2CH3 CH3
9-1.6 N NH-CH3 CH2CH3 CH3
9-1.7 CH OCH3 CH2CH3 CH2CH3
9-1.8 N O-CH3 CH2CH3 CH2CH3
9-1.9 CH OCH3 CH3 CH2CH3
9-1.10 CH O-CH3 CH3 CH2CH3
9-1.11 N NH-CH3 CH3 -dHs
Figure imgf000056_0002
9-1.14 N O-CH3 CH2CH3 -CβHs
9-1.15 N NH-CH3 CH2CH3 -CβHβ
9-1.16 CH OCH3 CH2CH3 -CβHs
9-1.17 N NH-CH3 CH3 -C8H -3-CF3
Figure imgf000057_0001
Compd. X AR7 Phys. data
9-2.16. CH OCH3 CH2CH3 4-OCF3 9-2.17. N O-CH3 CH2CH3 3-OCF3 9-2.18. N NH-CH3 CH2CH3 2-OCF3
Example P9-4: Preparation of 6-chloro-3-(4'-(1-ethoxyimino-2-hydroxyimino)propyl)benz- isoxazole of the formula
Figure imgf000058_0001
a) 4-Bromo-2'.4'-dichlorobenzophenone oxime:
Figure imgf000058_0002
Hydroxylammonium chloride (6.4 g) and pyridine (7.2 g) are added at room temperature to a solution of 4-bromo-2',4'-dichlorobenzophenone (15.1 g) in ethanol (75 ml). After being boiled for 10 hours under reflux, the reaction mixture is concentrated by evaporation using a rotary evaporator, and water and ethyl acetate are added to the residue. After washing the organic phase and evaporating the solution, a residue is obtained which is dissolved in hexane at 30°C and left to stand at 5°C. The solid that forms is filtered off with suction and dried in air, thereby yielding the title compound having a melting point of 125-126°C.
b) 3-(4'-Bromophenyl)-6-chlorobenzisoxazole:
Figure imgf000058_0003
20 ml of dimethylformamide are added to 10.4 g of the compound obtainable according to a). At 30-35°C, KOH (5.63 g) is added in portions. The mixture is then stirred at 45°C for 1 hour and then a further 0.94 g portion of KOH is added at 30°C and the mixture is stirred for a further 1 hour at 45°C to complete the reaction. Methanol (30 ml) and, after 10 minutes' stirring, water (120 ml) are added to the reaction mixture. After cooling to -5°C, the solid formed is filtered off and dried in air to yield the title compound having a melting point of 126-127°C.
c) 4-(6'-Chlorobenzoxazol-3'-vhbenzaldehvde:
Figure imgf000059_0001
A solution of 3-(4'-bromophenyl)-6-chlorobenzoxazole (43.2 g) in tetrahydrofuran (470 ml) is cooled to -70°C under argon. Within a period of one hour, an approx. 1.6M n-butyl lithium solution in hexane (100 ml) is added dropwise. After 1 hour at -70°C, the reaction mixture is brought to -45°C and a solution of N-formylpiperidine (17.5 g) in tetrahydrofuran (145 ml) is added within a period of 30 minutes. The temperature is then allowed to rise to room temperature and the mixture is stirred for two hours. 2N hydrochloric acid (280 ml) is added and the mixture is stirred for a further 2 hours at room temperature. The reaction mixture is taken up in methylene chloride and washed with saturated NaHCO3 solution and saturated NaCl solution. After evaporating off the solvent, the residue is stirred together with 200 ml of diethyl ether. Filtration yields the title compound having a melting point of 159-160°C.
d) 6-Chloro-3-(4'-(2-nitropropenyl)phenyl)benzisoxazole
Ammonium acetate (12.0 g) is added to 4-(6'-chlorobenzoxazol-3'-yl)benzaldehyde (35.2 g) and nitroethane (160 ml). The mixture is then stirred for 4 hours under reflux. The reaction mixture is cooled to approx. 60°C and at that temperature concentrated by evaporation in vacuo. The residue is taken up in ethyl acetate and washed with brine. Drying over Na2SO4 and evaporating off solvent at 50°C yields a residue, which is stirred together with tert-butyl methyl ether. The solid product obtained is filtered off with suction and dried in air, yielding the title compound having a melting point of 160-162°C. e) 6-Chloro-3-(4'-(2-oxopropyl)phenvπbenzisoxazole
Alcohol (30 ml) and water (29 ml) are added to 6-chloro-3-(4'-(2-nitropropenyl)phenyl)benz- isoxazole (18.2 g), iron granules (11.3 g) and iron(lll) chloride (0.18 g) and the mixture is heated to 70°C with stirring. Once the temperature has reached 70°C, 20 ml of concentrated hydrochloric acid are added dropwise in such a manner that the reaction temperature can be maintained at 70°C. After the addition is complete, the batch is stirred at 70°C for 90 minutes, a further 10 ml of concentrated hydrochloric acid are added dropwise and the stirring is continued for a further 2 hours. The reaction mixture is cooled, filtered over silica gel and diluted with ethyl acetate; the organic phase is extracted by shaking with water and saturated NaCl solution. After drying over MgSO4 and evaporating off the solvent, a sticky residue is obtained, which is purified by means of column chromatography (ethyl acetate/hexane 1 :5), yielding the title compound having a melting point of 109-110°C.
f) 6-Chloro-3-(4'-(1 -hvdroxyimino-2-oxo)propyl)benzisoxazole
Isopentyl nitrite (3.0 g) is slowly added dropwise at 20°C to 7.2 g of 6-chloro-3-(4'-(2-oxo- propyl)phenyl)benzisoxazole in methanol (37 ml). After the addition of 30 % sodium methanolate (5.7 g), stirring is carried out overnight at room temperature. The reaction mixture is concentrated by evaporation at 50°C; the residue is dissolved in water and rendered acidic with 10 % hydrochloric acid at 10°C. Ethyl acetate is added, the water phase separated and the organic phase washed with water. Drying over MgSO4 and concentration by evaporation yield a solid, which is stirred together with hexane, filtered off with suction and dried in air to yield the title compound having a melting point of 224-226°C.
g) 6-Chloro-3-(4'-(1 -ethoxyimino-2-oxo)propyl)benzisoxazole
Ethyl iodide (5.45 g) is added to 6-chloro-3-(4'-(1-hydroxyimino-2-oxo)propyl)benzisoxazole (7.01 g), acetonitrile (44 ml) and potassium carbonate (4.3 g). The batch is heated for 3 hours under reflux, cooled to room temperature and filtered, the filter being rinsed with acetonitrile. The filtrate is concentrated by evaporation using a rotary evaporator; the residue is taken up in ethyl acetate and washed with water and brine. Drying of the organic phase over Na2SO and concentration by evaporation yield the title compound having a melting point of 106-107°C. h^ 6-Chloro-3-(4'-(1-ethoxyimino-2-hvdroxyimino)propyl)benzisoxazole Pyridine (3.6 g) is added to 6-chloro-3-(4'-(1-ethoxyimino-2-oxo)propyl)benzisoxazole (7.20 g), ethanol (37 ml) and hydroxylammonium chloride (3.2 g). The batch is boiled under reflux for 2 hours. The reaction mixture is evaporated; the residue is washed with water, taken up in ethyl acetate and then washed with water. After drying of the organic phase over Mg2SO and concentration using a rotary evaporator, the residue is stirred when cold together with a little diethyl ether. The resulting solid product is filtered off with suction and dried in air to yield the title compound having a melting point of 218-219°C.
Starting from the compounds according to Examples P9-4/g) and P9-4/h), compounds 9-3.1 to 9-3.3 can be prepared analogously to the process variants a1), a2) and b).
Example P9-5: It is also possible to prepare the intermediates required for the other compounds listed in Table 9-3 in a manner analogous to that described in Example P9-4. The figures given in the column "Phys. data" denote melting points in °C.
Table 9-3: Compounds of the formula
Figure imgf000061_0001
Compd. X AR7 Phys. data
9-3.1 CH OCH3 CH2CH3 6-CI 105-110
9-3.2 N O-CH3 CH2CH3 6-CI 128-130
9-3.3 N NH-CH3 CH2CH3 6-CI 124-126
9-3.4 CH OCH3 CH2CH3 6-CI
9-3.5 N O-CH3 CH2CH3 6-CI
9-3.6 N NH-CH3 CH2CH3 6-CI Compd. X AR7 Phys. data
9-3.7 CH OCH3 CH2CH3 5-CI
9-3.8 N O-CH3 CH2CH3 5-CI
9-3.9 N NH-CH3 CH2CH3 5-CI
9-3.10 CH OCH3 CH2CH3 5,6-CI2
9-3.11 N O-CH3 CH2CH3 5,6-CI2
9-3.12 N NH-CH3 CH2CH3 5,6-CI2
9-3.13 CH OCH3 CH2CH3 6-CF3
9-3.14 N O-CH3 CH2CH3 6-CF3
9-3.15 N NH-CH3 CH2CH3 6-CF3
9-3.16 CH OCH3 CH2CH3 6-OCF3
9-3.17 N O-CH3 CH2CH3 6-OCF3
9-3.18 N NH-CH3 CH2CH3 6-OCF3
Example P10-1 : : Preparation of
Figure imgf000062_0001
0.95 g of 2-{2-[2-(4-bromophenyl)-2-methoxyimino-1 -methyl-ethylideneaminooxymethyl]- phenyl}-3-methoxy-acrylic acid methyl ester, 0.4 g of triethylamine, 0.25 g of tetrakis- triphenylphosphine-palladium(O), 3 ml of toluene and 0.28 g of diethyl phosphite are stirred under argon for 2 hours at 90°C. The reaction mixture is taken up in ethyl acetate, washed with water, dried and concentrated. Chromatography of the crude product on silica gel using ethyl acetate/hexane (1 :1) yields 0.93 g of product having a melting point of 125-126°C (compound 10-1.16).
Example P11: It is also possible to prepare the other compounds listed in Tables 10 and 11 in a manner analogous to that described in Example P10-1. Table B: Compounds of general formula
Figure imgf000063_0001
No. X Y R11 R-I2 (W)w
Figure imgf000063_0002
B.4 CH OCH3 4-CI-C6H5 4-CI-C6H5 O
B.5 N OCH3 4-CI-C6H5 3-CI-C6H5 O
B.6 N NHCH3 4-CI-C6H5 2-CI-C6H5 O
B.7 CH OCH3 2,4-CI2-C6H5 2,4-CI2-C6H5 O
B.8 N OCH3 2,4-CI2-C6H5 3,4-CI2-C6H5 O
B.9 N NHCH3 2,4-CI2-C6H5 2,5-Ck-CβHs O
B.10 CH OCH3 3-CF3-CgHs 3-CF3-C6H5 O
B.ll N OCH3 4-CF3-C6H5 4-CF3-C6H5 O
B.12 CH OCH3 C6H5O C6H5O O
B.13 N OCH3 C6H5O C6H5O O
B.14 CH OCH3 3,5-CI2-C6H5O 3,5-CI2-C6H5O O
B.15 CH OCH3 CH3O CH3O O
B.16 CH OCH3 CH3CH2O CH3CH2O O
B.17 N NHCH3 CH3O CH3O O
B.18 CH OCH3 4-CI-C6H5O 4-CI-C6H5O O
B.19 N NHCH3 3,5-CI2-C6H5O 3,5-CI2-C6H5O O
B.20 CH OCH3 4-CI-C6H5S 4-CI-C6H5S O
B.21 N NHCH3 4-Br-C6H5S 4-Br-C6H5S O
B.22 N OCH3 CH3CH S CH3CH S S
B.23 CH OCH3 4-CI-C6H5S 4-CI-C6H5S S
B.24 N OCH3 4-CI-C6H5S 3,5-CI2-C6H5O s
Figure imgf000064_0001
B.25 N NHCH3 CH3CH S 4-CI-C6H5S S
B.26 CH OCH3 CH3CH2O 4-CI-C6H5S S
B.27 N OCH3 CH3CH2O 4-CI-C6H5S S
B.28 N OCH3 4-CF3-C6H5 CH3CH2S O
B.29 N NHCH3 4-CF3-C6H5 CH3CH2S O
B.30 CH OCH3 4-CF3-C6H5 CH3S S
B.31 N NHCH3 4-CF3-C6H5 CH3S S
B.32 CH OCH3 4-Br-C6H5S CH3CH2O O
B.33 N OCH3 4-CI-C6H5S 3,5-CI2-C6H5O O
B.34 CH OCH3 CH3CH S CH3CH2S w=0
B.35 N OCH3 4-CI-C6H5S 4-CI-C6H5S w=0
B.36 CH OCH3 4-CI-C6H5S 3,5-CI2-C6H5O w=0
B.37 N OCH3 4-CI-C6H5S 3,5-CI2-C6H5O w=0
B.38 N OCH3 CH3CH2O 4-CI-C6H5S w=0
B.39 CH OCH3 C6H5O C6H5O w=0
B.40 N NHCH3 C6H5O C6H5O w=0
B.41 CH OCH3 4-CF3-C6H5 CH3S w=0
B.42 N NHCH3 4-CF3-C6H5 CH3S w=0
Table 10-1 : Compounds of general formula (1.10) wherein AR7 is CH3 and the combination of substituents X, Y, (W)w, Rn and R.2 for each compound corresponds to a line of Table B.
Compound of formula 1.10 wherein A-R7 is methyl and the substituents X, Y, (W)w, Rn and R12 correspond to line B.1 of Table B; m.p.: 103-104°C (compound 10-1.1).
Compound of formula 1.10 wherein A-R7 is methyl and the substituents X, Y, (W)w, R and Rι2 correspond to line B.12 of Table B; m.p.: 95-96°C (compound 10-1.12).
Table 10-2: Compounds of formula (1.10) wherein AR7 is CH2CH3 and the combination of substituents X, Y, (W)w, Rn and Rι2 for each compound corresponds to a line of Table B.
Table 10-3: Compounds of formula (1.10) wherein AR7 is CH2CH=CH2 and the combination of substituents X, Y, (W)w, Rn and R12 for each compound corresponds to a line of Table B. Table 10-4: Compounds of formula (1.10) wherein AR7 is CH2C≡CH and the combination of substituents X, Y, (W)w, Rn and R-|2 for each compound corresponds to a line of Table B.
Table 10-5: Compounds of formula (1.10) wherein AR7 is CH2CH2CH3 and the combination of substituents X, Y, (W)w, Rn and R12 for each compound corresponds to a line of Table B.
Table 10-6: Compounds of formula (1.10) wherein AR7 is CH(CH3)2 and the combination of substituents X, Y, (W)w, Rn and R12 for each compound corresponds to a line of Table B.
Table 10-7: Compounds of formula (1.10) wherein AR7 is CH2CH2CH2CH3 and the combination of substituents X, Y, (W)w, Rn and R12 for each compound corresponds to a line of Table B.
Table 10-8: Compounds of formula (1.10) wherein AR7 is CH(CH3)(CH2CH3) and the combination of substituents X, Y, (W)w, Rn and R12 for each compound corresponds to a line of Table B.
Table 10-9: Compounds of formula (1.10) wherein AR7 is C(CH3)3and the combination of substituents X, Y, (W)w, Rn and R12 for each compound corresponds to a line of Table B.
Table 10-10: Compounds of formula (1.10) wherein AR7 is CH2CF3and the combination of substituents X, Y, (W)w, R and R12 for each compound corresponds to a line of Table B.
Table 10-11 : Compounds of formula (1.10) wherein AR7 is CH2CH=C(CH3)2 and the combination of substituents X, Y, (W)w, Rn and R12 for each compound corresponds to a line of Table B.
Table 10-12: Compounds of formula (1.10) wherein AR7 is CH2CH=CCI2 and the combination of substituents X, Y, (W)w, Rn and R-|2 for each compound corresponds to a line of Table B.
Table 10-13: Compounds of formula (1.10) wherein AR7 is CH2Si(CH3)3 and the combination of substituents X, Y, (W)w, Rn and R12 for each compound corresponds to a line of Table B.
Table 10-14: Compounds of formula (1.10) wherein AR7 is CH2-c.propyl-2,2-CI2 and the combination of substituents X, Y, (W)w, Rn and R12 for each compound corresponds to a line of Table B.
Table 10-15: Compounds of formula (1.10) wherein AR7 is CH2CN and the combination of substituents X, Y, (W)WI Rn and R12 for each compound corresponds to a line of Table B. Table 10-16: Compounds of formula (1.10) wherein AR7 is CH2COOCH3and the combination of substituents X, Y, (W)w, Rn and R-|2 for each compound corresponds to a line of Table B.
Table 10-17: Compounds of formula (1.10) wherein AR7 is CH2COO-iso-C3H7 and the combination of substituents X, Y, (W)w, Rn and R12 for each compound corresponds to a line of Table B.
Table 10-18: Compounds of formula (1.10) wherein AR7 is C(=O)OC2H5 and the combination of substituents X, Y, (W)w, Rn and Rι2 for each compound corresponds to a line of Table B.
Table 10-19: Compounds of formula (1.10) wherein AR7 is C(=O)NHCH3 and the combination of substituents X, Y, (W)w, Rn and Rι2 for each compound corresponds to a line of Table B.
Table 10-20: Compounds of formula (1.10) wherein AR7 is C(=O)C(=O)OC2H5 and the combination of substituents X, Y, (W)w, Rn and R-|2 for each compound corresponds to a line of Table B.
Table 10-21: Compounds of formula (1.10) wherein AR is CH2C6H5and the combination of substituents X, Y, (W)w, Rn and R12 for each compound corresponds to a line of Table B.
Table 10-22: Compounds of formula (1.10) wherein AR7 is CH2C6H4-2-F and the combination of substituents X, Y and (W)w, Rn and R12 for each compound corresponds to a line of Table B.
Table 10-23: Compounds of formula (1.10) wherein AR7 is CH2C6H4-3-CI and the combination of substituents X, Y, (W)w, Rn and R 2 for each compound corresponds to a line of Table B.
Table 10-24: Compounds of formula (1.10) wherein AR7 is CH2C6H4-4-Br and the combination of substituents X, Y, (W)w, Rn and R12 for each compound corresponds to a line of Table B.
Table 10-25: Compounds of formula (1.10) wherein AR7 is CH2C6H4-3-CF3 and the combination of substituents X, Y, (W)w, Rn and Rι2 for each compound corresponds to a line of Table B.
Table 10-26: Compounds of formula (1.10) wherein AR is CH2C6H4-4-CF3and the combination of substituents X, Y, (W)w, Rn and Rι2 for each compound corresponds to a line of Table B. Table 11-1: Compounds of formula
Figure imgf000067_0001
wherein AR7 is CH3 and the combination of substituents X, Y, (W)w, Rn and R12 for each compound corresponds to a line of Table B.
Table 11 -2: Compounds of formula (1.11) wherein AR7 is CH2CH3 and the combination of substituents X, Y, (W)w, Rn and R-|2 for each compound corresponds to a line of Table B.
Table 11 -3: Compounds of formula (1.11) wherein AR7 is CH2CH=CH2 and the combination of substituents X, Y, (W)w, Rn and Rι2 for each compound corresponds to a line of Table B.
Table 11-4: Compounds of formula (1.11) wherein AR7 is CH2C=CH and the combination of substituents X, Y, (W)w, Rn and R12 for each compound corresponds to a line of Table B.
Table 11-5: Compounds of formula (1.11 ) wherein AR is CH2CH2CH3 and the combination of substituents X, Y, (W)w, Rn and Rι2 for each compound corresponds to a line of Table B.
Table 11 -6: Compounds of formula (1.11) wherein AR7 is CH(CH3)2 and the combination of substituents X, Y, (W)w, Rn and R-ι2 for each compound corresponds to a line of Table B.
Table 11 -7: Compounds of formula (1.11) wherein AR7 is CH2CH2CH2CH3 and the combination of substituents X, Y, (W)w, Rn and R-|2 for each compound corresponds to a line of Table B.
Table 11 -8: Compounds of formula (1.11) wherein AR7 is CH(CH3)(CH2CH3) and the combination of substituents X, Y, (W)w, Rn and R-|2 for each compound corresponds to a line of Table B.
Table 11-9: Compounds of formula (1.11) wherein AR7 is C(CH3)3and the combination of substituents X, Y, (W)w, Rn and R-|2 for each compound corresponds to a line of Table B.
Table 11-10: Compounds of formula (1.11) wherein AR7 is CH2CF3and the combination of substituents X, Y, (W)w, Rn and R12 for each compound corresponds to a line of Table B. Table 11-11 : Compounds of formula (1.11 ) wherein AR7 is CH2CH=C(CH3)2 and the combination of substituents X, Y, (W)w, Rn and Rι2 for each compound corresponds to a line of Table B.
Table 11-12: Compounds of formula (1.11) wherein AR7 is CH2CH=CCI2 and the combination of substituents X, Y, (W)w, Rn and R12 for each compound corresponds to a line of Table B.
Table 11-13: Compounds of formula (1.11 ) wherein AR7 is CH2Si(CH3)3 and the combination of substituents X, Y, (W)w, Rn and Rι2 for each compound corresponds to a line of Table B.
Table 11-14: Compounds of formula (1.11) wherein AR7 is CH2-c.propyl-2,2-CI2 and the combination of substituents X, Y, (W)w, Rn and R-|2 for each compound corresponds to a line of Table B.
Table 11-15: Compounds of formula (1.11) wherein AR7 is CH2CN and the combination of substituents X, Y, (W)w, Rn and R-|2 for each compound corresponds to a line of Table B.
Table 11-16: Compounds of formula (1.11) wherein AR7 is CH2COOCH3and the combination of substituents X, Y, (W)w, Rn and R-ι2 for each compound corresponds to a line of Table B.
Table 11-17: Compounds of formula (1.11) wherein AR7 is CH2COO-iso-C3H7 and the combination of substituents X, Y, (W)w, Rn and Rι2 for each compound corresponds to a line of Table B.
Table 11-18: Compounds of formula (1.11) wherein AR7 is C(=O)OC2H5 and the combination of substituents X, Y, (W)w, Rn and Rι2 for each compound corresponds to a line of Table B.
Table 11-19: Compounds of formula (1.11) wherein AR is C(=O)NHCH3and the combination of substituents X, Y, (W)w, Rn and R12 for each compound corresponds to a line of Table B.
Table 11-20: Compounds of formula (1.11) wherein AR7 is C(=O)C(=O)OC2H5 and the combination of substituents X, Y, (W)w, Rn and R12 for each compound corresponds to a line of Table B.
Table 11-21: Compounds of formula (1.11) wherein AR7 is CH2C6H5 and the combination of substituents X, Y, (W)w, Rn and R12 for each compound corresponds to a line of Table B. Table 11-22: Compounds of formula (1.11 ) wherein AR7 is CH2C6H4-2-F and the combination of substituents X, Y and (W)w, Rn and R12 for each compound corresponds to a line of Table B.
Table 11 -23: Compounds of formula (1.11) wherein AR7 is CH2C6H4-4-Br and the combination of substituents X, Y, (W)w, Rn and R12 for each compound corresponds to a line of Table B.
Table 11 -24: Compounds of formula (1.11) wherein AR7 is CH2C6H4-3-CF3 and the combination of substituents X, Y, (W)w, Rn and Rι2 for each compound corresponds to a line of Table B.
Table 11-25: Compounds of formula (1.11) wherein AR7 is CH2C6H4-4-CF3 and the combination of substituents X, Y, (W)w, R and R12 for each compound corresponds to a line of Table B.
Example P12-1 : Preparation of the compounds of the formula
Figure imgf000069_0001
2.4 g of 2-{2-[2-(4-bromophenyl)-2-methoxyimino-1-methyl-ethylideneaminooxymethyl]- phenyl}-3-methoxy-acrylic acid methyl ester, 0.7 g of sodium ter -butanolate, 0.25 g of tris(dibenzylacetone)dipalladium(0), 110 mg of 1 ,1-bis(diphenylphosphine)ferrocene, 40 ml of toluene and 0.77 g of 4-chloroaniline are stirred under an argon atmosphere for 4 hours at 70°C. The reaction mixture is taken up in diethyl ether, washed with brine, dried and concentrated. Chromatography of the crude product on silica gel using ethyl acetate/hexane (1 :19) yields 0.8 g of the title product having a melting point of 82-83°C (compound 12-1.3). Examole P12-2: Preparation of the compound of formula
Figure imgf000070_0001
0.55 g of sodium hydride (55 %) is added in portions to 3.5 g of 3-(4-(3-fluoromethyl- phenylamino)phenyl-2-hydroximino-3-methoximinopropane in 40 ml of dimethylformamide under an argon atmosphere in an ice bath. After one hour, 3.4 g of 2-(α-bromo-o-tolyl)-2- methoxyimino-acetic acid methyl ester are added and stirring is carried out for a further 20 hours at room temperature. 0.6 g of acetic acid is then added and the reaction mixture is concentrated. The residue is taken up in ethyl acetate; the mixture is washed with water, dried and concentrated. Chromatography of the residue on silica gel using ethyl acetate/- hexane (1 :9) yields 3.6 g of 2-{2-[2-(4-(3-fluoromethylphenylamino)-phenyl)-2-ethoxyimino- 1 -methyl-ethylideneaminooxymethyl]-phenyl}-3-methoxy-acrylic acid methyl ester having a melting point of 119-120°C (compound 12-1.69).
Example P12-3: Preparation of the compound of the formula
Figure imgf000070_0002
0.2 g of 2-{2-[2-(4-(4-chlorophenylamino)-phenyl)-2-methoxyimino-1 -methyl-ethylidene- aminooxymethyl]-phenyl}-3-methoxy-acryiic acid methyl ester and 7 ml of a 1 M solution of formylacetic acid anhydride in diethyl ether are stirred under argon for 12 hours at 25°C. The reaction mixture is concentrated. Chromatography of the residue on silica gel using ethyl acetate/hexane (1 :5) yields 0.03 g of the title product having a melting point of 145- 146°C (compound 12-1.64). Example P12-4: It is also possible to prepare the other compounds listed in Tables 12 and 13 in a manner analogous to that described in Examples P12-1 to P12-3.
Table C: Compounds of general formulae
Figure imgf000071_0001
Figure imgf000071_0002
No. X Y (R5)s (RδsJn R13
C.l N OCH3 4-CI n=0 H
C.2 N NHCH3 3-CI n=0 H
C.3 CH OCH3 4-CI n=0 H
C.4 CH OCH3 4-CI n=0 CH3
C.5 N OCH3 4-CI n=0 CH3
C.6 N NHCH3 3-CI n=0 CH3
C.7 CH OCH3 2-CI n=0 CH2CH3
C.8 N OCH3 4-CI n=0 CH22CH3
C.9 N NHCH3 4-CI n=0 CH2CH3
CIO N NHCH3 4-CI n=0 C(O)H
C.ll CH OCH3 4-CI n=0 C(O)CH3 No. X Y (R5)s (R55)n Rl3
C.12 CH OCH3 2.4-C.2 n=0 H
C.13 CH OCH3 2.4-C.2 n=0 CH3
C.14 N OCH3 2t4-CI2 n=0 CH3
C.15 CH OCH3 2,4-CI2 n=0 CH2CH3
C.16 N OCH3 2.4-C.2 n=0 C(O)H
C.17 CH OCH3 2,4-CI2 n=0 C(O)CH3
C.18 N NHCH3 2.4-CI2 n=0 C(O)CH3
C.19 N OCH3 4-CF3 n=0 H
C.20 N NHCH3 4-CF3 n=0 H
C.21 CH OCH3 4-CF3 n=0 CH3
C.22 N NHCH3 3-CF3 n=0 CH3
C.23 CH OCH3 4-CF3 n=0 CH2CH3
C.24 N NHCH3 4-CF3 n=0 CH2CH3
C.25 CH OCH3 3-CF3 n=0 C(O)H
C.26 N NHCH3 4-CF3 n=0 C(O)H
C.27 N NHCH3 4-CF3 n=0 C(O)CH3
Figure imgf000072_0001
C.29 N NHCH3 3-CF3 n=0 H
C.30 CH OCH3 3-CF3 n=0 CH2CH3
C.31 N NHCH3 3-CF3 n=0 CH2CH3
C.32 N OCH3 3-CF3 n=0 C(O)H
C.33 N NHCH3 3-CF3 n=0 C(O)CH3
C.34 CH OCH3 3-CI n=0 H
C.35 CH OCH3 4-NHCH3 n=0 H
C.36 CH OCH3 3-OCH3 n=0 CH3
C.37 CH OCH3 3,5-CI2 n=0 CH3
C.38 CH OCH3 3,4-CI2 n=0 /so-CH2CH2CH3
C.39 CH OCH3 4-Br n=0 CH2CH3
C.40 CH OCH3 4-C6H5 n=0 π-CH2CH2CH3
C.41 CH OCH3 2-CN n=0 CH2OCH3
C.42 CH OCH3 3-NO2 n=0 C(O)H
C.43 CH OCH3 3-C(O)CH3 n=0 C(O)C(O)CH3 No. X Y (R5)s (RssJn Rl3
C.44 CH OCH3 4-NHC(O)CH3 n=0 C(O)C(O)OCH3
C.45 CH OCH3 4-SFs n=0 C(O)CH2CH3
C.46 CH OCH3 3-OCF3 n=0 C(S)CH3
C.47 CH OCH3 4-CI n=0 C(S)SCH3
C.48 CH OCH3 3-CI 3-CI H
C.49 CH OCH3 4-CH3 2-Br H
C.50 CH OCH3 4-NHCH3 2-CN H
C.51 CH OCH3 3-OCH3 3-CI CH3
C.52 CH OCH3 3,5-CI2 2-F CH3
C.53 CH OCH3 3,4-CI2 2-OCH3 /so-CH2CH2CH3
C.54 CH OCH3 4-Br 3,5-CI2 CH2CH3
C.55 CH OCH3 4-C6H5 3-CH3 t7-CH2CH2CH3
C.56 CH OCH3 2-CN 3,5-F2 CH2OCH3
C.57 CH OCH3 3-NO2 2,3-F2 C(O)H
C.58 CH OCH3 3-C(O)CH3 3-NHCH3 C(O)C(O)CH3
C.59 CH OCH3 4-NHC(O)CH3 3-CI C(O)C(O)OCH3
C.60 CH OCH3 4-SFs 2-CI C(O)CH2CH3
C.61 CH OCH3 3-OCF3 3-SCH3 C(S)CH3
C.62 CH OCH3 4-CI 2,6-CI2 C(S)SCH3
Figure imgf000073_0001
C.64 CH OCH3 4-CI n = 0 C(O)H
C.65 CH OCH3 4-CF3 n = 0 C(O)H
Figure imgf000073_0002
C.67 CH OCH3 4-OCF3 n = 0 C(O)H
C.68 CH OCH3 2,4-F2 n = 0 H
Figure imgf000073_0003
C.71 N OCH3 4-OCF3 n = 0 C(O)H
C.72 N OCH3 2,4-F2 n = 0 H
C.73 N NCH3 4-OCF3 n = 0 H
C.74 N NCH3 2,4-F2 n = 0 H Table 12-1 : Compounds of formula 1.12 wherein AR7 is CH3 and the combination of substituents X, Y, (R5)s, (Rs5)n and R-ι3 for each compound corresponds to a line of Table C.
Compound of formula (1.12) wherein A-R7 is methyl and the substituents X, Y, (R5)s, ( ssJn and R13 correspond to line C.4 of Table C: m.p.: 126-127°C (compound 12-1.4).
Compound of formula (1.12) wherein A-R7 is methyl and the substituents X, Y, (R5)s, (Rs5)n and R13 correspond to line C.12 of Table C: m.p.: 132-133°C (compound 12-1.12).
Compound of formula (1.12) wherein A-R7 is methyl and the substituents X, Y, (R5)s, (R55)n and R.3 correspond to line C.24 of Table C: amorphous (compound 12-1.24).
Compound of formula (1.12) wherein A-R7 is methyl and the substituents X, Y, (R5)Sl (R5s)n and R-I3 correspond to line C.28 of Table C: m.p.: 83-84°C (compound 12-1.28).
Compound of formula (1.12) wherein A-R7 is methyl and the substituents X, Y, (R5), (R55)n and Ri3 correspond to line C.29 of Table C: m.p.: 76-77°C (compound 12-1.29).
Compound of formula (1.12) wherein A-R7 is methyl and the substituents X, Y, (R5)s, (R55)n and R.3 correspond to line C.63 of Table C: m.p.: 83-84°C (compound 12-1.63).
Compound of formula (1.12) wherein A-R7 is methyl and the substituents X, Y, (R5)s, (RssJn and R13 correspond to line C.64 of Table C: m.p.: 146-148°C (compound 12-1.64).
Compound of formula (1.12) wherein A-R7 is methyl and the substituents X, Y, (R5)s, (Rs5)n and R13 correspond to line C.65 of Table C: m.p.: 109-110°C (compound 12-1.65).
Compound of formula (1.12) wherein A-R7 is methyl and the substituents X, Y, (R5)s, (R∞),, and R13 correspond to line C.32 of Table C: m.p.: 104-105°C (compound 12-1.32).
Compound of formula (1.12) wherein A-R7 is methyl and the substituents X, Y, (R5)s, (R55)n and Ri3 correspond to line C.66 of Table C: m.p.: 74-85°C (compound 12-1.66).
Compound of formula (1.12) wherein A-R7 is methyl and the substituents X, Y, (R5)s, (R5s)n and R13 correspond to line C.67 of Table C: m.p.: 65-67°C (compound 12-1.67).
Compound of formula (1.12) wherein A-R7 is methyl and the substituents X, Y, (R5)s, (R^),, and R13 correspond to line C.68 of Table C: m.p.: 126-127°C (compound 12-1.68).
Compound of formula (1.12) wherein A-R7 is methyl and the substituents X, Y, (R5)s, (Rss)n and R13 correspond to line C.70 of Table C: m.p.: 122-123°C (compound 12-1.70). Compound of formula (1.12) wherein A-R7 is methyl and the substituents X, Y, (R5)s, (R55)n and R13 correspond to line C.71 of Table C: m.p.: 58-59°C (compound 12-1.71).
Compound of formula (1.12) wherein A-R is methyl and the substituents X, Y, (R5)s,
Figure imgf000075_0001
and R13 correspond to line C.73 of Table C: m.p.: 63-64°C (compound 12-1.73).
Table 12-2: Compounds of formula (1.12) wherein AR7 is CH2CH3 and the combination of substituents X, Y, (R5)s, (RssJn and R-|3 for each compound corresponds to a line of Table 2.
Compound of formula (1.12) wherein A-R7 is ethyl and the substituents X, Y, (R5)s, (R55)n and R13 correspond to line C.24 of Table C: m.p.: 56-57°C (compound 12-2.24).
Compound of formula (1.12) wherein A-R7 is ethyl and the substituents X, Y, (R5)s, (RS5)nand R-I3 correspond to line C.28 of Table C: m.p.: 90-91 °C (compound 12-2.28).
Compound of formula (1.12) wherein A-R7 is ethyl and the substituents X, Y, (R5)S) (R55R6)n and R13 correspond to line C.29 of Table C: m.p.: 168-169°C (compound 12-2.29).
Compound of formula (1.12) wherein A-R7 is ethyl and the substituents X, Y, (R5)s, (R6)nand R13 correspond to line C.33 of Table C: m.p.: 59-60°C (compound 12-2.33).
Compound of formula (1.12) wherein A-R7 is ethyl and the substituents X, Y, (R5)s, (R6)nand Rι3 correspond to line C.69 of Table C: resin (compound 12-2.69).
Compound of formula (1.12) wherein A-R7 is ethyl and the substituents X, Y, (R5)s, (R6)nand Rι3 correspond to line C.70 of Table C: m.p.: 132-133°C (compound 12-2.70).
Compound of formula (1.12) wherein A-R7 is ethyl and the substituents X, Y, (R5)s, (R6)nand R-I3 correspond to line C.71 of Table C: m.p.: 131-132°C (compound 12-2.72).
Compound of formula (1.12) wherein A-R7 is ethyl and the substituents X, Y, (R5)s, (R6)nand R13 correspond to line C.73 of Table C: m.p.: 69-70°C (compound 12-2.73).
Compound of formula (1.12) wherein A-R7 is ethyl and the substituents X, Y, (R5)s, (R55)nand R13 correspond to line C.74 of Table C: m.p.: 70-71 °C (compound 12-2.74).
Table 12-3: Compounds of formula (1.12) wherein AR7 is CH2CH=CH2 and the combination of substituents X, Y, (R5)s, (Rss)n and R13 for each compound corresponds to a line of Table 2.
Table 12-4: Compounds of formula (1.12) wherein AR7 is CH2C≡CH and the combination of substituents X, Y, (R5)s, (Rss)n and R13 for each compound corresponds to a line of Table 2. Table 12-5: Compounds of formula (1.12) wherein AR7 is CH2CH2CH3 and the combination of substituents X, Y, (R5)s, (Rss)n and R13 for each compound corresponds to a line of Table 2.
Table 12-6: Compounds of formula (1.12) wherein AR7 is CH(CH3)2 and the combination of substituents X, Y, (Rs)s. (Rss)n and R13 for each compound corresponds to a line of Table C.
Table 12-7: Compounds of formula (1.12) wherein AR7 is CH2CH2CH2CH3 and the combination of substituents X, Y, (R5)s, (Rss)n and R13 for each compound corresponds to a line of Table C.
Table 12-8: Compounds of formula (1.12) wherein AR7 is CH(CH3)(CH2CH3) and the combination of substituents X, Y, (R5)s, (Rss)n and R13 for each compound corresponds to a line of Table C.
Table 12-9: Compounds of formula (1.12) wherein AR7 is C(CH3)3and the combination of substituents X, Y, (R5)s, (Rss)n and R13 for each compound corresponds to a line of Table C.
Table 12-10: Compounds of formula (1.12) wherein AR7 is CH2CF3and the combination of substituents X, Y, (Rs)s, (RssJn and R13 for each compound corresponds to a line of Table C.
Table 12-11 : Compounds of formula (1.12) wherein AR7 is CH2CH=C(CH3)2 and the combination of substituents X, Y, (R5)s, (Rss)n and R13 for each compound corresponds to a line of Table C.
Table 12-12: Compounds of formula (1.12) wherein AR7 is CH2CH=CCI2 and the combination of substituents X, Y, (R5)s, (Rss)n and R13 for each compound corresponds to a line of Table C.
Table 12-13: Compounds of formula (1.12) wherein AR7 is CH2Si(CH3)3 and the combination of substituents X, Y, (R5)s, (Rss)n and R13 for each compound corresponds to a line of Table C.
Table 12-14: Compounds of formula (1.12) wherein AR7 is CH2-c.propyl-2,2-CI2 and the combination of substituents X, Y, (R5)s, (Rss)n and R13 for each compound corresponds to a line of Table C.
Table 12-15: Compounds of formula (1.12) wherein AR7 is CH2CN and the combination of substituents X, Y, (R5)s, (Rss)n and R13 for each compound corresponds to a line of Table C. Table 12-16: Compounds of formula (1.12) wherein AR7 is CH2COOCH3and the combination of substituents X, Y, (R5)s, (Rssin and R-|3 for each compound corresponds to a line of Table C.
Table 12-17: Compounds of formula (1.12) wherein AR7 is CH2COO-iso-C3H7 and the combination of substituents X, Y, (R5)s, (Rss)n and R-|3 for each compound corresponds to a line of Table C.
Table 12-18: Compounds of formula (1.12) wherein AR7 is C(=O)OC2H5 and the combination of substituents X, Y, (R5)s, (R55)n and R13 for each compound corresponds to a line of Table C.
Table 12-19: Compounds of formula (1.12) wherein AR7 is C(=O)NHCH3 and the combination of substituents X, Y, (R5)s, (Rssin and R13 for each compound corresponds to a line of Table C.
Table 12-20: Compounds of formula (1.12) wherein AR7 is C(=O)C(=O)OC2H5 and the combination of substituents X, Y, (Rs)s. (Rss)n and R13 for each compound corresponds to a line of Table C.
Table 12-21 : Compounds of formula (1.12) wherein AR is CH2C6H5and the combination of substituents X, Y, (R5)s, (Rss)n and R13 for each compound corresponds to a line of Table C.
Table 12-22: Compounds of formula (1.12) wherein AR is CH2C6H4-2-F and the combination of substituents X, Y, (R5)s, (Rss)n and R13 for each compound corresponds to a line of Table C.
Table 12-23: Compounds of formula (1.12) wherein AR7 is CH2C6H4-3-CI and the combination of substituents X, Y, (Rs)s, (Rss)n and R13 for each compound corresponds to a line of Table C.
Table 12-24: Compounds of formula (1.12) wherein AR7 is CH2C6H4-4-Br and the combination of substituents X, Y, (R5)s, (Rss)n and R13 for each compound corresponds to a line of Table C.
Table 12-25: Compounds of formula (1.12) wherein AR7 is CH2C6H4-3-CF3 and the combination of substituents X, Y, (R5)s, (Rss)n and R13 for each compound corresponds to a line of Table C. Table 12-26: Compounds of formula (1.12) wherein AR7 is CH2C6H4-4-CF3 and the combination of substituents X, Y, (R5)s, (R5s)n and R-|3 for each compound corresponds to a line of Table C.
Table 13-1 : Compounds of formula (1.13) wherein AR7 is CH3 and the combination of substituents X, Y, (Rs)s. (Rss)n and R13 for each compound corresponds to a line of Table C.
Table 13-2: Compounds of formula (1.13) wherein AR7 is CH2CH3 and the combination of substituents X, Y, (Rs)s, (Rss)n and R13 for each compound corresponds to a line of Table C.
Table 13-3: Compounds of formula (1.13) wherein AR7 is CH2CH=CH2and the combination of substituents X, Y, (Rs)s. (Rss)n and R-|3 for each compound corresponds to a line of Table C.
Table 13-4: Compounds of formula (1.13) wherein AR7 is CH2C≡CH and the combination of substituents X, Y, (R5)s, (Rss)n and R13 for each compound corresponds to a line of Table C.
Table 13-5: Compounds of formula (1.13) wherein AR7 is CH2CH2CH3 and the combination of substituents X, Y, (R5)s, (Rss)n and R-|3 for each compound corresponds to a line of Table C.
Table 13-6: Compounds of formula (1.13) wherein AR7 is CH(CH )2 and the combination of substituents X, Y, (Rs)s. (Rss)n and R13 for each compound corresponds to a line of Table C.
Table 13-7: Compounds of formula (1.13) wherein AR7 is CH2CH2CH2CH3 and the combination of substituents X, Y, (R5)s, (Rss)n and R13 for each compound corresponds to a line of Table C.
Table 13-8: Compounds of formula (1.13) wherein AR7 is CH(CH3)(CH2CH3) and the combination of substituents X, Y, (R5)s, (Rss)n and R13 for each compound corresponds to a line of Table C.
Table 13-9: Compounds of formula (1.13) wherein AR7 is C(CH3)3 and the combination of substituents X, Y, (Rs)s, (RssJn and R13 for each compound corresponds to a line of Table C. Table 14: Compounds of formula
Figure imgf000079_0001
The figures in the column "Phys. data" denote melting points in °C.
No. AR7 Phys. data
14.1 2-CI C2Hε CH OCH3 2 oil
14.2 2-CI C2Hε N OCH3 2 m.p. 83-85°C
14.3 2-CI C2Hs N NHCH3 2 oil
14.4 4-CI C2Hs CH OCH3 2 m.p. 90-92°C
14.5 4-CI C2Hs N OCH3 2 m.p. 85-87°C
14.6 4-CI C2H5 N NHCH3 2 oil
Figure imgf000079_0002
14.8 4-CF3 C2Hs N OCH3 2
14.9 4-CF3 C2H5 N NHCH3 2
14.10 2-CF3 C2Hs CH OCH3 2
14.11 2-CF3 C2Hε N OCH3 2
14.12 2-CF3 C2H5 N NHCH3 2
14.13 4-CF3 C2Hs N OCH3 3 oil
14.14 4-CF3 CH3 CH OCH3 3 resin
14.15 3-CF3 CH3 CH OCH3 4 oil
14.16 4-CF3 CH3 CH OCH3 4 resin
14.17 4-CF3 C2Hs N OCH3 4 oil
14.18 3-CF3 CH3 CH OCH3 4 oil
14.19 3-CF3 C2H5 N OCH3 4 oil
14.20 3-CF3 C2H5 N NHCH3 4 oil
14.21 3-CF3 C2Hδ N OCH3 3 oil
14.22 3-CF3 C2Hδ N NHCH3 3 resin Table 15: Compounds of formula
Figure imgf000080_0001
The figures in 1 the column "Phys. data" denote melting points in °C.
No. R5 AR7 X Y G-T Phys. data
15.1 H C2Hs CH 0CH3 CH2-CH2 oil
15.2 H Q2H5 N OCH3 CH2-CH2 oil
15.3 H C2Hδ N NHCH3 CH2-CH2 resin
15.4 H CH3 CH OCH3 CH2-S oil
15.5 H CH3 N OCH3 CH2-S resin
15.6 H CH3 N NHCH3 CH2-S 111-113
15.7 H C2H5 CH OCH3 CH2-S oil
15.8 H C2H5 N OCH3 CH2-S oil
15.9 H C2Hs N NHCH3 CH2-S resin
15.10 H CH2C≡CH CH OCH3 CH2-S oil
15.11 H CH2C≡CH N OCH3 CH2-S oil
15.12 H CHzCsCH N NHCH3 CH2-S resin
15.13 4-F C2Hs N OCH3 CH2-CO- resin
Formulation Examples
Formulations such as emulsifiable concentrates, solutions granules, dusts, wettable powders, emulsifiable concentrates, extruder granules, coated granules and suspension concentrates are of the same kind as mentioned in EP-A-736 252, examples F1 to F10. Accordingly, the said formulations mentioned in EP-A-736252 are included by reference in the subject matter of the present invention. Bioloαical Examples
A) Microbicidal action
Example B1 : Action against Phytophthora infestans on tomatoes a) Curative action
After a cultivation period of three weeks, tomato plants of the "Red Gnome" variety are sprayed with a zoospore suspension of the fungus and incubated in a humidity chamber at 18 to 20°C and saturated humidity. Humidifying is discontinued after 24 hours. When the plants have dried off, they are sprayed with a mixture containing a wettable powder formulation of the test compound at a concentration of 200 ppm. After the spray-coating has dried, the plants are again placed in the humidity chamber for 4 days. The number and size of the typical leaf blotches that have appeared after that time serve as a measure for evaluating the effectiveness of the test compounds.
b) Preventive-systemic action
A wettable powder formulation of the test compound at a concentration of 60 ppm (based on the volume of soil) is used to water the surface of the soil in which three-week-old tomato plants of the "Red Gnome" variety have been potted. After a waiting period of three days, the undersides of the leaves of the plants are sprayed with a zoospore suspension of Phytophthora infestans. The treated plants are then placed in a spraying cabinet for 5 days at 18 to 20°C and saturated humidity. After that period, typical leaf blotches appear, the number and size of which are used to evaluate the effectiveness of the test compounds.
Whereas infestation in untreated and infected control plants is 100 %, with the compounds of Tables 1 to 15 infestation is reduced to 20 % or less in both tests. In particular, with the compounds 1-4.2, 2-4.2, 3-4.2, 4-1.1 , 5.5, 6.3, 8.10 and 9-2.2 the infestation is still fully suppressed even at a concentration of 20 ppm of the test compound.
Example B2: Action against Plasmopara viticola (Bert, et Curt.) (Berl. et DeToni) on vines Vine cuttings of the "Chasselas" variety are cultivated in a greenhouse and are infected at the 10-leaf stage, on the undersides of the leaves, with a spore suspension of Plasmopara viticola. After being kept in a humidity chamber for 24 hours, the plants are sprayed with mixtures comprising the active ingredient in concentrations of 200 ppm, 60 ppm and 20 ppm. The plants are then kept in the humidity chamber for a further 7 days. After that time, the disease symptoms appear in the control plants. The number and size of the infection sites on the treated plants serve as a measure for evaluating the effectiveness of the test compounds.
In comparison with the control plants, the plants treated with compounds of Tables 1 to 15 exhibit an infestation of 20 % or less. In particular, with the compounds 1-4.2, 3-4.2, 4-1.2, 6.3, 8.10 and 9-2.2 complete curative action is still obtained even at a concentration of 20 ppm of the test compound.
Example B3: Action against Puccinia graminis on wheat a) Residual-protective action
6 days after sowing, wheat plants are sprayed to drip point with an aqueous spray mixture (0.02 % active ingredient), and infected 24 hours later with a uredospore suspension of the fungus. After an incubation period of 48 hours (conditions: 95 to 100 % relative humidity at 20°C), the plants are placed in a greenhouse at 22°C. Evaluation of rust pustule development is made 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 soil). Care is taken that the spray mixture does not come into contact with the parts of the plants above the soil. The treated plants are infected 48 hours later with a uredospore suspension of the fungus. After an incubation period of 48 hours (conditions: 95 to 100 % relative humidity at 20°C), the plants are placed in a greenhouse at 22°C. Evaluation of rust pustule development is made 12 days after infection.
The compounds of Tables 1 to 15 bring about a distinct reduction in the fungus infestation, in some cases to from 10 to 0 %. In particular, with the compounds 3-4.2, 4.1-1 , 5.4, 8.10, 12-1.3, 10-1.16 and 12-1.4 the disease is suppressed completely (0-5 % infestation).
Example B4: Action against Pyricularia oryzae on rice plants a) Residual-protective action
After a cultivation period of 2 weeks, rice plants are sprayed to drip point with an aqueous spray mixture (0.02 % active ingredient), and are infected 48 hours later with a conidia sus- pension of the fungus. Evaluation of fungus infestation is made 5 days after infection, du r- ing which period 95 to 100 % relative humidity and a temperature of 22°C are maintained.
b) Systemic action
2-week-old rice plants are watered with an aqueous spray mixture (0.006 % active ingredient, based on the volume of soil). Care is taken that the spray mixture does not come into contact with the parts of the plant above the soil. The pots are then filled with water so that the lowermost parts of the stems of the rice plants stand in water. After 96 hours, the plants are infected with a conidia suspension of the fungus and kept for 5 days at 95 to 100 % relative humidity and a temperature of 24°C.
The compounds of Tables 1 to 15 largely prevent the disease from breaking out on the i n- fected plants.
Example B5: Action against Erysiphe graminis on barlev 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) and dusted 3 to 4 hours later with conidia of the fungus. The infected plants are placed in a greenhouse at 22°C. The fungus infestation is evaluated 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 soil). Care is taken that the spray mixture does not come into contact with the parts of the plants above the soil. The treated plants are dusted 48 hours later with conidia of the fungus. The infected plants are placed in a greenhouse at 22°C. The fungus infestation is evaluated 10 days after infection. The compounds of Tables 1 to 15 in general are able to suppress infestation with the disease to less than 20 % and, in some cases, to suppress it completely.
Example B6: Action against Botrytis cinerea on apple fruits. Residual -protective action Artificially damaged apples are treated by applying drops of a spray mixture (0.02 % active ingredient) onto the damage sites. The treated fruits are then inoculated with a spore su s- pension of the fungus and incubated for one week at high humidity and about 20°C. The fungicidal action of the test compound is derived from the number of rotted damage sites. Compounds of Tables 1 to 15 are able to prevent the rot from spreading, in some cases completely.
B. Insecticidal action
Example B7: Action against Aphis craccivora
Pea seedlings are infested with Aphis craccivora, subsequently sprayed with a spray mixture comprising 100 ppm of the test compound and then incubated at 20°C. 3 and 6 days later the percentage reduction in population (% activity) is determined by comparing the number of dead aphids on the treated plants with that on untreated plants. The compounds of Tables 1 to 15 generally exhibit good activity in this test. In particular, compounds 1-4.2, 2-4.2, 3-4.2, 4-1.3, 4-1.7, 5.1 , 5.3 and 8.10 are more than 80 % effective in this test.
Example B8: Action against Diabrotica balteata
Maize seedlings are sprayed with an aqueous emulsion spray mixture comprising 100 ppm of the test compound. After the spray-coating has dried, the maize seedlings are populated with 10 Diabrotica balteata larvae in the second stage and then placed in a plastics container. 6 days later, the percentage reduction in population (% activity) is determined by comparing the number of dead larvae on the treated plants with that on untreated plants. The compounds of Tables 1 to 15 exhibit good activity in this test. In particular, compounds 1-4.2, 2-4.2, 4-1.2, 4-1.8, 5.5, 9-2.2, 12-1.3, 10-1.16 and 12-1.4 are more than 80 % effective in this test.
Example B9: Action against Heliothis virescens
Young soybean plants are sprayed with an aqueous emulsion spray mixture comprising 100 ppm of the test compound. After the spray-coating has dried, the plants are populated with 10 Heliothis virescens caterpillars in the first stage and then placed in a plastics container. 6 days later, the percentage reduction in 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 untreated plants. Most compounds of Tables 1 to 15 exhibit good activity in this test. In particular, compound 5.1 is more than 80 % effective in this test. Example B10: Action against Spodoptera littoralis
Young soybean plants are sprayed with an aqueous emulsion spray mixture comprising 100 ppm of the test compound. After the spray-coating has dried, the plants are populated with 10 Spodoptera littoralis caterpillars in the third stage and then placed in a plastics* container. 3 days later, the percentage reduction in 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 untreated plants. The compounds of Tables 1 to 15 exhibit good activity in this test.
C. Acaricidal action
Example B11 : Action against Tetranvchus urticae
Young bean plants are populated with a mixed population of Tetranychus urticae and sprayed one day later with an aqueous emulsion spray mixture comprising 100 ppm of the test compound. The plants are then incubated for 6 days at 25°C and subsequently evaluated. The percentage reduction in population (% activity) is determined by comparing the number of dead eggs, larvae and adults on the treated plants with that on untreated plants. The compounds of Tables 1 to 15 generally exhibit good activity in this test. In particular, compounds 1-4.2, 2-4.2, 3-4.2, 4-1.1 , 5.5, 6.3, 8.10, 9-2.2, 12-1.3, 10-1.16 and 12-1.4 are more than 80 % effective in this test.

Claims

What is claimed is:
1. A compound of formula
Figure imgf000086_0001
wherein either
X is CH or N, Y is ORi and Z is O, or
X is N, Y is NHR8 and Z is O, S or S(=O);
R. is hydrogen or C.-C4alkyl;
R8 is hydrogen or C.-C alkyl;
R2 is H, C╬╣-C4alkyl, halo-d-C4alkyl, C3-C6cycloalkyl, C╬╣-C alkoxymethyl, d-C4alkoxy, halo-C1-C4alkoxy, C╬╣-C4alkylthio, halo-C╬╣-C4alkylthio or CN;
R3 and R4 are each independently of the other H, C.-C alkyl, C.-C4alkoxy, OH, CN, NO2, a (d-C4alkyl)3-Si group, the alkyl groups being the same or different, halogen, (C.-C4alkyl)S(=O)m, (halo-C.-C4alkyl)S(=O)m, halo-d-C4alkyl or halo-C,-C4alkoxy; m is 0, 1 or 2;
R5 independently of any other is halogen, C.-C6alkyl, halo-C.-C6alkyl, C3-C$cycloalkyl, halo-C3-C6cycloalkyl, CrC6alkoxy, halo-CrCealkoxy, C.-Cealkylthio, halo-CrCealkyl- thio, C╬╣-C6alkylsulfinyl, halo-C╬╣-C6alkylsulfinyl, C.-C6alkyIsulfonyl, halo-C Cealkyl- sulfonyl, d-C╬▓alkylsulfonyloxy, halo-d-C╬▓alkylsulfonyloxy, C╬╣-C6alkoxy-C.-C╬▓alkyl, halo-CrC╬▓alkoxy-Ci-Cealkyl, d-Cealkylthio-d-C╬▓alkyl, halo-C╬╣-C6alkylthio-C╬╣-C6alkyl, C╬╣-C6alkylsulfinyl-C╬╣-C6alkyl, halo-C╬╣-C6alkylsulfinyl-C╬╣-C6alkyl, CrCealkylsulfonyl- C╬╣-C6alkyl, halo-Ci-Cealkylsulfonyl-d-Cealkyl, d-C6alkylcarbonyl, halo-d-C6alkyl- carbonyl, d-C6alkoxycarbonyl, halo-C╬╣-C6alkoxycarbonyl, C╬╣-C6alkylaminocarbonyl,
Figure imgf000086_0002
the alkyl groups being the same or different; C.-C6alkylaminothiocarbonyl, di(CrC6alkyl)aminothiocarbonyl, the alkyl groups being the same or different; C╬╣-C6alkylamino, di(d-C6alkyl)amino, the alkyl groups being the same or different; NO2, CN, SF5, thioamido, thiocyanatomethyl, trimethylsilyl; C╬╣-C alkylenedioxy or -CH=CH-CH=CH- each of which is unsubstituted or, depending on its substitution possibilities, mono- to tetra-substituted, the substituents of the d-C4alkylenedioxy or -CH=CH-CH=CH- group being selected from the group consisting of d-C4alkyl and halogen; aryl-Q-, heterocyclyl-Q-, aryl-Q-C╬╣-C6alkyl, aryl-Q-C2-C6alkenyl, heterocyclyl-Q-d-C6a!kyl or heterocyclyl-Q-C2-C6alkenyl, or aryl-Q-, heterocyclyl-Q-, aryl-Q-C╬╣-C6alkyl, aryl-Q-C2-C6alkenyl, heterocyclyl-Q-d-C6- alkyl or heterocyclyl-Q-C2-C6alkenyl each of which is, depending on its substitution possibilities, mono- to penta-substituted in the aryl or heterocyclyl ring, the substituents being selected independently of one another from the group consisting of halogen, C╬╣-C6alkyl, halo-d-C6alkyl, C3-C6cycloalkyl, haIo-C3-C6cycloalkyl, d-C6alkoxy, halo-d-C6alkoxy, CN, nitro and d-C6alkoxycarbonyl; and, when n is greater than 1 , the radicals R5 are the same or different; n is 0, 1 , 2, 3 or, if either a or b is 0, 4;
Q is a direct bond, -CH(OH)-, -C(=O)-, -S-, -S(=O) or -S(=O)2;
R9 is methyl, fluoromethyl or difluoromethyl; either
A is a direct bond, Ci-Cioalkylene, -C(=O)-, -C(=S)- or halo-d-Cioalkylene and
R7 is a radical R╬╣0; or
A is C╬╣-C╬╣0alkylene, -C(=O)-, -C(=S)- or halo-C╬╣-C╬╣oalkylene and
R7 is -CN, ORio, N(R╬╣o)2, the radicals R╬╣0 being the same or different, -SRio, -S(=O)R╬╣0 or -S(=O)2R╬╣0;
Rio is H, C╬╣-C6alkyl, C2-C8alkenyl, C2-C8alkynyl or C3-C6cycloalkyl, or d-C6alkyl, C2-C8- alkenyl, C2-C8alkynyl or C3-C6cycloalkyl each mono- or poly-substituted by substituents from the group consisting of halogen; -Si(C╬╣-C4alkyl)3, the alkyl groups being the same or different; d-C6alkoxycarbonyl or an aryl or heterocyclyl group that is unsubstituted or mono- or poly-substituted by substituents selected from the group consisting of halogen, C╬╣-C4alkyl and halo-C╬╣-C4alkyl; and
D is O, S, -S(=O) or S(=O)2;
G is C╬╣-C8alkylene;
T-Re is R6; -C(=N-O-A R77)-R6; -SiR14(R15)-R6; -C(=O)-R6; -C(R╬╣6)=C(R╬╣7)-R6; -CΓëíC-R6 or -D-R6;
R6 is d-dalkyl, aryl or heteroaryl; or aryl or heteroaryl each of which - depending on the substitution possibilities on the ring structure - is mono- to penta-substituted by substituents selected independently of one another from the group consisting of (R5)s; s is, depending on the substitution possibilities on the ring, 0, 1 , 2, 3, 4 or 5, the substituents R5 being independent of one another when s is greater than 1 ;
Ai and R^ are as defined above for A and R7; a is 0 or 1 ;
L is U-R╬╣8, P(O)vR╬╣╬╣R12, P(S)WR.1R12 or N(aryl)R╬╣3, the aryl radical being either unsubstituted or mono- to penta-substituted by substituents selected independently of one another from the group consisting of R5; v and w are 0 or 1 ;
U-R,╬▓ is -C(=O)-C(=O)-R╬╣8; -C(OH)-C(OH)-R╬╣8; -C(=N-O-A╬╣-R7)-R,8;
OC C6alkyl
Figure imgf000088_0001
p is from 0 to 4;
Rn and R12 are each independently of the other d-C6alkyl, halo-CrC6alkyl, C3-C6cyclo- alkyl, halo-C3-C6cycloalkyl, d-C6alkoxy, halo-d-C6alkoxy, d-C╬▓alkylthio, halo- CrC6alkylthio, aryl, heteroaryl, aryloxy, arylthio, heteroaryioxy or heteroarylthio; or aryl, heteroaryl, aryloxy, arylthio, heteroaryioxy or heteroarylthio each mono- to penta- substituted by R5, the substituents R5 being independent of one another; b is 0 or 1 , but a and b are not simultaneously 0;
R13 is hydrogen, C C6alkyl, halo-d-C6alkyl, C3-C6cycloalkyl, halo-C3-C6cycloalkyl,
CrC6alkylsulfinyl, halo-d-Cealkylsulfinyl, C╬╣-C6alkylsulfonyl, halo-d-C╬▓alkylsulfonyl, CrC╬▓alkoxy-C Cealkyl, halo-d-C╬▓alkoxy-d-C╬▓alkyl, d-C╬▓alkylthio-d-C╬▓alkyl, halo- CrCealkylthio-C C╬▓alkyl, C╬╣-C6alkylsulfinyl-C C6alkyl, halo-C C╬▓alkylsulfinyl- C C6alkyl, d-Cealkylsulfonyl-C.-C╬▓alkyl, halo-d-Cealkylsulfonyl-d-Cealkyl, for yl, C C6alkylcarbonyl, d-C6alkyl-C(=S)-, C1-C6alkylthio-C(=S)-, halo-d-C╬▓alkylcarbonyl, C C6alkoxycarbonyl, halo-C╬╣-C6alkoxycarbonyl, CrC6alkylaminocarbonyl, d-C4- alkoxyiminomethyl, di(C C6alkyl)aminocarbonyl, the alkyl groups being the same or different; d-C6alkylaminothiocarbonyl, di(d-C6alkyl)aminothiocarbonyl, the alkyl groups being the same or different; C C6alkyldicarbonyl, halo-d-C6alkyldicarbonyl, CrC6alkoxydicarbonyl, halo-CrC6alkoxydicarbonyl, C╬╣-C6alkylaminodicarbonyl, di(CrC6alkyl)aminodicarbonyl, the alkyl groups being the same or different; CrC6alkylaminodithiocarbonyl, di(C C6all<y╬╣)aminodithioc_arbonyl, the alkyl groups being the same or different; aryl, arylsulfinyl, aryl-C╬╣-C6alkylsulfinyl, arylsulfonyl, aryl- d-C6alkyl-sulfonyl, aryloxy-d-C╬▓alkyl, arylthio-d-C╬▓alkyl, aryl-d-C6alkylsu.finyl- d-C6aIkyl, aryl-d-C╬▓alkylsulfonyl-CrC╬▓alkyl, arylcarbonyl, arylalkylcarbonyl, aryloxy- carbonyl, arylalkoxycarbonyl, arylaminocarbonyl, aryloxyiminomethyl, di(aryl)amino- carbonyl, the aryl groups being the same or different; arylaminothiocarbonyl, di(aryl)aminothiocarbonyl, the aryl groups being the same or different; aryldicarbonyl, aryl-C C6alkyldicarbonyl, aryloxydicarbonyl, aryl-C╬╣-C6alkoxydicarbonyl, arylamino- dicarbonyl, di(aryl)aminodicarbonyl, the aryl groups being the same or different; ary- laminodithiocarbonyl, di(aryl)aminodithiocarbonyl, the aryl groups being the same or different; and the aryl groups in the afore-mentioned substituents being unsubstituted or mono- to penta-substituted by substituents R╬┤, the substituents R5 being independent of one another; unsubstituted or substituted heteroaryl, unsubstituted or substituted heteroarylcarbonyl, unsubstituted or substituted heteroarylsulfinyl, or unsubstituted or substituted heteroarylsulfonyl;
R and R15 are each independently of the other C╬╣-C4alkyl;
R.6 and R╬╣7 are each independently of the other hydrogen, d-dalkyl or halogen and
and, where applicable, their possible E/Z isomers, mixtures of E/Z isomers and/or tautomers, in each case in free form or in salt form, with the proviso (P1) that G is not -CH2- when R2 is methyl, R3 and R4 are hydrogen, D is oxygen, a is 1 , b is 0, and either in the group -SiRι4(Rι5)-R6 the radicals Rι , R15 and R6 are methyl, or in the group -C(Rι6)=C(Rι7)-R6 the radical R6 is methyl and the radical Rι7 is hydrogen or methyl; with the proviso (P2) that G is not Cι-C3alkylene when a is 1 , b is 0, T is a direct bond and R6 is Cι-C4alkyl; and with the further proviso (P3) that G is not -CH2- when Dϊs oxygen, a is 1 , b is 0, R2 is d-C6alkyl or C3-Cβcycloalkyl, T is a direct bond and R6 is unsubstituted or substituted phenyi.
2. A compound according to claim 1 of formula (I) in free form.
3. A compound according to claim 2 of formula (I) wherein X is CH and Z is O.
4. A compound according to claim 2 of formula (I) wherein X is N and Z is O.
5. A compound according to claim 2 of formula (I) wherein Y is OC╬╣-C4alkyl.
6. A compound according to any one of claims 3 to 5 of formula (I) wherein R2 is H, C╬╣-C alkyl, halo-d-C4alkyl or C3-C6cycloalkyl.
7. A compound according to any one of claims 3 to 6 of formula (I) wherein
R3 is H, d-dalkyl, C╬╣-C4alkoxy, OH, CN, NO2, halogen, halo-d-C4alkyl or halo- d-dalkoxy.
8. A compound according to any one of claims 3 to 7 of formula (I) wherein
R4 is H, d-C4alkyl, d-C4alkoxy, OH, CN, NO2, halogen, halo-C╬╣-C4alkyl or halo- d-dalkoxy.
9. A compound according to any one of claims 3 to 8 of formula (I) wherein R8 is H or d-C2alkyl.
10. A compound according to any one of claims 3 to 9 of formula (I) wherein R9 is methyl or fluoromethyl.
11. A compound according to any one of claims 3 to 10 of formula (I) wherein A is a direct bond, Ci-Cioalkylene or halo-d-C10alkylene, and
R7 is a radical R╬╣0.
12. A compound according to claim 11 of formula (I) wherein AR7 is methyl or ethyl.
13. A compound according to any one of claims 3 to 12 of formula (I) wherein a is 1 , n is 0, b is 0 and D is oxygen.
14. A compound according to claim 13 of formula (I) wherein a is 1 and G is C╬╣-C4alkylene.
15. A compound according to any one of claims 3 to 14 of formula (I) wherein
R6 is C╬╣-C alkyl, aryl, or aryl mono- to penta-substituted by substituents selected independently of one another from the group consisting of R5.
16. A process for the preparation of a compound as defined in claim 1 , formula (I), or, where applicable, an E/Z isomer, mixture of E/Z isomers and/or a tautomer thereof, in each case in free form or in salt form, which process comprises either a1 ) reacting a compound of formula
Figure imgf000091_0001
wherein X, Y, Z, R3, R4 and R╬▓ are as defined for formula (I) and X , is a leaving group, with a compound of formula
Figure imgf000091_0002
wherein a, b, n, A, D, G, T, L, R2, R5, R6 and R7 are as defined for formula (I) and wherein the provisos mentioned in claim 1 for the compounds of formula (I) apply, or
a2) reacting a compound of formula
Figure imgf000091_0003
wherein a, b, n, A, D, G, T, L, R2, R5, R6 and R7 are as defined for formula (I) and wherein the provisos mentioned above for the compounds of formula (I) apply, with a compound of formula
Figure imgf000092_0001
wherein X, Y, Z, R3, R4 and R8 are as defined for formula (I), or
b) to prepare a compound of formula (I) wherein Y is NHR8 and Z is O, reacting a compound of formula (I) wherein Y is OR1 with a compound of formula R8NH2 wherein R8 is as defined for formula (I), or
c) to prepare a compound of formula (I) wherein Y is NHR8 and Z is S, reacting a compound of formula (I) wherein Y is R8NH2 and Z is O with P4S10 or Lawesson's reagent, or
d) to prepare a compound of formula (I) wherein Z is SO, reacting a compound of formula (I) wherein Z is S with an oxidising agent,
and, in each case, if desired, converting a compound of formula (I) obtainable according to the process or by a different method, or an E Z isomer or tautomer thereof, in each case in free form or in salt form, into a different compound of formula (I) or an E/Z isomer or tautomer thereof, in each case in free form or in salt form, separating a mixture of E/Z isomers obtainable according to the process and isolating the desired isomer and/or converting a free compound of formula (I) obtainable according to the process or by a different method, or an E/Z isomer or tautomer thereof, into a salt, or converting a salt of a compound of formula (I), or of an E/Z isomer or tautomer thereof, obtainable according to the process or by a different method into the free compound of formula (I), or an E/Z isomer or tautomer thereof, or into a different salt.
17. A pesticidal composition which comprises at least one compound according to claim 1 of formula (I) or, where applicable, an E/Z isomer or tautomer thereof, in free form or in agrochemically acceptable salt form, as active ingredient in an effective active concentration, and at least one adjuvant.
18. A method of preparing a composition as described in claim 17, wherein the active ingr e- dient is intimately mixed and/or ground with the adjuvant(s).
19. The use of a compound as described in claim 1 , of formula (I), or where applicable, of an E/Z isomer or tautomer thereof, in free form or in agrochemically acceptable salt form, wherein the provisos P1 to P3 according to claim 1 apply, in the preparation of a compos i- tion according to claim 17.
20. The use of a compound as described in claim 1 , of formula (I), or of a composition as described in claim 17, wherein the provisos P1 to P3 according to claim 1 apply, in contro I- ling pests.
21. A method of controlling pests, wherein a compound as described in claim 1 , of fo r- mula (I), or a composition as described in claim 17, wherein the provisos P1 to P3 according to claim 1 apply, is applied to the pests or to their habitat.
22. A method according to claim 21 of protecting plant propagation material, wherein the propagation material or the planting site of the propagation material is treated.
23. Plant propagation material treated according to the method described in claim 22.
PCT/EP1998/003073 1997-05-27 1998-05-25 O-benzyl oxime ethers and their use as pesticides WO1998054125A1 (en)

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CN105199018A (en) * 2015-11-06 2015-12-30 常州久日化学有限公司 Novel oxime ester photoinitiator as well as preparation and application thereof

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Publication number Priority date Publication date Assignee Title
AU2009331476B2 (en) * 2008-12-23 2015-05-28 Basf Se Imine compounds for combating invertebrate pests

Citations (4)

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Publication number Priority date Publication date Assignee Title
WO1995018789A1 (en) * 1994-01-05 1995-07-13 Ciba-Geigy Ag Pesticides
WO1996016026A1 (en) * 1994-11-17 1996-05-30 Novartis Ag O-benzyl oxime ether derivatives and their use as pesticides
DE19540361A1 (en) * 1995-10-30 1997-05-07 Basf Ag Phenylacetic acid derivatives, processes and intermediates for their preparation and their use for controlling harmful fungi and animal pests
WO1997020809A1 (en) * 1995-12-07 1997-06-12 Novartis Ag Pesticides

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Publication number Priority date Publication date Assignee Title
WO1995018789A1 (en) * 1994-01-05 1995-07-13 Ciba-Geigy Ag Pesticides
WO1996016026A1 (en) * 1994-11-17 1996-05-30 Novartis Ag O-benzyl oxime ether derivatives and their use as pesticides
DE19540361A1 (en) * 1995-10-30 1997-05-07 Basf Ag Phenylacetic acid derivatives, processes and intermediates for their preparation and their use for controlling harmful fungi and animal pests
WO1997020809A1 (en) * 1995-12-07 1997-06-12 Novartis Ag Pesticides

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105199018A (en) * 2015-11-06 2015-12-30 常州久日化学有限公司 Novel oxime ester photoinitiator as well as preparation and application thereof
CN105199018B (en) * 2015-11-06 2017-03-22 常州久日化学有限公司 Oxime ester photoinitiator as well as preparation and application thereof

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