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WO1998028262A1 - Derives d'ether o-benzyl-oxime utilises comme pesticides - Google Patents

Derives d'ether o-benzyl-oxime utilises comme pesticides Download PDF

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Publication number
WO1998028262A1
WO1998028262A1 PCT/EP1997/007122 EP9707122W WO9828262A1 WO 1998028262 A1 WO1998028262 A1 WO 1998028262A1 EP 9707122 W EP9707122 W EP 9707122W WO 9828262 A1 WO9828262 A1 WO 9828262A1
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Prior art keywords
halo
formula
alkyl
compound
dalkyl
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PCT/EP1997/007122
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English (en)
Inventor
Ottmar Franz HÜTER
Saleem Farooq
Stephan Trah
Henry Szczepanski
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Novartis AG
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Ciba Geigy AG
Novartis AG
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Priority to AU57600/98A priority Critical patent/AU5760098A/en
Publication of WO1998028262A1 publication Critical patent/WO1998028262A1/fr
Anticipated expiration legal-status Critical
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    • 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
    • C07C251/34—Oximes with oxygen atoms of oxyimino groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals
    • C07C251/36—Oximes with oxygen atoms of oxyimino groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals with the carbon atoms of the oxyimino groups bound to hydrogen atoms or to acyclic carbon atoms
    • C07C251/40—Oximes with oxygen atoms of oxyimino groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals with the carbon atoms of the oxyimino groups bound to hydrogen atoms or to acyclic carbon atoms to carbon atoms of an unsaturated carbon skeleton
    • 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
    • C07C251/34—Oximes with oxygen atoms of oxyimino groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals
    • 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
    • C07C251/34—Oximes with oxygen atoms of oxyimino groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals
    • C07C251/36—Oximes with oxygen atoms of oxyimino groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals with the carbon atoms of the oxyimino groups bound to hydrogen atoms or to acyclic carbon atoms
    • C07C251/38—Oximes with oxygen atoms of oxyimino groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals with the carbon atoms of the oxyimino groups bound to hydrogen atoms or to acyclic carbon atoms to carbon atoms of a saturated carbon skeleton
    • 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

Definitions

  • the invention relates to compounds of formula
  • X is CH or N
  • Y is ORi and Z is O
  • R is H or C ⁇ -C 4 alkyl
  • R 2 is H, C ⁇ -C 4 alkyl, halo-C ⁇ -C 4 alkyi, C 3 -C 6 cycioalkyI, C 3 -C ⁇ cycloalkenyl, d-d- alkoxymethyl, C ⁇ -C 4 alkoxy, halo-C ⁇ -C 4 alkoxy, d-C 4 alky!thio or halo-C ⁇ -C 4 alkylthio, cyano or aryl;
  • I is O, 1 or 2;
  • R 5 and R ⁇ are each independently of the other C ⁇ -C 6 alkyl, halo-CrC 6 alkyl, C 3 -C 6 cycloalkyl, CrC ⁇ cycloalkenyl, halo-C3-C 6 cycloalkyl, d-dalkoxy, halo-CrC ⁇ alkoxy, d-Ce-alkyl- thio, halo-C ⁇ -C ⁇ alkylthio, C ⁇ -C 6 alkylsulfinyl, halo-d-C ⁇ aikylsulfinyl, CrC ⁇ -alkylsulfonyl, halo-C ⁇ -C 6 alkylsulfonyl, C ⁇ -C 6 alkylsulfonyloxy, halo-d-C 6 alkyl-sulfonyloxy, d-dalk- oxy-C ⁇ -C 6 alkyi, halo-C ⁇ -
  • R 55 is CrC 6 alkyl, halo-C ⁇ -C 6 alkyl, C 3 -C e cycloalkyl, d-CeCycloalkenyl, halo-C 3 -C 6 -cycl- oalkyl, C ⁇ -C 6 alkoxy, halo-d-C 6 alkoxy, C ⁇ -C 6 alkylthio, halo-d-C 6 alkylthio, d-C 6 alkyl- sulfinyl, halo-C ⁇ -C 6 alkylsulfinyl, C ⁇ -C 6 alkylsulfony1, halo-C ⁇ -C 6 alkylsulfonyl, C ⁇ -C ⁇ alkyl- sulfonyloxy, halo-d-C ⁇ alkylsulfonyloxy, d-C ⁇ alkoxy-C ⁇ -C ⁇ alkyl, halo-Ci-Cealk
  • R ⁇ e is hydrogen, C ⁇ -C ⁇ alkyl, halo-Ci-Cealkyl, C 3 -C 6 cycioalkyl, d-C 6 cycloalkenyl, halo- d-C ⁇ cycloalkyl, Ci-C ⁇ alkyisulfinyl, halo-C ⁇ -C 6 alkylsulfinyl, Ci-C ⁇ alkylsulfonyl, halo- Ci-C 6 alkylsulfonyl, Ci-C ⁇ alkoxy-Ci-Cealk l, halo-d-C ⁇ alkoxy-C ⁇ -C ⁇ alkyl, Ci-Ce- alkylthio-C ⁇ -C 6 alkyl, halo-d-C ⁇ alkylthio-Ci-dalkyl, C ⁇ -C ⁇ alkylsulfinyl-C ⁇ -C 6 alkyl, halo- C ⁇ -C 6 al
  • R 7 is a radical R ⁇ 0 ;
  • R 8 is H or d-dalkyl
  • R 9 is methyl, fluoromethyl or difluoromethyl
  • R10 is H, Ci-Cealkyl, C 2 -C ⁇ alkenyl, C 2 -C ⁇ alkynyi, C 3 -C ⁇ cycloalkyl, or CrC ⁇ alkyl, C 2 -C 8 alk- enyl, C 2 -C ⁇ alkynyl or C 3 -C ⁇ cycloalkyl, each of which is mono- or poly- substituted by substituents selected from the group consisting of halogen; or R 10 is -Si(C 1 -C 4 alkyl) 3l it being possible for the alkyl groups to be the same or different; C ⁇ -C ⁇ alkoxycarbonyl, or an aryl or heterocyclyl group that is unsubstituted or mono- or poly-substituted by substituents from the group consisting of halogen, d-dalkyl and halo-d-dalkyl; and p is 0, 1 or 2; and where applicable, their
  • a number of compounds of formula (I), and of the formulae (II) to (XIV) 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 to include all those possible isomeric forms and also mixtures thereof, for example racemates or E/Z isomeric mixtures, and also, optionally, salts thereof, even if these are 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 cycloalkyl, haloalkyl, alkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl, alkylcarbonyl, alkoxy- carbonyl, 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, isopen- tyl, neopentyl or isohexyl.
  • Alkenyl as a group perse and also as a structural unit of other groups and compounds, such as of cycloalkenyl and haloalkenyi, 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 or2-hexenyl, or branched, for example isopropenyl.
  • 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-ethynylpropvl 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,
  • Aryl is phenyl or naphthyl, especially phenyl.
  • 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 one nitrogen atom as hetero atom and optionally a further hetero atom, preferably nitrogen or sulfur, especially nitrogen.
  • Preferred heteroaryl moieties in the radical R 5 are pyrazinyl, 3'-pyridyI, 2'-pyridyl, 4'-pyridyl, 2'-pyrimidinyl,
  • Halogen as a group perse and also as a structural unit of other groups and compounds, such as of haloalkyl, haloalkenyi and haloalkynyl, is fluorine, chlorine, bromine or iodine, especially fluorine, chlorine or bromine, more especially fluorine or chlorine, very especially fluorine.
  • Haiosubstituted carbon-containing groups and compounds such as haloalkyl, haloalkenyi 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 haloalkenyi, 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 or CH
  • Haloalkynyl is, for example, CH 2 CsCF, CH 2 CHCCH 2 CI or CF 2 CF 2 CsCCH 2 F.
  • a number of compounds of formula (I), and of the formulae (III), (IV), (VI), (VIII), (X) and (XII) to (XV) given hereinafter, may, as is known to the person skilled in the art, be present in the form of tautomers, for example when R 7 is H.
  • any reference to those compounds should 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 (II) to (XV) 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-dalkanecarboxyiic 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, hydroxycarboxyiic 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, d-dalkane- or aryi-sulfonic acids, e.g. methane- or p-toluene- sulfonic acid.
  • compounds of formulae (I) to (VI), and (VIII) to (XV) 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 morpholine, piperidine, pyrrolidine, a mono-, di- or tri-lower alkylamine, e.g. ethyl-, diethyl-, triethyl- or dime- thyl-propyl-amine, or a mono-, di- or tri-hydroxy-lower alkylamine, e.g. mono-, di- or tri- ethanolamine. It is also possible for corresponding intemal 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 morpholine, piperidine, pyrrolidine, a mono-, di- or tri-low
  • any reference to the compounds of formulae (I) to (XV) or their salts is to be understood as including where appropriate also the corresponding salts or free compounds of formula (I), respectively.
  • X, Z, R 2 , R 3 , F , Re, R7. R9 and A are as defined above, and
  • Ri is d-dalkyl
  • R 5 is Ci-Cealkyl, halo-C ⁇ -C 6 alkyl, C 3 -C 6 cycloalkyl, C 3 -C 6 cycioalkenyl, halo-C 3 -C 6 - cycloalkyl, d-C ⁇ alkoxy, halo-Ci-dalkoxy, Ci-C ⁇ alkylthio, halo-C ⁇ -C 6 alkylthio, C ⁇ -C 6 alkylsulfinyl, halo-C ⁇ -C 6 alkylsulfinyl, C ⁇ -C 6 alkylsulfonyl, halo-d-C e alkylsulfonyl, C ⁇ -C 6 alkylsulfonyloxy, halo-C ⁇ -C 6 alkylsulfonyloxy, Ci-C e alkoxy-Ci-C 6 aIkyl, halo-C ⁇ -C 6
  • R 2 is H, Ci-dalkyl, halo-d-dalkyl or C3-C e cycloalkyl, cyano, aryl, preferably d-dalkyl, halo-Ci-dalkyl or cyclopropyl; especially Ci-dalkyl; more especially methyl;
  • R 3 is H, Ci-dalkyl, Ci-dalkoxy, OH, CN, N0 2 , halogen, halo-Ci-dalkyl or halo-d-d- alkoxy, preferably H, Ci-dalkyl, C ⁇ -C alkoxy or halogen, especially H, methyl, methoxy, chlorine or fluorine, more especially H;
  • FU is H, Ci-dalkyl, Ci-dalkoxy, OH, CN, N0 2 , halogen, halo-d-C alkyl or halo-d-d- alkoxy, preferably H, Ci-dalkyl, Ci-dalkoxy or halogen, especially H, methyl, methoxy, chlorine or fluorine, more especially H;
  • R 55 is d-dalkyl, halo-d-dalkyl, C 3 -C 6 cycloalkyl, C 3 -C 6 cycloalkenyl, halo-C 3 -C 6 - cycloalkyl, C ⁇ -C 6 alkoxy, halo-Ci-C ⁇ alkoxy, C ⁇ -C ⁇ alkylthio, halo-Ci-dalkylthio, d-C 6 alkyl- sulfinyl, halo-C ⁇ -C 6 alkylsulfinyl, d-C ⁇ alkylsulfonyl, halo-C ⁇ -C ⁇ alkylsulfonyl, Ci-d-alkylsulf- onyloxy, halo-CrC 6 alkylsulfonyloxy, C ⁇ -Cealkoxy-C ⁇ -C ⁇ alkyl, halo-C ⁇ -CealkoxyC
  • Ree is hydrogen, Ci-dalkyl, halo-d-dalkyl, d-dcycloalkyl, Crdcycloalkenyl, halo- C 3 -C 6 cycloalkyl, Ci-dalkylsulfinyl, halo-CrC 6 alkylsulfinyl, d-C ⁇ alkylsulfonyl, halo- C ⁇ -C 6 alkylsulfonyl, C ⁇ -Cealkoxy-C ⁇ -C 6 alkyl, halo-C ⁇ -C 6 alkoxy-C ⁇ -C 6 alkyl, d-dalkylthio- C ⁇ -C ⁇ alkyl, halo-C ⁇ -Cealkylthio-C ⁇ -C 6 alkyl, d-dalkylsulfinyl-Ci-dalkyl, halo-C ⁇ -C 6 alkyl- sulfinyl-C ⁇
  • Re is d-dalkyl, halo-Ci-dalkyl, d-dcycloalkyl, halo-d-dcycloalkyl, Ci-dalkoxy, halo- d-dalkoxy, Ci-dalkylthio, halo-d-daikylthio, Ci-dalkylsulfinyl, d-dalkoxy-Ci-dalkyl, halo-d-C ⁇ koxy-d-dalkyl, Ci-dalkylcarbonyl, halo-Ci-dalkylcarbonyl, Ci-dalkoxy- carbonyl, halo-Ci-dalkoxycarbonyl, halogen, N0 2 or CN; aryl-Q-, heterocyclyl-Q-; or aryl-Q- or heterocyclyl-Q-, each of which is, depending on its substitution possibilities, mono- to penta-substituted in the ary
  • R 8 is H or Ci-dalkyl, preferably Ci-dalkyl, especially methyl; (16) a compound of formula (I) wherein R 9 is methyl orfluoromethyl, especially methyl;
  • 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,
  • n, U, A, R 2 , R ⁇ and R 7 are as defined above for formula (I); or a2) reacting a compound of formula
  • n, A, U, R 2 , R 6 and R 7 are as defined for formula (I), optionally in the presence of a base, with a compound of formula which is known or can be prepared in accordance with methods known perse and wherein X, Y, Z, R 3 , * and R 9 are as defined for formula (I); or b) to prepare a compound of formula (I) wherein Y is NHR ⁇ and Z is O, reacting a compound of formula (I) wherein Y is ORi with a compound of formula R ⁇ NH 2 , which is known or can be prepared in accordance with methods known perse and wherein R 8 is as defined for formula (I); or c) to prepare a compound of formula (I) wherein Y is NHR 8 and Z is S, reacting a compound of formula (I) wherein Y is R 8 NH 2 and Z is O with P4S10 or Lawesson's reagent (2,4-bis- (methoxyphenyl)-l
  • R 5 and m are as defined above for formula (I), reacting a compound of formula (I), reacting a compound of formula (I), reacting a compound of formula (I), reacting a compound of formula (I), reacting a compound of formula (I), reacting a compound of formula (I), reacting a compound of formula (I), reacting a compound of formula (I), reacting a compound of formula (I), reacting a compound of formula (I), reacting a compound of formula (I), reacting a compound of formula (I), reacting a compound of formula (I), reacting a compound of formula (I), reacting a compound of formula (I), reacting a compound of formula (I), reacting a compound of formula (I), reacting a compound of formula (I), reacting a compound of formula (I), reacting a compound of formula (I), reacting a compound of formula (I), reacting a compound of formula (I), reacting a compound of formula (I), reacting a compound of formula (I),
  • A, X, Y, Z, R 2 , R 3 , R 4 , Re, R7, R9 and n are as defined for formula (I) and X 2 is a leaving group, especially bromine or iodine, more especially bromine, which is known or can be prepared in accordance with methods known perse, with a compound of formula which is known or can be prepared in accordance with a process known perse and wherein R 5 and m are as defined for formula (I), in the presence of a base or of a transition metal catalyst;
  • A, X, Y, Z, R 2 , R 3 , R , Re, Ree, R7, R9 and n are as defined for formula (I), optionally in the presence of a catalyst, especially copper acetate, with a compound of formula
  • R K and q are as defined for formula (I), which is known or can be prepared in accordance with methods known perse; or
  • DDQ benzoquinone
  • 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 7 AONH 2 (XI) which is known or can be prepared in accordance with methods known perse and wherein A and R? are as defined for formula (I);
  • n, A, R 2 , R 6 and R 7 are as defined for formula (I) and X 2 is a leaving group, especially bromine or iodine, more especially bromine, which is known or can be prepared in accordance with methods known perse, with an arylboric acid derivative of formula (VII); or
  • n, R 2 and R ⁇ are as defined for formula (I) and X 2 is a leaving group, especially bromine or iodine, more especially bromine, with an arylboric acid derivative of formula (VII) to form a compound of formula (X) wherein n, R 2 , R 5 and R 6 are as defined for formula (I), and reacting that compound, optionally in the presence of a base, either with a compound of formula R 7 AONH 2 (XI), or with H 2 NOH or with a salt thereof and then with a compound of formula R 7 AX 2 (IX); or
  • n, R 2 , R 6 , R 7 and X 2 are as defined for formula (VI), with an arylboric acid derivative of formula (VII), and reacting the resulting compound of formula (IV), optionally in the presence of a base, with H 2 NOH or with a salt thereof; or
  • the compounds of formulae (III), (IV), (VI), (VIII) and (X) are especially suitable for the production of pesticidally active end products of formula (I) or of other active ingredients having that partial structure. Insofar as they are novel, those compounds also form part of this invention.
  • the reactions described hereinbefore and hereinafter are carried out in a manner known perse, 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 of 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.
  • Suitable leaving groups Xi in the compounds of formula (II) are, for example, hydroxy, C ⁇ -C 8 alkoxy, halo-C ⁇ -C ⁇ alkoxy, Ci-dalkanoyloxy, mercapto, Ci-dalkylthio, halo-C ⁇ -C 8 alkyl- thio, d-dalkanesulfonyloxy, halo-C ⁇ -C 8 alkanesulfonyloxy, benzenesulfonyloxy, toluene- sulfonyloxy and halogen, preferably toluenesulfonyloxy, trifluoromethanesulfonyloxy 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 unsatu rated cycloalkylamines, basic heterocycies, ammonium hydroxides and carbocyclic amines.
  • DBU ,5-diaza- bicyclo[5.4.0]undec-5-ene
  • the reactants may be reacted with one another as they are, that is to say 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.
  • solvents or diluents include: aromatic, aliphatic and alicyclic hydrocarbons and halogenated hydrocarbons, such as benzene, toluene, xylene, mesitylene, Tetralin, chlorobenzene, dichloro- benzene, bromobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, trichlo- romethane, tetrachloromethane, dichloroethane, trichloroethene and tetrachloro-ethene; 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 mo- noethyl ether, ethylene glycol dimethyl ether,
  • bases used in excess such as triethylamine, pyridine, N-methylmorpholine or N,N-diethylaniline, may also serve as solvents or diluents.
  • the reaction is carried out advantageously in a temperature range of 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.
  • the reaction is preferably carried out under normal pressure.
  • the reaction may also be carried out without a protective gas atmosphere; preferably, however, it is carried out under a protective gas atmosphere, for example nitrogen or argon, especially nitrogen.
  • a protective gas atmosphere for example nitrogen or argon, especially nitrogen.
  • reaction time is not critical; 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.
  • the product is isolated in accordance with customary methods, for example by filtration, crystallisation, distillation or chromatography, or any suitable combination of those methods.
  • 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, especially sodium hydride.
  • the reactants may be reacted with one another as they are, that is to say without the addition of a solvent or diluent, for example in molten form.
  • a solvent or diluent for example in molten form.
  • an inert solvent or diluent or a mixture thereof is advantageous. Examples of such solvents or diluents include those mentioned in Variant a1/a2).
  • the reaction is carried out advantageously in a temperature range of 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.
  • the reaction is preferably carried out under normal pressure.
  • the reaction may be carried out without a protective gas atmosphere; preferably, however, it is carried out under a protective gas atmosphere, for example nitrogen or argon, especially nitrogen.
  • a protective gas atmosphere for example nitrogen or argon, especially nitrogen.
  • reaction time is not critical; 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.
  • the product is isolated in accordance with customary methods, for example by filtration, crystallisation, distillation or chromatography, or any suitable combination of those methods.
  • the reactants may be reacted with one another as they are, that is to say 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.
  • solvents or diluents include: aromatic, aliphatic and alicyclic hydrocarbons and halogenated hydrocarbons, such as benzene, toluene, xylene, mesitylene, Tetralin, chlorobenzene, dichloro- benzene, bromobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, trichlo- romethane, tetrachloromethane, dichloroethane, tiichloroethene and tetrachloro-ethene; 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 preferably carried out under normal pressure.
  • the reaction may be carried out without a protective gas atmosphere; preferably, however, it is carried out under a protective gas atmosphere, for example nitrogen or argon, especially nitrogen.
  • a protective gas atmosphere for example nitrogen or argon, especially nitrogen.
  • the reaction time is not critical; 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.
  • the product is isolated in accordance with customary methods, for example by filtration, crystallisation, distillation or chromatography, or any suitable combination of those methods.
  • Suitable oxidising agents are, for example, sodium perborate, inorganic peroxides, such as hydrogen peroxide, or organic per-acids, such as perbenzoic acid or peracetic acid, or mixtures of organic acids and hydrogen peroxide, for example acetic acid/hydrogen peroxide.
  • the reactants may be reacted with one another as they are, that is to say 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.
  • solvents or diluents include: aromatic, aliphatic and alicyclic hydrocarbons and halogenated hydrocarbons, such as benzene, toluene, xyiene, mesitylene, Tetralin, chlorobenzene, dichloro- benzene, bromobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, trichlo- romethane, tetrachloromethane, dichloroethane, trichloroethene and tetrachloro-ethene; 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 mo- noethyl ether, ethylene glycol dimethyl ether,
  • acids used in excess for example strong organic carboxylic adds, such as unsubstituted or substituted, for example, halo-substituted, d-dalkanecarboxylic acids, e.g. formic acid, acetic acid or propionic acid, may also serve as solvent or diluent.
  • 0°C to approximately +120°C preferably from approximately 0°C to approximately +40°C.
  • the reaction is preferably carried out under normal pressure.
  • the reaction may be carried out without a protective gas atmosphere; preferably, however, it is carried out under a protective gas atmosphere, for example nitrogen or argon, especially nitrogen.
  • reaction time is not critical; 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.
  • the product is isolated in accordance with customary methods, for example by filtration, crystallisation, distillation or chromatography, or any suitable combination of those methods.
  • Suitable leaving groups X 2 in the compounds of formulae (VI), (XII), (XIII) and (XIV) are, for example, hydroxy, Ci-dalkoxy, halo-C ⁇ -C 8 alkoxy, C ⁇ -C 8 alkanoyloxy, mercapto, d-dalkylthio, halo-d-dalkylthio, d-C ⁇ alkanesulfonyloxy, halo-C ⁇ -C 8 alkanesulfonyloxy, benzenesulfonyloxy, toluenesulfonyloxy and halogen, preferably toluenesulfonyloxy, trifluo- romethanesulfonyioxy and halogen, especially halogen, more especially bromine or iodine, especially bromine.
  • Suitable catalysts are especially transition metal catalysts, more especially iron, palladium, ruthenium, rhodium, nickel, zinc or platinum catalysts. Especially suitable are iron(l), nik- kel(0) and palladium(O) catalysts, especially Pd(PPh 3 ) .
  • Suitable bases for facilitating the reaction are, for example, alkali metal or alkaline earth metal hydroxides, hydrides, amides, alkanolates, acetates, carbonates, dialkylamides or al- kyisilylamides, alkylamines, alkylenediamines, unsubstituted or N-alkylated, saturated or unsaturated cycloalkylamines, basic heterocycies, ammonium hydroxides and carbocyclic amines.
  • DBU ,5-diaza- bicyclo[5.4.0]undec-5-ene
  • alkali metal and alkaline earth metal carbonates especially potassium carbonate.
  • the reactants may be reacted with one another as they are, that is to say without the addition of a solvent or a diluent, for example in molten form. Generally, however, the addition of an inert solvent or diluent or a mixture thereof is advantageous.
  • 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, trichloroethene and tetrachloroethe- ne; 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 (dimethoxyethan
  • bases used in excess such as triethylamine, pyridine, N-methylmorpholine or N,N-diethylaniline, may also serve as solvent or diluent.
  • bases used in excess such as triethylamine, pyridine, N-methylmorpholine or N,N-diethylaniline
  • Preferred solvents are water-miscible ethers and water, especially mixtures thereof, more especially ethylene glycol dimethyl ether/H 2 0/tetrahydrofuran.
  • the reaction is advantageously carried out in a temperature range of from approximately 40°C to approximately 180°C, especially from approximately 60°C to approximately 120°C, in many cases in the range from room temperature to the reflux temperature of the reaction mixture.
  • the reaction is preferably carried out under normal pressure.
  • the reaction may be earned out without a protective gas atmosphere; preferably, however, it is carried out under a protective gas atmosphere, for example nitrogen or argon, especially nitrogen.
  • a protective gas atmosphere for example nitrogen or argon, especially nitrogen.
  • reaction time is not critical; preference is given to a reaction duration of from approximately 0.1 to approximately 24 hours, especially from approximately 0.5 to approximately 10 hours.
  • the product is isolated in accordance with customary methods, for example by filtration, crystallisation, distillation or chromatography, or any suitable combination of those methods. Especially preferred conditions for the reaction are described in Examples P3c) and P3d).
  • the reactants may be reacted with one another as they are, that is to say without the addition of a solvent or diluent, for example in molten form.
  • a solvent or diluent for example in molten form.
  • an inert solvent or diluent or a mixture thereof is advantageous. Examples of such solvents or diluents include those mentioned in Variant e).
  • the reaction is advantageously carried out in a temperature range of from approximately 0°C to approximately 180°C, especially from approximately 80°C to approximately 110°C, in many cases in the range from room temperature to the reflux temperature of the reaction mixture.
  • the reaction is preferably carried out in closed vessels or apparatus at elevated pressure.
  • the reaction may be carried out without a protective gas atmosphere; preferably, however, it is carried out under a protective gas atmosphere, for example nitrogen or argon, especially nitrogen.
  • a protective gas atmosphere for example nitrogen or argon, especially nitrogen.
  • reaction time is not critical; preference is given to a reaction duration of from approximately 1 to approximately 100 hours, especially from approximately 80 to approximately 100 hours.
  • a suitable catalyst is required in most cases.
  • suitable catalysts copper or silver salts and copper or silver complexes, especially copper acetate.
  • the product is isolated in accordance with customary methods, for example by filtration, crystallisation, distillation or chromatography, or any suitable combination of those methods.
  • Suitable oxidising agents are oxides, such as Mn0 2 , Pd/C catalysts or benzoquinones, for example 2,3-dichloro-5,6-dicyano-1 ,4-benzoquinone.
  • the reactants may be reacted with one another as they are, that is to say without the addition of a solvent or diluent, for example in molten form.
  • a solvent or diluent for example in molten form.
  • an inert solvent or diluent or a mixture thereof is advantageous.
  • solvents or diluents include those mentioned in Variant e).
  • the reaction is carried out advantageously in a temperature range of from approximately
  • 0°C to approximately 180°C especially from approximately 0°C to approximately 40°C, in many cases in the range from room temperature to the reflux temperature of the reaction mixture.
  • the reaction is preferably carried out under normal pressure.
  • the reaction may be carried out also without a protective gas atmosphere.
  • reaction time is not critical; preference is given to a reaction duration of from approximately 1 to approximately 100 hours, especially from approximately 10 to approximately 20 hours.
  • the product is isolated in accordance with customary methods, for example by filtration, crystallisation, distillation or chromatography, or any suitable combination of those methods.
  • Suitable bases for facilitating the reaction are, for example, those mentioned in
  • the reactants may be reacted with one another as they are, that is to say without the addition of a solvent or diluent, for example in molten form.
  • a solvent or diluent for example in molten form.
  • an inert solvent or diluent or a mixture thereof is advantageous. Examples of such solvents or diluents include those mentioned in Variant a1/a2).
  • the reaction is carried out advantageously in a temperature range of from approximately 0°C to approximately 180°C, especially from approximately 60°C to approximately 120°C, in many cases in the range from room temperature to the reflux temperature of the reaction mixture.
  • the reaction is preferably carried out under normal pressure.
  • the reaction may be carried out also without a protective gas atmosphere; preferably, however, it is carried out under a protedive gas atmosphere, for example nitrogen or argon, especially nitrogen.
  • a protective gas atmosphere for example nitrogen or argon, especially nitrogen.
  • the reaction time is not critical; preference is given to a reaction duration of from approximately 0.1 to approximately 24 hours, especially from approximately 0.5 to approximately 5 hours.
  • the produd is isolated in accordance with customary methods, for example by filtration, crystallisation, distillation or chromatography, or any suitable combination of those methods.
  • the reaction is preferably carried out with hydroxylammonium chloride in ethanol, with pyridine at 90°C.
  • Suitable leaving groups X 3 in the compounds of formula (VIII) are, for example, those listed as examples of Xi in Variants a1/a2). Bromine and iodine are preferred.
  • Suitable bases for facilitating the readion are, for example, those listed in Variants a1/a2).
  • the reactants may be reacted with one another as they are, that is to say without the addition of a solvent or diluent, for example in molten form.
  • a solvent or diluent for example in molten form.
  • an inert solvent or diluent or a mixture thereof is advantageous. Examples of such solvents or diluents include those mentioned in Variants a1/a2).
  • the readion is carried out advantageously in a temperature range of 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.
  • the reaction is preferably carried out under normal pressure.
  • the reaction may be carried out without a protective gas atmosphere; preferably, however, it is carried out under a protedive gas atmosphere, for example nitrogen or argon, especially nitrogen.
  • a protective gas atmosphere for example nitrogen or argon, especially nitrogen.
  • the readion time is not critical; preference is given to a reaction duration of from approximately 0.1 to approximately 24 hours, especially from approximately 0.5 to approximately 5 hours.
  • the produd is isolated in accordance with customary methods, for example by filtration, crystallisation, distillation or chromatography, or any suitable combination of those methods.
  • a compound of formula (VIII) is readed with a compound of formula (IX) at from 0°C to 80°C, especially from 10°C to 60°C, in an inert sol- vent, especially a nitrile, especially acetonitrile, in the presence of a metal carbonate, especially potassium carbonate, and the compound of formula (IV) obtainable in that manner is then readed either according to Variant g1) with h ydroxylammonium chloride to form a compound of formula (III), or the compound of formula (IV) is readed further according to Variant a2).
  • the compounds of formulae (I), (III), (IV), (VIII), (X), (XII), (XIV) and (XV) 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 adive solvent, by chromatography on chiral adsorbents, for example high-pressure liquid chromatography (HPLC) on acetyl cellulose, with the aid of suitable microorganisms, by cleavage 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
  • a number of compounds of formulae (I) to (XV) 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 readion conditions.
  • the invention relates especially to the preparation processes described in Examples P1 to P7.
  • the compounds of formula (I) according to the invention are valuable preventive and/or curative active ingredients having a very advantageous biocidal spedrum 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 insedicidal, ovi- cidal and/or acaricidal adion of the compounds of the invention may manifest itself diredly, i.e.
  • the mentioned animal pests include, for example: of the order Lepidoptera, for example,
  • Amylois spp. Anticarsia gemmatalis, Archips spp., Argyrotaenia spp., Autographa spp., Busseola fusca, Cadra cautella, Carposina nipponensis, Chilo spp., Cho- ristoneura spp., Clysia ambiguella, Cnaphalocrocis spp., Cnephasia spp., Co- chylis spp., Coleophora spp., Crocidolomia binotalis, Cryptophlebia leucotreta,
  • Cydia spp. Diatraea spp., Diparopsis castanea, Earias spp., Ephestia spp., Eu- cosma spp., Eupoecilia ambiguella, Euprodis spp., Euxoa spp., Grapholita spp.,
  • Trichoplusia ni and Yponomeuta spp. of the order Coleoptera, for example, Agriotes spp., Anthonomus spp., Atomaria iinearis, Chaetocnema tibialis, Cosmopolites spp., Curculio spp., Dermestes spp.,
  • Diabrotica spp. Epilachna spp., Eremnus spp., Leptinotarsa decemlineata, Lis- sorhoptrus spp., Melolontha spp., Orycaephilus spp., Otiorhynchus spp.,
  • Phlydinus spp. Popillia spp., Psyliiodes spp., Rhizopertha spp., Scarabeidae,
  • Sitophiius spp. Sitotroga spp., Tenebrio spp., Tribolium spp. and Trogoderma spp.; of the order Orthoptera, for example, Blatta spp., Blattella spp., Gryllotalpa spp.,
  • Haematopinus spp. Linognathus spp., Pediculus spp., Pemphigus spp. and
  • Phylloxera spp. of the order Maliophaga, for example, Damalinea spp. and Trichodedes spp.; of the order Thysanoptera, for example,
  • Frankliniella spp. Hercinothrips spp., Taeniothrips spp., Thrips palmi, Thrips tab- aci and Scirtothrips aurantii; of the order Heteroptera, for example, Cimex spp., Distantiella theobroma, Dys- dercus spp., Euchistus spp., Eurygasterspp., Leptocorisa spp., Nezara spp., Pi- esma spp., Rhodnius spp., Sahlbergella singularis, Scotinophara spp.
  • Tria- toma spp. of the order Homoptera, for example, Aleurothrixus fioccosus, Aleyrodes brassicae, Aonidiella spp., Aphididae, Aphis spp., Aspidiotus spp., Bemisia tabaci, Ceroplaster spp., Chrysomphalus aonidium, Chrysomphalus dictyospermi, Coccus hesperidum, Empoasca spp., Eriosoma larigerum, Erythroneura spp., Gas- cardia spp., Laodelphax spp., Lecanium comi, Lepidosaphes spp., Macrosiphus spp., Myzus spp., Nephotettix spp., Nilaparvata spp., Paratoria spp., Pemphigus spp.
  • Siphonaptera for example, Ceratophyllus spp. and Xenopsylla che- opis
  • Thysanura for example, Lepisma saccharina
  • Acarina for example, Acarus siro, Aceria sheldoni, Aculus pointedendali, Ambiyomma spp., Argas spp., Boophilus spp., Brevipalpus spp., Bryobia praetiosa, Calipitrimerus spp., Chorioptes spp., Dermanyssus gallinae, Eotetranychus ca ⁇ ini, Eriophyes spp., Hyalomma spp., Ixodes spp., Olygonychus pratensis, Ornithodoros spp., Panonychus spp., Phyllocopt
  • the mentioned phytopathogenic fungi include, for example: of the class of the Fungi imperfedi, 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,
  • Rhizodonia spp. Hemileia spp. and Pucdnia 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 or 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 active ingredients 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, Plu- tella 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, Plu- tella 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 emulsifiable concentrates, suspension concentrates, diredly 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 emulsifiable concentrates, suspension concentrates, diredly 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-adive 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-adive compounds (surfactants).
  • Suitable solvents are, for example: optionally partially hydrogenated aromatic hydrocarbons, preferably the fractions of alkylbenzenes containing 8 to 12 carbon atoms, such as xyiene mixtures, alkylated naphthalenes or tetrahydronaph- thalene, aliphatic or cycloaliphatic hydrocarbons, such as paraffins or cyclohexane, alcohols, such as ethanol, propanol or butanol, glycols and their ethers and esters, such as propylene glycol, dipropylene glycol ether, ethylene glycol or ethylene glycol monomethyl or monoethyl ether, ketones, such as cyclohexanone, isophorone or diacetone alcohol, strongly polar solvents, such as N-methyl- pyrrolid-2-one, dimethyl sulfoxide or N,N-dimethylformamide, water, vegetable oils or epoxidised vegetable oils, such as rape
  • the solid carriers used are normally natural mineral fillers, such as calcite, talcum, kaolin, montmorillonite or attapulgite.
  • calcite calcite
  • talcum kaolin
  • montmorillonite kaolin
  • attapulgite a highly dispersed silicic acids or highly dispersed absorbent polymers.
  • Suitable granulated adsorp- tive carriers are porous types, such as pumice, broken brick, sepiolite or bento- nite; and suitable nonsorbent carriers are calcite or sand, in addition, a great number of granulated materials of inorganic or organic nature can be used, especially dolomite or pulverised plant residues.
  • suitable surface- active compounds are non-ionic, cationic and/or anionic surfactants or mixtures of surfactants having good emulsifying, dispersing and wetting properties.
  • the sur- fadants listed below are to be regarded merely as examples; many more surfactants customarily employed in formulation technology and suitable for use according to the invention are described in the relevant literature.
  • Non-ionic surfadants are preferably polyglycol ether derivatives of aliphatic or cy- cloaliphatic alcohols, saturated or unsaturated fatty adds and alkylphenols, said derivatives containing 3 to 30 glycol ether groups and 8 to 20 carbon atoms in the (aliphatic) hydrocarbon moiety and 6 to 18 carbon atoms in the alkyl moiety of the alkylphenols.
  • non-ionic surfactants are water-soluble adduds of polyethylene oxide with polypropylene glycol, ethylenediamino-polypropylene glycol and alkylpolypropylene glycol containing 1 to 10 carbon atoms in the alkyl chain, which adduds contain 20 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups. These compounds usually contain 1 to 5 ethylene glycol units per propylene glycol unit.
  • nonyl- phenol polyethoxyethanols castor oil polyglycol ethers, polypropylene/polyethylene oxide adducts, tributylphenoxy polyethoxyethanol, polyethylene glycol and octylphenoxypolyethoxyethanol.
  • Fatty acid esters of poiyoxyethylene sorbitan e.g. poiyoxyethylene sorbitan trioleate, are also suitable non-ionic surfadants.
  • Cationic surfactants are preferably quaternary ammonium salts which contain, as substituent, at least one d-ds-alky!
  • the salts are preferably in the form of halides, methyl sulfates or ethyl sulfates. Examples are stearyltrimethylammonium chloride and benzyl-di(2-chloroethyl)- ethylammonium bromide.
  • Suitable soaps are the alkali metal salts, alkaline earth metal salts and unsubstituted or substituted ammonium salts of higher fatty acids (C 10 -C 22 ), e.g. the sodium or potassium salts of oleic or stearic acid, or of natural fatty acid mixtures which can be obtained e.g. from coconut oil or tall oil; mention may also be made of fatty acid methyltaurine salts.
  • fatty sulfonates or sulfates are usually in the form of alkali metal salts, alkaline earth metal salts or unsubstituted or substituted ammonium salts and generally contain a d-dsalkyl radical, the alkyl moiety of acyl radicals also being included; there may be mentioned by way of example the sodium or calcium salt of lignosulfonic acid, of do- decyl sulfate or of a mixture of fatty alcohol sulfates obtained from natural fatty acids.
  • These compounds also comprise the salts of sulfated and sulfonated fatty alcohol ethylene oxide adducts.
  • the sulfonated benzimidazole derivatives preferably contain two sulfonic acid groups and one fatty acid radical containing approximately 8 to 22 carbon atoms.
  • alkylarylsulfonates are the sodium, calcium or triethanolammonium salts of dodecylbenzenesulfonic acid, di- butylnaphthalenesulfonic acid or of a condensate of naphthalenesulfonic acid and formaldehyde.
  • corresponding phosphates e.g. salts of the phosphoric acid ester of an addud of p-nonylphenol with 4 to 14 mol of ethylene oxide, or phospholipids.
  • 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 surfadants (in each case percentages are by weight).
  • 0 to 25%, preferably 0.1 to 20%, of the composition will preferably be formulated as concentrates
  • the end user will normally employ dilute formulations which have considerably lower adive ingredient concentrations.
  • Preferred formulations have especially the following composition (throughout, 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 adive 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 adive 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 in- sedicidal, acaricidal and/or fungicidal adive ingredients.
  • suitable additional adive ingredients include representatives of the following classes of compounds: organophosphorus compounds, nitrophenols and derivatives, for- mamidines, 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 adive ingredients for obtaining special effects, for example badericides, nematicides, moliuscicides or seledive 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 adive ingredients, for example to a specific particle size, and in the presence of at least one adjuvant, for example by intimately mixing and/or grinding the active ingredient or mixture of adive ingredients with the adjuvants).
  • 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 seleded in accordance with the intended objedives 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 adive 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 protedion 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 adive 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 adive ingredient is incorporated 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 proteding plant propagation material, e.g. seed, such as fruit, tubers or grains, or plant cuttings, from fungal infedions 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.
  • P1a 40 g of pyridine are added dropwise to 54 g of 4-bromophenylacetic acid in 255 g of acetic anhydride. The reaction mixture is stirred at 140°C for 20 hours and then concentrated. 250 ml of concentrated hydrochloric acid are added to the residue and the mixture is heated under reflux for 3 hours. The reaction mixture is poured into ice-water and extracted several times with ethyl acetate. The combined organic phases are washed with water and brine, dried and concentrated. Distillation of the crude product yields 38 g of 1-(4- bromophenyl)-propan-2-one having a boiling point of 70°C/0.2 bar.
  • P1b) 38 g of 1 -(4-bromophenyl)-propan-2-one and 23 g of isopentyl nitrite are placed in 250 ml of methanol. 39 g of a 30% solution of sodium methanolate in methanol are added dropwise with ice-cooling. The mixture is then stirred at room temperature for 2 hours. The reaction mixture is concentrated, water is added and the mixture is acidified with 2N hydrochloric acid. The suspension is filtered. The filter residue is taken up in ethyl acetate, washed with water, dried and concentrated.
  • Example P1e The other compounds listed in Table 1-1 may also be prepared in a manner analogous to that described in Examples P1a to P1d. In the column “phys. data", the temperatures indicated in each case denote the melting point of the compound in question; c- C 3 H 3 is cyclopropyl. Table 1 -1 : Compounds of formula
  • Example P1h The other compounds listed in Table 1-2 may also be prepared in a manner analogous to that described above. In the column "m.p.”, the temperatures indicated in each case denote the melting point in °C of the compound in question; c-C 3 H 3 is cyclopropyl.
  • Example P1p The other compounds listed in Table 1 -3 may also be prepared in a manner analogous to that described above.
  • the temperatures indicated in each case denote the melting point of the compound in question; c-C 3 H 3 is cyclopropyl.
  • Example P1n The other compounds listed in Table 1-4 may also be prepared in a manner analogous to that described above. In the column “phys. data", the temperatures indicated in each case denote the melting point in °C of the compound in question.
  • reaction of 3-(4-bromophenyl)-2- hydroximino-3-ethoximinopropane and 2-( ⁇ -bromo-o-tolyl)-2-methoxyimino-acetic acid methyl ester yields as product 2- ⁇ 2-[2-(4-bromo-phenyl)-2-ethoxyimino-1-methyl- ethylideneaminooxymethyl]-phenyl ⁇ -3-methoxyimino-acetic acid methyl ester having a melting point of 103-104°C (compound 2.2).
  • Example P2c ⁇ The other compounds listed in Table 2 may also be prepared in a manner analogous to that described in Examples P2a and P2b; c-C 3 H 3 and c-C 3 H 5 are cyclopropyl.
  • Example P3b ⁇ The other compounds listed in Table 3-1 may also be prepared in a manner analogous to that described above.
  • the column "m.p.” indicates the melting points in °C.
  • Example P3g The other compounds listed in Tables 3-2 to 89 may also be prepared in a manner analogous to that described in Examples P3c) to P3f). c-C 3 H 3 and c-C 3 H 5 are cyclopropyl. Table 3-2: Compounds of general formula
  • AR 7 is CH 3 and the combination of substituents X, Y, (R 5 ) m and (R ⁇ ) n for each individual compound corresponds to a line of Table A.
  • Table 5 Compounds of formula (la) wherein AR 7 is CH 2 CH 3 and the combination of substituents X, Y, (R 5 )m and (R ⁇ ) n for each individual compound corresponds to a line of Table A.
  • Table 7 Compounds of formula (la) wherein AR 7 is CH 2 C ⁇ CH and the combination of substituents X, Y, (R 5 ) ⁇ » and (R ⁇ ) worship for each individual compound corresponds to a line of Table A.
  • Table 8 Compounds of formula (la) wherein AR 7 is CH 2 CH 2 CH 3 and the combination of substituents X, Y, (Rs) m and (R ⁇ ) n for each individual compound corresponds to a line of Table A.
  • Table 9 Compounds of formula (la) wherein AR 7 is CH(CH 3 ) 2 and the combination of substituents X, Y, (R 5 )m and (R ⁇ ) n for each individual compound corresponds to a line of Table A.
  • Table 10 Compounds of formula (la) wherein AR 7 is CH 2 CH 2 CH 2 CH 3 and the combination of substituents X, Y, (R 5 )m and (R 6 ) n for each individual compound corresponds to a line of Table A.
  • Table 11 Compounds of formula (la) wherein AR 7 is CH(CH 3 )(CH 2 CH 3 ) and the combination of substituents X, Y, (R 5 )m and (R ⁇ ) n for each individual compound corresponds to a line of Table A.
  • Table 12 Compounds of formula (la) wherein AR 7 is C(CH 3 ) 3 and the combination of substituents X, Y, (Rs)m and (R 6 ) n for each individual compound corresponds to a line of Table A.
  • Table 13 Compounds of formula (la) wherein AR 7 is n-C 6 H i3 and the combination of substituents X, Y, (R 5 ) t n and (R ⁇ ) n for each individual compound corresponds to a line of Table A.
  • Table 14 Compounds of formula (la) wherein AR 7 is CH 2 F and the combination of substituents X, Y, ( s ) m and (R 6 ) n for each individual compound corresponds to a line of Table A.
  • Table 15 Compounds of formula (la) wherein AR 7 is CHF 2 and the combination of substituents X, Y, (Rs)m and (R 6 )n for each individual compound corresponds to a line of Table A.
  • Table 16 Compounds of formula (la) wherein AR 7 is CH 2 CF 3 and the combination of substituents X, Y, (R 5 ) m and (R ⁇ )n for each individual compound corresponds to a line of Table A.
  • Table 23 Compounds of formula (la) wherein AR 7 is CH ⁇ i ⁇ H ⁇ and the combination of substituents X, Y, (R 5 ) m and (R 6 )n for each individual compound corresponds to a line of Table A.
  • Table 24 Compounds of formula (la) wherein AR 7 is CH 2 -cyclopropyl-2,2-CI 2 and the combination of substituents X, Y, (R 5 ) m and (R 6 )n for each individual compound corresponds to a line of Table A.
  • Table 25 Compounds of formula (la) wherein AR 7 is CH 2 -cyclopropyl and the combination of substituents X, Y, (R 5 ) m and (R 6 ) n for each individual compound corresponds to a line of Table A.
  • Table 26 Compounds of formula (la) wherein AR 7 is CH 2 CN and the combination of substituents X, Y, (R 5 )m and (R ⁇ ) n for each individual compound corresponds to a line of Table A.
  • Table 27 Compounds of formula (la) wherein AR 7 is CH 2 COOCH 3 and the combination of substituents X, Y, (R 5 ) m and (R ⁇ )n for each individual compound corresponds to a line of Table A.
  • Table 28 Compounds of formula (la) wherein AR 7 is CH 2 COOC 2 H 5 and the combination of substituents X, Y, (R 5 ) m and (R 6 )n for each individual compound corresponds to a line of Table A.
  • Table 29 Compounds of formula (la) wherein AR 7 is CH 2 COO-iso-C 3 H 7 and the combination of substituents X, Y, (R 5 ) m and (R 6 ) n for each individual compound corresponds to a line of Table A.
  • Table 30 Compounds of formula (la) wherein AR 7 is CH(CH 3 )COOC 2 H 5 and the combination of substituents X, Y, (R 5 )m and (R 6 ) n for each individual compound corresponds to a line of Table A.
  • Table 34 Compounds of formula (la) wherein AR 7 is CH 2 C 6 H 5 and the combination of substituents X, Y, (R 5 ) m and (R 6 ) n for each individual compound corresponds to a line of Table A.
  • Table 35 Compounds of formula (la) wherein AR 7 is CH 2 C ⁇ H 4 -2-F and the combination of substituents X, Y and (R 5 ) m for each individual compound corresponds to a line of Table A.
  • Table 36 Compounds of formula (la) wherein AR 7 is CH 2 C 6 H 4 -3-F and the combination of substituents X, Y, (R 5 )m and (R 6 )n for each individual compound corresponds to a line of Table A.
  • Table 37 Compounds of formula (la) wherein AR 7 is CH 2 C ⁇ H -4-F and the combination of substituents X, Y, (R 5 ) m and (R ⁇ ) n for each individual compound corresponds to a line of Table A.
  • Table 38 Compounds of formula (la) wherein AR 7 is CH 2 C ⁇ H 4 -2-CI and the combination of substituents X, Y, (R 5 ) m and (R ⁇ ) n for each individual compound corresponds to a line of Table A.
  • Table 39 Compounds of formula (la) wherein AR 7 is CH 2 C ⁇ H 4 -3-CI and the combination of substituents X, Y, (R 5 ) m and (R 6 )n for each individual compound corresponds to a line of Table A.
  • Table 40 Compounds of formula (la) wherein AR 7 is CH 2 C ⁇ H 4 -4-CI and the combination of substituents X, Y, (R 5 ) m and (R 6 ) n for each individual compound corresponds to a line of Table A.
  • Table 41 Compounds of formula (la) wherein AR 7 is CH 2 C 6 H 4 -2-Br and the combination of substituents X, Y, (R 5 ) m and (R 6 )n for each individual compound corresponds to a line of Table A.
  • Table 42 Compounds of formula (la) wherein AR is CH 2 C 6 H 4 -3-Br and the combination of substituents X, Y, (R 5 ) and (R ⁇ )n for each individual compound corresponds to a line of Table A.
  • Table 43 Compounds of formula (la) wherein AR 7 is CH 2 C 6 H 4 -4-Br and the combination of substituents X, Y, (R 5 )m and (R 6 )n for each individual compound corresponds to a line of Table A.
  • Table 44 Compounds of formula (la) wherein AR 7 is CH 2 C ⁇ Hr2-CF 3 and the combination of substituents X, Y, (R 5 )m and (R 6 )n for each individual compound corresponds to a line of Table A.
  • Table 45 Compounds of formula (la) wherein AR 7 is CH 2 C 6 H 4 -3-CF 3 and the combination of substituents X, Y, (R 5 ) m and (R ⁇ ) n for each individual compound corresponds to a line of Table A.
  • Table 46 Compounds of formula (la) wherein AR 7 is CH 2 C ⁇ H 4 -4-CF 3 and the combination of substituents X, Y, (R 5 )m and (R ⁇ ) n for each individual compound corresponds to a line of Table A.
  • Table 47 Compounds of formula (lb) wherein AR 7 is CH 3 and the combination of substituents X, Y, (R 5 ) m and (R 6 ) n for each individual compound corresponds to a line of Table B.
  • Table 48 Compounds of formula (lb) wherein AR 7 is CH 2 CH 3 and the combination of substituents X, Y, (R 5 ) and (R 6 )n for each individual compound corresponds to a line of Table B.
  • Table 50 Compounds of fo ⁇ nula (lb) wherein AR 7 is CH 2 C ⁇ CH and the combination of substituents X, Y, (R 5 ) m and (R ⁇ ) n for each individual compound corresponds to a line of Table B.
  • Table 51 Compounds of formula (lb) wherein AR 7 is CH 2 CH 2 CH 3 and the combination of substituents X, Y, (R 5 ) m and (R ⁇ ) n for each individual compound corresponds to a line of Table B.
  • Table 52 Compounds of formula (lb) wherein AR 7 is CH(CH 3 ) 2 and the combination of substituents X, Y, (R 5 ) m and (R ⁇ ) n for each individual compound corresponds to a line of Table B.
  • Table 53 Compounds of formula (lb) wherein AR 7 is CH 2 CH 2 CH 2 CH 3 and the combination of substituents X, Y, (R 5 )m and (R ⁇ ) n for each individual compound corresponds to a line of Table B.
  • Table 54 Compounds of formula (lb) wherein AR 7 is CH(CH 3 )(CH 2 CH 3 ) and the combination of substituents X, Y, (R s ) m and (R ⁇ ) ⁇ for each individual compound corresponds to a line of Table B.
  • Table 55 Compounds of formula (lb) wherein AR 7 is C(CH 3 ) 3 and the combination of substituents X, Y, (R 5 ) m and (R ⁇ ) n for each individual compound corresponds to a line of Table B.
  • Table 56 Compounds of formula (lb) wherein AR 7 is n-C 6 H 13 and the combination of substituents X, Y, (R 5 )m and (R ⁇ ) n for each individual compound corresponds to a line of Table B.
  • Table 57 Compounds of formula (lb) wherein AR 7 is CH 2 F and the combination of substituents X, Y, (R 5 )m and (R ⁇ ) utilizat for each individual compound corresponds to a line of Table B.
  • Table 58 Compounds of formula (lb) wherein AR 7 is CHF 2 and the combination of substituents X, Y, (R 5 )m and (R ⁇ ) n for each individual compound corresponds to a line of Table B.
  • Table 59 Compounds of formula (lb) wherein AR 7 is CH 2 CF 3 and the combination of substituents X, Y, (R 5 ) m and (R ⁇ )n for each individual compound corresponds to a line of Table B.
  • Table 66 Compounds of formula (lb) wherein AR 7 is CH 2 Si(CH 3 ) 3 and the combination of substituents X, Y, (R 5 ) m and (R 6 )n for each individual compound corresponds to a line of Table B.
  • Table 67 Compounds of formula (lb) wherein AR 7 is CH 2 -cyclopropyl-2,2-CI 2 and the combination of substituents X, Y, (R 5 ) and (R 6 ) n for each individual compound corresponds to a line of Table B.
  • Table 68 Compounds of fo ⁇ nula (lb) wherein AR 7 is CH 2 -cyclopropyl and the combination of substituents X, Y, (R 5 ) and (R 6 )n for each individual compound corresponds to a line of Table B.
  • Table 69 Compounds of formula (lb) wherein AR is CH 2 CN and the combination of substituents X, Y, (R 5 ) m and (R 6 ) n for each individual compound corresponds to a line of Table B.
  • Table 70 Compounds of fo ⁇ nula (lb) wherein AR 7 is CH 2 COOCH 3 and the combination of substituents X, Y, (R 5 ) m and (R 6 )n for each individual compound corresponds to a line of Table B.
  • Table 71 Compounds of formula (lb) wherein AR 7 is CH 2 COOC 2 H 5 and the combination of substituents X, Y, (R 5 ) m and (R ⁇ )n for each individual compound corresponds to a line of Table B.
  • Table 72 Compounds of formula (lb) wherein AR 7 is CH 2 COO-iso-C 3 H 7 and the combination of substituents X, Y, (R 5 ) m and (R 6 ) n for each individual compound corresponds to a line of Table B.
  • Table 73 Compounds of fo ⁇ nula (lb) wherein AR 7 is CH(CH 3 )COOC 2 H 5 and the combination of substituents X, Y, (R 5 ) m and (R 6 ) n for each individual compound corresponds to a line of Table B.
  • Table 77 Compounds of formula (lb) wherein AR 7 is CH 2 C 6 H 5 and the combination of substituents X, Y, (R 5 ) m and (R 6 )n for each individual compound corresponds to a line of Table B.
  • Table 78 Compounds of formula (lb) wherein AR 7 is CH 2 C ⁇ H 4 -2-F and the combination of substituents X, Y and (R 5 )m for each individual compound corresponds to a line of Table B.
  • Table 79 Compounds of fo ⁇ nula (lb) wherein AR 7 is CH 2 C 6 H 4 -3-F and the combination of substituents X, Y, (R 5 ) m and (R 6 ) n for each individual compound corresponds to a line of Table B.
  • Table 80 Compounds of formula lb) wherein AR 7 is CH 2 C 6 H 4 -4-F and the combination of substituents X, Y, (R 5 )m and (R ⁇ ) n or each individual compound corresponds to a line of Ta- ble B.
  • Table 81 Compounds of formula Ib) wherein AR 7 is CH 2 C ⁇ H 4 -2-CI and the combination of substituents X, Y, (R 5 )m and (R 6 ) n or each individual compound corresponds to a line of Ta- ble B.
  • Table 82 Compounds of formula Ib) wherein AR 7 is CH 2 C ⁇ H4-3-CI and the combination of substituents X, Y, (R 5 ) m and (R 6 ) n or each individual compound corresponds to a line of Ta- ble B.
  • Table 83 Compounds of formula Ib) wherein AR 7 is CH 2 C ⁇ H 4 -4-CI and the combination of substituents X, Y, (R 5 ) m and (R 6 ) n or each individual compound corresponds to a line of Ta- ble B.
  • Table 84 Compounds of formula Ib) wherein AR 7 is CH 2 C 6 H 4 -2-Br and the combination of substituents X, Y, (R 5 ) and (R ⁇ ) n or each individual compound corresponds to a line of Ta- ble B.
  • Table 85 Compounds of formula Ib) wherein AR 7 is CH 2 C ⁇ H 4 -3-Br and the combination of substituents X, Y, (R 5 ) m and (R 6 ) n or each individual compound corresponds to a line of Ta- ble B.
  • Table 86 Compounds of formula Ib) wherein AR 7 is CH 2 C ⁇ H 4 -4-Br and the combination of substituents X, Y, (R 5 ) m and (R 6 ) n or each individual compound corresponds to a line of Ta- ble B.
  • Table 87 Compounds of formula Ib) wherein AR is CH 2 C 6 H 4 -2-CF 3 and the combination of substituents X, Y, (R 5 ) m and (R 6 ) n or each individual compound corresponds to a line of Ta- ble B.
  • Table 88 Compounds of formula Ib) wherein AR 7 is CH 2 C 6 H 4 -3-CF 3 and the combination of substituents X, Y, (R 5 )m and (R 6 )n or each individual compound corresponds to a line of Ta- ble B.
  • Table 89 Compounds of fo ⁇ nula Ib) wherein AR 7 is CH 2 C 6 H 4 -4-CF 3 and the combination of substituents X, Y, (R 5 )m and (R 6 ) n or each individual compound corresponds to a line of Ta- ble B.
  • Table B
  • Example F1 Emulsifiable concentrates a) b) c) active ingredient 25% 40% 50% calcium dodecylbenzenesulfonate 5% 8% 6% castor oil polyethylene glycol ether 5% . . (36 mol of ethylene oxide) tributylphenol polyethylene glycol ether 12% 4% (30 mol of ethylene oxide) cyclohexanone 15% 20% xylene mixture 65% 25% 20%
  • Finely ground active ingredient is mixed with adjuvants, affording an emulsifiable concentrate from which emulsions of any desired concentration can be obtained by dilution with water.
  • ExamDle F2 Solutions a) b) c) d) active ingredient 80% 10% 5% 95% ethylene glycol monomethyl ether 20% - - - polyethylene glycol (mol. wt. 400) - 70% - -
  • N-methylpyrrolid-2-one 20% - - epoxidised coconut oil - - 1% 5% benzine (boiling range: 160-190°C ) - - 94% - Finely ground active ingredient is mixed with adjuvants, affording a solution that is suitable for application in the form of microdrops.
  • the active ingredient is dissolved in dichloromethane, the solution is sprayed onto the carrier mixture and the solvent is evaporated off in vacuo.
  • Example F4 Dusts a) b) active ingredient 2% 5% highly dispersed silicic acid 1% 5% talcum 97% . kaolin - 90%
  • Ready-for-use dusts are obtained by mixing the active ingredient and carriers.
  • Example F5 Wettable powders a) b) c) active ingredient 25% 50% 75% sodium lignosulfonate 5% 5% - sodium lauryl sulfate 3% - 5% sodium diisobutylnaphthalenesulfonate - 6% 10% octylphenol polyethylene glycol ether - 2% - (7-8 mol of ethylene oxide) highly dispersed silicic acid 5% 10% 10% kaolin 62% 27% .
  • Example F6 Emulsifiable concentrate active ingredient 10% octylphenol polyethylene glycol ether 3%
  • Finely ground active ingredient is mixed with the adjuvants, affording an emulsifiable concentrate from which emulsions of any desired concentration can be obtained by dilution with water.
  • Example F7 Dusts a) b) active ingredient 5% 8% talcum 95% kaolin - 92%
  • Ready-to-use dusts are obtained by mixing the active ingredient and carriers and grinding the mixture in a suitable mill.
  • Example F8 Extruder granules active ingredient 10% sodium lignosulfonate 2% carboxymethylcellulose 1 % kaolin 87%
  • Active ingredient is mixed with the adjuvants, and the mixture is ground and moistened with water, extruded and granulated, and the granules are dried in a stream of air.
  • Example F9 Coated granules active ingredient 3% polyethylene glycol (mol. wt. 200) 3% kaolin 94%
  • Example F10 Suspension concentrate active ingredient 40% ethylene glycol 10% nonylphenol polyethylene glycol ether 6%
  • Finely ground active ingredient is mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired concentration can be obtained by dilution with water.
  • Example B1 Action against Phvtophthora infestans on tomatoes a) Curative action
  • a wettable powder formulation of the test compound is poured at a concentration of 60 ppm (based on the volume of soil) onto 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 specks appear, the number and size of which are used to evaluate the effectiveness of the test compounds.
  • Example B2 Action against Plasmooara viticola (Bert, et Curt.') (Bert, et DeTonn on vines a) Residual-preventive action
  • Vine cuttings of the "Chasselas" variery are cultivated in a greenhouse.
  • 3 plants are sprayed with a mixture comprising the active ingredient in a concentration of 200 ppm.
  • the plants are uniformly infected on the undersides of the leaves with a spore suspension of the fungus.
  • the plants are then kept in a humidity chamber for 8 days. After that time, distinct 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.
  • 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 a mixture 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 from Tables 1 to 89 exhibit an infestation of 20% or less.
  • 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. 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.
  • Example B4 Action against Erysiphe graminis on barley a) Residual-protective action
  • Barley plants about 8 cm in height are sprayed to drip point with an aqueous spray mixture (0.02% active ingredient) 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.
  • Wheat plants are sprayed at the 3-leaf stage with a spray mixture (60 ppm a.i.) prepared from a wettable powder formulation of the test compounds (2.8:1). 24 hours later, the treated plants are infected with a conidia suspension of the fungus. The plants are then incubated for 2 days at 90-100 % relative humidity and placed in a greenhouse at 20-24°C for a further 10 days. Fungal infestation is evaluated 13 days after infection. Using the compounds 3-2.47, 3-2.61, 3-2.85, 3-2.88, 3-2.89 and 3-2.72, less than 1 % of the wheat plants exhibit infestation.
  • Example B6 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.
  • 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.
  • Example B8 Action against Heliothis virescens
  • Young soybean plants are sprayed with an aqueous emulsion spray mixture comprising 100 ppm of test compound. After the spray-coating has dried, the plants are populated with 10 caterpillars of Heliothis virescens 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.
  • Example B9 Action against Spodoptera littoralis
  • Young soybean plants are sprayed with an aqueous emulsion spray mixture comprising 100 ppm of test compound. After the spray-coating has dried, the plants are populated with 10 caterpillars of Spodoptera littoralis 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.
  • Example B10 Action against Tetranychus 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 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 untreated plants with that on untreated plants.

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Abstract

L'invention concerne des composés représentés par la formule (I), dans laquelle X représente soit CH ou N, Y représente OR1 et Z représente O; soit N, Y représente NHR8 et Z représente O, S ou S(=O); U représente (a) ou (b); R1 représente H ou un alkyle C1-C4; R2 représente par exemple H, un alkyle C1-C4 ou un halo-C1-C4 alkyle; R3 et R4 représentent par exemple H, un alkyle C1-C4 ou un alkoxy C1-C4; l représente 0, 1 ou 2; R5 et R6 représentent par exemple un alkyle C1-C6, un halo-C1-C6 alkyle, un cycloalkyle C3-C6, un cycloalcényle C3-C6, un halo-C3-C6 cycloalkyle, un alkoxy C1-C6, un halo-C1-C6 alkoxy ou un alkylthio C1-C6; R55 représente par exemple un alkyle C1-C6, un halo-C1-C6 alkyle, un cycloalkyle C3-C6 ou un cycloalcényle C3-C6; R66 représente par exemple un hydrogène, un alkyle C1-C6, un halo-C1-C6 alkyle, un cycloalkyle C3-C6, un cycloalcényle C3-C6, un halo-C3-C6 cycloalkyle, un alkylsulfinyle C1-C6 ou un halo-C1-C6 alkylsulfinyle; m est égal à 0, 1, 2, 3, 4 ou 5; n est égal à 0, 1, 2, 3 ou 4; q est égal à 0, 1, 2, 3 ou 4; A est une liaison directe, un alkylène C1-C10, -C(=O)-, -C(=S)- ou un halo-C1-C10 alkylène, et R7 représente un radical R10; A représente par exemple un alkylène C1-C10 et R7 représente -CN, OR10, N(R10)2 ou -S(=O)pR10; R8 représente H ou un alkyle C1-C4; R9 représente un méthyle, un fluorométhyle ou un difluorométhyle; R10 représente par exemple H, un alkyle C1-C6, un alcényle C2-C8, un alcynyle C2-C8 ou un cycloalkyle C3-C6; l'invention concerne également, le cas échéant, leurs isomères E/ Z, leurs mélanges d'isomères E/ Z et/ ou leurs tautomères éventuels se présentant dans chaque cas sous une forme libre ou sous forme de sel, ces composés pouvant être utilisés comme matières actives agrochimiques.
PCT/EP1997/007122 1996-12-20 1997-12-18 Derives d'ether o-benzyl-oxime utilises comme pesticides Ceased WO1998028262A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU57600/98A AU5760098A (en) 1996-12-20 1997-12-18 O-benzyl oxime ether derivatives as pecticides

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Application Number Priority Date Filing Date Title
CH3139/96 1996-12-20
CH313996 1996-12-20

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WO1998028262A1 true WO1998028262A1 (fr) 1998-07-02

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AU (1) AU5760098A (fr)
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000017155A1 (fr) * 1998-09-22 2000-03-30 Bayer Aktiengesellschaft Composés de bis-oxime pesticides

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1995018789A1 (fr) * 1994-01-05 1995-07-13 Ciba-Geigy Ag Pesticides
WO1995021154A2 (fr) * 1994-02-04 1995-08-10 Basf Aktiengesellschaft Derives d'acide acetique phenylique, leur procede de preparation, produits intermediaires a cet effet et agents les contenant
WO1996016026A1 (fr) * 1994-11-17 1996-05-30 Novartis Ag Derives d'ether d'oxime d'o-benzyle et leur utilisation en tant que pesticides
WO1997001530A1 (fr) * 1995-06-27 1997-01-16 Novartis Ag Derives d'ether d'oxime o-benzylique et leur utilisation dans des compositions antiparasitaires a usage agricole

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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WO2000017155A1 (fr) * 1998-09-22 2000-03-30 Bayer Aktiengesellschaft Composés de bis-oxime pesticides
US6525092B1 (en) 1998-09-22 2003-02-25 Bayer Aktiengsellschaft Pesticidal bis-oxime compounds

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