WO1998028262A1 - O-benzyl oxime ether derivatives as pecticides - Google Patents

O-benzyl oxime ether derivatives as pecticides 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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halo
formula
alkyl
compound
dalkyl
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PCT/EP1997/007122
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French (fr)
Inventor
Ottmar Franz HÜTER
Saleem Farooq
Stephan Trah
Henry Szczepanski
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Novartis Ag
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Priority to AU57600/98A priority Critical patent/AU5760098A/en
Publication of WO1998028262A1 publication Critical patent/WO1998028262A1/en

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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

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); U is (a) or (b); R1 is H or C1-C4alkyl; R2 is, for example, H, C1-C4alkyl or halo-C1-C4alkyl; R3 and R4 are, for example, H, C1-C4alkyl or C1-C4alkoxy; l is 0, 1 or 2; R5 and R6 are, for example, C1-C6alkyl, halo-C1-C6alkyl, C3-C6cycloalkyl, C3-C6cycloalkenyl, halo-C3-C6cycloalkyl, C1-C6alkoxy, halo-C1-C6alkoxy or C1-C6alkylthio; R55 is, for example, C1-C6alkyl, halo-C1-C6alkyl, C3-C6cycloalkyl or C3-C6cycloalkenyl; R66 is, for example, hydrogen, C1-C6alkyl, halo-C1-C6alkyl, C3-C6cycloalkyl, C3-C6cycloalkenyl, halo-C3-C6cycloalkyl, C1-C6alkylsulfinyl or halo-C1-C6alkylsulfinyl; m is 0, 1, 2, 3, 4, or 5; n is 0, 1, 2, 3 or 4; q is 0, 1, 2, 3 or 4; A is a direct bond, C1-C10alkylene, -C(=O)-, -C(=S)- or halo-C1-C10alkylene and R7 is a radical R10; or A is, for example, C1-C10alkylene and R7 is -CN, OR10, N(R10)2 or -S(=O)pR10; R8 is H or C1-C4alkyl; R9 is methyl, fluoromethyl or difluoromethyl; R10 is, for example, H, C1-C6alkyl, C2-C8alkenyl, C2-C8alkynyl or C3-C6cycloalkyl; 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, can be used as agrochemical active ingredients.

Description

O-BENZYL OXIME ETHER DERIVATIVES AS PECTICIDES
The invention relates to compounds of formula
Figure imgf000003_0001
wherein either
X is CH or N, Y is ORi and Z is O, or
X is N, Y is NHRβ and Z is O, S or S(=0);
Figure imgf000003_0002
R, is H or Cι-C4alkyl;
R2 is H, Cι-C4alkyl, halo-Cι-C4alkyi, C3-C6cycioalkyI, C3-Cβcycloalkenyl, d-d- alkoxymethyl, Cι-C4alkoxy, halo-Cι-C4alkoxy, d-C4alky!thio or halo-Cι-C4alkylthio, cyano or aryl;
R3 and R4 are each independently of the other H, d-dalkyl, Cι-C4alkoxy, OH, SH, NH2, CN, N02, a (Cι-C4alkyl)3-Si group, it being possible for the alkyl groups to be the same or different, halogen, (Cι-dεlkyl)S(=O)ι, (halo-CrC4alkyl)S(=O)ι, halo-C1-C4alkyl or halo-Ci-dalkoxy, Cι-Cβalkylamino, di-Ci-dalkylamino, it being possible for the alkyl groups to be the same or different; arylamino or diarylamino, it being possible for the aryl groups to be the same or different;
I is O, 1 or 2;
R5 and Rβ are each independently of the other Cι-C6alkyl, halo-CrC6alkyl, C3-C6cycloalkyl, CrCβcycloalkenyl, halo-C3-C6cycloalkyl, d-dalkoxy, halo-CrCβalkoxy, d-Ce-alkyl- thio, halo-Cι-Cβalkylthio, Cι-C6alkylsulfinyl, halo-d-Cβaikylsulfinyl, CrCβ-alkylsulfonyl, halo-Cι-C6alkylsulfonyl, Cι-C6alkylsulfonyloxy, halo-d-C6alkyl-sulfonyloxy, d-dalk- oxy-Cι-C6alkyi, halo-Cι-C6alkoxy-Cι-C6alkyl, d-C6alkoxy-Cι-Cβalkoxy, Cι-C6alkyithio- d-Cβalkyl, halo-Cι-C6alkyfthio-Cι-C6alkyl, Ci-Cealk lsulfinvl-Ci-CβalkyI, halo-d-C6- alkylsulfinyl-CrCealkyl, Cι-C6all ylsulfonyl-CrC6all l, halo-Ci-CealkyJsulfonyl-CrCe- alkyl, formyl,
Figure imgf000004_0001
-CH=NO-C3-C6cycloalkyl, Cι-Cβalkylcarbonyl, halo-Cι-Cβalkylcarbonyl, d-C6alkoxy- carbonyl, halo-Ci-Cβalkoxycarbonyl, d-Cβalkylaminocarbonyl, Ci-dalkoxyimino- methyl, di(Cι-C6alkyl)aminocarbonyl, it being possible for the alkyl groups to the same or different; Ci-Cealkvlaminothiocarbonyl, di(d-C6alkyl)amino-thiocarbonyl, it being possible for the alkyl groups to be the same or different; Cι-Cβalkylamino, di(Cι-C6alkyl)amino, it being possible for the alkyl groups to be the same or different; aryiamino or diarylamino, it being possible for the aryl groups to be the same or different; halogen, NO2, CH, SF5, thioamido, thiocyanatomethyl or trimethylsilyl; aryl-Q-, heterocyclyl-Q-, aryl-Q-Cι-C6alkyl, aryl-Q-C2-C6alkenyl, heterocyclyl-Q-Ci-Cealkyl or heterocyclyl-Q-C2-Cβalkenyl, or aryl-Q-, heterocyclyl-Q-, aryl-Q-Ci-Cβalk l, aryl-Q-C2- Cβalkenyl, heterocyclyl-Q-d-Cβalkyl or heterocydyl-Q-CrCealkenyl, 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, Ci-Cealkyl, halo-Ci-Cealkyl, CrCecycloalkyl, halo- C3-C6cycloalk l, Ci-dalkoxy, halo-d-C6alkoxy, CN, nitro and Ci-Cβalkoxycarbonyl; wherein, when m and n are greater than 1 , the radicals R5 and Rβ may be the same or different; or two substituents R5 or two substituents Rβ form unsubstituted or mono- to tetra-substi- tuted Ci-dalkylenedioxy or -CH=CH-CH=CH- that are bonded to two adjacent carbon atoms of the phenyl ring in question, the substituents of the d-dalkylenedioxy or -CH=CH-CH=CH- group being selected from the group consisting of Ci-dalkyl and halogen;
R55 is CrC6alkyl, halo-Cι-C6alkyl, C3-Cecycloalkyl, d-CeCycloalkenyl, halo-C3-C6-cycl- oalkyl, Cι-C6alkoxy, halo-d-C6alkoxy, Cι-C6alkylthio, halo-d-C6alkylthio, d-C6alkyl- sulfinyl, halo-Cι-C6alkylsulfinyl, Cι-C6alkylsulfony1, halo-Cι-C6alkylsulfonyl, Cι-Cβalkyl- sulfonyloxy, halo-d-Cβalkylsulfonyloxy, d-Cβalkoxy-Cι-Cβalkyl, halo-Ci-Cealkoxy-Cr C6alkyl, Cι-Cβalkylthio-d-C6alkyl, halo-d-Cealkylthio-Ci-Cealkyl, Ci-Cealkylsulfinvl-d- C6alkyl, halo-Cι-C6alkylsulfinyl-Cι-Cealk l, Ci-Cβalkylsulfonyl-d-CβalkyI, halo- Ci-Cβalkylsulfonyl-Ci-Cβalkyl, Ci-Cealkylcarbonyl, halo-Ci-Ce-alkylcarbonyl, Ci-Cβalk- oxycarbonyl, halo-d-Cealkoxycarbonyl, Cι-Cβalkyl-aminocarbonyl, d-dalkoxyimino- methyl, di(d-C6alkyl)aminocarbonyl, it being possible for the alkyl groups to be the same or different; Ci-Cealkylaminothiocarbonyl, di(Cι-Cβalkyl)aminothiocarbonyl, it being possible for the alkyl groups to be the same or different; Ci-Cβalkylamino, di(Cι-C6alkyl)amino, it being possible for the alkyl groups to be the same or different, arylamino, diarylamino, alkylarylamino; halogen, NO2, CN, SF5, thioamido, thiocyana- tomethyl or trimethylsilyl; wherein, when q is greater than 1 , the radicals R55 are independent of one another;
Rβe is hydrogen, Cι-Cβalkyl, halo-Ci-Cealkyl, C3-C6cycioalkyl, d-C6cycloalkenyl, halo- d-Cβcycloalkyl, Ci-Cβalkyisulfinyl, halo-Cι-C6alkylsulfinyl, Ci-Cβalkylsulfonyl, halo- Ci-C6alkylsulfonyl, Ci-Cβalkoxy-Ci-Cealk l, halo-d-Cβalkoxy-Cι-Cβalkyl, Ci-Ce- alkylthio-Cι-C6alkyl, halo-d-Cβalkylthio-Ci-dalkyl, Cι-Cβalkylsulfinyl-Cι-C6alkyl, halo- Cι-C6alkylsulfinyl-Cι-C6alkyl, Ci-Cealk lsulfonyl-Ci-Cealkyl, halo-d-C6alkylsulfonyl- Cι-Cβalkyl, Cι-Cβalkylcarbonyl, halo-Ci-Cβalkylcarbonyl, d-C6alkoxycarbonyl, halo- d-Cealkoxycarbonyl, Ci-Cβalkylaminocarbonyl, Cι-C4alkoxyiminomethyl, di(d-C6- alkyl)aminocarbonyl, it being possible for the alkyl groups to be the same or different, Ci-Cβalkylaminothiocarbonyl, di(Cι-C6alkyl)aminothiocarbonyl, it being possible for the alkyl groups to be the same or different; halogen, NO2, CN, SF5, thioamido, thiocya- natomethyl or trimethylsilyl; m is 0, 1 , 2, 3, 4 or 5; n is 0, 1 , 2, 3 or 4; q is 0, 1 , 2, 3 or 4;
Q is a direct bond, O, S, -CH(OH)-, -C(=O)- or -S(=O)v-; v is 0, 1 or 2;
A is a direct bond, d-Cioalkylene, -C(=O)-, -C(=S)- or halo-Cι-Cιoalkylene and
R7 is a radical Rι0; or
A is Cι-C10alkylene, -C(=O)-, -C(=S)- or halo-d-doalkylene and
R7 is -CN, OR10, N(R10)2, it being possible for the radicals R10 to be the same or different, or -S(=0)pRιo;
R8 is H or d-dalkyl;
R9 is methyl, fluoromethyl or difluoromethyl;
R10 is H, Ci-Cealkyl, C2-Cβalkenyl, C2-Cβalkynyi, C3-Cβcycloalkyl, or CrCβalkyl, C2-C8alk- enyl, C2-Cβalkynyl or C3-Cβcycloalkyl, each of which is mono- or poly- substituted by substituents selected from the group consisting of halogen; or R10 is -Si(C1-C4alkyl)3l it being possible for the alkyl groups to be the same or different; Cι-Cβalkoxycarbonyl, 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 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 that n is not 0 when U is m- phenyl or p-phenyl, or when U is 4-chlorophenyi in the para position; and simultaneously Y is OCH3 or NHCH3; Z is oxygen; R2, AR7 and R9 are methyl, and R3 and R4 are H; and with the further proviso that n is not 0 when U is 4-trifluoromethylphenyl or 4-cyanophenyl, each in the para position; and simultaneously X is N; Y is OCH3; Z is oxygen; R2, AR7 and R9 are methyl; and R3 and R4 are H; to a process for the preparation of those compounds, E/Z isomers and tautomers and to the use thereof, to pesticides, the active ingredient of which is selected from those compounds, E/Z isomers and tautomers; 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 to 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, fully 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 (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. Preference is given to com- pounds of formula (I), and of the following formulae (III), (IV), (VI), (VIII), (XII), (XIV) and (XV), in which the C=N double bond indicated by an E is in the E configuration.
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 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.
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)-. 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 R5 are pyrazinyl, 3'-pyridyI, 2'-pyridyl, 4'-pyridyl, 2'-pyrimidinyl,
4'-pyrimidinyl, δ'-pyrimidinyl, 2'-thiazolyl, 2'-oxazolyl, 2'-thienyl, 3'-thienyl and δ'-thiazolyl.
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. Examples of 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 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. Haloalkenyi is, for example, CH2CH=CHCI, CH2CH=CCI2, CH2CF=CF2 orCH2CH=CHCH2Br. Haloalkynyl is, for example, CH2CsCF, CH2CHCCH2CI or CF2CF2CsCCH2F.
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 R7 is H. Hereinbefore and hereinafter 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. Furthermore, 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. Preference is given within the context of the invention to agrochemically acceptable salts. Hereinbefore and hereinafter 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. The same applies also to tautomers of compounds of formulae (I) to (XV) and salts thereof. In each case the free form is generally preferred.
A preferred embodiment within the context of the present invention is constituted by the compounds of formula (I) wherein
X, Z, R2, R3, F , Re, R7. R9 and A are as defined above, and
Y is ORn;
Ri is d-dalkyl;
R5 is Ci-Cealkyl, halo-Cι-C6alkyl, C3-C6cycloalkyl, C3-C6cycioalkenyl, halo-C3-C6- cycloalkyl, d-Cβalkoxy, halo-Ci-dalkoxy, Ci-Cβalkylthio, halo-Cι-C6alkylthio, Cι-C6alkylsulfinyl, halo-Cι-C6alkylsulfinyl, Cι-C6alkylsulfonyl, halo-d-Cealkylsulfonyl, Cι-C6alkylsulfonyloxy, halo-Cι-C6alkylsulfonyloxy, Ci-Cealkoxy-Ci-C6aIkyl, halo-Cι-C6- alkoxy-Ci-dalkyl, Ci-Cβalkylthio-d-CealkyI, halo-Cι-C6alkylthio-Cι-C6alkyl, Cι-C6- alkylsulfinyl-d-Cealkyl, halo-d-Cβalkylsulfinyl-d-Cβalkyl, Ci-Cβalkylsulfonyl-Ci-Ce- alkyl, halo-Cι-C6alkylsulfonyl-d-Cβalkyl, d-Cβalkylcarbonyl, halo-Cι-C6alkylcarbonyl, CrCβalkoxycarbonyl, halo-d-Cealkoxycarbonyl, Ci-C6alkylamino-carbonyl, C1-C4alkoxyiminomethyl, di(Cι-Cβalkyl)aminocarbonyl, it being possible for the alkyl groups to be the same or different; Cι-Cβalkylaminothiocarbonyl, di(Cι-Cβalkyl)amino- thiocarbonyl, it being possible for the alkyl groups to the same or different; d-C6alkylamino, di(d-C6alkyl)amino, it being possible for the alkyl groups to the same or different; arylamino or diarylamino, it being possible for the aryl groups to the same or different; halogen, NO2, CN, SF5, thioamido, thiocyanatomethyl or trimethylsilyl; aryl-Q-, heterocyclyl-Q-, aryl-Q-Cι-Cβalkyl, aryl-Q-C2-C6alkenyl, heterocyclyl-Q-d- C6alkyl or heterocyclyl-Q-C2-Cβalkenyl; or aryl-Q-, heterocyclyl-Q-, aryl-Q-Ci-Cealkyl, aryl-Q-C2-C6alkenyl, heterocyclyl-Q-Cι-C6alkyl 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, Cι-Cβalkyl, halo-d-Cβalkyl, C3-C6cycloalkyl, ha- lo-C3-Cβcycloalkyl, Cι-Cβalkoxy, halo-Ci-Cealkoxy, CN, nitro and Cι-C6alkoxycarbonyl; or two substituents R5 are unsubstituted or mono- to tetra-substituted d-dalkylene- dioxy or -CH=CH-CH=CH-, that are bonded to two adjacent carbon atoms of the phenyl ring, the substituents of the Ci-dalkylenedioxy or -CH=CH-CH=CH- group being selected from the group consisting of d-dalkyl and halogen; wherein, when m and n are greater than 1 , the radicals R5 and R6 may be the same or different; m is 1 , 2, 3, 4 or 5; n is 1 , 2, 3 or 4;
Q is a direct bond, O, S, -CH(OH)-, -C(=O)- or -S(=O)^; and v is O, 1 or2.
Especially preferred embodiments within the context of the invention - in each case taking into consideration the above-mentioned provisos - are:
(1) a compound of formula (I) wherein X is CH and Z is O;
(2) a compound of formula (I) wherein X is N and Z is O;
(3) a compound of formula (I) wherein Y is ORi, preferably Ci-dalkoxy, especially methoxy; (4) a compound of formula (I) wherein Z is O;
(5) a compound of formula (I) wherein
R2 is H, Ci-dalkyl, halo-d-dalkyl or C3-Cecycloalkyl, cyano, aryl, preferably d-dalkyl, halo-Ci-dalkyl or cyclopropyl; especially Ci-dalkyl; more especially methyl;
(6) a compound of formula (I) wherein
R3 is H, Ci-dalkyl, Ci-dalkoxy, OH, CN, N02, halogen, halo-Ci-dalkyl or halo-d-d- alkoxy, preferably H, Ci-dalkyl, Cι-C alkoxy or halogen, especially H, methyl, methoxy, chlorine or fluorine, more especially H;
(7) a compound of formula (I) wherein
FU is H, Ci-dalkyl, Ci-dalkoxy, OH, CN, N02, 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;
(8) a compound of formula (I) wherein U is phenyl, and
R5 is d-dalkyl, halo-d-dalkyl, C3-C6cycloalkyl, halo-C3-C6cycloalkyl, Ci-dalkoxy, halo- Ci-dalkoxy, Ci-dalkylthio, halo-Cι-C6alkylthio, Ci-Cβalkylsulfinyl, halo-Ci-Cβalkylsulfinyl, d-C6alkylsulfonyl, halo-Cι-C6alkylsulfonyl, d-C6alkylsulfonyloxy, halo-d-dalkylsulfonyl- oxy, Cι-Cβalkoxy-Cι-Cealkyl, halo-Cι-C6alkoxy-Cι-Cβalkyl, formyl, -CH=NO-Cι-C alkyl, Ci-Cealkylcarbonyl, halo-Cι-C6alkylcarbonyl, Cι-C6alkoxycarbonyl, halo-Ci-dalkoxy-car- bonyl, halogen, N02 or CN; aryl-Q-, heterocyclyl-Q-, aryl-Q-d-dalkyl or heterocyclyl-Q- Cι-Cβalkyl; or aryl-Q-, heterocyciyl-Q-, aryl-Q-Ci-dalkyl or heterocyclyl-Q-Cι-C6alkyl, 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, d-dalkyl, halo-Ci-dalkyl, d-dcycloalkyl, d-Cβalkoxy, halo- Ci-dalkoxy, CN, nitro and Ci-C4alkoxy-carbonyl; d-dalkylamino, di-Cι-Cβalkylamino, it being possible for the alkyl groups to be the same or different; arylamino or diarylamino, it being possible for the aryl groups to the same or different; or two substitunets R5 are unsubstituted or mono- to tetra-substituted d-d-alkylenedioxy or -CH=CH-CH=CH-, the substituents of the Ci-dalkylenedioxy or -CH=CH-CH=CH- group being selected from the group consisting of Ci-dalkyl and halogen; especially Ci-dalkyl, halo-Ci-dalkyl, C3-Cβcycloalkyl, Ci-dalkoxy, halo-d-dalkoxy, Ci-dalkylthio, halo-d-dalkylsulfinyl, halo-d-C alkylsulfonyl, halo-Ci-dalkylsulfonyloxy, formyl, -CH=NO-Cι-C4alkyl, halo-Ci-dalkylcarbonyl, halo-Cι-C4alkoxycarbonyl, halogen, aryl that is unsubstituted or substituted by halogen; or two substituents R5 are -CH=CH-CH=CH-; more especially methyl, halomethyl, Ci-dalkoxy,
Figure imgf000012_0001
formyl, -CH=NO- d-dalkyl, halogen, phenyl, bromophenyl; or two substituents R5 are -CH=CH-CH=CH-; methyl, trifluoromethyl, fluorine, bromine, chlorine, formyl, -CH=NO-CH3, -CH=CH-CH=CH- or 4-bromophenyl being especially preferred; wherein, when m is greater than 1 , the radicals R5 may be the same or different.
(9) a compound of formula (I) wherein U is and
Figure imgf000012_0002
R55 is d-dalkyl, halo-d-dalkyl, C3-C6cycloalkyl, C3-C6cycloalkenyl, halo-C3-C6- cycloalkyl, Cι-C6alkoxy, halo-Ci-Cβalkoxy, Cι-Cβalkylthio, halo-Ci-dalkylthio, d-C6alkyl- sulfinyl, halo-Cι-C6alkylsulfinyl, d-Cβalkylsulfonyl, halo-Cι-Cβalkylsulfonyl, Ci-d-alkylsulf- onyloxy, halo-CrC6alkylsulfonyloxy, Cι-Cealkoxy-Cι-Cβalkyl, halo-Cι-CealkoxyCι-C6alkyl, Cι-Cβalkylthio-Cι-Cβalkyl, halo-Ci-dalkvlthio-Ci-dalkyi, d-dalkylsulfinyl-Ci-Ce-alkyl, halo- Ci-Cβalkylsulfinyl-Ci-Cβalkyl, Ci-Cβalkylsulfonyl-Ci-Cealkyi, halo-Ci-Ce-alkylsulfonyl- Cι-Cβalkyl, Cι-Cβalkylcarbonyl, halo-Ci-Cealkylcarbonyl, Cι-Cβalkoxycarbonyl, halo-Ci-dalk- oxycarbonyl, d-Cβalkylaminocarbonyl, Cι-C4alkoxyiminomethyl, di(C -C6- alkyl)aminocarbonyl, it being possible for the alkyl groups to be the same or different; d-dalkylaminothiocarbonyl, di(Cι-Cβalkyl)aminothiocarbonyl, it being possible for the alkyl groups to the same or different; Cι-Cβalkylamino, di(Cι-dalkyl)amino, it being possible for the alkyl groups to be the same or different; arylamino, diarylamino, alkylarylamino; halogen, N02, CN, SF5, thioamido, thiocyanatomethyt or trimethylsilyl; especially d-dalkyl, halo-Ci-dalkyl, C3-C6cycloalkyl or halogen and q is 1 or 2; more especially methyl, trifluoror ethyl, fluorine or chlorine and q is 1 or 2;
Ree is hydrogen, Ci-dalkyl, halo-d-dalkyl, d-dcycloalkyl, Crdcycloalkenyl, halo- C3-C6cycloalkyl, Ci-dalkylsulfinyl, halo-CrC6alkylsulfinyl, d-Cβalkylsulfonyl, halo- Cι-C6alkylsulfonyl, Cι-Cealkoxy-Cι-C6alkyl, halo-Cι-C6alkoxy-Cι-C6alkyl, d-dalkylthio- Cι-Cβalkyl, halo-Cι-Cealkylthio-Cι-C6alkyl, d-dalkylsulfinyl-Ci-dalkyl, halo-Cι-C6alkyl- sulfinyl-Cι-Cβalkyl, Cι-Cβalkylsulfonyl-Cι-Cβalkyl, halo-Cι-Cβalkylsulfonyl-Cι-Cβalkyl, Cι-C6alkylcarbonyl, halo-Ci-dalkylcarbonyl, Cι-Cβalkoxycarbonyl, halo-Ci-dalkoxy- carbonyl, Cι-C6alkylaminocarbonyl, Ci-dalkoxyiminomethyl, di(Cι-Cealkyl)aminocarbonyl, it being possible for the alkyl groups to be the same or different; d-dalkylaminothio-car- bonyl, di(Cι-C6alkyl)aminothiocarbonyl, it being possible for the alkyl groups to be the same or different; halogen, N02, CN, SF5, thioamido, thiocyanatomethyl or trimethylsilyl; preferably hydrogen, methyl, trifluoromethyl, methylcarbonyl, trifluoromethylcarbonyl, me- thoxycarbonyl, trifluoromethoxycarbonyl, chlorine, fluorine, CN or methylsulfonyl;
(10) a compound of formula (I) wherein
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, N02 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 aryl or heterocyclyl ring, the substituents being selected independently of one another from the group consisting of halogen, Ci-dalkyl, halo-Ci-dalkyl, cycloalkyl, d-dalkoxy, halo-d-dalkoxy and CN; or two R6 are unsubstituted or mono- or di- substituted methylenedioxy or -CH=CH-CH=CH-, the substituents of the methylenedioxy or -CH=CH-CH=CH- group being selected from the group consisting of methyl and fluorine; especially d-dalkyl, halo-Ci-dalkyl, C3-dcycloalkyl, halo-C3-Cβcycloalkyl, Ci-dalkoxy, halo-Ci-dalkoxy, halogen, N02 or CN; or two substituents R6 are unsubstituted or mono- or di-substituted methylenedioxy or -CH=CH-CH=CH-, the substituents of the methylenedioxy or -CH=CH-CH=CH- group being selected from the group consisting of methyl and fluorine; preferably methyl, trifluoromethyl, methoxy, trifluoromethoxy, fluorine or chlorine; wherein, when n is greater than 1 , the radicals R6 may be the same or different.
(11 ) a compound of formula (I) wherein m is 1 , 2 or 3; especially 1 or 2;
(12) a compound of formula (I) wherein n is 0 or 1 ; especially 0;
(13) a compound of formula (I) wherein AR7 is methyl;
(14) a compound of formula (I) wherein AR7is ethyl;
(15) a compound of formula (I) wherein
R8 is H or Ci-dalkyl, preferably Ci-dalkyl, especially methyl; (16) a compound of formula (I) wherein R9is methyl orfluoromethyl, especially methyl;
(17) methoxyimino-{2-[2-methoxyimino-1 -methyl-2-(3'-trifluoromethyl-biphenyl-4-yl)- ethylideneaminooxymethyl]-phenyl}-acetic acid methyl ester.
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 imgf000014_0001
which is known or can be prepared in accordance with methods known perse and wherein X, Y, Z, R3, R4and R9are as defined for formula (I) and Xi is a leaving group, preferably in the presence of a base, with a compound of formula
Figure imgf000014_0002
wherein n, U, A, R2, Rβand R7are as defined above for formula (I); or a2) reacting a compound of formula
Figure imgf000014_0003
wherein n, A, U, R2, R6and R7 are as defined for formula (I), optionally in the presence of a base, with a compound of formula
Figure imgf000015_0001
which is known or can be prepared in accordance with methods known perse and wherein X, Y, Z, R3, * and R9 are as defined for formula (I); or b) to prepare a compound of formula (I) wherein Y is NHRβ and Z is O, reacting a compound of formula (I) wherein Y is ORi with a compound of formula RβNH2, 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 P4S10 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; or
e) to prepare a compound of formula (I) wherein U is
Figure imgf000015_0002
and R5 and m are as defined above for formula (I), reacting a compound of formula
Figure imgf000015_0003
wherein A, X, Y, Z, R2, R3, R4, Re, R7, R9 and n are as defined for formula (I) and X2 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
Figure imgf000016_0001
which is known or can be prepared in accordance with a process known perse and wherein R5 and m are as defined for formula (I), in the presence of a base or of a transition metal catalyst;
f) to prepare a compound of formula (I) whereiinn U is and R5 555,. R nee
Figure imgf000016_0002
and q are as defined above for formula (I), reacting a compound of formula
Figure imgf000016_0003
wherein A, X, Y, Z, R2, R3, 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
Figure imgf000016_0004
wherein RK and q are as defined for formula (I), which is known or can be prepared in accordance with methods known perse; or
g) to prepare a compound of formula (I) wherein U is and R5 and q
Figure imgf000016_0005
are as defined for formula (I), reacting a compound of formula (I) wherein U is wth an oxidising agent, preferably with 2,3-dichloro-5,6-dicyano-1 ,4-
Figure imgf000017_0001
benzoquinone (DDQ); and, in each case, if desired, converting a compound of formula (I) obtainable according to the process or in some other manner, 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 in some other manner, 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 in some other manner into a 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,
h) reacting a compound of formula (IV), wherein m, n, A, R2, R6 and R are as defined for formula (I), optionally in the presence of a base, with H2NOH or with a salt thereof; or
i1 ) reacting a compound of formula
Figure imgf000017_0002
wherein U, R2, R6 and n are as defined for formula (I), optionally in the presence of a base, with a compound of formula
Figure imgf000017_0003
which is known or can be prepared according to methods known perse and wherein A and R are as defined for formula (I) and Xs is a leaving group, especially bromine or iodine, to form a compound of formula (IV), and reacting that compound of formula (IV) with hydroxy- lamine or with a salt thereof, optionally in the presence of a basic or acid catalyst; or
i2) reacting a compound of formula
Figure imgf000018_0001
wherein U, R2, R5l Re and n are as defined for formula (I), optionally in the presence of a base, with a compound of formula
R7AONH2 (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);
k) to prepare a compound of formula (III) wherein U is B -H — (Rg)m and R5 and m
are as defined for formula (I), reacting a compound of formula
Figure imgf000018_0002
wherein n, A, R2, R6and R7are as defined for formula (I) and X2 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
I) to prepare a compound of formula (III) wherein U is and R5 and m
Figure imgf000018_0003
are as defined for formula (I), reacting a compound of formula
Figure imgf000019_0001
which is known or can be prepared in accordance with methods known per se and wherein n, R2and Rβare as defined for formula (I) and X2 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, R2, R5and R6are as defined for formula (I), and reacting that compound, optionally in the presence of a base, either with a compound of formula R7AONH2 (XI), or with H2NOH or with a salt thereof and then with a compound of formula R7AX2 (IX); or
m) to prepare a compound of formula (III) wherein U is and R5 and m
Figure imgf000019_0002
are as defined for formula (I), reacting a compound of formula
Figure imgf000019_0003
which is known or can be prepared in accordance with methods known perse and wherein n, R2, R6, R7and X2are 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 H2NOH or with a salt thereof; or
n) to prepare a compound of formula (III) wherein U is and R55, Ree
Figure imgf000019_0004
and q are as defined for formula (I), reacting a compound of formula (III) wherein U is and R55, Ree and q are as defined for formula (I) •* :τn an oxidising
Figure imgf000020_0001
agent; and, if desired, converting a compound of formula (III) obtainable according to the process or in some other manner, 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 in some other manner, 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 in some other manner into a free compound of formula (III), or an E/Z isomer or tautomer thereof, or into a different salt.
By virtue of their structure, 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.
Novel starting materials and intermediates used according to the invention to prepare the compounds of formula (I), the use of those starting materials and intermediates and the processes for their preparation also form part of this invention.
The observations made above in respect of E/Z isomers and tautomers of compounds of formula (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 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. The starting materials given hereinbefore and hereinafter that are used to prepare the compounds of formula (I) and, where applicable, their E/Z isomers and tautomers are known or can be prepared in accordance with methods known perse, for example according to the details given hereinafter.
Variant a1. a2):
Suitable leaving groups Xi in the compounds of formula (II) are, for example, hydroxy, Cι-C8alkoxy, halo-Cι-Cβalkoxy, Ci-dalkanoyloxy, mercapto, Ci-dalkylthio, halo-Cι-C8alkyl- thio, d-dalkanesulfonyloxy, halo-Cι-C8alkanesulfonyloxy, 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. 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, cyclohexylamine, N-cyclohexyl- N,N-dimethylamine, N,N-diethylaniline, pyridine, 4-(N,N-dimethylamino)pyridine, quinuclidi- ne, N-methylmorpholine, benzyltrimethylammonium hydroxide and 1 ,5-diaza- bicyclo[5.4.0]undec-5-ene (DBU).
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. Generally, however, the addition of an inert solvent or diluent or a mixture thereof is advantageous. Examples of such 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, dimethoxydiethyl ether, tetrahydrofuran and dioxane; ketones, such as acetone, methyl ethyl ketone and methyl isobutyl ketone; alco- hols, 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 hexamethylphosphoric acid triamide; nitrites, such as acetonitrile and propionitrile; and suifoxides, 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-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.
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.
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, especially sodium hydride.
Variant b):
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. Generally, however, the addition of 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.
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.
Especially preferred reaction conditions may be found in Example P3e).
Variant c):
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. Generally, however, the addition of an inert solvent or diluent or a mixture thereof is advantageous. Examples of such 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, tetrahydrofuran and dioxane; and suifoxides, such as dimethyl sulfoxide.
The reaction is carried out advantageously in a temperature range of from approximately
0°C to approximately +120°C, preferably from approximately 80°C to approximately +120°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. 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.
Variant d):
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. Generally, however, the addition of an inert solvent or diluent or a mixture thereof is advantageous. Examples of such 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, 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-methylpyrrolidone and hexamethyl- phosphoric acid triamide; nitriles, such as acetonitrile and propionitrile; and suifoxides, such as dimethyl sulfoxide. If the reaction is carried out in the presence of an organic acid or per- acid, 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.
The reaction is advantageously carried out in a temperature range of from approximately
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.
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.
Variant e):
Suitable leaving groups X2 in the compounds of formulae (VI), (XII), (XIII) and (XIV) are, for example, hydroxy, Ci-dalkoxy, halo-Cι-C8alkoxy, Cι-C8alkanoyloxy, mercapto, d-dalkylthio, halo-d-dalkylthio, d-Cβalkanesulfonyloxy, halo-Cι-C8alkanesulfonyloxy, 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(PPh3) .
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. 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, cyclohexylamine, N-cyclo- hexyl-N,N-dimethylamine, N,N-diethylaniline, pyridine, 4-(N,N-dimethylamino)pyridine, quinuclidine, N-methylmorpholine, benzyltrimethylammonium hydroxide and 1 ,5-diaza- bicyclo[5.4.0]undec-5-ene (DBU). Preference is given to 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. Examples of such 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 (dimethoxyethane), dimethoxydiethyl ether, tetrahydrofuran and dioxane; ketones, such as acetone, methyl ethyl ketone or methyl isobutyl ketone; alcohols, such as methanol, ethanol, propanol, isopropanol, butanol, ethylene glycol and glycerol; amides, such as N,N-dimethyl-formamide, N,N-diethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone and hexamethylphos- phoric acid triamide; nitriles, such as acetonitrile and propionitrile; and suifoxides, 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-methylmorpholine or N,N-diethylaniline, may also serve as solvent or diluent. Preferred solvents are water-miscible ethers and water, especially mixtures thereof, more especially ethylene glycol dimethyl ether/H20/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.
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 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).
Variant ft:
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. Generally, however, the addition of 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.
The 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.
The addition of a suitable catalyst is required in most cases. There may be mentioned as 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.
Especially preferred reaction conditions may be found in Example P3a).
Variants . n):
Suitable oxidising agents are oxides, such as Mn02, 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. Generally, however, the addition of 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 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.
The 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.
Especially preferred reaction conditions may be found in Example P3f).
Variant h):
Suitable bases for facilitating the reaction are, for example, those mentioned in
Variant 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. Generally, however, the addition of 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. 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.
Variant fl:
Suitable leaving groups X3 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. Generally, however, the addition of 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.
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.
In a preferred embodiment of the Variant, 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).
Especially preferred reaction conditions may be found in Example P1g).
Variants kV fl and ml:
The same conditions apply as for Variant e). Especially preferred readion conditions may be found in Examples P1f), P1i) and P1k).
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.
Mixtures of diastereoisomers and mixtures of racemates of compounds of formulae (I), (III), (IV), (VIII), (X), (XII), (XIV) and (XV) 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 fradional 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 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. 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 enantioseledive 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 adive isomer, for example enantiomer, or mixture of isomers, for example mixture of enantiomers, insofar as the individual components have different biological adivity.
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.
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 P7.
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 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. in the mortality of the pests, which occurs immediately or only after some time, for example during moulting, or of their eggs, or indiredly, for example in reduced oviposition and/or hatching rate, good adivity corresponding to a mortality of at least 50 to 60 %.
The mentioned animal pests include, for example: of the order Lepidoptera, for example,
Acleris spp., Adoxophyes spp., Aegeria spp., Agrotis spp., Alabama argillaceae,
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.,
Hedya nubiferana, Heliothis spp., Hellula undalis, Hyphantria cunea, Keiferia ly- copersicella, Leucoptera scitella, Lithocollethis spp., Lobesia botrana, Lymantria spp., Lyonetia spp., Malacosoma spp., Mamestra brassicae, Manduca sexta, Op- erophtera spp., Ostrinia nubilaiis, Pammene spp., Pandemis spp., Panolis flam- mea, Pedinophora gossypiella, Phthorimaea operculella, Pieris rapae, Pieris spp., Plutella xylostella, Prays spp., Scirpophaga spp., Sesamia spp., Spargan- othis spp., Spodoptera spp., Synanthedon spp., Thaumetopoea spp., Tortrix 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.,
Leucophaea maderae, Locusta spp., Periplaneta spp. and Schistocerca spp.; of the order Isoptera, for example, Reticulitermes spp.; of the order Psocoptera, for example, Liposcelis spp.; of the order Anoplura, for example,
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. and 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., Planococcus spp., Pseudaulacaspis spp., Pseudococcus spp., Psylla spp., Pulvinaria aethiopica, Quadraspidiotus spp., Rhopalosiphum spp., Saissetia spp., Scaphoideus spp., Schizaphis spp., Sitobion spp., Trialeurodes vaporariorum, Trioza erytreae and Unaspis citri; of the order Hymenoptera, for example, Acromyrmex, Atta spp., Cephus spp., Diprion spp., Diprionidae, Gilpinia polytoma, Hoplocampa spp., Lasius spp., Monomorium pharaonis, Neodiprion spp., Solenopsis spp. and Vespa spp.; of the order Diptera, for example,
Aedes spp., Antherigona soccata, Bibio hortulanus, Calliphora erythrocephala, Ceratitis spp., Chrysomyia spp., Culex spp., Cuterebra spp., Dacus spp., Droso- phila melanogaster, Fannia spp., Gastrophilus spp., Glossina spp., Hypoderma spp., Hyppobosca spp., Liriomyza spp., Lucilia spp., Melanagromyza spp., Musca spp., Oestrus spp., Orseolia spp., Osdnella frit, Pegomyia hyoscyami, Phorbia spp., Rhagoletis pomonella, Sciara spp., Stomoxys spp., Tabanus spp., Tannia spp. and Tipula spp.; of the order Siphonaptera, for example, Ceratophyllus spp. and Xenopsylla che- opis; of the order Thysanura, for example, Lepisma saccharina; and of the order Acarina, for example, Acarus siro, Aceria sheldoni, Aculus schlechtendali, Ambiyomma spp., Argas spp., Boophilus spp., Brevipalpus spp., Bryobia praetiosa, Calipitrimerus spp., Chorioptes spp., Dermanyssus gallinae, Eotetranychus caφini, Eriophyes spp., Hyalomma spp., Ixodes spp., Olygonychus pratensis, Ornithodoros spp., Panonychus spp., Phyllocoptruta oleivora, Polyphagotarsonemus latus, Psorop- tes spp., Rhipicephalus spp., Rhizoglyphus spp., Sarcoptes spp., Tarsonemus spp. and Tetranychus spp..
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,
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 some of the parts of the plants that grow later are also pro- teded 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 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, aubergines, sugar cane, tea, pepper, vines, hops, bananas and natural rubber plants, as well as ornamentals.
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.
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 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).
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 oil, castor oil, coconut oil or soybean oil, and silicone oils.
The solid carriers used, e.g. for dusts and dispersible powders, are normally natural mineral fillers, such as calcite, talcum, kaolin, montmorillonite or attapulgite. In order to improve the physical properties it is also possible to add highly dispersed silicic 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.
Depending on the nature of the compound to be formulated, 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. Further suitable 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. Representative examples are 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! radical and, as further substituents, unsubstituted or halogenated lower alkyl, benzyl or hydroxy-lower alkyl radicals. 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.
Both water-soluble soaps and water-soluble synthetic surface-adive compounds are suitable anionic surfadants. Suitable soaps are the alkali metal salts, alkaline earth metal salts and unsubstituted or substituted ammonium salts of higher fatty acids (C10-C22), 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. More frequently, however, synthetic surfadants are used, espedally fatty sulfonates, fatty sulfates, sulfonated benzimidazole derivatives or alkylarylsulfonates. The 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. Examples of alkylarylsulfonates are the sodium, calcium or triethanolammonium salts of dodecylbenzenesulfonic acid, di- butylnaphthalenesulfonic acid or of a condensate of naphthalenesulfonic acid and formaldehyde. Also suitable are 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.
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 surfadants (in each case percentages are by weight). Whereas commercial produds 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 %
The activity of the 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. Examples of 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), 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.
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 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. However, 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.
The 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.
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 : Preparation of 3-(4-bromophenyl)-2-hydroximino-3-ethoximinopropane
Figure imgf000040_0001
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. Chromatography of the crude produd on silica gel using ethyl acetate/hexane (1:9) yields 35 g of 1-(4-bromophenyl)-1-hydrox-imino- propan-2-one having a melting point of 190-191 °C. P1cϊ: 35 g of 1-(4-bromophenyl)-1-hydroximinopropan-2-one, 24 g of potassium carbonate and 27 g of ethyl iodide are stirred at 50°C for 5 hours. The reaction mixture is filtered and the filtrate is concentrated. The residue is taken up in ethyl acetate, washed with water and brine, dried and concentrated. Chromatography of the crude product on silica gel using ethyl acetate/hexane (1:19) yields 37 g of 1-(4-bromophenyl)-1-ethoximinopropan-2-one in the form of a syrup.
P1d): 21 g of pyridine and 19 g of hydroxylammonium chloride are added to 37 g of 1-(4- bromophenyl)-1-ethoximinopropan-2-one in 600 ml of ethanol and the mixture is stirred at 90°C for 2 hours. The readion mixture is concentrated, stirred with water and filtered. The filter residue is taken up in ethyl acetate, washed with water, dried and concentrated. 36 g of 1-(4-bromophenyl)-2-hydroximino-1-ethoximinopropane having a melting point of 157-158°C (compound 1-1.1) are obtained.
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- C3H3 is cyclopropyl. Table 1 -1 : Compounds of formula
Figure imgf000041_0001
Ex. No. AR7 phys. data
1-1.1 CH2CH3 4-Br m.p.: 157-158°C
1-1.2 CH2CH3 3-Br
1-1.3 CH2CH3 2-Br
1-1.4 CH2CH3 4-I
1-13 CH2CH3 3-I
1-1.6 CH2CH3 2-I
1-1.7 CH3 4-Br m.p.: 176-177°C
1-1.8 CH3 3-Br Ex.No. AR7 X2 phys. data
1-1.9 CH3 2-Br
1-1.10 CH3 4-I
1-1.11 CH3 3-I
1-1.12 CH3 2-I
1-1.13 CH2CβH -3-CF3 4-Br
1-1.14 CH2C≡CH 4-Br m.p.: 164-165°C
1-1.15 CH2CH=CCI2 4-Br
1-1.16 CH2CH=CH2 3-Br
1-1.17 CH2C≡CH 3-Br
1-1.18 CH2CH=CCI2 2-Br
1-1.19 CH2Si(CH3)3 2-Br
1-1.20 CH2-c-C3H3-2,2-CI2 2-Br
1-1.21 CH2COOC2H5 4-Br
1-1.22 CH(CH3)COOdH5 4-Br
1-1.23 CH2CF3 4-Br
1-1.24 n-dH7 4-Br
1-1.25 iso-C3H7 4-Br
1-1.26 n-C H9 4-Br
1-1.27 CH2CsCH 4-I
1-1.28 CH2CH=CCI2 4-Br
1-1.29 cyclopropyl 4-Br
Example P1f): Preparation of the compound of formula
Figure imgf000042_0001
1.1 g of 1-(4-bromophenyl)-1-ethoximinopropan-2-one, 1.4 g of potassium carbonate, 0.46 g of tetrakis-triphenylphosphinepalladium(O), 16 ml of dimethoxyethane, 12 ml of tetrahydrofuran, 16 ml of water and 0.9 g of 4-trifluoromethylphenylboric acid are stirred under an argon atmosphere at 75°C for 3 hours. The readion mixture is taken up in ethyl acetate, washed several times with water, dried and concentrated. Chromatography of the crude product on silica gel using ethyl acetate/hexane (1 :25) yields the title compound having a melting point of 109-110°C (compound 1-2.18).
Example P1Q): Preparation of the compound of formula
Figure imgf000043_0001
1.7 g of 1-(4-(3-trifluoromethylphenyl)phenyl)-1-hydroximinopropan-2-one, 0.9 g of potassium carbonate and 0.8 g of propargyl bromide in 10 ml of acetonitrile are stirred at 25 °C for 12 hours. The readion mixture is filtered and the filtrate is concentrated. The residue is taken up in ethyl acetate, washed with water and brine, dried and concentrated. Chromatography of the crude produd on silica gel using ethyl acetate/hexane (1:19) yields the title compound having a melting point of 87-88°C (compound 1-2.70).
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-C3H3 is cyclopropyl.
Table 1-2: Compounds of formula
Figure imgf000043_0002
Ex. No. AR7 (R5)n (Rβ)n m.p.
Figure imgf000043_0003
1-12 CH3 2-CH3 (n = 0)
1-2.3 CH2CH2CH3 2-CH3 (n = 0)
1-2.4 CH2CH3 4-CI (n = 0)
1-2.5 CH3 4-CI (n = 0)
1-2.6 CH2CH2CH3 4-CI (n = 0)
1-17 CH2CH3 3-CI (n = 0)
1-2.8 CH3 3-CI (n = 0) Ex.No. AR7 (R5)m (Rβ)n m.p.
1-2.9 CH2CH2CH3 3-CI (n = 0)
1-110 CH2CH3 2-CI (n = 0)
1-111 CH3 2-CI (n = 0)
1-112 CH2CH CH3 2-CI (n = 0)
1-113 CH2CH3 2,4-CI (n = 0)
1-114 CH3 2,4-CI (n = 0)
1-115 CH2CH2CH3 2,4-CI (n = 0)
1-116 CH2CH3 3-CF3 (n = 0)
1-117 CH3 4-CF3 (n = 0)
1-118 CH2CH3 4-CF3 (n = 0) 109-110°C
1-119 CH2CH2CH3 4-CF3 (n = 0)
1-120 CH2CH3 4-F (n = 0)
1-121 CH3 4-F (n = 0)
1-122 C H2C H2C H3 3-F (n = 0)
1-123 CH2CH3 3-F (n = 0)
1-124 CH3 3-F (n = 0)
1-125 CH2CH2CH3 4-F (n = 0)
1-126 CH2CeH4-3-CF3 4-CF3 (n = 0)
1-127 CH2CsCH 4-CF3 (n = 0)
1-128 CH2CH=CCI2 4-F (n = 0)
1-129 CH2CH=CH2 4-F (n = 0)
1-130 CH2CsCH 4-F (n = 0)
1-131 CH2CH=CCI2 3,5-CI (n = 0)
1-132 CH2Si(CH3)3 3,5-CI (n = 0)
1-133 CHrc-dH3-2,2-CI2 3,5-CI (n = 0)
1-134 CH2COOC2H5 4-OCH3 (n = 0)
1-135 CH(CH3)COOC2H5 4-OCH3 (n = 0)
1-136 CH2CF3 4-OCH3 (n = 0)
1-137 n-dH7 3-CI, 4-F (n = 0)
1-138 iso-C3H7 3-CI, 4-F (n = 0)
1-139 n-C4H9 3-CI, 4-F (n = 0)
1-140 CH2C«CH 2,3-(CH=CH)2 (n = 0) Ex.No. AR7 (R5)m (Rβ)n m.p.
1-141 CH2CH=CCI2 2,3-(CH=CH)2 (n = 0)
1-142 cyclopropyl 3,5-CF3 (n = 0)
1-143 CH3 3,5-CF3 (n = 0)
1-144 CH2CH2CH3 3,5-CF3 (n = 0)
1-145 CH2CH3 4-Br (n = 0)
1-146 CH3 4-Br (n = 0)
1-147 CH2CH2CH3 4-Br (n = 0)
1-148 CH2CH3 4-CH3 (n = 0)
1-149 CH2CsCH 4-CH3 (n = 0)
1-150 CH3 4-CH3 (n = 0)
1-151 CH2CH3 2-CH3 2-CH3
1-152 CH3 2-CH3 2-CH3
1-153 CH2CH2CH3 2-CH3 2-CH3
1-154 CH2CH3 4-CI 3-CI
1-155 CH3 4-CI 2-CI
1-156 CH2CH2CH3 3-CI 3-CI
1-157 CH2CH3 2,4-CI 2-CI
1-158 CH3 2,4-CI 2,3-CI
1-159 CH2CH2CH3 2,4-CI 3-CI
1-160 CH2CH3 3-CF3 3-CF3
1-161 CH3 2-CF3 3-CF3
1-162 C H2C H2C H3 3-CF3 3-CF3
1-163 CH2CH3 4-CF3 3-CF3
1-164 CH3 4-CI 2-CF3
1-165 CH2CH2CH3 3-F 2-F
1-166 CH2CH3 4-F 2-F
1-167 CH3 2-F 3-F
1-168 CH2CH2CH3 3,5-CI 3-CI
1-169 CH2CH3 2-CI 3-CI
1-170 CH2C≡CH 3-CF3 (n = 0) 87-88 Example Plfl: Preparation of the compound of formula
Figure imgf000046_0001
In a manner analogous to that given in Example P1f), reaction of 3-(4-bromophenyl)-2- hydroximino-3-methoximinopropane and 4-trifluorophenylboric acid yields the title compound having a melting point of 205-206°C (compound 1-3.17).
Example P1p: The other compounds listed in Table 1 -3 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 of the compound in question; c-C3H3is cyclopropyl.
Table 1-3: Compounds of formula
Figure imgf000046_0002
Ex.No. AR7 (Rs)m (Rβ)n m.p.
1-3.1 CH2CH3 2-CH3 (n = 0)
1-3.2 CH3 3-CF3 (n = 0)
1-3.3 CH2CH2CH3 2-CH3 (n = 0)
1-3.4 CH2CH3 4-CI (n = 0)
1-3.5 CH3 4-CI (n = 0)
1-3.6 CH2CH2CH3 4-CI (n = 0)
1-3.7 CH2CH3 3-CI (n = 0)
1-3.8 CH3 3-CI (n = 0)
1-3.9 CH2CH2CH3 3-CI (n = 0)
1-3.10 CH2CH3 2-CI (n = 0)
1-3.11 CH3 2-CI (n = 0) Ex.No. AR7 (Rs)m (Rβ)n m.p.
1-3.12 CH2CH CH3 2-CI (n = 0)
1-3.13 CH2CH3 2,4-CI (n = 0)
1-3.14 CH3 2,4-CI (n = 0)
1-3.15 CH2CH CH3 2,4-CI (n = 0)
1-3.16 CH2CH3 3-CF3 (n = 0)
1-3.17 CH3 4-CF3 (n = 0) 205-206°C
1-3.18 CH2CH CH3 4-CF3 (n = 0)
1-3.19 CH2CH3 4-F (n = 0)
1-3.20 CH3 4-F (n = 0)
1-3.21 CH2CH CH3 3-F (n = 0)
1-322 CH2CH3 3-F (n = 0)
1-3.23 CH3 3-F (n = 0)
1-3.24 CH2CH CH3 4-F (n = 0)
1-3.25 CH2CeH4-3-CF3 4-CF3 (n = 0)
1-3.26 CH2C≡CH 4-CF3 (n = 0)
1-3.27 CH2CH=CCI2 4-F (n = 0)
1-3.28 CH2CH=CH2 4-F (n = 0)
1-3.29 CH2CsCH 4-F (n = 0)
1-3.30 CH2CH=CCI2 3,5-CI (n = 0)
1-3.31 CH2Si(CH3)3 3,5-CI (n = 0)
1-3.32 CH2-c-C3H3-2,2-CI2 3,5-CI (n = 0)
1-3.33 CH2COOC2H5 4-OCH3 (n = 0)
1-3.34 CH(CH3)COOC2H5 4-OCH3 (n = 0)
1-3.35 CH2CF3 4-OCH3 (n = 0)
1-3.36 n-dH7 3-CI, 4-F (n = 0)
1-3.37 iso-C3H7 3-CI, 4-F (n = 0)
1-3.38 n-C4H9 3-CI, 4-F (n = 0)
1-3.39 CH2C≡CH 2,3-(CH=CH)2 (n = 0)
1-3.40 CH2CH=CCI2 2,3-(CH=CH)2 (n = 0)
1-3.41 cyclopropyl 3,5-CF3 (n = 0)
1-3.42 CH3 3,5-CF3 (n = 0)
1-3.43 CH2CH2CH3 3,5-CF3 (n = 0) Ex.No. AR7 (RΛ (Rβ)n m.p.
1-3.44 CH2CH3 4-Br (n = 0)
1-3.45 CH3 4-Br (n = 0)
1-3.46 CH2CH2CH3 4-Br (n = 0)
1-3.47 CH2CH3 4-CH3 (n = 0)
1-3.48 CH2C≡CH 4-CH3 (n = 0)
1-3.49 CH3 4-CH3 (n = 0)
1-3.50 CH2CH3 2-CH3 2-CH3
1-3.51 CH3 2-CH3 2-CH3
1-3.52 CH2CH2CH3 2-CH3 2-CH3
1-3.53 CH2CH3 4-CI 3-CI
1-3.54 CH3 4-CI 2-CI
1-3.55 CH2CH2CH3 3-CI 3-CI
1-3.56 CH2CH3 2,4-CI 2-CI
1-3.57 CH3 2,4-CI 2,3-CI
1-3.58 CH2CH2CH3 2,4-CI 3-CI
1-3.59 CH2CH3 3-CF3 3-CF3
1-3.60 CH3 2-CF3 3-CF3
1-3.61 CH2CH2CH3 3-CF3 3-CF3
1-3.62 CH2CH3 4-CF3 3-CF3
1-3.63 CH3 4-CI 2-CF3
1-3.64 CH2CH2CH3 3-F 2-F
1-3.65 CH2CH3 4-F 2-F
1-3.66 CH3 2-F 3-F
1-3.67 CH2CH2CH3 3,5-CI 3-CI
1-3.68 CH2CH3 2-CI 3-CI
1-3.69 CH2CsCH 3-CF3 (n = 0) 170°C (decomp.)
1-3.70 CH2C≡CH 2,4-CI (n = 0) 191°C (decomp.) Example P1I0: Preparation of the compound of formula
Figure imgf000049_0001
In a manner analogous to that described in Example P1f), reaction of 1 -(4-bromophenyl)-1 - hydroximino-propan-2-one with 3-trifluoromethylphenylboric acid yields the title compound having a melting point of 156-157°C (compound 1-4.6).
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.
Table 1-4: Compounds of formula
Figure imgf000049_0002
Ex. No. (Rs) (Rβ)n phys. data
1-4.1 2-CH3 (n = 0)
IA.2 4-CI (n = 0)
\ 3 3-CI (n = 0)
1-4.4 2-CI (n = 0)
1-43 2,4-CI (n = 0) 199-200
1-4.6 3-CF3 (n = 0) 156-157
IA.7 4-CF3 (n = 0) .8 3,5-CI (n = 0)
\Λ.9 4-OCH3 (n = 0)
1-4.10 3-CI, 4-F (n = 0)
1-4.11 2,3-(CH=CH)2 (n = 0)
1-4.12 3,5-CF3 (n = 0)
1-4.13 4-Br (n = 0)
1 14 4-CH3 (n = 0) Ex.No. (Rs)n (Rβ)n phys. data .15 2-CH3 2-CH3 .16 4-CI 3-CI
1-4.17 4-CI 2-CI .18 3-CI 3-CI .19 2,4-CI 2-CI
I .2D 2,4-CI 2,3-CI
1-4.21 2,4-CI 3-CI
1-4.22 3-CF3 3-CF3
1-4.23 2-CF3 3-CF3
1Λ24 4-CF3 3-CF3
1-4.25 4-CI 2-CF3 .26 3,5-CI 3-CI .27 2-CI 3-CI
Example P2a): Preparation of the compound of formula
Figure imgf000050_0001
2 g of sodium hydride are added, in portions, under an argon atmosphere, to 12.5 g of 3-(4- bromophenyl)-2-hydroximino-3-ethoximinopropane in 65 ml of dimethylfonmamide in an ice- bath. After 1 hour, 11 g of 2-(α-bromo-o-tolyl)-3-methoxy-acrylic acid methyl ester are added and the mixture is stirred at room temperature for a further 20 hours. 2.6 ml of acetic acid are then added to the reaction mixture which is then concentrated. The residue is taken up in ethyl acetate, washed with water, dried and concentrated. Chromatography of the residue on silica gel using ethyl acetate/hexane (1 :25) yields 2-{2-[2-(4-bromo-phenyl)-2-ethoxy- imino-1-methyl-ethylideneaminooxymethylJ-phenyl}-3-methoxy-acrylic acid methyl ester having a melting point of 76-78°C. (compound 2.1). Example P2b): Preparation of the compound of formula
Figure imgf000051_0001
In a manner analogous to that described in Example P2a), reaction of 3-(4-bromophenyl)-2- hydroximino-3-ethoximinopropane and 2-(α-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 P2cϊ: The other compounds listed in Table 2 may also be prepared in a manner analogous to that described in Examples P2a and P2b; c-C3H3and c-C3H5are cyclopropyl.
Table 2: Compounds of formula
Figure imgf000051_0002
11 CH 0 CH2CH3 CH3 4-Br 76-78
12 N 0 CH2CH3 CH3 4-Br 103-104
13 N NH CH2CH3 CH3 4-Br 117-118
14 CH 0 CH2CH3 CH3 3-Br 129-132
15 N 0 CH2CH3 CH3 3-Br 80-83
16 N NH CH2CH3 CH3 3-Br 108-110
17 CH 0 CH2CH3 CH3 2-Br
18 N 0 CH2CH3 CH3 2-Br
19 N NH CH2CH3 CH3 2-Br
110 CH 0 CH2CH3 CH3 4-1
111 N 0 CH2CH3 CH3 4-1
Figure imgf000052_0001
112 CH 0 CH2CH3 CH3 4-1
113 N 0 CH2CH3 CH3 4-1
114 CH 0 CH3 CH3 4-Br 118-120
115 N 0 CH3 CH3 4-Br 108-111
116 N NH CH3 CH3 4-Br 106-110
117 CH 0 CH3 CH3 3-Br 178-180
118 N 0 CH3 CH3 3-Br 125-127
119 N NH CH3 CH3 3-Br 125-127
120 CH 0 CH3 CH3 2-Br
121 N 0 CH3 CH3 2-Br
122 N NH CH3 CH3 2-Br
123 CH 0 CH3 CH3 4-1
124 N 0 CH3 CH3 4-1
125 CH 0 CH3 CH3 4-1
126 N 0 CH3 CH3 4-1
127 CH 0 CH2CβH4-3-CF3 CH3 4-Br
128 N 0 CH2C≡CH CH3 4-Br oil
129 N NH CH2CH=CCI2 CH3 4-Br
130 CH 0 CH2CH=CH2 CH3 3-Br
131 N 0 C2Hδ CH3 3-Br
132 N NH CH2C≡CH CH3 3-Br
133 CH 0 CH2CH=CCI2 CH3 2-Br
134 N 0 CH2Si(CH3)3 CH3 2-Br
135 N NH CH2-c-C3H3-2,2-CI2 CH3 2-Br
136 CH 0 CH2COOC2H5 CH3 4-Br 37 N 0 CH(CH3)COOC2H5 CH3 4-Br 38 CH 0 CH2CF3 CH3 4-Br
139 N 0 n-C3H7 CH3 4-Br
140 N 0 n-dH7 CH3 3-Br
141 N 0 n-C3H7 CH3 2-Br 42 CH 0 iso-C3H7 CH3 4-Br 43 N 0 n-C4H9 CH3 4-Br
Figure imgf000053_0001
145 CH 0 C2Hs CH3 3-Br
146 N 0 CH2C^CH CH3 4-1
147 N NH CH2C≡CH CH3 4-Br
148 CH 0 CH2CH=CCI2 CH3 4-Br
149 N 0 CH2CβH4-3-CF3 CH3 4-Br
150 CH 0 CH2CsCH CH3 4-Br oil
151 CH 0 CH3 C2Hs 4-Br 97-99
152 N 0 CH3 C2Hs 4-Br 114-115
153 N NH CH3 C2Hs 4-Br 105-107
154 CH 0 Hs Hs 4-Br 89-92
155 N 0 C2Hs C2Hs 4-Br 110-113
156 N NH C2Hs C2H5 4-Br 130-132
157 CH 0 CH3 C-dH5 4-Br resin
158 N 0 CH3 c-dH5 4-Br oil
159 N NH CH3 c-dHs 4-Br resin
160 CH 0 CH2CH3 c-C3Hs 4-Br
161 N 0 CH2CH3 c-dH5 4-Br
162 N NH CH2CH3 c-C3H5 4-Br
Example P3a): Preparation of a compound of formula
Figure imgf000053_0002
8.1 ml of 2,3-dimethylbutadiene and 10 mol %, based on the starting material, of copper acetate are added to 1.5 g of 2-{2-[2-(4-ethynyl-phenyl)-2-methoxyimino-1-methyl-ethyli- dene-aminooxymethyl]-phenyl}-3-methoxy-acrylic acid methyl ester in 3.5 ml of toluene, and the mixture is heated at 110°C in an autoclave for 92 hours. The reaction mixture is diluted with 90 ml of diethyl ether and washed with 90 ml of water. The aqueous phase is extracted with diethyl ether. The combined organic phases are dried over sodium sulphate and concentrated in vacuo. Chromatography of the crude product on silica gel (hexane:diethyl ether 3:1) yields the title compound having a melting point of 99-100°C (compound 3-1.14).
Example P3bϊ: 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.
Table 3-1 : Compounds of general formula
Figure imgf000054_0001
Ex. No. Y1 AR7 (Rκ)ς Rt36 m.p.
3-1.1 CH 0 CH3 3-CF3 H
3-12 N 0 CH3 5-CF3 H
3-1.3 N NH CH3 6-CH3 H
3-1.4 C 0 CH3 4-CI H
3-1.5 N 0 CH3 4-CI H
3-1.6 N NH CH3 q = 0 CH3
3-1.7 CH 0 CH3 4,5-CI2 C(0)CH3
3-1.8 N 0 CH3 4,5-CI2 C(0)OCH3 -1.9 N NH CH3 4,5-l2 C(0)CH3
3-1.10 CH 0 CH3 q = 0 CH2OH
3-1.11 N 0 CH3 4-CF3 C(0)NH2 -1.12 CH 0 CH3 4-CF3 Si(CH3)3 -1.13 N 0 CH3 4-CF3 H -1.14 CH 0 CH3 4,5-(CH3)2 H 99-100 -1.15 N 0 CH3 4,5-(CH3)2 H 103-111 -1.16 N NH C2Hs 3,4,5-Br3 H Examole P3c : Preparation of
Figure imgf000055_0001
1 g of 2-{2-[2-(4-bromo-phenyl)-2-ethoxyimino-1-methyl-ethylideneaminooxymethyl]-phenyl}- 3-methoxy-acrylic acid methyl ester, 0.7 g of potassium carbonate, 0.25 g of tetrakis- triphenylphosphinepalladium(O), 9 ml of dimethoxyethane, 6 ml of tetrahydrofuran, 9 ml of water and 0.33 g of o-methylphenylboric acid are stirred under an argon atmosphere at 75°C for 5 hours. The reaction mixture is taken up in ethyl acetate, washed with water, dried and concentrated. Chromatography of the crude product on silica gel using ethylaceta- te/hexane (1:19) yields the title compound having a melting point of 48-49°C (compound 3- 2.1).
Example P3d : Preparation of the compound of formula
Figure imgf000055_0002
In a manner analogous to that described in Example P3c), reaction of 2-{2-[2-(4-bromo- phenyl)-2-ethoxyimino-1-methyl-ethylideneaminooxymethyl]-phenyl}-3-methoxyimino-acetJc acid methyl ester and o-methylphenylboric acid yields the title compound having a melting point of 59-60°C (compound 3-2.2). Example P3e Preparation of
Figure imgf000056_0001
0.55 ml of an 8M solution of methylamine in ethanol is added to 0.6 g of 2-{2-[2-ethoxy- imino-1-methyl-2-(4-(2-methylphenyl)-phenyl)-ethylideneamino-oxy-methyl]-phenyl}-3- methoxyimino-acetic acid methyl ester in 5 ml of dimethylformamide, and the mixture is stirred at room temperature for 3 days. The reaction mixture is concentrated, taken up in ethyl acetate and washed with water, and the organic phase is dried, concentrated and filtered to yield the title compound having a melting point of 95-96°C (compound 3-2.3).
Example Pβft: Preparation of a compound of formula
Figure imgf000056_0002
300 mg of 2-{2-[2-(4-(4,5-dimethyl-cyclohexa-1,4-dienyl)-phenyl)-2-methoxyimino-1-methyl- ethylideneaminooxymethyl]-phenyl}-3-methoxy-acrylic acid methyl ester and 205 mg of 2,3-dichloro-5,6-dicyano-1 ,4-benzoquinone in 2 ml of toluene are stirred at room temperature for 16 hours. The reaction mixture is diluted with diethyl ether and washed with sodium hydrogen carbonate solution. The organic phase is dried over sodium sulfate and concentrated. Recrystallisation from hexane yields the title compound having a melting point of 138-141 °C (compound 3-2.101).
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-C3H3and c-C3H5are cyclopropyl. Table 3-2: Compounds of general formula
Figure imgf000057_0001
3-2.1 CH 0 CH2CH3 CH3 2-CH3 48-49°C
3-22 N 0 CH2CH3 CH3 2-CH3 59-60°C
3-2.3 N NH CH2CH3 CH3 2-CH3 95-96°C
3-2.4 C 0 CH2CH3 CH3 4-CI 135-136°C
3-2.5 N 0 CH2CH3 CH3 4-CI 90-91 °C
3-2.6 N NH CH2CH3 CH3 4-CI 63-64°C
3-2.7 CH 0 CH2CH3 CH3 2,4-CI 53-54°C
3-2.8 N 0 CH2CH3 CH3 2,4-CI 111-112°C
3-2.9 N NH CH2CH3 CH3 2,4-CI 180-181 °C
3-2.10 CH 0 CH2CH3 CH3 3-CF3 133-134°C
3-2.11 N 0 CH2CH3 CH3 3-CF3 142-143°C
3-2.12 CH 0 CH2CH3 CH3 4-CF3 143-144°C
3-2.13 N 0 CH2CH3 CH3 4-CF3 91-92°C -2.14 N NH CH2CH3 CH3 4-CF3 185-186°C -2.15 CH 0 CH2CH3 CH3 4-F 130-131 °C -2.16 N 0 CH2CH3 CH3 4-F 89-90°C -2.17 N NH CH2CH3 CH3 4-F 166-167°C -2.18 CH 0 CH2CH3 CH3 3,5-CI2 116-117°C -2.19 N 0 CH2CH3 CH3 3,5-CI2 94-95°C -220 N NH CH2CH3 CH3 3,5-CI2 91-92°C -221 CH 0 CH2CH3 CH3 4-OCH3 98-99°C -222 N 0 CH2CH3 CH3 4-OCH3 resin -2.23 N NH CH2CH3 CH3 4-OCH3 132-133°C -224 CH 0 CH2CH3 CH3 3-CI, 4-F 132-133°C
Figure imgf000058_0001
Figure imgf000059_0001
Figure imgf000060_0001
3-2.89 N NH CH3 CH3 4-CH3 107-108°C
3-2.90 N 0 CH3 CH3 3,5-(CF3)2 130-131 °C
3-2.91 N NH CH3 CH3 3,5-(CF3)2 126-127°C
3-2.92 N NH CH3 CH3 2,3-(CH=CH)2 117-118°C
3-2.93 CH 0 CH2C≡CH CH3 2-CH3 resin
3-2.94 CH 0 CH2C≡CH CH3 3-CF3 74°C (decomp.)
3-2.95 N 0 CH2CsCH CH3 3-CF3 94°C (decomp.)
3-2.96 CH 0 CH2C≡CH CH3 2,4-CI2 66°C (decomp.)
3-2.97 N 0 CH2C≡CH CH3 2,4-CI2 120°C (decomp.)
3-2.98 CH 0 CH3 c-CβHs 3-CF3 resin
3-2.99 N 0 CH3 C-CsHs 3-CF3 resin
3-2.100 N NH CH3 C-CβHs 3-CF3 72-75
3-2.101 CH 0 CH3 CH3 3,4-(CH3)2 138-141
3-2.102 N 0 CH3 CH3 3,4-(CH3)2
3-2.103 N NH CH3 CH3 3,4-(CH3)2
3-2.104 CH 0 CH3 C2Hδ 3-CF3 121-122
3-2.105 N 0 CH3 C2Hs 3-CF3 104-106
3-2.106 N NH CH3 C2Hs 3-CF3 142-143
Table 3-3: Comp lounds of formula
Figure imgf000060_0002
3-3.1 CH O CH3 4-CI 120-122°C
3-3.2 N O CH3 4-CI 144-145°C
3-3.3 N NH CH3 4-CI 155-156°C
3-3.4 C O CH3 2,4-CI2 117-120°C
Figure imgf000061_0001
3-3.5 N 0 CH3 2,4-Cla 123-125°C
3-3.6 N NH CH3 2,4-CI2 155-156°C
3-3.7 CH 0 CH3 3,5-CI2 147-149°C
3-3.8 N 0 CH3 3,5-CI2 126-128°C
3-3.9 N NH CH3 3,5-CI2 149-150°C
3-3.10 CH 0 CH3 4-CF3 161-163°C
3-3.11 N 0 CH3 4-CF3 122-125°C
3-3.12 N NH CH3 4-CF3 122-124°C -3.13 CH 0 CH3 2-CH3 113-114°C -3.14 N 0 CH3 2-CH3 100-102°C -3.15 N NH CH3 2-CH3 150-151 °C -3.16 CH 0 CH3 3-CF3 179-182°C -3.17 N 0 CH3 3-CF3 118-120°C -3.18 N NH CH3 3-CF3 112-113°C -3.19 CH 0 CH2CH3 4-CI 95°C -3.20 N 0 CH2CH3 4-CI 95-96°C -3.21 N NH CH2CH3 4-CI 114-116°C -3.22 CH 0 CH2CH3 3,5-CI2 120-122°C -3.23 N 0 CH2CH3 3,5-CI2 150-153°C -324 N NH CH2CH3 3,5-CI2 resin -325 CH 0 CH2CH3 2,4-Cla 100-103°C -326 N 0 CH2CH3 2,4-CI2 103-105°C -3.27 N NH CH2CH3 2,4-CI2 resin -328 CH 0 CH2CH3 2-CH3 76-78°C -3.29 N 0 CH2CH3 2-CH3 92-94°C -3.30 N NH CH2CH3 2-CH3 resin -3.31 CH 0 CH2CH3 3-CF3 112-115°C -3.32 N 0 CH2CH3 3-CF3 78-80°C -3.33 CH 0 CH2CH3 4-CF3 84-85°C -3.34 N 0 CH2CH3 4-CF3 110-111°C -3.35 N NH CH2CH3 4-CF3 135-137°C Table 4: Compounds of formula
Figure imgf000062_0001
wherein AR7 is CH3 and the combination of substituents X, Y, (R5)m and (Rβ)n for each individual compound corresponds to a line of Table A.
Table 5: Compounds of formula (la) wherein AR7 is CH2CH3and the combination of substituents X, Y, (R5)m and (Rβ)n for each individual compound corresponds to a line of Table A.
Table 6: Compounds of formula (la) wherein AR7 is CH2CH=CH2and the combination of substituents X, Y, (Rs)m and (Rβ)n for each individual compound corresponds to a line of Table A.
Table 7: Compounds of formula (la) wherein AR7 is CH2C≡CH and the combination of substituents X, Y, (R5)π» and (Rβ)„ for each individual compound corresponds to a line of Table A.
Table 8: Compounds of formula (la) wherein AR7 is CH2CH2CH3 and the combination of substituents X, Y, (Rs)m and (Rβ)n for each individual compound corresponds to a line of Table A.
Table 9: Compounds of formula (la) wherein AR7 is CH(CH3)2 and the combination of substituents X, Y, (R5)m and (Rβ)n for each individual compound corresponds to a line of Table A.
Table 10: Compounds of formula (la) wherein AR7 is CH2CH2CH2CH3 and the combination of substituents X, Y, (R5)m and (R6)n for each individual compound corresponds to a line of Table A.
Table 11 : Compounds of formula (la) wherein AR7 is CH(CH3)(CH2CH3) and the combination of substituents X, Y, (R5)m and (Rβ)n for each individual compound corresponds to a line of Table A. Table 12: Compounds of formula (la) wherein AR7 is C(CH3)3and the combination of substituents X, Y, (Rs)m and (R6)n for each individual compound corresponds to a line of Table A.
Table 13: Compounds of formula (la) wherein AR7 is n-C6Hi3and the combination of substituents X, Y, (R5)tn and (Rβ)n for each individual compound corresponds to a line of Table A.
Table 14: Compounds of formula (la) wherein AR7 is CH2F and the combination of substituents X, Y, ( s)m and (R6)n for each individual compound corresponds to a line of Table A.
Table 15: Compounds of formula (la) wherein AR7 is CHF2and the combination of substituents X, Y, (Rs)m and (R6)n for each individual compound corresponds to a line of Table A.
Table 16: Compounds of formula (la) wherein AR7 is CH2CF3and the combination of substituents X, Y, (R5)m and (Rβ)n for each individual compound corresponds to a line of Table A.
Table 17: Compounds of formula (la) wherein AR7 is CH2CH=CH2and the combination of substituents X, Y, (R5)m and (Rβ)n for each individual compound corresponds to a line of Table A.
Table 18: Compounds of formula (la) wherein AR7 is CH2CH=CHCH3and the combination of substituents X, Y, (R5)m and (Rβ)n for each individual compound corresponds to a line of Table A.
Table 19: Compounds of formula (la) wherein AR7 is CH2CH=C(CH3)2and the combination of substituents X, Y, (Rs)m and (Rβ)n for each individual compound corresponds to a line of Table A.
Table 20: Compounds of formula (la) wherein AR7 is CH2CH=CHCI and the combination of substituents X, Y, (R5)m and (R6)n for each individual compound corresponds to a line of Table A.
Table 21 : Compounds of formula (la) wherein AR7 is CH2CH=CCI2and the combination of substituents X, Y, (R5)m and (R6)n for each individual compound corresponds to a line of Table A.
Table 22: Compounds of formula (la) wherein AR7 is CH2C(CH3)=CH2and the combination of substituents X, Y, (R5)m and (Rβ)n for each individual compound corresponds to a line of Table A. Table 23: Compounds of formula (la) wherein AR7 is CH^i^H^and the combination of substituents X, Y, (R5)m and (R6)n for each individual compound corresponds to a line of Table A.
Table 24: Compounds of formula (la) wherein AR7 is CH2-cyclopropyl-2,2-CI2and the combination of substituents X, Y, (R5)m and (R6)n for each individual compound corresponds to a line of Table A.
Table 25: Compounds of formula (la) wherein AR7 is CH2-cyclopropyl and the combination of substituents X, Y, (R5)m and (R6)n for each individual compound corresponds to a line of Table A.
Table 26: Compounds of formula (la) wherein AR7 is CH2CN and the combination of substituents X, Y, (R5)m and (Rβ)n for each individual compound corresponds to a line of Table A.
Table 27: Compounds of formula (la) wherein AR7 is CH2COOCH3and the combination of substituents X, Y, (R5)m and (Rβ)n for each individual compound corresponds to a line of Table A.
Table 28: Compounds of formula (la) wherein AR7 is CH2COOC2H5and the combination of substituents X, Y, (R5)m and (R6)n for each individual compound corresponds to a line of Table A.
Table 29: Compounds of formula (la) wherein AR7 is CH2COO-iso-C3H7and the combination of substituents X, Y, (R5)m and (R6)n for each individual compound corresponds to a line of Table A.
Table 30: Compounds of formula (la) wherein AR7 is CH(CH3)COOC2H5and the combination of substituents X, Y, (R5)m and (R6)n for each individual compound corresponds to a line of Table A.
Table 31 : Compounds of formula (la) wherein AR7 is C(=0)OC2H5and the combination of substituents X, Y, (R5)m and (R6)n for each individual compound corresponds to a line of Table A.
Table 32: Compounds of formula (la) wherein AR7 is C(=0)NHCH3and the combination of substituents X, Y, (R5)m and (R6)n for each individual compound corresponds to a line of Table A. Table 33: Compounds of formula (la) wherein AR7 is C(=0)C(=0)OC2H5and the combination of substituents X, Y, (Rs)m and (R6)n for each individual compound corresponds to a line of Table A.
Table 34: Compounds of formula (la) wherein AR7 is CH2C6H5and the combination of substituents X, Y, (R5)m and (R6)n for each individual compound corresponds to a line of Table A.
Table 35: Compounds of formula (la) wherein AR7 is CH2CβH4-2-F and the combination of substituents X, Y and (R5)m for each individual compound corresponds to a line of Table A.
Table 36: Compounds of formula (la) wherein AR7 is CH2C6H4-3-F and the combination of substituents X, Y, (R5)m and (R6)n for each individual compound corresponds to a line of Table A.
Table 37: Compounds of formula (la) wherein AR7 is CH2CβH -4-F and the combination of substituents X, Y, (R5)m and (Rβ)n for each individual compound corresponds to a line of Table A.
Table 38: Compounds of formula (la) wherein AR7 is CH2CβH4-2-CI and the combination of substituents X, Y, (R5)m and (Rβ)n for each individual compound corresponds to a line of Table A.
Table 39: Compounds of formula (la) wherein AR7 is CH2CβH4-3-CI and the combination of substituents X, Y, (R5)m and (R6)n for each individual compound corresponds to a line of Table A.
Table 40: Compounds of formula (la) wherein AR7 is CH2CβH4-4-CI and the combination of substituents X, Y, (R5)m and (R6)n for each individual compound corresponds to a line of Table A.
Table 41 : Compounds of formula (la) wherein AR7 is CH2C6H4-2-Br and the combination of substituents X, Y, (R5)m and (R6)n for each individual compound corresponds to a line of Table A.
Table 42: Compounds of formula (la) wherein AR is CH2C6H4-3-Br and the combination of substituents X, Y, (R5) and (Rβ)n for each individual compound corresponds to a line of Table A. Table 43: Compounds of formula (la) wherein AR7 is CH2C6H4-4-Br and the combination of substituents X, Y, (R5)m and (R6)n for each individual compound corresponds to a line of Table A.
Table 44: Compounds of formula (la) wherein AR7 is CH2CβHr2-CF3and the combination of substituents X, Y, (R5)m and (R6)n for each individual compound corresponds to a line of Table A.
Table 45: Compounds of formula (la) wherein AR7 is CH2C6H4-3-CF3and the combination of substituents X, Y, (R5)m and (Rβ)n for each individual compound corresponds to a line of Table A.
Table 46: Compounds of formula (la) wherein AR7 is CH2CβH4-4-CF3and the combination of substituents X, Y, (R5)m and (Rβ)n for each individual compound corresponds to a line of Table A.
Table A
Figure imgf000066_0001
A.1 CH OCH3 2-CH3 (n = 0)
A.2 N OCH3 2-CH3 (n = 0)
A.3 N NHCH3 2-CH3 (n = 0)
A4 CH OCH3 4-CI (n = 0)
A.5 N OCH3 4-CI (n = 0)
A.6 N NHCH3 4-CI (n = 0)
A.7 CH OCH3 3-CI (n = 0)
A.8 N OCH3 3-CI (n = 0)
A.9 N NHCH3 3-CI (n = 0)
A.10 CH OCH3 2-CI (n = 0)
A.11 N OCH3 2-CI (n = 0)
A.12 N NHCH3 2-CI (n = 0)
A.13 CH OCH3 2,4-CI2 (n = 0)
A.14 N OCH3 2,4-CI2 (n = 0)
A.15 N NHCH3 2,4-Cla (n = 0)
A.16 CH OCH3 3-CF3 (n = 0)
A.17 N OCH3 3-CF3 (n = 0)
A.18 N NHCH3 3-CF3 (n = 0)
Figure imgf000067_0001
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o X z z o X z z o X z z o X z z o X z o X z z oX z o X z o X z z oX z o X
Figure imgf000068_0001
o X X x oo o X x ox ox o X
X o x x ox ox ox Oxx ooX ooX Oxx ooX ooX Oxx ooX ooX Oxx ooX ooX Oxx ooX ooX Oxx ooX ooX Oxx oX oX
X X JQ co co co co ^ to ω c u 3; co co j to co T co ω
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Figure imgf000068_0002
3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 X
II II II II II II II II II II II tt II II II II II II II II II II II II II II II II II II II II •?_»
O O 0 0 0 0 0 0 0 0 0 O 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0
Figure imgf000069_0001
Figure imgf000070_0001
A.115 N OCH3 2,5-CI 3-CH3
A.116 N NHCH3 2,5-CI 3-CH3
A.117 CH OCH3 4-Br 3-CH3
A.118 N OCH3 4-Br 3-CH3
A.119 N NHCH3 4-Br 3-CH3
A.120 CH OCH3 4-CI 3-CI
A.121 N OCH3 4-CI 3-CI
A.122 N NHCH3 4-CI 3-CI
A.123 CH OCH3 4-CI 2-CI
A.124 N OCH3 4-CI 2-CI
A.125 N NHCH3 4-CI 2-CI
A.126 N NHCH3 3-CI 3-CI
A.127 CH OCH3 2,4-Cla 2-CI
A.128 N OCH3 2,4-CI2 2-CI
A.129 N NHCH3 2,4-CI2 2-CI
A.130 CH OCH3 2,3-CI2 2-CI
A.131 N OCH3 2,3-CI2 2-CI
A.132 N NHCH3 2,3-CI2 2-CI
A.133 CH OCH3 3-CF3 3-CF3
A.134 N OCH3 2-CF3 3-CF3
A.135 CH OCH3 3-CF3 3-CF3
A.136 N OCH3 3-CF3 3-CF3
A.137 N NHCH3 4-CF3 2-CI
A.138 CH OCH3 4-F 3-F
A.139 N OCH3 4-F 2-F
A.140 N NHCH3 2-F 3-F
A.141 CH OCH3 2,6-CI2 3-CI
A.142 N OCH3 2,6-CI2 3-CI
A.143 N NHCH3 2,6-CI2 3-CI
A.144 CH OCH3 3-CI 3,5-CI2
A.145 N OCH3 3,5-CI2 2-CI
A.146 N NHCH3 3,4-CI2 3-CI
Figure imgf000071_0001
A.147 CH OCH3 4-OCH3 2-OCH3
A.148 N OCH3 3-OCH3 2-OCH3
A.149 N NHCH3 2-OCH3 2-OCH3
A.150 CH OCH3 2-CI, 4-F 3-CI, 5-F
A.151 N OCH3 3-CI 3-CI, 5-F
A.152 N NHCH3 3-F 3-CI, 5-F
A.153 CH OCH3 2,3-(CH=CH)2 2,3-(CH=CH)2
A.154 N OCH3 2,3-(CH=CH)2 2,3-(CH=CH)2
A.155 CH OCH3 3-F 3,5-(CF3)2
A.156 N OCH3 3-CF3 3,5-(CF3)2
A.157 N NHCH3 3-CF3 3,5-(CF3)2
A.158 CH OCH3 4-Br 2-Br
A.159 N OCH3 2-Br 2-Br
A.160 N NHCH3 4-Br 3-Br
A.161 CH OCH3 3-CH3 2-CH3
A.162 N OCH3 4-CHO (n = 0)
A.163 N NHCH3 4-CHO (n = 0)
A.164 CH OCH3 4-CHO (n = 0)
A.165 N OCH3 4-CH=NOCH3 (n = 0)
A.166 N NHCH3 4-CH=NOCH3 (n = 0)
A.167 CH OCH3 4-CH=NOCH3 (n = 0)
Table 47: Compounds of formula (lb) wherein AR7 is CH3 and the combination of substituents X, Y, (R5)m and (R6)n for each individual compound corresponds to a line of Table B.
Table 48: Compounds of formula (lb) wherein AR7 is CH2CH3and the combination of substituents X, Y, (R5) and (R6)n for each individual compound corresponds to a line of Table B.
Table 49: Compounds of formula (lb) wherein AR7 is CH2CH=CH2 and the combination of substituents X, Y, (R5)m and (Rβ)n for each individual compound corresponds to a line of Table B. Table 50: Compounds of foπnula (lb) wherein AR7 is CH2C≡CH and the combination of substituents X, Y, (R5)m and (Rβ)n for each individual compound corresponds to a line of Table B.
Table 51 : Compounds of formula (lb) wherein AR7 is CH2CH2CH3 and the combination of substituents X, Y, (R5)m and (Rβ)n for each individual compound corresponds to a line of Table B.
Table 52: Compounds of formula (lb) wherein AR7 is CH(CH3)2 and the combination of substituents X, Y, (R5)m and (Rβ)n for each individual compound corresponds to a line of Table B.
Table 53: Compounds of formula (lb) wherein AR7 is CH2CH2CH2CH3 and the combination of substituents X, Y, (R5)m and (Rβ)n for each individual compound corresponds to a line of Table B.
Table 54: Compounds of formula (lb) wherein AR7 is CH(CH3)(CH2CH3) and the combination of substituents X, Y, (Rs)m and (Rβ)π for each individual compound corresponds to a line of Table B.
Table 55: Compounds of formula (lb) wherein AR7 is C(CH3)3and the combination of substituents X, Y, (R5)m and (Rβ)n for each individual compound corresponds to a line of Table B.
Table 56: Compounds of formula (lb) wherein AR7 is n-C6H13and the combination of substituents X, Y, (R5)m and (Rβ)n for each individual compound corresponds to a line of Table B.
Table 57: Compounds of formula (lb) wherein AR7 is CH2F and the combination of substituents X, Y, (R5)m and (Rβ)„ for each individual compound corresponds to a line of Table B.
Table 58: Compounds of formula (lb) wherein AR7 is CHF2and the combination of substituents X, Y, (R5)m and (Rβ)n for each individual compound corresponds to a line of Table B.
Table 59: Compounds of formula (lb) wherein AR7 is CH2CF3and the combination of substituents X, Y, (R5)m and (Rβ)n for each individual compound corresponds to a line of Table B. Table 60: Compounds of formula (lb) wherein AR7 is CH2CH=CH2and the combination of substituents X, Y, (R5)m and (Rβ)n for each individual compound corresponds to a line of Table B.
Table 61 : Compounds of formula (lb) wherein AR7 is CH2CH=CHCH3and the combination of substituents X, Y, (R5)m and (R6)n for each individual compound corresponds to a line of Table B.
Table 62: Compounds of formula (lb) wherein AR7 is CH2CH=C(CH3)2and the combination of substituents X, Y, (R5)m and (R6)n for each individual compound corresponds to a line of Table B.
Table 63: Compounds of formula (lb) wherein AR7 is CH2CH=CHCI and the combination of substituents X, Y, (R5)m and (Rβ)n for each individual compound corresponds to a line of Table B.
Table 64: Compounds of formula (lb) wherein AR7 is CH2CH=CCI2and the combination of substituents X, Y, (R5)m and (R6)n for each individual compound corresponds to a line of Table B.
Table 65: Compounds of formula (lb) wherein AR7 is CH2C(CH3)=CH2and the combination of substituents X, Y, (R5)m and (R6)n for each individual compound corresponds to a line of Table B.
Table 66: Compounds of formula (lb) wherein AR7 is CH2Si(CH3)3and the combination of substituents X, Y, (R5)m and (R6)n for each individual compound corresponds to a line of Table B.
Table 67: Compounds of formula (lb) wherein AR7 is CH2-cyclopropyl-2,2-CI2and the combination of substituents X, Y, (R5) and (R6)n for each individual compound corresponds to a line of Table B.
Table 68: Compounds of foπnula (lb) wherein AR7 is CH2-cyclopropyl and the combination of substituents X, Y, (R5) and (R6)n for each individual compound corresponds to a line of Table B.
Table 69: Compounds of formula (lb) wherein AR is CH2CN and the combination of substituents X, Y, (R5)m and (R6)n for each individual compound corresponds to a line of Table B. Table 70: Compounds of foπnula (lb) wherein AR7 is CH2COOCH3and the combination of substituents X, Y, (R5)m and (R6)n for each individual compound corresponds to a line of Table B.
Table 71 : Compounds of formula (lb) wherein AR7 is CH2COOC2H5and the combination of substituents X, Y, (R5)m and (Rβ)n for each individual compound corresponds to a line of Table B.
Table 72: Compounds of formula (lb) wherein AR7 is CH2COO-iso-C3H7and the combination of substituents X, Y, (R5)m and (R6)n for each individual compound corresponds to a line of Table B.
Table 73: Compounds of foπnula (lb) wherein AR7 is CH(CH3)COOC2H5and the combination of substituents X, Y, (R5)m and (R6)n for each individual compound corresponds to a line of Table B.
Table 74: Compounds of foπnula (lb) wherein AR7 is C(=0)OC2H5and the combination of substituents X, Y, (R5)m and (R6)n for each individual compound corresponds to a line of Table B.
Table 75: Compounds of formula (lb) wherein AR7 is C(=0)NHCH3and the combination of substituents X, Y, (R5)m and (R6)n for each individual compound corresponds to a line of Table B.
Table 76: Compounds of formula (lb) wherein AR7 is C(=0)C(=0)OC2H5 and the combination of substituents X, Y, (R5)m and (R6)n for each individual compound corresponds to a line of Table B.
Table 77: Compounds of formula (lb) wherein AR7 is CH2C6H5and the combination of substituents X, Y, (R5)m and (R6)n for each individual compound corresponds to a line of Table B.
Table 78: Compounds of formula (lb) wherein AR7 is CH2CβH4-2-F and the combination of substituents X, Y and (R5)m for each individual compound corresponds to a line of Table B.
Table 79: Compounds of foπnula (lb) wherein AR7 is CH2C6H4-3-F and the combination of substituents X, Y, (R5)m and (R6)n for each individual compound corresponds to a line of Table B. Table 80: Compounds of formula lb) wherein AR7 is CH2C6H4-4-F and the combination of substituents X, Y, (R5)m and (Rβ)n or each individual compound corresponds to a line of Ta- ble B.
Table 81 : Compounds of formula Ib) wherein AR7 is CH2CβH4-2-CI and the combination of substituents X, Y, (R5)m and (R6)n or each individual compound corresponds to a line of Ta- ble B.
Table 82: Compounds of formula Ib) wherein AR7 is CH2CβH4-3-CI and the combination of substituents X, Y, (R5)m and (R6)n or each individual compound corresponds to a line of Ta- ble B.
Table 83: Compounds of formula Ib) wherein AR7 is CH2CβH4-4-CI and the combination of substituents X, Y, (R5)m and (R6)n or each individual compound corresponds to a line of Ta- ble B.
Table 84: Compounds of formula Ib) wherein AR7 is CH2C6H4-2-Br and the combination of substituents X, Y, (R5) and (Rβ)n or each individual compound corresponds to a line of Ta- ble B.
Table 85: Compounds of formula Ib) wherein AR7 is CH2CβH4-3-Br and the combination of substituents X, Y, (R5)m and (R6)n or each individual compound corresponds to a line of Ta- ble B.
Table 86: Compounds of formula Ib) wherein AR7 is CH2CβH4-4-Br and the combination of substituents X, Y, (R5)m and (R6)n or each individual compound corresponds to a line of Ta- ble B.
Table 87: Compounds of formula Ib) wherein AR is CH2C6H4-2-CF3and the combination of substituents X, Y, (R5)m and (R6)n or each individual compound corresponds to a line of Ta- ble B.
Table 88: Compounds of formula Ib) wherein AR7 is CH2C6H4-3-CF3and the combination of substituents X, Y, (R5)m and (R6)n or each individual compound corresponds to a line of Ta- ble B.
Table 89: Compounds of foπnula Ib) wherein AR7 is CH2C6H4-4-CF3and the combination of substituents X, Y, (R5)m and (R6)n or each individual compound corresponds to a line of Ta- ble B. Table B
Figure imgf000076_0001
B.1 CH OCH3 2-CH3 (n = 0)
B.2 N OCH3 2-CH3 (n = 0)
B.3 N NHCH3 2-CH3 (n = 0)
B.4 CH OCH3 4-CI (n = 0)
B.5 N OCH3 4-CI (n = 0)
B.6 N NHCH3 4-CI (n = 0)
B.7 CH OCH3 3-CI (n = 0)
B.8 N OCH3 3-CI (n = 0)
B.9 N NHCH3 3-CI (n = 0)
B.10 CH OCH3 2-CI (n = 0)
B.11 N OCH3 2-CI (n = 0)
B.12 N NHCH3 2-CI (n = 0)
B.13 CH OCH3 2,4-CI2 (n = 0)
B.14 N OCH3 2,4-CI2 (n = 0)
B.15 N NHCH3 2,4-CI2 (n = 0)
B.16 CH OCH3 3-CF3 (n = 0)
B.17 N OCH3 3-CF3 (n = 0)
B.18 N NHCH3 3-CF3 (n = 0)
B.19 CH OCH3 4-CF3 (n = 0)
B20 N OCH3 4-CF3 (n = 0)
B.21 N NHCH3 4-CF3 (n = 0)
B22 CH OCH3 4-F (n = 0)
B23 N OCH3 4-F (n = 0)
B24 N NHCH3 4-F (n = 0)
B25 CH OCH3 3-F (n = 0)
B.26 N OCH3 3-F (n = 0)
B27 N NHCH3 3-F (n = 0)
B28 CH OCH3 2-F (n = 0)
B29 N OCH3 2-F (n = 0)
B.30 N NHCH3 2-F (n = 0)
B.31 CH OCH3 3,5-CI2 (n = 0)
Figure imgf000077_0001
Figure imgf000078_0001
B.64 N OCH3 2-C(CH3)3 (n = 0)
B.65 N NHCH3 2-C(CH3)3 (n = 0)
B.66 CH OCH3 4-CH2CH3 (n = 0)
B.67 N OCH3 4-CH2CH3 (n = 0)
B.68 N NHCH3 4-CH2CH3 (n = 0)
B.69 CH OCH3 4-CH(CH3)2 (n = 0)
B.70 N OCH3 4-CH(CH3)2 (n = 0)
B.71 N NHCH3 4-CH(CH3)2 (n = 0)
B.72 CH OCH3 4-C(CH3)3 (n = 0)
B.73 N OCH3 4-C(CH3)3 (n = 0)
B.74 N NHCH3 4-C(CH3)3 (n = 0)
B.75 CH OCH3 2,4-CH3 (n = 0)
B.76 N OCH3 2,4-CH3 (n = 0)
B.77 N NHCH3 2,4-CH3 (n = 0)
B.78 CH OCH3 2,6-CH3 (n = 0)
B.79 N OCH3 2,6-CH3 (n = 0)
B.80 N NHCH3 2,6-CH3 (n = 0)
B.81 CH OCH3 2,4,6-CH3 (n = 0)
B.82 N OCH3 2,4,6-CH3 (n = 0)
B.83 N NHCH3 2,4,6-CH3 (n = 0)
B.84 CH OCH3 4-C6H5 (n = 0)
B.85 N OCH3 4-C6H5 (n = 0)
B.86 N NHCH3 4-CβHs (n = 0)
B.87 CH OCH3 4-0-C6H5 (n = 0)
B.88 N OCH3 4-0-C6H5 (n = 0)
B.89 N NHCH3 4-0-C6H5 (n = 0)
B.90 CH OCH3 4-N02 (n = 0)
B.91 N OCH3 4-N02 (n = 0)
B.92 N NHCH3 4-N02 (n = 0)
B.93 CH OCH3 4-CN (n = 0)
B.94 N OCH3 4-CN (n = 0)
B.95 N NHCH3 4-CN (n = 0)
Figure imgf000079_0001
Figure imgf000079_0002
Figure imgf000079_0003
Figure imgf000080_0001
B.128 N OCH3 2-Br 2-Br
B.129 N NHCH3 4-Br 4-Br
B.130 CH OCH3 3-CH3 2-CH3
B.131 N OCH3 4-CHO (n = 0)
B.132 N NHCH3 4-CHO (n = 0)
B.133 CH OCH3 4-CHO (n = 0)
B.134 N OCH3 4-CH=NOCH3 (n = 0)
B.135 N NHCH3 4-CH=NOCH3 (n = 0)
B.136 CH OCH3 4-CH=NOCH3 (n = 0)
Formulation ExamDles fthroui
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.
ExamDle F3: Granules a) b) c) d) active ingredient 5% 10% 8% 21% kaolin 94% - 79% 54% highly dispersed silicic acid 1% - 13% 7% attapulgite - 90% - 18%
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% .
Active ingredient is mixed with the adjuvants and the mixture is ground in a suitable mill, affording wettable powders which can be diluted with water to give suspensions of any desired concentration. Example F6: Emulsifiable concentrate active ingredient 10% octylphenol polyethylene glycol ether 3%
(4-5 mol of ethylene oxide) calcium dodecylbenzenesulfonate 3% castor oil polyethylene glycol ether 4%
(36 mol of ethylene oxide) cyclohexanone 30% xylene mixture 50%
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%
The finely ground active ingredient is uniformly applied, in a mixer, to the kaolin moistened with polyethylene glycol, yielding non-dusty coated granules. Example F10: Suspension concentrate active ingredient 40% ethylene glycol 10% nonylphenol polyethylene glycol ether 6%
(15 mol of ethylene oxide) sodium iignosulfonate 10% carboxymethylcellulose 1% aqueous formaldehyde solution (37%) 0.2% aqueous silicone oil emulsion (75%) 0.8% water 32%
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.
Biological Examples
A) Microbicidal action
Example B1 : Action against Phvtophthora 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 prepared from 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 specks 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 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.
Whereas infestation in untreated and infected control plants is 100%, with the compounds from Tables 1 to 89, especially with the compounds 3-2.17, 3-2.61, 3-2.85 and 3-2.89, infestation is reduced to 20% or less in both tests.
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. At the 10-leaf stage, 3 plants are sprayed with a mixture comprising the active ingredient in a concentration of 200 ppm. After the spray-coating has dried, 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. b) Curative action
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.
In comparison with the control plants, the plants treated with compounds from Tables 1 to 89 exhibit an infestation of 20% or less. In particular, with the compounds 3-2.23, 3-2.17,
3-2.61 and 3-2.89 complete curative action is still obtained even at a concentration of the test compound of 20 ppm. 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.
Compounds from Tables 1 to 89, especially compounds 3-2.61 , 3-2.88, 3-2.89 and 3-2.81 , bring about a reduction in the fungus infestation to from 10 to 0 %.
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.
Compounds from Tables 1 to 89 in general are able to suppress infestation with the disease to less than 20 % and, in some cases, to suppress it completely. Examole B5: Action against Septoria nodorum on wheat
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.
B. lnsecticidal action
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.
Compounds from Tables 1 to 89 exhibit good activity in this test. In particular, compounds 3-2.47, 3-2.48, 3-2.90, 3-3.1 , 3-3.11 and 3-3.33 exhibit an activity of more than 80 % in this test.
Example B7: 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.
Compounds from Tables 1 to 89 exhibit good activity in this test. In particular, compounds 3-2.7, 3-2.12, 3-2.13, 3-2.18, 3-220, 3-2.24, 3-2.27, 3-2.30, 3-2.34, 3-2.47, 3-2.49, 3-2.90, 3-2.91 , 3-2.94, 3-3.1, 3-3.7 and 3-3.22 exhibit an activity of more than 80 % in this test.
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.
Most compounds from Tables 1 to 89 exhibit good activity in this test. In particular, compounds 3-2.7, 3-2.11 , 3-2.18, 3-2.24, 3-2.27, 3-2.30, 3-2.47, 3-2.48, 3-2.49, 3-2.84, 3-2.90, 3-2.91 , 3-2.94, 3-3.11 , 3-3.12, 3-3.22, 3-3.31 , 3-3.32 and 3-3.33 exhibit an activity of more than 80 % in this test.
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.
Compounds from Tables 1 to 89 exhibit good activity in this test. In particular, compounds 3-2.7, 3-2.11, 3-2.12, 3-2.13, 3-2.18, 3-2.20, 3-2.24, 3-2.27, 3-2.31 , 3-2.32, 3-2.34, 3-2.47, 3-2.48, 3-2.49, 3-2.84, 3-2.90, 3-2.91, 3-2.94, 3-3.7, 3-3.12, 3-3.18, 3-3.22 and 3-3.32 exhibit an activity of more than 80 % in this test.
C. Acaricidal action
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.
Compounds from Tables 1 to 89 generally exhibit good activity in this test. In particular, compounds 3-2.7, 3-2.12, 3-2.13, 3-2.31, 3-2.32, 3-2.34, 3-2.47, 3-2.49, 3-2.68, 3-2.90, 3-2.94 and 3-3.26 exhibit an activity of more than 80 % in this test.

Claims

What is claimed is:
1. A compound of formula
Figure imgf000088_0001
wherein either
X is CH or N, Y is ORi and Z is O, pj
X is N, Y is NHRβ and Z is O, S or S(=0);
Figure imgf000088_0002
Ri is H or Cι-C4alkyl;
R2 is H, Cι-C4alkyl, halo-Cι-C4alkyl, Cs-Cβcycloalkyl, C3-C6cycloalkenyl, C1-G4- alkoxymethyl, Cι-C4alkoxy, halo-C1-C4alkoxy, Cι-C4alkylthio or halo-Cι-C4alkylthio, cyano or aryl;
R3 and R4 are each independently of the other H, CrC4alkyl, CrC4alkoxy, OH, SH, NH2, CN, N02, a (Cι-C4alkyl)3-Si group, it being possible for the alkyl groups to be the same or different, halogen, (Cι-C4alkyl)S(=0)ι, (halo-Cι-C4alkyl)S(=0)ι, halo-Cι-C4alkyl or halo-Cι-C4alkoxy, Cι-C6alkylamino, di-Cι-C6alkylamino, it being possible for the alkyl groups to be the same or different; arylamino or diarylamino, it being possible for the aryl groups to be the same or different;
I is 0, 1 or 2;
R5 and R6 are each independently of the other Cι-C6alkyl, halo-Cι-C6alkyl, C3-C6cycloalkyl, C3-C6cycloalkenyl, halo-C3-C6cycloalkyl, Cι-C6alkoxy, halo-Cι-C6alkoxy, CrC6-alkyl- thio, halo-Cι-Cβalkylthio, d-Cβalkyisulfinyl, halo-Ci-Cβalkylsulfinyl, Ci-Cβ-alkylsulfonyl, halo-Cι-C6alkylsulfonyl, Cι-Cβalkylsulfonyloxy, halo-Cι-Cβalkyl-sulfonyloxy, d-Cealk- oxy-CrCβalkyl, halo-Cι-C6alkoxy-Cι-C6alkyl, CrCβalkoxy-Ci-Cβalkoxy, Cι-Cealkylthio- Cι-Cβalkyl, halo-Cι-Cβalkylthio-Cι-C6alkyl, Cι-C6alkylsulfinyl-Cι-C6alkyl, halo-Cι-C6- alkylsulfinyl-d-Cβalkyl, Cι-C6alkylsulfonyl-Cι-Cβalkyl, halo-Ci-dalkylsulfonyl-Ci-d- alkyl, formyl, -CH=NO-d-Cβalkyl, -CH=NO-C2-Cβalkenyl, -CH=NO-C2-C8alkynyl, -CH=NO-C3-Cβcycloalkyl, Ci-dalkylcarbonyl, halo-Ci-dalkylcarbonyl, d-dalkoxy- carbonyl, halo-d-Cβalkoxycarbonyl, d-dalkylaminocarbonyl, d-C4alkoxyimino- methyl, di(Cι-Cβalkyl)aminocarbonyl, it being possible for the alkyl groups to the same or different; d-Cβall ylaminothiocarbonyl, di(C1-C6alkyl)amino-thiocarbonyl, it being possible for the alkyl groups to be the same or different; d-Cβalkylamino, di(CrC6alkyl)amino, it being possible for the alkyl groups to be the same or different; arylamino or diarylamino, it being possible for the aryl groups to be the same or different; halogen, N02, CN, SF5, thioamido, thiocyanatomethyl or trimethylsilyl; aryl-Q-, heterocyclyl-Q-, aryl-Q-Cι-Cβalkyl, aryl-Q-C2-Cβalkenyl, heterocyclyl-Q-Ci-daJkyl or heterocydyl-Q-d-dalkenyl, or aryl-Q-, heterocyclyl-Q-, aryl-Q-d-C6alkyl, aryl-Q-C2- C6alkenyl, heterocyclyl-Q-Cι-Cβalkyl or heterocyclyl-Q-Crdalkenyl, 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, Ci-dalkyl, halo-Cι-C6alkyl, C3-C6cycloalkyl, halo- C3-C6cycloalkyl, Ci-dalkoxy, halo-d-dalkoxy, CN, nitro and Ci-dalkoxycarbonyl; wherein, when m and n are greater than 1 , the radicals R5 and R6 may be the same or different; or two substituents R5 or two substituents R6 form unsubstituted or mono- to tetra-substi- tuted d-dalkylenedioxy or -CH=CH-CH=CH- that are bonded to two adjacent carbon atoms of the phenyl ring in question, the substituents of the d-C4alkylenedioxy or -CH=CH-CH-=CH- group being selected from the group consisting of Ci-dalkyl and halogen;
Rs5 is Ci-dalkyl, halo-Ci-dalkyl, C3-dcycloalkyl, C3-dcycloalkenyl, halo-C3-C6-cycl- oalkyl, Ci-dalkoxy, halo-Ci-dalkoxy, d-dalkylthio, halo-Cι-C6alkylthio, d-Cβalkyl- sulfinyl, halo-Cι-C6alkylsulfinyl, d-C6alkylsulfonyl, halo-Crdalkylsulfonyl, Cι-Cβalkyl- sulfonyloxy, halo-d-C6alkylsulfonyloxy, Ci-dalkoxy-Ci-dalkyl, halo-Cι-Cβalkoxy-Cι- Cβalkyl, Cι-C6alkylthio-Cι-Cβalkyl, halo-Cι-C6alkylthio-Cι-Cβalkyl, Cι-Cβalkylsulfinyl-Cι- dalkyl, halo-Cι-C6alkylsulfinyl-Cι-C6alkyl, Ci-dalkylsulfonyl-d-dalkyl, halo- Ci-Cβalkylsulfonyl-Ci-Cβalkyl, d-dalkylcarbonyl, halo-Cι-C6-alkylcarbonyl, d-dalk- oxycarbonyl, halo-Cι-Cβalkoxycarbonyl, Cι-dalkyl-aminocarbonyl, Ci-dalkoxyimino- methyl, di(Ci-Cealkyl)aminocarbonyl, it being possible for the alkyl groups to be the same or different; Ci-dalkylaminothiocarbonyl, di(d-C6all<yl)aminothiocarbonyl, it being possible for the alkyl groups to be the same or different; C -dalkylamino, di(Cι-Cβalkyl)amino, it being possible for the alkyl groups to be the same or different, arylamino, diarylamino, alkylarylamino; halogen, N0 , CN, SF5, thioamido, thiocyana- tomethyl or trimethylsilyl; wherein, when q is greater than 1 , the radicals RK are independent of one another;
Ree is hydrogen, Cι-C6alkyl, halo-d-C6alkyl, C3-Cβcycloalkyl, C3-dcycloalkenyl, halo- d-CβCycloalkyl, Ci-dalkylsulfinyJ, haio-Ci-Cβalkylsulfinyl, Cι-C6alkylsulfonyl, halo- Cι-C6alkylsulfonyl, Cι-C6alkoxy-Cι-Cβalkyl, halo-d-C6alkoxy-Cι-C6alkyl, d-C6- alkylthio-d-Cβalkyl, halo-Ci-dalkylthio-Ci-dalkyl, Ci-Cβalkylsulfinyl-d-Cβalkyl, halo- Cι-Cβalkylsulfinyl-Cι-Cβalkyl, Cι-Cβalkylsulfonyl-Cι-C6alkyl, halo-Ci-dalkylsulfonyl- Cι-Cβalkyl, Ci-dalkylcarbonyl, haio-Cι-Cβalkylcarbonyl, d-dalkoxycarbonyl, halo- Ci-Cβalkoxycarbonyl, Cι-C6alkylaminocarbonyl, Cι-C4alkoxyiminomethyi, di(d-Cβ- alkyl)aminocarbonyl, it being possible for the alkyl groups to be the same or different, Ci-dalkyiaminothiocarbonyl, di(Cι-C6alkyl)aminothiocarbonyl, it being possible for the alkyl groups to be the same or different; halogen, N02, CN, SF5, thioamido, thiocya- natomethyl or trimethylsilyl; m is 0, 1 , 2, 3, 4 or 5; n is 0, 1 , 2, 3 or 4; q is 0, 1 , 2, 3 or 4;
Q is a direct bond, O, S, -CH(OH)-, -C(=0)- or -S(=0)v-; v is 0, 1 or 2;
A is a direct bond, Cι-Cιoalkylene, -C(=0)-, -C(=S)- or halo-Cι-Cιoalkylene and
R7 is a radical Rι0; or
A is Cι-Cιoalkylene, -C(=0)-, -C(=S)- or halo-Cι-Cιoalkylene and
R7 is -CN, OR10, N(Rιo)2, it being possible for the radicals ι0 to be the same or different,
Figure imgf000090_0001
Rβ is H or Ci-dalkyl;
R is methyl, fluoromethyi or difluoromethyl;
Rio is H, Ci-dalkyl, C2-Cβalkenyl, C2-C8alkynyl, C3-C6cycloalkyl, or d-dalkyl, C2-Cβalk- enyl, C2-Cβalkynyl or C3-Cβcycloalkyl, each of which is mono- or poly- substituted by substituents selected from the group consisting of halogen; or Rio is -Si(d-C alkyl)3> i being possible for the alkyl groups to be the same or different; d-dalkoxycarbonyl, or an aryl or heterocyclyl group that is unsubstituted or mono- or poly-substituted by substituents from the group consisting of halogen, Cι-C4alkyl and halo-Ci-dalkyl; and p is 0, 1 or 2; 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 that n is not 0 when U is m-phenyl or p-phenyl, or when U is 4-chlorophenyl in the para position; and simultaneously Y is OCH3 or NHCH3; Z is oxygen; R2, AR7 and R9 are methyl, and R3 and R4 are H; and with the further proviso that n is not 0 when U is 4-trifluoromethylphenyl or 4-cyanophenyl, each in the para position; and simultaneously X is N; Y is OCH3; Z is oxygen; R2, AR7 and R9 are methyl; and R3 and R4 are H.
2. A compound according to claim 1 of formula (I) wherein X is CH and Z is O.
3. A compound according to claim 1 of formula (I) wherein X is N and Z is O.
4. A compound according to claim 1 of formula (I) wherein Y is ORi.
5. A compound according to any one of claims 1 to 4 of formula (I) wherein R2 is H, Ci-dalkyl, halo-Cι-C alkyl or C3-C6cycloalkyl, cyano or aryl.
6. A compound according to any one of claims 1 to 5 of formula (I) wherein
R3 is H, Ci-dalkyl, Ci-dalkoxy, OH, CN, N02, halogen, halo-d-dalkyl or halo-Cι-C4- alkoxy.
7. A compound according to any one of claims 1 to 6 of foπnula (I) wherein
R4 is H, Ci-dalkyl, d-dalkoxy, OH, CN, N02, halogen, halo-d-C4alkyl or halo-d-C4- alkoxy.
8. A compound according to any one of claims 1 to 7 of formula (I) wherein
Figure imgf000091_0001
R5 is Ci-dalkyl, halo-Ci-dalkyl, C3-C6cycloalkyl, halo-C3-C6cycloalkyl, d-dalkoxy, halo- d-dalkoxy, Ci-daJkylthio, halo-d-dalkylthio, d-dalkylsulfinyl, halo-Cι-Cβalkylsulfinyl, Ci-dalkylsulfonyl, halo-Ci-dalkylsulfonyl, d-dalkyisulfonyloxy, halo-Ci-dalkylsulfonyl- oxy, Ci-dalkoxy-d-dalkyl, halo-d-Cealkoxy-Ci-dalkyl, formyl, -CH=NO-d-C4alkyl, d-d- alkylcarbonyl, halo-Ci-dalkyicarbonyl, Cι-C6alkoxycarbonyl, halo-d-dalkoxycarbonyl, halogen, N02 or CN; aryl-Q-, heterocyclyl-Q-, aryl-Q-Cι-dalkyl or heterocyclyl-Q-Cι-C6alkyl; or aryl-Q-, heterocyclyl-Q-, aryl-Q-d-C6alkyl or heterocyclyl-Q-Cι-Cβalkyl, each of which is, depending on its substitution possibilities, mono- to penta-substituted in the aryl or heterocy- clyl ring, the substituents being selected independently of one another from the group consisting of halogen, Cι-C4-alkyl, halo-d-C4alkyl, d-dcycloalkyl, Ci-dalkoxy, halo-d-dalk- oxy, CN, nitro and d-d-alkoxycarυonyl; Ci-dalkylamino, di-d-dalkylamino, it being possible for the alkyl groups to be the same or different; arylamino or diarylamino, it being possible for the aryl groups to be the same or different; or two substituents R5 are unsubstituted or mono- to tetra-substituted d-dalkylenedioxy or -CH=CH-CH=CH-, the substituents of the Ci-dalkylenedioxy or -CH=CH-CH=CH- group being selected from the group consisting of d-dalkyl and halogen.
9. A compound according to claim 8 of formula (I) wherein m is 1 , 2 or 3.
10. A compound according to claim 9 of formula (I) wherein n is 0 or 1.
11. A compound according to any one of claims 1 to 10 of formula (I) wherein AR7 is methyl or ethyl.
12. A compound according to claim 1 of formula (I) wherein R8 is H or Ci-dalkyl.
13. A compound according to any one of claims 1 to 12 of formula (I) wherein R9is methyl orfluoromethyl.
14. A process for the preparation of a compound as defined in claim 1 , formula (I), or, where applicable, an E/Z isomer, a 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 imgf000093_0001
wherein X, Y, Z, R3, R4and R9are as defined for formula (I) and Xi is a leaving group, with a compound of formula
Figure imgf000093_0002
wherein n, U, A, R2, Rβand R7are as defined above for formula (I); or
a2) reacting a compound of formula
Figure imgf000093_0003
wherein n, A, U, R2, Rβand R are as defined for formula (I), with a compound of foπnula
Figure imgf000093_0004
wherein X, Y, Z, R3, R4 and R9 are as defined for formula (I); or
b) to prepare a compound of foπnula (I) wherein Y is NHR8 and Z is O, reacting a compound of formula (I) wherein Y is ORi with a compound of formula RβNH2 wherein Rβ is as defined for formula (I); or c) to prepare a compound of formula (I) wherein Y is NHRβ and Z is S, reacting a compound of formula (I) wherein Y is R8NH2 and Z is O with P Sι0 or 2,4-bis-(methoxyphenyl)-1 ,3- dithia-2,4-diphosphetane-2,4-disulfide ; or
d) to prepare a compound of foπnula (I) wherein Z is SO, reacting a compound of formula (I) wherein Z is S with an oxidising agent; or
e) to prepare a compound of foπnula (I) wherein U is and R5 and m
Figure imgf000094_0001
are as defined for formula (I), reacting a compound of formula
Figure imgf000094_0002
wherein A, X, Y, Z, R2, R3, FU, R6, R7, R9 and n are as defined in claim 1 for formula (I) and X2 is a leaving group, with a compound of formula
Figure imgf000094_0003
wherein R5 and m are as defined in claim 1 for formula (I), in the presence of a base or of a transition metal catalyst; or
f) to prepare a compound of formula (I) wherein U is
Figure imgf000094_0004
and q are as defined in claim 1 for formula (I), reacting a compound of formula
(XV),
Figure imgf000094_0005
wherein A, X, Y, Z, R2, R3, R4, R6, Rββ, R7, R9 and n are as defined in claim 1 for formula (I) with a compound of formula
Figure imgf000095_0001
wherein R55 and q are as defined in claim 1 for formula (I); or
g) to prepare a compound of formula (I) wherein U is and R5 and q
Figure imgf000095_0002
are as defined in claim 1 for formula (I), reacting a compound of formula (I) wherein U is
with an oxidising agent;
Figure imgf000095_0003
and in each case, if desired, converting a compound of foπnula (I) obtainable according to the process or in some other manner, 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 in some other manner, 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 in some other manner into a free compound of foπnula (I), or an E/Z isomer or tautomer thereof, or into a different salt.
15. A compound of formula
(I").
Figure imgf000095_0004
wherein U, n, A, R2, R6and R7are as defined in claim 1 for formula (I), and, where applicable, an E/Z isomer, a mixture of E/Z isomers and/or a tautomer thereof, in each case in free form or in salt form.
16. A compound of formula
Figure imgf000096_0001
wherein U, n, A, R2, Rβand R7are as defined in claim 1 for formula (I), and, where applicable, an E/Z isomer, a mixture of E/Z isomers and/or a tautomer thereof, in each case in free form or in salt form.
17. A pesticide comprising as active ingredient in an effective concentration at least one compound according to claim 1 of formula (I) or, where applicable, an E/Z isomer or tau to- mer thereof, in free form or in agrochemically acceptable salt form, and at least one adj u- vant.
18. A process for the preparation of a composition as described in claim 17, comprising i n- timately mixing and/or grinding the active ingredient with the adjuvant(s).
19. The use of a compound as described in claim 1, formula (I), or, where applicable, an E/Z isomer or tautomer thereof, in free form or in agrochemically acceptable salt foπn, in the preparation of a composition according to claim 17.
20. The use of a compound as described in claim 1 , formula (I), or of a composition as described in claim 17, for controlling pests.
21. A method of controlling pests, wherein a compound as described in claim 1 , of form u- la (I), or a composition as described in claim 17, is applied to the pests or to their habitat.
22. A method according to claim 21 for protecting plant propagation material, wherein the propagation material or the planting site of the propagation material is treated.
23. Plant propagation material treated in accordance with the method described in claim 22.
PCT/EP1997/007122 1996-12-20 1997-12-18 O-benzyl oxime ether derivatives as pecticides WO1998028262A1 (en)

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Publication number Priority date Publication date Assignee Title
WO2000017155A1 (en) * 1998-09-22 2000-03-30 Bayer Aktiengesellschaft Pesticidal bis-oxime compounds
US6525092B1 (en) 1998-09-22 2003-02-25 Bayer Aktiengsellschaft Pesticidal bis-oxime compounds

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