WO1997007103A2 - Pesticidal indazole derivatives - Google Patents
Pesticidal indazole derivatives Download PDFInfo
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- WO1997007103A2 WO1997007103A2 PCT/EP1996/003452 EP9603452W WO9707103A2 WO 1997007103 A2 WO1997007103 A2 WO 1997007103A2 EP 9603452 W EP9603452 W EP 9603452W WO 9707103 A2 WO9707103 A2 WO 9707103A2
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- 0 C[C@](*)(C=C*)C=C(C(C)=CC=NC)C(*)=*O Chemical compound C[C@](*)(C=C*)C=C(C(C)=CC=NC)C(*)=*O 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0803—Compounds with Si-C or Si-Si linkages
- C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
- C07F7/0812—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
- A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N55/00—Biocides, pest repellants or attractants, or plant growth regulators, containing organic compounds containing elements other than carbon, hydrogen, halogen, oxygen, nitrogen and sulfur
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- 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
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- 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
- C07C251/42—Oximes with oxygen atoms of oxyimino groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals with the carbon atom of at least one of the oxyimino groups bound to a carbon atom of a ring other than a six-membered aromatic ring
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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
- C07C251/48—Oximes with oxygen atoms of oxyimino groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals with the carbon atom of at least one of the oxyimino groups bound to a carbon atom of a six-membered aromatic ring
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C255/00—Carboxylic acid nitriles
- C07C255/49—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
- C07C255/54—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing cyano groups and etherified hydroxy groups bound to the carbon skeleton
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C255/00—Carboxylic acid nitriles
- C07C255/63—Carboxylic acid nitriles containing cyano groups and nitrogen atoms further bound to other hetero atoms, other than oxygen atoms of nitro or nitroso groups, bound to the same carbon skeleton
- C07C255/64—Carboxylic acid nitriles containing cyano groups and nitrogen atoms further bound to other hetero atoms, other than oxygen atoms of nitro or nitroso groups, bound to the same carbon skeleton with the nitrogen atoms further bound to oxygen atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/66—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
- C07C69/73—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of unsaturated acids
- C07C69/734—Ethers
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
- C07D231/54—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings condensed with carbocyclic rings or ring systems
- C07D231/56—Benzopyrazoles; Hydrogenated benzopyrazoles
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/02—Systems containing only non-condensed rings with a three-membered ring
Definitions
- the present invention relates to compounds of formula
- X is CH or N
- Y is OR 1 and Z is O
- R 1 is C 1 -C 4 alkyl
- R 2 is H, C 1 -C 4 alkyl, halo-C 1 -C 4 alkyl, C 3 -C 6 cycloalkyl, C 1 -C 4 alkoxymethyl, C 1 -C 4 alkoxy, halo-C 1 -C 4 alkoxy, C 1 -C 4 alkylthio, halo-C 1 -C 4 alkylthio or -CN;
- R 5 is unsubstituted or substituted C 1 -C 6 alkyI, C 1 -C 6 alkoxy, halo-C 1 -C 6 alkoxy, C 1 -C 6 - alkylthio, halo-C 1 -C 6 alkylthio, C 1 -C 6 alkylsulfinyl, halo-C 1 -C 6 alkylsulfinyl, C 1 -C 6 alkylsulfonyl, halo-C 1 -C 6 alkylsulfonyl, C 1 -C 6 alkylcarbonyl, halo- C 1 -C 6 alkylcarbonyl, C 1 -C 6 alkoxycarbonyl, halo-C 1 -C 6 alkoxycarbonyl, C 1 -C 6 alkylaminocarbonyi;
- R 6 is a C 2 -C 6 alkenyl or C 2 -C 6 alkynyl group that is unsubstituted or substituted by from 1 to 3 halogen atoms; a (C 1 -C 4 alkyl) 3 Si group wherein the alkyl groups may be identical or different; -CN; an unsubstituted or mono- to penta-substituted C 3 -C 6 cyclo alkyl, aryl or heterocyclyl group, the substituents being selected from the group consisting of halogen, C 1 -C 6 alkyl, halo-C 1 -C 6 alkyI, C 1 -C 6 alkoxy, halo-C 1 -C 6 alkoxy, phenoxy and -CN;
- R 7 is H, unsubstituted or substituted C 1 -C 6 alkyI, C 3 -C 6 cycloalkyl, a C 2 -C 6 alkenyl- or C 2 -C 6 alkynyl-group that is unsubstituted or substituted by from 1 to 3 halogen atoms; phenyl or mono- to penta-substituted phenyl, the substituents being selected from the group consisting of C 1 -C 4 alkyI, halo-C 1 -C 4 alkyI, halogen, C 1 -C 4 alkoxy and halo- C 1 -C 4 alkoxy;
- R 8 is H or C 1 -C 4 alkyl
- R 9 is CH 3 , CH 2 F or CHF 2 ;
- n 0, 1 or 2;
- n 0, 1 , 2, 3 or 4;
- p 0, 1 or 2
- E/Z isomers and, where appropriate, to the possible E/Z isomers, mixtures of E/Z isomers and/or tautomers thereof, in each case in free form or in salt form, to a process for the preparation of those compounds, E/Z isomers and tautomers and to the use of those compounds, E/Z isomers and tautomers, to pesticidal compositions comprising an active ingredient selected from those compounds, E/Z isomers and tautomers, to a process for the preparation of those compositions and to the use of those compositions, to intermediates, in free form or in salt form, for the preparation of those compounds, where appropriate to tautomers, in free form or in salt form, of those intermediates, to a process for the preparation of those intermediates and the tautomers thereof and to the use of those intermediates and the tautomers thereof.
- carbon-containing groups and compounds each contain from 1 up to and including 8, preferably from 1 up to and including 6, especially from 1 up to and including 4 and above all 1 or 2, carbon atoms.
- Alkyl both as a group per se and as a structural element of other groups and compounds, such as haloalkyl, alkoxy and alkylthio, is, in each case taking due account of the number of carbon atoms contained in the corresponding group or compound, either straight-chained, i.e. methyl, ethyl, propyl, butyl, pentyl or hexyl, or branched, e.g. isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl or isohexyl.
- Alkenyl both as a group per se and as a stuctural element of other groups and compounds, such as haloalkenyl, is, in each case taking due account of the number of carbon atoms contained in the corresponding group or compound, either straight-chained, such as vinyl, 1-methylvinyl, allyl, 1-butenyl or 2-hexenyl, or branched, such as isopropenyl.
- Alkynyl both as a group per se and as a stuctural element of other groups and compounds, such as haloalkynyl, is, in each case taking due account of the number of carbon atoms contained in the corresponding group or compound, either straight-chained, such as propargyl, 2-butynyl or 5-hexynyl, or branched, such as 2-ethynylpropyl or 2-propargylisopropyl.
- Cycloalkyl is cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.
- Alkylenedioxy is -O(alkylene)O-.
- Alkylene both as a group per se and as a stuctural element of other groups and
- Alkenylene is, in each case taking due account of the number of carbon atoms contained in the corresponding compound, either straight-chained, such as vin-1 ,2-ylene, all-1,3-ylene, but-1-en-1 ,4-ylene or hex-2-en-1 ,6-ylene, or branched, e.g. 1-methylvin-1,2-ylene.
- Alkynylene is, in each case taking due account of the number of carbon atoms contained in the corresponding compound, either straight-chained, such as propargylene, 2-butynylene or 5-hexynylene, or branched, e.g. 2-ethynylpropylene or 2-propargylisopropylene.
- Aryl is phenyl or naphthyl, especially phenyl.
- Heterocyclyl denotes a 5- to 7-membered aromatic or non-aromatic 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 containing a nitrogen atom as hetero atom and where appropriate a further hetero atom, preferably nitrogen or sulfur, especially nitrogen.
- Halogen both as a group per se and as a structural element of other groups and compounds, such as haloalkyl, haloalkenyl and haloalkynyl, is fluorine, chlorine, bromine or iodine, especially fluorine, chlorine or bromine, more especially fluorine or chlorine and above all fluorine.
- Halo-substituted carbon-containing groups and compounds such as haloalkyl, haloalkenyl or haloalkynyl, may be partially halogenated or perhalogenated, the halogen substituents in the case of multiple halogenation being identical or different.
- haloalkyl both as a group per se and as a structural element of other groups and compounds, such as halo- alkenyl, are methyl mono- to tri-substituted by fluorine, chlorine and/or by bromine, such as CHF 2 or CF 3 ; ethyl mono- to penta-substituted by fluorine, chlorine and/or by bromine, such as CH 2 CF 3 , CF 2 CF 3 , CF 2 CCl 3 , CF 2 CHCl 2 , CF 2 CHF 2 , CF 2 CFCl 2 , CF 2 CHBr 2 , CF 2 CHClF, CF 2 CHBrF or CClFCHClF; propyl or isopropyl each mono- to hepta-substituted by fluorine, chlorine and/or by bromine, such as CH 2 CHBrCH 2 Br, CF 2 CHFCF 3 ,
- Haloalkynyl is, for example, CH 2 C ⁇ CF, CH 2 C ⁇ CCH 2 Cl or
- Compounds of formula l having at least one basic centre are capable, for example, of forming acid addition salts.
- Those salts are formed, for example, with strong inorganic acids, such as mineral acids, for example 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, C 1 -C 4 alkanecarboxylic acids, for example acetic acid, saturated or unsaturated dicarboxylic acids, for example oxalic, malonic, succinic, maleic, fumaric or phthalic acid, hydroxycarboxylic acids, for example ascorbic, lactic, malic, tartaric or citric acid, or benzoic acid, or with organic sulfonic acids, such as unsubstituted or substituted, for example halo-substituted, C 1 -C
- compounds of formula l having at least one acid group are capable of forming salts with bases.
- Suitable salts with bases are, for example, metal salts, such as alkali metal or alkaline earth metal salts, for example sodium, potassium or magnesium salts, or salts with ammonia or an organic amine, such as morpholine, piperidine, pyrrolidine, a mono-, di- or tri-lower alkylamine, for example ethyl-, diethyl-, triethyl- or dimethyl-propylamine, or a mono-, di- or tri-hydroxy-lower alkylamine, for example mono-, di- or tri-ethanolamine.
- corresponding internal salts may also be formed. Preference is given within the scope of the invention to agrochemically advantageous salts. In view of the close
- any reference hereinbefore or hereinafter to the compounds of formula l is to be understood as including also the corresponding salts, where appropriate and expedient.
- the free form is generally preferred in each case.
- X is CH or N
- Y is OR 1 and Z is O
- R 1 is C 1 -C 4 alkyl
- R 2 is H, C 1 -C 4 alkyl, halo- C 1 -C 4 alkyl, C 3 -C 6 cycloalkyl, C 1 -C 4 alkoxymethyl, C 1 -C 4 alkoxy, halo-C 1 -C 4 alkoxy, C 1 -C 4 alkylthio, halo-C 1 -C 4 alkylthio or CN;
- R 3 and R 4 are each independently of the other H, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, OH, CN, NO 2 ; a (C 1 -C 4 alkyl) 3 Si group wherein the alkyl groups may be identical or different;
- R 5 C 1 -C 6 alkyI, halo-C 1 -C 6 alkyI, C 1 -C 6 alkoxy, halo-C 1 -C 6 alkoxy, C 1 -C 6 alkylthio, halo- C 1 -C 6 alkylthio, 0
- R 6 is a C 2 -C 6 alkenyl or C 2 -C 6 alkynyl group that is unsubstituted or substituted by from 1 to 3 halogen atoms; a (C 1 -C 4 alkyl) 3 Si group wherein the alkyl groups may be identical or different; CN; an unsubstituted or mono- to penta-substituted
- R 7 is H, C 1 -C 6 alkyI, halo- C 1 -C 6 alkyI, C 1 -C 4 alkoxy-C 1 -C 4 alkyl, C 3 -C 6 cycloalkyl,
- R 8 is H or C 1 -C 4 alkyI
- R 9 is CH 3 , CH 2 F or CHF 2 ;
- X is CH
- Y is OR., , preferably C 1 -C 2 alkoxy, especially methoxy
- R 1 is C 1 -C 2 alkyl
- R 2 is C 1 -C 4 alkyl, halo-C 1 -C 4 alkyl, cyclopropyl, halo-C 1 -C 4 alkylthio or CN,
- R 3 is H, C 1 -C 2 alkyl, C 1 -C 2 alkoxy, CN, NO 2 , CF 3 or halogen,
- R 4 is H, C 1 -C 2 alkyl, C 1 -C 2 alkoxy, CN, NO 2 , CF 3 or halogen,
- R 5 is C 1 -C 4 alkyl, halo-C 1 -C 4 alkyl, C 1 -C 4 alkoxy, halo-C 1 -C 4 alkoxy, halogen, NO 2 ; an unsubstituted or mono- to tetra-substituted C 1 -C 4 alkylenedioxy group, the substituents being selected from the group consisting of C 1 -C 4 alkyl and halogen; or QR 6 ,
- R6 is a C 2 -C 6 alkenyl or C 2 -C 6 alkynyl group that is unsubstituted or substituted by from 1 to 3 halogen atoms; an unsubstituted or mono- to penta-substituted C 3 -C 6 cycloalkyl, aryl or heterocyclyl group, the substituents being selected from the group consisting of halogen, C 1 -C 6 alkyI, halo-C 1 -C 6 alkyI, C 1 -C 6 alkoxy and CN;
- a C 2 -C 3 alkenyl or propynyl group that is unsubstituted or substituted by 1 or 2 halogen atoms; an unsubstituted or mono- to tri-substituted cyclopropyl or phenyl group, the substituents being selected from the group consisting of halogen, methyl, halomethyl, methoxy and CN;
- R 7 is C 1 -C 6 alkyI, preferably C 1 -C 2 alkyl, especially methyl;
- R 8 is C 1 -C 4 alkyl, preferably C 1 -C 2 alkyl,
- R 9 is methyl or CH 2 F, preferably methyl
- Q is a direct single bond, O or O(C 1 -C C alkylene), preferably O or O(C 1 -C 2 alkylene), especially O or O(methylene);
- m is 0 or 1 , preferably 0;
- n is 0, 1 , 2 or 3, preferably 0, 1 or 2;
- p is 0 or 1 , preferably 0;
- X is CH
- Y is OR 1
- Z is O
- R. is C 1 -C 2 alkyl
- R 2 is C 1 -C 3 alkyI, halo-C 1 -C 2 alkyl, cyclopropyl, halo-C 1 -C 2 alkylthio or CN,
- R 3 and R 4 are each independently of the other H, C 1 -C 2 aIkyl, C 1 -C 2 alkoxy, CF 3 or halogen,
- R 5 is C 1 -C 2 alkyl, halo-C 1 -C 2 alkyl, halogen or QR 6 ,
- R 6 is a C 2 -C 6 alkenyl or C 2 -C 6 alkynyl group that is unsubstituted or substituted by from 1 to 3 halogen atoms; an unsubstituted or mono- to tri-substituted C 3 -C 6 cycloalkyl or phenyl group, the substituents being selected from the group consisting of halogen, C 1 -C 6 alkyI, halo-C 1 -C 6 alkyI, C 1 -C 6 alkoxy and CN;
- R 7 s C 1 -C 2 alkyl
- R 9 is methyl or CH 2 F
- R 2 is C 1 -C 3 alkyI, halomethyl, cyclopropyl, halomethylthio or CN,
- R 3 and R 4 are each independently of the other H, methyl, methoxy, chlorine or fluorine, R 5 is methyl, fluorine, chlorine or QR 6 ,
- R 6 is a cyclopropyl or phenyl group that is unsubstituted or mono- to tri-substituted by halogen, methyl, halomethyl or by methoxy,
- R 7 is C 1 -C 2 alkyl
- R 9 is methyl
- Q is O or O(methylene), and n is 0, 1 or 2.
- the invention relates also to a process for the preparation of the compounds of formula I and, where appropriate, the E/Z isomers, mixtures of E/Z isomers and/or the tautomers thereof, in each case in free form or in salt form, which process comprises, for example: a) for the preparation of a compound of formula I wherein Y is OR 1 . and Z is O,
- X, R 1 , R 3 , R 4 and R 9 are as defined for formula I and X. is a leaving group, preferably in the presence of a base, with a compound of formula
- n, R 2 , R 5 and R 7 are as defined for formula I, or reacting a compound of formula
- n, X, R 2 , R 3 , R 4 , R 5 and R 7 are as defined for formula I, preferably in the presence of a base, with a compound of the formula X 3 R 9 , which is known or can be prepared analogously to corresponding known compounds and wherein R 9 is as defined for formula I and X 3 is a leaving group, or b) for the preparation of a compound of formula I wherein Y is NHR 8 and Z is O, reacting a compound of formula I wherein Y is O R 1 , obtainable, for example, in accordance with process variant a), with a compound of the formula NH 2 R 8 , which is known or can be prepared analogously to corresponding known compounds and wherein R 8 is as defined for formula I, or c) for the preparation of a compound of formula I wherein Z is S, reacting a compound of formula I wherein Y is NH 2 R 8 and Z is O, obtainable, for example, in accordance with process variant b), with P 4 S 10 or
- the invention relates also to a process for the preparation of compounds of formula III, in each case in free form or in salt form, which process comprises, for example: e) reacting a compound of formula
- n, R 2 and R 5 are as defined for formula I and X 2 is a leaving group, where appropriate in the presence of a base, with a compound of formula which is known or can be prepared analogously to corresponding known compounds and wherein R 7 is as defined for formula I, and in each case, if desired, converting a compound of formula III obtainable in accordance with the process or by another method, or an E/Z isomer or a 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 a tautomer thereof, in each case in free form or in salt form, separating a mixture of E/Z isomers obtainable in accordance with the process and isolating the desired isomer and/or converting a free compound of formula III obtainable in accordance with the process or by another method, or an E/Z isomer or a tautomer thereof, into a salt or converting a salt of a compound of formula III obtainable in accordance
- the invention relates also to a process for the preparation of compounds of formula IV, in each case in free form or in salt form, which process comprises, for example: f) reacting a compound of formula
- n, R 2 and R 5 are as defined for formula I and X 2 is as defined for formula IV, preferably in the presence of a base, with a C 1 -C 6 alkyl nitrite, preferably isopentyl nitrite, and in each case, if desired, converting a compound of formula IV obtainable in accordance with the process or by another method, or an E/Z isomer or a tautomer thereof, in each case in free form or in salt form, into a different compound of formula IV or an E/Z isomer or a tautomer thereof, in each case in free form or in salt form, separating a mixture of E/Z isomers obtainable in accordance with the process and isolating the desired isomer and/or converting a free compound of formula IV obtainable in accordance with the process or by another method, or an E/Z isomer or a tautomer thereof, into a salt or converting
- the invention relates also to a process for the preparation of compounds of formula VII, in each case in free form or in salt form, which process comprises, for example: g) for the preparation of a compound of formula VII wherein X is CH, reacting a compound of formula
- n, R 1 , R 2 , R 3 , R 4 , R 5 and R 7 are as defined for formula I, preferably in the presence of a base, with a formic acid C 1 -C 6 alkyl ester, preferably formic acid methyl ester, or h) for the preparation of a compound of formula VII wherein X is N, reacting a compound of formula VIII, preferably in the presence of a base, with a C 1 -C 6 alkyl nitrite, preferably isopentyl nitrite, and in each case, if desired, converting a compound of formula VII obtainable in
- an E/Z isomer or a tautomer thereof in each case in free form or in salt form, into a different compound of formula VII or an E/Z isomer or a tautomer thereof, in each case in free form or in salt form, separating a mixture of E/Z isomers obtainable in accordance with the process and isolating the desired isomer and/or converting a free compound of formula VII obtainable in accordance with the process or by another method, or an E/Z isomer or a tautomer thereof, into a salt or converting a salt of a compound of formula VII obtainable in accordance with the process or by another method, or of an E/Z isomer or of a tautomer thereof, into the free compound of formula VII or an E/Z isomer or a tautomer thereof or into a different salt.
- the invention relates also to a process for the preparation of compounds of formula VIII, in each case in free form or in salt form, which
- R 1 , R 3 and R 4 are as defined for formula I and X 1 is a leaving group, preferably in the presence of a base, and in each case, if desired, converting a compound of formula VIII obtainable in accordance with the process or by another method, or an E/Z isomer or a tautomer thereof, in each case in free form or in salt form, into a different compound of formula VIII or an E/Z isomer or a tautomer thereof, in each case in free form or in salt form, separating a mixture of E/Z isomers obtainable in accordance with the process and isolating the desired isomer and/or converting a free compound of formula VIII obtainable in accordance with the process or by another method, or an E/Z isomer or a tautomer thereof, into a salt or converting a salt of a compound of formula VIII obtainable in accordance with the process or by another method, or of an E/Z is
- the invention relates also to a process for the preparation of compounds of formula II, wherein X 1 is halogen, in each case in free form or in salt form, which process comprises, for example: j) reacting a compound of formula
- the reactions described hereinbefore and hereinafter are carried out in a manner known per se, for example in the absence or, customarily, in the presence of a suitable solvent or diluent or of a mixture thereof, the reactions being carried out as required with cooling, at room temperature or with heating, for example in a temperature range from approximately 0°C to the boiling temperature of the reaction medium, preferably from approximately 20°C to approximately +120°C, especially from 60°C to 80°C and, if necessary, in a closed vessel, under pressure, in an inert gas atmosphere and/or under anhydrous conditions.
- Especially advantageous reaction conditions can be found, for example, in the Examples.
- Suitable leaving groups X 1 and X 3 are, for example, halogens, C 1 -C 8 alkyI- or arylsulfonates, preferably halogens, especially chlorine or bromine, more especially bromine.
- Suitable bases for facilitating the reaction are, for example, alkali metal or alkaline earth metal hydroxides, hydrides, amides, alkanolates, acetates, carbonates,
- dialkylamides or alkylsilylamides or alkylamines, alkylenediamines, unsubstituted or N-alkylated, saturated or unsaturated cycloalkylamines, basic heterocycles, ammonium hydroxides and carbocyclic amines.
- DBU 1,5-diazabicyclo[5.4.0]undec-5-ene
- the reactants can be reacted with one another as such, i.e. without the addition of a solvent or diluent, for example in the melt. In most cases, however, the addition of an inert solvent or diluent or of a mixture thereof is advantageous.
- solvents or diluents examples include: aromatic, aliphatic and alicyclic hydrocarbons and halogenated hydrocarbons, such as benzene, toluene, xylene, mesitylene, tetralin (tetrahydronaphthalene), chlorobenzene, dichlorobenzene, bromobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, trichloromethane, tetrachloromethane,
- aromatic, aliphatic and alicyclic hydrocarbons and halogenated hydrocarbons such as benzene, toluene, xylene, mesitylene, tetralin (tetrahydronaphthalene), chlorobenzene, dichlorobenzene, bromobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, trichloromethane, te
- bases used in excess such as triethylamine, pyridine, N-methylmorpholine or N,N-diethylaniline, may also serve as solvents or diluents.
- a compound of formula III is reacted at from 0°C to approximately +120°C, preferably at room temperature, in an inert solvent, preferably N,N-dimethyl-formamide, in the presence of a base, preferably an inorganic base, especially sodium hydride, with a compound of formula II.
- the reactants can be reacted with one another as such, i.e. without the addition of a solvent or diluent, for example in the melt. In most cases, however, the addition of an inert solvent or diluent or of a mixture thereof is advantageous.
- solvents or diluents examples 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 or tetrachloroethene; esters, such as ethyl acetate; ethers, such as diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, tert-butyl methyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, dime
- the reaction is advantageously carried out in a temperature range from approximately 0°C to approximately +120°C, preferably from approximately 0°C to
- a compound of formula I wherein Y is OR 1 is reacted at from 0°C to approximately +120°C, preferably at room temperature, in an inert solvent, preferably ethanol, with a compound of the formula NH 2 R 8 .
- the reactants can be reacted with one another as such, i.e. without the addition of a solvent or diluent, for example in the melt. In most cases, however, the addition of an inert solvent or diluent or of a mixture thereof is advantageous.
- solvents or diluents examples 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 or tetrachloroethene; ethers, such as diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, tert-butyl methyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, dimethoxydiethyl ether, tetrahydr
- the reaction is advantageously carried out in a temperature range from approximately 0°C to approximately +120°C, preferably from approximately 80°C to
- a compound of formula I wherein Y is NH 2 R 8 and Z is O is reacted at from 80°C to approximately +120°C, preferably at 120°C, with P 4 S 10 .
- Suitable oxidising agents are, for example, inorganic peroxides, such as sodium perborate, or hydrogen peroxide, or organic peracids, such as perbenzoic acid or peracetic acid, or mixtures of organic acids and hydrogen peroxide, such as acetic acid/hydrogen peroxide.
- the reactants can be reacted with one another as such, i.e. without the addition
- esters such as ethyl acetate
- ethers such as diethyl ether
- glycol monomethyl ether ethylene glycol monoethyl ether, ethylene glycol
- ketones such as acetone, methyl ethyl ketone or methyl isobutyl ketone
- alcohols such as methanol, ethanol or propanol
- amides such as N,N-dimethylformamide, N,N-diethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone or
- nitriles such as acetonitrile or propionitrile
- acid or propionic acid may also serve as solvents or diluents.
- the reaction is advantageously carried out in a temperature range from approximately 0°C to approximately +120°C, preferably from approximately 0°C to
- a compound of formula I wherein Z is S is reacted at from 0°C to approximately +40°C, preferably at room temperature, in an organic acid, preferably acetic acid, with hydrogen peroxide.
- Suitable leaving X 2 groups are, for example, halogens, C 1 -C 8 alkyI sulfates or aryl sulfates, preferably halogens, especially chlorine or fluorine, more especially fluorine.
- the reactants can be reacted with one another as such, i.e. without the addition
- benzene toluene, xylene, mesitylene, tetralin, chlorobenzene, dichlorobenzene, bromobenzene, petroleum ether, hexane, cyclohexane, dichloromethane,
- esters such as ethyl acetate
- ethers such as diethyl ether
- glycol monomethyl ether ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, dimethoxydiethyl ether, tetrahydrofuran or dioxane; ketones, such
- amides such as N,N-dimethylformamide, N,N-diethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone or
- nitriles such as acetonitrile or propionitrile
- bases used in excess such as triethylamine, pyridine, N-methylmorpholine or N,N-diethylaniline, may also serve as solvents or diluents.
- the reaction is advantageously carried out in a temperature range from approximately 0°C to approximately +140°C, preferably from approximately 100°C to
- a compound of formula IV is reacted at from 100°C to approximately +140°C, preferably at approximately +140°C, with a compound of formula V.
- Suitable bases for facilitating the reaction are, for example, alkali metal or alkaline earth metal hydroxides, hydrides, amides, alkanolates, acetates, carbonates,
- ammonium hydroxides and carbocyclic amines The following may be mentioned
- 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,
- the reactants can be reacted with one another as such, i.e. without the addition of a solvent or diluent, for example in the melt. In most cases, however, the addition of an inert solvent or diluent or of a mixture thereof is advantageous.
- solvents or diluents examples 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 or tetrachloroethene; esters, such as ethyl acetate; ethers, such as diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, tert-butyl methyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, dime
- bases used in excess such as triethylamine, pyridine, N-methylmorpholine or N,N-diethylaniline, may also serve as solvents or diluents.
- the reaction is advantageously carried out in a temperature range from approximately 0°C to approximately +120°C, preferably from approximately 0°C to approximately +40°C.
- a compound of formula VI is reacted at from 0°C to approximately +40°C, preferably at room temperature, in an inert solvent, preferably an ether, especially 1,4-dioxane, with an alkyl nitrite, preferably isopentyl nitrite.
- Suitable bases for facilitating the reaction are, for example, alkali metal or alkaline earth metal hydroxides, hydrides, amides, alkanolates, acetates, carbonates,
- dialkylamides or alkylsilylamides or alkylamines, alkylenediamines, unsubstituted or N-alkylated, saturated or unsaturated cycloalkylamines, basic heterocycles,
- ammonium hydroxides and carbocyclic amines The following may be mentioned by way of example: sodium hydroxide, hydride, amide, methanolate, acetate or
- 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,
- solvents or diluents examples 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 or tetrachloroethene; esters, such as ethyl acetate; ethers, such as diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, tert-butyl methyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, dime
- bases used in excess such as triethylamine, pyridine, N-methylmorpholine or N,N-diethylaniline, may also serve as solvents or diluents.
- the reaction is advantageously carried out in a temperature range from approximately 0°C to approximately +120°C, preferably from approximately 0°C to approximately +40°C.
- a compound of formula VIII is reacted at from 0°C to approximately +40°C, preferably at room temperature, in an inert solvent, preferably an ether, especially tert-butyl methyl ether, with formic acid methyl ester.
- Suitable bases for facilitating the reaction are, for example, alkali metal or alkaline earth metal hydroxides, hydrides, amides, alkanolates, acetates, carbonates,
- dialkylamides or alkylsilylamides or alkylamines, alkylenediamines, unsubstituted or N-alkylated, saturated or unsaturated cycloalkylamines, basic heterocycles,
- ammonium hydroxides and carbocyclic amines The following may be mentioned
- the reactants can be reacted with one another as such, i.e. without the addition of a solvent or diluent, for example in the melt. In most cases, however, the addition of an inert solvent or diluent or of a mixture thereof is advantageous.
- solvents or diluents examples 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 or tetrachloroethene; esters, such as ethyl acetate; ethers, such as diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, tert-butyl methyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, dime
- bases used in excess such as triethylamine, pyridine, N-methylmorpholine or N,N-diethylaniline, may also serve as solvents or diluents.
- the reaction is advantageously carried out in a temperature range from approximately 0°C to approximately +120°C, preferably from approximately 0°C to approximately +40°C.
- a compound of formula VIII is reacted at from 0°C to approximately +40°C, preferably at room temperature, in an inert solvent, preferably an ether, especially 1,4-dioxane, with an alkyl nitrite, preferably isopentyl nitrite.
- Suitable bases for facilitating the reaction are, for example, alkali metal or alkaline earth metal hydroxides, hydrides, amides, alkanolates, acetates, carbonates, dialkylamides or alkylsilylamides, or alkylamines, alkylenediamines, unsubstituted or N-alkylated, saturated or unsaturated cycloalkylamines, basic heterocycles,
- ammonium hydroxides and carbocyclic amines The following may be mentioned
- 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,
- the reactants can be reacted with one another as such, i.e. without the addition of a solvent or diluent, for example in the melt. In most cases, however, the addition of an inert solvent or diluent or of a mixture thereof is advantageous.
- solvents or diluents examples 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 or tetrachloroethene; esters, such as ethyl acetate; ethers, such as diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, tert-butyl methyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, dime
- bases used in excess such as triethylamine, pyridine, N-methylmorpholine or N,N-diethylaniline, may also serve as solvents or diluents.
- the reaction is advantageously carried out in a temperature range from approximately 0°C to approximately +120°C, preferably from approximately 0°C to approximately +40°C.
- a compound of formula III is reacted at from 0°C to approximately +120°C, preferably at room temperature, in an inert solvent, preferably N,N-dimethylform- amide, in the presence of a base, preferably an inorganic base, especially sodium hydride, with a compound of formula XI.
- Suitable halogenating agents are, for example, elemental chlorine or bromine, thionyl chloride, sulfur dichloride, sulfuryl chloride, phosphorus trichloride, phosphorus tribromide, phosphorus pentachloride or N-bromosuccinimide, preferably N-bromosuccinimide.
- Suitable bases for facilitating the reaction are, for example, alkali metal or alkaline earth metal hydroxides, hydrides, amides, alkanolates, acetates, carbonates,
- ammonium hydroxides and carbocyclic amines The following may be mentioned
- 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,
- the reactants can be reacted with one another as such, i.e. without the addition of a solvent or diluent, for example in the melt. In most cases, however, the addition of an inert solvent or diluent or of a mixture thereof is advantageous.
- solvents or diluents examples 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 or tetrachloroethene; esters, such as ethyl acetate; ethers, such as diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, tert-butyl methyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, dime
- bases used in excess such as triethylamine, pyridine, N-methylmorpholine or N,N-diethylaniline, may also serve as solvents or diluents.
- the reaction is advantageously carried out in a temperature range from approximately 0°C to approximately +120°C, preferably from approximately 0°C to approximately +40°C.
- a compound of formula XII is reacted at from 0°C to approximately +120°C, preferably at room temperature, in an inert solvent, preferably dimethyl sulfoxide, in the presence of a base, preferably an inorganic base, especially potassium carbonate, with a compound of the formula X 3 R 9 , and the compound so obtainable is reacted with a halogenating agent, preferably N-bromosuccinimide.
- the compounds of formulae I, II, III, IV, VII, VIII and IX may be in the form of one of the possible isomers or in the form of a mixture thereof, for example depending on the number of asymmetric carbon atoms and the absolute and relative configuration thereof they may be 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 hereinbefore and hereinafter, even if stereochemical details are not specifically mentioned in each case.
- optical antipodes can be separated into the optical antipodes by known methods, for example by recrystallisation from an optically active solvent, by chromatography on chiral adsorbents, for example high-pressure liquid chromatography (HPLC) on acetyl cellulose, with the aid of suitable microorganisms, by cleavage with specific immobilised enzymes, 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
- the biologically more active isomer for example enantiomer, or mixture of isomers, for example mixture of enantiomers, will be isolated or synthesised, insofar as the individual components have differing biological activity.
- the compounds of formulae I, II, III, IV, VII, VIII and IX also be obtained in the form of their hydrates and/or may include other solvents, for example solvents used, where appropriate, for the crystallisation of compounds in solid form.
- the invention relates to all those forms of the process according to which a compound obtainable as starting material or intermediate at any stage of the process is used as starting material and all or some of the remaining steps are carried out, or a starting material is used in the form of a derivative or a salt and/or its racemates or antipodes or, especially, is formed under the reaction conditions.
- the invention relates especially to the preparation processes described in Examples P1 , P3, P5, P7 and P8.
- the invention relates also to those starting materials and intermediates used according to the invention for the preparation of the compounds of formula I, especially those compounds of formulae II, III, IV, VII, VIII and IX, that are novel, to the use thereof and to processes for the preparation thereof.
- the compounds of formulae II, III, IV and IX can be prepared analogously to Examples P1, P3 and P7 and P8, respectively.
- the compounds of formula I have a microbicidal spectrum that is especially advantageous for practical requirements in the control of phytopathogenic microorganisms, especially fungi. They have very advantageous curative, preventive and, in particular, systemic properties, and can be used in the protection of numerous cultivated plants. With the compounds of formula I it is possible to inhibit or destroy the pests which occur on plants or on parts of plants (the fruit, blossom, leaves, stems, tubers, roots) in different crops of useful plants, while at the same time parts of plants which grow later are also protected from phytopathogenic microorganisms.
- the compounds of formula I can also be used as dressing agents for protecting seed (fruit, tubers, grains) and plant cuttings against fungal infection as well as against
- Compounds of formula I are effective, for example, against the phytopathogenic fungi belonging to the following classes: Fungi imperfecti (especially Botrytis, also Pyricularia, Helminthosporium, Fusarium, Septoria, Cercospora, Cercosporella and Altemaria);
- Fungi imperfecti especially Botrytis, also Pyricularia, Helminthosporium, Fusarium, Septoria, Cercospora, Cercosporella and Altemaria
- Basidiomycetes e.g. Rhizoctonia, Hemileia, Puccinia. They are also effective against the class of the Ascomycetes (e.g. Venturia and Erysiphe, Podosphaera, Monilinia, Uncinula), but especially against the class of the Oomycetes (e.g. Phytophthora, Peronospora, Bremia, Pythium, Plasmopara).
- the compounds of formula I according to the invention are also valuable active ingredients in the field of animal pest control, while being well tolerated by warm-blooded animals, fish and plants.
- the compounds according to the invention are effective against insects and representatives of the order Acarina, such as those occurring on useful plants and omamentals in agriculture and horticulture, especially in plantations of cotton, vegetables and fruit, and in forestry.
- the compounds of the invention are suitable especially for controlling insects and representatives of the order Acarina in crops of fruit and vegetables, especially for controlling plant-destructive insects, such as Spodoptera littoralis, Heliothis virescens, Diabrotica balteata and Crocidolomia binotalis.
- Further areas of use of the compounds of the invention are in the protection of stocks and materials and in the hygiene sector, especially in the protection of domestic animals and productive livestock.
- the compounds according to the invention are effective against all or individual
- the action of the compounds of the invention may manifest itself, for example, in the mortality of the pests, which occurs immediately or only after some time, for example during moulting, or in reduced oviposition and/or hatching rate.
- the above-mentioned pests include: of the order Lepidoptera, for example,
- Agriotes spp. Anthonomus spp., Atomaria linearis, Chaetocnema tibialis, Cosmopolites spp., Curculio spp., Dermestes spp., Diabrotica spp., Epilachna spp., Eremnus spp.,
- Otiortiynchus spp. Phlyctinus spp., Popillia spp., Psylliodes spp., Rhizopertha spp.,
- 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 Mallophaga, for example,
- Scirtothrips aurantii of the order Heteroptera, for example,
- Leptocorisa spp. Leptocorisa spp., Nezara spp., Piesma spp., Rhodnius spp., Sahlbergella singularis, Scotinophara spp. and Triatoma spp.; of the order Homoptera, for example,
- Aleurothrixus floccosus Aleurothrixus floccosus, 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., Gascardia spp., Laodelphax spp., Lecanium corni, 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,
- 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., Drosophila melanogaster, Fannia spp., Gastrophilus spp., Glossina spp., Hypoderma spp., Hyppobosca spp.,
- Lepisma saccharina and of the order Acarina, for example,
- Boophilus spp. Brevipalpus spp., Bryobia praetiosa, Calipitrimerus spp., Chorioptes spp., Dermanyssus gallinae, Eotetranychus carpini, Eriophyes spp., Hyalomma spp., Ixodes spp., Olygonychus pratensis, Ornithodoros spp., Panonychus spp., Phyllocoptruta oleivora, Polyphagotarsonemus latus, Psoroptes spp., Rhipicephalus spp., Rhizoglyphus spp., Sarcoptes spp., Tarsonemus spp. and Tetranychus spp..
- the good pesticidal activity of the compounds according to the invention corresponds to a mortality of at least 50-60 % of the mentioned pests.
- the activity of the compounds of the invention and of the compositions comprising them can be substantially broadened and adapted to prevailing circumstances by the addition of other insecticides and/or acaricides.
- suitable additional active ingredients include representatives of the following classes of compounds: organophosphorus compounds, nitrophenols and derivatives, formamidines, ureas, carbamates, pyrethroids, chlorinated hydrocarbons, and Bacillus thuringiensis preparations.
- the compounds according to the invention are used in unmodified form or preferably together with the adjuvants conventionally employed in formulation technology, and are therefore formulated in known manner, e.g. into emulsifiable concentrates, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts or granules, or by encapsulation in e.g. polymer substances.
- the methods of application such as spraying, atomising, dusting, scattering or pouring, are chosen in accordance with the intended objectives and the prevailing circumstances.
- compositions, preparations or mixtures comprising the compound (active ingredient) and, where appropriate, solid or liquid adjuvants are prepared in known manner, for example by intimately mixing and/or grinding the active ingredient with the adjuvants, such as extenders, e.g. solvents or solid carriers, or surface active compounds (surfactants).
- adjuvants such as extenders, e.g. solvents or solid carriers, or surface active compounds (surfactants).
- Suitable solvents are, for example: aromatic hydrocarbons, preferably the fractions of alkylbenzenes containing 8 to 12 carbon atoms, such as xylene mixtures, alkylated naphthalenes, aliphatic or cycloaliphatic hydrocarbons, such as cyclohexane, paraffins or tetrahydronaphthalene, 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-2-pyrrolidone, dimethyl sulfoxide or N,N-dimethylformamide, water and vegetable oils or epoxidised vegetable oils, such as rape oil, castor oil, coconut oil or soybean oil
- the solid carriers used are normally natural mineral fillers such as calcite, talcum, kaolin, montmorillonite or attapulgite.
- Suitable granulated adsorptive carriers are porous types, such as pumice, broken brick, sepiolite or bentonite; and suitable nonsorbent carriers are calcite or sand.
- suitable nonsorbent carriers are calcite or sand.
- 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 having good emulsifying, dispersing and wetting properties.
- surfactants will also be understood as comprising mixtures of surfactants.
- Non-ionic surfactants are preferably polyglycol ether derivatives of aliphatic or cycloaliphatic alcohols, saturated or unsaturated fatty acids 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 adducts of polyethylene oxide with polypropylene glycol, ethylenediaminopolypropylene glycol and alkylpolypropylene glycol containing 1 to 10 carbon atoms in the alkyl chain, which adducts 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 of non-ionic surfactants are nonylphenol polyethoxyethanols, castor oil polyglycol ethers,
- polypropylene/polyethylene oxide adducts polypropylene/polyethylene oxide adducts, tributylphenoxypolyethoxyethanol, polyethylene glycol and octylphenoxypolyethoxyethanol.
- Fatty acid esters of polyoxyethylene sorbitan e.g. polyoxyethylene sorbitan trioleate, are also suitable non-ionic surfactants.
- Cationic surfactants are preferably quaternary ammonium salts which contain, as N-substituent, at least one C 8 -C 22 alkyl radical and, as further substituents, unsubstituted or halogenated lower alkyl, benzyl or hydroxy-lower alkyl radicals.
- the salts are preferably in the form of halides, methyl sulfates or ethyl sulfates. Examples are stearyltrimethyl-ammonium chloride and benzyl-di(2-chloroethyl)ethylammonium bromide. Both water-soluble soaps and water-soluble synthetic surface-active compounds are suitable anionic surfactants.
- 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. More frequently, however, synthetic surfactants are used, especially 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 C 8 -C 22- alkyl radical, which also includes the alkyl moiety of acyl radicals; there may be mentioned by way of example the sodium or calcium salt of lignosulfonic acid, of dodecyl sulfate or of a mixture of fatty alcohol sulfates obtained from natural fatty acids. These compounds also include the salts of sulfated and sulfonated fatty alcohol/ethylene oxide adducts.
- the sulfonated benzimidazole derivatives preferably contain 2 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, dibutylnaphthalenesulfonic acid or of a condensate of naphthalenesulfonic acid and formaldehyde.
- corresponding phosphates e.g. salts of the phosphoric acid ester of an adduct of p-nonylphenol with 4 to 14 mol of ethylene oxide, or
- surfactants listed above are to be regarded merely as examples; many other surfactants used in formulation technology that are suitable in accordance with the invention are described in the relevant literature.
- the pesticidal 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 a solid or liquid adjuvant, it generally being possible for 0 to 25%, preferably 0.1 to 20%, of the composition to be surfactants (in each case percentages are by weight).
- a solid or liquid adjuvant preferably 0.1 to 20%
- the end user will normally employ dilute formulations which have considerably lower active ingredient concentrations.
- Typical rates of concentration are from 0.1 to 1000 ppm, preferably from 0.1 to 500 ppm, active ingredient.
- the rates of application per hectare are generally from 1 to 1000 g of active ingredient per hectare, preferably from 25 to 500 g/ha.
- Preferred formulations have especially the following composition (throughout, percentages are by weight):
- Emulsifiable concentrates are:
- surfactant 1 to 30 %, preferably 10 to 20 %
- liquid carrier 5 to 94 %, preferably 70 to 85 %
- active ingredient 0.1 to 10 %, preferably 0.1 to 1 %
- solid carrier 99.9 to 90 %, preferably 99.9 to 99 %
- active ingredient 5 to 75 %, preferably 10 to 50 %
- surfactant 1 to 40 %, preferably 2 to 30 %
- active ingredient 0.5 to 90 %, preferably 1 to 80 %
- surfactant 0.5 to 20 %, preferably 1 to 15 %
- solid carrier 5 to 95 %, preferably 15 to 90 %
- active ingredient 0.5 to 30 %, preferably 3 to 15 %
- solid carrier 99.5 to 70 %, preferably 97 to 85 %
- compositions may also comprise further adjuvants, such as stabilisers, for example vegetable oils or epoxidised vegetable oils (e.g. epoxidised coconut oil, rape oil or soybean oil), antifoams, for example silicone oil, preservatives, viscosity regulators, binders and/or tackifiers, as well as fertilisers or other active ingredients for obtaining special effects.
- stabilisers for example vegetable oils or epoxidised vegetable oils (e.g. epoxidised coconut oil, rape oil or soybean oil), antifoams, for example silicone oil, preservatives, viscosity regulators, binders and/or tackifiers, as well as fertilisers or other active ingredients for obtaining special effects.
- 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
- Example P1/1 1-[4-(2,2-Dichlorocyclopropylmethoxy)-2,5-difluorophenyl]-propan-1-one 2-oxime (Compound No. 1.77 in Table 1)
- Hydrogen chloride gas is introduced into 350 ml of dioxane for 2 minutes and then 43.5 g of (2,2-dichlorocyclopropylmethoxy)-2,5-difluorophenyl]-propan-1-one, followed, dropwise, by 19.8 g of isopentyl nitrite, are added.
- the reaction mixture is stirred at room temperature for 24 hours and then hydrogen chloride gas is again introduced for 2 minutes and the reaction mixture is stirred for a further 30 hours at room temperature.
- the mixture is then rendered basic with triethylamine and concentrated by evaporation in vacuo.
- Example P3/1 1-[6-(2,2-Dichlorocyclopropylmethoxy)-5-fluoro-1-methyl-1 H-indazol-3-yl]- ethanone oxime (Compound No. 2.77 in Table 2)
- Example P5/1 2-[[[(1 - ⁇ 6-[(2,2-Dichlorocyclopropyl)methoxy]-5-fluoro-1-methylindazol-3-yl ⁇ - ethylidene)amino]oxy]methyl]- ⁇ -(methoxymethylene)phenylacetic acid methyl ester (Compound No. 3.77)
- Example P5/2 2-(2- ⁇ 1-[6-(4-Chlorophhnoxy)-1-methyl-1H-indazol-3-yl]-ethylideneaminooxy- methyl ⁇ -phenyl)-3-methoxyacrylic acid methyl ester (Compound No. 3.57)
- the reaction mixture is stirred at room temperature for 3 hours and then neutralised with glacial acetic acid.
- the reaction mixture is then concentrated by evaporation under a high vacuum and the residue is taken up in ethyl acetate, washed with water and brine, dried over sodium sulfate and concentrated by evaporation in vacuo.
- the crude product is chromatographed on silica gel with ethyl acetate admixed with from 5 to 20 % hexane, at 1.2 bar. Ether and hexane are added, yielding the title compound having a melting point of 124-125°C.
- the reaction mixture is stirred for 3 hours, neutralised with glacial acetic acid and then concentrated by evaporation under a high vacuum.
- the residue is taken up in ethyl acetate, washed with water and brine, dried over sodium sulfate and concentrated by evaporation.
- the crude product is chromatographed on silica gel with ethyl acetate admixed with from 5 to 20 % hexane, at 1.2 bar. Ether and hexane are added, yielding the title compound having a melting point of 95-96°C.
- Example P5/4 2-(2- ⁇ 1-[6-(4-Chlorophenoxy)-1-methyl-1H-indazol-3-yl]-ethylideneaminooxy-methyl ⁇ -phenyl)-2-methoxyimino-N-methylacetamide (Compound No. 5.57)
- Example P6 The other compounds listed in Tables 3 to 11 can also be prepared in a manner analogous to that described in Example P5.
- cProp denotes cyclopropyl.
- the figures represent the melting point in °C.
- the finely ground active ingredient is mixed with the adjuvants, giving an emulsifiable concentrate which can be diluted with water to give emulsions of any desired concentration.
- the finely ground active ingredient is mixed with the adjuvants, giving a solution that is suitable for use in the form of microdrops.
- the active ingredient is dissolved in dichloromethane and the solution is sprayed onto the carrier mixture and the solvent is evaporated off in vacuo.
- the active ingredient is mixed with the carriers, giving dusts that are ready for use.
- the 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 the desired concentration.
- Example F6 Emulsifiable concentrate
- the finely ground active ingredient is mixed with the adjuvants, giving an emulsifiable concentrate which can be diluted with water to give emulsions of any desired concentration.
- Ready-for-use dusts are obtained by mixing the active ingredient with the carrier and grinding the mixture in a suitable mill.
- the active ingredient is mixed with the adjuvants and the mixture is ground and moistened with water.
- the mixture is extruded and granulated and the granules are dried in a stream of air.
- the finely ground active ingredient is uniformly applied, in a mixer, to the kaolin moistened with polyethylene glycol. Non-dusty coated granules are obtained in this manner.
- the 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 Phytophthora infestans on tomatoes
- test compound formulated as a wettable powder is applied in a concentration of 60 ppm (based on the volume of the soil) to the soil surface of three-week-old tomato plants of the "Red Gnome" variety planted in pots. After a 3-day waiting period, the undersides of the leaves of the plants are sprayed with a zoospore suspension of Phytophthora infestans. The plants are then kept in a spray cabinet for 5 days at 18 to 20°C and 100 % humidity. After that time, typical leaf specks form, the number and size of which are used to evaluate the activity of the test compounds.
- Example B2 Action against Plasmopara viticola (Bert, et Curt.) (Berl. et DeToni) on vines a) Residual-preventive action
- Vine seedlings of the "Chasselas" variety are grown in a greenhouse. 3 plants are sprayed at the 10-leaf stage with a mixture (200 ppm active ingredient). After the spray coating has dried, the undersides of the leaves of the plants are infected uniformly with a spore suspension of the fungus. The plants are then kept in a humidity chamber for 8 days. After that time, the control plants exhibit marked symptoms of disease. The activity of the test compounds is evaluated on the basis of the number and size of the sites of infection on the treated plants. b) Curative action
- Vine seedlings of the "Chasselas” variety are grown in a greenhouse and the undersides of the leaves are infected at the 10-leaf stage with a spore suspension of Plasmopara viticola. After 24 hours in a humidity cabinet, the plants are sprayed with a mixture of the test compound (200 ppm active ingredient). Then the plants are kept in the humidity cabinet for a further 7 days. After that time, the control plants exhibit symptoms of disease. The activity of the test compounds is evaluated on the basis of the number and size of the sites of infection on the treated plants.
- Example B3 Action against Pythium debaryanum on sugar beet (Beta vulgaris)
- the fungus is cultivated on sterile oat grains and added to a soil/sand mixture.
- the soil so infected is introduced into plant pots and sown with sugar beet seeds.
- a wettable powder formulation of the test compounds is poured in the form of an aqueous suspension over the soil (20 ppm active ingredient, based on the volume of the soil).
- the pots are then placed in a greenhouse at 20-24°C for 2-3 weeks.
- the soil is kept uniformly moist by light spraying with water.
- the test is evaluated by determining the emergence of the sugar beet plants and the number of healthy and diseased plants.
- the fungus is cultivated on sterile oat grains and added to a soil/sand mixture.
- the soil so infected is introduced into plant pots and sown with sugar beet seeds which have been dressed with the test compounds formulated as dressing powders (1000 ppm active ingredient, based on the weight of the seeds).
- the pots containing the seeds are then placed in a greenhouse at 20-24°C for 2-3 weeks.
- the soil is kept uniformly moist by light spraying with water.
- the test is evaluated by determining the emergence of the sugar beet plants and the number of healthy and diseased plants.
- Example B4 Residual-protective action against Cercospora arachidicola on groundnuts 10 to 15 cm high groundnut plants are sprayed to drip point with an aqueous spray mixture (0.02% active ingredient) and are infected 48 hours later with a conidia suspension of the fungus. The plants are incubated for 72 hours at 21°C and high humidity and are then placed in a greenhouse until the typical leaf specks occur. The activity of the test compound is evaluated 12 days after infection and is based on the number and size of the leaf specks.
- wheat plants are sprayed to drip point with an aqueous spray mixture (0.02% active ingredient) and are 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 with an aqueous spray mixture (0.006% active ingredient, based on the volume of the soil). Care is taken that the spray mixture does not come into contact with the parts of the plants above the soil. After 48 hours the plants are infected 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 of formula I effect a marked reduction in fungus infestation.
- compounds 3.1 , 3.2, 3.15, 4.15 and 4.27 effect a reduction in fungus infestation of more than 90 %.
- Example B6 Action against Pyricularia oryzae on rice
- rice plants are sprayed to drip point with an aqueous spray mixture (0.02% active ingredient) and are infected 48 hours later with a conidia suspension of the fungus. Evaluation of fungus infestation is made 5 days after infection, during which period 95 to 100% relative humidity and a temperature of 22°C are
- 2-week-old rice plants are watered with an aqueous spray mixture (0.006% active ingredient, based on the volume of the soil). Care is taken that the spray mixture does not come into contact with the parts of the plants above the soil.
- the pots are then filled with water so that the lowermost parts of the stems of the rice plants stand in water. After 96 hours, the plants are infected with a conidia suspension of the fungus and are kept for 5 days at 95 to 100% relative humidity and a temperature of 24°C.
- Example B7 Residual-protective action against Venturia inaequalis on apples
- Apple cuttings with 10-20 cm long fresh shoots are sprayed to drip point with a spray mixture (0.02% active ingredient) and are infected 24 hours later with a conidia suspension of the fungus.
- the plants are incubated for 5 days at 90 to 100% relative humidity and are placed for a further 10 days in a greenhouse at 20 to 24°C. Scab infestation is evaluated 15 days after infection.
- Compounds of formula I of one of Tables 3 to 14 mainly have a lasting effect against scab diseases.
- compounds 3.1 , 3.2, 3.15 and 4.15 effect a reduction in fungus infestation of more than 90 %.
- Barley plants about 8 cm in height are sprayed to drip point with an aqueous spray mixture (0.02% active ingredient) and are dusted 3 to 4 hours later with conidia of the fungus.
- the infected plants are placed in a greenhouse at 22°C. 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 the soil). Care is taken that the spray mixture does not come into contact with the parts of the plants above the soil. The plants are dusted 48 hours later with conidia of the fungus. The infected plants are placed in a greenhouse at 22°C. Evaluation of fungus infestation is made 10 days after infection. Compounds of formula I are generally able to reduce disease infestation to less than 20%, and in some cases even completely. Compounds 3.1 , 3.2, 3.15, 4.15 and 4.27 reduce fungus infestation to less than 5 %.
- Example B9 Action against Podosphaera leucotricha on apple shoots
- Apple cuttings with about 15 cm long fresh shoots are sprayed with a spray mixture (0.06% active ingredient). After 24 hours, the treated plants are infected with a conidia suspension of the fungus and are placed in a climatic chamber at 70% relative humidity and 20°C. Fungus infestation is evaluated 12 days after infection.
- Example B10 Action against Botrytis cinerea on apple fruits
- the fungicidal activity of the test compound is derived from the number of rotted damaged sites.
- the compounds of formula I of Tables 3 to 14 are able to prevent the rot from spreading, in some cases completely.
- compounds 3.1 , 3.2, 3.15 and 4.15 reduce fungus infestation to less than 5 %.
- Example B11 Action against Helminthosporium gramineum
- Wheat grains are contaminated with a spore suspension of the fungus and are left to dry.
- the contaminated grains are dressed with a suspension of the test compound (600 ppm active ingredient, based on the weight of the seeds). 2 days later, the grains are placed on suitable agar dishes and, after a further four days, the development of the fungus colonies around the grains is assessed. The evaluation of the test compound is based on the number and size of the fungus colonies.
- Some of the compounds of formula I exhibit good activity, i.e. inhibition of the fungus colonies. In particular, compounds 3.1 , 3.2, 3.15, 4.15 and 4.27 reduce fungus infestation to less than 5 %.
- Example B12 Action against Colletotrichum Iagenarium on cucumbers
- cucumber plants are sprayed with a spray mixture (concentration 0.002%). 2 days later, the plants are infected with a spore suspension (1.5 ⁇ 10 5 spores/ml) of the fungus and are incubated for 36 hours at 23°C and high humidity. Incubation is then continued at normal humidity and about 22-23°C. The fungus infestation that has occurred is evaluated 8 days after infection. Fungus infestation is 100% on untreated and infected control plants.
- the compounds of formula I inhibit infestation with the disease in some cases almost completely.
- compounds 3.1 , 3.2, 3.3, 3.4, 3.15, 3.36, 4.27 and 5.103 reduce fungus infestation to less than 5 %.
- Example B13 Action against Fusarium nivale on rye
- Rye of the Tetrahell variety which is naturally infected with Fusarium nivale is dressed in a roller mixer with the test fungicide, the following concentrations being used: 20 or 6 ppm a.i. (based on the weight of the seed).
- the infected and treated rye is sown in October in the open with a seeder in plots 3 metres long and in 6 rows. Three replicates are carried out with each concentration.
- test crop is cultivated under normal field conditions (preferably in a region with unbroken snow cover during the winter months).
- the emergence is assessed in the autumn and the crop density/number of plants per unit area is assessed in the spring.
- the percentage of plants attacked by Fusarium is calculated in the spring immediately after the snow has melted.
- the number of infested plants is less than 5% in the present case.
- the plants that have emerged have a healthy appearance.
- Example B14 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.
- 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 are placed in a greenhouse for a further 10 days at 20-24°C.
- Fungus infestation is evaluated 13 days after infection. Less than 1 % of the wheat plants are infested.
- Example B15 Action against Rhizoctonia solani on rice
- 10-day-old rice plants are watered with a suspension (spray mixture) prepared from formulated test compound, without contaminating the parts of the plants above the soil.
- the plants are infected three days later by placing a barley straw infected with Rhizoctonia solani between the rice plants in each pot. Fungus infestation is evaluated after incubation for 6 days in a climatic chamber at a day temperature of 29°C and a night temperature of 26°C and at 95% relative humidity. Less than 5% of the rice plants are infested.
- the plants have a healthy appearance.
- Example B16 Action against Aphis craccivora
- Pea seedlings are infested with Aphis craccivora and then sprayed with a spray mixture comprising 100 ppm of test compound, and incubated at 20°C.
- the percentage reduction in the population is determined 3 and 6 days later by comparing the number of dead aphids on the treated plants with that on untreated plants.
- Maize seedlings are sprayed with an aqueous emulsion comprising 100 ppm of 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. The percentage reduction in the population (% activity) is determined 6 days later by comparing the number of dead larvae on the treated plants with that on untreated plants.
- Example B18 Action against Heliothis virescens
- Young soybean plants are sprayed with an aqueous emulsion comprising 100 ppm of test compound. After the spray coating has dried, the soybean plants are populated with 10 Heliothis virescens caterpillars in the first stage and then placed in a plastics container. The percentage reduction in the population and the percentage reduction in feeding damage (% activity) are determined 6 days later by comparing the number of dead caterpillars and the feeding damage on the treated plants with those on untreated plants.
- Young soybean plants are sprayed with an aqueous emulsion comprising 100 ppm of test compound. After the spray coating has dried, the soybean plants are populated with 10 Spodoptera littoralis caterpillars in the third stage and then placed in a plastics container. The percentage reduction in the population and the percentage reduction in feeding damage (% activity) are determined 3 days later by comparing the number of dead caterpillars and the feeding damage on the treated plants with those on untreated plants.
- Example B20 Feeding action against Ctenocephalides felis (systemic)
- the membrane is then placed on the cage.
- the vessel contains blood comprising 50 ppm of active ingredient and is heated to a constant temperature of 37°C.
- the fleas take up the blood through the membrane. Evaluation is effected 24 and 48 hours after the start of the test.
- the percentage reduction in population (% activity) is determined from a comparison of the number of dead fleas given treated blood with those given untreated blood. 24 hours after treatment the blood is replaced with fresh blood that has likewise been treated.
- Example B21 Action against Musca domestica
- a sugar cube is treated with a solution of the test compound in such a manner that, after drying overnight, the concentration of test compound in the sugar is 250 ppm.
- the treated cube is placed with a wet cotton wool swab and 10 Musca domestica adults of an OP resistant strain on an aluminium dish, covered with a glass beaker and incubated at 25°C. The mortality is determined after 24 hours.
- Example B22 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 comprising 100 ppm of test compound. The plants are then incubated for 6 days at 25°C and then evaluated. The percentage reduction in the population (% activity) is determined by comparing the number of dead eggs, larvae and adults on the treated plants with that on untreated plants.
- Boophilus microplus females which are replete with blood are affixed to a PVC plate and covered with a cotton wool swab.
- 10 ml of an aqueous test solution comprising 125 ppm of the test compound are poured over the test insects.
- the cotton wool swab is then removed and the ticks are incubated for 4 weeks until oviposition has taken place.
- the action against Boophilus microplus manifests itself either as mortality or sterility of the female or as ovicidal action in the eggs.
Abstract
Description
Claims
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US09/011,916 US5935908A (en) | 1995-08-15 | 1996-08-05 | Pesticidal indazole derivatives |
JP50889397A JP4083801B2 (en) | 1995-08-15 | 1996-08-05 | Insecticidal indazole derivatives |
DE69637267T DE69637267T2 (en) | 1995-08-15 | 1996-08-05 | PESTICIDE INDAZOLE DERIVATIVES |
EP96927683A EP0844993B1 (en) | 1995-08-15 | 1996-08-05 | Pesticidal indazole derivatives |
AU67421/96A AU6742196A (en) | 1995-08-15 | 1996-08-05 | Pesticidal indazole derivatives |
Applications Claiming Priority (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CH2340/95 | 1995-08-15 | ||
CH234095 | 1995-08-15 | ||
CH238195 | 1995-08-21 | ||
CH2381/95 | 1995-08-21 | ||
CH30596 | 1996-02-06 | ||
CH305/96 | 1996-02-06 |
Publications (2)
Publication Number | Publication Date |
---|---|
WO1997007103A2 true WO1997007103A2 (en) | 1997-02-27 |
WO1997007103A3 WO1997007103A3 (en) | 1997-03-20 |
Family
ID=27171979
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP1996/003452 WO1997007103A2 (en) | 1995-08-15 | 1996-08-05 | Pesticidal indazole derivatives |
Country Status (9)
Country | Link |
---|---|
US (1) | US5935908A (en) |
EP (1) | EP0844993B1 (en) |
JP (1) | JP4083801B2 (en) |
AT (1) | ATE374188T1 (en) |
AU (1) | AU6742196A (en) |
BR (1) | BR9603430A (en) |
DE (1) | DE69637267T2 (en) |
ES (1) | ES2294789T3 (en) |
WO (1) | WO1997007103A2 (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1999046263A2 (en) * | 1998-03-09 | 1999-09-16 | Bayer Aktiengesellschaft | Fungicidal benzoheterocyclyloxime |
WO2012081916A2 (en) * | 2010-12-17 | 2012-06-21 | 한국화학연구원 | Indazole derivative and a pesticide composition containing the same |
US10743535B2 (en) | 2017-08-18 | 2020-08-18 | H&K Solutions Llc | Insecticide for flight-capable pests |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6428814B1 (en) | 1999-10-08 | 2002-08-06 | Elan Pharma International Ltd. | Bioadhesive nanoparticulate compositions having cationic surface stabilizers |
JP2003518100A (en) | 1999-12-22 | 2003-06-03 | バイエル アクチェンゲゼルシャフト | Pyrazolylbenzyl ether derivatives containing fluoromethoxyimino groups and their use as pesticides |
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DE4213149A1 (en) * | 1992-04-22 | 1993-10-28 | Hoechst Ag | Acaricidal, insecticidal and nematicidal substituted (hetero) aryl-alkyl-ketone oxime-O-ether, process for their preparation, compositions containing them and their use as pesticides |
CZ291625B6 (en) * | 1994-01-05 | 2003-04-16 | Bayer Aktiengesellschaft | Oxime derivatives |
PL179345B1 (en) * | 1994-02-04 | 2000-08-31 | Basf Ag | Derivatives of phenyloacetic acid, method of and intermediate products for obtaining them and agents containing such derivatives |
MX9603175A (en) * | 1994-02-04 | 1997-04-30 | Basf Ag | Phenylthio acetic acid derivatives, process and intermediate products for their production and agents containing them. |
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1996
- 1996-08-05 EP EP96927683A patent/EP0844993B1/en not_active Expired - Lifetime
- 1996-08-05 ES ES96927683T patent/ES2294789T3/en not_active Expired - Lifetime
- 1996-08-05 WO PCT/EP1996/003452 patent/WO1997007103A2/en active IP Right Grant
- 1996-08-05 AU AU67421/96A patent/AU6742196A/en not_active Abandoned
- 1996-08-05 AT AT96927683T patent/ATE374188T1/en not_active IP Right Cessation
- 1996-08-05 US US09/011,916 patent/US5935908A/en not_active Expired - Fee Related
- 1996-08-05 JP JP50889397A patent/JP4083801B2/en not_active Expired - Fee Related
- 1996-08-05 DE DE69637267T patent/DE69637267T2/en not_active Expired - Fee Related
- 1996-08-14 BR BR9603430A patent/BR9603430A/en not_active Application Discontinuation
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Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1999046263A2 (en) * | 1998-03-09 | 1999-09-16 | Bayer Aktiengesellschaft | Fungicidal benzoheterocyclyloxime |
WO1999046263A3 (en) * | 1998-03-09 | 1999-11-11 | Bayer Ag | Fungicidal benzoheterocyclyloxime |
US6462039B1 (en) | 1998-03-09 | 2002-10-08 | Bayer Aktiengesellschaft | Fungicidal benzoheterocyclyloxime |
WO2012081916A2 (en) * | 2010-12-17 | 2012-06-21 | 한국화학연구원 | Indazole derivative and a pesticide composition containing the same |
WO2012081916A3 (en) * | 2010-12-17 | 2012-08-16 | 한국화학연구원 | Indazole derivative and a pesticide composition containing the same |
US10743535B2 (en) | 2017-08-18 | 2020-08-18 | H&K Solutions Llc | Insecticide for flight-capable pests |
Also Published As
Publication number | Publication date |
---|---|
AU6742196A (en) | 1997-03-12 |
ES2294789T3 (en) | 2008-04-01 |
EP0844993A2 (en) | 1998-06-03 |
BR9603430A (en) | 1998-12-29 |
JP4083801B2 (en) | 2008-04-30 |
WO1997007103A3 (en) | 1997-03-20 |
DE69637267D1 (en) | 2007-11-08 |
JPH11511149A (en) | 1999-09-28 |
ATE374188T1 (en) | 2007-10-15 |
EP0844993B1 (en) | 2007-09-26 |
US5935908A (en) | 1999-08-10 |
DE69637267T2 (en) | 2008-06-26 |
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