CA2323661A1 - Fungicide mixtures based on triple oxime ether derivatives and rhizoctonia fungicides - Google Patents
Fungicide mixtures based on triple oxime ether derivatives and rhizoctonia fungicides Download PDFInfo
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- CA2323661A1 CA2323661A1 CA002323661A CA2323661A CA2323661A1 CA 2323661 A1 CA2323661 A1 CA 2323661A1 CA 002323661 A CA002323661 A CA 002323661A CA 2323661 A CA2323661 A CA 2323661A CA 2323661 A1 CA2323661 A1 CA 2323661A1
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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
- A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
- A01N37/44—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a nitrogen atom attached to the same carbon skeleton by a single or double bond, this nitrogen atom not being a member of a derivative or of a thio analogue of a carboxylic group, e.g. amino-carboxylic acids
- A01N37/50—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a nitrogen atom attached to the same carbon skeleton by a single or double bond, this nitrogen atom not being a member of a derivative or of a thio analogue of a carboxylic group, e.g. amino-carboxylic acids the nitrogen atom being doubly bound to the carbon skeleton
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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
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/02—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing liquids as carriers, diluents or solvents
- A01N25/04—Dispersions, emulsions, suspoemulsions, suspension concentrates or gels
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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
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/02—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing liquids as carriers, diluents or solvents
- A01N25/04—Dispersions, emulsions, suspoemulsions, suspension concentrates or gels
- A01N25/06—Aerosols
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- A—HUMAN NECESSITIES
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- A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
- A01N37/18—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing the group —CO—N<, e.g. carboxylic acid amides or imides; Thio analogues thereof
- A01N37/22—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing the group —CO—N<, e.g. carboxylic acid amides or imides; Thio analogues thereof the nitrogen atom being directly attached to an aromatic ring system, e.g. anilides
- A01N37/24—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing the group —CO—N<, e.g. carboxylic acid amides or imides; Thio analogues thereof the nitrogen atom being directly attached to an aromatic ring system, e.g. anilides containing at least one oxygen or sulfur atom being directly attached to the same aromatic ring system
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- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
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- 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
- A01N43/50—1,3-Diazoles; Hydrogenated 1,3-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
- 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
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- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
- A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
- A01N43/78—1,3-Thiazoles; Hydrogenated 1,3-thiazoles
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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
- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
- A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
- A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
- A01N47/30—Derivatives containing the group >N—CO—N aryl or >N—CS—N—aryl
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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
- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
- A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
- A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
- A01N47/32—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing >N—CO—N< or >N—CS—N< groups directly attached to a cycloaliphatic 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
- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
- A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
- A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
- A01N47/38—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing the group >N—CO—N< where at least one nitrogen atom is part of a heterocyclic ring; Thio analogues thereof
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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
- C07C251/50—Oximes having oxygen atoms of oxyimino groups bound to carbon atoms of substituted hydrocarbon radicals
- C07C251/56—Oximes having oxygen atoms of oxyimino groups bound to carbon atoms of substituted hydrocarbon radicals of hydrocarbon radicals substituted by doubly-bound oxygen atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/02—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
- C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
- C07D233/58—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring nitrogen atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
- C07D277/02—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings
- C07D277/20—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D277/22—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
- C07D277/28—Radicals substituted by nitrogen atoms
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Abstract
The invention relates to fungicide mixtures comprised as active components a) phenylacetic acid derivatives of formula (I) in which the substituents and the index have the meanings cited in the description, and the salts thereof, and b) at least one compound of formulas (II) to (VII) in a synergistically effective quantity.
Description
FUNGICIDE MIXTURES BASED ON TRIPLE OXIME ETHER
DERIVATIVES AND RHIZOCTONIA FUNGICIDES
The present invention relates to fungicidal mixtures for controlling harmful fungi, comprising a) phenylacetic acid derivatives of the formula I
R\O~N\ ~N/O ~R2)m (I), RS ~ N R' I
O. Rs O
in which the substituents and the index have the following meaning:
X is NOCHg, CHOCH3 or CHCH3;
Y is oxygen or NR;
R1, R independently of one another are each hydrogen or C1-C4-alkyl;
R2 is cyano, nitro, trifluoromethyl, halogen, C1-C4-alkyl or C1-C4-alkoxy;
m is 0, 1 or 2, where the radicals R2 may be different if m is 2;
R3 is hydrogen, cyano, C1-C4-alkyl, C1-C4-haloalkyl or C3-C6-cycloalkyl;
R4, R6 independently of one another are each hydrogen, la are C1-C1o-alkyl, C3-C6-cycloalkyl, C2-Clo-alkenyl, C2-Clo-alkynyl, C1-Clo-alkylcarbonyl, C2-Clo-alkenyl-carbonyl, C3-Clo-alkynylcarbonyl or C1-C1o-alkyl-sulfonyl, where these radicals may be partially or fully halogenated or may carry one to three of the following groups: cyano, nitro, hydroxyl, mercapto, amino, carboxyl, aminocarbonyl, aminothiocarbonyl, halogen, C1-C6-alkyl, C1-C6-haloalkyl, C1-C6-alkyl-sulfonyl, C1-C6-alkylsulfoxyl, C1-C6-alkoxy, C1-C6-haloalkoxy, C1-C6-alkoxycarbonyl, C1-C6-alkylthio, C1-C6-alkylamino, di-C1-C6-alkylamino, C1-C6-alkylamino-carbonyl, di-C1-C6-alkylaminocarbonyl, C1-C6-alkyl-aminothiocarbonyl, di-C1-C6-alkylaminothiocarbonyl, CZ-C6-alkenyl, CZ-C6-alkenyloxy, C3-C6-cycloalkyl, C3-C6-cycloalkyloxy, heterocyclyl, heterocyclyloxy, benzyl, benzyloxy, aryl, aryloxy, arylthio, hetaryl, hetaryloxy and hetarylthio, where the cyclic groups for their part may be partially or fully halogenated or~may carry one to three of the following groups: cyano, vitro, hydroxyl, mercapto, amino, carboxyl, amino-carbonyl, aminothiocarbonyl, halogen, C1-C6-alkyl, C1-C6-haloalkyl, C1-C6-alkylsulfonyl, C1-C6-alkyl-sulfoxyl, C3-C6-cycloalkyl, C1-C6-alkoxy, C1-C6-haloalkoxy, C1-C6-alkyloxycarbonyl, C1-C6-alkyl-thio, C1-C6-alkylamino, di-C1-C6-alkylamino, C1-C6-alkylaminocarbonyl, di-C1-C6-alkylaminocarbonyl, C1-C6-alkylaminothiocarbonyl, di-C1-C6-alkylaminothio-carbonyl, Cz-C6-alkenyl, CZ-C6-alkenyloxy, benzyl, benzyloxy, aryl, aryloxy, arylthio, hetaryl, hetaryloxy, hetarylthio or C(=NORM)-An-Ra;
are aryl, arylcarbonyl, arylsulfonyl, hetaryl, hetaryl-carbonyl or hetarylsulfonyl, where these radicals may be partially or fully halogenated or may carry one to three of the following groups: cyano, vitro, hydroxyl, mercapto, amino, carboxyl, aminocarbonyl, aminothio-carbonyl, halogen, C1-C6-alkyl, CI-C6-haloalkyl, C1-C6-alkylcarbonyl, C1-C6-alkylsulfonyl, C1-C6-alkyl-sulfoxyl, C3-C6-cycloalkyl, C1-C6-alkoxy, C1-C6-halo-alkoxy, C1-C6-alkyloxycarbonyl, C1-C6-alkylthio, C1_C6-alkylamino, di-C1-C6-alkylamino, C1-C6-alkylamino-carbonyl, di-C1-C6-alkylaminocarbonyl, C1-C6-alkyl-aminothiocarbonyl, di-C1-C6-alkylaminothiocarbonyl, CZ-C6-alkenyl, C2-C6-alkenyloxy, benzyl, benzyloxy, aryl, aryloxy, hetaryl, hetaryloxy or C(=NORM)-An-Re;
R5 is hydrogen, is C1-C6-alkyl, C2-C6-alkenyl, CZ-C6-alkynyl, where the hydrocarbon radicals of these groups may be partially or fully halogenated or may carry one to three of the following radicals: cyano, vitro, hydroxyl, mercapto, amino, carboxyl, aminocarbonyl, aminothiocarbonyl, halogen, C1-C6-alkylaminocarbonyl, di-C1-C6-alkylamino-carbonyl, C1-C6-alkylaminothiocarbonyl, di-C1-C6-alkyl-aminothiocarbonyl, C1-C6-alkylsulfonyl, C1-C6-alkyl-sulfoxyl, C1-C6-alkoxy, C1-C6-haloalkoxy, C1-C6-alkoxy-carbonyl, C1-C6-alkylthio, C1-C6-alkylamino, di-C1-C6-alkylamino, CZ-C6-alkenyloxy, C3-C6-cycloalkyl, C3-C6-cycloalkyloxy, heterocyclyl, heterocyclyloxy, aryl, aryloxy, aryl-C1-C4-alkoxy, arylthio, aryl-C1-CQ-alkylthio, hetaryl, hetaryloxy, hetaryl-C1-C4-alkoxy, hetarylthio, hetaryl-C1-C4-alkylthio, where the cyclic radicals for their part may be partially or fully halogenated and/or may carry one to three of the following groups: cyano, vitro, hydroxyl, mercapto, amino, carboxyl, aminocarbonyl, aminothiocarbonyl, C1-C6-alkyl, C1-C6-haloalkyl, C1-C6-alkylsulfonyl, C1-C6-alkylsulfoxyl, C3C6-cycloalkyl (sic], C1-C6-alkoxy, C1-C6-haloalkoxy, C1-C6-alkoxycarbonyl, C1-C6-alkylthio, C1-C6-alkylamino, di-C1-C6-alkylamino, C1-C6-alkylamino-carbonyl,, di-C1-C6-alkylaminocarbonyl, C1-C6-alkyl-aminothiocarbonyl, di-C1-C6-alkylaminothiocarbonyl, C2-C6-alkenyl, C2-C6-alkenyloxy, benzyl, benzyloxy, aryl, aryloxy, arylthio, hetaryl, hetaryloxy, hetarylthio and C(=NORM)-An-R8;
is C3-C6-cycloalkyl, C3-C6-cycloalkenyl, heterocyclyl, aryl, hetaryl, where the cyclic radicals may be partially or fully halogenated or may carry one to three of the following groups: cyano, vitro, hydroxyl, mercapto, amino, carboxyl, aminocarbonyl, aminothio-carbonyl, halogen, C1-C6-alkyl, C1-C6-haloalkyl, C1-C6-alkylsulfonyl, C1-C6-alkylsulfoxyl, C3-C6-cyclo-alkyl, C1-C6-alkoxy, C1-C6-haloalkoxy, C1-C6-alkoxy-carbonyl, C1-C6-alkylthio, C1-C6-alkylamino, di-C1-C6-alkylamino, C1-C6-alkylaminocarbonyl, di-C1-C6-alkylaminocarbonyl, C1-C6-alkylaminothio-carbonyl, di-C1-C6-alkylaminothiocarbonyl, CZ-C6-alkenyl, CZ-C6-alkenyloxy, benzyl, benzyloxy, aryl, aryloxy, hetaryl and hetaryloxy;
where A is oxygen, sulfur or nitrogen and where the nitrogen carries hydrogen or C1-C6-alkyl;
DERIVATIVES AND RHIZOCTONIA FUNGICIDES
The present invention relates to fungicidal mixtures for controlling harmful fungi, comprising a) phenylacetic acid derivatives of the formula I
R\O~N\ ~N/O ~R2)m (I), RS ~ N R' I
O. Rs O
in which the substituents and the index have the following meaning:
X is NOCHg, CHOCH3 or CHCH3;
Y is oxygen or NR;
R1, R independently of one another are each hydrogen or C1-C4-alkyl;
R2 is cyano, nitro, trifluoromethyl, halogen, C1-C4-alkyl or C1-C4-alkoxy;
m is 0, 1 or 2, where the radicals R2 may be different if m is 2;
R3 is hydrogen, cyano, C1-C4-alkyl, C1-C4-haloalkyl or C3-C6-cycloalkyl;
R4, R6 independently of one another are each hydrogen, la are C1-C1o-alkyl, C3-C6-cycloalkyl, C2-Clo-alkenyl, C2-Clo-alkynyl, C1-Clo-alkylcarbonyl, C2-Clo-alkenyl-carbonyl, C3-Clo-alkynylcarbonyl or C1-C1o-alkyl-sulfonyl, where these radicals may be partially or fully halogenated or may carry one to three of the following groups: cyano, nitro, hydroxyl, mercapto, amino, carboxyl, aminocarbonyl, aminothiocarbonyl, halogen, C1-C6-alkyl, C1-C6-haloalkyl, C1-C6-alkyl-sulfonyl, C1-C6-alkylsulfoxyl, C1-C6-alkoxy, C1-C6-haloalkoxy, C1-C6-alkoxycarbonyl, C1-C6-alkylthio, C1-C6-alkylamino, di-C1-C6-alkylamino, C1-C6-alkylamino-carbonyl, di-C1-C6-alkylaminocarbonyl, C1-C6-alkyl-aminothiocarbonyl, di-C1-C6-alkylaminothiocarbonyl, CZ-C6-alkenyl, CZ-C6-alkenyloxy, C3-C6-cycloalkyl, C3-C6-cycloalkyloxy, heterocyclyl, heterocyclyloxy, benzyl, benzyloxy, aryl, aryloxy, arylthio, hetaryl, hetaryloxy and hetarylthio, where the cyclic groups for their part may be partially or fully halogenated or~may carry one to three of the following groups: cyano, vitro, hydroxyl, mercapto, amino, carboxyl, amino-carbonyl, aminothiocarbonyl, halogen, C1-C6-alkyl, C1-C6-haloalkyl, C1-C6-alkylsulfonyl, C1-C6-alkyl-sulfoxyl, C3-C6-cycloalkyl, C1-C6-alkoxy, C1-C6-haloalkoxy, C1-C6-alkyloxycarbonyl, C1-C6-alkyl-thio, C1-C6-alkylamino, di-C1-C6-alkylamino, C1-C6-alkylaminocarbonyl, di-C1-C6-alkylaminocarbonyl, C1-C6-alkylaminothiocarbonyl, di-C1-C6-alkylaminothio-carbonyl, Cz-C6-alkenyl, CZ-C6-alkenyloxy, benzyl, benzyloxy, aryl, aryloxy, arylthio, hetaryl, hetaryloxy, hetarylthio or C(=NORM)-An-Ra;
are aryl, arylcarbonyl, arylsulfonyl, hetaryl, hetaryl-carbonyl or hetarylsulfonyl, where these radicals may be partially or fully halogenated or may carry one to three of the following groups: cyano, vitro, hydroxyl, mercapto, amino, carboxyl, aminocarbonyl, aminothio-carbonyl, halogen, C1-C6-alkyl, CI-C6-haloalkyl, C1-C6-alkylcarbonyl, C1-C6-alkylsulfonyl, C1-C6-alkyl-sulfoxyl, C3-C6-cycloalkyl, C1-C6-alkoxy, C1-C6-halo-alkoxy, C1-C6-alkyloxycarbonyl, C1-C6-alkylthio, C1_C6-alkylamino, di-C1-C6-alkylamino, C1-C6-alkylamino-carbonyl, di-C1-C6-alkylaminocarbonyl, C1-C6-alkyl-aminothiocarbonyl, di-C1-C6-alkylaminothiocarbonyl, CZ-C6-alkenyl, C2-C6-alkenyloxy, benzyl, benzyloxy, aryl, aryloxy, hetaryl, hetaryloxy or C(=NORM)-An-Re;
R5 is hydrogen, is C1-C6-alkyl, C2-C6-alkenyl, CZ-C6-alkynyl, where the hydrocarbon radicals of these groups may be partially or fully halogenated or may carry one to three of the following radicals: cyano, vitro, hydroxyl, mercapto, amino, carboxyl, aminocarbonyl, aminothiocarbonyl, halogen, C1-C6-alkylaminocarbonyl, di-C1-C6-alkylamino-carbonyl, C1-C6-alkylaminothiocarbonyl, di-C1-C6-alkyl-aminothiocarbonyl, C1-C6-alkylsulfonyl, C1-C6-alkyl-sulfoxyl, C1-C6-alkoxy, C1-C6-haloalkoxy, C1-C6-alkoxy-carbonyl, C1-C6-alkylthio, C1-C6-alkylamino, di-C1-C6-alkylamino, CZ-C6-alkenyloxy, C3-C6-cycloalkyl, C3-C6-cycloalkyloxy, heterocyclyl, heterocyclyloxy, aryl, aryloxy, aryl-C1-C4-alkoxy, arylthio, aryl-C1-CQ-alkylthio, hetaryl, hetaryloxy, hetaryl-C1-C4-alkoxy, hetarylthio, hetaryl-C1-C4-alkylthio, where the cyclic radicals for their part may be partially or fully halogenated and/or may carry one to three of the following groups: cyano, vitro, hydroxyl, mercapto, amino, carboxyl, aminocarbonyl, aminothiocarbonyl, C1-C6-alkyl, C1-C6-haloalkyl, C1-C6-alkylsulfonyl, C1-C6-alkylsulfoxyl, C3C6-cycloalkyl (sic], C1-C6-alkoxy, C1-C6-haloalkoxy, C1-C6-alkoxycarbonyl, C1-C6-alkylthio, C1-C6-alkylamino, di-C1-C6-alkylamino, C1-C6-alkylamino-carbonyl,, di-C1-C6-alkylaminocarbonyl, C1-C6-alkyl-aminothiocarbonyl, di-C1-C6-alkylaminothiocarbonyl, C2-C6-alkenyl, C2-C6-alkenyloxy, benzyl, benzyloxy, aryl, aryloxy, arylthio, hetaryl, hetaryloxy, hetarylthio and C(=NORM)-An-R8;
is C3-C6-cycloalkyl, C3-C6-cycloalkenyl, heterocyclyl, aryl, hetaryl, where the cyclic radicals may be partially or fully halogenated or may carry one to three of the following groups: cyano, vitro, hydroxyl, mercapto, amino, carboxyl, aminocarbonyl, aminothio-carbonyl, halogen, C1-C6-alkyl, C1-C6-haloalkyl, C1-C6-alkylsulfonyl, C1-C6-alkylsulfoxyl, C3-C6-cyclo-alkyl, C1-C6-alkoxy, C1-C6-haloalkoxy, C1-C6-alkoxy-carbonyl, C1-C6-alkylthio, C1-C6-alkylamino, di-C1-C6-alkylamino, C1-C6-alkylaminocarbonyl, di-C1-C6-alkylaminocarbonyl, C1-C6-alkylaminothio-carbonyl, di-C1-C6-alkylaminothiocarbonyl, CZ-C6-alkenyl, CZ-C6-alkenyloxy, benzyl, benzyloxy, aryl, aryloxy, hetaryl and hetaryloxy;
where A is oxygen, sulfur or nitrogen and where the nitrogen carries hydrogen or C1-C6-alkyl;
n is 0 or 1;
R~ is hydrogen or C1-C6-alkyl and R8 is hydrogen or C1-C6-alkyl, and their salts, and b) at least one fungicide selected from fungicides of the formulae II to VII
CI ~ ~ CH2 \ ~ ~ ( I z ) NCONH
OCH (CH~2 CONH ~ ~ ( III ) 3o CF
OCH (CH3)2 CONH
F Br I.
H3C Br io CI O
~ / N N (vz) ~CONHCH(CH3)2 CI O
N ~ ~ (VII) N~
~N / O
CI
It is an object of the present invention to provide fungicidal mixtures having good fungicidal activity, in particular against fungal diseases in rice, exceeding the activity of the mixture components on their own.
We have found that this object is achieved by the mixtures as claimed in claim 1.
The compounds of the formula I are known per se and are described in the literature (WO 97/15552).
The fungicides of the formulae II to VII are also known and described in the literature. In addition, they are commercially available under the trade names mentioned below in brackets:
II: DE-A 27 32 257, common name: pencycuron (trade name:
Monceren~, from Bayer);
III:JP 01/104,514, common name: flutolanil (trade name: Moncut~, from Nihon Noyaku);
IV: US 3,937,840, common name: mepronil (trade name: Basitac~, from Kumiai);
V: common name: thifluzamide (trade name: Greatam~, from Monsanto);
VI: GB-A 1,312,536, US 3,755,350; common name: iprodione (trade name: Rovral~, from Rhone-Poulenc);
VII:AG Chem New Compound Review, Vol. 15 (1997), 50; common name:
furametpyr (trade name: Limber~, from Sumitomo).
Owing to their C=C and C=N double bonds, the preparation of the compounds I may yield E/Z isomer mixtures which can be separated into the individual compounds in a customary manner, for example by crystallization or chromatography.
However, if the synthesis yields isomer mixtures, a separation is generally not necessarily required since in some cases the individual isomers can be converted into one another during the preparation for use or upon use (for example under the action of light, acids or bases). Similar conversions may also occur after the use, for example in the treatment of plants in the treated plant or in the harmful fungus or animal pest to be controlled.
With regard to the C=X double bond, preference is given to the E
isomers of the compounds I (configuration based on the -OCH3 or the -CH3 group in relation to the -COZR1 group) with respect to their activity.
With regard to the -C(R3)=NOCH2- double bond, preference is given to the cis isomers of the compounds I (configuration based on the radical R3 in relation to the -OCHZ- group) with respect to their activity.
In the definitions of the compounds I given at the outset, collective terms were used which generally represent the following groups:
Halogen: fluorine, chlorine, bromine and iodine;
Alkyl: straight-chain or branched alkyl groups having 1 to 4, 6 or 10 carbon atoms, for example C1-C6-alkyl such as methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-di-methylpropyl, 1-ethylpropyl, hexyl, l,l-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl, 2-methyl-pentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethyl-1-methyl-propyl and 1-ethyl-2-methylpropyl;
Haloalkyl: straight-chain or branched alkyl groups having 1 to 6 carbon atoms, it being possible for some or all of the hydrogen atoms in these groups to be replaced by halogen atoms as mentioned above, for example C1-CZ-haloalkyl, such as chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichloro-fluoromethyl, chlorodifluoromethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro-2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl and pentafluoroethyl;
Cycloalkyl: monocyclic alkyl groups having 3 to 6 carbon ring members, for example cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl;
Alkenyl: straight-chain or branched alkenyl groups having 2 to 6 or 10 carbon atoms and a double bond in any position, for example C2-C6-alkenyl, such as ethenyl, 1-propenyl, 2-propenyl, 1-methyl-ethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl, 2-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl-1-butenyl, 2-methyl-1-butenyl, 3-methyl-1-butenyl, 1-methyl-2-butenyl, 2-methyl-2-butenyl, 3-methyl-2-butenyl, 1-methyl-3-butenyl, 2-methyl-3-butenyl, 3-methyl-3-butenyl, 1,1-dimethyl-2-propenyl, 1,2-dimethyl-1-propenyl, 1,2-dimethyl-2-propenyl, 1-ethyl-1-propenyl, 1-ethyl-2-propenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1-methyl-1-pentenyl, 2-methyl-1-pentenyl, 3-methyl-1-pentenyl, 4-methyl-1-pentenyl, 1-methyl-2-pentenyl, 2-methyl-2-pentenyl, 3-methyl-2-pentenyl, 4-methyl-2-pentenyl, 1-methyl-3-pentenyl, 2-methyl-3-pentenyl, 3-methyl-3-pentenyl, 4-methyl-3-pentenyl, 1-methyl-4-pentenyl, 2-methyl-4-pentenyl, 3-methyl-4-pentenyl, 4-methyl-4-pentenyl, 1,1-dimethyl-2-butenyl, 1,1-di-methyl-3-butenyl, 1,2-dimethyl-1-butenyl, 1,2-dimethyl-2-butenyl, 1,2-dimethyl-3-butenyl, 1,3-dimethyl-1-butenyl, 1,3-dimethyl-2-butenyl, 1,3-dimethyl-3-butenyl, 2,2-dimethyl-3-butenyl, 2,3-dimethyl-1-butenyl, 2,3-dimethyl-2-butenyl, 2,3-dimethyl-3-butenyl, 3,3-dimethyl-1-butenyl, 3,3-dimethyl-2-butenyl, 1-ethyl-1-butenyl, 1-ethyl-2-butenyl, 1-ethyl-3-butenyl, 2-ethyl-1-butenyl, 2-ethyl-2-butenyl, 2-ethyl-3-butenyl, 1,1,2-trimethyl-2-propenyl, 1-ethyl-1-methyl-2-propenyl, 1-ethyl-2-methyl-1-propenyl and 1-ethyl-2-methyl-2-propenyl;
Alkynyl: straight-chain or branched alkynyl groups having 2 to 10 carbon atoms and a triple bond in any position, for example Cz-C6-alkynyl, such as ethynyl, 2-propynyl, 2-butynyl, 3-butynyl, 1-methyl-2-propynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 1-methyl-2-butynyl, 1-methyl-3-butynyl, 2-methyl-3-butynyl, 1,1-dimethyl-2-propynyl, 1-ethyl-2-propynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl, 5-hexynyl, 1-methyl-2-pentynyl, 1-methyl-3-pentynyl, 1-methyl-4-pentynyl, 2-methyl-3-pentynyl, 2-methyl-4-pentynyl, 3-methyl-4-pentynyl, 4-methyl-2-pentynyl, 1,1-dimethyl-2-butynyl, 1,1-dimethyl-3-butynyl, 1,2-dimethyl-3-butynyl, 2,2-dimethyl-3-butynyl, 1-ethyl-2-butynyl, 1-ethyl-3-butynyl, 2-ethyl-3-butynyl and 1-ethyl-1-methyl-2-propynyl;
Hetero~clyl or heterocyclyloxy, heterocyclylthio and heterocyclylamino: three- to six-membered saturated or partially unsaturated mono- or polycyclic heterocycles which contain one to three heteroatoms selected from a group consisting of oxygen, nitrogen and sulfur and which are attached to the skeleton directly or (heterocyclyloxy) via an oxygen atom or (heterocyclylthio) via a sulfur atom or (heterocyclylamino) via a nitrogen atom, such as, for example, 2-tetrahydrofuranyl, oxiranyl, 3-tetrahydrofuranyl, 2-tetrahydrothienyl, 3-tetrahydro-thienyl, 2-pyrrolidinyl, 3-pyrrolidinyl, 3-isoxazolidinyl, 4-isoxazolidinyl, 5-isoxazolidinyl, 3-isothiazolidinyl, 4-isothiazolidinyl, 5-isothiazolidinyl, 3-pyrazolidinyl, 4-pyrazolidinyl, 5-pyrazolidinyl, 2-oxazolidinyl, 4-oxazolidinyl, 5-oxazolidinyl, 2-thiazolidinyl, 4-thiazolidinyl, 5-thiazoli-dinyl, 2-imidazolidinyl, 4-imidazolidinyl, 1,2,4-oxadiazolidin-3-yl, 1,2,4-oxadiazolidin-5-yl, 1,2,4-thiadiazolidin-3-yl, 1,2,4-thiadiazolidin-5-yl, 1,2,4-triazol-idin-3-yl, 1,3,4-oxadia-zolidin-2-yl, 1,3,4-thiadiazolidin-2-yl, 1,3,4-triazolidin-2-yl, 2,3-dihydrofur-2-yl, 2,3-dihydrofur-3-yl, 2,3-dihydrofur-4-yl, 2,3-dihydrofur-5-yl, 2,5-dihydrofur-2-yl, 2,5-dihydrofur-3-yl, 2,3-dihydrothien-2-yl, 2,3-dihydrothien-3-yl, 2,3-dihydro-thien-4-yl, 2,3-dihydrothien-5-yl, 2,5-dihydrothien-2-yl, 2,5-dihydrothien-3-yl, 2,3-dihydropyrrol-2-yl, 2,3-dihydro-pyrrol-3-yl, 2,3-dihydropyrrol-4-yl, 2,3-dihydropyrrol-5-yl, 2,5-dihydropyrrol-2-yl, 2,5-dihydropyrrol-3-yl, 2,3-dihydro-isoxazol-3-yl, 2,3-dihydroisoxazol-4-yl, 2,3-dihydroisoxazol-5-yl, 4,5-dihydroisoxazol-3-yl, 4,5-dihydroisoxazol-4-yl, 4,5-dihydroisoxazol-5-yl, 2,5-dihydroisothiazol-3-yl, 2,5-dihydroisothiazol-4-yl, 2,5-dihydroisothiazol-5-yl, 2,3-dihydroisopyrazol-3-yl, 2,3-dihydroisopyrazol-4-yl, 2,3-dihydroisopyrazol-5-yl, 4,5-dihydroisopyrazol-3-yl, 4,5-dihydroisopyrazol-4-yl, 4,5-dihydroisopyrazol-5-yl, 2,5-dihydroisopyrazol-3-yl, 2,5-dihydroisopyrazol-4-yl, 2,5-dihydroisopyrazol-5-yl, 2,3-dihydrooxazol-3-yl, 2,3-dihydrooxazol-4-yl, 2,3-dihydrooxazol-5-yI, 4,5-dihydrooxazol-3-yl, 4,5-dihydrooxazol-4-yl, 4,5-dihydrooxazol-5-yl, 2,5-dihydrooxazol-3-yl, 2,5-dihydrooxazol-4-yl, 2,5-dihydrooxazol-5-yl, 2,3-dihydrothiazol-2-yl, 2,3-dihydrothiazol-4-yl, 2,3-dihydrothiazol-5-yl, 4,5-dihydrothiazol-2-yl, 4,5-dihydrothiazol-4-yl, 4,5-dihydrothiazol-5-yl, 2,5-dihydrothiazol-2-yl, 2,5-dihydrothiazol-4-yl, 2,5-dihydrothiazol-5-yl, 2,3-dihydroimidazol-2-yl, 2,3-dihydroimidazol-4-yl, 2,3-dihydroimidazol-5-yl, 4,5-dihydroimidazol-2-yl, 4,5-dihydroimidazol-4-yl, 4,5-dihydroimidazol-5-yl, 2,5-dihydroimidazol-2-yl, 2,5-dihydroimidazol-4-yl, 2,5-dihydroimidazol-5-yl, 2-morpholinyl, 3-morpholinyl, 2-piperidinyl, 3-piperidinyl, 4-piperidinyl, 3-tetrahydropyridazinyl, 4-tetrahydropyridazinyl, 2-tetrahydropyrimidinyl, 4-tetrahydropyrimidinyl, 5-tetrahydro-pyrimidinyl, 2-tetrahydropyrazinyl, 1,3,5-tetrahydrotriazin-2-yl, 1,2,4-tetrahydrotriazin-3-yl, 1,3-dihydrooxazin-2-yl, 1,3-dithian-2-yl, 2-tetrahydropyranyl, 1,3-dioxolan-2-yl, 3,4,5,6-tetrahydropyridin-2-yl, 4H-1,3-thiazin-2-yl, 4H-3,1-benzothiazin-2-yl, 1,1-dioxo-2,3,4,5-tetrahydrothien-2-yl, 2H-1,4-benzothiazin-3-yl, 2H-1,4-benzoxazin-3-yl, 1,3-dihydro-oxazin-2-yl, 1,3-dithian-2-yI;
Aryl or aryloxv, arvlthio, ar~rlcarbonyl and arylsulfonyl:
aromatic mono- or polycyclic hydrogen radicals which are attached to the skeleton directly or (aryloxy) via an oxygen atom (-O-) or (arylthio) a sulfur atom (-S-), (arylcarbonyl) via a carbonyl group (-CO-) or (arylsulfonyl) via a sulfonyl group (-S02-), for example phenyl, naphthyl and phenanthrenyl or phenyloxy, naphthyloxy and phenanthrenyloxy and the corresponding carbonyl and sulfonyl radicals;
Hetaryl or hetaryloxy, hetarylthio, hetarylcarbonyl and hetarylsulfonyl: aromatic mono- or polycyclic radicals which, beside carbon ring members, can additionally contain one to four nitrogen atoms or one to three nitrogen atoms and one oxygen or one sulfur atom or one oxygen or one sulfur atom and which are attached to the skeleton directly or (hetaryloxy) via an oxygen atom (-O-) or (hetarylthio) a sulfur atom (-S-), (hetaryl-carbonyl) via a carbonyl group (-CO-) or (hetarylsulfonyl) via a sulfonyl group (-S02-), for example - 5-membered heteroaryl, containing one to three nitrogen atoms: 5-membered heteroaryl groups which, beside carbon atoms, can contain one to three nitrogen atoms as ring members, for example 2-pyrrolyl, 3-pyrrolyl, 3-pyrazolyl, 10 4-pyrazolyl, 5-pyrazolyl, 2-imidazolyl, 4-imidazolyl, 1,2,4-triazol-3-yl and 1,3,4-triazol-2-yl;
- 5-membered heteroaryl, containing one to four nitrogen atoms or one to three nitrogen atoms and one sulfur or oxygen atom or one oxygen or one sulfur atom: 5-membered heteroaryl groups which, beside carbon atoms, can contain one to four nitrogen atoms or one to three nitrogen atoms and one sulfur or oxygen atom or one oxygen or sulfur atom as ring members, for example 2-furyl, 3-furyl, 2-thienyl, 3-thienyl, 2-pyrrolyl, 3-pyrrolyl, 3-isoxazolyl, 4-isoxazolyl, 5-isoxazolyl, 3-isothiazolyl, 4-isothiazolyl, 5-isothiazolyl, 3-pyrazolyl, 4-pyrazolyl, 5-pyrazolyl, 2-oxazolyl, 4-oxazolyl, 5-oxazolyl, 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, 2-imidazolyl, 4-imidazolyl, 1,2,4-oxadiazol-3-yl, 1,2,4-oxadiazol-5-yl, 1,2,4-thiadiazol-3-yl, 1,2,4-thiadiazol-5-yl, 1,2,4-triazol-3-yl, 1,3,4-oxadiazol-2-yl, 1,3,4-thiadiazol-2-yl, 1,3,4-triazol-2-yl;
- benzo-fused 5-membered heteroaryl, containing one to three nitrogen atoms or one nitrogen atom and/or one oxygen or sulfur atom: 5-membered heteroaryl groups which, beside carbon atoms, can contain one to four nitrogen atoms or one to three nitrogen atoms and one sulfur or oxygen atom or one oxygen or one sulfur atom as ring members, and in which two adjacent carbon ring members or one nitrogen and one adjacent carbon ring member may be bridged by a buta-1,3-dien-1,4-diyl group;
- 5-membered heteroaryl bonded via nitrogen and containin4 one to four nitrogen atoms. or benzo-fused 5-membered heteroaryl.
bonded via nitrogen and containing one to three nitrogen a oms: 5-membered heteroaryl groups which, beside carbon atoms, can contain one to four nitrogen atoms and one to three nitrogen atoms, respectively, as ring members, and in which two adjacent carbon ring members or one nitrogen and one adjacent carbon ring member can be bridged by a buta-1,3-dien-1,4-diyl group, these rings being attached to the skeleton via one of the nitrogen ring members;
- f-membered heteroar~l containing one to three and one to four nitrocren atoms, respectively: 6-membered heteroaryl groups which, beside carbon atoms, can contain one to three nitrogen atoms and one to four nitrogen atoms, respectively, as ring members, for example 2-pyridinyl, 3-pyridinyl, 4-pyridinyl, 3-pyridazinyl, 4-pyridazinyl, 2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl, 2-pyrazinyl, 1,3,5-triazin-2-yl, 1,2,4-triazin-3-yl and 1,2,4,5-tetrazin-3-yl;
- benzo-fused 6-membered heteroaryl containing one to four nitrogen atoms: 6-membered heteroaryl groups in which two adjacent carbon ring members can be bridged by a buta-1,3-dien-1,4-diyl group, for example quinoline, isoquinoline, quinazoline and quinoxaline, and the corresponding oxy, thio, carbonyl or sulfonyl groups.
Hetarylamino: aromatic mono- or polycyclic radicals which, beside carbon ring members, can additionally contain one to four nitrogen atoms or one to three nitrogen atoms and one oxygen or one sulfur atom and which are attached to the skeleton via a nitrogen atom.
The specification "partially or fully halogenated" is meant to express that some or all of the hydrogen atoms in the groups thus characterized may be replaced by identical or different halogen atoms as mentioned above.
With respect to their biological activity, preference is given to compounds of the formula I in which m is 0.
Likewise, preference is given to compounds of formula I in which R1 is methyl.
Besides, preference is given to compounds I in which R3 is hydrogen, cyano, cyclopropyl, methyl, ethyl, 1-methylethyl or CF3.
Moreover, preference is given to compounds I in which R3 is methyl.
Besides, preference is given to compounds I in which R3 is cyano.
Furthermore, preference if given to compounds I in which R3 is cyclopropyl.
Additionally, preference is given to compounds I in which R3 is CF3.
Additionally, preference is given to compounds I in which R5 is hydrogen, cyclopropyl, methyl, ethyl, isopropyl, unsubstituted or substituted aryl or hetaryl.
Moreover, preference is given to compounds I in which R5 is methyl.
Additionally, preference is given to compounds I in which R5 is ethyl.
Moreover, preference is given to compounds I in which R5 is isopropyl.
Moreover, preference is given to compounds I in which R5 is cyclopropyl.
Moreover, preference is given to compounds I in which R5 is CF3.
Additionally, preference is given to compounds I in which RS is unsubstituted or substituted aryl or hetaryl.
Additionally, preference is given to compounds I in which R5 is unsubstituted or substituted pyridyl, pyrimidyl, pyrazinyl, pyridazinyl or triazinyl.
Additionally, preference is given to compounds I in which R5 is unsubstituted or substituted furyl, thienyl or pyrrolyl.
Additionally, preference is given to compounds I in which R5 is unsubstituted or substituted oxazolyl, thiazolyl, isoxazolyl, isothiazolyl, pyrazolyl or imidazolyl.
Additionally, preference is given to compounds I in which R5 is unsubstituted or substituted oxdiazolyl [sic], thiadiazolyl or triazolyl.
Moreover, preference is given to compounds I in which RS is phenyl which is unsubstituted or carries one or two of the following groups: nitro, cyano, hydroxyl, amino, aminocarbonyl, aminothiocarbonyl, halogen, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy, C1-C4-haloalkoxy, C1-C4-alkylamino, di-C1-C4-alkylamino, C1-C4-alkylsulfonyl, C1-C4-alkoxycarbonyl, C1-C4-alkylaminocarbonyl or di-C1-CQ-alkylaminocarbonyl.
Moreover, preference is given to compounds I in which R4 is hydrogen, C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, allyl, arylalkyl, hetarylalkyl, aryloxyalkyl, hetaryloxyalkyl, aryl or hetaryl.
Additionally, preference is given to compounds I in which R4 is C1-C6-alkyl.
Further preferred compounds I are disclosed in WO 97/15,552.
The compounds I which are contained in the mixtures according to the invention have excellent activity against a broad range of phytopathogenic fungi, in particular against fungi from the classes of the Ascomycetes, Deuteromycetes, Phycomycetes and Basidiomycetes.
They are especially important for controlling a large number of fungi in a variety of crop plants, such as cotton, vegetable species (for example cucumbers, beans, tomatoes, potatoes and cucurbits), barley, grass, oats, bananas, coffee, maize, fruit species, rice, rye, Soya, grapevine, wheat, ornamentals, sugar cane, and a variety of seeds.
They are particularly suitable for controlling the following phytopathogenic fungi: Erysiphe graminis (powdery mildew) in cereals, Erysiphe cichoracearum and Sphaerotheca fuliginea in cucurbits, Podosphaera leucotricha in apples, LJncinula necator in grapevines, Puccinia species in cereals, Rhizoctonia species in cotton, rice and lawns, Ustilago species in cereals and sugar cane, Venturia inaequalis (scab) in apples, Helminthosporium species in cereals and rice, Septoria nodorum in wheat, Botrytis cinera [sic] (gray mold) in strawberries, vegetables, ornamentals and grapevines, Cercospora arachidicola in groundnuts, Pseudocercosporella herpotrichoides in wheat and barley, Pyricularia oryzae in rice and lawns, Phytophthora infestans in potatoes and tomatoes, Plasmopara viticola in grapevines, Pseudoperonospora species in hops and cucumbers, Alternaria species in vegetables and fruit, Mycosphaerella species in bananas and Fusarium and Verticillium species.
The compounds II to VII are commercially available as fungicides.
When preparing the mixtures, it is preferred to employ the pure active ingredients I and II to VII, with which further active ingredients against harmful fungi or other pests, such as insects, arachnids or nematodes, or else herbicidal or growth-regulating active ingredients or fertilizers can be admixed.
The mixtures of the compounds I and at least one compound II to VII can be applied simultaneously, that is joined or separately, and have outstanding action against a wide range of phytopathogenic fungi, in particular from the classes of the Ascomycetes, Basidiomycetes, Phycomycetes and Deuteromycetes.
Some of them act systematically and are therefore also suitable for use as foliar and soil-acting fungicides.
They are especially important for controlling a large number of fungi in a variety of crop plants, such as cotton, vegetable species (for example cucumbers, beans, tomatoes, potatoes and cucurbits), barley, grass, oats, bananas, coffee, maize, fruit species, rice, rye, soya, grapevine, wheat, ornamentals, sugar cane, and a variety of seeds.
They are particularly suitable for controlling the following phytopathogenic fungi: Erysiphe graminis (powdery mildew) in cereals, Erysiphe cichoracearum and Sphaerotheca fuliginea in cucurbits, Podosphaera leucotricha in apples, Uncinula necator in grapevines, Puccinia species in cereals, Rhizoctonia species in cotton, rice and lawns, Ustilago species in cereals and sugar cane, Venturia inaequalis (scab) in apples, Helminthosporium species in cereals and rice, Septoria nodorum in wheat, Botrytis cinera [sic] (gray mold) in strawberries, vegetables, ornamentals and grapevines, Cercospora arachidicola in groundnuts, Pseudocercosporella herpotrichoides in wheat and barley, Pyricularia oryzae in rice and lawns, Phytophthora infestans in potatoes and tomatoes, Plasmopara viticola in grapevines, Pseudoperonospora species in hops and cucumbers, Alternaria species in vegetables and fruit, Mycosphaerella species in bananas and Fusarium and Verticillium species.
The mixtures according to the invention are particularly preferably utilizable for controlling Pyricularia oryzae.
The compounds I and at least one of the compounds II to VII can be applied simultaneously, either together or separately, or in succession, the sequence, in the case of separate application, generally not having any effect on the control results.
Depending on the nature of the desired effect, the application rates of the mixtures according to the invention are, in particular in areas under agricultural cultivation, from 0.01 to 8 kg/ha, preferably from 0.1 to 5 kg/ha, in particular from 0.5 5 to 3.0 kg/ha.
In the case of the compounds I, the application rates are from 0.01 to 2.5 kg/ha, preferably from 0.05 to 2.5 kg/ha, in particular from 0.1 to 1.0 kg/ha.
Correspondingly, in the case of the compounds II to VII, the application rates are from 0.001 to 5 kg/ha, preferably from 0.005 to 2 kg/ha, in particular from 0.01 to 1.0 kg/ha.
For seed treatment, the application rates of the mixture are generally from 0.001 to 250 g/kg of seed, preferably 0.01 to 100 g/kg, in particular 0.01 to 50 g/kg.
If phytopathogenic harmful fungi are to be controlled, the separate or joint application of the compounds I and at least one of the compounds II to VII is effected by spraying or dusting the seeds, the plants or the soils before or after sowing the plants, or before or after plant emergence.
The fungicidal synergistic mixtures according to the invention can be formulated for example in the form of ready-to-spray solutions, powder and suspensions or in the form of highly concentrated aqueous, oily or other suspensions, dispersions, emulsions, oil dispersions, pastes, dusts, materials for broadcasting or granules, and applied by spraying, atomizing, dusting, broadcasting or watering. The use form depends on the intended purpose; in any case, it should ensure as fine and uniform as possible a distribution of the mixture according to the invention.
The formulations are prepared in a known manner, for example by expanding the active ingredient with solvents and/or carriers, if desired by use of emulsifiers and dispersants. If the diluent used is water, it is also possible to use other organic solvents as auxiliary solvents. Suitable auxiliaries are essentially:
solvents, such as aromatics (for example xylene), chlorinated aromatics (for example chlorobenzenes), paraffins (for example mineral oil fractions), alcohols (for example methanol, butanol), ketones (for example cyclohexanone), amines (for example ethanolamine, dimethylformamide) and water; carriers, such as ground natural minerals (for example kaolins, clays, talc, chalk) and ground synthetic minerals (for example finely divided silica gel, silicates); emulsifiers, such as nonionic and anionic emulsifiers (for example polyoxyethylene fatty alcohol ethers, alkylsulfonates and arylsulfonates), and dispersants, such as ligninsulfite waste liquors and methylcellulose.
Suitable surfactants are the alkali metal salts, alkaline earth metal salts and ammonium salts of aromatic sulfonic acids, e.g.
ligno-, phenol-, naphthalene- and dibutylnaphthalenesulfonic acid, and of fatty acids, alkyl- and alkylarylsulfonates, alkyl, lauryl ether and fatty alcohol sulfates, and salts of sulfated hexa-, hepta- and octadecanols, or of fatty alcohol glycol ethers, condensates of sulfonated naphthalene and its derivatives with formaldehyde, condensates of naphthalene or of the naphthalenesulfonic acids with phenol and formaldehyde, polyoxyethylene octylphenol ether, ethoxylated isooctyl-, octyl-or nonylphenol, alkylphenol polyglycol ethers, tributylphenyl polyglycol ethers, alkylaryl polyether alcohols, isotridecyl alcohol, fatty alcohol ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers or polyoxypropylene [sic], lauryl alcohol polyglycol ether acetate, sorbitol esters, lignosulfite waste liquors or methylcellulose.
Powders, materials for broadcasting and dusts can be prepared by mixing or jointly grinding the compounds I and at least one of the compounds II to VII or the mixture of the compounds I and at least one of the compounds II to VII with a solid carrier.
Granules (eg. coated granules, impregnated granules or homogeneous granules) are usually prepared by binding the active ingredient, or active ingredients, to a solid carrier.
Fillers or solid carriers are, for example, mineral earths, such as silica gel, silicic acids, silica gels [sic], silicates, talc, kaolin, limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground synthetic materials, and fertilizers, such as ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas, and products of vegetable origin, such as cereal meal, tree bark meal, wood meal and nutshell meal, cellulose powders or other solid carriers.
The formulations generally comprise 0.1 to 95% by weight, preferably 0.5 to 90% by weight, of one of the compounds I and at least one of the compounds II to VII or of the mixture of the compounds I and at least one of the compounds II to VII. The active ingredients are employed in a purity of from 90~ to 100$, preferably 95~ to 100 (according to NMR or HPLC spectrum [sic]).
The corresponding formulations are applied by treating the harmful fungi, their habitat or the plants, seeds, soils, areas, materials or spaces to be kept free from them with a fungicidally effective amount of the mixture, or of the compounds I and at least one of the compounds II to VII in the case of separate application.
Application can be effected before or after infection by the harmful fungi.
Examples of such preparations comprising the active ingredients are:
I. A solution of 90 parts by weight of the active ingredients and 10 parts by weight of N-methylpyrrolidone; this solu-tion is suitable for use in the form of microdrops;
II. A mixture of 20 parts by weight of the active ingredients, 80 parts by weight of xylene, 10 parts by weight of the ad-duct of 8 to 10 mol of ethylene oxide and 1 mol of oleic acid N-monoethanolamide, 5 parts by weight of the calcium salt of dodecylbenzenesulfonate, 5 parts by weight of the adduct of 40 mol of ethylene oxide and 1 mol of castor oil;
a dispersion is obtained by finely distributing the solu-tion in water;
III. An aqueous dispersion of 20 parts by weight of the active ingredients, 40 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight of the adduct of 40 mol of ethylene oxide and 1 mol of castor oil;
IV. An aqueous dispersion of 20 parts by weight of the active ingredients, 25 parts by weight of cyclohexanol, 65 parts by weight of a mineral oil fraction of boiling point 210 to 280~C, and 10 parts by weight of the adduct of 40 mol of ethylene oxide and 1 mol of castor oil;
V. A mixture, ground in a hammer mill, of 80 parts by weight of the active ingredients, 3 parts by weight of the sodium salt of diisobutylnaphthalene-1-sulfonic acid, 10 parts by weight of the sodium salt of a lignosulfonic acid from a sulfite waste liquor and 7 parts by weight of pulverulent silica gel; a spray mixture is obtained by finely distribu-ting the mixture in water;
VI. An intimate mixture of 3 parts by weight of the active in gredients and 97 parts by weight of finely divided kaolin;
this dust comprises 3~ by weight of active ingredient;
VII. An intimate mixture of 30 parts by weight of the active in-gredients, 92 parts by weight of pulverulent silica gel and 8 parts by weight of paraffin oil which had been sprayed onto the surface of this silica gel; this formulation im-parts good adhesion to the active ingredient;
VIII. A stable aqueous dispersion of 40 parts by weight of the active ingredients, 10 parts by weight of the sodium salt of a phenolsulfonic acid/urea/formaldehyde condensate, 2 parts by weight of silica gel and 48 parts by weight of wa-ter; this dispersion may be diluted further;
IX. A stable oily dispersion of 20 parts by weight of the acti-ve ingredients, 2 parts by weight of the calcium salt of dodecylbenzenesulfonic acid, 8 parts by weight of fatty al-cohol polyglycol ether, 20 parts by weight of the sodium salt of a phenolsulfonic acid/urea/formaldehyde condensate and 88 parts by weight of a paraffinic mineral oil.
The synergistic activity of the mixtures according to the invention can be demonstrated by the following experiments:
The active ingredients, separately or together, are formulated as a 10~ emulsion in a mixture of 63~ by weight of cyclohexanone and 27~ by weight of emulsifier, and correspondingly diluted with water to the desired concentration.
Evaluation is carried out by determining the infected leaf areas in percent. These percentages are converted into efficacies. The efficacy (W_) is calculated as follows using Abbot's formula:
W = (1 - a)~100/~
a corresponds to the fungal infection of the treated plants in and ~ corresponds to the fungal infection of the untreated (control) plants in ~
An efficacy of 0 means that the infection level of the treated plants corresponds to that of the untreated control plants; an efficacy of 100 means that the treated plants were not infected.
The expected efficacies of the mixtures of the active ingredients were determined using Colby's formula [R.S. Colby, Weeds 15, 20-22 (1967)] and compared with the observed efficacies.
Colby's formula: E = x + y - x~y/100 E expected efficacy, expressed in ~ of the untreated control, when using the mixture of the active ingredients A and B at the concentrations a and b x efficacy, expressed in % of the untreated control, when using active ingredient A at the concentration a y efficacy, expressed in ~ of the untreated control, when using active ingredient B at the concentration b Use Examples - Activity against Pyricularia oryzae (protective) Leaves of potted rice seedlings cv "Tai-Nong 67" were sprayed to runoff point with an aqueous preparation of active ingredient which had been prepared from a stock solution comprising 10~ of active ingredient, 63$ of cyclohexanone and 27~ of emulsifier.
The following day, the plants were inoculated with an aqueous spore suspension of Pyricularia oryzae. The test plants were subsequently placed in climatized chambers at 22-24~C and 95-99$
relative atmospheric humidity for 6 days. The extent of the development of the disease on the leaves was then determined visually.
The visually determined values for the percentage of infected leaf area were converted into efficacies as percent of the untreated control. An efficacy of 0 means the same infection as in the untreated control, an efficacy of 100 means 0~ infection.
The expected efficacies for active compound combinations were determined using Colby's formula (Colby, S.R.: "Calculating synergistic and antagonistic responses of herbicide combinations", Weeds 15 20-22, 1967) and compared with the observed efficacies.
The following compound I' was used as component a):
CHs H3C~D~N~ ~N~O /
(z.) CH w N CH3NH N,O-CH3 H C~
The test results are shown in Tables 1 and 2 below:
Table 1:
Ex. Active ingredientConc. in ppm Efficacy in %
of the untreated control 5 1C None (100% infection) 0 2C Compound I' 2.0 20 0.5 0 3C Compound VII 2.0 0 0.5 0 Table 2:
Ex. Mixture according to Observed Calculated the invention (conc. in efficacy efficacy*) ppm) 15q 2 ppm I' + 2 ppm VII 35% 20%
5 0.5 ppm I' + 0.5 ppm 20% 0%
VII
*) calculated using Colby's formula The test results show that the observed efficacy for all mixing ratios is higher than the efficacy which had been calculated beforehand using Colby's formula.
R~ is hydrogen or C1-C6-alkyl and R8 is hydrogen or C1-C6-alkyl, and their salts, and b) at least one fungicide selected from fungicides of the formulae II to VII
CI ~ ~ CH2 \ ~ ~ ( I z ) NCONH
OCH (CH~2 CONH ~ ~ ( III ) 3o CF
OCH (CH3)2 CONH
F Br I.
H3C Br io CI O
~ / N N (vz) ~CONHCH(CH3)2 CI O
N ~ ~ (VII) N~
~N / O
CI
It is an object of the present invention to provide fungicidal mixtures having good fungicidal activity, in particular against fungal diseases in rice, exceeding the activity of the mixture components on their own.
We have found that this object is achieved by the mixtures as claimed in claim 1.
The compounds of the formula I are known per se and are described in the literature (WO 97/15552).
The fungicides of the formulae II to VII are also known and described in the literature. In addition, they are commercially available under the trade names mentioned below in brackets:
II: DE-A 27 32 257, common name: pencycuron (trade name:
Monceren~, from Bayer);
III:JP 01/104,514, common name: flutolanil (trade name: Moncut~, from Nihon Noyaku);
IV: US 3,937,840, common name: mepronil (trade name: Basitac~, from Kumiai);
V: common name: thifluzamide (trade name: Greatam~, from Monsanto);
VI: GB-A 1,312,536, US 3,755,350; common name: iprodione (trade name: Rovral~, from Rhone-Poulenc);
VII:AG Chem New Compound Review, Vol. 15 (1997), 50; common name:
furametpyr (trade name: Limber~, from Sumitomo).
Owing to their C=C and C=N double bonds, the preparation of the compounds I may yield E/Z isomer mixtures which can be separated into the individual compounds in a customary manner, for example by crystallization or chromatography.
However, if the synthesis yields isomer mixtures, a separation is generally not necessarily required since in some cases the individual isomers can be converted into one another during the preparation for use or upon use (for example under the action of light, acids or bases). Similar conversions may also occur after the use, for example in the treatment of plants in the treated plant or in the harmful fungus or animal pest to be controlled.
With regard to the C=X double bond, preference is given to the E
isomers of the compounds I (configuration based on the -OCH3 or the -CH3 group in relation to the -COZR1 group) with respect to their activity.
With regard to the -C(R3)=NOCH2- double bond, preference is given to the cis isomers of the compounds I (configuration based on the radical R3 in relation to the -OCHZ- group) with respect to their activity.
In the definitions of the compounds I given at the outset, collective terms were used which generally represent the following groups:
Halogen: fluorine, chlorine, bromine and iodine;
Alkyl: straight-chain or branched alkyl groups having 1 to 4, 6 or 10 carbon atoms, for example C1-C6-alkyl such as methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-di-methylpropyl, 1-ethylpropyl, hexyl, l,l-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl, 2-methyl-pentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethyl-1-methyl-propyl and 1-ethyl-2-methylpropyl;
Haloalkyl: straight-chain or branched alkyl groups having 1 to 6 carbon atoms, it being possible for some or all of the hydrogen atoms in these groups to be replaced by halogen atoms as mentioned above, for example C1-CZ-haloalkyl, such as chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichloro-fluoromethyl, chlorodifluoromethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro-2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl and pentafluoroethyl;
Cycloalkyl: monocyclic alkyl groups having 3 to 6 carbon ring members, for example cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl;
Alkenyl: straight-chain or branched alkenyl groups having 2 to 6 or 10 carbon atoms and a double bond in any position, for example C2-C6-alkenyl, such as ethenyl, 1-propenyl, 2-propenyl, 1-methyl-ethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl, 2-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl-1-butenyl, 2-methyl-1-butenyl, 3-methyl-1-butenyl, 1-methyl-2-butenyl, 2-methyl-2-butenyl, 3-methyl-2-butenyl, 1-methyl-3-butenyl, 2-methyl-3-butenyl, 3-methyl-3-butenyl, 1,1-dimethyl-2-propenyl, 1,2-dimethyl-1-propenyl, 1,2-dimethyl-2-propenyl, 1-ethyl-1-propenyl, 1-ethyl-2-propenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1-methyl-1-pentenyl, 2-methyl-1-pentenyl, 3-methyl-1-pentenyl, 4-methyl-1-pentenyl, 1-methyl-2-pentenyl, 2-methyl-2-pentenyl, 3-methyl-2-pentenyl, 4-methyl-2-pentenyl, 1-methyl-3-pentenyl, 2-methyl-3-pentenyl, 3-methyl-3-pentenyl, 4-methyl-3-pentenyl, 1-methyl-4-pentenyl, 2-methyl-4-pentenyl, 3-methyl-4-pentenyl, 4-methyl-4-pentenyl, 1,1-dimethyl-2-butenyl, 1,1-di-methyl-3-butenyl, 1,2-dimethyl-1-butenyl, 1,2-dimethyl-2-butenyl, 1,2-dimethyl-3-butenyl, 1,3-dimethyl-1-butenyl, 1,3-dimethyl-2-butenyl, 1,3-dimethyl-3-butenyl, 2,2-dimethyl-3-butenyl, 2,3-dimethyl-1-butenyl, 2,3-dimethyl-2-butenyl, 2,3-dimethyl-3-butenyl, 3,3-dimethyl-1-butenyl, 3,3-dimethyl-2-butenyl, 1-ethyl-1-butenyl, 1-ethyl-2-butenyl, 1-ethyl-3-butenyl, 2-ethyl-1-butenyl, 2-ethyl-2-butenyl, 2-ethyl-3-butenyl, 1,1,2-trimethyl-2-propenyl, 1-ethyl-1-methyl-2-propenyl, 1-ethyl-2-methyl-1-propenyl and 1-ethyl-2-methyl-2-propenyl;
Alkynyl: straight-chain or branched alkynyl groups having 2 to 10 carbon atoms and a triple bond in any position, for example Cz-C6-alkynyl, such as ethynyl, 2-propynyl, 2-butynyl, 3-butynyl, 1-methyl-2-propynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 1-methyl-2-butynyl, 1-methyl-3-butynyl, 2-methyl-3-butynyl, 1,1-dimethyl-2-propynyl, 1-ethyl-2-propynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl, 5-hexynyl, 1-methyl-2-pentynyl, 1-methyl-3-pentynyl, 1-methyl-4-pentynyl, 2-methyl-3-pentynyl, 2-methyl-4-pentynyl, 3-methyl-4-pentynyl, 4-methyl-2-pentynyl, 1,1-dimethyl-2-butynyl, 1,1-dimethyl-3-butynyl, 1,2-dimethyl-3-butynyl, 2,2-dimethyl-3-butynyl, 1-ethyl-2-butynyl, 1-ethyl-3-butynyl, 2-ethyl-3-butynyl and 1-ethyl-1-methyl-2-propynyl;
Hetero~clyl or heterocyclyloxy, heterocyclylthio and heterocyclylamino: three- to six-membered saturated or partially unsaturated mono- or polycyclic heterocycles which contain one to three heteroatoms selected from a group consisting of oxygen, nitrogen and sulfur and which are attached to the skeleton directly or (heterocyclyloxy) via an oxygen atom or (heterocyclylthio) via a sulfur atom or (heterocyclylamino) via a nitrogen atom, such as, for example, 2-tetrahydrofuranyl, oxiranyl, 3-tetrahydrofuranyl, 2-tetrahydrothienyl, 3-tetrahydro-thienyl, 2-pyrrolidinyl, 3-pyrrolidinyl, 3-isoxazolidinyl, 4-isoxazolidinyl, 5-isoxazolidinyl, 3-isothiazolidinyl, 4-isothiazolidinyl, 5-isothiazolidinyl, 3-pyrazolidinyl, 4-pyrazolidinyl, 5-pyrazolidinyl, 2-oxazolidinyl, 4-oxazolidinyl, 5-oxazolidinyl, 2-thiazolidinyl, 4-thiazolidinyl, 5-thiazoli-dinyl, 2-imidazolidinyl, 4-imidazolidinyl, 1,2,4-oxadiazolidin-3-yl, 1,2,4-oxadiazolidin-5-yl, 1,2,4-thiadiazolidin-3-yl, 1,2,4-thiadiazolidin-5-yl, 1,2,4-triazol-idin-3-yl, 1,3,4-oxadia-zolidin-2-yl, 1,3,4-thiadiazolidin-2-yl, 1,3,4-triazolidin-2-yl, 2,3-dihydrofur-2-yl, 2,3-dihydrofur-3-yl, 2,3-dihydrofur-4-yl, 2,3-dihydrofur-5-yl, 2,5-dihydrofur-2-yl, 2,5-dihydrofur-3-yl, 2,3-dihydrothien-2-yl, 2,3-dihydrothien-3-yl, 2,3-dihydro-thien-4-yl, 2,3-dihydrothien-5-yl, 2,5-dihydrothien-2-yl, 2,5-dihydrothien-3-yl, 2,3-dihydropyrrol-2-yl, 2,3-dihydro-pyrrol-3-yl, 2,3-dihydropyrrol-4-yl, 2,3-dihydropyrrol-5-yl, 2,5-dihydropyrrol-2-yl, 2,5-dihydropyrrol-3-yl, 2,3-dihydro-isoxazol-3-yl, 2,3-dihydroisoxazol-4-yl, 2,3-dihydroisoxazol-5-yl, 4,5-dihydroisoxazol-3-yl, 4,5-dihydroisoxazol-4-yl, 4,5-dihydroisoxazol-5-yl, 2,5-dihydroisothiazol-3-yl, 2,5-dihydroisothiazol-4-yl, 2,5-dihydroisothiazol-5-yl, 2,3-dihydroisopyrazol-3-yl, 2,3-dihydroisopyrazol-4-yl, 2,3-dihydroisopyrazol-5-yl, 4,5-dihydroisopyrazol-3-yl, 4,5-dihydroisopyrazol-4-yl, 4,5-dihydroisopyrazol-5-yl, 2,5-dihydroisopyrazol-3-yl, 2,5-dihydroisopyrazol-4-yl, 2,5-dihydroisopyrazol-5-yl, 2,3-dihydrooxazol-3-yl, 2,3-dihydrooxazol-4-yl, 2,3-dihydrooxazol-5-yI, 4,5-dihydrooxazol-3-yl, 4,5-dihydrooxazol-4-yl, 4,5-dihydrooxazol-5-yl, 2,5-dihydrooxazol-3-yl, 2,5-dihydrooxazol-4-yl, 2,5-dihydrooxazol-5-yl, 2,3-dihydrothiazol-2-yl, 2,3-dihydrothiazol-4-yl, 2,3-dihydrothiazol-5-yl, 4,5-dihydrothiazol-2-yl, 4,5-dihydrothiazol-4-yl, 4,5-dihydrothiazol-5-yl, 2,5-dihydrothiazol-2-yl, 2,5-dihydrothiazol-4-yl, 2,5-dihydrothiazol-5-yl, 2,3-dihydroimidazol-2-yl, 2,3-dihydroimidazol-4-yl, 2,3-dihydroimidazol-5-yl, 4,5-dihydroimidazol-2-yl, 4,5-dihydroimidazol-4-yl, 4,5-dihydroimidazol-5-yl, 2,5-dihydroimidazol-2-yl, 2,5-dihydroimidazol-4-yl, 2,5-dihydroimidazol-5-yl, 2-morpholinyl, 3-morpholinyl, 2-piperidinyl, 3-piperidinyl, 4-piperidinyl, 3-tetrahydropyridazinyl, 4-tetrahydropyridazinyl, 2-tetrahydropyrimidinyl, 4-tetrahydropyrimidinyl, 5-tetrahydro-pyrimidinyl, 2-tetrahydropyrazinyl, 1,3,5-tetrahydrotriazin-2-yl, 1,2,4-tetrahydrotriazin-3-yl, 1,3-dihydrooxazin-2-yl, 1,3-dithian-2-yl, 2-tetrahydropyranyl, 1,3-dioxolan-2-yl, 3,4,5,6-tetrahydropyridin-2-yl, 4H-1,3-thiazin-2-yl, 4H-3,1-benzothiazin-2-yl, 1,1-dioxo-2,3,4,5-tetrahydrothien-2-yl, 2H-1,4-benzothiazin-3-yl, 2H-1,4-benzoxazin-3-yl, 1,3-dihydro-oxazin-2-yl, 1,3-dithian-2-yI;
Aryl or aryloxv, arvlthio, ar~rlcarbonyl and arylsulfonyl:
aromatic mono- or polycyclic hydrogen radicals which are attached to the skeleton directly or (aryloxy) via an oxygen atom (-O-) or (arylthio) a sulfur atom (-S-), (arylcarbonyl) via a carbonyl group (-CO-) or (arylsulfonyl) via a sulfonyl group (-S02-), for example phenyl, naphthyl and phenanthrenyl or phenyloxy, naphthyloxy and phenanthrenyloxy and the corresponding carbonyl and sulfonyl radicals;
Hetaryl or hetaryloxy, hetarylthio, hetarylcarbonyl and hetarylsulfonyl: aromatic mono- or polycyclic radicals which, beside carbon ring members, can additionally contain one to four nitrogen atoms or one to three nitrogen atoms and one oxygen or one sulfur atom or one oxygen or one sulfur atom and which are attached to the skeleton directly or (hetaryloxy) via an oxygen atom (-O-) or (hetarylthio) a sulfur atom (-S-), (hetaryl-carbonyl) via a carbonyl group (-CO-) or (hetarylsulfonyl) via a sulfonyl group (-S02-), for example - 5-membered heteroaryl, containing one to three nitrogen atoms: 5-membered heteroaryl groups which, beside carbon atoms, can contain one to three nitrogen atoms as ring members, for example 2-pyrrolyl, 3-pyrrolyl, 3-pyrazolyl, 10 4-pyrazolyl, 5-pyrazolyl, 2-imidazolyl, 4-imidazolyl, 1,2,4-triazol-3-yl and 1,3,4-triazol-2-yl;
- 5-membered heteroaryl, containing one to four nitrogen atoms or one to three nitrogen atoms and one sulfur or oxygen atom or one oxygen or one sulfur atom: 5-membered heteroaryl groups which, beside carbon atoms, can contain one to four nitrogen atoms or one to three nitrogen atoms and one sulfur or oxygen atom or one oxygen or sulfur atom as ring members, for example 2-furyl, 3-furyl, 2-thienyl, 3-thienyl, 2-pyrrolyl, 3-pyrrolyl, 3-isoxazolyl, 4-isoxazolyl, 5-isoxazolyl, 3-isothiazolyl, 4-isothiazolyl, 5-isothiazolyl, 3-pyrazolyl, 4-pyrazolyl, 5-pyrazolyl, 2-oxazolyl, 4-oxazolyl, 5-oxazolyl, 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, 2-imidazolyl, 4-imidazolyl, 1,2,4-oxadiazol-3-yl, 1,2,4-oxadiazol-5-yl, 1,2,4-thiadiazol-3-yl, 1,2,4-thiadiazol-5-yl, 1,2,4-triazol-3-yl, 1,3,4-oxadiazol-2-yl, 1,3,4-thiadiazol-2-yl, 1,3,4-triazol-2-yl;
- benzo-fused 5-membered heteroaryl, containing one to three nitrogen atoms or one nitrogen atom and/or one oxygen or sulfur atom: 5-membered heteroaryl groups which, beside carbon atoms, can contain one to four nitrogen atoms or one to three nitrogen atoms and one sulfur or oxygen atom or one oxygen or one sulfur atom as ring members, and in which two adjacent carbon ring members or one nitrogen and one adjacent carbon ring member may be bridged by a buta-1,3-dien-1,4-diyl group;
- 5-membered heteroaryl bonded via nitrogen and containin4 one to four nitrogen atoms. or benzo-fused 5-membered heteroaryl.
bonded via nitrogen and containing one to three nitrogen a oms: 5-membered heteroaryl groups which, beside carbon atoms, can contain one to four nitrogen atoms and one to three nitrogen atoms, respectively, as ring members, and in which two adjacent carbon ring members or one nitrogen and one adjacent carbon ring member can be bridged by a buta-1,3-dien-1,4-diyl group, these rings being attached to the skeleton via one of the nitrogen ring members;
- f-membered heteroar~l containing one to three and one to four nitrocren atoms, respectively: 6-membered heteroaryl groups which, beside carbon atoms, can contain one to three nitrogen atoms and one to four nitrogen atoms, respectively, as ring members, for example 2-pyridinyl, 3-pyridinyl, 4-pyridinyl, 3-pyridazinyl, 4-pyridazinyl, 2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl, 2-pyrazinyl, 1,3,5-triazin-2-yl, 1,2,4-triazin-3-yl and 1,2,4,5-tetrazin-3-yl;
- benzo-fused 6-membered heteroaryl containing one to four nitrogen atoms: 6-membered heteroaryl groups in which two adjacent carbon ring members can be bridged by a buta-1,3-dien-1,4-diyl group, for example quinoline, isoquinoline, quinazoline and quinoxaline, and the corresponding oxy, thio, carbonyl or sulfonyl groups.
Hetarylamino: aromatic mono- or polycyclic radicals which, beside carbon ring members, can additionally contain one to four nitrogen atoms or one to three nitrogen atoms and one oxygen or one sulfur atom and which are attached to the skeleton via a nitrogen atom.
The specification "partially or fully halogenated" is meant to express that some or all of the hydrogen atoms in the groups thus characterized may be replaced by identical or different halogen atoms as mentioned above.
With respect to their biological activity, preference is given to compounds of the formula I in which m is 0.
Likewise, preference is given to compounds of formula I in which R1 is methyl.
Besides, preference is given to compounds I in which R3 is hydrogen, cyano, cyclopropyl, methyl, ethyl, 1-methylethyl or CF3.
Moreover, preference is given to compounds I in which R3 is methyl.
Besides, preference is given to compounds I in which R3 is cyano.
Furthermore, preference if given to compounds I in which R3 is cyclopropyl.
Additionally, preference is given to compounds I in which R3 is CF3.
Additionally, preference is given to compounds I in which R5 is hydrogen, cyclopropyl, methyl, ethyl, isopropyl, unsubstituted or substituted aryl or hetaryl.
Moreover, preference is given to compounds I in which R5 is methyl.
Additionally, preference is given to compounds I in which R5 is ethyl.
Moreover, preference is given to compounds I in which R5 is isopropyl.
Moreover, preference is given to compounds I in which R5 is cyclopropyl.
Moreover, preference is given to compounds I in which R5 is CF3.
Additionally, preference is given to compounds I in which RS is unsubstituted or substituted aryl or hetaryl.
Additionally, preference is given to compounds I in which R5 is unsubstituted or substituted pyridyl, pyrimidyl, pyrazinyl, pyridazinyl or triazinyl.
Additionally, preference is given to compounds I in which R5 is unsubstituted or substituted furyl, thienyl or pyrrolyl.
Additionally, preference is given to compounds I in which R5 is unsubstituted or substituted oxazolyl, thiazolyl, isoxazolyl, isothiazolyl, pyrazolyl or imidazolyl.
Additionally, preference is given to compounds I in which R5 is unsubstituted or substituted oxdiazolyl [sic], thiadiazolyl or triazolyl.
Moreover, preference is given to compounds I in which RS is phenyl which is unsubstituted or carries one or two of the following groups: nitro, cyano, hydroxyl, amino, aminocarbonyl, aminothiocarbonyl, halogen, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy, C1-C4-haloalkoxy, C1-C4-alkylamino, di-C1-C4-alkylamino, C1-C4-alkylsulfonyl, C1-C4-alkoxycarbonyl, C1-C4-alkylaminocarbonyl or di-C1-CQ-alkylaminocarbonyl.
Moreover, preference is given to compounds I in which R4 is hydrogen, C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, allyl, arylalkyl, hetarylalkyl, aryloxyalkyl, hetaryloxyalkyl, aryl or hetaryl.
Additionally, preference is given to compounds I in which R4 is C1-C6-alkyl.
Further preferred compounds I are disclosed in WO 97/15,552.
The compounds I which are contained in the mixtures according to the invention have excellent activity against a broad range of phytopathogenic fungi, in particular against fungi from the classes of the Ascomycetes, Deuteromycetes, Phycomycetes and Basidiomycetes.
They are especially important for controlling a large number of fungi in a variety of crop plants, such as cotton, vegetable species (for example cucumbers, beans, tomatoes, potatoes and cucurbits), barley, grass, oats, bananas, coffee, maize, fruit species, rice, rye, Soya, grapevine, wheat, ornamentals, sugar cane, and a variety of seeds.
They are particularly suitable for controlling the following phytopathogenic fungi: Erysiphe graminis (powdery mildew) in cereals, Erysiphe cichoracearum and Sphaerotheca fuliginea in cucurbits, Podosphaera leucotricha in apples, LJncinula necator in grapevines, Puccinia species in cereals, Rhizoctonia species in cotton, rice and lawns, Ustilago species in cereals and sugar cane, Venturia inaequalis (scab) in apples, Helminthosporium species in cereals and rice, Septoria nodorum in wheat, Botrytis cinera [sic] (gray mold) in strawberries, vegetables, ornamentals and grapevines, Cercospora arachidicola in groundnuts, Pseudocercosporella herpotrichoides in wheat and barley, Pyricularia oryzae in rice and lawns, Phytophthora infestans in potatoes and tomatoes, Plasmopara viticola in grapevines, Pseudoperonospora species in hops and cucumbers, Alternaria species in vegetables and fruit, Mycosphaerella species in bananas and Fusarium and Verticillium species.
The compounds II to VII are commercially available as fungicides.
When preparing the mixtures, it is preferred to employ the pure active ingredients I and II to VII, with which further active ingredients against harmful fungi or other pests, such as insects, arachnids or nematodes, or else herbicidal or growth-regulating active ingredients or fertilizers can be admixed.
The mixtures of the compounds I and at least one compound II to VII can be applied simultaneously, that is joined or separately, and have outstanding action against a wide range of phytopathogenic fungi, in particular from the classes of the Ascomycetes, Basidiomycetes, Phycomycetes and Deuteromycetes.
Some of them act systematically and are therefore also suitable for use as foliar and soil-acting fungicides.
They are especially important for controlling a large number of fungi in a variety of crop plants, such as cotton, vegetable species (for example cucumbers, beans, tomatoes, potatoes and cucurbits), barley, grass, oats, bananas, coffee, maize, fruit species, rice, rye, soya, grapevine, wheat, ornamentals, sugar cane, and a variety of seeds.
They are particularly suitable for controlling the following phytopathogenic fungi: Erysiphe graminis (powdery mildew) in cereals, Erysiphe cichoracearum and Sphaerotheca fuliginea in cucurbits, Podosphaera leucotricha in apples, Uncinula necator in grapevines, Puccinia species in cereals, Rhizoctonia species in cotton, rice and lawns, Ustilago species in cereals and sugar cane, Venturia inaequalis (scab) in apples, Helminthosporium species in cereals and rice, Septoria nodorum in wheat, Botrytis cinera [sic] (gray mold) in strawberries, vegetables, ornamentals and grapevines, Cercospora arachidicola in groundnuts, Pseudocercosporella herpotrichoides in wheat and barley, Pyricularia oryzae in rice and lawns, Phytophthora infestans in potatoes and tomatoes, Plasmopara viticola in grapevines, Pseudoperonospora species in hops and cucumbers, Alternaria species in vegetables and fruit, Mycosphaerella species in bananas and Fusarium and Verticillium species.
The mixtures according to the invention are particularly preferably utilizable for controlling Pyricularia oryzae.
The compounds I and at least one of the compounds II to VII can be applied simultaneously, either together or separately, or in succession, the sequence, in the case of separate application, generally not having any effect on the control results.
Depending on the nature of the desired effect, the application rates of the mixtures according to the invention are, in particular in areas under agricultural cultivation, from 0.01 to 8 kg/ha, preferably from 0.1 to 5 kg/ha, in particular from 0.5 5 to 3.0 kg/ha.
In the case of the compounds I, the application rates are from 0.01 to 2.5 kg/ha, preferably from 0.05 to 2.5 kg/ha, in particular from 0.1 to 1.0 kg/ha.
Correspondingly, in the case of the compounds II to VII, the application rates are from 0.001 to 5 kg/ha, preferably from 0.005 to 2 kg/ha, in particular from 0.01 to 1.0 kg/ha.
For seed treatment, the application rates of the mixture are generally from 0.001 to 250 g/kg of seed, preferably 0.01 to 100 g/kg, in particular 0.01 to 50 g/kg.
If phytopathogenic harmful fungi are to be controlled, the separate or joint application of the compounds I and at least one of the compounds II to VII is effected by spraying or dusting the seeds, the plants or the soils before or after sowing the plants, or before or after plant emergence.
The fungicidal synergistic mixtures according to the invention can be formulated for example in the form of ready-to-spray solutions, powder and suspensions or in the form of highly concentrated aqueous, oily or other suspensions, dispersions, emulsions, oil dispersions, pastes, dusts, materials for broadcasting or granules, and applied by spraying, atomizing, dusting, broadcasting or watering. The use form depends on the intended purpose; in any case, it should ensure as fine and uniform as possible a distribution of the mixture according to the invention.
The formulations are prepared in a known manner, for example by expanding the active ingredient with solvents and/or carriers, if desired by use of emulsifiers and dispersants. If the diluent used is water, it is also possible to use other organic solvents as auxiliary solvents. Suitable auxiliaries are essentially:
solvents, such as aromatics (for example xylene), chlorinated aromatics (for example chlorobenzenes), paraffins (for example mineral oil fractions), alcohols (for example methanol, butanol), ketones (for example cyclohexanone), amines (for example ethanolamine, dimethylformamide) and water; carriers, such as ground natural minerals (for example kaolins, clays, talc, chalk) and ground synthetic minerals (for example finely divided silica gel, silicates); emulsifiers, such as nonionic and anionic emulsifiers (for example polyoxyethylene fatty alcohol ethers, alkylsulfonates and arylsulfonates), and dispersants, such as ligninsulfite waste liquors and methylcellulose.
Suitable surfactants are the alkali metal salts, alkaline earth metal salts and ammonium salts of aromatic sulfonic acids, e.g.
ligno-, phenol-, naphthalene- and dibutylnaphthalenesulfonic acid, and of fatty acids, alkyl- and alkylarylsulfonates, alkyl, lauryl ether and fatty alcohol sulfates, and salts of sulfated hexa-, hepta- and octadecanols, or of fatty alcohol glycol ethers, condensates of sulfonated naphthalene and its derivatives with formaldehyde, condensates of naphthalene or of the naphthalenesulfonic acids with phenol and formaldehyde, polyoxyethylene octylphenol ether, ethoxylated isooctyl-, octyl-or nonylphenol, alkylphenol polyglycol ethers, tributylphenyl polyglycol ethers, alkylaryl polyether alcohols, isotridecyl alcohol, fatty alcohol ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers or polyoxypropylene [sic], lauryl alcohol polyglycol ether acetate, sorbitol esters, lignosulfite waste liquors or methylcellulose.
Powders, materials for broadcasting and dusts can be prepared by mixing or jointly grinding the compounds I and at least one of the compounds II to VII or the mixture of the compounds I and at least one of the compounds II to VII with a solid carrier.
Granules (eg. coated granules, impregnated granules or homogeneous granules) are usually prepared by binding the active ingredient, or active ingredients, to a solid carrier.
Fillers or solid carriers are, for example, mineral earths, such as silica gel, silicic acids, silica gels [sic], silicates, talc, kaolin, limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground synthetic materials, and fertilizers, such as ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas, and products of vegetable origin, such as cereal meal, tree bark meal, wood meal and nutshell meal, cellulose powders or other solid carriers.
The formulations generally comprise 0.1 to 95% by weight, preferably 0.5 to 90% by weight, of one of the compounds I and at least one of the compounds II to VII or of the mixture of the compounds I and at least one of the compounds II to VII. The active ingredients are employed in a purity of from 90~ to 100$, preferably 95~ to 100 (according to NMR or HPLC spectrum [sic]).
The corresponding formulations are applied by treating the harmful fungi, their habitat or the plants, seeds, soils, areas, materials or spaces to be kept free from them with a fungicidally effective amount of the mixture, or of the compounds I and at least one of the compounds II to VII in the case of separate application.
Application can be effected before or after infection by the harmful fungi.
Examples of such preparations comprising the active ingredients are:
I. A solution of 90 parts by weight of the active ingredients and 10 parts by weight of N-methylpyrrolidone; this solu-tion is suitable for use in the form of microdrops;
II. A mixture of 20 parts by weight of the active ingredients, 80 parts by weight of xylene, 10 parts by weight of the ad-duct of 8 to 10 mol of ethylene oxide and 1 mol of oleic acid N-monoethanolamide, 5 parts by weight of the calcium salt of dodecylbenzenesulfonate, 5 parts by weight of the adduct of 40 mol of ethylene oxide and 1 mol of castor oil;
a dispersion is obtained by finely distributing the solu-tion in water;
III. An aqueous dispersion of 20 parts by weight of the active ingredients, 40 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight of the adduct of 40 mol of ethylene oxide and 1 mol of castor oil;
IV. An aqueous dispersion of 20 parts by weight of the active ingredients, 25 parts by weight of cyclohexanol, 65 parts by weight of a mineral oil fraction of boiling point 210 to 280~C, and 10 parts by weight of the adduct of 40 mol of ethylene oxide and 1 mol of castor oil;
V. A mixture, ground in a hammer mill, of 80 parts by weight of the active ingredients, 3 parts by weight of the sodium salt of diisobutylnaphthalene-1-sulfonic acid, 10 parts by weight of the sodium salt of a lignosulfonic acid from a sulfite waste liquor and 7 parts by weight of pulverulent silica gel; a spray mixture is obtained by finely distribu-ting the mixture in water;
VI. An intimate mixture of 3 parts by weight of the active in gredients and 97 parts by weight of finely divided kaolin;
this dust comprises 3~ by weight of active ingredient;
VII. An intimate mixture of 30 parts by weight of the active in-gredients, 92 parts by weight of pulverulent silica gel and 8 parts by weight of paraffin oil which had been sprayed onto the surface of this silica gel; this formulation im-parts good adhesion to the active ingredient;
VIII. A stable aqueous dispersion of 40 parts by weight of the active ingredients, 10 parts by weight of the sodium salt of a phenolsulfonic acid/urea/formaldehyde condensate, 2 parts by weight of silica gel and 48 parts by weight of wa-ter; this dispersion may be diluted further;
IX. A stable oily dispersion of 20 parts by weight of the acti-ve ingredients, 2 parts by weight of the calcium salt of dodecylbenzenesulfonic acid, 8 parts by weight of fatty al-cohol polyglycol ether, 20 parts by weight of the sodium salt of a phenolsulfonic acid/urea/formaldehyde condensate and 88 parts by weight of a paraffinic mineral oil.
The synergistic activity of the mixtures according to the invention can be demonstrated by the following experiments:
The active ingredients, separately or together, are formulated as a 10~ emulsion in a mixture of 63~ by weight of cyclohexanone and 27~ by weight of emulsifier, and correspondingly diluted with water to the desired concentration.
Evaluation is carried out by determining the infected leaf areas in percent. These percentages are converted into efficacies. The efficacy (W_) is calculated as follows using Abbot's formula:
W = (1 - a)~100/~
a corresponds to the fungal infection of the treated plants in and ~ corresponds to the fungal infection of the untreated (control) plants in ~
An efficacy of 0 means that the infection level of the treated plants corresponds to that of the untreated control plants; an efficacy of 100 means that the treated plants were not infected.
The expected efficacies of the mixtures of the active ingredients were determined using Colby's formula [R.S. Colby, Weeds 15, 20-22 (1967)] and compared with the observed efficacies.
Colby's formula: E = x + y - x~y/100 E expected efficacy, expressed in ~ of the untreated control, when using the mixture of the active ingredients A and B at the concentrations a and b x efficacy, expressed in % of the untreated control, when using active ingredient A at the concentration a y efficacy, expressed in ~ of the untreated control, when using active ingredient B at the concentration b Use Examples - Activity against Pyricularia oryzae (protective) Leaves of potted rice seedlings cv "Tai-Nong 67" were sprayed to runoff point with an aqueous preparation of active ingredient which had been prepared from a stock solution comprising 10~ of active ingredient, 63$ of cyclohexanone and 27~ of emulsifier.
The following day, the plants were inoculated with an aqueous spore suspension of Pyricularia oryzae. The test plants were subsequently placed in climatized chambers at 22-24~C and 95-99$
relative atmospheric humidity for 6 days. The extent of the development of the disease on the leaves was then determined visually.
The visually determined values for the percentage of infected leaf area were converted into efficacies as percent of the untreated control. An efficacy of 0 means the same infection as in the untreated control, an efficacy of 100 means 0~ infection.
The expected efficacies for active compound combinations were determined using Colby's formula (Colby, S.R.: "Calculating synergistic and antagonistic responses of herbicide combinations", Weeds 15 20-22, 1967) and compared with the observed efficacies.
The following compound I' was used as component a):
CHs H3C~D~N~ ~N~O /
(z.) CH w N CH3NH N,O-CH3 H C~
The test results are shown in Tables 1 and 2 below:
Table 1:
Ex. Active ingredientConc. in ppm Efficacy in %
of the untreated control 5 1C None (100% infection) 0 2C Compound I' 2.0 20 0.5 0 3C Compound VII 2.0 0 0.5 0 Table 2:
Ex. Mixture according to Observed Calculated the invention (conc. in efficacy efficacy*) ppm) 15q 2 ppm I' + 2 ppm VII 35% 20%
5 0.5 ppm I' + 0.5 ppm 20% 0%
VII
*) calculated using Colby's formula The test results show that the observed efficacy for all mixing ratios is higher than the efficacy which had been calculated beforehand using Colby's formula.
Claims (5)
1. A fungicidal mixture, comprising as active components a) phenylacetic acid derivatives of the formula I
in which the substituents and the index have the following meaning:
X is NOCH3, CHOCH3 or CHCH3;
Y is oxygen or NR;
R1, R independently of one another are each hydrogen or C1-C4-alkyl;
R2 is cyano, nitro, trifluoromethyl, halogen, C1-C4-alkyl or C1-C4-alkoxy;
m is 0, 1 or 2, where the radicals R2 may be different if m is 2;
R3 is hydrogen, cyano, C1-C4-alkyl, C1-C4-haloalkyl or C3-C6-cycloalkyl;
R4, R6 independently of one another are each hydrogen, are C1-C10-alkyl, C3-C6-cycloalkyl, C2-C10-alkenyl, C2-C10-alkynyl, C1-C10-alkylcarbonyl, C2-C10-alkenylcarbonyl, C3-C10-alkynylcarbonyl or C1-C10-alkylsulfonyl, where these radicals may be partially or fully halogenated or may carry one to three of the following groups: cyano, nitro, hydroxyl, mercapto, amino, carboxyl, aminocarbonyl, aminothiocarbonyl, halogen, C1-C6-alkyl, C1-C6-haloalkyl, C1-C6-alkylsulfonyl, C1-C6-alkylsulfoxyl, C1-C6-alkoxy, C1-C6-haloalkoxy, C1-C6-alkoxycarbonyl, C1-C6-alkylthio, C1-C6-alkylamino, di-C1-C6-alkylamino, C1-C6-alkylaminocarbonyl, di-C1-C6-alkylaminocarbonyl, C1-C6-alkylaminothiocarbonyl, di-C1-C6-alkylaminothiocarbonyl, C2-C6-alkenyl, C2-C6-alkenyloxy, C3-C6-cycloalkyl, C3-C6-cyclo-alkyloxy, heterocyclyl, heterocyclyloxy, benzyl, benzyloxy, aryl, aryloxy, arylthio, hetaryl, hetaryloxy and hetarylthio, where the cyclic groups for their part may be partially or fully halogenated or may carry one to three of the following groups: cyano, nitro, hydroxyl, mercapto, amino, carboxyl, aminocarbonyl, aminothiocarbonyl, halogen, C1-C6-alkyl, C1-C6-haloalkyl, C1-C6-alkylsulfonyl, C1-C6-alkyl-sulfoxyl, C3-C6-cycloalkyl, C1-C6-alkoxy, C1-C6-haloalkoxy, C1-C6-alkyloxycarbonyl;
C1-C6-alkylthio, C1-C6-alkylamino, di-C1-C6-alkyl-amino, C1-C6-alkylaminocarbonyl, di-C1-C6-alkyl-aminocarbonyl, C1-C6-alkylaminothiocarbonyl, di-C1-C6-alkylaminothiocarbonyl, C2-C6-alkenyl, C2-C6-alkenyloxy, benzyl, benzyloxy, aryl, aryloxy, arylthio, hetaryl, hetaryloxy, hetarylthio or C(=NOR7)-A n-R8;
are aryl, arylcarbonyl, arylsulfonyl, hetaryl, hetarylcarbonyl or hetarylsulfonyl, where these radicals may be partially or fully halogenated or may carry one to three of the following groups:
cyano, nitro, hydroxyl, mercapto, amino, carboxyl, aminocarbonyl, aminothiocarbonyl, halogen, C1-C6-alkyl, C1-C6-haloalkyl, C1-C6-alkylcarbonyl, C1-C6-alkylsulfonyl, C1-C6-alkylsulfoxyl, C3-C6-cycloalkyl, C1-C6-alkoxy, C1-C6-haloalkoxy, C1-C6-alkyloxycarbonyl, C1-C6-alkylthio, C1-C6-alkylamino, di-C1-C6-alkylamino, C1-C6-alkylaminocarbonyl, di-C1-C6-alkylamino-carbonyl, C1-C6-alkylaminothiocarbonyl, di-C1-C6-alkylaminothiocarbonyl, C2-C6-alkenyl, C2-C6-alkenyloxy, benzyl, benzyloxy, aryl, aryloxy, hetaryl, hetaryloxy or C(=NOR7)-A n-R8;
R5 is hydrogen, is C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, where the hydrocarbon radicals of these groups may be partially or fully halogenated or may carry one to three of the following radicals: cyano, nitro, hydroxyl, mercapto, amino, carboxyl, amino-carbonyl, aminothiocarbonyl, halogen, C1-C6-alkyl-aminocarbonyl, di-C1-C6-alkylaminocarbonyl, C1-C6-alkylaminothiocarbonyl, di-C1-C6-alkylamino-thiocarbonyl, C1-C6-alkylsulfonyl, C1-C6-alkyl-sulfoxyl, C1-C6-alkoxy, C1-C6-haloalkoxy, C1-C6-alkoxycarbonyl, C1-C6-alkylthio, C1-C6-alkyl-amino, di-C1-C6-alkylamino, C2-C6-alkenyloxy, C3-C6-cycloalkyl, C3-C6-cycloalkyloxy, hetero-cyclyl, heterocyclyloxy, aryl, aryloxy, aryl-C1-C4-alkoxy, arylthio, aryl-C1-C4-alkylthio, hetaryl, hetaryloxy, hetaryl-C1-C4-alkoxy, hetarylthio, hetaryl-C1-C4-alkylthio, where the cyclic radicals for their part may be partially or fully halogenated and/or may carry one to three of the following groups: cyano, nitro, hydroxyl, mercapto, amino, carboxyl, aminocarbonyl, aminothiocarbonyl, C1-C6-alkyl, C1-C6-haloalkyl, C1-C6-alkylsulfonyl, C1-C6-alkylsulfoxyl, C3C6-cycloalkyl [sic], C1-C6-alkoxy, C1-C6-haloalkoxy, C1-C6-alkoxycarbonyl, C1-C6-alkylthio, C1-C6-alkyl-amino, di-C1-C6-alkylamino, C1-C6-alkylamino-carbonyl, di-C1-C6-alkylaminocarbonyl, C1-C6-alkyl-aminothiocarbonyl, di-C1-C6-alkylaminothiocarbonyl, C2-C6-alkenyl, C2-C6-alkenyloxy, benzyl, benzyloxy, aryl, aryloxy, arylthio, hetaryl, hetaryloxy, hetarylthio and C(=NOR7)-A n-R8;
is C3-C6-cycloalkyl, C3-C6-cycloalkenyl, heterocyclyl, aryl, hetaryl, where the cyclic radicals may be partially or fully halogenated or may carry one to three of the following groups:
cyano, nitro, hydroxyl, mercapto, amino, carboxyl, aminocarbonyl, aminothiocarbonyl, halogen, C1-C6-alkyl, C1-C6-haloalkyl, C1-C6-alkylsulfonyl, C1-C6-alkylsulfoxyl, C3-C6-cycloalkyl, C1-C6-alkoxy, C1-C6-haloalkoxy, C1-C6-alkoxycarbonyl, C1-C6-alkyl-thio, C1-C6-alkylamino, di-C1-C6-alkylamino, C1-C6-alkylaminocarbonyl, di-C1-C6-alkylamino-carbonyl, C1-C6-alkylaminothiocarbonyl, di-C1-C6-alkylaminothiocarbonyl, C2-C6-alkenyl, C2-C6-alkenyloxy, benzyl, benzyloxy, aryl, aryloxy, hetaryl and hetaryloxy;
where A is oxygen, sulfur or nitrogen and where the nitrogen carries hydrogen or C1-C6-alkyl;
n is 0 or 1;
R7 is hydrogen or C1-C6-alkyl and R8 is hydrogen or C1-C6-alkyl, and their salts, and b) at least one compound of the formulae II to VII
in a synergistically effective amount.
in which the substituents and the index have the following meaning:
X is NOCH3, CHOCH3 or CHCH3;
Y is oxygen or NR;
R1, R independently of one another are each hydrogen or C1-C4-alkyl;
R2 is cyano, nitro, trifluoromethyl, halogen, C1-C4-alkyl or C1-C4-alkoxy;
m is 0, 1 or 2, where the radicals R2 may be different if m is 2;
R3 is hydrogen, cyano, C1-C4-alkyl, C1-C4-haloalkyl or C3-C6-cycloalkyl;
R4, R6 independently of one another are each hydrogen, are C1-C10-alkyl, C3-C6-cycloalkyl, C2-C10-alkenyl, C2-C10-alkynyl, C1-C10-alkylcarbonyl, C2-C10-alkenylcarbonyl, C3-C10-alkynylcarbonyl or C1-C10-alkylsulfonyl, where these radicals may be partially or fully halogenated or may carry one to three of the following groups: cyano, nitro, hydroxyl, mercapto, amino, carboxyl, aminocarbonyl, aminothiocarbonyl, halogen, C1-C6-alkyl, C1-C6-haloalkyl, C1-C6-alkylsulfonyl, C1-C6-alkylsulfoxyl, C1-C6-alkoxy, C1-C6-haloalkoxy, C1-C6-alkoxycarbonyl, C1-C6-alkylthio, C1-C6-alkylamino, di-C1-C6-alkylamino, C1-C6-alkylaminocarbonyl, di-C1-C6-alkylaminocarbonyl, C1-C6-alkylaminothiocarbonyl, di-C1-C6-alkylaminothiocarbonyl, C2-C6-alkenyl, C2-C6-alkenyloxy, C3-C6-cycloalkyl, C3-C6-cyclo-alkyloxy, heterocyclyl, heterocyclyloxy, benzyl, benzyloxy, aryl, aryloxy, arylthio, hetaryl, hetaryloxy and hetarylthio, where the cyclic groups for their part may be partially or fully halogenated or may carry one to three of the following groups: cyano, nitro, hydroxyl, mercapto, amino, carboxyl, aminocarbonyl, aminothiocarbonyl, halogen, C1-C6-alkyl, C1-C6-haloalkyl, C1-C6-alkylsulfonyl, C1-C6-alkyl-sulfoxyl, C3-C6-cycloalkyl, C1-C6-alkoxy, C1-C6-haloalkoxy, C1-C6-alkyloxycarbonyl;
C1-C6-alkylthio, C1-C6-alkylamino, di-C1-C6-alkyl-amino, C1-C6-alkylaminocarbonyl, di-C1-C6-alkyl-aminocarbonyl, C1-C6-alkylaminothiocarbonyl, di-C1-C6-alkylaminothiocarbonyl, C2-C6-alkenyl, C2-C6-alkenyloxy, benzyl, benzyloxy, aryl, aryloxy, arylthio, hetaryl, hetaryloxy, hetarylthio or C(=NOR7)-A n-R8;
are aryl, arylcarbonyl, arylsulfonyl, hetaryl, hetarylcarbonyl or hetarylsulfonyl, where these radicals may be partially or fully halogenated or may carry one to three of the following groups:
cyano, nitro, hydroxyl, mercapto, amino, carboxyl, aminocarbonyl, aminothiocarbonyl, halogen, C1-C6-alkyl, C1-C6-haloalkyl, C1-C6-alkylcarbonyl, C1-C6-alkylsulfonyl, C1-C6-alkylsulfoxyl, C3-C6-cycloalkyl, C1-C6-alkoxy, C1-C6-haloalkoxy, C1-C6-alkyloxycarbonyl, C1-C6-alkylthio, C1-C6-alkylamino, di-C1-C6-alkylamino, C1-C6-alkylaminocarbonyl, di-C1-C6-alkylamino-carbonyl, C1-C6-alkylaminothiocarbonyl, di-C1-C6-alkylaminothiocarbonyl, C2-C6-alkenyl, C2-C6-alkenyloxy, benzyl, benzyloxy, aryl, aryloxy, hetaryl, hetaryloxy or C(=NOR7)-A n-R8;
R5 is hydrogen, is C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, where the hydrocarbon radicals of these groups may be partially or fully halogenated or may carry one to three of the following radicals: cyano, nitro, hydroxyl, mercapto, amino, carboxyl, amino-carbonyl, aminothiocarbonyl, halogen, C1-C6-alkyl-aminocarbonyl, di-C1-C6-alkylaminocarbonyl, C1-C6-alkylaminothiocarbonyl, di-C1-C6-alkylamino-thiocarbonyl, C1-C6-alkylsulfonyl, C1-C6-alkyl-sulfoxyl, C1-C6-alkoxy, C1-C6-haloalkoxy, C1-C6-alkoxycarbonyl, C1-C6-alkylthio, C1-C6-alkyl-amino, di-C1-C6-alkylamino, C2-C6-alkenyloxy, C3-C6-cycloalkyl, C3-C6-cycloalkyloxy, hetero-cyclyl, heterocyclyloxy, aryl, aryloxy, aryl-C1-C4-alkoxy, arylthio, aryl-C1-C4-alkylthio, hetaryl, hetaryloxy, hetaryl-C1-C4-alkoxy, hetarylthio, hetaryl-C1-C4-alkylthio, where the cyclic radicals for their part may be partially or fully halogenated and/or may carry one to three of the following groups: cyano, nitro, hydroxyl, mercapto, amino, carboxyl, aminocarbonyl, aminothiocarbonyl, C1-C6-alkyl, C1-C6-haloalkyl, C1-C6-alkylsulfonyl, C1-C6-alkylsulfoxyl, C3C6-cycloalkyl [sic], C1-C6-alkoxy, C1-C6-haloalkoxy, C1-C6-alkoxycarbonyl, C1-C6-alkylthio, C1-C6-alkyl-amino, di-C1-C6-alkylamino, C1-C6-alkylamino-carbonyl, di-C1-C6-alkylaminocarbonyl, C1-C6-alkyl-aminothiocarbonyl, di-C1-C6-alkylaminothiocarbonyl, C2-C6-alkenyl, C2-C6-alkenyloxy, benzyl, benzyloxy, aryl, aryloxy, arylthio, hetaryl, hetaryloxy, hetarylthio and C(=NOR7)-A n-R8;
is C3-C6-cycloalkyl, C3-C6-cycloalkenyl, heterocyclyl, aryl, hetaryl, where the cyclic radicals may be partially or fully halogenated or may carry one to three of the following groups:
cyano, nitro, hydroxyl, mercapto, amino, carboxyl, aminocarbonyl, aminothiocarbonyl, halogen, C1-C6-alkyl, C1-C6-haloalkyl, C1-C6-alkylsulfonyl, C1-C6-alkylsulfoxyl, C3-C6-cycloalkyl, C1-C6-alkoxy, C1-C6-haloalkoxy, C1-C6-alkoxycarbonyl, C1-C6-alkyl-thio, C1-C6-alkylamino, di-C1-C6-alkylamino, C1-C6-alkylaminocarbonyl, di-C1-C6-alkylamino-carbonyl, C1-C6-alkylaminothiocarbonyl, di-C1-C6-alkylaminothiocarbonyl, C2-C6-alkenyl, C2-C6-alkenyloxy, benzyl, benzyloxy, aryl, aryloxy, hetaryl and hetaryloxy;
where A is oxygen, sulfur or nitrogen and where the nitrogen carries hydrogen or C1-C6-alkyl;
n is 0 or 1;
R7 is hydrogen or C1-C6-alkyl and R8 is hydrogen or C1-C6-alkyl, and their salts, and b) at least one compound of the formulae II to VII
in a synergistically effective amount.
2. A fungicidal mixture as claimed in claim 1, which is conditioned in two parts, one part comprising the compound I
in a solid or liquid carrier and the other part comprising at least one of the compounds II to VII in a solid or liquid carrier.
in a solid or liquid carrier and the other part comprising at least one of the compounds II to VII in a solid or liquid carrier.
3. A method for controlling harmful fungi, which comprises treating the fungi, their habitat, or the materials, plants, seeds, soils, areas or spaces to be protected against fungal attack with a fungicidal mixture as claimed in claim 1 or 2, where the application of the compound I and at least one of the compounds II to VII may be carried out simultaneously, either together or separately, or in succession.
4. A method as claimed in claim 3, wherein the harmful fungi, their habitat or the plants, seeds, soils, areas, materials or spaces to be kept free from them are treated with from 0.005 to 1 kg/ha of a compound I as set forth in claim 1.
5. A method as claimed in claim 3, wherein the harmful fungi, their habitat or the plants, seeds, soils, areas, materials or spaces to be kept free from them are treated with from 0.01 to 1 kg/ha of at least one of the compounds II to VII as set forth in claim 1.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19812763 | 1998-03-24 | ||
| DE19812763.4 | 1998-03-24 | ||
| PCT/EP1999/001907 WO1999048365A1 (en) | 1998-03-24 | 1999-03-22 | Fungicide mixtures based on triple oxime ether derivatives and rhizoctonia fungicides |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2323661A1 true CA2323661A1 (en) | 1999-09-30 |
Family
ID=7862022
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002323661A Abandoned CA2323661A1 (en) | 1998-03-24 | 1999-03-22 | Fungicide mixtures based on triple oxime ether derivatives and rhizoctonia fungicides |
Country Status (12)
| Country | Link |
|---|---|
| EP (1) | EP1065927A1 (en) |
| JP (1) | JP2002507550A (en) |
| KR (1) | KR100557364B1 (en) |
| CN (1) | CN1294491A (en) |
| AU (1) | AU3331599A (en) |
| BR (1) | BR9908996A (en) |
| CA (1) | CA2323661A1 (en) |
| CO (1) | CO5050292A1 (en) |
| ID (1) | ID27443A (en) |
| IL (1) | IL138167A0 (en) |
| TW (1) | TW565431B (en) |
| WO (1) | WO1999048365A1 (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100345482C (en) * | 2000-12-18 | 2007-10-31 | 巴斯福股份公司 | Fangicide mixtures based on oxime ether derivatives |
| TW200531632A (en) * | 2004-01-15 | 2005-10-01 | Basf Ag | Fungicidal mixtures for controlling harmful fungi |
| US20080051285A1 (en) * | 2004-03-15 | 2008-02-28 | Basf Aktiengesellschaft | Fungicidal Mixtures For Controlling Rice Pathogens |
| US20080153824A1 (en) * | 2004-12-20 | 2008-06-26 | Basf Aktiengesellschaft | Method for Controlling Fungal Diseases in Leguminous Plants |
| DE102005034350A1 (en) * | 2005-07-22 | 2007-01-25 | Consortium für elektrochemische Industrie GmbH | Paints containing particles |
| WO2008135480A2 (en) * | 2007-05-02 | 2008-11-13 | Basf Se | Method for controlling specific fungal pathogen in soybeans by employing benodanil |
| JP2011201856A (en) * | 2010-03-03 | 2011-10-13 | Sumitomo Chemical Co Ltd | Plant disease controlling composition and method for controlling plant disease |
| JP5747542B2 (en) * | 2010-03-03 | 2015-07-15 | 住友化学株式会社 | Plant disease control composition and plant disease control method |
| CN103524418B (en) * | 2013-11-01 | 2016-03-23 | 青岛农业大学 | One group of 3-methylpyrazole compound |
| CN105076154B (en) * | 2014-05-08 | 2017-06-06 | 江苏龙灯化学有限公司 | A kind of bactericidal composition |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2814678B2 (en) * | 1990-03-29 | 1998-10-27 | 住友化学工業株式会社 | Agricultural and horticultural sterilizing composition |
| US6518304B1 (en) * | 1993-12-02 | 2003-02-11 | Sumitomo Chemical Company, Limited | Fungicidal composition |
| JP3470399B2 (en) * | 1994-07-14 | 2003-11-25 | 住友化学工業株式会社 | Fungicide composition |
| HU214916B (en) * | 1994-07-21 | 1998-07-28 | Basf Aktiengesellschaft | Synergetic fungicidal compositions and method of combating harmful fungi |
| JP3558405B2 (en) * | 1995-04-20 | 2004-08-25 | 三井化学株式会社 | Insecticidal fungicidal composition |
| TW401275B (en) * | 1995-09-25 | 2000-08-11 | Basf Ag | Compositions and methods of controlling harmful fungi |
| FR2739529B1 (en) * | 1995-10-05 | 1997-10-31 | Rhone Poulenc Agrochimie | FUNGICIDAL COMPOSITION COMPRISING A STROBILURIN-LIKE COMPOUND |
| DE19539324A1 (en) * | 1995-10-23 | 1997-04-24 | Basf Ag | Phenylacetic acid derivatives, processes and intermediates for their preparation and compositions containing them |
-
1999
- 1999-03-22 JP JP2000537431A patent/JP2002507550A/en active Pending
- 1999-03-22 ID IDW20001901A patent/ID27443A/en unknown
- 1999-03-22 CA CA002323661A patent/CA2323661A1/en not_active Abandoned
- 1999-03-22 KR KR1020007010552A patent/KR100557364B1/en not_active IP Right Cessation
- 1999-03-22 CN CN99804340A patent/CN1294491A/en active Pending
- 1999-03-22 IL IL13816799A patent/IL138167A0/en unknown
- 1999-03-22 BR BR9908996-3A patent/BR9908996A/en not_active Application Discontinuation
- 1999-03-22 AU AU33315/99A patent/AU3331599A/en not_active Abandoned
- 1999-03-22 EP EP99914529A patent/EP1065927A1/en not_active Withdrawn
- 1999-03-22 WO PCT/EP1999/001907 patent/WO1999048365A1/en active IP Right Grant
- 1999-03-24 CO CO99017848A patent/CO5050292A1/en unknown
- 1999-03-24 TW TW088104752A patent/TW565431B/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| IL138167A0 (en) | 2001-10-31 |
| KR20010042147A (en) | 2001-05-25 |
| ID27443A (en) | 2001-04-12 |
| JP2002507550A (en) | 2002-03-12 |
| KR100557364B1 (en) | 2006-03-10 |
| EP1065927A1 (en) | 2001-01-10 |
| CN1294491A (en) | 2001-05-09 |
| CO5050292A1 (en) | 2001-06-27 |
| WO1999048365A1 (en) | 1999-09-30 |
| AU3331599A (en) | 1999-10-18 |
| TW565431B (en) | 2003-12-11 |
| BR9908996A (en) | 2000-12-12 |
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