EP1926376A1 - Triazole-based fungicidal mixtures - Google Patents

Triazole-based fungicidal mixtures

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Publication number
EP1926376A1
EP1926376A1 EP06793222A EP06793222A EP1926376A1 EP 1926376 A1 EP1926376 A1 EP 1926376A1 EP 06793222 A EP06793222 A EP 06793222A EP 06793222 A EP06793222 A EP 06793222A EP 1926376 A1 EP1926376 A1 EP 1926376A1
Authority
EP
European Patent Office
Prior art keywords
formula
compound
mixtures
epoxiconazole
weight
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP06793222A
Other languages
German (de)
French (fr)
Inventor
Martin Semar
Dieter Strobel
Jens Bruns
Reinhard Stierl
Frank Werner
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Publication of EP1926376A1 publication Critical patent/EP1926376A1/en
Withdrawn legal-status Critical Current

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Classifications

    • 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
    • A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
    • A01N43/647—Triazoles; Hydrogenated triazoles
    • A01N43/653—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles

Definitions

  • the present invention relates to fungicidal mixtures containing
  • the invention relates to a method for controlling harmful fungi with mixtures of the compound I with at least one of the compounds II to V and the use of the compound I with at least one of the compounds II to V for the preparation of such mixtures and compositions containing these mixtures.
  • Epoxiconazole of the formula I and its use as a crop protection agent is described in EP-B 0 196 038.
  • Difenconazole of the formula IM is known from EP-A 0 1 12 284.
  • Hexaconazole of the formula IV is described in DE-A 30 42 303. Bromuconazole of Formula V is described in Pesticide Manual, 12th Ed. (2000), page 1 14 described.
  • the present inventions were mixtures as an object that show an improved action against harmful fungi, especially for certain indications with reduced total amount of applied drugs.
  • the mixtures defined above were found. It has also been found that, with simultaneous simultaneous or separate application of the compounds I and of an active compound II or, when using the compounds I and an active compound II, harmful fungi can be controlled better successively than with the individual compounds (synergistic mixtures).
  • the compounds I can be used as a synergist for a variety of different drugs. By simultaneous joint or separate application of the compound I with an active compound II, the fungicidal activity is increased to a superadditive extent.
  • the compounds I to V are capable of forming salts or adducts with inorganic or organic acids or with metal ions.
  • inorganic acids are hydrohalic acids such as hydrogen fluoride, hydrogen chloride, hydrogen bromide and hydrogen iodide, sulfuric acid, phosphoric acid and nitric acid.
  • suitable organic acids are formic acid, carbonic acid and alkanoic acids, such as acetic acid, trifluoroacetic acid, trichloroacetic acid and propionic acid, and also glycolic acid, thiocyanic acid, lactic acid, succinic acid, citric acid, benzoic acid, cinnamic acid, oxalic acid, alkylsulfonic acids (sulfonic acids having straight-chain or branched alkyl radicals having 1 to 20 carbon atoms), Arylsulfonic acids or - disulfonic acids (aromatic radicals such as phenyl and naphthyl which carry one or two sulfonic acid groups), alkylphosphonic acids (phosphonic acids with straight-chain or branched alkyl radicals having 1 to 20 carbon atom
  • the metal ions are, in particular, the ions of the elements of the second main group, in particular calcium and magnesium, the third and fourth main groups, in particular aluminum, tin and lead, and the first to eighth transition groups, in particular chromium, manganese, iron, cobalt, nickel, Copper, zinc and others. Particularly preferred are the metal ions of the elements of the subgroups of the fourth period.
  • the metals can be present in the various valences that belong to them.
  • the mixtures of the compound I and of an active compound II, or the simultaneous joint or separate use of the compound I and an active compound II are distinguished by an outstanding activity against a broad spectrum of phytopathogenic fungi, in particular from the class of the Ascomycetes, Deuteromycetes , Peronosporomycetes (syn. Oomycetes) and Basidiomycetes. They are partially systemically effective and can be used in crop protection as pickling, foliar and soil fungicides.
  • Cochliobolus species on corn, cereals, rice e.g. Cochliobolus sativus on cereals, Cochliobolus miyabeanus on rice
  • Drechslera species Pyrenophora species on maize, cereals, rice and turf, e.g. D.teres to barley or D. tritici-repentis to wheat
  • Fusarium and Verticillium species on various plants e.g. F. graminearum or F. culmorum on cereal or F. oxysporum on a variety of plants.
  • Plants such as e.g. tomatoes
  • Michrodochium nivale on cereals • Mycosphaerella species on cereals, bananas and peanuts, e.g. M. granicola on wheat or M.fijiensis on bananas
  • Peronospora species on cabbage and bulbous plants such as P. brassicae on cabbage or P. destructor on onion
  • Phytophthora species on various plants such as P. capsici on peppers, Plasmopara viticola on grapevines,
  • Pseudoperonospora on various plants e.g. P. cubensis on cucumber or P. humili on hops
  • Puccinia species on various plants e.g. P. triticina, P. striformins, P. hordei or P.graminis on cereals, or P. asparagi on asparagus
  • Venturia species scab
  • apples and pears like. e.g. V. inaequalis to apple.
  • the mixtures of the compounds I and of an active compound II are particularly suitable for controlling harmful fungi from the class of the Peronosporomycetes (syn. Oomycetes), such as Peronospora species, Phytophthora species, Plasmopara viticola and Pseudoperonospora species, in particular the corresponding species mentioned above.
  • Peronosporomycetes such as Peronospora species, Phytophthora species, Plasmopara viticola and Pseudoperonospora species, in particular the corresponding species mentioned above.
  • the mixtures of compounds I and II are also suitable for controlling harmful fungi in the protection of materials (eg wood, paper, paint dispersions, fibers or fabrics) and in the protection of stored products.
  • harmful fungi Ascomycetes such as Ophiostoma spp., Ceratocystis spp., Aureosidium pullulans, Sclerophoma spp., Chaetomium spp., Humicola spp., Petriella spp., Trichurus spp .; Basidiomycetes such as Coniophora spp., Coriolus spp., Gloeophlum spp., Lentinus spp., Pleurotus spp., Poria spp., Serpula spp.
  • Tyromyces spp. Deuteromycetes such as Aspergillus spp., Cladosporium spp., Penicillium spp., Trichodo- spp. ma spp., Alternaria spp., Paecilomyces spp. and Zygomycetes such as Mucor spp., moreover, in the protection of the following yeasts: Candida spp. and Saccharomyces cerevisae.
  • the compounds I are used by treating the fungi or the plants, seeds, materials or the soil to be protected against fungal attack with a fungicidally effective amount of the active ingredients.
  • the application can be done both before and after the infection of the materials, plants or seeds by the fungi.
  • the compounds I and active compounds II can be applied simultaneously together or separately or in succession, the sequence in the case of separate application generally having no effect on the control result.
  • the pure active ingredients I and at least one of the active ingredients II to V which can be further active against harmful fungi or against other pests such as insects, spider animals or nematodes or herbicidal or growth-regulating agents or fertilizers.
  • Active substances II to V for use. Under certain circumstances, however, mixtures of compound I with two or optionally several active components may be advantageous.
  • the compound I and the active compound II are usually employed in a weight ratio of from 100: 1 to 1: 100, preferably from 20: 1 to 1:20, in particular from 10: 1 to 1:10.
  • the compound I and the active ingredient IM are usually employed in a weight ratio of 100: 1 to 1: 100, preferably 20: 1 to 1:20, in particular 10: 1 to 1:10.
  • the compound I and the active ingredient IV are usually used in a weight ratio of 100: 1 to 1: 100, preferably 20: 1 to 1:20, in particular 10: 1 to 1:10 applied.
  • the compound I and the active ingredient V are usually used in a weight ratio of 100: 1 to 1: 100, preferably 20: 1 to 1:20, in particular 10: 1 to 1:10 applied.
  • the further active components are added to compound I in a ratio of from 20: 1 to 1:20.
  • the application rates of the mixtures according to the invention, especially in agricultural crops, depending on the nature of the compound and the desired effect at 5 g / ha to 2000 g / ha, preferably 20 to 900 g / ha, in particular 50 to 750 g / ha.
  • the application rates for the compound I are accordingly generally 1 to 1000 g / ha, preferably 10 to 900 g / ha, in particular 20 to 750 g / ha.
  • the application rates for the active compound II are accordingly generally from 1 to 2000 g / ha, preferably from 10 to 1500 g / ha, in particular from 40 to 1000 g / ha.
  • the application rates for the active ingredient IM are correspondingly generally 1 to 2000 g / ha, preferably 10 to 1500 g / ha, in particular 40 to 1000 g / ha.
  • the application rates for the active ingredient IV are correspondingly generally 1 to 2000 g / ha, preferably 10 to 1500 g / ha, in particular 40 to 1000 g / ha.
  • the application rates for the active ingredient V are correspondingly generally 1 to 2000 g / ha, preferably 10 to 1500 g / ha, in particular 40 to 1000 g / ha.
  • application rates of mixture of 1 to 1000 g / 100 kg of seed preferably 1 to 750 g / 100 kg, in particular 5 to 500 g / 100 kg, are generally used.
  • the method for controlling harmful fungi is carried out by the separate or combined application of compound I and at least one of the active ingredients II to V or a mixture of compound I and at least one of the active ingredients II to V by spraying or dusting the seeds, the plants or the soil before or after sowing the plants or before or after emergence of the plants.
  • the mixtures according to the invention or the compound I and at least one of the active compounds II to V can be converted into the customary formulations, e.g. Solutions, emulsions, suspensions, dusts, powders, pastes and granules.
  • the application form depends on the respective purpose; It should in any case ensure a fine and uniform distribution of the compound according to the invention.
  • the formulations are prepared in a known manner, for example by stretching the active ingredient with solvents and / or excipients, if desired with use of emulsifiers and dispersants.
  • Suitable solvents / auxiliaries are essentially: - water, aromatic solvents (eg Solvesso products, xylene), paraffins (eg petroleum fractions), alcohols (eg methanol, butanol, pentanol, benzyl alcohol), ketones (eg cyclohexanone, gamma-butyrolactone), pyrrolidones (NMP, NOP), Acetates (glycol diacetate), glycols, dimethyl fatty acid amides, fatty acids and fatty acid esters.
  • solvent mixtures can also be used
  • Excipients such as ground natural minerals (e.g., kaolins, clays, talc, chalk) and ground synthetic minerals (e.g., fumed silica, silicates); Emulsifiers such as nonionic and anionic emulsifiers (for example polyoxyethylene fatty alcohol ethers, alkyl sulfonates and arylsulfonates) and dispersants such as lignin-sulphite liquors and methylcellulose.
  • ground natural minerals e.g., kaolins, clays, talc, chalk
  • ground synthetic minerals e.g., fumed silica, silicates
  • Emulsifiers such as nonionic and anionic emulsifiers (for example polyoxyethylene fatty alcohol ethers, alkyl sulfonates and arylsulfonates) and dispersants such as lignin-sulphite liquors and methylcellulose.
  • the surface-active substances used are alkali metal, alkaline earth metal, ammonium salts of lignin sulfonic acid, naphthalenesulfonic acid, phenolsulfonic acid, dibutylnaphthalenesulfonic acid, alkylarylsulfonates, alkyl sulfates, alkyl sulfonates, fatty alcohol sulfates, fatty acids and sulfated fatty alcohol glycol ethers, and condensation products of sulfonated naphthalene and naphthalene derivatives with formaldehyde , Condensation products of naphthalene or naphthalenesulfonic acid with phenol and formaldehyde, polyoxyethylene octylphenol ether, ethoxylated isooctylphenol, octylphenol, nonylphenol, alkylphenol polyglycol ethers, tributylphenyl
  • mineral oil fractions of medium to high boiling point such as kerosine or diesel oil, coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, e.g. Toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes or their derivatives, methanol, ethanol, propanol, butanol, cyclohexanol, cyclohexanone, isophorone, strong polar solvents, e.g. Dimethylsulfoxide, N-methylpyrrolidone or water into consideration.
  • mineral oil fractions of medium to high boiling point such as kerosine or diesel oil, coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, e.g. Toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes or their derivative
  • Powders, dispersants and dusts may be prepared by mixing or co-grinding the active substances with a solid carrier.
  • Granules for example coated, impregnated and homogeneous granules, can be prepared by binding the active compounds to solid carriers.
  • Solid carriers are, for example, mineral earths, such as silica gels, silicates, talc, kaolin, Attaclay, limestone, lime, chalk, bolus, loess, clay, dolomite, diatomaceous earth, calcium and magnesium sulfate, magnesium oxide, ground plastics, fertilizers, such as ammonium sulfate, ammonium phosphate , Ammonium nitrate, ureas and vegetable products such as cereal flour, bark, wood and nutshell flour, cellulose powder and other solid carriers.
  • mineral earths such as silica gels, silicates, talc, kaolin, Attaclay, limestone, lime, chalk, bolus, loess, clay, dolomite, diatomaceous earth, calcium and magnesium sulfate, magnesium oxide, ground plastics, fertilizers
  • the formulations generally contain between 0.01 and 95 wt .-%, preferably between 0.1 and 90 wt .-% of the active ingredients.
  • the active ingredients are used in a purity of 90% to 100%, preferably 95% to 100% (according to NMR spectrum).
  • formulations are: 1. Products for dilution in water
  • a compound according to the invention 20 parts by weight of a compound according to the invention are dissolved in 70 parts by weight of cyclohexanone with the addition of 10 parts by weight of a dispersant, e.g. Polyvinylpyrrolidone dissolved. Dilution in water gives a dispersion.
  • a dispersant e.g. Polyvinylpyrrolidone dissolved. Dilution in water gives a dispersion.
  • the active ingredient content is 20% by weight
  • a compound according to the invention 15 parts by weight of a compound according to the invention are dissolved in 75 parts by weight of xylene with addition of calcium dodecylbenzenesulfonate and castor oil ethoxylate (in each case 5 parts by weight). Dilution in water results in an emulsion.
  • the formulation has an active ingredient content of 15% by weight.
  • a compound according to the invention 25 parts by weight of a compound according to the invention are dissolved in 35 parts by weight of xylene with addition of calcium dodecylbenzenesulfonate and castor oil ethoxylate (in each case 5 parts by weight).
  • This mixture is added to 30 parts by weight of water by means of an emulsifying machine (e.g., Ultraturax) and made into a homogeneous emulsion. Dilution in water results in an emulsion.
  • the formulation has an active ingredient content of 25% by weight.
  • 50 parts by weight of a compound according to the invention are finely ground with the addition of 50 parts by weight of dispersants and wetting agents and prepared by means of industrial equipment (for example extrusion, spray tower, fluidized bed) as water-dispersible or water-soluble granules. Dilution in water results in a stable dispersion or solution of the active ingredient.
  • the formulation has an active ingredient content of 50% by weight.
  • WP, SP Water-Dispersible and Water-Soluble Powders
  • 75 parts by weight of a compound according to the invention are ground in a rotor-stator mill with the addition of 25 parts by weight of dispersing and wetting agents and silica gel. Dilution in water results in a stable dispersion or solution of the active ingredient.
  • the active ingredient content of the formulation is 75% by weight.
  • 0.5 parts by weight of a compound according to the invention are finely ground and combined with 99.5 parts by weight of carriers. Common processes are extrusion, spray drying or fluidized bed. This gives a granulate for direct application with an active ingredient content of 0.5 wt .-%.
  • the active compounds can be used as such, in the form of their formulations or the application forms prepared therefrom, for example in the form of directly sprayable solutions, powders, suspensions or dispersions, emulsions, oil dispersions, pastes, dusts, scattering agents, granules by spraying, atomizing, dusting, Scattering or pouring are applied.
  • the forms of application depend entirely on the intended use; In any case, they should ensure as far as possible the finest distribution of the active compounds according to the invention.
  • Aqueous application forms can be prepared from emulsion concentrates, pastes or wettable powders (wettable powders, oil dispersions) by adding water.
  • the substances for the preparation of emulsions, pastes or oil dispersions, can be homogenized in water by means of wetter, tackifier, dispersant or emulsifier. But it can also be made of effective substance wetting, adhesion, dispersing or emulsifying and possibly solvent or oil concentrates, which are suitable for dilution with water.
  • the active compound concentrations in the ready-to-use preparations can be varied within wide ranges. In general, they are between 0.0001 and 10%, preferably between 0.01 and 1%.
  • the active ingredients can also be used with great success in the ultra-low-volume (ULV) process, it being possible to apply formulations containing more than 95% by weight of active ingredient or even the active ingredient without additives.
  • UUV ultra-low-volume
  • wetting agents To the active ingredients oils of various types, wetting agents, adjuvants, possibly also immediately before use (tank mix), are added. These agents are usually admixed to the compositions according to the invention in a weight ratio of 1: 100 to 100: 1, preferably 1:10 to 10: 1.
  • the compound I and at least one of the active ingredients II to V or the mixtures or the corresponding formulations are used by removing the harmful fungi, the plants, seeds, soils, surfaces, materials or spaces having a fungicidally effective amount the mixture, or the compound I and at least one of the active ingredients II to V in separate application, treated.
  • the application can be made before or after the attack by the harmful fungi.
  • the efficiency (W) is calculated according to the formula of Abbot as follows:
  • ⁇ corresponds to the fungal infestation of the treated plants in% and ⁇ corresponds to the fungal infestation of the untreated (control) plants in%
  • the infestation of the treated plants corresponds to that of the untreated control plants; at an efficiency of 100, the treated plants have no infestation.
  • the expected efficiencies for drug combinations were determined according to the Colby formula (Colby, SR (Calculating synergistic and antagonistic responses of herbicidal combinations, Weeds, 5, p 20 - 22, 1967) and compared with the observed efficiencies.
  • the active ingredient epoxiconazole and triticonazole was used as a commercial formulation.
  • the stock solution is pipetted into a microtiter plate (MTP) and diluted with an aqueous malt-based mushroom nutrient medium to the stated active substance concentration. This was followed by the addition of an aqueous spore suspension of Pyricularia oryzae.
  • MTP microtiter plate
  • the plates were placed in a water vapor saturated chamber at temperatures of 18 ° C. With an absorbance photometer, the MTPs were measured at 405 nm on the 7th day after inoculation. The measured parameters were consistent with the growth of drug-free
  • Efficiency 0 is the same infestation as in the untreated control, efficiency 100 is 0% infestation.
  • the expected efficiencies for drug combinations were determined according to the Colby formula (Colby, SR (Calculating synergistic and antagonistic responses of herbicidal combinations, Weeds, 5, p 20 - 22, 1967) and compared with the observed efficiencies.

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  • Life Sciences & Earth Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Pretreatment Of Seeds And Plants (AREA)

Abstract

The invention relates to fungicidal mixtures which comprise (1) the epoxiconazole of formula (I) or the salts or adducts thereof, and (2) the triticonazole of formula (II) or (3) the difenconazole of formula (III) or (4) the hexaconazole of formula (IV) or the bromuconazole of formula (V) in a synergistically effective amount. The invention also relates to a method for controlling parasitic fungi using mixtures from a compound (I) and at least one active substance (II), to the use of a compound (I) with active substances (II) for producing mixtures of the aforementioned kind, and to agents containing said mixtures.

Description

Fungizide Mischungen auf der Basis von TriazolenFungicidal mixtures based on triazoles
Beschreibungdescription
Die vorliegende Erfindung betrifft fungizide Mischungen, enthaltendThe present invention relates to fungicidal mixtures containing
(1 ) Epoxiconazol der Formel I(1) epoxiconazole of the formula I.
oder dessen Salze oder Addukteor its salts or adducts
undand
(2) Triticonazol der Formel Il(2) Triticonazole of the formula II
oderor
(3) Difenconazol der Formel(3) Difenconazole of the formula
oder or
(4) Hexaconazol der Formel IV(4) hexaconazole of formula IV
oderor
(5) Bromuconazol der Formel V(5) Bromuconazole of the formula V
in einer synergistisch wirksamen Menge.in a synergistically effective amount.
Außerdem betrifft die Erfindung ein Verfahren zur Bekämpfung von Schadpilzen mit Mischungen der Verbindung I mit mindestens einer der Verbindungen Il bis V und die Verwendung der Verbindung I mit mindestens einer der Verbindungen Il bis V zur Herstellung derartiger Mischungen sowie Mittel, die diese Mischungen enthalten.In addition, the invention relates to a method for controlling harmful fungi with mixtures of the compound I with at least one of the compounds II to V and the use of the compound I with at least one of the compounds II to V for the preparation of such mixtures and compositions containing these mixtures.
Aus der WO 03/073851 ist eine Reihe von Wirkstoffkombinationen von Prothioconazol mit einer Vielzahl anderer Triazole wie Epoxiconazol bekannt.From WO 03/073851 a number of drug combinations of prothioconazole with a variety of other triazoles such as epoxiconazole is known.
Epoxiconazol der Formel I und seine Verwendung als Pflanzenschutzmittel ist in der EP-B 0 196 038 beschrieben.Epoxiconazole of the formula I and its use as a crop protection agent is described in EP-B 0 196 038.
Triticonazol der Formel Il ist in der EP-A 0 378 953 beschrieben.Triticonazole of the formula II is described in EP-A 0 378 953.
Difenconazol der Formel IM ist aus der EP-A 0 1 12 284 bekannt.Difenconazole of the formula IM is known from EP-A 0 1 12 284.
Hexaconazol der Formel IV ist in der DE-A 30 42 303 beschrieben. Bromuconazol der Formel V ist in Pesticide Manual, 12th Ed. (2000), Seite 1 14 beschrieben.Hexaconazole of the formula IV is described in DE-A 30 42 303. Bromuconazole of Formula V is described in Pesticide Manual, 12th Ed. (2000), page 1 14 described.
Im Hinblick auf eine Senkung der Aufwandmengen und eine Verbreiterung des Wirkungsspektrums der bekannten Verbindungen lagen der vorliegenden Erfindungen Mischungen als Aufgabe zugrunde, die bei verringerter Gesamtmenge an ausgebrachten Wirkstoffen eine verbesserte Wirkung gegen Schadpilze, insbesondere für bestimmte Indikationen, zeigen.With regard to a reduction of the application rates and a widening of the spectrum of action of the known compounds, the present inventions were mixtures as an object that show an improved action against harmful fungi, especially for certain indications with reduced total amount of applied drugs.
Demgemäss wurden die eingangs definierten Mischungen gefunden. Es wurde außerdem gefunden, dass sich bei gleichzeitiger gemeinsamer oder getrennter Anwendung der Verbindungen I und eines Wirkstoffs Il oder bei Anwendung der Verbindungen I und eines Wirkstoffs Il nacheinander Schadpilze besser bekämpfen lassen als mit den Einzelverbindungen (synergistische Mischungen). Die Verbindungen I lassen sich als Synergist für eine Vielzahl verschiedener Wirkstoffe verwenden. Durch gleichzeitige gemeinsame oder getrennte Anwendung der Verbindung I mit einem Wirkstoff Il wird die fungizide Wirksamkeit in überadditivem Maße erhöht.Accordingly, the mixtures defined above were found. It has also been found that, with simultaneous simultaneous or separate application of the compounds I and of an active compound II or, when using the compounds I and an active compound II, harmful fungi can be controlled better successively than with the individual compounds (synergistic mixtures). The compounds I can be used as a synergist for a variety of different drugs. By simultaneous joint or separate application of the compound I with an active compound II, the fungicidal activity is increased to a superadditive extent.
Das Epoxiconazol der Formel IThe epoxiconazole of the formula I
ist aus der EP-B 0 196 038 bekannt. is known from EP-B 0 196 038.
Das Triticonazol der Formel IlThe triticonazole of the formula II
ist in der EP-A 0 378 953 beschrieben. Das Difenconazol der Formelis described in EP-A 0 378 953. The difenconazole of the formula
ist in der EP-A 0 1 12 284 beschrieben.is described in EP-A 0 1 12 284.
Das Hexaconazol der Formel IVThe hexaconazole of formula IV
ist in der DE-A 30 42 303 beschrieben.is described in DE-A 30 42 303.
Das Bromuconazol der Formel VThe bromuconazole of the formula V
ist in Pesticide Manual, 12th Ed. (2000), Seite 1 14 beschrieben.is in Pesticide Manual, 12th Ed. (2000), page 1 14 described.
Die Verbindungen I bis V sind wegen des basischen Charakters der in ihnen enthalte- nen Stickstoffatome in der Lage, mit anorganischen oder organischen Säuren oder mit Metallionen Salze oder Addukte zu bilden.Because of the basic character of the nitrogen atoms contained in them, the compounds I to V are capable of forming salts or adducts with inorganic or organic acids or with metal ions.
Beispiele für anorganische Säuren sind Halogenwasserstoffsäuren wie Fluorwasserstoff, Chlorwasserstoff, Bromwasserstoff und Jodwasserstoff, Schwefelsäure, Phos- phorsäure und Salpetersäure. Als organischen Säuren kommen beispielsweise Ameisensäure, Kohlensäure und Alkansäuren wie Essigsäure, Trifluoressigsäure, Trichloressigsäure und Propionsäure sowie Glycolsäure, Thiocyansäure, Milchsäure, Bernsteinsäure, Zitronensäure, Benzoesäure, Zimtsäure, Oxalsäure, Alkylsulfonsäuren (Sulfonsäuren mit geradkettigen oder verzweigten Alkylresten mit 1 bis 20 Kohlenstoffatomen), Arylsulfonsäuren oder - disulfonsäuren (aromatische Reste wie Phenyl und Naphthyl welche eine oder zwei Sulfonsäuregruppen tragen), Alkylphosphonsäuren (Phosphonsäuren mit geradkettigen oder verzweigten Alkylresten mit 1 bis 20 Kohlenstoffatomen), Arylphosphonsäu- ren oder -diphosphonsäuren (aromatische Reste wie Phenyl und Naphthyl welche eine oder zwei Phosphorsäurereste tragen), wobei die Alkyl- bzw. Arylreste weitere Substi- tuenten tragen können, z.B. p-Toluolsulfonsäure, Salizylsäure, p-Aminosalizylsäure, 2- Phenoxybenzoesäure, 2-Acetoxybenzoesäure etc.Examples of inorganic acids are hydrohalic acids such as hydrogen fluoride, hydrogen chloride, hydrogen bromide and hydrogen iodide, sulfuric acid, phosphoric acid and nitric acid. Examples of suitable organic acids are formic acid, carbonic acid and alkanoic acids, such as acetic acid, trifluoroacetic acid, trichloroacetic acid and propionic acid, and also glycolic acid, thiocyanic acid, lactic acid, succinic acid, citric acid, benzoic acid, cinnamic acid, oxalic acid, alkylsulfonic acids (sulfonic acids having straight-chain or branched alkyl radicals having 1 to 20 carbon atoms), Arylsulfonic acids or - disulfonic acids (aromatic radicals such as phenyl and naphthyl which carry one or two sulfonic acid groups), alkylphosphonic acids (phosphonic acids with straight-chain or branched alkyl radicals having 1 to 20 carbon atoms), arylphosphonic acids or diphosphonic acids (aromatic radicals such as phenyl and naphthyl which have one or two carry two phosphoric acid residues), wherein the alkyl or aryl radicals can carry further substituents, for example p-toluenesulfonic acid, salicylic acid, p-aminosalicylic acid, 2-phenoxybenzoic acid, 2-acetoxybenzoic acid, etc.
Als Metallionen kommen insbesondere die Ionen der Elemente der zweiten Haupt- gruppe, insbesondere Calzium und Magnesium, der dritten und vierten Hauptgruppe, insbesondere Aluminium, Zinn und Blei, sowie der ersten bis achten Nebengruppe, insbesondere Chrom, Mangan, Eisen, Kobalt, Nickel, Kupfer, Zink und andere in Betracht. Besonders bevorzugt sind die Metallionen der Elemente der Nebengruppen der vierten Periode. Die Metalle können dabei in den verschiedenen ihnen zukommenden Wertigkeiten vorliegen.The metal ions are, in particular, the ions of the elements of the second main group, in particular calcium and magnesium, the third and fourth main groups, in particular aluminum, tin and lead, and the first to eighth transition groups, in particular chromium, manganese, iron, cobalt, nickel, Copper, zinc and others. Particularly preferred are the metal ions of the elements of the subgroups of the fourth period. The metals can be present in the various valences that belong to them.
Bevorzugt sind Mischungen von Epoxiconazol mit Triticonazol.Preference is given to mixtures of epoxiconazole with triticonazole.
Weiterhin bevorzugt sind Mischungen von Epoxiconazol mit Difenconazol.Further preferred are mixtures of epoxiconazole with difenconazole.
Bevorzugt sind auch Mischungen von Epoxiconazol mit Hexaconazol.Preference is also given to mixtures of epoxiconazole with hexaconazole.
Weiterhin bevorzugt sind Mischungen von Epoxiconazol mit Bromuconazol.Further preferred are mixtures of epoxiconazole with bromuconazole.
Die Mischungen der Verbindung I und eines Wirkstoffs II, bzw. die gleichzeitige gemeinsame oder getrennte Verwendung der Verbindung I und eines Wirkstoffs Il zeichnen sich aus durch eine hervorragende Wirksamkeit gegen ein breites Spektrum von pflanzenpathogenen Pilzen, insbesondere aus der Klasse der Ascomyceten, Deutero- myceten, Peronosporomyceten (syn. Oomyceten) und Basidiomyceten. Sie sind zum Teil systemisch wirksam und können im Pflanzenschutz als Beiz, Blatt- und Bodenfungizide eingesetzt werden.The mixtures of the compound I and of an active compound II, or the simultaneous joint or separate use of the compound I and an active compound II are distinguished by an outstanding activity against a broad spectrum of phytopathogenic fungi, in particular from the class of the Ascomycetes, Deuteromycetes , Peronosporomycetes (syn. Oomycetes) and Basidiomycetes. They are partially systemically effective and can be used in crop protection as pickling, foliar and soil fungicides.
Besondere Bedeutung haben sie für die Bekämpfung einer Vielzahl von Pilzen an verschiedenen Kulturpflanzen wie Bananen, Baumwolle, Gemüsepflanzen (z.B. Gurken, Bohnen und Kürbisse), Gerste, Gras, Hafer, Kaffee, Kartoffeln, Mais, Obstpflanzen, Reis, Roggen, Soja, Tomaten, Wein, Weizen, Zierpflanzen, Zuckerrohr und einer Vielzahl von Samen. Speziell eignen sie sich zur Bekämpfung folgender Pflanzenkrankheiten:They are of particular importance for the control of a variety of fungi on various crops such as bananas, cotton, vegetables (eg cucumbers, beans and pumpkins), barley, grass, oats, coffee, potatoes, corn, fruit plants, rice, rye, soy, tomatoes , Wine, wheat, ornamental plants, sugar cane and a variety of seeds. In particular, they are suitable for controlling the following plant diseases:
• Alternaria Arten an Gemüse, Raps, Zuckerrüben und Obst und Reis , wie z.B. A.solani oder A. alternata an Kartoffeln und Tomaten • Aphanomyces Arten an Zuckerrüben und GemüseAlternaria species on vegetables, oilseed rape, sugar beets and fruits and rice, such as A.solani or A. alternata on potatoes and tomatoes • Aphanomyces species on sugar beet and vegetables
• Ascochyta-Arten an Getreide and Gemüse• Ascochyta species on cereals and vegetables
• Bipolaris- und Drechslera Arten an Mais, Getreide, Reis und Rasen, wie z.B. D.maydis an MaisBipolaris and Drechslera species on maize, cereals, rice and turf, e.g. D.maydis on corn
• Blumeria graminis (Echter Mehltau) an Getreide, • Botrytis cinerea (Grauschimmel) an Erdbeeren, Gemüse, Blumen und Weinreben,• Blumeria graminis (powdery mildew) on cereals, • Botrytis cinerea (gray mold) on strawberries, vegetables, flowers and vines,
• Bremia lactucae an Salat• Bremia lactucae on salad
• Cercospora Arten an Mais, Sojabohnen, Reis und Zuckerrüben• Cercospora species on corn, soybeans, rice and sugar beets
• Cochliobolus Arten an Mais , Getreide, Reis, wie z.B. Cochliobolus sativus an Getreide, Cochliobolus miyabeanus an ReisCochliobolus species on corn, cereals, rice, e.g. Cochliobolus sativus on cereals, Cochliobolus miyabeanus on rice
• Colletotricum Arten an Sojabohnen und Baumwolle• Colletotricum species of soybeans and cotton
• Drechslera Arten, Pyrenophora Arten an Mais, Getreide, Reis und Rasen, wie z.B. D.teres an Gerste oder D. tritici-repentis an Weizen• Drechslera species, Pyrenophora species on maize, cereals, rice and turf, e.g. D.teres to barley or D. tritici-repentis to wheat
• Esca an Weinrebe, verursacht durch Phaeoacremonium chlamydosporium, Ph. Aleophilum, und Formitipora punctata (syn. Phellinus punctatus)• Esca on grapevine caused by Phaeoacremonium chlamydosporium, Ph. Aleophilum, and Formitipora punctata (syn. Phellinus punctatus)
• Elsinoe ampelina an Weinrebe ,• Elsinoe ampelina on grapevine,
• Exserohilum Arten an Mais• Exserohilum species on corn
• Erysiphe cichoracearum und Sphaerotheca fuliginea an Gurkengewächsen,Erysiphe cichoracearum and Sphaerotheca fuliginea on cucurbits,
• Fusarium und Verticillium Arten an verschiedenen Pflanzen wie z.B. F. grami- nearum oder F. culmorum an Getreide oder F. oxysporum an einer Vielzahl vonFusarium and Verticillium species on various plants, e.g. F. graminearum or F. culmorum on cereal or F. oxysporum on a variety of
Pflanzen wie z.B. TomatenPlants such as e.g. tomatoes
• Gaeumanomyces graminis an GetreideGaeumanomyces graminis on cereals
• Gibberella arten an Getreide und Reis (z.B.. Gibberella fujikuroi an Reis)Gibberella species on cereals and rice (eg Gibberella fujikuroi on rice)
• Glσmerella cingulata an Weinrebe und anderen Pflanzen • Grainstaining complex an Reis• Glσmerella cingulata on grapevine and other plants • Grainstaining complex on rice
• Guignardia budwelli an Weinrebe• Guignardia budwelli on grapevine
• Helminthosporium Arten an Mais und Reis• Helminthosporium species on corn and rice
• lsariopsis clavispora an Weinrebe ,• Isariopsis clavispora on grapevine,
• Michrodochium nivale an Getreide • Mycosphaerella Arten an Getreide, Bananen und Erdnüssen, wie z.B. M. gra- minicola an Weizen oder M.fijiensis an Bananen• Michrodochium nivale on cereals • Mycosphaerella species on cereals, bananas and peanuts, e.g. M. granicola on wheat or M.fijiensis on bananas
• Peronospora-Arten an Kohl und Zwiebelgewächsen, wie z.B. P. brassicae an Kohl oder P. destructor an ZwiebelPeronospora species on cabbage and bulbous plants, such as P. brassicae on cabbage or P. destructor on onion
• Phakopsara pachyrhizi und Phakopsara meibomiae an Sojabohnen • Phomopsis Arten an Sojabohnen und Sonnenblumen, P. viticola an Weinrebe• Phakopsara pachyrhizi and Phakopsara meibomiae on soybeans • Phomopsis species on soybeans and sunflowers, P. viticola on grapevine
• Phytophthora infestans an Kartoffeln und Tomaten,• Phytophthora infestans on potatoes and tomatoes,
• Phytophthora Arten an verschiedenen Pflanzen wie z.B. P.capsici an Paprika, • Plasmopara viticola an Weinreben,Phytophthora species on various plants such as P. capsici on peppers, Plasmopara viticola on grapevines,
• Podosphaera leucotricha an Apfel,• Podosphaera leucotricha on apple,
• Pseudocercosporella herpotrichoides an Getreide,Pseudocercosporella herpotrichoides on cereals,
• Pseudoperonospora an verschiedenen Pflanzen wie z.B. P. cubensis an Gurke oder P. humili an HopfenPseudoperonospora on various plants, e.g. P. cubensis on cucumber or P. humili on hops
• Pseudopezicula tracheiphilai an Weinrebe ,• pseudo-pedicel tracheiphilai on grapevine,
• Puccinia Arten an verschiedenen Pflanzen wie z.B. P. triticina, P. striformins, P. hordei oder P.graminis an Getreide, oder P. asparagi an SpargelPuccinia species on various plants, e.g. P. triticina, P. striformins, P. hordei or P.graminis on cereals, or P. asparagi on asparagus
• Pyricularia oryzae , Corticium sasakii , Sarocladium oryzae, S.attenuatum, Entyloma oryzae, an Reis,Pyricularia oryzae, Corticium sasakii, Sarocladium oryzae, S.attenuatum, Entyloma oryzae, on rice,
• Pyricularia grisea an Rasen und Getreide• Pyricularia grisea on lawns and cereals
• Pythium spp. an Rasen, Reis, Mais, Baumwolle, Raps, Sonnenblumen, Zuckerrüben, Gemüse und anderen Pflanzen wie z.B. P.ultiumum an verschiedenen Pflanzen, P. aphanidermatum an Rasen • Rhizoctonia-Arten an Baumwolle, Reis, Kartoffeln, Rasen, Mais, Raps, Kartoffeln, Zuckerrüben, Gemüse und an verschiedenen Pflanzen wie z.B. R.solani an Rüben und verschiedenen Pflanzen,• Pythium spp. on turf, rice, corn, cotton, oilseed rape, sunflowers, sugar beets, vegetables and other plants such as e.g. P.ultiumum on various plants, P. aphanidermatum on lawns • Rhizoctonia species on cotton, rice, potatoes, turf, corn, oilseed rape, potatoes, sugar beets, vegetables and various plants such as e.g. R.solani on turnips and various plants,
• Rhynchosporium secalis an Gerste, Roggen und Triticale• Rhynchosporium secalis on barley, rye and triticale
• Sclerotinia Arten an Raps und Sonnenblumen • Septoria tritici und Stagonospora nodorum an Weizen,• Sclerotinia species on oilseed rape and sunflowers • Septoria tritici and Stagonospora nodorum on wheat,
• Erysiphe (syn. Uncinula) necator an Weinrebe• Erysiphe (syn. Uncinula) necator on grapevine
• Setospaeria Arten an Mais und Rasen• Setospaeria species on corn and turf
• Sphacelotheca reilinia an Mais• Sphacelotheca reilinia on corn
• Thievaliopsis Arten an Sojabohnen und Baumwolle • Tilletia Arten an Getreide• Thievaliopsis species on soybeans and cotton • Tilletia species on cereals
• Ustilago-Arten an Getreide, Mais und Zuckerrohr, wie z.B. U. maydis an MaisUstilago species on cereals, maize and sugarcane, such as U. maydis on corn
• Venturia-Arten (Schorf) an Äpfeln und Birnen wie. z.B. V. inaequalis an Apfel.• Venturia species (scab) on apples and pears like. e.g. V. inaequalis to apple.
Die Mischungen der Verbindungen I und eines Wirkstoffs Il eignen sich besonders zur Bekämpfung von Schadpilzen aus der Klasse der Peronosporomycetes (syn. Oomyce- ten), wie Peronospora-Arten, Phytophthora-Arten, Plasmopara viticola und Pseudope- ronospora-Arten, insbesondere der entsprechenden voranstehend genannten.The mixtures of the compounds I and of an active compound II are particularly suitable for controlling harmful fungi from the class of the Peronosporomycetes (syn. Oomycetes), such as Peronospora species, Phytophthora species, Plasmopara viticola and Pseudoperonospora species, in particular the corresponding species mentioned above.
Die Mischungen der Verbindungen I und Il eignen sich außerdem zur Bekämpfung von Schadpilzen im Materialschutz (z.B. Holz, Papier, Dispersionen für den Anstrich, Fasern bzw. Gewebe) und im Vorratsschutz. Im Holzschutz finden insbesondere folgende Schadpilze Beachtung: Ascomyceten wie Ophiostoma spp., Ceratocystis spp., Aureo- basidium pullulans, Sclerophoma spp., Chaetomium spp., Humicola spp., Petriella spp., Trichurus spp.; Basidiomyceten wie Coniophora spp., Coriolus spp., Gloeophyl- lum spp., Lentinus spp., Pleurotus spp., Poria spp., Serpula spp. und Tyromyces spp., Deuteromyceten wie Aspergillus spp., Cladosporium spp., Penicillium spp., Trichoder- ma spp., Alternaria spp., Paecilomyces spp. und Zygomyceten wie Mucor spp., darüber hinaus im Materialschutz folgende Hefepilze: Candida spp. und Saccharomyces cerevisae.The mixtures of compounds I and II are also suitable for controlling harmful fungi in the protection of materials (eg wood, paper, paint dispersions, fibers or fabrics) and in the protection of stored products. In wood preservation, particular attention is paid to the following harmful fungi: Ascomycetes such as Ophiostoma spp., Ceratocystis spp., Aureosidium pullulans, Sclerophoma spp., Chaetomium spp., Humicola spp., Petriella spp., Trichurus spp .; Basidiomycetes such as Coniophora spp., Coriolus spp., Gloeophlum spp., Lentinus spp., Pleurotus spp., Poria spp., Serpula spp. and Tyromyces spp., Deuteromycetes such as Aspergillus spp., Cladosporium spp., Penicillium spp., Trichodo- spp. ma spp., Alternaria spp., Paecilomyces spp. and Zygomycetes such as Mucor spp., moreover, in the protection of the following yeasts: Candida spp. and Saccharomyces cerevisae.
Die Verbindungen I werden angewendet, indem man die Pilze oder die vor Pilzbefall zu schützenden Pflanzen, Saatgüter, Materialien oder den Erdboden mit einer fungizid wirksamen Menge der Wirkstoffe behandelt. Die Anwendung kann sowohl vor als auch nach der Infektion der Materialien, Pflanzen oder Samen durch die Pilze erfolgen.The compounds I are used by treating the fungi or the plants, seeds, materials or the soil to be protected against fungal attack with a fungicidally effective amount of the active ingredients. The application can be done both before and after the infection of the materials, plants or seeds by the fungi.
Die Verbindungen I und Wirkstoffe Il können gleichzeitig gemeinsam oder getrennt oder nacheinander aufgebracht werden, wobei die Reihenfolge bei getrennter Applikation im allgemeinen keine Auswirkung auf den Bekämpfungserfolg hat.The compounds I and active compounds II can be applied simultaneously together or separately or in succession, the sequence in the case of separate application generally having no effect on the control result.
Bevorzugt setzt man bei der Bereitstellung der Mischungen die reinen Wirkstoffe I und mindestens einen der Wirkstoffe Il bis V ein, denen man weitere Wirkstoffe gegen Schadpilze oder gegen andere Schädlinge wie Insekten, Spinntiere oder Nematoden oder auch herbizide oder wachstumsregulierende Wirkstoffe oder Düngemittel beimischen kann.Preference is given to the preparation of the mixtures, the pure active ingredients I and at least one of the active ingredients II to V, which can be further active against harmful fungi or against other pests such as insects, spider animals or nematodes or herbicidal or growth-regulating agents or fertilizers.
Üblicherweise kommen Mischungen aus Verbindung I und mindestens einem derUsually mixtures of compound I and at least one of
Wirkstoffe Il bis V zur Anwendung. Unter Umständen können jedoch auch Mischungen der Verbindung I mit zwei oder ggf. mehreren Aktivkomponenten vorteilhaft sein.Active substances II to V for use. Under certain circumstances, however, mixtures of compound I with two or optionally several active components may be advantageous.
Die Verbindung I und der Wirkstoff Il werden üblicherweise in einem Gewichtsverhält- nis von 100:1 bis 1 :100, vorzugsweise 20:1 bis 1 :20, insbesondere 10:1 bis 1 :10 angewandt.The compound I and the active compound II are usually employed in a weight ratio of from 100: 1 to 1: 100, preferably from 20: 1 to 1:20, in particular from 10: 1 to 1:10.
Die Verbindung I und der Wirkstoff IM werden üblicherweise in einem Gewichtsverhältnis von 100:1 bis 1 :100, vorzugsweise 20:1 bis 1 :20, insbesondere 10:1 bis 1 :10 an- gewandt.The compound I and the active ingredient IM are usually employed in a weight ratio of 100: 1 to 1: 100, preferably 20: 1 to 1:20, in particular 10: 1 to 1:10.
Die Verbindung I und der Wirkstoff IV werden üblicherweise in einem Gewichtsverhältnis von 100:1 bis 1 :100, vorzugsweise 20:1 bis 1 :20, insbesondere 10:1 bis 1 :10 angewandt.The compound I and the active ingredient IV are usually used in a weight ratio of 100: 1 to 1: 100, preferably 20: 1 to 1:20, in particular 10: 1 to 1:10 applied.
Die Verbindung I und der Wirkstoff V werden üblicherweise in einem Gewichtsverhältnis von 100:1 bis 1 :100, vorzugsweise 20:1 bis 1 :20, insbesondere 10:1 bis 1 :10 angewandt.The compound I and the active ingredient V are usually used in a weight ratio of 100: 1 to 1: 100, preferably 20: 1 to 1:20, in particular 10: 1 to 1:10 applied.
Die weiteren Aktivkomponenten werden gewünschtenfalls im Verhältnis von 20:1 bis 1 :20 zu der Verbindung I zugemischt. Die Aufwandmengen der erfindungsgemäßen Mischungen liegen, vor allem bei landwirtschaftlichen Kulturflächen, je nach Art der Verbindung und des gewünschten Effekts bei 5 g/ha bis 2000 g/ha, vorzugsweise 20 bis 900 g/ha, insbesondere 50 bis 750 g/ha.If desired, the further active components are added to compound I in a ratio of from 20: 1 to 1:20. The application rates of the mixtures according to the invention, especially in agricultural crops, depending on the nature of the compound and the desired effect at 5 g / ha to 2000 g / ha, preferably 20 to 900 g / ha, in particular 50 to 750 g / ha.
Die Aufwandmengen für die Verbindung I liegen entsprechend in der Regel bei 1 bis 1000 g/ha, vorzugsweise 10 bis 900 g/ha, insbesondere 20 bis 750 g/ha.The application rates for the compound I are accordingly generally 1 to 1000 g / ha, preferably 10 to 900 g / ha, in particular 20 to 750 g / ha.
Die Aufwandmengen für den Wirkstoff Il liegen entsprechend in der Regel bei 1 bis 2000 g/ha, vorzugsweise 10 bis 1500 g/ha, insbesondere 40 bis 1000 g/ha.The application rates for the active compound II are accordingly generally from 1 to 2000 g / ha, preferably from 10 to 1500 g / ha, in particular from 40 to 1000 g / ha.
Die Aufwandmengen für den Wirkstoff IM liegen entsprechend in der Regel bei 1 bis 2000 g/ha, vorzugsweise 10 bis 1500 g/ha, insbesondere 40 bis 1000 g/ha.The application rates for the active ingredient IM are correspondingly generally 1 to 2000 g / ha, preferably 10 to 1500 g / ha, in particular 40 to 1000 g / ha.
Die Aufwandmengen für den Wirkstoff IV liegen entsprechend in der Regel bei 1 bis 2000 g/ha, vorzugsweise 10 bis 1500 g/ha, insbesondere 40 bis 1000 g/ha.The application rates for the active ingredient IV are correspondingly generally 1 to 2000 g / ha, preferably 10 to 1500 g / ha, in particular 40 to 1000 g / ha.
Die Aufwandmengen für den Wirkstoff V liegen entsprechend in der Regel bei 1 bis 2000 g/ha, vorzugsweise 10 bis 1500 g/ha, insbesondere 40 bis 1000 g/ha.The application rates for the active ingredient V are correspondingly generally 1 to 2000 g / ha, preferably 10 to 1500 g / ha, in particular 40 to 1000 g / ha.
Bei der Saatgutbehandlung werden im allgemeinen Aufwandmengen an Mischung von 1 bis 1000 g/100 kg Saatgut, vorzugsweise 1 bis 750 g/100 kg, insbesondere 5 bis 500 g/100 kg verwendet.In seed treatment, application rates of mixture of 1 to 1000 g / 100 kg of seed, preferably 1 to 750 g / 100 kg, in particular 5 to 500 g / 100 kg, are generally used.
Das Verfahren zur Bekämpfung von Schadpilzen erfolgt durch die getrennte oder gemeinsame Applikation von Verbindung I und mindestens einem der Wirkstoffe Il bis V oder einer Mischung aus Verbindung I und mindestens einem der Wirkstoffe Il bis V durch Besprühen oder Bestäuben der Samen, der Pflanzen oder der Böden vor oder nach der Aussaat der Pflanzen oder vor oder nach dem Auflaufen der Pflanzen.The method for controlling harmful fungi is carried out by the separate or combined application of compound I and at least one of the active ingredients II to V or a mixture of compound I and at least one of the active ingredients II to V by spraying or dusting the seeds, the plants or the soil before or after sowing the plants or before or after emergence of the plants.
Die erfindungsgemäßen Mischungen, bzw. die Verbindung I und mindestens einer der Wirkstoffe Il bis V können in die üblichen Formulierungen überführt werden, z.B. Lösungen, Emulsionen, Suspensionen, Stäube, Pulver, Pasten und Granulate. Die Anwendungsform richtet sich nach dem jeweiligen Verwendungszweck; sie soll in jedem Fall eine feine und gleichmäßige Verteilung der erfindungsgemäßen Verbindung gewährleisten.The mixtures according to the invention or the compound I and at least one of the active compounds II to V can be converted into the customary formulations, e.g. Solutions, emulsions, suspensions, dusts, powders, pastes and granules. The application form depends on the respective purpose; It should in any case ensure a fine and uniform distribution of the compound according to the invention.
Die Formulierungen werden in bekannter Weise hergestellt, z.B. durch Verstrecken des Wirkstoffs mit Lösungsmitteln und/oder Trägerstoffen, gewünschtenfalls unter Verwen- düng von Emulgiermitteln und Dispergiermitteln. Als Lösungsmittel / Hilfsstoffe kommen dafür im wesentlichen in Betracht: - Wasser, aromatische Lösungsmittel (z.B. Solvesso Produkte, XyIoI), Paraffine (z.B. Erdölfraktionen), Alkohole (z.B. Methanol, Butanol, Pentanol, Benzylalkohol), Keto- ne (z.B. Cyclohexanon, gamma-Butryolacton), Pyrrolidone (NMP, NOP), Acetate (Glykoldiacetat), Glykole, Dimethylfettsäureamide, Fettsäuren und Fettsäureester. Grundsätzlich können auch Lösungsmittelgemische verwendet werden,The formulations are prepared in a known manner, for example by stretching the active ingredient with solvents and / or excipients, if desired with use of emulsifiers and dispersants. Suitable solvents / auxiliaries are essentially: - water, aromatic solvents (eg Solvesso products, xylene), paraffins (eg petroleum fractions), alcohols (eg methanol, butanol, pentanol, benzyl alcohol), ketones (eg cyclohexanone, gamma-butyrolactone), pyrrolidones (NMP, NOP), Acetates (glycol diacetate), glycols, dimethyl fatty acid amides, fatty acids and fatty acid esters. In principle, solvent mixtures can also be used
- Trägerstoffe wie natürliche Gesteinsmehle (z.B. Kaoline, Tonerden, Talkum, Kreide) und synthetische Gesteinsmehle (z.B. hochdisperse Kieselsäure, Silikate); Emulgiermittel wie nichtionogene und anionische Emulgatoren (z.B. Polyoxy- ethylen-Fettalkohol-Ether, Alkylsulfonate und Arylsulfonate) und Dispergiermittel wie Lignin-Sulfitablaugen und Methylcellulose.Excipients such as ground natural minerals (e.g., kaolins, clays, talc, chalk) and ground synthetic minerals (e.g., fumed silica, silicates); Emulsifiers such as nonionic and anionic emulsifiers (for example polyoxyethylene fatty alcohol ethers, alkyl sulfonates and arylsulfonates) and dispersants such as lignin-sulphite liquors and methylcellulose.
Als oberflächenaktive Stoffe kommen Alkali-, Erdalkali-, Ammoniumsalze von Ligninsul- fonsäure, Naphthalinsulfonsäure, Phenolsulfonsäure, Dibutylnaphthalinsulfonsäure, Alkylarylsulfonate, Alkylsulfate, Alkylsulfonate, Fettalkoholsulfate, Fettsäuren und sulfa- tierte Fettalkoholglykolether zum Einsatz, ferner Kondensationsprodukte von sulfonier- tem Naphthalin und Naphthalinderivaten mit Formaldehyd, Kondensationsprodukte des Naphthalins bzw. der Naphtalinsulfonsäure mit Phenol und Formaldehyd, Polyoxyethy- lenoctylphenolether, ethoxyliertes Isooctylphenol, Octylphenol, Nonylphenol, Alkylphe- nolpolyglykolether, Tributylphenylpolyglykolether, Tristerylphenylpolyglykolether, Alkyl- arylpolyetheralkohole, Alkohol- und Fettalkoholethylenoxid-Kondensate, ethoxyliertes Rizinusöl, Polyoxyethylenalkylether, ethoxyliertes Polyoxypropylen, Laurylalkoholpoly- glykoletheracetal, Sorbitester, Ligninsulfitablaugen und Methylcellulose in Betracht.The surface-active substances used are alkali metal, alkaline earth metal, ammonium salts of lignin sulfonic acid, naphthalenesulfonic acid, phenolsulfonic acid, dibutylnaphthalenesulfonic acid, alkylarylsulfonates, alkyl sulfates, alkyl sulfonates, fatty alcohol sulfates, fatty acids and sulfated fatty alcohol glycol ethers, and condensation products of sulfonated naphthalene and naphthalene derivatives with formaldehyde , Condensation products of naphthalene or naphthalenesulfonic acid with phenol and formaldehyde, polyoxyethylene octylphenol ether, ethoxylated isooctylphenol, octylphenol, nonylphenol, alkylphenol polyglycol ethers, tributylphenyl polyglycol ethers, tristerylphenyl polyglycol ethers, alkylaryl polyether alcohols, alcohol and fatty alcohol ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers, ethoxylated polyoxypropylene , Laurylalkoholpoly- glycol ether acetal, sorbitol esters, Ligninsulfitablaugen and methyl cellulose into consideration.
Zur Herstellung von direkt versprühbaren Lösungen, Emulsionen, Pasten oder öldis- persionen kommen Mineralölfraktionen von mittlerem bis hohem Siedepunkt, wie Kero- sin oder Dieselöl, ferner Kohlenteeröle sowie Öle pflanzlichen oder tierischen Ursprungs, aliphatische, cyclische und aromatische Kohlenwasserstoffe, z.B. Toluol, Xy- lol, Paraffin, Tetrahydronaphthalin, alkylierte Naphthaline oder deren Derivate, Methanol, Ethanol, Propanol, Butanol, Cyclohexanol, Cyclohexanon, Isophoron, stark polare Lösungsmittel, z.B. Dimethylsulfoxid, N-Methylpyrrolidon oder Wasser in Betracht.For the preparation of directly sprayable solutions, emulsions, pastes or oil dispersions, there are mineral oil fractions of medium to high boiling point, such as kerosine or diesel oil, coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, e.g. Toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes or their derivatives, methanol, ethanol, propanol, butanol, cyclohexanol, cyclohexanone, isophorone, strong polar solvents, e.g. Dimethylsulfoxide, N-methylpyrrolidone or water into consideration.
Pulver-, Streu- und Stäubmittel können durch Mischen oder gemeinsames Vermählen der wirksamen Substanzen mit einem festen Trägerstoff hergestellt werden.Powders, dispersants and dusts may be prepared by mixing or co-grinding the active substances with a solid carrier.
Granulate, z.B. Umhüllungs-, Imprägnierungs- und Homogengranulate, können durch Bindung der Wirkstoffe an feste Trägerstoffe hergestellt werden. Feste Trägerstoffe sind z.B. Mineralerden, wie Kieselgele, Silikate, Talkum, Kaolin, Attaclay, Kalkstein, Kalk, Kreide, Bolus, Löß, Ton, Dolomit, Diatomeenerde, Calcium- und Magnesiumsulfat, Magnesiumoxid, gemahlene Kunststoffe, Düngemittel, wie z.B. Ammoniumsulfat, Ammoniumphosphat, Ammoniumnitrat, Harnstoffe und pflanzliche Produkte, wie Getreidemehl, Baumrinden-, Holz- und Nussschalenmehl, Cellulosepulver und andere feste Trägerstoffe. Die Formulierungen enthalten im allgemeinen zwischen 0,01 und 95 Gew.-%, vorzugsweise zwischen 0,1 und 90 Gew.-% der Wirkstoffe. Die Wirkstoffe werden dabei in einer Reinheit von 90% bis 100%, vorzugsweise 95% bis 100% (nach NMR-Spektrum) eingesetzt.Granules, for example coated, impregnated and homogeneous granules, can be prepared by binding the active compounds to solid carriers. Solid carriers are, for example, mineral earths, such as silica gels, silicates, talc, kaolin, Attaclay, limestone, lime, chalk, bolus, loess, clay, dolomite, diatomaceous earth, calcium and magnesium sulfate, magnesium oxide, ground plastics, fertilizers, such as ammonium sulfate, ammonium phosphate , Ammonium nitrate, ureas and vegetable products such as cereal flour, bark, wood and nutshell flour, cellulose powder and other solid carriers. The formulations generally contain between 0.01 and 95 wt .-%, preferably between 0.1 and 90 wt .-% of the active ingredients. The active ingredients are used in a purity of 90% to 100%, preferably 95% to 100% (according to NMR spectrum).
Beispiele für Formulierungen sind: 1. Produkte zur Verdünnung in WasserExamples of formulations are: 1. Products for dilution in water
A) Wasserlösliche Konzentrate (SL) 10 Gew. -Teile einer erfindungsgemäßen Verbindung werden mit 90 Gew. -Teilen Wasser oder einem wasserlöslichen Lösungsmittel gelöst. Alternativ werden Netzmittel o- der andere Hilfsmittel zugefügt. Bei der Verdünnung in Wasser löst sich der Wirkstoff. Man erhält auf diese Weise eine Formulierung mit einem Wirkstoffgehalt von 10 Gew.- %.A) Water-soluble concentrates (SL) 10 parts by weight of a compound of the invention are dissolved with 90 parts by weight of water or a water-soluble solvent. Alternatively, wetting agents or other adjuvants are added. When diluted in water, the active ingredient dissolves. This gives a formulation with an active ingredient content of 10% by weight.
B) Dispergierbare Konzentrate (DC)B) Dispersible Concentrates (DC)
20 Gew. -Teile einer erfindungsgemäßen Verbindung werden in 70 Gew.-Teilen Cyclo- hexanon unter Zusatz von 10 Gew.-Teilen eines Dispergiermittels z.B. Polyvinylpyrro- lidon gelöst. Bei Verdünnung in Wasser ergibt sich eine Dispersion. Der Wirkstoffgehalt beträgt 20 Gew.-%20 parts by weight of a compound according to the invention are dissolved in 70 parts by weight of cyclohexanone with the addition of 10 parts by weight of a dispersant, e.g. Polyvinylpyrrolidone dissolved. Dilution in water gives a dispersion. The active ingredient content is 20% by weight
C) Emulgierbare Konzentrate (EC)C) Emulsifiable Concentrates (EC)
15 Gew. -Teile einer erfindungsgemäßen Verbindung werden in 75 Gew.-Teilen XyIoI unter Zusatz von Ca-Dodecylbenzolsulfonat und Ricinusölethoxylat (jeweils 5 Gew.- Teile) gelöst. Bei der Verdünnung in Wasser ergibt sich eine Emulsion. Die Formulierung hat einen Wirkstoffgehalt von 15 Gew.-%.15 parts by weight of a compound according to the invention are dissolved in 75 parts by weight of xylene with addition of calcium dodecylbenzenesulfonate and castor oil ethoxylate (in each case 5 parts by weight). Dilution in water results in an emulsion. The formulation has an active ingredient content of 15% by weight.
D) Emulsionen (EW, EO)D) Emulsions (EW, EO)
25 Gew. -Teile einer erfindungsgemäßen Verbindung werden in 35 Gew.-Teilen XyIoI unter Zusatz von Ca-Dodecylbenzolsulfonat und Ricinusölethoxylat (jeweils 5 Gew.- Teile) gelöst. Diese Mischung wird mittels einer Emulgiermaschine (z.B. Ultraturax) in 30 Gew. Teile Wasser gegeben und zu einer homogenen Emulsion gebracht. Bei der Verdünnung in Wasser ergibt sich eine Emulsion. Die Formulierung hat einen Wirkstoffgehalt von 25 Gew.-%.25 parts by weight of a compound according to the invention are dissolved in 35 parts by weight of xylene with addition of calcium dodecylbenzenesulfonate and castor oil ethoxylate (in each case 5 parts by weight). This mixture is added to 30 parts by weight of water by means of an emulsifying machine (e.g., Ultraturax) and made into a homogeneous emulsion. Dilution in water results in an emulsion. The formulation has an active ingredient content of 25% by weight.
E) Suspensionen (SC, OD)E) suspensions (SC, OD)
20 Gew. -Teile einer erfindungsgemäßen Verbindung werden unter Zusatz von 10 Gew.-Teilen Dispergier- und Netzmitteln und 70 Gew.-Teilen Wasser oder einem organischen Lösungsmittel in einer Rührwerkskugelmühle zu einer feinen Wirkstoffsuspen- sion zerkleinert. Bei der Verdünnung in Wasser ergibt sich eine stabile Suspension des Wirkstoffs. Der Wirkstoffgehalt in der Formulierung beträgt 20 Gew.-% . F) Wasserdispergierbare und wasserlösliche Granulate (WG, SG)20 parts by weight of a compound according to the invention are comminuted with the addition of 10 parts by weight of dispersants and wetting agents and 70 parts by weight of water or an organic solvent in a stirred ball mill to a fine Wirkstoffsuspension sion. Dilution in water results in a stable suspension of the active ingredient. The active ingredient content in the formulation is 20% by weight. F) Water-dispersible and water-soluble granules (WG, SG)
50 Gew.-Teile einer erfindungsgemäßen Verbindung werden unter Zusatz von 50 Gew- Teilen Dispergier- und Netzmitteln fein gemahlen und mittels technischer Geräte (z.B. Extrusion, Sprühturm, Wirbelschicht) als wasserdispergierbare oder wasserlösliche Granulate hergestellt. Bei der Verdünnung in Wasser ergibt sich eine stabile Dispersion oder Lösung des Wirkstoffs. Die Formulierung hat einen Wirkstoffgehalt von 50 Gew.- %.50 parts by weight of a compound according to the invention are finely ground with the addition of 50 parts by weight of dispersants and wetting agents and prepared by means of industrial equipment (for example extrusion, spray tower, fluidized bed) as water-dispersible or water-soluble granules. Dilution in water results in a stable dispersion or solution of the active ingredient. The formulation has an active ingredient content of 50% by weight.
G) Wasserdispergierbare und wasserlösliche Pulver (WP, SP) 75 Gew.-Teile einer erfindungsgemäßen Verbindung werden unter Zusatz von 25 Gew.-Teilen Dispergier- und Netzmitteln sowie Kieselsäuregel in einer Rotor-Strator Mühle vermählen. Bei der Verdünnung in Wasser ergibt sich eine stabile Dispersion oder Lösung des Wirkstoffs. Der Wirkstoffgehalt der Formulierung beträgt 75 Gew.-%.G) Water-Dispersible and Water-Soluble Powders (WP, SP) 75 parts by weight of a compound according to the invention are ground in a rotor-stator mill with the addition of 25 parts by weight of dispersing and wetting agents and silica gel. Dilution in water results in a stable dispersion or solution of the active ingredient. The active ingredient content of the formulation is 75% by weight.
2. Produkte für die Direktapplikation2. Products for direct application
H) Stäube (DP)H) dusts (DP)
5 Gew.-Teile einer erfindungsgemäßen Verbindung werden fein gemahlen und mit 95 Gew.-Teilen feinteiligem Kaolin innig vermischt. Man erhält dadurch ein Stäubemittel mit einem Wirkstoffgehalt von 5 Gew.-%.5 parts by weight of a compound according to the invention are finely ground and intimately mixed with 95 parts by weight of finely divided kaolin. This gives a dust with an active ingredient content of 5 wt .-%.
J) Granulate (GR, FG, GG, MG)J) Granules (GR, FG, GG, MG)
0,5 Gew-Teile einer erfindungsgemäßen Verbindung werden fein gemahlen und mit 99,5 Gew.-Teilen Trägerstoffe verbunden. Gängige Verfahren sind dabei die Extrusion, die Sprühtrocknung oder die Wirbelschicht. Man erhält dadurch ein Granulat für die Direktapplikation mit einem Wirkstoffgehalt von 0,5 Gew.-%.0.5 parts by weight of a compound according to the invention are finely ground and combined with 99.5 parts by weight of carriers. Common processes are extrusion, spray drying or fluidized bed. This gives a granulate for direct application with an active ingredient content of 0.5 wt .-%.
K) ULV- Lösungen (UL)K) ULV solutions (UL)
10 Gew.-Teile einer erfindungsgemäßen Verbindung werden in 90 Gew.-Teilen eines organischen Lösungsmittel z.B. XyIoI gelöst. Dadurch erhält man ein Produkt für die Direktapplikation mit einem Wirkstoffgehalt von 10 Gew.-%.10 parts by weight of a compound according to the invention are dissolved in 90 parts by weight of an organic solvent, e.g. XyIoI solved. This gives a product for direct application with an active ingredient content of 10 wt .-%.
Die Wirkstoffe können als solche, in Form ihrer Formulierungen oder den daraus berei- teten Anwendungsformen, z.B. in Form von direkt versprühbaren Lösungen, Pulvern, Suspensionen oder Dispersionen, Emulsionen, Öldispersionen, Pasten, Stäubmitteln, Streumitteln, Granulaten durch Versprühen, Vernebeln, Verstäuben, Verstreuen oder Gießen angewendet werden. Die Anwendungsformen richten sich ganz nach den Verwendungszwecken; sie sollten in jedem Fall möglichst die feinste Verteilung der erfin- dungsgemäßen Wirkstoffe gewährleisten. Wässrige Anwendungsformen können aus Emulsionskonzentraten, Pasten oder netzbaren Pulvern (Spritzpulver, Öldispersionen) durch Zusatz von Wasser bereitet werden. Zur Herstellung von Emulsionen, Pasten oder Öldispersionen können die Substanzen als solche oder in einem Öl oder Lösungsmittel gelöst, mittels Netz-, Haft-, Dispergier- oder Emulgiermitttel in Wasser homogenisiert werden. Es können aber auch aus wirksamer Substanz Netz-, Haft-, Dispergier- oder Emulgiermittel und eventuell Lösungsmittel oder Öl bestehende Konzentrate hergestellt werden, die zur Verdünnung mit Wasser geeignet sind.The active compounds can be used as such, in the form of their formulations or the application forms prepared therefrom, for example in the form of directly sprayable solutions, powders, suspensions or dispersions, emulsions, oil dispersions, pastes, dusts, scattering agents, granules by spraying, atomizing, dusting, Scattering or pouring are applied. The forms of application depend entirely on the intended use; In any case, they should ensure as far as possible the finest distribution of the active compounds according to the invention. Aqueous application forms can be prepared from emulsion concentrates, pastes or wettable powders (wettable powders, oil dispersions) by adding water. For the preparation of emulsions, pastes or oil dispersions, the substances, as such or dissolved in an oil or solvent, can be homogenized in water by means of wetter, tackifier, dispersant or emulsifier. But it can also be made of effective substance wetting, adhesion, dispersing or emulsifying and possibly solvent or oil concentrates, which are suitable for dilution with water.
Die Wirkstoffkonzentrationen in den anwendungsfertigen Zubereitungen können in größeren Bereichen variiert werden. Im allgemeinen liegen sie zwischen 0,0001 und 10%, vorzugsweise zwischen 0,01 und 1 %.The active compound concentrations in the ready-to-use preparations can be varied within wide ranges. In general, they are between 0.0001 and 10%, preferably between 0.01 and 1%.
Die Wirkstoffe können auch mit gutem Erfolg im Ultra-Low-Volume-Verfahren (ULV) verwendet werden, wobei es möglich ist, Formulierungen mit mehr als 95 Gew.-% Wirkstoff oder sogar den Wirkstoff ohne Zusätze auszubringen.The active ingredients can also be used with great success in the ultra-low-volume (ULV) process, it being possible to apply formulations containing more than 95% by weight of active ingredient or even the active ingredient without additives.
Zu den Wirkstoffen können Öle verschiedenen Typs, Netzmittel, Adjuvante, gegebenenfalls auch erst unmittelbar vor der Anwendung (Tankmix), zugesetzt werden. Diese Mittel werden üblicherweise zu den erfindungsgemäßen Mitteln im Gewichtsverhältnis 1 :100 bis 100:1 , bevorzugt 1 :10 bis 10:1 , zugemischt.To the active ingredients oils of various types, wetting agents, adjuvants, possibly also immediately before use (tank mix), are added. These agents are usually admixed to the compositions according to the invention in a weight ratio of 1: 100 to 100: 1, preferably 1:10 to 10: 1.
Die Verbindung I und mindestens einer der Wirkstoffe Il bis V, bzw. die Mischungen oder die entsprechenden Formulierungen werden angewendet, indem man die Schad- pilze, die von ihnen freizuhaltenden Pflanzen, Samen, Böden, Flächen, Materialien oder Räume mit einer fungizid wirksamen Menge der Mischung, bzw. der Verbindung I und mindestens einem der Wirkstoffe Il bis V bei getrennter Ausbringung, behandelt. Die Anwendung kann vor oder nach dem Befall durch die Schadpilze erfolgen.The compound I and at least one of the active ingredients II to V or the mixtures or the corresponding formulations are used by removing the harmful fungi, the plants, seeds, soils, surfaces, materials or spaces having a fungicidally effective amount the mixture, or the compound I and at least one of the active ingredients II to V in separate application, treated. The application can be made before or after the attack by the harmful fungi.
Die fungizide Wirkung der Einzelverbindungen und der erfindungsgemäßen Mischungen ließ sich durch die folgenden Versuche zeigen.The fungicidal action of the individual compounds and of the mixtures according to the invention was demonstrated by the following experiments.
Der Wirkungsgrad (W) wird nach der Formel von Abbot wie folgt berechnet:The efficiency (W) is calculated according to the formula of Abbot as follows:
W = (1 - α/ß) 100W = (1-α / β) 100
α entspricht dem Pilzbefall der behandelten Pflanzen in % und ß entspricht dem Pilzbefall der unbehandelten (Kontroll-) Pflanzen in %α corresponds to the fungal infestation of the treated plants in% and β corresponds to the fungal infestation of the untreated (control) plants in%
Bei einem Wirkungsgrad von 0 entspricht der Befall der behandelten Pflanzen demjenigen der unbehandelten Kontrollpflanzen; bei einem Wirkungsgrad von 100 weisen die behandelten Pflanzen keinen Befall auf. Die zu erwartenden Wirkungsgrade für Wirkstoffkombinationen wurden nach der Colby- Formel (Colby, S. R. (Calculating synergistic and antagonistic responses of herbicide Combinations", Weeds, ^5, S. 20 - 22, 1967) ermittelt und mit den beobachteten Wirkungsgraden verglichen.With an efficiency of 0, the infestation of the treated plants corresponds to that of the untreated control plants; at an efficiency of 100, the treated plants have no infestation. The expected efficiencies for drug combinations were determined according to the Colby formula (Colby, SR (Calculating synergistic and antagonistic responses of herbicidal combinations, Weeds, 5, p 20 - 22, 1967) and compared with the observed efficiencies.
Colby Formel:Colby formula:
E = x + y - x-y/100E = x + y - x-y / 100
E zu erwartender Wirkungsgrad, ausgedrückt in % der unbehandelten Kontrolle, beim Einsatz der Mischung aus den Wirkstoffen A und B in den Konzentrationen a und b x der Wirkungsgrad, ausgedrückt in % der unbehandelten Kontrolle, beim Einsatz des Wirkstoffs A in der Konzentration a y der Wirkungsgrad, ausgedrückt in % der unbehandelten Kontrolle, beim Einsatz des Wirkstoffs B in der Konzentration bE expected efficiency, expressed as% of untreated control, using the mixture of active substances A and B at concentrations a and bx the efficiency expressed as% of untreated control, when using active substance A at the concentration ay the efficiency, expressed as% of untreated control, when using active substance B in concentration b
Der Wirkstoff Epoxiconazol und Triticonazol wurde als handelsübliche Formulierung verwendet.The active ingredient epoxiconazole and triticonazole was used as a commercial formulation.
Anwendungsbeispiel Nr. 1 - Aktivität gegen den Verursacher des Reisbrandes Pyricularia oryzae im Mikrotitter-Test (Pyrior)Application Example No. 1 - Activity against the cause of the rice blast Pyricularia oryzae in the microtiter test (Pyrior)
Die Stammlösung wird in eine Mikrotitterplatte (MTP) pipettiert und mit einem wässrigen Pilznährmedium auf Malzbasis auf die angegebene Wirkstoffkonzentration verdünnt. Anschließend erfolgte die Zugabe einer wässrigen Sporensuspension von Pyricularia oryzae. Die Platten wurden in einer wasserdampf-gesättigten Kammer bei Temperaturen von 18°C aufgestellt. Mit einem Absorbtionsphotometer wurden die MTPs am 7. Tag nach der Inokulation bei 405nm gemessen. Die gemessenen Parameter wurden mit dem Wachstum der wirkstofffreienThe stock solution is pipetted into a microtiter plate (MTP) and diluted with an aqueous malt-based mushroom nutrient medium to the stated active substance concentration. This was followed by the addition of an aqueous spore suspension of Pyricularia oryzae. The plates were placed in a water vapor saturated chamber at temperatures of 18 ° C. With an absorbance photometer, the MTPs were measured at 405 nm on the 7th day after inoculation. The measured parameters were consistent with the growth of drug-free
Kontrollvariante (=100%)und dem pilz- und wirkstofffreien Leerwert verrechnet, um das relative Wachstum in % der Pathogene in den einzelnen Wirkstoffen zu ermitteln.Control variant (= 100%) and the fungus-free and active substance-free blank value are calculated in order to determine the relative growth in% of the pathogens in the individual active substances.
Die visuell ermittelten Werte für den Prozentanteil befallener Blattfläche wurde zunächst gemittelt, dann in Wirkungsgrade als % der unbehandelten Kontrolle umgerechnet.The visually determined values for the percentage of affected leaf area were first averaged, then converted into efficiencies as% of the untreated control.
Wirkungsgrad 0 ist gleicher Befall wie in der unbehandelten Kontrolle, Wirkungsgrad 100 ist 0 % Befall. Die zu erwartenden Wirkungsgrade für Wirkstoffkombinationen wurden nach der Colby-Formel (Colby, S. R. (Calculating synergistic and antagonistic responses of herbicide Combinations", Weeds, ^5, S. 20 - 22, 1967) ermittelt und mit den beobachteten Wirkungsgraden verglichen. Efficiency 0 is the same infestation as in the untreated control, efficiency 100 is 0% infestation. The expected efficiencies for drug combinations were determined according to the Colby formula (Colby, SR (Calculating synergistic and antagonistic responses of herbicidal combinations, Weeds, 5, p 20 - 22, 1967) and compared with the observed efficiencies.
Aus den Ergebnissen der Versuche geht hervor, dass die erfindungsgemäßen Mischungen aufgrund des Synergismus erheblich besser wirksam sind, als nach der CoI- by-Formel vorausberechnet. From the results of the experiments, it is clear that the mixtures according to the invention are considerably more effective due to the synergism than predicted by the CoI by formula.

Claims

Patentansprüche claims
1. Fungizide Mischung, enthaltend1. Fungicidal mixture containing
(1 ) Epoxiconazol der Formel I(1) epoxiconazole of the formula I.
oder dessen Salze oder Addukteor its salts or adducts
und mindestens ein weiteres Triazol oder dessen Salze oder Addukte, ausgewählt ausand at least one other triazole or its salts or adducts selected from
(2) Triticonazol der Formel Il(2) Triticonazole of the formula II
oderor
(3) Difenconazol der Formel(3) Difenconazole of the formula
oder (4) Hexaconazol der Formel IVor (4) hexaconazole of formula IV
oderor
(5) Bromuconazol der Formel V(5) Bromuconazole of the formula V
in einer synergistisch wirksamen Menge.in a synergistically effective amount.
2. Fungizide Mischung nach Anspruch 1 , enthaltend Epoxiconazol der Formel I und Triticonazol der Formel II.2. Fungicidal mixture according to claim 1, containing epoxiconazole of the formula I and triticonazole of the formula II.
3. Fungizide Mischung nach Anspruch 1 , enthaltend Epoxiconazol der Formel I und Difenconazol der Formel IM.3. Fungicidal mixture according to claim 1, containing epoxiconazole of the formula I and difenconazole of the formula III.
4. Fungizide Mischung nach Anspruch 1 , enthaltend Epoxiconazol der Formel I und Hexaconazol der Formel IV.4. A fungicidal mixture according to claim 1, containing epoxiconazole of the formula I and hexaconazole of the formula IV.
5. Fungizide Mischung nach Anspruch 1 , enthaltend Epoxiconazol der Formel I und Bromuconazol der Formel V.5. Fungicidal mixture according to claim 1, containing epoxiconazole of the formula I and bromuconazole of the formula V.
6. Fungizide Mischung nach Anspruch 1 , dadurch gekennzeichnet, dass das Gewichtsverhältnis von Epoxiconazol der Formel I zu dem jeweiligen Triazol der Formeln Il bis V 100 : 1 bis 1 : 100 beträgt.6. Fungicidal mixture according to claim 1, characterized in that the weight ratio of Epoxiconazol of the formula I to the respective triazole of the formulas II to V is 100: 1 to 1: 100.
7. Verfahren zur Bekämpfung von Schadpilzen, dadurch gekennzeichnet, dass man die Schadpilze, deren Lebensraum oder die von ihnen freizuhaltenden Pflanzen, Samen, Böden, Flächen, Materialien oder Räume mit der fungiziden Mischung gemäß Anspruch 1 behandelt.7. A method for controlling harmful fungi, characterized in that the harmful fungi, their habitat or the plants to be kept free of them, Seeds, soils, areas, materials or spaces treated with the fungicidal mixture according to claim 1.
8. Verfahren nach Anspruch 7, dadurch gekennzeichnet, dass man die Verbindung der Formel I gemäß Anspruch 1 und mindestens eine Verbindung der Formel Il bis IV gemäß Anspruch 1 gleichzeitig, und zwar gemeinsam oder getrennt, oder nacheinander ausbringt.8. The method according to claim 7, characterized in that the compound of the formula I according to claim 1 and at least one compound of the formula II to IV according to claim 1 simultaneously, and jointly or separately, or successively auszustingt.
9. Verfahren nach Anspruch 7 oder 8, dadurch gekennzeichnet, dass man die fun- gizide Mischung oder die Verbindung der Formel I mit mindestens einer Verbindung der Formel Il bis V gemäß Anspruch 1 in einer Menge von 5 g/ha bis 2000 g/ha aufwendet.9. The method according to claim 7 or 8, characterized in that the fungicidal mixture or the compound of formula I with at least one compound of formula II to V according to claim 1 in an amount of 5 g / ha to 2000 g / ha spends.
10. Verfahren nach Anspruch 7 oder 8, dadurch gekennzeichnet, dass man die Ver- bindung I mit mindestens einer der Verbindungen Il bis V gemäß Anspruch 1 oder die Mischung gemäß Anspruch 1 in einer Menge von 1 g bis 1000 g pro 100 kg Saatgut anwendet.10. The method according to claim 7 or 8, characterized in that one applies the compound I with at least one of the compounds II to V according to claim 1 or the mixture according to claim 1 in an amount of 1 g to 1000 g per 100 kg of seed ,
1 1. Saatgut, enthaltend die Mischung gemäß Anspruch 1 in einer Menge von 1 g bis 1000 g pro 100 kg.1 1. Seed containing the mixture according to claim 1 in an amount of 1 g to 1000 g per 100 kg.
12. Verwendung der Verbindung I mit mindestens einer der Verbindungen Il bis V gemäß Anspruch 1 zur Herstellung eines zur Bekämpfung von Schadpilzen geeigneten Mittels.12. Use of the compound I with at least one of the compounds II to V according to claim 1 for the preparation of a suitable agent for controlling harmful fungi.
13. Fungizide Mittel, enthaltend die fungizide Mischung gemäß Anspruch 1 sowie einen festen oder flüssigen Träger. 13. A fungicidal composition containing the fungicidal mixture according to claim 1 and a solid or liquid carrier.
EP06793222A 2005-09-14 2006-09-05 Triazole-based fungicidal mixtures Withdrawn EP1926376A1 (en)

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EP2192837B1 (en) * 2007-09-18 2017-05-10 Basf Se Fungicidal mixtures of triticonazole and difenoconazole
CN101743972A (en) * 2010-01-22 2010-06-23 青岛奥迪斯生物科技有限公司 High-effect bactericidal composites with epoxiconazole and difenoconazole
WO2023139352A1 (en) * 2022-01-19 2023-07-27 UPL Corporation Limited Fungicidal combinations and methods for controlling phytopathogenic fungi

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US5266585A (en) * 1981-05-12 1993-11-30 Ciba-Geigy Corporation Arylphenyl ether derivatives, compositions containing these compounds and use thereof
CA1271764A (en) * 1985-03-29 1990-07-17 Stefan Karbach Azolylmethyloxiranes, their preparation and their use as crop protection agents
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JP2009509936A (en) 2009-03-12
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EA015733B1 (en) 2011-10-31
US20090270255A1 (en) 2009-10-29
BRPI0615840A2 (en) 2012-12-18
EA201000184A1 (en) 2010-06-30
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AU2006290811A1 (en) 2007-03-22
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CN101262767A (en) 2008-09-10
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