EP1926375A1

EP1926375A1 - Triazole-based fungicidal mixtures

Info

Publication number: EP1926375A1
Application number: EP06793098A
Authority: EP
Inventors: Martin Semar; Dieter Strobel; Jens Bruns; Reinhard Stierl; Frank Werner
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 2005-09-09
Filing date: 2006-08-31
Publication date: 2008-06-04
Also published as: CN101262766A; AU2006289120B2; WO2007028756A1; EA013476B1; CN101262766B; AU2006289120A1; CA2620194A1; UA89562C2; JP2009507805A; BRPI0615857A2; AR056065A1; EA200800678A1; US20090099020A1

Abstract

The invention relates to fungicidal mixtures which comprise (1) the epoxiconazole of formula (I) or the salts or adducts thereof, and (2) the fluquinconazole of formula (II) or the salts or adducts thereof 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

Fungicidal mixtures based on triazoles

description

The present invention relates to fungicidal mixtures containing

(1) epoxiconazole of the formula I.

or its salts or adducts

and

(2) Fluquinconazole of the formula II

or its salts or adducts

in a synergistically effective amount.

In addition, the invention relates to a method for controlling harmful fungi with mixtures of the compound I with the compound II and the use of the compound I with the compound II for the preparation of such mixtures and compositions containing these mixtures.

From WO 03/073851 a number of drug combinations of prothioconazole with a variety of other triazoles such as epoxiconazole is known. Epoxiconazole of the formula I and its use as a crop protection agent is described in EP-B 0 196 038.

The fluquinconazole of formula II is described in Pesticide Manual, 12th Ed. (2000), page 449.

With regard to a reduction of the application rates and a widening of the spectrum of action of the known compounds, the present invention was based on mixtures which show an improved action against harmful fungi, in particular for certain indications, with a reduced total amount of applied active substances.

Accordingly, the mixtures defined above were found. It has also been found that, with simultaneous simultaneous or separate application of the compound I and of an active compound II or, when using the compound I and an active compound II, harmful fungi can be controlled better successively than with the individual compounds (synergistic mixtures). Compound I can be used as a synergist for a variety of different agents. 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 epoxiconazole of the formula I

is known from EP-B 0196038.

The fluquinconazole of the formula II

is in Pesticide Manual, 12th Ed. (2000), page 449.

The compounds I and II are able to form salts or adducts with inorganic or organic acids or with metal ions because of the basic character of the nitrogen atoms contained in them.

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 radicals), wherein the alkyl or aryl radicals may carry further substituents, eg p-toluenesulfonic acid, salicylic acid, p-aminosalicylic acid, 2-phenoxybenzoic acid, 2-acetoxybenzoic acid, etc.

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.

They are particularly important 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.

Specifically, they are suitable for controlling the following plant diseases: Alternaria species on vegetables, oilseed rape, sugar beets and fruits and rice, such as.

A.solani or A. alternata on potatoes and tomatoes

• Aphanomyces species of sugar beets and vegetables

• Ascochyta species on cereals and vegetables

Bipolaris and Drechslera species on maize, cereals, rice and turf, e.g. D.maydis on corn

• Blumeria graminis (powdery mildew) on cereals,

• Botrytis cinerea (gray mold) on strawberries, vegetables, flowers and vines,

• Bremia lactucae on lettuce • Cercospora species on corn, soybeans, rice and sugar beets

Cochliobolus species on corn, cereals, rice, e.g. Cochliobolus sativus on cereals, Cochliobolus miyabeanus on rice

• Colletotricum species of soybeans and cotton

• Drechslera species, Pyrenophora species on maize, cereals, rice and turf, e.g. D.teres to barley or D. tritici-repentis to wheat

• Esca on grapevine caused by Phaeoacremonium chlamydosporium, Ph. Aleophilum, and Formitipora punctata (syn. Phellinus punctatus)

• Elsinoe ampelina on grapevine,

• Exserohilum species on corn • Erysiphe cichoracearum and Sphaerotheca fuliginea on cucurbits,

Fusarium and Verticillium species on various plants, e.g. F. graminearum or F. culmorum on cereal or F. oxysporum on a variety of plants such as e.g. tomatoes

• Gaeumanomyces graminis on cereals • Gibberella species on cereals and rice (eg Gibberella fujikuroi on rice)

• Glσmerella cingulata on grapevine and other plants

• Grainstaining complex on rice

• Guignardia budwelli on grapevine

• Helminthosporium species on maize and rice • Isariopsis clavispora on grapevine,

• 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

• Phakopsara pachyrhizi and Phakopsara meibomiae on soybeans

• Phomopsis species on soybeans and sunflowers, P. viticola on grapevine • Phytophthora infestans on potatoes and tomatoes,

Phytophthora species on various plants, e.g. P.capsici on paprika,

Plasmopara viticola on grapevines,

• Podosphaera leucotricha on apple, • Pseudocercosporella herpotrichoides on cereals,

Pseudoperonospora on various plants, e.g. P. cubensis on cucumber or P. humili on hops

• pseudo-pedicel tracheiphilai on grapevine,

Puccinia 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, on rice,

• Pyricularia grisea on lawns and cereals

• Pythium spp. on grass, rice, maize, cotton, oilseed rape, sunflowers, sugar beets, vegetables and other plants such as e.g. P.ultiumum at different

Plants, P. aphanidermatum on lawn

• Rhizoctonia species on cotton, rice, potatoes, turf, corn, oilseed rape, potatoes, sugar beet, vegetables and various plants such as e.g. R.solani on turnips and various plants, • Rhynchosporium secalis on barley, rye and triticale

• Sclerotinia species on oilseed rape and sunflowers

• Septoria tritici and Stagonospora nodorum on wheat,

• Erysiphe (syn. Uncinula) necator on grapevine

• Setospaeria species on corn and turf • Sphacelotheca reilinia on maize

• Thievaliopsis species on soybeans and cotton

• Tilletia species of cereals

Ustilago species on cereals, maize and sugarcane, such as U. maydis on corn

• Venturia species (scab) on apples and pears like. e.g. V. inaequalis to apple.

The mixtures of the compound I and of an active compound II are particularly suitable for controlling harmful fungi from the class of the Peronosporomycetes (syn. Oomyces), 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. 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., Gloeophyl lum spp., Lentinus spp., Pleurotus spp., Poria spp., Serpula spp. and Tyromyces spp., Deuteromycetes such as Aspergillus spp., Cladosporium spp., Penicillium spp., Trichoderm spp., Alternaria spp., Paecilomyces spp. and Zygomycetes such as Mucor spp., moreover, in the protection of the following yeasts: Candida spp. and Saccharomyces cerevisae.

Compound I is used by treating the fungi or the plants, seeds, materials or 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 compound 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.

In the preparation of the mixtures, the pure active ingredients I and II are preferably used, to which other active substances can be added against harmful fungi or against other pests such as insects, spider animals or nematodes or else herbicidal or growth-regulating active substances or fertilizers.

Usually, mixtures of compound I and the active ingredient II are used. 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 100: 1 to 1: 100, preferably 20: 1 to 1:20, in particular 10: 1 to 1:10.

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.

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. 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.

The method of controlling harmful fungi is by the separate or combined application of compound I and active compound II or a mixture of compound I and active compound II by spraying or dusting the seeds, plants or soils before or after sowing the plants or before or after the emergence of the plants.

The mixtures according to the invention or the compound I and the active compound II 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, e.g. by stretching the active ingredient with solvents and / or carriers, if desired using 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

Carriers 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.

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. For the production of directly sprayable solutions, emulsions, pastes or oil dispersions, 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, eg toluene, Xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes or derivatives thereof, methanol, ethanol, propanol, butanol, cyclohexanol, cyclohexanone, isophorone, strongly polar solvents, for example dimethylsulfoxide, N-methylpyrrolidone or water.

Powders, dispersants and dusts may be prepared by mixing or co-grinding the active substances with a solid carrier.

Granules, e.g. Coated, impregnated and homogeneous granules can be prepared by binding the active compounds to solid carriers. Solid carriers are e.g. Mineral earths, such as silica gels, silicates, talc, kaolin, attaclay, limestone, lime, chalk, bolus, loess, clay, dolomite, diatomaceous earth, calcium and magnesium sulphate, magnesium oxide, ground plastics, fertilizers, e.g. Ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas and vegetable products such as cereal flour, tree bark, wood and nutshell meal, 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).

Examples of formulations are: 1. Products for dilution in water

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) Dispersible Concentrates (DC)

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, for example polyvinylpyrrolidone. Dilution in water gives a dispersion. The active ingredient content is 20% by weight C) Emulsifiable Concentrates (EC)

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 substance content of 15% by weight.

D) Emulsions (EW, EO)

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) suspensions (SC, OD)

20 parts by weight of a compound of 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 active substance suspension. 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 parts by weight of a compound according to the invention are finely ground with the addition of 50 parts by weight dispersing and wetting agents and by means of technical equipment (eg extrusion, spray tower, fluidized bed) as water-dispersible or water-soluble granules produced. 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) Water-dispersible and water-soluble powders (WP, SP)

75 parts by weight of a compound according to the invention are ground with the addition of 25 parts by weight of dispersants and wetting agents and silica gel in a rotor-Strator mill. 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. Products for direct application

H) Dusts (DP) 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) Granules (GR, FG, GG, MG)

0.5 parts by weight of a compound according to the invention are finely ground and combined with 99.5 parts by weight of excipients. 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 solutions (UL)

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 .-%.

The active compounds can be used as such, in the form of their formulations or the use forms prepared therefrom, e.g. in the form of directly sprayable solutions, powders, suspensions or dispersions, emulsions, oil dispersions, pastes, dusts, scattering agents, granules by spraying, misting, dusting, scattering or pouring. 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. To prepare emulsions, pastes or oil dispersions, the substances, as such or dissolved in an oil or solvent, can be homogenized in water by means of wetting agents, tackifiers, dispersants or emulsifiers. 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.

Oils of various types, wetting agents, adjuvants, if appropriate also immediately before use (tank mix), may be added to the active substances. 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 compounds I and II, or the mixtures or the corresponding formulations, are applied by mixing the harmful fungi, the plants, seeds, soils, surfaces, materials or spaces to be kept free of them with a fungicidally effective amount of the mixture Compounds I and II with separate application, treated. The application can be made before or after the attack by the harmful fungi.

The fungicidal action of the individual compounds and of the mixtures according to the invention was demonstrated by the following experiments.

The active compounds were prepared separately or together as a stock solution with 25 mg of active ingredient, which with a mixture of acetone and / or dimethyl sulfoxide and the emulsifier Uniperol ^® EL (wetting agent with emulsifying and dispersing action based on ethoxylated alkylphenols) in the volume ratio solvent- Emulsifier from 99 to 1 ad 10 ml was filled. It was then made up to 100 ml with water. This stock solution was diluted with the described solvent-emulsifier-water mixture to the drug concentration given below.

The visually determined values for the percentage of affected leaf areas were converted into efficiencies as% of the untreated control:

The efficiency (W) is calculated according to the formula of Abbot as follows:

W = (1-α / β) 100

α corresponds to the fungal infestation of the treated plants in% and β corresponds to the fungal infestation of the untreated (control) plants in%

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, S.R. (Calculating Synergistic and Antagonistic Ac- tions of herbicide Combinations, Weeds, 5, p. 20-22, 1967) and compared with the observed efficiencies.

Colby formula: E = x + y - xy / 100 expected efficiency, expressed as% of untreated control, using the mixture of active substances A and B at concentrations a and b, expressed as% of untreated control, using active substance A at concentration a, efficiency in% of the untreated control, when using the active substance B in the concentration b

The active substances were formulated separately as stock solution with a concentration of 10000 ppm in DMSO.

The active ingredient epoxiconazole was used as a commercial formulation.

15 Application Example No. 1 - Activity against the cause of the gray mold Botrytis cinerea in the microtiter test (Botrci)

The stock solution is pipetted into a microtiter plate (MTP) and washed with an aqueous

Malt-based fungal nutrient diluted to the specified active substance concentration. Subsequently, an aqueous spore suspension of Botrytis cinerea was added. 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 compared with the growth of the drug-free control variant and the fungus-free and drug-free blank to the relative

To determine growth in% of the pathogens in the individual active substances.

The visually determined values for the percentage of affected leaf area were first averaged, then converted into efficiencies as% of the untreated control.

Efficiency 0 is the same infestation as in the untreated control, efficiency 100 30 is 0% infestation. The expected efficiencies for drug combinations were determined according to the Colby formula (Colby, S.R. (Calculating synergistic and antagonistic responses of herbicidal combinations, Weeds, supra, pp. 20-22, 1967) and compared with the observed efficiencies.

Claims

claims

1. Fungicidal mixture containing

(1) epoxiconazole of the formula I.

or its salts or adducts

and

(2) Fluquinconazole of the formula II

or its salts or adducts

in a synergistically effective amount.

2. Fungicidal mixture according to claim 1, characterized in that the weight ratio of epoxiconazole of the formula I to fluquinconazole of the formula II is 100: 1 to 1: 100.

3. A method for controlling phytopathogenic harmful fungi, characterized in that treating the harmful fungi, their habitat or the plants to be protected from them, the soil or seeds with the fungicidal mixture according to claim 1.

4. The method according to claim 3, characterized in that epoxiconazole of the formula I according to claim 1 and fluquinconazole of the formula II according to claim 1 simultaneously, and jointly or separately, or successively.

5. The method according to claim 3 or 4, characterized in that the fungicidal mixture or Epoxiconazol of the formula I with Fluquinconazol of the formula II according to claim 1 in an amount of 5 g / ha to 2000 g / ha.

6. The method according to claim 3 or 4, characterized in that applying the compounds I and II 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.

7. Seed containing the mixture according to claim 1 in an amount of 1 g to 1000 g per 100 kg.

8. Use of the compounds I and II according to claim 1 for the preparation of a suitable agent for controlling harmful fungi.

9. A fungicidal composition containing the fungicidal mixture according to claim 1 and a solid or liquid carrier.