EP1353557A1

EP1353557A1 - Fungicidal mixture

Info

Publication number: EP1353557A1
Application number: EP02708276A
Authority: EP
Inventors: Bernd Müller; Arne Ptock; Eberhard Ammermann; Reinhard Stierl; Gisela Lorenz; Siegfried Strathmann; Maria Scherer; Klaus Schelberger; Joachim Leyendecker; Manfred Hampel
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 2001-01-16
Filing date: 2002-01-12
Publication date: 2003-10-22
Also published as: WO2002054869A1; BR0206442A; US20040044060A1; KR20030066814A; PL369028A1; JP2005511474A; MXPA03005634A; CN1484492A

Abstract

The invention relates to fungicidal mixtures that contain, in a synergistically effective amount, A) imidazole derivatives of the formula (I), B) carbamates of the formula (II), and C) amide compounds of formula (III). The invention also relates to methods for controlling fungicidal parasites using mixtures of the compounds I, II and III, and to the use of compounds I and the compounds II for producing such mixtures.

Description

Fungicidal mixtures

description

The present invention relates to fungicidal mixtures comprising

A) Imidazole derivatives of the formula I.

in which R ¹ and R ^{2 are} halogen and phenyl, which may be substituted by halogen or -CC alkyl, or

R ¹ and R ² together with the bridging C = C double bond form a 3, 4-difluoromethylene dioxyphenyl group;

R ³ cyano o ^' the halogen, and

R ⁴ di- (-C - (_ ₄ -alkyl) amino or

Isoxazol-4-yl, which can carry two -CC ₄ alkyl radicals mean; and

in which n is 1 or 2 and Y is halogen, C 1 -C 4 -alkyl and CC -haloalkyl, where the radicals Y can be different if n is 2; and

C) Amide compounds of the formula III

in which Z ¹ and Z ^{2 are} identical or different and are halogen, nitro, cyano, Ci-Cs-alkyl, C ₂ -C ₈ alkenyl, C ₂ -C ₈ alkynyl, Ci-Cs-haloalkyl, C-Cs- Haloalkenyl, CC ₈ ~ haloalkynyl, Ci-C _δ alkoxy, Ci-Cs-haloalkoxy, Ci-Cs-haloalkylthio, Ci-C _ß- alkylsulfinyl or Ci-Cs-alkylsulfonyl;

in a synergistically effective amount.

In addition, the invention relates to methods for controlling harmful fungi with mixtures of the compounds I, II and III and the use of the compounds I and the compounds II for the production of such mixtures.

The imidazole derivatives of the formula I, their preparation and their action against harmful fungi are known from the literature (EP-A 298 196, O-A 97/06171).

The carbamates of the formula II are also known, their preparation and their action against harmful fungi are known from the literature (WO-A 93/15046; WO-A 96/01256 and WO-A 96/01258).

The compounds of formula III, their preparation and their action against harmful fungi are also known from the literature (EP-A 545 099).

With a view to reducing the application rates and improving the spectrum of action of the known compounds I, II and III, the present invention was based on the problem of mixtures which, with a reduced total amount of active compounds applied, have an improved action against harmful fungi (synergistic mixtures).

Accordingly, the mixture defined at the outset was found. It has also been found that, when the compounds I and the compounds II are used simultaneously or jointly or separately, or when the compounds I and the compounds II are used in succession, harmful fungi can be controlled better than with the individual compounds alone.

Formula I in particular represents imidazole derivatives of the formula I in which R ^{1 is} halogen, in particular chlorine and R ^{2 is} tolyl, in particular p-tolyl.

Equally preferred are compounds of the formula I in which R ^{4 is} dimethylamino. In addition, the compound of the formula Ia (common name: cyazofamid) is particularly preferred. It is known from EP-A 298 196.

Also preferred are compounds of the formula I in which R ¹ and R ² together with the bridging C = C double bond form a 3, 4-difluoromethylenedioxyphenyl group.

In addition, compounds of the formula I are preferred in which R ^{4 is} 3, 5-dimethylisoxazol-4-yl.

The compounds of the formula Ib in which X is halogen are particularly preferred.

Halogen stands for fluorine, chlorine, bromine and iodine. Compounds of the formula Ib in which X represents bromine (Ib.l) or chlorine (Ib.2) are particularly preferred.

Formula II represents in particular carbamates in which the combination of the substituents corresponds to one row of the following table:

Compounds of the formula II in which Y is in the para position are particularly preferred; these compounds are described by the formula Ha:

Likewise, particular preference is given to compounds of the formula II in which Y represents fluorine, chlorine, methyl or trifluoromethyl. Compounds II-3, II-6, 11-12 and 11-17, in particular compound II-6, are particularly preferred.

Of the compounds of the formula III, those in which the combination of the substituents corresponds to one row of the following table are particularly preferred:

Compounds III in which Z ^{1 represents} CF ₃ or halogen and Z ^{2 represents} halogen are particularly preferred.

The mixture of the compounds Ia, II-6 and III-5 is particularly preferred.

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

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.

Suitable organic acids, for example formic acid, carbonic acid and alkanoic acids such as acetic acid, trifluoroacetic acid, trichloroacetic acid and propionic acid and glycolic acid, lactic acid, succinic acid, citric acid, benzoic acid, cinnamic acid, oxalic acid, p-toluenesulfonic acid, salicylic acid, p-Aminosalizyl- acid, 2-phenoxybenzoic, 2 -Acetoxybenzoic acid in question. The ions of the elements chromium, manganese, iron, cobalt, nickel, copper, zinc, calcium, magnesium, aluminum, tin and lead are particularly suitable as metal ions. The metals can, if appropriate, be present in various valencies to which they are assigned.

When preparing the mixtures, preference is given to using the pure active ingredients I, II and III, to which further active ingredients can be admixed against harmful fungi or against other pests such as insects, arachnids or nematodes or else herbicidal or growth-regulating active ingredients or fertilizers.

The mixtures of the compounds I and II or the compounds I and II used simultaneously, together or separately, are distinguished by an excellent action against a broad spectrum of phytopathogenic fungi, in particular from the class of the Ascomycetes, Basidiomycetes, Phycomycetes and Deuteromycetes out. They are partly systemically effective and can therefore also be used as leaf and soil fungicides.

They are of particular importance for combating a large number of fungi on various crops such as cotton, vegetables (eg cucumber, beans, tomatoes, potatoes and squashes), barley, grass, oats, bananas, coffee, corn, fruit plants, rice, rye , Soy, wine, wheat, ornamental plants, sugar cane and a variety of seeds.

They are particularly suitable for combating the following phytopathogenic fungi: Erysiphe graminis (powdery mildew) on cereals, Erysiphe cichoracearum and Sphaerotheca fuliginea on pumpkin plants, Podosphaera leucotricha on apples, üncinula necator on vines, Puccinia cotton species on cereal species, Rhiz Rice and lawn, Ustilago species on cereals and sugar cane, Venturia inaequalis (scab) on apples, Helminthosporium species on cereals, Septoria nodorum on wheat, Botrytis cinera (gray mold) on strawberries, vegetables, ornamental plants and vines, cercospora arachidicola on peanuts, Pseudocercosporella herpotrichoides on wheat and barley, Pyricularia oryzae on rice, Phytophthora infestans on potatoes and tomatoes, Plasmopara viticola on vines, Pseudoperonospora species in hops and cucumbers, Alternaria species on vegetables and fruit, Mycosphaerella species in Ban Fusarium and Verticillium species.

They can also be used in material protection (eg wood protection), for example against Paecilomyces variotii. The compounds I, II and III can be applied simultaneously, that is jointly or separately, or in succession, the sequence in the case of separate application generally not having any effect on the control success.

The compounds I, II and III are usually used in a weight ratio of (1:11 and I: III) in each case 20: 1 to 1:20, in particular 10: 1 to 1:10, preferably 5: 1 to 1: 5.

The application rates of the mixtures according to the invention, especially for agricultural crop areas, are from 0.01 to 8 kg / ha, preferably 0.1 to 5 kg / ha, in particular 0.1 to 3.0 kg / ha, depending on the type of effect desired ,

The application rates for the compounds I are 0.01 to 1 kg / ha, preferably 0.05 to 0.5 kg / ha, in particular 0.05 to 0.3 kg / ha.

The application rates for the compounds II and III are accordingly from 0.01 to 1 kg / ha, preferably 0.02 to 0.5 kg / ha, in particular 0.05 to 0.3 kg / ha.

In the case of seed treatment, application rates of mixture of 0.001 to 250 g / kg of seed, preferably 0.01 to 100 g / kg, in particular 0.01 to 50 g / kg, are generally used.

If pathogenic harmful fungi are to be combated for plants, the compounds I, II and III or the mixtures of the compounds I, II and III are applied separately or together by spraying or dusting the seeds, the plants or the soil before or after sowing of the plants or before or after emergence of the plants.

The fungicidal synergistic mixtures according to the invention or the compounds I, II and III can be used, for example, in the form of directly sprayable solutions, powders and suspensions or in the form of high-strength aqueous, oily or other suspensions, dispersions, emulsions, oil dispersions, pastes, dusts, spreading agents or granules prepared and spray by comparison ^', atomizing, dusting, broadcasting or watering. The form of application depends on the intended use; in any case, it should ensure that the mixture according to the invention is as fine and uniform as possible. The formulations are prepared in a manner known per se, for example by adding solvents and / or carriers. Inert additives such as emulsifiers or dispersants are usually added to the formulations.

The alkali, alkaline earth, ammonium salts of aromatic sulfonic acids, e.g. Lignin, phenol, naphthalene and dibutylnaphthalenesulfonic acid, as well as of fatty acids, alkyl and alkylarylsulfonates, alkyl, lauryl ether and fatty alcohol sulfates, as well as salts of sulfated hexa-, hepta- and octadecanols or fatty alcohol glycol ethers, condensation products of sulfonated naphthalene and its derivatives , Condensation products of naphthalene or naphthalenesulfonic acids with phenol and formaldehyde, polyoxyethylene octylphenol ether, ethoxylated isooctyl, octyl or nonylphenol, alkylphenol or tributylphenyl polyglycol ether, alkylaryl polyether alcohols, isotridecyl alcohol, fatty alcohol, ethylenoxy polyoxyethylene, ethylenedoxyl, ethylenoxy polyoxyethylene, ethoxylated ethoxylated, ethoxylated Lauryl alcohol polyglycol ether acetate, sorbitol ester, lignin sulfite waste liquor or methyl cellulose into consideration.

Powders, materials for broadcasting and dusts can be prepared by mixing or grinding the compounds I or II together or the mixture of the compounds I, II and III with a solid carrier.

Granules (e.g. coating, impregnation or homogeneous granules) are usually produced by binding the active ingredient or ingredients to a solid carrier.

Mineral earths such as silica gel, silicas, silica gels, silicates, talc, kaolin, limestone, lime, chalk, bolus, loess, clay, dolomite, diatomaceous earth, calcium and magnesium sulfate, magnesium oxide, ground plastics serve as fillers or solid carriers, for example. as well as fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas and vegetable products such as cereal flour, tree bark, wood and nutshell flour, cellulose powder or other solid carriers.

The formulations generally contain 0.1 to 95% by weight, preferably 0.5 to 90% by weight, of one of the compounds I or II or the mixture of the compounds I, II and III. The active ingredients are used in a purity of 90% to 100%, preferably 95% to 100% (according to the NMR or HPLC spectrum). The compounds I, II and III, the mixtures or the corresponding formulations are used in such a way that the harmful fungi, their habitat or the plants, seeds, soils, areas, materials or spaces to be kept free by them are treated with a fungicidally effective amount of Mixture, or the compounds I and II treated separately.

The application can take place before or after the infestation by the harmful fungi.

example

The following experiments demonstrated the synergistic effect of the mixtures according to the invention:

The active ingredients were prepared separately or together as a 10% emulsion in a mixture of 63% by weight cyclohexanone and 27% by weight emulsifier and diluted with water in accordance with the desired concentration.

The evaluation was carried out by determining the affected leaf areas in percent. These percentages were converted into efficiencies. Efficiency (W) was determined using Abbot's formula as follows:

corresponds to the fungal attack on the treated plants in% and ß corresponds to the fungal attack on the untreated (control) plants in%

With an efficiency of 0, the infection of the treated plants corresponds to that of the untreated control plants; at an efficiency of 100, the treated plants showed no infection.

The expected efficacies of the active ingredient mixtures were calculated using the Colby formula [R.S. Colby, Weeds 15, 20-22 (1967)] and compared with the observed efficiencies.

Colby formula: E = x + y - x-y / 100

E expected efficiency, expressed in% of the untreated control, when using the mixture of active ingredients A and B in concentrations a and b x the efficiency, expressed in% of the untreated control, when using the active ingredient A in the concentration ay the efficiency, expressed in% of the untreated control, when using the active ingredient B in the concentration b

Example of use: Protective activity against vine peronospora caused by Plasmopara vi ticola

Leaves of potted vines of the "Müller-Thurgau" variety were sprayed to runoff point with aqueous active ingredient preparation which was prepared with a stock solution consisting of 10% active ingredient, 85% cyclohexanone and 5% emulsifier. The following day, the undersides of the leaves were inoculated with an aqueous zoospore suspension of Plasmopara vi ticola. The vines were then placed for 48 hours in a steam-saturated chamber at 24 ° C and then for 5 days in a greenhouse at temperatures between 20 and 30 ° C. After this time, the plants were again placed in a moist chamber for 16 hours in order to accelerate the sporangium carrier outbreak. The extent of the development of the infestation on the undersides of the leaves was then determined visually.

Table A - Individual substances

Table B - combinations according to the invention

• J_Q *) calculated according to the Colby formula

The results of the tests show that the observed efficiency in all mixing ratios is higher than calculated using the Colby formula.

15

20

25

30

35

40

45

Claims

Claims:

1. Fungicidal mixtures containing

A) Imidazole derivatives of the formula I.

in which R ¹ and R ^{2 are} halogen and phenyl, which can be substituted by halogen or Cχ-C-alkyl, or R ¹ and R ² together with the bridging C = C-double bond are a 3, 4-difluoromethylene dioxyphenyl group form;

R ³ cyano or halogen, and

R ⁴ di- (-C-alkyl) amino or

Isoxazol-4-yl, which can carry two -CC alkyl radicals mean; and

B) carbamates of the formula II,

in which n stands for 1 or 2 and Y is halogen, C ₁ -C ₄ alkyl, and Cι-C ₂ -haloalkyl, where the radicals Y can be different if n is 2; and

C) Amide compounds of the formula III

wherein Z ¹ and Z ² are the same or different and lie for Ha-, nitro, cyano, C ₈ alkyl, C ₂ -C ₈ alkenyl, C -Cs-alkynyl, Ci-Cs-haloalkyl, C -C ₈ -halogenalkenyl, C -C ₈ -halogenalkynyl, Cι-C ₈ alkoxy, C -Cs-haloalkoxy, Ci-Cs-haloalkylthio, Ci-Cs-alkylsulfinyl or Ci-Cs-alkylsulfonyl;

in a synergistically effective amount.

2. Fungicidal mixture according to claim 1, wherein the imidazole derivative I of the formula Ia

corresponds.

A fungicidal mixture as claimed in claim 1, where the imidazole derivative I of the formula Ib

where X is chlorine or bromine.

4. Fungicidal mixture according to claim 1, characterized in that the weight ratio of the compounds 1:11 and I: III is in each case 20: 1 to 1:20.

5. A method for combating harmful fungi, characterized in that the harmful fungi, their habitat or the plants, seeds, soils, areas to be kept free of them,

Materials or spaces treated with imidazole derivatives of the formula I according to claim 1, carbamates of the formula II and amide compounds of the formula III according to claim 1.

6. The method according to claim 5, characterized in that one

Imidazole derivatives of the formula I according to claim 1, carbamates of the formula II according to claim 1 and amide compounds of the formula III according to claim 1 simultaneously, that is jointly or separately, or in succession.

7. The method according to claim 5 or 6, characterized in that the imidazole derivatives of the formula I according to claim 1 are used in an amount of 0.01 to 2.5 kg / ha.

8. Process according to claims 5 to 7, characterized in that the carbamates of the formula II according to claim 1 are used in an amount of 0.01 to 10 kg / ha.

9. The method according to claims 5 to 8, characterized in that the amide compounds of the formula III according to claim 1 are used in an amount of 0.01 to 10 kg / ha.

10. Fungicidal composition which is conditioned in three parts, one part containing imidazole derivatives of the formula I according to claim 1 in a solid or liquid carrier and the other part carbamates of the formula II according to claim 1 and the third part amide compounds of the formula III according to claim 1 in a solid or liquid carrier.