EP1365654A1

EP1365654A1 - Fungicidal mixtures comprising benzophenone and imidazole derivatives

Info

Publication number: EP1365654A1
Application number: EP02710801A
Authority: EP
Inventors: Arne Ptock; Ingo Rose; Eberhard Ammermann; Reinhard Stierl; Gisela Lorenz; Siegfried Strathmann; Maria Scherer; Klaus Schelberger; Egon Haden
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 2001-01-18
Filing date: 2002-01-17
Publication date: 2003-12-03
Also published as: JP4188688B2; WO2002056689A1; AR032507A1; US20040053984A1; JP2004523516A

Abstract

The invention relates to fungicidal mixtures containing a) benzophenones of formula (I), where R<1> = chloro, methyl, methoxy, acetoxy, pivaloyloxy or hydroxy; R<2> = chloro or methyl; R<3> =H, halogen or methyl and R<4> = C1-C6 alkyl or benzyl, where the phenyl moiety of the benzyl group can be halo- or methyl-substituted and b) imidazole derivatives of formula (II), where Y = bromine or chlorine, in synergistically effective amounts. The invention further relates to a method for the treatment of noxious fungi with mixtures of compounds (I) and (II) and agents containing the same.

Description

Fungicidal mixtures of benzophenones and imidazole derivatives

description

The present invention relates to fungicidal mixtures containing

a) benzophenones of the formula I,

in the

R ^{1 represents} chlorine, methyl, methoxy, acetoxy, pivaloyloxy or hydroxy;

R ^{2 represents} chlorine or methyl;

R ^{3 represents} hydrogen, halogen or methyl; and

R ^{4 represents} Cχ-C ₆ alkyl or benzyl, where the phenyl part of the benzyl radical can carry a halogen or methyl substituent, and

b) imidazole derivatives of the formula II,

in which Y represents bromine or chlorine,

in a synergistically effective amount.

The invention also relates to methods for controlling harmful fungi with mixtures of the compounds I and II and agents conditioned in two parts. The compounds of formula I, their preparation and their activity against harmful fungi are known from the literature (EP-A 727 141; EP-A 897 904; EP-A 899 255; ΞP-A 967 196).

Mixtures of benzophenones of the formula I with other fungicidal active ingredients are known from EP-A 1 023 834.

Also known are the imidazole derivatives of the formula II, their preparation and their action against harmful fungi (WO-A 97/06171).

The object of the present invention was to provide further particularly effective mixtures for combating harmful fungi and in particular for certain indications.

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

We have found that this object is achieved by the mixtures defined at the outset. 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.

The mixtures according to the invention act synergistically and are therefore particularly suitable for controlling harmful fungi and in particular powdery mildew in cereals, vegetables, fruit, ornamental plants and vines.

The following compounds of formula I are preferred as mixing partners, the individual preferences taken on their own and to be read in combination.

Compounds I in which R ^{1 is} chlorine, methoxy, acetoxy or hydroxy are preferred, and compounds in which R ^{1 is} methoxy, acetoxy or hydroxy are particularly preferred. Compounds in which R ^{1 is} methoxy are very particularly preferred.

According to the invention, mixtures containing compounds I in which R ^{2 is} chlorine or methyl. Compounds I in which R ^{2 is} methyl are preferred. In addition, compounds I are preferred in which R ^{3 represents} hydrogen, methyl, chlorine or bromine and particularly preferably hydrogen, chlorine or bromine.

In addition, compounds I are preferred in which R ^{4 is} -C ₄ -alkyl or benzyl, where the phenyl part of the benzyl radical can carry a halogen or methyl substituent. Particular preference is given to compounds of the formula I in which R ^{4 is} C 1 -C ⁴ -alkyl and preferably methyl.

Also preferred are compounds of the formula I in which the substituents R ¹ , R ² , R ³ and R ^{4 have} the following meaning: R ¹ methoxy, acetoxy or hydroxy; R ² methyl; R ^{3 is} hydrogen, chlorine or bromine; and R ⁴ -CC ₄ alkyl.

In addition, compounds of the formula I are particularly preferred in which the substituents have the meanings given in the following table:

Compounds 1-18, 1-37 and in particular compound 1-28 are preferred as mixture component a).

Compounds of the formula II come as mixture component b)

where Y is bromine or chlorine.

Fungicidal mixtures which are preferred as component a) e ne of the compounds: 1-33, 1-35, 1-42, 1-44, 1-46, 1-60, or preferably 1-18, 1-28, 1- 37, and contain as component b) one of the compounds II.

Because of the basic character of the nitrogen atoms contained in them, the compounds II 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.

Examples of organic acids are formic acid, carbonic acid and alkanoic acids such as acetic acid, trifluoroacetic acid, trichloroacetic acid and propionic acid as well as glycolic acid, thiocyanic acid, lactic acid, succinic acid, citric acid, benzoic acid, cinnamic acid, oxalic acid, alkylsulfonic acids (sulfonic acids with branched or straight-chain chains) 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 carry one or two phosphoric acid residues), where the alkyl or aryl residues can carry further substituents, for example p-toluenesulfonic acid, salicylic acid, p-aminosalicylic acid, 2-phenoxybenzoic acid, 2-acetoxybenzoic acid etc.

In particular, the ions of the elements of the first to eighth subgroups, especially chromium, manganese, iron, cobalt, nickel, copper, zinc and, in addition, the second main group, especially calcium and magnesium, of the third and fourth main group come as metal ions Aluminum, tin and lead are considered. The metals can, if appropriate, be present in various valences which they can assume.

The quantitative ratio of the compounds I and II can be varied within wide ranges; the active compounds are preferably used in a weight ratio in the range from 1000: 1 to 1: 1, preferably 400: 1 to 10: 1 and particularly preferably 200: 1 to 50: 1.

When preparing the mixtures, use is preferably made of the pure active ingredients I and II, 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 Deutero- mycetes from. Some of them are systemically effective and can therefore also be used as leaf and soil fungicides.

They are particularly important for combating a large number of fungi on various crops such as cotton, vegetables (e.g. cucumbers, 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 squash plants, Podosphaera leucotricha on apples, Uncinula necator on vines, Puccinia species on cereals, Rhizo species Rice and lawn, Üstilago 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 Ba nanen and Fusarium and Verticillium species.

They can also be used in material protection (e.g. wood protection), for example against Paecilomyces variotii.

The compounds I and II 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 success of the control measures.

The application rates of the mixtures according to the invention, especially for agricultural crop areas, are from 0.01 to 10 kg / ha, preferably 0.1 to 5 kg / ha, in particular 0.2 to 3.0 kg / ha, depending on the type of effect desired ,

The application rates for the compounds I are 0.005 to 6.5 kg / ha, preferably 0.08 to 3.0 kg / ha, in particular 0.12 to 2.0 kg / ha.

The application rates for the compounds II are accordingly 0.005 to 3.5 kg / ha, preferably 0.02 to 2 kg / ha, in particular 0.08 to 1.0 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 and II or the mixtures of the compounds I and II are applied separately or together by spraying or dusting the seeds, the plants or the soil before or after the plants are sown or before or after the plants emerge.

The fungicidal synergistic mixtures according to the invention or the compounds I and II can be prepared, 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 and applied by spraying, atomizing, dusting, scattering or pouring. 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 known manner, e.g. by stretching the active ingredient with solvents and / or carriers, if desired using emulsifiers and dispersants, where in the case of water as diluent other organic solvents can also be used as auxiliary solvents. The following are essentially considered as auxiliaries: solvents such as aromatics (e.g. xylene), chlorinated aromatics (e.g. chlorobenzenes), paraffins (e.g. petroleum fractions), alcohols (e.g. methanol, butanol), ketones (e.g. cyclohexanone), amines (e.g. ethanolamine , Dimethylformamide) and water; Carriers such as natural stone powder (e.g. kaolins, clays, talc, chalk) and synthetic stone powder (e.g. highly disperse silica, silicates); Emulsifiers such as non-ionic and anionic emulsifiers (e.g. polyoxyethylene fatty alcohol ethers, alkyl sulfonates and aryl sulfonates) and dispersants such as lignin sulfite waste liquors and methyl cellulose.

The surface-active substances are the alkali metal, alkaline earth metal, ammonium salts of aromatic sulfonic acids, for example lignin, phenol, naphthalene and dibutylnaphthalenesulfonic acid, and of fatty acids, alkyl and alkylarylsulfonates, alkyl, lauryl ether and fatty alcohol sulfates, and salts of sulfated hexa- , Hepta- and octadecanols or fatty alcohol glycol ethers, condensation products of sulfonated naphthalene and its derivatives with formaldehyde, 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 ethylene oxide condensate oil, lauryl ether polyethylenethoxyl ether polyethylenethoxyl ethoxylated ethoxylated ethoxylated alcohols -Sulfite waste or methyl cellulose into consideration.

Powders, materials for broadcasting and dusts can be prepared by mixing or jointly grinding the compounds I or II or the mixture of the compounds I and II 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 soils such as silica gel, silicas, silica gels, silicates, talc, kaolin, limestone, lime, chalk, boluses, loess, clay, dolomite, diatomaceous earth, calcium and magnesium sulfate, magnesium oxide, ground plastics and fertilizers are used as fillers or solid carriers 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 of the mixture of the compounds I and II. The active ingredients are in a purity of 90% to 100%, preferably 95% to 100% (according to the NMR or HPLC spectrum) is used.

The compounds I or II, 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 of them are mixed with a fungicidally effective amount of the mixture, or of compounds I and II treated separately.

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

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

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

α corresponds to the fungal attack of the treated plants in% and ß corresponds to the fungal attack of 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 are calculated according to 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 bx the efficiency, expressed in% of the untreated control, when using active ingredient A in concentration ay der Efficiency, expressed in% of the untreated control, when using the active ingredient B in the concentration b.

Example of use 1: Protective activity against late blight on tomatoes caused by Phytophthora infestans

Leaves of potted plants of the "Large meat tomato St. Pierre" were treated with an aqueous suspension consisting of a stock solution consisting of 10% active ingredient, 85% cyclohexanone and 5 % Of emulsifier was sprayed on until dripping wet. The following day the leaves were infected with a cold aqueous zoospore suspension of Phytoph thora infes tans with a density of 0.25 x 10 ⁶ spores / ml. The plants were then placed in a water vapor-saturated chamber at temperatures between 18 and 20 ° C. After 6 days, the herb rot had developed so strongly on the untreated but infected control plants that the infestation could be determined visually in%.

The visually determined values for the percentage of leaf areas affected were converted into efficiencies as% of the untreated control. Efficiency 0 is the same as in the untreated control, efficiency 100 is 0%. The expected efficacies for combinations of active ingredients were determined using the Colby formula (Colby, S.R. (Calculating synergistic and antagonistic responses of herbicide combinations ", Weeds, 15th, pp. 20-22, 1967) and compared with the observed efficacies.

Table A

Table B

observed effect according to the invention

Combinations degrees degrees *)

Compound h-37

+ Compound II, Y = Br 100 48

5 + 0.05 ppm

Mixture 100: 1

Compound h-37

+ Compound II, Y = Br 100 74

5 + 0.1 ppm

10

Mixture 50: 1

Compound h-37

+ Compound II, Y = Br 100 87

5 + 0.2 ppm

15 mixture 25: 1

Compound h-37

+ Compound II, Y = Br 97 73

20 + 0.1 ppm

Mix 200: 1

20 compound h-37

+ Compound II, Y = Br 92 48

10 + 0.05 ppm

Mix 200: 1

Connection 37

25 + compound II, Y = Br 89 74

40 + 0.1 ppm

Mix 400: 1

Compound h-37

+ Compound II, Y = Br 92 48

30 20 + 0.05 ppm

Mix 400: 1

*) calculated according to the Colby formula

35 from the results of the experiment show that the obser ^¬ preparing efficiency is higher in all mixing ratios than the pre-calculated according to the Colby formula efficiency (from syn- erg 164A. XLS).

40

45

Claims

Claims:

1. Fungicidal mixtures containing

a) benzophenones of the formula I,

in the

R ^{1 represents} chlorine, methyl, methoxy, acetoxy, pivaloyloxy or hydroxy;

R ^{2 represents} chlorine or methyl;

R ^{3 represents} hydrogen, halogen or methyl; and

R ^{4 is} Cχ-C ₆ alkyl or benzyl, where the phenyl part of the benzyl radical can carry a halogen or methyl substituent, and

b) imidazole derivatives of the formula II,

in which Y represents bromine or chlorine,

in a synergistically effective amount.

2. Fungicidal mixtures according to claim 1, wherein in formula I

R ^{1 is} methoxy, acetoxy or hydroxy; R ^{2 is} methyl;

R ^{3 represents} hydrogen, chlorine or bromine; and

R ^{4 is} -C ₄ alkyl.

3. Fungicidal mixture according to claim 1, characterized in that the weight ratio of the benzophenones I to the imidazole derivatives of the formula II is 400: 1 to 10: 1.

4. A method for combating harmful fungi, characterized in that the harmful fungi, their habitat or the plants, seeds, soils, surfaces, materials or spaces to be kept free of them with benzophenones of the formula I according to claim 1 and imidazole derivatives of the formula II according to claim 1 treated.

5. The method according to claim 4, characterized in that benzophenones of the formula I according to claim 1 and I idazol derivative of the formula II according to claim 1 simultaneously, together or separately, or in succession.

6. The method according to claim 4 or 5, characterized in that the benzophenones of the formula I according to claim 1 in an amount of 0.02 to 2.0 kg / ha.

7. Process according to Claims 4 to 6, characterized in that the imidazole derivatives of the formula II according to Claim '1 are used in an amount of 0.08 to 3.0 kg / ha.

8. Fungicidal composition which is conditioned in two parts, one part containing benzophenones of the formula I according to claim 1 in a solid or liquid carrier and the other part containing imidazole derivatives of the formula II according to claim 1 in a solid or liquid carrier.