EP1353553A2

EP1353553A2 - Fungicidal mixtures

Info

Publication number: EP1353553A2
Application number: EP02703556A
Authority: EP
Inventors: Thomas Grote; 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: 2003-10-22
Also published as: AU2002237275A1; JP2004521886A; US20040054011A1; WO2002056685A2; AR032508A1; WO2002056685A3

Abstract

The invention relates to fungicidal mixtures containing a) benzophenones of formula (I), where R1 = chloro, methyl, methoxy, acetoxy, pivaloyloxy or hydroxy; R2= chloro or methyl; R3 = H, halogen or methyl and R4 = C1-C6 alkyl or benzyl, where the phenyl moiety of the benzyl group may be halo- or methyl-substituted and b) trisoximethers of formula (II), where X = NH or O; R5, R7, independently = C¿1?-C4 alkyl or cyclopropyl; R?6, R8¿, independently = C¿1?-C4 alkyl, C3-C4 alkenyl or cyclopropyl; in synergistically effective amounts. The invention further relates to the treatment of noxious fungi with mixtures of compounds (I) and (II) and agents containing the same.

Description

Fungicidal mixtures

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} Ci-Ce-alkyl or benzyl, where the phenyl part of the benzyl radical can carry a halogen or methyl substituent, and

b) trisoxime ethers of the formula II,

in which the substituents have the following meanings:

X NH or oxygen;

R ⁵ , R ⁷ independently of one another Cj _. -C alkyl or cyclopropyl;

R ⁵ , R ⁸ independently of one another -CC alkyl, C -C ₄ -alkenyl or cyclopropyl;

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 action against harmful fungi are known from the literature (EP-A 727 141; EP-A 897 904; EP-A 899 255; EP-A 967 196).

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

The trisoxy ethers of the formula II, their preparation and their action against harmful fungi are known (EP-A 876 332).

A possible synergistic effect between the specially substituted benzophenones of the formula I and the trisoxy ethers of the formula II was previously unknown.

With a view to lowering the application rates and improving the spectrum of action of the known compounds I and II, the present invention was based on mixtures which, with a reduced total amount of active compounds applied, have an improved activity 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.

The following compounds of the 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 ₁ -C ₄ -alkyl or benzyl, where the phenyl part of the benzyl radical can carry a halogen or methyl substituent. Particularly preferred are 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:

0

5

0

With regard to their use in the mixtures according to the invention, the trisoxime ethers II listed in Table 2 below are preferred. 5

Table 2

Compounds of the formula Ha are particularly preferred,

in which R ⁶ and R ^{8 is} methyl, ethyl, isopropyl or cyclopropyl, in particular methyl or ethyl. Particularly preferred; are the compounds II-1, II-3 and II-5.

Fungicidal mixtures which are preferred as component a) are one of the compounds: 1-33, 1-35, 1-42, 1-44, 1-46, 1-60, or preferably 1-18, 1-28, 1-37 , and as component b) one of the compounds: II-3, II-5 or preferably II-1.

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, carbonic acid, sulfuric acid, phosphoric acid and nitric acid.

Examples of suitable organic acids are formic acid, and alkanoic acids such as acetic acid, trifluoroacetic acid, trichloroacetic acid and propionic acid, and also glycolic acid, lactic acid, succinic acid, citric acid, benzoic acid, cinnamic acid, oxalic acid, p-toluenesulfonic acid, salicylic acid, p-aminosalicylic acid, 2-aminosalicylic acid, Phenoxybenzoic acid or 2-acetoxybenzoic acid.

In particular, the ions of the elements of the first to eighth subgroups, especially chromium, manganese, iron, cobalt, nickel, copper, zinc and in addition to the second main group, especially calcium and magnesium, the third and fourth main group, in particular aluminum, come as metal ions. Tin and lead into consideration. The metals can, if appropriate, be present in various valences which suit them.

When preparing the mixtures, preference is given to using the pure active compounds I and II, to which further active compounds against harmful fungi or against other pests such as insects, arachnids or nematodes or else herbicidal or growth-regulating active compounds or fertilizers can be admixed. 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-ycetes out. 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. 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 gra inis (powdery mildew) on cereals, Erysiphe cichoracearum and Sphaerotheca fuliginea on pumpkin plants, Podosphaera leucotricha on apples, Uncinula necator on vines, Puccinia cotton on cereals, Rhizo , 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, Plas opara viticola on vines, Pseudoperonospora species in hops and cucumbers, Alternaria species on vegetables and fruits, Mycospha Bananas as well as Fusariu 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 compounds I and II are usually used in a weight ratio of 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 in the case of agricultural cultivated areas, are from 0.01 to 8 kg / ha, preferably 0.1 to 5 kg / ha, in particular 0.1 to 3.0, depending on the type of effect desired kg / ha. The application rates for the compounds I are 0.005 to 5 kg / ha, preferably 0.08 to 3 kg / ha, in particular 0.06 to 2.0 kg / ha.

The application rates for the compounds II are accordingly 0.005 to 3 kg / ha, preferably 0.02 to 2 kg / ha, in particular 0.04 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 application form 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, e.g. by adding solvents and / or carriers. Inert additives such as emulsifiers or dispersants are usually added to the formulations.

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 naphthalene sulfonic acids, polyoxyethylene octylphenol ether, ethoxylated isooctyl, tribyl or nonylphenol, alkylphenol Isotridecyl alcohol, fatty alcohol ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ether or polyoxypropylene, lauryl alcohol polyglycol ether acetate, sorbitol ester, lignin sulfite waste liquor or methyl cellulose

Consideration.

Powder sprinklers and dusts can be prepared by mixing or grinding the compounds I or II together 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 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 according to the desired concentration diluted with water.

The evaluation was carried out by determining the affected leaf areas in percent. These percentages have been converted into efficiency levels. The efficiency () was determined according to 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 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 cucumber mildew caused by Sphaerotheca fuliginea

Leaves of cucumber seedlings of the "Chinese snake" variety grown in pots were sprayed to runoff point in the cotyledon stadiuiα with aqueous active ingredient preparation which was prepared from a stock solution consisting of 10% active ingredient, 85% cyclohexanone and 5% emulsifier. 20 hours after the spray coating had dried on, the plants were inoculated with an aqueous spore suspension of cucumber mildew (Sphaerotheca fuliginea). The plants were then cultivated in a greenhouse at temperatures between 20 and 24 ° C. and 60 to 80% relative atmospheric humidity for 7 days. Then the extent of Powdery mildew development determined visually in% of the cotyledon area.

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 substances were determined using the Colby formula (Colby, S.R. (Calculating synergistic and antagonistic responses of herbicide combinations ", Weeds, 15, pp. 20-22, 1967) and compared with the observed efficacies.

Table A

Table B

*) calculated according to the Colby formula

The results of the experiment show that the observed efficiency in all mixing ratios is higher than the efficiency calculated in advance by the Colby formula (from Synerg 166A. XLS).

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 represents} Ci-C _ß- alkyl or benzyl, where the phenyl part of the benzyl radical can carry a halogen or methyl substituent, and

b) trisoxime ethers of the formula II,

in which the substituents have the following meanings:

X NH or oxygen;

R ⁵ , R ⁷ independently of one another C 1 -C ₄ -alkyl or cyclopropyl;

R ^6, R ^{8 are} independently Cι-C ₄ alkyl, C -C ₄ alkenyl or cyclopropyl;

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, wherein the trisoxime ether II of the formula Ha,

in which R ⁵ and R ^{8 represent} methyl, ethyl, isopropyl or cyclopropyl.

4. Fungicidal mixture according to claim 1, characterized in that the weight ratio of the benzophenones I to the trisoxy ethers of the formula II is 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, materials or spaces to be kept free of them with benzophenones of the formula I according to claim 1 and trisoxime ethers of the formula II according to claim 1 treated

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

Benzophenones of the formula I according to claim 1 and trisoxime ethers of the formula II according to claim 1 simultaneously, namely together or separately, or in succession.

7. The method according to claim 5 or 6, characterized in that the benzophenones of the formula I according to claim 1 in an amount of 0.08 to 3 kg / ha.

8. Process according to Claims 5 to 7, characterized in that the trisoxime ethers of the formula II according to Claim 1 are used in an amount of 0.02 to 2 kg / ha.

9. Composition according to claim 1, 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 of trisoxime ether of the formula II according to claim 1 in a solid or liquid carrier ,