SK159199A3 - Fungicidal mixture - Google Patents

Abstract

The invention relates to a fungicidal mixture, containing a synergistically effective amount of a) a phenyl-benzyl ether derivative of formula (I.a), (I.b) or (I.c) and b) a carboxylic acid amide (II) selected from the group of compounds (IIa) and (IIb).

Description

Technical field

The invention relates to a fungicidal mixture and its use comprising a synergistically effective amount of a) a phenylbenzyl ether derivative of formula I and b) a carboxamide of formula II selected from the group of compounds.

SUMMARY OF THE INVENTION

The present invention relates to a fungicidal composition comprising

a) a phenylbenzyl ether derivative of the formula Ia, Ib or I.c

and

b) the carboxamide of formula II selected from the group of the compounds IIa and IIb of the _CH3

och ₃

in a synergistically effective amount.

The invention further relates to methods for controlling harmful fungi using mixtures of compounds I (l.a, l.b or l.c) and II (II.a or II.b) and to the use of compound I and compound II for the preparation of such mixtures.

The compounds of formula I, their preparation and their action against harmful fungi are described in the literature (EP-A 253 213; EP-A 254 426; EP-A 398 692).

Also described are carboxamides of formula II [11a: common name: Dimetomorph, EP-A 120 321; ll.b: proposed common name: Flumetover, AGROW no. 243 (1995), 22], their preparation and their action against harmful fungi.

It is an object of the present invention to provide compositions having an improved action against harmful fungi associated with a reduction in the total amount of active ingredients applied (synergistic compositions) in terms of reducing application rates and improving the spectrum of action of known compounds.

We have found that this object can be achieved by means of a mixture defined at the outset. In addition, we have found that better control of harmful fungi is possible by using Compound I and Compound II simultaneously or separately, or by using Compound I and Compound II sequentially than when individual compounds are used.

By virtue of their basic nature, compounds I and II are capable of forming salts or adducts with inorganic or organic acids or with metal ions.

Examples of inorganic acids are hydrohalic acids such as hydrofluoric acid, hydrochloric acid, hydrobromic acid and hydroiodic acid, and furthermore sulfuric acid, phosphoric acid and nitric acid.

Suitable organic acids are, for example, 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, acid cinnamic acid, oxalic acid, alkylsulfonic acids (sulfonic acids with linear or branched alkyl radicals having 1 to 20 carbon atoms), arylsulfonic acids or aryldisulfonic acids (aromatic residues such as phenyl and naphthyl bearing one or two sulfonic groups), alkylphosphonic acids (phosphonic acids with linear or branched alkyl radicals having 1 to 20 carbon atoms), arylphosphonic acids or aryldiphosphonic acids (aromatic residues such as phenyl and naphthyl bearing one or two phosphoric acid residues), the alkyl but or aryl residues may carry additional substituents, for example, ptoluenesulfonic acid, salicylic acid, p-aminosalicylic acid, 2-phenoxybenzoic acid, 2-acetoxybenzoic acid, and the like.

Suitable ions are, in particular, the ions of elements of the second main group, in particular calcium and magnesium, of the third and fourth main groups, in particular of aluminum, tin and lead, and of the first to eighth subgroup, in particular chromium, manganese, iron, cobalt, nickel, zinc, and more. Particularly preferred are the metal ions of the elements of the fourth period subgroup. Metals may exist in different powers that may belong to them.

• ¹ . ¹

In the preparation of the mixtures, it is preferable to use pure active ingredients I and II, to which additional active ingredients against harmful fungi or other pests such as insects, spiders or nematodes, or further herbicidal active ingredients or growth regulating active ingredients or fertilizers may be admixed

The mixtures of compounds I and II, or the simultaneous joint or separate use of compounds I and II, show an excellent action against a wide range of phytopathogenic fungi, in particular from the classes Ascomycetes, Basidiomycetes, Phycomycetes and Deuteromycetes. Some of them act systemically and can therefore also be used as foliar and soil fungicides.

They are particularly important for destroying a large number of fungi in a variety of crops such as cotton, vegetables (eg cucumbers, beans, tomatoes, potatoes and pumpkins), barley, grass, oats, banana, coffee, corn, fruit trees, rice, rye , soybean, vine, wheat, ornamental plants, sugar beet and a variety of seeds.

They are particularly suitable for destroying the following phytopathogenic fungi: Erysiphe graminis (powdery mildew) on grain, Erysiphe cichoracearum and Sphaerotheca fuliginea on pumpkins, Podosphaera leucotricha on apple trees, Uncinula necator on grape vine and rhizome, Puccinia species , Ustilago species for cereals and sugar beets, Venturia inaequalis (apple scab) on apple trees, Helminthosporium for cereals, Septoria nodorum on wheat, Botrytis cinerea (strawberry mold) on strawberries, vegetables, ornamental plants and grape vine, Cercolaospora arach , Pseudocercosporella herpotrichoides on wheat and barley, Pyricularia oryzae on rice, Phytophthora infestans on potatoes and tomatoes, Plasmopara viticola on grape vines, Pseudoperonospora on hops and cucumbers, Altemaria on vegetables and banana trees ium and Verticillium.

In addition, they can be used in the manufacture of materials (for example in the protection of wood), for example against Paecilomyces variotii.

• »»,

The compounds I and II may be used simultaneously, either together or separately, or sequentially, the sequence in the case of separate application generally having no effect on the result of the destruction measurements.

The compounds I and II are usually used in a weight ratio of from 20: 1 to 0.005: 1, preferably 10: 1 to 0.01: 1, particularly preferably 5: 1 to 0.2: 1.

Depending on the nature of the desired effect, the application rates of the mixtures according to the invention are, in particular in agricultural crops, from 0.01 to 8 kg / ha, preferably 0.1 to 5 kg / ha, particularly preferably 0.5 to 3.0 kg / ha .

The application rates of the compounds I are from 0.01 to 0.5 kg / ha, preferably 0.05 to 0.5 kg / ha, particularly preferably 0.05 to 0.3 kg / ha.

Correspondingly, in the case of compounds II, the application rates are from 0.005 to 1 kg / ha, preferably 0.1 to 0.5 kg / ha, particularly preferably 0.1 to 0.3 kg / ha.

For seed treatment, the application rates of the mixture are generally from 0.001 to 250 g / kg of seed, preferably 0.01 to 100 g / kg, particularly preferably 0.01 to 50 g / kg.

If phytopathogenic fungi are to be killed, separate or joint application of compounds I and II or mixtures of compounds I and II is carried out by spraying or dusting seeds, plants or soils, before or after sowing the plants or before or after emergence of the plants.

The fungicidal synergistic mixtures of the invention or compounds I and II can be prepared, for example, in the form of directly sprayable solutions, powders and suspensions, or in the form of highly concentrated aqueous, oily or other suspensions, dispersions, emulsions, oil dispersions, pastes, dusting agents, compositions, and applied by spraying, spraying in the form of a mist, spraying, scattering or potting. The form of use depends on the intended purpose; in any case, it should ensure the finest and uniform distribution of the composition of the invention.

The formulations are prepared in a manner known per se, for example by adding solvents and / or carriers. Inert preparations such as emulsifying or dispersing agents are usually admixed with the preparations.

Suitable surfactants are alkali metal salts, alkaline earth metal salts and ammonium salts of aromatic sulfonic acids such as lignin-, phenol-, naphthalene- and dibutylnaphthalenesulfonic acid, and fatty acids, alkyl- and alkylarylsulfonates, alkylsulfates, lauryl ether sulfates and sulfates. and salts of sulphated hexa-, hepta- and octadecanols, or glycol ethers of fatty alcohols, condensates of sulfonated naphthalene and its derivatives with formaldehyde, condensates of naphthalene or naphthalenesulphonic acids with phenol and formaldehyde, polyoxyethyleneoctylphenol ether, ethoxylated isooctyl esters, ochoxylate, n-octyl, alkylaryl polyether alcohols, isotridecyl alcohol, fatty alcohol / ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers or polyoxypropylene alkyl ethers, lauryl alcohol polyglycol ether acetate, sorbitol esters, lignin sulfide extracts or methylcellulose.

Powder, grit and dusting compositions can be prepared by mixing or co-grinding compounds I or II or a mixture of compounds I and II with a solid carrier.

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Granules (e.g. coated granules, impregnated granules or homogeneous granules) are usually prepared by binding the active ingredient (s) to a solid carrier.

As fillers or solid carriers, for example, mineral clays such as silica gel, kieselguhr, silica gels, silicates, talc, kaolin, limestone, lime, chalk, bolus, loess, II, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide , ground plastic materials and fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate, urea, and vegetable products such as cereal meal, tree bark meal, wood meal and nut shell meal, powdered cellulose or other solid carriers.

The formulations generally contain 0.1 to 95% by weight, preferably 0.5 to _Λ 90% by weight, of one of the compounds I or II or a mixture of the compounds I and II. The active ingredients are used in a purity of from 90% to 100%, preferably 95% to 100% (according to

NMR spectra or HPLC).

Compounds I or II or mixtures or corresponding preparations are used by treating the harmful fungi, their habitat or plants, seeds, soils, areas, materials or compartments to be protected from them with a fungicidally effective amount of the mixture or compounds I and II, in the case of a separate application.

Application can be carried out before or after attack by the harmful fungi.

DETAILED DESCRIPTION OF THE INVENTION

The synergistic effect of the compositions according to the invention was demonstrated by the following experiments:

The active ingredients were formulated, separately or together, as a 10% thick emulsion in a 63 wt. % cyclohexanone and 27 wt. emulsifying agent and diluted with water to the desired concentration.

Example 1 - Activity against Phytophthora infestans in tomatoes

The leaves of potato plants of the variety "GroBe Fleischtomate" were sprayed with spores until dripping with an aqueous suspension prepared from a basic solution of 10% active compound, 63% cyclohexanone and 27% emulsifier. The following day, the leaves were infected with an aqueous zoospore suspension of Phytophthora infestans. The plants were then placed in a water-saturated chamber at 19-18 ° C. After 6 days, untreated but infected control plants developed tomato mold to such an extent that the infection could be detected visually in percent.

Evaluation was performed by determining the percentage of affected leaf area. These percentages were converted to efficacy. Efficacy (E) was calculated as follows using the Abbot formula:

E = (1-α) Ί00 / β and corresponds to fungal infestation of the treated plants, expressed as a percentage. . _t • 't ¹ β corresponds to fungal infestation of untreated (control) plants, expressed as a percentage

Effectiveness 0 means that the degree of infestation of the treated plants corresponds to that of the untreated control plants; efficacy of 100 means that the treated plants were not infected.

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

Colby's formula:

E = x + y-x.y / 100

E the expected degree of effect, expressed as a percentage of the untreated control, using a mixture consisting of the active ingredients A and B at concentrations a and bx the degree of effect, expressed as a percentage of the untreated control, using active ingredient B at a concentration of b

The results are shown in Tables 1 and 2 below.

Table 1

Pr. Active ingredient Spray concentration of the active ingredient in ppm Effectiveness in% of untreated control 1 C Inspection (untreated) (100% assault 0 2C la 1.25 20 0.31 0 3C . Ib, 0.08 ; '0 4C Ha = dimethomorph 1.25 80 0.31 40 0.08 40 5C llb = flumetover 1.25 10 0.31 0 0.08 0

Table 2

Compositions of the invention Observed efficacy Calculated efficiency *) 1.25 ppm la + 1.25 ppm Ha (1: 1 mixture) 95 84 0.31 ppm la + 0.31 ppm Ha (1: 1 mixture) 70 40 1.25 ppm la + 1.25 ppm llb (1: 1 mixture) 75 28 0.31 ppm la + 0.31 ppm llb (1: 1 mixture) 40 0 0.08 ppm Ib @ + 0.08 ppm Ha) (1: 1 mixture) 90 76 0.08 ppm Ib @ + 0.08 ppm llb (1: 1 mixture) 95 60

*) calculated according to Colby's formula

Experimental results have shown that the observed efficacy in all blend ratios is higher than that calculated in advance using the Colby formula.

Claims (11)

PATENT CLAIMS What is claimed is: 1. A fungicidal composition comprising (a) a phenylbenzyl ether derivative of the formulas Ia, Ib or I.c, and b) a carboxamide of formula II selected from the group of compounds of formula IIa and IIb ci. t / \\ A fungicidal mixture according to claim 1, characterized in that it comprises a carboxamide of the formula IIa. The fungicidal mixture according to claim 1, characterized in that it comprises a carboxamide of formula IIb. The fungicidal mixture according to claim 1, characterized in that the weight ratio of the compounds i to the compound II is 20: 1 to 0.1: 2. A method of controlling harmful fungi, characterized in that the harmful fungi, their habitat or plants, seeds, soils, areas, materials or premises to be protected from them are treated with a compound of formula I as defined in claim 1 and a compound of formula II as defined in claim 1. A method according to claim 5, characterized in that compound I as defined in claim 1 and compound U as defined in claim 1 are applied simultaneously, that is, together or separately, or subsequently. Method according to claim 5, characterized in that the harmful fungi, their habitat or plants, seeds, soils, areas, materials or premises to be protected from them are treated with 0.01 to 0.5 kg / kg. ha of compound I as defined in claim 1. Method according to claim 5, characterized in that the harmful fungi, their living space or plants, seeds, soils, areas, materials or premises to be protected from them are treated with 0.05 to 1 kg / ha of the compound II as defined in claim 1. Use of compound I as defined in claim 1 for the preparation of a fungicidally effective synergistic mixture according to claim 1. Use of compound II as defined in claim 1 for the preparation of a fungicidally effective synergistic mixture according to claim 1. t ¹ I '' t ' Composition according to claim 1, characterized in that it comprises two parts, wherein one part contains the compound of formula I as defined in claim 1 in a solid or liquid carrier and the other part comprises the compound of formula II as defined in claim 1, in a solid or a liquid carrier.