SK199A3 - Fungicidal mixtures - Google Patents

Abstract

The invention concerns a fungicidal mixture which contains as active constituents: a1) the oxime ether carboxylic acid ester for formula (Ia) of one ot its salts or addition compounds; and/or a2) a carbamate of formula (Ib), in which X designates CH and N, n stands for 0, 1 or 2, and R designates halogen, C1-C4 alkyl and C1-C4 alkyl halide, of one its salts or addition products, wherein the R groups can be different when n stands for 2; and b) iminoctadines of formula (II) H2N-C(=NH)-NH-(CH2)8-NH-(CH2)8-NH-C(=NH)-NH2 of one of its salts or addition products, in a synergistically effective amount. The invention also concerns the use of this mixture as fungicide.

Description

Fungicidal mixtures

SUMMARY OF THE INVENTION

The present invention relates to a synergistic fungicidal composition comprising at least as active ingredients an oxime ether carboxylate of the formula Ia,

(Ia) or a salt or adduct thereof, and / or and ₂ ) a carbamate of the formula Ib,

in which

X is CH or N, n is 0, 1 or 2 and

R is halogen, C 1 -C 4 alkyl or C 1 -C 4 haloalkyl, wherein the radicals R may be different when n is 2, or a salt or adduct thereof, and

(b) iminoctadine of formula II;

H ₂ NC (= NH) -NH- (CH ₂ ) _e -NH- (CH ₂ ) _B -NH-C (= NH) -NH ₂ (11) or a salt or adduct thereof in a synergistically effective amount.

The invention further relates to methods for controlling harmful fungi with mixtures of compounds I and II and to the use of compound I and compound II for the preparation of such mixtures.

Compounds of formula Ia, their preparation and their action against harmful fungi have been described in EP-A 253 213. WO-A 96 / 01,256 and WO-A 96 / 01,258 disclose compounds of formula Ib, their preparation and their use. Compounds of formula II (common name: iminoctadine), their preparation and their action against harmful fungi are also known (cf. "Pesticide Manuall", p. 593).

It was an object of the present invention to provide compositions having improved activity against harmful fungi associated with reducing the total amount of active ingredients used (synergistic compositions) in terms of reducing application rates and improving the spectrum of activity of known compounds I and II.

Accordingly, we have found that this goal can be achieved using the mixture defined in the introduction. In addition, we have found that better control of harmful fungi is possible by simultaneous administration of compound I and compound II, that is, together or separately, or by application of compound I and compound II, rather than when individual compounds are used alone.

In particular, formula Ib means carbamates in which the combination of substituents corresponds to one row in the table below.

about

No. X rn 1.1 N 2-F I.2 N 3-F I.3 N 4-F I.4 N 2-Cl I.5 N 3-Cl I.6 N 4-Cl I.7 N 2-Br I.8 N 3-Br I.9 N 4-Br 1.10 N _2-CH3 1.11 N 3-CH ₃ 1.12 N _4-CH3 1.13 N 2-CH ₂ CH ₃ 1.14 N 3-CH ₂ CH ₃ 1.15 N 4-CH ₂ CH ₃ 1.16 N 2-CH (CH ₃ ) ₂ 1.17 N 3-CH _{(CH3) 2} 1.18 N 4-CH _{(CH3) 2} 1.19 N 2-CF ₃ I.20 N 3-CF ₃ 1.21 N 4-CF ₃ I.22 N 2,4-F _z I.23 N 2,4-Cl ₂ I.24 N 3,4-Cl ₂ I.25 N 2-Cl, _4-CH3 I.26 N 3-Cl, _4-CH3 I.27 CH 2-F I.28 CH 3-F I.29 CH 4-F I.30 CH 2-Cl 1.31 CH 3-Cl I.32 CH 4-Cl I.33 CH 2-Br I.34 CH 3-Br I.35 CH 4-Br

I.36 CH _2-CH3 I.37 CH 3-CH ₃ I.38 CH _4-CH3 I.39 CH 2-CH ₂ CH ₃ I.40 CH 3-CH ₂ CH ₃ 1:41 CH 4-CH ₂ CH ₃ I.42 CH 2-CH _{(CH3) z} I.43 CH 3-CH _{(CH3) 2} I.44 CH 4-CH _{(CH3) 2} I.45 CH 2-CF ₃ I.46 CH 3-CF ₃ I.47 CH 4-CF ₃ I.48 CH 2,4-F ₂ I.49 CH 2,4-Cl ₂ I.50 CH 3,4-Cl ₂ 1:51 CH 2-Cl, 4-CH 3 I.52 CH 3-Cl, 4-CH 3

Particularly preferred are compounds 1.12,1.23,1.32 and I.38.

Due to the basic nature of the oxime ether unit, compounds Ia and Ib 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, further carbonic acid, sulfuric acid, phosphoric acid and nitric acid.

Suitable organic acids are, for example, formic 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 having linear or branched alkyl radicals containing from 1 to 20 carbon atoms), arylsulfonic acids or aryldisulfonic acids (aromatic radicals such as phenyl and naphthyl to which one or two sulfonic groups are attached), alkylphosphonic acids acids (phosphonic acids having linear or branched alkyl radicals containing from 1 to 20 carbon atoms), arylphosphonic acids or aryldiphosphonic acids (aromatic radicals such as phenyl and naphthyl to which one or two acid radicals are attached phosphoric acid), wherein other substituents may be attached to the alkyl or aryl radicals, for example p-toluenesulfonic acid, salicylic acid, p-aminosalicylic acid, 2-phenoxybenzoic acid, 2-acetoxybenzoic acid and others.

Suitable metal ions are in particular the ions of elements of the first to eighth subgroups, in particular chromium, manganese, iron, cobalt, nickel, copper, zinc and others, as well as the second main group, especially calcium and magnesium, and the third and fourth main groups, especially aluminum, tin and lead. At the same time, the metals can be in the different powers that belong to them.

Pure active ingredients I and II are preferably used in the preparation of the mixtures, to which other active ingredients against harmful fungi or other pests such as insects, spiders or nematodes, or herbicidally active ingredients or growth regulators or fertilizers can be admixed.

The mixtures of compounds I and II, or the simultaneous joint or separate use of compounds I and II, are characterized by excellent activity against a wide range of phytopathogenic fungi, in particular from the classes Ascomycetes, Basidiomycetes, Phycomycetres and Deuteromycetes. Some act systemically and can therefore be used as foliar and soil fungicides.

They are particularly important for destroying a large number of fungi in different crops such as cotton, vegetables (eg cucumber, legume and pumpkin), barley, grass, oats, coffee, corn, fruit trees, rice, rye, soya, vine, wheat, ornamental plants, sugar beet and a variety of seeds.

They are particularly suitable for the control of the following phytopathogenic fungi: Erysiphe graminis (powdery mildew) on cereals, Erysiphe cichoracearum and Sphaerotheca fuliginea on pumpkins, Podosphaera leucotricha on apple trees, Uncicula necator on vines, Puccinia species on cereal, Rhinoceros on cereal Ustilago species on cereals and sugar beets, Venturia inaequalis (apple scab) on apple trees, Helminthosporium species on cereals, Septoria nodorum on wheat, Botrytis cinerea (strawberry mold) on strawberries, vegetables, ornamental plants and vines, Cercospora arachidicola herpotrichoides on wheat and barley, Pyricularia oryzae on rice, Phytophthora infestans on potatoes and tomatoes, Plasmopara viticola on grape vine, Alternaria species on vegetables and fruit trees and Fusarium and Verticillium species.

Furthermore, they can be used to protect materials (for example in the protection of wood), for example against Paecilomyces variotii.

The compounds I and II may be used simultaneously, together or separately or sequentially, in the case of separate use, this in principle has no effect on the result of the destruction measurements.

Compounds I and II are commonly used in a weight ratio of from 10: 1 to 0.05: 2, preferably 5: 1 to 0.05: 1, particularly preferably 1: 1 to 0.05: 1. In this regard, a number of compounds I refer to compound Ia or compound Ib, or a mixture thereof.

The application rates of the mixtures according to the invention are, in particular in the case of agricultural crops, from 0.01 to 7 kg / ha, preferably 0.01 to 5 kg / ha, particularly preferably 0.1 to 3 kg / ha, depending on the nature the desired effect.

In the case of the compounds I, the application rates are from 0.01 to 2.5 kg / ha, preferably 0.05 to 2.5 kg / ha, particularly preferably 0.1 to 1.0 kg / ha.

Correspondingly, in the case of the compounds II, the application rates are from 0.01 to 10 kg / ha, preferably 0.05 to 5 kg / ha, particularly preferably 0.05 to 2 kg / ha.

In 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 destroyed for plants, separate or joint application of compounds I and II or mixtures of compounds I and II can be effectively used by spraying or dusting the seeds, plants or soil before or after planting or before or after emergence of plants .

The fungicidal synergistic mixtures of the invention, or compounds I and II, can be formulated, for example, in the form of directly sprayable solutions, powders or suspensions, or in the form of highly concentrated aqueous, oily or other suspensions, dispersions, emulsions, oil dispersions, pastes, dusts, spray agents. or granules, and applied by spraying, atomizing, dusting, spraying or potting. The form of application depends on the intended use; in any case, a fine and even distribution of the composition according to the invention should be ensured.

The formulations are prepared in a manner known per se, for example by adding solvents and / or carriers. Typically, inert additives such as emulsifying or dispersing agents are mixed into the formulations.

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, alkyl sulfates, lauryl ether sulfates and sulfates. and salts of sulphated hexa-, hepta- and octadecanols or glycol ethers of fatty alcohols, condensates of sulphonated naphthalene and its derivatives with formaldehyde, condensates of naphthalene or naphthalenesulphonic acids, with phenol and formaldehyde, polyoxyethyleneoctylphenol ether, ethoxylated isooctyl- or octo-octyl- alkylaryl polyether alcohols, isotridecyl alcohol, fatty alcohol / ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers or polyoxypropylene, lauryl alcohol polyglycol ether acetate, sorbitol esters, lignin sulphite waste liquors or methylcellulose.

Powdered, dusting 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.

Granules (e.g. coated granules, impregnated granules or homogeneous granules) are conveniently 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, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground synthetic materials and fertilizers such as ammonium sulphate, ammonium phosphate, ammonium nitrate, ureas and products of vegetable origin such as cereal meal, tree bark meal, wood meal and nut shell meal, powdered cellulose or other solid carriers.

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

Compounds I or II or mixtures or corresponding formulations are used, wherein the harmful fungi, their habitat or plants, seeds, soil, areas, materials or compartments to be protected from them are treated with a fungicidally effective amount of the mixture, or of compounds I and II, in the case of separate administration.

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

DETAILED DESCRIPTION OF THE INVENTION

Efficacy against Botrytis cinerea

The active ingredients, prepared separately or together, are formulated as a 10% emulsion in admixture with 70% by weight. % cyclohexanone, 20 wt. % By weight of Nekanil ^R LN (Lutensol ^R AP6, an emulsifying and dispersing crosslinker based on ethoxylated alkylphenols) and 10 wt. Emulphor® EL (Emulan ^R EL, emulsifier based on ethoxylated fatty alcohols) and diluted with water to the desired concentration.

Neusiedler Ideal Elite ”chilli seedlings were sprayed to dropwise with an aqueous suspension containing 80% by weight of the active ingredient and 20% by weight of the emulsifying agent in the dry matter after developing 4-5 leaves. After spray drying, the plants were sprayed with a spore suspension of Botrytis cinerea and placed in a chamber at 22-24 ° C and high humidity. After 5 days, the disease developed on untreated plants that the necrosis of the leaves affected most of the leaves.

Evaluation was carried out by means of a percentage determination of the infected leaf areas. These percentages were converted into degrees of effect.

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

W = (β - α) * 100 / β and corresponds to fungal infestation of treated plants expressed as a percentage and β corresponds to fungal infestation of untreated (control) plants

An effect level of 0 means that the degree of infestation of the treated plants corresponds to that of the untreated control plants, an effect level of 100 means that the treated plants are not infected.

The expected degree of action of the active ingredient mixture was determined by the Colby formula [R.S. Colby, Weeds 15, 20-22 (1967)] and compared with the observed degree of effect.

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, use of the active ingredient B at a concentration of b

Effectiveness against Botrytis cinerea

Pepper seedlings (cultivar “Neusiedler Ideal Elite”) with 4 to 5 leaves developed were sprayed with a preparation of active ingredients. After spray drying, the plants were sprayed with a spore suspension of Botrytis cinerea and then left for 5 days in a chamber at 22-24 ° C and high humidity. The evaluation was performed visually.

Claims (9)

A fungicidal mixture, characterized in that it contains, as active ingredients, an oxime ether carboxylate of the formula Ia, CO2CH3 (Ia) or a salt or adduct thereof, and / or a ₂₎ a carbamate of formula Ib, and in which X is CH or N, n is 0, 1 or 2 and R is halogen, C 1 -C ₄ -alkyl or C 1 -C ₄ -haloalkyl, with radicals R may be different when n is 2, or a salt or adduct thereof, and (b) iminoctadine of formula II; H ₂ NC (= NH) -NH- (CH 2) e -NH- (CH ₂ ) a -NH-C (= NH) -NH ₂ (II) or a salt or adduct thereof in a synergistically effective amount. The fungicidal mixture according to claim 1, characterized in that the weight ratio of compound I or a salt or adduct thereof to compound II or a salt or adduct thereof is 10: 1 to 0.05: 2. A method for controlling harmful fungi, characterized in that the harmful fungi, their habitat or plants, seeds, soil, areas, materials or premises to be protected from them are treated with a compound of formula I or a salt or adduct thereof according to claim 1 and a compound of formula II or a salt or adduct thereof according to claim 1. The method according to claim 3, characterized in that the compound of formula I or a salt or adduct thereof according to claim 1 and the compound of formula II or a salt or adduct thereof according to claim 1 are applied simultaneously, i.e. together, separately or sequentially. Process according to claim 3 or 4, characterized in that the compound of the formula I or a salt or adduct thereof according to claim 1 is used in an amount of from 0.01 to 2.5 kg / ha. B Process according to any one of claims 3 to 5, characterized in that the compound of formula II or a salt or adduct thereof according to claim 1 is used in an amount of from 0.01 to 5 kg / ha. Use of a compound of formula I or a salt or adduct thereof according to claim 1 for the preparation of a fungicidally effective synergistic mixture according to claim 1. Use of a compound of formula II or a salt or adduct thereof according to claim 1 for the preparation of a fungicidally effective synergistic mixture according to claim 1. The composition of claim 1, which is prepared in two parts, wherein one part comprises compounds of formula I according to claim 1 in a solid or liquid carrier and the other part comprises compounds of formula II according to claim 1 in a solid or liquid carrier.