SK284256B6 - Fungicidal active agent combinations - Google Patents

Abstract

The novel active agent combinations of A) 8-t-butyl-2-(N- ethyl-N-n-propylamino)-methyl-1,4-dioxaspiro[5,4]-decan of formula (I) and B) 1-(4-chlorophenyl)-4,4-dimethyl-3-(1,2,4,- triazol-l-yl-methyl)-pentane-3-ol of formula (II) and C) a triazol derivative of formula (III) X = CH(OH) (=triadimenol) (IIIa) or X = CO (=triadimephon) (IIIb) have very good fungicidal properties.

Description

The invention relates to novel active compound combinations consisting of the known 8-t-butyl-2- (N-ethyl-N-propylamino) methyl-1,4-dioxaspiro [5,4] decane and two other known triazolyl derivatives, which are very well suited for destroying fungi.

BACKGROUND OF THE INVENTION

It is already known, 8-t-butyl-2- (N-ethyl-Nn-propylamino) -methyl-1,4-dioxaspiro [5.4] decane, 1- (4-chlorophenyl) -4,4-dimethyl- 3- (1,2,4-triazol-1-ylmethyl) -pentan-3-ol (tebuconazole), 1- (4-chlorophenoxy) -3,3-dimethyl-1- (1,2, 4-Triazol-1-yl) butan-2-ol (triadimenol) and 1- (4-chlorophenoxy) -3,3-dimethyl-1- (1,2,4-triazol-1-yl) - butan-2-one (triadimefon) have fungicidal properties (see EP-A 0 281 842, EP-A 0 040 345, DE-A 2 324 010 and DE-A 2 201 063).

It is further known that mixtures of 8-t-butyl-2- (N-ethyl-N-propylamino) methyl-1,4-dioxaspiro [5.4] decane and tebuconazole, or 8-t-butyl-2 - (N-ethyl-Nn-propylamino) -methyl-1,4-dioxaspiro [5,4] decane and triadimenol or triadimefon, or from tebuconazole and triadimenol or triadimefon may be used for the control of fungi (see EP-A 0 627 163 and EP-A 0 316 970). The efficacy of the individual components as well as the known mixtures of the corresponding two active substances is good. However, at very low rates of application, fungicidal efficacy in many cases lags behind expectations.

SUMMARY OF THE INVENTION

It has now been found that new combinations of active substances from

A. 8-t-Butyl-2- (N-ethyl-Nn-propylamino) -methyl-1,4-dioxaspiro [5.4] decane of formula (I) o- + _CH + (nc, H, -n

B. 1- (4-Chloro-phenyl) -4,4-dimethyl-3- (1,2,4-triazol-1-ylmethyl) -pentan-3-ol of formula (II)

OH

CH-CH3-CC (CH3) ₃

CH, I ‘+1.

(= Tebuconazole) N

N— ⁷

C. triazole derivative of formula (III)

(ΠΙ)

X = CH (OH) (= Triadimenol) (IIIa) or

X = CO (= Triadimefon) (Illb) have very good fungicidal properties.

Surprisingly, the fungicidal efficacy of the combinations according to the invention of the three active substances is considerably higher than the effects of the individual components or the effects of the first known mixtures of the two corresponding active substances. Thus, there is an unforeseeable true synergistic effect and not just the sum of the effects.

The active substances contained in the active substance combinations according to the invention and also possible combinations of two active substances are known (see EP-A 0 281 842, EP-A 0 040 345, DE-A 2 324 010, DE-A 2 201 063, EP-A 0 316 970 and EP-A 0 672 163).

When the active substances are present in the active compound combinations according to the invention in certain weight ratios, the synergistic effect is particularly evident. However, the weight ratios of the active ingredients in the active ingredient combinations may vary within a relatively wide range. In general, 0.1 to 1.5 parts by weight, preferably 0.1 to 1.0 parts by weight, of active compound of the formula (II) and 0.1 to 1.5 parts by weight, preferably 0.1 to 1.0 part by weight of the active compound of the formula (III).

The active compound combinations of the present invention have very good fungicidal properties and can be used to control phytopathogenic fungi such as Plasmodiophoromycetes, Oomycetes, Chytridomycetes, Zygomycetes, Ascomycetes, Basidiomycetes, Deuteromycetes and the like.

Non-limiting examples include some agents of fungal and bacterial diseases which fall under the above-mentioned:

Xanthomonas species, such as Xanthomonas oryzae.

Pseudomonas species, such as, for example, Pseudomonas lachrymans.

Erwinia species, such as Erwinia amylov'ora. Pythium species, such as Pythium ultimum.

Phytophthora species, such as, for example, Phytophthora infestans.

Pseudoperonospora species, such as, for example, Pseudoperonospora humuli or Pseudoperonospora cubensis.

Plasmopara species, such as, for example, Plasmopara viticola. Peronospora species, such as Peronospora pisi or Peronospora brassicae.

Erysiphe species, such as Erysiphe graminis.

Sphaerotheca species, such as Sphaerotheca fiiliginea.

Podosphaera species, such as, for example, Podosphaera leucotricha.

Venturia species, such as Venturia inaequalis. Pyrenophora species, such as Pyrenophora teres or Pyrenophora graminea (conidia form: Drechslera, synonym: Helminthosporium).

Cochliobolus species, such as Cochliobolus sativus (conidia form: Drechslera, synonym: Helminthosporium).

Uromyces species, such as Uromyces appendiculatus.

Puccinia species, such as Puccinia recondita. Tilletia species, such as Tilletia caries.

Ustilago species, such as Ustilago nuda or Ustilago avenae.

Pellicularia species, such as Pellicularia sasakii.

Pyricularia species, such as Pyricularia oryzae. Fusarium species, such as Fusarium culmorum. Botrytis species, such as Botrytis cinerea.

Septoria species, such as Septoria nodorum. Leptosphaeria species, such as Leptosphaeria nodorum.

Cercospora species, such as Cercospora canescens. Alternaria species, such as Alternaria brassicae. Pseudocercosporella species, such as, for example, Pseudocercosporella herpotrichoides.

The active compound combinations according to the invention can be used particularly successfully for the control of cereal diseases such as against Pyrenosphora teres, Erysiphe graminis, Rhynchosporium secalis, Leptosphaeria nodorum, Septoria tritici and Puccinia spp.

The good acceptability of the active ingredient combinations for plants at the concentrations necessary to control plant diseases permits the treatment of above-ground parts of plants, seedlings, seeds and soil.

The active substances can be converted into conventional preparations such as solutions, emulsions, suspensions, powders, foams, pastes, granulates, aerosols, active substances impregnated with natural and synthetic substances, microcapsules in polymerization substances and seed encapsulants, preparations with flammable additives such as smoke cartridges and the like, as well as hot or cold milling compositions.

These preparations can be prepared by known methods, for example by mixing the active ingredient with extenders, i.e. liquid solvents, under pressure with liquefied gases and / or solid carriers, optionally using surfactants, i.e. emulsifiers and / or dispersants, and / or foaming agents. agents.

If water is used as the extender, it is also possible, for example, to use organic solvents as co-solvents. Essentially suitable liquid solvents are: aromatics such as xylene, toluene or alkyl naphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons such as cyclohexane or paraffins such as petroleum fractions alcohols such as butyl alcohol or glycols as well as their ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, or strongly polar solvents such as dimethylformamide or dimethylsulfoxide as well as water.

Liquefied gaseous extenders or carriers are understood to be those liquids which are gaseous at normal temperature and under normal pressure, for example aerosol carrier gases such as halogenated hydrocarbons as well as butane, propane, nitrogen and carbon dioxide.

Suitable solid carriers are, for example, natural rock meals such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic rock meals such as highly disperse silicic acid, alumina and silicates. Suitable solid carriers for granulates are, for example, crushed and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite, as well as synthetic granules of inorganic and organic flours, as well as granules of organic materials such as sawdust, coconut shells. nuts, corn bars and tobacco stems.

Suitable emulsifying and / or foaming agents are, for example, nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters and polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ether, alkylsulfonates, alkylsulfates, arylsulfonates, and protein hydrolyses. Suitable dispersing agents are, for example, lignosulphite leachates and methylcellulose.

Adhesion enhancers such as carboxymethylcellulose and natural and synthetic, powdered, granular or latex polymers such as acacia, polyvinyl alcohol, polyvinyl acetate, as well as natural phospholipids such as cephalins and lecithins and synthetic phospholipids can be used in the formulations. Other additives may be mineral and vegetable oils.

Alternatively, dyes such as inorganic pigments, for example iron oxides, titanium dioxide and ferrocyanide blue, or organic dyes such as alizarin dyes, azo dyes and metal nicocyanine dyes can also be used.

Furthermore, trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc can be used.

The formulations generally contain from 0.1 to 95% by weight of active compounds, preferably from 0.5 to 90% by weight.

The active compound combinations according to the invention can be used in preparations in admixture with other known active substances, such as fungicides, acaricides, insecticides or herbicides, as well as in mixtures with fertilizers or plant growth regulators.

The active compound combinations can be used per se, in the form of their preparations or in dosage forms prepared therefrom, such as application solutions, emulsifiable concentrates, emulsions, suspensions, spray powders, soluble powders and granules.

The application is carried out by conventional means, for example by pouring, spraying, spraying, dusting, spraying, spraying, foaming, coating, dry pickling, wet pickling, sludge pickling, incrustation and the like.

When treating part of the plants, the concentrations of the active compounds in the use forms can be varied within a wide range. In general, this concentration is 1 to 0.0001% by weight, preferably 0.5 to 0.001% by weight.

In the treatment of seed, amounts of active compound of from 0.001 to 50 g per kilogram of seed, preferably 0.01 to 10 g, are generally required.

In soil treatment, active compound concentrations of 0.00001 to 0.1% by weight, preferably 0.0001 to 0.02% by weight, are required at the site of action.

The good fungicidal effect of the active compound combinations according to the invention is apparent from the following examples. While the individual active ingredients as well as combinations of the two corresponding active ingredients have weaknesses in the fungicidal effects, combinations of the three active ingredients have an effect which exceeds a simple sum of the effects as well as the effect of known combinations with a synergistic effect.

The synergistic effect of fungicides always lies in the fact that the fungicidal effect of the active substance combination is higher than the sum of the effect of the individually applied active substances.

DETAILED DESCRIPTION OF THE INVENTION

The use of the active compound combinations according to the invention follows from the following examples.

Example 1

Test for Pyrenophora teres (barley) / curative

Solvent: 10 parts by weight of N-methyl-pyrrolidone emulsifier: 0.6 parts by weight of alkyl aryl polyglycol ether

To make a suitable active ingredient preparation, 1 part by weight of active ingredient or a combination of active ingredients is mixed with the indicated amount of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.

To test the curative activity, young plants are sprayed with a conidia suspension of Pyrenophora teres. The plants are then left for 48 hours at 20 ° C and 100% relative humidity in an incubation chamber. They are then sprayed with the active compound preparation in the indicated application rate.

The plants are then placed in a greenhouse at a temperature of about 20 ° C and a relative humidity of about 80%.

Evaluation is performed 7 days after inoculation. In doing so, 0% means an effect equivalent to that of the control, whereas an effect level of 100% means that no attack was observed.

The active substances, the application rate and the results of the experiment are shown in Table 1 below.

Table 1

Pyrenophora teres test (barley / curative test)

active substance amount of active substance applied in g / h degree of effect in% of non-control known 250 38 <CHJŕ-O ^<0 l _of C, H ₅ (I) OH C) - / '% CH CH _{R a} - C-CíCHJ, - (L 250 62 OH O-CH-CH-C '> y, Λ in (M.> 250 68 according to the invention 83,33 81 (D ♦ } 33.33} (II) + + 83,33 (IIIa) (1: 1: 1)

Example 2

Test for Leptosphaeria nodorum (wheat) / curative

Solvent: 10 parts by weight of N-methyl-pyrrolidone emulsifier: 0.6 parts by weight of alkyl aryl polyglycol ether

To make a suitable active ingredient preparation, 1 part by weight of active ingredient or a combination of active ingredients is mixed with the indicated amount of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.

To test for curative activity, young plants are sprayed with a spore suspension of Leptosphaeria nodorum. The plants are then left for 48 hours at 20 ° C and 100% relative humidity in an incubation chamber. They are then sprayed with the active compound preparation in the indicated application rate.

The plants are then placed in a greenhouse at a temperature of about 15 ° C and a relative humidity of about 80%.

Evaluation is carried out 10 days after inoculation. In doing so, 0% means an effect equivalent to that of the control, whereas an effect level of 100% means that no attack was observed.

The active substances, the application rate and the results of the experiment are shown in Table 2 below.

Table 2

Test for Leptosphaeria nodorum (wheat) / curative

active substance amount of active substance applied degree of effect in% of unprocessed. control known 250 18 iw-OO ^ · ^c _of C, M, R ω OH Cl-CH2-CH2-C-CH3), - CH, 250 58 (II) 250 33 Cl ° "CH-C" C (CMJ, ( ^{N N} NU (Iii b;

active substance amount applied of the active substance degree of effect related to control % in progress. according to the invention 83.3 68 (D * 83.3 j (II)} ♦ + 83.3 (IIIb) (1: 1: 1) ABOUT) 125 75 4 * (II)} 02.5} + - (IIIb) 62.5 (2: 1: 1) (D 187.5 75 * * (II)} 31,25} + (IIIb) 31.25 (6: 1: 1)

SK 284256-6

Example 3

Puccinia test (wheat) / curative

Solvent: 10 parts by weight of N-methyl-pyrrolidone emulsifier: 0.6 parts by weight of alkyl aryl polyglycol ether

To make a suitable active ingredient preparation, 1 part by weight of active ingredient or a combination of active ingredients is mixed with the indicated amount of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.

For the curative activity test, young plants are inoculated with a suspension of Puccinia recondita spores in 0.1% aqueous agar solution. The plants are then left for 24 hours at 20 ° C and 100% relative humidity in an incubation chamber.

hours after inoculation, the plants are sprayed with the active compound preparation in the indicated application rate.

The plants are then placed in a greenhouse at a temperature of about 20 ° C and a relative humidity of about 80% to promote the development of rust spots.

Evaluation is carried out 10 days after inoculation. In doing so, 0% means an effect equivalent to that of the control, whereas an effect level of 100% means that no attack was observed.

The active substances, the application rate and the results of the experiment are shown in Table 3 below.

Table 3

Puccinia test (wheat) / curative

active substance active substance applied amount of active substance in g / h degree of effect in% of unprocessed. control known 12.5 79 } 12.5 1 · 4 - OH (í ^N v // N— ' (II) (M)

Table 3 (continued)

active substance amount of active substance applied in g / h degree of effect in% of unprocessed. control 12.5 S1 Ο, Η, -h ⁴ } 12.5 (I) 4- í OH CH — CH — CICH, Ä M (1.1) according to the invention 18.75 100 (I) + 6.25} (II)} + 6.25 (IIIa) (3: 1: 1)

Example 4

Test on Erysiphe (barley) / protective

Solvent: 10 parts by weight of N-methyl-pyrrolidone emulsifier: 0.6 parts by weight of alkyl aryl polyglycol ether

To make a suitable active ingredient preparation, 1 part by weight of active ingredient or a combination of active ingredients is mixed with the indicated amount of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.

In order to test the curative activity, young plants are sprayed with the preparation of active compound in the indicated application rate.

After spray drying, the plants are dusted with spores of Erysiphe graminis f. sp. hordei.

The plants are then kept at a temperature of about 20 ° C and 80% relative humidity in a greenhouse to promote the development of mildew spots.

Evaluation is performed 7 days after inoculation. In doing so, 0% means an effect equivalent to that of the control, whereas an effect level of 100% means that no attack was observed.

The active substances, the application rate and the results of the experiment are shown in Table 4 below.

Table 4

Erysiphe test (barley / protective

active substance amount of active substance applied in g / h degree of effect in% of untreated control known 12.5 34 } 12.5 ω J 4 · OH and C y - CH ₍ CH 2 -C 6 -CH 2 CH 2), CH, < ^N 'n W // N—' dl) (1: 1)

B. 1- (4-Chloro-phenyl) -4,4-dimethyl-3- (1,2,4-triazol-1-ylmethyl) -pentan-3-ol of formula (II)

OH

I

CH-CH - CC (CH _{3) 3}

CH _and (II) (= Tebuconazole) (j N

N '

and

C. triazole derivative of formula (III)

CH X C (CH 3) j (ΠΙ)

JJ

active substance amount of active ingredient applied in gfh degree of effect in% of unprocessed. control v / o-E-W C, H, N (D *} OH CH — CHC (CH3), I- / (IIIa) (1-1) 12.5 *} 12.5 34 according to the invention (D + (II)} + (IIIa) ¢ 2: 1: 1) 12.5 6.25} 6.25 67

X = CH (OH) (= Triadimenol) (IIIa) or

X = CO (= Triadimefon) (IIIb), wherein in the active compound combination the weight ratio of active compound of formula (1) to active compound of formula (II) is 1: 0.1 to 1: 1.5 and to active compound of formula (III) 1: 0.1 to 1: 1.5.

Method for destroying fungi, characterized in that fungi and / or their environment are treated with a combination of active substances according to claim 1.

Use of the active ingredient combination according to claim 1 for controlling fungi.

Process for the production of fungicidal compositions, characterized in that the active compound combinations according to claim 1 are mixed with fillers and / or surfactants.

Claims (1)

PATENT CLAIMS What is claimed is: 1. A fungicidal composition having a synergistic effect, comprising a combination of the active ingredients of A. 8-t-Butyl-2- (N-ethyl-N-n-propylamino) methyl-1,4-dioxaspiro [5,4] decane of formula (I)