BG63523B1 - Composition of fungicide active substances - Google Patents

Abstract

The composition has excellent fungicidal properties. It is a new combination of active substances, in particular of: A) 8-tert.-butyl-2-(N-ethyl-N-n-popylamino)-methyl-1,4-dioxyaspiro[5, 4]decane having the formula B)1-(4-chlorophenyl)-4,4-dimethyl-3-(1,2,4-triazol-1-yl-methyl)- pentan-3-ol(tebuconazole) having the formula and C) a triazole derivative having the formula where X = CH(OH) (=triadimenol) or X = CO (=triadimephon). 4 claims

Description

Technical field

The invention relates to a novel combination of active substances consisting of the known 8-tert-butyl-2- (N-ethyl-N-propylamino) -methyl-1,4-dioxaspiro [5,4] decane and the other two known triazolyl derivatives and is well suited to the fight against fungi.

8-tert-butyl-2- (N-ethyl-N-n-propylamino) -methyl-1,4-dioxaspiro [5,4] decane, 1- (4-chlorophenyl) -4,4-dimethyl-3 - (1,2,4-triazol-1-yl-methyl) -pentan-3-one (= tebuconazole), 1- (4-chlorophenoxy) -3,3-dimethyl-1- (1,2,4- triazol-1-yl) -butan-2-ol ( ^g triadimenol) and 1- (4-chloro-phenoxy) -3,3-dimethyl-1- (1,2,4-triazol-1-yl) -butane -2one ( ⁼ triadimephone) 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).

Mix it up

- from 8-tert-butyl-2- (L-ethyl-N-propylamino) -methyl-1,4-dioxaspiro [5,4] decane and tebuconazole

- or from 8-tert-butyl-2- (14-ethyl-L1-n-propylamino) -methyl-1,4-dioxaspiro [5,4] decane and triadimenol or triadimephone or

- tebuconazole and triadimenol or triadimephone can be used to combat fungi (see EP-A 0 627 163 and EP-A 0 316 970). Both the activity of the individual components and the known mixture of the two components is good. However, with very small amounts of application, there is still much to be desired in terms of fungicidal efficacy.

The new combination of active substances has very good fungicidal properties. Consists of

A) 8-tert-Butyl-2- (14-ethyl-N-propylamino) -methyl-1,4-dioxaspiro [5,4] decane

mule ^η 0 AND

(B) 1- (4-chlorophenyl) -4,4-dimethyl-3 (1,2,4-triazol-1-yl-methyl) -pentan-3-ol (- tebu-

and (C) a triazole derivative of form-

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

X ^g CO (= triadimefon) (ΙΠ6).

According to the invention, the fungicidal activity of the combination of the three active substances has a significantly higher activity than the activity of the individual components, respectively, than the activity of the known combinations of the two active substances. Therefore, there is an unpredictable true synergistic effect, not just a single complement to the activity.

The active substances contained in the combination according to the invention as well as the combination of two active substances are known (see EP-A 0 281 842, EP-A 0 040 345, DE-A 2 324 010 and DE-A 2 201 063, EP-A 0 316 970 and EP-A 0 627 163).

If the active substances in the combination of active substances according to the invention are in certain weight ratios, then the synergistic effect is particularly pronounced. The weight ratios of the active substances in the combination can vary over a relatively broad range. Generally, 0.1 to 1.5 parts by weight, preferably 0.1 to 1.0 parts by weight, of the active compound of formula I are given by weight. active substance of formula II and 0.1 to 1.5 parts by weight, preferably from 0.1 to 1.0 parts by weight of the active compound of formula III.

The combination of active substances according to the invention has very good fungicidal properties and can be used to control phytopathogenic fungi such as Plasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes, Deuteromycetes, etc.

For example, but not limited to the scope of the invention, some causes of fungal and bacterial diseases are listed:

Xanthomonas - species such as Xanthomonas oryzae;

Pseudomonas - species such as Pseudomonas lachrymans;

Erwinia - species such as Erwinia amylovora; Phythium - species such as Phythium uitimum; Phytophtora - species such as Phytophtora infestancs;

Pseudoperonospora - species such as Pseudoperonospora humuli or Pseudoperonospora cubensi;

Plasmopara - species such as Plasmopara viticola;

Perenospora - species such as Perenospora pisi or Perenospora brassicae;

Erysiphe - species such as Erysiphe gramminis;

Sphaerotheca - species such as Sphaerotheca fuliginea;

Podosphaera - species such as Podosphaera leucotricha;

Venturia - species such as Venturia inaequalis;

Pyrenophora - species such as Pyrenophora teres or Pyrenophora graminea (conidial form: Drechslera, syn: Helminthosporium);

Cochliobolus - species such as Cochliobolus sativus conidia: Drechslera, syn: 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 Pseudocercosporella herpotrichoides.

The combination of active substances of the invention is particularly suitable for combating cereal diseases such as Pyrenophora teres, Erysiphe graminis, Rhynchosporium secalis, Leptosphaeria nodorum, Septoria tritici and Puccinia spp.

The good tolerance of the plants to the combination of active substances in the concentration necessary for the control of plant diseases makes it possible to treat the aerial parts of the plants, the plant parts for planting and the seed as well as the soil.

The active substances can be formulated in conventional formulations such as solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols impregnated with the active substances of natural and synthetic substances, microcapsules in polymeric substances, and seed coatings, and more formulations with additives for combustion, such as cartridges, boxes or spirals for smoking, ULV-cold or hot mist-formulations.

These formulations are prepared in a known manner, for example by mixing the active substances with diluents, i. liquid solvents, liquefied gases and / or solid carriers, optionally using surfactants, i. e. emulsifiers and / or dispersants and / or foaming agents. In the case of using water as a diluent, organic solvents may, for example, be used as auxiliary solvents. Liquid solvents include mainly aromatic substances such as xylene, toluene or alkylnaphthalene, chlorinated aromatic or chlorinated aliphatic hydrocarbons such as chlorobenzene, chloroethylene or paraffins, for example petroleum fractions, alcohols such as butanol or glycol, and their ethers and esters ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, highly polar solvents such as dimethylformamide and dimethyl sulfoxide, as well as water. Liquid gaseous diluents or carriers are those liquids which are gaseous at ambient temperature and atmospheric pressure, for example aerosols derived from liquefied gas, such as halogenated hydrocarbons such as butane, propane, nitrogen and carbon dioxide. Suitable carriers, for example, are ground natural minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and synthetic minerals such as fine silica, aluminum oxide and silicates, such as solid carriers. for example, crushed and fractionated minerals such as fine silica, aluminum oxide and silicates. Suitable granular supports are suitable, for example, crushed and fractionated natural rocks such as calcite, marble, pumice, sepiolite and dolomite, as well as synthetic granules of inorganic and organic flours, as well as granules of organic substances such as bran, coconut shells, cobs corn and tobacco stems. Emulsifying or foaming agents include, for example, non-ionic and anionic emulsifiers such as polyoxyethylene fatty acid esters, polyoxyethylene fatty acid ethers, for example alkylarylpolyglycol ethers, alkylsulfonates, alkylsulfonates, allylsulfonylsulphines Suitable dispersants are, for example, lignin-sulfitablauge or methylcellulose.

The formulations may include adhesives such as carboxymethylcellulose, natural and synthetic polymers in the form of powders, granules or latex-like arabic, polyvinyl alcohol, polyvinyl acetate, as well as natural phospholipids such as cephalin and lecithin, and synthetic phospholipids. Other additives may be mineral and vegetable oils.

Dyes such as inorganic pigments, such as iron oxide, titanium oxide and ferrocyan blue, and organic dyes such as alizarin, azo and metal phthalocyanine dyes, and trace elements for nutrients such as iron salts, manganese, manganese, can be used in the formulations. , cobalt, molybdenum and zinc.

The formulations generally contain between 0.1 and 95% by weight. active substances, preferably between 0.5 and 90%

The combination of active substances of the invention may take the form of a mixture with other known active substances, such as fungicides, insecticides, acaricides and herbicides, as well as mixtures with fertilizers or plant growth regulators.

The combination of active substances can be used as such, in the form of formulations or as a ready-to-use form, such as ready-to-use solutions, emulsion concentrates, emulsions, suspensions, spray powders, soluble powders and granules.

The application is carried out in the usual way, for example, by irrigation, spraying, wetting, pouring, spraying, dry scrubbing, wet scrubbing, wet scrubbing, slurrying or inlaying.

When treating parts of plants, the concentrations of the active substances in their application forms may vary over a larger range. Generally, the limits are between 1 and 0.0001% by weight, preferably between 0.5 and 0.001%.

In the treatment of seed, amounts of the active substance of 0.001 to 50 g per kilogram of seed, preferably 0.01 to 10 g, are preferably used.

In soil treatment, concentrations of active substances of 0.00001 to 0.1% by weight, preferably 0.0001 to 0.02% by weight, are required. at the point of impact.

The good fungicidal activity of the combination of active substances of the invention is apparent from the following examples. While the individual active substances and the combination of two of them show defects in their fungicidal activity, the combination of the three active substances shows an activity that exceeds that of the total effect as well as that of the dual combination and shows a synergistic effect.

The synergistic effect of fungicides is when the fungicidal activity of the combination of active substances is greater than the sum of the activities of the separately administered active substances.

Examples of carrying out the invention

Example 1.

Pyrenophora teres - barley / curative test

Solvent - 10 parts by weight N-methyl-pyrrolidone

Emulsifier - 0.6 parts by weight alkylaryl polyglycester

To obtain the appropriate formulation of the active substances, 1 parts by weight were mixed. active substance or combination of active substances with the given amounts of solvent and emulsifier and the resulting concentrate is diluted with water to the desired concentration.

To test the healing activity, young plants were sprayed with a suspension of co4 nidinium from Pyrenophora teres. Plants stand for 48 h in an incubation chamber at 20 ° C and 100% relative humidity. The plants are then sprayed with the active substance preparation at the indicated rate of application.

Plants are placed in a vegetation house at a temperature of about 20 ° C and about 80% relative humidity.

Seven days after inoculation, the counting begins. In this case, 0% means activity that corresponds to the control, while 100% means activity where no infection is observed.

The active substances, application rates and test results are presented in the following table:

Table 1.

Pyrenophora teres - barley / curative test

active substance application rate in g / hake % activity on untreated control known: (SNLS-Οζχ ° CH ₂ - \ CjH / n (Ο 250 38 C »2 ύ (II) 250 62 Cl - ^^ - <> - <j> bC ^ (CHj) ₃ 0 (Illa) 250 68 according to the invention: (1) + (II) + (Illa) (1: 1: 1) 83.88 + 83.33 + 83.33 81

Example 2.

Leptosphaeria nodorum - experience (wheat) / curative

Solvent - 10 parts by weight N-methylpyrrolidone

Emulsifier - 0.6 parts by weight alkylaryl polyglycolether

To obtain the appropriate formulation of the active substances, 1 parts by weight were mixed. active substance or combination of 5θ active substances with the given amounts of solvent and emulsifier, and the resulting concentrate is diluted with water to the desired concentration.

To test the healing activity, young plants were sprayed with a spore suspension of Leptosphaeria nodorum. Plants stand for 48 h in an incubation chamber at 20 ° C and 100% relative humidity. The plants are then sprayed with the active substance preparation at the indicated rate of application.

Plants are placed in a vegetation house at a temperature of about 15 ° C and about 80% relative humidity.

Ten days after inoculation, the counting takes place. In this case, 0% means activity that corresponds to the control, while 100% means activity where no infection is observed.

The active substances, application rates and test results are presented in the following table.

Table 2

Leptosphaeria nodorum - experience (wheat) / curative

active substance application rate in g / hake % activity on untreated control known: SZN7P (1) 250 18 CIG ύ (II) 250 58 Ch — O-CH-C-C (CH3) c (B (nib) 250 33 according to the invention: (1) + (II) + (lllb) (1: 1: 1) 83.88 + 83.33 + 83.33 68 according to the invention: (1) + (II) + (yyyy) (2: 1: 1) 125 + 62.5 + 62.5 75 according to the invention: (I) + (II) + (lllb) (6: 1: 1) 187.5 + 31.25 + 31.25 75

Example 3.

Puccinia experience (wheat) / curative

Solvent - 10 parts by weight N-methyl-pyrrolidone

Emulsifier - 0.6 parts by weight alkylaryl polyglycolether

To obtain the appropriate formulation of the active substances, 1 parts by weight were mixed. active substance or combination of active substances with the given amounts of solvent and emulsifier and the resulting con- centrate thus obtained is diluted with water to the desired concentration.

To test the healing activity, young plants were inoculated with a suspension of Puccinia recondita spores in 0.1% agar solution. The plants were incubated for 24 h in an incubation chamber at 20 ° C and 100% relative humidity.

h after inoculation, the plants are sprayed with the active substance preparation at the indicated application rate.

Plants are placed in a growing house at about 20 ° C and about 80% relative humidity to create conditions for the disease to develop.

Ten days after inoculation, the counting takes place. In this case, 0% means activity that corresponds to the control, while 100% means activity where no infection is observed.

The active substances, application rates and test results are presented in the following table.

Table 3.

Puccinia experience (wheat) / curative

active substance application rate in g / hake % activity on untreated control known: “HDN ·· C3H7 n 12.5 (1) + 79 + 12.5 CH- <V-CHj-CH ^ - ^ GHjb CH3 0 (II) (1: 1) 'Xigg ·' C3H / P (I) 12.5 91 + + CI - / V - O - CH - CH - C (CHjh (Illa) 12.5 (1: 1) according to the invention: 18.75 + 6.25 + 100 (I) + (II) + (Illa) (3: 1: 1) 6.25

Example 4.

Erysiphe trial (barley) / safety

Solvent - 10 parts by weight N-methyl-pyrrolidone

Emulsifier - 0.6 parts by weight alkylaryl polyglycolether

To obtain the appropriate formulation of the active substances, 1 parts by weight were mixed. active substance or combination of active substances with the given amounts of solvent and emulsifier and the resulting concentrate diluted with water to the desired concentration,

For the test of protective activity, young plants are sprayed with the formulation with the indicated application rate.

After the spray has dried, the plants are sprayed with Erysiphe graminis f spores. sp. hordei.

Plants are placed in a vegetation house at a temperature of about 20 ° C and about 80% relative humidity to create conditions for the development of powdery mildew.

Ten days after inoculation, the counting takes place. In this case, 0% means activity that corresponds to the control, while 100% means activity where no infection is observed.

The active substances, application rates and test results are presented in the following table.

Table 4.

Erysiphe trial (barley) / safety

active substance application rate in g / hake % activity on untreated control known: CjHr'n 12.5 (!) 4 + ύ 12.5 34 (II) (1: 1) 12 5 (!) + 34 + ° and α - <Y - O - CH - CH - C (CHj) j 0 (Illa) (1 · 1) 12.5 according to the invention: 18.75 + 6.25 + 67 (1) + (II) + (Illa) (2: 1: 1) 6.25 _ _

Claims (4)

Claims A fungicidal agent comprising 8-tert-butyl-2- (Methyl-N-n-propylamino) -methyl-1,4-dioxaspiro [5,4] decane of formula _2- ^r / ^{3H, 1 n} (I) and 1- (4-chlorophenyl) -4,4-dimethyl-3- (1,2,4 triazol-1-yl-methyl) -pentan-3-ol of the formula and a triazole derivative of the formula X - CH (OH) (Sha) or X = CO (IIIb) $ in which the combination of active substances has a weight ratio of an active substance of formula I to an active substance of formula II between 1: 0.1 and 1: 1.5 and to an active IQ of formula III between 1 : 0.1 and 1: 1.5. A method of controlling mushrooms, characterized in that the combination of active substances according to claim 1 affects the fungi and / or their habitat. 15 Use of a combination of active substances according to claim 1 for the control of mushrooms. 4. A method for preparing a fungicidal agent, wherein the combination of active substances of claim 1 is mixed with diluents and / or surfactants.