DE10352264A1 - Fungicidal combination of active ingredients - Google Patents

Abstract

The invention relates to a drug combination consisting of the known 8-tert-butyl-1,4-dioxaspiro [4.5] decan-2-ylmethyl (ethyl) (propyl) amine (spiroxamine) on the one hand and other known active ingredients on the other hand and very good for Combating phytopathogenic fungi is suitable.

Description

The The invention relates to an active ingredient combination of the known 8-tert-butyl-1,4-dioxaspiro [4.5] decan-2-ylmethyl (ethyl) (propyl) amine (Spiroxamine) and other well-known active ingredients that are very good for fight of phytopathogenic fungi is suitable.

It It is already known that 8-tert-butyl-1,4-dioxaspiro [4.5] decan-2-ylmethyl (ethyl) (propyl) amine (Spiroxamine) has fungicidal properties (see EP-A-O 281 842). The effectiveness of this substance is good, but at low application rates in some cases to be desired.

Further it is already known that numerous azole derivatives and strobilurins for fighting can be used by mushrooms (see Pesticide Manual, 12th Edition (2000)). Also the effect However, these substances is not sufficient at low application rates.

und
der Verbindung der Formel (II) (Referenz: WO 96/16048)

und
der Verbindung der Formel (III) (Referenz: DE-A 196 02 095)
3-[1-[2-(4-<2-Chlorphenoxy>-5-fluorpyrimid-6-yloxy)-phenyl]-1-(methoximino)-methyl]-5,6-dihydro-1,4,2-dioxazin

sehr gute fungizide Eigenschaften besitzt.It has now been found that an active ingredient combination of 8-tert-butyl-l, 4-dioxaspiro [4.5] decan-2-ylmethyl (ethyl) (propyl) amine (spiroxamine) (Reference: EP-A 0 281 842) of the formula (I)

and
the compound of the formula (II) (Reference: WO 96/16048)

and
the compound of the formula (III) (Reference: DE-A 196 02 095)
3- [1- [2- (4- <2-chlorophenoxy> -5-fluorpyrimid-6-yloxy) -phenyl] -1- (methoximino) -methyl] -5,6-dihydro-1,4,2- dioxazine

has very good fungicidal properties.

Surprisingly is the fungicidal activity of the active ingredient combination of the invention the three active ingredients much higher than the sum of the effects the individual active ingredients or the effect of the previously known mixtures from two active ingredients. So there is an unpredictable, real synergistic effect before and not just an effect supplement.

The active ingredient of the formula (I) is known (cf., for example, EP-AO 281 842). The active compounds of the formulas (II) and (III) present in the active ingredient combination according to the invention in addition to the active ingredient of the formula (I) are also known (see References).

The following active ingredient combination is also known:
Active substance combination containing compounds of the formula (II) and (III): WO 98/47367.

If the active ingredients in the active ingredient combination according to the invention in certain weight ratios are present, the synergistic effect is particularly evident. However, you can the weight ratios the active ingredients in the drug combination in a relatively large area be varied.

In general, 1 part by weight of active ingredient of the formula (I)
0.1-10 parts by weight, preferably 0.2-5 parts by weight of active ingredient of the formula (II),
and
0.05-10 parts by weight, preferably 0.1-5 parts by weight of active compound of the formula (III).

The active compound combination according to the invention, applied simultaneously, together or separately, has very good fungicidal properties and leaves to fight of phytopathogenic fungi, such as Plasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes and Deuteromycetes deploy.

The Inventive drug combination is particularly suitable for combating cereal diseases, like Erysiphe, Cochliobolus, Pyrenophora, Rhynchosporium, Septoria, Fusarium, Pseudocercosporella and Leptosphaeria, Puccinia, Ustilago, Tilletia and Urocystis and to combat fungal attack on non-cereal crops, like wine, fruit, peanut, vegetables, for example Phythophthora, Plasmopara, Pythium and powdery mildew fungi such as Sphaerotheca or Uncinula and leaf spot pathogens such as Venturia, Alternaria and Septoria as well as Rhizoctonia, Botrytis, Sclerotinia and Sclerotium.

The good plant tolerance the drug combination in the fight against plant diseases necessary concentrations allows treatment of above ground Parts of plants; of plant and seed, and of the soil. The active ingredient combination according to the invention Can be used for foliar application or as a mordant.

The Inventive drug combination is also suitable for increasing crop yield. It is also mildly toxic and has good plant tolerance.

According to the invention, all Plants and parts of plants are treated. Among plants are here understood all plants and plant populations, as desired and undesirable Wild plants or crops (including naturally occurring crops). Crops can Be plants by conventional breeding and optimization methods or by biotechnological and genetic engineering methods or Combinations of these methods can be obtained, including transgenic ones Plants and including protected by plant variety rights or non-protectable plant varieties. Under plant parts are all above ground and underground Parts and organs of plants, such as shoot, leaf, flower and root By way of example, leaves, needles, stems, stems, flowers, fruiting bodies, fruits and Seeds as well as roots, tubers and rhizomes. To the plant parts belongs also harvested material as well as vegetative and generative propagation material, For example, cuttings, tubers, rhizomes, offshoots and seeds.

The Treatment according to the invention the plants and plant parts with the active ingredients are made directly or by affecting their environment, habitat or storage space the usual Treatment methods, e.g. by dipping, spraying, evaporating, misting, Sprinkle, spread and propagate material, in particular in seeds, further by single or multi-layer wrapping.

The Inventive drug combination can in the usual Formulations are translated as Solutions, Emulsions, suspensions, powders, foams, pastes, granules, aerosols, Very fine encapsulation in polymeric substances and in encapsulants for seeds, as well as ULV formulations.

These formulations are prepared in a known manner, for example by mixing the active compounds or Wirkstoffkombinationenm with extenders, ie liquid solvents, liquefied gases under pressure and / or solid carriers, optionally using surface-active Agents, ie emulsifiers and / or dispersants and / or foam-forming agents. In the case of using water as extender, for example, organic solvents can also be used as auxiliary solvents. Suitable liquid solvents are essentially: aromatics such as xylene, toluene or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons such as cyclohexane or paraffins, eg 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, strongly polar solvents such as dimethylformamide and dimethyl sulfoxide, and water. By liquefied gaseous diluents or carriers are meant liquids which are gaseous at normal temperature and under atmospheric pressure, for example aerosol propellants, such as butane, propane, nitrogen and carbon dioxide. Suitable solid carriers are: for example ground natural minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals, such as finely divided silica, alumina and silicates. As solid carriers for granules are: for example, broken and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite and synthetic granules of inorganic and organic flours and granules of organic material such as sawdust, coconut shells, corn cobs and tobacco stems. Suitable emulsifiers and / or foam-formers are: for example nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkylsulfonates, alkyl sulfates, arylsulfonates and protein hydrolysates. Suitable dispersants are: for example lignin-sulphite liquors and methylcellulose.

It can in the formulations adhesives such as carboxymethylcellulose, natural and synthetic powdery, granular or latex-shaped Polymers such as gum arabic, polyvinyl alcohol, Polyvinyl acetate, as well as natural Phospholipids, such as cephalins and lecithins, and synthetic phospholipids. Further Additives can mineral and vegetable oils be.

It can Dyes such as inorganic pigments, e.g. Iron oxide, titanium oxide, Ferrocyan blue and organic dyes such as alizarin, azo and Metal phthalocyanine dyes and trace nutrients, such as salts of iron, Manganese, boron, copper, cobalt, molybdenum and zinc are used.

The Formulations generally contain between 0.1 and 95% by weight Active ingredients, preferably between 0.5 and 90%.

The Inventive drug combination can be used as such or in their formulations also in mixture with other known fungicides, bactericides, acaricides, nematicides or insecticides - especially in the treatment of seeds - for example to widen the spectrum of action or To prevent development of resistance.

Also a mixture with other known active substances, such as herbicides or with fertilizers and growth regulators is possible.

The Compounds (I), (II) and (III) can be used simultaneously, namely jointly or separately, or applied one after another, where the sequence in separate application generally no Impact on the control done Has.

The Drug combination can be used as such, in the form of their formulations or the use forms prepared from it, such as ready-to-use Solutions, emulsifiable concentrates, emulsions, suspensions, wettable powders, soluble Powders and granules are used. The application happens in usual Way, e.g. by pouring, Spraying, spraying, Scattering, spreading, dry pickling, wet pickling, wet pickling, slurry treatment or encrusting.

At the Use of the active ingredient combination according to the invention can the application rates within a larger range, depending on the type of application be varied. In the treatment of plant parts are the Application rates of active ingredient combination generally between 0.1 and 10 000 g / ha, preferably between 10 and 1000 g / ha. In the Seed treatment are the application rates of drug combination in Generally between 0.001 and 50 g per kilogram of seed, preferably between 0.01 and 10 g per kilogram of seed. In the treatment the soil are the application rates of drug combination in general between 0.1 and 10,000 g / ha, preferably between 1 and 5,000 g / ha.

The good fungicidal action of the active compound combination according to the invention is evident from the following examples. While the individual active substances have weaknesses in the fungicidal action, show the combinations of three drugs an effect that goes beyond a simple sum of effects.

One synergistic effect is always present in fungicides, though the fungicidal action of the active ingredient combination is greater as the sum of the effects of the individually applied active ingredients.

X

den Wirkungsgrad beim Einsatz des Wirkstoffes A in einer Aufwandmenge von m g/ha bedeutet,

Y

den Wirkungsgrad beim Einsatz des Wirkstoffes B in einer Aufwandmenge von n g/ha bedeutet,

Z

den Wirkungsgrad beim Einsatz des Wirkstoffes C in einer Aufwandmenge von r g/ha bedeutet,

E₁

den Wirkungsgrad beim Einsatz der Wirkstoffe A und B in Aufwandmengen von m und n g/ha bedeutet und

E₂

den Wirkungsgrad beim Einsatz der Wirkstoffe A und B und C in Aufwandmengen von m und n und r g/ha bedeutet,

dann ist

und für eine Kombination aus 3 Wirkstoffen:

The expected effect for a given combination of 2 or 3 drugs can be calculated according to SR Colby ("Calculating Synergistic and Antagonistic Responses of Herbicide Combinations", Weeds 1967, 15, 20-22) as follows:
If

X

means the efficiency when using the active ingredient A at a rate of mg / ha,

Y

the efficiency when using the active ingredient B in an application rate of ng / ha means

Z

the efficiency when using the active ingredient C in an application rate of rg / ha means

E ₁

the efficiency when using the active compounds A and B in application rates of m and ng / ha means and

E ₂

the efficiency when using the active compounds A and B and C in application rates of m and n and rg / ha means

then

and for a combination of 3 agents:

there the efficiency is determined in%. It means 0% efficiency, which corresponds to that of the controller, while an efficiency of 100% means that no infestation is observed.

If the actual fungicidal effect is greater than calculated, the combination is over-additive in its effect, ie there is a synergistic effect. In this case, the actual observed efficiency must be greater than the value calculated for the expected efficiencies E ₁ and E ₂ calculated from the formula given above.

The Invention is illustrated by the following examples. The However, the invention is not limited to the examples.

Example 1 Erysiphe test (wheat) / curative Solvent: 10 parts by weight of N-methyl-pyrrolidone emulsifier: 0.6 part by weight of alkylaryl polyglycol ether

to Preparation of a suitable preparation of active ingredient one mixes with 1 part by weight of the active ingredient combination according to the invention the indicated amounts of solvent and emulsifier and diluted concentrate with water to the desired concentration.

to exam on curative efficacy are young plants with spores of Erysiphe graminis f.sp. tritici pollinated. 48 hours after inoculation, the plants with the active ingredient preparation sprayed in the specified rate.

The Plants are in a greenhouse at a temperature of about 20 ° C and a relative humidity of about 80% set up to to favor the development of mildew pustules.

7 Days after the inoculation the evaluation takes place.

The Inventive drug combination shows very good fungicidal properties.

Example 2 Erysiphe test (wheat) / protective Solvent: 10 parts by weight of N-methyl-pyrrolidone emulsifier: 0.6 part by weight of alkylaryl polyglycol ether

to Preparation of a suitable preparation of active ingredient one mixes with 1 part by weight of the active ingredient combination according to the invention the indicated amounts of solvent and emulsifier and diluted concentrate with water to the desired concentration.

to exam sprayed on protective activity you young plants with the preparation of active compound in the specified Application rate.

To The plants with spores of Erysiphe graminis f.sp. tritici pollinated.

The Plants are in a greenhouse at a temperature of about 20 ° C and a relative humidity of about 80% set up to to favor the development of mildew pustules.

7 Days after the inoculation the evaluation takes place.

The Inventive drug combination shows very good fungicidal properties.

Example 3 Puccinia test (wheat) / protective Solvent: 10 parts by weight of N-methyl-pyrrolidone emulsifier: 0.6 part by weight of alkylaryl polyglycol ether

to Preparation of a suitable preparation of active ingredient one mixes with 1 part by weight of the active ingredient combination according to the invention the indicated amounts of solvent and emulsifier and diluted concentrate with water to the desired concentration.

to exam Protective effectiveness is demonstrated by young plants with a spore suspension of Puccinia recondita in a 0.1% aqueous agricultural solution. After the spray coating has dried on, the plants are treated with the preparation of active ingredient sprayed in the specified rate. The plants remain 24 hours at 20 ° C and 100% relative humidity in an incubation cabin.

The Plants are then grown in a greenhouse at a temperature from about 20 ° C and a relative humidity of 80% set up to the Development of rust pustules to favor.

10 Days after the inoculation the evaluation takes place.

The Inventive drug combination shows very good fungicidal properties.

Claims (8)

Active substance combination containing a compound of the formula (I)

and a compound of the formula (II)

and a compound of the formula (III)

Means according to claim 1, characterized in that in the active ingredient combination the weight ratio of active ingredient of the formula (I) to the active ingredient of formula (II) 1: 0.1 until 1:10 and to active compound of the formula (III) 1: 0.05 to 1:10. Method of control of mushrooms, characterized in that a combination of active substances such in claim 1 defined on the fungi, their habitat or the plants, parts of plants, seeds, soils, surfaces, materials to be kept free of them or rooms allow to act. Method according to claim 3, characterized in that the compound (I) according to claim 1, the compound (II) according to claim 1 and the compound (III) according to claim 1 at the same time together or separately or in succession. Propagating material obtained by a method according to claim 3 was treated. Fungicidal compositions containing a content of one Active substance combination as defined in claim 1. Use of the active ingredient combination or agents such in the claims 1, 2 and 6 defined for control of mushrooms. Process for the preparation of fungicidal agents, characterized in that an active substance combination according to claim 1 mixed with extenders and / or surfactants.