WO2004045288A2

WO2004045288A2 - Fungicidal mixtures for controlling rice pathogens

Info

Publication number: WO2004045288A2
Application number: PCT/EP2003/012769
Authority: WO
Inventors: Jordi Tormo I Blasco; Thomas Grote; Eberhard Ammermann; Reinhard Stierl; Siegfried Strathmann; Ulrich Schöfl
Original assignee: Basf Aktiengesellschaft
Priority date: 2002-11-15
Filing date: 2003-11-14
Publication date: 2004-06-03
Also published as: WO2004045288A3; AU2003292023A1; TW200509796A; AU2003292023A8

Abstract

Disclosed are fungicidal mixtures for controlling rice pathogens, containing a synergistically effective amount of 1) a compound of formula (I), and 2) a compound of formula (II) as active components, methods for controlling destructive fungi by means of mixtures of compound I and compound II, the use of compounds I and II for producing such mixtures, and agents containing said mixtures.

Description

Fungicidal mixtures for controlling rice pathogens

description

The present invention relates to fungicidal mixtures for controlling rice pathogens, containing as active components

1) the compound of formula I,

and

2) the compound of formula II,

in a synergistically effective amount.

In addition, the invention relates to a method for controlling rice pathogens with mixtures of the compound I with the compound II and the use of the compound I with the compound II for the preparation of such mixtures and agents which contain these mixtures.

The compound of the formula I, 3'-bromo-2,3,4,6'-tetramethoxy-2 ', 6-dimethylbenzophenone, its preparation and its action against Ascomycetes, the harmful fungi causing mildew diseases, is known (provisional common name: metrafenone ; US 5945567; US 6001 883).

The compound II, 5-chloro-7- (4-methyl-piperidin-1-yl) -6- (2,4,6-trifluorophenyl) - [1,2,4] tri-azolo [1, 5 -a] pyrimidine, its preparation and its action against harmful fungi is also known from the literature (WO 98/46607). Mixtures of metrafenones with various active ingredients, including triazolopyrimidines, which are effective against mildew diseases are generally described in US Pat. No. 6,346,535. Compound II is included in the general disclosure of this document, but is not explicitly mentioned. The combination of metrafenone with compound II is therefore new.

Mixtures of triazolopyrimidines with different active ingredients are generally known from EP-A 988 790.

The synergistic mixtures described in EP-A 988 790 are described as being fungicidally active against various diseases of cereals, fruits and vegetables, in particular mildew on wheat and barley or gray mold on apples.

Due to the special cultivation conditions of rice plants, there are significantly different requirements for a rice fungicide than for fungicides used in cereals or

Fruit growing can be applied. There are serious differences in the method of application: In rice crops, the fungicide is usually applied to the soil directly at or shortly after sowing. The fungicide is absorbed into the plant via the roots and transported in the plant sap in the plant to the parts of the plant to be protected. A high system is therefore essential for rice fungicides. In cereal or fruit growing, on the other hand, the fungicide is usually applied to the leaves or the fruits, so the systemics of the active ingredients play a significantly smaller role in these crops.

Other pathogens are also typical in rice than in cereals or fruit. Pyricularia oryzae and Corticium sasakii (syn. Rhizoctonia solani AG 1-IA) are the causative agents of the most common diseases of rice plants. They do not occur to any appreciable extent in other crops. Rhizoctonia solani is the only agronomically important pathogen within the Agaricomycetidae subclass. In contrast to most other fungi, this fungus does not attack the plant via spores, but via a mycelial infection.

For these reasons, findings on the fungicidal activity of active ingredients in cereal or fruit growing cannot be transferred to rice crops.

Practical experience in agriculture has shown that the repeated and exclusive use of a single active ingredient in the control of harmful fungi in many cases leads to the rapid selection of those fungal strains that have developed a natural or adapted resistance to the active ingredient in question. A effective control of these fungi with the active ingredient in question is then no longer possible.

In order to reduce the risk of selecting resistant fungal strains, mixtures of various active substances are usually used today to combat harmful fungi. Combining active ingredients with different mechanisms of action can ensure long-term control success.

In view of effective resistance management and an effective control of rice pathogens with the lowest possible application rates, the present invention was based on mixtures which, with the smallest possible total amount of active ingredients applied, have a sufficient action against the harmful fungi.

Accordingly, the combination of active ingredients defined at the outset was found. It has also been found that, when the compounds I and the compound II are used simultaneously or separately or when the compounds I and the compound II are used in succession, rice pathogens can be better controlled than with the individual compounds.

Surprisingly, it was found that the fungicidal activity of compound II is considerably increased by combination with metrafenone. Thus, the combinations according to the invention, in particular at low application rates, enable a significantly more effective control of the rice pathogens than the mixtures with metrafenone proposed in US Pat. No. 6,346,535 for controlling mildew diseases.

In the preparation of the mixtures, preference is given to using the pure active ingredients I and II, to which, as required, further active ingredients against harmful fungi or other pests such as insects, arachnids or nematodes, or else herbicidal or growth-regulating active ingredients or fertilizers can be admixed.

The mixtures of the compounds I and II or the simultaneous joint or separate use of the compounds I and the compound II are notable for excellent activity against rice pathogens from the class of the> 4s-comycetes, deuteromycetes and basidiomycetes. They are highly systematic and can therefore be used for seed treatment as well as leaf and soil fungicides. They are of particular importance for controlling harmful fungi on rice plants and on their seeds, such as bipolaris and woodturners. They can be used particularly advantageously to combat Pyricularia oryzae, the cause of rice blight, and the leaf sheath disease of rice caused by Corticium sasakii (syn. Rhizoctonia solani).

The compounds I and the compound II can be applied simultaneously together or separately or in succession, the sequence in the case of separate application generally not having any effect on the success of the control measures.

The compounds I and the compound II are usually used in a weight ratio of 100: 1 to 1: 100, preferably 20: 1 to 1:50, in particular 5: 1 to 1:20.

Depending on the type of compound and the desired effect, the application rates of the mixtures according to the invention are 5 g / ha to 2000 g / ha, preferably 50 to 1500 g / ha, in particular 50 to 750 g / ha.

Accordingly, the application rates for the compound I are generally from 1 to 1000 g / ha, preferably from 10 to 750 g / ha, in particular from 20 to 500 g / ha.

Correspondingly, the application rates for compound II are generally from 1 to 1000 g / ha, preferably from 10 to 750 g / ha, in particular from 20 to 500 g / ha.

In the case of seed treatment, application rates of the mixture of 0.001 to 1 g / kg of seed, preferably 0.01 to 0.5 g / kg, in particular 0.01 to 0.1 g / kg, are generally used.

In the control of harmful pathogens for rice plants, the separate or joint application of the compounds I and II or the mixtures of the compounds I and II is carried out by spraying or pollinating the seeds, seedlings, plants or soils before or after sowing the plants or before or after emergence of the plants. The compounds are preferably applied jointly or separately by applying granules or by dusting the soil.

The mixtures according to the invention, or the compounds I and II, can be converted into the customary formulations, for example solutions, emulsions, suspensions, dusts, powders, pastes and granules. The form of application depends on the respective purpose; in any case, it should ensure a fine and uniform distribution of the compound according to the invention. The formulations are prepared in a known manner, for example by stretching the active ingredient with solvents and / or carriers, if desired using emulsifiers and dispersants. The following are essentially considered as solvents / auxiliaries:

Water, aromatic solvents (e.g. Solvesso products, xylene), paraffins (e.g. petroleum fractions), alcohols (e.g. methanol, butanol, pentanol, benzyl alcohol), ketones (e.g. cyclohexanone, gamma-butryolactone), pyrrolidones (NMP, NOP), acetates (Glycol diacetate), glycols, dimethyl fatty acid amides, fatty acids and fatty acid esters. In principle, solvent mixtures can also be used

Carriers such as natural stone powder (e.g. kaolins, clays, talc, chalk) and synthetic stone powder (e.g. highly disperse silica, silicates); Emulsifiers such as nonionic and anionic emulsifiers (e.g. polyoxyethylene fatty alcohol ethers, alkyl sulfonates and aryl sulfonates) and dispersants such as lignin sulfite liquors and methyl cellulose.

Alkali, alkaline earth, and ammonium salts of lignosulfonic acid, naphthalenesulfonic acid, phenolsulfonic acid, dibutylnaphthalenesulfonic acid, alkylarylsulfonates, alkyl sulfates, alkyl sulfonates, fatty alcohol sulfates, fatty acids and sulfated naphthalene naphthalene and sulfonated dehydrogenated naphthalene derivatives of sulfonated formaldehyde derivatives and sulfonated dehydrogenated naphthalenedaphthalene from sulfonates, as well as condensation products with sulfated naphthalenedaphthalene and sulfonated dehydrogenated naphthalenedaphthalene and sulfonated dehydrogenated naphthalenedaphthalene and sulfonated dehydrogenated naphthalenedaphthalene and sulfonated dehydrogenated naphthalenedaphthalene ether and condensation products , Condensation products of naphthalene or of naphthalene sulfonic acid with phenol and formaldehyde, polyoxyethylene octylphenol ether, ethoxylated isooctylphenol, octylphenol, nonylphenol, alkylphenol polyglycol ether, tri-butylphenyl polyglycol ether, trihylphenyl polyglycol ether, alkyl alcoholoxy ethoxylated alcohol, alkyl alcoholoxy ethoxylated alcohol , Laurylalkoholpolyglykoletheracetal, sorbitol ester, lignin sulfite waste liquors and methyl cellulose into consideration.

For the production of directly sprayable solutions, emulsions, pastes or oil dispersions, mineral oil fractions from medium to high boiling points, such as kerosene or diesel oil, furthermore coal tar oils as well as oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, e.g. Toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes or their derivatives, methanol, ethanol, propanol, butanol, cyclohexanol, cyclohexanone, isophorone, strongly polar solvents, e.g. Dimethyl sulfoxide, N-methylpyrrolidone or water into consideration.

Powders, materials for broadcasting and dusts can be prepared by mixing or grinding the active substances together with a solid carrier. Granules, for example coated granules, impregnated granules and homogeneous granules, can be prepared by binding the active ingredients to solid carriers. Solid carriers are, for example, mineral earths, such as silica gels, silicates, talc, kaolin, Attaclay, limestone, lime, chalk, bolus, loess, clay, dolomite, diatomaceous earth, calcium and magnesium sulfate, magnesium oxide, ground plastics, fertilizers, such as ammonium sulfate , Ammonium phosphate, ammonium nitrate, ureas and vegetable products such as cereal flour, tree bark, wood and nutshell flour, cellulose powder and other solid carriers.

The formulations generally contain between 0.01 and 95% by weight, preferably between 0.1 and 90% by weight, of the active ingredients. The active ingredients are used in a purity of 90% to 100%, preferably 95% to 100% (according to the NMR spectrum).

Examples of formulations are: 1. Products for dilution in water

A) Water-soluble concentrates (SL)

10 parts by weight of the active ingredients are dissolved in water or a water-soluble solvent. Alternatively, wetting agents or other aids are added. The active ingredient dissolves when diluted in water.

B) Dispersible concentrates (DC)

20 parts by weight of the active ingredients are dissolved in cyclohexanone with the addition of a dispersant e.g. Dissolved polyvinyl pyrrolidone. A dispersion results when diluted in water.

C) Emulsifiable concentrates (EC)

15 parts by weight of the active ingredients are dissolved in xylene with the addition of calcium dodecylbenzenesulfonate and castor oil ethoxylate (5% each). Dilution in water results in an emulsion.

D) Emulsions (EW, EO)

40 parts by weight of the active ingredients are dissolved in xylene with the addition of calcium dodecylbenzenesulfonate and castor oil ethoxylate (5% each). This mixture is introduced into water using an emulsifying machine (Ultraturax) and brought to a homogeneous emulsion. Dilution in water results in an emulsion.

E) suspensions (SC, OD)

20 parts by weight of the active ingredients are added in a stirred ball mill with the addition of dispersing and wetting agents and water or an organic solvent. crushed a fine active ingredient suspension. Dilution in water results in a stable suspension of the active ingredient.

F) Water-dispersible and water-soluble granules (WG, SG) 50 parts by weight of the active ingredients are finely ground with the addition of dispersants and wetting agents and are produced as water-dispersible or water-soluble granules by means of technical equipment (e.g. extrusion, spray tower, fluidized bed). Dilution in water results in a stable dispersion or solution of the active ingredient.

G) Water-dispersible and water-soluble powders (WP, SP)

75 parts by weight of the active ingredients are ground in a rotor-strator mill with the addition of dispersing and wetting agents and silica gel. Dilution in water results in a stable dispersion or solution of the active ingredient.

2. Products for direct application

H) dusts (DP)

5 parts by weight of the active ingredients are finely ground and intimately mixed with 95% finely divided kaolin. This gives a dust.

I) Granules (GR, FG, GG, MG)

0.5 part by weight of the active ingredients are finely ground and combined with 95.5% carriers. Common processes are extrusion, spray drying or fluidized bed. This gives granules for direct application.

J) ULV solutions (UL)

10 parts by weight of the active ingredients are dissolved in an organic solvent e.g. Xylene dissolved. This gives you a product for direct application.

The active ingredients as such, in the form of their formulations or the use forms prepared therefrom, e.g. in the form of directly sprayable solutions, powders, suspensions or dispersions, emulsions, oil dispersions, pastes, dusts, sprinkling agents, granules by spraying, atomizing, dusting, scattering or pouring. The application forms depend entirely on the purposes of use; in any case, they should ensure the finest possible distribution of the active compounds according to the invention.

Aqueous application forms can be prepared from emulsion concentrates, pastes or wettable powders (wettable powders, oil dispersions) by adding water. To produce emulsions, pastes or oil dispersions, the sub- punch as such or dissolved in an oil or solvent, homogenized in water by means of wetting agents, adhesives, dispersants or emulsifiers. However, it is also possible to prepare concentrates composed of an active substance, wetting agents, adhesives, dispersants or emulsifiers and possibly solvents or oil, which are suitable for dilution with water.

The active ingredient concentrations in the ready-to-use preparations can be varied over a wide range. In general, they are between 0.0001 and 10%, preferably between 0.01 and 1%.

The active ingredients can also be used with great success in the ultra-low-volume process (ULV), it being possible to apply formulations with more than 95% by weight of active ingredient or even the active ingredient without additives.

Oils of various types, wetting agents, adjuvants, herbicides, fungicides, other pesticides, bactericides can be added to the active compounds, if appropriate also only immediately before use (tank mix). These agents can be added to the agents according to the invention in a weight ratio of 1:10 to 10: 1.

The compounds I and II, or the mixtures or the corresponding formulations, are used in that the harmful fungi, the plants, seeds, soils, areas, materials or spaces to be kept free from them are mixed with a fungicidally effective amount of the mixture or the compounds I. and II when applied separately. The application can take place before or after the infestation by the harmful fungi.

The fungicidal activity of the compound and the mixtures can be demonstrated by the following tests:

The active ingredients were prepared separately or together as a stock solution with 0.25% by weight of active ingredient in acetone or DMSO. 1% by weight of emulsifier Uniperol® EL (wetting agent with emulsifying and dispersing action based on ethoxylated alkylphenols) was added to this solution and diluted with water to the desired concentration. Example of use - Protective activity against rice blight caused by Pyricula a oryzae

Leaves of 'Tai-Nong 67' rice seedlings grown in pots were sprayed to runoff point with an aqueous suspension in the active compound concentration given below. The following day, the plants were inoculated with an aqueous spore suspension of Pyricularia oryzae. The test plants were then placed in climatic chambers in 22 - 24 ° C and 95 - 99% relative humidity for 6 days, then the extent of the development of the infestation on the leaves was determined visually.

The evaluation is carried out by determining the affected leaf areas in percent. These percentages were converted into efficiencies.

Efficiency (W) is calculated using Abbot's formula as follows:

W = (1 - σ / £) - 100

σ corresponds to the fungal attack of the treated plants in% and ß corresponds to the fungal attack of the untreated (control) plants in%

With an efficiency of 0, the infection of the treated plants corresponds to that of the untreated control plants; with an efficiency of 100, the treated plants show no infection.

The expected efficacies of the active ingredient mixtures are calculated according to the Colby formula [R.S. Colby, Weeds 15, 20-22 (1967)] and compared with the observed efficiencies.

Colby formula: E = x + y - x-y / 100

E expected efficiency, expressed in% of the untreated control, when using the mixture of active ingredients A and B in concentrations a and b

the efficiency, expressed in% of the untreated control, when using the active ingredient A in the concentration a the efficiency, expressed in% of the untreated control, when using the active ingredient B in the concentration b The compounds A and B known from the mixtures described in US Pat. No. 6,346,535 as effective against mildew diseases were used as comparison compounds:

Table A - Individual substances

Table B - mixtures according to the invention

^k ) calculated efficiency according to the Colby formula Table C - Comparative tests - combinations known from US 6346535

*) Efficiency calculated according to the Colby formula

The results of the tests show that the mixtures according to the invention, at comparable application rates, show a significantly higher activity than the flour fungicides known from US Pat. No. 6,346,535, the mixtures of metrafenones with the compounds A or B.

Claims

claims

1. Fungicidal mixtures for controlling rice pathogens, containing as active components

1) the compound of formula I,

and

2) the compound of formula II,

in a synergistically effective amount.

2. Fungicidal mixtures according to claim 1, containing the compound of formula I and the compound of formula II in a weight ratio of 100: 1 to 1: 100.

3. Fungicidal composition comprising a liquid or solid carrier and a mixture according to claim 1 or 2.

4. A method for controlling rice-pathogenic harmful fungi, characterized in that the fungi, their habitat or the plants to be protected against fungal attack, the soil or seeds are treated with an effective amount of the compound I and the compound II according to claim 1 in synergistically effective amounts ,

5. The method according to claim 4, characterized in that the compounds I and II according to claim 1 simultaneously, jointly or separately, or in succession.

6. The method according to claim 4, characterized in that the mixture according to claims 1 or 2 is used in an amount of 5 g / ha to 2000 g / ha.

7. Process according to claims 4 and 5, characterized in that the mixture according to claims 1 or 2 in an amount of 0.001 to 1 g / kg

Seed applies.

8. The method according to claims 4 to 7, characterized in that the harmful fungus Pyricularia oryzae is controlled.

9. Seed containing the mixture according to claims 1 or 2 in an amount of 0.001 to 1 g / kg.

10. Use of the compound I and the compound II according to claim 1 for the preparation of a suitable agent for controlling rice-pathogenic harmful fungi.