EP1681928A1

EP1681928A1 - Fungicidal mixtures for controlling rice pathogens

Info

Publication number: EP1681928A1
Application number: EP04790894A
Authority: EP
Inventors: Jordi Tormo I Blasco; Thomas Grote; Maria Scherer; Reinhard Stierl; Siegfried Strathmann; Ulrich Schöfl
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 2003-10-29
Filing date: 2004-10-27
Publication date: 2006-07-26
Also published as: OA13277A; NZ546400A; CO5670338A2; US20070099939A1; WO2005041667A1; RS20060286A; IL174789A0; MA28162A1; UA80367C2; JP2007509881A; CR8364A; ZA200604229B; CN1874681A; EA200600831A1; NO20062012L; UY28591A1; AU2004285277A2; KR20060113909A; AR046565A1; MXPA06003937A

Abstract

Disclosed are fungicidal mixtures for controlling rice pathogens, containing 1) a triazolopyrimidine derivative of formula (I) and 2) carboxin of formula (II) at a synergistically effective quantity as active components. Also disclosed are methods for controlling rice pathogens with the aid of mixtures of compound (I) and compound (II), the use of compound (I) along with compound (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 triazolopyrimidine derivative of the formula I,

and

2) carboxin of the 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 I, 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 known from the literature (WO 98/46607).

The compound II, 2-methyl-5,6-dihydro- [1,4] oxathiin-3-carboxylic acid phenylamide, its preparation and its action against harmful fungi is also known from the literature (US 3454 391; common name: carboxin). It is widely used as a seed dressing on the market.

Mixtures of triazolopyrimidine derivatives with carboxin are generally known from EP-A 988790. Compound I is from the general disclosure of this document includes, but is not explicitly mentioned. The combination of compound I with carboxin is therefore new.

The synergistic mixtures known from EP-A 988 790 are fungicidally active against various diseases of cereals, fruits and vegetables, such as. B. powdery 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 that are used in cereal or fruit growing. There are differences in the application method: in addition to the foliar application used in many places, in modern rice cultivation the fungicide is applied directly to the soil 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. 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. Py cularia oryzae, Cochliobolus miyabeanus and Corticium sasakii (syn. Rhizoctonia solani) are the causative agents of the most important diseases of rice plants. Rhizoctonia solani is the only agronomically important pathogen within the Agarcomycetidae subclass. This fungus does not attack the plant via spores like most other fungi, but via a mycelial infection.

For this reason, findings on the fungicidal effects of 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. An effective control of these fungi with the active ingredient in question is then no longer possible.

In order to reduce the risk of selection of resistant fungal strains, mixtures of different active substances are usually used today to combat harmful fungi. Combining active ingredients with different mechanisms of action can ensure long-term control success. With regard to 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 a reduced total amount of active ingredients applied, have an improved action against the harmful fungi.

Accordingly, the mixtures defined at the outset were found. It has also been found that, when the compounds I and II are used simultaneously or separately or when the compounds I and II are used in succession, it is better to combat rice pathogens than with the individual active compounds.

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.

Fungicides selected from the following group are particularly suitable as further active ingredients in the above sense:

Acylalanines such as benalaxyl, ofurace, oxadixyl, amine derivatives such as aldimorph, dodemorph, fenpropidine, guazatine, iminoctadine, tridemorph,

Antibiotics such as cycloheximide, griseofulvin, kasugamycin, natamycin, polyoxin or streptomycin,

• azoles such as bitertanol, bromoconazole, cyproconazole, difenoconazole, Dinitrocona- zol, enilconazole, Fenbucoπazol, Fluquiconazol, flusilazole, flutriafol, hexaconazole, imazalil, ipconazole, myclobutanil, penconazole, Propicoπazol, prochloraz, Prothio- conazole, simeconazole, tetraconazole, triadimefon, triadimenol , Triflumizole, tritico-nazole,

• dicarboximides such as myclozolin, procymidone, • dithiocarbamates such as Ferbam, Nabam, Metam, Propineb, polycarbamate, ziram, Zineb,

• Heterocyclic compounds such as anilazine, boscalid, carbendazim, oxycarboxin, cyazofamid, Dazomet, famoxadone, fenamidone, fuberidazole, flutolanil, furamet-pyr, isoprothiolan, mepronil, nuarimol, probenazole, pyroquilon, thiiflazolamid, triadlazolamid, triadlazolamid, trifinylzilazol, triflamylazidyl, thioflazolid, trifinylzilazol, triflamylzilazol, trifluoric acid triforine,

Nitrophenyl derivatives such as binapacryl, dinocap, dinobuton, nitrophthal-isopropyl,

Phenylpyrroles such as fenpiclonil or fludioxonil,

• Other fungicides such as acibenzolar-S-methyl, carpropamide, chlorothalonil, cyflufamid, cymoxanil, diclomezin, diclocymet, diethofencarb, edifenphos, ethabo- xam, fentin acetate, fenoxanil, ferimzone, fosetyl, hexachlorobenzene, metrafenone, pencycuron, propamocarb, phthalide, toloclofos-methyl, quintozene, zoxamide,

Strobilurins such as fluoxastrobin, metominostrobin, orysastrobin or pyraclostrobin,

• Sulfenic acid derivatives such as Captafol, • cinnamic acid amides and analogues such as Flumetover.

In one embodiment of the mixtures according to the invention, a further fungicide III or two fungicides III and IV are added to the compounds I and II. Mixtures of the compounds I and II with a component IM are preferred. Mixtures of compounds I and II are particularly preferred.

The mixtures of the compounds I and II or the simultaneous joint or separate use of the compounds I and II are distinguished by an outstanding activity against rice pathogens from the classes of the Ascomycetes, Deuteromycetes and Basidiomycetes. They can be used for seed treatment, as well as leaf and soil fungicides.

They are of particular importance for combating harmful piizis on rice plants and on their seeds, such as Bipolaris and DrecΛs / era species, as well as Pyricularia oryzae. They are particularly suitable for combating the brown spot disease on rice caused by Cochliobolus miyabeanus.

In addition, the combination of compounds I and II according to the invention is also suitable for controlling other pathogens, such as, for. B. Septoria and Puccinia men in cereals and Alternaria and ßoyfrtf / ^' s species in vegetables, fruits and wine.

The compound 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 compound 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 2: 1 to 1:20.

If desired, the components IM and, if appropriate, IV are mixed in a ratio of 20: 1 to 1:20 to the compound I.

Depending on the type of compound and the desired effect, the application rates of the mixtures according to the invention are from 5 g / ha to 2 kg / 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 2000 g / ha, preferably from 10 to 1500 g / ha, in particular from 20 to 1000 g / ha.

When treating seeds, application rates of mixture of

I to 1000 g / 100 kg of seeds, preferably 1 to 750 g / 100 kg, in particular 5 to 500 g / 100 kg.

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 I and are preferably applied

II by spraying the leaves. The compounds can also be applied by applying granules or by dusting the floors.

The mixtures according to the invention, or the compounds I and II, can be converted into the customary formulations, e.g. 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 suitable as solvents / auxiliaries: water, aromatic solvents (for example Solvesso products, xylene), paraffins (for example petroleum fractions), alcohols (for example methanol, butanol, pentanol, benzyl alcohol), ketones (for example 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 (eg kaolins, clays, talc, chalk) and synthetic stone powder (eg highly disperse silica, silicates); Emulsifiers such as nonionic and anionic emulsifiers (eg polyoxyethylene fatty alcohol ethers, alkyl sulfonates and aryl sulfonates) and dispersants such as lignin sulfite waste 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 methylceiluiose 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, e.g. Coating, impregnation and homogeneous granules can be produced by binding the active ingredients to solid carriers. Solid carriers are e.g. Mineral earths, such as silica gels, silicates, talc, kaolin, attack clay, limestone, lime, chalk, bolus, loess, clay, dolomite, diatomaceous earth, calcium and magnesium sulfate, magnesium oxide, ground plastics, fertilizers, e.g. Ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas and vegetable products, such as grain flour, tree bark, wood and nutshell flour, cellulose powder and other solid carriers.

The formulations in general contain between 0.01 and 95% by weight, preferably between 0.1 and 90% by weight, of the active compounds. 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 dispersing agent e.g. Dissolved polyvinyl pyrrolidone. When diluted in water, a dispersion results.

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 comminuted in a stirred ball mill to form a fine active ingredient suspension with the addition of dispersing and wetting agents and water or an organic solvent. 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 dispersing and wetting agents and produced using technical equipment (e.g. extrusion, spray tower, fluidized bed) as water-dispersible or water-soluble granules. 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 mixed internally 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, oldispersions, pastes, dusts, sprinkling agents, granules by spraying, atomizing, dusting, scattering or pouring. The application forms depend entirely on the purposes; 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, old dispersions) by adding water. To prepare emulsions, pastes or old dispersions, the substances as such or dissolved in an oil or solvent can be 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 are usually 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, surfaces, materials or spaces to be kept free of them are mixed with a fungicidally effective amount of the mixture or Compounds I and II treated 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 - effectiveness against brown spot disease of rice caused by Cochliobolus miyabeanus with protective treatment

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 Cochliobolus miyabeanus. The test plants were then used Set up in climatic chambers at 22 - 24 ° C and 95 - 99% relative humidity for six days, then the extent of the development of the infestation on the leaves was determined visually.

The evaluation is carried out by determining the infected plants in percent. These percentages were converted into efficiencies.

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

W = (1 - α ß) '100 α 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 infestation 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 - xy / 100 E expected efficiency, expressed in% of the untreated control, when using the mixture of active ingredients A and B in concentrations a and bx the efficiency, expressed in% of the untreated control, when using the active ingredient A in the concentration ay the efficiency, expressed in% of the untreated control, when using the active ingredient B in the concentration b

Compounds A and B known from the sulfur mixtures described in EP-A 988 790 were used as comparative compounds:

Table A - Individual substances

Table B - mixtures according to the invention

*) Efficiency calculated according to the Colby formula Table C - comparative tests

*) Efficiency calculated according to the Colby formula

The results of the experiments show that the mixtures according to the invention show a significantly higher activity than the carboxin mixtures known from EP-A 988 790 due to their strong synergism, although the comparative compounds are more effective than compound I as single active compounds at the same application rates.

Claims

claims

1. Fungicidal mixtures for controlling rice pathogens, comprising 1) the triazolopyrimidine derivative of the formula I,

and

2) Carboxin of the formula

in a synergistically effective amount.

2. Fungicidal mixtures according to claim 1, containing the compound of formula I and the compounds 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 one of claims 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 from fungal attack, the soil or seeds are treated with an effective amount of the compound I and one of the compounds II according to claim 1.

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. The method according to any one of claims 4 to 6, characterized in that the harmful fungus Pynculaπa oryzae is controlled.

8. The method according to claims 4 or 5, characterized in that the mixture according to claims 1 or 2 is used in an amount of 1 to 1000 g / 100 kg of seed.

9. Seed containing the mixture according to claims 1 or 2 in an amount of 1 to 1000 g / 100 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.