MXPA06005944A - Fungicidal mixtures - Google Patents

Abstract

The invention relates to fungicidal mixtures containing the following active ingredients:1) a triazolopyrimidine derivative of general formula (I) and 2) dinocap of formula (II), composed of the dinitrophenol derivatives of formulae (IIa) and (IIb), in which n represents 0, 1 or 2, in a synergistically active quantity. The invention also relates to methods for controlling pathogenic fungi and to agents containing said fungicidal mixtures.

Description

FUNGICIDE MIXES TO COMBAT PATHOGENS OF RICE Description The present invention relates to fungicidal mixtures for combating rice pathogens, which contain as active components: (1) the thiazolopyrimidine derivative of the formula I, (2) dinocap of formula II, composed of dinitrophenol derivatives of the formulas Na and llb, where n is 0, 1 or 2, in an active synergetic quantity.

Furthermore, the invention relates to a process for combating rice pathogens with mixtures of compound I with mixed product II and the use of compound I with mixed product II for obtaining such mixtures, as well as products containing them.

Compound I, 5-chloro-7- (4-methyl-piperidin-1-yl) -6- (2,4,6-trifluoro-phenyl) - [1, 2,4] tri- azolo [1 , 5-a] pyrimidine, its preparation and effect against harmful fungi are also known from the literature (WO 98/46607).

Mixtures of triazolopyrimidine derivatives with other active ingredients are generally known from EP-A 988 790 and US 6 268 371.

The known synergistic mixtures of EP-A 988 790 are described as efficient against different diseases of cereals, fruits and legumes, such as oidium in wheat and barley or gray mold in apples.

The mixtures mentioned in US 6 268 371 are described as efficient, especially against rice diseases.

The mixed product II is composed of the compounds lia and llb, 2,6-dinitro-4-octyl-phenylcrotonate and 2,4-dinitro-6-octylphenylcrotonate, where "octü" represents a mixture of 1-methylheptyl, 1- ethylhexyl and 1-propylpentyl, its preparation and its effect against harmful fungi are also known from the literature (US 2 526 660 and US 2 810 767, common denomination: dinocap) and has been established for a long time on the market as a fungicide against diseases caused by powdery mildew.

The fungicidal effect of the known mixtures is not always fully satisfactory, especially its effect against harmful fungi of the oomycete class leaves something to be desired.

Practical experiences in agriculture have shown that the repeated and exclusive use of an individual active ingredient in the fight against harmful fungi results in many cases to a rapid selection of those strains of fungi, which have developed a natural resistance or adapted against the corresponding active principle. So, it is no longer possible to fight this fungus effectively with the corresponding active principle.

To reduce the danger of the selection of strains of resistant fungi, mixtures of different active ingredients are usually used today. Thanks to the combination of active ingredients with different mechanisms of action can ensure the success of the treatment for a long period.

For an effective management of the resistances and to effectively combat harmful fungi with application quantities as low as possible, the object of the present invention are mixtures that with an application amount as low as possible in active principle achieve a satisfactory effect against fungi harmful.

Therefore, the mixtures defined at the beginning were found. Furthermore, it has been found that harmful fungi can be more effectively controlled by applying si-mul'taneamente jointly or separately, compound I and dinocap II or applying compound I and dinocap II successively, than with the individual components ( 1) or (2) (synergistic mixtures).

The mixtures of the compounds I and II or the compound I and the compounds II applied simultaneously together or separately, stand out as being excellently effective against rice pathogens of the class of Ascomycetes, Deuteromycetes, Oomycetes and basidiomycetes. They are suitable for use as foliar and soil fungicides.

They are especially important for combating a myriad of fungi in different plant crops, such as bananas, cotton, legumes (eg cucumbers, beans and cucurbits), barley, grass, oats, coffee, potatoes, corn, fruits, rye, soy, tomatoes, wine, wheat, ornamental plants, sugar cane, countless seeds.

They are especially suitable for combating the following phytopathogenic fungi: Blumeria graminis (powdery mildew) in cereals, Erysiphe cichoracearum and Sphaerotheca fuligi-nea in cucurbits, Podosphaera leucotricha in apples, Uncinula necatoren vid, Puccinia species in cereals, Rhizoctonia species in cotton, rice and turf, Ustilago species in cereals and sugar cane, Venturia inaequalis in apples, Bipolaris and Drechslera species in cereals, rice and turf, Septoria nodorum in wheat, Botrytis cinerea in strawberries, legumes, ornamental plants and vine, species of Mycosphaerella in bananas, peanuts and cereals, Pseudocercosporella herpotrí-choid? S in wheat and barley, Phytophthora infestans in potatoes and tomatoes, species of Pseudoperonospora in cucurbits and hops, Plasmopara viticulture in grapevines, Alternate species in legumes and fruits, as well as species of Fusarium and Verticillium.

In addition, they can be used in the protection of materials (eg wood), for example, against Paecilomyces variotii.

The mixtures according to the invention are especially suitable for combating noxious fungi of the oomycete class.

The biological behavior of the oomycetes is very different from that of the ascomycetes, deuteromycetes and basidiomycetes, since oomycetes are biologically more related to algae than to fungi, so that knowledge about the fungicide activity of active ingredients against "fungi" genuine ", such as. Ascomycetes, Deuteromycetes, and Basidiomycetes can only be transferred limitedly to Oomycetes.

Oomycetes produce economically important damages in various plant crops. In many regions, infections caused by Phytophthora infestans in potatoes and tomatoes are the most important fungal diseases of plants. In viticulture the peronospora of the vine causes considerable damage.

Preferably, the pure active ingredients of the formula I and the formulas Ia and IIb are used in the preparation of the mixtures, to which, if necessary, other active ingredients against harmful fungi or other parasites, such as insects, can be added. arachnids or nematodes, or also active ingredients that regulate growth or fertilizers.

As other active ingredients in the above-mentioned sense, especially fungicides selected from the following group are suitable: • acylalanines, such as benalaxyl, ofurace, oxadixyl, • amine derivatives, such as aldimorf, dodemorf, fenpropidin, guazatin, iminoctadine, tridemorph, • anilinipyrimidines, such as pyrimethanil, mepanipyrim or cyprodinil, • antibiotics, such as cycloheximide, griseofulvin, kasugamycin, natamycin, polioxin or streptomycin, • azoles, such as bitertanol, bromoconazole, ciproconazole, diphenoconazole, dinitro-conazole, enilconazole, epoxiconazo.-n-butanol, fluquiconazole, flusilazole, flutriafol, hexaconazole, imazalil, pconazole, metconazole, myclobutanil, penconazole, propiconazole, prochloroaz, prothioconazole, simeconazole, tetraconazole, triadimefonone, triadimenol, triflumizole, triticonazole, dicarboximides, such as myclozoline, procymidone, dithiocarbamates, such as ferbam, nabam, metam, propineb, polycarbamate, ram, zineb, • heterocyclic compounds, such as anilacin, boscalide, oxycarboxin, cyzofamide, dazomet, famoxad Ona, fenamidone, fuberidazole, flutolanil, furametpir, isopropanol, mepronil, nuarimol, probenazole, pyroquilone, silthiopham, thiabendazole, thiifuzamide, thiadinyl, tricyclazole, triforin, • nitrophenyl derivatives, such as binapacryl, dinobutone, nitroftal-isopropyl , • other fungicides, such as acibenzolar-S-methyl, carpropamide, cyflufenamide, cymoxanil, diclomezine, diclocimet, dietofencarb, edifenfos, etaboxam, fentina-acetate, phenoxanil, ferimzone, fosetyl, hexachlorobenzene, metrafenone, penicuruthone, propamocarb, phthalide, toloclofos-methyl, quintozene, zoxamide, • strobilurins, such as fluoxastrobin, methominostrobin, orisastrobin or pyratroporbine, • sulfenic acid derivatives, such as captafol, • cinnamic acid amides and the like, such as flumetover.

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

The compound I and the dinocap of the formula II can be applied simultaneously, jointly or separately, or in succession, the order of application being unimportant in the separate application on the success of the treatment.

Compound I and dinocap of formula II are usually used in a weight ratio of 100: 1 (1: 11) to 1: 100, preferably 10: 1 to 1:50, especially 5: 1 to 1: 20. .

Components III and IV are added, optionally, in a ratio of 20: 1 to 1:20 to compound I.

The application rates of the mixtures according to the invention vary, depending on the type of compound and the desired effect, from 5 g / ha to 4000 g / ha, preferably, 100 to 1500 g / ha, especially, 100 to 100 g / ha. .

The application rates for compound I vary correspondingly, by general rule, from 1 to 1000 g / ha, preferably 10 to 750 g / ha, especially 20 to 500 g / ha.

The application rates for dinocap II vary correspondingly, as a rule, from 1 to 3000 g / ha, preferably from 100 to 1500 g / ha, especially from 100 to 1000 kg / ha.

In the treatment of the seeds, amounts in the mixture are generally applied from 1 to 1000 g / 100 kg of seeds, preferably 1 to 200 g / 100 kg, especially 5 to 100 g / 100 kg.

If the plants wish to fight pathogenic fungi, compound I and dinocap II or mixtures of compound I and dinocap II are applied by spraying or dusting the seeds, plants or soil before or after planting of the plants or before or after the emergence of the plants. Preferably, the compounds are applied by spraying the leaves.

The mixtures of the invention or the compound I and dinocap of the formula II can be converted into the customary formulations, for example: solutions, emulsions, suspensions, powders, pastes and granules. The form of application depends on the corresponding application end; in any case a fine and uniform distribution of the compound of the invention should be ensured.

The formulations are prepared in known manner, for example, by diluting the active principle with solvents and / or supports, if desired, using emulsifiers and dispersants. As solvents / auxiliary substances, substantially, for this purpose: water, aromatic solvents (eg Solvesso products, xylene), paraffins (eg petroleum fractions), alcohols (eg methane !, butanol, pentanol, benzyl alcohol), ketones (eg cyclohexanone) , gamma-butyrolactone), pyrrolidones (NMP, NOP), acetates (glycol diacetate), glycols, dimethyl fatty acid amides, fatty acids and fatty acids. Basically, solvent mixtures can also be used, - support substances, such as powders of natural stones (eg kaolins, clays, talc, chalk) and synthetic stone powders (eg highly disperse silicic acid, silicates); emulsifiers, such as non-ionogenic and anionic emulsifiers (eg polyoxyethylene fatty alcohol ethers, alkyl sulfonates and aryl sulfonates) and dispersants, such as sulphite residual liquors and methylcellulose. Suitable surfactants are the alkali metal, alkaline earth metal and ammonium salts of lignin sulphonic acid, naphthalenesulfonic acid, phenolsulfonic acid, dibutyl naphthalisulfonic acid, alkylaryl sulphonates, alkyl sulphates, alkyl sulfonate, fatty alcohol sulphates, fatty acids and glycol ethers of sulphonated fatty alcohol, in addition, sulfonated naphthalene condensates and naphthalene derivatives with formaldehyde, naphthalene-naphthalene or naphthalene sulfonic acid-phenol and formaldehyde, polyoxyethylene octylphenylene ether, ethoxylated isooctylphenol, octylphenol, nonylphenol, alkylphenyl polyglycol ethers , tributylphenyl polyglycol ether, tristearylphenyl polyglycol ether, polyether alkylaryl alcohols, alcohol and fatty alcohol / ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers, ethoxylated polyoxypropylene, polyglycol ether acetal lauryl alcohol, sorbitol esters , residual lyes lignin-sulphites and methylcellulose.

Suitable substances for the preparation of directly sprayable solutions, emulsions, pastes or oil dispersions are: fractions of mineral oil from medium boiling point to high, such as eg kerosene or diesel oil, in addition, coal tar oils, and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, for example, toluene, xylene, paraffin, tetrahydro-naphthalene, alkylated naphthalenes and their derivatives, methanol, ethanol, propanol, butanol, cyclohexanol, cyclohexanone, isophorone, strongly polar solvents , for example, dimethyl sulfoxide, N-methylpyrrolidone and water.

Powders, spraying and spraying agents can be prepared by mixing or grinding together the active substances with a solid support.

Granules (eg coated, impregnated or homogeneous granules) can be prepared by binding the active ingredient to a solid support. Examples of solid carriers are minerals such as silica gel, silicas, silica gels, silicates, talc, kaolin, limestone, lime, bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium oxide land magnesium, ground plastics, and fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas and plant products such as cereal powders, bark, wood and nutshell meal, cellulose powders or other solid supports.

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

Examples of formulations are: 1. Products for dilution with water A) Water soluble concentrates (SL) parts by weight of the active ingredients are dissolved in water or in a water-soluble solvent. Alternatively, humectants or other auxiliaries may be added. The active ingredient dissolves when it is diluted with water.

B) Dispersible concentrates (DC) parts by weight of the active ingredients are dissolved in cyclohexanone by adding a dispersant, for example, polyvinylpyrrolidone. Diluting with water, a dispersion is obtained.

C) Emulsifiable concentrates (EC) parts by weight of the active ingredients are dissolved in xylene by adding calcium dodecylbenzenesulfonate and castor oil ethoxylate (5% respectively).

Diluting with water, an emulsion is obtained.

D) Emulsions (EW, EO) 40 parts by weight of the active ingredients are dissolved in xylene by adding calcium dodecylbenzenesulfonate and castor oil ethoxylate (5% respectively). This mixture is introduced into water by means of an emulsifier (Ultraturrax) and transformed into a homogeneous emulsion. Diluting with water, an emulsion is obtained.

E) Suspensions (SC, OD) In a ball mill, 20 parts by weight of the active ingredients are comminuted by adding a dispersant, humectant and water or an organic solvent, obtaining a fine suspension of active ingredient. By diluting with water, a stable suspension of the active ingredient is obtained.

F) Granules dispersible in water and granules soluble in water (WG, SG) 50 parts by weight of the active ingredients are finely ground, adding dispersants and wetting agents, and transformed into water-dispersible or water-soluble granules by technical devices (for example, extruder, spray tower, fluidized bed). By diluting with water, a dispersion or stable solution of the active principle is obtained.

G) Dispersible powders in water and water soluble powders (WP, SP) 75 parts by weight of the active ingredients are ground in a rotor-stator mill adding dispersant, humectants and silica gel. Diluting with water, a stable dispersion or solution is obtained with the active principle. 2. Products for direct application H) Sprayable powders (DP) parts by weight of the active ingredients are ground finely and intimately mixed with 95% of a finely divided kaolin. A sprayable powder is obtained.

I) Granules (GR, FG, GG, MG) 0.5 parts by weight of the active ingredients are ground finely and associated with 95.5% support. Current methods are: extrusion, spray drying and fluidized bed. Granules are obtained that can be applied without dilution.

J) Ultra low volume solutions (UL) parts by weight of the active ingredients are dissolved in an organic solvent, for example, xylene. A product is obtained which can be applied without dilution. The active principles can be used as such, in the form of their formulations or the forms of application prepared therefrom, for example, as solutions, powders, suspensions or dispersions, emulsions, directly sprayable oil dispersions, pastes, sprayable powders, spraying or watering agent. The forms of application depend entirely on the purpose of application, but in any case it is necessary to ensure a distribution as fine as possible of the active ingredients according to the invention.

Aqueous application forms can be prepared from emulsion concentrates, pastes or wettable powders (sprayable powders, oil dispersions) by adding water. To prepare emulsions, pastes or oil dispersions, substances can be homogenized as such or dissolved in an oil or solvent in water with the aid of a humectant, adhesion promoter, dispersant or emulsifier. Alternatively, compound concentrates of the active substance, humectant, tackifier, dispersant or emulsifier, if appropriate, solvent or oil, may be prepared and such concentrates are suitable to be diluted with water.

The active substance concentrations in ready-to-use preparations can vary widely. In general, they vary from 0.0001 to 10%, preferably from 0.01 to 1%.

The active ingredients can also be used successfully in the ultra low volume (ULV) process, formulations with more than 95% by weight of active ingredient, or even the active ingredient without additives, can be applied.

Several types of oil, humectants, adjuvants, herbicides, fungicides or other pesticides or bactericides can be added to the active ingredients, if necessary, just before application (tank mixture). These agents can be mixed with 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 applied, treating the harmful fungi, the plants, seeds, floors, surfaces, materials or enclosures to be kept free of them, with an active fungicidal amount of the mixture or of the compounds I and II in the separate application. The application can be done before or after the infection by the harmful fungi.

The fungicidal effect of the compound and the mixtures can be demonstrated by the following tests: The active ingredients are prepared separately or together as a stock solution with 0.25% by weight of active ingredient in acetone or DMSO. To this solution is added 1% by weight of Uniperol® EL emulsifier (humectant with emulsifying effect based on ethoxylated alkylphenols) and diluted with water to the desired concentration.

Application examples - Efficiency against grape peronospora caused by Plas-mopara viticola The leaves of vine grown in pots of the variety "Riesling" were sprayed until they dripped with aqueous suspensions of the active ingredient concentration indicated below, the next day the reverse sides of the leaves were inoculated with an aqueous suspension of zoospores of Plasmopara viticola. Next, the plants were placed, first, for 48 hours in a chamber saturated with steam at 24 ° C and then for 5 days in the greenhouse at temperatures between 20 and 30 ° C. After this time the plants were again placed for 16 hours in a humid chamber to accelerate the development of sporangia. The development of the infection on the reverse sides of the leaves was then visually determined.

The visually determined values for the percentage of infected leaf surface were converted into action degrees as% of the untreated control: The degree of action (W) is calculated according to Abbot's formula as follows: W = (1 - s /) - 100 a is equivalent to the fungal infection of the plants treated in% and ß is equivalent to the fungal infection of the untreated plants (control) in% Given a degree of action equal to 0, the infection of the treated plants is equivalent to that of the untreated control plants; in case of an action grade of 100, the treated plants do not present any.

The expected degrees of action of the mixtures of active ingredients are determined by means of Colby's formula (Colby, SR (Calculating synergistic and antagonistic responses of herbicide combinations), Weeds, 15, pp. 20-22, 1967) and compared to the observed degrees of action.

Colby's formula: E = x + y - xy / 100 E means the expected degree of action, translated in% of the untreated control, when using the mixture from the active ingredients A and B in the concentrations a and bx is the degree of action, translated in% of the untreated control, when using the active principle A in the concentration a and is the degree of action, translated in% of the untreated control, when using the active principle B in the concentration b.

Table A - Individual active principles Table B - Mixtures according to the invention *) degree of action calculated according to Colby's formula From the results of the tests it is clear that the observed degree of action is with all the mixing ratios higher than the pre-calculated degree according to the Coiby formula.

Claims (10)

Claims

1. Fungicide mixtures, which contain (1) the triazolopyrimidine derivative of the formula I (2) the dinocap of formula II, composed of dinitrophenol derivatives of the formulas lia and llb, where n is 0, 1 or 2, in an active synergetic quantity.

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

3. Fungicidal product, containing a liquid or solid support and a mixture according to claims 1 or 2.

4. Procedure for combating harmful fungi of the oomycete class, characterized in that fungi, their habitat or the materials, plants, soil or seeds to be protected against fungal infection are treated with an active synergistic amount of the fungi. compound I and dinocap II according to claim 1.

5. Process according to claim 4, characterized in that the compounds I and lia and llb according to claim 1 are simultaneously applied together or separately, or successively.

6. Process according to claim 4, characterized in that the mixture according to claims 1 or 2 is applied on the plants or the soil to be protected against infection by fungi in an amount of 5 g / ha to 4000 g / ha.

7. Process according to claims 4 and 5, characterized in that the mixture according to claims 1 or 2 is applied in an amount of 1 to 1000 g / 100 kg of seeds.

8. Process according to claims 4 to 7, characterized in that the noxious fungus, Plasmopara viticola, is combated.

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

10. Use of compound I and compound II according to claim 1 for obtaining a product suitable for combating oomycetes.