MXPA06008276A - Fungicide mixtures based on a triazolopyrimidine derivative - Google Patents

Abstract

The invention relates to fungicide mixtures containing:1) the triazolopyrimidine derivative of formula (I), and 2) fenarimol of formula (II), as active constituents, in a synergistically active quantity. The invention also relates to methods for controlling pathogenic fungi with mixtures of compound (I) and compound (II), to the use of compound (I) and compound (II) for producing such mixtures, and to agents containing said mixtures.

Description

FUNGICIDE MIXES Description The present invention relates to fungicidal mixtures for combating harmful fungi, which contains as active components 1) the idriazolopyrimidine derivative of the formula I, 2) fenarimol of the formula II, in a synergistic canonical accliva.

In addition, the invention relates to a process for combating rice pathogens with mixtures of compound I with compound II and the use of compound I with compound II for obtaining such mixtures, as well as products containing these mixtures .

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

Compound II, (4-chloro-phenyl) - (2-chloro-phenyl) -pyrimidin-5-yl-methanoi, its preparation and its effect against harmful fungi are also known from the literature (GB 12 18 623; common denomination: fenarimol).

Mixtures of iazolipyrimidine derivatives with other acidic principles 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 as fungicides with numerous diseases of cereals, fruits and legumes, such as, for example, powdery mildew in wheat and barley or gray mold in apples. The known mixtures of US 6 268 371 are described as effective fungicides, especially against rice pathogens. The fungicidal effect of known mixtures against harmful fungi of the oomycete class leaves something to be desired.

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 the Oomycetes.

Oomycetes produce economically important damages in various plant crops. In many regions, infections caused by Phytophthora infestans in the potato and tomato culíivo are the most important fungal diseases of plañías. In the viículíura the peronospora of the vine causes considerable damage.

Practical experiences in agriculture have shown that the repeated and exclusive use of a single active principle in the fight against harmful fungi results in many cases to a rapid selection of those strains of fungi, which have developed a natural or adaptive resistance to the corresponding fungi. acivo principle. In the future, it is no longer possible to combat this fungus effectively with the corresponding negative principle.

To reduce the danger of the selection of strains of resistant fungi, mixtures of different acíivos principles are used nowadays. Thanks to the combination of active principles with different mechanisms of action, the success of the treatment can be ensured for a long period.

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

Initially, the mixtures found at the beginning were found. In addition, it has been found that, when applying compound I and compound II simul- feeneously, jointly or separately, or when applying compound I and compound II successively, it is possible to combat better rice pathogens, which the individual compounds, (synergistic mixtures).

The mixtures of compound I and compound II or compound I and compound II applied simulinely together or separately, stand out as being excellently effective against rice pathogens of the class of Ascomycetes, Deuteromycetes, Oomycetes and Basidiomycetes. They can be used in phytosanitation as foliar and soil fungicides.

They are especially important for combating a myriad of fungi in different plantain 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 fungal fungi: Blumeria graminis (powdery mildew) in cereals, Erysiphe cichoracearum and Sphaerotheca fuligi-nea in cucurbiíáceas, Podosphaera leucotricha in apples, Uncinula necator in vine, Puccinia species in cereals, Rhizoctonia species in cotton, rice and turf, Ustilago species in cereals and sugarcane, Venturia inaequalis in apples, Bipolaris and Drechslera species in cereals, rice and turf, Septoria nodorum in ire, Botrytis cinerea in strawberries, legumes, ornamental wafers and vine, species of Mycosphaerella in bananas, peanuts and cereals, Pseudocercosporella herpotri-choides in ire and barley, Phytophthora infestans in potatoes and tomatoes, species of Pseudoperonospora in cucurbiíáceas and hops, Plasmopara viticulture in grapevine, species of Alternaria in legumes and fruits, as well as species of Fusarium and Verticillium.

They are especially suitable for combaising harmful fungi of the oomycete class in different climates, such as legumes (eg cucumbers, beans and cucurbits), especially downy mildew in tomatoes and paras caused by Phytophthora infes-tans, as well as the powdery mildew (perenospora of the vine), caused by Plasmopara viticola.

Additionally, it is suitable for use in the protection of materials (eg wood), for example conifer Paecilomyces varíotii.

Compound I and compound II can be applied simultaneously together or separately or successively. The order in the separate application, generally, does not affect in any way the success of the treatment.

Preferably, pure active substances I and II are used in the preparation of the mixtures, to which other active substances can be added against harmful fungi or other parasites, such as insects, arachnids or nematodes, or else herbicidal or growth regulating substances. or fertilizers.

Like other active principles in the above-mentioned sense, especially the selected active principles of the following groups are appropriate: • acylalanines, such as benalaxyl, meialaxyl, ofurace, oxadixyl, • amine derivatives, such as aldimorf, dodemorf, phenpropimorf, fenpropidin, guazatin, iminoctadine, tridemorph, • anilinopyrimidines, such as pyrimethanil, mepanipyrim or cyprodinil, • antibiotics, such as cycloheximide, griseofulvin, kasugamycin, natamycin, polyoxin or streptomycin, • azoles, such as bitertanol, bromoconazole, ciproconazole, diphenoconazole, diniiroaceazole, enilconazole, epoxiconazole, fenbuconazole, fluquiconazole, flusilazole, flu- idaro, hexaconazole, imazalil, ipconazole, meconazole , myclobu- nyl, penconazole, propiconazole, prochlorozole, profioconazole, simeconazole, tebuconazole, teiraconazole, idriadime- pone, iardimenol, udiflumizol, ichigoconazole, • dicarboximides, ial as mylozoline, • diiocarbamaphos, iales such as ferbam, nabam, meiam, propineb, polycarbamazine, - ram.ziram, zineb, • heyerocyclic compounds, such as anilacin, ben omilo, boscalide, carbendazole, carboxy, oxycarboxim, ciazofamide, dazomei, dilianone, famoxadone, phenamidone, fuberidazole, flutolanil, furameipyr, isoproyiolane, mepronium, nuarimol, probenazole, pyroquilone, quinoxifen, silthiopham, thiabendazole, thifluzamide, iadinyl, íriciclazol, irliforina, • copper fungicides, such as bordeaux broth, copper acetamide, copper oxychloride, basic copper sulfate, • nitrophenyl derivatives, such as binapacril, dinocap, dinobutone, niiopofalisopropyl, • phenylpyrroles, such as fenpiclonil or fludiosonil, • sulfur, • other fungicides, such as acibenzolar-S-methyl, benthiavalicarb, carpropamide, cytotoxanil, cyflifenamide, cymoxanil, diclomezine, diclocimet, dieofencarb, edifenfos, etaboxam, fenhexamide, phenylaine, phenoxanyl, ferimzone, fluazinam, phosphorous acid, foseiyl, phenoxylamino, iprovalicarb, hexachlorobenzene, phenone, methylisothiocyanate, pencicuron, propamocarb, phthalide, amioleophosphoryl, quintozene, zoxamide, • strobilurins, such as azoxysyrobin, dimoxysyrobin, fluoxastrobin, kresoximmethyl, methominosilobin, orisastrobin, pyraclostrobin or trifloxysyrobin, • sulfenic acid derivatives, such as capyafol , capían, folpeí, • cinnamic acid amides and analogs, such as dimetomorph, flumetover or flumorf.

In one embodiment of the mixtures according to the invention, compounds I and II are mixed with another fungicide III or two fungicidal rings IV and IV.

The mixtures of compounds I and II with a compound III are preferred. Mixtures of compounds I and II as active compounds are especially preferred.

Compound I and compound II can be applied simultaneously or separately or successively. The order in the separate application, generally, does not affect in any way the success of the trip.

Compound I and compound II are usually applied in a weight ratio of 100: 1 to 1: 100, preferably, 20: 1 to 1:20, especially 10: 1 to 1:10.

The components III and optionally IV are added, if desired, in a ratio of 20: 1 to 1: 20 with the 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 1000 kg / ha, preferably from 50 to 900 g / ha, especially from 50 to 750 g. /he has.

The application rates for the compound I vary correspondingly, as a rule, from 1 to 1000 g / ha, preferably from 10 to 900 g / ha, especially from 20 to 750 g / ha.

The application amounts for compound II. they vary correspondingly, as a rule, from 1 to 1000 g / ha, preferably from 10 to 500 g / ha, especially from 40 to 350 g / ha.

In seed processing, seeds are usually used in the mixture from 1 to 1000 g / 100 kg of seeds, preferably from 1 to 200 g / 100 kg, especially from 5 to 100 g / 100 kg.

The process for combating harmful fungi is carried out by separate or combined application of compound I and compound II or mixtures of compound I and compound II, by pulverizing or dusting the seeds, the plants or the soil before or after the emergence of molds. plants.

The mixtures of the invention or the compounds I and II can be converted into the customary formulations, for example: solutions, emulsions, suspensions, powders, passages 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 a known manner, for example, by diluting the active principle with solvents and / or supports, if desired, using emulsifiers and dispersants. As disolveníes / auxiliary subsides are appropriate, subsancially, for this purpose: water, aromatic solvents (eg Solvesso products, xylene), paraffins (eg petroleum fractions), alcohols (eg methanol, butanol, pentanol, benzyl alcohol), ketones (eg cyclohexanone, gamma-butyrolactone), pyrrolidones (NMP, NOP), acetylates (glycol diacetate), glycols, dimethyl acid amides, fatty acids and degrees. Basically, solvent mixtures, support substrates, such as natural stone powders (eg kaolins, clays, falco, fiza) and syn speic stone powders (eg, allymethylated silicic acid, silicates) can also be used; emulsifiers, such as non-ionogenic and anionic emulsifiers (eg polyoxyethylene fatty alcohol ethers, alkyl sulphonates and aryl sulphonates) and dispersants, such as sulphide residual liquors and methyl cellulose.

Suitable tenso-acids are the alkali metal, alkaline earth metal and ammonium salts of lignin sulphonic acid, naphthalenesulfonic acid, phenolsulfonic acid, dibuyl-naph-allynesulfonic acid, alkylaryl sulphonates, alkyl sulphaides, alkyl sulfonates, fatty alcohol sulfates, fatty acids and glycol ethers of sulphated fatty alcohol, in addition, sulfonated naphthalene condensates and naphthalene derivatives with formaldehyde, naphthalene or naphthalene sulfonic acid condensates with phenol and formaldehyde, polyoxyethylene oleylphenyl ether, ethoxylated isooctylphenol, octylphenol, nonylphenol, alkylphenyl polyglycol ethers, tributylphenyl polyglycol ether, tristearylphenyl polyglycol ether, polyether alkylaryl alcohols, alcohol and fatty alcohol condensates / ethylene oxide, ethoxylated castor oil, polyoxyethylene alkyl ethers, epoxylated polyoxypropylene, polyglycol ether acetal lauryl alcohol, sorbitol esters, bleaches lignin-sulphite esiduales 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, tetrahydronaphthalene, 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 substrates with a solid support.

Granules (eg coated, impregnated or homogeneous granules) can be prepared by bonding the active ingredient with a solid support. Examples of solid charges are: mineral fibers, such as silica gel, silicic acids, silica gels, silicates, talc, kaolin, limestone, lime, bolus, loess, clay, dolomite, diatomaceous earth, calcium sulfate and sulphate. of magnesium, magnesium oxide, ground plastics, as well as fertilizers, such as ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas and vegetable products, such as cereal flour, bark, wood and nut shells powders , 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 solution. Alternately, you can add humecides or other auxiliaries. The active ingredient dissolves when 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 eioxylate (5% respectively). Diluting with water, an emulsion is obtained.

D) Emulsions (EW, EO) 40 parts by weight of the active principles 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 principles 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 principles are ground finely, 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-esiafor mill adding dispersant, humecerous 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 mixed intimately 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. You get a product that can be applied without dilution The active ingredients 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 agent 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 solvents or dissolved in an oil or dissolved in water with the aid of a wetting agent, adhesion agent, dispersant or emulsifier. Alternately, compound concentrates of the acrylic, wetting, tackifying, dispersing or emulsifying properties may be prepared, if appropriate, solvent or oil, and those concentrated 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, bringing the noxious fungi, pineapples, seeds, floors, surfaces, materials or enclosures to be kept free of them, with an active fungicidal quantity 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 mixtures can be demonstrated by means of the following tests: The active ingredients are prepared separately or jointly as a stock solution with 0.25% by weight of the active principle in acetyone or DMSO. To this solution is added 1% by weight of Uniperol® EL emulsifier (emulsifier moistened with ethoxylated alkylphenols) and diluted with water to the desired concentration.

Application examples - Efficiency against grape peronospora caused by Plasmopara 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 of 20 and 30 ° C. After this time the plañías were placed again for 16 hours in a humid chamber to accelerate the development of sporangia. Then the development of the infection on the reverse sides of the leaves was visually determined.

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

The expected action levels of the active ingredient mixtures are determined by means of Colby's formula (Colby, SR (Calculating synergistic and antagonistic responses of herbicide combinaiions ", 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, expressed in% of the non-irritated conírol, when using the mixture from the active principles 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 non-framed 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 can be seen that the mixtures according to the invention in all the mixing ratios are markedly more effective than that which had been precalculated according to the Colby formula.

Claims (10)

Claims

1. Fungicide mixtures, which come together 1) the Iriazolopyrimidine derivative of the formula 2) fenarimol of the formula II, in an active synergy.

2. Fungicidal mixtures according to claim 1, which contain the compound of the formula I and the compound of the formula 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 combaising harmful rice pathogenic fungi, characterized in that the fungi, their habia or the plants, plañís, the soil or the seeds to be protected against fungal infection are irrigated, with a synergistic acidic content of the compound I and a compound II according to claim 1.

5. Process according to claim 4, characterized in that the compounds I and ll according to claim 1 are applied simultaneously in a joint or separate form, or in succession.

6. Process according to claim 4, characterized in that the mixture according to claims 1 or 2 is applied in an amount of 5 g / ha up to 1000 g / ha.

7. Process according to claims 4 to 6, characterized in that noxious fungi of the oomycete class are combated.

8. 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.

9. Seeds containing the mixture according to claims 1 or 2 in an amount of 1 to 300 g / 100 kg.

10. Use of compound I and compound II according to claim 1 for the production of an appropriate product for combaising harmful fungi.