MXPA06009226A - Fungicidal mixtures for controlling rice pathogens - Google Patents

Abstract

The invention relates to fungicidal mixtures controlling rice pathogens containing in the form of active agents:1) a triazolopyrimidine derivative of formula (I) and 2) vinclozolin of formula (II) in synergistically active quantities and to a method for controlling rice pathogens by means of the mixture of the compounds (I) and (II), thereby making it possible to produce said mixtures and the products containing them.

Description

Fungicide mixtures to combat rice pathogens Description The present invention relates to fungicidal mixtures for combating rice pathogens, which contain as active components: 1) the thiazolopyrimidine derivative of the formula 2) vinclozoline of formula II, in an active synergetic quantity.

Furthermore, the invention relates to a process for combating rice pathogens with mixtures of compound I with compounds II and to the use of compound I with compounds II for obtaining such mixtures, as well as to products that contain 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).

The compound II, 3- (3,5-dichloro-phenyl) -5-methyl-5-vinyl-oxazolidin-2,4-dione its preparation and effect against harmful fungi are known from the literature (DE-OS 22 07 576 common denomination: vinclozolin).

Mixtures of trialzolopyrimidine derivatives with vinclozin are generally known from EP-A 988 790. Compound I is included in the general disclosure of this patent, but is not explicitly mentioned therein. The combination of compound I with vinclozolin e new.

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.

To effectively combat rice pathogens with the lowest possible application rates, the present invention was aimed at providing mixtures which, with a small amount of total application in active principle, had an improved effect against a broad spectrum of rice pathogens.

Due to the special conditions in the cultivation of rice plants, fungicides for rice must meet very different requirements, than those used in cereals or fruits. There are differences in the method of application: In addition to the application on the leaves practiced in many places, the modern cultivation of rice usually applies the fungicide directly during or just after sowing on the ground. The fungicide is absorbed by the roots of the plant and transported by means of the sap in the plant to the parts of the plant to be protected. On the contrary, in cereal or fruit crops the fungicide is usually applied on the leaves or fruits, so in these crops the systemic plays a much less important role.

In addition, in rice crops there are other typical pathogens than in cereals or fruits. Pyricularia oryzae, Corticium solani (Syn. Rhizoctonia sasakii) are the pathogens that produce the most important diseases in rice plants. Rhizoctonia sasaki is the only important pathogen in agriculture within the subclass of Agarico-mycetidae. This fungus infects the plant not like most other fungi by spores, but by means of a mycelial infection.

For this reason, knowledge can not be transferred regarding the fungicidal action of the cultivation of cereals or fruits to rice crops.

In order to effectively combat rice pathogens with the lowest possible application rates, the present invention was aimed at providing mixtures which, with a small amount of total application in active principle, have an improved effect against harmful fungi.

Therefore, the mixtures defined at the beginning were found. Surprisingly, it has been found that rice pathogens with the vinclozoline mixtures defined above are attacked much more efficiently than with the vinclozoline mixtures of the triazolopyrimidine compounds known from EP-A 988 790. Furthermore, it has been found that that by applying the compounds I and the compounds II simultaneously, jointly or separately, or by applying the compounds I and compounds II successively, it is possible to combat better rice pathogens, than with the individual compounds.

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.

As other active ingredients in the sense indicated above, the active principles selected from the following groups are especially suitable: • acylalanines, such as benalaxyl, metalaxyl, ofurace, oxadixyl, • amine derivatives, such as aldimorf, dodemorf, phenpropimorf, fenpropidin, guazatin, iminoctadine, tridemoiiy • anilinopyrimidines, 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, epoxiconazole, fenbuconazole, fluquiconazole, flusilazole, flutriafol, hexaconazole, imazalil, pconazole, metconazole , myclobutanil, penconazole, pro piconazole, prochloroaz, prothioconazole, simeconazole, tebuconazole, tetraconazole, triandimephone, triadimenol, triflumizole, triticonazole, dicarboximides, such as mylozoline, • dithiocarbamates, such as ferbam, nabam, maneb, mancozeb, metam , metiram, propineb, polycarbamate, thiram, ziram, zineb, • heterocyclic compounds, such as anilacin a, benomyl, boscalide, carbendazole, carboxy, oxycarboxim, ciazofamide, dazomet, dithianone, famoxadone, phenamidone, fenarimol, fuberidazole, flutolanil, furametpir, isoprothiolane, mepronil, nuarimol, pentiopyrad, probenazole, pyroquilone, quinoxifene, siltiofam, thiabendazole, thifluzamide, thiophanate-methyl, thiadinyl, tricyclazole, triforine, • nitrophenyl derivatives, such as binapacryl, dinocap, dinobutone, nitroftal- isopropyl, • phenylpyrroles, such as phenpiclonil or fludiosonil, • sulfur or copper fungicides, • other fungicides , such as acibenzolar-S-methyl, benthiavalicarb, carpropamide, chlorothalonil, cyflufenamide, cymoxanil, diclomezine, diclocimet, dietofencarb, edifenfos, etaboxam, fenhexamide, fentina-acetate, fenoxanil, ferimzone, fluazinam, fosetyl, fosetyl-aluminum, acid phosphorous, iprovalicarb, hexachlorobenzene, metrafenone, methylisothiocyanate, pencicuron, propamocarb, phthalide, toloclofos-methyl, quintozene, zoxamide, • estrobi lurins, such as azoxystrobin, dimoxystrobin, fluoxastrobin, kresoxim-methyl, methominostrobin, orisastrobin, pyraclostrobin or trifloxystrobin, • sulfenic acid derivatives, such as captafol, captan, dicloflunanide, tolylfluanid, • cinnamic acid amides and the like, dimetomorf, flumetover or flumorf.

In one embodiment of the mixtures according to the invention, compounds 1 and II are mixed with another fungicide III or two other fungicides III and IV.

As components II and optionally IV, anilinopyrimidines and heterocyclic compounds are especially suitable.

Mixtures of compounds I and II with a component III are preferred.

Especially preferred are mixtures of compounds I and II.

The mixtures of the compounds I and II or the compounds 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 and Basidiomycetes. They present a systemic high and, therefore, are suitable to be used for the treatment of seeds and as foliar and soil fungicides.

They are especially important for combating harmful fungi in rice plants and their seeds, such as Bipolaris and Drechslera species, as well as Pyricularia oryzae. They are especially suitable for combating the burning of rice caused by Pyricula-ría oryzae.

In addition, the combination according to the invention of compounds I and II is also suitable for combating other pathogens, such as Septoria and Puccinia species in cereals and Alternaria and Boytritis species in legumes, fruits and wine.

The compound I and the compound 11 can be applied simultaneously together or separately or successively, so that they can develop their fungicidal effect together. The order e? the separate application, generally, does not affect in any way the success of the treatment.

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.

Components III and optionally IV are added, if desired, in a ratio of 20: 1 to 1: 20 with 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 2000 kg / ha, preferably from 50 to 1500 g / ha, especially from 50 to 1000 g. /he has.

The application rates for 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 accordingly, as a rule, from 1 to 1500 g / ha, preferably from 10 to 1000 g / ha, especially from 20 to 750 g / ha. d In the treatment of seeds, amounts in the mixture are usually used 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.

To combat phytopathogenic fungi in rice crops, the separate or combined application of compounds I or II or of the mixture of compounds I and II is carried out by spraying seeds, seedlings, plants or is soil before or after planting. the plants or before or after the emergence of the plants. Preferably, the compounds can also be applied in the form of granules or powdering the soil. In another preferred variant of the process, the compounds are applied by spraying the leaves.

The mixtures of the invention or the compounds I and II can be transformed 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 methanol, butanol, pentanol, benzyl alcohol), ketones (e.g. cyclohexanone, gamma-butyrolactone), pyrrolidones (NMP, NOP), acetates (glycol diacetate), glycols, dimethylgreased 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, naphthalene sulfonic acid, phenolsulfonic acid, dibutyl naphthalisulfonic acid, alkylaryl sulfonates, alkyl sulfates, alkyl sulfonate, 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 octyl-phenyl ether, ethoxylated isooctylphenol, octylphenol, nonylphenol, alkylphenyl polyglycol ethers, tributylphenyl polyglycol ether, tristearyl phenyl polyglycol ether, polyether alkylaryl alcohols, alcohol and fatty alcohol condensates / ethylene oxide, ethoxylated castor oil, polyoxyethylene alkyl ethers, ethoxylated polyoxypropylene, polyglycol ether acetal lauryl alcohol, sorbitol esters, bleaches residual lig nino-sulphites and methylcellulose.

Substances suitable for the preparation of directly sprayable solutions, emulsions, pastes or dispersions of oil 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, tetrahydronaphthalin, alkylated naphthalenes and their derivatives, methanol, ethanol, propanol, butanol, cyclohexanol, cyclohexanone, isophorone, solvents strongly polar, 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 fillers are: mineral soils, such as silica gel, silicic acids, silicate gels, silicates, talc, kaolin, limestone, lime, bolus, loess, clay, dolomite, diatomaceous earth, calcium sulfate and magnesium sulfate, oxide magnesium, 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 powder, cellulose powder 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 finely ground and intimately mixed with 95% or 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% or 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 such or dissolved in an oil or solvent in water with the aid of a humectant, adhesion promoter, dispersant or emulsifier. Alternatively, concentrates composed of the active substance, wetting agent, tackifier, dispersant or emulsifier, if appropriate, solvent or oil, can 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.

Compounds I and II or mixtures or the corresponding formulations are applied, treating the harmful fungi, plants, seeds, soils, surfaces, materials 0 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 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 example - Protective efficiency against rice burning caused by Pyricularia oryzae The leaves of rice seedlings grown in pots of the variety "Tai-Nong 67" were sprayed until they dripped with an aqueous suspension of the concentration of active principle indicated below. The next day the plants were inoculated with an aqueous spore suspension of Pyricularia oryzae. Next, the test plants were placed for 6 days in climatic chambers at 22 - 24 ° C and 95 - 99% relative humidity of the air. The extent of infection development in the leaves was then visually determined.

The evaluation was carried out determining the infected plants in percent. These percentage values became degrees of action.

The degree of action (W) is calculated according to Abbot's formula as follows: 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 action levels of the active ingredient mixtures 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 with 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 b is the degree of action, translated in% of the untreated control, when using the active principle A in the concentration a is the degree of action, translated in% of the untreated control, when using the active principle B in the concentration b.

As the comparative active ingredients, the known compounds A and B of the vinclozoline mixtures described in EP-A 988 790 were used: Table A - Individual active ingredients Table B - Mixtures according to the invention *) degree of action calculated according to Colby's formula Table C - Comparative assays Known vinclozoline mixtures of EP-A 988 780 *) degree of action calculated according to Colby's formula From the results of the tests it is clear that the mixtures according to the invention, thanks to a strong synergism, are markedly more effective than the vinclozoline mixture of the known comparative compounds of EP-A 988 790.

Claims (10)

Claims Fungicide mixtures, which contain

1) the triazolopyrimidine derivative of the formula 2) vinclozoline of formula II, in an active synergetic quantity.

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. Product containing a liquid or solid support and a mixture according to claims 1 or 2.

4. Procedure for combating harmful rice pathogenic fungi, 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 compound I and compounds 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 manner, or successively.

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 to 2000 g / ha.

7. Method according to one of claims 4 to 6, characterized in that the noxious fungus, Pyricularia oryzae, is 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 1000 g / 100 kg.

10. Use of compound I and compound II according to claim 1 for obtaining an appropriate product for combating harmful fungi.