MXPA06007753A - Fungicidal mixtures for the control of rice pathogens - Google Patents

Abstract

The invention relates to fungicidal mixtures for the control of fungal pests harmful to plants, comprising the active components 1) the triazolopyrimidine derivative of formula (I), and 2) tridemorph of formula (II), in which n=10, 11, 12 (60-70%) or 14, in a synergistically-effective amount, method for the control of fungal pests using mixtures of compound (I) with the compounds (II), the use of compound (I) with the compounds (II) for the production of such mixtures and means comprising said mixtures.

Description

FUNGICIDE MIXES Description The present invention relates to fungicidal mixtures intended to combat phytopathogenic noxious fungi, which contain as active components 1) the triazolopyrimidine derivative of the formula I and 2) tridemorph of formula II CH, CH3- (CH2) -N O CH, wherein n represents 10, 11, 12 (60-70%) or 14, in a synergistically effective amount. Furthermore, the invention relates to a method for combating noxious fungi with mixtures of compound I with compounds II and the use of compound I with compounds II in the preparation of such mixtures, as well as agents containing such mixtures. Compound I, 5-chloro-7- (4-methyl-piperidin-1-yl) -6- (2,4,6-trifluorophenyl) - [1,2,4] triazole [1,5-a] ] pyrimidine, its preparation and its action against harmful fungi, is known from the specialized literature (WO 98/46607).

The mixture of the N-alkylmorpholine II derivatives, whose main component is 2,6-dimethyl-4-tridecylmorpholine, its preparation and its action against harmful fungi are also known from the specialized literature (DE-AS 11 64 152 its common name is tridemorph). Mixtures of triazolopyrimidines with other agents are known to the public by EP-A 988 790 and US 6,268,371. The synergistic mixtures described in EP-A 988 790 are described as effective fungicides in the fight against various diseases of cereals, fruits and vegetables, such as mildew which affects wheat and barley or gray rot, which affects The apples. The mixtures known from US 6,268,371 are described as effective fungicides, in particular when they are applied against rice pathogens. The objective that was intended to be achieved with the present invention, so that the fight against phytopathogenic fungi was effective with low possible inputs, was to obtain mixtures that would have a better effect in the fight against these fungi, and at the same time reduce the total proportion of the input of active agents applied (synergistic mixtures). Pointing to that goal, the mixtures defined at the beginning of the present were found. In addition it was found that if compound I and compound II were applied simultaneously, either jointly or separately, or if compound I and compound II were applied in succession, the action against harmful fungi was more successful than if each one by itself. The mixtures of compound I and of compounds II and, where appropriate, the simultaneous application, either together or separately, of compound I and of compounds II, stand out for the outstanding effectiveness of which they give proof against a broad spectrum of phytopathogenic fungi, in particular those of the class of Ascomycetes, Deuteromycetes, Oomycetes and Basidiomycetes. They can be used in the protection of plants as fungicides applied on the leaves or on the ground. They have special importance to combat a plurality of fungi that affect various crop plants such as bananas, cotton, vegetables (for example, cucumbers, beans and cucurbits), barley, grass, oats, coffee , potatoes, corn, fruit plants, rice, rye, soybeans, tomatoes, grapes, wheat, ornamental plants, sugar cane and a plurality of seeds. They are apt to fight profitably the following phytopathogenic fungi: Blumeria graminis (true mildew) that affects cereals; Erysiphe cichoracearum and Sphaerotheca fuliginea, which affect cucurbits; Podosphaera leucotricha, which affects apples; Uncinula necator, which affects the vines; Puccinia species, which affect cereals; the Rhizoctonia species, which affect cotton, rice and turf; the Ustilago species that affect cereals and sugarcane; Venturia inaequalis, which affects apples; the species of Bipolaris and Drechslera, which affect cereals, rice and grass; Septoria nodorum, which affects wheat; Botrytis cinerea, which affects strawberries, vegetables, ornamental plants and vines; Mycosphaerella species, which affect bananas, peanuts and cereals; Pseudocercosporella herpotrichoides, which affects wheat and barley; Pyricularia oryzae, which affects rice; Phytophthora infestans, which affects potatoes and tomatoes; Pseudoperonospora species, which affect cucurbits and hops; Plasmopara viticola, which affects the vines; Alternaria species that affect vegetables and fruits, as well as Fusarium and Verticillium species. The compounds according to the invention are of particular importance in combating the harmful fungi that affect rice plants and their seed, such as the Bipolaris and Drechsleria species, as well as the Pyricularia oryzae. They lend themselves especially to fight the disease caused by Cochliobolus miyabeanus, which generates brown spots. In rice the typical pathogens are other than in cereals or fruit. The Pyricularia oryzae and the Corticium sasakii (synonym: Rhizoctonia solani) are the causes of the most important diseases of rice plants. Rhizoctonia solani is the only major pathogen in agriculture within the subclass of Agaricomycetidae. This fungus does not attack, like most other fungi, by means of spores, but by infection of the mycelium. They are also applicable to protect materials (eg woods), for example against Paecilomyces variotii.

When the mixtures are prepared, preference is given to the pure active compounds I and II, to which, as needed, other compounds active against harmful fungi or harmful animals such as insects, arachnids and nematodes, or also herbicidally active compounds can be added. or growth regulators, or fertilizers. Other active compounds that come into account for these purposes are in particular fungicides selected from the following group: • Acylalanines such as benalaxyl, ofurace, oxadixyl, • Derivatives of amines such as aldimorph, dodemorph, guazatine, iminoctadine, • Anilinopyrimidines such as pyrimethanil, mepanipyrim or cyprodinil, • Antibiotics such as cycloheximide, griseoñilvina, kasugamycin, natamycin, polyoxin or streptomycin • azoles such as bitertanol, bromoconazol, cyproconazole, difenoconazole, dinitroconazol, enilconazole, epoxiconazole, fenbuconazole, fluquiconazol, flusilazole, flutriafol, hexaconazole, imazalil, ipconazole, metconazole, myclobutanil, penconazole , propiconazole, prochloraz, prothioconazole, simeconazole, tetraconazole, triadimefon, triadimenol, triflumizole, triticonazole, • Dicarboximides such as myclozolin, procymidon, • Dithiocarbamates such as ferbam, nabam, metam, propineb, polycarbamate, ziram, zineb • Heterocyclic compounds such as anilazin, boscalid, oxycarboxin, cyazofamid, dazomet, famoxadon, fenamidon, iberiberidazole, flutolanil, furametpyr, isoprothiolan, mepronil, nuarimol, probenazole, pyroquilon, silmiofam, thiabendazole, thifluzamid, thiadinyl, tricyclazole, triforine, • Nitrophenyl derivatives such as binapacryl, dinobuton, nitrophthalisopropyl , • Other fungicides such as aci Benzolar-S-methyl, carpocramid, cyflufenamid, cymonaxil, diclomezin, diclocymet, diethofencarb, edifenphos, ethaboxam, fentin acetate, phenoxanil, ferimzone, fosetyl, hexachlorobenzene, metrafenon, propamocarb, phthalid, toloclofos-methyl, quintozene, zoxamid, • Strobilurins such as fluoxastrobin, metominostrobin, orisastrobin or pyraclostrobin, • Derivatives of sulphide acids such as captafol, • Cinnamic acid amides and analogs such as flumetover. In one embodiment of the mixtures according to the invention, compounds I and II are added, by mixing them, another fungicide III or two other fungicides III and IV. Mixtures of the compounds I and II with a component III are preferred. Particularly preferred are mixtures of compounds I and II. The compound I and the compounds II can be applied at the same time, either jointly or separately, or successively, the order of application usually having no influence on the result when the application is separate. Compound I and compounds II are usually applied in a weight ratio of 100: 1 to 1: 100, preferably 20: 1 to 1:50, in particular 10: 1 to 1: 10.

If desired, the components III and optionally IV are added to the compound I, by mixing them with it, in a weight ratio of 20: 1 to 1: 20. The amounts that are consumed in the mixtures according to the invention vary, depending on the species of the compound and the desired effect, between 5 g / ha and 1000 g / ha, preferably between 50 and 850 g / ha, preferably 50 to 750 g /he has. Ordinarily, the amounts that are consumed in the case of compound I vary, as appropriate, between 1 and 1000 g / ha, preferably between 10 and 750 g / ha, in particular between 20 and 500 g / ha. Ordinarily, the quantities that are consumed in the case of the compounds II oscillate, as appropriate, between 1 and 1000 g / ha, preferably between 10 and 750 g / ha, in particular, between 20 and 500 g / ha. When the seeds are treated, amounts of input ranging from 1 to 1000 g / 100 kg of seed, preferably from 1 to 200 g / 100 kg, in particular from 5 to 100 g / kg, are generally used in the mixture. 100 kg. When it comes to combating harmful fungi, the separate or combined application of the compounds I and II, or of the mixtures of the compounds I and II, is carried out by rolling or spraying them on the seeds, the newly sprouted seed plants, the plants or soils, before or after sowing the plants, or before or after germination. Preferably, the compounds are applied by spraying the leaves with them. The combined or separate application of the compounds can also be carried out by application of granules or by spraying on the floors.

The mixtures according to the invention or, where appropriate, the compounds I and II can be converted into the customary formulations, for example solutions, emulsions, suspensions, powders, pastes and granules. The form of application depends on the purpose pursued in each case; in any case, the aim is always to ensure a fine and uniform distribution of the compound according to the invention. The formulations are prepared in known manner, for example by diluting the active substance with solvents and / or carriers, and if desired, employing emulsifiers or dispersants. For this purpose, substantially as solvents / coadjuvants are considered: water, aromatic solvents (for example, Solvesso products, xylene), paraffins (for example, petroleum fractions), alcohols (for example, methanol, butanol, pentanol, alcohol). benzyl), ketones (for example, cyclohexanone, butriolactone gamma (?)), pyrrolidones (NMP, NOP), acetates (glycolic diacetate), glycols, fatty acid dimethylamides, fatty acids and fatty acid esters. In principle, mixtures of solvents can also be used. Carriers such as natural rock powders (eg, kaolins, clays, talc, chalk) and synthetic rock powders (eg, high dispersion silicic acid, silicates); emulsifiers as non-ionogenic and anionic emulsifiers (for example, polyoxyethylene ether fatty alcohol, alkylsulfonates and arylsulfonates) and dispersing agents such as the residual lignin sulphite and methyl cellulose. The alkali metal, alkaline earth metal and ammonium salts of lignisulfonic acid, naphthalenesulfonic acid, phenolsulfonic acid, dibutylnaphthalene sulfonic acid, alkylarylsulfonates, alkyl sulphates, alkyl sulphonates, fatty alcohol sulfates, fatty acids and glycol ethers are used as surfactants. of sulphated fatty alcohols, as are the condensation products of sulfonated naphthalene and the naphthalene derivatives with formaldehyde, the condensation products of naphthalene or, where appropriate, of naphthalenesulfonic acid, with phenol and formaldehyde, the polyoxyethylene ether octylphenol, isooctylphenol, octylphenol, nonylphenol ethoxylates, alkylphenol polyglycol ether, tributylphenyl polyglycol ether, trichylphenylpolyglycol ether, alkylaryl polyester alcohols, ethylene oxide condensates of alcohols and fatty alcohols, castor oil ethoxylated, the alkyl polyoxyethylene ether, the ethoxylated polyoxypropylene, the polyglycol ether acetal of lauryl alcohol, sorbitol esters, the residual ligninsulfite liquors and the methylcellulose. For the preparation of directly sprayable oily solutions, emulsions, pastes and dispersions, fractions of mineral oil with medium to high boiling point, such as kerosene or diesel, as well as coal tar oils and oils of high molecular weight, are included. plant or animal origin, aliphatic, cyclic and aromatic hydrocarbons, for example, toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes or their derivatives, methanol, ethanol, propanol, butanol, cyclohexanol, cyclohexanone, isophorone, strongly polar solvents, for example, dimethylsulfoxide, N-methylpyrrolidone or water.

Agents in the form of powder, dusts and sprays can be prepared by mixing or grinding together the active substances with a solid carrier. Granules, for example coating granules, impregnation granules or homogenates, can be prepared by binding the active substances to solid carriers. Solid carriers are, for example, mineral soils such as silica gels, silicates, talc, kaolin, attaclay, limestone, lime, chalk, bolus, loess, clay, dolomite, diatomaceous earth, calcium sulfate and magnesium sulfate, magnesium oxide, ground synthetic substances, fertilizers, such as, for example, ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas and vegetable products, such as cereal flour, bark meal of tree, wood and walnut shell, cellulose powder and other solid carriers. The formulations usually contain between 0.01 and 95% by weight, preferably between 0.1 and 90% by weight of the active compounds. The active compounds are applied, when these formulations are made, with a purity of 90% to 100%, preferably between 95% and 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 compounds are dissolved in water or in a water-soluble solvent. As an alternative, humectants or other adjuvants are added. When diluted in water, the active compound dissolves. B) Dispersible Concentrates (DC) 20 parts by weight of the active compounds are dissolved in cyclohexanone, by adding a dispersant, for example polyvinylpyrrolidone. When diluted in water, a dispersion occurs. C) Emulsifiable concentrates (EC) 15 parts by weight of the active compounds are dissolved in xylene, adding calcium dodecylbenzenesulfonate and ethoxylated castor oil (5% each). When diluted in water, an emulsion is produced. D) Emulsions (EW, EO) 40 parts by weight of the active compounds in xylene are dissolved, adding calcium dodecylbenzenesulfonate and ethoxylated castor oil (5% each). This mixture is put in water by an emulsifying machine (Ultraturax) and converted into a homogeneous emulsion. When diluted in water, an emulsion is produced. E) Suspensions (SC, OD) 20 parts by weight of the active compounds are comminuted in a ball mill with agitator mechanism, with dispersants, humectants and water, or an organic solvent added, until they become a fine suspension of the active compounds. When diluted in water, a stable suspension of the active compound is produced. F) Water-dispersible and water-soluble granules (WG, SG) 50 parts by weight of the active compounds are ground finely by adding dispersants and wetting agents and by means of technical instruments (for example, extrusion, spray tower, fluidized bed) they are converted into granules water-dispersible or water-soluble. When diluted in water, a stable dispersion or a stable solution of the active compound is produced. G) Water-dispersible and water-dispersible powders (WP, SP) 75 parts by weight of the active compounds are milled in a rotor-stratum mill, with dispersants and wetting agents added, as well as silica gel. When diluted in water, a stable dispersion or a stable solution of the active compound is produced. 2. Products for direct application H) Powder (DP) 5 parts by weight of the active compounds are ground finely and mixed with 95% kaolin in fine particles. In this way a sprayable agent is obtained. I) Granules (GR, FG, GG, MG) 0.5 parts by weight of the active compounds are ground finely and bound with 95.5% carriers. Processes commonly used to achieve this are extrusion, spray drying or fluidized bed. In this way, a granulate is obtained for direct application. J) ULV (UL) solutions 10 parts by weight of the active compounds are dissolved in an organic solvent, for example xylene. In this way, a product is obtained for direct application. The active compounds can be applied as such, in the form of their formulations or of the application forms prepared from these formulations, for example, in the form of directly sprayable solutions, powders, suspensions or dispersions, emulsions, oil dispersions, pastes. , sprayable agents, dusts, granules, those that are applied either by rolling them, nebulizing them, pulverizing them, sprinkling them or pouring them. The forms of application depend entirely on the purposes of use; in any case, they should guarantee as far as possible the finest of the distributions of the active compounds according to the invention. The aqueous application forms can be prepared from emulsion concentrates, pastes or wettable powders (sprayable powders, oil dispersions) by adding water. For the preparation of emulsions, pastes or oily dispersions, the substances, either as such or dissolved in oil or solvents, can be homogenized in water by means of humectants, adhesives, dispersants or emulsifiers. However, it is also possible to prepare concentrates consisting of active substance, humectants, adhesives, dispersants or emulsifiers and optionally solvents or oil, capable of being diluted in water. The concentrations of active compounds in the preparations ready to be applied can be varied in larger intervals. Usually, these ranges from 0.0001 to 10%, preferably from 0.01 to 1%. The active compounds can also be used successfully in the ultralow volume process (ULV), it being possible to produce formulations with more than 95% by weight of active compound and even the active compound without additions. To the active compounds can be added oils of various types, humectants, adjuvants, herbicides, fungicides, other pesticides, bactericides, if necessary, just immediately before use (tankmix).

These agents can be added to the agents according to the invention, by mixing them with them, which is usually carried out in a weight ratio of 1:10 to 10: 1. The compounds I and II or, where appropriate, the mixtures or the corresponding formulations, are applied by treating the harmful fungi, plants, seeds, soils, surfaces, materials or spaces that must be kept free of these fungi, with a quantity of the mixture or, where appropriate, of the compounds I and II when applied separately, which is effective as a fungicide. The application can be done before or after the infestation caused by the harmful fungi. The fungicidal action of the compound and the mixtures can be shown through the following tests: The active compounds were prepared, either separately or together as a stock solution, with 0.25% by weight of active compound in acetone or DMSO . To that solution was added 1% by weight of Uniperol® EL emulsifier (humectant with emulsifying and dispersing effect based on ethoxylated alkylphenols) and diluted with water to achieve the desired concentration. Application example - Efficacy shown against the disease of brown spots of rice caused by Cochliobolus miyabeanus when the treatment is done for protection purposes Leaves of rice shoots of the variety "Tai-Nong 67", grown in pots, were sprayed with an aqueous suspension of the concentration of active compounds indicated below, to the point where the leaves dripped. The next day, the plants were inoculated with an aqueous spore suspension of Cochliobolus miyabeanus. Next, the plants were placed for 6 days in acclimated chambers at 22-24 ° C and 95-99% > of relative humidity of the air. Then, it was visually determined to what extent the infection had developed on the leaves. The evaluation was done by checking the percentage of the surface of the leaves that had been affected. The percentages were transformed into degrees of effectiveness. The degree of effectiveness (W) is calculated as follows, according to the formula of Abbot: W = (l - s / ß) 100 a represents the percentage of physical infestation in the treated plants and ß represents the percentage of fungal infestation in the untreated plants (which serve for control) When the degree of effectiveness is 0, the infestation of the treated plants is equivalent to that of the control plants not submitted to treatment; When the degree of efficacy is 100, the treated plants show no signs of infestation. The degrees of efficacy that can be expected in the mixtures of active compounds are determined according to the formula of Colby [R.S.

Colby, Weeds 15, 20-22 (1967)] and compared with the observed degrees of efficacy. Colby's formula: E = x + y - xy / 100 E The degree of efficacy that can be expected, expressed in percentages, of the plants subjected to control without having been given treatment, when the mixture of compounds A and B is applied in the concentrations a and bx the degree of effectiveness, expressed in percentages, of the plants under control that have not received treatment, when the active compound A is applied in the concentration and the degree of efficiency, expressed in percentages, of the plants under control that have not received treatment, when the active compound B is applied in the concentration b Table A - Individual active compounds Table B - Mixtures according to the invention *) Degree of effectiveness calculated according to Colby's formula From the results of the tests it is inferred that the mixtures according to the invention, due to their strong synergism, are considerably more efficient than anticipated by Colby's formula

Claims (10)

1. CLAIMS 1. Fungicidal mixtures for combating harmful fungi, characterized in that they contain 1) the triazolopyrimidine derivative of the formula I and 2) tridemorph of formula II CH, CH3- (CH2) -N O / CH, wherein n represents 10, 11, 12 (60-70%) or 14, in a synergistically effective amount.
2. 2. Fungicidal mixtures according to claim 1, characterized in that they 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. 3. Agents characterized in that they contain a liquid or solid carrier and a mixture according to one of claims 1 or 2.
4. 4. Process for combating harmful fungi, characterized in that the fungi, their biotope or the plants, the soil or the seed there is to protect from fungal infestation, are treated with an effective amount of compound I and compound II according to claim 1.
5. Method according to claim 4, characterized in that the compounds I and II according to claim 1, apply simultaneously, either together or separately, or successively.
6. 6. Process according to claim 4 or 5, characterized in that harmful fungi that are pathogenic of rice are combated.
7. Method according to claims 4 to 6, characterized in that the compounds I and II according to the claim 1, or the mixtures according to claim 1 or 2, are applied in an amount ranging from 5 g / ha to 1000 g / ha.
8. Method according to claims 4 to 6, characterized in that the compounds I and II according to claim 1, or the mixture according to claim 1 or 2, are applied in an amount ranging from 1 to 1000 g per 100 kg of seed.
9. 9. Seed characterized in that it contains the mixture according to claims 1 or 2 in an amount of 1 to 1000 g / 100 kg.
10. 10. Use of compounds I and II according to claim 1 for preparing an agent suitable for combating harmful fungi.