MXPA06005238A - Fungicidal mixtures for controlling rice pathogens - Google Patents

Abstract

The invention relates to fungicidal mixtures for controlling rice pathogens, which comprise as the active components:1) the triazolopyrimidine derivative of formula (I), and 2) a dithiocarbamate II selected from thegroup including manganese ethylenebis(dithiocarbamate) zinc complex (II.1), manganese ethylenebis(dithiocarbamate) (II.2), zinc ammoniate ethylenebis(dithiocarbamate) (II.3), zinc ethylenebis(dithiocarbamate) (II.4) and bis(dimethylthiocarbamoyl)disulfide (II.5) in a synergistically effective amount. The invention also relates to methods for controlling rice pathogens with mixtures of compound I with the compounds II and to the use of compound I with the compounds II for producing the aforementioned mixtures, and to agents that contain said 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 Y 2) a dithiocarbamate selected from the group: manganese ethylenebis (dithiocarbamate), zinc complex (11.1), manganese ethylenebis (dithiocarbamate) (II.2), zinc ammonium ethylenebis (dithiocarbamate) (II.3), ethylenebis ( zinc dithiocarbamate) (II.4) and bis (dimethylthiocarbamoyl) disulfide (11.5) 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 products containing them.

Compound I, 5-chloro-7- (4-methyl-p-peridin-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 compounds II, their preparation and their effect against harmful fungi are also known from the literature: 11.1: common name: mancozeb; US 3,379,610 II.2: common denomination: maneb; US 2,504,404 11.3: common name: metiram; US 3,248,400 II.4: common denomination: zineb; US 2,457,674 II.5: common denomination: tiram; DE 642 532).

Mixtures of triazolopyrimidine derivatives with mancozeb 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 the dithiocarbamates is 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.

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 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 crops of cereals or fruits 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 sasakii (Syn. Rhizoctonia solani) are the pathogens that produce the most important diseases in rice plants. Rhizoctonia solani is the only important pathogen in agriculture within the subclass of Agarico-mycetidae. This fungus infects the plant not like most of the other fungi by spores, but by means of an infection of the mycelium.

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 mancozeb mixtures defined above are attacked much more efficiently than with the mancozeb 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, together or separately, or by applying the compounds I and the compounds II successively, it is possible to combat better rice pathogens, than with the individual compounds.

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, Deuteromi-Ketos 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 evil of the leaf sheaths of rice caused by Corticium sasakii.

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.

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

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.

The following list of fungicides with which the compounds according to the invention can be mixed serves to illustrate the possible combinations, but is not to be construed as limiting: • acylalanines, such as benalaxyl, metalaxyl, ofurace, oxadixyl, • amine derivatives, such as aldimorf, dodemorf, fenpropimorf, 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, cyproconazole, diphenoconazole, dinitroconazole, enilconazole, epoxiconazole, fenbuconazole, fluquiconazole, flusilazole, flutriafol, hexaconazole, imazalil, ipconazole, metconazole , myclobutanil, penconazole, pro piconazole, prochloroaz, prothioconazole, simeconazole, tebuconazole, tetraconazole, triandimephone, triadimenol, triflumizole, triticonazole, dicarboximides, such as mylozoline, • dithiocarbamates, such as ferbam, nabam, maneb, propineb, polycarbamate , zyram, • heterocyclic compounds, such as anilazine, benomyl, boscalide, carbendazim, carboxy, oxycarboxim, ciazofamide, dazomet, dithianone, famoxadone, phenamidone, fuberidazole, flutolanil, furametpir, isoprothiolane, mepronil, nuarimol, probenazole, pyroquilone, silthiopham, thiabendazole, tifluzamide, thiadinyl, tricyclazole, trifo- raine, • nitrophenyl derivatives , such as binapacryl, dinocap, dinobutone, nitroftal- isopropyl, • phenylpyrroles, such as phenpiconil or fludioxonil, • sulfur • other fungicides, such as acibenzolar-S-methyl, carpropamide, chlorothalonil, cyfluphenamide, cymoxanil, dazomet, diclomezine, diclocimet, dietofencarb, edifenfos, etaboxam, fenhexamida, fentina-acetate, fenoxanilo, ferimzona, fluazinam, fosetilo, fosetilo aluminum, phosphorous acid, iprovalicarb, hexachlorobenzene, metrafenona, metilisotiocianato, pencicurona, propamocarb, ftalida, toloclofos-methyl, quintozeno, zoxamida, • strobilurins, such as azoxystrobin, dimoxystrobin, fluoxastrobin, kresoxim-methyl, methominostrobin, orisastrobin, picoster bina, pyraclostrobin or trifloxystrobin, • sulfenic acid derivatives, such as captafol, captan, diclofluanide, folpet, tolyl fluoranid • cinnamic acid amides and analogs, such as dimetomorph, flumetover or flumorf.

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

The active principles mentioned above are especially suitable for mixtures of compounds I and 11.2 or I and 11.3 as active principle III.

Mixtures are particularly preferred, in which a strobilurin, a cinnamic acid amide or one of the heterocyclic compounds mentioned above are present.

In addition, active compounds III are also preferred as the fosetyl, the fosetyl-aluminum or the phosphorous acid, especially the mixtures, which contain the compounds I and II and one component III. Mixtures, which contain compound I and a compound II as active components, are especially preferred.

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

Compound I and compound II are usually applied in a weight ratio of 100: 1 to 1: 100, preferably 5: 1 to 1:20, especially 1: 1 to 1:20.

Components III and IV are added, if appropriate, 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 II and the desired effect, from 5 g / ha to 6000 kg / ha, preferably from 50 to 2500 g / ha, especially from 50 to 1000. g / ha.

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 rates for compound 11.1 vary correspondingly, as a rule, from 1 to 2000 g / ha, preferably from 10 to 1500 g / ha, especially from 20 to 750 g / ha.

The application rates for compound II.2 vary correspondingly, as a rule, from 1 to 2500 g / ha, preferably from 10 to 2000 g / ha, especially from 20 to 1000 g / ha.

The application rates for compound II.3 vary correspondingly, as a rule, from 1 to 2000 g / ha, preferably from 10 to 1500 g / ha, especially from 20 to 1000 g / ha.

The application rates for compound 11.4 vary correspondingly, as a rule, from 1 to 2000 g / ha, preferably from 10 to 1500 g / ha, especially from 20 to 1000 g / ha.

The application rates for compound II.5 vary correspondingly, as a rule, from 1 to 6000 g / ha, preferably from 10 to 3500 g / ha, especially from 20 to 1000 g / ha.

In seed treatment, quantities are usually used in the mixture from 1 to 1000 g / 100 kg of seeds, preferably from 1 to 750 g / 100 kg, especially from 5 to 500 g / 100 kg.

To combat phytopathogenic fungi in rice crops, the separate or combined application of the compounds I or II or of the mixture of compounds I and II is carried out by spraying the seeds, the seedlings, the plants or it is soil before or after the sowing of the plants or before or after the emergence of the plants. Preferably, the compounds can be 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 Solv products, xylene), paraffins (eg petroleum fractions), alcohols (eg methanol, butanol, pentanol, benzyl alcohol), ketones (eg 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-ionic 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 sulfates, alkyl sulfonate, fatty alcohol sulfates, fatty acids and glycol ethers of sulphated fatty alcohols, in addition, sulfonated naphthalene condensates and naphthalene derivatives with formaldehyde, naphthalene-naphthalene or naphthalene sulfonic acid-phenol and formaldehyde-polyoxyethylene octyl-phenyl ether, ethoxylated isooctylphenol, octylphenol, nonylphenol, alkylphenyl polyglycol ethers , tributylphenyl polyglycol ether, tristearylphenyl polyglycol ether, polyether alkylalkyl alcohols, alcohol and fatty alcohol / ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers, ethoxylated polyoxypropylene, polyglycol ether acetal lauryl alcohol, sorbitol esters , residual liquors li gnino-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, 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 charges are: mineral earth, such as silica gel, silicic acid, silica gel, silicates, talc, kaolin, limestone, lime, bolus, loess, clay, dolomite, diatomaceous earth, calcium sulfate and magnesium sulfate , 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 powder, wood and nut shells, powders of cellulose 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) Powdered 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 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 - Efficiency against rice leaf pod disease caused by Corticium sasakii Rice plants of the variety "Tai-Nong 67" in pots were sprayed until they dripped with an aqueous suspension of the concentration in active principle indicated below. The next day, oat grains infected with Corticium sasakii were placed on the pots (each time 5 grains per pot). Next, the plants were placed in a climatic chamber at 26 ° C and maximum air humidity. After 11 days the disease had developed so strongly in infected but untreated control plants that the infestation could be visually evaluated in percent.

The evaluation was carried out determining the infected plants in percent. These percentage values were converted into action degrees.

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 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 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 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.

The known compounds A and B of the mancozeb mixtures described in EP-A 988 790 were used as comparative active principles: Table A - Individual active principles Table B - Mixtures according to the invention *) degree of action calculated according to Colby's formula *) 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 dithiocarbamate mixtures of the known comparative compounds of EP-A 988 790.

Claims (11)

Claims

1. Fungicide mixtures, which contain 1) the triazolopyrimidine derivative of the formula 2) a dithiocarbamate II selected from the group: manganese ethylenebis (dithiocarbamate), zinc complex (11.1), manganese ethylenebis (dithiocarbamate) (II.2), zinc ammonium ethylenebis (dithiocarbamate) (II.3), ethylenebis (dithiocarbamate) zinc (II.4) and bis (dimethylthiocarbamoyl) disulfide (II.5) in an active synergetic quantity.

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

3. Fungicidal mixtures according to claims 1 or 2, which contain, as dithiocarbamate, one of the compounds II.1, II.2, II.3 or II.5.

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

5. 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 a compound II according to claim 1.

6. Process according to claim 5, characterized in that the compounds I and II according to claim 1 are applied simultaneously in a joint or separate manner, or in succession.

7. Process according to claim 4, characterized in that the mixture according to claims 1 to 3 is applied in an amount of 5 g / ha to 6000 g / ha.

8. Method according to one of claims 5 to 7, characterized in that the noxious fungus, Corticium sasakii, is combated.

9. Process according to claims 5 and 6, 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.

10. Seeds containing the mixture according to claims 1 to 3 in an amount of 1 to 1000 g / 100 kg.

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