EP1746891A1

EP1746891A1 - Fungicide mixtures for controlling pathogenic agents of rice

Info

Publication number: EP1746891A1
Application number: EP05741772A
Authority: EP
Inventors: Jordi Tormo I Blasco; Thomas Grote; Maria Scherer; Reinhard Stierl; Siegfried Strathmann; Ulrich Schöfl
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 2004-05-07
Filing date: 2005-04-27
Publication date: 2007-01-31
Also published as: CN1949974A; US20070208039A1; NO20065507L; BRPI0510544A; MXPA06011750A; AU2005245260A1; KR20070007959A; PE20060111A1; WO2005112642A1; UA80792C2; EA200602012A1; JP2007536304A; IL178559A0; NZ550841A; ZA200610179B; CR8707A; TW200539806A; AR048779A1; CA2562635A1; UY28888A1

Abstract

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

Description

Fungicidal mixtures for controlling rice pathogens

description

The present invention relates to fungicidal mixtures for controlling rice pathogens containing as active components

1) the triazoloule I,

and

2) Dodine of the formula

in a synergistically effective amount.

In addition, the invention relates to a method for controlling rice pathogens with mixtures of the compound I with the compounds II and the use of the compound I with the compounds II for the preparation of such mixtures and compositions containing these mixtures.

The compound I, 5-chloro-7- (4-methylpiperidin-1-yl) -6- (2,4,6-trifluorophenyl) - [1,2,4] triazolo [1.5 -a] pyrimidine, their preparation and their action against harmful fungi are known from the literature (WO 98/46607).

The compound II, 1-dodecylguanidinium acetate, their preparation and their action against harmful fungi are also known from the literature (US Pat. No. 2,867,562, common name Dodine).

Mixtures of triazolopyrimidine derivatives with dodine are generally proposed in EP-A 988 790. Compound I is of the general disclosure of this However, font is not explicitly mentioned. The combination of compound I with Dodine is new.

The synergistic mixtures known from EP-A 988790 are effective as fungicidal against various diseases of cereals, fruits and vegetables, such. As mildew on wheat and barley or gray mold on apples.

Due to the specific cultivation conditions of rice plants, there are clearly different requirements for a rice fungicide than for fungicides used in cereal or fruit production. Differences exist in the application method: in addition to the leaf application applied in many places, the fungicide is usually applied to the soil directly at, or shortly after sowing, in modern rice cultivation. The fungicide is absorbed into the plant via the roots and transported in the plant sap in the plant to the plant parts to be protected. In cereal or fruit growing, on the other hand, the fungicide is usually applied to the leaves or fruit, so in these crops the systemics of the active ingredients play a much smaller role.

Also in rice other pathogens are typical than in grains or fruits. Pyricularia oryzae and Corticium sasakii (syn. Rhizoctonia solani) are the causative agents of the most important diseases of rice plants. Rhizoctonia solani is the only agriculturally significant pathogen within the subclass Agaricomycetidae. This fungus does not attack the plant like most other fungi via spores, but via a mycelial infection.

For this reason, findings on the fungicidal effects of grain or fruit are not transferable to rice crops.

With regard to an effective control of rice pathogens with the lowest possible application rates of the present inventions were mixtures as a task that show improved action against the harmful fungi with a reduced total amount of applied drugs.

Accordingly, the mixtures defined above were found. It has surprisingly been found that rice pathogens can be controlled significantly better with the dodine mixtures defined at the beginning than with the dodine mixtures of the triazolopyrimidine compounds known from EP-A 988 790. It has also been found that with simultaneous simultaneous or separate application of the compounds I and the compounds II or when using the compounds I and the compounds II can be successively combat rice pathogens better than with the individual compounds.

Preference is given to the preparation of the mixtures, the pure active ingredients I and II, which can be added as needed further active against harmful fungi or other pests such as insects, spider animals or nematodes, or herbicidal or growth-regulating agents or fertilizers.

In particular, fungicides selected from the following group are suitable as further active ingredients in the above sense:

Acylalanines such as benalaxyl, metalaxyl, ofurace, oxadixyl,

Amine derivatives such as aldimorph, dodemorph, fenpropimorph, fenpropidin, guazatine, iminoctadine, spiroxamine, tridemorph, anilinopyrimidines such as pyrimethanil, mepanipyrim or cyprodinil,

Antibiotics such as cycloheximide, griseofulvin, kasugamycin, natamycin, polyoxin or streptomycin,

• Azoles such as bitertanol, bromoconazole, cyproconazole, difenoconazole, dinitroconazole, enilconazole, epoxiconazole, fenbuconazole, fluquiconazole, flusilazole, flutriafol, hexaconazole, imazalil, ipconazole, metconazole, myclobutanil, penconazole, propynazole, prochloraz, prothioconazole, simeconazole, tebuconazole , Tetraconazole, triadimefon, triadimol, triflumizol, triticonazole,

Dicarboximides such as iprodione, myclozoline, procymidone, vinclozolin,

Dithiocarbamates such as Ferbam, Nabam, Maneb, Mancozeb, Metam, Metiram, Propineb, Polycarbamate, Thiram, Ziram, Zineb,

Heterocyclic compounds such as anilazine, benomyl, boscalid, carbendazim, carboxine, oxycarboxine, cyazofamide, dazomet, dithianone, famoxadone, fenamidone, fenarimol, fuberidazole, flutolanil, furametpyr, isoprothiolane, mepronil, nuarimol, penthiopyrad, picobenzamide, probenazole, proquinazide, Pyrifenox, Pyroquilon, Quinoxyfen, Silthiofam, Thiabendazole, Thifluzamide, Thiophanate-methyl, Tiadinil, Tricyclazole, Triforine,

Copper fungicides such as Bordeaux broth, copper acetate, copper oxychloride, basic copper sulfate,

Nitrophenyl derivatives, such as binapacryl, dinocap, dinobutone, nitrophthalic-isopropyl, phenylpyrroles, such as fenpiclonil or fludioxonil,

• sulfur,

Other fungicides such as acibenzolar-S-methyl, benthiavalicarb, carpropamide, chlorotriazole, cyflufenamide, cymoxanil, diclomethine, diclocymet, diethofencarb, edfenphos, ethaboxam, fenhexamide, fentin acetate, fenoxanil, ferimzone, fluaziamine, fosetyl, Fosetyl-aluminum, iprovalicarb, hexachlorobenzene, mandipropamide, Metrafenone, Pencycuron, Propamocarb, Phosphoric Acid, Phthalide, Toloclofos- methyl, Quintozene, Zoxamide,

Strobilurins such as azoxystrobin, dimoxystrobin, enestroburin, fluoxastrobin, cresoxime-methyl, metominostrobin, orysastrobin, picoxystrobin, pyraclostrobin or trifloxystrobin,

Sulfenic acid derivatives such as captafol, captan, dichlofluanid, folpet, tolylfluanid,

Cinnamic acid amides and analogues such as dimethomorph, flumetover or flumorph.

In one embodiment of the mixtures according to the invention, fertilizers I and II are admixed with a further fungicide III or two fungicides IM and IV.

Mixtures of compounds I and II with a component III are preferred. Particular preference is given to mixtures of the compounds I and II.

The mixtures of the compounds I and II or the simultaneous joint or separate use of the compounds I and the compound II are distinguished by an outstanding activity against rice pathogens from the class of the Ascomycetes, Deuteromycetes and Basidiomycetes. They have a high system and can therefore be used for seed treatment as well as foliar and soil fungicides.

They are of particular importance for the control of harmful fungi on rice plants and their seeds, such as bipolaris and Drechslera species, and Pyricularia oryzae. In particular, they are useful for controlling the sheath disease of rice caused by Corticium sasakii.

In addition, the inventive combination of compounds I and II is also suitable for controlling other pathogens, such. B. Septoria, Phakopsora and Puccinia species in soy and cereals and Alternaria and Boytritis A inen in vegetables, fruits and wine.

The compound I and the compound II can be applied simultaneously together or separately or in succession, the sequence in the case of separate application generally having no effect on the control result.

The compound I and the compound II are usually used in a weight ratio of 100: 1 to 1: 100, preferably 2: 1 to 1:20, especially 1: 1 to 1:15 applied. The components III and IV are optionally added in a ratio of 20: 1 to 1:20 to the compound I.

The application rates of the mixtures according to the invention are, depending on the nature of the compound and the desired effect at 0.1 kg / ha to 3 kg / ha, preferably 0.5 to

2 kg / ha.

The application rates for the compound I are accordingly generally 1 to 1000 g / ha, preferably 10 to 900 g / ha, in particular 20 to 750 g / ha.

The application rates for compound II are generally 0.1 to

3 kg / ha, preferably 0.5 to 2 kg / ha, in particular 1 to 1.5 kg / ha.

In seed treatment, application rates of mixture of 1 to 1000 g / 100 kg of seed, preferably 1 to 200 g / 100 kg, in particular 5 to 100 g / 100 kg are generally used.

In the control of pathogenic harmful fungi, the separate or combined application of the compounds I and II or the mixtures of the compounds I and II by spraying or dusting the seeds, seedlings, plants or soils before or after sowing the plants or before or after the emergence of the plants. Preferably, the application is carried out by spraying the leaves. The application of the compounds together or separately can also be carried out by granule application or dusting of the soil.

The mixtures according to the invention, or the compounds I and II, can be converted into the customary formulations, e.g. Solutions, emulsions, suspensions, dusts, powders, pastes and granules. The application form depends on the respective purpose; It should in any case ensure a fine and uniform distribution of the compound according to the invention.

The formulations are prepared in a known manner, for example by stretching the active ingredient with solvents and / or excipients, if desired using emulsifiers and dispersants. Suitable solvents / auxiliaries are essentially 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), acetates (glycol diacetate), glycols, dimethyl fatty acid amides, fatty acids and fatty acid esters. In principle, solvent mixtures can also be used Carriers such as ground natural minerals (eg kaolins, clays, talc, chalk) and ground synthetic minerals (eg highly disperse silicic acid, silicates); Emulsifiers such as nonionic and anionic emulsifiers (eg polyoxyethylene fatty alcohol ethers, alkyl sulfonates and arylsulfonates) and dispersants such as lignin liquors and methylcellulose.

The surface-active substances used are alkali metal, alkaline earth metal, ammonium salts of lignin sulfonic acid, naphthalenesulfonic acid, phenolsulfonic acid, dibutylnaphthalenesulfonic acid, alkylarylsulfonates, alkyl sulfates, alkyl sulfonates, fatty alcohol sulfates, fatty acids and sulfated fatty alcohol glycol ethers, and condensation products of sulfonated naphthalene and naphthalene derivatives with formaldehyde , Condensation products of naphthalene or naphthalenesulfonic acid with phenol and formaldehyde, polyoxyethylene octylphenol ether, ethoxylated isooctylphenol, octylphenol, nonylphenol, alkylphenol polyglycol ethers, tributylphenyl polyglycol ethers, tristerylphenyl polyglycol ethers, alkylaryl polyether alcohols, alcohol and fatty alcohol ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers, ethoxylated polyoxypropylene , Laurylalkoholpoly- glycol ether acetal, sorbitol esters, Ligninsulfitablaugen and methyl cellulose into consideration.

For the preparation of directly sprayable solutions, emulsions, pastes or oil dispersions, there are mineral oil fractions of medium to high boiling point, such as kerosine or diesel oil, coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, e.g. Toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes or their derivatives, methanol, ethanol, propanol, butanol, cyclohexanol, cyclohexanone, isophorone, strong polar solvents, e.g. Dimethylsulfoxide, N-methylpyrrolidone or water into consideration.

Powders, dispersants and dusts may be prepared by mixing or co-grinding the active substances with a solid carrier.

Granules, e.g. Coated, impregnated and homogeneous granules can be prepared by binding the active compounds to solid carriers. Solid carriers are e.g. Mineral earths, such as silica gels, silicates, talc, kaolin, attaclay, limestone, lime, chalk, bolus, loess, clay, dolomite, diatomaceous earth, calcium and magnesium sulphate, magnesium oxide, ground plastics, fertilizers, e.g. Ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas and vegetable products such as cereal flour, tree bark, wood and nutshell meal, cellulose powder and other solid carriers.

The formulations generally contain between 0.01 and 95 wt .-%, preferably between 0.1 and 90 wt .-% of the active ingredients. The active substances are thereby ner purity of 90% to 100%, preferably 95% to 100% (by NMR spectrum) used.

Examples of formulations are: 1. Products for dilution in water

A) Water Soluble Concentrates (SL)

10 parts by weight of the active ingredients are dissolved in water or a water-soluble solvent. Alternatively, wetting agents or other adjuvants are added. When diluted in water, the active ingredient dissolves.

B) Dispersible Concentrates (DC)

20 parts by weight of the active compounds are dissolved in cyclohexanone with addition of a dispersant, e.g. Polyvinylpyrrolidone dissolved. Dilution in water gives a dispersion.

C) Emulsifiable Concentrates (EC)

15 parts by weight of the active compounds are dissolved in xylene with the addition of calcium dodecylbenzenesulfonate and castor oil ethoxylate (in each case 5%). Dilution in water results in an emulsion.

D) Emulsions (EW, EO)

40 parts by weight of the active compounds are dissolved in xylene with addition of calcium dodecylbenzenesulfonate and castor oil ethoxylate (in each case 5%). This mixture is introduced into water by means of an emulsifier (Ultraturax) and brought to a homogeneous emulsion. Dilution in water results in an emulsion.

E) suspensions (SC, OD)

20 parts by weight of the active ingredients are comminuted with the addition of dispersants and wetting agents and water or an organic solvent in a stirred ball mill to a fine active ingredient suspension. Dilution in water results in a stable suspension of the active ingredient.

F) Water-dispersible and water-soluble granules (WG, SG)

50 parts by weight of the active ingredients are finely ground with the addition of dispersing and wetting agents and prepared by means of technical equipment (for example extrusion, spray tower, fluidized bed) as water-dispersible or water-soluble granules. Dilution in water results in a stable dispersion or solution of the active ingredient.

G) Water-dispersible and Water-Soluble Powders (WP, SP) 75 parts by weight of the active compounds are added with the addition of dispersants and wetting agents. How to grind silica gel in a Rotor-Strator mill. Dilution in water results in a stable dispersion or solution of the active ingredient.

2. Products for direct application

H) dusts (DP)

5 parts by weight of the active ingredients are finely ground and intimately mixed with 95% finely divided kaolin. This gives you a dust.

I) Granules (GR, FG, GG, MG)

0.5 parts by weight of the active ingredients are finely ground and combined with 95.5% excipients. Common processes are extrusion, spray drying or fluidized bed. This gives granules for direct application.

J) ULV solutions (UL)

10 parts by weight of the active compounds are dissolved in an organic solvent, e.g. Xylene dissolved. This gives you a product for direct application.

The active compounds can be used as such, in the form of their formulations or the use forms prepared therefrom, e.g. in the form of directly sprayable solutions, powders, suspensions or dispersions, emulsions, oil dispersions, pastes, dusts, scattering agents, granules by spraying, misting, dusting, scattering or pouring. The forms of application depend entirely on the intended use; In any case, they should ensure as far as possible the finest distribution of the active compounds according to the invention.

Aqueous application forms can be prepared from emulsion concentrates, pastes or wettable powders (wettable powders, oil dispersions) by adding water. To prepare emulsions, pastes or oil dispersions, the substances, as such or dissolved in an oil or solvent, can be homogenized in water by means of wetting agents, tackifiers, dispersants or emulsifiers. But it can also be made of effective substance wetting, adhesion, dispersing or emulsifying and possibly solvent or oil concentrates, which are suitable for dilution with water.

The active compound concentrations in the ready-to-use preparations can be varied within wide ranges. In general, they are between 0.0001 and 10%, preferably between 0.01 and 1%. The active ingredients can also be used with great success in the ultra-low-volume (ULV) process, it being possible to apply formulations containing more than 95% by weight of active ingredient or even the active ingredient without additives.

To the active ingredients oils of various types, wetting agents, adjuvants, herbicides, fungicides, other pesticides, bactericides, optionally also just before use (tank mix), are added. These agents can be added to the inventive compositions, which usually takes place in a weight ratio of 1:10 to 10: 1.

The compounds I and II, or the mixtures or the corresponding formulations, are applied by mixing the harmful fungi, the plants, seeds, soils, areas, materials or spaces to be kept free of them with a fungicidally effective amount of the mixture or of the compounds I and II in the case of separate application. The application can be made before or after the attack by the harmful fungi.

The fungicidal activity of the compound and the mixtures can be demonstrated by the following experiments:

The active compounds were prepared separately or together as a stock solution with 0.25% by weight of active ingredient in acetone or DMSO. To this solution was added 1% by weight of emulsifier Uniperol® EL (wetting agent with emulsifying and dispersing action based on ethoxylated alkylphenols) and diluted with water according to the desired concentration.

Example of use - Action against brown spot disease of rice caused by Cochliobolus miyabeanus in protective treatment

Leaves of potted rice seedlings of the cultivar 'Tai-Nong 67' were sprayed to drip point with aqueous suspension in the concentration of active compound stated below at 22-24 ° C and 95-99% relative humidity for 6 days, then the extent of infestation on the leaves was visually determined.

The evaluation is made by determining the infected leaf areas in percent. These percentages were converted into efficiencies. The efficiency (W) is calculated according to the formula of Abbot as follows:

W = (1-α / β) -100

α corresponds to the fungal infestation of the treated plants in% and β corresponds to the fungal infestation of the untreated (control) plants in%

With an efficiency of 0, the infestation of the treated plants corresponds to that of the untreated control plants; at an efficiency of 100, the treated plants have no infestation.

The expected efficiencies of the drug mixtures are according to the Colby formula [R.S. Colby, Weeds 15, 20-22 (1967)] and compared with the observed efficiencies.

Colby's formula: E = x + y - x-y / 100

E expected efficiency, expressed as% of untreated control, using the mixture of active substances A and B at concentrations a and bx the efficiency expressed as% of untreated control, when using active substance A at the concentration ay the efficiency, expressed as% of untreated control, when used. of the active substance B in the concentration b

As comparative compounds, the compounds A and B known from the mixtures described in EP-A 988 790 were used:

Table A - Single agents

Table B - mixtures according to the invention

*) calculated efficiency according to the Colby formula

Table C - Comparative Experiments

*) calculated efficiency according to the Colby formula From the results of the experiments it is apparent that the mixtures according to the invention are significantly more effective even at low application rates against the brown spot disease by strong synergism than the dodine mixtures of the comparison compounds proposed in EP-A 988780.

Claims

claims

1. Fungicidal mixtures for controlling pathogenic harmful fungi, containing

1) the triazolopyrimidine derivative of the formula I,

and 2) dodine of formula II,

in a synergistically effective amount.

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

3. A composition comprising a liquid or solid carrier and a mixture according to any one of claims 1 or 2.

4. A method for controlling pathogenic harmful fungi, characterized in that treating the fungi, their habitat or the plants to be protected against fungal attack, the soil or seeds with an effective amount of the compound I and the compound II according to claim 1.

5. The method according to claim 4, characterized in that the compounds I and II according to claim 1 at the same time, and jointly or separately, or successively auszustingt.

6. The method according to claims 4 or 5, wherein the harmful fungus Cochliobolus miyabeanus is combated.

7. The method according to any one of claims 4 to 6, characterized in that the compounds I and II according to claim 1 or the mixtures according to claims 1 or 2 in an amount of 0.1 g / ha to 3 kg / ha expends.

8. The method according to any one of claims 4 to 6, characterized in that applying the compounds I and II according to claim 1 or the mixture according to claims 1 or 2 in an amount of 1 to 1000 g / 100 kg of seed.

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

10. Use of the compounds I and II according to claim 1 for the preparation of a suitable agent for controlling harmful fungi.