EP1708574A1

EP1708574A1 - Fungicidal mixtures

Info

Publication number: EP1708574A1
Application number: EP05706887A
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: 2004-01-20
Filing date: 2005-01-14
Publication date: 2006-10-11
Also published as: OA13360A; TW200533290A; EA200601241A1; WO2005067716A1; NZ548473A; UY28723A1; MXPA06007650A; CA2552240A1; BRPI0506913A; NO20063079L; AP1762A; AU2005204451A1; ZA200606904B; ECSP066704A; AP2006003696A0; CO5700676A2; CN1909784A; JP2007518729A; US20080064692A1; AR048148A1

Abstract

The invention relates to fungicidal mixtures comprising the following active components: 1) the triazolopyrimidine derivative of formula (I), and 2) a fluoxastrobin of formula (II) in a synergistically active quantity. The invention also relates to a method for combating phytopathogenic fungi using mixtures of compounds (I) and (II), to the use of compounds (I) and (II) for producing mixtures of this type and to agents that contain said mixtures.

Description

Fungicidal mixtures

description

The present invention relates to fungicidal mixtures containing as active components

1) the triazolopyrimidine derivative of the formula I,

and

2) Fluoxastrobin of formula II

in a synergistically effective amount.

In addition, the invention relates to a method for controlling phytopathogenic harmful fungi with mixtures of the compound I with the compounds II and the use of the compound I with the compounds II for the production of such mixtures and agents which contain these mixtures.

The compound I, 5-chloro-7- (4-methyl-piperidin-1-yl) -6- (2,4,6-trifluorophenyl) - [1,2,4] tri-azolo [1,5 -a] pyrimidine, its preparation and its action against harmful fungi is known from the literature (WO 98/46607).

The compound II, {2- [6- (2-chlorophenoxy) -5-fluoropyrimidin-4-yloxy] phenyl} - (5,6-dihydro- [1,4,2] dioxazin-3- yl) -methanone-0-methyl-oxime, their preparation and their action against harmful fungi is also known from the literature (WO 97/27189; common name fluoxastrobin). Mixtures of triazolopyrimidine derivatives with synthetic strobilurin derivatives are generally proposed in EP-A 988 790. Mixtures of triazolopyrimidines with other active ingredients are known from US 6268 371. Compound I is included in the general disclosure of these publications, but is not explicitly mentioned. Fluoxastrobin belongs to the class of strobilurin active ingredients, but is also not mentioned in the aforementioned publications. The combination of compound I with fluoxastrobin is new.

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

The mixtures known from US 6268371 are described as fungicidally active, especially against rice pathogens.

With a view to reducing the application rates and widening the spectrum of action of the known compounds, the present invention was based on mixtures which, with a reduced total amount of active compounds applied, have an improved activity against harmful fungi (synergistic mixtures).

Accordingly, the mixtures defined at the outset were found. It has also been found that, when the compound I and the compound II are used simultaneously or separately, or when the compound I and the compound II are used in succession, harmful fungi can be combated better than with the individual compounds (synergistic mixtures).

The mixtures of the compound I and the compound II or the simultaneous joint or separate use of the compound I and the compound II are distinguished by an outstanding activity against a broad spectrum of phytopathogenic fungi, in particular from the class of the Ascomycetes, Deuteromycetes, Oomycetes and Basidiomycetes. Some of them are systemically effective and can be used in plant protection as leaf and soil fungicides.

They are particularly important for combating a large number of fungi on various crops such as bananas, cotton, vegetables (e.g. cucumbers, beans and squashes), barley, grass, oats, coffee, potatoes, corn, fruit plants, rice, rye, soybeans, tomatoes , Wine, wheat, ornamental plants, sugar cane and a variety of seeds. They are particularly suitable for combating the following phytopathogenic fungi: Blumeria graminis (powdery mildew) on cereals, Erysiphe cichoracearum and Sphaerotheca fuliginea on pumpkin plants, Podosphaera leucotricha on apples, Uncinula necator on vines, Puccinia-Aroct on cereals, rhizomes Cotton, rice and lawn, Ustilago species on cereals and sugar cane, Venturia inaequalis on apples, Bipolaris and Drechslera species on cereals, rice and lawn, Septoria nodumum on wheat, Botrytis cinerea on strawberries, vegetables, ornamental plants and Vines, Mycosphaerella species on bananas, peanuts and cereals, Pseudocercosporella her- potrichoides on wheat and barley, Pyricularia oryzae on rice, Phytophthora infestans on potatoes and tomatoes, Pseudoperonospora species on pumpkin plants and hops, Plasmopara viticola on vines, Alternaria Vegetable and fruit types, as well as Fusaria and Verticillium species.

They are used advantageously to control rice pathogens from the class of Ascomycetes, Deuteromycetes and Basidiomycetes. In particular, they can be used to control harmful fungi on rice plants and on their seeds, such as Bipolaris and Drechslera species, as well as Pyricularia oryzae and Corticium sasakii, the cause of the leaf sheath disease.

Furthermore, they are particularly advantageous for controlling harmful fungi from the Oomycetes class, in particular Phytophthora infestans on potatoes and tomatoes and Plasmopara viticola on vines.

They can also be used in material protection (e.g. wood protection), for example against Paecilomyces variotii.

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 not having any effect on the success of the control measures.

In the preparation of the mixtures, preference is given to using the pure active ingredients I and II, to which, as required, further active ingredients against harmful fungi or other pests such as insects, arachnids or nematodes, or else herbicidal or growth-regulating active ingredients or fertilizers can be admixed.

Fungicides selected from the following group are particularly suitable as further active ingredients in the above sense:

Acylalanines such as benalaxyl, metalaxyl, ofurace, oxadixyl, Amine derivatives such as aldimorph, dodine, 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, epoxiconazole, fenbuconazole, fluquiconazole, flusilazole, flutriafol, hexaconazole, imazalil, ipconazole, metconazole, myclobutanilone, penconazolone , Triadimefon, triadimenol, triflumizol, triticonazole,

Dicarboximides such as iprodione, myclozolin, procymidone, vinclozolin,

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

• Heterocyclic compounds such as anilazine, benomyl, boscalid, carbendazim, carboxin, oxycarboxin, cyazofamid, dazomet, dithianon, famoxadone, fenamidon, fenarimol, fuberidazole, flutolanil, furametpyr, isoprothiolan, mepronazolifene, proquinolifene, proquinolifene, proquinolifene, proquinolifene, proquinolifene, proquinolifene, proquinolifene, proquinolifene, proquinolifene, proquinolifene, proquinolifene, proquinolifene, proquinolifene, nuquin Pyroquilon, quinoxyfen, silthofam, thiabendazole, thifluzamide, thiophanate-methyl, tiadinil, tricyclazole, triforins,

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

Nitrophenyl derivatives, such as binapacryl, dinocap, dinobutone, nitrophthal-isopropyl,

Phenylpyrroles such as fenpiclonil or fludioxonil,

• sulfur,

• Other fungicides such as acibenzolar-S-methyl, benthiavalicarb, carpropamide, chlorothalonil, cyflufenamide, cymoxanil, Dazomet, diclomezin, diclocymet, diethofen-carb, edifenphos, ethaboxam, fenhexamide, fentin acetate, fenoroxaneil, ferim , Fosetyl, fosetyl aluminum, iprovalicarb, hexachlorobenzene, metrafenone, pencycuron, propamocarb, phthalide, toloclofos-methyl, quintozene, zoxamide, • strobilurins such as azoxystrobin, dimoxystrobin, cresoxim-methyl, metominostrobin, picoxifrobin, oroxystrobinro or,

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

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

Mixtures of the compounds I and II with an active ingredient III are preferred selected from the anilinopyrimidines, azoles, dithiocarbamates, heterocyclic compounds, sulfonic acid derivatives, cinnamic acid derivatives or the other fungicides mentioned, in particular the azoles mentioned. Mixtures of the compounds I and II with an active ingredient III are particularly preferred selected from the group cyprodinil, epoxiconazole, fluquiconazole, metconazole, prochloraz, prothioconazole, tebuconazole, triticonazole, Mancozeb, Metiram, boscalid, dithianon, chlorothalonil, metrafenone, and dimamethomol, propamocarb ,

In one embodiment of the mixtures according to the invention, a further fungicide IV is added to compounds II and III. The aforementioned active ingredients III are suitable as component IV.

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

The compound I and the compound II are usually used in a weight ratio of 100: 1 to 1: 100, preferably 20: 1 to 1:20, in particular 10: 1 to 1:10.

If an active ingredient III is present, the compounds I, II and III are usually used in a weight ratio of 100: 1: 5 to 1: 100: 20, preferably 20: 1: 1 to 1:20:20, in particular 10: 1: 1 applied until 1:10:10.

If desired, components IV are mixed in a ratio of 20: 1 to 1:20 to the mixtures of the compounds I, II and III.

Depending on the type of compound and the desired effect, the application rates of the mixtures according to the invention are 5 g / ha to 1000 g / ha, preferably 50 to 900 g / ha, in particular 50 to 750 g / ha.

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

Accordingly, the application rates for the compound II are generally from 1 to 750 g / ha, preferably from 20 to 500 g / ha, in particular from 50 to 250 g / ha.

Correspondingly, the application rates for the compounds III are generally from 1 to 1000 g / ha, preferably from 10 to 500 g / ha, in particular from 40 to 350 g / ha.

In the case of seed treatment, application rates of mixture of 1 to 300 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 phytopathogenic harmful fungi, the compounds I and II or the mixtures of the compounds I and II are applied separately or jointly by spraying or pollinating the seeds, seedlings, plants or soils before or after the plants are sown or before or after emergence of the plants. The compounds are preferably used by spraying the leaves. The compounds can be applied jointly or separately by applying granules or by dusting the floors.

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 form of application depends on the respective purpose; in any case, it should ensure a fine and uniform distribution of the compound according to the invention.

The formulations are prepared in a known manner, e.g. by stretching the active ingredient with solvents and / or carriers, if desired using emulsifiers and dispersants. The following are essentially suitable as solvents / auxiliaries: water, aromatic solvents (for example Solvesso products, xylene), paraffins (for example petroleum fractions), alcohols (for example methanol, butanol, pentanol, benzyl alcohol), ketones (for example cyclohexanone, gamma-butryolactone) , 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 natural stone powder (e.g. kaolins, clays, talc, chalk) and synthetic stone powder (e.g. highly disperse silica, silicates); Emulsifiers such as nonionic and anionic emulsifiers (e.g. polyoxyethylene fatty alcohol ethers, alkyl sulfonates and aryl sulfonates) and dispersants such as lignin sulfite liquors and methyl cellulose.

Alkali, alkaline earth, and ammonium salts of lignosulfonic acid, naphthalenesulfonic acid, phenolsulfonic acid, dibutylnaphthalenesulfonic acid, alkylarylsulfonates, alkyl sulfates, alkyl sulfonates, fatty alcohol sulfates, fatty acids and sulfated naphthalene naphthalene and sulfonated dehydrogenated naphthalene derivatives of sulfonated formaldehyde derivatives and sulfonated dehydrogenated naphthalenedaphthalene from sulfonates, as well as condensation products with sulfated naphthalenedaphthalene and sulfonated dehydrogenated naphthalenedaphthalene and sulfonated dehydrogenated naphthalenedaphthalene and sulfonated dehydrogenated naphthalenedaphthalene and sulfonated dehydrogenated naphthalenedaphthalene ether and condensation products , Condensation products of naphthalene or of naphthalene sulfonic acid with phenol and formaldehyde, polyoxyethylene octylphenol ether, ethoxylated isooctylphenol, octylphenol, nonylphenol, alkylphenol polyglycol ether, tri-butylphenyl polyglycol ether, trihylphenyl polyglycol ether, alkyl alcoholoxy ethoxylated alcohol, alkyl alcoholoxy ethoxylated alcohol , Laurylalkoholpolyglykoletheracetal, sorbitol ester, lignin sulfite and methyl cellulose into consideration. Mineral oil fractions of medium to high boiling point, such as kerosene or diesel oil, also coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, for example toluene, are used to produce directly sprayable solutions, emulsions, pastes or oil dispersions. Xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes or their derivatives, methanol, ethanol, propanol, butanol, cyclohexanol, cyclohexanone, isophorone, strongly polar solvents, for example dimethyl sulfoxide, N-methylpyrrolidone or water.

Powders, materials for broadcasting and dusts can be prepared by mixing or grinding the active substances together with a solid carrier.

Granules, e.g. Coating, impregnation and homogeneous granules can be produced by binding the active ingredients to solid carriers. Solid carriers are e.g. Mineral earths, such as silica gels, silicates, talc, kaolin, attack clay, limestone, lime, chalk, bolus, loess, clay, dolomite, diatomaceous earth, calcium and magnesium sulfate, 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 flour, cellulose powder and other solid carriers.

The formulations generally contain between 0.01 and 95% by weight, preferably between 0.1 and 90% by weight, of the active ingredients. The active ingredients are used in a purity of 90% to 100%, preferably 95% to 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 ingredients are dissolved in water or a water-soluble solvent. Alternatively, wetting agents or other aids are added. The active ingredient dissolves when diluted in water.

B) Dispersible concentrates (DC) 20 parts by weight of the active compounds are dissolved in cyclohexanone with the addition of a dispersant, for example polyvinylpyrrolidone. When diluted in water, a dispersion results. C) Emulsifiable concentrates (EC)

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

D) Emulsions (EW, EO)

40 parts by weight of the active ingredients are dissolved in xylene with the addition of calcium dodecylbenzenesulfonate and castor oil ethoxylate (5% each). This mixture is introduced into water using an emulsifying machine (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 in a stirred ball mill to form a fine active ingredient suspension with the addition of dispersing and wetting agents and water or an organic solvent. 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 produced using technical equipment (e.g. 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 ingredients are ground in a rotor-strator mill with the addition of dispersing and wetting agents and silica gel. 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 a dust.

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

0.5 part by weight of the active ingredients are finely ground and combined with 95.5% carriers. 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 ingredients are dissolved in an organic solvent e.g. Xylene dissolved. This gives you a product for direct application.

The active ingredients 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, sprinkling agents, granules by spraying, atomizing, dusting, scattering or pouring. The application forms depend entirely on the purposes of use; in any case, they should ensure the finest possible 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, adhesives, dispersants or emulsifiers. However, wetting agents, adhesives, dispersants or emulsifiers, and possibly solvents or oil, can also be prepared from active substance and are suitable for dilution with water.

The active ingredient concentrations in the ready-to-use preparations can be varied over a wide range. 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 process (ULV), it being possible to apply formulations with more than 95% by weight of active ingredient or even the active ingredient without additives.

Various types of oils, wetting agents, adjuvants, herbicides, fungicides, other pesticides and bactericides can be added to the active compounds, if appropriate also only immediately before use (tank mix). These agents can be added to the agents according to the invention, which is usually done in a weight ratio of 1:10 to 10: 1.

The compounds I and II, or the mixtures or the corresponding formulations, are used in that the harmful fungi, the plants, seeds, soils, surfaces, materials or spaces to be kept free from them are mixed with a fungicidally effective amount of the mixture or the compounds I and II with separate application, treated. The application can take place before or after the infestation by the harmful fungi.

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

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

The evaluation is carried out by determining the affected leaf areas in percent. These percentages were converted into efficiencies.

Efficiency (W) is calculated using Abbot's formula as follows:

W = (1 - σ / 0) ^' 1 OO

a corresponds to the fungal attack of the treated plants in% and

ß corresponds to the fungal infection 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; with an efficiency of 100, the treated plants show no infection.

The expected efficacies of the active ingredient mixtures are calculated according to the Colby formula [R.S. Colby, Weeds 15, 20-22 (1967)] and compared with the observed efficiencies. Colby formula: E = x + y - x-y / 100

E expected efficiency, expressed in% of the untreated control, when using the mixture of active ingredients A and B in concentrations a and b

x the efficiency, expressed in% of the untreated control, when using the active ingredient A in the concentration a y the efficiency, expressed in% of the untreated control, when using the active ingredient B in the concentration b

Example of use 1 - Efficacy against the leaf sheath disease on rice caused by Corticium sasakii

Pots with rice plants of the "Tai-Nong 67" variety were sprayed to runoff point with an aqueous suspension in the active ingredient concentration given below. On the following day, oat grains infected with Corticium sasakii were placed on the pots (5 grains per pot). The plants were then removed set up in a chamber at 26 ^C and maximum air humidity After 11 days, the leaf sheath disease on the untreated but infected control plants had developed to such an extent that the infestation could be determined visually in%

Table B - mixtures according to the invention

*) Efficiency calculated according to the Colby formula Application example 2 - Efficacy against vine peronospora caused by Plasmopara viticola

Leaves of potted vines of the "Riesling" variety were sprayed to runoff point with an aqueous suspension in the active ingredient concentration given below. The following day, the undersides of the leaves were coated with an aqueous zoo spore inoculation of plasmopara viticola. The vines were then placed for 48 hours in a steam-saturated chamber at 24 ° C and then for 5 days in a greenhouse at temperatures between 20 and 30 ° C. After this time, the plants were again placed in a moist chamber for 16 hours in order to accelerate the sporangium carrier outbreak. The extent of the development of the infestation on the undersides of the leaves was then determined visually.

Table C - Individual active substances

Table D - mixtures according to the invention

*) Efficiency calculated according to the Colby formula

The results of the tests show that the mixtures according to the invention are significantly more effective than calculated using the Colby formula.

Claims

claims

1. Containing fungicidal mixtures for controlling harmful fungi

1) the triazolopyrimidine derivative of the formula I,

and

2) fluoxastrobin of formula II,

in a synergistically effective amount.

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

3. Agent containing a liquid or solid carrier and a mixture according to one of claims 1 or 2.

4. A method for combating harmful fungi, characterized in that the fungi, their habitat or the plants to be protected against fungal attack, the soil or seeds are treated 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 simultaneously, jointly or separately, or in succession.

6. Process according to claims 4 and 5, characterized in that the compounds I and II according to claim 1 or the mixtures according to claims 1 or 2 are used in an amount of 5 g / ha to 1000 g / ha.

7. The method according to claims 4 and 5, characterized in that the compounds I and II according to claim 1 or the mixture according to claims 1 or 2 in an amount of 1 to 300 g / 100 kg of seed.

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

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