EP1740050A1

EP1740050A1 - Fungicidal mixtures

Info

Publication number: EP1740050A1
Application number: EP05759107A
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: 2004-04-21
Filing date: 2005-04-15
Publication date: 2007-01-10
Also published as: EA200601839A1; CN1942100A; AR048619A1; AU2005235414A1; ZA200609628B; TW200603735A; CA2559433A1; NZ550175A; MXPA06010607A; WO2005102051A1; JP2007533677A; KR20070004106A; NO20065044L; IL178013A0; US20070219238A1; BRPI0509534A

Abstract

The invention relates to fungicidal mixtures that contain, as the active components, 1) the triazolopyrimidine derivative of formula (I), and 2) a copper fungicide (II) in a synergistically effective amount. The invention also relates to methods for controlling parasitic fungi using mixtures of compound (I) with the fungicide (II), and to the use of compound (I) with the fungicide (II) for producing such mixtures, 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) a copper fungicide II,

in a synergistically effective amount.

In addition, the invention relates to a method for controlling harmful fungi with mixtures of the compound I with the fungicide II and the use of the compound I with the fungicide!

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, their preparation and their action against harmful fungi is known from the literature (WO 98/46607).

The fungicidal activity of copper compounds since the beginning of the 20th century generally known (see. The Pesticide Manual, 10 ^th Ed., Pp 229-232, Brit. Crop Protec tion Council, Surrey, Great Britain, 1994).

Mixtures of triazolopyrimidines with copper oxychloride are generally known from EP-A 988 790.

The synergistic mixtures known from EP-A 988 790 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. Your fungi- However, the cidal activity against harmful fungi from the Oomycetes class leaves something to be desired.

The biological behavior of Oomycetes differs significantly from that of Ascomycetes, Deuteromycetes, and Basidiomycetes, because Oomycetes are biologically more related to algae than to fungi. Therefore, knowledge about the fungicidal activity of active substances against "real fungi", such as Ascomycetes, Deuteromycetes, and Basidiomycetes can only be transferred to Oomycetes to a very limited extent.

Oomycetes cause economically significant damage to various crops. In many regions, infections caused by Phytophthora infestans are the most important plant diseases in potato and tomato cultivation. In viticulture, considerable damage is caused by vine peronospora.

Practical experience in agriculture has shown that the repeated and exclusive use of a single active ingredient in the control of harmful fungi in many cases leads to the rapid selection of those fungal strains that have developed a natural or adapted resistance to the active ingredient in question. An effective control of these fungi with the active ingredient in question is then no longer possible.

In order to reduce the risk of selecting resistant fungal strains, mixtures of different active ingredients are preferably used today to combat harmful fungi. Combining active ingredients with different mechanisms of action can ensure long-term control success.

With regard to effective resistance management and an effective control of phytopathogenic harmful fungi at the lowest possible application rates, in particular harmful fungi from the Oomycetes class, the present invention was based on mixtures which, with a reduced total amount of active ingredients applied, have an improved activity against harmful fungi ,

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

The commercially available copper-containing active ingredients are generally suitable as copper fungicides II, since the fungicidal action starts from the copper ion. Are in use Copper oxychloride 11-1, (basic) copper carbonate II-2, copper hydroxide II-3, copper oxide II- 4, (basic) copper acetate II-5, Bordeaux broth II-6, copper sulfate II-7, copper oxysulfate (tribasic copper sulfate) II -8, copper oxychloride sulfate II-9, dicopper chloride trihydroxide 11-10, copper dihydrazinium disulfate 11-11, oxine copper 11-12, copper bis (3-phenylsalicylate) 11-13, tricopper dichloride dimethyldithiocarbamate 11-14 and copper 8-quinolinate 11-15 in question. Mixtures of different copper fungicides II can also be used.

The mixtures of the compound I and the fungicide II or the simultaneous joint or separate use of the compound I and the fungicide 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. They can be used in plant protection as leaf, pickling and soil fungicides.

They are particularly suitable for combating a large number of fungi on various crops such as bananas, cotton, vegetables (e.g. cucumber, beans and pumpkin family), barley, grass, oats, coffee, potatoes, corn, fruit plants, rye, soy, tomatoes, wine , Wheat, ornamental plants, sugar cane and especially rice, as well as a variety of seeds.

They are of particular importance for combating the following phytopathogenic fungi: Blumeria graminis (powdery mildew) on cereals, Erysiphe cichoracearum and Sphaerotheca fuliginea on squash plants, Podosphaera leucotricha on apples, Uncinula necatoran vines, Puccinia-Arieu on cereals, Aronia species 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 no- dorum on wheat, Botrytis cinerea on strawberries, vegetables, ornamental plants and vines, Mycosphaerella arlerx on bananas, peanuts and cereals, Pseudocercosporella herpotrichoides on wheat and barley, Pyricularia oryzae on rice, Phakopsora arias on soybeans, Phytophthora infestans on potatoes and tomatoes, Pseudoperonospora arenas on pumpkin plants and hops, Alternicola rara, plasmopara Outside of vegetables and fruits as well as Fusarium and Verticillium species.

They are particularly suitable for combating harmful fungi from the Oomycetes class on various crops such as vegetables (e.g. cucumbers, beans and squashes), especially late blight on tomatoes and potatoes, which is caused by Phytophthora infestans, and false vine mildew ( Vine peronospora), caused by Plasmopara viticola. They can also be used in material protection (eg wood protection), for example against Paecilomyces variotii.

The compound I and the fungicide 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.

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, enilconazole, epoxiconazole, fenbuconazole, fluquiconazole, flusilazole, flutriafol, hexaconazole, imazalil, ipconazole, metconazol, penocolazolol, myocazolol, myocazolol, myclazol, myclazol, myclazol, myocazolol, myclazol, myclazol, myclazol, myclazol, myclazol , Tetraconazole, tri-dimefon, triadimenol, triflumizole, 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, cyazofamidite, dazonometone , Famoxadone, fenamidon, fenarimol, fuberidazole, flutolanil, furametpyr, isoprothiolan, mepronil, nuarimol, penthiopyrad, picobenzamide, probenazol, procinazid, pyrifenox, pyroquilon, quinoxyfen, silthiofam, thiflazidazol, thilazazilol, thiabendazol Triforine

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, cyfiufenamide, cymoxanil, diclomezin, diclocymet, diethofencarb, edi fenphos, ethaboxam, fenhexamide, fentin acetate, fenoxanil, ferimzone, fluazi- nam, fosetyl, fosetyl aluminum, iprovalicarb, hexachlorobenzene, mandipropamide, metrafenone, pencycuron, propamocarb, phosphorous acid, phthalide, toloclofene, methyl, quoxamide, quintone Strobilurins such as azoxystrobin, dimoxystrobin, enestroburin, fluoxastrobin, cresoxim-methyl, metominostrobin, orysastrobin, picoxystrobin, pyraclostrobin or trifloxystrobin,

Sulfenoic 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, a further fungicide III or two fungicides III and IV are added to the compounds I and II.

Mixtures of compounds 1 and II with a component III are preferred. Mixtures of compounds I and II are particularly preferred.

The compound I and the fungicide II are usually used in a weight ratio of 100: 1 to 1: 100, preferably 2: 1 to 1:20, in particular 1: 1 to 1:15.

Components III and IV are optionally mixed in a ratio of 20: 1 to 1:20 to the compound I.

Depending on the type of compound and the desired effect, the application rates of the mixtures according to the invention are 0.1 to 10 kg / ha, preferably 0.5 to 5 kg / ha, in particular 0.5 to 2 kg / 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.

The application rates for the fungicide II are accordingly generally from 0.1 to 10 kg / ha, preferably 0.5 to 5 kg / ha, in particular 0.5 to 2 kg / ha.

In the case of seed treatment, application rates of the mixture of 0.1 to 2.5 kg / 100 kg of seed, preferably 1 to 1.0 kg / 100 kg, in particular 1 to 0.5 kg / 100 kg, are generally used. The method for controlling harmful fungi is carried out by the separate or joint application of the compound I and the fungicide II or the mixtures of the compound I and the fungicide II by spraying or dusting the seeds, the plants or the soil before or after the plants are sown or before or after emergence of the plants.

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 metal, alkaline earth metal, ammonium salts of lignosulfonic acid, naphthalenesulfonic acid, phenolsulfonic acid, dibutylnaphthalenesulfonic acid, alkylaryisulfonates, alkyl sulfates, alkyl sulfonates, fatty alcohol sulfates, fatty acids and sulfated naphthalene naphthalene and sulfonated dehydrogenated naphthalenethane from sulfonates and also condensation products with sulfonated formaldehyde derivatives of sulfonated formaldehyde derivatives and sulfonated dehydrogenated naphthalenedaphthalene and sulfonated dehydrogenated naphthalenedaphthalene with sulfonated formaldehyde derivatives and sulfonated dehydrogenated naphthalenedaphthalene and sulfonated dehydrogenated naphthalenedaphthalene ether and condensation products, as well as condensation products with sulfated naphthalene and ethylenatedethane derivatives of sulfonated naphthalenedaphthalene with sulfonated dehydrogenated naphthalenedaphthalene 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 waste liquors 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, xy-, are used to produce directly sprayable solutions, emulsions, pastes or oil dispersions. lol, 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, for example coated granules, impregnated granules and homogeneous granules, can be prepared by binding the active ingredients to solid carriers. Solid carriers are mineral earth ^'n, such as silica gels, silicates, talc, kaolin, attaclay, limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, Caicium- and magnesium sulfate, magnesium oxide, ground plastics, fertilizers such as 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 ingredients are dissolved in cyclohexanone with the addition of a dispersing agent e.g. Dissolved polyvinyl pyrrolidone. 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-dodecylbenzene sulfonate and castor oil ethoxylate (5% each) dissolved. 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, for example xylene. 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, for example in the form of directly sprayable solutions, powders, suspensions or dispersions, emulsions, oil dispersions, pastes, dusts, scattering agents, granules by spraying, atomizing, dusting, scattering or Pouring can be applied. The application forms depend entirely on the purposes; 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, it is also possible to prepare concentrates composed of an active substance, wetting agents, adhesives, dispersants or emulsifiers and possibly solvents or oil, which 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.

Oils of various types, wetting agents, adjuvants, herbicides, fungicides, other pesticides, 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 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 when applied separately. 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 emulsifier 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.

Example of use - activity against late blight on tomatoes caused by Phytophthora infestans in protective treatment

Leaves of potted tomato plants were sprayed to runoff point with an aqueous suspension in the active compound concentration given below. The following day, the leaves were washed with an aqueous suspension of sporangia

Phytophthora infestans infected. The plants were then placed in a water vapor-saturated chamber at temperatures between 18 and 20 ° C. After 6 days, the blight on the untreated but infected control plants had developed so strongly that the infestation could be determined visually in%.

The visually determined values for the percentage of leaf areas affected were converted into efficiencies as% of the untreated control:

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

W = (1 - α / β) 100

α 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 infection 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 for combinations of active ingredients were determined using the Colby formula (Colby, SR (Calculating synergistic and antagonistic responses of herbicide combinations ", Weeds, 15, pp. 20-22, 1967) and compared with the observed efficacies. Colby formula: E = x + y - xy / 100

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

Compounds A and B known from the copper oxychloride mixtures described in EP-A 988 790 were used as comparative compounds:

Table A - Individual substances

Table B - mixtures according to the invention

*) Efficiency calculated according to the Colby formula

Table C - Comparative experiments Copper oxychloride mixtures known from EP-A 988 780

*) Efficiency calculated according to the Colby formula

The results of the experiments show that the mixtures according to the invention are considerably more effective than the known mixtures due to their strong synergism.

Claims

claims

1. Containing fungicidal mixtures for controlling harmful fungi

1) the triazolopyrimidine derivative of the formula I,

and

2) a copper fungicide II, in a synergistically effective amount.

2. Fungicidal mixtures according to claim 1, containing as copper fungicide II an active ingredient from the group copper oxychloride 11-1, (basic) copper carbonate II-2, copper hydroxide II-3, copper oxide II-4, (basic) copper acetate II-5, Bordeaux broth II-6, copper sulfate II-7, copper oxysulfate II-8, copper oxychloride sulfate II-9, dikupferchlorid trihydroxide 11-10, copper dihydrazinium disulfate 11-11, oxine-copper 11-12, copper-bis- (3rd phenyl salicylate) 11-13, tricopper dichloride dimethyl dithiocarbamate 11-14 and copper 8-quinolinate 11-15.

3. Fungicidal mixtures according to claims 1 or 2, containing the compound of formula I and a copper fungicide II in a weight ratio of 100: 1 to 1: 100.

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

5. A method for controlling 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.

6. The method according to claim 5, characterized in that the compounds I and II according to claims 1 or 2 simultaneously, together or separately, or in succession.

7. The method according to claim 5, characterized in that one applies the mixture according to one of claims 1 to 3 in an amount of 0.1 to 10 kg / ha _. ,

8. The method according to claims 5 to 7, characterized in that harmful fungi from the class of the Oomycetes are controlled.

9. The method according to claims 5 and 6, characterized in that the mixture according to claims 1 or 2 is used in an amount of 0.1 to 2.5 kg / 100 kg of seed.

10. Seed containing the mixture according to one of claims 1 to 3 in an amount of 0.1 to 2.5 kg / 100 kg.

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