EP1830642A1

EP1830642A1 - Fungicidal mixtures

Info

Publication number: EP1830642A1
Application number: EP05819687A
Authority: EP
Inventors: Markus Gewehr; Reinhard Stierl; Matthias NIEDENBRÜCK; Udo HÜNGER
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 2004-12-23
Filing date: 2005-12-21
Publication date: 2007-09-12
Also published as: CN101087522A; US20080076747A1; CA2590364A1; KR20070093122A; WO2006069714A1; AU2005321580A1; BRPI0519236A2; JP2008525352A; CN101087522B; IL183677A0

Abstract

The inventive fungicidal mixtures contain the following active components: 1) strobilurin derivatives of formula (I), and 2) at least one type of active substance (II) selected from a carbamate group in a synergistically active quantity. Said invention also relates to a method for controlling harmful fungi by means of the mixtures of the compound (I) and the active substances (II), to the use of the compound (I) and the active substances (II) for producing said mixtures and to agents containing said mixtures.

Description

Fungicidal mixtures

description

The present invention relates to fungicidal mixtures containing as active components

1) the strobilurin derivative of the formula I,

and

2) at least one active ingredient II selected from the group of carbamates:

Mancozeb, Maneb, Metam, Metiram, Ferbam, Propineb, Thiram, Zineb, Ziram, Diethofencarb, Iprovalicarb, Flubenthiavalicarb, Propamocarb,

Methyl 3- (4-chlorophenyl) -3- (2-isopropoxycarbonylamino-3-methylbutyrylamino) propanoate and

{2-Chloro-5- [1- (3-methyl-benzyloxyimino) -ethyl] -benzyl} -carbamic acid methyl ester, {2-chloro-5- [1- (6-methylpyridin-2-ylmethoxyimino) - ethyl] -benzyl} -carbamic acid methyl ester; in a synergistically effective amount.

Moreover, the invention relates to a method for controlling harmful fungi with mixtures of the compound I with active compounds II and the use of the compound I with active compounds II for the preparation of such mixtures and compositions containing these mixtures.

The Strobilurinderivat of formula I, 2- {2- [3- (4-chlorophenyl) -1-methyl-allylidenaminooxymethyl] -phenyl} -3-methoxy-acrylic acid methyl ester, referred to as the component 1 above, its preparation and its action against harmful fungi is known from the literature (EP-A 936 213, common name: Enestroburin).

The active compounds II mentioned above as component 2, their preparation and their action against harmful fungi are generally known (cf .: http://www.hclrss.demon.co.uk/index.htmn; they are commercially available. Mancozeb, manganese ethylenebis (dithiocarbamate) (polymer) complex zinc salt

(US 3,379,610),

Maneb, manganese ethylene bis (dithiocarbannate) (US 2 504 404);

Metam, methyldithiocarbamic acid (US 2,791,605); Metiram, zinc ammonium ethylenebis (dithiocarbamate) (U.S. 3,248,400);

Propineb, zinc propylene bis (dithiocarbamate) polymer (BE 611 960);

Ferbam, iron (3+) dimethyldithiocarbamate (US 1,972,961);

Thiram, bis (dimethylthiocarbamoyl) disulphide (DE 642 532);

Ziram, dimethyldithiocarbamate; Zineb, zinc ethylene bis (dithiocarbamate) (US 2 457 674);

Diethofencarb, isopropyl 3,4-diethoxycarbanilate;

Iprovalicarb, [(1S) -2-methyl-1- (1-p-tolyl-ethylcarbamoyl) -propyl] -carbamic acid isopropyl ester (EP-A 472 996);

Flubenthiavalicarb (benthiavalicarb), {(S) -1 - [(1 R) -1- (6-fluoro-benzothiazol-2-yl) ethylcarbamoyl] -2-methyl-propyl} -carbamic acid isopropyl ester (JP-A 09/323 984);

Propamocarb, [3- (dimethylamino) propyl] propylcarbamate (DE 15 67 169).

The compounds without common name, their preparation and their fungicidal action are also known: 3- (4-chloro-phenyl) -3- (2-isopropoxycarbonylamino-3-methyl-butyrylamino) -propanoic acid methyl ester (formula HA, EP-A 10 28 125)

Carbamatoxime ethers (Formula H-B; EP-A 12 01 648)

wherein X is N (II-B-1) or CH (II-B-2).

With regard to a reduction of the application rates and a widening of the spectrum of action of the known compounds, the present invention was based on mixtures which show an improved action against harmful fungi, in particular for certain indications, with a reduced total amount of applied active substances.

Accordingly, the mixtures defined above were found. It has also been found that with simultaneous joint or separate application Compound I and an active compound II or when using the compound I and an active compound II successively control harmful fungi better than with the individual compounds (synergistic mixtures). Compound I can be used as a synergist for a variety of different agents. By simultaneous co-administration or separate use of the compound I with an active compound II, the fungicidal activity is increased to a superadditive extent.

The mixtures of the compound I and of an active compound II, or the simultaneous joint or separate use of the compound I and an active compound II are distinguished by an outstanding activity against a broad spectrum of phytopathogenic fungi, in particular from the class of Ascomycetes, Deutero - mycetes, oomycetes and basidiomycetes. They are in part systemically effective and can be used in crop protection as foliar and soil fungicides.

They are of particular importance for the control of a variety of fungi on various crops such as bananas, cotton, vegetables (eg cucumbers, beans and pumpkins), barley, grass, oats, coffee, potatoes, corn, fruit plants, rice, rye, soy, tomatoes , Wine, wheat, ornamental plants, sugar cane and a variety of seeds.

Advantageously, they are suitable for controlling the following phytopathogenic fungi: Blumeria graminis (powdery mildew) on cereals, Erysiphe cichoracearum and Sphae- rotheca fuliginea on cucurbits, Podosphaera leucotricha on apples, Uncinula necator on vines, Pucc / n / a species on cereals, Rhizoctonia A anen on cotton, rice and turf, Ustilago A anen on grain and sugarcane, Venturia inaequalis on apples, Bipolaris and Drechslera species on cereals, rice and turf, Sepfor / a species of wheat, Botrytis cinerea on strawberries, vegetables , Ornamental plants and vines, Mycophaerella plants on bananas, peanuts and cereals, Pseudocercosporella herpotriodorides on wheat and barley, Pyricularia oryzae on rice, Phytophthora infestans on potatoes and tomatoes, Pseudoperonospora plants on cucurbits and hops, Plasmopara viticola on vines , Alternaria species on vegetables and fruits as well as Fusarium and Verticillium Aύen.

The mixtures of compound I and of an active compound II are particularly suitable for combating Alternaria and Sofryf / s species.

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

Usually, mixtures of compound I with an active ingredient II are used. Under certain circumstances, however, mixtures of compound I with two or optionally several active components may be advantageous.

As further active components in the above sense, especially the above-mentioned active compounds II and in particular the above-mentioned preferred active ingredients in question.

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

If desired, the further active components are added to compound I in a ratio of from 20: 1 to 1:20.

Depending on the nature of the compound and the desired effect, the application rates of the mixtures according to the invention are from 5 g / ha to 2000 g / ha, preferably from 50 to 900 g / ha, in particular from 50 to 750 g / 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 the active compound II are correspondingly generally 1 to 2000 g / ha, preferably 10 to 900 g / ha, in particular 40 to 500 g / ha.

In seed treatment, application rates of mixture of 1 to 1000 g / 100 kg of seed, preferably 1 to 750 g / 100 kg, in particular 5 to 500 g / 100 kg, are generally used.

The method for controlling harmful fungi is carried out by the separate or combined application of the compound I and the active compound II or the mixtures of the compound I and the active ingredient II by spraying or dusting the seeds, the plants or the soil before or after sowing the plants or before or after emergence of the plants. The mixtures according to the invention or the compound I and the active compound II can be converted into the customary formulations, for example 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, e.g. by stretching the active ingredient with solvents and / or carriers, 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

Excipients such as ground natural minerals (e.g., kaolins, clays, talc, chalk) and ground synthetic minerals (e.g., fumed silica, silicates); Emulsifiers such as nonionic and anionic emulsifiers (for example 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 production of directly sprayable solutions, emulsions, pastes or oil dispersions come mineral oil fractions of medium to high boiling point, such as kerosene or diesel oil, coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, eg toluene, Xy- JoI, 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 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 flour, 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 compounds are used in a purity of 90% to 100%, preferably 95% to 100% (according to NMR spectrum).

For seed treatment, the formulations in question give, after dilution of from two to ten times, active compound concentrations of from 0.01 to 60% by weight, preferably from 0.1 to 40% by weight, in the ready-to-use preparations.

Examples of formulations according to the invention are: 1. Products for dilution in water

A Water-soluble concentrates (SL, LS)

10 parts by weight of the active ingredients are dissolved with 90 parts by weight of water or a water-soluble solvent. Alternatively, wetting agents or other adjuvants are added. When diluted in water, the active ingredient dissolves. This gives a formulation with 10 wt .-% active ingredient content.

B Dispersible Concentrates (DC)

20 parts by weight of the active compounds are dissolved in 70 parts by weight of cyclohexanone with the addition of 10 parts by weight of a dispersant, e.g. Polyvinylpyrrolidone dissolved. Dilution in water gives a dispersion. The active ingredient content is 20% by weight

C Emulsifiable Concentrates (EC)

15 parts by weight of the active compounds are dissolved in 75 parts by weight of xylene with addition of calcium dodecylbenzenesulfonate and castor oil ethoxylate (in each case 5 parts by weight). Dilution in water results in an emulsion. The formulation has 15% by weight active ingredient content. D emulsions (EW, EO, ES)

25 parts by weight of the active compounds are dissolved in 35 parts by weight of xylene with addition of calcium dodecylbenzenesulfonate and castor oil ethoxylate (in each case 5 parts by weight). This mixture is added to water by means of an emulsifying machine (e.g., Ultraturax) in 30 parts by weight and made into a homogeneous emulsion. Dilution in water results in an emulsion. The formulation has an active ingredient content of 25% by weight.

E suspensions (SC, OD, FS)

20 parts by weight of the active ingredients are comminuted with the addition of 10 parts by weight of dispersants and wetting agents and 70 parts by weight of water or an organic solvent in a stirred ball mill to a fine active substance suspension. Dilution in water results in a stable suspension of the active ingredient. The active ingredient content in the formulation is 20% by weight.

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

50 parts by weight of the active ingredients are finely ground with the addition of 50 parts by weight of dispersants 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 substance. The formulation has an active ingredient content of 50% by weight.

G Water-dispersible and water-soluble powders (WP, SP, SS, WS) 75 parts by weight of the active compounds are ground in a rotor-stator mill with the addition of 25 parts by weight of dispersing and wetting agents and silica gel. Dilution in water results in a stable dispersion or solution of the active ingredient. The active ingredient content of the formulation is 75% by weight.

H gel formulations

In a ball mill, 20 parts by weight of the active ingredients, 10 parts by weight of dispersant, 1 part by weight of gelling agent and 70 parts by weight of water or an organic solvent are ground to a fine suspension. Dilution with water results in a stable suspension with 20% by weight active ingredient content.

2. Products for direct application

I dusts (DP, DS)

5 parts by weight of the active ingredients are finely ground and intimately mixed with 95 parts by weight of finely divided kaolin. This gives a dust with 5 wt .-% active ingredient content. J Granules (GR, FG, GG, MG)

0.5 parts by weight of the active ingredients are finely ground and combined with 99.5 parts by weight of carriers. Common processes are extrusion, spray drying or fluidized bed. This gives a granulate for direct application with 0.5 wt .-% active ingredient content.

K ULV solutions (UL)

10 parts by weight of the active compounds are dissolved in 90 parts by weight of an organic solvent, e.g. XyIoI solved. This gives a product for direct application with 10 wt .-% active ingredient content.

For seed treatment, water-soluble concentrates (LS), suspensions (FS), dusts (DS), water-dispersible and water-soluble powders (WS, SS), emulsions (ES), emulsifiable concentrates (EC) and gel formulations (GF) are usually used. These formulations can be applied to the seed undiluted or, preferably, diluted. The application can be done before sowing.

Preference is given to using FS formulations for seed treatment. Typically, such formulations contain 1 to 800 g / l active ingredient, 1 to 200 g / l surfactants, 0 to 200 g / l antifreeze, 0 to 400 g / l binder, 0 to 200 g / l dyes and solvents, preferably water.

The active compounds may be used as such, in the form of their formulations or the forms of use 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 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. For the preparation of emulsions, pastes or oil dispersions, the substances, as such or dissolved in an oil or solvent, can be homogenized in water by means of wetter, tackifier, dispersant or emulsifier. 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, possibly also just immediately before use (tank mix), are added. These agents can be added to the compositions according to the invention in a weight ratio of 1: 100 to 100: 1, preferably 1:10 to 10: 1.

As adjuvants in this sense are in particular: organically modified polysiloxanes, eg Break Thru S 240 ^® ; Alcohol alkoxylates, eg. As Atplus 245 ^®, Atplus MBA 1303 ^®, Plurafac LF 300 ^® and Lutensol ON 30 ^®; EO-PO block polymers, eg. B. Pluro- nic RPE 2035 ^® and Genapol B ^®; Alcohol ethoxylates, eg. As Lutensol XP 80 ^®; and sodium dioctylsulfosuccinate, e. B. Leophen RA ^®.

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 when applied separately. The application can be made before or after the attack by the harmful fungi.

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

drug treatment

For the microtiter tests, the active ingredients were formulated separately as stock solution with a concentration of 10,000 ppm in DMSO. The active compounds were prepared separately or together as a stock solution with 25 mg of active ingredient, which with a mixture of acetone and / or DMSO and the emulsifier Uniperol® EL (wetting agent with emulsifying and dispersing action based on ethoxylated alkylphenols) in the volume ratio solvent- Emulsifier from 99 to 1 ad 10 ml was filled. It was then made up to 100 ml with water. This stock solution was diluted with the described solvent-emulsifier-water mixture to the drug concentration given below.

evaluation

In the microtiter tests, the measured parameters were compared with the growth of the drug-free control variant and the fungus-free and active substance-free blank to determine the relative growth in% of the pathogens in the individual active ingredients.

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

The efficiency (W) is calculated according to the formula of Abbot as follows:

W = (1-σ / 0) -100

a corresponds to the fungal infestation of the treated plants in% and ß 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 efficacies for drug combinations were determined according to the Colby formula (Colby, S.R. (Calculating synergistic and antagonistic responses of herbicide combinations), Weeds, 15, pp. 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 using active substance B in concentration b Use Example 1 Activity Against the Causative Agent of Gray Mold Botrytis cinerea in the Microtiter Test

The stock solutions were mixed according to the ratio, pipetted into a microtiter plate (MTP) and diluted with an aqueous fungus nutrient medium based on malt to the stated active compound concentration. This was followed by the addition of an aqueous spore suspension of Botrytis cinerea. The plates were placed in a water vapor saturated chamber at temperatures of 18 ° C. With an absorption photometer, the MTPs were measured at 405 nm on the 7th day after inoculation.

Application Example 2 - Efficacy against barley spot disease caused by Pyrenophora teres in protective use

Leaves of potted barley seedlings were sprayed to drip point with aqueous suspension in the concentration of active compound given below. Five days after the test plants were treated with an aqueous spore suspension of Pyrenophora [syn. Drechslera] teres, the causative agent of net blotch inoculation. Subsequently, the test plants were placed in the greenhouse at temperatures between 20 and 24 ⁰ C and 95 to 100% relative humidity. After 6 days, the extent of disease development was determined visually as% of total leaf area.

Use Example 3 - Efficacy against tomato blight caused by Alternaria solani

Leaves of potted plants of the "Golden Queen" variety were sprayed to drip point with an aqueous suspension in the concentration of active compound specified below. The following day, the leaves were infected with an aqueous spore suspension of Alternaria solani in 2% biomalt solution with a density of 0.17 x 10 ⁶ spores / ml. Subsequently, the plants were placed in a water vapor-saturated chamber at temperatures between 20 and 22 ° C. After 5 days, the disease on the untreated, but infected control plants had developed so strongly that the infestation could be determined visually in%.

The results of the experiments show that the mixtures according to the invention are considerably more effective due to the synergism than predicted according to the CoI by formula.

Claims

claims

1. Fungicidal mixtures for controlling phytopathogenic harmful fungi containing two active components:

1) the strobilurin derivative of the formula I,

and

2) at least one active ingredient II selected from the group of carbamates:

Mancozeb, Maneb, Metam, Metiram, Ferbam, Propineb, Thiram, Zineb, Cyram, Diethofencarb, Iprovalicarb, Flubenthiavalicarb, Propamocarb, 3- (4-Chloro-phenyl) -3- (2-isopropoxycarbonylamino-3-methyl-butyrylamino ) - methyl propanoate and

{2-Chloro-5- [1- (3-methyl-benzyloxyimino) -ethyl] -benzyl} -carbamic acid methyl ester, {2-chloro-5- [1- (6-methylpyridin-2-ylmethoxyimino) - ethyl] benzyl} -carbamic acid methyl ester;

in a synergistically effective amount.

2. Fungicidal mixtures according to claim 1, containing as active ingredient Il Mancozeb or Metiram.

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

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

5. A method for controlling phytopathogenic harmful fungi, which comprises 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 an active compound II according to claim 1.

6. The method according to claim 5, characterized in that the compounds I and II according to claim 1 simultaneously, and jointly or separately, or sequentially ausbringt.

7. The method according to claims 5 or 6, characterized in that the compounds I and II according to claim 1 or the mixture according to one of claims 1 to 3 in an amount of 5 g / ha to 2000 g / ha.

8. The method according to claims 5 or 6, characterized in that the compounds I and II according to claim 1 or the mixture according to one of

Claims 1 to 3 applied in an amount of 1 to 1000 g / 100 kg of seed.

9. Seed containing the mixture according to any one of claims 1 to 3 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.