AU2002339474A2

AU2002339474A2 - Fungicidal mixtures

Info

Publication number: AU2002339474A2
Application number: AU2002339474A
Authority: AU
Inventors: Eberhard Ammermann; Josef Appel; Erich Birner; Gisela Lorenz; Klaus Schelberger; Gerd Stammler; Reinhard Stierl; Siegfried Strathmann
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 2001-09-12
Filing date: 2002-09-03
Publication date: 2003-03-24
Anticipated expiration: 2022-09-03
Also published as: ES2242070T3; KR20090097201A; WO2003022053A1; TWI313584B; CA2460032A1; UA78230C2; DE50203365D1; SI1427284T1; KR100934049B1; HUP0401815A3; PL367723A1; PT1427284E; CN1553772A; EP1427284A1; PL206673B1; ZA200402743B; AP2004003017A0; KR100975472B1; NZ531682A; EA200400371A1

Description

PF 52893 Fungicidal mixtures The present invention relates to fungicidal mixtures, comprising A) at least one active strobilurin compound selected from al) carbamates of the formula I H3 in which T is CH or N, n is 0, 1 or 2 and R is halogen, Cl-C 4 -alkyl or C 1

-C

4 -haloalkyl, where the radicals R may be different if n is 2, and/or a2) the phenyl acetic acid derivatives of the formulae IIa to IIf IIa IIb IIc IId IIe N-N O 9 OCH N

CH

3 PF 52893 2 O O H CO, 0 Y z

N

in which X is CH or N; and Y and Z are identical or different and are in each case hydrogen or halogen; and B) the compound of the formula III

O

S CN S CN IIf

III

in a synergistically effective amount.

Moreover, the invention relates to methods for controlling harmful fungi using mixtures of the compounds I and/or IIa-f and III and the use of the compounds I and/or IIa-f and III for preparing such mixtures.

The compounds of the formula I, their preparation and their action against harmful fungi are known from the literature (WO-A 96/01256 and 96/01258).

The formula I represents in particular carbamates in which the combination of the substituents corresponds to one row of the following table: Table 1: No. T Rn I.1 N 2-F 1.2 N 3-F 1.3 N 4-F 1.4 N 2-C1 N 3-C1 1.6 N 4-C1 1.7 N 2-Br 1.8 N 3-Br 1.9 N 4-Br 1.10 N 2-CH 3 PF 52893 No. T R 1. 11 N 3-CH 3 1.12 N 4 -CH 3 1.13 N 2-CH 2

CH

3 1.14 N 3-CH 2

CH

3 1.15 N 4-CH 2

CH

3 1.16 N 2-CH(CH 3 2 1.17 N 3-CH(CH 3 2 1.18 N 4-CH(CH 3 2 1.19 N 2-CF 3 1.20 N 3-CF 3 1.21 N 4-CF 3 1.22 N 2,4-F 2 1.23 N 2,4-Cl 2 1.24 N 3,4-Cl 2 1.25 N 2-Cl, 4-CH 3 1.26 N 3-Cl, 4-CH 3 1.27 CH 2-F 1.28 CH 3-F 1.29 CH 4-F 1.30 CH 2-Cl 1.31 CH 3-Cl 1.32 CH 4-Cl 1.33 CH 2-Br 1.34 CH 3-Br 1.35 CH 4-Br 1.36 CH 2-CH 3 1.37 CH 3-CH 3 1.38 CH 4-CH 3 1.39 CH 2-CH 2

CH

3 1.40 CH 3-CH 2

CH

3 1.41 CH 4-CH 2

CH

3 1.42 CH 2-CH(CH 3 2 1.43 CH 3-CH(CH 3 2 1.44 CH 4-CH(CH 3 2 1.45 CH 2-CF 3 1.46 CH 3-CF 3 1.47 CH 4-CF 3 1.48 CH 2,4-F 2 1.49 CH 2,4-Cl 2 PF 52893 No. T Rn 1.50 CH 3,4-C12 1.51 CH 2-C1, 4-CH 3 1.52 CH 3-C1, 4-CH 3 The compounds of the formulae IIa-f, their preparation and their action against harmful fungi are likewise known from the literature.

The formula IIf represents in particular compounds in which the combination of the variables X, Y and Z corresponds to one row of the table below: Table 2: No. X Y Z IIf.1 N F Cl IIf.2 N F H IIf.3 CH F H IIf.4 CH F H N Cl Cl IIf.6 N Cl H IIf.7 CH Cl H IIf.8 CH Cl Cl The compounds II are known in particular from: No. common name Literature IIa kresoxim-methyl EP-A 253 213 IIb dimoxystrobin EP-A 477 631 IIc trifloxystrobin EP-A 460 575 IId metominostrobin EP-A 398 692 IIe azoxystrobin EP-A 382 375 IIf.l fluoxastrobin WO-A 97/27189 Particular preference is given to the compounds 1.12, 1.23, 1.32 and 1.38. Particular preference is given to mixtures which comprise the compound 1.32 (common name: Pyraclostrobin). In another embodiment of the mixtures according to the invention, preference is given to the compound of the formula IIa.

4The compound of the formula III (common name: dithianon) and processes for its preparation are described in GB-A 857 383.

PF 52893 It is an object of the present invention to provide mixtures which have improved activity against harmful fungi combined with a reduced total amount of active compounds applied (synergistic mixtures), with a view to reducing the application rates and improving the activity spectrum of the known compounds.

We have found that this object is achieved by the mixtures defined at the outset. Moreover, we have found that applying the compounds I and/or IIa-f and III simultaneously, i.e. together or separately, or applying the compounds I and/or IIa-f and III in succession provides better control of harmful fungi than is possible with the individual compounds alone.

In relation to the C=CH or C=N double bonds, the compounds of the formulae IIa-f can be present in the E or the Z configuration (in relation to the carboxylic acid function). Accordingly, they can be used in the mixture according to the invention either as pure E or Z isomers or as E/Z isomer mixtures. The E/Z isomer mixture or the Z isomer is preferably used, the Z isomer being particularly preferred.

The C=N double bond of the oxime ether group in the side chain of the compound IIc can exist as pure E or Z isomers or as an E/Z isomer mixture. The compounds IIa-f can be used in the mixtures according to the invention either as isomer mixtures or as pure isomers.

Owing to their basic character, the compounds I, and IIa-f are capable of forming salts or adducts with inorganic or organic acids or with metal ions.

Examples of inorganic acids are hydrohalic acids such as hydrofluoric acid, hydrochloric acid, hydrobromic acid and hydriodic acid, carbonic acid, sulfuric acid, phosphoric acid and nitric acid.

Suitable organic acids are, for example, formic acid and alkanoic acids, such as acetic acid, trifluoroacetic acid, trichloroacetic acid and propionic acid, and also glycolic acid, thiocyanic acid, lactic acid, succinic acid, citric acid, benzoic acid, cinnamic acid, oxalic acid, alkylsulfonic acids (sulfonic acids having straight-chain or branched alkyl radicals with 1 to 20 carbon atoms), arylsulfonic acids or aryldisulfonic acids (aromatic radicals, such as phenyl and naphthyl, which carry one or two sulfo groups), alkylphosphonic acids (phosphonic acids having straight-chain or branched alkyl radicals with 1 to 20 carbon atoms), arylphosphonic acids or aryldiphosphonic acids (aromatic PF 52893 6 radicals, such as phenyl and naphthyl, which carry one or two phosphoric acid radicals), it being possible for the alkyl or aryl radicals to carry further substituents, eg.

p-toluenesulfonic acid, salicylic acid, p-aminosalicylic acid, 2-phenoxybenzoic acid, 2-acetoxybenzoic acid, etc.

Suitable metal ions are, in particular, the ions of the elements of the second main group, in particular calcium and magnesium, of the third and fourth main group, in particular aluminum, tin and lead, and of the first to eighth subgroup, in particular chromium, manganese, iron, cobalt, nickel, copper and zinc, and others. Particular preference is given to the metal ions of the elements of the subgroups of the fourth period. The metals can be present in the various valencies which they can assume.

When preparing the mixtures, it is preferred to employ the pure active compounds I and/or IIa-f and III, with which further active compounds against harmful fungi or other pests, such as insects, arachnids or nematodes, or else herbicidal or growth-regulating active compounds or fertilizers can be admixed as required.

The mixtures of the compounds I and/or IIa-f and III, or the simultaneous, joint or separate use of the compounds I and/or IIa-f and III, have outstanding action against a wide range of phytopathogenic fungi, in particular from the classes of the Ascomycetes, Deuteromycetes, Phycomycetes and Basidiomycetes.

Some of them act systemically and are therefore also suitable for use as foliar and soil-acting fungicides.

They are especially important for controlling a large number of fungi in a variety of crop plants, such as cotton, vegetable species (for example cucumbers, beans and cucurbits), barley, grass, oats, coffee, maize, fruit species, rice, rye, soya, grapevine, wheat, ornamentals, sugar cane, and a variety of seeds.

They are particularly suitable for controlling the following phytopathogenic fungi: Erysiphe graminis (powdery mildew) in cereals, Erysiphe cichoracearum and Sphaerotheca fuliginea in cucurbits, Podosphaera leucotricha in apples, Uncinula necator in grapevines, Puccinia species in cereals, Rhizoctonia species in cotton, rice and lawns, Ustilago species in cereals and sugar cane, Venturia inaequalis (scab) in apples, Helminthosporium species in cereals, Septoria nodorum in wheat, Botrytis cinerea (gray mold) in strawberries, vegetables, ornamentals and grapevines, Cercospora arachidicola in groundnuts, PF 52893 7 Pseudocercosporella herpotrichoides in wheat and barley, Pyricularia oryzae in rice, Phytophthora infestans in potatoes and tomatoes, Pseudoperonospora species in cucurbits and hops, Plasmopara viticola in grapevines, Alternaria species in vegetables and fruit and Fusarium and Verticillium species.

Furthermore, they can be used in the protection of materials in the protection of wood), for example against Paecilomyces variotii.

The compounds I and/or IIa-f and III can be applied simultaneously, either together or separately, or in succession, the sequence, in the case of separate application, generally not having any effect on the control results.

The compounds I and/or IIa-f and III are usually applied in a weight ratio of from 10:1 to 1:100, preferably from 1:1 to 1:20, in particular from 1:1 to 1:10 (I and/or IIa-f III).

Depending on the nature of the desired effect, the application rates of the mixtures according to the invention are, for the compounds I and/or IIa-f from 5 to 500 g/ha, preferably from to 500 g/ha, in particular from 50 to 200 g/ha.

Correspondingly, the application rates of the compound III are usually from 5 to 2000 g/ha, preferably from 10 to 1000 g/ha, in particular from 50 to 750 kg/ha.

For seed treatment, the application rates of the mixture are generally from 0.001 to 100 g/kg of seed, preferably 0.01 to g/kg,,in particular 0.01 to 10 g/kg.

If phytopathogenic harmful fungi are to be controlled, the separate or joint application of the compounds I and/or IIa-f or of the mixtures of the compounds I and/or IIa-f and III is effected by spraying or dusting the seeds, the plants or the soils before or after sowing, or before or after plant emergence.

The fungicidal synergistic mixtures according to the invention, or the compounds I and/or IIa-f and III, can be formulated for example in the form of ready-to-spray solutions, powders and suspensions or in the form of highly concentrated aqueous, oily or other suspensions, dispersions, emulsions, oil dispersions, pastes, dusts, materials for broadcasting or granules, and applied by spraying, atomizing, dusting, broadcasting or watering. The use form depends on the intended purpose; in any PF 52893 8 case, it should ensure as fine and uniform a distribution as possible of the mixture according to the invention.

The formulations are prepared in a manner known per se, eg. by adding solvents and/or carriers. It is usual to admix inert additives, such as emulsifiers or dispersants, with the formulations.

Suitable surfactants are the alkali metal salts, alkaline earth metal salts and ammonium salts of aromatic sulfonic acids, eg.

ligno-, phenol-, naphthalene- and dibutylnaphthalenesulfonic acids, and of fatty acids, alkyl- and alkylarylsulfonates, alkyl, lauryl ether and fatty alcohol sulfates, and salts of sulfated hexa-, hepta- and octadecanols, or of fatty alcohol glycol ethers, condensates of sulfonated naphthalene and its derivatives with formaldehyde, condensates of naphthalene or of the naphthalenesulfonic acids with phenol and formaldehyde, polyoxyethylene octylphenol ether, ethoxylated isooctyl, octyl or nonylphenol, alkylphenol polyglycol ethers, tributylphenyl polyglycol ethers, alkylaryl polyether alcohols, isotridecyl alcohol, fatty alcohol/ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers or polyoxypropylene alkyl ethers, lauryl alcohol polyglycol ether acetate, sorbitol esters, lignosulfite waste liquors or methylcellulose.

Powders, materials for broadcasting and dusts can be prepared by mixing or jointly grinding the compounds I and/or IIa-f and III or the mixture of the compounds I and/or IIa-f and III with a solid carrier.

Granules (eg. coated granules, impregnated granules or homogeneous granules) are usually prepared by binding the active compound, or active compounds, to a solid carrier.

Fillers or solid carriers are, for example, mineral earths, such as silica gel, silicic acids, silicates, talc, kaolin, limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground synthetic materials, and fertilizers, such as ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas and products of vegetable origin, such as cereal meal, tree bark meal, wood meal and nutshell meal, cellulose powders or other solid carriers.

The formulations generally comprise from 0.1 to 95% by weight, preferably from 0.5 to 90% by weight, of one of the compounds I and/or IIa-f and III or of the mixture of the compounds I and/or IIa-f and III. The active compounds are employed in a purity of PF 52893 9 from 90% to 100%, preferably from 95% to 100% (according to NMR spectrum or HPLC).

The compounds I and/or IIa-f and III, the mixtures or the corresponding formulations are applied by treating the harmful fungi, the plants, seeds, soils, areas, materials or spaces to be kept free from them with a fungicidally effective amount of the mixture, or of the compounds I and/or IIa-f and III in the case of separate applications. Application can be effected before or after infection by the harmful fungi.

The fungicidal activity of the compound and of the mixtures can be demonstrated by the following experiments: The active compounds are prepared separately or together as a strength emulsion in a mixture of 70% by weight of cyclohexanone, by weight of Nekanil® LN (Lutensol® AP6, wetting agent having emulsifying and dispersing action based on ethoxylated alkyl phenols) and 10% by weight of Emulphor® EL (Emulan® EL, emulsifier based on ethoxylated fatty alcohols) and diluted with water to the desired concentration.

Evaluation is carried out by determining the infected leaf areas in percent. These percentages are converted into efficacies. The expected efficacies of the active compound mixtures are determined using Colby's formula Colby, Weeds 15, 20-22 (1967)] and compared with the observed efficacies.

Colby's formula: E x y -x'y/100 E expected efficacy, expressed in of the untreated control, when using the mixture of the active compounds A and B at the concentrations a and b x efficacy, expressed in of the untreated control, when using active compound A at a concentration of a y efficacy, expressed in of the untreated control, when using active compound B at a concentration of b The efficacy is calculated as follows using Abbot's formula: E (1 a/P)9100 a corresponds to the fungal infection of the treated plants in and 13 corresponds to the fungal infection of the untreated (control) plants in An efficacy of 0 means that the infection level of the treated plants corresponds to that of the untreated control plants; an efficacy of 100 means that the treated plants were not infected.

Use Example 1 activity against apple scab (Venturia inaequalis on apple trees) During a summer season, the leaves of outdoor apple trees of the cultivar "Golden Delicious" were sprayed to runoff point eight times at intervals of 10 to 16 days using an aqueous suspension which had been prepared from a stock solution comprising 10% of active compound, 85% of cyclohexanone and 5% of emulsifier or mixtures of active compounds in the ratios given below. Owing to the natural infection pressure, the leaves were periodically infected by airborne spores or by wetting with aqueous spore suspensions of Venturia inaequalis. The climatic conditions supported the development of the foliar scab to such an extent that at the time of evaluation towards the end of the season virtually all leaves were infected with scab. The infection was determined visually in The values determined visually for the percentage of infected leaf areas were converted into efficacies in of the untreated control. An efficacy of 0 means the same degree of infection as in the untreated control, an efficacy of 100 means 0% infection.

PF 52893 11 The expected efficacies of the active compound combinations were determined using Colby's formula (Colby, S. R. "Calculating synergistic and antagonistic responses of herbicide Combinations", Weeds, pp. 20-22, 1967) and compared with the observed efficacies.

Table 3: Comparative tests Conc. of active compound in the Ex. spray liquor in g Active compound Efficacy in of the of active sub- untreated control stance/ha 1C 100 g/ha Compound I. 32 from Tab. 1 2C 100 g/ha Compound IIa 66 188 g/ha 16 3C Compound III 375 g/ha 33 4C (100% infection) Control untreated Table 4 Mixtures according to the invention Ex. Mixtures according to the Observed ef- Calculated invention (conc. in g/ha) ficacy efficacy* 100 (1.32) 188 (III) 93 87 6 100 (IIa) 188 (III) 91 71 7 100 (IIa) 375 (III) 90 77 using Colby's formula Use example 2 activity against peronospora of vines caused by Plasmopara viticola Leaves of potted vines of the cultivar "MUller-Thurgau" were sprayed to runoff point with an aqueous preparation of active compound which had been prepared from a stock solution comprising 10% of active compound, of cyclohexanone and 5% of emulsifier. The next day, the undersides of the leaves were inoculated with an aqueous zoospore suspension of Plasmopara viticola. The vines were then initially placed in a water-vapor-saturated chamber at 24 0 C for 48 hours and then in a greenhouse at 20-30 0 C for 5 days. After this period of time, the plants were again placed in a moist chamber for 16 hours to promote sporangiophore eruption. The extent to which the infection had developed on the undersides of the leaves was then determined visually.

The values determined visually for the percentage of infected leaf area were converted into efficacies in percent of the untreated control as described above. The expected efficacies of the active compound combinations were determined using Colby's formula and compared with the observed efficacies.

PF 52893 Table 5: Comparative tests Conc. of active Ex. compound in the compound Efficacy in of the spray liquor in untreated control ppm 4 8C 2 Compound IIc 33 1 22 4 9C 2 Compound IIe 1 66 20 44 20 Compound III 10 33 22 1CV (89% infection) Control untreated 0 Table 6 Mixtures according to the invention Ex. Mixtures according to the Observed Calculated invention (conc. in ppm) efficacy efficacy* 12 4 (IIc) 40 (III) 94 Mixture 1:10 13 2

I

Ic) 20 (III) 89 62 Mixture 1:10 14 1 (IIc) 10 (III) Mixture 1:10 83 47 14 4 (IIc) 20 (III) 9 Mixture 1:5 1 14 2 (IIc) 10 (III) Mixture 1:5 83 14 1 (IIc) 5 (III) 14 Mixture 1:566 39 14 2 (IIc) 5 (III) 61 47 Mixture 1:2.5 14 4 (IIc) 5 (III) 89 Mixture 1:1.25 14 2 (IIe) 20 (III) 94 84 Mixture 1:10 4 14 1 (IIe) 10 (III) Mixture 1:10 8 14 1 (IIe) 5 (III) Mixture 1:5 7 using Colby's formula PF 52893 13 The test results show that in all cases the observed efficacy is higher than the efficacy calculated beforehand using Colby's formula.

Claims

1. A fungicidal mixture, comprising A) at least one active strobilurin compound selected from al) carbamates of the formula I N.N in which T is CH or N, n is 0, 1 or 2 and R is halogen, Cj-C 4 -alkyl or Cl-C 4 -haloalkyl, where the radicals R may be different if n is 2, and/or a2) the phenyl acetic acid derivatives of the formulae ha to Ihf CH3 0 Iha H 3 CH 3 0 H H 3 H3I~ CH3CH 3 1 O NX& CF 3 I 0 W-OCH li H 3 0 W- OCH 3 d CH 3 I '1 I J IN 0 .OCH 3 N 1 H 3 PF 52893 I~O' Ii H CO 0 Y Z in which X is CH or N; and Y and Z are identical or different and are in each case hydrogen or halogen; and B) the compound of the formula III 0 S CN I I III in a synergistically effective amount.

2. A fungicidal mixture as claimed in claim i, comprising the compound 1.32. 0 0. 1.32 Y OCH 3CH3

3. A fungicidal mixture as claimed in claim i, comprising the compound of the formula IIa.

4. A method for controlling harmful fungi, which comprises treating the harmful fungi, their habitat, or the plants, seeds, soils, areas, materials or spaces to be kept free from them with a compound of the formula I and/or IIa-f as set forth in claim 1 and the compound of the formula III as set forth in claim i.

A method as claimed in claim 4, which comprises treating the harmful fungi, their habitat or the plants, seeds, soils, areas, materials or spaces to be kept free from them with from 5 to 500 g/ha of at least one compound I and/or IIa-f as set forth in claim i.

6. A process as claimed in claim 4, which comprises treating the harmful fungi, their habitat, or the plants, seeds, soils, areas, materials or spaces to be kept free from them with PF 52893 16 from 5 to 2000 g/ha of the compound III as set forth in claim 1.

7. The use of the compounds of the formulae I and/or IIa-f as set forth in claim 1 for preparing a mixture as claimed in claim 1.

8. The use of the compound of the formula III as set forth in claim 1 for preparing a mixture as claimed in claim 1.