Patent Publication Number: US-2009227450-A1

Title: Triazole-Based Fungicidal Mixtures

Description:
The present invention relates to fungicidal mixtures, comprising 
     (1) epoxiconazole of the formula I 
     
       
         
         
             
             
         
       
         
         
           
             or its salts or adducts 
             and
 
(2) picoxystrobin of the formula II
 
           
         
       
    
     
       
         
         
             
             
         
       
     
     in a synergistically effective amount. 
     Moreover, the invention relates to a method for controlling harmful fungi using mixtures of the compound I with the compound II and to the use of the compound I with the compound II for preparing such mixtures, and also to compositions comprising these mixtures. 
     A number of active compound combinations of pyraclostrobin with a large number of other triazoles such as epoxiconazole is known from WO 97/40688. 
     A number of mixtures of dimoxystrobin with triazoles such as epoxiconazole is known from EP-A 0 645 091. 
     Epoxiconazole of the formula I and its use as crop protection agent are described in EP-B 0 196 038. 
     Picoxystrobin of the formula II is described in EP-A 0 326 330. 
     It is an object of the present inventions, with a view to reducing the application rates and broadening the activity spectrum of the known compounds, to provide mixtures which, at a reduced total amount of active compounds applied, exhibit improved activity against harmful fungi, in particular for specific indications. 
     We have found that this object is achieved by the mixtures defined at the outset. Moreover, we have found that simultaneous, that is joint or separate, application of the compound I and an active compound II or successive application of the compound I and an active compound II allows better control of harmful fungi than is possible with the individual compounds (synergistic mixtures). The compound I can be used as synergist for a large number of different active compounds. By simultaneous joint or separate application of the compound I and an active compound II, the fungicidal efficacy is increased in a superadditive manner. 
     Epoxiconazole of the Formula I 
     
       
         
         
             
             
         
       
     
     is known from EP-B 0 196 038. 
     Picoxystrobin of the Formula II 
     
       
         
         
             
             
         
       
     
     is described in EP-A 0 326 330. 
     Owing to the basic character of their nitrogen atoms, the compounds I and II are capable of forming salts or adducts with inorganic or organic acids and with metal ions, respectively. 
     Examples of inorganic acids are hydrohalic acids, such as hydrogen fluoride, hydrogen chloride, hydrogen bromide and hydrogen iodide, sulfuric acid, phosphoric acid and nitric acid. 
     Suitable organic acids are, for example, formic acid, carbonic 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 of 1 to 20 carbon atoms), arylsulfonic acids or aryldisulfonic acids (aromatic radicals, such as phenyl and naphthyl, which carry one or two sulfonic acid groups), alkylphosphonic acids (phosphonic acids having straight-chain or branched alkyl radicals of 1 to 20 carbon atoms), arylphosphonic acids or aryldiphosphonic acids (aromatic radicals, such as phenyl and naphthyl, which carry one or two phosphoric acid groups), where the alkyl or aryl radicals may carry further substituents, for example 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 also of the elements of transition groups one to eight, in particular chromium, manganese, iron, cobalt, nickel, copper, zinc, and others. Particular preference is given to the metal ions of the elements of transition groups of the fourth period. The metals can be present in the various valencies that they can assume. 
     The mixtures of the compound I and an active compound II, or the compound I and an active compound II applied simultaneously, that is jointly or separately, has/have excellent activity against a broad spectrum of phytopathogenic fungi, in particular from the classes of the Ascomycetes, Deuteromycetes, Peronosporomycetes (syn. Oomycetes) and Basidiomycetes. Some of them are systemically effective and can be employed in crop protection as fungicides for seed dressing, as foliar fungicides and as soil fungicides. 
     They are of particular importance for the control of a large number of fungi on various crop plants such as bananas, cotton, vegetable species (for example cucumbers, beans and cucurbits), barley, grass, oats, coffee, potatoes, corn, fruit plants, rice, rye, soybeans, tomatoes, grapevines, wheat, ornamental plants, sugar cane and a large number of seeds. 
     They are especially suitable for controlling the following plant diseases:
           Alternaria  species on vegetable species, oilseed rape, sugar beet and fruit and rice, such as, for example,     A. solani  or  A. alternata  on potatoes and tomatoes,     Aphanomyces  species on sugar beet and vegetable species,     Ascochyta  species on cereals and vegetable species,     Bipolaris  and  Drechslera  species on corn, cereals, rice and lawn, such as, for example,  D. maydis  on corn,     Blumeria graminis  (powdery mildew) on cereals,     Botrytis cinerea  (gray mold) on strawberries, vegetable species, flowers and grapevines,     Bremia lactucae  on lettuce,     Cercospora  species on corn, soybeans, rice and sugar beet,     Cochliobolus  species on corn, cereals, rice, such as, for example,  Cochliobolus sativus  on cereals,  Cochliobolus miyabeanus  on rice,     Colletotricum  species on soybeans and cotton,     Drechslera  species,  Pyrenophora  species on corn, cereals, rice and lawn, such as, for example,  D. teres  on barley or  D. tritici - repentis  on wheat,   Esca on grapevines, caused by  Phaeoacremonium chlamydosporium, Ph. Aleophilum , and  Formitipora punctata  (syn.  Phellinus punctatus ),     Elsinoe ampelina  on grapevines,     Exserohilum  species on corn,     Erysiphe cichoracearum  and  Sphaerotheca fuliginea  on cucumber species,     Fusarium  and  Verticillium  species on various plants, such as, for example,  F. graminearum  or  F. culmorum  on cereals or  F. oxysporum  on a large number of plants, such as, for example, tomatoes,     Gaeumanomyces graminis  on cereals,     Gibberella  species on cereals and rice (for example  Gibberella fujikuroi  on rice),     Glomerella cingulata  on grapevines and other plants,   Grainstaining complex on rice,     Guignardia budwelli  on grapevines,     Helminthosporium  species on corn and rice,     Isariopsis clavispora  on grapevines,     Michrodochium nivale  on cereals,     Mycosphaerella  species on cereals, bananas and peanuts, such as, for example,  M. graminicola  on wheat or  M. fijiensis  on bananas,     Peronospora  species on cabbage and bulbous plants, such as, for example,  P. brassicae  on cabbage or  P. destructor  on onion,     Phakopsara pachyrhizi  and  Phakopsara meibomiae  on soybeans,     Phomopsis  species on soybeans and sunflowers,  P. viticola  on grapevines,     Phytophthora infestans  on potatoes and tomatoes,     Phytophthora  species on various plants, such as, for example,  P. capsici  on bell-peppers,     Plasmopara viticola  on grapevines,     Podosphaera leucotricha  on apple,     Pseudocercosporella herpotrichoides  on cereals,     Pseudoperonospora  on various plants, such as, for example,  P. cubensis  on cucumber or  P. humili  on hops,     Pseudopezicula tracheiphilai  on grapevines,     Puccinia  species on various plants, such as, for example,  P. triticina, P. striformins, P. hordei  or  P. graminis  on cereals, or  P. asparagi  on asparagus,     Pyricularia oryzae, Corticium sasakii, Sarocladium oryzae, S. attenuatum, Entyloma oryzae  on rice,     Pyricularia grisea  on lawn and cereals,     Pythium  spp. on lawn, rice, corn, cotton, oilseed rape, sunflowers, sugar beet, vegetable species and other plants, such as, for example,  P. ultiumum  on various plants,  P. aphanidermatum  on lawn,     Rhizoctonia  species on cotton, rice, potatoes, lawn, corn, oilseed rape, potatoes, sugar beet, vegetable species and on various plants, such as, for example,  R. solani  on beets and various plants,     Rhynchosporium secalis  on barley, rye and triticale,     Sclerotinia  species on oilseed rape and sunflowers,     Septoria tritici  and  Stagonospora nodorum  on wheat,     Erysiphe  (syn.  Uncinula )  necator  on grapevines,     Setospaeria  species on corn and lawn,     Sphacelotheca reilinia  on corn,     Thievaliopsis  species on soybeans and cotton,     Tilletia  species on cereals,     Ustilago  species on cereals, corn and sugar cane, such as, for example,  U. maydis  on corn,     Venturia  species (scab) on apples and pears, such as, for example,  V. inaequalis  on apple.       

     The mixtures of the compound I and an active compound II are particularly suitable for controlling harmful fungi from the class of the Peronosporomycetes (syn. Oomycetes), such as  Peronospora  species,  Phytophthora species, Plasmopara viticola  and Pseudo- peronospora  species, in particular the corresponding species mentioned above. 
     The mixtures of the compounds I and II are furthermore suitable for controlling harmful fungi in the protection of materials (for example wood, paper, paint dispersions, fibers or fabrics) and in the protection of stored products. In the protection of wood, particular attention is paid to the following harmful fungi: Ascomycetes, such as  Ophiostoma  spp.,  Ceratocystis  spp.,  Aureobasidium pullulans, Sclerophoma  spp.,  Chaetomium  spp.,  Humicola  spp.,  Petriella  spp.,  Trichurus  spp.; Basidiomycetes, such as  Coniophora  spp.,  Coriolus  spp.,  Gloeophyllum  spp.,  Lentinus  spp.,  Pleurotus  spp.,  Poria  spp.,  Serpula  spp. and  Tyromyces  spp., Deuteromycetes, such as  Aspergillus  spp.,  Cladosporium  spp.,  Penicillium  spp.,  Trichoderma  spp.,  Alternaria  spp.,  Paecilomyces  spp. and Zygomycetes, such as  Mucor  spp., additionally in the protection of materials the following yeasts:  Candida  spp. and  Saccharomyces cerevisae.    
     The compound I is applied by treating the fungi or the plants, seed, materials or the soil to be protected against fungal attack with a fungicidally effective amount of the active compounds. Application can be both before and after the infection of the materials, plants or seeds by the fungi. 
     When preparing the mixtures, it is preferred to employ the pure active compounds I and II, to which further compounds active against harmful fungi or other pests, such as insects, arachnids or nematodes, or else herbicidal or growth-regulating active compounds or fertilizers can be added. 
     Usually, mixtures of compound I and the active compound II are employed. However, in certain cases mixtures of the compound I with two or, if appropriate, more active components may also be advantageous. 
     The compound I and the active compound II are usually employed in a weight ratio of from 100:1 to 1:100, preferably from 20:1 to 1:20, in particular from 10:1 to 1:10. 
     The further active components are, if desired, added in a ratio of from 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, especially on agricultural crop areas, are from 5 g/ha to 2000 g/ha, preferably from 20 to 900 g/ha, in particular from 50 to 750 g/ha. 
     Correspondingly, the application rates for the compound I are generally from 1 to 1000 g/ha, preferably from 10 to 900 g/ha, in particular from 20 to 750 g/ha. Correspondingly, the application rates for the active compound II are generally from 1 to 2000 g/ha, preferably from 10 to 1500 g/ha, in particular from 40 to 1000 g/ha. 
     In the treatment of seed, application rates of mixture are generally from 1 to 1000 g/100 kg of seed, preferably from 1 to 750 g/100 kg, in particular from 5 to 500 g/100 kg. 
     The method for controlling harmful fungi is carried out by the separate or joint application of compound I and active compound II or a mixture of compound I and active compound II by spraying or dusting the seeds, the plants or the soils before or after sowing of 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 use form depends on the particular intended purpose; in each case, it should ensure a fine and even distribution of the compound according to the invention. 
     The formulations are prepared in a known manner, for example by extending the active compound with solvents and/or carriers, if desired using emulsifiers and dispersants. Solvents/auxiliaries suitable for this purpose are essentially:
         water, aromatic solvents (for example Solvesso products, xylene), paraffins (for example mineral oil fractions), alcohols (for example methanol, butanol, pentanol, benzyl alcohol), ketones (for example cyclohexanone, gamma-butyrolactone), pyrrolidones (NMP, NOP), acetates (glycol diacetate), glycols, fatty acid dimethylamides, fatty acids and fatty acid esters. In principle, solvent mixtures may also be used,   carriers such as ground natural minerals (for example kaolins, clays, talc, chalk) and ground synthetic minerals (for example highly disperse silica, silicates); emulsifiers such as nonionogenic and anionic emulsifiers (for example polyoxyethylene fatty alcohol ethers, alkylsulfonates and arylsulfonates) and dispersants such as lignosulfite waste liquors and methylcellulose.       

     Suitable surfactants used are alkali metal, alkaline earth metal and ammonium salts of lignosulfonic acid, naphthalenesulfonic acid, phenolsulfonic acid, dibutylnaphthalenesulfonic acid, alkylarylsulfonates, alkyl sulfates, alkylsulfonates, fatty alcohol sulfates, fatty acids and sulfated fatty alcohol glycol ethers, furthermore condensates of sulfonated naphthalene and naphthalene derivatives with formaldehyde, condensates of naphthalene or of naphthalenesulfonic acid with phenol and formaldehyde, polyoxyethylene octylphenyl ether, ethoxylated isooctylphenol, octylphenol, nonylphenol, alkylphenyl polyglycol ethers, tributylphenyl polyglycol ether, tristearylphenyl polyglycol ether, alkylaryl polyether alcohols, alcohol and fatty alcohol ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers, ethoxylated polyoxypropylene, lauryl alcohol polyglycol ether acetal, sorbitol esters, lignosulfite waste liquors and methylcellulose. 
     Substances which are suitable for the preparation of directly sprayable solutions, emulsions, pastes or oil dispersions are mineral oil fractions of medium to high boiling point, such as kerosene or diesel oil, furthermore coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, for example toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes or their derivatives, methanol, ethanol, propanol, butanol, cyclohexanol, cyclohexanone, isophorone, highly polar solvents, for example dimethyl sulfoxide, N-methylpyrrolidone and water. 
     Powders, materials for spreading and dustable products can be prepared by mixing or concomitantly grinding the active substances with a solid carrier. 
     Granules, for example coated granules, impregnated granules and homogeneous granules, can be prepared by binding the active compounds to solid carriers. Examples of solid carriers are mineral earths such as silica gels, silicates, talc, kaolin, attaclay, limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground synthetic materials, fertilizers, such as, for example, 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 and other solid carriers. 
     In general, the formulations comprise from 0.01 to 95% by weight, preferably from 0.1 to 90% by weight, of the active compounds. The active compounds are employed in a purity of from 90% to 100%, preferably 95% to 100% (according to NMR spectrum). 
     The following are examples of formulations: 1. Products for dilution with water 
     A) Water-Soluble Concentrates (SL) 
     10 parts by weight of a compound according to the invention are dissolved in 90 parts by weight of water or in a water-soluble solvent. As an alternative, wetting agents or other auxiliaries are added. The active compound dissolves upon dilution with water. In this way, a formulation having a content of 10% by weight of active compound is obtained. 
     B) Dispersible Concentrates (DC) 
     20 parts by weight of a compound according to the invention are dissolved in 70 parts by weight of cyclohexanone with addition of 10 parts by weight of a dispersant, for example polyvinylpyrrolidone. Dilution with water gives a dispersion. The active compound content is 20% by weight. 
     C) Emulsifiable Concentrates (EC) 
     15 parts by weight of a compound according to the invention 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 with water gives an emulsion. The formulation has an active compound content of 15% by weight. 
     D) Emulsions (EW, EO) 
     25 parts by weight of a compound according to the invention 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 introduced into 30 parts by weight of water by means of an emulsifying machine (e.g. Ultraturrax) and made into a homogeneous emulsion. Dilution with water gives an emulsion. The formulation has an active compound content of 25% by weight. 
     E) Suspensions (SC, OD) 
     In an agitated ball mill, 20 parts by weight of a compound according to the invention are comminuted with addition of 10 parts by weight of dispersants and wetting agents and 70 parts by weight of water or an organic solvent to give a fine active compound suspension. Dilution with water gives a stable suspension of the active compound. The active compound content in the formulation is 20% by weight. 
     F) Water-Dispersible Granules and Water-Soluble Granules (WG, SG) 
     50 parts by weight of a compound according to the invention are ground finely with addition of 50 parts by weight of dispersants and wetting agents and prepared as water-dispersible or water-soluble granules by means of technical appliances (for example extrusion, spray tower, fluidized bed). Dilution with water gives a stable dispersion or solution of the active compound. The formulation has an active compound content of 50% by weight. 
     G) Water-Dispersible Powders and Water-Soluble Powders (WP, SP) 
     75 parts by weight of a compound according to the invention are ground in a rotor-stator mill with addition of 25 parts by weight of dispersants, wetting agents and silica gel. Dilution with water gives a stable dispersion or solution of the active compound. The active compound content of the formulation is 75% by weight. 
     2. Products to be Applied Undiluted 
     H) Dustable Powders (DP) 
     5 parts by weight of a compound according to the invention are ground finely and mixed intimately with 95 parts by weight of finely divided kaolin. This gives a dustable product having an active compound content of 5% by weight. 
     J) Granules (GR, FG, GG, MG) 
     0.5 part by weight of a compound according to the invention is ground finely and associated with 99.5 parts by weight of carriers. Current methods are extrusion, spray-drying or the fluidized bed. This gives granules to be applied undiluted having an active compound content of 0.5% by weight. 
     K) ULV Solutions (UL) 
     10 parts by weight of a compound according to the invention are dissolved in 90 parts by weight of an organic solvent, for example xylene. This gives a product to be applied undiluted having an active compound content of 10% by weight. 
     The active compounds can be used 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, dustable products, materials for spreading, or granules, by means of spraying, atomizing, dusting, spreading or pouring. The use forms depend entirely on the intended purposes; they are intended to ensure in each case the finest possible distribution of the active compounds according to the invention. 
     Aqueous use forms can be prepared from emulsion concentrates, pastes or wettable powders (sprayable 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 a wetting agent, tackifier, dispersant or emulsifier. However, it is also possible to prepare concentrates composed of active substance, wetting agent, tackifier, dispersant or emulsifier and, if appropriate, solvent or oil, and such concentrates are suitable for dilution with water. 
     The active compound concentrations in the ready-to-use preparations can be varied within relatively wide ranges. In general, they are from 0.0001 to 10%, preferably from 0.01 to 1%. 
     The active compounds may also be used successfully in the ultra-low-volume process (ULV), it being possible to apply formulations comprising over 95% by weight of active compound, or even to apply the active compound without additives. 
     Oils of various types, wetting agents or adjuvants may be added to the active compounds, even, if appropriate, not until immediately prior to use (tank mix). These agents are typically admixed with the compositions according to the invention in a weight ratio of from 1:100 to 100:1, preferably from 1:10 to 10:1. 
     The compounds I and II or 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, in the case of separate application, of the compounds 1 and 11. Application can be before or after the infection by harmful fungi. 
     The fungicidal action of the individual compounds and of the mixtures according to the invention was demonstrated by the tests below. 
     The active compounds, separately or jointly, were prepared as a stock solution comprising 25 mg of active compound which was made up to 10 ml using a mixture of acetone and/or dimethyl sulfoxide and the emulsifier Uniperol® EL (wetting agent having an emulsifying and dispersing action based on ethoxylated alkylphenols) in a ratio by volume of solvent/emulsifier of 99:1. The mixture was then made up to 100 ml with water. This stock solution was diluted with the solvent/emulsifier/water mixture described to give the concentration of active compound stated below. 
     The visually determined percentages of infected leaf areas were converted into efficacies in % of the untreated control: 
     The efficacy (E) is calculated as follows using Abbot&#39;s formula: 
         E =(1−α/β)·100 
     α corresponds to the fungicidal infection of the treated plants in % and
 
β corresponds to the fungicidal 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 are not infected. 
     The expected efficacies of active compound combinations were determined using Colby&#39;s formula (Colby, S. R. “Calculating synergistic and antagonistic responses of herbicide combinations”, Weeds, 15, 20-22, 1967) and compared with the observed efficacies. 
     Colby&#39;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 the active compound A at the concentration a   y efficacy, expressed in % of the untreated control, when using the active compound B at the concentration b   
     The active compounds were formulated separately as a stock solution having a concentration of 10 000 ppm in DMSO. 
     The active compound epoxiconazole was used as a commercial formulation. 
    
    
     USE EXAMPLE NO. 1 
     Activity Against the Gray Mold Pathogen  Botrytis cinerea  in the Microtiter Test (Botrci) 
     The stock solution is pipetted onto a microtiter plate (MTP) and diluted to the stated active compound concentration using a malt-based aqueous nutrient medium for fungi. An aqueous spore suspension of  Botrytis cinerea  was then added. The plates were placed in a water vapor-saturated chamber at temperatures of 18° C. Using an absorption photometer, the MTPs were measured at 405 nm on day 7 after the inoculation. The measured parameters were compared to the growth of the active compound-free control variant and the fungus- and active compound-free blank value to determine the relative growth in % of the pathogens in the individual active compounds. 
     The visually determined values for the percentage of infected leaf area were initially converted into a mean value and then 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. The expected efficacies for active compound combinations were determined using Colby&#39;s formula (Colby, S. R. (Calculating synergistic and antagonistic responses of herbicide combinations”, Weeds, 15, pp. 20-22, 1967) and compared to the observed efficacies. 
     
       
         
           
               
               
               
               
               
               
               
             
               
                   
               
               
                 Active compound/ 
                   
                   
                   
                 Effect calculated 
                   
                 Level of 
               
               
                 active compound 
                 Conc. 
                   
                 Observed 
                 according to 
                   
                 synergism 
               
               
                 combination 
                 (ppm) 
                 Ratio 
                 effect (%) 
                 Colby (%) 
                 Synergism 
                 (%) 
               
               
                   
               
             
            
               
                   
               
            
           
           
               
               
               
               
               
               
               
            
               
                 Epoxiconazole 
                 0.063 
                   
                 48 
                   
                   
                   
               
               
                   
                 0.016 
                   
                 15 
               
               
                 Picoxystrobin 
                 0.25 
                   
                 3 
               
               
                   
                 0.004 
                   
                 0 
               
               
                 Epoxiconazole + 
                 0.063 
                 1:4 
                 100 
                 49 
                 Yes 
                 51 
               
               
                 Picoxystrobin 
                 0.25 
               
               
                 Epoxiconazole + 
                 0.016 
                 4:1 
                 51 
                 15 
                 Yes 
                 36 
               
               
                 Picoxystrobin 
                 0.004