WO2010132169A1

WO2010132169A1 - Fungicidal active compound compositions for turf treatment

Info

Publication number: WO2010132169A1
Application number: PCT/US2010/031239
Authority: WO
Inventors: Ed Vandenberg; Richard Rees
Original assignee: Bayer CropScience LP
Current assignee: Bayer CropScience LP
Priority date: 2009-05-15
Filing date: 2010-04-15
Publication date: 2010-11-18
Anticipated expiration: 2011-11-15
Also published as: JP5635080B2; CN102427723B; JP2012526813A; KR101696208B1; KR20140014391A; EP2429287A1; EP2429287A4; CN102427723A

Abstract

The present invention relates to novel compositions comprising a fungicide that inhibits mitochondrial respiration at the QoI site, (QoI inhibitor), a contact fungicide, a demethylation inhibitor and pigments, which are highly suitable for controlling unwanted phytopathogenic fungi. Moreover, the fungicidal compositions are able to control mold and fungus infection in glasses, in particular turf grasses.

Description

BCS 09-6004 P WE/ 15 7 2009

- 1 -

Fungicidal active compound compositions for turf treatment

The piescnt invention iclatcs to novel compositions comprising a fungicide that inhibits mitochondrial respiration at the QoI site, (QoI inhibitor), a contact fungicide, a dcmcthylation inhibitoi and pigments, which aic highly suitable foi conti oiling unwanted phytopathogenic fungi Moreovci, the fungicidal compositions ate able Io contiol mold and fungus infection in glasses, in paiticulai tuif glasses

Fine tuif grass species aic giown on golf course gtccns, faiiways and tee boxes, as well as tuif farms and many othci locations. In noithein tcgions, such as Canada and the not them United States, which aie subject to temperate climates in the late summer and eaily fail and snow conditions in late fall and cat Iy wintci cciiain moulds such as dollar spot, Sclei otinia homeocωpa, and snow molds, such as Microdochitim nivale, Typhula incatnata and Tγplnda Uhikω iemis, represent a chronic pioblcm foi turf glass giowcts

If left untieatcd in the late summei and fall, tuif gt ass is predisposed to damage caused by Sclerotinia homeocaψa in the late summei and fall and the snow molds in late fall and over winter to spring S homeocatpa attacks most tuif grasses giown in the South Bent grass, common and hybrid beimuda grass and zoysia aie most susceptible to S homeocaipa attacks The doilat spot disease occuis fiom spring through fall, and is most active during moist periods of warm days (about 7O⁰F to about 85⁰F) and cool nights (about 60⁰F) in the spring, early summei and fall

Wheie the mold infection is extensive, the secovciy of the tuif glass can be delayed well into the giowing season and seriously affect the ability of the tuif grass to lccovcs , leaving aicas of dead patches Fuithei, tui f glasses weakened or damaged by these molds aic exliemciy slow to iccovei in the spring and aic often invaded by undcsiiable oppoi tunistic weedy giass species such as creeping bent glass (Agrostis palusti is) and annual bluegiass (Poa aimua)

A typical snow mold pievention piogiam tcquiies a mold inhibiting fungicide to be applied to turf giass prioi to peimaπent wintci snow covei Typical piograms consist of thtee applications pnor to peimancnt snow covei and an additional application afler the snow covet is gone in the spring Several commercial fungicide pioducts have been appioved foi use against dollar spot and snow mould species

COMPASS™ (irifloxystiobin; (αE)- α(meihoxyimino)-2-[[[(E)-[I-[3- (trifluoiomethylphcnyl]cthylidine]-amino]oxy]methyl]bcnzenacelic acid methyl cstei) is an aromatic dioxime fungicide which has been appiovcd foi the contioE of leaf spot, Fmω intn patch and blown patch diseases in tut f gtass Trifloxystiobiπ is a quinone outside inhibitoi (QoI) and a member of the class of aromatic dioxime fungicides described in U S Pat No 5,238,956 BCS 09-6004

- 2 -

ROVRAI. GREEN GT^{1 M} (iprodione; 3-(3,5-dichioropheny])W-(l-methylcthyl)-2_s4-dioxo-l- imidazolidinccaboximide) is a dicaiboximidc fungicide foi pink snow mold control at a rate of 250 ml/ 100m² and for gray snow mould control at a ialc of 375 ml/ 100m². lpiodionc is a member of the class of 3-phcπyl hydantoin compounds described in U. S, Pat No. 3,755,350,

The effectiveness of iprodione to control the spread of snow mold in turf grasses (especially the gray snow molds T. lncamata and T ishikariemh) is highly variable due to the varying amounts of fungus inoculums, the varying length of snow cover under which snow mould inoculums thrive and the varying winlcr temperatures that exist across the country from year to year. Thus, in order to effectively control against a spectrum of snow moulds a iclativcly high dose may be required as well as multiple applications.

Phthalocyanines ate known pigments having many applications, such as pigments for inks and coatings and even for turf grass paints Sec, for example, DE 2,51 1,077 and .JP 03/221576 Copper phthalocyaninc has been used, but only in combination with certain othei active ingredients, foi enhancing turf quality. For example, U.S. Pat. No. 5,599,804 describes a method of combating fungi and enhancing turf quality in turf grass by applying in specific ratios ccitain phthalocyanines in combination with phosphorous acid or an alkaline earth metal salt thereof or with certain røonocster salts of phosphorous acid U S . Pal No 5,643,852 describes a method of enhancing turf quality in turf giass by applying in specific ratios certain phthalocyanines in combination with (i) phosphorous acid or an alkaline earth metal salt thereof or certain monoester salts of phosphorous acid and (ii) certain ethylene bisdiihiocarbamatc contact fungicides U.S. Pat. No. 5,336,661 describes a method of treating bent grass and enhancing turf quality by applying in specific iatios (i) ccitain monoester salts of phosphorous acid and (ii) a metallic ethylene bisdilhiocarbaniate contact fungicide. This patent also describes a specific composition containing a combination of aluminum tris(O cthylphosphonate) (fosctyl-al) and a manganese-zinc ethylene bisdithiocarbamate complex (mancozeb) used in a foim (FORE fungicide) believed to have contained an unknown amount of the phthalocyaπine compound Pigment Blue 15

Since the ecological and economical demands made on modem fungicides arc increasing constantly, for example with respect to activity spectrum, toxicity, selectivity, application rate, formation of iesidues and favourable manufacture, and theie can fuilhcrmoic be problems, for example, with lesistancc, there is a constant need to develop novel fungicides which, at least in some areas, help to overcome the disadvantages mentioned

The picscnt invention provides active compound combinations or compositions which achieve the object at least in some aspects, BCS 09-6004

- .3 -

Suiprisingly, it has now been found that the active compound combinations or compositions accoiding to the invention do not only exhibit an additive effect of the activity of the individual components, but a synergistic effect. Therefore, fπstly, the customary application rate of the individual substances can be reduced. Secondly, the active compound combinations according to the invention offer a high degice of activity against phytopathogens even in cases whcic the individual compounds are employed in amounts where, foi their pait, they no longer show (sufficient) activity. In principle, this allows, firstly, the activity spectrum to be broadened and, secondly, belter safely during handling,

In addition to the fungicidal synergistic activity, the active compound combinations according to the invention have further surprising properties which, in a wider sense, may also be called synergistic, such as, for example: broadening of the activity spechum, for example to resistant pathogens of plant diseases; lower application iatcs of the active compounds; sufficient control of pests with the aid of the active compound combinations according to the invention even at application rales where the individual compounds show no oi virtually no activity; advantageous behavioui during formulation or during use, for example during grinding, sieving, emulsifying, dissolving or application; improved storage stability and light stability; advantageous iesidue formation; improved loxicological or ecotoxicological behavioui; improved properties of the plant, for example better growth, increased harvest yields, a better developed root system, a largci leaf area, greener leaves, stronger' shoots, less seed required, lower' phototoxicity, mobilization of the defence system of the plant, good compatibility with plants. Thus, the use of the active compound combinations or compositions accoiding to the invention contributes considerably to keeping young plant stems healthy, which inci cases, fot example, the winter survival of the cereal seed treated, and also safeguards quality and yield. Moreover, the active compound combinations according to the invention may contribute to enhanced systemic action. Even if the individual compounds of the combination have no sufficient systemic properties, the active compound combinations according to the invention may stilt have this property. In a siniHai manner, the active compound combinations according to the invention may result in higher persistency of the fungicidal action.

It has now been found that active compound combinations comprising

A) at least one phthalocyaninc pigment and

B) i) at least one QoI inhibitor fungicide and

at least one fungicide selected fron the group consisting of

ii) a contact fungicide and BCS 09-6004

^„ 4 - iii) a DMI-fungicidc,

show supcrioi mold conlroE abilities than compositions with similai fungicides but without the pigments

QoI inhibitor fungicides (i) include azoxystrobin, cncstrobin, picoxystrobin, pyraclostrobiπ, krcsoxim-methyl, trifloxysliobin, dimoxystrobin, metominostiobiπ, orysastrobin, famoxadone, fluoxastrobin, fcnamidone, pyribcncaib, preferred are azoxystrobin, pyiaclostrobin, trifloxystrobiπ and fluoxastiobin, particular preferred is irifloxystiobin.

Contact fungicides (ii) include PP-fungicidcs such as fludioxinil, dicatboimides such as iprodione, chlozoiinate, procymidone, viπclozolin, AH-fungicides such as biphenyl, chloioneb, dicloian, quintozcne (PCNB), tccnazenc (TCNB), tolclofos-methyl, dithiocarbamates such as ferbam, mancozeb, mancb, metiram, propincb, thiiam, ziπeb and ziram, phthalimidcs such as captan, captafol and folpet, chloronilriles such as chlorothalonil, sulfamides such as dichlofluanid and toiyfluanid, guanidines, such as dodine, guazatinc and iminooctadine, triazine such as anilazine and qυinones such as dithianon; pencyuron, validamycin, inorganic fungicides, such as copper and sulphur products. Preferred contact fungicides are iprodione, fludioxinil and chlorothalonil, particular preferred are iprodione and fludioxinil which involve signal transduction in their mode of action.

DMI-fυngicidcs (demethylation inhibitors) include triazoies such as azaconazole, bitcrtanol, bromuconazolc, cyproconazoic, difcnoconazolc, diniconazole, diniconazole-M, epoxiconazofe, etaconazole, fenbuconazolc, fluquinconazole, flusilazoie, flutiiafol, hexaconazole, imibcncoπazole, ipconazolc, metconazolc, myclobutanil, penconazole, propiconazole, prothioconazole, simcconazolc, tcbuconazole, tetiaconazole, triad imefon, triadimenol and tiiticonazole, piefeπed arc prothioconazole, tebuconazole, propiconazole and triticonazole, particular prefeπcd arc piopiconazolc and triticonazole.

Prcfaiably the composition according to the invention comprises as compound B) i) trifloxystrobin as QoI inhibitor fungicide, ii) iprodione as contact fungicide and iii) tiitriconazolc as DMl- fuπgicide. Most preferably the composition according to the invention comprises i) trifloxystrobin as QoI inhibitor fungicide and ii) iprodione as contact fungicide.

Suitable pigments A) include phthalocyanincs

Suitable phthalocyanines are substituted copper phthalocyanincs which may be substituted from 1 to 4 times on each isoindolc gioup independently, Examples of suitable substituents for the isoindole groups of copper phthaiocyanine dyes include but are not limited to halogen, unsubstituted or substituted lower alkyl, lower alkoxy, alkylamino, alkylthio, ammonium, BCS 09-6004

- 5 - sulfonato, sulfonate alkyl, sulfate, phosphate, phosphonate, and caiboxylatc. The ionic or ionizablc substituents can have as counterions the alkali metals, preferably lithium, sodium, or potassium, the alkaline earth metals, prcfciably beryllium, magnesium, calcium, strontium, and barium, and various ammonium ions By the terms lower alkyl and lower aikoxy are genet ally meant alkyl groups of from 1 to 6 carbon atoms and aikoxy groups of from 1 to 6 caibon atoms

Suitable copper phthalocyanines aic commercially available and include but aie not limited to Pigment Blue 16, Vat Blue 29, Pigment Blue 15, Hcliogcn Green GG, Ingrain Blue 14, Ingrain Blue 5, Ingrain Blue 1 , Pigment Gieen 37, and Pigment Green 7. In one prcfeired embodiment, the copper phthalocyaπine is Pigment Blue 15, also known as phthalocyanine blue and Green pigment (Green 7)

Preferably the composition according to the invention comprises as compound A) a green pigment (Gieen 7)

According to the invention, the term "active compound combination" means various possible combinations of the active compounds mentioned above, such as, for example, rcadymixcs, tank mixes (which is to be understood as meaning spray mixtures prepared prior to application from the foundations of the individual active compounds by mixing and diluting) or combinations thereof (for example, a binary rcadymix of two of the active compounds mentioned above is converted with a formulation of the third individual substance into a tank mix). Accoiding to the invention, the individual active compounds may also be used successively, i.c one after the other, within a reasonable interval of a few hours or days, and, in the treatment of seed, also, for example, by applying a plurality of layers comprising different active compounds. Preferably, it is immaterial in which order the individual active compounds may be employed,

The present invention furthermore relates to compositions comprising the active compound combinations according to the invention. Preferably, the compositions are fungicidal compositions comprising agriculturally suitable carriers or extenders.

According to the invention, carrier' is to be understood as meaning a natural or- synthetic, organic or inorganic substance which is mixed oi combined with the active compounds for better applicability, in particular for application to plants ot plant parts or seeds The carrier, which may be solid or liquid, is generally inert and should be suitable for use in agriculture.

Suitable solid carriers arc: for example ammonium salts and natural ground minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, monlmorillonile or diatomaceous earth, and ground synthetic minerals, such as finely divided silica, alumina and natural or synthetic silicates, resins, waxes, solid fertilizers, water, alcohols, especially butanol, organic solvents, mineral oils and vegetable oils, and also derivatives thereof. It is also possible to use mixtures of such carriers. Solid carriers suitable for granules BCS 09-6004

- 6 - arc: for example crushed and fractionated natural minerals, such as calcitc, maible, pumice, scpiolite, dolomite, and also synthetic gianuSes of inorganic and oiganic meals and also granules of organic material, such as sawdust, coconut shells, maize cobs and tobacco stalks Suitable emulsificrs and/or foam-formers are: for' example nonionic and anionic cmulsifiers, such as polyoxycthylene fatly acid esters, polyoxyethylcne fatty alcohol ethers, for example alkylaiyl polyglycol ethers, alkylsulphonates, alkyl sulphates, arylsulphonatcs, and also protein hydrolysates, Suitable dispcrsants are: for example lignosulphite waste liquors and mclhylccHulose.

Suitable liquefied gaseous extenders or carriers are liquids which arc gaseous at ambient tcmperture and under atmospheric pressure, for example aeiosol piopcllants, such as butane, propane, nitrogen and carbon dioxide.

Tackifiers, such as carboxymethylcellulose and natural and synthetic polymers in the form of powders, granules and laticcs, such as gum aiabic, polyvinyl alcohol, polyvinyl acetate, or' else natural phospholipids, such as cephalins and lecithins and synthetic phospholipids can be used in the formulations. Other possible additives arc mineral and vegetable oils

If the extender' used is water, it is also possible for example, to use organic solvents as auxiliary solvents. Suitable liquid solvents are essentially: aromatic compounds, such as xylene, toluene or alkylnaphthalenes, chlorinated aromatic compounds or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroelhylcncs or¹ methylene chloride, aliphatic hydrocarbons, such as cyclohexane oi¹ paraffins, for example mineral oil fractions, mineral and vegetable oils, alcohols, such as butanol or glycol, and also ethers and esters thereof, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanonc, strongly potai solvents, such as dimethylformamidc and dimethyl sulphoxide, and also water¹.

The compositions according to the invention may comprise additional further components, such as, for example, surfactants. Suitable surfactants are emulsifieis, dispctsants or wetting agents having ionic or nonionic properties, or mixtures of these surfactants. Examples of these are salts of potyacrylic acid, salts of lignosulphonic acid, salts of phenoisulphonic acid or^' naphthalenesulphonic acid, polycondensales of ethylene oxide with fatty alcohols or with fatty acids or with fatty amines, substituted phenols (preferably alkylphcnols or as y [phenols), sails of sulphosuccinic esters, taurine derivatives (preferably alkyl tamatcs), phosphoric esters of polyethoxylaicd alcohols or phenols, fatty esters of polyols, and derivatives of the compounds containing sulphates, suiphonates and phosphates The presence of a surfactant is required if one of the active compounds and/or one of the inert cairicrs is insoluble in water and when the application takes place in water. The proportion of surfactants is between 5 and 40 per cent by weight of the composition according to the invention . BCS 09-6004

- 7 -

It is possible Io use colorants such as inorganic pigments, for example iron oxide, titanium oxide, Prussian blue, and organic dyes, such as alizarin dyes, azo dyes and metal phthalocyaninc dyes, and trace nutrients, such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.

If appropriate, other additional components may also be present, for example protective colloids, binders, adhesivcs, thickeners, thixotiopic substances, penetrants, stabilizers, sequestring agents, complex foimeis Li general, the active compounds can be combined with any solid or liquid additive customarily used for' foπnulation purposes.

In general, the compositions according to the invention comprise between 0,05 and 99 per cent by weight of the active compound combination according to the invention, preferably between 5 and 60 pes cent by weight, particularly preferably between 10 and 40 per cent by weight, vciy particularly picfcrably 20 and .30 per cent by weight.

According to another aspect, the composition according to the invention comprises between 2 and 10 per cent by weight, preferably between 4 and 9 per cent by weight, particularly preferably between 5 and 7 per cent by weight compound A), between 1 and 3,3 per cent by weight, preferably between 1,0 and 2,5 per cent by weight, particularly preferably between 1,2 and 2,0 per cent by weight compound Bi) and between 20 and 50 per cent by weight, preferably between 20 and 40 per cent by weight, particularly psefeiably between 20 and 30 per cent by weight compound Bii) and/or Biii), the sum of the compounds adding up to 100 per cent by weight.

The fungicidal compositions according to the invention can be used for the curative or protective control of phytopalhogenic fungi The compositions according to the invention may be applied to healthy or diseased turfs. Prophylactic application to healthy turf may be helpful in preventing turf diseases. Application to turf containing one or more turf diseases is helpful in treating the one or more turf diseases Some pathogens of fungal diseases which can be treated according to the invention may be mentioned by way of example, but not by way of limitation:

Spring, summer and fall diseases: Dollar Spot (Lanzia ,ψp and MoeUerodiscw spp), Brown Patch (Rhizoctoma solaπii), Large Patch (Rhkoctonia solani), Rapid Blight, Rust {Puccinia spp ), Fusarium Blight (Fmarium spp ) Pink Patch, Curvulaiia (Curvulaiϊa spj and Necrotic Ring Spot (Lβptosphaeria korrae), Leaf Spots such as Heiminthospoπum Leaf Spot caused by Drechslera spp, pathogens, Corticum Red Thread (Laefisan^'a fiiciformk) and Anthracnose (Colletoirichum).

Winter diseases: Fusarium Patch (Pink Snow Mold (Mici odochiwn nivalis)) and Gray Snow Mold (Typlmla spp.,), Pink Snow Mold (Fusarium nivale) BCS 09-6004

The described compositions arc also helpful in improving turf quality aftei snow cover release in spring,

The fungicidal compositions accoiding to the invention can be used for lurfgrass disease control on golf courses, sod farms, and institutional areas wheic fine tuif is grown

The active compound combinations or compositions according to the invention can be used as such or, depending on their respective physical and/or chemical properties, in the form of their formulations or the use forms prepared therefrom, such as aerosols, capsule suspensions, cold- fogging concentrates, warm-fogging concentrates, encapsulated granules, fine granules, ilowable concentrates for the treatment of seed, ready~to~usc solutions, dustablc powdcis, emulsifiable concentrates, oil-in-water emulsions, water-in-oil emulsions, maciogranules, microgranules, oil- dispersiblc powders, oil-misctbEc flowable concentrates, oil-miscible liquids, foams, pastes, pesticide- coated seed, suspension concentrates, suspoemulsioπ concentrates, soluble concentrates, suspensions, weltable powders, soluble powders, dusts and granules, water-soluble granules or tablets, water- soluble powdeis for the treatment of seed, wettable powders, natuial products and synthetic substances impregnated with active compound, and also microencapsulations in polymeric substances and in coating materials for' seed, and also ULV cold-fogging and warm-fogging formulations.

The formulations mentioned can be prepared in a manner known per se, for example by mixing the active compounds or the active compound combinations with at least one solvent or diluent, emulsifier, dispersant and/or binder¹ or' fixing agent, water lepellanl, appropr iate siccatives and UV stabilizers and, if appropriate, dyes and pigments, and also further processing auxiliaries.

The treatment accoiding to the invention of the plants and plant parts with the active compound combinations or compositions is carried out directly or by action on their surroundings, habitat or stosage space using customaiy treatment methods, for' example by dipping, spraying, atomizing, irrigating, evaporating, dusting, fogging, broadcasting, foaming, painting, spreading-on, watering (drenching), drip ungating and, in the case of propagation material, in particular in the case of seeds, furthermore as a powder for' diy seed treatment, a solution for seed treatment, a water-soluble powder for slurry treatment, by incrusting, by coating with one or more coats, etc,

The compositions according to the invention do not only comprise ready-to-use compositions which can be applied with suitable apparatus to the plant or the seed, but also commercial concentrates which have to be diluted with water priot to use

The active compound combinations accoiding to the invention can be present in commercial foimulations and in the use forms prepared from these formulations as a mixture with other active BCS 09-6004

- 9 - compounds, such as insecticides, alliactnnls, sterilanls, bactericides, acaricides, nematicides, fungicides, giowlh regulators or herbicides

The picscnt invention can be practiced with all turfgtasscs, including cool season tuilgrasses and warm season lurfgiasses. Examples of cool season turfgrasscs ai"c bluegrasscs {Poa spp ), such as Kentucky blucgiass {Poa pratemis L ), rough bluegrass (Poa trivialis L.), Canada bluegrass (Poa compressa L), annual bluegrass (Poa annuci L,..), upland bluegrass (Poa glaticantha Gaudin), wood bluegiass (Poa nemoraUs L ), and bulbous biuegrass {Poa bulbosa L); the bentgrasses and redtop (Agrostis ψp), such as creeping bcntgiass (Agrostis palustris Huds,), colonial bentgiass (Agrostis /emu's Sibth.), velvet bcntgrass (Agrostis canina L), South German Mixed Bentgrass (Agrostis spp including Agrosth tenim Sibth , Agrostis canina L., and Agrostis palustris Huds..), and redtop (Agrostis alba L ); the fescues (Festuai spp), such as red fescue (Festuca rubra L spp. rubra), creeping fescue (Festuca i ubra L ), chcwings fescue {Festuca rubra comnnitata Gaud.), sheep fescue (Festuca ovina L,,), hard fescue (Festuca iongifotia Thuill.), hail¹ fescue (Feslucu capillata Lam ), tall fescue (Festuca anmdmacea Schicb.), meadow fescue (Festuca elanor L); the ryegrasses (Lolium spp.), such as annual ryegrass (Lolium nntltifloi urn Lam.), perennial ryegrass (Lolium pereime L.), italian ryegrass (Lolium muJtiflonim Lam ); and the whcatgrasses (Agropyron spp.. ), such as fairway wheatgiass (Agropyron cristatum [L) Gacitn.), crested wheatgiass {Agropyron desertorum (Fisch.) Schult ), and western wheatgiass (Agropyron smilhii Rydb,) Othei cool season turfgrasscs include beachgrass (Ammophύ^' a breviligitlata Fein), smooth bromegtass (Broimis biennis Leyss ), cattails such as Timothy (Phleum pratense L ), sand cattail (Phleuin subulatum L), orchaidgrass (Dactylis gbmerata L), weeping alkaligrass {Puccitiellia distans (L.) Pail .) and crested dog's-tail (Cγnosurus cristatus L )

Examples of warm season turfgj asses include Bermudagrass {Cynodoπ spp L. C. Rich), zoysiagiass (Zoysia spp WiIkL)₅ St. Augustine grass {Stenotaphrum secimdatuin Walt Kunlze), centipedcgrass

(Eremochloa ophiuroides Munro Hack.), carpetgrass (Axonopus affinis Chase), Bahia glass

(Paspahtm notation Fluggc), Kikuyugrass (Pennisetum clandeslinum Hochst ex Chiov ), buffalo giass (Buchloe dacryloids (NuIt.) Engelm.), Blue gramma (Botitebiia gracilis (H.B..K ) Lag ex

Griffiths), seashore paspalum {Paspalum vaginatuin Swaitz) and sideoats grama (Bouteloua curtipenduia (Michx Ton,), Cool season turfgiasses are generally preferred for treatment according to the invention. More prefcitcd is bluegrass, bentgrass and redtop, fescue, and ryegrass . Bcntgiass is most preferred.

The application rate of the active compound combinations according to the invention is BCS 09-6004

- JO -

« when treating leaves: fiom 100 to I O 000 g/ha, preferably fiom 3000 to 5 500 g/lia, particulaily prcfciably fiom 1000 to 3 500 g/ha (when the application is catiicd out by watering oi chipping, it may even be possible to reduce the application late, in particular when ineit substrates such as sock wool oi pet lite aie used)

These application rates arc mentioned only by way of example and not by way oi limitation in the sense of the invention.

The active compound combinations or compositions accoiding to the invention can thus be employed foi piotccting plants for a cctlain pes iod of time aftci treatment against attack by the pathogens mentioned The pet tod for which protection is piovided extends gencially for 1 to 28 days, piefeiably 1 to 14 days, afiei the licatmeπt of the plants with the active compounds, Ot for up to 200 days after seed tieatment

The good fungicidal activity of the active compound combinations according to the invention is demonsUated by the example below, Wlicicas the individual active compounds have weaknesses in the fungicidal activity, the combinations exhibit an activity which exceeds a simple addition of activity

In fungicides, a syneigistic effect is always picscnt when the iungicidal activity of the active compound combinations is gicatci than the expected activity which, for a given combination of 2 or 3 active compounds, is calculated as foliows accoiding to S R Colby ("Calculating Syneigistic and Antagonistic Responses of Hctbicidc Combinations", Weeds J967, 15, 20-22):

If

X is the efficacy when active compound A is applied at an application iatc of m g/ha,

Y is the efficacy when active compound B is applied at an application rate of n g/ha,

Ej is the efficacy when the active compounds A and B aic applied at application rates of m and n g/ha, lespectivcly, and

E₂ is the efficacy when the active compounds A and B and C aie applied at application iates of m and n and i g/ha, respectively,

X Y . — Λ T T - then ¹⁰° BCS 09-6004

- 1 1 -

(X x Y + X x Z + Y x Z) X x Y x Z or E, = X + Y + Z - +

100 10 000

Here, the efficacy is dctcimincd in % 0% means an efficacy wliieh coπesponds to that of the control, whereas an efficacy of 100% means that no infection is observed

If the actual fungicidal activity is greater than calculated, the activity of the combination is supeiadditive, i.e. a syneigistic effect is present. In this case, the efficacy actually observed must be greatei than the value, calculated using the formula given above, for the expected efficacy Ei .

The invention is illustiated by the example below, (However, the invention is not limited to the example )

BCS 09-6004

- 12 -

Examplcs

To determine the superiority of vaϋous compositions compiisc a QoI inhibitor fungicide, a contact fungicide, and a dcmethylalion inhibitor with pigments over a composition containing three classes of fungicides but without pigments, trials weie conducted at the following sites: 1. University of Massachusetts, Vermont Site; 2. Univeisily of Wisconsin, Sentry Site; .3, University of Wisconsin, Iron Mountain Site; 4. University of Wisconsin, Champion Ml Site; 5 University of Wisconsin, Edina MN Site; 6. Oregon State University, Sun River Site; 1, Washington State University, McCaIl Site; 8. Washington State Univcisity, Chewelah Site; and 9. Washington State University Pullman Site.

A general procedure for¹ the application of the compositions described is as follows Treatment plots were, for' example, 6 feel x 7 (3,8 m²) feet with three ieplicalions in a randomized complete-block design. Treatments were applied from late-October to mid-November, In several instances, the compositions were applied at SO GPA with a bicycle-wheeled CO₂ pressurized (40 psi = 2,8 bar) sprayer with 1 1008 flat fan Tee.Jet nozzles.

Several sites have intermittent snow cover' throughout the winter with periods of continuous snow covei . Once the snow melted, or' is mechanically removed, individual plots were evaluated foi pink (M nivale) and/oi gray (Typhiilci ψp ) snow mold disease severity (% area infected) and turf glass quality (rated on a scale of 1 to 9, with 9 being excellent).

Table 1 shows the effect of a composition containing differing amounts of a QoI inhibitor fungicide (trifloxysttobin), a contact fungicide (iprodione), a demcthylation inhibitor (tiiticonazoie) and a pigment (phthalocyanine Green pigment) in comparison with a standard combination of three classes of fungicides combined for snow mold control that does not contain any pigments (INSTRATA*, mariufactutcd by SYNGENTA) on Turf Quality (1O\ or Turf Coloi (TCl The scale is fiom 1 to 9 with 1 = poor and 9 = excellent. INSTRATA*' was used as a control because it is a snow mold product that has three classes of fungicides but docs not have any pigments.

BCS 09-6004

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Table 1:

" Sites: 1 University of Massachusetts, Vermont site; 2 University of Wisconsin, Sentry Site; 3 Univetsity of Wisconsin, Iron Mountain Site; 4. University of Wisconsin, Champion MI Site; 5. University of Wisconsin, Edina MN Site; 6 OSU, Sun River Site; 7. Washington Stale University McCaII Site; 8. Washington State Univetsity Chewelah Site; 9 Washington State University Pullman Site.

b A = trifloxystrobin; B = ipiodionc; C = Phthalocyaiiine Green pigment (Green 7); D = tiiticonazole (3 Ib ai/gal = 358 g/L) .

c IN STRATA* = commercial standard without pigment (piopiconazole + fϊudioxinil + chlorothaloiiil).

d Pink snow mold site.

c (A + B + C): 123 g/100 m².

r (A + B + C): 151 g/100 m²,

A composition comprising A + B + C + D is the equivalent of INSTRATA* + a pigment. In other woi ds, using such a composition, a direct comparison can be made to demonstrate the superior effects of a composition containing the three classes of fungicides with a pigment vs. a composition BCS 09-6004

- 14 - containing only the three classes of fungicides (i e , without a pigment). The iesults show that in every site where the composition containing the three classes of fungicides with a pigment is used, the TQ and TC aie superior to INSTRATA*. This means that the turf recovers better and looks better using the composition containing the thice classes of fungicides with a pigment vs. INSTRATA*,

The results from site 9, in which a composition comprising two fungicides (A + B) and C show that the composition of two fungicides and a pigment is at least as good as INSTRATA*, if not slightly better. This is surprising because IN STRATA* has three fungicides (but no pigment). Li other words, an effect similar to using three fungicides can be achieved by the use of two fungicides and a pigment,

Table 2 shows the effect of a composition containing differing amounts of a QoI inhibitor fungicide (tiifloxystrobin), a contact fungicide (ipradione), a demethylation inhibitor (triticonazole) and a pigment (phthalocyanine Green pigment) in comparison with INSTRATA* on percentage disease infestation by site.

Table 2:

! Pink snow mold site

¹ (A + B + C): 123 g/100 m^z BCS 09-6004

- 15 - r (A + B + C): 151 g/l OO m²

The results in Table 2 show that the composition containing the three classes of fungicides with a pigment cures about the same percentage of disease infestation as INSTRATA*. In other words, the composition disclosed is as effective as INSTRATA* in killing mold. The supetior benefits of a composition additionally comprising a pigment, such as a phthalocyanine, include better recovery of the turf after the winter, during the spring green up; belter health of the turf; and better aesthetics (the turf looks visual better)

The Qoϊ inhibitor fungicide, contact fungicide, the demcthylation inhibitor; and the pigment may be In any ratio within the composition. Examples of suitable ratios are shown in Table 3,

Table 3:

^B the amount of the contact fungicide is kept constant as a icfeicnce point

Other exemplaty compositions of trifloxystrobin, ipiodionc, and phthalocyanine Green pigment include those shown in Table 4, suspended in watci .

Table 4:

BCS 09-6004

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Table 5 shows the superior effects of a composition containing 1,47 g/L of trifloxyslrobin, 29,41 g/L of iprodioπe, 3,14 g/L of ti iticonazole, and 6 g/L of phlhalocyaninc over a commercially available solution of INSTRATA* The four -component, composition and INSTRATA* weie applied to a bent grass/Poα plot at Westmounl Golf & Count! y Club in Kitchener, Ontario, Canada.

Table 5:

As the iesults show, application of the four "Component composition of trifloxyslrobin, iprodione, triticonazole, and phthalocyaninc is superior to INSTRAT A^®. Not only does the four-component composition provide better' disease control than INSTRATA* (as measured by the % area affected) - 0% vs. 2% but the TQ is better¹ 8,7 to 9 vs. 6,6, Additionally, excellent results can be achieved by using significantly lower amounts of the composition (100 mL/100 m² to 177,5 mL/nr) vs INSTRATA* (300 mL/m²).. This is significant not only from an environmental perspective in thai fewer chemicals are applied to the soil but also from an economic perspective in lower¹ costs,

Without being bound by theory, it is believed that the various fungicides act in synergy with the pigment, thereby resulting in the superior¹ effects observed.

Further¹ trials we;e carried out in Europe, data displayed in the following.

Trials were set up to investigate the efficacy and effect on turf qualitiy of the combination of two active ingredients (Trifloxystrobin, QoI inhibitor fungicide and Iprodione, contact fungicide) and (he pigment (Phthalocyanine). The fungicidal compounds wcie applied individually, in combination BCS 09-6004

- 17 -

(withoul Lhe pigment) and in combination including the pigment al two different concenttations. These tiealmcnts were compaied to commercial standaid products.

Trials were conducted in various places in UK and Germany in 2008 and were between end of .July to early December depending on the individual disease. Trial design was a randomized complete-block with 4 replications and a plot area of 4 to 6,25 m². Products were applied as spray application with 400 to 500 L water volume / ha. For application air pressurized sprayers witli a teejet or flatfan noozle were used, operated at 2,2 to 3,0 bar Two applications were caπicd out at 28 day interval.

Trials were evaluated in 14 to 28 day intervals up to 72 days after' the first application. Turf diseases: Pink snow mold (Microdσchium nivale), Rust (Puccinia spp), Red thread (Laetisω Ia fucifσrmis) were assessed as % infected canopy area per plot. Turf quality (color and / or density) was judged on an ordinal scale Data is displayed as average over all assessments.

Table 6 shows the effect of a composition containing differing amounts of a QoI inhibitor fungicide (ti ifloxystrobin), a contact fungicide (iprodione), and a pigment (phlhalocyanine Green pigment) in comparison with commercial standards which do not contain any pigments (DACONlL,, and AMlSTAR₅ both manufactured by SYNGENTA) on Turf Quality (TCP and/or' Turf Color (JC) . Data is displayed on a scale from 1 Io 9 with i = pool and 9 = excellent.

Table 6: TurfQuallily, Scale 1 to 9 with 1 = poor and 9 = excellent

BCS 09-6004

- 1!

" Sites: 1 UK, East Lothian; 2 UK, Middle Lothian; 3 Get many, south; 4 UK, Essex

A ~ tiifloxyslrobin; B = iproclione; C = Phthalocyanine Gtccn pigment (Green 7)

c DACONIL* = comma cial standard without pigment (chloiotlialonil)

Λ AJVIIST AR *= commercial standaid without pigment (azoxysti obin)

The data of table 6 shows an impiovemcnt of tuif quality in those plots whcie the the compounds A and B were combined with compound C The tieatmcnt with compounds A and B alone and the combination A + B achieved a lowci quality scoie than for A + B + C The results aie suppotted by the scoi es for the commercial standaid, which do not contain compound C and achieved lower scores as well

Table 7 shows the effect of a composition containing diffeiing amounts of a QoI inhibitor fungicide (tiifloxystrobin), a contact fungicide (iprodione) and a pigment (phthalocyanine Green pigment) in compaiison with DACONlL * or AMISTAR* on pcicentagc disease infestation by site

Table 7: % diseased area, Indication Puccinia spp on turf

BCS 09-6004

. 19 -

" Sites: 1 Germany, easl; 2 UK, Essex

The data in Table 7 shows that the combination of the compounds A + B + C achieved a better control of the tuif pathogen Puccinia spp than the combination of the compounds A + B only (without the pigment C) This effect was emphasized by the finding that the combination of compounds A + B + C outpes foimcd the combination A + B even at reduced ai concentration.

Claims

BCS 09-6004- 20 -Patent Claims:

1. Active compound combinations compi ising

A) at least one phthalocyanine pigment and

B) i) at least one QoI inhibitoi fungicide and

at least one fungicide selected fton the group consisting of

ii) a contact fungicide and

lit) a DMl-fungicidc.

2 Active compound combinations according to Claim 1 , wheie compound B) compiises i) ti ifloxystrobin as QoI inhibitor fungicide, ii) iprodiπe as contact fungicide and iii) triticonazole as DMl-fungicide

3. Active compound combinations according io Claims 1, wheic compound B) compiises i) trifioxystrobin as QoI inhibitoi fungicide and ii) ipiodione as contact fungicide

4 Active compound combinations accoiding to any of Claims 1 to 3, whcic compound A) is a green pigment (Green 7)

5 Active compound combinations accoiding to any oi Claims I Lo 4 which arc fungicidally active

6 Compositions comprising active compound combinations accoiding to any of Claims 1 to 5

7 Compositions accoiding to Claim 6, compi ising further auxiliaiics, solvents, caπicis, surfactants oi extenders

8 Method foi contolJing phytopathogenic fungi in tm f gsass pioteclion, characterized in that active compound combinations accoiding to any of Claims 1 to 5 oi compositions accoiding to Claim 6 oi 7 ate applied to tuif giass

9 Method for impioving turf quality after snow cover ielease in spring, characterized in that active compound combinations accoiding to any of Claims I to 5 oi compositions accoiding to Claim 6 oi 7 aie applied to tuif glass

10 Method according to Claim 8 or 9, chaiacteiized in that the active compounds A), Bi), Bii) and Biii) are applied simultaneously oi in succession BCS 09-6004

- 21 -

1 1 Method accoiding to any of Claims 8 to 10, chaiaclcrizcd in that in the treatment of lui f glass lϊom 100 to 10 000 g/ha are used.

12 Use of active compound combinations accoiding to any of Claims 1 to 5 ot of compositions according to Claim 6 or 7 foi conϋolling unwanted phytopathogenic fungi in tuif gsass protection,

13 Use of active compound combinations according to any of Claims 1 to 5 or of compositions accoiding to Claim 6 oi 7 for foi improving tuif quality after snow cover release in spring

14 Tuif grass ticated with active compound combinations accoiding to any of Claims 1 to 5 or with compositions accoiding to Claim 6 or 7