WO2002067679A1 - Fungicidal mixtures - Google Patents

Fungicidal mixtures Download PDF

Info

Publication number
WO2002067679A1
WO2002067679A1 PCT/EP2001/001823 EP0101823W WO02067679A1 WO 2002067679 A1 WO2002067679 A1 WO 2002067679A1 EP 0101823 W EP0101823 W EP 0101823W WO 02067679 A1 WO02067679 A1 WO 02067679A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
composition
formula
compound
biosynthesis inhibitor
Prior art date
Application number
PCT/EP2001/001823
Other languages
French (fr)
Inventor
Henry Van Tuyl Cotter
Gunter Reichert
Ewald Sieverding
Petrus Martinus Franciscus Emanuel Jegerings
Original Assignee
Basf Aktiengesellschaft
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Basf Aktiengesellschaft filed Critical Basf Aktiengesellschaft
Priority to PCT/EP2001/001823 priority Critical patent/WO2002067679A1/en
Publication of WO2002067679A1 publication Critical patent/WO2002067679A1/en

Links

Classifications

    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N35/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical
    • A01N35/04—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical containing aldehyde or keto groups, or thio analogues thereof, directly attached to an aromatic ring system, e.g. acetophenone; Derivatives thereof, e.g. acetals

Definitions

  • the present Invention relates to a fungicidal composition compri sing a fungicidally acceptable carrier and/or surface active agent and synergistically effective amounts of
  • R 1 represents Ci-C ⁇ -alkyl or Ci-Cg-haloalkyl
  • R 2 and R 4 each independently represent halogen or C ⁇ -C 2 -haloalkyl
  • R 3 is hydrogen, halogen, Ci ⁇ C 2 -haloal- kyl, C ⁇ -C 2 -alkoxy or C ⁇ -C 2 -haloalkoxy .
  • the fungicidal compound of formula I to be used according to the present invention is known for example from US-A 5,773,663 and EP-A 897 904.
  • the class of melanin biosynthesis inhibitors (MBI) (C) are chemical compounds which are capable of diminishing the in-vivo synthesis of melanin by inhibiting any of the reductase and/or dehy- dratase enzymes which are responsible for converting tetrahydro- xynaphthalene into dihydroxynaphthalene.
  • MBI melanin biosynthesis inhibitors
  • This class of compounds includes the following known compounds: carpropamid
  • fungicidal compounds of formula II to be used according to the present Invention are known for example from US patent US 5,593,996 and from International patent applications WO 98/46607 and WO 98/46608.
  • US 5,773,663 suggests to combine fungicidal benzophenone deriva- tives with other fungicides such as 4, 6-dinitro-o-cresol, benala - xyl, benomyl, captafol, captan, carbendazim, chlorothalonil, copper, cymoxanil, dichlofluanid, dichlone, difenoconazole, dimetho- morph, diniconzole, dinocap, dithianon, fenpiclonil, fenpropio- morph, hymaxazol, imazalil, iprodione, isoprothiolane, kasugamy- cin, mancozeb, mepronil, mercuric Oxide, oxadixyl, oxolinic acid, penconazole, propineb, pyrifenox, thiabendazole, thiram, tolclo- fos-
  • EE x+y-x»y/100 wherein x is the efficacy in % compared with an untreated control upon treatment with a fungicidal active ingredient A at a dose rate a; y is the efficacy in % compared with an untreated control upon- treatment with a fungicidal active ingredient B at a dose rate b; EE is the expected efficacy with a combination of fungicidal active ingredients A and B at a dose of a + b, respectively.
  • the present Invention includes a fungicidal composition
  • a fungicidal composition comprising an acceptable carrier and/or surface active agent and syner- gistically effective amounts of the compound of formula I, and at least one fungicidal active ingredient selected from the following the following groups (A) , (B) , (C) , (D) and (E) :
  • the present Invention also includes a method of controlling the growth of phytopathogenic fungi at a locus which comprises ap- plying synergistically effective amounts of at least one benzophenone of formula I and at least one fungicidally active ingredient selected from the following classes (A) , (B) , (C) , (D) and (E) as defined above to the locus.
  • Preferred ergosterol biosynthesis inhibiotors of group (A) are selected from the group consisting of fenarimol [ (R, S) -2, 4' -dich- loro-alpha- (pyrimidin-5-yl)benzhydrol alcohol], fenpropimorph t (R, S) cis-4- [3- (4-tertbutyl-phenyl) -2-methylpropyl] -2, 6-dimethyl- morpholine] , fenpropidine [ (R, S) -1- [3- [4- (1, 1-dimethylethyDphe- nyl] -2-methylpropyl]piperidine] , spiroxamine [8- (1, 1-dimethyle- thyl) -N-ethyl-N-propyl-1, 4-dioxaspiro-4 , 5-decane-2-methan-amine] and triforine [1, 1' -piperazine-1, 4-di
  • Another group of ergosterol biosynthesis inhibiotors are azole derivatives of formulae IIIA and IIIB,
  • E represents a linking group selected from the groups (a) , (b) , (c) , (d) and (e) :
  • X 1 represents a C ⁇ -C alkyl or an optionally substituted phenyl group
  • X 2 and X 3 each independently represent a hydrogen atom or a C ⁇ C alkyl group
  • X 4 represents an alkyl or cyclopropylalkyl group
  • X 5 represents a hydroxy or cyano group
  • X 6 represents an optionally substituted phenyl group
  • X 7 represents a halogen atom; q is 1, 2 or 3; and f is 0 or 2;
  • X 7 and q have the meaning given for formula IIIA
  • E represents a group of formula -N(X 8 ) - (CH 2 ) s -0-, in which X 8 represents a hydrogen atom or a C ⁇ C alkyl group and s is an integer from 1 to 6.
  • Particularly preferred azole derivatives of group (A) are selected from the group consisting of cyproconazole [2- (4-chlorphe- nyl) -3-cyclopropyl-l- (1H-1, 2 , 4-triazol-l-yl) butan-2-ol] , epoxico- josole [(2RS, 3SR) -1- [3- (2-chlorophenyl) -2- (4-fluorophenyl) oxi - ran-2-ylmethyl] -1H-1 , 2 , 4-triazole] , flusilazole [Bis (4-fluorophe- nyl)methyl (1H-1, 2, 4-triazol-l-ylmethyl) silane] , metconazole [IRS, 5RS;1RS,5SR) -5- (4-chlorobenzyl) -2 , 2-dimethyl-l- (1H-1 , 2 , 4-triazol-l-ylmethyl) cyclopen
  • Preferred strobilurine derivatives of group (B) are the compounds of formula IV,
  • W represents N or CH
  • B represents a -0-, -0CH-, -CH 0- or pyrimid-4 , 6-dioxydiyl- group;
  • R 12 represents a methyl group;
  • R 13 represents a methoxy or a methylamino group
  • R 14 represents a hydrogen or halogen atom or a cyano, a C ⁇ _ alkyl or a C ⁇ _ haloalkyl group
  • s is 0 , 1 or 2 ;
  • azoxystrobin [methyl (E) -2- (2- [6- (2-cyanophenoxy)py- rimidin-4-yloxy] phenyl) -3-methoxyacrylate] or kresoxim methyl [methyl- (E) -methoximino [alpha- (o-tolyloxy) -o-tolyl] acetate] .
  • Preferred melanin inhibitors of group (C) are selected from the group consisting of carpropamid [ (IR, 3S/1S, 3R) -2 , 2-dichloro- N- ( (R) -1- (4-chlorophenyl) ) -l-ethyl-3-methylcyclopropanecarboxa- mide] , chlobenthiazone, dichlocymet [N- (R) -1- (2 , 4 ,dichlorphe- nyl) ethyl) - (S) -2-cyano-3, 3-dimethylbutanamid] , pyroquilon [1,2,5, 6-tetrahydropyrrolo [3,2, 1-ij ] quinolin-4-one] , phthalide, tricyclazole [5-methyl-l, 2, 4-triazolo [3 , 4-b] benzothiazole] and certain phenoxyamides , which are known for example from Japanese patent application JP 5-9165-A and
  • Preferred compounds of group (D) are selected from the group consisting of acibenzolar (BION) [benzo (1, 2, 3) thiadiazole-7-carbon- saure thio-methylester] , cyprodinil [N- (4-cyclopropyl-6-methyl- pyrimidin-2yl) -aniline] , dodine [1-dodecylguanidinium acetate], ethirimol [5-butyl-2-ethylamino-4-hydroxy-6-methylpyridine] , famo- xadone [3-anilino-5-methyl-5- (4-phenoxypheny1) -1, 3-oxazoli - dine-2, 4 , dione] , fenpiclonil [4- (2, 3-dichlorophenyl)pyr- role-3-carbonitrile] , fluazinam [3-chloro-N- [3-chloro-2, 6 , dini- tro-4- (
  • Preferred triazolopyrimidines of group (E) are the compounds of
  • R 2 represents a fluorine atom
  • R 3 represents a hydrogen or fluorine atom
  • R 4 represents a fluorine or chlorine atom.
  • compositions of three active ingredients which comprise one compound of formula I and two different compounds selected from the groups (A) , (B) , (C) , (D) and (E) , preferably one strobilurine compound selected from group (B) and one ergosterol biosynthesis inhibitor of group (A) , in particular kresoxim-methyl and epoxiconazole or kresoxim-methyl and fenpropimorph.
  • compositions comprising one compound of formula I and two different compounds of group (D) , in particular dimethomorph [(E,Z) 4- [3- (4-chlorophenyl) -3 , 4-dimethoxyphenyl) -acroloyl] -morpholine] and mancozeb
  • co-formulations comprising the following constituents :
  • a carrier for the benzophenone of formula I; - at least one compound selected from the classes (A) through (E) as defined above; optionally an adjuvant selected from the group consisting of polyalkoxylated alcohols, triglycerides and amines, in particular Synperonic 91-6, which is commercially available from Uniqema, formerly ICI Surfactants; optionally a foam breaking agent.
  • an adjuvant selected from the group consisting of polyalkoxylated alcohols, triglycerides and amines, in particular Synperonic 91-6, which is commercially available from Uniqema, formerly ICI Surfactants; optionally a foam breaking agent.
  • the compound of formula I and the compound selected from the classes (A) through (E) as defined above are to be applied toge- ther, in synergistically effective amounts. These synergistic mixtures exhibit an extraordinary efficacy against a broad range of phytopathogenic fungi, in particular against fungi from the classes ascomycetes, basidiomycetes,oomycetes and deuteromycetes .
  • the mixture according to the Invention may be preferably applied for controlling phytopathogenic fungi of the genera: Achlya, Al ternaria, Balansia, Bipolaris, Blumeria, Botrytis, Cer ⁇ cospora, Cochlioholus, Curvularia, Cylindrocladium, Drechslera, Entyloma, Erysiphe, Fusarium, Gaeumannomyces , Gerlachia, Gibbe - rella, Guignardia, Leptosphaeria, Magnaporthe, Mucor, Mycosphae - rella, Myrofcheciuin, Nigrospora, Peronospora, Phoma, Pseudopero- nospora, Pseudocercosporella, Phytophthora, Puc
  • the mixtures according to the Invention are in particular applied for controlling the above phytopathogenic fungi on monocotylydo- neous plants, such as barley and wheat, rice and turf grases or fruit crops such as pomefruits, stonefruits and vines as well as all kinds of vegetables and ornamentals.
  • the application rate of the compound of formula I according to this invention is usually in the range of 1 to 2000 grams of active ingredient (g a.i.) per hectare (ha), with rates between 20-500 g a.i. /ha often achieving satisfactory control.
  • the opti- mal rate for a specific application will depend on the crop(s) under cultivation and the predominant species of infesting fungi, and readily may be determined by established biological tests known to those skilled in the art.
  • the preferred application rate of the compound of formula I is in the range of 10 to 500 g a.i. /ha, preferably 20-300 g a.i. /ha.
  • the optimal rate for the compound of group (b) including the classes (A) through (E) will, however, depend an the crop(s) under cultivation and the level of infestation by the fungus, and can readily be determined by established biological tests.
  • the ratio (by weight) of the compound of formula I to the fungi - cidal active ingredient of the classes (A) through (E) as defined above is as a rule, from 100 : 1 to 1 : 100.
  • the preferred ratio formula I : (A) through (E) may vary, e.g., from about 10 : 1 to about 1 : 10, in particular from about 5 : 1 to about 1 : 5, most preferred from 2 : 1 to 1 : 2.
  • the preferred relative ratios (by weight) are as follows: compound of formula I: 200 to 1, preferably 20 to 1;
  • 1 st compound of (A) to (E) 1 to 100, preferably 1 to 10;
  • 2nd compound of (A) to (E) 1 to 100, preferably 1 to 10.
  • the active compounds can be corformulated together in a suitable ratio according to the present invention, together with usual carriers or diluents and/or additives known in the art.
  • the invention further provides a fungicidal composition which comprises a carrier and, as active ingredient, at least one compound of formula I as defined above and at least one fungicidal active ingredient selected from the classes (A) through (E) as defined above.
  • a method of making such a composition is also provided which com- prises bringing the compound of formula I and the fungicidal active ingredient selected from the classes (A) through (E) as defined above into association with at least one carrier. It is also envisaged that different isomers or mixtures of isomers of the fungicidal active ingredient selected from the classes (A) through (E) may have different levels or spectra of activity and thus compositions may comprise individual isomers or mixtures of isomers .
  • a composition according to the invention preferably contains from 0.1 % to 99.9%, preferably 0.2 to 80 % by weight (w/w) of active ingredients .
  • a carrier in a composition according to the invention is any material with which the active ingredient is formulated to facili- tate application to the locus to be treated, which may for example be a plant, seed, foliage, soil, or into the water where the plant grow, or to the roots or to facilitate storage, transport or handling.
  • a carrier may be a solid or a liquid, including material which is normally a gas but which has been compressed to form a liquid.
  • compositions may be manufactured into e.g. emulsion concentrates, solutions, oil in water emulsions, wettable powders, soluble powders, suspension concentrates, dusts, granules, water dispersible granules, tablets, micro-capsules, gels and other formulation types by well established procedures. These procedures include intensive mixing and/or milling of the active ingre- hi-ients with other substances, such as fillers, solvents, solid carriers, surface active compounds (surfactants), and optionally solid and/or liquid auxilaries and/or adjuvants.
  • the form of application such as spraying, atomizing, dispersing or pouring may be chosen like the compositions according to the desired objectives and the given circumstances.
  • Solvents may be aromatic hydrocarbons, e.g. Solvesso[ 200, substituted naphthalenes, phthalic acid esters, such as dibutyl or dioctyl phthalate, aliphatic hydrocarbons, e.g. cyclohexane or paraffins, alcohols and glycols as well as their ethers and esters, e.g. ethanol, ethyleneglycol mono- and dimethyl ether, ketones such as cyclohexanone, strongly polar solvents such as N-methyl-2-pyrrolidone, or ⁇ -butyrolactone, higher N-alkylpyrrolidones, e.g.
  • aromatic hydrocarbons e.g. Solvesso[ 200, substituted naphthalenes, phthalic acid esters, such as dibutyl or dioctyl phthalate
  • aliphatic hydrocarbons e.g. cyclohexane or paraffins
  • N-octylpyrrolidone or N-cyclohexylpyr- rolidone epoxidized plant oil esters, e.g. methylated coconut or soybean oil ester and water. Mixtures of different liquids are often suitable.
  • Solid carriers which may be used for dusts, wettable powders, water dispersible granules, or granules, may be mineral fillers, such as calcite, talc, kaolin, montmorillonite or attapulgite or others. The physical properties may be improved by addition of highly dispersed silica gel or polymers. Carriers for granules may be porous material, e.g. pumice, kaolin, sepiolite, bento- nite; non-sorptive carriers may be calcite or sand or others. Additionally, a multitude of pre-granulated inorganic or organic materials may be used, such as dolomite or crushed plant residues .
  • Pesticidal compositions are often formulated and transported in a concentrated form which is subsequently diluted by the user before application.
  • a carrier which is a surfactant facilitates this process of dilution.
  • at least one carrier in a composition according to the invention is a surfactant.
  • the composition may contain at two or more carriers, at least one of which is a surfactant.
  • Surfactants may be nonionic, anionic, cationic or zwitterionic substances with good dispersing, emulsifying and wetting properties. Surfactants may also mean mixtures of individual surfactants .
  • compositions of the invention may for example be formulated as wettable powders, water dispersible granules, dusts, granules, solutions, emulsifiable concentrates, emulsions, suspension con- centrates and aerosols.
  • Wettable powders usually contain 5 to 90% w/w of active ingredient and usually contain in addition to solid inert carrier, 3 to 10% w/w of dispersing and wetting agents and, where necessary, 0 to 10% w/w of stabilizer (s) and/or other addi- tives such as penetrants or stickers.
  • Dusts are usually formula ⁇ ted as a dust concentrate having a similar composition to that of a wettable powder but without a dispersant, and may be diluted in the field with further solid carrier to give a composition usually containing 0.5 to 10% w/w of active ingredient.
  • Water dispersible granules and granules are usually prepared to have a size between 0.15 mm and 2.0 mm and may be manufactured by a variety of techniques. Generally, these types of granules will contain 0.5 to 90% w/w active ingredient and 0 to 20% w/w of additives such as stabilizer, surfactants, slow release modifiers and binding agents.
  • Emulsifiable concentrates consist of relatively small granules having a relatively high concentration of ac ⁇ tive ingredient.
  • Emulsifiable concentrates usually contain, in addition to a solvent or a mixture of solvents, 1 to 80% w/v active ingredient, 2 to 20% w/v emulsifiers and 0 to 20% w/v of other additives such as stabilizers, penetrants and corrosion inhibitors.
  • Suspension concentrates are usually milled so as to obtain a stable, non-sedimenting flowable product and usually contain 5 to 75% w/v active ingredient, 0.5 to 15% w/v of dispersing agents, 0.1 to 10% w/v of suspending agents such as protective colloids and thixotropic agents, 0 to 10% w/v of other additives such as defoamers, corrosion inhibitors, stabilizers, penetrants and stickers, and water or an organic liquid in which the active ingredient is substantially insoluble; certain organic solids or inorganic salts may be present dissolved in the formulation to assist in preventing sedimentation and crystalization or as antifreeze agents for water.
  • Aqueous dispersions and emulsions for example compositions obtained by diluting the formulated product according to the inven- tion with water, also lie within the scope of the invention.
  • the biological activity of the active ingredient can also be increased by including an adjuvant in the formulation or the spray dilution.
  • An adjuvant is defined here as a substance which can increase the biological activity of an active ingredient but is not itself significantly biologically active.
  • the adjuvant can either be included in the formulation as a coformulant or car- rier, or can be added to the spray tank together with the formulation containing the active ingredient.
  • compositions may preferably be in a concentra- ted form whereas the end user generally employs diluted compositions.
  • the compositions may be diluted to a concentration down to 0.001 % of active ingredient.
  • the doses usually are in the range from 0.01 to 10 kg a.i. /ha.
  • SC-I 2 active ingredient compound I 100.0 g Dispersing agent Soprophort FL 3) 30.0 g Antifoaming agent Rhodorsilt 426R 3) 1.5 g
  • SC-A-E active ingredient fungicide selected from classes 200.0 g
  • the formulation SC-A-E comprising a compound selected from the classes (A) through (E) is in-tank mixed with any of the other formulations SC-I 2, SC-I 3, or DC-I which comprise compound I.
  • the active ingredients are added to the tank mix together each as solo formulation.
  • the present Invention relates to a kit for the preparation of a spray mixture consisting of two separate contain- ments :
  • a containment which comprises at least one benzophenone I, conventional carriers and optionally adjuvants;
  • a containment which comprises at least one active ingredient selected from the classes (A) through (E) .
  • the said kit will consist of two bottles with dispensing means which allow the easy and correct addition of the active ingredients (a) and (b) to the tank mix.
  • the formulation SC-I + A-E comprising benzophenone I and a fungicidal active ingredient selected from the classes (A) through (E) as defined above can be used directly for preparing the tank mix according to the present invention.
  • a composition according to the invention preferably contains from 0.5% to 95% by weight of active ingredients.
  • compositions may preferably be in a concentrated form whereas the end-user generally employs diluted compositions.
  • the compositions may be diluted down to a concentration of 0.0001 % of active ingredients.
  • compositions of this invention can be applied to the plants or their environment simultaneous with or in succession with other active substances.
  • active substances can be either fertilizers, agents which donate trace elements or other preparations which influence plant growth.
  • they can also be other fungicides, selective herbicides, insecticides, bacteri- cides, nematicides, algicides, molluscidides, rodenticides , viru- cides, compounds inducing resistance into plants, biological control agents such as viruses, bacteria, nematodes, fungi and other microorganisms, repellents of birds and animals, and plant growth regulators, or mixtures of several of these preparations, if appropriate together with other carrier substances conventionally used in the art of formulation, surfactants or other addi - tives which promote application.
  • insecticidal compounds are alpha-cypermethrin, benfu- racarb, BPMC, buprofezine, carbosulfan, cartap, chlorfenvinphos , chlorpyrifos-methyl, cycloprothrin, cypermethrin, esfenvalerate, ethofenprox, fenpropathrin, flucythrinate, flufenoxuron, hydrame- thylnon, imidacloprid, isoxathion, MEP, MPP, nitenpyram, PAP, permethrin, propaphos, pymetrozine, silafluofen, tebufenozide, teflubenzuron, temephos, terbufos, tetrachlorvinphos and triaza- mate.
  • biological control agents are: Bacillus thuringien- sis, Verticillium lecanu, Aufographica califomica NPV, Beauvaria bassiana, Ampelomyces quisqualis, Bacilis subtilis, Pseudomonas cholororaphis, Pseudomonas fluorescens, Steptomyces grtseoviridis and Trichoderma harzianum.
  • Examples of chemical agents that induce systemic acquired resistance in plants such are: isonicotinic acid or derivatives thereof, 2, 2-dichloro-3 , 3-dimethylcyclopropylcarboxylic acid.
  • the present Invention is of wide applicability in the protection of crops, trees, residential and ornamental plants against fungal attack.
  • Preferred crops are cereals, such as wheat and barley, rice as well as mecanics and apples.
  • the duration of the protection is normally dependent an the individual compound selected, and also a variety of external factors, such as climate, whose impact is normally mitigated by the use of a suitable formulation.
  • the trials are carried out under greenhouse conditions in residual or curative applications.
  • the fungicides are applied in single treatments, or in a combination comprising a benzophenone I and a compound selected from the classes (A) through (E) as defined above.
  • the compounds are applied in form of an aqueous spray mix obtained from concentrated formulation or the technical material .
  • Seed is planted in 6 cm diameter plastic pots and maintained in the greenhouse.
  • test compounds are sprayed with a three nozzle overhead fungicide sprayer to near run-off.
  • a single nozzle overhead track sprayer is used for application of the compounds to cereals at a rate of 200 1/ha. Plants are then allowed to air-dry.
  • Inoculation precedes treatment in the case of curative evaluations and follows treatment in case of residual evaluations.
  • plants are set up on greenhouse benches with bottom watering mats and inoculated by dusting them with conidia from infected plants. Between inoculation and treatment for curative evaluations and between treatment and inoculation for residual evaluations, plants are maintained in the greenhouse with bottom watering.
  • an aqueous spore suspension of the pathogen is applied to the plant and the plants are kept 1-2 days in a moist infection chamber before being returned to the greenhouse where they are maintained by bottom watering.
  • disease in treated plants disease control 100- x 100% disease in untreated plants
  • Technical compounds are formulated in a solvent/surfactant system consisting of 5% acetone and 0.05% Tween 20 in deioni- zed water. Compounds are dissolved in acetone prior to addition of the water; the Tween 20 can be added through either the acetone or the water. Dilutions are made using the solvent/surf ctant system. Formulated compounds are prepared using deionized water.
  • Apples (Malus X domestica Borkh.) variety "Golden Delicious” are disinfected by washing them briefly in 70 % ethanol. After drying the apples are marked with four short equal-distant lines indicating the positions to be wounded.
  • the tank mixes were obtained from technical material of I and different formulations of different active ingredients.
  • the active ingredients, the type of formulations, the observed and expected efficacies with different rates are given in Table II:
  • the tank mixes were obtained from technical material of I and different formulations of different active ingredients.
  • the ac- 5 tive ingredients, the type of formulations, the observed and ex ⁇ pected efficacies with different rates are given in Table V:
  • the tank mixes were obtained from technical material of I and different formulations of different active ingredients.
  • the active ingredients, the type of formulations, the observed and expected efficacies with different rates are given in Table VI:
  • the tank mixes were obtained from technical material of I and different formulations of different active ingredients.
  • the active ingredients, the type of formulations, the observed and expected efficacies with different rates are given in Table VIII:
  • the tank mixes were obtained from technical material of I and different formulations of different active ingredients.
  • the active ingredients, the type of formulations, the observed and expected efficacies with different rates are given in Table IX:
  • the tank mixes were obtained from technical material of I and different formulations of different active ingredients.
  • the active ingredients, the type of formulations, the observed and expected efficacies with different rates are given in Table X:
  • the tank mixes were obtained from technical material of I and different formulations of different active ingredients.
  • the active ingredients, the type of formulations, the observed and expected efficacies with different rates are given in Table XI: Table XI
  • the tank mixes were obtained from technical material of I and AP-4.
  • the active ingredients, the type of formulations, the observed and expected efficacies with different rates are given in Table XIII:

Abstract

The invention relates to a novel fungicidal composition comprising a fungicidally acceptable carrier and/or surface active agent together with, and synergistically effective amounts of (a) a benzophenone of formula (I) and (b) at least one fungicidally active ingredient selected from groups (A), (B), (C), (D) and (E): (A) an ergosterol biosynthesis inhibitor; (B) a strobilurine derivative; (C) a melanin biosynthesis inhibitor; (D) a compound selected from the group consisting of acibenzolar, benomyl, captan, carboxin, chlorothalonil, copper, cyprodinil, dinocap, dithianon, dimethomorph, dodine, ethirimol, famoxadone, fenpiclonil, fluazinam, mancozeb, metalaxyl, pyrifenox, sulfur, vinclozolin; and (E) a triazolopyrimidine of formula (II), in which R1 represents C¿1?-C6-alkyl or C1-C6-haloalkyl, and R?2 and R4¿ each independently represents halogen or C¿1?-C2-haloalkyl and R?3¿ is hydrogen, halogen or C¿1?-C2-haloalkyl, C1-C2-alkoxy or C1-C2-haloalkoxy, and to a method of controlling the growth of phytopathogenic fungi at a locus which comprises applying synergistically effective amounts of (a) at least one benzophenones of formula (I) and (b) at least one fungicidal active ingredient selected from the groups (A), (B), (C), (D) and (E) to the locus.

Description

FUNGICIDAL MIXTURES
The present Invention relates to a fungicidal composition compri sing a fungicidally acceptable carrier and/or surface active agent and synergistically effective amounts of
(a) the benzophenone of formula I and
Figure imgf000002_0001
(b) at least one fungicidally active ingredient selected from the following groups (A) , (B) , (C) , (D) and (E) :
(A) an ergosterol biosynthesis inhibitor;
(B) a strobilurine derivative;
(C) a melanin biosynthesis inhibitor;
(D) a compound selected from the group consisting of acibenzolar, benomyl, captan, carboxin, chlorothalonil , copper, cyprodinil, dinocap, dithianon, dimethomorph, do- dine, ethirimol, famoxadone, fenpiclonil, fluazinam, man- cozeb, metalaxyl, pyrifenox, sulfur, vinclozolin; and
(E) a triazolopyrimidine of formula II,
Figure imgf000002_0002
in which R1 represents Ci-Cβ-alkyl or Ci-Cg-haloalkyl, and R2 and R4 each independently represent halogen or Cχ-C2-haloalkyl and R3 is hydrogen, halogen, Ci~C2-haloal- kyl, Cι-C2-alkoxy or Cι-C2-haloalkoxy .
The fungicidal compound of formula I to be used according to the present invention is known for example from US-A 5,773,663 and EP-A 897 904.
The compounds of the classes (A) , (B) and (D) are known from The Pes ticide Manual 11th. edition 1997, Editor Clive Tomlin.
The class of melanin biosynthesis inhibitors (MBI) (C) are chemical compounds which are capable of diminishing the in-vivo synthesis of melanin by inhibiting any of the reductase and/or dehy- dratase enzymes which are responsible for converting tetrahydro- xynaphthalene into dihydroxynaphthalene. This class of compounds includes the following known compounds: carpropamid
[ (1R,3S/1S,3R) -2,2-dichloro-N-( (R) -1- (4-chlorophenyl) )-l-ethyl- 3-methylcyclopropanecarboxamide] , chlobenthiazone, dichlocymet [N- (R) -1- (2,4,dichlorphenyl) ethyl) - (S) -2-cyano-3 , 3-dimethylbuta- namid] , pyroquilon [1, 2 , 5, 6-tetrahydropyrrolo [3 , 2, 1-ij] quino- lin-4-one] , phthalide, tricyclazole [5-methyl-l, 2, 4-tria- zolo [3, 4-b]benzothiazole] and certain phenoxya ides , which are known for example from Japanese patent application JP 5-9165-A and from EP-A 262 393, in particular the mixture of (2R)- and
(2R/S) -N- (1-cyano-l, 2-dimethyl-propyl) -2- (2 , 4-dichlorophe- noxy) -propionamide named fenoxanil.
The fungicidal compounds of formula II to be used according to the present Invention are known for example from US patent US 5,593,996 and from International patent applications WO 98/46607 and WO 98/46608.
US 5,773,663 suggests to combine fungicidal benzophenone deriva- tives with other fungicides such as 4, 6-dinitro-o-cresol, benala - xyl, benomyl, captafol, captan, carbendazim, chlorothalonil, copper, cymoxanil, dichlofluanid, dichlone, difenoconazole, dimetho- morph, diniconzole, dinocap, dithianon, fenpiclonil, fenpropio- morph, hymaxazol, imazalil, iprodione, isoprothiolane, kasugamy- cin, mancozeb, mepronil, mercuric Oxide, oxadixyl, oxolinic acid, penconazole, propineb, pyrifenox, thiabendazole, thiram, tolclo- fos-methyl, triadimefon, triflumizole, triforine validamycin A, vinclozolin, zineb and ziram.
However, there is no hint that such mixtures show synergistic effects and can advantageously be used for controlling diseases such as wheat powdery mildew, wheat leaf rust and wheat Septoria leaf blotch, Botrytis diseases and others.
Synergistic mixtures of certain benzophenone derivatives as 3-bromo-2 ' , 6-dimethyl-2 , 4 ' , 5 ' , 6 ' -tetramethoxybenzophenone are disclosed in EP-A 1 023 834.
Surprisingly, a strong synergy between the compound of formula I and the fungicidally active ingredients selected from the classes (A) , (B) , (C) , (D) and (E) as described above in greenhouse and field trials was found when these two compounds were in-tank mixed and when the activity of these mixtures was compared with that of the solo activity of each active ingredient. A mixture of fungicides shows synergistic effect if the fungici¬ dal activity of the mixture is larger than the sum of activities of the separately applied compounds. The expected fungicidal ac¬ tivity for a given mixture of two fungicides can also be calcula- ted as follows (See Colby. S.R., "Calculating synergistic and antagonistic response of herbicide combinations", Weeds 15, pp 20-22 (1967) :
EE = x+y-x»y/100 wherein x is the efficacy in % compared with an untreated control upon treatment with a fungicidal active ingredient A at a dose rate a; y is the efficacy in % compared with an untreated control upon- treatment with a fungicidal active ingredient B at a dose rate b; EE is the expected efficacy with a combination of fungicidal active ingredients A and B at a dose of a + b, respectively.
If the actual efficacy (E) exceeds the expected (calculated) one (EE) , the mixture displays a synergistic effect.
The present Invention includes a fungicidal composition comprising an acceptable carrier and/or surface active agent and syner- gistically effective amounts of the compound of formula I, and at least one fungicidal active ingredient selected from the following the following groups (A) , (B) , (C) , (D) and (E) :
(A) an ergosterol biosynthesis inhibitor;
(B) a strobilurine derivative, (C) a melanin biosynthesis inhibitor,
(D) a compound selected from the group consisting of acibenzolar
(BION) , benomyl, captan, carboxin, chlorothalonil, copper, cyprodinil, dinocap, dithianon, dimethomorph, dodine, ethiri- mol, famoxadone, fenpiclonil, fluazinam, mancozeb, metalaxyl , pyrifenox, sulfur and vinclozolin, and
(E) an azolopyrimidine of formula II.
The present Invention also includes a method of controlling the growth of phytopathogenic fungi at a locus which comprises ap- plying synergistically effective amounts of at least one benzophenone of formula I and at least one fungicidally active ingredient selected from the following classes (A) , (B) , (C) , (D) and (E) as defined above to the locus.
Preferred ergosterol biosynthesis inhibiotors of group (A) are selected from the group consisting of fenarimol [ (R, S) -2, 4' -dich- loro-alpha- (pyrimidin-5-yl)benzhydrol alcohol], fenpropimorph t (R, S) cis-4- [3- (4-tertbutyl-phenyl) -2-methylpropyl] -2, 6-dimethyl- morpholine] , fenpropidine [ (R, S) -1- [3- [4- (1, 1-dimethylethyDphe- nyl] -2-methylpropyl]piperidine] , spiroxamine [8- (1, 1-dimethyle- thyl) -N-ethyl-N-propyl-1, 4-dioxaspiro-4 , 5-decane-2-methan-amine] and triforine [1, 1' -piperazine-1, 4-diyl-di- [N- (2 , 2 , 2-trichlore- thyl) formamide] .
Another group of ergosterol biosynthesis inhibiotors are azole derivatives of formulae IIIA and IIIB,
Figure imgf000005_0001
wherein E represents a linking group selected from the groups (a) , (b) , (c) , (d) and (e) :
Figure imgf000005_0002
(a) (b) (c)
Figure imgf000005_0003
<d> (e) in which X1 represents a Cχ-C alkyl or an optionally substituted phenyl group; X2 and X3 each independently represent a hydrogen atom or a Cι~C alkyl group; X4 represents an alkyl or cyclopropylalkyl group; X5 represents a hydroxy or cyano group;
X6 represents an optionally substituted phenyl group;
X7 represents a halogen atom; q is 1, 2 or 3; and f is 0 or 2;
Figure imgf000006_0001
wherein X7 and q have the meaning given for formula IIIA, and E represents a group of formula -N(X8) - (CH2) s-0-, in which X8 represents a hydrogen atom or a Cι~C alkyl group and s is an integer from 1 to 6.
Particularly preferred azole derivatives of group (A) are selected from the group consisting of cyproconazole [2- (4-chlorphe- nyl) -3-cyclopropyl-l- (1H-1, 2 , 4-triazol-l-yl) butan-2-ol] , epoxico- nazole [(2RS, 3SR) -1- [3- (2-chlorophenyl) -2- (4-fluorophenyl) oxi - ran-2-ylmethyl] -1H-1 , 2 , 4-triazole] , flusilazole [Bis (4-fluorophe- nyl)methyl (1H-1, 2, 4-triazol-l-ylmethyl) silane] , metconazole [IRS, 5RS;1RS,5SR) -5- (4-chlorobenzyl) -2 , 2-dimethyl-l- (1H-1 , 2 , 4-triazol-l-ylmethyl) cyclopentanol] , myclobutanil [2- (4-chlorophe- nyl) -2- (1H-1, 2 , 4-triazol-l-ylmethyl) hexanenitrile] , penconazole
[1- (2 , 4-dichloro-beta-propylphenetyl) -1H-1, 2, 4-triazole] , proch- loraz [1-N-propyl-N- [2- (2,4, 6-trichlorophenoxy) ethyl] carbamoyli - midazole] , propiconazole [ (R, S) -1- [2- (2 , 4-dichlorophenyl) -4-pro- pyl-1, 3-dioxolan-2-ylmethyl] -1H-1, 2 , 4-triazole] , tebuconazole
[ (R, S) alpha-2- (4-chlorophenyl) ethyl-alpha- (1, 1-dimethyle- thyl) -1H-1, 2 , 4-triazol-l-ethanol] , triadimefon [1- (4-chlorophe- noxy) -3 , 3-dimethyl-l- (1H-1, 2 , 4-triazol-l-yl) butanone] and triadi- menol [1- (4-chlorophenoxy) -3, 3-dimethyl-l- (1H-1, 2, 4-tria- zol-l-yl)butan-2-ol] . Most preferred are epoxiconazole, metconazole, myclobutanil and prochloraz .
Preferred strobilurine derivatives of group (B) are the compounds of formula IV,
Figure imgf000006_0002
wherein
W represents N or CH;
B represents a -0-, -0CH-, -CH 0- or pyrimid-4 , 6-dioxydiyl- group; R12 represents a methyl group;
R13 represents a methoxy or a methylamino group; R14 represents a hydrogen or halogen atom or a cyano, a Cι_ alkyl or a Cι_ haloalkyl group; and s is 0 , 1 or 2 ;
in particular azoxystrobin [methyl (E) -2- (2- [6- (2-cyanophenoxy)py- rimidin-4-yloxy] phenyl) -3-methoxyacrylate] or kresoxim methyl [methyl- (E) -methoximino [alpha- (o-tolyloxy) -o-tolyl] acetate] .
Preferred melanin inhibitors of group (C) are selected from the group consisting of carpropamid [ (IR, 3S/1S, 3R) -2 , 2-dichloro- N- ( (R) -1- (4-chlorophenyl) ) -l-ethyl-3-methylcyclopropanecarboxa- mide] , chlobenthiazone, dichlocymet [N- (R) -1- (2 , 4 ,dichlorphe- nyl) ethyl) - (S) -2-cyano-3, 3-dimethylbutanamid] , pyroquilon [1,2,5, 6-tetrahydropyrrolo [3,2, 1-ij ] quinolin-4-one] , phthalide, tricyclazole [5-methyl-l, 2, 4-triazolo [3 , 4-b] benzothiazole] and certain phenoxyamides , which are known for example from Japanese patent application JP 5-9165-A and from EP-A 262 393, in particular the mixture of (2R)- and (2R/S) -N- (1-cyano-l, 2-dimethyl-pro- pyl) -2- (2 , 4-dichlorophenoxy) -propionamide named fenoxanil.
Preferred compounds of group (D) are selected from the group consisting of acibenzolar (BION) [benzo (1, 2, 3) thiadiazole-7-carbon- saure thio-methylester] , cyprodinil [N- (4-cyclopropyl-6-methyl- pyrimidin-2yl) -aniline] , dodine [1-dodecylguanidinium acetate], ethirimol [5-butyl-2-ethylamino-4-hydroxy-6-methylpyridine] , famo- xadone [3-anilino-5-methyl-5- (4-phenoxypheny1) -1, 3-oxazoli - dine-2, 4 , dione] , fenpiclonil [4- (2, 3-dichlorophenyl)pyr- role-3-carbonitrile] , fluazinam [3-chloro-N- [3-chloro-2, 6 , dini- tro-4- (trifluoromethyl) -phenyl] -5- ( trifluoromethyl) -2-pyridina- mine] , mancozeb [manganese ethylenebis (dithiocarbamate) (polyme- ric) complex with Zinc salt] and metalaxyl [methyl N- (2-methoxya- cetyl)-N- (2,6-xylyl) -DL-alaninate] .
Preferred triazolopyrimidines of group (E) are the compounds of
Figure imgf000007_0001
wherein R2 represents a fluorine atom;
R3 represents a hydrogen or fluorine atom; R4 represents a fluorine or chlorine atom.
Particularly preferred are the azolopyrimidines of formula II se- lected from the group consisting of 5-chloro-6- (2-chloro-6- fluorophenyl) -7- (2,2, 2-trifluoroethylamino) -[1,2,4] tria- zolo [1, 5-a]pyrimidine coded AP-3 and 5-chloro-6- (2, 4 , 6-trifluoro- phenyl) -7- [2- (1, 1, 1-trifluoro)propylamino] - [1,2,4] triazolo- [1, 5-a] pyrimidine coded AP-4 , most preferred is AP-4.
A particularly preferred embodiment of this invention are compositions of three active ingredients which comprise one compound of formula I and two different compounds selected from the groups (A) , (B) , (C) , (D) and (E) , preferably one strobilurine compound selected from group (B) and one ergosterol biosynthesis inhibitor of group (A) , in particular kresoxim-methyl and epoxiconazole or kresoxim-methyl and fenpropimorph.
Another particularly preferred embodiment of the invention are compositions comprising one compound of formula I and two different compounds of group (D) , in particular dimethomorph [(E,Z) 4- [3- (4-chlorophenyl) -3 , 4-dimethoxyphenyl) -acroloyl] -morpholine] and mancozeb
Preferred are co-formulations, comprising the following constituents :
a carrier; the benzophenone of formula I; - at least one compound selected from the classes (A) through (E) as defined above; optionally an adjuvant selected from the group consisting of polyalkoxylated alcohols, triglycerides and amines, in particular Synperonic 91-6, which is commercially available from Uniqema, formerly ICI Surfactants; optionally a foam breaking agent.
The compound of formula I and the compound selected from the classes (A) through (E) as defined above are to be applied toge- ther, in synergistically effective amounts. These synergistic mixtures exhibit an extraordinary efficacy against a broad range of phytopathogenic fungi, in particular against fungi from the classes ascomycetes, basidiomycetes,oomycetes and deuteromycetes .
Therefore, they can be applied advantageously against a broad range of diseases in different crops. They may be applied as leaf, stem, root, into-water, seed dressing, nursery box or soil fungicides . The mixture according to the Invention may be preferably applied for controlling phytopathogenic fungi of the genera: Achlya, Al ternaria, Balansia, Bipolaris, Blumeria, Botrytis, Cer¬ cospora, Cochlioholus, Curvularia, Cylindrocladium, Drechslera, Entyloma, Erysiphe, Fusarium, Gaeumannomyces , Gerlachia, Gibbe - rella, Guignardia, Leptosphaeria, Magnaporthe, Mucor, Mycosphae - rella, Myrofcheciuin, Nigrospora, Peronospora, Phoma, Pseudopero- nospora, Pseudocercosporella, Phytophthora, Puccinia, Pyreno - phora, Pyricularia, Pythium, Rhizoctonia, Rhizopus, Rhynchospo - riu , Sarocladium, Sclerophthora, Sclerotium, Septoria, Tilletia, Uncinula, Us tilago, Ustilaginoidea, and Ven turia, in particular the species Blumeria graminis f.sp. tri tici , Cercospora beticola, Septoria tri tici , Erysiphe cichoracearum, Puccinia recondi ta and Pyrenophora teres .
The mixtures according to the Invention are in particular applied for controlling the above phytopathogenic fungi on monocotylydo- neous plants, such as barley and wheat, rice and turf grases or fruit crops such as pomefruits, stonefruits and vines as well as all kinds of vegetables and ornamentals.
The application rate of the compound of formula I according to this invention is usually in the range of 1 to 2000 grams of active ingredient (g a.i.) per hectare (ha), with rates between 20-500 g a.i. /ha often achieving satisfactory control. The opti- mal rate for a specific application will depend on the crop(s) under cultivation and the predominant species of infesting fungi, and readily may be determined by established biological tests known to those skilled in the art.
In general, the preferred application rate of the compound of formula I is in the range of 10 to 500 g a.i. /ha, preferably 20-300 g a.i. /ha.
The optimal rate for the compound of group (b) including the classes (A) through (E) will, however, depend an the crop(s) under cultivation and the level of infestation by the fungus, and can readily be determined by established biological tests.
The ratio (by weight) of the compound of formula I to the fungi - cidal active ingredient of the classes (A) through (E) as defined above is as a rule, from 100 : 1 to 1 : 100. The preferred ratio formula I : (A) through (E) may vary, e.g., from about 10 : 1 to about 1 : 10, in particular from about 5 : 1 to about 1 : 5, most preferred from 2 : 1 to 1 : 2. In the three-ways-compositions according to the present invention, i.e. the compositions containing one compound of formula I and two different compounds selected from the classes (A) through (E) , the preferred relative ratios (by weight) are as follows: compound of formula I: 200 to 1, preferably 20 to 1;
1 st compound of (A) to (E) : 1 to 100, preferably 1 to 10;
2nd compound of (A) to (E) : 1 to 100, preferably 1 to 10.
The active compounds can be corformulated together in a suitable ratio according to the present invention, together with usual carriers or diluents and/or additives known in the art.
Accordingly the invention further provides a fungicidal composition which comprises a carrier and, as active ingredient, at least one compound of formula I as defined above and at least one fungicidal active ingredient selected from the classes (A) through (E) as defined above.
A method of making such a composition is also provided which com- prises bringing the compound of formula I and the fungicidal active ingredient selected from the classes (A) through (E) as defined above into association with at least one carrier. It is also envisaged that different isomers or mixtures of isomers of the fungicidal active ingredient selected from the classes (A) through (E) may have different levels or spectra of activity and thus compositions may comprise individual isomers or mixtures of isomers .
A composition according to the invention preferably contains from 0.1 % to 99.9%, preferably 0.2 to 80 % by weight (w/w) of active ingredients .
A carrier in a composition according to the invention is any material with which the active ingredient is formulated to facili- tate application to the locus to be treated, which may for example be a plant, seed, foliage, soil, or into the water where the plant grow, or to the roots or to facilitate storage, transport or handling. A carrier may be a solid or a liquid, including material which is normally a gas but which has been compressed to form a liquid.
The compositions may be manufactured into e.g. emulsion concentrates, solutions, oil in water emulsions, wettable powders, soluble powders, suspension concentrates, dusts, granules, water dispersible granules, tablets, micro-capsules, gels and other formulation types by well established procedures. These procedures include intensive mixing and/or milling of the active ingre- dients with other substances, such as fillers, solvents, solid carriers, surface active compounds (surfactants), and optionally solid and/or liquid auxilaries and/or adjuvants. The form of application such as spraying, atomizing, dispersing or pouring may be chosen like the compositions according to the desired objectives and the given circumstances.
Solvents may be aromatic hydrocarbons, e.g. Solvesso[ 200, substituted naphthalenes, phthalic acid esters, such as dibutyl or dioctyl phthalate, aliphatic hydrocarbons, e.g. cyclohexane or paraffins, alcohols and glycols as well as their ethers and esters, e.g. ethanol, ethyleneglycol mono- and dimethyl ether, ketones such as cyclohexanone, strongly polar solvents such as N-methyl-2-pyrrolidone, or γ-butyrolactone, higher N-alkylpyrrolidones, e.g. N-octylpyrrolidone or N-cyclohexylpyr- rolidone, epoxidized plant oil esters, e.g. methylated coconut or soybean oil ester and water. Mixtures of different liquids are often suitable.
Solid carriers, which may be used for dusts, wettable powders, water dispersible granules, or granules, may be mineral fillers, such as calcite, talc, kaolin, montmorillonite or attapulgite or others. The physical properties may be improved by addition of highly dispersed silica gel or polymers. Carriers for granules may be porous material, e.g. pumice, kaolin, sepiolite, bento- nite; non-sorptive carriers may be calcite or sand or others. Additionally, a multitude of pre-granulated inorganic or organic materials may be used, such as dolomite or crushed plant residues .
Pesticidal compositions are often formulated and transported in a concentrated form which is subsequently diluted by the user before application. The presence of small amounts of a carrier which is a surfactant facilitates this process of dilution. Thus, preferably at least one carrier in a composition according to the invention is a surfactant. For example, the composition may contain at two or more carriers, at least one of which is a surfactant.
Surfactants may be nonionic, anionic, cationic or zwitterionic substances with good dispersing, emulsifying and wetting properties. Surfactants may also mean mixtures of individual surfactants .
The compositions of the invention may for example be formulated as wettable powders, water dispersible granules, dusts, granules, solutions, emulsifiable concentrates, emulsions, suspension con- centrates and aerosols. Wettable powders usually contain 5 to 90% w/w of active ingredient and usually contain in addition to solid inert carrier, 3 to 10% w/w of dispersing and wetting agents and, where necessary, 0 to 10% w/w of stabilizer (s) and/or other addi- tives such as penetrants or stickers. Dusts are usually formula¬ ted as a dust concentrate having a similar composition to that of a wettable powder but without a dispersant, and may be diluted in the field with further solid carrier to give a composition usually containing 0.5 to 10% w/w of active ingredient. Water dispersible granules and granules are usually prepared to have a size between 0.15 mm and 2.0 mm and may be manufactured by a variety of techniques. Generally, these types of granules will contain 0.5 to 90% w/w active ingredient and 0 to 20% w/w of additives such as stabilizer, surfactants, slow release modifiers and binding agents. The so-called "dry flowables" consist of relatively small granules having a relatively high concentration of ac¬ tive ingredient. Emulsifiable concentrates usually contain, in addition to a solvent or a mixture of solvents, 1 to 80% w/v active ingredient, 2 to 20% w/v emulsifiers and 0 to 20% w/v of other additives such as stabilizers, penetrants and corrosion inhibitors. Suspension concentrates are usually milled so as to obtain a stable, non-sedimenting flowable product and usually contain 5 to 75% w/v active ingredient, 0.5 to 15% w/v of dispersing agents, 0.1 to 10% w/v of suspending agents such as protective colloids and thixotropic agents, 0 to 10% w/v of other additives such as defoamers, corrosion inhibitors, stabilizers, penetrants and stickers, and water or an organic liquid in which the active ingredient is substantially insoluble; certain organic solids or inorganic salts may be present dissolved in the formulation to assist in preventing sedimentation and crystalization or as antifreeze agents for water.
Aqueous dispersions and emulsions, for example compositions obtained by diluting the formulated product according to the inven- tion with water, also lie within the scope of the invention.
Of particular interest in enhancing the duration of the protective activity of the compounds of this invention is the use of a carrier which will provide slow release of the pesticidal com- pounds into the environment of a plant which is to be protected. The biological activity of the active ingredient can also be increased by including an adjuvant in the formulation or the spray dilution. An adjuvant is defined here as a substance which can increase the biological activity of an active ingredient but is not itself significantly biologically active. The adjuvant can either be included in the formulation as a coformulant or car- rier, or can be added to the spray tank together with the formulation containing the active ingredient.
As a commodity the compositions may preferably be in a concentra- ted form whereas the end user generally employs diluted compositions. The compositions may be diluted to a concentration down to 0.001 % of active ingredient. The doses usually are in the range from 0.01 to 10 kg a.i. /ha.
Examples of formulations which can be used according to the invention are:
SC-I 2 active ingredient compound I 100.0 g Dispersing agent Soprophort FL 3) 30.0 g Antifoaming agent Rhodorsilt 426R 3) 1.5 g
Dispersing agent Rhodopolt 23 3) 2.0 g Antifreezing agent Propylene glycol 80.0 g Biocidal agent Proxelt GXL > - - 1.0 g
Water to 1000 ml
SC-A-E active ingredient fungicide selected from classes 200.0 g
(A) through (E) Dispersing agent Soprophort FL 3) 25. .0 g Antifoaming agent Rhodorsilt 426R 3) 1. 5 g Dispersing agent Rhodopolt 23 3) 2. 0 g Antifreezing agent Propylene glycol 80. 0 g Biocidal agent Proxelt GXL 4> 1. 0 g Water to 100C ) ml
SC-I + A-E active ingredient compound I 60.0 g active ingredient fungicide selected from classes 120.0 g
(A) through (E)
Dispersing agent Soprophort FL 3> 25.0 g Antifoaming agent Rhodorsilt 4268 3> 1.5 g Dispersing agent Rhodopolt 23 3> 2.0 g Antifreezing agent Propylene glycol 80.0 g Biocidal agent Proxelt GXL > 1.0 g Water to 1000 ml
DC-I 1 active ingredient compound I 100.0 g Wetting agent Pluronict PE6400 3> 50.0 g Dispersing agent Lutensolt TO 12 2' 50.0 g Solvent benzyl alcohol to 1000 ml 1) Product commercially available from Witco
2> Product commercially available from BASF Aktiengesllschaft
3) Product commercially available from Rhone-Poulenc
4) Product commercially available from Zeneca
The formulation SC-A-E comprising a compound selected from the classes (A) through (E) is in-tank mixed with any of the other formulations SC-I 2, SC-I 3, or DC-I which comprise compound I.
In a preferred embodiment the active ingredients are added to the tank mix together each as solo formulation.
Therefore, the present Invention relates to a kit for the preparation of a spray mixture consisting of two separate contain- ments :
(i) a containment which comprises at least one benzophenone I, conventional carriers and optionally adjuvants;
(ii) a containment which comprises at least one active ingredient selected from the classes (A) through (E) .
In a preferred embodiment the said kit will consist of two bottles with dispensing means which allow the easy and correct addition of the active ingredients (a) and (b) to the tank mix.
The formulation SC-I + A-E comprising benzophenone I and a fungicidal active ingredient selected from the classes (A) through (E) as defined above can be used directly for preparing the tank mix according to the present invention.
A composition according to the invention preferably contains from 0.5% to 95% by weight of active ingredients.
As commodity the compositions may preferably be in a concentrated form whereas the end-user generally employs diluted compositions. The compositions may be diluted down to a concentration of 0.0001 % of active ingredients.
The compositions of this invention can be applied to the plants or their environment simultaneous with or in succession with other active substances. These other active substances can be either fertilizers, agents which donate trace elements or other preparations which influence plant growth. However, they can also be other fungicides, selective herbicides, insecticides, bacteri- cides, nematicides, algicides, molluscidides, rodenticides , viru- cides, compounds inducing resistance into plants, biological control agents such as viruses, bacteria, nematodes, fungi and other microorganisms, repellents of birds and animals, and plant growth regulators, or mixtures of several of these preparations, if appropriate together with other carrier substances conventionally used in the art of formulation, surfactants or other addi - tives which promote application.
Examples of insecticidal compounds are alpha-cypermethrin, benfu- racarb, BPMC, buprofezine, carbosulfan, cartap, chlorfenvinphos , chlorpyrifos-methyl, cycloprothrin, cypermethrin, esfenvalerate, ethofenprox, fenpropathrin, flucythrinate, flufenoxuron, hydrame- thylnon, imidacloprid, isoxathion, MEP, MPP, nitenpyram, PAP, permethrin, propaphos, pymetrozine, silafluofen, tebufenozide, teflubenzuron, temephos, terbufos, tetrachlorvinphos and triaza- mate.
Examples of biological control agents are: Bacillus thuringien- sis, Verticillium lecanu, Aufographica califomica NPV, Beauvaria bassiana, Ampelomyces quisqualis, Bacilis subtilis, Pseudomonas cholororaphis, Pseudomonas fluorescens, Steptomyces grtseoviridis and Trichoderma harzianum.
Examples of chemical agents that induce systemic acquired resistance in plants such are: isonicotinic acid or derivatives thereof, 2, 2-dichloro-3 , 3-dimethylcyclopropylcarboxylic acid.
The present Invention is of wide applicability in the protection of crops, trees, residential and ornamental plants against fungal attack. Preferred crops are cereals, such as wheat and barley, rice as well as eines and apples. The duration of the protection is normally dependent an the individual compound selected, and also a variety of external factors, such as climate, whose impact is normally mitigated by the use of a suitable formulation.
The following examples further illustrate the present invention. It should be understood, however, that the invention is not limited solely to the particular examples given below.
EXAMPLES
General Methods
The trials are carried out under greenhouse conditions in residual or curative applications. The fungicides are applied in single treatments, or in a combination comprising a benzophenone I and a compound selected from the classes (A) through (E) as defined above. The compounds are applied in form of an aqueous spray mix obtained from concentrated formulation or the technical material .
I. Cereals and Dicots - Greenhouse
1. Seed is planted in 6 cm diameter plastic pots and maintained in the greenhouse.
2. When the primary leaf is fully expanded in the case of cereals or several leaves are present in the case of dicots, formulated test compounds are sprayed with a three nozzle overhead fungicide sprayer to near run-off. Alternatively, a single nozzle overhead track sprayer is used for application of the compounds to cereals at a rate of 200 1/ha. Plants are then allowed to air-dry.
3. Inoculation precedes treatment in the case of curative evaluations and follows treatment in case of residual evaluations. For inoculation of powdery mildew disease, plants are set up on greenhouse benches with bottom watering mats and inoculated by dusting them with conidia from infected plants. Between inoculation and treatment for curative evaluations and between treatment and inoculation for residual evaluations, plants are maintained in the greenhouse with bottom watering. For inoculation of non-powdery mildew diseases, an aqueous spore suspension of the pathogen is applied to the plant and the plants are kept 1-2 days in a moist infection chamber before being returned to the greenhouse where they are maintained by bottom watering.
4. Disease an the foliage as percent leaf area with disease symptoms/signs is evaluated about 7 days after inoculation. In the case of wheat, the tips and bases of the leaves are excluded from the evaluation.
disease in treated plants disease control = 100- x 100% disease in untreated plants
FORMULATION, REFERENCE COMPOUNDS AND CONTROLS:
1. Technical compounds are formulated in a solvent/surfactant system consisting of 5% acetone and 0.05% Tween 20 in deioni- zed water. Compounds are dissolved in acetone prior to addition of the water; the Tween 20 can be added through either the acetone or the water. Dilutions are made using the solvent/surf ctant system. Formulated compounds are prepared using deionized water.
2. Two kinds of controls are included:
Plants treated with the solvent/surfactant solution and inoculated (Solvent Blank) Untreated plants which are inoculated (Inoculated Control) .
For the field study formulated benzophenone I and formulated compounds from the classes (A) through (E) were used.
Evaluation of the disease:
Assessments of the diseases took place at the indicated day after the application of the compounds. Per cent infected leaf area infected was evaluated. The efficacy of the compounds/compounds mixtures to control the diseases was calculated by using the formula given above under item 4 :
II. Apple Fruit Botrytis Greenhouse
1. Apples (Malus X domestica Borkh.) variety "Golden Delicious" are disinfected by washing them briefly in 70 % ethanol. After drying the apples are marked with four short equal-distant lines indicating the positions to be wounded.
2. Corresponding with the marks, four holes are poked around the apple equator with a pipette tip. 10 ml of the treatment solution are pipetted into each hole.
3. Three hours after application, 10 ml of a conidial suspension of Botrytis cinerea are pipetted into each hole. For incubation, the treated/inoculated apples are stored for five days. 4. Disease occurs as rotten apple tissue surrounding the inoculated wounds. The diameter of the rotten zone around Bach wound is measured.
FORMULATION, REFERENCE COMPOUNDS AND CONTROLS:
1. Technical compounds are formulated in a solvent system consisting of 5% acetone and 0.05% Tween 20 in deionized water. Compounds are dissolved in acetone prior to dilution with water. Formulated compounds are prepared using deionized water. 2. Three kinds of controls are included:
Apples treated with the solvent solution and inoculated (Solvent Blank) . Untreated apples which are inoculated (Inoculated Control) . Untreated apples which are not inoculated (Uninoculated Con¬ trol) .
Evaluation of the disease:
Assessments of the diseases took place at the indicated day after the application of the compounds. Per cent infected leaf area in¬ fected was evaluated. The efficacy of the compounds/compounds mixtures to control the diseases was calculated by using the for¬ mula: mean of diameters on treated apples disease control = 100- x 100% mean of diameters on untreated apples
Determination of synergy:
Synergy was calculated using the % disease control values of spe- cific treatments for the two COLBY formula given hereinabove
Example 1
Fungicidal efficacy of the mixture of compound I + other fungici des (4 day residual) against Erysiphe cichoracearum on cucumbers The tank mixes were obtained from technical material of I and different formulations of different active ingredients. The active ingredients, the type of formulations, the observed and expected efficacies with different rates are given in Table I:
Table I
Figure imgf000018_0001
Figure imgf000019_0001
Figure imgf000020_0001
Figure imgf000021_0001
Example 2
Fungicidal efficacy of the mixture of I + other fungicides 14 day residual) against Puccinia recondi ta an wheat
The tank mixes were obtained from technical material of I and different formulations of different active ingredients. The active ingredients, the type of formulations, the observed and expected efficacies with different rates are given in Table II:
Table II
Figure imgf000021_0002
Figure imgf000022_0001
Figure imgf000023_0001
Example 3
Fungicidal efficacy of the mixture of I + other fungicides (4 day residual) against Leptosphaeria nodorum an wheat The tank mixes were obtained from technical material of I and different formulations of different active ingredients. The active ingredients, the type of formulations, the observed and expected efficacies with different rates are given in Table III:
Table III
Figure imgf000024_0001
Figure imgf000025_0001
Example 4
Fungicidal efficacy of the mixture of I + other fungicides (4 day residual) against Puccinia recondi ta an wheat The tank mixes were obtained from technical material of I and different formulations of different active ingredients. The ac¬ tive ingredients, the type of formulations, the observed and ex¬ pected efficacies with different rates are given in Table IV:
Table IV
Figure imgf000026_0001
Figure imgf000027_0001
Example 5
Q Fungicidal eucacy of the mixture of I + other fungicides (4 day residual) against Leptosphaeria nodorum an wheat
The tank mixes were obtained from technical material of I and different formulations of different active ingredients. The ac- 5 tive ingredients, the type of formulations, the observed and ex¬ pected efficacies with different rates are given in Table V:
Table V
0
5
0
5
0
Figure imgf000027_0002
Figure imgf000028_0001
Example 6
Fungicidal efficacy of the mixture of I + other fungicides (4 day residual) against Erysiphe cichoracearum on cucumbers
The tank mixes were obtained from technical material of I and different formulations of different active ingredients. The active ingredients, the type of formulations, the observed and expected efficacies with different rates are given in Table VI:
Table VI
Figure imgf000028_0002
Figure imgf000029_0001
10
15
20
25
30
35
Figure imgf000030_0001
Example 7
4 Fungicidal efficacy of the mixture of I + Myclobutanil (4 day residual) against Puccinia recondi ta an wheat
The tank mixes were obtained from technical material of I and Myclobutanil. The type of formulation, the observed and expected " efficacies with different rates are given in Table VII: Table VII
Figure imgf000031_0001
Example 8
Fungicidal efficacy of the mixture of I + other fungicides (4 day residual) against Pyrenophora teres an barley
The tank mixes were obtained from technical material of I and different formulations of different active ingredients. The active ingredients, the type of formulations, the observed and expected efficacies with different rates are given in Table VIII:
Table XIII
Figure imgf000031_0002
Figure imgf000032_0001
Figure imgf000033_0001
Example 9
Fungicidal efficacy of the mixture of I + other fungicides (4 day residual) against Erysiphe cichoracearum an cucumbers
The tank mixes were obtained from technical material of I and different formulations of different active ingredients. The active ingredients, the type of formulations, the observed and expected efficacies with different rates are given in Table IX:
Table IX
Figure imgf000033_0002
Figure imgf000034_0001
Figure imgf000035_0001
Example 10
Fungicidal efficacy of the mixture of I + other fungicides (4- day residual) against Puccinia recondi ta an wheat
The tank mixes were obtained from technical material of I and different formulations of different active ingredients. The active ingredients, the type of formulations, the observed and expected efficacies with different rates are given in Table X:
Table X
Figure imgf000035_0002
Figure imgf000036_0001
Figure imgf000037_0001
Example 11
Fungicidal efficacy of the mixture of I + other fungicides (4 day residual) against Pyrenophora feres an barley
The tank mixes were obtained from technical material of I and different formulations of different active ingredients. The active ingredients, the type of formulations, the observed and expected efficacies with different rates are given in Table XI: Table XI
Figure imgf000038_0001
0
5
0
5
Figure imgf000039_0001
n Example 12
Fungicidal efficacy of the mixture of I + metconazole (2 day curative) against blumeria graminis f . sp. tri tici on wheat
5 The tank mixes were obtained from technical material of I and metconazole. The type of formulations, the observed and expected efficacies with different rates are given in Table XII:
Table XII 0
5
Figure imgf000039_0002
Figure imgf000040_0001
Example 13
Fungicidal efficacy of the mixture of I + triazolopyrimidine AP-4 (1 day residual) against Uncinula neca tor on vine
The tank mixes were obtained from technical material of I and AP-4. The active ingredients, the type of formulations, the observed and expected efficacies with different rates are given in Table XIII:
Table XIII
Figure imgf000040_0002

Claims

What is claimed is:
1. A fungicidal composition comprising a fungicidally acceptable carrier and/or surface active agent together with, and synergistically effective amounts of
(a) the benzophenone of formula I and
Figure imgf000041_0001
(b) at least one fungicidally active ingredient selected from the following groups (A) , (B) , (C) , (D) and (E) :
(A) an ergosterol biosynthesis inhibitor;
(B) a strobilurine derivative;
(C) a melanin biosynthesis inhibitor;
(D) a compound selected from the group consisting of acibenzolar, benomyl, captan, carboxin, chlorothalonil, copper, cyprodinil, dinocap, dithianon, dimethomorph, dodine, ethirimol, famoxadone, fenpiclonil, fluazinam, mancozeb, metalaxyl, pyrifenox, sulfur, vinclozolin; and
(E) a triazolopyrimidine of formula II,
Figure imgf000041_0002
in which R1 represents Cι~C6-alkyl or Ci-Cδ-haloalkyl, and R2 and R4 each independently represents halogen or Cχ-C2-haloalkyl and R3 is hydrogen, halogen or Cι-C2-halo- alkyl, Cι-C2-alkoxy or Cι~C2-haloalkoxy.
2. A composition as claimed in claim 1, wherein the ergosterol biosynthesis inhibitor of group (A) is epoxiconazole, flusilazole, metconazole, myclobutanil, penconazole, prochloraz, propiconazole, tebuconazole, triadimefon and triadimenol.
3. A composition as claimed in Claim 1, wherein the ergosterol biosynthesis inhibitor of group (A) is selected from fenarimol, fenpropimorph, fenpropidine, spiroxamine, triforine and cyproconazole.
4. A composition as claimed in claim 1, wherein the strobilurine derivative of group (B) is selected from azoxystrobin and kresoxim-methyl .
5. A composition as claimed in claim 1, which comprises one compound of formuia I, one strobilurine compound selected from group (B) and one ergosterol biosynthesis inhibitor of group (A) , or one compound of formula I and two different compounds of group (D) .
6. A composition as claimed in claim 1, wherein the melanin biosynthesis inhibitor of group (C) is selected from capropamid, chlobenthiazone, dichlocymet, pyroquilon, phthalide, tricy- clazole and fenoxanil.
7. A composition as claimed in claim 1, wherein the triazolopyrimidine of group (E) is a compound of formula II,
Figure imgf000042_0001
wherein R2 represents a fluorine atom;
R3 represents a hydrogen or fluorine atom; R4 represents a fluorine or chlorine atom.
8. A composition as claimed in claim 7, wherein the triazolopy- rimidine of formula II is selected from the group consisting of 5-chloro-6- (2-chloro-6-fluorophenyl) -7- (2,2, 2-trifluoroe- thylamino) [1, 2, 4] triazolo [1, 5-a] pyrimidine and 5-chloro-6- (2,4, 6-trifluorophenyl) -7- [2- (1, 1, 1-tri- fluoro)propylamino] [1,2,4] triazolo [1, 5-a] pyrimidine.
9. A composition as claimed in Claim 1, wherein the ratio (by weight) of the benzophenone of formula I to the fungicidal compound selected from the groups (A) , (B) , (C) , (D) and (E) is from 1 : 10 to 10 : 1.
10. Method of controlling the growth of fungi at a locus which comprises applying a composition as claimed in claim 1 to the locus .
11. Method of controlling the growth of powdery mildew at a locus which comprises applying a composition as claimed in claim 1 to the locus.
PCT/EP2001/001823 2001-02-19 2001-02-19 Fungicidal mixtures WO2002067679A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/EP2001/001823 WO2002067679A1 (en) 2001-02-19 2001-02-19 Fungicidal mixtures

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/EP2001/001823 WO2002067679A1 (en) 2001-02-19 2001-02-19 Fungicidal mixtures

Publications (1)

Publication Number Publication Date
WO2002067679A1 true WO2002067679A1 (en) 2002-09-06

Family

ID=8164297

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2001/001823 WO2002067679A1 (en) 2001-02-19 2001-02-19 Fungicidal mixtures

Country Status (1)

Country Link
WO (1) WO2002067679A1 (en)

Cited By (33)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004045288A2 (en) * 2002-11-15 2004-06-03 Basf Aktiengesellschaft Fungicidal mixtures for controlling rice pathogens
WO2006040123A3 (en) * 2004-10-12 2006-06-29 Bayer Cropscience Ag Fungicidal active ingredient combinations containing fluoxastrobin
WO2007107244A1 (en) * 2006-03-20 2007-09-27 Bayer Cropscience Ag Algae-controlling agents
US7285555B2 (en) 2003-09-24 2007-10-23 Wyeth Holdings Corporation 6-aryl-7-halo-imidazo[1,2-a]pyrimidines as anticancer agents
US7419982B2 (en) 2003-09-24 2008-09-02 Wyeth Holdings Corporation Crystalline forms of 5-chloro-6-{2,6-difluoro-4-[3-(methylamino)propoxy]phenyl}-N-[(1S)-2,2,2-trifluoro-1-methylethyl][1,2,4]triazolo[1,5-a]pyrimidin-7-amine salts
JP2009509994A (en) * 2005-09-29 2009-03-12 シンジェンタ パーティシペーションズ アクチェンゲゼルシャフト Fungicidal composition
US7507739B2 (en) 2003-09-24 2009-03-24 Wyeth 6-[(substituted)phenyl]triazolopyrimidines as anticancer agents
WO2009103813A2 (en) * 2008-02-22 2009-08-27 Basf Se Fungicidal compositions comprising 3'-bromine-2,3,4,6'-tetramethoxy-2'-6-dimethylbenzophenone
WO2012101660A1 (en) * 2011-01-28 2012-08-02 Deepak Pranjivandas Shah Pesticidal composition comprising sulphur, a fungicide and an agrochemical excipient
CN102805083A (en) * 2012-09-02 2012-12-05 陕西上格之路生物科学有限公司 Sterilizing combination containing metrafenone and triazole fungicide
CN102823597A (en) * 2012-09-13 2012-12-19 陕西上格之路生物科学有限公司 Sterilization compound containing metrafenone and quinoxyfen
CN102835399A (en) * 2012-09-27 2012-12-26 陕西上格之路生物科学有限公司 Metrafenone-containing bactericidal composition
WO2012161235A3 (en) * 2011-05-24 2013-04-04 Ishihara Sangyo Kaisha, Ltd. Fungicidal composition and method for controlling plant diseases
CN103053531A (en) * 2011-10-21 2013-04-24 深圳诺普信农化股份有限公司 Bactericide composition
CN103053538A (en) * 2011-10-21 2013-04-24 深圳诺普信农化股份有限公司 Fungicide composition
CN103120170A (en) * 2011-11-18 2013-05-29 深圳诺普信农化股份有限公司 Bactericidal composition
CN103329916A (en) * 2013-07-25 2013-10-02 联保作物科技有限公司 Sterilizing composite and preparation thereof
CN103651394A (en) * 2013-12-17 2014-03-26 北京燕化永乐生物科技股份有限公司 Sterilization composition containing Jiean-peptide
CN103858872A (en) * 2014-03-15 2014-06-18 海南正业中农高科股份有限公司 Metrafenone-containing pesticide composition
CN103858884A (en) * 2012-12-12 2014-06-18 陕西美邦农药有限公司 Sterilization composition containing metrafenone and methoxy acrylate
CN104756987A (en) * 2014-01-04 2015-07-08 陕西标正作物科学有限公司 Sterilization composition, pesticide, and use of composition and pesticide
CN104855386A (en) * 2015-05-28 2015-08-26 东莞市瑞德丰生物科技有限公司 Sterilizing combination using metrafenone as main component
CN105028426A (en) * 2015-06-09 2015-11-11 柳州市天姿园艺有限公司 Composition for preventing and treating anthracnose of vanda coerulea
CN105766962A (en) * 2016-05-06 2016-07-20 江苏丰登作物保护股份有限公司 Bactericide composition containing metrafenone and pyraclostrobin and application thereof
CN105815314A (en) * 2012-12-12 2016-08-03 陕西美邦农药有限公司 Sterilization composition containing metrafenone and strobilurin
CN105851041A (en) * 2016-04-30 2016-08-17 广东中迅农科股份有限公司 Fungicidal composition containing metrafenone and prochloraz
CN105900990A (en) * 2012-05-31 2016-08-31 陕西韦尔奇作物保护有限公司 Phenoxyquinoline-containing sterilization composition
WO2016194741A1 (en) * 2015-05-29 2016-12-08 石原産業株式会社 Fungicidal composition and method for controlling plant diseases
CN106538534A (en) * 2016-10-26 2017-03-29 广东中迅农科股份有限公司 A kind of complex composition containing metrafenone and 2-cyano-3-amino-3-phenylancryic acetate
CN106857510A (en) * 2017-04-17 2017-06-20 北京科发伟业农药技术中心 Fungicidal composition containing metrafenone
CN108849922A (en) * 2018-08-03 2018-11-23 河南科技大学 A kind of bactericidal composition, fungicide and its application
CN112568227A (en) * 2020-12-27 2021-03-30 贵州发来地农业科技有限公司 Nutritional roxburgh rose powdery mildew pesticide and application thereof
CN112586503A (en) * 2020-12-22 2021-04-02 江西禾益化工股份有限公司 Cyazofamid-containing bactericidal composition and application thereof

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0897904A1 (en) * 1997-08-20 1999-02-24 American Cyanamid Company Fungicidal 2-methoxybenzophenones
EP1023837A2 (en) * 1999-01-29 2000-08-02 American Cyanamid Company Non-aqueous, emulsifiable concentrate formulation
EP1023834A1 (en) * 1999-01-29 2000-08-02 American Cyanamid Company Fungicidal mixtures
WO2000072677A1 (en) * 1999-05-26 2000-12-07 Bayer Aktiengesellschaft Fungicidal compositions
WO2000076317A1 (en) * 1999-06-14 2000-12-21 Syngenta Participations Ag Fungicidal combinations

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0897904A1 (en) * 1997-08-20 1999-02-24 American Cyanamid Company Fungicidal 2-methoxybenzophenones
EP1023837A2 (en) * 1999-01-29 2000-08-02 American Cyanamid Company Non-aqueous, emulsifiable concentrate formulation
EP1023834A1 (en) * 1999-01-29 2000-08-02 American Cyanamid Company Fungicidal mixtures
WO2000072677A1 (en) * 1999-05-26 2000-12-07 Bayer Aktiengesellschaft Fungicidal compositions
WO2000076317A1 (en) * 1999-06-14 2000-12-21 Syngenta Participations Ag Fungicidal combinations

Cited By (47)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004045288A3 (en) * 2002-11-15 2004-07-29 Basf Ag Fungicidal mixtures for controlling rice pathogens
WO2004045288A2 (en) * 2002-11-15 2004-06-03 Basf Aktiengesellschaft Fungicidal mixtures for controlling rice pathogens
US7915266B2 (en) 2003-09-24 2011-03-29 Wyeth Holdings Corporation 6-aryl-7-halo-imidazo[1,2-a]pyrimidines as anticancer agents
US7285555B2 (en) 2003-09-24 2007-10-23 Wyeth Holdings Corporation 6-aryl-7-halo-imidazo[1,2-a]pyrimidines as anticancer agents
US7419982B2 (en) 2003-09-24 2008-09-02 Wyeth Holdings Corporation Crystalline forms of 5-chloro-6-{2,6-difluoro-4-[3-(methylamino)propoxy]phenyl}-N-[(1S)-2,2,2-trifluoro-1-methylethyl][1,2,4]triazolo[1,5-a]pyrimidin-7-amine salts
US7507739B2 (en) 2003-09-24 2009-03-24 Wyeth 6-[(substituted)phenyl]triazolopyrimidines as anticancer agents
WO2006040123A3 (en) * 2004-10-12 2006-06-29 Bayer Cropscience Ag Fungicidal active ingredient combinations containing fluoxastrobin
JP2009509994A (en) * 2005-09-29 2009-03-12 シンジェンタ パーティシペーションズ アクチェンゲゼルシャフト Fungicidal composition
WO2007107244A1 (en) * 2006-03-20 2007-09-27 Bayer Cropscience Ag Algae-controlling agents
KR101374119B1 (en) 2006-03-20 2014-03-17 바이엘 크롭사이언스 아게 Algae-controlling agents
JP2011512388A (en) * 2008-02-22 2011-04-21 ビーエーエスエフ ソシエタス・ヨーロピア Bactericidal composition comprising 3'-bromo-2,3,4,6'-tetramethoxy-2 ', 6-dimethylbenzophenone
AU2009216678B2 (en) * 2008-02-22 2013-11-21 Basf Se Fungicidal compositions comprising 3'-bromine-2,3,4,6'-tetramethoxy-2'-6-dimethylbenzophenone
WO2009103813A3 (en) * 2008-02-22 2010-08-12 Basf Se Fungicidal compositions comprising 3'-bromine-2,3,4,6'-tetramethoxy-2'-6-dimethylbenzophenone
WO2009103813A2 (en) * 2008-02-22 2009-08-27 Basf Se Fungicidal compositions comprising 3'-bromine-2,3,4,6'-tetramethoxy-2'-6-dimethylbenzophenone
US9538761B2 (en) 2011-01-28 2017-01-10 Deepak Pranjivandas Shah Pesticidal composition comprising sulphur, a fungicide and an agrochemical excipient
WO2012101660A1 (en) * 2011-01-28 2012-08-02 Deepak Pranjivandas Shah Pesticidal composition comprising sulphur, a fungicide and an agrochemical excipient
WO2012161235A3 (en) * 2011-05-24 2013-04-04 Ishihara Sangyo Kaisha, Ltd. Fungicidal composition and method for controlling plant diseases
CN103053538B (en) * 2011-10-21 2014-09-10 深圳诺普信农化股份有限公司 Fungicide composition
CN103053531A (en) * 2011-10-21 2013-04-24 深圳诺普信农化股份有限公司 Bactericide composition
CN103053538A (en) * 2011-10-21 2013-04-24 深圳诺普信农化股份有限公司 Fungicide composition
CN103120170A (en) * 2011-11-18 2013-05-29 深圳诺普信农化股份有限公司 Bactericidal composition
CN105900990A (en) * 2012-05-31 2016-08-31 陕西韦尔奇作物保护有限公司 Phenoxyquinoline-containing sterilization composition
CN102805083A (en) * 2012-09-02 2012-12-05 陕西上格之路生物科学有限公司 Sterilizing combination containing metrafenone and triazole fungicide
CN102823597A (en) * 2012-09-13 2012-12-19 陕西上格之路生物科学有限公司 Sterilization compound containing metrafenone and quinoxyfen
CN102835399A (en) * 2012-09-27 2012-12-26 陕西上格之路生物科学有限公司 Metrafenone-containing bactericidal composition
CN102835399B (en) * 2012-09-27 2014-04-30 陕西上格之路生物科学有限公司 Metrafenone-containing bactericidal composition
CN105815314B (en) * 2012-12-12 2018-08-03 陕西美邦农药有限公司 A kind of bactericidal composition containing metrafenone and methoxy acrylic
CN103858884A (en) * 2012-12-12 2014-06-18 陕西美邦农药有限公司 Sterilization composition containing metrafenone and methoxy acrylate
CN105815314A (en) * 2012-12-12 2016-08-03 陕西美邦农药有限公司 Sterilization composition containing metrafenone and strobilurin
CN103329916B (en) * 2013-07-25 2014-06-11 联保作物科技有限公司 Sterilizing composite and preparation thereof
CN103329916A (en) * 2013-07-25 2013-10-02 联保作物科技有限公司 Sterilizing composite and preparation thereof
CN103651394B (en) * 2013-12-17 2014-11-05 北京燕化永乐生物科技股份有限公司 Sterilization composition containing Jiean-peptide
CN103651394A (en) * 2013-12-17 2014-03-26 北京燕化永乐生物科技股份有限公司 Sterilization composition containing Jiean-peptide
CN104756987B (en) * 2014-01-04 2016-08-24 陕西标正作物科学有限公司 A kind of bactericidal composition, agricultural chemicals and application thereof
CN104756987A (en) * 2014-01-04 2015-07-08 陕西标正作物科学有限公司 Sterilization composition, pesticide, and use of composition and pesticide
CN103858872A (en) * 2014-03-15 2014-06-18 海南正业中农高科股份有限公司 Metrafenone-containing pesticide composition
CN104855386A (en) * 2015-05-28 2015-08-26 东莞市瑞德丰生物科技有限公司 Sterilizing combination using metrafenone as main component
US10172357B2 (en) 2015-05-29 2019-01-08 Ishihara Sangyo Kaisha, Ltd. Fungicidal composition and method for controlling plant diseases
WO2016194741A1 (en) * 2015-05-29 2016-12-08 石原産業株式会社 Fungicidal composition and method for controlling plant diseases
CN105028426A (en) * 2015-06-09 2015-11-11 柳州市天姿园艺有限公司 Composition for preventing and treating anthracnose of vanda coerulea
CN105851041A (en) * 2016-04-30 2016-08-17 广东中迅农科股份有限公司 Fungicidal composition containing metrafenone and prochloraz
CN105766962A (en) * 2016-05-06 2016-07-20 江苏丰登作物保护股份有限公司 Bactericide composition containing metrafenone and pyraclostrobin and application thereof
CN106538534A (en) * 2016-10-26 2017-03-29 广东中迅农科股份有限公司 A kind of complex composition containing metrafenone and 2-cyano-3-amino-3-phenylancryic acetate
CN106857510A (en) * 2017-04-17 2017-06-20 北京科发伟业农药技术中心 Fungicidal composition containing metrafenone
CN108849922A (en) * 2018-08-03 2018-11-23 河南科技大学 A kind of bactericidal composition, fungicide and its application
CN112586503A (en) * 2020-12-22 2021-04-02 江西禾益化工股份有限公司 Cyazofamid-containing bactericidal composition and application thereof
CN112568227A (en) * 2020-12-27 2021-03-30 贵州发来地农业科技有限公司 Nutritional roxburgh rose powdery mildew pesticide and application thereof

Similar Documents

Publication Publication Date Title
EP1023834B1 (en) Fungicidal mixtures
WO2002067679A1 (en) Fungicidal mixtures
EP0988790B1 (en) Fungicidal mixtures
US6268371B1 (en) Fungicidal mixtures
RU2434382C2 (en) Combinations of imazalil and silver compounds
US6277856B1 (en) Fungicidal mixtures
US6596775B2 (en) Enhancement of the efficacy of benzoylbenzenes
JP2023078328A (en) Synergistic mixtures for fungal control in cereals
JP2753932B2 (en) Microbicide
JP2008525347A (en) Disinfectant mixture
NZ337622A (en) Fungicidal combinations comprising a 4-phenoxyquinoline and another fungicide
JP2001524499A (en) Fungicidal combination comprising thieno [2.3-d] pyrimidin-4-one
US6521628B1 (en) Fungicidal mixtures
KR20010080945A (en) Fungicidal combinations comprising thieno[2,3-d]pyrimidin-4-one
US6699874B2 (en) Fungicidal mixtures
KR100686791B1 (en) Fungicidal mixtures
US6696497B2 (en) Fungicidal mixtures
EP1023835A1 (en) Enhancement of the efficacy of benzoylbenzenes
JP2006517521A (en) Bactericidal mixtures based on triazolopyrimidine derivatives and azoles
MXPA99008084A (en) Fungicide mixtures
KR20010032654A (en) Fungicidal combinations comprising thieno[2,3-d]pyrimidin-4-one

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BY BZ CA CH CN CR CU CZ DE DK DM DZ EE ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NO NZ PL PT RO RU SD SE SG SI SK SL TJ TM TR TT TZ UA UG UZ VN YU ZA ZW

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): GH GM KE LS MW MZ SD SL SZ TZ UG ZW AM AZ BY KG KZ MD RU TJ TM AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE TR BF BJ CF CG CI CM GA GN GW ML MR NE SN TD TG

DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
121 Ep: the epo has been informed by wipo that ep was designated in this application
REG Reference to national code

Ref country code: DE

Ref legal event code: 8642

122 Ep: pct application non-entry in european phase
NENP Non-entry into the national phase

Ref country code: JP