OA17655A - Pesticide compounds, use thereof and method of protection of plants. - Google Patents

Abstract

The invention provides use of compounds of general formula Cu2SO3.MSO3.2H2O, wherein M is Cu, Mn or Fe, for the protection of plants against fungal diseases. Further, it encompasses a method of protecting plants against fungal diseases and a pesticidal preparation comprising at least one compound of said general formula.

Description

The invention provides use of compounds of general formula Cu2SO3.MSO3.2H2O, wherein M is Cu, Mn or Fe, for the protection of plants against fungal diseases. Further, it encompasses a method of protecting plants against fungal diseases and a pesticidal préparation comprising at least one compound of said general formula.

O.A.P.I. - B.P. 887, YAOUNDE (Cameroun) - Tel. (237) 222 20 57 00- Fax: (237) 222 20 57 27- Site web: http:/www.oapi.int - Email: oapi@oapi.int

Pesticide compounds, use thereof and method of protection of plants

Field of Art

The présent invention relates to compounds possessing pesticidal activities, to use thereof for prophylaxis and treatment of plant infections caused by fungal pathogens, to a method of protection of plants against fungal pathogens, and to a pesticide préparation containing these compounds.

¹⁰ Background Art

Fungal diseases belong among key pathogens in agricultural production. These pathogens must be controlled in order to prevent further infection of the plants. Apart from causing the decrease of yields, fungi represent a significant health risk for both humans and animais, because they contaminate crops with mycotoxins - products of their own metabolism. The control of fungal diseases therefore has a considérable économie impact.

Various fungicidal products containing organic or inorganic active substances are known in the art and commercially available. The organic substances usually show a high fungicidal activity, however, the application thereof often results in accumulation of toxic residues of xenobiotic organic substances in the environment and in agricultural products entering the food chain. Among the inorganic substances, the low-soluble Cu(II)-compounds are widely used, the fungicidal effect of which is known since 1882 (Bordeaux mixture comprising cupric hydroxide). In general, these compounds show a rather low activity and they must be applied in massive doses (e.g., the recommended dose of cupric oxychloride [CuC12.3Cu(OH)2], commecrially available under the trade name Kuprikol 50, is 4 to 5 kg per hectar, which corresponds to 2.0 to 2.5 kg of copper per hectar). High doses of copper compounds burden the soil and resuit in an undesirable ί i copper accumulation (Kaplan M., J. Plant Nutr. 1999,22, 237-244).|

EP 1471787 discloses a fungicidal préparation allowing to decrease the overall copper| dose by using a mixture of cupric hydroxide and at least one other copper compoundj selected from CuC12.3Cu(OH)₂, basic cupric sulphate, Bordeaux mixture and cupric-\ calcium oxychloride. This mixture allows to increase the effectivity ca 1.4-times,| compared to the individual compounds.j l l g

I

The US patent application 2009/136581 discloses fungicide and bactéricide préparation comprising cupric hydroxide and water-soluble carboxylic acid dérivative as a chelating agent. This mixture allowed to decrease the overall copper dose 1.5-times compared to cupric hydroxide itself or 6.3-times compared to CuC12.3Cu(OH)2 while maintaining the same effect. The decrease of the copper dose according to EP 1471787 and US

2009/136581, however, is still not sufficient.

WO 2010/076038 discloses fungicide préparations based on temary mixtures of cupric salicylate sait, cupric hydroxide and a component comprising copper and/or calcium hydroxide-chloride or hydroxide-sulphate. The document shows the synergism of these components using the example of Plasmopara viticola mould, but it does not deal with the optimalization of the overall dose of copper per hectar.

There still exists the need for novel pesticide préparations providing copper which would be active at very low application doses and without toxic effects on the plants.

Disclosure of the Invention

The aim of the invention is achieved according to the présent invention by the provision of novel pesticide préparations comprising double salts of general formula

Cu2SO3.MSO3.2H2O, wherein M is Cu, Mn or Fe, their composition, préparation and use. The synthesis, structure and chemical properties of these compounds are known (Silva L. A., Andrade J. B., J. Braz. Chem. Soc., 2004, 15(2), 170-177), but their fungicidal effects were not yet disclosed.

In particular, the compound Cu2SO3.CuSO3.2H2O (Chevreul's sait) shows a particularly high fungicidal activity. This double sait contains copper in two oxidation states: Cu²⁺ and Cu⁺. Its low solubility is exploited in metallurgical industry for hydrometallurgical séparation of copper from solutions containing Cu²⁺ ions (US 4070183). The compound can be prepared by several processes, typically by réduction of Cu²⁺ compounds in an aqueous solution using compounds of S⁴⁺ (SO₂, HSCh^- etc.) at an elevated température . (Calban T. et al., Chem. Eng. Comm. 2009, 196, 1018-1029).

The object of the invention is the use of compounds of general formula

Cu2SO3.MSO3.2H2O (I) wherein M is Cu, Mn or Fe, for the protection of plants against fungal diseases.

| I I | I i

The object of the invention is also a method of protection of plants against fungal diseases, in which at least one compound of the general formula (I) is applied to seeds, plant, fruits or into soil.

Another object of the invention is a pesticidal, in particular fungicidal, préparation for protection of plants, comprising at least one compound of the general formula (I).

The préparation may further contain auxiliary substances such as fillers, surfactants, antioxidants, defoaming agents and other auxiliaries.

Fillers are natural or synthetic organic or inorganic substances which when mixed with the active substance (I) facilitate its application. The filler must be inert and acceptable for use in agriculture. Examples are kaolin, montmorilonite, atapulgite, bentonite, calcite; dolomite, natural or synthetic silicates and aluminosilicates, fertilizers, water or minerai’ and plant oîls and dérivatives thereof. Mixtures of these fillers can be used as well. The content of the filler in the mixtures is preferably 1 to 90 % w/w, in wettable powders preferably 15 to 80 % w/w, in suspension concentrâtes preferably 5 to 35 % w/w.

Surfactants are ionic or non-ionic dispergation agents, soakîng agents or emulgators. Examples are salts of naphthalenesulphonic, phenolsulphonic and ligninsulphonic acids, polycondensates of ethylene oxide with fatty acids or amines, substituted phénols (in particular alkylphenols and arylphenols), salts of sulphosuccïnic acid esters, salts of alkylbenzenesulphonic acid, taurin dérivatives (in particular alkyltaurates), esters of phosphoric acid with polyethoxylated alcohols or phénols, esters of fatty acids with polyols, and dérivatives thereof containing sulphate, sülphonate or phosphate moiety. The contant of the surfactant in the mixtures is preferably 2 to 60 % w/w.

Antioxidants are any compounds acceptable for use in agriculture which are able to stabilize the compounds of the general formula (I) against oxidation. Preferably, compounds containing S⁴⁺ are used, e.g., NaHSOj, Na₂SO₂, Na₂S₂C>5 or K₂S₂0s. The content of the antioxidant in the préparation is preferably 0,01 to 10 % w/w.

Defoaming agents are any compounds decreasing the foam stability. Preferably, siliconebased compounds are used.

Further auxiliaries are colloid stabilizers, adhesives, binders and rhéologie modifïers. Generally, a compound of the general formula (I) can be combined with any liquid or solid additive commonly used for pesticide or fertilizer formulations.

The préparation of the présent invention preferably contains 1 to 99 % w/w of the compound of general formula (I). When formulated as a wettable powder, it preferably contains 10 to 90 % w/w, most preferably 40 to 80 % w/w of the compound of general formula (I). When formulated as a suspension concentrate, it preferably contains 1 to 50 % w/w, most preferably 5 to 30 % w/w of the active compound (I).

In a preferred embodiment, the compound of general formula (1) is Cu2SO3.CuSO3.2H2O.

The préparations of the invention can be provided as various formulations, suitable for application in agriculture as such or after dilution, such water-dispergable granules or microgranules, wettable powders, water-dispergable tablets, suspensions, suspension concentrâtes, water-dispergable pastes, emulgable powders, emulgable granules or microgranules, emulgable suspension concentrations, microemulsions, colloid solutions containing nano- or micropartïcles of the compound of general formula (I). Wettable powders can be filled into soluble wrappers, the use of which prevents undesirable dusting or breathing-in the powder by the user.

For the above-listed applications, the compound of general fomula (I) has preferably grain size smaller than 100 pm, more preferably smaller than 75 pm, even more preferably smaller than 50 pm.

The préparation of the invention can contain further substances, such as insecticides, fiingicides, bactéricides, attractants, acaricides, pheromones and further substances showing biological effects. The presence of these compounds broadens the spectrum of effects of the préparation. Particularly advantageous are combinations with other fungicides. The substances that can be used in such broad-spectrum préparations are, e.g.,

- substances capable of inhibitïng nucleic acid synthesis, such as benalaxyl, benalaxylM, bupirimate, clozylacone, dimethirimol, ethirimol, furalaxyl, hymexazol, mefenoxam, metalaxyl, metalaxyl-M, ofurace, oxadixyl, oxolinic acid;

- substances capable of inhibitïng mitose and cell division, such as benomyl, carbendazim, diethofencarb, ethaboxam, fuberidazole, pencycuron, thiabendazol, thiophanate-methyl, zoxamid;

- substances capable of inhibitïng breathing, such as diflumetorim, boscalid, carboxin, fenfuram, flutolanil, furametpyr, furmecyclox, mepronil, oxycarboxîn, penthiopyrad, thifluzamid, amisulbrom, azoxystrobin, cyazofamid, dimoxystrobin, enestrobin, famoxadone, fenamidone, fluoxastrobin, kresoxim-methyl, metominostrobin, orysastrobin, picoxystrobin, pyraclostrobin, trifloxystrobin

- substances capable of inhibitïng oxidative phosphorylation, such as dinocap, fluazinam, meptyldinocap;

- substances capable of ATP synthesis inhibition, such as fentin acetate, fentin chlorid, fentin hydroxide, silthiofam;

- substances capable of inhibitïng aminoacid and protein biosynthesis, such as andoprim, blasticidin-S, cyprodinil, kasugamycin, kasugamycin hydrochlorid hydrate, mepanipyrim, pyrimethanil;

- substances capable of inhibitïng signal transmission, such as fenpiclonil, fludioxonil, chinoxyfen;

substances capable of inhibitïng lipid and membrane component synthesis, such as bifenyl, chlozolinate, edifenphos, etridiazol, iodocarb, iprobenfos, iprodione, isoprothiolan, procymidon, propamocarb, propamocarb hydrochlorid, pyrazophos, tolclofos-methyl, vinclozolin;

- substances capable of inhibitïng ergosterol biosynthesis, such as aldimorph, azaconazol, bitertanol, bromuconazol, cyproconazol, diclobutrazol, difenoconazol, diniconazol, diniconazol-M, dodemorph, dodemorph acetate, epoxiconazol, etaconazol, fenarimol, fenbuconazol, fenhexamid, fenpropidin, fenpropimorph, fluquinconazol, flurprimidol, flusilazol, flutriafol, furconazol, furconazol-cis, hexaconazol, imazalil, imazalil. sulfate, imibenconazol, ipconazol, metconazol, myclobutanil, naftifin, nuarimol, oxpoconazol, paclobutrazol, pefurazoate, penconazol, prochloraz, propiconazol, prothioconazol, pyributicarb, pyrifenox, simeconazol, spiroxamin, tebuconazol, terbinafin, tetraconazol, triadimefon, triadimenol, tridemorph, triflumizole, triforin, triticonazol, uniconazol, viniconazol, voriconazol;

- substances capable of inhibiting cell wall synthesis, such as benthiavalicarb, dimethomorph, flumorph, iprovalicarb, mandipropamid, polyoxins, polyoxorim, validamycin A;

- substances capable of inhibiting melamine biosynthesis, such as carpropamid, diclocymet, fenoxanil, ftalid, pyroquilon, tricyklazol;

«

- substances capable of inducing résistance towards pathogens and insect pests, such as acibenzolar-S-methyl, probenazol, tiadinii;

- substances with a wide range of therapeutic effects, such as Bordeaux misture, captafol, captan, chlorothalonil, copper naphtcnane, copper(II) oxide, copper(II) oxychloride, copper-calcium oxychloride, copper(II) hydroxide, copper(II) sulphate, basic copper(II) sulphate, dichlofluanid, dithianon, dodine, dodine free base, ferbam, fluorofolpet, folpet, guazatine, guazatine acetate, iminoktadin, iminoktadîn albesilate, iminoktadin triacetate, mancopper, mancozeb, maneb, metiram, zinc metiram, copper(II) bis(8-hydroxyquinolinate), propineb, sulphur and sulphur-containing préparations, such as calcium polysuiphide, tolylfluanid, zineb, ziram;

- compounds selected from the following list: (2E)-2-(2-{[6-(3-chloro-2methylphenoxy)-5-fluorpyrimidm-4-yl]oxy}phenyl)-2-(methoxyimino)-N- methyl ace t amide, (2E)-2- {2-[( {[( l E)-1 -(3-{ [(E)-1 -fluoro-2phenylvinyl]oxy}phenyl)ethylidene]amïno}oxy)methyl]phenyl}-2-(methoxyimmo)N-methylace tamide, 1 -(4-chlorophenyl)-2-( 1 H-1,2,4-triazol-1 -yl)cycloheptanol, 1 -[(4methoxyphenoxy)methyl]-2,2-dimethylpropyl-1 H-imidazole-1 -carboxylate, 1 -methylN-[2-( 1,1,2,2-tetrafluoroethoxy)phenyl]-3-(trifluoromethyl)-1 H-pyrazole-4carboxamide, 2,3,5,6-tetrachloro-4-(methylsulphonyl)pyridine, 2-butoxy-6-iodo-3propyl-4H-chromen-4-one, 2-chloro-N-( 1,1,3-trimethyl-2,3-dihydro-l H-inden-4yl)nicotinamide, 2-phenylphenol and salts thereof, 3-(difluoromethyl)-l-methyl-N-[2(l,l,2,2-tetrafluoroethoxy)phenyl]-lH-pyrazole-4-carboxamide, 3-(difluoromethyl)N-[(9R)-9-isopropyl-l ,2,3,4-tetrahydro-l ,4-methanonaphthalen-5-yl]-1 -methyl- 1Hpyrazole-4-carboxamide, 3-(difluoromethyl)-N-[(9S)-9-isopropyl-1,2,3,4-tetrahydro1,4-methanonaphthalen-5-yl]-1 -methyl- lH-pyrazole-4-carboxamide, 3(difluoromethyl)-N-[4'-(3,3-dimethylbut-1 -yn-1 -yl)biphenyl-2-yl]-1 -methyl-1Hpyrazole-4-carboxamide, 3,4,5-trichloropyridine-2,6-dicarbonitrile, 3-(5-(4chlorophenyl)-2,3-dimethylisoxazolidin-3-yI]pyridine, 3-chioro-5-(4-chlorophenyl)-4-

(2,6-difluorophenyl)-6-methylpyridazine, ,4-(4-chlorophenyl)-5-(2,6-difluorophenyl)3,6-dimethylpyridazine, 5-chloro-7-(4-methylpiperidin-l-yl)-6-(2,4,6trifluorophenyl)[ 1,2,4]triazolo[ 1,5-a]pyrimidine, 8-hydroxyquinoline sulphate, benthiazol, bethoxazin, capsimycïn, carvone, chinomethionat, cufraneb, cyflufenamid, cymoxanil, dazomet, debacarb, dichlorofen, diclomezine, dicloran, difenzoquat, difenzoquat methylsulfate, diphenylamin, ecomate, ferimzone, flumetover, fluopicolid, fluoroimid, flusulfamid, fosetyl-aluminium, fosetyl-calcium, fosetylsodium, hexachlorbenzen, irumamycin, isotianil, methasulfocarb, methyl (2E)-2-{2[( {cyclopropyl [(4-methoxypheny l)imino] methyl} thio)methyl]phenyl} -3methoxyacrylate, methyl l-(2,2-dimethyl-2,3-dihydro-lH-inden-l-yl)-lH-imidazole5-carboxylate, methyl isothiocyanate, metrafenon, mildiomycin, N-(3',4'-dichloro-5fluorobiphenyl-2-yl)-3-(difluoromethyl)-l-methyl-lH-pyrazole-4-carboxamide, N-(3ethyl-3,5,5-trimethylcyclohexyl)-3-(formylamino)-2-hydroxybenzamide, N-(4-chloro2-nïtrophenyl)-N-ethyl-4-methylbenzenesulphonamïde, N-(4-chlorobenzyl)-3-[3methoxy-4-(prop-2-yn- l-yloxy)phenyl]propanamide, N-[(4chlorophenyl)(cyano)methyl]-3-[3-methoxy-4-(prop-2-yn-lyloxy)phenyl]propanamide, N-[(5-bromo-3-chloropyridin-2-yl)methyl]-2,4dichloronicotinamide, N-[l-(5-bromo-3-chloropyridin-2-yl)ethyl]-2,4dichloronicotinamide, N-[l -(5-bromo-3-chloropyridin.-2-yl)ethyl]-2-fluoro-4iodonicotinamide, N-[2-( 1,3-dimethylbuty l)phenyl]-5-fluoro-1,3-dimethyl-1Hpyrazol-4-carboxamide, N-{(Z)-[(cyclopropylmethoxy)imino][6-(difluoromethoxy)2,3-difluoro phenyl] methyl} -2-phenylacetamide, N- {2-[ 1,1 '-bi(cyclopropy l)-2yl]phenyl}-3-(difluoromethyl)-l-methyl-lH-pyrazole-4-carboxamide, N-{2-[3-chloro5-(trifluoromethyl)pyridin-2-yl]ethyl)-2-(trifluoromethyl)benzamÎde, natamycine, Nethyl-N-methyl-N'- {2-methyl-5 -(trifluorom ethyl)-4-[3 (trimethylsilyl)propoxy]phenyl}imidoformamide, N-ethyl-N-methyl-N'-{2-methyl-5(difluoromethyl)-4-[3-(trimethylsilyl)propoxy]phenyl) imido formamide, nickel(II) dimethyldithiocarbamate, nitrothal-îsopropyl, O-{ l-[(4-methoxyphenoxy)methyl]-2,2dimethylpropyl] lH-imidazole-l-carbothioate, octhilinon, oxamocarb, oxyfenthiin, pentachlorofenol and salts thereof, phosphonic acid and salts thereof, piperalin, · propamocarb fosetylate, propanosin-sodium, proquînazid, pyribencarb, pyrrolnitrine, quïntozene, S-allyl-5-amino-2-isopropyl-4-(2-methylphenyl)-3-ôxo-2,3-dihydro-1Hpyrazole-l-carbothioate, tecloftalam, tecnazene, triazoxid, trichlamid, valiphenal, zarilamid;

- compounds with bactericïdal effects, such as bronopol, dichlorofen, nitrapyrin, nickel(II) dimethyldithiocarbamate, kasugamycin, octhilinon, furancarboxylic acid, oxytetracyclin, probenazol, streptomycin, tecloftalam, copper(ïï) sulphate and further compounds and préparations containing copper.

S

The préparation of the invention can be used for both curative and prophylactic protection of plants against fungal pathogens in such a way that it is applied to the plants, seeds, fruits or into the soil in which the plants are grown. The crops that can be protected by this method include, e.g., cotton plant, flax, grapevine, crops of the family 10 Rosaceae (e.g., apple tree, pear tree, apricot tree, almond tree, peach tree, strawberry plant), Ribesioidae, Juglandaceae, Betulaceae, Anacardiaceae, Fagaceae, Moraceae, Oleaceae, Actinidaceae, Lauraceae, Musaceae, Rubiaceae, Theaceae, Sterculiceae, Rutaceae (e.g., lemon tree, orange tree, grapefruit), Solanaceae (e.g., tomato), Liliaceae, Asteraceae (e.g. lettuce), Umbelliferae, Cruciferae, Chenopodiaceae, Cucurbitaceae, 15 Papilionaceae (e.g., peas), Graminae (e.g., com, grass or cereals such as wheat, barley, oaf rye or triticale), Asteraceae (e.g., sunflowers), Poaceae (e.g., rice, sorghum), Cucurbitaceae (e.g., cucumber, pumpkin, melon, marrow), Brassicaceae (e.g., cabbage), Cruciferae (e.g., râpe plant), Apiaceae (e.g., canots, parsley, celery), Alliaceae (e.g., onîon), Fabacae (e.g., peanut), Papilionaceae (e.g., soybean, lens, peas, beans), 20 Solanaceae (e.g., potatoes, pepper), Chenopodiaceae (e.g., sugar beet, spinach); in general, agricultural, technical and horticultural crops and their genetically modified homologues.

The préparation of the invention can preferably be used for the protection of the cereals 25 of the family Graminae, e.g., wheat, barley, oat, rye or triticale.

The préparation of the invention can be used for prophylaxis or treatment of, e.g., the following diseases caused by the pathogens of the généra:

Altemaria, caused by, e.g., Altemaria solani;

Aspergillus, caused by, e.g., Aspergillus flavus;

Blumeria, caused by, e.g., Blumeria graminis;

Botrytis, caused by, e.g., Botrytîs cinerea;

Bremia, caused by, e.g., Bremia lactucae;

Cercospora, caused by, e.g., Cercospora beticola;

Cladosporum, caused by, e.g., Cladosporium cucumcrinum;

Claviceps, caused by, e.g., Claviceps purpurea;

Cochliobolus caused by, e.g., Cochliobolus sativus;

Colletotrichum, caused by, e.g., Colletotrichum lindemuthanium;

Corticium, caused by, e.g., Corticium graminearum;

Cycloconium, caused by, e.g., Cycloconium oleaginum;

Diaporthe, caused by, e.g., Diaporthe citri;

Diplodia, caused by, e.g., Diplodia maydis

Elsinoe, caused by, e.g., Elsinoe fawcettii;

Esca, caused by,*e.g., Phaemoniella clamydospora;

Eutypa, caused by, e.g., Eutypa lata;

Fusarium, caused by, e.g., Fusarium oxysporum, Fusarium culmorum, Fusarium solani,

Fusarium graminearum, Fusarium verticillioides or Fusarium moniliforme; Gaeumannomyces, caused by, e.g., Gaeumannomyces graminis;

Gibberella, caused by, e.g., Gibberella zeae nebo Gibberella fujikuroi;

Gloeosporium, caused by, e.g., Gloeosporium laeticolor;

Glomerella, caused by, e.g., Glomerella cingulata;

Guignardia, caused by, e.g., Guignardia bidwelli;

Gymnosporangium, caused by, e.g., Gymnosporangium sabinae;

Helminthosporium, caused by, e.g., Helminthosporium solani;

Hemileia, caused by, e.g., Hemileia vastatrix;

Leptosphaeria, caused by, e.g., Leptosphaeria maculans nebo Leptosphaeria nodorum;

Magnaporthe, caused by, e.g., Magnaporthe grisea;

Microdochium, caused by, e.g., Microdochium nivale;

Monilinia, caused by, e.g., Monilinia laxa;

Monographella, caused by, e.g., Monographella nivalis;

Mycosphaerella, caused by, e.g., Mycosphaerella graminicola, Mycosphaerella arachidicola or Mycosphaerella fijiensis;

Nectria, caused by, e.g.. Nectria galligena;

Ophiostoma, caused by, e.g., Ophiostoma ulmi (Brisman) Nannf.;

Pénicillium, caused by, e.g., Pénicillium expansum nebo Pénicillium brevicompactum;

Peronospora, caused by, e.g., Peronospora pisi nebo P. brassicae;

Phaeosphaerîa, caused by, e.g., Phaeosphaeria nodorum;

Phakopsora, caused by, e.g., Phakopsora pachyrhizi nebo Phakopsora meibomiae;

Phoma, caused by, e.g., Phoma beta, Phoma batata nebo Phoma solani;

Phomopsis, caused by, e.g., Phomopsis viticola

Phytophthora, caused by, e.g., Phytophthora infestans nebo Phytophthora cactorum;

Plasmopara, caused by, e.g., Plasmopara viticola;

Podosphaera, caused by, e.g., Podosphaera leucotricha;

Pseudoperonospora, caused by, e.g., Pseudoperonospora humuli nebo Pseudoperonospora cubensis;

Puccinia, caused by, e.g., Puccinia recondita;

Pyrenophora, caused by, e.g., Pyrenophora teres;

Pythium, caused by, e.g., Pythium ultimum;

Ramularia, caused by, e.g., Ramularia collo-cygni;

Rhizoctonia, caused by, e.g., Rhizoctonia solani;

Rhizopus, caused by, e.g., Rhizopus arrhizus nebo Rhizopus stolonifer;

Rhynchosporium, caused by, e.g., Rhynchosporium secalis;

Sclerotinia, caused by, e.g., Sclerotinia sclerotiorum;

Sclerotium, caused by, e.g., Sclerotium rolfsii;

Septoria, caused by, e.g., Septoria apii nebo Septoria lycopercisi;

Sphacelotheca, caused by, e.g., Sphacelotheca reiliana;

Sphaerotheca, caused by, e.g., Sphaerotheca fuliginea;

Tapesia, caused bÿ, e.g., Tapesia acufonnis;

Taphrina, caused by, e.g., Taphrina deformans;

Thielaviopsis, caused by, e.g., Thielaviopsis basicola;

Tilletia, caused by, e.g., Tilletia caries;

Typhula, caused by, e.g., Typhula incamata;

Uncinula, caused by, e.g., Unctnula necator;

Urocystis, caused by, e.g., Urocystis occulta;

Uromyces, caused by, e.g., Uromyces appendiculatus;

Ustilago, caused by, e.g., Ustilago nuda;

Venturia, caused by, e.g., Venturia inaequalis;

Verticilium, caused by, e.g., Verticilium alboatrum.

The préparation can preferably be used for protection against diseases caused by the pathogens of the genus Fusarium.

il

In a particularly preferred embodiment, the préparation is in the form of suspension concentrate and contains 5 to 30 wt. % of the compound of general formula (I), 5 to 45 wt. % of filler, 2 to 60 wt. % of surfactant, solvent and optionally further auxiliary substances. The solvent is preferably water.

S

The dose of the compound of general formula (I) at foliar application can be in the range of 10 to 1500 g/ha, preferably 25 to 500 g/ha, more preferably 50 to 250 g/ha.

Examples of carrving out the Invention

Example I

Préparation of wettable powders containing compounds of general formula (I)

Wettable powders A to E were prepared from the following raw materials by thorough 15 mixing, grinding and meshing through a 44 pm mesh.

Raw material	Formulation [wt. %]
A	B	C	D	E
Cu2SO3.CuSO3.2H2O	70			50	50
Cu2SO3.MnSO3.2H2O		70		20
Cu2SO3.FeSO3.2H2O			70		20
Sodium polynaphthalenesuphfonate	4	4	4	4	4
Kaolin (particle size 1.4 pm)	26	26	26	26	26 ·

Example 2

Préparation of suspension concentrâtes comprising compounds of general formula (I)

Suspension concentrâtes F to J were prepared according to the following procedure: kaolin was suspended and hydrated in water. Sodium polynaphthalenesulphonate and compound of general formula (I) were added. The mixture was homogenized.

Stabilized suspension concentrâtes K to O were prepared according to the following procedure: kaolin was suspended and hydrated in water. Sodium polynaphthalenesulphonate, compound of general formula (I) and sodium hydrogensulphite solution were added. The mixture was homogenized.

Raw material	Formulation [wt. %]
F	G	H	I	J	K	L	M	N	O
Cu2SO3.CuSO3.2H2O	IS			10	10	15			10	10
Cu2SO3.MnSO3.2H2O		15		5			15		5
Cu2SO3.FeSO3.2H2O			15		5			15		5
Sodium polynaphthalenesulphonate	3	3	3	3	3	3	3	3	3	3
Kaolin (particle size 1.4 pm)	35	35	35	35	35	35	35	35	35	35
Sodium hydrogensulphite, 35% solution						I	1	1	1	1
Water	47	47	47	47	47	46	46	46	46	46

Example 3

Funga! mycélium growth inhibition assay

The assay for inhibitory activity of compounds of general formula (I) to radial growth 10 and morphological effects to mycelia was carried out in agar by a multiple dilution method. The compound was diluted to concentrations shown in the Table in potato dextrose agar prepared in accordance with manufacturer's instructions. Pétri dishes were filled with the thus prepared agar and aseptically inoculated with a dise of the diameter of 0.4 cm eut from a 7-day agar culture of the respective fungus. Controls were prepared in 15 an analogous manner, using stérile distilled water instead of compound of general formula (1). The Pétri dishes were incubated for Ί days at 21 ^DC and then the diameter of the colonies was measured. The percentage of inhibition of radial growth of the respective fungus was calculated according to the following équation: inhibition [%] = (DC-DT)/D0100, wherein DC is the diameter of control colony and DT is the diameter 20 of the colony grown on the agar containing the respective amount of compound of general formula (I). Standard déviation corresponds to averages from 3 réplications.

The results are shown in Tables 1 and 2. The compound Cu2SO3.CuSO3.2H2O inhibited the growth of ail tested mycelia (Table 1). Individual micelia hâve shown a variation in the sensitivity to the compound and concentration dependency on the fungicide dose was observed. The tested mycelia exhibited significant morphological changes, such as sparse 5 or atypical growth (Table 2) which is bénéficiai for fungicidal use.

Table 1: Percentage of radial growth inhibition

Mycélium	Cu2SO3.CuSO3.2H2O [mg/mL agar]
0.3	0.4	0.5
Fusarium oxysporum	6.72 ± 0.05 % *>	59.70 ±0.16% 0	97.76 ± 0.00 %
Fusarium verticillioides	“2.81 ± 0.00 %	19 10 ± 0.16 % 25	~30.90 ± 0.00 %*>
Pénicillium brevicompactum	77.78 ± 0.09 %	95.24 ± 0.00 %	100.00 ±0.00%
Pénicillium expansum	98.37 ± 0.05 %	96.75 ± 0.05 %	100.00 ±0.00%
Aspergillus flavus	97.67 ± 0.05 %	98.84 ± 0.05 %	100.00 ±0.00%
Aspergillus fumigatus	100.00 ±0.00%	100.00 ± 0.00 %	100.00 ± 0.00 %

^l) sparse mycélium ²⁾ sparse yeast-like growth of the mycélium lû

Table 2: Morphological changes of mycelia

Mycélium	Cu2SO3.MnSO3.2H2O [mg/mL agar]	CU2S O3 .FeS O3.2 H2O [mg/mL agar]
0.5	0.9	0.5	0.9
Fusarium oxysporum	sparse yeastlike growth of the mycélium	sparse yeastlike growth of the mycélium	sparse yeastlike growth of the mycélium	sparse yeastlike growth of the mycélium
Aspergillus flavus	inhibition of sporulation, changes in pigmentation	atypical growth, irregular and very sparse mycélium	changes in pigmentation around the colony	changes in pigmentation around the colony

Example 4

Field trial with crops

In 2010 and 2011, field trials using Triticum aestivum L. and Hordeum vulgare L. were performed. The experimental field was chosen in a warm région suitable for beet cultivation, with sufficient précipitation, soil type was brown earth. The plants were treated using a common agrotechnology, with the exception of the application of fungicidal protection. Instead, the compound Cu2SO3.CuSO3.2H2O was applied in the form of foliar spraying of wettable powder A prepared according to Example 1, in the dose according to Table 3, in the growth phase BBCH 62 (flowering), when the cereals are typically treated against the Fusarium mould infection of the ear. The broadscale commercial fungicidal préparation Horizon 250 EW (Bayer) containing tebuconazol as the active substance was used as a control, in the dose recommended by the manufacturer (Table 3). Water was used as the négative control.

At the end of the végétative season, the crops were harvested and the yield was determined. For both crops, positive effect on the yield was observed, the yield increased by 3.2 to 10.1 % (see Table 3). No phytotoxic effects were observed, neither occurence of fusarioses or other fongal diseases. In comparison with the recommended dose of the commercial fongicide Horizon 250 EW, the yield was similar or higher. The total dose of copper per hectar corresponding to the lower application dose of Cu2SO3.CuSO3.2H2O (125 g/ha), which was fully sufficient to ensure the protective fungicidal effect, is 61 g/ha, that is 30 to 40 times less than for the usual dose of préparations containing CuCl₂.3Cu(OH)₂.

In 2011, a high concentration of Cu2SO3.CuSO3.2H2O (625 g/ha) was tested for both crops. No phytotoxic effects were observed even at this dose.

Table 3

Crop	Year	Dose of Cu2SO3.CuSO3.2H2O [g/ha]	Horizon 250 EW [ml/ha]	Yield [t/ha]	% of the control
Triticum aestivum	2010	125	—	7.34	104.7
—	1000	7.00	100.0
—.	—	7.01	100.0
2011	125	—	8.45	108.1
625	—	8.60	110.1
— ,	1000	8.08	103.4
—	— ·	7.81	100.0
Hordeum vulgare	2011	125	—	8.65	103.2
625	—	8.73	104.2
—	1000	8.73	104.2
—	—	8.38	100.0

Claims (5)

1. Use of compounds of general formula (I)

Cu2SO3.MSO3.2H2O (I) wherein M is Cu, Mn or Fe, for protection of plants against fungal diseases.

2. Use according to claim 1, wherein the compound of general formula (I) is Cu2SO3.CuSO3.2H2O.

3. A method of protecting plants against fungal diseases, characterized in that at least one 15 compound of general formula (I)

Cu2SO3.MSO3.2H2O (I) wherein M is Cu, Mn or Fe

20 is applied to seeds, plant, fruits or into soil.

4. The method according to claim 3, wherein the compound of general formula (I) is applied using folîar application in the amount in the range of 10 to 1500 g/ha, preferably 25 to 500 g/ha, more preferably 50 to 250 g/ha.

5. The method according to claim 3 or 4, wherein the compound of general formula (I) is

Cu2SO3.CuSO3.2H2O.

6. Pesticidal, in particular fungicidal, préparation for protection of plants, characterized in 30 that it contains at least one compound of general formula (I)

Cu2SO3.MSO3.2H2O

d) wherein M is Cu, Μη or Fe, preferably in the amount of 1 to 99 wt. %.

7. The préparation according to claim 6, further containing auxiliary substances selected 5 from the group comprising fillers, surfactants, antioxidants, defoamers and further auxiliaries.

8. The préparation according to claim 6 or 7, wherein the compound of general formula (I) is Cu₂SO₃.CuSO₃.2H₂O.

9. The préparation according to any of claims 6 to 8, wherein the compound of general formula (I) has a particle size smaller than 100 pm, preferably smaller than 75 pm, more preferably smaller than 50 pm.

15 10. The préparation according to any of claims 6 to 9, which further comprises at least one substance selected from the group comprising insecticides, fongicides, bactéricides, attractants, akaricides, pheromones and further biologically active substances.

Π. The préparation according to any of claims 6 to 10, which is in the form of 20 suspension concentrate and contains 5 to 30 wt. % of the compound of general formula (I), 5 to 45 wt. % of filler, 2 to 60 wt. % of surfactant, solvent and optionally further auxiliary substances.

Abstract

Title

5 Pesticide compounds, use thereof and method of protection of plants

The invention provides use of compounds of general formula Cu2SO3.MSO3.2H2O, wherein M is Cu, Mn or Fe, for the protection of plants against fungal diseases. Further, 10 it encompasses a method of protecting plants against fungal diseases and a pesticidal préparation comprising at least one compound of said general formula.