KR100686791B1 - Fungicidal mixtures - Google Patents

Abstract

The present invention provides an acceptable carrier and / or surface active agent and a synergistically effective amount of (a) at least one azopyrimidine of formula (1) and (b) at least one melanin biosynthesis inhibitor (MBI), preferably phenoxyamide of formula (2) Fungicidal composition comprising a; And spraying at least one synergistically effective amount of at least one azolopyrimidine (a) and at least one MBI (b) of the growth site to a growth site, the method of inhibiting the growth of phytopathogenic fungi at the growth site.

Where

R ¹ , R ² , L, A and n have the meanings given in claim 1;

R ⁵ -R ⁹ , Y and m have the meanings given in claim 2.

Azolopyrimidines, melanin biosynthesis inhibitors, fungicidal compositions

Description

Fungicidal mixtures {FUNGICIDAL MIXTURES}

The present invention provides a carrier and / or surface active agent and a synergistically effective amount of (a) at least one azolopyrimidine of formula (1) and (b) Pyricularia oryzae, a causative agent of febrile disease It relates to a fungicidal composition comprising at least one fungicidal active ingredient that can inhibit melanin biosynthesis.

Formula 1

Where

R ¹ and R ² each independently represent hydrogen or an optionally substituted alkyl, alkenyl, alkynyl, alkadienyl, aryl, heteroaryl, cycloalkyl, bicycloalkyl or heterocyclyl group, or

R ¹ and R ^{2 together} with the neighboring nitrogen atom represent an optionally substituted heterocyclic ring,

R ³ represents hydrogen or a halogen atom or an alkyl group,

R ⁴ represents hydrogen or an alkyl or aryl group,

L represents a halogen atom or an optionally substituted alkyl or alkoxy group,

A represents N or CR ⁵ , wherein R ⁵ has the meaning given for R ⁴ ,

n is 0 or an integer between 1 and 5;

Fungicidal compounds of Formula 1 are known from US Pat. Nos. 4,567,263 and US 5,593,996.

The melanin biosynthesis inhibitor (MBI) class can reduce melanin synthesis in vivo by inhibiting reductase and / or dehydratase enzymes, which convert tetrahydroxynaphthalene into dihydroxynaphthalene. It is a chemical compound. Compounds of this class include the following known compounds: capropamide, clobenthiazion, diclocimet, pyroquilon, phthalide, tricyclazole and certain phenoxyamides, for example EP 0 262 393 and Japanese Patent Application JP 5-9165-A.

However, there is no indication as to the compound of formula 1 combined with MBI. It is also not implied whether such a mixture can be advantageously used to control rice pests such as blast and rice blots.

Surprisingly, a strong synergy between the compounds of formula 1 and MBI in the field test was found when these two compounds were mixed in a tank and the activity of these co-formulations was compared to the activity of the solo formulation of each active ingredient.

Fungicide mixtures have a synergistic effect if the fungicidal activity of the mixture is greater than the sum of the separately applied compound activities. The expected fungicidal activity for a given two fungicide mixtures can be calculated as follows: Colby, S.R., "Calculating synergistic and antagonistic response of herbicide combinations", Weeds 15, pp 20-22 (1967).

EE = x + y-xy / 100

Where

x is the percent efficacy compared to the untreated control when the fungicidal active ingredient A was treated with the amount of a;

y is the percentage efficacy compared to the untreated control when the fungicidal active ingredient B was treated with the amount b;

EE is the anticipated efficacy of using the fungicidal active ingredient A and B combination in the amount of a + b.

If the actual potency (E) exceeds the expected (calculated) value (EE), the mixture shows a synergistic effect.

Summary of the Invention

The present invention includes fungicidal compositions comprising an acceptable carrier and / or surfactant and a synergistically effective amount of at least one compound of Formula 1, and at least one melanin biosynthesis inhibitor (MBI).

The present invention also includes a method of inhibiting the growth of phytopathogenic fungi at a growth site, comprising spraying at least one synergistically effective amount of at least one azolopyrimidine of Formula 1 and at least one MBI on the growth site.

Detailed Description of the Preferred Embodiments

이

(여기서, L¹은 할로겐 원자, 바람직하게는 불소 또는 염소를 나타내고, L²와 L³는 각각 독립적으로 수소 원자 또는 할로겐 원자, 특히 불소를 나타내며, 특히 L¹이 불소를 나타내고, L²가 수소를 나타내며 L³가 염소를 나타내거나 L¹-L³가 불소를 나타내고/나타내거나 Hal은 염소 원자를 나타냄)를 나타내는 것들을 포함한다. 특히 바람직한 양태에서 아졸로피리미딘은 화학식 1a의 화합물이다.Preferred compounds of formula (1) represent a 6-membered heterocyclic ring, in particular a 4-methylpiperidine ring, in which R ¹ and R ^{2 together} with the neighboring nitrogen atoms, or R ¹ is C _1-6 alkyl, in particular iso Propyl group, C _1-6 haloalkyl, especially 2,2,2-trifluoroethyl or 1,1,1-trifluoroprop-2-yl group, or C _3-8 cycloalkyl group, in particular cyclopentyl Or represents a cyclohexyl group and R ² represents a hydrogen atom or a C _1-6 alkyl group

this

(Wherein L ¹ represents a halogen atom, preferably fluorine or chlorine, L ² and L ³ each independently represents a hydrogen atom or a halogen atom, in particular fluorine, in particular L ¹ represents fluorine, L ² represents hydrogen And L ³ represents chlorine, L ¹ -L ³ represents fluorine and / or Hal represents a chlorine atom. In a particularly preferred embodiment the azopyrimidine is a compound of formula 1a.

Where

L and n have the meaning given in Formula 1,

R ¹ represents an alkyl or haloalkyl group,

R ² represents a hydrogen atom, or

R ¹ and R ² together represent an optionally substituted alkylene group having 3 to 6 carbon atoms in the main chain, where one CH ₂ group can be replaced with O or NH,

Hal represents a halogen atom.

Particular preference is given to the following azolopyrimidines: 5-chloro-6- (2-chloro-6-fluorophenyl) -7- (4-methylpiperid-1-yl)-[1,2,4] Triazolo [1,5-a] pyrimidine (coding name azolopyrimidine A), 5-chloro-6- (2-chloro-6-fluorophenyl) -7-isopropylamino- [1,2, 4] triazolo [1,5-a] pyrimidine (codename Azolopyrimidine B), 5-chloro-6- (2-chloro-6-fluorophenyl) -7- (2,2,2 -Trifluoroethylamino)-[1,2,4] triazolo [1,5-a] pyrimidine (coded name azolopyrimidine C) and 5-chloro-6- (2,4,6-tri Fluorophenyl) -7- (1,1,1-trifluoroprop-2-ylamino)-[1,2,4] triazolo [1,5-a] pyrimidine (coding name azopyrimidine D).

Preferred MBIs include capropamide, clobenthiazion, dicyclocymet, pyroquilon, phthalide and tricyclazole.

Phenoxyamides of formula (2) are also preferred MBI:

Formula 2

Where

R ⁵ and R ⁶ each independently represent a hydrogen atom or an optionally substituted alkyl group;

R ⁷ independently represents a hydrogen atom or an optionally substituted alkyl group;

R ⁸ and R ⁹ each independently represent a hydrogen atom or an optionally substituted alkyl or alkenyl group; R ⁸ and R ⁹ may together represent an alkylene group;

Each Y independently represents a halogen atom or an optionally substituted alkyl or alkenyl group or a cyano or nitro group;

m is 0 or an integer 1,2,3 or 4.

Particularly preferred phenoxyamides are the compounds of formula 2a.

Where

R ⁹ , Y and m have the meanings given above,

는

를 나타내며,Especially

Is

Indicates

Y 'represents a hydrogen atom or a methyl group and / or

R ⁹ represents a C _1-8 alkyl group.

N- (1-cyano-1,2-dimethyl-propyl) -2- (2,4-dichlorophenoxy) -propionamide, in particular (2R)-and (2R / S) -N- (1-cya No-1,2-dimethyl-propyl) -2- (2,4-dichlorophenoxy) propionamide (coded name propionamide E) and N- (1-cyano-1-ethyl-propyl) -2- ( Most preferred is 2,4-dichloro-3-methylphenoxy) propionamide (coding name propionamide F).

Preferred formulations of the invention include those comprising the following ingredients:

A carrier;

At least one azolopyrimidine of the formula (1);

At least one MBI, in particular phenoxyamide of formula 2;

Optionally a defoamer, in particular a mixture of perfluoroalkylphosphonic acid and / or perfluoroalkylphosphinic acid, in particular Defoamer SF or Fluowett PL commercially available from Clariant GmbH.

The compound of formula 1 and MBI may be sparged together in a synergistically effective amount. These synergistic mixtures exhibit particular potency against a wide range of phytopathogenic fungi, particularly fungi of the classes of ascomycetes, basidiomycetes and deuteromycetes. Thus, they can be advantageously applied to rice pests. They are permeable transitional and can be sprayed into water, seed dressings, nurseries or soil fungicides, as in leaves.

The mixtures according to the invention are preferably applied to control phytopathogenic fungi of the following genus: Pyricularia, Rhizoctonia, Cochliobolus, Sercosphora (Cercospora), Magnaporthe, Alternaria, Drechslera, Fusarium, Gerlachia, Achlya, Slerotium ( Sclerotium, Gibberella, Mycosphaerella, Balansia, Sarocladium, Pythium, Phoma, Phytophthora, Bipolaris Bipolaris, Curvularia, Sarocladium, Nigrospora, Entyloma, Sclerophthora, Cylindrocladium, Gemannomices (Gaeumannomyces), Myrothecium, Muco, Rhizopus, Tilletia, Ustilago, Ustilaginoidea, Bipolaris, Sclerotium, Botrytis, Venturia, Eritife (Erysiphe), Septoria, Puccinia, Leptosphaeria and Pseudocercosporella, in particular Rhizoctonia solani, Cochliobolus miyaveanus (Cochliobolus miyabeanus), Sparulina oryzina, Leptosphaeria slavini and Pyricularia oryzae species.

The application rate of the compound of formula (1) according to the invention is generally in the range of 5 to 2000 grams of active ingredient (g a.i.) per hectare, often with a ratio of 30-500 g a.i./ha to achieve satisfactory relief. The optimum rate for a particular application will depend on the cultivated crop (s) and predominantly infected fungal species but can be readily determined by existing biotests by those skilled in the art.

In general, the preferred spreading rate of the compound of formula 1 is in the range of 10 to 500 g a.i./ha, more preferably in the range of 30-300 g a.i./ha.

The optimal rate of MBI will depend on the level of infection by the cultivated crop (s) and fungi, which can easily be determined through existing biological tests.

The (weight) ratio of compound of formula (I): MBI is generally from 1: 100 to 100: 1. Preferred ratios of Formula 1: MBI may vary, for example, from about 1:50 to about 50: 1, especially from about 1: 4 to about 4: 1.

The active compound will be formulated in a suitable ratio according to the invention with the usual carriers and / or additives known in the art.

The present invention therefore further provides a fungicidal composition comprising as a carrier and the active ingredient at least one compound of formula (I) as defined above and at least one MBI.

There is also provided a process for the preparation of such a composition comprising combining the compound of formula 1 and MBI as defined above with at least one carrier. It is also contemplated that different isomers or mixtures of isomers of Formula 1 and / or MBI may have different levels or ranges of activity so that the compositions may comprise individual isomers or mixtures of isomers.

The composition according to the invention preferably contains 0.1% to 99.9%, preferably 0.2% to 80% (weight / weight) of the active ingredient.

In the compositions according to the invention, the carrier is a substance used in the formulation of the active ingredient, which makes it easy to spray, store, or spray the plant, seed, leaf, or growth site to be treated, such as the water in which the plant grows, or the root, To facilitate transportation or handling. The carrier may be a solid or a liquid, and also includes a substance which is usually present as a gas and liquefied upon compression.

The composition may be, for example, emulsion or emulsion concentrates, solutions, oil-in-water emulsions, wettable powders, soluble powders, suspension concentrates, solutions, dusts, granules, water dispersible granules, tablets, aerosols, microcapsules, gels and It can be prepared in other formulation types by well established procedures. These processes involve strong mixing and / or milling of the active ingredient with other materials such as fillers, solvents, solid carriers, surface active compounds (surfactants), and optionally solid and / or liquid auxiliaries and / or auxiliaries. . Spray forms such as spraying, spraying, dispersing or pouring can be selected as in the case of compositions according to the desired purpose and given circumstances.

200, 치환 나프탈렌, 디부틸 또는 디옥틸 프탈레이트와 같은 프탈산 에스테르, 지방족 탄화수소, 예를 들면, 사이클로헥산 또는 파라핀, 알콜과 글리콜 및 이들의 에테르 및 에스테르, 예를 들면, 에탄올, 에틸렌글리콜 모노- 및 디메틸 에테르, 사이클로헥사논과 같은 케톤, N-메틸-2-피롤리돈, 또는 γ-부티로락톤과 같은 강한 극성 용매, 고급 알킬 피롤리돈, 예를 들면, n-옥틸피롤리돈 또는 사이클로헥실피롤리돈, 에폭시화된 식물유 에스테르, 예를 들면, 메틸화된 코코넛 또는 대두유 에스테르 및 물일 수 있다. 상이한 액체 혼합물도 종종 적당하다.The solvent is an aromatic hydrocarbon, for example Solvesso

200, phthalic acid esters such as substituted naphthalene, dibutyl or dioctyl phthalate, aliphatic hydrocarbons such as cyclohexane or paraffin, alcohols and glycols and their ethers and esters such as ethanol, ethylene glycol mono- and dimethyl Ketones such as ethers, cyclohexanone, strong polar solvents such as N-methyl-2-pyrrolidone, or γ-butyrolactone, higher alkyl pyrrolidones such as n-octylpyrrolidone or cyclohexylpi It may be a rollidone, epoxidized vegetable oil ester such as methylated coconut or soybean oil ester and water. Different liquid mixtures are also often suitable.

Dust, wettable powders, water dispersible granules, or solid carriers available for granulation may be mineral fillers such as calcite, talc, kaolin, montmorillonite or attapulgite. Physical properties can be improved by adding highly dispersed silica gel or polymer. The granular carrier may be a porous material such as pumice, kaolin, sepiolite, bentonite; The non-sorbable carrier may be calcite or sand and the like. In addition, many pre-granulated inorganic or organic materials can be used, such as dolomite or ground plant residue.

Insecticidal compositions are often formulated and transported in concentrated form and diluted by the user prior to subsequent application. The presence of a small amount of carrier which is a surfactant facilitates this dilution process. Thus, at least one carrier in the composition according to the invention is preferably a surfactant. For example, the composition may contain at least one surfactant in two or more carriers.

The surfactant may be a nonionic, anionic, cationic or zwitterionic material with good dispersibility, emulsification and wettability depending on the nature of the compound of formula 1 to be formulated. Surfactant may also mean a mixture of individual surfactants.

The wettable powders of the present invention suitably contain from 5 to 90% by weight of active ingredient and further solid inert carriers, from 3 to 10% by weight of dispersant and wetting agent and, if necessary, from 0 to 10% by weight of stabilizer. (S) and / or other additives such as penetrants or fixatives. The dust can be formulated in the form of a dust concentrate with a composition similar to the wettable powder, except that it does not contain a dispersant, and is diluted in the field with an additional solid carrier and generally contains 0.5 to 10% by weight of the active ingredient. One composition is provided. Water dispersible granules and granules can have a size of 0.15 mm to 2.0 mm and can be prepared by various techniques. In general, these granules will contain from 0.5 to 90% by weight of active ingredient and from 0 to 20% by weight of additives such as stabilizers, surfactants, slow release modifiers and binders. Emulsifiable concentrates may further comprise solvents or solvent mixtures, from 1 to 80% by volume of active ingredient, from 2 to 20% by volume of emulsifier and from 0 to 20% by volume of stabilizer, penetrant and corrosion inhibitor. It may contain an additive. Suspension concentrates are suitably milled to obtain a stable, non-precipitate, flowable product and are typically 5 to 75% by weight active ingredient, 0.5 to 15% by volume dispersant, 0.1 to 10% by volume Suspending agents such as protective colloids and thixotropic agents, 0 to 10% by weight / volume of antifoams, other additives such as corrosion inhibitors, stabilizers, penetrants and fixatives, and water or organic liquids, wherein the active ingredient is substantially insoluble Specific organic solids or inorganic salts can be dissolved in the formulation to prevent precipitation and crystallization or in the form of cryoprotectants).

Aqueous dispersions and emulsions, for example compositions obtained by dilution with water, according to the invention, are also within the scope of the invention.

Of particular note with regard to enhancing the duration of the protective activity of the compounds of the invention is the use of a carrier which provides a slow release of the pesticidal compound into the plant environment to be protected.

Adjuvants may be included in the spray dilution to increase the biological activity of the active ingredient. Adjuvants are defined herein as substances which do not have significant biological activity by themselves but which can increase the biological activity of the active ingredient. Adjuvants may be included in the formulation in the form of co-formulations or carriers, or may be added to the spray tank together with the formulation containing the active ingredient.

At the time of sale, the composition may preferably be in the form of a concentrated composition but the end user generally uses the diluted composition. The composition may be diluted to an active ingredient concentration of up to 0.001%. The amount of use is generally in the range of 0.01 to 10 kg a.i./ha.

Examples of formulations which can be used according to the invention are as follows:

SC-A

Active ingredient Azolopyrimidine A 100.0 g

Dispersant Morwet D425 ¹⁾ 25.0 g

PE10500²⁾ 5.0 gDispersant Pluronic

PE10500 ²⁾ 5.0 g

426R³⁾ 1.5 gAntifoam Rhodorsil

426R ³⁾ 1.5 g

23³⁾ 2.0 gDispersants Rhodopol

23 ³⁾ 2.0 g

Cryoprotectant Propylene Glycol 80.0 g

GXL⁴⁾ 1.0 gBiocide Proxel

GXL ⁴⁾ 1.0 g

To 1000 ml of water

SC-B / SC-D

Active ingredient Azolopyrimidine B or D 100.0 g

FL³⁾ 30.0 gDispersant Soprophor

FL ³⁾ 30.0 g

426R³⁾ 1.5 gAntifoam Rhodorsil

426R ³⁾ 1.5 g

23³⁾ 2.0 gDispersants Rhodopol

23 ³⁾ 2.0 g

Cryoprotectant Propylene Glycol 80.0 g

GXL⁴⁾ 1.0 gBiocide Proxel

GXL ⁴⁾ 1.0 g

To 1000 ml of water

SC-E

Active ingredient Propionamide E 200.0 g

FL³⁾ 25.0 gDispersant Soprophor

FL ³⁾ 25.0 g

426R³⁾ 1.5 gAntifoam Rhodorsil

426R ³⁾ 1.5 g

23³⁾ 2.0 gDispersants Rhodopol

23 ³⁾ 2.0 g

Cryoprotectant Propylene Glycol 80.0 g

GXL⁴⁾ 1.0 gBiocide Proxel

GXL ⁴⁾ 1.0 g

To 1000 ml of water

SC-A / E

Active ingredient Azolopyrimidine A 60.0 g

Active ingredient Propionamide E 120.0 g

FL³⁾ 25.0 gDispersant Soprophor

FL ³⁾ 25.0 g

426R³⁾ 1.5 gAntifoam Rhodorsil

426R ³⁾ 1.5 g

23³⁾ 2.0 gDispersants Rhodopol

23 ³⁾ 2.0 g

Cryoprotectant Propylene Glycol 80.0 g

GXL⁴⁾ 1.0 gBiocide Proxel

GXL ⁴⁾ 1.0 g

To 1000 ml of water

DC-A

Active ingredient Azolopyrimidine A 100.0 g

PE6400²⁾ 50.0 gWetting Agent Pluronic

PE6400 ²⁾ 50.0 g

TO 12²⁾ 50.0 gDispersants Lutensol

TO 12 ²⁾ 50.0 g

To 1000 ml of solvent benzyl alcohol.

DC-B

Active ingredient Azolopyrimidine B 100.0 g

PE6400²⁾ 50.0 gWetting Agent Pluronic

PE6400 ²⁾ 50.0 g

TO 12²⁾ 50.0 gDispersants Lutensol

TO 12 ²⁾ 50.0 g

To 1000 ml of solvent benzyl alcohol.

1) Products marketed by Witco

2) Products marketed by BASF AG, Germany

3) Products marketed by Rhone-Poulenc

4) Products marketed by Zeneca

Formulation SC-E with Propionamide E is mixed in tank with other formulations SC-A, SC-B, SC-D, DC-A or DC-B, including Azolopyrimidine A, B or D.

In a preferred embodiment the active ingredients are added together in a tank mix, each in the form of a solo formulation.

Thus, the present invention provides two separate formulations.

(i) a formulation comprising at least one azolopyrimidine of formula 1, in particular Azolopyrimidine A, B, C or D, conventional adjuvants and carriers;

(ii) a kit for the preparation of a spray mixture consisting of a formulation comprising at least one MBI, preferably phenoxyamide of formula 2, in particular Propionamide E or F, conventional adjuvants and carriers:

In a preferred embodiment the kit comprises two bottles with dispersing means allowing easy and accurate addition of formulations (i) and (ii) to the tank mix.

Formulation SC-A / E comprising Azolopyrimidine A and Propionamide E can be used to prepare tank mixes directly according to the invention.

The composition according to the invention preferably contains 0.5% to 95% by weight of active ingredient.

The composition of the present invention may be diluted to a concentration of 0.0001% of the active ingredient.

The composition of the present invention can be applied to the plant or its environment simultaneously or continuously with other active substances. These other active substances can be fertilizers, preparations that provide trace elements or other preparations that affect plant growth. However, they also contain selective herbicides, insecticides, fungicides, fungicides, nematicides, acaricides, molluscicides, insecticides, salvirus, compounds that induce resistance to plants, viruses, bacteria, nematodes, fungi and other microorganisms; Mixtures with many of these preparations, such as biological remedies, algae and animal repellents, and plant growth regulators, or, optionally, other carrier materials, surfactants, or other additives that promote sparging. Can be.

Examples of other fungicidal compounds include anilazine, azoxystrobin, benalacyl, benomil, vinapacryl, bitteranol, blasticidine S, Bordeaux mixture, bromuconazole, burimate, captapol, captan, Copper-containing compounds such as carbendazim, carboxycin, chlorothalonil, clozolinate, copper oxychloride, and copper sulfate, cycloheximide, cynosanyl, sipopuram, ciproconazole, ciprodinyl, dicloflu Anid, Diclone, Dichloran, Diclobutrazole, Diclomezine, Dietofencarb, Difenokazole, Diflumethorim, Dimethymolol, Dimethomorph, Diniconazole, Dinocap, Ditalimfoss , Dithianon, dodemol, dodine, edifene force, epoxyconazole, etaconazole, etirimole, erythrodiazole, pamoxadon, phenafanil, phenarimol, fenbuconazole, fenfuram, phenhexamide, Fenpiclonil, phenpropidine, phenpropimorph, fentin, fentin Cetate, fentin hydroxide, perimzone, fluazinam, fludioxonyl, flumetober, fluquinconazole, flusilazole, flusulfamid, flutolanyl, flutriafol, follpet, pocetyl aluminum , Fuberidazole, furalacyl, furametpyr, guaztine, hexaconazole, imazaryl, imineoctadine, ifconazole, iprodione, iprovalicab, isoprothiolane, kasugamycin, chitazine P , Cresoxime-methyl, mancozeb, maneb, mepanipyrim, mepronyl, metallaxyl, metconazole, metfuroxam, michaelrobutanyl, neoazin, nickel dimethyldithiocarbamate, nitrotal iso Propyl, nourimol, opuras, organic mercury compounds, oxadixyl, oxycarboxycin, fenconazole, pencicuron, phenazine oxide, polyoxine D, polyram, probenazole, prochloraz, procimidion , Propamocarb, propiconazole, propineb, pyrazophos, flute Phenox, pyrimethanyl, pyroxifur, quinomethionate, quinoxifen, quintogen, spiroxamine, SSF-126, SSF-129, streptomycin, sulfur, tebuconazole, teclophthalam, tecnazen , Tetraconazole, thibendazole, tifluzamide, thiophenate-methyl, thiram, toclofosmethyl, tolifluanide, triadimefon, triadimenol, triazbutyl, triazoxide, tride Morph, triflumizol, tripolin, triticonazole, validamycin A, vinclozoline, XRD-563, zarylamide, geneb, ziram.

Examples of pesticidal compounds include alpha-cypermethrin, benfuracarb, BPMC, buprofezin, carbosulphan, cartab, chlorfenbinfos, chlorpyriphos-methyl, cycloprotrin, cipermethrin, es Fenvalyrate, Etofenprox, Fenpropatrine, Flucitrinate, Flufenoxuron, Hydramethylnon, Imidacloprid, Isoxation, MEP, MPP, Nitenpyram, PAP, Fermethrin, Propaphos , Pymetrozine, silafluorene, tebufenozide, teflubenzuron, temefos, terbufos, tetrachlorbinfos and triamate.

Examples of biological control agents include Bacillus thuringiensis, Verticillium lecanii, Autographica californica NPV, Beauvaria bassiana, and Ampeloma. Ampelomyces quisqualis, Bacillus subtilis, Pseudomonas fluorescens, Streptomyces griseoviridis and Trichoderma harzianum.

Examples of chemical agents that induce permeability acquired resistance in plants are isnicotinic acid or derivatives thereof, 2,2-dichloro-3,3-dimethylcyclopropylcarboxylic acid and BION.

The present invention has a wide range of applications in protecting crops and ornamentals from fungal attack. Preferred crops are rice, in particular paddy fields. The duration of protection generally depends on the individual compound selected and on various external factors, such as climate, the effect of which is usually mitigated by using a suitable formulation.

The following examples illustrate the invention in detail. However, it should not be understood that the present invention is limited only to the specific examples given below.

Example

Use Formulated Azolopyrimidine A, B or D (100 g / l DC-A or DC-B; 100 g / l SC-D) and Propionamide E (200 g / l SC-E) formulated for field studies .

Field tests of the method of the invention are carried out in rice fields of the Philippines, Brazil and Japan.

Materials and spraying methods:

Seeds of varieties 'IR-50' are sown in sandy / cultivated soil in a plastic box of 0.07 m2 (0.23x0.3 m). After 14 days, in the Z14 / 20 growth stage, the plants are first sprayed with the fungicidal compound. Weigh the formulated compound and dilute with water. Spray 1000, 200 and 400 g of active ingredient per ha with a manual nebulizer using a 1000 liter spray volume / ha. The amounts of single compounds and mixtures thereof are given in the results table below. Three identical boxes are required per treatment. Spraying is repeated 7 days after the initial application with the same compound / compound mixture at the same amount and spray volume / ha.

Assessment of the pest:

Evaluation of blast and rice blot is performed on day 14 after the first application of the compound (= day 7 after the second application). Calculate% infected leaf area. The following formula is used to assess the efficacy of the compound / mixture of compounds for disease control:

Synergy Measurement:

The synergy is assessed using the percent control value of the specific treatment for the two COLBY equations given above.

Example 1 Control of Bleeding Caused by Pycurulari Duck

Infection with Pycurulari aurise

Three hours after compound sparging (when the plant is dry), in vitro growth conidia suspensions of pyricularia aurise are inoculated on rice leaf surfaces using a manual sprayer. The conidia concentration is about 1 million / ml. The plants are placed in a wet chamber with a relative humidity of about 100% for 24 hours at 24-26 ° C. The plants are taken outdoors until the blast evaluation.

delete

The formulations sprayed, the amount of active ingredient sprayed (expressed in grams of active ingredient per hectare), the results expressed in terms of pest control efficacy and the estimates calculated according to the Colby equation are shown in Table 1 below.

Control of blasting DC-A and DC-B and SC-E expressed as experimental values when applied alone or as a mixture efficacy(%) Formulation Usage (g / ha) Experimental value Estimates DC-A 200 24 - DC-A 400 65 - DC-B 200 28 - DC-B 400 61 - SC-E 100 18 - SC-E 200 41 - DC-A + SC-E 200 + 100 84 38 DC-A + SC-E 400 + 100 87 72 DC-B + SC-E 200 + 100 73 41 DC-B + SC-E 400 + 100 76 68

Example 2 Control of Raiztonia Solani

Raithononia Solani's Infection

Three hours after the second sparging of the compound / compound mixture, the plant is inoculated with the inoculum on the surface of the planted soil to inoculate the plant with Raiztonia solani (growing in rice flour-chaff medium). The plant is placed in the wet chamber for 24 hours. The plants are then taken outdoors until the rice blot is evaluated.

The sprayed formulation, the amount of sprayed active ingredient (expressed in grams of active ingredient per hectare), the results expressed in pest control efficacy and the expected efficacy calculated by the Colby equation are shown in Table 2 below. Disease symptoms (heating and rice staining) are assessed 7 days after the second application of the product (DAT).

Percentage of rice blot control of DC-A and DC-B and SC-E expressed as predicted using the COLBY equation and in the case of spraying alone or in mixtures: efficacy(%) Formulation Usage (g / ha) Experimental value Estimates DC-A 200 45 - DC-A 400 87 - DC-B 200 75 - DC-B 400 85 - SC-E 100 18 - SC-E 200 23 - DC-A + SC-E 200 + 100 88 55 DC-A + SC-E 400 + 100 89 89 DC-B + SC-E 200 + 100 98 79 DC-B + SC-E 400 + 100 95 88

Example 3 Control of Pycurulari Duck

For another experiment, the varieties "Koshihikari" paddy, which are grown in Japanese fields, were grown in seedling boxes, planted in fields of 10 m 2, and then transferred to plants with formulations SC-A and SC-E. And the mixture in the tank of these formulations is diluted with water and then sprayed and sprayed 1 liter per compartment using a spraying device. Compound A is formulated at 100 g / l SC.

Each treatment is spread over three compartments (three replicates). There are also untreated compartments. After 15 days of the second treatment, 17% of the untreated rice leaf area (control) was infected with blasting. Disease levels (% infected leaf area) are also assessed in the treated plants and the efficacy of the treatment is measured in%. The efficacy of the mixtures and the solo compounds according to the invention is given in Table 3.

Control of blasting SC-A and SC-E expressed as experimental values when applied alone or as a mixture efficacy(%) Formulation Usage (g / ha) Experimental value Estimates SC-A 50 41 - SC-A 100 71 - SC-A 200 72 - SC-E 100 83 - SC-E 150 91 - SC-E 200 93 - SC-A + SC-E 50 + 100 96 90 SC-A + SC-E 100 + 100 97 95 SC-A + SC-E 50 + 150 95 95

Example 4 Control of Pycurulari Duck

Rice varieties IAC-165 are planted directly in the field plots of Brazil. Each field compartment is 9 m 2 and each treatment is repeated three times. Overhead irrigation is used for constant germination and disease development, but artificial inoculation is not necessary if there is sufficient disease in itself.

Each treatment is sprayed twice with 1000 L water volume / ha at 7 day intervals. At 14 days after the first application, pest control is visually assessed.

The effects of the mixtures according to the invention (SC-D + SC-E) and the solo compounds are given in Table 4.
Control of blasting SC-D and SC-D expressed as experimental values when applied alone or as a mixture efficacy(%) Formulation Usage (g / ha) Experimental value Estimates SC-D 30 8 - SC-E 100 4 - SC-D + SC-E 30 + 100 29 12

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result:

As a result given in Tables 1-4, it can be seen that a mixture of MBI such as phenoxyamide, and azolopyrimidine shows a synergistic effect.

The present invention inhibits the growth of phytopathogenic fungi by applying a synergistically effective amount of at least one azopyrimidine of formula (1) and at least one MBI to the growth site.

Claims (11)

With an acceptable carrier, or surfactant, or with an acceptable carrier and surfactant Synergistically effective amount of (a) at least one azopyrimidine of formula (1), and (b) inhibit one or more melanin biosynthesis, selected from the group consisting of capropamide, clobenthiazion, diclocimet, pyroquilon, phthalide, tricyclazole and phenoxyamide of formula (2) Fungicidal active ingredients Fungicidal composition comprising a. Formula 1

Where R ¹ and R ² each independently represent hydrogen or an optionally substituted alkyl, alkenyl, alkynyl, alkadienyl, aryl, heteroaryl, cycloalkyl, bicycloalkyl or heterocyclyl group, or R ¹ and R ^{2 together} with the adjacent nitrogen atom represent an optionally substituted heterocyclic ring, R ³ represents hydrogen or a halogen atom or an alkyl group, R ⁴ represents hydrogen or an alkyl or aryl group, L represents a halogen atom or an optionally substituted alkyl or alkoxy group, A represents N or CR ⁵ , wherein R ⁵ has the meaning given to R ⁴ , n is 0 or an integer between 1 and 5; Formula 2

Where R ⁵ and R ⁶ each independently represent a hydrogen atom or an optionally substituted alkyl group; R ⁷ independently represents a hydrogen atom or an optionally substituted alkyl group; R ⁸ and R ⁹ each independently represent a hydrogen atom or an optionally substituted alkyl or alkenyl group; R ⁸ and R ⁹ together may represent an alkylene group; Each Y independently represents a halogen atom or an optionally substituted alkyl or alkenyl group or a cyano or nitro group; m is 0 or an integer 1,2,3 or 4. The composition of claim 1 wherein the fungicidal active ingredient capable of inhibiting melanin biosynthesis is phenoxyamide of formula (2). The composition of claim 1 wherein the azolopyrimidine is a compound of Formula 1a. Formula 1a

Where L and n have the same meaning as in the case of Formula 1, R ¹ represents an alkyl or haloalkyl group, R ² represents a hydrogen atom, or R ¹ and R ² together represent an optionally substituted alkylene group having 3 to 6 carbon atoms in the main chain, where one CH ₂ group can be replaced with O or NH, Hal represents a halogen atom. The compound of claim 3 wherein Hal represents a chlorine atom,

end

or A composition containing a compound of Formula 1a, wherein 5. The compound of claim 4, wherein the azolopyrimidine is 5-chloro-6- (2-chloro-6-fluorophenyl) -7- (4-methylpiperid-1-yl)-[1,2,4] Triazolo [1,5-a] pyrimidine, 5-chloro-6- (2-chloro-6-fluorophenyl) -7-isopropylamino- [1,2,4] triazolo [1,5- a] pyrimidine, 5-chloro-6- (2-chloro-6-fluorophenyl) -7- (2,2,2-trifluoroethylamino)-[1,2,4] triazolo [1 , 5-a] pyrimidine, and 5-chloro-6- (2,4,6-trifluorophenyl) -7- (1,1,1-trifluoroprop-2-ylamino)-[1 , 2,4] triazolo [1,5-a] pyrimidine. The composition of claim 2 wherein the phenoxyamide is a compound of Formula 2a. Formula 2a

Where R ⁹ , Y and m have the meanings given above. The method of claim 6,

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And a compound of formula 2a wherein Y 'represents a hydrogen atom or a methyl group. 8. The composition of claim 7, wherein R ⁹ contains a compound of formula 2a representing a C _1-8 alkyl group. The composition according to claim 1, wherein the weight ratio of the fungicidal active ingredient (b): azopyrimidine (a) of formula (1), which can inhibit melanin biosynthesis, is from 0.1: 1 to 10: 1. Spraying a growth site with a synergistically effective amount of one or more azolopyrimidines of Formula 1 as defined in claim 1 and a fungicidal active ingredient capable of inhibiting one or more melanin biosynthesis as defined in claim 1, A method of controlling the growth of phytopathogenic fungi at the growth site. Spraying a growth site with a synergistically effective amount of one or more azolopyrimidines of Formula 1 as defined in claim 1 and a fungicidal active ingredient capable of inhibiting one or more melanin biosynthesis as defined in claim 1, How to control rice disease in growing areas.