KR20070017198A - Triazolopyrimidine derivative-based fungicide mixtures - Google Patents

Abstract

The present invention relates to fungicidal mixtures comprising, as active ingredients, 1) a triazolopyrimidine derivative of formula (I), and 2) at least one component of formula (II) in a synergistically effective amount.

<Formula I>

<Formula II>

Where variables have the following meanings:

A is O or N;

B is N or a direct bond;

G is C or N;

R ¹ is alkyl;

R ² is alkoxy;

R ³ is halogen

Methods of controlling pathogenic fungi using mixtures of compounds of formula (I) and formula (II), the use of compounds of formula (I) and formula (II) to prepare such mixtures, and formulations comprising these mixtures are described.

Active ingredient, triazolopyrimidine, fungicidal, control

Description

Triazolopyrimidine derivative-based fungicidal mixture {TRIAZOLOPYRIMIDINE DERIVATIVE-BASED FUNGICIDE MIXTURES}

The present invention relates to fungicidal mixtures comprising, as active ingredients, 1) triazolopyrimidine derivatives of formula (I), and 2) at least one compound of formula (II) in a synergistically effective amount.

Wherein the variables are as described below:

A is O or N;

B is N or a direct bond;

G is C or N;

R ¹ is C ₁ -C ₄ -alkyl;

R ² is C ₁ -C ₄ -alkoxy;

R ³ is halogen

The invention also relates to a process for the control of harmful fungi using mixtures of compounds of formula (I) and formula (II), the use of compounds of formula (I) and formula (II) for the preparation of said mixtures, and also to compositions comprising these mixtures.

Compound of Formula I, 5-chloro-7- (4-methylpiperidin-1-yl) -6- (2,4,6-trifluorophenyl)-[1,2,4] triazolo [1 , 5-a] pyrimidine, its preparation and its action against harmful fungi are known from WO 98/46607.

The compounds of the formula (II), their preparation and their action against harmful fungi are likewise known from WO 97/48684; WO 02/094797; WO 03/14103.

Mixtures of triazolopyrimidines with other active compounds are known in a general manner from EP-A 988 790 and US 6 268 371.

It is an object of the present invention to provide a mixture (synergistic mixture) with improved activity against harmful fungi with a reduced total amount of active compound applied, in terms of reducing the application rate of known compounds and broadening the activity spectrum.

We have found that this object is achieved by the mixture defined at the outset. In addition, the inventors have found that it is better to control the compounds of formula (I) and formula (II) simultaneously, ie together or separately, or to apply the compounds of formula (I) and formula (II) successively to harmful fungi than is possible with the individual compounds. Was found to allow (synergistic mixture).

The use of compounds of formula (I) and compounds of formula (II), or simultaneously, i.e. together or separately, allows the use of compounds of formula (I) and formula (II) in a wide range of phytopathogenic fungi, in particular Ascomycetes , deuteromycetes . ( Deuteromycetes ), Oomycetes ( Oomycetes ) and Basidiomycetes ( basidiomycetes ) is characterized by high activity. It can be used for crop protection as foliar fungicides, fungicides for seed dressing and soil-acting fungicides.

These include various crops such as bananas, cotton, vegetables (eg cucumbers, beans and gourds), barley, grass, oats, coffee, potatoes, corn, fruits, rice, rye, soybeans, tomatoes, grapevines, It is particularly important for controlling a large number of fungi of wheat, ornamental plants, sugar cane and also of multiple seeds.

It is particularly suitable for controlling the following phytopathogenic fungi: cereals Blumeria graminis (powdery mildew), gourd Erysiphe cichoracearum and Sphaerotheca fuliginea ), Apple grapes grapefruit leukotrica ( Podosphaera) leucotricha ), Uncinula necator of grapevines , Puccinia species of cereals, Rhizoctonia species of cotton, rice and grass, Ustilago species of cereals and sugar cane, Apple Venturia Equalius inaequalis ), Bipolaris and Drechslera species in cereals, rice and grass, Septoria species in wheat, Botrytis cinerea in berries, vegetables, ornamentals and grapevines ), bananas, peanuts and mozzarella (Mycosphaerella) to Mikko spa cereal species, barley, wheat and also of course included Sergio Hernandez Relais des Koh Portree (Pseudocercosporella herpotrichoides), flute Kula Leah duck ashes of rice (Piricularia oryzae ), Phahopsora species of soybean, Phytophthora of potatoes and tomatoes infestans), also of gourds and hop Faroe North Fora (Pseudoperonospora) species, Playa sumo para Beatty Cola (Plasmopara viticola) of grape vines, fruits and altereuna Ria (Alternaria) of vegetable species, and also Fusarium (Fusarium) and Berger Verticillium species.

It can also be used for the protection of materials (eg for wood), for example against Paecilomyces variotii .

The compounds of formula (I) and formula (II) may be applied simultaneously, ie together or separately, or sequentially, and when applied separately, the sequence usually does not have any effect on the results of the control measures.

In the definition of the variables given in formula (II), collective terms representing the following substituents are used:

Halogen: fluorine, chlorine, bromine and iodine;

Alkyl: saturated straight or branched hydrocarbon radicals having 1 to 4 carbon atoms, for example C ₁ -C ₄ -alkyl such as methyl, ethyl, n-propyl, 1-methylethyl, n-butyl, 1-methylpropyl , 2-methylpropyl or 1,1-dimethylethyl.

Preferred are compounds of formula II, wherein R ¹ is n-propyl, or n-butyl, in particular n-propyl.

In addition, particular preference is given to compounds of the formula (II) in which R ³ is iodine or bromine, in particular iodine.

Compounds of formula (II) represent compounds of formulas (II.1), (II.2) and (II.3), in particular as variables are described for compounds of formula (II).

Compounds of formula II.1 wherein R ¹ is n-propyl, R ² is n-propoxy and R ³ is iodine are known by the common name "propquinazide (compound II.1-1)". Mixtures of the compound of formula I with proquinazide are preferred embodiments of the invention.

Another preferred embodiment of the invention is a mixture comprising a compound of formula I and a compound of formula II.2.

Preferred are mixtures comprising a compound of formula (I) and one of compounds of formula (II.2)

A further preferred embodiment of the invention relates to a mixture of a compound of formula (I) and one of compounds of formula (II.3)

Particular preference is given here to mixtures of compounds of the formula I with compounds II.3-6 or II.3-12, in particular II.3-6.

In the preparation of the mixture, preference is given to using purely active compounds of the formulas (I) and (II), as necessary for further active compounds against harmful fungi or other pests such as insects, arachnids or nematodes, or for herbicidal or growth-controlling Active compounds or fertilizers can be added.

Other suitable active compounds in the sense are fungicides, in particular selected from the group:

Acylalanine, such as benalacyl, metallaxyl, opurase, oxadixyl,

Amine derivatives such as aldimorphs, dodines, dodemorphs, fenpropormorphs, fenpropidines, guaztines, iminottadines, spiroxamines, tridemorphs,

Anilinopyrimidines such as pyrimethanyl, mepanipyrim or ciprodinyl,

Antibiotics such as cycloheximid, griseofulvin, kasugamycin, natamycin, polyoxine or streptomycin,

Azoles such as bitertanol, bromoconazole, ciproconazole, diphenoconazole, dinitroconazole, enylconazole, epoxyconazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol, Hexaconazole, imazaryl, ifconazole, metconazole, miclobutanyl, fenconazole, propicosol, prochloraz, prothioconazole, simeconazole, tebuconazole, tetraconazole, tri Adimepon, triadimenol, triflumisol, triticazole,

Dicarboxymides such as iprodione, myclozoline, procmidone, vinclozoline,

Dithiocarbamates such as ferbam, nabam, maneb, mancozeb, metham, metiram, propineb, polycarbamate, thiram, giram, geneb,

Heterocyclic compounds such as anilazin, benomil, boscalid, carbendazim, carboxycin, oxycarboxycin, cyazopamide, dazomet, dithianon, pamoxadon, phenamidon, phenarimol, fuberi Dazole, flutolanyl, furametpyr, isoprothiolane, mepronyl, nourimol, penthiopyrad, picobenzamide, probenazole, pyridoxox, pyroquilon, quinoxifen, silthiofam, thia Bendazole, tifluzamide, thiophanate-methyl, thiadinil, tricyclazole, tripolin,

Copper fungicides such as Bordeaux mixture, copper acetate, copper oxychloride, basic copper sulfate,

Nitrophenyl derivatives such as vinapacryl, dinocap, dinobutone, nitrophthalisopropyl,

Phenylpyrroles such as fenpiclonyl or fludioxonil,

Sulfur,

Other fungicides such as acibenzola-S-methyl, ventiavalicarb, carpropamide, chlorothalonil, cyflufenamide, cymoxanyl, diclomazine, diclocimet, dietofencarb , Ediffeneforce, etaboksam, phenhexamide, pentine acetate, phenoxanyl, perimzone, fluazinam, pocetyl, pocetyl-aluminum, iprovalicab, hexachlorobenzene, mandipropamide, Methrafenone, phosphorous acid, peniculon, propamocarb, phthalide, toloclofos-methyl, quintogen, succiamide,

Strobiliurines such as azocystrobin, dimoxistrobin, enestroburin, fluoxastrobin, cresoxime-methyl, metominostrobin, orissastrobin, pecocystrobin, pyraclostrobin or tripleoxystrobin ,

Sulfenic acid derivatives such as captapol, captan, diclofloanide, polpet, tolylufluoride,

Cinnamid and similar compounds such as dimethomorph, flumetober or flumorph.

In one embodiment of the mixture according to the invention, further fungicides III or two fungicides III and IV are added to the compounds of the formulas (I) and (II).

Preferred are mixtures of compounds of formula I and formula II and component III. Especially preferred are mixtures of compounds of formula I and formula II.

The compounds of formula (I) and formula (II) are usually applied in a weight ratio of from 100: 1 to 1: 100, preferably from 20: 1 to 1:20, in particular from 10: 1 to 1:10.

Component III and, if appropriate, Component IV, are added to the compound of Formula I in the ratio of 20: 1 to 1:20 as needed.

Depending on the type of compound and the desired effect, the application rate of the mixtures according to the invention is from 5 g / ha to 1000 g / ha, preferably from 50 to 900 g / ha, in particular from 50 to 750 g / ha.

Correspondingly, the application rate of the compound of formula I is usually 1 to 1000 g / ha, preferably 10 to 900 g / ha, in particular 20 to 750 g / ha.

Correspondingly, the application rate of the compound of formula II is usually 1 to 1000 g / ha, preferably 10 to 900 g / ha, in particular 40 to 750 g / ha.

In seed treatment, the application rate of the mixture is usually from 1 to 1000 g, preferably from 1 to 750 g and in particular from 5 to 500 g per 100 kg of seed.

A method for controlling harmful fungi is to separately formulate compounds of formula (I) and formula (II), or mixtures of compounds of formula (I) and formula (II) by spraying or dusting seeds, plants, or soil before or after planting or before germination. By or together.

The mixtures according to the invention, or the compounds of the formulas (I) and (II), can be converted into conventional formulations such as solutions, emulsions, suspensions, fines, powders, pastes and granules. The form of use depends on the specific purpose; In each case they should distribute the compound according to the invention finely and uniformly.

The formulations are prepared in a known manner, for example by extending the active compound with a solvent and / or carrier, if necessary using emulsifiers and dispersants. Suitable solvents / adjuvant for this purpose are essentially

Water, aromatic solvents (for example from Solvesso, xylene), paraffins (for example mineral oil fractions), alcohols (for example methanol, butanol, pentanol, benzyl alcohol), ketones (for example cyclo Hexanon, gamma-butyrolactone), pyrrolidone (NMP, NOP), acetates (glycol diacetate), glycols, fatty acid dimethylamides, fatty acids and fatty acid esters (in principle, solvent mixtures may be used),

Carriers such as ground natural minerals (eg kaolin, clay, talc, chalk) and ground synthetic minerals (eg highly dispersed silica, silicates); Emulsifiers such as nonionic and anionic emulsifiers (eg polyoxyethylene fatty alcohol ethers, alkylsulfonates and arylsulfonates) and dispersants such as lignin sulfite waste liquors and methylcellulose.

Suitable surfactants used are alkalis of lignosulfonic acid, naphthalenesulfonic acid, phenolsulfonic acid, dibutylnaphthalenesulfonic acid, alkylarylsulfonates, alkyl sulfates, alkylsulfonates, fatty alcohol sulfates, fatty acids and sulfated fatty alcohol glycol ethers. Metal, alkaline earth metal and ammonium salts, also condensates of sulfonated naphthalene and naphthalene derivatives with formaldehyde, condensates of naphthalene or naphthalenesulfonic acid with phenols and formaldehyde, polyoxyethylene octylphenyl ethers, ethoxylated isooctylphenols, octylphenols , Nonylphenol, alkylphenyl polyglycol ether, tributylphenyl polyglycol ether, tristearylphenyl polyglycol ether, alkylaryl polyether alcohol, alcohol and fatty alcohol / ethylene oxide condensate, ethoxylated castor oil, polyoxyethylene alkyl Ether, ethoxylated polyoxypropylene, lau An alcohol polyglycol ether acetal, sorbitol esters, lignin, sulfite waste liquid, and methyl cellulose.

Suitable materials for the preparation of immediately sprayable solutions, emulsions, pastes or oil dispersions are mineral oil fractions with medium to high boiling points, such as kerosene or diesel oils, also coal tar oils, and vegetable or animal oils, aliphatic, cyclic and aromatic Hydrocarbons such as toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalene or derivatives thereof, methanol, ethanol, propanol, butanol, cyclohexanol, cyclohexanone, isophorone, high polar solvents such as dimethyl sulfoxide , N-methylpyrrolidone and water.

Powders, spreading materials and dustable products can be prepared by mixing or co-pulverizing the active material with a solid carrier.

Granules such as coated granules, impregnated granules and homogeneous granules can be prepared by binding the active compound to a solid carrier. Examples of solid carriers are mineral soils such as silica gel, silicates, talc, kaolin, atacclay, limestone, lime, chalk, church clay, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground synthetic Materials, fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate, urea, and products of plant origin such as grain flour, bark flour, wood flour and nutshell flour, cellulose powder and other solid carriers.

Typically, the formulation comprises 0.01 to 95% by weight of active compound, preferably 0.1 to 90% by weight. The active compound is used in a purity (according to the NMR spectrum) of 90% to 100%, preferably 95% to 100%.

Examples of such formulations are as follows:

1. Products diluted with water

(A) Water Soluble Concentrate (SL)

10 parts by weight of the active compound were dissolved in water or an aqueous solvent. As an alternative, wetters or other auxiliary substances are added. The active compound dissolves when diluted with water.

(B) Dispersible Concentrates (DC)

20 parts by weight of the active compound were dissolved in cyclohexanone by addition of a dispersant such as polyvinylpyrrolidone. Dilution with water gives a dispersion.

(C) emulsifiable concentrate (EC)

15 parts by weight of the active compound (at 5% concentration each) was dissolved in xylene by addition of calcium dodecylbenzenesulfonate and castor oil ethoxylate. Dilution with water gives an emulsion.

(D) emulsions (EW, EO)

40 parts by weight of the active compound (at 5% concentration each) was dissolved in xylene by addition of calcium dodecylbenzenesulfonate and castor oil ethoxylate. This mixture was introduced into water using an emulsifier (Ultraturrax) to make a homogeneous emulsion. Dilution with water gives an emulsion.

(E) Suspension (SC, OD)

In a stirred ball mill, 20 parts by weight of the active compound were ground by addition of a dispersant, a wetting agent and water or an organic solvent to prepare a fine active compound suspension. Dilution with water gives a stable suspension of the active compound.

(F) Water Dispersible Granules and Water Soluble Granules (WG, SG)

50 parts by weight of the active compound were finely ground by the addition of dispersant and wetting agent and water-dispersible or water-soluble granules were prepared using an apparatus (eg extruder, spray tower, fluidized bed). Dilution with water gives a stable dispersion or solution of the active compound.

(G) Water Dispersible Powders and Water Soluble Powders (WP, SP)

75 parts by weight of active compound were ground in a rotor-stator mill by addition of dispersant, wetting agent and silica gel. Dilution with water gives a stable dispersion or solution of the active compound.

2. Products to be Applied Undiluted

 (H) Dustable Powder (DP)

5 parts by weight of the active compound were ground finely and intimately mixed with the finely ground 95% kaolin. This gives a dustable product.

(I) granules (GR, FG, GG, MG)

0.5 parts by weight of the active compound was ground finely and combined with the 95.5% carrier. Typical methods are extrusion, spray-drying or fluidized beds. This gives the granules to be applied undiluted.

(J) ULV Solution (UL)

10 parts by weight of the active compound were dissolved in an organic solvent such as xylene. This provides a product to be applied in the undiluted state.

The active compound may itself be in the form of a formulation thereof or in the form of use prepared therefrom, eg, directly sprayable solutions, powders, suspensions or dispersions, emulsions, oil dispersions, pastes, dustable products, spraying substances or granules In form, it can be used by spraying, atomizing, dusting, spraying, or pouring. The form of use depends entirely on the intended purpose; In each case it is intended to make the finest distribution of the active compounds according to the invention.

Aqueous use forms can be prepared by adding water to emulsion concentrates, pastes or wettable powders (sprayable powders, oil dispersions). In order to prepare emulsions, pastes or oil dispersions, the substances dissolved on their own or in oils or solvents can be homogenized in water using wetting agents, tackifiers, dispersants or emulsifiers. However, it is also possible to prepare concentrates consisting of the active substances, wetting agents, tackifiers, dispersants or emulsifiers and, where appropriate, solvents or oils, which concentrates are suitable for dilution with water.

The concentration of active compound in ready-to-use formulations can vary relatively broadly. Typically this is 0.0001 to 10%, preferably 0.01 to 1%.

The active compounds can also be used successfully in ultra-low-volume (ULV) processes to apply formulations containing more than 95% by weight of active compound, or even active compounds without additives.

If appropriate, even before use, various types of oils, wetting agents, adjuvants, herbicides, fungicides, other insecticides or fungicides may be added to the active compound (tank mix). This agent is admixed with the composition according to the invention, typically in a weight ratio of 1:10 to 10: 1.

Compounds or mixtures or corresponding formulations of formulas (I) and (II), where the fungicidally effective amount of the mixture, or individually, applies a plant, seed, soil, region, material or space to be kept free of harmful fungi, harmful fungi. Is applied by treating with a fungicidally effective amount of the compounds of the formula Application can be carried out before or after infection with harmful fungi.

The fungicidal effect of the compounds and mixtures can be demonstrated by the following test:

The active compounds were prepared individually or together as stock solutions comprising 0.25% by weight of active compound in acetone or DMSO. To the solution was added 1% by weight of the emulsifier Uniperol® EL (wetting agent with emulsifying and dispersing activity based on ethoxylated alkylphenols) and the mixture was diluted with water to the desired concentration.

Examples of use-activity against wheat powdery mildew caused by erypsipe (syn. Bluemeria ) graminis, which is specialized in wheat, for 5 days.

The leaves of potted wheat seedlings of the variety "Kanzler" were sprayed until the aqueous suspension with the concentration of the active compound described below was run off. An emulsion of the stock solution was prepared as described above. After applying the active compound for 5 days, the plants were dusted with spores of wheat powdery mildew (Ericife (synonym Blue Mary) graminis, which specialize in wheat). The test plants were then placed in greenhouses at temperatures of 20 ° C. to 24 ° C. and relative humidity of 60 to 90%. After 7 days, the incidence of powdery mildew was visually measured for percent infection of the total leaf area.

The visually determined percentage of infected leaf area was converted to the% efficacy of the untreated control.

Efficacy (E) was calculated using the following Abbot formula:

E = (1-α / β)

α is the percent fungal infection rate of the treated plants,

β is the percent fungal infection rate of untreated (control) plants.

Efficacy 0 means that the infection level of the treated plant corresponds to that of the untreated control plant; Efficacy 100 means that the treated plant is not infected.

The expected efficacy of the mixture of active compounds is measured using the Colby formula, Colby, SR, "Calculating synergistic and antagonistic responses of herbicide combinations", Weeds, 15, 20-22, 1967 and observed The efficacy was compared.

Colby Formula:

E = x + y-xy / 100

E is the expected efficacy of the untreated control, expressed in%, when using a mixture of active compounds A and B at concentrations a and b,

x is the potency of the untreated control expressed in% when using active compound A at concentration a,

y is the potency of the untreated control, expressed in%, when using active compound B at concentration b.

Individual active compounds Example Active compound Concentration of active compound in spray solution [ppm] % Efficacy of untreated control One Control group (untreated) - (77% infection) 2 I 50 12.5 35 9 3 II.1-1 (Proquinazide) 25 12.5 80 67 4 II.2-1 25 12.5 74 61 5 II.2-2 25 12.5 80 61

Mixture according to the invention  Example Mixture Concentration Mixing Ratio of Active Compounds  Observed efficacy Calculated efficacy ^* )  6 I + II.1-1 12.5 + 25 ppm 1: 2  99  80  7 I + II.1-1 50 + 12.5 ppm 4: 1  87  79  8 I + II.2-1 12.5 + 25 ppm 1: 2  99  76  9 I + II.2-1 50 + 12.5 ppm 4: 1  93  74  10 I + II.2-2 12.5 + 25 ppm 1: 2  99  82  11 I + II.2-2 50 + 12.5 ppm 4: 1  87  74 ^* ) Efficacy calculated using Colby formula

Individual active compounds Example Active compound Concentration of active compound in spray solution [ppm] % Efficacy of untreated control 12 Control group (untreated) - (88% infection) 13 I 12.5 9 14 II.2-3 3.125 66 15 II.2-5 3.125 54

Mixture according to the invention  Example Mixture Concentration Mixing Ratio of Active Compounds  Observed efficacy Calculated efficacy ^* )  16 I + II.2-3 12.5 + 3.125 ppm 4: 1  89  69  17 I + II.2-5 12.5 + 3.125 ppm 4: 1  92  58 ^* ) Efficacy calculated using Colby formula

The test results suggest that thanks to strong synergy, the mixtures according to the invention are significantly more effective than predicted using Colby's formula.

Claims (12)

A fungicidal mixture for controlling phytopathogenic harmful fungi comprising 1) a triazolopyrimidine derivative of formula (I), and 2) at least one compound of formula (II) in a synergistically effective amount. <Formula I>

<Formula II>

Wherein the variables are as described below: A is O or N; B is N or a direct bond; G is C or N; R ¹ is C ₁ -C ₄ -alkyl; R ² is C ₁ -C ₄ -alkoxy; R ³ is halogen The fungicidal mixture of claim 1 comprising as a compound of formula II a compound of formula II.1-1 (proquinazide). <Formula II.1-1>

The fungicidal mixture of claim 1 comprising the compound of formula II.2. <Formula II.2>

(here, R ¹ is n-propyl or n-butyl; R ² is methoxy, ethoxy, or isopropoxy; R ³ is iodine The fungicidal mixture of claim 1 comprising the compound of formula II.3 as a compound of formula II. <Formula II.3>

(here, R ¹ is n-propyl or n-butyl; R ² is ethoxy, n-propoxy, isopropoxy or n-butoxy; R ³ is bromine or iodine The fungicidal mixture according to any one of claims 1 to 4, comprising the compounds of formula (I) and formula (II) in a weight ratio of 100: 1 to 1: 100. A composition comprising a liquid or solid carrier and a mixture according to any one of claims 1 to 5. A method for controlling phytopathogenic harmful fungi comprising treating a fungus, its habitat, or a seed, soil or plant to be protected from a fungal attack with an effective amount of the compounds of formula I and formula II according to claim 1. 8. Process according to claim 7, wherein the compounds of formula (I) and formula (II) according to claim 1 are applied simultaneously, ie together or separately, or sequentially. The process according to claim 7 or 8, wherein the compound of formula (I) and formula (II) according to claim 1 or the mixture according to any one of claims 1 to 5 is applied at 5 g / ha to 1000 g / ha. Way. The compound according to any one of claims 6 to 8, wherein the compound of formula (I) and formula (II) according to claim 1 or the mixture according to any one of claims 1 to 5 is used in an amount of 1 to 1000 g per 100 kg of seeds. How to apply in the quantity. A seed comprising the mixture according to any one of claims 1 to 5 per 100 kg of seeds in an amount of 1 g to 1000 g. Use of the compounds of formula (I) and formula (II) according to claim 1 for preparing a composition suitable for controlling harmful fungi.