KR20070029197A - Fungicidal mixtures based on oxime ether derivatives - Google Patents

Abstract

The invention relates to fungicidal mixtures containing: A) triazolopyrimidine of formula (I) and B) oxime derivatives of formula (II), wherein the index and substituents have the following meaning: X = C1-halogen alkyl or C1-halogen alkoxy; R= halogen, alkyl, halogen alkyl, alkoxy or halogen alkoxy; n= 0, 1, 2 or 3 in a synergistically effective amount. The invention also relates to a method for controlling harmful fungi with mixtures of compounds (I) and (II), to the agents containing said mixtures and to the utilization of compounds (I) and (II) for the production of said mixtures. ® KIPO & WIPO 2007

Description

Fungicidal mixture based on oxime ether derivatives {FUNGICIDAL MIXTURES BASED ON OXIME ETHER DERIVATIVES}

The present invention relates to fungicidal mixtures comprising A) triazolopyrimidine derivatives of formula (I) and B) oxime ether derivatives of formula (II) in a synergistically effective amount.

Wherein the indices and substituents are as defined below:

X is C ₁ -haloalkyl or C ₁ -haloalkoxy;

R is halogen, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -haloalkyl, C ₁ -C ₄ -alkoxy or C ₁ -C ₄ -haloalkoxy;

n is 0, 1, 2 or 3)

The present invention also relates to methods of controlling harmful fungi using mixtures of compounds of formula I and formula II, compositions comprising these compounds and the use of compounds of formula I and formula II for the preparation of said mixture.

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.

Mixtures of triazolopyrimidines with other active compounds are disclosed in EP-A 988 790 and US 6 268 371.

Oxime ether derivatives of formula (II) and methods for their preparation are also known (WO 96/19442, EP-A 10 17 670 and EP-A 10 17 671).

WO 98/53689, WO 99/31980 and WO 00/36917 disclose mixtures of oxime ether derivatives of formula II with other active compounds.

It is an object of the present invention to provide a mixture for controlling harmful fungi and particularly effective for certain indications.

It is an object of the present invention to reduce the application rate of known compounds of formulas (I) and (II) and to broaden the activity spectrum, with mixtures having an improved effect on harmful fungi with reduced total amounts of active compounds applied (synergistic mixtures). To provide.

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 for harmful fungi to apply the compounds of formula (I) and formula (II) simultaneously, ie together or separately, or to apply the compounds of formula (I) and formula (II) sequentially than the individual compounds alone. It was found to allow control.

The mixtures according to the invention act synergistically and are therefore particularly suitable for controlling harmful fungi and especially powdery mildew fungi of cereals, vegetables, fruits, ornamental plants and grapevines.

The mixture according to the invention preferably comprises a compound of formula (I) and a compound of formula (II) as the active compound.

Among the compounds of formula (II), it is preferred that X is a trifluoromethyl or difluoromethoxy group. Also particularly preferred are compounds of formula II, wherein the index n is zero.

Particular preference is given to compounds of the formula (II) listed in Table 1 below.

Compounds II.1 and in particular II.14 are preferred for use in the mixtures according to the invention.

The ratio of compounds of Formula I and Formula II may vary over a wide range; Preferably, the active compound is used in a weight ratio of 100: 1 to 1:50, preferably 50: 1 to 1: 2, in particular 20: 1 to 1: 1.

In the preparation of the mixture, preference is given to using pure active compounds of the formulas (I) and (II), further active compounds against harmful fungi or other pests such as insects, arachnids or nematodes, or herbicidal or growth-modulating active compounds or Fertilizer may be added.

Mixtures of compounds of formula (I) and formula (II), or at the same time, ie together or separately, are used to provide a broad range of phytopathogenic fungi, in particular Ascomycetes , Basidiomycetes. And Deuteromycetes steel. Some of these act invasive and can also be used as foliar- and soil-acting fungicides.

These include various crops, such as cotton, vegetables (e.g. cucumbers, beans, tomatoes, potatoes and gourds), barley, grass, oats, bananas, coffee, corn, fruits, rice, rye, soybeans, grapevines, Of particular importance is the control of a large number of fungi of wheat, ornamental plants, sugar cane and many seeds.

It is particularly suitable for controlling the following phytopathogenic fungi: cereals Blumeria graminis (powdery mildew), gourd Erysiphe cichoracearum and Sphaerotheca pulleynea . fuliginea ), apple grapes, 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 ), Phytophthora infestans of potatoes and tomatoes, Pseudoperonospora species of gourds and hops, Plasmopara of grapevines viticola), vegetables and altereuna Ria (Alternaria) kinds of fruits, and also Fusarium (Fusarium) and Verbier tisil Leeum (Verticillium) species.

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.

Depending on the nature of the effect desired, the application rate of the mixtures according to the invention is in particular from 5 g / ha to 2000 g / ha, preferably from 50 to 1500 g / ha, in particular from 50 to 750 g / ha, on a farmed area basis.

Here, the application rate of the compound of the formula (I) is 10 to 1000 g / ha, preferably 20 to 750 g / ha, in particular 20 to 500 g / ha.

Correspondingly, the application rate of the compound of formula II is 5 to 1500 g / ha, preferably 10 to 750 g / ha, in particular 20 to 500 g / ha.

In seed treatment, the application rate of the mixture is usually from 0.001 to 1 g, preferably from 0.01 to 0.5 g, in particular from 0.01 to 0.1 g per kg of seed.

In the control of phytopathogenic harmful fungi, the application of the compounds of the formulas (I) and (II), or mixtures of the compounds of the formulas (I) and (II), individually or together, may be applied to seeds, plants or before or after planting or seeding. By spraying or dusting the soil.

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 added to 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 (wettable 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. Alternatively, a concentrate may be prepared which consists of the active substance, wetting agent, tackifier, dispersant or emulsifier, and where appropriate the solvent or oil, which concentrate is 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, immediately before use, various types of oils, wetting agents, adjuvants, herbicides, fungicides, other pesticides or fungicides may be added to the active compound (tank mix). This agent may be admixed with a formulation according to the invention, typically in a weight ratio of 1:10 to 10: 1.

The synergistic activity of the mixtures according to the invention can be demonstrated by the following experiments:

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 solution was diluted with water to the desired concentration.

Infected leaf areas were evaluated by measuring in percentage. This percentage was converted to efficacy. 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.

Expected efficacy of mixtures of active compounds can be found in the Colby formula, R.S. Colby, Weeds, 15, 20-22, 1967] and compared with the observed efficacy.

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.

Example 1 Efficacy of Brown Rust in Wheat Induced by Puccinia Recondita

On the leaves of potted wheat seedlings of the cultivar "Kanzler", dusting spores of rust disease (Puccinia recondita) were dusted. It was then placed in a chamber with high atmospheric humidity (90-95%) at 20-22 ° C. for 24 hours. During this time, the spores germinate and infiltrate the germination tube into the leaf tissue. The next day, the infected plants were sprayed until the aqueous suspension with the concentration of active compound described below was run down. The coating was dried after spraying and the test plants were incubated for 7 days in a greenhouse at a temperature of 20 ° C. to 22 ° C. and a relative atmospheric humidity of 65 to 70%. Then, the incidence of the rust fungus on the leaves was measured.

Individual active compounds Experiment number Active compound Concentration of active compound in spray solution [ppm] % Efficacy of untreated control One Control group (untreated) 0 (90% infection) 2 I 4 1 89 0 3  II.14 1 0.25 0.06 0 0 0

Mixture according to the invention  Experiment number Mixture Concentration Mixing Ratio of Active Compounds  Observed efficacy Calculated efficacy ^* )  4 I + II.14 4 + 0.25 ppm 16: 1  97  89  5 I + II.14 1 + 0.06 ppm 16: 1  22  0  6 I + II.14 4 + 1 ppm 4: 1  99  89  7 I + II.14 1 + 0.25 ppm 4: 1  33  0  8 I + II.14 1 + 1 ppm 1: 1  67  0 ^* ) Efficacy calculated using Colby formula

Example 2 Activity against Wheat Flour Disease Induced by Forma specialis ( tritici ) Erysipei (syn. Bluemeria ) Graminis

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. 24 hours after spraying, the coating was dried and dusted with spores of wheat powdery mildew (Ericife (syn. Bluemeria) Graminis, a parasitic specialized 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 by infection of the total leaf area (%).

Individual active compounds Experiment number Active compound Concentration of active compound in spray solution [ppm] % Efficacy of untreated control 9 Control group (untreated) 0 (99% infection) 10 I 4 1 0.25 60 9 0 11 II.1 0.25 70

Mixture according to the invention  Experiment number Mixture Concentration Mixing Ratio of Active Compounds  Observed efficacy Calculated efficacy ^* )  12 I + II.1 4 + 0.25 ppm 16: 1  98  88  13 I + II.1 1 + 0.25 ppm 4: 1  95  73  14 I + II.1 0.25 + 0.25 ppm 1: 1  95  70 ^* ) Efficacy calculated using Colby formula

The test results suggest that at all mixing ratios the observed efficacy of the mixtures according to the invention is significantly higher than predicted using Colby's formula.

Claims (12)

A fungicidal mixture comprising A) a triazolopyrimidine derivative of formula I, and B) an oxime ether derivative of formula II in a synergistically effective amount. <Formula I>

<Formula II>

Wherein the indices and substituents are as defined below: X is C ₁ -haloalkyl or C ₁ -haloalkoxy; R is halogen, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -haloalkyl, C ₁ -C ₄ -alkoxy or C ₁ -C ₄ -haloalkoxy; n is 0, 1, 2 or 3) The fungicidal mixture of claim 1 wherein the weight ratio of the compound of formula I to the oxime ether derivative of formula II is from 100: 1 to 1:50. The oxime ether derivative of formula II.1, N- [cyclopropylmethoxyimino- (2,3-difluoro-6-trifluoromethylphenyl) methyl] -2-phenyl Fungicidal mixture comprising acetamide. <Formula II.1>

The oxime ether derivative of formula II.14, N- [cyclopropylmethoxyimino- (6-difluoromethoxy-2,3-difluorophenyl) methyl] -2-. Fungicidal mixture comprising phenylacetamide. <Formula II.14>

A fungicidal composition comprising the fungicidal mixture according to any one of claims 1 to 4 and a solid or liquid carrier. A plant, seed, soil, region, material or space which is to be kept free of harmful fungi, its habitat or harmful fungi, is prepared by the compounds of formula I according to claim 1 and the oxime ether derivatives of formula II according to claim 1 or A method for controlling phytopathogenic harmful fungi comprising treating with a synergistically effective amount of the composition according to claim 3. The process according to claim 6, wherein the compound of formula (I) according to claim 1 and the oxime ether derivative of formula (II) according to claim 1 are applied simultaneously, ie together or separately, or sequentially. 8. Process according to claim 6 or 7, wherein the compound of formula (I) according to claim 1 is applied in an amount of 0.01 to 2.5 kg / ha. 8. Process according to claim 6 or 7, wherein the oxime ether derivative of formula (II) according to claim 1 is applied in an amount of 0.01 to 1 kg / ha. 8. A process according to claim 6 or 7, wherein the compounds of formula (I) and formula (II) according to any one of claims 1 to 4 are applied in an amount of 0.001 to 1 g per kg of seed. A seed comprising the mixture according to any one of claims 1 to 4 per kg of seed in an amount of 0.001 g to 1 g. Use of the compounds of formula (I) and formula (II) according to claim 1 for preparing a composition suitable for controlling harmful fungi.