HU193034B - Synergetic fungicide composition - Google Patents

Abstract

SUMMARY OF THE INVENTION The present invention relates to a synergistic fungicide which comprises, as active ingredient, a) an acylaniline derivative of formula (I) wherein X = CH- or nitrogen, Ru and Rt, hydrogen or covalently bonded together, Y is methoxymethyl or benzyl, b) comprises a mixture of 2-cyano-N- (ethylcarbamoyl) -2- (methoxyimino) acetamide of formula (II) and (c) optionally a mixture of a fungicidal agent. - och3 HjCj — Nh — CO --- NH - CO || -1-

Description

ι

FIELD OF THE INVENTION The present invention relates to a fungicide, in particular a synergistic fungicide for controlling fungi of the subclass Oomycetes.

Although many fungicides, including fungicides of the subclass Oomycetes, are known, more effective fungicides are needed. (U. S. Patent No. 1,470,740, German Patent Publication No. 2,801,428, Proc.Brit. Crop.Prot.Conf. 1979, 353)

We have determined that it is an active ingredient

a) an active compound of the formula I effective against fungi of the subclass Oomycetes, wherein X = CH or N, R _a and R * are hydrogen or together form a covalent bond, Y is methoxymethyl or benzyl;

(b) Fungicides containing the active ingredient of the formula (II) hereinafter referred to as the international free name of cimoxanyl [1- (2-cyano-2-methoxyiminoacetyl) -3-ethylurea] (c) and optionally a contact antifungal agent they are particularly effective in preventing or combating fungal diseases.

Particularly preferred are the active compounds of the formula I in which

X = CH-, R _a and R 1, hydrogen, Y methoxymethyl (international free name is metalaxyl);

X = CH, R _u and R, a hydrogen atom, Y is a benzyl group (common name: benalaxyl);

X is nitrogen, R _a and R _are covalent bonds, Y is a methoxymethyl group (internationally known as oxadixyl).

The active compounds of the formula I are known or can be prepared by known methods. (British Patent No. 1,500,581).

Cimoxanyl is also a known systemic fungicide which is effective against Plasmopara spp. and Phytopthora spp. (French Patent No. 2,254,276).

It has been found that, when used in combination with an active ingredient of the formula I, cimoxanyl has a surprisingly and significantly increased activity against fungi.

The risk of fungal resistance to the active ingredient of the formula I is also substantially reduced when used with cimoxanilla. In addition, the combination or method of the present invention has surprisingly potent acyl alanine drug resistance in the field against Phytophthora spp. and Plasmopara spp. strains, as evidenced by the significant reduction in the resistance factor (90% fungal efficacy against resistant and susceptible strains). Field strains resistant to the acylalanine drug substance used herein are defined as Oomycetes fungi which have become resistant to fungicides containing acylalanine derivatives (see, for example, Resistance to acylalanine-type fungicides in Peronosporales, 1981, 5, 558). Furthermore, the combination according to the invention is effective against a wider range of fungi compared to fungicides which can be controlled with fungicides containing the individual active substances alone.

The present invention is therefore a synergistic agent for controlling fungi, in particular fungi of the class Oomycetes such as Phytophthora spp., Plasmopara spp., Peronospora spp., Pseudoperonospora spp., Sclerophthora spp., Bremia spp. and Pythium spp. in crops, mainly in vineyards, tomatoes, hops, cocoa, tobacco, potatoes and lettuce, and in eucalyptus.

The term "crop" as used herein denotes any desired plant.

Preferably, the active compounds of the formula I are applied in an amount of 100-400 g / ha, in particular 150300 g / ha, for example 200 g / ha, 40-160 g / ha, in particular 60120 g / ha, for example 80 g / ha cimoxanil.

Other pesticides, such as fungicides, bactericides, insecticides, acaricides, herbicides, or plant growth regulators, may also be used in combination with the above-mentioned active ingredients to enhance the activity or broaden the spectrum of activity of the present invention; it is particularly advantageous to use an additional contact fungicide.

Particularly preferred contact fungicides for use with the fungicide of the invention are copper-containing fungicides, i.e. copper (II) oxychloride, copper (II) calcium sulfate; and folpet (N-trichloromethylthio-phthalimide) and mancozeb (manganese zinc-ethylene-bis / dithiocarbamate) or mixtures thereof. The additional contact fungicide or fungicides are usually applied in an amount of 200-2000 g / ha. The use of mancozeb as an additional fungicide is particularly suitable because it has a synergistic effect with the combination of the active ingredient of the formula I with cimoxanil.

The fungicides of the invention contain the compound of formula I and cimoxanyl as active ingredient.

In the compositions according to the invention, the weight ratio of active ingredient of formula I to cimoxanyl is preferably from 10: 1 to 1: 3, particularly preferably from 5: 1 to 1: 1, in particular from 4: 1 to 2: 1, for example 2.5: 1. The synergistic effect of the agent of the present invention is apparent from various experimental data in the following tables, and the synergism is illustrated, for example, by a 1: 0.3 to 1: 3 weight ratio of the active ingredient of formula I and cimoxanyl.

If the agent of the invention contains an additional contact antifungal agent,

-2193034 preferably has a weight ratio of active ingredient of formula (I) to contact antifungal agent. 1: 2 to 1:10 and, if mancozeb or folpet is used, the weight ratio is particularly preferably 1: 4 to 1: 9, in particular 1: 5 to 1: 8, for example 1: 7. It is particularly advantageous to add mancozeb to the agent of the invention.

The agent of the present invention may be in the form of any conventional form, for example, twin pack, immediate dissolution granules, suspension concentrates or wettable powders with agriculturally acceptable excipients. The agents may be prepared in conventional manner, for example, by mixing the active ingredients with excipients such as diluents or carriers and other formulation excipients such as surfactant additives.

By diluent is meant any liquid or solid, agriculturally acceptable substance that can be added to the active ingredients to form it in a more or less usable form and that its efficacy is achieved at the appropriate and desirable concentration. The diluent may be, for example, talc, kaolin, diatomaceous earth, xylene or water.

Spray agents such as water-dispersible concentrates or wettable powders contain surfactant additives such as wetting and dispersing agents such as formaldehyde and naphthalene sulfonate condensation products, alkylaryl sulfonate, lignin sulfonate, fatty acid alkylsulfoxylate, ethoxylated sulfate, and the like.

Generally, the compositions will contain from 0.01% to 90% by weight of the active ingredient, from 0% to 20% by weight of an agriculturally acceptable surfactant and from 10% to 99.99% by weight of a solid or liquid carrier or diluent. optionally in combination with contact antifungal agents. The concentrated agents of the invention are generally 2 to 80% by weight, preferably

They contain 5-70% by weight of the active ingredient. Direct use agents may contain, for example, 0.0120% by weight, preferably 0.01-5% by weight, of the active ingredient.

The invention is illustrated by the following examples.

A) Example of an action

Fungicidal efficacy against acylalanine fungicide-resistant Phytophthora infestans

3-5-leaf young tomato roots grown in pots were sprayed with an aqueous spray containing the following active ingredients:

The mixture is: 0.05-0,0002% by weight of active ingredient of the formula I and 0.05-0,0002% by weight of cimoxanyl;

Mixture B: 0.05-0,0002% by weight of active ingredient of the formula I and 0.2-0.003% by weight of a contact fungicidal active ingredient such as mancozeb, folpet or copper-containing active ingredients.

Two hours later, or 4, 8, 16, 32 or 64 hours later, the treated plants or leaves 5 were thoroughly washed, for example with an amount of artificial rain corresponding to 10-50 mm / hour. Two hours after the washing operation, the treated plants or leaves were infected with a spore suspension (10 ⁵ spores / ml) of ¹⁰ 'of the strain Phytophthora infestans against the active ingredient of the formula (I).

The plants were then placed in a tent with 100% relative humidity, 16 ° C ambient temperature and 16 hours light. The degree of fer15 contamination was determined after 4-5 days compared to untreated, similarly infected plants or leaves. Plants treated with Mixture A showed a ² θ complete absence of fungal infection, whereas Mixture B showed significantly less fungal efficacy. Similar results were obtained in vineyards tested against acylalanine fungicide resistant Plasmopara viticola strains.

B) Functional Example Synergistic effect

In this study, the fungicidal efficacy of agents containing the compound of formula (I) and cimoxanil alone was compared with that of the agent containing the compound of formula (I) in combination with cimoxanil. The possible synergistic effect between the two active substances was determined using the following Colby equation:

In equations A and B, the fungicidal efficacy of the active ingredients when used alone and p is the fungal efficacy that would theoretically be achieved with the mixture if there was no interaction between the active ingredients. If p is less than the experimentally determined fungicidal effect, then synergism is created.

5q Young tomato shoots grown in pots were sprayed with an aqueous spray containing the active ingredient of the formula I and cimoxanil alone or in the form of an agent of the invention. The active ingredient of the formula (I) and cimoxanyl were used at a concentration of 0.01250.00002% w / v until the juice was dripping from the leaves.

Two hours later, the treated plants were inoculated with ₆₀ suspensions of Phytophthora infestans spores, and placed in a 100% relative humidity, 16 ° C ambient temperature and 16 hours illuminated tent. The degree of infestation was determined after 4-6 days, the treated plants with untreated ^b5, as compared to infected plants. An analogous study was performed

-3193034

Plasmopara viticola also on vines infected with fungi.

The efficacy beyond the cumulative effect was established as shown in the following tables. 5

In the tables, 1 is the title of the active ingredient oxadixil. cymoxanil, mancozeb M is the abbreviation for the underlined numerical value of the Colby p-values and the experiments show without the underscore ¹ θ fungicidal activity letileg set.

Table I

Phytophthora on tomato 15

1 J - J ⁰ Cim. i. 2 8 32 ppm 0 1 0 60 80 100 2 10 I 80 64 90 82 100 8 ₍ 40 100 76 100 88 100 32 | 60 100 84 100 92 100

ppm | _____L ³⁰

II. spreadsheet

Phytophthora on tomato

--- ₇ --------------------------------- \ I 0 0.2 0.6 1.8 5 , 4 ppm

CiiíJ

--- 4 --------------------------------

0 0 0 0.2 I ° 10 0.6 20 1.8 (20 20 5.4 pPM J40 I 40

20 30 0 20 30 _0 20 40 20 36 60 40 52

40 70 50 40 90 ⁶⁰ 40 90 ⁶⁵ 52 100 ⁸⁰ 64 100

III. Table Plasmopara solon

T

I l address signal 0 0.2 0.6 1.8 5.4 ppm 55 1 ⁰ 1 0 0 30 50 60 0.2 | 0 ³⁰ 0 40 30 55 50 ⁷ ° 6O 0.6 20 40 ₂₀ 50 44 60 60 ⁸ ° 68 60 1.8 50 ⁵ ° 50 80 65 90 75 ¹ °irl 80 5.41 60 ⁶ ° 60 90 72 100 80 ¹ °° 84 ppm ¹ 1 65

ARC. spreadsheet

Phytophthora on tomato

I, 0 0.125 0.375 1.13 3 ^ 38

---- --- ---- ---—----- -

 Γ -V-1 Title. | 0 0.9 2.7 8.1 24.3 pPM ---- _r 0 I 0 10 20 40 60 0.1 0 2, 5 - 30 50 80 .... 10 20 40 οϋ 0.3 l 0 35 40 10 20 ⁶⁰ 40 ⁹ ° -0 0.9; 20 45 28 ⁵⁰ 36 52 100 _r „60 ² ' ⁷ I 35 50 41 48 ^WU 61 ^WU 74 PPm J Table V.

Plasmopara on grapes

I ! ⁰ 0 125 0,375 1.13 3.38 pPM H - ⁰ 0 9 2.7 8 1 24.3 Title. 1 pPM 0 ΐ ° 30 50 60 70 0.1 , ⁰ 30 30 ⁶⁰ 70 60 100 50 70 0.3 20 50 70 80 100 44 60 EB 76 0.9 1 40 1 60 80 100 100 58 70 76 82 2.7 60 80 100 100 100 _nn 72 80 84 88 pPM 1

I-V. Based on the data in Table 3, which justify the synergism, the synergistic factor can be determined using the Wadley equations:

,, "A + b + ...

EC 90 (theory) = --r

- _ 4EC90 EC90 EC90 ^and EC90 (elm). (Accompanied).

In the formulas, a, b, etc. the weight ratio of the active ingredients used in the mixture; EC 90, EC 90 (Accompanying) and EC 90 (conc.) Are the 90% fungicidal concentration of the active substance, experimentally determined, as well as experimentally determined, as determined by experiment. SF is the synergistic factor (for synergism value = 1).

The synergistic factor determined under greenhouse conditions in tomato (Phytophthora infestans) and grape (Plasmopara viticola) with a mixture of active ingredient I and cimoxanyl and active ingredient I, cimoxanyl and mancozeb calculated by the Wadley equations:

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8

VI. spreadsheet

1 / CIMTIG Tomato (Phyt.) SF ^<2 > Grapes (Plasm.) EC 90 SF elm. small. EC 90 El. (2) small. 1: 0 17 - - 19 1: 0.3 21 7 3.0 23 11 2.1 1: 1 31 10 3.1 26 5 5.2 1: 3 49 16 3.1 30 4 7.5 0: 1 - 125 36 I / Cim. / M 1: 0.3: 7 69 29 2.4 49 16 3.1 1: 2.4: 7 76 32 2.4 46 6 7.7

* weight ratio (2) Wadley equations.

In carrier synergistic fungicidal effect

Metalaxyl, a mixture, cymoxanil and _EC90 values (EC90 _'s) resistant strain of Phytophthora infestans in tomatoes and Plasmopara viticola on sensitive and resistant strains were determined on tomato vines. The theoretical EC ₉₀ value (EC 90 _e / _m .) Was calculated according to Wadley and the synergistic factor (SF, EC 90 _e ; _m / EC 90 µ.,.) Was determined. A synergistic effect was observed (SF> I).

The results are shown in the following table.

Phytophthora inf. Plasmopara viticola

(tomato) resistant sensitive EC90 _{e £ w} EC90 _{k {s} (solo,) resistant EC90 _ elm. ^{EC9 (} V SF SF EC90 is _small SF Metalaxil (M) 9971 4 36 Cimoxanil (C) 41 27 29 (M): (C) (crowd- gold) 1: 0.16 225 94 2.7 5 3 1.7 36 9 4.0 1: 0.4 125 47 2.7 5 3 1.7 35 6 5.8 1: 1 72 24 3.0 7 2 3.4 34 5 6.2

In vitro synergistic fungicidal action

Wild (sensitive and resistant) isolated from Peperonia obtusifolia Phytophthora nicotianae var. 8 to 10-day cultures of parasitica strains were placed in Petri dishes filled with agar mycelium discs. Resistant strains were selected in vitro by placing the mycelial disk of wild strains in 50 pg / ml metalaxyl solution. After 5 days of incubation at 25 ° C, ED 50 was determined by measuring the radial growth. The fungi were then treated with a mixture of benalaxyl, cimoxanyl, and a mixture of benalaxyl and cimoxanyl at ^{55 to} 8 different concentrations (1.3, 10, 30, 100, 300 and 600 pg / ml). The experimental ED ₅₀ value was calculated from dose-response curves. Synergistic factor agent containing the mixture of cymoxanil and benalaxyl according Wadlev cuff ⁶⁰ Totten out.

The following results were obtained (SF> 1 synergistic).

-5193034

Tribe

agent

Phytophthora nicotianae var. parasitica I-sensitive I-resistant NL-sensitive NL-resistant

ED ₅₀ SF ED _SO SF ED _SO SF ED ₅₀ SF

cymoxanil benalaxyl C: B 1: (weight (C) (B) 5 9.0 10.5 1.7 6.01 13.8 141.6 30.0 1.83 21.2 5.4 2.1 2.94 13.0 69.7 18.1 2.21 ratio) 1: 1 2.0 4.85 19.8 1.27 2.4 3.59 13.4 1.64

In the bioassays, the active compounds of the formula I were used in the form of a 25% wettable powder of the following composition and diluted with water before use:

kaolin 65% diatomaceous earth 2% sodium lauryl sulphate 3% sodium lignin sulphonate 5% active substance 25%

Cimoxanil was used in the form of an aqueous composition of a 50% wettable powder with the following composition:

kaolin 40% diatomaceous 2% sodium laureth sulfate 3% Sodium Iigninszulfonát 5% cymoxanil 50%

Mancoceb was obtained from a commercially available 80% wettable powder formulation by dilution with water (Dithiane M-45 *).

The following examples illustrate the composition of the agents of the invention.

Wettable powders

THE The active ingredient of formula (I) B C D E F G t ^ in H material) 8 10 17 10 40 37 10 25 cimoxanil 3.2 contact fungicides, for example 5 20 10 24 20 5 10 mankoceb 56 25 - - 25 copper (II) oxide chloride - copper (II) -kalcium- 10 - 17.5 sulfate - 5 - - 18.5 folpet - surfactant: wetting agent (sodium alkyl naphthalene) 43 30 sulfonate) 1 dispersant (Sodium ligninszul- 1 1 1 1 1 1 1 spin) 5 diluent: 5 5 5 5 5 5 5 silica 5 5 5 5 5 5 5 5 kaolin 21.8 34 9 39 25 28 13 54 Prussian - - - 4 - -

The ingredients are mixed together to form the agent, and the mixture is ground and mixed again.

In general, the active compounds are employed in industrial purity.

The composition of the active substance, which consists of active substances of industrial purity, is as follows:

Example J Oxadixil (Industrial, 95%) 10.5% ₆₀ Cimoxanyl (Industrial, 95%) 5.3% Mancozeb (Industrial, 80%) 31.3% Copper (II) Oxychloride (57% Copper) 17.5% Copper (II) Calcium Sulphate (27% Copper) 18.7% Sodium Isopropyl Naphtha ⁶⁵ Linulfonate 1.0 1%

-6193034 silica 6.0% sodium lignin sulfonate 5.0% kaolin 5.7%

Example K)

Suspension powder (440 g / liter)

4.2% Oxadixil (Industrial, 95%)

1.7% cimoxanyl (industrial, 95%)

35.0% mancozeb (industrial, 80%)

4.0% sodium lignin sulfonate

6.0% by weight 1,2-propylene glycol (antifreeze)

0.3% xanthan resin

0.5% citric acid

48.3% water

100.0%

To prepare the agent, the ingredients are blended, wet ground and blended again.

Example L)

Granules (67% by weight)

8.4% Oxadixil (Industrial, 95%)

3.4 t% cimoxanil (industrial, 95 t%)

70.0% mancozeb (industrial, 80%)

10.0% sodium lignin sulfonate

7.7% by weight of kaolin

0.5% citric acid.

To prepare the agent, the ingredients are mixed and ground and then granulated in a cauldron or fluidized bed.

The granules are highly dispersible in water and form a sprayable suspension.

Claims (5)

1. Synergistic fungicide, characterized in that the active ingredient is present in an amount of 0.0004-80% by weight. a) an acylaniline derivative of the formula I in the formula X = CH or N, R _a and R 1, hydrogen or together form a covalent bond and γ is a methoxymethyl or benzyl group - 5 b) a 10: 1 to 1: 3 by weight mixture of 2-cyano-N- (ethylcarbamoyl) -2- (methoxy-amino) -acetamide of the formula UO, and c) optionally containing at least one of manganese-cyrylethylene bis (dithiocarbamate), N-trichloromethylthio- ^10- phthalimide, copper (II) oxychloride and copper (II) calcium sulfate; a liquid diluent, preferably at least one of silicate, kaolin and a water and surfactant additive, preferably a wetting or dispersing agent. Fungicide according to claim 1, characterized in that it contains an acylaniline derivative of the formula (I) in which X = CH, R _a and R * are hydrogen and Y is a methoxymethyl group. 3. The fungicide of claim 1, characterized in that it comprises (I) subjecting acyl aniline derivative of the formula I, where X = CH- .képletében '. És.Rt Ra, H ^25, and Y is benzyl. Fungicide according to Claim 1, characterized in that it contains an acylaniline derivative of the formula (I): In the formula, X is nitrogen, R _a and R * together form a covalent bond and Y is a methoxymethyl group. 5. The fungicide according to any one of claims 1 to 3, characterized in that man contains ³⁵ g of zinc ethylene bis (dithiocarbamate). 1 drawing, 2 formulas