DD221343A5 - FUNGICIDAL AGENTS - Google Patents

Abstract

The present invention relates to novel fungicidal compositions which contain as active ingredient at least one new azolylethylbenzyl ether derivative of the formula other extenders and / or surface-active agents. The products have a microbicidal action. They are unsuitable for use as pesticides and can be used to combat cereal diseases, Venturia species and rice diseases with particular success.

Description

in which

A represents a nitrogen atom in which CH is R ^{1 is} optionally substituted phenyl, R ^{2 is} hydrogen, alkyl or optionally substituted phenyl, R ^{3 is} hydrogen, alkyl, alkenyl or alkynyl, X is halogen, alkyl, alkoxy, alkylthio, haloalkyl, haloalkoxy or Haloalkylthio and η stands for the numbers O, 1 or 2, and its acid addition salts and metal salt complexes, in addition to extenders and / or surface-active agents.

2. A method for combating fungi, characterized in that azolylethyl benzyl ether derivatives of the formula (I) in point 1 is allowed to act on fungi or their habitat.

3. Use of azolylethyl benzyl ether derivatives of the formula (I) in item 1, characterized in that they are used to combat fungi.

4. Use of azolylethyl benzyl ether derivatives of the formula (I) in point 1, characterized in that they are used as pesticides.

5. A process for the preparation of fungicidal agents, characterized by mixing azolylethyl benzyl ether derivatives of the formula (I) in item 1 with extenders and / or surface-active agents.

Field of application of the invention

The present invention relates to novel azolylethyl benzyl ether derivatives and their use as fungicides. Characteristic of known technical solutions It has already been disclosed that certain azolylethyl ether derivatives, such as, for example, 1-butyloxy-1- (2,4-dichlorophenyl) -2- (1,2,4-triazol-1-yl) -ethan or 1- (4-chlorobenzyloxy) -1- (2,4-dichlorophenyl) -2- (imidazol-1-yl) -ethane, have generally good fungicidal properties (compare DE-OS 2547953 and US-PS 3717655) , However, the effect of these compounds is not always satisfactory in certain areas of indication, especially at low application rates and concentrations.

Object of the invention

The new azolylethyl benzyl ether derivatives have strong fungicidal properties. Surprisingly, the compounds used according to the invention show a higher activity than the azolyl ethyl ether derivatives 1-butyloxy-1- (2,4-dichlorophenyl) -2- (1,2,4-triazol-1-yl) known from the prior art. -ethan and 1- (4-chlorobenzyloxy) -1- (2,4-dichlorophenyl) -2- (imidazol-1-yD-ethane, which are constitutionally and functionally obvious compounds represents.

Explanation of the essence of the invention

The invention has for its object to provide new fungicidal agents available. There have been new azolylethyl benzyl ether derivatives of the general formula

(I)

: C = N-OR * ⁵

; U

in which - - - -

A is a nitrogen atom or the CH group,

R ^{1 represents} optionally substituted phenyl,

R ^{2 is} hydrogen, alkyl or optionally substituted phenyl,

R ^{3 is} hydrogen, alkyl, alkenyl or alkynyl,

X is halogen, alkyl, alkoxy, alkylthio, haloalkyl, haloalkoxy or haloalkylthio and

η stands for the numbers O, 1 or 2,

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and their acid addition salts and metal salt complexes found.

The compounds of formula (I) may be in syn and anti form; they are predominantly mixtures of both forms.

It has furthermore been found that the azolylethylbenzyl ether derivatives of the formula (I) are obtained when azolylethanols of the formula

IR ¹ -CH-CH ₂ -N (II)

in which

A and R ^{1 have} the abovementioned meaning,

with benzyl halides of the formula

JHaL - CH ₂ - (CT) (III)

= N-OR ³

in which

Hal is halogen, in particular bromine or chlorine, and R ² , R ³ , X and η have the abovementioned meaning, in the presence of a base and in the presence of an organic diluent, or in an aqueous-organic two-phase system in the presence of a phase transfer catalyst, implements.

Optionally, an acid or a metal salt can subsequently be added to the compounds of the formula (I) thus obtained.

The azolylethyl benzyl ether derivatives of the invention are generally defined by the formula (I). In this formula are preferable

A represents a nitrogen atom, the CH group;

R ^{1 represents} optionally monosubstituted or disubstituted by identical or different substituents phenyl, preferably being mentioned as substituents: halogen, alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 2 carbon atoms, haloalkyl and haloalkoxy each having 1 to 2 carbon atoms and 1 to 5 identical or different halogen atoms, such as fluorine and chlorine atoms and optionally substituted by halogen phenyl and phenoxy;

R ^{2 is} hydrogen, straight-chain or branched alkyl having 1 to 4 carbon atoms or optionally mono- or disubstituted by identical or different substituents phenyl, wherein as substituents preferably the already mentioned in R ¹ phenyl substituents in question;

R ^{3 is} hydrogen, straight-chain or branched alkyl having 1 to 4 carbon atoms or alkenyl and alkynyl having in each case 2 to 4 carbon atoms;

X is halogen, straight-chain or branched alkyl, alkoxy and alkylthio each having 1 to 4 carbon atoms or haloalkyl, haloalkoxy and haloalkylthio each having 1 to 2 carbon atoms and 1 to 5 identical or different halogen atoms, such as fluorine and chlorine atoms; and the index

η for the numbers 0,1 or 2.

Especially preferred are those compounds of formula (I) in which A represents a nitrogen atom or the CH group;

R ^{1 represents} optionally mono- or disubstituted by identical or different substituents phenyl, wherein as substituents may be mentioned: fluorine, chlorine, bromine, methyl, ethyl, methoxy, trifluoromethyl, trifluoromethoxy, phenyl, chlorophenyl and phenoxy;

R ^{2 is} hydrogen, methyl, ethyl, isopropyl, or optionally mono- or di-ore, identical or different, by fluorine, chlorine, methyl, methoxy and trifluoromethyl. substituted phenyl;

R ^{3 is} hydrogen, methyl, ethyl, n-propyl, η-butyl, allyl or propargyl;

X is fluoro, chloro, bromo, methyl, methoxy, methylthio, trifluoromethyl, trifluoromethoxy or trifluoromethylthio; and the index

η stands for the numbers 0 or 1.

Most preferred are those compounds of formula (I) in which A represents a nitrogen atom or the CH group;

R ^{1 represents} optionally mono- or disubstituted by identical or different chlorine or methyl-substituted phenyl; R ^{2 is} hydrogen or methyl;

R ^{3 is} methyl; and the index

η assumes the value.

Preferred compounds according to the invention are also addition products of acids and those azolylethyl benzyl ether derivatives of the formula (I) in which the substituents A, R ¹ , R ² , R ³ and X and the index η have the meanings which are already preferred for these Substituents and the index η were called.

The acids which may be added include, preferably, hydrohalic acids, e.g. Hydrochloric acid and hydrobromic acid, especially hydrochloric acid, furthermore phosphoric acid, nitric acid, mono- and bifunctional carboxylic acids and hydroxycarboxylic acids, e.g. Acetic acid, maleic acid, succinic acid, fumaric acid, tartaric acid, citric acid, salicylic acid and lactic acid, as well as sulfonic acids such as p-toluenesulfonic acid and 1,5-naphthalenedisulfonic acid.

Other preferred compounds of the invention are addition products of salts of metals of II. To IV.Haupt- and the I. and II. And IV. To VIII. Subgroup and those azolylethyl benzyl ether derivatives of the formula (I) in which

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Substituents A, R ¹ , R ² , R ³ and X and the index η have the meanings which have already been mentioned as preferred for these substituents and the index η.

Here, salts of copper, zinc, manganese, magnesium, tin, iron and nickel are particularly preferred. Suitable anions of these salts are those which are derived from those acids which lead to physiologically acceptable addition products. Particularly preferred such acids in this context are the hydrohalic acids, such as. Hydrochloric acid and hydrobromic acid, nitric acid and sulfuric acid.

If, for example, 1- (2,4-dichlorophenyl) -2- (1,2,4-triazol-1-yl) -2-ethanol and 4-methoxyiminomethylbenzyl bromide are used as starting materials, the course of the reaction of the process according to the invention can be characterized by the following formula schema are reproduced:

+ Base

- HBr

The Azolylethanole required as starting materials in carrying out the process according to the invention are generally defined by the formula (II). In this formula, A and R ¹ preferably represent the meanings which have already been mentioned as preferred in the description of the substances of the formula (I) according to the invention for these radicals.

The azolylethanols of formula (II) are known (see for example DE-OS 2431407, 2638470 and 1940388); or they can be obtained in a well-known manner by reacting the corresponding α-bromo (chloro) ketones with imidazole or 1,2,4-triazole in the presence of an inert organic solvent, such as acetone, and in the presence of an acid binder , For example, as potassium carbonate, preferably in the boiling heat and the Azolylethanone thus obtained in the usual manner with complex hydrides, such as sodium hydride, or reduced with aluminum isopropylate.

The benzyl halides also required as starting materials for the process according to the invention are generally defined by the formula (III). In this formula, R ² , R ³ , X and the index η preferably represent the meanings which have already been mentioned in the description of the substances of the formula (I) according to the invention as being preferred for these radicals and the index.

The benzyl halides of the formula (III) are known or can be obtained in a generally known manner by reacting corresponding carbonyl compounds with hydroxylamine (derivatives) in the presence of a solvent, preferably an alcohol, at temperatures between 20 and 100 ° C. implements. In this case, the hydroxylamine (derivative) is preferably used in the form of a salt, in particular as hydrochloride, optionally in the presence of an acid binder, such as sodium acetate. The isolation is done in the usual way. The benzyl bromides of formula (III) can also be obtained by reacting corresponding toluene derivatives in a well-known manner with N-bromosuccinimide.

Suitable diluents for the process according to the invention are preferably inert organic solvents.

These include preferably ketones, such as diethyl ketone, in particular acetone and methyl ethyl ketone; Nitriles, such as propionitrile, in particular acetonitrile; Ethers, such as tetrahydrofuran or dioxane; aliphatic and aromatic hydrocarbons, such as petroleum ether, benzene, toluene or xylene; halogenated hydrocarbons, such as methylene chloride, carbon tetrachloride, chloroform or chlorobenzene; and esters, such as ethyl acetate.

Bases which may be used for the process according to the invention are all customary organic and inorganic bases.

These preferably include tertiary amines, for example triethylamine, or pyridine and alkali metal hydroxides or alkali metal carbonates, for example sodium and potassium hydroxides, and also alkali metal hydrides such as, for example, sodium hydride.

The reaction temperatures can be varied within a substantial range when carrying out the process according to the invention. Generally carried out between 0 ⁰ C and 150 ⁰ C, preferably between 20 ° C and 100 ° C.

When carrying out the process according to the invention, preference is given to working with equimolar amounts. However, it is also possible to use one of the components in an excess. The workup and isolation of the reaction products by conventional methods. In a preferred embodiment, the reaction according to the invention in a two-phase system, such as aqueous sodium or potassium hydroxide / toluene or methylene chloride, carried out, optionally with the addition of 0.1-1 mol of a phase transfer catalyst, such as an ammonium or phosphonium compound, for example be mentioned benzyl-dodecyl-dimethyl-ammonium chloride and triethylbenzylammonium chloride.

The acid addition salts of the compounds of formula (I) can be readily prepared by conventional salt formation techniques, e.g. by dissolving a compound of formula (I) in a suitable inert solvent and adding the acid, e.g.

Hydrochloric acid, and in a known manner, e.g. by filtration, isolated and optionally purified by washing with an inert organic solvent.

The metal salt complexes of the compounds of formula (I) can be obtained in a simple manner by conventional methods, such. B. by dissolving the metal salt in alcohol, eg. For example, ethanol and adding to compounds of formula (I). Metal salt complexes can be prepared in known manner, e.g. by filtration, isolation and optionally by recrystallization.

The active compounds according to the invention have a strong microbicidal action and can be used practically for controlling unwanted microorganisms. The active substances are suitable for use as pesticides.

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Crop protection fungicides are used to control Plasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes, Deuteromycetes.

The good plant tolerance of the active ingredients in the necessary concentrations for controlling plant diseases allows treatment of aboveground plant parts, of plant and seed, and the soil.

As plant protection agents, the active compounds according to the invention can be used to combat cereal diseases, such as Leptosphaeria nodorum, with particularly good results. Mildew, rust, Cochliobolus sativus and Pyrenophora teres; of Venturia species such as Venturia inaequalis and rice diseases such as Pyricularia oryzae and Pellicularia sasakii.

The substances according to the invention also show good fungicidal properties in vitro.

The active compounds can be converted into the customary formulations, such as solutions, emulsions, wettable powders, suspensions, powders, dusts, foams, pastes, soluble pulpers, granules, aerosols, suspension emulsion concentrates, seed powders, active substance-impregnated natural and synthetic substances , Very fine encapsulation in polymeric materials and in coating compositions for seeds, also in formulations with fuel packs, such as smoke cartridges, doses, spirals and others as well as ULV KaIt and warm mist formulations.

These formulations are prepared in a known manner, for. Example, by mixing the active compounds with extenders, that is liquid solvents, liquefied gases under pressure and / or solid carriers, optionally with the use of surfactants, emulsifiers and / or dispersants and / or foam-forming agents. In the case of using water as an extender z. As well as organic solvents can be used as auxiliary solvent. Suitable liquid solvents are essentially: aromatics, such as xylene, toluene, or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, for. As petroleum fractions, alcohols such as butanol or glycol and their ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strong polar solvents such as dimethylformamide and dimethyl sulfoxide, and water; with liquefied gaseous extenders or carriers are meant liquids which are gaseous at normal temperature and under normal pressure, eg. B. aerosol propellants, such as halogenated hydrocarbons as well as butane, propane, nitrogen and carbon dioxide; as solid carriers are: z. Natural minerals such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals such as fumed silica, alumina and silicates; As solid carriers for granules are: z. Crushed and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite and synthetic granules of inorganic and organic flours and granules of organic material such as sawdust, coconut shells, corn cobs and tobacco stalks; suitable emulsifiers and / or foam formers are: e.g. nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, e.g. Alkylaryl polyglycol ethers, alkylsulfonates, alkyl sulfates, arylsulfonates and protein hydrolysates; suitable dispersants are: e.g. Lignin-sulphite liquors and methylcellulose.

Adhesives such as carboxymethyl cellulose, natural and synthetic powdery, granular or latex-type polymers such as gum arabic, polyvinyl alcohol, polyvinyl acetate may be used in the formulations.

Dyes such as inorganic pigments, e.g. Iron oxide, titanium oxide, ferrocyan blue and organic dyes such as alizarin, azo, metal phthalocyanine dyes and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.

The formulations generally contain between 0.1 and 95% by weight of active compound, preferably between 0.5 and 90%.

The active compounds according to the invention may be present in the formulations or in the various application forms in admixture with other known active compounds, such as fungicides, bactericides, insecticides, acaricides, nematicides, herbicides, bird repellents, growth promoters, plant nutrients and soil conditioners.

The active compounds can be used as such, in the form of their formulations or the use forms prepared therefrom by further dilution, such as ready-to-use solutions, emulsions, suspensions, powders, pastes and granules. The application is done in the usual way, for. By pouring, dipping, spraying, spraying, misting, vaporizing, injecting, silting, spreading, dusting, spreading, dry pickling, wet pickling, wet pickling, slurry pickling or encrusting.

In the treatment of parts of plants, the drug concentrations in the use forms can be varied within a substantial range. They are generally between 1 and 0.0001 wt .-%, preferably between 0.5 and 0.001%.

In seed treatment, in general, amounts of active ingredient of 0.001 to 50 g per kilogram of seed, preferably 0.01 to 10 g, are needed.

When treating the soil, drug concentrations of 0.00001 to 0.1% by weight, preferably 0.0001 to 0.02% by weight, are required at the site of action.

embodiments

Preparation Examples ___. - GH ₂ / IN - jsr I Examples ι ^,. J) -OH- 0 CH ₂ - N GH = U-OCH ₃ ^ ^

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12.9 g (0.05 mol) of 1- (2,4-dichlorophenyl) -2- (1,2,4-triazol-1-yl) ethanol and 0.5 g of triethylbenzylammonium chloride are dissolved in a 2-phase mixture Dissolved 100 ml of methylene chloride and 15 ml of 50% sodium hydroxide solution and treated dropwise with rapid stirring with 12.9 g (0.06 mol) of 3-bromomethyl-benzaldehyde O-methyl oxime ether. The mixture is stirred for 3 hours at room temperature, the aqueous phase separated and the organic phase washed several times with water. After drying over sodium sulfate, the organic phase is concentrated and the residue is stirred with diisopropyl ether. This gives 9.2 g (45% of theory) of 1- (2,4-dichlorophenyl) -1- (3-methoximinomethyl-benzyloxy) -2- (1,2,4-triazol-1-yl) -ethane of melting point 125 to 128 ° C.

Preparation of the starting product

A mixture of 44.7 g (0.3 mol) of 3-methylbenzaldehyde O-methyl oxime ether, 53.7 g (0.3 mol) of N-bromosuccinimide and 0.5 g of azodiisobutyronitrile in 200 ml of carbon tetrachloride is refluxed for 4 hours. After removal of the resulting succinimide, the solution is concentrated on a rotary evaporator and the residue is distilled. This gives 37.6 g (55% of theory) of 3-bromomethyl-benzaldehyde O-methyloximether of boiling point 90 to 95 ° C / 0.5mbar.

In a corresponding manner and according to the method of the invention, the compounds of the following table of the general formula

(I)

R ¹ --CH - CH, - N

C = N-OR ³

Erha Lten: Ex.

Physi kai. constant

CH = N-OCH ₃ N CH = N-OCH ₃ CH

D)

CH = N-OCH ₃

Tough OeL Tough OEL Tough Oel

NMR data for the above examples m (CDCI ₃ InTMS): S 4.35 ppm (2H); Example 2: G m 7.35 ppm (3H); s 3.9 ppm (3H); S 4.3 ppm (2H); S 8.05 ppm (1H); m 5.1 ppm (1H); 7.2 ppm (4H); s 7.85 ppm (1H); m 7.95 ppm (1H); m 4.35 ppm (2H); Example 3: m S 8.0 ppm (1H); s 3.95 ppm (3H); 4.1 ppm (2H); m 4.95 ppm (1H); m 7.2 ppm (10H); m 4.3 ppm (2H); Example 4: m m 7.25 ppm (8H); s 3.95 ppm (3H); 4.1 ppm (2H); m 4.9 ppm (1H); 6.85 ppm (2H); s 7.95 ppm (1H)

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use Examples

In the following examples, the compounds indicated below are used as comparative substances:

Cl (A) ~

(B)

χ ENT ₃

Example A

Leptosophaeria nodorum test (wheat) / protective

Solvent: 100 parts by weight of dimethylformamide

Emulsifier: 0.25 parts by weight of alkylaryl polyglycol ether

To prepare a suitable preparation of active compound, 1 part by weight of active compound is mixed with the specified amounts of solvent and emulsifier and diluted as a concentrate with water to the desired concentration.

To test for protective activity, young plants are sprayed with the preparation of active compound in a dewy manner. After the spray coating has dried on, the plants are sprayed with a conidia suspension of Leptosphaeria nodorum. The plants remain 48 hours at 20 ⁰ C and 100% relative humidity in an incubation cabin.

The plants are placed in the greenhouse at a temperature of about 15 ° C and a relative humidity of about 80%.

10 days after the inoculation the evaluation takes place.

A clear superiority in the effectiveness over the prior art show in this testz. B. the compounds according to the following preparation examples: 3.1 and 4.

Example B '

Venturia test (apple) / protective

Solvent: 4.7 parts by weight of acetone

Emulsifier: 0.3 part by weight of alkylaryl polyglycol ether

To prepare a suitable preparation of active compound, 1 part by weight of active compound is mixed with the indicated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.

To test for protective activity, young plants are sprayed with the preparation of the active ingredient until dripping wet. After the spray coating has dried on, the plants with an aqueous conidia suspension of the apple scab (Venturia inaequalis) and then remain are inoculated at 20 ⁰ C and 100% relative humidity in an incubation for 1 day.

The plants are then placed in the housing at 20 ⁰ C and a relative humidity of about 70%.

12 days after the inoculation the evaluation takes place.

A clear superiority in the effectiveness over the prior art show in this test z. B. the compounds according to the following preparation examples: 2,3 and 1.

Claims (1)

-1- 262 124 Invention claims: 1. Fungicidal agent, characterized in that it contains as active ingredient at least one azolylethyl benzyl ether derivative of the general formula i 1 / ^Α ~ ϊΐ ! R '- GH - CHU - W II ; δ ² ^ -ν (D, «Before ^z n