DD286504A5 - FUNGICIDES AND METHOD FOR CONTROLLING PLANT-FLAVORING MUSHROOMS - Google Patents

Abstract

Fungicidal agents, the azolylmethylsilanes of the general formula I in which X is a nitrogen atom or a CH group, Y is an oxygen or sulfur atom, R is a straight-chain or branched alkyl radical having 1 to 6 C atoms, an unsubstituted or mono- or polysubstituted Halogen-substituted phenyl radical, a thienyl or biphenylyl radical or a C 6 H 5 SCH 2 group, R 1 is an unsubstituted or mono- or polysubstituted by alkyl groups having 1 to 3 C atoms, alkoxy groups having 1 to 3 C atoms or by halogen phenyl, m is one of Numbers zero or 1 and n is one of the numbers 1, 2 or 3 or plant physiologically acceptable Saeureadditionssalze or plant physiologically acceptable metal complexes thereof in addition to conventional excipients and tracer, as well as their preparation and use and a method for controlling phytochemical fungi. Formula I {fungicidal agents; Azolylmethylsilan; phenyl; thienyl; biphenylyl; combating; mushrooms; Saeureadditionssalz; Metal complex}

Description

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Fungicidal agents and methods of controlling phytopathogenic fungi

Field of application of the invention

The invention relates to fungicidal compositions containing new azolylmethylsilanes in addition to conventional excipients and carriers and a process for their preparation and their use. Field of application is the agricultural industry.

Characteristic of the known state of the art

U.S. Patent 3,692,798 discloses alkyl, alkylphenyl or phenylsilylmethylimidazoles having antifungal properties. US Pat. No. 4,510,136 describes alkyl-, alkylphenyl- or phenylsilylalkyltriazoles whose phenyl radicals may be many times substituted with fungicidal properties. EP-A 148.026 discloses fungicidal silylmethylimidazoles and -triazoles which contain unsaturated alkyl groups. However, the fungicidal action of these known compounds is not always completely satisfactory in all fields of application.

Aim of the Erfingung

The aim of the invention was to develop new fungicidal agents, which are characterized by a particularly strong fungicidal action.

Explanation of the essence of the invention

It was an object of the present invention to develop new, particularly effective fungicidal compositions and possibilities for their preparation. The invention therefore fungicidal agents which are characterized in that at least one azolylmethylsilane of the general formula I of the formula sheet in which X is a nitrogen atom or a -CH group, Y is an oxygen or sulfur atom, R is a straight-chain or branched alkyl radical 1 to 6 C

Atoms, an unsubstituted or mono- or polysubstituted by halogen phenyl, a thienyl or biphenylyl or a C6H5-S-CH2 group, R ^ is an unsubstituted or mono- or polysubstituted by alkyl groups having 1 to 3 carbon atoms, alkoxy phenyl substituted with 1 to 3 carbon atoms or halogen, m is one of the numbers zero or 1 and η one of the numbers 1, 2 or 3, or at least one plant physiologically acceptable acid addition salt or at least one plant physiologically acceptable metal complex thereof in addition to conventional auxiliaries and carriers contain.

According to the invention, in the formula I> ', a nitrogen atom or a -CH group, preferably ε! Η nitrogen atom, Y denotes an oxygen or a sulfur atom, preferably a sulfur atom, R denotes a straight-chain or branched Aikylresi: with 1 to 6 C-atoms , an unsubstituted or mono- or polysubstituted by halogen, phenyl, a thienyl or Biphanylylrest or a C6H5-S-CH2 group, preferably an unsubstituted or mono- or polysubstituted by halogen phenyl or dsn Biphenylylrest, more preferably an unsubstituted or by Halogen mono- or polysubstituted phenyl radical, R ^ is an unsubstituted or mono- or polysubstituted by alkyl groups having 1 to 3 carbon atoms, alkoxy groups having 1 to 3 carbon atoms or halogen-substituted phenyl radical, preferably an unsubstituted or halogen-substituted phenyl radical, m one of the numbers zero or 1, preferably 1 and η one of the numbers 1, 2 or 3, preferably 1.

The term alkyl is to be understood depending on the number of carbon atoms given, for example, one of the following groups: methyl, ethyl, propyl, butyl, pentyl, hexyl and their isomers, such as. B. isopropyl, isobutyl, tert-butyl, be: .- butyl, isopentyl, etc. The term alkoxy depending on the number of carbon atoms given, for example, a methoxy, ethoxy, propoxy or iso-propoxy group to understand. Halogen is fluorine, chlorine or bromine.

Preferred compounds are those in which X is a nitrogen atom, Y is a sulfur atom and R and R \ independently of one another are an unsubstituted or mono- or polysubstituted by halogen phenyl radical or R is the biphenylyl radical and η and m are each the number 1.

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Very particular preference is given to the following compounds:

Methyl (2,4-dichlorophenyl) (phen> lthiumethyl) (l, 2,4-triazol-l-ylmethyl) 3ilan

Methyl-phenyl (phenylthiomethyl) (l, 2,4-triazol-l-ylmethyl) silane

Methyl (i-biphenyl-4-yl) (phenylthiomethyl) (l, 2,4-triazol-l-ylmethyl,) silane

The novel compounds may also be present in the form of their acid addition salts or their metal complexes. As acid addition salts are salts of inorganic or organic acids, for example hydrochlorides, nitrates, hydrogen sulfates, methosulfates, as metal complexes z. As copper, zinc, manganese, tin, iron and nickel complexes into consideration.

Furthermore, it has been found that nr n is the compounds of general formula I according to the invention of formula I in which X, Y, R, Ry, m and η have the abovementioned meaning, by reacting a compound of general formula VI of the formula sheet, in the Y, R, Ri ₁ m and η have the cb-mentioned meaning with an AlkaÜ3alz of imidazole or triazole optionally in the presence of an inert diluent to give a compound of general formula I of the formula sheet.

For the preparation of the new Azolylmethylsilane be set, for example, a compound of general formula II of the formula sheet, in which k is zero or 1, with a compound of general formula III of the formula sheet, in which R has the abovementioned meaning and in the M lithium or Sodium, optionally in the presence of a diluent inert under the reaction conditions, to give a compound of general formula IV of the formula sheet in which R and k have the abovementioned meaning, optionally leaves the resulting reaction product of general formula IV without isolating it with a compound of general formula V of the formula sheet in which Y, R 1, k, m and η have the abovementioned meaning and M 1 denotes sodium or lithium, c in the presence of a diluent inert under the reaction conditions, give compound of general formula VI of the formula sheet, in which Y, R, R \, m and η have the abovementioned meaning reacts and sets the compounds of general formula VI thus obtained with an alkali metal salt of imidazole or triazole optionally in

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Presence of an inert diluent under the reaction conditions finally to a compound of general formula I of the formula sheet to.

The starting compound of the general formula II of the formula sheet in which k is the number zero and the starting compound of the general formula IV of the formula sheet in which k is the number zero and R is methyl, are commercial products. The compound of the general formula II in which k is 1 may be obtained by reaction of methyl dichloro-chloromethyl-silane with bromochloromethane at low temperatures, optionally in the presence of an inert diluent, the r, o obtained compound without separate isolation can be implemented further.

The reaction is preferably carried out at temperatures of -100 bi3 -50 ⁰ C, more preferably between -100 and -80 ⁰ C in an organic diluent, such as. For example, pentane, hexane, benzene, toluene, xylene, diethyl ether, diisopropyl ether, petroleum ether, tetrahydrofuran and combinations of these diluents, wherein diethyl ether and / or hexane are preferred by presenting bromochloromethane and methyl-dichloro-chloromethyl-sullan in preferably equimolar ratio and Addition of a preferably equimolar amount of n-butyllithium. This procedure is new.

The resulting methyl-chloro-bis-chloromethyl-silane can then be reacted directly without further purification with a compound of general formula III of the formula sheet.

The reactive compounds of the general formula III or of the general formol V of the formula sheet in which R and R 1 have the abovementioned meaning and M and M 1 represent lithium can be synthesized, for example, by reacting a compound RBr or Ri- (Y) nv ( ^CH 2) nk- ^{ßr in which} K ^Dzw · ^R l have ^the indicated meaning, with butyl lithium in an organic diluent, for example in tetrahydrofuran or diethyl ether at temperatures of -100 to 0 ⁰ C, preferably at -80 to -60 ⁰ C, are produced. For the preparation of the reactive compounds of the general formula V, in which Μχ denotes lithium, it is also possible to use compounds of the general formula Ri- (Y) _n -, - - (CH 2) nk "H · ^η presence of a preferably equimolar amount of tetra-

methylenediamine optionally in the presence of a diluent such as. B. tetrahydrofuran be reacted with butyl lithium.

The preparation of the sodium salts of the compounds of general formulas III and V can be carried out by known and customary methods of organic chemistry, for example using sodium hydride in the presence of an organic diluent.

The reaction of the compounds of general formula II of the formula sheet with compounds of general formula III of the formula sheet to compounds of general formula IV of the formula sheet is carried out for example in the presence of a diluent at low temperatures of about -ICO ⁰ C to 0 ⁰ C, in particular at temperatures of bie -75 -60 ⁰ C. Suitable diluents for example, organic solvent, diethyl ether and tetrahydrofuran are particularly preferably used. The reaction product of general formula IV of the formula may be worked up by customary F. extraction method and tamped for example by distillation or column chromatography. In many cases, however, the resulting compound of general formula IV without purification or isolation directly with a compound of general formula V of the formula sheet, in which Y, R \, k, m and η have the abovementioned meaning and Mj is sodium or lithium , around.

The reaction of the compounds of general formula IV with compounds of general formula V to give compounds of general formula VI of the formula sheet in which Y, R, Ri, m and η have the abovementioned meaning, can be carried out in the presence of a diluent at low temperatures of about 80 bie 0 ⁰ C, in particular at temperatures from -75 to -60 ⁰ C take place. Suitable diluents are, for example, organic solvents such as pentane, hexane, benzene, toluene, xylene, diethyl ether, diisopropyl ether, petroleum ether, tetrahydrofuran and combinations of these diluents, with diethyl ether and / or tetrahydrofuran being preferred. To remove dee resulting inorganic salt, the reaction product of general formula VI is optionally worked up by conventional Kxtraktionsmethoden, wherein about the reaction mixture Was3er added and the organic phase extracted several times with water. The organic phase is dried and the solvents are

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removed. The residue can be purified by distillation or column chromatography.

The reaction of the compounds of general formula VI with an alkali metal salt of imidazole or triazole to give a compound of general formula I of the formula sheet in which X, Y, R, R ₁ m and η have the abovementioned meaning, is usually carried out in the presence of a solution or diluent at temperatures between about 0 and 200 ⁰ C, preferably between 20 and 100 ⁰ C as solvents or diluents are polar, organic solvents such. As methanol, ethanol, tetrahydrofuran, dimethylformamide or dimethyl sulfoxide, with dimethylformamide being particularly preferred. The workup is carried out, for example, by conventional extraction methods, by about the reaction mixture, an organic, immiscible with water solvent such. For example, ethyl acetate, dichloromethane, diethyl ether, etc., and water, the organic phase is washed with water and dried. After removal of the solvent, the purification of the residue can be carried out for example by column chromatography.

For the preparation of the compounds of general formula I of the formula sheet in which R is a, methyl radical, m is the number K-l and η is 2 and X and R \ have the abovementioned meaning, it is also possible to proceed in such a way that a compound the general formula IV of the formula sheet, in which R is a methyl radical and k is zero, in an organic diluent, preferably in diethyl ether with a Hydrierrp.ittel preferably reduced with lithium aluminum hydride to dimethyl-chloromethyl-silane and this compound after a cleaning operation, the For example, in a distillation can be reacted with a styrene of the general formula VII of the formula sheet in which Ri has the abovementioned meaning. The reaction is preferably carried out in the presence of a diluent, in particular in the presence of cyclohexane and in the presence of a catalyst, in particular in the presence of hexachloroplatinic acid at temperatures from room temperature to 80 ⁰ C, preferably from 50 to 60 ⁰ C.

The product of the general formula VI of the formula sheet in which R is methyl, m is the number zero and η is the number 2 is then described in the above

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with an alkali salt of imidazole or triazole to give a compound of the general formula I of the formula sheet in which R is methyl, m is the number zero and η is 2 and R 1 and X have the abovementioned meaning, and in which worked up and cleaned as described above.

The preparation of the acid addition salts, which may optionally also represent a purification step, can be carried out by dissolving the base of a compound of general formula I in a solvent such as acetone, ethyl acetate or diisopropyl ether and precipitating the acid addition salt by addition of acid or by addition of acid and a nonpolar solvent such as diethyl ether, diisopropyl ether, hexane, heptane. The purification can be carried out expediently by recrystallization.

To prepare the metal complexes, the compounds of general formula I of the formula sheet can be dissolved in a solvent such as acetone, methylene chloride, chloroform, methanol, ethanol, isopropanol, preferably in acetone or ethanol, and a solution of a metal salt can be added. The precipitate which may have precipitated is isolated and dried, or the residue left after evaporation of the solvent is crystallized or subjected to a chromatographic purification operation.

In all reactions, the starting materials are usually used in a stoichiometric ratio. An excess of one or the other may be quite advantageous in individual cases.

The Azolylmethylsilane invention exhibit excellent fungicidal properties and thus represent an enrichment of the art. They are effective against a wide range of phytopathogenic fungi, z. B. against fungi from the classes of Oomycetes, Ascomycetes, Basidiomycetes and Deuteromycetes.

The good plant tolerability and the systemic action in the concentrations necessary for the treatment of plant diseases allow the treatment of aboveground plant parts, of planting and seed.

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Examples of crops are cereals such as wheat, barley, rye or oats, as well as ornamental plants, wine, apple and cucumber.

With particularly good results, the agents according to the invention can be used, for example, for controlling the following plant diseases:

Cercospora beticola (Cercospora leaf spot disease) on turnips

Cochliobolus sativus (Helminthosporiose) on cereals

Erysiphe graminis f.spec.tritici (powdery mildew) on wheat

Erysiphe graminis f.spec.hordei (powdery mildew) on barley

Fusarium culrnorum (fusariosis) on cereals

Monographella nivalis (snow mold) on cereals

Phaeosphaeria nodorum (brown furred) on cereals

Puccinia recondita (brown rust) on wheat

Puccinia coronata (crown rust) on oats

Venturia inaequalis (apple scab) on apples

Uncinula iecator (powdery mildew) on wine

Depending on their field of application, the new active compounds can be converted into the customary formulations, such as solutions, wettable powders, emulsion concentrates, emulsions, suspensions, powders, foams, pastes, granules, aerosols, active-ingredient-impregnated natural and synthetic substances, ultra-fine encapsulations in polymeric substances and in encapsulants for seed, also in formulations with fuel packs, such as smoke cartridges, doses, spirals, etc., as well as ULV KaIt and warm mist formulations.

These formulations are prepared in a known manner, for. B. by mixing the Wirk3toffe with diluents ^ so liquid solvents * under pressure liquefied gases and / or solid carriers, optionally with the use of teasides, emulsifiers and / or dispersing and / or wetting agents 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 chlorine

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benzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons such as cyclohexane or paraffins, e.g. As petroleum fractions, alcohols such as butanol or .Glykol, and their ethers and Lster, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents such as dimethylformamide and dimethylsulfoxide, and water. By liquefied, gaseous diluents or carriers are meant liquids which are gaseous at normal temperature and under normal pressure, for. B. aerosol propellants, such as Halogenkol ·. such as butane, propane, nitrogen and carbon dioxide; as solid carriers _and ger3toffe are: z. Natural goetine powders such as kaolins, alumina, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and synthetic products such as fumed silica; Alumina and silicates; As solid carriers for granules are: z. For example, crushed and fractionated natural rocks such as calcite, niarmor, pumice, sepiolite, dolomite and synthetic granules of inorganic and organic mills, as well as granules of organic material such as sawdust, coconut shells, corncobs and tobacco stalks; suitable emulsifiers and / or foaming agents are: z. Nonionic and ionic surfactants, such as polyoxyethylene sorbitan acid esters, Na-oleylmethyltrauride, polyoxyethylene-fatty acid esters, polyoxyethylene fatty alcohol ethers, e.g. B. Alkylarylpolyglykolether, alkyl sulfonates, alkyl sulfates, Arylsulforate, aryl sulfates and Arylalkyisulfonate and protein hydrolysates; as dispersants in question: z. As lignosulfonates Koridensationsprodukte of arylsulfonates with formaldehyde or methylcellulose.

Adhesive and thickening agents such as carboxymethylcellulose, methylcellulose, natural and synthetic powdery, granular and stearic polymers can be used in the formulations, such as Gumcii arabicum, polyvinyl alcohol, polyvinyl acetate, as well as natural phospholipids such as cephalins and lecithins and synthetic phospholipids. Other additives may be mineral and vegetable oils

It may colorants, wte inorganic Pigme'le, z. And organic dyes such as alizarin, azo and metal phthalocyanine dyes and trace nutrients such as iron / manganese salts, Bl » ¹ , copper, cobalt, molybdenum and zinc. be used.

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 can 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, protective substances against growth attack, growth substances, plant substances 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 casting, dipping, spraying, spraying, atomizing, vaporizing, injecting, silting, dusts, spreading, dry pickling, wet pickling, wet pickling, slurry pickling or incinerating "3n.

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 the application of the active ingredients for the treatment of fungal infections, the application rates are between 0.015 and 4 kg of active ingredient / ha area. For surface protection of trees and fruits, the active compounds may also be used in conjunction with Kurstofstoffdispersionen 0.25% to 5%, based on the weight of the dispersion. In the seed treatment are generally drug amounts of 0.001 to 50 g per kilogram of seed, preferably 0.01 to 10 g needed. For treatment of the soil, active ingredient concentrations of 0.00001 to 0.1% by weight, preferably 0.0001 to 0.02%, are required at the site of action.

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Working Examples Example 1 Methyl-1-dichloro-phenyl-phenyl-thiomethyl-XXl-triazol-1-yl-methy-silane

Preparation of the lithium salt of thioanisole:

18.6 g of tetramethylenediamine (0.16 mol) and 20.0 g of thioanisole (0.16 mol) were added in ml of tetrahydrofuran with stirring at 0 ⁰ C with 100 ml of a 1.6 molar n-butyllithium solution in hexane and in this Temperature stirred for one hour. The resulting lithium salt of thioanisole was used without isolation in reaction step b).

a) methyl (2,4-dichlorophenyl) chloro-chloromethyl-silane

36.1 g of l-bromo-2,4-dichlorobenzene (0.16 mol) were mixed with 26.2 g of methyl-dichlorochloromethyl-silane (0.16 mol) in 100 ml of tetrahydrofuran with stirring at -70 ⁰ C with 100 ml a 1.6 molar n-ButyÜithlumlösung in hexane

 The resulting methyl (2,4-dichlorophenyl) chloro-chloromethyl-silane was used without isolation in reaction step b).

b) Methyl (2,4-dichlorophenyl) (phenylthiomethyl) chloromethyl-silane

The solution of methyl (2,4-dichlorophenyl) chloro-chlormathyl-silane, which was obtained by the above procedure, was cooled to -70 ⁰ C and dropwise added with the suspension of the lithium salt of the Thioanisols obtained as described above. After the reaction was allowed to warm to room temperature and water and diethyl ether were added

 The organic phase was washed with water, dried, evaporated and the residue was purified by column chromatography

Yield: 34.7 g (60 % - theory) H ¹ NMR: 0.8 (s, 3H) j 2.8 (s, 2H); 3,4 (s, 2H); 7.3-7.6 m, 8H);

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c) Meth) l (2, A-dichlorophene) 1) (phenylthiomethyl) (l, 2,4-triazol-1-ylmethyl) silane

34.7 g of MethyKZ.A-dichlorophenylXphenylthiomethyD-chloromethyl-silane (0.096 mol) were treated with 200 ml of dimethylformamide at room temperature with 10.5 g of the sodium salt of 1,2,4-triazole (0.115 mol) and 2 hours at this temperature touched.

Thereafter, water and ethyl acetate were added, shaken out and the organic phase was washed with water and dried. After evaporation of the solvent, the residue was purified by column chromatography

 Yield: 14.5 g (38% of theory)

Example 2 Methylphenyl (3,5-dichlorophenylthiomethyl) (L _> 2 ₎ 4-triazol-1-ylmethyl) silane

Preparation of methyl chloro-bis-chloromethyl-silane:

20.7 g of bromochloromethane (0.16 mol) were cooled in 150 ml of diethyl ether with 26.6 g of methyl dichloro-chloromethyl-silane (0.16 mol) and about 3 g of lithium bromide with stirring to -10.0 ⁰ C. At this temperature, 100 ml of a 1.6 molar n-butyllithium solution in hexane were slowly added dropwise. The resulting methyl-chloro-bis-chloromethyl-silane was used without isolation in the reaction step a).

a) Methyl-phenyl-bis-chloromethyl-silane

The solution of the methyl-chloro-lis-chloromethyl-silane, which was obtained according to the above procedure, was added at -70 ⁰ C with 80 ml of a 2-molar solution of phenyllithium in a benzene - Diethyletherqemisch (7: 3). After warming to room temperature, the mixture was stirred for 12 hours, the organic phase was extracted by shaking with water, dried and vacuum distilled.

Kp: 64 - 66 ⁰ C at 0.5 Torr

H ¹ NMR: 0.3 (s, 3H); 2.9 (m, 4H); 7.2-7.3 (m, 3H); 7.4 (m, 2H);

b) Methyl phenyl O.S-dichlorophenylthiomethyldichloromethylsilane

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4.4 g of 3,5-dichlorothiophenol (0.025 mol) in 40 ml of dimethylformamide were added with stirring at room temperature with 4.0 g of sodium methylate (30% solution in methanol). This solution was dissolved at 0 ^° C. in a solution of

5.5 g of methyl phenyl-bis-chloromethyl-silane (0.025 mol) in 15 ml of dimethylformamide was added dropwise. After completion of the addition, 100 ml of water and 150 ml of diethyl ether were added, the organic phase was washed with water, dried and evaporated. The residue was purified by column chromatography.

Yield: 3.0 g (60% of theory)

H ^ NMR: 0.7 (s, 3H); 2.6 (m, 2H); 3.5 (m, 2H); 7.1-7.7 (m, 8H)

c) Methylphenyl (3,5-dichlorophenylthiomethyl) (l, 2,4-triazol-1-ylmethyl) silane

The preparation was carried out according to Example Ic from 1.5 g of Na salt of 1,2,4-triazole (0.016 mol) and 3.0 g of methyl phenyl (3,5-dichlorophenylthiomethyl) chloromethylsilane (0.008 mol) from stage b).

 Yield: 0.8 g (25% of theory)

Example 3 Dimethyl (4-bromophenylethyl (1,3-imidazol-1-ylmethyl) silane

a) dimethyl chloromethylsilane

45 g of dimethyl chloro-chloromethyl-silane in 30 ml of diethyl ether were added at 0 ^° C. with 80 ml of a 1 molar ethereal lithium aluminum hydride solution. Now 50 ml of dibutyl ether were added and condensed at 0 ⁰ C in a high vacuum in a cold trap. The resulting solution was distilled.

Yield: 18.5 g (55% of theory.) Kp: 80 - 88 ⁰ C, η $ 1.4180

b) Dimethyl (4-bromophenylethyl) chloromethyl-silane

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4.2 g of dimethyl chloromethyl-silane (0.04 mol) were admixed with 7.1 g of 4-bromostyrene (0.04 mol) and 50 ml of cyclohexane. After addition of 10 mg hexachloroplatinic acid (dissolved in a little isopropanol) was stirred at 50 to 60 ⁰ C for 3 hours. Then the solvent was evaporated and the residue was distilled.

Bp: 143-145 ⁰ C at 2.5 torr

Yield: 6.9 g (67% of theory)

H ¹ NMR: 0.1 (s, 6H); 0.9-1.0 (m, 2H); 2.5-2.6 (m, 2H), 2.7 (s, 2H, 7.0 (d, 2H), 7.3 (d, 2H)

c) Dimethyl (4-bromophenylethyl (1,3-imidazol-1-ylmethyl) silane

The preparation was carried out in 2.3 g of dimethyl (4-bromophenylethyl) chloromethylsilane (0.009 mol) and 1 g of the sodium salt of 1,3-imidazole (0.011 mol) according to Example Ic

 Yield: 0.8 g (31% of theory)

In one of the above procedures, the compounds 4 to 21 were synthesized using the corresponding starting materials.

No. R rl X Y m η 4 methyl phenyl N S 1 1 5 methyl phenyl CH S 1 1 6 n-butyl phenyl N S 1 1 7 phenyl 4-chlorophenyl N S 1 1 8th 4-fluorophenyl phenyl N S 1 1 9 3,5-dichlorophenyl phenyl N S 1 1 10 C ₆ H ₅ -S-CH ₂ - phenyl CH S 1 1 11 l, l-biphenyl-4-yl phenyl N S 1 1 12 2-thienyl phenyl N S 1 1 13 methyl phenyl N - 0 2 14 methyl 4-toluyl N - 0 2 15 methyl 4-methoxyphenyl N - 0 2 16 methyl 4-fluorophenyl N - 0 2 17 methyl 4-Fluorphiinyl CH - 0 2 18 methyl 4-chlorophenyl N - 0 2 19 methyl 4-bromophenyl N - 0 2 20 methyl 4-Chloromethyl N 0 1 3 21 methyl 2,4-dichlorophenyl N 0 1 3

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18 Physical Data of the New Connections.

Connection 1

HlNMR: 0.7 (s, 3H); 2.9 (s, 2H); 4.5 (s, 2H); 7.3 (m, lH); 7.4 (m, 5H); 7.6 (m, 2H); 8.0 ( _3> 1H); 8.1 (s, lH);

Connection 2

H ¹ NMR: 0.7 (s, 3H); 2.6 (m, 2H); 4.2 (m, 2H); 7.0 (m, 2H); 7.5 (m, 4H); 7.6 (rn, 2H); 8.0 (d, 2H);

Connection 3

H ¹ NMR: 0.1 (s, 6H); 0.9-1.0 (m, 2H); 2.5-2.6 (m, 2H); 3.5 (s, 2H); 6.8 (s, 1H) j 7.0 (m, 3H); 7.3 (m, 3H);

Connection 4

H ¹ NMR: 0.3 (s, 6H); 2,3 (s, 2H); 3.9 (s, 2H); 7.2 (m, lH); 7.3 (m, 4H); 7.9 (s, lH); 8.0 (S ₁ IH);

Connection 5

H ¹ NMR: 0.3 (s, 6H); 2,3 (s, 2H); 3.8 (s, 2H); 6.9 UJ ₁ IH); 7.1 (s.lH); 7.3-7.4 (m, 5H), 7.6 (s, 1H);

Connection 6

H ¹ NMR: 0.3 (s, 3H); 0.8-1.0 (m, 5H); 1.4-1.5 (m, 4H); 2,4 (s, 2H); 4.0 (s, 2H); 7.3 (m.lH); 7.4 (m, 4H); 8.0 (s.lH) 8.1 (s, lH);

Compound 7H ¹ NMR: 0.7 (s, 3H); 2.8 (m, 2H); 4.2 (m, 2H); 7.3 - 7.6 (m, 9H); 8.0 (s, 2H);

Connection 8

H ¹ NMR: 0.7 (s, 3H); 2.7 (m, 2H); 4.3 (m, 2H); 7.1 - 7.2 (m, 3H); 7.4 (m, 4H); 7.5-7.6 (m, 2H); 8.0 (d, 2H);

? 8 6 5 O 4

Connection 9

H ¹ NMR: 0.7 (s, 3H); 2.7 (m, 2H); 4.2 (m, 2H); 7.3 (m, lH); 7.4 (m, 5H); 7.5 (m, 2H); 8.0 (3,1H); 8.1 (s.lH);

Connection 10

H ¹ NMR: 0.3 (s, 3H); 2.4 ( ₃ , 4Η); 3.9 (s, 2H); 7.0 - 7.3 (m.lOH); 7.7 (s, lH); 7.8

Connection 11

H ¹ NMR: 0.7 (s, 3H); 2.8 (s, 2H); 4.2 (s, 2H); 7.3-7.7 (m, 14H); 8.0 (d, 2H);

Connection 12

H ¹ NMR: 0.5 (s, 3H); 2.5 (m, 2H); 4.0 (m, 2H); 7.1-7.3 (m, 5H); 7.3 (m, 2H) i 7.6 (m.lH); 7.8 (m, 2H);

Connection 13

H ¹ NMR: 0.1 (9.6H) ₅ 0.9-1.0 (m, 2H); 2.6 (m, 2H); 3.7 (m, 2H); 7.1-7.3 (m, 5H); 7.8 (3.2H);

Connection 14

H ¹ NMR: 0.1 ( ₃ , 6H); 0.9 (m, 2H); 2,3 (s, 3H); 2.7 (m, 2H); 3.7 (d, 2H); 6.9 - 7.2 (m, 4H); 7.9 (d, 2H);

Connection 15

H ¹ NMR: 0.1 (s, 6H); 0.9-1.0 (m, 2H), 2.5-2.6 (m, 2H); 3.7 (s, 2H); 3.8 (s, 3H); 6.8 (d, 2H); 7.1 (d, 2H); 7.9 (d, 2H);

Connection 16

H ¹ NMR: 0.1 (s, 6H); 0.9-1.0 (m, 2H); 2.5-2.6 (m, 2H); 3.7 (s, 2H); 6.9 - 7.0 (m, 2H); 7.1 - 7.2 (m, 2H); 7.9 (d, 2H);

98 6SO 4

Connection 17

H ¹ NMR: 0.1 ( ₈ , 6H) i 0.9-1.0 (m, 2H); 2.5-2.6 (m, 2H); 3.5 (s, 2H); 6.8 (s, lH); 6.9-7.1 (m, 5H); 7.3 (s, lH);

Connection 18

H ¹ NMR: 0.1 (s, 6H); 0.9-1.0 (m, 2H); 2.5-2.6 (m, 2H) j 3.7 (s, 2H); 7.1 (d, 2H); 7.2 (d, 2H); 7.9 (d, 2H) j

Connection 19

H ¹ NMR: 0.1 (s, 6H); 0.9-1.0 (m, 2H); 2.5-2.6 (m, 2H); 3.7 (s, 2H) i 7.0 (d, 2H); 7.3 (d, 2H); 7.9 (d, 2H);

Connection 20

H ¹ NMR: 0.1 (s, 6H), G, 7 - 0.8 (m, 2H); 1.7-1.8 (m, 2H); 3.7 (s, 2H); 3.8 (m, 2H), 6.7 (d, 2H); 7.1 (d, 2H); 7.8 (s, lH); 7.9 (s.lH);

Connection 21

H ¹ NMR: 0.1 (s, 3H); 0.7 (m, 2H); 1.7 (m, 2H); 3.7 ( ₃ , 2H); 3.9 (m, 2H); 6.7 (d, lH); 7.1 (m.lH); 7.3 (m, lH); 7.8 (s.lH); 7.9 ( _3> 1H);

Example 22 Methyl-phenyl-C 1 -fluorophenyl-thiomethyl-XXl-triazolyl-1-yl-methy-dsilane.HCl

0.5 g of a solution of methyl phenyl (4-fluorophenylthiomethyl) (l, 2 / »- triazolyl-lylmethyDsilan (compound of Example 8) in 15 ml of acetone were added dropwise with stirring with an HCl-saturated diisopropyl ether solution until the strongly acidic reaction. After stirring for a short time, 20 ml of diisopropyl ether were added and the mixture was stirred at room temperature under moist coagulum for several hours, and the precipitate was filtered off with suction, washed with diisopropyl ether and dried to give 0.4 g (72% of the theoretical e) crystalline product a melting point of 115 to 117 ⁰ C.

28050 4

21 Example 23

Meth> -l-phenyl (4-fluorophenylthiometh) l) (l _> 2 _> 4-triazolyl-1-ylmethyl) 3- silane.HNO 3

was prepared according to the procedure of Example 22 using the appropriate starting materials. Melting point: 111-113 ⁰ C.

Example 24 Methyl (2,4-aichlorophenyl) (phenylthiomethyl) (l, 2,4-triazolyl-1-ylmethyl) silane. CuSO 4

0.394 g of a solution of methyl (2,4-dichlorophenyl) (phenylthiomethyl (l, 2,4-triazolyl-1-ylmethyl) silane (1 mmol) in 10 ml of methanol were treated with a solution of 0.25 g of copper (II After prolonged stirring, the solvent was evaporated and the oily evaporation residue was taken up in a little methyl acetate, followed by the careful addition of diethyl ether to precipitate a turquoise solid, which was filtered off with suction, washed with diethyl ether and dried was to give 0.43 g (77.5% of theory) of the Titelverbtndung having a melting point 154-157 ⁰ C.

Example 25 Methyl ( 2,4-dichlorophenylX-phenylthymethylXl _> 2 _> 4-triazolyl-ylmethyl) silane.CuCl 2

was obtained according to the procedure of Example 24 using acetone as a solvent and copper (II) chloride. 2H 2 O as a metal salt

Melting point: 164-168 ⁰ C.

Example 26 Emulsifiable concentrate

? 8 6 5 O 4

10% active ingredient of compound 1

25% 4-butyrolactone

55% xylene

10% Atlox 3335B

The active ingredient was stirred well with the excipients, whereby a concentrate was obtained from the ml '. Water emulsions of any desired concentration can be prepared.

Example 27 Spray Powder

10% active ingredient of the compound 13 80% Attaclay 10% Arkopan T ^R

The active ingredient was mixed intimately with the aggregates in a mixer and ground through rollers and mills, thereby obtaining a wettable powder of excellent wettability which can be diluted with water to give suspensions of any desired concentration.

Set game A

In vitro tests

Cooled culture media were inoculated with an aqueous suspension of hyphae parts and / or conidiospores of the respective test pieces. Filter plates (diameter 5 mm) were soaked in aqueous 0.001 bi3 0.2% dispersions of the active ingredient formulations and placed on the inoculated nutrient media.

The minimum inhibitory concentration (MIC) was used for the assessment. This is the concentration of the active ingredient in the dispersion that completely inhibits growth of the fungus.

As standards, A: propiconazole (1- (2- (2,4-dichlorophenylM-propyl-1,3-dioxolan-2-ylmethyl) -1H-l, 2,4-triazole) and B: thiabendazole (2- (2-) A-thiazyclyD-benzirpidazole).

The following toadstools were also tested according to this method:

a) Cercospora beticola (grown on potato extract, carrot extract and agar)

b) Cochliobolus sativus (grown on biomalt and agar)

c) Fusarium culmorum (pulled on oat flake pulp and agar)

d) Monogoaphella nivalis (pulled on oat flake extract and agar)

e) Phaeosphaeria nodorum (grown on yeast extract, glucose and agar)

test fungus

Results 100 connection 22 default 50 1 7 10 - A B 50 5 5 1 - 10 - 50 - 50 100 _ - - 10 _ - 25 25

a b c d e

Example B

Protective effect of the compound against powdery mildew (Erysiphe cichoracearum) on cucumbers

Ten day old cucumber plants were sprayed with an aqueous dilution of the formulated active ingredient.

After the spraying liquid had dried, the plants were inoculated with conidiospores of infested cucumber plants. The treated plants then remained in the greenhouse under given conditions

 14 days after the artificial infection, the infection with Erysiphe cichoracearum was evaluated.

In this case, for example, the compound 1 in an activity concentration of 10 ppm and the compounds 2, 4, 5, 7 and 13 in a concentration of 100 ppm completely prevented the onset of the disease.

24 Example C

Protektivä Effect of the compounds against powdery mildew (Erystphe graminie) on wheat and barley

Barley and wheat plants in the early 2-leaf stage were sprayed to drip point with an aqueous dilution of the formulated active ingredient. After the spraying liquid had dried on, the plants were inoculated with conidiospores of infested plants. The treated plants then remained in the greenhouse under given conditions.

8 bi3 10 days after the artificial infection, the infection was evaluated with Erysiphe graminis.

In this case, for example, compound 1 in an active compound concentration of 10 ppm and compounds 7 and 13 in a concentration of 100 ppm completely prevented the onset of the disease.

Example D

Protective effect of the compounds against wheat brown rust (Puccinia recondita) on wheat

Wheat plants in the early 2-leaf stage were sprayed to drip point with an aqueous dilution of the formulated active ingredient. After the spray liquid has dried, inoculation was carried out with uredospore obtained from infected plants. Subsequently, the tea plants were incubated for 24 hours at 20 ⁰ C and about 95% humidity in a climate chamber

 Until the complete onset of disease on the control plants, the test plants were under given conditions in the greenhouse.

In this test, for example, compounds 1 and 7 in a concentration of 50 ppm completely prevented the infestation of the test plants.

Example FI

Protective effect of the compounds against oat crown rust (Puccinia coronata) on oats

28450 4

Oat plants in the early 2-leaf stage were sprayed to drip point with an aqueous dilution of the formulated active ingredient. After the spray liquid has dried, inoculation was carried out with uredospore obtained from infected plants. Subsequently, the test plants were incubated for 24 hours at 20 ⁰ C and about 95% humidity in a climate chamber

 At the time of the complete onset of disease on the control plants, the test plants were in the greenhouse under given conditions.

In this test, for example, compounds 1 and 13 in a concentration of 50 ppm sufficiently prevented the infestation of the plants.

Example F

Protective effect of the compounds against wheat leaf drought (Phaeosphaeria nodorum) on wheat

Wheat plants in the early 2-Blatt.tadium were sprayed with an aqueous dilution of the formulated drug to dripping wet. After the spray liquid has dried on, it was inoculated with an aqueous suspension of Pyknidiospores of Phaeosphaeria nodorum.

Subsequently, the test plants were incubated for 36 to 48 hours at 20 ⁰ C and about 95% humidity in a climate chamber.

Until z'.in the full onset of disease on the control plants, the test plants were under given conditions in the greenhouse.

In this test, for example, the compounds 1, 7 and 13 in a concentration of 20ü ppm completely or sufficiently prevented the infestation of the plants.

Example G

Protective effect of compounds against powdery mildew (Uncinula necator) on wine

2 months old wine cuttings were sprayed to drip point with an aqueous dilution of de3 formulated drug. After the spray liquid had dried, the inoculation was carried out with conidiospores of Uncinula necator.

98650 4

Until the complete onset of disease on the control plants, the test plants were under given conditions in the greenhouse.

In this test compound 1 still prevented in a concentration of 1.56 ppm 100% infestation of the test plants.

Example H

Protective effect of the compounds against apple scab (Venturia inaequalis)

2 months old apple cuttings were sprayed to drip point with an aqueous dilution of the formulated drug. After the spray liquid had dried on, it was inoculated with a conidiosporene suspension of Venturia inaequalis.

(- 95 ° C Humidity 90 20 ⁰⁾ and then three weeks held up to full outbreak of disease on the control plants under greenhouse conditions the plants were thereafter for 3 days in a humid chamber.

In this test compound 1 still prevented the attack of the test plants in a concentration of 6.25 ppm 100%.

Example J

Protective effect of the compounds against Cercospora leaf spot disease (Cercospora beticola) on beets

15 to 20-day-old beet plants were sprayed to drip point with an aqueous dilution of the formulated active ingredient.

After the spray coating had dried, the inoculation was carried out with a conidiosporene suspension of Cercospora beticola. This was followed by a 48-hour incubation in the humid chamber.

Until the complete onset of disease on the control plants (8 to 10 days), the test patches were kept under humid greenhouse conditions.

In this test compound 1 still prevented in a concentration of 1.65 ppm 100% infestation of the test plants.

FüTmelblatt

~ 27-

050

OH.

K-Ei-CH _n - NCH.

Cl-Si-CH ₂ Cl • ι

(CH ₂ ) _k

Cl

 ? -

a - μ

Iiich.

R-Si-CH ₂ Cl

(CH ₀ )

2'k

Cl

IV

^R i -

R ₁ - CH = CH _? VII

CH.

R-Si-CH ₂ Cl

(CH ₂ ) _n

VI

Claims (6)

28450 claims 1. Fungicidal agent, characterized in that it comprises at least one Azolylmethylsilan the general formula I of the Fciineiblattes in the X is a nitrogen atom or a -CH group,
Y is an oxygen or sulfur atom, R is a straight-chain or branched alkyl radical having 1 to 6 C atoms, an unsubstituted or mono- or polysubstituted by halogen phenyl, a thienyl or Biphenylylreet or a CoHs-SC ^ group, R \ is an unsubstituted or one or more times Alkyl groups having 1 to 3 carbon atoms, alkoxy groups having 1 to 3 carbon atoms or by halogen-substituted phenyl, m is one of the numbers zero or 1 and η one of the numbers 1, 2 or 3, at least one plant physiologically acceptable acid addition salt or at least a plant-physiologically acceptable metal complex thereof in addition to conventional excipients and carriers. 2. Fungicidal agent according to claim 1, characterized in that they are at least sif. Azolylmethylsilan of the general formula I, in which X is a nitrogen atom, Y is a sulfur atom and R and Ri independently of one another unsubstituted or mono- or polysubstituted by halogen phenyl and m and η are each the number 1, a plant physiologically acceptable acid addition salt or a pflanzenphyaiologisch compatible Metal complex thereof in addition to conventional excipients and carriers included. 3. Fungicidal agent according to claim 1 containing methyl (2,4-dichlorophenyl) (phenylthiomethyl) (l, 2,4-triazol-l-ylmethyl) silane, a plant physiologically acceptable acid addition salt or a plant-physiologically compatible) metal complex davcn addition to conventional auxiliary and excipients 4. A method for controlling phytopathogenic fungi, characterized in that fungicidal agents containing azolylmethylsilanes of the general formula I according to claim 1 or their plant physiologically acceptable acid addition salts or their plant-physiologically acceptable metal complexes in addition to conventional excipients and carriers act on the fungi or their habitat leaves. 5. Use of Azolylmethylsilanen of the general formula I according to claim 1, characterized in that they are used for controlling phytopathogenic fungi. 6. A process for the preparation of fungicidal compositions, characterized in that at least one Azolylmethylsilan the general formula I according to claim 1 or their plant physiologically acceptable Sävireadditionssalze or their plant-physiologically acceptable metal complexes mixed with extenders and / or surface-active agents. Here ία 4 pin