DE3801233A1 - Microbicide - Google Patents

Abstract

Novel 1-phenoxyphenyl-2-triazolylethanol ethers of the formula I <IMAGE> in which R1 is halogen, R2 is halogen or methyl and R3 is C1-C4-alkyl, C1-C4-haloalkyl, C2-C6-alkoxyalkyl, C3-C6-alkenyl, C3-C6-alkynyl or cyclopropyl and their phytophysiologically acceptable acid addition salts have outstanding microbicidal, in particular phytofungicidal, properties. They can be used for the control and/or preventive protection of crop plants against infections by microorganisms. The preparation of these active substances and compositions containing them are described.

Description

The present invention relates to new 1-phenoxyphenyl-2-triazolyl ethanol ether as well as a microbicidal agent that acts as an active ingredient at least one compound of formula I below or one Acid addition compound thereof contains, the preparation of this Compounds or the compositions containing them and methods for Control or prevention of plant infestation by phytopathogenic Microorganisms.

The 1-phenoxyphenyl-2-triazolyl ethanol ether correspond to that Formula I.

wherein

R 1 halogen, R₂Halogen or methyl and R₃C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₂-C₈-alkoxyalkyl, C₃-C₆-alkenyl, C₃-C₆ alkynyl or cyclopropyl

mean, and acid addition salts of these compounds with plant physiology compatible organic and inorganic acids.

All organic come as salt formers with compounds of formula I. and inorganic acids in question, insofar as they are plant physiological form compatible salts.  

Examples of salt-forming acids are inorganic acids: hydrohalic acid such as hydrofluoric acid, hydrochloric acid, Hydrobromic acid or hydroiodic acid and sulfuric acid, Phosphoric acid, phosphorous acid, nitric acid and organic Acids such as acetic acid, trifluoroacetic acid, trichloroacetic acid, Propionic acid, tartaric acid, glycolic acid, lactic acid, succinic acid, Citric acid, benzoic acid, cinnamic acid, oxalic acid, formic acid, Benzenesulfonic acid, p-toluenesulfonic acid, methanesulfonic acid, salicylic acid, p-aminosalicylic acid, 2-phenoxybenzoic acid or 2-acetoxybenzoic acid. These acids are obtained by methods known per se the relevant free compounds of formula I added.

The compounds of formula I are stable at room temperature. they can be found in the agricultural sector or related fields in particular preventive and curative to combat harmful plants Use microorganisms. The active ingredients of formula I stand out in wide application concentrations due to a very good fungicide Effect and problem-free application.

The compounds in which show good microbicidal activity

R₁fluor, chlorine or bromine, R₂Fluor, chlorine, bromine or methyl and R₃C₁-C₄-alkyl, C₃-C₆-alkenyl, C₃-C₆-alkynyl or cyclopropyl

mean, in particular the following compounds:

2- [4- (4-chlorophenoxy) -2-chlorophenyl] -1- (1H-1,2,4-triazol-1-yl) -2-methoxyethane,
2- [4- (4-chlorophenoxy) -2-chlorophenyl] -1- (1H-1,2,4-triazol-1-yl) -2- allyloxyethane,
2- [4- (4-chlorophenoxy) -2-bromophenyl] -1- (1H-1,2,4-triazol-1-yl) -2-methoxyethane,
2- [4- (4-bromophenoxy) -2-chlorophenyl] -1- (1H-1,2,4-triazol-1-yl) -2-methoxyethane,
2- [4- (4-chlorophenoxy) -2-bromophenyl] -1- (1H-1,2,4-triazol-1-yl) -2- allyloxyethane,
2- [4- (4-bromophenoxy) -2-chlorophenyl] -1- (1H-1,2,4-triazol-1-yl) -2- allyloxyethane,
2- [4- (4-bromophenoxy) -2-bromophenyl] -1- (1H-1,2,4-triazol-1-yl) -2-methoxyethane,

as well as their salts with plant physiology compatible organic and inorganic acids.

The preparation of the 1-phenoxyphenyl-2-triazolyl ethanol ether Formula I is done by condensation of a 4-phenoxy-acetophenone of formula II with 1H-1,2,4-triazole of formula III or one Metal salt thereof according to the equation

In these formulas, R₁ and R₂ have the formula I given Meaning while Me is hydrogen or a metal cation and X is a nucleofugic leaving group such as B. halogen, especially chlorine, bromine or iodine, but also a benzenesulfonyloxy, p-tosyloxy, Trifluoroacetyloxy or preferably a lower alkyl sulfonyloxy like Mesyloxy group means. The resulting 2- (diphenyl ether) -1- (1H-1,2,4-triazole) -ethan-2-one of the formula IV

wherein R₁ and R₂ have the meaning given under formula I, are then using hydrogen or a hydrogen donor reduced and the carbinol of formula V obtained  

wherein R₁ and R₂ have the meaning given under formula I with a compound of formula VI

R₃-Y (VI)

wherein R₃ has the meaning given above and Y is a reactive Leaving group represents, etherified.

For this implementation, an acetophenone halide of formula II and 1H-1,2,4-triazole is used, the reaction is advantageously in the presence of a base and a catalytic amount of potassium iodide made in a ketone as a solvent.

The solvent should be anhydrous and can be made from acetone, Methyl ethyl ketone, cyclohexanone exist. In addition to ketones come as Solvents also include ethers such as diethyl ether, dioxane or tetrahydrofuran in question.

A tertiary amine such as triethylamine, methylpyridine is used as the base or an inorganic base, preferably an alkali metal carbonate or bicarbonate used.

The reduction is carried out in an inert organic solvent Presence of hydrogen or, preferably, a hydrogen releasing agents such as sodium borohydride or lithium aluminum hydride used.

In the reductions or hydrogenations of the ketone compounds Formula IV to carbinols of the formula V result in R, S mixtures, the composition of which is used for the hydrogenation Catalyst or depending on the reducing agent.  

The solvents mentioned here are the ethers mentioned above or lower alkanols such as methanol, ethanol, propanol, isopropanol used.

The carbinol of formula V obtained with a compound of Formula VI R₃-Y etherified. Halides come as leaving groups Y, especially chlorides, bromides and iodides, as well as alkyl sulfonic acid residues, Toluenesulfonic acid residues, etc. into consideration.

The above-mentioned ethers and also hydrocarbons come as solvents such as hexane, benzene, toluene or chlorinated hydrocarbons into consideration. Furthermore, as reaction inert diluents e.g. B. N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, Acetonitrile or Hexamethylphosphorsäuretriamid used will.

The reaction temperatures in these reactions are between 0 ° C and the boiling point of the reaction mixture.

The starting materials of formula II are known or can in themselves known way by condensation of a 4-haloacetophenone with a phenol or a 4-hydroxyacetophenone with halobenzene and subsequent halogenation can be obtained, according to the equation

The ethers of the formula I have a chiral center and can be in an R and S shape occur. Generally arises in the Preparation of these substances is a mixture of both enantiomers. This can be done in the usual way, e.g. B. by fractional Crystallization of salts of optically active, strong acids into which split pure optical antipodes. Both enantiomers can have different biological activities.

The present invention relates to all pure enantiomers as well their mixtures with each other.

It has surprisingly been found that the inventive Compounds of formula I a very practical for needs favorable spectrum of microbicides against phytopathogenic fungi and Have bacteria. You have very beneficial curative, systemic and especially preventive properties and leave work to protect numerous crops. With the Active ingredients of formula I can on plants or on parts of plants (Fruits, flowers, foliage, stems, bulbs, roots) of different Crops contain the microorganisms that occur or destroyed, with parts of the plant growing later remain spared from such microorganisms.

The active ingredients of formula I are against the following classes belonging to phytopathogenic fungi: Fungi imperfecti (e.g. Botrytis, Helminthosporium, Fusarium septoria, Cercospora and Alternaria); Basidiomycetes (e.g. the genera Hemileia, Rhizoctonia, Puccinia); they also act against the class of Ascomycetes (e.g. Venturia, Podosphaera, Erysiphe, Monilinia, Uncinula). In addition, the compounds of the formula I have a systemic action. they can also be used as dressing agents for the treatment of seeds (fruits, Tubers, grains) and plant cuttings to protect against fungal infections as well as against phytopathogenic fungi occurring in the soil be used.  

The active compounds according to the invention are particularly good Plant tolerance.

The invention also relates to the use of the compounds of Formula I for combating phytopathogenic microorganisms, in particular plant-damaging fungi or the preventive prevention of a Infested with plants.

In addition, the present invention also includes manufacturing agrochemical agent, which is characterized by the intimately mixing the active substance with one or more therein described substances or groups of substances. Is included also a method of treating plants that are characterized by Application of the compounds of formula I or the new agents distinguished.

As target cultures for the areas of indication disclosed here apply in the context of this invention z. B. the following types of plants: Cereals: (wheat, barley, rye, oats, rice, sorghum and relatives); Beets: (sugar and fodder beets); Core, stone and Soft fruit: (apples, pears, plums, peaches, almonds, cherries, Strawberries, raspberries and blackberries); Legumes: (beans, lentils, peas, Soy); Oil crops: (rapeseed, mustard, poppy seeds, olives, sunflowers, coconut, Castor, cocoa, peanuts); Cucumber Family: (Pumpkin, Cucumber, Melon); Fiber plants: (cotton, flax, hemp, jute); Citrus fruits: (Oranges, lemons, grapefruit, tangerines); Vegetables: (spinach, Lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes, Paprika); Laurel family: (avocado, cinnamonum, camphor) or Plants such as corn, tobacco, nuts, coffee, sugar cane, tea, grapevines, Hops, banana and natural rubber plants and ornamental plants (Flowers, shrubs, deciduous trees and conifers like conifers). This list is not a limitation.

Active ingredients of the formula I are usually in the form of compositions used and can be used simultaneously or in succession other active ingredients on the area or plant to be treated  are given. These other active ingredients can be fertilizers, Trace element mediators or others influencing plant growth Be preparations. However, selective herbicides, Insecticides, fungicides, bactericides, nematicides, molluscicides or Mixtures of several of these preparations, along with if necessary other carriers customary in formulation technology, Surfactants or other application-promoting additives.

Suitable carriers and additives can be solid or liquid and correspond to the substances useful in formulation technology, such as B. natural or regenerated mineral substances, Solvent, dispersant, wetting, adhesive, thickening, binding or Fertilizers.

A preferred method of applying an active ingredient Formula I or an agrochemical agent, the at least one this contains active ingredients, is the application to the foliage (Leaf application). Number of applications and application rate depend on the infestation pressure for the corresponding Pathogen (type of mushroom). The active ingredients of formula I can also reach the plant through the roots through the roots (systemic effect) by comparing the location of the plant with a liquid preparation or soaks the substances in solid form brings the floor, e.g. B. in the form of granules (floor application). However, the compounds of the formula I can also be applied to seeds can be applied (coating) by placing the grains in either impregnates the liquid preparation of the active ingredient or it with a solid preparation coated. They are also special If other types of application are possible, e.g. B. the targeted Treatment of plant stems or buds.

The compounds of formula I are unchanged or preferably together with those in formulation technology usual tools used and are therefore z. B. emulsion concentrates, spreadable pastes, directly sprayable or dilutable solutions, diluted emulsions, wettable powders,  soluble powders, dusts, granules, by encapsulation in z. B. polymeric materials processed in a known manner. The application procedures such as spraying, atomizing, dusting, scattering, Brushing or pouring are the same as the type of agent desired goals and given circumstances chosen. Favorable application rates are generally from 50 g to 5 kg of active ingredient (AS) per ha, preferably 100 g to 2 kg AS / ha, especially at 100 g to 600 g ai / ha.

The formulations, i.e. H. the the active ingredient of formula I and optionally containing a solid or liquid additive Agents, preparations or compositions are known in the art Made way, e.g. B. by intimate mixing and / or grinding the active ingredients with extenders, such as. B. with solvents, solid carriers, and optionally surface-active compounds (Surfactants).

Possible solvents are: aromatic hydrocarbons, prefers the fractions C₈ to C₁₂, such as. B. xylene mixtures or substituted naphthalenes, phthalic esters such as dibutyl or Dioctyl phthalate, aliphatic hydrocarbons such as cyclohexane or Paraffins, alcohols and glycols and their ethers and esters, such as Ethanol, ethylene glycol, ethylene glycol monomethyl or ethyl ether, Ketones such as cyclohexanone, strongly polar solvents such as N-methyl-2- pyrrolidone, dimethyl sulfoxide or dimethylformamide, and optionally epoxidized vegetable oils such as epoxidized coconut oil or Soybean oil; or water.

As solid carriers, e.g. B. for dusts and dispersible Powders, like natural rock flours, are usually used Calcite, talc, kaolin, montmorillonite or attapulgite. For improvement the physical properties can also be highly disperse Silicic acid or highly disperse absorbent polymers added will. Porous types come as granular, adsorptive granulate carriers such as B. pumice, broken brick, sepiolite or bentonite, as not sorptive carrier materials e.g. B. calcite or sand in question. About that  In addition, a variety of pre-granulated materials can be inorganic or organic nature such as dolomite or crushed Plant residues can be used. Particularly advantageous application-promoting additives that lead to a strong reduction of the application rate are also natural (animal or vegetable) or synthetic phospholipids from the series of Kephalins and lecithins, which can be obtained from soybeans, for example can win. Usable commercial mixtures are e.g. B. Phosphatidylchlorine Mixtures. Synthetic phospholipids are e.g. B. Dioctanoylphosphatidylcholine and dipalmitoylphosphatidylcholine.

Depending on the nature of the surface active compounds formulating active ingredient of formula I non-ionic, cation and / or anionic surfactants with good emulsifying, dispersing and Network properties into consideration. Surfactant mixtures are also among surfactants to understand.

Suitable anionic surfactants can be both water-soluble Soaps, as well as water-soluble synthetic surface-active Connections.

The soaps are the alkali, alkaline earth or, if appropriate substituted ammonium salts of higher fatty acids (C₁₀-C₂₂), such as e.g. B. the Na or K salts of oleic or stearic acid, or of natural fatty acid mixtures, e.g. B. from coconut or tallow oil can be won. Furthermore, the fatty acid methyl laurine salts to mention.

However, so-called synthetic surfactants are used more frequently, in particular Fatty alcohol sulfonates, fatty alcohol sulfates, sulfonated Benzimidazole derivatives or alkyl sulfonates.

The fatty alcohol sulfonates or sulfates are usually as Alkali, alkaline earth or optionally substituted ammonium salts before and have an alkyl radical with 8 to 22 carbon atoms, wherein Alkyl also includes the alkyl portion of acyl residues, e.g. B. the Na-  or Ca salt of lignin sulfonic acid, the dodecylsulfuric acid ester or a fatty alcohol sulfate mixture made from natural fatty acids. This subheading also includes the salts of sulfuric acid esters and sulfonic acids of fatty alcohol-ethylene oxide adducts. The sulfonated Benzimidazole derivatives preferably contain 2-sulfonic acid groups and a fatty acid residue with 8-22 carbon atoms. Alkylarylsulfonates are z. B. the Na, Ca or triethanolamine salts of dodecylbenzenesulfonic acid, dibutylnaphthalenesulfonic acid, or one Naphthalenesulfonic acid-formaldehyde condensation product.

Corresponding phosphates such as. B. salts of Phosphoric acid ester of a p-nonylphenol (4-14) ethylene oxide adduct in question.

The primary nonionic surfactants are polyglycol ether derivatives of aliphatic or cycloaliphatic alcohols, saturated or unsaturated fatty acids and alkylphenols in Question the 3 to 30 glycol ether groups and 8 to 20 carbon atoms in the (aliphatic) hydrocarbon radical and 6 to 18 carbon atoms may contain in the alkyl radical of the alkylphenols.

Other suitable nonionic surfactants are the water-soluble, 20 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups containing polyethylene oxide adducts with polypropylene glycol, Ethylene diaminopolypropylene glycol and alkyl polypropylene glycol with 1 to 10 carbon atoms in the alkyl chain. The mentioned compounds usually contain per propylene glycol Unit 1 to 5 ethylene glycol units.

Examples of nonionic surfactants are nonylphenol polyethoxyethanols, Castor oil polyglycol ether, polypropylene-polyethylene oxide adducts, Tributylphenoxypolyethyleneethanol, polyethylene glycol and Octylphenoxypolyethoxyethanol mentioned.

Also come fatty acid esters of polyoxyethylene sorbitan like that Polyoxyethylene sorbitan trioleate into consideration.  

The cationic surfactants are primarily quaternary Ammonium salts which have at least one alkyl radical as N-substituents contain with 8 to 22 carbon atoms and as further substituents low, optionally halogenated alkyl, benzyl or low Have hydroxyalkyl radicals. The salts are preferably as Halides, methyl sulfates or ethyl sulfates, e.g. B. the stearyltrimethylammonium chloride or the benzyldi (2-chloroethyl) ethylammonium bromide.

The agrochemical preparations usually contain 0.1 to 99% by weight, in particular 0.1 to 95% by weight, of active compound of the formula I, 99.9 to 1% by weight, in particular 99.8 to 5% by weight, of a solid or liquid additive and 0 to 25 wt .-%, in particular 0.1 to 25% by weight of a surfactant.

While concentrated goods are preferred as a commodity, the end user usually uses diluted agents.

The agents can also contain other additives such as stabilizers, defoamers, Viscosity regulators, binders, adhesives and fertilizers or contain other active ingredients to achieve special effects.

Such agrochemicals are part of the present Invention.

The following example describes the production of an active ingredient of formula I. Temperatures in this example are in Celsius degrees indicated. Press in millibars (mbar).

1. Manufacturing examples 1.1. Preparation of 2- [4- (4-chlorophenoxy) -2-chlorophenyl] -1- (1H-1,2,4-triazol-1-yl) -2-methoxyethane

To a suspension of 0.9 g 55% sodium hydride dispersion in 30 ml of dimethylformamide are added dropwise while stirring and passing Nitrogen within 20 minutes a solution of 6.8 g of 2- [4- (4-chlorophenoxy) - 2-chlorophenyl] -1- (1H-1,2,4-triazol-1-yl) ethan-2-ol in 20 ml of dimethylformamide, the reaction mixture being at 23 ° 35 ° warmed. The mixture is then stirred at 38 ° for 3 hours. Then 2.5 g of dimethyl sulfate are added dropwise within one hour added and stirred for a further 16 hours at 37 ° -39 °.

After cooling to room temperature, the reaction mixture is opened Poured 200 ml of water and extracted 3 times with 100 ml of ethyl acetate each. The organic phases are combined, three times each Washed 200 ml of water, dried over sodium sulfate, filtered and the solvent evaporated under vacuum.

The liquid residue is over for cleaning with ethyl acetate chromatographed a silica gel column. The title link is called yellow oil obtained, n: 1.5869.

1.2. Preparation of 2- [4- (4-bromophenoxy) -2-chlorophenyl] -1- (1H-1,2,4-triazol-1-yl) -2-meth-oxyethane

To a suspension of 0.35 g 55% sodium hydride dispersion in 20 ml of dimethylformamide are added dropwise while stirring and passing Nitrogen within 20 minutes a solution of 3.1 g of 2- [4- (4-bromophenoxy) - 2-chlorophenyl] -1- (1H-1,2,4-triazol-1-yl) ethan-2-ol in 10 ml of dimethylformamide, the reaction mixture being at 23 °  35 ° warmed. The mixture is then stirred at 38 ° for 3 hours. Then 1.0 g of dimethyl sulfate are added dropwise within one hour added and stirred for a further 16 hours at 37 ° -39 °. After cooling to room temperature, the reaction mixture is opened Poured 200 ml of water and extracted 3 times with 100 ml of ethyl acetate each The organic phases are combined, three times each Washed 200 ml of water, dried over sodium sulfate, filtered and the solvent evaporated under vacuum. The liquid residue is over for cleaning with ethyl acetate chromatographed a silica gel column. The title link is called yellow oil obtained, n: 1.5978.

The required starting products are manufactured as follows:

1.3. Synthesis of 2- [4- (4-bromophenoxy) -2-chlorophenyl] -1- (1H-1,2,4-triazol-1-yl) ethan-2 - one

To a solution of 5.8 g (14.7 mmol) of 2- [4- (4-bromophenoxy) -2-chlorophenyl] - (1H-1,2,4-triazol-1-yl) ethan-2-one in 40 ml of methanol one with stirring and passing nitrogen through at room temperature in portions 0.56 g (14.7 mmol) of sodium borohydride within 15 minutes. The reaction mixture warms from 22 ° to 38 °. After everything has been added, let in for 4 hours Continue stirring room temperature, then give 2.2 g of conc. Hydrochloric acid and a little later 22 ml of 10% sodium bicarbonate solution. The title product turns out to be crystalline. It is filtered off with water washed and dried. 5.5 g of 2- [4- (bromophenoxy) -2- chlorphenyl] -1- (1H-1,2,4-triazol-1-yl) ethan-2-ol as beige crystalline Powder. Melting point 115-118 ° C.

1.4. Synthesis of 2- [4- (4-bromophenoxy) -2-chlorophenyl] -1- (1H-1,2,4-triazol-1-yl) ethan-2-one

A mixture of 8.7 g (21.5 mmol) of 2- [4- (4-bromophenoxy) -2-chlorophenyl) - 1-bromethan-2-one, 1.63 g (23.7 mmol), 1,2,4-triazole, 3.26 g (23.7 mmol) potassium carbonate and a catalytic amount of 0.3 g of potassium iodide in 80 ml of absolute butan-2-one is added during Stirred for 24 hours at room temperature. Then another 0.15 g is added (2.1 mmol) 1,2,4-triazole and heated under for 6 hours Stir to 45 °. After cooling to room temperature, it will Filtered reaction mixture, the filtrate treated with activated carbon, filtered again and concentrated on a rotary evaporator. The residue is recrystallized from ethanol. A beige-white remains crystalline powder of 2- [4- (4-bromophenoxy) -2-chlorophenyl] - (1H- 1,2,4-triazol) ethan-2-one, which melts at 171-173 °.

In the same way, the compounds listed in Table 1 produced.

Table 1

2. Formulation examples for solid active ingredients of the formula I (% = weight percent)

The active ingredient is mixed well with the additives and in one suitable grinder well ground. You get wettable powder that is dilute with water to form suspensions of any desired concentration to let.

2.2 Emulsion concentrate

Active ingredient from table 110% octylphenol polyethylene glycol ether 3% (4-5 mol ethylene oxide)
Ca-dodecylbenzenesulfonate 3% castor oil polyglycol ether (35 mol ethylene oxide) 4% cyclohexanone 30% xylene mixture 50%

This concentrate can be diluted with water to make emulsions any desired concentration.

Ready-to-use dusts are obtained by adding the active ingredient the carrier is mixed and ground on a suitable mill.

2.4 Extruder granules

Active ingredient from table 110% Na lignin sulfonate 2% Carboxymethyl cellulose 1% Kaolin87%

The active ingredient is mixed with the additives, ground and moistened with water. This mixture is extruded and then dried in an air stream.

2.5 coating granules

Active ingredient from table 1 3% Polyethylene glycol (MG * 200) 3% Kaolin94% (* MG = molecular weight)

The finely ground active ingredient is mixed with the in a mixer Polyethylene glycol moistened kaolin evenly applied. On in this way, dust-free coating granules are obtained.

2.6 Suspension concentrate

Active ingredient from table 140% ethylene glycol 10% nonylphenol polyethylene glycol ether 6% (15 mol ethylene oxide)
N-lignin sulfonate 10% carboxymethyl cellulose 1% 37% aqueous formaldehyde solution 0.2% silicone oil in the form of a 75% aqueous emulsion 0.8% water 32%

The finely ground active ingredient becomes intimate with the additives mixed. A suspension concentrate is thus obtained, from which by diluting with water suspensions of any desired concentration can be produced.

3. Biological examples Example 3.1: Action against Puccinia graminis on wheat a) Residual protective effect

Wheat plants are made 6 days after sowing with a spray powder of the active ingredient spray liquor (0.006% active ingredient) sprayed. After 24 hours, the treated plants infected with a uredospore suspension of the fungus. After a Incubation for 48 hours at 95-100% relative humidity and about 20 ° C the infected plants in a greenhouse set up at approx. 22 ° C. Assessment of rust pustule development occurs 12 days after infection.

b) Systemic effect

Wheat plants are made from wettable powder 5 days after sowing poured spray liquor (0.002% active ingredient, based on the soil volume). After 48 hours, the treated plants with an uredospore suspension of the fungus infected. After 48 hours incubation at 95-100% relative humidity and about 20 ° C the infected Plants placed in a greenhouse at approx. 22 ° C. The assessment rust pustules develop 12 days after infection.  

Compounds from Table 1 show good against Puccinia fungi Effectiveness. Show untreated but infected control plants a Puccinia infestation of 100%. Compounds No. 2, 5, 10, 11, 13 and 16 reduce the Puccinia infestation to 0 to 10%.

Example 3.2: Action against Cercospora arachidicola on peanut plants Residual protective effect

10-15 cm high peanut plants are made with a spray powder Active substance produced spray liquor (0.02% active substance) sprayed and 48 hours later with a conidia suspension from Fungus infected. The infected plants are kept for 72 hours incubated at approx. 21 ° C and high humidity and then until the typical leaf spots appear in a greenhouse set up. The fungicidal activity is assessed for 12 days after infection, based on the number and size of those occurring Stains.

Compared to untreated but infected control plants (Number and size of the spots = 100%) showed peanut plants, that were treated with active ingredients from Table 1, a strong reduced Cercospora infestation. Among other things, this prevents the connections Nos. 2, 5, 10, 11, 13 and 16 the appearance of spots almost completely (infestation = 0-10%).

Example 3.3: Action against Erysiphe graminis on barley a) Residual protective effect

Barley plants with a height of about 8 cm are made from a wettable powder Spray liquor (0.02% active substance) sprayed. After 3-4 hours, the treated plants with Conidia of the mushroom pollinated. The infected barley plants will set up in a greenhouse at approx. 22 ° C and the fungal attack assessed after 10 days.  

b) Systemic effect

8 cm high barley plants are made from a spray powder of Poured spray liquor produced (0.006% active ingredient, based on the volume of the earth). Care was taken to ensure that do not spray the spray mixture with the aerial parts of the plant Came into contact. After 48 hours, the treated plants with Conidia of the mushroom pollinated. The infected barley plants will set up in a greenhouse at approx. 22 ° C and the fungal attack assessed after 10 days.

Compounds from the table show good activity against erysiphe- Mushrooms. Show untreated but infected control plants on the other hand, an Erysiphe infestation of 100%.

Example 3.4: Residual protective action against Venturia inaequalis on apple shoots

Apple cuttings with 10-20 cm long fresh shoots are with a Spray liquor made from wettable powder of the active ingredient (0.06% Active substance) sprayed. After 24 hours, the treated ones Plants infected with a conidia suspension of the fungus. The Plants are then grown at 90-100% relative humidity for 5 days incubated and in one for another 10 days Greenhouse set up at 20-24 ° C. The scab infestation lasts 15 days assessed after infection. Show connections from the table good effectiveness against Venturia. Untreated but infected Shoots, on the other hand, have a 100% Venturia infestation.

Example 3.5: Action against Botrytis cinerea on beans Residual protective effect

Bean plants with a height of about 10 cm are made from a wettable powder powder Spray liquor (0.02% active substance) sprayed with the active ingredient. After 48 hours, the treated plants with a Conidia suspension of the fungus infected. After incubation of the infected plants for 3 days at 95-100% relative humidity and 21 ° C the fungal attack is assessed.  

Compounds from the table inhibit the fungal infection very strongly. In contrast, untreated but infected control plants have one Botrytis infestation of 100%.

Example 3.6: Action against Tilletia caries on wheat

Winter barley artificially infected with burn spores from Tilletia caries of the Probus variety (3 g dry spore material per 1 kg Seed) is placed on a mixing roller with the fungicide to be tested pickled, with a concentration of 60 ppm AS (based on the Weight of the seed) is used.

The infected and treated wheat is grown outdoors in October using a seeder on plots of 2 m in length and 3 rows of seeds sown with triple repetition.

To determine the drug activity at the time of Ripeness the percentage of Tilletia-infected ears counted.

Compounds from the table show good activity against Tilletia. Show untreated but infected control plants however, a Tilletia infestation of 100%.

Example 3.7: Action against Helminthosporium gramineum on barley

Naturally infected with Helminthosporium gramineum Winter barley of the "C1" variety is mixed on a mixing roll with the testing fungicide stained, a concentration of 60 ppm AS (based on the weight of the seed) is used.

The infected and treated barley is grown outdoors in October using a seeder on plots of 2 m in length and 3 rows of seeds sown with triple repetition.

Until the infestation is evaluated, the trial planting is normal Cultivated field conditions.  

To determine the drug activity at the time of The percentage of Helminthosporium infested Blades counted.

The compounds in Table 1 show good activity against Helminthosporium. They inhibit fungal infection up to 0-5% during untreated infected control plants a helminthosporium Show 100% infestation.

Claims (10)

1. 1-phenoxyphenyl-2-triazolyl ethanol ether of the formula I. whereinR₁Halogen, R₂Halogen or methyl and R₃C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₂-C₈-alkoxyalkyl, C₃-C₆-alkenyl, C₃-C₆-alkynyl or cyclopropyl mean, and the acid addition salts with plant-physiologically harmless organic and inorganic acids. 2. 1-phenoxyphenyl-2-triazolyl ethanol ether of the formula I according to claim 1, where R₁fluor, chlorine or bromine, R₂Fluor, chlorine, bromine or methyl and R₃C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₂-C₈-alkoxyalkyl, C₃-C₆-alkenyl, C₃-C₆-alkynyl or cyclopropyl mean. 3. 1-phenoxyphenyl-2-triazolyl ethanol ether of the formula I according to Claim 1, wherein R₁fluor, chlorine or bromine, R₂Fluor, chlorine, bromine or methyl and R₃C₁-C₄-alkyl, C₃-C₆-alkenyl, C₃-C₆-alkynyl or cyclopropyl mean. 4. 2- [4- (4-chlorophenoxy) -2-chlorophenyl] -1- (1H-1,2,4-triazol-1-yl) -2-methoxyethane,
2- [4- (4-chlorophenoxy) -2-chlorophenyl] -1- (1H-1,2,4-triazol-1-yl) -2- allyloxyethane,
2- [4- (4-chlorophenoxy) -2-bromophenyl] -1- (1H-1,2,4-triazol-1-yl) -2-methoxyethane,
2- [4- (4-bromophenoxy) -2-chlorophenyl] -1- (1H-1,2,4-triazol-1-yl) -2-methoxyethane,
2- [4- (4-chlorophenoxy) -2-bromophenyl] -1- (1H-1,2,4-triazol-1-yl) -2- allyloxyethane,
2- [4- (4-bromophenoxy) -2-chlorophenyl] -1- (1H-1,2,4-triazol-1-yl) -2- allyloxyethane,
2- [4- (4-Bromophenoxy) -2-bromophenyl] -1- (1H-1,2,4-triazol-1-yl) -2-methoxyethane, according to claim 4. 5. Process for the preparation of 1-phenoxyphenyl-2-triazolylethanol ether of the formula I. in which R₁ is fluorine, chlorine or bromine, R₂ is fluorine, chlorine, bromine or methyl and R₃C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₂-C₈-alkoxyalkyl, C₃-C₆-alkenyl, C₃-C₆-alkynyl or cyclopropyl, and their acid addition salts, characterized in that 1H-1,2,4-triazole or a metal salt thereof is condensed with a 4-phenoxy-acetophenone whose formula II wherein R₁ and R₂ have the meaning given above and X is a nucleofugic leaving group, and the resulting 2- (diphenyl ether) - 1- (1H-1,2,4-triazole) ethan-2-one of the formula IV wherein R₁ and R₂ have the meaning given above, reduced with hydrogen or a hydrogen donating agent and the carbinol of the formula V obtained wherein R₁ and R₂ have the meaning given above, etherified with a compound of the formula VIR₃-Y (VI) wherein R₃ has the meaning given above and Y represents a reactive leaving group. 6. Agent for combating or preventing infestation by microorganisms, characterized in that it contains an effective amount of a 1-phenoxyphenyl-2-triazolylethanol ether of the formula I in addition to inert formulation auxiliaries whereinR₁Halogen, R₂Halogen or methyl and R₃C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₂-C₈-alkoxyalkyl, C₃-C₆-alkenyl, C₃-C₆-alkynyl or cyclopropyl means, or contains a physiologically acceptable acid addition salt of such a compound. 7. A method for producing an agent according to claim 6, characterized in that an active ingredient of formula I or an acid addition salt with suitable solid or liquid Additives and surfactants intimately mixed.   8. Procedures to combat or prevent infestation of Cultivated plants by phytopathogenic microorganisms and / or for Regulation of plant growth, characterized in that a compound defined according to claims 1 to 4 Formula I applied to the plant or its location. 9. Use of compounds of formula I according to claim 1 or agents containing them for combating and / or for preventive purposes Prevention of microorganism infestation. 10. Use according to claim 9, characterized in that it the microorganisms are phytopathogenic fungi.