DK161199B - 1-AZOLYL-2-ARYL-3-FLUORALKAN-2-OILS OR OTHER THEREOF, ACID ADDITIONAL SALTS, QUATERNARY AZOLIUM SALTS AND METAL COMPLEXES THEREOF, PROCEDURES FOR THE PREPARATION OF AN EXAMPLE - Google Patents

Description

in

DK 161199 B

The present invention relates to novel substituted 1-azolyl-2-aryl-3-fluoro-alkan-2-ols and ethers thereof of the following Formula I, acid addition salts, quaternary azolium salts and metal complexes thereof. The invention further relates to a process for the preparation of these compounds as well as to microbicidal agents containing as active substance at least one of these compounds. The invention also relates to a method for controlling or protecting against attacks on cultured plants by microorganisms, preferably plant-damaging fungi.

The compounds of the invention are peculiar in that they have the general formula OR, R.

I I

Az-CH2-C-c-F (I)

Ar is R 3 where Az is 1H-1,2,4-triazole or 1H-imidazole, Ar is phenyl, phenyl substituted with halogen or alkyl, phenoxyphenyl or phenoxyphenyl substituted with halogen or alkyl, hydrogen, C1-C6 alkyl or Cø-Cs alkenyl, R₂ is hydrogen or fluorine, and R R is hydrogen, C--Cg alkyl or 4-chlorophenoxy, or are acid addition salts, quaternary azolium salts or metal complexes thereof.

By alkyl itself or as a constituent of another substituent, depending on the number of carbon atoms indicated, for example, the following groups are meant: methyl, ethyl, propyl, butyl, pentyl, hexyl, etc. and their isomers such as e.g. isopropyl, isobutyl, tert-butyl and isopentyl.

By halogen is meant herein and hereinafter fluorine,

DK 161199B

2 chlorine, bromine or iodine, preferably fluorine, chlorine or bromine. Alkenyl means e.g. propenyl (1), allyl, butenyl (1), butenyl (2) or butenyl (3).

Thus, the present invention relates to the free compounds of formula I, acid addition salts, quaternary azolium salts and metal complexes thereof. The free compounds, especially the 1H-1,2,4-triazole derivatives of formula I, are preferred.

Examples of salt forming acids include inorganic acids such as hydrogen halide acids, e.g. hydrogen fluoride acid, hydrochloric acid, hydrobromic acid or hydrogen iodide acid, as well as sulfuric acid, phosphoric acid, phosphoric acid and nitric acid, and organic acids such as acetic acid, trifluoroacetic acid, trichloroacetic acid, propionic acid, formic acid, benzenesulfonic acid, p-toluenesulfonic acid or p-toluenesulfonic acid.

Metal complexes of formula I consist of the basic organic molecule and an inorganic or organic metal salt, e.g. the halides, nitrates, sulfates, phosphates, acetates, trifluoroacetates, trichloroacetates, propionates, tartrates, sulfonates, salicylates, benzoates, etc., of the elements of the third and fourth major groups of the periodic system, such as aluminum, tin or lead , as well as from first to eighth side groups, such as chromium, manganese, iron, cobalt, nickel, zirconium, copper, zinc, silver, mercury, etc. The side group elements are preferred in the fourth period. The metals can be present in the various possible valences.

The metal complexes of formula I may be single- or multi-core, i. they may contain one or more organic moieties as ligands. Complexes with the metals copper, zinc, manganese, tin and zirconium are preferred.

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Compounds of formula I are at room temperature stable oils, resins or especially solids which are characterized by extremely valuable microbicidal properties. They can be used in the agricultural sector or related fields for the preventive or curative control of plant harmful microorganisms. For this purpose, the triazolylmethyl derivatives encompassed by Formula I are preferred. The present active substances of Formula I are distinguished by 10 low application concentrations, by having a very good plant fungicide effect and by being able to be used without problems. In addition, they also have a growth regulator, especially growth inhibitory effect, especially with tropical cover crops.

Because of their pronounced microbicidal and especially plant fungicidal activity, the following compound groups are preferred:

Compounds of formula I wherein Az means 1H-1,2,4-triazole or 1H-imidazole, Ar means unsubstituted or halogen or alkyl substituted phenyl or unsubstituted or halogen or alkyl substituted phenoxyphenyl means hydrogen, R2 means hydrogen or fluorine, and R 3 means hydrogen, C 1 -C 4 alkyl or 4-chlorophenoxy and acid addition salts, quaternary azolium salts and metal complexes thereof.

Within this group, particularly preferred are those compounds of formula I wherein Az is 1H-1,2,4-triazole, Ar is unsubstituted or in the 2- and / or 4-position with methyl or halogen, preferably fluorine or chlorine, substituted phenyl or phenoxyphenyl, R 2 is hydrogen, R 2 is hydrogen or fluorine, and R 3 is hydrogen, C 1 -C 4 alkyl or 4-chlorophenoxy.

4

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Examples of fungicidal particularly preferred single compounds include: 1- (1H-1,2,4-triazol-1-yl) -2- (2,4-dichlorophenyl) -3-fluorobutan-2-ol, 5 - (1H-1,2,4-triazol-1-yl) -2- (2-chloro-4-fluorophenyl) -3-fluorobutan-2-ol, 1- (1H-1,2,4-triazol-1-yl) 1-yl) -2- (2,4-dichlorophenyl) -3-fluoro-pentan-2-ol, 1- (1H-1,2,4-triazol-1-yl) -2- (2,4-dioxide) dichlorophenyl) -3-fluoro-4-methylpentan-2-ol, 1- (1H-1,2,4-triazol-1-yl) -2- (2-chloro-4-fluorophenyl) -3-fluoro pentan-2-ol, 1- (1H-1 * 2,4-triazol-1-yl) -2- (2,4-dichlorophenyl) -3- (4-chloro-phenoxy) -3-fluoropropan-2-one ol, 1- (1H-1,2,4-triazol-1-yl) -2- [p- (4-chlorophenoxy) phenyl] -3-fluoropropan-2-ol, 1- (1H-1,2) (4-Triazol-1-yl) -2- (4-chlorophenyl) -3-fluorohexan-2-ol, 1- (1R-1,2,4-triazol-1-yl) -2- (2,4) -dichlorophenyl) -3-fluoro-hexan-2-ol, 1- (1H-1,2,4-triazol-1-yl) -2- (2,4-dichlorophenyl-3,3) -difluoro-pentane -2-ol, 1- (1H-1,2,4-triazol-1-yl) -2- (2,4-dichlorophenyl) -3-fluoro-4-methylpentan-2-ol, 1- (1H -1,2,4-triazol-1-yl) -2- [p- (4-bromophenoxy) phenyl] -3,3-difluoropropan-2-ol, 1- (1H-1,2,4-triaz ol-1-yl) -2- [p- (4-fluorophenoxy) phenyl] -3,3-difluoropropan-2-ol, 1- (1H-1,2,4-triazol-1-yl) -2- [p- (4-chlorophenoxy) phenyl] -3,3-30 difluoropropan-2-ol and 1- (1H-1,2,4-triazol-1-yl) -2- [p- (4-chlorophenoxy) 2-methyl-phenyl] -2-hydroxy- / 3-fluoropropane.

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Compounds of formula I are prepared by first reacting an oxirane of formula

Ar-c - (II) I 1 R - C-R, / i j

F

with an azole of formula 5 M-Az (III) for a compound of formula

OH

Ar-c-CH -Az (la) I 2 R0-C-R_

1 i -i F

and, if necessary, converting the alcohol 1a in a conventional manner, e.g. by reaction with a compound of formula 10 \ -W (IV) to an ether of formula I wherein the substituents R 1, R 2, R 2, Ar and Az of formulas 1a, II, III and IV M means hydrogen or preferably a metal atom, especially an alkali metal atom such as Li, Na or K, and W means OH or a conventional leaving group.

Common cleavage groups are known from the literature.

The reaction II with III to Ia is optionally carried out in the presence of condensing or acid binding agents.

Such may be, for example, organic or inorganic bases, e.g. tertiary amines such as trialkylamines (trimethylamine, triethylamine, tripropylamine, etc.), pyridine and pyridine bases (4-dimethylaminopyridine, 4-pyrrolidylamino-pyridine, etc.), oxides, hydrides and hydroxides, carbonates and hydrogen carbonates of alkali metals and alkaline earth metals 6

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clay (CaO, BaO, NaOH, KOH, NaH, Ca (OH) 2, KHCC> 3, NaHCC> 3,

Ca (HCO3) 2 / K2CO3 (Na2CO3) and alkali metal acetates such as CH3COONa or CH3COOK. In addition, alkali metal alcohols such as C CH ^O ONa, n-CgH ^O ONa, etc. are also suitable. In some cases, it may be advantageous to first convert the free azole III (M = hydrogen! / For example in situ with an alcoholate / to the corresponding salt and then react with the oxirane of formula II). of 1,2 / 4-triazolyl derivatives, usually 1,3,4-triazolyl isomers, which can be separated from each other in the usual manner, for example, with different solvents are usually formed parallel to this.

The reaction (II with III to Ia) is preferably carried out in a relatively polar / non-reaction-inert organic solvent / e.g. Ν, Ν-dimethylformamide, Ν, Ν-dimethylacetamide, dimethylsulfoxide, acetonitrile, benzonitrile and others. Such solvents can be used in combination with other reaction-inert solvents, e.g. benzene, toluene, xylene, hexane, petroleum ether, chlorobenzene, nitrobenzene and others. The reaction temperatures are within a temperature range of 0-150 ° C, preferably 20-100 ° C.

Moreover, this reaction (II with III to Ia) can be carried out in the same way as already known reactions of other oxiranes with azoles (cf. German publication no.

29 12 288).

In said partial reactions, the intermediates can be isolated from the reaction medium and, if desired, before the further reaction is carried out, purified using one of the conventional methods, e.g. by washing, digestion, extraction, crystallization, chromatography, distillation, etc.

The further reaction from Ia to I occurs in cases where W in Formula IV means a conventional leaving group, in the absence or preferably in the presence of a reaction inert solvent.

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The following solvents are suitable, for example: N, N-dimethylformamide, Ν, Ν-dimethylacetamide, hexamethylphosphoric acid triamide, dimethylsulfoxide, 2-methyl-3-pentanone etc. Also mixtures of these solvents where they are mixed with each other or with other common inert organic solvents, e.g. with aromatic hydrocarbons such as benzene, toluene, xylenes etc. can be used. In many cases, working in the presence of a base such as an alkali metal hydride, hydroxide or carbonate, to promote the reaction rate. However, it may also be advantageous to first convert the alcohol of formula Ia (R 2 = OH) in a manner known per se, e.g. by reaction with a strong base, to a suitable metal salt.

Suitable strong bases are e.g. alkali metal and alkaline earth metal hydrides (NaH, KH, Ca 2, etc.) and alkali metal organic compounds such as e.g. butyllithium or alkali metal tert-butoxide. In addition, alkali metal hydroxides such as NaOH or KOH can also be used when operating in an aqueous two-phase system and in the presence of a phase transfer catalyst.

However, one can also first convert the alcohol of formula Ia to an alkali metal alcoholate in the usual manner before the further reaction, and then react it with a compound of formula IV (wherein W means a cleavage group). Thus, one advantageously works in the presence of a crown ether. At M = K, especially in the presence of 18-krone-6, at M = Na, especially in the presence of 15-krone-5.

Thereby, the reaction is conveniently carried out in a reaction inert medium. Suitable solvents are e.g.

30 ethers and ether-like compounds, e.g. dilavalkyl ethers (diethyl ether, diisopropyl ether, tert-butyl methyl ether, etc.), tetrahydrofuran, dioxane and aromatic hydrocarbons such as benzene, toluene and xylenes.

For example, for the organic water-immiscible phase, the following solvents may be used: Aliphatic and aromatic hydrocarbons such as pentane, hexane,

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) hexane, petroleum ether, ligroin, benzene, toluene, xylenes, etc., halogenated hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride, ethylene dichloride, 1,2-dichloroethane, tetrachlorethylene, etc., or aliphatic ethers such as diethyl ether, diisopropyl ether, t-butyl methyl ether, etc. Examples of suitable phase transfer catalysts are: Tetraalkylammonium halides, hydrogen sulfates or hydroxides such as tetrabutylammonium chloride, bromide, iodide, triethylbenzylammonium chloride, bromide phosphonium salts can also be used. The reaction temperatures are usually between 30 ° and 130 ° C or at the boiling point of the solvent or solvent mixture.

In cases where W in formula IV represents a hydroxy group, a condensation reaction is advantageously carried out.

Both reaction partners are heated under reflux in a suitable solvent.

Thus, in principle, solvents which are inert to the reaction partners and suitably form azeotropes with water can be used. For example, suitable for this purpose. aromatic hydrocarbons such as benzene, toluene and xylenes, or halogenated hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, tetrachlorethylene and chlorobenzene, but also ethereal compounds such as tert-butyl methyl ether, dioxane and others. In many cases, the compound of formula III itself can be used as a solvent. In this condensation reaction, one is suitably employed in the presence of a strong acid, e.g. paratoluene sulfonic acid, and at the boiling temperature of the azeotropic mixture.

To prepare the ethers of formula I, one can also first replace the free OH group of the compounds of formula Ia with one of the above-mentioned common cleavage groups W and then react it with a compound of formula IV (W = OH).

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The starting compounds of formula III are generally known or can be prepared using methods known per se.

The oxiranes of formula II are novel and constitute particularly developed intermediates for the preparation of the valuable active substances of formula I. Due to their structural nature, they can be readily converted to the compounds of formula Ia. In addition, the compounds of Formula II are partially fungicidal against harmful fungi of the Ascomycetes, Basidiomycetes or Fungi imperfecti families.

Epoxides of formula II can be prepared in a manner known per se from ketones of formula R 2 | 2

Ar-C-C-F (V)

II I

° R3 by reaction with dimethylsulfonium methylide or dimethyl-oxosulfonium methylide (Corey and Chaykovsky, JACS, 1962, 84, 3782).

The ketones of formula V can be prepared using literature 20 per se known in the art (cf. J. Leroy, J. Org. Chem. 6, 206 (1981) or Houben-Weyl, Vol. V / 3, page 211). ) from the corresponding known α-bromo ketones by usual replacement of bromine with fluorine or they can be prepared by acylating the basic aromatics with fluorinated carboxylic acid derivatives, e.g. according to 25 Friedel-Crafts.

In the preparation of all the starting, intermediate and end products mentioned herein, in principle, unless in the individual cases unless expressly stated otherwise, one or more reaction-inert solvents or diluents may be present. For example, aliphatic and aromatic hydrocarbons such as benzene, toluene,

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10 xylenes and petroleum ether, halogenated hydrocarbons such as chlorobenzene, methylene chloride, ethylene chloride, chloroform / carbon tetrachloride and tetrachlorethylene, ethers or ether-like compounds f such as dialkyl ethers (diethyl ether, diisopropyl ether, tert-butyl methyl ether, etc.), anisole, dihydro, dihydro , such as acetonitrile and propionitrile, β, β-dialkylated amides such as dimethylformamide, dimethyl sulfoxide, ketones such as acetone, diethyl ketone and methyl ethyl ketone, and mixtures of such solvents.

In many cases it may also be advantageous if the reaction or partial step of a reaction is carried out under a protective gas atmosphere and / or in absolute solvents.

Suitable protective gases are inert gases such as nitrogen, helium, argon or in some cases also carbon dioxide.

The compounds of formula Γ1 i2

Az - CH, - C - C - F (I) 2 I I

Ar is not adjacent to the substituents Ar and OR ^ always has an asymmetric C atom C * and can therefore exist in two enantiomeric forms. Usually, in the preparation of these compounds, a mixture of the two enantiomers is formed.

This mixture can be digested into the pure optical antipodes in the usual manner, e.g. by fractional crystallization of salts with optically active, strong acids. The enantiomers can have different biological effects, so e.g. in one form the fungicide and in the other the plant regulating effect prevail. At the same spectrum of effects, there may also be a gradual difference in activity. If the groups and R 1 are different, then another asymmetric center (*) occurs, causing the existence of diastereomeric mixtures (threo and erythro forms) which can be separated by physical methods.

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The present invention relates to all pure enantiomers or diastereomers and mixtures thereof.

The disclosed process is, including all sub-steps, an important component of the present invention.

Surprisingly, it has now been found that compounds of formula I have a highly beneficial microbicidal spectrum for phytopathogenic fungi and bacteria for practical purposes.

They have very beneficial curative, systemic and especially preventive properties and can be used to protect 10 numerous cultural plants. The active compounds of formula I can control or eradicate microorganisms that occur on plants or parts of the plant (fruits, flowers, foliage, stems, tubers, roots) from various crops, since later growing plant parts are also protected against such microorganisms.

The active compounds of formula I are effective against phytopathogenic fungi belonging to the following classes: Fungi imperfect! (e.g., Botrytis, Helminthosporium, Fusarium, Septoria, Cercospora and Alternari ^, Basidiomyceter (e.g.

20 genera Hemileia, Rhizocotonia and Puccinia); in particular, they are effective against fungi belonging to the class Ascomyceter (e.g. Venturis, Podosphaera, Erysiphe, Monilinia and Uncinula). In addition, the compounds of formula I have a systemic effect. They can also be used as a dressing agent for the treatment of plant propagating material (fruits, tubers and grains) and plant cuttings for protection against fungal infections as well as against phytopathogenic fungi occurring in the soil.

Thus, the invention also relates to microbicidal agents as well as the use of compounds of formula I for the control of 30 phytopathogenic microorganisms, especially plant-damaging fungi or preventive protection against plant attacks.

The compositions of the invention are characterized in that they contain as a microbicidal component a compound of the invention.

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The method of the invention for controlling or protecting against attacks on cultured plants by phytopathogenic microorganisms is characterized by applying a compound of the invention to the plant or its growing site.

For example, as target cultures for the indicated ranges herein, within the scope of the invention, the following plant species apply: Cereals, such as wheat, barley, rye, oats, rice, sorghum and related cereals, beets such as sugar beet and fodder beets, kernel, stone and berry fruit, such as apple, pear, 10 plum, peach, almond, cherry, strawberry, raspberry and blackberry, legumes such as beans, lentils, peas and soy, oil crops such as canola, mustard, poppy, olive, sunflower, coconut, castor, cocoa and peanut , cucumber plants such as pumpkin, cucumbers and melons, fiber plants such as cotton, flax, hemp and jute, citrus fruits such as oranges, lemons, grapefruit and mandarins, vegetables such as spinach, main salad, asparagus, cabbage, carrots, onions, tomatoes, potatoes and peppers, laurel plants such as avocado, cinnamon and camphor, or plants such as maize, tobacco, nuts, 20 coffee, sugar cane, tea, grapes, hops, banana and natural cauliflower plants and ornamental plants (cow rveblomster).

Active compounds of formula I are usually used in the agricultural sector in the form of preparations and may be applied to the areas or plants to be treated at the same time as 25 or after application of other active substances. These other active substances may be fertilizers, trace element intermediates or other preparations affecting plant growth.

It may also be selective herbicides, insecticides, fungicides, bactericides, nematodicides, molluscicides or mixtures of several of these compositions together with any other carriers, surfactants or other application promoting additives commonly used in the formulation technique.

Suitable carriers and additives may be solid or liquid and correspond to the useful substances used in the formulation technique, such as e.g. natural

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13 or regenerated minerals / solvents / dispersants wetting agents, adhesives / thickening agents, binders or fertilizers.

A preferred method of applying an active substance of formula I or an agrochemical agent containing at least one of the active substances is application to the foliage (foliage application). The number of applications and amount of application thus depends on the degree of attack of the corresponding developer (fungal species). However, the active substances of formula I can also reach the plants through the root network (systemic effect) by watering the plants' growth site with a liquid solution or adding the soil to the compounds in solid form, e.g. in the form of granules (soil application). However, the compounds of formula I may also be applied to coating grains by either wetting the grains with a liquid composition of the active substance or applying a layer of a solid composition to them. In addition, other application methods are possible in special cases, e.g. controlled treatment of the plant stems or buds.

The compounds of formula I are used for this purpose in unchanged form or preferably with the aids commonly used in the formulation technique and are therefore processed in a known manner, e.g. for emulsion concentrates, irradiated pastes, direct sprayable or dilute solutions, diluted emulsions, spray powders, soluble powders, powder preparations, granules or by encapsulation in e.g. polymeric substances. The methods of application, such as spraying, misting, spraying, spraying, laying or watering, are also selected along with the nature of the agent, taking into account the desired objectives and conditions. Favorable amounts of application usually equate to from 50 g to 5 kg of active substance (AS) per day. ha, preferably from 100 g to 2 kg AS / ha, in particular from 35 200 g to 600 g AS / ha,

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The formulations, ie. the agents containing the active compound of formula I and optionally a solid or liquid additive, the compositions or compositions are prepared in known manner, e.g. by thorough mixing and / or grinding the active substances with excipients such as e.g. with solvents, solid carriers and optionally surfactants (surfactants).

As solvents may be used aromatic hydrocarbons, preferably fractions Cg to C. /, As xylsubstances or substituted naphthalene, phthalic acid esters such as dibutyl or dioctyl phthalate, aliphatic hydrocarbons such as cyclohexane or paraffins, alcohols ethers and esters thereof, such as ethanol, ethylene glycol, ethylene glycol monomethyl or ethyl ether, ketones such as cyclohexanone, highly polar solvents such as N-methyl-2-pyrrolidone, dimethylsulfoxide or dimethylformamide, and optionally epoxidized plant oils such as epoxidized coconut oil or soybean oil, or water.

As solid carriers, e.g. For powder preparations and dispersible powders, natural stone flour, such as calcite, talc, kaolin, montmorillonite or atta pulgite, is generally used. To improve the physical properties, high-dispersion silicic acid or high-dispersive absorbent polymerisates can also be added. Granular absorbent granular carriers may be used as porous type such as e.g. pumice, crushed brick, sepiolite or bone tonite, and as non-absorbent carriers, for example, calcite or sand may be used. In addition, a large number of pre-granulated materials of inorganic or organic nature can be used, such as in particular dolomite or finely divided plant residues. Particularly advantageous application-promoting additives which can significantly reduce the amount of use are also natural (animal or vegetable) or synthetic phospholipids from the series of kephalins and lecithins, such as e.g. phosphatidylethanolamine, phosphatidylserine, phosphatidylcholine, sphingomyelin, phosphatidylinositol, phosphatidylglycerol,

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15 lysolecithin, plasma allogeneic or cardiolipin / which can be extracted, for example, from animal or vegetable cells, especially from brain, heart, liver, egg yolks or soybeans. Usage mixtures commercially available are e.g. phosphatidylcholine mixtures. Synthetic phospholipids are e.g. dioctanoylphosphatidylcholine and dipalmitoylphosphatidylcholine.

As surfactants, depending on the nature of the active substance of formula I to be formulated, nonionic, cat and / or anionic surfactants having good emulsifying, dispersing and wetting properties can be used. Surfactants are also meant surfactant mixtures.

Suitable anionic surfactants may be so-called water-soluble soaps as well as water-soluble synthetic surfactants.

As soaps, for example, alkali metal, alkaline earth metal or optionally substituted ammonium salts of higher fatty acids may be used, or the K salts of oleic or stearic acid, or of natural fatty acid mixtures which can be extracted, for example, from coconut oil or tallow oil. Furthermore, fatty acid methyl laurine salts can be used.

However, so-called synthetic surfactants are often used, especially fatty sulfonates, fatty sulfates, sulfonated benzimidazole derivatives or alkyl lauryl sulfonates.

The fatty sulfonates or fatty sulfates are generally present as alkali metal, alkaline earth metal or optionally substituted ammonium salts and contain an alkyl group of 8-22 C atoms, the alkyl also comprising the alkyl portion of acyl groups, e.g. The Na or Ca salt of lignin sulfonic acid, of dodecyl sulfuric acid ester or of a fatty alcohol sulfate mixture prepared from natural fatty acids. These include the salts of the sulfuric acid esters and sulfonic acids of fatty alcohol-ethylene oxide adducts. The sulfonated benzimidazole derivatives

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Preferably, 16 levels contain 2-sulfonic acid groups and a fatty acid group of 8-22 C atoms. Alkylarylsulfonates are e.g.

The Na / Ca or triethanolamine salts of dodecylbenzenesulfonic acid, of dibutylnaphthalenesulfonic acid or of naphthalene sulfonic acid formaldehyde condensation product.

Furthermore, similar phosphates / e.g. salts of the phosphoric acid ester of a p-nonylphenol (4-14) ethylene oxide adduct.

As nonionic surfactants, poly-glycol ether derivatives of aliphatic or cycloaliphatic alcohols, saturated or unsaturated fatty acids and alkyl phenols which may contain 3-30 glycol ether groups and 8-20 C atoms in the (aliphatic) hydrocarbon group are used primarily and 6-18 C atoms in the alkyl group of the alkyl phenols.

Other suitable nonionic surfactants are the water-soluble 20-250 ethylene glycol ether groups and 10-100 propylene glycol ether groups containing polyethylene oxide adducts with polypropylene glycol, ethylene diaminopolypropylene glycol and alkyl polypropylene glycol having 1-10 C atoms in the alkyl chain. The said compounds generally contain 1-5 ethylene glycol units per liter. propylene glycol unit.

Examples of nonionic surfactants include nonylphenol polyethoxyethanols, castor oil polyglycol ethers, polypropylene polyethylene oxide adducts, tributylphenoxy polyethanol, polyethylene glycol and octylphenoxypolyethoxyethanol.

Furthermore, fatty acid esters of polyoxyethylene sorbitan such as polyoxyethylene sorbitan trioleate can be used.

The cationic surfactants are primarily quaternary ammonium salts containing as N substituents at least one alkyl group having 8-22 C atoms, and as additional substituents optionally containing halogenated lower alkyl or benzyl groups or lower hydroxyalkyl groups. The salts are present

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17 preferably provides as halides, methyl sulfates or ethyl sulfates, e.g. stearyltrimethylammonium chloride or benzyldi (2-chloroethyl) -ethylammonium bromide.

The surfactants 5 commonly used in the formulation technique are described, inter alia, in the following publications: "Mc Cutcheon's Detergents and Emulsifiers Annual" BC Publishing Corp., Ridgewood New Jersey / 1981.

Helmut Stache "Tendid-Taschenbuch" Carl Hauser-Verlag Munchen / Wien 1981.

The agrochemicals generally contain 0.1-99%, in particular 0.1-95% of active substance of formula I, 99.9-1%, especially 99.8-5% of a solid or liquid additive and 0-25%, especially 0.1-25% surfactant.

While a concentrated commodity is preferred as a commodity, the end consumer usually uses a dilute agent.

The compositions of the invention may also contain other additives such as stabilizers, anti-foaming agents, viscosity regulators, binders, adhesives, and fertilizers and other active agents to obtain special effects.

The invention is further illustrated in the following examples in which percentages and parts are by weight. DMSO means dimethyl sulfoxide, DMF means dimethylformamide. Pressure is given in millibars (mb) or bar (b).

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Preparation Examples

Example H1; Preparation of fl1

.- / OH Λ \ I

Cl - / - - G-CHF-C2 = = CH2

A

li II • -N

1- (1H-1,2,4-triazol-1-yl) -2- (2,4-dichlorophenyl) -3-fluoro-pentan-2-ol-a) Preparation of Preparation: / C1 ♦ - · Cl- (> -c-chf-2H5 o 1- (2,4-dichlorophenyl) -2-fluoro-butanone

To a mixture of 77 g of 1- (2,4-dichlorophenyl) -2-bromobutanone 10 and 500 mg of 18-krone-6 in 750 ml of absolute acetonitrile, 31 g of dry potassium fluoride are added and the mixture is slowly heated to 100 ° -110 with stirring. ° C. After approx. 48 hours the reaction is complete (Control: gas chromatographic or with NMR). The reaction mixture is now poured into 2 liters of ice water and extracted several times with diethyl ether. The combined extracts are washed with water, dried with sodium sulfate and evaporated. Yield: 57 g of oily product. [H-F coupling constant 50 Hz] Boiling point: 77-78 ° C / 0.008 mbar.

b) Preparation of Another Pre-Step: 1- [2- (2,4-Dichlorophenyl) -2- (1-fluoropropyl) -oxirane

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19 8 g of 80% sodium hydride are suspended in 300 ml of absolute DMSO.

To this, 68 g of trimethyloxosulfonium iodide is added portionwise with stirring under a nitrogen atmosphere. After the hydrogen evolution is complete and the exothermic reaction is quenched, the mixture is stirred for 2 more hours at room temperature. Then, a solution of 57 g of 1- (2,4-dichlorophenyl) -2-fluorobutanone in 100 ml of THF is added dropwise over 30 minutes, the resulting mixture is stirred for 3 hours and finally diluted with ice water to five times the volume. 10 is extracted several times with diethyl ether. The mixed extracts are washed with water, dried with sodium sulfate and freed from the solvent in vacuo. Yield: 55 g in the form of a brown oil.

c) Preparation of the final product: A mixture of 55 g of 2- (2,4-dichlorophenyl) -2- (1-fluoropropyl) oxirane, 30 g of 1,2,4-triazole and 3.5 g of potassium tert. butylate in 500 ml of DMF is stirred for 20 hours at 80 ° C. Then, the reaction solution is cooled to room temperature, poured into 2 liters of ice water and extracted several times with diethyl ether. The combined extracts are washed with water, dried over sodium sulfate and evaporated. Yield of 1- (1H-1,2,4-triazol-1-yl) -2- (2,4-dichlorophenyl) -3-fluoropentan-2-ol: 26 g in the form of colorless crystals. Mp. 204-206 ° C.

Example H2: Preparation of

- / C1 OH

25 «- <> -Cl ch2

A

li II

1- (1H-1,2,4-triazol-1-yl) -2- (2,4-dichlorophenyl) -3- (4-chlorophenoxy) -3-fluoropropan-2-ol a) Preparation of pre-step: scl _ / f

Cl - (C - CH

I II

·· L! '0 Br

DK 161199 B

1- (2,4-dichlorophenyl) -2-bromo-2-fluoroethanone To one. solution of 20.7 g of α-fluoro-2,4-dichloroacetophenone in 100 ml of carbon tetrachloride is added at 40-45 ° C a solution of 16 g of bromine in 100 ml of carbon tetrachloride. After approx.

5 1 hour the brown solution is discolored. The mixture is stirred for one hour and finally it is shaken with an aqueous sodium hydrogen carbonate solution and evaporated in vacuo. The oily residue is then distilled in high vacuum. Yield: 17 g. Boiling point: 89-92 ° C / 0.02 mbar.

(B) Preparation of Another Pre-Step: · - · · - »·

C1-6 -C-CHF-O-yl -Cl2 / π · as · 11 a = α 0 1- (2,4-dichlorophenyl) -2- (4-chlorophenoxy) -2-fluoroethanone 12, 8 g of chlorophenol and 13.8 g of potassium carbonate are stirred in 200 ml of acetone for 1 hour. To this suspension is added dropwise 28 g of 1- (2,4-dichlorophenyl) -2-bromo-2-fluoroethanone in 50 ml of acetone and the mixture is heated at reflux for 3 hours. After cooling to room temperature, the colorless saline precipitate is filtered off, the acetone removed in vacuo and diethyl ether added. The ether solution is washed with water, dried with sodium sulfate, filtered and evaporated. The oily crude product crystallizes after digesting with n-hexane. Yield: 21.5 g in the form of yellow crystals. Mp. 85-87 ° C.

c) Preparing another step: · - · · - ·

Cl ¢. C Cl s s s · 1 · ° 2- (2,4-dichlorophenyl) -2- (4-chlorophenoxyfluoromethyl) oxirane

DK 161199 B

21 g of 80% sodium hydride is stirred under nitrogen atmosphere in 80 ml of DMSO and 10.3 g of trimethyl oxosulfonium iodide are added portionwise. After the exothermic reaction is quenched, the mixture is stirred for an additional hour at room temperature, then a solution of 2- (2,4-dichlorophenyl) -2- (4-chlorophenoxy) -2-fluoroethanone is added dropwise in 30 ml of THF, the resulting mixture is stirred for another 5 hours at 25-30 ° C and finally poured into 1 liter of water. The product is extracted with diethyl ether, the extracts washed with water, dried over sodium sulfate, filtered and evaporated. Yield: 15 g in the form of a yellowish oil.

(d) Preparation of the final product:

A solution of 13 g of 2- (2,4-dichlorophenyl) -2- (4-chlorophenoxyfluoromethyl) oxirane, 4 g of 1,2,4-triazole and 0.5 g of potassium tert-butylate in 100 ml of DMF is stirred for 15 hours at 80-100 ° C. After cooling to room temperature, the reaction solution is poured into 500 ml of water, which separates the crude product as oil. It is extracted with diethyl ether, the combined extracts washed with water, dried over sodium sulfate, filtered and evaporated. Yield: 11 g of an oily product which crystallizes by digestion with n-hexane. Yield of the purified product: 7 g. 155-157 ° C.

Similarly, the compounds listed below can be prepared:

DK 161199 B

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DK 161199B

30

Formulation Examples for Liquid Active Substances of Formula I (% = wt%) ___ ~ _

Fl. Emulsion concentrates a) b) c)

Active substance according to the table 25% 40% 50% 5 Ca-dodecylbenzenesulfonate 5% 8% 6%

Castor oil polyethylene glycol ether (35 moles of ethylene oxide) 5%

Tributylphenoyl-polyethylene glycol ether (30 moles of ethylene oxide) - 12% 4% Cyclohexanone - 15% 20%

Xylene blend 65% 25% 20%

By dilution with water, emulsions of any desired concentration can be prepared from such concentrations.

15 F2. Solutions a) b) c) d)

Active substance according to the table 80% 10% 5% 95%

Ethylene glycol monomethyl ether 20%

Polyethylene glycol MV 400 - 70% N-Methyl-2-pyrrolidone - 20% Epoxidized Coconut Oil - - 1% 5%

Gasoline (boiling range 160-190 ° C) - - 94% (MV = Molecular Weight)

The solutions are suitable for use in the form of very small droplets.

25 F3. Granules a) b)

Active substance according to the table 5% 10%

Kaolin 94% High-dispersion silicic acid 1%

Attapulgite - 90% 30 The active substance is dissolved in methylene chloride, sprayed onto the support material and then the solvent is evaporated in vacuo.

DK 161199 B

31 F4, Powder a) b)

Active substance according to the table 2% 5% High-dispersion silicic acid 1% 5%

Talc 97% 5 Kaolin - 90%

By thoroughly mixing the carriers with the active compound, ready-made powder preparations are obtained.

Formulation Examples for Solids of Formula 1 (% = wt%) - 10 F5. Spray Powders a) b) c)

Active substance according to the table 25% 50% 75%

5% 5% of lignin sulfonate

NaLauryl Sulfate 3% - 5%

Na-diisobutylnaphthalenesulfonate - 6% 10% Octylphenol polyethylene glycol ether (7-8 moles of ethylene oxide) - 2% - High dispersant silicic acid 5% 10% 10%

Kaolin 62% 27%

The active compound is thoroughly mixed with the additives and thoroughly ground in a suitable mill. Spray powders are available which can be diluted with water to suspensions of any desired concentration.

F6. Emulsion Concentrate

Active substance according to the table 10% Octylphenol polyethylene glycol ether 4-5 moles ethylene oxide) 3%

Ca-dodecylbenzenesulfonate 3%

Castor oil polyglycol ether (35 moles of ethylene oxide) 4% Cyclohexanone 30%

Xylene Mixture 50%

From this concentrate, emulsions of any desired concentration can be prepared by dilution with water.

DK 161199 B

32 F7. Powder center a) b)

Active substance according to the table 5% 8%

Talc 95%

Kaolin - 92% 5 Ready-to-use powders are obtained by mixing the active compound with the carrier and subsequent grinding on a suitable mill.

F8. Extruded granules

Active substance according to the table 10% 10 Na lignin sulfonate 2%

Carboxymethyl cellulose 1%

Kaolin 87%

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

F9. coating Granules

Active substance according to the table 3%

Polyethylene Glycol (Molecular Weight 200) 3% Kaolin 94%

The finely ground active substance is uniformly placed in a mixing apparatus on the kaolin wetted with polyethylene glycol. In this way dust-free coating granules are obtained.

F10. Suspension concentrate Active substance according to the table 40%

Ethylene glycol 10%

Nonylphenol polyethylene glycol ether (15 moles of ethylene oxide) 6%

10% Carboxymethyl cellulose 1% 37% aqueous formaldehyde solution 0.2%

Silicone oil in the form of a 75% aqueous emulsion 0.8%

Water 32%

will DK 161199 B

33

The finely ground active compound is thoroughly mixed with the additives. In this way a suspension concentrate is obtained which, by dilution with water, gives suspensions of any desired concentration.

5 Biological Examples

Example B1 Effect against Puccinia graminis on wheat a) Residual protective effect

Wheat plants are sprayed 6 days after sowing with a spray liquid (0.02% active ingredient) prepared from a spray powder containing the active substance. After 24 hours, the treated plants are infected with a uredosporesus pension of the fungus. After incubation for 48 hours at a humidity of 95-100% and at a temperature of approx. At 20 ° C, the infected plants are placed in a greenhouse at approx.

22 ° C. The rust development is assessed 12 days after infection.

b) Systemic effect

For wheat plants, 5 days after sowing, a spray liquid (0.006% active substance, based on soil volume) 20 is prepared from a spray powder containing the active substance. After 48 hours, the treated plants are infected with an uredospores suspension of the fungus. After incubation for 48 hours at a humidity of 95-100% and a temperature of approx. At 20 ° C, the infected plants are placed in a greenhouse at approx. 22 ° C. Assess the development of rust 12 days after infection.

The compounds from the table show a very good effect against Puccinia fungi. Untreated but infected control plants exhibit a 100% Puccinia attack.

Compounds 1-10, 13, 14, 16, 18, 19, 24, 32-34, 40-46 and 48-52 inhibit the Puccinia attack to 0-5%.

DK 161199B

34

Example B2; Impact against Cercospora arachidicola on ground _ nut plants ..........

Residue Protective Effect 10-15 cm tall peanut plants are sprayed with a spray liquid (0.006% active substance) made from a spray powder containing the active substance and 48 hours later the plants are infected with a conidial suspension of the fungus. The infected plants are incubated for 72 hours at a temperature of approx. 21 ° C and high humidity, after which they are placed in a greenhouse until typical leaf spots appear. The fungicidal effect is assessed 12 days after infection based on the number and size of the spots occurring.

Compared to untreated but infected control plants (number and size of spots = 100%), peanut plants treated with the active substances listed in the table exhibit a greatly reduced cercospora attack.

Thus, in the above experiments, compounds 1-9, 13, 18, 19, 24, 32, 37, 40-46 and 49-53 almost completely prevent the occurrence of stains (0-10%).

Example B3: Effect against Erysiphae graminis on barley a) Residuai protective effect

Ca. 8 cm tall barley plants are sprayed with a spray liquid (0.002% active substance) prepared from a spray powder 25 containing the active substance. After 3-4 hours, the treated plants are pollinated with conidia of the fungus. The infected barley plants are placed in a greenhouse at approx. 22 ° C and the fungal attack is evaluated after 10 days.

b) Systemic effect 30 To approx. 8 cm tall barley plants are poured a spray liquid (0.006% active substance, calculated on the soil volume) made of a spray powder containing the active substance.

Care is taken to ensure that the spray liquid does not come into contact with the plant's aboveground parts. After 48 hours for

DK 161199B

35 races the treated plants are pollinated with conidia of the fungus. The infected barley plants are recommended in a greenhouse at approx. 22 ° C and the fungal attack is evaluated after 10 days.

Compounds of formula I exhibit good efficacy against Eryse 5 fungal fungi. Untreated but infected control plants show a 100% Erysiphe attack. Compounds from Tables 1-10, 13, 14, 16, 18, 19, 24, 32, 34, 37, 40-46 and 48-53 inhibit the fungal attack on barley to 0-5%, especially compound no.

2 causes a complete reduction of the attack.

Example B4: Residual protective effect against Venturia _inaegualis on apple shoots_ Apple cuttings with 10-20 cm long fresh shoots are sprayed with a spray liquid (0.006% active substance) prepared from a spray powder containing the active compound. After 15 24 hours, the treated plants are infected with a conidia suspension of the fungus. The plants are incubated for 5 days at a relative humidity of 90-100% and then left for a further 10 days in a greenhouse at 20-24 ° C. The scab attack is assessed 15 days after the infection. Compounds no.

20 1-6, 8, 9, 13, 16, 18, 19, 32, 40, 42, 44-46 and 48-52 inhibit the disease attack to less than 10%. Untreated but infected control shots exhibit a 100% Venturia attack.

Example B5: Effect against Botrytis cinerea on beans

Residual protective effect 2 3 Approx. 10 cm tall bean plants are sprayed with a spray liquid (0.02% active substance) prepared from a spray powder containing the active compound. After 48 hours, the treated plants are infected with a conidial suspension of the fungus. After an incubation of the infected plants for 3 days at a relative humidity of 95-100% and at a temperature of 21 ° C the fungal attack is assessed. The compounds from the table in many cases greatly inhibit the fungal attack. At a concentration of 0.02%, compounds 1-6, 8, 9, 13, 14, 19, 24, 32, 34, 40,

.. DK 161199 B

36 42, 44, 45, 46 as well as 48-52 appear to be fully effective. The disease attack ranges from 0-8%.

Botrytis attack on untreated but infected bean plants is 100%.

Example B6; Effect against Pyricularia oryzae on rice plants Residual protective effect

Rice plants are sprayed after 2 weeks of growth with a spray liquid (0.002% active ingredient) prepared from a spray powder containing the active compound. After 48 hours, the treated plants are infected with a conidiesus pension of the fungus. After 5 days incubation at a relative humidity of 95-100% and at a temperature of 24 ° C the fungal attack is assessed.

Rice plants which have been treated with a spray liquid containing as active substance one of the compounds no.

13 or # 32, compared to untreated control plants (100% infestation), a fungal attack of less than 10%.

Claims (12)

Compounds according to claim 1, characterized in that R 1 is hydrogen, R 3 is hydrogen, C 1-4 alkyl or 4-chlorophenoxy, and Az, Ar and R 2 have the meanings given in claim 1. Compounds according to claim 2, characterized in that Az means 1H-1,2,4-triazole, Ar means unsubstituted or in the 2- and / or 4-position with methyl or halogen substituted phenyl or phenoxyphenyl, and R1, R2 and R3 has the meanings specified in claim 2. Compound according to Claim 1, characterized in that it is selected from 1- (1H-1,2,4-triazol-1-yl) -2- (2,4-dichlorophenyl) -3-fluoro-butanone. 2-ol, 1- (1H-1,2,4-triazol-1-yl) -2- (2-chloro-4-fluorophenyl) -3-fluorobutan-2-ol, 1- (1H-1,2) (4-Triazol-1-yl) -2- (2,4-dichlorophenyl) -3-fluoro-pentan-2-ol, 1- (1H-1,2,4-triazol-1-yl) -2- (2,4-dichlorophenyl) -3-fluoro-4-methylpentan-2-ol, 1- (1H-1,2,4-triazol-1-yl) -2- (2-chloro-4- fluorophenyl) -3-5 fluoropentan-2-ol, 1- (1H-1,2,4-triazol-1-yl) -2- [p- (4-chlorophenoxy) phenyl] -3-fluoropropan-2-ol , 1- (1H-1,2,4-triazol-1-yl) -2- (2,4-dichlorophenyl) -3- (4-chlorophenoxy) -3-fluoropropan-2-ol and acid addition salts, quaternary azolium salts and metal complexes thereof. A compound according to claim 1, characterized in that it is selected from 1- (1H-1,2,4-triazol-1-yl) -2- (4-chlorophenyl) -3-fluorohexan-2-ol, 1- (1H-1,2,4-triazol-1-yl) -2- (2,4-dichlorophenyl) -3-fluoro-hexan-2-ol, 1- (1H-1,2,4-triazole) -1-yl) -2- (2,4-dichlorophenyl) -3,3-difluoropentan-2-ol, 1- (1H-1,2,4-triazol-1-yl) -2- ( 2,4-dichlorophenyl) -3-fluoro-4-methylpentan-2-ol, 1- (1H-1,2,4-triazol-1-yl) -2- [p- (4-bromophenoxy) phenyl] - 3,3-difluoropropan-2-ol, 1- (1H-1,2,4-triazol-1-yl) -2- [p- (4-fluorophenoxy) phenyl] -3,3-difluoropropan-2-ol ol, 1- (1H-1,2,4-triazol-1-yl) -2- [p- (4-chlorophenoxy) phenyl] -3,3-difluoropropan-2-ol, 1- (1H-1, 2,4-triazol-1-yl) -2- [p- (4-chlorophenoxy) -2-methyl-phenyl] -2-hydroxy-3-fluoropropane and acid addition salts, quaternary azolium salts and metal complexes thereof. Compound according to claim 1, characterized in that it is 1- (1H-1,2,4-triazol-1-yl) -2- (2,4-dichlorophenyl) -3- (4-chlorophenoxy) -3 -fluorpropan-2-ol. DK 161199 B Compound according to claim 1, characterized in that it is 1- (1H-1,2,4-triazol-1-yl) -2- (2-chloro-4-fluorophen-yl) -2-propenyloxy-3 -fluorpentan. Compound according to claim 1, characterized in that it is 1- (1H-1,2,4-triazol-1-yl) -2- (4-fluorophenyl) -2- (4-chlorobenzyloxy) -3- fluoropropan. A compound according to claim 1, characterized in that it is 1- (1H-1,2,4-triazol-1-yl) -2- (2,4-dichlorophenyl) -2-methoxy-3-fluorobutane. Process for the preparation of compounds of formula I according to claim 1, characterized in that first an oxirane of the formula 0 Ar-c-CH 2 (II) I 2 R, -CR, L in 5 F is reacted with an azole with the formula 15 M-Az (HI) into a compound of the formula OH Ar-C-CH -Az '(Ia) I 2 R - CR, F and, if necessary, the alcohol 1a converts in a conventional manner, e.g. by reaction with a compound of formula DK 161199B RX-W (IV) to an ether of formula I wherein the substituents R 1, R 2, R 3, Ar and Az of formulas Ia, II, III and IV have the meanings given in formula I , M means hydrogen or a metal atom, and W means OH or a common leaving group. 11. A means for controlling or protecting against attack by microorganisms, characterized in that it, in addition to the usual carrier materials, comprises at least one. active component 10 contains a compound according to claim 1. An agent according to claim 11, characterized in that it contains 0.1-99% effective compound of formula I, 99.9-1% solid or liquid additive and 0-25% surfactant. A method for controlling or protecting against attacks on crop plants by phytopathogenic microorganisms, characterized in that a compound according to claim 1 is applied to the plant or its growing site.