CS250237B2 - Fungicide and method of its efficient component production - Google Patents

Abstract

Es werden 1-Azolyl-2-aryl-3-fluor-alkan-2-ole der allgemeinen Formel I beschrieben, worin

• Az für 1H-1,2,4-Triazol, 4H-1,2,4-Triazot oder 1H-Imidazol steht;
• Ar einen unsubstituierten oder substituierten aromatischen Rest aus der Reihe Phenyl, Biphenyl, Phenoxyphenyl und Naphthyl bedeutet;
• R, für Wasserstoff, C,-C₄-Alkyl, C₃-C₅-Alkenyl oder Benzyl steht;
• R₂ Wasserstoff, Fluor oder C₁-C₆-Alkyl bedeutet; und
• R₃ Wasserstoff, Fluor, C₁-C₆-Alkyl, C₁-C₆-Haloalkyl, C₁-C₆-Alkoxy, C,-C₆-Alkylthio, Phenyl, Phenoxy, Phenylthio oder C₃-C₇-Cycloalkyl steht, wobei jeder aromatische Substituent oder aromatische Anteil eines Substituenten unsubstituiert oder ein- oder mehrfach durch Halogen, C₁-C₄-Alkyl, C₁-C₄-Alkoxy, C,-C₄-Haloalkyl, Nitro und/oder Cyanosubstituiert ist; unter Einschluss der Säureadditionssalze, quaternären Azoliumsalze und Metallkomplexe.

Es werden ferner Methoden zur Herstellung dieser Produkte offenbart sowie agrochemische Mittel, die als Wirkstoff eine dieser Verbindungen enthalten. Ferner wird ein Verfahren zur Bekämpfung phytopathogener Mikroorganismen mit Hilfe dieser Substanzen beschrieben.

Description

The present invention relates to fungicidal compositions which contain as active ingredient new, substituted 1-azolyl-2-aryl-3-fluoroalkan-2-oles and ethers thereof of the general formula I as well as their acid addition salts, quaternary azole salts and metal complexes. The present invention further relates to a process for the preparation of these active substances. The invention also relates to the preparation of said compositions as well as to the use of active substances or compositions for combating harmful fungi, preferably for combating fungi damaging plants.

The novel compounds of this invention are compounds of formula I or-h

I Ί

Az — CH2 — C — C — F 'II ^{Ar R} 3 (I) wherein

Az is 1H-1,2,4-triazolyl or 1H-imidazolyl,

Ar is an optionally substituted aromatic radical selected from the group consisting of phenyl or phenoxyphenyl;

R 1 is hydrogen, methyl, C 3 alkenyl or benzyl, and

R 3 is hydrogen, C 1 -C 4 alkyl or phenyl, each aromatic substituent or aromatic portion of the substituent being optionally substituted one or more times with halogen and / or methyl, including acid addition salts, quaternary azolium salts and metal complexes .

The term "alkyl" by itself or as a component of another substituent means, for example, according to the number of said carbon atoms, the following groups: methyl, ethyl, propyl, butyl, and their isomers such as isopropyl, isobutyl, tert-butyl group. Halogen is understood herein to mean fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine. Alkenyl means 1-propenyl, allyl.

The present invention relates to the free compounds of formula I, their acid addition salts, quaternary azolium salts and metal complexes. Preferred are free compounds, especially 1H-1,2,4-triazole derivatives within the scope of Formula I.

As an example of salt-forming acids, the following inorganic acids can be used:

Hydrohalic acids such as hydrofluoric acid, hydrochloric acid, hydrobromic acid or hydroiodic acid as well as sulfuric acid, phosphoric acid, phosphorous acid, nitric acid and organic acids such as acetic acid, trifluoroacetic acid, trichloroacetic acid, propionic acid, formic acid benzenesulfonic acid, p-toluenesulfonic acid or methanesulfonic acid.

The metal complexes of the compounds of formula I consist of a basic organic molecule and an organic or inorganic metal salt, for example, halides, nitrates, sulfates, phosphates, acetates, trifluoroacetates, trichloroacetates, propionates, tartrates, sulfonates, salicylates, benzoates etc. the main groups of the periodic system elements such as aluminum, tin or lead, as well as the first to eighth sub-groups of the periodic system elements such as chromium, manganese, iron, cobalt, nickel, zirconium, copper, zinc, silver, mercury etc. elements of the 4th subgroup.

These metals may be present in different valencies corresponding to them. Complexes of compounds of formula I with metals may exist as mononuclear or multinuclear, i. They may contain one or more portions of an organic molecule as ligands. Complexes with copper, zinc, manganese, tin and zirconium metal are preferred.

The compounds of formula I are stable oils at room temperature, resins or predominantly solids, which have very valuable microbicidal properties. They can be used preventively and curatively in agricultural and related fields for combating fungi which damage plants, with triazolyl methyl derivatives being preferred within the compounds of the formula I. The active compounds of the formula I according to the invention are characterized by very good fungicidal activity in plant protection and problem-free application at low application rates. In addition, the compounds also have the ability to control the growth of plants, in particular to inhibit the growth of plants, especially in the case of plants which are grown in tropical areas for covering crops against erosion.

Fungicidally particularly preferred individual substances are, for example, the following compounds:

1- (1H-1,2,4-triazol-1-yl) -2- (2,4-dichlorophenyl) -3-fluorobutan-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-fluoropentan-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-fluoropentan-2-ol,

1- (1H-1,2,4-triazol-1-yl) -2- (2,4-dichlorophenyl) -3- (4-chlorophenoxy) -3-fluoropropane-2-01,

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- (1H-1,2,4-triazol-1-yl) -2- (2,4-dichlorophenyl) -3-fluoro-hexan-2-ol,

1- (1H-1,2,4-triazol-1-yl) -2- [p- (4-chlorophenoxy) -2-methylphenyl) -2-hydroxy-3-fluoropropane.

The compounds of the formula I are prepared according to the invention by reacting the oxirane of the formula II

in which

Ar and R ₃ have the meanings stated above, with an azole of formula III

Az — Az (III) in which

Az is as defined above and

M is hydrogen or preferably a metal atom, in particular an alkali metal atom such as lithium, sodium or potassium, first to form a compound of formula Ia

OH

Ar-C-CH ₂ -A

H — C — R ₃

F (1a) wherein

6

Ar, Az and R ₃ are as defined above, and optionally the alcohol of formula Ia is converted in a conventional manner, for example by reaction with a compound of formula IV

R-W (IV) wherein

R ₍ as defined above and

W represents a hydroxyl group or a conventional leaving group, to an ether of formula I.

Conventional leaving groups are known in the literature.

The reaction of compounds of formulas II and III to form compounds of formula Ia is carried out in the presence of condensing or acid binding agents. Suitable such organic and inorganic bases, for example tertiary amines, such as trialkylamines (trimethylamine, triethylamine, tripropylamine, etc.), pyridine and pyridine bases (4-dimethylaminopyridine, 4-pyrrolidylaminopyridine, etc.), oxides, hydrides and hydroxides, carbonates and alkali metal and alkaline earth metal bicarbonates (calcium oxide, barium oxide, sodium hydroxide, potassium hydroxide, sodium hydride, calcium hydroxide, potassium bicarbonate, sodium bicarbonate, calcium bicarbonate, potassium carbonate and sodium carbonate), as well as alkali metal acetates such as acetate sodium or potassium acetate.

In addition, alkali metal alkoxides such as sodium ethoxide, sodium n-propoxide, etc. are also suitable. In some cases, it may be advantageous to convert the free azole of formula III (M = hydrogen) first, for example in situ by treatment with an alkoxide, to the corresponding salt. and this is then reacted with an oxirane of formula II. In the preparation of the 1,2,4-triazole derivatives, 1,3,4-triazolyl isomers are generally also produced in parallel in parallel, which can be separated in the usual manner, for example with different solvents.

This reaction (of the compound of formula II with the compound of formula III to give the compound of formula Ia) is preferably carried out in a relatively polar but inert reaction organic solvent such as Ν, Ν-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, acetonitrile, benzonitrile and others. Such solvents may be in combination with other solvents inert under the reaction conditions, for example benzene, toluene, xylene, hexane, petroleum ether, chlorobenzene, nitrobenzene and others. The reaction temperatures range from 0 ° C to 150 ° C, preferably from 20 ° C to 100 ° C.

Otherwise, this reaction (of the compound of formula II with a compound of formula III to give a compound of formula Ia) can be carried out analogously to the already known reactions of other oxiranes with azoles (cf. DE-OS 2912 288).

In the partial reactions mentioned, the intermediates can be isolated from the reaction medium and, if desired, can be purified in the usual manner, for example by washing, digesting by extraction, crystallization, chromatography, distillation, etc. before the next reaction.

Further reaction of compounds of formula Ia to compounds of formula I is carried out in cases where W in formula IV is a conventional leaving group, in the absence or preferably in the presence of a solvent inert under the reaction conditions.

For example, the following solvents are suitable:

N, N-dimethylformamide,

N _in N - (β-β-β-acetyl), hexamethylphosphoric triamide, dimethylsulfoxide, m-methyl-2-piperidone, etc.

Mixtures of these solvents with each other or with other customary inert organic solvents, for example aromatic hydrocarbons such as benzene, toluene, xylenes, etc. may also be used.

In many cases, it has been found expedient to work to increase the reaction rate in the presence of a base such as an alkali metal hydride, hydroxide or carbonate. It may also be advantageous for the alcohol of formula Ia (R _t = OH) is first converted in a known manner, for example by reaction with a strong base to a suitable metal salt.

Suitable strong bases are, for example, alkali metal hydrides and alkaline earth metal hydrides (sodium hydride, potassium hydride, calcium hydride, etc.) and alkali metal organic compounds such as butyllithium or alkali metal tert-butoxide, in addition alkali hydroxides may also be used metals such as sodium hydroxide or potassium hydroxide when operating in an aqueous two-phase system and in the presence of a phase transfer catalyst.

However, it is also possible to first convert the alcohol of formula (Ia) into an alkali metal alkoxide before the next reaction, and then react it with compounds of formula (IV) (wherein W is a leaving group), preferably in the presence of a crown ether. In the case of Μ = K, in particular 18-crown-6 is employed; in the case of M = Na, the reaction is preferably carried out in the presence of 15-crown-5.

The reaction is expediently carried out in a medium which is inert to the reactants. Suitable solvents are, for example, ethers and ether compounds, for example di (lower) alkyl ethers (diethyl ether, diisopropyl ether, tert-butyl methyl ether, etc.), tetrahydrofuran, dioxane and aromatic hydrocarbons such as benzene, toluene or xylenes.

For the organic, water-immiscible phase, for example, the following solvents are suitable: aliphatic and aromatic hydrocarbons such as pentane, hexane, cyclohexane, petroleum ether, ligroln, benzene, toluene, xylenes, etc., halogenated hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride, ethylenedichlor, 1,2-dichloroethane, tetrachlorethylene etc. or aliphatic ethers such as diethyl ether, diisopropyl ether, tert-butyl methyl ether, etc. Examples of suitable phase transfer catalysts are: tetraalkylammonium halides, tetraalkyl hydrogen sulphates or tetraalkylammonium hydroxides such as tetrabutylammonium chloride. tetrabutylammonium bromide, tetrabutylammonium iodide; triethylbenzylammonium chloride, triethylbenzylammonium bromide, tetrapropylammonium chloride, tetrapropylammonium bromide, tetrapropylammonium iodide; etc.

Phosphonium salts are also suitable as phase transfer catalysts. Reaction temperatures are generally between 30 ° C and 130 ° C, optionally up to the boiling point of the solvent or solvent mixture.

In cases where in formula IV the symbol W represents a hydroxyl group, a condensation reaction is preferably carried out. Both reactants are heated under reflux in a suitable solvent.

Solvents which are inert to the reactants and which form an azeotropic mixture with water are preferably used in this case. Aromatic hydrocarbons such as benzene, toluene, xylenes or halogenated hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, tetrachlorethylene, chlorobenzene, but also ether compounds such as tert-butyl methyl ether, dioxane and others are suitable for this purpose. In many cases, the compound of formula III may itself be used as a solvent. This condensation reaction is expediently carried out in the presence of a strong acid, for example paratoluenesulfonic acid, and at the boiling points of the azeotropic mixture.

For the preparation of ethers of formula I, it is also possible to exchange the free hydroxyl group in the compounds of formula Ia first with one of the abovementioned leaving groups W, and then to react the compound thus obtained with a compound of formula IV (sW =? OH).

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

The oxiranes of formula (II) are novel and are particularly developed intermediates for the preparation of valuable active compounds of formula (I). By virtue of their structure, these compounds can be easily converted into compounds of formula (Ia). family Ascomycetes. Basidiomycetes or Fungi imperfecti.

The epoxides of the formula II can be prepared in a manner known per se from the ketones of the formula V

H

Ar = C-C-F (V) o R 3 wherein

Ar and R 3 are as defined above, by reaction with dimethylsulfonium methylide or dimethyloxosulfonium methylide (cf. Corey and Chaykovsky, JACS, 1962, 84, 3,782).

The ketones of formula V can be obtained by methods known per se from the literature [cf. J. Leroy, J. Org. Chem. 46, 206 (1981) or Houben-Weyl, Vol. V / 3, p. 211] from the corresponding known α-bromoketones by conventional fluorine exchange or can also be prepared by acylating the basic aromatics with fluorinated carboxylic acid derivatives, for example by Friede-Crafts reaction.

In principle, unless otherwise expressly stated in the individual cases, the starting materials, intermediates and reaction products mentioned herein are prepared in the presence of one or more solvents or diluents inert to the components of the reaction mixture. Aliphatic and aromatic hydrocarbons such as benzene, toluene, xylenes, petroleum ether; halogenated hydrocarbons such as chlorobenzene, methylene chloride, ethylene chloride, chloroform, carbon tetrachloride, tetrachlorethylene; ethers and ether compounds such as dialkyl ethers (diethyl ether, diisopropyl ether, tert-butyl methyl ether, etc.), anisole, dioxane, tetrahydrofuran; nitriles such as acetonitrile, propionitrile; N, N-dialkylated amides such as dimethylformamide; dimethylsulfoxide; ketones such as acetone, diethyl ketone, methylene ketone, and mixtures of such solvents with each other.

In many cases, it may also be advantageous if the reactions or reaction stages are 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 certain cases, carbon dioxide.

Compounds of formula (I)

QR /

Ar 'i ^c í ^r t

In which the general symbols have the abovementioned 250237 we, in each case adjacent to the substituents Ar and OR 1, always have an asymmetric C * carbon atom and can therefore exist in two enantiomeric forms. Generally, in the preparation of these compounds, a mixture of both enardiomers is formed which can be resolved in the usual manner, for example by traction crystallization of salts with optically active, strong acids, into pure optical antipodes.

Enantiomers may have different biological effects. Thus, for example, in one form, the tungicidal effect may be predominant and the other tormic effect may be plant growth regulating. There may also be a graduated difference in activity with the same spectrum of action. When R ₃ is not hydrogen, then there is another center. asymmetry), which leads to the existence of diastereomeric mixtures (threo- and erythro-throma) which can be separated by physical methods.

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

The method of manufacture described, including all sub-steps thereof, is an important part of the present invention.

Surprisingly, it has been found that the compounds of formula I have great practical requirements. favorable spectrum of microbicidal activity against tytopathogenic fungi and bacteria. Said compounds have very advantageous curative, statistical and especially preventive properties and can be used to protect numerous crop plants. The active compounds of the formula I can be used to continue or destroy microorganisms occurring on plants or on parts of plants (fruits, flowers, leaves, stems, tubers, roots) of various useful plants, while remaining protected from such microorganisms and later grown parts of plants.

The active substances are active against thyopathogenic agents. fungi belonging to the following classes: Fungi impertecti (for example Botrytis, Helrainthosporium, Fusarium, Septoria, Cercospora and Allernaria); Basidiomycetes (for example, families Hemileia, Rhizoctonia, Puccinia); in particular, they are effective against fungi of the Ascomycetes class (e.g. Venturia, Podosphaera, Erysiphe, Monilinia, Uncin ^1a) .

In addition, the compounds of formula I are also systemically active. Furthermore, these compounds can be used as seed dressings for the treatment of seed (fruits, tubers, seeds) and plant seedlings to protect against fungal infections as well as against the tytopathogenic fungi that occur in the soil.

Accordingly, the present invention provides tungicidal compositions which contain at least one compound of formula I as an active ingredient, as well as the use of the compounds of formula I to combat thyto-pathogenic microorganisms, in particular fungi damaging plants or to prevent plant attack.

In addition, the present invention also encompasses the production of agrochemical compositions by thoroughly mixing the active ingredient with at least one of the substances or groups of substances described herein. The invention also relates to a process for the treatment of plants, which comprises applying compounds of the formula I or novel compositions.

Suitable crop plants to which the abovementioned application possibilities apply include, for example, the following plant species in the context of the present invention: cereals (wheat, barley, rye, oats, rice, sorghum and related plants); beet (sugar beet and fodder beet); fruit trees bearing fruit with kernels, stones and berries (apple, plum, peach, almond, cherry, strawberry, raspberry and blackberry); legumes (tazol, lentils, peas, soybeans); oilseeds (rape, mustard, poppy, olive, sunflower, coconut, castor oil, cocoa, groundnut); cucurbits (pumpkins, cucumbers, melons); pulp (cotton, flax, hemp, jute); citrus trees (orange, lemon, biggest lemon, mandarin); various vegetables (spinach, lettuce, asparagus, cabbage, carrot, onion. tomatoes, potatoes, peppers); laurel plants (avocado, cinnamon, bark beetle) or other plants such as maize, tobacco, butternut, coffee, sugarcane, tea, vine, hops, banana and rubber tree, as well as ornamental plants (CcmpositEe).

The active compounds of the formula I are usually used in the formulations and can be applied to the treated metal sheets or plants simultaneously or sequentially with the other active compounds. These other active substances may be both fertilizers, trace element compositions or other preparations which influence the growth of plants. They may also be selective herbicides, insecticides, tungicides, bactericides, nematocides, molluscicides or mixtures of these formulations together with, optionally, other carriers, surfactants or other application aids used in the preparation of such formulations.

Suitable carriers may be solid or liquid and correspond to those used in the preparation of such compositions, such as natural or regenerated minerals, solvents, dispersants, wetting agents, adhesives, thickeners, binders or fertilizers.

A suitable method of applying an active compound of the formula I or an agrochemical composition comprising at least one of these active compounds is represented by application to the leaves of plants. The number of applications depends on the extent of infestation for the corresponding disease agent (fungus species). However, the active compounds of the formula I can also be fed to the plant via. soil and roots (systemic effect) by watering the place where plants grow, or by applying the active ingredients to the soil in solid form, for example in the form of a granulate (soil application). However, the compounds of formula I can also be applied to the seeds (Coating) by either impregnating the seeds with a liquid active ingredient preparation or by forming a solid active ingredient layer thereon. In addition, other modes of application are possible in special cases, such as the deliberate treatment of plant stems or buds.

The compounds of the formula I are used in this application in unchanged form or preferably together with auxiliaries customary in the preparation of such compositions and are therefore processed, for example, into emulsion concentrates, paint pastes, sprayable or dilutable solutions, diluted emulsions , wettable powders, soluble powders, dusts, granules and compositions encapsulated in, for example, polymeric substances in a manner known per se. Application procedures, such as spraying, fogging, dusting, sprinkling, coating or watering, as well as the type of formulation, are selected in accordance with the desired objectives and conditions. Favorable application rates are generally in the range of 50 g to 5 kg of active ingredient per ha, preferably in the range of 100 g to 2 kg of active ingredient, in particular 200 grams to 600 g of active ingredient per hectare.

Said formulations, i.e. compositions comprising the active compound of the formula I and optionally a solid or liquid additive, concentrates or dosage forms are prepared in a known manner, for example by thoroughly mixing and / or grinding the active compounds with carriers, such as solvents, solid carriers and optionally surfactants (surfactants).

Suitable solvents are: aromatic hydrocarbons, preferably C8-C12 fractions, such as mixtures of xylenes or substituted naphthalenes, phthalic acid esters such as dibutyl phthalate or dioctyl phthalate, aliphatic hydrocarbons such as cyclohexane or paraffins, alcohols, and glycols such as and their ethers and esters, such as ethanol, ethylene glycol, ethylene glycol monomethyl ether or ethylene glycol monomethyl ether, ketones such as cyclohexanone, strongly polar solvents such as N-methyl-2-pyrrolidone, dimethylsulfoxide or dimethylformamide, and optionally epoxidized oil plants such as epoxidized coconut oil or soya oil or water.

As solid carriers, for example for dusts and dispersible powders, natural stone flours such as limestone, talc, kaolin, montmorillonite or attapulgite are generally used. Highly dispersed silicic acid or highly dispersed absorbent polymers may also be added to improve physical properties. Suitable granular adsorptive granular carriers are porous types such as pumice, brick pulp, sepiolite or bentonite; as non-sorptive carriers, for example, limestone or sand. In addition, a variety of pre-granulated materials of inorganic or organic origin, such as in particular dolomite or comminuted plant residues, may be used.

Particularly preferred application-promoting additives which may lead to a significant reduction in the amount used are furthermore natural (animal or plant) or synthetic phospholipids from the series of cephalins and lecithins such as phosphatidylethanolamine, phosphatidylserine, phosphatidylcholine, sphingomyelin, phosphatidylinositin, phosphatidysolecin, phosphatidysolecin cardiolipin, which can be obtained, for example, from animal or plant cells, in particular from the brain, heart, liver, yolk or soybeans. Commercially available mixtures are, for example, phosphatidylcholine mixtures. Synthetic phospholipids are, for example, dioctanoylphosphatidylcholine and dipalmitoylphosphatidylcholine.

Suitable surfactants are, according to the type of active compound to be treated, of the formula I, non-ionic, cationic and / or anionic surfactants, with good emulsifying, dispersing and wetting properties. Surfactants are also understood as meaning mixtures of surfactants.

Suitable anionic surfactants can be both so-called water-soluble soaps and water-soluble synthetic surfactants.

Soaps include alkali metal, alkaline earth metal or optionally substituted ammonium salts of higher fatty acids (C 10 -C 22), or salts of sodium or potassium oleic acid or stearic acid, or mixtures of natural fatty acids which they are obtained, for example, from coconut oil or tallow. Mention should also be made of mixtures of methyl taurine with fatty acids.

However, so-called synthetic surfactants are used more frequently, especially fatty sulfonates, fatty sulfates, sulfonated benzimidazole derivatives or alkylarylsulfonates.

Fatty sulfonates or sulfates are generally present in the form of alkali metal, alkaline earth metal or optionally substituted ammonium salts and contain an alkyl radical of 8 to 22 carbon atoms, the alkyl radical may also include an alkyl portion of the acyl radicals, such as e.g. the sodium or calcium salt of the ligninsulphonic acid dodecylsulphuric acid ester or a mixture of sulphated fatty alcohols which have been made from natural fatty acids. Also included are salts of sulfuric acid esters and sulfonic acids of fatty alcohol adducts with ethylleoxide. The sulfonated benzimidazole derivatives preferably contain 2 sulfo250237 new acid residues and a fatty acid residue of up to 22 carbon atoms.

Alkylarylsulfonates are, for example, sodium, calcium or triethanolammonium salts of dodecylbenzenesulfonic acid, dibutylnaphthalenesulfonic acid, or a naphthalenesulfonic acid-formaldehyde condensation product.

Corresponding phosphates, such as, for example, phosphoric acid ester salts of 4-14 moles of ethylene oxide with p-nonylphenol, are also suitable.

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

Other suitable non-ionic teusides are the water-soluble adducts of polyethylene oxide to propylene glycol, ethylenediaminopolypropylene glycol and C1-C10 alkylpolypropylene glycol containing 20 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups. The compounds generally contain from 1 to 5 units of ethylene glycol per propylene glycol unit.

Examples of nonionic surfactants include nonylphenolpolyethoxyethanols, castor oil polyglycol ethers, polypropylene adducts with polyethylene oxide, tributylphenoxypolyethoxyethanol, polyethylene glycol and octylphenoxypolyethoxyethanol.

Also suitable are fatty acid esters of polyoxyethylene sorbitan, such as polyoxyethylene sorbitan trioleate.

The cationic surfactants are in particular quaternary ammonium salts which contain at least one alkyl radical having 8 to 22 carbon atoms as substituents on the nitrogen atom and, as further substituents, lower or halogenated alkyl, benzyl or lower hydroxyalkyl radicals. These salts are preferably in the form of halides, methyl sulfates or ethyl sulfates, such as stearyltrimethylammonium chloride or benzyl di- (2-chloroethyl) ethylammonium bromide.

Surfactants common in the preparation of such compositions are described, inter alia, in the following publications:

MC Cutcheon's Detergents and Emulsifiers Annual BC Publishing Corp., Ringewood, New Jersey, 1981.

Helmut Stache ,, Tensid - Taschenbuch “Caer Hauser - Verlag Munich / Vienna 1981.

Agrochemical compositions generally contain 0.1 to 99% of active compound of the formula I, in particular 0.1 to 95% of active compound of the formula

99.9 to 1%, in particular 99.8 to 5% of a solid or liquid additive and 0 to 25%, in particular 0.1 to 25% of surfactants.

While concentrated formulations are preferred on the market, the end consumer generally uses dilute formulations.

These compositions may also contain other additives, such as stabilizers, anti-foaming agents, viscosity regulators, binders, adhesives, as well as fertilizers or other active ingredients, to achieve special effects.

Such agrochemical compositions are part of the present invention.

The following examples serve to illustrate the invention in more detail without limiting the scope of the invention in any way. Percentages and parts refer to weight.

Examples illustrating the method of production of active ingredients:

Example 1 ad II1

Preparation of 1- (1H-1,2,4-triazol-1-yl) -2- (2,4-dichlorophenyl) -3-fluoropentan-2-ol

a) Production of the starting material, i.e. 1- (2,4-dichlorophenyl) -2-fluorobutanone

To a mixture of 77 g of 1- (2,4-dichlorophenyl) -2-bromobutanone and 500 mg of 18-crown-6 in 750 ml of absolute acetonitrile is added 31 absolute potassium fluoride and the mixture is slowly heated to 100-110 ° C with stirring. . After about 48 hours, the reaction is complete (check by gas chromatography or NMR spectrum).

The reaction solution was then poured onto 2 liters of ice water and extracted several times with diethyl ether. The combined extracts were washed with water, dried over sodium sulfate and evaporated. Yield 57 g oily for 250237

(a) Preparation of the starting material, ie 1- (2,4-dichlorophenyl) -2-bromo-2-fluoroethanone duct [coupling constant H — F 50 Hz],

Boiling point 77-78 ° C / 0.8 Pa.

b) Production of another starting material, ie 2- (2,4-dlchlorophenyl) -2- (1-fluoropropyl) oxirane

Cl /

80 g of sodium hydride are suspended in 300 ml of absolute dimethylsulfoxide. 68 g of trimethyloxosulfonium iodide are added in portions to the suspension obtained under a nitrogen atmosphere with stirring. After the evolution of hydrogen ceased and the exothermic reaction subsided, the mixture was stirred at room temperature for 2 hours. A solution of 57 g of 1- (2,4-dichlorophenyl) -2-fluorobutanone in 100 ml of tetrahydrofuran is then added dropwise over 30 minutes, the resulting mixture is stirred for 3 hours and then diluted to 5-fold with ice water and extracted several times with diethyl ether. The combined extracts were washed with water, dried over sodium sulfate and freed of solvent in vacuo. Yield: 55 g as a brown oil.

(c) Production 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-butoxide in 500 ml of dimethylformamide is stirred for 20 hours at a temperature of 80 ° C. The reaction solution was cooled to room temperature, poured onto 2 liters of ice water, extracted several times with diethyl ether. The combined extracts were washed with water, dried over sodium sulfate and concentrated. The yield of 1- (1H-1,2,4-triazol-1-yl) -2- (2,4-dichlorophenyl) -3-fluoropentan-2-ol was 26 g as colorless crystals. Mp 204-206 ° C.

Example H 2

Preparation of 1- (1H-1,2,4-triazol-1-yl) -2- (2,4-dichlorophenyl) -3- (4-chlorophenoxy) -3-fluoropropan-2-ol

To a solution of 20.7 g of α-fluoro-2,4-dichloroacetophenone in 100 ml of carbon tetrachloride, a solution of 16 g of bromine in 100 ml of carbon tetrachloride is added at a temperature of 40 ^° C to 45 ° C. After about 1 hour, the brown solution discolored. The solution was stirred for a further 1 hour and then extracted with aqueous sodium bicarbonate and evaporated in vacuo. The oily residue is then distilled under high vacuum. Yield 17 g., Boiling point 89-92 ^C C / 2 mmHg.

b) Production of additional starting material, i.e. 1- (2,4-dichlorophenyl) -2- (4-chlorophenoxy) -2-fluoroethanone

Cl

12.8 g of chlorophenol and 13.8 g of potassium carbonate were stirred for 1 hour in 200 ml of acetone. 28 g of 1- (2,4-dichlorophenyl) -2-bromo-2-fluoroethanone in 50 ml of acetone are added dropwise to this suspension, and the mixture is refluxed for 3 hours. After cooling to room temperature, the colorless precipitate was filtered off, the acetone was removed in vacuo and diethyl ether was added. The ether solution was washed with water, dried over sodium sulfate, filtered and the filtrate was concentrated.

The oily crude product crystallized upon digestion with n-hexane. Yield 21.5 g as yellowish crystals. Mp 85-87 ° C.

(c) Production of other starting material:

2- (2,4-dichlorophenyl) -2- (4-chlorophenoxyfluoromethyl) oxirane

Cl _r .J

ClC '^ —Cl' ' \ W

9 g of 80% sodium hydride are stirred under a nitrogen atmosphere in 80 ml of dimethylsulfoxide and 10.3 g of trimethyloxosulfonium iodide are added in portions. After the exothermic reaction has ceased, the mixture is stirred for 1 hour at room temperature, then a solution of 2- (2,4-dichlorophenyl) -2- (4-chlorophenoxy) -2-fluoroethanone in 30 ml of tetrahydrofuran is added dropwise, the resulting mixture is further stirred 5 hours at 25-30 ° C and then poured over 1 liter of water. The product was extracted with diethyl ether, the extracts washed with water, dried over sodium sulfate, filtered and the filtrate concentrated. Yield 15 g as a yellowish oil.

(d) Production of the final product:

A solution of 2- (2,4-dichlorophenyl) -2- (4-chlorophenoxyfluoromethyl) oxirane (13 g), 1,2,4-triazole (4 g) and potassium tert-butoxide (0.5 g) in DMF (100 ml) was stirred at 80-50 for 15 hours. After cooling to room temperature, the reaction solution was poured into 500 ml of water, whereupon the crude product precipitated as an oil which was extracted with diethyl ether, the combined extracts were washed with water, dried over sodium sulfate, filtered and concentrated. 11 g of oily crude product, which crystallizes on digestion with n-hexane, yields 7 g of pure product, m.p. 155 DEG-157 DEG C .;

Example H3

Preparation of 1- (1H-1,2,4-triazol-1-yl) -2- [p- (4-chlorophenoxy) phenyl] -2-methoxy-3-fluoropropane

(Compound No. 34)

To 0.7 g of a sodium hydride dispersion (55% in mineral oil) in 20 ml of dimethylformamide, a solution of 5 g of 1- (1H-1,2,4-triazol-1-yl) -2- was added dropwise under stirring under nitrogen. p- (4-chlorophenoxy) phenyl [-3-fluoropropan-2-ol, 25 ml dimethylformamide and 3 ml absolute tetrahydrofuran.

The mixture was stirred until the hydrogen evolution had ceased at 30 ° C. The reaction mixture was then allowed to cool to room temperature and 1 ml of methyl iodide was added dropwise. The reaction mixture was stirred at room temperature for about 12 hours, then poured into saturated sodium chloride solution and extracted three times with ethyl acetate. The combined extracts were washed twice more with dilute sodium chloride solution, dried over sodium sulfate, filtered, and concentrated. The crude product was purified by column chromatography on silica gel (eluting with dichloromethane: methanol 9: 1).

Compound No. 34 is obtained as a highly viscous oil. Yield 5 g, i.e. 96% of theory. n _D ⁵⁰ = 1.5998.

The following compounds can also be prepared in an analogous manner:

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Compounds of formula

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Combining Ar R t R 3 X physical constants to a number

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Combining Ar Rj R ₃ X physical constants to a number

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Examples illustrating the composition and preparation of compositions for liquid active substances of formula I (% =% by weight)

Fl. Emulsion concentrate

and) (b) C) active ingredient from the table calcium dodecylbenzene- 20 ° / o 49% 50% sulfonic acids of castor oil polyethylene glycol ether (36 mol 5% 8% 6% ethylene oxide) tributylphenylpolyethylene glycol- 5% - - ether (30 mol ethylene oxide) - 12% 4% cyclohexanone - 15% 20% mixture of xylenes 65% 25% 20%

Emulsions of any desired concentration can be prepared from such concentrates by diluting with water.

F2. Solutions

and) (b) C) (d) active substance from table 80% 10% 5% 95 ° / o ethylenglycolmonoethyl- ether 20% - - polyethylene glycol (molecular weight 400) - 70% - - N-methyl-2-pyrrolidone - 20% - - epoxidized coconut oil - - 1% 5% petrol (boiling range 160-190 ° C) - - 94% -

These solutions are suitable for applications in the form of minimal drops.

F3. Granulate active ingredient from table kaolin highly dispersed silicic acid attapulgit _a) _____%

%

b)%

%

The active substance is dissolved in methylene chloride, the solution is sprayed onto the carrier and the solvent is then evaporated off under vacuum.

F4. Dust:

and) (b) active substance from table 2% 5 o / o highly dispersed acid siliceous 1% 5% talc 97% - kaolin - 90%

By thoroughly mixing the carrier substances with the active substance, a directly usable dust is obtained.

Examples illustrating the composition and preparation of solid carrier compositions of Formula I:

(% ~ o / o by weight)

F5. Wettable powder:

and) (b) C) active substance from table 25% 50% 75% ligninsulfon sodium acid 5% 5% - sodium lauryl sulfate 3% - 5% natriumdiisobutylnaftalen- sulfonate - 8 ° / o 10% octylphenolpolyethylene glycol- ether (7 to 8 moles of ethylene oxide) - 2% - highly dispersed acid siliceous 5% 10 o / _o 10% kaolin 62 27% - The active ingredient is well mixed with ingredients calcium dodecylbenzenesulfonic acid and the mixture is ground well in a suitable mill. acid 3% nu. A wettable powder is obtained which can be used castor oil polyglycol ether Dilute with water to suspensions each required (35 moles of ethylene oxide) 4 O / o concentration. cyclohexanone 30% mixture of xylenes 50% F6. bulsion concentrate: active substance from table 10% From this concentrate can be produced by diluting the emulsion with water each required octylphenolpolyethylene glycol ether concentration. (4 to 5 moles of ethylene oxide) 3% F7. Dust: and) (b) active substance from table 5% 8 o / _o talc 95% - kaolin - 92%

The active ingredient is mixed with the carrier and ground in a suitable mill. A directly usable dust is thus obtained.

F8. Granules obtained by extrusion:

active ingredient from table 10% lignin sulphonic acid sodium salt 2% carboxymethylcellulose 1% kaolin 87%

The active ingredient is mixed with the ingredients, ground and moistened with water. This mixture is processed on an extruder and then dried in an air stream.

F9. Coated granulate:

active ingredient from table 3% polyethylene glycol (molecular weight 200) 3% kaolin 84%

The finely divided active substance is uniformly applied to a kaolin moistened with polyethylene glycol in a mixer. In this way, the coated granulate is dust-free.

F10. Suspension concentrate:

active substance from table 40 O / o ethylene glycol 10 O / o uonylphenolpolyethylene glycol ether (15 mol ethylene oxide) 6 o / o ligninsulfonic acid sodium salt 10 O / o carboxymethylcellulose 1 O / o 37% aqueous formaldehyde solution 0.2% silicone oil in the form of 75% aqueous emulsion 0.8% water 32 O / o

The finely divided active ingredient is intimately mixed with the ingredients. This gives a suspension concentrate from which suspensions of any desired concentration can be prepared by diluting with water.

Examples illustrating biological activity:

5 0 2.3 7

Example 1 and d Β 1.

Effect against grass rust (Pucciuia graminis) on wheat

a) Rozidally-protective effect

Wheat plants are sprayed with a suspension made from a wettable powder to effect the substance (concentration 6 days after sowing)

After 24 hours, the treated plants are infected with a uredospore suspension of grass rust. After incubation for 48 hours at 95-100% relative humidity and a temperature of about 20 ^° C, the infected plants are placed in a greenhouse at a temperature of about 22 ° C. infection.

b) Systemic effect

Wheat plants are covered 5 days after sowing with a suspension made of wettable powder of the active ingredient (0.008% active ingredient based on soil volume). After 48 hours, the treated plants are infected with a fungal uredospore suspension. After incubation for 43 hours at 95-100% relative humidity and at about 20 ° C, the infected plants are placed in a greenhouse at about 22 T. Assessment - development of rust stacks is carried out 12 days after infection.

The compounds of the table show a very good action against Puccinia rust. Untreated but infected control plants show 100% Pucclnia rust attack. Among others, compounds 1-22 suppress Puccinia rust infestations to 0-5% by 23-28 and 30-33.

Example 1. a d B 2

Effect against Cercospora arachidicola on. peanuts

a) A residual-protective effect of up to 15 cm tall groundnut plants is sprayed oily with a suspension made of wettable powder of the active ingredient (0.006% active ingredient) and after 48 hours the plants are infected with a conidia suspension of fungi. The infected plants are incubated for 72 hours at a temperature of about 21 [deg.] C. under high humidity and then placed in a greenhouse until the spots on the leaves show up. Assessment of the fungal effect is performed 12 days after infection based on the number and size of the spots occurring.

Compared to untreated but infected plants (number and size of spots = 100%), peanut plants treated with the active substances in the table show a strongly reduced attack on the fungus Cercospora. Thus, compounds 1 to 9, 13, 16, 17, 18, 19, 22, 23 to 28 and 31 prevent the staining from occurring almost completely (0-10% attack) in the above experiments.

Example B 3

Effect on powdery mildew (Erysiphe gra.minis) on barley

a) R j ektivní ektivní ot ektivní ot ot ot ektivní ot ot

About 8 cm high barley plants are sprayed with a suspension made from a wettable powder of the active ingredient (0.002% active ingredient). After 3-4 hours, the treated plants are dusted with conidia of the fungus. Thus infected barley plants are placed in a greenhouse at a temperature of about 22 ° C and the fungal infestation is assessed after 10 days.

bj Systemic effect

About 8 cm high barley plants are covered with a suspension made from a wettable powder of active ingredient (0.006% active ingredient per volume of soil). Care is taken that the suspension does not come into contact with the aerial parts of the plants. After 48 hours, the treated plants are dusted with conidia of the fungus. Infected barley plants are exposed in a greenhouse at about 22 ° C and after 10 days the fungal infestation is assessed.

The compounds of formula I show good activity against Ervsiphe. Untreated. however, infected control plants show 100% Erysiphe attack. Many other compounds of the table suppress compounds 1 to 10, 13, 14, 15, 16, 17, 18, 19, 21, 22, 23-28 and 30 to 33 barley fungus infestations to 0 to 5%, especially Compound No. 2 completely prevents fungal attack.

Example B 4

R f ^^ (^ d ^ u ^] ^ No - p ^ ⁱ otektivní activity against apple scab (Venturia inaequalis) on apple shoots

Apple seedlings with fresh shoots of 10 to 20 cm in length are sprayed with a suspension made from a wettable powder of the active ingredient (0.006% active ingredient). After 24 hours, the treated plants are infected with a fungal conidia suspension. The plants are then incubated for 5 days at 90-100% relative humidity for a period of time. they are placed in a greenhouse at 20-24 ° C for a further 10 days. Scab infestation is assessed 15 days after infection. Compounds 1 to 6, 8, 9, 13, 15, 16, 17, 19, 24, 26 to 28 and 30 to 33 control disease infestations to less than 10%. In contrast, untreated but infected control shoots were completely attacked (100% attack).

CI (A)

Example Β 5

Effect against gray mold (Botrytis pinerea) on bean

Residual-protective effect

About 10 cm tall bean plants. are sprayed with a suspension which was prepared from a wettable powder of the active ingredient [0.02% active ingredient].

After 48 hours, the treated plants are infected with a conidia suspension of the fungus. After incubating the infected plants for 3 days at 95-100% relative humidity and 21 ° C, the fungal infestation is assessed. The compounds of the table suppress fungal infection very strongly in many cases. At a concentration of 0.02%, for example, compounds 1 to 6, 8, 9, 13, 14, 17, 18, 19, 21, 24, 26, 27, 28 and 30 proved to be completely effective. .

In untreated but infected bean plants the infection with gray (Botrytis cinerea) was 100%.

Example B 6

Activity against Pyricularia oryzane on rice plants has a protective effect

After two weeks of cultivation, the rice plants are sprayed with a suspension prepared from a wettable powder of the active ingredient (concentration 0.002%). After 48 hours, the treated plants are infected with a conidia suspension of the fungus. After 5 days of incubation at 95-100% relative humidity and 24 ° C, the degree of fungal infestation is assessed.

Rice plants that have been treated with a spray suspension containing as an active ingredient any of the compounds of the table, such as Compound No. 13 or 19, exhibit a fungal infestation of less than 10% compared to untreated control plants (100% attack).

Comparative experiments:

For comparison with the active compounds according to the invention, the following structurally closest comparable substances were tested in the following tests:

Compound No. 2 (according to the invention) (i)

compound No. 150 [known from European patent no.

594)

Compound A of the present invention differs from the prior art comparative compound (i) in only one structural element, i.e., a fluorine atom on the carbon atom at the 3 (* C) position of the aliphatic carbon chain. The introduction of this fluorine atom at a specific coordination site of the molecule makes a significant difference in physicochemical behavior:

substance solubility in water at 25 ° C

A 0.05 ppm and 40.0 ppm

Thus, surprisingly, Compound A according to the invention exhibits a lower water solubility and correspondingly increased lipophilicity compared to the previously known Compound (i) by a factor of 800. These physicochemical properties of the active ingredient play an important role in application to the plant. At high water solubility, the active substance is easily washed off the leaves, while the low water solubility associated with a correspondingly high lipophilicity, the penetration potential of the active substance to penetrate the lipophilic layer of the leaves increases, thereby improving the plant uptake and application rate fungicidal effect.

This results in a prolonged interval of taking part throughout the treatment period and thus a reduction in the total amount used throughout the entire vegetation season.

In the following experiments carried out under real conditions (field trial) the long-term activity of the above-mentioned substances A and i was tested.

Test 1

Long-term effect against rust (Puccinia hordei) on barley

Two spatially separated field plots with a cultivated area of 4 m ^{2 each} are sown with barley and, after rooting, sprayed with a spray suspension prepared from a wettable powder (62.5 g of active substance per ha). 24 hours after application, the plants are inoculated with a standard suspension of uredospore of Puccinia hordei. These parcels are then exposed for several weeks to natural weather conditions such as day and night rhythm, sunlight, rainfall, etc., and the development of rust stacks on the surface of plant leaves is evaluated and compared to development. on untreated but also infected plants grown under field conditions. The experiment is repeated three times. Evaluation of the experiment is carried out 5 weeks after application of the active substance. The results of the experiment are summarized in Table 1 below.

Test 2

Long-term effect against rust [Puccinia triticina] on wheat

Two spatially separated field plots with a cultivated area of 4 m ^{2 each} were sown with wheat and, after rooting, sprayed with a spray suspension prepared from a wettable powder (62.6 g of active ingredient per ha). 24 hours after application, the plants are inoculated with a standard suspension of uredospore of the fungus Puccinia triticina. The plots are exposed for several weeks to natural weather conditions, such as daytime and night rhythm, sunlight, rainfall, etc., and the development of rust clusters on the first leaves of plants throughout the experiment is examined and compared with the development of rust clusters on untreated but also infected plants grown under field conditions. The experiment is repeated three times. Evaluation of the experiment is carried out 5 weeks after application of the active substance. The test results are summarized in Table 1 below.

Table 1

Test results:

tested fungal infestations 5 weeks after application of test 1 test 2

Puccinia hordei on barley Puccinia triticina on wheat

relative to control absolute relative to control absolute AND 11% 10% 8% 7% and 71% 68% 52% 48% No- treated control 100% 96%  100% 82%

In the tests 1) and 2) described above against phytopathogenic fungi, compound A (a compound of the invention) still provides virtually complete protection of the crop plant (fungus attack 11% and 8%; control 100% / o) even 5 weeks after application. infestation with said species of phytopathogenic fungi, while the immediate closest comparable compound (i) known in the art has no fungicidal effect that would be useful for practical application under field conditions (fungal attack of 71% and 52%, respectively).

Thus, the compound (A) of the invention in this field experiment. clearly exceeds the reference substance. (i) known in the art.

Claims (4)

A fungicidal composition, characterized in that, in addition to the carrier substances or additives, at least one active ingredient is a compound of the formula I ORj H I I Az — CH _{9 —} C — C — F I I Ar R j (I) in which Az is 1H-1,2,4-triazolyl or 1H-imidazolyl, Ar is an optionally substituted aromatic radical selected from the group consisting of phenyl or phenoxyphenyl; R 1 is hydrogen, methyl, C 3 alkenyl or benzyl, and R _i is hydrogen, alkyl having 1 to 4 carbon atoms or phenyl group, each aromatic substituent or aromatic moiety of a substituent is optionally mono- or polysubstituted by halogen and / or methyl group, or an acid addition salt, quaternary azoliovou salt or complex with metal. 2. A composition according to claim 1, wherein the active ingredient is a compound of formula (I) selected from the group consisting of 1- [1H-1,2,4-triazol-1-yl] -2- (2,4-dichlorophenyl) -3-fluorobutan-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-fluoropentan-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-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. 3. A composition according to claim 1, wherein the active ingredient is a compound of formula (I) selected from the group consisting of OF THE INVENTION 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-fluorohexan-2-ol, 1- (1H-1,2,4-triazol-1-yl) -2- [p- (4-chlorophenoxy) -2-methylphenyl] -2-hydroxy-3-fluoropropane. 4. A process according to claim 1, which comprises reacting an oxirane of the formula II АГ .- (/ '. CH' fi ^- C ^{- Rg} I ^J in which Ar and R.n are as defined in 1, with an azole of formula III M — Az (III) in which Az is as defined in point 1, and M is hydrogen or a metal atom, first to form a compound of formula Ia OH Ar — C — Cfy — Az (Ia) H — C — R3 AND F in which Ar, Az and Rj are as defined above, and optionally the alcohol of formula Ia is converted in a conventional manner, for example by reaction with a compound of formula IV Rx-W (IV) wherein R1 is as defined in point 1, W represents a hydroxyl group or a leaving group, to an ether of formula I.