CS241521B2 - Method of new arylphenylethers derivatives production - Google Patents

Description

The present invention relates to a process for the preparation of the novel substituted arylphenyl ethers derivatives of formula (I) below, as well as their acid addition salts and their copper complexes. The novel aryl phenyl ether derivatives are used to combat phytopathogenic fungi in plant protection.

The novel valuable arylphenyl ether derivatives of the invention correspond to the general formula I

I I c- o / - N, -J (n in which

Y is -CH- or -N =,

R _a and R _b are each independently hydrogen, halogen, C 1 -C 3 alkyl or methoxy,

U and V are independently C 1 -C 3 alkyl or together are one of the following alkylene bridges

R1 and R2 are each independently hydrogen, C1-C3alkyl or -CH2-Z-Rr, where

Z is oxygen or sulfur, and R 7 is hydrogen, C 1 -C 3 alkyl, C 3 -C 3 alkenyl, pin alkenyl, phenyl, chloro or methyl substituted phenyl, benzyl or chloro or methyl substituted a benzyl group,

R 5, R 6 and R 5 are each independently hydrogen or (C 1 -C 3) alkyl, the total number of carbon atoms in R 1, R 1 and R 5 not exceeding 6, and

Ar represents a group of the formula

whereas

R _c , R _d and R _e are each independently hydrogen, halogen, C 1 -C 4 alkyl, C 1 -C 3 alkoxy, trifluoromethyl or nitro, and also include acid addition salts of the compounds of formula (I) and complexes of the compounds of formula I with copper.

Depending on the number of carbon atoms mentioned, the term "alkyl" alone or as a component of another substituent is, for example, the following groups: methyl, ethyl, propyl, butyl, etc., as well as their isomers such as isopropyl, isobutyl, tert-butyl, sec-butyl, etc. .

The term "alkenyl" means, for example, 1-propenyl, allyl, 1-butenyl, 2-butenyl or 3-butenyl.

Halogen is herein to be understood as fluorine, chlorine, bromine or iodine, preferably chlorine or bromine.

The present invention relates to a process for the preparation of the free compounds of the formula I, their addition salts with inorganic and organic acids as well as their complexes with copper salts.

Salts are in particular addition salts with physiologically acceptable inorganic or organic acids (in accordance with the intended use).

Suitable physiologically acceptable inorganic and organic acids are, for example, hydrohalic acids, for example hydrochloric acid, hydrobromic acid or hydroiodic acid, sulfuric acid, phosphorous acid, phosphoric acid, nitric acid or halogenated fatty acids, such as acetic acid, trichloroacetic acid. an acid and oxalic acid or sulfonic acids such as benzenesulfonic acid and methanesulfonic acid.

The copper-compound complexes of formula I consist of a basic organic molecule and an inorganic or organic copper salt, for example, halides, nitrate, sulfate, phosphate, tartrate, copper. The copper cation can be present in the various valencies that it owns.

The compounds of formula (I) are stable oils, resins or solids at room temperature and have very valuable fungicidal properties in plant protection. The compounds can therefore be used in agriculture and related fields to combat phytopathogenic microorganisms.

One of the fungicide groups that is important for use in plant protection is represented by the compounds of formula (I) wherein:

Y is —CH = or —N =,

R _a and R _h are each independently hydrogen, halogen, C 1 -C 3 alkyl or methoxy,

U and V are independently C1-C3 alkyl or together form one of the following alkylene bridges

whereas

R1 and R2 are each independently hydrogen, C1-C3alkyl or -CH2-Z-R7, wherein:

Z is oxygen or sulfur,

R 7 is hydrogen, C 1 -C 3 alkyl, C 3 -C 4 alkenyl, methoxyethyl, phenyl, chloro or methyl-substituted phenyl, benzyl or chloro or methyl-substituted benzyl,

R 1, R 6 and R 5 are each independently hydrogen or C 1 -C 3 alkyl, the total number of carbon atoms in R 5, R 4 and R 5 not exceeding 6, and

where

R _c , R _d and R _e are each independently hydrogen, halogen, C 1 -C 4 alkyl, C 1 -C 3 alkoxy, trifluoromethyl or nitro, as well as their acid addition salts and their copper complexes .

A preferred class of agriculturally useful fungicides are compounds of formula I, including their salts and copper complexes, wherein Y is -CH = or -N =, R _a and R _b are each independently hydrogen, halogen or C 1 -C 3 alkyl. and Ar represents a group of formula

where

R _c , R _d and R _e are each independently hydrogen, halogen, trifluoromethyl or C 1 -C 3 alkyl, and

U and V have the meanings given in formula I.

This group will be referred to as Group Ib.

Within subgroup Ib, those compounds of the formula I are preferred as plant protection fungicides in which U and V are independently C1 -C3 alkyl or together represent one of the following alkylene groups' R. babo j R $ in which

R 1, R 2, R 3, R d and R 5 are each independently hydrogen or C 1 -C 4 alkyl, with the total number of carbon atoms in R 3, R 4 and R 5 not exceeding 6.

This group will be referred to as group 1c.

Another preferred class of agriculturally preferred fungicides are those compounds of formula I wherein Y is —CH— or —N =, Ar is as defined for Formula I, R _a , R _b , R _c , R _d and R _e are independently of each other. each of hydrogen, chloro, bromo, fluoro, methyl, methoxy or nitro, U and V are each independently C 1 -C 3 alkyl or together form the alkylene groups represented by formula I, wherein R 1, R 2, R 5, R 4, R 5 and R 6 independently of one another are hydrogen or C 1 -C 3 alkyl or R 1 is -CH-O-R 7, wherein R 7 is C 1 -C 3 alkyl, C 1 -C 3 alkoxy substituted alkyl C 2 -C 4 alkenyl, C 3 -C 4 alkenyl or phenyl.

This group will hereinafter be referred to as group Id.

Among the fungicides of subgroup Id, those compounds in which U and V together form an unsubstituted or singly substituted ethylene or propylene bridge are particularly preferred.

This group will hereinafter be referred to as Group Ie.

Thus, for example, the following substances belong to particularly advantageous agriculturally useful individual substances:

2- [p- (phenoxy) phenyl] -2- [1- (1H-1,2,4-triazolyl) methyl] -4-methyl-1,3-dioxane,

2- [p- (phenoxy) phenyl] -2- [1- (1H-1,2,4-triazolyl) methyl] -4-ethyl-1,3-dioxane,

2- [p- (phenoxy) phenyl] -2- (1- (1H-1,2,4-triazolyl) methyl) -4-methyl-1,3-dioxolane,

2- [p- (phenoxy) phenyl] -2- [1- (1H-1,2,4-triazolyl) methyl] -4-ethyl-1,3-dioxolane,

2- [p- (4'-Bromophenoxy) phenyl] -2- [1- (1H-1,2,4-triazolylmethyl) -4-ethyl-1,3-dioxolane, [p- (phenoxy) - 2'-methylphenyl] -2- [1- (1H-1,2,4-triazolyl) methyl] -4-ethyl-1,3-dioxolane,

2- [p- (3‘, 4‘-dichlorophenoxy) phenyl] -2- (1- (1H-1,2,4-triazolyl) methyl) -4-methoxymethyl-1,3-dioxolane,

- [p- (3 ', 4'-dichlorophenoxy) phenyl] -2- (1- (1H-1,2,4-triazolyl) methyl) -4-ethyl-1,3-dioxolane, complex 2 - [ p- (4'-chlorophenoxy) phenyl] -2- (1- (1H-1,2,4-triazolyl} methyl) -4-ethyl-1,3-dioxolane with copper sulfate,

2- [p- (4'-chlorophenoxy) -2-methylphenyl] -2- (1- (1H-1,2,4-triazolyl) methyl] -4-methyl-1,3-dioxolane, salt 2 - [p- (phenoxy) -2'-methylphenyl] -2- [1- (1H-1,2,4-triazolyl) methyl] -4-ethyl-1,3-dioxolane with nitric acid,

2- (p- (4'-chlorophenoxy) phenyl] -2- [1- (1H-1,2,4-triazolylmethyl) -4-ethyl-1,3-dioxolane.

According to the invention, the compounds of the formula I and their acid addition salts as well as their copper complexes are prepared by the preparation of a carbonyl group in a compound of the formula IV

in which

Ar, R _a , R _b and Y, as defined above, are converted in an organic solvent at a temperature of 60 to 160 ° C by reaction with a trialkyl ester of a C 1 -C 12 orthocarboxylic acid, wherein the C 1 -C 12 alkyl groups are optionally substituted with halogen or alkoxy of 1 to 6 carbon atoms, or in the presence of an acid, by reaction with at least two moles of a monovalent alcohol of formula Va

U — OH (Va) wherein

U is as defined above, or by reaction with a diol of formula Vb

HO — U ---- V — OH (Vb) wherein

U and V have the meanings given above, per group of formula V

-, c o o

I I

U ---- V (V) in which

U and V have the meanings given above, whereupon the optionally obtained free compound is converted by reaction with an organic or inorganic acid into an acid addition salt, the obtained acid addition salt is optionally converted by reaction with an alkali metal carbonate, bicarbonate or hydroxide or optionally the free compound obtained or the acid addition salt obtained is converted into a copper complex by reaction with a copper salt.

In the process of the invention, intermediates and end products can be isolated from the reaction mixture and optionally purified by generally conventional methods, for example, extraction, crystallization, chromatography, distillation, etc.

The conversion of the carbonyl group in the compounds of formula IV to the group of formula V is carried out by reaction with a trialkyl of 1 to 12 carbon atoms in the alkyl of an orthocarboxylic acid, the alkyl of 1 to 12 carbon atoms being optionally substituted by halogen or alkoxy of 1 to 6 carbon atoms; in the presence of an acid with at least 2 mol of a monovalent alcohol of formula U-OH (Va) to give compounds of formula I wherein U and V are

With the same, optionally substituted groups of 1 to 12 carbon atoms, or by reaction with a diol of formula Vb

HO-U ------ V-OH (Vb) to give compounds of formula I wherein U and V together represent some of the alkylene bridges defined above. Hereby, the symbols Ar, Y, R _a, R _b, U and V as defined under formula I.

This ketalization reaction can be carried out according to already known ketalization reactions, for example analogously to the method of 2-bromomethyl-2,4-diphenyl-1,3-dioxolane, cf. Synthesis, 1974 (I), 23j.

In a preferred embodiment of the ketalization, both reactants are heated for several hours together with the reagent forming the mixture in a conventional organic solvent at reflux. Suitable azeotropic mixtures are, for example, benzene, toluene, xylene, chloroform or carbon tetrachloride, and the addition of a strong acid such as p-toluenesulfonic acid may be advantageous to accelerate the reaction. Useful organic solvents in this case are, for example, aromatic hydrocarbons such as benzene, toluene, xylene etc., saturated hydrocarbons such as n hexane or saturated halogenated hydrocarbons such as 1,1,1-trichloroethane.

Other methods of ketalization are also feasible, for example by reacting a ketone of formula IV, which is ketalized with an alcohol or phenol different from the alcohols or diols of formula Va or Vb, and this is then recrystallized by reaction with excess alkanol of formula Va, optionally with a diol of formula Vb to form compounds of formula I.

The compounds obtained according to the invention can be converted into other compounds of formula I by methods known per se.

Thus, for example, the obtained compounds can be recrystallized to other compounds of formula I. For example, in compounds of formula I in which U and V are the same and are optionally substituted C 1 -C 12 alkyl radicals, they can be replaced by reaction with 1 mol of another optionally substituted C 1 -C 12 alkanol of formula Vc

V-OH (Vc) group U by one group V or by reaction with a diol of formula Vb both groups U by a divalent radical. The re-crystallization is carried out in a customary manner, for example in the presence of an acidic condensing agent such as mineral acid, sulfonic acid or a strong carboxylic acid, for example hydrochloric or hydrobromic acid, sulfuric acid, p-toluenesulfonic acid or trifluoroacetic acid, preferably under distillation or azeotrope-distillation removal of easily boiling reaction products.

In addition, optionally additional substituents can be introduced into the carbocyclic aryl moieties of the compounds obtained by the process of the invention into the radical Ar and / or R a _and R _b , respectively. Thus, for example, halogen can be introduced by reaction with a halogen in the presence of a Lewis acid such as iron (III), zinc or antimony (III) halide or N-chlorosuccinimide.

Further, nitro groups can be reduced, for example with suitable complex hydrides, for example lithium aluminum hydride, to amines, then these amines can be diazotized, for example by treatment with nitrous acid, and the diazonium formed can then be replaced by halogen or alkoxy. Likewise, halogen can be replaced by an alkyl group by reaction with a metal alkyl derivative, for example an alkyl lithium or alkyl magnesium halide.

When the compounds of the formula I are obtained in the form of bases, they can be converted into the corresponding salts by treatment with inorganic or organic acids or they can be converted into metal complexes of the formula I by treatment with preferably equimolar amounts of metal salts. Conversely, the salts of formula I can be converted, for example, by reaction with an alkali metal carbonate or bicarbonate or an alkali metal hydroxide into the free bases of formula I.

The starting ketones of formula IV may be prepared by the haiogenation of methylarylketones of formula XIV to give compounds of formula XV

CO-CH3-Each (xv) and further reacting compounds of formula XV with an azole of formula II

Msz / ~ = N

V (l / f where

Me means metal,

Y is -CH = or -N = and Hal is preferably chloro or bromo, while

Ar, R _a , R _b are as defined above. The described process variants are also an object of the invention.

In all the described ketalization reactions of a ketone with substituted α, β- or α, γ-diol, predominantly mixtures of diastereomers of the resulting ketal are formed. Correspondingly, mixtures of diastereomers of the end products of the formula I are generally formed from the starting ketones. The compounds of the formula I can exist, for example, in the following two diesteromeric forms

Ar-O-O-CO-CH3

Rs (λιν:

Ar- O

Ar-O.

p

O ^ O L

types

R.

with.

o ^c n

AJ -¾ ^Y

Ή

CH 2 (XVI) (xvin

The type A configuration is referred to herein as the "trans" -isomer.

I_Λ

Ή

CH 2 Rcf.

(λ \ Ι! I)

The symbols in the spatially represented patterns have the following meanings:

^> o «b8B ^{= after} ___ = h. ,,,, = in front of the plane shown

The type B configuration is also referred to as the "cls" isomer in the following.

Separation of the two diastereomers can be performed, for example, by traction crystallization or by chromatography (thin layer chromatography, dilution chromatography, column chromatography, high pressure liquid chromatography, etc.). Both of these isomers show different biological activity. Generally, mixtures of diastereomers are used for practical purposes.

The invention relates to all isomeric compounds of the formula I, their salts and their metal complexes.

A process for the preparation of the compounds of formula I is part of this invention.

Some of the starting materials and intermediates used in the process of the invention are known compounds or can be prepared by methods known per se.

1- (β-aryl) ethylimidazolyl ketals in which aryl is substituted phenyl or naphthyl are cited as fungicides in the following publications:

U.S. Patent Nos. 3,575,999,

(+420) 936 470, (+420) 4101 664,

101,666 and 4,156,008.

Surprisingly, it has been found that the compounds of formula I have a very favorable spectrum of microbicidal activity against phytopathogenic fungi and bacteria for practical requirements and further possess antifungal and / or anticulsive properties which establish their utility as drug active ingredients. Thus, these compounds have very advantageous curative, preventive and systemic properties in plant protection and can be used to protect crop plants. The active substances of the formula I can control or destroy the occurring microorganisms on plants or on parts of plants (such as fruits, flowers, (XI X) leaves, stems, tubers and roots) of various useful plants, while remaining protected against such microorganisms. later grown parts of plants.

The active substances are particularly active against phytopathogenic fungi belonging to the following groups:

Ascomycetes, such as

Venturia,

Podosphaera,

Erysiphe,

Monilinia,

Uncinula,

Basidiomycetes such as

Hemileia,

Rhizoctonia,

Puccinia,

Fungi imperfecti such as Botrytis,

Helminthosporium,

Fusarium,

Septoria,

Cercospora and Alternaria.

In addition, the compounds of formula I are also systemically active. They can also be used as mordants for the treatment of seed (fruits, tubers, grains) and plant seedlings for protection against fungal infections, as well as for phytopathogenic fungi occurring in the soil.

The active compounds according to the invention are particularly well tolerated by crop plants.

The invention therefore also relates to microbicidal compositions, as well as to the use of the compounds of the general formula L for combating phytopathogenic microorganisms, in particular fungi harmful to plants, or preventively preventing the attack of plants.

In addition, the present invention also encompasses the production of agrochemical compositions which consist in the positive mixing of the active ingredient with one or more of the substances described herein, or a group of substances.

The invention also relates to a process for the treatment of plants which is characterized by the application of the compounds of the formula I and of the novel compositions.

Suitable crop plants for the areas of indication described herein include, for example, the following plant species:

cereals such as wheat, barley, rye, oats, rice, sorghum and related plants, beets such as sugar beet, fodder beet, fruit trees bearing fruit with kernels, seeds and berries, such as apple, pear, plum, peach, almond, cherry, strawberry, raspberry, blackberry, legume, such as beans, lentils, peas, soybean, oilseed rape, mustard, poppy, olive tree, sunflower, coconut, castor, cacao, peanut, pumpkin plant, such as pumpkins, cucumbers, melons, fibrous plants such as cotton, flax, hemp, jute, citrus fruit trees such as orange, lemon, tangerine, tangerine, various vegetables such as spinach, lettuce, asparagus, cabbage, carrots, onions, tomatoes, potatoes, peppers, laurel plants such as avocado (Porsea gratissima), cinnamon icecar, camphor, or other plants such as corn, tobacco, butternut, coffee, sugarcane, tea, vine, hops, banana and rubber, as well as ornamental plants (Compositae).

The active compounds of the formula I are used in agriculture usually in the form of compositions and can be applied simultaneously or sequentially with other active compounds, either to the treated area of the plant or to a part of the plants. These other active substances in the case of plant protection products are represented as fertilizers, trace elements or other preparations which influence the growth of the plants. However, they may also be selective herbicides, insecticides, fungicides, bactericides, nematicides, moluscicides or mixtures of several of these preparations, together with, if appropriate, other conventional carriers, surfactants or other additives which improve the application possibilities.

For all of these compositions, suitable carriers and additives may be solid or liquid substances and correspond to non-toxic substances serving in their respective formulations, such as regenerated minerals, solvents, dispersants, wetting agents, adhesives, thickeners or binders.

One preferred method used in agriculture to apply an active compound of formula I or an agrochemical composition to an infected plant is by application to the leaves of the plants. The number of applications and the amount used depend on the disease state for the corresponding disease agent (fungus species). However, the active compounds of the formula I can also be fed to the plant via soil via the root system (systemic effect). However, the compounds of formula I may also be applied to the seeds of the plants (Coating) by either impregnating the seeds with a liquid preparation of the active substance or by providing them with a liquid preparation of the active substance. In addition, other applications are possible in special cases, such as the deliberate treatment of plant stems or buds.

The compounds of the formula I are used in unchanged form or preferably together with auxiliaries customary in the preparation of agrochemical preparations and are therefore processed into emulsion concentrates, paint pastes, sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granules, by encapsulation, for example, into polymeric substances in a known manner. Application procedures, such as spraying, fogging, dusting, sprinkling, coating or watering, as well as the type of compositions, are selected appropriately according to the desired objectives and proportions. A favorable application rate is generally between 50 g to 5 kg of active ingredient per hectare, preferably from 100 g to 2 kg of active ingredient per hectare, in particular 200 g to 600 g of active ingredient per hectare.

Agrochemical compositions containing the active compound of the formula I and optionally a solid or liquid additive and concentrates or other preparations of this type are prepared in a known manner, for example by thoroughly mixing and / or grinding the active compounds with fillers, such as solvents, solid carriers and optionally with surfactants.

Suitable solvents are aromatic hydrocarbons, preferably fractions containing 8 to 12 carbon atoms, such as mixtures of xylenes or substituted naphthalenes, phthalic acid esters such as dibutyl phthalate or dioctyl phthalate, aliphatic hydrocarbons such as cyclohexane or paraffinic hydrocarbons, alcohols and glycols, and their ethers and esters, such as ethanol, ethylene glycol, ethylene glycol monomethyl ether or ethylene glycol monoethyl ether, ketones such as cyclohexanone, strongly polar solvents such as N-methyl-2-pyrrolidone, dimethylsulfoxide or dimethylformamide, and optionally epoxidized vegetable oils such as epo16 xidized coconut oil or soybean 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 absorbent polymers may also be added to improve physical properties. Suitable granular adsorptive carriers for the granulates are porous types, such as pumice, brick pulp, sepiolite or bentonite, as non-sorptive carrier materials, for example limestone or sand. In addition, a large number of pre-granulated materials of inorganic or organic origin, such as in particular dolomite or comminuted plant residues, may be used.

Suitable surface-active compounds are non-ionic, cationic and / or anionic surfactants having good emulsifying, dispersing and wetting properties. Surfactants are also understood as meaning mixtures of surfactants.

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

Soaps include alkali metal, alkaline earth metal, or the corresponding, optionally substituted ammonium salts of higher fatty acids (C 10 -C 22), such as sodium or potassium salts of oleic acid or stearic acid, or mixtures of natural fatty acids, which are obtained, for example, from coconut oil or tallow oil. The fatty acid salts of methyl taurine must also be mentioned.

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

Fatty sulphonates or fatty sulphates generally exist with alkali metals, alkaline earth metals or optionally as substituted ammonium salts and contain an alkyl radical of 8 to 22 carbon atoms, the alkyl also including an alkyl portion of the acyl radicals, such as sodium or calcium lignin sulphonate an acid, a dodecylsulfuric acid ester or a mixture of sulfated fatty alcohols made from natural fatty acids. This also includes salts of sulfuric acid esters and sulfonic acids of fatty alcohol adducts with ethylene oxide. The sulfonated benzimidazole derivatives preferably contain 2 sulfo groups and a fatty acid radical of 8 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.

Also suitable are corresponding phosphates, such as salts of the phosphoric acid ester of the p-nonylphenol adduct with ethylene oxide (4 to 14).

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

Other suitable nonionic surfactants are the water-soluble adducts of polyethylene oxide with polypropylene glycol, ethylenediaminopolypropylene glycol and an alkylpolypropylene glycol of 1 to 10 carbon atoms in the alkyl chain 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 derived from polyoxyethylene sorbitan, such as polyoxyethylene sorbitan trioleate.

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

Surfactants useful in the manufacture of the agrochemical compositions of the invention are described, inter alia, in the following publications: Mc Cutcheon ' s Detergents and Emulsifiers Annual Mc Publishing Corp., Ringwood, New Jersey, 1980 Sisely and Wood, " Encyclopedia of Surface Active Agents " , Inc. New York, 1980.

Agrochemical preparations generally contain from 0.1 to 99% of active compound of the formula I, in particular from 0.1 to 95% of active compound of the formula I, from 99.9 to 1%, in particular from 99.8 to 5% of solid or liquid additives, 25%, in particular 0.1 to 25% of surfactants.

While concentrated formulations are preferred as commercial products, generally dilute formulations are used for the final use.

The agrochemical 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 particular effects.

The following examples serve to illustrate the invention in greater detail without restricting it. Percentages and parts refer to weight.

Examples illustrating the method of production of active ingredients:

Example 1

Preparation of 2- [p- (phenoxy) phenyl] -2- (1H-1,2,4-triazolylmethyl) -4-n-propyl-1,3-dioxolane

C-CH, -N (n-N y-J)

10.3 parts of 1- (p-phenoxyphenyl) -2- (1,2,4-triazolyl-1-yl) ethanone nitrate, 6.1 parts of 1,2-pentanediol, 6.9 parts of p-toluenesulfonic acid, 20 parts of 1- of pentanol and 200 parts of xylene are refluxed for 6 days using a water separator, and after cooling to room temperature, the reaction mixture is washed twice with 200 ml of dilute sodium hydroxide and twice with 200 ml of water each time. The oily residue is chromatographed over a 1 meter silica gel column using ethyl acetate as the eluent, and the oily residue crystallizes slowly after evaporation of the solvent to give beige crystals, mp 68.5-71 ° C.

Example 1a

Preparation of 2- [p- (4‘-chlorophenoxy) -2‘-methylthenyl] -2- [1- (1H-1,2,4-triazolylmethyl)] -4,5-dimethyl-1,3-dioxolane

11.7 parts of 1- [p- (4'-chlorophenoxy) -2'-methylphenyl] -2- (1H-1,2,4-triazolyl) ethanone nitrate, 8.1 parts of 2,3-butanediol 7.5 parts of p-toluenesulfonic acid, 22 parts of 1-pentanol, and 250 parts of chloroform were heated to reflux for 220 hours using a water trap and the resulting water was bound in a trap by means of a molecular sieve. The reaction mixture was washed with water (2.times.250 ml) and then washed with water (3.times.300 ml), the organic phase was dried over sodium sulfate, filtered and the solvent was removed in vacuo. The title compound was obtained as a highly viscous oil.

n _D ^{22 15} = 1.5717.

Example 1 b

Preparation of 2- (p-phenoxyphenyl) -2- [1- (lH-l, 2,4-trialylmethyl)] -4-hydroxymethyl-l, 3-dioxolane .-, / ZrN ¹

16.5 parts of 1- (p-phenoxyphenyl) -2- (1H-1,2,4-triazolyl) ethanone hydrochloride, 10 parts of triethyl orthoformate, 15 parts of glycerine and a catalytically effective amount of p-toluenesulfonic acid are introduced into 250 parts of toluene and the mixture was heated to 100 ° C with stirring. The reaction was continued until no more ethanol and ethyl formate distilled off. The reaction mixture was then cooled to room temperature, washed twice with 250 ml of 2 N sodium carbonate solution and then with water until neutral, dried over sodium sulfate and the solvent was evaporated. The oily residue was purified by silica gel column chromatography using ethyl acetate as eluent. Evaporation of the eluent left a mixture of diastereomers as a very viscous mass which crystallized upon addition of hexane. Melting point 111-122 ° C.

Example 1c

Preparation of 2- [p- (4'-fluorophenoxy) -2'-methylphenyl] -2- [1- (1H-1,2,4-trlazolylmethyl) -1,3-dioxanone

18.7 parts of 1- [p- (4'-chlorophenoxy) -2'-methyl-phenyl] -2- (1H-1,2,4-triazolyl] ethanone nitrate, 9 parts of 1,3-propanedil 6.1 parts of p-toluenesulfonic acid and 300 parts of diethylene glycol dimethyl ether were heated to reflux with stirring, and the reaction water was distilled off azeotropically, and the reaction was terminated when the temperature reached 160 ° C by distillation. The reaction mixture is cooled to room temperature, poured onto 500 ml of water, extracted three times with 150 ml of ethyl acetate each time, the organic phases are combined, washed once with 200 ml of dilute sodium hydroxide solution and then with water until neutral, dried over sodium sulfate and The residue was chromatographed on a silica gel column using ethyl acetate as eluent to give beige crystals, m.p. 127-137 ° C.

The following reaction products can also be prepared in an analogous manner (unless otherwise stated, mixtures of diastereomers with different ratios) of formula I are obtained:

In the following tables, the symbol A for the type A and B diastereomers has the same meaning as for the type B diastereomer.

Table 1

Compounds of formula XXI

including isomeric forms:

compound number Rio Y salt physical data 1.1 H N - 1.1. Mp 100-102 ° C 1.2 H N HNOs 1.3 H CH - 1.4 CH3 N - 1.1. Mp 85-92 ° C 1.5 CHs N HCl 1.6 ch ₃ N CuCl2 1.7 CH3 CH - 1.8 CH3 N Mn (NO 2) 2 1.9 C2H5 N - 1.1. 81.5 - 83.5 ° C 1.10 C2H5 N HNO3 1.11 C2H5 N ZnCl2 1.12 C2H5 N Mn (NO 2) 2 1.13 C2H5 N FeCls 1.14 C2H5 CH - Light brown oil 1.15 C2H5 CH CuCL · 1.16 C ₃ H ₇ -n CH - 1.17 C3H7-n N - 1.1. 68.5 - 71 ° C 1.18 C ₃ H ₇ -n N ZnCl2 1.19 C3H7-n N HCl 1.20 CaH5-n N - 1.21 C4H9-n CH - 1.22 CH2Cl N - 1.23 CH2OH N - 1.1. Mp 111-122 ° C

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N viscous oil no ²⁶ = 1,5865 A N - 1.1. 83 DEG -85 DEG C. B N mp 107-109 ° C A

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Λ- AND ^R 11 (XX li) including isomeric forms merge- Ru R12 Y salt physical data nina number 2.1 CH3 O2H5 CH _ 2.2 CH3 O2H5 N - 2.3 CH3 G2H5 CH HNOs 2.4 CH3 C2H5 N HNOs 2.5 CH3 C3H7 — n CH - 2.6 CHs C3H7 — n N - 2.7 CH3 G3H7 — n N HNOs 2.8 CH3 C3H7 — n N Mn (NO 3) 2 2.9 CH3 CH3 CH - 2.10 CHj CH3 CH CuCli2 2.11 CH3 C2H5 CH Mn (NO 2) 2 2.12 CH3 C2H5 CH CuCl'2 2.13 CH3 C2H5 N CuCl2 2.14 CH3 C2H5 N ZnCh 2.15 CH3 C2H5 N Mn (NO 2) 2 2.16 CH3 C2H5 N FeCb 2.17 CH3 CH3 N - oil; n _D ²³ = 1.5643 2.18 CH3 CH3 N HNO3 2.19 C2H5 CH3 CH MnCla 2.20 C2H5 CHs N MnCfe 2.21 C2H5 CH3 CH H2SO4 2.22 O2H5 CH3 CH ZnCfe 2.23 C2H5 C2H5 CH - 2.24 C2H5 C2H5 CH H2SO4 2.25 C2H5 C2H5 N - 2.26 C2H5 C2H5 N HNOs 2.27 C2H5 O2H5 N HCl 2.28 C2H5 C3H7 — n N - 2.29 C2H5 C3H7 — i N _ 2.30 C2H5 C3H7 — n CH _ 2.31 G2H5 C3H7 — n N HCl 2.32 C2H5 G2H5 N Mn (NO 3) 2 2.33 CH3 G2H5 N (COOH), 2 2.34 CH3 C2H5 CH (COOH) | 2.35 CH3 C3H7 — i N - 2.36 CH3 C3H7 — i N H2SO4 2.37 (CH2) 4- CH - 2.38 (CH2) 4- CH HNOs 2.39 (CH2) 4- N - 2.40 (CH2) 4- N Mn (NO 3) 2 2.41 (CH2) 4- N (COOH) 2 2.42 (CH2) 4- N ZnCfe 2.43 (CH ₂ ) 4- N HCl 2.44 (CH2) 4- CH ZnCfe

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3.384 H C2H5 Cl Η NO2 H CH - oil, n _D 28 = 1,5941

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241521 Table 5

Compounds of formula

including isomeric forms:

Compound No. Rll R12 R17 Rie Y salt physical data 5.1 CH3 C2H5 2-C1 H CH - 5.2 CH3 C2H5 2-C1 H N - 5.3 CH3 C2H5 2-C1 6-C1 CH HNO3 5.4 CH3 C2H5 2-CH3 H N HN03 5.5 CH3 C3H7-n 2-C1 H CH - 5.6 CH3 C3H7-n 2-C1 H N - 5.7 CH3 CsH7-n 3-C1 H N HNO3 5.8 CH3 C3H7-n 3-C1 6-C1 N Mn (NO 3) 3 5.9 CH3 CH3 2-C1 H CH - 5.10 CH3 CH3 2-C1 6-C1 CH CuCb 5.11 CH3 C2H5 2-C1 H CH Mn (NO 3) 2 5.12 CH3 C2H5 2-CH3 6-CH3 CH CuCb 5.13 CH3 CH3 2-CH3 H N HNO3 1.1. Mp 158-160 ° C 5.14 CH3 CH3 2-CH3 H N HBr 1.1. 192—204% 5.15 CH3 C2H5 2-CH3 H N Mn (NO 3) 2 5.16 CH3 C2H5 2-NO2 H N FeCl3 5.17 CH3 CH3 2-C1 H N - 5.18 CH3 CH3 2-C1 5-C1 N HNOs 5.19 C2H5 CH3 3-C1 H CH MnCb 5.20 C2H5 CH3 2-CH3 H N MnCb 5.21 C2H5 CH3 2-CH3 H N CuCb 5.22 C2H5 CH3 2-C1 5-C1 H ZnCb 5.23 C2H5 C2H5 2-Br H CH - 5.24 H C2H5 2-OCH 3 6-OCH 3 CH - 5.25 H H 2-C1 H N - 5.26 H H 2-C1 H CH - 5.27 H H 2-C1 6-C1 CH - 5.28 H H 2-C1 H N Mn (NO3) 2 5.29 H H 2-C1 6-C1 N - 5.30 H CH3 2-C1 H N - 5.31 H CH3 2-C1 H N HNOs 5.32 H CH3 2-C1 6-C1 N - 5.33 H CH3 2-C1 H CH - 5.34 H CH3 2-OCH 3 6-OCH 3 CH - 5.35 H CH3 3-C1 H N - 5.36 H CH3 2-CH3 H N HNO3 t. t. 132—134% 5.37 H CH3 3-CH3 H N - 5.38 H C2H5 3-CH3 H CH CuCb 5.39 H C2H5 2-CH3 6-CH3 N - 5.40 H C2H5 2-CH3 H N HNO3 mp 108-110 ° C 5.41 H C2H5 2-Br 5-Br N - 5.42 H C2H5 2-C1 H N - oil, n _D ²² = 1.5620 5.43 H C3H7-n 2-C1 H N - 5.44 H CsH7-n 2-C1 6-C1 N - 5.45 H C3H7-I 2-CH3 H N  - 5.46 H C3H7-I 2-CH3 H CH - 5.47 H C3H7-I 2-OCH 3 6-OCH 3 N MnCb 5.48 C2H5 C2H5 2-C1 H N - 5.49 C2H5 C2H5 2-C1 H N HNOs

Compound No. Rll R12 R17 R18 Y salt physical data 5.50 CzHs i C2H5 2-C1 6-C1 N HCl 5.51 H H 2-OCH 3 6-OCH 3 CH - 5.52 C2H5 C 3 H 7 -I 2-CH3 H N - 5.53 H C2H5 2-OCH 3 6-OCH 3 N - 5.54 H C2H5 2-OCH 3 6-OCH 3 N - 5.55 H H 2-OCH 3 6-OCH 3 N - 5.56 CH3 C2H5 3-C1 H N (COOH) 2 5.57 CH3 C2H5 2-CH3 6-CH3 CH (COOH) 2 5.58 CH3 C3H7-1 2-C1 H -N - 5.59 CH3 C3H7-I 2-C1 6-C1 N H2SO4 5.60 - (CH ₂ ) 4- 2-C1 H CH - 5.61 - (CH 2) 4— 2-C1 H CH HNO3 5.62 - (CH ₂ ) 4- 2-C1 H N - 5.63 - (CH2J4- 3-C1 H N Mn (NO 3) 2 5.84 - (CH2) 4- 3-C1 6-C1 N (COOH) 2 5.65 - (C, H2) 4- 3-C1 5-C1 N ZnCh 5.66 - (CH2) 4- 3-C1 6-C1 N HCl 5.67 _ (CH2) 4- 2-C1 H CH ZnClz 1.1. 103-106 ° C 5.68 H H 2-CH3 H CH - 5.69 CH3 CH3 2-CH3 H CH - yellow resin n _D 50 = 1.5476 5.70 H C3H7-n 2-CH3 H CH - 5.71 H CH2OCH3 2-CH3 H CH - resin 5.72 H CH3 2-CH3 H CH resin, n _D 5 ° = 1.5557 5.73 H C2H5 2-CH3 H CH - 5.74 H CH2OH 2-CH3 H CH - oil, n _D ⁵⁰ = 1.5482 5.75 H CH2OCH3 2-CH3 H N - 5.76 H C2H5 2-CH3 H N - resin n _D ⁵⁰ = 1.5502 5.77 H H 2-CH3 H N - mp 103-105 ° C 5.78 H C3H7-n 2-CH3 H N - resins, n _D ⁵⁰ = 1.5467 5.79 H CH2OH 2-C1 H CH - 5.80 H C2H5 2-Br H CH - resin, n _D ²² = 1.5765 5.81 H C2H5 2-C1 H CH - 5.82 H CH2OCH3 2-C1 H CH - 5.83 H CH2OCH3 2-C1 H N - 5.84 H CH2OH 2-Br H CH - 5.85 H CH2OCH3 2-Br H CH - 5.86 CH3 CH3 2-Br H N - 5.87 H CH2OCH3 2-Br H N - 5.88 H CH2OH 3-NO2 H CH - 5.89 H C3H7-n 3-NO2 H N - 5.90 H C2H5 2-Br H N - 5.91 H C2H5 3-NO2 H CH - 5.92 H CH3 3-NO2 H CH - 5.93 H C2H5 3-NO2 H N - 5.94 H CH3 3-NO2 H N - 5.95 H CH2OH 3-CH3 H CH - 5.96 H CH2OCH3 3-CH3 H N - 5.97 H C2H5 2-NO2 H CH - 5.98 H CH2OCH3 2-NO2 H CH - 5.99 H CH2OCH3 2-NO2 H N - n _D ^{20 -5} = 1.5692 5.100 H C2H5 3-CH3 H CH - 5.101 H CH12OCH3 3-CH3 H CH - 5.102 H C2H5 3-CH3 . H N - n _D 22 = 1.5577 5.103 H CH2OH 2-NO2 H CH - 5.104 H C2H5 2-NO2 H N -

Compound No. Rll R12 R17 R18 Y salt physical data 5.105 2-CH3 H 2-CH3 5-CH3 CH viscous product, n _D s ° = 1.5463 5.106 H C3H7-n 2-CH3 H N - oil, n _D ²² = 1.5461 A 5.107 H C3H7-n 2-CH3 H N - viscous oil n _D 22 = 1.5468 B 5.108 H C2H5 3-CH3 H N - resins, n _D 50 = 1.5638 5.109 H C2H5 3-CH3 H CH - resins, n _D ⁵⁰ = 1.5732 5.110 H C2H5 2-C2H5 H N HNO3 mp 132-134 ° C 5.111 H C2H5 2-CH3 H CH (COOH) 2 mp 115-118 ° C 5.112 H C2H5 2-C2H5 H N - oil, n _D ²² = 1.5642 5.113 H C2H5 3-CH3 H N - oil, n _D ²² = 1.5631, A 5.114 H C2H5 3-CH3 H N - oil, n _D ²² = 1.5633 5.115 H C2H5 2-C2H5 H CH -. brown resin 5.116 H CH3 2-C2H5 H CH HNO3 mp 105-119 ° C 5.117 H CH3 2-C2H5 H CH - viscous oil 5.118 H CH3 2-C2H5 H N HNO3 mp 136-138 ° C 5.119 H C2H5 2-CH3 H CH HCl mp 166-171 ° C 5.120 H C2H5 2-CH3 H CH H2SO4 . mp 136-138 ° C 5.121 H C2H5 2-CH3 H CH CH3SO3H mp 98-106 ° C 5.122 H C2H5 2-CH3 H CH HNO3 mp 96-98 ° C 5.123 H C2H5 2-C2H5 H CH HNO3 mp 134-137 ° C 5.124 H C2H5 2-CH3 H CH - oil, 5.125 H C2H5 2-CH3 H CH - oil, B 5.126 H C3H7-n 2-CH3 5-CH3 N - n _D ²³ = 1.55 80 5.127 H C2H5 2-CH3 5-CH3 N - mp 73-75 ° C 5.128 H CHs 2-CH3 5-CH3 N - mp 93-95 ° C 5.129 CH3 CH3 2-CH3 5-CH 2 N - mp 59-62 ° C 5.130 H CH3 2-CH3 5-CH3 CH -. n _D 23 = 1.5751 5.131 H Cl2H5 2-CH3 3-CH 3 N HNOs mp 103-105 ° C 5.132 H Cl2H5 2-CH3 3-CH 3 CH HNO3 mp 126-128 ° C

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Examples of fungicidal compositions which contain liquid active compounds of the formula I ('% =% by weight'):

2. Emulsion concentrate

and) (b) C) the active substance of Tables 1 to 10 25% 40 o / o 50 o / o calcium salt dodecylbenzenesulfonic acid 5% 8 o / o 6 o / o castor oil polyethylene glycol ether (36 moles of ethylene oxide) 5% - - tributylfeinoylpolyethylene glycol ether (30 mol ethylene oxide) - 12% 4% cyclohexanone - 15% 20% mixture of xylenes 65 θ / o ^- 25 o / o 20 o / o

Emulsions of any desired type can be prepared from such concentrates by dilution with water.

imported concentrations. 3. Solutions and) (b) C) (d) the active substance of Tables 1 to 10 80% 10% 5% 95% ethylene glycol monomethyl ether 20% - - - polyethylene glycol (molecular weight 400) - 70% - - N-methyl-2-pyrrolidone - 20% - - epoxidized coconut oil - - 1% 6 ° / o benzine (boiling point 160—190 ° C) - - 94% - These solutions are suitable for application in in the form of minimal drops. 4. Granulate and) (b)

the active substance of Tables 1 to 10 5% 10% kaolin 94% -. highly disperse silicic acid 1% - attapulgit - 90%

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

5. Dust

(a) (b) the active substance in Tables 1 to 10, highly dispersed silicic acid talc kaolin

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

% - 5%% 5%% - - 90%

Examples of fungicidal compositions which contain solid active compounds of the formula I (% =% by weight)

6. Wettable powder Active ingredient from Tables 1 to 10 Sodium salt of lignin sulphonic acid Sodium lauryl sulphate Sodium diisobutylnaphthalenesulphonate Octylphenolipolyethylene glycol ether (7 to 8 moles of ethylene oxide) High-disperse silica Kaolin

The active ingredient is well mixed with the other ingredients and the mixture is ground well in a suitable mill. A wettable powder is obtained which can be diluted with water to suspensions of any desired concentration.

7. Emulsion concentrate Active ingredient from Tables 1 to 10 10% octylphenolpolyethylene glycol ether (4 to 5 moles of ethylene oxide) 3% calcium dodecylbenzenesulfonic acid 3% polyglycol ether of castor oil (35 moles of ethylene oxide) 4% cyclohexanone 30% o / _o mixture of xylenes 50%

Emulsions of any desired concentration can be prepared from this concentrate by dilution with water.

8. Dust

active substance and) (b) from Tables 1 to 10 5% 8% talc 95% - kaolin __ 92%

The active ingredient is mixed with the carrier and ground in a suitable mill. A dust is obtained which can be directly applied.

9. Granules obtained by extrusion active ingredient from Tables 1 to 10 10% sodium lignin sulphonate 2% carboxymethylcellulose 1% kaolin 87%

and) (b) C) 25% 50% 75% 5% 5% -. 3% - 5% - 6% 10%

- 2% 5% 10% 10% 27% -

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

10. Coated granulate Active substance from Tables 1 to 10 3% polyethylene glycol (molecular weight 200) 3% kaolin 94%

The finely divided active ingredient is applied evenly to kaolin moistened with polyethylene glycol in a mixer. In this way a non-dusted coated granulate is obtained.

11. Suspension concentrate Active ingredient from Tables 1 to 10 40% ethylene glycol 10% nonylphenolpolyethylene glycol ether (15 mol ethylene oxide) 6% lignin sulphonic acid sodium 10% carboxymethylcellulose 1%

37% aqueous formaldehyde solution 0.2% silicone oil 75% aqueous emulsion 0.8% water 32%

The finely divided active ingredient is intimately mixed with the remaining ingredients. A suspension concentrate is obtained from which suspensions of each desired concentration can be prepared by dilution with water.

Examples of pharmaceutical formulations

12. Masti

An ointment containing 5% 2- [p- (4-chloro-241521-phenoxy) phenyl] -2- (1-imidazolyl) -4-ethyldioxolane can be prepared as follows:

Ingredients:

Active substance 5.0% Vaseline 45.0% Paraffin oil 19.6% Cetyl alcohol 5.0% Beeswax 5.0% Sorbitan sesquiolole 5.0% p-Hydroxybenzoic acid ester 0.2% Demineralized water up to 100 0%

Fatty substances and emulsifiers are melted together. The preservative is dissolved in water and the solution is emulsified at an elevated temperature in the melt of fatty substances. After cooling, the active ingredient suspension is incorporated into 1 part of the fatty substance melt to form an emulsion.

13. Cream

A cream containing 10% 2- [p- (chlorophenoxy) phenyl] -2- (1-imidazolylmethyl) -4-ethyl-1,3-dioxolane can be obtained as follows:

Ingredients:

Active ingredient 10.0% Isopropyl palmitate 8.0% Cetyl palmitate 1.5% Silicone oil 100 0.5% Sorbitan monostearate 3.0% PoLysorbate 60 3.5%

1,2-propylene glycol PH 20,0% acrylic acid polymer 0,5% triethanolamine 0,7% water, demineralised up to 100,0 ° / o

The acrylic acid polymer is suspended in a mixture of demineralized water and 1,2-propylene glycol. Triethanolamine is then added with stirring to give a mucilaginous substance. A mixture of isopropyl palmitate, cetyl palmitate, silicone oil, sorbitan monostearate and polysorbate is heated to about 75 ° C and incorporated with stirring into a mucilaginous substance which has also been heated to a temperature of

2B about 75 ° C. The cream base composition, cooled to room temperature, is then used to produce the active ingredient concentrate. The concentrate is homogenized by means of a flow homogenizer and then added in portions to the matrix.

A cream containing 5% 2- [p- (chlorophenoxy) phenyl] -2- (1-imidazolylmethyl) -4-ethyl-1,3-dioxolane can be prepared as follows:

Ingredients:

Active substance 5.0% cetyl palmitate pH 2.0% cetyl alcohol PH 2.0% triglyceride mixture of saturated medium fatty acids 5.0% stearic acid 3.0% glycerin stearate PH 4.0% polyhydroxyethylene stearyl ether 1.0% microcrystalline cellulose 0.5 %

1,2-propylene glycol, distilled 20,0% water, demineralised up to 100,0%

Cetyl alcohol, cetyl palmitate, triglyceride mixture, stearic acid and glycerin stearate are melted together. The microcrystalline cellulose is dispersed in one part of water. The polyhydroxyethylene stearyl ether is dissolved in the remainder of the water and propylene glycol and mucilage are added to the solution. The fatty phase is then added to the aqueous phase with stirring and the mixture is cooled with stirring. Finally, the active ingredient is rubbed with one part of the matrix and then the comminuted mass is incorporated into the rest of the cream.

14. Hydrogel

A transparent hydrogel containing 5% 2- [p- (chlorophenoxy) phenyl] -2- (1-imidazolylmethyl) -4-ethyldioxolane is prepared as follows:

Ingredients:

active substance . 5 o / o propylene glycol 10 to. 20% isopropanol 20% hydroxypropyl methylcellulose 2% water to 100%

The hydroxypropyl methylcellulose is swollen in water. The active ingredient is dissolved in a mixture of isopropanol and propylene glycol. Thereafter, the active ingredient solution is mixed with the swollen cellulose derivative and optionally fragrances (0.1%) are added.

15. Foam spray

A foam spray containing 1% 2- [p- (chlorophenoxy) phenyl] -2- (1-imidazolylmethyl) -4-ethyl-1,3-dioxolane can be prepared as follows:

Ingredients:

active substance 1.00% cetyl alcohol PH 1.70% paraffin oil, viscous 1.00% isopropyl myristate 2.00% polyhydroxyethylene stearyl ether 2.40% sorbitan monostearate 1.50%

1,2-propylene glycol pH 5,00% methylparaben 0,18% propylparaben 0,02% glycerin stearate 0,10% water, demineralised up to 100,00%

Cetyl alcohol, paraffin oil, isopropyl myristate, polyhydroxyethylene stearyl ether and sorbitan stearate are melted together. Methyl propylparaben is dissolved in hot water. The melt and the solution are then mixed. The active ingredient, which is suspended in propylene glycol, is incorporated into the matrix. Glycerin stearate is then added and the mixture is brought to final volume with water.

Performance:

ml of the mixture is filled into an aluminum container. The can is fitted with a valve and the propellant is pressed in under pressure.

16. Capsules

Gelatin capsules containing 200 mg of [p- (phenoxy) phenyl] -2- (1- (1H-1,2,4-triazolyl) methyl] -1,3-dioxane as active ingredient may be prepared, for example, by the following: as follows:

Composition (for 1000 capsules):

active substance 100 g lactose, milled 100 g

The active ingredient and lactose (finely divided) are well mixed with each other. The powder obtained is sieved and 0.20 g in portions are filled into gelatin capsules.

17. Tablets

Tablets containing 25 mg of the active ingredient, for example 2- [p- (phenoxy) phenyl] -2- (1- (1H-1,2,4-triazolyl) methyl-1,3-dioxane), can be obtained as follows:

Ingredients (for 1,000 tablets):

active substance 2.5 g lactose 100.7 g wheat starch 7,5 g polyethylene glycol 6 000 5.0 g talc 5.0 g magnesium stearic acid salt 1.8 g demineralized water as required

Production:

All solids are first sieved through a 0.6 mm sieve. The active ingredient, lactose, talc, magnesium stearate and half of the starch are then admixed. A further half of the starch is suspended in 40 ml of water and this suspension is added to a boiling solution of polyethylene glycol in 100 ml of water, and the mixture is optionally granulated after the addition of water. The granulate is dried overnight at 35 ° C, passed through a 1.2 mm sieve and pressed into concave tablets of about 6 millimeters in diameter on both sides.

Tablets containing 100 mg of the active ingredient, for example 2- [p- (phenoxy) phenyl] -2- [1- (1H-1,2,4-triazolyl) methyl] -1,3-dioxane, may be prepared by the following: as follows:

Ingredients (for 1000 tablets):

Active ingredient lactose Wheat starch Polyethylene glycol 6 000 Talc Magnesium stearic acid Demineralized water

Production:

100.0 g 50.7 g

7.5 g 5.0 g 5.0 g

1.8 g as needed

All solid components are first passed through a sieve with a mesh size of 0.6 mm. The active ingredient, lactose, talc, magnesium stearate and 1/2 starch are then mixed. The other half of the starch is suspended in 40 milliliters of water and this suspension is added to a boiling solution of polyethylene glycol in 100 milliliters of water, and the mixture, optionally after the addition of water, is granulated. The granulate is dried overnight at 35 ° C, passed through a 1.2 mm sieve and then pressed into two-sided concave tablets about 6 mm in diameter.

Tablets containing 75 mm of the active ingredient, for example 2- [p- (phenoxy) -unyl] -2- (1- (1H-1,2,4-triazolyl) methyl) -1,3-dioxane, may be prepared as follows:

Ingredients (for 1,000 tablets):

Active ingredient lactose Wheat starch Polyethylene glycol 6000 Talc Magnesium stearic acid Demineralized water

75.0 g 100.7 g

7.5 g 5.0 g 5.0 g

1.8 g as needed

All solid components are first passed through a sieve with a mesh size of 0.6 mm. The active ingredient, lactose, talc, magnesium stearate and 1/2 starch are then mixed. The other half of the starch is suspended in 40 ml of water and this suspension is added to a boiling solution of polyethylene glycol in 100 ml of water and the mixture, optionally after addition of water, is granulated. The granulate is dried overnight at 35 ° C, then sieved through a 1.2 mm sieve and pressed into two-sided concave tablets about 6 mm in diameter.

Pharmaceutical preparations containing any of the other compounds listed in Tables 1 to 10 can also be prepared in an analogous manner.

Examples illustrating biological activity:

For the following examples, which illustrate biological activity (Examples 18 to 22), the following products A to D, which are known on the market, were simultaneously tested for comparison purposes:

A = 'Maneb' = manganese ethylene bis-dithiocarbamate

B = 'Mancozeb' = Manganese-zinc ethylene bis-dithiocarbamate

C = "Fentin Acetate" = triethyl enyltin acetate ·

D = "Forpet" = N-trichloromethylthiophthalimide. Example 18

Effect against rust (Puccinia graminis) on wheat

(a) Residual protective effect

Wheat plants are sprayed with a suspension made of wettable powder (active ingredient concentrate) 6 days after sowing, with the active ingredient concentration in the spray suspension being 0.06%. After 24 hours, the treated plants are infected with a fungal uredospore suspension. After incubation for 48 hours at 95 to 100% relative humidity and at about 20 ^° C, the infected plants are placed in a greenhouse at about 22 ° C. Assessment of rust development is performed 12 days after infection.

b) Systemic effect

Wheat plants are covered 5 days after sowing with a suspension made from a wettable powder of the active ingredient (concentration 0.006% active ingredient, based on soil volume). After 48 hours, the treated plants are infected with a fungal uredospore suspension. After incubation for 48 hours at 95 to 100% relative humidity and about 20 ° C, the infected plants are placed in a greenhouse at about 22 ° C. Assessment of rust development is performed 12 days after infection.

The compounds of Tables 1 to 10 show good activity against Puccinia. Untreated but infected control plants are 100% infected with Puccinia.

The results are shown in the following table:

a] Residual protective action against Puccinia graminis compound infestation compound infestation number% number%

1.9 0—5 3.274 0 1.17 0-1 3.279 0—2 1.24 0-1 3.287 0—5 1.26 0—4 3.292 0—4 2.17 0—5 3.311 0—3 3.1 0—1 3.314 0 3.2 0 3.340 0—2 3.6 0 3.348 0—1 3.7 0 3.373 0—2 3.8 0-4 3.376 0—4 3.12 0—1 4.2 1—3 3.26 0—5 4.15 5—12 3.51 0—2 4.23 5—7 3.52 0—2 4.50 0—5 3.54 0—2 4.55 0—4 3.55 0—3 4.57 0-3 3.70 0—4 4.66 0—5 3.75 0—4 4.70 3—5 3.78 0—3 4.77 0—4 3.83 0—2 4.78 92—97 3.85 5—7 4.81 90—95 3.86 0—2 4.89 90—93 3.127 0—1 4.90 100 ALIGN! 3.133 0 4.91 0-4 3.155 0 4.92 0 3.156 0 4.93 2—4 3.160 4—7 4.94 0—2 3.162 0—1 4.113 0—2 3.164 0 4.116 0-4 3.168 0 5.13 0 3.171 0—4 5.14 4—5 3.172 0—4 5.36 0—5 3.176 0—3 5.40 0—4 3.177 0-4 5.70 0-2 3.193 0—5 5.71 0 3.212 0-4 5.76 0 3.213 0—3 5.78 0—2 3.220 0—4 6.8 0—1 3.226 0-4 7.7 4—7 3.227 0-3 7.33 3—5 3.231 0 8.66 4—5 3.232 0 AND 0—5 3.233 0 (B) 0—1 3.234 0 C 5-7 3.263 0—1 D 0—2 3.267 0 control 90—95

In addition, compound 6.8 has an excellent systemic effect, among other things. Infestation with Puccinia was completely suppressed (0% attack). This effect was also found with a considerably reduced application rate of 0.006%. Example 19

Activity against Cercospora arachidicola on peanuts up to 15 cm tall peanuts are sprayed with a spray suspension (0.02% active ingredient) which was made from a wettable powder of the active ingredient. After 48 hours, the plants are infected with a conidia suspension of the fungus. The infected plants are incubated at about 21 ° C and high humidity for 72 hours and then placed in a greenhouse until typical spots on the leaves. Assessment of fungicidal effect is performed 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%), groundnut plants treated with the active substances of Tables 1 to 10 exhibit significantly reduced Cercospora infestation. Antibody against Cercospora arachidicola:

compound attack number ° / o

1.1 0—4 1.4 2—5 1.9 0 1.14 7—10 1.17 0 1.24 0 1.25 0 1.26 0—2 1.27 0—1 2.17 0 3.1 0 3.2 5—10 3.6 0—4 3.7 0 3.11 0 3.51 0—4 3.52 0—3 3.54 0—3 3.55 0 3.75 5—10 3.78 0 3.85 0 3.86 0 3.127 0—1 3.133 0—4 3.155 5—9 3.156 0 3.162 0—5 3.171 0—3 3.172 0 3.176 0 3.177 0—1 3.212 0—5 3.213 2—3 3.220 4—5 3.221 0 3.226 0—3 3.231 0 3.232 0 3.233 0 Example 20 Action against powdery mildew (Erysiphe graminis) on barley

(a) Residual protective effect

About 8 cm high barley plants are sprayed with a suspension (0.02% active ingredient) which was made from a wettable powder of the active ingredient. After 3-4 hours, the treated plants are dusted with conidia of the fungus. Infected barley plants are then placed in a greenhouse at about 22 ° C and after 10 days the fungal infestation is assessed.

(b) Systemic effect:

the results are shown in the following table: compound attack number % 3.234 0 3.267 3—4 3.292 0—4 3.314 0 3.348 0—2 4.15 0 4.23 1 4.50 0 4.57 7—9 4.59 3—5 4.66 7—10 4.89 93—98 4.90 0—3 4.91 0—2 4.92 0—2 4.93 0 4.94 0 4.113 0 4.116 0 5.13 0 5.14 5—7 5.36 0 5.40 5—7 5.70 0 5.71 0 5.73 0 5.75 0 5.76 0—2 5.77 0-2 5.78 0 6.1 0 6.8 0 7.33 0—1 7.34 0 8.72 0 AND (B) 0 95—100 C 93—96 D 94—98 control 100 ALIGN!

About 8 cm tall barley plants are covered with a suspension (concentration 0.006% active ingredient, based on the volume of soil), which was made of a wettable powder of the active ingredient. 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 placed in a greenhouse at a temperature of about 22 ° C and after 10 days the fungal infestation is assessed.

The compounds of formula I show a good residual protective effect against powdery mildew (Erysiphe graminis). Untreated but infected control plants show 100% powdery mildew attack.

The test results are summarized in the following table:

Action against powdery mildew (Erysiphe graminis)

compound attack compound attack number % 5 číslo % 1.1 0—4 3.287 5—7 1.4 4—7 3.292 5—8 1.9 0 3.311 0 1.14 30 3.314 0 1.17 0 3.340 10 1.23 0 3.348 10—15 1.24 0—5 3.373 0—3 1.25 0 4.2 5—7 1.26 0 4.15 0 1.27 0—3 4.23 2—5 2.17 0—4 4.50 0 3.1 0 4.57 0 3.2 0 4.59 0 3.6 0 4.66 2—5 3.7 0 4.77 0 3.8 0 4.78 0 3.11 0 4.81 0 3.12 0-4 4.89 0 3.26 2—5 4.90 0 3.51 0 4.91 0 3.52 0—3 4.92 0 3.54 0—3 4.93 0 3.55 0 4.94 0 3.70 0 4.113 3—5 3.75 0 4.116 2—3 3.78 0 5.13 0 3.85 7—8 5.14 0 3.86 0 5.36 0 3.103 5—9 5.40 0 3.127 0—5 5.70 98—100 3.133 0-1 5.71 100 ALIGN! 3.156 0 5.73 97—100 3.160 0 5.75 96—100 3.162 0—2 5.76 100 ALIGN! 3.164 0 5.77 2—5 3.168 0 5.78 0 3.171 2—5 5.106 0 3.172 0—3 5.107 0 3.174 7—9 6.1 0 3.176 5—6 6.8 3—6 3.177 0—3 6.17 0 3.193 0 6.79 0 3.212 0—5 6.80 7—10 3.213 4—5 7.3 0 3.220 10 7.7 0 3.221 5—8 7.21 0 3.226 0 7.33 0-3 3.227 0—3 1.34 5—8 3.231 4-5 8.66 0 3.232 5 8.69 0 3.233 3—5 8.72 0—2 3.234 7—9 10.7 0 3.263 0—4 AND 4-5 3.267 0—2 (B) 0 3.274 0 C 0—5 3.279 11 D 5—7 control 0

Example 21 of the active ingredient. After 24 hours, the treated thorns are infected with a conidia suspension. The plants are then incubated for 5 days against apple scab (Venturia at 90-100% inaequalis relative humidity) on apple shoots and placed in a greenhouse at 20-24 ° C for a further 10 days. The attack-

Apple seedlings with 10 to 20 cm long fresh shoots are sprayed with a suspension (concentration 0.06% active ingredient), by 15 days post infection. The test results are in the following tables: evident from the following that was made of a wettable powder Effect against Venturia inaequalis compound attack compound attack number % number % 1.4 5-7 4.59 11—15 1.9 7—10 4.66 7—15 1.17 5—8 4.78 0 1.24 5—8 4.81 0—5 1.26 9—13 4.89 5-10 2.17 7—9 4.90 0-3 3.1 8—11 4.91 8 3.6 10 4.92 0—3 3.7 5—10 4.93 14—16 3.11 7—10 4.94 12—14 3.52 5—12 4.113 0 3.55 0 4.116 0 3.85 5—10 5.13 0—5 3.86 0 5.14 5—7 3.156 5—9 5.36 5—10 3.160 8—13 5.40 5—10 3.164 8—13 5.70 8—10 3.172 7—13 5.73 8—11 3.176 8—14 5.75 8—11 3.177 5—9 5.76 10—15 3.213 5—10 6.1 5-10 3.221 5—9 6.8 0—5 3.233 6—11 10.7 7—9 3.314 14-15 AND 100 ALIGN! 4.15 8—9 (B) 100 ALIGN! 4.23 7—10 C 100 ALIGN! 4.50 0 D 100 ALIGN!

Untreated but infected shoots show 100% infestation with Venturia inaequalis.

Example 22

Effect against gray mold (Botrytis cinerea) on bean

Residual protective effect

The about 10 cm tall bean plants are sprayed with a suspension (0.02% active ingredient) which was made from a wettable powder of the 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. In many cases, the compounds of Tables 1 to 10 suppress fungal infection very strongly.

The results are shown in the following table:

Effect against Botrytis cinerea:

compound attack compound attack number % number %

1.1 2-5 1.4 0 1.9 2—5 1.17 2—5 3.6 4—5 3.7 0 3.12 5—10 3.51 5—15 3.55 5-10 3.86 0 3.226 5—7 3.231 5—10 3.267 8—12 3.311 5—10 4.15 0—3 4.50 5—7 4.59 0 4.66 0 4.78 5—7

4.90 10-12 4.91 10—12 4.92 9—11 4.93 0 4.113 0—5 5.13 0—3 5.36 0 5.40 5—10 5.70 7—10 5.71 0—5 5.73 2—5 5.75 0 5.76 15—20 5.78 25 6.1 8—10 6.8 5—10 7.3 5—11 7.33 0 8.72 0

Plants that have been treated with Compounds A, B, C or D, as well as untreated control plants, show 100% infection with Botrytis cinerea.

None of the comparative products A to D currently on the market had any remarkable fungicidal effect at the low test concentrations used in these tests. In all tests, the infestation reached more than 90% and thus practically did not differ from untreated control plants.

Claims (8)

SUBJECT VYNALEZU A process for the preparation of novel arylphenyl ethers derivatives of the general formula I Ar- O- -AND- O-Uy -í-ó Rb i-zN CH- _N I YJ (1) in which Y represents a group --CH = or - N =, R _a and R _b independently represent an atom, a hydrogen atom, a halogen atom, an alkyl group with 1 to 3 carbon atoms or methoxy, U and V are independently C1-C3 alkyl or together form one of the following alkylene groups; or where R 1 and R 2 are each independently hydrogen, C 1 -C 3 alkyl or formula i, I, ... —CH2 — Z — R7, wherein Z is oxygen or sulfur; and \ R 7 is hydrogen, C 1 -C 3 alkyl, C 3 -C 4 alkenyl, methoxyethyl, phenyl, chloro or methyl-substituted phenyl, benzyl or chloro or methyl-substituted benzyl, R 5, R 4 and R 5 are each independently hydrogen or C 1 -C 3 alkyl, with the total number of carbon atoms in R 3, R 4 and R 5 not exceeding 6; and Ar represents a group wherein R _c , R _d and R _e are each independently hydrogen, halogen, C 1 -C 4 alkyl, C 1 -C 3 alkoxy, trifluoromethyl or nitro, as well as their acid addition salts and complexes thereof % with copper, characterized in that the carbonyl group in the compound of formula IV C-CH, -N / - N 'in J y or IV) in which: Ar, R _a , R b and Y are as defined above, converted in an organic solvent at a temperature of 60 to 160 ° C by reaction with an orthocarboxylic acid trialkyl ester having 1 to 12 carbon atoms in the alkyl group and having 1 to 12 carbon atom alkyl groups optionally substituted by halogen or alkoxy having 1 to 6 carbon atoms, or in the presence of an acid by reaction with at least 2 mol of a monovalent alcohol of formula Va U — OH (Vaj in which U is as defined above, or by reaction with a diol of formula Vb HO-U ---- V-OH (Vb) wherein U and V are as hereinbefore defined, whereupon optionally the free compound obtained by the above process is converted by reaction with an organic or inorganic acid into an acid addition salt; or the free compound or acid addition salt obtained is converted by reaction with a copper salt into a copper complex. 2. The process of item 1, for producing compounds of formula I, wherein: Y is -CH = or -N =, R _a and R _b are each independently hydrogen, halogen, C 1 -C 3 alkyl or methoxy, U and V are independently C1-C3 alkyl or together form one of the following alkylene groups <H> whereas R1 and Ra are each independently hydrogen, C1-C3alkyl or -CH2-Z-R7, wherein: Z is oxygen or sulfur; and R 7 is hydrogen, C 1 -C 3 alkyl, C 3 -C 4 alkenyl, methoxyethyl, phenyl, chloro or methyl-substituted phenyl, benzyl or chloro or methyl-substituted benzyl, R 3, R 4 and R 5 are each independently hydrogen or C 1 -C 3 alkyl, the total number of carbon atoms in R 3, R 4 and R 5 being no more than 6, Ar represents a group of the formula wherein U and V are as defined above for a group of formula V 241321 where R _c , R _d and R _e are each independently hydrogen, halogen, C 1 -C 4 alkyl, C 1 -C 3 alkoxy, trifluoromethyl or nitro, and their acid addition salts and copper complexes characterized in that the carbonyl group in the compound of formula (IV) is converted in an organic solvent at a temperature of 60 to 160 ° C by reaction with a trialkyl ester of an orthocarboxylic acid containing from 1 to 12 carbon atoms in the alkyl group having 1 to 12 carbon atoms are optionally substituted by halogen or alkoxy of 1 to 6 carbon atoms, or in the presence of an acid by reaction with at least 2 mol of a monovalent alcohol of formula Va or by reaction with a diol of formula Vb to a group of formula V, wherein the substituents in formulas Va, Vb, IV and V are as defined above, whereupon the compound obtained is optionally converted to adi an acid or salt complex with copper. Process according to either of Claims 1 and 2, characterized in that the corresponding compounds of the general formulas (IV), (Va) and (Vb) are used as starting materials, to give compounds of the general formula (I) in which: Y is -CH = or -N =, R _a and R _b are each independently hydrogen, halogen or C 1 -C 3 alkyl, Ar represents a group of the formula wherein R _c , R d and R d are independently hydrogen, halogen or C 1 -C 3 alkyl, and U and V have the meaning given in 1 or 2. Process according to either of Claims 1 and 2, characterized in that the corresponding compounds of the general formulas (IV), (Va) and (Vb) are used as starting materials to give compounds of the general formula (I) in which: U and V are independently C 1 -C 3 alkyl or together form one of the following alkylene groups wherein: R 1, R 2, R 3, R 1 and R 5 are each independently hydrogen or C 1 -C 3 alkyl, the total number of carbon atoms in R 5, R 4 and R 5 not exceeding 6, Ar represents a group of the formula wherein R _c , R _d and R independently of one another are hydrogen, halogen or C 1 -C 3 alkyl, and Y represents —CII = or —N =. Process according to either of Claims 1 or 2, characterized in that the corresponding compounds of the general formulas (IV), (Va) and (Vb) are used as starting materials, to give compounds of the general formula (I) in which: Y is —CH = or —N =, Ar is as defined in point 1 or 2, R _a , R _b , R _c , R _d and R _e are each independently hydrogen, chloro, bromo, fluoro, methyl, methoxy or nitro, U and V are, independently of one another, a (C 1 -C 3) alkyl group or together form one of the alkylene groups defined in (1) or (2), wherein R 1, R 2, R 3 and R 4 are each independently hydrogen or C 1 alkyl; or R 1 is -CH 2 -O-R 7, wherein R 7 is hydrogen, C 1 -C 3 alkyl, C 3 -C 4 alkenyl or phenyl. Process according to either of Claims 1 and 2, characterized in that the corresponding compounds of the formulas IV, Va and Vb are used as starting materials to give 2- [p- (phenoxy) phenyl] -2- [1- (1H-1,2,4-triazolyl) methyl] -4-ethyl-1,3-dioxolane, 2- [p- (phenoxy) phenyl] -2- [1- (1H-1,2,4-iriazolyl) methyl] -4-methyl-1,3-dioxane, 2- [p- (4'-chlorophenoxy) phenyl] -2- [1- (1H-1,2,4-triazolyl) methyl] -4-ethyl-1,3-dioxolane, 2- [p- (phenoxy) -2-chlorophenyl] -2- [1- (1H-1,2,4-triazolyl) methyl] 4-ethyl-1,3-dioxolane. Process according to either of Claims 1 and 2, characterized in that the corresponding compounds of the formulas IV, Va and Vb are used as starting materials to give 2- [ρ- (3 ‘, 4‘-dichlorophenoxy) phenyl] -2- [1- (1H-1,2,4-triazolyl) methyl] -4-methoxymethyl-1,3-dioxolane, 2- [p- (3 ', 4'-dichlorophenoxy) phenyl] -2- [1- (1H-1,2,4-triazolyl) methyl] -4-ethyl-1,3-dioxolane, 2- [2- p- (4'-chlorophenoxy) phenyl] -2- [1- (1H-1,2,4-triazolyl) methyl] -4-ethyl-1,3-dioxolane with copper sulfate, 2 - [(2-methyl-4-phenoxy) phenyl] -2- (1-imidazolylmethyl) -4-ethyl-1,3-dioxolane, 2-p- (phenoxy) -2-methylphenyl] -2- [1- (1H-1,2,4-triazolyl) methyl] -4-ethyl-1,3-dioxolane, 2- [p- (4'-chlorophenoxy) -2-methylphenyl] -2- [1- (1H-1,2,4-triazolyl) methyl] -4-methyl-1,3-dioxolane, 2- [p- (4'-chlorophenoxy) phenyl] -2- [1- (1H-1,2,4-triazolyl) methyl] -3,4-dimethyl-1,3-dioxolane, 2- {p - [(4‘-bromophenoxy) phenyl] -2- [1- (1H-1,2,4-triazolyl] methyl] -4-ethyl-1,3-dioxolane, 2- [p- (phenoxy) -2-chlorophenyl] -2- [1- (1H-1,2,4-triazolyl) methyl] -4-methyl-1,3-dioxane, 2- [p- (4'-bromophenoxy] phenyl] -2- [1- (1H-1,2,4-triazolyl) methyl] -4-n-propyl-1,3-dioxolane, 2- [p- (4'-Trifluorophenoxy) phenyl] -2- [1- (1H-1,2,4-triazolyl) methyl] -4-ethyl-1,3-dioxolane 2- [p- (4'-chlorophenoxy) -2-methylphenyl] -2- [1- (1H-1,2,4-trlazolyl) methyl] -4-ethyl-1,3-dioxolane, 2- [p- (4'-chlorophenoxy) -2-methylphenyl] -2- (1H-imidazolylmethyl) -4-ethyl-1,3-dioxolane. Process according to one of Claims 1 or 2, characterized in that the corresponding compounds of the formulas IV, Va and Vb are used as starting materials to give 2- {p- (4'-chlorophenoxy) -2-chlorophenyl] -2- [1- (1H-1,2,4-triazolyl) methyl-4-ethyl-1,3-dioxolane, 2- [(2-ethyl-4-phenoxy] phenyl] -2- [1- (1H-1,2,4-triazolyl] methyl] -4-methyl-1,3-dioxolane with nitric acid.