CS241523B2 - 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 arylphenyl ether derivatives are used to combat phytoipathogenic fungi in plant protection.

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

Ji) in which

Y is —CH = or —N—,

R a _and R _b are each independently hydrogen, halogen, C 1 -C 3 alkyl or ^n- ethoxy

U and V are each independently a C 1 -C 3 alkyl group or together represent any of the following alkylene bridges

whereas

R ₁ and R ₂ are each independently hydrogen, C 1 -C 3 alkyl or -CH ₂ -Z-R ₇ where

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 ₅ , R ₁ and R ₅ not exceeding * 6, and

Ar represents a group of the formula

whereas

R _c , R _rt and R _c 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. and oxalic acid or sulfonic acids such as benzenesulfonic acid and methanesulfonic acid.

The complexes of copper and compounds of formula I consist of a basic organic molecule and an inorganic or organic salt of copper, for example a halide, nitrate, sulfate, phosphate, copper tartrate. 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 plant protection properties. 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 _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 bridges

read or take

R 1 and R ₂ are each independently hydrogen, C 1 -C 3 alkyl or -CH ₂ -Z-R ₇ where

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 _3i R ₄ and R ₅ are independently hydrogen or alkyl having from 1 * to 3 carbon ·., Atoms, the total number of carbon atoms in R _3, R ₄ and R ₅ does not exceed the number * 6, and

Ar represents a group of the formula

where

R _c , R j 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 group of agriculturally použitel241523 NYCHA fungicides are compounds of formula I, including their salts and complexes with copper, in which Y is -CH = or -N =, R _{and Rb} are independently hydrogen, halogen or alkyl having from 1 to 3 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

in which

Ri, R _2, R _3, R ₄ and R ₅ are independently hydrogen or alkyl having 1 to 4 carbon atoms, the total number of carbon atoms in R substituenteeh _3, R _4, and _R does not exceed the number 6.

This group will be referred to as Ic.

Another preferred group of agricultural preferred fungicides are those compounds of formula I wherein Y is -CH = or - N =, Ar has the meanings mentioned ρο · ά Formula I, R _n, R _b, R _c, R _e and R j are each independently hydrogen, chloro, bromo, fluoro, methyl, methoxy or nitro, U and V are independently C1-C3 alkyl or together form the alkylene groups represented by formula I, wherein R1 _; R _2, R, R / ,, R5 and _R6 are independently hydrogen or alkyl having 1-3 carbon atoms or R _t is -CH ₂ -O-R ₇ wherein R ₇ is an alkyl group having 1 to C 3 -C 3 alkoxy, C 1 -C 3 alkoxy substituted by C 2 -C 4 alkyl, 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- (phenoxyphenyl) -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- [β- (4‘-bromophenoxy) phenyl] -2- [1- (1H-1,2,4-triazolyl) methyl] -4-ethyl-1,3-dioxolane,

2- [p- (phenoxy) -2'-methylphenyl] -2- [1- (TH-1,2,4-triazolyl) methyl] -4-ethyl-1,3-dioxolane,

2- [p- (3 ', 4 ^: -dichlorophenoxyphenyl) -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- [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-triazolyl) methyl] -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 carrying out at temperatures from 0 ° C to 220 ° C, in particular at 80-170 ° C and preferably in a polar organic solvent, which are inert under the reaction conditions, the compounds of formulas VIII and IX condense with each other

yj (IX) (VIII) ¹ wherein X ₃ and X ₄ are -O-Me, wherein

Me is hydrogen or preferably a metal cation and the other of these is aryloxy-interchangeable and

R _a , R _b , U, V and Y are as defined 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 optionally with reaction with an alkali carbonate, bicarbonate or hydroxide The metal is converted to the free compound or the optionally obtained free compound or the acid addition salt obtained is converted by reaction with a copper salt to a copper complex.

The metal cations Me are, for example, alkali metal cations, for example lithium, sodium or potassium, or alkaline earth metal cations, for example magnesium, calcium, strontium or barium.

In the process of the present invention, the intermediates and end products can be isolated from the reaction mixture and, if desired, purified by generally conventional methods such as extraction, crystallization, chromatography, distillation, etc.

The above process is preferably based on compounds of formulas VIII and IX, wherein X ₃ is a -OMe group and X ₄ is a nucleofugile leaving group, or vice versa, X ₃ is a nucleoeffective leaving group, and X ₄ is a -OMe group. . Hereby, the symbols R _and R · ,, U, V, Y and Ar as defined in formula I. Me means preferably hydrogen.

The reaction is preferably carried out under the following conditions:

Nucleavable cleavable groups are, for example, reactive esterified hydroxy groups, such as hydroxy groups esterified with hydrofluoric acid, hydrochloric acid, hydrobromic acid or hydroiodic acid or a lower alkanoic acid, optionally substituted with benzene or halenesulfonic acid, for example methane, ethane, benzene, p, fluoro-sulfonic acid.

The reaction is preferably carried out in a relatively polar but inert organic solvent such as, for example, Ν, am-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, acetonitrile, benzonitrile and others. Such solvents may be used in combination with other solvents which are inert under the reaction conditions, such as aliphatic or aromatic hydrocarbons, for example benzene, toluene, xylene, hexane, petroleum ether, chlorobenzene, nitrobenzene and others.

Elevated temperatures from 0 to 220 ° C, preferably 80 to 170 ° C are preferred. The reaction mixture is expediently heated to reflux.

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 compounds obtained can be recalculated to other compounds of formula I. For example, compounds of formula I in which U and V are the same and are optionally substituted alkyl radicals of 1 to 12 carbon atoms can be replaced by reaction with 1 mol of another, optionally substituted (C 1 -C 12) alkanor 1 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 recrystallization is carried out in a customary manner, for example in the presence of an acidic condensing agent such as a mineral acid, a sulfonic acid or a strong carboxylic acid, for example hydrochloric or hydrobromic acid, sulfuric acid, β-toluenesulfonic acid or trifluoroacetic acid, preferably under distillation or distillation removal of easily boiling reaction products.

In addition, optionally additional substituents may be introduced into the carbocyclic aryl moieties of the compounds obtained by the process of the invention into the radical Ar and / or R _and optionally R 1. Thus, for example, halogen can be introduced by reaction with a halogen in the presence of a Lewis acid such as iron (III), zinc, boron or antimony (III) or N-chlorosuccinimide.

Further, nitro groups can be reduced, for example with suitable complex hydrides, for example lithium aluminum hydride, to amines, these amines then 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 ketones of formula (IV) may be prepared by halogenation of methylarylketones of formula (XIV)

to form compounds of formula XV

and further reacting compounds of Formula XV with an azole of Formula II / -N-MeyasJ (m wherein

Y represents —CH— or —N = a

Hal is preferably chlorine or bromine, while

Ar, R _a , R _b are as defined above.

The ketals of formula IX are obtained by reacting the starting ketone with a suitable alcohol or diol.

The described process variants are also part of this invention.

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

Ar-0 / rN / - J

Ar-O

R

with.

^{Rf =} 0 / rN

Typy-J r ^J types / \

V (Wf)

R «

ÍXVJ /

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

?C

R (XVIII)

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

............... - for

- = v ► = in front of the plane shown

The type B configuration is referred to herein as the " cis "

Separation of the two diastereomers can be carried out, for example, by fractional crystallization or by chromatography (thin layer chromatography, dilution chromatography, column chromatography, high pressure liquid chromatography, etc.), both of which exhibit different biological activity.

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

Some of the starting materials and intermediates used in the process of the invention are known compounds, others 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 and bactericides in the following publications:

U.S. Pat

575 999,

936 470,

101 664,

101 666 a

156 008.

It has surprisingly 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 antimycotic and / or anticonvulsant properties which establish their utility as drug active substances. Thus, these compounds have very advantageous curative, preventive and systemic properties in plant protection and can be used to protect crop plants. The active compounds of the formula I can control or destroy microorganisms occurring on plants or parts of plants (such as fruits, flowers, leaves, stems, tubers and roots) of various useful plants, while remaining protected from such microorganisms and 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,

Rhizoctonla,

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 formula I for combating phytopathogenic microorganisms, in particular fungi which are harmful to plants or preventively prevent the attack of plants.

In addition, the present invention also encompasses the production of agrochemical compositions which consist in mixing the active ingredient thoroughly with one or more of the substances described herein or with 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 or of 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-bearing fruit with kernels, seeds and berries, for example:

apple tree, pear, plum, peach, almond, cherry, strawberry, raspberry, blackberry,

241323 legumes such as beans, lentils, peas, soybean, oilseeds such as rape, mustard, poppy, olive tree, sunflower, coconut, castor, cacao, groundnuts, cucurbits such as pumpkins, cucumbers, melons, fibrous plants such as cotton, flax, hemp, jute, citrus-fruit trees, such as orange, lemon, tangerine, mandarin, various vegetables such as spinach, lettuce, asparagus, cabbage, carrots, onions, tomatoes, potatoes, paprika, laurel plants such as avocado (Porsea gratissima), cinnamon, camphor, or other plants such as maize, tobacco, butternut, coffee, sugarcane, tea, grapevine, hops, banana and rubber, as well as ornamental Plants (Compositae J.

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, bactericiruses, nematicides, molluscicides or mixtures of several of these preparations, together with, if appropriate, other conventional carriers, surfactants or other additives which improve application possibilities.

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

One preferred method used in agriculture to apply the active compound of the formula I or the agrochemical composition to the 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), but the active compounds of the formula I can also be fed to the plant via soil via the root system (systemic effect). The compounds of formula I may, however, 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, encapsulation into, for example, polymeric substances in a known manner.

Application procedures, such as spraying, fogging, dusting, sprinkling, coating or watering, as well as the type of agent, are selected appropriately, according to the desired objectives and conditions. 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. surfactants and optionally surfactants (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, such as alcohols and glycols. and their ethers and esters, such as ethanol, ethylene glycol, ethylene glycolmoriomethyl ether or ethylene glycol monoethyl ether, ketones such as cyclohexanone, strongly polar solvents such as N-methyl-2H-pyrrolidone, dimethylsulfoxide or dimethylformamide, and optionally epoxidized vegetable oils such as epoxidized coconut oil or soya 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 disperse silicic acid or 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, and 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.

Depending on the type of active compound to be treated, non-ionic, cationic and / or anionic surfactants having good emulsifying, dispersing and wetting properties are suitable as surface-active compounds. Surfactants are also understood as meaning mixtures of surfactants.

Suitable anionic surfactants can be both water-soluble soaps and water-soluble synthetic 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 o-stearic acid or mixtures of natural fatty acids It is also necessary to mention the salts of fatty acids with methyl taurine, for example from coconut oil or tallow oil.

However, so-called synthetic surfactants, in particular fatty sulfonates, fatty sulfates, sulfonated benzimidazole derivatives or alkylarylsulfonates, are more commonly used.

Fatty sulphonates or fatty sulphates are generally present as alkali metal, alkaline earth metal or optionally substituted ammonium salts and contain an alkyl radical of 8 to 22 carbon atoms, the alkyl also including the alkyl portion of the acyl radicals, such as is, for example, the sodium or calcium salt of ligninsulphonic acid, dodecylsulphuric acid ester or a mixture of sulphated 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 C 8 -C 22 fatty acid residue. 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, p-olylglycol ether derivatives 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 residue and 6 to 18 atoms carbon 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 non-ionic surfactants include nonylphenol polyethoxyethanols, castor oil polyglycol ethers, polypropylene adducts with polyethylene oxide, tributylphenoxy polyethoxyethamol, polyethylene glycol and octylphenoxypolyethoxyethanol.

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

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

Surfactants useful in the manufacture of the agrochemical compositions of the present invention are described, inter alia, in the following publications: Mc Cutcheon ' s Detergents and Emulsifiers Annual MC Publishing Corp., Ringwood New Jersey, 1980 Sisely & Wood, Encyclopedia of Surface Active Agents, Chemical Publishing Co. ., 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 a surfactant.

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.

Examples illustrating the production method:

Example 1

Preparation of 2- [p- (2-nitro-4-trifluoromethylphenoxy) phenyl] -2- (1-imidazolylmethyl) -4-ethyl-1,3-dioxolane

(3,263)

8.3 parts of 2- (p-hydroxyphenyl) -2- (1-imidazolylmethyl) -4-ethyl-1,3-dioxolane are dissolved in 300 ml of dimethylsulfoxide and 1.84 parts of ground potassium hydroxide are added to the solution at which temperature rises. from 23 to 36 ° C. After heating to 70 degrees Celsius for two hours, 7.4 parts of 4-chloro-3-nitrobenzitrifluoride in 100 ml of dimethylsulfoxide are added dropwise with stirring at 70 degrees Celsius and stirred at 70 ° C for 3 hours. After cooling to room temperature, the reaction mixture is poured onto 2000 ml of water and extracted twice with 200 ml of diethyl ether. The combined extracts were washed twice with 70 ml of water each time, dried over sodium sulfate and the solvent was evaporated. The oily residue was purified by silica gel column chromatography using ethyl acetate as eluent. After evaporation of the solvent, the mixture of diastereomers remains as a viscous mass. After digestion with petroleum ether, colorless crystals having a melting point of 96-102 ° C are obtained.

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, A indicates a type A diastereomer and B indicates a type B diastereomer.

2415 23

W'Tabulka 1

Compounds of formula XXI

R wherein isomeric forms are also included:

R ₁₀ Y salt physical data nina number

1.1 H N - mp 100-102 ° C 1.2 H N HNiO ₃ 1.3 H CH - 1.4 ch ₃ N - mp 85-92 ° C 1.5 ch ₃ N HCl 1.6 ch ₃ N CuCl ₂ 1.7 ch ₃ CH - 1.8 ch ₃ N MNI (NO _{3) 2} 1.9 C ₂ H ₅ N - mp 81.5-83.5 ° C 1.10 c ₂ h ₅ N HNO _a 1.11 c ₂ h ₅ N ZnCl ₂ 1.12 C ₂ H ₅ N Μπι (ΝΟ _{3) 2} 1.13 c ₂ h ₅ N FeCl ₃ 1.14 c ₂ h ₅ CH - light brown oil 1.15 c ₂ h ₅ CH CuCl ₂ 1.16 C ₃ H ₇ -n CH - 1.17 C ₃ H ₇ -n N - mp 68.5-71 ° C 1.18 C ₃ H ₇ -n N ZnCl ₂ 1.19 C ₃ H ₇ -n N HCl 1.20 CiHg-n N - 1.21 C4H9-11 CH - 1.22 . CH ₂ C1 N - 1.23 ch ₂ oh N - mp 111-122 ° C 1.24 CH ₂ OCH 2 Q -Cl N - viscous oil no ²⁶ = 1,5865 A 1.25 c ^ ochj-Q-ci N - mp 83-85 ° C B 1.26 N - mp 107-109 ° C A 1.27 N - mp 90-94 ° C B 1.28 ch ₂ oh CH - mp 118-1123 ° C 1.29 ch ₂ and ₃ CH - 1.30 c ₂ h ₅ N 1/2 C111SO4 1.31 ch ₂ oc ₂ h ₅ N - 1.32 ch ₂ and ₃ N - 1.33 CH2OCH2CH2OCH3 N -

Table 2

Compounds of formula XXII

R.

A41

R.

H (XXII)

including isomeric forms.

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5.1 ch ₃ c ₂ h ₅ 2-C1 H CH 5.2 ch, c ₂ h ₅ 2C1 H N - 5.3 ch ₃ C ₂ H ₅ 2-C1 6-01 CH HNO, 5.4 ch ₃ c ₂ h _{5 2-CH,} H N HNO ·, 5.5 CH, C, H ₇ -n 2-C1 H CH - 5.6 CH, C, H ₇ -n 2-C1 H N - 5.7 ch ₃ C, H ₇ -n 3-C1 H N HNO ;, 5.8 CH, C-, H ₇ -n 3-C1 6-C1 N Min (NO ₃ ) ₂ 5.9 CH, CH ·, 2-C1 H CH - 5.10 CH, CH ·, 2-C1 6-C1 CH CuCl ₂ 5.11 CH, c ₂ h _p 2-C1 H CH MIB (NO _{3) 2} 5.12 CH, c ₂ h ₅ 2-CH, 6-CH, CH CuC1 ₂ 5.13 ch ₃ CH, 2-CH, H N ΗΝΌ3 mp 158-160 ° C 5.14 CH, CH, _2-CH3 H N HBr mp 192-204 ° C 5.15 CH, C ₂ H ₅ 2-CH ;, H N Mn _{(NO3) 2} 5.16 CH, c ₂ h ₅ 2-NO ₂ H N FeCl ₃ 5.17 CH ₃ CH, 2-CI H N - 5.18 ch ₃ ch ₃ 2-C1 5-C1 N hno ₃ 5.19 c ₂ h ₅ ch ₃ 3-C1 H CH MnCl ₂ 5.20 c ₂ h ₅ CH, 2-CH, H N M, nCl ₂ 5.21 c ₂ h ₅ CH, _2-CH3 H N CuCl ₂ 5.22 c ₂ h ₅ CH, 2-C1 5-C1 N ZnCl ₂ 5.23 c ₂ h ₅ c ₂ h ₅ 2-Br H CH - 5.24 H c ₂ h ₅ 2-OCH ₃ 6-OCH, 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 CH, 2-C1 H N - 5.31 H CH, 2-C1 H N HNO3 5.32 H ch ₃ 2-C1 6-C1 N - 5.33 H CH, 2-C1 H CH - 5.34 H CH, 2-OCH, G-OCH, CH - 5.35 H CH, 3-C1 H N 5.36 H CH, 2-CH, H N ΗΝΌ3 mp 132-134 ° C 5.37 H CH, 3-CH ₃ H N - 5.38 H c ₂ h ₅ 3-CH, H CH CuCl ₂ 5.39 H c ₂ h ₅ 2-CH ·, 6-CH, N - 5.40 H c ₂ h ₅ 2-CH, H N HNO ₃ mp 108-110 ° C 5.41 H C2H5 2-Br 5-Br N - 5.42 H C ₂ H ₅ 2-C1 H N - oil, n _D ²² = 1.5 6 20 5.43 H C ₃ H ₇ -n 2-C1 H N 5.44 H C ₃ H ₇ -n 2-C1 6-C1 N - 5.45 H C ₃ H ₇ -i 2-CH, H N - 5.46 I-I C ₃ H ₇ -i 2-CH, H CH - 5.47 H C, H ₇ -t 2-OCH, 6-OCH, N MnCl ₂ 5.48 C2H5 c ₂ h ₅ 2-C1 H N - 5.49 C2H5 C ₂ H ₅ 2-C1 H N HNO ₃ 5.50 C2H5 c ₂ h ₅ 2-C1 6-C1 N HCl 5.51 ! H H 2-OCH ₃ 6-OCH 3 CH -

Rn R, 2 r ₁₇ ^R 18 Y salt physical data C2H5 C3H7-I 2-CH3 H N - H c ₂ h ₅ 2-OCH ·) 6-OCH'i N - H C ₂ H ₅ 2-OCH ·, 6-OCH 3 N - H H 2-OCH ·, 6-OCH 3 N - ch ₃ c ₂ h ₅ 3-C1 H N (COOHh ch ₃ c ₂ h ₅ 2-CH3 6-CH3 CH (COOH) ₂ ch ₃ C3H ₇ -í 2-C1 H N - ch ₃ C 1 H-y-1 2-C1 6-C1 N H ₂ SO ₄ - (CH ₂ ) ₄ - 2-C1 H CH - - (CH ₂ ) ₄ - 2-C1 H CH HNO3 - (CH _{2) 4} - 2-C1 H N - - (CH ₂ ) ₄ - 3-C1 H N Qn (NO ₃ )? - (CH _{2) 4} - 3-C1 6-C1 N (COOH) ₂ - (CH _{2) 4} - 3-C1 5-C1 N ZnCl? - (GH _{2) 4} - 3-C1 6-C1 N HCl - (CH ₂ ) ₄ - 2-C1 H CH ZnCl? H H 2-CH ·, H CH - mp 103-106 ° C ch ₃ CH, 2-CH ·, H CH - H C ₃ H ₇ -n 2-CHa H CH - yellow resin n _D ⁵⁰ = 1.5476 H CH ₃ OCH ₃ 2-CH3 H CH - resin H CH ·, 2-CH3 H CH  - H c ₂ h ₅ 2-CH, H CH - resins, n _D ⁵⁰ = 1.5557 H ch ₂ oh 2-CH ·. H CH - H ch? och ·. 2-CH ·, H N • __ oil, n _D ⁵⁰ - 1.5482 H c ₂ h ₅ 2-CH ·, H N - resin, n _D ⁵⁰ = 1.550) 2 H H 2-CH ·, H N - mp 103-105 ° C H CgHy-n 2-CH ;, H N - resins, n _D ⁵⁰ = 1.5467 H CH ₂ OH 2-C.l H CH - H c ₂ h ₅ 2-Br H CH - H c ₂ h ₅ 2-C1 H CH - resin, n _D ²² = 1.5765 H CH ₂ 0CH ·, 2-C1 H CH - H CH ₂ OCH ₃ 2-C1 H N - H ch ₂ oh 2-Br H CH - H ch ₂ and ₃ 2-Br H CH - ch ₃ CH ·, 2-Br H N - H CH ₃ OCH ₃ 2-Br H N - H CH _? OH 3-NO ₂ H CH - H C ,, H ₇ -n 3-NO ₂ H N - H c ₂ h ₅ 2-Br H N  - H C2H5 3-NO, H CH  - H ch ₃ 3-NO ₂ H CH  - H c ₂ h ₅ 3-NO? H N  - H ch ₃ 3-NO ₂ H N - H ch ₂ oh 3-CH ·, H CH - H ch ₂ och _p 3-CH ·, H N - H c ₂ h ₅ 2-NO ₂ H CH - H ch ₂ and ₃ 2-NO ₂ H CH - H ch ₂ and ₃ 2-NO? H N - H c ₂ h ₅ 3-CH ·, H CH - n _D 20.5 ₌ 1.5692 H ch ₂ and ₃ 3-CH, H CH H c ₂ h ₅ 3-CH ·, H N . - m _D ²² 1.5577 H CH2OH 2-NO ₂ H CH - H c ₂ h ₅ 2-NO? H N - 2-CH 3 H 2-CH3 5-CH3 CH - · viskóaní product, n _D ⁵⁰ = 1.5463 H C ₃ H ₇ -n 2-CH3 Ø | 8 N —- oil, n _D ²² = 1.5461, A H C ₃ H ₇ -n 2-CHa H N - viscous oil, n _D ²² = 1.5468, B H C ₂ H ₅ 3-CH3 H N  - resin,

compound number Rh ^r 12 r ₁₇ ^R 18 Y salt physical data 5.109 H c ₂ h ₅ 3-CHg H CH - resin, n _D 50 = 1.5732 5.110 H C ₂ H ₅ 2-CoHr H N hno ₃ mp 132-134 ° C 5.111 H C ₂ H ₅ 2-CH ·, H CH (COOH) ₂ mp 115-118 ° C 5.112 H C ₂ H ₅ 2-C ₂ H ₅ H N - oil, n _D ²² = 1.5642 5.113 H C ₂ H ₅ 3-CH ·, H N - oil, n _D ²² - 1.5631, A 5.114 H c, h ₅ 3-CH, H N - oil, n _D ²² = 1.5633 5.115 H c, h ₅ 2-C ₂ H ₅ H CH - brown resin 5.116 H CH ·, 2-C 9 H 5 H CH HNO3 mp 105-119 ° C 5.117 H CH ·, 2-C ₂ H ₅ H CH - viscous oil 5.118 H CH ·, 2-C ₂ H ₅ H N HNO ·, mp 136-138 ° C 5.119 H c ₂ H ₅ 2-CH, H CH HCl mp 166-171 ° C 5.120 H c ₂ h ₅ 2-CH ·, H CH h ₂ Sat ₄ mp 136-138 ° C 5.121 H C ₂ H ₅ 2-CH ·, H CH ch ₃ Sat ₃ h mp 98-106 ° C 5.122 H C ₂ H ₅ 2-CH ·, H CH hno ₃ mp 96-98 ° C 5.123 H c ₂ h ₅ 2-C ₂ H ₅ H CH hno ₃ mp 134-137 ° C 5.124 H c ₂ h ₅ 2-CH ·, H CH - oil, 5.125 H c ₂ h ₅ 2-CH ·, H CH - oil, B 5.126 H C ₃ H ₇ -n 2-CHg 5-CH3 N - n _D ²³ = 1.5580 5.127 H No. ₂ H ₅ 2-CH ·, _5-CH3 N - mp 73-75 ° C 5.128 H ch ₃ 2-CH ·, _5-CH3 N - mp 93-95 ° C 5.129 ch ₃ ch ₃ 2-CH3 5-CH3 N - mp 59-62 ° C 5.130 H ch ₃ 2-CHg 5-CH ·, CH -. n _D ²³ = 1.5751 5.131 H c ₂ h ₅ 2-CH ·, 3-CHg N HNO3 mp 103-105 ° C 5.132 H c ₂ h ₅ 2-CHg 3-CH3 CH hno ₃ mp 126-128 ° C

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Examples of fungicidal compositions which contain liquid active compounds of the formula I (θ / ο == o / o by weight):

2. Emulsin concentrate

and) (b) C) the active substance of Tables 1 to 10 25% 40% 50 o / o calcium dodecylbenzenesulfonic acid acid 5% 8% 6% castor polyethylene glycol ether oils (36 moles of ethylene oxide) 5 θ / ο - - tributylphenoylpolyethylene glycol- ether (30 mol ethylene oxide) - 12 O / o 4 o / o cyclohexanone - 15 o / o 20 o / o mixture of xylenes 65 o / o 25% 20 o / o Of such concentrates, they may be dilution with water prepare emulsions for each required concentration. 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% 5% gasoline (boiling point 160—190 ° Cj - - 94% - These solutions are suitable for application in minimal form drops. 4. Granulate aj bj the active substance of Tables 1 to 10 5% 10 o / o kaolin 94 ^! % - highly dispersed acid siliceous 1 «/ o -. 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

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the active substance of Tables 1 to 10 2 o / o 5% highly dispersed silicic acid 1% 5% talc 97% - kaolin - 90 O / o

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

Examples of fluoride formulations which contain solid active compounds of the formula I ('% = -% / w / w):

6. Wettable powder; and (b) (c) active substance of Tables 1 to 10 sodium ligninsulphonic acid sodium lauryl sulphate sodium diisobutylnaphthalenesulphonate octylphenolpolyethylene glycol ether (7 to 8 moles of ethylene oxide) visocedisperse silica kaolin

25% 50% 75% 5% 5% - 3% - 5% - 6% 10% _ 2% _ 5% 10% 10% 62 27% -

calcium dodecylbenzenesulfonic acid

The active ingredient mixes well with the others! The ingredients are well ground in a suitable mill to give a wettable powder that can be diluted with water to suspensions of any desired concentration.

7. Emulsion concentrate active substance from Tables 1 to 10 10% oiktyilphenolpolyethylene glycol ether 3% (4 to 5 molar ethylene oxide)

8. Acid dust 3% castor oil polyglycol ether (35 m, ol ethylene oxide) 4% cyclohexanion 30% xylene mixture 50%

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

(b) active substance in Tables 1 to 10 5% 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. Granulate obtained by extrusion of ligniinsulfonic acid sodium salt 10% active ingredient of Tables 1 to 10 10% natmumlignin sulphate 2% carboxymethylcellulose 1% kaolin 87% carboxymethylcellulose 1%

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

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% nonylphenioilpolyethylene glycal ether (15 mol ethylene oxide) 6%

The finely divided active ingredient is intimately mixed with the remaining ingredients. A suspension of any desired concentration can be prepared by dilution with water.

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 ethyl ethyl bis-dithiocarbamate

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

C = 'Fentin Acetate' = tryphenyicin acetate

D = "Forpet" = N-trichloromethylthiophthalimide

Example 1 8

Effect against rust (Puccinia graminis) on wheat> a) Residual protective effect

Wheat plants are sprayed with a suspension made of a 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 95-100% relative humidity 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

5 days after sowing, the wheat plants are covered with a suspension made of a wettable powder of active substance (concentration 0.006% of active substance per volume of soil). At 48 hours, the treated plants are infected with a uredospior fungus suspension. After incubation for 48 hours at 95-100% 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. Individual results are shown in the following table:

Residual protective effect against Compound number% Puccinia gramiinis compound number attack 1.9 0—5 3.279 0—2 1.17 0—1 3.287 0—5 1.24 0—1 3.2912 0—4 1.26 0—4 3.311 0—3 2.17 0-5 3.314 0 3.1 0—1 3.340 0—2 3.2 0 3.348 0-1 3.6 0 3.373 0—2 3.7 0 3.376 0—4 3.8 0—4 4.2 1—3 3.12 0—1 4.15 5-12 3.26 0—5 4.23 5-7 3.51 0—2 4.50 0—5 3.52 0—2 4.55 0—4 3.54 0—2 4.57 0—3 3.55 0—3 4.66 0—5 3.70 0-4 4.70 3—5 3.75 0—4 4.77 0—4 3.78 0—3 4.78 0-4 3.83 0-2 4.81 0 3.85 5—7 4.89 2-4 3.86 0—2 4.90 0-2 3.127 0—1 4.91 0—2 3.133 0 4.92 0-4 3.155 0 4.93 0 3.156 0 4.94 4-5 3.160 4—7 4.113 0—5 3.162 0—1 4.116 . 0—4 3.164 0 5.13 0—2 3.168 0 5.14 0 3.171 0—4 5.36 0 3.172 0—4 5.40 0—2 3.176 0—3 5.70 0—1 3.177 0—4 5.71 4—7 3.193 0-5 5.76 3-5 3.212 0—4 5.78 4-5 3.213 0—3 6.8 0—5 3.220 0-4 7.7 0-1 3,226 0—4 7.33 5—7 3.227 0—3 8.66 0-2 3.231 0 AND 90—95 3.232 0 (B) 92—97 3.233 0 C 90—95 3.234 0 D 90—93 3.263 0-1 kontrlota 100 ALIGN! 3.267 0 3.274 0

26

In addition, it zid konidii hiornby. The infected plants are po value No 6.8 excellent systemic effect. incubate diobium at about 21 ° C for 72 hours The infestation with Puccinia was degrees Celsius and at high humidity la suppressed (0% attack). This effect and then placed in the greenhouse until · it was also possible to find out at a significantly lower occurrence of typical spots on the leaves. Posiou- application rate 0.006 «/ o. The fungicidal effect is determined for 12 days after infection, and that • based on the number and Example 19 bones of occurring spots. Compared with untreated but infi- Effect against Cercospora ar .; ichidicola na forged control plants (number and peanut plants stain size = 100%), show plants groundnuts that have been treated with 10 to 15 cm tall groundnut plants active substances from Tables 1 to 10 considerably they are oily sprayed with a spray suspension reduced attack sponge Cercospora. Poison- (0,02% of active substance) which: was manufacturing- noticeable results are listed in the following of a wettable powder active substance. table: After 48 hours, the plants are infected with a suspension. Effect against Cercospora arachidicola: Compound number% compound number attack% 1.1 0—4 3.267 3—4 1.4 2—5 3.292 0—4 1.9 0 3.314 0 1.14 7—10 3.348 0—2 1.17 0 4.15 0 1.24 0 4.23 1 1.25 0 4.50 0 1.26 0—2 4.57 0—3 1.27 0—1 4.59 0—2 2.17 0 4.66 0—2 3.1 0 4.89 0 3.2 5—10 4.90 0 3.6 0-4 4.91 0 3.7 0 4.92 0 3.11 0 4.93 0 3.51 0—4 4.94 5—7 3.52 0—3 4.113 0 3.54 0—3 4.116 5—7 3.55 0 5.13 0 3.75 5—10 5.14 0 3.78 0 5.36 0 3.85 0 5.40 0 3.86 0 5.70 0—2 3.127 0—1 5.71 0—2 3.133 0—4 5.73 0 3.155 5—9 5.75 0 3.156 0 5.76 0 3.162 0-5 5.77 0-1 3.171 0—3 5.78 0 3.172 0 6.1 0 3.176 0 6.8 0 3.177 0—1 7.33 7—9 3.212 0-5 7.34 3—5 3.213 2—3 8.72 7—10 3.220 4—5 AND 93—98 3.221 0 (B) 95—100 3.226 0—3 C 93—96 3.231 0 D 94—98 3.232 0 control 100 ALIGN! 3.233 0 3.234 0

Example 20 bj Systemic effect: Effect against powdery mildew (Erysiphe gra- About 8 cm tall barley plants minis) barley with a suspension (concentration 0.006% related substances related to volume of soil], which aj Residual protective effect was made of wettable powder. substances. Care must be taken that the suspension About 8 cm tall plants barley is - that there was no contact with the above-ground parts sprayed with a suspension (with a concentration of 0.02% plant. After 48 hours, the treated plants active substance), which was made of dusts with conidia mushrooms. Infected readable powder of the active substance. After 3 to 4 barley plants are placed in a greenhouse at During the hours the treated plants are dusted with co- a temperature of about 22 ° C and a pH of approx 10 days to be assessed nidiemi mushrooms. Infected barley plants fungus infestation. is then placed in a greenhouse at a temperature of about Compounds of formula I show good 22 ° C and after 10 days the infestation is assessed dual protective effect against powdery mildew sponge. (Erysiphe gramimis). Untreated however infected control plants show 100% attack by grass powdery mildew, The test results are summarized in the following- Table: Effect against powdery mildew Erysiphe graminis compound number attack% compound number * attack% 1.1 0—4 3.212 0—5 1.4 4—7 3.213 4-5 1.9 0 3.220 10 1.14 30 3.221 5—8 1.17 0 3.226 0 1.23 0 3.227 0—3 1.24 0—5 3.231 4-5 1.25 0 3.232 5 1.26 0 3.233 3—5 1.27 0—3 3.234 7—9 2.17 0—4 3.263 0—4 3.1 0 3.267 0-2 3.2 0 3.274 0 3.6 0 3.279 11 3.7 0 3.287 5—7 3.8 0 3.292 5—8 3.11 0 3.311 0 3.12 0—4 3.314 0 3.26 2—5 3.340 10 3.51 0 3.348 10—15 3.52 0—3 3.373 0—3 3.54 0—3 4.2 5—7 3.55 0 4.15 0 3.70 0 4.23 2—5 3.75 0 4.50 0 3.78 0 4.57 0 3.85 7—8 4.59 0 3.86 0 4.66 2—5 3.103 5—9 4.77 0 3.127 0-5 4.78 0 3.133 0—1 4.81 0 3.156 0 4.89 0 3.160 0 4.90 0 3.162 0—2 4.91 0 3.164 0 4.92 0 3.168 0 4.93 0 3.171 2—5 4.94 0 3.172 0—3 4.113 3—5 3.174 7—9 4.116 2—3 3.176 5—6 5.13 0 3.177 0—3 5.14 0 3.193 0 5.36 0 5.40 0

compound number attack% compound number attack% 5.70 2—5 7.3 0 5.71 0 7.7 0 5.73 0 7.21 0—2 5.75 0 7.33 0 5.76 0 7.34 4—5 5.77 3—6 8.66 0 5.78 0 8.69 0-5 5.106 0 8.72 5—7 5.107 7—10 10.7 0 6.1 0 AND 98—100 6.8 0 (B) 100 ALIGN! 6.17 0 C 97—100 6.79 0—3 D 96—100 6.80 5—8 control 100 ALIGN!

Example 21 to the active ingredient. After 24 hours, the treated plants are infected with a fungal conidia suspension.

Residual protective effect against scab- The plants are then incubated for 5 days of apple trees (Venturia inaequalis) at 90 up to 100% relative air humidity; and Banks of apple tree they are placed in a greenhouse at 20-24 ° C for a further 10 days. The attack- Apple seedlings with 10 up to 20 cm d.lou- by 15 days post-infection. You- with fresh fresh shoots Spray sus- sledky test are evident from the following pensions (concentration 0.06% active substance), bulky: which was made of wettable powder. Effect against Venturia inaequalis compound number attack% Compound 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 13—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 A 100 4.15 8—9 B 100 4.23 7—10 C 100 4.50 0 D 100

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

Example 22

Effect against gray mold (Botrytis cinerea) on bean

Residual prititive effect

About 10 cm tall bean plants have an effect against Botrytis cinerea:

Compound number% sprayed with a suspension (at a concentration of 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 at 21 ° C, 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:

Compound 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% attack by Botrytis cinerea.

None of the comparative products A to D, which are common in the market, achieved a remarkable fungicidal effect at the low test concentrations used in these tests. In all tests, the challenge amounted to more than 90% and thus practically no different from untreated control plants.

Claims (8)

SUBJECT 1. A process for the preparation of novel derivatives of airylphenyl ethers of the formula I according to the invention having 1 to 3 carbon atoms or a methoxy group; U and V are, independently of one another, a (C1-C3) alkyl group or together form one of the following alkylene groups //) in which: Y is —CH = or - N =, R _a and R _b are each independently hydrogen, halogen, alkyl where R 1 and R ₂ are each independently hydrogen, alkyl having 1. to 3 carbon atoms, or a group of formula -CH ₂ -Z-R ₇ 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 _; j, R / and R, are independently hydrogen or alkyl having 1 to 3 carbon atoms, the total number of carbon atoms in R _J, R _Z and R ₅ does not exceed the number 6, and Ar represents a group wherein R _c , R i and R _e are each independently hydrogen, halogen, C 1 -C 4 alkyl, C 1 -C 3 alkoxy, trifluoromethyl or nitr. group, as well as their acid addition salts and their copper complexes, characterized in that at temperatures of 0 ° C to 220 ° C, in particular at temperatures of 80 to 170 ° C, and preferably in a polar organic solvent which is In general, the compounds of formulas VIII and IX condense with each other _Ar-Χ:! (VIII)? 3R (IX) with an organic or inorganic acid to form an acid addition salt, the resulting acid addition salt is optionally converted into the free compound by treatment with a carbonate, bicarbonate or an alkali metal hydroxide, or converting the free compound or acid addition salt obtained by treatment 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 C 1 -C 3 alkyl or together form one of the following alkylene groups wherein: R, and R _z are independently hydrogen, alkyl of 1-3 carbon atoms or -CH ·> -Z-R _7, wherein Z is oxygen or sulfur; and R ₇ is hydrogen, C 1 -C 3 alkyl, C 3 -C 4 alkenyl, methoxymethyl, phenyl, chloro or methyl-substituted phenyl, benzyl or chloro or methyl-substituted benzyl, R ₁ , R 2, and R ₅ are each independently hydrogen or C 1 -C 3 alkyl, the total number of carbon atoms in the substituents R 5 _; , R ₄ and R.-, does not exceed 6, Ar represents a group of the formula wherein R _c , R _d and R _e are independently of one another wherein one of X ₃ and X ₄ is -O-Me, wherein Me is hydrogen or preferably a metal cation, the other of which is an aryloxy-exchangeable residue, whereupon the optionally free compound obtained by the above approach is converted by reaction of a hydrogen atom, a halogen atom, a C1-C4 alkyl group, an alkoxy group C 1 to 3 carbon atoms, trifluoromethyl or nitro, and their acid addition salts and copper complexes, characterized in that at temperatures of 0 ° C to 220 ° C, in particular at temperatures of 80 to 170 degrees Celsius and preferably in the polar The compounds of formulas VIII and IX condense with each other in an organic solvent which is inert under the reaction conditions Ar = X ₃ (VIII) (IX) wherein one of X ₃ and X ₄ is -O-Me, wherein Me is hydrogen or, preferably, a metal cation, and the other is aryloxy-substituted radical, whereupon the compound obtained is optionally converted into an acid addition salt or a copper complex. Process according to either of Claims 1 and 2, characterized in that the corresponding compounds of the general formulas (VIII) and (IX) are used as starting materials to give compounds of the general formula (I) in which: Y is -CH- or -N-, Ra and Rj are each independently hydrogen, halogen or C 1 -C 3 alkyl, Ar represents a group of the formula wherein R _c , R 1 and R _e are each independently hydrogen, halogen or C 1 -C 3 alkyl, and U and V have the meaning given in point 1 or 2. Process according to either of Claims 1 and 2, characterized in that the corresponding compounds of the general formulas (VIII) and (IX) are used as starting materials to give compounds of the general formula (I) in which: U and V are, independently of one another, an alkyl group having from 1 to 3 carbon atoms or taken together to form one of the following alkylene groups R @ 1, R @ 3 or R @ _5, and wherein: R 1, R ₂ , R ₁ , R ₃ , R ₃ and R ₅ are each independently hydrogen or an alkyl group having 1 to 3 carbon atoms, the total number of carbon atoms in the substituents R ₃ , R 2, and R ₅ not exceeding 6, Ar represents a group of the formula wherein R 1, R 1 and R 1. are independently hydrogen, halogen or (C1-C3) -alkyl, and Y represents —CH— or - N =. Process according to either of Claims 1 and 2, characterized in that the corresponding compounds of the general formulas (VIII) and (IX) are used as starting materials, to give compounds of the general formula (I) in which: Y is -CH = or. —N =, Ar has the meaning given in point 1 or 2 of the following description of the trans -isomer. R _a , R b, R _c , Ret and R _e are each independently hydrogen, chloro, bromo, fluoro, methyl, methoxy, or nitro, U and V are, independently of one another, an alkyl group having from 1 to 3 carbon atoms or together form one of the alkyl groups defined in 1 or 2, wherein R 1, R ₂ , R ₃ and R ₄ , R ₅ are independently · Hydrogen or an alkyl group having 1 to 3 carbon atoms or R ₁ represents a group -CH ₂ -O-R ₇ , wherein R ₇ represents hydrogen, an alkyl group having 1 to 3 carbon atoms, an alkenyl group having 3 to 4 carbon atoms, or phenyl group. Process according to one of Claims 1 or 2, characterized in that the corresponding compounds of the general formulas (VIII) and (IX) are used as starting materials to give 2- [p- (phenoxy) phenyl] -2- (1- (1H-1,2,4-trlazolyl) methyl] -4-ethyl-1,3-dioxolane, 2- [p- (phenoxy) phenyl] -2- [1- (1H-1,2,4-triazolyl) methyl] -4-methyl-1,3-dloxane, 2- [p- ^(4! Chlorophenyldiguanide phenoxy) phenyl] -2- [1- (1H-1,2,4-triazolyl them -ethyl j-4-ethyl-3-dioxoilaniu, 2- [p- (phenoxy) -2-chlorophenyl] -2- [1- (1H-1,2,4-triazolyl) methyl] -4-ethyl-1,3-dioxolain, 7. A method according to any one of claims 1 or 2, characterized in that the corresponding compounds of the general formulas (VIII) and (IX) are used as starting materials, 2- [p- (3 ', 4'-Dichlorophenoxy) phenyl] -2- [1- (1H-1,2,4-triazole; olylmethyl) -4-methoxymethyl] -1,3-dioxolane , 2- [p- (3 ', 4'-Dichlorophenoxy) phenyl] -2- [1- (1H-1,2,4-itriazolyl) methyl] -4-ethyl-1,3-dioxolane, complex 2 - [p- (4'-chlorophenoxy) phenyl] -2- [1- (1H-1,2,4-triaolyl) methyl] -4-ethyl-1,3-dioixolain with copper sulphate, 2 - [(2-methyl-4-phenoxy) phenyl] -2- (1-imidazoilylmethyl) -4-ethyl-1,3-dioxolane, 2- [p- (phenoxy) -2-methylphenyl] -2- [1- (1H-1,2,4-thiazolyl) methyl] -4-ethyl-1,3-dioxolane, 2- [p - (4'-chlorophenoxy) -2-methylphenyl] -2- [1- (1H-1,2,4-triazoilyl) methyl] -4-methyl-1,3-dioxolane, 2- [p- (4‘-Chlorophenoxy) phenyl] -2- [1- (1H-1,2,4-triazoilyl) 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-1,5-dtaxam, 2- [p- (4'-biphenylphenoxy) phenyl] -2- [1- (1H-1,2,4-triazolyl) methyl] -4-n-propyl-1,3-dioxolane, 2- [p- (4'-difluorophenoxy) phenyl] -2- [1- (1H-1,2,4-triazolyl) imethyl] -4-ethyl-1,3-dioxolane, 2- [p- (4'-Chlorophenoxy) -2-methylphenyl] -2- [1- (1H-1,2,4-triazolyl) methyl] -4-ethyl-1,3-dioxolane , 2- [β- (4‘-chlorophenoxy) -2-methylphenyl] -2- (1H-imidazolylmethyl) -4-ethyl-1,3-dioxolane. 8. The method of any one of items 1 or 2, characterized in that the corresponding compounds of the general formulas (VIII) and (IX) are used as starting materials to form 2- [p- (4'-chlorophenoxy) -2-chlorophenynyl] -2- [1- (1H-1,2,4-triazolyl) methyl] -4-ethyl-1,3-dicxolam, salt 2 - [(2-ethyl-4-phenoxy) phenyl] -2- [1- (1H-1,2,4-triazoilyl) methyl] -4-methyl-1,3-dioxolane with nitric acid.