NO160580B - ARYLPHENYLETER DERIVATIVES AND APPLICATION OF THE SAME. - Google Patents

Description

1

The present invention relates to substituted arylphenyl-

ether derivatives of the following formula I as well as their acid addition salts and metal complexes. It also relates to agrochemicals containing as active ingredient at least one of the compounds of formula I, and their use for combating or protecting plants against phytopathogenic microorganisms.

Against the phenyl-triazolylmethyl ketals according to technical

kens represented by USP 4,160,838, USP 4,156,008, USP

4,106,666, DE 29 40 133, USP 3,575,999 and GB 2,027,701,

exhibits the compounds according to the present invention

nelse, whose molecular structure is extended by a (substituted)

phenoxy group in the para position on the phenyl ring, a completely unexpected and greatly improved plate fungicide effect.

The arylphenyl ether derivatives according to the present invention have

formula I

where Y is -CH= or -N=,

Ra and Rb, independently of each other, are hydrogen, halogen, Cj_-

C3-alkyl or C1-C3-alkoxy,

Ar means unsubstituted or by halogen, C₁-C₁ alkyl,

nitro and/or CF3, a one or more substituted phenyl,

U and V independently of each other are C₁-C₁ alkyl or

together form one of the following alkylene bridges

wherein R 1 and R 2 independently of each other are hydrogen, C 1 -C 4 -alkyl or is the group -CH 2 -O-R 7 , wherein

R7 is hydrogen, C1-C4~alkyl, C3-C4~alkenyl, a halogen, C1-C3-alkyl, one or more substituted phenyl or benzyl;

R 3 , R 4 and R 5 independently of each other mean hydrogen or C 1 -C 4 alkyl, the total number of carbon atoms in R 3 , R 4

and R5 does not exceed the number 6,

as well as their acid addition salts and metal complexes.

The substituent Ar has optionally substituted phenyl, e.g. the formula

where Rc, R( and Re independently of each other are hydrogen, halogen, C1~C4 alkyl, nitro or CF3.

By the term alkyl itself or as a component of another substituent, it is meant according to the number of the specified carbon atoms, e.g. the following groups: methyl, ethyl, propyl, butyl, pentyl or hexyl, as well as their isomers such as e.g. isopropyl, isobutyl, tert.-butyl, sec.-butyl, isopentyl etc.. Alkenyl means e.g. propenyl-(1), allyl, butenyl-(1), butenyl-(2) or butenyl-(3). Halogen here and in the following means fluorine, chlorine, bromine or iodine, preferably chlorine or bromine.

The invention relates to the free compounds of formula I as well as their addition salts with inorganic and organic acids, as well as their complexes with metal salts.

Salts according to the invention are in particular addition salts with physiologically compatible inorganic or organic acids in relation to the purpose of use.

With regard to the use as a microbicide in plant protection, physiologically compatible inorganic and organic acids are e.g. hydrohalic acid, e.g. hydrochloric, bromic or hydroiodic acid, sulfuric acid, phosphoric acid, phosphoric acid, nitric acid, possibly halogenated fatty acids, such as acetic acid, trichloroacetic acid and oxalic acid, or sulphonic acids such as benzenesulphonic acid and methanesulphonic acid.

Metal complexes with formula I consist of the underlying organic molecule and an inorganic or organic metal salt, e.g. the halides, nitrates, sulphates, phosphates, tartrates, etc., of copper, manganese, iron, zinc, and other metals. In this way, the metal cations can be present in different values.

The compounds of formula I are at room temperature stable oils, resins or solids which are distinguished by very valuable physiological, such as microbicide, e.g. plant fungicidal properties. Thus, they can be used in the agricultural sector or related areas when combating phytopathogenic microorganisms.

Particularly preferred compounds of formula I are the following: - 2-(p-(4-chlorophenoxy)-o-chlorophenyl)-2-(1-(1H-1,2,4-tri-azolyl)-methyl)-4 —ethyl-1,3-dioxolane, - 2-(p-(4-chlorophenoxy)-o-chlorophenyl)-2-(1-(1H-1,2,4-tri-azolyl)-methyl)-4- methyl-1,3-dioxolane, - 2-(p-(4-bromophenoxy)-o-chlorophenyl)-2-(1-(1H-1,2,4-tri-azolyl)-methyl-4-methyl- 1,3-dioxolane, - 2-(p-(4-chlorophenoxy)-o-chlorophenyl)-2-(l-(1H-1,2,4-tri-azolyl)-methyl)-4-propyl-l ,3-dioxolane, - 2-(p-(4-fluorophenoxy)-o-chlorophenyl)-2-(1-(1H-1,2,4-tri-azolyl)-methyl)-4,5-dimethyl- 1,3-dioxolane, - 2-(p-(4-chlorophenoxy)-o-chlorophenyl)-2-(1-(1H-1,2,4-tri-azolyl)-methyl)-4-methoxymethyl-1 ,3-dioxolane, and - 2-(p-(4-chlorophenoxy)-o-methylphenyl)-2-(1-(1H-1,2,4-triazolyl)-methyl-4-methyl-dioxane... .-The compounds of formula I can be prepared in the following way, whereby

A) condenses a compound of formula II

where Me is hydrogen or a metal cation, with a compound of formula III where X means a nucleofuge leaving group, or B) in a compound of formula IV transfers the carbonyl group in a group of formula V,

or

C) for the preparation of compounds of formula I, where

U and V together form a group with the formula -CH2-CH(CH2ZR^)- and means a residue different from hydrogen R^, condenses compounds of formula VI and VII

where one of the residues X 1 and X 2 means a hydroxy or mercapto optionally present in salt form, e.g. with formula -Z-Me, and the other a nucleophilic leaving group X or both X^ and X2 are hydroxy groups, with each other or D) condense compounds iried formulas VIII and IX

where one of the residues X^ and X^ means a group -O-Me, where Me is hydrogen or preferably a metal cation,' and the other means a residue exchangeable with aryloxy, with each other

or

E) intramolecularly decarboxylates a compound of form1

and, if desired, converts a compound obtained by the method into another compound of formula I and/or transfers a free compound obtained by the method into an acid addition salt, an acid addition salt obtained by the method into the free compound or into another acid addition ionic salt, or a free compound obtained by the method or an acid addition salt obtained by the method in a metal complex.

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

Nucleofuge leaving groups are e.g. reactive esterified hydroxy groups such as with a halohydrogen acid, e.g. with fluorine, chlorine, bromine or hydroiodic acid or a lower alkane, optionally substituted benzene or halogen sulphonic acid, e.g. hydrosky groups esterified with methane, ethane, benzene, p.toluene or fluorosulfonic acid.

The reaction of an azole of formula II

where Y is -CH= or -N= and Me is preferably a metal atom, especially an alkali metal atom, with a compound of formula

III

where Ar, R 3. , R, JD, U and V have the meaning given in formula I and X means e.g. halogen, especially chlorine, bromine or iodine, or benzenesulfonyloxy, p-tosyloxy, trifluoroacetyloxy or preferably lower alkylsulfonyloxy such as e.g. mesyloxy, is preferably carried out in a relatively polar but reaction-inert organic solvent, e.g. N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide, acetonitrile, benzonitrile and others. Such solvents can be used in combination with other reaction-inert solvents such as aliphatic or aromatic hydrocarbons, e.g. benzene, toluene, xylene, hexane, petroleum ether, chlorobenzene, nitrobenzene, etc.

If X means chlorine or bromine, alkali iodide (such as NaJ or KJ) can conveniently be added to speed up the reaction. Increased temperatures from 0 to 220°C, preferably 80-170°C, are advantageous. Suitably, reaction mixtures are heated under reflux.

In those cases where in formula II Me is hydrogen, the process is carried out in the presence of a base. Examples of such bases are inorganic bases such as the oxides, hydroxides, carbonates and bicarbonates of alkali and alkaline earth metals as well as e.g. tart. amines such as triethylamine, triethylenediamine, piperidine, pyridine, 4-dimethylaminopyridine, 4-pyrrolidylpyridine, etc.

With this and the following manufacturing variants, the intermediate and final products from the reaction medium can be purified in isolation and,

if desired, with a generally common method, e.g. by extraction, crystallization, chromatography, distillation, etc.

The transfer of the carbonyl group in the compounds of formula IV to the group of formula V takes place by reaction with an ortho-carboxylic acid tri-C^-C^2_alkyl ester whose C^-C^2~ alkyl groups are optionally substituted by halogen or C^-Cg- alkoxy, or in the presence of an acid with at least 2 Mol of a monohydric alcohol of formula U-OH (Va), whereby the compounds of formula I are obtained, where U and V mean the same, optionally substituted C^-C-^2~ alkyl groups , or by reaction with a diol of formula Vb

whereby the compounds of formula I are obtained, where U and V together are one of the previously defined alkylene bridges. Here, Ar, Y, R a , R, JD, U and V have the meanings given in formula I,

This ketalization reaction can be carried out analogously to already known ketalization reactions, e.g. analogous to the preparation of 2-bromomethyl-2,4-diphenyl-1,3-dioxolane (Synthesis, 1974 (I), 23).

In the preferred embodiment of the ketalization, both reaction partners are heated for several hours together with an azeotrope former in a common organic solvent under reflux. As an azeotrope-former, e.g. benzene, toluene, xylene, chloroform or carbon tetrachloride where appropriate, in order to speed up the reaction an addition of a strong acid such as e.g. p-toluenesulfonic acid, may be beneficial. Usable organic solvents are in this case e.g. aromatic hydrocarbons such as benzene, toluene, xylene etc., saturated hydrocarbons such as n-hexane or saturated halogenated hydrocarbons such as e.g. 1,1,1-trichloroethane.

Other ketalization methods can also be carried out, e.g.

by reacting a ketone IV that is ketalized with an alcohol or phenol that is different from the alkanols or the diols of formula Va or Vb, and re-ketalizes this by reaction with an excess of alkanol Va or diol Vb to (I). The output product is available e.g. according to one of the progress variants A), D) and E).

The preparation of the compounds of formula I where the substituents U and V according to variant C) together are -CH2~CH(CH2ZR7)-occurs e.g. by reaction of a compound of formula VI with a compound of formula VII, where X 1 means a group -ZH and X 2 a group X. The reaction is preferably carried out in reaction-inert organic solvents. Suitable for this, e.g. N,N-dimethylformamide, N,N-dimethylacetamide, hexamethylphosphoric triamide, dimethylsulfoxide, 4-methyl-3-pentanone, etc. Also mixtures with other reaction-initiated solvents, e.g. with aromatic hydrocarbons such as benzene, toluene, xylene, etc. can be used. In some cases, it may be beneficial to work in the presence of a base to speed up the reaction rate. Such bases are e.g. alkali metal hydrides or alkali metal carbonates. In certain cases it may also be beneficial to first transfer connections*; VI in a known manner in a suitable metal salt.

This preferably occurs by reaction of VI with a Na compound, e.g. sodium hydride, sodium hydroxide, etc. This salt from VI is then reacted with the compound of formula VII. In order to increase the reaction rate, in some cases it is also possible to work at increased temperatures, preferably 80°C to 130°C, resp. at the boiling point of the solvent.

In an analogous manner, the compounds of formula VI and VII, where X 1 is a group X and X 2 is a group -ZH, can also be reacted.

In the condensation reaction of compounds of formula VI and VII, where X₂ and X₂ are hydroxy, which leads to the products of formula I, where Z is oxygen, the reactants can be heated in a suitable solvent under reflux, while at the same time the resulting water is distilled off azeotropically from the reaction mixt. Suitable solvents are aromatic hydrocarbons such as toluene or alcohol HO-R^.

With this reaction, one works appropriately in presence

of a strong acid, e.g. p-toluenesulfonic acid.

In variant D), the starting point is preferably the compounds of formula VIII and IX, where X^ is a group -OMe and X^ is a nucleofuge leaving group or vice versa, X^ is the nucleofuge leaving group and X^ forms the group -OMe. Here Ra, Rjy U. V, Y and Ar have the meanings given in formula I; Me is preferably hydrogen. The reaction is preferably carried out under the conditions described in variant A).

In variant E) the compound of formula X to be decarboxylated, accessible by ketalization of a compound of formula XI, is described, analogously to under B)

which in turn is obtained by reacting a compound of formula Ar-OH XII with a difunctional derivative of the carboxylic acid, e.g. with phosgene, a haloformic acid lower alkyl ester or a divalereallyl or diphenyl carbonate and further reaction with a compound of formula XIII

dried or heated in a high-boiling solvent such as a high-boiling ether, e.g. diphenyl ether or ethylene glycol dimethyl ether, to approx. 120° - 220°C.

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

Thus, one can e.g. reketalize compounds according to the method to other compounds of formula I. E.g. can in compounds of formula I, where U and V are the same, optionally substituted, C^-C12-alkyl radicals U, by reaction with 1 Mol of another, optionally substituted C^-C^2-alkanol of formula V-OH (Vc), replace a group U with a group V or by reaction with a diol of formula Vb replace both groups U with a divalent residue. The transketalization takes place in the usual way, e.g. in the presence of an acidic condensing agent such as a mineral, sulphonic or strong carboxylic acid, e.g. of hydrochloric or bromic acid, sulfuric acid, p-toluenesulfonic acid or trifluoroacetic acid, preferably under distillative resp. azeotropic-distillative removal of low-flowing reaction products.

In addition, in the carbocyclic aryl parts of the compounds according to the method, additional substituents can optionally be introduced in the residue Ar and/or the groups Ra, respectively. R^. Thus, one can e.g. by reaction with a halogen in the presence of a Lewis acid such as an iron, zinc, boron or antimohalide, or by treatment with N-chlorosuccinimide, introduce halogen.

In addition, nitro groups can be reduced to amines, e.g. by means of suitable complex hydrides, e.g. with lithium aluminum hydride, diazotize these, e.g. by means of nitric acid, and the formed diazonium group replaced in the usual way with halogen or alkoxy. Likewise, halogen can be replaced by alkyl by reaction with an alkyl metal compound, e.g. with an alkyllithium or alkylmagnesium halide.

When the compounds of formula I are obtained as bases, they can be transferred with the help of inorganic or organic acids into corresponding salts or with the help of preferably equimolar amounts of metal salts in metal complexes of formula I. Conversely, the salts of formula I can e.g. by reaction with alkali (hydrogen) carbonate or alkali hydroxide is transferred into the free bases of formula I.

The starting ketals of formula III are obtained from the underlying methyl aryl ketone of formula XIV

by reaction with the desired diol in an inert solvent, e.g. a halogenated hydrocarbon (such as methylene chloride, ethylene chloride, chloroform, carbon tetrachloride, etc.) and by simultaneous or subsequent halogenation. To speed up the reaction, an addition of p-toluenesulfonic acid is advantageous. The ketones of formula IV can be prepared by halogenation of the starting ketones XIV to XV

and further reaction of XV, analogous to variant A, with an azole of formula II. Here Hal is preferred for chlorine or bromine.

The ketals III, VI, IX and X are obtained analogously to variant B by reaction of the starting ketone, e.g. of formula IV with a suitable alcohol or diol.

The starting substances of formula III, IV, VI, X and XI, which were developed specifically for the preparation of the compounds of formula I according to the invention, are new.

In all described ketalization reactions of a ketone with a substituted OÉ, (3 - or ot, y-diol, mixtures of diastereomers of the resulting ketal are preferentially formed. Correspondingly, it is generally formed from the starting ketones

stereomeric mixtures of the final products I. The compounds

in

with formula I can e.g. exist in the following two diastereomeric forms:

The configuration of type A is denoted here and in the following by the "trans" isomer.

The symbols in the rendered structures have the following meanings:

.... = behind

<=>i

= in front of the drawing plane.

The configuration of type B shall be designated corresponding to the "cis" isomer. The separation of the two diastereomers can take place e.g. by fractional crystallization or by chromatography (thin-layer, thick-layer, column chromatography, high-pressure liquid chromatography, etc.). The two isomers show different biological effects. In general, the diastereomer mixtures are used for practical purposes.

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

Some of the starting materials and intermediate products used in methods A, B, C, D and E are known, others can be produced by methods known per se. Some are new; their manufacture shall be described here.

1-( P -aryl)-ethylimidazolyl ketals, where aryl is substituted phenyl or naphthyl, are cited in the following references as fungicides and bactericides: US-No.': 3,575,999, 3,936,470, 4,101,664, 4,101,666, 4 156 008.

It was surprisingly established that compounds of formula I against phytopathogenic fungi and bacteria in a practical context have a very favorable microbicide spectrum. Thus, they have very beneficial curative, preventive and systemic plant therapeutic properties and can be used in cultivated plant protection. With the active substances of formula I, microorganisms that occur on plants or plant parts (fruit, flower, leaves, stem, tuber, roots) of various beneficial crops can be reduced or destroyed, as later growing plant parts are also spared from such microorganisms. The active substances are particularly effective against the following groups of phytopathogenic fungi: Ascomycetes (eg Venturia, Podosphaera, Erysiphe, Monilinia, Uncinula); Basidiomycetes (eg Hemileia, Rhizoctonia, Puccinia family);

Fungi imperfecti (eg botrytis, helminthosporium, fusarium, septoria, cercospora and alternaria). Furthermore, the compounds of formula I act systemically. They can also be used as mordants when treating seeds (fruit, tubers, grains) and plant cuttings to protect them against fungal infections as well as phytopathogenic fungi that occur in the soil. The active substances according to the invention are particularly distinguished by their good plant compatibility.

The invention thus also relates to microbicidal agents and the use of the compound of formula I in the fight against phytopathogenic microorganisms, especially fungi which are harmful to plants, respectively. the preventive effect against plant attack.

As target cultures for the indicated areas of indication apply within the scope of this invention, e.g. the following plant species: Cereals: (wheat, barley, rye, oats, rice, sorghum and related); beets: (sugar and fronds); stone, stone and berry fruits: (apples, pears, plums, peaches, almonds, morels, strawberries, raspberries and blackberries); legumes: (beans, lentils, peas, soya); oil crops: (rapeseed, mustard, poppy, olives, sunflower, coconut, castor, cocoa, peanuts) cucurbits: (pumpkins, cucumbers, melons); fiber crops: (cotton, flax, hemp, jute); citrus fruits: (oranges, lemons, grapefruit, tangerines); vegetable varieties: (spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes, paprika); laurel plants: (advocado, cinnamonum, camphor) or plants such as maize, tobacco, nuts, coffee, sugar beet, tea, vines, hops, banana and natural rubber plants, as well as ornamental plants (Compositer).

Active substances with formula I are used in the agricultural sector usually in the form of compositions and can be applied simultaneously or after each other with additional active substances on the surfaces, plants or plant parts to be treated. In the case of plant protection products, these additional active substances can be fertilizers, trace element mediators or other preparations that affect plant growth. But there can also be selective herbicides, insecticides, fungicides, bactericides, nematicides, molluscicides or mixtures of several of these preparations, together with any additional carriers, surfactants or other application-promoting additives that are common in the formulation technique.

For all > formulations, suitable carriers and additives can be solid or liquid and corresponding non-toxic substances such as e.g. natural or regenerated mineral substances, dissolving, dispersing, wetting, adhesive, thickening or binding agents which are appropriate in the corresponding formulation technique.

An agriculturally preferred method of application

of an active ingredient of formula I or an agrochemical on an infested plant is the application to the foliage (foliar application). The number of applications and the amount of use depends on the attack pressure of the corresponding infection (fungus). However, the active substances with formula I can also reach the roots through the soil (systemic effect), when you drench the plant's growth site with a liquid preparation or bring the substance in solid form into the soil, e.g. in the form of granules (soil application). However, the compounds of formula I can also be applied to the seed grains (coating), by soaking the grains either with a liquid preparation of the active substance or coating them with a solid preparation.

In addition to this, in special cases it is possible to use other types of application, e.g. targeted treatment of the plant stem or buds.

The compounds of formula I are used here in unchanged form or preferably together with auxiliaries that are common in the agrochemical formulation technique and are therefore prepared in the usual way to e.g. emulsion concentrates, ironable pastes, directly sprayable or dilutable solutions, diluted emulsions, spray powders, soluble powders, nebulizers, granules, by encapsulation in e.g. polymeric substances. Methods of application such as spraying, fogging, atomizing, spreading, coating or pouring are chosen as are the nature of the agents in accordance with the intended goals and given conditions. Favorable amounts of use are generally 50 g - 5 kg of active substance (AS) per have; preferably 100 g - 2 kg AS/ha, especially at 200 g - 600 g AS/ha.

The agrochemical formulations, i.e. the agents containing the active substance of formula I and possibly a solid or liquid additive, the preparations or compositions are prepared in a known manner, e.g. by intimate mixing and/or grinding of the active substance with the excipients such as e.g. solvents, solid carriers and possibly surface-active compounds (surfactants).

Relevant solvents are: aromatic hydrocarbon substances, preferably the fraction Cg - C-^, such as e.g. xylene mixtures or substituted naphthalenes, phthalic esters such as dibutyl or dioctyl phthalate, aliphatic hydrocarbons such as cyclohexane or paraffins, alcohols and glycols and their ethers and esters, such as ethanol, ethylene glycol, ethylene glycol monomethyl or ethyl ether, ketones such as cyclohexanone, strongly polar solvents such as N-methyl-2-pyrrolidone, dimethylsulfoxide or dimethylformamide, as well as optionally epoxidized vegetable oils such as epoxidized coconut oil or soya oil; or water.

As solid carriers, e.g. for nebulizers and dispersible powders, natural stone flours such as calcite, talc, kaolin, montmorillonite or attapulgite are usually used. To improve the physical properties, highly dispersed silicic acid or highly dispersed absorbent polymers may also be added. As granular, adsorptive granule carriers are porous types such as e.g. pumice stone, broken brick, sepiolite or bentonite relevant, as non-sorptive carrier materials are e.g. calcite or sand topical. In addition to this, a number of pre-granulated materials of an inorganic or organic nature can be used, such as especially dolomite or chopped up plant residues.

As surface-active compounds, non-ionic, cationic and/or anion-active surfactants with good emulsifying, dispersing and wetting properties come into consideration, depending on the nature of the active substance of formula I to be formulated. Surfactants also include surfactant mixtures.

Suitable anionic surfactants can be so-called water-soluble soaps as well as water-soluble synthetic surface-active compounds.

As saps, mention may be made of alkali, alkaline earth or optionally substituted ammonium salts from higher fatty acids (C^q-C22^ ' such as e.g. the Na or K salts from oleic or stearic acid, or from natural fatty acid mixtures such as .can be extracted from the coconut or tallow oil.In addition, the fatty acid methyl lauric salts should also be mentioned.

More often, however, so-called synthetic surfactants are used, especially fatty sulfonates, fatty sulfates, sulfonated benzimidazole derivatives or alkylaryl sulfonates.

Fat sulfonates or sulfates are usually present

as alkali, alkaline earth or optionally substituted ammonium salts and has an alkali residue with 8-22 C atoms, with alkyl also including the alkyl part of the acyl residues, e.g.

The Na or Ca salt of the lignin sulphonic acid, the dodecyl sulfuric acid ester or a fatty alcohol sulphate mixture which is prepared from natural fatty acids. The salts from sulfuric acid esters and the sulphonic acids from fatty alcohol-ethyleneoxy adducts are also included here. The sulphonated benzimidazole derivatives preferably contain 2-sulphonic acid groups and a fatty acid residue with 8-22 C atoms. The alkylarylsulfonates are e.g. The Na, Ca or triethanolamine salts of dodecylbenzenesulfonic acid, dibutylnaphthalenesulfonic acid or a naphthalenesulfonic acid-formaldehyde condensation product.

In addition, corresponding phosphates such as e.g. salts from the phosphoric acid ester of a p-nonylphenol-(4-14)-ethyleneoxy adduct relevant.

Non-ionic surfactants are primarily polyglycoether derivatives from aliphatic or cycloaliphatic alcohols, saturated or unsaturated fatty acids and alkylphenols which may contain 3 - 30 glycol ether groups and 8 - 20 carbon atoms in the (aliphatic) hydrocarbon residue and 6 - 18 carbon atoms in the alkyl residue of the alkylphenols.

Further suitable non-ionic surfactants are water-soluble polyethylene oxide adducts containing 20 - 250 ethylene glycol ether groups and 10 - 100 propylene glycol ether groups, on polypropylene glycol, ethylene diamino polypropylene glycol and alkyl polypropylene glycol with 1-10 carbon atoms in the alkyl chain. Said compounds usually contain 1-5 ethylene glycol units per propylene glycol unit.

Examples of nonionic surfactants include nonyl-ferriol polyethoxyethanols, castor oil polyglycol ethers, polypropylene-polyethylene oxide adducts, tributylphenoxypolyethoxyethanol, polyethylene glycol and octylphenoxypolyethoxyethanol.

In addition, fatty acid esters from polyoxyethylene sorbitan such as polyoxyethylene sorbitan trioleate also come into consideration.

With regard to the cationic surfactants, it concerns above all quaternary ammonium salts which contain as N-substituent at least one alkyl residue with 8-22 C atoms and as an additional substituent has lower, possibly halogenated alkyl, benzyl or lower hydroxyalkyl residues. The salts are preferably present as halides, methyl sulphates or ethyl sulphates, e.g. the stearyl-trimethylammonium chloride or the benzyldi(2-chloroethyl)ethylammonium bromide.

The surfactants that are common in the agrochemical formulation technique are, among others, described 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", Chemical Publishing Co., Inc. New York, 1980.

The agrochemical preparations usually contain 0.1 -

99%, especially 0.1 - 95% active substance with formula I, 99.9 -

1%, especially 99.8 - 5% of a solid or liquid additive, including 0 - 25%, especially 0.1 - 25%, of a surfactant.

While concentrated products are preferred as merchandise, the consumer usually uses diluted products.

The agrochemical agents may also contain additional additives such as stabilizers, antifoam, viscosity regulators, binders, adhesives as well as fertilizers and other active substances to achieve special effects.

Such agrochemicals are part of the present invention.

The invention' shall be explained in more detail by means of the following examples without restricting this. Temperatures are indicated in degrees Celsius, pressure in mbar. Percentages and parts refer to the weight. RT means room temperature, t means hour.

Production examples:

Example 1

Manufacture of

2-/ p-(phenoxy)- phenyl/- 2-/ l-( 1H- 1, 2, 4- triazolyl)- methyl/- 4- methyl- 1, 3- dioxane a) Preparation of the intermediate product

2-/ p-(phenoxy)-phenyl/- 2- bromomethyl- 4- methyl- l, 3- dioxane 10 parts 2-^p-(phenoxy)-phenyl/-2-oxy-l-bromomethane and 4 parts 1 ,3-butanediol is heated in 40 ml of absolute toluene in the presence of 0.2 parts of catalytically active p-toluenesulfonic acid for 3 h under reflux, the water that forms being separated with a water separator. After cooling to RT, the reaction mixture is washed twice with 20 ml of water, dried over sodium sulfate, filtered, the solvent is evaporated and the crude product is recrystallized from isopropanol. Colorless crystals. Temp. 96-106°C.

b) Production of the final product

3.3 parts of 1,2,4,triazole sodium salt and a catalytically effective amount of potassium iodide are stirred in 40 ml of dimethyl sulfoxide together with 10.2 parts of the 2-/p-(phenoxy)-phenyl7-2-bromomethyl produced under a) -4-methyl-1,3-dioxane for 30 h at an internal temperature of +120°C. After cooling to room temperature, 300 ml of water are added, extracted three times with 30 ml of ethyl acetate, the combined extracts are washed twice with 20

ml of water, dried over sodium sulphate, filtered and the solvent evaporated. The oily residue is purified by column chromatography (silica gel/ethyl acetate). After the eluent evaporates, the oily residue crystallizes after the addition of petroleum ether. Brownish crystals. Temp. 99.5-101°C.

Example 2

Manufacture of

2-/p-(4-chloro-2-methylphenoxy)-phenyl/- 2-(1-imidazolylmethyl)-4- methoxymethyl-1,3- dioxolane 16 parts 2-/p-(4-chloro-2-methylphenoxy) )-phenyl/-2-(1-imidazolylmethyl)-4-hydroxymethyl-1,3-dioxolane is dissolved in 150 ml of N,N-dimethylformamide and mixed under a flow of nitrogen and stirring with 1.9 parts of 55% sodium hydride dispersion and heated for 2 h to 80°C. After cooling to RT, 6.3 parts of methyl iodide are added dropwise while stirring over the course of 1 h, the reaction mixture is heated to 60°C for 2 h and diluted with 800 ml of ice water and extracted three times with 300 ml of ethyl acetate. The collected extracts are washed twice with 50 ml of water, dried over sodium sulphate, filtered and the solvent is evaporated. The residue is purified by column chromatography (silica gel/acetone-ethyl acetate (1:1)). After the eluent mixture has evaporated, the diastereomer mixture is brought to crystallization by treatment with hexane. Beige crystals; Temp. 92-106°C.

Example 3

Synthesis of

2-/p-(3- Chlorophenoxy)-phenyl/- 2-( 1- imidazolylmethyl)- 4- ethyl-1, 3- dioxolane

1.2 parts of imidazole sodium salt and a catalytically effective amount of potassium iodide are stirred in 50 ml of dimethylformamide together with 4 parts of 2-/p-(3-chlorophenoxy)-phenyl/-2-bromomethyl-4-ethyl-1,3-dioxolane in 17 h at an internal temperature of 125°C.

After cooling, the brown reaction mixture is mixed with 150 ml of water, extracted three times with 50 ml of ethyl acetate, the combined extracts are washed twice with 50 ml of water, dried over sodium sulphate, filtered and the solvent is evaporated. The oily crude product is chromatographed over a 35 cm long silica gel column using acetone/ethyl acetate (1:1). After the eluent evaporates, the oily residue crystallizes after the addition of petroleum ether. Light yellowish crystals. Temp. 69-71°C.

Example 4

Manufacture of

2-/p-(4-chlorophenoxy)-phenyl/- 2-(1- imidazolylmethyl)-4- ethyl-1, 3- dioxolane

a) The synthesis of the intermediates

and c) Manufacture of

2-/p- ( 4- chlorophenoxy)-phenyl/- 2- methyl- 4- ethyl- 1, 3- dioxolane

37 parts of 4-(p-chlorophenoxy)-acetophenone and 18 parts of 1,3-butanediol are heated in 400 ml of absolute toluene in the presence of 2 parts

t

catalytically active p-toluenesulfonic acid for 14 h on a water separator under reflux. After cooling to RT, the reaction mixture is washed twice with 400 ml of water, dried over sodium sulfate, filtered, the solvent evaporates and the crude product is chromatographed for purification over a 1 m long silica gel column using ligroin/hexane/ethyl acetate/toluene (5:3:1:1 ). The product is obtained as a light yellowish oil.

22

n£<z>: 1.5527.

0) Manufacture of

2-/p-(4-chlorophenoxy)-phenyl/-2-bromomethyl-4-ethyl-1,3-dioxolane 36.8 parts of the 2-/p-(4-chlorophenoxy)-phenyl prepared under <\) /-2-methyl-4-ethyl-1,3-dioxolane is heated to the boiling point in 350 ni chloroform. Under illumination with a 150 W irradiation lamp, 19.4 parts of bromine, dissolved in 50 ml of chloroform, are added dropwise and then heated for 2 h under reflux. After cooling to RT, the reaction mixture is washed twice with 200 ml of water, dried over sodium sulphate, filtered and the solvent is removed by water jet vacuum. For purification, the crude product is chromatographed over a 1 m long silica gel column using toluene. The product is obtained as a yellow oil. n^<3>: 1.5805.

b) The synthesis of the final product

4.4 parts imidazole sodium chloride salt and a catalytic agent

amount of potassium iodide is stirred in 80 ml of dimethylformamide together with 14.7 parts of the 2-β-(4-chlorophenoxy)-phenyl/-2-bromomethyl-4-ethyl-1,3-dioxolane prepared according to A) for 17 h at a bath temperature of 125°C. After cooling to room temperature, the reaction mixture is poured into 600 ml of water, extracted three times with 200 ml of ethyl acetate, the combined organic phases are washed twice with 200 ml of water, dried over sodium sulphate, filtered and the solvent is evaporated. The oil-active residue is chromatographed over a 50 cm long silica gel column using acetone/ethyl acetate (1:1). After the eluent evaporates, the product is obtained as a brown oil;

n£<5>: 1.5750.

Example

Synthesis of

2-/ p-(phenoxy)-phenyl/- 2-( 1H- 1, 2, 4- triazolylmethyl)- 4- ethyl-1, 3- dioxolane 17 parts 2-^p-(phenoxy)-pheny]_7- 3-bromomethyl-4-ethyl-1,3-dioxolane, 8.4 parts of potassium carbonate, 4.2 parts of 1,2,4-triazole and a catalytically effective amount of sodium iodide are stirred in 100ml of dimethylsulfoxide for 24 hours at an internal temperature of 125° C. After cooling to RT, the reaction mixture is poured into 600 ml of water, extracted three times with 200 ml of ethyl acetate, the combined extracts are washed twice with 200 ml of water, dried over sodium sulphate, filtered and the solvent is evaporated. The oily residue is chromatographed over a 50 cm long silica gel column using chloroform/ether (1:1). After the eluent evaporates, the oily residue crystallizes after the addition of petroleum ether. White crystals. Temp. 81.5-83.5°C. Example ^ Synthesis of

2-/ p-(phenoxy)-phenyl/- 2-( 1H- 1, 2, 4- triazolylmethyl)- 1, 3-dioxane

14 parts of 2-^p-phenoxyphenyl/-2-bromomethyl-1,3-dioxane, 7.2 parts of potassium carbonate, 3.6 parts of 1,2,4-triazole and a catalytically active amount of potassium iodide are stirred in 100 ml of dimethyl sulfoxide for 20 h at an internal temperature of 14 0°C. After cooling to RT, add 600 ml of water, extract three times with 200 ml of ether, the combined extracts are washed twice

times with 200 ml of water, dried over sodium sulphate, filtered and the solvent evaporated. The oily residue is chromatographed over a 50 cm long silica gel column using chloroform/ether (1:1). After the eluent evaporates, the residue crystallizes after the addition of petroleum ether. White crystals; Temp. 129-130°C.

Example 7

Synthesis of

2-/p-(phenoxy)-phenyl/- 2-( 1H- 1, 2, 4- triazolylmethyl)- 4- hydroxymethyl- 1, 3- dioxolane

4.5 parts of 2-^p-phenoxyphenyl/-2-bromomethyl-4-hydroxymethyl-1,3-dioxolane, 2.2 parts of potassium carbonate, 1.1 parts of 1,2,4-triazole and a catalytically effective amount of potassium iodide are stirred in 50 ml of dimethyl sulphoxide for 4 h at an internal temperature of 140°C. After cooling to RT, 600 ml of water is added, extracted with 200 ml of ethyl acetate, the combined extracts are washed with 200 ml of water, dried over sodium sulphate, filtered and the solvent evaporated. The oily residue is chromatographed over a 50 cm long silica gel column using acetone. After the eluent evaporates, the oily residue crystallizes after the addition of petroleum ether. Beige crystals; Temp. 111-122°C.

Example 3

Synthesis of

2-/p-(phenoxy)-phenyl/- 2-( 1H- 1, 2, 4- triazolylmethyl- 4- n-propyl- 1, 3- dioxolane

10.3 parts of the nitrate from 1-(p-phenoxyphenyl)-2-(1,2,4-triazolyl-1-yl)-ethanone, 6.1 parts of 1,2-pentanediol, 6.9 parts of p-toluenesulfonic acid , 20 parts of 1-pentanol and 200 parts of xylol are heated on the water separator under reflux and washed after cooling to RT twice with 200 ml of diluted caustic soda and twice with 200 ml of water. The organic phase is dried over sodium sulphate, filtered and the solvent

evaporates. The oily residue is chromatographed over a 1 m long silica gel column using ethyl acetate. After the eluent evaporates, the oily residue crystallizes slowly. Beige crystals; Temp. 68.5-71°C.

EXAMPLE Bl.

Manufacture of

2-[2'-methyl-4'-phenoxy)-phenyl]-2-(1-imidazolylmethyl)-4-ethy 1-1,3- diox' solan a) Preparation of the starting substance

2- methy1- 4- phenoxy- phenacylbr oiriide

36.6 parts of 2-methyl-4-phenoxy-acetophenone are mixed in 160 ml of acetic acid at 35°C during 1 1/2 hours with 25.9 parts of bromine. After completion of the dripping, it is stirred after 1 hour at room temperature, then poured into 1 liter of ice water and extracted twice, each time with 100 ml of ether. The combined organic extracts are washed well with water, dried over sodium sulfate, filtered, the solvent is evaporated and the crude product is digested with hexane.

Brown crystals. SMP. 60-61°C

b) Production of the intermediate product

2-[(2'-methyl-4'-phenoxy)-phenyl]-2-bromomethyl-4-ether-T,3"-dioxolane

85.4 parts of 2-methyl-4-phenoxyphenacyl bromide prepared under a) and 25.2 parts of 1,2-butanediol are heated in 250 ml of absolute toluene in the presence of 1 part of catalytically active p-to-

luenesulfonic acid for 24 hours on a water separator under reflux cooling. After cooling to room temperature, the reaction mixture is washed three times, each time with 250 ml of water, dried over sodium sulphate, filtered and the solvent is evaporated. The product is obtained as a reddish-brown oil.

c) Synthesis of the final product

9.5 parts of the 2-[(2'-methyl-4<1->phenoxy)-phenyl]-2-bromomethyl-4-ethyl-1,3-dioxolane prepared under b), 2.4 parts of imidazole and 4.0 parts of potassium tert-butylate are stirred in 50 ml of dimethylsulfoxide for 30 hours at an internal temperature of 110°C. After cooling to room temperature, 300 ml of water are added, extracted three times, each time with 150 ml of ethyl acetate, the combined extracts are washed neutral with water, dried over sodium sulphate, filtered, the solvent is evaporated and the oily residue is chromatographed over a 50 cm long silica gel column using ethyl acetate. Product-50

is obtained as a reddish oil. ND : 1.5550.

EXAMPLE B2

Manufacture of

2-[ p- phenoxy)- phenyl]- 2-[ 1-( 1H- T, 2, 4- triazolyl)- methyl]- 1, 3-dioxolane 11 parts 2-[p-(phenoxycarbonyloxy)-phenyl]- 2-[1-(1H-1,2,4-triazolyl)-methyl]-1,3-dioxolane is then heated (about 10 hours) to 130° C. in 200 ml of ethylene glycol diethyl ether until the evolution of carbon dioxide has ended. The solvent is then distilled off under reduced pressure. After cooling to room temperature, the oily crude product is taken up in 500 ml of diethyl ether, washed twice, each time; with 100 ml of water, dried over sodium sulphate, filtered and the solvent evaporated. The remaining crystals pure-.' seen by recrystallization from ethyl acetate/cyclohexane in the presence of activated carbon. White crystals with a melting point of 100 to 102°C are obtained.

EXAMPLE B3

Preparation of the A and B diastereomers of

2-[ p-(phenoxy)-phenyl]^ 2-(1H-1,2,4-triazolylmethyl)- 4-( p-chlorobenzyloxymethyl)- 1,3-dioxolane

14.1 parts of 2-[p-phenoxy)-phenyl]-2-(1H-1,2,4-triazolylmethyl)-4-hydroxymethyl-1,3-dioxolane in 100 ml of absolute dioxane are added dropwise while stirring and while carrying out nitrogen at room temperature to 1.8 parts of a 55%1 ig na-r*. triium hydride dispersion in 100 ml of absolute dioxane and heated for 3 hours at 80°C. After cooling to room temperature with stirring during 1/2 hour, 8.6 parts of p-chlorobenzyl bromide in 50 parts of absolute dioxane are added dropwise, the reaction mixture is heated for 3 hours to 50°C, diluted after cooling to room temperature with 1200 ml of ice water and extracted three times , each time with 200 ml of ethyl acetate. The combined extracts are washed twice, each time with 70 ml of water, dried over sodium sulphate, filtered and the solvent evaporated. The remaining diastereomer mixture is separated by column chromatography (silica gel) ethyl acetate). After evaporation of the ethyl acetate, diastereomer B becomes solid. Temp. 83-85°CDiastereomer A remains after drying in high-vacuum as a tough, light brown oil; nD 2 6: 1.5865.

Analogous to the described preparation examples, the following end products with formula I (if nothing else is noted, as diastereomer mixtures with different mixing ratios) can also be prepared:

In the following tables, A stands for diastereomers

of types A and B correspondingly for a diastereomer of the type

B.

Formulation examples for agrochemical agents containing liquid active substances of formula I (% = weight percentage) From such concentrates, emulsions can be prepared in any concentration by diluting with water.

The solutions are suitable for application in the form of small drops.

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

By intimately mixing carrier substances with the active substance, a ready-to-use dusting agent is obtained.

Formulation examples for agrochemical agents, containing solid active substances of formula I (% = percentage by weight)

This concentrate can be diluted with water to produce emulsions in any concentration.

A ready-to-use powder is obtained when the active substance is mixed with the carrier material and ground together with a suitable grinder.

The active substance is mixed with the additives, ground together and moistened with water. This mixture is extruded and then dried in a stream of air.

In a mixing device, the finely ground active ingredient is applied evenly to kaolin that is moistened with polyethylene glycol.

In this way, dust-free encapsulation granules are obtained.

The finely ground active substance is intimately mixed with the additives. A suspension concentrate is thus obtained, with which, by diluting with water, suspensions can be prepared in any concentration.

Biological examples

Example T9

Action against Puccinia graminis on wheat

a) Residual protective effect

Wheat plants were sprayed 6 days after sowing with a

injection liquid prepared from the active ingredient's injection

powder (0.06% active substance). After 24 hours, the treated plants were infected with a uredospore suspension of the fungus. After an incubation of 48 hours at 95-100% relative humidity and approx. 20°C, the infected plants were placed in a weighing house at approx. 22°C. The assessment of rust fungus development took place 12 days after the infection.

b) Systemic effect

On wheat plants, 5 days after sowing, a spray bag was completely prepared from the active substance's spray powder (0.006% active substance in relation to soil volume). After 48 hours, the treated plants were infected with a uredospore suspension of the fungus. After an incubation of 48 hours at 95-100% relative humidity and approx. 20°C, the infected plants were placed in a weighing house at approx. 22°C. The assessment of rust fungus development took place 12 days after the infection.

The compounds from table 1-10 show a good effect against Pucciniå fungi. Untreated but infected control plants showed a Puccinia attack of 100%. Among others, the compounds No. 1.9, 1.17, 1.24, 1.26, 2.17, 3.1, 3.2, 3.6 to 3.8, 3.12, 3.26, 3.51, 3.52, 3.54, 3.55, 3.70, 3.75, 3.78, 3.83, 3.825, 3.165, 3.167 inhibited 3.133, 3.155, 3.156, 3.160, 3.162, 3.164, 3.168, 3.171, 3.172, 3.176, 3.177, 3.193,

3.212, 3.213, 3.220, 3.226, 3.227, 3.231 til 3.234, 3.263, 3.267, 3.274, 3.279, 3.287, 3.292, 3.311, 3.314, 3.340, 3.348, 3.373, 3.376, 3.384, 3.386, 4.2, 4.15, 4.23, 4.50,

4.55, 4.57, 4.66, 4.70, 4.77, 4.78, 4.81, 4.89 to 4.94,

4.113, 4.116, 4.136, 4.138 to 4.147, 5.13, 5.14, 5.36, 5.40, 5.70, 5.71, 5.76, 5.78, 5.105, 5.113, 5.117, 6.8, 6.82, 6.93, 5.6 - 7.37, 8.6 - 7.3.7, 5.6 - 7.3.7% residual-protective treatment. Beyond this, connection no. 6.8 showed full

systemic effect (0% attack) also after, a dilution to 0.006%.

Example 2Q

Action against Cercospora arachidicola on peanut plants - 10-15 cm tall peanut plants were sprayed with a spray liquid (0.02% active stubble) prepared from spray powder from the active substance and infected 48 hours later with a conidien suspension of the fungus. The infected plants were incubated for 72 hours at approx. 21°C and high humidity and then placed in a weighing house until the typical leaf spots appeared. The assessment of the fungicidal effect took place 12 days after infection based on the number and size of the spots.

When compared with untreated but infected control plants (number and size of spots = 100%), the peanut plants treated with the active substances from Tables 1 - 10 showed a greatly reduced Cercospora attack. Thus, compounds Nos. 1.1, 1.4, 1.9, 1.14, 1.17, 1.24 to 1.27, 2.17, 3.1, 3.2, 3.6, 3.7, 3.11, 3.51, 3.52, 3.54, 3.55, 3.57, 3.78, 3.85, 3.127, 3.186, 3.187 prevented , 3.155, 3.156, 3.162, 3.171, 3.172, 3.176, 3.177, 3.212, 3.213, 3.220, 3.221, 3.226, 3.231, 3.232, 3.233, 3.234, 3.267, 3.292, 3.314, 3.348, 3.384 til 3.388, 4.15, 4.23, 4.50 , 4.57, 4.59, 4.66, 4.89 til 4.94, 4.113, 4.116, 4.136 til 4.148, 5.13, 5.14, 5.36, 5.40, 5.70, 5.71, 5.73, 5.75 til 5.78, 5.105 til 5.110, 5.113 til 5.118, 6.1, 6.8, 6 ,93, 6.94, 7.33, 7.34 and 8.72 in the above experiment almost completely the formation of spots (0 to 5%).

Example 21

Effect against Erysiphae gramlnis on barley

a) Residual protective effect

About. 8 cm tall barley plants were sprayed with a spray liquid made from the active substance's spray powder (0.02% active substance). After 3-4 hours, the treated plants were dusted with conidia of the fungus. The infected barley plants were placed in a greenhouse at approx. 22°C and the fungal attack was evaluated after 10 days.

b) Systemic effect

In approx. 8 cm high barley plants it was completely a spray liquid

which was made from the active substance's spray powder (0.006% active substance in relation to soil volume). Care was taken here that the surface liquid did not come into contact with the above-ground plant parts. After 48 hours, the treated plants were pollinated with conidia of the fungus. The infected barley plants were placed in a greenhouse at approx. 22°C and the fungal attack was assessed after 10 days.

Compounds of formula I showed a good residual protective effect against Erysiphe fungi. Untreated but infected con-r troll plants showed an Erysiphe attack of 100%. Among other compounds from Table 1 -* 10, there were compounds No. 1.1, 1.4, 1.9, 1.14, 1.17, 1.23 to 1.27, 2.17, 3.1, 3.2, 3.6 to 3.8, 3.11, 3.12, 3.26, 3.51, 3.52, 3.54, 3.55, 3.70, 3.75, 3.78, 3.85, 3.86, 3.103, 3.127, 3.133, 3.156, 3.160, 3.162, 3.164, 3.168, 3.171, 3.172, 3.174, 3.176, 3.177, 3.193, 3.212, 3.213, 3.220, 3.221, 3.226, 3.227, 3.231, 3.232 til 3.234, 3.263, 3.267, 3.274, 3.279, 3,287, 3.292, 3.311, 3.314, 3.340, 3.348, 3.378, 3.383 til 3.388, 4.2, 4.15, 4.23, 4.50, 4.57, 4.59, 4.66, 4.77, 4.78, 4.81, 4.89, to 4.94, 4.113, 4.116, 4.137, 4.139, 4.140, 4.141, 4.146, 4.148, 4.150, 5.13, 5.14, 5.36, 5.40, 5.70. 5.71, 5.73, 5.75 to 5.78, 5.106 to 5.114, 6.1, 6.8, 6.17, 6.79, 6.80 6.82, 6.93, 7.3, 7.7, 7.21, 7.33, 7.34, 8.66, 8.69, 8.72 and 10.7 inhibited fungal attack on build on less than 5%. Compound No. 4.50 also showed this effect in the soil treatment (systemic effect!) and at a dilution to 0.006%.

Example 22

Residual protective effect against Venturia inaequalls' on apple sprouts.

Apple cuttings with 10-20 cm long new sprouts were sprayed with a spray liquid made from the active substance's spray powder (0.06% active substance). After 24 hours, the treated plants were infected with a conidial suspension of the fungus. The plants were then incubated for 5 days at 90-100% relative humidity and for a further 10 days placed in a greenhouse at 20-24°C. The scab attack was assessed 15 days after the infection. Connections no. 1.4, 1.9, 1.17, 1.24, 1.26, 2.17, 3.1, 3.6, 3.7, 3.11, 3.52, 3.55, 3.85, 3.86, 3.156, 3,156, 3,160, 3.164, 3.172, 3,176, 3.177, 3.213, 3.221, 3.221, 3.221, 3.221, 3.221, 3.221, 3.221, 3.221, 3.221, 3.221, 3.221, 3.221, 3.221, 3.221, 3.221, 3.221, 3.221, 3.221, 3.221, 3.221, 3.221, 3.221, 3.221, 3.221, 3.221, 3.221, 3.221, 3.221, 3.221, 3.221, 3.221. 3,383 to 3,387, 4.15, 4.23, 4.50, 4.59, 4.66, 4.78, 4.81, 4.89, 4.90 to 4.94, 4.113, 4.116, 4.137 to 4.141, 4.146 to 4.150, 5.13, 5.13, 5.14, 5.36, 5.70, 5.70, 5.70, 5.70, 5.70, 5.70, 5.70, 5.70. , 5.76, 5.106 to 5.110, 5.112 to 5.114, 5.118, 6.1, 6.8, 6.93 and 10.7 and others inhibited the disease attack to less than 10%. Untreated but infected shoots showed a 100% Venturia attack.

EXAMPLE 23

Effect against Botrytis cinerea on beans

Residual protective effect

About. 10 cm high bean plants were sprayed with a spray solution consisting of the active substance's spray powder (0.002% active substance). After 48 hours, the treated plants were infected with a conidial suspension of the fungus. After an incubation of the infected plants for 3 days at 95-100% relative humidity and 21°C, the fungal attack was assessed. Compounds from Table 1-10 inhibited the fungal infection very strongly in many cases. At a concentration of 0.002%, e.g. compounds Nos. 1.1, 1.4, 1.9, 1.17, 3.6, 3.7, 3.12, 3.51, 3.55, 3.86, 3.226, 3.231, 3.267, 3.311, 4.15, 4.50, 4.59, 4.66, 4.78, 4.93, 5.13, 5.13, 4.13, 4.91 , 5.40, 5.70, 5.71, 5.73, 5.75, 5.76, 5.78, 6.1, 6.8, 7.3, 7.33 and 8.72 proved to be fully effective (disease attack 0 - 5%). Botrytis attack for untreated but infected bean plants was 100%.

Azole derivatives according to the present invention in which the phenyl group is substituted in the para position with a phenoxy group are compared with respect to fungicidal activity with compounds according to the state of the art, which have a hydrogen, a methoxy group or a phenyl group as substituents on the phenyl group in the para position.

1. Compounds included in the test report 1.1 Compounds according to the state of the art 1.2 Compounds according to the present invention

2. Trial procedures

2. 1. Residual protective effect against 1-1 on wheat.

Six days after sowing, wheat plants were sprayed with a spray liquid prepared from a wettable powder of the active agent (200, 20 and 2ppm of the active agent). After 24 hours, the treated plants were infected with a uredospore suspension of the fungus. After an incubation time of 48 hours at approx. 25°C with 95-100% rel humidity, the infected plants were placed in a greenhouse at 22°C. An assessment of the development of the number of rust pustules was made 14 days after infection. The size and number of typical leaf spots found after the experiment served as a criterion for the evaluation of the effectiveness of the investigated compounds.

2. 2 Effect against 2- 2 on peanut plants

Three-week-old peanut plants were sprayed with a spray liquid prepared from a wettable powder of the active substance. (200, 20 and 2 ppm of the active compound). The treated plants were sprayed after approx. 12 hours with a conidospore suspension of the fungus. The infected plants were then incubated for 24 hours at 90% relative humidity, and then placed in a greenhouse at approx. 22°C. The size and number of typical leaf spots found after the treatment was considered a criterion for evaluating the effectiveness of the investigated substances.

2. 3 Residual protective effect against 3- 3 on barley

Building plants approx. 8 cm high were sprayed with a syringe of liquid prepared from a wettable powder of the active substance (200, 20 and 2 ppm of the active substance). The treated plants were pollinated with conidiospores of the fungus after 3-4 hours. The infected barley plants were evaluated after 10 days. The size and number of typical fungus growths found on the leaves after the experiment was considered a criterion for evaluating the effectiveness of the investigated compounds.

2. 4. Residual protective effect against 4-4 on apple shoots

Apple seedlings with 10-20 cm fresh shoots were sprayed with a spray liquid prepared from a wettable powder of the active substance (200, 20 and 2 ppm of the active substance). The treated plants were sprayed after 24 hours with a conidiospore suspension of the fungus. The plants were incubated for 6 days at 90-100% relative humidity and for a further 10 days they were kept at 20-24°C in a greenhouse. The extent of the scabies infection was assessed after 15 days of infection. The size and number of typical leaf spots found after the experiment served as a criterion for the evaluation of the effectiveness of the investigated compounds.

As each concentration in the above experiments was carried out in 3 parallels, each point in the following table should be understood to mean an average value of 3 experimental results.

3. Conclusion

3. 1. Results for compounds according to the state of the art jjt= in phytotdxic effects observed 3.2 Results for compounds according to the present invention

4. Conclusion

In the above-described phytopathogenic experiments 2.1 to 2.4, the phenoxyphenyl derivatives according to the present invention exhibit considerably better activity than the structurally closest compounds A-N according to the state of the art.

Claims (10)

1. Connections, characterized by formula I where Y is -CH= or -N=; Ra and Rb, independently of each other, are hydrogen, halogen, C 1 -C 3 alkyl, C 1 -C 4 alkoxy; Ar means unsubstituted or by halogen, C₁-C₁-alkyl, , nitro and/or CF3et one or more multiply substituted phenyl U and V independently of each other are a C1-c4 alkyl or to together form one of the following alkylene bridges while <R>log<R>2'<u>independently are hydrogen, C^-Cg -alkyl, or is the group -Cf^O-R^, the idet <R>7 is hydrogen, C₁-C₁ alkyl, C₃-C₁-alkenyl, et by halogen, C 1 -C 3 alkyl, one or more substituted phenyl or benzyl. R 3 , R 4 and R 5 independently of each other mean hydrogen or C1~C4-alkyl, the total number of carbon atoms in R3, R4 and R5 do not exceed the number 6, as well as their acid addition salts and metal complexes. 2. Compound according to claim 1, characterized in that it is similar to 2-(p-(4-chlorophenoxy)-o-chlorophenyl)-2-(1-(1H-1,2,4-triazolyl)-methyl)-4- ethyl-1,3-dioxolane. 3. Compound according to claim 1, characterized in that it is similar to 2-(p-(4-chlorophenoxy)-o-chlorophenyl)-2-(1-(1H-1,2,4-triazolyl)-methyl)-4- methyl-1,3-dioxolane. 4. Compound according to claim 1, characterized in that it is similar to 2-(p-(4-bromophenoxy)-o-chlorophenyl)-2-(1-(1H-1,2,4-triazolyl)-methyl-4-methyl- 1,3-dioxolane. 5. Compound according to claim 1, characterized in that it is similar to 2-(p-(4-chlorophenoxy)-o-chlorophenyl)-2-(1-(1H-1,2,4-triazolyl)-methyl)-4- propyl-1,3-dioxolane. 6. Compound according to claim 1, characterized in that it is similar to 2-(p-(4-fluorophenoxy)-o-chlorophenyl)-2-(1-(1H-1,2,4-triazolyl)-methyl)-4, 5-dimethyl-1,3-dioxolane. 7. Compound according to claim 1, characterized in that it is similar to 2-(p-(4-chlorophenoxy)-o-chlorophenyl)-2-(1-(1H-1,2,4-triazolyl)-methyl)-4- methoxyrneti1-1,3-dioxo-1 an. 8. Compound according to claim 1, characterized in that it is similar to 2-(p-(4-chlorophenoxy)-o-methylphenyl)-2-(1-(1H-1,2,4-triazolyl)-methyl)-4- methyl dioxane. 9. Use of a compound of formula (I) according to claim 1 for combating and/or preventing an attack by microorganisms such as phytopathogenic fungi on plants. 10. Means for use in combating and/or preventing microorganism attack on plants, characterized in that it contains at least one compound of formula I, as well as common carriers and excipients.