CS241507B2 - Fungicide for plants protection and method of active substances production - Google Patents

Abstract

The invention relates to novel arylphenyl ether derivatives of the formula <IMAGE> wherein Y is -CH= or -N=, Ra and Rb, each independently of the other, are hydrogen, halogen, C1-C3alkyl, C1-C3alkoxy or nitro, Ar is phenyl or naphthyl, each unsubstituted or mono- or polysubstituted by halogen, C1-C7alkyl, C1-C7alkoxy, nitro and/or CF3, U and V, each independently of the other, are C1-C12alkyl which is unsubstituted or substituted by halogen or C1-C6alkoxy, or together form one of the following alkylene bridges <IMAGE> wherein R1 and R2, each independently of the other, are hydrogen, C1-C12alkyl or C1-C12alkyl which is mono- or polysubstituted by halogen; phenyl or phenyl which is mono- or polysubstituted by halogen and/or C1-C3alkyl; or are the -CH2-Z-R7 group, wherein Z is oxygen or sulfur and R7 is hydrogen, C1-C8alkyl or C1-C8alkyl which is substituted by C1-C2alkoxy; C3-C4alkenyl, prop-2- ynyl, 3-haloprop-2-ynyl, phenyl or phenyl which is mono- or polysubstituted by halogen, C1-C3alkyl, C1-C3alkoxy, nitro and/or CF3; benzyl or benzyl which is mono- or polysubstituted by halogen, C1-C3alkyl and/or C1-C3alkoxy, R3, R4 and R5, each independently of the other, are hydrogen or C1-C4alkyl, the total number of carbon atoms in R3, R4 and R5 not exceeding 6, and R6 is hydrogen or C1-C3alkyl, together with the acid addition salts and metal complexes thereof. These compounds may be used in agriculture or related fields for controlling phytopathogenic microorganisms, and as antimycotic and/or anticonvulsive and anxiolytic agents in the pharmaceutical field, for example for controlling parasitic fungi in warm-blooded animals and/or for treating different forms of epilepsy, states of anxiety, tension and excitation, and/or manic states of mind.

Description

The present invention relates to a fungicidal composition for combating phytopathogenic fungi or preventing phytopathogenic fungal attack which comprises as active ingredient the novel substituted arylphenyl ethers derivatives of the general formula I below, as well as their acid addition salts and their copper complexes. The invention further relates to a process for the preparation of these novel compounds.

The arylphenyl ether derivatives which are used as active substances correspond to the general formula I

in which:

Y is -CH = or -N =, R _a and R _b are independently hydrogen,

halogen, alkyl. C 1 -C 3 or methoxy

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

whereas

R 1 and R 5 are each independently hydrogen, C 1 -C 3 alkyl or -CH 2 -Z-R 7, wherein:

Z is oxygen or sulfur; and

R? is hydrogen, (C1-C3) -alkyl, (C3-C4) alkenyl, methoxyethyl, phenyl, chloro or methyl-substituted phenyl, benzyl or chloro or methyl-substituted benzyl,

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

Ar represents a group of the formula

whereas

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

The term "alkyl" by itself or as a component of another substituent, depending on the number of carbon atoms mentioned, is, for example, the following groups: methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl or dodecyl; such as isopropyl, isobutyl, tert-butyl, sec-butyl, isopentyl, 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 both to the free compounds of the general formula (I) and to their addition salts with inorganic and organic acids, as well as their complexes with copper salts.

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

The copper complexes of formula I consist of a basic organic molecule and an inorganic or organic copper salt, for example, halides, nitrates, sulphates, phosphates, tartrates etc. of copper. In doing so, 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 are characterized by very valuable fungicidal effects in plant protection. The compounds can therefore be used in agriculture and related fields to combat phytopathogenic fungi.

Accordingly, the present invention provides a fungicidal plant protection agent for controlling phytopathogenic fungi or preventing phytopathogenic fungi, characterized in that it contains, as an active ingredient, at least one compound of the formula I as defined above or an acid addition salt thereof as an active ingredient. or its copper complex.

A preferred class of agriculturally useful fungicides are compounds of formula I, including their salts and copper complexes, wherein Y is -CH = or -N =, R _a and R _b are each independently hydrogen, halogen or an alkyl group having 1 to 3 carbon atoms,

Ar represents a group of the 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 below the formula

AND.

This group will be referred to as group 1b.

Within subgroup 1b, those compounds of formula I are preferred as plant protection fungicides in which U and V are independently of one another an alkyl group having from 1 to 3 carbon atoms or together represent one of the following alkylene groups

in which

R 1, R 2, R 3, R d and R 5 are each independently hydrogen or C 1 -C 4 alkyl, the total number of carbon atoms in R 5, R 6 and R 5 being not more than 6, referred to as 1c.

Another preferred group of agricultural preferred fungicides are those compounds of formula I wherein Y is -CH = or -N =, Ar has the meaning given under formula I, R _a, R _b, R _c, R _d and R _e are independently each of hydrogen, chloro, bromo, fluoro, methyl, methoxy or nitro, U and V are independently alkyl having 1 to 3 carbon atoms or taken together to form the alkylene groups represented by formula I, wherein R 1, R 2, R 3, R 4, R 5 and R 6 is independently hydrogen or C 1 -C 3 alkyl or R 1 is -CH 2 -O-R 7, wherein R 7 is hydrogen, C 1 -C 3 alkyl, C 3 -C 4 alkenyl, or phenyl; 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 (Compound No. 6, 8)

2- [p- (phenoxy) phenyl] -2-) 1- (1H-1,2,4-triazolylmethyl) -4-ethyl-1,3, -dioxane (Compound No. 6.17)

2- [p- (phenoxy) phenyl] -2- [1- (1H-1,2,4-triazolyl) methyl] -4-methyl-1, 3-dioxolane (Compound No. 1.4)

2- [p- (phenoxy) phenyl] -2- [1- (1H-1,2,4-triazolyl) methyl] -4-ethyl 1-1,3-dioxolane (Compound No. 1.9)

2- [p- (4‘-Bromophenoxy) phenyl] -2- [1- (1H-1,2,4-triazolyl) methyl] -4-ethyl-1,3-dioxolane (Compound No. 3.103)

2- [p- (phenoxy) -2'-methylphenyl] -2- [1- (1H-1,2,3-triazolyl) methyl] -4-ethyl-1,3-dioxolane (Compound No. 5.76)

2- [p- (3 ', 4'-dichlorophenoxy) phenyl] -2- [1- (1H-1,2,4-triazolyl) methyl] -4-methoxymethyl-1,3-dioxolane (Compound No. 3.177 )

2- [p- (3 ', 4'-dichlorophenoxy) phenyl] -2- [1- (1H-1,2,4-triazolyl) methyl] -4-ethyl-1,3-dioxolane (compound no. 3.172) 2- [p- (4'-chlorophenoxy) phenyl] -2- [1- (1H-1,2,4-triazolyl) methyl] -4-ethyl-1,3-dioxolane complex with copper sulfate ( Compound No. 5.76)

2- (p- (4‘-chlorophenoxy) -2-methylphenyl] -2-

- [1- (1H-1,2,4-triazolyl) methyl] -4-methyl-1,3-dioxolane (Compound No. 4.113) 2- [p- (phenoxy) -2'-methylphenyl] -2 - [1-

- (1H-1,2,4-triazolyl) methyl] -4-ethyl-1,3-dioxolane with nitric acid (Compound No 4.140)

2- [p- (4'-chlorophenoxy) phenyl] -2- [1- (1H-1,2,4-triazolyl) methyl] -4-ethyl-1,3-dioxolane (Compound No. 3.6).

The compounds of the formula I and their acid addition salts as well as their copper complexes according to the invention are prepared by carrying out at temperatures from 0 to 220 ° C, in particular at temperatures from 80 ° C to 170 ° C and preferably in the polar an organic solvent which is inert under the reaction conditions provides compounds of formula II in the reaction

Me-N-y (II) wherein

Me represents a hydrogen atom or a metal cation with the compounds of formula III

in which

Ar, R _a, R _b, U а V have the abovementioned meanings and

X is a nucleofugile leaving group, whereupon the optionally obtained free compound is converted by reaction with an organic or inorganic acid into an acid addition salt, the resulting acid addition salt is optionally converted by reaction with an alkali metal bicarbonate, carbonate or hydroxide into the free compound or the compound or acid addition salt obtained therefrom is converted into a copper complex by reaction with a copper salt.

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.

Nucleic acid leaving groups are, for example, reactively esterified hydroxy groups such as hydrohalic acid, e.g. hydrofluoric acid, hydrochloric acid, hydrobromic acid, or hydroiodic acid, or a lower alkanoic acid, optionally substituted with benzene or halosulfonic acid. an acid, such as methane, ethane, benzene, p-toluene or fluorosulfonic acid, esterified hydroxy groups.

Reaction of the azole of formula II

(II) in which:

Y is —CH = or —N = a

Me is preferably a metal atom, in particular an alkali metal atom, with a compound of formula III

in which

Ar, Ra, Rb, U and V have the meanings given in formula Ia

X is, for example, halogen, in particular chlorine, bromine or iodine, or benzenesulfonyloxy, p-tosyloxy, trifluoroacetyloxy or preferably lower alkylsulfonyloxy, such as mesyloxy, preferably in a relatively polar but inert organic solvent, for example Ν, Ν -dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, acetonitrile, benzonitrile and others. Such solvents may be used in combination with other inert solvents such as aliphatic or aromatic hydrocarbons such as benzene, toluene, xylene, hexane, petroleum ether, chlorobenzene, nitrobenzene and others.

If X is chlorine or bromine, an alkali metal iodide (such as NaJ or KJ) may conveniently be added to accelerate the reaction. Preferred are elevated temperatures of from 0 to 220 degrees Celsius, preferably from 80 to 70 ° C. Suitably, the reaction mixture is heated to reflux.

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 alkali and alkaline earth metal oxides, hydroxides, hydrides, carbonates and bicarbonates, as well as, for example, tertiary amines such as triethylamine, triethylenediamine, piperidine, pyridine, 4-dimethylaminopyridine, 4-pyrrolidylpyridine etc.

In this and the following production variants, the intermediates and end products can be isolated from the reaction mixture, and optionally purified by one of the conventional methods, for example, extraction, crystallization, chromatography, distillation, etc.

The compounds obtained as described above 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, in the compounds of formula I in which U and V are the same and are optionally substituted alkyl radicals of 1 to 12 carbon atoms, substituted C 1 -C 12 alkanol

V-OH (Vc) U group by one V group or by reaction with a diol of formula Vb, both U groups being a bivalent radical. The re-crystallization 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, p-toluenesulfonic acid or trifluoroacetic acid, preferably under distillation or azeotropically - distillation removal of easily boiling reaction products.

Further, 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 the group R a and R b, respectively. Thus, for example, halogen can be introduced by reaction with a halogen in the presence of a Lewis acid such as iron (III), zinc, boron or antimony (III) halide or N-chlorosuccinimide.

Further, nitro groups can be reduced, for example, with suitable complex hydrides, for example lithium aluminum hydride, to amines, 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 may 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 by treatment with preferably equimolar amounts of metal salts.

415 0 7 lead to complexes of the formula I with metals. 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.

The starting ketals of formula III can be obtained from the basic methylarylketones of formula XIV

₃ (xiv) by reaction with the desired diol in an inert solvent, for example a halogenated hydrocarbon (such as methylene chloride, ethylene chloride, chloroform, carbon tetrachloride, etc.) and simultaneous or subsequent halogenation. Addition of p-toluenesulfonic acid is preferred to accelerate the reaction.

Ketones of formula IV can be prepared by halogenating the starting ketones of formula XIV to compounds of formula XV

Ar @ ^{1 R} @ b (XV) and further reacting compounds of formula XV, analogously to the process of the invention, with an azole of formula II. Hal is preferably chlorine or bromine.

The ketals of formula III are obtained by reacting a starting ketone, for example of formula IV, with a suitable alcohol or diol.

The described process variant is also an object of the present invention.

All of the ketalization reactions of a ketone with a substituted α, β- or α, γ-diol are predominantly resulting in mixtures of diastereomers of the resulting · ketal. 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 both diastereomeric forms:

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

(XI к)

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

........ = for

- in front of the plane shown

The V-type configuration is accordingly referred to herein as the &quot; cis &quot; isomer.

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

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

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

Some of the starting materials and intermediates used in the process of the invention are known compounds, others can be produced by methods known per se. Some of the compounds are novel; their production is described herein.

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 and 4,156,008.

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 ingredients. Thus, these compounds have very advantageous curative, preventive and systemic properties in plant protection and can be used to protect crop plants. The active 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,

X2

Erysiphe,

Monilinia,

Uncinula;

Basidiomycetes such as

I-Iemileia,

Rliizoctonia,

Puccinia;

Fungi imperfecti, such as

В o tr у ths,

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 seeds (fruits, tubers, grains) and plant seedlings for protection against fungal infections as well as against 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 controlling phytopathogenic microorganisms, in particular fungi which are harmful to plants, or preventively preventing the attack of plants.

In addition, the present invention also encompasses the production of agrochemical compositions which consist in 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 and of the novel compositions.

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

cereals such as wheat, barley, rye, oats, rice, sorghum and related plants;

beet, such as sugar beet, fodder beet;

fruit-bearing fruit trees with kernels, seeds and berries: for example, apple, pear, plum, peach, almond, cherry, strawberry, raspberry and blackberry;

legumes such as beans, lentils, peas, soybeans, oilseeds; for example, canola, mustard, poppy, olive tree, sunflower, coconut, castor oil, cacao, peanut;

pumpkin plants such as pumpkins, cucumbers, melons;

fibrous plants such as cotton, flax, hemp, jute;

citrus-fruit-bearing fruit trees such as orange, lemon, tangerine, mandarin;

various vegetables; for example, spinach, lettuce, asparagus, cabbage, carrots, onions, tomatoes, potatoes, peppers;

laurel plants such as avocado (Persea gratissima), cinnamon, camphor;

or other plants, such as corn, tobacco, butternut, coffee, sugarcane, tea, grapevine, hops, banana and rubber, as well as ornamental plants (Compositae).

The active compounds of the formula I are used in agriculture usually in the form of preparations and can be applied simultaneously or sequentially with other active compounds, either to the area to be treated, to the plants 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 can also be selective herbicides, insecticides, fungicides, bactericides, nematicides, molluscucides or mixtures of several of these preparations, together with, if appropriate, other customary carriers, surfactants or other additives which improve the 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 their respective formulations, such as regenerated minerals, solvents, dispersants, wetting agents, adhesives, thickeners or binders.

One preferred method used in agriculture to apply an active compound of formula I or an agrochemical composition to an infected plant is to apply to the leaves of the plants. The number of applications and the amount used depend on the state of attack for the respective disease agent (fungus species). However, the active compounds of the formula I can also be fed to the plant via the soil via the root system (systemic effect), by pouring the place where the plant grows with a liquid medium or by incorporating the substances in solid form into the soil, for example granules (soil application) . However, the compounds of the formula I can also be applied to plant seeds (Coating) by either impregnating the seeds with a liquid preparation of the active substance or by coating with a solid preparation. In addition, in other cases, other applications are possible, 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

4 1 5 О 7 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, encapsulations, for example into polymeric substances in a known manner . Application procedures, such as spraying, fogging, dusting, sprinkling, coating or watering, as well as the type of compositions, are selected appropriately according to the desired objectives and proportions. A favorable application rate is generally between 50 g and 5 kg of active ingredient per hectare; preferably from 100 g to 2 kg per ha, in particular 200 g to 600 g of active ingredient per ha.

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

Suitable solvents are aromatic hydrocarbons, preferably fractions containing 8 to 12 carbon atoms, such as mixtures of xylenes or substituted naphthalenes, violet esters such as dibutyl phthalate or di-octyl phthalate, aliphatic hydrocarbons such as cyclohexane or paraffin hydrocarbons, alcohols and glycols, and their ethers and esters, such as ethanol, ethylene glycol, ethylene glycol monomethyl ether or ethylene glycol monoethyl ether, ketones such as cyclohexanone, strongly polar solvents such as N-methyl-2-pyrrolidone, dimethylsulfoxide or dimethylformamide, and optionally epoxidized vegetable oils such as epoxidized coconut oil or soybean oil, or water.

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

Suitable surface-active compounds are non-ionic cationic and / or anionic surfactants with good emulsifying, dispersing and wetting properties. Surfactants are also to be 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 stearic acid, or mixtures of natural fatty acids, which are obtained, for example, from coconut oil or tallow oil. The fatty acid salts of methyl taurine must also be mentioned.

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

Fatty sulfonates or fatty sulfates generally exist 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 an alkyl portion of the acyl radicals, such as sodium or potassium salt. ligninsulfonic acid, dodecylsulfuric acid ester or a mixture of sulfated fatty alcohols made from natural fatty acids. This also includes salts of sulfuric acid esters and sulfonic acids of fatty alcohol adducts with ethylene oxide. The sulfonated benzimidazole derivatives preferably contain 2 sulfo groups and a fatty acid radical of 8 to 22 carbon atoms. Alkylarylsulfonates are, for example, sodium, calcium or triethanolammonium salts of dodecylbenzenesulfonic acid, dibutylnaphthalenesulfonic acid, or the condensation product of naphthalenesulfonic acid and formaldehyde.

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 aliphatic or cycloaliphatic polyglycol ether derivatives. 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 carbon atoms in the alkyl radical of the alkyl phenols.

Other suitable nonionic surfactants are the water-soluble adducts of polyethylene oxide with polypropylene glycol, ethylenediaminopropylpropylene glycol and an alkylpolypropylene glycol of 1 to 10 carbon atoms in the alkyl chain containing 20 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups. The compounds generally contain from 1 to 5 units of ethylene glycol per propylene glycol unit.

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

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

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

Surfactants useful in the manufacture of the agrochemical compositions of the invention are described, inter alia, in the following publications: "Mc Cutcheon with Detergens 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.

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 compositions are preferred as commercial products, generally dilute compositions 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 substances to achieve particular effects.

Such agrochemical compositions are part of the present invention.

The following examples serve to illustrate the invention in greater detail without restricting it. Temperatures are given in degrees Celsius, pressures in Pa. Percentages and parts refer to weight.

Examples illustrating the method of production of active ingredients:

Example 1

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

(a) Production of the intermediate of formula XX

2- [p- (phenoxy) phenyl] -2-bromomethyl-4-methyl-1,3-dioxane parts of 2- [p- (phenoxy) phenyl] -2-oxy-1-bromoethane and 4 parts of 1,3 -butanediol in 40 ml of absolute toluene is heated in the presence of 0.2 part of catalytically active p-toluenesulfonic acid for 3 hours under reflux, the resulting water is separated by means of a water separator. After cooling to room temperature, the reaction mixture is washed twice with 20 ml of water each time, dried over sodium sulfate, filtered, the solvent is evaporated and the crude product is recrystallized from isopropanol. Colorless crystals of m.p. 96 DEG-106 DEG C. are obtained.

(b) Production of the final product

3.3 parts of 1,2,4-triazole sodium salt and a catalytically effective amount of potassium iodide in 40 ml of dimethyl sulfoxide are mixed with

10.2 parts of 2- [p- (phenoxy) phenyl] -2-bromomethyl-4-methyl-1,3-dioxane produced according to a) for 30 hours at an internal temperature of + 120 degrees Celsius. After cooling to room temperature, 300 ml of water are added, the reaction mixture is extracted three times with 30 ml of ethyl acetate each time, the combined extracts are washed twice with 20 ml of water each time, dried over sodium sulfate, filtered and the solvent is evaporated. The oily residue was purified by silica gel column chromatography using ethyl acetate as eluent. After evaporation of the solvent, an oily residue crystallizes upon addition of petroleum ether. Brownish crystals of m.p. 99.5-101 ° ^{C are obtained} .

Example 2

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

ct (3.12)

1.2 parts of imidazole sodium salt and a catalytically effective amount of potassium iodide are mixed together with 4 parts of 2- [p- (3-chlorophenoxy) phenyl] -2-bromomethyl-4-ethyl-1,3-dioxolane in 50 ml of dimethylformamide. 17 hours at 125 ° C internal temperature. After cooling, 150 ml of water are added to the brown reaction mixture, extracted three times with 50 ml of ethyl acetate each time, the combined extracts are washed twice with 50 ml of water each time, dried over sodium sulfate, filtered and the solvent is evaporated. The oily crude product was chromatographed over a 35 cm silica gel column eluting with acetone / ethyl acetate (1: 1). After evaporation of the solvent, the oily residue crystallized upon addition of petroleum ether. Light yellow crystals of m.p. 69-71 ° C are obtained.

Example 1 a d 3

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

a) Syntézamezlproduktů • - - - F) - - - - Preparation of 2- [p- (4-chlorophenoxy jfenyl] -2-methyl-4-e.thyl-l, 3-dioxolane ^{Whose CH2>}

37 parts of 4- (p-chlorophenoxy) acetophenone and 18 parts of 1,2-butanediol are heated in 400 ml of absolute toluene in the presence of 2 parts of catalytically active p-toluenesulfonic acid 14. hours at reflux using a water separator. After cooling to room temperature, the reaction mixture was washed twice with 400 ml of water, dried over sodium sulfate, filtered, the solvent was evaporated and the crude product was chromatographed on a 1 meter silica gel column using ligroin, hexane, ethyl acetate and ethyl acetate. toluene (5: 3: 1: 1). The product is obtained in the form of a slightly yellowish oil.

n ₀ 22 = 1.5527.

β) - Production of 2- [p- (4-chlorophenoxy) phenyl] -2-bromoethyl-4-ethyl-1,3-dioxolane

36.8 parts of 2- [p- (4-chlorophenoxy) phenyl] -2-methyl-4-ethyl-1,3-dioxolane, prepared according to a), is heated to boiling in 350 ml of chloroform. Under illumination with a -150 W light bulb, 19.4 parts of bromine, which is dissolved in 50 ml of chloroform, are added dropwise, and the reaction mixture is then heated under reflux for 2 hours. After cooling to room temperature, the reaction mixture is washed twice with 200 ml of water each time, dried over sodium sulfate, filtered and the filtrate is evaporated in a water-jet vacuum. In order to purify the crude product, chromatography is carried out on a 1-meter-long silica gel column using - - - toluene as the eluent. The product is obtained in the form of a yellow oil. т? 3 - 1.5805.

b) synthesis of the final product

4.4 parts of imidazole sodium salt and a catalytically effective amount of potassium iodide in 80 ml of dimethylformamide are co-heated with bromomethyl-4-ethyl-1,3-dioxolane prepared according to β] for 17 hours 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 each time, the combined organic phases are washed twice with 200 ml of water each, dried over sodium sulfate, filtered and the solvent is evaporated. The oily residue is chromatographed over a 50 cm silica gel column using 1: 1 acetone / ethyl acetate as eluent. After evaporation of the solvent, the product is obtained in the form of a brown oil. n _D ^2G 1.5750.

Example 4

Preparation of 2- [p- (phenoxy) phenyl] -2- (1H-1,2,4triazoiylmethyl] -4-ethyl-l, 3-dioxolaiiu _сн г сн ^сн ₃ 2 ~ (1.9) parts of 2- [p- ( Phenoxy) phenyl] -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 100 ml of dimethylsulfoxide 24. After cooling to room temperature, the reaction mixture is poured onto 600 ml of water, extracted three times with 200 ml of ethyl acetate each time, the combined extracts are washed twice with 200 ml of water each time, dried over sodium sulfate, filtered and the solvent is evaporated. The oily residue is chromatographed over a 50 cm silica gel column using a 1: 1 mixture of chloroform and ether as the eluent, and the solvent is evaporated to give white crystals, m.p. 81.5-83. 5 ° C.

Example 5

Synthesis of 2- [p- (phenoxy) phenyl] -2- (1H-1,2,4-triazolylmethyl) -1,3-dioxane

3.6 parts of 1,2,4-triazole and a catalytically effective amount of potassium iodide are stirred in 100 ml of dimethyl sulfoxide for 20 hours at an internal temperature of 140 ° C. After cooling to room temperature, 600 ml of water are added, extracted three times with 200 ml of ether each time, the combined extracts are washed twice with 200 ml of water each, dried over sodium sulfate, filtered and the solvent is evaporated. The oily residue is chromatographed over a 50 cm silica gel column using a 1: 1 mixture of chloroform and ether as eluent. After evaporation of the solvent, the residue crystallizes with a melting point of 129-130 ° C.

Example 6

Synthesis of 2- [p- (phenoxy) phenyl] -2- (1H-1,2,4-triazolylmethyl) -4-hydroxymethyl-1,3-dioxolane

CH ₂ OH (1.23)

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 iodide of potassium potassium was stirred in 50 ml of dimethyl sulfoxide for 4 hours at an internal temperature of 140 ° C. After cooling to room temperature, 600 ml of water are added, extraction is carried out twice with 200 ml of ethyl acetate, the combined extracts are washed twice with 200 ml of water each time, dried over sodium sulfate, filtered and the solvent is evaporated. The oily residue is chromatographed over a 50 cm silica gel column using acetone as the eluent. After evaporation of the solvent, an oily residue crystallizes upon addition of petroleum ether. Beige crystals of m.p. 111-122 ° C are obtained.

Example 7

Preparation of 2 - [(2'-methyl-4'-phenoxy) phenyl] -2- (1-imidazolylmethyl) -4-ethyl-1,3-dioxolane

(5.73)

(a) Preparation of 2-methyl-4-phenoxyphenacyl bromide (starting material) (6.1) parts of 2- [p- (phenoxy) phenyl] -2-bromomethyl-1,3-dioxane, 7,2 parts of potassium carbonate, phenyl ] -2- [1- (lH-l, 2,4-triazolylmethyl) -4-ethyl] -1,3-dioxolane сн ₃ O ^"0_ Cyf ^CH2 O ^r о

To 36.6 parts of 2-methyl-4-phenoxyacetophenone in 160 ml of acetic acid, 25.9 parts of bromine are added at 35 degrees Celsius over 1 1/2 hours. After the addition was complete, the reaction mixture was further stirred at room temperature for 1 hour, then poured into 1 liter of ice-water and extracted twice with 100 ml of ether each time. The combined organic extracts were washed well with water, dried over sodium sulfate, filtered, the solvent was evaporated and the crude product was digested with hexane. Brown crystals of m.p. 60-61 ° C are obtained.

b) Preparation of 2 - [(2'-methyl-4'-phenoxy) phenyl] -2-bromomethyl-4-ethyl-1,3-dioxolane (intermediate)

CH ₃

85.4 parts of 2-methyl-4-phenoxyphenacylbromide prepared according to 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-toluenesulfonic acid for 24 hours under reflux condenser using a water separator. After cooling to room temperature, the reaction mixture was washed three times with 250 ml of water each time, dried over sodium sulfate, filtered and the solvent was evaporated. Obtained as a red-brown oil.

c) Synthesis of the final product

9.5 parts of 2 - [(2'-methyl-4'-phenoxy) phenyl] -2-bromomethyl-4-ethyl-1,3-dioxolane, prepared according to b), 2.4 parts of imidazole and 4 parts. A portion of potassium tert-butoxide was stirred in 50 ml of dimethyl sulfoxide for 30 hours at an internal temperature of 110 ° C. After cooling to room temperature, 300 ml of water are added, the mixture is extracted three times with 150 ml of ethyl acetate each time, the combined extracts are washed with water until neutral, dried over sodium sulfate, filtered, the solvent is evaporated and the oily residue chromatographed over 50 cm. silica gel column using ethyl acetate as eluent. The product is obtained as a reddish oil. n _D ⁵⁰ 1.5550.

Cl

parts of 2- [p- (4‘-chlorophenoxy) -2‘-methylphenyl] -2-bromomethyl-4-ethyl-1,3-dioxolane,

13.3 parts of 1,2,4-triazole sodium salt and 1 part of sodium iodide are stirred in 200 ml of hexamethylphosphoric triamide for 24 hours at an internal temperature of 80 ° C. After cooling the reaction mixture to room temperature, the mixture was poured into 600 ml of water and extracted three times with 300 ml of ethyl acetate each time. The combined organic extracts were washed with water until neutral, dried over sodium sulfate, filtered, the solvent was evaporated and the oily residue was chromatographed over a 50 cm silica gel column eluting with ethyl acetate. The title compound is obtained as a brown resin. n _D ²² = 1.5718.

Example 9

Preparation of 2- [p (4‘-chlorophenoxy) -2‘-methylphenyl] -2- [1- (1H-1,2,4-triazolylmethyl) -4-methyl-1,3-dioxolane

CH ₃

51.4 parts of 2- [p- (4'-chlorophenoxy) -2'-methylphenyl] -2-bromomethyl-4-methyl-1,3-dioxolane, 24.2 parts of 1,2,4-triazole sodium and 0.8 parts of sodium iodide are stirred in 150 ml of sulfolane at 220 ^DEG C. for 5 hours. The reaction mixture is then cooled to room temperature, poured onto 300 ml of water and extracted three times with 250 ml of ethyl acetate each time. The combined extracts were washed twice with 200 ml of water each time, dried over sodium sulfate, filtered and the solvent was distilled off under reduced pressure. The oily residue is chromatographed on a silica gel column using ethyl acetate as the eluent. After evaporation of the eluent, the mixture of diastereomers remains as the eluent as a viscous product mixture of diastereomers. n _D ⁵⁰ = 1.5600.

Example 10

Example 8

Preparation of 2- [p- (4'-chlorophenoxy) -2'-methylProduction 2- [p- (4-trifluoromethylphenoxy) phenyl] -2- [1- (1H-1,2,4-triazolylmethyl) -4-ethyl -1,3-dioxolane

2B

7.4 parts of 1,2,4-triazole sodium salt and a catalytically effective amount of potassium iodide are stirred in 150 ml of dimethylsulfoxide together with 27 parts of 2 [p-4-trifluoromethylphenoxyKenyl] -2-bromomethyl-4-ethyl-1,3- of dioxolane for 36 hours at an internal temperature of 100 ° C. After cooling, the brown reaction mixture is poured onto 800 ml of water, extracted three times with 200 ml of ethyl acetate each time, the combined extracts are washed twice with 500 ml of water each, dried over sodium sulfate, filtered and the solvent is evaporated. The oily crude product was chromatographed over a 70 cm long silica gel column using 1: 1 chloroform / ether as eluent. Evaporation of the eluent gave a crystalline product. The white crystals melt at 106-107 ° C.

Example 11

Preparation of 2- [p- (4'-chlorfencxy) -2 -chlcrfe- ^s. nyl] -2- [1- [1H-tetriazdylmethyl] -4-ethyl] -1,3-dioxolane

8.5 parts of 1,2,4-triazole sodium salt, 1 part of potassium iodide and 18 parts of 2- [p- (4-chlorophenoxy) phenyl] -2-bromomethyl-4-methyl-1,3-dioxolane are stirred in 80 ml of hexamethylphosphoric triamide for 3 days at an internal temperature of 50 ° C. The brown reaction mixture is then poured onto 500 ml of water and extracted three times with 200 ml of ether each time. The combined organic extracts were washed twice with 200 ml of water each time, dried over sodium sulfate, filtered and the solvent was evaporated. The oily residue is chromatographed on a 35 cm silica gel column using chloroform / ether (1: 1) as eluent for purification. Evaporation of the solvent gave an oily residue and the addition of petroleum ether gave a crystalline product as yellow crystals, m.p. 81-84 ° C.

Example 1 d

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

CH _3, 5.4 parts of 2 - (N - (4 ^^. ^^ 10 ^ phenoxy-chlorphenyl NVL.] -2-bromomethyl-4-ethyl-3-dicxclanu, 2.3 parts of sodium salt of 1, The 2,4-triazole and a catalytically effective amount of sodium iodide are stirred in 20 ml of hexamethylphosphoric triamide for 12 hours at an internal temperature of 160 DEG C. After cooling the reaction mixture to room temperature, the mixture is poured into 150 ml of water and extracted three times. The combined organic extracts were washed until neutral, dried over sodium sulfate, filtered, the solvent was evaporated and the oily residue was chromatographed over a 20 cm silica gel column eluting with ethyl acetate. yellowish highly viscous oil n _D ²¹ ' ⁵ = 1.5773.

Example 12

Preparation of 2- [p- (4-chlorophenoxy) phenyl] -2- [1- (1H-1,2,4-triazolylmethyl) -4-methyl] -1,3-dioxolane

3.6 parts of the sodium salt of 1,2,4-O, and a catalytically effective amount of potassium iodide is stirred in 30 ml of hexamethylphosphoric triamide together with 8 parts of 2- [p- (4-chlorophenoxy) (phenyl) -2-bromomethyl-4,5-dimethyl-1,3-dioxolane at 20 ° C for 10 days. 150 ml of water are then added to the brown reaction mixture and the mixture is extracted three times with 100 ml of ethyl acetate each time. The combined extracts were washed twice with 100 ml of water each time, dried over sodium sulfate, filtered and the solvent was evaporated. The oily residue crystallized upon addition of ether. Yellow crystals of m.p. 95-97 ° C are obtained.

Example 1 4

Preparation of 2- [p- [4'-bromophenoxy) -2'-chlorophenyl] -2- [1- (1H-1,2,4-triazdyl) methyl] -4-methyl-1H-dioxolane

241 27

15.6 parts of 2- [p- (4'-bromophenoxy) -2'-chlorophenyl] -2-bromomethyl-4-methyl-1,3-dioxolane,

6.2 parts of 1,2,4-triazole sodium salt and 0.3 parts of sodium iodide were stirred in 40 ml of 1-methyl-2-pyrrolidone for 16 hours at an internal temperature of 150 ° C. After cooling to room temperature, 250 ml of water were added to the reaction mixture and extracted twice with 200 ml of ethyl acetate each time. The combined organic extracts were washed with water until neutral, dried over sodium sulfate, filtered and the solvent was evaporated. The oily residue was purified by silica gel column chromatography using ethyl acetate as eluent. Evaporation of the eluent gave a mixture of diastereomers as a viscous product. n _D ²² · 5 = 1.5897.

Example 15

Preparation of 2- [p- (4‘-chlorophenoxy) -2‘-chlorophenyl] -2- [1- (1H-1,2,4-triazolyl) methyl] -4-methyl-1,3-dioxane

parts of 2- [pt (4‘-chlorophenoxy) -2 6-chlorophenyl] ·· 2-bromomethyl-4-methyl-1,3-dioxane, 6.4 parts of sodium salt. 1,2,4-rlazole and a catalytically effective amount of sodium iodide are stirred in 50 ml of sulfonate for 7 hours at 200 ° C. The reaction mixture was cooled to room temperature, poured into 200 ml of water and extracted three times with 70 ml of ethyl acetate each time. The combined extracts were washed neutral, dried over sodium sulfate, filtered and the solvent was evaporated. The oily residue is chromatographed over a 25 cm silica gel column using ethyl acetate as the eluent. After evaporation of the eluent the product crystallizes. The white crystals melt at 104-106 ° C.

Example 16

Preparation of 2- [p- (4-bromophenoxy) phenyl] -2- [1- (1H-1,2,4-triazolyl) methyl] -4-n-propyl-1,3-dioxolane ^ CH ₂ CH ₂ CH ₃

6.5 parts of 1,2,4-riazole sodium salt, 1 part of potassium iodide and 25 parts of 2- [p- (4-bromophenoxy) phenyl] -1,2-benzomethyl-4-n-propylthio 1,3-dioxolane are mixed in 150 ml. of dimethyl sulfoxide for 60 hours at an internal temperature of 90 ° C. After cooling to room temperature, the reaction mixture is poured onto 800 ml of water and extracted three times with 250 ml of ethyl acetate each time. The combined organic phases were washed twice with 200 ml of water each time, dried over sodium sulfate and the solvent was evaporated. The oily residue is chromatographed on a silica gel column using a 1: 1 mixture of chloroform and ether as the eluent. Evaporation of the solvent gave an oily residue from which the title compound crystallized as yellow crystals upon addition of petroleum ether. Mp 81-83 ° C.

Example 17

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

ch ₃

11.9 parts of 2- [pt (4t-Chlorophenoxy) phenyl] 1,2-bromomethyl-4-methyl-1,3-dloxane, 3.1 parts by volume

1,2,4-triazole, 6.2 parts of potassium carbonate and 0.5 parts of potassium iodide were stirred in 50 ml of dimethylsulfoxide for 85 hours at an internal temperature of 110 ° C. After cooling to room temperature, the brown reaction mixture was poured into 300 ml of water and extracted three times. 100 ml of ether each. The combined extracts were washed twice with 100 ml of water each time, dried over sodium sulfate, filtered and evaporated. The oily residue is chromatographed over a 40 cm silica gel column eluting with methylene chloride / ether (1: 1). After evaporation of the solvent, a mixture of diastereomers remains as a viscous mass. nn ²⁵ = 1.5748.

Example 18

Preparation of 2- [p- (4‘-bromophenoxy) -2‘-methylphenyl] -2- [1- (1Htl, 2,4-triazolyl) methyl] -4-ethylthi., 3-dioxolane

13.9 parts of β-t-4-bromophenoxy-4-methylphenyl] -2-bromomethyl-4-ethyl-1,3-dioxolane,

5.3 parts of 1,2,4-riazole sodium salt and 0.2 parts of sodium iodide are stirred in 30 ml of 1-methyl-2-pyrrolidone for 12 hours at 155 ° C. After cooling to room temperature, 200 ml of water was added to the reaction mixture, and the mixture was extracted three times with 100 ml of ethyl acetate each time. The combined extracts were washed with water until neutral, dried over sodium sulfate, filtered and the solvent was evaporated. For purification, the oily yellow residue is chromatographed over a silica gel column using ethyl acetate as the eluent. The title compound is obtained in the form of a yellow resin. n _D ²⁰ = 1.5778.

Example 19

Preparation of 2- [p- (4'-chlorophenoxy) -2'-chlorophenyl] -2- [1- (1H-1,2,4-triazolyl) methyl] -4-n-propyl-1,3-dioxolane .

Ct

THgCH? ^CH 3

3.7 parts of 2- [p- ^{(4'-chlorophenyl:} xy) -2-chlorophenyl] -2-bromomethyl-4-n-propyl-l, 3-dioxolane, 1.5 parts of sodium salt of 1,2, Of 4-triazole and 0.1 part of sodium iodide are stirred in 25 ml of hexamethylphosphoric triamide at 170 ° C for 14 hours. After cooling to room temperature, the reaction mixture is poured into 100 ml of water and extracted twice with 40 ml of ethyl acetate each time. The combined extracts were washed with water until neutral, dried over sodium sulfate, filtered and the solvent was evaporated. The oily residue was purified by silica gel column chromatography using ethyl acetate as eluent. The title compound is obtained in the form of a yellow resin. n _D ²¹ = 1.5707.

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

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

Table 1

Compounds of formula XXI ¹ --X

(xxi) including isomeric forms:

compound number Rio Y salt physical data 1.1 H N - 11. 100-102 ° C 1.2 H N HNO3 1.3 H CH - 1.4 CH3 N - mp 85-92 ° C 1.5 CHs N HCl 1.6 CHs N CuC12 1.7 CH3 CH - 1.8 CH3 N Mn (NO 3) 2 1.9 C2H5 N - mp 81.5 '- 83.5 ° C 1.10 C2H5 N HN03 1.11 C2H5 N ZnC12 1.12 C2H5 N Mn (NO 2) 2 1.13 C2H5 N FeCls 1.14 C2H5 CH - light brown oil 1.15 C2H5 CH CuC12 1.16 C3H7-n CH - 1.17 C3H7-n N -. mp 68.5-71 ° C 1.18 C3H7-I1 N ZnC12 1.19 CsH7-n N HCl 1.20 CiH9-n N - 1.21 CiH9-n CH - 1.22 CH2Cl N - 1.23 CH2OH N - mp 111-122 ° C

compound number Rio Y salt physical data 1.24 CH;> 0C ^H OC ^C1 · N - viscous oil n _D 20 = 1.5865 A 1.25 N - mp 83-85 ° C B 1.26 сь _г о- / 2 ^ -сн ₃ N - mp 107-109 ° C A 1.27 N - mp 90-94 ° C B 1.28 CH 2 OH CH - mp 118-123 ° C 1.29 CH2OCH3 CH - 1.30 C2H5 N 1/2 CuSOá 1.31 CH2OC2H5 N -. 1.32 CH2OCH3 N - 1.33 CH2OCH2CH2OCH3 N -

Table 2

Compounds of formula XXII

^R 11 ^R12 (xxn) salt physical data including isomeric forms Y compound number Rli R12 2.1 CH3 C2H5 CH - 2.2 CH3 C2H5 N - 2.3 CH3 C2H5 CH HNO3 2.4 CH3 C2H5 N HN03 2.5 CH3 C3H2-n CH -. 2.6 CH3 C3H7-n N - 2.7 CH3 C3H7-n N HNO3 2.8 CH3 C3H7-n N Mn (NO 3) 2 2.9 CH3 CH3 CH - 2.10 CHs CH3 CH CuClž 2.11 CHs C2H5 CH Mn (NO 3) 2 2.12 CH3 C2H5 CH CuCl2 2.13 CH3 C2H5 N CuC12 2.14 CH3 C2H5 N ZnClz 2.15 CH3 C2H5 N Mn (NO 3) 2 2.16 CH3 C2H5 N FeCl3 2.17 CH3 CH3 N - oil; ^.delta. = 1.5643 2.18 CH3 CH3 N HNO3 2.19 C2H5 CH3 CH MnC12 2.20 C2H5 CH3 N MnC12 2.21 C2H5 CH3 CH H2SO4

^R 12 Y salt physical data nina number

2.22 C2H5 CHs CH ZnCl2 2.23 C2H5 C2H5 CH - 2.24 C2H5 C2H5 CH H2SO4 2.25 C2H5 C2H5 N - 2.26 C2H5 C2H5 N HN03 2.27 C2H5 C2H5 N HCl 2.28 C2H5 C5H7-n N - 2.29 C2H5 C3H7-I N - 2.30 C2H5 C3H7-n CH - 2.31 C2H5 C3H7-n N HCl 2.32 C2H5 C2H5 N Mn (NO 3) 2 2.33 CH3 C2H5 N (COOH) 2 2.34 CH3 C2H5 CH (C00H) 2 2.35 CH3 C3H7-I N - 2.36 CH3 C3.H7-1 N H2SO4 2.37 - (CH2) 4- CH - 2.38 - (CH2) 4- CH HN03 2.39 - (CH2) 4—— N - 2.40 - (CH 2) 4 - N Mn (NO 3) 2 2.41 - (CH 2) 4 - N (COOH) 2 2.42 - (CH 2) 4 - N ZnCl2 2.43 - (CH 2) 4 - N HCl 2.44 - (CH 2) 4 - CH ZnC12

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Examples of compositions according to the invention (agrochemical compositions) which contain ka32 active ingredients of the formula I (% =% by weight):

8. Emulsion concentrate:

C)

and)

(b)

the active substance of Tables 1 to 10 25% 40% 50% calcium dodecylbenzenesulfonic acid acid 5% 8% 6% castor polyethylene glycol ether oils (36 moles of ethylene oxide) 5% - - tributylphenylpolyethylene glycol ether (30 mol ethylene oxide) - 12% 4% cyclohexanone - 15% 20% mixture of xylenes 65% 25% 20% Of such concentrates, they may be dilution with water prepare emulsions each pose- concentration. 9. 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% benzine (boiling point 160 to 190 ° C) - - 94 ·% -

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

10. СгапиШ:

and) (b) the active substance of Tables 1 to 10 5% 10% kaolin 94% - highly dispersed silicic acid 1% - attapulgit - 90% The active ingredient is dissolved in methylene chloride and sprayed onto the carrier and dissolve- the dough is then evaporated in vacuo. 11. Dust: and) (b) the active substance of Tables 1 to 10 2% 5% highly dispersed silicic acid 1% 5% talc 97% - kaolin - 90% Thorough mixing of carrier substances with Examples of agrochemical means that the active substance is directly available re contain solid effective compounds of formula I dust. (% =% by weight) 12. Wettable dust: and) (b) C) the active substance of Tables 1 to 10 25% 50% 75% ligninsulfonic acid sodium salt 5% 5% - sodium lauryl sulfate 3% - 5% sodium diisobutylnaphthalenesulfonate - 6% 10% octylphenolpolyethylene glycol ether (7 to 8 moles of ethylene oxide) - 2% - highly dispersed silicic acid 5 ·% 10%) 10% kaolin 62 27% -

The active ingredient is well mixed with the other ingredients and the mixture is ground well calcium dodecylbenzenesulfonic acid 3 ·% suitable mill. A wettable powder is obtained, polyglycolethers of castor oil which can be diluted with water to suspensions every (35 moles of silyl oxide) 4% desired concentration. cyclohexanone 30% mixture of xylenes 50% 15. Emulsion concentrate: From this concentrate, they can dilution the active substance of Tables 1 to 10 10% with water to prepare emulsions each octylphenolpolysthylsnglkkolethea concentration. (4 to 5 moles of ethylene oxide) 3% 14. PPprra: and) (b) the active substance of Tables 1 to 10 5% 8% talc 95% - kaolin - 92%

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

15. Extruded granules:

active ingredient from Tables 1 to 10 10% nalignin sulphonate 2% carboxymethylcellulose 1% kaolin 87%

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.

16. Coated granulate:

active ingredient 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.

17. Suspension concentrate:

active ingredient from Tables 1 to 10 40% ethylene glycol 10% nonylphenolpolyethylene glycol ether (15 mol ethylene oxide) 6% lignin sulphonic acid sodium salt 10% carboxymethylcellulose 1%

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

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

Examples of pharmaceutical formulations:

17. Maati:.

Ointment containing 5% 2- [p- (4-chlorophenoxy) phenyl] -2- (1-imidazolyl) -4-ethyldioxolane can be prepared as follows:

Ingredients:

Active ingredient 5% Vaseline 45% Paraffin oil 19.1% Cetyl alcohol 5% Beeswax 5.0% Soabilane-quinoleate 5.0% p-Hydroxybenzoic acid ester у 0.2% demineralized water up to 100.0 *%

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

18. КгГш:

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

Ingredients:

active substance 10.0% itopropyl palmital 8.0% celyl palmilate 1.5% silicone oil 100 1.5 ·% toabitanium monostearate 3.0% polysorbate 60 3.5%

1,2-propylene glycol PH 20.0% acrylic acid polymer 0.5% triethanolamine 0.7% water demineralised up to 100.0%

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

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

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

Ingredients:

Active ingredient 5,0% o o cetyl palmitate PH _with 2,0% cetyl alcohol PH 2,0% triglyceride mixture of saturated medium fatty acids 5,0% stearic acid 3,0% o o glycerin stearate PH 4,0% polyhydroxyethyleneacetyl stearyl ether 1,0 % microcrystalline cellulose 0.5%

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

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

20. Hydrogel:

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

Ingredients:

active ingredient 5% propylene glycol 10 to 20% isopropanol 20% hydroxypropyl methylcellulose 2% water up to 100%

Thereafter, the active ingredient solution is mixed with the swollen cellulose derivative and optionally fragrances (0.1%) are added.

21. Foam spray:

man make

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

Ingredients:

1.00%

1,70%

1.00%

2.00% active ingredient cetyl alcohol PH paraffin oil, viscous isopropyl myristate, polyhydroxyethyleneacetyl stearyl ether 2,40% sorbitant monostearate 1,2-propyl ethyl glycol PH methylparaben prop-hen glycerin stearate water, demineralised up to

1.50%

5,00%

0.18%

0.02%

0,10% 100,00%

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

Performance:

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

22. Capsules:

Gelatin capsules containing 200 mg of [p- (phenoxyphenyl) -2- [1- (1H-1,2-thiazolyl) methyl] p-dioxane as active ingredient can be prepared, for example, as follows:

Composition (for 1000 capsules):

active substance lactose, ground

100 g

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

23. Tablets:

The hydroxy-propyl-meth-cellulose is swollen in water and the active substance is dissolved in a mixture of isopropanol and propylene glycol.

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

Ingredients (for 1,000 tablets):

active substance 25.0% lactose 100.7% wheat starch 7.5% polyethylene glycol 6000 5.0 ° / o talcum5.0 g magnesium stearate1.8 g demineralized water as needed

Production:

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

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

Ingredients (for 1000 tablets):

Active ingredient 100.0g lactose 50.7g wheat starch 7.5g polyethylene glycol 6000 5.0g talcum 5.0g magnesium stearic acid 1.8g demineralized water as needed

Production:

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

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

Ingredients (for 1,000 tablets):

active ingredient 75.0g lactose 100.7g wheat starch 7.5g polyethylene glycol 6000 5.0g talc 5.0 g magnesium stearic acid 1.8 g demineralized water as needed

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

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

Examples illustrating biological activity:

For the following examples, which illustrate biological activity (Examples 24 to 28), the following products A to D, which are known on the market, were simultaneously tested for comparison purposes:

A = 'Maneb' = manganese ethylene bis-dithiocarbamate

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

G = "Fentin Acetate" = triphenyltin acetate

D = "Forpet" = N-trichloromethylthiophthalimide

Example 24

Effect against rust (Puccinia graminis) on wheat

(a) Residual protective effect

Wheat plants are sprayed with a suspension made of wettable powder (active ingredient concentrate) 6 days after sowing, the active ingredient concentrate 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 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.

b) Systemic effect

5 days after sowing, the wheat plants are covered with a suspension made of a wettable powder of the active substance (concentration 0.006% of active substance, based on the volume of soil). After 48 hours, the treated plants are infected with a fungal uredospore suspension. After incubation for 48 hours at 95-10% relative air humidity and about 20 ° C, the infected plants are placed in a greenhouse at about 22 ° C. The development of the development is performed 12 days after infection.

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

The results are shown in the following table:

(a) Residual protective action against Puccinia graminis

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

In addition, Compound No. 6.8 shows an excellent systemic effect, among others. Infestation with Puccinia was completely suppressed (0% attack). This effect was possible ж ^ М ·! also at a markedly reduced applied amount of 0.006%.

Example 25

Activity against Ceircospora arachidicola on groundnut plants Up to 15 cm high groundnut plants are sprayed with a spray suspension (0.0.2% of active ingredient) which was made of a wettable powder of the active ingredient. After 48 hours, the plants are infected with a conidia suspension of the fungus. The infected plants are incubated at about 21 ° C and high humidity for 72 hours and then placed in a greenhouse until typical spots on the leaves. Assessment of fungicidal effect is performed 12 days after infection, based on the number and size of the spots occurring.

Compared to untreated but infected control plants (number and size of spots = 100 ° / o), peanut plants treated with the active substances of Tables 1 to 10 show a significantly reduced attack by Cercospora. Individual results are shown in the following table:

Effect against Cercospora arachidicola: compound number attack% compound number attack%

1.1 0-4 3.234 0 1.4 2—5 3.267 3-4 1.9 0 3.292 0—4 1.14 7—10 3.314 0 1.17 0 3.348 0—2 1.24 0 4.15 0 1.25 0 4.23 1 1.26 0—2 4.50 0 1.27 0—1 4.57 0—3 2.17 0 4.59 0—2 3.1 0 4.66 0—2 3.2 5—10 4.89 0 3.6 0—4 4.90 0 3.7 0 4.91 0 3.11 0 4.92 0 3.51 0—4 4.93 0 3.52 0—3 4.94 5—7 3.54 0—3 4.113 0 3.55 0 4.116 5—7 3.75 5—10 5.13 0 3.78 0 5.14 0 3.85 0 5.36 0 3.86 0 5.40 0 3.127 0—1 5.70 0—2 3.133 0-4 5.71 0—2 3.155 5—9 5.73 0 3.156 0 5.75 0 3.162 0-5 5.76 0 3.171 0—3 5.77 0—1 3.172 0 5.78 0 3.176 0 6.1 0 3.177 0—1 6.8 0 3.212 0—5 7.33 7—9 3.213 2—3 7.34 3—5 3.220 4—5 8.72 7—10 3.221 0 AND 93—98 3.226 0—3 В 95—100 3.231 0 C 93—96 3.232 0 D 94—98 3.233 0 control 100 ALIGN!

Example 26

Action against powdery mildew (Erysiphe g-raminis) on barley

(a) Residual proactive effect

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

(b) Systemic effect:

They are poured into a suspension (concentration 0.006% of active ingredient, based on the volume of soil) which has been made from a wettable powder of the active ingredient. Care is taken that the suspension does not come into contact with the aerial parts of the plants. After 48 hours, the treated plants are dusted with conidia of the fungus. Infected barley plants are placed in a greenhouse at a temperature of about 22 ° C and after 10 days the fungal infestation is assessed.

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

The test results are summarized in the following table:

About 8 cm tall barley plants are effective 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

compound number attack% compound number assault '’ 5.40 0 7.3 0 5.70 2—5 Ί.Ί 0 5.71 0 7.21 0—2 5.73 0 7.33 0 5.75 0 7.34 4-5 5.76 0 8.66 0 5.77 3—5 8.69 0—5 5.78 0 8.72 5—7 5.106 0 10.7 0 5.107 7—10 AND 98—100 6.1 0 (B) 100 ALIGN! 6.8 0 C 97—100 6.17 0 D 96—100 6.79 0—3 control 100 ALIGN! 6.80 5—8

Example 27

Residual protective effect against apple scab (Venturia inaequalis ·) on apple shoots

Apple seedlings with 10-20 cm long fresh shoots are sprayed with a suspension (concentration of 0.06% active ingredient) which was made from a wettable powder of the active ingredient. After 24 hours, the treated plants are infected with a fungal conidia suspension. The plants are then incubated for 5 days at 90-100% relative air humidity for a further 10 days. placed in a greenhouse at 20 24 ° C. Scab infestation is evaluated 15 days after infection. The results of the test are shown in the following table:

Effect against Venturia inaequalis

compound number attack% compound number attack% 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 AND 100 ALIGN! 4.15 8—9 (B) 100 ALIGN! 4.23 7—10 C 100 ALIGN! 4.50 0 D 100 ALIGN!

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

Example 28

Effect against gray mold (Botrytis cinerea) on bean

Residual protective effect

The about 10 cm tall bean plants are sprayed with a suspension (0.02% active ingredient) which was made from a wettable powder of the active ingredient. After 48 hours, the treated plants are infected with a conidia suspension of the fungus. After incubating the infected plants for 3 days at 95-100% relative humidity and 21 ° C, the fungal infestation is assessed.

In many cases, the compounds of Tables 1 to 10 suppress fungal infection very strongly.

The results are shown in the following table:

Effect against Botrytis cinerea:

compound number attack% 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

compound infestation% number

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, V, C or D, as well as untreated control plants, show 100% infection with Botrytis cinerea.

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

Claims (12)

SUBJECT OF THE INVENTION 1,2,4-trioxoolyl) methyl N-methyl-1,1'-oxolanine with nitric acid. CLAIMS 1. A fungicidal agent for the protection of plants for controlling phytopaithogenic fungi or for preventing infestation by у topathogenic fungi, characterized in that, in addition to the carrier substances, it contains at least one compound of the general formula I in which: Y confused —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 taken together are any of the following alkylene bridges (I) R @ ₁ R @ ³ phy or clasp one compound of formula (I) in which:. U and V are, independently of one another, an alkyl group having 1 to 3 carbon atoms or together are one of the following alkylene groups wherein: R 1 and R 2 are each independently hydrogen, C 1 -C 3 alkyl or -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 3, R 4 and R 5 are each independently hydrogen or C 1 -C 3 alkyl, wherein the total number of carbon atoms in R 3, R 6 and R 5 does not exceed 6, and Ar represents a group of the formula wherein R c, R d and R e are each independently hydrogen, halogen, C 1 -C 4 alkyl, C 1 -C 3 alkoxy, trifluoromethyl or nitro or an acid addition salt thereof or a copper complex thereof. 2- [p- ((‘‘ - 1 1) c 1 ^ € ny>> j y y -2 -2 -2-chloxlenyl) -2- - (1H [1,2,4-triazxlyl) methyl-4-ethyl-1, 3-dioxolane and 2 - [(2-ethyl-4-phenoxy) phenyl] -2- [1- (1H- (I) in which " Y is --CH-- or --N.dbd.Ra and Rb are each independently hydrogen, halogen, C1-C3alkyl or methoxy; U and V are independently of one another an alkyl group having 1 to 3 carbon atoms or together form one of the following alkylene bridges wherein: R 1 and R 2 independently of one another represent a hydrogen atom, an alkyl group. C 1-C uhlíku-C - skupinu. of the formula · —CH ^ Z · ^, where:: · Z · means · oxygen or x · sulfur, R 7 is hydrogen, alkyl having 1 to 3 carbon atoms; a (C 3 -C 4) alkenyl group, a methoxy group, a phenyl group, a chlorine or methyl-substituted phenyl group, a benzyl group or a chlorine or methyl group, R 5, R d and R 5 are independently from each other an alkyl group having 1 to 3 carbon atoms, wherein the total number of carbon atoms in the substituents R 3, R 3 and R 5 does not exceed 6, and Ar represents a group of the formula wherein R _c , R _d and R _e independently represent one of the following alkylene bridges hydrogen, halogen, C 1 -C 4 alkyl, C 1 -C 3 alkoxy, trifluoromethyl or nitro, and addition salts thereof acids and copper complexes, characterized in that at a temperature of from 0 to 220 ° C, in particular at temperatures of from 80 to 170 ° C and preferably in a polar organic solvent which is inert under the reaction conditions, the compound of the formula II is condensed. = (Me) -N (Y) wherein Me means hydrogen or a metal cation and Y is as defined above, with a compound of formula III wherein: X is a nucleofugic leaving group and Ar, R _a , R _b , U and V have the meanings given above, whereupon the optionally obtained free compound is converted by reaction with an organic or inorganic acid into an acid addition salt, the obtained acid addition salt is optionally converted into a free compound by reaction with carbonate, bicarbonate or alkali metal hydroxide, or the obtained free compound or the acid addition salt obtained is converted by reaction with copper selenium to copper complex. 2- [p- (4‘-Sulfonylbutyl-1 H-imidazo) -2- [1 H -imidazo] (4-ethyl-1,3-dioxox) (rope). 2- [p- (4'-chlorophenoxy) -2-methylphonyl] -2- [1- [1H-1,2,4-triazole-4-yl] methyl] -4-ethyl-1,3-dicxolane , 2- [p- (4'-Frifluorophenoxy) phenyl] -2- [1- (1H- -1,2,4-triazolyl) methyl] -3-ethyl-1,3-dloxolane; 2- [p- (4'-Bromophenoxy) phenyl] -2- (1- (1H-1,2,4-triazazyl) methyl) -4-n-propyl-1,3-diox, olanem, ' 2- [p- (phenoxy) -2-chlorophenyl] -2- [1- (1H-1,2,4-triazolyl) methyl] -4-methyl-1,3-dioxane, 2- (p - [(4‘-Bromophenoxy) phenyl] -2- [1- (1H-1,2,4-triazolyl) methyl] -4-ethyl-1,3-dioxolane, 2- [p- (4'-chlorophenoxyphenyl) -2- [1- [1H-1,2,4-triazolyl) methyl] -3,4-dimethyl-1,3-dioxolane, 2- [p- [4'-chlorophenoxy] -2-methylphenyl] -2- [1- (1H-1,2,4-triazolyl) methyl] -4-methyl-1,3-dioxolane, 2- [p- (phenoxy) -2-methylphenyl] -2- [1- (1H-1,2,4-riazxlyl) methyl] -4-ethyl-1,3-dicxolan, 2 - [(2-methyl-4-phenoxy) phenyl] -2- [1-imidazolylmethyl) -4-ethyl-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] -1'-ethyl-1,3-dioxolane with copper sulfate, 2- [p- (3 3, 4‘-dichlorophenoxy) phenyl] -2- [1- (1Η · -1,2,4-triazolyl) methyl] -4-methoxymethyl-1,3-dioxolane, 2- [p- (phenoxy) -2-chlorophenyl] -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-1H-dioxolane, 2- [p- (phenoxy) phenyl] -2- [1- (1H-1,2,4-triazolyl) methyl] -4-methyl-1,3-dioxane, 2- [p- (phenoxy) phenyl] -2- [1- [1H-1,2,4-triazolyl) methyl] -4-ethyl-1,3-dimethylsilane, · 2. A composition according to claim 1, characterized in that, as ^one active ingredient at least one compound of formula I wherein Y is —CH = or - N ~, R a and R _b are independently hydrogen, halogen or C 1 -C 3 alkyl; Ar represents a group of the formula wherein R _c , R d and R e are each independently hydrogen, halogen or C 1 -C 3 -alkyl U and V have the meanings given in point 1. 3. A composition according to claim 2, wherein: - how the active ingredient comprises: Rj W or in which R 1, R 2, R 3, R d and R 5 are each independently hydrogen or an alkyl group having from 1 to 3 carbon atoms, the total number of carbon atoms in R 3, R 4 and R 5 being not more than 6, Ar represents a group of the formula Rc in which · * R _c , Rd and Ro are each independently hydrogen, halogen or C 1 -C 3 alkyl, Y represents —CH = or —N—, and Ra and Rb are as defined in point 1. 4. A composition according to claim 1, wherein the active ingredient comprises at least one compound of formula (I) wherein: Y is —CH = or — ‰, Ar is as defined in point 1, R a, R b, R c, R d and R e are independently hydrogen, chloro, bromo, fluoro, methyl, methoxy or nitro; U and V are independently. on . - (C 1 -C 3) alkyl, or taken together, represent one of the alkylene groups mentioned in (1), wherein R 1, R 2, R 3, R d, R 5 and R 6 are each independently hydrogen or or (C 1 -C 3) -alkyl or R 1 is -CH 2 -O-R 7, wherein R 7 is hydrogen, (C 1 -C 3) alkyl, (C 3 -C 4) alkenyl, or phenyl- group. / Composition according to one of Claims 1 to 4, characterized in that it contains, as active ingredient, a compound of the formula I selected from the group consisting of: Composition according to one of Claims 1 to 4, characterized in that it contains at least one compound of the formula I selected from the group consisting of: Composition according to one of Claims 1 to 4, characterized in that it contains, as the active ingredient, at least one compound of the formula I selected from the group consisting of: 8. A process for the preparation of an active ingredient according to claim 1 of formula I 9. The process of item 8 for producing compounds of formula I (I) wherein: Y is -CH = or -N =, R _a and R t are independently hydrogen, halogen, C 1 -C 3 alkyl or methoxy; U and V are independently C 1 -C 3 alkyl or wherein R 1 and R 2 are each independently hydrogen, C 1 -C 3 alkyl, or a group of the formula —СНг — Z — R2, where 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, and Z is oxygen or sulfur, R3, R4 and R5 are each independently hydrogen or (C1-C3) -alkyl, the total number of carbon atoms in the substituents Из, Rd and Rs does not exceed 6 and Ar represents a group of the formula wherein R _c , R d and R _e are each independently hydrogen, halogen, C 1 -C 4 alkyl, C 1 -C 3 alkoxy, trifluoromethyl or nitro and their acid addition salts and copper complexes, characterized by: characterized in that, at temperatures of from 0 to 220 ° C, in particular at temperatures of from 80 to 170 degrees Celsius, and preferably in a polar organic solvent which is inert under the reaction conditions, the compound of the formula II (II) in which: Me represents a hydrogen atom or a metal cation and Y is as defined above, with a compound of formula III wherein: X is a nucleofugile cleavable group and Ar, R _a , R b, U and V have the meanings given above, whereupon any compound obtained is converted into an acid addition salt or a complex with copper. 10. A process according to claim 9, wherein the corresponding compounds of the formulas II and III are used as starting materials to give the compounds mentioned in point 5. 11. Process according to claim 9, characterized in that the corresponding compounds of the general formulas II and III are used as starting materials to give the compounds mentioned under 6. 12. A process according to claim 9, wherein the corresponding compounds of the formulas II and III are used as starting materials to give the compounds mentioned in point 7.