CS241547B2 - Fungicide and method of active component production - Google Patents

Abstract

Novel N-alkylated 3-phenyl-4-cyanopyrrole derivatives of the formula I <IMAGE> wherein R1 and R2, each independently of the other, are hydrogen, halogen, methoxy or methylthio, R3 is hydrogen or C1-C8 haloalkyl, Y is hydroxy, halogen or the -O-C(O)-R4 group, and R4 is hydrogen, C1-C8 alkyl, C1-C8 haloalkyl, C2-C6 alkenyl, 2-tetrahydrofuryl, 2-tetrahydropyranyl, C1-C6 alkoxycarbonyl or the -CH(R5)-XR6 group, wherein X is oxygen or sulfur, R5 is hydrogen or C1-C3 alkyl, and R6 is C1-C6 alkyl, (C1-C6 alkoxy)-C1-C6 alkyl, C3-C6 alkenyl, C3-C6 alkynyl, phenyl or phenyl which is substituted by halogen, C1-C6-alkyl, C1-C6 alkoxy, or C1-C6 alkoxycarbonyl, are useful as microbicidal agents for controlling phytopathogenic micro-organisms.

Description

The present invention relates to a fungicidal composition comprising, as an active ingredient, the novel N-alkylated 3-phenyl-4-cyanopyrrole derivatives of formula (I) below. 4-cyanopyrrole, which can be used to combat harmful fungi, in particular to combat fungi damaging plants.

It has been found that the novel N-alkylated 3-phenyl-4-cyanopyrrole derivatives of formula (I)

(AT

R.> represents a hydrogen atom or a haloalkyl group having 1 to 8 carbon atoms,

Y represents a hydroxy group, a halogen atom or a group -O-C (O) -R ₄ , wherein R 2 represents a hydrogen atom, a C 1 -C 8 alkyl group, a C 1 -C 8 haloalkyl group, a C 2 -C 6 alkenyl group carbon atoms, 2-tetrahydrofuryl, 2-tetrahydroxy: ropranyryl, alkoxycarboinyl having 1 to 6 carbon atoms in the alkoxy moiety, or is -CH (R ₅ ) -X-R ₆ wherein:

X is oxygen or, sulfur,

R ₅ represents hydrogen or an alkyl group having 1 to 3 carbon atoms and

R ₆ represents an alkyl group having 1 to 6 carbon atoms, an alkoxyalkyl group having 1 to 6 carbon atoms in the α-alkoxy moiety having 1 to 6 carbon atoms in the alkyl portion, an alkenyl group having 3 to 6 carbon atoms, an alkynyl group having 3 to 6 carbon atoms or optionally halogen, C 1 -C 6 alkyl, C 1 -C 6 alkoxy, C 1 -C 6 alkyl substituted phenyl, are characterized by extremely valuable fungicidal properties.

in which

R 1 and R ₂ are independently hydrogen, halogen, methoxy or methylthio.

Accordingly, the present invention provides a fungicidal composition, characterized in that it contains at least one N-alkylated 3-phenyl-4-cyanopyrrole derivative of the formula I as defined above as an active ingredient.

The term alkyl alone or as a component of other substituents means, for example, according to the number of said carbon atoms, the following groups: methyl, ethyl, propyloxy, butyl, pentyl, hexyl, etc., as well as their isomers such as isopropyl , isobutyl, tert-butyl, isopentyl, etc.

Haloalkyl means an alkyl group substituted with one halogen up to perhalogenated alkyl groups such as CH ₂ C1, CHC1 _2, CC1 _3, CH ₂ Br, СНВг _2, CBr _2, CF ?, СНз _3l CC12F, CC1 ₂ -CHC1 ₂ CH _2i CH ₂ F, CJ ₃ etc.

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

Alkenyl means, for example, vinyl, 1-propeinyl, allyl, 1-butenyl, 2-butynyl, 3-butenyl, etc., as well as alkyl chains which are interrupted by multiple C double bonds. --C.

Alkynyl means, for example, N-propynyl, propargyl, 1-butynyl, 2-butynyl, etc., preferably propargyl.

The compounds of formula (1) are normally stable oils, resins, or predominantly crystalline solids which exhibit extremely valuable fungicidal properties. These substances can be used, in particular, under field conditions and in agriculture or in related fields, curatively and, in particular, preventively to combat fungi harmful to plants.

The active compounds of the formula I according to the invention are distinguished by high fungicidal activity and problem-free at wide application concentrations. applications in the field.

Due to their pronounced fungicidal activity, the following groups of substances are preferred in increasing order:

(a) Compounds of formula (I) wherein:

R, occupies position 2 and

R ₂ occupies the 3-position, both of which are independently hydrogen, halogen, methoxy or methylthio;

R ₃ is hydrogen or C 1 -C 4 haloalkyl, and

Y represents a hydrogen group, a halogen atom or a group -O-C (O) -R 1 'wherein

R ₄ is C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, 2-tetrahydrofuryl, 2-tetrahydropyranyl, C 1 -C 2 alkoxycarbonyl, or -CH ( R ₅ is-X R _C , where

X is oxygen or, sulfur,

R 5 is hydrogen or methyl, and

R ₆ represents an alkyl group having 1 to 6 carbon atoms, an alkoxyalkyl group having 1 to 3 carbon atoms in the alkoxy group and having 1 to 3 carbon atoms in the alkyl portion, an alkenyl group having 3 to 6 carbon atoms, an alkynyl group having 3 to 6 carbon atoms or optionally fluorine, chlorine, bromine, methyl, methoxy and / or alkoxycarbonyl having 1 to 3 carbon atoms in the ₍ alkoxy part substituted phenyl) group.

(b) Compounds of formula (I) wherein:

R1 is hydrogen, 2-C1, 2-methoxy or 2-methylthio,

R ₂ is hydrogen or 3-C1,

R ₃ is hydrogen or C 1 -C 4 haloalkyl, and

Y represents a hydroxy group, a chlorine group or a group of the formula -O-C (O) -R ₄ , wherein

R ₄ is C 1 -C 4 alkyl, C 1 -C 3 haloalkyl, 2-tetrahydrofuryl, 2-tetrahydropyranyl, C 1 -C 2 alkoxycarbonyl or -CH ₂ -OR ₆ , where

R ₆ represents a C 1 -C 4 alkyl group, a C 1 -C 3 alkylalkyl group and a C 1 -C 3 alkyl group, a C 3 -C 6 alkynyl group, or optionally fluorine, chlorine, bromine, methyl a methoxy group, a methoxy group, an ethoxycarbonyl group and / or a methoxycarbonyl substituted phenyl group.

c) Compounds of formula I wherein R 1 is hydrogen, 2-Cl, 2-methoxy or 2-methylthio,

R ₂ is hydrogen or 3-C1,

R ₃ represents a hydrogen atom or trichloromethyl and

Y represents a hydroxy group, a chlorine atom, or an -O- <C (OO-R4 _{) group} , wherein

R ₄ is C 1 -C 4 alkyl, C 1 -C 2 haloalkyl, 2-tetraihydrofuryl, 2-tetrahydropyranyl, methoxycarbonyl or -CH ₂ OR ₆ , wherein:

_Fi R represents an alkyl group having 1 to 4 carbon atoms, methoxymethyíovou group ethoxymethylovQu, allyl, propargyl, phenyl sku241547 PinII or fluorine, chlorine, bromine, methyl, methoxy not take / / a · methoxykarboinylovou group substituted phenyl.

Particularly preferred individual compounds are, for example:

The following individual compounds (a) to (u), which are particularly advantageous in particular for their potent fungicidal action in the protection of plants under field conditions:

N- (•• hydroxymethyl) -3- (3-chlorophenyl) -4-cyanopyrrole

(b) N- (1-acetyl-ethoxy-2, 3 'trichloroethyl) -3-

- (2,3-cdcphenyl) -4-cyanopyrrole

c) N- (1-hydroxy-2,2,2-trichloroethyl) -3- (2-methylthiophenyl) -4-cyanopyrrole

d) N- (1-Hydroxy-2,2,24-trichloroethyl) -3-

- (2,3-Dichlorophenyl) -4-cyanopyrrole

e) N- _(2-3 ldiydroxy 2,2drichlorethyl j-3-

- (2-, Methoxyphenyl) -4-cyanopyrrolidine-N- (1-methoxyacetyloxy-2,2,2-trichloroethyl) -3- (2,3-dicyclohexyl) -4-cyanopyrrole

g) N- (1-hydroxy-2,2,2-trichloroethyl) -3 (3-methoxyphenyl) -4-cyanopyrrole

h) N- (methoxyacetyloxymethyl) -3- (2,3'-dichlorophenyl) -4-cyanopyrrole

i) N- (1-hydroxy-2,2,2-trichloroethyl) -3-

- (2-Chlorophenyl) -4-cyanopyrirole

k) N- (chloromethyl) -3- (3-methoxyphenyl) -4-alkyl

l) N- [1- (n-butylcarbonyloxy) -2,2,2-trichloroethyl] -3- (2,3-dichlorophenyl) -4-cyanopyrrole;

m) N- (1,2,2,2-tetramethyl) -3- (3-methoxyphenyl) -4-cyanopyrrole

η) N- [1- (n-propyloxyacetyloxyl) -2,2,2-trichloroethyl) -3- (2,3-difluorophenyl) -4-cyanopyrrole

o) N- (1,2,2,2-nitro-α) -3- (3-bromophenyl) -4-cyanopyrrole

p) N- [1- (n-butoxyacetyloxy) -2,2,2-trichiOTiethyl) -3- (2,3-dichlorophenyl) -4-cyanopyrrole

q) N- [1- (isopropoxyacetyloxy) -2,2,2-trichloroethyl) -3- (2-chlorophenyl) -4-cyanopyrrole

(r) N- (1- (n-butoxyaicetyloxy) ethyl) -3- (2,3-ΦοΙΙο ^π) -4-cyanopyrrole

s) N- [1-methyl-oxo-2,3-dimethyl-oxy) -2,2,2-chloroethyl) -3- (2-methylthiophenyl) -4-cyanopyrrole

t) N- [1- (propoxyglyloxyacetyloxy) -2,2,2-trifluoromethyl] -3- (2,3-dihiloirophenyl) -4-cyanopyrrole; and

u) N- (methoxyacetyl) -3- (2-chlorophenyl) -4-cyanopyrrole;

According to the invention, the novel compounds of the formula I are prepared by reacting, in the presence of a solvent, at a temperature between 0 ° C and 200 ° C, the B-phenyl-4-cyanopyrrole derivative of the formula II

in which

R1 and R2 are as defined above, with the aldehyde of formula III

R 5 - CHO (III) wherein

R @ 1 is as defined above, optionally in the presence of an acidic or basic catalyst, to form a hydroxy derivative of the formula Ia

Ca) in which

Ri, R? and R3 has the meanings given above, and the compound of formula (Ia) obtained is then, if desired, converted, by treatment with a halogenating agent or acylating agent, with exchange of the free hydroxyl group by another radical Y to another derivative of formula I.

241S47

This exchange is preferably carried out in such a way that the compound of the formula Ia is used. in the presence of an inert solvent, if desired, by treatment with an acid of formula IV

R 2, -COOH (IV) wherein

Rz, has from above. or a reactive acid derivative thereof, in particular an acid halide, for example an acid chloride or an acid bromide, or an acid anhydride, as an acylating agent, at temperatures between 0 ° C and 150 ° C directly to the acyloxy derivative of the general formula Ib

CH o / X li (I b) in which

R _h R ?, R> and Rz They have a meaning given above, or • the free hydréxyloivá group in compound Ia obecnéroo vzoirce exchange treatment halo / halogen enaeníňo agent, preferably .atomem chlorine or bromine, whereupon the resulting halogenated product If desired, converted, optionally in the presence of a solvent which is inert under the reaction conditions, at temperatures between 0 ° C and 150 ° C and optionally in the presence of a reaction catalyst by reaction with a salt of formula V

RfCOQ® M® (V) wherein

Na ⁺ or potassium K ⁺ , to a compound of formula Ib.

The reaction of compounds of formula II with aldehydes of formula III can be carried out in the presence or absence of solvents inert under the reaction conditions or mixtures of such solvents. Suitable solvents are, for example, aromatic hydrocarbons, such as benzene, toluene or xylenes, halogenated hydrocarbons, such as chloro-benzene, aliphatic hydrocarbons, such as petoolether, ethers and lithium compounds, such as dialkyl ethers (diethyl ether, diisopropyl ether, tert-butylmethylethane, etc.), fetyl ether. di.oxa, n, tetrahydrofuran, dimethylformamide etc.

The reaction of the compounds of formula II with the compounds of formula III is preferably carried out without solvents, but using an excess amount of the aldehyde of formula III. Depending on the type of aldehyde (III), it is carried out in solution or in the melt. The addition of acidic or basic catalysts has a favorable effect on the reaction rate. Suitable acid catalysts are, for example, anhydrous hydrohalic acids and mineral acids such as hydrochloric acid, hydrobromic acid or sulfuric acid but also concentrated hydrochloric acid. As the basic catalysts, for example, triacylaminimino (triethylamine, triethylamine, dimethylethylamine, etc.), alkali metal carbonates and alkaline earth metal carbonates (such as sodium carbonate, barium carbonate, magnesium carbonate, potassium carbonate, etc.) or alkali metal alkoxides (such as sodium methoxide, sodium ethoxide, potassium isopropioxide, potassium tert-butoxide.

The temperatures in this reaction generally range between 0 ° C and 200 ° C, preferably between 0 ° C and 160 ° C, and the reaction time is 1 to 24 hours, in particular 1 to 4 hours.

The exchange of the free hydroxyl group in the compounds of formula (Ia) by the group Y is preferably carried out in a solvent which is inert under the reaction conditions. Examples of such solvents include: aromatic and aliphatic hydrocarbons, such as benzene, toluene, xylenes, petroleum ether, ligroin or cyclohexane; halogenated hydrocarbons such as chlorobenzene, methylene chloride, ethylene chloride, chloroform, tetracyclomethane or tetrachlorethylene; ethers and ether compounds, such as diethyl ether, diisopropyl ether, tert-butyl methyl ether, dimethoxyethane, dioxane, tetrahydrofuran or anisole; esters such as ethyl acetate, propyl acetate or butyl acetate; nitriles such as acetonitrile; or compounds such as dimethylsulfoxide, dimethylformamide and mixtures of such solvents with each other.

The introduction of the group Y is carried out by conventional methods. When Y is a chlorine atom, the reagent used is, for example, an alkali metal or alkaline earth metal cation, such as an alkali metal or alkaline earth metal cation such as for example a cation of calcium Ca ⁺⁺ , magnesium Mg ⁺⁺ , sodium phosphorous, phosphorus trichloride or preferably thionyl chloride. The process is generally carried out at temperatures ranging from 0 ° C to +120 ° C.

When Y = thunder, phosphorus tribromide or phosphorus tribromide is preferably used, and the reaction is carried out at a temperature of from 0 ° C to 0 ° C. + 50 ° C. When Y is a group, -O- (O) -R /, then the corresponding acid halide, especially the acid chloride, is usually used as the reagent, and it is expedient if the reaction is carried out at temperatures from -20 ° C to -20 ° C. + 50 ° C, preferably at temperatures from -10 ° C to + 30 ° C and in the presence of a weak base such as pyridine or triethylamine. In addition, α-dialkylaminopyridines such as 4- dimethyl- or 4-diethylaminopyridine.

The reaction of the compounds of the formula I in which Y is halogen, in particular chlorine or bromine, with the salts of the general formula V is carried out usually in the presence of customary inert solvents or solvent mixtures. Examples of such solvents include: aromatic and aliphatic hydrocarbons such as benzene, toluene, xylenes, petroleum ether, ligroin or cyclohexane; ethers and ether compounds, such as dialquieters, for example diethyl ether, diisopropanol, tert-butyl ethyl ether, dimethoxyethane, dioxane, tetrahydrofuran or anisole; esters such as ethyl acetate, propyl acetate or butyl acetate; nitriles such as acetonitrile; or compounds such as dimethylsulfoxide, dimethylformamide and mixtures of such solvents with each other.

The addition of catalytic amounts of crown ether, such as 18-crown-6 or 15-crown-5, is beneficial for the reaction. The reaction temperatures in this reaction are generally between 0 ° C and 150 ° C, preferably between 20 and 80 ° C. The reaction time is 1 to 24 hours.

In a preferred embodiment, the preparation of the compounds of the formula Ib, in particular those in which R 3 is a trichloromethyl group or a hydrogen atom, using the compounds of the formula II as starting materials, is carried out in a single process. ·. working stage. The process is preferably carried out in one of the abovementioned inert solvents or diluents. Particularly suitable are, for example, ether compounds such as tetrahydrofuran. The reaction is carried out in the presence of a weak base such as a trialkylmiin, for example triethylamine, or pyridine. Chlorail or paraformaldehyde is used as reagents. The reaction may be accelerated by the addition of a catalyst such as 1,8-diazabicyclo [5.4.0.0] undec-7-ene [DBU J.

The temperatures in this first reaction step are between -10 ° C and +100 ° C, preferably between 0 ° C and 50 ° C and the reaction time is 0.5 to 2 hours. Intermediately, a hydroxy derivative of the formula Ia is formed which is not isolated but is present in the same reaction solution at a temperature of -30 ° C to +30 ° C, preferably at a temperature of -10 ° C to 0 ° C and in the presence of a catalytic amount of 4-dialkylaminopyr. of an idine, preferably d-dimethylamino-pyridine, reacts with a compound of formula IV. The reaction time for this step 2 is 0.5 to 16 hours.

The starting compounds of the formulas (III), (IV) and (V) are known compounds or are prepared by methods known per se.

Some of the pyrrole derivatives of formula (II) are known from the literature. Thus, for example, the process and the chemical properties of 4-cyano-3-enpyridine-III are described in Tetrahedron Letters No. 52, pp. 5,337-5,340 (1972). However, there are no data on the biological activity of this compound.

N-acetylated substituted 3-phenyl-4-cyanopyrrole derivatives are known in the literature. Thus, for example, DE-OS 2 927 480 describes pyrrole fungicides of the general formula VI as fungicides

in which

X represents a halogen atom, a lower alkyl group or a lower halogen group and n represents 0, 1 or 7

British Patent Specification; The "07" is furthermore as stabilizers against "No" ¹ .

heat stabilizers and world stabilizers for polyvinyl chloride based plastics known pyrrole derivatives of the general formula VII ''

(Vil) in which

R @ 1 represents an acyl group, an alkoxycarbonylalkyl group, etc.,

R 5, R 8 mean hydrogen atom, aryl group, etc.,

R 10 represents hydroxy, mercapto, etc.

Other pyrrole derivatives of formula VIII and R5

Ri (vin) in which

Rj. represents an alkyl group which is optionally substituted with acyloxy, etc.,

R @ 1 represents a hydrogen atom, an alkyl group, a cyano group, etc., described in DE-OS 2 028 363 as polymerization catalysts for vinyl chloride.

The known pyrrole derivatives are either ineffective against phytopathogenic microorganisms or, although they exhibit a fungicidal effect in plant protection in a greenhouse, but under field conditions their effect is not reproducible due to their instability to the environment. These known pyrrole derivatives are therefore not suitable for practical use in agriculture, horticulture or related fields of application.

The new pyrrole derivatives of the general formula I according to the invention therefore represent a valuable enrichment of the state of the art, - since it has been surprisingly found that the new pyrrole derivatives of the general formula I have a very favorable microbicidal spectrum for practical (field) conditions and requirements. against phytopathogenic fungi and bacteria.

These novel compounds can be used not only in peasants or in related areas to combat harmful microorganisms on crop plants, but also to protect stocks for the preservation of perishable goods. The compounds of the formula I have very advantageous curative, systemic and, in particular, preventive properties and can be used to protect a number of crop plants, in particular field crops. The active compounds of the formula I can control or destroy the microorganisms occurring on the plants or on parts of the plants (fruits, flowers, leaves, stems, tubers, roots) of various useful plants, whereupon the later grown parts of the plants remain protected from such microorganisms.

The active compounds of the formula I are active, for example, against phytopathogenic fungi, which belong to the following classes:

Ascomycetes, for example Erysiphe, Sclerotinia, Fusarium, M onilinia, Helminthosp orium; Basidicmycetes such as Puc12 cinla, Tilletia, Rhizoctonia; as well as Oomyoetes such as Phytophthoira, belonging to the class Phycomycetes.

As a plant protection agent, the compounds of the formula I can be used with particularly good results against important harmful fungi of the genus Fungi imperfecti, such as Cercosptaa, Piricularia and, in particular, Botrytis. Species fungi Botrytis spec. (Botrytiis cinerea, Botrytis aliLii) is a significant economic detrimental factor due to rot caused by gray mold on grapevines, strawberries, apples, onions and other fruits and vegetables. In addition, some of the compounds of formula I, for example -compound 1.3, can be successfully used for the protection of perishable goods, both of plant and animal origin. Thus, said compounds destroy fungi such as Penicillium, Aspergillus, Rhizopus, Fusarium, Helminthosporium. Nigrospora and Alternaria as well as bacteria, such as buttery and yeast bacteria, such as Candida.

As a plant protection agent, the compounds of formula I have a very favorable spectrum of effects for practical use in agriculture to protect crop plants without adversely affecting these crop plants.

The active compounds according to the invention can furthermore be used as gauges for the treatment of seed (fruits, tubers, grains) and plant seedlings for protection against fungal infections as well as against phytopathogenic fungi which occur in the soil.

Accordingly, the present invention also relates to fungicidal compositions as well as to the use of the compounds of formula I for combating phytopathogenic fungi damaging plants, or for preventing preventive infestation of plants and stocks of plant or animal origin.

In addition, the present invention also encompasses the production of (agro) chemical compositions which consist in thorough mixing of the active ingredient with one or more of the substances or groups described herein. The invention also relates to a process for the treatment of plants or stored goods, which comprises applying compounds of the formula I or new compositions to the plants, to a part of the plants, to the places where the plants grow or to a substrate.

Possible crop plants to which the abovementioned fields of application are applicable include, for example, the following plant species in the context of the present invention: - carbohydrates (wheat, barley, rye, oats, rice, sorghum - and related plants); beet (sugar beet and fodder beet); fruit trees bearing fruit - with kernels, stone fruits and berries (apple tree, - pear, plum, peach, almond, cherry, strawberry, raspberry, o-legume); -proteins (beans, lentils, peas, soybeans); oilseeds (rape,

14 mustard, poppy seed, clivovalk, sunflower, coconut, castor oil, cocoa, oilseed oasis); pumpkin plants (pumpkins, cucumbers, melons); pulp (cotton, flax, hemp, jute); citrus trees (ora.nžcwík, lemon, biggest lemon, tangerine); various vegetables (spinach, lettuce, asparagus, cabbage, carrots, onions, tomatoes., potatoes, peppers); laurel plants (avocado, cinnamon, camphor) or other plants such as maize, tobacco, butternut, coffee, sugarcane, teacup, grapevine, hops, banana and rubber tree as well as ornamental plants (Compositae).

Compounds of formula (I) are used in unchanged form, or preferably together with auxiliaries which are usually used in the preparation of such formulations, and processed in known manner, for example, into emulsion concentrates, pastes which can be applied by coating, directly injectable solutions or to further dilute solutions, dilute emulsions, wettable powders, soluble powders, dusts. granules also encapsulated, for example, in polymeric substances. Application procedures, such as spraying, fogging, dusting, sprinkling, coating or watering, as well as the type of composition, are selected in accordance with the desired objectives and conditions. A favorable application rate is generally between 0.01 and at most 2 k @ -1 of active ingredient per. 100 kg of protected substrate. However, this application rate depends very much on the substrate structure (surface area, consistency, moisture content) on the environmental influences.

In the context of the present invention, stored, merchandise and stock goods are understood to mean plant and / or animal natural substances, as well as products of their further processing, for example the following natural life cycle plants, as well as plant parts thereof (stems, leaves, tubers, seeds, fruits, grains) that occur in a freshly harvested state or in a form obtained by further processing (dried, moistened, ground, ground, heat treated). Examples which are not within the scope of the present invention that limit the application area include the following harvested products: - cereals (such as wheat, barley, rye, oats, sorghum and related), beets such as carrots, sugar beet and fodder beet, pome fruits, stone fruits and berries [such as apples, pears, plums, peaches, almonds, cherries, strawberries, blackberries, blueberries), legume fruits (such as beans, pea lentils, soybeans); oilseeds (like canola, mustard, poppy, olives, sunflowers, coconut, castor oil, cocoa, pods of oilseed); pumpkin plants (such as pumpkins, cucumbers, melons); pulp (such as cotton, flax, hemp, jute, nettle); citrus fruits; various types of vegetables (such as spinach, lettuce, asparagus, various types of brassica), onions, tomatoes, pa prika; laurel plants (avocado, cinnamon, camphor) or maize, tobacco, nuts, coffee, cane, tea, grapes, chestnuts, hops, bananas, grass and hay.

Natural products of animal origin include, in particular, dried meat and fish processing products such as dried meat, dried fish, meat concentrates, bone meal, fish meal and dry animal feed.

The treated stocks with the treatment of the compounds of formula I permanently protect against fungal attack and other undesirable microorganisms. This avoids the formation of toxic and partially carcinogenic fungi (aflatoins and 00111). The goods are protected from deterioration and their quality is retained for a long time. stocks and stored goods susceptible to attack by microorganisms such as yeast, bacteria and especially fungi.

A preferred method of administering the active ingredient is to spray or wet the substrate with a liquid formulation or to mix the substrate with a solid form of active ingredient processing.

The described method of preservation is part of the present invention.

The active compounds of the formula I are usually used in the form of compositions and can be applied to the treated areas, plants or substrates simultaneously or sequentially with other active compounds. These other active ingredients may be both fertilizers, trace elements or other preparations which affect the growth of plants. They may also be selective herbicides, insecticides, fungicides, bactericides, nematicides, molluscicides or mixtures of these preparations together with, optionally, other carriers, surfactants or other application aids used in the preparation of such compositions.

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

A preferred method of applying an active compound of the formula I or an (agro) chemical composition comprising at least one of these active compounds is to apply to the leaves of the plants. The number of applications and the application rate depend on the degree of infestation for the corresponding agent (species - fungi). However, the active compounds of formula (I) can also reach the plant via the soil via roots (systemic effect), by pouring in a liquid preparation in the place where the plant grows or by incorporating the substances in solid form into the soil, e.g. ).

Compounds of Formula I-se. however, they can also be applied to the seeds (Coating) by either impregnating the seeds with a liquid preparation of the active ingredient or by coating them with a solid preparation. In addition, other applications are possible in special cases, for example the deliberate treatment of plant stems or buds.

The compounds of the formula I are used in this application in unchanged form or preferably together with auxiliaries which are customary in the preparation of such compositions and are therefore processed, for example, into emulsion concentrates, pastes which can be applied by spraying, directly sprayable solutions or solutions. dilute emulsions, wettable powders, soluble powders, dusts, granules, and for compositions encapsulated, for example, in polymeric substances, in a manner known per se. Application procedures, such as spraying, fogging, dusting, sprinkling, coating or watering, as well as the nature of the composition, are selected in accordance with the desired objectives and conditions. A favorable application rate is generally in the range of from 50 g to 5 kg of active ingredient per ha; it is preferably from 100 g to 2 kg of active substance per ha, in particular from 200 g to 600 g of active substance per ha.

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

Suitable solvents include aromatic hydrocarbons, preferably C8-C12 fractions, such as mixtures of xylenes or substituted niaphthalenes, phthalic esters such as dibutyl phthalate or dioctyl phthalate, aliphatic hydrocarbons such as cyclohexane or paraffins, alcohols and glycols and their ethers and esters, such as ethanol, ethyl, nglycol, ethylene glycol monomethyl ether or ethylene glycolimionoethyl ether, ketones such as cyclohexiainoin, strongly polar solvents such as N-methyl-2, -pyrrolidone, dimethylsulfoxide or dimethylformamide, and optionally epoxide vegetable oils, 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, mointmiorillonite or attapulgite are generally used. Also, high silicic acid or high silicic absorbent polymers can be added to improve physical properties. Suitable granular adsorptive granule carriers are porous types such as pumice, brick pulp, sepiolite or bentonite; as non-sorptive carriers, for example, limestone or sand. In addition, a variety of pre-granulated materials of inorganic or organic origin, such as in particular dolomite or comminuted plant residues such as cork flour or sawdust, may be used.

Particularly preferred adjuvants which may lead to a significant reduction in the amount of active ingredient used are furthermore natural (animal or plant) or synthetic phospholipids from the series of cephalins and lecithins, such as phosphatidylethanolamine, phosphaididylserine, phosphatidylcholine, sphingomyeLin, phosphatidylolimine, phosphatidylolimine, phosphatidylinositin, , plasmalogen or cardiolipin, which can be obtained, for example, from animal or plant cells, in particular from the brain, heart, lungs, liver, yolk or soybeans.

Suitable commercially available mixtures are, for example, phosphatidylcholine mixtures. Synthetic phospholipids are, for example, dioctanoylphosphatidylcholine and dipalmitoylphosphatidylcholine.

Suitable surfactants are, according to the type of active compound to be treated, nonionic, cationic and / or anionic surfactants having good emulsifying, dispersing and wetting properties. Surfactants are also understood as meaning mixtures of surfactants.

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

Soaps include alkali metal, alkaline earth metal, or 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 can be obtained, for example, from coconut oil or tallow. Fatty acid salts with methyltaurine must also be mentioned.

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

Fatty sulfonates or sulfates are generally in the form of alkali metal, alkaline earth metal or optionally substituted ammonium salts and contain an alkyl moiety of from 8 to 22 carbon atoms, the alkyl moiety may also include an alkyl moiety of acyl moieties such as e.g. sodium or calcium salt of ligninsulphonic acid, dodecylsulphuric acid ester or mixtures of sulphated fatty alcohols which have been made from natural fatty acids. This also includes the salts of sulfuric acid esters and suifonic acids of fatty alcohol adducts with ethylene oxide. The sulfonated benzimidazole derivatives preferably contain 2 sulfonic acid residues and a fatty acid residue of 8 to 22 carbon atoms.

Alkylarylsulfoinates are, for example, sodium, calcium or alcohols. triethanclammonium salts of donecylbenzenesulfonic acid, dimethylaminophosphoric acid or a condensation product of naphthalene of lionic acid and formaldehyde.

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

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

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

Examples of non-ionic t-isides are nonylphenolpolyenioxyethanol, castor oil polyglycol ethers, polypropylene polyether adducts, tributylphenoxypolyethoxyethanol, polyethylene glycol, and octvlphenoxypolyethohethaol.

Fatty acid esters of polyoxyethylene glycol are also contemplated. Vo polvox j (t ^ T y y ^ ^ y y y y y ^ ^).

The canonical surfactants are predominantly quaternary ammonium salts which, as substituents on the nitrogen atom, contain at least one alkyl radical having p-22 atoms. As further substituents, they contain lower or optionally halogenated alkyl, benzyl or lower hydroxyl residues. These salts are preferably in the form of - ha-, logenides, methylsulphates or ethylsulphates, such as, for example, stearyltriethylamanluine chloride or benzyl di- (2-chloroethyl) - (2-chloroethyl) -. and harmless animals.

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

"Mc Cut-Cheoin's Detergents and Emulsifiers Annual", BC Publishing - Corp., Ridgewoos New Jersey, 1981.

Helmut-Stache „Tensid - · Taschenbuch“

Cari Hanser - Verlag, Munich / Wien

1981.

Agrochemical compositions generally contain from 0.1 to 99%, 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 a solid or liquid additive and from 0 to 23%, especially 0.1 to 25% surfactant.

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

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

Such agro-chemical compositions are part of the present invention.

The following examples serve to illustrate the invention in greater detail without restricting it in any way. Percentages are by weight and parts are by weight.

Examples illustrating the method of manufacture of active ingredients:.

Example H1

Preparation of N-hydroxymethyl-3- (2-chlorophenyl) -4-cyanopyrrole

(Compound - No. 1.1)

0.3 g of 3- (2-chlorophenyl) -4-cyanopyrrole, 9.9 g of panformaldehyde and 0.8 g of triethylamine are mixed well and then the mixture is heated with stirring at a bath temperature of 90 ° C. . take after 1 hour and 15 minutes of room temperature, taking on a ski ·· welcome product. Pre-toluene is obtained from above in the form of brownish rats. The resulting melt is then cooled to melt and solidified by crystallization from the lead products.

Mp 94-97 ° C.

r

Preparation of N-chloromethyl-3- (2-chlorophenyl) -4-cyclohexyl

(Compound 2.1) η

К 60 ml thionyl chloride with vigorous stirring · in several portions 48 g of ^{N-hydroxymie,} ethyl-3- ^(2-Chloro, rphenyl) -4''kya ^| pyrrole to maintain a slight gas evolution. After gas evolution had ceased, the reaction mixture was stirred at room temperature for 2 hours and then stirred at 35-40 ° C for 2.5 hours. After cooling to room temperature, toluene was added and the mixture was concentrated. The residue is recrystallized from diethyl ether / petroleum ether to give the above product as beige crystals.

Melting point 97-99 ° C.

Example H3

Preparation of N-acetoxymethyl-3- (2-chlorophenyl) -4-cyanopyrrole

CH _of CH ₃ OC (compound no. 3.2)

41.4 g of N-hydroxymethyl-3- (2-chlorophenyl) -4-cyainpyrrole are dissolved in 350 ml of pyridine and 1.8 g of 4-dimethylaminopyridine are added. Subsequently, 21.4 ml of acetic anhydride are added dropwise slowly at 0 to 7 ° C and the mixture is stirred at 0 ° to 7 ° C for 12 hours. The reaction mixture was poured into ice water and extracted twice with ethyl acetate. The extracts were washed twice with ice-cold diluted hydrochloric acid and then washed twice with a partially saturated aqueous sodium chloride solution.

It is then dried over sodium sulphate, filtered and the filtrate is concentrated. The residue was recrystallized from diethylleither hexane to give the title compound as colorless crystals. Melting point 91-95 ° C.

Example H4

Preparation of N- (1-acetyloix-2,2,2-trichloroethyl) -3- (2,3-dichlorophenyl) -4-cyanopyrrole

CH O \ C C ₃ C OC-CH ₃

2.4 g of 3- (2,4-dichlorophenyl) -4-cyanopyrrole in 50 ml of tetrahydrofuran were gradually added dropwise to 1.2 ml of chloral and 1.8 ml of triethylamine. The reaction mixture was stirred at 25 ° C for 1.5 h, then 0.1 g of 4-dimethylaminopyridine was added and the mixture was cooled to -10 ° C. A solution of 0.9 ml of acetyl chloride in 10 ml of tetrahydrofuran is now added dropwise at -10 to -5 ° C and the reaction mixture is then stirred at 0 ^° C for 30 minutes and then stirred at room temperature for 1 hour, filtered and the filtrate is filtered. thicken. The residue was dissolved in diethylleither, the ethereal solution was washed twice with a partially saturated sodium chloride solution, dried over sodium sulfate, filtered, and the filtrate was concentrated. The crude product was recrystallized from diethyl ether / petroleum ether to give the title compound as colorless crystals.

Melting point 111-113 ° C.

Example H5

Preparation of N-chloromethyl-3- (2,3-dichlorophenyl) -4-cyanopyrrole

(Compound 2.4)

To 23.7 g of 3- (2,3-dichlorophenyl) -4-cyanopyrrole dissolved in 300 ml of tetrahydrofuran was added 7.5 g of paraformaldehyde followed by 1.5 [alpha], 8-diazabicyclo [5.5.0] undec-7. -einu. The reaction mixture was stirred at room temperature for 3 hours. Thereafter, 21.7 ml of thiioinyl chloride are added dropwise with stirring at 20-30 ° C to the hydroxymethyl derivative formed. The reaction mixture was then stirred at room temperature for 16 hours, then poured onto ice water and extracted twice with ethyl acetate.

The combined organic extracts were washed twice more with semi-saturated sodium chloride solution, dried over sodium sulfate, filtered and concentrated. Crystallization of the residue from a mixture of ether and petroleum ether gave the title compound as beige crystals. Melting point 132-133 ° C.

Example H6

Preparation of N- (1-hydroxy-2,2,2-trichloethyl) -3 (2,3-dichlorophenyl) -4-cyanopyrrole (Compound No. 3.4)

4 1'5 4-7

Cl £ OH (Compound No. 1.3)

To 64.1 g of 3-cyano · 4- (2 _J 3-dichlorophenyl] pyrrole and 1.2 ml of triethylamine in 400 ml of tetrahydrofuran at 20 to 29 · C was added dropwise 39.6 ml chloiralu. Next, the reaction mixture 2.4 ml of triethylamine and then 1.2 ml of diazabicyclo [5.4.0] undec-7-ene were added again, and the clear solution was stirred at room temperature for 2 hours and then at 0-5 ° C for 14 hours. C. The solution is poured onto a mixture of dilute hydrochloric acid and ice and then extracted twice with ethyl acetate, and the organic extracts are then washed with cold, partially saturated sodium chloride solution, dried over sodium sulfate, filtered and concentrated. The residue from a mixture of ether and pstrolethe.ru gave the title compound as colorless crystals, mp 117 ° C [dec.].

Example H7

Preparation of N- [1- (methoxyacetyloxy-1,2,2-trichloroethyl) -3- (2,3-dichlorophenyl) -4-cyanopyrrole

0.2 ml of 1,8-diazabicyclo [5.4.0] undec-5-ene and then 2.3 ml of chloral. The solution was cooled to -5 ° C and then 3.3 ml of triethylamine was added dropwise. After stirring for 1 hour at -5 ° C, 2.2 ml of methoxyacetic acid chloride, which is dissolved in 10 ml of tetrahydrofuran, is slowly added dropwise at -10 to -5 ° C. After stirring for 1 hour at the temperature of the hot bath, the reaction mixture was poured into ice water and then extracted twice with ethyl acetate. The organic extracts were then washed twice with dilute hydrochloric acid and then twice with cold, partially saturated sodium chloride solution, dried over sodium sulfate, filtered and concentrated. Crystallization of the residue from petroleum ether gave the title compound as colorless crystals. Mp 88-90 ° C.

Example H 8

Preparation of N- [(methoxyacetyloxy) methyl] -3- (2,3-dichlorophenyl) -4-cyanopyrrole cAVr ™

Cl γ

CH2O-C-CH2OCfHi

O (Compound No. 3.22)

4.5 g of 3-cyano-4- (2,3'Cd'Tito-phenyl-pyrrole) are dissolved in 50 ml of tetrahydrofuran and 0.65 g of paraformaldehyde, 3.0 ml of triethylamine and 0.5 ml of 1 are added to the obtained solution. 8-diazabicyclo [5.4.0] undec-5-ene.

The reaction mixture was stirred at room temperature for 2 hours to give a clear solution. 2.0 ml of ethoxyacetic acid chloride are then slowly added dropwise with stirring at 5 ° C. After an additional 2.5 hours at 0-5 ° C, the mixture was filtered and the filtrate was concentrated. Crystallization of the residue from a mixture of ether and petroleum ether gave the above product as colorless crystals. Melting point 72-75 ° C.

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

(Compound No. 3.5)

4.8 g of 3-cyano- (2,3-dichloro-phenyl) -pyrrole are dissolved in 50 ml of tetrahydrofuran and added to this solution at room temperature.

Table 1

Compounds of formula

in which

Y represents a hydroxyl group:

compound number

Ri

Rs of physical constant

1.1 2-C.l H H mp 94-97 ° C 1.2 H 3-C1 H mp 72-74 ° C 1.3 2-C1 3-C1 CC1 ₃ mp 117 ° C (decomposition) 1.4 H 2-SCH3 CC1 ₃ mp 85 ° C (decomposition) 1.5 2-C1 H CC1 ₃ mp 70-76 ° C (decomposition) 1.6 2-C1 3-C1 H 137-140 C 1.7 H 3-C1 CC1 ₃ 1.8 2-SCH ₃ H H 1.9 2-OCH 3 H H resin 1.10 2-OCH 3 H CC13 1.11 H H H mp 81-84 ° C 1.12 H 3-OCH3 H 1.13 H 3-OCH3 CC1 ₃ resin 1.14 H 3-SCH3 CC1 ₃ 1.15 H 3-SCH3 H resin 1.16 2-OCH 3 з-осн _э H 1.17 2-OCH 3 3-OCH ₃ cclg 1.18 H 3-Br H mp 65-69 ° C 1.19 H 3-Br CC1 ₃ 1.20 H 3-F H mp 75-77 ° C 1.21 2-F. H H 1.22 H 3-F CC1 ₃ 1.23 H 3-J CC1 ₃ 1.24 H 3-J H

Table 2

Compounds of general formula

wherein Y is chlorine.

compound number Ri R2 R3 physical constants 2.1 2-C1 H H mp 97-99 ° C 2.2 H 3-C1 H mp 77-79 ° C 2.3 2-C1 H CC13 2.4 2-C1 3-C1 H mp 132-133 ° C 2.5 2-C1 3-C1 cci ₃ mp 152-157 ° C 2.6 H 3-C1 CC1 ₃ 2.7 2-SCHo H H 2.8 2-SCH3 H CC13 2.9 2-OCH 3 H H 2.10 2-OCH 3 H CC13 2.11 H 3-OCH3 H resin 2.12 H 3-OCH3 CC1 ₃ resin 2.13 H 3-SCH3 H 2.14 H 3-SCH3 CC13 2.15 2-OCH 3 3-OCHt H 2.16 2-OCH 3 3-OCH3 CCI3 2.17 H 3-Br H mp 71-74 ° C 2.18 H 3-Br CCI3 semi-crystalline product 2.19 H 3-F H Mp 80-83 ° C 2.20 2-F H H 2.21 H 3-F CCI3 2.22 H 3-J CC13 2.23 H 3-J H mp 59-65 ° C 2.24 H 3-OCH3 CHC1 ₂ 2.25 H 3-OCH3 CHC1 ₂ resin 2.26 H 3-SCH3 CH2Cl

Compounds of general formula

RfCH-Y

in which the compound represents a group —OC (O) R4). R ₃ Rz. physical constants ^R i r ₂ 3.1 2-C1 H CC1 ₃ CH ₃ mp 100-108 ° C 3.2 2-C1 H H CH ₃ mp 91-95 ° C 3.3 H 3-C1 ось CH ₃ mp 118-120 ° C 3.4 2-C1 3-C1 CC13 CH ₃ mp 111-113 ° C 3.5 2-C1 3-C1 CC1 ₃ CH ₂ OCH ₃ mp 88-90 ° C 3.6 2-SCH ·) H ccl ·} CH ₃ mp 139-141 ° C 3.7 2-OCH-i 2-C1 H CC1 ₃ CH ₃ mp 106-108 ° C 3.8 H H CC13 3.9 2-C1 H H CH ₂ OCH ₍ mp 112-114 ° C 3.10 H 3-C1 CCI, CH _(CH3) resin 3.11 H 3-C1 CC1 ₃ (СН ₂ ) ₃₁ СНз 3.12 H 3-C1 CC1 ₃ CH ₂ Br 3.13 H 3-C1 cclq CF3 3.14 H 3-C1 H СНз 3.15 H 3-C1 H СНС1 ₂ 3.16 2-C1 3-C1 CCI, С ₂ Н ₅ mp 137-141 ° C 3.17 2-C1 3-C1 CCI, (С ₂ ) ₃ С ₃ n _D ⁵⁰ 1.5548 3.18 2-C1 3-C1 CC13 СН ₂ С1 mp 143-151 ° C 3.19 2-C1 3-C1 CC1 ₃ н resin 3.20 2-C1 3-C1 H СНз mp 95-99 ° C 3.21 2-C1 3-C1 H С (СН ₃ ) ₃ mp 86-88 ° C 3.22 2-C1 3-C1 H СН ₂ ОСН ₃ mp 72-75 ° C 3.23 2-C1 3-C1 H СС1 ₃ 3.24 2-C1 3-C1 H н 3.25 2-OCH ₃ 2-OCH ₃ H CC13 С (СН ₃ , Ь resin 3.26 H CC1 ₃ СН ₂ С1 3.27 2-OCHj H CC1 ₃ н 3.28 2-OCHj H H СС1 ₃ 3.29 2-OCH 3 H H сн ₃ semi-crystalline product 3.30 2-OCH 3 H H СН ₂ ОСН ₃ 3.31 2-SCH3 H CC13 from _{2 to 5} 3.32 2-SCH3 H CClg СН ₂ С1 3.33 2-SCH3 H CC1 ₃ СН ₂ ОСН ₃ semi-crystalline product 3.34 2-SCH ₃ H H СНз 3.35 2-SCH3 H H С ₂ Н ₅ 3.36 2’SCH <. 2-C1 H H СС1з 3.37 3-C1 H СН ₂ С1 mp 113-115 ° C 3.38 2-C1 3-C1 H С ₂ н ₅ resin 3.39 2-C1 3-C1 H С ^ НдНП n _D ⁵⁰ 1.5571 3.40 2-C1 3-C1 CC13 С (СНз) _э mp 146-147 ° C 3.41 H H CC13 CH2OCH3 1.1. 121 DEG -122 DEG 3.42 2-C1 3-C1 CC13 С ₂ н ₅ semi-crystalline product 3.43 2-C1 3-C1 H СН ₂ Вг mp 88-90 ° C 3.44 2-C1 3-C1 CC1 ₃ СН ₂ Вт mp 132-135 ° C 3.45 2-C1 3-C1 CC13 СН ₂ ОС ₂ Н ₅ mp 115-117 ° C 3.46 2-C1 3-C1 H СН ₂ ОС ₂ Н ₅ mp 83-85 ° C 3.47 2-C1 H CC1 ₃ СН ₂ ОСН ₉ mp 116-118 ° C 3.48 H H H СН ₂ ОСН ₃ mp 78-79 ° C 3.49 2-C1 3-C1 H СН ₂ О С3Н7-П mp 87-88 ° C

number Ri r ₂ R ₃ r ₄ 3.50 2-Cl 3-Cl cci ₃ CM ₂ OC ₃ H ₇ -n 3.51 2-Cl 3-Cl H CH ₂ OC ₄ H ₉ -n 3.52 2-Cl 3-C1 cci ₃ CH ₂ OC ₄ H ₉ -n 3.53 2-Cl 3-Cl H СН ₂ ОС ₉ Н ₁₃ , -п 3.54 2-Cl 3-Cl CC1 ₃ CH ₂ OC ₆ H ₁₃ -n 3.55 2-Cl H H CH 2 OCHICHah 3.56 2-Cl H CC1 ₃ CH ₂ OCH (CH ₃ ) ₂ 3.57 2-Cl 3-Cl H CH ₂ OCH (CH ₃ ) ₂ 3.58 2-Cl 3-Cl ССЦ CH ₂ OCH (CH ₃ ) ₂ 3.59 2-Cl 3-Cl H СНгОСЩСН-ЗСаНд 3.60 2-Cl 3-Cl CC13 CH ₂ OCH (CH ₃ ) C ₂ H ₅ 3.61 2-Cl 3-Cl H CH ₂ OC (CH ₃ ) ₃ 3.62 2-Cl 3-Cl CC13 CH ₂ OC (CH ₃ ) ₃ 3.63 2-Cl H H CH ₂ OCH _{2 and} CH _2! OCH ₃ 3.64 2-Cl H ccl-i CH ₂ OCH ₂ CH ₂ OCH ₃ 3.65 2-Cl 3-Cl H CH ₂ OCH ₂ CH ₂ OCH ₃ 3.66 2-Cl 3-Cl cclj CH ₂ OCH ₂ CH ₂ OCH ₃ 3.67 2-Cl 3-Cl H CH ₂ OCH ₂ , CH = CH ₂ 3.68 2-Cl 3-Cl CC1 ₃ CH ₂ OCH ₂ CH = CH ₂ 3.69 2-Cl 3-Cl H CH ₂ OCH ₂ C = CH 3.70 2-Cl 3-Cl ССЦ CH ₂ OCH ₂ = CH 3.71 2-Cl 3-Cl H CH ₂ OC ₆ H ₅ 3.72 2-Cl 3-Cl CC1 ₃ CH ₂ OC ₆ H ₅ 3.73 2-Cl 3-Cl H CH ₂ OC ₆ H ₃ C1 ₂ (3.5) 3.74 2-Cl 3-Cl CC1 ₃ CH ₂ OC ₆ H ₃ C1 ₂ (3.5) 3.75 2-Cl 3-Cl H CH ₂ OC ₆ H ₃ C1 ₂ (2.4) 3.76 2-Cl 3-Cl ССЦ CH ₂ OC ₆ H ₃ C1 ₂ (2.4) 3.77 2-Cl H H 2-Tetnahydirofuryl 3.78 2-Cl H CCI, 2-tetriahydrofuryl 3.79 2-Cl 3-Cl H 2-Tetnahydrofuryl 3.80 2-Cl 3-Cl CC13 2-Tetnahydrofuryl 3.81 2-Cl H h ' CH ₂ SCH ₃ 3.82 2-Cl H CC1 ₃ CH ₂ SCH ₃ 3.83 H H H CH ₂ SCH ₃ 3.84 H H CC1 ₃ CH ₂ SCH ₃ 3.85 2-Cl 3-Cl H CH ₂ SCH ₃ 3.86 2-Cl 3-Cl CC1 ₃ CH2SCH3 3.87 2-Cl 3-Cl h ‘ CH ₂ SCH (CH ₃ ) C ₂ H ₅ 3.88 2-Cl 3-Cl CC1 ₃ CH ₂ SCH (CH ₃ ) C ₂ H ₅ 3.89 2-Cl H H CH ₂ SCH (CH ₃ ) C ₂ H ₅ 3.90 2-Cl H CC1 ₃ CH ₂ SCH (CH ₃ ) C ₂ H ₅ 3.91 2-Cl 3-Cl H CH ₂ SC ₄ H ₉ -n 3.92 2-Cl 3-Cl CC1 ₃ CH ₂ SC ₄ H ₉ -n 3.93 2-Cl 3-Cl H CH ₂ SC (CH ₃ ) ₃ 3.94 2-Cl 3-Cl CC1 ₃ CH ₂ SC (CH ₃ ) 3 3.95 2-Cl 3-Cl H C (O) OC ₂ H ₅ 3.96 2-Cl H H CH ₂ SC _e H ₅ 3.97 2-Cl H ССЦ CH, SC ₆ H ₅ . 3.98 2-Cl 3-Cl H CH ₂ SC ₆ H ₅ 3.99 2-Cl 3-Cl CCI ₃ CH ₂ sc ₆ H ₅ 3.100 2-Cl H H CH = CH ₂ 3.101 2-Cl H CC1 ₃ CH = CH ₂ 3.102 2-Cl 3-Cl H CH = CH ₂ 3.103 2-Cl 3-Cl CC1 ₃ CH = CH ₂ 3.104 2-Cl 3-Cl H CH = CH = CH ₃ 3.105 2-Cl 3-Cl CC13 CH = CH = CH ₃ 3.106 2-Cl H H CH = CH-CH ₃ 3.107 2-Cl H CC1 ₃ CH — CH — CH ₃ 3.108 H H H CH ₂ C1 3.109 H 3-OCH3 H CH ₃ 3.110 H 3-OCH3 CC1 ₃ CH ₃ 3.111 H 3-OCH3 CC1 ₃ CH ₃

physical constants

mp 76-78 ^Q C

mp 71-74 ° C

mp 89-91 ° C

mp 69-76 ° C

mp 74-75 ° C

mp 112-115 ° C

mp 71-73 ° C

mp 70-74 ° C

mp 99-101 ° C n _D ⁵⁰ 1.5472

mp 65-67 ° C

mp 86-88 ° C

mp 109-111 ° C n _D ⁵⁰ 1.5732

mp 119-121 ° C n _D ⁵⁰ 1.5803

mp 125-157 ° C mp 154-156 ° C

mp 102-110 ° C mp 157-159 ° C n _D ⁵⁰ 1.5672

mp 142-149 ° C

mp 96-98 ° C

mp 156-160 ° C resin

mp 111-113 ° C

mp 106-108 ° C

mp 107-109 ° C

mp 83-84 ° C

241S47

compound number Ri r ₂ R ₃ R < physical constants 3.112 H 3-OCH3 H CH ₃ resin 3.113 2-OCH 3 3-OCH3 H CH2OCH3 resin 3.114 2-OCH 3 3-OCH3 H CH ₃ 3.115 H 3-Br CClg CH ₂ OCH ₃ 3.116 H 3-Br H CH ₃ 3.117 H 3-F H CH ₃ 3.118 2-F H H CH2OCH3 3.119 H 3-F CC1 ₃ CH ₃ Examples illustrating Ingredients and preparation resources for liquid active substances

се I:

(% -% by weight).

F 1. Emulsion concentrate

a) b) c)

active substance from tables 25% 40% 50% calcium salt of dodecylbenzene of lionic acid 5% 8% 6% castor oil polyethylene glycol ether [36 moles of ethylene oxide) 5% tribuitylphenylpolyethyleinglycol ether (30 mol ethylene oxide) 12% 4% cyclohexanone - 15% 15 ° / o mixture of xylenes 65% 25% 20%

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

F 2. Solutions

• and) b] ( (d) active substance from tables 80% 10% 5 % 95% ethylenglyikolmionomeithyl- 20% ether - - polyethylene glycol (molecular weight 400) - 70% - N-methyl-2-pyrrolidane - 20% - epoxy coconut oil - - 1 % 5% petrol (boiling point in the range "/O 160-190 ° C) - - 94 -

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

F 3. Granulate

a) b)

active substance from tables 5 «/ 0 10% kaolin 94% - highly dispersed acid siliceous 1% - attapulgit - 90%

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

F 4. Dusting ___ a) ______________________________ b) _________ Active substance from the tables 2% 5% highly dispersed ffŽS- ». Silica 1% 5%

talc kaolin 97% 90% Thoroughly mixing the carrier substances with Examples illustrating composition and preparation The active substance is obtained directly - compositions for solid carriers of formula I: dusting. (% = o / o by weight) F 5. Wettable powder and) Bc) active substance from tables 25% 50% (2 votes) ligninsulfon sodium acid 6 ° / o 5 o / o _ sodium lauryl sulfate 3% - 5% natriumdiisobutylnaftalen- sulfonate - 6% 10% о к t у lf en o l p o 1 у eth у 1 engl y; ko 1- ether (7 to 8 moles of ethylene oxide) - 2 o / o - highly dispersed acid siliceous 5% 10 ° / by 10% kaolin 62 27 o / ₀ _ The active ingredient is well mixed with the ingredients dodecylbenzenesulfonate calcium and the mixture is ground well in a suitable mill. acid 3% nu. A wettable powder is obtained which can be polyglycol ether of castor oil Dilute with water to suspensions each required (35 moles of ethylene oxide) 4% concentration. cyclohexanone 30 o / o mixture of xylenes 50 o / o F 6. Emulsion concentrate They can be formed from this concentrate produce active substance from tables 10% diluting each emulsion with water octylphenolpolyethylene glycol ether concentration. (4-5 moles of ethylene oxide) 3% F 7. Dusting and) b] active substance from tables 5% 8% talc 95% - kaolin 92% The active ingredient is mixed with the carrier and F 9. Coated granulate: the mixture is ground in a suitable mill . So a directly usable dust is obtained. active substance from tables 3% polyethylene glycol (molecular F 8. Extruded granules: weight 200) 3% kaolin 94 ° / o active substance from tables 10% ligninsulfonic acid sodium salt 2% The finely divided active substance is in the mix- kar b ох у m e t h у lc elu l z z a 1% or evenly applied to the kaolin moistened kaolin 87% polyethylene glycol. In this way to obtain a coated granulate that is simple The active substance is mixed with additives, mixture of dust. is ground and moistened with water. This siměs is processed on an extruder and then

is dried in a stream of air.

4'154'7

F 10. Suspension concentrate:

active substance from tables 40 % ethylene glycol 10 % nonylphenolpolyethylene glycol ether (15 mol ethylene oxide) 6 % ligninsulfonic acid sodium salt 10 % carboxymethylcellulose 1 % 37% aqueous form of formaldehyde 0.2% silicone oil in the form of 75% aqueous emulsions 0.8% water 32 % The finely divided active substance is thorough-

mixed with ingredients. A suspension concentrate is thus obtained from which suspensions of any desired concentration can be prepared by diluting with water.

Examples · illustrating biological activity:

Example Β1

Effect against grass rust (Puccinia graminis) on wheat

(a) Residual-pirotective effect:

Wheat plants are sprayed with the active ingredient suspension (0.06% active ingredient) made of wettable powder 6 days after sowing. After 24 hours, the treated plants are infected with a fungal uredospore suspension. After an incubation period of 48 hours at 95-100% relative humidity and about 20 ° C, the infected plants are placed in a greenhouse where they are stored at about 22 ° C. Assessment of the development of rust deposits is performed 12 days after infection.

(b) Systemic effect:

Wheat plants are flooded 5 days after sowing with an active ingredient suspension prepared from a wettable powder, the concentration of active ingredient per volume of soil being 0.006%. After 48 hours, the treated plants are infected with a fungal uredospore suspension. After an incubation period of 48 hours at 95 to 100% relative humidity and about 20 ° C, the infected plants are placed in a greenhouse where they are kept at about 22 ° C. Assessment of the development of rust deposits is performed 12 days after infection.

The compounds according to the invention of Tables 1 to 3 show a good action against grass rust (Puccinia graminis) not only in the above-described greenhouse experiment but also in the field trial. Untreated but infected control plants show 100% ^. % infestation of grass rust (Puccinia graminis). Among other compounds, compounds 1.2 to 1.5, 1.9, 1.13, 2.11, 2.12, 2.18, 3.2, 3.4 to 3.7, 3.37 to 3.40, 3.42 to 3.46, 3.51, 3.52, 3.57, 3.70, 3.73 to 3.76 and 3.94 attack of grass rust (Puccinia graminis) to 0 to 10%.

Example B 2

Activity against Cercospora arachidicola on groundnut plants

(a) The residual protective effect of a groundnut plant up to 15 cm tall is oily sprayed with the active ingredient suspension (concentration 0.006% active ingredient), which was produced from a wettable powder. 48 hours after spraying, the plants are infected with a conidia suspension of the fungus. The infected plants are then incubated for 72 hours at a temperature of about 21 [deg.] C. under high humidity and then kept in a greenhouse until typical spots on the leaves are present. Assessment of fungicidal effect is performed 12 days after infection, based on the number and size of the spots occurring.

b) The systemic effect of up to 15 cm tall peanut plants is covered with an oil-based suspension of the active substance which has been made from a wettable powder, the concentration of active substance based on the soil volume being 0.06%. After 48 hours, the spared plants are infected with a conidia suspension of the fungus and then incubated at about 21 ° C and high humidity for 72 hours. The plants are then placed in a greenhouse and the fungal infestation is assessed after 11 days.

Compared to untreated but infected control plants (number and size of spots = 100%), peanuts which have been treated in the greenhouse or in the field with the active ingredients of Tables 1 to 3 show a strongly reduced attack by Cercospora. Thus, compounds 1.3, 1.6, 3.4, 3.5, 3.17, 3.18, 3.20, 3.49, 3.51, 3.52, 3.57, 3.67, 3.69, 3.70, 3.75 and 3.95 almost completely (8% attack) prevent Cercospora from infecting.

Example B 3

Effect against gray mold (Botrytis cinerea) on bean

Residual-protective effect:

The about 10 cm high bean plants are sprayed with the active ingredient suspension at a concentration of 0.02% active ingredient, which was made from a wettable powder of the active ingredient. After 48 hours, the treated plants are infected with a conidia suspension of the fungus. After 3 days of incubation of the infected plants for 3 days at 95-100% relative humidity and at 21 ° C, the fungal infestation is evaluated. The compounds of Tables 1 to 3 very strongly suppress fungal infection not only in the above-described model experiment but also under field conditions. When finished 241547 tnaci 0,0? % proved to be fully effective (0-5% disease), for example, compounds Nos. 1.1 to 1.6, 1.9, 1.11, 1.13, 1.15,

1.18, 1.20, 2.1, 2.2, 2.4, 2.5, 2.11, 2.12, 2.17

2.18, 2.19, 2.23, 3.1 to 3.7, 3.9, 3.16 to 3.22, 3.26, 3.30, 3.33, 3.37, 3.38, 3.39 to 3.52, 3.56 to 3.60, 3.65 to 3.80, 3.95, 3.103, 3.105, 3.108, 3.112 and 3.113.

Some of these compounds exhibit the same effect even at half the applied amount. The attack on untreated but infected bean plants is 100 why. Intermediates 16 and 24 are equally effective.

Example B 4

Effect against gray mold (Botrytis cinerea) on apples

Artificially damaged apples are treated by dropping an active substance suspension made of a wettable powder of the active substance instead of an injury. The treated fruits are then inoculated with a suspension of spores of gray mold (Botrytis cinerea) and incubated for 1 week at high humidity and at a temperature of about 20 ° C.

In the evaluation of the experiment, the rot-infected lesions are calculated and the fungicidal effect of the test substance is derived from this data. Among other compounds, they suppress compounds 1.1 to 1.6, 1.9,

1.11, 1.13, 1.15, 1.18, 1.20, 2.1, 2.2, 2.4, 2.5

2.11, 2.12, 2.17, 2.18, 2.19, 2.23, 3.1 to 3.7, 3.9, 3.16 to 3.22, 3.26, 3.30, 3.33, 3.37, 3.38, 3.39 to 3.52, 3.56 to 3.60, 3.65 to 3.80, 3.95, 3.103, 3.105, 3.108, 3.112 and 3.113 compared to n-treated control fruits (100% infestation) almost completely. Intermediates 16 and 24 are equally effective.

Example B5

Effect against Piricularia oryzae on rice

After 2 weeks of cultivation, the rice plants are sprayed with a 0.02% active ingredient suspension, which is 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 5 days of incubation at 95-100% relative humidity at 24 ° C, fungal infestation is assessed. The compounds of the invention of the formula I show a good effect on the control of fungal attack by Piricularia in this test;

For example, compounds number 1.3, 1.6,

2.2, 2.4, 3.1 to 3.5, 3.7, 3.17, 3.18, 3.20, 3.21,

3.44 to 3.47, 3.49, 3.51, 3.52, 3.57, 3.67, 3.70,

3.75 and 3.95 reduce fungal attack to less than 10%, and this effect could also be achieved under field conditions.

Example B 6

Effect against Potato Root (Rhizoctoinia solani on Crucifix)

Effect after soil application

The fungus is cultivated on sterile millet grains and a mixture of soil and sand is added. The infected soil is filled into dishes and ^{1 of the} soil is planted with the seeds of the brassica. Immediately after sowing, the soil is watered with a scientific suspension of the active ingredient which has been prepared from a wettable powder of the active ingredient. The concentration of the active ingredient is 20 ppm of active ingredient per volume of soil. The trays are then placed in a greenhouse for 2-3 weeks, where they are kept at about 24 ° C and kept in a moistened state with a gentle shower. The evaluation of this test determines the growth of the brassica plants. After treatment with suspensions prepared from wettable powder containing, as active substance, compounds number 1.3, 2.1, 3.20 or 3.37, over 80% of the brassica seeds are produced and the plants have a healthy appearance.

Example B 7

Residual-protective effect on apple scab (Venturia inaequalis) - test on apple shoots

Apple seedlings with fresh shoots of 10 to 20 µm are sprayed with the active ingredient suspension prepared from a wettable powder, the active ingredient concentration being 0.006%. After 24 hours, the treated plants are infected with a fungal conidia suspension. The plants are then incubated for 5 days at 90-100% relative humidity and maintained for 10 additional days in a greenhouse at 20-24 degrees Celsius. Scab infestation is assessed 15 days after infection. Compounds of formula I exhibit good activity against the causative agent of apple scab (Venturia inaequalis), in particular compounds number 1.2, 1.3, 3.4, 3.5, 3.17, 3.18, 3.20, 3.22, 3.27, 3.39, 3.71 and 3.95 suppress scab attack compared to untreated control plants to less than 20%. Compounds No. 1.3, 3.4, 3.5 to 3.17 make it possible to achieve this effect in a field trial even at a dose of 0.002%.

Example B 8

Effect against Helminthosporium gramineum

The wheat grains are contaminated with the spore suspension of the fungus and allowed to dry again.

The contaminated grains are then soaked with a sus241547 pension of the test substance (600 ppm by weight of seed) made of wettable powder. After two days, the grains are placed in suitable 3gar trays and after four days the development of hunting colonies around The number and size of the fungal colonies serve as a basis for evaluating the effect of the test compounds.

In this connection, the compounds of Tables 1 to 3, in particular the compounds of Table 3, substantially prevent fungal attack (0-10% attack).

Example 1 a d B 9

Effect against Fusarium niva le}

The wheat grains are contaminated with the spore suspension of the fungus and allowed to dry again. The contamination of the grains is carried out by pickling with a suspension of the test substance which has been prepared from the corresponding wettable powder (600 ppm active substance based on seed weight). After two days, the grains are placed on top. appropriate agar plates and, after an 'additional' 4 days, the development of fungal colonies around the grains is assessed. The number and size of the fungal colonies serve as a basis for assessing the effect of the test compounds.

For grains that were treated with a wettable powder containing as active ingredient one of the compounds of Tables 1 to 3, the development of fungal colonies was almost suppressed (0 to 5% attack).

Example '1 a. D' B 10 Ockranazrm '' '

a) '' Short-term 'finger' test mold. on wet '' corn.

Dry corn kernels intended for animal feed (batches of 80 g) are well mixed with the active ingredients of Tables 1 to 3 in the form of an aqueous suspension, emulsion or solution in sealable plastic beakers. The amount of active ingredient is measured to give a concentration of 0.06% of active ingredient, based on dry maize weight. The moistened paper strip provides a moisture-saturated atmosphere in beakers filled with corn and then sealed. After 2 to 3 weeks of incubation at about 20 ° C, the mixed populations of fungi begin to develop spontaneously on maize samples which have been treated with water only. Artificial contamination · No need to perform. The degree of fungal development after 3 weeks serves to evaluate the efficacy of the compounds of formula I.

(b) Long-term wet maize mold test

I. Corn samples which are not infected with mold after 3 weeks of incubation are incubated for a further 2 months. After each month, a visual evaluation is performed according to the same criteria as in test a).

II. The test is carried out in essentially the same manner as in tests (a) and (b), but the test substance is tested for 6 months at a concentration of 2000, 600 and 200 ppm of active substance (based on dry maize weight).

Treatment of the compounds of formula I of Tables 1 to 3 produced molds on moist corn. in all three tests (a), b1) and Ы1), both in the short term (3 weeks) and long term (6 months) completely suppressed.

Thus, for example, compounds Nos. 1.1 to 1.6, 1.9, 1.11, 1.13, 1.15, 1.18 and 1.20 as well as the other compounds of Tables 2 and 3 in all three tests (a), (b1) and (b1) almost completely prevent attack. of fungi (0-5% attack) at a test compound concentration of 600 ppm.

In similar experiments in which any type of grain (for example oats), hay, beet pulp or soybeans was used instead of fodder maize, the same results of several months' sustained protection were observed when treated with the above active compounds of formula I.

Claims (15)

1. A fungicidal composition, characterized in that it contains at least one compound of the formula I as active ingredient. RjCH-Y Němž in which Ri and R2 are independently hydrogen, halogen, methoxy, ^or: methylthio, R3 represents a hydrogen atom or a (C1-C8) haloalkyl group, Y is hydroxy, halogen or -O-C (O) -R 4, wherein R 4 is hydrogen, C 1 -C 8 alkyl, C 1 -C 8 haloalkyl, C 2 -C 6 alkenyl, 2-tetrahydrofuryl, 2-tetrahydropyrianyl, C 1 -C 6 alkoxycarbonyl alkoxycarbonyl or a group of formula -CH (Rr) -XR ₆ wherein ' X is oxygen or sulfur, R 5 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms and. R 8 is C 1 -C 6 alkyl, alkoxyalkyl. (C 1 -C 6) -alkoxy and (C 1 -C 6) -alkyl, (C 3 -C 6) alkenyl, (C 3 -C 6) alkynyl or optionally halogen, (C 1 -C 6) -alkyl C 1 -C 6 alkoxy, and / or C 1 -C 6 alkoxycarbonyl in the alkoxy moiety substituted by a phenyl group. 2. A composition according to claim 1, wherein the active ingredient comprises at least one compound of formula (I) wherein: R1 is a residue in the 2-position and R2 is a residue in the 3-position of the phenyl ring, the radicals independently of one another being hydrogen, halogen, methoxy, or methylthio, R 3 is hydrogen or C 1 -C 4 haloalkyl, and Y is hydroxy, halogen or -O · C (O] -R _4, wherein R2 represents an alkyl group of 1 to 6 OF THE INVENTION OF THE INVENTION are carbon atoms, haloalkyl of 1 to 6 carbon atoms, 2-tetnahydrofuryl, 2-tetrahydropyranyl, alkoxycarbonyl of 1 to 2 carbon atoms in the alkoxy moiety, or a group of the formula —CHfRr — XRg, wherein X represents an oxygen atom or a sulfur atom, R ₅ represents a hydrogen atom or a methyl group, and R ₆ represents an alkyl group having 1 to 6 carbon atoms, an alkoxyalkyl group having 1 to 3 carbon atoms in the alkoxy group and having 1 to 3 carbon atoms in the alkyl portion, an alkenyl group having 3 to 6 carbon atoms, an alkynyl group having 3 to 6 atoms carbon or optionally fluorine, chlorine, bromine, methyl, methoxy and / or alkoxycarbonyl having 1 to 3 carbon atoms in the alkoxy part substituted by a phenyl group. 3. A composition according to claim 1, wherein the active ingredient comprises at least one compound of formula (I) wherein: R ₁ represents a hydrogen atom, 2-chloro, 2-methoxy or 2-methylthio, R2 is hydrogen or 3-chloro, R 3 is hydrogen or C 1 -C 4 haloalkyl, and Y represents a hydroxy group, a chlorine group or a group of the formula -O-C (Oj-R4) wherein R 4 represents a C 1 -C 4 alkyl group, a C 1 -C 3 haloalkyl group, a 2-tetrahydrofuryl group, a 2-tetrahydrocarbonyl group, a C 1 -C 2 alkoxycarbonyl group the carbon atoms in the alkoxy moiety or the group -CH 2 -OR ₆ , wherein R 6 is C 1 -C 4 alkyl, C 1 -C 3 alkoxyalkyl of up to about 3 carbon atoms in the alkyl moiety, C 3 -C 6 alkenyl, C 3 -C 6 alkynyl, or optionally fluorine, chlorine, bromine, methyl, methoxy, ethoxycarbonyl and / or methoxycarbonyl substituted phenyl. 4. A composition according to claim 1, wherein the active ingredient comprises at least one compound of formula (I) wherein: R ₁ represents a hydrogen atom, 2-chloro, 2-methoxy or 2-methylthio, R2 represents a hydrogen atom or 3-chloro, R3 represents a hydrogen atom or a trichloromethyl group and Y is hydroxy, chloro or -O-C (O) -R / _n wherein R4 is C1-C4alkyl, haloalkyl; 1 to 2 carbon atoms, 2-tetrahydrofuryl 415. 2 4 7, 2-tetrahydropyranyl group, a methoxycarbonyl group or a -CH ₂ OR _6, wherein R ₆ is C 1-4 alkyl, methoxymethyl, ethoxymethyl, methoxyethyl, allyl, propargyl, phenyl or chloro, fluoro, bromo, methyl, methoxy or / and methoxycarbonyl substituted phenyl. 5. A composition according to claim 1, wherein the active ingredient comprises at least one compound selected from the group consisting of: N- (hydroxymethyl) -3- [3-chlorophenyl] -4-cyanopyrrole, N- (1-hydroxy-2,2,2-trichloroethyl) -3- (3-methoxyphenyl) -4-cyanipyrrole, N- (chloromethyl) -3- (3-methoxyphenyl) -4-cyanopyrrole, N - (1,2,2; 4- (4-chloroethyl) -3- (3-methoxyphenyl) -4-cyanopyrrole); and N- (1,2,2,2-tetroahloroethyl) -3- (3-bromophenyl) -4-cyanopyrrole. 6. A composition according to claim 1, wherein the active ingredient comprises at least one compound selected from the group consisting of: N- (l-acetyloxy-2,2,2 - ^гichlore, ethyl) -3- (2,3-dic chlorophenyl) -4-cyanopyrrole, N- (1-Hydroxy-2,2,2-chloroethyl) -3- (2,3-dichlorophenyl) -4-cyanopyridine, N- (1-Methylacetyloxy-2,2,2-trichloroethyl) -3- (2,3-dichlorophenyl) -4-quinopyrrole, N- (methoxyationhyloxymethylmethyl) -3- [2,3-dichlorophenyl) -4-cyanopyrrole, N- [1- (n-butylcarbonyl-yl) -2,2,2-trichloroethyl] -3- (2,3-dichlorophenyl) -4-cyanopyrrole, N- [1- (n-propoxyacetyloxy) -2,2,2-richloroethyl] -3- (2,3-dichlorophenyl) -4-cyanopyrrole, N [1- (n-butoxyacetyloxy) -2,2,2-tichloroethyl] -3- (2,3-dichlorophenyl) -4-cyanopyrrole, N- [1- (n-butoxyacetyloxy) ethyl] -3- (2,3-dichlorophenyl) -4-xyanopyrrole, N- [1- (Propylaminoethyl yloxy) -2,2,2-trichloroethyl] -3- (2,3-dichlorophenyl) -4-cyanopyrrole . 7. The composition of claim 1, wherein the active ingredient comprises at least one compound selected from the group consisting of: N- (1-11X4 * 1.2-2.2X00X10 ^ 111) -3- (2-methylthiophenyl) -4-cyanopyrrole), N- (1-hydroxy-2,2-trimethyl) -3- (2-methoxyphenyl) -4-cyano; N- (1-hydroxy-2,2,2'-cyclohexyl) -3- (2-chlorophenyl) -4-cyanopyrrole, N- [1- (isopropyloxyethyl) -2,2,2-trichloroethyl) -3- (2-chlorophenyl) -tethanone bromide2, N- [1- (methoxyacetyl) -2,2,240-4,101-ethyl] -3- (2-ethylthiophenyl) -4-cyanopyrrole, N- (ETR methcxr ^{and c} 1) -3- (2-chlorophenyl) -4-cyanopyrrole. 8. A process for the preparation of an active ingredient as claimed in claim 1, wherein, in the presence of a solvent, the compound 346-4-4 is reacted at temperatures between - 0 ° C and 200 ° C. ??? ??? ??? ?????? ??? R 1 and R 2 are as defined in 1, with an aldehyde of formula III R ₃ —CHO (III) wherein R @ 1 has the meaning given in item 1, optionally in the presence of an acidic or basic catalyst, to form a compound of formula (Ia) in which: Rh ₂ and R 3 have the meanings given in (1) and the compound of formula (Ia) obtained is then, if desired, converted by treatment with a halogenating agent or an acylating agent with a different hydroxyl group with another Y radical into another derivative of formula I. 9. The process of claim 8, wherein the compound of formula Ia is converted by treatment with an acid of formula IV in the presence of an inert solvent, if any. R, -COOH (IV) wherein R4 is as defined in item 1, or a reactive acid derivative thereof, as an acylating agent, at temperatures between 0 ° C and 150 ° C directly to the acyloxy derivative of Formula 1b (Ib) wherein: R b R 2, R 3 and R 4 are as defined in 1, or the free hydroxyl group in the compound of formula Ia is replaced by a halogen atom with a haloignant, followed by optionally converting the halogenated product in the presence of a solvent under reaction conditions inert, at temperatures between 0 ° C and 150 ° C and optionally in the presence of a reaction catalyst by reaction with a salt of formula V of? -COO® M® (v) wherein to a compound of formula 1b. Process according to one of Claims 8 or 9, characterized in that the corresponding compounds of the formulas II to V are used as starting materials to give compounds of the formula I in which: R is a radical at position 2 and R ₂ is a radical at position 3 · phenyl ring and · the radicals are independently hydrogen, halogen, methoxy or methylthio, R3 represents a hydrogen atom or a (C1-C4) haloalkyl group, and Y represents a hydroxy group, a halogen atom or a group of the formula (O) -r ₄ , in which R 4 represents a C 1 -C 6 alkyl group, a C 1 -C 6 haloalkyl group, a 2-tetrahydro-furyl group, a 2-tetriahydropyranyl group, a C 1 -C 2 alkoxycarbonyl group or a group of the formula -CH.RJ-XRc, where X is oxygen or * sulfur, R 5 represents a hydrogen atom or a methyl group; R ₆ represents an alkyl group having 1 to 3 carbon atoms, an alkoxyalkyl group having 1 to 3 carbon atoms in the alkoxy group and having 1 to 3 carbon atoms in the alkyl portion, an alkenyl group having 3 to 6 carbon atoms, an alkynyl group having 3 to 6 atoms or optionally fluorine, chlorine, bromine, methyl, methoxy and / or alkoxycarbonyl having 1 to 3 carbon atoms in the alkoxy moiety substituted by phenyl. 11. A process according to any one of claims 8 or 9, characterized in that the corresponding compounds of the formulas (II) to (V) are used as starting materials to produce compounds of the formula (I) in which: R * represents a hydrogen atom, a 2-chloro, a 2-methoxy group or a 2-methylthio group, R2 is hydrogen or 3-chloro, R 3 is hydrogen or C 1 -C 4 haloalkyl, and Y represents a hydroxy group, a chlorine atom or a group -O-СЮ) - R4, where R 4 is a C 1 -C 4 alkyl group as defined in item 1 and is an alkali or alkaline earth metal cation, carbon atoms, a C 1 -C 3 hailngenalkyl group, 2-tetrahydrofuryl, 2-tetrahydrohydropyranyl. in group alkioxykaríbonylavou group having 1-2 carbon atoms in the alkoxy moiety or a group -CH ·> -OR _g wherein R ₆ is C 1 -C 4 alkyl, C 1 -C 3 alkoxyalkyl, C 1 -C 3 alkyl, C 3 -C 6 alkenyl, C 3 -C 6 alkynyl or optionally fluorine, chlorine, bromine, methyl, methoxy, ethoxycarbonyl or phenyl substituted by methoxycarbonyl. Process according to one of Claims 8 or 9, characterized in that the corresponding compounds of the formulas II to V are used as starting materials to give compounds of the formula I in which: R _{@ 1} is hydrogen, 2-chloro, 2-methoxy or 2-methylthio, R ₂ represents hydrogen or 3-chl'or, R ₃ represents a hydrogen atom or a trichloro-methyl group and Y is hydroxy, chloro or -O-C (O) -R ₄ , wherein R ₄ is C 1 -C 4 alkyl, halooalkyl, C 1 -C 2 alkyl, 2-tetrahydrofuryl group, 2-tetrahydropyranyl group , a methoxycarbonyl group or a group -CH ₂ OR _g , wherein R _g is C 1 -C 4 alkyl, methoxymethyl, ethoxymethyl, methoxyethyl, α, Hyl, propargyl, phenyl or fluorine, chlorine, bromine, methyl, methoxy and / or methoxy-substituted phenyl group. Process according to one of Claims 8 or 9, characterized in that the corresponding compounds of the formulas II to V are used as starting materials to form N- (hydroxymethyl) -3- (3-chlorophenyl-4-cyampyrroil), N- (1-Hydroxy-2 ', 2,2-trichloroethyl) -3- - (3-methoxyphenyl) -4-cyanopyrrole, N- (chloromethyl) -3- (3-methoxyphenyl) -4-cyanopyrrole, N (1,2,2,2-tetrachliorethyl) -3- (3-methoxylphenyl) -4-cyanopyrrole, N- (1,2,2,2-trifluoromethyl) -3- (3-bromophenyl) -4-cyanopyrrole. Process according to one of Claims 8 or 9, characterized in that the corresponding compounds of the formulas II to V are used as starting materials to give N- (1-acetyloxy-2,2,2-trichloroethyl) -3- (2,3-dichlorophenol) -4-cyclohexanediol, N- (1-hydroxy-2,2,2-trichloroethyl) -3- - (2,3-dichlorophenyl) -4-cyanopyrrole, N- (1-теШохуасе1у1оху 2,2,2-1г1сЬ1огe (ethyl) -3- (2,3-dichkrfenyl) -4-cyanopyrrole ^and, N- (methoxyacetyloxymethyl) -3- - (2,3-dichlorophenyl) -4-cyanopyrrole, N- [1- (n-butylcarbamate ^and carbonyloxy) -2,2,2-'trichlorethyl] -3- (2,3-diichlorfenyl) -4-kya.npy.rrolu, N- [1- (n-propoixyacetyloxy) -2,2,2-trichloroethyl] -3- (2,3-dichlorophenyl) -4-cyanopyrrole, N- [1- (n-butoxyacetyl) -2,2,2-trichloroethyl] -3- (2,3-dichlorophenyl) -4-cyanopyrrole, N - [1- (n-butoxyaceityloxy) ethyl] -3- - [2,3-dichlorophenyl] -4-cyanopyrrole, N- [1- (propargyloxyacetyloxy) -2,2,2-trichloroethyl] -3- (2,3-dichlorophenyl) -4-cyanopyrrole. Process according to one of Claims 8 or 9, characterized in that the corresponding compounds of the formulas II to V are used as starting materials to give N- (1-Hydroxy-2,2,2-trichloroethyl) -3-2-methylthiophenyl) -4-cyanopyrrole, N- (1-Hydroxy-2,2,2-trichloroethyl) -3- - (2-methoxyphenyl) -4-cyanopyrrole, N- (1-Hydroxy-2,2,2-trichloroethyl) -3- - (2-chlorophenyl) -4-cyanopyrrole, N- [1- (isoipropoxyaicetyloxy) -2,2,2-trichloroethyl] -3- (2-chlorophenyl) -4-cyanopyrrole, 39 40 N- [1- (methoxyacetyloxy) -2,2,2-trichloroethyl] -3- (2-methylthiophenyl) -4-cyanopyrrole a. N- [methoxyacetyl] -3- (2-chlorophenyl) -4-cyano-pyrrole.