NO842422L - 3-PHENYL-4-CYANOPYRROL DERIVATIVES, PROCEDURES FOR THE PREPARATION AND USE OF THESE AS MICROBICIDES - Google Patents

Description

The present invention relates to new N-alkylated 3-phenyl-4-cyanopyrrole derivatives with subsequent formula I, their preparation, and microbicidal agents, which contain at least one of the title compounds as active ingredient. The invention further relates to the production of the aforementioned agents and the use of the new active substances and agents for combating harmful microorganisms, especially plant-damaging fungi.

New compounds with the general formula I are described herein

in which

R 1 and R 2 independently of each other are hydrogen, halogen, methoxy or methylthio;

R 1 means hydrogen or C 1 -C 8 haloalkyl;

Y is hydroxy, halogen or the group -O-C(O)-R^; wherein R 1 means H, C 1 -C 8 alkyl, C 1 -C 8 haloalkyl, . C 2 -C 8 -alkeny 1, 2-tetrahydrofuryl, 2-tetrahydropyranyl, C 1 -C 4 -alkoxycarbonyl or the group -CH(R 4 )-XR 4 , wherein

X is oxygen or sulfur;

R 1 - means hydrogen or C 1 -C 2 -alkyl, and R 6 is C 2 -C 8 -alkyl, (C 1 -C 8 -alkyloxy) -C 2 -C 8 -alkyl, C 3 -C 6 -alkenyl, C 1 -C 8 -alkyny 1 or ;unsubstituted or with .halogen, C₁-C₆-alky 1, ■ C₁-C₆-alkoxy, C-₆-C₆-alkoxycarbonyl substituted phenyl.

By the term itself, alkyl or as a component of another substituent is meant, depending on the number of carbon atoms indicated, e.g. the following groups: methyl, ethyl, propyl, butyl, pentyl, hexyl etc., as well as their isomers, such as e.g. iso-propyl, isobutyl, tert.-butyl, isopentyl, etc..-Haloalkyl means a mono- up to perhalogenated alkyl substituents, such as e.g. CH2C1, CIIC12,CC13, CH2Br, CHBr2 , CBr3, CH2F, CHF2, CF2, CC12F, CC12-CHC12, CH2CH2F, CJ3, etc.. By halogen is meant here and in the following fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine. Alkenyl controls e.g. vinyl, propenyl-(1), allyl, butenyl-(1), butenyl-(2), butenyl-(3), etc. as well as alkyl chains interrupted by multiple C=C double bonds. Alkynyl means e.g. propynyl-(2), propargyl, butynyl-(1), butynyl-(2), etc., preferably propargyl.

The compounds of formula I are stable oils, resins or predominantly crystalline solids under normal conditions, which are distinguished by very valuable microbicidal properties. Above all, they can be used under open field conditions in agriculture or related areas curatively and especially preventively for combating plant-damaging microorganisms. The active ingredients of formula I according to the invention excel within broad application concentrations by a high fungicidal activity and unproblematic use in open fields.

Due to their pronounced microbicidal activity, the following groups of substances are increasingly preferred in ascending order: a) Compounds with formula I, in which R-^ is in the 2-position and R2 is in the 3-position and independently of each other means H, . halogen, methoxy or methylthio, R 3 means hydrogen or C 1 -C 4 -haloalkyl, and Y means hydroxy, halogen or the group -O-C(O)-R 4 ; wherein R 4 means C 1 -C 8 -alkyl, C 1 -C 8 -haloalkyl, 2-tetrahydrofuryl, 2-tetrahydropyranyl, C 1 -C 2 - alkoxycarbonyl or the group -CH(R 4 )-XR 8 ; wherein X is oxygen or sulfur,

is hydrogen or methyl, and •

<R>6means C^-Cg-alkyl, (C-,-C3-Alkoxy)-C^-C^-alkyl, C3-C6~alkenyl, C3~C(--alkyny 1 or unsubstituted or with fluorine, chlorine , bromine, methyl, methoxy and/or C 1 -C 3 -alkoxycarbonyl substituted phenyl..

b) The compounds of formula I, in which R-^ means H, 2-C1, 2-methoxy or 2-methylthio;. R 2 means II or 3-Cl; R3 means

■hydrogen or C^-C^-haloalkyl, and Y means OH, chlorine or the group -0-C(0)-R4 #wherein R4 means C-^-C^-alkyl, C^-C^-haloalkyl, 2- tetrahydrofuryl, 2-tetrahydropyra-riyl, C-^-C2- alkoxycarbonyl 1 or the group -CI-^-ORg, wherein R6 is C1-C4-alkyl, (C^-C-^-alkoxy)-C1-C3-alkyl , C3-C"6-alkynyl or unsubstituted or with fluorine, chlorine, bromine, methyl, methoxy, • ethoxycarbonyl and/or methoxycarbonyl substituted phenyl.

c) Compounds of formula I, where R-1 is H, 2-C1, 2-methoxy or 2-methylthio; R 2 is K or 3-Cl; R3 is hydrogen

or CC13 and Y is Oll, chlorine or the group -O-C(O)-R4; .wherein R 4 means C 1 -C 4 -alkyl, C 1 -C 2 -haloalkyl 1,2-tetrahydrofuryl, 2-tetrahydropyranyl, methoxycarbonyl or the group -C 1 -C 2 OR 8 ; wherein Rg is C-1-C4-alkyl, methoxymethyl, ethoxymethyl, methoxyethyl, allyl, propargyl, phenyl or phenyl substituted with fluorine, chlorine, bromine, methyl, methoxy and/or methoxycarbonyl.

Particularly preferred single compounds are, for example:

In the following, the single compounds a to u are particularly preferred due to their strong plant fungicidal effect under open field conditions:

a) N-(hydroxymethyl)-3-(3-chlorophenyl)-4-cyanopyrrole,

b) N-(1-acetyloxy-2,2,2-trichloroethyl)-3-(2,3-dichlorophenyl)-4-cyano-pyrrole, c) N-(1-hydroxy-2,2,2-trichloroethyl) )-3-(2-methylthiophenyl)-4-cyano-pyrrole, d) Nr (1-hydroxy-2,2,2-trichloroethyl)-3-(2,3-dichlorophenyl)-4-cyano-pyrrole , e) N-(1-hydroxy-2,2,2-trichloroethyl)-3-(2-methoxyphenyl)-4-cyano-pyrrole, f) N-(1-methoxyacetyloxy-2,2,2-trichloroethyl) -3-(2,3-dichlorophenyl)-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-cyanopyrrole,

k) N-(chloromethyl)-3-(3-methoxyphenyl)-4-cyanopyrrole,

1) H-ti-(n-butylcarbonyloxy)-2,2,2-trichloroethyl]-3-(2,3-dichlorophenyl)-4-cyanopyrrole,

rn) N-(1,2,2,2-tetraethyl)-3-(3-methoxyphenyl)-4-cyanopyrrole,

n) N-[1-(n-propoxyacetyloxy)-2,2,2-trichloroethyl]-3-(2,3-dichlorophenyl)-4-cyanopyrrole,

o) N-(1,2,2,2-tetrachloroethyl!)-3-(3-bromophenyl)-4-cyanopyrrole, p) N- [ 1-(n-butoxyacetyloxy)-2,2,2-trichloroethyl] -3-(2,3-dichlorophenyl)-4-cyanopyrrole,

q) N-[1-(isopropoxyacetyloxy)-2,2,2-trichloroethyl]-3-(2 -

chlorophenyl)-4-cyanopyrrole,

r) •N- [1-(n-butox<y>acet<y>lox<y>)ethyl]-3-(2,3-dichlorophen<y>1)-4-cyanopyrrole,

s) N-[1-(methoxyacetyloxy)-2,2,2-trichloroethyl]-3-(2-methyl-thiopheryl)-4-cyanopyrrole,

t) N-[1-(propargyloxyacetyloxy)-2,2,2-trichloroethyl]-3-(2,3-dichlorophenyl)-4-cyanopyrrole,

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

The new compounds of formula I can be prepared according to the invention by reacting a 3-phenyl-4-cyanopyrrole derivative with formula II

with an aldehyde of the formula III to a hydroxy derivative of the formula Ia - and, if desired, transfers the latter by replacing the free OH group with another residue Y in one of the other products of the formula I, whereby this replacement takes place by either transferring a compound of formula Ia with an acid of formula IV or preferably with one of its reactive acid derivatives, especially acid halides, such as e.g. acid chloride or acid bromide, or with an acid anhydride in an acyloxy product of formula Ib or by replacing the free OH group in a compound of formula Ia first in the usual way with a halogen, preferably chlorine or bromine and, if desired, transfers the now halogenated product by reaction with a salt of the formula -\7

in a compound of formula Ib, wherein the substituents in formulas Ia, Ib, II, III, IV and V have the meanings given under formula I, M<+>means a metal cation, preferably an alkaline earth or especially alkali metal cation, such as .ex.

<++><+>+ + •<+>

Ca, Mg. , Na or K .

The reaction of compounds of formula II with aldehydes of formula III can be carried out with or without reaction-initiated solvents or solvent mixtures. Especially suitable are e.g. aromatic hydrocarbons, such as benzene, toluene or xylenes; halogenated hydrocarbons, such as chlorobenzene; aliphatic hydrocarbons such as petroleum; ether and , ether-like. f or5-.. bonds, such as dialkyl ethers (diethyl ether, diisopropyl ether, tert-butyl methyl ether, etc.), furan, dimethoxyethane, dioxane, tetrahydrofuran; dimethylformamide, etc.

The reaction of compounds of formula II with compounds of the formula. III is advantageously carried out without a solvent, but with an excess amount of aldehyde III. Depending on the type of aldehyde III, one works in solution or in a melt. Here, the addition of acidic or basic catalysts has a beneficial effect on the reaction rate. As acid catalysts, e.g. anhydrous hydrogen halides and mineral acids, such as HC1, HBr or I^SO^, but also concentrated hydrochloric acid in speech. As basic catalysts, one can, for example, use trialkylamines (trimethylamine, triethylamine, dimethylethylamine, etc.), alkali and alkaline earth carbons (such as Na2C03,

BaCO^, MgCO^, I^CO^, etc.) or alkali alcoholates (such as NaOCH3, NaOC2H5, KO(iso-G3H7) , KO (t.-butyl) ).■' The temperatures for this reaction are generally between 0° C and 200°C, preferably 0°C and 160°C, and the reaction duration is 1 to 24 hours, especially 1 to 4 hours.

The replacement of the free hydroxyl group in the compounds

with formula Ia with a group Y is preferably carried out in a reaction-ionized solvent. Examples of such solvents are: aromatic and aliphatic hydrocarbons such as benzene, toluene, xylene, petroleum ether, ligroin or cyclohexane; halogenated hydrocarbons, such as chlorobenzene, methylene chloride, ethylene chloride, chloroform, carbon tetrachloride or tetrachloroethylene; ethers and ether-like compounds such as diethyl ether, diisopropyl ether, t-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 blan-

dings of such solvents with each other.

The introduction of the group Y takes place by usual methods. Does Y mean chlorine is used as a reagent, e.g. phosphorus oxychloride, phosphorus trichloride, phosphorus pentachloride or preferably thionyl chloride. Man generally works at temperatures from 0° to +120°C. If Y is equal to bromine, phosphorus tribromide or phosphorus pentabromide is preferably used and the reaction is carried out at 0° to +50°C. If Y is the group -0-C (0)-R'4, the corresponding acid halide, especially acid chloride, is normally used as reagent.' Below, it is appropriate if the reaction is carried out at . temperatures from -20° to +50°C, preferably -10°C to +30°C and in the presence of a weak base such as pyridine or triethylamine. Furthermore, 4-dialkyl-aminopyridines such as 4-dimethyl- or 4-diethylaminopyridine can be added as catalysts to speed up the reaction.

The reaction of compounds of formula I, in which Y is halogen, especially chlorine or bromine, takes place with salts of formula V normally in the presence of a common inert. solvent or solvent mixture. Examples of such solvents are: aromatic and aliphatic hydrocarbons such as benzene, toluene, xylenes, petroleum ether, ligroin or cyclohexane; ethers and ether-like compounds such as dialkyl ether, e.g. diethyl ether, diisopropyl ether, t-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 addition of the catalytic amounts of a crown ether, such as 18-krone-6 or 15-krone-5 has a very favorable effect on the course of the reaction with this conversion. The reaction temperatures are generally between 0° and 150°C, preferably 20 to 80°C. The reaction duration is 1 to 24 hours.

In a factory embodiment, the preparation of compounds of formula Ib, especially those with R-^=, is carried out. CCl^ or R,= H, starting from compounds of formula II, in a so-called one-boiler process. Here you work with advantage in one of the above-mentioned solvents or diluents, and particularly suitable are e.g. etheric compounds, such as tetrahydrofuran and in the presence of a weak base, such as trialkylamine (triethylamine) or pyridine. Chloral or paraformaldehyde are used as reagents. The reaction can be catalyzed by the addition of a catalyst ■such as 1,8-diazabicyclo-[5,4,0]undec-7-ene [=DBU]. The temperatures in this first reaction step are at -20° to +100°C, preferably 0° to 50°C and the reaction time from 0 .5 to .2 hours. A hydroxy derivative of the formula Ia is formed intermediately, which is not isolated, but is reacted in the same reaction solution at -30°C to +30°C, preferably -10°C to 0°C and in the presence of catalytic amounts of a 4-dialkylamine. pyridine, preferably 4-dimethylaminopyridine, with a compound of formula IV. The reaction duration for this second step is 0.5 to 16 hours.

The starting compounds with the formulas III, IV and V are generally known or are prepared by methods known per se. •

Some of the compounds pyrrolene with the formula II are known from the literature. Thus, e.g., is described the production method and the chemical properties of 4-cyano-3-phenyl-pyrrole in Tetrahydron Letters Nr. 52, pp. 5337-5340 (19.72). Nothing is said about the compound's biological effect.

N-acetylated substituted 3-phenyl-4-cyanopyrrole derivatives are known from the literature. Thus, e.g., is described pyrroles of formula VI in which X. means a halogen atom, a lower alkyl or lower haloalkyl group, and n is 0, 1 or 2, in DE-OS 2,927,480 as fungicides.

Further- are pyrrole derivatives of the formula VII

with

R-, = acyl, alkoxycarbonylalkyl-alkyl...

Rg, Rg = H, aryl .... R-^q = hydroxy, mercapto

known from British patent 2,078,761 as heat and light stabilizers for PVC plastics.

Further pyrrole derivatives of formula VIII

with

R-^= alkyl, optionally substituted with acyloxy ...

R5= H, alkyl, CN ...

are mentioned as polymerization catalysts for vinyl chloride in DE-OS. 2.02 8.36 3.

The known pyrrole derivatives are either inactive against plant-pathogenic organisms or show a clear plant-fungicidal effect in greenhouses, but which are not reproducible under outdoor conditions due to their instability to environmental influences. They are therefore not in practice suitable for use in agriculture, horticulture or related areas of application. The new pyrrole derivatives of formula I according to the present invention are, on the other hand, a valuable enrichment of the state of the art, because it has surprisingly been found that new

pyrrole derivatives with formula I have a very favorable microbicide spectrum against phytopathogenic fungi and bacteria for practical (outdoor) needs. However, they can not only be used in field cultivation or similar areas of application for combating harmful micro-organisms on cultivated plants, but

in addition to storage protection for the conservation of perishable goods. Compounds of formula I have very advantageous curative, systemic and special preventive properties and can be used for the protection of numerous cultivated plants, especially open field crops. With the active substances of formula I, microorganisms that act on plants or plant parts can

(fruits, flowers, foliage, stem, tubers, roots)

in various beneficial crops is inhibited or eliminated, whereby later growing plant parts are also spared from such microorganisms.

The microorganisms are, for example, effective against phytopathogenic fungi belonging to the following classes: Ascomycetes, e.g. Erysiphe, Sclerotinia, Fusarium, Monilinia, Helminthosporium; Basidio-mycetes such as e.g. Puccinia, Tilletia, Rhizoctonia; as well as Oomycetes such as Phytophtora belonging to the class Phycomyce-res. As pesticides, the compounds of formula I can be used with particularly good results against important harmful fungi from the family Fungi imperfecti, thus e.g. against Cercospora, Piricularia and above all against Botrytis, Botrytis species (B. cinerea, B. allii) together with the gray molds are a significant economic damage factor for grapes, strawberries, apples, onions and other fruit and vegetable species. In addition, some of the compounds of formula I; e.g. connection no. 1.2,

can be used with good results for the protection of perishable goods of vegetable or animal origin. They fight molds such as penicillin, Aspergillus, Rhizopus, Furasium, Helminthosporium, Nigrospora and Alternaria as well as bacteria such as butyric acid bacteria and yeasts such as C.andida.

As pesticides, the compounds of formula I have a very favorable spectrum of action for practical use in agriculture for the protection of cultivated plants without adversely affecting them in the case of unwanted side effects.

They can also be used as mordants for the treatment of seed material (fruits, tubers, grains) and plant cuttings for protection against fungal infections and against phytopathogenic fungi that occur in the soil.

The invention thus also relates to microbicidal agents and the use of the compounds of formula I for control

of phytopathogenic microorganisms, especially plant-damaging fungi, nen. preventive prevention of attacks on plants and supplies of vegetable or animal origin.

In addition, the present invention also includes the production of (agro) chemical agents which are characterized by thorough mixing of the active substance with one or more substances described herein according to substance groups. Also included is a method for treating plants or storage material which is characterized by applying the compounds of formula I acc. the new agent on the plants, plant parts, their growing place or the substrate.

As target crops for plant protection apply within the scope of this invention e.g. the following plant species: cereals: (wheat, barley, rye, oats, rice, sorghum and related); roots (sugar beet and beetroot); stone, stone and berry fruit: (apples, pears, plums, peaches, almonds, cherries, strawberries, raspberries and blackberries); legumes: (beans, lentils, peas, soy); care crops: (rapeseed, mustard, poppies, olives, sunflowers, coconuts, ricinus, cocoa, peanuts); Cucumber crops: (grass, tubers, cucumbers, melons); fiber crops: (cotton, flax, hemp, jute); citrus fruits: (oranges, lemons, tangerines, grapefruit); vegetables: (spinach, lettuce, asparagus , cabbage, types, carrots, onions, tomatoes, potatoes, peppers); laurel crops: (avocado, cinnamon, camphor) or plants such as corn, tobacco, nuts, coffee, sugarcane, tea, grapes, hops, bananas or natural rubber plants and ornamental plants (composites).

As a storage preservative, the compounds of formula I are used in unchanged form or preferably together with the usual aids within the formulation technique and processed e.g. for emulsion concentrates, spreadable pastes, directly sprayable or dilutable solutions, diluted emulsions, sprayable powders, soluble powders, dusting agents, granules. by pre-creations in e.g. polymeric substances in a known manner.. The method of application, such as spraying, fogging, atomizing, spreading, coating or pouring, and the form of the agent are adapted to the intended goals and the circumstances at hand. Favorable usage quantities are generally 0.01 to a maximum of 2 kg of active substance per 100 kg of substrate to be protected, but they depend quite significantly on the nature of the substrate (surface size, consistency, moisture content) and its environmental impact.

In the present invention, storage and storage material means vegetable and/or animal natural substances and their further processing products, e.g. the subsequent plants that have been removed from the natural life cycle, whose plant parts (stems, leaves, tubers, seeds, fruits, grains),

which is available in a freshly harvested state or in further processed form (pre-dried, moistened, chopped, ground, roasted). As examples which have no limiting character in the field of application within the scope of this invention, the following cultures are meant: cereals (such as wheat, barley, rye, oats, rice, sorghum and related); roots (such as carrots, sugar beets and beets); stone fruit and berries (such as apples, pears, peaches, almonds, cherries, strawberries, raspberries and blackberries, plums); legumes (such as beans, lentils, peas, soy); oil crops (such as rapeseed, mustard, poppies, olives, sunflowers, coconut, castor, cocoa, peanuts); vegetable crops (such as pumpkins, cucumbers, melons); fiber crops (such as cotton, flax, hemp, jute, nettle); citrus fruits; vegetable varieties (such as spinach, lettuce, asparagus, cabbages), onions, tomatoes, potatoes, peppers): bay plants >■ (such as avocado, cinnamon, camphor) or maize, tobacco, nuts, coffee, sugar cane, tea, grapes, chestnuts , hops, bananas, grass and.hay..

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

The treated storage material is protected during treatment

with compounds of formula I before attack by molds and other undesirable microorganisms. This prevents the formation of toxic and partly carcinogenic molds (aflatoxins and ochratoxins), the material is preserved against rotting and its quality is maintained for a longer period of time. The method according to the invention can be used on all dry and moist storage and storage materials, which can be attacked by microorganisms such as yeast, bacteria and especially molds.

A preferred method for applying the active ingredient. consists in spraying or wetting the substrate with a liquid preparation or in mixing the substrate with a solid one. preparation of the active substance. The described conservation method is part of the present invention.

The active substances of formula I are normally used in the form of mixtures and can be given simultaneously or in sequence with additional active substances on the surface, the plants or the substrate to be treated. These additional active substances can both be fertilisers, trace element mediators or other preparations that affect plant growth. However, they can also be selective herbicides, insecticides, fungicides, bactericides, nematicides, molluscicides or mixtures of several of these preparations, together with possibly further common carrier substances within the formulation technique, surfactants or other application aids.

Suitable carriers and additives can be solid or liquid and correspond to the appropriate substances within the formulation technique, such as e.g. natural or regenerated mineral ■substances, dissolving, dispersing, wetting, binding, thickening agents; binding or thickening agents.

A preferred method of application of an active ingredient of formula I acc. an (agro)chemical that contains at least one of these active substances is applied to the foliage (foliar application). The number, applications and amount of use depend on the degree of infection for the corresponding source (type of fungus). However, the active substances with formula I can also enter the plant's roots through the soil (systemic effect), by soaking the plant's growing area with a liquid preparation or bringing the substances into the soil in solid form, e.g. in the form of granules (soil application). However, the compounds of formula I can also be applied to seed grains (Coating), either soaking the grains with a liquid preparation of active ingredients or coating them with a solid preparation. In addition, in special cases further application types are possible, thus e.g. targeted treatment of the plant stems or buds.

The compounds of formula I are used below in unchanged form or preferably together with the auxiliaries common in the formulation technique and are formulated e.g. for emulsion concentrates, spreadable pastes, directly sprayable or dilutable solutions, diluted emulsions, sprayable powders, soluble powders, dusting agents, granules, when encapsulating in e.g. polymeric substances in a known manner. The application processes such as spraying, fogging, atomizing, spreading, ironing or pouring are chosen depending on the objective of the present circumstances, such as the nature of the agent. Favorable amounts of use are generally 50 g to 5 kg of active substance (AS) per hectares; preferably 100 to 2 kg AS/ha, especially at 200 g to 600 g AS/ha.

The formulations, i.e. the agents, preparations or mixtures containing the active substances of formula I and possibly a solid or liquid additive, are prepared in an unknown manner, e.g. by thoroughly mixing and/or grinding the active ingredient with stretching agents, such as e.g. with solvents, solid carriers, and possibly surface-active compounds (surfactants).

Suitable solvents include: aromatic hydrocarbons, preferably the fractions Cg to such as e.g. xylene mixtures or substituted naphthalenes, phthalic acid esters such as dibutyl or dioctyl phthalate, aliphatic hydrocarbons such as cyclohexane or paraffins, alcohols and glycols. as well as their ethers and esters, such as ethano], ethylene glycol, ethylene glycol monomethyl or ethyl ether, ketones such as cyclohexanone, strongly polar solvents such as N-methyl-2-pyrrolidone, dimethylsulfoxide or dimethylformamide, as well as possibly epoxidized vegetable oils such as epoxidized coconut oil, sunflower oil or soybean oil, or water.

As solid carriers. e.g. for dusting agents and dispersible powders, natural stone flours are usually used, such as calcite, talc, kaolin, montmorillonite or attapulgite.

To improve the physical properties, highly dispersed silicic acid or highly dispersed polymers with absorbency can also be added. Porous types, such as e.g. pumice stone, pieces of brick, sepiolite or bentonite, as non-adsorbing carrier materials, e.g. calcite or true, in speech. In addition, several granulated materials of an inorganic or organic nature, such as dolomite or chopped plant residues, such as e.g. cork flour or sawdust is used.

Especially advantageous, application-promoting additives, which can lead to a strong reduction in the amount of use,

are further natural (animal or vegetable) or synthetic phospholipids from the series kephalins and lecithins, such as e.g. phosphatidylethanolamine, phosphatidylserine, phosphatidylcholine, sphingomyelin, phosphatidylinositol, phosphatidylglycerol, lysolecithin, plasmalogens or cardiolipin, which one e.g. can be extracted from animal or vegetable cells, especially brain, heart, lung, liver, egg white or soybeans. Usable commercial mixtures are e.g. phosphate-idylcholine mixtures. Synthetic phospholipids are e.g. di-octanoylphosphatidylcholine and dipalmititoylphosphatidylcholine.

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

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

Soaps can be mentioned as alkali, alkaline earth or possibly substituted ammonium salts of higher fatty acids (C]_o~C22^ such as, for example, the Na or K salts of oleic or stearic acid, or of natural fatty acid mixtures, such as e.g. can be extracted from coconut or tallow oil Fatty acid methyl lauric salts should also be mentioned.

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

The fatty sulfonates or sulfates are generally present as alkali, alkaline earth or optionally substituted ammonium salts and exhibit an alkali residue with 8 to 22 C atoms, under which alkyl also includes the alkyl part of acyl residues, e.g. The Na or Ca salt of lignin sulphonic acid, of the dodecyl sulfuric acid ester or a fatty alcohol sulphate mixture prepared from natural fatty acids. These also include the salts of sulfuric acid esters and sulphonic acids of fatty alcohol-ethylene oxide adducts. The sulphonated benzimidazole derivatives preferably contain 2-sulphonic acid groups and a fatty acid residue with 8-22 C atoms. Alkylarylsulfonates are e.g. The Na, Ca, or triethanolamine salts of dodecylbenzenesulfonic acid, dibutylnaphthalenesulfonic acid, or a naphthalene sulfonic acid-formaldehyde condensation product.

Furthermore, corresponding phosphates, such as e.g. salts of the phosphoric acid ester of a p-nonylphenol-(4-(14-ethylene oxide) adduct in question.

Non-ionic surfactants are primarily polyglycol ether derivatives of aliphatic or cycloaliphatic alcohols, saturated or unsaturated fatty acids and alkylphenols, which can 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 residue of the alkylphenols.

Further suitable nonionic surfactants are the water-soluble polyethylene oxide adducts with polypropylene glycol, ethylene-diaminopolypropylene glycol and alkyl polypropylene glycol containing 20 to 250 ethylene glycol ether groups and 10 to 100

g propylene glycol ether groups with 1 to 10 carbon atoms in the alkyl chain. These compounds normally contain per propylene glycol unit 1 to 5 ethylene glycol units.

Examples of nonionic surfactants include nonylphenol-polyethoxyethanols, castor oil polyglycol ethers, polypropylene-polyethylene oxide adducts, tributylphenoxypolyethyleneethanol, polyethyleneglycol and octylphenoxypolyethoxyethanol.

Furthermore, fatty acid esters of polyoxyethylene sorbitan such as the polyoxyethylene sorbitan trioleate also come into consideration.

The cationic surfactants are above all quaternary ammonium salts, which as an N-alkyl substituent contain at least one alkyl residue with 8 to 22 C atoms and as further substituents lower, optionally halogenated alkyl, benzyl or lower hydroxyalkyl residues. The salts are preferably present as halides, methyl sulphates or ethyl sulphates, e.g. stearyltrimethylammonium chloride or the benzyldi(2-chloroethyl)ethylammonium bromide. In the area of stock protection, additives which are unthinkable for human and animal nutrition are preferred.

The usual surfactants within the formulation technique are, among other things, a. described in the following publications: "Mc Cutcheon's Detergents and Emulsifiers Annual" BC Publishing Corp., Ridgewood New Jersey, 1981.

Helmut Stache "Tensid-Taschenbuch" Carl Hanser-Verlag, Munchen/Vienna 1981.

The agrochemical preparations usually contain 0.1 to 99%, in particular 0.1 to 95% active substance of formula I, 99.9 to 1%, in particular 99.8 to 5%, of a solid or liquid additive and 0 to 25 %, especially 0.1 to 25% of a surfactant.

Although concentrated agents are preferred as a commercial product, the end consumer usually uses diluted agents.

The agents may also contain further additives, such as stabilisers, foam suppressors, viscosity regulators, binders, adhesion agents, as well as fertilizers or other active substances to achieve special effects.

Such (agro)chemical agents are a component of the present invention.

The following examples serve to illustrate the invention in more detail and not to limit it. Temperatures are given in degrees Celsius. Percentages and parts refer to the weight. The following symbols are used for this: h = hour, d = day; min = minutes; RT = room temperature; N = normality; abs. = absolute, anhydrous; DMSO = dimethyl sulfoxide; DMF = dimethylformamide. The pressure values are given in millibar mB or Bar b. THF means tetrahydrofuran.

FR EMS TO LL IN GS EX S EMI? LE R

Eksemgel_Hl: Preparation of

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

..■60.8 g of 3-(2-chlorophenyl)-4-cyanopyrrole, 9.9 g of paraformaldehyde and 0.8 g of triethylamine were mixed well and then, with stirring, heated at 90°C bath temperature. The resulting melt was cooled after 1 h 15 min to RT, below which it solidified glassy. The recrystallization from toluene gave the above-mentioned product in the form of brownish crystals, m.p. 9 4-97°C...

Example_H2: Production of

N-chloromethyl-3-(2-chlorophenyl)-4-cyanopyrrole

To 60 ml of thionyl chloride, 48 g of N-hydroxymethyl-3-(2-chlorophenyl)-4-cyanopyrrole were added under vigorous stirring in several portions so that medium gas evolution was maintained. After the end of gas evolution, the mixture was stirred for a further 2 h at RT and then 2.5 h at 35-40°C. After cooling to RT, toluene was added and the mixture evaporated. The residue was recrystallized from diethyl ether/petroleum ether and gave the above-mentioned product in the form of beige crystals. Temp. 97-99°C.

Example H3: Production of

N- Acetyloxymethyl- 3-( 2- chlorophenyl)- 4- cyanopyrrole

41.4 g of N-hydroxymethyl 1-3-(.2-chlorophenyl)-4-cyanopyrrole was dissolved in 350 ml of pyridine and 1.8 g of 4-dimethylaminopyridine was added. Then 21.4 ml of acetic anhydride was slowly added dropwise at 0 to 7°C and the mixture stirred for 12 h at 0° to 7°C. The reaction mixture was then poured onto ice water and extracted twice with ethyl acetate. The extracts were washed twice with dilute, ice-cold hydrochloric acid and twice with half-saturated, aqueous sodium chloride solution, dried over sodium sulfate, filtered and the filtrate concentrated. The residue was recrystallized from diethyl ether/hexane, whereby the above-mentioned product precipitated out in the form of colorless crystals.-M.P. 91-95°C.

Example H4: Production of

N-(1- acetyloxy- 2, 2, 2- trichloroethyl)- 3-( 2, 3- dichlorophenyl)- 4-cyanopyrrole

To 2.4 g of 3-(2,4-dichlorophenyl)-4-cyanopyrrole in 50 ml of THF, 1.2 ml of chloral and 1.8 ml of triethylamine were successively added dropwise. The reaction mixture was stirred at 25°C for 1.5 h, added 0.1

g of 4-dimethylaminopyridine and cooled to -10°C. At -10° to

-5°C a solution of 0.9 ml acetyl chloride in 10 ml THF was then added dropwise very slowly and the reaction mixture was then stirred for 30 minutes at 0°C and then 1 h at RT, filtered and the filtrate evaporated. The crude product was dissolved in diethyl ether, the ether solution was washed twice with half-saturated sodium solution, dried over sodium sulfate, filtered and the filtrate

steamed. The crude product was recrystallized from diethyl ether/petroleum ether to give colorless crystals of the above product. Temp. 111-113°C.

Example H5: 4 Production of

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

To 23.7 g of 3-(2,3-dichloro-phenyl)-4-cyanopyrrole dissolved in 300 ml of THF was added 7.5 g of paraformaldehyde and then 1.5 g of 1,8-diazabicyclo[5,5,0 ]undec-7-eh. It is stirred for 3 hours

RT..Then, with stirring, 21.7 ml of thioriyl chloride is added dropwise at 20° to 30°C to the hydroxymethyl derivative water formed. The reaction mixture is stirred for 16 h at RT, then poured onto ice water and the mixture is extracted twice with ethyl acetate. The combined organic extracts are washed twice more with halogenated sodium chloride solution, dried over sodium sulfate, filtered and evaporated. Crystallization of the residue from ether/petroleum ether gives the above product in the form of beige crystals. Temp. 132-133°C.

N-(1-hydroxy-2,2,2-trichloroethyl)-3-(2,3-dichlorophenyl)-4-cyanopyrrole.

To 64.1 g of 3-cyano-4-(2,3-dichlorophenyl)-pyrrole and 1.2 ml of triethylamine in 400 ml of THF are added dropwise at 20°C to 29°C 39.6 ml of chloral. A further 2.4 ml of triethylamine and then 1.2 ml of diazabicyclo[5,4,0]urdec-7-ene are then added, and the clear solution is first stirred for 2 h at RT, then for 14 h at 0° to 5°C. The solution is then poured onto dilute hydrochloric acid and ice and the mixture is extracted twice with acetic acid ethyl ether. The organic extracts are washed three times with cold, half-saturated sodium chloride solution, dried over sodium sulfate, filtered and evaporated. Crystallization of the residue from ether/petroleum ether gives the desired product as colorless crystals. Temp. 117°C (decomposition).

' Example H7 : Manufacture, of

H-[ 1- methoxyacetyloxy)- 2, 2, 2- trichloroethyl]- 3-( 2, 3- dichloro-phenyl)- 4- cyanopyrrole 4.8 g 3-cyano-4-(2,3-dichlorophenyl)- pyrrole. Dissolve 150 ml of tetrahydrofuran and add at room temperature 0.2 ml of DBU and . then 2.3 ml of chloral. The solution is cooled to -5°C, then 3.3 ml of triethylamine is added dropwise. After stirring for 1 hour at -5°C, 2.2 ml of methoxyacetic acid chloride, dissolved in 10 ml of THF, are slowly added dropwise at -10° to -5°C. After stirring for 1 hour with a thawing cooling bath, ice water is poured and the mixture is extracted twice with acetic acid ethyl ester. The organic extracts are washed twice with cold dilute hydrochloric acid and twice with cold half-saturated sodium chloride solution, dried over sodium sulphate, filtered and evaporated. Crystallization of the residue from petroleum ether gives the above-mentioned product as colorless crystals. Temp. 88-90°C.

E xample H8: Production of •

N- [ ( methoxyacetyioxy.) methyl] — 3- ( 2 , 3- dichlorophenyl) - 4- cyanopyrrole

4.5 g of 3-cyano-4-(2,3-dichlorophenyl)-pyrrole are dissolved in 50 ml of tetrahydrofuran and 0.65 g of paraformaldehyde, 3.0 ml of triethylamine and 0.5 ml of DBU are added. The mixture is stirred for 2 h at RT, during which a clear solution occurs. 2.0 ml of ethoxyacetic acid chloride are then slowly added dropwise with stirring at 5°C. After a further 2.5 h at 0° to 5°C, filter and concentrate the filtrate. Crystallization of the residue from ether/petroleum ether gives the above product as colorless crystals, m.p. 72-75°C.

In an analogous way, the compounds in the following table can also be prepared:

Formulation examples of liquid active substances with formula I (% = weight%)

Emulsions of any desired concentration can be prepared from such concentrates by dilution with water. The active substance is dissolved in methylene chloride, sprayed onto the carrier and the solvent is then evaporated in a vacuum.

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

The active substance is mixed well with the additives and ground well in a suitable mill. You get spray powder that can be diluted with water to form suspensions of any desired concentration.

From this concentrate, emulsions with any desired concentration can be prepared by dilution with water.

Ready-to-use dusting agents are obtained when the active ingredient is mixed. with the carrier is ground in a suitable mill.

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

The finely ground active ingredient is applied in a mixer evenly to kaolin moistened with polyethylene glycol. In this way get. one dust-free casing granules.

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

Biological Examples

Example Bl: Effect against Puccinia graminis on wheat

a) Residual protective effect

Wheat plants were sprayed 6 days after sowing with a

spray liquid (0.06% active substance) made from a spray powder of the active substance. After 24 hours, the treated plants were infected with a uredospore suspension of the fungus. There is an incubation time of 48 hours at 95-100% relative humidity and. about. 20°C, the infected plants were placed in a greenhouse at approx. 22°C. The assessment of rust pustule development' took place 12 days after infection.

b) Systemic effect A spray liquid (0.006% active substance in relation to the soil volume) prepared from spray powder of the active substance was poured into wheat plants 5 days after sowing. After 48 hours, the treated plants were infected with a uredospore suspension of the fungus. After an incubation of 4 8 hours at 95-100

% relative humidity and approx. 20°C, the infected plants were placed in a greenhouse at approx. 22°C. The assessment of rust pustule development took place 12 days after' the infection.

The compounds from tables 1 to 3 showed a good effect against Puccinia fungi not only in the above-mentioned greenhouse test, but also in the open field. Untreated but infected control plants showed a Puccinia attack of 100%. Among other things, compounds No. 1.2-to 1.5,1.9,1.13,2.11, 2.12, 2.18, 3.2, 3.4 to 3.7, .337 to 3.42 to 3 inhibited. 46, 3.51, 3. 52 , 3 :57, 3.70, 3.73 to 3.76 and 3.94 ^Puccinia attack to 0 to 10%.

E xample B2: Effect against Cercospora ara chidicola on ground-nut plants'

a) Residual protective effect

10 - 15 cm tall peanut plants were sprayed with a spray liquid (0.006% active substance) prepared from a syringe pump of the active substance and infected 48 hours later with a conidial suspension of the fungus. The infected plants were ■

incubated 72 hours at approx. '21 C and high humidity and' then set up in a greenhouse until typical leaf spots, rot. The evaluation of the fungicidal effect took place 12 days after the infection based on the number and size of the appearing spots.

b) S ystem effect

A spray liquid (0.06% active substance in relation to the soil volume) prepared from a spray powder of the active ingredient is poured into 10-15 cm tall peanut plants. After 48 hours, the treated plants were infected with a conidia suspension of the fungus and incubated for 7 2 hours at approx. 21°C and high humidity. The plants were then set up in greenhouses and assessed after 11 days of fungal attack.

In comparison with untreated but infected control plants (number and size of spots = 100%), peanut plants that were treated in a greenhouse or in the open field with active substances from tables 1 to 3 showed a greatly reduced Cer- . cospora attack. 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 , prevented

3.69, 3.70, 3.75 and 3.95 Cercospora attack almost completely (8%) .

Example B3: Effect against Botrytis cinerea on beans Residual protective effect

About. 10 cm tall bean plants were sprayed with a spray liquid (0.02% active substance) prepared from a spray powder of the active substance. After 48 hours, the treated plants were infected with a conidia suspension of the fungus. After an incubation of the infected plants for 3 days at 95-100% humidity and 21°C, the fungal attack was assessed. The compounds from tables 1 to 3 not only inhibit the fungal infection very strongly in the above-mentioned 'model test', but also in the open field. At a concentration of 0.02%, the compounds No. 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, 31.1 to 3.7, 3.9, 3.16 to 3. 22 , 3.26 , 3.30,. 3. 33,' 3. 3<7>, 3.38, 3.39 to 3.52, 3.56 to 3.60, 3.65 tii: 3.80,. 3.95, 3.103, 3.105, 3.108,

3.112 and 3.113 as fully effective (disease attack 0 to 5%). Some representatives show this effect even with half the amount of use. The attack of untreated, but infected bean plants was 100%. The intermediate products no. 16 and 24 also work just as well.

Example B4: Effect against Botrytis cinerea on apple fruit Artificially damaged apples were treated, with a spray liquid made from a spray powder of the active substance being dripped onto the damaged areas. The treated fruits were then inoculated with a spore suspension of Botrytis cinerea and incubated for a week at a high humidity and approx. 20°C.

During the assessment, the rotten damage sites were counted and the fungicidal effect of the test substance derived from this. Among others, compounds No. 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, 31.1 to 3.7, 3.9 inhibited . ) almost completely. The interwoven products no. 16 and 24 also work just as well.

Example B5: Effect against Piricularia oryzae on rice Rice plants were sprayed after 2 weeks of germination with a spray liquid (0.02% active substance) prepared from a spray powder of the active substance.; After 48 hours, the treated plants were infected with a conidial suspension of the fungus. After 5 days of incubation at 95-100% relative humidity and 24°C, the fungal attack was assessed. Compounds of formula I showed a good inhibition of the Piricularia attack, thus e.g. compounds Nos. 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, 3.55 and 3.9; they reduced the attack to less than 10%, during which this effect could also be achieved under open field conditions.

Example B6: Effect against Rhizoctonia solani on cabbage Effect after soil application

The fungus was cultivated on sterile millet grains and added to a soil-sand mixture. The infected soil was filled into shells and sown with cabbage seeds. Shortly after sowing, the experimental preparation, which was formulated as a spray powder, was poured as an aqueous suspension over the soil (20 ppm active substance in relation to the soil volume). The soil bowls were then set up for 2-3 weeks at approx. 24°C in the greenhouse and always kept evenly moist by light showering. When assessing the experiment, the growth of the cabbage plants was assessed.

'After treatment with the spray powder, which as an active sub-state contained one of . the connections no.'... 1. 3 , . 2 .1, 3.20 or 3.37, over 80% of the cabbage seeds germinated and the plants had a healthy appearance.

Example B7: Residual protective effect against Venturia inaequalis on apple shoots

Apple cuttings with 10-20 cm long fresh shoots were sprayed

with a spray liquid (0.006% active substance) made from a spray powder of active substances. After 24 hours, the treated plants were infected with a conidia suspension of the fungus. The plants were then incubated for 5 days at 90-100% relative humidity and set up for 10 further days in a growth-. house at 20-24°C. Scabies attack was assessed 15 days after infection. Compounds of formula I showed good activity against Venturia sources, especially compounds 1.2, 1.3, 3.4, -- 3.5, 3.17, 3.18, 3.20, 3.22, 3.37, 3.39, 3.71 and 3.95 heme, met.scurve attack compared to untreated control plants to less than 20%. Compounds Nos. 1.3, 3.4,

3.5 and 3.17 achieved this in the open, even in a dosage of 0.002%....

E xample B8: Effect against Helminthosporium gramineum Wheat grains are contaminated with a spore suspension of the fungus and dried again. The contaminated grains are stained with a suspension. of the test substance produced from spray powder (600 ppm active substance in relation to the weight of the seeds). After 2 days, the grains are placed in suitable agar dishes and after a further 4 days, the development of the fungal colonies around the grains is assessed. The number and size of the fungal colonies are used to assess the quality of the experimental product. Below that, the compounds from tables 1 to 3, especially from table 3, prevented fungal growth to a large extent. grip (0 to 10%) .

E xample B9.: Effect against Fusarium nivale

Wheat grains are contaminated with a spore suspension of the fungus and dried again. The contaminated grains are stained with a suspension of the test substance prepared from spray powder (600 ppm active substance in relation to the weight of the seeds). After two days, the grains are placed on suitable agar plates and after a further 4 days the development of the fungal colonies around the grains is assessed. The number and size of the fungal colonies are used to judge the trial products.

In the case of grains that have been treated with spray powder, which as active ingredient contains one of the compounds from tables 1 -

3, the development of the fungal colonies was almost completely suppressed (0 to 5%).

Example B10: Grain protection: (Grainpreservative Test)

a) Short-term treatment against mold on damp maize Dried maize grains intended as animal feed (portions of 80 g) are mixed well in resealable plastic cups with active ingredients from the tables. 1 to 3 in the form of an aqueous suspension, emulsion or solution. The substance application is so great that a concentration of 0.06% AS is achieved in relation to the maize dry weight. A moistened piece of paper ensures a moisture-saturated atmosphere in the cups that are filled with corn and then closed. After 2-3 weeks of incubation at approx.' At 20°C, a mixed population of molds developed spontaneously in the maize samples treated only with water. An artificial infection is unnecessary. The extent of fungal development after 3 weeks serves to assess the effect of the compounds of formula I. b) Long-term test against mold on damp maize I. The maize samples which after 3 weeks had no fungal attack are incubated for two further months. After each month, a visual credit assessment takes place according to the same criteria as in the a trial. II. The test execution takes place in principle in the same way as under a and b, but the test substance is tested at 2000, 600 and 200 ppm AS (in relation to the maize dry weight) for 6 months.

When treated with compounds of formula I from Tables 1 to 3, the formation of molds on moist corn in all three experiments a, bl and be suppressed both in the short term (3 weeks) and in the long term (6 months).

Thus prevented e.g. compounds 1.1 to 1.6, 1.9, 1.11, 1.13, 1.15, 1.18 and 1.20 as well as some representatives from

tables 2 and 3 in all three trials a, bl and b at a sample concentration of 600 ppm AS the mold attack almost completely (0-5% attack).

In similar experiments, in which, instead of formaizet, pre-grain (oats), hay, carrot slices or pig beans were used, similar results of several months of protection were observed when treated with the above-mentioned active substances of formula I.

Claims (10)

1. Connections, characterized by . formula I in which R 1 and R 2 independently of each other mean hydrogen, halogen, methoxy or methylthio, R 1 -represents hydrogen or C 1 -C 4 -haloalkyl; Y means hydroxy, halogen or the group -O-C(O)-r^; under which R 4 means H, C 1 -C 8 -alkyl, C 1 -C 8 -haloalkyl, C 2 -C 8 -alkenyl, 2-tetrahydrofuryl, 2-tetrahydropyranyl, C 1 -C 8 -alkoxycarbonyl or the group -CH ( R^.)-XRg , wherein X means oxygen or sulfur; R 1 means hydrogen or C 1 -C 2 -alkyl, and R 6 is C 1 -C 8 -alkyl, (C 1 -C 8 -alkoxy) -C 1 -C 8 -alkyl, C 3 -C 8 -alkenyl, C 1 -C 8 -alkyny1 or unsubstituted or with halogen, C -C 8 -C 8 -alkyl, C 1 -C 8 -alkoxy and/or C 1 -C 8 -alkyloxycarbonyl substituted phenyl. 2. Compounds of formula I according to claim 1, characterized in that Ri is in the 2-position and R2 is in the 3-position in the phenyl ring and independently of each other is hydrogen, halogen, methoxy or methylthio, R^ is hydrogen or C-^-C ^ -h al o <g> enalkyl, and Y is hydroxy, halogen or the group -0-C(0)-R4,- where • R^ ■means C^ -C 8 -alkyl, C-^-C 8 -haloalkyl, 2-tetrahydrofuryl, 2-tetrahydropyranyl, C^ -C 4 -alkyloxycarbonyl or the group -CH(R^)-XRg , where X means oxygen or sulphur, Rc means hydrogen or methyl, and R6 means C-^-Cg-alkyl, (C-^-C-^-alkok sy)-C^-C^-alkyl, C3-Cg-alkenyl, C3-Cg-alkyny1 or unsubstituted or fluorine, chlorine, bromine, methyl, methoxy and/or C 1 -C 3 -alkoxycarbonyl substituted phenyl. 3. Compounds with formula I according to claim 2, characterized in that stands for H, 2-C1, 2-methoxy or 2-methylthio; R 2 is H or 3-C 1 , R 3 is hydrogen or C 1 -C 2 -haloalkyl, and Y is hydroxy, chlorine or the group -O-(C (0)-R 2 ); wherein R 2 is C - 2 -C ^-alkyl, C-^-C-j-haloalkyl, 2-tetrahydrofuryl, 2-tetrahydropyranyl, C-^-C'2-Alkoxycarbonyl or the group -CR^-ORgj wherein Rg is <C>1<-> C4-alkyl, (C-^-C3-Alkoxy)-C^-C^-alkyl, C3 - <C> g-alkenyl, C3 -Cg-alkynyl or unsubstituted or with fluorine, chlorine, bromine, methyl, methoxy, ethoxycarbonyl and/or methoxycarbonyl substituted phenyl. 4. Compounds of formula I according to claim 3. characterized in that means H, 2-Cl,. 2-methoxy or 2-methylthio; R 2 means H or 3-C 1 ; R3 is. hydrogen or CC13 and Y is hydroxy, chlorine or the group -O-C (0)-R^ ; wherein R^ is C-^-C^ alkyl, C-^-C^ haloalkyl,' 2-tetrahydrofuryl, 2-tetrahydropyranyl, methoxycarbonyl or the group -CH 2 0R^^ where Rg is C-^-C^-alkyl, methoxymethyl, ethoxymethyl, methoxyethyl, allyl, . propargyl, phenyl or with fluorine, chlorine, bromine, methyl, methoxy and/or methoxycarbonyl substituted, phenyl.. 5. Compound of formula I according to kravl, characterized in that it is selected from: N-(hydroxymethyl)-3-(3-chlorophenyl)-4-cyanopyrrole, N-(1-hydroxy-2,2,2-trichloroethyl)-3-(3-methoxyphenyl)-4-cyanopyrrole, N-(chloromethyl)-3-(3-methoxyphenyl)-4-cyanopyrrole, N-(1,2,2,2-tetrachloroethyl)-3-(3-methoxyphenyl)-4-cyanopyrrole, N-(1,2,2,2-tetrachloroethyl)-3-(3-bromophenyl)-4-cyanopyrrole,. 6. Compound with formula I. according to claim 2, characterized in that it is selected from the series: N-(1-acetyloxy-2,2,2-trichloroethyl)-3-(2,3-dichlorophenyl)-4-cyanopyrrole, N-. (1-hydroxy-2,2,2-trichloroethyl)-3-(2,3-dichlorophenyl)-4-cyanopyrrole, N-(1-methoxyacetyloxy-2,2,2-trichloroethyl)-3-(2,3-dichloro-phenyl)-4-cyanopyrrole, N-(methoxyacetyloxymethyl)-3-(2;3-dichlorophenyl)-4-cyanopyrrole, N-[1-(n-butylcarbonyloxy)-2,2,2-trichloroethyl]-3-(2,3-dichlorophenyl)-4^-cyanopyrro, N-[1-(n-propoxyacetyloxy)-2,2,2-trichloroethyl]-3-(2,3-dichlorophenyl)-4-cyanopyrrole, N-[1-(n-butoxyacetyloxy)-2,2,2-trichloroethyl]-3-(2,'3-dichloro-phenyl)-4-cyanopyrrole, N-[1-(n-butoxyacetyloxy)ethyl].-3-(2,3-dichlorophenyl)-4-cyanopyrrole,' N-[1-(propargyloxyacetyloxy)-2,2,2-trichloroethyl]-3-(2,3-dichlorophenyl)-4-cyanopyrrole. 7. Compound with formula I according to claim 1, characterized in that it is selected from the series: 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-ti-(isopropoxyacetyloxy)-2,2,2-trichloroethyl]-3-(2-chlorophenyl)-4-cyanopyrrole, N-[1-(methoxyacetyloxy)-2,2,2-trichloroethyl]-3-(2-methylthio-phenyl)-4-cyanopyrrole, N-(methoxyacetyl)-3-(2-chlorophenyl)-4-cyanopyrrbl. 8. Microbicidal agent for combating or preventing an attack on living plants and/or preserving perishable storage materials of vegetable or animal origin, characterized in that it contains a compound of formula I as at least one active ingredient. 9. - Procedure for combating or preventing an attack on cultivated plants by phytopathogenic microorganisms, characterized by applying a compound of formula I to the plants, ■ the plant parts or their place of growth. 10. Procedure for conservation according to for the protection of storage or storage material of vegetable and/or animal origin against harmful microorganisms, characterized by . that the material is treated with a microbicidally effective amount of at least one compound of formula I.