BG61035B1 - Thiazolyl-5-carbonamide derivatives and plant control preparations - Google Patents

Abstract

The invention relates to thiazolyl-5-carbonamide derivatives of the formula to their acid addition salts and metal salt complexes, and to agrochemicals containing as active substance a compound of this group. The invention also relates to a method for the preparation of the compounds and for their use in the control of microorganisms damaging plants, in particular against fungal diseases.

Description

TECHNICAL FIELD

The invention relates to novel thiazolyl-5-carbonamide derivatives, to a process for their preparation, and to agrochemical agents containing at least one compound from this group as an active ingredient. The invention also relates to a process for the preparation of said agents, and to their use, as well as the active ingredients, for combating microorganisms, in particular microorganisms that damage plants, primarily fungi.

TECHNICAL ESSENCE

OF THE INVENTION

The compounds according to the invention correspond to general formula I and include their corresponding acid addition salts and metal salt complexes.

In this formula R ₃ represents 2-furanyl, 2-thienyl, 3-furanyl or 3-thienyl, R ₁ and R ₂ independently of one another represent a/ C ₃ -C ₆ ~cycloalkyl, which is unsubstituted or substituted by methyl or methylthio, b/ the group -CH ₂ -XR ₄ , and c/ one of the two substituents R _[ or R ₂ also represents hydrogen or a C, -C ₄ -alkyl radical, in which case X represents oxygen or sulfur, R ₄ represents C, -C ₄ -alkyl, which is unsubstituted or may be substituted by halogen, or in the case of C ₂ -C ₄ -alkyl also by C _t -C ₃ -aakokcH, or where R ₄ represents C ₃ -C ₄ -alkenyl, C ₃ -C ₄ -alkynyl or a phenyl or a benzyl group, the aromatic ring of which is unsubstituted or may be substituted by halogen, C1- _C2 -alkyl, _C1 - _C2 -alkoxy, _CF3 or _NOr

By “alkyl” alone or as a component of other substituents, such as haloalkyl or alkoxy, is meant, depending on the number of carbon atoms, for example methyl, ethyl, propyl, butyl, as well as their isomers isopropyl, isobutyl, tert.-butyl or sec. .butyl. Halogen, designated as “hal”, represents fluorine, chlorine, bromine or iodine. Halogenalkyl means simple to perhalogenated radicals, such as for example CHCl ₂ , CH ₂ F, CCl ₃ , CH ₂ Cl, CHF ₂ , CF ₃ , CH ₂ CH ₂ Br, C ₂ Cl ₅ , CH ₂ Br,. CHBrCl 5 etc. Cycloalkyl means, depending on the number of carbon atoms, for example cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.

The compounds of the general formula I are stable oils or solids at ordinary temperatures and are distinguished by valuable microbicidal properties. They can be used in the agricultural sector or related areas for preventive purposes or for the control of plant-damaging microorganisms. The active ingredients of the general formula I according to the invention are distinguished not only by their excellent microbicidal, in particular fungicidal, action at low use concentrations, but also by their particularly good tolerance by plants.

The compounds of general formula 1 have an asymmetric carbon atom adjacent to the nitrile group. They can therefore be separated in the usual manner into optical antipodes. These antipodes have different microbicidal activities.

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

The salts according to the invention are in particular addition salts with safe organic or inorganic acids, such as hydrochloric, hydrobromic or hydroiodic acid, sulfuric acid, phosphoric acid, phosphorous acid, nitric acid, or organic acids such as acetic acid, trifluoroacetic acid, trichloroacetic acid, propionic acid, glycolic acid, thiocyanic acid, lactic acid, succinic acid, citric acid, benzoic acid, cinnamic acid, oxalic acid, formic acid, benzenesulfonic acid, paratoluenesulfonic acid, methanesulfonic acid, salicylic acid, paraaminosalicylic acid, 2-phenoxybenzoic acid, 2-acetoxybenzoic acid or 1,2-naphthalenedisulfonic acid.

The metal salt complexes of the general formula I consist of an organic molecule and an inorganic or organic metal salt, for example halides, nitrates, sulfates, phosphates, acetates, trifluoroacetates, trichloroacetates, propionates, tetrates, sulfonates, salicylates, benzoates, etc. of elements from the second main group, such as calcium or magnesium, and from the third or fourth main group, such as aluminum, tin or lead, as well as from the first to eighth subgroups, such as chromium, manganese, iron, cobalt, nickel, copper, zinc, etc. Elements from the subgroups of the fourth period are preferred. The metals can occur in different valencies. The metal complexes can have one or more nuclei, i.e. they can contain one or more parts of organic molecules as ligands.

An important group of plant fungicides and insecticides are those compounds of general formula I, in which one of the two substituents R ₍ u R ₂ denotes C ₃ -C ₆ -cycloalkyl, which is unsubstituted or substituted by methyl or methylthio, and the other substituent represents d/ cyclobutyl, cyclopropyl, methylcyclopropyl or methylthiocyclopropyl, e/ the group -CH ₂ -XR ₄ or e/ hydrogen or C, -C ₄ -alkyl, while R ₃ , X and R ₄ have the meanings indicated above.

These compounds may be further referred to as Group 1A compounds.

Among the compounds of group 1A, those in which one of the two substituents R and _R2 represents _C3 - _C6 -cycloalkyl and the other represents cyclobutyl or cyclopropyl, while _R3 has the indicated meaning (group 1AA), and among them again those in which R1 and _R2 represent cyclopropyl, may be mentioned as preferred.

Important compounds of group IA are also those in which Rj represents C ₃ -C ₆ -cycloalkyl, which is unsubstituted or may be substituted by methyl or methylthio, R ₂ represents hydrogen or C 1 -C 6 -alkyl, or the group -CH ₂ XR ₄ , X represents oxygen or sulfur and R ₄ represents C 1 -C 6 -alkyl, which is unsubstituted or substituted by fluorine, or in the case of representing C ₂ -C ₄ -alkyl, may also be substituted by C 1 -C 6 -alkoxy, or R ₄ represents allyl, propargyl, phenyl or benzyl, wherein the aromatic rings of the latter residues are unsubstituted or may be substituted by one or two fluorine, chlorine, methyl, ethyl, methoxy or trifluoromethyl substituents, while R ₃ has the previously indicated meaning (group 1B).

Preferred are those compounds of group IB in which X represents oxygen (group IBB).

Important compounds within the IBB group are those in which Rj represents cyclobutyl, cyclopropyl, methylcyclopropyl or methylthiocyclopropyl,

R ₂ - hydrogen, C 1 -C ₄ -alkyl or -CH ₂ -OR ₄ , wherein

R1 represents C1-C4 alkyl which is unsubstituted or may be substituted by fluorine, methoxy or ethoxy, or where _R4 represents allyl, propargyl, phenyl, chlorophenyl, fluorophenyl, benzyl, chlorobenzyl or fluorobenzyl (subgroup 1b).

Within group 1b, compounds in which R ₁ represents cyclopropyl are preferred.

R ₂ - hydrogen, C 1-4 alkyl or -CH ₂ -OR ₄ , wherein

R ₄ represents methyl, ethyl, fluoromethyl, difluoromethyl, trifluoromethyl, allyl, propargyl, phenyl or benzyl, while

R ₃ has the indicated meanings /=subgroup 1bb/.

Particularly preferred compounds within group 1bb are those in which R ₂ represents hydrogen, C 1 -C 1 -alkyl, methoxymethyl or ethoxymethyl.

Important compounds are also those of group 1a, in which R, denotes hydrogen, C,C ₄ -alkyl or the group -CH ₂ -XR ₄ , X denotes oxygen or sulfur and

R, denotes C1-C4-alkyl, unsubstituted or substituted by fluorine, or in the case of _C2 - _C4- alkyl, may be substituted by C1- _C3 -alkoxy, or where _R4 denotes allyl, propargyl, phenyl or benzyl, the aromatic rings of the latter residues being unsubstituted or substituted by one or two fluorine, chlorine, methyl, ethyl, methoxy or trifluoromethyl substituents, while

R ₂ represents C ₃ -C ₆ -cycloalkyl which is unsubstituted or may be substituted by methyl or methylthio, while

R ₃ has the meanings already indicated /group 1C/, and in particular those in which X represents oxygen /=group 1CC/.

Within this group, 1CC is presented3

II III 1111.11 honor such compounds in which R, denotes hydrogen, C,-C ₄ -alkyl or -CH ₂ -OR ₄ ,

R ₂ - cyclobutyl, cyclopropyl, methylcyclopropyl or methylthiocyclopropyl and

R4 represents C1-C4-alkyl which is unsubstituted or may be substituted by fluorine, or in the case where _R4 represents _C2 - _C4 -alkyl it may also be substituted by methoxy or ethoxy, or in which in addition

_R4 represents allyl, propargyl, chlorobenzyl, fluorobenzyl, benzyl, chlorophenyl or fluorobenzyl, while

R ₃ has the given meanings /=subgroup 1c/.

Among these compounds are in particular compounds in which R ₍ 15) represents hydrogen, C1-C3-alkyl, methoxymethyl or ethoxymethyl.

Also important compounds are those triazolyl-5-carbonamide derivatives of general formula I, in which one of the two substituents R1 and _R2 represents the group _-CH2 - _XR4 , and the other substituent represents hydrogen, C1-C4 alkyl or -CH2-XR4.

4’

X stands for oxygen or sulfur,

R ₃ has the meanings specified above and

R, denotes C1-C4-alkyl which is unsubstituted or may be substituted by fluorine, or in the case of _C2 - _C4 -alkyl, may be substituted by C1-C4-alkoxy, or in the formula _R4 represents allyl, propargyl, phenyl or benzyl, the aromatic ring of the latter residues being unsubstituted or may be substituted by one or two of the substituents fluorine, chlorine, methyl, ethyl, methoxy or trifluoromethyl /=subgroup 1D/. 35

Among these compounds from group 1D, those with advantages are those in which

Rj represents the group -CH ₂ -OR ₄

R ₂ represents hydrogen, C 1 -C ₄ -alkyl or -CH .-OR ., 40

4’

R ₃ has the meanings specified above and

R 1 represents C 1 -C 4 alkyl which is unsubstituted or substituted by fluorine, methoxy or ethoxy, or in which R ₄ represents allyl, propargyl, phenyl, chlorophenyl, fluorophenyl, benzyl, chlorobenzyl or fluorobenzyl (subgroup IIID).

Subgroup 1DD includes those compounds of formula I in which R ₄ represents methyl, ethyl, fluoromethyl, difluoromethyl, trifluoromethyl, allyl, propargyl, phenyl or benzyl (=subgroup 1d).

Particularly preferred are the compounds of the last mentioned subgroup 1e in which _R2 is hydrogen or C1-C4-alkyl. Also particularly preferred from subgroup 1e are compounds in which R1 and _R2 independently of one another are methoxymethyl or ethoxymethyl.

Furthermore, among the compounds of subgroup 1D, those compounds have advantages in which

R1 represents hydrogen, C1- _C4- alkyl or the group _-CH2 - _OR4 ,

R, means -CH,-O-R,,

R ₃ has the meanings given above and R 4 represents C 1 -C 4 alkyl which is unsubstituted or substituted by fluorine, methoxy or ethoxy, or R ₄ represents allyl, propargyl, phenyl, chlorophenyl, fluorophenyl, benzyl, chlorobenzyl or fluorobenzyl (=subgroup 1E).

Among the compounds of group IE, those compounds in which R ₄ represents methyl, ethyl, fluoromethyl, difluoromethyl, trifluoromethyl, allyl, propargyl, phenyl or benzyl (=subgroup 1EE) are preferred.

Particularly preferred among the compounds of group IEE are those in which R1 represents hydrogen or C1-C4 alkyl.

An important group of plant fungicides are furthermore those compounds of formula I, in which either [a/R _] denotes CH ₃ , C ₂ H ₅ , n-C ₃ H ₇ , isoC ₃ H ₇ , CH ₂ -O-CH ₃ , CH ₂ -O-C ₂ H ₅ or cyclopropyl, and

_R2 represents cyclopropyl, or in which R1 represents _CH2 -O- _CH3 , _CH2 -O- _C2H5 , _CH2 - _O - _CHF2 or cyclopropyl and _R2 represents C ₍ -C3 ₎ -alkyl and

R ₃ has the meanings indicated at the beginning /subgroup “alpha”/.

Among these compounds from the “alpha” group, one of the preferred subgroups can be mentioned as the one in which

R, means CH ₃ , C ₂ H ₅ , n-C ₃ H ₇ or isoC ₃ H ₇ and

R ₂ means cyclopropyl /subgroup "beta"/.

Furthermore, among the compounds of the “alpha” group, another preferred subgroup can be mentioned that in which

R denotes CH ₂ -O-CH ₃ , CH ₂ -O-C ₂ H ₅ or cyclopropyl and

R ₂ means CH ₃ , C ₂ H ₅ , n-C ₃ H ₇ , iso-C ₃ H ₇ or cyclopropyl /subgroup “gamma”/.

The compounds of general formula I are prepared by reacting thiazolyl5-carboxylic acid of formula V

or its acid halide, ester or acid anhydride with aminoacetonitrile of formula II

CN ¹ /II/

H ₂ N - CH - R ₃ in the presence or absence of a condensing agent or an acid acceptor, in which the substituents R , R ₂ and R ₃ have the meanings given for formula I. It is expedient to separate the amino component II in a slight excess relative to the component V /for example up to 2 molar equivalents/.

Acid halide is primarily understood to mean chloride, bromide or iodide, acid ester is understood to mean readily reactive derivatives of C- _C6 alcohols, for example methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, amyl ester, etc. The reaction of V with II is carried out in the absence or preferably in the presence of a condensing agent, respectively an acid acceptor /proton acceptor/.

An acid halide of formula V can also be prepared “in situ” from thiazolyl-5-carboxylic acid by reacting the same with reactants II in the presence of a thionyl halide, for example SOCl ₂ and imidazole. This variant of the method is included in the process described above.

The reaction temperature range is -20°C to 150°C, preferably -5° to +80°C.

Proton acceptors include, for example, inorganic or organic bases, such as alkali or alkaline earth compounds, for example hydroxides, oxides or carbonates of lithium, sodium, potassium, magnesium, calcium, strontium and barium, or also hydrides, such as sodium hydride. Organic bases include, for example, tertiary amines, such as triethylamine, triethylenediamine, pyridine, 4-dimethylaminopyridine.

Although not required, solvents or diluents can be used for the reaction. Examples that may be mentioned include: halogenated hydrocarbons, in particular chlorinated hydrocarbons, such as tetrachloroethylene, tetrachloroethane, dichloropropane, methylene chloride, dichlorobutane, chloroform, tetrachloromethane, trichloroethane, trichloroethylene, pentachloroethane, 1,2-dichloroethane, 1,1-dichloroethane, 1,2-cisdichloroethane, chlorobenzene, fluorobenzene, bromobenzene, dichlorobenzene, dibromobenzene, chlorotoluene; ethers such as ethylpropyl ether, methyltert-butyl ether, n-butylethyl ether, di-n-butyl ether, di-iso-butyl ether, diisoamyl ether, diisopropyl ether, anisole, cyclohexylmethyl ether, diethyl ether, ethylene glycol dimethyl ether, tetrahydrofuran, dioxane, thioanisole, dichlorodiethyl ether, nitro group-containing hydrocarbons such as nitromethane, nitroethane, nitrobenzene, chloronitrobenzene, o-nitrotoluene; nitriles such as acetonitrile, butyronitrile, isobutyronitrile, benzonitrile, meta-chlorobenzonitrile; aliphatic or cycloaliphatic hydrocarbons such as heptane, hexane, octane, nonane, cymene, gasoline fractions within a boiling range of 70°C to 190°C, cyclohexane, methylcyclohexane, decalin, petroleum ether, ligroin, trimethylpentane such as 2,3,3-trimethylpentane; esters such as ethyl acetate, acetethyl acetate, isobutyl acetate; amides, for example formamide, methylformamide, dimethylformamide; ketones such as acetone, methylethylketone; optionally also water. Mixtures of the solvents and diluents mentioned are also contemplated.

The starting products of formula II can be obtained according to the Streckner synthesis by reacting Aldehyde III with hydrocyanic acid, respectively with alkaline cyanide /for example sodium cyanide/, in the presence of ammonia or an ammonium salt:

Rj-CHO + HCN /alkaline cyanide NH/NH ₄ Q II

It is advisable to use a binary solvent system consisting on the one hand of an ether /diethyl ether, dioxane, tetrahydrofuran, etc./ or aromatic hydrocarbon /benzene, toluene, xylene/ and on the other hand of water and to operate at 0° to 100°C.

The starting products of general formula V are obtained by reacting a thioamide of formula VI with an α-halogen-β-ketoester of general formula

II III II III II formula VII to thiazolyl-5-carboxylic acid ester with formula Va nh ₂ I

R,-C _t

S

O - C - R ₂ + CH - COOR's'

Hal

Va

VI VII where R' is a C^Cg-hydrocarbon, and then, if desired, is converted to the carboxylic acid V by saponification. The reaction can be carried out in a protic solvent such as an alcohol or in an aprotic solvent such as benzene, toluene, cyclohexane, etc. In some cases, the addition of a proton acceptor such as sodium acetate /acetic acid or a tertiary base/ e.g. pyridine, triethylamine, etc./ is necessary. Initially, the reaction is carried out at temperatures between -20°C and +40°C, preferably at -20°C to +20°C. It is then heated to +30°C to 140°C, preferably from +50°C to +110°C. If, for example, benzene, toluene or cyclohexane is used, the water that is separated can be removed with a water separator.

According to another variant of the process, the intermediate of formula V can also be prepared by first acylated a thioamide of formula VI with an acid halide of formula VIII to give an N-acylthioamide of formula IX nh ₂ nh ₂ -co - r ₂

R. - С + Hal-CO-R, ------► R. - C ¹ ъ ^{2 1} * ss

VI VIIIix

It is therefore expedient to work in an inert solvent such as acetonitrile or tetrahydrofuran. A tertiary base such as pyridine, triethylamine, 4-dimethylaminopyridine, etc. is preferably used as proton acceptor. The reaction should take place in the temperature range from -40°C to +80°C, preferably -20°C to +20°C. Compound IX is then condensed with a halogen ester of formula X to give a thiazolyl-5-carboxylic acid ester of formula Va and then, if desired, converted in the usual manner to compound V:

NH -CO - R ₂ ¹ Λ, 50

R, - C + Hal-CH,-COOR· ► Va ’ g

S

IXX

In the cyclization, the N-acylthioamide IX is treated in a protic solvent (such as a lower alcohol) or an aprotic solvent with an alcoholate (e.g. CH ₃ -ONa) or with NaH at a temperature of -40°C to +20°C, preferably -30°C to 0°C, and then the halogen ester X is added at a temperature of -20°C to +30°C, preferably -10°C to +10°C. This is followed by heating for several hours at a temperature of +40°C to 120°C, preferably +60°C to +100°C, to remove the water of reaction.

In the above-mentioned formulas Va to X, the substituents R 1 and R ₂ have the meanings given for formula I.

The described methods of preparation, including all steps, are an integral part of the invention.

The novel intermediates of formula V and their esters with C1- _C6 alcohols are another component of the invention, preferably those in which _R1 and _R2 have the meanings indicated for the "alpha" subgroup.

Surprisingly, it has been found that the compounds of formula I have a very advantageous biocidal spectrum for practical purposes for combating phytopathogenic microorganisms, in particular fungi. They have very advantageous medicinal and therapeutic properties and are used for the protection of numerous cultivated plants. With the active substances of formula I, pests that have appeared on plants or plant parts (fruits, flowers, foliage, stems, tubers, roots) of various useful crops can be limited or eliminated, whereby the later growing parts of the plants also remain protected from phytopathogenic microorganisms.

The compounds of formula 1 are effective, for example, against the following phytopathogenic fungi belonging to various classes: Fungi imperfecti /in particular Botrytis, also Pyricularia, Fusarium, Helminthosporium, Septoria, Cercospora, Alternaria/, Basidiomycetes /for example Rhizoctonia, Hemileia, puccinia/. They are also effective against the class Ascomycetes /for example Venturia and Erysiphe, Podosphaera, Monilinia, Uncinula/, but above all against Oomycetes /for example Phytophthora, Peronospora, Bremia, Pythium, Plas toraga/. The compounds of formula I can also be used as coating agents for the treatment of seeds (fruits, tubers, grains) and plant buds to protect against fungal infections, as well as against phytopathogenic fungi occurring in the soil.

The invention also relates to agents containing compounds of formula I as active ingredients, in particular plant protection agents, as well as to their use in the agricultural sector or in related fields.

Furthermore, the invention also includes the preparation of these agents, which is characterized by homogenizing the active substance with one or more of the substances or groups of substances described herein. Also included is a method for treating fungi, which is characterized by the use of the novel compounds of formula I, respectively the novel agents.

For the plant protection application shown here within the scope of the invention, the following plant species are considered as target crops: cereals /wheat, barley, rye, oats, rice, corn, sorghum and related species/, beets /sugar and fodder beets/, nuts, stone fruits and grapes /apples, pears, plums, peaches, almonds, cherries, strawberries, grapes, raspberries and blackberries/, pods /beans, lentils, peas, soybeans/, oilseed crops /rapeseed, mustard, poppy, olive, sunflower, coconut, castor, cocoa, peanuts/, cucurbits /pumpkins, cucumbers, watermelons/, fiber crops /cotton, hemp, flax, jute/, citrus fruits /oranges, lemons, grapefruits, tangerines/, vegetable species /spinach, salads, asparagus, cabbage species, carrots, onions, tomatoes, potatoes and peppers/, laurel plants /avocado, cinnamon, camphor/ or plants such as tobacco, walnuts, coffee, sugar cane, tea, black pepper, surfaces or plants. These other active substances can be both fertilizers, micronutrient carriers and other preparations influencing plant growth. Selective herbicides, as well as insecticides, fungicides, bactericides, nematicides, molluscicides or mixtures of several of these preparations, together with other carriers, surfactants or additives customary in formulation technology, can also be used here.

Suitable carriers and additives may be solid or liquid and may be appropriate to the objectives of the formulation technique, for example natural or regenerated mineral substances, solvents, solubilizers, dispersants, wetting agents, adhesion promoters, thickeners, binders or fertilizing agents.

A preferred method of applying the active substance of formula 1, or the agrochemical agent containing at least one of these active substances, is application to the foliage (foliar application). The frequency of application and the application rates are determined in this case depending on the intensity of the attack of the respective pathogen. The active substances of formula I can also be introduced through the soil via the root system into the plants (systemic action), by watering the plant site with a liquid preparation or by incorporating the substances in solid form into the soil, i.e. in the form of granules (soil application). In the case of crops grown in water, such granules can be dosed into water-filled rice fields. The compounds of formula I can also be applied to seed grains, whereby the grains are either soaked in a liquid preparation of the active substance or a layer of solid preparation is applied to them.

The compounds of the general formula I are therefore used in unmodified form or preferably together with auxiliaries customary in formulation technology. It is expedient for this purpose to process them into emulsion concentrates, brushable pastes, directly sprayable or dilutable solutions, dilutable emulsions, soluble powders, sprayable solutions, dusting agents, granules by encapsulation in, for example, polymeric substances. The application methods such as spraying, aerosolizing, dusting, sprinkling, brushing or pouring are selected, as is the type of agent, in accordance with the intended purpose and the specific conditions. Favorable application rates are generally in the range of 50 g to 5 kg active substance per ha, preferably from 25 g to 2 kg active substance per ha, in particular from 30 g to 300 g active substance per ha.

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

Suitable solvents include: aliphatic hydrocarbons, preferably the C ₈ to C 10 fractions such as xylene mixtures or substituted naphthalenes, phthalic acid esters such as dibutyl or dioctyl phthalate, aliphatic hydrocarbons such as cyclohexane or paraffins, alcohols or glycols, as well as their ethers and esters such as ethanol, ethylene glycol, ethylene glycol monomethyl or ethyl ether, ketones such as cyclohexanone, highly polar solvents such as N-methyl-2-pyrrolidone, dimethyl sulfoxide or dimethylformamide, and optionally epoxidized vegetable oils such as epoxidized coconut oil or soybean oil, or water.

As solid carriers, for example for dusting agents and soluble powders, natural mineral flours such as calcite, talc, kaolin, montmorillonite or attapulgite are generally used.

Particularly useful application-supporting additives, which can lead to a significant reduction in consumption amounts, are furthermore natural /animal or plant/ or synthetic phospholipids from the group of cephalin and lecithin, which can be obtained, for example, from soybeans.

Surface-active compounds, depending on the type of active substance to be formulated, include nonionic, cationic and/or anionic surfactants with good emulsifying, dispersing and wetting properties. Surfactants are also to be understood as mixtures of surfactants.

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

Soaps are alkaline, alkaline earth or optionally substituted ammonium salts of higher fatty acids /C ₁₀ -C ₂₂ /, for example sodium or potassium salts of oleic or stearic acid, or of mixtures of natural fatty acids, which can be obtained for example from coconut oil or tallow, besides which methyl laurine salts of fatty acids can also be mentioned.

Nonionic surfactants include polyglycol ether derivatives of aliphatic or cycloaliphatic alcohols, saturated or unsaturated fatty acids and alkylphenols, which may contain 3 to 30 glycol ether groups and 8 to 20 carbon atoms in the (aliphatic) hydrocarbon residue and 6 to 18 carbon atoms in the alkyl residue of the alkylphenol.

As examples of nonionic surfactants, mention may be made of nonylphenolpolyethoxyethanols, ricin polyglycol ether, polypropylene-polyethylene oxide adducts, tributylphenoxypolyethyleneethanol, polyethylene glycol and octylphenoxypolyethoxyethanol.

In addition, fatty acid esters of polyoxyethylene sorbitan, such as polyoxyethylene sorbitan trioleate, are also contemplated.

Cationic surfactants are primarily quaternary ammonium salts which contain at least one alkyl radical with 8 to 22 carbon atoms as N-substituent and lower, optionally halogenated alkyl, benzyl or lower hydroxyalkyl radicals as other substituents.

Other surfactants used in the formulation technique can be taken from the relevant specialized literature or are known to those skilled in the art.

The anionic, nonionic or cationic surfactants used in the formulation technique are known to specialists or can be taken from the relevant specialized literature:

-''McCutcheon's Detergents and Emulsifiers Annual", Me Publishing Corp., Glen Rock, New Jersey, 1988

-M. and J. Asn, "Encyclopedia of Surfactans", Vol. I-Ill, Chemical Publishing Co., New York, 1980-1981.

-Dr. Helmut Stache “Tensid-Tasdchenbuch”, Carl Hanser Verlag, Muenchen / Wien, 1981.

The agrochemical preparations generally contain 0.1 to 99%, in particular 0.1 to 95% of active ingredient of formula 1, 99.9 to 1%, in particular 99.9 to 5% of solid or liquid additives and 0 to 25%, in particular 0.1 to 25% of surfactant.

While commercial products often prefer concentrated products, the end user usually uses diluted products.

The agents may also contain other additives such as stabilizers, defoamers, viscosity regulators, binders, adhesion promoters, as well as fertilizers or other active substances to achieve special effects.

Examples of implementation of the invention

The following examples serve to further illustrate the invention without limiting it.

Examples of obtaining the active substances

Example 1a. Preparation of 2-methoxymethyl-4-methylthiazole-5-carboxylic acid ethyl ester with ₃

CH ₃ OSH ₂ - X-COOS ₂ H ₅

31.3 g of ethyl chloroacetic acid ester were mixed in 400 ml of benzene at room temperature with vigorous stirring with 20 g of methoxythioacetamide and heated under reflux using a water separator for 4.5 h. After cooling to room temperature, the benzene reaction solution was diluted with 500 ml of ethyl acetate, washed twice with 80 ml of 10% sodium hydroxide solution and twice with 50 ml of water, dried over sodium sulfate and filtered. The solvent mixture was removed by evaporation. The remaining yellow oil was crystallized by trituration with diisopropyl ether. The colored beige crystals melted at 36-37°C.

b/ preparation of 2-methoxymethyl-4-methylthiazole-5-carboxylic acid

CH ₃

CH ₃ OCH ₂ - soon

22.1 g of ethyl ester of 2-methoxymethyl-4-methylthiazole-5-carboxylic acid are mixed at room temperature with 6.7 g of 85% potassium hydroxide in 100 ml of ethanol and then heated for 18 h under reflux. After cooling, the ethanol is removed by distillation and the residue is dissolved in 200 ml of water. After stirring with activated carbon, the mixture is filtered and the filtrate is acidified with concentrated hydrochloric acid with intensive stirring. The resulting yellowish crystals are separated by filtration, washed with water and dried. After recrystallization from tetrahydrofuran /petroleum ether /35-45°C/ /=10:1/ the crystals formed melt at 168-169.5°C.

c/ preparation of 2-(2-methoxymethyl-3-methylthiazolyl-5-carbonylamino)-2-(3-thienyl)-acetonitrile

To 3.5 g of methoxymethyl-4-methylthiazolyl-5-carboxylic acid in 40 ml of pyridine were added dropwise 2.38 g of thionyl chloride with stirring at 0°C over 1/4 h. After stirring for 1 h at 0°C, 3.5 g of 2-(3-thienyl)-aminoacetonitrile hydrochloride were added and the mixture was stirred for a further 18 h under nitrogen. After adding 200 ml of ice water and 100 ml of ethyl acetate with stirring, the mixture was acidified with 50 ml of concentrated hydrochloric acid, the organic phase was separated and extracted once more with 70 ml of ethyl acetate. The combined extracts were washed twice with 100 ml of 1N hydrochloric acid and once with 100 ml of saturated sodium bicarbonate solution, dried over sodium sulfate, filtered and the solvent evaporated. The residue in the form of a yellowish oil was allowed to crystallize by trituration with diisopropyl ether. The pale yellow crystals melted at 111-113°C.

Example 2. Preparation of 2-(2-methyl-4-cyclopropylthiazole-5-carbonylamino)-2-(3-thienyl)-acetonitrile.

8.75 g of 2-(3-thienyl)-aminoacetonitrile hydrochloride are suspended in 200 ml of ethyl acetate and after cooling to +5°C, 12 g of triethylamine are added with stirring for 5 min. With intensive stirring for 1 h, 10 g of 2-methyl-4-cyclopropylthiazole-5-carboxylic acid chloride in 100 ml of ethyl acetate are added dropwise at 5°C, after which stirring is continued for 2 h at room temperature, 100 ml of water are added and the aqueous phase is removed. The ethyl acetate solution is washed twice more with 50 ml of water, dried over sodium sulfate, filtered and the solvent is removed by evaporation. The resulting oil is purified by column chromatography over silica gel /tetrahydrofuran:hexane = 1:1/. After evaporation of the solvent mixture, the resulting brown oil was triturated with petroleum ether (50-70°C) for crystallization and recrystallized from hexane/dichloromethane. The beige colored crystals melted at 108-110°C.

In a similar way, the following compounds can be obtained:

Table 1: Compounds with formula

T = 2-furanyl

T ₂ = 3-furanyl

T ₃ = 2-thienyl

T = 3-thienyl 4

CP= cyclopropyl

United. ^R < ^R2 R ₃ Physical constant No.

1 H Wednesday T, 2 -sn ₃ Wednesday T ₄ Melting point: 108-110°C 3 - ^with l Wednesday ^T h Melting point: 116-117°C 4 n -sn base ₃ T ₄ 5 Wednesday Wednesday ^T 4 Melting point: 93-95°C 6 n Wednesday T ₄ 7 Wednesday -sn ₂ osn ₃ Vol. 1 8 -sn ₃ Wednesday t, Melting point: 67-68°C 9 -CH ₂ OCH ₃ Wednesday ^t ₄ Melting point: 135-136.5°C 10 -s ₂ n ₅ -sn ₂ osn ₃ T ₄ 11 Wednesday n ^T 4 12 -sn ₃ Wednesday t ₂ Melting point: 91-93°C SCH 13 n ^T 4 14 -CH ₂ OCH ₃ n ^T , 15 Wednesday -sn ₃ ^T , 16 Wednesday -CH ₂ OCH ₃ ^T 4 17 -CH ₂ OCH ₃ -sn osn T ₄ 18 -sn ₃ Wednesday ^T h Melting point: 135-136°C 19 -s ₂ n ₅ -CH ₂ OC ₂ H ₅ T, 20 Cyclobutyl -sn ₃ T ₄ 21 -sn ₂ osn ₃ n ^T ₄ 22 -sn ₃ Cyclobutyl T ₄ 23 -CH ₂ OC ₂ H ₅ Wednesday t ₄ 24 Wednesday -sn ₃ t ₄ Melting point: 132-134°C 25 -sd -CH OCJL T 2 5 2 Ι. 5 4 26 Wednesday -ch ₂ ochf ₂ ^T h 27 -sn ₃ -CH ₂ OCH ₃ T, 10

28 -sn ₂ osn ₃ -ch ₂ ochf ₂ ^t ₄ 29 Cyclohexyl -sn ₃ ^T 4 30 -sn ₂ os ₂ n ₅ -sn ₂ osn ₃ ^t , 31 Wednesday -sn ₃ ^T 2 32 -sn ₃ -sn ₂ osn ₃ ^T h Melting point: 77-81°C 33 Wednesday -sn ₂ os ₂ n ₅ t. 34 ^S z ⁿ 7- ^H Wednesday ^T 4 Melting point: 114-115°C 35 -sn ₂ osn ₃ -sn ₃ T, Melting point: 80-81°C 36 -sn ₂ os ₂ n ₅ n ^T 4 37 -CH ₂ OCH ₂ CH ₂ OCH ₃ -sn ₃ T ₄ 38 -ch ₂ sch ₃ - ^CH h ^T 4 39 Wednesday -sn ₃ ^T h Melting point: 127-130°C 40 -sn ₃ -sn ₂ osn ₃ ^T 2 41 -CH ₂ OC ₂ H ₅ -sn ₂ osn ₃ ^T 4 42 Wednesday -sn ₂ os ₂ n ₅ ^T 4 43 -ch ₂ ochf ₂ n ^T 4 44 -S _z n ₇ -N -sn ₂ osn ₃ T ₄ sn, 45 -sn ₂ osn ₃ ^T 4 sn, 46 -sn ₃ t ₄ 47 -CH ₂ OCH ₂ CH ₂ OCH ₃ Wednesday ^T 4 48 -sn ₂ osn ₃ -sn ₃ ^T 2 Melting point: 79-80°C 49 -sn ₃ sn ₂ os ₃ ^t ₄ 50 -sn ₂ osn ₂ sn=sn ₂ - ^CH h t ₄ zCH ₃ 51 — -sn osn t ₄ 52 -ch ₂ and ₂ cf ₃ n t ₄ 53 -sn ₃ -sn ₂ os ₂ n ₅ ^t . 54 -sn ₂ osn ₃ -sn ₃ ^T h Melting point: 96-98°C 55 -C ₃ H ₇ -iso Wednesday ^T 4 Melting point: 132-133°C 56 - ^CH h t ₄ SCH, 57 —And Wednesday t ₄ 58 -sn ₂ ax ₂ ax ₂ ax ₃ -sn ₂ osn ₃ T ₄ 59 -sn ₃ -sn ₂ os ₂ n ₅ T ₄ 60 -sn ₂ o-sn ₂ -s=sn -sn ₃ T ₄ 61 -CH ₂ O <g> -sn ₃ t ₄ 62 -ch ₂ and ₂ cf ₃ -sn ₃ T ₄ 63 -ch ₂ ochf ₂ Wednesday ^T 4 SCH, 64 —and -sn ₂ osn ₃ Vol. 65 CP -s ₂ n ₅ Vol. 66 -sn ₃ -sn ₂ os ₃ n ₇ - iso T _A 4 SCH, 67 —and -sn ₃ T, 68 -sn ₂ osn ₃ -sn ₃ T ₄ Melting point: 111-113°C 69 -ch ₂ o-tO^f -sn ₃ T ₄

II III IIIIIIIIIIII

70 -sn ₂ os ₂ n ₅ SCH, -ch ₃ T. 71 —And _{-CH2OCH3 ​} ^T4 72 _{-CH2OCHF2 ​} -ch ₂ and ₃ T. 73 -sn _{3 -CH2OCHF2 ​} T, SCH, 74 ___ko -CH ₃ ^τ 3 75 -C ₃ H ₇ -iso _{-CH2OC2H5 ​ ​} L 76 -ch ₂ and ₃ -kO> -CH ₃ ^τ ₄ 77 -CP -c ₂ h ₅ T ₄ Melting point: 116-117.5°C 78 -c ₂ h ₅ CP ^T 2 Melting point: 84-86°C 79 _{-CH2OC2H5 ​ ​} -CH ₃ T ₂ SCH, 80 -CH ₃ T ₂ 81 -C ₄ H ₉ -norm CP T. SCH, 82 —and _{-CH2OC2H5 ​ ​} T. 83 -CH ₃ -ch ₂ ochf ₂ ^τ ₄ 84 -ch ₂ ochf _{2 -CH2OCH3 ​} ^T ₄ 85 -CH ₂ OCH ₂ -<g>Cl -CH ₃ ^T ₄ 86 CP CP ^τ · Melting point: 86-88°C SCH, 87 -ch ₃ ^T 4 88 -CH ₃ -ch ₂ and ₂ cf ₃ ^τ ₄ 89 -CH _n OCH ₂ CF ₃ CP ^T ₄ 90 -c ₂ h ₅ CP T ₄ Melting point: 81-83°C SCH 91 _{-CH2OC2H5 ​ ​} τ ₄ 92 -C ₄ H ₉ -norm CP ^τ ₄ n ^g / 1.5723 93 _{-CH2OC2H5 ​ ​} -CH ₃ T ₃ 94 - ^with l CP T. Melting point: 73-75°C 95 -sn ₂ osn ₃ CP T, Melting point: 81-83°C 96 -ch ₂ oc ₂ h _s -CH ₃ T ₄ 97 ^{- C2H5} _{-CH2OCH3 ​} T, 98 _{-CH2OCHF2 ​} -CH ₃ ^τ . 99 -ch ₂ and ₂ cf ₃ -ch ₂ and ₃ T ₄ SCH, 100 -c ₂ h ₅ T ₄ 101 -ch ₂ ochf ₂ -SL τ ₄ 102 -CH ₂ OCH-C ₂ H ₅ I -CH ₃ τ ₄ CH ₃ 103 -CH ₂ OCH ₂ CH ₂ OCH ₃ -CH ₃ T, 104 _{-CH2OCH3 ​} -c ₂ h ₅ τ ₄ Melting point: 111-112°C 105 -ch ₂ ochcf ₂ -ch ₃ τ ₄ 106 -ch ₂ and ₂ cf ₃ -c ₂ h ₅ T ₄ 107 -CP -C ₃ H ₇ -iso T ₄ Melting point: 108-111°C 108 -ch ₂ ochf ₂ -C ₃ H ₇ -iso T,

109 110 111 112 -sn ₂ os ₂ n ₅ -ch ₂ ochf ₂ -sn ₂ os ₂ n ₅ SCH, — -c ₂ h ₅ -ch ₃ - ^c l -C ₃ H _? -norm T. T; ^T 4 ^T < Oil Melting Point 126-129°C 113 _{-CH2OCH3 ​} -C ₃ H _? -iso 114 -ch ₂ ochf ₂ -C ₃ H ₇ -iso ^T 4 115 -CH ₂ OCH ₂ CH ₂ OCH ₃ -s ₂ n ₅ ^T 4 116 _{-CH2OC2H5 ​ ​} -C ₃ H ₇ -iso ^T 4 117 -ch ₂ and ₂ cf ₃ -sn ₃ ^T , 118 _{-CH2OC2H5 ​ ​} -s ₂ n ₅ ^T h Melting point 96-97°C 119 _{-CH2OCH3 ​} -s ₂ n ₅ ^T h Melting point 78-83»C 120 CP -s ₂ n ₅ t ₃ Melting point 106-109°C 121 _{-CH2OCH3 ​} Wednesday ^T h Melting point 104-106°C 122 _{-CH2OCH3 ​} -s ₂ n ₅ t ₂ Melting point 81-83°C 123 _{-CH2OCH3 ​} Wednesday Melting point 105-106°C 124 _{-CH2OCH3 ​} -s ₂ n ₅ T, Melting point 104-105°C 125 -C ₃ H ₇ -iso Wednesday T, Melting point 89-92°C 126 -C ₃ H ₇ -iso Wednesday ^T h Melting point 129-131°C 127 -C ₃ H _? -iso Wednesday L Melting point 109-110°C 128 -C ₃ H ₇ -norm Wednesday t, Melting point 86-87°C 129 -C ₃ H _? -norm Wednesday T ₃ Melting point 74-76°C 130 -C ₃ H ₇ -norm Wednesday T ₂ Melting point 81-83°C 131 -ch ₂ ochf ₂ -sn ₃ ^T h 132 -ch ₂ ochf ₂ -s ₂ n ₅ t. 133 -ch ₂ ochf ₂ -s ₂ n ₅ ^T 2 134 -ch ₂ ochf ₂ - ^with l ^T h 135 -ch ₂ ochf ₂ Wednesday T, 136 -ch ₂ ochf ₂ Wednesday t ₂ 137 -ch ₂ ochf ₂ Wednesday ^T h 138 CP Wednesday T ₂ Melting point 103-105°C 139 CP Wednesday T ₃ Melting point 123-126°C 140 CP -C ₃ H ₇ -norm T, Melting point 1O6-1O8°C 141 CP -C ₃ H ₇ -iso T ₂ Melting point 108-110°C 142 CP -C ₃ H ₇ -iso T, Melting point 97-100° 143 -ch ₂ and ₃ -C ₃ H ₇ -iso T ₃ Melting point 89-91°C 144 CP -C ₃ H ₇ -norm T ₂ Melting point 111-114°C 145 CP -C ₃ H ₇ -iso Tz Melting point 101-103°C 146 _{-CH2OC2H5 ​ ​} Wednesday T, Melting point 116-118°C 147 -ch ₂ and ₃ -C ₃ H ₇ -norm T ₃ Melting point 98-101°C 148 _{-CH2OC2H5 ​ ​} Wednesday Tz Melting point 123-125°C 149 -ch ₂ and ₃ -C ₃ H ₇ -iso T, Melting point 87-90°C 150 -ch ₂ and ₃ -C ₃ H ₇ -norm T, Melting point 91-94°C 151 CP -C ₃ H ₇ -norm t ₃ Melting point 103-106°C 152 -ch ₂ and ₃ -C ₃ H ₇ -norm t ₂ Melting point 85-87°C 153 _{-CH2OCH3 ​} -C ₃ H ₇ -iso T ₂ Melting point 93-95°C 154 CP -C ₃ H ₇ -norm T ₄ Melting point 114-120° 155 _{-CH2OCH3 ​} -C ₃ H _? -norm T ₄ Melting point 124-126°C 156 _{-CH2OC2H5 ​ ​} Wednesday T ₂ Melting point 109-111»Su

II III! .11 III II

Table 2: Intermediates with general formula V

CP = cyclopropyl

Compound No. R,

Physical constants

2.1 Wed. photo ₃ Melting point: 198-200°C 2.2 Wed. with ₂ n ₅ Melting point: 96-97° 2.3 Wed. C ₃ H ₇ -norm Melting point: 104-106°C 2.4 Wed. C ₃ H ₇ -iso Melting point: 84-87°C 2.5 photo ₃ Wed. Melting point: 190-191°C 2.6 with ₂ n ₅ Wed. Melting point: 158-159°C 2.7 C ₃ H _? -iso Wed. Melting point: 122-123°C 2.8 C ₃ H ₇ -norm Wed. Melting point: 161-162°C 2.9 -sn ₂ osn ₃ photo ₃ Melting point: 168-169.5°C 2.10 -sn ₂ osn ₃ with ₂ n ₅ Melting point: 146-147°C 2.11 -sn ₂ osn ₃ Wed. Melting point: 159-161°C 2.12 -sn,os,n, CH, Melting point: 185-186°C 2 2 5 3 2.13 -sn ₂ os ₂ n ₅ with ₂ n ₅ Melting point: 114-115°C 2.14 -sn ₂ os ₂ n ₅ Wed. Melting point: 132-134°C 2.15 Wed. Wed. Melting point: 102-104°C 2.16 -ch ₂ ochf ₂ photo ₃ 2.17 -ch ₂ ochf ₂ with ₂ n ₅ 2.18 -ch ₂ ochf ₂ Wed. 2.19 -sn ₂ osn ₃ C ₃ H ₇ -norm 2.20 -CH ₂ OCH ₃ C ₃ H _? -iso

In the presence of a catalyst, for example HCl, the corresponding C ₁ -C ₆ -alkyl esters of these carboxylic acids can be readily obtained from the acids in Table 2 by esterification with methanol, ethanol or one of the isomers of the alcohols propanol, pentanol or hexanol.

2. Examples of formulations of the active substances of formula I /% = weight percentages/

2.1. Powder for suspension for

spray a/ b/ with/ Active substance from table 1 25% 50% 75% Sodium ligninsulfonate 5% 5% - Sodium lauryl sulfate 3% - 5% Sodium diisobutyl naphthalenesulfonate - 6% %

Octyl phenol polyethylene glycol ether /7-8 mol ethylene oxide/ - 2% Highly dispersed silicic acid 5% 10% 10%

Kaolin 62% 27% The active substance is mixed with the additives well and ground in a suitable mill. A powder is obtained for the preparation of spray suspensions, which can be diluted with water to suspensions of any desired concentration.

2.2. Emulsion concentrate Active substance from table 1 10%

Octylphenol polyethylene glycol ether /4-5 mol ethylene oxide/ 3%

Calcium dodecylbenzenesulfonate 3% Castor oil polyglycol ether /35 mol ethylene oxide/ 4%

Cyclohexanone 34%

Xylene mixture 50%

Emulsions of any desired concentration can be obtained from the concentrate by diluting with water.

2.3 . Dusting agent a/ b/ Active substance from table 1 5% 8% Talc 95% - Kaolin - 92%

Ready-to-use dusting agents are obtained, with the active substance being

mixtures with a carrier and the resulting mixture is ground a suitable mill. 2.4. Extruded granulate Active substance from table 1 % N -Ligninsulfonate 2% Carboxymethylcellulose 1% Kaolin 87%

The active ingredient is mixed with additives, ground and moistened with water. This mixture is extruded and then dried in an air stream.

2.5. Coated granules

Active substance from table 1 3%

Polyethylene glycol /mol. weight 200/ 3% Kaolin 94%

The finely ground active ingredient is applied in a mixer to kaolin moistened with polyethylene glycol. In this way, a dust-free, coated granulate is obtained.

2.6. Suspension concentrate

Active substance from table 1 40%

Ethylene glycol 10%

Nonylphenol polyethylene glycol ether /15to1 ethylene oxide/ 6%

N-Ligninsulfonate 10%

Carboxymethylcellulose 1%

37% aqueous solution of formaldehyde 0.2%

Silicone oil in the form of a 75% aqueous emulsion 0.8%

Water 32%

The finely ground active substance is homogenized with the additives. A suspension concentrate is obtained, from which, by dilution with water, suspensions of any desired concentration can be obtained.

3. Biological examples

I. Action against Phytophthora infestans in tomatoes.

a/ Action on infected plants.

Tomato plants of the “Red Dwarf” variety are sprayed after three weeks of cultivation with a suspension of zoospores of the fungus and incubated in a cabin at 18 to 20°C and air with saturated humidity. After 24 h, the humidification is interrupted. After the plants have dried, they are sprayed with a solution containing active substances formulated from powder for the preparation of a spray suspension in a concentration of 600, 200 or 60 ppm. After the sprayed layer has dried, the mushrooms are placed back in a humid cabin for 4 days. The number and size of the characteristic spots on the leaves that have appeared during this time are a measure for assessing the activity of the test substances.

b/ Preventive systemic action.

Formulated as a powder for the preparation of spray solutions, the active substance is applied at a concentration of 60 ppm /based on the volume of soil/ to the soil surface of 3-week-old potted tomato plants of the “Cherven Gnom” variety. After a three-day stay, the lower part of the leaves of the plants is sprayed with a suspension of zoospores of Phytophthora infestans. They are kept for 5 days in a cabin at 18 to 20°C with saturated air humidity. After this time, characteristic spots form on the leaves, the number and size of which serve to assess the activity of the test substances.

The following compounds from Table 1 achieved suppression of fungal attack below 10%: No. 2, 3, 5, 8, 9, 12, 18, 24, 32, 34, 35, 39, 48, 54, 55, 63, 68, 77, 78, 90, 93, 95, 98, 104, 107, 110, 111, 113, 116, 118 to 130 and 138 to 156.

II. Action against Plasmopara viticola (Bert, et Curt) (Bert, et De Joni) on grapevine.

a/ preventive treatment with residual effect

Grapevine canes of the “Chasselas” variety are grown in a greenhouse. Three plants in the “tenth leaf” stage are sprayed with a solution prepared from a powder formulated for the production of spray solutions of the active substance (active substance 200 ppm). After the sprayed layer has dried, the leaves of the plants on the reverse side are sprayed with a suspension of fungal spores evenly. The plants are then kept for 8 days in a humid chamber. During this time, the symptoms of the disease on control plants become clearly visible. The number and size of the infected areas on the treated plants serves as a measure for assessing the activity of the test compounds.

b/ action on infected plants

Grapevine canes of the “Chasselas” variety are grown in a greenhouse and at the “tenth leaf” stage are sprayed with a suspension of Plasmoparaviticola spores on the back of the leaves. After a 24-hour stay in the humid cabin, the plants are sprayed with a solution of the active substance, which is obtained from a powder formulated as an active substance for the preparation of spray suspensions /500 ppm active substance/. The plants are then kept in the humid cabin for another seven days. During this time, the symptoms of the disease appear on control plants. The number and size of the infected areas on the treated plants serve as a measure of the assessment of the activity of the test substances.

With all compounds mentioned in Example 1, suppression of the manifestations of the disease of less than 10% is achieved.

III. Action against Pythium debaryanum on sugar beet /Beta vulgaris/.

a/ soil application

The fungus is cultivated on sterile oat grains and added to a mixture of soil and sand. Flower pots are filled with the soil thus infected and sugar beet seeds are sown in them. Immediately after sowing, the soil is watered with the test preparations formulated as powder for spray suspensions /20 ppm active substance, based on the volume of soil/. The pots are then placed in a greenhouse for 2-3 weeks at 20-24°C. The soil is kept constantly and evenly moist by lightly spraying with water. The germination of the sugar beet plants, as well as the number of healthy and diseased plants, are determined in the evaluation of the experiment.

b/ surface treatment of seeds The fungus is cultivated on sterile oat grains and added to a mixture of soil and sand. Flower pots are filled with the soil thus infected and sugar beet seeds are sown in them, which are surface treated with powder preparations /1000 ppm active substance, based on the weight of the seeds/. The sown pots are kept for 2-3 weeks in a greenhouse at 20-24°C. In this case, the soil is kept constantly evenly moist by lightly spraying with water. When assessing the results of the experiment, the germination of the sugar beet seeds, as well as the number of healthy and diseased plants, are determined.

With the compounds in Table 1, germination was achieved in over 80% of cases. The corresponding control plants germinated in less than 30% of cases and had an unhealthy appearance.

Claims (21)

1. Thiazolyl-5-carbonamide derivatives of formula I, their acid addition salts and metal salt complexes in which formula R ₃ means 2-furanyl, 2-thienyl, 3-furanyl or 3-thienyl and R ₍ u R ₂ independently of each other have the following meanings: a/ C ₃ -C ₆ cycloalkyl, which is unsubstituted or substituted by methyl or methylthio, b/ the group -CH ₂ -XR ₄ and c/ one of the two substituents R 1 or R ₂ also denotes hydrogen or C 1 -C ₄ alkyl, wherein in addition X stands for oxygen or sulfur, R represents C1-C4 alkyl which is unsubstituted or substituted by halogen, or in the case of _C2 - _C4 alkyl, may also be substituted by C1-C4 alkoxy, or _R represents _C3 - _C4 alkylene, _C3 - _C4 alkynyl or a phenyl group or a benzyl group, the aromatic ring of which is unsubstituted or substituted by halogen, by C1-C4 alkyl, by C1-C4 alkoxy, by trifluoromethyl or by a nitro group. 2. Compounds of formula I according to claim 1, in which one of the two substituents R1 and R2 represents C1-C3 cycloalkyl, which may be unsubstituted or substituted by methyl or methylthio and the other substituent represents: d/ cyclobutyl, cyclopropyl, methylcyclopropyl or methylthiocyclopropyl, e/ the group -CH ₂ -XR ₄ or e/ hydrogen or C ₍ -C ₄ , while R ₃ , X and R ₄ have the meanings given above. 3. Compounds of formula I according to claim 2, in which one of the two substituents R ₃ and R ₂ represents C ₃ -C ₆ cycloalkyl and the other represents cyclobutyl or cyclopropyl, while R ₃ has the meanings indicated above. Compounds of formula I according to claim 3, in which R1 and _R2 denote cyclopropyl. 5. Compounds of formula I according to claim 2, wherein R1 represents hydrogen or C1- _C4 alkyl or the group _-CH2 - _XR4 , X represents oxygen or sulfur and R, represents C,-C,alkyl which is unsubstituted or substituted by fluorine, or if it is _C2 - _C4alkyl , it may also be substituted by a C1- _C3alkoxy group, or in which _R4 represents allyl, propargyl, phenyl or benzyl, the aromatic rings of the latter being unsubstituted or substituted by one or two substituents such as fluorine, chlorine, methyl, ethyl, methoxy or trifluoromethyl, while R ₂ represents C ₃ -C ₆ cycloalkyl, which may be unsubstituted or substituted by a methyl or methylthio group, while R ₃ has the meanings already described. Compounds according to claim 5, wherein X represents oxygen. 7. Compounds according to claim 6, wherein R1 represents hydrogen, C1- _C4 alkyl or _-ch2 - _or4 , R ₂ represents cyclobutyl, cyclopropyl, methylcyclopropyl or methylthiocyclopropyl and R1 represents C1-C4 alkyl which is unsubstituted or substituted by fluorine or in the case of representing _C2 - _C4 alkyl, may also be substituted by a methoxy or ethoxy group or in which R ₄ represents allyl, propargyl, phenyl, chlorophenyl, fluorophenyl, benzyl, chlorobenzyl or fluorobenzyl, while R ₃ has the meanings already described. 8. Compounds according to claim 7, wherein R ₂ represents cyclopropyl and R ₄ is methyl, ethyl, fluoromethyl, difluoromethyl, trifluoromethyl, allyl, propargyl, phenyl or benzyl. 9. Compounds according to claim 8, wherein R1 represents hydrogen, C1-C6 alkyl, methoxymethyl or ethoxymethyl. 10. Compounds of formula I according to claim 1, in which one of the two substituents R1 and _R2 represents the group _-CH2 - _XR4 and the other substituent represents hydrogen, C1-C4alkyl or -CH-XR4. X stands for oxygen or sulfur R ₃ has the meanings described above and R, represents C,-C,alkyl which is unsubstituted or substituted by fluorine, or if _C2 - _C4 , it may also be substituted by C1-C4alkoxy, or _R4 may represent alkyl, propargyl, phenyl or benzyl, the aromatic rings of the latter being unsubstituted or substituted by one or two substituents such as fluorine, chlorine, methyl, ethyl, methoxy or trifluoromethyl. 11. Compounds according to claim 10, wherein R, denotes the group -CH ₂ -OR ₄ , R ₂ represents hydrogen, C 1-4 alkyl or -ch ₂ -or ₄ , R ₃ has the meanings given above and R ₄ represents C 1 -C 4 alkyl which may be unsubstituted or substituted by fluorine, methoxy or ethoxy or where R ₄ represents allyl, propargyl, chlorophenyl, fluorophenyl, benzyl, chlorobenzyl or fluorobenzyl. 12. Compounds according to claim 11, wherein R ₂ represents C 1 -C 4 alkyl. 13. Compounds of formula I according to claim 1, wherein either a) Rj represents methyl, ethyl, n-propyl, methoxymethyl, ethoxymethyl, CH ₂ -O-CHF ₂ or cyclopropyl and R ₂ represents cyclopropyl, or where b) R ₄ represents methoxymethyl, ethoxymethyl, difluoromethoxymethyl or cyclopropyl and R ₂ represents C 1-4 C 10 alkyl and R ₃ has the meanings given above. Compounds of formula I according to claim 13, wherein R1 represents methyl, ethyl, n-propyl or isopropyl and R2 represents cyclopropyl. 15. Compounds of formula 1 according to claim 13, wherein R1 represents methoxymethyl, ethoxymethyl or cyclopropyl and R ₂ is methyl, ethyl, n-propyl, isopropyl or cyclopropyl. 5 16. A method for preparing thiazolyl-5-carbonamide derivatives of formula I and their acid addition salts and metal salt complexes according to claim 1, characterized in that thiazolyl-5-carboxylic acid of formula V or its acid halide, ester or acid anhydride is reacted with aminoacetonitrile of formula II CN I h ₂ n - ch - r ₃ at least one compound of general formula I according to claim 1, together with a suitable carrier. 17. A microbicidal agent for combating plant diseases, characterized in that it contains as an active substance nay and its C1-C2 esters, wherein R1 and _R2 have the meanings specified in formula 1 according to claim 1. 18. A composition according to claim 17, characterized in that it contains as active substance a compound according to claims 2 to 15. 19. A method for combating plant diseases, respectively for protecting plants from diseases, characterized in that a compound of general formula 1 according to claim 1 is applied to the plants, to their living space, to parts of the plants or to the propagation material of the plants. 20. Compound with formula V in a given case of a condensing agent or an acid acceptor, in which the substituents R _p R ₂ u R ₃ have the meanings given for formula 1. 21. A compound of formula V and its _C1 - _C6 esters according to claim 20, wherein R, ^{R2 and} R3 have the meanings given for formula I according to claim 13.