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 agrochemicals which contain at least one compound of this group as an active substance. The invention also relates to a method for the preparation of the aforementioned agents, as well as their use, as well as the active substances, for the control of microorganisms, in particular against microorganisms that damage plants, mainly against fungi.

TECHNICAL NATURE

OF THE INVENTION

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

In this formula, R ₃ means 2-furanyl, 2-thienyl, 3-furanyl or 3-thienyl, R ₁ and R ₂ independently represent a / C ₃ -C ₆ -cycloalkyl which is unsubstituted or substituted by methyl or methylthio, the (b) -CH ₂ -XR _{4 group} , and c) one of the two substituents R ₁ or R ₂ also denotes hydrogen or a C 1 -C ₄ -alkyl radical, whereupon X represents oxygen or sulfur, R ₄ is C, -C ₄ -alkyl which is unsubstituted or may be substituted by halogen, or in the case of C ₂ -C ₄ -alkyl also with C _t -C ₃ -aakokcH, or where R ₄ represents a C ₃ - C ₄ -alkenyl, C ₃ -C ₄ -alkynyl or one phenyl and or a benzyl group whose aromatic ring is unsubstituted or may be substituted by halogen, C 1 -C ₂ -alkyl, C ₁ -C ₂ -alkoxy, CF ₃ or NO _r

By "alkyl" alone or as an integral part of other substituents, such as haloalkyl or alkoxy, it is to be understood according to the number of said carbon atoms, for example, methyl, ethyl, propyl, butyl, and their isomers isopropyl, isobutyl, tert-butyl or sec .butyl. Halogen, referred to as "hal", is fluorine, chlorine, bromine or iodine. Haloalkyl means simple to perhalogenated residues such as 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 general formula I at 10 ordinary temperatures are stable oils or solids that have valuable microbicidal properties. They can be used in the agricultural sector or related fields preventively or to combat plant-borne microorganisms. The active substances of the invention of general formula I are distinguished at low concentrations of use not only by superior microbicidal activity, in particular 20 fungicidal action, but also by particularly good tolerance to plants.

Adjacent to the nitrile group, the compounds of general formula I have an asymmetric carbon atom. They can therefore be divided 25 as usual into optical antipodes. These antipodes have different microbicidal activity.

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

The salts according to the invention are in particular addition salts with safe 35 organic or inorganic acids such as chlorine, bromo or hydrochloric acid, sulfuric acid, phosphoric acid, phosphoric acid, nitric acid, or organic acids such as acetic acid, 40 trifluoroacetic acid, trichloroacetic acid, propionic acid, glycolic acid, thiocyanic acid, lactic acid, succinic acid, citric acid, benzoic acid, cinnamic 45 acid, oxalic acid, formic acid, benzenesul onic acid, p-toluenesulfonic acid, methanesulfonic acid, salicylic acid, paraaminosalitsilova acid, 2-phenoxybenzoic acid 50, 2-acetoxybenzoic acid or 1,2-naphthalene-disulfonic acid.

The metal salt complexes of 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, salicylates and salicylates. elements of the second major group, such as calcium or magnesium, and of the third or fourth major group, such as aluminum, tin or lead, and the first to eight subgroups such as chromium, manganese, iron, cobalt, nickel, copper, zinc and etc. The elements of the subgroups of the fourth period are preferred. Metals may appear in different valences. Metal complexes may have one or more nuclei, i. E. they may contain one or more parts of organic molecules such 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 is C ₃ -C ₆ -cycloalkyl which is unsubstituted or substituted with methyl or methylthio and the other substituent is r (cyclobutyl, cyclopropyl, methylcyclopropyl or methylthiocyclopropyl, e) the group -CH ₂ -XR ₄ or e) hydrogen or C 1 -C ₄ -alkyl, while R ₃ , X and R ₄ have the above meanings.

These compounds may hereinafter be referred to as compounds of group 1A.

Among the compounds of group 1A, preferred may be those in which one of the two substituents R and I ₂ is C ₃ -C ₆ -cycloalkyl and the other represents cyclobutyl or cyclopropyl, while R ₃ has the indicated meaning (group 1AA). and among them again those in which R, u R ₂ denote cyclopropyl.

Important compounds of the group IA are also those in which Rj represents a C ₃ -C ₆ -cycloalkyl, which is unsubstituted or may be substituted with methyl or methylthio, R ₂ represents hydrogen or C ^ C ^ alkyl, or the group -CH ₂ XR ₄ , X stands for oxygen or sulfur and R ₄ stands for C ₁ -C ₄ alkyl which is unsubstituted or substituted by fluorine or, in the case of C ₂ -C ₄ alkyl, may also be substituted by C 1 -C alkoxy, or R ₄ is allyl, propargyl, phenyl or benzyl, where the aromatic rings of the last mentioned radicals are unsubstituted or may be substituted HR h one or two substituents, fluorine, chlorine, methyl, ethyl, methoxy or trifluoromethyl, whereas R ₃ has the same significance as before / group 1B /.

Preferred are those compounds of group IB, wherein X is oxygen (group 1BB).

Important compounds within the IBB group are those wherein R1 is cyclobutyl, cyclopropyl, methylcyclopropyl or methylthiocyclopropyl,

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

R 1 represents C 1 -C 4 alkyl which is independently 4 or 4 substituent or may be substituted by fluorine, methoxy or ethoxy, or where R ₄ represents allyl, propargyl, phenyl, chlorophenyl, fluorophenyl, benzyl, chlorobenzyl or fluorobenzyl (subgroup 1b) .

Within group 1b, such compounds are preferred in which R ₁ is cyclopropyl,

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

R ₄ stands for methyl, ethyl, fluoromethyl, difluoromethyl, trifluoromethyl, allyl, propargyl, phenyl or benzyl, until

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

Particularly preferred compounds within the 1bb group are those wherein R ₂ is hydrogen, C 1 -C 6 alkyl, methoxymethyl or ethoxymethyl.

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

R 1 is C 1 -C-alkyl, unsubstituted or substituted by fluorine, or in the case where it is C ₂ -C ₄ -alkyl, may be substituted by C ₃ -Calkoxy, or where R ₄ is allyl, propargyl, phenyl or benzyl, wherein the aromatic rings of the last moieties are unsubstituted or substituted with one or two substituents fluorine, chlorine, methyl, ethyl, methoxy or trifluoromethyl until

R ₂ means C ₃ -C ₆ -cycloalkyl which is unsubstituted or may be substituted by methyl or methylthio until

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

Within this group, the 1CS is pred3

II III 1111.11 respect such compounds wherein R 1 is hydrogen, C 1 -C ₄ -alkyl or -CH ₂ -OR ₄ ,

R ₂ is cyclobutyl, cyclopropyl, methylcyclopropyl or methylthiocyclopropyl, and

R ₁ represents C ₁ -C ₄ alkyl which is unsubstituted or may be substituted by fluorine or, if R ₄ represents C ₂ -C ₄ alkyl, it may also be substituted by methoxy or ethoxy , or in which

R ₄ means allyl, propargyl, chlorobenzyl, 10 fluorobenzyl, benzyl, chlorophenyl or fluorobenzyl, while

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

Among these compounds are in particular compounds wherein R ₍ represents hydrogen, C 1 -C 3 -alkyl, methoxymethyl or ethoxymethyl).

Important compounds are also those triazolyl-5-carbonamide derivatives of general formula I, in which one of the two substituents Rt and R ₂ represents the group -CH ₂ -XR ₄ and 20 the other substituent represents hydrogen, C-C alkyl or -CH .-XR ,,

4 '

X stands for oxygen or sulfur,

R ₃ has the meanings given above and

R 1 represents C ₁ -C ₄ -alkyl which is unsubstituted or optionally substituted by fluorine or, in the case of C ₁ -C ₄ -alkyl, may be substituted by C 1 -C 6 alkoxy, or in the formula R ₄ represents allyl, propargyl, phenyl or benzyl, wherein the aromatic 30 ring of the last mentioned residues is unsubstituted or may be substituted by one or two substituents fluorine, chlorine, methyl, ethyl, methoxy or trifluoromethyl / = subgroup 1D /. 35

Among these compounds in the 1D group, there are advantages in which

R 1 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 given 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 denotes allyl, propargyl, phenyl, chlorophenyl, fluorophenyl, benzyl, 45 chlorobenzyl or fluorobenzyl (subgroup ND).

Included in the 1DD subgroup are those compounds of formula I in which R ₄ represents methyl, ethyl, fluoromethyl, difluoromethyl, trifluoromethyl, allyl, propargyl, phenyl or 50 benzyl (= subgroup 1e).

Particularly preferred are the compounds of the last mentioned subgroup Ie, in which R ₂ is hydrogen or C 1 -C 6 alkyl. Particularly preferred from subgroup Ie are also compounds wherein R and R ₂ independently represent methoxymethyl or ethoxymethyl.

In addition, among the compounds of subgroup 1D, those compounds wherein

R 1 represents hydrogen, C 1 -C ₄ -alkyl or the group -CH ₂ -OR ₄ ,

R1 stands for -CH, -O-R3.

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

Among the compounds in the IE group, 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 the IEE group are those wherein R! means hydrogen or C 1 -C 6 alkyl.

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

R ₂ represents cyclopropyl, or in which b / R, represents CH ₂ -O-CH ₃ , CH ₂ -O-C ₂ H ₅ , CH ₂ -O-CHF ₂ or cyclopropyl and R ₂ represents C ₍ -C ₃ - alkyl and

R ₃ has the meanings given to it (alpha subset).

Among these compounds in the alpha group one of the preferred subgroups may be one in which

R, is CH _3, C ₂ H _5, n-C ₃ H ₇ or izoS ₃ H ₇ and

R ₂ means cyclopropyl (beta).

In addition, among the compounds in the alpha group, another preferred subgroup may be one in which

R 1 represents CH ₂ -O-CH ₃ , CH ₂ -O-C ₂ H ₅ or cyclopropyl, and

R ₂ represents CH ₃ , C ₂ H ₅ , n-C ₃ H ₇ , iso-C ₃ H ₇ or cyclopropyl (gamma subgroup).

The compounds of general formula I are prepared by reacting thiazolyl 5-carboxylic acid of formula V

or an acid halide, ester or acid anhydride thereof with an aminoacetonitrile of formula II

CN ¹ / II /

H ₂ N - CH - R ₃ in the presence or in the absence of a condenser or acid acceptor, respectively, wherein the substituents R, R ₂ and R ₃ have the meanings given for formula I. It is appropriate to separate amino component II in a slight excess from component V (for example up to 2 moleq).

As the acid halide should be understood primarily chloride, bromide or iodide, such as an acid ester should be understood readily reactive derivatives with C ₆ alcohols, such as methyl, ethyl, propyl, isopropyl, butyl, tert, butyl, amyl ester and others. The interaction of V with II is carried out in the absence or preferably in the presence of a condensing agent, respectively, of an acid acceptor (proton acceptor).

An acid halide of formula V can also be obtained "in situ" from thiazolyl-5carboxylic acid by reacting it 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 previously.

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

For example, proton acceptors are inorganic or organic bases, such as alkaline or alkaline earth compounds, for example, hydroxides, oxides or carbonates of lithium, sodium, potassium, magnesium, calcium, strontium and barium, or hydrides such as sodium hydride. For example, tertiary amines such as triethylamine, triethylenediamine, pyridine, 4-dimethylaminopyridine may be mentioned as organic bases.

Although not required, the reaction may be solubilized or diluted, respectively. For example, the following may be mentioned: halogenated hydrocarbons, in particular chlorinated hydrocarbons such as tetrachloroethylene, tetrachloroethane, dichloropropane, methylene chloride, dichlorobutane, chloroform, tetrachloromethane, trichloroethane, 1,2-dichloroethane, 1,2-dichloroethane, 1,2-dichloroethane, 1,2-dichloroethane -cisdichloroethane, chlorobenzene, fluorobenzene, bromobenzene, dichlorobenzene, dibromobenzene, chlorotoluene; ethers, ethyl ether, methyltert-butyl ether, n-butylethyl ether, di-butyl ether, diisobutyl ether, diisopropylether, anisole, cyclohexylmethyl ether, diethyl ether, ethyl ether, ethyl ether , nitrobenzene, chloronitrobenzene, o-nitrotoluene; nitriles such as acetonitrile, butyronitrile, isobutyronitrile, benzonitrile, meta-chlorobenzonitrile; aliphatic or cycloaliphatic hydrocarbons such as heptane, hexane, octane, nonane, cymole, gasoline fractions within a boiling range from 70 ° C to 190 ° C, cyclohexane, methylcyclohexane, decalin, petroleum ether, ligroin, trimethylpentane as 2,3,3 -trimethylpentane; esters such as ethyl acetate, acetyl acetate, isobutyl acetate; amides, for example formamide, methylformamide, dimethylformamide; ketones such as acetone, methyl ethyl ketone; in one case also water. Mixtures of said solvents and diluents are also contemplated.

The starting materials of the formula II can be obtained according to the synthesis of Ströckner by reacting Aldehyde III with hydrocyanic acid, respectively with alkaline cyanide (eg sodium cyanide), in the presence of ammonia or 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 one ether (diethyl ether, dioxane, tetrahydrofuran, etc.) or aromatic hydrocarbon (benzene, toluene, xylene) and, on the other hand, water at 0 ° to 100 ° C.

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

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

R, -C _t

S

O - C - R ₂ + CH - COOR 's'

Hal

Va

VI VII wherein R 'is a C 1 -C 8 hydrocarbon, and then, as desired, 10 is passed through saponification to the carboxylic acid V. The reaction may be carried out in a protic solvent such as alcohol or in an aprotic solvent such as benzene, toluene, cyclohexane, etc. In some 15 cases, the addition of a proton acceptor such as sodium acetate / acetic acid or tert-base (eg pyridine, triethylamine, etc.) is required. Initially, the reaction is carried out at temperatures between -20 60 ° 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, it is used in benzene, toluene or cyclohexane, then the separated water can be removed with a water separator.

According to another variant of the method, the intermediate of formula V can also be obtained by thioamide of formula VI being acylated first by an acid halide of formula 30 VIII to N-acylthioamide of formula IX nh ₂ nh ₂ -co - r ₂

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

VI VIIIix

Therefore, it is appropriate to operate in an inert solvent such as acetonitrile or tetrahydrofuran. The tertiary acceptor is preferably a tertiary base such as 40 pyridine, triethylamine, 4-dimethylaminopyridine and the like. 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 halogenester of Formula X to a thiazolyl-5-carboxylic acid ester of Formula Va and then, if desired, typically converted to Compound V:

NH -CO - R ₂ ¹ Λ, 50

R, - C + Hal-CH, -COOR · ► Va 'r

S

IXX

On cyclization, N-acylthioamide IX is treated in a protic solvent (such as a lower alcohol) or an aprotic solvent with an alcoholate (for example). CH ₃ -ONa /, or with NaH at -40 ° C to + 20 ° C, preferably -30 ° C to 0 ° C, and then halogenester X is added at -20 ° C to +30 ° C, preferably at -10 ° C to + 10 ° C. The water is then removed from the reaction for several hours at a temperature of + 40 ° C to 120 ° C, preferably from + 60 ° C to + 100 ° C.

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

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

The new intermediates of formula V and their esters of C 1 -C ₆ -alcohols are another constituent of the invention, especially those in which R _t and R ₂ have the meanings given to the alpha subgroup.

Surprisingly, it has been found that the compounds of Formula I have for practical use a very favorable biocidal spectrum for combating phytopathogenic microorganisms, in particular fungi. They have very beneficial healing and therapeutic properties and are used to protect numerous cultivated plants. With the active substances of the formula I the pests or limbs / roots of different useful crops can be restricted or eliminated on the plants or parts of the plants / fruits, blossom, leaves, stems, roots / of various beneficial crops, while also the later grown parts of the plants remain protected against phytopathogenic microorganisms.

The compounds of formula 1 are effective, for example, against the following phytopathogenic fungi belonging to different classes: Fungi imperfecti (in particular Botrytis, in addition Pyricularia, Fusarium, Helminthosporium, Septoria, Cercospora, Alternaria), Basidiomyceten (e.g. Rhizoctonia, Hemileia). In addition, they are effective against the class Ascomyceten (eg Venturia u Erysiphe, Podosphaera, Monilinia, Uncinula), but above all against Oomyceten (eg Phytophthora, Peronospora, Bremia, Pythium, Torg Plas). The compounds of formula I can also be used as coating agents in the treatment of seeds / fruits, tubers, grains / and plant sprouts for protection against fungal infections, and against phytopathogenic fungi emerging in the soil.

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

In addition, the invention also includes the preparation of these agents, which is characterized by homogenization of the active substance with one or more of the substances described herein, respectively groups of substances. Also included is a method of treating mushrooms, which is distinguished by the use of new compounds of formula I, respectively, new agents.

For the crop protection application shown herein, the following plant species are considered as target crops: cereals / wheat, barley, rye, oats, rice, maize, sorghum and related species /, beet / sugar and fodder beet /, nuts, stone fruits and grapes / apples, pears, plums, peaches, almonds, cherries, strawberries, grapes, raspberries and blackberries /, pods / beans, lentils, peas, soybeans /, oilseeds / rapeseed, mustard, poppy, olive , sunflower, coconut, castor, cocoa, peanut /, cucumber / pumpkin, kras sheep, watermelons /, fiber / cotton, hemp, flax, jute /, citrus fruits / oranges, lemons, grapefruits, tangerines /, vegetable species / spinach, salads, asparagus, cabbage, carrots, onions, potatoes and pepper /, bay leaves / avocado, cinnamonium, camphor / or plants such as tobacco, nuts, coffee, sugar cane, tea, pepper, surfaces or plants. These other active substances can be both fertilizers, mediators of micronutrients, as well as other preparations affecting plant growth. Also selective herbicides, as well as insecticides, fungicides, bactericides, nematocides, molluscicides or mixtures of several of these preparations may be used herein together with other conventional formulations, surfactants or application enhancing agents, as appropriate.

Suitable carriers and additives may be solid or liquid and conform to the purposes of the formulation technique, for example natural or regenerated minerals, solutions, solubilizers, dispersants, wetting agents, adhesion enhancers, thickeners, binders or fertilizers.

A preferred method of application of the active substance of Formula 1, respectively, of the agrochemical agent containing at least one of these active substances, is application to the leaf mass (leaf application). The frequency of application and the amounts of consumption are thus determined according to the intensity of the attack of the respective agent. The active compounds of formula I may also be introduced through the soil through the root system of the plants (systemic action), the plant site being irrigated with liquid preparation or the substances in solid form being introduced into the soil, i. in the form of granulate / soil application /. In water-grown crops with such granules, water-filled rice fields can be dosed. The compounds of formula I may also be applied to seed kernels, whereby the kernels are either irrigated in a liquid preparation of the active substance, or a layer of solid preparation is applied to them.

The compounds of general formula I are therefore used in unaltered form or preferably in conjunction with conventional formulation aids. For this purpose, it is appropriate to process them to emulsion concentrates, brush-pasted, directly sprayed or diluted solutions, diluted emulsions, soluble powders, spray solutions, dusting agents, granules by encapsulation in, for example, polymeric substances. Methods of application such as spraying, aerosolization, dusting, sprinkling, brushing or watering shall be chosen as well as the type of agent in accordance with the set objectives and the specific conditions. Beneficial consumption amounts are generally in the range of 50 g to 5 kg of active substance per ha, preferably from 25 g to 2 kg of active substance per ha, in particular from 30 g to 300g of active substance per ha.

The wording, i. containing the active substance of formula I and optionally solid or liquid additives, preparations or compositions are obtained in a known manner, for example by mixing and / or grinding the active substance with excipients, such as solvents, solid carriers and optionally a surface active compounds (surfactants).

As solvents are aliphatic hydrocarbons, preferably the fractions C _g to C as xylene mixtures or substituted naphthalenes, phthalates such as dibutyl phthalate or dioctyl phthalate, aliphatic hydrocarbons such as cyclohexane or paraffins, alcohols and glycols and their ethers and esters, such as ethanol, 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 o epoxidized coconut oil or soybean oil or water.

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

Particularly useful adjuvants that can lead to a significant reduction in consumption are, in addition, natural / animal or vegetable / or synthetic phospholipids from the cephalin and lecithin group, which can be obtained, for example, from soy beans.

Surfactants, depending on the type of active substance to be formulated, are considered non-ionic, cationic and / or anionic surfactants with good emulsifying, dispersing and wetting properties. Surfactants should also be understood as a mixture of surfactants.

Suitable anionic surfactants may be so-called. water-soluble soaps as well as water-soluble synthetic surfactants.

Soaps are alkaline, alkaline earth or optionally substituted higher fatty acid ammonium salts (C ₁₀ -C ₂₂ ), for example, sodium or potassium salts of oleic or stearic acid, or of mixtures of natural fatty acids which may be obtained for example, from coconut oil or tallow, they may also mention the fatty acid methyl laurine salts.

Non-ionic 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 6 carbon and 18 carbon atoms. the alkyl residue of alkylphenol.

Examples of non-ionic surfactants include nonylphenolpolyethoxyethanol, ricinpolyglycolether, polypropylene polyethylene oxide adducts, tributylphenoxypolyethylene ethanol, polyethylene glycol and octylphenoxypolyethoxyethanol.

They also include fatty acid esters of polyoxyethylene sorbitan, such as polyoxyethylene sorbitan trioleate.

Cationic surfactants are primarily quaternary ammonium salts containing at least one alkyl residue of 8 to 22 carbon atoms as an N-substituent and, as other substituents, lower, optionally halogenated alkyl, benzyl or lower hydroxyalkyl residues.

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

Anionic, non-ionic or cationic surfactants used in the formulation technique are known to those skilled in the art or may 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, Munich / Wien, 1981.

Agrochemical preparations generally contain 0.1 to 99%, in particular 0.1 to 95% of active substance 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% surfactant.

While more concentrated products are preferred for commercial products, end users generally use diluted means.

The agents may also contain other additives such as stabilizers, depleters, viscosity regulators, binders, adhesive enhancers, and fertilizers or other active substances for special effects.

Examples of carrying out the invention

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

Examples of the preparation of the active substances

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

CH ₃ OCH ₂ - X-SEA ₂ H ₅

31.3 g of chloroacetic acid ethyl ester are mixed in 400 ml of benzene at room temperature with vigorous stirring with 20 g of methoxythioacetamide and refluxed using a 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% soda 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 were melted at 36-37 ° C.

b) Preparation of 2-methoxymethyl-4methylthiazole-5-carboxylic acid

CH ₃

CH ₃ OCH ₂ - co

22.1 g of 2-methoxymethyl4-methylthiazole-5-carboxylic acid ethyl ester was combined at room temperature with 6.7 g of 85% en potassium hydroxide in 100 ml of ethanol and then heated at reflux for 18 h. After cooling, the ethanol was removed by distillation and the residue was dissolved in 200 ml of water. After stirring with activated carbon, the mixture was filtered and the filtrate was acidified with concentrated hydrochloric acid with vigorous stirring. The resulting yellowish crystals were 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-3methylthiazolyl-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 with stirring at 0 ° C for 1/4 h 2.38 g of thionyl chloride. 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 leakage. After the addition of 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 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 was evaporated. The yellowish oil residue is allowed to crystallize by trituration with diisopropyl ether. The pale yellow crystals melt at 111-113 ° C.

Example 2. Preparation of 2- (2-methyl4-cyclopropylthiazole-5-carbonylamino) -2- (3-thienyl) -acetonitrile.

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

The following compounds can be prepared in an analogous manner:

Table 1: Compounds of formula

T = 2-furanyl

T ₂ = 3-furanyl

T ₃ = 2-thienyl

T = 3-thienyl 4

CP = cyclopropyl

Comp. ^R < ^R 2 R ₃ Physical constant No

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

28 - SN ₂ BAS ₃ -ch ₂ ochf ₂ ^t ₄ 29 Cyclohexyl -Sn ₃ ^T 4 30 -sw ₂ axis ₂ n ₅ - SN ₂ BAS ₃ ^t , 31 Wed. -Sn ₃ ^T 2 32 -Sn ₃ - SN ₂ BAS ₃ ^{T with} Melting point: 77-81 ° C 33 Wed. -sw ₂ axis ₂ n ₅ t. 34 ^C c ⁿ 7 ^N Wed. ^T 4 Melting point: 114-115 ° C 35 - SN ₂ BAS ₃ -Sn ₃ T, Melting point: 80-81 ° C 36 -sw ₂ axis 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 of T} 4 39 Wed. -Sn ₃ ^{T with} Melting point: 127-130 ° C 40 -Sn ₃ - SN ₂ BAS ₃ ^T 2 41 -CH ₂ OS ₂ H ₅ - SN ₂ BAS ₃ ^T 4 42 Wed. -sw ₂ axis ₂ n ₅ ^T 4 43 -ch ₂ ochf ₂ n ^T 4 44 -C _h H ₇ -H - SN ₂ BAS ₃ T ₄ dream, 45 - SN ₂ BAS ₃ ^T 4 dream, 46 -Sn ₃ t ₄ 47 -CH ₂ OCH ₂ CH ₂ OCH ₃ Wed. ^T 4 48 - SN ₂ BAS ₃ -Sn ₃ ^T 2 Melting point: 79-80 ° C 49 -Sn ₃ dream ₂ os ₃ ^t ₄ 50 -sw ₂ os ₂ sleep = sleep ₂ - ^{CH of} t ₄ zCH ₃ 51 - -sn t ₄ 52 -ch ₂ och ₂ cf ₃ n t ₄ 53 -Sn ₃ -sw ₂ axis ₂ n ₅ ^t . 54 - SN ₂ BAS ₃ -Sn ₃ ^{T with} Melting point: 96-98 ° C 55 -C ₃ H ₇ -is Wed. ^T 4 Melting point: 132-133 ° C 56 - ^{CH of} t ₄ SCH, 57 "And Wed. t ₄ 58 -sn ₂ os ₂ sleep ₂ os ₃ - SN ₂ BAS ₃ T ₄ 59 -Sn ₃ -sw ₂ axis ₂ n ₅ T ₄ 60 -sw ₂ o-ss ₂ -s = ss -Sn ₃ T ₄ 61 -CH ₂ O <g> -Sn ₃ t ₄ 62 -ch ₂ och ₂ cf ₃ -Sn ₃ T ₄ 63 -ch ₂ ochf ₂ Wed. ^T 4 SCH, 64 —And - SN ₂ BAS ₃ T. 65 CP -with ₂ n ₅ T. 66 -Sn ₃ -sn ₂ axis ₃ n ₇ - from T _A 4 SCH, 67 —And -Sn ₃ T, 68 - SN ₂ BAS ₃ -Sn ₃ T ₄ Melting point: 111-113 ° C 69 -ch ₂ o-tO ^ f -Sn ₃ T ₄

II III ΙΙΙΙΙίΙ

70 -sw ₂ axis ₂ n ₅ SCH, -ch ₃ Τ. 71 "And -CH ₂ OCH ₃ ^T 4 72 -CH ₂ OCHF ₂ -ch ₂ och ₃ Τ. 73 -Sn ₃ -CH ₂ OCHF ₂ Τ, SCH, 74 ___ko -CH ₃ ^τ 3 75 -C ₃ H ₇ -is -CH ₂ OC ₂ H ₅ L 76 -ch ₂ och ₃ -kO> -CH ₃ ^τ ₄ 77 -CP -c ₂ h ₅ Τ ₄ Melting point: 116-117.5 ° C 78 -c ₂ h ₅ CP ^Τ 2 Melting point: 84-86 ° C 79 -CH ₂ OC ₂ H ₅ -CH ₃ Τ ₂ SCH, 80 -CH ₃ Τ ₂ 81 -C ₄ H ₉ -norm CP Τ. SCH, 82 —And -CH ₂ OC ₂ H ₅ Τ. 83 -CH ₃ -ch ₂ ochf ₂ ^τ ₄ 84 -ch ₂ ochf ₂ -CH ₂ OCH ₃ ^Τ ₄ 85 -CH ₂ OCH ₂ - <g> Cl -CH ₃ ^Τ ₄ 86 CP CP ^τ · Melting point: 86-88 ° C SCH, 87 -ch ₃ ^Τ 4 88 -CH ₃ -ch ₂ och ₂ cf ₃ ^τ ₄ 89 -CH _n OCH ₂ CF ₃ CP ^Τ ₄ 90 -c ₂ h ₅ CP Τ ₄ Melting point: 81-83 ° C SCH 91 -CH ₂ OC ₂ H ₅ τ ₄ 92 -C ₄ H ₉ -norm CP ^τ ₄ n ^g / 1.5723 93 -CH ₂ OC ₂ H ₅ -CH ₃ Τ ₃ 94 - ^with l CP Τ. Melting point: 73-75 ° C 95 - SN ₂ BAS ₃ CP Τ, Melting point: 81-83 ° C 96 -ch ₂ oc ₂ h _s -CH ₃ Τ ₄ 97 - ^C 2 ^H 5 -CH ₂ OCH ₃ Τ, 98 -CH ₂ OCHF ₂ -CH ₃ ^τ . 99 -ch ₂ och ₂ cf ₃ -ch ₂ och ₃ Τ ₄ SCH, 100 -c ₂ h ₅ Τ ₄ 101 -ch ₂ ochf ₂ - Next 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 Τ, 104 -CH ₂ OCH ₃ -c ₂ h ₅ τ ₄ Melting point: 111-112 ° C 105 -ch ₂ ochcf ₂ -ch ₃ τ ₄ 106 -ch ₂ och ₂ cf ₃ -c ₂ h ₅ Τ ₄ 107 -CP -C ₃ H ₇ -is Τ ₄ Melting point: 108-111 ° C 108 -ch ₂ ochf ₂ -C ₃ H ₇ -is Τ,

109 110 111 112 CH ₂ axis ₂ n ₅ -ch ₂ ochf ₂ CH ₂ Axis ₂ H ₅ SCH, - -c ₂ h ₅ -ch ₃ - ^with l -C ₃ H _? -norm T. T; ^T 4 ^T < Butter Melting point 126-129 ° C 113 -CH ₂ OCH ₃ -C ₃ H _? -is 114 -ch ₂ ochf ₂ -C ₃ H ₇ -is ^T 4 115 -CH ₂ OCH ₂ CH ₂ OCH ₃ -with ₂ n ₅ ^T 4 116 -CH ₂ OC ₂ H ₅ -C ₃ H ₇ -is ^T 4 117 -ch ₂ och ₂ cf ₃ -Sn ₃ ^T , 118 -CH ₂ OC ₂ H ₅ -with ₂ n ₅ ^{T with} Melting point 96-97 ° C 119 -CH ₂ OCH ₃ -with ₂ n ₅ ^{T with} Melting point 78-83 »p 120 CP -with ₂ n ₅ t ₃ Melting point 106-109 ° C 121 -CH ₂ OCH ₃ Wed. ^{T with} Melting point 104-106 ° C 122 -CH ₂ OCH ₃ -with ₂ n ₅ t ₂ Melting point 81-83 ° C 123 -CH ₂ OCH ₃ Wed. Melting point 105-106 ° C 124 -CH ₂ OCH ₃ -with ₂ n ₅ T, Melting point 104-105 ° C 125 -C ₃ H ₇ -is Wed. T, Melting point 89-92 ° C 126 -C ₃ H ₇ -is Wed. ^{T with} Melting point 129-131 ° C 127 -C ₃ H _? -is Wed. L Melting point 109-110 ° C 128 -C ₃ H ₇ -norm Wed. t, Melting point 86-87 ° C 129 -C ₃ H _? -norm Wed. T ₃ Melting point 74-76 ° C 130 -C ₃ H ₇ -norm Wed. T ₂ Melting point 81-83 ° C 131 -ch ₂ ochf ₂ -Sn ₃ ^{T with} 132 -ch ₂ ochf ₂ -with ₂ n ₅ t. 133 -ch ₂ ochf ₂ -with ₂ n ₅ ^T 2 134 -ch ₂ ochf ₂ - ^with l ^{T with} 135 -ch ₂ ochf ₂ Wed. T, 136 -ch ₂ ochf ₂ Wed. t ₂ 137 -ch ₂ ochf ₂ Wed. ^{T with} 138 CP Wed. T ₂ Melting point 103-105 ° C 139 CP Wed. 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 -is T ₂ Melting point 108-110 ° C 142 CP -C ₃ H ₇ -is T, Melting point 97-100 ° 143 -ch ₂ och ₃ -C ₃ H ₇ -is 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 -is Tz Melting point 101-103 ° C 146 -CH ₂ OC ₂ H ₅ Wed. T, Melting point 116-118 ° C 147 -ch ₂ och ₃ -C ₃ H ₇ -norm T ₃ Melting point 98-101 ° C 148 -CH ₂ OC ₂ H ₅ Wed. Tz Melting point 123-125 ° C 149 -ch ₂ och ₃ -C ₃ H ₇ -is T, Melting point 87-90 ° C 150 -ch ₂ och 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 och ₃ -C ₃ H ₇ -norm t ₂ Melting point 85-87 ° C 153 -CH ₂ OCH ₃ -C ₃ H ₇ -is T ₂ Melting point 93-95 ° C 154 CP -C ₃ H ₇ -norm T ₄ Melting point 114-120 ° 155 -CH ₂ OCH ₃ -C ₃ H _? -norm T ₄ Melting point 124-126 ° C 156 -CH ₂ OC ₂ H ₅ Wed. T ₂ Melting point 109-111 »Su

II III! .11 III II

Table 2: Intermediates of general formula V

CP = cyclopropyl

Compound # R,

Physical constants

2.1 Wed. dream ₃ Melting point: 198-200 ° C 2.2 Wed. s 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 -is Melting point: 84-87 ° C 2.5 dream ₃ Wed. Melting point: 190-191 ° C 2.6 s ₂ n ₅ Wed. Melting point: Mp 158-159 ° C 2.7 With ₃ H _? -is Wed. Melting point: 122-123 ° C 2.8 C ₃ H ₇ -norm Wed. Melting point: 161-162 ° C 2.9 - SN ₂ BAS ₃ dream ₃ Melting point: Mp 168-169.5 ° C 2.10 - SN ₂ BAS ₃ s ₂ n ₅ Melting point: 146-147 ° C 2.11 - SN ₂ BAS ₃ Wed. Melting point: Mp 159-161 ° C 2.12 -sn, axis, n, CH, Melting point: 185-186 ° C 2 2 5 3 2.13 -sw ₂ axis ₂ n ₅ s ₂ n ₅ Melting point: 114-115 ° C 2.14 -sw ₂ axis ₂ n ₅ Wed. Melting point: 132-134 ° C 2.15 Wed. Wed. Melting point: 102-104 ° C 2.16 -ch ₂ ochf ₂ dream ₃ 2.17 -ch ₂ ochf ₂ s ₂ n ₅ 2.18 -ch ₂ ochf ₂ Wed. 2.19 - SN ₂ BAS ₃ C ₃ H ₇ -norm 2.20 -CH ₂ OCH ₃ With ₃ H _? -is

In the presence of a catalyst, for example HC1 may be readily prepared from the acids of Table 2 by esterification with methanol, ethanol or one of the isomers of alcohols propanol, pentanol or hexanol corresponding C ₁ -C ₆ alkyl esters of these carboxylic acids.

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

2.1. Powder for suspension for

spraying a / b / w 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 lenglycolether / 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. 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 of 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 dilution with water.

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

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

mixtures with the carrier and the resulting mixture is ground suitable mill. 2.4. Extruded granulate Active substance of Table 1 % N-ligninsulfonate 2% Carboxymethylcellulose 1% Kaolin 87%

The active substance is mixed with the additives, ground and wetted with water. This mixture is extruded and then air-dried.

2.5. Granulate in the shell

Active substance of Table 1 3%

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

The finely divided active substance is applied in a mixer to polyethylene glycol moistened kaolin. In this way, a powder free granule is coated.

2.6. Suspension concentrate

Active substance of Table 1 40%

Ethylene glycol 10%

Nonylphenol polyethylene glycol ether / 15 to 1 ethylene oxide / 6%

N-ligninsulfonate 10%

Carboxymethylcellulose 1%

37% aqueous formaldehyde solution 0.2%

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

Water 32%

The finely divided 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 / Effect on infected plants.

The red gnome tomato plants are sprayed after three weeks of cultivation with a suspension of zoospores of the sponge and incubated in a cabin at 18 to 20 ° C and air with saturated humidity. After 24 h, the humidification was interrupted. After the plants have dried, they are sprayed with a solution containing powdered formulations for the preparation of a spray suspension of the active substances at a concentration of 600, 200 or 60 ppm. After the spray coating has dried, the mushrooms are again placed in a humid cabin for 4 days. The number and size of the characteristic spots on the leaves that emerged during this time are a measure in 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 (relative to soil volume) to the soil surface of potted red gnome tomato plants at 3 weeks of age. After a three-day stay, the lower part of the leaves of the plants is sprayed with a zoospore suspension of Phytophthora infestans. They are kept for 5 days in a cabin at 18 to 20 ° C with saturated humidity. After this time, characteristic spots on the leaves are formed, the number and size of which serve to evaluate the activity of the test substances.

The following compounds of Table 1 achieved a suppression of fungal attack below 10%: # 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 a vine.

a / preventive treatment with residual action

Chasselas vine sticks are grown in a greenhouse. Three plants in the tenth leaf stage were sprayed with an active ingredient solution (200 ppm active ingredient) obtained from the powder formulated for production. After the spray coating has dried, the leaves of the plants on the reverse side are sprayed with a sponge spore suspension evenly. The plants were then kept in a humidified chamber for 8 days. During this time the symptoms of the disease on the control plants are clearly manifested. The number and size of contaminated sites on treated plants serves as a measure to evaluate the activity of the test compounds.

b / action in infected plants

Chasselas vines are grown in a greenhouse and sprayed with Plasmoparaviticola spores on the back of the leaves in the tenth leaf stage. After 24 hours in the wet cabin, the plants are sprayed with a solution of the active substance, which is obtained from a powder formulated for the preparation of suspensions for spraying the active substance (500 ppm active substance). The plants are then kept in the damp cabin for seven more days. During this time, the symptoms of the disease on control plants are manifested. The number and size of contaminated sites on treated plants serve to measure the activity of the test substances.

All of the compounds listed in Example 1 achieved a suppression of disease manifestations below 10%.

III. Action against Pythium debaryanum on sugar beet (Beta vulgaris).

a / soil application

The fungus is cultured on sterile oat grains and added to a mixture of soil and sand. Soiled soil is filled with flower pots and sowed sugar beet seeds. Immediately after sowing the test preparations formulated as powder for spray suspensions, the soil was irrigated (20 ppm active substance, relative to the volume of the soil). The pots are then placed in a greenhouse at 20-24 ° C for 2-3 weeks. By gently spraying with water, the soil is kept constantly evenly moist. The estimation of experience determines the emergence of sugar beet plants, as well as the number of healthy and diseased plants.

b / surface treatment of seeds The fungus is cultured on sterile oat grains and added to a mixture of soil and sand. The contaminated soil is filled with flower pots and seeded with sugar beet, which has been surface-treated with powdered preparations (1000 ppm active substance by weight of seeds). The seeded pots were kept in the greenhouse for 2-3 weeks at 20-24 ° C. In doing so, the soil is kept constantly evenly moist by gently spraying with water. When evaluating the results of the experiment, the germination of the sugar beet seeds and the number of healthy and diseased plants are determined.

The compounds of Table 1 achieved an emergence of over 80% of cases. Appropriate control plants emerge in less than 30% of cases and have an unhealthy appearance.

Claims (21)

1. Thiazolyl-5-carbonamide derivatives of formula I, their acid addition salts and complexes of metal salts in which formula R ₃ means 2-furanyl, 2-thienyl, 3-furanyl or 3-thienyl and R ₍ u R ₂ independently 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, in addition X stands for oxygen or sulfur, R is C1-C6 alkyl. which is not 4-14 substituted or substituted by halogen, or in the case of C ₂ -C ₄ alkyl, may also be substituted by C 1 -C ₄ alkoxy, or R ₄ represents C ₃ -C ₄ alkylene, C ₃ -C _{A 4-} alkynyl or phenyl group or a benzyl group whose aromatic ring is unsubstituted or substituted by halogen with C1-C6-alkyl, C1-C-alkoxy, trifluoromethyl or nitro. Compounds of formula I according to claim 1, wherein one of the two substituents R, u R, represents C-C, cycloalkyl, 12 3 6 which may be unsubstituted or substituted by methyl or methylthio group and the other substituent means: d) cyclobutyl, cyclopropyl, methylcyclopropyl or methylthiocyclopropyl, e) the -CH ₂ -XR _{4 group} or e) hydrogen or C ₍ -C ₄ ) R ₃ , X and R ₄ have the meanings given above. Compounds of formula I according to claim 2, wherein one of the two substituents R ₃ and R ₂ is C ₃ -C ₆ cycloalkyl and the other is cyclobutyl or cyclopropyl, while R ₃ has the above meanings. Compounds of formula I according to claim 3, wherein R 1 and R ₂ are cyclopropyl. Compounds of formula I according to claim 2, wherein R 1 represents hydrogen or C] _-C4 alkyl or a group -CH ₂ -XR _4, X stands for oxygen or sulfur and R 1 represents C 1 -C 6 alkyl which is unsubstituted or substituted by fluorine or, if C ₂ -C ₄ alkyl, may also be substituted by C 1 -C ₃ alkoxy, or in which R ₄ denotes allyl, propargyl , phenyl or benzyl, wherein the aromatic rings of the latter may be unsubstituted or with one or two substituents such as fluorine, chlorine, methyl, ethyl, methoxy or trifluoromethyl substituted until R ₂ means C ₃ -C ₆ cycloalkyl which may not be or is substituted by methyl or methylthio, while R ₃ has the meanings already described. Compounds according to claim 5, wherein X is oxygen. 7. Compounds according to claim 6, wherein R 1 represents hydrogen, C 1 -C ₄ alkyl or -ch ₂ -or ₄ , R ₂ means cyclobutyl, cyclopropyl, methylcyclopropyl or methylthiocyclopropyl, and R 1 is C ₁ -C ₄ alkyl which is unsubstituted or substituted by fluorine or, if it is C ₂ -C ₄ alkyl, may also be substituted by methoxy or ethoxy or in which R ₄ means allyl, propargyl, phenyl, chlorophenyl, fluorophenyl, benzyl, chlorobenzyl or fluorobenzyl, while R ₃ has the meanings already described. Compounds according to claim 7, wherein R ₂ is cyclopropyl and R ₄ stands for methyl, ethyl, fluoromethyl, difluoromethyl, trifluoromethyl, allyl, propargyl, phenyl or benzyl. Compounds according to claim 8, wherein R1 represents hydrogen, C1-6alkyl, methoxymethyl or ethoxymethyl. Compounds of formula I according to claim 1, wherein one of the two substituents R 1 and R ₂ represents the group -CH ₂ -XR ₄ and the other substituent represents hydrogen, C 1 -C 4, alkyl or -CH-XR 3. X stands for oxygen or sulfur R ₃ has the meanings given above and R 1 represents C 1 -C 6 alkyl which is unsubstituted or substituted by fluorine or, if C ₂ -C ₄ , may also be substituted by C 1 -C 4 alkoxy, or R ₄ may represent alkyl, propargyl , phenyl or benzyl, wherein the aromatic rings of the latter may not be or are substituted by one or two substituents such as fluorine, chlorine, methyl, ethyl, methoxy or trifluoromethyl. Compounds according to claim 10, wherein R 1 represents the group -CH ₂ -OR ₄ , R ₂ represents hydrogen, C 1 -C 4 alkyl or -ch ₂ -or ₄ , R ₃ has the meanings given above and R ₄ is C 1 -C 4 alkyl which may not be or may be substituted by fluorine, methoxy or ethoxy or where R ₄ is allyl, propargyl, chlorophenyl, fluorophenyl, benzyl, chlorobenzyl or fluorobenzyl. Compounds according to claim 11, wherein R ₂ is C 1 -C 4 alkyl. Compounds of formula I according to claim 1, wherein or a) R1 is methyl, ethyl, n-propyl, methoxymethyl, ethoxymethyl, CH ₂ -O-CHF ₂ or cyclopropyl and R ₂ means cyclopropyl, or where (b) R ₄ means methoxymethyl, ethoxymethyl, difluoromethoxymethyl or cyclopropyl, and R ₂ is C 1 -C 4 alkyl and R ₃ has the meanings given above. Compounds of formula I according to claim 13, wherein R 1 is methyl, ethyl, n-propyl or isopropyl and R is cyclopropyl. Compounds of formula I according to claim 13, wherein R 1 represents methoxymethyl, ethoxymethyl or cyclopropyl and R ₂ denotes methyl, ethyl, n-propyl, isopropyl or cyclopropyl. 5 A process for the preparation of thiazolyl-5carbonamide derivatives of formula I and their acid addition salts and complexes of metal salts according to claim 1, characterized in that thiazolyl-5- 10 carboxylic acid of formula V or its acid halide, ester or an acid anhydride is reacted with an aminoacetonitrile of formula II CN I h ₂ n - chn - r _{3 at} least one compound of the general formula I according to claim 1, together with a suitable carrier. A microbicidal plant disease control agent, characterized in that it contains both its C 1 -C 2 esters as the active substance, wherein R 1 and R ₂ have the meanings given in formula 1 according to claim 1. An agent according to claim 17, characterized in that it contains, as an active substance, a compound according to claims 2 to 15. 19. A method of controlling plant diseases, respectively, for protecting plants from diseases, characterized in that a compound of the general formula I according to claim 1 is applied to the plants, to their living space, to the plant parts or to the propagation plant. plant material. A compound of formula V, optionally a condenser or acid acceptor, wherein the substituents R _p R ₂ and R ₃ have the meanings given for formula 1. A compound of formula V and its C ₁ -C ₆ esters according to claim 20, wherein R, ^UR 2 have the meanings given for formula I according to claim 13.