DD261735A5 - MEANS OF PREVENTING OR PREVENTING AN EMERGENCY BY MICROORGANISMS - Google Patents

Abstract

The invention relates to means for controlling or preventing infestation by microorganisms. According to the invention, as active ingredient in the novel microbicidal agents, novel compounds of the formula are used, wherein R 1 is hydrogen, halogen, C 1 -C 2 -alkyl or CF 3, R 2 is halogen or C 1 -C 2 -alkyl, R 3 is C 1 -C 5 -alkyl or C 3 -C 5 -alkenyl; R 4 is hydrogen, C 1 -C 4 -alkyl, C 3 -C 4 -alkenyl or R 5, R 6 and R 7 independently of one another represent hydrogen, nitro, halogen, cyano, C 1 -C 3 -alkyl, C 1 -C 3 -alkoxy, C 1 -C 3 -haloalkoxy or CF 3, and Y represents a nitrogen atom or the CH group, including its acid addition salts, quaternary azolium salts and metal salt complexes having microbicidal properties. formula

Description

Field of application of the invention

The invention relates to compositions for controlling or preventing infestation by microorganisms containing new substituted aryl-fluoro-azolyl-alkanols and their ethers and their acid addition salts, quaternary Azolrumsalze and metal salt complexes. The invention further relates to the preparation of these substances. The invention also relates to the preparation of said agents and the use of the active ingredients or the agents for controlling harmful microorganisms, preferably phytopathogenic fungi, in particular Piricularia species. The compositions according to the invention are used in agriculture and in the protection of stored products.

Characteristic of the known state of the art

There is no information available on which fungicidal compounds have hitherto been used to control or prevent infestation by microorganisms.

Object of the invention

The aim of the invention is the provision of new agents which are suitable for controlling or preventing infestation by microorganisms.

Explanation of the essence of the invention

The invention has for its object to find new compounds which are suitable as active ingredient in agents having the desired properties.

According to the invention as active ingredient in the novel microbicidal agents compounds of the general formula

H _N

OH

applied,

R _{1 is} hydrogen, halogen, C ₂ alkyl or CF ₃ ;

R _{2 is} halogen or C ₁ -C ₂ alkyl;

R ₃ is C _r C ₅ alkyl oderCrCs alkenyl;

R _{4 is} hydrogen, C _r C ₄ alkyl, C ₃ -C ₄ alkenyl or

the group -CH2- »f. y, where

R ₅ , R ₆ and R ₇ independently of one another represent hydrogen, nitro, halogen, cyano, C ₁ -C ₃ -alkyl, C ₁ -C ₃ -alkoxy, C ₁ -C ₃ -HaIOalkoxy or CF ₃ , and

Y represents a nitrogen atom or the CH group, including their acid addition salts, quaternary azolium salts and metal salt complexes

 Compounds of formula I falling within the scope of formula Γ,

where: = R ₃ F j ==

R _{1 is} hydrogen, halogen, C _r C ₂ alkyl or CF ₃ ;

R _{2 is} halogen or C ₁ -C ₂ -alkyl or CF ₃ ;

R _{3 is} C _r C ₄ alkyl;

R _{4 is} hydrogen, C ₁ -C ₄ -alkyl, C ₃ -C ₄ -alkenyl or

/ V ^s

the group -CH2- · ^ ^ ·, where

R ₅ , R ₆ and R ₇ independently of one another represent hydrogen, nitro, halogen, cyano, C ₁ -C ₃ -alkoxy, C ₁ -C ₃ -alkoxy, C ₁ -C ₃ -HaIOalkoxy or CF ₃ , and

Y represents a nitrogen atom or the CH group represent a narrower range of preferred compounds. Under alkyl, depending on the number of carbon atoms given, for example, methyl, ethyl and the isomers of propyl and butyl, such as. For example, n-propyl, isopryl, isobutyl or tert-butyl. Alkenyl is z. B. for propenyl (1), allyl, butenyl (2) or butenyl (3) and is preferably allyl. Halogen is fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine.

The present invention encompasses both the free compounds of formula I and their acid addition salts, quaternary azolium salts and metal salt complexes. The free compounds within the scope of formula I, in particular the 1H-1,2,4-triazole derivatives, are preferred.

Examples of acids which can be added are inorganic acids: hydrohalic acid such as hydrofluoric acid, hydrochloric acid, hydrobromic acid or hydriodic acid and sulfuric acid, phosphoric acid, phosphorous acid, nitric acid and organic acids such as acetic acid, trifluoroacetic acid, trichloroacetic acid, propionic acid, formic acid, benzenesulfonic acid, p-toluenesulfonic acid, methanesulfonic acid, Maleic acid, succinic acid, tartaric acid, fumaric acid, salicylic acid, lactic acid or sorbic acid.

The metal salt complexes consist of the underlying free compound of formula I and an inorganic or organic metal salt, for example the halides, nitrates, sulfates, phosphates, acetates, trifluoroacetates, trichloroacetates, propionates, tartrates, sulfonates, salicylates, benzoates, etc. of the elements of the third and third fourth main group such as aluminum, tin or lead and the first to eighth subgroup such as chromium, manganese, iron, cobalt, nickel, zirconium, copper, zinc, silver, mercury, etc. Preferably, the subgroup elements of the 4th period. The metals can be present in the various valences that belong to them. The metal salt complexes of Fomel I can occur mononuclear or polynuclear, d. H. they may contain one or more organic moieties as ligands. Complexes with the metals copper, zinc, manganese, tin and zirconium are preferred.

For the preparation of QuaternierUngsprodukten the compounds of formula (I) are preferably alkyl or aralkyl halides, sulfates or sulfonates, such as methyl iodide, dimethyl, diethyl or monomethyl sulfate, Benzylchiorid or bromide, methyl or ethyl p-toluenesulfonate Question.

The acidification products of the compounds of the formula (I) can be prepared in a simple manner by conventional methods, e.g. by reacting the reaction components in a suitable solvent such as acetonitrile or acetone

be obtained and in a known manner, for. B. by precipitation with a suitable precipitant such. B. diethyl ether and suction and are purified by washing with an inert organic solvent.

The compounds of formula I are stable at room temperature oils, resins or predominantly solids, which are characterized by very valuable microbicidal properties. They can be used in the agricultural sector or related fields in a preventive and curative manner for the control of plant-damaging microorganisms, the treiszoiymethyl derivatives within the scope of formula I being preferred. The active compounds of the formula I according to the invention are distinguished at low application concentrations by a very good plant-fungicidal action and problem-free application.

Because of their pronounced microbicidal, especially plant-fungicidal action, the following substance groups are preferred:

Compounds of the formula I, in which

a) R ₁ ZR ₂ 2,4-Cl ₂ or 2,4- {CH ₃ ) ₂ ; R _{3 is} C ₁ -C ₂ -alkyl;

R _{4 is} hydrogen, C 1 -C 3 -alkyl, allyl or 2,4-dichlorobenzyl; and

Y is a nitrogen atom or the CH group.

b) R, / R _{2 is} 2,4-Cl ₂ or 2,4- (CH ₃ ) ₂ ; R _{3 is} C ₁ -C ₃ alkyl or C ₁ -C 4 alkenyl;

R _{4 is} hydrogen, C ₁ -C ₃ alkyl, allyl, or 2,4-dichlorobenzyl;

Y is a nitrogen atom or the CH group.

c) Ft, hydrogen, chlorine or methyl; R ₂ "fluoro, chloro or methyl;

R ₃ is C _r C ₄ alkyl or allyl;

R ₄ Ci-C ₄ alkyl or C ₃ -C ₄ alkenyl; and

Y is a nitrogen or the CH group.

Of these, the following compounds are particularly preferred, in which represent:

under a) Ri / R ₂ 2,4-Cl ₂

, R ₃ CH ₃

R _{4 is} hydrogen and

Y is a nitrogen atom; under b) R, / R ₂ 2,4-CI ₂ ;

R _{3 is} CH ₃ , n-propyl or allyl

R _{4 is} hydrogen or methyl; and

Y is a nitrogen atom;

lower) R _{1 is} hydrogen, chlorine or methyl;

R _{2 is} fluorochloro or methyl;

R _{3 is} methyl, n-propyl, n-butyl, tert-butyl or allyl;

R _{4 is} methyl, n-propyl, η-butyl, allyl or but-2-enyl; and

Y is a nitrogen atom or the CH group.

Particularly preferred compounds in their biological activity are, for example: 1- (2,4-dichlorophenyl) -1-methyl-2-fluoro-2- (1H-1,2,4-triazol-1-yl) -ethanol (No. 1.1); 1- (2,4-pichlorophenyl) -1-n-propyl-2-fluoro-2- (1H-1,2,4-triazol-1-yl) -ethanol (# 1.5); 1- (1,2-bichlorophenyl) -1-n-propyl) -2-fluoro-2- (1H-imidazol-1-yl) -ethanol (# 1.6); 1- (2,4-dimethylphenyl) -1-methyl-2-fluoro-2- (1H-1,2,4-triazol-1-yl) -ethanol (No.1.7) 1- (2,4-dimethylphenyl ) -1-n-propyl-2-fluoro-2- (1H-1,2,4-triazol-1-yl) -ethanol (# 1.10); 1- (4-fluorophenyl-1-methyl-2-fluoro-2-fluoro-2- (1H-1,2,4-triazol-1-yl) ethanol (Nr.1.11);

1- (2-chloro-4-fluorophenyl) -1-n-propyl-2-fluoro-2- (1H-1,2,4-triazol-1-y |) ethanol (Nr.1.26); 1- (2,4-dichlorophenyl) -1-n-butyl-2-fluoro-2- (1H-1,2,4-triazol-1-yl (-ethanol (# 1.33); i ^ -Chlorophenyl) it.butyl ^ -fluoro ^ -ie-I ^ Atriazol-i-yD-ethanoKNr.i ^); '

1- (4-chlorophenyl) -1-allyl-2-fluoro-2- (1H-1,2,4-triazol-1-yl) -ethanol (# 1.36); 1- (2,4-dichlorophenyl) -1-methyl-1-methoxy-2-fluoro-2- (1H-1,2,4-triazol-1-yl) -ethane (No.2.1); i ^^ - Dichlorophenyl-i-methyl-in-propoxy-fluoro-dH-i ^ atriazol-i-yD-ethane (iMr.2.3) 1- (2,4-dichlorophenyl) -1-methyl-1- n-propoxy-2- (1H-imidazol-1-yl) -ethane (No.2.4) i ^^ - Dichlorophenyl-i-methyl-in-butoxy-fluoro-dH-i ^^ - triazole-i- yD-ethane (No.2.5); 1- (2,4-dichlorophenyl) -1-methyl-1-allyloxy-2-fluoro-2- (1H-1,2,4-triazol-1-yl) ethane (Nr2.6); 1- (2,4-dichlorophenyl) -1-methyl-1-allyloxy-2- (1H-imidazol-1-yl-ethane (No.2.7) 1- (2,4-dichlorophenyl) -1-methyl-1 -but-2-enoxy-2-fluoro-2- (1H-1,2,4-triazol-1-yl) -ethane (No.2.8); I ^ ADichlorophenyl-in-propyl-T-methoxy-fluoro ^ -dH-i ^^ -triazol-i-yl-ethane (No.2.15), 1- (2,4-dichlorophenyl) -1-n-propyl-1-methoxy-2- (1H-imidazole-1 -yl (-ethane (No.2.16);

i ^^ - Dichloro-phenyi-i-propyl-i-allyloxy-fluoro-dH-i ^ atriazol-i-yD-ethane (No.2.18); 1- (2,4-dimethylphenyl) -1-methyl-1-methoxy-2-fluoro-2- (1H-1,2,4-triazol-1-yl) ethane (Nr.2.19); 1- (2,4-dichlorophenyl) -1-allyl-1-methoxy-2-fluoro-2- (1H-1,2,4-triazol-1-yl (-ethane (No.2.51); ^ -Dichlorophenyl-in-propyl-i-methoxy-fluoro-dH-1-atriazol-i-yD-ethane (No.2.52) Compounds of the formula Ia (alkanol derivatives)

-o-wa.

(La),

(3

are prepared according to the invention by adding a ketone derivative of the formula II

with a compound of formula IV ".

R ₃ MgX. - · (IV)

as Grignard reagent in an inert solvent, wherein Ri, R ₂ and R _{3 have} the meanings given under formula I and X is halogen, in particular bromine or iodine.

The reaction is carried out in the manner of the Grignard reaction (see Nützel, Houben-Weyl Bd., 13/2 a, pages 47-527) normally carried out in diethyl ether; However, other solvents, such. For example, higher ethers, such as tetrahydrofuran, dioxane, dibutyl ether or anisole, and also ethylene glycol ethers or diethylene glycol ethers are suitable. In addition, bases such as pyridine can be used. Suitable reaction temperatures are those of -80 ° to 50 ⁰ C, preferably -60 ° to ± 0 ° Cin question. Compound of formula Ib.

are prepared according to the invention by reacting a compound of the formula (Ia)

y-K 9^H ¥S-l?

_R2 _ / S XL ₁ / (la),

^ y h

or a compound of the formula

/ '"V-JLJL /'" "! (In),

-O

H-C!

each with a compound of formula V. ,

R ₄ -W (V)

to react.

Compounds of the formula Ic.

wherein R ₃ 'is C ₃ -C ₅ alkenyl, are prepared according to the invention by reacting a compound of formula

/ 'Ϊ ^(ll)

Ύ = ·

with a silane compound of formula VI

R ₃ '-Si (Alk) ₃ ' (VI)

wherein AIkCi-C ₄ -Alkyl, preferably methyl, in the presence of a Lewis acid. (Ref.Tetrah Letters [1976] 1295-1298). ,

Compounds of formula I c can be prepared by hydrogenation in the presence of a catalyst, for. B. of palladium / activated carbon, in compounds of formula Id

(Ld),

wherein R _{3 represents} "C ₃ -C ₅ alkyl.

In addition, ether compounds of the formula I b in which R _{3 is} a C ₃ -C 8 alkenyl can also be hydrogenated in the manner described above to give the corresponding alkyl compounds of the formula Ib.

In the processes described above, R ₁ , R ₂ , R ₃ , R ₄ and Y correspond to the meanings given under formula I, W is -OH, -OM or a so-called leaving group and Z represents the group -OM or a leaving group, wherein M represents an alkali or alkaline earth metal, with the proviso that in the reactants la and III on the one hand and V on the other hand, an -OM group having one leaving group or two hydroxy groups react with each other.

Among a leaving group are herein and hereinafter substituents such as halogen (such as fluorine, chlorine, bromine or iodine, preferably chlorine or bromine); Sulfonyloxy groups, preferably -OSO ₂ -R ₈ ; Acylkoxygruppen, preferably -OCO-R ₈ or Isoharnstoffreste, preferred

-0-C * NR ₉

NHRio

are understood, wherein R ₈ , R ₉ and R independently of each other are CrCrAlky ^ CrCa-haloalkyl or optionally substituted by halogen, methyl, nitro, trifluoromethyl and / or methoxy-substituted phenyl.

In the reaction of compounds of the formula Ia with formula V in which W is a leaving group, the reaction is carried out in the absence or preferably in the presence of a reaction-inert solvent. For z. For example, the following solvents:

N, N-dimethylformamide, Ν, Ν-dimethylacetamide, hexamethylphosphortriamide, dimethylsulfoxide, 2-methyl | r2-pentanone, etc .. Also, mixtures of these solvents with each other or with other conventional inert organic solvents, such as. For example, with aromatic hydrocarbons such as benzene, toluene, xylenes, etc. can be used. In addition, water is preferably used as the solvent. In some cases, it may prove advantageous to accelerate the reaction rate in the presence of a base such. As an alkali metal hydride, hydroxide or carbonate to work. However, it may also be advantageous that the alkanol of the formula I a first in a known per se, for. B. by reaction with a strong base, converted into a suitable metal salt.

Suitable strong bases are for. As alkali and alkaline earth metal hydrides (NaH, KH, CaH ₂ , etc.) and alkali organic compounds such. Butyllithium or alkali tert-butoxide. In addition, it is also possible in aqueous solution or suspension using water-soluble organic solvents, for. As dioxane, acetone, N, N-dimethylformamide, as a solubilizer or in a two-phase system of water and a water-immiscible solvent, eg. As CH ₂ Cl ₂ , ether, methyl, ethyl ketone, preferably using water-soluble bases, such as KOH, NaOH, Na ₂ CO ₃ , to work. Especially when using two-phase systems, it is advantageous to phase transfer catalysts, eg. B. quaternary alkylammonium salts, add.

In cases where starting from an alkali metal alcoholate of formula III (Z = -OM with M = alkali metal, such as potassium or sodium) and this with a compound of formula V (wherein W is a leaving group) is reacted, it works advantageously in the presence of a crown ether. At M = K, especially in the presence of 18Krone-6; at M = Na, especially in the presence of 15 crown-5.

-The reaction is conveniently carried out in a reaction-inert medium. Suitable solvents are, for. For example, ether and etherärtige compounds, for. B. Diniederalkyleth.er (diethyl ether, diisopropyl ether, tert-butyl methyl ether, etc.), tetrahydrofuran, dioxane and aromatic hydrocarbons such as benzene, toluene or xylenes.

For the organic phase, which is immiscible with water, z. Examples of suitable solvents are aliphatic and aromatic hydrocarbons, such as pentane, hexane, cyclohexane, petroleum ether, ligroin, benzene, toluene, xylenes, etc., halogenated hydrocarbons, such as dichloromethane, chloroform, carbon tetrachloride, ethylene dichloride, 1,2-dichloroethane, Tetrachlorethylene, etc., or aliphatic ethers such as diethyl ether, diisopropyl ether, t-butylmethyl ether, etc. Examples of suitable phase transfer catalysts are: tetraalkylammonium halides, hydrogen sulfates or hydroxides such as tetrabutylammonium chloride, bromide; Tetrapropylammonium chloride, bromide, iodide; etc .. As phase transfer catalysts and phosphonium salts come into consideration. The reaction temperatures are generally between 30 ° and 130 ⁰ C, or at the boiling point of the solvent or solvent mixture.

In those cases where compounds of the formula Ia are reacted with those of the formula V in which W represents a hydroxy group, a condensation reaction is advantageously carried out. Both reactants are obtained in a suitable solvent at ^{reflux: +} zt.

This solvent can be used in principle, which behave inert to the reactants and expediently form azeotropes with water. For this purpose, for example, aromatic hydrocarbons such as benzene, toluene, xylenes or halogenated ^ hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, tetrachlorethylene, chlorobenzene, but also etherärtige compounds such as tert-butyl methyl ether, dioxane and others are suitable , In some cases, the compound of formula III itself can be used as a solvent. In this condensation reaction is advantageously carried out in the presence of a strong acid, for. As para-toluenesulfonic acid and at boiling temperatures of the azeotropic mixture.

In other cases, in which the substituent Zin formula III stands for one of the usual leaving groups and Win formula V stands for a hydroxy group, it is expedient first to convert the alkanol of the formula Ia into a suitable metal salt in a manner known per se and then mix this with the compound of the formula Formula III, as already described, implement. Compounds of the formula III in which Z is one of the customary leaving groups defined above and the remaining substituents are as defined under formula I can be prepared from the alcohols of the formula Ia by exchanging their free hydroxy group for a leaving group Z.

The replacement of the free hydroxyl group in the compound of formula Ia against a leaving group Z is preferably carried out in a reaction-inert solvent. Examples of such solvents are: aromatic and aliphatic

Hydrocarbons, such as benzene, toluene, xylenes, petroleum ether, ligroin or cyclohexane; halogenated hydrocarbon oils chlorobenzene, methylene chloride, ethylene chloride, chloroform, carbon tetrachloride or tetrachlorethylene; Ethers and ethereal compounds such as diethyl ether, diisopropyl ether, tert-butyl methyl ether, dimethoxyethane, dioxane, tetrahydrofuran or anisole; Esters such as ethyl acetate, propyl acetate or butyl acetate; Nitriles ₍ such as acetonitrile or compounds such as dimethyl sulfoxide, dimethylformamide and mixtures of such solvents with one another.

The introduction of leaving group Z is carried out by customary methods. Does this chlorine, where is used as a reagent z. As phosphorus oxychloride, phosphorus trichloride, phosphorus pentachloride or preferably thionyl chloride used. It is generally carried out at temperatures of 0 ° to +120 ⁰ C. In the case of Z = bromine is preferably used phosphorus tribromide or phosphorus pentabromide and performs the reaction at 0 ° to + 50 ⁰ C by. If Z stands for one of the groups -OCO-R ₈ or

-0-C = NR ₉ NHRio

usually the corresponding acid chloride or amidinochloride is used as reagent. It is expedient if the reaction is carried out at temperatures of -20 ° to +50 ⁰ C, preferably -10 ° to + 3O ⁰ C, and in the presence of a weak base such as pyridine or triethylamine.

The Azolyfluorketone of formula II used as starting materials are partially known from the literature (see, EP-OO 27177). They can be prepared by known methods by

a) compounds of the formula VII

with bromine or chlorine in the presence of an acidic solvent and optionally in the presence of a hydrogen halide acceptor and in the corresponding azolyl bromine (chlorine) ketones the bromine (chlorine) exchanged in the usual way for fluorine, or

b) compounds of the formula VIII

(VIII)

with imidazole or 1,2,4-triazole in the presence of an acid binder and in the presence of a solvent, wherein R ₁ , R ₂ and Y have the meanings given under formula I.

For the preparation of the compounds of the formula Ic, the Lewis acids used are, for example, TiCl ₄ , AlCl ₃ , GaCl ₃ or InCl ₃ .

The temperature is -10 ° to 150 ° C in this reaction, preferably 0 ° to 50 ⁰ C.

The hydrogenation von.Verbindungen of formula Ic and compounds of formula Ib (ether) in which R ₃ is a C ₃ -C ₅ alkenyl is, at temperatures from 0 ° to 100 ⁰ C, preferably 10 ° to 5O ⁰ C, carried out. Hydrogenated media are used as solvents or diluents.

In the preparation of all the starting, intermediate and end products mentioned herein, in principle, unless specifically specified in detail, one or more reaction-inert solvents or diluents may be present. In question, for example, aliphatic and aromatic hydrocarbons, such as benzene, toluene, xylenes, petroleum ether; halogenated hydrocarbons, such as chlorobenzene, methylene chloride, ethylene chloride, chloroform, carbon tetrachloride, tetrachlorethylene; Ethers and ethereal compounds ₍ such as dialkyl ethers (diethyl ether, diisopropyl ether, tert-butyl methyl ether

etc.) anisole, dioxane, tetrahydrofuran; Nitriles, such as acetonitrile, propionitrile; N, N-dialkylated amides, such as dimethylformamide; dimethyl sulfoxide; Ketones, such as acetone, diethyl ketone, methyl ethyl ketone and mixtures of such solvents with one another. In

In some cases it may also be advantageous if the reaction or partial steps of a reaction are carried out under a protective gas atmosphere and / or absolute solvents and / or a reaction catalyst, for example KJ, is added. Suitable inert gases are inert gases ₍ such as nitrogen, helium, argon or, in certain cases, carbon dioxide.

The process described for the preparation of the compounds of the formula I according to the invention, including all partial steps, forms part of the present invention.

The compounds of the formula I have two asymmetric centers (*)

(D,

and thus form two diastereomeric enantiomeric pairs. In general, a mixture of the two racemates is formed in the preparation, which can usually be separated or at least enriched by crystallization or chromatography on silica gel. Where two melting points are given in Tables 1 and 2, these refer to the two racemates. The two racemates can be prepared by the usual methods of enantiomer separation, z. B, by fractional crystallization of the tartaric acid salts or by chromatography on opt. active carriers, dissect into the Anitpoden.

It has now surprisingly been found that, in contrast to known fungicides, the compounds of the formula I according to the invention additionally show a particularly pronounced activity against Piricularia species, in particular against Piricularia oryzae (rice blast). The fungus species Piricularia oryzae belongs to the fungi imperfecti and forms as fructification organs only Knnidinsnoren as asexual secondary fruit form. It represents one of the economically most important harmful factors in rice crops

because it infects the rice plants at all stages of growth (seedlings, leaves, stems, spikes, etc.) throughout the growing season. Depending on the location of the fungus and the stage in which the rice plants are infected, various English names are used for the disease: z. Leaf blast, which may cause the leaves to wither and lead to disturbed growth, Ear blast for infections of the panicle or parts of the panicle; "Neckblast" for the infestation of the panicle base, causing the panicle to bend and no or only abnormal grains are formed, "Node blasts" for the kinking of the stalks on the Nodes. Piricularia oryzae spreads through conidiospores, which are formed in humid weather in masses and are transported by the wind over long distances. In areas where there is a prolonged disruption of rice production over the year, conidiospores are formed on seedlings of infected seeds on crop residues (for example, straw and grass stored in the field) at the start of the growing season. When rice is grown throughout the year, crops of various ages often coexist, promoting the transmission of the disease through conidia that are constantly forming. Piriformia infestation generally results in very high crop failures and, in view of the fact that rice, after wheat and maize, is currently the world's third largest acreage under cereal crops, represents a major economic damage.

With the compounds of formula I, the Piriculariabefall can be successfully and easily controlled in all growth stages. In addition, the active ingredients of formula I are also active against the phytopathogenic fungi belonging to the following classes: fungi imperfecti (e.g., Botrytis, Helminthosporium, Fusarium, Septoria, Cercospora and Alternaria); Basidiomycetes (eg the genera Hemileia, Rhizocotonia, Puccinia); Ascomycetes (eg Venturia, Pddosphaera, Erysiphe, Monilinia, Uncinula). Moreover, the compounds of the formula I act systematically. They can also be used as a seed dressing for the treatment of seeds (fruits, tubers, grains) and plant cuttings for the protection of fungal infections and against occurring in the soil phytopathogenic fungi.

Furthermore, compounds of the formula I can be used successfully for the protection of perishable goods of plant or animal origin. They fight e.g. Molds such as Penicillium, Aspergillus, Rhizopus, Fusarium, Helminthosporium, Nigrospora and Alternaria, and bacteria such as butyric acid bacteria and yeasts such as Candida.

The compounds of the formula I can thus be used in the protection of stored products (eg for cereals, silages, hay, etc.). The compounds of the formula I thus show a very favorable for practical needs microbicidal spectrum against phytopathogenic fungi and bacteria. In particular, they have very advantageous preventive and additionally systemic properties and can be used for the protection of numerous crop plants, but preferably in rice crops. With the active compounds of the formula I, the occurring microorganisms can be contained or destroyed on plants or on parts of plants (fruits, flowers, foliage, stems, tubers, roots), whereby later growing plant parts are spared from such microorganisms.

The invention thus also relates to microbicidal agents and to the use of the compounds of the formula I for controlling phytopathogenic microorganisms, in particular plant-damaging fungi or, above all, for the preventive and systemic prevention of infestation with plants.

In addition, the present invention also includes the preparation of agrochemical agents characterized by the intimate mixing of the active substance with one or more substances or substance groups described herein. Also included is a method for the treatment of plants, which is characterized by application of the compound of formula I or the new agent.

In addition to the main crop rice, as target crops for the indications disclosed herein within the scope of this invention, for example, the following plant species are considered: cereals (wheat, barley, rye, oats, sorghum and relatives); Beets (sugar and fodder beets); Pome, stone and berry fruits (apples, pears, plums, peaches, almonds, cherries, peanuts, cranberries and blackberries); Legumes (beans, lentils, peas, soybeans); Oil crops (rape, mustard, poppy, olives, sunflowers, coconut, castor, cocoa, peanuts); Cucumbers (squash, cucumbers, melons); Fiber plants (cotton, flax, hemp, jute); Citrus fruits (oranges, lemons, grapefruit, mandarins); Vegetables (spinach, lettuce, asparagus, cabbage, carrots, onions, tomatoes, potatoes, peppers); Laurel family (avocado, cinnamonum, camphor) or plants such as corn, tobacco, nuts, coffee, sugar cane, tea, vines, hops, banana and natural rubber plants and ornamental plants (composites). Active ingredients of the formula I are usually used in the form of compositions and can be added to the surface or plant to be treated simultaneously or successively with further active ingredients. These further active ingredients may be fertilizers, trace element mediators or other preparations which influence plant growth. However, they may also be selective herbicides, insecticides, fungicides, bactericides, nematicides, molluscicides or mixtures of several of these preparations, together with optionally further customary in formulation technology excipients, surfactants or other application-promoting additives.

Suitable carriers and additives may be solid or liquid and correspond to the substances useful in formulation technology, such as. As natural or regenerated mineral substances, solvents, dispersants, wetting agents, adhesives, thickeners, binders or fertilizers.

A preferred method of applying an active ingredient of the formula I or of an agrochemical composition containing at least one of these active ingredients is application to the foliage (foliar application). Number of applications depend on the infestation pressure for the corresponding pathogen (type of fungus) or the type of growth influencing. The active ingredients of the formula I can also get through the soil through the root system in the plants (systematic effect) by soaking the location of the plants with a liquid preparation or introducing the substances in solid form in the soil, eg. B. in the form of granules (soil application). However, the compounds of the formula I can also be applied to seed grains (coating) by impregnating the grains either with a liquid preparation of the active ingredient or coating them with a solid preparation. In addition, other types of application are possible in special cases, such. As the targeted treatment of plant stems or buds.

The compound of formula I are used in unchanged form or preferably together with the usual in formulation technology aids and are therefore z. To emulsion concentrates, spreadable pastes, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granules, by encapsulation in e.g. processed polymeric substances in a known manner. The application methods such as spraying, misting, dusting, scattering, brushing or pouring are chosen in the same way as the type of means according to the desired goals and the given conditions. Cheap application rates are generally at 10g to 5kg of active substance (AS) ie ha; preferably 100a to 2ka AS / ha. in particular at 200a to 100n AS / ha

The formulations i. the agents, preparations or compositions containing the active substance of formula I and, where appropriate, a solid or liquid additive, are prepared in known manner, e.g. by intimately mixing and / or grinding the active compounds with extenders, such as. As with solvents, solid carriers, and optionally surfactants (surfactants).

Suitable solvents are: Aromatic hydrocarbons, preferably the fractions C ₈ to Ci ₂ , wiez. B.

Xylene mixtures or substituted naphthalenes, phthalic acid esters, such as dibutyl 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, strongly polar solvents; methyl-2-pyrrolidone, dimethyl sulfoxide or dimethylformamide, as well as epoxidised vegetable oils such as epoxidised coconut oil or _t soybean oil; or water.

As solid carriers, for. For example, for dusts and dispersible powders, natural minerals are generally used, such as calcite, talc, kaolin, montmorillonite or attapulgite. To improve the physical properties, it is also possible to add highly dispersed silicic acid or highly dispersed absorbent polymers. As granular, adsorptive granule carriers are porous types ₍ such as pumice, Zielgelbruch, Sepioiit or bentonite, non-sorptive carrier materials such as calcite or sand in question.) In addition, a variety of vorgranulierten materials of inorganic or organic nature such as especially dolomite or crushed plant residues are used.

Depending on the nature of the active compound of the formula I to be formulated, suitable surface-active compounds are nonionic, cationic and / or anionic surfactants having good emulsifying, dispersing and wetting properties. Surfactants are also surfactant mixtures.

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

As soaps are the alkali metal, alkaline earth metal or optionally substituted ammonium salts of higher fatty acids (Ci ₀ -C ₂₂ ), such as

z. As the Na or K salts of oleic or stearic acid, or of natural fatty acid mixtures, the z. B. can be obtained from coconut or tallow oil. Furthermore, the fatty acid methyltaurine salts should be mentioned.

Frequently, however, so-called synthetic surfactants are used, especially fatty sulfonates, fatty sulfates, sulfonated benzimidazole derivatives or alkyl sulfonates.

The fatty sulfonates or sulfates are typically present as alkali, alkaline earth or ammonium substituted ammonium salts and have an alkali radical of 8 to 22 carbon atoms, alkyl also including the alkyl moiety of acyl radicals, e.g. the Na or Ca salt of lignosulfonic acid, of the dodecylsulfuric acid ester or of a fatty alcohol sulfate mixture prepared from natural fatty acids.

This subheading also covers the salts of sulfuric acid esters and sulfonic acids of fatty alcohol-ethylene oxide adducts. The sulfonated benzimidazole derivatives preferably contain 2-sulfonic acid groups and a fatty acid residue having 8-22 C atoms.

Alkylarylsulfonates are z. As the Na, Ca or triethanolamine salts of dodecylbenzenesulfonic acid, dibutylnaphthalenesulfonic acid, or a naphthalenesulfonic acid-formaldehyde condensation product.

Furthermore, corresponding phosphates wiez. B. salts of the phosphoric acid ester of a p-NonylphenoI- (4-14) -Ethylenoxyd adduct in question.

Suitable nonionic surfactants are primarily 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 radical and 6 to 18 carbon atoms in the alkyl radical of the alkylphenols ,

Further suitable nonionic surfactants are the water-soluble 20 to 250 ethylene glycol ether groups and 10 to 100 g propylene glycol ether groups contain polyethylene oxide adducts of polypropylene glycol, ethylenediaminopolypropylene glycol and alkylpolypropylene glycol having 1 to 10 carbon atoms in the alkyl chain. The compounds mentioned usually contain 1 to 5 ethylene glycol units per propyglycol unit.

Nonylphenolpolyethyoxyethanols, castor oil polyglycol ethers, polypropylene-polyethylene oxide adducts, tributylphenoxypolyethyleneethanol, polyethylene glycol and octylphenoxypolyethanol may be mentioned as examples of nonionic surfactants.

Also suitable are fatty acid esters of polyoxyethylene sorbitan, such as the polyoxyethylene sorbitan trioleate.

The cationic surfactants are, above all, quaternary ammonium salts which contain at least one alkyl radical having 8 to 22 carbon atoms as N substituents and have lower, optionally halogenated, alkyl, benzyl or lower hydroxyalkyl radicals as further substituents. The salts are preferably in the form of halides, methylsulfates or ethylsulfates, e.g. The stearyltrimethylammonium chloride or the benzenedi (2-chloroethyl) ethylammonium bromide.

For the preparation of compositions according to the invention which contain the active ingredients of the formula I as active components, the surfactants described above can be used together with further auxiliaries according to the methods customary in formulation technology.

The agrochemical preparations generally contain 0.1 to 99%, in particular 0.1 to 95% active ingredient of the formula 1.99.9 to 1%, in particular 99.8 to 5% of a solid or liquid Zusatzstoifes and 0 to 25% , in particular 0.1 to 25% of a surfactant.

While merchandise is more likely to be concentrated, the end user typically uses diluted funds.

The compositions may also contain other additives such as stabilizers, defoamers, viscosity regulators, binders, adhesives and fertilizers or other active ingredients to achieve special effects.

Such agrochemical agents are part of the present invention.

embodiment

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

Preparation Examples

Example 1: Preparation of 1- (2,4-dichlorophenyl) -1-methyl-2-fluoro-2- (1H-1,2,4-triazol-1-yl) -ethanol

Cl

OH H

CH ₃ F

27.4 g of 2,4-dichloro-ü) -triazolyl-cu-fluoro-acetophenone are dissolved in a mixture of 10O ml of diethyl ether and 10O ml of tetrahydrofuran and cooled to -65 ⁰ C. With vigorous stirring, a Grignard solution, which was prepared from 15 g of methyl iodide and 24.5 g of magnesium in 200 ml of diethyl ether, is added dropwise so that the temperature does not rise above -60 ⁰ C.

With stirring, the reaction mixture is warmed to room temperature and left at this temperature for one hour.

Then, with gentle cooling, 100 ml of a saturated solution of ammonium chloride are added dropwise.

For workup, the organic phase is separated, washed neutral with brine, dried over sodium sulfate and evaporated under vacuum. The residue consists of 27,0g of a light oil.

In high pressure chromatography, this oil is found to consist of two components with a peak ratio of 1: 1.3 (two pairs of enantiomers).

With the aid of diisopropyl ether, the oil can be crystallized, wherein the racemate, which is present in a larger amount, crystallized and then melts at 149 ° C-155 ° C. The spectroscopic data are consistent with the expected structure. In particular, an OH group is clearly visible in the IR spectrum. In the proton NMR spectrum, the OH group appears at 6.75 ppm and the CH ₃ group is visible at 1.90 ppm. The two peaks of the HF coupling are at 6.98 and

Example 2: Preparation of 1-Fluoro-1- (1-H-1,2,4-triazol-1-yl) -2-methyl-2-methoxy-2- (2,4-dichlorophenyl) -propane

29.0 g of the compound of Example 1 are dissolved in 500 ml of methylene chloride. 1 g of tert-butylammonium bromide and 50 ml of 50% strength potassium hydroxide solution are added at 0 ⁰ C to the solution. At a temperature between 0 and +5 ⁰ C 10ml of methyl iodide are added dropwise. When stirring at 0-5 ⁰ C falls in the course of two hours, the potassium bromide completely. To complete the reaction, the mixture is stirred for another two hours at room temperature, whereupon the organic phase is separated off, washed neutral with water and dried with sodium sulfate. This gives 30.0 g of a light oil. This can be brought to crystallization with the aid of cyclohexane and di-iso-propyl ether. The resulting crystal mixture melts after drying between 97 ⁰ C and 103 ⁰ C.

The HPLC shows that it is almost exclusively a mixture of the two pairs of enantiomers.

The NMR spectrum shows the two CH ₃ groups at 2.00 and 3.40 ppm, as well as the two peaks of the HF coupling at 6.60 and

Example 3: Preparation of 1- (2,4-dichlorophenyl) -1-allyl-2-fluoro-2- (1H-1,2,4-triazol-1-yl) -ethanol

Cl- y

'~ * CH₂-CH = CH₂

27.4 g of 2,4-dichloro-ü) -triazolyl-ü) -fluoro-acetophencn are dissolved in 150 ml of dichloromethane. In the absence of air (in a stream of nitrogen) 9.5 g of titanium tetrachloride are added at 20 ° C. After stirring for 5 minutes, 11.5 g of trimethyl-allylsilane are added, the temperature rising to about 28 ° C. within 5 minutes. After 5 min., The brown-red emulsion is poured onto ice water, carefully made alkaline with Na ₂ CO ₃ and extracted twice with ethyl acetate.

The ethyl acetate solution is dried with sodium sulfate and evaporated in vacuo. The residue consists of 29,0g of a dark brown oil. Upon cooling, this can be made to crystallize. By recrystallization from an ethyl acetate / diethyl ether mixture to obtain 12.0 g (67%) of a at 127 ⁰ C-128 ° C melting product.

Example 4: Preparation of 2- (2,4-dichlorophenyl) -1-fluoro-1- (1H-1,2,4-triazol-1-yl) -pentanol- (2)

31.6 g of the compound of Example 3 are hydrogenated with the aid of Pd / activated carbon in ethyl acetate at room temperature and under atmospheric pressure. After filtration and evaporation under vacuum, 31.8 g of a pale oil are obtained. With the aid of ethyl acetate, it can be brought to crystallize and after recrystallization from a mixture of ether and ethyl acetate to obtain 26.5 g of crystals of melting point 108 ° C-109 ° C.

Example 5: Production of i

CH ₂ -CH = CH ₂

31.6 g of the compound of Example 3 are methylated analogously as described in Example 2. After work-up, 32.5 g of a pale oil are obtained. This is subjected to short path distillation at 13Pa at 140X.

This gives 26.2 g of colorless oil.

Analogously to the examples described above, the compounds tabulated below can be prepared.

Table 1

>'~ Λ _Ϊ ^Η

 - <.; - j-

· = · R ₃

No. Ri R ₂ R ₃ Y physical data 1.1 Cl Cl CH ₃ N Mp 149-155 ° C 1.2 Cl Cl CH ₃ CH 1.3 Cl Cl C ₂ H ₅ : N 1.4 Cl Cl C ₂ H ₅ CH 1.5 Cl Cl C ₃ H ₇ (Ii) N Mp. 108-109 ⁰ C 1.6 Cl Cl C ₃ H ₇ (Ii) CH Oei 1.7 CH ₃ CH ₃ CH ₃ N Oei 1.8 CH ₃ CH ₃ C ₂ H ₅ N 1.9 CH ₃ CH ₃ C ₂ H ₅ . CH 1.10 1.11 1.12 CH ₃ HH CH ₃ FF C ₃ H ₇ (Ii) CH ₃ CH ₃ NN> CH OeI ^ 130-132 ⁰ C * mp. 74-76 ⁰ C * 1.13 H F C ₂ H ₅ N 1.14 1.15 1.16 H H H F Cl Cl C ₃ H ₇ (Ii) CH ₃ CH ₃ NN CH ^ 28-130 ⁰ C * mp ^N 86-88 ⁰ C * 1.17 H Cl C ₂ H ₅ N · 1.18 H Cl C ₂ H ₅ CH 1.19 H Cl C ₃ H ₇ (n) N 1.20 H br CH ₃ N 1.21 H br C ₂ H ₅ N 1.22 F f CH ₃ N 23.1. F F C ₂ H ₅ N 1.24 Cl F CH ₃ N 1.25 Cl. F C ₂ H ₅ N 1.26 Cl F C ₃ H ₇ (Ii) N resin 1.27 Cl br CH ₃ N

* («Diastereoinera pairs)

Continuation: Table 1

No. Ri R ₂ C ₂ H ₅ Y physical data 1.28 Cl br CH ₃ N 1.29 Cl CH ₃ C ₂ H ₅ N 1.30 Cl CH ₃ CH ₃ N 1.31 CH ₃ H CH ₃ N Mp. 141-143 ⁰ C 1:32 CH ₃ Cl C ^ H ₉ Cn) N Mp 134-135 ° C 1:33 Cl Cl CitHgCtert) N Oei 1:34 H Cl allyl N Mp 128-130 ⁰ C 1:35 Cl Cl allyl N Mp 127-128 ° C 1:36 H Cl N Mp. 106-108 ⁰ C

Table 2

? - · · C-

· = · Ra

No. Ri R ₂ R ₃ CH ₃ Y physical data 2.1 Cl Cl CH ₃ CH ₃ N Mp. 97-103 ⁰ C 2.2 Cl Cl CH ₃ C ₃ H ₇ (Ii) CH 2.3 Cl Cl CH ₃ C ₃ H ₇ (Ii) N Oei 2.4 Cl Cl CH ₃ C ₁ H ₉ (Ii) CH ₂ CH = CH ₂ CH resin 2.5 2.6 Cl Cl Cl Cl CH ₃ CH ₃ CH ₂ CH = CH ₂ N N OeI, bp ₁ _ 150 ⁰ C 1, Jp resin 2.7 Cl Cl CH ₃ CH ₂ CH = CH-CH ₃ CH Oei 2.8 Cl Cl CH ₃ CH ₃ N resin 2.9 Cl Cl C ₂ H ₅ CH ₃ N 2.10 Cl Cl C ₂ H ₅ C ₃ H ₇ (n) CH 2.11 Cl Cl C ₂ H ₅ CH ₂ CH (CH ₃ ) ζ N 2.12 Cl Cl C ₂ H ₅ CH ₂ CH = CH ₂ N 2.13 Cl Cl C ₂ H ₅ CH ₂ C (CH ₃ ) = CH ₂ N 2.14 Cl Cl C ₂ H ₅ CH ₃ N 2.15 Cl Cl C ₃ H ₇ (n) CH ₃ N Oei 2.16 Cl Cl C ₃ H ₇ Cn) C ₃ H ₇ (n) CH Oei 2.17 Cl Cl C ₃ H ₇ (Ii) CH ₂ CH = CH ₂ N resin 2.18 Cl Cl C ₃ H ₇ (Ii) CH ₃ N Oei 2.19 CH ₃ CH ₃ CH ₃ CH ₃ N Oei 2.20 CH ₃ CH ₃ CH ₃ CH ₃ CH Oei 2.21 CH ₃ CH ₃ C ₂ H ₅ CH ₃ N Oei 2.22 CH ₃ CH ₃ C ₃ H ₇ CH ₃ N 2.23 H F CH ₃ CtH ₉ (Ii) N 2.24 H F CH ₃ CH ₂ CH = CH-CH ₃ N 2.25 H F CH ₃ CH ₃ N 2.26 H F C ₂ H ₅ C ₃ H ₇ (n) N 2.27 H F C ₂ H ₅ CH ₂ -CH-CH ₂ N 2.28 H F C ₂ H ₅ CH ₃ N 2.29 H F C ₃ H ₇ (Ii) N

Continuation: Table 2

No. Ri R ₂ Rs rn allyl CH ₃ Y physical data 30.2 H Cl CH ₃ CH ₃ C ₃ H ₇ U) CH ₃ N 115-116 ° C 2.31 H Cl CH ₃ CH ₃ CH 2:32 H Cl CH ₃ C ₃ H ₇ (Ii) N 2:33 H Cl CH ₃ CH ₂ CH ¹¹ CH ₂ N 2:34 H ' Cl C ₂ H ₅ CH ₃ N 2:35 H Cl C ₂ H ₅ CH ₃ CH 2:36 H Cl C ₂ H ₅ C ₃ H ₇ (n) N 2:37 H Cl C ₂ H ₅ CH ₂ CH = CH ₂ N 2:38 H Cl C ₃ H ₇ (n) CH ₃ N 2:39 H br CH ₃ CH ₃ N 2:40 H Br. C ₂ H ₅ CH ₃ N 2.4.1 F F CH ₃ CH ₃ N 2:42 F F C ₂ H ₅ CH ₃ N 2:43 Cl F CH ₃ CH ₃ N 2:44 Cl F C ₂ H ₅ CH ₃ N * 2:45 Cl F C ₃ H ₇ CH ₃ N 2:46 Cl br CH ₃ CH ₃ N 2:47 Cl br C ₂ H ₅ CH ₃ N 2:48 Cl CH ₃ CH ₃ CH ₃ N 2:49 Cl CH ₃ C ₂ H ₅ CH ₃ N 2:50 Cl Cl CH ₃ CH ₂ -C ₅ H ₃ (Cl) ₂ U, 4) N 140-142 ⁰ C 2:51 Cl Cl N Oei 2:52 Cl Cl N Oei

Table 3

No. Ri R ₂ R ₃ Ri, R ₅ Y X physikal. dates 3.1 Cl Cl CH ₃ CH ₃ CH ₃ N CH ₃ OSO ₃ Mp 164 ° -166 ° C

Formulation Examples (% = wt%)

1. Emulsion concentrates Active ingredient from the tables Ca-dodecylbenzenesulfonate castor oil polyethylene glycol ether (36 mol ethylene oxide) tributylphenyl polyethylene glycol ether (30 mol ethylene oxide) cyclohexane

xylenes

From such concentrates, emulsions of any desired concentration can be prepared by dilution with water.

b) -17- 261735 c) a) 40% 50% 25% 8th% 6% 5% - - 5%. 12% 4% 15% 20% - 25% 20% 65%

2. Solutions

Active ingredient from the tables Ethylene glycol monomethyl ether Polyethylene glycol MG 400 N-methyl-2-pyrrolidoh Epoxydated coconut oil Gasoline (boiling limit 160-190 ⁰ C) (MW = molecular weight)

The solutions are suitable for use in the form of very small drops.

a) b) c) d) 80% 10% 5% 95 ° / 20% - - - - 70% - - - 20% - - - - 1% 94%

3. Granules

Active ingredient from the tables kaolin

  Highly dispersed silica attapulgite

b)

90%

The active ingredient is dissolved in methylene chloride, sprayed onto the carrier and the solvent is then evaporated in vacuo.

4. Dusts Active substance from the tables Fumed silica Talc Kaolin

b)

90%

Intimate mixing with excipients with the active ingredient gives ready-to-use dusts.

5. Spray powder

Active substance from the tables Na lignosulfonate Na lauryl sulfate

Na-diisobutylnaphthalenesulfonate Octylphenol polyethylene glycol ether (7-8 mol ethylene oxide) Highly dispersed silica kaolin

a) b) O 25% 50% 75% 5% 5% - 3% - 5% - 6% 10% 2% 5% 10% 10% 62% 27%

The active ingredient is well mixed with the additives and ground well in a suitable mill. This gives wettable powders which can be diluted with water to give suspensions of any desired concentration.

6. Emulsion concentrate Active substance from the tables Octylphenol polyethylene glycol ether (4-5 mol ethylene oxide) Ca dodecyl benzene sulphonate Ricinusölpolyglykolether (35 mol ethylene oxide) Cyclohexanone

xylenes

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

a) b) 5% 8 ⁰ X 85%

7. Dust

Active ingredient from the tables

talc

Kaolin - 95%

Ready-to-use dusts are obtained by milling the active ingredient mixed with the carrier on a suitable mill.

8. extruder granules

Active substance from the tables 10%

Na lignosulfonate 2%

Carboxymethylcellulose 1%

Kaolin 87%

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

9. Serving Granules

Active substance from the tables 3%

Polyethylene glycol (MG200) 3%

Kaolin 94%

(MW = molecular weight)

The finely ground active ingredient is applied evenly in a mixer to the kaolin moistened with polyethylene glycol. In this way, dust-free coating granules are obtained.

10. suspension concentrate

Active substance from the tables 40%

Ethylene glycol 10%

Nony! Phenol polyethylene glycol ether

(15 moles of ethylene oxide) 6%

N-lignosulfonate 10%

Carboxymethylcellulose 1%

37% aqueous formaldehyde solution 0.2%.,

Silicone oil in the form of a 75%

aqueous emulsion 0.8%

Water 32%

The finely ground active substance is intimately mixed with the additives. This gives a suspension concentrate from which suspensions of any desired concentration can be prepared by dilution with water.

Biological examples Example 1: Action against Piricularia oryzae on rice

a) Residual-protective action

Rice plants were sprayed after two weeks of cultivation with a spray of active ingredient prepared spray mixture 0.02% active ingredient). After 48 hours, the treated plants were infected with a conidia suspension of the fungus. After 5 days of incubation at 95-100% relative humidity and 24 ° C, the fungal infection was assessed.

b) Systemic effect

To two-week rice plants, a spray mixture prepared from wettable powder of the active ingredient was poured (0.006% active substance based on the volume of soil). Then the pots were filled with water to the extent that the lowest stem parts of the rice plants were in the water. After 96 hours, the treated rice plants were infected with a conidia suspension of the fungus. After incubation of the infected plants for 5 days at 95-100% relative humidity and about 24 ⁰ C, the fungal infection was assessed.

The untreated but infected control plants showed a fungal attack of 100% in the two tests a and b. Rice plants treated with compounds from the tables showed a reduction of fungal attack to 0 to 25%. Compounds Nos. 1.1,1.5,1.6,1.7,1.10,1.11,1.15.1.26,1.33,1.34-1.36,2.1,2.3-2.8,2.15-3.19,2.51 and 2.52 completely suppressed fungal infestation (0% infestation).

Example 2: Action against Puccinia graminis on wheat a) Residual-protective action

Wheat plants were sprayed 6 days after sowing with a spray mixture prepared from wettable powder of the active ingredient (0.02% active substance). After 24 hours, the treated plants were infected with a uredospore suspension of the fungus. After incubation for 48 hours at 95-100% relative humidity and about 20 ⁰ C, the infected plants were placed in a greenhouse at about 22 ° C. The assessment of rust pustule development was 12 days after infection.

b) Systemic effect

5 days after sowing, a spray mixture prepared from spray powder of the active substance was poured into wheat plants (0.006% of active substance based on the soil volume). After 72 hours, the treated plants were infected with a uredospore suspension of the fungus. After incubation for 48 hours at 95-100% relative humidity and about 20 ⁰ C, the infected plants were placed in a greenhouse at about 22 ⁰ C. The assessment of rust pustule development was made 12 days after infection.

Compounds from the tables showed a very good action against Puccinia mushrooms. Untreated but infected control plants had a Puccinia infestation of 100%. Among others, Compounds Nos. 1.1,1.5,1.6,1.7,1.10, 1.11,1.15,1.2.3,1.33,1.34-1.36,2.1,2.3-2.8,2.15-2.19,2.51 and 2.52 almost completely inhibited Puccinia infestation (0 up to 5% infestation).

Example 3: Action against Erysiphe graminis on barley

a) Residual-protective effect

Barley plants about 8 cm high were sprayed with a spray mixture (0.02% active substance) prepared from the spray powder of the active ingredient. After 24 hours, the treated plants were pollinated with conidia of the fungus. The infected barley plants were placed in a greenhouse at about 22 ⁰ C and assessed the fungal infection after 10 days.

b) Systemic effect

To a barley plants about 8 cm high, a spray mixture prepared from wettable powder of the active ingredient was poured (0.006% active substance based on the volume of the soil). Care was taken to ensure that the spray mixture did not come into contact with the aboveground plant parts. After 72 hours, the treated plants were pollinated with conidia of the fungus. The "infected barley plants were placed in a greenhouse at about 22 ° C and assessed the fungal infection after 10 days.

Compounds of formula I showed good activity against Erysiphe mushrooms. Untreated but infected control plants had an Erysiphe infestation of 100%. Among other compounds in the tables, compounds Nos. 1.1, 1.5, 1.6, 7.1, 10, 11, 11, 1, 12, 12, 16, 8, 11, 12, 21, 21, 21, 18, 21, 21, 18, 21, 21, 21, 21, 21, 21, 21, 21, and 21, inhibited fungal infestation in barley to 0 to 5%.

Example 4: Action against Cercospora arachidicola on peanut plants

a) Residual-proptektive effect

10-15 cm high peanut plants were sprayed with a spray liquor prepared from active ingredient spray powder (0.006% active ingredient) and infected 48 hours later with a conidia suspension of the fungus. The infected plants were incubated for 72 hours at about 21 ⁰ C and high humidity and then placed in a greenhouse until the appearance of the typical leaf spot.

The evaluation of the fungicidal activity takes place 12 days after the infection based on the number and size of the spots occurring

Systematic effect

b) To 10-15cm high peanut plants, a spray mixture prepared from wettable powder of the active ingredient was poured (0.06% active substance based on the volume of the earth). After 48 hours, the treated plants were infected with a conidia suspension of the fungus and incubated for 72 hours at about 21 ° C and high humidity. Subsequently, the plants were placed in the greenhouse and assessed after 11 days of fungal infestation.

Compared to untreated but infected control plants (number and size of spots = 100%), peanut plants treated with active ingredients from the tables showed a greatly reduced Cercospora infestation. Thus, Compounds Nos. 1.1,1.5,1.6,1.7,1.10,1.11,1.15,1.26,1.33,1.34-1.36,2.1,2.3-2.8,2.15-2.19,2.51 and 2.52 almost completely prevented the occurrence of stains in the above experiments (0 to 10%).

Example 5: Residual-protective action against Venturia inaequalis on apple shoots

Apple cuttings with 10-20cm long fresh shoots were sprayed with a spray mixture of active ingredient prepared spray powder (0.06% active ingredient). After 24 hours, the treated plants were infected with a conidia suspension of the fungus. The plants are incubated and placed for 10 more days in a greenhouse at 20-24 ⁰ C. The scab infestation was assessed 15 days after the infection. Compounds Nos. 1.1,1.5,1.6,1.7,1.10,1.11,1.15,1.2,13,1.3,1.34-1.36, 2.1, 2.3-2.8, 2.15-2.19,2.51 and 2.52 inhibited the disease infestation to less than 10%. Control plants were 100% infested.

Claims (17)

1. A composition for controlling or preventing an infestation by microorganisms, characterized in that it comprises as active component at least one compound of the formula I. # in which R ₅ , R ₆ and R ₇ independently of one another are hydrogen, nitro, halogen, cyano, C ₁ -C ₃ -alkyl, C ₁ -C ₃ -alkoxy, C _r C ₃ -haloalkoxy or CF ₃ , and Y represents a nitrogen atom or the CH group, including their acid addition salts, quaternary azolium salts and metal salt complexes in addition to additives and / or surface-active agents. 2. Composition according to claim 1, characterized in that it comprises as active component at least one compound of the formula Γ contains, in which R 1 is hydrogen, halogen, C ₁ -C ₂ -alkyl or CF ₃ ; R _{2 is} halogen or C ₁ -C ₂ -alkyl; R _{3 is} C ₁ -C ₄ -alkyl; R _{4 is} hydrogen, C ₁ -C ₄ -alkyl, C ₃ -C ₄ -alkenyl or the group - CH ₂ -v / * where R ₅ , R ₆ and R ₇ independently of one another are hydrogen, nitro, halogen, cyano, C ₁ -C ₃ -alkyl, C ₁ -C ₃ -alkoxy, C _r C ₃ -haloalkoxy or CF ₃ , and Y represents a nitrogen atom or the CH group, including their acid addition salts, quaternary azolium salts and metal salt amines in addition to additives and / or surface-active agents. 3. Composition according to claim 2, characterized in that in the compounds of formula Γ R ₁ ZR ₂ 2,4-Cl ₂ or 2,4- (CH ₃ ) ₂ ; R _{3 is} C ₁ -C ₂ alkyl; and R _{4 is} hydrogen, C ₁ -C ₃ -alkoxy-I, allyl or 2,4-dichlorobenzyl Y is a nitrogen atom or the CH group
mean. 4. Composition according to claim 2, characterized in that in the compounds of formula Γ R ₁ ZR ₂ 2,4-Cl ₂ ; R ₃ is CH _3; and R _{4 is} hydrogen; and Y is a nitrogen atom
mean. 5. Composition according to claim 1, characterized in that in the compounds of the formula IR ₁ ZR ₂ 2,4-Cl ₂ or 2,4- (CH ₃ ) ₂ ; R ₃ is C _r C ₃ -AlkyloderC ₃ -C ₄ alkenyl; R _{4 is} hydrogen, C _r C ₃ alkyl, allyl or 2,4-dichlorobenzyl; and Y is a nitrogen atom or the CH group
mean. 6. A composition according to claim 1, characterized in that in the compounds of formula I Ri is hydrogen, chlorine or methyl; R _{2 is} fluorine, chlorine or methyl; R ₃ is C _r C ₄ alkyl or allyl; R ₄ is C _r C ₄ alkyl or C ₃ -C ₄ -AlkenyI; and Y is a nitrogen atom or the CH group
mean. 7. Composition according to claim 5, characterized in that in the compounds of formula IR ₁ ZR ₂ 2,4-Cl ₂ ; R ₃ is CH _3; n-propyl or allyl; R _{4 is} hydrogen or methyl; and Y is a nitrogen atom
mean. 8. Composition according to claim 6, characterized in that in the compounds of formula IR ₁ hydrogen, chlorine or methyl; R _{2 is} fluorine, chlorine or methyl; R _{3 is} methyl, n-propyl, n-butyl, tert. Butyl or allyl; R _{4 is} methyl, n-propyl, η-butyl, allyl or but-2-enyl; Y is a nitrogen atom or the CH group
mean. 9. Composition according to claim 2, characterized in that the compound of formula Γ is selected from the group: 1- (2,4-dichlorophenyl) -1-methyl-2-fluoro-2- (1H-1,2,4-triazol-1-yl) -ethanol; 1- (2,4-dichlorophenyl) -1-methyl-l-methoxy-2-fluoro- (1H-1,2,4-triazol-1-yl) ethane. 10. Composition according to claim 1, characterized in that the compound of the formula I is selected from the group: 1- (2,4-dichlorophenyl) -1-n-propyl-2-fluoro-2- (1H-1,2,4-triazol-1-yl) -ethanol; 1- (1,2-dichlorophenyl) -1-n-propyl) -2-fluoro-2- (1 H -imidazol-1-yl) -ethanol; 1- (2,4-dimethylphenyl) -1-methyl-2-fluoro-2- (1H-1,2,4-triazol-1-yl) ethanol; 1- (2,4-dimethylphenyl) -1-n-propyl-2-fluoro-2- (1H-1,2,4-triazol-1-yl) ethanol; 1- (4-fluorophenyl) -1-methyl-2-fluoro-2- (1H-1,2,4-triazol-1-yl) ethanol; 1- (4-chlorophenyl) -1-methyl-2-fluoro-2- (1H-1,2,4-triazol-1-yl) ethanol; 1- {2-chloro-4-fluorophenyl) -1-n-propyl-2-fluoro-2- (1H-1,2,4-triazol-1-yl) ethanol; 1- (2,4-dichlorophenyl) -1-n-butyl-2-fluoro-2- (1H-1,2,4-triazol-1-yl) ethanol; i ^ -ChlorphenyD-i-t-Butyl ^ -fluoro ^ -ie-i ^^ - triazol-i-yD-ethanol; 1- (2,4-dichlorophenyl) -1-allyl-2-fluoro-2- (1H-1,2,4-triazol-1-yl) ethanol; 1- (4-chlorophenyl) -1-allyl-2-fluoro-2- (1H-1,2,4-triazol-1-yl) ethanol; 1- (2,4-dichlorophenyl) -1-methyl-1-methoxy-2-fluoro-2- (1H-1,2,4-triazol-1-yl) ethane; 1- (2,4-dichlorophenyl) -1-methyl-1-n-propoxy-2-fluoro-2- (1H-1,2,4-triazol-1-yl) -ethane; 1- (2,4-dichlorophenyl) -1-methyl-1-n-propoxy-2- (1H-imidazol-1-yl) -ethane; 1- (2,4-dichloro-phenyl) -1-methyl-1-n-butoxy-2-fluoro-2- (1H-1,2,4-triazol-1-yl) -ethane; 1- (2,4-dichlorophenyl) -1-methyl-1-allyloxy-2-fluoro-2- (1H-1,2,4-triazol-1-yl) -ethane; 1- (2,4-dichlorophenyl) -1-methyl-1-allyloxy-2-fluoro-2- (1H-imidazol-1-yl) -ethane; 1- (2,4-dichlorophenyl) -1-n-propyl-1-methoxy-2-fluoro-2- (1H-1,2,4-triazol-1-yl) ethane; 1- (2,4-dichlorophenyl) -1-n-propyl-1-methoxy-2- (1 H -imidazol-1-yl) -ethane; 1- (2,4-dichlorophenyl) -1-n-propyl-1-n-propoxy-2-fluoro-2- (1H-1,2,4-triazol-1-yl) ethane; 1- (2,4-dichlorophenyl) -1-n-propyl-1-allyloxy-2-fluoro-2- (1H-1,2,4-triazol-1-yl) -ethanol; 1- (2,4-dimethylphenyl) -1-methyl-1-methoxy-2-fluoro-2- (1H-1,2,4-triazol-1-yl) ethane; 1- (2,4-dichlorophenyl) -1-allyl-1-methoxy-2-fluoro-2- (1H-1,2,4-triazol-1-yl) ethane; 1- (2,4-dichlorophenyl) -1-n-propyl-1-methoxy-2-fluoro-2- (1H-1,2,4-triazol-1-yl) -ethane. 11. Composition according to claim 1, characterized in that it contains 0.1 to 99% of an active ingredient of the formula 1,99,9 to 1% of a solid or liquid additive and 0 to 25% of a surfactant. 12. Composition according to claim 2, characterized in that it contains 0.1 to 99% of an active ingredient of the formula Γ, 99.9 to 1% of a solid or liquid additive and 0 to 25% of a surfactant. 13. A composition according to claim 11, characterized in that it contains 0.1 to 95% of an active ingredient of the formula 1,99,8 to 5% of a solid or liquid additive and 0.1 to 25% of a surfactant. 14. Composition according to claim 2, characterized in that it contains 0.1 to 95% of an active ingredient of the formula I ', 99.8 to 5% of a solid or liquid additive and 0.1 to 25% of a surfactant. 15. A method for controlling or preventing an infestation of crop plants by phytopathogenic microorganisms, characterized by applying a defined according to claim 1 means containing a compound of formula I to the plant or its location. 16. The method according to claim 15, characterized in that one as defined in claim 2 defined agent containing a compound of formula appl applied to the plant or its location. 17. Use of agents containing a compound of the formula I according to claim 1, characterized in that they are used for the control and / or preventive prevention of infestation of microorganisms. 18. Use of agents according to claim 17, containing a compound of formula Γ according to claim 2, characterized in that they are used for the control and / or preventive prevention of infestation of microorganisms.