DE4222542A1 - Triazolyl butane derivatives - Google Patents

Abstract

New triazolyl-butane derivates have the formula (I), in which (A) stands for a ketone group or for a CH(OH) grouping and (R) stands for ethyl, n-propyl, isopropyl, branched butyl, straight or branched chain alkyl with more than 4 carbon atoms, possibly substituted cycloalkylalkyl, alkenyl, alkinyl or for a grouping having the formulae (a), (b), (c), (d), (e), (f) or (g). Also disclosed are the acid addition salts and metal salt complexes of these derivates, a process for preparing these new substances and their use as fungicides.

Description

The present invention relates to new triazolyl-butane Derivatives, a process for their preparation and their Use as a fungicide.

It is already known that certain triazolylbutane Derivatives have fungicidal properties (see. DE-OS 30 48 267 and EP-OS 0 226 916). So you can game 2,2-dimethyl-1-phenyl-4- (1,2,4-triazol-1-yl) - octan-3-ol, 2,2-dimethyl-1- (4-methylphenyl) -4- (1,2,4- triazol-1-yl) octan-3-ol and 2,2-dimethyl-1- (4-chloro phenyl) -4- (1,2,4-triazol-1-yl) octan-3-ol to combat of mushrooms. The effect of these substances is good but leaves at low application rates in some cases to be desired.

There have now been new triazolyl-butane derivatives of the formula

in which
A represents a keto group or a CH (OH) group and
R for ethyl, n-propyl, isopropyl, branched butyl, straight-chain or branched alkyl having more than 4 carbon atoms, optionally substituted cycloalkylalkyl, alkenyl, alkynyl or for a grouping of the formula

stands, as well as their acid addition salts and metal salt complexes found.  

The triazolyl-butane derivatives of the formula (I) in which A stands for a CH (OH) group, two neighboring bears asymmetrically substituted carbon atoms. they can therefore in the two geometric isomers (threo and erythro form) exist, which differ proportions may arise. The verb of formula (I), in which A is a keto group stands, have an asymmetrically substituted carbon substance atom. In both cases, the connections of the Formula (I) in various optical isomer forms are present in different proportions may arise. The present invention relates to both the isomer mixtures and the individual iso meren.

Furthermore, it was found that the new triazolyl butane derivatives of the formula (I) and their acid adddi tion salts and metal salt complexes obtained when one Triazolyl ketone of the formula

with compounds of the formula

R-X (III)

in which
R has the meanings given above and
X stands for an electron-withdrawing leaving group,
in the presence of a base and in the presence of a diluent or in an aqueous-organic two-phase system in the presence of a phase transfer catalyst and, if appropriate, the resulting keto compounds of the formula

in which
R has the meanings given above, either
α) with complex hydrides in the presence of a diluent, or
β) reacted with aluminum isopropylate in the presence of a diluent,
and optionally then adding an acid or a metal salt to the triazolylbutane derivatives of the formula (I) thus obtained.

Finally it was found that the new triazolyl butane derivatives of the formula (I) and their acid adddi tion salts and metal salt complexes very good fungicidal Possess properties.

Surprisingly, the inventive ones stand out Substances with a better fungicidal effect than that most similar in constitution, from the prior art known compounds of the same indication. So excel fen the substances according to the invention z. B. the 2,2-dimethyl 1-phenyl-4- (1,2,4-triazol-1-yl) octan-3-ol and 2,2-dime thyl-1- (4-methylphenyl) -4- (1,2,4-triazol-1-yl) octane 3-ol and the 2,2-dimethyl-1- (4-chlorophenyl) -4- (1,2,4- triazol-1-yl) octan-3-ol, which is structurally close the known substances with the same direction of action regarding their fungicidal properties.

In addition, the new triazolyl butane derivatives are the Formula (I) interesting intermediates for the preparation other crop protection agents. So z. B. those compounds in which A is CO in Convey oximes, oxime ethers, hydrazones or ketals. The those compounds in which A represents a CH (OH) group pation, can be converted into ether or  by reaction with acyl halides or carbamoylchlo riden converted into acyl or carbamoyl derivatives the.

The triazolyl butane derivatives according to the invention are generally defined by formula (I).

A represents a keto group or a CH (OH) group tion.

R preferably represents ethyl, n-propyl, isopropyl, iso-butyl, sec-butyl, tert-butyl, straight chain or branched alkyl of 5 to 12 carbon atoms, for optionally by 1 to 3 alkyl groups with 1 to 4 carbon atoms each sub substituted cycloalkylalkyl with 3 to 7 carbons atoms in the cycloalkyl part and 1 to 4 carbons atoms in the alkyl part, for straight-chain or branched alkenyl with 3 to 12 carbon atoms, for straight-chain or branched alkynyl with 3 up to 12 carbon atoms or for a grouping of the formula

Is particularly preferred
R for ethyl, n-propyl, isopropyl, isobutyl, sec-butyl, tert-butyl, straight-chain or branched alkyl having 5 to 10 carbon atoms, for where appropriate by 1 to 3 methyl and / or ethyl groups Substituted cycloalkylalkyl with 3 to 6 carbon atoms in the cycloalkyl part and 1 or 2 carbon atoms in the alkyl part, for straight-chain or branched alkenyl with 3 to 10 carbon atoms, for straight-chain or branched alkynyl with 3 to 10 carbon atoms or for a grouping of the formula

Preferred substances according to the invention are also additions products from acids and triazolyl butane derivatives of Formula (I) in which A and R indicate the above as preferred have given meanings.

Acids that can be added include: preferably hydrohalic acids, such as. B. the chlorine  hydrochloric acid and hydrobromic acid, in particular hydrochloric acid, also phosphoric acid, Nitric acid, sulfuric acid, mono- and bifunctional Carboxylic acids and hydroxycarboxylic acids, such as. B. Vinegar acid, maleic acid, succinic acid, fumaric acid, wine acid, citric acid, salicylic acid, sorbic acid and Lactic acid and sulfonic acids, such as. B. p-toluenesulfone acid, 1,5-naphthalenedisulfonic acid or camphorsulfone acid, as well as saccharin and thiosaccharin.

Preferred compounds according to the invention are also Addition products from salts of metals from II. To IV. Main and I. and II. As well as IV. To VIII. In addition group of the periodic table of the elements and triazolyl butane derivatives of the formula (I) in which A and R are the have the meanings given above as preferred.

Here are salts of copper, zinc, manganese, magne sium, tin, iron and nickel especially before moves. Anions of these salts are those in Be that derive from such acids that to lead physiologically contractual addition products. Particularly preferred such acids are in this Connection the hydrohalic acids, such as. B. the Hydrochloric acid and hydrobromic acid, fer ner phosphoric acid, nitric acid and sulfuric acid.

Examples of substances according to the invention are those in the following table listed triazolyl butane deri called vate.  

Table 1

If 1- (4-bromophenyl) -2,2-dimethyl-4- (1,2,4- triazol-1-yl) -butan-3-one and 3-methyl-butyl-bromide as Starting materials, the course of the fiction process according to the following formula become clear:

If 2,2,5-trimethyl-1- (4-bromophenyl) -4- is used (1,2,4-triazol-1-yl) octan-3-one as a starting material and Sodium borohydride as a reducing agent, the Ver course of the method according to the invention by the following Formula scheme to be illustrated:

That when carrying out the inventive method rens required 1- (4-bromo-phenyl) - as the starting product 2,2-dimethyl-4- (1,2,4-triazol-1-yl) butan-3-one Formula (II) is known (see EP-OS 0 226 916).

Formula (III) provides a general definition of the compounds required as reaction components when carrying out the process according to the invention. In this formula, R preferably represents those radicals which have already been mentioned for this substituent in connection with the description of the triazolylbutane derivatives of the formula (I) according to the invention. X preferably represents chlorine, bromine, iodine, 4-methylphenylsulfonyloxy, the group -O-SO ₂ -OR ¹ or NR ¹ ₃ , where R ^{1 represents} methyl, ethyl, n-propyl or isopropyl.

The compounds of formula (III) are generally be known substances in organic chemistry.  

As diluents come when performing the inert in the first stage of the process according to the invention organic solvents in question. Preferably usable are aromatic hydrocarbons, such as benzene, toluene or xylene, also halogenated hydrocarbons, such as Methylene chloride, carbon tetrachloride, chloroform or Chlorobenzene, as well as esters such as ethyl acetate, continue Amides, such as dimethylformamide, and also strongly polar solvents solvents such as dimethyl sulfoxide.

As bases come in performing the first stage of the method according to the invention all the usual organi and inorganic acid binders. Alkali metal hydroxides or are preferably usable Alkali metal carbonates, such as sodium and potassium hydroxide, Sodium carbonate and potassium carbonate.

The reaction temperatures can be carried out the first stage of the process according to the invention in can be varied over a wide range. In general you work at temperatures between 0 ° C and 100 ° C, preferably between 20 ° C and 100 ° C.

When performing the first stage of the fiction The method is based on 1 mol of triazolyl ketone of formula (II) preferably 1 to 2 moles on a ver binding of formula (III). The processing takes place according to usual methods. In general, this is how that the reaction mixture is mixed with water, the resulting mixture with a little mixed with water baren organic solvent extracted, the organi phases, washes, dries and constricts and ver  Residual residue if necessary according to the usual metho cleans it.

The first stage of the method according to the invention can also in a two-phase system, e.g. B. from a system aqueous sodium or potassium hydroxide solution / toluene or methylene chloride, optionally with the addition of 0.1 to 1 mol a phase transfer catalyst, for example one Ammonium or phosphonium compound such as benzyldodecyl dimethyl-ammonium chloride or triethyl-benzyl-ammonium chloride.

Both the first stage and the second stage of the The method according to the invention are generally described under Normal pressure carried out. However, it is also possible each under increased or reduced pressure work.

Those who carried out the first stage of the inventions keto compounds arising according to the process of the formula (Ia) can either be complex Hydrides (variant α) or aluminum isopropylate (Vari ante β) can be reduced.

As complex hydrides come when performing the second stage of the method according to the invention (variant α) preferably sodium borohydride and lithium aluminum hydride in question.

As diluents come when performing the second stage of the method according to Va riante α polar organic solvents. Before  alcohols, such as methanol or etha, can also be used nol, isopropanol or butanol, and ethers such as diethyl ether or tetrahydrofuran, or water in a mixture with an alcohol.

The reaction temperatures can be carried out the second stage of the method according to the invention Variant α varies within a certain range become. Generally one works at temperatures between 0 ° C and 30 ° C, preferably between 0 ° C and 20 ° C.

When performing the second stage of the fiction The process according to variant α is based on 1 mol Keto compound of formula (Ia) an equivalent amount or an excess of complex hydride. The Refurbishment is carried out using customary methods. Generally mean you proceed in such a way that the reaction mixture with Water added, with a water-immiscible organic solvent extracted, the combined organi phases dry and constrict. But it is also possible Lich, the reaction mixture first with dilute, aq acid, e.g. B. hydrochloric acid, then alka and then in the previously described level way of working.

When performing the second stage of the fiction method according to variant β come as a dilution medium preferably alcohols, such as isopropanol, or Koh Hydrogen oils such as benzene in question.

When performing the second stage of the fiction Method according to variant β can the reaction  temperatures can be varied over a wide range. Generally one works at temperatures between 20 ° C and 120 ° C, preferably between 50 ° C and 100 ° C.

When performing the second stage of the fiction The procedure according to variant β is based on 1 mol Keto compound of formula (Ia) generally 1 to 2 moles of aluminum isopropylate. The processing he follows according to usual methods. Generally you go in such a way that the reaction mixture is concentrated, the remaining residue with dilute, aqueous Treated acid or base, then with one with water little miscible organic solvent extracted, the combined organic phases dry and concentrate.

The triazolyl butane derivatives according to the invention mel (I) can be added in acid addition salts or metal salt Complexes are transferred.

For the production of acid addition salts of the verbin The formulas of formula (I) are preferably those Acids in question that are already associated with the Description of the acid addition salts according to the invention were mentioned as preferred acids.

The acid addition salts of the compounds of formula (I) can in a simple manner according to usual salt formation methods, e.g. B. by dissolving a compound of formula (I) in a suitable inert solvent and adding the acid, e.g. B. hydrochloric acid can be obtained and in a known manner, e.g. B. by filtering, iso liert and optionally by washing with an inert organic solvents can be cleaned.  

For the production of metal salt complexes of the compounds The salts of the formula (I) are preferably those of metals in question that are already related the description of the metal salt com plexes were mentioned as preferred metal salts.

The metal salt complexes of the compounds of the formula (I) can be done in a simple manner using customary procedures will hold so z. B. by dissolving the metal salt in Alcohol, e.g. B. ethanol and adding to compounds of Formula (I). One can know metal salt complexes in known Way, e.g. B. by filtering, isolating and given if clean by recrystallization.

The active compounds according to the invention have a strong mi have a crobicidal effect and can be used as fungicides be set.

Fungicides are used in crop protection for fighting Plasmodiophoromycetes, Oomycetes, Chytri diomycetes, zygomycetes, ascomycetes, basidiomycetes, Deuteromycetes.

Some pathogens of fungal and bacterial diseases that fall under the generic names listed above may be mentioned as examples, but not by way of limitation:
Xanthomonas species, such as Xanthomonas oryzae;
Pseudomonas species, such as Pseudomonas lachrymans;
Erwinia species, such as Erwinia amylovora;
Pythium species, such as Pythium ultimum;
Phytophthora species, such as Phytophthora infestans;
Pseudoperonospora species, such as Pseudoperonospora humuli or Pseudoperonospora cubensis;
Plasmopara species, such as Plasmopara viticola;
Peronospora species, such as Peronospora pisi or P. brassicae;
Erysiphe species, such as Erysiphe graminis;
Sphaerotheca species, such as Sphaerotheca fuliginea;
Podosphaera species, such as Podosphaera leucotricha;
Venturia species, such as Venturia inaequalis;
Pyrenophora species, such as Pyrenophora teres or P. graminea;
(Conidial form: Drechslera, Syn: Helminthosporium);
Cochliobolus species, such as Cochliobolus sativus;
(Conidial form: Drechslera, Syn: Helminthosporium);
Uromyces species, such as Uromyces appendiculatus;
Puccinia species, such as Puccinia recondita;
Tilletia species, such as Tilletia caries;
Ustilago species, such as Ustilago nuda or Ustilago avenae;
Pellicularia species, such as Pellicularia sasakii;
Pyricularia species, such as Pyricularia oryzae;
Fusarium species, such as Fusarium culmorum;
Botrytis species, such as Botrytis cinerea;
Septoria species, such as Septoria nodorum;
Leptosphaeria species, such as Leptosphaeria nodorum;
Cercospora species, such as Cercospora canescens;
Alternaria species, such as Alternaria brassicae;
Pseudocercosporella species, such as Pseudocercosporella herpotrichoides.

The good plant tolerance of the active ingredients in the necessary to combat plant diseases Kon centers allows treatment from above ground Parts of plants, of seedlings and soil.

The active compounds according to the invention are particularly suitable others to control Pyricularia oryzae on rice and to combat cereal diseases, such as Leptosphae ria nodorum, Cochliobolus sativus, Pyrenophora teres, Pseudocercosporella herpotrichoides, Puccinia recondita, Erysiphe and Fusarium species. They also show the inventions substances according to the invention have a very good action against Unci nula also have a broad in vitro effect.

The substances according to the invention can be in the usual Formulations are transferred, such as solutions, emulsions NEN, suspensions, powders, foams, pastes, granules, Aerosols, very fine encapsulations in polymeric substances and in coating compositions for seeds, as well as ULV formulations. These formulations are produced in a known manner provides, e.g. B. by mixing the active ingredients with stretch agents, i.e. liquid solvents, are under pressure liquefied gases and / or solid carrier fen, if necessary using surfaces active agents, i.e. emulsifiers and / or dispersers yawing and / or foaming agents. In the event of the use of water as an extender can, for. B. also organic solvents as auxiliary solvents be used. As liquid solvents come in essential in question: aromatics, such as xylene, toluene, or  Alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, Chlorethylene or methylene chloride, aliphatic carbons Hydrogen, such as cyclohexane or paraffins, e.g. B. petroleum fractions, alcohols, pointed butanol or glycol as well their ethers and esters, ketones, such as acetone, methylethyl ketone, methyl isobutyl ketone or cyclohexanone, strong polar solvents such as dimethylformamide and dimethyl sulfoxide and water; with liquefied gaseous Excipients or carriers are such liquids keiten meant, which at normal temperature and below Normal pressure are gaseous, e.g. B. aerosol propellants, such as Butane, propane, nitrogen and carbon dioxide; as fixed Carriers come into question: z. B. natural rock flours, such as kaolins, clays, talc, chalk, quartz, Attapulgite, montmorillonite or diatomaceous earth and syn thetic rock powder, such as highly disperse silica, Alumina and silicates; as solid carriers for Granules are possible: B. broken and fractio nated natural rocks such as calcite, marble, pumice, Sepiolite, dolomite and synthetic granules inorganic and organic flours and granules organic material such as sawdust, coconut shells, Corn cobs and tobacco stalks; as emulsifying and / or Foaming agents are possible: B. not ionogenic and anionic emulsifiers, such as polyoxyethylene Fatty acid esters, polyoxyethylene fatty alcohol ethers, e.g. B. Alkylaryl polyglycol ether, alkyl sulfonates, alkyl sulfates, Aryl sulfonates and protein hydrolyzates; as a disperser middle come into question: z. B. lignin sulfite and Methyl cellulose.  

Adhesives such as carboxy can be used in the formulations methylcellulose, natural and synthetic powdery, granular or latex-shaped polymers can be used, such as Gum arabic, polyvinyl alcohol, polyvinyl acetate, as well natural phospholipids, such as cephalins and lecithins, and synthetic phospholipids. Other additives can mineral and vegetable oils.

Dyes such as inorganic pigments, e.g. B. Iron oxide, titanium oxide, ferrocyan blue and organic color substances such as alizarin, azo and metal phthalocyanine color substances and trace nutrients such as salts of iron, manganese, Boron, copper, cobalt, molybdenum and zinc are used the.

The formulations generally contain between 0.1 and 95 percent by weight of active ingredient, preferably between 0.5 and 90%.

The active compounds according to the invention can be found in the formulation stances in a mixture with other known active ingredients such as fungicides, insecticides, acaricides and Her bicidal and in mixtures with fertilizers and wax regulators.

The active ingredients as such, in the form of their formu lations or the application forms prepared from them such as ready-to-use solutions, emulsifiable concentrates, Emulsions, foams, suspensions, wettable powders, pastes, soluble powders, dusts and granules become. The application is done in the usual way, e.g. B.  by pouring, spraying, spraying, scattering Ver dusting, foaming, brushing, etc. It is further possible, the active ingredients according to the ultra-low-volume ver drive or apply the drug preparation or inject the active ingredient into the soil yourself. It can also the seeds of the plants are treated.

When using the substances according to the invention, the on wall quantity depending on the type of application in a larger Range can be varied. This is how the active ingredient concentrations are trations in the treatment of parts of plants in the Application forms in general between 1 and 0.0001% by weight, preferably between 0.5 and 0.001%. In the Seed treatment are generally active ingredient amounts from 0.001 to 50 g per kg of seed, preferably 0.01 to 10 g needed. When treating the soil are effective substance concentrations from 0.00001 to 0.1% by weight preferably from 0.0001 to 0.02%, required at the site of action such.

The production and use of the invention Fabrics are shown in the following examples.

Manufacturing examples example 1

A solution of 2.2 g (0.0383 mol) of potassium hydroxide in 10 ml of water is stirred at room temperature quickly into a solution of 8 g (0.0248 mol) of 1- (4-bromo phenyl) -2,2-dimethyl-4- (1,2,4-triazol-1-yl) butan-2-one and 5.8 g (0.0383 mol) of 3-methylbutyl bromide in 70 ml Dropped in dimethyl sulfoxide. It is cooled so that the temperature of the reaction mixture does not exceed 40 ° C increases. When the addition is complete, the reaction mixture stirred for a further 5 hours at 40 ° C and then with water transferred. It is extracted several times with methylene chloride, washes the combined organic phases twice Water and concentrated by stripping off the solvent reduced pressure. The remaining residue will with diethyl ether as the eluent on silica gel chromato graphed. Concentrating the eluate gives 4.5 g (46.3% of theory) of 2,2,5-trimethyl-1- (4-bromophenyl) 4- (1,2,4-triazol-1-yl) octan-3-one in the form of an oil.

¹ H-NMR (CDCl ₃ / TMS):
δ = 7.89 ppm (1 H)
δ = 8.29 ppm (1H).

Example 2

A solution of 0.11 g (0.0029 mol) of sodium borohydride in 5 ml of water is stirred at room temperature in a Solution of 3.5 g (0.0089 mol) of 2,2,5-trimethyl-1- (4-bromo phenyl) -4- (1,2,4-triazol-1-yl) octan-3-one in 50 ml metha dropped in nol. The reaction mixture is still 2 hours stirred at room temperature and then reduce reduced pressure. Then water is added and the resulting mixture several times with methylene chloride ex trahed. The combined organic phases are over Dried sodium sulfate and under reduced pressure constricted. In this way, 2.7 g (77% of the Theory) on 2,2,5-trimethyl-1- (4-bromophenyl) -4- (1,2,4- triazol-1-yl) -octan-3-ol in the form of a solid substance from Melting point 65 ° C.

According to the methods given above, the in the following table 2 verbal formula manufactured.

Table 2

The δ values given in Table 2 denote signals in the ¹ H-NMR spectrum (CDCl ₃ / TMS).

In the following usage examples, the verb of the formulas listed below as Ver same substances used:

(Known from DE-OS 30 48 267)  

Example A Leptosphaeria nodorum test (wheat) / protective

Solvent: 100 parts by weight of dimethylformamide
Emulsifier: 0.25 parts by weight of alkylaryl polyglycol ether.

For the preparation of a suitable preparation of active ingredient mix 1 part by weight of active ingredient with the specified quantities of solvent and emulsifier and dilute that Concentrate with water to the desired concentration.

To test for protective effectiveness, young people are sprayed Plants dewy moist with the active ingredient preparation. According to the plants are dried with a Sprayed conidia suspension of Leptosphaeria nodorum. The plants remain at 20 ° C. and 100% RH for 48 hours latent humidity in an incubation cabin.

The plants are grown in a greenhouse at a tempe 15 ° C and a relative humidity of approximately 80%.

Evaluation is carried out 10 days after the inoculation.

In this test, the compounds according to the invention show (2), (4), (6), (10), (11), (13), (14), (16), (18), (20), (21) and (23) to (27) at a concentration of 250 ppm in the spray liquor a much better we kung as the comparison substances (A) and (B).  

Example B Pseudocercosporella herpotrichoides test (wheat) / protective

Solvent: 100 parts by weight of dimethylformamide
Emulsifier: 0.25 parts by weight of alkylaryl polyglycol ether.

For the preparation of a suitable preparation of active ingredient mix 1 part by weight of active ingredient with the specified quantities of solvent and emulsifier and dilute that Concentrate with water to the desired concentration.

To test for protective effectiveness, young people are sprayed Plants dewy moist with the active ingredient preparation. According to the spray coating will dry the plants on the Culm base with spores of Pseudocercosporella herpotri choides inoculated.

The plants are grown in a greenhouse at a tempe temperature of approx. 10 ° C and a relative humidity of approximately 80%.

Evaluation is carried out 21 days after the inoculation.

In this test, the substances (2) according to the invention show (3) and (4) at a concentration of 250 ppm in the Spray liquor has a much better effect than the Ver like substance (C).  

Example C Pyricularia test (rice) / protective

Solvent: 12.5 parts by weight of acetone
Emulsifier: 0.3 part by weight of alkylaryl polyglycol ether.

For the preparation of a suitable preparation of active ingredient mix 1 part by weight of active ingredient with the specified amount of solvent and dilute the concentrate with Water and the specified amount of emulsifier on the ge wanted concentration.

To test for protective efficacy one splashes young rice plants with the active ingredient preparation up to Dripping wet. After the spray coating has dried off the plants with an aqueous spore suspension of Pyricularia oryzae inoculated. Then the Plant in a greenhouse at 100% rel. Humidity activity and 25 ° C.

The evaluation of the Disease.

In this test, the compounds according to the invention show (4), (12), (14), (16) and (21) to (24) for a conc tration of 0.025 wt .-% in the spray liquid better effect than the comparison substance (A).  

Example D Uncinula test (vine) / protective

Solvent: 4.7 parts by weight of acetone
Emulsifier: 0.3 part by weight of alkyl aryl polyglycol ether.

For the preparation of a suitable preparation of active ingredient mix 1 part by weight of active ingredient with the specified quantities of solvent and emulsifier and dilute that Concentrate with water to the desired concentration.

To test for protective efficacy one splashes young plants with the active ingredient preparation up to Dripping wet. After the spray coating has dried on, the Plants with conidia of the fungus Uncinula necator be dusting.

The plants are then at 23 to 24 ° C and at a relative humidity of approx. 75% in the crop set up house.

Evaluation is carried out 14 days after the inoculation.

In this test, the compounds according to the invention show (1) to (5), (9) and (14) to (22) at a concentration tion of 25 ppm in the spray mixture has an efficiency of 100%.

Claims (8)

1. Triazolyl-butane derivatives of the formula in which
A represents a keto group or a CH (OH) grouping and
R for ethyl, n-propyl, isopropyl, branched butyl, straight-chain or branched alkyl having more than 4 carbon atoms, optionally substituted cycloalkylalkyl, alkenyl, alkynyl or for a grouping of the formula stands, as well as their acid addition salts and metal salt complexes. 2. Triazolyl-butane derivatives of the formula (I) according to claim 1, in which
A represents a keto group or a CH (OH) group and
R for ethyl, n-propyl, isopropyl, iso-butyl, sec-butyl, tert-butyl, straight-chain or branched alkyl having 5 to 12 carbon atoms, for optionally by 1 to 3 alkyl groups each having 1 to 4 carbon atoms substituted cycloalkylalkyl with 3 to 7 carbon atoms in the cycloalkyl part and 1 to 4 carbon atoms in the alkyl part, for straight-chain or branched alkenyl with 3 to 12 carbon atoms, for straight-chain or branched alkynyl with 3 to 12 carbon atoms or for a grouping of the formula stands. 3. triazolyl-butane derivatives of the formula (I) according to claim 1, in which
A represents a keto group or a CH (OH) group and
R represents ethyl, n-propyl, isopropyl, iso-butyl, sec-butyl, tert-butyl, straight-chain or branched alkyl having 5 to 10 carbon atoms, for cycloal which is optionally substituted by 1 to 3 methyl and / or ethyl groups kylalkyl with 3 to 6 carbon atoms in the cycloalkyl part and 1 or 2 carbon atoms in the alkyl part, for straight-chain or branched alkenyl with 3 to 10 carbon atoms, for straight-chain or branched alkynyl with 3 to 10 carbon atoms or for a grouping of the formula stands. 4. Process for the preparation of triazolyl-butane derivatives of the formula in which
A represents a keto group or a CH (OH) group and
R for ethyl, n-propyl, isopropyl, branched butyl, straight-chain or branched alkyl having more than 4 carbon atoms, optionally substituted cycloalkylalkyl, alkenyl, alkynyl or for a grouping of the formula stands, as well as of their acid addition salts and metal salt complexes, characterized in that triazole ketone of the formula with compounds of the formula R-X (III) in which
R has the meanings given above and
X stands for an electron-withdrawing leaving group,
in the presence of a base and in the presence of a diluent or in an aqueous-organic two-phase system in the presence of a phase transfer catalyst and optionally the resulting keto compounds of the formula in which
R has the meanings given above,
either
α) reacted with complex hydrides in the presence of a diluent, or
β) reacted with aluminum isopropylate in the presence of a diluent,
and optionally then adding an acid or a metal salt to the triazolylbutane derivatives of the formula (I) thus obtained. 5. Fungicidal agents, characterized by a content on at least one triazolylbutane derivative of For mel (I) according to claim 1 or on an acid addi tion salt or metal salt complex of a triazolyl butane derivative of formula (I). 6. Use of triazolyl-butane derivatives of the formula (I) according to claim 1 or their acid addition Salts and metal salt complexes to combat Mushrooms. 7. Method of combating fungi, characterized thereby records that triazolyl-butane derivatives of For mel (I) according to claim 1 or its acid addition Salts or metal salt complexes on the mushrooms and / or whose habitat brings out.   8. Process for the preparation of fungicidal compositions, characterized in that triazolyl-butane Derivatives of formula (I) according to claim 1 or their Metal salt complexes or acid addition salts with Extenders and / or surfactants mixed.