EP0000017B1 - 1-(2-phenylethyl)-triazolium salts, their preparation and their use as fungicides - Google Patents

Description

The invention relates to 1- (2-phenylethyl) triazolium salts, a process for their preparation and their use as fungicides.

It has already been known that 1- [ß-aryl-ß- (R-oxy) ethyl] imidazoles, such as e.g. 1- [ß-butoxy-ß- (4'-chlorophenyl) ethyl] imidazole and 1- [ß-aryl-ß- (R-oxy) ethyl] triazoles, e.g. 1- [ß-Allyloxy-β- (4'-chlorophenyl) ethyl] -1,2,4-triazole, have a good fungicidal activity (cf. DE-OS 2 063 857 and 2 640 823). However, their effect is not always completely satisfactory in certain indication areas, particularly when low amounts and concentrations are applied. Furthermore, it has generally been known for a long time that zinc ethylene 1,2-bisdithiocarbamidate is a good means of combating fungal plant diseases [cf. Phytopathology 33, 1113 (1963)]. However, its use as a seed dressing is only possible to a limited extent, since it is not very effective at low application rates and concentrations.

in welcher

• R für Halogen, Alkyl mit 1 bis 4 Kohlenstoffatomen, gegebenenfalls durch Halogen substituiertes Phenyl oder Phenoxy steht,
• n für ganze Zahlen von 0 bis 3 steht,
• R¹ für die Gruppe -0-R², für Alkylmercapto oder Alkylcarbonyloxy mit jeweils 1 bis 4 Kohlenstoffatomen im Alkylteil steht,
• R² für Alkenyl mit 2 bis 4 Kohlenstoffatomen und für gegebenenfalls durch Halogen substituiertes Benzyl steht,
• R³ für Alkyl mit 1 bis 6 Kohlenstoffatomen, für Pinakolyl und für gegebenenfalls durch Halogen substituiertes Benzyl oder Benzoylmethyl steht, und
• Z für Halogen steht,

gefunden. Sie weisen starke fungizide Eigenschaften auf.There have now been the 1- (2-phenylethyl) triazolium salts of the general formula I

in which

• R represents halogen, alkyl having 1 to 4 carbon atoms, phenyl or phenoxy optionally substituted by halogen,
• n stands for integers from 0 to 3,
• R ^{1 represents} the group -0-R ² , alkylmercapto or alkylcarbonyloxy each having 1 to 4 carbon atoms in the alkyl part,
• R ^{2 represents} alkenyl having 2 to 4 carbon atoms and benzyl optionally substituted by halogen,
• R ^{3 represents} alkyl having 1 to 6 carbon atoms, pinacolyl and benzyl or benzoylmethyl optionally substituted by halogen, and
• Z represents halogen,

found. They have strong fungicidal properties.

in welcher

• R, R¹ und n die oben angegebene Bedeutung haben, mit Halogeniden der allgemeinen Formel III

in welcher

• R³ die oben angegebene Bedeutung hat und
• X für Halogen steht,

in Gegenwart eines Verdünnungsmittels in an sich bekannter Weise umsetzt und gegebenenfalls das Halogenid in den so erhaltenen Triazolium-Halogeniden ebenfalls in an sich bekannter Weise gegen ein anderes Halogenid austauscht.Furthermore, it was found that the 1- (2-phenylethyl) triazolium salts of the general formula I are obtained if 1-phenyl-2-triazolyl-ethyl derivatives of the general formula II

in which

• R, R ¹ and n have the meaning given above, with halides of the general formula III

in which

• R ^{3 has} the meaning given above and
• X represents halogen,

reacted in the presence of a diluent in a manner known per se and, if appropriate, the halide in the triazolium halides thus obtained is likewise exchanged for another halide in a manner known per se.

In some cases it proves advantageous to use appropriate reactive esters instead of the halides of the general formula III, which are obtained by reacting the corresponding alcohols with the corresponding acids.

Surprisingly, the 1- (2-phenylethyl) triazolium salts according to the invention show a considerably higher fungicidal activity, in particular against rust and mildew types, than the 1- [ß-aryl-ß- (R-oxy) known from the prior art. ethyl] imidazoles and triazoles, for example 1- [ß-butoxy-ß- (4'-chlorophenyl) ethyl] imidazole, which are chemically and functionally obvious substances, and as the zinc-ethylene-1, 2-bis-dithiocarbamidate, which is a known substance with the same direction of action. The active compounds according to the invention thus represent an enrichment of the technology.

If [1- (2,4-dichlorophenyl) -2- (1,2,4-triazol-1-yl) ethyl] - (2,4-dichlorobenzyl) ether and monochloropinacoline are used as starting materials, the reaction can proceed can be represented by the following formula:

The alkyl part preferably occurs at the nitrogen atom 4 of the 1,2,4-triazol-1-yl radical, as can be seen from the nuclear magnetic resonance data; depending on the reactivity of the alkyl halide and the starting product of the general formula II, however, alkylation on nitrogen atom 1 of the 1,2,4-triazol-1-yl radical can also be carried out. Both types of compounds and the mixtures obtained in this alkylation are claimed according to the invention.

The 1-phenyl-2-triazolylethyl derivatives to be used as starting materials are generally defined by the general formula 11.

The starting materials of the general formula II are known (cf. DE-OS 25 47 953, DE-OS 26 40 823, DE-OS 26 28 419 and DE-OS 26 45 496). They can be obtained by the processes described there, e.g.

in welcher

• R und n die oben angegebene Bedeutung haben und
• M für ein Alkalimetall, vorzugsweise Lithium, Natrium und Kalium, eine quarternäre Ammonium-oder Phosphoniumgruppe steht,

mit einem Halogenid der allgemeinen Formel V

in welcher

• R² die oben angegebene Bedeutung hat und
• Hal für Chlor oder Brom steht,

in Gegenwart eines organischen Lösungsmittels, wie beispielsweise Dioxan oder Chloroform, bei Temperaturen zwischen 20 und 120°C umsetzt. Zur Isolierung der Endprodukte wird das Reaktionsgemisch vom Lösungsmittel befreit und der Rückstand mit Wasser und einem organischen Lösungsmittel versetzt. Die organische Phase wird abgetrennt, in üblicher Weise aufgearbeitet und gereinigt.a) Alkanolates of 1-hydroxy-1-phenyl-2-triazolyl-ethane derivatives of the general formula IV

in which

• R and n have the meaning given above and
• M represents an alkali metal, preferably lithium, sodium and potassium, a quaternary ammonium or phosphonium group,

with a halide of the general formula V

in which

• R ^{2 has} the meaning given above and
• Hal represents chlorine or bromine,

in the presence of an organic solvent, such as dioxane or chloroform, at temperatures between 20 and 120 ° C. To isolate the end products, the reaction mixture is freed from the solvent and the residue is mixed with water and an organic solvent. The organic phase is separated off, worked up and purified in a conventional manner.

In a preferred embodiment, the procedure is advantageously carried out in such a way that a 1-hydroxy-1-phenyl-2-triazolylethane derivative is used, the latter being converted into the alkali metal alcoholate of the general formula IV in a suitable inert solvent by means of alkali metal hydride or alkali metal amide , and the latter is reacted immediately without isolation with a halide of the general formula V, the compounds of the general formula II being obtained in one operation with the emergence of alkali halide.

According to a further preferred embodiment, the preparation of the alkanolates of the general formula IV and the reaction with the halide of the general formula V are advantageously carried out in a two-phase system, such as, for example, aqueous sodium hydroxide solution or potassium hydroxide solution / toluene or methylene chloride, with the addition of a phase transfer catalyst, such as ammonium or phosphonium compounds.

• b) die den Alkanolaten der allgemeinen Formel IV zugrunde liegenden 1-Hydroxy-1-phenyt-2-triazolyl-äthane mit entsprechenden Säureanhydriden nach bekannten Methoden, z.B. in molaren Mengen in Gegenwart eines inerten organischen Lösungsmittels, beispielsweise Aceton, oder mit einem Überschuß and Säureanhydrid und in Gegenwart eines sauren oder basischen Katalysators, beispielsweise Natriumacetat, bei Temperaturen zwischen 0 und 150°C umsetzt und die Verbindungen der allgemeinen Formel 11 in üblicher Weise isoliert, oder
• c) 1-Halogen-1-phenyl-2-triazolyl-äthane der allgemeinen Formel VI
  
  in welcher
  • R und n die oben angegebene Bedeutung haben und
  • X für Halogen steht,
  
  mit Alkylmercaptanen mit Alkylresten enthaltend 1 bis 4 Kohlenstoffatome in bekannter Weise in Gegenwart eines inerten organischen Lösungsmittels, beispielsweise Aceton, und in Gegenwart eines Säurebindemittels, beispielsweise Kaliumcarbonat, bei Temperaturen zwischen 60 und 100°C umsetzt.

Individual starting materials of the general formula 11 can also be obtained if one

• b) the 1-hydroxy-1-phenyt-2-triazolylethane on which the alkanolates of the general formula IV are based, with corresponding acid anhydrides by known methods, for example in molar amounts in the presence of an inert organic solvent, for example acetone, or with an excess and Acid anhydride and in the presence of an acidic or basic catalyst, for example sodium acetate, at temperatures between 0 and 150 ° C and the compounds of general formula 11 isolated in a conventional manner, or
• c) 1-Halogen-1-phenyl-2-triazolyl-ethane of the general formula VI
  
  in which
  • R and n have the meaning given above and
  • X represents halogen,
  
  with alkyl mercaptans with alkyl radicals containing 1 to 4 carbon atoms in a known manner in the presence of an inert organic solvent, for example acetone, and in the presence of an acid binder, for example potassium carbonate, at temperatures between 60 and 100 ° C.

The 1-hydroxy-1-phenyl-2-triazolyl-ethane derivatives on which the alkanolates of the general formula IV are based are known (cf. DE-OS 24 31 407 and DE-OS 25 47 953).

The 1-halogen-1-phenyl-2-triazolyl-ethane derivatives of the general formula VI are also known (cf. DE-OS 25 47 954).

The halides also to be used as starting materials are generally defined by the general formula III.

The starting materials of the general formula III are generally known compounds of organic chemistry, or they can be obtained in a generally known and customary manner.

Polar organic solvents are preferably used as diluents for the reaction according to the invention. These preferably include nitriles, such as acetonitrile; Sulfoxides such as dimethyl sulfoxide; Formamides such as dimethylformamide; Ketones such as acetone; Ethers such as diethyl ether and tetrahydrofuran and chlorinated hydrocarbons such as methylene chloride and chloroform.

The reaction temperatures can be varied within a wide range in the process according to the invention. In general, between about 0 to 120 ° C, preferably at 20 to 90 ° C, or at the boiling point of the solvent.

The process according to the invention is preferably carried out in molar amounts. The compounds of the general formula I are isolated in a customary manner.

The halogen ion exchange, which may be carried out in accordance with the process according to the invention, is carried out in a generally known manner (cf. DE-OS 2 504 114) by using the 1- (2-phenylethyl) triazolium halides of the general formula converted into the corresponding triazolium hydroxides by means of a base or an anion exchange resin and then reacted with an appropriate acid.

The active substances according to the invention have a strong fungitoxic effect. They do not damage crops in the concentrations necessary to control fungi. For these reasons, they are suitable for use as crop protection agents for combating fungi. Fun gitoxic agents in crop protection are used to control Plasmodiophoromycetes, Oomycetes Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes, Deuteromycetes.

The active compounds according to the invention have a broad spectrum of activity and can be used against parasitic fungi which attack above-ground parts of plants or attack the plants from the ground, and against seed-borne pathogens. They are particularly effective against parasitic fungi on above-ground parts of plants.

As crop protection agents, the active compounds according to the invention can be used with particularly good success for combating Venturia species, such as against the pathogen causing apple scab (Fusicladium dendriticum), for powdery mildew fungi, for example for combating powdery mildew (Podosphaera leucotricha) and powdery mildew, and for other cereal diseases.

Of particular note is the partially systemic effect of the substances. This is how plants can be protected against fungal attack if the active ingredient is supplied to the aerial parts of the plant via the soil and the roots.

The active compounds according to the invention can be used as crop protection agents for treating seeds or soil and for treating above-ground parts of plants.

The active compounds according to the invention can be converted into the customary formulations, such as solutions, emulsions, suspensions, powders, pastes and granules. These are made in a known manner, e.g. by mixing the active ingredients with extenders, that is to say liquid solvents, pressurized liquefied gases and / or solid carriers, if appropriate using surface-active agents, that is to say emulsifiers and / or dispersants and / or foam-generating agents. If water is used as an extender, e.g. organic solvents can also be used as auxiliary solvents. The following are essentially suitable as liquid solvents: aromatics, such as xylene, toluene, benzene or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylene or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, e.g. Petroleum fractions, alcohols, such as butanol or glycol, and their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents, such as dimethylformamide and dimethyl sulfoxide, and water; Liquefied gaseous extenders or excipients are those liquids which are gaseous at normal temperature and pressure, e.g. Aerosol propellants such as dichlorodifluoromethane or trichlorofluoromethane; as solid carriers: natural rock flour, such as kaolin, clay, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic rock powder, such as highly disperse silica, aluminum oxide and silicates; as an emulsifier; nonionic and anionic emulsifiers such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, e.g. Alkylaryl polyglycol ether, alkyl sulfonates, alkyl sulfates, aryl sulfonates and protein hydrolyzates; as a dispersant: e.g. Lignin, sulfite liquor and methyl cellulose.

The active compounds according to the invention can be present in the formulations in a mixture with other known active compounds, such as fungicides, insecticides, acaricides, nematicides, herbicides, bird repellants, growth agents, plant nutrients and agents which improve soil structure.

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

The active compounds can be used as such, in the form of their formulations or in the use forms prepared therefrom by further dilution, such as ready-to-use solutions, emulsions, suspensions, powders, pastes and granules. They are used in the usual way, e.g. by pouring, spraying, spraying, dusting, scattering, dry pickling, wet pickling, wet pickling, slurry pickling or incrusting.

When used as leaf fungicides, the active compound concentrations in the use forms can be varied within a substantial range. They are generally between 0.1 and 0.00001 percent by weight. Preferably between 0.05 and 0.0001%.

In the case of seed treatment, amounts of active compound of 0.001 to 50 g per kilogram of seed, preferably 0.01 to 10 g, are generally required.

For soil treatment, amounts of active ingredient from 1 to 100 g per soil, in particular 10 to 200 g, are required.

The versatile examples are shown in the following examples.

Example A Podosphaera test (apple) / protective

The amount of active ingredient required for the desired active ingredient concentration in the spray liquid is mixed with the stated amount of solvent and the concentrate is diluted with the stated amount of water which contains the additives mentioned.

The spray liquid is used to spray young apple seedlings, which are in the 4- to 6-leaf stage, until they drip wet. The plants remain in the greenhouse for 24 hours at 20 ° C and a relative humidity of 70%. Then they are inoculated by dusting with conidia of the powdery mildew pathogen (Podosphaera leucotricha) and placed in a greenhouse with a temperature of 21 to 23 ° C and a relative humidity of approx. 70%.

The infestation of the seedlings is determined 10 days after the inoculation. The rating values received are converted into percent infestation. 0% means no attack, 100% means that the plants are completely infected.

Active substances, active substance concentrations and results are shown in the table below:

Example B Fusidadium test (apple) / protective

The amount of active ingredient required for the desired active ingredient concentration in the spray liquid is mixed with the stated amount of solvent and the concentrate is diluted with the stated amount of water which contains the additives mentioned.

The spray liquid is used to spray young apple seedlings, which are in the 4- to 6-leaf stage, until they drip wet. The plants remain in the greenhouse for 24 hours at 20 ° C. and a relative humidity of 70%. They are then inoculated with an aqueous conidia suspension of the apple scab pathogen (Fusicladium dendriticum) and incubated for 18 hours in a humid chamber at 18 to 20 ° C and 100% relative humidity.

The plants then come back into the greenhouse for 14 days.

The infestation of the seedlings is determined 15 days after the inoculation. The rating values received are converted into percent infestation. 0% means no infection, 100% means that the plants are completely infected.

Active substances, active substance concentrations and results are shown in the table below:

Example C Shoot treatment test / powdery mildew / protective (leaf-destroying mycosis)

To prepare a suitable preparation of active compound, 0.25 part by weight of active compound is taken up in 25 parts by weight of dimethylformamide and 0.06 part by weight of alkylaryl polyglycol ether, and 975 parts by weight of water are added. The concentrate is diluted with water to the desired final concentration of the spray mixture.

To test for protective activity, the single-leafed barley young plants of the Amsel variety are sprayed with the preparation of active compound as dewy. After drying, the barley plants are dusted with spores from Erysiphe graminis var. Hordei.

After 6 days of dwell time of the plants at a temperature of 21 to 22 ° C and a humidity of 80 to 90%, the stocking of the plants with mildew pustules is evaluated. The degree of infestation is expressed as a percentage of the infestation of the untreated control plants. 0% means no infection and 100% the same degree of infection as in the untreated control. The lower the mildew infestation, the more effective the active ingredient.

Active substances, active substance concentrations in the spray mixture and degrees of infestation are shown in the table below.

Example D Barley powdery mildew test (Erysiphe graminis var. Hordei) / systemic (fungal cereal sprout disease)

The active ingredients are used as powdered seed treatment agents. They are produced by stripping the respective active ingredient with a mixture of equal parts by weight of talc and kieselguhr to a fine powdery mixture with the desired active ingredient concentration.

For seed treatment, shake barley seed with the stripped active ingredient in a sealed glass bottle. The seeds are sown with 3 x 12 seeds in flower pots 2 cm deep in a mixture of a volume of Fruhstorfer uniform earth and a volume of quartz sand. Germination and casserole take place under favorable conditions in the greenhouse. 7 days after sowing, when the barley plants have unfolded their first leaf, they are covered with fresh spores from Erysiphe graminis var. hordei dusted and at 21 to 22 ° C and 80 to 90% rel. Humidity and 16 _- hour exposure cultivated further. The typical mildew pustules form on the leaves within 6 days.

The degree of infestation is expressed as a percentage of the infestation of the untreated control plants. 0% means no infection and 100% the same degree of infection as in the untreated control. The lower the mildew infestation, the more effective the active ingredient.

Active substances, active substance concentrations in the seed treatment agent as well as its application rate and the percentage of mildew infestation are shown in the table below.

Example E Mycelium growth test Culture medium used:

Ratio of solvent mixture to culture medium:

2 parts by weight of solvent mixture

The amount of active ingredient required for the desired active ingredient concentration in the culture medium is mixed with the stated amount of the solvent mixture. The concentrate is thoroughly mixed with the liquid nutrient medium cooled to 42 ° C in the stated ratio and poured into Petri dishes with a diameter of 9 cm. Control plates are also set up without admixture.

When the culture medium has cooled down and is solid, the plates are inoculated with the fungus species listed in the table and incubated at about 21 ° C.

The evaluation takes place after 4-10 days depending on the growth rate of the mushrooms. In the evaluation, the radial mycelial growth on the treated culture media is compared with the growth on the control culture media. Mushroom growth is rated using the following indicators:

Active substances, active substance concentrations and results are shown in the following table:

Manufacturing examples example 1

20.7 g (0.05 mol) of [1- (2,4-dichlorophenyl) -2- (1,2,4-triazol-1-yl) ethyl (2,4-dichlorobenzyl) ether and 6 , 7 g (0.05 mol) of monochloropinacoline are refluxed in 50 ml of acetonitrile for 12 hours. Then allowed to cool, the precipitated solid is filtered off, washed with acetone and dried. 10.9 g (40% of theory) of 1- [2- (2,4-dichlorobenzyloxy) -2- (2,4-dichlorophenyl) ethyl] tert-butylcarbonylmethyl-1, 2,4-triazolium are obtained -chloride with a melting point of 216-218 ° C.

Manufacture of intermediate products

25.8 g (0.1 mol) of 1-hydroxy-1- (2,4-dichlorophenyl) -2- (1,2,4-triazol-1-yl) -ethane are dissolved in 125 ml of dioxane and with stirring added dropwise to a mixture of 4 g of 80% sodium hydride and 100 ml of dioxane. The mixture is then heated under reflux for one hour. After cooling, 20 g (0.1 mol) of 2,4-dichlorobenzyl chloride are added dropwise to the sodium salt thus obtained at room temperature. The mixture is then heated under reflux for several hours, allowed to cool and concentrated by distilling off the solvent. The residue is mixed with water and methylene chloride, the organic phase is separated off, dried over sodium sulfate and concentrated. The solid residue is recrystallized from ligroin. 29 g (70% of theory) of [1- (2,4-dichlorophenyl) -2- (1,2,4-triazol-1-yl) ethyl] - (2,4-dichlorobenzyl) ether of Melting point 84 ° C.

25.6 g (0.1 mol) of co- (1,2,4-triazol-1-yl) -2,4-dichloroacetophenone are dissolved in 300 ml of methanol and at 5 to 10 ° C. with stirring in portions with 4 g (0.1 mol) sodium borohydride added. The mixture is then stirred for an hour at room temperature and heated to boiling for one hour. After the solvent has been distilled off, the residue is briefly heated with 200 ml of water and 40 ml of concentrated hydrochloric acid. After the reaction mixture has been made alkaline with sodium hydroxide solution, the solid reaction product can be filtered off. After recrystallization from ligroin / isopropanol, 21.3 g (82% of theory) of 1-hydroxy-1- (2,4-dichlorophenyl) -2- (1,2,4-triazol-1-yl- ether of Melting point 90 ° C.

269 g (1 mol) of ω-bromo-2,4-dichloroacetophenone are dissolved in 250 ml of acetonitrile. The solution is added dropwise to a refluxing suspension of 69 g (1 mol) of 1,2,4-triazole and 150 g of potassium carbonate in 2 l of acetonitrile. After heating under reflux for 20 hours, the cooled suspension is filtered, the filtrate is freed from the solvent and the residue is added.

Acetate ethyl acetate, washed with water, dried over sodium sulfate and freed from the solvent. The ethyl acetate residue crystallized out when added with isopropanol. After recrystallization from ligroin / isopropanol, 154 g (60% of theory) of ω- (1,2,4-triazol-1-yl) -2,4-dichloroacetophenone with a melting point of 117 ° C. are obtained.

Example 2

20.7 g (0.05 mol) of [1- (2,4-dichlorophenyl) -2- (1,2,4-triazol-1-yl) ethyl] - (2,6-dichlorobenzyl) ether and 13.4 g (0.05 mol) of 2,4-dichlorobenzoylmethyl bromide are refluxed in 250 ml of chloroform for 15 hours. The mixture is allowed to cool and concentrated by distilling off the solvent in vacuo. The residue is briefly boiled with acetone. After cooling, the crystalline residue is filtered off, washed with acetone and dried. 5.6 g (16.5% of theory) of 1- [2- (2,6-dichlorobenzyloxy) -2- (2,4-dichlorophenyl) ethyl] -2,4-dichlorobenzoylmethyl-1 are obtained, 2,4-triazolium bromide with a melting point of 202 ° C.

Example 3

20.7 g (0.05 mol) of 1- (2,4-dichlorophenyl) -2- (1,2,4-triazol-1-yl) ethyl] - (2,6-dichlorobenzyl) ether and 7 , 1 g (0.05 mol) of methyl iodide in 100 ml of acetonitrile are heated under reflux for 12 hours. Then allowed to cool, the precipitated solid is filtered off, washed with acetone and dried. 26.7 g (96.7% of theory) of 1- [2- (2,6-dichlorobenzyloxy) -2- (2,4-dichlorophenyl) ethyl] methyl-1,2,4-triazolium are obtained. iodide, melting point 228-230 ° C (dec.).

The following compounds of the formula I are obtained in an analogous manner:

Claims (4)

1. 1-(2-Phenylethyl)-triazolium salts of the general formula

in which

R represents halogen, alkyl with 1 to 4 carbon atoms and phenyl or phenoxy optionally substituted by halogen,

n represents integers from 0 to 3,

R¹ represents the group -O-R2, alkylmercapto or alkylcarbonyloxy with in each case 1 to 4 carbon atoms in the alkyl part,

R² represents alkenyl with 2 to 4 carbon atoms and benzyl optionally substituted by halogen,

R³ represents alkyl with 1 to 6 carbon atoms, pinacolyl and benzyl or benzoylmethyl optionally substituted by halogen and

Z represents halogen.

2. Process for the preparation of 1-(2-phenylethyl)-triazolium salts according to Claim 1, characterised in that 1-phenyl-2-triazolyl-ethyl derivatives of the general formula

in which

R, R' and n have the meaning given in Claim 1 are reacted with halides of the general formula

in which

R³ has the meaning given in Claim 1,

in the presence of a diluent in a manner known per se and the halide in the resulting triazolium halides is optionally replaced by another halide also in a manner known per se.

3. Fungicidal agents characterised in that they contain at least one 1-(2-phenylethyl)-triazolium salt according to Claim 1.

4. Use of 1-(2-phenylethyl)-triazolium salts according to Claim 1 for combating fungi.