EP0000018B1 - Metal salt complexes of 1-phenyl-2-triazolyl-ethane derivatives, their preparation and their use as fungicides - Google Patents

Description

The invention relates to new metal salt complexes of 1-phenyl-2-triazolyl-ethyl derivatives, a process for their preparation and their use as fungicides.

It has already been known that 1- [ß-aryl-ß- (R-oxy) ethyl] imidazoles, e.g. 1- [ß-Bu-toxy-ß- (4'-chlorophenyl) ethyl)] - imidazole) and 1- [ß-aryl-ß- (R-oxy) ethyl] triazoles, e.g. 1- [ß-allyl-oxy-ß- (4'-chlorophenyl) ethyl] -1,2,4-triazole, have a good fungicidal activity (cf. German Offenlegungsschriften 2063857 and 2640823). 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 Fluor, Chlor, Brom und für Alkyl mit 1 bis 4 Kohlenstoffatomen steht, ferner für gegebenenfalls durch Fluor, Chlor oder Brom substituiertes Phenyl oder Phenoxy steht,
• R¹ für die Gruppierungen -O-R² oder -O-CO-R³ steht, wobei
• R² und R³ für Alkyl, Alkenyl und Alkinyl mit jeweils bis zu 4 Kohlenstoffatomen, ferner für gegebenenfalls im Arylteil durch Fluor, Chlor, Brom oder Alkyl mit 1 bis 5 Kohlenstoffatomen substituiertes Benzyl stehen,
• A für ein Chlorid-, Nitrat- oder Sulfat-Anion steht,
• Me für die Metalle Kupfer, Zink, Mangan, Magnesium, Zinn, Eisen und Nickel steht,
  • n für ganze Zahlen von 0 bis 3 steht,
  • p für ganze Zahlen von 1 bis 4 steht und
  • x für ganze Zahlen von 1 bis 4 steht,

gefunden. Sie weisen starke fungizide Eigenschaften auf.The metal salt complexes of 1-phenyl-2-triazolyl-ethyl derivatives of the formula have now been identified as new compounds

in which

• R represents fluorine, chlorine, bromine and alkyl having 1 to 4 carbon atoms, furthermore represents phenyl or phenoxy which is optionally substituted by fluorine, chlorine or bromine,
• R ^{1 represents} the groupings -OR ² or -O-CO-R ³ , where
• R ² and R ^{3 represent} alkyl, alkenyl and alkynyl each having up to 4 carbon atoms, furthermore benzyl optionally substituted in the aryl part by fluorine, chlorine, bromine or alkyl having 1 to 5 carbon atoms,
• A represents a chloride, nitrate or sulfate anion,
• Me stands for the metals copper, zinc, manganese, magnesium, tin, iron and nickel,
  • n stands for integers from 0 to 3,
  • p stands for integers from 1 to 4 and
  • x represents integers from 1 to 4,

found. They have strong fungicidal properties.

in welcher

• R,R' und n die oben angegebene Bedeutung haben,
• mit Metallsalzen der Formel lll
  
  in welcher
• kfür beliebige Zahlen von 0 bis 12 steht und Me, A und p die oben angegebene Bedeutung haben, in Gegenwart eines Lösungsmittels umsetzt.

Furthermore, it was found that the metal complexes of the formula are obtained when 1-phenyl-2-triazolyl-ethyl derivatives of the formula 11

in which

• R, R 'and n have the meaning given above,
• with metal salts of the formula III
  
  in which
• k represents any number from 0 to 12 and Me, A and p have the meaning given above, in the presence of a solvent.

Surprisingly, the metal complexes of 1-phenyl-2-triazolyl-ethyl derivatives 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 ) -ethyl] -imidazoles and -triazoles, for example 1- [ß-butoxy-ß- (4'-chlorophenyl) -ethyl] -imidazole, which are chemically and effectively obvious substances, and as the zinc-ethylene-1,2 -bis-dithio- carbamidate, which is a known substance with the same direction of action. The active ingredients according to the invention thus represent an enrichment of technology.

If [1- (2,4-dichlorophenyl) -2- (1,2,4-triazol-1-yl) ethyl] allyl ether and copper (||) -chloride are used as starting materials, then the reaction sequence can be represented by the following formula:

Formula 1 generally defines the 1-phenyl-2-triazolyl-ethyl derivatives to be used as starting materials.

Some of the starting materials of the formula II are known (cf. DT-OS 2547953 and DT-OS 2640823), and in part they are the subject of proprietary, older applications which do not yet belong to the prior art (cf. German patent applications P2628419 from June 24, 1976 and P 2645496 from October 8, 1976). Starting substances of the formula not yet known can be obtained by the processes described therein, for example by

a) Alkanolates of 1-hydroxy-1-phenyl-2-triazolyl-ethane derivatives of the formula IV

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 Formel V
  
• in welcher
• R¹ 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.

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 formula V
  
• in which
• R ^{1 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 expediently started from a 1-hydroxy-1-phenyl-2-triazolylethane derivative, the latter in a suitable inert solvent using alkali metal hydride or alkali metal amide in the alkali metal alcoholate of the formula IV transferred, and the latter is reacted immediately without isolation with a halide of the formula V, the compounds of the formula 11 being obtained in one operation with the emergence of alkali halide.

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

• - mit entsprechenden Säureanhydriden nach bekannten Methoden, z.B. in molaren Mengen in Gegenwart eines inerten organischen Lösungsmittels, beispielsweise Aceton, oder mit einem Überschuss an Säureanhydrid und in Gegenwart eines sauren oder basischen Katalysators, beispielsweise Natriumacetat, bei Temperaturen zwischen 0 und 150°C umsetzt und die Verbindungen der Formel in üblicher Weise isoliert, oder
• - mit entsprechenden Isocyanaten nach bekannten Methoden, z.B. in molaren Mengen in Gegenwart eines inerten organischen Lösungsmittels, beispielsweise Benzol, und in Gegenwart eines Katalysators, beispielsweise Dibutylzinndilaurat, bei Temperaturen zwischen 0 und 100°C umsetzt und die Verbindungen der Formel in üblicher Weise isoliert.

The starting materials of formula II can also be obtained if one
b) the 1-hydroxy-1-phenyl-2-triazolyl-ethanes on which the alkanolates of the formula IV are based

• - With appropriate 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 of 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 the formula isolated in a conventional manner, or
• - With appropriate isocyanates by known methods, for example in molar amounts in the presence of an inert organic solvent, for example benzene, and in the presence of a catalyst, for example dibutyltin dilaurate, at temperatures between 0 and 100 ° C and the compounds of the formula isolated in a conventional manner.

The 1-hydroxy-1-phenyl-2-triazolyl-ethane derivatives on which the alkanolates of the formula IV are based are known (cf. DT-OS 2431407 and DT-OS 2547953).

The 1-halogen-1-phenyl-2-triazolyl-ethane derivatives of the formula VI are also known (cf. DT-OS 2547954).

Examples of the 1-phenyl-2-triazolyl-ethyl derivatives of the formula 11 to be used as starting materials according to the invention are the following compounds in Tables 1, 2 and 3:

The required metal salts of formula 111 are well known, easily accessible compounds.

Suitable diluents for the reaction according to the invention are water and all inert organic solvents. These preferably include alcohols such as methanol and ethanol, ketones such as acetone or ethyl methyl ketone, and ethers such as e.g. Diethyl ether and dioxane.

The reaction temperatures can be varied over a wide range. Generally one works between 0 and 40 ° C, preferably between 15 and 30 ° C.

When carrying out the process according to the invention, the stoichiometric amount (depending on the oxidation state of the metal) of the compound of the formula 11 is employed per mol of the metal salt 111. These ratios can be exceeded by up to 20 mol% without significant reduction in yield. Working up is carried out in a manner which is customary and generally known for organic compounds, e.g. by suctioning off the precipitated complex and cleaning by recrystallization, e.g. from alcohol.

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. Fungitoxic 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 parts of the plants above ground 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 apple scab pathogen (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, chlorethylenes 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 carriers mean 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 ethers, 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% 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% 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 1000 g per cbm of soil, in particular 10 to 200 g, are required.

The versatile examples are shown in the following examples.

Example A

• Lösungsmittel: 4,7 Gew.-Teile Aceton
• Emulgator: 0,3 Gew.-Teile Alkyl-aryl-polyglykol-ether
• Wasser: 95,0 Gew.-Teile

Fusieladium test (apple) / protective

• Solvent: 4.7 parts by weight of acetone
• Emulsifier: 0.3 part by weight of alkyl aryl polyglycol ether
• Water: 95.0 parts by weight

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 return to 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 B

Man vermischt die für die gewünschte Wirkstoffkonzentration in der Spritzflüssigkeit nötige Wirkstoffmenge mit der angegebenen Menge des Lösungsmittels und verdünnt das Konzentrat mit der angegebenen Menge Wasser, welches die genannten Zusätze enthält.

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 by dusting them 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 obtained are converted into% 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 an air 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) / ystemic
(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 3x12 seeds in flower pots 2cm 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 dusted with fresh spores of Erysiphe graminis var. Hordei and at 21 to 22 ° C and 80 to 90% rel. Humidity and 16-hour exposure further cultivated. 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% means 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

Mycelial growth test Medium used:

Ratio of solvent mixture to culture medium:

Composition 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 to 10 days, depending on the growth rate of the fungi. 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 table below:

Manufacturing examples example 1

4,25 g (0,025 Mol) Kupferdichlorid (CuCl₂ x 2 H₂0) werden in 40 ml Wasser gelöst und unter Rühren zu 14,9g (0,05 Mol) [1-(2,4-Dichlorphenyl)-2-(1,2,4-triazol-1-yl)-ethyl]-allyl-ether, gelöst in 100 ml Ethanol, getropft. Nach dreistündigem Rühren bei Raumtemperatur wird der Feststoff abgesaugt, mit Diethylether gewaschen und getrocknet. Man erhält 13,5 g (75% der Theorie) an Bis-[1-(2,4-Dichlorphenyl)-2-( 1,2,4-triazol-1-yl)-ethyl]-allyl-ether)-kupfer (ll)-chlorid vom Schmelzpunkt 158 bis 160°C.

4.25 g (0.025 mol) of copper dichloride (CuCl ₂ x 2 H ₂ 0) are dissolved in 40 ml of water and with stirring to 14.9 g (0.05 mol) of [1- (2,4-dichlorophenyl) -2- (1,2,4-triazol-1-yl) ethyl] allyl ether, dissolved in 100 ml of ethanol, added dropwise. After stirring for three hours at room temperature, the solid is filtered off with suction, washed with diethyl ether and dried. 13.5 g (75% of theory) of bis- [1- (2,4-dichlorophenyl) -2- (1,2,4-triazol-1-yl) ethyl] allyl ether are obtained - copper (II) chloride melting point 158 to 160 ° C.

Manufacture of intermediate products

25,7g (0,1 Mol) 1-Hydroxy-1-(2,4-dichlorphenyl)-2-(1,2,4-triazol-1-yl)-ethan werden in 125 ml Dioxan gelöst und unter Rühren zu einer Suspension von 4 g 80%igem Natriumhydrid in 150 ml Dioxan getropft. Danach wird eine Stunde unter Rückfluss erhitzt. Nach dem Abkühlen werden bei Raumtemperatur zu dem so erhaltenen Natriumsalz 22,1 g (0,1 Mol) Allylbromid zugegeben. Anschliessend erhitzt man 8 Stunden unter Rückfluss, lässt abkühlen und engt durch Abdestillieren des Lösungsmittels ein. Der Rückstand wird mit Wasser und Methylenchlorid versetzt, die organische Phase abgetrennt, über Natriumsulfat getrocknet und eingeengt. Es verbleiben 29,3 g

[1-(2,4-Dichlorphenyl)-2-(1,2,4-triazol-1-yl)-ethyl]-allyl-ether mit dem Brechungsindex , wobei die Ausbeute praktisch quantitativ ist.

25.7 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 added with stirring a suspension of 4 g of 80% sodium hydride in 150 ml of dioxane. The mixture is then heated under reflux for one hour. After cooling, 22.1 g (0.1 mol) of allyl bromide are added to the sodium salt thus obtained at room temperature. The mixture is then heated under reflux for 8 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. There remain 29.3 g

[1- (2,4-dichlorophenyl) -2- (1,2,4-triazol-1-yl) ethyl] allyl ether with the refractive index, the yield being practically quantitative.

25.6 g (0.1 mol) of ω- (1,2,4-triazo) -1-yt) -2,4-dichloro-acetophenone are dissolved in 300 ml of methanol and added at 5 to 10 ° C. with stirring in portions 4g (0.1 mol) of sodium borohydride were added. The mixture is then stirred at room temperature for one hour 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) ethane are obtained from the melting point 90 ° C.

269 g (1 mol) of ω-bromo-2,4-dichloroacetophenone are dissolved in 250 ml of acetonitrile. This 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 refluxing for 20 hours, the cooled suspension is filtered, the filtrate is freed from the solvent and the residue is taken up in acetic acid, washed with water, dried over sodium sulfate and freed from the solvent. The ethyl acetate residue crystallizes out when it is mixed with isopropanol.

After recrystallization from ligroin / isopropanol, 154 g (60% of theory) of ω- (1,2,4-triazole) -1 -yl) -2,4-dichloroacetophenone with a melting point of 117 ° C. are obtained.

Example 2

1,7 g (0,0083 Mol) Mangandichlorid werden in 40 ml Wasser gelöst und unter Rühren zu 5,3 g (0,0166 Mol) [1-(4-Phenoxyphenyl)-2-(1,2,4-triazol-1-yl)-ethyl]-allyl-ether, gelöst in 100 ml Ethanol, getropft. Man lässt 1,5 Stunden bei Raumtemperatur rühren. Das abgeschiedene Öl wird dekantiert und mit Petrolether verrieben, wobei es durchkristallisiert. Der Feststoff wird abgesaugt und getrocknet. Man erhält 5,5 g (87% der Theorie) an Bis-([1-(4-Phenoxyphenyl)-2-(1,2,4-triazol-1-yl)-ethyl]-allyl-ether)-mangan(ll)-chlorid vom Schmelzpunkt 180 bis 200°C.

1.7 g (0.0083 mol) of manganese dichloride are dissolved in 40 ml of water and, with stirring, 5.3 g (0.0166 mol) of [1- (4-phenoxyphenyl) -2- (1,2,4-triazole -1-yl) ethyl] allyl ether, dissolved in 100 ml of ethanol, added dropwise. The mixture is stirred at room temperature for 1.5 hours. The separated oil is decanted and triturated with petroleum ether, whereby it crystallizes through. The solid is suction filtered and dried. 5.5 g (87% of theory) of bis - ([1- (4-phenoxyphenyl) -2- (1,2,4-triazol-1-yl) ethyl] allyl ether) manganese are obtained (II) chloride of melting point 180 to 200 ° C.

Example 3

3,5 g (0,025 Mol) Zinkdichlorid werden in 40 ml Wasser gelöst und unter Rühren zu 17 g (0,05 Mol) 1-(2,4-Dichlorphenyl)-1-trimethylacetoxy-2-(1,2,4-triazol-1-yl)-ethan, gelöst in 100 ml Ethanol, getropft. Nach dreistündigem Rühren bei Raumtemperatur wird der Feststoff abgesaugt und getrocknet. Man erhält 13,1 g (72% der Theorie) Bis-[1-(2,4-Dichlorphenyl)-1-trimethylaceto- xy-2-(1,2,4-triazol-1-yl)-ethan]-zink(ll)-chlorid vom Schmelzpunkt 160°C.

3.5 g (0.025 mol) of zinc dichloride are dissolved in 40 ml of water and, with stirring, 17 g (0.05 mol) of 1- (2,4-dichlorophenyl) -1-trimethylacetoxy-2- (1,2,4- triazol-1-yl) -ethane, dissolved in 100 ml of ethanol, added dropwise. After stirring for three hours at room temperature, the solid is suction filtered and dried. 13.1 g (72% of theory) of bis- [1- (2,4-dichlorophenyl) -1-trimethylaceto-xy-2- (1,2,4-triazol-1-yl) ethane] - are obtained. zinc (II) chloride melting at 160 ° C.

Manufacture of the starting product

25,8g (0,1 Mol) 1-(2,4-Dichlorphenyl)-1-hydroxy-2-(1,2,4-triazol-1-yl)-ethan werden in 200 ml Dioxan gelöst und unter Rühren zu einem Gemisch aus 6 g 80%igem Natriumhydrid und 100 ml Dioxan getropft. Darrach wird ca. % Stunde unter Rückfluss erhitzt. Nach dem Abkühlen werden bei Raumtemperatur zu dem so erhaltenen Natriumsalz 24 (0,2 Mol) Trimethylessigsäurechlorid in 100 ml Dioxan zugetropft. Man lässt über Nacht bei Raumtemperatur rühren, engt durch Abdestillieren des Lösungsmittels im Vakuum ein und nimmt den Rückstand in Chloroform auf. Die Chloroformlösung wird mit Wasser gewaschen, über Natriumsulfat getrocknet und wiederum eingeengt. Der Rückstand kann direkt weiter umgesetzt werden.

25.8 g (0.1 mol) of 1- (2,4-dichlorophenyl) -1-hydroxy-2- (1,2,4-triazol-1-yl) ethane are dissolved in 200 ml of dioxane and added with stirring a mixture of 6 g of 80% sodium hydride and 100 ml of dioxane was added dropwise. Darrach is heated under reflux for about% hour. After cooling, 24 (0.2 mol) of trimethyl acetic acid chloride in 100 ml of dioxane are added dropwise to the sodium salt thus obtained. The mixture is stirred overnight at room temperature, concentrated by distilling off the solvent in vacuo and the residue is taken up in chloroform. The chloroform solution is washed with water, dried over sodium sulfate and again concentrated. The backlog can be implemented immediately.

The compounds of Table 4 below are obtained analogously to Examples 1 to 3.

The following compounds of the general formula can be prepared in a corresponding manner:

Claims (4)

1. Metal salt complexes of 1-phenyl-2-triazolyl- ethyl derivates of the general formula

in which

R represents fluorine, chlorine, bromine and alkyl with 1 to 4 carbon atoms, also phenyl or phenoxy optionally substitute by fluorine, chlorine or bromine,

R¹ represents the groupings -0-R or -0-CO-R³, wherein R² and R³ represent alkyl, alkenyl and alkinyl with in each case up to 4 carbon atoms, also benzyl optionally substituted in the aryl part by fluorine, chlorine, bromine or alkyl with 1 to 4 carbon atoms,

A represents a chloride, nitrate or sulphate anion,

Me represents the metalls copper, zinc, manganese, magnesium, tin, iron and nickel,

n represents integers from 0 to 3,

p represnets integers from 1 to 4 and

x represents integers from 1 to 4.

2. Process for the preparation of metal salt complexes of 1-phenyl-2-triazolyl-ethyl derivatives, characterised in that 1-phenyl-2-triazolyl-ethyl derivatives of the formula

in which

R, R¹ and n have the meaning given in claim 1, are reacted with metal salts of the formula

in which

k represents any numbers from 0 to 12 and

Me, A and p have the meaning given in claim 1,

in the presence of a solvent.

3. Fungicidal compositions, characterised in that they contain at least one metal complex of the 1-phenyl-2-triazolyl-ethyl derivatives according to claim 1.

4. Use of metal salt complexes of 1-phenyl-2-tria- zolylethyl derivatives according to claim 1 for combating fungi.