DE2503337A1 - Copper imidazole complex fungicide - bis (methyl diphenyl-imidazol-1-ylacetate)-copper chloride - Google Patents

Abstract

Bis(methyl alpha, alpha-diphenyl-alpha-imidazol-1-ylacetate) copper (II) chloride of formula (A) is new: Cpd. (A) has higher fungicidal activity than known N-trityl-imidazoles esp. against mildews, e.g. Erysyphe and Podosphaera spp., and can be prepd by reacting methyl alpha, alpha-diphenyl-alpha-imidazol-1-ylacetate with CuCl2 in a diluent at 0-40 degrees C.

Description

Bis- (diphenyl-imidazolyl- (1) acetic acid-methyl ester) -copper- (II) -chloride, Process for its preparation as well as its use as a fungicide The present Invention relates to the new bis (diphenylimidazolyl (1) acetic acid methyl ester) copper (II) chloride, a process for its manufacture and its use as a fungicide.

It has already become known that N-trityl-imidazole, such as.

N-triphenylmethyl-imidazole and 1- (2-chlorophenyl-diphenyl-methyl) -imidazole, Have good fungicidal effectiveness (see US Pat. No. 3,321,366 and German Offenlegungsschrift 1,670,976 or the corresponding British patent specification 1 260 588). It is also known that N-trityl-imidazolium salts have a fungicidal effect are (compare German Offenlegungsschrift 1 670 977 or the corresponding British Patent 1,260,211j. Similar imidazole derivatives, but with a disubstituted one Triphenylmethyl radical are also described, these compounds are intended under be effective against mold fungi, among other things (see German Offenlegungsschrift 2,213,853 or the equivalent South African patent 73-1981). However, the effect of all these substances against phytopathogenic fungi is low Application rates and concentrations not always fully satisfactory. Besides, the Plant tolerance at higher concentrations is not always entirely satisfactory.

It has been found that the new ris- (di: phenyl-imidazolyl- (1) -acetic acid methyl esterj-copper- (IIj-chloride of the formula has strong fungicidal properties.

It has also been found that the metal complex of the formula (1) is obtained when the compound of the formula with copper dichloride (CuCl2 x 2 n; 20) in the presence of a diluent.

Surprisingly, the metal complex according to the invention shows good results Plant tolerance has a significantly higher fungicidal effectiveness, in particular against powdery mildew than the N-trityl-imidazole known from the prior art, which are the closest active ingredients.

The active ingredient according to the invention is thus an enrichment of the Technology.

If di phenyl-imidazolyl- (1) -acetic acid methyl ester and copper (II) chloride are used as starting materials, the course of the reaction can be represented by the following equation: The derivative of the formula (II) to be used as the starting material is known (see German laid-open specification 1 925 994 or the corresponding British patent specification 1 289 224; for the preparation see also the experimental section).

The diluent used for the reaction according to the invention is water and all inert organic solvents.

These preferably include alcohols such as methanol and ethanol; Ketones, such as acetone; and ethers such as diet ether and dioxane.

The reaction temperatures can be varied within a relatively wide range will. In general, one works between 0 and 40 ° C., preferably between 15 and 25 ° C.

When carrying out the process according to the invention, one sets up 1 ol of the metal salt is the stoichiometric amount (corresponding to the oxidation state of the metal) of the compound of the formula (Li). Exceeding this ratio by up to 20 lviolw can take place without a significant reduction in yield. The work-up takes place in a manner customary and generally known for organic compounds, E.g. by simply sucking off the accumulated product.

The active ingredient according to the invention has a strong fungitoxic effect on. It damages crops in the concentrations required to control fungi not. For these reasons it is suitable for use as a pesticide to control suitable for mushrooms. Fungitoxic agents in crop protection are used for Control of Archimycetes, Phycomycetes, Ascomycetes, Basidiomycetes and Fungiimperfecti.

The active ingredient according to the invention has a very broad spectrum of activity and can be used against parasitic fungi that affect parts of plants above ground infested or attacking the plants from the ground as well as against seed-transmissible ones Pathogens.

It is particularly effective against parasitic fungi aerial parts of plants such as Erysiphe species, Podosphaera species, Venturia species; also against Pyricularia and Pellicularia species. It should be emphasized that the inventive Active ingredient not only has a protective effect, but also has a curative effect is, d. H. can also be used after infection.

The substance according to the invention can be used as a plant protection agent for seeds. and soil treatment as well as for the treatment of above-ground parts of plants.

The substance according to the invention is well tolerated by plants. He owns only low warm-blooded toxicity and is due to its low odor and its good tolerance for human skin not uncomfortable to handle.

The active ingredient according to the invention can be used in the customary formulations be transferred, such as solutions, emulsions ,.

Suspensions, powders, pastes and granulates. These are known in Manufactured in a manner such as by mixing the active ingredient with relaxants, i.e. liquid solvents, pressurized liquefied gases and / or solids Carriers, optionally with the use of surface-active agents, that is Emulsifiers and1 or dispersants and / or foam-generating agents. in the If water is used as an extender, organic solvents, for example, can also be used can be used as co-solvents. The liquid solvents used are essentially in question: aromatics such as xylene, toluene, benzene or alkylnaphthalenes, chlorinated Aromatics or chlorinated aliphatic hydrocarbons such as chlorobenzenes and chloroethylenes 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, are strong polar solvents such as dimethylformamide and dimethyl sulfoxide, and water; with Liquefied gaseous extenders or carriers are such liquids meant which are gaseous at normal temperature and under normal pressure, e.g. Aerosol propellants such as dichlorodifluoromethane or trichlorofluoromethane; as fixed Carriers: natural rock flour, such as kaolins, Clays, talc, Chalk, quartz, attapulgite, montmorillonite, or diatomaceous earth, and synthetic rock flour, such as finely divided silica, aluminum oxide and silicates; as emulsifier: non-ionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, e.g., alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates and aryl sulfonates; as dispersants: e.g. lignin, sulphite waste liquors and methyl cellulose.

The active ingredient according to the invention can be used as a mixture in the formulations with other known active ingredients, such as fungicides, insecticides, acaricides, Nematicides, selective herbicides, bird repellants, growth substances, Plant nutrients and soil structure improvers.

The formulations generally contain between 0.1 and 95% by weight Active ingredient, preferably between 0.5 and 90 s.

The active ingredient can be used as such, in the form of its formulations or the use forms prepared therefrom by further dilution, such as ready-to-use Solutions, emulsions, suspensions, powders, pastes and granulates can be used.

It is used in the usual way, e.g. by pouring, spraying, Spraying, dusting, scattering, dry pickling, moist pickling, wet pickling, slurry pickling or encrusting.

When used as a foliar fungicide, the active ingredient concentration can can be varied in the application forms over a wide range. She lies in generally between 0.1 and 0.00001 percent by weight, preferably between 0.05 and 0.0001.

In the treatment of seeds, an amount of the active ingredient is generally used from 0.01 to 50 g per kilogram of seed, preferably from 0.01 to 10 g, is required.

The good fungicidal effectiveness of the active ingredient according to the invention goes from the examples below.

Example A: Sprout treatment test / powdery mildew / protective (leaf-destroying Mycosis) To produce an appropriate preparation of active ingredient, 0.25 parts by weight are used Active ingredient in 25 parts by weight of dimethylformamide and 0.06 part by weight of emulsifier Alkylaryl polyglycol ether and add 975 parts by weight of water. The concentrate it is diluted with water to the desired final concentration of the spray mixture.

To test for protective effectiveness, the single-leafed ones are sprayed Young barley plants of the Amsel cultivar with the preparation of the active compound are dewy. To After drying, the barley plants are dusted with spores of Erysiphe graminis var. hordei.

After 6 days of residence time of the plants at a temperature of 21 up to 22 0C and a humidity of 80 to 90% one evaluates the stocking of the plants with powdery mildew pustules.

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

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

Table A Sprout Treatment Test / Cereal Meal Dew / Protective Active ingredients Active ingredient concentration in ffi der tration in the untreated Spray mixture in control Weight% untreated 100 Cp RC <25.0 r- / 0.003 7j5.0 0.001 85.0 (known) 0.01 77.5 9 IC 9 O, Ol 77.5 At CH3 (known) Cu, cCIO;) H3 C12 o0: Oolo2s l22: 5s 0.001 31.3 Example B Sprout treatment test / cereal dew / curative (leaf-destroying mycosis) To produce an appropriate preparation of active ingredient, 0.25 parts by weight of active ingredient in 25 parts by weight of dimethylformamide and 0.06 part by weight of emulsifier alkylaryl polyglycol ether are added, 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 curative effectiveness one proceeds in a corresponding way but in reverse order as for the test for protective effectiveness. the Treatment of the single-leaved young barley plants with the active compound preparation takes place 48 hours after inoculation if the infection is already manifest.

After 6 days of residence time of the plants at a temperature of 21 Up to 220C and a humidity of 80 to 9oS one evaluates the stocking of the plants with powdery mildew pustules. The degree of infestation is expressed as a percentage of the infestation of the untreated Control plants expressed. 0% means no infestation and 100 the same Degree of infestation as in the untreated control. The active ingredient is all the more effective the lower the powdery mildew infestation.

Active ingredients, active ingredient concentrations in the spray liquor and degrees of infestation are shown in the table below: Table B Sprout treatment test / powdery mildew / curative Active ingredients Active ingredient concentration in% of tration in the untreated Spray mixture in control Weight% untreated - 100 0.003 47.5 wsCt 0.001 100 (known) 0.01 0.01 57.5 C - <: H3 (known) CO-cocH3 Cu 2 C), 01 16.3 Cu 0.0025 28.8 0.001 27.5 Example C Podosphaera test (apple powdery mildew) / Protective solvent: 4.7 parts by weight acetone Emulsifier: 0.3 parts by weight alkyl aryl polyglycol ether Water: 95 parts by weight The amount of active ingredient required for the desired concentration of active ingredient in the spray liquid is mixed with the specified amount of solvent and dilutes the concentrate with the specified amount of water, which contains the additives mentioned.

Young apple seedlings are sprayed with the spray liquid are in the 4 - 6 leaf stage, up to dripping wet.

The plants remain at 200 ° C. and a relative atmospheric humidity for 24 hours of 70% in the greenhouse.

They are then pollinated with conidia of the apple powdery mildew pathogen (Podosphaera leucotricha inoculated and placed in a greenhouse with a temperature brought from 21 to 23 0C and a relative humidity of approx. 70%.

10 days after the inoculation, the percentage of the seedlings is infected untreated, but also inoculated control plants determined.

0% means no infestation, 100% means that the infestation is exactly the same is high as in the control plants.

Active ingredients, active ingredient concentrations and results are shown in the table below, Table C Podosphaera test / Protective Active ingredient infestation in% of the infestation of the unaffected acted control at one Active ingredient concentration (in%) of 0.00125 0.00062 26 41 Ir I ;. (known) co-OCH3 tS) 2 C12 1 7 0 (LNI 2 Example D Erysiphe test Solvent: 4.7 parts by weight acetone Emulsifier: 0.3 parts by weight alkyl aryl polyglycol ether Water: 95 parts by weight The amount of active ingredient required for the desired concentration of active ingredient in the spray liquid is mixed with the specified amount of solvent and the concentrate is diluted with it the specified amount of water, which contains the additives mentioned.

The spray liquid is used to spray young cucumber plants with about three leaves to dripping wet. The cucumber plants are left to dry 24 hours in the greenhouse. Then they are inoculated with the conidia of the fungus Erysiphe cichoreacearum pollinated. The plants are then at 23 to 240C and an approximately own relative humidity in the greenhouse.

After 12 days, the infestation of the cucumber plants as a percentage of the untreated, however, inoculated control plants were also determined. 0% means no infestation, 100% means that the infestation is just as high as in the control plants.

Active ingredients, active ingredient concentrations and results are shown in the table below: Table D Erysiphe test Active ingredient infestation in ffi the infestation of the un- treated control at a Active ingredient concentration of 0§00025 0.000125 34 46 Qi 6ì} W. (known) CO-OCH3 Cu C12 2 9 N <% NI Example E Mycelium growth test Nutrient medium used: 20 parts by weight of agar-agar 200 parts by weight of potato decoction 5 parts by weight of malt 15 parts by weight of dextrose 5 parts by weight of peptone 2 parts by weight of disodium hydrogen phosphate 0.3 parts by weight of calcium nitrate Ratio of solvent mixture to nutrient medium composition 2 parts by weight of solvent mixture 100 parts by weight of agar medium 19 parts by weight of acetone 0.01 part by weight of emulsifier alkyl aryl polyglycol ether 1; 80 parts by weight of water 2 parts by weight of solvent mixture The amount of active substance required for the desired concentration of active substance in the nutrient medium is mixed with the stated amount of the solvent mixture. The concentrate is mixed thoroughly with the liquid nutrient medium, cooled to 429C, in the specified proportions and poured into Petri dishes with a diameter of 9 cm. Furthermore, control plates are set up without adding any preparation.

If the nutrient medium is cold and solid, the plates are filled with dei. in the T *; ç! 1.e specified mushroom species inoculated and incubated at about 21 ° C.

The evaluation is carried out after 4-10 days, depending on the rate of growth of the fungi. During the evaluation, the radial mycelial growth on the treated culture media is compared with the growth on the introl culture media. The rating of the fungal growth is done with the following key figures 1 no fungal growth to 3 very strong growth inhibition to 5 moderate growth inhibition to 7 weak growth inhibition 9 growth equal to the untreated control active ingredients, active ingredient concentrations and results are shown in the following table, Table E. Mushrooms H Mycelium growth test i.e. O , l rl F (El Fc cd ocdcI1 o OU w C6 * d (> 0 C) +>«> D a> A o cd a, rl H cd 0 Active ingredients active ingredient con- ewS <o- cdo.HO N (d 0> oH centering oo o- O <h hS- m ppm O0Ocd1iO0 10 dd 9 9 9 5 9 5 cI (known) ¼ CF3 Nope ' L NC 9 x HCl 9 99 9 9 7 3 (known) Table E (continued) Mushrooms CD Mycelium growth test is: m 0> H, I c4-d H kdk h k "= S rl k OQ, a, -P ap d (d cl o rb <d od O cd rl Li rl 4m Active ingredients Active ingredient concentration ocdcd H cd <09 oh th nh hhm. h 2 Co 0 Active ingredients active ingredient concentration ppm T-'WO hkP v 0cd NcdHcd 0> m concentration ppm -. 10 O0Ocdo0S x 9 ¢ x X CH3 -CH = CH-CH = CH-COOH 9 9 9 7 9 9 1 nS v 1 (known) O-OCH3 CU (I C12 5151 31 <fN3 J Manufacturing example: 8.5 g (0.05 mol) of copper dichloride (CuCl2 x 2 HzO) are dissolved in 20 Lnl of water and, with stirring, add 21.9 g (0.075 mol) of methyl di phenylimidazolyl (1) acetic acid, dissolved in 200 ml of ethanol, added dropwise. After stirring for one hour at room temperature, the precipitate formed is filtered off with suction and washed with a little ether. 14 g (51.8% of theory) are obtained

Theory) turquoise crystals of bis- (diphenyl-imidazolyl- (l) -acetic acid methyl ester) copper (II) chloride, melting point 1970C (decomp.).

Representation of the precursors methyl benzilic ester 450 g benzilic acid are with 4.5 liters of methanol and 150 ccm conc. Sulfuric acid in a 10 liter stirred flask Heated to the boil for 3 hours. Most of the methanol is distilled off in vacuo. The remaining crystal mass is filtered off with suction on a glass suction filter after cooling and deprecated.

Then this is in a mortar with ice and soda solution until alkaline reaction worked through.

It is suctioned off and washed well with water. The ester becomes moist recrystallized from methanol. 406 g (85 "of theory) methyl benzilate are obtained with a melting point of 0 72 C.

Di phenyl chloroacetic acid methyl ester 323 g benzilic acid methyl ester are mixed with 287 g of phosphorus pentachloride and in a 2-liter stirred flask in one Bath heated by 700C. When the mass becomes a little sticky, the bath is removed and the violent reaction up to the boiling point of the phosphorus oxychloride undermines Liquefaction within controllable limits. It will be another 4 hours in a bath heated to boiling of 120 ° C. The phosphorus oxychloride is distilled off in vacuo. After cooling, the residue is treated with 670 cc of ice water and with methylene chloride shaken out.

The solution is made slightly alkaline with sodium bicarbonate solution Reaction shaken out. The combined organic phases are stirred with stirring dried with sodium sulfate with the addition of sodium bicarbonate and after distilling off of the solvent immediately distilled in vacuo.

333 g (95% of theory) of methyl bisphenyl chloroacetate are obtained with a boiling point Epo 3 = 1420C.

(The compound can, however, also be used raw, since it is without First run distilled with only a small residue.) Diphenyl-imidazolyl- (l) -acetic acid methyl ester 300 g of methyl phenyl chloroacetate are mixed with 405 g of imidazole in 2.9 liters Acetonitrile heated to boiling for 19 hours. After distilling off the solvent 1500 cc of water are added and the mixture is extracted with methylene chloride.

The solvent layer is washed over again with water Dried sodium sulfate and the iviethylene chloride was distilled off in vacuo. Of the The residue is recrystallized from 1.5 liters of ethyl acetate. 188 g (56% the theory Di phenyl-imidazolyl- (1) -acetic acid methyl ester with a melting point of 1550C.

Claims (6)

Claims 14 Bis (diphenylimidazolyl (1) acetic acid methyl ester) copper (11) chloride of the formula 2. Process for the preparation of bis (diphenyl-imidazolyl- (1) -acetic acid methyl ester) -cup r - (II) chloride, characterized in that the compound of the formula with copper dichloride in the presence of a diluent. 3. Fungicidal agents, characterized by a content of bis- (diphenyl-imidazolyl- (1 ) methyl acetate) copper (II) chloride according to claim 1. 4. A method of combating fungi, characterized in that bis (diphenylimidazolyl (1) acetic acid methyl ester) copper (11) chloride according to claim 1 can act on fungi or their habitat. 5. Use of bis (diphenylimidazolyl (1) methyl acetate) copper (II) chloride according to claim 1 for combating fungi. 6. Process for the production of fungicidal agents, characterized in that that bis-diphenyl-imidazolyl- (1) -acetic acid methyl ester) copper (11) chloride according to claim 1 mixed with extenders and / or surface-active agents.