DE3431856A1 - Fungicidal agents based on acylaniline derivatives - Google Patents

Abstract

The invention relates to novel fungicidal synergistic active substance combinations composed of cyclopropanecarboxanilides of the formula (I) <IMAGE> in which Ar<1> represents optionally substituted phenyl and R represents hydrogen or a cyclopropylcarbonyl radical and a known fungicidal acylaniline of the formula (II) <IMAGE> in which Ar<2> represents optionally substituted phenyl, R<1> represents optionally substituted alkyl or heterocyclyl and R<2> represents optionally substituted alkyl, cycloalkyl or heterocyclyl.

Description

Acylaniline derivative based fungicides

The invention relates to new fungicidal synergistic combinations of active ingredients from special, partly known cyclopropanecarboxylic acid anilides and known fungicidal acylanilines.

It is already known that certain cyclopropanecarboxylic anilides have herbicidal or pesticidal properties (see, for example, US Pat. No. 3,306,727; Dutch patent application 66/5488 of April 29, 1965; J. Agricult. Food Chem. , 15: 501-507 (1967); U.S. Patent 4,193,787; DE-OS 1 803 084; U.S. Patent 3,277,107).

Related about a synergistic effect of these compounds nothing is known about fungicides.

It is also known that certain N-acylanilines have fungicidal properties (see e.g. DE-OSn 2 513 732, 2 515 091, 2 724 786, 2 922 759, 2 903 612, 2,940,189; 3,030,026 and U.S. Patent 3,933,860). Their effect is, however, in particular at low application rates and concentrations; not always in all areas of application completely satisfactory.

It has been found that the new active ingredient combinations of the special, partly known cyclopropanecarboxylic acid anilides of the formula (I) in which Ar1 represents optionally substituted phenyl and R represents hydrogen or a cyclopropylcarbonyl radical, on the one hand, and known fungicidal acylanilines of the general formula (II) in which Ar2 stands for optionally substituted phenyl, R1 stands for optionally substituted alkyl or heterocyclyl and R2 stands for optionally substituted alkyl, cycloalkyl or heterocyclyl, on the other hand have a particularly high fungicidal activity.

Surprisingly, the fungicidal action is that of the invention Combinations of active ingredients from the partly known cyclopropanecarboxylic anilides of the formula (I) on the one hand and the known fungicidal acylanilines of the formula (II) on the other hand, higher than the effect of the individual components (synergistic effect).

The active ingredient combinations according to the invention are thus an enrichment of technology.

Those to be used for the active ingredient combinations according to the invention special, partly known cyclopropanecarboxylic acid anilides are represented by the formula (I) generally defined. Preferred are compounds of the formula (1) in which Ar1 for optionally mono- or polysubstituted, identically or differently substituted Phenyl, with possible substituents: halogen, cyano, nitro, and in each case straight-chain or branched alkyl, alkoxy, alkylthio, haloalkyl, haloalkoxy or haloalkylthio each having 1 to 4 carbon atoms and optionally 1 to 9 identical or different halogen atoms and R for hydrogen or represents a cyclopropylcarbonyl radical.

Compounds of are particularly preferred as components of the mixture Formula (1) in which Ar1 optionally represents one to three, identical or different substituted phenyl, possible substituents being: fluorine, chlorine, Bromine, iodine, cyano, nitro, methyl, ethyl, methoxy, methylthio, trifluoromethyl, trifluoromethoxy or trifluoromethylthio and R for hydrogen or for a cyclopropylcarbonyl radical stands.

Some of the compounds of the formula (I) are known (cf., for example, DE-OS 1 803 084; US Pat. No. 3,462,486; US Pat. No. 3,277,107; J. Agricult. Food. Chem. 15, 501-507 (1967 ); U.S. Patent 3,306,727). The not yet known representatives can be prepared in analogy to known processes in which, for example, anilines of the formula (III) Ar1 -NH2 (III) in which Ar1 represents optionally substituted aryl, with acylating agents of the formula (IV), in which A stands for an electron-withdrawing group such as halogen or cyclopropylcarbonyloxy, optionally in the presence of a diluent such as toluene, optionally in the presence of an acid binder such as potassium carbonate, and optionally in the presence of a catalyst such as dimethylformamide at temperatures between + 200C and + 1500C, or alternatively, if aryl isocyanates of the formula (V), Ar1-N = C = O (V) in which Ar1 has the meaning given above, with cyclopropanecarboxylic acid of the formula (VI) optionally in the presence of a diluent such as toluene at temperatures between + 200C and + 1500C.

The fungicidally active acylanilines to be used as mixture components of formula (II) have already been described in the literature (cf. e.g. DE-OSn 2 513 732; 2,515,091; 2,724,786; 2,903,612; 2,922,759; 2,940,189; 3,030,026; U.S. Patent 3,933 860; EP-OS 26 873).

Preferred mixing partners of the formula (II) are in particular the following compounds: The weight ratios of the groups of active substances in the combinations of active substances can fluctuate within a relatively wide range. In general, 0.01 to 50 parts by weight of active ingredient of the formula (II), preferably 0.02 to 20 parts by weight, 0.05 to 5 parts by weight of the last group are particularly preferred per part by weight of compounds of the formula (I) by weight Compound of formula (II).

The active ingredient combinations according to the invention have a strong microbicidal effect Effect on and can come in handy for combating unwanted microorganisms can be used. The active ingredient combinations are for use as pesticides suitable.

Fungicidal agents in crop protection are used for control of Plasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes, Deuteromycetes. The good plant tolerance of the active ingredient combinations Allowed in the concentrations required to combat plant diseases a treatment of above-ground parts of plants, of vegetation and seeds, and des Soil.

The active ingredient combinations according to the invention can be used against parasitic fungi that attack above-ground parts of plants or the plants attack from the ground, as well as seed-borne pathogens. Particularly practical Have meaning Combinations of active ingredients as seed dressing against phytopathogenic fungi that are transmitted with the seeds or in the soil occur and attack the cultivated plants from there. These are seedling diseases, Root rot, stem, stem, leaf, flower, fruit and seed diseases, the especially caused by Oomycetes. Due to the systemic effect The plants of one mix partner are often a long time after dressing still protected from pathogens that attack different parts of the shoot can. The active ingredient combinations can also be used as soil treatment agents against phytopathogenic fungi are used and act against root rot caused by, for example Pathogens of the genus Pythium and Phytophthora are caused.

However, the active ingredient combinations according to the invention also show excellent results Effect against pathogens when applied directly to the above-ground parts of the plant on various cultivated plants, such as Phytophthora species, Peronospora species, Plasmopara species, Pseudoperonospora species, Sclerospora species.

The active ingredient combinations can be converted into the customary formulations such as solutions, emulsions, wettable powders, suspensions, powders, dusts, Foams, pastes, soluble powders, granulates, aerosols, suspension emulsion concentrates, Seed powder, active ingredient-impregnated natural and synthetic substances, ultra-fine encapsulation in polymeric substances and in coating compounds for seeds, also in formulations with Burning sets, such as incense cartridges, cans, spirals, etc. as well as ULV cold and warm mist formulations. These Formulations are prepared in a known manner, for example by mixing the Active ingredients with extenders, i.e. liquid solvents, under pressure liquefied gases and / or solid carriers, if necessary using of surface-active agents, i.e. emulsifiers and / or dispersants and / or foam-generating agents.

In the case of using water as an extender, e.g. organic solvents can be used as auxiliary solvents. As a liquid solvent are essentially: aromatics, such as xylene, toluene, or alkyl naphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, 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, strongly polar solvents such as dimethylformamide and dimethyl sulfoxide, as well as water; with liquefied gaseous extenders or carriers such liquids are meant which are at normal temperature and under normal pressure are gaseous, e.g. aerosol propellants such as halogenated hydrocarbons and butane, Propane, nitrogen and carbon dioxide; as solid carriers are possible: e.g. natural rock flour, such as kaolins, clays, talc, chalk, quartz, attapulgite, Montmorillonite or diatomaceous earth and synthetic rock powder, such as highly dispersed Silica, aluminum oxide and silicon kate; as carriers for Granules are possible: e.g. broken and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite and synthetic granules made from inorganic and organic flours as well as granules made of organic material such as sawdust, coconut shells, Corn on the cob and tobacco stalks; come as emulsifying and / or foam-producing agents in question: e.g. non-ionic and anionic emulsifiers, such as polyoxethylene fatty acid esters, Polyoxyethylene fatty alcohol ethers, e.g. alkylaryl polyglycol ethers, alkyl sulfonates, Alkyl sulfates, aryl sulfonates and protein hydrolysates; come as a dispersant in question: e.g. lignin sulphite waste liquors and methyl cellulose.

Adhesives such as carboxymethyl cellulose, natural and synthetic powdery, granular or latex-like polymers are used such as gum arabic, polyvinyl alcohol, polyvinyl acetate, as well as natural phospholipids, such as cephalins and lecithins, and synthetic phospholides.

Further additives can be mineral and vegetable oils.

Dyes such as inorganic pigments, e.g.

Iron oxide, titanium oxide, ferrocyan blue and organic dyes such as Alizarin, azo or metal phthalocyanine dyes and trace nutrients such as salts iron, manganese, boron, copper, cobalt, molybdenum and zinc can be used.

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

The active compound combinations according to the invention can be used in the formulations or in the various application forms as a mixture with other known active ingredients present, such as fungicides, bactericides, insecticides, acaricides, nematicides, Herbicides, bird repellants, growth substances, plant nutrients and Soil structure improvers.

The active ingredient combinations can be used as such, in the form of their 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 watering, dipping, spraying, Spraying, atomizing, vaporizing, injecting, silting up, spreading, dusting, Spreading, dry pickling, moist pickling, wet pickling, slurry pickling or encrusting.

When treating parts of plants, the drug concentrations can be varied in the application forms over a wide range. You are in generally between 1 and 0.0001% by weight, preferably between 0.5 and 0.001% by weight.

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

When treating the soil, the active ingredient concentrations are 0.00001 up to 0.1% by weight, preferably from 0.0001 to 0.02% by weight, required at the site of action.

The following application examples serve to explain: example A Phytophthora test (tomato) / protective solvent: 4.7 parts by weight of acetone Emulsifier: 0.3 parts by weight of alkyl aryl polyglycol ether Active ingredient preparation is mixed 1 part by weight of active ingredient with the specified Quantities of solvent and emulsifier and dilute the concentrate with water on the desired concentration.

To test for protective effectiveness, young plants are sprayed with the active ingredient preparation to runoff. After the spray coating has dried on the plants are treated with an aqueous spore suspension of Phytophthora infestans inoculated.

The plants are in an incubation cabinet with 100% relative Humidity and about 200C.

Evaluation is carried out 3 days after the inoculation.

Table A Phytophthora test (tomato) / protective active ingredients or infestation in% with an active ingredient combination substance concentration of 50 ppm 47 25 ppm 69 50 ppm 64 25 ppm 73 Mixture (II-5) 50 ppm + (I-1) 50 ppm 6 Mixture (II-5) 25 ppm + (I-1) 25 ppm 32 Example B Downy mildew test (Kohl) / protective Solvent: 4.7 parts by weight acetone Emulsifier: 0.3 parts by weight alkyl aryl polyglycol ether To produce an appropriate preparation of active ingredient, 1 part by weight of active ingredient is mixed with the stated amounts of solvent and emulsifier and the concentrate is diluted with water to the desired concentration.

To test for protective effectiveness, young plants are sprayed with the active ingredient preparation until wet. 24 hours after treatment the plants inoculated with an aqueous spore suspension of Peronospora brassicae and then remain at 180C and 100% rel. Humidity in one Greenhouse chamber.

Evaluation is carried out 7 days after the inoculation.

Table B Downy mildew test (cabbage) / protective active ingredients or infestation in% with an active ingredient combination substance concentration of 0.5 ppm 18 0.25 ppm 41 2 ppm 36 mixture (II-7) 0.5 ppm + (I-1) 2 ppm 0 mixture (II-7) 0.25 ppm + (I-1) 1 ppm 9 production examples: Example 1 11.7 g (0.11 mol) of 98% strength are added dropwise with stirring to a mixture of 13.0 g (0.1 mol) of 3-chloroaniline, 15.2 g (0.11 mol) of potassium carbonate and 200 ml of toluene Cyclopropanoyl chloride and then heated under reflux for 3 hours.

The cooled reaction mixture is diluted with 100 ml of ethyl acetate and washed successively with water, 1 molar hydrochloric acid and again with water, dried over sodium sulfate and concentrated in vacuo. The oily residue crystallizes from petroleum ether. 10.0 g (92% of theory) of 3'-chlorocyclopropanecarboxylic acid anilide are obtained from melting point 1440C to 1450C.

Example 2 and Example 3 and 32 g (0.3 mol) of 98% strength cyclopropanecarboxylic acid chloride are added dropwise to a solution of 23.6 g (0.2 mol) of 3-aminobenzonitrile and 5 drops of dimethylformamide in 400 ml of toluene, and the reaction mixture is refluxed for 4.5 hours.

After cooling to 50 ° C., the precipitate is filtered off with suction with petroleum ether washed and dried at 400C. This gives 21.7 g (58.3% of theory) 3'-Cyancyclopropanecarboxylic acid anilide with a melting point of 1420C to 1440C.

The mother liquor is successively twice with 100 ml of 10 hydrochloric acid, Washed 200 ml of sodium hydrogen carbonate solution and 400 ml of water over sodium sulfate dried and evaporated in vacuo. The residue is made from ethyl acetate-petroleum ether recrystallized. This gives 13.5 g (35.4% of theory) of N- (3-cyanophenyl) -di (cyclopropanecarbox) -imide from melting point 137 0C to 1390C.

The following cyclopropanecarboxylic acid anilides of the general formula (I) are obtained in a corresponding manner: Example No.Ar1 R Sec ~ melting point / ° C ~ 7 C1 4 X - H 149-150 CH3 F3C 5½- H 118-119 02N 6 W - H 146-148 Example No. Ar1 R Sch R ScLmeftzunt / 0C? Cl 7 2 - H 167-168 C1 C1 8 C1 -C to 107-108 I. H3Cs 9 \ H 96-97 H3C 10 H3C \: and 4: 1.5392 O

Claims (8)

Claims 1. Fungicidal agents, characterized by a content of an active ingredient combination consisting of at least one cyclopropanecarboxylic acid anilide of the formula (I) in which Ar 1 represents optionally substituted phenyl and R represents hydrogen or a cyclopropylcarbonyl radical, and at least one acylaniline of the formula (II) in which Ar2 stands for optionally substituted phenyl, R1 stands for optionally substituted alkyl or heterocyclyl and R2 stands for optionally substituted alkyl, cycloalkyl or heterocyclyl. 2. Fungicidal agents according to claim 1, containing at least one active ingredient of the formula (I), in which Ar1 is optionally mono- or polysubstituted, identically or differently substituted phenyl, possible substituents being: halogen, cyano, nitro, as well as straight-chain or branched ones Alkyl, alkoxy, alkylthio, haloalkyl, haloalkoxy or haloalkylthio each having 1 to 4 carbon atoms and optionally 1 to 9 identical or different halogen atoms and R represents hydrogen or a cyclopropylcarbonyl radical and one of the active ingredients of the formula (II) listed below or or or or or or or 3. Fungicidal agents according to claim 1, containing at least one active ingredient of the formula (I), wherein Ar1 is optionally mono- to triple, identically or differently substituted phenyl, possible substituents being: fluorine, chlorine, bromine, iodine, cyano, Nitro, methyl, ethyl, methoxy, methylthio, trifluoromethyl, trifluoromethoxy or trifluoromethylthio and R represents hydrogen or a cyclopropylcarbonyl radical and one of the active ingredients of the formula (II) listed below or or or oaer or or or 4. Fungicidal agents according to claim 1, characterized in that in the active ingredient combinations the weight ratio of a cyclopropanecarboxylic acid anilide of the formula (I) to an acylaniline of the formula (II) is between 1: 0.01 and 1:50. 5. Fungicidal agents according to Claims 1 and 4, characterized in that that in the combinations the weight ratio of a cyclopropanecarboxylic acid anilide of the formula (I) to an acylaniline of the formula (II) is between 1: 0.02 and 1:20. 6. A method of combating fungi, characterized in that an active ingredient combination according to claim 1 on fungi and / or their habitat can act. 7. Use of fungicidal agents according to claim 1 for control of mushrooms. 8. A process for the production of fungicidal agents, characterized in that that one active ingredients resp. the active ingredient combinations according to claim 1 with extenders and / or surfactants mixed.