DE3309765A1 - Fungicidal agents - Google Patents

Abstract

The present invention relates to novel fungicidally active combinations which contain, on the one hand, a known fungicide and, on the other hand, a vegetable oil or a lecithin or linoleic acid.

Description

Fungicides

The invention relates to new combinations with a fungicidal effect, the besides a known fungicide on the one hand a vegetable dl or a lecithin or linoleic acid on the other hand. The agents according to the invention have a higher effect than the known fungicide components.

It is already known that, for example, 1- (4-chlorophenoxy) -3,3-dimethyl-1- (1H-1,2 r 4-triazol-1-yl) -2-butanone can be used as a fungicide (see e.g. R. Regulator, "Chemistry of pesticides and pesticides", Vol. 4, page 208, Springer Verlag Berlin-Heidelberg-New York 1977).

It is also known that additives of mineral oils to crop protection formulations can increase the effectiveness of these formulations. However, these formulations show often has disadvantages, e.g. an emulsifiable dl can cause the spray liquid to roll down. of the Plants increase or phytotoxic effects are observed. These disadvantages and others can be prevented by adding lecithin (cf. HU patent no.

176.051).

It is also known that lecithin is its colloidal, surface-active, emulsifying and physiological properties because of their versatile uses can. For example, lecithin emulsions are produced in pest control have good stability and adhesive strength (cf. Ullmanns Encyklopadie der technical chemistry, vol. 11, pages 549-550, 1960).

In addition, insecticidal aid compositions are known which in addition to an insecticide, a vegetable bl, a vegetable flour and surface-active Contain aids (cf. Offenlegungsschrift 2 730 205).

It is also known that the effectiveness of crop protection agents, such as fungicides or growth regulators, by adding a surface-active one Substance in concentrations higher than those used to reduce surface tension required quantities, can be increased (cf. GB 2 057 265). To these surface-active Lecithin also counts substances.

It has now surprisingly been found that the new combinations exist from a known fungicide from Group I, exemplified by the following Active ingredients are: I. a) 1,4-Benzoquinone-1-benzoylhydrazone-4-oxime b) 6-methyl-2-oxo-1,3-dithiolo (4,5-b) -quinoxaline c) N- / 2,2,2-trichloro-1- (3,4-dichloroaniline) -ethyl7-formamide d) N-dichlorofluoromethanesulfenyl-N ', N'-dimethyl-N-phenyl sulfamide e) O-ethyl-S, S-diphenyl-phosphoric acid ester f) Bios-phenyl- (3-trifluoromethyl-phenyl) -1- (1,2,4-triazolyl) -methane g) 2- (2-furanyl) -1H-benzimidazole h) 1- (4-chlorophenoxy) -3,3-dimethyl-1- (1H-1,2,4-triazol-1 -yl) -2-butanone i) ß- [1,1'-biphenyl) - 4-yloxy] -α- (1,1-dimethylethyl) -1H-1,2,4-triazol-1-ethanol j) 1- (4-chlorophenoxy) -1- (1H-imidazol-1-yl) -3,3-dimethyl-2-butanone k) ß- (4-chlorophenoxy) -α- (1,1-dimethylethyl) -1H-1 , 2,4-triazol-1-ethanol l) N- (4-chlorobenzyl) -N-cyclopentyl-N'-phenylurea and a vegetable oil from group II, of which the following may be mentioned as examples: II. 1. a) Sesame oil b) Sunflower oil c) Olive oil d) Corn oil e) castor oil f) Cotton oil g) Soybean oil or II.2.2 a) Linoleic acid of the formula CH3 - (CH2) 4-CH = CH-CH2-CH = CH- (CH2) 7-COOH or 2. b) a lecithin has a particularly broad fungicidal activity exhibit.

Particularly preferred from group I are the compounds under b), h) and i) and from group II 1a), lb), 2a) and 2b).

It can be described as surprising that the combinations according to the invention show an increase in effectiveness that far exceeds the effectiveness of conventional fungicide formulations goes beyond, whereby the vegetable oils or their constituents have no effect of their own in the concentrations applied. This increase in effectiveness of plant protection products by adding known but ineffective compounds is particularly important, as this increases the concentration of active ingredients with the same good result reduced and thus the environmental impact is reduced. Farther The easy handling of such combinations should be emphasized, as tank mixes can be used, i.e. the fungicide is suspended in water on site and the vegetable oil or its individual component, which may be an emulsifier is added, added. The mixture can be applied directly, whereby E.g. no stability issues arise, which is a further advantage. on the other hand can be active ingredient and vegetable oils or their individual components in itself In a known way, also process into finished formulations.

The new fungicide combinations are therefore a valuable asset in the context of fungus control.

Fungicidal agents in crop protection are used for control of Plasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes, Deuteromycetes.

The good plant tolerance of the substances or combinations of substances allowed in the concentrations necessary for combating plant diseases a treatment of above-ground parts of plants, of vegetation and seeds and des Soil.

The active compound combinations according to the invention can be used as crop protection agents Among other things, it is also used to combat the pathogen causing brown rust from wheat and bean rust will.

The increased effect of the combinations according to the invention is particularly pronounced at certain concentration ratios. However, you can the weight ratios of the components in the combinations in relatively large Areas can be varied. In general, 1 part by weight of the fungicide is used Group I 0.1 to 10 parts by weight of one of the substances from group II, preferably 0.4-5, S parts by weight of a substance from group II.

The active ingredients or active ingredient combinations can be converted into the usual Formulations such as solutions, emulsions, suspensions, powders, Foams, pastes, granulates, aerosols, active ingredient-impregnated natural and synthetic Substances, finest encapsulation in polymeric substances and in coating compounds for seeds, also in formulations with burning charges, such as incense cartridges, cans and spirals and the like, as well as ULV cold and warm mist formulations.

These formulations are prepared in a known manner, z..B. by mixing the active ingredients with extenders, i.e. liquid solvents, liquefied gases under pressure and / or solid carriers, optionally using 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 solution middle are essentially: aromatics, such as xylene, toluene, or alkylnaphthalenes, 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 as well as butane, propane, Nitrogen and carbon dioxide; as solid carriers come into question: e.g. natural Ground rock, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic minerals such as highly dispersed silica, Alumina and silicates; as solid carriers for granulates 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 and granulates made from organic material such as sawdust, coconut shells, corn on the cob and tobacco stalks; as emulsifiers and / or foam-generating agents are possible: e.g. non-ionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, Polyoxyethylene fatty alcohol ethers, e.g. B. 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 iatex-shaped polymers are used such as gum arabic, polyvinyl alcohol, polyvinyl acetate.

Dyes such as inorganic pigments, e.g.

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

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

The combinations according to the invention can be in the form of finished formulations can be applied. The components included in the combinations but can also be mixed as individual formulations when used, i.e. in form can be used by tank mixes. For better emulsifiability preferably the component from group II is a customarily used emulsifier added up to about 10% of the weight fraction of component II.

The active compound combinations according to the invention can be used in the formulations or in the various application shape in mixture with others known active ingredients are present, such as fungicides, bactericides, insecticides, acaricides, Nematicides, herbicides, bird repellants, growth substances, plant nutrients and soil conditioners.

The active ingredients 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, slurrying, spreading, dusting, Spreading, dry pickling, moist pickling, wet pickling, slurry pickling or encrusting.

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

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

When treating the soil, the active ingredient concentrations are 0.00001 up to 0t1 wt.% ,. preferably. from 0.0001 to 0.02% ,. required at the place of work.

The good fungicidal effect of the new combinations is evident from the following Examples. While the individual components weaken in the fungicidal effect have, the combinations show a broad fungicidal effect.

Example 1 Puccinia test (wheat) / protective solvent: 0.001 % Xylene Emulsifier: 0.001% Ca-ABS-n-Dedecylbenzenesulfonic acid calcium For production In an appropriate preparation of the active compound, the oil is first emulsified in increased Amounts of emulsifier and solvent. By then adding a corresponding Overconcentrated active ingredient solution, the desired concentrations are obtained.

To test for protective effectiveness, young plants are treated with a Spore suspension of Puccinia recondita in a 0.1% aqueous agar solution inoculated. After drying, the plants are sprayed with the preparation of the active compound dewy. The plants remain at 200 ° C. and 100% rel. For 24 hours. humidity in an incubation cabin.

The plants are in a greenhouse at a temperature of approx. 200C and a relative humidity of approx. 80% set up for the development to benefit from rust pustules.

Table A Puccinia test / protective active ingredient or active ingredient active ingredient concentration Disease infestation combination tration in ppm in% 1- (4-chlorophenoxy) -3,3-dimethyl-1- 125 85 (1H-1,2,4-trizol-1-yl) -2-butanone (I h) (known) sesame oil (II / 1a) / known) 60 100 (% infestation) 120 sunflower oil (II / 1b) (known) 60 100 120 lecithin (II / 2b) (known) 60 100 120 according to the invention (Ih) + (II / 1a) 125 + 60 50 125 + 120 50 (Ih) + (II / 1b) 125 + 60 70 125 + 120 50 (Ih) + (II / 2b) 125 + 60 85 125 + 120 50 example B Uromyces test (French bean) / protective solvent: 0.001% xylene emulsifier: 0.001% Ca-ABS-n-Dedecylbenzenesulfonic acid calcium For the production of an appropriate In the preparation of active ingredient, the oil is first emulsified in increased amounts of emulsifier and solvents. By then adding a correspondingly overconcentrated Active ingredient solution, the desired concentrations are obtained.

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 uredospore suspension of the bean rust pathogen (Uromyces appendiculatus) inoculated and left in a dark humid chamber for 1 day at 20 to 220C and 100% relative humidity.

The plants are then kept under intense light for 9 days 20 to 220C and a relative humidity of 70 to 80% in the greenhouse set up.

Evaluation is carried out 10 days after the inoculation.

A clear superiority in effectiveness compared to the state of the technology show in this test e.g.

the compounds according to the following preparation examples: Table B Uromyces test / protective Active ingredients or active ingredient-active ingredient concentrations-disease infestation combination tration in ppm in% 1- (4-chlorophenoxy) -3,3-dimethyl-1- (1H-1,2,4-triazol-1-yl) -2-butanone 125 50 (ih) (known) Sesame oil (II / 1a) 40 0 (known) 80 0 Sunflower oil (II / 1b) 40 0 (known) 80 0 Lecithin (II / 2b) 40 0 100% attack (known) 80 0 Linoleic acid (II / 2a) 40 0 (known) 80 0 according to the invention (Ih) + (II / 2a) 125 + 40 10 125 + 80 15 (Ih) + (II / 1b) 125 + 40 10 125 + 80 10 (Ih) + (II / 2b) 125 + 40 50 125 + 80 30 (Ih) + (II / 1a) 125 + 40 50 125 + 80 20

Claims (6)

Claims PN '1.i Fungicidal agents, characterized by a Content of an active ingredient combination consisting of (I) one of the following Active ingredients from the fungicide group a) 1,4-Benzoquinone-l-benzoylhydrazone-4-oxime b) 6-methyl-2-oxo-1,3-dithiolo (4,5-b) -quinoxaline c) N- / 2,2,2-trichloro-1- (3,4-dichloroaniline) -ethyl7-formamide d) N-dichlorofluoromethanesulfenyl-N ', N'-dimethyl-N-phenyl sulfamide e) O-ethyl-S, S-diphenyl-phosphoric acid ester f) bis-phenyl- (3-trifluoromethyl-phenyl) -1- (1,2,4-triazolyl) -methane g) 2- (2-furanyl) -1H-benzimidazole h) 1- (4-chlorophenoxy) -3,3-dimethyl-1- (1H-1,2,4-triazol-1-yl) -2-butanone i) ß - [(1,1'-bisphenyl) -4-yloxy] -α- (1,1-dimethylethyl) -1H-1,2,4-triazol-1-ethanol j) 1- (4-chlorophenoxy) -1- (1H-imidazol-1-yl) -3,3-dimethyl-2-butanone k) ß- (4-chlorophenoxy) -α- (1,1-dimethylethyl) -1H-1,2,4-triazole-1-ethanol l) N- (4-chlorobenzyl) -N-cyclopentyl-N'-phenylurea and a vegetable dl from group II X a) sesame oil b) sunflower oil c) olive oil d) Corn oil e) Castor oil f) Cotton oil g) Soybean oil or 2a) Linoleic acid of the formula CH3- (CH2) 4-CH = CH-CH2-CH = CH- (CH2) 7-COOH or b) a lecithin. 2. Fungicidal agents according to claim 1, characterized in that in the combinations the weight ratio of a fungicide from group 1 for a substance from group II is between 1: 0.1 and 1:10. 3. Fungicidal agents according to Claims 1 and 2, characterized in that that in the combinations the weight ratio of one fungicide from the group I for a substance from group II is between 1: 0.4 and 1: 5.5. 4. A method of combating fungi, characterized in that an active ingredient combination according to claim 1 can act on fungi or their habitat leaves. 5. Use of active ingredient combinations according to Claim 1 for combating of mushrooms. 6. Process for the production of fungicidal agents, characterized in that that an active ingredient combination according to claim 1 with extenders and / or surface-active Means mixed up.