CH686161A5 - Synergistic fungicidal compsn. for plants - Google Patents

Abstract

Microbicidal compsn. for use in plants comprises: (a) a pyrimidine deriv. of formula (I), a phenoxy cpd. of formula (II) or a phenoxy cpd. of formula (III) or a salt or metal complex of them; and (b) 4-cyclopropyl-6-methyl-N-phenyl-2-pyrimidineamine (IV) or a salt or metal complex of (IV). X = H, halo, R, RO, CF3, CN, thiocarbamoyl or NO2; Y = H or F; Z = halo, CN, NO2, R, CF3 or phenyl, phenoxy or benzyl (all opt. substd. by 1-3 halo, CN, NO2, R, RO or CF3); n = 0-3; U = O or CH2O; A = halo, R, RO or CF3; n = 0-3; R = 1-4C alkyl. Component (a) is pref. methyl (E)-2-(2-(6-(2-cyanophenoxy)pyrimidin-4-yloxy)phenyl)-3- methoxyacrylate (Ia), methyl (E)-2-methoximino-2-(alpha-(o- tolyloxy)-o-tolyl)acetate, 2-(2-phenoxyphenyl)-(E)-2-methoximino- N-methylacetamide or 2-(2-(2,5-dimethylphenoxymethyl)phenyl)-(E)- 2-methoxyimino-N-methylacetamide.

Description

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description

The present invention relates to new microbicidal two-component mixtures with a synergistically increased activity and methods for using such mixtures in crop protection.

Component I is a strobilurin-analogous compound of the formula IA

IA

in which mean:

X is hydrogen, halogen, CHIU-alkyl, Ci-C4-alkoxy, trifluoromethyl, cyano, thiocarbamoyl or nitro, and

Y is hydrogen or fluorine; (Reference: EP-A 382 375)

or formula IB

CHgON

IB

in which mean:

Z are identical or different halogen, cyano, nitro, Cr-Ct-alkyl, Ci-C4-alkoxy, trifluoromethyl, optionally up to triply substituted phenyl, optionally up to triply substituted phenoxy, optionally up to triply substituted benzyl, and n 0 to 3 . (References: EP-A 253 213 and EP-A 400 417)

Component II is the 2-anilinopyrimidine of the formula II

CH,

II

4-Cyclopropyl-6-methyl-N-phenyl-2-pyrimidinamine or one of its salts or its metal complexes (reference: EP-A 310 550).

If Z in formula IB is phenyl, phenoxy or benzyl, the aromatic groups can be substituted up to three times the same or different by halogen, cyano, nitro, Ci-C4-alkyl, Ci-C4-alkoxy, trifluoromethyl.

The invention also relates to salts and metal complexes of the compounds I and II.

Among the acids that can be used to prepare salts of the formula I or II are:

Hydrohalic acid such as hydrofluoric acid, hydrochloric acid, hydrobromic acid or hydriodic acid as well as sulfuric acid, phosphoric acid, nitric acid and organic acids such as acetic acid, trifluoroacetic acid, trichloroacetic acid, propionic acid, glycolic acid, thiocyanic acid, lactic acid, succinic acid, citric acid, benzoic acid, cinnamic acid, oxalic acid, formic acid, Benzolsulfonsäu-re, p -Toluenesulfonic acid, methanesulfonic acid, salicylic acid, p-aminosalicylic acid, 2-phenoxybenzoic acid, 2-acetoxybenzoic acid or 1,2-naphthalene disulfonic acid.

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The term salts also includes metal complexes of basic components I and II. These complexes can optionally affect only one component or both components independently. It is also possible to produce metal complexes which combine the two active ingredients I and II to form a mixed complex.

Metal complexes consist of the underlying organic molecule and an inorganic or organic metal salt, for example the halides, nitrates, sulfates, phosphates, acetates, trifluoroacetates, trichloroacetates, propionates, tartrates, sulfonates, salicylates, benzoates etc. of the elements of the second main group such as calcium and magnesium and the third and fourth main groups such as aluminum, tin or lead and the first to eighth subgroups such as chromium, manganese, iron, cobalt, nickel, copper, zinc etc. The subgroup elements of the 4th period are preferred. The metals can be present in the various valences that they have. The metal complexes can occur in one or more cores, i.e. they can contain one or more organic moieties as ligands.

Halogen means fluorine, chlorine, bromine and iodine; fluorine, chlorine and bromine are preferred.

The alkyl part in the Cr-C4-alkyl groups and Cr-C4-alkoxy groups is methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl and tert-butyl; methyl and methoxy are preferred.

Thiocarbamoyl means the residue -CS-NH2.

The compounds of the formula IA and IB occur in the E and Z form on account of their aliphatic or imino double bond. Atropisomers can also occur. Formulas IA and IB are intended to encompass all possible isomers and mixtures thereof.

The compounds IA and IB are preferred in the E form.

Preferred mixtures are those in which in compound IA

X is hydrogen, chlorine, methyl, methoxy, trifluoromethyl or cyano, and

Y represents hydrogen or fluorine;

methyl 2- (2- [6- (2-cyanophenoxy) pyrimidin-4-yloxy] phenyl} -3-methoxyacrylate is very particularly preferred,

and in particular the E isomer, which is to be mentioned here and hereinafter as IA *.

Mixtures in which IB

Z is chlorine, methyl, methoxy, trifluoromethyl or cyano, and n is 0, 1 or 2; is very particularly preferred

Methyl 2-methoximino-2- [a- (o-tolyloxy) -o-tolyl] acetate,

and in particular the E isomer, which is to be mentioned here and in the following IB *.

Further agrochemical active substances such as insecticides, acaricides, nematicides, herbicides, growth regulators and fertilizers, but in particular further microbicides, can also be added to the active substance mixture according to the invention.

It has now surprisingly been found that mixtures of components I and II have not only an additive action in their fungicidal action, but also a clear, synergistically increased action.

The mixture according to the invention has the particular advantage of preventing resistance formation in plant diseases, since the microbicidal action of the two components I and II can be attributed to different biochemical mechanisms. While type I strobilurin analogues inhibit mitochondrial respiration by blocking electron transfer at the cytochrome in complex, the activity of pyrimininamine II is based on the inhibition of amino acid synthesis.

The present invention therefore represents a very substantial enrichment of the technology.

In addition to the two-component mixture, the present invention also relates to a method for combating fungi, which is characterized by treating an area infected or endangered by fungi in any order or simultaneously with a) an active ingredient of the formula I or one of its salts, and with b) the active ingredient of the formula I or one of its salts, the salts also being able to be selected such that both active ingredients are bound to an acid residue or, in the case of a metal complex, to a central metal cation.

Favorable mixing ratios of the two active ingredients are l: ll = 1:20 to 10: 1, preferably l: ll = 1: 6 to 3: 1.

In many cases, mixtures are advantageous in which the mixing ratio of the pure active substances is 1: ll = 1: 3 to 1: 1, e.g. 1: 2, 2: 3, 2: 5, 3: 4.

The active compound mixtures I + II according to the invention have very advantageous curative, preventive and systemic fungicidal properties for protecting plants. The present active ingredient mixtures on plants or on parts of plants (fruits, flowers, leaves, stems, tubers, roots) of different useful cultures can be used to contain or destroy the microorganisms which occur, with plant parts which are subsequently growing being spared by such microorganisms.

The active substance mixtures are active against the phytopathogenic fungi belonging to the following classes: Ascomycetes (e.g. Venturia, Podosphaera, Erysiphe, Monilinia, Uncinula); Basidiomycetes (e.g. the genus Hemileia, Rhizoctonia, Puccinia); Fungi imperfecti (e.g. Botrytis, Helminthosporium, Rhynchosporium, Fusarium, Septoria, Cercospora, Alternaria, Pyricularia and especially Pseudocer-cosporella herpotrichoides). The active ingredient mixtures have a systemic effect. You can also use it as a mordant

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for the treatment of seeds (fruits, tubers, grains) and plant cuttings to protect against fungal infections and against phytopathogenic fungi occurring in the soil. The active substance mixtures according to the invention are distinguished by particularly good plant tolerance and by being environmentally friendly.

In the context of this invention, target cultures for the indication areas disclosed herein include, for example the following types of plants: cereals: (wheat, triticale, barley, rye, oats, rice, sorghum and relatives); Beets: (sugar and fodder beets); Pome, stone and berry fruits: (apples, pears, plums, peaches, almonds, cherries, strawberries, raspberries and blackberries); Legumes: (beans, lentils, peas, soy); Oil crops: (rapeseed, mustard, poppy seeds, olives, sunflowers, coconut, castor bean, cocoa, peanuts); Cucumber Family: (Pumpkin, Cucumber, Melon); Fiber plants: (cotton, flax, hemp, jute); Citrus fruits: (oranges, lemons, grapefruit, mandarins); Vegetables: (spinach, lettuce, asparagus, cabbage, carrots, onions, tomatoes, potatoes, peppers); Laurel plants: (avocado, cinnamonum, camphor) or plants such as corn, tobacco, nuts, coffee, sugar cane, tea, grapevines, hops, banana and natural rubber plants and ornamental plants (flowers, shrubs, deciduous trees and conifers such as conifers). This list is not a limitation.

The active substance mixtures according to the invention are particularly effective as fungicides in cereals, in potatoes, in vines and in fruit growing; very particularly preferred in cereals and on fruit and vegetable crops.

The active ingredient mixtures of the formulas I and II are usually used in the form of compositions. The active compounds of the formula I and the active compound of the formula II can be applied simultaneously, but also in succession on the same day to the area or plant to be treated, together with any other carriers, surfactants or other application-promoting additives customary in formulation technology.

Suitable carriers and additives can be solid or liquid and correspond to the substances useful in formulation technology, e.g. natural or regenerated mineral substances, solvents, dispersants, wetting agents, adhesives, thickeners, binders or fertilizers.

A preferred method for applying a mixture of active ingredients which contains at least one of each of these active ingredients I and II is the application to the aerial parts of the plants, in particular the foliage (leaf application). The number of applications and the application rate depend on the biological and climatic living conditions for the pathogen. The active ingredients can also get into the plant through the roots through the root system (systemic effect) by soaking the location of the plant with a liquid preparation or introducing the substances into the soil in solid form, e.g. in the form of granules (floor application). The compounds of formulas I and II can be used for seed treatment e.g. applied to seeds (coating) by either soaking the tubers or grains one after the other in a liquid preparation of an active ingredient or coating them with an already combined moist or dry preparation. In addition, other types of application to plants are possible in special cases, e.g. the targeted treatment of the buds or the infructescences.

The compounds of the combination are used in unchanged form or preferably together with the auxiliaries customary in formulation technology and are therefore used, for example, to emulsion concentrates, spreadable pastes, directly sprayable or dilutable solutions, diluted emulsions, wettable powders, soluble powders, dusts, granules, or by encapsulation in e.g. polymeric materials processed in a known manner. The methods of application such as spraying, atomizing, dusting, scattering, brushing or pouring are selected in the same way as the type of agent, in accordance with the intended goals and the prevailing conditions. Favorable application rates of the active ingredient mixture are generally 5 g to 1000 g ai / ha, preferably 50 g to 700 g ai / ha, particularly preferably 60 g to 500 g ai / ha. For seed treatment, the application rates are 0.5 g-800 g, preferably 5 g-100 g ai per 100 kg of seed.

The formulations are prepared in a known manner, e.g. by intimately mixing and / or grinding the active ingredients with extenders, e.g. with solvents, solid carriers, and optionally surface-active compounds (surfactants).

Possible solvents are: Aromatic hydrocarbons, preferably the fractions Os to Ci2, such as Xylene mixtures or substituted naphthalenes, phthalic acid esters such as dibutyl or dioctyl phthalate, aliphatic hydrocarbons such as cyclohexane or paraffins, alcohols and glycols and their ethers and esters such as ethanol, ethylene glycol, ethylene glycol monomethyl ether or ethyl ether, ketones such as cyclohexanone, strongly polar solvents N-methyl-2-pyrrolidone, dimethyl sulfoxide or dimethylformamide, and optionally epoxidized vegetable oils such as epoxidized coconut oil or soybean oil; or water.

As solid carriers, e.g. For dust and dispersible powders, natural rock powder is usually used, such as calcite, TaLkum, kaolin, montmorillonite or attapulgite. To improve the physical properties, highly disperse silica or highly disperse absorbent polymers can also be added. As granular, adsorptive granulate carriers come porous types such as Pumice stone, broken brick, sepiolite or bentonite, as non-sorptive carrier materials e.g. Calcite or sand in question. In addition, a large number of pregranulated materials of inorganic or organic nature, such as, in particular, dolomite or comminuted plant residues can be used.

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Depending on the nature of the active compounds of the formulas I and II to be formulated, suitable surface-active compounds are nonionic, cationic and / or anionic surfactants with good emulsifying, dispersing and wetting properties. Surfactants are also understood to mean surfactant mixtures.

The surfactants commonly used in formulation technology include published in the following publications:

- "Mc Cutcheon's Detergents and Emulsifiers Annual" MC Publishing Corp., Glen Rock, New Jersey, 1988.

- M. and J. Ash, Encyclopedia of Surfactants, Vol. I-III, Chemical Publishing Co., New York, 1980-1981.

Particularly advantageous, application-promoting additives are natural or synthetic phospholipids from the series of kephalins and lecithins, such as Phosphatidylethanolamine, Phosphatidylserine, Phosphatidylglycerin, Lysolecithin.

The agrochemical preparations generally contain 0.1 to 99%, in particular 0.1 to 95%, active ingredients of the formulas I and II, 99.9 to 1%, in particular 99.9 to 5% of a solid or liquid additive and 0 to 25%, in particular 0.1 to 25% of a surfactant.

While concentrated products are preferred as a commodity, the end user generally uses diluted products.

Such (agro) chemical agents are part of the present invention.

The following examples serve to illustrate the invention, where “active ingredient” means a mixture of compound I and compound II in a specific mixing ratio.

Wettable powder a)

b)

c)

Active ingredient [1:11 = 4: 1 (a), 1: 1 (b), 1: 2 (c)]

25%

50%

75%

Na lignin sulfonate

5%

5%

-

Na lauryl sulfate

3%

-

5%

Na diisobutylnaphthalenesulfonate

-

6%

10%

Octylphenol polyethylene glycol ether (7-8 moles of ethylene oxide)

-

2%

-

Fumed silica

5%

10%

10%

kaolin

62%

27%

-

The active ingredient is mixed well with the additives and ground well in a suitable grinder. Spray powder is obtained which can be diluted with water to form suspensions of any desired concentration.

Emulsion concentrate

Active ingredient (l: ll = 2: 3) 10%

Octylphenol polyethylene glycol ether (4-5 mol ethylene oxide) 3%

Ca-dodecylbenzenesulfonate 3%

Castor oil polyglycol ether (35 moles of ethylene oxide) 4%

Cyclohexanone 30%

Xylene mixture 50%

From this concentrate, emulsions of any desired dilution can be prepared by dilution with water, which can be used in crop protection.

Dusts a)

b)

c)

Active ingredient [l: ll = 1: 4 (a); 1: 5 (b) and 1: 1 (c)]

5%

6%

4%

talc

95%

-

-

kaolin

-

94%

-

Stone powder

-

-

96%

Ready-to-use dusts are obtained by mixing the active ingredient with the carrier and grinding it in a suitable mill. Such powders can also be used for dry dressing for seeds.

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Extruder granules

Active ingredient (1:11 = 3: 4)

14%

Na lignin sulfonate

2%

Carboxymethyl cellulose

1%

kaolin

83%

The active ingredient is mixed with the additives, ground and moistened with water. This mixture is extruded and then dried in an air stream.

Coating granules

Active ingredient (l: ll = 3: 5) 8% ~

Polyethylene glycol (MG 200) 3%

Kaolin 89%

(MW = molecular weight)

The finely ground active ingredient is applied evenly in a mixer to the kaolin moistened with polyethylene glycol. In this way, dust-free coating granules are obtained.

Suspension concentrate

Active ingredient (l: ll = 3: 7) 40%

Propylene glycol 10%

Nonylphenol polyethylene glycol ether (15 mol Et oxide) 6%

Na lignin sulfonate 10%

Carboxymethyl cellulose 1%

Silicone oil (in the form of 75% aqueous emulsion) 1%

Water 32%

The finely ground active ingredient is intimately mixed with the additives. This gives a suspension concentrate from which suspensions of any desired dilution can be prepared by dilution with water. Such dilutions can be used to treat living plants and plant propagation material by spraying, watering or immersing them and to protect them against microorganisms.

Biological examples

The following experiments were carried out with mixtures of the individual compounds IA * and II or IB * and II mentioned above. The improvements in their effectiveness in the following and other biological experiments are largely representative of the improvements in effectiveness in other representatives of Formula I.

Fungicides always have a synergistic effect if the fungicidal activity of the active ingredient combination is greater than the sum of the effects of the individually applied active ingredients.

The expected effect E for a given combination of active ingredients, e.g. two fungicides, obeys the so-called COLBY formula and can be calculated as follows (COLBY, LR. "Calculating synergistic and antagonistic responses of herbicide combinations". Weeds 15, pages 20-22, 1967) (LIMPEL and al., 1062 "Weeds control by ... certain combinations". Proc. NEWCL, Vol. 16, pp. 48-53): (g AS / ha = grams of active ingredient per hectare)

X =% effect by fungicide I at p g AS / ha Y =% effect by fungicide II at q g AS / ha

E = the expected effect of the fungicides I + II at p + q g AS / ha application rate (additive effect),

then according to Colby: E = X + Y - ^ ^

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If the effect actually observed (O) is greater than the expected effect, the combination of the combination is superadditive, i.e. there is a synergistic effect.

Example 1: Effect of aeaen Botrytis cinerea on vines

Vine seedlings 5 weeks old are sprayed with a suspension prepared from the formulated test substance and, after 2 days, infected with a conidia suspension of B.cinerea. After 4 days incubation at 21 ° C and 95-100% clean. Air infestation in the greenhouse is assessed.

This results in a synergistically increased fungicide effect with different mixing ratios of components I + II.

Example 2: Action against Venturia inaeoualis on apples

Apple cuttings with 10 to 20 cm long fresh shoots are sprayed to runoff point with a spray mixture prepared from the formulated active ingredient or combination of active ingredients. After 24 hours, the treated plants are infected with a conidia suspension of the fungus, then the treated plants are incubated for 5 days at 90-100% relative atmospheric humidity and 20 ° C. and set up in a greenhouse at 20-24 ° C. for a further 10 days. The fungal infection is assessed 15 days after the infection.

This results in a synergistically increased fungicide effect with different mixing ratios of components I + II.

Example 3: Action against Pseudocercosporella herpotrichoides on wheat

10 day old wheat plants are sprayed to runoff point with a spray mixture prepared from the formulated active ingredient or combination of active ingredients. After 48 hours, the treated plants are infected with a conidia suspension of the fungus (wheat or Rye type), then the treated plants are incubated for 2 days at 90-100% relative atmospheric humidity and 20 ° C. and for a further 8 weeks in one Climatic chamber set up at 12 ° C. The fungal infection is assessed 9 weeks after the infection.

This results in a synergistically increased fungicide effect with different mixing ratios of components I + II.

Example 4: Action against Ervsiphe araminis on winter wheat

In pots with a diameter of 16 cm, around 20 plants of the winter wheat variety «Bernina» are grown in the greenhouse at 20 ° C and 60% relative humidity for 12 hours during the day or at 16 ° C and 80% relative humidity during the night. At the beginning of the tillering (EC 21) the plants with an isolate of Erysiphe graminis f.sp. tritici inoculated.

3 days after the inoculation, the individual active ingredient or the fungicide mixture is applied as an aqueous suspension with a spray bar under field conditions with a water application rate of 500 l / ha. 4 days or 11 days after application, the change in the infestation on the leaf surface present during the inoculation is determined (evaluation of the primary infestation). Each of the attempts runs in 3 repetitions.

This results in a synergistically increased fungicide effect with different mixing ratios of components I + II.

Example 5: Action against Pvrenophora teres on barley

6-day-old barley plants are sprayed to runoff point with a spray mixture prepared from the formulated active ingredient or combination of active ingredients. After 2 days, the plants are inoculated with spore suspension of Pyrenophora teres and incubated in the greenhouse at 21 ° C. and 90-100% atmospheric humidity. After a week, the fungal attack is assessed. This results in a synergistically increased fungicide effect with different mixing ratios of components I + II.

Example 6: Action against Phvtophtora infestans on tomatoes

After growing for three weeks, tomato plants are sprayed to runoff point with an aqueous spray mixture (0.02% active substance) prepared from wettable powder of the active ingredient and infected 24 hours later with a sporangia suspension of the fungus. After 5 days incubation at 21 ° C and 95-100% clean. Air infestation in the greenhouse is assessed.

This results in a synergistically increased fungicide effect with different mixing ratios of components I + II.

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Example 7: Effect of aea Plasmopara viticola on vines

Vine seedlings in the 4 to 5 leaf stage are sprayed to runoff point with an aqueous spray mixture (0.02% active substance) made from wettable powder of the active ingredient and infected 24 hours later with a sporangia suspension of the fungus. After 6 days incubation at 21 ° C and 90-100% clean. Air infestation in the greenhouse is assessed.

This results in a synergistically increased fungicide effect with different mixing ratios of components I + II.

Example 8: Effect of aeaen Alternaria solani

The Alternaria strain becomes 20% in one week. V8 agar grown at 22 ° C in the dark. To test the fungicide activity, graded active ingredient concentrations are incorporated into V8 agar, on the surface of which A. solani is inoculated in the Petri dish. Each concentration runs in 4 repetitions. After 7 days, the radial growth of the fungus or its inhibition is determined.

This results in a synergistically increased fungicide effect with different mixing ratios of components I + II.

Claims (18)

Claims 1. Plant microbicidal composition comprising two active ingredient components, characterized in that component I is a compound of the formula IA CH3OHC, .COOCH3 IA N. N Y in which mean: X is hydrogen, halogen, Ci-C4-alkyl, Ci-C4-alkoxy, trifluoromethyl, cyano, thiocarbamoyl or nitro, and Y is hydrogen or fluorine; or formula IB CH30N ^ V _COOCH 3rd IB in which mean: Z is the same or different halogen, cyano, nitro, Ci-C4-alkyl, Ci-C ^ alkoxy, trifluoromethyl, optionally up to triply substituted phenyl, optionally up to triply substituted phenoxy, optionally up to triply substituted benzyl, and n 0 to 3; and that component II is the 2-anilinopyrimidine of the formula II 8th 5 10th 15 20th 25th 30th 35 40 45 50 55 60 65 CH 686 161 A5 CH3 N = / " 4-Cyclopropyl-6-methyl-N-phenyl-2-pyrimidinamine or one of its salts or its metal complexes. 2. Composition according to claim 1, wherein the compounds of the formulas IA and IB are in the E form. 3. Composition according to claim 1, wherein component I is a compound of formula IA. 4. Composition according to claim 3, wherein in compound IA X is hydrogen, chlorine, methyl, methoxy, trifluoromethyl or cyano, and Y is hydrogen or fluorine. 5. A composition according to claim 4, wherein compound IA is methyl 2- {2- [6- (2-cyanophenoxy) pyrimidin-4-yloxy] phenyl} -3-methoxyacrylate. 6. Composition according to claim 5, wherein the compound IA is in the E form. 7. Composition according to claim 1, wherein component I is a compound of formula IB. 8. Composition according to claim 7, wherein in compound IB Z is chlorine, methyl, methoxy, trilluormethyl or cyano, and n is 0, 1 or 2. 9. A composition according to claim 8, wherein the compound IB is methyl 2-methoximino-2- [a- (o-tolyloxy) -o-to-lyl acetate. 10. Composition according to claim 9, wherein the compound IB is in the E form. 11. Composition according to claim 1, characterized in that the weight ratio l: ll = 1:20 to 10: 1. 12. Composition according to claim 11, characterized in that the weight ratio is l: ll = 1: 6 to 3: 1. 13. Use of an agent according to claim 1 for controlling and preventing plant diseases. 14. A method for combating and preventing plant diseases, characterized in that one in a sequence or at the same time treated with a component infested or endangered by fungi with component I and component II according to claim 1. 15. The method according to claim 14, wherein a compound of the formula IA according to claim 1 is used as component I. 16. The method according to claim 15, wherein as component I the compound according to claim 6 is used. 17. The method according to claim 14, wherein a compound of formula IB according to claim 1 is used as component I. 18. The method according to claim 17, wherein the compound I according to claim 10 is used as component I. 9