WO2003059067A1 - Fungicidal mixtures on the basis of oxime ether derivatives and guanidine derivatives - Google Patents

Abstract

Disclosed are mixtures for controlling harmful fungi and insects, containing oxime ether derivatives of formula (I) as an active component (A), in which the substituents have the following meaning: X NH or oxygen; R1 and R3 independently of each other hydrogen, cyano, alkyl, cyclopropyl, or haloalkyl; R2 and R4 independently of each other hydrogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, or haloalkynyl; and (B) the compound of formula (II) in a synergistically active quantity. Also disclosed are methods for controlling harmful fungi with mixtures of compounds I and II.

Description

FUNGICIDAL MIXTURES BASED ON OXIMETHER DERIVATIVES AND GUANIDINE DERIVATIVES

description

The present invention relates to mixtures for controlling harmful fungi and insects, which are active components

A) Oxime ether derivatives of the formula I.

in der die Substituenten die folgende Bedeutungen haben:

in which the substituents have the following meanings:

X NH or oxygen;

R ¹ , R ³ independently of one another hydrogen, cyano, C 1 -C ₄ -alkyl, cyclopropyl or C 1 -C ₄ -haloalkyl;

R ² , R ⁴ independently of one another hydrogen, Ci-C ^ alkyl, ^C ₃ -C ₆ alkenyl, Ca-C _ß alkynyl, -C-C ₄ haloalkyl, C _ß -Cg haloalkenyl or C ₃ -C ₆ haloalkynyl;

and

B) the compound of formula II

in einer synergistisch wirksamen Menge enthalten.

contained in a synergistically effective amount.

The object of the present invention was to provide mixtures which, on the one hand, have a good fungicidal action, in particular against fungus diseases in rice, and at the same time have a good insecticidal action (synergistic mixtures) when the total amount of active compounds applied is reduced. Since pests are usually found in large numbers in the climatic regions in which rice is grown, a combination of fungicidal and insecticidal activity is desirable. This object is achieved according to the invention by the mixtures according to claim 1. Surprisingly, it was found that compound II, which itself is not fungicidally active, enhances the fungicidal activity of the oxime ether derivatives of the formula I. Compound II thus acts as an adjuvant.

The compounds of formula I and their preparation are known per se and described in the literature (WO-A 97/15552).

The insecticide of formula II is also known (common name: clothianidin) and described in the literature (EP-A 376 279).

Because of their biological activity, compounds I are preferred in which R ¹ and R ^{3 represent} hydrogen, cyano, cyclopropyl, methyl, ethyl, 1-methylethyl or CF ₃ .

Compounds I are particularly preferred in which R ¹ and R ^{3 are} C ¹ -C ₄ -alkyl.

Furthermore, compounds I are particularly preferred in which R ^{1 is} methyl.

Furthermore, compounds I are preferred in which R ^{1 is} CF ₃ .

Furthermore, compounds I are preferred in which R ² and R ^{4 represent} hydrogen, cyclopropyl, methyl, ethyl, isopropyl.

In addition, compounds I are preferred in which R ^{4 is} methyl.

Furthermore, compounds I are preferred in which R ^{4 represents} ethyl or isopropyl.

Oxime ether derivatives of the formula I in which X represents NH are particularly preferred.

In particular, in view of their use in the mixtures according to the invention with the compound II, the compounds I compiled in the following Table 1 are preferred. Table 1

Oxime ether derivatives of the formula I.

The compounds I contained in the mixtures according to the invention are distinguished by an excellent action against a broad spectrum of phytopathogenic fungi, in particular against fungi from the classes of the Ascomycetes, Deuteromycetes, Phycomycetes and Basidiomycetes. They are particularly important for combating a large number of fungi on various crops such as cotton, vegetables (eg cucumbers, beans, tomatoes, potatoes and squashes), barley, grass, oats, bananas, coffee, corn, fruit plants, rice, rye , Soy, wine, wheat, ornamental plants, sugar cane and a variety of seeds.

They are particularly suitable for combating the following phytopathogenic fungi: Blumeria graminis (powdery mildew) on cereals, Erysiphe cichoracearum and Sphaerotheca fuliginea on pumpkin plants, Podosphaera leucotricha on apples, Uncinula necator on vines, Puccinia species on cereals, Rhizoonia species, Cotton anonia Rice and lawn, Ustilago species on cereals and sugar cane, Venturia inaequalis (scab) on apples, Helminthosporium species on cereals and rice, Septoria nodorum on wheat,

Botrytis cinera (gray mold) on strawberries, vegetables, ornamental plants and vines, Cercospora arachidicola on peanuts, Pseudo-cercosporella herpotrichoides on wheat and barley, Pyricularia oryzae on rice and lawn, Phytophthora infestans on potatoes and tomatoes, Plasmopara viticola on vines, pseudoperon - in hops and cucumbers, Alternaria species in vegetables and fruits, Mycosphaerella species in bananas and Fusarium and Verticillium species.

The compound of formula II is used to control animal pests from the class of the insects, arachnids and nematodes. It can be used in crop protection as well as in the hygiene, storage protection and veterinary sectors to control animal pests. It is particularly suitable for controlling the following animal pests:

• Insects from the order of the butterflies (Lepidoptera), for example Agrotis ypsilon, Agrotis segetum, Alabama argilla- cea, Anticarsia gemmatalis, Argyresthia conjugella, Autographa gamma, Bupalus piniarius, Cacoecia murinana, Capua reticulana, Chei atobone brumistura, choroidal, choroidal, choroidal, choroidal, choroidal, choroidal, choroidal and choroidal Cirphis unipuncta, Cydia pomonella, Dendrolimus pini, Diaphania nitidalis, Diatraea grandiosella, Earias insulana, Elasmopalpus lignosellus, Eupoecilia ambiguella, Evetria bouliana, Feltia subterranea, Galleria ellonella, Grapholitha funebranais, Grapholitha funolesanaa Hellula undalis, Hibernia defoliaria, Hyphantria cunea, Hyponomeuta malinellus, Keiferia lycopersi- cella, Lambdina fiscellaria, Laphygma exigua, Leucoptera cof- feella, Leucoptera scitella, Lithocolletis blancardella, Lobe- sia botia, Lia- siaegeia triactia, loxia triactia, loxia triactia, loxia triactia, loxia triactia, loxia triactia, loxia triactia, loxia liaopia , Malacoso a neustria, Mamestra brassicae, Orgyia pseudotsugata, Ostrinia nubilalis, Panolis flammea, Pectinophora gossypiella, Peridroma saucia, Phalera bucephala, Phthorimaea operculella, Phyllocnistis citrella, Pieris brassicae, Plathypena scabra, Plutella xylostella, pseudo doplusia includens, Rhyacionia frustrana, Scrobipalpula abso- luta, Sitotroga cerealella , Sparganothis pilleriana, Spodoptera frugiperda, Spodoptera littoralis, Spodoptera litura, Thaumato- poea pityocampa, Tortrix viridana, Trichoplusia ni and Zeira- phera canadensis,

Beetles (Coleoptera), e.g. Agrilus sinuatus, Agriotes lineatus, Agriotes obscurus, Amphimallus solstitialis, Anisandrus dispar, Anthonomus grandis, Anthonomus pomoru, Atomaria linearis, Blastophagus piniperda, Blitophaga undata, Bruchus rufimanus, Bruechus pisorum, Bruchus lentisu- losa, Byisc , Cerotoma trifurcata, Ceuthorrhynchus assimilis, Ceuthorr- hynchus napi, Chaetocnema tibialis, Conoderus vespertinus, Crioceris asparagi, Diabrotica longicornis, Diabrotica 12-punc- tata, Diabrotica virgiferisisobirisisinutinis, thilobisinisis, epilachinisis, epilachnis, varilobinisis, epilachnis, varilobinisis, epilachnis, varilobinisis, epilachnis, hib , Hypera postica, Ips typographus, Le a bilineata, Lema melanopus, Leptinotarsa decemlineata, Limonius californi- cus, Lissorhoptrus oryzophilus, Melanotus communis, Meligethes aeneus, Melolontha hippocastani, Melolontha melolontha, a Oule oryzae, Otiorrhynchus sulcatus, Otiorrhynchus ovatus, Phaedon cochleariae, Phyllotreta chrysocephala, Phyllophaga sp., Phyllopertha hortic ola, Phyllotreta nemorum, Phyllotreta striolata, Popillia japonica, Sitona lineatus and Sitophilus granaria,

• Two-winged (Diptera), e.g. Aedes aegypti, Aedes vexans, Anas- trepha ludens, Anopheles maculipennis, Ceratitis capitata, Chrysomya bezziana, Chrysomya hominivorax, Chrysomya macella- ria, Contarinia sorghicola, Cordylobia anthropophaga, Culex pi piens, Dacus cucurbitae, Dacus oleae, Dasineura brassicae, fan- nia canicularis, Gasterophilus intestinalis, Glossina orsitans, Haematobia irritans, Haplodiplosis equestris, Hylemyia platura, Hypoderma lineata, Liriomyza sativae, Liriomyza trifolii, Lucilia caprina, Lucilia cuprina, Lucilia sericata pectoral, Lyco- rica pomica, Lyco- rica, lorica- tica, Lyco- rica, lorica- rica, lalica- rorica p , Muscina stabulans, Oestrus ovis, Oscinella frit, Pegomya hysocyami,

Phorbia antiqua, Phorbia brassicae, Phorbia coarctata, Rhagoletis cerasi, Rhagoletis pomonella, Tabanus bovinus, Tipula ole-racea and Tipula paludosa,

Thrips (Thysanoptera), for example Frankliniella fusca, Frankliniella occidentalis, Frankliniella tritici, Scirtothrips citri, Thrips oryzae, Thrips pal i and Thrips tabaci, Hymenoptera (Hymenoptera), for example Athalia rosae, Atta cephalotes, Atta sexdens, Atta texana, Hoplocampa minuta, Hoplocampa testudinea, Monomorium pharaonis, Solenopsis geminata and Solenopsis invicta,

Bugs (Heteroptera), e.g. Acrosternum hilare, Blissus leucopterus, Cyrtopeltis notatus, Dysdercus cingulatus, Dysdercus intermedius, Eurygaster integriceps, Euschistus impictiventris, Leptoglossus phyllopus, Lygus lineolaris, Lygus pratensis, Nezara quadrodisulais, and Pyanma viridula, Pies

Plant suckers (Homoptera), e.g. Acyrthosiphon onobrychis, Adelges laricis, Aphidula nasturtii, Aphis fabae, Aphis pomi, Aphis sambuci, Brachycaudus cardui, Brevicoryne brassicae, Ce- rosipha gossypii, Dreyfusia Nordmannianae, Dreyfusia picisacumaolapiolausolaapiaaculapiaolusiapiaaciae, dyfusia picisaciae, dyfusia pod Macrosiphon rosae, Megoura viciae, Metopolophium dirhodum, Myzodes persicae, Myzus cerasi, Nilaparvata lugens, Pemphigus bursarius, Perkinsiella saccharicida, Phorodon humuli, Psylla mali, Psylla piri, Rhopa- lomyzus papalisisiphapis, Malaidis malapisis, Malaidis, Malaidis, Malopal graminum, Schizoneura lanuginosa, Tria- leurodes vaporariorum and Viteus vitifolii,

Termites (Isoptera), e.g. Calotermes flavicollis, Leucotermes flavipes, Reticulitermes lucifugus and Termes natalensis,

Straight wing aircraft (Orthoptera), e.g. Acheta domestica, Blatta orien- talis, Blattella germanica, Forficula auricularia, Gryllotalpa gryllotalpa, Locusta migratoria, Melanoplus bivittatus, Melanoplus femur-rübrum, Melanoplus mexicanus, Melanoplus sanguini- pes, Melanoplus spretus, Ameranascocentina, peranfacetana, nomadascacrata america, Nomadascocentica, nomanascetacanae, Nomadascacratae, Nomadascacetana, Nomadascacratae, Nomadascacratae, Nomadascacrata america, Nomadascocentiae, Nomadascacrata se, Nomadascecentica, Peranaceticus periculum , Stauronotus maroccanus and Tachycines asynamorus,

• Arachnoidea such as arachnids (Acarina), for example Amblyomma america- num, Amblyomma variegatum, Argas persicus, Boophilus annulatus, Boophilus decoloratus, Boophilus microplus, Brevipalpus phoeni- eis, Bryobia praetiosa, Dermacentor silvarum shini, Eotetronii, Iotetranyi ricinus, Ixodes rubieundus, Ornithodorus moubata, Otobius me- gnini, Paratetranychus pilosus, Dermanyssus gallinae, Phyllo- coptruta oleivora, Polyphagotarsonemus latus, Psoroptes ovis, Rhipicephalus appendiculchinus tibiiecantinus, Thipiophychinus, Rhipicephysinabus Tetranychus telarius and Tetranychus urticae. • Nematodes such as root-bile nematodes, eg Meloidogyne hapla, Meloidogyne incognita, Meloidogyne javanica, cyst-forming nematodes, eg Globodera rostochiensis, Heterodera avenae, Heterodera glycines, Heterodera schachtii, Heterodera trifolius, longica-lenticular, and lenticular chelitis, long- and lenticular chelitis dipsaci, Heliocotylenchus mul- ticinctus, Longidorus elongatus, Radopholus similis, Rotylen- chus robustus, Trichodorus primitivus, Tylenchorhynchus clay- toni, Tylenchorhynchus dubius, Pratylenchus neglectus, Praty- lenchuschususatati curatusi, Praty- lenchususususatati curatus, Praty- lususususususatati, Praty- lusus penetraty curatus, Praty- lenchusususususatati curatusi, Praty- undusususususatansi, Praty- lenchusususususatansi, Praty- lenchusususususatansi,

The compounds I and II are usually used in a weight ratio of 20: 1 to 1: 200, in particular 10: 1 to 1: 180, preferably 2: 1 to 1: 160.

The amount of active ingredient used to control animal pests is generally from 0.01 to 2.0, preferably from 0.02 to 1.0, kg / ha under field conditions.

The mixtures according to the invention can particularly preferably be used to control plant diseases and insect pests in rice.

The compounds I and the compound II can be applied simultaneously, that is jointly or separately, or in succession, the sequence in the case of separate application generally not having any effect on the success of the control measures.

The application rates of the mixtures according to the invention, especially for agricultural crop areas, are from 0.01 to 8 kg / ha, preferably 0.1 to 5 kg / ha, in particular 0.5 to 3.0 kg / ha, depending on the type of effect desired ,

The application rates for the compounds I are 0.01 to 2.5 kg / ha, preferably 0.05 to 2.5 kg / ha, in particular 0.1 to 1.0 kg / ha.

In the case of seed treatment, application rates of mixture of 0.001 to 250 g / kg of seed, preferably 0.01 to 100 g / kg, in particular 0.01 to 50 g / kg, are generally used.

If pathogenic harmful fungi are to be combated for plants, the compounds I and the compound II or the mixtures of the compounds I and the compound II are applied separately or together by spraying or dusting the seeds, the plants or the soil before or after sowing the plants or before or after the emergence of the plants.

The mixtures according to the invention can be prepared, for example, in the form of directly sprayable solutions, powders and suspensions or in the form of high-strength aqueous, oily or other suspensions, dispersions, emulsions, oil dispersions, pastes, dusts, scattering agents or granules and by spraying, atomizing, dusting, scattering or pouring can be used. The form of application depends on the intended use; in any case, it should ensure that the mixture according to the invention is as fine and uniform as possible.

The formulations are prepared in a known manner, e.g. by stretching the active ingredient with solvents and / or carriers, if desired using emulsifiers and dispersants, and in the case of water as diluent other organic solvents can also be used as auxiliary solvents. The following are essentially considered as auxiliaries: solvents such as aromatics (eg xylene), chlorinated aromatics (eg chlorobenzenes), paraffins (eg petroleum fractions), alcohols (eg methanol, butanol), ketones (eg cyclohexanone), amines (eg ethanolamine , Dimethylformamide) and water; Carriers such as natural stone powder (e.g. kaolins, clays, talc, chalk) and synthetic stone powder (e.g. highly disperse silica, silicates); Emulsifiers such as non-ionic and anionic emulsifiers (e.g. polyoxyethylene fatty alcohol ethers, alkyl sulfonates and aryl sulfonates) and dispersants such as lignin sulfite waste liquors and methyl cellulose.

The surface-active substances are the alkali metal, alkaline earth metal and ammonium salts of aromatic sulfonic acids, for example lignin, phenol, naphthalene and dibutylnaphthalenesulfonic acid, and of fatty acids, alkyl and alkylarylsulfonates, alkyl, lauryl ether and fatty alcohol sulfates, and salts of sulfated hexa- , Hepta- and octadecanols or fatty alcohol glycol ethers, condensation products of sulfonated naphthalene and its derivatives with formaldehyde, condensation products of naphthalene or naphthalenesulfonic acids with phenol and formaldehyde, polyoxyethylene octyl phenol ether, ethoxylated isooctyl, octyl or nonyl phenol ether, phenyl or alkyl phenol, Alkylaryl polyether alcohols, isotridecyl alcohol, fatty alcohol ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers or polyoxypropylene, lauryl alcohol polyglycol ether acetate, sorbitol esters, lignin sulfite waste liquors or methyl cellulose. Powders, materials for broadcasting and dusts can be prepared by mixing or jointly grinding the compounds I and the compound II or the mixture of the compounds I and the compound II with a solid carrier.

Granules (e.g. coating, impregnation or homogeneous granules) are usually produced by binding the active ingredient or ingredients to a solid carrier.

The following fillers or solid carriers are used, for example: • Mineral earths such as silica gel, silicas, silica gels, silicates, talc, kaolin, limestone, lime, chalk, boluses, loess, clay, dolomite, diatomaceous earth, calcium and magnesium sulfate, magnesium oxide, ground plastics, and Fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas and vegetable products such as cereal flour, tree bark, wood and nutshell flour, cellulose powder or other solid carriers.

The formulations generally contain 0.1 to 95% by weight, preferably 0.5 to 90% by weight, of one of the compounds I and the compound II or the mixture of the compounds I and the compound II used in a purity of 90% to 100%, preferably 95% to 100% (according to the NMR or HPLC spectrum).

The compounds I and compound II, the mixtures or the corresponding formulations are used in such a way that the harmful fungi, their habitat or the plants, seeds, soils, areas, materials or spaces to be kept free of them are mixed with a fungicidally effective amount of the mixture, or the

Compounds I and compound II treated separately.

The application can take place before or after the infestation by the harmful fungi.

Examples of such preparations that contain the active ingredients are:

I. a solution of 90 parts by weight of the active ingredients and 10 parts by weight of N-methylpyrrolidone, which is suitable for use in the form of tiny drops; II. A mixture of 20 parts by weight of the active ingredients, 80 parts by weight

Parts of xylene, 10 parts by weight of the adduct of 8 to 10 moles of ethylene oxide and 1 mole of oleic acid-N-monoethanolamide, 5 parts by weight of calcium salt of dodecylbenzenesulfonic acid, 5 parts by weight of the adduct of 40 moles of ethylene oxide and 1 mole of castor oil; a dispersion is obtained by finely distributing the solution in water;

III. an aqueous dispersion of 20 parts by weight of the active ingredients, 40 parts by weight of cyclohexanone, 30 parts by weight of isobutanol,

20 parts by weight of the adduct of 40 moles of ethylene oxide and 1 mole of castor oil;

IV. An aqueous dispersion of 20 parts by weight of the active ingredients, 25 parts by weight of cyclohexanol, 65 parts by weight of a mineral oil fraction with a boiling point of 210 to 280 ° C. and 10 parts by weight of the adduct of 40 moles of ethylene oxide 1 mole of castor oil;

V. a mixture of 80 parts by weight of the active ingredients, 3 parts by weight of the sodium salt of diisobutylnaphthalene-1-sulfonic acid, 10 parts by weight of the sodium salt of a lignosulfonic acid from a sulfite waste liquor and 7 parts by weight of powder silica gel; a spray mixture is obtained by finely distributing the mixture in water; VI. an intimate mixture of 3 parts by weight of the active ingredients and 97 parts by weight of finely divided kaolin; this dust contains 3% by weight of active ingredient;

VII. An intimate mixture of 30 parts by weight of the active ingredients, 92 parts by weight of powdered silica gel and 8 parts by weight of paraffin oil which has been sprayed onto the surface of this silica gel; this preparation gives the active ingredient good adhesion;

VIII. A stable aqueous dispersion of 40 parts by weight of the active ingredients, 10 parts by weight of the sodium salt of a phenolsulfonic acid-urea-formaldehyde condensate, 2 parts by weight of silica gel and 48 parts by weight of water, which is further diluted can be;

IX. a stable oily dispersion of 20 parts by weight of the active ingredients, 2 parts by weight of the calcium salt of dodecylbenzenesulfonic acid, 8 parts by weight of fatty alcohol polyglycol ether,

20 parts by weight of the sodium salt of a phenolsulfonic acid-urea-formaldehyde condensate and 88 parts by weight of a paraffinic mineral oil.

applications

The synergistic effect of the mixtures according to the invention can be demonstrated by the following experiments:

The active ingredients are prepared separately or together as a 10% emulsion in a mixture of 63% by weight cyclohexanone and 27% by weight emulsifier and according to the desired concentration diluted with water.

The evaluation is carried out by determining the affected leaf areas in percent. These percentages are converted into efficiency levels. The efficiency (W) is determined according to Abbot's formula as follows: w = (1 - α / ß) -100

α corresponds to the fungal attack of the treated plants in% and ß corresponds to the fungal attack of the untreated (control) plants in%

With an efficiency of 0, the infection of the treated plants corresponds to that of the untreated control plants; at an efficiency of 100, the treated plants showed no infection.

The expected efficacies of the active ingredient mixtures were calculated using the Colby formula [R.S. Colby, Weeds 15, 20-22 (1967)] and compared with the observed efficiencies.

Colby formula: E = x + y - x-y / 100

E expected efficiency, expressed in% of the untreated control, when using the mixture of active ingredients A and B in concentrations a and bx the efficiency, expressed in% of the untreated control, when using active ingredient A in concentration ay, the efficiency, expressed in% of the untreated control when using the active ingredient B in the concentration b

Example of use: Protective activity against rice blight caused by Pyricularxa oryzae

Leaves of "Tai-" rice seedlings grown in pots

Nong 67 "were sprayed to runoff point with aqueous preparation of active compound, which was prepared with a stock solution consisting of 10% active compound, 85% cyclohexanone and 5% emulsifier. The following day, the plants were inoculated with an aqueous spore suspension of Pyricularia oryzae. The test plants were then placed in climatic chambers at 22 to 24 ° C. and 95 to 99% relative atmospheric humidity for 6 days, and the extent of the development of the infestation on the leaves was then determined visually. The visually determined values for the percentage of leaf areas affected were converted into efficiencies as% of the untreated control. The expected efficacies for combinations of active ingredients were determined using the Colby formula [RS Colby, "Calculating synergistic and antagonistic responses of herbicide combinations", Weeds, 15, pp. 20-22 (1967)] and compared with the observed efficacies.

Table 1: Comparative tests

Table 2: Mixtures according to the invention

berechneter Wirkungsgrad nach der Colby-Formel Aus den Ergebnissen des Versuches geht hervor, daß der beobachtete Wirkungsgrad in allen Mischungsverhältnissen deutlich höher ist, als nach der Colby-Formel vorausberechnet.

Efficiency calculated using the Colby formula The results of the experiment show that the observed efficiency in all mixing ratios is significantly higher than calculated using the Colby formula.

Claims

claims 1 . Mixtures for crop protection, containing as active components A) Oxime ether derivatives of the formula I.

in which the substituents have the following meanings: X NH or oxygen; R ¹ , R ³ independently of one another are hydrogen, cyano, _Cι-C4 alkyl, cyclopropyl or Cι-C ₄ haloalkyl; R ^2, R ⁴ are independently hydrogen, Cχ-C ₄ alkyl, C ₃ -C ₆ alkenyl, C ₃ -C ₆ alkynyl, Cι ~ C ₄ haloalkyl, C ₃ -C ₆ haloalkenyl or C ₃ - cg-haloalkynyl; and B) the compound of formula II

in a synergistically effective amount. 2. Mixtures according to claim 1, containing as component A the compound 1-4:

3. Mixture according to claims 1 or 2, wherein components A and B are present in mixing ratios of 20: 1 to 1: 200. 4. A method for combating phytopathogenic harmful fungi, characterized in that the fungi, their habitat or the materials, plants, seeds, soils, areas or spaces to be protected against fungal attack are treated with a fungicidal mixture according to one of claims 1 to 3 , wherein the application of compound I and compound II can be carried out simultaneously, that is jointly or separately, or in succession. 5. The method according to claim 4, characterized in that treating the harmful fungi, their habitat or the plants, seeds, soils, surfaces, materials or spaces to be kept free by them with 0.005 to 1 kg / ha of a compound I according to claims 1 or 2. 6. The method according to claim 4, characterized in that the harmful fungi, their habitat or the plants, seeds, soils, surfaces, materials or spaces to be kept free of them are treated with 0.01 to 1 kg / ha of the compound II according to claim 1.