JP4463558B2 - Oxime ether derivative sterilization mixture - Google Patents

Description

〔式中、置換基は下記の意味を有する：
Xは、NHまたは酸素であり;
R¹、R³は、互いに独立に、水素、シアノ、C₁-C₄-アルキル、シクロプロピルまたはC₁-C₄-ハロアルキルであり;
R²、R⁴は、互いに独立に、水素、C₁-C₄-アルキル、C₃-C₆-アルケニル、C₃-C₆-アルキニル、C₁-C₄-ハロアルキル、C₃-C₆-ハロアルケニルまたはC₃-C₆-ハロアルキニルである。〕
で表されるオキシムエーテル誘導体と、
（Ｂ）式ＩＩ：

で表される化合物と
を相乗効果を有する量で含む。 The invention relates to a mixture for the control of harmful fungi and insects, which mixture as active ingredient
(A) Formula I:

[Wherein the substituents have the following meanings:
X is NH or oxygen;
R ¹ and R ³ independently of one another are hydrogen, cyano, C ₁ -C ₄ -alkyl, cyclopropyl or C ₁ -C ₄ -haloalkyl;
R ² and R ⁴ are independently of each other hydrogen, C ₁ -C ₄ -alkyl, C ₃ -C ₆ -alkenyl, C ₃ -C ₆ -alkynyl, C ₁ -C ₄ -haloalkyl, C ₃ -C ₆ -Haloalkenyl or C ₃ -C ₆ -haloalkynyl. ]
An oxime ether derivative represented by:
(B) Formula II:

And a compound having a synergistic effect.

  The object of the present invention is a mixture having a good fungicidal action, in particular a fungicidal action against fungal diseases in rice, and at the same time a good insecticidal action, wherein the total amount of active compound supplied is reduced (Synergistic mixture). In areas with climatic conditions where rice grows, there are generally very large amounts of harmful insects, so a combination of bactericidal and insecticidal action is desirable.

  The inventors have found that the above problem is solved by the mixture according to claim 1 according to the present invention. Surprisingly, the inventors have found that compound II (compound II itself has no bactericidal action) enhances the bactericidal activity of the oxime ether derivative represented by formula I. Compound II therefore acts as an adjuvant.

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

  Insecticides of the formula II are likewise known (generic name: clothianidin) and are described in the literature (European Patent Application Publication No. 376279).

Preferred are compounds I in which R ¹ and R ³ are hydrogen, cyano, cyclopropyl, methyl, ethyl, 1-methylethyl or CF ₃ based on their biological activity.

Particularly preferred are compounds I in which R ¹ and R ³ are C ₁ -C ₄ -alkyl.

Even more particularly preferred are compounds I in which R ¹ is methyl.

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

Further preferred are compounds I in which R ² and R ⁴ are hydrogen, cyclopropyl, methyl, ethyl, isopropyl.

Furthermore, compounds I in which R ⁴ is methyl are preferred.

Furthermore, compounds I in which R ⁴ is ethyl or isopropyl are preferred.

  Particularly preferred are oxime ether derivatives of formula I wherein X is NH.

  In particular, in view of use with Compound II in the mixture of the present invention, Compound I according to Table 1 below is preferred.

本発明の混合物に含まれる化合物Ｉは、広範なスペクトルの植物病原性真菌、特に子嚢菌類、不完全菌類、藻菌類および担子菌類の真菌に対して顕著な活性を示す。 Oxime ether derivatives represented by formula I

The compounds I contained in the mixtures according to the invention show significant activity against a broad spectrum of phytopathogenic fungi, in particular fungi of ascomycetes, imperfect fungi, algae and basidiomycetes.

  They include strawberries, vegetables (eg cucumbers, legumes, tomatoes, potatoes and cucumbers), barley, grass, oats, bananas, coffee, corn, fruits, rice, rye, soybeans, grapes, It is particularly important in controlling a large number of fungi in various crop plants such as wheat, ornamental plants, sugarcane and various seeds.

  They are powdery mildew (cereals) in cereals, Erysiphe cichoracearum and cucumber powdery mildews (Sphaerotheca fuliginea) in cucumbers, Podosphaera leucotricha in apples, uncunula cinne in grapes Puccinia species in cereals, Rhizoctonia species in straw, rice and lawn, Ustilago species in cereals and sugarcane, Venturia inaequalis (decubitus) in apples, cereals and Helminthosporium species in rice, Septoria nodorum in wheat, Botrytis cinera in strawberries, vegetables, decorative plants and grapes (cells in peanuts) Cercospora arachidicola, wheat and barley in Pseudocercosporella herpotrichoides, rice and lawn, rice blast fungus (Pyricularia oryzae), potato and tomato potato infestants (Phytophthora infestans) Plasmopara viticola, Pseudoperonospora species in cucumbers and hops, Alternaria species in vegetables and fruits, Mycosphaerella species in Fusarium and Fusarium species It is particularly suitable for controlling a plant-causing fungus called Verticillium species.

  The compounds of the formula II are used for animal pest control of insects, arachnids and nematodes. The compounds can be used for the control of animal pests in crop protection, in the hygiene and protection sector of stored products, and in the veterinary sector. It is particularly suitable for controlling the following animal pests.

  Lepidoptera insects such as Agrotis ypsilon, Agrotis segetum, Alabama argillacea, Anticarsia gemmatalis, Anticarsia gemmatalis Argyresthia conjugella, Autographa gamma, Bupalus piniarius, Cacoecia murinana, Capua reticulana, Kematobia Burma Cheimatobia brumata, Choristoneura fumiferana, Sorihisura occidentalis, Sirphis unipunta (Cirphis u nipuncta, Cydia pomonella, Codlinga, Dendrolimus pini, Diaphania nitidalis, Diatraea grandiosella, Anarias inulana Misdia Olinga, Elasmopalpus lignosellus, Eupoecilia ambiguella, Evetria bouliana, Feltia subellaall, melia , Grapholitha funebrana, Grapholitha molesta, Heliothis armigera, giant Tobacco, Heliothis virescens, Heliothis zea, Hellula undalis, Hibernia defoliaria, Hyuntria tria American white human, Hyponomeuta malinellus, Keiferia lycopersicella, Lambdina fiscellaria, Laphygma exigua, terro opt , Leucoptera scitella, Lithocolletis blancardella, Lobesia botrana, Loxozo Loxostege sticticalis, Lymantria dispar (Maimaiga), Limantria monacha (Lymantier monacha), Rionetia clerkella (Lyonetia clerkella), Malacosoma osmao , Mamestra brassicae (Otoga), Orgyia pseudotsugata, Ostrinia nubilalis (European red moth), Panoris flammea (Panolis flammea), Pectimiphora s Peridroma saucia (Niseta Manayaga), Phalera bucephala, Fusorimaea Opelcrera ( Phthorimaea operculella, Phyllocnistis citrella, Pieris brassicae, Plathypena scabra, Plutella pella, Plutella xyste , Pseudoplusia includens, Rhyacionia frustrana, Scrobipalpula absoluta, Sitotroga cerealella, Sparganosi argano Pirlia (Spodoptera frugiperda), Spodoptera littoralis, Spodoptera litura, Spodoptera lituraali Matopoea-Pichokanpa (Thaumatopoea pityocampa, Torr Trix-Viridana (Tortrix viridana), Trichoplusia ni (trichoplusia ni, Trichoplusia ni) and Zeirafera canadensis (Zeiraphera canadensis).

  Beetles (Coleoptera), for example, Agrilus sinuatus, Agriotes lineatus, Agriotes obscurus, Amphimallis solstitial, Sandy (Anisandrus dispar), Anthonomus grandis (Anthonomus grandis), Anthonomus pomorum (Anthonomus pomorum), Atomaria linearis, Blastophagus piniperda (Blastophagus pinifaga) Blitophaga undata), Bruchus rufimanus (Bruchus rufimanus), Bruchus pisorum (Bruchus pisorum), Brutus lentis (Bruch) us lentis), Byctiscus betulae (Byctiscus betulae), Cassida nebulosa (Cassida nebulosa), Cerotoma trifurcata (Cerotoma trifurcata), Ceusorilischurishys Chaetocnema tibialis, Conoderus vespertinus, Criocelis asparagi, Diablotica longicornis, Diablotica-12-Puntadia-puncta-brothica・ Virgifera (Diabrotica virgifera), Epiracna varivestis (Ingententou), Epitrix Hiltipenis (Epit rix hirtipennis, Eutinobothrus brasiliensis, Hyrobius abietis, Hypera brunneipennis, Hipera postica, Alfafa Weevil), Ips typographus (Ips typographus), Lema bilineata, Lema melanopus, Leptinotarsa decemlineata, Lonicinos calforius , Lissorhoptrus oryzophilus, Melanotus communis, Meligethes aeneus, Meloronsa hippocastani (M elolontha hippocastani), Melolontha melolontha (European long-tailed beetle), Aurema oryzae, Ortiorrhynchus sulcatus, Otiortus chu, Otiorus Phaedon cochleariae, Phyllotreta chrysocephala, Phyllophaga sp., Phyllopertha horticola, Pyllopertha horticola, Pyllopertha ritico -Japonica (Popillia japonica), Sitona lineatus and Sitophilus granaria.

  Diptera, such as Aedes aegypti, Aedes vexans, Anastrepha ludens, Anopheles maculipennis, capitata , Chrysomya bezziana, Chrysomya hominivorax, Chrysomya macellaria, Contarinia gorma, Contarinia sol anthropophaga), Culex pipiens, Acajeca, Dacus cucurbitae, Dacus oleae ( Dacus oleae, Dasineura brassicae, Fannia canicularis, Gasterophilus intestinalis, Glossina morsitan, Glossina morsitan, Glossina morsitan・ Iritans (Haematobia irritans), Haplodiplosis equestris, Hylemyia platura, Hypoderma lineata, Liriomyza torie Trifolii (Liriomyza trifolii), Lucilia caprina, Lucilia cuprina, Lucilia celica (L ucilia sericata, Lycoria pectoralis, Mayetiola destructor, Musca domestica, Muscina stabulans, Osc ovis, sheep flies, Oscinella frit, Pegomya hysocyami, Phorbia antiqua, Phorbia brassicae, Phorbia coarctgo, R cerasi, Rhagoletis pomonella, Tabanas bovines, Tipula oleracea and Tipula palud osa).

  Thrips (Total), eg Frankliniella fusca, Frankliniella occidentalis, Frankliniella tritici, Scirt sri rip citri), Thrips oryzae, Thrips palmi, Thrips tabaci, Thrips tabaci.

  Hymenoptera (Hymenoptera), for example, Athalia rosae, Atta cephalotes, Atta sexdens, Atta texana, Hoprocampa Minota (Hoplocampa minuta), Hoplocampa testudinea, Monomorium pharaonis (Monomorium pharaonis), Solenopsis geminata (Solenopsis geminata) and Solenopsis invicta (Solenopsis invicta inviciota invicta

  Heterogenes (Hemiptera) such as Acrosternum hilare, Blisssus leucopterus, Cyrtopeltis notatus, Dysdercus cingulatus, Akahoshikamemushi Dysdercus intermedius, Eurygaster integriceps, Euschistus impictiventris, Leptoglossus phyllopus, islig L lineolais Lygus pratensis (Nezara viridula), Piesma quadrata, Solubea insulari (Solubea insulari) s) and Thyanta perditor.

  Homobacteria (Homoptera), for example, Acyrthosiphon onobrychis, Adelges laricis, Aphidula nasturtii, Aphis fabae, Aphis fabae, Aphis fabae , Aphis pomi, Aphis sambuci, Brachycaudus cardui, Brevicoryne brassicae, Cerosi gossi (Dreyfusia nordmannianae), Dreyfusia piceae, Dysaphis radicola, Dysaulacorthum pseudosolani, Empoaska fabae sca fabae, potato leafhopper, Macrosiphum avenae, Macrosiphum euphorbiae, Macrosiphum rosgo, virosiame, pori, urae・ Dilodam (Metopolophium dirhodum), Myzodes persicae, Myzus cerasi, Nilaparvata lugens, Pemfigas bursarius bur Perkinsiella saccharicida), Forodon humuli, Psylla mali, Psila piri Psylla piri, Rhopalomyzus ascalonicus, Rhopalosiphum maidis, corn aphids, Sappaphis mala, Sappaphis mali, Sizaphis, schizaphis Midria aphids, Schizoneura lanuginose, Trialurodes vaporariorum, Viteus vitifolii, Vineus vitifolii.

  Termites (Isoptera), for example, Calotermes flavicollis, Leucotermes flavipes, Reticulitermes lucifugus and Termes natalensis.

  For example, Aceta domestica (European green cricket), Bratta orientalis (Blatta orientalis), Blattella germanica (Forebicula), Forficula auricularia (Forficula auricularia) Nutsalworm, Gryllotalpa gryllotalpa, Locusta migratoria, Melanoplus bivittatus, Melanoplus femulus rubrum Melanoplus sanguinipse, Melanoplus spretus, Nomadakris Septemfaciata Nomadacris septemfasciata, Periplaneta americana, American cockroach, Schistocerca americana, Schistocerca peregrina, Stauronotus marocomotus maroccanus maruscanus asynamorus).

  Spiders, spiders (mites), such as Amblyomma americanum, Amblyomma variegatum, Argas persicus, Boophilus annulatus, Boophilus decoloratus, Boophilus microplus (Brown tick), Brevipalpus phoenicis, Bryobia praetiosa (Clover spider mite), Dermacentor silvarum (Dermacentor sil) Eotetranychus carpini, Eriophyes sheldoni, Hyalomma truncatum, Ixodes ricinus, Ixodes rubies Ixodes rubicundus, Ornithodorus moubata, Otobius megnini, Paratetranychus pilosus, Dermanyssus gallinae, Dermanyssus gallinae, Phyllocoptruta oleivora), Polyphagotarsonemus latus (Chanophorite mite), Psoroptes ovis (Psoroptes ovis), Ripicephalus appendiculatus, phalisphalisp Sarcoptes scabiei, Tetranychus cinnabarinus (Tetranychus cinnabarinus), Tetranychus kanzaw (Tetranychus kanzaw) ai (Kanzawa spider mite), Tetranychus pacificus (Tetranychus pacificus), Tetranychus telarius (Tetranychus telarius) and Tetranychus urticae (Namidani).

  Nematodes, root ball nematodes, etc. Potato cyst nematode (Globodera rostochiensis), Heterodera avenae, soybean cyst nematode (Heterodera glycines), sugar beet nematode (Heterodera schachtii), clover cyst nematode (Heterodera trifolii), tem and leaf nematode ), E.g., Belonolimus longicaudatus, Ditylenchus destructor, Ditylenchus dipsaci, Heliocotylenchus multicinctus, long edolus Nanaemoglisenchu (Radopholus similis), Rotylenchus robustus, Trichodols primitivus, Ishkusenchu (Tylenchorhynchus claytoni), Tylenchorlectus ), Pratylenchus penetrans, Pratylenchus curvitatus and Pratylenchus goodeyi.

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

  In order to control animal pests under outdoor conditions, the active compound application rate is generally 0.01 to 2.0 kg / ha, preferably 0.02 to 1.0 kg / ha.

  The mixtures according to the invention can be used particularly suitably for the control of plant diseases and harmful insects in rice.

  Compound I and compound II can be applied simultaneously, ie together or separately or sequentially. When applied separately, the order generally does not affect the results of the control treatment.

  Depending on the type of effect desired, the application rates of the mixtures according to the invention are 0.01-8 kg / ha, preferably 0.1-5 kg / ha, in particular 0.5-3.0 kg / ha, especially in the crop region.

The application rate of compound I is 0.01 to 2.5 kg / ha, preferably 0.05 to 2.5 kg / ha, especially 0.1 to 1.0 kg / ha. When seeds are treated, the application rate of the mixture is generally 0.001 to 250 g / kg (per 1 kg seed), preferably 0.01 to 100 g / kg, especially 0.01 to 50 g / kg.

  When controlling pathogenic harmful fungi, application of Compound I and Compound II separately or together, or application of a mixture of Compound I and Compound II may be carried out before or after sowing of the plant or before or after emergence of the plant. By spraying or dusting seeds, plants or soil.

  The mixtures according to the invention are for example in the form of instant spray solutions, powders and suspensions, or highly concentrated aqueous, oil-based and other suspensions, dispersions, emulsions, oily dispersions, pastes, powders Can be formulated in the form of a full spray material or granules and can be applied by spraying, atomization, dusting, full spray or irrigation. The form of use depends on the desired application. In any case, the mixture according to the invention must be distributed as sufficiently and uniformly as possible.

  The formulations are prepared in a known manner, for example by increasing the active ingredient with solvents and / or carriers, optionally with emulsifiers and dispersants, but other organic solvents as auxiliary when water is used as diluent. It is also possible to use it as a solvent. Suitable auxiliaries for this purpose are essentially aromatic compounds (eg xylene), chlorinated aromatic compounds (eg chlorobenzene), paraffins (eg mineral oil fractions), alcohols (eg methanol, butanol), ketones Solvents (such as cyclohexanone), amines (such as ethanolamine, dimethylformamide) and water; crustal natural minerals (such as kaolin, clay, talc, chalk), and crustal synthetic minerals (such as highly dispersed silica, silicates) Carriers; emulsifiers such as nonionic and anionic emulsifiers (eg polyoxyethylene aliphatic alcohol ethers, alkyl sulfonates and aryl sulfonates) and dispersants such as lignin-sulfite waste liquors and methylcellulose.

  Suitable surfactants include alkali metal salts, alkaline earth metal salts and ammonium salts of aromatic sulfonic acids such as lignosulfonic acid, phenolsulfonic acid, naphthalenesulfonic acid and dibutylnaphthalenesulfonic acid; fatty acids, alkylsulfonates, alkylaryls Alkali metal, alkaline earth metal and ammonium salts of sulfonates, alkyl lauryl ethers and aliphatic alcohol sulfonates; salts of sulfated hexa, hepta and octadecanol, or salts of aliphatic alcohol glycol ethers; sulfonated naphthalene and it Condensates of derivatives of and formaldehyde; condensates of naphthalene or naphthalenesulfonic acid with phenol and formaldehyde; polyoxyethylene octylphenol ether; Isooctyl, octyl or nonylphenols; alkylphenyl polyglycol ethers; tributylphenyl polyglycol ethers; alkylaryl polyether alcohols; isotridecyl alcohol; aliphatic alcohol / ethylene oxide condensates; ethoxylated castor oil; Ethylene alkyl ethers or polyoxypropylene alkyl ethers; lauryl alcohol polyglycol ether acetate; sorbitol esters; lignosulfite waste liquor; or methylcellulose.

  Powders, dust spreaders, and powders can be prepared by comminuting Compound I and Compound II or a mixture of Compound I and Compound II with a solid carrier or grinding together.

  Granules, such as coated granules, impregnated granules, or uniform granules, are usually prepared by binding one or more active compounds to a solid support.

  Examples of fillers or solid carriers include crustal minerals such as silica, silica gel, silicate, talc, kaolin, limestone, lime, chalk, ball clay, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide There are crust synthetic materials, fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate, urea, and plant-derived products such as cereal meal, bark flour, wood flour and nutshell flour, cellulose powder and other solid carriers.

  In general, the formulation comprises 0.1 to 95% by weight, preferably 0.5 to 90% by weight, of one of Compound I and Compound II or a mixture of Compound I and Compound II. The active compounds are used in a purity of 90% to 100%, preferably 95% to 100% (NMR spectrum or HPLC basis).

  Compound I and Compound II, a mixture or corresponding formulation comprises a sterilizing effective amount of a mixture of plants, seeds, soil, areas, materials or spaces in which harmful fungi, their habitat, or their fungi are to be maintained, Alternatively, when applied separately, it is applied by treating with a sterilizing effective amount of Compound I and Compound II.

  Application can take place before or after infection by harmful fungi.

The following are examples of formulations containing active compounds:
I. A solution of 90 parts by weight of active compound and 10 parts by weight of N-methylpyrrolidone. This solution is suitable for use in the form of microdroplets.

II. 20 parts by weight of active compound, 80 parts by weight of xylene, 10 parts by weight of adduct of 8-10 moles of ethylene oxide and 1 mole of oleic acid N-monoethanolamide, 5 parts by weight of calcium salt of dodecylbenzenesulfonic acid, 40 moles A mixture of 5 parts by weight of an adduct of ethylene oxide and 1 mole of castor oil. A dispersion is obtained by finely dispersing the solution in water.

III. An aqueous dispersion of 20 parts by weight of active compound, 40 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight of an adduct of 40 moles of ethylene oxide and 1 mole of castor oil.

IV. An aqueous dispersion of 20 parts by weight of active compound, 25 parts by weight of cyclohexanol, 65 parts by weight of a mineral oil fraction having a boiling point of 210-280 ° C, and 10 parts by weight of an adduct of 40 moles of ethylene oxide and 1 mole of castor oil.

V. 80 parts by weight of active compound, 3 parts by weight of sodium salt of diisobutylnaphthalene-1-sulfonic acid, 10 parts by weight of sodium salt of lignosulfonic acid obtained from sulfite waste liquor and 7 parts by weight of powdered silica gel are mixed and pulverized with a hammer mill Mixture. A spray mixture is obtained by finely dispersing the mixture in water.

VI. Homogeneous mixture of 3 parts by weight of active compound and 97 parts by weight of finely divided kaolin. This powder contains 3% by weight of active compound.

VII. A homogeneous mixture of 30 parts by weight of active compound, 92 parts by weight of powdered silica gel and 8 parts by weight of paraffin oil sprayed onto the surface of the silica gel. This formulation imparts good adhesion to the active compound.

VIII. A stable aqueous dispersion of 40 parts by weight of active compound, 10 parts by weight of sodium salt / urea / formaldehyde condensate of phenolsulfonic acid, 2 parts by weight of silica gel and 48 parts by weight of water. This dispersion may be further diluted.

IX. 20 parts by weight of active compound, 2 parts by weight of calcium salt of dodecylbenzenesulfonic acid, 8 parts by weight of aliphatic alcohol polyglycol ether, 20 parts by weight of sodium salt / urea / formaldehyde condensate of phenolsulfonic acid and 88 parts by weight of paraffinic mineral oil Stable oily dispersion.

Use Examples The synergistic activity of the mixtures according to the invention can be demonstrated in the following experiments:
The active compounds are formulated separately or together as a 10% emulsion of a mixture of 63% by weight cyclohexanone and 27% by weight emulsifier and diluted to the desired concentration with water.

Assessment is performed by determining the infected leaf area in percent. Convert that percentage to efficacy. Efficacy ( W ) is calculated using the Abbot equation as follows:

W = (1−α / β) · 100
Where
α corresponds to the fungal infection rate (%) of the treated plant;
β corresponds to the fungal infection rate (%) of untreated (control) plants.

  A potency of 0 means that the level of infection of the treated plant corresponds to the level of the untreated control plant, and a potency of 100 means that the treated plant was free of infection.

The expected efficacy of the active compound mixture is determined using the Colby equation [RS Colby, Weeds 15 , 20-22 (1967)] and compared to the measured efficacy value.

Colby's formula E = x + y−x · y / 100
Where
E is the expected efficacy expressed as a percentage of the untreated control when using a mixture of active compounds A and B at concentrations a and b;
x is the potency expressed as a percentage of the untreated control when active compound A is used at concentration a;
y is the potency expressed as a percentage of the untreated control when active compound B is used at concentration b.

Example of use: protection against rice blast caused by Pyricularia oryzae Sprayed to the pour point. This aqueous preparation was prepared from a stock solution containing 10% active compound, 85% cyclohexanone and 5% emulsifier. The next day, the plants were inoculated with an aqueous suspension of Pyricularia oryzae spores. The test plants were then placed in a chamber adjusted to 22-24 ° C. and relative atmospheric humidity 95-99% for 6 days. The degree of leaf infection occurrence was measured visually.

The value measured visually for the percentage of infected leaf area was converted to efficacy expressed as a percentage of the untreated control. The expected efficacy of the active compound combination was determined using Colby's formula [RS Colby, “Calculating synergistic and antagonistic responses of herbicide Combinations”, Weeds 15 , 20-22 (1967)] and compared to the measured efficacy value.

  From the test results, it can be seen that the measured efficacy is greater than the value calculated in advance using the Colby equation at all mixing ratios.

Claims (5)

As active ingredient A, compound I-4 :

When,
(B) Formula II:

A crop protection mixture comprising a compound represented by: The mixture according to claim 1 , wherein the active ingredients A and B are present in a mixing ratio of 20: 1 to 1: 200. A method for controlling plant pathogenic harmful fungi, the harmful fungi, the material to be protected from its habitat locations or fungal attack, plants, seeds, soils, areas or spaces, according to claim 1 or 2 crops Said process comprising the step of treating with a protective mixture, wherein the application of compound I-4 and compound II may be carried out simultaneously, ie together or separately or sequentially. Treating said harmful fungus, its habitat or plant, seed, soil, area, material or space to be free of said harmful fungus with 0.001 to 1 kg / ha of compound I-4 according to claim 1 The method of claim 3 . Treating said plant, seed, soil, area, material or space to be maintained free of said harmful fungus, its habitat or its harmful fungus with 0.01 to 1 kg / ha of compound II according to claim 1; The method of claim 3 .