CN1320855C - Fungicidal mixtures based on 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 oxime ether derivatives and guanidine derivatives

The present invention relates to mixtures for controlling harmful fungi and insects, which mixtures contain as active ingredients synergistically effective amounts of:

A) oxime ether derivatives of formula I:

Wherein each substituent is defined as follows:

X is NH or oxygen;

R ¹ and R ³ are independently hydrogen, cyano, C ₁ -C ₄ alkyl, cyclopropyl or C ₁ -C ₄ haloalkyl;

R ² and R ⁴ are independently 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 halogen Alkenyl or C ₃ -C ₆ haloalkynyl;

and

B) compound of formula II:

It was an object of the present invention to provide mixtures (synergistic mixtures) which have a good fungicidal action and at the same time a good insecticidal action especially against fungal diseases in rice, and a reduced total application rate of active compounds. Because in the climatic regions where rice grows, harmful insects are usually also present in large numbers, both fungicidal and insecticidal effects are required.

We have found that this object is achieved according to the invention by the mixture as claimed in claim 1 . We have surprisingly found that the compound II, which itself has no fungicidal effect, increases the fungicidal activity of the oxime ether derivatives of the formula I. Compound II is therefore used 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 insecticides of the formula II are likewise known (common name: clothianidin) and described in the literature (EP-A 376 279).

Due to the biological activity of compounds of formula I, compounds of formula I wherein R ^{and R} are hydrogen, cyano, cyclopropyl, methyl, ethyl, 1-methylethyl or _CF are preferred.

Particular preference is given to compounds I in which R ¹ and R ³ are C ₁ -C ₄ -alkyl.

Furthermore, particular preference is also given to compounds I in which R ¹ is methyl.

Furthermore, preference is also given to compounds I in which R ¹ is CF ₃ .

Furthermore, preference is also given to compounds I in which ^R2 and ^R4 are hydrogen, cyclopropyl, methyl, ethyl, isopropyl.

Furthermore, preference is also given to compounds I in which R ⁴ is methyl.

Furthermore, preference is also given to compounds I in which R ⁴ is ethyl or isopropyl.

Particular preference is given to oxime ether derivatives of the formula I in which X is NH.

Especially in view of their use in the present invention in admixture with compounds II, compounds I summarized in Table 1 below are preferred.

Table 1

Oxime ether derivatives of formula I:

serial number R ¹ R ² R ³ R ⁴ x I-1 h h h h NH I-2 h _CH3 h _CH3 NH I-3 _CH3 h _CH3 h NH I-4 _{CH3 CH3 CH3 CH3} NH I-5 _CH3 Ring-C ₃ H _{5 CH3} Ring-C ₃ H ₅ NH I-6 _CH3 CH ₂ CH _{3 CH3} CH ₂ CH ₃ NH I-7 _CH3 CH(CH ₃ ) _{2 CH3} CH(CH ₃ ) ₂ NH I-8 _CH3 CH ₂ CH=CH _{2 CH3} CH ₂ CH=CH ₂ NH I-9 CF ₃ h CF ₃ h NH I-10 CF _{3 CH3} CF _{3 CH3} NH

I-11 CF ₃ CH(CH ₃ ) ₂ CF ₃ CH(CH ₃ ) ₂ NH I-12 CN h _CH3 h NH I-13 CN _{CH3 CH3 CH3} NH I-14 h h h h o I-15 h _CH3 h _CH3 o I-16 _CH3 h _CH3 h o I-17 _{CH3 CH3 CH3 CH3} o I-18 _CH3 Ring-C ₃ H _{5 CH3} Ring-C ₃ H ₅ o I-19 _CH3 CH ₂ CH _{3 CH3} CH ₂ CH ₃ o I-20 _CH3 CH(CH ₃ ) _{2 CH3} CH(CH ₃ ) ₂ o I-21 _CH3 CH ₂ CH=CH _{2 CH3} CH ₂ CH=CH ₂ o I-22 CF ₃ h CF ₃ h o I-23 CF _{3 CH3} CF _{3 CH3} o I-24 CN h _CH3 h o I-25 CN _{CH3 CH3 CH3} o

The compounds I present in the mixtures according to the invention have significant activity against a wide range of phytopathogenic fungi, especially selected from the class Ascomycetes, Deuteromycetes, Phycomycetes and Basidiomycetes fungi.

They are effective in various crops such as cotton, vegetable varieties (such as cucumbers, beans, tomatoes, potatoes and cucurbits), barley, grasses, oats, bananas, coffee, corn, fruit varieties, rice, rye, soybeans, It is especially important to control a large number of fungi in vines, wheat, ornamentals, sugar cane and various seeds.

They are particularly suitable for controlling the following phytopathogenic fungi: Blumeriagraminis (Powdery mildew) on cereals, Erysiphe cichoracearum and Sphaerotheca fuliginea on cucurbits, Apple powdery mildew ( Podosphaeraleucotricha), Uncinula necator on vines, Puccinia on cereals, Rhizoctonia on cotton, rice and turf, Black necator on cereals and sugarcane Ustilago spp., Venturia inaequalis (scab) on apples, Helminthosporium spp. on cereals and rice, Septoria nodorum on wheat , Botrytiscinerea (botrytis cinerea) on strawberries, vegetables, ornamentals and grape vines, Cercospora arachidicola on peanuts, Pseudocercosporella herpotrichoides on wheat and barley, rice and Pyricularia oryzae on lawns, Phytophthorainfestans on potatoes and tomatoes, Plasmopara viticola on grapevines, Pseudoperonospora on hops and cucumbers , Alternaria on vegetables and fruits, Mycosphaerella on bananas, and Fusarium and Verticillium.

The compounds of formula II are useful for controlling animal pests selected from insects, arachnids and nematodes. It can be used in crop protection, in the field of hygiene and protection of stored products and in the field of veterinary medicine for controlling animal pests. The compounds are particularly suitable for controlling the following animal pests:

Insects of the order Lepidoptera (Lepidoptera), such as Agrotis ypsilon, Agrotis segetum, Alabama argillacea, Anticarsia gemmatalis, Argyresthia conjugella, Autographa gamma, tree looper (Bupalus piniarius) ), Cacoecia murinana, Capua reticulana, Cheimatobia brumata, Choristoneura fumiferana, Choristoneura occidentalis, Cirphisunipuncta, Cydia pomonella, Dendrolimus pini, Diaphanianiitidalis, Diatraea grandiosella, Eariasinsulana, Elasmopalpus lignosellus, Eupoecilia ambiguella, Evetria bouliana, Feltia subterranea, Galleria mellonella, Grapholitha funebrana, pear Small borer (Grapholitha molesta), cotton bollworm (Heliothis armigera), tobacco budworm (Heliothisvirescens), corn earworm (Heliothis zea), rice borer (Hellula undalis), Hibernia defoliaria, American white moth (Hyphantria cunea), Hyponomeuta malellus, tomato Keiferia lycopersicella, Lambdina fiscellaria, Beet Spodoptera (Laphygmaexigua), Coffee Leaf Miner (Leucoptera coffeeella), Spiral Miner (Leucoptera scitella), Lithotis blancardella, Grape Berry Torch (Lobesia botrana), Beet Netting Loxostege sticticalis, Lymantria dispar, Lymantriamonacha, Lyonetia clerkella, Malacosomaneustria, Mamestra brassicae, Orgyia pseudotsugata, Ostrinia nubilalis), Pectinophoragossypiella, Pectinophoragossypiella, Peridroma saucia, Phalera bucephala, Phthorimaea operculella, Citrus leaf miner (Phyllocnistis citrella), European white butterfly (Pieris brassicae), clover moth (Plathypena scabra), diamondback moth (Plutellaxylostella), soybean armyworm (Pseudoplusia includesens), Rhyacionia frustrana, Scrobipalpula absoluta, wheat moth (Sitotroga cerealella), grape leaf tortrix (Sparganothis pilleriana), Spodoptera frugiperda, Spodoptera littoralis, Spodoptera litura, Thaumatopoeapityocampa, Tortrix viridana, Trichoplusia ni and Zeirapheracanadensis,

Beetles (Coleoptera) such as Agrilus sinuatus, Agriotes lineatus, Agriotes obscurus, Amphimallus solstitialis, Anisandrus dispar, Mexican boll weevil (Anthonomus grandis), apple blossom weevil (Anthonomus pomorum), sugar beet hidden eating beetle (Atomaria linearis), vertical pit beetle (Blastophagus piniperda), Blitophaga undata, broad bean elephant (Bruchus rufimanus), pea elephant (Bruchus pisorum), European lentil elephant (Bruchus lentis), Byctiscus betulae, Cassida nebulosa, Cerotomatrifurcata, Ceuthorrhynchus assimilis, Ceuthorrhynchus napi, Chaetocnema tibialis, Conoderus vespertinus, Stone beetle Crioceris asparagi, Diabrotica longicornis, Diabrotica 12-punctata, Diabrotica virgifera, Epilachna varivestis, Epitrix hirtipennis, Eutinobothrus var. brasiliensis), pine bark beetle (Hylobius abietis), Egyptian clover leaf elephant (Hypera brunneipennis), alfalfa leaf elephant (Hypera postica), spruce octopus (Ipstypographus), tobacco negative mudworm (Lema bilineata), black horned Lemamelanopus, Leptinotarsa decemlineata, Limonius californicus, Rice water weevil (Lissorhoptrus oryzophilus), Melanotus communis, Meligethes aeneus, Melolontha hippocastani, May beetle (Melolontha melolontha), Oulema oryzae, Ortiorrhynchus sulcatus, Strawberry root weevil (Otiorrhynchus ovatus), Horseradish root beetle (Phaedon cochleariae), Phyllotreta chrysocephala, Leaf-eating beetle (Phyllophaga) genus, Phyllopertha horticola, Phyllotreta nemorum, Phyllotreta striolata, Popillia japonica, Sitona lineatus and Valley elephant (Sitophilus granaria),

Diptera (Diptera) such as Aedes aegypti, Aedes vexans, Anastrepha ludens, Anopheles maculipennis, Ceratitis capitata ), Chrysomyabezziana, Chrysomya hominivorax, Chrysomya macellaria, Contarinia sorghicola, Cordylobia anthropophaga, Culexpiens, melon fly, Dacus oleae, rape leaf gall , Fannia canicularis, Gasterophilus intestinalis, Glossina morsitans, Haematobia irritans, Haplodiplosis equestris, Hylemyia platura, Hypoderma lineata, Vegetable spotted bug Liriomyza sativae, Liriomyza trifolii, Lucilia caprina, Lucilia cuprina, Lucilia sericata, Lycoria pectoralis, Mayetiola destructor, Musca domestica, Stable rot fly (Muscina stabulans), sheep fly (Oestrus ovis), European wheat straw fly (Oscinella frit), hydrangea spring fly (Pegomyahysocyami), Phorbia antiqua, turnip fly (Phorbia brassicae), Phorbia coarctata, cherry fruit fly (Rhagoletis cerasi), apple fruit fly (Rhagoletis pomonella), Tabanus bovinus, Tipula oleracea and European giant mosquito (Tipula paludosa),

Thrips (Thysanoptera), such as Frankliniella fusca, Frankliniella occidentalis, Frankliniella tritici, Scirtothrips citri, Rice thrips ( Thrips oryzae), Thrips palmi and Thrips tabaci,

Insects of the order Hymenoptera (Hymenoptera), such as Athalia rosae, Atta cephalotes, Atta sexdens, Atta texana, Hoplocampa minuta, Hoplocampa testudinea, Monomorium pharaonis, Solenopsis geminata and fire ants (Solenopsis invicta),

Insects of the suborder Heteroptera (Heteroptera), such as Acrosternum hilare, Blissus leucopterus, Cyrtopeltis notatus, Dysdercus cingulatus, Dysdercus intermedius , Eurygasterintegriceps, Euschistus impictiventris, Leptoglossusphyllopus, Lygus lineolaris, Lygus pratensis, Nezara viridula, sugar beet netting Stinkbugs (Piesma quadrata), Solubea insularis and Thyanta perditor,

Insects of the suborder Homoptera (Homoptera), for example Acyrthosiphon onobrychis, Adelges laricis, Aphidula nasturtii, sugar beet aphid (Aphis fabae), apple aphid (Aphispomi), elderberry aphid (Aphis sambuci), Brachycaudus cardui, Brevicoryne brassicae, Cerosipha gossypii, Dreyfusia nordmannianae, Dreyfusia piceae, Dysaphis radicola , Dysaulacorthum pseudosolani, Empoascafabae, Macrosiphum avenae, Macrosiphumeuphorbiae, Macrosiphon rosae, Megoura viciae, wheat Metopolophium dirhodum, Myzodes persicae, Myzuscerasi, Nilaparvata lugens, Pemphigus bursarius, Perkinsiella saccharicida, Phorodon humuli ), Psylla mali, Psylla piri, Rhopalomyzus ascalonicus, Rhopalosiphum maidis, Sappaphis mala, Sappaphis mali, Schizaphis graminum, Ulmus cotton aphid (Schizoneura lanuginosa), whitefly (Trialeurodes vaporariorum) and grape phylloxera (Viteus vitifolii),

termites (Isoptera), such as Calotermes flavicollis, Leucotermes flavipes, European termites (Reticulitermes lucifugus) and Termes natalensis,

Insects of the order Orthoptera (Orthoptera), such as Acheta domestica, Blatta orientalis, Blattella germanica, Forficula auricularia, Gryllotalpa gryllotalpa, Locusta migratoria, Melanoplus bivittatus, Melanoplus femur-rubrum, Melanoplus mexicanus, Melanoplus sanguinipes, Melanoplus spretus), striped red locust (Nomadacris septemfasciata), American cockroach (Periplaneta americana), American desert locust (Schistocerca americana), Schistocerca peregrina, Stauronotus maroccanus and family disease katydid (Tachycines asynamorus),

Arachnoidea, such as spiders (Acarina), e.g. long star tick (Amblyomma americanum), tropical flower tick (Amblyomma variegatum), Persian sharp edge tick (Argaspersicus), cow tick (Boophilus annulatus), Boophilus decoloratus, Boophilus microplus, Brevipalpus phoenicis, Bryobia praetiosa, Dermacentor silvarum, Eotetranychus carpini, Eriophyes sheldoni, Hyalommatruncatum, Ixodes ricinus, Ixodes rubicundus, Ornithodorus moubata, Otobius megnini, Paratetranychus pilosus, Dermanyssus gallinae, Phyllocoptruta oleivora, Polyphagotarsonemus latus ), Psoroptes ovis, Rhipicephalus appendiculatus, Rhipicephalus evertsi, Sarcoptesscabiei, Tetranychus cinnabarinus, Tetranychuskanzawai, Tetranychus pacificus, Tetranychus pacificus ( Tetranychustelarius) and two-spotted spider mite (Tetranychus urticae),

Nematodes such as root-knot nematodes such as Meloidogyne hapla, Meloidogyne incognita, Meloidogyne javanica; cyst nematodes such as Globodera rostochiensis, oat Cyst nematodes (Heterodera avenae), soybean cyst nematodes (Heterodera glycines), sugar beet cyst nematodes (Heterodera schachtii), clover cyst nematodes (Heterodera trifolii); and stem and leaf nematodes such as Belonolaimus longicaudatus ), Ditylenchus destructor, Ditylenchus dipsaci, Heliocotylenchus multicinctus, Longidoruselongatus, Radopholus similis, Rotylenchus robustus ), Trichodorus primitivus, Tylenchorhynchus claytoni, Tylenchorhynchus dubius, Pratylenchus neglectus, Pratylenchus penetrans, Pratylenchus curvitatus and Pratylenchus goodeyi.

Compounds I and II are generally administered in a weight ratio of 20:1 to 1:200, especially 10:1 to 1:180, preferably 2:1 to 1:160.

Under outdoor conditions, for controlling animal pests, the active compound application rates are generally from 0.01 to 2.0 kg/ha, preferably from 0.02 to 1.0 kg/ha.

The mixtures according to the invention can be used with particular preference for controlling plant diseases and harmful insects in rice.

Compound I and compound II can be applied simultaneously, ie together or individually, or in succession, the order of application generally not having any influence on the effectiveness of the control measures in the case of individual application.

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

The application rate of compound I is 0.01-2.5 kg/ha, preferably 0.05-2.5 kg/ha, especially 0.1-1.0 kg/ha.

For seed treatment, the application rate of the mixture is generally 0.001-250 g/kg seed, preferably 0.01-100 g/kg, especially 0.01-50 g/kg.

If it is desired to control phytopathogenic harmful fungi, the compound I and the compound II or the combination of the compound I and the compound II are applied alone or in combination by spraying or dusting the seed, the plant or the soil before or after sowing the plants or before or after the emergence of the plants mixture.

The mixtures according to the invention can be formulated, for example, in the form of ready-to-spray solutions, powders and suspensions or highly concentrated aqueous, oily or other suspensions, dispersions, emulsions, oil dispersions, pastes, powders, broadcasting materials or granules and passed through Apply by spraying, misting, dusting, broadcasting or pouring. The use forms depend on the desired purpose; in any case it should ensure that the mixture according to the invention is distributed as finely and homogeneously as possible.

The formulations are prepared in a known manner, for example by mixing the active compounds with solvents and/or carriers, if necessary using emulsifiers and dispersants, and if water is used as diluent, other organic solvents can also be used as auxiliary solvents. Auxiliaries suitable for this purpose are mainly solvents such as aromatic solvents (such as xylene), chlorinated aromatic solvents (such as chlorobenzene), paraffins (such as mineral oil fractions), alcohols (such as methanol, butanol), ketones (such as cyclohexanone), amines (such as ethanolamine, dimethylformamide) and water; carriers such as ground natural minerals (such as kaolin, clay, talc, chalk) and ground synthetic minerals (such as finely divided silica, silicates); emulsifiers such as nonionic and anionic emulsifiers (such as polyoxyethylene fatty alcohol ethers, alkyl sulfonates and aryl sulfonates) and dispersants such as lignosulfite waste liquor and methyl cellulose white.

Suitable surfactants are aromatic sulfonic acids such as lignosulfonic acid, phenolsulfonic acid, naphthalenesulfonic acid and dibutylnaphthalenesulfonic acid and alkali metal, alkaline earth metal and ammonium salts of fatty acids, alkyl- and alkyl Aryl sulfonates, alkyl sulfates, lauryl ether sulfates and fatty alcohol sulfates and salts of sulfated cetyl-, heptadecan- and stearyl alcohols, or salts of fatty alcohol glycol ethers, sulfonate Condensates of naphthalene and its derivatives with formaldehyde, condensates of naphthalene or naphthalenesulfonic acid with phenol and formaldehyde, polyoxyethylene octylphenol ethers, ethoxylated isooctylphenol, octylphenol or nonylphenol , Alkylphenyl Polyglycol Ether, Tributylphenyl Polyglycol Ether, Alkylaryl Polyether Alcohol, Isotridecanyl Alcohol, Fatty Alcohol/Ethylene Oxide Condensate, Ethoxylated Castor Oil , polyoxyethylene alkyl ether or polyoxypropylene alkyl ether, lauryl polyglycol ether acetate, sorbitol ester, lignosulfite waste liquor and methylcellulose.

Powders, spreading materials and dusts can be prepared by mixing or grinding together the compound I and the compound II or a mixture of the compound I and the compound II with solid carriers.

Granules (eg coated, impregnated or homogeneous granules) are usually prepared by binding one or more active compounds to a solid carrier.

Fillers or solid carriers are, for example, mineral earths such as silica, silica gel, silicates, talc, kaolin, limestone, lime, chalk, basalt, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide ; Ground synthetic materials; Fertilizers such as ammonium sulphate, ammonium phosphate, ammonium nitrate, urea; Products of plant origin such as grain flour, bark flour, wood flour and nut shell flour; Cellulose flour or other solid carriers.

The formulations generally comprise 0.1-95% by weight, preferably 0.5-90% by weight, of compound I and compound II or a mixture of compound I and compound II. The active compounds are used in a purity of 90-100%, preferably 95-100% (according to NMR spectroscopy or HPLC).

Compounds I and II, mixtures or corresponding formulations by treating harmful fungi, their habitats or plants, seeds, soil requiring control of harmful fungi with a fungicidally effective amount of the mixture or in the case of individual application, compounds I and II , area, material or space.

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

Examples of such formulations containing active compounds are:

1. 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 microdroplets;

II.20 parts by weight active compound, 80 parts by weight xylene, 10 parts by weight 8-10mol ethylene oxide and 1mol oleic acid N-monoethanolamide adduct, 5 parts by weight calcium dodecylbenzenesulfonate, 5 parts by weight A mixture of 40 mol of an adduct of ethylene oxide and 1 mol of castor oil; a dispersion is obtained by finely distributing this solution in water;

III.20 parts by weight of active compound, 40 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight of the adduct of 40mol ethylene oxide and 1mol castor oil;

IV. 20 parts by weight of active compound, 25 parts by weight of cyclohexanol, 65 parts by weight of mineral oil fractions with a boiling point of 210-280° C. and 10 parts by weight of an adduct of 40 mol ethylene oxide and 1 mol castor oil;

V. 80 parts by weight of active compound, 3 parts by weight of sodium diisobutylnaphthalene 1-sulfonate, 10 parts by weight of sodium lignosulfonate from sulfite waste liquor and 7 parts by weight of powdered silica gel were ground in a hammer mill a mixture; a spray mixture is obtained by finely distributing the mixture in water;

VI. A homogeneous mixture of 3 parts by weight of active compound and 97 parts by weight of finely divided kaolin; the 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 on the surface of the silica gel; this formulation imparts good adhesion to the active compound;

VIII. Stable aqueous dispersion of 40 parts by weight of active compound, 10 parts by weight of sodium salt of phenolsulfonic acid/urea/formaldehyde condensate, 2 parts by weight of silica gel and 48 parts by weight of water; the dispersion can be further diluted;

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

Application example

The synergistic activity of the mixture of the present invention can be confirmed by following test:

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

Evaluation is carried out by measuring the infected leaf area (%). These percentages were converted to efficacy. Potency (W) was calculated using Abbot's formula as follows:

W=(1-α/β)·100

a corresponds to the fungal infection (%) of the treated plants, and

b corresponds to the fungal infection (%) of untreated (control) plants.

An efficacy of 0 means that the degree of infection of the treated plants corresponds to that of the untreated control plants; an efficacy of 100 means that the treated plants are not infected.

The expected efficacy of a mixture of active compounds is determined using the Colby formula [RS Colby, Weeds (Weeds) 15 , 20-22 (1967)] and compared to the observed efficacy.

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

E is the expected potency when using a mixture of active compounds A and B at concentrations a and b, expressed in % relative to the untreated control,

x is the potency of active compound A at concentration a in % relative to the untreated control, y is the potency of active compound B at concentration b in % relative to the untreated control.

Example of use: Protective activity against rice blast caused by Pyricularia oryzae

Leaves of potted rice seedlings of the cultivar "Tai-Nong67" were sprayed to runoff with an aqueous formulation of active compound consisting of a stock solution containing 10% active compound, 85% cyclohexanone and 5% emulsifier preparation. The plants were inoculated the next day with an aqueous spore suspension of Magnaporthe oryzae. The test plants are then placed in a climatic chamber for 6 days at 22-24° C. and 95-99% relative atmospheric humidity. The degree of infestation development on the leaves was then assessed visually.

The determination of the percent infected leaf area was converted into a % efficacy relative to the untreated control. The expected efficacy of active compound combinations was determined using the Colby formula [R.S. Colby, "Calculation of synergistic and antagonistic responses of herbicide combinations", Weeds (Weeds, 15, pp. 20-22 (1967)) and compared with the observed efficacy Compared.

Table 1: Comparative Test

active compound Concentration of active compound in spray solution [ppm] % potency compared to untreated control Control (untreated) (89% infected) 0 I-4 820.5 776610 II 80205 000

Table 2: Mixtures of the invention

The mixture of the present invention Observed efficacy Calculated potency ^* ) I-4+II8+5ppm mixing ratio 1.6:1 97 77 I-4+II8+20ppm mixing ratio 1:2.5 94 77 I-4+II8+80ppm mixing ratio 1:10 97 77 I-4+II2+20ppm mixing ratio 1:10 83 66 I-4+II0.5+5ppm mixing ratio 1:10 twenty one 10 I-4+II0.5+20ppm mixing ratio 1:40 32 10  I-4+II0.5+80ppm mixing ratio 1:160 twenty one 10

^* ) Potency calculated using Colby's formula

The test results showed that the observed potency at all mixing ratios was higher than that previously calculated using Colby's formula.

Claims (6)

1. A mixture for crop protection comprising as active components a synergistically effective amount of the following components: A) oxime ether derivatives of formula I: Wherein each substituent is defined as follows: X is NH or oxygen; R ¹ and R ³ are independently hydrogen, C ₁ -C ₄ alkyl, cyclopropyl or C ₁ -C ₄ haloalkyl; R ² and R ⁴ are independently 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 halogen Alkenyl or C ₃ -C ₆ haloalkynyl; and B) compound of formula II:

2. The mixture as claimed in claim 1, comprising compound I-4 as component A:

3. The mixture as claimed in claim 1 or 2, wherein components A and B are present in a mixing ratio of 20:1 to 1:200. 4. A method for preventing and controlling phytopathogenic harmful fungi, comprising treating fungi, its habitat or materials, plants, seeds, soil that need to be prevented and controlled from fungal infestation with the fungicidal mixture required by any one of claims 1-3 , area or space, wherein the application of compound I and compound II can be carried out simultaneously or sequentially. 5. The method as claimed in claim 4, wherein the harmful fungus, its habitat or plants, seeds, soil, areas, materials or spaces that need to be prevented and controlled are treated with 0.005-1kg/ha as claimed in claim 1 or 2 Said Compound I treatment. 6. The method as claimed in claim 4, wherein harmful fungi, its habitat or plants, seeds, soil, areas, materials or spaces that need to be prevented and controlled are treated with 0.01-1kg/ha of the fungus as claimed in claim 1 Compound II treatment.