WO2009043686A2

WO2009043686A2 - Fungicidal mixtures

Info

Publication number: WO2009043686A2
Application number: PCT/EP2008/061809
Authority: WO
Inventors: Ulf Groeger; Egon Haden; Siegfried Strathmann; Matthias NIEDENBRÜCK
Original assignee: Basf Se
Priority date: 2007-09-27
Filing date: 2008-09-05
Publication date: 2009-04-09
Also published as: AR068572A1; UY31368A1; WO2009043686A3

Abstract

The invention relates to fungicidal mixtures containing kresoxim-methyl and simeconazole as the active components in a synergistically effective amount. The invention also relates to methods for controlling fungal pests, using the active substances, and to the use of the active substances for producing such mixtures, and to agents containing said mixtures.

Description

Fungicidal mixtures

description

The present invention relates to fungicidal mixtures containing as active components

1) kresoxime-methyl of the formula I,

and

2) simeconazole of formula II,

in a synergistically effective amount.

In addition, the invention relates to a method for controlling harmful fungi with mixtures of the compound I with the compound II and the use of the compounds düng I with the compound II for the preparation of such mixtures and compositions containing these mixtures.

The strobilurin active ingredient kresoxime-methyl described above as component 1 is (E) -methoxyimino [α- (o-tolyloxy) -o-tolyl] -acetic acid methyl ester, its preparation and its action against harmful fungi are known from the literature (EP-A 253 213). , The strengthening and crop-increasing effect of strobilurin active ingredients on plants is also known (US Pat. No. 7,098,170).

The active ingredient simeconazole mentioned above as component 2 is (RS) -2- (4-fluorophenyl) -1- (1 / - / - 1, 2,4-triazol-1-yl) -3- (trimethylsilyl) propane-2 -ol, its production and action against harmful fungi is also known (Proc. BCPC Conf. - Pests Dis., Vol. 2, p. 557 (2000)).

With regard to a reduction of the application rates and a widening of the spectrum of action of the known compounds, the present invention The object of the invention is to provide an improved action against harmful fungi, in particular for certain indications, with a reduced total amount of applied active substances.

Accordingly, the mixtures defined above were found. It has also been found that with simultaneous joint or separate application of the compound I and the compound II or when using the compound I and the compound II successively control fungi better than with the individual compounds (synergistic mixtures). By simultaneous joint or separate application of the compound I with the compound II, the fungicidal activity is increased to a superadditive extent.

The mixtures of the compound I and the compound II, or the simultaneous joint or separate use of the compound I and the compound II are distinguished by a strengthening and crop-increasing effect on plants, in particular legumes, and an outstanding activity against a broad spectrum of phytopathogenic fungi, in particular of the class of the Ascomycetes, Deuteromycetes, Basidiomycetes and Peronosporomycetes (Syn. Oomycetes). They are partially systemically effective and can be used in crop protection as foliar, pickling and soil fungicides.

They have a particularly high effectiveness in combating a variety of fungi on various crops such as bananas, cotton, vegetables (eg cucumbers, beans and pumpkins), barley, grass, oats, coffee, potatoes, corn, fruit plants, rice, rye, soybeans , Tomatoes, wine, wheat, ornamental plants, sugar cane and a variety of seeds, especially in soy and rice. In addition, they have special significance for the control of fungi in cereals, such as wheat, in particular Septoria species.

In particular, they are suitable for controlling the following plant diseases:

Alternaria species on vegetables, oilseed rape, sugarbeet, fruit, rice, soybeans, as well as on potatoes (for example A. solani or A. alternata) and tomatoes (for example A. solani or A. alternata) and Alternaria ssp. (Earhocks) on wheat, Aphanomyces species on sugar beet and vegetables, Ascochyta species on cereals and vegetables e.g. Ascochyta tritici (leaf drought) on wheat, Bipolaris and Drechslera species on maize (eg D. maydis), cereals, rice and turf, Blumeria graminis (powdery mildew) on cereals (eg wheat or barley), Botrytis cinerea (gray horse) on strawberries , Vegetables, flowers, vines and wheat (cereal), Bremia lactucae on salad,

Cercospora species on corn, rice, sugar beets and, for example, Cercospora sojina (leaf spot) or Cercospora kikuchii (leaf spot) on soybeans, Cladosporium herbarum (earwars) on wheat,

Cochliobolus species on corn, cereals (e.g., Cochliobolus sativus) and rice (e.g., Cochliobolus miyabeanus),

Colletotricum species on cotton and e.g. Colletotrichum truncatum (antracnose) on soybeans

Corynespora cassiicola (leaf spot) on soybeans,

Dematophora necatrix (root / stem rot) on soybeans,

Diaporthe phaseolorum (stalk disease) on soybeans,

Drechslera species, Pyrenophora species on maize, cereals, rice and turf, barley (e.g., D. teres) and wheat (e.g., D. tritici-repentis),

Esca on grapevine caused by Phaeoacremonium chlamydosporium, Ph. Ale- ophilum, and Formitipora punctata (syn. Phellinus punctatus),

Elsinoe ampelina on grapevine,

Epicoccum spp. (Earhorses) on wheat, Exserohilum species on maize,

Erysiphe cichoracearum and Sphaerotheca fuliginea on cucurbits,

Fusarium and Verticillium species on different plants: e.g. F. graminearum or

F. culmorum (root rot) on cereals (e.g., wheat or barley) or e.g. F. oxysporum on tomatoes and Fusarium solani (stalk disease) on soybean Gaeumanomyces graminis (root black) on cereals (for example wheat or barley),

Gibberella species on cereals and rice (e.g., Gibberella fujikuroi),

Glomerella cingulata on grapevine and other plants,

Grainstaining complex on rice,

Guignardia budwelli on grapevine, Helminthosporium species on maize and rice, Isariopsis clavispora on grapevine,

Macrophomina phaseolina (root / stem rot) on soybeans,

Michrodochium nivale (snow mold) on cereals (for example wheat or barley),

Microsphaera diffusa (powdery mildew) on soybeans, Mycosphaerella species on cereals, bananas and peanuts, e.g. M. graminicola on wheat or M. fijiensis on bananas,

Peronospora species on cabbage (e.g., P. brassicae), bulbous plants (e.g., P. destructor), and e.g. Peronospora manshurica (downy mildew) on soybeans

Phakopsara pachyrhizi (soybean rust) and Phakopsara meibomiae (soybean rust) on soya beans,

Phialophora gregata (stalk disease) on soybeans

Phomopsis species on sunflowers, grapevine (e.g., P. viticola) and soybean (e.g.

Phomopsis phaseoli),

Phytophthora species on various plants e.g. P. capsici on peppers, Phytopthora megasperma (leaf / stem rot) on soybeans, Phytophthora infestans on potatoes and tomatoes,

Plasmopara viticola on vines, Podosphaera leucotricha on apple,

Pseudocercosporella herpotrichoides (straw break) on cereals (wheat or barley), Pseudoperonospora on various plants e.g. P. cubensis on cucumber or P. humili on hops, pseudo-pedicel tracheiphilai on grapevine,

Puccinia species on various plants e.g. P. triticina, P. striformins, P. hordei or P. graminis on cereals (for example wheat or barley) or asparagus (for example P. asparagi),

Pyricularia oryzae, Corticium sasakii, Sarocladium oryzae, S. attenuatum, Pyrenophora tritici-repentis (leaf drought) on wheat or Pyrenophora teres (net spots) on barley, Entyloma oryzae on rice, Pyricularia grisea on lawn and cereals, Pythium spp. on lawn, rice, maize, wheat, cotton, oilseed rape, sunflowers, sugar beet, vegetables and other plants (eg P. ultiumum or P. aphanidermatum), Ramularia collo-cygni (Ramularia / sunburn complex / Physiological leaf spots) Barley,

Rhizoctonia species on cotton, rice, potatoes, turf, corn, oilseed rape, potatoes, sugar beets, vegetables and various other plants, e.g. Rhizoctonia solani (root / stem rot) on soybeans or Rhizoctonia cerealis (pointed eye spot) on wheat or barley,

Rhynchosporium secalis on barley, rye and triticale, Sclerotinia species on rape, sunflower and e.g. Sclerotinia sclerotiorum (stalk disease) or Sclerotinia rolfsii (stalk disease) on soybeans, Septoria glycines (leaf stain) on soybeans,

Septoria tritici (Blattseptoria) and Stagonospora nodorum on wheat, Erysiphe (syn. Uncinula) necator on grapevine, Setospaeria species on corn and turf, Sphacelotheca reilinia on corn, Stagonospora nodorum (Ear septoria) on wheat, Thievaliopsis species on soybean and cotton, Tilletia species on cereals,

Typhula incarnata (snow) on wheat or barley, Ustilago species on cereals, maize (e.g., U. maydis) and sugarcane, Venturia species (scab) on apples (e.g., V. inaequalis) and pears.

The mixtures of compounds I and II are also suitable for controlling harmful fungi in the protection of materials (eg wood, paper, paint dispersions, fibers or fabrics) and in the protection of stored products. In wood preservation, particular attention is paid to the following harmful fungi: Ascomycetes such as Ophiostoma spp., Ceratocystis spp., Aureosidium pullulans, Sclerophoma spp., Chaetomium spp., Humicola spp., Petriella spp., Trichurus spp .; Basidiomycetes such as Coniophora spp., Coriolus spp., Gloeophyl lum spp., Lentinus spp., Pleurotus spp., Poria spp., Serpula spp. and Tyromyces spp., Deuteromycetes such as Aspergillus spp., Cladosporium spp., Penicillium spp., Trichoderm spp., Alternaria spp., Paecilomyces spp. and Zygomycetes such as Mucor spp., moreover, in the protection of the following yeasts: Candida spp. and Saccharomyces cerevisae.

The compounds I and II can be applied simultaneously together or separately or one after the other, the sequence in the case of separate application generally having no effect on the control result.

In certain circumstances, it may be advantageous to add one or more other active ingredients to the active ingredients I and II.

Such further active ingredients in the above sense are preferably selected from the following list:

azoles

- triazoles: bitertanol, bromuconazoles, cyproconazole, difenoconazole, diniconazole, enilconazole, epoxiconazole, fenbuconazole, flusilazole, fluquinconazole, flutriol, hexaconazole, imibenconazole, ipconazole, metconazole, myclobutanil, penconazole, propiconazole, prothioconazole, tebuconazole, tetraconazole, triadimenol , Triadimefon, triticonazole;

- imidazoles: cyazofamide, imazalil, pefurazoate, prochloraz, triflumizole;

Benzimidazoles: benomyl, carbendazim, fuberidazole, thiabendazole; - Other: Ethaboxam, Etridiazole, Hymexazole;

strobilurins

Azoxystrobin, Dimoxystrobin, Enestroburin, Fluoxastrobin, Metominostrobin, Picoxy-strobin, Pyraclostrobin, Trifloxystrobin, Orysastrobin, (2-Chloro-5- [1- (3-methylbenzyl-oxyimino) -ethyl] -benzyl) -carbamic acid methyl ester, (2 Ethyl chloro-5- [1- (6-methyl-pyridin-2-ylmethoxyimino) -ethyl] -benzyl) -carbamic acid, 2- (ortho- (2,5-dimethyl-phenyl-oxymethylene) -phenyl) -3- methoxy-methyl acrylate;

carboxamides

- Carboxylic acid anilides: benalaxyl, benodanil, boscalid, carboxin, mepronil, fenfuram, fenhexamide, flutolanil, furametpyr, metalaxyl, ofurace, oxadixyl, oxycarboxin,

Penthiopyrad, thifluzamide, tiadinil, 4-difluoromethyl-2-methyl-thiazole-5-carboxylic acid (4'-bromo-biphenyl-2-yl) -amide, 4-difluoromethyl-2-methyl-thiazole-5-carboxylic acid - (4'-trifluoromethyl-biphenyl-2-yl) -amide, 4-difluoromethyl-2-methyl-thiazole-5-carboxylic acid (4'-chloro-3'-fluoro-biphenyl-2-yl) - amide, 3-Difluoromethyl-1-methyl-pyrazole-4-carboxylic acid (3 ', 4'-dichloro-4-fluoro-biphenyl-2-yl) -amide, 3,4-dichloro-isothiazole-5 carboxylic acid (2-cyanophenyl) amide, N- (4'-bromobiphenyl-2-yl) -4-difluoromethyl-2-methylthiazole-5-carboxamide, N- (4'-trifluoromethylbiphenyl-2 yl) -4-difluoromethyl-2-methyl thiazole-5-carboxamide, N- (4'-chloro-3'-fluorobiphenyl-2-yl) -4-difluoromethyl-2-methylthiazole-5-carboxamide, N- (3 \ 4'-dichloro-4- fluorobiphenyl-2-yl) -3-difluoromethyl-1-methyl-pyrazole-4-carboxamide, N- (3 ', 4'-dichloro-5-fluorobiphenyl-2-yl) -3-difluoromethyl-1-methylpyrazole-4 carboxamide; 3,4-dichloro-N- (2-cyanophenyl) isothiazole-5-carboxamide; N- (2 ', 4'-difluorobiphenyl-2-yl) -1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxamide; N- (2 ', 4'-dichlorobiphenyl-2-yl) -1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxamide; N- (2 ', 4'-difluorobiphenyl-2-yl) -3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxamide; N- (2 ', 4'-dichlorobiphenyl-2-yl) -3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxamide; N- (2 ', 5'-difluorobiphenyl-2-yl) -1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxamide; N- (2 ', 5'-dichlorobiphenyl-2-yl) -1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxamide; N- (2 ', 5'-difluorobiphenyl-2-yl) -3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxamide; N- (2 ', 5'-dichlorobiphenyl-2-yl) -3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxamide; N- (3 ', 5'-difluorobiphenyl-2-yl) -1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxamide; N- (3 ', 5'-dichlorobiphenyl-2-yl) -1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxamide, N- (3', 5'-difluorobiphenyl-2-yl) 3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxamide; N- (3 ', 5'-dichlorobiphenyl-2-yl) -3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxamide; N- (3'-fluorobiphenyl-2-yl) -1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxamide, N- (3'-chlorobiphenyl-2-yl) -1-methyl-3-trifluoromethyl -1 H -pyrazole-4-carboxamide; N- (3'-fluorobiphenyl-2-yl) -3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxamide, N- (3'-chlorobiphenyl-2-yl) -3-difluoromethyl-1 -methyl-1H-pyrazole-4-carboxamide; N- (2'-fluorobiphenyl-2-yl) -1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxamide; N- (2'-chlorobiphenyl-2-yl) -1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxamide; N- (2'-fluorobiphenyl-2-yl) -3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxamide; N- (2'-chlorobiphenyl-2-yl) -3-difluoro-methyl-1-methyl-1H-pyrazole-4-carboxamide; N- (2'-fluoro-4'-chloro-5'-methyl-biphenyl-2-yl) -1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxamide; N- (3 ', 4', 5'-trifluorobiphenyl-2-yl) -1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxamide; N- (3 ', 4', 5'-trifluorobiphenyl-2-yl) -1-methyl-3-difluoromethyl-1H-pyrazole-4-carboxamide; N- (2 ', 4', 5'-trifluorobiphenyl-2-yl) -1-methyl-3-difluoromethyl-1H-pyrazole-4-carboxamide; N- (3 ', 4', 5'-trifluorobiphenyl-2-yl) -3-chlorofluoromethyl-1-methyl-1H-pyrazole-4-carboxamide; N- [2- (1,1,3,3,3-hexafluoropropoxy) phenyl] -1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxamide; N- [2-

(1,1,3,3,3-hexafluoropropoxy) -phenyl] -3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxamide, N- [2- (2-chloro-1, 1,2-trifluoroethoxy) phenyl] -1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxamide; N- [2- (2-chloro-1,1,2-trifluoroethoxy) phenyl] -3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxamide; N- [2- (1,1,2,2-tetrafluoroethoxy) phenyl] -3-difluoro-methyl-1-methyl-1H-pyrazole-4-carboxamide; N- [2- (1,1,2,2-tetrafluoroethoxy) phenyl] -1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxamide; N- (4 '- (trifluoromethylthio) biphenyl-2-yl) -3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxamide; N- (4 '- (trifluoro-methylthio) -biphenyl-2-yl) -1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxamide; 5-Fluoro-1,3-dimethyl-1H-pyrazole-4-carboxylic acid [2- (1, 2-dimethyl-propyl) -phenyl] -amide; - Carboxylic acid morpholides: Dimethomorph, Flumorph;

Benzoic acid amides: flumetover, fluopicolide (picobenzamide), zoxamide; - Other carboxamides: carpropamide, diclocymet, mandipropamide, flumetone, carpropamide, N- (2- {4- [3- (4-chlorophenyl) prop-2-ynyloxy] -3-methoxyphenyl} ethyl) -2- methanesulfonylamino-3-methylbutyramide, N- (2- {4- [3- (4-chlorophenyl) -prop-2-ynyloxy] -3-methoxyphenyl} ethyl) -2-ethanesulfonylamino-3-methyl-butyramide;

Nitrogen-containing heterocyclyl compounds

Pyridines: Pyrifenox, 3- [5- (4-Chloro-phenyl) -2,3-dimethyl-isoxazolidin-3-yl] -pyridine;

Pyrimidines: bupirimate, cyprodinil, ferimzone, fenarimol, mepanipyrim, nuarimol, pyrimethanil; - Piperazine: Triforine "

- Pyrroles: fludioxonil, fenpiclonil;

- Morpholines: aldimorph, dodemorph, fenpropimorph, tridemorph;

Dicarboximides: iprodione, procymidone, vinclozolin;

- Other: acibenzolar-S-methyl, anilazine, captan, captafol, dazomet, diclomethine, fenoxanil, folpet, fenpropidin, famoxadone, fenamidone, octhilinone, probenazole, proquinazide, pyroquilon, quinoxyfen, tricyclazole, 5-chloro-7- ( 4-methyl-piperdin-1-yl) -6- (2,4,6-trifluorophenyl) - [1,2,4] triazolo [1,5-a] pyrimidine, 5-chloro-7- (4-Methylpiperidin-1-yl) -6- (2,4,6-trifluorophenyl) - [1,2,4] triazolo [1,5-a] pyrimidine, 6- (3,4-dichloro-phenyl) -5-methyl- [1,2,4] triazolo [1,5-a] pyrimidin-7-ylamine, 6- (4-tert-butylphenyl) -5-methyl- [1,2,4] triazolo [1, 5-a] pyrimidin-7-ylamine, 5-methyl-6- (3,5,5-trimethyl-hexyl) - [1, 2,4] triazolo [1,5-a] pyrimidine 7-ylamine, 5-methyl-6-octyl- [1,2,4] triazolo [1,5-a] pyrimidin-7-ylamine, 6-methyl-5-octyl- [1, 2,4] triazolo [1,5-a] pyrimidin-7-yl-amine, 6-ethyl-5-octyl- [1,2,4] triazolo [1,5-a] pyrimidin-7-ylamine, 5-ethyl-6 octyl- [1,2,4] triazolo [1,5-a] pyrimidin-7-ylamine, 5-ethyl-6- (3,5,5-trimethyl-hexyl) - [1, 2,4] tri azolo [1,5-a] pyrimidin-7-ylamine, 6-octyl-5-propyl- [1, 2,4] triazolo [1,5-a] pyrimidin-7-yl-amine, 5-methoxymethyl-6-octyl- [1,2,4] triazolo [1,5-a] pyrimidin-7-ylamine, 6 -Octyl-5-trifluoromethyl- [1,2,4] triazolo [1,5-a] pyrimidin-7-ylamine and 5-trifluoromethyl-6- (3,5,5-trimethyl-hexyl) - [1, 2 , 4] triazolo [1,5-a] pyrimidin-7-ylamine, 2-butoxy-6-iodo-3-propyl-chromen-4-one, 3- (3-bromo-6-fluoro-2-methyl) indole-1-sulfonyl) - [1, 2,4] triazole-1-sulfonic acid dimethylamide;

Carbamates and dithiocarbamates

Dithiocarbamates: Ferbam, Mancozeb, Maneb, Metiram, Metam, Propineb, Thiram, Zineb, Ziram; Carbamates: diethofencarb, flubenthiavalicarb, iprovalicarb, propamocarb,

Methyl 3- (4-chlorophenyl) -3- (2-isopropoxycarbonylamino-3-methylbutyrylamino) propionate, N- (1- (1 - (4-cyanophenyl) ethanesulfonyl) -but-2-yl) -carbamic acid (4-fluorophenyl) ester;

Other fungicides

- guanidines: dodine, iminoctadine, guazatine;

- Antibiotics: Kasugamycin, Polyoxins, Streptomycin, Validamycin A; Organometallic compounds: fentin salts;

Sulfur-containing heterocyclyl compounds: isoprothiolanes, dithianone;

Organophosphorus compounds: edifenphos, fosetyl, fosetyl-aluminum, Iprobenfos, pyrazophos, tolclofos-methyl, phosphorous acid and their salts; Organochlorine compounds: thiophanates methyl, chlorothalonil, dichlofluanid, toluylfluanid, flusulfamides, phthalides, hexachlorobenzene, pencycuron, quintozene;

Nitrophenyl derivatives: binapacryl, dinocap, dinobuton;

- Inorganic active substances: Bordeaux broth, copper acetate, copper hydroxide, copper oxychloride, basic copper sulphate, sulfur; - Other: Spiroxamine, Cyflufenamid, Cymoxanil, Metrafenone.

The active compounds can also be used in the form of their agriculturally acceptable salts. Usually come for alkali or alkaline earth salts, such as sodium, potassium or calcium salts in question.

The compound I and the compound II are usually used in a weight ratio of 100: 1 to 1: 100, preferably 20: 1 to 1:20, in particular 10: 1 to 1:10 applied.

If desired, the further active components are added to compound I in a ratio of from 20: 1 to 1:20.

Depending on the nature of the compound and the desired effect, the application rates of the mixtures according to the invention are from 5 g / ha to 2000 g / ha, preferably from 50 to 900 g / ha, in particular from 50 to 750 g / ha.

The application rates for the compound I are accordingly generally 1 to 1000 g / ha, preferably 10 to 900 g / ha, in particular 20 to 750 g / ha.

The application rates for the active compound II are correspondingly generally 1 to 2000 g / ha, preferably 10 to 900 g / ha, in particular 40 to 500 g / ha.

In seed treatment, e.g. By dusting, coating or impregnating seeds, in general application rates of mixture of 1 to 1000 g / 100 kg of seed, preferably 1 to 750 g / 100 kg, in particular 5 to 500 g / 100 kg are used.

When used in material or storage protection, the application rate of active ingredient depends on the type of application and the desired effect. Usual application rates in material protection are, for example, 0.001 g to 2 kg, preferably 0.005 g to 1 kg of active ingredient per cubic meter of material treated. The method for controlling harmful fungi is by the separate or combined application of the compound I and the compound II or the mixtures of the compound I and the compound II by spraying or dusting the seeds, the plants or the soil before or after sowing the plants or before or after emergence of the plants.

The mixtures according to the invention, or compound I and compound II, can be converted into the customary formulations, e.g. Solutions, emulsions, suspensions, dusts, powders, pastes and granules. The application form depends on the respective purpose; It should in any case ensure a fine and uniform distribution of the compound according to the invention.

The formulations are prepared in a known manner, e.g. by stretching the active compound with solvents and / or excipients, if desired with use of emulsifiers and dispersants. Suitable solvents / auxiliaries are essentially:

• water, aromatic solvents (eg Solvesso products, xylene), paraffins (eg petroleum fractions), alcohols (eg methanol, butanol, pentanol, benzyl alcohol), ketones (eg cyclohexanone, gamma-butyrolactone), pyrrolidones (NMP, NOP), Acetates (glycol diacetate), glycols, dimethyl fatty acid amides, fatty acids and fatty acid esters.

In principle, solvent mixtures can also be used

Carriers such as ground natural minerals (e.g., kaolins, clays, talc, chalk) and ground synthetic minerals (e.g., fumed silica, silicates); Emulsifiers such as nonionic and anionic emulsifiers (e.g., polyoxyethylene fatty alcohol ethers, alkyl sulfonates and aryl sulfonates) and dispersants such as lignin

Sulfite liquors and methylcellulose.

The surface-active substances used are alkali metal, alkaline earth metal, ammonium salts of lignin sulfonic acid, naphthalenesulfonic acid, phenolsulfonic acid, dibutylnaphthalenesulfonic acid, alkylarylsulfonates, alkyl sulfates, alkyl sulfonates, fatty alcohol sulfates, fatty acids and sulfated fatty alcohol glycol ethers, and condensation products of sulfonated naphthalene and naphthalene derivatives with formaldehyde , Condensation products of naphthalene or naphthalenesulfonic acid with phenol and formaldehyde, polyoxyethylene octylphenol ether, ethoxylated isooctylphenol, octylphenol, nonylphenol, alkylphenol polyglycol ethers, tributylphenyl polyglycol ethers, tristerylphenyl polyglycol ethers, alkylaryl polyether alcohols, alcohol and fatty alcohol ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers, ethoxylated polyoxypropylene , Laurylalkoholpoly- glycol ether acetal, sorbitol esters, Ligninsulfitablaugen and methyl cellulose into consideration.

For the production of directly sprayable solutions, emulsions, pastes or oil dispersions, mineral oil fractions of medium to high boiling point, such as kerosene or diesel oil, also coal tar oils and oils of vegetable or animal origin. Crack, aliphatic, cyclic and aromatic hydrocarbons, for example toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes or their derivatives, methanol, ethanol, propanol, butanol, cyclohexanol, cyclohexanone, isophorone, strongly polar solvents, for example dimethylsulfoxide, N-methylpyrrolidone or water into consideration.

Powders, dispersants and dusts may be prepared by mixing or co-grinding the active substances with a solid carrier.

Granules, e.g. Coated, impregnated and homogeneous granules can be prepared by binding the active compounds to solid carriers. Solid carriers are e.g. Mineral earths, such as silica gels, silicates, talc, kaolin, attaclay, limestone, lime, chalk, bolus, loess, clay, dolomite, diatomaceous earth, calcium and magnesium sulphate, magnesium oxide, ground plastics, fertilizers, e.g. Ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas and vegetable products such as cereal flour, bark, wood and nutshell flour, cellulose powder and other solid carriers.

The formulations generally contain between 0.01 and 95 wt .-%, preferably between 0.1 and 90 wt .-% of the active ingredient. The active ingredients are used in a purity of 90% to 100%, preferably 95% to 100% (according to NMR spectrum).

Examples of formulations are: 1. Products for dilution in water

A Water-soluble concentrates (SL, LS)

10 parts by weight of the active ingredients are dissolved with 90 parts by weight of water or a water-soluble solvent. Alternatively, wetting agents or other adjuvants are added. When diluted in water, the active ingredient dissolves. This gives a formulation with 10 wt .-% active ingredient content.

B Dispersible Concentrates (DC)

20 parts by weight of the active compounds are dissolved in 70 parts by weight of cyclohexanone with the addition of 10 parts by weight of a dispersant, e.g. Polyvinylpyrrolidone dissolved. Dilution in water gives a dispersion. The active ingredient content is 20% by weight

C Emulsifiable Concentrates (EC)

15 parts by weight of the active compounds are dissolved in 75 parts by weight of xylene with addition of calcium dodecylbenzenesulfonate and castor oil ethoxylate (in each case 5 parts by weight). Dilution in water results in an emulsion. The formulation has 15% by weight active ingredient content. D emulsions (EW, EO, ES)

25 parts by weight of the active compounds are dissolved in 35 parts by weight of xylene with addition of calcium dodecylbenzenesulfonate and castor oil ethoxylate (in each case 5 parts by weight). This mixture is added to water by means of an emulsifying machine (e.g., Ultraturax) in 30 parts by weight and made into a homogeneous emulsion. Dilution in water results in an emulsion. The formulation has an active ingredient content of 25% by weight.

E suspensions (SC, OD, FS)

20 parts by weight of the active ingredients are comminuted with the addition of 10 parts by weight of dispersants and wetting agents and 70 parts by weight of water or an organic solvent in a stirred ball mill to a fine active substance suspension. Dilution in water results in a stable suspension of the active ingredient. The active ingredient content in the formulation is 20% by weight.

F Water-dispersible and water-soluble granules (WG, SG)

50 parts by weight of the active ingredients are finely ground with the addition of 50 parts by weight of dispersants and wetting agents and prepared by means of technical equipment (for example extrusion, spray tower, fluidized bed) as water-dispersible or water-soluble granules. Dilution in water results in a stable dispersion or solution of the active substance. The formulation has an active ingredient content of 50% by weight.

G Water-dispersible and water-soluble powders (WP, SP, SS, WS) 75 parts by weight of the active compounds are ground in a rotor-stator mill with the addition of 25 parts by weight of dispersing and wetting agents and silica gel. Dilution in water results in a stable dispersion or solution of the active ingredient. The active ingredient content of the formulation is 75% by weight.

H gel formulations (GF)

In a ball mill, 20 parts by weight of the active ingredients, 10 parts by weight of dispersant, 1 part by weight of swelling agent ("gelling agent") and 70 parts by weight of water or of an organic solvent are ground to a fine suspension the dilution with water gives a stable suspension with 20 wt .-% active ingredient content.

2. Products for direct application

I dusts (DP, DS)

5 parts by weight of the active ingredients are finely ground and intimately mixed with 95 parts by weight of finely divided kaolin. This gives a dust with 5 wt .-% active ingredient content.

J Granules (GR, FG, GG, MG)

0.5 parts by weight of the active ingredients are finely ground and treated with 99.5 parts by weight of connected. Common processes are extrusion, spray drying or fluidized bed. This gives a granulate for direct application with 0.5 wt .-% active ingredient content.

K ULV solutions (UL)

10 parts by weight of the active compounds are dissolved in 90 parts by weight of an organic solvent, e.g. XyIoI solved. This gives a product for direct application with 10 wt .-% active ingredient content.

For seed treatment, water-soluble concentrates (LS), suspensions (FS), dusts (DS), water-dispersible and water-soluble powders (WS, SS), emulsions (ES), emulsifiable concentrates (EC) and gel formulations (GF) are usually used. These formulations can be applied to the seed undiluted or, preferably, diluted. The application can be done before sowing.

The active compounds may be used as such, in the form of their formulations or the forms of use prepared therefrom, e.g. in the form of directly sprayable solutions, powders, suspensions or dispersions, emulsions, oil dispersions, pastes, dusts, litter, granules by spraying, misting, dusting, scattering or pouring. The forms of application depend entirely on the intended use; In any case, they should ensure the finest possible distribution of the active compounds according to the invention.

Aqueous application forms can be prepared from emulsion concentrates, pastes or wettable powders (spray powders, oil dispersions) by adding water. For the preparation of emulsions, pastes or oil dispersions, the substances, as such or dissolved in an oil or solvent, can be homogenized in water by means of wetter, tackifier, dispersant or emulsifier. However, it is also possible to prepare from active substance wetting, adhesion, dispersing or emulsifying agents and any solvents or oil concentrates which are suitable for dilution with water.

The active compound concentrations in the ready-to-use preparations can be varied within wide ranges. In general, they are between 0.0001 and 10%, preferably between 0.01 and 1%.

The active ingredients can also be used with great success in the ultra-low-volume (ULV) process, it being possible to apply formulations containing more than 95% by weight of active ingredient or even the active ingredient without additives.

The active substances may include oils of various types, wetting agents, adjuvants, herbicides, fungicides, other pesticides, bactericides, if appropriate also only be added immediately before application (tank mix). These agents can be added to the compositions according to the invention in a weight ratio of 1: 100 to 100: 1, preferably 1:10 to 10: 1.

applications

The fungicidal activity of the compounds and the mixtures can be demonstrated by the following experiments:

Microtiter tests

The active ingredients were formulated separately or together as stock solution with a concentration of 10,000 ppm in DMSO. The active ingredient simeconazole was used as a commercially available formulation (SANLIT WP, Sankyo Agro) and diluted with water in relation to the active ingredient.

The measured parameters were compared with the growth of the drug-free control variant and the fungus- and drug-free blank to determine the relative growth in% of the pathogens in the individual drugs.

The determined values for the percentage of relative growth were first averaged, then converted into efficiencies as% of the drug-free control variant. Efficiency 0 is the same growth as in the drug-free control variant, efficiency 100 is 0% growth. The efficiencies to be expected for drug combinations were determined according to the Colby formula (Colby, S.R. (Calculating Synergistic and Antagonistic Ac- tions of herbicide Combinations, Weeds, 15, pp. 20-22, 1967) and compared with the observed efficiencies.

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

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

Application Example No. 1 Activity against the causative agent of the late blight Phytophthora infestans in the microtiter test The stock solution was pipetted into a microtiter plate (MTP) and diluted with water to the stated drug concentration. This was followed by the addition of an aqueous pea-based zoospore suspension of Phytophthora infestans. The plates were placed in a water vapor saturated chamber at temperatures of 18 ° C. Using an absorbance photometer, the MTPs were measured at 405 nm on the 7th day after inoculation.

Table A - Single agents

Table B - mixtures according to the invention

^* ) calculated efficiency according to the Colby formula

Greenhouse experiments

The active compounds were prepared separately or together as a stock solution with 25 mg of active ingredient, which with a mixture of acetone and / or DMSO and the emulsifier Uniperol® EL (wetting agent with emulsifying and dispersing action based on ethoxylated alkylphenols) in the volume ratio solvent- Emulsifier from 99 to 1 ad 10 ml was filled. It was then made up to 100 ml with water. This stock solution was diluted with the described solvent-emulsifier-water mixture to the drug concentration given below.

Use Example 2 - Protective efficacy against Septoria leaf spot disease of wheat caused by Septoria tritici

Leaves of potted wheat seedlings of the "Riband" variety were sprayed to drip point with aqueous suspension in the concentration of active compound specified below. The suspension or emulsion was prepared from a stock solution containing 10% active ingredient in a mixture consisting of 85% cyclohexanone and 5% emulsifier. 24 hours after the spray coating had dried on, they were inoculated with an aqueous spore suspension of Septoria tritici. The suspension contained 2.0 x 10 ⁶ spores / ml. The test plants were then placed in the greenhouse at temperatures between 18 and 22 ° C and a relative humidity near 100%. After 2 weeks, the extent of disease development was determined visually in% infestation of the total leaf area.

The visually determined values for the percentage of affected leaf areas were converted into efficiencies as% of the untreated control:

The efficiency (W) is calculated according to the formula of Abbot as follows:

W = (1-α / β) 100

α corresponds to the fungal infestation of the treated plants in% and β corresponds to the fungal infestation of the untreated (control) plants in%

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

The expected efficiencies for drug combinations were determined according to the Colby formula (Colby, S.R. (Calculating Synergistic and Antagonistic Ac- tions of herbicide Combinations, Weeds, 5, p. 20-22, 1967) and compared with the observed efficiencies.

Colby formula:

E = x + y - x-y / 100

Use Example 3 - Curative Efficacy Against Soy Rust Caused By

Phakopsora pachyrhizi

Leaves of potted soybean seedlings were inoculated with a spore suspension of soybean rust (Phakpsora pachyrhizi). Thereafter, the pots were for 24

Hours in a chamber with high humidity (90 to 95%) and 23 to 27 ⁰ C provided. The infected plants were incubated after 2 days with the above described sprayed solution to the dripping point in the concentration of active substance specified below. After the spray coating, the test plants were cultivated in the greenhouse at temperatures between 23 and 27 ⁰ C and 60 to 80% relative humidity for 14 days. Then the extent of rust fungus development on the leaves was determined.

From the results of the experiments, it is clear that the mixtures according to the invention are considerably more effective due to the synergism than predicted by the CoI by formula.

Claims

claims

1. Fungicidal mixtures containing as active components:

1) kresoxime-methyl of the formula I,

and

2) simeconazole of formula II,

in a synergistically effective amount.

2. Fungicidal mixtures according to claim 1, containing the compound of formula I and the compound of formula II in a weight ratio of 100: 1 to 1: 100.

3. Fungicidal mixtures according to claim 1 or 2, containing a further active ingredient.

4. A fungicidal composition containing a liquid or solid carrier and a mixture according to any one of claims 1 to 3.

5. A method for controlling phytopathogenic harmful fungi, which comprises treating the fungi, their habitat or the plants to be protected against fungal attack, the soil or seeds with a synergistically effective amount of the compound I and the compound II according to claim 1.

6. The method according to claim 5, characterized in that the compounds I and II according to claim 1 simultaneously together or separately, or sequentially ausbringt.

7. The method according to claim 5 or 6, characterized in that it is applied in soybean, rice, or cereal crops.

8. The method according to any one of claims 5, 6 or 7, characterized in that one spends the compounds I and II according to claim 1 or the mixture according to one of claims 1 to 4 in an amount of 5 g / ha to 2000 g / ha ,

9. The method according to any one of claims 5, 6 or 7, characterized in that the compounds I and II according to claim 1 or the mixture according to one of claims 1 to 3 in an amount of 1 to 1000 g / 100 kg of seed applies.

10. The method according to any one of claims 5, 6 or 7, characterized in that Septoria species are combated.

1 1. Seed containing a mixture according to any one of claims 1 to 3 in an amount of 1 to 1000 g / 100 kg.

12. Use of the compounds I and II according to claim 1 for the preparation of an agent according to claim 4.