EP2066175A1 - Method for controlling fungal pests - Google Patents

Abstract

A method for controlling fungal pests which display a resistance to carboxamide fungicides consists of applying a fungicidally effective amount of a compound of the general formula (I), where -R means for example: formula (II) or formula (III), and where -X is either -Cl or -F, and where -Z- means for example a group: formula (III), preventively to the plants.

Description

 Method for controlling harmful fungi

description

The present invention relates to a method of controlling harmful fungi having a resistance to carboxylic acid amide fungicides.

For decades, numerous different chemical groups have been used to control harmful fungi on crops such as grain or wine. On the one hand, these compounds are intended to prevent or at least reduce the infestation of crops with harmful fungi and, on the other hand, in the concentration used, do not lead to any lasting damage to the crop.

An economically important group of fungicidal compounds are the so-called carboxylic acid amide fungicides (Carboxylic Acid Amide Fungicids), which u. a. hamper the biosynthesis of phospholipids in the harmful fungi. Carboxylic acid amide fungicides include, but are not limited to, various cinnamic acid amide derivatives (see, for example, U.S. 5,952,496), valinamide carbamates (see, for example, DE 4026966), mandelic acid amides, and other carboxylic acid amide derivatives. Important constituents of commercial products include the carboxylic acid amide fungicides dimethomorph, benthiavalicarb, flumorph, iprovalicarb and mandipropamide.

The cinnamic acid derivatives described in US Pat. No. 5,952,496 have also proven to be of particular importance for the control of harmful fungi. These can be formulated, for example, in solution, as an aqueous emulsion or as a powder preparation and applied in this form to useful plants.

In recent years, practical experience in agriculture has shown that the repeated use of certain fungicidal active substances in the control of harmful fungi can lead to a rapid selection of those fungal strains which have developed a natural or adapted resistance to the active substance in question. Numerous genes allow the fungi to detoxify the fungicides, which makes effective control of these harmful fungi with the active ingredient more difficult.

It has also been found that these fungal strains often also develop cross-resistance to other drugs based on the same mechanism of action. This will require the use of drug types based on a different mechanism of action. However, drugs with a new mechanism of action are only limited available and finding new mechanisms of action is a complicated process. The development of new drugs that show no cross-resistance with the known drugs proves to be time-consuming and costly.

As an important group of fungicides against numerous plant pathogens, active ingredients have been established, which have in common the effect of influencing phospholipid biosynthesis. These compounds practice u. a. an effect on the cell wall of harmful fungi. The above-mentioned carboxylic acid amide fungicides belong to this group of active ingredients.

An object of the present invention is to provide a novel method of controlling harmful fungi that may already have resistance to certain fungicides. The process should be technically easy to use, lead to an efficient prevention or elimination of harmful fungi and can be applied gently to various types of crops.

The object is achieved by a method for controlling harmful fungi which are resistant to individual carboxylic acid amide fungicides, which comprises applying a fungicidally effective amount of a compound of general formula (I) to the plants, the seeds and / or the soils before or after Sowing of the plants or before or after the expiry of the plants applies, which happens in particular preventive.

The process according to the invention uses a fungicidally effective amount of a compound of the general formula (I)

where -R is a radical:

OCH. OC ₂ H ₅ or OCH. C ≡ CH where -X is either -Cl or -F

and

where -Z- means:

CH CO NO

or

CH-co-NH-CH, CH ₂ -

O CK C ≡ CH

The method is particularly suitable for controlling harmful fungi of the Plasmopara type, in particular Plasmopara viticola.

In the method according to the invention for controlling harmful fungi, preference is given to using a compound of the general formula (I) in which

-R means: -OCH ₃ ,

-X means: -Cl or -F

and -Z- means:

CH CO NO

where both the Z isomer, the E isomer or mixtures of both isomers can be used,

or a compound of general formula (I), wherein -R means: OCH ₂ C ≡ CH

-X means: -Cl

and -Z- means:

CH-co-NH-CH ₉ CH,

O CH ₂ C = CH

In the process, the compound of the general formula (I) or a salt of this compound is usually applied in an amount of 1 to 1000 g / ha or in quantities of 1 to 1000 g / 100 kg of seed.

In the method for controlling harmful fungi, the compound of the general formula (I) is preferably applied to the underside of the leaves of the plants to be treated. The treated plants may in particular also be grapevines.

It is also possible to use a compound of general formula (I) in combination with one or more other fungicides, e.g. B. also in combination with another carboxylic acid amide fungicide.

Another object of the invention is the use of a compound of general formula (I) for the preparation of a fungicidal preparation for preventive PiIz- control in crops, especially in already occurred resistances. Likewise, the use of a compound of general formula (I) for the prevention of cross-resistance in fungal control of crops is the subject of this invention.

The abovementioned active compounds of the general formula (I) can be used in particular for controlling Plasmopara viticola, e.g. be used on grapevines.

In addition, the compounds of general formula (I) are also suitable for controlling harmful fungi from the class of Peronosporomyctes (Oomycetes), such as:

a) Peronospora species on cabbage and bulbous plants, such as P. brassicae on cabbage or P. destructor on onion, b) Phytophthora infestans on potatoes and tomatoes,

c) Phytophthora species on various plants, e.g. P.capsici on paprika,

d) Plasmopara viticola on vines,

e) Pseudoperonospora on various plants, e.g. P. cubensis on cucumber or P. humili on hops,

f) Pythium spp. on turf, rice, corn, cotton, oilseed rape, sunflowers, sugar beets, vegetables and other plants such as e.g. P. ultimum on various plants, P. aphanidermatum on lawn,

g) Sclerospora species on various plants, e.g. S. graminicola on millet.

Numerous resistances against carboxylic acid amide fungicides have already been developed in various strains of the aforementioned pathogens. In view of the spread of harmful fungi which have developed resistance, the present invention is based on a control method with which such resistant fungal strains can be controlled inexpensively and effectively with currently available active ingredients.

It is known that the pathogens that have developed resistance to certain drugs are often also cross-resistant to them [see, e.g. Lyr, H .; "Modern Selective Fungicides", Chapter 12, Gustav Fischer Verlag, Jena, Stuttgart, New York (1995)].

Surprisingly, it has now been found that carboxylic acid amide fungicide-resistant harmful fungi can be effectively combated with compounds of the general formula (I) if the compounds are used preventively.

The method according to the invention is preferably suitable for the preventive control of Plasmopara harmful fungi, in particular of Plasmopara viticola strains. Plas- mopara viticola, the downy mildew of the vine, is also known as vine peronospora. On the vine leaves, it first forms roundish, yellowish, oily, translucent spots on the upper side of the leaves, later in humid weather, dense white mushroom grass on the underside.

The infestation spots soon turn brown and dry up. The more damaged leaves fall off prematurely ("leaf fall disease"). In the same way as leaves and young ones Berries can also affect all green vine parts, shoot tips, tendrils and inflorescences. Berries, for example, turn brown and shrink. The fungus Plasmo- para viticola penetrates through the stomata into the tissue of the green Reborgane. The infection then takes place via zoospores floating in a water film. In the vicinity of stomata they settle and form a germ tube. With the help of nutritional organs, the fungus takes valuable food from the host plant.

The disease is of particular economic importance, as an epidemic-like occurrence is possible, and the grape infestation can cause severe loss of yield up to the total loss of the harvest. Furthermore, infestation with Plasmopara increases the frost sensitivity of the vine.

The o. G. The method is applied by treating the fungi or the plants, seeds, materials and / or the soil to be protected against fungal attack with a fungicidally effective amount of the compound of the formula (I). The application can take place before as well as promptly with the infection, but preferably before the infection of the materials, plants or seeds by the fungi.

The compounds of the formula (I) can be prepared by customary processes. They can be converted into the usual 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 ingredient with solvents and / or carriers, if desired using emulsifiers and dispersants.

Suitable solvents / auxiliaries are essentially:

a) 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

b) carriers such as ground natural minerals (eg kaolins, clays, talc, chalk) and ground synthetic minerals (eg fumed silica, silicates); Emulsifiers such as non-ionic and anionic emulsifiers (eg polyoxygenated ethylene fatty alcohol ethers, alkyl sulfonates and arylsulfonates) and dispersants such as lignin-sulphite liquors and methylcellulose.

As surfactants u. a. Alkali, alkaline earth, ammonium salts of lignosulfonic acid, naphthalenesulfonic acid, phenolsulfonic acid, dibutylnaphthalenesulfonic acid, alkylarylsulfonates, alkyl sulfates, alkyl sulfonates, fatty alcohol sulfates, fatty acids and sulfated fatty alcohol glycol used, also condensation products of sulfonated naphthalene and naphthalene derivatives with formaldehyde, condensation products of naphthalene and naphthalenesulfonic acid with phenol and formaldehyde, polyoxyethyleneoctylphenol ethers, ethoxylated isooctylphenol, octylphenol, nonylphenol, alkylphenolpolyglycol ethers, tributylphenylpolyglycol ethers, tristerylphenylpolyglycol ethers, alkylarylpolyether alcohols, alcohol and fatty alcohol-ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers, ethoxylated polyoxypropylene, lauryl alcohol polyglycol ether acetal, sorbitol esters, lignosulphite liquors and methylcellulose.

For the preparation of directly sprayable solutions, emulsions, pastes or oil dispersions, there are mineral oil fractions of medium to high boiling point, such as kerosene or diesel oil, coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, e.g. Toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes or their derivatives, methanol, ethanol, propanol, butanol, cyclohexanol, cyclohexanone, isophorone, strong polar solvents, e.g. 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, tree bark, wood and nutshell meal, cellulose powder and other solid carriers.

Seed treatment formulations may additionally contain binders and / or gelling agents and optionally dyes.

Binders can be added to increase adhesion of the active ingredients to the seed after treatment. Suitable binders are, for example, EO / PO Block copolymer surfactants, but also polyvinyl alcohols, Ppolyvinylpyrrolidone, polyacrylates, polymethacrylates, polybutenes, polyisobutylenes, polystyrenes, polyethyleneamines, Polyethylenamide, polyethylenimines (Lupasol ^®, Polymin ^®), polyethers, polyurethanes, polyvinyl acetates, Tylose and copolymers of these polymers. Is a suitable overall liermittel example, carrageen (Satiagel ^®).

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).

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.

For seed treatment, the formulations in question give, after dilution of from two to ten times, active compound concentrations of from 0.01 to 60% by weight, preferably from 0.1 to 40% by weight, in the ready-to-use preparations.

Examples of common formulations are:

Products for dilution in water

A) Water Soluble Concentrates (SL)

10 parts by weight of a compound I according to the invention 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 an active ingredient content of 10% by weight.

B) Dispersible Concentrates (DC)

20 parts by weight of a compound I according to the invention are dissolved in 70 parts by weight of cyclohexanone with the addition of 10 parts by weight of a dispersant, for example polyvinylpyrrolidone. Dilution in water gives a dispersion. The active ingredient content is 20% by weight. C) Emulsifiable Concentrates (EC)

15 parts by weight of a compound I according to the invention are dissolved in 75 parts by weight of xylene with the 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 an active substance content of 15% by weight.

D) Emulsions (EW, EO)

25 parts by weight of a compound I according to the invention 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 by means of an emulsifying machine (e.g., Ultraturax) in 30 parts by weight of water 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)

20 parts by weight of a compound I according to the invention 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 give 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 a compound I according to the invention are finely ground with the addition of 50 parts by weight dispersing and wetting agents and by means of technical equipment (eg extrusion, spray tower, fluidized bed) as water-dispersible or water-soluble Granules produced. Dilution in water results in a stable dispersion or solution of the active ingredient. The formulation has an active ingredient content of 50% by weight.

G) Water-dispersible and water-soluble powders (WP, SP)

75 parts by weight of a compound I according to the invention 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.

Products for direct application

H) dusts (DP)

5 parts by weight of a compound I according to the invention are finely ground and intimately mixed with 95 parts by weight of finely divided kaolin. This gives a dust with an active ingredient content of 5 wt .-%. J) Granules (GR, FG, GG, MG)

0.5 part by weight of a compound I according to the invention are finely ground and combined with 99.5 parts by weight of carriers. Common processes are extrusion, spray drying or fluidized bed. This gives a granulate for direct application with an active ingredient content of 0.5 wt .-%.

K) ULV solutions (UL)

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

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, scattering agents, 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 (wettable 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. But it can also be made of effective substance wetting, adhesion, dispersing or emulsifying and possibly solvent or oil concentrates, which are suitable for dilution with water.

To the active ingredients oils of various types, wetting agents, adjuvants, herbicides, fungicides, other pesticides, bactericides, possibly also just immediately before use (tank mix), are added. 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.

As an adjuvant in this sense are in particular: organically modified polysiloxanes, eg Break Thru S 240 ^® ; Alcohol alkoxylates, eg. As Atplus 245 ^®, Atplus MBA 1303 ^®, Plurafac LF 300 ^® and Lutensol ON 30 ^®; EO-PO block polymers, eg. B. Pluro- nic RPE 2035 ^® and Genapol B ^®; Alcohol ethoxylates, eg. As Lutensol XP 80 ^®; and sodium dioctylsulfosuccinate, e. B. Leophen RA ^®. The application rates are depending on the application pressure and type of effect desired between 1 and 100Og, preferably 20 and 750g active ingredient per ha. The fungicidal compositions according to the invention generally contain between 0.1 and 95, preferably between 0.5 and 90 wt. -% of one or more active substances. In the seed treatment, in general, amounts of active ingredient of from 1 to 1000 g, preferably from 1 to 200 g, in particular from 5 to 100 g, per kilogram of seed are required. 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 the protection of the material are, for example, from 0.001 g to 2000 g, preferably from 0.005 g to 1000 g of active ingredient per cubic meter of material treated.

In the method according to the invention, the use of compounds of general formula (I) may also be carried out in combination with other active substances, e.g. with herbicides, insecticides, growth regulators, other fungicides or with fertilizers. When mixing the preparations containing the compound of the formula (I) with the other fungicides, enlargement of the fungicidal activity spectrum is obtained in many cases.

The following list of fungicides with which the compounds according to the invention can be used together is intended to explain the possible combinations:

a) strobilurins

Azoxystrobin, dimoxystrobin, enestroburine, fluoxastrobin, kresoxim-methyl, metominostrobin, picoxystrobin, pyraclostrobin, trifloxystrobin, orysastrobin, (2-chloro-5- [1- (3-methyl-benzyloxyimino) -ethyl] -benzyl) -carbamic acid methyl ester, (2-Chloro-5- [1- (6-methylpyridin-2-ylmethoxyimino) ethyl] benzyl) -carbamic acid methyl ester, 2- (ortho- (2,5-dimethylphenyl-oxymethylene) -phenyl) -3- methoxy-methyl acrylate;

b) Carboxylic acid amides

- Carboxylic acid anilides: Benalaxyl, Benodanil, Boscalid, Carboxin, Mepronil, Fenfuram, Fenhexamid, 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'-fluorobiphenyl-2-yl) -amide, 3-difluoromethyl-1-methyl-pyrazole-4-carboxylic acid (3 ' , 4'-dichloro-4-fluoro-biphenyl-2-yl) -amide, 3-difluoromethyl-1-methyl-pyrazole-4-carboxylic acid (3 ', 4'-di-chloro-5-fluoro) biphenyl-2-yl) -amide, 3,4-dichloro-isothiazole-5-carboxylic acid (2-cyano-phenyl) -amide; - Carboxylic acid morpholides: Dimethomorph, Flumorph; Benzoic acid amides: flumetover, fluopicolide (picobenzamide), zoxamide;

Other carboxamides: carpropamide, diclocymet, mandipropamide, N- (2- (4- [3- (4-chloro-phenyl) -prop-2-ynyloxy] -3-methoxyphenyl) -ethyl) -2-methanesulfonylamino 3-methyl-butyramide, N- (2- (4- [3- (4-chloro-phenyl) -prop-2-ynyloxy] -3-methoxy-phenyl) -ethyl) -2-ethanesulfonyl-amino-3-methyl- butyramide;

c) Azoles

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

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

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

d) Nitrogen-containing heterocyclyl compounds

Pyridines: fluazinam, pyrifenox, 3- [5- (4-chlorophenyl) -2,3-dimethylisoxazolidin-3-yl] pyridine; Pyrimidines: bupirimate, cyprodinil, ferimzone, fenarimol, mepanipyrim, nuarimol, pyrimethanil;

- piperazines: triforins;

- Pyrroles: fludioxonil, fenpiclonil;

- Morpholines: aldimorph, dodemorph, fenpropimorph, tridemorph; Dicarboximides: iprodione, procymidone, vinclozolin;

- others: acibenzolar-S-methyl, anilazine, captan, captafol, dazomet, diclomethine, fenoxanil, folpet, fenpropidin, famoxadone, fenamidone, octhilinone, probenazole, proquinazide, pyroquilon, quinoxyfen, tricyclazole, 5-chloro-7- ( 4-methyl-piperidin-1-yl) -6- (2,4,6-trifluorophenyl) - [1,2,4] triazolo [1,5-a] pyrimidine, 2-butoxy-6- iodo-3-propyl-chromen-4-one, 3- (3-bromo-6-fluoro-2-methylindol-1-sulfonyl) - [1, 2,4] triazole-1-sulfonic acid dimethylamide;

e) carbamates and dithiocarbamates

Dithiocarbamates: Ferbam, Mancozeb, Maneb, Metiram, Metam, Propineb, Thiram, Zineb, Ziram;

Carbamates: Diethofencarb, Flubenthiavalicarb, Iprovalicarb, Propamocarb, 3- (4-chlorophenyl) -3- (2-isopropoxycarbonylamino-3-methyl-butyrylamino) -propionic acid methyl ester, N- (1 - (1 - (4-cyanophenyl ethanesulfonyl) -but-2-yl) carbamic acid (4-fluorophenyl) ester; f) 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, toiylfluanid, flusulphamides, 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, Metrafenon.

The active ingredients mentioned as further component, their preparation and their action against harmful fungi are generally known or they are commercially available. In particular, the following compounds are mentioned:

Benalaxyl, methyl Λ / - (phenylacetyl) -Λ / - (2,6-xylyl) -DL-alaninate (DE 29 03 612); Metalaxyl, methyl Λ / - (methoxyacetyl) -Λ / - (2,6-xylyl) -DL-alaninate (GB 15 00 581);

Ofurace, (RS) -α- (2-chloro-Λ / -2,6-xylylacetamido) -γ-butyrolactone [CAS RN 58810-48-3]; Oxadixyl, Λ / - (2,6-dimethylphenyl) -2-methoxy-Λ / - (2-oxo-3-oxazolidinyl) acetamide (GB 20 58 059);

Aldimorph, "4-alkyl-2,5 (or 2,6) -dimethylmorpholine" containing 65-75% 2,6-dimethylmorpholine and 25-35% 2,5-dimethylmorpholine containing more than 85% 4- dodecyl

2,5 (or 2,6) -dimethylmorpholine, wherein "alkyl" also includes octyl, decyl, tetradecyl and

Hexadecyl having a cis / trans ratio of 1: 1 [CAS RN 91315-15-0];

Dodine, 1-dodecylguanidinium acetate (Plant Dis. Rep. 41, p.1029 (1957)); Dodemorph, 4-cyclododecyl-2,6-dimethylmorpholine (DE-A 1198125);

Fenpropimorph, (RS) -c / s-4- [3- (4-tert-butylphenyl) -2-methylpropyl] -2,6-dimethylmorpholine (DE-A 27 52 096);

Fenpropidin, (RS) -I- [3- (4-th / f-butylphenyl) -2-methylpropyl] piperidine (DE-A 27 52 096);

Guazatine, mixture of the reaction products obtained from the amidation of technical lminodi (octamethylene) diamine containing various guanidines and polyamines [CAS RN 108173-90-6];

Iminoctadin, 1, 1 '-lminodi (octamethylene) diguanidine (Congr. Plant Pathol., 1, p

(1968);

Spiroxamine, (8-tert-butyl-1,4-dioxaspiro [4.5] dec-2-yl) diethylamine (EP-A 281 842); Tridemorph, 2,6-dimethyl-4-tridecylmorpholine (DE-A 1 164 152);

Pyrimethanil, 4,6-dimethylpyrimidin-2-yl-phenylamine (DD-A 151 404); Mepanipyrim, (4-methyl-6-prop-1-ynyl-pyrimidin-2-yl) -phenylamine (EP-A 224 339);

Cyprodinil, (4-cyclopropyl-6-methylpyrimidin-2-yl) -phenylamine (EP-A 310550);

Cycloheximide, 4 - {(2R) -2 - [(1S, 3S, 5S) -3,5-dimethyl-2-oxocyclohexyl] -2-hydroxyethyl} piperidine-2,6-dione [CAS RN 66- 81-9]; Griseofulvin, 7-chloro-2 ', 4,6-trimethoxy-6'-methylspiro [benzofuran-2 (3H), 1'-cyclohex-2'-ene] -3,4'-dione [CAS RN 126-07 -8th];

Kasugamycin, 3-O- [2-Amino-4 - [(carboxymiminomethyl) amino] -2,3,4,6-tetradeoxy-α-D-araö / no-hexopyranosyl] -Dc /? / Ro-inositol [CAS RN 6980-18-3];

Natamycin, (8 pounds, 14 pounds, 16 pounds, 18 pounds, 20 pounds) - (1R, 3S, 5RJR, 12R, 22R, 24S, 25R, 26S) -22- (3-amino-3,6 -dideoxy-.beta.-D-mannopyranosyloxy) -1,3,26-trihydroxy-12-methyl-10-oxo-6,1 1, 28-trioxatricyclo [.sub.SI.O] octacosa-.delta.Hi.e.i [theta] O pentaene ^ S-carboxylic acid [CAS RN

7681-93-8];

Polyoxyn, 5- (2-amino-5-O-carbamoyl-2-deoxy-L-xylonamido) -1- (5-carboxy-1,2,3,4-tetrahydro-2,4-dioxopyrimidin-1-yl ) -1, 5-dideoxy-β-D-allofuranuronic acid [CAS RN 22976-86-9];

Streptomycin, 1,1 '- {1-L- (1,3,5 / 2,4,6) -4- [5-deoxy-2-O- (2-deoxy-2-methylamino-α-L- glucopyranosyl) -3-C-formyl-α-L-xyxofuranosyloxy] -2,5,6-trihydroxycyclohex-1, 3-ylene} diguanidine (J. Am. Chem. Soc. 69, p.1234 (1947));

Bitertanol, β - ([1,1'-biphenyl] -4-yloxy) -α- (1, 1-dimethylethyl) -1H-1,2,4-triazole-1-ethanol (DE 23 24 020);

Bromuconazole, 1 - [[4-bromo-2- (2,4-dichlorophenyl) tetrahydro-2-furanyl] methyl] -1H-1, 2,4-triazole (Proc. 1990 Br. Crop. Prot. Conf. - Pests Dis., Vol. 1, p. 459);

Cyproconazole, 2- (4-chlorophenyl) -3-cyclopropyl-1 - [1, 2,4] triazole-1-yl-butan-2-ol

(US 4,664,696); Difenoconazole, 1 - {2- [2-chloro-4- (4-chlorophenoxy) phenyl] -4-methyl- [1,3-dioxolan-2-ylmethyl} -1 H- [1,2,4] triazole ( GB-A 2 098 607);

Diniconazole, (β 1) -β - [(2,4-dichlorophenyl) methylene] -α- (1, 1-dimethylethyl) -1H-1, 2,4-triazole-1-ethanol (Noyaku Kagaku, 1983, Vol. 8, p. 575);

Enilconazole (imazalil), 1 - [2- (2,4-dichlorophenyl) -2- (2-propenyloxy) ethyl] -1H-imidazole (Fruits 28, p. 545, 1973);

Epoxiconazole, (2RS, 3SR) -1 - [3- (2-chlorophenyl) -2,3-epoxy-2- (4-fluorophenyl) propyl] -1 H-

1, 2,4-triazole (EP-A 196 038);

Fenbuconazole, α- [2- (4-chlorophenyl) ethyl] -α-phenyl-1 H-1,2,4-triazole-1-propanenitrile

(Proc., 1988 Br. Crop Prot. Conf. - Pests Dis., Vol. 1, p. 33); Fluquinconazole, 3- (2,4-dichlorophenyl) -6-fluoro-2- [1,2,4] triazole-1-yl-3H-quinazolin-4-one

(Proc. Br. Crop Prot. Conf.-Pests Dis., 5-3, 41 1 (1992));

Flusilazole, 1 - {[bis (4-fluorophenyl) methylsilanyl] methyl} -1 H- [1,2,4] triazole (Proc. Br. Crop

Prot. Conf.-Pests Dis., Vol. 1, p. 413 (1984));

Flutriafol, α- (2-fluorophenyl) -α- (4-fluorophenyl) -1H-1, 2,4-triazole-1-ethanol (EP-A 15 756); Hexaconazole, 2- (2,4-dichlorophenyl) -1 - [1, 2,4] triazole-1-yl-hexan-2-ol

(CAS RN 79983-71-4); Ipconazole, 2 - [(4-chlorophenyl) methyl] -5- (1-methylethyl) -1- (1H-1 _! 2,4-triazol-1-ylmethyl) cyclopentanol (EP-A 267 778),

Metconazole, 5- (4-chlorobenzyl) -2,2-dimethyl-1 - [1, 2,4] triazole-1-ylmethylcyclopentanol

(GB 857,383); Myclobutanil, 2- (4-chlorophenyl) -2- [1, 2,4] triazole-1-ylmethylpentanenitrile

(CAS RN 88671-89-0);

Penconazole, 1- [2- (2,4-dichlorophenyl) pentyl] -1 H- [1,2,4] triazole (Pesticide Manual, 12.

Edition 2000, p. 712);

Propiconazole, 1 - [[2- (2,4-dichlorophenyl) -4-propyl-1,3-dioxolan-2-yl] methyl] -1H-1, 2,4-triazole (BE 835,579);

Prochlorazole, imidazole-1-carboxylic acid-propyl- [2- (2,4,6-trichlorophenoxy) -ethyl] -amide

(US 3,991,071);

Prothioconazole, 2- [2- (1-chlorocyclopropyl) -3- (2-chlorophenyl) -2-hydroxypropyl] -2,4-dihydro- [1,2,4] triazole-3-thione (WO 96/16048) ; Simeconazole, α- (4-fluorophenyl) -α - [(trimethylsilyl) methyl] -1H-1,2,4-triazole-1-ethanol

[CAS RN 149508-90-7],

Tebuconazole, 1- (4-chlorophenyl) -4,4-dimethyl-3- [1,2,4] triazole-1-ylmethylpentan-3-ol

(EP-A 40 345);

Tetraconazole, 1- [2- (2,4-dichlorophenyl) -3- (1,1,2,2-tetrafluoroethoxy) propyl] -1H-1, 2,4-triazole (EP-A 234 242);

Triadimefon, 1- (4-chlorophenoxy) -3,3-dimethyl-1- (1H-1, 2,4-triazol-1-yl) -2-butanone (BE

793 867);

Triadimenol, β- (4-chlorophenoxy) -α- (1, 1-dimethylethyl) -1H-1, 2,4-triazole-1-ethanol (DE-A

23 24 010); Triflumizole, (4-chloro-2-trifluoromethylphenyl) - (2-propoxy-1 - [1, 2,4] triazole-1-yl-ethylidene) -amine (JP-A 79/1 19 462);

Triticonazole, (5 lbs) -5 - [(4-chlorophenyl) methylene] -2,2-dimethyl-1- (1 H -1, 2,4-triazol-1-ylmethyl) cyclopentanol (FR 26 41 277);

Iprodione, 3- (3,5-dichlorophenyl) -2,4-dioxo-imidazolidine-1-carboxylic acid isopropylamide (GB 13 12 536);

Myclozoline, (RS) -3- (3,5-dichlorophenyl) -5-methoxymethyl-5-methyl-1,3-oxazolidine-2,4-dione [CAS RN 54864-61-8];

Procymidone, Λ / - (3,5-dichlorophenyl) -1,2-dimethylcyclopropane-1,2-dicarboximide (US Pat

3,903,090); Vinclozoline, 3- (3,5-dichlorophenyl) -5-methyl-5-vinyl-oxazolidine-2,4-dione (DE-A

22 07 576);

Ferbam, iron (3+) dimethyldithiocarbamate (US 1,972,961);

Nabam, disodium ethylenebis (dithiocarbamate) (U.S. 2,317,765);

Maneb, manganese ethylene bis (dithiocarbamate) (US 2 504 404); Mancozeb, manganese ethylene bis (dithiocarbamate) polymer complex zinc salt

(GB 996 264); Metam, methyldithiocarbamic acid (US 2,791,605);

Metiram, zinc ammonium ethylenebis (dithiocarbamate) (U.S. 3,248,400);

Propineb, zinc propylene bis (dithiocarbamate) polymer (BE 611 960);

Polycarbamate, bis (dimethylcarbamodithioato-κS, κS ') [μ - [[1,2-ethanediylbis [carbamodithioato-κS, κS']] (2 -)]] di [zinc] [CAS RN 64440-88-6 ];

Thiram, bis (dimethylthiocarbamoyl) disulfide (DE-A 642 532);

Ziram, dimethyldithiocarbamate [CAS RN 137-30-4];

Zineb, zinc ethylene bis (dithiocarbamate) (US 2 457 674);

Anilazine, 4,6-dichloro- / V- (2-chlorophenyl) -1 _! 3 _! 5-triazine-2-amine (US 2,720,480); Benomyl, 2-acetylaminobenzimidazole-1-carboxylic acid butylamide (US 3,631,176);

Boscalid, 2-chloro-Λ / - (4'-chlorobiphenyl-2-yl) nicotinamide (EP-A 545 099);

Carbendazim, (1 H-benzimidazol-2-yl) -carbamic acid methyl ester (US 3,657,443);

Carboxin, 5 _! 6-dihydro-2-methyl-Λ-phenyl-1,4-oxathiin-3-carboxamide (US 3,249,499);

Oxycarboxine, 5,6-dihydro-2-methyl-1,4-oxathiin-3-carboxanilide 4,4-dioxide (US 3,399,214);

Cyazofamide, 4-chloro-2-cyano-Λ /, Λ / -dimethyl-5- (4-methylphenyl) -1 / - / - imidazole-1-sulfonamide (CAS RN 120116-88-3];

Dazomet, 3,5-dimethyl-1, 3,5-thiadiazinane-2-thione (Bull Soc Soc. Chim. Fr. Vol. 15, p.

891 (1897)); Diflufenzopyr, 2- {1- [4- (3,5-difluorophenyl) semicarbazono] ethyl} nicotinic acid

[CAS RN 109293-97-2];

Dithianone, 5,10-dioxo-5,10-dihydronaphtho [2,3-b] [1,4] dithiine-2,3-dicarbonitrile

(GB 857,383);

Famoxadone, (/? S) -3-anilino-5-methyl-5- (4-phenoxyphenyl) -1,3-oxazolidine-2,4-dione [CAS RN 131807-57-3];

Fenamidone, (S) -1-anilino-4-methyl-2-methylthio-4-phenylimidazolin-5-one

[CAS RN 161326-34-7];

Fenarimol, α- (2-chlorophenyl) -α- (4-chlorophenyl) -5-pyrimidinemethanol (GB 12 18 623);

Fuberidazole, 2- (2-furanyl) -1 / - / - benzimidazole (DE-A 12 09 799); Flutolanil, α, α, α-trifluoro-3'-isopropoxy-o-toluanilide (JP 1 104514);

Furametpyr, 5-Chloro-Λ / - (1,3-dihydro-1,1,3-trimethyl-4-isobenzofuranyl) -1,3-dimethyl-1H-pyrazole-4-carboxamide [CAS RN 123572-88- 3];

Isoprothiolane, diisopropyl 1, 3-dithiolan-2-ylidenemalonate (Proc. Insectic. Fungic. Conf.

8, Vol. 2, p. 715 (1975)); Mepronil, 3'-isopropoxy-o-toluanilide (U.S. 3,937,840);

Nuarimol, α- (2-chlorophenyl) -α- (4-fluorophenyl) -5-pyrimidinemethanol (GB 12 18 623);

Fluopicolide (picobenzamide), 2,6-dichloro-N- (3-chloro-5-trifluoromethylpyridin-2-ylmethyl) benzamide (WO 99/42447);

Probenazole, 3-allyloxy-1,2-benzothiazole 1,1-dioxide (Agric., Biol. Chem. 37, p.737 (1973);

Proquinazide, 6-iodo-2-propoxy-3-propylquinazolin-4 (3H) -one (WO 97/48684); Pyrifenox, 2 ', 4'-dichloro-2- (3-pyridyl) acetophenone (ZZ) -O-methyloxime (EP 49 854);

Pyroquilone, 1, 2,5,6-tetrahydropyrrolo [3,2,1 -] quinolin-4-one (GB 139 43 373)

Quinoxyfen, 5,7-dichloro-4- (4-fluorophenoxy) quinoline (U.S. 5,240,940);

Silthiofam, Λ / -allyl-4,5-dimethyl-2- (trimethylsilyl) thiophene-3-carboxamide [CAS RN 175217-20-6];

Thiabendazole, 2- (1, 3-thiazol-4-yl) benzimidazole (U.S. 3,017,415);

Thifluzamide, 2 ', 6'-dibromo-2-methyl-4'-trifluoromethoxy-4-trifluoromethyl-1,3-thiazole-5-carboxanilide [CAS RN 130000-40-7];

Thiophanate-methyl, 1, 2-phenylenebis (iminocarbonothioyl) bis (dimethylcarbamate) (DE-A 19 30 540);

Tiadinil, 3-chloro-4,4-dimethyl-1, 2,3-thiadiazole-5-carboxanilide [CAS RN 223580-51-6];

Tricyclazoles, 5-methyl-1,2,4-triazolo [3,4-b] [1,3] benzothiazoles [CAS RN 41814-78-2];

Triforines, Λ /, Λ / '- {piperazine-1, 4-diylbis [(trichloromethyl) methylene]} diformamide

(DE-A 19 01 421); 5-Chloro-7- (4-methyl-piperidine-1-yl) -6- (2,4,6-trifluoro-phenyl) - [1,2,4] triazolo [1,5-a] pyrimidine (WO 98/46607);

Bordeaux broth, mixture of CuSO ₄ × 3Cu (OH) ₂ × 3CaSO ₄ [CAS RN 8011-63-0]

Copper acetate, Cu (OCOCH ₃ ) ₂ [CAS RN 8011-63-0];

Copper oxychloride, Cu ₂ Cl (OH) ₃ [CAS RN 1332-40-7]; Basic copper sulfate, CuSO ₄ [CAS RN 1344-73-6];

Binapacryl, (RS) -2-sec-butyl-4,6-dinitrophenyl 3-methylcrotonate [CAS RN 485-31-4];

Dinocap, a mixture of 2,6-dinitro-4-octylphenyl crotonate and 2,4-dinitro-6-octylphenyl crotonate, where "octyl" is a mixture of 1-methylheptyl, 1-ethylhexyl and 1-

Propylpentyl is (US 2 526 660); Dinobutone, (RS) -2-sec-butyl-4,6-dinitrophenyl isopropyl carbonate [CAS RN 973-21-7];

Nitrothal isopropyl, diisopropyl 5-nitroisophthalate (Proc. Br. Insectic. Fungic. Conf.

Vol. 2, p. 673 (1973));

Fenpiclonil, 4- (2,3-dichlorophenyl) -1H-pyrrole-3-carbonitrile (Proc., 1988 Br. Crop Prot.

Conf. - Pests Dis., Vol. 1, p. 65); Fludioxonil, 4- (2,2-difluorobenzo [1,3] dioxol-4-yl) -1H-pyrrole-3-carbonitrile (The Pesticide

Manual, Ed .: The British Crop Protection Council, 10th Edition 1995, p. 482);

Acibenzolar-S-methyl, methyl 1, 2,3-benzothiadiazole-7-carbothioate

[CAS RN 135158-54-2];

Flubenthiavalicarb (benthiavalicarb), {(S) -1 - [(1 R) - 1- (6-fluorobenzothiazol-2-yl) -ethylcarbamoyl] -2-methylpropyl} -carbamic acid isopropyl ester (JP-A 09/323 984) ;

Carpropamide, 2,2-dichloro-Λ / - [1- (4-chlorophenyl) ethyl] -1-ethyl-3-methylcyclopropanecarboxamide [CAS RN 104030-54-8];

Chlorothalonil, 2,4,5,6-tetrachloroisophthalonitrile (US 3,290,353);

Cyflufenamid, (Z) -Λ / - [α- (Cyclopropylmethoxyimino) -2,3-difluoro-6- (trifluoromethyl) benzyl] -2-phenylacetamide (WO 96/19442);

Cymoxanil, 1- (2-cyano-2-methoxyiminoacetyl) -3-ethylurea (U.S. 3,957,847); Diclomezine, 6- (3,5-dichlorophenyl-p-tolyl) pyridazine-3 (2 / - /) -one (US 4 052 395)

Diclocymet, (RS) -2-cyano- / V - [(/?) - 1- (2,4-dichlorophenyl) ethyl] -3 _! 3 -dimethylbutyramide

[CAS RN 139920-32-4];

Diethofencarb, isopropyl 3,4-diethoxycarbanilate (EP-A 78 663); Edifenphos, O-ethyl S, S-diphenyl phosphorodithioate (DE-A 14 93 736)

Ethaboxam, Λ / - (cyano-2-thienylmethyl) -4-ethyl-2- (ethylamino) -5-thiazolecarboxamide

(EP-A 639 574);

Fenhexamide, N- (2,3-dichloro-4-hydroxyphenyl) -1-methylcyclohexanecarboxamide (Proc.

Br. Crop Prot. Conf. - Pests Dis., 1998, vol. 2, p. 327); Fentin acetate, triphenyltin (US 3,499,086);

Fenoxanil, Λ / - (1-cyano-1,2-dimethylpropyl) -2- (2,4-dichlorophenoxy) propanamide

(EP-A 262 393);

Ferim zone, (Z) -2'-methylacetophenone-4,6-dimethylpyrimidin-2-ylhydrazone

[CAS RN 89269-64-7]; Fluazinam, S-chloro-N - ^ - chloro ^^ - dinitro ^ - rifluoromethyophenyl-S-rifluoromethyl) -pyridinamine (The Pesticide Manual, Ed.: The British Crop Protection Council, 10th Edition 1995, p. 474 );

Fosetyl, Fosetyl aluminum, ethyl phosphonate (FR 22 54 276);

Iprovalicarb, [(1S) -2-methyl-1- (1-p-tolyl-ethylcarbamoyl) -propyl] carbamic acid isopropyl ester (EP-A 472 996);

Hexachlorobenzene (C.R. Seances Acad. Agric. Fr., Vol. 31, p. 24 (1945);

Mandipropamide, (RS) -2- (4-chlorophenyl) -Λ / - [3-methoxy-4- (prop-2-ynyloxy) phenethyl] -2-

(prop-2-ynyloxy) acetamide (WO 03/042166);

Metrafenone, 3'-bromo-2,3,4,6'-tetramethoxy-2 ', 6-dimethylbenzophenone (U.S. 5,945,567); Pencycuron, 1- (4-chlorobenzyl) -1-cyclopentyl-3-phenylurea (DE-A 27 32 257);

Penthiopyrad, (RS) -Λ / - [2- (1,3-dimethylbutyl) -3-thienyl] -1-methyl-3- (trifluoromethyl) -1H-pyrazole-4-carboxamide (JP 10/130268);

Propamocarb, 3- (dimethylamino) propylcarbaminsäureisopropylester (DE-A 15 67 169);

Phthalide (DE-A 16 43 347); Toloclofos-methyl, O-2,6-dichloro-p-tolyl 0,0-dimethyl phosphorothioate (GB 14 67 561);

Quintoene, pentachloronitrobenzene (DE-A 682 048);

Zoxamide, (RS) -3,5-dichloro-Λ / - (3-chloro-1-ethyl-1-methyl-2-oxopropyl) -p-toluamide

[CAS RN 156052-68-5];

Captafol, Λ / - (1,1,2,2-tetrachloroethylthio) cyclohex-4-ene-1,2-dicarboximide (Phytopatholgy 52, p. 754 (1962));

Captan, N- (trichloromethylthio) cyclohex-4-ene-1,2-dicarboximide (US 2,553,770);

Dichlofluanid, N-dichlorofluoromethylthio-Λ / ', Λ /' - dimethyl-Λ / -phenylsulfamide

(DE-A 11 93 498);

Folpet, Λ / - (trichloromethylthio) phthalimide (US 2 553 770); Tolylfluanid, Λ / -dichlorofluoromethylthio-Λ / ', Λ /' - dimethyl-Λ / -p-tolylsulfamide

(DE-A 11 93 498); Dimethomorph, 3- (4-chlorophenyl) -3- (3,4-dimethoxyphenyl) -1-morpholin-4-yl-propenone

(EP-A 120 321);

Flumetover, 2- (3,4-dimethoxyphenyl) -Λ / -ethyl-α, α, α-trifluoro-Λ / -methyl-p-toluamide

[AGROW No. 243, 22 (1995)]; Flumorph, 3- (4-fluorophenyl) -3- (3,4-dimethoxyphenyl) -1-morpholin-4-yl-propenone (EP-A

860 438),

4-Difluoromethyl-2-methyl-thiazole-5-carboxylic acid (4'-bromo-biphenyl-2-yl) -amide, 4-difluoro-methyl-2-methyl-thiazole-5-carboxylic acid (4'-trifluoromethyl -biphenyl-2-yl) -amide, 4-difluoromethyl-2-methyl-thiazole-5-carboxylic acid (4'-chloro-3'-fluorobiphenyl-2-yl) -amide, 3-difluoro- Methyl-1-methyl-pyrazole-4-carboxylic acid (3 ', 4'-dichloro-4-fluoro-biphenyl-2-yl) -amide

(WO 03/66610),

3,4-Dichloro-isothiazole-5-carboxylic acid (2-cyano-phenyl) -amide (WO 99/24413);

N- (2- (4- [3- (4-chloro-phenyl) -prop-2-ynyloxy] -3-methoxyphenyl) -ethyl) -2-methanesulfonylamino-3-methylbutyramide, N- (2- (4- [3- (4-chloro-phenyl) -prop-2-ynyloxy] -3-methoxyphenyl) -ethyl) -2-ethanesulfonylamino-3-methylbutyramide (WO 04/49804);

3- [5- (4-Chloro-phenyl) -2,3-dimethyl-isoxazolidin-3-yl] -pyridine (EP-A 10 35 122);

2-butoxy-6-iodo-3-propyl-chromen-4-one (WO 03/14103);

3- (3-Bromo-6-fluoro-2-methylindol-1-sulfonyl) - [1, 2,4] triazole-1-sulfonic acid dimethylamide

(EP-A 10 31 571); (2-Chloro-5- [1 - (3-methyl-benzyloxyimino) -ethyl] -benzyl) -carbamic acid methyl ester, (2-

Methyl chloro-5- [1- (6-methylpyridin-2-ylmethoxyimino) ethyl] benzyl) carbamate (EP-A 12 01 648);

Methyl 3- (4-chlorophenyl) -3- (2-isopropoxycarbonylamino-3-methylbutyrylamino) propionate (EP-A 10 28 125); Azoxystrobin, 2- {2- [6- (2-cyano-1-vinyl-penta-1,3-dienyloxy) -pyrimidin-4-yloxy] -phenyl} -

3-methoxy-acrylic acid methyl ester (EP-A 382 375),

Dimoxystrobin, (E) -2- (methoxyimino) -N-methyl-2- [α- (2,5-xylyloxy) -o-tolyl] -acetamide

(EP-A 477 631);

Fluoxastrobin, (E) - {2- [6- (2-chlorophenoxy) -5-fluoropyrimidin-4-yloxy] phenyl} (5,6-dihydro-1,2,2-dioxazin-3-yl) -methanone-O methyloxime (WO 97/27189);

Kresoxim-methyl, (E) -methoxyimino [α- (o-tolyloxy) -o-tolyl] acetic acid methyl ester (EP-A

253 213);

Metominostrobin, (E) -2- (methoxyimino) -N-methyl-2- (2-phenoxyphenyl) acetamide (EP-A

398 692); Orysastrobin, (2E) -2- (methoxyimino) -2- {2 - [(3E, 5E, 6E) -5- (methoxyimino) -4,6-dimethyl-

2,8-dioxa-3,7-diazanona-3,6-dien-1-yl] phenyl} -N-methylacetamide (WO 97/15552);

Picoxystrobin, 3-methoxy-2- [2- (6-trifluoromethyl-pyridin-2-yloxymethyl) -phenyl] -acrylic acid methyl ester (EP-A 278 595);

Pyraclostrobin, N- {2- [1- (4-chlorophenyl) -1H-pyrazol-3-yloxymethyl] phenyl} (N-methoxy) carbamic acid methyl ester (WO 96/01256); Trifloxystrobin, (E) -methoxyimino-{(E) -α- [1- (α, α, α-trifluoro-m-tolyl) ethylideneaminooxy] -o-tolyl} -acetic acid methyl ester (EP-A 460 575);

2- [ortho- (2,5-dimethylphenyl-oxymethylene) -phenyl] -3-methoxy-acrylic acid methyl ester (EP-A 226 917); 5-Chloro-7- (4-methylpiperidin-1-yl) -6- (2,4,6-trifluorophenyl) - [1,2,4] triazolo [1,5-a] pyrimidine (WO 98/46608);

3,4-dichloro-N- (2-cyanophenyl) -isothiazole-5-carboxylic acid amide (WO 99/24413),

Compounds of the formula III (WO 04/049804);

N- (2- (4- [3- (4-chloro-phenyl) -prop-2-ynyloxy] -3-methoxyphenyl) -ethyl) -2-methanesulfonylamino-3-methylbutyramide and N- (2- (4- [3- (4-chloro-phenyl) -prop-2-ynyloxy] -3-methoxyphenyl) -ethyl) -2-ethanesulfonylamino-3-methylbutyramide (WO 03/66609);

2-butoxy-6-iodo-3-propyl-chromen-4-one (WO 03/14103);

3- (3-Bromo-6-fluoro-2-methylindol-1-sulfonyl) - [1, 2,4] triazole-1-sulfonic acid dimethylamide

(WO 03/053145); Methyl 3- (4-chlorophenyl) -3- (2-isopropoxycarbonylamino-3-methylbutyrylamino) propanoate (EP-A 1028125).

The compounds of general formula (I) may be used with said other fungicides together in generally conventional formulations, e.g. as solutions, emulsions, suspensions, dusts, powders, pastes and granules. The type of application depends on the respective purpose. The formulations are prepared by known methods.

The formulations generally contain between 0.01 and 95% by weight, preferably between 0.1 and 90% by weight of active ingredients.

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 ingredient 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.

To the active ingredient of the general formula (I) it is possible to add oils of various types, wetting agents, adjuvants, herbicides, other fungicides, other pesticides, bactericides, if appropriate also immediately before use (tank mix). These agents can be added to the compositions according to the invention in a weight ratio of 1:10 to 10: 1.

The fungicidal action of compounds of the general formula (I) against resistant harmful fungi can be demonstrated by the following experiments: Example 1 / Preparation of the test solutions

Starting from four different carboxylic acid amide fungicides, four parent preparations are prepared with the respectively indicated amounts of the active ingredient in water.

Stock solution A was prepared from dimethomorph ((E, Z) -4- [3- (4-chlorophenyl) -3- (3,4-dimethoxyphenyl) acryloy] morpholine) at 150 g / l as dispersible concentrate (d.c.).

Stock B was prepared from mandipropamide ((RS) -2- (4-chlorophenyl) -N- [3-methoxy-4- (prop-2-ynyloxy) phenethyl] -2- (prop-2-ynyloxy) acetamide) 40g / l emulsifiable concentrate (ec) produced.

Stock solution C was prepared from iprovalicarb

(isopropyl 2-methyl-1 - [(1-p-tolylethyl) carbamoyl] - (S) -propylcarbamate) as

50% water dispersible granules (w.g.) produced.

Stock solution D was prepared from Benthiavalicarb

(isopropyl [(S) -I - {[(R) -1- (6-fluoro-1,3-benzothiazol-2-yl) ethyl] carbamoyl} - = 2-methylpropyl] carbamate) as a 10% wettable powder ( wp).

Example 2:

Investigation of the effectiveness of the four carboxylic acid amide fungicides against sensitive and resistant Plasmopara viticola strains.

Four weeks old grape plants (Riesling) with 6-8 leaves are treated with 50 ml of a fungus-containing solution (200,000 spores per milliliter of the fungus Plasmopara viticola). Both experiments with sensitive and resistant strains are carried out.

The fungicidal active ingredients described in Example 1 are applied both one day before the treatment with the harmful fungi (preventive treatment) and in each case one day after the treatment with the harmful fungi (curative treatment). After treatment with the harmful fungi, the plants are allowed to stand at 95% humidity and a temperature of 18 ° C overnight. This is followed by an observation phase for 6 days and a final evaluation on the 6th day, the test plants are exposed to daylight for 12 hours each and left in the dark for 12 hours.

To enhance the formation of spores, the undersides of the vine leaves are sprayed with water for 24 hours before the end of the evaluation and allowed to stand.

The evaluation of the experiments is carried out by a determination of the percentage of diseased leaf area of each plant. A high percentage value means a high degree of harmful fungus disease, a low percentage value means a low level of harmful fungus disease.

Results:

For the curative treated with stock solution A plants resulted in an affected leaf area of 70% for the resistant fungi and an infestation of 0% for the sensitive fungi. Preventive treatment resulted in an affected leaf area of 0.5% for the resistant fungi and 0% infestation for the sensitive fungi.

For the plants treated with the stock solution B, a curative treatment resulted in an attack of 65% of the leaf area for the resistant fungi and an infestation of 0% for the sensitive fungi. The preventive treatment resulted in an attack of 8% of the leaf area for the resistant fungi and an infestation of 0% of the leaf area for the sensitive fungi.

For the plants treated with the stock solution C, curative treatment resulted in an attack of 75% of the resistant fungi and an infestation of 0% in the sensitive fungi. Preventive treatment resulted in an attack of 70% of the area for the resistant fungi and an attack of 0% of the surface for the sensitive fungi.

For the plants treated with the stock solution D, curative treatment resulted in an attack of 70% of the area for the resistant fungi and an infestation of 0% for the sensitive fungi. Preventive treatment resulted in an attack of 55% of the surface area for the resistant fungi and an infestation of 0% of the surface area for the sensitive fungi.

In a control experiment in which the test plants were sprayed with only one drug-free test solution, resulted in curative treatment infestation of 68% of the area for the resistant fungi and an infestation of 65% of the area for the sensitive fungi. In the comparative experiment with preventive treatment, an area of 75% of the surface when applied to the resistant fungi and an infestation of 80% of the area in the sensitive fungi. From these comparative studies it can be seen that all four fungicidal active ingredients (carboxylic acid amide fungicides) have a high efficacy in the curative and preventive treatment of sensitive fungal strains.

In the case of the resistant fungal strains, however, preventive treatment with dimethomorph and treatment with mandipropamide were effective, whereas treatment with iprovalicarb and benthiavalicarb did not produce satisfactory results.

Claims

claims

1. A process for controlling harmful fungi which exhibit resistance to carboxylic acid amide fungicides, which comprises using a fungicidally effective amount of a compound of the general formula (I)

where -R means:

OChL OC ₂ H ₅ or OCH. C ≡ CH

where -X is either -Cl or -F

and

where -Z- means:

CH CO NO

or

CH CO NH CH ₉ CH ₅

O CH ₂ C≡CH

preventively applying to the plants, seeds and / or soils before or after sowing the plants or before or after plant spillage.

2. A method for controlling harmful fungi according to claim 1, characterized in that the harmful fungus Plasmopara-, Peronospora, Phytophthora, Pseudoperonospora, Pythium and / or Sclerospora species are controlled.

3. A method for controlling harmful fungi according to one of the claims 1 or 2, characterized in that a compound of the general formula (I) is used, in which

-R means:

OCH 3 'OC ₂ H ₅ or OCH. C ≡ CH

-X means -Cl or -F

and -Z- means:

CH CO NO

4. A method for controlling harmful fungi according to one of the claims 1 to 3, characterized in that one uses a compound of general formula (I), wherein

-R means:

OCH 3 'OC ₂ H ₅ or OCH. C ≡ CH

-X means -Cl

and the -Z- is CH CO NH-CH, CH.

O CH. C ≡ CH

5. A method for controlling harmful fungi according to one of the claims 1 to 4, characterized in that the compound of the general formula (I) is used in an amount of 1 to 1000 g / ha.

6. A method for controlling harmful fungi according to one of the claims 1 to 5, characterized in that the compound of general formula (I) in amounts of 1 to 1000g / 100kg seed is applied.

7. A method for controlling harmful fungi according to one of the claims 1 to 6, characterized in that the compound of the general formula

(I) is applied to the underside of the leaves of the plants to be treated.

8. A method for controlling harmful fungi according to one of the claims 1 to 7, characterized in that it is treated vines in the treated plants.

9. A method for controlling harmful fungi according to one of the claims 1 to 8, characterized in that one uses a compound of general formula (I) in combination with another fungicide.

10. A method for controlling harmful fungi according to one of the claims 1 to 9, characterized in that one uses a compound of general formula (I) in combination with a further carboxylic acid amide fungicide.

1 1. Use of a compound of the general formula (I)

where -R means:

OCH ₃ , OC ₂ H ₅ or OCH ₂ C ≡ CH where -X is either -Cl or -F

and

where -Z- means:

CH CO NO

or

CH-CO NH-CH. CH.

O CH. C ≡ CH

for the preparation of a fungicidal preparation for the preventive control of fungi in crops.

12. Use of a compound of the general formula (I)

where -R means:

OCH ₃ , OC ₂ H ₅ or OCH ₂ C ≡ CH

where -X is either -Cl or -F

and where -Z- means:

CH CO NO

or

CH CO NH CH ₉ CH ₅

O CH ₂ C = CH

for the prevention of cross-resistance in fungal control of crops.