WO2007065843A2 - Use of gibberellin as safener for azoles for prevention of fungal pests - Google Patents

Abstract

The invention relates to the use of gibberellin of formula (I), where R = H or OH and the dotted line indicates that at this ring position either a C- C single bond or a C=C double bond is present, as safener for at least one azol (2), selected from azaconazol, bitertanol, bromuconazol, cyproconazol, difenoconazol, diniconazol, enilconazol, epoxiconazol, fluquinconazol, fenbuconazol, flusilazol, flutriafol, hexaconazol, imibenconazol, ipconazol, metconazol, myclobutanil, penconazol, propiconazol, prothioconazol, simeconazol, triadimefon, triadimenol, tebuconazol, tetraconazol, triticonazol, prochloraz, pefurazoat, imazalil, triflumizol, cyazofamid, benomyl, carbendazim, thiabendazol, fuberidazol, ethaboxam, etridiazol, hymexazol, or the salts or adducts thereof, for the prevention fungal pests. The invention further relates to the use of compounds (I) and (2) in a method for the prevention of fungal pests with mixtures of compounds (I) and (2) and the use of compounds (I) and (2) for the production of such mixtures and agents comprising said mixtures.

Description

 Use of gibberellin as a safener for azoles to control harmful fungi

Description The present invention relates to

(1) Use of gibberellin of formula I.

in welcher

in which

R represents a hydrogen atom or a hydroxyl group and the dashed line indicates that either a C-C single bond or a C = C double bond is present at the position of the ring, as safener for (2) at least one azole selected from azaconazole, Bitertanol, bromuconazole,

Cyproconazole, difenoconazole, diniconazole, enilconazole, epoxiconazole, fluquinconazole, fenbuconazole, flusilazole, flutriafole, hexaconazole, imibenconazole, iponazolone, metconazole, myclobutanil, penconazazole, propiazonolol, propiconazolone, propiconazolone, propiconazolone, propiconazolone, propiconazolone, propiconazolone, propiconazolone Triticonazole, prochloraz, pefurazoate, imazalil, triflumizole, cyazofamid, benomyl, carbendazim, thiabendazole, fuberidazole, ethaboxam, etridiazole, hymexazole, or its salts or adducts to combat harmful fungi. In addition, the invention relates to the use of the compounds I and the azole (2) in a process for combating harmful fungi with mixtures of the compounds I and (2) and the use of the compounds I and (2) for the production of such mixtures and agents which Mixtures included. Gibberellin of the formula I and mordants which contain it in a mixture with azoles, such as triticonazole, are known from WO 02/069715. The mixture of gibberellic acid and tebuconazole is described as the only biological example. The azoles (2) are all known from the literature and are commercially available.

From Montfort, F. et al., Pesticide Science 46 (4), 1996, 1996, pp. 315-322 it is known that the use of triazoles such as triticonazole for the treatment of seeds or crop plants can have a negative influence on plant growth . A negative effect in the treatment with azoles, for example, could be a greatly reduced growth in length. This effect has been described in the wheat crop. The object of the present invention was to find a safener which eliminates the negative effects of the azoles in relation to plant growth with a constant fungicidal action.

Accordingly, the initially defined use of gibberellin as a safener for azoles was found to combat harmful fungi. It has also been found that gibberellin and azole can be used simultaneously, together or separately. It has also been found that gibberellin and azole can be used to prepare an agent. The gibberellin of formula I.

in welcher

in which

R represents a hydrogen atom or a hydroxyl group and the dashed line indicates that either a C-C single bond or a C = C double bond is present at the position of the ring is described in WO 02/069715.

Formula I comprises the Gibberellins of the formulas 1-1 to I-4.

(1-1) Gibberellin A ₁

(I-2) Gibberellin A ₃

 (Gibberellic acid)

 (I-3) Gibberellin A.

 and

(I-4) Gibberellin A ₇

Gibberellic acid of the formula (I-2) is particularly preferred. The azoles mentioned above as component (2), their preparation and their action against harmful fungi are generally known (cf.

http://www.hclrss.demon.co.uk/index.html); they are commercially available.

Azaconazole 1 - [[2- (2,4-dichlorophenyl) -1, 3-dioxolan-2-yl] methyl] -1 H-1, 2,4-triazole CAS RN [50207-31-0],

 Bitertanol, ß - ([1, 1 '-Biphenyl] -4-yloxy) -α- (1, 1-dimethylethyl) -1 H-1, 2,4-triazole-1-ethanol

(DE 23 24 020),

 Bromuconazole, 1 - [[4-bromo-2- (2,4-dichlorophenyl) tetrahydro-2-furanyl] methyl] -1 H-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] triazol-1-yl-butan-2-ol

(U.S. 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, (ßE) -ß - [(2,4-dichlorophenyl) methylene] -α- (1, 1-dimethylethyl) -1 H-1, 2,4-triazole-1-ethanol (Noyaku Kagaku, 1983, Vol . 8, p. 575),

Enilconazole (imazalil), 1- [2- (2,4-dichlorophenyl) -2- (2-propenyloxy) ethyl] -1 H-imidazole

(Fruits, 1973, vol. 28, p. 545),

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

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

 Fluquinconazole, 3- (2,4-dichlorophenyl) -6-fluoro-2- [1,2,4] triazol-1-yl-3H-quinazolin-4-one (Proc. Br. Crop Prot. Conf -Pests Dis., 5-3, 411 (1992));

 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),

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

Crop Prot. Conf. Pests Dis., 1, 413 (1984));

Flutriafol, α- (2-fluorophenyl) -α- (4-fluorophenyl) -1 H-1, 2,4-triazole-1-ethanol (EP 15 756),

Hexaconazole, 2- (2,4-dichlorophenyl) -1- [1,2,4] triazol-1-yl-hexan-2-ol (CAS RN

 [79983-71-4]);

 Imibenconazole, (4-chlorophenyl) methyl N- (2,4-dichlorophenyl) -1 H-1, 2,4-triazole-1-ethane imidothioate ((Proc. 1988 Br. Crop Prot. Conf. - Pests Dis. Vol. 2, p. 519),

Ipconazole, 2 - [(4-chlorophenyl) methyl] -5- (1-methylethyl) -1 - (1 H-1, 2,4-triazol-1-yl-methyl) cyclopentanol (EP 267 778),

 Metconazole, 5- (4-chloro-benzyl) -2,2-dimethyl-1 - [1, 2.4] triazole-1-methyl-cyclopentanol

(GB 857 383);

 Myclobutanil, 2- (4-chlorophenyl) -2- [1, 2,4] triazol-1-ylmethylpentanitrile (CAS RN

[88671-89-0]);

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

Ed. (2000), page 712);

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

Prothioconazole, 2- [2- (1-chloro-cyclopropyl) -3- (2-chlorophenyl) -2-hydroxypropyl] -2,4-dihydro- [1,2,4] triazol-3-thione (WO 96/16048);

 Simeconazole, α- (4-fluorophenyl) -α - [(trimethylsilyl) methyl] -1 H-1,2,4-triazole-1-ethanol

[CAS RN 149508-90-7],

 Triadimphone, 1 - (4-chlorophenoxy) -3,3-dimethyl-1 - (1 H-1, 2,4-triazol-1-yl) -2-butanone; Triadimenol, ß- (4-chlorophenoxy) -α- (1, 1-dimethylethyl) -1 H-1, 2, 4-triazole-1-ethanol;

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

(EP-A 40 345);

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

Triticonazole, (5E) -5 - [(4-chlorophenyl) methylene] -2,2-dimethyl-1 - (1 H-1, 2,4-triazol-1 - ylmethyl) cyclopentanol (FR 26 41 277), Prochloraz, imidazole-1-carboxylic acid propyl- [2- (2,4,6-trichlorophenoxy) ethyl] amide (US

3,991,071);

 Pefurazoate, 4-pentenyl 2 - [(2-furanylmethyl) (1 H -imidazol-1-ylcarbonyl) amino] butanoate

[CAS RN 101903-30-4],

Triflumizole, (4-chloro-2-trifluoromethyl-phenyl) - (2-propoxy-1 - [1, 2,4] triazol-1 -yl-ethylidene) - amine (JP-A 79/1 19 462)

 Cyazofamide, 4-chloro-2-cyano-N, N-dimethyl-5- (4-methylphenyl) -1 H-imidazole-1 sulfonamide (CAS RN 1201 16-88-3],

 Benomyl, 2-acetylamino-benzoimidazole-1-carboxylic acid butylamide (US 3,631,176); Carbendazim, (1 H-benzoimidazol-2-yl) carbamic acid methyl ester (US 3,657,443);

Thiabendazole, 2- (1, 3-thiazol-4-yl) benzimidazole (US 3,017,415),

 Fuberidazole, 2- (2-furanyl) -1 H-benzimidazole (DE 12 09 799),

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

(EP-A 639 574),

Etridiazole (US 3260588),

 Hymexazole, 5-methyl-1, 2-oxazol-3-ol (JP 518249, JP 532202).

Because of the basic character of the nitrogen atoms they contain, the azoles (2) are able to form salts or adducts with inorganic or organic acids or with metal ions.

Examples of inorganic acids are hydrohalic acids such as hydrogen fluoride, hydrogen chloride, hydrogen bromide and hydrogen iodide, sulfuric acid, phosphoric acid and nitric acid.

Examples of organic acids are formic acid, carbonic acid and alkanoic acids such as acetic acid, trifluoroacetic acid, trichloroacetic acid and propionic acid as well as glycolic acid, thiocyanic acid, lactic acid, succinic acid, citric acid, benzoic acid, cinnamic acid, oxalic acid, alkylsulfonic acids (sulfonic acids with straight-chain alkyl radicals, or branched-chain alkyl radicals) or branched chain alkyl radicals, Arylsulfonic acids or - disulfonic acids (aromatic radicals such as phenyl and naphthyl which carry one or two sulfonic acid groups), alkylphosphonic acids (phosphonic acids with straight-chain or branched alkyl radicals having 1 to 20 carbon atoms), arylphosphonic acids or -diphosphonic acids (aromatic radicals such as phenyl and naphthyl which one or carry two phosphoric acid residues), where the alkyl or aryl residues can carry further substituents, for example p-toluenesulfonic acid, salicylic acid, p-aminosalicylic acid, 2-phenoxybenzoic acid, 2-acetoxybenzoic acid etc.

In particular, the ions of the elements of the second main group, in particular calcium and magnesium, the third and fourth main group, in particular aluminum, tin and lead, and the first to eighth subgroups, in particular chromium, manganese, iron, cobalt, nickel, come as metal ions. Copper, zinc and others in dress. The metal ions of the elements of the subgroups of the fourth period are particularly preferred. The metals can be present in the various valences that they have. As described at the outset, in many crops, dressing the seeds with fungicides causes a delay or decrease in emergence and a poorer establishment of the crop at the start of the crop.

The use of the mixtures of the compounds I and (2) or the simultaneous joint or separate use of one of the compounds I and (2) are distinguished by the fact that these have negative effects on the plants which, depending on the dose, also Fluquinconazole or gibberellin may or may not occur or not occur as strongly. In addition, the mixtures have excellent activity against a broad spectrum of phytopathogenic fungi, in particular from the class of the Ascomycetes, Basidiomycetes, Deuteromycetes and Peronosporomycetes (syn. Oomycetes). Some of them are systemically effective and can be used in plant protection as foliar, stain and soil fungicides.

They are particularly important for combating a large number of fungi on various crops such as bananas, cotton, vegetables (eg cucumber, beans, tomatoes and squashes), barley, grass, oats, coffee, potatoes, corn, fruit plants, rice, rye , Soy, wine, wheat, ornamental plants, sugar cane and a variety of seeds. They are particularly suitable for combating the following plant diseases:

 Alternaria types of vegetables, rapeseed, sugar beet and fruit and rice, such as

 A.solani or A. alternata on potatoes and tomatoes

 • Aphanomyces species on sugar beets and vegetables

 • Ascochyta species on cereals and vegetables

Bipolaris and Drechslera species on maize, cereals, rice and turf, such as

 D.maydis on corn

 Blumeria graminis (powdery mildew) on cereals,

 Botrytis cinerea (gray mold) on strawberries, vegetables, flowers and grapevines,

• Bremia lactucae on lettuce

 • Cercospora species on corn, soybeans, rice and sugar beets

 Cochliobolus species on corn, cereals, rice, such as Cochliobolus sativus on cereals, Cochliobolus miyabeanus on rice

 • Colletotricum species on soybeans and cotton

• Drechslera species, Pyrenophora species on corn, cereals, rice and turf, such as D.teres on barley or D. tritici-repentis on wheat • Esca on grapevine caused by Phaeoacremonium chlamydosporium, Ph. Aleophilum, and Formitipora punctata (syn. Phellinus punctatus)

 • Exserohilum species on maize

 Erysiphe cichoracearum and Sphaerotheca fuliginea on cucumber plants, Fusarium and Verticillium species on various plants such as F. graminearum or F. culmorum on cereals or F. oxysporum on a variety of plants such as tomatoes

 • Gaeumanomyces graminis on cereals

 • Gibberella species on cereals and rice (e.g. Gibberella fujikuroi on rice) • Grain training complex on rice

 • Helminthosporium species on corn and rice

 • Michrodochium nivale on cereals

 Mycosphaerella species on cereals, bananas and peanuts, such as M. gramicola on wheat or M. fijiensis on bananas

Peronospora species on cabbage and onion plants, such as P. brassicae on cabbage or P. destructor on onion

 • Phakopsara pachyrhizi and Phakopsara meibomiae on soybeans

 • Phomopsis species on soybeans and sunflowers

 Phytophthora infestans on potatoes and tomatoes,

Phytophthora species on various plants such as P.capsici on bell pepper,

Plasmopara viticola on vines,

 Podosphaera leucotricha on apple,

 Pseudocercosporella herpotrichoides on cereals,

 Pseudoperonospora on various plants such as P. cubensis on cucumber or P. humili on hops

 Puccinia species on different plants such as P. triticina, P. striformins, P. hordei or P. graminis on cereals, or P. asparagi on asparagus

 Pyricularia oryzae, Corticium sasakii, Sarocladium oryzae, S.attenuatum, Entyloma oryzae, on rice,

• Pyricularia grisea on lawns and cereals

 • Pythium spp. on lawn, rice, corn, cotton, rapeseed, sunflowers, sugar beets, vegetables and other plants such as P.ultiumum on various plants, P. aphanidermatum on lawn

 Rhizoctonia species on cotton, rice, potatoes, lawn, maize, rapeseed, potatoes, sugar beets, vegetables and on various plants such as R.solani on beets and various plants,

 • Rhynchosporium secalis on barley, rye and triticale

 • Sclerotinia species on rapeseed and sunflowers

 Septoria tritici and Stagonospora nodorum on wheat,

• Erysiphe (syn. Uncinula) necator on grapevine

 • Setospaeria species on maize and lawn

• Sphacelotheca reilinia on corn • Thievaliopsis species on soybeans and cotton

 • Tilletia species on cereals

 Ustilago species on cereals, corn and sugar cane, such as U. maydis on corn

• Venturia species (scab) on apples and pears like. e.g. V. inaequalis on apple.

The use of compounds I and (2) for combating soybean rust (Phakopsara pachyrhizi and Phakopsara meibomiae) has proven particularly useful, particularly in the treatment of soybean seeds. In addition, the compounds I and (2) can be used to control harmful fungi such as Paecilomyces variotii in the protection of materials (e.g. wood, paper, dispersions for painting, fibers or fabrics) and in the protection of stored products.

The compounds I and (2) can be applied simultaneously, that is jointly or separately, or in succession, the sequence in the case of separate application generally not having any effect on the growth of the plants and the success in controlling them.

In the use according to the invention, preference is given to using pure active ingredients I and (2), to which further active ingredients are used to combat harmful fungi or against others

Pests such as insects, arachnids or nematodes or herbicidal or growth-regulating active ingredients or fertilizers can be added.

Mixtures of compounds I and (2) are usually used. Under certain circumstances, however, mixtures of the compounds I and (2) with possibly a plurality of active components may also be advantageous, such as, for example, mixtures of the compounds I and (2) with further fungicides.

The mixing ratio (weight ratio) of the compounds I and (2) is selected so that the described safener action occurs, for example compound I: compound (2) such as 100: 1 to 1: 100, in particular 10: 1 to 1:10 , for example 5: 1 to 1: 5, in particular 3: 1 to 1: 3, preferably 2: 1 to 1: 2. The safener effect of the mixture is shown by the fact that the negative effect of azole on plant growth does not or does not occur as strongly.

If desired, the further active components are mixed in a ratio of 20: 1 to 1:20 to the compounds I and (2).

Depending on the type of compound and the desired effect, the application rates of the mixtures used, especially in the case of agricultural cultivated areas, are from 5 g / ha to 2000 g / ha, preferably from 20 to 900 g / ha, in particular from 50 to 750 g / ha . Accordingly, the application rates for the compound I are generally from 1 to 1000 g / ha, preferably from 10 to 900 g / ha, in particular from 20 to 750 g / ha.

The application rates for the active ingredient (2) are generally from 1 to 1000 g / ha, preferably 10 to 900 g / ha, in particular 40 to 750 g / ha.

In the case of seed treatment, 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 generally used.

The use of the compounds I and (2) according to the invention in the process for combating harmful fungi is carried out by the separate or joint application of the compounds I and (2) or a mixture of the compounds I and (2) by spraying or dusting the seeds and the plants or the soil before or after sowing the plants or before or after emergence of the plants.

When using the compounds I and (2) according to the invention, these can be converted into the customary formulations, e.g. Solutions, emulsions, suspensions, dusts, powders, pastes and granules. The form of application depends on the respective purpose; in any case, it should ensure a fine and uniform distribution of the compounds I and (2).

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. The following are essentially considered as solvents / auxiliaries:

 Water, aromatic solvents (e.g. Solvesso products, XyIoI), paraffins (e.g. petroleum fractions), alcohols (e.g. methanol, butanol, pentanol, benzyl alcohol), ketones (e.g. cyclohexanone, gamma-butryolactone), 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 natural powdered rock (e.g. kaolins, clays, talc, chalk) and synthetic powdered rock (e.g. highly disperse 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 methyl cellulose.

Suitable surfactants are alkali metal, alkaline earth metal salts, sulfonic acid ammonium salts of lignosulfonic acid, naphthalenesulfonic acid, phenolsulfonic acid, dibutylnaphthalenesulfonic acid, alkylarylsulfonates, alkyl sulfates, alkylsulfonates, fatty alcohol sulfates, fatty acids and sulfated fatty alcohol glycol ethers, furthermore condensates of sulfonated naphthalene and naphthalene derivatives with formaldehyde , Condensation products of Naphthalene or the naphthalene sulfonic acid with phenol and formaldehyde, polyoxyethylene octylphenol ether, ethoxylated isooctylphenol, octylphenol, nonylphenol, alkylphenol polyglycol ether, tributylphenyl polyglycol ether, tristerylphenylpolyglycol ether, alkyl aryl ethylene polyethylenethylene alcohol, ethoxylated alcohol ethoxylated alcohol, ethoxylated alcohol ethoxylated alcohol glycol ether acetal, sorbitol esters, lignin sulfite liquors and methyl cellulose.

For the production of directly sprayable solutions, emulsions, pastes or oil dispersions, mineral oil fractions from medium to high boiling points, such as kerosene or diesel oil, furthermore 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, strongly polar solvents, e.g. Dimethyl sulfoxide, N-methylpyrrolidone or water into consideration.

Powders, materials for broadcasting and dusts can be prepared by mixing or grinding the active substances together with a solid carrier.

Granules, e.g. Coating, impregnation and homogeneous granules can be produced by binding the active ingredients to solid carriers. Solid carriers are e.g. Mineral soils, such as silica gels, silicates, talc, kaolin, attack clay, limestone, lime, chalk, bolus, loess, clay, dolomite, diatomaceous earth, calcium and magnesium sulfate, 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 flour, cellulose powder and other solid carriers.

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

Examples of formulations are: 1. Products for dilution in water A) Water-soluble concentrates (SL)

 10 parts by weight of active ingredients I and (2) are dissolved with 90 parts by weight of water or a water-soluble solvent. Alternatively, wetting agents or other aids are added. The active ingredients dissolve when diluted in water. A formulation with an active substance content of 10% by weight is obtained in this way.

B) Dispersible concentrates (DC)

20 parts by weight of active ingredients I and (2) are in 70 parts by weight of cyclohexanone Addition of 10 parts by weight of a dispersant, for example polyvinylpyrrolidone, dissolved. When diluted in water, a dispersion results. The active substance content is 20% by weight C) Emulsifiable concentrates (EC)

 15 parts by weight of active ingredients I and (2) are dissolved in 75 parts by weight of xylene with addition of calcium dodecylbenzenesulfonate and castor oil ethoxylate (5 parts by weight each). 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 the active ingredients I and (2) are dissolved in 35 parts by weight of xylene with the addition of calcium dodecylbenzenesulfonate and castor oil ethoxylate (5 parts by weight in each case). This mixture is added to 30 parts by weight of water using an emulsifying machine (e.g. Ultraturax) and brought to 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 active ingredients I and (2) are added with 10 parts by weight

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

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

 50 parts by weight of active ingredients I and (2) are finely ground with the addition of 50 parts by weight of dispersing and wetting agents and produced as technical equipment (e.g. 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 ingredients. 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 active ingredients I and (2) are ground in a rotor-strator 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 ingredients. The active substance content of the formulation is 75% by weight.

2. Products for direct application

H) dusts (DP)

5 parts by weight of active ingredients I and (2) are ground finely and with 95 parts by weight finely divided kaolin intimately mixed. This gives a dusting agent with an active ingredient content of 5% by weight.

J) Granules (GR, FG, GG, MG)

0.5 part by weight of active ingredients I and (2) are ground finely and combined with 99.5 parts by weight of carriers. Common processes are extrusion, spray drying or fluidized bed. This gives granules for direct application with an active substance content of 0.5% by weight. K) ULV solutions (UL)

 10 parts by weight of active ingredients I and (2) 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 substance content of 10% by weight. The active ingredients as such, in the form of their formulations or the use forms prepared therefrom, e.g. in the form of directly sprayable solutions, powders, suspensions or dispersions, emulsions, oil dispersions, pastes, dusts, sprinkling agents, granules by spraying, atomizing, dusting, scattering or pouring. The forms of application depend entirely on the purposes of 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. To prepare emulsions, pastes or oil dispersions, the substances as such or dissolved in an oil or solvent can be homogenized in water by means of wetting agents, adhesives, dispersants or emulsifiers. However, it is also possible to prepare concentrates composed of an active substance, wetting agents, adhesives, dispersants or emulsifiers and possibly solvents or oil, which are suitable for dilution with water.

The active substance concentrations in the ready-to-use preparations can be varied over a wide range. 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 process (ULV), it being possible to apply formulations with more than 95% by weight of active ingredient or even the active ingredient without additives. Various types of oils, wetting agents, adjuvants, and possibly only immediately before use (tank mix) can be added to the active ingredients. These Agents are usually added to the agents according to the invention in a weight ratio of 1: 100 to 100: 1, preferably 1:10 to 10: 1.

The compounds I and (2), the mixtures or the corresponding formulations are used by the harmful fungi, the plants, seeds, soils, surfaces, materials or spaces to be kept free of them with a fungicidally effective amount of the mixture, or the compounds I and (2) treated separately. The application can take place before or after the infestation by the harmful fungi.

The safener activity of the compounds I and (2) was demonstrated by the following experiments.

Selectivity of pickling treatments on soybean Example 1

"Hutcheson" seeds were dressed with various amounts of active ingredients. Triticonazole was used as the finished formulation. Gibberellic acid

 (Gibberellin A3) (GA3) was dissolved with 10% acetone and 90% water. Seeds treated with 10% acetone and 90% water served as a control.

100 pickled grains per variant were sown in sand. The seed pans were placed between 18 and 22 ° C in a greenhouse. 3 weeks after sowing, the plant height was determined and averaged for 10 randomly selected plants.

Example 2

"Hutcheson" seeds were dressed with various amounts of active ingredients. Fluquinconazole was used as a finished formulation. Gibberellic acid (Gibberellin A3) (GA3) was dissolved with 10% acetone and 90% water. Seeds treated with 10% acetone and 90% water served as a control.

100 pickled grains per variant were sown in sand. The seed pans were placed between 18 and 22 ° C in a greenhouse. 3 weeks after sowing, the plant height was determined and averaged for 10 randomly selected plants.

Example 3

Efficacy of GA as a safener in soybeans to compensate for influences on length growth

 Soybean seeds were treated with an azole or azole with GA in the amounts indicated and sown.

 The hypocotyl length was measured 9 days after sowing.

Example 4 Effectiveness of GA as a safener in soybeans in order to compensate for influences on emergence

 Soybean seeds were specified with an azole or azole with GA in the

Quantities stained and sown.

 The proportion of accumulated seeds was counted 8 days after sowing.

Claims

Claims 1. (1) Use of gibberellin of formula I.

 in which R represents a hydrogen atom or a hydroxyl group and the dashed line indicates that there is either a C-C single bond or a C = C double bond at the site of the ring, as a safener for (2) at least one azole selected from azaconazole, bitertanol, Bromucona- zol, cyproconazole, difenoconazole, diniconazole, enilconazole, epoxiconazole, fluquinconazole, fenbuconazole, flusilazole, flutriafol, hexaconazole, Imiben- conazole, ipconazole, metconazole, myclobutanil, penconazole, propiconazole, Prothioconazole, simeconazole, triadimefon, triadimenol, tebuconazole, tetraconazole, triticonazole, prochloraz, pefurazoate, imazalil, triflumizole, cyazofamid, benomyl, carbendazim, thiabendazole, fuberidazol, dazurazolam, or ethabidoxolam, or ethabidoxolam. 2. Use according to claim 1, characterized in that the Gibberellins are selected from

(1-1) Gibberellin A ₁ 15

(I-2) Gibberellin A ₃  (Gibberellic acid)

 (I-3) Gibberellin A. and

(I-4) Gibberellin A ₇ 3. Use according to claim 2, characterized in that the gibberellic acid of the formula (I-2) is used as gibberellin. 4. Use according to one of claims 1 to 3, characterized in that the azole is selected from epoxiconazole, fluquinconazole, flutriafol, metconazole, propiconazole, prothioconazole, tebuconazole, triticonazole or prochloraz. Use according to claim 4, characterized in that the azole is selected from epoxiconazole, fluquinconazole, flutriafol, metconazole, prothioconazole, tebuconazole or triticonazole. Use according to claim 5, characterized in that the azole is selected from epoxiconazole, fluquinconazole, flutriafol, metconazole or triticonazole. 7. Use according to one of claims 1 to 6, characterized in that the weight ratio of gibberellin of formula I to azole (2) is 100: 1 to 1: 100. 16 8. Use according to claim 1, characterized in that the harmful fungi, their habitat or the plants, seeds, soils, surfaces, materials or spaces to be kept free of them are treated with gibberellin of the formula I and at least one azole. 9. Use according to claim 8, characterized in that the compounds of the formulas I and the azole (2) according to claim 1 are applied simultaneously, that is jointly or separately, or in succession. 10. Use according to claim 8 or 9, characterized in that the Compounds of the formula I and the azole (2) according to claim 1 in an amount of 5 g / ha to 2000 g / ha. 1 1. Use according to claim 8 or 9, characterized in that the compounds I and the azole (2) according to claim 1 in an amount of 1 g to 1000 g per 100 kg of seed. 12. Use of the compounds I and the azole (2) according to claim 1 for  Production of an agent suitable for controlling harmful fungi. 13. Use according to claim 12, characterized in that the agent contains, in addition to the compounds of the formulas I and the azole (2), a solid or liquid carrier. 14. Use according to one of claims 1 to 13, characterized in that one uses the compounds I and the azole (2) according to claim 1 for controlling soybean rust. 15. Use according to claim 11, characterized in that the compounds I and the azole (2) are used for the treatment of soybean seeds. 17th