DE3333449A1 - Fungicidal agents - Google Patents

Abstract

The present invention relates to novel fungicidal active substance combinations of known, fungicidal 2,2-bisfluoromethyl-5-cyclohexyl-4-(1,2,4-triazol-1-yl)-3-pentanols of the formula <IMAGE> and their acid addition salts and metal salt complexes as the first component, and (A) wettable sulphur and/or (B) polyhaloalkylthio derivatives and/or (C) a guanidine derivative and/or (D) an aromatic carboxylic acid derivative and/or (E) dithiocarbamates and/or (F) benzimidazole derivatives and/or (G) derivatives of imidazoles and triazoles and/or (H) a phosphoric acid ester and/or (I) a tetrahydroquinoline derivative and/or (J) S,N-heterocyclic compounds and/or (K) a urea derivative and/or (L) a sulphonamide derivative and/or (M) a polyhydroxyether derivative and/or (N) a triazine derivative and/or (O) a copper complex salt and/or (P) an N-formyl derivative and/or (Q) a morpholine derivative and/or (R) a quinoxoline derivative and/or (S) a dicarboximide derivative as the second component.

Description

Fungicides

The present invention relates to new fungicidal active ingredient combinations from known fungicidal 2,2-bisfluoromethyl-5-cyclohexyl-4- (1,2,4-triazol-1-yl) -3-pentanols and other known fungicidal agents.

It is already well known that mixtures containing 1,2,4-triazole derivatives, such as 1- (4-chlorophenoxy) -3,3-dimethyl-1- (1,2,4-triazol-1-yl) -2-butanone, in combination with other known fungicides a considerably higher effect than the individual components have (cf. e.g.

the German Offenlegungsschrift 25 52 967 ELeA 16 710]).

However, the effectiveness of these active ingredient mixtures is not at all Areas of application fully satisfactory.

It has been found that new active ingredient combinations of pure diastereomers or diastereomer mixtures of 2,2-bisfluoromethyl-5-cyclohexyl-4- (1,2,4-triazol-1-yl) -3-pentanol of the formula (I) and their acid addition salts and metal salt complexes and (A) network sulfur and / or (B) polyhaloalkylthio derivatives of the formulas (IIa) R1 = (CH3) 2N-SO2-, (DICHLOFLUANID) (IIb) R1 and R2 = Haloalkyl = CCl3 (CAPTAN) (IIc) R1 and R2 = Haloalkyl = -CCl3 (FOLPET) (IId) R1 and R2 = Haloalkyl = -.CCl2-CHCl2 (CAPTAFOL) and / or (C) a guanidine derivative of the formula (DODINE) and / or (D) an aromatic carboxylic acid derivative of the formula (TETRACHLORPHTHAtID) and / or (E) dithiocarbamates of the formulas (Va) R1 = H, M = Zn (ZINEB) (Vb) R1 = H, M = Mn (MANEB) (Vc) Mixture of (Va) and (Vb) (MANCOZEB) (Vd) R1 = CH3, M = Zn (PROPINEB) and / or (F) benzimidazole derivatives of the formulas <FUBERIDAZOLE) (CARBENDAZIM) and / or (G) derivatives of imidazoles and triazoles of the formulas (VIIa) X = Cl, A = CO (TRIADIMEFON) (VIIb) X = Cl, A = CH (OH) (TRIADIMENOL) (FUNGAFLOR) (PROCHLORAZ) (VIIf) R1 = Cl, R2 = H, A = -CH2CH2-, X = H, Y = H (VIIg) R1 = CL, R2 = H, A = -CH2CH2-, X = F, Y = H (VIIh ) R1 = Cl, R2 = H, A = -CH2CH2-, X = F, Y = F (VIIi) R1 = CL, R2 = H, A = -CH = CH-, X = H, Y = H (VIIj ) R1 = Cl, R2 = CH3, A = -OCH2-, X = H, Y = H (VIIk) R1 = Cl, R2 = CH3, A = -OCH2-, X = F, Y = H R2 = H, A = -OCH2-, X = H, Y = H (VIIm) R1 = Cl, Rt = CL, A = -OCH2-, X = F, Y = H (VIIn) R1 = CH30N = CH- , R2 = H, A = -OCH2-, X = H, Y = H and / or (H) a phosphoric acid ester of the formula (EDIFENPHOS) and / or (I) a tetrahydroquinoline derivative of the formulas (IXa) Hal = Br (IXb) Hal = Cl (LILOLiDONE) and / or (J) S, N-heterocycle compounds of the formulas ¢ RICYCLAZOLE) (FLUBENZIMINE) and / or (K) a urea derivative of the formula (PENCYCURON) and / or (L) a sulfonamide derivative of the formula (PROBENAZOLE) and / or (M) a polyhydroxyether derivative of the formula (VALIDAMYCIN) and / or (N) a triazine derivative of the formula (ANILAZINE) and / or (0) a copper complex salt of the formula (COPPER OXINATE) and / or (P) an N-formyl derivative of the formula (CHLORANIFORMETHANE) and / or (Q) morpholine derivatives of the formulas (TRIDEMORPH) (FENPROPEMORPH) and / or (R) a quinoxaline derivative of the formula (CHINOMETHIONATE) and / or (S) a dicarboximide derivative of the formulas (PROCYMIDONE) (VINCHLO ZOLIN) (IPRODIONE) have a particularly high fungicidal effectiveness.

Surprisingly, the fungicidal effect is that of the invention Combinations of active ingredients much higher than the effect of the individual components and possibly also as the sum of the individual components (synergistic effect). The discovery of these combinations of specific compounds of the formula (1) and the active ingredients of the above groups (A), (B), (C), (D), (E), (F), (G), (H), (I), (J), (K), (L), (M), (N), (O), (P), (Q), (R) and (S) thus represent a a valuable asset to technology.

The compounds of the formula (I) to be used specifically for the combination according to the invention are clearly characterized by the above definition of the invention. The following compounds may be mentioned in detail: (Ia): Threo form (absolute configuration: RR / SS) (Ib): Hydrochloride of (Ia) (Ic): Erythro form (absolute configuration: RS / SR) (Id): Hydrochloride of (Ic) The compounds of formula (I) and their preparation are known (cf. DE-OS 29 51 163 CLeA 20 068] and the preparation examples).

The compounds of the above to be used as mixture components listed groups (A), (B), (C), (D), (E), (F), CG), CH), (I), CJ), CK), (L), (M), (N), (O), (P), (Q), (R) and (S) have already been described in the literature; see the following information (A): R. Wegler, 'Chemistry of Plant Protection and Pest Control', Volume 2, page 51, Springer Verlag Berlin / Heidelberg / New York, 1970; (B): R. Wegler, loc.cit., pages 95, 108, 109 and 110; (C): R. Wegler, loc. Cit., Page 70; (D): K.H.Büchel, 'Plant protection and pest control', page 146, Georg Thieme Verlag, Stuttgart, 1977; (E): R. Wegler, loc. Cit., Pages 65 and 66; (F): DE-AS 12 09 799, DE-OS 19 32 297, US-PS 30 10 968; (G): DE-AS 22 01 063, DE-AS 23 24 010, DE-OS 20 63 857, DE-AS 24 29 523, DE-OS 30 18 866, DE-OS 32 02 601, German patent application P 32 37 400 of October 8, 1982 [LeA 21 9653; (H): R. Wegler, loc. Cit., Page 132; (I) : German patent application P 32 34 529 of September 17, 1982 CLeA 21 962, US 39 17 838; (J): DE-OS 22 50 077, DE-OS 20 62 348; (K): DE-OS 27 32 257; (L): K.H.Büchel, loc.cit., Page 142; (M): Chem. Commun. 1972, No. 12, pp. 747-748; (N): R. Wegler, loc. Cit., Page 120; (0): R. Wegler, loc. Cit., Page 112; (P): R. Wegler, loc. Cit., Page 97 (Q): K.H.Büchel; loc.cit., page 149; DE-OS 26 56 747; (R): R. Wegler, loc.cit., Page 128 and (S): K.H.Büchel, loc.cit., Page 148.

Combinations of active ingredients from the threo form of 2,2-bisfluoromethyl-5-cyclohexyl-4- (1,2,4-triazol-1-yl) -3-pentanol are preferred of the formula (Ia) and an active ingredient of the formulas (IIa), (IIb), (IIc) or (IId); and / or an active ingredient of the formula (IiI); and / or an active ingredient of the formula (IV); and / or an active ingredient of the formulas (Va), (Vb), (Vc) or (Vd); and / or one Active ingredient of the formulas (VIIe); and / or an active ingredient of formula (VIII); and or an active ingredient of the formula (IXa); and / or an active ingredient of the formula (Xa); and or an active ingredient of the formula (XI); and / or an active ingredient of the formula (XII); and or an active ingredient of the formula (XIII).

To an active ingredient combination of the 2,2-bisfluoromethyl-5-cyclohexyl-4- (1,2,4-triazol-1-yl) -3-pentanols of formula (1) and the active ingredients from groups (A) or

CB) or (C) or (D) or (E) or (F) or (G) or

(H) or (i) or (J) or (K) or (L) or (M) or

(N) or (0) or (P) or (Q) or (R) and / or <5) can still additional active ingredients (e.g. as third-party components) are added.

The weight ratios of the active ingredient groups in the active ingredient combinations can fluctuate in relatively large areas. In general, it accounts for 1 part by weight on compound of F = re1 (I) 0.01 to 500 parts by weight of active ingredient from the active ingredient classes (A) to (S), preferably 0.02 to 200 parts by weight from the latter, particularly preferred 0.2 to 50 parts by weight.

The active ingredient combinations according to the invention have a strong microbicidal effect Effect on and can come in handy for combating unwanted microorganisms be used; they are suitable for use as pesticides.

Fungicidal agents in crop protection are used for control of Plasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes, Deuteromycetes.

The good plant tolerance of the active ingredient combinations in the Kaicentrations necessary to aggravate plant diseases permitted a treatment of above-ground parts of plants, of vegetation and seeds, and des Soil.

The active ingredient combinations according to the invention are very broad Spectrum of activity and can be used against parasitic fungi that are above ground Parts of plants are attacked or attack the plants from the ground, as well as seed-borne Pathogens. Such combinations of active ingredients are of particular practical importance as seed dressings against phytopathogenic fungi that are transmitted with the seed or occur in the soil and attack the crops from there. It acts it is seedling diseases, root rot, stem, stem, leaf, flower, Fruit and seed diseases, particularly caused by Tilletia urocystis, Ustilago, Septoria, Typhula, Rhvnchosporium, Helminthosporium and Fusarium species will. The plants become through the systemic effect of the one mixing partner often protected from pathogens for a long time after the dressing attack different parts of the shoot, e.g.

powdery mildew and rust fungi. The drug oinations can next to it can also be used as a soil treatment agent against phytopathogenic fungi and act against root rot and tracheomycoses caused e.g. by pathogens of the Genera Pythium, Verticillium, Ph, alophora, Rhizoctonia, Fusarium and Thielaviopsis caused.

However, the active ingredient combinations according to the invention also show excellent results Effect with direct application cation of the above-ground parts of the plant against pathogens on various crops, such as powdery mildew fungi (Erysiphe, Uncinula, Sphaerotheca, Podosphaera species, Leveillula taurica), rust fungi, Venturia species, Cercospora AdBn, Alternar ja species, Botrytis species, Phytthora species, Peronospora species, Fusarium species, Pyrenctioca species, coccl ioboiu s-Aden, Septoria species, P seudocerc osporel la herpotrichoides, Pyr icularia oryzae, Pellicularia sasakii.

The active ingredients can be converted into the usual formulations, such as solutions, emulsions, suspensions, powders, foams, pastes, granulates, aerosols, Active ingredient-impregnated natural and synthetic materials, fine encapsulation in polymers Substances and in coating compounds for seeds, also in formulations with fuel charges, such as smoking cartridges, cans, coils and the like, as well as ULV cold and warm smoke formulations.

These formulations are prepared in a known manner, for example by Mixing the active ingredients with extenders, i.e. liquid solvents, under Liquefied gases under pressure and / or solid carriers, if appropriate using surface-active agents, i.e. emulsifiers and / or dispersants and / or foam-generating agents. In the case of using water as an extender For example, organic solvents can also be used as auxiliary solvents. The following liquid solvents are essentially: aromatics, such as xylene, Toluene, or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic Hydrocarbons such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic Hydrocarbons, such as cyclohexane or paraffins, e.g. petroleum fractions, Alcohols such as butanol or glycol and their ethers and esters, ketones such as acetone, Methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents, such as dimethylformamide and dimethyl sulfoxide, and water; with liquefied gaseous Extenders or carriers are liquids that are meant to be used in normal Temperature and under normal pressure are gaseous, e.g. aerosol propellants such as halogenated hydrocarbons as well as butane, propane, nitrogen and carbon dioxide; come as solid carriers in question: e.g. natural rock flour, such as kaolins, clays, talc, chalk, Quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic rock powder, such as finely divided silica, aluminum oxide and silicates; as solid carriers for granulates are possible: e.g. broken and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite and synthetic granules made from inorganic and organic flours as well as granules made of organic material such as sawdust, coconut shells, Corn on the cob and tobacco stalks; come as emulsifying and / or foam-producing agents in question: e.g. non-ionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, Polyoxyethylene fatty alcohol ethers, e.g. alkylaryl polyglycol ethers, alkyl sulfonates, Alkyl sulfates, aryl sulfonates and protein hydrolysates; come as a dispersant in question: e.g. lignin sulphite waste liquors and methyl cellulose.

Adhesives such as carboxymethyl cellulose, natural and synthetic powdery, granular or latex-like polymers are used be like Gum arabic, polyvinyl alcohol, polyvinyl acetate, as well natural phospholipids such as cephalins and lecithins and synthetic phospholipids. Further additives can be mineral and vegetable oils.

Dyes such as inorganic pigments, e.g.

Iron oxide, titanium oxide, ferrocyan blue and organic dyes such as Alizarin, azo and metal phthalocyanine dyes and trace nutrients such as salts of iron, manganese, boron, ferrous, cobalt, molybdenum and zinc can be used.

The formulations generally contain between 0.1 and 95 percent by weight Active ingredient, preferably between 0.5 and 90 0, The active ingredients according to the invention can be mixed in the formulations or in the various application forms present with other known active ingredients, such as fungicides, bactericides, insecticides, Acaricides, nematicides, herbicides, bird repellants, growth substances, Plant nutrients and soil structure improvers.

The active ingredients can be used as such, in the form of their formulations or the use forms prepared therefrom by further dilution, such as ready-to-use Solutions, emulsions, suspensions, powders, pastes and granulates can be used. It is used in the usual way, e.g. by watering, dipping, spraying, Spraying, atomizing, vaporizing, injecting, silting up, spreading, dusting, Spreading, dry pickling, moist pickling, wet pickling, slurry pickling or encrusting.

When treating parts of plants, the concentrations of active substances can be reduced can be varied in the application forms over a wide range. You are in generally between 1 and 0.0001% by weight, preferably between 0.5 and 0.001%.

In the treatment of seeds, amounts of active ingredient of 0.001 to 50 g per kilogram of seed, preferably 0.01 to 10 g, are required.

When treating the soil, the active ingredient concentrations are 0.00001 up to 0.1% by weight, preferably from 0.0001 to 0.02% by weight, required at the site of action.

The following application examples serve as an explanation.

Example A Pyricularia test (rice) / protective solvent: 12.5 parts by weight Acetone emulsifier: 0.3 parts by weight of alkylaryl polyglycol ether Appropriate preparation of active ingredient, 1 part by weight of active ingredient is mixed with the specified amounts of solvent and dilute the concentrate with water and the specified amount of emulsifier to the desired concentration.

To test for protective effectiveness, young rice plants are sprayed with the active ingredient preparation to runoff. After the spray coating has dried the plants are inoculated with an aqueous spore suspension of Pyricularia oryzae. The plants are then in a greenhouse at 100 * rel.

Humidity and 250C.

The disease infestation is evaluated 4 days after the inoculation.

To achieve synergism between the active ingredients used in these experiments to show, the results were based on the method proposed by R.S. Colby described method (Calculating Synergistic and Antanogistic Responses of Herbicide Combinations; Weeds 15, 20-22, 1967). The expected infestation in% of the untreated control (E) was calculated according to equation X. Y E = 1 00 calculated. Here, X and Y mean the disease incidence - expressed in% of the untreated control - that the two Allow preparations for separate use. There is a synergistic effect before when the fungicidal effect of the active ingredient combinations is greater than that of the individually applied active ingredients. In this case the actually observed one must Infestation must be lower than the value calculated from the above formula for the expected infestation (E).

Table A Pyricularia test (rice) / protective active ingredients active disease ingredient fall in% of the concentration untreated control in% (Ia) (known) 0.0025 50 0.001 70 (IV) (known) 0.001 70 (TETRACHLORPHTHALID) 0.0005 90 (xII) (known) 0.001 50 (PROBENAZOLE) 0.0005 70 (VIIe) (known) 0.001 70 (PROCHLORAZ) 0.0005 70 Tabel A (continued) observed expected infestation after infestation (E) effective. use after application W i r k s t o f f conc. of the mixture of the mixture in X in% of the untreated Control mixture of (Ia) and (IV) 0.0025 (mixing ratio 2.5: 1) + 0.001 10 35 Mixture of (Ia) and (IV) 0.0025 (mixing ratio 5: 1) + 0.0005 3 45 Mixture of (Ia) and (XII) 0.0025 (mixing ratio 2.5: 1) + 0.001 10 25 mixture from (Ia) and (XII) 0.0025 (mixing ratio 5: 1) + 0.0005 10 35 mixture of (Ia) and (XII) 0.001 (mixing ratio 1: 1) + 0.001 10 35 mixture of (Ia) and (XII) 0.001 20 49 (mixing ratio 2: 1) + 0.0005 mixture of (Ia) and (VIie) 0.0025 15 35 (mixing ratio 2.5: 1) + 0.001 mixture of (Ia) and (VIIe) 0.0025 15 35 (mixing ratio 5: 1) + 0.0005 mixture of (Ia) and (VIIe) 0.001 20 49 (mixing ratio 1: 1) + 0.001 Example B Pellicularia test (Rice) / protective solvent: 12.5 parts by weight acetone emulsifier: 0.3 parts by weight Alkylaryl polyglycol ethers For the production of an expedient active ingredient preparation 1 part by weight of active ingredient is mixed with the specified amount of solvent and dilute the concentrate with water and the specified amount of emulsifier to the desired Concentration.

To test for effectiveness, young rice plants in the 3 to 4 leaf stage are used sprayed dripping wet. The plants remain in the greenhouse until they have dried off. Afterward the plants are inoculated with Pellicularia sasakii and at 250C and 100% relative Humidity set up.

The disease infestation is evaluated 5 to 8 days after the inoculation.

To achieve synergism between the active ingredients used in these experiments to show, the results were based on the method proposed by R.S. Colby described method (Calculating Synergistic and Antagonistic Responses of Herbicide Combinations; Weeds 15, 20-22, 1967). The expected infestation in% in the untreated control was calculated according to the equation E = X Y 100. Here, X and Y mean the disease infestation - expressed in% of the untreated control - that the two preparations in one allow separate application.

There is a synergistic effect when the fungicidal effect the active ingredient combination is greater than that of the individually applied active ingredients. In this case, the actually observed infestation must be less than that from The value calculated using the above formula for the expected infestation (E).

Table B Pellicularia test (rice) / protective active ingredient active ingredient Disease infestation concentration in% of unhandling in% control (Ia) (known) 0.0025 50 0.001 70 0.0005 90 (XI) (known) 0.0001 70 (PENCYCURON) 0.00005 100 (XIII) (known) 0.001 30 (VALIDAMYCIN) 0.0005 70 Table B (continued) observed expected infestation after infestation (E) after act. Application application Active ingredient conc. Of the mixture of the mixture in% in X of the untreated control Mixture of (Ia) and (XI) 0.0025 (mixing ratio 25: 1) + 0.0001 10 35 mixture from (Ia) and (XI) 0.001 (mixing ratio 10: 1) + 0.0001 25 49 mixture of (Ia) and (XI) 0.0025 25 50 (mixing ratio 50: 1) + 0.00005 mixture of (Ia) and (XI) 0.001 50 70 (mixing ratio 20: 1) + 0.00005 mixture of (Ia) and (XIII) 0.001 (mixing ratio 1: 1) + 0.001 10 21 mixture of (Ia) and (XIII) 0.0005 (mixing ratio 1: 2) + 0.001 10 27 mixture of (Ia) and (XIII) 0.0025 (Mixing ratio 5: 1) + 0.0005 10 35 Example C Erysiphe test (Barley) / protective solvent: 100 parts by weight dimethylformamide emulsifier: 0.25 part by weight of alkylaryl polyglycol ether for the production of an expedient active ingredient preparation 1 part by weight of active ingredient is mixed with the stated amounts of solvent and emulsifier and dilutes the concentrate with water to the desired concentration.

To test for protective effectiveness, young plants are sprayed dew damp with the active ingredient preparation. After the spray coating has dried on the plants with spores of Erysiphe graminis f.sp. hordei pollinated.

The plants are in a greenhouse at a temperature of approx. 200C and a relative humidity of approx. 80% set up for the development to benefit from powdery mildew pustules.

Evaluation is carried out 7 days after the inoculation.

To achieve synergism between the active ingredients used in this experiment to show, the results were based on the method proposed by R.S. Colby described method (Calculating Synergistic and Antagonistic Responses of Herbicide Combinations; Weeds 15, 20-22, 1967). The he wait infestation in% of untreated Control was calculated according to E 100 100 equation. Here, X and Y mean the disease incidence - expressed in% of the untreated control - that the two Allow preparations for separate use.

There is a synergistic effect when the fungicidal effect the active ingredient combination is greater than that of the individually applied active ingredients. In this case, the actually observed infestation must be less than that from The value calculated using the above formula for the expected infestation (E).

Table C Erysiphe test (barley) / protective active ingredient active ingredient concentration of the disease in% in the spray of the untreated broth in% by weight of the control (Ia) (known) 0.00025 83.7 (Vd) (PROPINEB) (known) 0.025 45.7 observed expected Infestation after infestation (E) application of the after application Mix the mix in% of the untreated control Mixture of (Ia) and (Vd) 0.00025 3.7 38.3 +0.025 (Mixing ratio 1: 100) Example D Leptosphaeria nodorum test (wheat) / protective solvent: 100 parts by weight of dimethylformamide emulsifier: 0.25 part by weight of alkylaryl polyglycol ether To produce an appropriate preparation of active ingredient, 1 part by weight of active ingredient is mixed with the stated amounts of solvent and emulsifier and the concentrate is diluted with water to the desired concentration.

To test for protective effectiveness, young plants are sprayed dew damp with the active ingredient preparation. After the spray coating has dried on the plants were sprayed with a conidia suspension of Leptosphaeria nodorum.

The plants remain at 200 ° C. and 100% relative atmospheric humidity for 48 hours in an incubation cabin.

The plants are in a greenhouse at a temperature of about 150C and a relative humidity of about 80 liters.

Evaluation is carried out 10 days after the inoculation.

To achieve synergism between the active ingredients used in this experiment to show, the results were based on the method proposed by R.S. Colby described method (Calculating Synergistic and Antagonistic Responses of Herbicide Combinations; Weeds 15, 20-22, 1967). The expected infestation in% of untreated control was determined according to the equation E = X. Y 100 calculated. Included X and Y mean the disease infestation - expressed in% of the untreated control - which the two preparations allow for separate use.

There is a synergistic effect when the fungicidal effect the active ingredient combination is greater than that of the individually applied active ingredients. In this case, the actually observed infestation must be less than that from The value calculated using the above formula for the expected infestation (E).

Table D Leptosphaeria nodorum test (wheat) / protective active ingredient active ingredient disease concentration infestation in% in the Konin% by weight trolle (Ia) (known) 0.005 100 (IId) CAPTAFOL) (known) 0.01 82.5 (XIV) tXNILAZIN) 0.005 64.8 (known) observed expected Infestation after infestation (E) Application according to application the mixture dung the mi- schung in% of the untreated control Mixture of (Ia) and (IId) (Mixing ratio 1: 2) 0.005 50.0 82.5 +0.01 Mix of (Ia) and (XIV) (Mixing ratio 1: 1) 0.005 50.0 64.8 +0.005 Production examples: Example 1: (Ia): threo form (absolute configuration: RR / SS) (Ib): hydrochloride of (Ia) (Ic): erythro form (absolute configuration: RS / SR) (Id): hydrochloride of (ic) 151, 1 g (0.51 mol) of 2,2-bisfluoromethyl-5-cyclohexyl-4- (1,2,4-triazol-1-yl) -3-pentanone are dissolved in 500 ml of methanol and cooled with ice / sodium chloride 24.5 g of sodium borohydride are added in portions so that the internal temperature can be kept at 0OC to 10 ° C. The mixture is allowed to stir for 15 hours at room temperature, 1 l of 2N hydrochloric acid and then 50 ml of saturated soda solution, mixed with 50 ml of 40% sodium hydroxide solution, are added dropwise with ice cooling until neutralization. The resulting precipitate is filtered off with suction, the organic phase is extracted twice with 500 ml of methylene chloride each time and the combined methylene chloride phases are washed twice with 1 l of water each time. The precipitate and the methylene chloride phase are then combined, the solution is washed with 1 liter of water and the solvent is distilled off.

147.4 g of oil are obtained which are taken up in 500 ml of diethyl ether and saturated with 150 ml of hydrogen chloride Diethyl ether added will. The solvent is distilled off and colorless crystals are obtained 500 ml of ethyl acetate are added. After standing for two hours, suction is performed. 133.5 g of compound (Ib) with a melting point of 1380 ° C. to 1420 ° C. are obtained.

The mother liquor is concentrated and the residue is redissolved from 150 ml Recrystallized ethyl acetate. 16.9 g of the compound (Id) are obtained as a precipitate from melting point 1580C to 1620C.

49 g of the compound (Ib) are suspended in 300 ml of methylene chloride and shaken with 150 ml of saturated soda solution. The organic phase is separated off and the solvent is distilled off. 35 g of compound (Ia) with a melting point are obtained 1080C to 1100C.

The connection is obtained in a corresponding manner from the connection (Id) (Ic) melting point 1220C.

Claims (7)

Patent claims 1. Fungicidal agent, characterized by a content of an active ingredient combination of pure diastereomers or diastereomer mixtures of 2,2-bisfluoromethyl-5-cyclohexyl- (1,2,4-triazol-1-yl) -3-pentanol of the formula tI) and their acid addition salts and metal salt complexes and (A) network sulfur and / or (B) polyhaloalkylthio derivatives of the formulas (IIa) R1 = (CH3) 2N-S02-, (IIb) R1 and R2 = Haloalkyl = CCl3 (IIc) R1 and R = Haloalkyl = -CCl3 (IId) R¹ and R² = Haloalkyl = -.CCt2-CHCL2 and / or (C) a guanidine derivative of the formula and / or (D) an aromatic carboxylic acid derivative of the formula and / or (E) dithiocarbamates of the formula (Va) R1 = H, M = Zn (Vb) R1 = H, M = Mn (Vc) mixture of (Va) and (Vb) (Vd) R1 = CH3, M = Zn and / or (F) benzimidazole- Derivatives of the formulas and / or (G) derivatives of imidazoles and triazoles of the formulas (VIIa) X = Cl, A = CO (VIIb) x = CL, A = CH (OH) (VIIf) R1 = CL, R2 = H, A = -CH2CH2-, X = H, Y = H (VIIg) R1 = Cl, R2 = H, A = -CH2CH2-, X = F, Y = H (VIIh ) R1 = CL, R2 = H, A = -CH2CH2-, X = F, Y = F (VIIi) R1 = CL, R2 = H, A = -CH = CH-, X = H, Y = H (VIIj ) R1 = Cl, R2 = CH3, A = -OCH2-, X = H, Y = H (VIIk) R1 = Cl, R² = CH3, A = -OCH2-, X = F, Y = H R² = H, A = -OCH2-, X = H, Y = H (VIIm) R1 = Cl, R2 = Cl, A = -OCH2-, X = F, Y = H (VIIn) R1 = CH30N = CH- , R2 = H, A = -OCH2-, X = H, Y = H and / or (H) a phosphoric acid ester of the formula and / or (I) a tetrahydroquinoline derivative of the formulas (IXa) Hal = Br (IXb) Hal = Cl (IXc) and / or (J) S, H-heterocycle compounds of the formulas and / or (K) a urea derivative of the formula and / or (L) a sulfonamide derivative of the formula and / or (M) a polyhydroxyether derivative of the formula and / or (N) a triazine derivative of the formula and / or (0) a copper complex salt of the formula and / or (P) an N-formyl derivative of the formula and / or (O) morpholine derivatives of the formulas and / or (R) a quinoxaline derivative of the formula and / or (S) a dicarboximide derivative of the formulas 2. Fungicidal agent according to claim 1, characterized in that the weight ratio of 2,2-bis-fluoromethyl-5-cyclohexyl-4- (1,2,4-triazol-1-yl) -3-pentanol in the active substance combination to the active ingredients from the active ingredient classes (A) to (S) is between 1: 0.01 and 1: 500. 3. Fungicidal agent according to Claims 1 and 2, characterized in that that the weight ratio is between 1: 0.02 and 1: 200. 4. Fungicidal agent according to Claims 1 and 2, characterized in that that the weight ratio is between 1: 0.2 and 1:50. 5. A method of combating fungi, characterized in that an active ingredient combination according to claim 1 can act on fungi or their habitat leaves. 6. Use of active compound combinations according to Claim 1 for combating of mushrooms. 7. A process for the production of fungicidal agents, characterized in that that an active ingredient combination according to claim 1 with extenders and / or surface-active Means mixed up.