IL93443A - Trifluoromethyl-phenylazolylmethyl-oxirane derivatives and fungicides containing these compounds - Google Patents

Abstract

Trifluoromethylphenylazolylmethyloxiranes of the general formula I <IMAGE> in which R<1> represents hydrogen, halogen, nitro, phenyl, phenoxy, alkyl, alkoxy, haloalkyl or haloalkoxy, and, moreover, R<1> together with the phenyl ring can also form a naphthyl radical which is unsubstituted or substituted, n represents an integer from 1 to 5, R<2> represents ortho- or para-trifluoromethyl, X represents CH or N, and their acid addition salts and metal salts which are tolerated by plants, and fungicides containing these compounds.

Description

o iN o>¾>3nn ni>*io3 >!?ιηρι Trifluoromethylphenylazolylmethyloxirane derivatives and fungicides containing these compounds BASF Aktiengesellschaft C. 79955 93443/3 - 1 - The present invention rel ates to novel azol e compounds and fungicides containing these .

EP-A 94 564 (corresponding to Israel Patent No . 68433) discloses azolylmethyloxiranes, in particular 2-(l,2,4-triazol-l-ylmethyl)-2- (4-chlorophenyl)-3-(3-trifluoromethyl)oxirane whose fungicidal action is not satisfactory in all cases.

Hence the object of the present invention was to provide azolylmethyloxiranes with an improved action.

We have now found that compounds of the formula n where R1 is hydrogen, halogen, nitro, phenyl, phenoxy, C^-Cs- alkyl, C^-Cs-alkoxy, C^-C^-haloalkyl , C^-Cs-haloalkoxy and, furthermore, Rl together with the phenyl nucleus can also form naphthyl which is unsubstituted or substituted by R1, n is an integer from 1 to 5 , R2 is ortho- or para-trifluoromethyl, X is CH or N and the acid addition salts or metal salts thereof which are tolerated by plants, have a better fungicidal action, especially against diseases of cereals, than known azolylmethyloxiranes.

The, compounds of the formula I contain chiral centers and are generally obtained in the form of race- mates or diastereomeric mixtures of erythro and threo forms. The erythro and threo diastereomers of the compounds according to the invention can be separated in a - 2 - O.Z. 0050/40637 conventional manner, for example on the basis of their different solubilities or by column chromatography, and isolated in pure form. Pure enantiomers can be obtained by conventional methods from a diastereomer isolated in such a way. Both the pure diastereomers or enantiomers and the mixtures thereof produced in the synthesis are used as fungicidal agents.

Examples of R1 are: halogen such as fluorine, chlorine, bromine or iodine, nitro, phenyl or phenoxy, eg. in the para position, ^C^-alkyl or C^-Cs-alkoxy, each alkyl being methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl or neopentyl, Ci-C-haloalkyl or Cx-C^-haloalkoxy, especially mono- to perhalogenated alkyls such as CH2C1, CHC12, CC13, CH2F, CHF2, CH2Br, CHBrCl, CF2C1, C2F5, CF2- CHF2 CH2CH2C1, CH2CHC12, CH2CH2Br, C3F7 and, in particular, CF3.

In addition, R1 can form, together with the phenyl nucleus to which it is bonded, a naphthyl, eg. 1-naphthyl or 2-naphthyl, which in turn can be substituted one or more times by the radicals mentioned above for R1. n is an integer from 1 to 5, in particular 1 to 3.

Examples of acid addition salts are the hydro-chlorides, hydrobromides , sulfates, nitrates, phosphates, oxalates or dodecylbenzenesulfonates . The activity of the salts derives from the cation so that generally the anion is immaterial. The salts of the active compounds according to the invention are prepared by reacting the azolyl-methyloxiranes (I) with suitable acids.

Metal salts of the active compounds I or their salts can be formed with, for example, copper, zinc, tin, manganese, iron, cobalt or nickel by reacting the azolyl-methyloxiranes with corresponding metal salts.

The compounds of the formula I can be prepared by a) reacting a compound of the formula II - 3 - O.Z. 0050/40637 where R1 and R2 have the stated meanings, and L is a leaving group which can be replaced nucleophili- cally, with a compound of the formula III ίΧ^Ν-Μβ III N- where Me is hydrogen or a metal, and X has the stated meaning, or b) converting a compound of the formula IV where R1, R2, n and X have the stated meanings, into the epoxide and, where appropriate, converting the resulting compounds into their salts with acids which are tolerated by plants.

Reaction a) is carried out, if Me is hydrogen, in the presence or absence of a solvent or diluent and with or without the addition of an inorganic or organic base and of a reaction accelerator.

The preferred solvents and diluents include ketones such as acetone, methyl ethyl ketone or cyclo-hexanone, nitriles such as acetonitrile or propionitrile, alcohols such as methanol, ethanol, iso-propanol, n-butanol or glycol, esters such as ethyl acetate, methyl - 4 - O.Z. 0050/40637 acetate or butyl acetate, ethers such as tetrahydrofuran, diethyl ether, methyl tert-butyl ether, dlmethoxyethane, dioxane or diisopropyl ether, amides such as dimethyl-formamide, dimethylacetamide or N-methylpyrrolidone, as well as dimethyl sulfoxide, sulfolane or mixtures thereof.

Examples of suitable bases, which can also be used as acid-binding agents in the reaction, are alkali metal hydroxides such as lithium, sodium or potassium hydroxide, alkali metal carbonates such as sodium, potassium or cesium carbonate, or sodium, potassium or cesium bicarbonate, pyridine or 4-dimethylaminopyridine, alkali metal hydrides such as lithium, sodium or potassium hydride, alkali metal amides such as of sodium or potassium, as well as sodium or potassium tert-butoxide, triphenylmethyllithium, -sodium or -potassium, and naphthyllithium, -sodium or -potassium. However, it is also possible to use other conventional bases.

Suitable and preferred reaction accelerators are metal halides such as sodium iodide or potassium iodide, quaternary ammonium salts such as tetrabutylammonium chloride, bromide, iodide or bisulfate, benzyltriethyl-ammonium chloride or bromide or crown ethers such as 12-crown-4, 15-crown-5, 18-crown-6 , dibenzo-18-crown or dicyclohexano-18-crown-6.

The reaction is generally carried out at from 10 to 150°C, in particular 20 to 120°C, under atmospheric or superatmospheric pressure, continuously or batchwise.

If Me is a metal, reaction a) can be carried out in the presence of a solvent or diluent and at from -10 to 150°C, in particular 0 to 120 "C, preferably 20 to 80°C. When a solvent is present, the reaction is expediently carried out at the boiling point of the solvent.

The preferred solvents and diluents include amides such as dimethylformamide, diethylformamide, dimethylacetamide, diethylacetamide, N-methylpyrrolidone, hexamethylphosphoric triamide, sulfoxides such as - 5 - O.Z. 0050/40637 dimethyl sulfoxide and, finally, sulfolane.

Suitable solvents and diluents for reaction b) are ketones such as acetone, methyl ethyl ketone or cyclohexanone, nitriles such as acetonitrile or propio-nitrile, alcohols such as methanol, -ethanol, iso-propa-nol, n-butanol or glycol, esters such as ethyl acetate, methyl acetate or butyl acetate, ethers such as tetra-hydrofuran, diethyl ether, dimethoxyethane, dioxane, diisopropyl ether or methyl tert-butyl ether, amides such as dimethylformamide, dimethylacetamide or N-methyl-pyrrolidone, as well as dimethyl sulfoxide, sulfolane or mixtures thereof.

The novel starting compounds II are obtained by epoxidation of the corresponding olefins V: (cf. 6. Dittus in Houben-Weyl-Miiller, Methoden der Organischen Chemie, Georg Thieme Verlag, Stuttgart, 1965, vol. VI, 3, pages 385 et seq. ) .

Compound V is prepared by halogenating or oxidizing olefins of the formula VI in the allyl position by conventional methods.

Suitable halogenating reagents are N-chloro- and N-bromosuccinimide. Examples of solvents are halohydro-carbons such as carbon tetrachloride, trichloroethane or methylene chloride. The halogenation is generally carried 6 - O.Z. 0050/40637 out at from 20 to 100°C.

The allyl oxidation is carried out with peresters such as tert-butyl perbenzoate or tert-butyl peracetate in the presence of a heavy metal salt such as copper(I) chloride or copper(I) bromide. The oxidation is usually carried out in inert solvents such as dichloromethane, toluene, xylene, chloroform, tetrachloromethane or dichloromethane at from 10 to 100 SC.

The allyl halides V and the allyl alcohols with L = OH obtained in this way are subsequently converted into the corresponding epoxides II and VII.

For this, the olefins V are oxidized with peroxy-carboxylic acids such as perbenzoic acid, 3-chloroper-benzoic acid, 4-nitroperbenzoic acid, monoperphthalic acid, peracetic acid, perpropionic acid, permaleic acid, monopersuccinic acid, perpelargonic acid or trifluoroper-acetic acid in inert solvents, preferably chlorinated hydrocarbons, eg. methylene chloride, chloroform, carbon tetrachloride or dichloroethane, but possibly also in acetic acid, ethyl acetate, acetone or dimethylformamide, in the presence or absence of a buffer such as sodium acetate, sodium carbonate, disodium hydrogen phosphate or Triton B.

The reaction is carried out at from 10 to 100°C, and the reaction can be catalyzed with, for example, iodine, sodium tungstate or light. Also suitable for the oxidation are alkaline solutions of hydrogen peroxide (about 30 % strength) in methanol, ethanol, acetone or acetonitrile at 25 to 30°C, and alkyl hydroperoxides, eg. tert-butyl hydroperoxide, cumene hydroperoxide and - 7 - O.Z. 0050/40637 cyclohexyl hydroperoxide, with or without the addition of a catalyst, eg. sodium tungstate, pertungstic acid, molybdenum hexacarbonyl or vanadyl acetylacetonate. Some of these oxidizing agents can be generated in situ.

Whereas the resulting epoxy halides II (L -halogen) can be immediately reacted by process a), the corresponding epoxy alcohols VII are converted into reactive esters which are then reacted with the compounds III by process a) .

The reactive esters which are reacted with III are prepared by conventional methods (Houben-Weyl-Miiller, Methoden der Organischen Chemie, Georg Thieme Verlag, Stuttgart, 1955, volume 9, pages 388, 663, 671). Examples of such esters are methanesulfonates, trifluoromethane-sulfonates, 2,2,2-trifluoroethanesulfonates , nonafluoro-butanesulfonates, 4-methylbenzenesulfonates, 4-bromo-benzenesulfonates, 4-nitrobenzenesulfonates or benzene-sulfonates .

The compounds V can be prepared by conventional methods for olefin synthesis (Houben-Weyl-Miiller, Methoden der Organischen Chemie, Georg Thieme Verlag, Stuttgart, 1972, volume V, lb).

Furthermore, the epoxy alcohols VII can be prepared by oxidation and subsequent reduction of the propenals obtainable as described in DE-A 37 22 886.

These substituted propenals are dissolved in alcohols such as methanol, ethanol, n- or iso-propanol or buta-nols, or solvent mixtures . containing these alcohols are used, and are oxidized with hydrogen peroxide, cyclohexyl peroxide, tert-butyl hydroperoxide or cumene hydroperoxide with the addition of bases. The resulting formyl-oxirane can be reduced without further purification to the corresponding epoxy alcohol VII with basic sodium borohydride solution or catalytically.

The examples which follow illustrate the preparation of the active compounds! - 8 - O.Z. 0050/40637 Preparation Examples I Preparation of the starting materials EXAMPLE A 4 . 2 g of sodium hydroxide in 30 ml of water are added to a solution of 40 g of 2-trifluoromethylbenz-aldehyde in 300 ml of methanol. The reaction mixture is cooled to 10°C, and 35 g of phenylacetaldehyde are rapidly added, during which the solution warms to 30-40 °C. The mixture is stirred at 40 eC for 10 hours and then 200 ml of water are added to the colorless reaction solution, and the resulting emulsion is extracted by shaking with methyl tert-butyl ether. The organic phase is separated off, dried over sodium sulfate and concentrated. Filtration of the residue through a silica gel column (ethyl acetate/n-hexane = 1 : 3 ) results in an 80 % yield of E/Z-2-phenyl-3- ( 2-trifluoromethylphenyl)prope-nal.

EXAMPLE B 52 g of E/Z-2-phenyl-3- ( 2-trifluoromethylphenyl)-propenal are dissolved in 300 ml of methanol, and 2 . 2 ml of concentrated sodium hydroxide solution are added. The reaction solution is stirred at 0°C while 14 . 3 g of hydrogen peroxide (approximately 50 % strength) are slowly added dropwise, during which the internal tempera-ture does not exceed 30 eC. After the addition is complete, the mixture is stirred at room temperature for 6 hours and subsequently 2 . 35 g of sodium borohydride dissolved in a little 10 % strength sodium hydroxide solution are added. The reaction mixture is stirred at room temperature for 18 hours and then 200 ml of water are added, and the resulting emulsion is extracted by shaking with methylene chloride. The organic phase is then dried over sodium sulfate and concentrated, and the residue is recrystallized from isopropanol. A 62 % yield of cis-2-hydroxymethyl-2-phenyl-3- ( 2-trifluoromethylphenyl)oxirane is obtained. - 9 O.Z. 0050/40637 EXAMPLE C 37.5 g of 4-methylbenzenesulfonyl chloride are added to a solution of 49 g of cis-2-hydroxymethyl-2-phenyl-3-(2-trifluoromethylphenyl)oxirane in 200 ml of dichloromethane and 53 g of triethylamine at room temperature. After 24 hours, the reaction mixture is washed with aqueous sodium bicarbonate solution and water, dried over sodium sulfate and evaporated under reduced pressure. 55 g of cis-2-(4-methylbenzenesulfonyloxymethyl)-2-phenyl-3-(2-trifluoromethylphenyl)oxirane are obtained from the residue and subsequently reacted with triazole as in the following example.

II Preparation of the final products EXAMPLE 1 5.2 g of sodium hydroxide are added to a solution of 9.4 g of 1,2,4-triazole in 100 ml of N-methylpyr-rolidone, and the mixture is heated at 50 "C for 30 minutes. After it has cooled to room temperature, 57 g of cis-2- ( 4-methylbenzenesulfonyloxymethyl) -2-phenyl-3-( 2-trifluoromethylphenyl)oxirane dissolved in 100 ml of N-methylpyrrolidone are slowly added dropwise, and the mixture is stirred at room temperature for 12 hours. Subsequently 200 ml of water are added, and the mixture is extracted several times with methyl tert-butyl ether; the organic phase is washed twice with water, dried over sodium sulfate and concentrated. Crystallization from methyl tert-butyl ether/n-hexane results in a 75 % yield of cis-2- (1,2, 4-triazol-l-ylmethyl) -2-phenyl-3-( 2-tri-fluoromethylphenyl)oxirane with melting point 132-134 °C (compound no. 1).

The compounds listed in the table can be prepared as in Example 1: 10 O.Z. 0050/40637 Table NO. Rl R2 X M.p. (°C)/IR n 5 1 H 2-CF3 N 132-134 2 2-Cl 2-CF3 N 1506, 1315, 1172, 1124, 1038, 771 3 2-F 2-CF3 N 4 4-Cl 2-CF3 N 117-119 5 4-F 2-CF3 N 110-112 10 6 2,4-F2 2-CF3 N 7 2,4-Cl2 2-CF3 N 8 4-Br 2-CF3 N 9 4-OCF3 2-CF3 N 10 4-OCH3 4-CF3 N 15 11 H 4-CF3 N 12 2-Cl 4-CF3 N 13 2-F 4-CF3 N 14 4-Cl 4-CF3 N 15 4-F 4-CF3 N 20 16 2,4-F2 4-CF3 N 17 2,4-Cl2 4-CF3 N 18 4-Br 4-CF3 N 19 4-OCF3 4-CF3 N 20 4-OCH3 4-CF3 CH 25 21 H 2-CF3 CH 132-134 22 2-Cl 2-CF3 CH 1503, 1315, 1170, 1124, 1038, 770 cm"1* 23 2-F 2-CF3 CH 24 4-Cl 2-CF3 CH 30 25 4-F 2-CF3 CH 127-130 26 2,4-F2 2-CF3 CH 27 2,4-Cl2 2-CF3 CH 28 4-Br 2-CF3 CH 29 4-OCF3 2-CF3 CH 35 40 890092 11 O.Z. 0050/40637 Table - continued - No. Ri R2 X M.p. (°C) 530 4-0CH3 4-CF3 CH 31 H 4-CF3 CH 32 2-Cl 4-CF3 CH 33 2-F 4-CF3 CH 34 4-C 4-CF3 CH 1035 4-F 4-CF3 CH 1512, 1326, 1125, 1068, 840 36 2,4-F2 4-CF3 CH 37 2,4-Cl2 4-CF3 CH 38 4-Br 4-CF3 CH 39 4-OCF3 4-CF3 CH 1540 4-OCH3 4-CF3 CH *) 2:1 c is/trans mixture 20 25 30 35 40 12 O.Z. 0050/40637 Generally speaking, the novel compounds are extremely effective on a broad spectrum of phytopathogenic fungi, in particular those from the Asco-mycetes and Basidiomycetes classes. Some of them have a systemic action and can be used as foliar and soil fungicides.

The fungicidal compounds are of particular interest for controlling a large number of fungi in various crops or their seeds, especially wheat, rye, barley, oats, rice, Indian corn, lawns, cotton, soybeans, coffee, sugar cane, fruit and ornamentals in horticulture and viticulture, and in vegetables such as cucumbers, beans and cucurbits.

The novel compounds are particularly useful for controlling the following plant diseases: Erysiphe graminis in cereals, Erysiphe cichoracearum and Sphaerotheca fuliginea in cucurbits, Podosphaera leucotricha in apples, Uncinula necator in vines, Puccinia species in cereals, Rhizoctonia species in cotton and lawns, list il ago species in cereals and sugar cane, Venturia inaequalis (scab) in apples, Septoria nodorum in wheat, Botrytis cinerea (gray mold) in strawberries and grapes, Cercospora arachidicola in groundnuts, Pseudocercosporella herpotrichoides in wheat and barley, Pyricularia oryzae in rice, Hemileia vastatrix in coffee, Alternaria solani in potatoes and tomatoes, Sclerotium rolfsii in groundnuts and lawn varieties, Fusarium and Verticillium species in various plants.

The compounds are applied by spraying or dusting the plants with the active ingredients, or treating the seeds of the plants with the active ingredients. They may be applied before or after infection of the plants or seeds by the fungi.

The novel substances can be converted into conventional formulations such as solutions, emulsions, suspensions, dusts, powders, pastes and granules. The application forms depend entirely on the purposes for which they are intended; they should at all events ensure a fine and uniform distribution of the active ingredient. The formulations are produced in known manner, for example by extending the active ingredient with solvents and/or 13 O.Z. 0050/40637 carriers, with or without the use of emulsifiers and dispersants; if water is used as solvent, it is also possible to employ other organic solvents as auxiliary solvents. Suitable auxiliaries for this purpose are solvents such as aro atics (e.g., xylene), chlorinated aromatics (e.g., chlorobenz-enes), paraffins (e.g., crude oil fractions), alcohols (e.g., methanol, butanol), ketones (e.g., cyclohexanone), amines (e.g., ethanolamine, dimethylformamide) , and water; carriers such as ground natural minerals (e.g., kaolins, aluminas, talc and chalk) and ground synthetic minerals (e.g., highly disperse silica and 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 waste liquors and methylcellulose.

The fungicidal agents generally contain from 0.1 to 95, and preferably from 0.5 to 90, wt of active ingredient. The application rates are from 0.02 to 3 kg or more of active ingredient per hectare, depending on the type of effect desired. The novel compounds may also be used for protecting materials, for example against wood-destroying fungi such as Conio-phora puteana and Polystictus versicolor. The novel active ingredients may also be employed as fungicidally effective components of oily wood preservatives for protecting wood against wood-discoloring fungi. The agents are applied by treating, e.g., impregnating or painting, the wood with them.

The agents and the ready-to-use formulations prepared from them, such as solutions, emulsions, suspensions, powders, dusts, pastes and granules, are applied in conventional manner, for example by spraying, atomizing, dusting, scattering, dressing or watering.

Examples of formulations are given below. 1. 90 parts by weight of compound no. 5 is mixed with 10 parts by weight of N-methyl-ct-pyrrolidone. A mixture is obtained which is suitable for application in the form of very fine drops.

II. 20 parts by weight of compound no. 21 is dissolved in a mixture consisting of 80 parts by weight of xylene, 10 parts by weight of the adduct of 8 to 10 moles of ethylene oxide and 1 mole of oleic acid-N-monoethanolamide, 5 parts by weight of the calcium salt of dodecylbenzene-sulfonic acid, and 5 parts by weight of the adduct of 40 moles of ethylene oxide and 1 mole of castor oil. By pouring the solution into water and uniformly distributing it therein, an aqueous dispersion is obtained. 14 O . Z . 0050/40637 III. 20 parts by weight of compound no. 25 is dissolved in a mixture consisting of 40 parts by weight of cyclohexanone, 30 parts by weight of iso- butanol, 20 parts by weight of the adduct of 40 moles of ethylene oxide and 1 mole of castor oil. By pouring the solution into water and finely 5 distributing it therein, an aqueous dispersion is obtained.

IV. 20 parts by weight of compound no. 5 is dissolved in a mixture consisting of 25 parts by weight of cyclohexanol, 65 parts by weight of a mineral oil fraction having a boiling point between 210 and 280°C, and 10 10 parts by weight of the adduct of 40 moles of ethylene oxide and 1 mole of castor oil. By pouring the solution into water and uniformly distributing it therein, an aqueous dispersion is obtained.

V. 80 parts by weight of compound no. 1 is well mixed with 3 parts by 15 weight of the sodium salt of di isobutylnaphthalene-ct-sulfonic acid, 10 parts by weight of the sodium salt of a lignin-sulfonic acid obtained from a sulfite waste liquor, and 7 parts by weight of powdered silica gel, and triturated in a hammer mill. By uniformly distributing the mixture in water, a spray liquor is obtained. 20 VI. 3 parts by weight of compound no. 21 is intimately mixed with 97 parts by weight of particulate kaolin. A dust is obtained containing 3% by weight of the active ingredient. 25 VII. 30 parts by weight of compound no. 1 is intimately mixed with a mixture consisting of 92 parts by weight of powdered silica gel and 8 parts by weight of paraffin oil which has been sprayed onto the surface of this silica gel. A formulation of the active ingredient is obtained having good adherence. 30 VIII. 40 parts by weight of compound no. 5 is intimately mixed with 10 parts by weight of the sodium salt of a phenolsulfonic acid-urea- formaldehyde condensate, 2 parts of silica gel and 48 parts of water to give a stable aqueous dispersion. Dilution in water gives an aqueous 35 dispersion.

IX. 20 parts by weight of compound no. 25 is intimately mixed with 2 parts by weight of the calcium salt of dodecylbenzenesulfonic acid, 8 parts by weight of a fatty alcohol polyglycol ether, 2 parts by weight 40 of the sodium salt of a phenolsulfonic acid-urea-formaldehyde condensate and 68 parts by weight of a paraffinic mineral oil. A stable oily dispersion is obtained. 15 O.Z. 0050/40637 In these application forms, the agents according to the invention may also be present together with other active ingredients, for example herbicides, insecticides, growth regulators, and fungicides, and may furthermore be mixed and applied together with fertilizers. Admixture with other fun-gicides frequently results in an increase in the fungicidal spectrum.

For the following experiment, the active ingredient 2-(l, 2, 4-triazol-l-yl-methyl)-2-(4-chlorophenyl)-3-(3-trifluoromethyl)-oxirane (A) disclosed in EP-A 94,564 was employed.

Use Example Action on Botrytis cinerea in pimientos Pimiento seedlings of the "Neusiedler Ideal Elite" variety with 4 to 5 well developed leaves were sprayed to runoff with aqueous suspensions containing (dry basis) 80% of active ingredient and 20% of emulsifier. After the sprayed-on layer had dried, the plants were sprayed with a conidial suspension of the fungus Botrytis cinerea and kept in a high-humidity chamber at 22 to 24°C. After 5 days, the disease had spread on the untreated control plants to such an extent that the necroses covered the major portion of the leaves.

The results show that active ingredients nos. 1, 5, 21 and 25, applied as 0.05wt% spray liquors, had a better fungicidal action (0 - 10% attack) than comparative agent A (80% attack).

Claims (5)

, ΖΑ 0050/40637 We claim:

1. . Tri fluorometh 1 hen lazolylmeth lo iranes of the general formula I where R 1 is hydrogen, halogen, nitro, phenyl, phenoxy, Cj-Cs-alkyl, Cj-C5-alkoxy, Ci-C- -haloalkyl, Cj-Cs-haloalkoxy and, furthermore, Ri together with the phenyl nucleus may also form naphthyl which is unsubstituted or substituted by Ri, n is an integer from 1 to 5, is ortho- or para-trifluoromethyl, X is CH or N, and the acid addition salts and metal salts thereof which are tolerated by plants.

2. A process for the manufacture of trifIuoro eth lphenyl azolylmethyl- oxiranes of the formula I as set forth in claim 1 , wherein a) a compound of the formula II where R and R2 have the above meanings and L is a nucleophi 1 ic- ally substitutable leaving group, is reacted with a compound of the formula III ^X^N-Me Γ. I I", N 1 ,ΖΑ 17 0050/40637 where Me is hydrogen or a metal atom and X has the above meanings, or b) a compound of the formula IV where R1, R2, n and X have the above meanings, is epoxidized, and the compounds thus obtained are if desired converted into their salts with plant-tolerated acids.

3. A fungicidal agent containing a compound of the formula I as set forth in claim 1.

4. A fungicidal agent containing an inert additive and a fungicidally effective amount of a compound of the formula I where is hydrogen, halogen, nitro, phenyl, phenoxy, Ci-Cs-alk l, Ci-C5-alkoxy, Ci-C. -haloalkyl, Cj-Cs-haloalkoxy and, furthermore, Rl together with the phenyl nucleus may also form naphthyl which is unsubstituted or substituted by Rl, is an integer from 1 to 5, is ortho- or para-trifluoromethyl, is CH or N, or an acid addition salt or metal salt thereof which is tolerated by plants. ,ΖΑ 18 0050/40637

5. A process for combating fungi, wherein a fungicidally effective amount of an azolylmethyloxirane of the general formula I where RI is hydrogen, halogen, nitro, phenyl, phenoxy, Ci-Cs-alky , Ci-C5~alkoxy, Ci-C -haloalkyl, Cj-Cs-haloalkoxy and, furthermore, Rl together with the phenyl nucleus may also form naphthyl which is unsubstituted or substituted by R , n is an integer from 1 to 5, R2 is ortho- or para-trifluoromethyl, X is CH or N, or a plant-tolerated acid addition salt or metal salt thereof is allowed to act on the fungi, or the materials, areas, timber, plants or seed threatened by fungus attack. A compound of the formula I as set forth in claim 1, where R is hydrogen, R2 is 2-CF3 and X is N. A compound of the formula I as set forth in claim 1, where Rl is 4-fluorine, R2 is 2-CF3 and X is N. A compound of the formula I as set forth in claim 1, where Rl is hydrogen, R2 is 2-CF3 and X is CH. A compound of the formula I as set forth in claim 1, where Rl is 4-fluorine, R2 is 2-CF3 and X is CH. For the AppHemb DR. RPNHOLD COHN AMD PARTNERS •y