AU621721B2

AU621721B2 - Trifluromethylphenylazolylmethyloxiranes, the preparation thereof and the use thereof as crop protection agents

Info

Publication number: AU621721B2
Application number: AU51178/90A
Authority: AU
Inventors: Eberhard Ammermann; Bernd Bireckoven; Stefan Karbach; Gisela Lorenz; Rainer Seele; Hubert Smuda; Guenter Wegner
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 1989-03-10
Filing date: 1990-03-09
Publication date: 1992-03-19
Anticipated expiration: 2010-03-09
Also published as: HU901383D0; JP2947287B2; DE3907729A1; ZA901834B; DK0386557T3; CA2011087C; DE59000151D1; NZ232844A; ATE77086T1; JPH02268182A; HU206434B; EP0386557A1; IL93443A0; EP0386557B1; GR3005671T3; AU5117890A; KR900014370A; HUT53782A; IL93443A; CA2011087A1

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

1~I 621 72 1 orml COMMONWEALTH OF AUSTRALIA PATENTS ACT 1952-69 COMPLETE SPECIFICATION

(ORIGINAL)

Class Ir Application Number: Lodged: Complete Specification Lodged: Accepted: Published: Priority C C t Related Art: C t C c nt. Class i ,t Name of Applicant: St t tt t Address of Applicant C iC i BASF AKTIENGESELLSCHAFT 6700 Ludwigshafen, Federal Republic of Germany.

STEFAN KARBACH, RAINER SEELE, GUENTER WEGNER, HUBERT SMUDA, BERND BIRECKOVEN, GISELA LORENZ, EBERHARD

AMMERMANN.

WATERMARK PATENT TRADEMARK ATTORNEYS.

LOCKED BAG NO. 5, HAWTHORN, VICTORIA 3122, AUSTRALIA Actual Inventor Address for Service Complete Specification for the invention entitled: TRIFLUOROMETHYLPHENYLAZOLYLMETHYLOXIRANES, THE PREPARATION THEREOF AND THE USE THEROF AS CROP PROTECTION AGENTS The following statement is a full description of this invention, including the best method of performing it known to US O.Z. 0050/40637 Trifluoromethylphenylazolylmethyloxiranes, the preparation thereof and the use thereof as crop protection agents The present invention relates to novel azole compounds, a process for the preparation thereof and fungicides containing these.

EP-A 94 564 discloses azolylmethyloxiranes, in particular 2-(1,2,4-triazol-1-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 0 0 ,r.

0 0 a 00 0 0 0 0 000000 0 0 0 0 0 00 ooo 000 0 o*, 0000 0 0 0000 0000 0 00 QQ o 00 0 00 0o a 0 0 0 t 0 t 15 0 R 2 I N-CH 2-C--CH

N=

-k Rl where (bu+ exc<dying 4-fiuoro) R is hydrogen, halogenA nitro, phenyl, phenoxy, C 1

-C

5 alkyl, Ci-Cs-alkoxy, Ci-C 4 -haloalkyl, Cl-C-haloalkoxy and, furthermore, R 1 together with the phenyl nucleus 20 can also form naphthyl which is unsubstituted or substituted by R 1 n is an integer from 1 to

R

2 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 racemates 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 *^r-1 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 R 1 are: halogen such as fluorine, chlorine, bromine or iodine, nitro, phenyl or phenoxy, eg. in the para position, C,-C 5 alkyl or C 1

-C

5 -alkoxy, each alkyl being methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl or neopentyl, Ci-C 4 -haloalkyl or Cl-C 4 -haloalkoxy, H L especially mono- to perhalogenated alkyls such as CH 2 C1, 15 CHCl 2 CC1 3

CH

2 F, CHF 2 CHzBr, CHBrCl, CF 2 Cl, C 2

F

5

CF

2

CHF

2

CH

2

CH

2 Cl, CHCHC 2 CH CH 2 Br, C 3

F

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

SExamples of acid addition salts are the hydro- 25 chlorides, hydrobromides, sulfates, nitrates, phosphates, St 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 accord- Sing to the invention are prepared by reacting the azolylmethyloxiranes 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 azolylmethyloxiranes with corresponding metal salts.

The compounds of the formula I can be prepared by a) reacting a compound of the formula II

!S

t 3 O.Z. 0050/40637 0 R 2 L-CH 2-C CH R1 I n where R 1 and R 2 have the stated meanings, and L is a leaving group which can be replaced nucleophilically, with a compound of the formula III XxN-Me III I

N

where Me is hydrogen or a metal, and X has the stated meaning, or S b) converting a compound of the formula IV tc R2 NC

IV

n i where R 1

R

2 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 Sor 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 cyclohexanone, nitriles such as acetonitrile or propionitrile, alcohols such as methanol, ethanol, iso-propanol, nbutanol or glycol, esters such as ethyl acetate, methyl

I-:

i' 4 O.Z. 0050/40637 acetate or butyl acetate, ethers such as tetrahydrofuran, diethyl ether, methyl tert-butyl ether, dimethoxyethane, dioxane or diisopropyl ether, amides such as dimethylformamide, 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, 0o o alkali metal hydrides such as lithium, sodium or potas- 0 sium hydride, alkali metal amides such as of sodium or o 0- 15 potassium, as well as sodium or potassium tert-butoxide, 0 o-oo triphenylmethyllithium, -sodium or -potassium, and .a.s naphthyllithium, -sodium or -potassium. However, it is o "o also possible to use other conventional bases.

0oo00 0o 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- 0000 ammoniur chloride or bromide or crown ethers such as 12- 0 crown-4, 15-crown-5, 18-crown-6, dibenzo-18-crown or 25 dicyclohexano-18-crown-6.

o 0 The reaction is generally carried out at from to 150 0 C, in particular 20 to 120 0 C, under atmospheric or 0o. superatmospheric pressure, continuously or batchwise.

00 If Me is a metal, reaction a) can be carried out 30 in the presence of a solvent or diluent and at from to 150°C, in particular 0 to 120 0 C, preferably 20 to 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 i t1 ,I N.rl. i 1Ij~-ii- i- 5 O.Z. 0050/40637

U

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 propionitrile, alcohols such as methanol, ethanol, iso-propanol, n-butanol or glycol, esters such as ethyl acetate, methyl acetate or butyl acetate, ethers such as tetrahydrofuran, diethyl ether, dimethoxyethane, dioxane, diisopropyl ether or methyl tert-butyl ether, amides such as dimethylformamide, dimethylacetamide or N-methylpyrrolidone, as well as dimethyl sulfoxide, sulfolane or mixtures thereof.

The novel starting compounds II are obtained by epoxidation of the corresponding olefins V: i f i R2 La

CH-CD

R I ctrl t c~tc irso o P L1 r (cf. G. Dittus in Houben-Weyl-MUller, 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 R2

CH,

<C

in the allyl position by conventional methods.

Suitable halogenating reagents are N-chloro- and N-bromosuccinimide. Examples of solvents are halohydrocarbons such as carbon tetrachloride, trichloroethane or methylene chloride. The halogenation is generally carried I; Yi: I -C ii'i 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°C.

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.

0 R 2 HO--

C--CH

VII

RI

n For this, the olefins V are oxidized with peroxycarboxylic acids such as perbenzoic acid, 3-chloroperbenzoic acid, 4-ritroperbenzoic acid, monoperphthalic oao acid, peracetic acid, perpropionic acid, permaleic acid, ao"o monopersuccinic acid, perpelargonic acid or trifluoroper- °o acetic acid in inert solvents, preferably chlorinated 4. 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 1 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 0 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 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-Miller, Methoden der Organischen Chemie, Georg Thieme Verlag, Stuttgart, 1955, volume 9, pages 388, 663, 671). Examples 0 00 o0oo of such esters are methanesulfonates, trifluoromethaneo 15 sulfonates, 2,2,2-trifluoroethanesulfonates, nonafluoro- 0 000 butanesulfonates, 4-methylbenzenesulfonates, 4-bromo- I benzenesulfonates, 4-nitrobenzenesulfonates or benzenesulfonates.

o The compounds V can be prepared by conventional methods for olefin synthesis (Houben-Weyl-Mller, Methoden der Organischen Chemie, Georg Thieme Verlag, o0u Stuttgart, 1972, volume V, lb).

Furthermore, the epoxy alcohols VII can be 0 prepared by oxidation and subsequent reduction of the o 25 propenals obtainable as described in DE-A 37 22 886.

0 These substituted propenals are dissolved in alcohols such as methanol, ethanol, n- or iso-propanol or butanols, or solvent mixtures containing these alcohols are 'used, and are oxidized with hydrogen peroxide, cyclohex-yl peroxide, tert-butyl hydroperoxide or cumene hydroperoxide with the addition of bases. The resulting formyloxirane 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-trifluoromethylbenzaldehyde 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 The mixture is stirred at 40 0 C 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 concen- 0 °o trated. Filtration of the residue through a silica gel Soo 15 column (ethyl acetate/n-hexane 1:3) results in an 80 Soooo. yield of E/Z-2-phenyl-3-(2-trifluoromethylphenyl)propeoooo nal.

o so EXAMPLE B oo 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 0oO0o reaction solution is stirred at 0°C while 14.3 g of o00, hydrogen peroxide (approximately 50 strength) are oo o slowly added dropwise, during which the internal tempera- .oo. 25 ture does not exceed 30"C. After the addition is coma plete, the mixture is stirred at room temperature for 6 hours and subsequently 2.35 g of sodium borohydride coo dissolved in a little 10 strength sodium hydroxide o1 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.

It 1*~ 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-2phenyl-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-methylpyrrolidone, and the mixture is heated at 50"C for minutes. After it has cooled to room temperature, 57 g of cis-2-(4-methylbenzenesulfonyloxymethyl)-2-phenyl-3-(2trifluoromethylphenyl)oxirane dissolved in 100 ml of Nmethylpyrrolidone 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; 25 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-trifluoromethylphenyl)oxirane with melting point 132-134°C (compound no. 1).

The compounds listed in the table can be prepared as in Example 1:

'II.

,44 44 I I (I LE

I

0.Z. 0050/40637 Table 0. R2 n M.p. (OC)/IR 1 2 3 00 0 4 0 0.

~00 5 6 000~ 7 0 8 0 0 9 c~00 0015 11 12 13 0000 14 0 0 0000 15 0 0 0 z 0 20 16 00 0 17 0000 1 O 0 19 21

H

2-Cl 2-F 4-Cl 4-F 2, 4-F 2 2, 4-Cl 2 4-Br 4-0CF 3 4-OCH 3

H

2-Cl 2-F 4-Cl 4-F 2, 4-F 2 2, 4-Cl 2 4-Br 4-0CF 3 4-OCH 3

H

2-Cl 2-F 4-Cl 4-F 2, 4-F 2 2, 4-Cl 2 4-Br 4-OCF 3 2-CF 3 2-CF 3 2-CF 3 2-CF 3 2-CF 3 2-CF 3 2-C F3 2-CF 3 2-CF 3 4-CF 3 4-CF 3 4-CF 3 4-CF 3 4-CF 3 4-CF 3 4-CF 3 4-CF3 4-CF 3 4-CF 3 4-CF 3 2-C F 3 2-CF 3 2-CF 3 2-CF 3 2-CF 3 2-CF 3 2-CF 3 2-CF 3 2-CF3 132-134 1506, 1315, 1172, 1124, 1038, 771 cm- 1 117-119 110-112 132-134 1503, 1315, 1170, 1124, 1038, 770 ml 23 24 25 26 27 28 29 127-130

I-

890092 0.Z. 0050/40637 Table continued

R

2 X M.P. 0 0) 30 31 32 33 34 35 36 37 38 39 40 4-OCH 3

H

2-Cl 2-F 4-Cl 4-F 2, 4-F 2 2, 4-Cl 2 4-Br 4-OCF 3 4-OCH 3 4-C F 3 4-CF 3 4-CF3 4-CF 3 4-CF3 4-CF 3 4-CF 3 4-C F 3 4-CF 3 4-CF 3 4-CF3 1512, 1326, 1125, 1068, 840 cm- 1 4 4 r~ 444' *4444 2:1 cis/trans mixture 4 *1 j.

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 Ascomycetes and Basidiomycetes classes. Some of them have a systemic action and can be used as foliar and soil fungicides.

I

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 S plant diseases: 0 Erysiphe graminis in cereals, n Erysiphe cichoracearum and Sphaerotheca fuliginea in cucurbits, Podosphaera leucotricha in apples, o 0 0 Uncinula necator in vines, I o o Puccinia species in cereals, Rhizoctonia species in cotton and lawns, Ustilago species in cereals and sugar cane, Venturia inaequalis (scab) in apples, Septoria nodorum in wheat, Botrytis cinerea (gray mold) in strawberries and grapes, 025 Cercospora arachidicola in groundnuts, 0o o Pseudocercosporella herpotrichoides in wheat and barley, I o Pyricularia oryzae in rice, Hemileia vastatrix in coffee, Alternaria solani in potatoes and tomatoes, Sclerotium rolfsii in groundnuts and lawn varieties, ons

C

eo Fusarium and Verticillium species in various plants.

So 0 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 1, 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 aromatics xylene), chlorinated aromatics chlorobenzenes), paraffins crude oil fractions), alcohols methanol, butanol), ketones cyclohexanone), amines ethanolamine, dimethylformamide), and water; carriers such as ground natural minerals kaolins, aluminas, talc and chalk) and ground synthetic minerals highly disperse silica and silicates); emulsifiers such as nonionic and anionic emulsifiers 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 Coniophora puteana and Polystictus versicolor. The novel active ingredients may also be employed as fungicidally effective components of oily wood pre- I servatives for protecting wood against wood-discoloring fungi. The agents are applied by treating, impregnating or painting, the wood with them.

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

Examples of formulations are given below.

I. 90 parts by weight of compound no. 5 is mixed with 10 parts by weight of N-methyl-c-pyrrolidone. A mixture is obtained which is suitable for application in the form uf 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-Nmonoethanolamide, 5 parts by weight of the calcium salt of dodecylbenzenesulfonic 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.

L..

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 isobutanol, 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 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 0 C, and 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.

0 ft V. 80 parts by weight of compound no. 1 is well mixed with 3 parts by weight of the sodium salt of diisobutylnaphthalene-a-sulfonic acid, 10 parts by weight of the sodium salt of a lignin-sulfonic acid obtained S from a sulfite waste liquor, and 7 parts by weight of powdered silica gel, o *O and triturated in a hammer mill. By uniformly distributing the mixture in -water, a spray liquor is obtained.

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.

0 o o I5 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 0o 8 parts by weight of paraffin oil which has been sprayed onto the surface 0 0 S of this silica gel. A formulation of the active ingredient is obtained having good adherence.

VIII. 40 parts by weight of compound no. 5 is intimately mixed with parts by weight of the sodium salt of a phenolsulfonic acid-ureaformaldehyde condensate, 2 parts of silica gel and 48 parts of water to give a stable aqueous dispersion. Dilution in water gives an aqueous 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 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.

0.

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 fungicides frequently results in an increase in the fungicidal spectrum.

For the following experiment, the active ingredient 2-(1,2,4-triazol-l-ylmethyl)-2-(4-chlorophenyl)-3-(3-trifluoromethyl)-oxirane disclosed in EP-A 94,564 was employed.

Use Example Action on Botrytis cinerea in pimientos r. t15 Pimiento seedlings of the "Neusiedler Ideal Elite" variety with 4 to well developed leaves were sprayed to runoff with aqueous suspensions containing (dry basis) 80% of active ingredient and 20% of emulsifier.

i After the sprayed-on layer had dried, the plants were sprayed with a S' conidial suspension of the fungus Botrytis cinerea and kept in a highhumidity chamber at 22 to 24 0 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.

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

L

Claims

1. Trifluoromethylphenylazolylmethyloxiranes of the general formula I 0 R2 N-CH 2 I, S R1 N=~ where buf o<cjui q q--f(uoro) R 1 is hydrogen, alogen nito, phenyl, phenoxy, C 1 -C 5 -alkyl, C 1 -C 5 -alkoxy, C 1 -C 4 -haloalkyl, C 1 -C 5 -haloalkoxy and, furthermore, R1 together with the phenyl nucleus may also form naphthyl which is unsubstituted or substituted by R1, n is an integer from 1 to R 2 is ortho- or para-trifluoromethyl, X is CH or N, oon and the acid addition salts and metal salts thereof which are S tolerated by plants. 0000 0 6 0

2. A fungicidal agent containing inert additives and a fungicidally effective amount of a compound of the formula I 0 R 2 [XN-CH2-C- CH- I, N- I R1 n where (ku- ek-av f'uoro) R 1 is hydrogen, halogenq nitro, phenyl, phenoxy, C-C 5 -aikyl, C-C5-alkoxy, C 1 -C 4 -haloalkyl, C 1 -C 5 -haloalkoxy and, furthermore, R1 together with the phenyl nucleus may also form naphthyl which is unsubstituted or substituted by R 1 n is an integer from 1 to R 2 is ortho- or para-trifluoromethyl, X is CH or N, US etc. 17 O.Z. 0050/40637 and the acid addition salts and metal salts thereof which are tolerated by plants.

3. A process for combating fungi, wherein a fungicidally effective amount of an azolylmethyloxirane of the general formula I 0 R2 N-CH-C--CH I, R1 1n e ,.where b et 4-Woro R 1 is hydrogen, halogen A nitro, phenyl, phenoxy, C 1 -C 5 -alkyl, C 1 -C 5 -alkoxy, C 1 -C 4 -haloalkyl, C 1 -C 5 -haloalkoxy and, furthermore, R 1 together with the phenyl nucleus may also form naphthyl which S is unsubstituted or substituted by R 1 4 n is an integer from 1 to R 2 is ortho- or para-trifluoromethyl, X is CH or N, I or a plant-tolerated acid addition salt or metal salt thereof is S 20 allowed to act on the fungi, or the materials, areas, timber, plants or seed threatened by fungus attack. I 0

4. A compound of the formula I as set forth in claim 1, where R1 is hydrogen, R2 is 2-CF 3 and X is N. tie S c

5. A compound of the formula I as set forth in claim 1, where R1 is 4-fluorine, R2 is 2-CF 3 and X is N.

6. A compound of the formula I as set forth in claim 1, where R1 is hydrogen, R 2 is 2-CF 3 and X is CH.

7. A oefflpound of the formula I as set forth in claim 1, whore P is 4i fluorin, R 2 is 2 CF3 and X is Cl. DATED THIS 8th day of March, 1990 BASF AKTIENGESELLSCHAFT WATERMARK PATENT TRADEMARK ATTORNEYS, The Atrium, 290 Burwood Road, A HAWTHORN. VICTORIA 3122.