CS253748B2 - Fungicide and process for preparing active compound - Google Patents

Abstract

Compounds of the formula <IMAGE> in which R, Hal and Z, which are as defined in the description, and their preparation are described. The compounds are suitable for use as fungicides.

Description

The present invention relates to a fungicidal composition which contains novel azolderivatives as an active ingredient. The invention further relates to a process for the preparation of these novel compounds.

European Patent Application 94 564 discloses azolderivatives, in particular 2- (1, 2, 3,

2,4-triazol-1-yimethyl) -2- (4-chlorophenyl) -3- (2,4-dichlorophenyl) oxirane, the effect of which as fungicides is not satisfactory in all cases.

It has now been found that the compounds of formula I

in which

R is C 1 -C 4 alkyl, bisphenyl or phenyl, wherein the phenyl moiety is optionally substituted by halogen, phenoxy or C 1 -C 4 alkyl, and

Hal represents a fluorine, chlorine or bromine atom, as well as their acid addition salts and salts with copper, zinc, manganese, iron, cobalt and nickel, which are compatible with plants, have a better fungicidal action, in particular against cereal diseases than known azolderivatives.

The compounds of the formula I contain chiral centers and are generally obtained in the form of racemates, optionally in the form of mixtures of diastereoisomers of erythro and threo forms. The erythro- and threo-diasteroomers can be separated into the pure form in the customary manner in the compounds according to the invention, for example on the basis of their different expandability or columnar chrmatocgaphia. From such uniform pairs of diastereomers, uniform enantiomers can be obtained by known methods. Both the single diastereomers and / or the diastereomers or the enantiomers as well as mixtures thereof resulting from the synthesis can be used as fungicidal agents.

In formula (I), R is, for example, methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, isobutyl, tert-butyl, p-biphenyl, phenyl, 2-chlorophenyl, 3- chlorophenyl, 4-chlorophenyl, 4-fluorophenyl, 4-bromophenyl, 2,4-dichlorophenyl, 3,4-dichlorophenyl,

3,5-dichlorophenyl, 3-chloro-4-methylphenyl, 4-methylphenyl, ethylphenol, 4-isopropylphenyl, 4-tert-butylrinyl, 4-phenoxyphenyl, and the like. 3-phenoxyphenyl group. <

Addition salts are, for example, hydrogen chloride, bromides, sulphates, nitrates, phosphates, oxalates or dodecyl fluorosulfonates. The effectiveness of these salts is determined by their cation, so the importance of the anion is inferior. The compounds of formula I are prepared according to the invention. by reacting the atollyrmethyloxiranes of the formula I with suitable acids.

The co-compounds of the active compounds of the formula I or their salts may be formed, for example, with copper, zinc, manganese, iron, cobalt or nickel. These compounds are prepared. by reacting the azolylmethyloxiranes of the formula I with strict metal salts.

Accordingly, the present invention provides a fungicidal composition, characterized in that it contains at least one azolymeetloxirane of the formula I as active ingredient.

Hal

(I) in which:

R is C 1 -C 4 alkyl, bisphenyl or phenyl, the phenyl moiety optionally substituted with halo, phenoxy or C 1 -C 4 allyl,

Hal represents a fluorine, chlorine or bromine atom, or an addition salt thereof with a salt of copper, zinc, manganese, iron, cobalt and nickel, which salts by plants, and an inert additive.

The compounds of formula (I) according to the invention are prepared by treating the product of formula (II) with an acid or by tolerating the corresponding intermediates.

(II) in which:

L-azole of formula III means a nutleolilnd substituted leaving group, reacted with the corresponding

D - (III), wherein a, hydrogen or metal, and the compounds thus obtained are optionally converted by zinc, manganese, have the above

Me means in its copper-containing physiologically acceptable acid or copper, iron, cobalt and nickel copper.

In addition to the processes of the invention, the compounds of formula (I) may be prepared by:

b) reacting the compound of formula II in which the hydroxy group is reacted with the compound

R and Hal are as defined above and L is of formula IV

ΓΠ-ΛΊ (IV) in which

Y is carbon or sulfur, or is

c) a compound of formula V wherein:

R and Hal are as hereinbefore defined, epoxidized, or se

d) a compound of formula VI

(VI) in which:

R is as defined above, reacted with a compound of formula VII

S (O) _n --CH

Hal

(VII) in which:

Hal is as defined above,

2

R and R, which may be the same or different from each other, are methyl or phenyl and n is 0 or 1, and the compounds thus obtained are optionally converted into their salts with physiologically acceptable acids.

The reaction according to the invention is carried out when Me represents a hydrogen atom, optionally in the presence of a solvent or diluent, optionally with the addition of an inorganic or base and optionally with the addition of a reaction accelerator at temperatures between 10 and 120 ° C. Preferred solvents or diluents include ketones such as acetone, methyl ethyl ketone or cyclohexanone, nitriles such as acetonitrile, esters such as ethyl acetate, ethers such as diethyl ether, tetrahydrofuran or dioxane, sulfoxides such as dimethylsulfoxide, amides such as dimethylformamide, dimethylacetamide or N-methylpyrrolidone sulfolane or the corresponding mixture.

Suitable bases which may optionally be used in the reaction as acid binding agents are, for example, an alkali metal hydroxide such as lithium hydroxide, sodium hydroxide or potassium hydroxide; alkali metal carbonates such as sodium carbonate or potassium carbonate or sodium bicarbonate or potassium bicarbonate. 1,2,4-triazole, pyridine or 4-dimethylaminopyridine can also serve as bases when used in excess. Use yourself. however, other conventional bases may also be used.

Suitable reaction accelerators are preferably metal halides, such as sodium iodide or potassium iodide, quaternary ammonium salts, such as tetrabutylammonium chloride, tetrabutylammonium bromide, or tetrabutylammonium iodide, benzyltriethylammonium chloride or benzyltriethylammonium bromide or crown ethers, such as 12-crown ethers, such as 12-crown ethers. , dibenzo-18-Crown-6 or dicyclohexano-18-Crown-6.

The reaction is generally carried out at temperatures between 20 and 150 ° C under atmospheric conditions or under pressure, continuously or discontinuously.

In the reaction according to the invention, the symbol is. If it is a metal atom, the reaction according to the invention is carried out optionally in the presence of a solvent or diluent and optionally with the addition of a strong inorganic or organic base at temperatures between -10 and 120 ° C. Preferred solvents or diluents include dimethylformamide, diethylormamide, dimethylacetamide, diethyl acetamide, N, N, N-methyl, N, N, N, N-hexamethylthioforriaride, sulfoxides, such as dimeethyl sulfoxide, and finally sulfolane. ,

Suitable bases which may optionally be used in the reaction as acid binding agents are, for example, alkali metal hydrides such as alcohol, sodium hydride and potassium hydride, alkali metal amides such as sodium amide and potassium amide, sodium tert-butoxide or potassium tert-butoxide, alcohol, sodium or kaliurtrifenilretyl and naphthalene liqueur, -natruum, or -salts. '

For variant b), suitable diluents are polar organic solvents, such as nitrides, for example aceoonotrol, sulfoxides, for example dimethylamide, formamides, for example dimethylethyl, ethers, ketones for example acetone, ethers, for example, diethyl ether, tetrahydrofuran, and especially chlorinated hydrocarbons, for example, chloroform, and chloroform.

In general, the reaction is carried out at temperatures between 0 and 100 ° C, preferably at 20 to 80 ° C. The presence of the solvent is expediently carried out at the boiling point of the absent solvent.

In carrying out process (b), one mole of the compound of formula II (L = OH) is used, preferably a mole of carbon-1'-1,2,4-thiazole (1) or carbonyl-bis-irirazole (1) or 1 mole Sulfonyl-is-1,2,4-roiazole ((), optionally Sulfonyl-bis-irirazole (1) or sultenyl-bis-1,4,4-roiazole (1), optionally sulfonyl-L-bis-imidazo) (Lud) produced in situ. In order to isolate the compounds of formula (I), the solvent is stripped off, the residue is taken up in an organic solvent and washed with water.

The novel starting compounds of formula II are prepared by epoxidation _; of the corresponding olefins of formula IX

R ^Ha *

L-CHa-c-CH- ^(IX) wherein

L, R and Hal had the meanings given above (cf. G. Dittus in Houbben-Weyl-Muller, Methoden der Organischen Chemie, Georg Thieme Verlag, Stuttgart, 1965, Vol. VE, 3rd p. 385 and later).

Compounds of formula (IX) are prepared by reacting olefins of formula (X)

(X) in which

R and Hal are as hereinbefore defined, halogen or oxide; by methods known per se at the position of the allyl group.

Suitable halogenating agents are N-chlorosuccinimide and N-boorsukkinimid halogenated hydrocarbons such terrachlorreranu tr ^ ^ c ^ i ^, ^ c ^ i ^ e ^ 1 ^ <^ nu or reerlennhloridu, whereby this halo ^g enační rea ^for ce ^{p p} s rovádí te ^ okch ϋζΐ · ²⁰ and ¹⁰⁰ ° C. ^The ox: ^IR (^ ^{i k} u s amyl ^p ins are used peresterl as t-butyl perbenzoic acid or peracetic acid in reoc.bžrylesreož přítomnooti heavy metal salt such as the chloride or bromide měěiného měělnnho. Work is yet in inert solvents at temperatures between 10 and 100 ° C.

The allyl halides or allyl alcohols of the formula IX thus obtained are then converted to the corresponding epoxides of the formula II (L = halogen or hydroxyl group). For this purpose, the olefins of the formula IX are oxidized with peroxylaric acids, i.e. perbenzoic acid, 3-chloroerbenzoic acid, 4-nitroperbenzoic acid, monnopertalic acid, acetic acid, peroropionic acid, permaleinic acid, mono-oxo-succinic acid, perpiperidine. Acid or trifluoroacetic acid in inert solvents, preferably in chlorinated hydrocarbons, for example in methylene chloride, chloroform, tetrachlorobutane, dichloroethane or optionally also in acetic acid, ethyl acetate, acetone or dimethylformamide, optionally in the presence of a buffer such as acetate The reaction is carried out at temperatures between 10 ° C and 100 ° C and the reaction is optionally catalysed by iodine, sodium tungstate or light, and alkaline solutions of hydrogen peroxide (about 3θ4) in methanol are also suitable for oxidation. , ethanol, acetone or p at temperatures ranging from 25 to 30 ° C, as well as allyl tetrahydroferroriums, for example tert-butylhydroxybromide, with the addition of a catalyst, for example sodium tungstate, perhydrotartic acid, morybdenhexacarbonyl, or nadylacetylacrylate. Said oxidizing agent may be partially prepared in situ.

While the epoxy halogens of formula II (L = halogen) thus obtained can be reacted immediately according to the process of the invention, the corresponding biphenylalrhols of formula II (L = OH) can be reacted with compounds of formula IV according to variant b) or converted to reactive esters which are then reacted with compounds of formula III by the process of the invention.

The preparation of the reactive esters which react with the compounds of the formula III is carried out according to generally known methods (Houben-Weel-MMller, Methan der organischen Chemie, Georg Thieme Veelag, Stuttgart, 1955, Vol. 9, pp. 388, 663, 671]. Such esters are, for example, methanesulfonic acid esters, trifluoromethanesulfonic acid esters, esters.

2,2,2-trifluoromethylsulfonate acids, ionaflurrbutansulphonic acid esters, 4-betylbenzenesulfonic acid esters, 4-bromobenzenesulfonic acid esters, 4-nitrobenzenesulfonic acid esters or benzenesulfonic acid esters.

Compounds of formula (X) may be prepared in accordance with methods well known in the art for the synthesis of olefins (Houbbeyeyl-Muller, Methoen der organischen Chemie, Georg Thieme Verlag, Stuttgart, 1972, Vol. V, 1b).

Process c) is carried out analogously to the epoxidation of the compound of formula IX.

The starting compounds of the general formula V are known (DE-OS 25 49 '798) and can be prepared according to the methods mentioned therein.

In process d) according to the invention, the azo-1-ketones of the known zither (e.g. DE-OS 20 63 875) of the general formula VI are reacted with the sulfur compounds of the general formula VII.

The alkylidene sulfurates of formula VII (n = 0) and oxysulfurates of formula VII (n = 1) 'are prepared according to known general methods (cf. e.g. WA Benjamin, Menlo Park 1972, p. 712 and other in situ and inert solvents, preferably in ethers such as tert-butyl bromide, tetrahydrofuran or the like. in mixtures of both or in hydrocarbons, such as pentane, hexane or petroleum, at temperatures between -78 and 30 ° C, by reaction with azolesHetones of formula VI.

The compounds of formula (I) thus obtained are isolated by conventional methods, optionally purified and optionally treated with salts to form salts.

The non-limiting examples illustrate the preparation of the active compounds of formula I.

I. Production of starting materials

Example A

To a solution of 194.5 g of 2-chlorbeezyllrifenylfosfoniumchloridu and 800 ml of absolute methanol at l tepJotě at ⁰ ° C ^{gives 30 g} methyl Hoxie ^f oo ^d u ^with copper in ³⁰⁰ ml of absolute ^¹H mmfanolu and after half an hour, 60 g of acetophenone. The reaction solution was then boiled · 3 hours under reflux, ^p ot ^é salt ^{characterized} mxstnoo the precipitated at ^the i-odfi filtered ^and the filter's ^d steamed in vacuo. Digestion of ^the US ^P t ^k etroletheeem (boiling temperature between approximately ^50-7 0 ° C.) tr ^ e ^ ^ lhosmnoxid separated and the solution odpaaí in vacuo. The residue is taken up in 1 J.tr ^ em tftřachformfthřnu and added with 81.7 g of N-bromssukčnimidu 4G п ^ ^ ^ хп 2.2 RA ~ _Z o0fomáoflné kyseeiny and the mixture was refluxed. After completion of the reaction, the succinimide is separated off, the filtrate is evaporated in vacuo and the residue is recrystallized from meeanol. Yield: 65.5 g (43% of theory) of Z1 - (- chloro-phenyl) -2-vinyl-2-biphenylprop-1-one. Mp ⁷⁸ ° C.

EXAMPLE B g of Z1 - (- (phosphinyl)) - 2-phenyl-3-bromoprop-1-ene was refluxed in 500 ml of chloroform together with 23 g of 3-chloroepooybenzoic acid. After completion of the reaction, the Saga chloroOcrmová washed with aqueous sodium Tydra ^g efnUtičitřii solution and water to remove any remnants kyseeiny dried with ·. sodium sulfate and evaporated in vacuo. The residue gave 41.3 g (70.2%) l · bromrf] ^ - 22f (^ i ^ i ^ l-з- (2-chloro, phen ^yl) fxirřnu which is then further processed. Responses with trazzce according to the following example.

II. Manufacture of finished products

EXAMPLE 1 1 g of 1,2,4-triazole and 5 g of sodium hydride (80% dispersion in mineral oil) are suspended in 150 ml of Ν, Ν-dimethylethyl chloride at room temperature at room temperature. of this suspension is added a solution of g-brf-mrtf122-pheny1-3- (trifluorenyl) oxiane in 150 ml of Ν, dir-dimethylformamide. After 8 hours, the reaction solution was poured into water and extracted with ethyl acetate. The organic base was washed with water, dried over sodium sulfate and the solvent was evaporated in vacuo. From dissopropyletheru 24 g of Z-2- (1 -, 4-L-triřУfУ yУrfťyl) -2- (lfnil) -3 - (- chУorSeiyУ) foiranu m.p. ¹ 50 ^° (compound ^no. 1 .

The compounds of the following table can also be prepared in an analogous manner to that described in Example 1.

Table

(AND)

number R Hal • melting point (° C) isomer • 1 ^C 6 ^H 5 Cl - - 164-166 OF 2 ^4_C1C 6 ^H 4 * Cl '166 OF 3 4-biphenyl Cl 191 of 4 2,4-Cl ² C ₆ ^{H 3} Cl OF 5 2-Cl-C6H4 Cl of '6' ² - ^F - ^C 6 ^{H 4} Cl of 7 4-CH ₃ -C ₆ H ₄ Cl 140 of 8 4-F-C-H 4 6 4 Cl 136 t z 9 3-Br 4-FC ₆ H 3 _R Cl 129-130 of 10 4-Br-C ₈ H ₄ Cl of 11 ^{3-4-Cl 2 C} 6 ^{H 3} Cl of 12 ' Werc.C ^ -C ^ Cl of 13 Cl of 14 ^3,5- ^ ^2- ^ ³ Cl of 15 Dec p-YY-O-YY- Cl of 16 4-Cl-C8H3. 6 4 F 138-140 of 17 ^C 6H5 F 139 of 18 p-biphenyl F of 19 Dec 2,4-CL 2 → C 8 H 3 F ' 117 of 20 May 2-C1-RR F of 21 2-F - ^c 6 ^h 4 F 128 of 22nd ^{4-CH3 'C} 6 ^H 4 F 131 of 23 ^4-FC 6 ^H 3 F 114 of 24 3-B16-4-F-C6H 3 F 106 of 25 4-B 6 -C, H 4 6 4 F of 26 3,4-Cl ₂ -C ₆ H ₃ F of 27 Mar: 4-t-C ₄ H ₉ -C ₆ H ₄ F of 28 3-Cl-C, H ₄ 6 4 F of 29 ^3-5 - ^CL2 - ^CgH3 F of 30 ^nC 6 ^H 5 - ^O - ^C 6 ^H 4 F of 31 -4 - ^ - ^ 4 Br of 32 ^C 6H5 Br 153 of 33 p-biphenyl Br of 34 ² < ^{4-cl2- c} 6 « ³ Br of 35 2-C 1 -C 6 H 4 Br of 36 ^{2-F-6 «4} Br of 37 ^{4-C 3 -C} 6 ^H4 Br of 38 4-FC ₆ H3 . Br of 39 3-Br- ^4- F-C 8 H 4 Br of

Continuation table

number R Hal melting point (° C) osomer ⁴⁰ 4- ^Br - ^c ₆ ^H 4 Br OF 41 3,4-Cl ₂ -C ₆ H ₃ Br OF 42 4-terc.C ₄ H ₉ -C ₄ H _g Br OF 43 ³ “ ^C1 ” ^C 6 ^H 4 Br OF 44 3,5-Cl ₂ -C ₆ H ₃ Br OF 45 ^{2 C} 6 ^H 5 ° ^C 6 ^H 4 Br OF 46 ^CH 3 Cl 91 OF 47 ^CH 3 F OF 48 CHj ВГ of 49 t-RR F OF 50 t-C ₄ H ₉ Cl of 51 t-C ₄ H ₉ Br OF

Example 52

Compound No. 1, i.e. Z-2- (1,2,4-triazol-1-ylmethyl) -2- (phenyl) -3- (2-chlorophenyl) oxirane, is dissolved in diisopropyl ether and gaseous gas is introduced into the solution. hydrogen chloride. The hydrochloride forms in the process and is separated from the solution and separated.

Example 53

. Compound 1 was dissolved in acetone and _t a concentrated aqueous solution of copper sulphate. A barium salt of Compound (1) is formed which is separated from the solution and separated.

The novel compounds exhibit, in general, excellent activity against a wide range of phytopathogenic fungi, especially in the classes Ascomycetes and Basidiomycetes. These compounds are partially systemically active and can be used as foliar fungicides and soil fungicides.

Of particular interest are fungicidal active compounds for controlling a variety of fungi on a variety of crop plants or on their seeds, in particular wheat, rye, barley, oats, rice, corn, grasses, cotton, soy, coffee, sugarcane, fruit trees and ornamental plants. , horticulture, in the cultivation of vines, as well as vegetables such as cucumbers, beans and pumpkin plants.

The novel compounds are particularly suitable for combating the following plant diseases:

grass powdery mildew (Erysiphe graminis) on cereals, cucumber powdery mildew (Erysiphe cichoracearum) and Sphaerothea fuliginea on cucurbits / apple powdery mildew (Podosphaera leucotricha) on apple trees, powdery mildew (Uncinula necator) on grapevine species, grape vine species, Puocin species and grasses, Ustilago species on cereals and sugar cane, apple scab (Venturia inaequalis) on apple trees, weevil (Septoria nodorum) on wheat,

Λ »gray mold (Botrytis .cinerea) on strawberry and grapevine,

Cercospora. arachidicola on ptdzernnice oily, brown spots of barley (Pyrenophora teres) on barley,.

Pseudooceroopporlla herpptrichoides on wheat and barley, _

Pyricularia oryzae on rice,

Hemileia vastatrix on coffee, brown specks of potato leaves (Alternaria solani) on potatoes and tomatoes,

Sclerotlim rolfsii on peanuts and various grass species, as well as Fusarium and Veeticililm species. different kinds of plants.

The compounds are applied by spraying or dusting the plants with the active compounds or treating the seeds with the active compounds. Application is carried out before or after infection of plants or seeds by fungi.

The novel compounds can be converted into conventional compositions such as solutions, emulsions, suspensions, powders, pastes and granules. The administration forms are fully guided by the intended use. These dosage forms should in any case ensure a fine and uniform distribution of the active ingredient. The formulations are prepared in a manner known per se, for example by mixing the active compound with solvents and / or carriers, optionally with emulsifiers and dissolvents, and other organic solvents can also be used as co-solvents when water is used as the diluent. Suitable excipients for this purpose are essentially: solvents such as aromatic hydrocarbons (e.g. xylene, benzene), chlorinated aromatic hydrocarbons (e.g. chlorobenzenes), paraffinic hydrocarbons (e.g. petroleum fractions), alcohols (e.g. meeanol, butanoo), ketones (for example cyclohexanone), amines (for example eranolaine, OimethyltoimamiO) and water: carriers such as natural stone meal (for example kaolins, clays, maize, chalk) and synthetic stone meal (for example highly disperse silicic acid, silicates); emulsifiers such as nonionic and anionic emulsifiers. (for example, polyoxyethylenes, fatty alcohols, alkylsulfates and arrhoxides) and dispersants such as lignin, sulfite waste liquors, and methyl cellulose.

The fungicidal compositions generally contain between 0.1 and 95% of the active ingredient, preferably between 0.5 and 90% of the active ingredient. active substance.

Depending on the type of effect required, the quantities applied vary between 0.02 and 3 kg of active substance or more per ha. These novel compounds can be used. also in the protection of materials. When the active substances are applied in the protection of maatellins, inter alia, in combating wood-destroying fungi, Coniophora puteana and Polypisris, the active substances are attracted in the usual manner. The novel active compounds can also be used as fungicidally active components of oily wood preservatives for the purpose of protecting wood against fungi which cause wood coloring. The application is carried out by treating the wood with such agents, for example, by impregnating or painting with such agents.

The compositions or ready-to-use preparations made from such compositions, such as solutions, emulsions, powders, dusts, pastes or granules, are applied in a known manner, for example by spraying, fogging, treating, spreading, pickling or potting.

The following are examples of such products:

I. 90 parts by weight of Compound (2) are mixed with 10 parts by weight of N-mityl-1-methyl-1 to give a solution which is suitable for application in the form of minimum drops. . *

II. 20 parts of the mono-mono-compound 8 are dissolved in an emulsion consisting of 80 parts by weight of xylene, 10 parts of the mono-adduct of 8 to 10 moles of ethylene oxide with 1 mole of N-ooonootanolamide oleic acid, 5 parts of calcium dodexylbenzene sulfonic acid and 5 parts. of the addition product. 40 mol of four moles with 1 mol of castor oil. Pouring this sieve! into water and finely dispersed in water to form an aqueous dispersion.

III. 20 parts by weight of compound No. 17 is dissolved in an oil consisting of parts by weight of cyclohexanone, 30 parts by weight of mineral oil, 20 parts by weight of addition product of 40 moles of ethylene oxide with 1 mol of castor oil. Pouring and gently dispersing the solution in water yields an aqueous dispersion.

IV. 20 parts by weight of compound 2 are dissolved in a solution consisting of 25 parts by weight of cyclohexanol, 65 parts by weight of mineral oil fraction boiling at 210 DEG-280 DEG C. and 10 parts by weight of adducts of 40 moles of ethylene oxide with 1 mole of castor oil. oils. Pouring and gently dispersing the solution in water results in an aqueous dispersion.

V. 80 parts by hmoSnnseních compound no. 8 is well mixed with 3 parts of sodium mrnoonootnloi diiesbutylíaftaleí-alpha _have lSonsvé acid, 10 parts mmoOnostolmi sodium lignosulphonate waste liquor from eulfisovýcm and 7 parts by MIM> Snostníoi siliRagelu pulverized and triturated in a hammer mill. By gently dispersing this salt in the water, spraying eeepenze is obtained.

VI. 3 parts of the clay compound No. 17 are thoroughly mixed with 97 parts of finely dispersed kaolin. In this way, a dust containing 3% by weight of the active ingredient is obtained.

VII. 30 parts of Option 1 are thoroughly mixed with a mixture of 92 parts of powdered silica and 8 parts of mono-paraffin oil which is sprayed onto the surface of the silica gel. This is an effective preparation with good ahehehi.

The mixture is thoroughly mixed with 10 parts of a homogeneous acid, moiety and formic acid, 2 parts of a stable aqueous dispersion.

VIII. 40 parts of the mono-sodium compound of the sodium salt of the condensation product of phenolulonic monoelectric liquids and 48 parts of water. In this way, it is thoroughly mixed with 2 parts by weight of mono-fatty acid polyglylol ether.

IX 22 NETHERLANDS. 2. Compounds of sodium dodecylbenzenesulfonic acid calcium, 8 alcohols, 2 parts of the sodium salt of the condensation product of phthalic acid, urea and formaldehyde, and 68 parts of ml of paraffinic mineral oil. In this way, a stable oil dispersion is obtained.

The formulations according to the invention can also be present in these dosage forms together with other active substances, such as herbicides, insecticides, fungicides, growth regulators or also with fertilizers, which are mixed with the active substances and applied together. When mixed with fungicides, this is achieved in many pastes. Improved! fuígiciíííhs of the spectrum.

The following list of fungicides that can be broken down is intended to elucidate, but not limit, these combination ionsose.

the compounds of the invention,

Funnicides which can be refracted with compounds according to, for example, the following compounds:

The present invention includes sulfur, dithiocarbamates and derivatives thereof such as ferric dimethyldimethyldithiocarbamate, zinc diaatyldithiocarbamate, zinc ethylenebis-di-dithiocarbamate, mesylate, ethylenediamine-bisametamethylamine diaminothiamethane amine tetraacetate, amethylenedioamine thiamethane amine tetraacetate. zinc ethoxymethyl-, 3'-dihydrocarbamate, zinc amaonic acid complex, zinc, N'-propyltin-bis-dihiacarbamate, Ν, Ν'-propyl-β-dihiacarbamate, Ν, 1'-Pilylpropylleabbs- (thiocarbamoil) di-sulfide;

пг.оо ^ г - ^. у, such as dini-o- (1-aatilheet.l) oenyllrotonate,

1-sec-butyl-4,6-dinitriftayl-3,3-dimethylaarylate,

2- sec -butyl-4,6-diairiktanyliiopicpylcarriaate, 5'-nitroisiftalic acid diisopropyl ester;

heterocyclic compounds such as

2-he pltade cc 1-2-iaidd,

2,4-dichloo-б- (o cCliirbahina) -s-trhaoia, 0, O-dihtylftalimidifisfinaihioiá, alpha-L-Ahaia bЬi ⁸ "(diIltltalamino) fosfiaylJ fenalllr 3-2-4-triazole,

2,3-dicyano-1,4-dithiaiaihrachinoa, 2-thia-l, S-dithio- [4,5-b] quinoxaline, 1- (butylcarbamoyl) -2-benzimidazolecarboxylic acid meesterester, 2-methoxycarboaylamiaobealoidazal; ,

2- (thiazal-4-yl) -4-imidazole,

N- (1,1,2,2-lithium-chlorine-thiyl) terbhldrifibliaid, N-trichliraethylthiitetrbhldrpfibliaid, --trichliraethylthioOtbliaid,

N-Dichlorofluoroatylthio-N ', N'-diattyl-N-phenol-dbamhd sulfuric acid, t-hiholyzyl-ticicilaretlyl-1,2,3-thhbdhboil, 2-rhodanomatylthiabreazioal,

1,4-dichloro-2,5-dhaethoxybeaoea,

4- (2-Chloroylhydrazaaa) -3-amino-5-isoaazoloa, pyridine-tllo-1-oxide,

8-hydroxylhialamine, or a salt thereof with an aluminum,

2,3-dihldro-5-carboabahido-.alpha.-ayl-1,4-axaahine;

2,3 dhhydro 5-karboxaaalhdo ^{mat-6-yl-1-1.4} axabhiin dioaid-4,4-anilide of 2-meeyl-5,6-dihydro-4H-pyran-3-karroxylové acid anilide 2lmetylfuran 3-carboaylic acid, aaili.d 2,5-dhaebabyluran-3-carboaylic acid, 2,4,5-bhimethyfluanazilabbaaylic acid aailide, 2,5-dhaethylfuraa-3-carboxylic acid cyclohexylamide, N-cyclohexyl-N-meihoxybmid 2 5-Dimethylbutyl-3-carbobutyric acid, 2-methylbenzoic acid aailide, 4-iodo-benzoic acid aailide, 4-iodo-benzoic acid, 5-dimethylamino-2,2,2-trichloroethyl acetal, piperazine-1, 4-dlytebra - (1,2,2, - (-) - - (10) - (-) - O), 1- (3,4-dichloroanilanol) -fluoromethyl-2,2,2-brichloride,

2,6-dimethyl-N-tridecylmorpholine or its salts,

2,6-Dimethyl-N-ciclodododecylmmofolin or its salts,

N- (3- (β-β-β-β-β-γ-γ-γ-γ-γ-γ-γ-γ-γ-γ-γ)) Dimethylmorpholine

N- [з ^(p -ttrc. ButylfenyD ^ -methyl ^ yl ^ lprl ^p i ^p eri ^di n, ^{1- [2- (2, 4-dichloro} tn ^{f -1) -} 4 ^- e ^ l- ^ ^{y - l, 3} -dixolan-2-yl.et ^yl] -lH-l, ^2, 4-Ьг1 ^г1-1 - ^[2 - ^(2, 4-dichlolffen ^ L ^ N ^ ¹ PPR - ^{- 3} -dioxolan-2-y1et ^{yl] -1H-1, 2,} 4-tfiazol ^- (n-ppooplL ^- - "(2,4, G-trčchlofl roxyityl) -N - ^ 01111-3101x1-10 ^ 1--,

1- (4tcllrffenrx ^yl) -3,3-dirnettli-L (lH-1,2,4-tfiazol 1-1- ^yl) -2-butanone,

1- (4-chlorophenyl) -3,3-dimethyl-1- (1H-1,2,4-triazol-1-yl) -2-butanol,

1- (1-O-phenylphenyl) -3,3-dimethyl-1- (1H-1,2,4-thiazol-1-yl) -2-butanol,

-10- (2-chlorophen-1) - 1 H-chlorophthyl) -5- (piperidin-1-yl) -1H-chlorophenyl;

^{5-buty1-2-dimtУylamino-4-yl} hydrrx -6-meth ^y 1ppyimidin _t bis- (y-y1 cllrf0t) -3-pyriuld-Nutt-nol,

1,2-bis- (3-ethoxycarbonyl-2-oxyl) benzene,

1,2- bis- (3-methocarbones ---- Уhioureidido) benzene as well as various fungicides, such as doddeylguu-dineateate,

3- [з- ^{(3, 5-diol} and ^y f ^{first -2-ox y} c ^y k ¹ o ^h e ^ J ^ ^{1.) -2-hydroxy-droxyy} Jglutarimid, hexa-Gln-benzene ,

DL-imidyl-N- (2'-dimethylfin-11-N-furlyl-1-ylate, meylestif DL-N- (2,6-diimtylphen-11-l- (2'-uetloxyylacetyl) al-ninl),

N- (2,6-diethylphenyl) -N-trifluoromethyl-D, L-2-aminobutyric acid, DL-N- (2,6-dimethylphenyl-1) --- (0-ylacetyl) alanine methyl ester,

Б-шоУх) ---- ^ -) - ³ '(3,5-dichlrrftnyl) -2,4-dioxxr-, з-oxa-zridin,

3- [3, -dicllortenχ ---- meУχ ---- melhrxymotyl] -1,3-oxxsoridine--, 4-dione,

3- (3 - dich1rrtdnyl) 1 - rspprppχl-ab-emry1hydanУoin, - (3, 5-dichlorft-yl) bromide 1, ya---diueeylcykloyrr ^p t 2 - ^^^ ^ 0 0X110 acid

2-cyano- [n- (1-ethylamino-rbonyl) -2-mL-oxioino] -cl-oid,

1- [_ 2- (2, bdicHorfe- ¹ !) ^ 1 ^ 1) -: 131 ^{, 2} , ⁴ ^ г1 ^ г1, 2,4'-1'Шог-101- (1--1,2,4 ^) ^^ 0 ^ 1-1 ^ 6 ty Dbe-zz ^^^^ oh ^, - (3-chloro-2,6-di-trifluoro-4-trifluoromethylphenyl) -Orifluoro-3- (chloro-2-chloro-2-nitro-pyridine) ,

1 - [[bis] - (4 &lt; 1 &gt; -2-y-5-methyl) -butyl] -1H-1,2,4-yphiazole.

Pro -ásseddající. experiments which imply biological activity, the known compound - (1,2,4-oxazol-yloelyl) -1- (4-chlorophenyl) -3- (2, 4-chlorophenol) was used as the substance. 4-Dichlorophenyl) oxa (A) (ref. EP 94 564).

T essl

Effects on powdery mildew (Erysiphe graminis var. УгШо!)

The leaves of the Itohu wheat seedlings in the pots were sprayed with an aqueous spray suspension containing 80% of active ingredient and 20% of emulsifier in the dry matter and dusted with oidia (syOraui) for 24 hours after spraying. (Erysiphe graminis vat.. frstl experimental ^{é-i- 1} ^ m ^ the children of Shen ^d u ^ ^p ^ s ^^ оУ ¹ meti ²⁰ and ²² ° C and at 75 to 80% s-fiHtiv vlhkossi air. After 7 days, the degree of mildew infestation is determined.

The result of the experiment shows that, for example, the use of compounds 2, 8, 16, 21, 23 and 17 in the form of 0.025%, 0.006% or 0.0 015% (% him &apos; fungicide activity (97%, compared to the known active ingredient A (90%).

Test 2

Activity against wheat rust (Puccinia recondita)

Leaves of wheat seedlings of the species Frtthgold. growing in a pot is dusted with spores of wheat rust (Puccinia recondiia). The pots are then placed in a high humidity chamber (90-95%) for 24 hours at 20-22 ° C, during which time the spores germinate and the germs of the spores penetrate the leaf tissue, and then infected plants are spotted to the dripping stage. After drying the spray layer, the test plants are placed in a greenhouse at temperatures between 20-22 ° C and 65-70% relative humidity. rust wheat on leaves.

The result of the experiment shows that, for example, the use of compounds Nos. 1, 2, 3, 7, 8, 9, 16, 23, 24 and 17 in the form of a 0.006% or 0.0 015% active ingredient suspension results in a better fungicidal effect ( 97% than the known active ingredient (A) (70%.

Test '3

Activity against brown barley hardness (Pyrenophora teres)

The barley seedlings of the Asse species are sprayed at the 2-leaf stage up to the drip-off stage with aqueous suspensions containing 80% of active ingredient and 20% of emulsifier in the dry matter. After 24 hours, the plants are onoculated with a suspension of spores of brown fungi with barley (Pyrenophora teres) and are placed in an air-conditioned, high-humidity, air-conditioned mite at 18 ° C for 48 hours. The plants are then placed in a greenhouse at 20-22 ° C and 70% relative humidity for an additional 5 days. After this time, the degree of development of the disease symptoms is determined.

The result of the experiment is to show that, for example, using compounds 1, 2, 3, 16, 21, 24 and 8 in the form of a 0.05% suspension of the active substance, a good functional effect is obtained (97%).

Claims (6)

SUBJECT OF THE INVENTION A fungicidal composition, characterized in that it contains at least one azslylmethylsxirad of the general formula I "Hal" as an active ingredient. -CH ₂ -C -CH wherein R is C 1 -C 4 alkyl, biphenyl or phenyl, wherein the phenyl moiety is optionally substituted by halogen, phenoxy or C 1 -C 4 alkyl and, Hal means fluorine, chlorine or bromine, or an acid-acceptable acid addition salt thereof or a copper, zinc, manganese, iron, cobalt and nickel salt thereof together with an inert carrier. 2. A composition according to claim 1, wherein the active ingredient is at least one azolylmethyloxirane of formula I wherein R is phenyl, 4-fluorophenyl, or 4-chlorophenyl, and Hal is chlorine or fluorine. 3. The composition of claim 1 vyznnauuící in that the active ingredient comprises from - 2- _(1-r 2,4 tričZol - l1l · -mety1) -2- (4-fluorfeny1) -3- (2- chlorophenyl) oxirane. 4. A composition according to claim 1 comprising Z-2- (1 2,4- (4-Chloro-phenyl) -3- (2-chloro-phenyl) -. 5. A composition according to claim 1, wherein the active ingredient is Z-2- (1, 2,4-Triazol-1-yl-methyl-2- (phenyl) -3- (2-chlorophenyl) oxirane. 6. A process for the preparation of an active ingredient according to claim 1, wherein the corresponding intermediate of formula II, wherein the formula wherein (II) is a nucleophilically substituted leaving group and wherein Hal has the meaning given in point 1, is reacted. with the corresponding azole III [= ^N _f I N — Me N = / (III) Me is hydrogen or metal, and the compounds thus obtained are optionally converted into their salts with physiologically acceptable acids or into their salts with copper, zinc, iron, cobalt and nickel.