DK156608B - FUNGICID AGENT CONTAINING TRIAZOLYL DERIVATIVES AND PROCEDURES TO COMBAT FUNGI - Google Patents

Abstract

Fungicidal agents which contain triazolyl derivatives of the formula <IMAGE> in which Ar, Z, Y, X, R<1> and R<2> are as defined in the description.

Description

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The present invention relates to fungicidal agents containing triazolyl derivatives or salts thereof or metal complex compounds thereof, and to a method of combating phytopathogenic fungi therewith. The fungicidal agent of the invention is peculiar to the characterizing part of claim 1.

It is well known that triazole derivatives, e.g. 2,2-dimethyl-4- (1,2,4-triazol-1-yl) -5-phenylpentan-3-one (see German Publication 26 38 470) has a fungicidal effect. The effect of these substances is not always sufficient at lesser amounts and concentrations. In addition, their fungitoxic effect is associated with a high phytotoxicity, such that the concentrations required for the control of phytopathogenic fungi such as e.g. the control of mildew, scab or rust fungi also damages important cultural plants or greatly inhibits their growth. Therefore, these compounds are not always suitable for controlling phytopathogenic fungi and not in all culture plants.

It has now been found that compounds of formula I

Ar - Z "" Y X — j {} -R2 I

A is R 2 O N in which R and R are hydrogen, alkyl of 1 to 5 C atoms or phenyl, Ar represents phenyl which may be substituted one or more times with fluoro, chloro, bromo nitro, trifluoromethyl, alkyl or alkoxy, each having 1 to 5 C atoms, and Z - having the meaning CH = C or CH 2 -CH, and X represents a -CO-, -CH (OH) - or - CH (OR 3) - ^ 3 group, where R represents an alkyl group having 1 to 8 4 4 C atoms or a -CO-R group, R represents an alkyl group having 1 to 5 C atoms, or salts or metal-

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2 complex compounds thereof, are extremely effective against harmful fungi, especially of the group ascomycetes and basiomyomycetes} and exhibit a very good plant tolerance

The compounds of formula I contain chiral centers 5 and / or double bonds and are usually available in the form of racemates or as diastereomer mixtures or xom Z and E isomer mixtures. The diastereomers and E and Z isomers can be separated for certain of the compounds of the invention by means of soy chromatography or by solubility differences and can be obtained in pure form. Further, from the common diastereomers, the common enantiomers can be obtained by known methods.

Agents containing these are also encompassed by the present invention. When using the compounds of the invention as fungicides, both the common diastereomers, enantiomers or the geometric isomers Z "and E" as well as the mixtures obtained by the syntheses are suitable. These mixtures are preferably used.

1 2 20 R and R represent e.g. hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, iso-butyl, tert-butyl, n-pentyl or phenyl.

Ar represents, for example, phenyl, 4-fluorophenyl, 2-chlorophenyl, 3-chlorophenyl, 4-chlorophenyl, 4-bromophenyl, 2,4-dichlorophenyl, 3,4-dichlorophenyl, 3,5-dichloro-2 -methoxyphenyl, 2,3,4-trichlorophenyl, 2-methoxyphenyl, 2,4-dimethoxyphenyl, 3-methoxyphenyl, 4-methoxyphenyl, 4-ethoxyphenyl, 4-tert-butoxyphenyl, 4-methylphenyl, 4-ethylphenyl, 4-isopropylphenyl, 4-tert.-butylphenyl, 3-nitrophenyl, 4-nitrophenyl, 3-trifluoromethylphenyl and 4-trifluoromethylphenyl.

X represents e.g. a carbonyl group (C = O) or a reduction alcohol (-CH-OH) produced thereof,

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3 may be etherified (to -CH-OR ^) or esterified (to -CH-OCOR ^). For example, R 5 may mean methyl, ethyl, n-propyl, n-butyl, n-pentyl or n-hexyl.

The compounds can be prepared by:

3a * converts 1,2,4-triazole with α-bromoketones of formula II

Ar-CIL-CHBr-CO v Γ ~ 0 /> ** 1 2 wherein R, R and Ar have the above meanings, or

b) reacting an aryl methyl halide of formula III

Ar-CH2-Y '' III,

wherein Ar is as defined above and Y'represents chlorine or bromine, with an 1- (1,3-dioxan-5-yl) -2- (1,2,4-triazolazolyl (s)) -ethane -l-one of formula IV

CH 5 -CO / O 2 .2 Y 2) -R 2 O 'in ° \ -1 R1 2 wherein R and R have the above meanings, or

c) reacting an aldehyde of formula V

Ar - CH = 0 V

wherein Ar has the above meanings, with the 1- (1,3-dio-xan-5-yl) -2- (1,2,4-triazoly1- (1)) -ethane-1-one derivative of formula IV

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4 and then optionally reduces the compounds produced and optionally subsequently converts them into esters or ethers.

The reaction (a) optionally occurs in the presence of a solvent or diluent, optionally with the addition of an inorganic or organic base and optionally with the addition of a reduction promoter at temperatures between 10 and 120 ° C. Among the preferred solvents and diluents are ketones such as acetone, methyl ethyl ketone or cyclohexanone, nitriles such as acetonitrile, esters such as acetic acid methyl ester, ethers such as diethyltether, tetrahydrofuran or dioxane, sulfoxides as dimethylsulfoxide, amides as dimethylsulfoxide, amides as dimethylsulfoxide, -don, in addition sulfolane or similar mixtures thereof.

Suitable bases, which may be further used as an acid binding agent in the reaction, are e.g. alkali hydroxides such as lithium, sodium or potassium hydroxide; alkali carbonates such as sodium or potassium carbonates or sodium and potassium hydrogen carbonate, excess 1,2,4-triazole, pyridine or 4-dimethylaminopyridine. Other common bases can also be used.

In particular, as reaction promoters, metal halides such as sodium iodide or potassium iodide, quaternary ammonium salts such as tetrabutylammonium chloride, bromide or iodide, benzyl triethylammonium chloride or bromide or crown ether such as 12-crown-4, 15-crown-5, 18-crown-6, 6-crown-6 -18-krone-6 or dicyclohexane-18-krone-6.

The reaction b) is optionally carried out 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. Among the preferred solvents and diluents are amides such as dimethylformamide, diethylformamide, dimethylacetamide, diethylacetamide,

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5 amide, N-methylpyrrolidone, hexamethylphosphoric triamide, sulfoxides such as dimethyl sulfoxide and finally sulfolane.

Suitable bases, which may also be used as an acid binding agent in the reaction, are e.g. alkali hydrides such as lithium, sodium and potassium hydride, alkali amides such as sodium and potassium amide, additional sodium or potassium tert.-butoxide, lithium, sodium or potassium triphenylmethyl and naphthalene-lithium, sodium, or potassium.

The aldehydes V are condensed with compounds IV optionally 2q in the presence of a solvent or diluent and optionally with the addition of an inorganic or organic base and / or acid at temperatures between -10 and 150 ° C, optionally under azeotropic separation of the reaction water. Among the preferred solvents and diluents include water, alcohols such as methanol, ethanol, isopropanol and tert-butanol, hydrocarbons such as n-hexane, n-heptane, n- and iso-octane, cyclohexane, tetrahydronaphthalene, decahydronaphthalene, toluene , xylene, cumene; amides such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone and ethers 2q such as diethyl ether, methyl tert-butyl ether, dioxane, tetrahydrofuran or similar mixtures.

The reaction is usually carried out at temperatures between 20 and 150 ° C, without pressure or under pressure, continuous or discontinuous.

The 1- (1,3-dioxan-5-yl) -2- (1,2,4-triazolyl- (1)) -ethane-1-ones

of formula IV are novel. For example, they can is obtained by reacting the 1- (1,3-dioxan-5-yl) -2-halo-ethane-1-ones of formula VI

β-ch 2 -co wherein R 1 and R 2 have the above meanings, and Y represents 30 chlorine or bromine, with the sodium salt of 1,2,4-triazole.

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6

The compounds of formula VI are also novel.

These are available e.g. by reaction of known (1,3-dioxan-5-yl) -ethane-1-ones of formula VII

ILC-COn / + ° 2

3 RI \ _ O "'R VII

17 wherein Rx and R have the above meanings, e.g. with the 5-pyrrolidone-bromo complex described by D.P. Wyman and P. R. Kaufman, J. Org. Chem. 29, 1956 (1964).

The ketones prepared according to a, b or c are optionally reduced in the presence of a solvent or diluent, at temperatures between -20 to 150 ° C, at normal pressure or under elevated pressure with hydrogen in the presence. of a catalyst, with complex boron or aluminum hydrides, with aluminum isopropoxide and isopropanol, with sodium dithionite or electrochemically.

Suitable solvents or diluents for this reduction are e.g. water, methanol, ethanol, isopropanol, acetic acid, diethyl ether, tetrahydrofuran, dioxane, vinegar ester, toluene, dimethylformamide or similar mixtures.

catalytic hydration, platinum or palladium catalysts are used on inert carriers and hydrogenated at pressures from 2 to 80 bar until no further hydrogen uptake occurs.

The hydrides used as reducing agents are e.g. sodium borohydride or lithium aluminum hydride.

The alcohols of formula I thus obtained (X = CHOH) can

is etherified with alkylating agents of formula VIII

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7 V - R3 VIII, wherein R3 is as defined above, and V represents chlorine or bromine, optionally in the presence of a solvent or diluent forming a 1 or 2-phase system, optionally with the addition of an inorganic base, and -5 by addition of a reaction promoter and / or phase transfer catalyst.

For this purpose, the following solvents or diluents are suitable: diethyl ether, tetrahydrofuran, dioxane, n-pentane, monohalogenated hydrocarbons having 2-6 C atoms, e.g. chloroethane, bromethane, 1-chloropropane, 1-bromopropane, 1-chlorobutane, 1-bromobutane, 1-chloropentane, 1-bromopentane, 1-chlorohexane, 1-bromohexane, additional cyclohexane, methylene chloride, chloroform, toluene or dimethylformamide .

As inorganic bases, e.g. Mention is made of: alkali and alkaline earth hydroxides, e.g. sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide, alkali and alkaline earth carbonates such as sodium carbonate, potassium carbonate, sodium bicarbonate, potassium hydrogen carbonate, calcium carbonate, barium carbonate, alkali or alkaline earth carbonates, e.g. sodium methylate, sodium ethylate, magnesium methylate, sodium isopropylate or potassium tert-butylate.

Suitable reaction promoters are e.g. metal halides such as sodium bromide, sodium iodide, potassium bromide, potassium iodide, tertiary amines such as e.g. 4-dimethylaminopyridine or 4-pyrrolidinopyridine, crown ethers such as 12-crown-4, 14-crown-5, 18-crown-6, dibenzoe-18-crown-6 or dicyclohexano-18-crown-6 or azoles such as imidazole and 1, 2,4-triazole.

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8

As phase transfer catalysts, e.g. quaternary ammonium salts such as tetrabutylammonium chloride, bromide, iodide or hydrogen sulfate, benzyl triethylammonium chloride, methylthiooctylammonium chloride and bromide and phosphonium salts such as tetrabutylphosphonium bromide and iodide and pentomium

The esterification of the alcohols of formula I (X = CHOH) may be carried out with acid chlorides or anhydrides of formula Y-CO-R 2 (IX) or (R 2 -CO 2 OCX) optionally in the presence of a solvent or diluent, optionally un - adding acid binder and optionally adding a reaction promoter. For this purpose, the same solvents and bases as for the etching can be used. Further, tertiary amines such as trimethylamine, triethylamine, N, N-dimethylaniline, N, N-dimethylcyclohexylamine, N-methylpiperidine or pyridine can be used as bases.

With the aid of suitable bases such as, for example, alkali hydrides such as sodium hydride or alkali or alkaline earth alcoholates 20 as sodium methylate, the alcohols may also be converted to their alcoholate salts at first reaction and then converted to these.

The compounds of formula I prepared are isolated in the usual manner, optionally the compounds are purified and optionally reacted with acids or metal salts for the salts or metal complexes.

The following examples illustrate the preparation of the compounds of the present invention, and biological comparisons of the effect of certain of the compounds of this invention are listed.

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EXAMPLE 1 a) Preparation of starting material

To a solution of 144 g (1 mole) of 5-acetyl-5-methyl-1,3-dioxane and 83.5 g (1 mole) of pyrrolidone in 500 ml of tetrahydrofuran is dropped in the lab of two hours at 50 ° C. a solution of 498 g (1 mole) of pyrrolidone-bromine complex in one liter of tetrahydrofuran. After stirring for 8 hours at 50 ° C, the white precipitate of pyrrolidone hydrobromide washed with 50 ml of tetrahydrofuran is filtered off and the filtrate is evaporated in vacuo. 220 g (99¾) of rat, oily 1- (5-methyl-1,3-dioxan-5-yl) -2-bromo-ethan-1-one are obtained.

To a suspension of pure nitrogen, 100.1 g (1.1 mole) of sodium 1,2,4-triazolid in 300 ml of tetrahydrofuran was added dropwise a solution of 223 g (1 mole) of 1- (5 m (15-methyl-1,3-dioxan-5-yl) -2-bromo-ethan-1-one in 200 ml of tetrahydrofuran in the two-hour lab at 25 ° C. After 8 hours of refluxing, the inorganic precipitate is filtered off and the filtrate is evaporated to half.

The mixture is seeded and left to stand overnight at +3 ° C. The precipitate 20 is aspirated, washed with 30 ml of cold (+5 ° C) tetrahydrofuran, then with 80 ml of ether and finally with 100 ml of n-pentane and terres. 184 g (87.2¾) of 1- (5-methyl-1,3-dioxan-5-yl) -2- (1,2,4-triazolyl- (1)) ethan-1-one are obtained as white crystals having a melting point of 95 to 97 ° C.

B) Preparation of the final product

To a suspension of 13.2 g (0.55 mole) of sodium hydride under pure nitrogen stirred in 100 ml of dimethylformamide, a solution of 105.5 (0.5 mole) of 1- (5-methyl-1,3-dioxane) is added dropwise. 5-yl) -2- (1,2,4-triazolyl- (1)) -ethane-1-one in 100 ml of dimethylformamide at 20 to 25 ° C. After three hours of stirring at 25 ° C, a solution of 81 g (0.5 g) is added dropwise

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10 moles of 4-chlorobenzyl chloride in 50 ml of dimethylformamide, and the reaction mixture is stirred an additional 14 hours. Gently drop 50 ml of ice water and evaporate the mixture in vacuo. The residue is shaken between 400 ml of methylene chloride and 200 ml of water, the organic phase is washed three times with 200 ml of water per ml. time, which is then quenched over Na ^ SO ^ and evaporated. 112 g (66.8%) of 1- (5-methyl-1,3-dioxan-5-yl) -2- (1,2,4-triazolyl- (1)) -3- (4-chlorophenyl) are obtained. ) -propan-1-one as a pale yellow resin.

1 H NMR (80 MHz / CDCl 3): = 0.87 (s, 3H), 3.1-3.6 (m, 4H), 3.95-4.4 (t, 2H), δ , 5-5.0 (2 dd, additional 2H), 5.65-5.95 (q, 1H), 6.8-7.3 (m, 4H), 7.8 (s, 1H), 8.0 ppm (s, 1H).

EXAMPLE 2

To a solution of 90 g (0.269 mol) of 1- (5-methyl-1,3-dioxan-5-yl) -2- (1,2,4-triazolyl- (1)) - 3- (4- chlorophenyl) propan-1-one in 250 ml of methanol is added portionwise between 0 and + 5 ° C 11.5 g (0.3 mol) of sodium borohydride. After 12 hours of stirring, the mixture is evaporated at 20 ° C. The residue is stirred with 200 ml of 20% potassium for one hour and extracted with 500 ml of methylene chloride. The organic phase is washed three times with 50 ml of water per ml. The mixture is stirred over sodium sulfate and evaporated. The residue is crystallized by the addition of 20 ml of ether at +5 ° C. 45 g (49.6%) of 1- (5-methyl-1,3-dioxan-5-yl) -2-25 (1,2,4-triazolyl- (1)) -3- (4- chlorophenyl) -propan-l-ol. as - white crystals having a melting point of 152 to 154 ° C.

EXAMPLE 3

With vigorous stirring, a mixture of 15.2 g (0.045 mol) of 1- (5-methyl-1,3-dioxan-5-yl) -2- (1,2,4-triazolyl- (1)) is heated. ) -3- (4-chlorophenyl) -propan-1-ol, 100 g of 1-chloropropane ·, 3 g of tetrabutylammonium hydrogen sulfate and

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11 65 g 50¾ baking soda for 36 hours at 30 ° C. The mixture is then added with 300 ml of water and extracted twice with 150 ml of methylene chloride per ml. walk. The combined extracts are shaken eight times with 100 ml of water. once, terres 5 over magnesium sulfate and evaporate. The residue crystallizes after the addition of 20 ml of petroleum ether and 5 ml of ether. 12 g (7 0.3 Si) 1- (5-methyl-1,3-dioxan-5-yl) -1n-propoxy-2- (1,2,4-triazolyl- (1)) -3 - (4-chlorophenyl) -oropane as white crystals, mp 94 to 96 ° C.

• EXAMPLE 4

A mixture of 20 g (0.053 mol) of 1- (5-methyl-1,3-dioxan-5-yl) -2- (1,2,4-triazolyl- (1)) - 3- (2.4 dichlorophenyl) -propan-1-ol (see Example 35), 2 g of imidazole and 100 ml of propionic acid are stirred for 10 hours at 60 ° C, then evaporates 1; passport. The residue is dissolved in 250 ml of ether and stirred for 30 minutes with 100 ml of a 6% sodium bicarbonate solution. The organic phase is triturated over sodium sulfate and evaporated in vacuo, finally at 50 ° C and 0.1 mbar.

17.1 g (75.4¾) of 1- (5-methyl-1,3-dioxan-5-yl) -1-acetoxy-2- (1,2,4-triazolyl- (1)) are obtained. 3- (2,4-dichlorophenyl) propane as a light brown resin. 1 H NMR (80 MHz / CDCl 3): = 0.85 (s, 3H), 1.15-1.4 (t, 3H), 2.4-3.2 (q, 2H), 3.3 -3.6 (m, 2H), 3.8-4.2 (m, 2H), 4.6-5.1 (2 dd, additional 2H), 6.1 (s, 1H), 6, 5-7.6 (2 tt, further 4H), 8.1 (s, 1H) and 8.28 ppm (s, 1H).

EXAMPLE 5

Under water separation and at reflux, a mixture of 12.7 g (0.06 mol) of 1- (5-methyl-1,3-dioxan-5-yl) -2- (1,2,4-triazolyl- (1 ) - Ethane-1-one, 10.8 g (0.06 mol) of 2.4-30 dichlorobenzaldehyde, 1 g of piperidine, 0.5 g of acetic acid and 150 ml of toluene for 10 hours. The mixture is cooled, washed three times with 80 ml of water per ml. aisle, terres over sodium sulfate and

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12 is evaporated in vacuum. The residue is dissolved in 250 ml of acetonitrile, decolorized at 40 ° C with 1 g of activated carbon, evaporated to 40 ml and cooled to 0 ° C. The colorless precipitate is aspirated, washed with ether (40 ml) and terres. 18.4 g (83.33) of 5- (5-methyl-1,3-dioxan-5-yl) -2- (1,2,4-triazolyl- (1)) - 3- ( 2,4-dichlorophenyl) -propen-1-one, mp 133-135 ° C.

EXAMPLE 6

To a solution of 36.1 g (0.1 mole) of 1- (5-methyl-1,3-dioxan-5-yl) -2- (1,2,5-triazolyl- (1)) -3 - (2,4-dichlorophenyl-propyl-1-one in 250 ml of methanol is added 4.5 g (0.118 mol) of sodium borohydride at between -5 and 0 ° C. After 14 hours of stirring at 22 ° C, the white precipitate is suctioned off and the filtrate is evaporated in vacuo. The precipitate and residue 25 are combined and stirred for half an hour with 3 liters of methylene chloride and 500 ml of 10 ml of potash at 25 ° C. The organic layer is separated, washed three times with 100 ml of water. The residue is crystallized by the addition of 10 ml of ether to give 31.3 g (84.6%) of 1- (5-methyl-1,3-dioxan-5-yl) - 2- (1,2,4-triazolyl- (1)) - 3- (2,4-dichlorophenyl) -propen-1-ol as colorless crystals having a melting point of 190 - 192 ° C.

EXAMPLE 7

A mixture of 14 g (0.0378 mol) of 1- (5-methyl-1,3-dioxan-5-yl) -2- (1,2,4-triazolyl- (1)) - 3- (3 , 4-Dichlorophenyl) -propen-1-ol (Example 25), 1 g of imidazole and 80 g of acetanic anhydride are stirred for 8 hours at 70 ° C and then evaporated in vacuo. The residue is read into 300 ml of ether and stirred for half an hour with 100 ml of 6% sodium bicarbonate solution. The organic phase is triturated over sodium sulfate and evaporated in vacuo, finally evaporated at 50 ° C and 0.1 mbar. 10.8 g (69.3 µl of theoretical yield) of 1- (5-methyl-1,3-dioxan-5-yl) -1-acetoxy-2- (1,2,4-triazo-2-yl) are obtained.

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13-yl- (1)) - 3- (3,4-dichlorophenyl) -propen-2 as a pale yellow resin.

1 H NMR (80 MHz / CDCl 3): = 0.6 (s, 3H), 2.08 (s, 3H), 3.2-3.4 (m, 2H), 3.8-4.0 ( g, 2H), 4.4-4.9 (2 dd, further 2H), 5.5 (s, 1H), 6.3-7.4 (m, further 4H), 8.0 ( s, 1H) and 8.2 ppm (s, 1H).

Similarly, the precursors listed in the following table can be made.

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DK 156608 B

27

The compounds of this invention and their salts and metal complexes exhibit excellent efficacy against a wide range of plant pathogenic fungi, especially of the group of ascomycètes and basidyomycetes. They are partly systemic and can be used in soybean and soil fungicides. In addition, they can be used in material protection, among other things, to control wood-decomposing fungi such as Conoiphra puteana and Polystictus versicolor.

Particularly interesting is the use of the fungicidal compounds for the control of a variety of fungi in different species: cultural plants and in particular, on white, rye, barley, oats, rice, maize, cotton, soy, coffee, sugar cane, fruit and ornamental plants, for horticulture, as well as in vegetables such as. cucumbers, banner and pumpkin.

15 The compounds of the invention are particularly suitable for the control of declining plant diseases:

Erysiphe graminis (real mildew) in cereals,

Erysiphe cichoriacearum in pumpkin,

Podosphaera leucotricha on apples, 20 Uncinula necator on wine,

Puccinia species in cereals,

Rhizoctonia solani on cotton,

Ustilago species in cereals and sugarcane,

Venturia inaequalis (scab) on apples, 25 Septoria nodorum on wheat,

Brotytis cinera (grass mold) on strawberries and wine ,,

Phtophthora infestans (false mildew) on potatoes and tomatoes.

The compounds are used by spraying plants 30 or spraying pesticides thereon, or by treating the seeds with the active compounds. The application is done father or after the attack of the fungi on the plants

DK 156608 B

28 or fraene.

The compounds of the invention can be transferred to conventional formulations such as e.g. solutions, emulsions, pensions, spellings, powders, pastes and granules.

5 The mode of use depends entirely on the mode of use; they must in all cases be in a fine and uniform distribution of the active compound. The compositions are prepared in the usual manner e.g. by adding solvents and / or carriers to the active compound, optionally employing emulsifiers and dispersants, in which case water can be used as a diluent, but also other organic solvents as auxiliary solvents. As auxiliaries for this purpose, the following are available: solvents such as aromatics (eg xylene, benzene), chlorinated aromatics (eg chlorobenzene), paraffins (eg petroleum fractions), alcohols (e.g., methanol, butanol), amines (e.g., ethanolamine, dimethylformamide), and water; carriers such as e.g. natural stone flour such as kao-20 linen, clay soil, talc, chalk and synthetic stone flour (e.g.

hay dispersed silicic acid, silicates); emulsifiers other than ionic and anionic emulsifiers (e.g., polyoxyethylene fatty alcohol ether, alkyl sulfonates and aryl sulfonates) and dispersants such as lignin, sulfite liquor and methyl cellulose.

The fungicidal agents usually contain between 0.1 and 95, preferably between 0.5 and 90% by weight of the active compound.

Depending on the desired power, the amount used ranges from 0.1 to 3 kg of active compound or more per liter. ha.

The compounds in question can also be used among others to combat wood decomposing fungi such as Coniophora

DK 156608 B

29 puteana and Polystictus versicolor. With the use of the active compound for material protection e.g. as a fungicide for paints and blood polyvinyl chloride, the amount used is 0.05 to 5% by weight, calculated actively on the total weight of the colors or micronutriable polyvinyl chlorides to be preserved. The present compounds can also be used as an active ingredient in oily wood preservatives to protect the wood from wood decaying fungi. The use is made 10 in the way that the wood is treated with the means e.g.

brush or soak the tree with the means.

The agent or preparations thereof are used as solutions, emulsions, suspensions, powders, stoves, pastes or granules in a manner known per se in e.g. spraying, spraying, forming, stretching, pickling or pouring.

In 20 parts by weight of compound # 6 are mixed in 3 parts by weight of the sodium salt of isobutylnaphthalene sulfonic acid, 17 parts by weight of the sodium salt of a lignin sulfonic acid from a sulfite liquor and 60 parts by weight of powdered silicic acid and formatted on a hammer flour. By finely dividing the mixture into 20,000 parts by weight of water, a dispersive solution containing 0.1% Si of the active compound is obtained.

25 II parts by weight of the compound of Example 15 are thoroughly mixed with 97 parts by weight of finely divided kaolin. In this way, a stoving agent containing 3% by weight of the active compound is obtained.

III 30 parts by weight of the compound of Example 1 are thoroughly mixed with a mixture of 92 parts by weight of powdered silica gel and 8 parts by weight of paraffin oil and sprayed onto the surface of the silica gel. At that time

DK 156 6 Ο 8 B

there is a preparation of the active compound with good adhesion.

IV 40 parts by weight of the compound of Example 21 are thoroughly mixed with 10 parts of sodium salt of a phenolic sulfonic acid-urea-formaldehyde condensate, 2 parts of silica gel and 48 parts of water. A stable aqueous dispersion is obtained.

Dilution with 100,000 parts by weight of water gives an aqueous dispersion containing 0.04% by weight of the active compound.

10 V 20 parts of the compound of Example 33 are mixed thoroughly with 2 parts potassium salt of dodecylbenzenesulfonic acid, 8 parts fatty alcohol polyglycol ether, 2 parts sodium salt of a phenolic sulfonic acid urea-formaldehyde condensate and 68 parts of a paraffinic mineral oil. You get a stable oil dispersion.

We mix 90 parts by weight of the compound of Example 1 with 10 parts by weight of N-methyl-α-pyrrolidone and obtain a solution suitable for use in very small drops.

20 VII 20 parts by weight of the compound of Example 16 is dissolved in a mixture consisting of 80 parts by weight of xylene, 10 parts by weight of the addition product of 8 to 10 moles of ethylene oxide on 1 mole of oleic acid N-monoethanolamide, 5 parts by weight of calcium salt of dodecylbenzenesulfonic acid and 5 parts by weight of the addition product of 40 moles of ethylene oxide on 1 mole of castor oil. By precipitating and decomposing the solution into 100,000 parts by weight of water, an aqueous dispersion containing 0.02% by weight of the active compound is obtained.

30 VIII 20 parts by weight of the compound of Example 25 are dissolved in a mixture consisting of 40 parts by weight of cyclohexa-

DK 156608 B

31 non, 30 parts by weight of isobutanol, 20 parts by weight of the addition product of 7 moles of ethylene oxide on 1 mole of iso-octylphenol and 10 parts by weight of the addition product of 40 moles of ethylene oxide on 1 mole of castor oil. By pouring out and finely dividing the solution into 100,000 parts by weight of water, an aqueous dispersion containing 0.02% by weight of the active compound is obtained.

IX 10 parts by weight of the compound of Example 88, 20 parts by weight of polyoxyethylene sorbitan monolaurate (2 Tw / one 10 20), 20 parts by weight of methanol and 50 parts by weight of water are stirred to a solution containing 10% by weight of the active compound. By adding additional water, a highly diluted solution can be prepared.

The agents of the invention may be admixed with other active compounds, e.g. herbicides, insecticides, growth regulators and fungicides or also by means of wetting agents and applied with these. By mixing with fungicides, a broader spectrum of efficacy is thus often obtained. In a whole series of these fungicide mixtures, synergistic effects, e.g. the overall effect of the combination preparation is more rigorous than the added effects of the simple components.

Fungicides which can be combined with the subject compounds are e.g. dithiocarbamates and derivatives thereof such as f.

25 items

Ferridimethyldithiocarbamate, zinc dimethyldithiocarbamate, manganese ethylene bisthiocarbamate, manganese-zinc-ethylenediamine bis-dithiocarbamate, zinc ethylene bisthiocarbamate, tetramethylthiuramide sulfides, 32

DK 156608 B

ammonia complex of zinc (N, N-ethylene bis-dithiocarbamate and N, N'-polyethylene-bis- (thiocarbamoyl) disulfide, zinc (N, N'-propylene-bis-dithiocarbamate), ammonia complex of tin (N, N '-propylene bis-dithiocarbamate) and 5N, N'-polypropylene-bis (thiocarbamoyl) disulfide; nitrophenol derivatives such as dinitro (1-methylheptyl) phenylcrotonate, 2-sec -butyl-4,6-dinitrophenyl-3,3-dimethylacrylate, 2-sec-butyl-4,6-dinitrophenyl isopropyl carbonate; heterocyclic compounds such as e.g.

N-trichloromethylthio-tetrahydrophthalimide, N-trichloromethylthiophthalimide, 2-heptadecyl-2-imidazole acetate, 2,4-dichloro-6- (o-chloroanilino) -s-triazine, 0.0-diethyl-phthalimidophosphonate ionate, 5 -amino-1- (bis- (dimethylamino) -phosphinyl) -3-phenyl-1,2,4-triazole, 5-ethoxy-3-trichloromethyl-1,2,4-thiadiazole, 2,3-dicyano-1,4 -dithioanthrachinone, 2-thio-1,3-dithio- (4,5-b) -quinoxaline, 1-butylcarbamoyl-2-benzimidazole-carbamic acid methyl ester, 2-methoxycarbonylamino-benzimidazole, 2-rhodanmethylthio-benzthiazole, 4- (2) -chlorophenylhydrazono) -3-methyl-5-isoxazolone, pyridine-2-thiol-1-oxide, 8-hydroquinoline or the copper salt thereof, 2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxathiin-4, 4-di-oxide, 2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxathiine, 2- (furyl-2) -benzimidazole, piperazine-1,4-diyl-bis-1- (2, 2,2-trichloroethyl) -formamide, 2-thiazolyl- (4-benzimidazole, 5-butyl-2-dimethylamino-4-hydroxy-6-methyl-pyramidine, bis- (p-chlorophenyl) -3-pyridine methanol,

DK 156608 B

33 1,2-bis (3-ethoxycarbonyl-2-thioureido) benzene, 1,2-bis- (3-methoxycarbonyl-2-thioureido) benzene, and various fungicides such as e.g. dodecylguanidine acetate, 3- (2- (3,5-dimethyl-2-oxycyclohexyl) -2-hydroxyethyl) -glutarimide, hexachlorobenzene, N-dichlorofluoromethylthio-NjN'-dimethyl-N-phenyl-sulfuric acid diamide, 10 D , L-methyl-N- (2,6-dimethyl-phenyl) -N-futyl (2) -alaninate, D, LN- (2,6-dimethyl-phenyl) -N- (2'-methoxyacetyl) -alanine methyl ester, 5-nitro-isophthalic acid di-isopropyl ester, 2,5-dimethyl-furan-3-carbonic anilide, 2,5-dimethyl-furan-3-carbonic acid cyclohexylamide, 2-methyl-benzoic anilide, 1- (3 , 4-dichloroanilino) -1-formylamino-2,2,2-trichloroethane, 2,6-dimethyl-N-tridecyl-morpholine or its salts, 2,6-dimethyl-N-cyclododecyl-morpholine or its salts, 2,3-dichloro -1,4-naphthoquinone, 1,4-dichloro-2,5-dimethoxybenzene, p-dimethylaminobenzene diazine sodium sulfonate, 1-chloro-2-nitro-propane and polychloronitrobenzenes such as pentachlorone nitrobenzene, methyl isocyanate, fungicidal antibiotics such as griseofulvin , tetrafluorodichloroacetone, 1-phenylthiosemicar bazide, burgundy, nickel-containing compounds and so on v / 1st

The following examples show the biological effect of the 30 compounds. As a comparative compound, 2,2-dimethyl-4- (1,2,4-triazol-1-yl) -5-phenyl-pentan-3-one (A) is used (German Publication No. 26 38 470).

DK 156608 B

EXAMPLE A Wheatmeal.

Leaves of wheat seedlings growing in herb pots of the "Jubilar" variety are sprayed with an aqueous emulsion of 80% (wt.%) Of active compound and 20% emulsifier 5 and seeded after drying the spray with oidia (spore) of wheat mildew (Erysiphe graminis var. tritici). The seal plants are then placed in greenhouses at temperatures between 20 and 22 ° C and at 75 to 80% relative humidity. After 10 days, the development of the mildew attack is stopped. In this experiment, especially, the compounds of Examples 2, 3, 4, 9, 12, 17, 20, 21, 27, 50, 52, 60 and 92 showed a better effect than A.

Table 1

Active compound Infestation of leaves after spraying with ..% ig active solution _0.025 0.006_0.0015 2 0 0 1 3 0 0 2 4 0 0 1 9 0 0 0 12 0 12 17 0 0 1 20 0 0 2 21 0 1 2-3 27 0 0 1 50 000 '52 0 0 1 60 0 0 2 92 0 0 0

Table 1 (continued) 35

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Active connection Attack of leaves after spraying with ..? Ôig active / reading _0,025 0.006 0.0015

Comparative A 2 2-3 2-3

Control (untreated) 5 0 = no attack, escalated to 5 = total attack.

EXAMPLE B

Whewed brown rust.

Leaves of wheat seed of the "Caribo" variety, which grows 1 herb pots, are pollinated with spores of brown rust (Puccinia 5 recondita). Then place the pots for 24 hours: at 20 to 22 ° C in a chamber with high humidity (90 to 95%). · For 10 months, the spores germinate and the germinated spores penetrate the leaf tissue. The infected plants are then sprayed with a 0.025 wt.% Aqueous 10 spray liquid containing 80¾ active compound and 20¾ lignin sulfonate in the tar until they drip.

After tarring the sprayed, the pre-plant plants are placed in greenhouses at temperatures between 20 and .22 ° C and at 65 to 70¾ relative humidity. Eight days after 15 beds, the development of rust fungi on the leaves.

In this experiment, in particular, the compounds 16 and 50 appear to be better than A.

Table 2

Active compound Leaf infestation after spraying with 0.25-oig d-ctive reading 16 0 50 0

Active compound Leaf infestation after spraying with 0.25 ° C active solution

Table 2 (continued) 36

DK 156608 B

Comparative A 2

Control (untreated) 5 0 = no attack, escalated to 5 = total attack.

EXAMPLE C Akurmelduq ♦

Leaves of cucumber seedlings growing in herb pots are sprayed with an aqueous emulsion of 80¾ active compound and 20¾ emulsifier and after drying the sprinkled powder with oidia (spores) of cucumber mildew (Erysiphe cichoracearum). The test plants are then placed in greenhouses at temperature-e-r-between-am · -20 and · 22- ° C and at 75 to 80¾ relative humidity. After 10 days the extent of mildew fungus development is assessed.

The results are given in the table below. All compounds tested were better than Comparative Compound A.

Table 5

Active compound Attack of leaves after spraying -Dr · _____ ninq with 0, Q12-? Ôiq active solution 2 0 3 1 4 0 6 0 12 0

Active compound Leaf infestation after spraying with no.

DK 156608 B

Table 3 (continued) 15 1 16 0 17 1 18 1 19 1 20 0 21 0 22 0 23 0 24 1 25 0 30 0 33 0 39 0 41 1 44 0 45 0 47 1 49 1 50 0 51 2 52 0 53 0 54 0 55 1 56 0 58 0 59 0 62 0 66 '0 68 0 74 0

Active compound Leaf infestation after spraying with Q, Q12 ° ° active solution

Table 3 (continued) 38

DK 156608 B

77 0 78 0 80 0 90 0 92 0 94 0 95 0 97 0 107 0 109 0 112 0 114 0 119 0 120 0 121 0 122 0

Comparative A 2-3

Control (untreated) 5 0 = no attack, escalated to 5 = total attack.

EXAMPLE D

Septoria nodorum on wheat.

Leaves of wheat plants of the "Jubilar" variety growing in herb pots were sprayed to drip water with aqueous spray solutions having 0.1% / wt.% Active compound emulsified therein. After drying the sprayed on-board plants, a spore slurry from mushrooms of Septoria nodorum was placed and placed at 16 to 18 ° C in a room with high humidity to obtain optimum conditions for fungal development.

DK 156608 B

39 gen. After 14 days, the disease had developed so strongly on the untreated control plants that the spots on the leaves covered the entire leaf predominantly. .........

In this test, especially, the compounds of Examples 60 and 73 exhibit strong activity over the untreated control.

Table 4

Active compound Extent of attack by leaves after treatment with 0.1% -in active solution 60 0 73 1

Control (untreated) 5 0 = no attack, escalated to 5 = total attack.

EXAMPLE E

Botrytis cinerea on pepper.

10 Pepper seedlings of the "Neusiedler Idéal Elite" variety were sprayed until they were drip water, after the fourth to ferrite leaves were well developed, with 0.1% aqueous suspension containing 80¾ active compound and 20¾ sodium lignin sulfonate in the substance. . After drying the sprayed 15, the plants were sprayed with a conidial slurry of the fungus

Botrytis cinerea and placed at 22 to 24 ° C in a high humidity chamber to obtain optimum conditions for fungal development. After 5 days, the disease had developed so strongly on the untreated control plants that the emerged leaf necrosis covered the predominant part of the leaves.

40

DK 1566 Ο 8 B

The results are given in the table below.

Table 5

Active compound Leaf necrosis after spraying.

_no_with 0, l% ig active solution_ 21 2 27 1 34 1 33 2

Control (untreated) 5 0 = no attack, escalated to 5 = total attack.

EXAMPLE F

Phytophthora infestans on tomatoes.

Leaves of tomato plants of the "Professor Rudloff" variety were sprayed with aqueous suspensions containing 80% by weight of the active compound and 20% of sodium lignin sulphonate in the tar. 0.05 and 0.025% spray liquid m (calculated on the tar substance) was used. After tarring, the leaves were infected with a zoospore slurry of Phytophthora infestans. The plants were then placed 10 in a water vapor-saturated chamber at temperatures between 16 and 18 ° C. After 5 days, the disease had developed so strongly on the untreated but infected control plants that the fungicidal effect of the compounds could be assessed.

The results are shown in the table below.

Table 6 41

DK 156608 B

Active compound Leaf infestation after spray no.? Oigactif solution _0.05_0.025_ 27 1 1 50 0 0

Comparative A4 4

Control (untreated) 5. 0 = inte-t attack, stair t up to 5 = tôt ait attack.

Claims (3)

1. A fungicidal agent, characterized in that it contains as an active ingredient a triazolyl derivative of the formula Ar - Z— y— - X - / R 2 R 2 alkyl or phenyl, Ar represents a phenyl group which may be substituted one or more times by fluorine, chlorine, bromine, nitro, trifluoromethyl, C1-6 alkyl or C1-6 alkoxy, Z1-6 Y represents CH = C or CH ^ -CH, and 10. represents a -CO-, -CH (OH) - or -CH (OR ^) group, 4 wherein R represents a C C g g alkyl group - or a -CO-R group - Δ pe, where R represents an alkyl group or salts or metal complexes thereof. 2. A fungicide according to claim 1, characterized in that it contains as triazolyl derivative of formula I wherein R 2 and R 2 represent hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl or phenyl, Ar phenyl, 4-fluorophenyl, 4-chlorophenyl, 4-bromo-phenyl, 2,4-dichlorophenyl, 3,4-dichlorophenyl or 4-ethoxy-phenyl, and X represents a -CO-, -CH (OH) - or -CH (ORR ^) group, wherein R ^ represents ethyl, n-butyl, acetyl or propionyl. 3. A method for controlling phytopathogenic fungi, DK 156608 B, characterized in that a fungicidal agent according to claim 1 is allowed to affect these or in the places, plants or soils threatened by suicide attacks. CS '